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’- pU8-C 197

NBS

PUBLICATIONS

NSRDS-NBS 61, Part II

U.S. DEPARTMENT OF COMMERCE /

National Bureau of Standards
NATIONAL BUREAU OF STANDARDS

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The National Bureau of Standards was reorganized, effective April 9, 1978.
Hsffisna! Sure&n of Standards

APR 2 7 19?§

Physical Properties Data Compilations

Relevant to Energy Storage. '5)C 100

i) 5 ? ^

II. Molten Salts: Data on Single

and Multi-Component Salt Systems

G. J. Janz, C. B. Allen, N. P. Bansal,

R. M. Murphy, and R. P. T. Tomkins

Molten Salts Data Center,

Cogswell Laboratory

Rensselaer Polytechnic Institute

Troy, New York 12181

NSRDS)

(VflX 9t-vv u 0 fu i ( ( p

,

. ; i.

: ,r ; : /

; / U.S. DEPARTMENT OF COMMERCE, Juanita M. Kreps, Secretary

Jordan J. Baruch, Assistant Secretary for Science and Technology

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

Issued April 1979
Library of Congress Cataloging in Publication Data (Revised)

Main entry under title: Physical properties data compilations relevant to energy storage. (Nat. stand, ref. data ser. : NSRDS-NBS 61, pt. 1,2-)

"National Standard Reference Data System.”

Bibliography: p. CONTENTS: 1. Molten salts: eutectic data--

2. Molten salts: data on single and multi-component salt systems.

Supt. of Docs, no.: 03.48:61

1. Energy storage. 2. Fused salts. 3. Eutectics. I. Janz, George J.

II. Series: United States. National Bureau of Standards. National stand- ard reference data series ; NSRDS-NBS 61 , pt. 1

- QC100.U573 no. 61, pt. 1 , etc. 602’.ls [621] 77-10824

NSRDS-NBS 61, Part II

Nat. Stand. Ref. Data Ser., Nat. Bur. Stand. (U.S.),[61, Part II, 442 pages (Apr. 1979)

CODEN: NSRDAP

© 1979 by the Secretary of Commerce on Behalf of the United States Government

U.S. GOVERNMENT PRINTING OFFICE

WASHINGTON: 1979

For sale by the Superintendent of Documents, U.S. Government Printing Office Washington, D.C. 20402

Stock Number 003-003-02061-6
Foreword

The National Standard Reference Data System provides access to the quantitative data of physical science, critically evaluated and compiled for convenience and readily accessible through a variety of distribution channels. The System was established in 1963 by action of the President’s

Office of Science and Technology and the Federal Council for Science and Technology, and

responsibility to administer it was assigned to the National Bureau of Standards.

NSRDS receives advice and planning assistance from a Review Committee of the National

Research Council of the National Academy of Sciences-National Academy of Engineering. A number of Advisory Panels, each concerned with a single technical area, meet regularly to examine

major portions of the program, assign relative priorities, and identify specific key problems in

need of further attention. For selected specific topics, the Advisory Panels sponsor subpanels

which make detailed studies of users’ needs, the present state of knowledge, and existing data re- sources as a basis for recommending one or more data compilation activities. This assembly of

advisory services contributes greatly to the guidance of NSRDS activities.

The System now includes a complex of data centers and other activities in academic insti- tutions and other laboratories. Components of the NSRDS produce compilations of critically

evaluated data, reviews of the state of quantitative knowledge in specialized areas, and computations of useful functions derived from standard reference data. The centers and projects also

establish criteria for evaluation and compilation of data and recommend improvements in ex- perimental techniques. They are normally associated with research in the relevant field. The technical scope of NSRDS is indicated by the categories of projects active or being

planned: nuclear properties, atomic and molecular properties, solid state properties, thermodynamic and transport properties, chemical kinetics, and colloid and surface properties.

Reliable data on the properties of matter and materials are a major foundation of scientific

and technical progress. Such important activities as basic scientific research, industrial quality control, development of new materials for building and other technologies, measuring and correcting

environmental pollution depend on quality reference data. In NSRDS, the Bureau’s responsibility

to support American science, industry, and commerce is vitally fulfilled.

Ernest Ambler, Director

III
Preface

This series of publications is aimed at providing physical properties data on materials used in energy

storage systems. It was inspired by a requirement in the Department of Energy’s Division of Energy

Storage Systems for materials property data needed by its contractors in the timely development of energy

storage devices. As prime contractor for this program, the Lawrence Livermore Laboratory (LLL) has

requested the Office of Standard Reference Data (OSRD) to manage the task of gathering the data, using its established network of data centers and other identified sources of expertise. The OSRD monitors the

progress of work, reviews the results, and conveys the numerical data to LLL where the data are converted

for entry into an automated data storage and retrieval system. Every effort is made to supply data which

have been critically examined in light of the latest knowledge concerning theory and experiment. However

it must be recognized that in a rapidly moving technology some of the data will be superseded rather quickly

as new materials and techniques are introduced. Thus access to the data via computer terminal as well as publication in this series should help provide the practitioner with timely and useful data which he requires

to solve his problems in energy storage. Funding for this series of projects from the Department of Energy,

Division of Energy Storage, through the Lawrence Livermore Laboratory, is gratefully acknowledged.

IV
Contents

Page Page

Introduction 2 Systems and Properties Evaluated 2 Fundamental Constants, Symbols, and Units. . 3 Treatment of Data - . 4 Value Judgements 5 Data Tables 6 Acknowledgements 8 References to Introduction 8

Systems Index

LiF NaF

KFLiCl

NaCl

KC1 . . . MgCl

2 CaCl

2 A1C1 3 L^COj

Na,CO,

V°3

LiNOj

NaNOj

kno

3 ^* 2^4

Na

2 S0

4

Sulfur

1020

30

3849

64

818896 102

113

124

132

142

155

167

172

179

185

Na

2 S Na

2 S2 Na

2 S3 Na

2 S

4

LiBr . . . Lil . . . . LiCl-KCl . NaCl-KCl . LiCl-AlClj

NaCl -AlClj

KC1-A1C1

3

. NaCl-CaCl

2

NaF-KF

LiF-LiCl

NaCl-KCl-AlClj . . LiCl-KCl-CaCl

2

. • LiCl-NaCl-KCl . . . LiF-LiCl-LiBr . . . LiF-LiCl-Lil . . . Li2C0

3 -Na

2 C03 -K

2 C0

3 Li2C0

3 -Na2 C0

3

. . . Li

2 C0

3 -K2 C03

. . . Na

2 C03 -K

2 C03

.

. . NaNOj-KNOj ....

LiN0

3 -NaN0

3 -KN03

. Li

2 S0

4 -K

2 S04

.

. . Li

2 S04 -Na

2 S04 -K2 S04 NaCl-Li,SO. . . . . 2 4

197

201

203

206

209

212

218

224

243

260

266

277

285

295

307

315

322

329

332

337

340

343

356

371

384

396

412

417

424

428

V
'

Jf
Physical Properties Data Compilations

Relevant To Energy Storage

II. Molten Salts: Data On Single And Multi-Component Salt Systems

G. J. Janz, C. B. Allen, N. P. Bansal, R. M. Murphy, and R. P. T.

Molten Salts Data Center3 Cogswell Laboratory 3 Rensselaer Polytechnic Institute } Troy 3 New York 12181

The present work provides selected data with

value judgements for a set of 49 salt systems of

interest as candidate materials for thermal energy

storage sub-systems and for electrochemical energy

storage systems. The physical properties assessed

are: melting points; phase diagrams; eutectic

compositions; density; surface tension; viscosity;

electrical conductivity; diffusion constants for

ions; heat of fusion; heat capacity; volume change

on fusion; vapor pressure; thermal conductivity

(liquid and solid); and cryoscopic constant. The

status of corrosion studies in the form of annotated

bibliographic summaries, and salient observations on safety and hazards are also reported. A summarizing

series of tables is provided as index to the datagaps status for this set of candidate materials.

Key words: Corrosion; data compilation; electrochemical energy storage materials; molten salts;

physical properties; safety and hazards; thermal

energy storage materials; thermal properties;

thermodynamic properties; transport properties.

Tomkins

1
1. Introduction

The present communication reports

the results of some work undertaken, in

part, to meet the need for an evaluated

data file for salt systems to. be stored

in the LLL Data Banks for Energy Research

at Livermore. [1,2,3] 1 The situation

encountered by thb user (research

scientist; design and development engineer) may be briefly illustrated by the

following two examples.

The first point encountered is that

the store of information on molten salts

is considerable and is largely unevaluated. It exists partly as primary

research literature and partly compiled

in some of the emerging secondary

and tertiary literature (numerical data

projects, handbooks, bibliographies).

An analysis of the 1974 publications [4]

in this area of materials science may be

summarized as follows.

A total of more than 1300

research papers were published

in 1974, in some 290 scientific

and technical journals of

some 16 different countries.

Approximately 140 descriptors

(keywords) were required to

index these research papers

by physical properties and/or

subject matters.

Thus for an informed use of the accumulated knowledge in this relatively

specialized area of materials science

the user needs guidance, not only as to

what is already established and how it

can be accessed but, equally important,

on the reliability, namely to what degree

are the data adequate for "decision steps"

in design and development applications.

The second point encountered is the

diversified nature of the information

required. For example, in thermal

energy storage, the "data needs" that the

user encounters include:

melting point data; phase diagrams;

heats of fusion; heat capacities;

thermal conductivities; volumechanges on melting; viscosities;

thermal diffusivity; expansion

coefficients; vapor pressures;

thermal stabilities; nucleation;

corrosion; safety and hazards;

interfacial properties; estimation methods,...

The present compilation was undertaken,

thus, to provide a data base for the

informed use of the accumulated knowledge

on molten salts, particularly for applications to thermal energy storage and

figures in brackets indicate literature

references

.

for energy storage electrochemically , as in advanced batteries.

The recommendations advanced by the

Phase-Change Storage Systems Group [5]

provide some guidelines and criteria for

the selection of the candidate materials

(salt systems). These, together with,

the data requirements for electrochemical

applications, and two practical considerations, from the viewpoint of economy,

are summarized in table 1.1. These

principles and recent assessments of

advanced batteries research, thermal and

solar energy storage applications (see

for example [5-10], for partial list)

may be used to reduce the very large

number of salt systems to a relatively

short list, as summarized in table 1.2.

Specific examples of the systems thus

included are:

molten carbonates (Li2C03,

Na2CC>3, K2CO3) and their

mixtures; relevance: high

temperature fuel cells

technology; thermal energy

storage - electric utilities load- levelling

• molten sodium polysulfides

(Na?Sx ) ; relevance: sodiumsulfur advanced battery

technology; transportation;

load- levelling

• molten chlorides, and

nitrates; for example: (a)

LiCl-KCl eutectic; relevance: supporting

electrolyte in ESB (advanced

battery technology) ; (b)

nitrate eutectics; relevance:

thermal energy storage

• low melting mixtures; salt

hydrates; Na2S04 • 1 OH2O , m.pt.

32°C; relevance: thermal

energy storage subsystems

The present communication reports

the results of critical evaluations for

some 26 single-salt systems and 23 mixtures

(binary and ternary systems; including

eutectics)

.

2. Systems and Properties Evaluated

A list of the salt systems for which

results are reported herewith is in table

1.3. The arrangement follows the Anion

Classification used elsewhere for molten

salts [see: 11,15]. Within an anion family

the salts are ordered by cations. There

are exceptions, e.g. the Na2S-Sulfur system

is listed as Na2Sx since the concern is

with polysulfide mixtures, and Sulfur, itself not a salt, has been included to com- plete this system. The physical properties

are listed in table 1.4.

2
Table 1.1. Criteria for the selection

of candidate materials

Table 1.3. List of salt systems

a A. (For thermal energy storage systems (PCM) and for electrochemical energy

b storage (ESB)

1. Thermodynamic properties 2. Chemical properties

(i) suitable melting point (i) safety

(ii) high heat of fusion (ii) stability

(iii)

(iv)

congruent melting

small volume change on melting

(iii) non-corrosive to container materia

(v) high thermal conductivity

(vi) heat capacity

(vii) density 3. Economy

(viii) surface tension (i) inexpensive

(ii) availability

—R.

* Additional considerations for electrochemical

energy storage (ESB)

(i) electrical conductivity (iv) cryoscopic constant

(ii) diffusion constants for ions (v) emf series of metals

(iii) transport numbers for ions (vi) reference electrodes

(vii) thermodynamic activity coefficients

a (PCM); phase-change materials;

k (ESB) ; electrochemical storage batteries

Table 1.2. Likely candidates list

(salt systems)

A. Systems utilizing single salts (I . I la and I.IIb)

I. Cations II. Anions

a U~

lithium chlorides bromides

sodium nitrates iodides

potassium carbonates sulfates magnesium polysulfides phosphates

calcium fluorides thiocyanates

barium hydroxides vanadates

nitrites borates

sulfides tungstates

chromates

formates

acetates

B. Systems utilizing mixtures of salts

(a)

(b)

(c)

Eutectics (2 or more salts from Eutectics (2 or more salts from Eutectics (2 or more salts from

I.IIa)

I.IIb) I.IIa, I.IIb)

C. Systems utilizing salt hydrates

Congruently melting salts with water of hydration

System Material System Material

Sing le salts Salt mixtures

1 LiF 27 LiCl-KCl

2 NaF 28 NaCl-KCl

3 KF 29 LiCl-AlCl

j

4 LiCl 30 NaCl-AlClj

5 NaCl 31 KC1-A1C1

j

6 KC1 32 NaCl-CaCl

2 7 MgCl

2 33 Na

2 Sx

8 CaCl

2 34 NaF-KF

9 Aid j 35 LiF-tiCl

10 Li

2 C03 36 NaCl-KCl-AlCl

j

11 Na

2 COj 37 LiCl-KCl-CaCl2 12 k

2 co3 38 LiCl-NaCl-KCl

13 LiNOj 39 LiF-LiCl-LiBr

14 NaNOj 40 LiF-LiCl-Lil

IS KN0

3 41 Li,C0,-Na 7 C0^-K,C0,

16 Li

2 S04 42 Li2 COj-Na2 COj

17 Na

2 S04 43 Li2 C03 -K2 CO

J 18 K

2 S°4 44 Na,CO^-K,CO,

19 Sulfur 45 NaNOj -KNOj

20 Na

2 S 46 LiNOj-NaNOj-KNOj

21 Na

2 S2 47 Li2 S0

4 -K

2 S0

4 22 Na

2 S

3 48 Li

2 S04 -Na2 S04 -K2 S0

4 23 N®2 S

4 49 NaCl-Li

2 S04 24 Na

2 S5 2S LiBr

26 Lil

Table 1.4. List of physical properties

Storage mode

PCM ESB

1 . melting temperatures X X

2. phase diagram (liquidus-solidus) X X

3. density of melt X X

4. surface tension (wetting) X X

5. viscosity X X

6. electrical conductivity X

7. hazards (safety) X X

8. containment (corrosion) X X

9. diffusion constants for ions X

10. heat of fusion X X

11. heat capacity X X

12. volume change on melting (%) X X

13. vap.or pressure X X

14. thermal conductivity (melt) X X

IS. thermal conductivity (solid) X X

16. cryoscopic constant X X

3. Fundamental Constants,

Symbols and Units

The fundamental constants and

glossary of symbols and units are in

tables 1.5 and 1.6, respectively.

3
Table 1.5. Fundamental constants One-Dimensional Analysis

Symbol Name Value

N Avogadro constant 6 . 022S2 1 0.00028 x 10 2J mol' 1

F Faraday constant 96,487.0 t 1.6 Coulombs mol' 1

, (23,060.9 1 0.4 cal V' 1 equiv.' 1

)

0 Electronic charge 1.60210 x 10' 19 Coulombs

R Gas constant 8.3143 i 0.0012 J K"

1 mol’ 1 1.98716 t 0.00029 cal K^mol' 1

4. Treatment of Data

Statistical Analysis of Data

The recommended data values were

selected based on the estimates of

precision and uncertainty of the data

surveyed in the literature. The Percent

Departure also provided a guideline. The

Percent Departure is defined as:

Percent Departure =

"compared value" - "tabulated value"

"tabulated value"

Here "compared value" and "tabulated

value" refer to the literature value and

the value recommended in the present work.

Both the "compared value" and the "tabulated value" were calculated from statistically derived equations since the results

had to be interpolated to common temperatures and common compositions. Where the

data sets from two or more studies were

merged to provide the data base for the

recommended values (either to extend the

temperature range, or to fix the confidence level) this has been noted in the

data tables. Unless otherwise noted, all

values were recalculated to the Kelvin

temperature scale and are thus reported

throughout

.

All calculations were made on the

digital computer facilities at Rensselaer

Polytechnic Institute. The data set of

the recommended study were recalculated

by a one-dimensional analysis, using the

method of least squares, to establish

equations indicating the variations of

the physical quantities with temperature

at the experimental compositions. If the

data base was sufficient, calculations

using a two-dimensional analysis, with a stepwise multiple regression routine were

undertaken. In this way a physical

property- temperature -compos it ion matrix

was developed. A result of this analysis

is that it enables intercomparisions of

property values at either common temperatures or at common compositions.

The criterion for choosing the

equation of best fit in the one-dimensional analysis was the standard error

of estimate.

Table 1.6. Glossary of symbols and units

Symbol Physical quantity Units 8

a Thermodynamically defined activity dimensionless

A Pre-exponential factor as in text

C Concentration mol 3 C P Heat capacity cal K"

1 mol1

D Diffusion coefficient 2 -1 cm sec

E Energy of activation cal mol Heat of fusion kcal mol 1

k

f Cryoscopic constant K mol' 1 kg'

1

K d Equilibrium dissociation constant atm.

M

1 Apparent molecular weight . -1

g mol

Dr vap Vapor pressure mm Hg

t Temperature (Celsius) °C T Temperature (Kelvin) K T

m Melting temperature °C

T

o Ideal glass transition temperature K

V

s Molar volume of solid 3 . -1 cm mol

4V

f Change in molar volume on fusion 3 , -1 cm mol

(AV

f /Vs )t Percent molar volume change dimensionless

X Mol fraction dimensionless

Y Surface tension dyn cm

1

n Viscosity cp or poise

< Electrical conductance ohm 1 cm

1

X Thermal conductivity1* cal cm ^ec 1 K

1

p Density

- 3 g cm

a For conversion to the SI system of units:

1 ohm ^cm *1 x 10

2 P ^ 1

1 g cm

3

1 x 10

3 Kg cm

5

1 cp = 1 x 10 3 N s m

2

1 dyn cm * = 1 x 10

3 N m

1

1 cal mol" 1 = 4.184 J mol' 1 sec = s

h For conversion

to : multiply by:

mW m"

1 K"

1 4.184 x 10 3

W m'V 1 4.184 x 10

2

J cm

1 sec

1 K

1 4.184 kcal m"

1 hr" 1 K*

1 3.600 x 10 2

BTU ft" 1 hr" 1 F

1 2.419 x 10 2

This was defined by

s n - q

where y e

= the experimental value at each

temperature, y

= the value calculated from

the least squares equation at the same

temperature as y e , n = the number of

experimental data points, and q

= the

number of coefficients in the least square

equation (2 for linear, 3 for quadratic).

The standard error of estimate was computed from the residuals in the leastsquares routine.

4
Two-Dimensional Analysis

The computer programs consisted of

the four routines, STPRG, CORRE, LOC and

MSTR; the latter two are storage routines

which have no effect on the accuracy of

the results. In addition a subroutine

STOUT was used to print the results of

each regression step and the subroutine

MATRIX, for printing a matrix of numerical

values from the thus derived equation.

The abbreviated Doolittle method was used to select the variables entering the

regression and for calculation of coefficients. The independent variable included

in each step of the analysis was selected

by computing the reduction of sums of

squares of each variable. The variable

causing the largest reduction was added

to the equation and deleted from the

table of sums of squares. The coefficients, intercept and statistical parameters

for the new equation were computed and

printed. This procedure was repeated

until the maximum proportion of sums

of squares to the total reduced was less

than a limit set by the programmer.

The independent variables used in the

initial selection were chosen from a generalized procedure, which generated 30

combinations of the input variables

using powers, reciprocals, logarithmic

and exponential quantities. It was

found that the procedure consistently

selected the equation (T + C)^, so that

the working program used nine independent

variables. After the final equation was produced, it was transferred to the

MATRIX routine, which recalculates values

at rounded compositions and temperatures,

within specified boundary conditions. In

the presentation of the matrix, due

cognizance is taken of the experimental

range of investigation and of the phase

relationships for the system so that

values are always "interpolated" rather

than "extrapolated". The final step in

the procedure involves the residual

analysis (giving the deviations of the

original values from those computed from

the "best-fit" equations).

In the programs used (vide infra) , a summary of significant parameters is

printed by the computer at each step in

the regression analysis. These are: the sum of the squares reduced, S^; the ratio

Si/D where D is defined below; and the

cumulative sum of these variables,7 S

c um and P cum . These quantities give an indication of the effect of each variable

in the final equation. The programmers

limit on P was always in the range

0.0001 < P cum < 0.001.

The standard error in the estimated

y values adjusted for degrees of freedom,

is then given by:

s D S

cum

q

- 1

55

- 2 where D = £ (y - y) , y

= experimental

values, y

= average of all experimental

values, and q

= the number of independent

variables in the equations.

An F value analysis of variance was used to determine if a particular model

was acceptable.' Tables of F values

indicate that values greater than 2.0 are acceptable for the routine used here. In

all cases values of F were greater than

1000. The F value is defined as:

P

_ S cum/

q

(D - S ) / (n - q v - 1) cunr v n

where S , q, D, and n are defined above,

cum ’ n ’

5. Value Judgements

(a) Precision

Estimates of precision were based on standard error of estimate analysis. The

standard error of estimate is the end

result of a statistical analysis of the

numerical data, and the statistical

analysis depends on various factors, such

as the number of data points, the nature

of the concentration dependence and the

temperature dependence of the particular

physical property. The precision is the

standard error expressed as a percent

value. As a general guide, about 60% of

the results lie within the estimate of

precision, 95% within twice this value and

approximately 99% within three times the

value. Where the preceding approach was

not possible, we refer to the published

error estimates of the original authors.

(b) Accuracy

Accuracy estimates were based on assessments of experimental details

including method of measurements, techniques, analytical characterization of

chemicals, and intercomparisions with

results from the same and/or different

laboratories. The accuracy estimates

are more subjective than the estimates of

precision. The numerical values are reported to more significant figures than

justified by the accuracy for internal

consistency (i.e., the values fall within

the limits of precision analysis)

For eutectic melting point data,

values are reported without limits of

5
accuracy. This is largely because

the experimental details (i.e., cooling/

heating curves) are insufficient

for accuracy estimates.

The various measurement techniques

encountered are summarized in table 1.7.

The range is considerable and shows some

aspects of the complexities and difficulties in this part of the task, i.e.

firming up accuracy estimates. Descriptions of experimental details, particularly for molten salts studies, may be

found in recent surveys [11-15] , and

it is sufficient to note some particular

points encountered in the present task.

The most widely used techniques appear to

be: Archimedean (density), maximum

bubble pressure (surface tension)

,

capillary and oscillating sphere

(viscosity), ac bridge (electrical

conductance) , chronopotent iometry

(diffusion), drop calorimetry (heat of

fusion; heat capacity), dilatometric

(volume change on fusion) mass spectrometry-Knudsen cell (vapor pressure) , hot

wire (thermal conductivity) , and heats of

fusion (cryoscopic constants). The

accuracy estimates based on these appear

reasonably sound.

Concerning electrical conductivity,

however, it is now apparent that the

quartz capillary dipping cell technique

leads to values as much as 3-5% too high

at temperatures greater than 900°C [16]

.

Table 1.7. High temperature experimental techniques

Density

Archimedean

dilatometric

flotation

maximum bubble

pycnometric

Surface tension

maximum bubble

Wilhelmy slide plate

pin detachment

capillary rise

sessible bubble

pendant drop

Viscosity

capillary

oscillating sphere

oscillating cylinder

falling sphere

Electrical conductance

dc bridge

ac bridge

transformer bridge

Cryoscopic constants freezing point lowering

(dilute solution)

freezing point depression

(phase-rule)

from heats of fusion

Vapor pressure

manometry

(sickle or spoon gauge)

dew point

boiling/reduced pressures

vapor transpiration

Knudsen effusion

Mass spectrometry and

Knudsen effusion

Heat of fusion

Heat capacity

isothermal calorimetry

drop calorimetry

differential -scanning

calorimetry (DSC)

phase-rule (freezing

point data)

solution calorimetry

Volume change on mel ting

gas manometry

dilatometric

pellet expansivity

Thermal conductivity

(liquid, solid)

hot wire - absolute and

transient

modified hot wire

concentric cylinder - absolute

and transient

optical plane - absolute and

transient

radial heat flux

linear heat flux

flat plate - steady state comparative method

others

Diffusion

chronopotent iometry

linear sweep voltammetry

dc polarography

oscillographic polarography

faradaic impedance

chronoamperometry

rotating disc electrode

porous frit

electrophoresis

wave-front interferometry

capillary

6
A further point of some concern relative

to conductance data is an error noted

[17] in a USSR 1970 textbook of physical

chemistry. In the English translation of

Ya. Gerasimov’s "Physical Chemistry",

the composition of the conductance cell

calibration standard 1 demal solution is

specified as 74.1352 g KC1 rather than

the internationally accepted value,

71.1352 g KC1. This should not be overlooked as a possible contributing factor

to discrepancies arising in published

conductance data.

An emerging aspect relative to

viscosity data is recognition [16] of the

extreme care that must be given to

features of experimental des ign/technique

if the damped oscillation method (oscillating sphere) is to be used with

confidence. As noted in the data sheets,

it is apparent that the recommended

viscosity values forNaCl may be as much

as 251 too high at 900°C, even though the

technique, as conventionally used, should

be capable of an accuracy better than

±5%. An example selected from diffusion

studies may be used to illustrate the

situation encountered in analyzing the

results from independently completed

studies of the same systems. The results

for various metal ions in the molten

LiCl-KCl eutectic (500°) [18-23] are summarized in table 1.8. Our critical

evaluation places highest reliance to the

results of Heus and Egan in this example.

With reference to chronopotent iometry , it

Table 1.8. Diffusion coefficients of

metal ' ions in LiCl-KCl at 500°C

a Chronopotentiometry at Pt electrodes

b Chronopotentiometry at Pt electrodes

c Polarography at dropping bismuth electrodes

d Linear sweep voltammetry at Pt electrodes

e Linear sweep voltammetry at glassy carbon

electrodes

is of interest to note that applications

to complex systems, such as the electrolytes of the Li/S battery systems and

molten carbonate fuel cell systems now

appear possible. Meaningful values for

the derived diffusion coefficients should

follow directly from the analysis

advanced by Vallet and Braunstein [24]

for electrochemical flux equations in

binary mixtures of molten salts.

6. Data Tables

Values are reported throughout on the

Kelvin temperature scale with the exception

of the melting point data. The Celsius

scale was retained for melting points for

ease of reference to source materials.

Information has been included relative to

two aspects that do not lend themselves

readily to critical assessments, namely

Corrosion and Containment, and Safety and

Hazards. For these two aspects the information is reported simply in an annotated

bibliography format to provide ready

access to the relevant source literature

on a "need" basis.

A summary of systems for which no information is available has been prepared

using a physical properties classification.

This is in table 1.9. From the latter,

the data-gaps status is readily realized;

for example, inspection shows that for

the sodium polysulfides (Na/S battery;

sulfur electrode) there is no information

for heats of fusion, heat capacities,

diffusion, and volume changes on melting.

Table 1.9. Data gaps status

Melting point Surface tension

No data gaps Na

2 s Na

2 S2 Phase diagrams LiCl-AlCl

j

No data gaps NaCl-AlClj

kci-aici

3 Density NaCl-KCl-AlCl

3 LiCl-KCl-CaCl

2 Na

2 S LiCl-NaCl-KCl

Na

2 S2 LiF-LiCl-LiBr

LiCl-KCl-CaCl

2 LiF-LiCl-Lil

LiCl-NaCl-KCl LiNO, -NaNO, -KNO, LiF-LiCl-Lil

Li,SO,-K,SO.

LiN0

3 -NaN0

3 -KN03 Li,SO.-Na,SO. -K^SOa LqSO^ -Na^SO^ -k

? so1 NaCl-Li-SO.

Electrical conductivity

Na

2 S Viscosity

Na,S,

LioSO.

2 4 Na

2 S4 Na,SO. Na,S c 2 < LiCl-KCl-CaCl

2 Na

2 S LiF-LiCl-LiBr

Na

2 S2 LiF-LiCl-Lil

Na,S 4 Li

2 S04 -Na2 S04 -K

2 S04

2 4 NaCl-Li-SO.

Z 4 Na

2 s5 LiCl-AlClj

KC1-A1C1, Volume change on melting NaF-KF Na

2 s LiF-LiCl Na

2 s2 NaCl-KCl-AlCl

3 KC1-A1C1

3 LiCl-KCl-CaCl

2 Na

2 S

x LiCl-NaCl-KCl NaCl-KCl-AlClj

LiF-LiCl-LiBr LiCl-KCl-CaCl

2 LiF- LiCl-Lil LiCl-NaCl-KCl

LiNOj-NaNOj- KNOj LiF-LiCl-LiBr

li

2 S04 -K

2 S0

4 LiF-LiCl-Lil

Li

2 S04 -Na

2 S04 -K2 S04 LiNOj-NaNOj- KNOj

Li

2 S0

4 -Na2 S04 -K

2 S0

4 NaCl-Li

2 S04 NaCl-Li

2 S04

(table continued)

7
Table I. 9. --Continued 7. Acknowledgements

Diffusion Heat capacity

LiF MgCl

2 A1C1

3 K

2 C03 Li

2 S0

4 Na

2 S0

4 k

2 so

4 Na

2 S Na

2 S2 Na,S. Na^

3

Na

2 S

s LiBr

Lil

Na

2 S2 Na,S,

Na

2 S4 Na

2 S

5 NaCl-KCl LiCl-AlClj

NaCl - A1C1

3 KC1-A1C1

3 NaCl-CaCl

2 Na

2 S

x NaF-KF

LiF-LiCl NaCl-KCl-AlCl

3 LiCl-KCl-CaCl

2 LiCl-NaCl-KCl LiCl-AiCl

3 LiF-LiCl-LiBr

KC1-A1C1.

LiF-LiCl-Lil

Na

2 S

x NaF-KF

Li

2 C0

3 -Na2 C0, LiNO, - NaNO, - KNO, LiF-LiCl

Li 7 SO . - K 7 S0

.

NaCl -KC1 - AlClj

Li 7 S0a - Na 7 S0. -

K

7 S0. LiCl - KC1 -CaCl

2 LiCl-NaCl-KCl

LiF-LiCl -LiBr Vapor pressure LiF-LiCl-Lil ^*2^4

NaCl-Li

2 S04 Na

2 s LiCl-KCl

Heat of fusion LiCl-AlCl

3 NaF-KF

Na

2 S2 LiF-LiCl

Na

2 S

3 NaCl-KCl-AlCl

3 Na

2 S4 NaCl-KCl

LiCl - KC1 -CaCl

2 LiCl -NaCl - KC1 Na

2 S

x LiF- LiCl - LiBr LiF-LiCl -LiBr LiF-LiCl - Li

I

LiF-LiCl - Li

I

NaN0

3 -KN03 LiNOj-NaNOj-KNOj Li

2 S04 -K2 S04 Li

2 S0

4 -K

2 S04 Li

2 S0

4

- Na

2 S0

4

-

K

2 S04 Li

2 S04 -Na2 S04 -K2 S04 NaCl-Li

2 S04

Thermal conductivity Thermal conductivity

liquid solid

KF KF Aicij CaCl

2 *2 C0

3 Aid 3 Li

2 S04

k

2 c°

3 Na

2 S0

4 Li

2 so4 K

2 so

4 Na

2 S04 Na

2 S2 K

2 so

4 Na

2 S

4 Na

2 S Na

2 S5 Na

2 S2 Lil Na

2 S3 NaCl" KC1 Na

2 S

4 LiCl-AlClj Na

2 S5 KC1-A1C1

3 LiBr

NaCl -CaCl

2 Lil Na

2 Sx NaCl-KCl NaF-KF LiCl - AlClj LiF-LiCl NaCl -AlClj NaCl-KCl-AlClj KCl-AlClj

LiCl - KC1 -CaCl

2 NaCl -CaCl2 LiCl-NaCl-KCl Na

2 Sx LiF- LiCl - LiBr NaF-KF

LiF-LiCl - Li I LiF-LiCl

Li

2 C0^-Na2 C03 -K2 C0j NaCl - KC1 - AlClj LijCOj-KjCOj LiCl - KC1 -CaCl

2 Na

2 C03 -K2 C03 LiCl - NaCl - KC1 LiN0

3 -NaN0

3 -KN03 LiF-LiCl -LiBr

Li

2 S04 -K

2 S0

4 LiF-LiCl -Lil

Li

2 S0

4 -Na

2 S0

4 -K

2 S0

4 Li2 C03 -Na2 C03 -K2 C03 NaCl-Li

2 S04 Li2 C03 K2 C03 Na

2 COjK2 C0

3 Cryoscopic constant

NaN0

3 -KN0

3

Na

2 S

2

LiNOj - NaNOj - KNOj

Li

2 S04 -K2 S04 Na ? S, Na

2 S4

Li 7 S0

4 -Na2 S0

4 -K

2 S04 NaCl-Li

2 S0

4 NaCl-KCl

Na

2 S

x LiF- LiCl - LiBr LiF-LiCl - Li I NaN0

3 -KN0

3 LiN0

3 -NaN03 -KN03 Li

2 S04 -K2 S04 Li

2 S04 -Na2 S04 -K2 S0

4

We acknowledge with pleasure prepublication-results from various

colleagues during the course of this work,

and in particular L. G. Marianowski and

H. Maru, Institute of Gas Technology

(molten carbonates), G. E. Slack, General

Electric Research Center (thermal conductivities) and D. D. Wagman, Thermodynamics

Data Center, NBS (heats of fusion),

B. Cleaver, Southampton, U. K. and

R. Tegman, Umea, Sweden (molten polysulfides), F. Feher and H. D. Lutz, Cologne,

FDR (molten sulfur), Lt . Col. L. A. King,

USAF Academy, and H. A. 0ye , Trondheim,

Norway (molten AICI 3 and mixtures) . We

express thanks to the following for input

on matters of precision and accuracy

estimates, particularly for densities,

surface tensions, viscosities, and

electrical conductivities of molten salts:

J. Braunstein (Oak Ridge National Laboratory), T. E j ima (Tohoku University, Japan),

H. H. Emons (Bergakademie Freiberg, DDR),

M. Chemla (Universite Paris, France),

J. A. A. Ketelaar (University of Amsterdam,

Netherlands) , K. Matiasovsky (Slovak

Academy of Sciences, Bratislava, Czechoslovakia) , D. A. Nissen (Sandia Livermore

Laboratories), H. A. 0ye (NTH,' Trondheim,

Norway), L. Suski (Polish Academy of

Sciences, Krakow, Poland), and S. Zuca

(CCF, Bucharest, Rumania).

The completion of this work owes much

to the participation of Candace Bornt,

Elizabeth Schoonmaker, Eric Boskin, Jeff

Baechler, Ray Rein, John Gual, Valerie

Beane, Debbi DeBoer, David Aronson, Tim

Walker and Adam Martinez at the MSDC-RPI.

We acknowledge this with pleasure

We thank L. H. Gevantman, (OSRD-NBS)

and T. M. Quick' (LLL - Univ. California)

for constructive suggestions and continued

interest throughout the course of this

work

.

8. References to Introduction

[1] Hampel, V. E., Data Management

Group, Lawrence Livermore Laboratory, Univ. California, and

Gevantman, L. H. , Office of

Standard Reference Data, National

Bureau of Standards.

[2] Hampel, V. E., Henry, E. A., Kuhn,

R. W. , and Lyles, L., "Acquisition

,

Storage , Retrieval , display , and

Utilization of Computerized Data

in the DLL Data Bank of Physical

and Chemical Properties" , Proc.

5th International CODATA Conference

(1976), Pergamon Press, N. Y.

(1978)

.

8
[3] Hampel, V. E., and Quick, T. M.

,

"Research Leading to the Production and Early Use of

Numeric Data Banks of Materials

Properties and Systems Analysis"

,

(Project Summary); Proc. 2nd

Ann. Thermal Energy Storage

Contractors' Information Exchange

Mtg . ORNL-Conf-T10955 (1977);

NTIS, U. S. Dept. Commerce,

Springfield, Va.

[4] "1974 Molten Salts Bibliography",

Molten Salts Data Center Technical Publication Series, MSDC-RPI,

Troy, N. Y. (1975)

[5] "Phase Change Storage Systems

Report", Proceedings NSF ERDA

Workshop in Solar Energy Storage

Subsystems, p. 169; NSF-RA-75-

041 (1975); NTIS, U. S. Dept.

Commerce, Springfield, Va.

[6] "Proceedings of a Symposium in

Advanced Battery Research Design

and Development"

,

ANL-76-8 (1976);

NTIS, U. S. Dept. Commerce,

Springfield, Va.

[7] "Survey of High Temperature

Thermal Energy Storage", Bramlette, T. T., Green, R. M.

,

Barthel, J. J., Oltesen, D. K.

,

Schafer, C. T., and Brumleve,

T. D. , Sandia Labs. Energy

Report: SAND 75-8063 (1976);

NTIS, U. S. Dept. Commerce,

Springfield, Va.

[8] "Storage of Low Temperature Heat",

Wettermark, G. , and Kowalewska,

J., Swedish Council for Building

Research Report, Stockholm,

Sweden, September, 1976.

[9] "Report < on the Conference on Thermodynamics and National

Energy Problems"

,

(National

Academy of Science Report - 1974); NTIS, U. S. Dept.

Commerce, Springfield, Va.

[10] "Redox Bulk Energy Storage System",

CR-135206 (Exxon Research and

Engineering Co., (1977), NTIS,

U. S. Dept. Commerce, Springfield,

Va.

[11] Janz, G. J., "Molten Salts Handbook", Academic Press, N. Y.

(1967)

[12] Bockris, J. O'M., White, J. L. , and

Mackenzie, J. D. , "Physicochemical Measurements at High

Temperatures", Butterworths

,

London (1959)

[13] Corbett, J. D. , and Duke, F. R. , in

"Techniques of Itiorganic Chemistry ", Vol. 1, Wiley-Interscience, N. Y. (1963).

[14] Bailey, R. A., and Janz, G. J.,

in "The Chemistry of Non-Aqueous

Solvents", Vol. 1, Academic

Press , N. Y. (1966) .

[15] Janz, G. J., Tomkins, R. P. T.,

Allen, C. B., Downey, J. R. , Jr.,

Gardner, G. L., Krebs, U. , and

Singer, S. K. , "Molten Salts,

Vol. 4, Ft. 2, Chlorides and

their Mixtures : Electrical

Conductance , Density , Viscosity

,

and Surface Tension Data", J.

Physical and Chemical Ref. Data,

4, 871 (1975), and earlier

Tssues, this series.

[16] MSDC-RPI, "Molten Salts' Calibration

Quality Data Project", unpublished

work (1978)

[17] Janz, G. J. , and Tomkins, R. P. T.

,

J. Electrochem. Soc., 124, 55C

(1977) .

[18] Laitinen, H. A., and Ferguson, W. S. 3 Anal. Chem., 2_9, 4 (1957).

[19] Laitinen, H. A., and Gaur , H. C.,

Anal. Chim. Acta, 1_8 , 1 (1958).

[20] Thalmayer, C. E., Bruckenstein , S.,

and Gruen, D. M. , J. Inorg. Nucl.

Chem., 26_, 347 (1964).

[21] Heus , R. J., and Egan, J. J., J.

Electrochem. Soc., 107, 825

(1960)

[22] Naryshkin, I. I., Yurkinskii, V. P.,

and Stangrit, P. T., Elektrokhimiya, 5^, 1043 (1969); 5, 1476

(1969)

[23] Behl, W. K. , J. Electrochem. Soc.,

118, 889 (1971).

[24]

Vallet, C. E. , and Braunstein, J.

,

J. Phys. Chem., 81, 2438 (1978).

9
I. Lithium Fluoride: LiF

1. Melting Temperature (T ) Melting point:

848° + 2 °C [1]

References [1-16].

2. Density (p)

Measurement method: Archimedean technique [17]

p = 2.3581 - 4.902 x 10” 4 T (1.1)

precision: + 0,11% uncertainty: v + 0.5%

Table 1.1. Densities from equation (1.1)

T(K)

P (g cm

-3

)

T(K)

P (g cm

-3

) 1140 (1.7993) 1230 1.7552

1150 1 .7944 1240 1.7502

J.160 1.7895 1250 1.7454

1170 1.7846 1260 1.7404

1180 1 . 7797 1270 1.7355

1190 1.7748 1280 1 .7306

1200 1.7699 1290 1.7257

1210 1.7650 1300 1.7208

1220 1.7601 1310 1.7159

Value in parenthesis extrapolated beyond experimental temperature range.

References [17-20].

3. Surface Tension (y)

Measurement method: maximum bubble pressure [21]

y

= 346.49 - 9.88 x 10

_2

T (1.2)

precision: ± 0.3% uncertainty: ^ + 3%

For numerical values: see table 1.2

References [21-22].

4. Viscosity (r\)

Measurement method: oscillating sphere [20]

n = 18.549 x 10~ 2 exp (5610/RT) (1.3)

precision: + 0.9% uncertainty: ^ +20%

For numerical values: see table 1.3

References [20,23].

5. Electrical Conductance (k)

Measurement method: ac; Kelvin bridge [24]

k = -15.0389 + 3.53546 x 10" 2 T - 1.28145 x 10" 5 T

2 (1.4)

precision: + 0.3% uncertainty: ^ + 5%

For numerical values: see table 1.4

References [17, 24-27].

10
LiF

Table 1.2. Surface tension from equation (1.2)

T(K)

Y (dyn cm *) T(K)

Y (dyn cm *)

1160 231.9 1350 213.1

1170 230.9 1360 212.1

1180 229.9 1370 211.1

1190 228.9 1380 210.1

1200 227.9 1390 209.2

1210 226.9 1400 208.2

1220 226.0 1410 207.2

1230 225.0 1420 206.2

1240 224.0 1430 205.2

1250 223.0 1440 204.2

1260 222.0 1450 203.2

1270 221.0 1460 202.2

1280 220.0 1470 201.3

1290 219.0 1480 200.3

1300 218.1 1490 199.3

1310 217.1 1500 198.3

1320 216.1 1510 197 .

3

1330 215.1 1520 196.3

1340 214.1 1530 195.3

Table 1.3. Viscosity from equation (1.3)

T(K)

n(cp

)

T(K)

n(cp)

1140 2.21 1240 1 .81

1160 2 .11 1260 1 .74

1180 2.03 1280 1 .68

1200 1 .95 1300 1 .63

1220 1 .88 1320

1340

1.57

1.53

Table 1.4. Electrical conductance from equation (1.4)

T(K)

K (ohm 1 cm 1

)

T(K)K (ohm 1 cm 1 ) 1140 8 . 612 1230 9 .060

1150 8.672 1240 9 .097

1160 8 .729 1250 9 . 132

1170 8 .784 1260 9 .164

1180 8 .837 1270 9 .193

1190 8 .886 1280 9 .220

1200 8 .934 1290 9 . 244

1210 9 .978 1300 9 .266

1220 9 .021 1310 9 .285

11
LiF

6.

Safety and Hazards

A. Hazard rating [28-30]

(i) Toxicity - severe

(ii) Vapor pressure: at m.pt. (848 °C) , ^ 8.8 x 10' 3 mm;

at 1080 °C, ^ 1 mm

7 (iii) U.S. occupational standards: 3.4 mg m air

B. Disaster hazards [31-33]

(i) Molten salt bath "explosion": i.e,, explosive generating of

steam due to bulk water "carry-over" and/or equipment

failure; i.e., explosive expansion of "trapped" air.

(ii) Fluorides, when heated to decomposition, or contacted

with acids, emit highly toxic fumes.

References [28-33].

7

.

Corrosion

Table 1.5. Corrosion studies from primary research literature

Studies Ref erences

Cr 34

Ni-Cr-Fe alloys (INOR-8;

Hastelloys N, B, W,...) 36-41

A1 42

Cb-Zr (99-1) 43-44

Ta-W-Zr-Cb (28-10.5-0.9-60.6)

Ta-W-Cb (10-10-80) 44

Electrochemical behavior of

oxide ions and related species in

molten fluorides

45-47

Electro-analytical studies in

molten fl-uorides 48

Annotated corrosion biblio. 49

Corrosion: molten fluorides

(survey) 50

References [ 04 -oij.

8. Diffusion

No diffusion studies reported.

9. Heat of Fusion

Measurement method: drop calorimetry [16,53]

Table 1.6. Heat of fusion

AH

f -1

(kcal mol ) Uncertainty

6.43 ^ ± 0.8%

References [16, 52-55].

12
LiF

10.

Heat Capacity (Cp)

Measurement method: drop calorimetry [53]

C ='8.351 + 6.134 x 10' 3 T - 1.4694 x 10 4 T'

2 (1.5)

P

precision: ^ + 0.2% uncertainty: ^ + 1.5%

Table 1.7. Heat capacity from equation (1.5)

T(K)

C

P (cal K Vol 1 )

T(K)

C

i p (cal K

-L mol 1 ) 1120 15.21 1280 16.19

1130 15. 27 1290 16.26

1140 15.33 1300 16.32

1150 15.39 1310 16.38

1160 15.46 1320 16 . 44

1170 15.52 1330 16.50

1180 15.58 1340 16.56

1190 15.64 1350 16.62

1200 15.70 1400 16 . 93

1210 15.76 1500 17.55

1220 15.82 1600 18 .16

1230 15.89 1700 18.77

1240 15.95 1800 19.39

1250 16 . 01 1900 20.00

1260 16 .07 2000 20.62

1270 16.13 1

References [1,16,53,54,56],

11.

Volume Change on Melting ( AF

Measurement method: capillary [57]

Table 1.8. Volume change on melting

( A V / V ) r s Uncertainty

29.4% ^ ± 2%

References [ 57] .

12.

Vapor r Pressure (pr ) vap

Measurement method: effusion [60,61]; boiling point [58,62];

estimated from data base [63]

log p

= A + B/T (1.6)

Table 1.9. Coefficients of equation (1.6), precisions, and uncertainties

T range

(K)

A -B Precision Uncertainty

1121-1160 8.4768 11793 ^±0.6% ^ ±5 %

1170-1620 9 .7633 13250 ^±3.1% ^±10%

1630-1930 9 . 0006 11896 ^±0.8% ^±5%

13
LiF

Table 1.10. Vapor pressure from equations in table 1.9

T P T P

( K ) ( mm ) ( K ) ( mm )

1120 0.0089 1630 50.4

1125 0.0099 1640 55.8

1130 0.0110 1650 61.8

1135 0.0122 1660 68 .

3

1140 0.0136 1670 75.4

1145 0.0150 1680 83.1

1150 0 . 0167 1690 91.5

1155 0.0185 1700 100.7

1160 0.0204 1710 110.6

1180 0.034 1720 121 .

4

1200 0.053 1730 133.1

1220 0.080 1740 145.8

1240 0.12 1750 159.5

1260 0.18 1760 174.4

1280 0 .26 1770 190.4

1300 0.37 1780 207.7

1320 0.53 1790 226.4

1340 0.75 1800 246 .

4

1360 1.05 1810 268.1

1380 1 . 45 1820 291 .

3

1400 1.99 1830 316.3

1420 ' 2 .71 1840 343 .

1

1440 3.65 1850 371.8

1460 4 .87 1860 402 .

6

1480 6.47 1870 435.6

1500 8.51 1880 470.9

1520 11.12 1890 508.7

1540 14.43 1900 549.0

1560 18 .61 1910 592.0

1580 23 . 84 1920 637 .

9

1600 30.34 1930 686.9

1620 38.40

-References [58-63].

13. Thermal Conductivity ( liquid

)

(A

^

) Measurement method: quasi-steady state [64]

precision: not estimated uncertainty: ^ + 25%

The results were reported in graphical form only.

14
LiF

Table 1.11. Thermal conductivity of melt

T

4

X x 10

(K) (cal cm sec K ) 1143 41.

3

X values at other temperatures in the range 1200-1450 K are reported in

graphical form in [64]

References [51,64] .

14. Thermal Conductivity (solid) (X ) s Measurement method: absolute stationary [65]

precision: not estimated uncertainty: v + 10%

The results were reported in graphical form only.

Table 1.12. Thermal conductivity of solid

T(K)

X x 10 3 (cal cm

-3

' sec"1 ) 300 34.9

400 25.1

500 19 .

3

600 15.8

700 14.7

800 13.4

900 13.6

1000 14.3

Values interpolated from the graphical presentation in [65]

References [64-69]

15. Cryoscopic Constant (k^)

Measurement method: calculated from AH£

Table 1.13. Cryoscop

[70]

ic constant

k

f (K mol-^kg"-1-) Uncertainty

10.4 ± 0.8%

References [16,52-54,70-78].

16. References

[1] Stull, D. R., and Prophet, H. , JANAF Thermochemical Tables

,

2nd Ed.,

NSRDS-NBS 37; U. S. Gov't Printing Office, Washington, D. C. (1971).

[2] Rossini, F. D., Wagman, D. D., Evans, W. H. , Levine, S., and Jaffe,

I., Selected Values of Chemical Thermodynamic Properties 3 NBS,

Circ. 500; U. S. Gov't Printing Office, Washington, D. C. (1952).

[3] Chu, Y. A., and Belyaev, A. I., Izv. Vysch. Ucheb. Zaved., Tsvet.

Met., 2, 69 (1959).

[4] Kostenska, I., Corba, J., and Malinovsky, M. , Chemicke Zvesti, 28,

546 (1976).

15
LiF

[5] Holm, J. L,, Ph.D. Thesis, Univ. of Trondheim, NTH, Norway (1963) i

[6] Malinovsky, M., and Matiasovsky, K. , Hutnicke Listy., 24(7),

515 (1969).

[7] Holm, J. L., and Holm, B. J., Acta Chem. Scand., 24_, 2535 (1970).

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Puskin, N. A., and Baskov, A. V., Zh. Russ. Fiz. Khim. Obshch.,

135, 82 (1913).

[11] Rolin, M., Bull. Soc. Chim. Fr . , 2271 (1969).

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778 (1969).

[13] Thoma , R. E., Sturm, B. J., and Guinn, E. J., Molten Salt Solvents

for Fluoride Volatility Processing of Aluminum ^Matrix Nuclear

Fuel Elements , USAEC-ORNL 3594 (1964).

[14] Dergunov, E. P., Dokl . Akad. Nauk. SSSR, 60,(7), 1185 (1948).

[15] Fedotiev, P. P., and Timiofeff, K., Z. anorg. allgm. Chem.,

206, 263 (1932).

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[18] Jaeger, F. M., Z. Anorg. Chem., 94_, 288 (1916).

[19] Schinke, H. , and Sauerwald, F., Z. anorg. allgm. Chem., 284,

131 (1956).

[20] Sipriya, G. J., and Vetyukov, M. M. , J. Appl. Chem. (USSR),

36, 1849 (1962).

[21] Ellis, R. B., Prog. Rpt. USAEC Contract AT (40-1) -2073 (1961).

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E. L., USAEC Research and Development Report, Contract No.

AT-33-1GEN- 53 , MLM-1086, March 1959.

[24] Winterhager, H. , and Werner, L., Forschungaber . Wirtsch.

Verkehrsministeriums Nordrhein-Westfalen, No. 438 (1957).

[25] Ryschkewitsch , E., Z. Elektrochem . , 3_9, 531 (1933).

[26] Yim. E. W, , and Feinleib, M. , J. Electrochem. Soc., 104, 622

(1957)

.

[27] Bronstein, H. R., and Bredig, M. A., Chemistry Division

Semiannual Progress Report, Oak Ridge National

Laboratory, ORNL-2782, 59 (1959).

[28] "Dangerous Properties of Materials"3 Sax, N- I., Van Nostrand

Reinhold Co., N. Y. (1969).

[29] "Registry of Toxic Effects of Chemical Substances ", Christensen,

H. E. and Lubinbyhl, T. T., eds . , U.S. Dept. H.E.W., U.S. Gov t Printing Office, Washington, D.C. (1975).

16
LiF

[30] Vapor pressure, calculated (see p. 14, this work).

[31] "Potential Hazards in Molten Salt Baths for Heat Treatment

of Metals", National Board Fire Underwriters Research

Report No . 2 (1954).

[32] "Handbook of Reactive Chemical Hazards", Bretherwick, L,,

Butterworths Co., London (1975).

[33] Janz, G. J., Tomkins, R. P.T., Downey, J. R. , Jr., and Allen, C. B.,

"Safety and Hazards", Chapter in "Eutectic Data,, ERDA TID- 271 63 -PI

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[34] Brasunas, A., Metal Progli., 6_2, 88 (1952).

[35] Grimes, W. R. , Blankenship, F. F., Keilholtz, G. W. , Poppendiek, H. F.,

and Robinson, M. T., Proc. Second Un. N. Inter. Conf, on Peaceful

Uses of At. Energy, Geneva, 28_, 99 (1 958).

[36] Oak Ridge National Laboratory, Molten Salt Reactor Program,

Semiannual Progress Report, ORNL-3708 (1964).

[37] Bettes, E. S., Nucl . Sci. Eng., 2^, 804 (1 957).

[38] DeVan, J. H. , and Evans, R. B., Proceedings Conf. Corros. React.

Materials, 557 (1962).

[39] Koger, J. W. , Corrosion, 3_0, 1 25 (1974).

[40] Koger, J. W. , ORNL-RM-4286 (1972); Nucl. Sci. Abstr., 29,

8256 (1974).

[41] Oak Ridge National Laboratory, "The Development Status of Molten

Salt Breeder Reactors"

,

Rpt. ORNL -481 2 -UC -8 0 ; NTIS, U. S. Dept.

Commerce, Springfield, Va., (Aug. 1972).

[42] Lukashenko, E. E., and Reutova, G. A., Nov. Teor. Tekhnol.

Metall . Protsessov, 119 (1973).

[43] Boser, 0.,' "Study of Safety Aspects of High-Temperature Thermal

Energy Storage Systems", NSF No. AER 75-20605, (December, 1975)

[44] Harrison, R. W. , and Hendrixson, W. H. , "Lithium Fluoride

Bellows Capsule Tests", General Electric Company,

Cincinnati, Ohio, Jan. 1970, Contract NAS 3-8523.

[45] Harrison, R. W. , and Hendrixson, W. H., "Compatibility of

Columbium Base Alloys with Lithium Fluoride", General

Electric Company, Space Division, Cincinnati, Ohio,

March, 1970, NASA CR-1526.

[46] Mathews, A. L., and Baes, C. F., Inorg. Chem. , 7_, 373 (1968).

[47] Manning, D. L., and Mamantov, G., J. Electrochem. Soc., 124,

480 (1977).

[48] Ting, G., Baes, C. F., Bamberger, C. E., and Mamantov, G.,

J. Inorg. Nucl. Chem., 3_9, 1803 (1977).

[49] Manning, D. L., and Mamantov, G., J. Electroanal . Chem.

(in press) (1978)

[50] Janz, G. J., and Tomkins, R. P. T., Corrosion, 34_ (in press)

(1978) .

17
LiF

[51] Eichelberger , J. L., (Pennwalt Corpn.) "Investigations of

Metal Fluoride Thermal Energy Storage Materials:

Availability s Cost , Chemistry ", ERDA Rpt COO-2990-6; NTIS,

U. S. Dept. Commerce Springfield, Va. (Dec., 1976).

[52] Petit, G., and Cremieu, A., Compt. Rend., 245 , 360 (1956).

[53] Macleod, A. C., J. Chem. Soc., Faraday Trans. I, 69,

2026 (1973).

[54] Voskresenskaya, N. K. , Sokolov, V. A., Banashak, E. I.,

and Schmidt, N. E., Akad . Nauk. SSSR, Izv. Fiz Khim. Anal.,

2_7 , 233 (1956).

[55] Dworkin, A. S., and Bredig, M. , J. Phys . Chem., 64 , 269

[I960).

[56] Clusius, K. , Goldmann, J., and Perlick, A., Z. Naturforsch .

,

4A , 424 (1949).

[57] Schinke, H. , and Sauerwald, F., Z. anorg. allgm. Chem.,

287, 313 (1956); ibid., 284, 131 (1956); ibid., 304,

2S_ (1960) .

[58] von Wartenberg, H. , and Schulz, H., Z. Elektrochem. , 27 , 568 (1921).

[59] Sense, K. A., and Stone, R. W. , J. Phys. Chem., 62 , 1411 (1958).

[60] Eisenstadt, M., Rothberg, G. M., and Kusch, P., J. Chem.

Phys. , 29, 797 (1958) .

[61] Scheffe, R. S., and Margrave, J. L., J. Chem. Phys., 31 , 1682 (1959).

[62] Ruff, 0., Schmidt, G., and Mugdan, S., Z. anorg. allgm.

Chem. , 1_2_3 , 83 (1922) .

[63] Janz, G. J., et al., (MSDC-RPI); merge of v.p. data of

ref. (58,60,61 and 62) (unpublished work, 1978).

[64] Sreenivasan ., K . ,' and Altman, M. , J. Eng. for Power, 189

(July, 1969).

[65] Petrov, A. V., Tsypkina, N. S., and Logachev, Yu. A.,

Sov. Phys. Solid State, 1_6, 39 (1974).

[66] Srinivasan, R., and Krishnan, R. S., "Thermal Conductivity "

,

in "Progress in Crystal Phy sics", Vol. 1, (R. S. Krishnan,

ed.), Interscience, New York, 1958.

[67] Ballard, S. S., McCarthy, K. A., and Davies, W. C., Rev. Sci.

Inst. , 21 , 905 (1950) .

[68] Ioffe, A. V., and Ioffe, A. F., Dokl . Akad. Nauk SSSR, 97 , 821 (1954).

[69] Spindler, P., Moore, J. P., and Graves, R. S., Proc . 9th

Conf. Thermal Conductivity, Ames, Iowa, 6-8 Oct., 1969;

Phys. Abstr., 73_, 3882 (1970).

[70] Janz, G. J. et al . , (MSDC-RPI) unpublished work (1977).

[71] Zarzycki, G., Compt. Rend., 234 , 1370 (1952).

[72]

Petit, G., and Bourlange, C., Compt. Rend., 237 , 457 (1953).

18
LiF

[73] Thoma, R. E., USAEC-ORNL-2548 (1959).

[74] Deadmore, D. L., and Machin, J. S., J. Phys . Chem., 6A_, 824 (1960).

[75] Scarpa, G., Atti Accad. Nazi. Lincei Rc . , 2A11 , 476 (1915).

[76] Schmit z -Dumont , 0., and Heckmann, I., Z. anorg . allgm. Chem.,

260 , 49 (1949).

[77] Bergman, A. G., and Dergunov, E. P., Dokl . Akad. Nauk. SSSR,

31, 753 (1941).

[78] Cantor, S., Ward, W. T., and Robbins, G. D., USAEC-ORNL-3262

(1962)

19
II. Sodium Fluoride: NaF

1. Melting Temperature (T ) Melting point:

995° + 3 °C [1,11] . References [1-15].

2. Density (p)

Measurement method: Archimedean technique [16]

p = 2.7550-6.36 x 10" 4 T (2.1)

precision: + 0.15% uncertainty: ^ + 0.51

Table 2.1. Densities from equation (2.1)

T (K) p(g cm-3

) TOO p(g cm

-3

) 1280 1.941 1330 1.909

1290 1.935 1340 1.903

1300 1.928 1350 1.896

1310 1.922 1360 1.890

1320 1.915 1370 1.884

References [12,16-29].

3. Surface Tension (y)

Measurement method: maximum bubble pressure [30]

y

= 289.60 - 8.20 x 10' 2 T (2.2)

precision: ^ + 0.5% uncertainty: ^ + 8%

Table 2.2. Surface tension from equation (2.2)

T(K)

Y (dyn cm 3 )

T

(K)

Y (dyn cm 3 ) 1270 185.5 1320 181.4

1280 184.6 1330 180.5

1290 183.8 1340 179.7

1300 183.0 1350 178.9

1310 182.2 1360 178.1

References [30-32],

4 . Viscosity (r\)

Measurement method: oscillating

n

= 3.970 x 10' 2 precision: ^ + 1,3%

sphere [12]

exp (9831/RT)

uncertainty

:

(2.3)

'V' + 15%

see table 2.3.

2 0

For numerical values:
Table 2.3. Viscosity from equation (2.3)

T(K)

n (cp)

T(K)

n (cp )

1290 1 .84 1390 1 .40

1300 1.78 1400 1 . 36

1310 1.73 1410 1.33

1320 1 .68 1420 1 .29

1330 1 . 64 1430 1 . 26

1340 1.59 1440 1 .23

1350 1 .55 1450 1 . 20

1360 1 .51 1460 1 . 18

1370

1380

1 .47

1.43

1470 1.15

References [12].

Electrical Conductance (k)

Measurement method: ac ; Kelvin bridge [33]

k = 1.4633 + 2,7354 x 10" 3 T (2,4)

precision: + 0.2% uncertainty: ^ + 4%

Table 2.4. Electrical conductance from equation (2,4)

T(K)

K

( ohm 1 cm 1 )

T(K)

K (ohm 1 cm 1

) 1270 4. 937 1350 5 .156

1280 4 .965 1360 5 .183

1290 4 .992 1370 5 . 211

1300 5 . 019 1380 5 .238

1310 5.047 1390 5 .265

1320 5 .074 1400 5 .293

1330 5.101 1410 5.320

1340 5 .129 1420 5 . 348

References [33-37].

Safety and Hazards

A. Hazard rating [38-40]

(i) Toxicity - severe

(ii) Vapor pressure: at m.pt. (995°C) , ^ 0,5 mm; at 1050°C, ^ 1mm

(iii) U. S. o'ccupational standards! 5,5 mg m" 3 (air)

B. Disaster hazards [38,41-43]

(i) Molten salt bath "explosions"; i,e., explosive generation of

steam due to bulk water "carry-over" and/or equipment

failufe; i.e., explosive expansion of "trapped" air.

(ii) Fluorides, when heated to decomposition, or contacted with

acids, emit highly toxic fumes.

References [38-43].

Corrosion

see table 2.5.
NaF

Table 2.5. Corrosion studies from primary research literature

Studies References

Cr 44

Ni-Cr-Mo alloys (INOR- 8 ; Hastelloys B, W, and N) 45,46

SSNi-12P 47

Quartz 48

A1 49

Various metals 50

Corrosion studies in molten salts

with NaF as one component (e.g..

Cl, CO 3 ,

. , .

)

51-67,74,75

Electro-chemical behavior of

oxide ions and related species

in molten fluorides

68-70

Electroanalytical studies in molten

fluorides 71

Annotated corrosion biblio. 72

Corrosion: molten fluorides (survey) 73

References [44-75] ,

8. Diffusion

Measurement method: capillary [76-77]

List of diffusing species investigated in NaF as solvent

Na

+

Sodium, Na

+ (self -diffusion)

DNa

+ = 3.08 x 10" 3 exp [-8700/RT] (2.5)

precision: + 3% uncertainty: ^ + 201

Table 2.6. Self -dif fus ion coefficients from equation (2.5)

T(K)

W x f

5 (cm 2 sec 3 )

T(K)

D„ + x 10 5 Na T

(cm 2 sec 1 ) 1290 10.34 1360 12.31

1300 10.61 1370 12.61

1310 10.89 1380 12.90

1320 11.17 1390 13.20

1330 11.45 1400 13.50

1340 11.74 1410 13.80

1350 12.02

References [76-77]

9. Heat of Fusion (A H°)

Measurement method: drop calorimetry [79]

22
NaF

Table 2.7. Heat of fusion

AH°

* _i (kcal mol ) Uncertainty

8.03 ^ ± 0.5%

References [15,78-81].

10.

Beat Capacity (Cp)

Measurement method: drop calorimetry [79]

C = 10.91 + 4.654 x 10' 3 T - 9.3836 x 10 4 T

-2 (2.6)

P

precision: ^ + 0.2% uncertainty: ^ ± 1%

Table 2.8. Heat capacity (liquid) from equation (2.6)

T(K)

C

P 1 -! (cal K

_1 mol 1 )

T(K)

C P (cal K~1 mol -3

) 1270 16.76 1420 17.47

1280 16.81 1430 17.52

1290 16.86 1440 17.57

1300 16.90 1450 17 . 61

1310 16.95 1460 17.66

1320 17 . 00 1470 17 . 71

1330 17 . 05 1480 17.76

1340 17 . 09 1490 17 .80

1350 17 . 14 1500 17 .85

1360 17.19 1600 18 . 32

1370 17 . 24 1700 18.79

1380 17 . 28 1800 19.25

1390 17.33 1900 19.73

1400

1410

17.38

17.42

2000 20.19

References [78-80, 82-84].

11.

Volume Change on Melting (AF^J

Measurement method: crystallization pycnometry [86]

Table 2.9. Volume change on melting

< 4 VV Uncertainty

24.0% ^ ± 2%

References [85-86].

12.

Vapor Pressure (

vap

) Measurement method: boiling point [87,88] j transpiration [89]

log p

= 8.5954 - 11331/T (2.7)

precision: 'v ± 1.3% uncertainty: ^ + 5%

For numerical values: see table 2.10

23
NaF

Table 2.10. Vapor pressures from equation (2,7)

T(K)

P(mm)

T(K)

P(mm)

1280 0.55 1640 48 .56

1300 0.76 1660 58 . 82

1320 1 .03 1680 70.92

1340 1.38 1700 85 . 14

1360 1 .84 1720 101 .

1380 2.42 1740 121.2

1400 3 . 18 1760 143 .

1420 4.13 1780 169 .

1440 5 .33 1800 199 .

1460 6.83 1820 234 .

1480 8 o 70 1840 273.7

1500 11 . 00 1860 318 .

1520 13.83 1880 370 .

1540 17 . 28 1900 428 .

1560 21.48 1920 494 .

1580 26.54 1940 568 .

1600

1620

32 . 62

39 . 90

1960 652 .

References [87-90],

13. Thermal Conductivity (liquid) (X^)

Measurement method: coaxial cylinder [91]

X = -14,85 x 10’ 3 + 14.071 x 10" 6 T (2,8)

precision: not estimated uncertainty: ^ + 25%

Results were reported in graphical form only.

Table 2.11. Thermal conductivity of melt from equation (2,8)

T

(K)

X x 10 4 (cal cm

sec -K

-1

)

T(K)

X x 10 4 (cal cm

sec

-

K

-1

) 1270 30.2 1310 35.8

1280 31.6 1320 37.2

1290 33.0 1330 38.6

1300 34.4

Eq. obtained by fitting the interpolated data from the graphical

presentation in [91].

References [91]

14. Thermal Conductivity (solid) (\ ) s Measurement method: absolute stationary state [92]

precision: not estimated uncertainty: ^ t 10%

Results were reported in graphical form only.

For numerical values: see table 2.12.

24
NaF

Table 2.12. Thermal conductivity of solid

T(K)

X x 10 3 (cal cm

-

sec -

K

-1

)

T(K)

X x 10 3 (cal cm

-1 sec -1 K~ 3

300 36.1 700 14.1

400 25 .

8

800 12.6

500 20.1 900 11.5

600 16.2 1000 11.2

Sole investigation in this temperature range; values interpolated

from the graphical presentation in [92].

References [92-93].

15. Cryoscopic Constant

Measurement method: calculated from AH£ [94]

Table 2.13. Cryoscopic constant

k

f Uncertainty

, il - 1 , mol kg )

16 .

'v ± 0.5%

References [78-81,94-105].

16. References

[1] Rossini, F. D., Wagman, D. D., Evans, W. H. , Levine, S., and

Jaffe, I., Selected Values of Chemical Thermodynamic Properties 3 NBS Circ. 500 ; U. S. Gov't Printing Office, Washington, D. C. (1952)

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2577 (1959).

[3] Mal'tsev, V. T., and Bukalova, G. A., Zh. Neorg. Khim., 10(6)

,

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[5] Rolin, M., and Rey, M. , Bull. Soc. Chim. Fr., (9), 2785 (1965).

[6] Barton, C. J. , Bratcher, L. M., and Grimes, W. R., Unpublished,

cited ref. in Phase Diagrams of Nuclear Reactor Materials”

,

R. E. Thoma 3 ed; USAEC - ORNL - 2 54 8 (1959).

[7] Grjotheim, K. , ’'Contribution to the Theory of Aluminum Electrolysis”3 Kgl. Norske. Videns. Selsk. Skrifter No. 5, Trondheim, Norway (1956)

[8] Phillips, N. W. F., Singleton, R. H., and Holl ingshead , E. A., J.

Electrochem. Soc., 102(12), 690 (1955).

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Fuseya, G., Sugihara, C., Nagao, N. , and Teraoka, B., J. Electrochem.

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D. C. (1971).

[12] Abramov, G. A., Vetyukov, M. M., Gupalova, I. P., Kostyukov,

A. A., and Lozhkin. L. N. , "Theoretical Principles of Electrometallurgy of Aluminum

3 (in Russ.) Metallu.rgizdat , Moscow (1953).

25
NaF

[13] Holm, J.L., Ph,D. Thesis, Univ. Trondheim, NTH, Norway (1963).

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[35] vide infra ref. [19].

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U. S. Gov't Printing Office, Washington, D. C. (1975).

2 6

[39]
NaF

[40] Vapor pressure, calculated (see p, 24, this work).

[41] " Potential Hazards in Molten Salt Baths for Heat Treatment of

Metals ", National Board Fire Underwriters Research Report No,

2 (1 954).

[42] " Handbook of Reactive Chemical Hazards”, Bretherwick, L.,

Butterworths Co., London Cl 975).

[43] Janz, G. J. , Tomkins, R. P. T., Downey, J, R. , Jr., and Allen, C. B,,

"Safety and Hazards, Chapter in "Euteetie Data", ERDA TID-271 63 -PI

NTIS, U. S. Dept. Commerce, Springfield, Va , (1977),

[44] Brasunas, A., Metal Prog,, 62^ 88 (1952),

[45] Bettes, E. S., Nucl. Sci, Eng,, 2_, 804 (1957),

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G. M., ORNL-1934, Oak Ridge Natl, Lab., (1956),

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Commerce, Springfield, Va,, (Aug, 1972),

[48] Heimann, R, , Glastech, Ber,, 43_, 83 (1 970),

[49] Lukashenko, E, E., and Reutova, G. A,, Nov, Teor, Tekhnol,

Metall. Protsessov,, 119 (1973),

[50] Koger, J, W. , Corrosion, 3_0 , 1 25 (1 974),

[51] Khan, I, A., Ber, Kernfor schungsanlage Juelich, Juel-608-RW, (1969),

[52] Khan, I. A., Inst, Reaktorwerkst . , Kernforschungsanlage , Juel718 -RW (1970),

[53] Bowles, P, J,, and Newdick, P. C, , Electroplating and Metal

Finishing, 24_, 6 (1971),

[54] DeVan, J, H, , " Examinations of Hump Impellers from Sodium and

Fused Salt Hump Endurance Tests", ORNL CF-61-4-77, Oak Ridge

National Lab., (1961),

[55] Adamson, G. M. , Manly, W, D,, and Crouse, S, R, , "Corrosion by

Molten Fluorides", ANP Materials Meeting ORNL-2685 , Cl 9 58),

I [56] Huntley, W, R. , and Gnadt, P. A,, Oak Ridge Nat'l Lab,, Report

ORNL-TM-3863 , C1973); Nucl. Sci, Abstr,, 27_, 12446 (1973),

[57] Gill, C. B,, Straumanis, M, E,, and Schlechten, W. B,, J,

Electrochem. Soc,, 102 , 42 (1955),

[58] Litman, A, P., "Corrosion of Volatility Pilot Plant Mark I

INOR-S Hydro fluorinator and Mark III , Hickel Fluorinator

after Fourteen Dissolution Runs ", ORNL-3253, Oak Ridge

Nat'l Lab. , (1962)

,

[59] Litman, A. P., and Goldman, A. E,, "Corrosion Associated with

Fluoridation in the Oak Ridge Hat ( l Lab , Fluoride

Volatility Process", ORNL-2832, Oak Ridge Nat'l Lab, (J-961),

[60] Manly, W. D., Coobs, J, H. , DeVan, J, H. , Douglas D, A,,

Inouye, H. , Patriarca, P,, Roche, T, K. , and Scott, J, L,,

"Metallurgical Problems in Molten Fluoride Systems", Proc.

2nd U. N. Inter. Conf. Peaceful Uses of At. Energy, 7_, 223 (1958).

27
NaF

[61] Oak Ridge Nat'l Lab., Molten Salt Reactor Program Semiannual

Progress Report for Period Ending July 31, 1964, ORNL-3708,

(1964)

[62] Vreeland, D. C., Hoffman, E. E., and Manly, W. D., Nucleonics,

11, 36 (1953).

[63] Boser, 0., "Study of Safety Aspects of High Temperature Thermal

Energy Storage Systems ", NSF No, AER 75-20605 , (Dec. 1 975).

[64] Grimes, W. R. , and Cuneo , D. R. , "Molten Salts as Reactor Fuels'

3 Reactor Handbook, 2nd ed . , 1_, 425 (1955),

[65] Shimotake, H. , and Hesson, J, C,, Adv . Chem, Series, No, 64,

149 (1967).

[66] Boser, 0., Study of Safety Aspects of High Temperature Thermal

Energy Storage Systems 3 ERDA Thermal Energy Storage Info,

Exchange Mtg., Cleveland, NSF-AER 75-20605 (Sept. 1976),

[67] Venkatasetty , H. V. , "Thermodynamic Properties and Corrosion

Characteristics of Thermal Energy Storage Eutectic Mixtures"3 paper presented at 152n^ Meeting of the Electrochemical Soceity,

Atlanta, Ga., (October, 1977).

[68] Mathews

,

A. L . , and Baes , C . F . , Inorg. Chem., 7_, 373 (1968)

[69] Manning

,

D. L. and Mamantov, G., J. Electrochem. Soc., 124,

[70] Ting, G., Baes, C. F., Bamberger, C. E., and Mamantov, G.,

J, Inorg, Nucl. Chem., 3_9, 1803 (1977).

[71] Manning, D. L., and Mamantov, G., J. Electroanal, Chem.,

(in press) (1978).

[72] Janz, G. J., and Tomkins, R. P. T., Corrosion, 3_4 (in press)

(1978).

[73] Eichelberger , J. L., (Pennwalt Corp.) "Investigations of Metal

Fluoride Thermal Energy Storage Materials: Availability 3 Cost 3 Chemistry" ERDA Rpt COO2990-6; NTIS, U. S. Dept. Commerce,

Springfield, Va . , (Dec. 1976).

[74] Kochergen, V. P., and Ignat'eva, N. I., Russ. J. Inorg. Chem.,

6(9), 1086 (1961).

[75] Ozeryanaya, I. N. , Volodin, V. P., and Smirnov, M. V., Zashchita

Metalov (USSR), 2, 230 (1969).

[76] Grjotheim, K. , Malinovsky, M., Matiasovsky, K,, Zuca, S., and

0ye , H. A., J. Chim. Phys . , 145 (1969).

[77] Grjotheim, K. , and Zuca, S., Acta Chem. Scand., 2_2, 531 (1968),

[78] O'Brien, C. J., and Kelley, K. K., J. Amer. Chem. Soc., 7

, 5616 (1957).

[79] Macleod, A. C., J. Chem. Soc. -Faraday Trans. I, 6_9, 2026 (1973).

[80] Frank, W. B., J. Phys. Chem., 65_, 2081 (1961).

[81] Kelley, K. K. , U. S. Bur. Mines, Bulletin 476 (1949).

[82] Vide infra ref. [11]

[83] Lyashenko, V. S., Metallurg., 1_0, 85 (1 935).

28
NaF

[84] Krestonikov, A. N., and Karetnikov, G. A,, Legie Metal,, 3^

29 (1934).

[85] Schinke, H. , and Sauerwald, F., Z, anorg . allgm, Chem,, 287,

313 (1956); ibid,, 28£, 131 (1956); ibid,, 304, 25 (19FDJ.

[86] Landon, G. J. , and Ubbelohde, A, R, , Trans, Faraday Soc,,

52, 647 (1956)

,

[87] von Wartenberg, H, , and Schulz, H, , Z, Elektrochem , , 27, 568

(1921) .

[88] Sense, K. A., Alexander, C, A,, Bowman, R, E,, and Filbert,

R. B. , Jr., J, Phys . Chem., 6l_, 337 (1957); Sense, K. A,,

Alexander, C, A., Bowman, R. E., Stone, R. W, , and Filbert,

R. B., Jr,, J, Phys. Chem,, (O, 384 (1957).

[89] Ruff, 0., Schmidt, G., and Mugdan, S,, Z, anorg. allgm, Chem,,

123, 82 (1922).

[90] Janz,G.J., et al . , (MSDC-RPI) - calculations merging V,P,

data base of ref. 87-89 (unpublished work, 1978),

[91] Polyakov, P. V. , and Mozhaev, V. M., High Temp,, 13 , 600 (1975),

[92] Petrov, A, V. , Tsypkina, N. S,, and Logachev, Yu, A,, Sov,

Phys. Solid State, 1_6, 65 (1974),

[93] Ioffe, A. V., and Ioffe, A. F., Dokl, Akad , Nauk SSSR, 97,

821 (1954),

^

[94] Janz, G. J., et al., (MSDC-RPI) unpublished work (1977).

[95]

Petit, G., and Bourlange, C., Compt. Rend. Acad. Sci. (Paris),

240, 457 (19531,

[96] Hoenen, P. H . J., Z. physik. Chem., 83, 513 (1913)

[97] Zarzycki, G. , Compt. Rend., 234, 1370 (1952).

[98] Doucet , Y .

,

492 (1956)

Bizouard, M., and Netzer, C., Compt. Rend., 242,

[99] Rol in , M . , J . Four. Elec. , 61, 157 (1952)

[100] Rolin, M. , J . Four. Elec., 62, 11 (1953).

[101] Cantor , S . , ibid . , 65 , and Ward. W. T., J. Phys. Chem.,

2208 (1961).

67_, 1868 , 2766 (1963);

[102] Thoma , R. E. , Hebert, G. M., Insley, H., and Weaver, C. F., Inorg.

Chem. , 2, 1005 (1963)

[103] Bergman, A. G., and Dergunov, E. P., Dokl. Akad. Nauk SSSR, 31 , 753 (1941).

[104] Schmit z -Dumont , 0., Bergerhoff, G., and Hartert, E., Z. anorg.

allgm. Chem., 283, 314 (1956).

[105]

Amadori, M., Atti Accad. Nazi. Lincei. Rc . , 2211, 366 (1913).

29
Ill

Potassium Fluoride: KF

1. Melting Temperature ( T^

)

Melting point:

856° + 3 °C [3,4]

References [1-8] .

Density (p)

Measurement method: Archimedean technique [9]

p

= 2.6464 - precision: + 0.16 ! 6.515 x 10' 4 T (3.1)

uncertainty: ^ + 0.6 !

Table 3.1. Densities from equation (3.1)

TOO p(g cm -3

) T(K) p(g cm 3

) 1130 1.9102 1210 1.8581

1140 1.9037 1220 1.8516

1150 1.8972 1230 1.8451

1160 1.8907 1240 1.8385

1170 1.8841 1250 1.8320

1180 1.8776 1260 1.8255

1190 1.8711 12 7 0 1.8190

1200 1.8646 1280 1.8125

1290 1.8060

References [9-12].

3. Surface Tension (y)

Measurement method: maximum bubble pressure [13]

Y

= 176.666 + 7.392 x 10' 3

T - 3.330 x 10~ 5 T

2 (3.2)

precision: + 0.2% uncertainty: ^ + 5%

Table 3.2. Surface tension from equation (3.2)

T(K)

Y (dyn cm *) T(K)

Y (dyn cm 3 ) 1200 137.6 1400 121.7

1210 136.9 1410 120.9

1220 136.1 1420 120.0

1230 135.4 1430 119.1

1240 134.6 1440 118.3

1250 133.9 1450 117.4

1260 133.1 1460 116.5

1270 132.,

3

1470 115.6

1280 131.6 1480 114.7

1290 130.8 1490 113.8

1300 130.0 1500 112.8

1310 129.2 1510 111.9

1320 128.4 1520 111.0

1330 127.6 1530 110.0

1340 126.8 1540 109.1

1350 126.0 1550 108.1

1360 125.1 1560 107.2

1370 124.3 1570 106.2

1380 123.5

1390 122.6

30
References [13]

KF

Viscosity (r\)

Measurement method: oscillating sphere [14]; uncertainty ± 20%

Table 3.3 Viscosity

T n (K) (cp)

1246 .1.59

References [14]

Electrical Conductance (<)

Measurement method: ac technique [15]

k = 9.2728 x 10' 2 + 3.0628 x

10" 3 T (3.3)

precision: + 0.5% uncertainty: ^ + 5%

Table 3.4. Electrical conductance from equation (3.3)

T K T K (K) ( ohm 1 cm 1

) (K) ( ohm 1 cm 1 ) 1130 3 .554 1220 3.829

1140 3 .584 1230 3 .860

1150 3 . 615 1240 3 .891

1160 3.646 1250 3 .921

1170 3.676 1260 3 .952

1180 3.707 1270 3.982

1190 3.737 1280 4 . 013

1200 3 .768 1290 4 . 044

1210 3.799

References [11,15-21].

Safety and Hazards

A. Hazard rating [22-24]

(i) Toxicity - severe

(ii) Vapor pressure: at m.pt. (856°C), ^ 0.5 mm;

at 900°C, ^ 1 mm

-3

(iii) U. S. occupational standards: 7.6 mg m {air)

B. Disaster hazards [22,25-27]

(i) Molten salt bath "explosions": i.e., explosive generation of steam due to bulk water "carry-over and/or

equipment failure; i.e., explosive expansion of

"trapped" air

(ii) Fluorides , when heated to decomposition, or contacted with acids, emit highly toxic fumes

References [22-27].
KF

7 . Corrosion

Table 3.5. Corrosion studies from primary research literature

Studies References

Cr 28

Ni-Cr-Fe 29 , 30

INOR-8 30-33

A1 34,35

Ni-Mo-Cr-Fe (Hastelloy) 36

Inconel 33,37

Electro-chemical behavior of

oxide ions and related species

in molten fluorides

38-40

Electro-analytical studies in

molten fluorides 4 1 • Annotated corrosion biblio. 42

Corrosion: molten fluorides (survey) 43

References [28-43].

8. diffusion

Measurement method: capillary [44]

List of diffusing species investigated in KF as solvent

K

+

Potassium, K (self -diffusion)

-3

D^+ = 2.46 x 10 exp [ -7 500/RT] (3.4)'

precision: + 2.51 uncertainty: m + 20‘

Table 3.6. Self -diffus ion coefficients from equation (3.4)

T(K)

D k+ x 10 5 (cm 2 sec *)

T(K)

D k+ x 10 5 (cm 2 sec *)

1140 8.97 1220 11.15

1150 9.24 1230 11.43

1160 9.50 1240 11.72

1170 9.77 1250 12.01

1180 10 0 04 1260 12.30

1190 10.31 1270 12.59

1200 10.59 1290 13.19

1210 10.87

References [44]

32
KF 9.

Heat of Fusion (A Hj.)

Measurement method: drop calorimetry [45]

Table 3.7. Heat of fusion

AH 0f -1 Uncertainty

(kcal mol )

7 .05 ^ ±0.5%

1

References [45-49] .

10.

Heat Capacity (C

)

Measurement method: drop calorimetry [45]

C = 11.845 + 2.762 x 10" 3 T - 9.11157 x 10 4 T"

2 (3.5)

P

precision: ^ + 0.2% uncertainty: ^ + 1%

Table 3.8. Heat capacity from equation (3.5)

T(K)

C

P, , (cal K

1 mol 1

)

T00

C P,

(cal K ^mol 1

) 1130 14.89 1370 15.58

1150 14.95 1390 15 . 64

1170 15 . 01 1400 15. 66

1190 15 . 07 1410 15.69

1200 15.09 1430 15.75

1210 15.12 1450 15.81

1230 15.18 1470 15 .86

1250 15 . 24 1490 15.92

1270 15 . 30 1500 15.95

1290 15.35 1600 16.23

1300 15 . 38 1700 16.51

1310 15.41 1800 16.79

1330 15.47 1900 17 . 07

1350 15.52 2000 17.35

References [45,50-53].

11.

Volume Change on Melting (AF^J

Measurement method: capillary technique [54]

Table 3.9. Volume change on melting

(AV

f /V

s

) Uncertainty

17.2% ^ ± 3%

References [ 54]

12.

Vapor Pressure (

va ^

)

Measurement method: boiling point [55-56]

log p

= 8.4262 - 9820/T (3.6)

precision: a- + 0.01% uncertainty: ^ + 5%

3 3

For numerical values: see table 3.10.
KF

Table 3.10. Vapor pressure from equation (3.6)

T(K)

P(mm)

T(K)

P

( mm)

1550 123.2 1670 351.

1560 135 .

1680 381.0

1570 148 .

1690 412 .

1580 162 .

1700 446 .

1590 177.9 1710 482.5

1600 194.4 1720 521.1

1610 212 .

1730 562.2

1620 231.5 1740 606 .

1630 252 .

1750 652 .

1640 274 .

1760 702 .

1650 298.3 1770 755.4

1660 324 .

References [55-57].

13. Thermal Conductivity (liquid)

No thermal conductivity studies reported.

14. Thermal Conductivity (solid) (X ) No thermal conductivity studies reported.

15.

16.

Cryoscopic Constant

Measurement method: calculated

Table 3.11.

from AH| [58]

Cryoscopic constant

k Uncertainty -l f -1.

(K mol kg )

20.9 ^ ± 0.5%

References [45,46,48,53,58-65].

References

[1] Phillips, B., Warshaw, C. M. , and Mockrin, I., J. Amer. Ceram.

Soc. , 49 (12) , 631 (1966)

[2] Fedotiev, P. P., and Timiofeff, K. , Z. anorg'. allgm. Chem., 206 , 263 (1932).

[3] Rossini, F. D., Wagman, D. D., Evans, W. H. , Levine, S., and Jaffe

I., "Selected Values of Chemical Thermodynamic Properties , NBS

Circ. 500; U. S. Gov't Printing Office, Washington, D. C. (1952)

[4] Stull, D. R. , and Prophet, H. (eds.), "JANAF Thermochemical Tables

2nd Ed."; NSRDS-NBS 37, U. S. Gov't Printing Office, Washington,

D. C. (1971).

[5] Barton, C. J., Bratcher, L. M.. and Grimes,. W. R. , Cited in

"Phase diagrams of Nuclear Reactor Materials" R. E. Thoma

,

ed., USAEC-ORNL-2548 (1959).

[6] Dergunov, E. P., Doklad. Akad . Nauk. SSSR, 6_0 (7), 1185 (1948).

[7] Jenssen, B. , Ph.D. Thesis, Univ. of Trondheim (NTH), Norway (1969)

[8] Johnson, J. W. , and Bredig, M. A., J. Phys . Chem., 6_2 , 604 (1958).

34
KF

[9]

Yaffe, I. S., and van Artsdalen, E. R., Chemistry Division Semiannual Progress Report, Oak Ridge National Laboratory, ORNL2159, p. 77 (1956).

[10] Schinke, H. , and Sauerwald, F., Z, anorg . allgm. Chem., 284, 131

(1 956).

[11] Jaeger, F. M., and Kapma, B., Z. Anorg. Chem., 113 , 27 (1920),

[12] Yim, E. W. , and Feinleib, M, , J. Electrochem. Soc . , 104, 627

(1957). —

[13] Jaeger, F. M. , Z. anorg. allgm. Chem,, 1 01 , 1 (1917)-,

[14] Sheiko, I. N. , Tr . Vses, Sovesch. Fiz, Rasplav. Solei. 2 nd Kiev

1963 , p. 79 (1965) .

[15] Bronstein, H. R. , and Bredig, M, A., Chemistry Division Semiannual Progress Report, Oak Ridge National Laboratory, ORNL2782, 59 (1959),

[16] Arndt, K. , and Kalass, W. , Z. Elektrochem . , 3_0, 1 2 (1924).

[17] Ryschkewitsch, E,, Z. Elektrochem,, 3_9, 531 (1933),

[18] Argyriades, D., Dissertation. Aachen (1955).

[19] Yaffe, I. S., and van Artsdalen, E. R., J, Phys. Chem,, 60,

1125 (1956).

[20] Winterhager, H. , and Werner, L,, Forschungsber , Wirtsch,

Verkehr sminister iums Nordrhein-Westfalen, No. 438 (1957),

[21] Yim, E. W. , and Feinleib, M., J. Electrochem. Soc., 104, 622,

662 (1957).

[22] "Dangerous Properties of Materials", Sax, N, I,, Van Nostrand

Reinhold Co . , N. Y. (1969)

[23] "Registry of Toxic Effects of Chemical Substances"

,

Christensen,

H. E., and Lubinbyhl , T. T., eds., U. S. Dept, H.E.W,; U. S.

Gov't Printing Office, Washington, D, C. (1975),

[24] Vapor pressure, calculated (see p. 34, this work),

[25] "Potential Hazards in Molten Salt Baths for Heat Treatment of

Metals", National Board Fire Underwriters Research Report

No. 2 (1954),

[26] "Handbook of Reactive Chemical Hazards", Bretherwick, L.,

Butterworths Co., London (1975).

[27] Janz, G. J., Tomkins, R. P, T., Downey, J. R., Jr., and Allen, C. B.,

"Safety and Hazards", Chapter in "Eutectic Data", ERDA TID - 271 63 -PI

NTIS, U. S. Dept. Commerce, Springfield, Va, (1977),

[28] Brasunas, A., Metal Progr , , 6_2, 88 (1952),

[29] Grimes, W. R,, Blankenship, F, F,, Keilholtz, G, W, , Poppendiek,

H. F., and Robinson, M. T., Proc. Sec. U. N. Inter. Conf.

Peaceful Uses of Atomic Energy, Geneva, 28_, 99 (1958).

[30] Oak Ridge Nat'l Lab., Molten Salt Reactor Program Semiannual

Progress Report, ORNL-3708, (1964).

[31] Bettis, E. S., Nucl . Sci. Eng., 2_, 804 (1957).

35
KF

[32] Shimotake, H,, and Hesson, J, C,, Adv. Chem, Series, 64_, 149 (1967).

[33] Manly, W. D., et al , , "Construction Materials for Molten Salt

Reactors", Ch. 1 3 in "Fluid. Fuel Reactors ", Lane, J. A,, MacPherson,

H. G,, and Maslan, F., eds,, Addi son-rWesley Co. Inc. Publ . (1958).

[34] Pizzini, S., Magistris, A., and Sternheim, G., Corrosion Sci., 4,

345 (1964).

[35] Lukashenko, E. E., and Reutova, G. A,, Nov. Teor. Tekhnol. Metall.

Protsessov, 119 (1973).

[36] Koger, J, W, , Corrosion, 3^0, 125 (1974),

[37] Grimes, W, R, , and Cuneo , D, R, , "Molten Salts as Reactor Fuels",

Reactor Hdbk. , 1_, 425 (1955).

[38] Mathers, A. L t , and Baes, C, F., Inorg. Chem,, 7_, 373 (1968).

[39] Manning, D, L,, and Mamantov, G t , J. Electrochem. Soc., 124,

480 (1977). ~~

[40] Ting, G., Baes, C. F,, Bamberger, C. E,, and Mamantov, G., J,

Inorg, Nucl , Chem., 3_£, 1803 (1977).

[41] Manning, D. L., and Mamantov, G., J. Electroanal. Chem.

(in press) (1 978 )

,

[42] Janz, G, J., and Tomkins, R. P. T., Corrosion, 34 (in press)

(1978)

[43] Eichel berger , J, L., (Pennwalt Corpn,) "Investigations of Metal

Fluoride Thermal Energy Storage Materials : Availability , Cost, Chemistry", ERDA Rpt COO2990-6; NTIS, U. S, Dept,

Commerce, Springfield, Va . (Dec. 1976).

[44] Grjotheim, K. , and Zuca, S., Acta Chem. Scand., Iff, 531 (1968).

[45] Macleod, A. C., J, Chem. Soc. Faraday Trans I, 6_9, 2026 (1973).

[46] Petit, G., and Cremieu, A,, Compt. Rend., 243 , 360 (1956).

[47] Lyashenko, V. S., Metallurgy (USSR), 1£, 35 (1935); see also

Rossini, F. D., Wagman, D. D,, Evans, W. H., Levine, S.,

Jaffe, I,,' NBS Circ. 500 (1952),

[48] Kelley, K. K. , U. S. Bureau Mines, Bull, 476 (1949); 393 (1936),

[49] Dworkin, A, S., and Bredig, M., J. Phys. Chem,, 6£, 269 (1960).

[50] Douglas, T, B,, Brookhaven National Laboratory, Report NO. BNL-2446

(1954); Trans, Amer . Soc. Mech. Eng , , 7_9, 23 (1957)

[51] vide infra ref. [4 7] .

[52] Westrum, E . F , , and Pitzer , K, S

, J. Amer. Chem. Soc

[53] Lyashenko, V, S., Metallurgy (USSR), 1£, 35 (1935).

[54] Schinke, H. , and Sauerwald, F., Z, anorg . allgm, Chem., 287 , 313

(1956).; ibid,, 284, 131 (1956); ibid., 30£, 25 (1960).

[55] von Wartenberg, H, , and Schulz, H. , Z, El ektrochem . , 27_, 568 (1921).

[56] Ruff. 0., Schmidt, G., and Mugdan, S., Z. anorg, allgm. Chem.,

123, 83 (1922).

36
KF

[57] Janz, G. J., et al . , (MSDC-RPI); calculations merging V.P. data

(ref. 55,56) (unpublished work, 1978).

[58] Janz, G. J., et al., (MSDC-RPI) unpublished work (1977).

[59] Hoenen, P. H. J., Z. physik. Chem., 8_3, 513 (1913).

[60] Rolin, M., J. Four. Elec., 6^, 157 (1952); ibid, (P2, 11 (1953).

[61] Zarzycki, G., Compt. Rend., 234 , 1370 (1952).

[62] Petit, G., and Bourlange, C., Compt. Rend., 237 , 457 (1953).

[63] Kurnakov, N. S., and Wrzesnewsky, J. B., Z. anorg. allgm. Chem.,

74, 89 (1912).

[64] Amadori, M. , Atti. Accad. Nazi. Lincei Rc . , 2211 , 366 (1913).

[65] Sandonnini, C., and Scarpa, G., ibid., 2211 , 163 (1913).

3 7
IV. Lithium Chloride: LiCl

1. Melting Temperature (T ) Melting point:

610° ± 2

0 C [2,6]

References [1 - 15 ]

.

2 . Density ( p

)

Measurement method: Archimedean technique [3]

p = 1.8842 - 4.328 x 10~ 4 T (4.1)

precision: ± 0.34% uncertainty: 'v ± 0.5%

Table 4.1. Densities from equation (4.1)

T P T P (K) (g cm -3

) (K) (g cm -3

)

910 1.4904 990 1.4557

920 1.4860 1000 1.4514

930 1.4817 1010 1.4471

940 1.4774 1020 1.4427

950 1.4730 1030 1.4384

960 1.4687 1040 1.4341

970 1.4644 1050 1.4298

980 1.4601

References [1,3,9,11-14,16-28].

3.

Surface Tension (y)

Measurement method: maximum bubble pressure [29]

Y =180.42 - 5.83 x 10

_2

T (4.2)

precision: ± 0.3% uncertainty: ^ ± 0.5%

Table 4.2. Surface tension from equation (4.2)

T(K)

Y (dyn cm *) T(K)

Y (dyn cm *)

890 128.5 1030 120.4

900 128.0 1040 119.8

910 127.4 1050 119.2

920 126.8 1060 118.6

930 126.2 1070 118.0

940 125.6 1080 117.5

950 125.0 1090 116.9

960 124.5 1100 116.3

970 123.9 1110 115.7

980 123.3 1120 115.1

990 122.7 1130 114.5

1000 122.1 1140 114.0

1010 121.5 1150 113.4

1020 121.0

References [18,24,29-33].

38
LiCl

4. Viscosity (r\)

Measurement method: oscillating sphere [106]

n = 11.038 x 10' 2 exp [4563.9/RT] (4.3)

precision: ^ ± 0.6% uncertainty: 'v ± 10%

Table 4.3. Viscosity from equation (4.3)

T(K)

n (cp)

T(K)

n (cp)

900 1.417 1010 1.073

910 1.377 1020 1 . 049

920 1.340 1030 1.027

930 1.305 1040 1.005

940 1.271 1050 0.984

950 1.239 1060 0.964

960 1.208 1070 0.944

970 1.178 1080 0.926

980 1 .150 1090 0 .908

990 1.123 1100 0.891

1000 1.098 1110 0.874

References [13,34-40,106],

5. Electrical Conductance (k)

Measurement method: ac technique [3,19]

k = -2.0647 + 12.1271 x 10

_3

T - 3.7641 x 10" 6 T

2 (4.4)

precision: ^ ± 0.05% uncertainty: ^ ± 2.5%

Table 4.4. Electrical conductance from equation (4.4)

T(K)

K (ohm 1 cm 1

)

T(K)K (ohm 1 cm 1 ) 910 5.854 990 6.252

920 5 .906 1000 6.298

930 5 .958 1010 6.344

940 6.009 1020 6.389

950 6.059 1030 6.433

960 6.108 1040 6.476

970 6 . 157 1050 6.519

980 6.205

References [3,12,15,17,19,20,24,25,27,35,37,41-51].

6. Safety and Hazards

A. Hazard rating [52-54]

(i) Toxicity - slight

(ii) Vapor pressure: at m.pt. (610°C) , ^ 25 x 10

_2

mm;

at 780°G, ^ 1 mm

B. Disaster hazards [52,55-57]

(i) Molten salt bath "explosions": i.e., explosive generation of

steam due to bulk water "carry-over" and/or equipment failure;

i.e., explosive expansion of "trapped" air.

39
LiCl

(ii) Chlorides evolve highly toxic chloride fumes when heated to

decomposition, or contacted with acids.

References [52-57].

7. Corrosion

Table 4.5. Corrosion studies from primary research literature

Stud les References

Mg, Ni, Zr, Ti 59

Ti, Zr, Hf, ThCl 4 60

Artnco Fe 58,61

Solubility of metal oxides (Ni,

Ca, Zn, Mg) 59 ,62

Thermodynamics of corrosion 59,63,64

Corrosion - annotated biblio. 65

Electrochemical aspects 66

Reviews: corrosion - molten salts 67-69

References [58-69]

8. Diffusion

Measurement method: cited in tabulations

List of diffusing species investigated in LiCl as solvent

Li

+

, Cl", Na

+

, Rb

+

, Cs

+

, Pb

2+

, Ag

+

, Zr

2+

, Mo

3+

, Cl

2 precision: in table 4.6.2 uncertainty: in table 4.6.1

Table 4.6.1. Diffusion techniques, uncertainties, and species

Diffusion technique

of recommended 9tudy

Uncertainty (in

values of D) Species

capillary ^±20%

4- — 4- + 4- Li , Cl , Na , Rb , Cs

chronopotentiometry ^±10% Pb 2+

, Ag

+

, Zr 2+

, Mo 3+

Faradaic impedance ^±50% ci 2

Equation

D = A exp [ - E/RT] (4.5)

For values of eq. parameters and precisions: see table 4.6.2.

40
LiCl

Table 4.6.2. Parameters of diffusion equation (4.5), precisions,

and recommended study

Species A x 10 3 (cm 2 sec 3 )

E (cal mol x ) Temp, range

(K) • Precision Recommended study

Li+ linear eq ua t ion 883-1033 72

Cl" linear equation 883-1033 72

Na + 2.10 5850 928-1085 ^±1.52 75

Rb + 2.06 6740 928-1091 . ^±3.52 75

Cs

+

0 . S 3 6440 925-1089 '>-±4% 75

Pb 2 + 2.74 7479 903-1150 ^±32 76

Ag

+ 2.46 5516 911-1089 'Vi 22 71

Zr 2 + 2.95 7596 973-1105 vt52 70

Mo 3 + 1.89 7194 935-1083 vt6% 74, 78

Cl 2 1.09 x 10

-7 -32,211 935-1100 ^±2 62 77

No entry in precision column indicates estimates not possible since results were

reported as equations only'

For Li

+

, D Li+ =[10.6 + 0.0307 (T-883) ]xl0" 5

; for Cl", D^- = [ 5 . 8 + 0 . 0117 (T- 883) ] xlO

Table 4.6.3. Self-diffusion coefficients from equations in table 4.6.2

T(K) \i+ x

_ 105

(cm 2 sec *)

D

ci - X_105

(cm 2 sec 1 ) 880 9.91 5.76

900 11.12 6.00

920 11.74 6.23

940 12 . 35 6.47

960 12.96 6.70

980 13.58 6.93

1000 14.19 7.17

1020 14.81 7.40

1040 15.42 7.64

For numerical values of other diffusing species: see table 4.6.4. (next page)

References: Li

+

, 72; Cl', 72; Na

+

, 75; Rb

+

, 75; Cs

+

, 75; Pb

2+

, 76,-79;

Ag

+

, 71; Zr

2+

, 70; Mo

3+

, 74 , 78 ; Cl 2> 77.

9. Heat of Fusion (A H^.)

Measurement method: drop calorimetry [80]

Table 4.7. Heat of Fusion

AH°

^ Uncertainty -1

(kcal mol ) 4.76 * ± 1%

41
LiCl

References [2,10,80-82].

Table 4.6.4. Diffusion coefficients, D x 10** (cm^ sec ^")

, from equations

in table 4.6.2

T(K) Na+

Rb +

Cs +Pb 2 + Ag

+

Zr 2 +

Mo 3 + Cl 2 900 4.18

910 4.38 11.64

930 8.86 5.37 2.85 4.79 12.43 3.85

950 9.47 5.80 3.07 5 . 21 13.24 4.18 280.5

970 10.09 6.24 3.29 5.66 14.06 5.73 4.52 197.3

990 10.73 6 .70 3.52 6.12 14.90 6 . 21 4.88 140.8

1010 11.38 7.17 3.76 6.60 15.75 6.70 5.24 101.8

1030 12.05 7 .65 4.00 7.09 16.61 7.21 .5.62 74.5

1050 12.72 8.15 4.25 7.60 17.49 7.74 6.01 55.2

1070 13.40 8.65 4.50 8.13 18.37 8.28 6.41 41.4

1090 14.10 9.17 4.76 8.67 19 .27 8.84 6.82

1110 9.23 9.42

1130 9.80

1150 10.38

10. Heat Capacity (C

)

Measurement method: drop calorimetry + averaged [10,83,84]

-Cp

* 17.535 - 2.26 x 10

_3

T (4.6)

precision: ± 0.1% uncertainty: ^ ± 2%

Table 4.8 . Heat capacity from equation (4.6)

T(K)

C

P, 1 (cal K

1 mol'-1 ) T(K)

C

P, -1 (cal K”1 mol 1 )

900 15.501 1060 15.139

920 15.456 1080 15 . 094

940 15.411 1100 15.049

960 15.365 1120 15 . 004

980 15.320 1140 14 .959

1000 15. 275 1160 14 .913

1020 15. 230 1180 14 .868

1040 15 . 185 1200 14 .823

References [10,83-84].

11 . Volume Change on Melting (AF^J

Measurement method: capillary

Table 4.9.

technique [85 1

Volume change on melting

< A W Uncertainty

26.2% ^ ± 2%

4 2
LiCl

References [85] .

12. Vapor r Pressure (pr ) vap

Measurement method: effusion [89]; Rodebush [92]

log p

= 8.2848 - 8741/T (4.7)

precision: ^ ± 1.20% uncertainty: ^ ± 5%

Table 4.10. Vapor pressure from equation (4.7)

T P T P (K) (mm) (K) (mm)

890 0 . 029 1140 4 .14

900 0 . 037 1150 4 .83

910 0.048 1160 5 .62

920 0 . 061 1170 6.51

930 0.077 1180 7 .54

940 0.097 1190 8 .70

950 0 . 121 1200 10 . 01

960 0.151 1210 11.50

970 0 .188 1220 13 . 18

980 0 . 232 1230 15 . 08

990 0 .285 1240 17 .20

1000 0 .350 1250 19.59

1010 0.427 1260 22.26

1020 0 . 519 1270 25 . 24

1030 0 .629 1280 28.57

1040 0 .759 1290 32.27

1050 0 . 912 1300 36.39

1060 1.09 1310 40.95

1070 1 . 31 1320 46.01

1080 1 .55 1330 51.60

1090 1.84 1340 57.77

1100 2 .18 1350 64.56

1110 2 .57 1360 12 . 04

1120 3 .02 1370 80 . 26

1130 3.54

References [86-93].

13. Thermal Conductivity (liquid) (\ ) Measurement method: transient hot wire

precision: not estimated

[94]

uncertainty: ^ ± 20%

Table 4.11. Thermal conductivity of melt

T X jx 10 4 (K) (cal cm

-1 sec-1 K"1 ) 943 10. 88

1043 11.55

References [94-96].

43
LiCl

14. Thermal Conductivity (solid) (X ) s Measurement method: modified hot wire [96]

precision: not estimated uncertainty: ^ ± 10%

Table 4.12. Thermal conductivity of solid

L T

(K)

A x 10 i-i

(cal cm

-l sec K ) 823 to m. pt. 36.07

References [96]

Cryoscopic Constant (k^J

Measurement method: calculated from &H° [97]

Table 4.13. Cryoscopic constant

k

f Uncertainty

(K mol- 4kg

- l)

13.8

T—

a +1 References [7,80,97-105].

16. References

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[15]
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31 (1967).

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(1964)

[40] Bondarenko, N. , Fiz. Khim. Elektrokhim. Rasplav. Solei Shlakov, Tr.

Vses. Sov. 1st., 277 (1969).

45
LiCl

[41] Ryschkewitsch , E., Z. Elektrochem . , 39^, 531 (1933).

[42] Biltz, W. , and Klemm, W. , Z. physik. Chem. , 110 , 318 (1924).

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Verkehrsministeriums Nordrhein-Westfalen, No. 341 (1956).

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[45] Bizouard, M. , Ann. Phys . 6^, 851 (1961).

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Elektrokhim. Rasplavlen. Solei Akad. Ukr. SSR, Inst. Obshch.

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3 Christensen, H. E.,

and Lubinbyhl, T. T., eds . , U. S. Dept. H. E. W. , U. S. Gov’t Printing Office, Washington, D. C. (1975).

[54] Vapor pressure, calculated (see p. 43, this work).

[55] "Potential Hazards In Molten Salt Baths for Heat Treatment of Metals

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[56] "Handbook of Reactive Chemical Hazards"

,

Bretherwick, L., Butterworths

Co . , London (1975) .

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,

"Safety and Hazards"3 Chapter in "Eutectic Data"3 ERDA TID- 27163-PI

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1827 (1964). “r_

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46
LiCl

[66] Johnson, K. E., "Electrochemical Approaches To Corrosion In Molten Salts ",

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Reactions and Processes", The Electrochemical Society, Inc., Princeton,

N. J. , p. 581 (1975)

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Electrochem. , f, 47 (1965) .

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[83] vide infra ref. [6].

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Russ. J. Inorg. Chem., 4_, (1), 98 (1959).

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[92]

Beusman, C., USAEC ORNL-2323 (1957).

47
LiCl

[93] Janz, G. J., et al., (MSDC-RPI) ; calculations merging vapor pressure

data base o£ ref. 89, 92 (unpublished work, 1978).

[94] McDonald, J., and Davis, H. T., Phys . Chem. Liq., 2_, 119 (1971).

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,

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79, 344 (1975).

48
V. Sodium Chloride: NaCl

1. Melting Temperature (T ) Melting point:

800° ± 2

0 C [4]

References [1-16] .

2 . Density ( p ) Measurement method: Archimedean technique [14]

p = 2.1393 - 5.430 x 10

_4

T (5.1)

precision: ± 0.11 uncertainty: ^ ± 0.5%

Table 5.1. Densities from equation (5.1)

T(K)

P (g cm'3)T(K)

P

( g cm" 3 ) 1080 1.553 1190 1.493

1090 1 .547 1200 1 .488

1100 1.542 1210 1.483

1110 1.537 1220 1.477

1120 1.531 1230 1.471

1130 1.526 1240 1.466

1140 1.520 1250 1 .461

1150 1 .515 1260 1.455

1160 1.509 1270 1 .450

1170 1.504 1280 1.444

1180 1.499 1290 1 .439

References [14,17-45],

3.

Surface Tension (y)

Measurement method: maximum bubble pressure [46]

Y

= 191.4 - 7.19 x 10

_2

T (5.2)

precision: ± 0.2% uncertainty: ^ ± 1%

Table 5.2. Surface tension from equation (5.2)

T(K)

Y (dyn cm *) T(K)

Y (dyn cm 1

) 1080 113.5 1170 107.0

1090 112.8 1180 106.3

1100 112.1 1190 105.6

1110 111.3 1200 104.9

1120 110.6 1210 104.1

1130 109.9 1220 103.4

1140 109 .

1230 102.7

1150 108 .

5

1240 102.0

1160 107.7 1250 101.3

References [10,37,46-57].

49
NaCl

Viscosity (r\)

Measurement method: oscillating cylinder [201]

n = 8.931 x 10" 2 exp [5248. 1/RT] (5.3)

precision: ± 0.051 uncertainty: % ± 3%

Table 5.3. Viscosity from equation (5.3)

T(K)

n (cp)

T

(K)

n (cp)

1090 1 . 008 1150 0.888

1100 0.986 1160 0.871

1110 0.965 1170 0.854

1120 0.944 1180 0.838

1130 0.925 1190 0.822

1140 0.906 1200 0.807

The above viscosities are based on recent results from Trondheim (H. A. 0ye

,

private communication to G. J. Janz (1978), see [201]) and receive additional

support from work in progress at Bucharest (S. Zuca, private communication to

G. J. Janz (1978)). These values supersede the data reference base [45].

Earlier values are as much as 40% too high at 1090K and this departure

decreases uniformly to ^ 10% at 1240K.

References [45,58-67,200,201].

Electrical Conductance (k)

Measurement method: ac technique [1]

- 2 , - 6^2

k = -4.0896 + 1.1528 x 10 T - 4.0534 x 10 ~T

precision: ^ ± 0.27% uncertainty: % ± 2

(5.4)

Table 5.4. Electrical conductance from equation (5.4)

T(K)

K (ohm 1 cm 1 )T(K)

K (ohm 1 cm 1 ) 1100 3.687 1200 3 .907

1110 3 .712 1210 3 .925

1120 3 . 737 1220 3 . 941

1130 3.761 1230 3.957

1140 3.785 1240 3 .973

1150 3.807 1250 3 .987

1160 3.820 1260 4 . 001

1170 3.849 1270 4.013

1180 3 .869 1280 4 . 025

1190 3.889 1290 4 . 036

References [1,14,20,21,30,32,45,61,65,68-93].
NaCl

6. Safety and Hazards

A. Hazard rating [94-96]

(i) Very low

(ii) Vapor pressure: at m.pt. (800°C) , ^ 0.34 mm;

at 860°C, ^ 1 mm

B. Disaster hazards [94,97-99]

(i) Molten salt bath "explosions": i.e., explosive generation of steam

due to bulk water "carry-over" and/or equipment failure;

i.e., explosive expansion of "trapped" air.

(ii) When bulk NaCl is heated at high temperatures, vapor is evolved

which is particularly irritating to the eyes; when heated to

decomposition or contacted with acids, highly toxic chloride

fumes are evolved.

References [94-99]

7. Corrosion

Table 5.5. Corrosion studies from primary research literature

Studies References

Mo 100

Armco Fe 101-103

NiCr 104

Ti, Zr, Hf, ThCl 4 105

Cr 106

Cr, Fe-Cr 107

Ni alloys - 108

Ni-Cr-Al , Ni-Cr-W-Fe, Ni-Cr

Mg, Ni, Zr, Ti 109

Au, Pt, MgO , A1 2 0 3 , Zirconia [NaCl with added

Na 2 0] 110

Electrochemical aspects

of corrosion 111,112

Corrosion - annotated biblio. 113

Thermodynamic redox potentials

(diagrammatic analysis) 109,114,115

Reviews: corrosion in

molten salts 116-118

References [100-118] .

8. Diffusion

Measurement method: cited in tabulations

List of diffusing species investigated in NaCl as solvent

Na

+

, Cl', Li

+

, K

+

, Rb

+

, Cs

+

, Ca

2+

, Pb

2+

, Ag

+

, Cd

2+

7 4+ 1-3+ n 2+ ,2-f ti,4+ t T 3 +tt 4 + n unn Zr jFo 9 Co y N'L jTh ? U ? 2

? •

Zr

2 +

51
NaCl

The italicized species indicate studies with insufficient data-sets for

characterization of temperature dependence of diffusion coefficients. For

these species, see: table 5.6.5.

precision: in table 5.6.2 uncertainty: in table 5.6.1

Table 5.6.1. Diffusion techniques, uncertainties, and species

Diffusion technique

of recommended study

Uncertainty

(in values of D) Species

capillary

chronopotentiometry

rotating disc electrode

^ ± 20%

^ ± 10%

~ ± 20%

Na

+

, Cl", Li+

, K+

, Rb +

, Cs +, Ca 2+

Pb 2+

, Ag

+

, Cd 2+

, Zr 2+

, Zr 4 +, Th 4+

, U 3+, U

4 +,

Co 2+

, Ni 2+

, Cl 2 Fe 3+

, HC1, Cl 2

Equation

D = A exp [ -E/RT] (5.5)

For values of eq. parameters , and precisions

see table 5.6.2

For numerical values: see tables 5.6.3, 5.6.4, and 5.6.5

References: Na

+

, 119-121, 122, 125, 135; Cl , 119, 120, 122, 125, 135;Li + ,121

K

+

, 121; Rb

+

, 121, 125; Cs

+

, 121, 125; Ca

2+

, 136; Pb

2+

, 126, 132;

Ag

+

, 133, 148; Cd

2+

, 135, 137; Fe

3+

, 123; Zr

2+

, 129, 138; Zr

4+

, 130, 138; Th

4+

, 128; U

3+

, 131, 140; U

4+

, 131; Cl

2

, 127, 141-143;

Co

2+

, 146; Ni

2+

, 147; HC1, 124.

9. Beat of Fusion (A E°^)

Measurement method: drop calorimetry [12,13]

Table 5.7. Heat of fusion

AH °f (kcal mol - -*-) Uncertainty

6. 73 ^ ± 0.5%

References [5,12,13,149,150].

52
NaCl

Table 5.6.2. Parameters of diffusion equation (5.5), precisions, and

recommended study

Species A x 10 3 E Temp range Precis ion Recommended

(cm z sec 1 ) (cal mol 3 ) (K) study

Na

+

2 .

7140 1090-1295 ^±3% 122

Cl" 1.9 7430 1100-1310 ^±3% 122

Li + 1.38 5450 1090-1250 . 'vi 2.5% 121

K+ 1.92 6780 1100-1240 ^±2.3% 121

Rb + 2.04 7140 1105-1250 ^±3.6% 121

Cs +3 .57 8620 1100-1250 ^±4% 121

Ca 2 + 2.26 8270 1110-1220 'vi 0.04% 136

Pb 2 + 3.06 8492 1085-1190 ^±1.3% 126

Ag

+

4 . 66 8404 1095-1190 ^±1.4% 133

Cd 2 +

2 .97 8055 1100-1155 ^±3% 137

Fe 3 + 22.9 13800 1120-1215 ^±0.08% 123

Zr 2 + 4.46 8910 960-1215 129,138

Zr 4 +3 .63 9335 1070-1220 130,138

Th 4 +

7 .27 10666 965-1210 128

U

3 + 2.19 7 733 1085-1205 140

u 4+ 3.80 9335 920-1205 131

Cl 2 2.02 x 10~ 2 -7554 1100-1225 ^±4.6% 141,143

No entry in precision column indicates estimates not possible, since results

were reported as equations only.

Table 5.6.3. Self -diffusion coefficients from equations in table 5.6.2

T(K)

D

Na+ *

_105

(cm 2 sec 1

)

D C1- x 105

( cm 2 sec 1

) 1090 7.77

1100 8 . 01 6.35

1110 8.25 6.54

1120 8 o 49 6.74

1140 8.99 7.15

1160 9.48 7.57

1180 9.99 7.99

1200 10.51 8.42

1220 11.04 8.86

1240 11.58 9.31

1260 12.12 9.77

1280 12.68 10.23

1300 13.24 10.70

1310 10.94

53
NaCl

c 2 -

Table 5.6.4. Diffusion coefficients, D x 10 (cm sec ), from equations

in table 5.6.2

T(K) Li+

K+Rb +

Cs +

Ca 2 +Pb 2 +

Ag

+ Cd 2 + F e 3 + Zr 2 +

Zr 4 + Th 4 +

U

3 +

U

4 +

Cl 2 920 2.30

940 2 . 57 960 4.18 2.71 2.85

980 4.59 3 . 04 3.15

1000 5.03 3.39 3.46

1020 5.50 3.77 3.80

1040 5.98 4 .17 4.15

1060 6.49 4.60 4.52

1080 5.85 7.02 4.69 5.05 5.96 4 .90 1100 11.40 8.63 7 .78 6.92 6.29 9.97 7.45 7.57 5.07 5.52 6.37 5 .31 63 . 99 1120 11.92 9.12 8.25 7.42 5.50 6.74 10.67 7 .96 8.14 5.47 4 . 64 6.03 6.78 5.73 60.16

1140 12.44 9.63 8.72 7 . 94 5.87 7.20 11.41 8.48 8.73 5.89 5.18 6.56 7.21 6.17 56.68

1160 12.97 10.13 9.21 8.48 6.25 7 . 69 12.16 9.02 9.34 6.32 5.75 7.11 7 . 65 6.62 53.51

1180 13.50 10.65 9.71 9.04 6.64 8.18 12.93 9.98 6.77 6.36 7 . 69 8.09 7 . 09 50.62

1200 14.04 11.18 10.21 9.61 7 . 04 10.63 7 . 24 7 . 02 8.30 8.55 7 . 58 47.97

1220 14.57 11.71 10.73 10.19 7.46 11.30 7.72 7.72 45.55

1240 15.11 12.25 11.25 10.80

1250 15.38 11.51 11.10

Table 5.6.5. Diffusion coefficients for species not included in

tables 5.6.3 and 5.6.4

Species T(K)D x 10 5

( cm 2 sec 1

) Recommended

study

Co 2 + 1079 2 .12 146

N i

2 + 1078 2 . 81 147

HC1 1148 31 .

1173 25.0 124

1223 17 .

Heat Capacity (C ) Measurement method: drop calorimetry [13]

C = 25.24 - 7.52 x 10" 3 T (5.6)

precision: ^ ± 0.11 uncertainty: o, ± 0.5%

Table 5.8. Heat capacity from equation (5.6)

T

C

P T

C

p (K) (cal K

-1 mol - l

)

(K) (cal K^mol ) 1100 16.97 1200 16.22

1120 16.82 1220 16.07

1140 16.67 1240 15 . 92

1160 16.52 1260 15.76

1180 16.37 1280 15.61

1300 15.46

References [13,151-153]

54
NaCl

11 . Volume Change

Measurement

on Melting (A7^J

method: densities [26]

Table 5.9. Volume change on melting

(AV

f /Vs

) Uncertainty

26.06% ^ ± 0.3%

References [23,26,154-160].

12. Vapor r Pressure (pr ) vap

Measurement methods: boiling point [163] ; Rodebush-Dixon [165]

log p

= 8.4459 - 9565/T (5.7)

precision: ^ ± 0.6% uncertainty: ^ ± 5%

Table 5.10. Vapor pressure from equation (5.7)

T P T P (K) (mm) (K) (mm)

1250 6 .22 1400 41.1

1260 7 . 16 1410 45 .

9

1270 8 . 21 1420 51 .

3

1280 9 . 40 1430 57.2

1290 10.7 1440 63 .

6

1300 12 .

3

1450 70.7

1310 13 .

9

1460 78 .

1320 15 .

8

1470 86 .

9

1330 18 .

0

1480 96 .

1340 20 .

3

1490 106 .

3

1350 22 .

9

1500 117 .

3

1360 25 .

9

1510 129.3

1370 29.1 1520 142 .

3

1380 32.7 1530 156.4

1390 36 .

References [161-170].

13, Thermal Conduotivity (liquid) (X^)

Measurement method: coaxial cylinder steady state [173

X = 1.868 x 10' 3 + 4.73 x 10' 7 T (5.8)

precision: not estimated uncertainty: ^ ± 20%

Results were reported in graphical form only.

Table 5.11. Thermal conductivity of melt from equation (5.8)

T(K)

X x 1

0

4 (cal cm

-

* sec

-1 K

-

)

T(K)

4

X x 10

(cal cm"-*’ sec

-1 K

-1

) 1100 23.88 1160 24.17

1110 23.93 1170 24.21

1120 23.98 1180 24.26

1130 24.02 1190 24.31

1140 24.07 1200 24.36

1150 24.12

Eq. obtained by fitting the interpolated data from the graphical presentation

5 5
NaCl

14. References [171-173].

Thermal Conductivity (solid) (X ) ° s Measurement method: not cited [180]

precision: not estimated uncertainty: not estimated

Insufficient information for estimate of precision and uncertainty

Table 5.12. Thermal conductivity of solid

T

(K)

X x 10 3 (cal cm" sec"^" 1 ) 80 84.0

100 62.4

120 47.5

140 38.0

160 32.4

180 28.5

200 25.6

220 23.2

240 21.1

260 19.1

280 17.4

300 15.8

320 14.5

340 13.6

360 12.9

380 12.2

400 11.6

420 11.0

440 10.5

460 9.6

References [174-184]

IS. Cryoscopic Constant

Measurement method: cryoscopy; and calc'd [185,186]

Table 5.13. Cryoscopic constant

k

f Uncertainty

-1 -1.

(K mol kg ) 20.0 ^ ± 0.5%

References [185-199]

16.

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56
NaCl

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NaCl

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NaCl

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59
NaCl

[92] Matiasovsky, K., Danek, V. , and Lillebuen, B., Electrochim. Acta, 17,

463 (1972).

[93] Poincare, L., Ann. Chim. Phys., 2_1 , 289 (1890).

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,

Sax, N. I., Van Nostrand Reinhold

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Christensen, H. E.,

and Lubinbyhl, T. T., eds . , U. S. Dept. H. E. W. , U. S. Gov't Printing

Office, Washington, D. C. (1975).

[96] Vapor pressure, calculated (see p. 55 , this work).

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,

National Board Fire Underwriters Research Report No. 2 (1954).

[98]

[99]

[ 100 ]

[ 101 ]

[ 102 ]

[103]

[104]

[105]

[106]

[107]

[108]

[109]

[HO]

[HI]

[ 112 ]

[113]

[114]

"Handbook of Reactive Chemical Hazards ", Bretherwick, L., Butterworths

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S. D. , and Shamanova, N. D. , Zashch. Metal., 11 , 66 (1975).

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1085 (1961).

Kochergin, V. P., and

3 (1969).

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Shevrina, Z., Uch. Zap

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Krasil'nikova, N. A., Ozeryanaya, I. N. , and Smirnov, M. V., Zashch.

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Krasil'nikova, N. A. , Ozeryanaya, I. N. , Smirnov, M. V., and Shamanova,

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Littlewood, R. , J. Electrochem. Soc., 109, 525 (1962).

Stern, K. H. , Panayappan, R. , and Flinn, D. R. , Proceedings Intern.

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Johnson, K. E., "Electrochemical Approaches to Corrosion In Molten Salts"

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Janz, G. J., and Tomkins, R. P. T., Corrosion, 34^ (in press) (1978).

Edeleanu, C., and Littlewood, R. , Electrochimica Acta, 3, 195 (1960).
NaCl

[115] Littlewood, R. , and Argent, E. A., Electrochimica Acta, 4, 114 (1961).

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6_8 , 1838 (1964).

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Metal., No. 1 , 64 (1971).

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J. Phys. Chem., 44, 1197 (1970).

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Nauch. Tsentr. Akad. Nauk. SSSR, 18^, 57 (1972).

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Posokhin, Yu. V., Elektrokhimiya, 1_0 , 1599 (1974).

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Elektrokhim. Akad. Nauk, SSSR, Ural. Fil., 13, 3 (1969).

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Elektrokhimiya, 1_0^, 770 (1974).

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336 (1962).

[133] Sternberg, S., and Herdlicka, C., Rev. Chim. (Roumaine), 1_7, 343 (1972).

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2_4 , 1282 (1956).

[135] Koster, J., Ph.D. Thesis, Amsterdam (1971).

[136] Ichikawa, K. , Shimoji, M. , and Niwa, K. , Ber. Bunsen Physik. Chem.,

69, 248 (1965).

[137] Herdlicka, C., and Sternberg, S., Rev. Chim. (Roumaine), 2_0, 1051 (1975).

[138] Borodina, N. P., Smirnov, M. V. , and Komarov, V. E. , Tr. Inst. Elektrokhim. Ural. Fil. Akad. Nauk. SSSR, 17_, 56 (1971).

[139] Smirnov, M. V. , and Shebanov, 0. M. , Electrochem. Molten Solid

Electrolytes (Ed., A. N. Baraboshkin) , 5_, 53 (1967).

[140] Smirnov, M. V., Komarov, V. E. , and Borodina, N. P., Tr. Inst.

Elektrokhim. Ural. Fil. Akad. Nauk. SSSR, 19^, 29 (1973).

61
NaCl

[141] Leonova, L. S., Ryabukhin, Yu. M. , and Ukshe, E. A., Elektrokhimiya

,

5, 210 (1969).

[142] Ryabukhin, Yu. M. , Russ. J. Phys . Chem., 39_ f 1563 (1965).

[143] Bezukladnikov, A. B., and Bezvoritnyi, V. A., Fiz. Khim. Elektrokhim.

Rasplav. Solei Shlakov, Proc. 3rd All. Union Conf . , Khimiya,

Leningrad, p. 262 (1968).

[144] Lewis, J. W. E., and Singer, K. , J. Chem. Soc., Faraday Trans. II,

71, 41 (1975).

[145] Lantelme, F., Turq, P., Quentrec, B., and Lewis, J. W. E., Mol. Phys.,

2_8 , 1537 (1974).

[146] Delimarskii, Yu. M. , Grishchenko, V. F., and Pafkhomenko, N. I., Ukr.

Khim. Zh. , 4^, 1123 (1975)

[147] Delimarskii, Yu. K ., Grishchenko , V. F. , and Parkhomenko, N. I.,

Elektrokhimiya, 12_, 200 (1976).

[148] Ukshe, E. A., Ryabukhin, Yu. M. , and Volkova, S. V., Izv. Akad. Nauk.

SSSR, Metal ly , No. 4, 89 (1965).

[149] Marchidan, D. I., and Gambino, M. , Mem. Presentes a la Soc. Chim.

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1954 (1966).

[150] Kelley, K. K. , U. S. Bureau Mines, Bull. 476 (1949).

[151] vide infra ref. [4].

[152] Vilcu, R. , and Misdolea, C., J. Chem. Phys., 46^, 906 (1967).

[153] Bockris, J. O'M., and Richards, N. E., Proc. Roy. Soc. (London), A241

44 (1957).

[154] Eucken, A., Z. angew Chem., 5_5 , 163 (1942).

[155] Schinke, H. , and Sauerwald, F., Z. anorg. allgm. Chem., 287, 313 (1956);

ibid., 284_, 131 (1956); ibid., 304 , 25 (1960).

[156] Eucken, A., and Dannohl, P., Z. Elektrochem. , 4_0, 814 (1934).

[157] Bredig,' M. A., and Johnson, J. W. , Rept. ORNL-1940, p. 19.

[158] Bockris, J. O'M., Pilla, A., and Barton, J. L., Rev. Chim. (Roumaine)

,

7, 59 (1962).

[159] Davies, W. D. , Rogers, S. E., and Ubbelohde, A. R. , Proc. Royal Soc.,

220 , 14 (1953).

[160] Landon, G. J., and Ubbelohde, A. R. , Trans. Faraday Soc., 52^ , 647 (1956).

[161] Maier, C. G., U. S. Bur. Mines, Bull. 360 (1925).

[162] Topor, L. , J. Chem. Thermo., 4, 739 (1972).

[163] Barton, J. L., and Bloom, H. , J. Phys. Chem., <50, 1413 (1956).

[164] Kangro, W. , and Wieking, H. W. , Z. phys. Chem., 183A , 199 (1938-9).

[165] Fiock, E. F., and Rodebush, W. H., J. Amer. Chem. Soc., 4_8, 2522 (1926).

[166] Greiner, B. , and Jellinek, K. , Z. phys. Chem., 165A , 97 (1933).

[167] von Wartenberg, H. , and Albrecht, P., Z. Elektrochem., 27_, 162 (1921).

[168] Ruff, 0., and Mugdan, S., Z. anorg. allgm. Chem., 117 , 147 (1921).

62
[169]

[170]

[171]

[172]

[173]

[174]

[175]

[176]

[177]

[178]

[179]

[180]

[181]

[182]

[183]

[184]

[185]

[186]

[187]

[188]

[189]

[190]

[191]

[192]

[193]

[194]

[195]

[196]

[197]

[198]

[199]

[ 200 ]

[ 201 ]

NaCl

Horiba, S., and Baba, H., Bull. Chem. Soc. Japan, 3^, 11 (1928).

Janz, G. J., et al., (MSDC-RPI) ; merge of V. P. data base (ref. 163,

165) (unpublished work, 1978).

Eucken, A., and Kuhn, G., Z. Phys . Chem., 134 , 193 (1928).

Bystrai, G. P., Desyatnik, V. N. , and Zlakazov, V. A., Sov. Atomic

Ener. , 36, 654 (1974)

Fedorov, V. I., and Machuev, V. I., High Temp., 8(, 858 (1970).

Srinivasan, R. , and Krishnan, R. S., "Thermal Conductivity" in "Prog.

Crystal Physics"3 Vol. 1, (R. S. Krishnan, ed.), Interscience, New

York, 1958.

Bridgman, P. W. , "Physics of High Pressures

3 G. Bell and Sons, London,

i 9 49 . Smirnov, I. A., Sov. Phys. Solid State, 8_, 21 (1966) .

Zakharov, V. M. , Sov. Phys. Solid State, 9_, 1183 (1967).

Ioffe, A. V., and Ioffe, A. F., Dokl. Akad. Nauk SSSR, 97, 821 (1954);

8_7 , 369 (1952).

Eucken, A., Ann. Phys., 3£, 185 (1911).

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1445 (1962).

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Petrov, A. V., Tsypkina, N. S. , and Logachev, Yu. A., Sov. Phys. Solid

State , 16, 39 (1974)

Aim, U., and Backstrom, G. , High Temp. High Press., 7_, 235 (1975).

Compton, A. H. , Phys. Rev., 7_, 341 (1916).

Riccardi, R. , and Benaglia, C., Gazz. Chim. Ital., 9_1., 315 (1961).

Janz, G. J., et al . , (MSDC-RPI) unpublished work (1977).

Petit, G., and Bourlange, C., Compt. Rend., 237 , 457 (1953).

Hoenen, P. H. J., Z. Physik. Chem., 8_3, 513 (1913).

Rolin, M., J. Four. Elec., 62_, 11 (1953).

Darmois, E. , and Zarzycki, G. , Compt. Rend., 233 , 1110 (1951).

Van Artsdalen, E. R. , J. Tenn. Acad. Sci., 2_9 , 122 (1954).

Doucet, Y. , Bizouard, M. , and Netzer, C., Compt. Rend., 242 , 492 (1956).

Harrison, J., Petit, G. , and Plancel. R. , Compt. Rend., 241 , 402 (1955).

Harrison, J., Compt. Rend., 214 , 298, 488 (1955).

Cook, C. M., and Dunn, W. E., J. Phys. Chem., 6_5 , 1505 (1961).

Johnstone, H. F., Weingartner, H. C., and Winsche, W. E., J. Amer. Chem.

Soc. , 64 , 241 (1942) . Murgulescu, 1. G. , and Sternberg, S., Z. Physik. Chem., 219 , 114 (1962).

Kamenetskii, M. V. , Tsvetn. Metal., 3_1, 39 (1958).

Markov, B. F., and Chernov, R. V. , Ukr. Khim. Zh. , 25_, 279 (1959).

Brockner, W. , Grjotheim, K. , Ohta, T., and 0ye, H. A., Ber Bunsen Ges., 79, 344 (197 5 ) . Torxiep, K., and 0ye , H. A., Ber Bunsen Ges., 82, (1978).

6 3
VI Potassium Chloride: KCl

1. Melting Temperature (T ) Melting point:

770° ± 1°C [4,9]

References [1-17].

2.

Density (p)

Measurement method: Archimedean technique [2]

p = 2.1359 - 5.831 x 10

_4

T (6.1)

precision: ± 0.5% uncertainty: ^ ± 0.5%

Table 6.1. Densities from equation (6.1)

T(K)

P (g cm-3

)

T(K)

P (g cm -3

) 1060 1.5178 1130 1.4770

1070 1.5120 1140 1.4712

1080 1.5062 1150 1.4653

1090 1.5003 1160 1.4595

1100 1.4945 1170 1.4537

1110 1.4887 1180 1.4478

1120 1.4828 1190

1200

1.4420

1.4362

References [2,3,6,8,10-12,14,16-49] .

3.

Surface Tension (y)

Measurement method: derived from ref. 20, 50, 51, 52, 57, 59, 61, 62 [56]

y

= 179.1168 - 7.6026 x 10

_2

T (6.2)

precision: ^ ± 0.26% uncertainty: ^ ± 0.5%

Table 6.2. Surface tension from equation (6.2)

T(K)

Y

(dyn cm 3

)

T(K)

Y (dyn cm 3 ) 1080 97.01 1190 88.65

1090 96.25 1200 87 . 89

1100 95.49 1210 87.13

1110 94.73 12 20 86.37

1120 93.97 1230 85.61

1130 93.21 1240 84.84

1140 92.45 1250 84.08

1150 91.69 1260 83.32

1160 90.93 1270 82.56

1170 90.17 1280 81.80

1180 89.41

References [29,35,50-64].

64
KC1

4. Viscosity (r\)

Measurement method: oscillating sphere [226]

n = 7.32 x 10‘ 2 exp [5601. 7/RT] (6.3)

precision: ^ ± 0.6% uncertainty: ^ ± 3%

Table 6.3. Viscosity from equation (6.3)

T(K)

n (cp)

T(K)

n (cp)

1070 1.020 1130 0.887

1080 0.996 1140 0.868

1090 0.972 1150 0.850

1100 0.950 1160 0.832

1110

1120

0.928

0.907

1170 0.815

References [35,37,43,65-72,226].

5. Electrical Conductance (<)

Measurement method: ac technique [2]

k = -3.99005 + 9.0222 x 10

_3

T - 3.000 x 10

_6

T

2 (6.4)

precision: ± 0.41% uncertainty: ± 1%

Table 6.4. Electrical conductance from equation (6.4)

T(K)K (ohm 1 cm *) T(K)

K (ohm 1 cm 1 ) 1060 2 .203 1140 2 .396

1070 2.229 1150 2.418

1080 2.255 1160 2.439

1090 2.280 1170 2.459

1100 2 .304 1180 2.479

1110 2 .328 1190 2.498

1120 2.352 1200 2.517

1130 2.374

References [2,3,6-8,10,14,15,20-22,32,34,47,71,73-112].

6 Safety and Hazards

A . Hazard rating [113,114]

(i) Very low

(ii) Vapor pressure: at m. pt. (770°C), ^ 0.42 mm; at

820° C, % 1 mm

B. Disaster hazards [116-118]

(i) Molten salt bath "explosions": i.e., explosive generation

of steam due to bulk water "carry-over" and/or equipment

failure; i.e., explosive expansion of "trapped" air

65
KC1

(ii) Chlorides evolve highly toxic fumes when heated to

decomposition, or contacted with acids

References [113-118] . Corrosion

Table 6.5. Corrosion studies from primary research literature

Studies References

Armco Fe; various steels 119,120,125,1

Cr 121

Cr, Fe-Cr 122

Mg, Ni, Zr, Ti 123

Ti, Zr, Hf, ThCl

A 124

Solubility of oxides

(Ni, Ca, Zn, Mg) 123,128

Electrochemical aspects 129

Corrosion - annotated biblio. 130

Thermodynamic approach 123,131,132

Reviews: corrosion in

molten salts 133-135

References [119-135]

Diffusion

Measurement method: cited in tabulations

K

+

, Cl", Na

+

Zr

2 + Zr4 +

species investigated in

_ _ + + 2+ ,2 +

, Rb , C s , Ca , Pb , 3 + _ 3 + 2+ 2 + Mo , Fe , Co , Ni ,

+ . + + , 2 + Cu , Ag , Au , Cd

4+ Tr 3+ „4 + Th U' U Cl.

HCl

The italicized species indicate studies with insufficient data-sets for

characterization of temperature dependence of diffusion coefficients. For

these species, see table 6.6.5.

precision: in table 6.6.2 uncertainty: in table 6.6.1

Table 6.6.1. Diffusion techniques, uncertainties and species

Diffusion technique Uncertainty

of recommended study (in values of D) Species

capillary ^ ± 20% K+

, Cl“, Na

+

, Rb +

, Cs+, Ca 2+

chronopotentiometry ^ ± 10% Pb2+

, Ag

+

Cd 2+ Zr 2 +

Zr 4+

, Mo^+, Th 4+

, U 3+, U 4+ . Cl 2 , Cu +

, Au+,

Co 24_

, Ni 2 +

rotating disc electrode ^ ± 20% Fe 3 +

, HCl

66
KC1

Equation:

D = A exp [ -E/RT] (6.5)

Table 6.6.2. Parameters of diffusion equation (6.5), precisions, and

recommended study

Species A x 10 3 (cm 2 sec 3 )

E (cal mol 3

)

T emp. range

(K)

Precision Recommended

study

K+ 1.80 6880 1070 - 1260 149

Cl" 1.80 7130 1065 - 1260 149

Na

+

3 . 03 7820 1070 - 1275 136

Rb

+ 2.06 7070 1070 - 1275 136

Cs

+ 1.09 5600 1070 - 1275 136

Ca 2 + 1.29 7920 1055 - 1175 *±0. 2% 165

Pb 2 +2 .46 8165 1065 - 1175 *±1.9% 151

Ag

+

3 .30 7709 1060 - 1190 *±2.4% 147

Cd 2 + 1.12 6209 1050 - 1135 *±2.4% 156

Zr 2 + 9.75 11500 965 - 1210 144

Zr 4 +

7 . 94 11897 1070 - 1195 145

Mo 3 + 6.64 10874 900 - 1100 157

Fe 3 + 0.213 18830 1123 - 1213 *±0.1% 139

Th 4 +

7 .46 11458 1000 - 1200 143

U

3 +

2 .45 8877 1050 - 1210 161

U

4 + 3.09 10067 920 - 1205 146

Cl 2 data set does not f

t either exponent i.al or lin er equations

No entry in precision column indicates estimates not possible since

results were reported as equations only.

Data set for CI 2 in table 6.6.5

67
KC1

Table 6.6.3. Self-diffusion coefficients

T(K)D r+

x 10 5

(cm 2 sec 1 )

D C1- * 105

( cm 2 sec 1 )

1060 6.10

1070 7 . 08 6.29

1080 7.29 6.49

1100 7.73 6.89

1120 8.18 7 .31

1140 8.63 7 .73

1160 8 .16

1180 9 .57 8 . 60

1200 10.05 9.05

1220 10.54 9.50

1240 11 . 03 9 .97

1260 11.53 10.43

Table 6.6.4. Diffusion coefficients, D x 10^ (cm^sec ^)

,

from equations in table 6.6.2

T(K) Na

+

Rb

+ Cs

+

Ca 2 +

Pb 2 + Ag

+ eg +

O Zr 2 + Zr 4 +

Mo 3 +

Fe 3 + Th 4 +

U

3 +

u 4+

. 900 1.52

920 1.73 1.25

940 1.97 1.41

960 2.35 2.22 1.58

980 2.66 2.49 1.76

1000 2.99 2.79 2.34 1.95

1020 3.35 3.11 2.62 2.15

1040 3.73 3.44 2.92 2.37

1050 2.90 5.71 3.94 3.62 3.07 3.48 2.48

1060 3.00 5.10 8.49 5.87 4.15 3.80 3.24 3.62 2.60

1070 7 .66 7.41 7.83 3.11 5.29 8.79 6.04 4.36 2.95 3.99 3.41 3.77 2.71

1080 7.92 7.64 8.02 3.22 5.48 9.09 6.20 4.59 3.11 4.18 3.58 3.91 2.84

1100 8.47 8.11 8.41 3.44 5.87 9.70 6.54 5.06 3.44 4.59 3.95 4.22 3.09

1120 9.02 8.59 8.80 3.67 6.27 10.33 6.88 5.56 3.79 4.51 4.33 4.54 3.35

1140 9.60 9.09 9.20 3.91 6.69 10.98 7.22 6.08 4.16 5.23 4.74 4.87 3.63

1160 10.19 9.59 9.60 4.15 7.12 11.64 6.64 4.55 6.03 5.17 5.21 3.92

1180 10.79 10.10 10.00 4.40 7.56 12.32 7.23 4.97 6.93 5.63 5.56 4.22

1190 11.10 10.36 10.21 12.66 7 . 53 5.18 7.41 5.87 5.74 4.38

1200 11.41 10.62 10.41 7.84 5.41 7.92 6.11 5.92 4.53

1210 11.72 10.88 10.61 8.16 8.45 6.11 4.69

1220 12.04 11.15 10.82

1240 12.68 11.69 11.23

1260 13.33 12.23 11.64

1280 14 . 00 12.78 12.06

68
KC1

Table 6.6.5. Diffusion coefficients for species not

included in table 6.6.3 and 6.6.4

Species T(K)

D x io 5 (cm 2 sec *)

Recommended

study

Cu

+ 1088 2 . 14 141

Au

+ 1088 2.20 141

Co 2 + 1079 1.86 166

Ni 2 + 1078 2.35 167

HC1 1123 31.0 140,163

1153 35 .

0

1183 37.0

Cl 2 1085 18.0 155

1110 21.7

1117 23 .

1143 23 .

5

1173 24 .

0

*

References K

Ca

Zr

154, 155, 164; Cu

+

, 141; Au

+

, 141; Co

2+

y 149; Cl ', 149; Na' , 136 , 137 , 162; Rb , 136; Cs , 136;

2 +

, 165; Pb , 151

,

152; Ag

+

, 141, 147, 148; Cd , 156;

2 +

, 144, 158; -7 4 + Zr > 145, 158, 159; Mo 3+

., 148 , 150, 157;

3 +

, 139; Th4+

, 143, 160; u

3+

, 161

u

4+ ,' 146; ci 2 , 138, 142,

166; Ni 2+

, 167;

HC1 , 140, 163.

9. Heat of Fusion (A Hj.)

Measurement method: drop calorimetry [169]

Table 6.7. Heat of fusion

ah° Uncertainty

(kcal mol ) 6.34 ^ ± 1%

References [4,5,169-173].

10 . Heat Capacity

Measurement method: drop calorimetry [174]

Table 6.8. Heat capacity

C Temp . range Uncertainty

P - -i (cal K

i mol -1-) (K)

17 . 58 1050-1173 ^ ± 18%

6 9

References [172,174-176].
KC1

11.

Volume Change on Melting *( AFj.)

Measurement method: densities [24]

Table 6.9. Volume change on melting

< A W Uncertainty

22 . 27% ^ ± 0.4%

References [24,177-184].

12.

Vapor r Pressure (pr ) uap

Measurement methods: transpiration [185]; boiling pt. [187];

Rodebush-Dixon [189] ; Rodebush [196]

log p

= 8.2800 - 9032/T (6.6)

precision: ^ ± 0.7% uncertainty: ^ ± 5%

Table 6.10. Vapor pressure from equation (6.6)

T P T P (K) (mm) (K) (mm)

1180 4.22 1360 43.5

1190 4 .90 1370 48.7

1200 5.67 1380 54.3

1210 6.54 1390 60.6

1220 7.53 1400 67.4

1230 8 . 65 1410 74.9

1240 9.91 1420 83 .

1250 11.3 1430 92.0

1260 12 .

1440 101.8

1270 14.7 1450 112.5

1280 16.7 1460 124.1

1290 19.0 1470 136.7

1300 21.5 1480 150 .

1310 24.3 1490 165.3

1320 27 .

1500 181.4

1330 30 .

8

1510 198 .

1340 34.7 1520 217 .

1350 38.9 1530 238 .

References [185-198].

13.

Thermal Conductivity (liquid) (

Measurement method: coaxial cylinder, modified hot wire [202,203],

X = -23.43 x 10" 4

+ 4.103 x 10' 6

T (6.7)

precision: not estimated uncertainty: % ± 20%

Results were reported in graphical or equation forms only.

Eq. obtained by fitting the mean values of [202] and [203]. For [202]

values were interpolated from the graphical presentation.

For numerical values: see table 6.11.

70
KC1

Table 6.11. Thermal conductivity of melt from equation (6.7)

T(K)

X x 10 4 (cal cm

-

sec

-

K

-1

)

T(K)

X x 10 4 (cal cm-1 sec -1 K M

1050 19.63 1130 22.93

1060 20.06 1140 23.34

1070 20.47 1150 23.75

1080 20.88 1160 24.16

1090 21.29 1170 24 . 58

1100 21.70 1180 24 .99

1110 22 . 11 1190 25.40

1120 22.52 1200 25.81

References [199-205].

14. Thermal Conductivity (solid) (X

)

Measurement method: not cited [208]

precision: not estimated uncertainty: not estimated

Insufficient information for estimate of precision and uncertainty

Table 6.12. Thermal conductivity of solid

T(K)

A x 10 3 (cal cm

-

sec

-

K

-

)

T(K)

A x 10 3 (cal cm-1 sec-1 K

-1

)

85 80.0 280 17 .

100 64 .

0

300 15.7

120 50.0 320 14.4

140 41.0 340 13.4

160 34.4 360 12.4

180 30.0 380 11.7

200 26.6 400 11 .

220 23.5 420 10.6

240 21.0 440 10.1

260 19.0 460 9.2

References [206-213].

15. Cryoscopic Constant (/c^J

Measurement method: calculated

Table 6.13.

from AH^

Cryoscopic

[214]

constant

k _f

, -i -i Uncertainty

(K mol x kg ) 25.4 ^ ± 1%

References [169,214-225].

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5, 190 (1969).

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Ural. Nauch. Tsentr., Akad., Nauk, SSSR, No. 17 , 56 (1971).

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68, 58 (1964).

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69, 248 (1965).

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Khim. Zh. , U, 1123 (1975) .

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Elektrokhimiya, 12_, 200 (1976) .

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Bredig , (1959)

[171] Marchidan, D. I., and Gambino, M. , Mem. Presentes a la Soc. Chim.

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1954 (1966).

[172] Kelley, K. K. , U. S. Bureau Mines, Bulletin 47.6 (1949).

[173] Aukhurst, E., Bjorge, G. , Flood, H. , and Forland, T., Ann. N. Y. Acad.

Sci. , 79, 830 (1960)

[174] Douglas, T. B. , Brookhaven National Laboratory, Report Number BNL-2446

(1954); Trans. Amer. Soc. Mech. Eng., _79, 23 (1957).

[175] vide infrd ref [9].

[176] Dworkin, A. S. , Oak Ridge National Laboratory, private communication

(Dec. 1 , 1964); cited in JANAF Thermo chemical Tables, 2nd Ed., (1971).

[177] Bockris, J.O'M., Pilla, A., and Barton, J. L., J. Phys. Chem., 64_, 507

(1960)

[178] Landon, G. J., and Ubbelohde, A. R. , Trans. Faraday Soc., 5_2 , 647 (1956)

[179] Eucken, A., Z. Angew. Chem., 5_5 , 163 (1942).

[180] Schinke, H. , and Sauerwald, F. , Z. anorg. allgm. Chem., 287, 313 (1956);

ibid., 2TM, 131 (1956); ibid., 304- , 25 (1960).

[181] Eucken, A., and Dannohl , P., Z. Elektrochem. , 4_0_, 814 (1934).

[182] Bredig, M. A., and Johnson, J. W. , Rept. ORNL-1940, p. 19.

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7, 59 (1962).

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220, 14 (1953).

[185]

Schrier, E. E. , and Clark, H. M. , J. Phys. Chem., 6]_, 1259 (1963).

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[186] Topor, L., J. Chem. Thermo., £, 739 (1972).

\ [187] Barton, J. L., and Bloom, H. , J. Phys. Chem., ££, 1413 (1956).

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[189] Fiock, E. F., and Rodebush, W. H. , J. Amer. Chem. Soc., £8, 2522 (1926).

[190] Belyaev, I. N. , and Kesarev, V. V. , Zhur. Neorg. Khim. , £4, 2875 (1969);

Russ. J. Inorg. Chem., £4(10), 1516 (1969).

[191] Halstead, W. D., Trans. Faraday Soc., £6, 1966 (1970).

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9(4), 1017 (1964); Russ. J. Inorg. Chem., 9(4), 556 (1964).

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"Progress in Crystal Physics" Vol. 1, (R. S. Krishnan, ed.)

Interscience, New York 1958.

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1445 (1962).

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Solid State, ££, 39 (1974).

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7 9
KC1

[216] Hoenen, P. H. J., Z. Physik. Chem. , 83_, 513 (1913).

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et Kinetics , p. 492 (1955).

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Zh. Neorgan. Khim. , 9^, 1687 (1964).

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572 (1911).

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79, 344 (1975).

80
VII

Magnesium Chloride: MgCl

1. 2 Melting Temperature (

m

) Melting point:

714° ±

2 °C [3,12]

References [1-15] .

2.

Density (p)

Measurement method: Archimedean technique [16]

P = 1.976 - 3.02 x 10' 4 T (7.1)

precision: ± 0.15% uncertainty: ^ ± 0.2%

Table 7.1. Densities from equation (7.1)

T(K)

P (g cm -3

)

T(K)

P_

(g cm 3

)

1000 (1.675) 1120 1.638

1020 1 .668 1140 1.632

1040 1.662 1160 1 . 626

1060 1.656 1180 (1.620)

1180 1.650 1200 (1.614)

1100 1 . 644 1220 (1.608)

1240 (1.602)

Values in parentheses are extrapolated.

References [2,7-10,16-21].

3.

Surface Tension (y)

Measurement method: maximum bubble pressure [14]

Y

= 76.73 - 1.0 x 10" 2 T (7.2)

precision: ^ ± 0.4% uncertainty: ^ ± 0.8%

Table 7.2. Surface tension from equation (7.2)

T(K)

Y (dyn cm 3 )

T(K)

Y (dyn cm 1 ) 990 66.8 1110 65.6

1000 66 .

1120 65.5

1010 66.6 1130 65.4

1020 66.5 1140 65.3

1030 66.4 1150 65.2

1040 66.3 1160 65.1

1050 6 6.2 1170 65.0

1060 66.1 1180 64.9

1070 66.0 1190 64.8

1080 65.9 1200 64.7

1090 65.8 1210 6 4.6

1100 65.7

References [1,14,22-25] .

81
MgCl

2 Viscosity (x\)

Measurement method: oscillating sphere [26,27]

n = 14.903 - 2.039 x 10

_2

T + 7.625 x 10" 6

T

2 (7.3)

precision: ± 2.29% uncertainty: 'v ± 5%

Equation (7.3) averaged from [26-27]

Table 7.3. Viscosity from equation (7.3)

T(K)

a(cp)

T(K)

a (cp)

1000 2.14 1080 1.78

1010 2.09 1090 1.74

1020 2.04 1100 1 .70

1030 1 .99 1110 1 .66

1040 1.94 1120 1.63

1050 1 .90 1130 1.60

1060 1 .86 1140 1 .57

1070 1.82

References [26,27],

Electrical Conductance (k)

Measurement method: ac technique [11]

< = -0.605419 + 1.34949 x 10

_3

T + 2.94264 x 10" 7 T

2 (7.4)

precision: ± 0.24% uncertainty: ^ ± 2%

Table 7.4. Electrical conductance from equation (7.4)

T(K)K (ohm 1 cm 1 )

T(K)K (ohm 1 cm 1 ) 1000 1.038 1120 1.275

1020 1.077 1140 1.315

1040 1.116 1160 1.356

1060 1.156 1180 1 .397

1080 1.195 1200 1.438

1100 1.235 1220 1.479

1240 1.520

References [5,7,11,24,26,28-32].

Safety and Hazards

A. Hazard rating [33-35]

(i) Slight

(ii) Vapor pressure: at m.pt. (714°C)

^ 0.11 mm; at 820°C, ^ 1 mm

B. Disaster hazards [33,36-38]

(i) Molten salt bath "explosions": i.e., explosive generation of

steam due to bulk water "carry-over" and/or equipment

failure; i.e., explosive expansion of "trapped" air.

82
MgCl

2

(ii) Chlorides evolve highly toxic fumes when

heated to decomposition, or contacted with acids.

References [33-38].

7.

Corrosion

Table 7.5. Corrosion studies from primary research literature

S tud ie s References

Zr 39

Mg, Ni, Zr, Ti 40

Ti, Zr, Hf, ThC 1^

41

Thermodynamics of corrosion 41-43

Electrochemical approach 44,45

Corrosion in molten salts/

annotated biblio. 46

References [39-46] .

8. Diffusion

No diffusion studies reported

9. Heat of Fusion (AHj.)

Measurement method: drop calorimetry [6]

Table 7.6. Heat of fusion

AH°

(kcal mol ) Uncertainty

10.30 ^ ± 0.5%

10 .

References [6,47,48].

Heat Capacity

Measurement method: drop calorimetry [6,49]

Table 7.7. Heat capacity

C P

v Temp, range Uncertainty

(cal K

- lmol - -*-) (K)

22 . 1 987-1500 ^ ± 0.5%

8 3

References [6,12,16,47,49].
MgCl

2 11 . Volume Change

Measurement

on Melting (AV^J

method: densities [16]

Table 7.8. Volume change on melting

< A W Uncertainty

30.46% ^ ± 2%

References [lb,5UJ.

12. Vapor r Pressure (pr ) vap

Measurement method: boiling pt. [52]

log p

= - 11735/T - 4.076 log T + 23.15 (7.5)

precision: ^ ± 0.51 uncertainty: •*> ± 51

Table 7.9. Vapor pressure from equation (7.5)

T(K)

P(mm)

T(K)

—

P(mm)

1210 7 . 69 1320 34.70

1220 8.94 1330 39.25

1230 10.35 1340 44.31

1240 11.95 1350 49.91

1250 13.77 1360 56.11

1260 15.83 1370 62.95

1270 18.14 1380 70.51

1280 20.75 1390 78.82

1290 23.68 1400 87 .‘95 1300 26.95 1410 97.97

1310 30 .62

References [51-53].

13. Thermal Conductivity (liquid) (

J Measurement method: constriction technique [54]

X = -8.571 x 10' 3 + 11.231 x 10‘ 6

T (7.6)

precision: not estimated uncertainty: ^ ± 20%

Results were reported in graphical or equation forms only.

Table 7.10. Thermal conductivity of melt from equation (7.6)

T(K)

X x 10 4 (cal cm

-1 sec-1 K~ 1 )

T(K)

X x 10 4 (cal cm

-1 sec-1 K

_1

) 1020 28.85 1080 35.58

1030 29.97 1090 36.71

1040 31.09 1100 37.83

1050 32.22 1110 38.95

1060 33.34 1120 40.08

1070 34.46

Reference [54]

84
MgCl

2

Thermal ConductivityJ (solid) (X ) s Measurement method: constriction technique [54]

precision: not estimated uncertainty: ^ ± 10%

Table 7.11. Thermal conductivity of solid

T(K)

X x 10 4 (cal cm“ 1 sec' 1 K

- *

)

T(K)

X x 10 4 (cal cm-1 sec

_1 K~ *

)

373 43.4 673 10.5

473 25.3 773 10.5

573 14.3 873 15.5

923 20.0

Sole investigation; values interpolated from the graphical presentation.

Reference [54]

Cryoscopic Constant- (k

Measurement method: calculated from AH£ [55]

Table 7.12. Cryoscopic constant

References

k

f (K mol-^kg ) Uncer ta int y

17 . 90 'v. ± 0.5%

,55-57]

References

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Selected Values of Chemical Thermodynamic Properties , NBS Circ. 500;

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[ 8 ]

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Royal. Soc. (London), A255 , 558 (1960).

8 5
[ 12 ]

MgCl

2 Stull, D. R. , and Prophet, H. (eds.), JANAF Thermochemical Tables 3 2nd Ed., NSRDS-NBS 37, U. S. Gov't. Printing Office, Washington,

D. C. (1971).

[13]

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,

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24, 489 (1970).

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Obshch. Neorgan. Khim., 70 (1965).

[33] "dangerous Properties of Materials"

,

Sax, N. I., Van Nostrand Reinhold

Co. , N. Y. (1969) .

[34] "Registry of Toxic Effects of Chemical Substances"3 Christensen, H. E.,

and Lubinbyhl, T. T., eds . , U. S. Dept. H. E. W. , ; U. S. Gov't. Printing

Office, Washington, D. C. (1975).

[35] Vapor pressure, calculated (see p. 84, this work).

[36] "Potential Hazards In Molten Salt Baths for Heat Treatment of Metals

3 National Board Fire Underwriters Research Report No. 2 (1954).

[37] "Handbook of Reactive Chemical Hazards

3 Bretherwick, L., Butterworths

Co . , London (1975) .

86
[38]

MgCl

2 Janz, G. J., Tomkins, R. P. T., Downey, J. R. , Jr., and Allen, C. B.,

"Safety and-. Hazards" Chapter in "Eutectic Data"3 ERDA TID-27163-P1

NTIS, U. S. Dept. Commerce, Springfield, Va., (1977).

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,

Ural. Nauch. Tsentr. Akad. Nauk SSSR, 1_9 , 69 (1973).

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Posokhin,* Yu. V., and Puzanova, T. A., Fiz. Khim. Elektrokhim. Rasplav.

Solei Shlakov, 1, 115 (1969)

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Salts", Proceedings of the European Conference on the Development

of Molten Salts Applications", p. 203, (1973), Battelle, Geneva.

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Proceedings International Symposium on Metal-Slag-Gas Reactions and

Processes, The Electrochemical Society, Inc., Princeton, N. J. , p.

581 (1975).

[46] Janz, G. J., and Tomkins, R. P. T., Corrosion, 34_, (in press) (1978).

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(1954); Trans. Am. Soc. Mech. Eng., 79, 23 (1957).

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12,(3), 791 (1967); Russ. J. Inorg. Chem., 12(3), 414 (1967).

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[57] Menge , 0., Z. anorg. allgm. Chem., 7_2, 162 (1911).

8 7
VIII.. Calcium Chloride: CaC^

1.

Melting Temperature (!F^7

Melting point:

782° ± 5°C [1,2, 4, 7]

References [1-17] .

2.

Density ( p ) Measurement method: Archimedean technique [14]

p = 2.5261 - 4.225 x 10' 4 T (8.1)

precision: ± 0.21 uncertainty: ^ ± 0.91

Table 8.1. Densities from equation (8.1)

T(K)

P (g cm 3

)

T(K)

P (g cm 3

) 1060 2 .0783 1150 2 . 0402

1070 2 .0740 1160 2 . 0360

1080 2 . 0698 1170 2 .0318

1090 2 . 0656 1180 2.0276

1100 2 . 0614 1190 2 .0233

1110 2.0571 1200 2 . 0191

1120 2.0529 1210 2 . 0149

1130 2 . 0487 1220 2 . 0107

1140 2 . 0445 1230 2 . 0064

References [14,18-20]*

3.

Surface Tension (y)

Measurement method: maximum bubble pressure [13]

y

= 223.79 - 7.28 x 10' 2 T (8.2)

precision: ± 0.3% uncertainty: ^ ± 0.5%

Table 8.2. Surface tension from equation (8.2)

T(K)

Y (dyn cm 3 )

T(K)

Y

(dyn cm 3 ) 1040 148.1 1130 141.5

1050 147.4 1140 140.8

1060 146.6 1150 140.1

1070 145.9 1160 139.3

1080 145.2 1170 138.6

1090 144.4 1180 137.9

1100 143.7 1190 137.2

1110 143.0 1200 136.4

1120 142.3

References [13,21,22] .

88
CaCl

2 Viscosity

(h)

Measurement method: oscillating (liquid filled) cylinder [23]

n = 619.541 - 1.54489 T + 1.29259 x 10' 3 T

2

- 3.61856 x 10

_7

T

3 (8.3)

precision: ± 3.5% uncertainty: -v ± 30%

Table 8.3. Viscosity from equation (8.3)

T(K)

n(cp)

T(K)

n (cp)

1060 3 . 34 1150 2.03

1070 3.11 1160 1.96

1080 2.90 1170 1 .89

1090 2.72 1180 1.83

1100 2 .57 1190 1.77

1110 2.43 1200 1 .72

1120 2.31 1210 1 .66

1130 2 . 20 1220 1 .59

1140 2.11 1230

1240

1.52

1.44

References [15,23,24].

Electrical Conductance (k)

Measurement method: ac technique [16]

k = 19.628 exp (-4749/RT) (8.4)

precision: ± 0.25% uncertainty: v ± 2.0%

Table 8.4. Electrical conductance from equation (8.4)

T K T K (K) (ohm 1 cm 1 ) (K) (ohm -^cm *)

1060 2 . 059 1150 2.457

1070 2 .103 1160 2 . 501

1080 2.147 1170 2 . 546

1090 2.191 1180 2 .590

1100 2.235 1190 2 .634

1110 2.279 1200 2.679

1120 2.324 1210 2.723

1130 2 . 368 1220 2.768

1140 2.412 1230 2 . 812

References [14,16,20,25-32].

Safety and Hazards

A. Hazard rating [33-35]

(i) Very low

(ii) Vapor pressure: at m.pt. (782°C), ^ 2 x 10" 4 mm; at

1230°C, v 1 mm

B . Disaster hazard s [33,36-38]

(i) Molten salt bath "explosions": i.e., explosive generation of steam due to bulk water "carry-over" and/or equipment failure; i.e., explosive expansion of "trapped" air.
CaCl

2

(ii) Chlorides evolve highly toxic fumes when heated

to decomposition, or contacted with acids.

References [33-38].

7. Corrosion

Table 8.5. Corrosion studies from primary research literature

Studies References

Zr 39

Ti, Zr, Hf, ThCl^ 40

Pb, Pb-Bi 41

Electrochemical aspects 42,43

Thermodynamic approach 44-46

Corrosion in molten salts/

annotated biblio. 47

Reviews: Corrosion in molten

salts 48-50

References [39-50]

8. Diffusion

Measurement method: capillary [51]

List of diffusing species investigated in CaCl

2 as solvent

Ca

2+

, Cl*

precision: not estimated uncertainty: ^ ± 10%

Data reported in equation form only.

Equations

D = A exp [-E/RT] (8.5)

Table 8.6 . 1. Parameters of diffusion equation (8.5)

Species A x 10 3 (cm 2 sec 1 )E (cal mol 3 ) Temp, range

(K)

Ca 2 + 0.38 6130 1060-1280

Cl” 1.90 8860 1060-1290

For numerical values: see table 8.6.2.

9 0

References [51,52].
CaCl

2 Table 8.6.2. Self-diffusion coefficients from equations in table 8.6.1

T(K)

D

C a 2+ X

_ 105

( cm 2 sec 1 )

D C1- x

_ 105

( cm 2 sec 1 ) 1060 2.07 2.83

1080 2.18 3.06

1100 2.30 3.30

1120 2.42 3.55

1140 2.54 3.80

1160 2.66 4.07

1180 2.78 4.34

1200 2.91 4.62

1220 3.03 4.91

1240 3.16 5.21

1260 3.28 5.52

1280 3.41 5.83

1290 5.99

9. Heat of Fusion (AH^.)

Measurement method: drop calorimetry [1,3,4]

Table 8.7. Heat of fusion

AH!

f Uncertainty -1

(kcal mol ) 6.78 'v ± 0.5%

References [1,3,4].

10. Heat Capacity (C ) Measurement method: drop calorimetry [1]

C = 29.08 - 3.48 x

10' 3 T (8.6)

P

precision : ± 0.2% uncertainty: ^ ± 1%

Table 8.8. Heat capacity from equation (8.6)

T(K)

C

P (cal K~ 1 mol 1 )

T(K)

C p (cal K“^mo

-1

) 1055 25 . 41 1260 24 . 70

1060 25.39 1280 24.63

1080 25.32 1300 24 .56

1100 25.25 1320 24.49

1120 25.18 1340 24 .42

1140 25 . 11 1360 24 . 35

1160 25 . 04 1380 24.28

1180 24. 97 1400 24 . 21

1200 24.90 1500 23.86

1220 24 . 83 1600 23.51

1240 24 . 76 1700 23.16

References [1,4,7].

91
CaCl

11. Volume Change on Melting (AV^J

Measurement method: capillary technique [54]

Table b.y. volume change on melting

(AV

f /Vg

) Uncertainty

0.9% ^ ± 15%

References [53-55].

12. Vapor r Pressure (pr ) vap

Measurement methods: effusion [56]; boiling pt. [57]

log p

= 8.4073 - 12622/T f 8 . 7)

precision: ^ ± 3% uncertainty: ^ ± 10%

Table 8.10. Vapor pressure from equation (8.7)

T P T P (K) (mm) (K) (mm)

1120 0 . 0014 1420 0.330

1140 0.0022 1440 0.439

1160 0 . 0034 1460 0 .578

1180 0 . 0051 1480 0.757

1200 0 . 0077 1500 0.983

1220 0.0115 1520 1.269

1240 0 . 0169 1540 1 .626

1260 0.0245 1560 2 . 071

1280 0 . 0352 1580 2 .622

1300 0 . 0499 1600 3 .300

1320 0.0700 1620 4.130

1340 0.0973 1640 5 .140

1360 0 .134 1660 6 .363

1380 0.182 1680 7 .838

1400 0 . 246 1700 9 . 607

References [56-58].

13. Thermal Conductivity (liquid) (A^J

Measurement method: coaxial

A = -22.88 x 1 -8.68 x 10

precision: ±

cylinder [60]

0" 2 + 31.18 x 10" 5 T

9 t

2 - 1 1 3 7.53 x 10 1

i

( 8 . 8 )

uncertainty: ^ ± 20%

Table 8.11. Thermal conductivity of melt from equation (8.8)

T(K)

A x 104 (cal cm

-1 sec

-1

K'" 1 )

T(K)

A x 10 4 (cal cm-^ec" 1 K

_1

) 1070 26.80 1110 36.64

1080 30.03 1120 37.82

1090 32.74 1130 38.47

1100 34.95

9 2

References [59,60].
CaCl

2

14. Thermal Conductivity (solid) (\ ) ° s No thermal conductivity studies reported

15. Cryoscopic Constant (kj.)

Measurement method: calculated from AH£ [4]

Table 8.12. Cryoscopic constant

k rf Uncertainty

(K mol-^-kg

-

’*') 35.5 ^ ± 1%

References [1,4,61-63].

16.

References

[1] Moore, G, E., J. Amer. Chem. Soc., 65_, 1700 (1943).

[2] Rossini, F. D., Wagman, D. D., Evans, W. H. , Levine, S., and Jaffe, I.,

"Selected Values of Chemical Thermodynamic Properties , NBS Circ. 500;"

U. S. Gov't Printing Office, Washington, D. C. (1952).

[3] Chiotti, P., Gartner, G. J., Stevens, E. R. , and Saito, Y. , J. Chem.

Eng. Data, 11 , 571 (1966).

[4] Dworkin, A. S., and Bredig, M. A., J. Phys . Chem., 67_, 69 7 (1963).

[5] Darmois, G., and Petit, G., Bull. Soc. Chim. Fr., 511 (1958).

[6] Emons , H. H. , and Richter, D. , Z. Anorg. Chem., 339 , 91 (1965).

[7] Stull, D. R. , and Prophet, H. (eds.), "JANAF Thermochemical Tables

3 2nd Ed., NSRDS-NBS 37, U. S. Gov't Printing Office, Washington, D. C.

(1971) .

[8] Story, B., and Clarke, I. T., J. Metals, 9, 1449 (1957).

[9] Argyriades, D. , Ph.D. Thesis, Techn. Hochschule (Aachen); FDR (1954).

[10] Fuseya, G., and Ouchi, K. , Denki Kagaku, ll_, 254 (1949).

[11] Potter, E. V., St. Clair, H. W. , and Huber, R. W. , U. S. Bur. Mines,

Rpt . 4858 (1952).

[12] Lillebuen, B. , Ph.D. Thesis, Univ. Trondheim (NTH), Norway (1969).

[13] Ellis, R. B., USAEC Contract AT (40 - 1

) - 2 0 73 , Prog. Rpt. (1961).

[14] Yaffe, I. S., and van Artsdalen, E. R. , USAEC-ORNL- 2159 (Semi-Ann.

Prog. Rpt., p. 77) (1956).

Janz, G. J. , and Reeves, R. D., Trans. Faraday Soc . , 61

,

2305 (1965).

Bockris, J. O'M., Crook, E. H., Bloom, H. , and Richards , N . E . , Proc

Royal Soc. (London), A255, 558 (1960).

[17] Douglas, T. B., Trans. ASME, 79_, 23 (1957).

[18] Arndt, K., and Lowenstein, W. , Z. Elektrochem. , 1_5, 789 (1909).

[19] vide infra: ref. [11].

[20] Arndt, K. , and Gessler, A., Z. Elektrochem., 14, 665 (1908).

93
CaCl-2

[21] Lantratov, M. F., Zhur. Prik. Khim. , 34^, 1249 (1961).

[22] Lehman, D. S., Ph.D. Thesis, Indiana University, USA (1959).

[23] Karpachev, S., and Stromberg, A., Zhur. Fiz. Khim., 11_, 852 (1938).

[24] Crook, E. H. , Ph.D. Thesis, Univ. Pennsylvania, USA (1959).

[25] Arndt, K. , Z. Elektrochem. , L2, 337 (1906).

[26] Biltz, W. , and Klemm, W. , Z. anorg. Chem. , 152 , 225, 267 (1926).

[27] Ryschkewitsch , E., Z. Elektrochem., 3J9, 531 (1933).

[28] Lee, E., and Pearson, E. P., Trans. Electrochem. Soc., 8_8, 171 (1945).

[29] Vereschet ina , I. P., and Luzhnaya, N. P., Izv. Sekt.—Fiz. Khim.

Anal., Inst. Obshch. Neorg. Khim., Akad. Nauk, SSSR, 2_5, 188 (1954).

[30] Winterhager, H. , and Werner, L., Forschungsber . Wirtsch. Verkehrsminis

teriums Nordrhein-Westfalen, No. 341 (1956).

[31] Poincare, L., Ann. Chim. Phys . , 2^, 289 (1890).

[32] Clarke, I. T. , and Story, B., J. Metals, 9_, 1149 (1957).

[33] "Dangerous Properties of Materials ", Sax, N. I., Van Nostrand Reinhold

Co., N. Y. (1969).

[34] "Registry of Toxic Effects of Chemical Substances ", Christensen, H. E.,

and Lubinbyhl, T. T., eds., U. S. Dept. H. E. W. ; U. S. Gov’t

Printing Office, Washington, D. C. (1975).

[35] Vapor pressure, calculated (see p. 92, this work).

[36] "Potential Hazards In Molten Salt Baths for Heat Treatment of Metals "

,

National Board Fire Underwriters Research Report No. 2 (1954).

[37] "Handbook of Reactive Chemical Hazards ", Bretherwick, L., Butterworths

Co., London (1975).

[38] Janz, G. J. , Tomkins, R. P. T., Downey, J. R. , Jr., and Allen, C. B.

,

"Safety and Hazards" Chapter in "Eutectic Data"} ERDA TID- 27163-PI

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[39] Thai, V., Ozeryanaya, I. N., and Smirnov, M. V., Tri. Inst.

Elektrokhim. , Ural. Nauch. Tsentr. Akad. Nauk SSSR, 1_9, 69 (1973).

[40] Smirnov, M. V., Kudyakov, V. Ya., Loginov, Ya. A., Rossokhin, E. G.,

Posokhin, Yu. V., and Puzanova, T. A., Fiz. Khim. Elektrokhim.

Rasplav. Solei Shlakov, 1^, 115 (1969) .

[41] Vasin, B. D. , Nichkov, I. F., and Raspopin, S. P., Izv. Vyssh. Ucheb

Zaved., Tsvet. Met., 15^, 102 (1972).

[42] Pizzini, S., "Materials Problems In The Industrial Applications of

Molten Salts" , Proceedings of the European Conference On The

Development of Molten Salts Applicat ions'-' , p. 203 (1973); Battelle,

Geneva

[43] Johnson, K. E., "Electrochemical Approaches to Corrosion In Molten Salts" , Proceedings International Symposium on Metal-Slag-Gas Reactions and

Processes, The Electrochemical Society Inc., Princeton, N. J., p. 581

(1975)

[44] Littlewood, R. , J. Electrochem. Soc., 109 , 525 (1962).

[45]

Edeleanu, C., and Littlewood, R. , Electrochimica Acta, _3, 195 (1960).

9 4
CaCl

2

[46] Littlewood, R. , and Argent, E. A., Electrochimica Acta, 4_, 114 (1961)

[47] Janz, G. J., and Tomkins, R. P. T., Corrosion, _34 (in press) (1978).

[48] Smirnov, M. V. , and Ozeryanaya, I. N. , Nauki Tekh. Korros . Zashch.

Korros., 2_, 171 (1973).

[49] Ketelaar, J. A. A., Chemie. Ing. Techn., 4_5, 667 (1973).

[50] Inman, D., and Wrench, N. S. , Brit. Corr. J., ]L , 246 (1966).

[51] Bockris, J. O'M., Richards, S. R. , and Nanis, L., J. Phys . Chem. , 69 . 1627 (1965).

[52] Ichikawa, K. , Shimoji, M. , and Niwa, K. , Ber. Bunsen. Physik Chem.,

69, 248 (1965).

[53] Bockris, J. O'M., Pilla, A., and Barton, J. L. , Rev. Chim. (Roumaine)

7, 59 (1962). '

[54] Schinke, H. , and Sauerwald, F., Z. anorg. allgm. Chem., 287, 313

(1956); ibid., 284, 131 (1956); ibid., 304, 25 (1960).

[55] Bockris, J. O'M., Pilla, A., and Barton, J. L., J. Phys. Chem., 64,

507 (1960).

[56] Hildebrand, D. L., and Potter, N. D. , J. Phys. Chem., 67_, 2231 (1963)

[57] Novikov, G. I., and Gavryuchenkov, F. G., Zh. Neorg. Khim. , 9^(2),

475 (1964); Russ. J. Inorg. Chem., 9(2), 260 (1964).

[58] Janz, G. J., et al . , (MSDC-RPI); merge of V. P. data base (ref. 56,

57); (unpublished work, 1978).

[59] Bystrai, G. P., Desyatnik, W N. , and Zlakazov, Z. A., High Temp.,

13, 606 (1975).

[60] Polyakov, P. V. , and Gildebrandt, E. M. , High Temp., 12_, 1166 (1974).

[61] Janz, G. J., et al., (MSDC-RPI) unpublished work (1977).

[62] Sandonnini, C., Gazz. Chim. Ital., 44 (I) , 290 (1914).

[63] Menge , 0., Z. anorg. allgm. Chem., 72_ , 162 (1911).

95
IX. Aluminum Chloride: AICI 3 1.

Melting Temperature (T ) Melting point:

192° ± 1°C (at 2.3 atm)

sublimes at 180. 1°C [4,5]

References [1-5,7-10].

2

.

density ( p

)

Measurement method: Archimedean technique [1]

p = 2.18725 - 5.4045 x 10

_4

T - 1.13544 x 10" 5 T

2 + 3.04126

precision: ± 0.15% uncertainty: ^ ± 2%

Table 9.1. Densities from equation (9.1)

T

(K)

P_

(g cm 3

)

T(K)

P (g cm 3

) 465 1.287 515 1.169

470 1.277 520 1.15 5 475 1.266 525 1.142

480 1.256 530 1.127

485 1.243 535 1.113

490 1.231 540 1 . 098

495 1.219 545 1.082

500 1 .207 550 1.066

505 1.195 555 1.050

510 1.182 560 1.033

References [1-3,8,11,12].

3.

Surface Tension (y)

Measurement method: capillary rise [13]

y

= 42.43 - 7.04 x 10' 2 T (9.2)

precision: ± 0.4% uncertainty: ^ ± 1%

Table 9.2. Surface tension from equation (9.2

T

(K)

Y (dyn cm 1 )

T(K)

Y (dyn cm *)

480 8.64 540 4.41

490 7 . 93 550 3 .71

500 7 . 23 560 3 . 01

510 6.53 570 2.30

520 5.82 580 1.60

530 5.12 590 0.89

References [13] .

4.

Viscosity (r\)

Measurement method: oscillating cylinder [ 6 ]

n = 3.2146 - 9.6606 x 10

_3

T + 7.4554 x 10

_6

T

2 (9.3)

9 6

10" 8

T

3 (9.1)
A1C1

3

precision: ± 0.39% uncertainty: ^ ± 5%

Table 9.3. Viscosity from equation (9.3)

T n T 0 (K) (cp) (K) (cp)

470 0.321 520 0.207

480 0.295 530 0 . 189

490 0.271 540 0.172

500 0.248 550 0.157

510 0.227 560 0.143

References [1-3,6,8,13].

5. Electrical Conductance (k)

Measurement method: ac technique [1-3,8]

< = 7.0270 x 10' 6

- 3.6646 x 10* 8 T + 4.8623 x 10 _11

T

2 (9.4)

precision: ^ ± 1.7% uncertainty: ^ ± 3%

Table 9.4. Electrical conductance from equation (9.4)

T(K)K X 10?

(ohm 1 cm 1 )

T(K)K x 10 7_ (ohm 1 cm 1 ) 475 5.91 500 8 . 60

480 6.40 505 9 .21

485 6.91 510 9.84

490 7 .45 515 10.50

495 8.01

References [1-3,8,14,15].

6. Safety and Hazards

A. Hazard rating [16-18]

(i) Toxicity - severe

(ii) Vapor pressure: sublimes; at 100°C, ^ 1 mm

B. Disaster hazards [16,19-21]

(i) Molten salt bath "explosions": i.e., explosive generation of

steam due to bulk water "carry-over" and/or equipment failure;

i/e., explosive expansion of "trapped" air.

(ii) Chlorides evolve highly toxic fumes when heated to

decomposition, or contacted with acids. Reacts exothermically

with moisture, to evolve HC1 fumes.

References [16-21].

97
aici

3

7.

Corrosion

Table 9.5. Corrosion studies from primary research literature

Studies References

metals 22

Ca 23

A1 24

A1 , Ag, Au , Cu, Mo, Ni,

Pd, Ti, Fe, Pt, stainless

steel 25

Electrochemical approach 26,27

Thermodynamics of corrosion 28-30

Corrosion, annotated biblio. 31

Reviews 32-34

References [22-34].

8. Diffusion

No diffusion studies reported

9. Heat of Fusion (A H8.)

Measurement method: drop calorimetry [7]

Table 9.6. Heat of fusion

AH ° (kcal mol ) Uncertainty

8. 5 ^ ± 3%

References [4,7,35,36].

10.

Heat Capacity (C

)

Measurement method: drop calorimetry [7]

Table 9.7. Heat capacity

C

P Temp, range Uncertainty

(cal K

-

f mo 1

)

(K)

30 473-504 ^ ± 3 %

References [4,7,36].

98
A1C1

3

11.

Volume Change on Melting (A V ~)

Measurement method: capillary technique [37]

Table 9.8. Volume change on melting

(AV,/V ) r s Uncertainty

83.0% ~ ± 0.5%

References [37]

12.

Vapor r Pressure (pr ) vap

Measurement method: isoteniscope [43]

log p

= 7.42055 - 1948. 55/T (9.5)

precision: ^ ± 0.1% uncertainty: ^ ± 3%

Table 9.9. Vapor pressure from equation (9.5)

T P T P (K) (mm) (K) (mm)

455 1374 495 3049

460 1530 500 3338

465 1699 505 3648

470 1882 510 3980

475 2081 515 4335

480 2297 520 4714

485 2529 525 5117

490 2779 530 5547

References [38-43].

13.

Thermal Conductivity (liquid) (X^)

No thermal conductivity studies reported.

14.

Thermal Conductivitys (solid) (X ) s No thermal conductivity studies reported.

15.

Cryoscopic Constant (kJ

Measurement method: calculated from AH£ [44]

Table 9.10. Cryoscopic constant

k f (K mol

_1 kg-1

) . Uncertainty

6.7 ^ ± 3%

References [7,44].

16.

References

[1] King, L. A., and Seegmiller, D. W. , J. Chem. Eng. Data, 1_6, 23

9 9

(1971) .
A1C1

3

[2] Grothe, K. H. , Kleinschmidt , P., and Franke, L., Z. anorg. allgm. Chem.

391 , 255 (1972).

[3] Kleinschmidt, P., Ph.D. Thesis, Univ. Hannover, FDR (1968).

[4] Stull, D. R., and Prophet, H. , "jANAF Thermo chemical Tables" 2nd Ed.,

NSRDS-NBS 37; U. S. Gov't Printing Office, Washington, D. C. (1971).

[5] Rossini, F. D., Wagman , D. D., Evans, W. H., Levine, S.,‘and Jaffe, I.,

'Selected. Values of Chemical Thermodynamic Properties3 NES Circ. 500;"

U. S. Gov't Printing Office, Washington, D. C. (1952).

[6] Brockner, W. , Torklep, K. , and 0ye , H. A., Bunsenber ichte , submitted (1978) .

[7] Fischer, W. , Z. anorg. allgm. Chem., 200 , 332 (1931).

[8]

Biltz, W. , and Voigt, A., Z. anorg. allgm. Chem., 126 , 39 (1923).

[9]

Boston, C. R. , J. Chem. Eng. Data, VL, 262 (1966).

[10] Douglas, T. B., Trans. ASME, 7_9 , 23 (1957).

[11] Boston, C. R. , J. Chem. and Eng. Data, 13_, 117 (1968).

[12] Kryagova, A. I., Zhur . Obshchei Khim . , 9_, 1755 (1939).

[13] Nisel'son, L. A., and Sokolova, T. D. , Russ. J. Inorg. Chem., 2^0, 827

(1965).

[14] Kalita, P. T. , and Plotnikov, V. A., Zhur. Fiz. Khim., 62, 2195 (1930).

[15] Kryagova, A. I., Zh. Obshch. Khim., 9_, 2061 (1939).

[16] "Dangerous Properties of Materials"3 Sax, N. I., Van Nostrand Reinhold

Co. , N.Y. (1969)

[17] "Registry of Toxic Effects of Chemical Substances

3 Christensen, H. E.,

and Lubinbyhl, T. T., eds., U. S. Dept. H. E. W. ; U. S. Gov't

Printing Office, Washington, D. C. (1975).

[18] Vapor pressure, calculated (see p. 99, this work).

[19] "Potential Hazards In Molten Salt Baths for Heat Treatment of Metals"3 National Board Fire Underwriters Research Report No. 2 (1954).

[20] "Handbook of Reactive Chemical Hazards'

3 Bretherwick, L., Butterworths

Co., London (1975).

[21] Janz, G. J., Tomkins, R. P. T. , Downey, J. R. , Jr., and Allen, C. B.

,

"Safety and Hazards

3 Chapter in "Eutectic Data ", ERDA TID-27163-P1

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[22] Usov, P. M. , and Zaralin, A. N., Fiz. Khim. Elektrokhim. Rasplav.

Tverd. Elektrolit. Tezisy Dokl, 2_, 87 (1973).

[23] L 'vov, A. L., and Grilomedov, A. A., Fiz. Khim. Elektrokhim. Rasplav.

Tverd. Elektrolit. Tezisy Dokl, 2_, 85 (1973).

[24] Hoff, H., Electrochim. Acta, 16, 1357 (1971).

[25] Notaya, T., Ishikawa, T., and Midorikawa, R. , Hokkaido Daigaku

Kogakubu Kenkyu Hokoku, 5_5, 63 (1970).

[26] Pizzini L. , "Materials Problems In the Industrial Applications of Molten

Salts?' 3 Proceedings of the European Conference On the Development of

Molten Salts Applications, p . 203, Battelle, Geneva (1973).

100
aici

3

[27] Johnson, K. E., "Electrochemical Approaches To Corrosion In Molten Salts",

Proceedings International Symposium on Metal -Slag-Gas Reactions

and Processes, The Electrochemical Society, Inc., Princeton, N. J.

p. 581 (1975).

[28] Littlewood, R. , J. Electrochem. Soc., 109 , 525 (1962).

[29] Edeleanu, C., and Littlewood, R. , Electrochimica Acta, 3^, 195 (1960).

[30] Littlewood, R. , and Argent, E. A., Electrochimica Acta, 4_, 114 (1961).

[31] Janz, G. J., and Tomkins, R. P. T., Corrosion, _34, (in press) (1978).

[32] Smirnov, M. V. , and Ozeryanaya, I. N., Nauki Tekh. Korros. Z,ashch.

Korros. , 2, 171 (1973)

[33] Inman, D. , and Wrench, N. S., Brit. Corr. J., 1_, 246 (1966).

[34] Ketelaar, J. A. A., Chemie Ing. Techn. , 45_, 667 (1973).

[35]

Biltz, W. , and Voigt, A., Z. anorg. allgm. Chem. , 126 , 47 (1923).

[36] McDonald, R. A., (Dow Chemical Co.) unpublished measurements, cited

in JANAF Thermochemical Tables 3 2nd Ed. (1971).

[37] Schinke, H. , and Sauerwald, F., Z. anorg. allgm. Chem., 287, 313

(1956); ibid., 284, 131 (1956); ibid., 304, 25 (1960).

[38] Naryshkin, I. I., Zhur. Fiz. Khim. , 13 , 690 (1939).

[39] Denisova, N. D., and Baskova, A. P., Zhur. Fiz. Khim., 43, 2353

(1969); Russ. J. Phys . Chem., 43(19), 1317 (1969).

[40] Danov, S. M. , Candidate's Thesis, Gorky (1963).

[41] Nisel'son, L. A., Pustil'nik, A. I., Gavrilov, 0. R. , and Rodin, V. A.,

Zhur. Neorg. Khim., 10(10), 2339 (1965); Russ. J. Inorg. Chem.,

10(10), 1271 (1965).

[42] Smits, A., and Meijering, J. L., Z. Phys. Chem., 41B, 98 (1938).

[43] Viola, J. T., Seegmiller, D. W. , Fannin, A. A., Jr., ana King, L. A.,

J. Chem. Eng. Data, 2_2, 367 (1977).

[44] Janz, G. J., et al . , (MSDC-RPI) unpublished work (1977).

101
X. Lithium Carbonate: Ll

2 C03 1.

Melting Temperature (T ) Melting point:

723° + 3 °C [1-3,8]

References [1-14].

2.

Density (p)

Measurement method: Archimedean technique [1]

P = 2.2026 - 3.729 x 10

_4

T (10.1)

precision: ± 0.1% uncertainty: ^ ± 0.5%

Table 10.1. Densities from equation (10.1)

T

(K)

P (g cm 3 )

T(K)

P (g cm” 3 )

1010 1.8260 1070 1.8036

1020 1.8222 1080 1.7999

1030 1.8185 1090 1.7961

1040 1.8148 1100 1. 7924

1050 1.8111 1110 1.7887

1060 1.8073 1120 1.7850

References [1,15].

3.

Surface Tension (y)

Measurement method: pin detachment [1]

y

= 284.59 - 4.06 x 10

_2

T (10.2)

precision: + 0.1% uncertainty: ^ + 0.3%

Table 10.2 Surface tension from equation (10.2)

T(K)

Y (dyn cm *) T(K)

Y (dyn cm 1

)

1020 243.2 1080 240.7

1030 242.8 1090 240.3

1040 242.4 1100 239.9

1050 242.0 1110 239.5

1060 241.6 1120 239.1

1070 241.1 1130 238.7

References [1,16] ,

4.

Viscosity (r\)

Measurement method: oscillating (liquid -filled) cylinder [17]

n = -5259.12 + 14,8091 T -13,8581 x 10^ 3

T

2 + 4.31294 x 10‘ 6 T

3 (10.3)

precision: ^ + 3% uncertainty: 'v + 30%

102
Ll

2 C0

3

Table 10.3. Viscosity from equation (10.3)

T(K)

n (cp )

1050 4 . 65

1060 4 . 35

1070 4.02

1080 3 .68

1090 3 .37

1100 3.11

1110 2.93

1120 2 .84

References [17,18].

5. Electrical Conductance (<)

[ 1 ] 3 T + 4.3873 x 10' 6 T

2 (10.4)

uncertainty: ^ + 1.5%

Measurement method: ac technique

k = 0.9877 - 1.3529 x 10

precision: + 0.007%

Table 10.4. Electrical conductance from equation (10.4)

T(K)

K (ohm -

cm 1

)

T(K)K (ohm 1 cm 1

) 1010 4 . 097 1070 4.563

1020 4.172 1080 4.644

1030 4.249 1090 4.726

1040 4.326 1100 4.808

1050 4.404 1110 4.892

1060 4.483 1120 4.976

References [1,19-24].

6. Safety and Hazards

A. Hazard rating [25-27]

(i) Inhalation hazard: slight; toxic dose (human):

0.7 mg/kg (oral)

(ii) Vapor pressure: [CO 2 equilibrium dissociation

pressure is ^ 10 mm at approx. 730°C]

Li

2 cc3

<: Li

2 0 + C02 (10,5)

B. Disaster hazards [25,28-30]

(i) Molten salt bath "explosions": i.e. explosive generation

of steam due to bulk water "carry-over" and/or equipment

failure; i.e, explosive expansion of "trapped" air.

(ii) When heated with C0

2 pressures less than equilibrium dissociation pressures, decomposes to form alkali metal

oxide; the toxicology and disaster hazards are the same

as those of very caustic solutions, i.e. react with

water or steam (exothermic) to form solutions that are markedly aggressive to all body tissues (chemical burns).

Lithium carbonate itself is classified as a strong caustic.

103
Li

2 C0

3

References [25-30].

7. Corrosion

Table 10.5. Corrosion studies from primary research literature

Studies References

Ti alloy 31

Au, Pt, Ag, Ni, Au-Pd 32

Pt, Au, Ag, MgO, BN 33,34

Ag, Co, Ni 35

Metals, alloys 36

Pt, Pd, Rh, Ir (C>2 environment) 37

Ag (C>2 + CO; H

2 + CO

2 environment) 38

Ag (0

2

; Li

2 C0

3-Li

2 0) 14

Pt (N

2

; Li

2C0

3-Li

2 0) 39,40

Pt, Au (Ar; L^CO^L^O) 41

Ag, Pt, Ni; porcelain, quartz

(L^CO^L^O; N

3 atmosphere) 10

Acid-base relationships in

molten carbonates 42-46

Hydrolysis (^0) reactions 14,44,46,47

Corrosion in molten salts:

annotated bibliography 48

Molten carbonates: fuel cells;

thermal energy storage; coal

gasification; power plant stack

gases 49-54

References [10,14,31-54].

8 . Diffusion

Measurement method: capillary [55,56]

List of diffusing species investigated in L^CO^ as solvent

Na

+

, C0

3

2

'

precision: -v + 3.51 uncertainty: ^ + 10%

Equation

D = A exp [-E/RT] (10.6)

104
Li^CO^

Table 10.6.1. Parameters of diffusion equation (10.6)

Species A x 10 3 E Temp, range

(cm 2 sec 1

) (cal mol *) (K)

Na

+ 1.32 9630 1080-1180

co|" 1.35 9740 1120-1265

Table 10.6.2. Diffusion coefficients from equations in table 10.6.1

T(K)

D xt + x 10 5 NaT

(cm 2 sec 1 )

T(K)

D

cof-

* 105

(cm 2 sec 1 )

1080 1.48 1120 1.69

1090 1.55 1140 1.83

1100 1.61 1160 1.97

1120 1.74 1180 2.12

1140 1.88 1200 2.27

1160 2.02 1220 2.43

1170 2.10 1240 2.59

1260 2.76

References [55,56].

9. Heat of Fusion (A H°)

Measurement method: drop calorimetry [11,57]

table 10.7. Heat of fusion

AH °f Uncertainty -1

(kcal mol ) 9.8 ^ ± 10%

10 .

References [11,57,58].

Heat Capacity ( C ) Measurement method: drop calorimetry [57]

C

p

= 30.85 + 13.54 x 10" 3 T (10.7)

precision: ^ + 0,3% uncertainty: ^ + Q { 5%

Table 10.8. Heat capacity from equation (10.7)

T(K)

C

P,

i (cal . K~ -1- m o 1 ~ 1 ) T(K)

C (cal K ^-mol 1 ) 1000 44 .39 1080 45.47

1010 44 . 53 1090 45.61

1020 44.66 1100 45.74

1030 44.80 1110 45.88

1040 44. 93 1120 46.01

1050 45.07 1130 46.15

1060 45.20 1140 46.29

1070 4 5.34 1150 46.42

References [57,58].

105
Li^COj

11, Volume Change on Melting ( hV

Measurement method: estimated; from densities [59]

Table 10.9. Volume change on melting

(4V

f /Vs

) Uncertainty

6.9% ^ ± 8 %

References [ 59] .

12. Vapor Pressure (p ) r vap

Measurement method: cited with each data set [14,50,60].

No systematic studies of vaporization as "molecular carbonate"

have been reported, viz:

Ll

2 C0

3 U)

Li o C0 , rs 2 3 (g)

( 10 . 8 )

Relative to the decomposition of molten carbonates, and other possible

processes contributing to vaporization, the data for Li

2 C0, are as follows.

Decomposition processes:

C0

2 dissociation and equilibrium pressures for molten L^CO-^

Li

2 C0

3 (ft)

Pco

2 = K

d

Ll 2°(£)

Li

2 C0

3 (ft)/

+ CO

Li20

2 (g)

U)

(10.9)

( 10 . 10 )

Here p is the equilibrium C0

2 dissociation pressure, and a the thermodynamically defined activity. For practical purposes, eq. (10.10) is

generally expressed in the mol fraction scale [X] as:

PC0

2

= K

d

The values of the equilibrium C0

2 pressures depend on both the oxide

and carbonate content; the values will not be unique unless the composition is exactly defined, i.e. the oxide content. Further, the

values will depend on the "quality" of the carbonate, and its previous

history.

Ll

2 C0

3 Li 2°(£)

( 10 . 11 )

(i) Equilibrium dissociation constant,

Measurement method: analytical technique [14]

log K

d

= -9970/T + 6.12 (10.12)

precision; not estimated uncertainty; v + 1-6

106
Li^COj

Table 10 . 10 . 1 . CO

2 dissociation constant from equation ( 10 . 12)

T K

d T K

d

(K) (atm) (K) (atm)

(800) (4.5 7x10“ 7) 1050 4. 21xl0 -4

(850) (2 . 46xl0 -6

) 1100 1. 14xl0 -3

(900) (1 . 10x10“ 5) 1150 2 . 82xl0 -

3

(950) (4 . 22x10" 5) 1200 6.48x10 3 1000 1 . 41x10“ 4

(ii) Equilibrium CO

2 dissociation pressures

Measurement method: dynamic TGA technique [60]

log p (mm) =

- 1703jL64 + 17>96 ( 10 . 13)

precision: ^ + 0.5% uncertainty: ^ + 5 $

Table 10.10.2. Equilibrium CO 9 dissociation pressures of

L^COj^ from equation (10.13)

T(K)

pfmm) T(K)

(P (mm)

obs v ’

d

calc ’

d

obsv'd calc '

d

1000 8.5 46 1 080 155 256

1020 18.3 73 1100 300 376

1040 38.3 113 1120 567 546

1060 78.1 171

The p(obsv'd) were for L

2 CO 3 with oxide content ^ 2.3 x 10"

mol/mol carbonate, eq, ,(10.13). The p(calc’d) follow from the data

in table 10 . 10.1 and eq. ( 10 . 11 ).

It appears, from the preceding, that equilibrium was not attained by

the dynamic technique except possibly at the upper temperatures.

The CO 2 dissociation pressure data reported by Lebeau (1905 ) , Johnston

(1908), and Howarth (1930) are understood if the (mol L^O/mol Li 2 C0 3 ) ratios were, respectively: 3 x 10" 2

, 8 x 10" 2

, and 16 x 10~ 2

. Vaporization of molten carbonates:

Measurement method: critical analysis [50]

Since O 2 , H 2 , and water vapor are present in fuel cell operations, the

effects of these, [through contributing reactions leading to the formation of hydroxides, oxides, peroxides, and reduced alkali metals]

should be considered. Such factors have been critically re-examined

by Maru et al., (1976). Some of the possible contributing reactions,

(relative to vaporization losses) are:

107
Li 2 C0

3

M 0 CO, , s 2 3 (£,) — M2 ° 0Q

+ C°2 (g)

(10.14)

M

2 C0

3 (it) + ^°2(g)

=* M

2 0 2(O

+ C°2 (g) (10,15)

M

2 C0

3 (a)

* H2° (g) —r 2M0H

Ct)

+ C °2 Cg)

(.10,16)

M

2 C0

3 (a)

+ H

2 (g ) «

" 2M (0

+ H

2°(g)

+ C0

2 (g)

(10,17)

Calculations o£ the vaporization losses due to hydroxide requires con- sideration of the hydrolysis equilibrium (10,16) and the thermodynamic

activity of the hydroxide in the molten carbonate. While the data are

insufficient for quantitative calculations, it is apparent from such

considerations that hydroxides are the major diluents (under fuel cell

conditions), e.g. up to 6 mol % LiOH can be expected in molten Li 2C 03 . Using the vapor pressures of the molten hydroxides at fuel cell temperatures, as guidelines, viz:

Hydroxide: LiOH NaOH KOH Li

2 (0H)

p (atm) : 1

7

1 0

rH 10' 6 10" 7

and assuming thermodynamic equilibrium between the feed gases and the

molten carbonate, one predicts that the vaporization losses (due to

hydroxide species) would be in the order:

K

2 C0

3

> Li

2 C03 * Na

2 C03

The processes are undoubtedly more complex, for deviations from this

order have been observed, e.g., Li 2 C0 3 > K 2CO 3

. Such observations may

be understood thermodynamically if the local activity of Li 2CC>3 > that

in the bulk electrolyte, or if the vapor saturation with LiOH > KOH.

A more exact account is not possible without additional . data

References [14,50,60-67].

13. Thermal Conductivity (liquid) (X^)

Measurement method: steady state, radial heat flux [ 68 ]

X = -3.2535 x 10

" 3 + 7.961 x 10

_6

T (10.18)

precision: not estimated uncertainty: ^ t 201

Results were reported in graphical and equation forms only.

Table 10,11. Thermal conductivity of melt from equation (10.18)

T(K)

X x 10 4 (cal cm

-1 sec

-1 K-1

)

T(K)X x 10 4 (cal cm

-1 sec

-1 K

-1

) 1000 47 . 08 1160 59.81

1020 48.67 1180 61.40

1040 50.26 1200 63.00

1060 51.85 1220 64 .59

1080 53.44 1240 66.18

1100 55 . 04 1260 67.77

1120 56.63 1280 69.37

1140 • 58.22 1300 70.96

References [ 68 ]

108
Ll

2 CU3

14. Thermal Conductivity (solid) (X ) Measurement method

: absolute steady state radial heat flux [ 68 ]

X = 24.26 x

- 3 10 0 - 49.04 x 10‘ 6

T + 28 .19 x

- 9 2 10 T (420-640 K) (10.19)

X = 18.17 x

- 3 10

0 - 30.95 x 10" 6

T + 16 ,28 x

-9 2 10 T (700-1000 K) ( 10 , 20) precision: not estimated uncertainty: ^ + 10 %

Results were reported in equation and graphical forms only.

Table 10.12. Thermal conductivity of solid from equations (10,19) and (10.20)

T(K)

X x 10 3 (cal cm

-1 sec

-1 K-1

)

T(K)X x 10 3 (cal cm

-1 sec

_1 K

_1

) 420 8 . 64 740 4.18

440 8 . 14 760 4 . 05

460 7 . 67 780 3 .93

480 7.22 800 3.83

500 6.79 820 3.74

520 6.38 840 3 . 66

540 6 . 00 860 3 .59

560 5.64 880 3 . 54

580 5.30 900 3. 50

600 4 . 98 920 3.47

620 4 . 69 940 3.46

640 4 .42 960 3 .46

700 4.48 980 3.47

720 4 .32 1000 3 .50

References [ 68 ]

.

15. Cryoscopic Constant

Measurement method: calculated

Table 10.13.

from AH| [59]

Cryoscopic constant

16.

k f (K mo I - -*- kg - -*-) Uncertainty

14. 9 ^ ± 10%

References [11,59,69,70],

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Ll

2 C0

3

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Ill
Li

2 C0

3

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[68] Egorov, B. N. , and Revyakina, M. P., Teplofiz. Vys . Temp., 8_, 1299 (1970).

[69] Janz, G. J., Neuenschwander, W. , and Kelly, F. J., Trans. Faraday

Soc., 5J9, 841 (1963); see also Janz, G. J., and Lorenz, M. R.,

J. Chem. Eng. Data, 6^, 321 (1961).

[70] Sinistri, C., and Franzosini, P., Rec . Sci. ii A3_, 449 (1963).

112
XI. Sodium Carbonate: Na2C0^

2 . Melting Temperature (T ) Melting point:

858° + 1°C [1-5,11]

References [1-20] .

2. density ( p)

Measurement method: Archimedean technique [1]

p = 2.4797 - 4.487 x 10' 4 T (11.1)

precision: + 0.7% uncertainty: ^ + 1%

Table 11.1. Densities from equation (11.1)

T(K)

P (g cm 3 )

T(K)

P (g cm 3

) 1140 1.9682 1210 1.9368

1150 1 .9637 1220 1.9323

1160 1 .9592 1230 1.9278

1170 1 .9547 1240 1.9233

1180 1 . 9502 1250 1.9188

1190 1.9457 1260 1.9143

1200 1.9413 1270

1280

1.9099

1.9054

References [1,21] .

2. Surface Tension (y)

Measurement method: pin detachment [1]

Y

= 268.51 - 5.02 x

10' 2 T (11.2)

precision: + 0.1% uncertainty: ^ + 0.3%

Table 11.2. Surface tension from equation (11.2)

T(K)

Y (dyn cm 3 )

T(K)

Y (dyn cm 1 ) 1140 211.3 1220 207.3

1150 210.8 1230 206.8

1160 210.3 1240 206.3

1170 209.8 1250 205.8

1180 209 .

3

1260 205.3

1190 208.8 1270 204.8

1200 208.3 1280 204.3

1210 207.8 1290 203.8

References [1] .

4 . Viscosity (r\)

Measurement method: oscillating (liquid -filled) cylinder [22]

n = 3.832 x 10' 5 exp (26260/RT) (11.3)

precision: ^ + 0.5% uncertainty: ^ + 25%

For numerical values: see table 11.3

113
Na

2 C0

3

Table 11.3. Viscosity from equation (11.3)

T(K)

n(cp)

1160 3.40

1170 3.08

1180 2.80

1190 2 .55

1200 2.32

1210 2.12

1220 1 .94

1230 1 .78

1240 1.63

References [22,23].

5. Electrical Conductance (k)

Measurement method: ac technique [1]

k = 13.758 exp

precision: + 0.13%

( -3527/RT) (11.4)

uncertainty: ^ + 1.5%

Table 11.4. Electrical conductance from equation (11.4)

T

(K)

K (ohm 1 cm 1 )

T(K)K (ohm 1 cm 1

) 1140 2 .900 1200 3 .134

1150 2 . 939 1210 3 .173

1160 2.978 1220 3 .211

1170 3 . 018 1230 3 . 249

1180 3.057 1240 3.288

1190 3.096

References [1,9,12,24-27].

6. Safety and Hazards

A. Hazard rating [28-30]

(i) Moderate

(ii) Vapor pressure: [C0 2 equilibrium dissociation pressure

is ^ 1 mm at 950°C]

Na

2 C0

3 Na,0 + CO, (11.5)

B. Disaster hazards [31-33]

(i) Molten salt bath "explosions": i.e. explosive generation of

steam due to bulk water "carry-over" and/or equipment

failure; i.e, explosive expansion of "trapped" air.

(ii) When heated with C0

2 pressures less than equilibrium

dissociation pressures, decomposes to form alkali

metal oxide; the toxicology and disaster hazards are

the same as those of very caustic solutions, i.e. re- act with water or steam (exothermic) to form solutions

that are markedly aggressive to all body tissues • (chemical burns)

References [28-33].

114
Na

2 C0

3

7. Corrosion

Table 11.5. Corrosion studies from primary research literature

S tud ie s References

Silica 34

Pt 35

Metals 36

Cu-Zn 37

Pt, Au, Ag, MgO 38-41

Pt, Pd, Rh, Ir (O 2 environment ) 42

Alumina (Monofrax-A) 59 , 61

Au, Ag, AI 2 O 3 (O 2 environment, Na 2 C 03 ~Na 20 ) 5

Al 2C> 3

> Pt (N 2 atmosphere,

Na 2 C 03 ~Na 20 ) 3,43,44

quartz, porcelain, Ag, Pt,

Ni, (N 2 atmosphere;

Na 2 C0 3 -Na 2 0) 45

Boron nitride 41,58

Na- 3-alumina 58

Fe [ Na 2 CO 3 -NaX ; X = F,

Cl, Br, I] 59

Acid-base relationships

in molten carbonates 46-49

Hydrolysis (H 2 O) reactions 5,50,51

Corrosion in molten salts:

annotated bibliography 52

Molten carbonates: fuel

cells; thermal energy

storage; coal gasification;

power plant stack gases 53-57,59

References [3,5,34-61].

8. Diffusion

Measurement method: capillary [62]

List of diffusing species investigated in Na2C0^ as solvent

Na

+

, COj"

precision: ^ + 1,5%, Na

+

; * + 0,61, CO^" uncertainty: ^ + 101

115
Equation

Na

2 C03

D = A exp [-E/RT] (11.6)

Table 11.6.1. Parameters of diffusion equation (11.6)

Species Ax 1 0

3

( cm 2 s ec 1

)

E (cal mol 1 ) Temp, range

(K)

Na

+ 10.0 12,170 1180-1320

CO 3

"" 2 .86 10,620 1170-1335

Table 11.6.2. Self -diffus ion coefficients from equations in table (11.6.1)

T(K)

D»a* * ]°

5 (cm 2 sec 1

)

D

c 0 y

x 105

(cm 2 sec 1 )

1170 2.97

1180 5.57 3.09

1200 6.07 3.33

1220 6.60 3 . 58

1240 7 .16 3 . 84

1260 7.74 4 . 11

1280 8 .35 4.40

1300 8.99 4 . 69

1320 9 .66 4.99

1340 5 .30

References [62-64].

9. Heat of Fusion (&H°)

Measurement method: drop calorimetry [2,7,67]

table 11.7. Heat of fusion

AH °f (kcal mol ^)

Uncertainty

7 .

^ ± 4 % References [2,5,7,65-67].

10. Heat Capacity (<7^7

Measurement method: drop calorimetry [7]

C = 33.99 + 10.70 x 10' 3 T (11.7)

P

precision: a- + 0.5% uncertainty: ^ + 5%

Table 11.8. Heat capacity from equation (11.7)

T(K)

C

P . . (cal K ^ol -1

)

T(K)

C P , (cal K

_1 mol -1

)

1130 46.08 1180 46.62

1140 46.19 1190 46.72

1150 46.30 1200 46.83

1160 46.40 1210 46.94

1170 46.51

References [2,5,7,65,67].

1 16
Na

2 C03

11. Volume Change on Melting (L

V

Measurement method: estimated from densities [68]

Table 11.9. Volume change on melting

( A V f / V ) t S Uncertainty

16.2% * ± 8%

References [68] .

Vapor Pressure (p . ) r r vap

Measurement method: cited with each data set [5,54,69]

No systematic studies of vaporization as "molecular carbonate"

have been reported, viz:

Na

2 C0 3U) —Na

2 C0

3(g)

tn ' 8)

Relative to the decomposition of molten carbonates and other possible

processes contributing to vaporization, the data for Na

2 C03 are as follows.

Decomposition processes:

C0

2 dissociation and equilibrium pressures for molten Na

2 C03

Na

2 C0

3 (£)

Na 2°(£)

+ CO,

2 (g)

(11.9)

CO,

= K Na

2 C0

3 ( £' Na 2°U)

( 11 . 10 )

Here p is the equilibrium CO 2 dissociation pressure, and a the thermodynamically defined activity. For practical purposes, eq. (11.10) is

generally expressed in the mol fraction scale [X] as:

Na

2 C0

3 ( £)/

tNa

2°(£)

( 11 . 11 )

The values of p rn thus depend on the quality of the "carbonate", i.e.

the oxide content 2 as well as carbonate. This will vary with the previous history. For example, conventional vacuum drying at elevated temperatures, where the sample is heated under dynamic vacuum, may lead to

oxide formation if the pressures are less than the CO 2 equilibrium pressures. It is apparent that the P^q? equilibrium values will be unique

only if the composition of the "carbonate" is exactly defined, i.e.

the oxide content of carbonate.

(i) Equilibrium dissociation constant, .

Measurement method: emf technique [5]

log K

d

=

~ 1

-^—°- + 6.99 (11.12)

precision: not estimated uncertainty: ^ + 1%

117
Na

2 C03

Table 11.10.1. C0

2 dissociation constant from equation (11.12)

T

(K)

K

d

(atm)

T(K)K

d

(atm)

(800) (3.09x 10" 13

) (1050) (1.36 "x 10~ 8) (850) (4.34 x 10“ 12

) (1100) (6.43 x 10“ 8

) (900) (4.54 x 10 -11

) 1150 2.66 x 10 -7

(950) (3.71 x 10 -1 °) 1200 9.77 x 10" 7 (1000) (2.45 x 10" 9

)

(ii) Equilibrium C0

2 dissociation pressures

Measurement method: dynamic TGA technique [69]

log p (mm) =

1 3 2 4

_

. 5

+ ^ 2 . 6 1 (11.13)

precision: ^ + 0.5% uncertainty: ^ + 5%

Table 11.10.2. Equilibrium CC>

2 dissociation pressures from equation (11.13)

T p (mm) T p

(

mm)

_

(K) ob s v ’

d

calc'

d

(K) obs v ’

d

calc ’

d

1130 7.8 7.8 1150 12.4 13.5

1140 9.9 10.2 1160 15.6 17 .

The p(mm) (calc'd) were calculated from the data in table 11,8,1 and

eq. (11.11) and assuming Na20 content, ^ 1.5 x 10' 5 mol/mol Na 2 C03 , and

eq. (11.13).

The thermal dissociation of anhydrous Na

2 CC>3 to C02 (eq. 11.9) has

been studied by Johnston (1908), Howarth and Turner (1930), Kroger

and Stratmann (1961), and Spedding and Mills (1965). The CO 2 dissociation pressure data sets are understood from the preceding, if

the mol Na 20 per mol Na 2 C 03 , were, respectively: ^ 2 x 10" , 3 x 10 -2

, ^ 8 x 10 -4

, and ^ 1.4 x 10" 4

.

Vaporization of molten carbonates:

Measurement method: critical analysis [54]

The "vaporization” observations, based on electrolyte losses from high

temperature molten carbonate fuel cells studies, and the thermodynamics

of the associated reactions have been critically examined by Maru et al.

(1976). For a summary of the results, refer: Li

2

CC> 3

, present work.

References [5,54,62,69-76].

13. Thermal Conductivity (liquid) (\

Measurement method: steady state radial heat flux [77]

X = 1.181 x 10' 3

+ 2.816 x 10" 6

T [11.14]

precision: not estimated uncertainty: ^ ± 20%

Results were reported in graphical and equation forms only.

118
^

200^

Table 11.11. Thermal conductivity of melt from equation (11.14)

T(K)

X x 10 4 (cal cm

sec -

K

_1

)

T(K)

X x 10 4 (cal cm -

sec

- *

)

1140 43.91 1210 45.88

1150 44.19 1220 46.17

1160 44.48 1230 46.45

1170 44.76 1240 46.73

1180 45.04 1250 47 . 01

1190 45.32 1260 47.29

1200 45.60

References [77]

14. Thermal Conductivity (solid) (X ) Measurement method: absolute steady state radial heat flux [78].

X = 9.97 x 10' 5 + 8.57 x 10' 6 T - 9.87 x 10" 9 T

2 (540-580 K) (11.15)

X = 2.04 x 10' 2

- 3.35 x 10' 5 T + 16.14 x 10’ 9 T

2 (700-1135 K ) (11.16)

precision: not estimated uncertainty: ^ + 10%

Results were reported in equation and graphical forms only.

Table 11.12. Thermal conductivity of solid from equations (11,15) and (11.16)

T(K)

X x 10 3 (cal cm

-1 sec

-1 K

_1

)

T(K)

X x 10 3 (cal cm

see -

) 540 1.85 880 3.40

550 1.83 900 3 . 31

560 1 . 80 920 3.23

570 1.78 940 3.16

580 1.75 960 3.10

700 4 .85 980 3.05

720 4 . 64 1000 3 . 02

740 4 . 44 1020 3 . 00

760 4.25 1040 3; 00

780 4 . 08 1060 3.00

800 3 .92 1080 3.03

820 3.77 1100 3.06

840 3.64 1120 3 .10

860 3 .51

References [78] .

15. Cryosoopio Constant (hj.)

Measurement method: calculated from AH£ [68]

Table 11.13. Cryoscopic constant

f Uncertainty

(K mol~ 1 kg" 1

)

37 . 9 ^ ± 3%

References [2,68,79].

119
Na^COj

16. References

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[2] Rolin, M. , and Recapet, J. M., Bull. Soc. Chim. France, 2104 (1964).

[3] Bouaziz, R., and Papin, G., Compt. Rend. Acad. Sci,, Paris* 266,

series C, 1530 (1968).

[4] Tegman, R., and Warmquist, B., Acta Chem. Scand. , 26, 413 (1968).

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600"; U . S. Gov't Printing Office, Washington, D. C. (1952).

[7] Janz, G. J., Neuenschwander , E., and Kelly, F. J., Trans. Faraday

Soc. , 59^, 841 (1963) .

[8] Stern, K. , "High Temperature Properties and Decomposition of Inorganic Compounds. II. Carbonates"3 NSRDS-NBS-30 ; U. S.

Gov't Printing Office, Washington, D. C. (1969).

[9] Braun, F., Pogg. Ann., 154, 190 (1875).

[10] Carnelley, N. , J. Chem. Soc., 489 (1876); ibid, 281 (1878).

[11] Stull, D. R. , and Prophet, H. , (eds,}, "JANAP Thermochemical Tables"3 2nd Ed., NSRDS-NBS 37, U. S. Gov't Printing Office, Washington,

D. C. (1971).

[12] Arndt, K. , Z. Elektrochem. , 12, 337 (1906).

[13] Hiittner, L., and Tamman, G., Z. anorg . Chem., 43, 215 (1905).

[14] Sackur, 0., Z. Elektrochem., 16, 649 (1910).

[15] Eitel, W. , and Skaliks, W. , Z. anorg. Chem., 183 , 263 (1929).

[16] Reisman, A., Holtzberg, F., and Banks, E., J. Amer. Chem.

Soc. , 80, 37 (1958) .

[17] Belyaev, I. N. , and Sholokovich, M. L., J. Appl . Chem. USSR,

25, 733 (1952).

[18] Sato, T., Tech. Rpts. Tohoku Univ., 11, 403 (1934).

[19] Makarov, S. Z., and Shalgina, M. P., Proc. Acad. Sci., USSR,

Div. Chem. , 5, 69 (1940)

[20] Sementsova, A. K. , and Bergman, A. G., J. Gen. Chem., USSR,

26, 992 (1956).

[21] Brunner, E., Z. Angew. Chem., 38, 350 (1904).

[22] Janz, G. J., and Saegusa, F., J. Electrochem. Soc., 110, 452 (1963).

[23] Vorobev, G. V., Pal'guev, S. F., and Karpachev, S. V., Trudy No. 6

(1965); Inst. Electrochem. Ural. Acad. Sci., Eng. Trans.

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Fiz-Khim. Ana:l . Obsch. Neorg Khim. Akad . Nauk SSSR, 26, 164 (1955).

[25] Ward, A. T., and Janz, G. J., Electrochim. Acta, 10, 849 (1965).

120
Na

2 C0

3

[26] Spedding, P. L., J. Electrochem. Soc., 120 , 1049 (1973).

[27] Ryschkewitsch , E., Z. Elektrochem . , 3_9, 531 (1933).

[28] "Dangerous Properties of Materials ", Sax, N. I., Van Nostrand

Reinhold Co., N. Y. (1969).

[29] "Registry of Toxic Effects of Chemical Substances "

,

Christensen,

H. E., and Lubinbyhl, T. T. , eds., U. S. Dept. H.E.W; U. S. Gov’t

Printing Office, Washington, D. C. (1975).

[30] Vapor pressure, calculated (see p. 118, this work).

[31] "Potential Hazards in Molten Salt Baths for Heat Treatment of Metals"

,

National Board Fire Underwriters Research Report No, 2 (1954),

[32] "Handbook of Reactive Chemical Hazards ", Bretherwick, L,,

Butterworths Co,, London (1975),

[33] Janz, G. J., Tomkins, R, P. T., Downey, J, R, , Jr., and Allen, C, B.,

"Safety and Hazards ", Chapter in "Eutectic Data", ERDA TID 271 63 -PI

NTIS, U. S. Dept. Commerce, Springfield, Va, (1977),

[34] Cable, M., and Martlew, D., Glass Technol , , 12 , 142 (1971).

[35] Schneider, Yu. G., Kondrat'ev, Yu. N., and Maksimov, N. N.

,

Zashch. Metal, 9, 199 (1973),

[36] Ozeryanaya, I. N. , Penyagina, 0. P., Manukhina, T. I., and

Smirnov, M. V., Fiz. Khim. Elektrokhim. Rasplav. Solei Tverd.

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[37] Sizintseva, N. F., Stepanov, G. K., and Belyaeva, G. I., Tr. Inst.

Elektrokhim., Ural. Nauch. Tsentr; Akad. Nauk, USSR, 1_9, 92 (1973).

[38] Janz, G. J., Conte, A., and Neuenschwander , E., Corrosion, 1_9, 292

(1963)

[39] Janz, G. J., and Conte, A., Corrosion, 2_0, 237 (1964).

[40] Rodigina, E. N., and Stepanov, G. K. , Trudy Inst. Elektrokhim. Ural.

Fil. Akad. Nauk, SSSR, 3, 77 (1962).

[41] Janz, G. J., and Lorenz, M. R. , Rev. Sci. Instruments, 32 , 130 (1961).

[42] Scheer, J. J. , van Arkel, A. E., and Heyding, R. D., Can. J. Chem.,

33, 683 (1955).

[43] Rol in

,

M., and Recapet, J. M. , Bull

Soc . Chim . Fr .

,

2110 (1964)

[44] Papin, G., Michaud , M.

,

and Bouaziz, R . , C . V . Acad

Sc . , Paris

,

268 ,

[45] Cohen-Adad, R., Michaud, M., Said, J., and Rollet, A. P.,

Bull. Soc. Chim. Fr., 356 (1961).

[46] Dubois, J., "Chemical and Electrochemical Reactions of Molten Alkali

Carbonates as Fuel Cell Electrolytes ", Ph.D. Thesis, Fac. Sci.

Univ. Paris, France (1964).

[47] Ingram, M. D., and Janz, G. J., Electrochim. Acta, 1_0, 783 (1965).

[48] Busson, N. , Palous, S., Buvet, R., and Millet, J., Compt. Rend,,

260 , 720, 6097 (1965).

[49]

Ingram, M. D., Baron, B. , and Janz, G. J. , Electrochim. Acta,

U, 1629 (1966).

121
Na2C0^

[50] Janz, G. J., J. Chem. Ed., 44_, 581 (1967).

V [51] Busson

,

N. , Palous, S. , Millet, J., and Buvet, R., Electrochim

Acta

,

12, 910 (1967).

[52] Janz, G . J. , and Tomkins, R. P. T.

,

Corrosion

,

34 (in press) , (1978)

[53] Maru, H. C., et al . (Institute of Gas Technology), "Molten Salt

Thermal Energy Storage Systems: Salt Selections", Rpt . COO-2888-1,

ERDA Contract No. E (11-1) -2888 ; NTIS, U. S, Dept. Commerce,

Springfield, Va. (Aug. 1976).

[54] Maru, H. C., et al. (Institute of Gas Technology) , "Fuel Cell Research

on Second Generation Molten Carbonate Systems: II, Characteristics

of Carbonate Melts", Quarterly Status Rpt., Project 8984, ERDA

Contract No. 31-109-38-3552, (Sept. 1976).

[55] Atomics International; "Development of a Molten Carbonate Process for

Removal of Sulfur Dioxide from Power Plant Stack Gases ", Progress

Rpt. No. 2, U. S. Public Health Services, Contract PH 86-67^128,

Canoga Park, Ca. (1968).

[56] Grahtham, L. F., and Ferry, R. B,, "Corrosion in Alkali Metal

Carbonate-Based Melts", Proc, International Symp . Fused Salts,

J. P. Pemsler, bd , , Electrochemical Soc . , Inc., Princeton,

N. J., 270 (1976).

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,

Proceedings of the 11th Intersociety Energy Conversion Engineering

Conference, 1_ , 280 (Sept, 1976).

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Va. (May 1977) .

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Coal Gasification Process ", Extended Abstracts, American Chemical

Soc. Meeting, Wasnington, D. C. (1971).

[60] Kochergin, V. P., and Ignat 'eva, N. I., Russ. J. Inorg. Chem., 6^, (9), 1086 (1961),

[61] Bonar. J. A., Clark, C. B., and Sandmeyer, K. H. . "Interaction of

Oxide Refractories with the Environment of High Temperature Rex- actors", p. 807, in Proceedings Int . Symposium in Metal-Slag Gas Reactions and Processes; Electrochem. Soc., Inc., Princeton, N. J. (1975).

[62] Spedding, P. L., and Mills, R. , J. Electrochem. Soc., 112, 594

(1965).

[63] Mills, R. , and Spedding, P. L., J. Phys. Chem., 7_0_, 4077 (1966).

[64] Djordjevic, J., and Hills, G. J., Trans. Faraday Soc., _56, 269 (1960).

[65] May, M., TAPPI, !V5, 511 (1952).

[66] Ginzburg, D. M. , Zhur. Obshchei Khim., 2_6, 968 (1956); Chem. Abs

(ACS) , 51, 1717c.

[67] vide infra Ref [11 ]

.

[68] Janz, G. J., et al . , (MSDC-RPI) unpublished work (1977).

[69] Janz, G. J., and Lorenz, M. R,, J. Chem. Eng. Data, £, 94 (1964).

122
Na

2 C0

3

[70] Johnston, J., Z. Phys . Chem. Stoichiometry and Verwandschaf f slehre

,

62_, 330 (1908).

[71] Howarth, J. T., and Turner, W. E. S., J. Soc. Glass Technology,

1_5 , 360 (1931); ibid., 14_, 394 (1930).

[72] Kroger, C., and Stratmann, J., Glastechn. Ber . , 3_4, 311 (1961).

[73] Broers, G. H. J., "High Temperature Galvanic Fuel Cells”, Ph.D.

Thesis; Univ. Amsterdam (1958).

[74] Broers, G. H. J., and Schenke, M "Long-Run Experiments on High

Temperature Molten Carbonate Fuel Cells”, Chapter in "Hydrocarbon

Fuel Cell Technology ", Baker, B. S., ed . , Academic Press, N. Y.

(1965)

[75] McQuade, J. M. , Hamlen, R. P., and Nelson, R. P., "Alkali Carbonate

Fuel Cell", U. S. Patent 3,268,365 (1966) Aug. 23; (assigned to

General Electric Co) .

[76] Trachtenberg, I., and Cole, D. F., " Electrolyte Studies in Molten

Carbonate Fuel Cells”, Chapter in "Fuel Cell Systems III", Baker,

B. S., ed . , Amer . Chem. Soc. Advances in Chemistry Series 90 , 268-280 (1969).

[77] Egorov, B. N. , and Revyakina, M. P. , Teplofiz. Vys. Temp., 8_, 1299 (1970).

[78] Egorov, B. N. , and Revyakina, M. P., High Temp., 8^, 1220 (1970).

[79] Janz, G. J., Neuenschwander , W. , and Kelly, F. J., Trans. Faraday

Soc., 5_9, 841 (1963); see also Janz, G. J. and Lorenz, M. R. , J. Chem. Eng. Data, 6_, 321 (1961).

123
XI I. Potassium Carbonate: K^CO^ 1.

Melting Temperature (T ) Melting point:

898° + 3 °C [1-3,9]

References [1-14].

2.

Density (p)

Measurement method: Archimedean technique [6]

p = 2.4141 - 4.421 x 10' 4 T (12.1)

precision: ^ + 0.71 uncertainty: ^ + 1%

Table 12.1. Densities from equation (12.1)

T(K)

P (g cm -3

)

T(K)

P_

(g cm 3

) 1180 1.8924 1230 1.8703

1190 1.8880 1240 1.8659

1200 1.8836 1250 1.8615

1210 1.8792 1260 1.8571

1220 1 .8747 1270 1.8526

1280 1.8482

References [6,15] .

3.

Surface Tension (y)

Measurement method: pin detachment [6]

Y

= 337.85 - 21.71 x 10

_2

T + 6.25 x 10" 5 T

2 (12.2)

precision : + 0.1% uncertainty: ^ + 0.3%

Table 12.2. Surface tension from equation (12.2)

T(K)

Y (dyn cm *) T(K)

Y

-i (dyn cm 1 )

1190 168.0 1240 164.7

1200 167 .

1250 164.1

1210 166.7 1260 163.5

1220 166.0 1270 162.9

1230 165.4 1280 162.4

References [ 6 ]

4 . Viscosity ( n

)

Measurement method: oscillating (liquid-filled) cylinder [16]

n = 1.161 x 10" 5 exp (29,487/RT) (12.3)

precision: ^ + 1.23% uncertainty: ^ + 30%

For numerical values: see table 12.3

124
K

2 co3

Table 12.3. Viscosity from equation (12.3)

T(K)

n (cp )

1190 3.02

1200 2.72

1210 2.46

1220 2.22

1230 2.01

1240 1 .83

1250 1 .66

References [16,17].

5. Electrical Conductance ( <

)

Measurement method: ac technique

k = 11,027 exp

precision: + 0. 081

[ 6 ] (-3941/RT) (12.4)

uncertainty: ^ + 1.5%

Table 12.4, Electrical conductance from equation (12.4)

T(K)

K (ohm 1 cm 1 )T(K)K (ohm 1 cm 1 ) 1180 2 . 053 1240 2.227

1190 2.083 1250 2 .256

1200 2 .112 1260 2 . 285

1210 2 . 141 1270 2.313

1220 2.170 1280 2.342

1230 2.199

References [6,10,18-22].

6. Safety and Hazards

A. Hazard rating [23-25]

(i) Severe

(ii) Vapor pressure: [ CO 7 equilibrium dissociation pressure

is ^ 1 mm at approx .1 08 0 °C

]

K

2 C03 K

2 0 + C02 (12.5)

B. Disaster hazards [26-28]

(i) Molten salt bath "explosions": i.e. explosive generation

of steam due to bulk water "carry-over" and/or equipment

failure; i.e., explosive expansion of "trapped" air.

(ii) When heated with CO 2 pressures less than equilibrium dissociation pressures, decomposes to form alkali metal oxide;

the toxicology and disaster hazards are the same as those

of very caustic solutions, i.e. react with water or steam

(exothermic) to form solutions that are markedly aggressive

to all body tissues (chemical burns) . Potassium carbonate

itself is classified as a strong caustic.

. 125
References [23-28].

K

2 C03

7.

Corrosion

Table 12.5. Corrosion studies from primary research literature

Studies

SS

(K, Mg / CO 3 ) (K 2 C0 3 , KC1, KF)

(K/CO , F, Cl)

3 Acid-base relationships in

molten carbonates

Hydrolysis (H 2 0) reactions

Corrosion in molten salts:

annotated bibliography

Molten carbonates: fuel

cells; thermal energy

storage; coal gasification

power plant stack gases

Ref erences

29

30-33

34-36

37

29,38-42

References [29- 42],

8. Diffusion

No diffusion studies reported ,

9. Heat of Fusion

Measurement method: drop calorimetry [2,3]

Table 12.6. Heat of fusion

AH°

1 -i (kcal mol ) Uncertainty

6.6 a, ± 1.0%

References [2,3,43].

10. Heat Capacity (C )

Measurement method: drop calorimetry [3]

C

p

= 36.95 + 10.64 x 10" 3 T (12,61

precision: ^ + 0.5% uncertainty: + 0.5%

For numerical values: see table 12.7

126
K

2 C03

Table 12.7. Heat capacity from equation (12.6)

T(K)

C

P . . (cal K

_1 mol 1 )

T(K)

C

P (cal K

-1 mol -1

) 1170 49.40 1210 49 . 82

1180 49.51 1220 49.93

1190 49.61 1230 50.04

1200 49.72 1240 50.14

1250 50.25

References 12,3,43],

11. Volume Change on Melting CtVj.1

Measurement method: estimated; from densities [44]

Table 12.8. Volume change on melting

< 4 VV Uncertainty

16.4% A ± 8%

References [44] .

12. Vapor r Pressure (pr ) uap

Measurement method: cited with each data set [36,38,45].

No systematic studies of vaporization as "molecular carbonate" have

been reported, viz:

K

2 C0

3(£)

K

2 C0

3(g)

( 12,7 )

Relative to the decomposition of molten carbonates and other possible

processes contributing to vaporization, the data for K^CO,. are as follows.

Decomposition processes:

CC>2 dissociation and equilibrium pressures for molten

K

2 C0

3 (a)

pco

2 K

d

K 2°U)

+ C0

2(g)

(12 ' 8 ^

a K

2 C03 (Jl)/ a K

2 0(Jl) (12.9)

Here p is the equilibrium dissociation pressure, and a the thermodynamically

defined activity. For practical purposes, eq.(12.9)Ts expressed in the mol

fraction scale [X] as:

' K

2 C0

3(V

K 2° (£)

( 12 . 10 )

It is clear that the values of p^Q , thus, depend on the quality of the

"carbonate", i.e. the oxide content as well as carbonate. The p^ equilibrium values will be unique only if the composition of the "carbonate"

is exactly defined, e.g., mols K 2 0/mol K 2 CO 3 ,

127
K

2 C0

3

In the vacuum drying of carbonates, where the sample is heated under

dynamic vacuum, the oxide content may be increased through this thermal

dissociation if the pressures are less than the C0 2 equilibrium pressures.

(i) Equilibrium dissociation constant,

Measurement method: emf technique [36]

log K

d

=

" 17

d

- 5-° +7.44 (12.11)

precision: not estimated uncertainty: 'v- + 1 %

Table 12.9.1. C0

2 dissociation constant from equation (12.11)

T(K)

K

d

(atm)

T(K)

K

d

(atm)

(800) (1.34 x 10~ 15

) (1050) (2.75 x 10" 10

) (850) (2.75 x 10" 14

) (1100) (1.63 x 10~ 9

) (900) (4.04 x 10~ 13

) (1150) (8.28 x 10 -9

) (950) (4.47 x 10" 12

) 1200 3.67 x 10" 8 (1000) (3.89 x 10" 11

) -

(ii) Equilibrium C0

2 dissociation pressures

Measurement method: Knudsen effusion technique [45]

log p (mm) = -10838. 67 + g < 63 (12.12)

precision: ^ ± 0.2% uncertainty: ^ + 5%

Table 12.9.2. Equilibrium CC> 2 dissociation pressures of K^COjU)

from equation ( 12 . 12 )

T (K)

p (mm) T(K)

p (mm)

obsv’d calc’d obs v ’

d

calc’d

1170 0.23 0.17 1200 0.39 0.40

1180 0.28 0.22 1210 0.47 0.53

1190 0.33 0 . 30

The p(mm) (calc’d) were calculated from the data in table 12.9.1 and

eq. (12.10), and assuming K 2 0 content, 7 x 10

~ 5 mol/mol K 2 CO 3 , eq. (12,12)

Additional thermal dissociation data (anhydrous K 2 CO 3 to C0 2 ) have been

reported by Lebeau (1905) , Howarth and Turner (1930) , and Dubois and

Millet (1968). The CO 2 pressures can be brought into accord if corrections

for the oxide content is made. From the preceding, these are, respectively

^ 8 x 10 ~ 6

, ^ 6 x 10 ~ 3, and ^ 2 x 10 " 3

. Vaporization of molten carbonates:

Measurement method: critical analysis [38]

128
K

2 co

3 The various "vaporization" observations, based on electrolyte losses

from high temperature molten carbonate fuel cells, and the thermodynamics of the associated reactions, have been critically examined

by Maru et al. (1976). For a summary of the results, refer: L^CO^,

present work.

References [36,38,45-52],

13. Thermal Conductivity (liquid) ( A

^

J

No thermal conductivity studies reported.

14. Thermal Conductivity (solid) (A ) ° s No thermal conductivity studies reported.

15. Cryoscopic Constant

Measurement method: calculated from AH£ [44]

Table 12.10. Cryoscopic constant

k

f Uncertainty

-1 -1,

(K mol kg )

57 .

i

—

a +i

References [2,44,53] .

16. References

[1] Reisman, A., J. Amer . Chem. Soc., 8_0, 3558 (1958),

[2] Rolin, M., and Recapet, J. M., Bull Soc, Chim. France, 2104 (1964),

[3] Janz, G. J., Neuenschwander , E., and Kelly, F. J., Trans. Faraday

Soc. , 59, 841 (1963)

[4] Rossini, F. D., Wagman, D. D., Evans, W. H,, Levine, S., and Jaffe,

I., "Selected Values of Chemi-cal Thermodynamic Properties , NBS

Circ. 500", U, S, Gov T t Printing Office ; Washington, D. C, 0,9521,

[5] Stern, K., "High Temperature Properties and Decomposition of Inorganic Compounds. II. Carbonates", NSRDS-NBS- 30 ; U. S,

Gov’t Printing Office, Washington, D. C. (1969).

[6] Janz, G. J., and Lorenz, M. R. , J. Electrochem. Soc., 108 , 1052 (1961).

[7] Braun, F., Pogg . Ann., 1 54 , 190 (1875),

[8] Carnelley, N. , J. Chem. Soc,, 489 (1876); ibid., 281 (1878).

[9] Stull, D, R. , and Prophet, H, (eds.) "JANAF Thermochemical Tables ",

2nd Ed., NSRDS-NBS 37, U, S. Gov’t Printing Office, Washington,

D. C. (1971)

[10] Arndt, K. , Z. Elektrochem. , 1_2 , 337 (1906),

[11] Hiittner, L., and Tammen, G,, Z. anorg . Chem,, 4_3 , 215 (1905),

[12] Sackur, 0,, Z. Elektrochem., 16^, 649 (1910),

[13] Belyaev, I, N., and Sholokovich, M. L., J. Appl . Chem, USSR, 2

5

, 733 (1952).

[14] Markov, S. Z., and Shulgina, M. P., Proc. Acad. Sci. USSR, Div. Chem.,

5_, 69 (1940).

129
[15] Brunner , E .

,

Z. Angew. Chem., 38_, 350 (1906) .

[16] Jsn z j G

and Saegusa , F . , J. Electrochem. Soc., 110, 452 (1963)

[17] Vorobev, G. v., Pal'guev, S. F . , and Karpachev, S. V. , Trudy No. 6 (1965); Inst. Electrochem. Urals. Acad. Sci., Eng. Trans.

Electrochem. Solid and Liq. Electrolytes, 3^ 33 (1966). Consultants

Bureau, New York (1966).

[18] Ward, A. T., and Janz, G. J., Electrochim. Acta, 1_0, 849 (1965).

[19] Vide infra ref. [7] .

[20] Spedding, P. L., J. Electrochem. Soc., 120 , 1049 (1973).

[21] Ryschkewitsch , E., Z. Elektrochem . , 3_9 , 531 (1933).

[22] Vorobev, G. V., Karpachev, S. V. , and Pal'guev, S. F., Izv. Sekt. Fiz.

Khim. Anal. Obshch. Neorg. Khim. Akad. Nauk SSSR 2_6, 164 (1955).

[23] "Dangerous Properties of Materials ", Sax, N. I., Van Nostrand

Reinhold Co . , N. Y. (1969) .

[24] Registry of Toxic Effects of Chemical Substances"

,

Christensen,

H. E., and Lubinbyhl, T. T., eds . , U. S. Dept. H.E.W., U. S.

Gov't Printing Office, Washington, D. C. (1975).

[25] Vapor pressure, calculated (see p. 128, this work)

[26] "Potential Hazards in Molten Salt Baths for Heat Treatment of Metals"

,

National Board Fire Underwriters Research Report No. 2 (1954).

[27] "Handbook of Reactive Chemical Hazards", Bretherwick, L.,

Butterworths Co., London (1975).

[28] Janz, G. J., Tomkins, R. P. T.*, Downey, J. R. , Jr., and Allen, C. B.,

" Safety and Hazards ", ChapteP in' "Eutectic Data", ERDA TID- 271 63 -PI

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[29] Maru, H. C, , et al . (Institute of Gas Technology), "Molten Salt Thermal

Energy Storage Systems: Salt Selection ", Rpt . COO- 2888 -1 , ERDA

Contract No. E (11 -1 ) - 28 88 ; NTIS, U. S. Dept. Commerce, Springfield,

Va. (Aug. 1976).

[30] Dubois, J., "Chemical and Electrochemical Reactions of Molten Alkali

Carbonates as Fuel Cell Electrolytes"

,

Ph.D. Thesis, Fac. Sci.

Univ. Paris, France (1964).

[31] Ingram, M. D., and Janz, G. J., Electrochim. Acta, 10_, 783 (1965).

[32] Busson, N., Palous, S., Buvet, R., and Millet, J. , Compt. Rend.,

260 , 720, 6097 (1965).

[33] Ingram, M. D., Baron, B. , and Janz, G. J., Electrochim. Acta, 11 , 1629 (1966).

[34] Janz, G. J. , J. Chem. Ed., 44, 581 (1967).

[35] Busson, N., Palous, S., Millet, J., and Buvet, R. , Electrochim.

Acta, 1_2 , 910 (1967).

[36] Andersen, B. K. , "Thermodynamic Properties of Molten Alkali

Carbonates", Ph.D. Thesis, Tech. Univ. Denmark (1975).

[37] Janz, G. J., and Tomkins, R. P. T., Corrosion, ^4 (in press) (1978).

130
[38]

k

2 co

3

Maru, H. C., et al . (Institute of Gas Technology), "Fuel Cell

Research on Second Generation Molten Carbonate Systems: II.

Characteristics of Carbonate Melts ", Quarterly Status Rpt.,

Project 8984, ERDA Contract No. 31-109-38-3552 (Sept. 1976).

[39] Botts, W. V., Kohl, A. L., and Trilling, C. A., "Low BTU Gasification

of Coal by Atomics International’s Molten Salt Process", "Proceedings of the llth Intersociety Energy Conversion Engineering

Conference" 280 (Sept. 1976).

[40] Cover, A. E., Schreiner, W. C., and Skaperdas, G. T., "The Kellogg

Coal Gasification Process ", Extended Abstracts, American Chemical

Soc. Meeting, Washington, D. C. (1971).

[41] Atomics International, "Development of a Molten Carbonate Process for

Removal of Sulfur Dioxide from Power Plant Stack Gases ", Progress

Rpt. No. 2, U. S. Public Health Services, Contract PH 86-67-128,

Canoga Park,. Ca. (1968).

[42] Grantham, L. F., and Ferry, R. B., "Corrosion in Alkali Metal Carbonate - Based Melts", Proc. International Symp . Fused Salts;

J. P. Pemsler, Ed., Electrochemical Soc., Inc., Princeton, N. J.

,

270 (1976).

[43] Vide infra ref. [9] ,

[44] Janz, G. J., et al , , (MSDC-RPI) unpublished work (1977).

[45] Kroger, C., and Stratmann, J., Glastechn. Ber . , 34_, 311 (1961).

[46] Lebeau, P., Annal de Chimie et de Physique, (5 , 422 (1905).

[47] Howarth, J. T., and Turner, W. E. S., J, Soc. Glass Technology, 1

5

, 360 (1931); ibid., 14_, 394 (1930).

[48] Dubois, J., and Millet, J. , Compt. Rend., 266C , 852 (1968).

[49] Broers, G, H. J., "High Temperature Galvanic Fuel Cells", Ph.D.

Thesis, Univ. Amsterdam (1958),

[50] Broers, G. H. J, , and Schenke, M. , "Long-Run Experiments on High

Temperature Molten Carbonate Fuel Cells", Chapter in Hydrocarbon

Fuel Cell Technology ", Baker, B. S., ed . , Academic Press, N. Y,

(1965) .

[51] McQuade, J. M. , Hamlen, R. P., and Nelson, R. P., "Alkali Carbonate Fuel Cell", U. S. Patent 3,268,365 (1966) Aug. 23,

(assigned to General Electric Co) .

[52] Trachtenberg, I., and Cole, D. F., "Electrolyte Studies in Molten

Carbonate Fuel Cells", Chapter in "Fuel Cell Systems III", Baker,

B. S., ed., Amer, Chem. Soc. Advances in Chemistry Series 90 , 268-280 (1969).

[53] Janz, G. J., Neuenschwander , E., and Kelly, F. J, , Trans. Faraday

Soc., 5_9, 841 (1963); see also Janz, G. J, and Lorenz, M. R. , J. Chem. Eng. Data, 6, 321 (1961).

131
XIII. Lithium Nitrate: LiNO^

1. Melting Temperature (T ) Melting point:

253° + 2 °C [5-7,12]

References [1-12] .

2. Density (p)

Measurement method: Archimedean technique [13]

p = 2.070 - 5.49 x 10" 4 T (13.1)

precision: ^ + 0.051 uncertainty: % + 1%

Table 13.1. Densities from equation (13,1)

T(K)

P , (g cm d

)

T(K)

P (g cm

-3

)

550 1.767 630 1.724

560 1 . 762 640 1 .718

570 1.757 650 1 .713

580 1.751 660 1.707

590 1 . 745 670 1 . 702

600 1 .740 680 1 .696

610 1.735 690 1 .691

620 1.729

References [13-16].

5. Surface Tension (y)

Measurement method: plate detachment [17]

y

= 144.92 - 5,50 x 10

_2

T (13.2)

precision: + 0.5% uncertainty: ^ +

Table 13,2. Surface tension from equation

1 %

(13.2)

T(K)

X (dyn cm x )

T(K)

X (dyn cm x )

570 113.6 680 107.5

580 113.0 690 107.0

590 112.5 700 106.4

600 111.9 710 105.9

610 111.4 720 105.3

620 100.8 730 104.8

630 110.3 740 104.2

640 109.7 750 103.7

650 109.2 760 103.1

660 108.6 770 102.6

670 108.1 780 102.0

References [17-19].

132
LiN0

3

4 . Viscosity fn)

Measurement method: capillary [9]

n = 70.567 - 20.188 x 10

_2

T + 14.976 x 10~ 5 T

2 (13.3)

precision: v + 1.1% uncertainty: ^ + 2%

Table 13,3. Viscosity from equation (13.3)

T(K)

n(cp

)

T(K)

0(cp

)

540 5.222 600 3.352

550 4 .835 610 3 . 146

560 4.479 620 2 .969

570 4.152 630 2.822

580 3.856 640 2 .705

590 3.589 650 2 .619

References [9,11,20-22].

5. Electrical Conductance (k)

Measurement method: dc technique [16]

k = -1.5242 + 3.4674 x 10" 3 T + 1.8027 x 10~ 6 T

2 (13.4)

precision: + 0.6% uncertainty: ^ + 1.5%

Table 13.4. Electrical conductance from equation (13.4)

T K T K (K) (ohm 1 cm 1

) (K) (ohm 1 cm 1 ) 550 0.928 600 1.205

560 0 . 983 610 1.262

570 1.038 620 1 .318

580 1.093 630 1.376

590 1.149 640 1.433

References [13,15,16,23,24].

6. Safety and Hazards

A. Hazard rating [4,25,26]

(i) Inhalation: low; ingestion: moderate (toxicity)

(ii) Vapor pressure: LiNO^ decomposes just above its

m.pt. (253°C) to LiN02 and oxygen. If the container

material is inert (glass is not) , oxides of nitrogen

are absent.

B. Disaster hazards [27-29]

(i) Molten salt bath "explosions": i.e. explosive generation

of steam due to bulk water "carry-over" and/or equipment failure; i.e., explosive expansion of "trapped"

air

(ii) On decomposition, nitrates emit toxic fumes (oxides

of nitrogen) viz:

133
LiN0

3

MN0

3 —v MN02 + HO

2 (13.5.1)

2MN0

2 M

2 0 + NO + N0

2 (13.5,2)

The subsequent decomposition reactions are complex; if the gas phase

is continuously removed, the nitrite decomposition (above) to NO and

NO 2 is dominant. If the gas phase is not immediately removed, the NO

may re-oxidize the nitrite to nitrate.

(iii) Nitrates are powerful oxidizing agents; violent (explosive)

reactions possible in molten nitrates and carbonaceous

materials (organic cpds oils; carbon;...); aluminum alloys

and bath sludges (e.g. iron oxides); magnesium alloys.

Dangerous

References [4,25-29]

Corrosion

Table 13.5. Corrosion studies from primary research literature

Studies Ref er enc e s

Fe 30

Cu 31

Thermodynamic approach 32,33

Electrochemical approach 34,35

Annotated corrosion biblio. 36

Reviews/ corrosion 37-39

References [30-39] .

Diffusion

Measurement method: cited in tabulations

List of diffusing species investigated in LiN0

3 as solvent.

Li

+

, N0

3

, Na

+

, K

+

, Rb

+

, Cs

+

, Tl

+

, Ag

+

, Br'.

precision: in table 13,6,2 uncertainty: in table 13,6,1

Table 13.6.1. Diffusion techniques, uncertainties, and species

Diffusion technique Uncertainty

of recommended study (in values of D) Spec ies

capillary ^ + 5% L

+

, NO 3 chronopotentiometry ^ ± 10 % Ag+

electrophoresis

interferometry

~ ± 20 % ^ + 20 %

Na+,Cs+ , K+,Rb+,Tl , Br

~

Equation

D - A exp [ -E/RT] (13.6)
LiN0

3

Table 13.6.2. Parameters of diffusion equation (13.6), precisions,

and recommended study

Species A x 10 3

( cm 2 sec

-

] )

E (cal mo 1

”

1 )

Temp, range

(K)

Precision Recommended

study

Li + 2.47 5490 540-590 *±1 .7% 40

NO 3 1. 95 6340 540-590 *±3.3% 40

Na

+ 0.43 3550 540-670 41

K+ 2.33 5776 540-615 *±11 % 45

Rb + 0.87 4898 545-665 *±3.6% 45

Cs + 0.66 4540 540-675 41

Tl +

3 . 95 6780 535-630 *±7.8 % 43

Ag

+ 16.1 7900 530-590 *±4.5% 46

Br" 1 . 58 6290 530-625 *±10 % 47

No entry in precision column indicates estimates not possible since

results were reported as equations only.

References Li

+

, 40; NO^ , 40; Na

+

, 41,45; K

+

, 45; Rb

+

, 45

Tl

+

, 43; Ag

+

, 42,44,46; Br", 47.

Cs

+

, 41,45;

Table 13.6.3. Self -diffusion coefficients

T D t .+ x 10 5 Li T DNOi * 105

(K) (cm 2 sec

- 1 ) (cm 2 sec

-1

)

540 1.48 0.53

550 1 . 63 0.59

560 1 .78 0.65

570 1 . 94 0.72

580 2.11 0.80

590 2.29 0.87

135
LiN0

3 Table 13.6.4. Diffusion coefficients,

? -

* D x 10 5 (cm sec )

T(K) Na +

K+ Rb + Cs

+

Tl + Ag

+

Br

530 0.63 0.89 0.40

540 1.57 1.07 0.91 0.96 0.71 1 . 02 0.45

560 1.77 1.30 1 . 07 1 .12 0.89 1.33 6.55

580 1 . 98 1 .55 1.24 1 . 28 1.10 1.70 0.67

590 2 . 08 1 .69 1.33 1.37 1 . 22 1 . 91 0.74

600 2.19 1.83 1.43 1.47 1.34 0.81

610 2.30 1 .99 1 .53 1 .56 1.47 0.88

620 2.41 2 . 14 1 . 63 1 . 66 1 . 61 0.96

630 2 .52 1.74 1.76 1.76 1 . 04

650 2.75 1 . 96 1 . 96

660 2.87 2 . 08 2 . 07

670 2.99 2 .20 2.18

680 2.29

9.

Heat of Fusion (&H°)

Measurement method: reaction calorimetry [48]

Table 13.7. Heat of fusion

AH°

f Uncertainty

(kcal mol )

5 .96 ^ ± 1.5%

References [5,8,48,49].

10.

Heat Capacity (C

Measurement method: drop calorimetry [50]

Table 13.8. Heat capacity

C (cal K mol )

Temp . range

(K)

Uncertainty

26 .^ 540-670 'v ± 2%

References [8,50] .

11.

Volume Change on Melting

Measurement method: capillary technique [51]

Table 13.9. Volume change on melting

( A V / V ) r s Uncertainty

21.4% ^ ± 3%

References [51,52].

136
LiN0

3

12. Vapor r Pressure ( p ) *yap

Measurement method: critical analysis (NSRDS study) [4]

LiN0

3 is unstable just above its m.pt. (250°C) viz:

LiN0

3

> LiN0

2 + hO? .(13.7)

Onset of this decomposition at approx. 290°C has been reported. Thermodynamically it is predicted that the decomposition to oxide and N0

2

, viz:

2 LiN0

3

> Li

2 0 + 2N0

2 + hO2 (13.8)

is negligible to approx. 327°C.

LiN0

2 is stable jap to 300°C, and slow decomposition at 'v 350°C has

been noted, i.e.

2 LiNO

2 —* Li

2 0 + NO + N0

2 (13.9)

The product gases, NO and N0

2

, may re-oxidize the nitrite to LiN0

3 if not removed.

The "equilibrium pressures" thus reported for molten LiNO-j by Centnerzwer

and Blumenthal (1936) apply to "infinitely dilute" solutions of LiN0

2 in the melts.

References [4,53-55],

13. Thermal Conductivity ( liquid ) Ck.)

& Measurement method: concentric cylinder [60]

X = 11.935 x 10' 4

+ 5.00 x 10" 7 T (13.10)

precision: not estimated uncertainty: ^ + 20%

Results were reported in equation form only.

Table 13,10, Thermal conductivity of melt from equation (13.10)

T(K)

X x 10 4 (cal cm -

sec -

K

_1

)

T(K)

X x 10 4 (cal cm -

sec -

K

-i

)

530 14 .59 640 15.14

540 14 . 64 650 15.19

550 14 .69 660 15 . 24

560 14.74 670 15.29

570 14.79 680 15.34

580 14 .84 690 15.39

590 14.89 700 15.44

600 14 . 94 710 15.49

610 14 . 99 720 15.54

620 15.04 730 15 ,59

630 15 .09

References [56-61].

137
LiNO

14.

Thermal Conductivity (solid) (X ) s Measurement method: comparative, flat slab [62]

precision: not estimated uncertainty: ^ + 10%

Table 13.11, Thermal conductivity of solid

T A x 1

4 (K) (cal cm

-1 sec

-1 K~ 1

)

525 32 .

527 32.7

References [56,62],

15.

Cryoscopic Constant

Measurement method: calculated from AH£ [63]

Table 13.12. Cryoscopic constant

k

f (K mo 1 “ ^ kg

-

1

)

Uncertainty

6 . 36 ^ ± 1.5%

References [8,63-68].

16.

References

[1] Dworkin , A. S., and Bredig, M. A., J. Phys. Chem., 67_, 697 (1963).

[2] Franzosini, P., and Sinistri, C., Ric . Sci, Part 2, A3_, 411

(1973)

[3] Rossini, F. D., Wagman, D. D., Evans, W. H. , Levine, S.,and Jaffe

1., "Selected Values of Chemical Thermodynamic Properties, NBS

Circ. 500 ", U. S. Gov’t Printing Office, Washington, D. C. (1952)

[4] Stern, K, , nHigh Temperature Properties and decomposition of In - organic Salts, III. Nitrates and Nitrites"

,

J. Phys, Chem. Ref

Data, 1, 747-772 (1972).

[5] Schiirmann, E., and Nedeljkovic, Lj .

,

Ber . Bunsenges. Physik, Chem.

74., 462 (1970).

[6] Doucet, Y., and Vallet, C., Compt . Rend. Acad. Sci. (Paris), 259 , 1517 (1964).

[7] Riccardi, R. , and Sinistri C., Ric. Sci. Rend. Ser . A, 8_, 1026

(1965)

[8] Franzosini, P., and Sinistri, C., Ric. Sci. Rend. Ser. A, 3_, 411 (1963).

[9] Janz, G. J., Lurie, S., and Gardner, G. L., J. Chem. Eng. Data,

23, 14 (1978).

[10] Brillant, S., Ph.D. Thesis, Univ. Strasbourg, Fr . (1967); J. Chim.

Phys. , 6_5 , 2138 (1968) .

[11] Murgulescu, I. G., and Zuca, S., Electrochim. Acta, 1^, 1383

(1966) .

[12] Kelley, K. K. , U. S. Bureau Mines, Bull. 584 (1960).

138
LiN0

3

[13]

[14]

[15]

[16]

[17]

[18]

[19]

[ 20 ]

[ 21 ]

[ 22 ]

[23]

[24]

[25]

[26]

[27]

[28]

[29]

[30]

[31]

[32]

[33]

[34]

[35]

Jaeger, F. M. , and Kapma, B., Z. anorg. Chem., 1 13 , 27 (1920).

Smith, G. P., and Petersen, G. F., J. Chem. and Eng. Data, 6_, 493 (1961).

Ketelaar, J. A. A., and De Nooyer, B., Koninkl. Nederl. Akad

Wetensch. , Proc . Ser. B, 7_5, 97 (1972).

King, L. A., and Duke, F. R., J. Electrochem. Soc., Ill, 712

(1964) . Bertozzi, G., and Sternheim, G., J. Phys . Chem., 6_8 , 2908 (1964).

Addison, C. C., and Coldrey, J. M., J. Chem. Soc., 468 (1961).

Jaeger, F. M. , Z. anorg. allgm. Chem., 101 , 1 (1917).

Goodwin, H

2_5 , 469

. M. , and Mailey, R. D., Phys.

(1907); 26, 28 (1908).

Rev. , 23, 22 (1906)

Dantuma, R . S. , Z. anorg. Chem., 175, 1 (1928)

Prot senko

,

38_, 2355

P. I., and Razumovskaya , 0. N

(1965)

. , Zh. Prikl. Khim .

,

Doucet, Y.

(1959) .

, and Bizouard, M. , Bull. Soc. Chim

France

,

1570

Buckle, E.

60, 2144

R. , and Tsaoussoglou , P. E.,

(1964) . Trans

Faraday Soc . ,

"Dangerous Properties of Materials", Sax, N. I., Van Nostrand

Reinhold Co. , N. Y. (1969)

"Registry of Toxic Effects of Chemical Substances", Christensen,

H. E., and Lubinbyhl, T. T., eds., U. S. Dept. H.E.W; U. S. Gov’t

Printing Office, Washington, D. C. (1975).

"Potential Hazards in Molten Salt Baths for Heat Treatment of

Metals ", National Board Fire Underwriters Research Report No. 2 (1954)

"Handbook of Reactive Chemical Hazards" Bretherwick, L., Butterworths

Co., London (1975).

Janz.! G. J. , Tomkins, R. P. T., Downey, J. R., Jr., and Allen, C. B.,

"Safety and Hazards", Chapter in "Eutectic Data", ERDA TID-27163 PI;

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

Arvia, A. J., Podesta, J. J.,

Acta, 17, 33 (1972)

Notoya, T., Denki Kagaku, 41 , Conte, A., and Ingram, M. D.,

Bartlett, H. E., and Johnson,

(1966)

and Piatti, R. C. V., Electrochim.

779 (1973).

Electrochimica Acta, 13 , 1551 (1968).

K, E., Canad. J. Chem., £4, 2119

Pizzini, S., "Materials Problems in the Industrial Applications of

Molten Salts", Proceedings of the European Conference on the

Development of Molten Salts Applications, p. 203 (1973).

Battelle, Geneva.

Johnson, K. E., "Electrochemical Approaches to Corrosion in Molten

Salts", Proceedings International Symposium on Metal -Slag -Gas

Reactions and Processes, The Electrochemical Society, Inc.,

Princeton, N. J., p. 581 (1975).

139
LiN0

3

[36] Janz, G. J., and Tomkins, R. P. T. , Corrosion, 34, (in press)

(1978) .

[37] Inman, D., and Wrench, N. S. , Brit. Corr . J. , 1_ , 246 (1966).

[38] Ketelaar, J. A. A., Chemie Ing. Techn. , 4_5, 667 (1973).

[39] Smirnov, M. V., and Ozeryanaya, I. N., Nauki . Tech. Korros. Zashch.

Korros., 2_, 171 (1973).

[40] Dworkin, A. S., Escue, R. B., and van Artsdalen , E. R., J. Phys. Chem.

,

64, 872 (1960).

[41] Kwak, J. C. T., and Ketelaar, J. A. A., J. Phys. Chem., 7_3 , 94 (1969).

[42] Sjoblom, C. A., and Behn, A., Z. Naturforsch. , 23A , 1774 (1968).

[43] Okada, I., and Gustafsson, S. E., Electrochim. Acta, 18_, 275 (1973).

[44] Mazzocchin, G. A., and Schiavon, G., J. Electroanal. Chem., 38, 229

(1972) .

[45] Arvidsson, T. E. G., Afsenius, S. A., and Gustafsson, S. E., J. Chem.

Phys. , 53_, 2621 (1970) .

[46] Sternberg, S. , and Herdlicka, C., Rev. Chim. (Roumaine), 1_4, 991

(1969)

[47] Arvidsson, T. E. G., Afsenius, S. A., and Gustafsson, S. E., Z.

Naturforsch., 26A, 752 (1971).

[48] Kleppa, 0. J., and McCarty, F. G., J. Chem. Eng. Data, 8_, 331 (1963).

[49] Goodwin, H. M., and Kalmus, H. T. , Phys. Rev., 28, 1 (1909); see also

Ref. [3]

[50] Douglas, T. B. , Brookhaven National Laboratory, Report No. BNL-2446

(1954); Trans. Amer . Soc . Mech. Eng., 7_9, 23 (1957).

[51] Schinke, H. , and Sauerwald, F., Z. anorg . allgm. Chem., 304, 25 (1960);

ibid., 2_8_4 , 131 (1956); ibid., 287_, 313 (1956).

[52] Shimoji, M. , Disc. Faraday Soc., 3_2_, 128 (1961).

[53] Bordyushkova , E. A., Protsenko, P. I., and Venerovskaya , L. N.

,

J. Appl . Chem., USSR, 40^, 1386 (1967).

[54] Centnerzwer, M. , and Blumenthal, L., Bull. Internat. Acad. Polon.

Sci . , A, 470 (1936)

[55] Protsenko, P. I., and Bordyushkova, E. A., Russ. J. Inorg. Chem.,

10, 657 (1965).

[56] Turnbull, A. G., Ph.D. Thesis, Imperial College of Science and

Technology, London, 1959.

[57] Gustafsson, S. E., Hailing, N. , and Kjellander, R.A.E., Z. Naturforsch., 23a , 682 (1968).

[58] Jamieson, D. T. , Irving, J. B., and Tudhope, J. S., "Liquid Thermal

Conductivity ", HMSO, Edinburgh, 1975.

[59] White, L. R. , and Davis, H. T. , J. Chem. Phys., 47, 5433 (1967).

[60] McDonald, J., and Davis, H. T., J. Phys. Chem., 7_4, 725 (1970).

[61] McDonald, J., Ph.D. Thesis, University of Minnesota, 1969.

140
LiN0

3

[62] Tye, R. P., Bourne, J. G., and Disjerlais, A, 0., "'Thermal Energy

Storage Material Thermophy steal Property Measurement and Heat

Transfer Impact", ERDA-TES Program, Contract NAS-3-19716, Dynatech

R/D (1976).

[63] Janz, G. J. , et al . , (MSDC-RPI) unpublished work (1977),

[64] Doucet, Y., and Bizouard, M, , Compt, Rend,, 242 , 2137 [1956),

[65] Doucet, Y. , Proc. 6th Int . Mtg . Intern, Comm. Electrochem, Thermodyn,

Kinet., p. 492 (1955).

[66] Harkins, W. D., and Clark, G. L., J. Amer. Chem, Soc,, 37_, 1816 (1915),

[67] Holmes, E. 0., O'Connell, E., and Hankard , F., J, Amer. Chem. Soc.,

7_3 , 2885 (1951).

[68] Sinistri, C., and Franzosini, P., Ric, Sci,, A3, 419 (1963),

141
NaN0

3

XIV, Sodium Nitrate: NaNO,

1. Melting Temperature (T ) Melting point:

307° + 1°C [1,9]

References [1-12] .

2. Density (p)

Measurement method: Archimedean technique [13]

p = 2.3339 - 7.665 x 10

_4

T (14.1)

precision: ^ 0.1% uncertainty: ^ + 1%

Table 14.1. Densities from equation (14.1)

T(K)

P (g cm 3

)

T(K)

P (g cm-3

) 590 1.882 640 1.843

600 1.874 650 1.836

610 1.866 660 1 .828

620 1 .859 670 1 .820

630 1.851 680 1.813

690 1 . 805

References [13-27].

3.

Surface Tension (yl

Measurement method: maximum bubble pressure [28]

Y

= 155.4 - 6.13 x 10" 2 T (14.2)

precision: + 0.3% uncertainty: ^ + 0,5%

Table 14,2, Surface tension from equation (14.2)

T(K)

Y (dyn cm *) T(K)

Y (dyn cm 1 ) 590 119.4 740 110.2

600 118.8 750 109.6

610 118.1 760 109.0

620 117.5 770 108.3

630 116.9 780 107.7

640 116.3 790 107.1

650 115 .

800 106.5

660 115.1 810 105.9

670 114.5 820 105.3

680 113.9 830 104.7

690 113.2 840 104.0

700 112.6 850 103.4

710 112 o 0 860 102.8

720 111.4 870 102.2

730 110.8 880 101.6

References [28-33].

142
NaN0

3 4.

Viscosity (pi

Measurement method: capillary [37,40]

n

= 25.0987 - 6.0544 x 10~ 2 T + 3.8709 x 10~ 5 T

2 [14. 3)

precision: ^ + 0.6% uncertainty: ^ +3%

Table 14.3, Viscosity from equation [14.3)

T(K)

0

(cp )

T(K)

n(cp)

590 2 . 85 670 1 .91

600 2 .71 680 1 .83

610 2.57 690 1 .75

620 2.44 700 1.69

630 2 .32 710 1.63

640 2 . 21 720 1 .57

650 2.10 730 1 .53

660 2.00

References [34-40].

5.

Electrical Conductance (k)

Measurement method: ac technique [26]

k = -2.234486 + 6.533061 x 10" 3 T - 1.730567 x 10“ 6 T

2 [14.4)

precision: + 0.05% uncertainty: ^ + 1%

Table 14.4. Electrical conductance from equation (14.4)

T(K)K (ohm 1 cm 1 )T(K)K (ohm 1 cm 1

) 590 1.018 650 1.281

600 1 . 062 660 1 .323

610 1.107 670 1.366

620 1 .151 680 1.408

630 1.195 690 1 . 449

640 1.238 700 1 .491

References [14,25,26,41-47].

6.

Safety and Hazards

A. Hazard rating [4,48,49]

[i) Inhalation: low; ingestion: permitted as a food

additive

[ii) Vapor pressure: NaNO? [m.pt. 307°C) melts without

decomposition; the melt is stable in air to approx.

500°C; at higher temperatures, decomposes to form

NaNC^ and oxygen, viz:

NaN0

3

< NaN0

2 + hO

2 [14.5)

143
NaN0

3

At 800°K, for example, the value of the equilibrium constant for this reaction has been

reported as 1,34 x 10 " .

B. Disaster hazards [4,48,50-52]

(i) Molten salt bath "explosions": i.e, explosive generation

of steam due to bulk water "carry-over" and/or

equipment failure; i.e., explosive expansion of

"trapped" air.

(ii) On decomposition, nitrates emit toxic fumes (oxides

of nitrogen) viz:

2MN0

3 —* 2MN02 + 02 (14.6.1)

2MN0

2 * M2 0 + NO + N0

2 (14.6.2)

The subsequent decomposition reactions are complex;

if the gas phase is continuously removed, the nitrite

decomposition (above) to NO and N0

2 is dominant.

(iii) Nitrates are powerful oxidizing agents; violent

(explosive) reactions possible in molten nitrates

and carbonaceous materials (organic cpds., oils,

carbon,.,..); aluminum alloys and bath sludges (e.g.

iron oxides); magnesium alloys. Dangerous,

References [4,48-52],

7. Covvo sion

Table 14,5, Corrosion studies from primary research literature

Studies Ref er ences

Fe 53,55,57

Fe , Co , Ni 54

Cu 56

Pt , S , steel 58

Oxide species 59

Electrochemical approach 60,61

Thermodynamic redox diagrams 62,63

Annotated corrosion biblio. 64

Reviews/molten salts 65-67

References [53-67],

8. Diffusion

Measurement method: cited in tabulations

List of diffusing species investigated in NaN0

3 as solvent

Na

+

, NO’, K

+

, Rb

+

, Cs

+

, Sr

2+

3 Ba

2+

,

Tl +

, Ag

+

, F

’

, Br\ I", CC> 3

’ , SO^

144
NaN0

3

The italicized species indicate studies with insufficient

data-sets for characterization of temperature dependence

of diffusion coefficients. For these species, see table 14.6.5.

precision: in table 14.6.2. uncertainty: in table 14.6.1.

Table 14,6,1. Diffusion techniques, uncertainties, and species

Diffusion techniques

of recommended study

Uncertainty

(in values of D)

Species

capillary * ± 10 % v + 100 %

Na

+

, NO 3 , K+

Sr 2+

, Ba 2+

, Tl + chronopotentiometry * ± 10 % Ag

+ interferometry * + 30% Rb , F, Br, I,

2 - 2 - CO 3 , S 0 4 electrophoresis * ± 25% Cs +

, Tl +

Equation

D = A exp[ -E/RT] (.14,7)

For values of eq. parameters and precisions: see table 14.6.2.

For numerical values: see tables 14.6.3 - 14,6.5,

References: Na

+

, 69-71, 75, 80, 81, 83-90, 100; N0

3

, 69, 84;

K

+

, 90, 91; Rb

+

, 79; Cs

+

, 70, 75, 79, 83, 85, 88;

Ag

+

, 68, 77, 78, 82, 91-96, 99; F~, 98; Br", 98;

l‘, 98; CO

2 ', 98; SO

2 ’, 98; Sr

2+

, 73; Ba

2+

, 73;

Tl

+

, 73, 87.

Table 14.6.2. Parameters of diffusion equation (14.7),

precisions, and recommended study

Species A x 10 3

(cm 2 sec"1

)

E (cal mol -1

)

Temp . range

(K)

Precision Recommended

study

Na + 1.29 4347 600-670 *±2.3% 80

NO 3 0. 90 5080 585-650 *±1.4% 69,84

K+ 1.199 5144 590-670 *±1.3% 90

o' +

0. 694 4682 580-670 *±4 .5% 79

Cs 0.85 4740 580-720 75

Ag

+

1 . 07 4645 590-670 *±2 . 6 % 99

F~ 0.782 5730 620-650 *± 6 .9% 98

Br" 1 .312 5671 590-670 *±7.4% 98

i" 1.712 5994 590-660 *±6 . 6 % 98

cor 1 .103 6432 590-650 *±6 . 2 % 98

soj" 0.762 5888 590-650 *±4.2% 98

No entry in precision column indicates estimate not possible since

results were reported as equations only.

145
NaN0

3

Table 14.6.3, Self ^diffusion coefficients

T(K)

D + x 10 5 Na T

(cm 2 sec -

)

D _ x 10 5 NO 3 (cm 2 sec" 1

)

580 1.10

590 1.18

600 3 .37 1.27

610 3.57 1.36

620 3.79 1.46

630 4 . 00 1.56

640 4 .23 1 .66

650 4.46 1.76

660 4 .69

670 4 . 93

Table 14,6,4. Diffusion coefficients, D x 10^ (cm^sec"^)

T (K) K+

Rb +

Cs

+ A g + F~ Br” I~ CO 3 ”

S 04

~

580 1.19 1 .39

590 1.49 1 . 28 1.49 2 . 04 o

1

—

1 . 03 .0.457 0.502

600 1 . 60 1 . 37 1 . 60 2.17 1.13 1 .12 0.501 0.546

610 1.72 1.46 1.70 2.32 1 . 22 1.22 0.547 0.592

620 1.84 1. 55 1 .81 2 .47 0.746 1 .31 1.32 0.596 0 . 641

630 1 . 97 1 . 65 1 . 93 2 . 62 0.804 1.41 1.43 0.647 0.691

640 2.10 1.75 2 . 05 2 .77 0.863 1 .52 1 . 54 0.701 0.744

650 2 . 23 1.85 2 .17 2 . 93 0.925 1 . 63 1 . 65 0.758 0.799

660 2 .37 1 . 95 2.29 3.10 1 . 74 1.77

670 2 .52 2 . 06 2 .42 3.27 1 .85

680 2 .55

700 2 .82

720 3 . 09

Table 14.6.5. Diffusion coefficients for species not included

in tables 14,6.3 and 14,6,4

Species T(K)D x 10 5 (cm 2 sec

-1

)

Recommended

study

Sr 2 + 618 4 .

74

633 4.4

Ba 2 + 633 3 .74

Tl + 589 1.83 87

603 3 .90 74

633 4.30

146
NaN0

3

9. Heat of Fusion 6Atf^i

Measurement method: reaction calorimetry [12]

Table 14.7. Heat of fusion

AH ° (kcal mol ) Uncertainty

3 .70 ^ ± 1.0%

References [2,5,7-9,12,101-109],

10. Heat Capacity (C^

)

Measurement method: drop calorimetry; DSC [5,110]

Table 14.8. Heat capacity

C Temp, range Uncertainty

/ ~1 P "lx (cal K mol ) (K)

37 .

0

600-700 ± 5%

References [5,8,12,110],

11. Volume Change on Melting (AF^J

Measurement method: capillary technique [111]

Table 14.9. Volume change on melting

(AV /V) r s Uncertainty

10.7% ^ ± 5%

References [111-113],

12. Vapor Pressure (

p

, ) r r vap

Measurement method: critical evaluation; NSRDS study [4]

The stability of NaNO^ (crystalline) relative to the hypothetical

decomposition:

2NaN0 7 :^Na 9 0 + 2N0 9 + %0 ? (14.8)

3 (c)

2 (s)

2 (g)

2 (g)

may be illustrated by the values of K . .m predicted thermodynamically. ^

Table 14.10.1. Equilibrium dissociation constants and

pressures for equation (14.6)

T(K) 298 . 15 400 500 600 700 800

K . . - m. (equil ) 2 . 29xl0" 81

2. 80xl0“ 55 -40 3.58x10

-3 0 2.42x10

-24

6.24x10 1. 6xl0

-1

P (atm)

-27

5.53x10 4 . 56xl0" 18

6 . 57xl0~ 15

1 . 61xlO

_9

2 . 85xl0

-7

2 . Ixl0“ 5

NaNOj (m.pt. 307°C)

in air to ^ 500°C.

onsets

melts without decomposition; the molten salt is stable

At higher temperature the decomposition to nitrite

NaN0 7 <=*NaN0 + %0 (14.9)

3 0O 2 U) 2

147
NaNO

3

If the gas phase is not removed, a nitrate -nitrite interconversion

equilibrium is established since NaNO^ reacts with 0-. Values for the

equilibrium constant, from an experimental study are as follows:

Table 14.10.2. Equilibrium dissociation constants and

pressures for equation (14.7)

T (K) 800 850 900 950 1000

K . .. m [xl 0^ ] equil 1 . 34 3. 62 8 .80 19.5 398

Since NaNO^ is soluble in NaNO- and the solution is virtually ideal,

Kequilra * Po? I XNaN0 2 / XNaN0 3

] ( 14 ' 10 > The enthalpy of reaction, AH° 2 98 .i> from these data, is 26.13 kcal.

If the gas phase is continuously removed, the nitrite decomposition

proceeds by decomposition to oxide and nitrogen oxides:

2NaN0

2 V=^Na

2 0 + NO + N0

2 (14.11)

If the nitrite decomposition is carried out in an inert atmosphere, the

first decomposition product is N^, and this is accompanied by increasing

concentration of O

2 as the reaction proceeds. The evolution of N 2 has

been attributed to the formation of a super-oxide (which subsequently decomposes to Na

2Oand oxygen).

References [4,114-120],

IS. Thermal Conductivity (liquid) (X

Measurement method: concentric cylinder [125]

X = 9.696 x 10' 4

+ 6.28 x 10' 7 T (14.12)

precision: not estimated uncertainty: ^ ± 20%

Results were reported in equation form only.

14 .

References [121-128],

Thermal Conductivity (solid) (X ) ^ s Measurement method: steady state

X = 9.466 x 10' 4

+ precision: not estimated

Results were reported in equation

concentr ic

8.02 x 10

uncer

form only

cyl ind

~ 7 t (1

tainty

er [ 1

4.13)

% +

28]

10 %

148
NaN0

3

Table 14.12. Thermal conductivity of solid from equation (14.13)

T(K)A x 10 4 (cal cm" 1 see -

K

-1

)

T(K)

A x 10 4 (cal cm" 1 sec" 1 K" 1

).

500 13.48 550 13.88

510 13.56 560 13 .96

520 13 . 64 570 14 . 04

530 13.72 580 14.12

540 13 .80

References [128] .

15. Cryosaopic Constant (kj.)

Measurement method: calculated from aH£ [101]

Table 14.13. Cryoscopic constant

k

-1-1 Uncertainty

(K mol kg )

15 .

^ ± 1%

References [12 , 101 , 107 , 108 , 129-132]

16, References

[1] Dworkin, A. S., and Bredig, M. A., J, Phys. Chem., 67_, 697 (1963),

[2] Rossini, F. D., Wagman, D. D., Evans, W, H. , Levine, S, , and Jaffe,

I., "Selected Values of Chemical Thermodynamic Properties , NBS

Circ, 500 "; U. S. Gov't Printing Office, Washington, D. C. (1952).

[3] Franzosini, P., and Sinistri, C. , Ricerca Sci. Rc . (ii) , A3, 411

(1973). ~

[4] Stern, K. , "High Temperature Properties and Decomposition of In- organic Salts. III. Nitrates and Nitrites ", J. Phys. Chem. Ref.

Data, 1, 747-772 (1972).

[5] Mustajoki, A., Ann. Acad. Sci. Fenn. A6, _5 , 17 (1 957).

[6] Puschin, N. A., and Radoicic, M., Z. anorg . Chem., 233 , 4f (1937).

[7] Sokolov, V. A., and Schmidt, N. E., Izv, Sek. Fiz. Khim. Anal. Inst.

Obschch. Neorg, Khim. Akad . Nauk, USSR., 2_6, 123 (1955).

[8] Goodwin, H. M. , and Kalmus, H. T., Phys. Rev., 28_, 1 (1909).

[9] Kelley, K. K. , U. S. Bur. Mines, Bull. 477 (1950).

[10] McAuley, W. J., Rhodes, E., and Ubbelohde, A. R., Proc . Royal Soc.,

(London), 289A , 151 (1966).

[11] deNooijer, B, , Ph.D. Thesis, Univ. Amsterdam, Netherlands (1965).

[12] Janz, G. J. , Kelly, F. J., and Perano, J, L., J. Chem. Eng. Data,

9, 133 (1964).

[13] Bloom, H. , and Heymann, E., Proc. Roy. Soc., 188 , 392 (1947).

[14] Sandonnini, C., Gazz. Chim. Ital., 501 , 289 (1920).

14 9
NaN0

3

[15] Lorenz, R. , Frei, H., and Jabs, /\. , Z. Phys . Chem. , 61_, 468 (1908)

[16] Grothe, H. , Z. Elektrochem. , 5_3, 362 (1949).

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and Kalmus , H . T.

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150
NaN0

3

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,

Christensen,

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Metals"

,

National Board Fire Underwriters Research Report

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25 (1972).

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Reactions and Processes, The Electrochemical Society, Inc.,

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(1966).

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151
NaN0

3

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Interscience, New York, p. 535 (1964).

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(1922).

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Chem. Phys., 53, 2621 (1970).

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(1976)

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(1966)

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,

J. Amer. Chem. Soc. , _78, 1772 (1956) .

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(1960)

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(1954)

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(1963)

152
NaN0

3

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363 (1969).

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Congress, Montreal (1961).

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by ref. 68.

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J. Chem. Eng. Data, _8, 364 (1963).

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(1960); ibid., 2_8_4 , 131 (1956); ibid., 2_8_7 , 313 (1956).

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Soc. , 22_0 , 14 (1953) .

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J. App 1 . Chem. USSR, 40, 1386 (1967).

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153
NaN0

3

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of Molten Salts", W. A. Benjamin, Inc., New York, p. 106, 1967.

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Refer: McLaughlin, E., Chem. Rev., 6_4, 389 (1964).

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Naturfors ch . , 23a , 44 (1968).

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18, 1171 (1965).

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Technology, London, 1959.

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[132] Janz, G. J., et al . , (MSDC-RPI) unpublished work (1977).

154
XV. Potassium Nitrate: KNO^

1. Melting Temperature (Tm

) Melting point:

337° + 1°C [1,2,4,13]

References [1-15] .

2. Density (p)

Measurement method: Archimedean technique [16]

p = 2.315 - 7.29 x 10" 4 T (15.1)

precision: + 0.1% uncertainty: ^ + 0.5%

Tab'le 15.1. Densities from equation (15.1)

T

(K)

P (g cm-3

)

T

(K)

P (g cm-3

) 620 1 .863 750 1.768

630 1 .856 760 1.761

640 1 . 848 770 1 .754

650 1.841 780 1 . 746

660 1.834 790 1 .739

670 1.827 800 1.732

680 1 . 819 810 1.725

690 1.812 820 1.717

700 1 .805 830 1.710

710 1.797 840 1.703

720 1 .790 850 1.695

730 1.783 860 1.688

740 1.776 870 1 .681

References [7,16-24].

3.

Surface Tension (y)

Measurement method: pin detachment [25]

y

= 156.99 - 7.50 x 10

_2

T (15.2)

precision: + 0.1% uncertainty: ^ + 1.0%

Table 15.2. Surface tension from equation (15.2).

T(K)

Y

(dyn cm *) T(K)

Y

(dyn cm 1 )

610 111.2 700 104.5

620 110.5 710 103.7

630 109 .

720 103.0

640 109.0 730 102.2

650 108.2 740 101.5

660 107.5 750 100.7

670 106.7 760 100.0

680 106.0 770 99.2

690 105.2

References [12,25-29].

155
4.

KN°3

Viscosity (r\)

Measurement method: capillary and oscillational techniques [40]

n = 28.404 - 67.52062 x 10

_3

T + 0.4220783 x 10" 4 T

2 (15.3)

precision: ^ + 0.9% uncertainty: ^ + 2.0%

Table 15.3. Viscosity from equation (15.3)

T(K)

n(cp)

T(K)

n(cp)

620 2.77 700 1 .82

630 2.62 710 1 .74

640 2.48 720 1 .67

650 2 .35 730 1.61

660 2 .23 740 1 .55

670 2.11 750 1 .51

680 2.01 760 1.47

690 1 .91

References [7,8,10,15,30-43].

5. Electrical Conductance (k)

Measurement method: ac technique [9]

< = -2.11923 + 5.71490 x 10

_3

T - 3.01492 x 10

_6

T

2 (15.4)

precision: + 0.1% uncertainty: ^ ± 1.0% >

Table 15.4. Electrical conductance from equation (15.4)

T K T K (K) (ohm 1 cm 1 ) (K) (ohm 1 cm 1 ) 620 0.649 720 0.951

630 0.681 730 0.979

640 0.713 740 1 . 006

650 0.744 750 1.034

660 0.775 760 1.060

670 0.805 770 1.087

680 0.835 780 1.113

690 0.865 790 1.138

700 0.894 800 1.163

710 0.923 810 1 . 188

References [9,16,17,19,23,31,44-50]

6. Safety and Hazards

A. Hazard rating [4,51,52]

(i) Inhalation: low; ingestion: permitted as a food

additive

(ii) Vapor pressure: KNOj (m.pt. 337°C) melts without

decomposition to a liquid which is stable in air

at least to 530°C; between 550° and 750°C, the

quasi-equilibrium sets up:

KN0

3 KN0

2 + %0

2 (15.5)

156
KN0

3

(i)

(ii)

(iii)

i.e., the two salts interconvert in this temperature

range (but: see below)

B. Disaster hazards [51,53-55]

Molten salt bath "explosions": violent generation of

steam due to bulk water "carry-over" and/or equipment

failure; sudden explosive expansion of "trapped" air.

On decomposition, nitrates emit toxic fumes (oxides of

nitrogen) viz:

MN0

3 2MN0-

MNO

2- m

2 ° ^2

NO NO,

(15.6.1)

(15.6.2)

The subsequent decomposition reactions are complex;

if the gas phase is continuously removed, the nitrite

decomposition (above) to NO and N0

2 is dominant.

In the temperature range 550-600°C, and under oxygen,

the conversion of KN0 2 to KNO3 goes to completion; between 650-750°C, the two salts interconvert (see above),

KNO3 becoming increasingly unstable; above 800°C, the

nitrite decomposition: 2 KN0

2

~ to completion.

K 2° +N

2 + ! / 2 o

2 goes

Nitrates are powerful oxidizing agents; violent (explosive) reactions possible in molten nitrates and

carbonaceous materials (organic cpds., oils, carbon,,

aluminum alloys and bath sludges (e.g. iron oxides);

magnesium alloys. Dangerous.

.);

References [4,51-55].

7. Corrosion

Table 15.5. Corrosion studies from

primary research literature

Studies References

Fe 56

Pt, Rh, Ag 57

Oxide species 58

Electrochemical approach 59,60

Thermodynamic redox diagrams 61,62

Reviews / corro sion : molten salts 63-65

Annotated corrosion biblio. 6 6

References [56-66].

8. Diffusion

Measurement method: cited with each diffusing species

List of diffusing species investigated in KNC>

3 as solvent

K

+

, NOj, Li +, Na

+

, Rb

+

, Cs

+

, Sr

2+

, Ba

2+

, Tl

+

, Ag

+

, Br~, I~

The italicized species indicate studies with insufficient data-sets

for characterization of temperature dependence of diffusion coefficients. For these species, see table 15.6.5.

157
KNOj

precision: in table 15.6.2 uncertainty: in table 15.6.1

Table 15.6.1. Diffus ion techniques , uncertainties, and species

Diffusion technique

of recommended study

Uncertainty

(in values of D)

Species

capillary "o + 20% K

+

, NO;, Li+

% ± 100% Tl +

, Br”, i”

chronopotentiometry ^ + 10% Sr 2 +

, Ag

+ polarography % + 50% Ba 2+

, Tl +

, Br”, l”

interferometry 'v + 30% + + +

’ Na , Rb , Cs

Equation

D = A exp [ -E/RT] (15.7)

For values of eq. parameters, and precisions: see table 15.6.2.

For numerical values : see tables 15. 6 . 3

- 15.6.5.

References

K

+

, 68 , 71 , 74, 77, 79, 87 ; NC1 3 , 6 8 ; N a , 70, 72, 73

,

77, 80, 87 ; Rb

+

, 73; Cs

+

y 73; Sr

2+

, 70, 81;; Ag

Hh , 70, 75,

76, 83- 86 ; Li

+

, 72; Ba

2 +

y 67, 69; Tl

+

, 67, 69; Br , 67,

69; i". 67 , 69.

Table 15.6.2. Parameters of diffusion equation (15.7),

precisions, and recommended study

Species A x 10 3 (cm 2 sec -1

)

E (cal mol -

)

Temp . range

(K)

Precision Recommended

study

+

K 1 . 48 5674 615-700 ^±3% 74,79

no; 1.42 5760 620-660 ^±2.7% 68

Na +

2 . 925 6237 620-690 ^±4 .2% 73

Rb +

1 . 026 5321 610-725 ^±6.2% 73

Cs + 0.593 4781 610-730 ^±6 .8% 73

Sr 2 + 6.63 8150 620-690 -v±4 .5% 81

Ag

+

1 .53 5280 620-720 76-

No entry in precision column indicates estimates not possible since

the results were reported as equations only.

158
KN0

3

Table 15.6.3. Self-diffusion coefficients

T

(K)

D k+ x 10 5

(cm 2 sec -1

)

d

no;

*' io*

(cm 2 sec -1

) 610 1 .37

620 1.48 1 .32

630 1.59 1 .43

640 1 .71 1 .53

650 1.83 1 . 64

660 1 .96 1.76

670 2.09

680 2 .22

690 2.36

700 2.50

Table 15.6.4. Diffusion coefficients

T(K)

D x 10 5 (cm 2 sec -1

)

Na +

Rb

+

Cs +

Sr 2 +

> 00 +

610 1.27 1.15

620 1.85 1.37 1 .22 0.888 2.11

630 2.01 1.46 1 .30 0.986 2 .25

640 2.17 1.56 1.38 1 . 09 2.41

650 2.34 1.67 1.46 1 . 21 2.57

660 2.52 1 .77 1.55 1 . 33 2 .73

670 2 .70 1 .89 1 . 63 1.46 2 .90

680 2.89 2 . 00 1.72 1 .59 3 . 07

690 3.09 2.12 1 .81 1 . 74 3 . 25

710 2.36 2 . 00 3 . 63

720 2 .49 2.10 3.82

730 2 . 62 2.19

Table 15.6.5. Diffusion coefficients for species not

included in tables 15.6.3 and 15.6.4

Species T(K)

D x 10 5 (qm 2 sec -1

) Recommended

study

Li

+ 625 2 .

72

645 2 . 6 Ba 2 +

643 2.1 70

Tl

+ 618 3.2 70

638 3 .

3

653 3.4

Br" 633 3 .

0

70

i" 633 3.0 70

9. Heat of Fusion (A Hj,)

Measurement method: reaction calorimetry [88]

Table 15.7. Heat of fusion

AH °f Uncertainty -1

(kcal mol ) 2.41 ^ ± 1%

References [1,3,5,88-92].

159
KNO

3

10. Heat Capacity J Measurement method: drop calorimetry [94]

Table 15.8. Heat capacity

C P Temp, range Uncertainty

(cal K~lmol ) (K)

32.4 610-663 ^ ± 1.5%

References [90,93,94].

11. Volume Change on Melting (AT^J

Measurement method: capillary technique [95]

Table 15.9. Volume change on melting

(A VV Uncertainty

3 . 3% ^ ± 1.5%

References [95,96].

12. Vapor Pressure (

VOp

)

Measurement method: critical evaluation; NSRDS study [4]

KNO, (m.pt. 337°C) melts without decomposition. The melt is stable

in air to at least 530°C. Decomposition reactions lead to the interconversion equilibrium:

KNO, +=T*KN0 9 + h0 7 (15.8)

3 U) (O (g)

over a limited temperature range. Values of the equilibrium constant,

from an experimental study, are in table 15.10.

Table 15.10. Equilibrium dissociation constants for equation (15.8)

T (K) 823.1 873 .921.1 973 .1023 .

K m [ xl 0^

] equil 0.88 2 . 7 6.2 21 .

28.0 .

and the enthalpy for this reaction, from these data, is AH298.1 = 27.6 ± 1.2

kcal mol' 1 . In an oxygen atmosphere, in the temperature range

550°-600°C, the conversion of nitrite to nitrate goes to completion.

From 650°-750°C, KN0 2 becomes increasingly more unstable. Experi-

_

mentally it has been^shown that the above reaction attains equilibrium

in the range 650° to approx. 800°C. Above 800°C, the nitrite decomposition is dominant:

2 KN0

2 * K

2 0 + N

2 +

3 / 2 0

2 (15.9)

160
KN°

3

If O 2 is removed, the nitrite decomposition leads to

various oxides of nitrogen, e.g.

the formation of

2KN0

2 K

2 0 + N02 + NO (15.10)

and the processes are more complicated.

References [4,13,97-102]

13. Thermal Conductivity (liquid) (\

)

Measurement method: concentric cylinder [105]

X = 5.665 x 10

_4

+ 8.7 x 10

_7

T (15.11)

precision: not estimated uncertainty: ^ + 20%

Results were reported in equation form only.

Table 15.11. Thermal conductivity of melt from equation (15.11)

T(K)

X x 10 4 (cal cm - 1 s ec

- 1 K" 1 )

T(K)

X x 10 4 (cal cm

sec - 1 K

-1

1

610 10.97 680 11 . 58

620 11 .06 690 11 . 67

630 11.15 700 11.76

640 11 .23 710 11 . 84

650 11.32 720 11 . 93

660 11.41 730 12 . 02

670 11.49

References [103-113] .

14. Thermal Conductivity (solid) (\ ) s Measurement method: comparative technique [114]

precision: not estimated uncertainty: ^ + 10%

Results were reported in graphical form only.

Table 15.12. Thermal conductivity of solid

T(K)

4

X x 10

(cal cm

4 sec

4 K

-4

)

T(K)

4

X x 10-

, 1 "I -1-1,

(cal cm sec K )

353 22 . 9 408 19 .

363 23 .

413 19.4

373 23 .

423 19.6

383 23.7 433 20 .

393 24.1 443 20 .

6

403 20.3 453 21.0

Sole investigation in the temperature range 350-450 K; values

interpolated from the graphical presentation in [114] . References [104,114].

161
15 .

KNO.

Cryoscopic Constant (k^J

Measurement method: calculated from AH| [115]

Table 15.13. Cryoscopic constant

k _f Uncertainty

1 -H 60 ^4

i

—

i 1

—W &O

31.0 v ± 1%

References [3,115-119].

1 6. References

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Janz, G. J. , and Saegusa, F. , J. Electrochem. Soc., 110 , 452 (1963).

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6, 850 (1961).

162
[ 21 ]

kno

3

Petersen, G. F. , Ewing, W. M. , and Smith, G. P., J. Chem. and

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,

M. R. , Rev. Sci. Instr. , 3^, 18 (1960)

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R. , J. Phys. Chem. , 62

,

1142 (1958).

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,

C. C. , and Coldrey, J. M. , J. Chem. Soc. , 468 (1961).

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,

F. M. , Z . anorg

allgm. Chem.

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6

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Khim. , 26., 3267 (1956) .

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307 (1964).

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Gardner, G. L., Krebs, U. , and Singer, S. K. , J. Phys. Chem. Ref.

Data, 4, 871 (1975).

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Scand. , 24_, 510 (1970) .

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n, 156 (1966).

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[45] Sandonnini, A., Gazz. Chim. Ital., 501 , 289 (1920).

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163
KN0

3

[49] Cowen, H. C. , and Axon, H. J., Trans. Faraday Soc., 5_2, 242 (1956).

[50] Ketelaar, J. A. A., and De Nooyer, B., Koninkl. Nederl . Akad. Wetensch.,

Proc. Ser. B., 7_5, 97 (1972).

[51] "Dangerous Properties of Materials ", Sax, N. I., Van Nostrand

Reinhold Co. , N. Y. (1969)

[52] "Registry of Toxio Effects of Chemical Substances' Christensen, H. E.

,

and Lubinybyhl, T. T. , eds., U. S. Dept. H.E.W; U. S. Gov't Printing

Office, Washington, D. (1975).

[53] "Potential Hazards in Molten Salt Baths for Heat Treatment of Metals"

,

National Board Fire Underwriters Research Report No. 2. (1954).

[54] "Handbook of Reactive Chemical Hazards"

,

Bretherwick, L. , Butterworths

Co., London (1975).

[55] Janz, G. J., Tomkins, R. P. T. , Downey, J. R., Jr., and Allen, C. B.

,

"Safety and Hazards ", Chapter in "Eutectic Data"3 ERDA TID - 271 63 -PI

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[56] Noytaya, T. , and Midorikawa, R. , Denki Kagaku, 3J5, 930 (1971).

[57] Johnson, K. E. , Elec trochimica Acta, 11_, 129 (1966).

[58] Johnson, K. E. , Zacharias, P. S. , and Matthews, J. , "Proceedings

Intern. Symp. Molten Salts", The Electrochem. Soc., Princeton,

N. J. , p. 603 (1976)

[59] Johnson, K. E., "Electrochemical Approaches to Corrosion in Molten

Salts", Proceedings International Symposium on Metal - Slag -Gas

Reactions and Processes, The Electrochemical Society, Inc.,

Princeton, N. J. , p. 581 (1975).

[60] Pizzini, S., "Materials Problems in the Industrial Applications of

Molten Salts", Proceedings of the European Conference on the

Development of Molten Salts Applications, Battelle, Geneva,

p. 203 (1973),

[61] Conte, A., and Ingram, M. D. , Electrochimica Acta, 13_, 1551 (1968).

[62] Bartlett, H. E., and Johnson, K. E., Canad. J. Chem. , 44_, 2119 (1966).

[63] Smirnov, M. V., and Ozeryanaya, I. N. , Nauki Tekh. Korros. Zashch.,

Korros. , 2, 171 (1973)

[64] Inman, D. , and Wrench, N. S., Brit. Corr. J. , , 246 (1966).

[65] Ketelaar, J. A. A., Chemie. Ing. Techn. , 4_5, 667 (1973).

[66] Janz, G. J. , and Tomkins, R. P. T. , Corrosion, 34., (in press) (1978).

[67] Delimarskii, Yu. K. , and Markov, B. F. , "Electrochemistry of Fused

Salts", Sigma Press, Washington, D. C., Chap. 8 (1961).

[68] Dworkin, A. D. , Escue, R. B. , and van Art sdalen , E. R. , J. Phys.

Chem. , 64, 872 (1960)

[69] Klemm, A., in "Molten Salt Chemistry", (M. Blander, ed.), WileyInterscience , New York, p. 535 (1964).

[70] Lorenz, R. , Raumerful lung und Ionengewegl ichkeit , Leipzig, p. 207

(1922)

[71] Ketelaar, J. A. A., and Honig, E. P. , J. Phys. Chem., 6_8 , 1596 (1964).

[72] Aperce, J. P., Lantelme, F. , and Chemla, M. , C. R. Acad. Sci. Paris,

Ser. C, 2_64 , 461 (1967).

164
[73]

kno

3

Arvidsson, T. E. G., Afsenius, S. A., and Gustafsson, S. E., J.

Chem. Phys., 5_3, 2621 (1970).

[74] Zuca, S. , and Constantinescu , M. , Rev. Chim. (Roumaine), 1

1 385 (1972).

[75] Sjoblom, C. A., and Behn, A., Z. Naturforsch. , 23A , 1174 (1968).

[76] Mazzocchin, G. A., and Schiavon, G., J. Electroanal. Chem., 38 , 229 (1972).

[77] Lantelme, F. , and Chemla, M. , Bull. Soc. Chim. France, 169 , 969 (1963).

[78] Bowcott, J. E. L. , and Plunkett, B. A., Electrochim. Acta, 14^, 363

(1969) .

[79] Zuca, S., and Constantinescu, M. , Z. Naturforsch., 28A , 51 (1973).

[80] Ketelaar,'J. A. A., and Kwak, J. C. T. , J. Phys. Chem., 71 , 1149 (1967)

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, 1861 (1976).

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21, 1153 (1976).

[84] Sternberg, S., and Visan, T. , Rev. Chim. (Roumaine), V8, 221 (1973).

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[87] Honig, E. P., and Ketelaar, J. A. A., Trans. Faraday Soc., 6_2, 190

. (1966).

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(1968)

[90] Goodwin, H. M. , and Kalmus , H. T. , Phys. Rev., 28_, 1 (1909).

[91] Sokolov, V. A., and Schmidt, N. E., Izvest. Sekt. Fiz. Khim. Anal.,

26_, 123 (1955); ibid., 27 , 217 (1956).

[92] Magneron, E. , Diplomes d'Etudes Superieures, Paris (1959).

[93] Douglas, T. B., Brookhaven National Laboratory, Report No. BNL-2446

(1954); Trans. Amer. Soc. Mech. Eng., 7j), 23 (1957).

[94] Clark, R. P. , J. Chem. Eng. Data, 1_8_, 67 (1973).

[95] Schinke, H. , and Sauerwald, F., Z. anorg. allgm. Chem., 304, 25 (1960);

ibid., _284 , 131 (1956); ibid., 28J7 , 313 (1956).

[96] Shimoji, M. , Disc. Faraday Soc., 3_2 , 128 (1961).

[97] Bond, B. D., and Jacobs, P. W. M. , J. Chem. Soc., A, 2565 (1966).

[98] Freeman, E. S. , J. Amer. Chem. Soc., 7_9, 838 (1957).

[99] Bartholomew, R. F. , J. Phys. Chem., 7_0, 3442 (1966).

[100] Sirotkin, G. D. , Russ. J. Inorg. Chem., £, 1180 (1959).

[101] Oza, J. M. , J. Indian Chem. Soc., 2_2 , 173 (1945).

165
KN0

3

[102] Oza, J. M. , and Walawalkar, B. R. , J. Indian Chem. Soc., _22_, 243 (1945).

[103] Turnbull, A. G., Aust. J. Appl. Sci., 1_2, 324 (1961).

[104] Turnbull, A. G., Ph.D. Thesis, Imperial College of Science and Technology,

London, 1959.

[105] McDonald, J. , and Davis, H. T. , J. Phys . Chem., 7_4> “'725 (1970).

[106] Gustafsson, S. E. , Hailing, N. D. , and Kjellander, R. 0., Z. Naturforsch. , 23a , 44 (1968)

[107] Jamieson, D. T. , Irving, J. B., and Tudhope , J. A., "Liquid Thermal

Conductivity

, HMSO, Edinburgh (1975).

[108] White, L. R. , and Davis, H. T. , J. Chem. Phys., 47, 5433 (1967).

[109] White, L. R. , Doctoral Diss., University of Minnesota, 1967.

[110] Bloom, H. , Rev. Pure Appl. Chem., 9_, 139 (1959); "The Chemistry of

Molten Salts"3 W. A. Benjamin, Inc., New York, p. 106, 1967.

[111] Bloom, H. , Doroszkowski , A., and Tricklebank, S. B. , Aust. J. Chem.,

1_8, 1171 (1965).

[112] McLaughlin, E., Chem. Rev., 64., 389 (1964).

[113] McDonald, J. , Doctoral Diss., University of Minnesota, 1969.

[114] Yoshida, I., and Sawada, S., J. Phys. Soc. Japan, 1_5, 199 (1960).

[115] Janz, G. J. , et al. , (MSDC-RPI) unpublished work (1977).

[116] Hoenen, P. H. J., Z. physik. Chem., 83^, 513 (1913).

[117] Doucet, Y. , Proc. 6th Mtg. Intern. Comm. Electrochem. Thermodyn.

Kin. , p. 492 (1955)

[118] Mustajoki, A., Ann. Acad. Sci. Fenn. A6, 8 (1958).

[119] Doucet, Y. , and Bizouard, M. , Compt. Rend., 242 , 2137 (1956).

166
XVI. Lithium Sulfate: L^SO^

1. Melting Temperature (T ) Melting point:

859° ± 3°C [1-3]

References [1-9] .

2. Density (p)

Measurement method: Archimedean technique [10,11]

p = 2.4641 - 4.061 x 10

_4

T (16.1)

precision: ± 0.021 uncertainty: ^ ± 1%

Table 16.1. Densities from equation (16.1)

T(K)

P (g cm-3

)

T(K)

P (g cm

-3

)

1140 2 . 001 1200 1.977

1150 1.997 1210 1 .973

1160 1.993 1220 1.969

1170 1.989 1230 1.965

1180 1.985 1240 1 .961

1190 1.981 1250 1.957

References [10,11].

3.

Surface Tension (y)

Measurement method: maximum bubble pressure [10]

Y

= 300.96 - 6.72 x 10

_2

T (16.2)

precision: ± 0.11 uncertainty: ^ ± 1%

Table 16.2. Surface tension from equation (16.2)

T(K)

y

(dyn cm 1 )

T

(K)

y

(dyn cm

1130 225.0 1260 216.3

1140 224.

1270 215.6

1150 223.7 1280 214.9

1160 223.0 1290 214.3

1170 222.3 1300 213.6

1180 221.7 1310 212.9

1190 221.0 1320 212.3

1200 220.3 1330 211.6

1210 219.6 1340 210.9

1220 219 .

1350 210.2

1230 218.3 1360 209.6

1240 217.6 1370 208.9

1250 217.0

References [10,12].

167
Ll

2 S04

4. Viscosity (r\)

No data.

5. Electrical Conductance (k)

Measurement method: ac technique [13]

k = -19.5390 + 35.410 x 10" 3

T - 12.7951 x 10' 6

T

2 (16.3)

precision: ^ ± 0.5% uncertainty: ^ ± 5%

Table 16.3. Electrical conductance from equation (16.3)

T

(K)

K (ohm ^m *)T

(K)

K (ohm L cm x ) 1145 4.231 1175 4.403

1150 4.261 1180 4.429

1155 4.291 1185 4.455

1160 4.320 1190 4.480

1165 4.348 1195 4.504

1170 4.376 1200 4.528

References [13,39].

6. Safety and Hazards

A. Hazard rating [14-16]

(i) Unknown (the "toxic" qualities of sulfates, in general, are

those of the cations with which the sulfate -is combined)

(ii) Vapor pressure: Li-SO- decomposes just above its m.pt. (859°C) , evolving aggressive and toxic fumes (S0

3

; SC>

2 ), viz:

Li

2 S0

4 Li

2 0 + S0

3 (16.4.1)

S0

3 S02 + h0

2 (16.4.2)

B. Disaster hazards [16-19]

(i) Molten salt bath "explosions": i.e., explosive generation of steam

due to bulk water "carry-over" and/or equipment failure; i.e.,

explosive expansion of "trapped" air

(ii) When heated to decomposition, sulfates decompose, evolving

SO3, which in turn dissociates to SO2 and O2 (see above); toxic,

corrosive fumes

References [14-19]

168
Ll

2 S0

4

7

Corrosion

Table 16.4. Corrosion studies from primary research literature

Studies Ref er enc e s

Metals 20,21

Metals, Fe 22

Ag 23

Thermodynamic redox diagrams 20,23,24,25

Electrochemical approach 26

Reviews: molten salts corrosion 27-29

Corrosion: annotated biblio. 30

References [20-30].

8. Diffusion

No diffusion studies reported.

9. Heat of Fusion (LH^,)

Measurement method: drop calorimetry [8,9]

Table 16.5. Heat of fusion

AH°

f Uncertainty -1

(kcal mol ) 1.79 ^ ± 2%

References [4-9,31].

10.

Heat Capacity ( C^

Measurement method: drop calorimetry [8,9]

Table 16.6. Heat capacity

c D Temp, range Uncertainty

(cal K"lmol~l) (K)

48.3 1132-1179 -v ± 0.5%

References [8,9] .

11.

Volume Change on Melting (AF^J

Measurement method: estimated from densities [32]

Table 16.7. Volume change on melting

(AV./V ) r s Uncertainty

1 . 2% ^ ± 8%

References [32 ]

169
Li

2 S0

4

12. Vapor r Pressure (pr ) vap

Measurement method: critical evaluation; NSRDS study [1]

L^SO^ (m. pt. 859°C) decomposes not far above its melting point,

with the evolution of SO^, S0

2

, and oxygen:

Li

2 S0

4 4=^ Li2 0 + S0

3 (16.5)

SOj -« S0

2 + JsO

2 (16.6)

The Li

2 0 is soluble in molten Li

2 S04

. Measurements of the decomposition

pressure have not been reported. Thermal data appear insufficient for

such pressures to be calculated thermodynamically.

References [1,33,34].

IS. Thermal Conductivity (liquid) (

\

No thermal conductivity studies reported.

14. Thermal ConductivityJ (solid) (X ) s No thermal conductivity studies reported.

15. Cryoscopic Constant

Measurement method: calculated

Table 16.8.

from AHr [32]

Cryoscopic constant

k .f Uncertainty

(K mol~-*-kg - l)

156 ^ ± 2%

References [8,9,31,32,35-38].

16. References

[1] Stern, K. , "High Temperature Properties and Decomposition of Inorganic

Salts. I. Sulfates"

,

NSRDS-NBS-7; U. S. Gov't Printing Office,

Washington, D. C. (1966).

[2] Rossini, F. D., Wagman, D. D., Evans, W. H. , Levine, S., and Jaffe, I.,

"Selected Values of Chemical Thermodynamic Properties , NBS Circ. 500,"

U. S. Gov't Printing Office, Washington, D. C. (1952).

[3] Wagman, D. D., Evans, W. H. , Harlow, I., and Dudley, R. , Amer . Inst.

Physics Handbook, Sec. 4. p. 170-216; McGraw Hill Book Co., New York,

N. Y. (1963).

[4] Nolte, G. , and Kordes, E. , Z. anorg. allgm. Chem. , 371 , 149 (1969).

[5] Schwiete, H. E., and Ziegler, G., Ber. dtsch. keram. Ges., 3_5, 193 (1958).

[6] Kelley, K. K. , U. S. Bur. Mines, Bulletin 393, 87, 136 (1936).

[7] Petit, G., and Bourlange, C., Compt. Rend. Acad. Sci. (Paris), 245,

1788 (1957).

[8] Clark, R. P., J. Chem. Eng. Data, 2_0 , 17 (1975).

[9] Voskresenskaya ,N. K. , and Banashek, E. I., Izv. Sekt. Khim. Anal., Akad.

Nauk SSSR, 25, 150 (1954).

170
Ll

2 S0

4

[10] Jaeger, F. M. , Z. anorg. Chem., 101, 1 (1917).

[11] Kvist, A., Z. Naturforsch. , 22a, 208 (1967).

[12] Semenchenko, K. , and Shikhobalova , L. P., Zh. Fiz. Khim. , 21 , 707 (1947).

[13] Kvist, A., and Lunden, A., Z. Naturforsch., 20a, 235 (1965).

[14] "Dangerous Properties of Materials ", Sax, N. I., Van Nostrand Reinhold

Co., N. Y. (1969).

[15] "Registry of Toxic Effects of Chemical Substances", Christensen, H. E.,

and Lubinbyhl, T. T., eds., U. S. Dept. H. E. W. , U. S. Gov't

Printing Office, Washington, D. C. (1975).

[16] "High Temperature Properties and Decomposition of Inorganic Salts. Part

1. Sulfates ", Stern, K. H. , U. S. Dept. Commerce NBS-NSRDS- 7-\ U. S.

Gov't Printing Office, Washington, D. C. (1966).

[17] "Potential Hazards In Molten Salt Baths for Heat Treatment of Metals "

National Board Fire Underwriters Research Report No. 2 (1954).

[18] "Handbook of Reactive Chemical Hazards", Bretherwick, L., Butterworths

Co . , London (1975) .

[19] Janz, G. J., Tomkins, R. P. T., Downey, J. R. , Jr., and Allen, C. B.,

"Safety and Hazards" Chapter in "Eutectic Data", ERDA TID-27163-P1

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[20] Rahmel, A., Electrochim. Acta, 13, 495 (1968).

[21] Dubois, J., and Richard, J. , Rev. Gen. Therm., 12, 805 (1973).

[22] Burrows, B. W. , and Hills, G. J. , J. Inst. Fuel, 39, 168 (1966).

[23] Rahmel, A., Corros. Sci., 13, 833 (1973).

[24] Bartlett, H. E. , and Johnson, K. E., Canad. J. Chem., 44, 2119 (1966).

[25] Baudo, G., and Tamba, A., Brit. Corrosion J., 4, 129 (1969).

[26] Johnson, K. E., "Electrical Approaches to Corrosion in Molten Salts",

Proceedings International Symposium on Metal - Slag-Gas Reactions and

Processes, The Electrochemical Society, Inc., Princeton, N. J.

p. 581 (1975).

[27] Smirnov, M. V., and Ozeryanaya, I. N. , Nauki. Tekh. Korros. Zashch.

Korros . , 2 , 171 (1973) .

[28] Inman, D. , and Wrench, N. S., Brit. Corr. J., 1, 246 (1966).

[29] Ketelaar, J. A. A., Chemie Ing. Techn. , 45, 667 (1973).

[30] Janz, G. J., and Tomkins, R. P. T., Corrosion, 34, (in press) (1978).

[31] Riccardi, R. , Gazz. Chim. Ital., 91, 1479 (1962).

[32] Janz, G. J.,et al., (MSDC-RPI) unpublished work (1977).

[33] Jaeger, F. M. , Z. anorg. Chem., 101, 178 (1917).

[34] Spitsyn, I., and Shostak, V. I., Zh. Obshch. Khim., 19, 1801 (1949).

[35] Kordes, E. , Z. Elektrochem. , 60 , 629 (1956).

[36] Kordes, E., Ziegler, G., and Proeger, J., Z. Elektrochem., 58, 168 (1954)

[37]

ngl

Grjotheim, K. , and Urnes, S., Z. Elektrochem., 60, 626 (1956).

Forland, T.. and Krogh-Moe, J. , Z. Elektrochem., 61, 1342 (1957).

[39] Kvist, A.; private communication to G. J. Janz (1978).

171
XVII. Sodium Sulfate: Na 0 SO„

1. Melting Temperature (T ) Melting point:

884° + 2°C [1,2]

References [1-9]

2. Density ( p ) Measurement method: Archimedean technique [6]

p = 2.6523 - 5.034 x 10' 4 T (17.1)

precision: ± 0.06% uncertainty: 'v ± 0.5%

Table 17.1. Densities from equation (17.1)

T(K)

P_

(g cm 3

)

T(K)

P (g cm 3

)

1180 2 . 058 1230 2 . 033

1190 2 . 053 1240 2 . 028

1200 2 . 048 1250 2.023

1210 2 . 043 1300 1.99 8

1220 2 . 038 1350 1.973

References [6,10-13],

3. Surface Tension (y)

Measurement method: maximum

Y

= 639.95 - 66.48

precision: ±

bubble pressure [6]

x 10' 2 T + 24.3 x 10' 5 T

2

0.6% uncertainty: ^ ±

(17.2)

8 %

Table 17.2. Surface tension from equation (17.2)

T(K)

Y (dyn cm 3 ) T

(K) (dyn cm

1180 193.8 1270 187 .

1190 193.0 1280 187.1

1200 192.1 1290 186.7

1210 191 .

1300 186.4

1220 190.6 1310 186.1

1230 189.9 1320 185.8

1240 189.2 1330 185.6

1250 188.6 1340 185.4

1260 188.1 1350 185.3

References [6,14].

4. Viscosity (r\)

Measurement method: oscillational viscometer [55]

n = 14.8 x 10' 2 exp (9990/RT) (17.3)

precision: not estimated uncertainty: ^ ± 25%

172
Na

2 S0

4 Table 17.3. Viscosity from equation (17.3)

T

(K)

n (cp)

T

(K)

n (cp)

T

(K)

n (cp)

1240 8.53 1320 6.68 1400 5.37

1260 8 . 00 1340 6.31 1420 5.10

1280 7.52 1360 5.97 1440 4.86

1300 7.08 1380 5.66 1460 4.63

References [55]

5. Electrical Conductance (k)

Measurement method: ac technique [4]

k = -1.42689 + 3.18608 x 10’ 3 T (17.3)

precision: ^ ± 0 . 1 % uncertainty: ^ ± 2%

Table 17,3. Electrical conductance from equation (17.3)

T(K)

K

(

hm 1 cm 1 )

T(K)K (ohm 1 cm *)

1180 2 . 333 1220 2.460

1190 2.365 1230 2 .492

1200 2 .396 1240 2 .524

1210 2.428

References [4,15] ,

6. Safety and Hazards

A, Hazard rating [16-18]

(i) Unknown (the "toxic" qualities of sulfates, in

general, are those of the cations with which the

sulfate is combined)

(ii) Vapor pressure: At the m.pt, of Na 2 S 0

^ (884°C),

the vapor pressures due to volatilization and due

to decomposition (to oxides of sulfur) are;

'v < 1

3mm a nd ^ < 1

^ ^mm

respectively; at 1500°C, the vapor pressure

(volatilization) is ^ 1 mm.

B. Disaster hazards [16,19-21]

(i) Molten salt bath "explosions": i.e., explosive generation

of steam due to bulk water "carry-over" and/or

equipment failure; i.e., explosive expansion of

"trapped" air

(ii) Sulfates, when heated to decomposition, evolve

SO 3 , which in turn dissociates to SO 2 and O 2 ; toxic, aggressive fumes.

References [16-21].

173
7 . Corrosion

Na

2 S0

4

Table 17.5. Corrosion studies from

primary research literature

Studies Ref er ence s

Ni, Co

Co-W, Ni-W, Co-Mo,

Cr-Ni, Co-Cr,

Ni-Cr-Mo, Co-Cr-Mo,

Co-Cr-Nb, Co-Cr-Ta,

Ni-Cr-Al, Co-Cr-Mn,

Co-Cr-Fe

Ni ~

Metals

Metals, Fe

Ag

"Hot corrosion" studies

Thermodynamic redox diagrams

Electrochemical aspects

Corrosion: molten salts

(reviews)

Annotated corrosion biblio.

22,29

23,24

25,26

27

28

30

25,27,31,32

33

34-36

37

References [22-37].

8. diffusion

No diffusion studies reported.

9. Heat of Fusion (A H

Measurement method: drop calorimetry [1,8]

Table 17.6. Heat of fusion

AH °f Uncertainty -1

(kcal mol ) 5.63 ^ ± 1%

References [1,7-9,38].

10. Heat Capacity ( C )

tr Measurement method: drop calorimetry [1,8]

Table 17.7. Heat capacity

C Temp, range Uncertainty

P

i 1 (cal K Tmol ) (K)

47.3 1157-1850 ^ ± 1%

References [1,8,39].

11. Volume Change on Melting ( AF

Measurement method: estimated from densities [40]

Table 17.8. Volume change on melting

<AV

f /V

s

) Uncertainty

18.7% v ± 8%

References [40].

174
Na-,S0

4 12. Vapor Pressure (

vap

Measurement method: merged from [41] (transpiration) and [46]

(Knudsen mass spectrometer)

log p

= 8.9796 - 15980/T (17. ) precision: ± 1.3% uncertainty: ^ ± 15%

Table 17.9. Vapor pressure from equation (17.5)

T(K)

4

p x 10

(mm)

T(K)

4 p x 1

(mm)

1200 0.46 1340 11 .

1210 0 .59 1350 13 .

1220 0.76 1360 17 .

1230 0.97 1370 20.7

1240 1.24 1380 25 .

1250 1.57 1390 30 .

1260 1.98 1400 36 .

1270 2.49 1410 44 .

1280 3 .13 1420 53 .

1290 3 . 91 1430 63 .

1300 4 .87 1440 76.3

1310 6.04 1450 91.0

1320 7.47 1460 108 .

1330 9.22 1470 128 .

Thermal Decomposition

All metal sulfates decompose on heating, eventually, with tne evolution

of S0 3 , which in turn dissociates to S0 2 and 02- Na

S °4 0- pt • ° C ) melts to form a stable fluid; no weight loss was observed at ^ 90°

o c • At

1000°C and 1200°C, after 2 hrs, losses of 0.04 wt . ^and 1.05 wt. -

0 , re- spectively, were noted. Analysis of the residue indicated both decomposition

and volatilization had contributed. Decomposition pressure data for the

melt have not been reported.

The equilibrium decomposition data for NapSC^ (crystalline) near the m.pt.,

i.e. 827°C, ca3culated from thermal and thermodynamic values are:

Na

2 S0

4

Na

2 S04

(c)

(c)

Na

2 0

Na

2 0

+ SO- K, 8.22 x 10' 20

( 17 -6 ) (c)

(c)

(gV

+ S0 7 + h0 7 ; K, 1.38 X 10

2 (g)

2 (g)

-19

(17.7 )

and the corresponding equilibrium pressures are in table 17 JO.

Table 17.10, Equilibrium dissociation pressures

T (K) P S0

2 (atm) Pso2 (atm) '

, S0

3 (atm) P total (atm)

1100 -13 3.37x10 -13 1.69x10 8 . 22xl0' 20

5 . 06xl0" 3

References: [14,41-47].

IS. Thermal Conductivity (liquid) (X^)

No thermal conductivity studies reported.

175
Na

2 S04 Thermal Conductivity (solid) (\

)

No thermal conductivity stud ies reported

Cryoscopic Constant (kj>)

Measurement method: calculated from AH£ [40]

Table 17.11. Cryoscopic constant

k .f Uncertainty

(K mol ^kg-l)

67 .

v ± 2%

References [9,40,48-54],

References

[1] Coughlin, J. P., J. Amer, Chem. Soc , , 7_7_, 8 68 (1955),

[2] Stull, D. R., and Prophet, H., "JANAF Thermo chemical Tables','

2nd ed . , NSRDS-NBS 37; U, S. Gov't Printing Office, Washington,

D‘. C. (1971).

[3] Stern, K., "High Temperature Properties and Decomposition of Inorganic Compounds. I. Sulfates", NSRDS-NBS-7, U. S.

Gov’t Printing Office, Washington, D. C, (1969),

[4] Kvist, A., Z. Naturf or sch . , 22a , 208, 467 (1967),

[5] Wagman, D. D., Evans, W. H., Harlow, I., and Dudley, R., "Amer. Inst.

Physics Handbook", Sec. 4, p. 170-216, McGraw Hill Book Co.,

New York, N. Y. (1963)

[6] Jaeger, F. M., Z. anorg . allgm. Chem., 101 , 1 (1917).

[7] Petit, G., and Bourlange, C., Compt. Rend. Acad. Sci. (Paris)

Ser. C., 245, 1788 (1957).

[8] Denielou, L., Fournier, Y., Petitet, J. P., and Tegui, C.,

Compt. Rend. Acad. Sci. (Paris) Ser. C., 269 , 1577 (1969).

[9] Flood, H., Forland , T., and Nesland, A., Acta Chem. Scand.,

_5 , 11 93 (1 951).

[10] Bertozzi, G., and Sternheim, G., J. Phys. Chem., 6_8, 2908

(1964) .

[11] Kvist, A., Z. Naturforsch. , 21a , 1221 (1966); 21a , 1601 (1966).

[12] Jaeger, F. M. , and Kahn, S., Koninkl . Ned. Akad . Vn Wetenschapen

Proc. Ser. B., 1_9, 381 (1961).

[13] Kvist, A., and Schroeder, K. , Z. Naturforsch., 23A , 676 (1968)..

[14] Stern, K. H., and Weise, E. L., "High Temperature Properties and

Decomposition of Inorganic Salts, Part 1. Sulfates . " NSRDS-NBS-7; U. S. Gov’t Printing Office, Washington, D. C.

(1966)

[15] Arndt, K. , Z. El ektrochem . , 1, 337 (1906).

[16] "dangerous Properties of Materials", Sax, N. I., Van Nostrand

Reinhold Co., N. Y. (1969).

[17] "Registry of Toxic Effects of Chemical Substances"

,

Christensen,

H. E., and Lubinbyhl, T. T., eds., U . S. Dept. H.E.W.; U. S.

Gov’t Printing Office, Washington, D. C. (1975).

176
Na

2 S04

[18] Vapor pressure, calculated (see p, 175, this work).

[19] " Potential Hazards in Molten Salt Baths for Hieat Treatment of Metals"

National Board Fire Underwriters Research Report No. 2 (1954).

[20] "Handbook of Reactive Chemical Hazards", Bretherwick, L., Butterworths

Co . , London (197 5)

[21] Janz, G. J., Tomkins, R. P. T., Downey, J. R. , Jr., and Allen, C. B.,

"Safety and Hazards" Chapter in "Eutectic Data", ERDA TID-27163-P1

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[22] Stringer, J., and Whittle, D. P., Metal-Slag -Gas Reactions and Processes, p. 665, Procr Internat. Sym. Electrochem. Soc. , Foroulis,

Z. A., and Smeltzer, W. W. , eds . , (1975).

[23] Goebel, J. A., and Petit, F. S., Met. Trans., £, 1943 (1970),

[24] Sequeira, C. A. C., Tecnica (Lisbon), 37_, 33 (197 5).

[25] Rahmel , A., Electrochim. Acta, £3, 495 (1968).

[26] Dubois, J., and Richard, J., Rev. Gen, Therm,, £2, 805 (1973).

[27] Burrows, B. W. , and Hills, G. J., J. Inst. Fuel, 3_9, 168 (1966).

[28] Rahmel, A., Corros. Sci., 13_, 833 (1973).

[29] Romeo, G., and McKee, D. W. , J. Electrochem. Soc., 1 22 (2) , 188 (1975).

[30] "Metal-Slag -Gas Reactions and Processes"

Proc . Internat, Symposium,

Foroulis, Z. A., and Smeltzer, W. , eds,, The Electrochemical

Soc., Princeton, N. J. (1975).

[31] Baudo, G., and Tamba, A., Brit. Corrosion J., £, 129 (1969).

[32] Bartlett, H. E,, and Johnson, K. E., Canad. J. Chem., £4, 2119 (1966).

[33] Johnson, K. E., "Electrochemical Approaches to Corrosion In Molten

Salts ", Proceedings International Symposium on Metal-Slag-Gas

Reactions and Processes, The Electrochemical Society, Inc.,

Princeton, N. J., p. 581 (1975).

[34] Smirnov, M. V., and Ozeryanaya, I. N., Nauki Tekh, Korros.

Zashch. Korros., £, 171 (1973).

[35] Ketelaar, J. A. A., Chemie Ing. Techn., £5, 667 (1973).

[36] Inman, D., and Wrench, N. S., Brit. Corr . J., £, 246 (1966).

[37] Janz, G. J., and Tomkins, R. P. T., Corrosion, 3£ (in press)-- (1978).

[38] Wagman, D. D., Jobe, T. L., Domalski, E. S., and Schumm, R. H.

cited in "Amer . Inst. Phys. Handbook " 3rd ed , , McGraw-Hill

Book Co . , N. Y. (1972)

[39] Popov, M. M., and Ginzburg, D. M., J. Gen. Chem. USSR, 2_6, 1107 (1956)

[40] Janz, G. J.,et al . , (MSDC-RPI) unpublished work (1977).

[41] Fryxell, R. E., Trythall, C. A., and Perkins, R. J., Corrosion,

£9, 423 (1973).

[42] Kroger, C., and Stratman, J., J. Glastech. Ber . , ££, 311 (1961).

[43] Duval, T., and Duval, C., Anal. Chim. Acta, _2, 97 (1948).

[44] Hegedus, A. J., and Fukker, K., Z. anorg. allgm. Chem., 284 , 20 (1956)

177
Na

2 S04

[45] Spitsyn, I., and Shostak, V. I., J, Gen. Chem. USSR, 1_9, 1801 (1949).

[46] Fryburg, G. C., and Kohl, F. J., NASA, Lewis Res. Center, Cleveland,

Ohio; private communication to G. J. Janz (Feb. 1978).

[47] Kohl, F. J., Stearns, C. A., and Fryburg, G. C., p. 649, "Metal-Slag-Gas

Reactions and Processes," Foroulis, Z. A., and Smeltzer, W. W. , eds., The Electrochem. Soc . , Princeton, N. J. (1975).

[48] Petit, G., and Darmois, E., Compt. Rend., 238 , 261 (1954).

[49] Rossini, F. D., Wagman, D. D., Evans, W. H. , Levine, S., and Jaffe,

I, 3 "Selected Values of Chemical Thermodynamic Properties , NBS

Circ. 500"3 U. S. Gov't Printing Office, Washington, D. C. (1952).

[50] Grjotheim, K. , Malvorsen, T., and Urnes, S., Can. J. Chem., 37 , 1170 (1959).

[51] Kelley, K. K., U. S. Bur. Mines, Bull. 601, (1962).

[52] Wolters, A., Neues Jahrb. Mineral. Geol. Palaont. Berlage Bd .

,

30, 55 (1 91 0).

[53] Kordes, E., Ziegler, G., and Proeger, H. J., Z. Elektrochem . , 58 , 168 (1954).

[54] Kordes, E., Z. Elektrochem., 60_, 629 (1956).

[55] Tanutrov, I. N. , Kostenskii, B. P., Moissev[ G, K. , and Okenev, A. I,,

Trudi Electrokhimii , SSSR, 17, 41 (1971).

178
XVIII. Potassium Sulfate: K

2 SO4

1. Melting Temperature (T^)

Melting point:

1069° + 3 °C [1-3]

References [1-11] .

2. Density (p)

Measurement method: Archimedean technique [12]

p = 2.47497 - 4.5108 x 10' 4 T (18.1)

precision: ^ ± 0.06% uncertainty: ^ ± 1 %

Table 18.1. Densities from equation fl8.1)

T(K)

P (g cm 3

)

T(K)

P_

(g cm 3

) 1350 1.866 1390 1.848

1360 1.861 1400 1.843

1370 1.857 1410 1.839

1380 1 . 853

References [7,12,49-51].

3.

Surface Tension (y ) Measurement method: maximum bubble pressure [ 6 ]

y

= 245.20 - 7.65 x 10

_2

T (18.2)

precision: ± 0.1% uncertainty: ^ ± 0.5%

Table 18.2. Surface tension from equation (18.2)

T(K)

Y (dyn cm 3 )

T(K)

Y (dyn cm *)

1350 141.9 1380 139 .

1360 141.2 1390 138.9

1370 140.4

References [6,7,10,13-15].

4. Viscosity (r\)

No data.

5. Electrical Conductance (k)

Measurement method: ac technique [ 8 ]

k = -0.806035 + 2.01030 x 10* 3 T (18.3)

precision: 'v ± 0.13% uncertainty: ^ ± 3%

For numerical values: see table 18.3

•’179
K

2 S0

4

Table 18,3. Electrical conductance from equation (18.3)

T(K)

K (ohm 1 cm 1

)

T(K)K

(

hm 1 cm 1 ) 1342 1.892 1352 1 . 912

1344 1.896 1354 1.916

1346 1.900 1356 1.920

1348 1.904 1358 1.924

1350 1 . 908 1360 1 . 928

References [5,8,16-19].

6.

Safety and Hazards

A. Hazard rating [20-22]

(i) Inhalation: not reported; ingestion: severe (toxicity)

(ii) Vapor pressure: at m.pt. (1069°C), p

^ 0.07 mm.

K 2 SO 4 melts to form a stable fluid; at 1270°C,

p

^ 1 mm; the decomposition pressures (due to dis

sociation to SO3

, S0 2 , and oxygen) in this temperature range are < 10 ”^ mm.

B. Disaster hazards [20,23-25]

(i) Molten salt bath "explosions": i.e., explosive generation of

steam due to bulk water "carry-over" and/or equipment

failure; i.e., explosive expansion of "trapped" air.

(ii) Sulfates, when heated to decomposition, evolv.e SO 3 , which, in turn, dissociates to SC^ and C^; toxic,

aggressive fumes.

References [20-25].

7.

Corrosion

Table 18.4. Corrosion studies from primary

research literature

Studies Ref erences

Metals 26

Metal s , Fe 27

Ag 28

Electrochemical approach 29

Thermodynamic redox diagrams 26,27,30,31

Molten salts corrosion: reviews 32-34

Annotated corrosion biblio. 35

References [26-35].

8.

Diffusion

No diffusion studies reported.

180
9.

10 .

11 .

12 .

Heat of Fusion (A H°)

Measurement method: averaged value; cryoscopy [2,9,36]

Table 18.5. Heat of fusion

AH °f

! Uncertainty

(kcal mol ) 8 . 7 v ± 4 %

References [2,9,36]

Heat Capacity (C ) Measurement method: drop calorimetry [37]

Table 18.6. Heat capacity

C

p . Temp, range Uncertainty

(cal K'lmol - -*- ) (K)

47 .

1342-1400 ^ ± 3%

References [37] . Volume Change on Melting (A

Measurement method: estimated; from densities [38]

Table 18.7. Volume change on melting

(AV

f /Vs

) Uncertainty

26 . 9% ^ ± 8%

References [38 ]

Vapor Pressure (

va-p

Measurement method: Knudsen effusion and transpiration [39]

log p

= 8.2510 - 12700/T (18.4)

precision: not estimated uncertainty: ^ ± 101

Results reported in equation form.

Table 18.8. Vapor pressure from equation (18.4)

T P T P (K) (mm) (K) (mm)

1350 0.070 1510 0 .692

1360 0 .082 1520 0.787

1370 0.096 1530 0.892

1380 0.112 1540 1 . 01

1390 0 .130 1550 1 .14

1400 0.151 1560 1 .29

1410 0.175 1570 1 . 45

1420 0 .203 1580 1 . 63

1430 0.234 1590 1 . 83

1440 0.270 1600 2 .06

1450 0.311 1610 2 . 31

1460 0 .357 1620 2 .58

1470 0.409 1630 2 .88

1480 0.468 1640 3.21

1490 0 .534 1650 3 .58

1500 0 . 609 1660 3 .98

181
k

2 so4 Thermal decomposition: critical analysis; NSRDS study [1]

All metal sulfates eventually decompose, evolving SO

3 which, in turn dissociates

to SO2 and O 2

. K 7 SO4 (m.pt. 1069°C) melts without significant decomposition.

The weight loss observed at 1000°C after 2 hrs was barely measurable, whereas

at 1200°C, and comparable time, the weight loss was ^ 3.6%. The interpretation

of these data as due to two simultaneous processes, sublimation and decomposition

is in conflict. High temperature thermal data are insufficient to resolve the

discrepancies

References [1,39-451.

13. Thermal Conductivity (liquid) (X

No thermal conductivity studies reported.

14. Thermal Conductivity (solid) (X ) s No thermal conductivity studies reported.

15. Cryoscopic Constant

Measurement method: calculated from AH| [38]

Table 18.9. Cryoscopic constant

k.

f Uncertainty

(K mol'^kg - -*-)

71.7 ^ ± 4%

References [2,9,36,38,46-48],

16.

References

[1] Stern, K. , "High Temperature Properties and Decomposition of

Inorganic Salts. I. Sulfates ”

,

NSRDS-NBS-7 ; U. S. Gov t Printing Office, Washington, D. C. (1966).

[2] Rossini, F. D. , Wagman, D. D., Evans, W. H., Levine, S., and

Jaffe, I., "Selected Values of Chemical Thermodynamic

Properties , NBS Circ. 500", U. S. Gov't Printing Office,

Washington, D. C. (1952).

[3] Kelley, K. K .," Contributions to the Data in Theoretical

Metallurgy . XIII and XIV", U. S. Bur. Mines. Bull. 592 , 149 pp (1961)

[4] Wagman, D. D., Evans, W. H., Harlow, I., and Dudley, R., Amer.

Inst. Phys. Handbook, Sec. 4, p. 170-216, McGraw Hill Book

Co. , N. Y. (1963) .

[5] Arndt, K. , Z. Elektrochem . , 1_2, 337 (1906).

[6] Neithamer, R. W. , and Peake, J. S., J. Chem. Eng. Data, (>, 197 (1961).

[7] Jaeger, F. M., Z. anorg. allgm. Chem., 10^, 1 (1917).

[8] Kvist, A., Z. Naturfor sch . , 21a , 1221, 1601 (1966).

[9] Petit, G., and Bourlange, C., Compt. Rend. Acad. Sci. (Paris),

245, 1788 (1957).

[10]

Sokolova, I. D., and Voskresenskaya, N. K., Russ. J. Phys.

Chem., 3_6, 502 (1962).

182
[11] Douglas, T. B. , Trans. Amer. Soc. Mech. Eng., 7_9, 23 (1957).

[12] Neithamer, R. W. , and Peake, J. S., J. Chem. and Eng. Data 6, 197 (1961).

[13] vide infra ref. [1],

[14] Bertozzi, G., and Soldani, G. , J. Phys. Chem., 7_1 , 1536 (1967).

[15] Semenchenka, V. K., and Shikhobalova , L. P., Zh. Fiz. Khim.,

21, 1387 (1947).

[16] Matiasovsky, K., Danek, V., and Lillebuen, B., Electrochim.

Acta, 17, 463 (1972)

[17] Polishchuk, A. F., Shurkahal, T. M. , et al . , Ukr . Khim.- Zh.

39, 760 (1973).

[18] Markov, B. F., Polishchuk, A. F., et al . , Ukr. Khim. Zh.

39, 262 (1963).

[19] Biltz, W. , and Klemm, W. , Z. anorg. allgm. Chem., 152, 267

(1926) .

[20] "Dangerous Properties of Materials ", Sax, N. I., Van Nostrand

Reinhold Co . , N. Y. (1969)

[21] "Registry of Toxic Effects of Chemical Substances'', Christensen,

H. E., and Lubinbyhl , T. T., eds., U. S. Dept. H.E.W; U. S.

Gov't Printing Office, Washington, D. C. (1975).

[22] Vapor pressure, calculated (see p. 181, this work).

[23] "Potential Hazards in Molten Salt Baths for Heat Treatment of

Metals", National Board Fire Underwriters Research Report

No. 2 (1954).

[24] "Handbook of Reactive Chemical Hazards", Bretherwick, L.,

Butterworths Co., London (1975),

[25] Janz, G. J., Tomkins, R. P. T., Downey, J. R. , Jr., and Allen, C. B.,

"Safety and Hazards" Chapter in "Eutectic Data", ERDA TID- 27163 -PI

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[26] Rahmel , A., Electrochim. Acta, 1_3^ 495 (1968).

[27] Burrows, B. W. , and Hills, G. J., J. Inst. Fuel, 39, 168 (1966).

[28] Rahmel, A., Corros. Sci., 13_, 833 (1973).

[29] Johnson, K. E., "Electrochemical Approaches to Corrosion in

Molten Salts", Proceedings International Symposium on MetalSlag-Gas Reactions and Processes, The Electrochemical Society,

Inc., Princeton, N. J., p. 581 (1975).

[30] Bombara, G., Baudo , G., and Tamba, A., Corrosion Sci., 8_, 393 (1968).

[31] Baudo, G., and Tamba, A., Brit. Corrosion J. , 4, 129 (1969).

[32] Smirnov, M. V., and Ozeryanaya, I. N., Nauki . Tekh. Korros.

Zashch. Korros., 2_, 171 (1973).

[33] Inman, D., and Wrench, N. S., Brit. Corr. J., ]L , 246 (1966).

[34] Ketelaar, J. A. A., Chemie Ing. Techn., 4_5, 667 (1973).

[35] Janz, G. J., and Tomkins, R. P. T., Corrosion, 34, (in press)

(1978) .

[36] Kelley, K. K., U. S. Bur. Mines, Bull. 610 (1962).

183
[37]

K

2 S0

4 Douglas, T. B., Brookhaven National Laboratory, Report No.

BNL-2446 (1954); Trans. Am. Soc. Mech. Eng., 79, 23 (1957).

[38] Janz, G. J., et al . , (MSDC-RPI) unpublished work (1977).

[39] Halstead, W. D., Trans. Faraday Soc., 66_, 1966 (1970).

[40] Dubois, J., and Millet, J., Compt. Rend., 266C , 852 (1968).

[41] Hegediis, A. J., and Fukker, K., Z. anorg . allgm. Chem., 284,

20 (1956)

[42] Malard, C., Bull. Soc. Chim. France, 2296 (1961).

[43] Spitsyn, I., and Shostak, V. I., J. Gen. Chem. USSR, 19, 1801

(1949) .

[44] Kroger, C., and Stratmann, J., Glastechn. Ber . , 3j4, 311 (1961)

[45] Briner, E., Pamm , G., and Paillard, H., Helv. Chim. Acta, 31 , 2220 (1948); 32, 635 (1949).

[46] Plato, W. , Ber. dtsch. Chem. Ges., 3_6, 2357 (1903).

[47] Kordes, E . , Z . Elektrochem .

,

6J3 , 629 (1956)

[48] Kordes, E

_58 , 168

. , Ziegler , G . , and

(1954) . Proeger , H. J., Z. Elektrochem.,

[49] Kvist, A

, Z . Naturforsch .

,

21a, 1221 (1966) 21 a, 1601

(1966).

[50] Jaeger, F. M. , Kahn, S., Koninkl . Ned. Akad. Vn Wetenschapen

Proc. Ser. B., 19 , 381 (1961).

[51] Kvist, A., Schroeder, K. , Z. Naturforsch. 23a, 676 (1968).

184
XIX. Sulfur

1. Melting Temperatures (T

Melting points [1-3,46]

Monoclinic: 115° ± 0.5°C

Rhombic: 110 °C

Transition temperature:

Rhombic * monoclinic: 95°C

Figure 19.1. Sulfur phase diagram

References [1-7,46].

2. Density (p)

Measurement method: dilatometer [8-10]

p = a - bT (19.1)

Table 19.1. Parameters of equation (19.1), precisions and uncertainties

Temp,. range(K) a b x 10 3 Prec ision Uncer tainty

394-428 2 .1365 0 • 84 6 + 0. 01% y±0 .5%

451-718 2 . 0445 0.610 +0.09% %+0. 5%

185
Sulfur

Table 19.2. Densities from equations in table 19.1

T(K)

P (g cm 3

)

T(K)

P (g cm 3

) 400 1 .7982 560 1.7027

420 1 . 7813 580 1.6905

440 (1.771) 600 1.6783

460 1. 7637 620 1.6661

480 1 .7515 640 1.6538

500 1.7393 660 1.6416

520 1.7271 680 1.6294

540 1 . 7149 700 1.6172

550 1 .7088 710 1 .6111

Value in brackets interpolated.

References [8-13].

3. Surface Tension ( y ) Measurement method: capillary rise; maximum bubble pressure [14]

y

= 102.1 - 0.105 T (388-432 K) (19.2)

Y

= 81.2 - 0.0566 T (432-707 K) (19.3)

precision: ^ ± 0.5% uncertainty: 'v ± 1%

Table 19.3. Surface tension from equations (19.2) and (19.3)

T(K)

Y (dyn cm 1 )

T(K)

Y (dyn cm 1 )

380 (62.2) 510 52.3

385 (61.7) 520 51.8

390 61.1 530 51.2

395 60.6 540 50.6

400 60.1 550 50.0

405 59 .560 49.5

410 59.0 570 48 .

415 58.5 580 48.4

420 58.0 590 47 .

425 57.5 600 47 .

430 56.9 610 46.7

440 56.3 620 46.1

450 55.7 630 45.5

460 55.2 640 45.0

470 54.6 650 44.4

480 54.0 660 43.8

490 53.5 670 43.3

500 52.9 680 42.7

690 42.1

700 41.6

References [8,12,14].

4. Viscosity (r\)

Measurement method: capillary; rolling ball; and modified capillary [15,16

n = a + bT + cT

2 (19.4)

precision: in table 19.4 uncertainty: 'v ± 1.5%

186
Sulfur

Table 19.4. Parameters of equation (19.4) and precisions

a x 10“ 3 -b x 10" 2 c x 10 2 T range (K) Precision

31.8865 1.1359i 10.1212 466-533 ^±3.5%

9 • 312 5 0.3148 2.6654 544-589 ^±2 . 9%

Table 19.5. Viscosity from equations in table 19.4

T(K)

n (p)

T(K)

n(p)

T(K)

h (P)

322 .0.759 427.6 0.065 511.0 250

333 .

0.491 430.4 0.067 522 .

160

344.3 0.342 432 .

0.12 533.2 110

355 .0.253 436 .

120 544.3 74

366 .

0.193 438.8 210 555 .

52

377.6 0.149 444.3 460 566.5 34

388 .0.119 455 .

890 577 .

22

394.3 0.110 461.0 930 588. 7 18

399 .

0.100 466.5 910 590 (14)

405 .0.089 472 .

820 600 ( 10 ) 411.0 0.080 477.6 730 610 (7)

416.5 0.074 488.7 570 620 (5)

422 .0.067 499.9 390 630 (3.5)

Values in parenthesis, by extrapolation

References [15-17].

5, Electrical Conductance CkI

Measurement method: dc technique [67,68],

k = 2,60 x 10 -3

exp [ -22265/RT] (490-690 K) (19,5)

precision: ^ + 5% uncertainty: ^ + 10%

Table 19.6.1. Electrical conductance 3

T(K)

ic x 10 14

Co hm 1 cm 1 )

T(K)

K x 10 14

(ohm

’-1 cm

” 1 ) 398.15 0.9 428.15 1.8

403 .15 1 . 2 433.15 1 .

408,15 1.4 438 .15 1.8

413.15 1.7 443.15 2 ,

418 . 15

423.15

2 . 05

2.4

448.15 2.7

Experimental values [67]; zone refined sulfur

187
Sulfur

g Table 19.6.2. Electrical conductance from equation (19.5)

T(K)

x x 10 12

(o hm^ 1 cm 1 )

T(K)

K X 10 1

(ohm" 1 cm

-1

)

490 0.305 600 20.16

500 0.481 610 27 . 38

510 0.747 620 36.82

520 1.14 630 49.05

530 1.71 640 64.77

540 2 . 53 650 84.79

550 3 .69 660 110.1

560 5 . 31 670 141 .

570 7 .54 680 181 .

580 10.59 690 230.3

590 14 .69

a Zone refined sulfur [68]

Table 19.6.3. Electrical conductivities of molten

sulfur of various purities

Sulfur quality K 2c 1 0

1 4

( o hm -1 cm" 1 ) 448.15 K 533 .15 K 615 K 628 K

zone refined [67,68] 2 .

194 3178 4633

resublimed [66] b

refluxed with MgO [67, 69]

3 16 130

"hot spot" reflux [67,70] a 22 320

oxidation method [67,71] 2 .

Zone refined sulfur

doped with 0.02% benzil [67] 43

doped with 0.015% bromine [67] 1100

doped with 0.2% bromine [67] 22000

Resublimed sulfur

saturated with Na 2 S 5 [66] c

a Hydrocar bon content : 3.7 x 10 4 % [69,72]; 5.2 x 10 4 -6 [70,72];

8.2 x 10" 4 % [71,72]

b

K, 1 x 10 _8 ohm _1 cm -1

C <, 1 x 10 7 ohm -^cm ^ for data at other temperatures in the range

576-690K, see [66]

References [18-23,66-72].

188
Sulfur

6. Safety and Hazards

A. Hazard rating [24-26]

(i) low

(ii) vapor pressure: at m.pt. of sulfur (115°C), ^ 0.03 mm;

increases rapidly to 1 mm at ^ 185°C; the boiling point

(atmospheric pressure) is ^ 444. 6°C

B. Disaster hazards [24,27-29]

(i) When heated to decomposition, sulfur burns

formation of SOp and SO^ ; toxic aggressive

with the

fumes

References [24-29]

7

.

Corrosion

Table 19.7. Corrosion studies from primary research literature

References [30-33].

8.

Diffusion

Measurement method: cited in tabulations

List of diffusing species investigated in sulfur as solvent

P, s The italicized species indicate studies with insufficient data-sets

for characterization of temperature -dependence of diffusion coefficients. For these species: see table 19.8.4

Equation

D = A exp [ -E/RT] (19.6)

precision: in table 19.8.2 uncertainty: in table 19.8.1

189
Sulfur

Table 19.8.1 Diffusion techniques, uncertainties, and species

Diffusion technique Uncertainty

of recommended study (in values of D) Species

capillary

porous frit

~ + 20 %

'v* + 2 0%

3 2 p

3 5 S

Table 19,8,2, Diffusion equation parameters, precision,

and recommended study

Species A x 10 3 (cm 2 sec

-1

)

E (cal mol” 1 ) Temp , rang e CK)Pr ec is ion Recommend ed

study

3 5 s 281700 15167 395-420 ± 5.5% 73

35 S 0. 218 5348 540-590 ± 2.5% 73

Table 19,8.3. Diffusion coefficients of sulfura

T(K)

D x 10 6 (cm 2 sec" 1 )

T(K)

D x 10 6 (cm 2 sec" 1

)

T(K)

D x 10 6 (cm 2 sec" 1 )

395.6 1 . 05 431 .

1.45 488.1 0.95

396.1 1.20 436.1 1 , 31 504.1 0.80

398.1 1,45 436.5 1.24 509.1 0.83

399.1 1.52 440.6 1.17 513.1 0.91

412.1 2 . 50 443.1 1 . 53 541.1 1 .55

414.6 2.80 453.1 1 . 03 546.1 1 .52

421.1 3 . 90 456.1 0.90 547 .1 1 . 23

422.1 3 .85 458.1 0.86 551.1 2 . 05

422 .

2.42 465.1 0.71 565 .

1 . 90

426.1 2 .45 47 2.1 0.71 580.1 2.34

427 .

6

2 . 90 474 .1 0.84 580.1 2.10

428.1 3.22 479.1 0.87 589.1 2 .26

a Exp er im en t a 1 values of diffusion coefficients.

Table 19.8.4. Diffusion coefficients for species not

included in table 19.8.3.

Species T D x 10 6 Ref . (K) (cm'1 sec )

P 387 0.82 34

References: P, 34; S, 73.

190
Sulfur

9. Heat of Fusion ( Measurement method: adiabatic calorimetry [35]

Table 19.9. Heat of fusion

AH°

t _i (kcal mol ) Uncertainty

3 . 07

a ^ ± 0.5%

a calc'd as Sg

References [1,6,35-45].

Heat Capacity (C ) Measurement method: adiabatic calorimetry [36,42,43]

Table 19.10. Heat capacity a

c C T P T P (K) (cal K

-

mol ~ 1 ) (K) (cal K

_1 mo

-1

)

393 7 .40 498 8 . 53

398 7 .42 503 8.52

403 7 . 44 508 8 . 51

408 7 .46 513 8 .51

413 7 .49 518 8.50

418 7 . 54 523 8 . 50

423 7 . 61 528 8 .50

428 7 .83 533 8.50

432 8 0 3 3 538 8.51

435 12.48 543 8 .51

438 11.59 548 8 .52

443 10.70 553 8 . 53

448 10.13 558 8 .55

453 9.73 563 8 .56

458 9.46 568 8 .56

463 9.22 573 8 .57

468 8.98 578 8.60

473 8.83 583 8 . 62

478 8.73 588 8.65

483 8.66 593 8.68

488 8.57 598 8.70

493 8.55

uncertainty: -v ± 1%

^he data cannot be expressed as a simple equation since there is an abrupt

increase in at ^ 428 K (155°C) peaking at ^ 432 K (159°C)

References [1,5,6,35,36,42,43,46,47] .

11. Volume Change on Melting (AF^J

Measurement method: estimated [48]

Table 19.11. Volume changes and uncertainties

Transition

monoclinic liquid

.liquid -^liquid

(ring) (polymer)

Temp (°C)

115

159

Uncertainty

^+ 5 % ^+ 3 %

References [48-51].

191
Sulfur

12. Vapor Pressure (pr ) vap

Measurement method: isoteniscope ; modified dew point [55]

log p

= A + B/T (19.7)

Table 19.12. Parameters of equation (19.7), temperature range, and precisions

Temp, range

(K)

A -B Precision

413-453 9 o 3614 4263 0 7 ±0.72%

463-613 8.1246 3682.3 + 1.2%

613-653 7 „ 5549 3347.6 + 5.2%

663-693 7.4553 3282.5 +0.01%

693-723 7.4254 3261.7 ±0o01%

Table 19.13. Vapor pressure from equations in table 19.12

T P T P (K) (mm) (K) (mm)

420 0.16 580 59.7

430 0.28 590 76.5

440 0.47 600 97.1

450 0.77 610 122.5

460 1.32 620 143.1

470 1 .95 630 174.3

480 2.84 640 211.0

490 4.07 650 254.0

500 5 .75 660 303.6

510 8.02 670 359.8

520 11.0 680 424.7

530 15.0 690 499.0

540 20 .

700 583.2

550 26 .

710 678.4

560 35.4 720 785.7

570 46.2 730 906.4

References [52-57].

13. Thermal Conductivity (liquid) (X^)

Measurement method: horizontal plate

precision: not estimated

[58]

uncertainty:^ ± 20%

For numerical values: see table 19.14

192
Sulfur

Table 19.14. Thermal conductivity of melt

T(K)

A x 10 4 (cal chi

'-1 sec

~ 1 K

_1

)

T(K)

A x 10 4 (cal cm

see -K

-1

) 388 3.14 438 3.36

393 3 .16 443 3 .40

403 3.21 453 3 . 51

413 3.26 463 3. 60

423 3.31 473 3 . 69

433 3 .36 483 3 .78

References [58-64].

14. Thermal Conductivity (solid) ( A^ J Measurement method: steady state linear heat flow [63]

precision: not estimated uncertainty: ^ ± 101

Table 19.15. Thermal conductivity of solid

T(K)A x 10 4 (cal cm -1 sec" 1 K

-1

) Rhomb

c Sulfur

285 . 03 6.58

292 . 61 6.56

306.38 6.42

316.76 6.33

322.26 6.28

332.26 6.22

337.27 6 .17

347.23 6 . 08

354.80 6.00

Monoclinic Sulfur

369.65 3. 69

370.94 3 . 67

371.41 3 . 58

376.17 3 . 67

378.38 3.72

382.13 3 . 58

383 .10 3 . 64

384.16 3.53

384.75 3 .72

386.38 3 . 58

386.92 3.80

388 . 11 3.53

388 . 67 3 . 64

References [63-65],

193
Sulfur

15. Cryoscopic Constant

Measurement method: calculated from AH£ [48]

Table 19.16. Cryoscopic constant

k

f (K mol ‘'’kg 1)

Uncertainty

25.0 ^ ± 0.5%

References [48]

References

[1] West, E. D., J. Amer. Chem. Soc., 81, 29 (1959).

[2] Tuller, W. N., ed., "The Sulfur Data Book ", McGraw-Hill Book Co., N. Y.

(1954) .

[3] Komarek, K. L. , Miller, E., and Schick, G., Monatsh. Chem. , 104,

1139 (1973).

[4] Rosen, E., and Tegman, R. , Chemica Scripta, 2_, 221 (1972).

[5] Eastman, E. D. , and McGavock, W. C., J. Amer. Chem. Soc., _59, 145 (1937).

[6] Oelsen, W. , and Oelsen, 0., Z. Elektrochem. , 6_0^, 157 (1956).

[7] Feher, F., and Hellwig, H. , Z. anorg. allgm. Chem., 294 , 71 (1958).

[8] Kellas , A. M. , J. Am. Chem. Soc., 113 , 903 (1918).

[9] Matson, R. F., Freeport Sulfur Co., cited in : "The Sulfur Data Book"

,

Tuller, W. N. , ed . , McGraw-Hill, N. Y. (1954).

[10] Feher, F., and h'ellurgand, E., Z. anorg. allgm. Chem., 294 , 63 (1958).

[11] Mondain-Monval , P., and Schneider, P., Bull. Soc. Chem., 4_3, 1302 (1928).

[12] Shirai, T., Nippon Kagaku Zasshi , 7

, 696 (1951).

[13] Rosental, S. , Bull. Soc. Acad. Polon. Sci. Krakow, A, 377 (1928).

[14] Fanel 1 i

,

R. , J. Amer. Chem. Soc., 72, 4016 (1950).

[15] Fanelli

,

R. , J. Amer. Chem. Soc., 68 , 1832 (1945).

[16] Bacon, R. F., and Fanelli, R. , J. Amer . Chem . Soc . , 65

,

639 (1943).

[17] Doi , T . , Rev. Phys. Chem., Japan, 33, 41 (1963); ibid., 3_2 , 7 (1962)

[18] Feher, F., and Lutz, H. D. , Z. anorg. allgm. Chem., 333 , 216 (1964).

[19] Gordon, C. K. , Phys . Rev., 95_, 306 (1954).

[20] Foussereau, G. E. M. , Compt. Rend., 95, 216 (1882); J. de Physique, 4, 189

(1885) .

[21] Wigand, A., Ber. d. Dtsch Phys. Ges., 1_0, 495 (1908).

[22] Black, D. H. , Proc. Cambridge Phil. Soc., 22_, 393 (1924).

[23] Monkman, J., Proc. Roy. Soc., 4d3, 136 (1889).

[24] "Dangerous Properties of Materials", Sax, N. I., Van Nostrand Reinhold

Co. , N. Y. (1969)

[25] "Registry of Toxic Effects of Chemical Substances", Christensen, H. E., and

Lubinbyhl, T. T., eds . , U. S. Dept. H. E. W. , U. S. Gov't Printing

Office, Washington, D. C. (1975).

194
Sulfur

[26] Vapor pressure, calculated (see p.192, this work).

[27] "Potential Hazards In Molten Salt Baths for Heat Treatment of Metals ",

National Board Fire Underwriters Research Report No. 2 (1954).

[28] "Handbook of Reactive Chemical Hazards ", Bretherwick, L., Butterworths

Co . , London (1975)

[29] Janz, G. J., Tomkins, R. P. T., Downey, J. R. , Jr., and Allen, C. B.

"Safety and Hanzards"

Chapter in "Eutectic Data"

ERDA TID-27163-P1

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[30] West, J. R., Chem. Engineering, p. 225 (October, 1946).

[31] Szawlovska-Wallisch , K. , Czas. Tech. (Krakow), M (5) , 44 (1970).

[32] Stafford, K. N. , Metal Rev., 1£ (138), 153 (1969).

[33] Foroulis, Z. A., "Oxidation of Iron In Sulfur Vapor At Electrical Temperatures ”, p. 522 in Proceedings Intern. Symp . on Metal -Slag-Gas Reactions

and Processes, The Electrochemical Soc. , Princeton, N. J. (1975).

[34] Poczynajlo, A., Nukleonika, 2_0 , 999 (1975).

[35] Feher, F., Gorier, G. P., and Lutz, H. D., Z. anorg. allgm. Chem., 382,

135 (1971).

[36] Komarek, K. L. , Miller, E., and Schick, G., Monatsh., 104 , 1139 (1973).

[37] Neumann, K. , Z. physik. Chem., A1 71 , 416 (1934).

[38] Mondain-Monval , P., Bull Soc. Chem. (France), 3£, 1349 (1926).

[39] Tammann, G., "Crystallization and Melting", J. A. Barth Publ., Leipzig

(1903)

[40] Wigand, A., Z. physik. Chem., 6£, 273 (1908).

[41] Irataka, I., Sci. Repts., Tohoku Univ. (Japan), Ser. I, £, 99 (1919).

[42] Braune, H. , and Moller, 0., Z. Naturforsch. , £, 210 (1954).

[43] Yoshioka, T., Sci. Repts. , Tohoku Univ. (Japan), Ser. I., £4, 136 (1960).

[44] Lewis, G. N. , and Randall, M. , J. Amer. Chem. Soc., 3_3 , 476 (1911).

[45] Stratton, K. , and Partington, J. R. , Phil. Mag. [6], £3, 436 (1922).

[46] Stull, D. R. , and Prophet, H. (eds . ) , "JANAF Thermochemical Tables", 2nd

Ed., NSRDS-NBS -37 ; U. S. Gov't Printing Office, Washington, D. C. (1971).

[47] Bradley, R. S., Trans. Faraday Soc., 5_0 , 1182 (1954).

[48] Janz, G. J., et al., (MSDC-RPI) unpublished work (1977).

[49] Density data cited in "The Sulfur Data Book", Tuller, W. N. , ed., pp . 16,

17; McGraw-Hill Book Co., N. Y. (1954).

[50] MacKnight, W. J., and Tobolsky, A. V., sulfur density data cited in

"Elemental Sulfur - Chemistry and Physics", Meyer, B., ed., p. 103,

J. Wiley (Interscience) Publ., N. Y. (1965).

[51] Poulis, J, A., and Massen, C. H. , densities of sulfur (liquid. . . and

liquid

(p 0 iymer )

, cited in "Elemental Sulfur - Chemistry l ringJ

and Physics", Meyer, B., ed., p. 115, J. Wiley (Interscience) Publ.,

N. Y. (1965).

Ruff, 0., and Graf, H. , Z. Anorg. Chem,, 5_£, 209 (1908).

Matthies, R. , Physik. Z., 7, 395 (1906).

[52]

[53]

195
Sulfur

[54] Bodenstein, P., Z. Phys . Chem. , 20^ 113 (1899).

[55] West, W. A., and Menzies, A. W. C., J. Phys. Chem., 3J5, 1880 (1929).

[56] Braune, H. , Peter, S., and Neveling, V. , Z. Naturforsch. , M, 32 (1951).

[57] Rau, H. , Kutty, T. R. N. , and Guedes de Carvalho, J. R. F., J. Chem.

Thermo. , 5, 833 (1973)

[58] Kaye, G. W. C., and Higgens, W. F. , Proc. Roy. Soc., 122A , 633 (1929).

[59] Turnbull, A. G. , Ph.D. Thesis, Imperial College of Science and Technology,

London, 1959.

[60] "Landolt-Bornstein Tables!,' 6_, (No. 5), p. 72, Springer -Verlag , Berlin, 1968.

[61] Borison, V. M. , and Zasetskii, L. P., Trudi. Gos. Nauchn. Issled. Inst.

Gorno. Khim. Syrya, 6^, 436 (1960).

[62] Chatterji, D. , "Development of Sodium- Sulfur Batteries for Utility

Applications", EPRI EM-266 (Dec. 1976).

[63] Sugawara, A., J. Appl. Phys., 36^ 2375 (1965).

[64] Yoshizawa, Y. , Sugawara, A., and Yamada, E., J. Appl. Phys., 35, 1354

(1964) .

[65] vide infra ref. [61] .

[66] Cleaver, B. , Davies, A. J., and Hames, M. D. , Electrochim. Acta, 18^, 719

(1973)

[67] Feher, F., Heider, R. , Barnert, D. , and Lutz, H. D. , Z. anorg. allg. Chem.,

399 , 77 (1973).

[68] Barnert, D., Dissertation, Univ. Cologne, 1973.

[69] Bacon, R. F. , and Fanelli, R. , Ind. Eng. Chem., 34^, 1043 (1942).

[70] Wartenberg, H. V. , Z. anorg. allg. Chem., 286 , 243 (1956); 297 , 226 (1958).

[71] Murphy, T. J. , Clabaugh, W. S., and Gilchrist, R. , J. Res. Nat. Bu. Stand.,

64A , 355 (1960).

[72] Fehrer, F., Lutz, H. D., and Obst, K., Z. anal Chem., 224 , 407 (1967); , Krautscheid, S., Dissertation, Univ. Cologne (1967).

[73] Saxton, R. L. , and Drickamer, H. G., J. Chem. Phys., 21^, 1362 (1953).

196
XX. Sodium Sulfide: Na£S

1. Melting Temperature ( T^)

Melting point:

1170° ± 10°C [1,4-8]

References [1-9]

2. Density (p)

No data.

3. Surface Tension (y)

No data.

4. Viscosity (r\)

No data.

5. Electrical Conductance (k)

No data.

6.

Safety and Hazards

A. Hazard rating [10,11]

(i) Inhalation: variable

• as sulfides and polysulfides, the rating is similar to

sodium hydroxide

• on reaction with moisture/water, is liberated; the

inhalation hazard rating for H^S is severe; i.e., highly toxic

(ii) vapor pressure: no data

B. Disaster hazards [10,12-14]

(i) Molten sulfides and polysulfides may react violently (explosively)

with strong oxidants: H 2 S evolved on contact with moisture/water

can form explosive mixtures with air; H^S, highly toxic.

(ii) Sulfides and polysulfides when heated to decomposition, or contacted with water, steam, acids, produce highly toxic fumes

(oxides of sulfur, ^S) . Dangerous.

References [10-14].

7.

Corrosion

For corrosion studies, see sodium polysulfides, Na ? S

Z X

8.

Diffusion

No diffusion studies reported with molten Na

2 S as solvent.

197
Na

2 S

10 ,

Heat of Fusion (k Hj.)

Measurement method: calc’d [19]

Table 20.1. Heat of fusion

AH ° (kcal mol ) Uncertainty

5.0 ^ ± 20%

References [3,15-19].

Heat Capacity (£7 ) Measurement method: estimated [18,20]

C = 21.516 + 2.24 x 10

_4

T (20.1)

P

precision: ^ ± 0.2% uncertainty: ^ ± 5-10%

Table 20.2. Heat capacity from equation (20.1)

T(K)

C

P . (cal K

_

mo 1 -

)

T(K)

C

P (cal K'^ol' 1 ) 1300 21.807 1480 21.848

1320 21.812 1500 21.852

1340 21.816 1600 21.874

1360 21.821 1700 21.897

1380 21.825 1800 21.919

1400 21.830 1900 21.942

1420 21 .834 2000 21.964

1440 21.839

1460 21.843

11 .

References [18,20,21].

Volume Change on Melting (A V „)

No data; but see NaF, NaCl , NaNO^...

12. Vapor Pressure (p , ) r vap

No vapor pressure data.

Caution: When heated to decomposition, or contacted with water vapor,

is liberated (highly toxic).

13. Thermal Conductivity (liquid) ( A ) Measurement method: comparative technique [22]

precision: not estimated uncertainty: ^ ± 201

For numerical values: see table 20.3.

198
Na

2 S

Table 20.3. Thermal conductivity of melt

T(K)

X x 10 4 (cal cm

s ec" 1 K

-1

) Sample

type

573 4.06 a 623 4 .06

573 8.36 b

623 8.36

aNa 7 S-C-S composite with the graphite fibers randomly oriented.

L ^ DNa

2 S-C-S composite with the graphite fibers oriented in the direction

of heat flow.

References [22] .

14. Thermal Conductivity (solid) (X ) s No thermal conductivity studies reported.

15. Cryoscopic Constant

Measurement method: calculated from AH° [23]

Table 20.4. Cryoscopic constant

-

f -1

(K mol '•kg ) Uncertainty

20 .

'v ± 3%

Reference [23]

16.

References

[1] Rosen, E., and Tegman, R. , Chimica Scripta, 2_, 221 (1972).

[2] Pearson, T., and Robinson, P., J. Chem. Soc., p. 1473 (1930).

[3] Rossini, F. D., Wagman, D. D. , Evans, W. H. , Levine, S., and Jaffe, I.,

"Selected Values of Chemical Thermodynamic Properties , NBS Circ.

500 ; U. S. Gov't Printing Office, Washington, D. C. (1952).

[4] Bunzel, E. G., and Kohlmeyer, E. J., Z. Anorg. Chem., 254 , 1 (1947).

[5] Tegman, R. , and Warnqvist, B., Acta Chem. Scand., 26_, 413 (1972).

[6] Courtois, G., Compt. Rend., 207 , 1220 (1938).

[7] Ovechkii, E. K. , Shevtsova, L. I., Voitsekhovskii , A. E., and

Kuznetsova, L. V. , Zh. Neorg. Khim., 16^, 3156 (1971).

[8] Ovechkii, E. K. , Shevtsova, L. I., Voitsekhovskii, A. E., Oboznaya,

L. I., and Kuznetsova, L. V., Zh. Neorg. Khim., 18_, 1084 (1973).

[9] Ley, P. , Chem. Zeit., 8_5 , 859 (1934).

[10] "Dangerous Properties of Materials", Sax, N. I., Van Nostrand Reinhold

Co. , N. Y. (1969) .

[11] "Registry of Toxic Effects of Chemical Substances"

Christensen, H. E ., and Lubinbyhl, T. T., eds., U. S. Dept. H. E. W. , U. S. Gov't Printing

Office, Washington, D. C. (1975).

199
[ 12 ]

[13]

[14]

[15]

[16]

[17]

[18]

[19]

[ 20 ]

[ 21 ]

[ 22 ]

[23]

Na

2 5

’’Potential Hazards In

National Board Fire

Molten Salt Baths for Heat Treatment of Metals"

,

Underwriters Research Report No. 2 (1954).

"Handbook of Reactive Chemical Hazards ", Bretherwick, L., Butterworths

Co., London (1975).

Janz,: G. J., Tomkins, R. P. T., Downey, J. R. , Jr., and Allen, C. B. , •"Safety and Hazards"

,

Chapter in "Eutectic Data", ERDA TID-27163-P1

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

Kelley, K. K. , U. S. Bur. Mines, Bull. 393, p. 115 (1936).

Friedrich, L. P., Metall. u. Erz., U, 167, 196 (1914).

Landolt-Bornstein, in "Zahlenwert und Funktionen aus Physik. Chemie.,

Astronomie, Geophysik und Technik", 6th Ed., II (4) p. 202, Bartels,

J., Borchers, H. , Ten Bryggencate, P. , Hausen, H. , Hellwege, K. H.

,

Shaefer, K. L. , and Schmidt, E. (eds.), Springer-Verlag, New York- (1961).

Stull, D. R. , and Prophet, H. (eds.), "JAHAF Thermochemical Tables", 2nd.

Ed., NSRDS-NBS 37; U.S. Gov't Printing Office, Washington, D. C. (1971).

Wagman, D. D. , Nat. Bur. Stds . , U. S. Dept. Comm, (unpublished work),

private communication to G. J. Janz (Mar., 1978).

Barin, I., and Knacke , 0 "Thermochemical Properties of Inorganic

Substances Springer-Verlag, N. Y. (1973).

Kubachewski, 0., Evans, E. L. L. , and Alcock, C. B Metallurgical

Thermochemistry" Pergamon Press, London (1967).

Chatterji, D. , General Electric Co., R. 8 D. Center, "Development of

Sodium- Sul fur Batteries for Utility Applications"

,

EPRI EM-266 (Dec.

1976) . Janz, G. J., et al., (MSDC-RPI) unpublished work (1977).

200
XXI. Sodium Disulfide: ^282

1. Melting Temperature (T ) Melting point:

482° ± 2

0 C [1]

References [1,2] .

Density (p)

No data; however, see sodium polysulfides, Na2S

x

.

Surface Tension (y)

No data; however, see sodium polysulfides, Na2S

x>

Viscosity (r\)

No data; however, see sodium polysulfides, Na ? S .

L. A

Electrical Conductance (<)

No data; however, see sodium polysulfides, Na2S

x>

Safety and Hazards

No data; see Na

2 S and Na

2 Sx for observations on hazards

Vapor pressure: the sulfur pressure above molten ^282 at ^ 1000°C is

approx. 15 mm.

Corrosion

For corrosion studies, see sodium polysulfides, Na2S

x> Diffusion

No diffusion studies reported .

Heat of Fusion (H

H

j.)

No data; however, see sodium polysulfides, Na ? S,

L u

10 .

11 .

12 .

&

13 .

Heat Capacity (Cp)

No data; however, see sodium polysulfides, Na2S

x

.

Volume Change on Melting (&Vj?)

No data; however, see sodium polysulfides, Na 9 S x> Vapor r Pressure (pr ) vap

See sodium polysulfides, Na2S

x

, for equilibrium vapor pressures of sulfur

above molten polysulfides.

Thermal Conductivity (liquid)

No thermal conductivity studies reported

201
Na

2 S2

14. Thermal Conductivity (solid) (X ) ^ s No thermal conductivity studies feported.

15. Cryoscopic Constant

No data.

(k

f

>

16. References

[1] Rosen, E.

[2] Rosen, E.

and Tegman, R.

and Tegman, R.

Acta Chem. Scand., 2_5, 3329 (1971).

Chimica Scripta, 2_ , 221 (1972).

202
XXII. Sodium Trisulfide: Na

2 S^

1. Melting Temperature (Tm

) Melting point:

2 30 ° C [4]

References [1-4] .

2. Density (p)

See sodium polysulfides, Na

2 S x

,

3. Surface Tension (y)

See sodium polysulfides, Na^S^.

4. Viscosity (r\)

See sodium polysulfides, Na

2 S x

.

5. Electrical Conductance (k)

See sodium polysulfides, Na

2 S x

.

6. Safety and Hazards

No data; however,. see Na

2 S and Na

2 S x for observations on hazards.

Vapor pressure: the sulfur pressure above molten Na2 S

3 is approx. 10 mm

at 750°C, and ^300 mm at %1000°C.

References [5]

7. Corrosion

For corrosion studies; see sodium polysulfides, Na

2 S x

*

8. Diffusion

No diffusion studies reported with molten Na

2 S^ as solvent.

9. Heat of Fusion (h HZ)

No data; however, see sodium polysulfides, Na

2 S x

.

10. Heat Capacity (C )

No data; however, see sodium polysulfides, Na

2 S x

.

11. Volume Change on Melting ( LV

Measurement method: estimated [6]

Table 22.1. Volume change on melting

(AV

f /V

s

) Uncertainty

3.5% % ± 5-10%

References [6]

203
12 . Vapor c Pressure (pr ) vap

See sodium polysulfides, Na

2 Sx

, for equilibrium vapor pressures of sulfur

above molten polysulfides.

13. Thermal Conductivity (liquid) fX^)

Measurement method: comparative technique [7]

precision: not estimated uncertainty: ^ ± 20%

Table 22.2. Thermal conductivity of melt

T(K)

X x 10 4 (cal cm" 1 sec" 1 K

-1

) Sample

573 6.45 a 623 6.45

573 10.76 b

623 10.76

573 5.23 c 623 5.23

573 9.56 d

623 9.56

^a 2^3 _<"'^ composite with the graphite fibers randomly oriented.

Na

2 S

3 _C ' S comP osite with the graphite fibers oriented in the direction

of heat flow.

^ a 2^3 _<"”^ composite with the graphite fibers randomly oriented, loading

fraction of the cell one-half of that in (a) above ^a 2^3 _(""^ composite with the graphite fibers oriented in the direction of

heat conduction and with a loading fraction of the cell corresponding to

one-half of that in (b) above

References [7]

14.

Thermal Conductivity (solid) (X ) ° s No thermal conductivity studies reported.

15.

Cryoscopic Constant ( k

^)

No data.

16.

References

[1] Rosen, E., and Tegman, R. , Acta Chem. Scand., 25_, 3329 (1971).

[2] Rosen, E., and Tegman, R. , Chimica Scripta, 2_, 221 (1972).

[3] Oei , D. G., Inorg. Chem., 12, 435, 438 (1973).

[4] Janz, G. J., Downey, J. R. , Jr., Coutts, J. C., Roduner, E., and

Wasilczyk, G. , Inorg. Chem., 15, 1751, 1755, 1759 (1976).

[5] Tiberg, A., and Tiberg, J. , Acta Chemica Scand., 24, 991 (1970).

J 204
[ 6 ]

[7]

Na

2 S

3

Janz, G. J.,et al . , (MSDC-RPI) unpublished work (1977).

Chatterji, D. , General Electric Co., R. § D. Center, "Development

of Sodium-Sulfur Batteries for Utility Application"3 EPRI EM-266

(Dec., 1976).

205
XXIII. Sodium Tetrasulf ide : Na

2 S

4 1.

Melting Temperature CT^l

Melting point:

294° + 2 °C [1]

References [1-4] .

2.

Density C p)

Measurement method: pycnometric [3]

precision: not estimated uncertainty: ^ ± 31

Table 23.1. Densities

T P 00 (g cm-3

) 623 1.827

673 1.776

723 1.678

For densities of polysulfides with non- stoichiometric compositions, see:

sodium polysulfides, Na^^.

References [3]

3.

Surface Tension Cy I Measurement method: Wilhelmy slide plate method [3]

precision: not estimated uncertainty: ^ ± 3%

Table 23.2. Surface tension

T Y (K) (dyn cm-1

)

623 136

673 134

713 130

For surface tension of polysulfides with non- stoichiometric compositions,

see: sodium polysulfides, Na^^.

References [3] .

4. Viscosity Cnl

No data; however, see sodium polysulf ides , Na^^.

5. Electrical Conductance C<1

No data; however, see sodium polysulfides, Na^^.

206
6.

Safety and Hazards

No data, however, see Na£S and for observations on hazards

Vapor pressure: the sulfur vapor pressure above molten Na 9 S 4 is 'v 18 mm

at approx. 500°C , ^ 200 mm at approx. 700°C,and ^ 1 atm at approx. 850°C.

References [5,6]

7. Corrosion

For corrosion studies, see sodium polysulfides, Na ? S .

L, X

8. Diffusion

No diffusion studies reported.

9. Heat of Fusion (AH^.}

No data; however, see sodium polysulfides, Na ? S .

10.

Heat Capacity (C J No data; however, see sodium polysulfides, Na^S^.

11.

Volume Change on Melting (A7^J

Table 23.3. Volume change on melting

Measurement method: estimated [7]

(AV

f /Vs

) Uncertainty

7 . 0% ~ ± 10%

References [7]

12. Vapor r Pressure ( rp ) yap

See: sodium polysulfides, Na

2 Sx , for equilibrium vapor pressures of

sulfur above molten polysulfides.

13. Thermal Conductivity C liquid ) CX

No thermal conductivity studies reported.

14.

Thermal Conductivity Csolid) CX ) s No thermal conductivity studies reported.

15. Cryoscopic Constant

No data.

£ V

16. References

[1] Rosen, E., and Tegman, R. , Acta Chem. Scand., 2_5, 3329 (1971).

[2] Rosen, E., and Tegman, R. , Chimica Scripta, 2_, 221 (1972).

[3] 0ei , D. G., Inorg. Chem., L2, 435, 438 (1973).

207
[ 4 ] Janz, G. J., Downey, J. R.,Jr., Coutts, J. C., Roduner, E.,

and Wasilczyk, G., Inorg. Chem. , 15, 1751, 1755, 1759 (1976).

[5] Tiberg, A., and Tiberg, J., Acta Chemica Scand., 24_, 991 (1970).

[6] Tegman, R. , "Thermodynamic Studies of High Temperature Equilibria. XI.

Temperature Dependence of Equilibria Between Sulfur Vapor and Species in

Na 9 S Melts ", Chem. Scripta (to be published); see also: Tegman, R.

,

PhTD^f Thesis (1974), Umea, Sweden.

[7] Janz, G. J., et al., (MSDC-RPI) unpublished work (1977).

208
XXIV. Sodium Pentasulfide : ^ a

2. 2^5

Melting Temperature CT

Melting point:

264° + 10°C [1-4] . References [1-4]

2. Density Cp)

Measurement method: pycnometric [3]

precision: not estimated uncertainty: ^ ± 3%

Table 24.1. Densities

T P (K) (g cm-3

) 623 1.754

673 1.728

723 1.669

For densities of polysulfides with non- stoichiometric compositions, see:

sodium polysulfides, Na

2 S . References [3]

3.

Surface Tension (y)

Measurement method: plate, detachment [3]

precision: not estimated uncertainty: 'u ± 3$

Table 24.2. Surface tension

T Y (K) (dyn cm-1

) 633 121

673 116

703 114

For surface tension of polysulfides with non- stoichiometric compositions

see: sodium polysulfides, Na ? S . Z X

References [3]

4. Viscosity fn)

No data; however, see sodium polysulfides, Na ? S . Z X

5. Electrical Conductance Ck)

No data; however, see sodium polysulfides, Na 0 S^.

209
Na

2 S5

6. Safety and Hazards

No data; however, see Na

2 S and Na2 S^ for observations on hazards.

Vapor pressure: forequil. sulfur vapor pressures over some molten

polysulfides see e.g., Na

2 S2

> Na

2 S^ and N^S^.

7. Corrosion

For corrosion studies, see sodium polysulfides, Na

2 S^_.

8. Diffusion

No diffusion studies reported with molten Na

2

S,_ as solvent.

9. Heat of Fusion ( AH

No data; however, see sodium polysulfides, Na

2 S x<

10. Heat Capacity CC ) No data; however, see sodium polysulfides, Na ? S . Z X

11. Volume Change on Melting

Measurement method: estimated [5]

Table 24.3. Volume change on melting

< 4 VV Uncertainty

5.0% ^ ± 10%

References [ 5]

12. Vapor c Pressure ipc 1 vap

See: sodium polysulfides, Na

2 S x

, for equilibrium vapor pressures of

sulfur above molten polysulf ides

13. Thermal Conductivity (liquid) (A^)

No thermal conductivity studies reported.

14. Thermal Conductivity (solid) (X )

No thermal conductivity studies reported.

15. Cryoscopic Constant Ckj.)

No data,

16. References

[1] Rosen, E., and Tegman, R. , Acta Chem. Scand., 2_5, 3329 (J-971).

[2] Rosen, E., and Tegman, R. , Chimica Scripta, 2_, 221 (1972).

[3] Oei , D. G., Inorg. Chem., 12, 435,438 (1973}.

[4] Janz, G. J., Downey, J. R., Jr., Coutts, J. C., Roduner, E., and

Wasilczyk, G., Inorg. Chem., 1_5, 1751 , 1755, 1759 (1976).

210
Na

2 S

5

[5] Janz , G . J et al . , CMSDC-RPI) 9 unpublished work 0-277}

211
1. XXV. Lithium Bromide: LiBr

Melting Temperature CT^l

Melting point:

552° + 3°C [1,2,33]

References [1-9,33],

2.

density C pi

Measurement method: Archimedean technique [3]

p = 3.Q6546 - 6.5146 x l(f 4 T C25.ll

precision: ^ ± 0.021 uncertainty: -v ± 1.51

Table 25.1. Densities from equation (25.1)

T(K)

P (g cm 3

)

T(K)

P (g cm 3

) 830 2 .5247 930 2 .4596

840 2 .5182 940 2.4531

850 2 .5117 950 2 .4466

860 2 .5052 960 2 . 4401

870 2 .4987 970 2.4335

880 2 .4922 980 2.4270

890 2 . 4857 990 2 . 4205

900 2 .4791 1000 2.4140

910 2.4726 1010 2 . 4075

920 2 .4661 1020 2 .4010

References [3-5,8,10,11].

3.

Surface Tension (y)

Measurement method: maximum bubble pressure [12]

y

= 185.2 - 6.91 x

10' 2 T (25.2)

precision: not estimated uncertainty: ^ ± 1 %

Table 25.2. Surface tension from equation C25.2)

T(K)

y (dyn cm 1 )

T(K)

x (dyn cm *)

860 125.8 990 116.8

870 125.1 1000 116.1

880 124.4 1010 115.4

890 123.7 1020 114.7

900 123.0 1030 114.0

910 122.3 1040 113.3

920 121.6 1050 112.6

930 120.9 1060 112.0

940 120.2 1070 111.3

950 119.5 1080 110.6

960 118.9 1090 109.9

970 118.2 1100 109.2

980 117.5 1110 108.5

References [12-14] .

212
LiBr

4.

Viscosity Cr\)

Measurement method: oscillating sphere [7]

n = 13.8907 - 2.30413 x 10' 2 T + 1.0167 x 10

_5

T

2

precision: ± 0.71 uncertainty: ^ ± 251

Table 25.3. Viscosity from equation (25.3)

T(K)

n (cp)

T(K)

n (cp)

870 1.536 960 1.141

880 1.488 970 1.107

890 1.437 980 1.075

900 1.389 990 1.044

910 1.342 1000 1.016

920 1.298 1010 0.993

930 1.256 1020 0.966

940 1.215 1030 0.944

950 1.177 1040 0.924

References [6,7] .

5.

Electrical Conductance C<)

Measurement method: ac technique [3]

k = -1.1362 + 8.6159 x 10

_3

T - 1.86212 x 10

_6

T

2 (25.4)

precision: ± 0.47% uncertainty: ^ ± 3.5%

Table 25.4. Electrical conductance from equation (25.

T(K)K (ohm 1 cm *T(K)K (ohm 1 cm 1

) 830 4.7322 930 5.2660

840 4.7872 940 5.3174

850 4 . 8419 950 5.3683

860 4 .8963 960 5.4189

870 4 .9502 970 5 .4692

880 5 . 0038 980 5.5190

890 5.0570 990 5 .5685

900 5 .1098 1000 5.6176

910 5.1622 1010 5.6663

920 5. 2143 1020 5.7147

References [3,8,9,11,15-17].

6.

Safety and Hazards

A. Hazard rating [18-20]

(i) Toxicity - moderate

(ii) Vapor pressure: at m.pt. (552°C) , 'v 9.2 x 10~ 3 mm;

at 750°C, ^ 1 mm

(25.3)

213
LiBr

B. Disaster hazards [18,21-23]

(i) Molten salt bath "explosions": i.e., explosive generation of

steam due to bulk water "carry-over" and/or equipment

failure; i.e., explosive expansion of "trapped" air

Cii) Bromides when heated to decomposition, or contacted

with acids, emit highly toxic fumes

References [18-23].

7. Corrosion

Table 25.5. Corrosion studies from primary research literature

References [24-30] . Diffusion

No diffusion studies reported.

Heat of Fusion CkHj.)

Measurement method: drop calorimetry [2]

Table 25.6. Heat of fusion

AH°

^ i Uncertainty

(kcal mol )

4 .22 ^ ± 1%

References [2,31].

10. Heat Capacity (-C ) Measurement method: drop calorimetry [32]

Table 25.7. Heat capacity

c

p Temp, range Uncertainty

(cal K ^ipol (K)

15.60 823-883 'v ±2%

References [32,33].

11. Volume Change on Melting ( AF^J

Measurement method: capillary technique [34]

Table 25.8. Volume change on melting

<AV

f /V

s

> Uncertainty

24.3 % ^ ± 3%

Reference [34]

8 .

9.

214
LiBr

12 . Vapor Pressure Cp , 1 r r vap

Measurement method: boiling point

log p

- 8.6340

precision: ^ ± 2.70%

138]

- 8803/T C25

uncertainty

5]v ± 10%

Table 25.9.1. Vapor pressure from equation (_2 5.5)

T P T P (K) (mm ) (K) (mm)

1290 64 .

1420 272 .

1300 72.9 1430 300.7

1310 82 .

1440 331.7

1320 92 .

1450 365 .

1330 103 .

1460 402.3

1340 116.0 1470 442 .

1350 129 .1480 485.3

1360 144.9 1490 532.0

1370 161.6 1500 582 .

1380 179 .

1510 637 .

1390 199 .

1520 695.9

1400 221.9 1530 759 .

1410 245.9

Measurement method: effusion [37]

precison: not estimated uncertainty: ^ ± 5%

Table 25.9.2. Additional vapor pressure data

T P (K) (mm)

861 5.61 x lO" 2

References [35-38] .

IS. Thermal Conductivity ( liquid

( A Measurement method: transient hot wire [39,40]

precision: not estimated uncertainty: ^ ± 20%

Table 25.10. Thermal conductivity of melt

References [39,40].

215
LiBr

14. Thermal Conductivity Csolidl CA 1 o No thermal conductivity studies reported.

15. Cryoscopic Constant

Measurement method: calculated from AHj [41]

Table 25.11. Cryoscopic constant

kf

-1

(K mol -

"*-kg ) Uncertainty

27 .^ ± 1%

References [2,41,42]

16.

References

[1] Rossini, F. D., Wagman, D. D., Evans, W. H., Levine, S., and Jaffe,

I., "Selected Values of Chemical Thermodynamic Properties , NBS

Circ. 500; U. S. Gov't Printing Office, Washington, D. C. (1952).

[2] Dworkin, A. S., and Bredig, M. A., J. Phys . Chem. , 64, 269 (1960).

[3] Yaffe, I. S., and van Artsdalen, E. R., J. Phys. Chem., 6_0, 1125

(1956) .

[4] Brunner, E., Z. angew. Chem., 3_8, 350 (1904).

[5] Schinke, H., and Sauerwald, F., Z. anorg. allgm. Chem., 287,

313 (1956).

[6] Karpachev, S., and Stromberg, A., Zhur. Fiz. Khim. , 11^, 852 (1938).

[7] Murgulescu, I. G., and Zuca, S., Z. physik. Chem., 218 , 379 (1961).

[8] Smirnov, M. V., Khokhlov, V. A., Stepanov, V. P., and Shumov, Yu. A.

Tr. Inst. Elektrokhim. Ural. Nauchn. Tsentr Akad. Nauk SSSR,

20, 3 (1973).

[9] Mehta, 0. P., Indian J. Chem., 12_, 816 (1974).

[10] Holm, J. L., Acta Chem. Scand., 2_5, 5 (1971).

[11] Zuca, S., and Olteanu, M., Private Communication to G. J. Janz,

October (1974)

[12] Smirnov, M. V., and Stepanov, V. P., "Physical Chemistry and Electro

chemistry of Molten and Solid Electrolytes . I. Structure and

Properties of Electrolytes"3 Reports of All-Union Conference,

Sverdlovsk, June (1973).

[13] Kipov, I. G., Zadumkin, S. N., and Temrokov, A. I., Zh. Fiz. Khim.,

44, 2618 (1970)

[14] Berge, B., and Holm, J. L ., "Surface Tension of Binary Mixtures of

Molten Salts

Rapport til Norges Tekniske H0gskoles Fond (1970).

[15] Mehta, 0. P., Lantelme, F., and Chemla, M., Electrochim. Acta,

14, 505 (1969)

[16] Bizouard, M. , Ann. Phys. (Paris), 6_, 851 (1961).

[17] Andryushchenko, Yu. I., and Bergman, A. G., Zh. Fiz. Khim., 39 , 353 (1965).

216
LiBr

[18] "Dangerous Properties of Materials", Sax, N. 1., Van Nostrand

Reinhold Co., N. Y. (1969-1.

[19] "Registry of Toxic Effects of Chemical Substances"

Christensen,

H. E., and Lubinbyhl, T. T., eds . , U. S. Dept. H. E. W., U. S.

Gov’t Printing Office, Washington, D. C. (1975).

[20] Vapor pressure, calculated Csee P* 215, this work).

[21] "Potential Hazards In Molten Salt Baths for Heat Treatment of Metals ",

National Board Fire Underwriters Research Report No. 2 (1954).

[22] "Handbook of Reactive Chemical Hazards", Bretherwick, L., Butterworths

Co . , London (1975)

[23] Janz, G. J. , Tomkins, R. P. T., Downey, J. R. , Jr., and Allen, C. B.

"Safety and Hazards ", Chapter in "Eutectic Data", ERDA TID-27163-P1

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[24] Janz, G. J "Molten Salts Handbook" Academic Press, N. Y. 388 (1967).

[25] Mackenzie, J. D., "Physico-Chemical Measurements at High Temperatures"

J. O'M. Bockris, J. L. White and J. D. Mackenzie, eds., Butterworths

Ltd., London and N. Y. (1959).

[26] Johnson, K. E., "High Temperature Technology", 3rd Inst. Symposium,

Butterworths Ltd., London (1969).

[27] Smirnov, M. V., and Ozeryanaya, I. N. , Nauki. Tekh. Korros. Zashch.

Korros, 2, 171 (1973)

[28] Inman, D., and Wrench, N. S., Brit. Corr., J., 1_, 246 (1966).

[29] Ketelaar, J. A. A., Chemie Ing. Techn., 4_5 , 667 (1973).

[30] Janz, G. J., and Tomkins, R. P. T., Corrosion, 3_4 (in press) (1978).

[31] Blanc, M. , Compt. Rend., 246 , 570 Cl 9 58).

[32] Dworkin, A. S., COak Ridge National Laboratory); unpublished work

(1964), cited in "JANAF Thermochemical Tables" 2nd Ed. (1971).

[33] Stull, D. R. , and Prophet, H. feds.), 'ifANAF Thermochemical Tables",

2nd Ed., NSRDS-NBS 37; U. S. Gov't Printing Office, Washington,

D. C. (1971) .

[34] Schinke, H., and Sauerwald, F., Z. anorg. allgm. Chem. , 304, 25 (1960);

ibid., 284, 131 (1956); ibid., 287_, 313, (1956).

[35] von Wartenberg , H . , and Schulz, H., Z. Elektrochem . , 27_, 568 (1921).

[36] Belyaev, I. N., and Kesarev, V. V., Zhur. Neorg. Khim., 15(5)

1418 (1970); Russ. J. Inorg. Chem., 15, 727 (1970).

[37] Miller, R. C., and Kusch, P., J. Chem. Phys . , 2_5 , 860 (1956).

[38] Ruff, 0., and Mugdan, S., Z. anorg. allgm. Chem., 117 , 147 (1921).

[39] McDonald, J., and Davis, H. T., Phys. Chem. Liq., 2_, 119 (1971).

[40] Jamieson, D. T., Irving, J. B., and Tudhope, J. S., "Liquid Thermal

Conductivity", HMSO, Edinburgh, 1975.

[41] Janz, G. J.,et al . , (MSDC-RPI) unpublished work (1977).

[42] Aukrust, E., Bjorge, B., Flood, H., and Forland, T., Ann. N. Y.

Acad. Sci., 79, 830 (1960).

217
XXVI. Lithium Iodide: Lil

1.

Melting Temperature CT^)

Melting point:

469° + 3 °C [1,2,27]

References [1-7,27].

2.

Density (p)

Measurement method: Archimedean technique [5]

p = 3.79045 - 9.1780 x 10

_4

T (26.1)

precision:^ ± 0.011 uncertainty: ^ ± 2%

(partial decomposition of Lil reported at higher experimental temperatures)

Table 26.1. Densities from equation (26.1)

T P T P_

(K) (g cm 3

) (K) (g cm 3

)

760 3 . 0931 830 3.0289

770 3.0839 840 3 . 0197

780 3 .0747 850 3.0105

790 3 . 0656 860 3.0013

800 3.0564 870 2 .9922

810 3.0472 880 2 .9830

820 3 .0380

References [5-7] .

3.

Surface Tension (y)

Measurement method: maximum bubble pressure [8]

y

= 140.7 - 5.65 x 10

_2

T (26.2)

precision: not estimated uncertainty: ^ ± 1%

Table 26.2. Surface tension from equation (26.2)

T

(K)

Y (dyn cm 1 )

T(K)

Y (dyn cm 3 ) 860 92.1 990 84.8

870 91.5 1000 84.2

880 91.0 1010 83.6

890 90.4 1020 83.1

900 89 .

1030 82.5

910 89 .

1040 81.9

920 88.7 1050 81.4

930 88.1 1060 80.8

940 87.6 1070 80.2

950 87 .

1080 79.7

960 86.5 1090 79.1

970 85.9 1100 78.5

980 85 .

1110 78.0

References [8,9] .

218
Lil

4.

Viscosity Cn)

Measurement method: oscillating sphere [4]

n

= 17.1411 - 3.14517 x 10

_2

T + 1.54597 x 10

_5

T

2 C26.3)

precision: ± 0.4% uncertainty: ^ ± 25%

Table 26.3. Viscosity from equation C26.3]

T(K)

n (cp)

T(K)

n(cp)

830 1.69

840 1.63

750 2.25 850 1.58

760 2 .17 860 1.53

770 2 .09 870 1.48

780 2 . 01 880 1.44

790 1 .94 890 1.39

800 1.87 900 1.36

810 1.81 910 1.32

820 1. 75 920 1.29

References [4,10] .

5,

Electrical Conductance CkJ

Measurement method: ac technique [11]

k = -3.64062 + 1.47826 x 10

_2

T - 6.28111 x 10

_6

T

2 (26.4)

precision: ± 0.060% uncertainty: ^ ± 2.5%

Table 26.4. Electrical conductance from equation (26.4)

T(K)

K (ohm 1 cm 1 )

T(K)

K (ohm 1 cm *)

760 3.9662 820 4. 2577

770 4.0179 830 4 .3019

780 4.0684 840 4 .3448

790 4.1176 850 4.3865

800 4 .1655 860 4.4269

810 4.2122 870 4.4660

880 4 .5039

References [3,5-7,11].

6.

Safety and Hazards

A. Hazard rating [12-14]

(i) Similar in toxicity to LiBr; moderate

(ii) Vapor pressure: at m.pt. (469°C) , <v 2.8 x 10~ 3 mm;

at 700°C, ^ 1 mm

B. Disaster hazards [12,15-17]

Ci) Molten salt bath "explosions": i.e., explosive generation of

steam due to bulk water "carry-oyer" and/or equipment

failure; i.e., explosive expansion of "trapped" air

219
Lil

Cii] Iodides when heated to decomposition can evolve highly

toxic fumes of iodine and iodides; dangerous

References {12-17] .

7 . Corrosion

Table 26.5. Corrosion studies from primary research literature

Stud ies References

Supremax glass 18-20

Molten salts corrosion: reviews 21-23

Annotated corrosion biblio. 24

References [18-24] .

8 . Diffusion

No diffusion studies reported.

9. Heat of Fusion f AffjU

Measurement method: drop calorimetry [25]

Table 26.6. Heat of fusion

AH ° Uncertainty

(kcal mol )

3 .50 ^ ± 1.5%

References [25]

10. Heat Capacity J Measurement method: drop calorimetry [26]

Table 26.7. Heat capacity

C

P Temp . range Uncertainty

(cal K~-*-mol ) (K)

15.10 742-802 ^ ± 2%

References [26,27].

11. Volume Change on Melting (AV^,)

Measurement method: estimated; from densities [28]

Table 26.8. Volume change on melting

(AV

f /V

s

) Uncertainty

24 . 7% v ± 8 %

References [ 28] .

220
Lil

12.

Vapor Pressure Cp i c vap

Measurement method: boiling point [29]

log p

= 8.5901 - 8270/T C2 6 . 5

precision: ^ ± 1.51 uncertainty: ^ ± 101

Table 26.9. Vapor pressure from equation (26.5)

T P T P (K) (mm) (K) (mm)

1230 73 .

1330 235 .

1240 83 . 3 1340 262 .

1250 94.2 1350 291.2

1260 106 .

1360 323.0

1270 119 .

1370 357 .

1280 134 .

1380 395.7

1290 151 .

1390 437 .

1300 169 .

1400 481.9

1310 189 .

1410 530.7

1320 211 .

References [29,30].

13.

Thermal Conductivity (liquid)

No thermal conductivity studies reported.

14. Thermal Conductivity (solid) (X ) s No thermal conductivity studies reported.

15. Cryoscopic Constant (k^)

Measurement method: calculated from AH£ [28]

Table 26.10. Cryoscopic constant

k .f

„ -i -i Uncertainty

(K mol kg ) 41.8 ^ ± 1.5%

References [25,28].

16.

References

[1] Johnson, J. W., and Bredig, M. A., unpublished data; cited in:

Dworkin, A. S., and Bredig, M. A., J. Phys . Chem. , 64, 269 (1960).

[2] Rossini, F. D., Wagman, D. D., Evans, W. H., Levine, S., and Jaffe,

I ., "Selected Values of Chemical Thermodynamic Properties, NBS

Circ. 500U. S. Gov't Printing Office, Washington, D. C. (1952).

[3] Karl, W. , and Klemm, A., Z. Naturforsch . , 19a , 1619 (1964).

[4] Karpachev, S., and Stromberg, A., Zhur. Fiz. Khim., 11, 852 (1938).

[5] Yaffe, I. S., and van Artsdalen, E. R. , J. Phys. Chem., 6_0, 1125 (1956).

221
Lil

[6] Smirnov, M. V. , Khokhlov, V. A., Stepanov, V. P., and Shumov, Yu. A.,

Tr. Inst. Electrokhim. Ural. Nauchn . Tsentr Akad . Nauk SSSR, 20

3 (1973) .

[7] Zuca, S., and Oltaneau, M. , pre -publ icat ion results to MSDC-RPI

(October 1974) .

[8] Smirnov, M. V. , and Stepanov, V. P., '!Physical Chemistry and Electrochemistry of Molten and Solid Electrolytes . I-. Structure and

Properties of Electrolytes." Reports of All-Union Conference,

Sverdlovsk, June (1973)

[9] Kipov, I. G., Zadumkin, S. N., and Temporov, A. I., Zh. Fiz. Khim.,

44, 2618 (1970).

[10] Murgulescu, I. G., and Zuca, S., Rev. Chim. (Roumaine), 123 (1965).

[11] Johnson, C. E., pre-publication communication to MSDC-RPI (1968)

[12] "dangerous Properties of Materials ", Sax, N. I., Van Nostrand

Reinhold Co . , N. Y. (1969)

[13] "Registry of Toxic Effects of Chemical Substances"3 Christensen,

H. E., and Lubinbyhl, T. T., eds., U. S. Dept. H.E.W., U. S. Gov't

Printing Office, Washington, D. C. Cl 97 5).

[14] Vapor pressure, calculated (see p. 221, this work).

[15] "Potential Hazards in Molten Salt Baths for Heat Treatment of Metals"3 National Board Fire Underwriters Research Report No. 2 (1954).

[16] "Handbook of Reactive Chemical Hazards

3 Bretherwick, L., Butterworths

Co . , London (1975)

[17] Janz, G. J., Tomkins, R. P. T., Downey, J. R. , Jr., and Allen, C. B.,

"Safety and Hazards"3 Chapter in "Eutectic Data ", ERDA TID-27163-P1

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[18] Janz, G. J ., "Molten Salts Handbook}' Academic Press, N. Y. 388 (1967).

[19] Mackenzie, J. D., "Physico-Chemical Measurements at High Temperatures

3 J. O'M. Bockris, J. L. White and J. D. Mackenzie, eds., Butterworths

Ltd., London and N. Y. (1959).

[20] Johnson, K. E., "High Temperature Technology"3 3rd Inst. Symposium,

Butterworths Ltd., London (1969).

[21] Smirnov, M. V., and Ozeryanaya, I. N., Nauki Tekh. Korros . Zashch.

Korros . , 2, 171 (1973) .

[22] Ketelaar, J. A. A., Chemie Ing. Techn., 4_5, 667 Cl 973).

[23] Inman, D., and Wrench, N. S., Brit. Corr. J., 1^, 246 (1966).

[24] Janz, G. J., and Tomkins, R. P. T., Corrosion, 3_4 (in press) (1978).

[25] Dworkin, A. S., and Bredig, M. A., J. Phys . Chem. , 64^, 269 (1960).

[26] Dworkin, A. S., (Oak Ridge National Laboratory); unpublished work

(1964), cited in "JANAF Thermochemical Tables" 2nd ed. (1971).

[27] Stull, D. R., and Prophet, H. (eds.), "JANAF Thermochemical Tables 3" 2nd ed., NSRDS-NBS 37; U. S. Gov't Printing Office, Washington,

D. C. (1971).

[28] Janz, G. J., et al., (MSDC-RPI), unpublished work (1977).

[29] Ruff, 0., and Mugdan, S., Z. anorg. allgm. Chem., 117 , 147 (1921).

222
Lil

[30] von Wartenberg, H., and Schulz, H., Z. Elektrochem. , 27, 568 (1921)

223
XXVII. Lithium Chloride-Potassium Chloride: LiCl-KCl

1. Melting Temperatures (Tm

)

Pure substance melting points:

LiCl : 610°C

KC1 : 770°C

Eutectic melting point:

355°C, composition: 58.5 mol % LiCl

Figure 27.1. LiCl-KCl phase diagram

References [1-3]

Density ( p ) Measurement method: Archimedean technique [4]

Two- independent -variable equation

p = a + bT + cC + dT 3 + eC

3

+ fTC 2 (C = mol % LiCl) (27.1)

precision: ± 0.15% uncertainty: ^ ± 0.5%

Table 27.1. Coefficients for two- independent -variable equation (27.1)

a b x 10 4 c x 10 3 d x 10 1

e x 10 7 f x 10 8

1.98715 -5.89069 2.02443 5.31098 1.21294 -2.16826

224
LiCl-KCl

_ 7 Table 27.2. Densities (g cm ) from two - independent -variable equation (27.1)

References [4-24].

3. Surface Tension (y)

Measurement method: maximum bubble pressure [10,11]

Single variable equation

y

= a - bT (27.2)

precision: in table 27.3 uncertainty: ^ ± 0.51

Table 27.3. Coefficients of equation (27.2), and precisions

Mol % LiCl a b x 1

2 Precision

10 187.4541 8 .30993 ± 0.13%

15 189 . 5651 8 .49146 ± 0.08%

22 196 . 2269 9 .16605 ± 0 . 20%

30 190.9364 8 .69217 ± 0.24%

40 189 . 4704 8 .45251 ± 0. 25%

50 187 . 3435 8 . 08096 ± 0.21%

58 189 . 5657 8.23478 ± 0.70%

69 188.3650 7 .82852 ± 0.22%

79 183.5300 7 . 10111 ± 0.38%

90 183.3852 6.75324 ± 0 . 20%

225
LiCl-KCl

Two- independent -variable equation

y

= a + bT + cC + dT 2 + eC

2 + fTC + gTC 2 (C = mol % KC1) (27.3)

precision: v ± 0.4% uncertainty: v ± 1%

Table 27.4. Coefficients for two-independent-variable equation (27.3)

a b x 1

2 c x 1

2 d x 1

6 e x 1 0

3 f x 10 4 g x 1

6

177 . 43373 -5.43167 34.0743 -3 .73703 -3 .19922 -7 . 20291 5 .57068

Table 27.5. Surface tension (dyn cm ^) from equations in table 27.3

Mol Z LiCl

T(K) 90 79 69 58 50 40 30 22 15 10

660 135.22

680 133.57

700 131.92

720 130.28

740 128.63

760 126.98

780 127.30 125.33 124.31

800 125.74 123.69 122 . 70 820 124.17 122.04 121.08

840 123.88 122.61 120.39 119.46

860 122.46 121.04 118.75 117.85

880 123.96 121.04 119.47 117.10 116.23 115.09

900 122.61 119.62 115.45 114.61 113.40

920 121.26 118.20 113.81 113.00 111.71 110.97

940 119.90 116 . 78 111.38 110.02 109 .23 960 118.56 115.36 109.77 108.33 107.49

980 117.20 113.94 108.15 106.64 105.75 106.40

1000 115.85 112.52 106.53 104.95 104.01 104.57

1020 114.50 111.10 104.92 103.25 102 .28 102.73 102.95

1040 113.15 100.54 100.90 101.25 101.03

1060 111.80 98.80 99.07 99.56 99.37

1080 97.86 97.71

1100 96.16 96.04

References [4-11,25].

4 . Viscosity ( r\) Measurement method: oscillating sphere [13]

n = a + bT + cT

precision: in table 27.6

+ dT (27.4)

uncertainty: v ± 15'

226
LiCl-KCl

Table 27.6. Coefficients of equation (27.4), and precisions

LiCl

(mol %)

a -b x 10 2 c x 10 6 d x 10 9 Precis ion

0 13.5546 2.0050 7.8613 0 ±0.76%

60 8.5113 0.7401 -4.8633 4.8121 ±0.59%

100 10.0147 0.5158 -13.0241 9.2997 ±1.36%

n = A exp (E/RT) (27.5)

precision: in table 27.7 uncertainty:^ ± 5%

Table 27.7. Coefficients of equation (27.5), and precisions

LiCl

(mol %)

A x 10 2 E (cal mol-1

) Precis ion

20 7.037 5707 ±0.69%

30 9.019 5097 ±1.69%

40 7.793 5337 ±1.01%

50 7.860 5249 ±1.09%

80 8.893 4980 ±0.98%

Table 27.8. Viscosity (cp) from equations in tables 27.6,

Mol Z L 1 C 1

( K ) 100 80 60 50 40 30 20 0

890 1.46

900 1.60 1.42

910 1.54 1.40 1.38

920 1.49 1.36 1.33 1.45 1.47

930 1.43 1.32 1 . 29 1 . 35 1.40 1.42

940 1.38 1.28 1.25 1.31 1 . 36 1 . 38 950 1.33 1.24 1.22 1.27 1 . 32 1.34

960 1 . 29 1.21 1.18 1.23 1 . 28 1.31

970 1.24 1.18 1.15 1.20 1.24 1.27 1 .36 980 1.20 1.15 1.12 1.17 1.21 1.24 1 . 32 990 1.17 1.12 1.09 1.13 1.18 1.20 1 . 28 1000 1.13 1.09 1.06 1.10 1.14 1.17 1.24

1010 1.10 1.06 1.03 1.08 1.11 1.14 1 . 21 1020 1.07 1.04 1.01 1.05 1.09 1.12 1 .18 1030 1.05 1.01 0.99 1.02 1 . 06 1.09 1 . 14 1040 1.02 0.99 0.97 1.00 1.03 1.06 1.11

1050 1.01 0.97 0.95 0.97 1.01 1.04 1.09

1060 0.99 0.95 0.93 0.95 0.98 1.01 1.06

1070 0.98 0.93 0.92 0.93 0.96 0.99 1.03

1080 0.97 1.01

1090 1.04

1100 1.01

1110 0.99

1120 0.96

1130 0.94

1140 0.92

1150 0.89

References [4-14,26-29].

and 27.7.

227
LiCl-KCl

5. Electrical Conductance (k)

Measurement method: ac technique [4]

k = a + bT + cT

2 (27.6)

precision: in table 27.9

uncertainty: ^ ± 0.5% at T < 1050 , and increasing to

^ ± 4% for T > 1050

Table 27.9. Coefficients of equation (27.6), and precisions

Mol % LiCl -a b x 10 2 - c x 1

6 Precision

0 5 .5231 1 .1714 4 . 1800 ±0.19%

19 . 96 5 .9678 1 . 2866 4 .7560 ±0.17%

40.45 8 . 5932 1 . 8845 7 .8109 ±0.24%

58 .80 5 . 6492 1.3732 5.1788 ±0.18%

70.36 11.0108 2 .7461 13 . 2471 ±0.49%

81.77 6.7217 1.8182 7.4002 ±0.09%

100 7.3766 2 .2747 9 . 0623 ±0.35%

For numerical values: see table 27.10.

228
LiCl-KCl

Table 27.10. Specific conductance (ohm '*'cm *) from

equations in table 27.9

Mol % LiCl

T(K) 100 81.77 70.36 58 . 80 40.45 19.96 0

670 1.227

'

690 1.360

710 1.490

730 1.976 1.615

750 2 .133 1.737

770 2.280 1 .854

790 2.416 1 .967

810 3 . 150 2 . 541 2.076

830 3.271 2 . 656 2 . 181

850 3 .386 2 .760 2 . 281

870 3.495 2 .854 1.890

890 3 .599 1 .992

910 5 . 819 2 . 087

930 5 . 940 2.177

950 6.054 2.260

970 6.161 2.337

990 6.261 2.408 2.108

1010 6.353 2.472 2 .175

1030 6.439 2.239

1050 6 . 517 2 .298

1070 2.354 2 .225

1090 2.406 2.279

1110 2.454 2 .329

1130 2.376

1150 2.420

1170 2.460

1190 2 .497

References [4-11,28,30-37].

6. Safety and Hazards

A. Hazard rating [38-40]

(i) Toxicity: LiCl, slight; KC1, slight.

(ii) Vapor pressure: eutectic (m.pt. 355°C) : ^ 1 mm

at 800°C (estimated).

B. Disaster hazards [38,41-43]

(i) Molten salt bath "explosions": i.e., explosive generation

of steam due to bulk water "carry-over" and/or

equipment failure; i.e., explosive expansion

of "trapped" air.

229
LiCl-KCl

(ii) Chlorides evolve highly toxic chloride fumes

when heated to decomposition, or contacted

with acids.

References [38-43].

7. Corrosion

Table 27.11. Corrosion studies from primary research literature

Studies Ref erences

Cu 44

Fe 45, 46

U-Bi 47

Cr , Pt 48

Cu, CuO; Pt, PtO; Bi, Bi^O-;

Ni, NiO J 49

Zn-rare earth metal alloys 50

Ni 51

Ag, Cu, Ni, Co, Au 52

T i-Al-Mo53

Pt 54

Mild steel, Armco iron 55, 56

Various steels 57

Mo, Ni, Nb, various steels,

various Inconels (LiCl-KCl, with

FeS and FeS^ as additives) 58

(trace amts) 59

Emf . series 48

Electrochemical approach 60

Thermodynamic principles (redox

d iagr ams

)

61-63

Annotated corrosion biblio. 64

Reviews: corrosion in molten salts 65-67

References [44-67].

230
LiCl-KCl

8 . Diffusion

Measurement method: cited in tabulations

List of diffusing species investigated in LiCl-KCl as solvent

Na T1 Ge

2 + Pb

2+

. Sb 3+

Cd

2+

, Eg 2±

3 Y

2+

_ Cr

3+

, Mo

3+

, [MoCl

2+ . 3 + „ 3+

La

} 3 + 3-

5 +3+

Ft

Er

3+

Pu

3 +

Ce'

Tm

Pu

3+

4+"

Py

Yb

Am

Ed

3+

J 3 + Lu

Cm

3+

J 3+

3 +

'

Bi

3+

, Cu

+

, Ag

+

, Au

+

, Zn

2+

3 V0

2+

3 Nb 2 +

3 Nb

3+

, Nb.Cl 3 [TaCl ] 2 ~

3 Mn

2+

, Fe

2+

, Co

2+

, Ni^ +

, Pd2+

}

Sm

Z+

3 Eu

+

3 Gd

2+

3 Tb

2+

3 Dy

2+

3 Ho

2+

3 U

3+

, U

4+

, U0

2+

, Np

3+

, Np

4+

, NpO+ EpO

2 *

2

~ „ : 2 - .. . 2 - .....

0 VO. Cr0‘ Mo0‘ s

2 ~

3 Cl 03 HCl 3 h 9 o. X 6 6

Mo0

2 C1 23 po'4

The italicized species indicate studies with insufficient data-sets

for characterization of temperature-dependence of diffusion co- efficients. For these speciesrsee table 27.12.4.

Equation D = A exp [-E/RT] (27.7)

precision: in table 27.12.2 uncertainty: in table 27.12.1

Table 27.12.1. Diffusion techniques, uncertainties, and species

Diffusion technique

of recommended study

Uncertainty

(in values of D)

Species

capillary ^ ± 10% Na , Cu , U

4

, U0|

+ + + 3

chronopotentiometry ^ ± 10% Cu , Ag , Au , La , Nb 3+

, Mo 3+

, Fe 2+

, Ni 2+, Ce 3+

, U 3+, U 4+

, Np 3+

, N p

4 +

, Pu 3+

, Pu 4

, Am 3

, Cm 3+

, Ge 2+

, Zn 2

, Hg 2, V

5+

, V0 2+, Nb 3 C

8 , TaClf~, Mo C 1 5 ~

, W

3 +

, Pd 2+

, Np0 2 , Np0| +

, 0 2_

, VO3, CroJ", MoO?

-

, Mo 0 2 C1 2 , POq", S

2 ”,

Cl 2 , HC1, H 2 0

voltammetry ^ ± 20% Bi 3+

, Tl

+

, Cd 2+

, Cr 3+, Mn 2+

, Co 2+

polarography ^ ± 2 0% Sb 3+

, Pd 2+

, Pt 2+

rotating disc electrode ^ ± 20% Y

3 +

, Pr 3 +

, Nd 3 +

, Sm 3 +

, Eu 3 +

, Gd 3 +

, Tb 3 +

, Dy 3+, Ho 3+

, Er 3+

, Tm 3+ ,Yb 3+

, Lu3

For diffusion equation parameters, and precisions: see table 27.12.2

231
LiCl-KCl

Table 27.12.2 Diffusion equation parameters, precisions, and

recommended study

Species A x 1

3

( cm2 sec 1

)

E (cal mol 1 )

Temp, range

(K)

Precision Recommended

study

Tl

+

3 . 08 6498 650-810 93

Pb 2+

2 . 84 7313 650-810 93

Bi 3+ 6.03 10067 630-800 93

Cu

+ 0.601 4550 670-750 116

Ag

+ 1.32 5800 670-870 83

Au

+

1 . 14 6300 670-870 83

Cd 2+

5 . 94 8502 640-800 93

La 3 +

2 . 69 7688 710-940 79

Nb 3+ 2 . 18 7000 670-870 86

Cr 3 + 6.35 10424 690-810 93

Mo 3+ 3 . 89 9212 810-1190 77,104

Mn 2+ 10.9 9706 640-810 93

Fe 2 + 1.53 7200 670-870 83

Co

2+ 2 .45 8054 670-820 93

Ni 2 + 1.56 7100 670-870 83

Ce 3 + 1.78 7 67 0 670-920 109

U

3 + 1.739 8502 650-810 ±4.1% 91

U

4 + 1.13 6300 640-880 ± 3% 90

u*

+a

5. 788 8757 690-820 ± 3. 6% 91

Csl +

o <N

:=> 1.76 7500 665-800 ± 0.14% 90

Np 3 +

3 . 05 8699 670-920 ± 3% 85

Np‘t + 3.447 8787 670-820 ±4.6% 110

Pu 3 + 3.314 8792 670-920 ± 2% 122

Pu 4 + 5.918 9665 670-920 ±2.1% 84

Am 3 +

5 . 657 9770 670-920 ±8.3% 92

Cm 3 +

8 .799 10397 670-820 ± 14% 125

No entry in precision column indicates estimates not^possible since

results were reported as equations only.

^he italicized U^

+ is for a study in presence of added F ions, diffusing species is uncertain.

232
LiCl-KCl

Table 27.12.3 (Part 1). Diffusion coefficients, D x 10^(cm^sec

equations in table 27.12.2

from

T(K) Tl +

Pb 2 + Bl 3 +Cu

+

Ag

+ Au+

. Cd 2 +

La 3 + Nb 3 +Cr 3 + Mo 3 + Mn 2 +

Fe 2 +

Co 2 +

630

640 650

670

690

710

730

750

770

790

800 810

830 850

870

890

930

950

970 990 1010

1030

1050

1070

1090

1110

1130

1150

1170

1190

2.01

2.34

2.69

3.08 3.49

3.93

4.41

4.91

5.17

5.43

0.99

1.17

1.37 1.59

1.84

2.10

2.39

2.69

2.85 3.02

0.194

0.220

0.248

0.314

0.390

0.480

0.584

0.702

0.837

0.989

1.07

1.97 2.18

2.39

2.61

2.84

1.69

1.92

2.16

2.42

2.69

2.98

3.28

3.44

3.59

3.92

4.26

4.61

1.00

1.15

1.31

1.48

1.66

1.86

2.06

2.17

2.28

2.50

2.74

2.98

0.742

0.822

1.00

1.20

1.43

1.69

1.98

2.29

2.64

2.83

1.16

1.34

1.55

1.77 2.01

2.14

2.27

2.54 2.84

3.15

3.48

4.20

1.14

1.32 1.53

1.75

1.99

2.25

2.52

2.67

2.82 3.13

3.46

3.80

0.317

0.393

0.481

0.582

0.698

0.829

0.901

0.977 1.27

1.46

1.66

1.89

2.13

2.66

2.96

3.27

3.60

3 . 95 4.32

4.70

5.11

5.53

5.97 6.43

6.90

7.40

7.91

0.528

0.594

0.743

0.918

1.12

1.35

1.62

1.92

2.25

2.43

2 . 62

0.685

0.802

0.93

1.07

1.22

1.38

1.56

1.65

1.75

1.94

2.15

2.38

0.578

0.689

0.813

0.950

1.10

1.27

1.45

1-.54 1.64

5 2 -

Table 27.12.3 (Part 2) Diffusion coefficients, D x 10 (cm sec ), from

equations in table 27.12.2

T

(K) Ni 2 + Ce 3 +

U

3 +

U“ +

u‘* + aU 02

+ Np 3 +

NP ^ +

Pu 3 +

Pu 4 + Am 3 + Cm 3 +

630

640 0.797

650 0.241 0.860

670 0.753 0.560 0.293 0.995 0.629 0.443 0.469 0.449 0.416 0.368 0.357

690 0.879 0.662 0.353 1.14 0.974 0.741 0.536 0.568 0.544 0.514 0.455 0.448

710 1.02 0.775 0.420 1.30 1.17 0.864 0.640 0.680 0.651 0.626 0.556 0.554

730 1.17 0.899 0.495 1.47 1.38 1.00 0.758 0.806 0.773 0.756 0.672 0.678

750 1.33 1.04 0.579 1.65 1.62 1.15 0.890 0.948 0.908 0.903 0.804 0.821

770 1.51 1.18 0.671 1.84 1.89 1.31 1.04 1.11 1.06 1.07 0.954 0.985

790 1.69 1.34 0.773 2.04 2.19 1.48 1.20 1.28 1.22 1.25 1.12 1.17

800 1.79 1.43 0.827 2.15 2.34 1.57 1.28 1.37 1.31 1.35 1.21 1.27

810 1.89 1.52 0.883 2.26 2.51 1.37 1.47 1.41 1.46 1.31 1.38

830 2.11 1.70 2.48 1.56 1.60 1.69 1.51

850 2.33 1.90 2.71 1.77 1.82 1.94 1 . 74 870 2.57 2.11 2.95 1.99 2.05 2.21 1.99

890 2.33 2.23 2.30 2.50 2.26

910 2.56 2.48 2.56 2.82 2 .55

Q. 4 ~h •• • The U in italics is for a diffusion study in the presence of added F ions .

233
LiCl-KCl

Table 27.12.4. Diffusion coefficients for species not included in

table 27.12.3

Species T(K)

D x 10f

(cm 2 sec 1 ) Recommended

study

Spec ies T<K)

D x 10$

(cm 2 sec 3

) Recommended

study

Na

+ 677 1.97 116 Gd 3+ 673 0.054 124

755 2.65 Tb 3 + 673 0.046 124 Ge 2 + 723 2.2 129 Dy 3+ 673 0.043 124

Sb 3 + 723 1.2 108 Ho 3+ 673 0.045 124

Zn 2+ 723 1.15 74, 96, 99 Er 3 + 673 0.046 124

Hg 2 + 723 1.67 132 Tm 3 + 673 0.056 124

y 3+ 673 0.057 126 Yb 3 + 673 0.080 124

V

5 + 723 0.8 112 Lu 3 + 673 0.060 124 vo

2+ 723 2.68 88 NpO 2 673 0.48 123 Nb 2 +

723 3.5 94 NpO 2 + 673 0.20 123

Nb 3 C 1 8 773 3.2 135 0 2 “ 673 1.6 76 948 9.3 713 2.6 [TaCl 6 ] 2_a 773 9.0 105 753 4.8

873 25 .

783 7

2 948 46.0 VO 3 723 0.76 131 [MoC1 6 ] 3 873 1.43 127 2- Cr 0 u 723 0.96 118, 137 973 2.89

1023 3.8 M0 O 4 723 1.64 130

W

3 +

723 0.71 137 Mo 0 2 C

2 723 1.08 130

Pd 2 +

723 1.39 108 po^" 723 0.80 119

758 1.68 107

s

2 " 693 0.312 121

Pt 2 +723 1.49 108

Cl, 673 6 . 0 114, 115

Pr 3 673 0.037 124 723 16 Nd 3 + 673 0.064 124 773 17 843 23 Sm 3 673 0.153 124 HC1 677 18 133, 134

Eu 3 673 0.111 124 735 25 793 21 a

[TaCl 6 ] 2 "; values of diffusion coefficients H 2 0 723 1.77 117 appear improbable: possibly a factor of 10 too high

References

Na

+

, 116; Tl\ 68 , 72, 73, 93, 96, 98; Ge

2 +

) 129; Pb

2+

, 68 , 70,

72-74, 93, 96, 100 , 101, 136; Sb 3 +

, 108; Bi 3 +, 69, 70, 74, 93, 96

108, 136 ; Cu

+

, 69, 83, 93, 95, 96 , 116, 136; Ag

+

, 69-73, 83, 93,

96, 97, 120, 136; Au

+

, 83; Zn , 74, 96, 99; Cd

2+

, 68 - 70, 74, 91,

93, 95, 96 , 98 -101 , 128; Hg

2 +

» 132 . y

3 * 126 ; La

3 +

, 79 , 324; V

5+

, 112 ; vo

2+

, 88 ; Nb 2 +

, 94; Nb 3 +, 86 , 94; Nb

3 C18

, 135 ; TaCl 2 ', 105;

Cr 3 +

, 81, 89, 93, 98, 102, 103 ; Mo

3 +

9 77' ' 9 104 ; MoCl 3 ', 127 ; W

3+

, 137

» « 2 + Mn , 93, 99, 106; Fe

2 +

9 83, 46; Co

2+

, 68 , 82 , 93 , 98,

101 ; Ni 2 *

, 75, 80, 83, 95, 96, 98, 101 , 106 ; Pd

2+

, 107, 108 ; Pt

2+

108; Ce

3 +

, 109, 124; Pr , 124; Nd 3 +

9 124 ; Sm

3+

, 124; Eu

3 +

% 124; ’ Gd 3 +

, 124 ; Tb 3 +

; 124 ; Dy

3+

;, 124 u 3 +

; Ho , 124; Er

3+

, 124 • tTM

3 +

; Tm , 124;

Yb 3 +

, 124 ; Lu

3+

, 124 ; u

3+

, 78, 91, 113 ; u

4+

, 70, 78, 84, 85 , 90,

91, 110 , 113; U0

2+

, 90, 113; Np

3 +

9 85, 92; Np^ , 84, 110 , 113;

NpO*, 123; NpO 2 *

, 123; Pu

3+

, 91, 92, 111, 122; Pu

4+

, 84; Am 3 *,

92; Cm

3+

, 125; O

2 ", 76; VO 3 , 131; CrO 2 ", 87, 118; MoO 2 ", 130;

MoO^Cl

2

, 130; PO^", 119; S

2 ", 121; Cl

2

, 114, 115; HC1, 133, 134;

H

2 0, 117.

234
9.

LiCl-KCl

Heat of Fusion ( AH^.)

Measurement method: drop calorimetry [138,139]

Table 27.13. Heat of fusion of eutectic

AH ° -X (kcal mol ) Uncertainty

3 . 13 'V ± 1%

References [138-140],

10. Heat Capacity (Cl

Measurement method: drop calorimetry [138]

Table 27.14. Heat capacity of eutectic

C T emp . range Uncertainty

P,

(cal K Imo 1 ) (K)

17 .

625-852 'v ± 3.5%

References [138,140].

11. Volume Change on Melting (AV^.)

Measurement method: estimated from densities [141]

Table 27.15. Volume change on melting of eutectic

Binary mixture

(mol % LiCl)

( A V - / V ) r s Uncertainty

58 .

15 . 8% m ± 5%

References [141]

Vapor r Pressure (p ) * vap

No vapor pressure studies reported.

Thermal Conductivity (liquid) (\ n ) £ Measurement method: transient hot wire [142]

Precision: not estimated, uncertainty: m + 201

Table 27.16. Thermal conductivity of eutectic melt

T A x 10^

(K) (cal cm

- ^sec~^K - l

626.5 16.5

12 .

12 .

References [142]

235
LiCl-KCl

14.

Thermal Conductivity (solid) (X ) s Measurement method: transient hot wire [142]]

Precision: not estimated, uncertainty: ^ + 10%

Table 27.1.7. Thermal conductivity of solid

Sole investigation.

References [142] .

IS. Cryoscopic Constant (k,J

Measurement method: calc'd from AH£ [141]

Table 27.18. Cryoscopic constant of eutectic

k rf Uncertainty

(K rool'

1 kg

_1

)

14 .

'v. ± 1%

References [139,141,143,144].

16

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LiCl-KCl

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LiCl-KCl

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240
LiCl-KCl

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Elektrokhim, Ural Fil. Akad. Nauk SSSR, 5_, 41 (1964).

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and Duyckaerts

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G.‘, Inorg. Nucl. Chem. Lett., 5

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241
LiCl-KCl

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Elektrokhimiya , _5, 1476 (1969).

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Phys. Chem., 62, 248 (1958).

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(N.F.) , 94_, 1 (1975) .

242
XXVIII, Sodium Chloride - Potassium Chloride: NaCl-KCl

1. Melting Temperatures (T ) Pure substance melting points:

NaCl : 8 00°C

KC1 : 77 0°C

Solid solution, minimum melting point:

685°C, composition: 50 mol % NaCl

Figure 28.1. NaCl-KCl phase diagram

References [1-3] .

2. Density (p)

Measurement method: Archimedean technique [4]

Single variable equation

p = a + bT (28.1)

precision: in table 28.1 uncertainty: ^ + 0.51

Table 28.1. Coefficients for single variable equation (28.1),

and precisions

Mol % NaCl a -b x 10 4 Precision

0 2 . 1376 5 . 8445 ±0.03%

20.75 2 .1377 5.8127 ±0 . 01%

41.00 2 .1342 5.7477 ±0.02%

51.23 2.1314 5 .6793 ±0.01%

65.15 2 . 1338 5 .5749 ±0.01%

72.94 2 .1374 5.5900 ±0.02%

84.77 2.1400 5 .5381 ±0.02%

100 2.1365 5 .4052 ±0.05%

243
NaCl-KCl

Two - independent -var iabl e equation

p = a + bT + cC 3 + dTC + eCT 2 (Omol % KC1) (28.2)

precision: + 0.11% uncertainty: ^ + 0.5%

Table 28.2. Coefficients for two - independent -var iabl e equation (28.2)

a b x 10 4 c x 10® d x 10 7 e x 1 0

1 ®

2 . 14250 -5 .45436 2.79726 -9.89901 2 .78444

Table 28.3. Densities (g cm’ 3

) from equations (28,1) and (28.2)

Mol % NaCl

T

(K) 100 84.77 72.94 65.15 51.23 50.00 41.00 20.75 0

945

960 1.586 1.588 1.582

975 1.578 1.574

990 1.584 1.582 1.569 1.571 1.565

1005 1.576 1.574 1.561 1.557 1.554

1020 1.567 1.565 1.552 1.554 1.548 1.545

1035 1.559 1.557 1.544 1.539 1.536

1050 1.550 1.548 1.535 1.537 1.531 1.527

1065 1.550 1.542 1.540 1.527 1.522 1.519 1.515

1080 1.553 1.542 1.534 1.532 1.518 1.520 1.513 1.510 1.506

1095 1.545 1.534 1.525 1.523 1.510 1.505 1.501 1.498

1110 1.537 1 .525 1.517 1.515 1.501 1.508 1.496 1.493 1.489

1125 1 .528 1.517 1.509 1.507 1.493 1.488 1.484 1.480

1140 1.520 1.509 1.500 1.498 1.484 1.486 1.479 1.475 1.471

1155 1.512 1.500 1.492 1.490 1.475 1.470 1.466 1.463

1170 1.504 1.492 1.483 1.482 1.467 1.462 1.458 1.454

1185 1.496 1.484 1.475 1.473 1.449 1.445

1200 1.488 1.440 1.436

1215 1.480

1230 1.472

1245 1.464

1260 1.455

1275 1.447

1290 1.439

References [4-19],

3. Surface Tension (y)

Measurement method: maximum bubble pressure [11]

Single variable equation

y = a + bT (28.3)

precision: + 0,2% uncertainty: ^ t 2%

244
NaCl-KCl

Table 28.4. Coefficients for single variable equation (28.3)

Mol % NaCl a -b x 10 2

0 176.8 7.5

10 178.1 7.5

25 178.0 7.4

40 177.3 7.2

50 179.3 7.2

60 180.4 7.2

75 181.2 7.0

90 183.5 6.8

100 187.0 6.8

Two - independent -variable equation

Y

= a + bT + cC + dC 2 + eC

3 + fTC 2 + gCT 2 (C = mol % KC1) (28.4)

precision: + 0.201 uncertainty: ^ + 2 %

Table 28.5. Coefficients for two-independent-variable equation (28.4).

a b x 10 2 c x 102 d x 10 3 e x 10 5 f x 10 8 g x 10 8

186 . 76500 -6.77993 -3.41591 3.42500 -1.28519 -3.15694 -3.79717

Table 28.6. Surface tension (dyn cm ^) from equations in table 28.4

Mol X NaCl

T ( K ) 100 90 75 60 50 40 25 10 0

980 116.9 112.6 109.8 108 . 7 106.7 105.5 104.6

990 116.2 111.9 109.1 108.0 106.0 104.7 103.9

1000 119.0 115.5 111.2 108.4 107.3 105.3 104.0 103.1

1010 118.3 114.8 110.5 107.7 106.6 104.6 103.3 102.4

1020 117.6 114.1 109.8 107.0 105.9 103.9 102.5 101.6

1030 117.0 113.5 109.1 106.2 105 .

103.1 101.8 100.9

1040 116.3 112.8 108.4 105.5 104.4 102.4 101.0 100.1

1050 115.6 112.1 107.7 104.8 103.7 101.7 100.3 99.4

1060 114.9 111.4 107.0 104.1 103.0 101.0 99.6 98.6

1070 114.2 110.

106.3 103.4 102.3 100.3 98.8 97.9

1080 113.6 110.1 105.6 102.6 101.5 99.5 98.1 97.1 95.8

1090 112.9 109.4 104.9 101.9 100.8 98.8 97.3 96.4 95 .

1100 112.2 108 . 7 104.2 101.2 100.1 98.1 96.6 95.6 94.3

1110 111.5 108.0 103.5 100 .

99.4 97.4 95 .

94.9 93.6

1120 110.8 107.3 102.8 99.8 98.7 96.7 95.1 94.1 92.8

1130 110.2 106.7 102.1 99.0 97.9 95.9 94.4 93.4 92.1

1140 109.5 106.0 101.4 98.3 97.2 95.2 93.6 92.6 91.3

1150 10 8.8 105.3 100.7 97.6 96.5 94.5 92.9 91.9 90.6

1160 108.1 104.6 100.0 96.9 95.8 93.8 92.2 91.1 89 .

1170 107.4 103.9 99 .

96.2 95.1 93.1 91.4 90.4 89.1

1180 106.8 88.3

1190 106.1 87.6

1200 105.4 86.8

1210 104.7 86.1

1220 104.0 85.3

References [4-12,19-23].

245
NaCl-KCl

4. Viscosity (r\)

Measurement method: oscillating sphere [7]

n = a + bT + cT

2 + dT 3 (28.5)

precision: in table 28.7 uncertainty: ^ ± 25%

Table 28.7. Coefficients of equation (28.5), and precisions

NaCl

(mol %)

a -b x 10 2 c x 10 6 d x io 9 Precision

0 1 .7091 -1 .5846 -27.7213 11.5836 ±0.57 %

20.75 14 .1361 1 . 9076 5.0784 1 .2900 ±0 .29%

41.00 11.6454 1 .1612 -1 .9476 3 .4160 ±0.55%

51.23 18 . 3576 2 .5649 7.1721 1 .6990 ±0 .61%

65.15 16.2796 2.0228 3.0276 2 .5895 ±0 .38%

84.77 15.2401 1.4962 -3.3789 4.9174 ±0 .25%

n = A exp (E/RT) (28.6)

precision: in table 28.8, uncertainty: ^ t 5%

Table 28.8. Coefficients of equation (28.6), and precisions

LiCl

(mol %)

A x 10 2 E (cal mol -

) Precis ion

72.90 2 . 231 8699 ±0.60%

100 1 .821 9341 ± 0 .47%

Table 28.9. Viscosity (cp) from equations in tables 28.7 and 28.8

Mol X NaCl

T

( K ) 100 84.77 72.90 65.15 51.23 41.00 20.75 0

1000 1.777 1.668 1.580 1.502

1010 1.702 1.605 1.519 1.450

1020 1.631 1.545 1.460 1.400 1.331

1030 1.565 1.486 1.404 1.351 1.285

1040 1.557 1.502 1.430 1.351 1.305 1.241

1050 1.498 1.443 1.376 1.300 1.260 1.199

1060 1.441 1.387 1.324 1.252 1.217 1.158 1.154

1070 1.387 1.335 1.274 1.206 1.175 1.119 1.116

1080 1.335 1.285 1.226 1.162 1.136 1.082 1.080

1090 1.285 1.238 1.181 1.121 1.098 1.047 1.046

1100 1.307 1.239 1.194 1.139 1.083 1.062 1.014 1.014

1110 1.258 1.195 1.152 1.098 1.047 1.028 0.983 0.984

1120 1.211 1.153 1.112 1.060 1.014 0.996 0.954 0.957

1130 1.167 1.114 1.074 1.024 0.984 0.966 0.926 0.931

1140 1.125 1.078 1.038 0.990 0.956 0.937 0.900 0.908

1150 1.086 1.044 1.004 0.959 0.930 0.911 0.877 0.887

1160 1.048 1.013 0.972 0.931 0.907 0.887 0.855 0.869

1170 1.012 0.985 0.941 0.904 0.887 0.864 0.835 0.853

References [4-12,16,19,23-27].

246
NaCl-KCl

5. Electrical Conductance (k)

Measurement method: ac technique [4]

k = a + bT + cT 2 (28 .7)

precision: in table 28,10 uncertainty: v + 4% at T > 1050 K

Table 28.10. Coefficients of equation (28.7), and precisions

Mol % NaCl -a b x 1

2 - c x 1 0

5 Precision

0.00 5.5231 1.1714 0.4180 ±0.19%

20.40 2 .9567 0.7368 0.2270 ±0.29%

41 . 00 6.3093 1.3765 0.5147 ±0.22%

51 . 23 3 . 3119 0.8380 0.2641 ±0.40%

65.15 3 .1690 0.8265 0.2477 ±0.19%

72.94 4.0668 1.0120 0.3317 ±0.30%

84. 77 1 .3797 0.5656 0.1274 ±0.24%

100. 00 2.3356 0.7783 0.2118 ±0.22%

Table 28.11. Specific conductance (ohm ^cm ^

) from equations in table 28.10

Mol X NaCl

T(K) 100.00 84.77 72.94 65.15 51.23 41.00 20.40 0.00

940

950 960 2.299 2.162

970 2.517 2.332 2.200

980 2.552 2.364 2.237

990 2.586 2.396 2.273

1000 2.736 2.619 2.427 2.309

1010 2.771 2.652 2.458 2.343 2.169

1020 2.805 2.684 2.488 2.376 2.197

1030 2.838 2.716 2.518 2.408 2.224

1040 3.125 2.870 2.748 2.547 2.439 2.251

1050 3.154 2.902 2.778 2.575 2.469 2.277

1060 3.184 2.933 2.809 2.603 2.498 2.303 2.197

1070 3.214 2.964 2.839 2.631 2.526 2.328 2.225

1080 3.600 3.243 2.993 2.868 2.658 2.553 2.353 2.252

1090 3.632 3.272 3.023 2.897 2.685 2.579 2.377 2.279

1100 3.663 3.300 3.052 2.925 2.710 2.604 2.401 2.304

1110 3.694 3.329 3.079 2.953 2.736 2.628 2.425 2.329

1120 3.724 3.357 3.107 2.981 2.761 2.651 2.448 2.353

1130 3.755 3.385 3.133 3.008 2.785 2.673 2.471 2.376

1140 3.784 3.412 3.159 3.034 2.809 2 .694 2.493 2.399

1150 3.814 3.440 3.184 3.060 2.832 2.714 2 . 514 2.420

1160 3.843 3.467 3.209 3.085 2.855 2.732 2.536 2.440

1170 3.871 3.494 3.233 3.110 2.877 2.750 2.556 2.460

1180 3.899 3.520 3.256 3.135 2.899 2.767 2.577 2.479

1190 3.927 3.547 3.279 3.159 2.597 2.497

1200 3.954 3.573 3.301 3 . 182 2.616

1210 3.981 3.205

1220 4.007

1230 4.033

1240 4.059

1250 4.084

1260 4.108

1270 4.133

1280 4.156

1290 4.180

References [4-13,19,28-39].

6. Safety and Hazards

A. Hazard rating [40-42]

(i) Toxicity: NaCl, very low; KC1 , slight

(ii) Vapor pressure: no data for mixture; but see: NaCl, KC1.

247
NaCl-KCl

B. Disaster hazards [40,43-45]

(i) Molten salt bath "explosions": i.e., explosive generation

of steam due to bulk water "carry-over" and/or equipment

failure; i.e., explosive expansion of "trapped" air.

(ii) Chlorides evolve highly toxic fumes when

heated to decomposition or contacted with acids.

References [40-45]

7 . Corrosion

Table 28.12. Corrosion studies from primary research literature

Studies References

Ni, Fe 46

Zr, Be, Ti, Hf, U 47

Ni-Cr-Fe 48

Ti 49,50

Cr 0 + C electrode

2 3 51

Fe 52

Ni-Cr 53

Fe, Ni 54

Steel 3 55

Ni-Fe 46,56

Au, Pt, W 57

Several metals 58

Fe 59

Ni 60

Zr 47

Rh 61

A1 62

Cr, Fe-Cr 63

W 64

Emf . series 58

Thermodynamic redox diagrams 46,65

Electrochemical approach 66,67

Reviews (molten salts corrosion) 68-70

Annotated corrosion biblio. 71

References [46-71]

248
NaCl-KCl

8. Diffusion

Measurement method: cited in tabulations

List of diffusing species investigated in NaCl-KCl as solvent

Be

2+

, Mg

2+

, Al

3+

, Tl\ Pb

2+

, Cu

+

3 Ag

+

, Zn

2+

, Cd 2+

, Y

3+

, Zr

2+

, Zr

4+

, ZrF

2 ", Hf 2+

, Hf

4+

, HfF 2 ", Nb 2+

, Nb 3+

, Nb-Clg , KNbF

Cr

3+

, Mo 3+

, W

4 +

, W

5+

, Fe

2+

, Co

2+

, Ni +3 Ni 2+

, Th

4+

, U

3 +

u

4 +

, uo

2+

, po

3

4 ~, ci

2

, net, so

3

, co

2

.

The italicized species indicate studies with insufficient data-sets for

characterization of temperature dependence of diffusion coefficients.

For these species see table 28.13.4.

Equation: D = A exp [-E/RT] (28.8)

precision: in table 28.13.2 uncertainty: in table 28.13.1

Table 28.13.1. Diffusion techniques, uncertainties, and species

Diffusion techniques

of recommended study

Uncertainty

(in values of D)

Species

chronopotent iome try <\i± 10% Be

Ag

2 +

+ Mg

Cd 2

2 +

Al

r3 +

3 +

T

.2 + ZrFg . Hf 2

‘

Nb 2+

, Nb 3+

, K 2 NbF 7 , W

4+

Fe 2 + Th 4

Hf

N+

Z r

^

' , Zr

Hf Fg

Pb

4 +

2 +

.2 + UO 2 , CI 2 , Zn , Nb 3 Cl 8 , CO 2

, N i" S0 3 , C0 2

N i

» +

F 0 4 ~.

galvanostatic 2 0 % Cr 3 +

vo 1 tamme try 20 % Cu

rotating disc electrode 20 % HC1

249
NaCl-KCl

Table 28.13.2. Diffusion equation parameters, precisions,

and recommended study

Species A x 10 3

( cm 2 sec 1 )

E (cal mol 1

) Temp, range

(K)

Pr ec is ion Recommended

study

Be 2+ 5.27 10700 950-1070 83

Mg 2 +

3 . 80 8328 1020-1120 103

Al 3+ 1.096 6543 950-1090 89

Tl +

5 .16 8526 945-1040 ±2.6% 94

Pb 2 + 1.582 7678 970-1200 ±3.4% 90

Ag

+ 1.91 6411 980-1150 ±2.8% 87

Cd 2+ 1.63 7030 950-1070 96

Y

3 +

1 .49 8359 950-1090 76

Zr 2+5 .40 11100 970-1170 ±0.4% 86

Zr 4+ 6.20 9800 970-1170 86

Zr F 3 . 60 14963 970-1070 72

Hf 2 + 2.73 7950 970-1170 84

Hf 4 +

4 .40 9200 970-1170 120

HfF 9 .55 12767 950-1130 100

Nb 2+

9 . 12 9152 970-1110 85

Nb 3 +

4 .36 10500 970-1110 85

Cr 3 +

5 . 75 11472 1020-1120 82 w

4+ 11.38 12643 970-1130 81 w

5+ 15.21 13480 970-1130 81

Fe 2 + 6.53 9839 960-1180 79

Th“+ 17.46 127 76 950-1100 78

Th"*'6 60.26 15897 950-1100 78

u 3+2 .83 8800 950-1170 110

u 4+ 9.55 11797 950-1160 110 uo 2 +

2 . 94 10726 950-1120 110

Cl 2 linear equation3 1010-1110 111

No entry in precision column indicates estimate not possible since results

were reported as equations only.

a Cl 2

: D = 0.95 x 10 3 - 0.9 x 10 6 (T-931)

0

2 h Th k+ : The italics indicate that in this study, the diffusion of Th 4 + was investigated in the presence of added F ions; diffusing

species uncertain.

250
NaCl-KCl

Table 28.13.3 (Part 1). Diffusion coefficients D x 1 0^ (cm^sec )

from equations in table 28.13.2

T

(K) Be 2 + Mg 2 +

Al 3 + Tl +

Pb 2 +

Ag

+

. Cd 2 +y 3+ Zr 2+ Zr 4 + ZrFg" Hf 2 +

Hf 4 +

Hf Fg

-

950 1.82 3.42 5.64 3.93 1.78 1.10

970 2.05 3.68 6.19 2.95 4.25 1.95 1.70 3.84 1.53 4.41 3.72 1 .27 980 2.17 3.81 6.47 3.07 7 . 10 4.41 2.04 1.81 4.04 1.66 4.60 3.91 1.36

1000 2.42 4.07 7.07 3.32 7 . 53 4.74 2.22 2.02 4.47 1.93 5.00 4.29 1.55

1020 2.69 6.24 4.34 7 . 69 3.58 8.08 5.08 2.41 2.26 4.93 2.24 5.40 4.70 1.76

1040 2.97 6.75 4.62 8.33 3.85 8.58 5.43 2.61 2.51 5.41 2.58 5.83 5.13 1 .98 1060 3.28 7.29 4.91 4.13 9.10 5.79 2.82 2.78 5.91 2.96 6.27 5.58 2.23

1070 3.44 7 . 56 5.05 4.27 9.36 5.97 2.92 2.92 6.17 3.16 6.49 5.81 2 . 3 6 1090 8.13 5.34 4.57 9.90 3.14 3.21 6.72 6.95 6.29 2.63

1100 8.41 4.72 10.17 3.36 7.00 7.19 6.54 2.78

1120 9.01 5.02 10.71 3.68 7 .58 7.67 7.05 3.08

1130 5.18 10.99 3.85 7.87 7.92 7.31 3.24

1150 5.50 11.55 4.20 8.51 8.42 7.85

1170 5.82 4.56 9.16 8.93 8.41

1190 6.15

1200 6.32

[ Al 3 +

; for Al 3 + conc'ns < 0.18 wtZ]

Table 28.13.3 (Part 2). Diffusion coefficients, D x 10^(cm^sec ^),

from equations in table 28.13.2

T(K) Nb 2 +

Nb 3 +

Cr 3 + w

4+ W 5+ Fe 2 + Th 4+ Th h +

U

3 +

U

4 + CM +

3 O CM Cl 2 950 2.01 1.33 2.67 1.84 1 . 00 960 3.76 2.15 1.45 2.81 1.97 1.06

970 7.90 1.88 1.61 1.40 3.96 2. 31 1.58 2 . 94 2.10 1.13

980 8.30 1.99 1.72 1.50 4.17 2.47 1.72 3.08 2 . 23 1.19

990 8.70 2.10 1.84 1.61 4.39 2 . 64 1.86 3.23 2.37 1.26

1000 9.11 2.21 1.96 1.72 4. 62 2.82 2 . 02 3.38 2.52 1.33

1010 9.54 2.33 2.09 1.84 4.85 3.00 2.19 3.53 2.67 1.40 87 .

1020 9.97 2.45 2.00 2 . 22 1.97 5.09 3.19 2.36 3 . 68 2 . 83 1.48 87 .

1040 10.88 2.71 2.23 2.51 2.23 5.59 3.61 2 .75 4 . 00 3.17 1 . 64 85.2

1060 11.83 2.98 2.48 2.81 2.53 6.11 4.05 3.18 4 . 34 3.53 1.81 83.4 1070 12.32 3 . 12 2.61 2.98 2 . 68 6.38 4.29 3.41 4 .51 3.72 1.89 82.5

1090 13.33 3.42 2.88 3.32 3 . 01 6.95 4.79 3 . 91 4.87 4.12 2.08 80.7

1100 13.85 3.57 3.02 3.50 3.19 7.24 5.05 4 .18 5 . 05 4.33 2.17 79.8 1110 14.38 3.73 3.17 3.69 3.37 7 . 54 5.24 4.54 2.27 78.9

1120 3.32 3.88 3.56 7.85 5.43 4.76 2.37 1130 4.08 3.76 8.16 5.62 4.99

1150 8.81 6.02 5.47 1170 9.48 6.43 1180 9.83

lTh k

; italicized indicates study with

added F~ ions; diffusing species uncertain]

251
NaCl-KCl

Table 28.13.4. Diffusion coefficients for species not

included in table 28.13.3

Species T(K)

D x 1 0

5 (cm 2 sec 1

) Recommended

study

Cu

+ 773 6.7 116

1123 23.0 114,115

Zn 2 + 973 4.6 91,93

Nb 3 Cl 8 948 8.6 124

K 2 NbF 7 1023 4 .

121

Mo 3 + 1000 2 . 9 101

Co 2 + 973 2 . 04 102

1079 2.59

Ni+ 1003 70 106

N i

2 + 978 2.36 91,104,105,106

1080 2 .87

PO 4 " 1053 0.82 122

HC1 988 10 75,112

1068 25

1093 27

1180 30

S0 3 1023 20 117

C0 2 973 17 125

Temperature dependence of D reported in graphical form.

References

Be

2+

, 83; Mg

2+

, 103; Al

3+

, 89; Tl

+

, 94, 119; Pb 2+

, 73,88,90,91 , 93,95,107,108; Cu

+

, 114-116; Ag

+

, 72,87,88,91,95; Zn

2+

, 91,93;

Cd 2+

, 80,88,91,93,95-98; Y

3+

, 76; Zr

2+

, 72,86,99; Zr

4+

, 72,86;

ZrF

2 ', 72; Hf

2+

, 84; Hf 4+, 100,120; HfF 2 \ 100; Nb

2+

, 85; Nb

3+

, 85;

Nb

3 Cl

g

, 124; K

2 NbF

?

, 121; Cr

3+

, 82,118; Mo

3 ", 101; W

4+

, 81; W

5+

, 81; Fe

2+

, 79; Co

2+

, 102; Ni

+

, 106; Ni 2+

, 91,104-106; Th4+

, 78;

U

3+

, 109,110,123; U

4+

, 109,110,123; U0 2+

, 92,109,110, 123; PO

3 ",

122; Cl

2

, 74,77,111,113 ; HC1, 75,112; S0

3

, 117; CC>

2

, 125

9. Heat of Fusion (AHj.)

No data.

10. Heat Capacity J

No data.

252
NaCl-KCl

11.

Volume Change on Melting (AF^J

Measurement method: capillary technique [126]

Table 28.14. Volume change on melting of minimum melting

solid solution

( AV / V ) r s Uncertainty

14.8% 'V' ± 4 %

References [126] .

12.

Vapor Pressure (p , ) r r vap

Measurement method: transpiration [127]

precision: not estimated uncertainty: ^ + 10%

Table 28.15. Vapor pressure(mm)

References [127,128],

13. Thermal Conductivity (liquid)

No thermal conductivity studies reported.

14. Thermal Conductivity (solid) (A^J

No thermal conductivity studies reported.

15. Cryoscopic Constant (kj>)

No data.

16. References

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253
NaCl-KCl

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254
NaCl-KCl

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255
NaCl-KCl

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,

Zh. Priklad. Khim., 46, 1918 (1973).

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Battelle, Geneva,

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SSSR, Ser . Khim. Nauk, 6^ 70 (1967).

256
NaCl-KCl

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Elektrokhim. Rasplav. Solei Shlakov, 262 (1968).

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2 57
NaCl-KCl

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898, A53 (1965). (Cited by Ref. 96).

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,

7, 725 (1971).

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258
NaCl-KCl

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XXIX. Lithium Chloride -Aluminum Chloride: LiCl-AlCl^

1. Melting Temperature (T ) Pure substance melting points:

LiCl : 610°C

A1C1

3

: 192°C

Eutectic melting point:

114°C, composition: 40 mol % LiCl

0 20 40 60 80 100

AICI 3 MOL % LiCl LiCl

Figure 29.1. LiCl-AlCl, phase diagram

References [1-3]

2 . Density (p

)

Measurement method: dilatometric technique [3]

Two- independent -variable equation

p f

a + bC + cT + dC 2 + eCT + fC 2 T (C=Mol % A1C1

3

) (29.1)

precision: + 0.11% uncertainty: v + 1%

Table 29,. 1. Coefficients for two - independent -variable equation (29.1)

a b x 10

2 3 c x 104 d x 10

5 e x 10

7 f x 10

2.47542 -2.02834 -2.15321 1 .97633 5 .76140 -5 . 91700

260
LiCl -AlClj

_ 3 Table 29.2. Densities (g cm ) from equation (29.1)

T(K) 50.00 55.00

Mol % AlC

60.00

3 65 . 00 70.00 75.00

420 1.6396

430 1.6321

440 1.6246

450 1 .6170

460 1.6095

470 1 .6020 1 .5937 1.5814 1 .5651 1.5448 1 .5204

480 1.5945 1 . 5860 1.5732 1.5560 1.5346 1 .5088

490 1.5870 1 .5782 1 .5649 1.5470 1.5244 1.4972

500 1.5795 1.5705 1.5566 1.5379 1.4856

510 1.5719 1.5628 1 .5484 1 .5288 1.4740

520 1.5644 1.5550 1 . 5401 1 .4624

530 1 .5569 1.5319

540 1.5236

References [ 3 - 5 ]

3. Surface Tension (y)

No data.

4. Viscosity ( nJ

No data.

5.

Electrical Conductance (k)

Measurement method: ac technique [7]

Single variable equation

k = A exp (-E/RT) (29.2)

precision: in table 29.3 uncertainty: ^ ± 5%

Table 29.3. Coefficients of equation (29.2), and precisions

Mol % A1C1

3 A

E -1

(cal mol ) Precis ion

49.25 4 . 09405 2168 ± 4.40

55 . 00 4.49855 2536 ± 1.50

59.98 3 . 98840 2650 ± 1.00

64.92 3 . 11955 2614 ± 0.69

69.99 2.99865 2800 ± 0.16

75.10 1 . 68110 2579 ± 0.83

Two- independent- variable - equation

k = a + bC + cT + eCT + fC

2 T (29.3)

precision: + 5.1% uncertainty ^ + 5%

261
LiCl-AlCl

3

Table 29.4. Coefficients for two-independent-variable

equation (29.3)

a b x 10 2 c x

10"^ 4 d x 10 ex 10^ f x 10 7 -1.86688 2 .69890 7 .40140 -0.50263 -1.30430 5 . 1200

Table 29.5. Specific conductance (ohm ^ cm from equations

in table 29.3

Mol % A1C1

3

T(K) 49.25 55.00 59 . 98 64.92 69.99 75.10

420

430 0.23128 0.17944

440 0.34301 0.24742 0.19255 0.15693

450 0.36244 0.26389 0.20596 0.16771

460 0. 38205 0.28067 0.21967 0.17872

470 0.40182 0.29774 0.23364 0.18993 0.10626

480 0.42173 0.31507 0.24787 0.20133 0.15924 0.11255

490 0.44176 0.33264 0.26233 0.21291 0.11894

500 0.46187 0.35042 0.27701 0.22466 0.12541

510 0.48206 0.36841 0. 29188 0.23655 0.13195

520 0.50231 0.38657 0.30693 0.24858 0.13857

530 0.52259 0.40489 0.32215 0.26073

540 0.54290 0.42335 0.33751 0.27299

550 0.56321 0.44194 0.35301

560 0.58352 0.46063 0.36863

570 0.60381 0.47942 0.38436

580 0.62407 0.49829

590 0.64428 0. 51723

600 0.66445

610 0.68455

620 0.70459

References [4 - 7 ]

6. Safety and Hazards

A. Hazard rating [8,9]

(i) Toxicity: LiCl, slight; AlCl^, severe.

(ii) Vapor pressure: appreciable; see [23, 24]

B. Disaster hazards [8,10-12]

(i) Molten salt bath "explosions": i.e., explosive generation

of steam due to bulk water "carry-over" and/or equipment

failure; i.e., explosive expansion of "trapped" air.

(ii) Chlorides when heated to decomposition, or contacted with

acids, emit highly toxic fumes; A1C1, reacts exothermically

with moisture/water evolving HC1 fumes.

References [8-12].

262
LiCl-AlCl

3

7.

Corrosion

Table 29.6. Corrosion studies from primary research literature

S tud ies References

Pyrex glass, Pt, quartz, silica 4-6

Electrochem. approach 13,14

Thermodynamic redox diagrams 15-17

Reviews: corrosion 18-20

Annotated biblio. 21

References [4-6,13-21].

8. Diffusion

No diffusion studies reported.

9. Heat of Fusion ( Measurement method: estimated [22]

Table 29.7. Heat of fusion of eutectic

AH°

f Uncertainty -1

(kcal mol )

5 . 8 ^ ± 5%

10 .

References [22]

Heat Capacity (C ) No data.

11 . Volume Change

Measurement

on Melting (AV^J

method: estimated from densities [ 22 ]

Table 29.8. Volume Change on melting

Binary eutectic

(mol % LiCl)

< 4 VV Uncertainty

40 36.4% ^ ± 5%

References [22]

12. Vapor Pressure (pr ) vap

Measurements in progress [23,24H

References E 2 3 , 2 4

263
LiCl-AlCl.

13. Thermal Conductivity (liquid) (X^J

No thermal conductivity studies reported.

14. Thermal ConductivityJ (solid) (X ) s No thermal conductivity studies reported,

15.

Cryoscopic Constant

Measurement method: estimated [22]

Table 29.9. Cryoscopic constant

Binary mixture k

f Uncertainty

(mol % LiCl) (K mol'^kg - !)

60 4 . 07 ^ ± 5%

References [22]

16.

References

[1] Kendal, J. , Crittenden, E. D. , and Miller, H. K. , J. Amer. Chem. Soc.,

45, 963 (1923).

[2] Janz, G. J., Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T.,

"Eutectic Data" - 2 vols.; ERDA TID- 27163-PI 6 P 2 ; NTIS, Washington,

D. C. (1977); see also, "Physical Properties Data Compilation Relevant

To Energy Storage. I. Molten Salts: Eutectic Data", NSRDS-NBS- 61

,

U. S. Gov't Printing Office, Washington, D. C. (1978).

[3] Carpio, R. A., King. L. A., and Fannin, A. A., Jr., J. Chem. Eng. Data

(submitted) 1978.

[4] Moss, R. H. , Diss. Abstr., 15^, 8 (1955).

[5] Yamaguti, Y. and Sisido, S., J. Chem. Soc. Japan, 6_2, 304 (1941).

[6] Grothe, H. , Aluminium, 38^, 320 (1962).

[7] Carpio, R. A., King, L. A., Kibler, F. C., Jr., and Fannin, A. A., Jr.,

J. Electrochem. Soc. (submitted); private communication to G. J. Janz

(April 1978) .

[8] "Dangerous Properties of Materials ", Sax, N. I., Van Nostrand Reinhold

Co. , N. Y. (1969)

[9] "Registry of Toxic Effects of Chemical Substances", Christensen, H. E.

,

and Lubinbyhl, T. T. , eds., U. S. Dept. H. E. W. , U. S. Gov't Printing

Office, Washington, D. C. (1975).

[10] "Potential Hazards in Molten Salt Baths for Heat Treatment of Metals",

National Board Fire Underwriters Research Report No. 2 (1954).

[11] "Handbook of Reactive Chemical Hazards", Bretherwick, L., Butterworths Co.,

London (197 5) .

[12] Janz, G. J., Tomkins, R. P. T., Downey, J. R. , Jr., and Allen, C. B.,

"Safety and Hazards" Chapter in "Eutectic Data", NTIS, U. S. Dept.

Commerce, Springfield, Va. (1977).

[13] Pizzini, S., "Materials Problems In the Industrial Application of Molten

Salts", Proceedings International Symposium on Metal -Slag-Gas

Reactions and Processes", The Electrochemical Society, Inc., Princeton,

N. J. , p. 581 (1975) . 264
LiCl -AlClj

[14] Johnson, K. E., "Electrochemical Approaches To Corrosion In Molten

Salts ", "Proceedings International Symposium on Metal-Slag-Gas

Reactions and Processes", The Electrochemical Society, Inc.

Princeton, N.J., p. 581 (1975).

[15] Littlewood, R. , J. Electrochem. Soc., 109 , 525 (1962).

[16] Edeleanu, C., and Littlewood, R. , Electrochimica Acta, _3, 195 (1960).

[17] Littlewood, R. , and Argent, E. A., Electrochimica Acta, 4_, 114 (1961).

[18] Inman, D. , and Wrench, N. S., Brit. Corr. J., 1_, 246 (1966).

[19] Smirnov, M. V. , and Ozeryanaya, I. N. , Nauki Tekh. Korros. Zashch.

Korros. , 2, 171 (1973)

[20] Ketelaar, J. A. A., Chemie Ing. Techn., 45_, 667 (1973).

[21] Janz, G. J.-j and Tomkins, R. P. T., Corrosion, _34 (in press) (1978).

[22] Janz, G. J., et al . , (MSDC-RPI) unpublished work (1977).

[23] King, L. A., [Frank J. Seiler Research Laboratories (AFSC) , USAF] private

communication to G. J. Janz (December 1977).

[24] Linga, H. , Motzfeldt, K. , and 0ye , H. A., Preprint: "Vapor pressure

of molten alkali chloride-aluminum chloride mixtures" (1978).

265
XXX. Sodium Chloride -Aluminum Chloride: NaCl-AlCl^

1. Melting Temperatures (T ) Pure substance melting points:

NaCl : 800°C

A1C1

3

: 192°C

Eutectic melting point:

105-108°C, composition: 36.8 mol % NaCl

Figure 30.1. NaCl-AlCl^ phase diagram

References [ 1 - 5 ]

2. Density (p)

Measurement method: flotation technique [6]

p = a + bT (30.1)

precision: in table 30.1 uncertainty: ^ + 5%

Table 30.1. Coefficients of equation (30.1), and precisions

Mol % NaCl a -b x 10 3 Precision

0.0 2 .371 2 .330 ±0.14%

27.0 2 . 011 0.920 ±0.07%

38 .

2 . 034 0.866 ±0.04%

48.0 2 .068 0.838 ±0.05%

266
NaCl-AlCl

3

Table 30.2. Densities (g cm from equations in table (30.1)

T (K)

Mol % NaCl

48.0 38.2 27 .

o

400 1.733

410 1.724

420 1.716

430 1.708

440 1.699 1 . 653

450 1.691 1 . 644

460 1.682 1.635 1.588

470 1.674 1.627 1.579

480 1.666 1.618 1.570 1.252

490 1.657 1.609 1.561 1.229

500 1.649 1.601 1 .551

510 1. 641 1.592 1 . 542

520 1 . 632 1 .583 1 .533

530 1.624 1.575 1.524

540 1.615 1 .566 1.515

550 1 . 607 1.505

560 1 .598 1.496

570 1.487

580 1.478

590 1.469

600 1.459

610 1.450

References [6-18].

3. Surface Tension (y)

No data.

4. Viscosity (r\)

Measurement method: oscillation cylinder [19]

n

= A exp (E/RT) (30.2)

precision: in table 30.3 uncertainty: ^ + 5%

267
NaCl-AlCl

3

Table 30.3. Parameters of equation (30.2), temperature

range, and precisions

Mol %

A1C1

3

Temp, range

(K)

A x 10 3 E (cal mol 1

) Precision

50.00 453-577 7 .2702 3285 .

± 1 . 11 %

55 . 00 455-574 6 .8398 3413 .

±0.99%

59.99 448-578 5 .7828 3661.1 ±1.48%

64 .96 443-577 4.9477 3850.2 ±1.29%

69.92 453-573 4 . 2341 3966 .

±0 .75%

74.80 468-579 3 .6622 3977.5 ±0.52%

79.72 472-575 2 .8309 3985 .

±1.25%

Table 30.4. Viscosity (cp) from equations in table 30.3

Mol % AICI

3 T(K) 50.00 55.00 59 . 99 64 .96 69.92 74.80 79 . 72

440

450 3.469 3 .667

460 2 . 645 2 .863 3.174 3.339 3 . 246

470 2 .450 2 . 644 2 .914 3 . 053 2 .960 2 .590

480 2.277 2 .450 2 . 686 2 .802 2. 709 2 .370 1 . 848

490 2 .123 2 .278 2 .483 2.580 2 .489 2.177 1 .697

500 1 . 984 2 .124 2 .304 2 .384 2.294 2 . 006 1 .564

510 1.859 1 . 985 2 . 143 2 . 210 2 . 121 1 .854 1 .445

520 1.747 1.861 1 .999 2 . 054 1 .967 1. 720 1.340

530 1.645 1 .748 1.870 1.915 1 . 830 1 .599 1 .246

540 1.553 1.646 1 .753 1.789 1.707 1.491 1 .162

550 1 .469 1.554 1.648 1.676 1 .596 1 .394 1.086

560 1 .392 1.470 1 .552 1 .574 1 .496 1 .306 1.017

570 1 .322 1.393 1.465 1 .481 1 . 405 1.227 0.955

References [6-16,19].

5. Electrical Conductance (k)

Measurement method: ac technique [14]

k = a + bT + cT

2 (30.3)

precision: in table 30.5, uncertainty: ^ + 4%

268
NaCl-AlCl

3

Table 30.5. Coefficients of equation (30.3), and precisions

Mol % NaCl -a b x 10 3 c x 10 6 Precision

18 . 9 0.2067 0.6780 0 ±0.63%

19 .

0.1839 0.6342 0 ±0.87%

30.9 0.4258 1.3836 0 ±0. 69%

31.0 -0.6993 -3 .3027 4 .8037 ±2.07%

42 .

0.5852 1. 9443 0 ±0.95%

49.2 0.6548 2.4082 0 ±1.32%

50.0 0.7966 2.7366 0 ±0.52%

Table 30.6. Specific conductance (ohm ^cm ^) from

equations in table 30.5

T Mol % NaCl

(K) 50.0 49 .

42 .

31.0 30. 9 19 .

18 .

420 0.160

430 0.167

440 0.176

450 0.186 0.197

460 0.462 0.453 0.309 0.197 0.211

470 0.490 0.477 0.329 0 . 208 0.224

480 0.517 0.501 0.348 0. 221 0. 238 0.121 0.119

490 0.544 0.525 0.368 0.234 0.252 0.127 0.126

500 0.572 0.549 0.387 0.249 0 .133 0.132

510 0.599 0.573 0.406 0.264 0.140 0.139

520 0.626 0.598 0.426

530 0.654 0. 622 0.445

540 0. 681 0.646 0.465

References [6-16,20].

6. Safety and Hazards

A. Hazard rating [21-23]

(i) Toxicity: NaCl, very low; AlCl^, severe

(ii) Vapor pressure: appreciable; see Table 30.11.2 (p . 27 3) and C 5 6

B. Disaster hazards [24-26]

(i) Molten salt bath "explosions": i.e. explosive generation

of steam due to bulk water "carry-over" and/or equipment

failure; i.e., explosive expansion of "trapped" air.

(ii) Chlorides, when heated to decomposition, or contacted with acids,

emit highly toxic fumes; AICI 3 reacts exothermically with

moisture/water, to evolve HC1 fumes.

References C21-26,56U

269
NaCl-AlCl

3

7 . Corrosion

Table 30.7. Corrosion studies from primary research literature

S tudies References

Al, Ag, Cu, Mo, Ni, Pd, Ti,

Fe, Pt, stainless steels 27

quartz, pyrex glass, Pt,

Ni, vycor 6,14,20,28

Thermodynamic and electrochemical

approach 29-31

Reviews (molten salts corrosion) 32-34

Annotated corrosion biblio. 35

References [6,14,20,27-35].

8. Diffusion

Measurement method: cited in tabulations

List of diffusing species investigated in NaCl-AlCl^ as solvent

m + 0 2 + D , 2 + + + ^2 + Na , Sn 3 Pb , Cu , Ag , Cd . u 4+

, r

Ti 2 + Zr

4 + Nb 5 + Fe

3 +

The italicized species indicate studies with insufficient data-sets for

characterization of temperature dependence of diffusion coefficients,

these species, see table 30.8.4.

precision: in table 30.8.2 uncertainty: in table 30.8

Table 30.8.1. Diffusion techniques, uncertainties, and species

Diffusion technique

of recommended study

Uncertainty

(in values of D)

Species

chronopotentiometry *vilO% U

4+

, Na

+

, Sn 2+

, Pb 2+

, T

2+

, i"

cyclic voltammetry ^±2 0% Zr 4 +

, I~

linear sweep voltammetry 'vi 2 0% Sn 2+

, Pb 2+

, Cu+

, Cd 2+

, Ti 2+

, Nb 5+

pulse polarography 'Vi 2 0%

— 4" o 4- I , Ag , Fe 3

chronoamperometry 'vi 2 0% T

2 +

, Fe 3 +

rotating disc electrode 'vi 2 0% Fe 3 +

Equation D = A exp[-E/RT] (30.4)

For

270
NaCl-AlClj

Table 30.8.2. Diffusion equation parameters, precisions,

and recommended study

Species A x 103_ (cm2 sec 1) E (cal mol !) Temp, range

(K) Precision Recommended

8 tudy

(a) NaCl-AlCl., (eutectic)

U‘* + 3.82 4150 520-670 m

CD 37

(b) NaCl-AlCl, (50 mol X NaCl)

Nb5

+ 1.99 5033 430-570 ^9. 2X 38

D“ + 8.36 5324 520-670 e N) OO H 37 (O NaCl-AlCl

3 (48 mol X NaCl)

Zr 4 + 15.17 6859 450-490 -H2X 41

Table 30.8.3. Diffusion coefficients, D x 10^ (cm^ sec

- '*'), from equations in table 30.8.2

T(K)

Eutectic melt 50 mol % NaCl 48 mol % NaCl

U

4 + Nb 5 +

U

4 +

Zr 4 +

430 0.550

450 0.715 0. 707

4 60 0.808 0.836

470 0.909 0.980

480 1.02 1.14

490 1.1$ 1.32

500 1 .26

520 6 .88 1.53 4.84

540 7 . 98 1.83 5 . 85

560 9.16 2 .16 6.99

570 9.78 2 . 34 7 . 60

590 11.08 8 . 91

610 12.44 10.34

630 13.87 11.89

650 15.36 13 . 55

670 16.91 15.33

271
NaCl -AlClj

Table 30.8.4. Diffusion coefficients for species

not included in table 30.8.3

Species Melt composition

(mol % NaC 1

)

T00

D x 10 5 (cm 2 sec -1

) Recommended

study

Na

+

37 413 0.10 43

Sn

2 +

33 .

433 0 .12 45

48 433 0.19 44

a

Pb 2 +

33 .

433 0.27 45

48 433 0 . 24 44

a

Cu

+

48 433 0.53 44 a

Ag

+

50 448 0.30 42

Cd 2 +

48 433 0.18 44 a

Ti 2+ 35 458 0.295 39

0.275

0.424

35 533 0.60 39

Fe 3 +

50 448 0.91 42

523 2 .20 36

I~ 37 448 0.202 40

0 . 107

0.241

50 448 0.268 40

0.211

0.243

a

Ref:- : [44] reported data in graphical form in the temperature range

430-500 K.

References: Na

+

, 43; Sn

2+

, 45; Pb

2+

, 44, 45; Cu

+

, 44; Ag

+

, 42; Cd

2+

, 44;

Ti

2+

, 39; Zr

4+

, 41; Nb

5+

, 38; Fe

3+

, 36, 42; U

4+

, 37; i", 40

9. Heat of Fusion ( AH °)

Measurement method: estimated [46]

Table 30,9. Heat of fusion of eutectic

AH°

* _ (kcal mol ) Uncertainty

7 .

^ ± 5 % References [46]

10 . Heat Capacity f J No data.

272
NaCl -A1C1

j

11. Volume Change on Melting

Measurement method" estimated from densities [46]

Table 3D. 10. Volume change on melting

Binary eutectic

(mol % NaCl)

(AV /V ) f s Uncertainty

36 .

35 . 9% ^ ± 5%

References [46]

12. Vapor r Pressure (pr ) vap

Measurement method: isoteniscope [47]

log p

= A + B/T (30.5)

precision: in table 30.11.1 uncertainty: v + 5%

Table 30.11.1. Parameters of equation (30.5), and precisions

Mol % AICI3 A -B Precis ion Temp . range

(K)

53.790 4 .71496 1771.0 ±3.53% 431-491

54.250 5 . 94281 2304.5 ±4.96% 418-524

55 . 513 5.77583 2177.5 ±5.43% 415-476

58.062 6.72729 2416 .

±1.93% 379-521

60.977 7 . 34912 2542 .

±1.32% 408-524

62.677 7 .27205 2427 .

±1.0 2% 410-524

63 . 046 7 .09260 2304 .

±1.11% 407-530

65 . 904 6.66296 1952.0 ± 0 . 43% 429-524

66.036 7 . 20848 2208 .

± 0 . 80% 427-524

69.277 6 .96901 1951 .

±0.35% 439-523

70.255 7.04376 1956.6 ±0.07% 448-483

73.929 7 .14703 1894 .

± 0 .16% 455-524

Table 30.11.2. Vapor pressure (mm) from equations in table 30.11.1

Mol % aici 3 T

( K ) 53.790 54.250 55.513 58.062 60.977 62.677 63.046 65.904 66.036 69.277 70.255 73.929

380 2.33

390 3.40

400 4.85

410 6.81 14.03 22.46 29.57

420 2.86 3.90 9.41 19.72 31.07 40.25

430 3.83 5.15 12 . 80 27.27 42.34 54.00 132.87 118.21

440 4.90 5.07 6.71 17.18 37.16 56.89 71.48 168.50 154.57 341.63

450 6.02 6.63 8.65 22.75 49.94 75.44 93.46 211.44 199.95 428.67 496.32

460 7.33 8.57 11.02 29.77 66.27 98.83 120.77 262.72 255.63 532.61 617.00 1066.37

470 8.85 10.96 13.89 38.51 86.88 127.99 154.37 323.43 323.42 655 . 66 759.95 1304.81

480 10.60 13.86 49.28 112.62 163.97 195.31 394.73 405 . 18 800.17 927.93 1583.20

490 12.61 17.37 62.44 144.46 207.96 244.75 477.85 502.98 968 . 63 1905.89

500 21.57 78.36 183.45 261.25 303.95 574.07 618.99 1163.64 2277.39

510 26.56 97.47 230.80 325.28 374.28 684.72 755.60 1387 .87 2702.36

520 32.44 120.22 287 . 82 401.59 457.20 811.19 915.30 1644 .14 3185.60

For vapor pressure of mixtures with 0-50 moll AlCl^, see [56[

References [47- 54,56]].

273
NaCl-AlCl

13. 3

Thermal Conductivity (liquid) ( X J Measurement method: steady state concentric cylinder [55]

precision: not estimated uncertainty: ^ + 20%

Table 30.12. Thermal conductivity of eutectic melt

T X x 10^

(K) (cal cm~i s ec~f K“1

)

467 5.3

References [55]

14.

Thermal Conductivityu (solid) (X ) s No thermal conductivity studies reported.

IS. Cryoscopic Constant f Measurement method: estimated [46]

Table 30.13. Cryoscopic constant of eutectic

Binary eutectic

(mol % NaCl

)

k

f (K mol - lkg~l) Uncertainty

36.8 4 .

^ ± 5%

References [46 ]

.

16.

References

[1] Robertson, W. D. , "Binary Phase Diagrams of Halide Salts"s (Vols. 1 and

2), Yale University, New Haven, Conn., USAEC Report AT(30-1) 2723 (1966)

[2] Janz, G. J. , Downey, J. R. , Jr., Allen, C. B. , and Tomkins, R. P. T.,

"Eutectic Data"-! vols.; ERDA-TID-27163-P1 § P2 ; NTIS, Washington,

D. C. (1977).

[3] Janz, G. J. , Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T.,

"Physical Properties Data Compilation Relevant to Energy Storage. I.

Molten Salts: Eutectic Data", NSRDS -NBS - 61 ; U. S. Gov’t Printing Office

Washington, D. C. (1978).

[4] Chretien, A., and Eskilk, L., Compt. Rend., 217 , 451 (1943).

[5] Shvartsman, V. I., Zapiski Inst. Khim. Akad. Nauk SSSR, 7_, No. L, 3 (1940)

[6] Boston, C. R., J. Chem. and Eng. Data, n, 262 (1966).

[7] Kryagova, A. I., Zh. Obshch. Khim., 9, 1759 (1939).

[8] Trifonov, N. A., Izv. Akad. Nauk SSSR, Otd. Tekh. Nauk. Mashinovet.

Soveshch. V. Yazkosti Zhii. Kolloid Rast., 2, 76 (1944).

[9] Kryagova, A. I., Zhur. Obshch. Khim., 9_, 1755 (1939).

[10] Kalita, P. T., and Plotnikov, V. A., Zhur. Fiz. Khim., 62_, 2195 (1930).

[11] Kryagova, A. I., Zh. Obshch. Khim., 9, 2061 (1939).

[12] Boston, C. R. , J. Chem. and Eng. Data, 1_3 , 117 (1968).

[13] Howie, R. L., and Macmillan, D. W. , J. Inorg. Nucl. Chem., 33^, 3681 (1970)

[14] Yamaguti, Y. , and Sisido, S., J. Chem. Soc. Japan, 59, 1311 (1938).

274
NaCl-AlCl

3

[15] Moss, R. H., Diss. Abs . , 15, 8 (1955).

[16] Yamaguti, Y. , and Sisido, S., J. Chem. Soc. Japan, 62_, 304 (1941).

[17] Midorikawa, R. , J. Electrochem. Soc. Japan, 2_3, 310 (1954).

[18] Fannin, A. A., Kibler, F. C., King, L. A., and Seegmiller, D. A., J. Chem.

Eng. Data, 19, 266 (1974); Air Force Systems Command, U. S. Air

Force Technical Report SRL-TR-74-0020 , September (19/4).

[19] Brockner, W. , Torklep, K. , and 0ye , H. A., Bunsenber ichte , submitted (1978).

[20] Midorikawa, R. , J. Electrochem. Soc. Japan, 2_4 , 23 (1956).

[21] " Dangerous Properties of Materials", Sax, N. I., Van Nostrand Reiphold

Co., N. Y. (1969).

[22] "Registry of Toxic Effects of Chemical Substances ", Christensen, H. E,, and

Lubinbyhl, T. T., eds . , U. S. Dept. H. E. W. , U. S. Gov't Printing

Office, Washington, D. C. , (1975).

'[23] Vapor pressure, calculated (see p. 273, this work).

[24] "Potential Hazards in Molten Salt Baths for Heat Treatment of Metals"

National Board Fire Underwriters Research Report No. 2 (1954).

[25] "Handbook of Reactive Chemical Hazards", Bretherwick, L., Butterworths

Co . , London (1975) .

[26] Janz, G. J. , Tomkins, R. P. T., Downey, J. R. , Jr., and Allen, C. B.,

"Safety and Hazards", Chapter in "Eutectic Data", ERDA TID - 27 1 63 - PI

NTIS, U. S. Dept. Commerce, Springfield, Va . (1977).

[27] Notoya, T., Ishikawa, T., and Midorikawa, R. , Hokkaido Daigaku Kogakubu

Kenkyu Hokoku, 5_5, 63 (1970).

[28] Kinosz, 0. L., and Haupin, W. E., Proceedings Intern. Symp . Molten

Salts, p. 375 (1976); The Electrochemical Soc., Princeton, N. J.

[29] Pizzini, S., "Materials Problems in the Industrial Applications of Molten

Salts", Proceedings of the European Conference on the Development

of Molten Salts Applications, p, 203 (1973); Battelle, Geneva.

[30] Johnson, K. E., "Electro chemical Approaches to Corrosion in Molten

Salts", Proceedings International Symposium on Metal -Slag -Gas Reactions

and Processes, The Electrochemical Society, Inc., Princeton, N. J.

p. 581 (1975).

[31] Edeleanu, C., and Littlewood, R. , Electrochimica Acta, _3, 195 (1960).

[32] Smirnov, M.V., and Ozeryanaya, I. N. , Nauki Tekh. Korros., Zashch,

Korros., 2_, 171 (1973).

[33] Inman, D. , and Wrench, N. S., Brit. Corr. J. , 1_, 246 (1966).

[34] Ketelaar, J. A. A., Chemie Ing. Techn. , 4-5, 667 (1973).

[35] Janz, G. J. , and Tomkins, R. P. T., Corrosion, 34_ (in press) (1978).

[36] Chovnyk, N. G., and Myshalov, M. V., Soviet. Electrochem., 6_, 1583 (1970).

[37] Martinot, L., Gerard, Th. , and Duyckaerts, G., Inorg. Nucl. Chem. Lett.,

9, 657 (1973).

[38] Ting, G., Fung, K. W. , and Mamantov, G., J. Electrochem. Soc., 123, 624

(1976) .

[39] Fung, K. W. , and Mamantov, G., J. Electroanal. Chem., 3_5^ 27 (1972).

[40] Marassi, R. , Chambers, J. 0., and Mamantov, G., J. Electroanal. Chem., 69,

345 (1976).

275
NaCl-AlCl

3

[41] Gilbert, B. , Mamantov, G., and Fung, K. W. , Inorg. Chem. , 1^4 , 1802 (1975).

[42] Boxall, L. G., Jones, H. L., and Osteryoung, R. A., J. Electrochem.

[43] Soc., 121, 212 (1974).

Gilbert, B., Brotherton, D. L., and Mamantov, G., J. Electrochem. Soc.,

121 , 773 (1974).

[44] Francini, M. , Martini, S„, and Monfrini, C., Electrochim. Metall., 2,

3 (1967).

[45] Delimarskii, Yu. K. , and Makogon, V. F., Zashchita Metallov, 5, 128 (1969)

[46] Janz, G. J., et al . , (MSDC-RPI) unpublished work (1977).

[47] Viola, J. T., King, L. A., Fannin, Jr., A. A., and Seegmiller, D. A.,

"The Vapor Pressure of Aluminum Chloride Systems. Ill. Vapor Pressure

of Aluminum Chloride-Sodium Chloride Melts", private communication to

G. J. Janz (MSDC-RPI), December, 1977; J. Chem. Erg. Data, accepted

for publication (1978).

[48] Naryshkin, I. I., Zh. Fiz. Khim. , 13, 690 C 1939 )

[49] Galitskii , N. V., Russ. J. Inorg. Chem., 13, 1607 (1968).

[50] Dewing, E. W. , J. Amer. Chem. Soc., 77_, 2639 (1955).

[51] Davey, T. R. A., Floyd, J. M. , and Marcantonio, P. J. , "The AlCl^-NaCl

System-Vapor Pressures and Liquidus ", paper read at AIME Meeting,

New York, N. Y. (1971) .

[52] Rogers, L., Div. Mineral Chem., CSIRO, Australia (1962); unpublished

results; cited by Davey, ref. 51.

[53] Narita, T., Ishikawa, T., and Midorikawa, R. , Denki Kagaku, 3_6, 300 (1968)

[54] Plotnikov, V. A., Fortunatov, N. S., and Galinkes, V. S., Zh. Prikl. Khim.

6, 1025 (1933).

[55] Turnbull, A. G., Ph.D. Thesis, Imperial College of Science and Technology,

London, 1959.

[56] Linga, H. , Motzfeldt, K., and 0ye , H. A., Preprint: "Vapor pressure

of molten alkali chlor ide - aluminum chloride mixture" (1978).

276
XXXI. Potassium Chloride-Aluminum Chloride: KCl-AlCl^

1. Melting Temperatures

Pure substance melting points:

KC1 : 770°C

A1C1

3

: 192°C

Eutectic melting point:

128°C, composition: 33 mol % KC1

Figure 31.1. KCl-AlCl^ phase diagram

References [1-3]

2. Density (p)

Measurement method: float technique [4]

p = a + bT (31.1)

precision: in table 31.1 uncertainty: ^ + 0.5%

Table 31.1. Coefficients of equation (31.1), and precisions

Mol. % KC1 a -b x 10 3 Precision

20 . 00 2 . 0252 1.0038 ±0.11%

33.33 1 .9889 0.7901 ±0.14%

50.03 1 . 9556 0.6622 ±0.05%

66.66 1.9734 0.6101 ±0.02%

For numerical values: see table 31.2

277
KC1-A1C1

3

_ 3 Table 31.2. Densities (g cm ) from equations

in table 31.1

Mol % KC1

T (K) 66.66 50.03 33.33 20.00

480 1.543

500 1.594 1.523

520 1 .578 1 .503

540 1 .562 1.483

560 1.547

580 1.531

600 1 . 515

620 1.499

640 1.483

660 1.468

680 1.452

700 1 .436

720 1.420

740 1.466 1 .404

760 1.452 1 .389

780 1.439 1.373

800 1.426

820 1.413

840 1.399

860 1.386

880 1.373

900 1 .360

920 1.346

940 1 .333

960 1 . 388 1.320

980 1 .376 1.307

1000 1 .363 1.293

1020 1 .351 1.280

1040 1 .339 1.267

References [4-12],

3. Surface Tension Cyl

No data.

4. Viscosity (r\)

No data.

278
KC1-A1C1

3

5. Electrical Conductance (k)

Measurement method: ac technique [5,9]

k = a + bT + cT

2 (31.2)

precision: in table 31.3 uncertainty: ^ t 31

Table 31.3.1. Coefficients of equation (31.2), and precisions

Mol % KC1 -a b x 10 3 c x 1 0

^ Precision

19 .

0.0842 0.1364 0 .5637 ±0.50%

19.75 0 . 2107 0.6730 0 ±0.74%

28.80 0.4986 1.6155 -0.4808 ±0. 21%

30.75 0.2948 0.7560 0.4625 ±0.52%

39.45 0.5271 1.5402 0 ±1.18%

49.35 0.7979 2 .1891 0 ±0.74%

Table 31.3.2. Coefficients of equation (31.2) and precisions

for additional mixtures

Mol % KC1 -a b x 10 3 -c x 10^ Precision

40 1.60616 4 .5104 2 . 0094 ±0.01%

50 1 . 06946 3 .3785 1 .2854 ±0.36%

60 0.24510 0 .6700 0.0 ±2 . 03%

70 0 .11300 0.8500 0.0 ±1.99%

80 0.17700 1.0000 0.0 ±0 . 00%

90 0.29910 1 .2000 0.0 ±0.68%

100 -0.19590 2 .2500 0.0 ±1 .30%

uncertainty: ^ ± \%

-

-

Table 31.4.1. Specific conductance (ohm cm ) from equations

in table 31.3.1.

Mol % KC1

T 49 .35 39.45 30.75 28.80 19 . 75 19.4

(K)

470 0.1544 0.1056 0 .1044

480 0.2122 0.1746 0 .1660 0.1123 0 . 1111

490 0.2276 0.1867 0.1775 0 .1191 0.1180

500 0.2430 0 .1988 0.1889 0 .1258 0.1249

510 0.2584 0 .2111 0 .2002 0.1325 0 .1320

520 0.2738 0 .2234 0 .2114 0.1393 0.1392

530 0.3623 0.2892 0 .2358 0.2225 0.1460 0.1464

540 0.3842 0.3046 0 . 2483 0.2335 0.1527 0 .1538

550 0 .4061 0 .3200 0 .2609 0.1595 0 .1613

560 0.4280 0 .3354 0.2736 0.1662

570 0.5599 0 .2864

279
KC1-A1C1

3

Table 31.4.2. Specific conductance (ohm ^cm from equations

in table 31.3.2.

Mol % KC 1

T 40 50 60 70 80 90 100

( K ) 880 0.807 0.908

900 0.826 0.930

920 0.843 0.951

940 0.858 0.971

960 0.872 0.989

980 0.884 1.007 0 . 902 0.946

1000 0.895 1 . 024 0.915 0 .963

1020 0.904 1 . 039 0.929 0.980

1040 0.911 1.054 0.942 0.997

1060 0.917 1 .067 1.955 1 . 014

1080 1.080 0.969 1 . 031 1.257 1.595 2 . 234

1100 1.092 0.982 1 . 048 1.277 1.619 2 .279

1120 1 .102 0.996 1.065 1.297 1.643 2 .324

1140 1.112 1 . 009 1 . 082 1 .317 1 .667 2.369

1160 1 .120 1.022 1.099 1 .337 1 .691 2.414

1180 1 .127 1.036 1 . 116 1 . 357 1 .715 2.459

1200 1 .134 1 . 049 1 .133 1.377 1 .739 2 .504

1220 1 . 139 1.063 1 .150 1 .397 1.763 2.549

1240 1.143 1.076 1.167 1 . 417 ' 1.787 2.594

1260 1.147 1 . 089 1 . 184 1 .437 1 . 811 2 . 639

References [4-6,8,9,11-16],

6. Safety and Hazards

A. Hazard rating [17-19]

(i) Toxicity: KC1, slight; AlCl^, severe

(ii) Vapor pressure: appreciable; see [32-34H and Table 31.9 (p - 28 2)

B. Disaster hazards [17,20-22]

(i) Molten salt bath "explosions": i.e. explosive generation

of steam due to bulk water "carry-over" and/or equipment

failure; i.e., explosive expansion of "trapped" air.

(ii) Chlorides, when heated to decomposition, or contacted with acids,

emit highly toxic fumes; AICI 3 reacts exothermically with

moisture/water to evolve HC1 fumes.

References [17-22].

280
KC1-A1C1

3

7. Corrosion

Table 31.5. Corrosion studies from primary research literature

Studies Ref er ences

Quartz, vycor, Ni, Pt 4,5,9,23

Electrochemical approach 24,25

Thermodynamic redox diagrams 26

Annotated corrosion biblio. 27

Reviews: molten salts corrosion 28-30

References [4,5,9,23-30],

8. Diffusion

No diffusion studies reported with molten KCl-AlCl^ as solvent.

9. Heat of Fusion (Aff^)

Measurement method: estimated [31]

Table 31.6. Heat of fusion of eutectic

10 .

11 .

AH °f Uncertainty -1

(kcal mol )

6 . 9 ^ ± 5%

References

Heat Capacity

No data.

Volume Change

Measurement

[31].

(C ) P

on Melting (A Vj.)

method: estimated from densities [31]

Table 31.7. Volume change on melting

Binary eutectic

(mol % KC1

< 4 VV Uncertainty

33 35.5% ^ ± 5%

References [31]

Vapor Pressure (pr ) vap

Measurement method: static technique [32]

log p

= A + B/T (31.3)

precision: in table 31,8 uncertainty: ^ + 10%

281
KC1-A1C1

3

Table 31.8. Parameters of equation (31.3), and precisions

Mo 1 % A1 C 1 3 A -B Temp . range

(K)

Precision

50 .

7.3950 5860 861-1073 ± 1.87%

48 .

9 .2386 7846 905-1073 ± 3.50%

42.4 8 .9430 7634 917-1029 ± r. io%

36 .

8 .4231 7212 943-1037 ± 0 . 90%

For vapor pressure of mixtures with 0-50 mol% AlCl^, see [34H

Table 31.9. Vapor pressure (mm) from equations in table 31.8

T(K)

Mol % A1C1 3 36 .

42 .48 .50.1

870 4

6 880 5.4

890 6 .

900 7 . 7 910 4.1 9

0 920 4 .

5.1 10 .

930 5 .

6 .

12.4

940 6 . 6 7.8 14 .

950 6 . 8 8 . 1 9 .

16 .

960 8.1 9.8 11 .

19.5

970 9 . 7 11 .

14.1 22.6

980 11 .

14 .

17 .

26.0

990 13 .

17 .

20.6 29 .9

1000 16 .

20 .

24.7 34 .

1010 19 .

24.2 29 . 5 39 . 2 1020 22.5 28 .

35 .

44 .

1030 26 .

34.0 41 .

50 .

1040 49 .

57 . 6 1050 58.4 65 . 2 1060 68.7 73.6

1070 80 .

82 .

References C 3

2 - 3 4 .

IS. Thermal Conductivity (liquid) (X^)

No thermal conductivity studies reported.

14. Thermal Conductivity (solid) (X )

No thermal conductivity studies reported.

15 . Cryoscopic Constant

Measurement method: estimated [31]

Table 31.10. Cryoscopic constant of eutectic

k

f (K mol~-*-kg~l)

Uncertainty

5 .

^ ± 5%

References [31]

282
KC1-A1C1

3

16. References

[1] Robertson, W. D., "Binary Phase Diagrams of Halide Salts", (Vols. 1 and 2),

Yale Univ. , New Haven, Conn., USAEC Report AT (30-1) 2723 (1966).

[2] Janz, G. J. , Downey, J. R. , Jr., Allen, C. B. , and Tomkins, R. P. T.,

"Eutectic Data" - 2 Vols.; ERDA-TID- 27163-PI 8 P2 ; NTIS, Washington,

D. C. (1977).

[3] Janz, G. J., Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T.,

"Physical Properties Data Compilations Relevant to Energy Storage . J.

Molten Salts: Eutectic Data", NSRDS-NBS- 61 ; U. S. Gov't Printing Office,

Washington, D. C. (1978).

[4] Morrey, J. R. , and Carter, D. G. , J. Chem. and Eng. Data, 13, 94 (1968).

[5] Yamaguti, Y. , and Sisido, S. , J. Chem. Soc. Japan, 62, 304 (1941).

[6] Grothe, H. , Z. Elektrochem. , 53, 362 (1949).

[7] Moss, R. H. , Diss. Abs., 15, 8 (1955).

[8] Gruen, D. M. , and 0ye , H. A., Inorg. Chem., 4, 1173 (1965).

[9] Boston, C. R. , Grantham, L. F., and Yosim, S. F. , J. Electrochem. Soc.,

117, 28 (1970).

[10] Midorikawa, R. , J. Electrochem. Soc. Japan, 23, 310 (1954).

[11] Shvartsman, V. I., Zapiski Inst. Khim. Akad. Nauk USSR, 7, [1], 3 (1940).

[12] Boston, C. R., J. Chem. Eng. Data

-

, 13 , 123 (1968).

[13] Grothe, H. , Aluminium, 38, 320 (1962).

[14] V ide infra [ 7 ]

[15] Midorikawa, R. , J. Electrochem. Soc. Japan, 24, 23 (1956).

[16] Boston, C. R. , J. Chem. Eng. Data, 13_, 117 (1968).

[17] "Danqerous Properties of Materials"

Sax, N. I., Van Nostrand Reinhold

Co. , N. Y. (1969)

[18] "Registry of Toxic Effects of Chemical Substances", Christensen, H. E.,

and Lubinbyhl, T. T., eds . , U. S. Dept. H. E. W. , U. S. Gov't Printing

Office, Washington, D. C. (1975).

[19] Vapor pressure, calculated (see p.282, this work).

[20] "Potential Hazards In Molten Salt Baths for Heat Treatment of Metals ",

National Board Fire Underwriters Research Report No. 2 (1954).

[21] "Handbook of Reactive Chemical Hazards", Bretherwick, L., Butterworths

Co., London (1975).

[22] Janz, G. J., Tomkins, R. P. T. , Downey, J. R. , Jr., and Allen, C. B.,

"Safety and Hazards ", Chapter in "Eutectic Data", ERDA-TID- 271 63 -Pi

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[23] Kinosz, D. L., and Haupin W. , Proceedings Intern. Symp . Molten Salts,

p. 375, (1976); The Electrochem. Soc., Princeton, N. J.

[24] Pizzini, S., "Materials Problems in the Industrial Applications of Molten

Salts", Proceedings of the European Conference on the Development of

Molten Salts Applications, p. 203, (1973); Battelle, Geneva.

J 283
KC1-A1C1

3

[25] Johnson, K. E., "Electrochemical Approaches to Corrosion in Molten Salts",

"Proceedings International Symposium on Metal -Slag -Gas Reactions and

Processes, The Electrochemical Society, Inc., Princeton, N. J., p. 581

(1975) .

[26] Littlewood

,

R. , J. Electrochem. Soc . , 109 , 525 (1962)

[27] Janz, G. J. , and Tomkins, R. P. T . , Corrosion

,

34 (in press) (1978)

[28] Smirnov, M. V. , and Ozeryanaya, I . N . , Nauki Tekh

Korros. Zashch

171 (1973).

[29] Inman, D. , and Wrench, N. S., Brit. Corr. J., 1_, 246 (1966).

[30] Ketelaar, J. A. A., Chemie Ing. Techn. , 4_5 , 667 (1973).

[31] Janz, G. J., et al., (MSDC-RPI) unpublished work (1977).

[32] Grothe, H. , Z. Elektrochem . , 54_, 216 (1950).

[33] Linga, H. , Motzfeldt, K. , and 0ye , H. A., Light Metals, AIME (1977).

[34] Linga, H. , Motzfeld, K. , and 0ye, H. A., Preprint: "Vapor pressures

of alkali chloride-aluminum chloride mixtures" (1978).

284
XXXII. Sodium Chloride-Calcium Chloride: NaCl-CaCl

2

1. Melting Temperatures (T ) Pure substance melting points:

NaCl : 8 00°C

CaCl

2

: 782°C

Eutectic melting point:

500°C, composition: 48 mol I NaCl

Figure 32.1. NaCl-CaCl

2 phase diagram

References [1-3] .

2. density (p)

Measurement method: Archimedean technique [4]

Single variable equation

p = a + bT (32.1)

precision: in table 32,1 uncertainty: ^ + 1!

Table 32.1. Coefficients of single variable equation (32.1),

and precisions

Mol. % NaCl a -b x 10 4 Precision

0 2.4986 3.976 ±0.05%

19 .

2 .4651 4.444 ±0.03%

22 .

2.4637 4.554 ±0 . 02%

35 . 9 2 .4925 5.367 ±0.18%

49 .

2 .3800 4 .955 ±0.02%

67.5 2 .1791 4 . 006 ±0 .01%

85 .

2 .1305 4.546 ±0 . 01%

100 .

2 .1319 5.297 ±0.04%

285
NaCl-CaCl

2

Two- independent -variable equation

p = a + bT + cC + dC 2 (C = mol % CaCl

2

) (32.2)

precision: + 0.18% uncertainty: ^ + 1%

Table 32.2. Coefficients of two-independent-variables equation (32,2)

a b x 10 4 c x 1

3 d x 10 5

2 . 06606 -4.72915 6.20063 -1.04771

_3 Table 32.3. Densities (g cm ) from equations

in table 32.1

T (K) Mol % NaCl

100 85 .

67 .

49 .35 .

22 .19 .

0

1040 2 . 003

1050 1.998

1060 1 . 855 1.994

1070 1.850 1 .990 2 . 073

1080 1.845 1.913 1.972 1.985 2.069

1090 1.555 1.635 1.742 1.840 1 .908 1 .967 1.981 2 . 065

1100 1 .549 1 . 630 1.738 1.835 1.903 1.963 1.976 2 . 061

1110 1.544 1.626 1.734 1.830 1.897 1.958 1.972 2.057

1120 1 .539 1 .621 1.730 1 .825 1.892 1 . 954 1.967 2 . 053

1130 1.533 1 . 617 1.726 1.820 1.887 1.949 2.049

1140 1 . 528 1.612 1.722 1 .815 1.881 1 . 945 2.045

1150 1.523 1.608 1.718 1.810 1.876 1.940

1160 1 .517 1.603 1 .805 1.871 1.935

.117 0 1 . 512 1.599 1.865 1 . 931

References [4-23].

3. Surface Tension (y)

Measurement method: maximum bubble pressure [16]

y

= a + bT (32.3)

precision: ^ + 0.8% uncertainty: ^ + 0.5%

286
T(K)

830

840 850

860

870

880 890

900 910

920 930

940

950

960 970

980 990

1000

1010

1020

1030

1040

1050

1060

1070

10 80 1090

1100

1110

1120

1130

1140

NaCl-CaCl

2

Table 32,4. Parameters of equation (32,3)

Mol % NaCl a -b x 10 2

0 205.83 5.61

20 224.81 8.37

23.72 211.92 7.40

30 204.57 7.00

35 199.68 6.66

40 204.49 7.36

50 194.15 6.62

60 201.34 7.55

70 206.22 8.24

80 206.36 8.42

90 199.67 7 . 90

100 198.14 7.80

Table 32.5. Surface tension (dyn cm from

equations in table 32.4

Mol Z NaCl

100 90 80 70 60 50 40 35 30 23.72 20 0 139.20 143.40

138.54 142.67

137.88 141.93

137.22 141.19

136.56 140.46

134.90 135.89 139.72 141.07

134.15 135.23 138.99 140.41

133.39 134.57 138.25 139.74

132.64 133.91 137.51 139.07

131.88 133.25 136.78 138.41

131.13 132.58 136.04 137.74 139.47

130.37 131.92 135.31 137.08 138.77

127.94 129.62 131.26 134.57 136.41 138.07

127.12 128. 86 130.60 133.83 135.74 137.37

126.29 128.11 129.94 133.10 135.08 136.67 140.14

125.47 127.35 129.27 132.36 134.41 135.97 139.40 142.78

124.64 126.60 128.61 131.63 133.75 135.27 138.66 141.95

123.82 125.84 127.95 130.89 133.08 134.57 137.92 141.11

123.00 125.09 127.29 130.15 132.41 133.87 137.18 140.27 149.17

120.48 122.17 124.33 126.63 129.42 131. 75 133.17 136.44 139.44 148.61

119.63 121.35 123.58 125.96 128.68 131.08 132.47 135.70 138.60 148.05

118.79 120.52 122. 82 125 . 30 127.95 130.42 131.77 134.96 137.76 147 . 49 117.95 119.70 122.07 124.64 127.21 129.75 131.07 134.22 136.93 146.93

117.11 118.88 121.31 123.98 126.47 129.08 130.37 133.48 136.09 146.36

115.14 116.27 118.05 120.56 123.32 125 . 74 128.42 129.67 132.74 135.25 145.80

113.90 114. 35 115.42 117.23 119.80 128.97 132.00 134.41 145.24

113.12 113.56 114.58 116.40 131.26 133.58 144.68

112.34 112.77 113.74 115.58 130.52 144.12

111.56 111.98 112.90 114.76 143.56

110.78 111.19 112.06 143.00

110.00 110.40 142.44

141.88

287
NaCl -CaCl

2

References [4-18,24,25].'

Viscosity (r\)

Measurement method: oscillating sphere [10]

n = a + bT + cT

2 + dT 3 (32.4)

precision: in table 32.6 uncertainty: ^ + 25%

Table 32.6. Parameters of equation (32.4), and precisions

NaCl

(mol 1) a b x 10 2 c x 10 5 d x 10 9 Precision

0 69.3492 -10.3644 3.5858 3.8776 0.73Z

10 20.1917 2.8465 -8.3002 39.9729 0.34%

20 30.0118 -0.1588 -5.5677 32.2866 0.41%

AO 12.1701 0.9805 -3.4259 16.2560 0.67%

50 44.5576 -8.7561 6.2253 -15.5917 0.65%

60 10.4758 1.2168 -3.6226 16.8297 0.68%

70 19.1369 -1.1116 -1.3786 8.9463 0.58%

80 33.3003 -3.3357 -0.9395 12.5058 0.69%

90 30.9838 -2.2958 -2.2975 17.8387 0.64%

100 [-22.9126] [4.8514] [-2.4000] 0

Table 32.7. Viscosity (cp) from equations

in table 32.6

Mol « NaCl

( K ) 100 90 80 70 60 50 40 20 10 0

930 4 . 00 4.43 4.73

940 3 . 88 4.31 4 .62 950 3.77 4 .19 4.50

960 3.66 4 . 08 4 . 39 970 3.55 3.97 4 .28 980 3 .42 3.45 3.86 4.18 5.37

990 3.30 3.35 3.76 4.07 5 .20 1000 3.05 3.18 3.25 3 . 66 3.97 5.03

1010 2 . 91 3.06 3.15 3.56 3 .87 4 .88 1020 2 .77 2.95 3.06 3.47 3.78 4.73

1030 2.64 2 .84 2 . 97 3 . 38 3 . 69 4.59 5.13 4 . 88 1040 2.51 2.73 2.88 3 .29 3 . 60 4 . 46 4 . 98 4.71

1050 2.20 2.39 2.62 2 . 80 3 . 20 3.51 4 . 34 4 . 84 4 . 55 1060 2 . 08 2.28 2 . 52 2.72 3.12 3.43 4.22 4.71 4 . 40 1070 1.97 2.17 2.42 2 . 64 3 . 04 3.35 4.12 4 . 59 4.25

1080 1 . 86 2.07 2.32 2 . 56 2 . 96 3 . 28 4.03 4 .47 4 . 12 1090 1 .76 1 .97 2.23 2 . 49 2 .89 3.21 3.94 4 . 37 4 .00 1100 [ 1 . 41 ] 1 .67 1 .88 2 .14 2.43 2 .82 3.14 3.87 4.27 3 .89 1110 [ 1 . 37 ] 1 . 59 1 . 80 2.05 2.37 2 .74 3 . 08 3.81 4 . 19 3 .79 1120 [ 1 . 32 ] 1 .51 1.72 1 . 96 2.31 2 . 68 3.02 3.75 4.11 3 . 70 1130 [ 1 . 26 ] 1 .44 1.65 1 .88 2.25 2 . 61 2.96 3.71 4.05 3 .61 1140 [ 1 . 20 ] 1 . 38 1 . 59 1 . 80 2.20 2 . 54 2.91 3 . 68 3.99 3 . 54

Values in brackets are based on minimal data base.

References [4-18]
NaCl-CaCl

2

5. Electrical Conductance (k)

Measurement method: ac technique [14]

k = a + bT + cT

2 (32.5)

precision: in table 32.8 uncertainty: ^ + 1.5%

Table 32.8. Parameters of equation (32.5),' and precisions

Mol % NaCl -a b x 10 3 -c x 1

7 Precision3,

33 .[3.4536] [ 6 . 1849] [ 9 .4099]

51.8 3 .9865 7 .7171 17 . 9443 ±0.07%

73 . 6 [3.9759] [8.6268] [ 23 . 5295]

88 .-[0.2981] [2.5926] —

£

No entry, indicates insufficient data for precision estimates

Table 32,9.1 Specific conductance (ohm'^cm"^)

from equations in table 32,8

T(K)

Mol % NaCl

88.5 73.6 33 .

970 [1.660]

980 [2.219] [1.704]

990 [2.259] [1.747]

1000 [2.298] [1.790]

1010 [2.337] [1.833]

1020 [2.375] [1.876]

1030 [2.414] [1 . 919]

1040 [2.451] [1.961]

1050 [2.488] [ 2 . 003]

1060 [3.046] [2.525] [2.045]

1070 [3.072] [2.561] [2.087]

1080 [3 . 098] [2.597]

Values in brackets are based on minimal data base.

Table 32.9.2. Specific conductance for additional mixture

(51.8 mol % NaCl)

T(K)

K (ohm 'em ') T(K)

_

K (ohm 'em ')

830 1 . 183 960 1.768

840 1.230 970 1 .811

850 1.277 980 1.853

860 1.323 990 1.895

870 1.369 1000 1. 936

880 1 . 415 1010 1.977

890 1.460 1020 2 . 018

900 1.505 1030 2 . 058

910 1.550 1040 2 . 098

920 1 . 594 1050 2 .138

930 1.638 1060 2 .177

940 1.682 1070 2 .216

950 1.725 1080 2 .255

References [4-19,21,26-28].

289
NaCl-CaCl

2 6.

Safety and Hazards

A. Hazard rating [29-31]

(i) Toxicity: NaCl, very low; CaCl

2

, very low.

(ii) Vapor pressure: no data for mixture; but see,

NaCl; CaCl

2

.

B. Disaster hazards [29,32-34]

(i) Molten salt bath "explosions": i.e. explosive generation

of steam due to bulk water "carry-over” and/or

equipment failure; i.e., explosive expansion of

"trapped" air.

(ii) Chlorides, when heated to decomposition, or contacted with acids, emit highly toxic fumes.

References [29-34],

7.

Corrosion

Table 32.10. Corrosion studies from primary research' 1 iterature

References [11,14,15,21,35-43],

8.

Diffusion

Measurement method: chronopotentiometry [44]

Diffusing species investigated in NaCl-CaCl

2 as solvent:

precision: insufficient data for estimate

Table 32.11. Diffusion coefficients and uncertainties

Species T

, D x 10 Uncertainty

(K) ( cm^ sec"-*-)

„ 2 +

Fe 873 2 .36 ^ ± 10%

References [44]

290
9.

10 .

NaCl -CaCl

2 Heat of Fusion

Measurement method: estimated [45]

Table 32.12. Heat of fusion of eutectic

AH°

^ -1 Uncertainty

(kcal mol ) 5.7 ^ ± 5%

References [45]

Heat Capacity (C^

No data.

11.

Volume Change on Melting fAV^J

Measurement method: estimated from densities [46],

Table 32.13. Volume change on melting

Binary eutectic (A V /V ) Uncertainty

(mol % NaCl) I s

48 14 .5% ^ ± 8%

References [46]

12,

Vapor Pressure Cp ) rap

Measurement method: Rodebush-Dixon [47]

Table 32.14. Vapor pressures (mm)

Mol % NaCl 1373 K 1423 K Mol % NaCl 1373 K 1423 K

13 1 .46 2.90 84 24.48 41 . 10

29 3 .77 7 . 32 86 25.71 43.18

42 7.37 13.79 88 27.19 46.08

53 11 . 35 18.37 90 28.43 47.70

61 14 . 30 24.79 91 28.87 48.91

69 17.47 30 . 08 100 32 .07 56 . 34

78 20.92 36.05

Values at 100% NaCl are 8-10% higher than the recommended

vapor pressure for NaCl at 1373 and 1423 K.

References [47]

13. Thermal Conductivity (liquid)

No thermal conductivity studies reported.

14. Thermal Conductivity (solid) (\ ^)

No thermal conductivity studies reported.

15. Cryoscopic Constant (%„)

Measurement method: estimated [45]

291
NaCl-CaCl

2

Table 32.15. Cryoscopic constant

Binary eutectic k

(mol % NaCl

)

f (K mol"lkg - l) Uncertainty

48 17 .

^ ± 5%

References [45].

16. References

[ 1 ]

[ 2 ]

[3]

[4]

[5]

[ 6 ]

[7]

[ 8 ]

[9]

[ 10 ]

[ 11 ]

[ 12 ]

[13]

[14]

[15]

[16]

[17]

[18]

[19]

[ 20 ]

[ 21 ]

Robertson, W. D., "Binary Phase Diagrams of Halide Salts", ( Vol.

1+2), Yale University, New Haven, Conn., USAEC Report AT(30-1)

2733 (1966).

Janz, G. J., Downey, J. R., Jr., Allen, C. B., and Tomkins, R. P. T.

"Eutectic Data" - 2 vols; ERDA-TID- 271 63 -PI § P2; NTIS, Washington

D. C. (1977).

Janz, G. J., Downey, J. R., Jr., Allen, C. B., and Tomkins, R. P. T.

"Physical Properties Data Compilations Relevant to Energy Storage

I. Molten Salts: Eutectic Data", NSRDS -NBS - 61 ; U, S. Gov't

Printing Office, Washington, D. C. (1978),

Lillebuen, B., Ph.D. Thesis, The Technical University of Norway,

Trondheim, Norway, (1969).

Alabyshev, A. F., and Kulakovskaya , N. Ya., Trudy, Leningrad.

Tekhnol. Inst. Im. Leningrad. Soveta, 12^, 1 52 (1946).

Ryschkewitsch , E., Z. Elektrochem . , 3_9, 531 (1933).

Barzakovskii

,

V. P . , Izv. Sekt

Fiz. Khim. , 5, 825 (1940)

Bar zakovskii

,

V. P . , Leningrad

Gos . Inst. Prik. Khim., Sbornik

Rabot. , 3_3 , 5 (1940) .

Bar zakovskii , V. P., Zhur. Priklad. Khim . , 13 , 1117 (1940).

Ver eshchet ina , I. P., and Luzhnaya, N. P., Izv. Sekt. Fiz. Khim.

Anal . , 2_5 , 188 (1954) . Lantratov, M. F., and Moiseeva, 0. F., J. Appl . Chem. (USSR), 33 , 2194 (1960); Zh. Priklad. Khim., 33^, 2225 (1960).

Bochkareva, N. N., Kochergin, V. P., and Mlynskaya, T. P,, Russ.

J. Inorg. Chem., 14. , 711 (1969),

Egerev, D. I., and Zolotarev, V. I., J. Appl. Chem. (USSR),

42, 1123 (1969); Zhur. Priklad. Khim., 42_, 1184 (1969).

Clarke, I. T., and Story, B., J. Metals, 9., 1449 (1957).

Nikolio, R., Grjotheim, K., and 0ye, H. A., Acta Chem. Scand.,

24, 489 (1970).

Lantratov, M. F., Zhur, Priklad. Khim., 3_4 , 1249 (1961); J. Appl.

Chem., USSR, 34_, 1190 (1961).

Fuseya, G., and Ouchi, K., Denki Kagaku, 17 , 254 (1949).

Grjotheim, K., Holm, J. L., Lillebuen, B., and 0ye, H. A., Trans.

Faraday Soc., 67_, 640 (1971).

Sandonnini, C., Gazz. Chim. Ital,, _50, 289 ([192 0),

Bukhalova, G. A., and Sementsova, D. V,, Russ. J. Inorg. Chem.,

1_5 , 411 (1970); Zh. Neorg. Khim., 1_5, 806 (1970).

Brautigam, G., Emons, H. H., and Vogt, H. , Z. Chem,, 1_0, 344 (1970).

292
NaCl -CaCl

2

[22] Brautigam, G., and Emons, H. H. , Z. anorg. allgm. Chem., 394,

271 (1972). -

[23] Seltveit, A., and Flood, A., Acta Chem. Scand., 12(5) , 1036 (1958).

[24] Bar zakovskii , V. P., Izv. Akad . Nauk. SSSR Otdel . Khim. Nauk. , 5,

825 (1940).

[25] Grjotheim, K. , Holm, J. L., Lillibuen, B., and 0ye , H. A., Inst.

Inorg. Chem., Technical University of Norway, N-7034, Trondheim,

Norway (1971)

[26] Luzhnaya, N. P., Evseeva, N. N., and Vereshchetina , N. P., Zhur

Neorg. Khim., 1, 1490 (1956); Russ. J. Inorg. Chem., 1, 35 (1956).

[27] Emons, H. H., Brautigam, G., and Vogt, H., Z. anorg. allgm. Chem.,

394, 263 (1972).

[28]

Markov, B. F., DokladyAkad. Nauk. SSSR, 102, 1163 (1955).

[29] "Dangerous Properties of Materials "

Sax, N. I., Van Nostrand

Reinhold Co . , N. Y. (1969)

[30] "Registry of Toxic Effects of Chemical Substances ", Christensen,

H. E., and Lubinbyhl , T. T., eds., U. S. Dept. H. E. W. , U. S.

Gov't Printing Office, Washington, D. C. (1975).

[31] Vapor pressure, calculated (see p. 291, this work).

[32] "Potential Hazards in Molten Salt Baths for Heat Treatment of Metals"

National Board Fire Underwriters Research Report No. 2 (1954).

[33] "Handbook of Reactive Chemical Hazards ", Bretherwick, L., Butterworths

Co . , London (197 5)

[34] Janz, G. J., Tomkins, R. P. T. , Downey, J, R. , Jr., and Allen, C. B.,

"Safety and Hazards", Chapter in "Eutectic Data", ERDA TID-27163-P1

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[35] Kochergin, V, P., Bochkarena, N. N., and Yarysheva, I. A., Zashch.

Metal., 6, 457 (1970).

[36] Smirnov, M. V., Kudyakov, V. Ya., Logina, Ya. A,, Rossokhin, E. G.,

Posokhin, Yu. V., and Puzanova, T, A., Fiz. Khim. Elektrokhim.

Rasplav. Solei Shlakov, 1_, 115 (1969).

[37] Littlewood, R., J. Electrochem. Soc., 109, 525 (1962),

[38] Pizzini, S., "Materials Problems in the Industrial Applications of

Molten Salts", Proceedings of the European Conference on the

Development of Molten Salts Applications, p. 203 (1973); Batelle,

Geneva

[39] Johnson, K. E., "Electrochemical Approaches to Corrosion in Molten

Salts", Proceedings International Symposium on Metal -Slag -Gas

Reactions and Processes, The Electrochemical Society, Inc.,

Princeton, N. J., p. 581 (1975).

[40] Smirnov, M. V., and Ozeryanaya, I. N., Nauki Tekh, Korros. Zaschch

Korros . , 2, 171 (1973)

[41] Inman, D., and Wrench, N. S., Brit. Corr. J., 1^, 246 (1966).

[42] Ketelaar, J. A. A., Chemie Ing. Techn., 4_5, 667 (1973).

[43] Janz, G, J,, and Tomkins, R. P. T., Corrosion, 34_ (in press) (1978).

[44] Wood, J. M., Paper presented at 111^ Meeting, The Electrochemical

Soc., Washington, D. C., May 1957.

293
NaCl - CaCl

[45] Janz, G. J,, et al . , (MSDC-RPI) unpublished work (1977),

[46] Maru, H. C., Dullea, J. F., and Huang, V. S., "Molten Salt Thermal

Energy Storage Systems: Salt Selection " , ERDA Tech. Report COO2888-1; (8981); NTIS, U. S. Dept. Commerce, Springfield, Va.

(Aug. 1976).

[47] Topor, L. , and Moldoveanu, I., Rev. Chim, (Roumaine) , 21*, 495 (1976).

294
XXXIII. Sodium Polysulfides: Na

2 S x

(2, , 5.2)

1. Melting Temperatures ( T^)

Pure substance melting points:

Na

2 S : 1 1 7 0

0 C

Sulfur115°C

Compound melting

Na

2 S2

: 482°C

Na

2 S3

: 230°C

Na

2 s

4

: 294°C

Na

2 S

5

: 2 5 5

° C

Eutectic melting-points:

Eutectic 1: 235°C, composition:

Eutectic 2: 237°C, • composition:

Na

2 S2 -Na

2 S

4 (50 mol % Na

2 S^-Na

2 S^ (33.3 mol

Figure 33.1. Na

2 S x phase diagram

References [1-11]

2 . Density (p J Measurement method: modified dilatometric [12]

p = a + bT (33.1)

precision: in table 33,1 uncertainty: ^ +

Na

2 S

2

)

% Na

2 S4

)

0,0

295
Na

2 sx

Table 33.1. Parameters of equation (33.1), and precisions

Melt Wt % S Temp, range

(K) a -b x 10 3 Precision

N a 2S 3 . o 67 .

590 - 683 2 .2270 0.5658 ±0.18%

Na 2 S 3.3 69.7 576 - 689 2 .3802 0.7989 ±0.40%

Na 2 S 3.7 72.0 563 - 669 2 .2538 0.5459 ±0.13%

Na 2S 4.4 75 .

571 - 680 2 .2687 0.6664 ±0.26%

Na 2 s 4.8 77.0 573 - 683 2 .3056 0.7156 ±0.27%

Table 33.2. Densities (g cm from equations

in table 33.1

T (K) Na 2 S 3.0 Na 2 s 3 .3 Na 2 S 3 .7 Na 2 S 4 ,4 Na 2 S 4 .8 560

570

580 1.9169

1 . 9426

1.9372 1 . 8822 1.8905

590 1 .9089 1.9317 1 .8756 1.8834

600 1.8875 1.9009 1.9263 1.8689 1.8762

610 1.8818 1.8929 1 .9208 1 .8622 1 .8691

620 1.8762 1 . 8850 1 .9153 1.8556 1.8619

630 1.8705 1.8770 1 . 9099 1 . 8489 1.8547

640 1.8648 1 .8690 1 . 9044 1. 8422 1.8476

650 1.8592 1.8610 1.8990 1.8356 1.8404

660 1.8535 1 .8530 1.8935 1.8289 1.8333

670 1.8479 1.8450 1.8223 1.8261

680 1.8422 1.8370 1 . 8156 1.8190

References [12,13],

3. Surface Tension (y)

Measurement method: maximum bubble pressure [12]

Y

= a + bT (33.2)

precision: in table 33.3 uncertainty: % + 1,5%

296
Na

2 S x

Table 33.3. Parameters of equation (33.2), and precisions

Melt Wt % s Temp, range

(K)

a -b x 10 2 Precision

Na 2 s 3 .67 .

583-691 210.22 6.070 ±0.4%

Na 2S 3 .68.5 588-673 237.21 11.98 ±0.4%

Na 2 s 3 . 3 69 .

586-671 191 . 61 6.496 ±0.3%

Na 2 s 3 .

71.5 589-677 162.00 3.395 ±0.2%

Na 2s 3 .

72.4 539-676 153.62 3.592 ±0.2%

Na 2 s 4.

74.0 556-641 163.08 5 . 809 ±0.4%

Na 2 S 4 . 3 75.1 602-676 168.25 6.729 ±1.0%

Na 2 s 4 .

76.3 562-671 169 . 80 7.100 ±0.5%

Na 2S 4 . 8 76.8 625-688 182 .95 9.153 ±1.2%

Na 2s 5 .

78.4 616-661 138.74 3.901 ±0.4%

Table 33.4. Surface tension (dyn cm from equations in table 33.3

T(K) Na 2 S 3 , 0 Na 2 S 3 . i Na 2 S 3 .

Na 2 S 3 . 6 N a ^

S 3 # 9 N

2 S 4 # i N a 2 S 4 # 3 N a 2

S 4 * 7 Na 2 S 4 # g N a 2 S 5 2

530

540 134.22

550 133.86

560 133.51 130.54

570 133.13 129.96 129.33

580 132.79 129.38 128.64

590 174.41 166.52 153.28 141.97 132.43 128.80 127.93

600 173.80 165.32 152.63 141.63 132.07 128.22 127.22

610 173.19 164.12 151.98 141.29 131.71 127.64 127.20 126.52

620 172.59 162.93 151.33 140.95 131.35 127.06 126.53 125.81 114.56

630 171.98 161.73 150.68 140.61 130.99 126.48 125.85 125.10 125.29 114.17

640 171.37 160.53 150.03 140.27 130.63 125.90 125.18 124.39 124.37 113.78

650 170.77 159.33 149.38 139.94 130.27 124.51 123.68 123.46 113.39

660 170. 16 158.13 148. 73 139.60 129.91 123.83 122.94 122.54 113.00

670 169.55 156.94 148.09 139.26 129.55 123.16 122.23 121.63

680 168.94 120.71

690 168.34

References [12]

297
4 . Viscosity ( r\) Measurement method: modified capillary [12]

n = A exp [E /R(T-To) ] (33.3)

precision: in table 33.5 uncertainty: ^ + 5%

Table 33.5. Parameters of equation (33.3) , and precisions

Melt Wt

% S Temp, range

(K)

A(cp)

E

n Ccal mol 1 ) Tq

(K)

Precision

Na 2 S 3 . i 68.4 577-653 0.5624 2018 332 ±0.5%

Na 2 S 3 # 3 70.0 589-647 0.3370 2683 288 ± 0 . 1 % Na 2 S 36 71.7 558-646 0.6193 1906 342 ± 0 . 2 % Na 2 S 3 > 9 73.1 533-652 0.4046 2221 326 O 00 +1 Na 2 S 4 # i 74.0 587-641 0.4070 2234 328 ± 0 . 2 % Na 2 S 4 # 3 75.1 572-675 0.8071 1438 390 ±0,4%

Na 2 S 4 # 7 76.8 557-654 0.4684 1963 356 ± 0 . 6 % Na 2 S 5 _ 2 78.5 620-648 1.7411 742.1 465 ±0.3%

For Na 2 S 3 ^ g , viscosity values at temperatures less than 553 K are

for the supercooled melt.

Table 33.6. Viscosity (cp) from equations in table 33.5

T(K) Na 2 S 3 . l Na 2 S 3 .

Na 2 S 3 . g N a 2 S 3 . 9 Na 2 S 4 . i Na 2 S 4 o 3 Na 2 S 4 ,Na 2 Ss

2

540 75.03

550 59.43

560 50.43 48.02 59. 38 570 41.58 39.48 47.35

580 33.76 34.84 32.96 36.39 38.53

590 28.81 29.46 29.62 27.90 29.72 30.08 31.92

600 24.87 25.53 25.50 23.91 25.39 25.32 26.85

610 21.70 22.32 22.19 20.71 21.93 24.65 22.89

620 19.12 19.67 19.51 18.12 19.13 18.76 19.75 19.37

630 16.98 17.46 17.31 15.99 16;84 16.46 17.23 16.74

640 15.20 15.61 15 .48 14.22 14.94 14.59 15.18 14.71

650 13.71 12.74 13.01 13.48

660 11.77

670 10.70

References [12 ]

5. Electrical Conductance ( k ) Measurement method: Wayne-Kerr ac technique [14]

k = A exp [-E /R(T-To) ] (33.4)

precision: in table 33.7 uncertainty: ^ + 2.51

298
Na-S

2 x

Table 33.7. Parameters of equation (33.4), and precisions

Melt Wt % S Temp . range

(K)

_ A

(ohm 1 cm 1

)

E cal mol 1 To

(K)

P re c i s ion

Na 2 S 2 .i 60.0 728-840 5.4770 736.1 499 ±1.3%

N a 2 S 2 .

66.1 642-698 3 .8590 595.4 458 ±0.9%

Na 2 s 3.0 67 . 5 582-693 7 . 0407 1362 329 ±0.5%

Na 2 S 3.2 70.1 458-694 7 . 0650 1402 330 ±1.0% • Na 2 S 3,8 72.3 428-694 7 . 0860 1541 325 ±0.7%

Na 2 S 4,2 74 .

456-671 6 .2783 1475 341 ±1.4%

Na 2 S 5.1 77.8 477-681 5.7935 1513 344 ±1 . 0 %

For the following polysulf ides , conductivity measurements have been

extended into the supercooled liquid state region [refer phase

diagram]: Na 2 S 2 . i (T < 7 48K) ; Na 2 S 3 , 2 (T < 5 38K) ; Na 2 S 3 , 8 (T < 553K) ; Na 2 S 4 . 2 (T < 543K) ; Na 2 S 5 (T < 533K).

Table 33.8.1. Specific conductance (ohm ^cm from

equations in table 33.7

T

(K) Na 2^2,9 Na 2 S 3 . 0 Na 2 S 3 . 2 Na 2 S 3 . e Na 2 S 4 . 2 Na 2 ^ 5 , 1 430 0.0044

440 0.0084

450 0.0143

460 0.0311 0.0227 0.0123

470 0.0458 0.0337 0.0199

480 0.0640 0.0476 0.0301 0.0215

490 0.0859 0.0645 0.0431 0.0315

500 0.1114 0.0843 0.0589 0.0440

510 0.1402 0.1071 0.0777 0.0591

520 0.1724 0.1328 0.0993 0.0767

530 0.2075 0.1613 0.1237 0.0967

540 0.2455 0.1923 0.1506 0.1192

550 0.2860 0.2257 0.1801 0.1439

560 0.3288 0.2614 0.2118 0.1708

570 0.3736 0.2991 0.2456 0.1996

580 0.4202 0.3386 0.2812 0.2302

590 0.5095 0.4684 0.3798 0.3186 0.2625

600 0.5613 0.5179 0.4224 0.3574 0.2963

610 0.6142 0.5686 0.4663 0.3976 0.3313

620 0.6679 0.6202 0.5114 0.4390 0.3675

630 0.7223 0.6726 0.5574 0.4813 0.4047

640 0.7771 0.7256 0.6043 0.5245 0.4428

650 0.8105 0.8324 0.7791 0.6518 0.5683 0.4816

660 0.8756 0.8878 0.8329 0.7000 0.6128 0.5211

670 0.9390 0.9434 0.8870 0.7485 0.6577 0.5611

680 1.001 0.9990 0.9412 0.7975 0.6014

690 1.060 1.055 0.9954 0.8467

700

299
Na^S

2 x

Table 33.8.2. Specific conductance for additional mixture, Na ? S

T K T K (K) (ohm 1 cm 1 ) (K) (ohm cm 1

) 730 1.102 790 1 .534

740 1.178 800 1.600

750 1.252 810 1.664

760 1 . 325 820 1.727

770 1 . 396 830 1.789

780 1.466 840 1.848

References [14] .

6. Safety and Hazards

A . Hazard rating [15-17]

(i) Inhalation: variable

• as sulfides and polysulfides, the rating is similar to

sodium hydroxide

• on reaction with moisture/water, H2S is liberated; the

inhalation hazard rating for H2S is severe; i.e., highly

toxic

(ii) Vapor pressure: the sulfur pressure above some molten

polysulfide compositions has been reported, e.g., at ^ 1000°C,

the sulfur pressures above Na2S2, ^283, and ^2^4 are respectively, ^ 15 mm, ^ 300 mm, and % 2000 mm.

B. Disaster hazards [15,18-20]

(i) Molten sulfides and polysulfides may react violently

(explosively) with strong oxidizers; H2S evolved on contact

with moisture/water can form explos ive mixtures with air;

H2S, highly toxic.

(ii) Polysul f ides , when heated to decomposition, or contacted

with water, steam, acids, produce highly toxic fumes

(oxides of sulfur; ). Dangerous.

References [15-20].

7. Corrosion

Table 33.9.1. Corrosion screening studies [21-23]

Extensively corroded materials

TaB

2

, ZrC , VN , VC, Nb B

2

, ZrSi

2

, TiSi

2

, CrB

2 ,ZrN,

CrC, CaTiO^ (+ 0.3% F

2 0^ )

, ano d i z ed Ti, Ti

Corrosion protection from sulfide or oxide film formation

Zr, C r S

2

, TiC, ZrB 2> TiN, Si,TaC, TaN, AISI 446

stainless steel, Inconel600 and 601, Mo

300
Table 33.9.1. - - Continued

Intrinsically Corrosion Resistant Materials

Cr

2 0

3> Mo S

^ , ZrC>2 > La

0 84 Sr0 16 Cr °3’ Ti0-2 ( sin 8 le

crystal and polycrystalline doped with Ta) . SrTiO^,

CaTiO^ (+ 3.0% Fe

2 0

3

) Polyphenylene (PpH) , Polyphenylene-graphite composites, oxidized stainless

steels , NiO

Table 33.9.2.-- Corrosion studies: static techniques [21-23]

(i) All metals and alloys are attacked to some

extent. Sulfides of metals appear to be thermodynamically more stable than the unreacted metals.

(ii) Certain metals - Fe, Cu, Ni, Au , and Ti - are rapidly corroded, i.e., rapid dissolution of the

sulfide product in the polysulfides

(iii) With the metals Cr, Hf, Zr and Mo the attack is

less severe, i.e., apparently a slow dissolution

of the sulfide product in the polysulfides

(iv) Alloys containing an appreciable concentration

of Cr 20%) are slowly attacked at a rate

similar to that for Cr metal itself. Both

ferritic and austenitic stainless steels and

several grades of Inconel exhibit this characteristic; i.e., apparently an accumulation of Cr

sulfide in the corrosion inhibiting layer.

(v) The oxides of the reactive metallic elements

studied thus far are instr insically stable in

molten polysulfide; i.e., correlates with the

relative thermodynamic stabilities of oxides and

sulfides of these elements

(vi) In general, metallic borides, carbides, nitrides,

and silicides are rapidly attacked.

(vii) Certain forms of carbon are stable. Graphite,

vitreous carbon, and a thermosetting polyphenylene resin have been found to be

intrinsically stable.

Table 33.9.3. Corrosion studies from primary research literature:

dynamic studies (electrochemical) [21,24,25,27]

Studies Cond it ions

Fe (99.98%) Steady-state current-potential

measurements

18-8 SS anodic and cathodic corrosion properties

E-Brite - SS pre-oxidized (750°C, 1 hr); anodic

and cathodic

AISI-446-SS pre-oxidized (750°C, 20 hr);

anodic and cathodic

Fe-Co-Ni -

301
Na

2 Sx

Table 33.9.4. Corrosion studies from primary research literature:

various additional studies [21-23,26]

Studies Cond itions

AISI-446-SS preoxidized; static corrosion

E-Br ite-SS studies at 300 , 350 ° C

,

4 00 ° C

pr e-oxid ized ; statis corrosion

AISI-446-SS studies; various polysulfide

compositions (Na^S^, Na^ S 4

, N a

2 S 5

)

Fe, Zr, Hf static corrosion studies in Na^^

AISI-446-SS static corrosion studies in Na

2

S Corrosion in molten

salts annotated bibliography

Metal sulfides saturation solubilities

t solute solvent solubility

(°C) (polysulf ide) (mg/g)

Na 2 S 5 71.4'

375 CrS Na 2 S 4 46.

x 10

-3

Na 2 s 3.2 40.6

Na 2 S 2.74 6.0

N3o S c 3.42

375 MnS Na

2 s

4

2 . 12

Na

2

S

3 2 1 . 18

0.50

Na 2 s 5 0.17

375 FeS Na 2 S 4 1/28

Na 2 s 3.2 2.72

Na 2 S 2 .74 3 .99

Na 2 S

5 0.15

375 NiS Na 2 S

4 0.47

Na 2

S

3 2 1.18

Na 2 S

2. 7 4 4.64

325 CrS Na 2 S

4 30

FeS 0.6

300 FeS N a

2 S

5 0.1

NiS 0.1

300 FeS Na 2 S 2 q 2 NiS 0.8

References [21-27],

8. Diffusion

No diffusion studies reported.

9. Heat of Fusion (AH^,)

No data.

302
10 . Heat Capacity (C )

No data.

Na 9 S

2 x

11 . Volume Change on Melting ay

No data.

12. Vapor r Pressure (pr ) vap

Measurement method: transpiration; emf. [28-30]

Polysulfides exhibit equilibrium sulfur vapor pressures. The equilibrium

sulfur pressures for a series of polysulfides covering the composition range

from Na 2 Si i7 to Na 2 S 5 >5 reported herewith have been calculated from the

Tegman data-base [28-30]

Vaporization studies of molten polysulfides as molecular polysulfide

species have not been reported. In the Tegman studies of sulfur equilibrium

pressures, the observation is reported that a faint condensate due to

polysulfide molecular species was evident in the temperature range of

1173-1273 K. From this it is apparent that the vapor pressures as molecular

polysulfides are much smaller than the equilibrium sulfur pressures, i.e.

possibly more comparable to the alkali metal halides.

Equilibrium sulfur pressures for Na

2 S x log p

= A + B/T (33.5)

precision: in table 33.10.1 uncertainty: ^ + 101

Table 33.10.1. Parameters of equation (33.5)

precisions, and temp, range

Na 2S x A -B Precision Temp, range

(K) Ha 2 S x A -B Precision Temp, range

(K) Na 2 S 1

. 70 8.132 8656 0.0* 1073-1173 Na 2 S 3. 70 9.710 6804 + 10* 523-873

Ua 2 s 1 . e 0 7.814 8139 0.0* 1073-1173 Na 2®3 . 80 9.720 6734 + 10* 523-873

Na 2 S 1 >90 6.456 6424 + 30* 973-1173 N fl 2S 3 , 9 0 9.726 6669 + 10* 523-873

Na 2 S 2 . 00 6.547 6285 0.0* 973-1073 Na 2

S 4 , 00 9.737 6611 + 10* 523-873

Na 2s 2 . 16.327 5912 + 5* 873-1073 Na 2 S 4 . 10 9 .752 6566 + 5* 523-873

^ a 2® 2 . 2 0 5.636 5182 + 10* 873-1073 Ne 2 S 4 . 2 0 9.768 6516 + 10* 523-873

Na 2S2 . 30 5.736 5164 0.0* 873-973 Ha 2S4 . 30 9.783 6469 + 8* 523-873

Na 2 S 2 . 40 7.497 6707 + 30* 773-973 Na 2 S 4 . 40 9.797 6418 ± 7* 523-873

Na 2 S 2 . 50 7.159 6275 ± 30* 773-973 Na 2

S 4 . 50 9.808 6375 ± 5* 523-873

Nb 2S2 . 6 0 8.082 6948 ± 15* 623-973 Na 2

S 4 . go 9.814 6331 + 10* 523-873

Na 2 S 2 . 70 8.254 6928 ± 15* 623-973 Na 2 S 4 , 7 0 9.813 6286 t 5* 523-873

Na 2 ®2 . 8 0 9.077 7356 ± 3* 623-873 Na 2® 4 . 8 0 9.805 6238 ± 5* 523-873

Na 2 S 2 . 9 0 9.209 7319 ± 3* 623-873 Na 2 S 4 , 90 9.787 6186 ± 5* 573-873

Na 2 S 3 . 00 9.396 7330 ± 2* 573-873 Na 2 S 5 . 0 0 9.757 6130 + 5* 573-873

Na 2 S 3 . 10 9 . 316 7146 ± 2* 523-873 Na 2 s 5 . 1 0 9 .775 6112 + 5* 573-873

^a 2® 3 . 2 0 9.367 7065 ± 3* 523-873 N a 2 S 5 . 2 0 9 . 715 6041 ± 4* 623-873

Na 2 S 3. 30 9 . 399 6979 + 4* 523-873 N3 2 S 5 , 30 9 . 629 5955 ± 8* 623-873

Na 2S 3 . 40 9.421 6894 ± 6* 523-873 Ha 2

S 5 . 4 0 9 . 316 5692 + 8* 673-873

Na 2 S 3 . 50 9.568 6888 ± 62 523-873 Na 2 s S. 50 7.330 4033 0.0* 773-873

Na 2 S 3 . 6 0 9.566 6802 ± 6* 523-873 Na 2

s 5 . 6 0 7.870 4486 0.02 773-873

NoteFor the composition ranges Na 2 Si

7 -Na 2 S 2 , 5 and Na 2 S 5 data-sets were very limited (i.e.' 3 values).

4 -Na 2 S 5 t, the

303
Na-S

2 x

Table 33.10.2. Equilibrium sulfur pressures for

some polysulfides from equations in table 33.10.1

P (mm)

T(K) Na 2 S 2

Nil 2 S 2 . 5 Na 2 S 3 Na 2^3 .

Na 2 S 4 Na 2 . 5 Na 2 S 5 ^ a 2 S 5.

540 0.0008 0.0031 0.0101 0.0254

560 0.0023 0.0085 0.0266 0.0647

580 0.0006 0.0061 0.0218 0.0656 0.1542

600 0.0015 0.0151 0.0523 0.1524 0.3470

620 0.0037 0.0353 0.1186 0.3355 0.7411

640 0.0088 0.0786 0.2555 0.7032 1.5096

660 0.0195 0.1666 0.5252 1.4090 2.9453

680 0.0414 0 . 33 7 7 1.0350 2.7102 5.5245

700 0.0841 0.6577 1.9621 5.0218 9.9968

720 0.1642 1.2341 3.5897 8.9916 17.5031

740 0.3095 2.2382 6.3565 15.6005 29.7317

760 0.5640 3.9341 10.9224 26.2933 49.1150

780 0.1301 0.9967 6.7179 18.2542 43.1446 79.0733 144.3749

800 0.2067 1.7120 11.1687 29.7340 69.0643 124 . 3096 194.4262

820 0.321 ' 2 . 8640 18.1135 47.2943 108.0473 191.1592 258.0551

840 0 . 4 88 ‘t 4.6753 28.7080 73.5810 165.4699 287.9958 337.9208

860 0.7286 7.4601 44.5350 112.1489 248.4358 425.6952 436.9892

880 1.0674

900 1.5374

920 2.1795

940 3.0442

960 4.1932

980 1.3606

1000 1.8281

1020 2.4279

1040 3.1896

1060 4.1472

References [6,28-33].

13. Thermal Conductivity (liquid) (A^)

No thermal conductivity studies reported,

14. Thermal Conductivity (solid) (X ) No thermal conductivity studies reported,

15. Cryoscopic Constant

No data.

16.

References

[1] Rosen, E. , and Tegman, R. , Acta Chem. Scand., 2_3, 3329 (1971).

[2] Rosen, E., and Tegman, R. , Chimica Scripta, 2_, 221 (1972).

[3] Oei , D. G., Inorg. Chem., 12., 435, 438 (1973).

[4] Janz, G. J., Downey, J. R. , Jr., Coutts, J. C. , Roduner, E. , and

Wasilczyk, G. , Inorg. Chem., 15, 1751, 1755, 1759 (1976).

[5] Janz, G. J., Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T.

,

"Eutectic Data". - 2 vols.; ERDA-TID- 27163-PI 8 P2; NTIS,

Washington, D. C. (1977).

304
[6] Pearson, T. G., and Robinson, P. L., J. Chem. Soc., 1473 (1930).

[7] Feher, F. , and Berthold, H. J., Z. anorg. Chem., 273 , 144 (1953).

[8] Rule, A., and Thomas, J. S., J. Chem. Soc., 105 , 177 (1914).

[9] Cleaver, B., and Davies, A. J., Electrochim. Acta, 18^, 733 (1973).

[10] Miles, L. J., and Wynn-Jones, I., Proc. Br . Ceram. Soc., 1_9, 179 (1971).

[11] Janz, G. J., Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T.,

" Physical Properties Bata Compilations Relevant to Energy Storage . I.

Molten Salts: Eutectic Data", NSRDS -NBS - 6 1 ; U. S. Gov’t Printing

Office, Washington, D. C. (1978).

[12] Cleaver, B., and Davies, A. J. , Electrochim. Acta, 1_8 , 727 (1973).

[13] Oei, D. G., Inorg. Chem., L2, 438 (1973).

[14] Cleaver, B., Davies, A. J., and Hames, M. D. , Electrochimica Acta,

18, 719 (1973).

[15] "Dangerous Properties of Materials", Sax, N. I., Van Nostrand Reinhold

Co., N. Y. (1969).

[16] "Registry of Toxic Effects of Chemical Substances", Christensen,

H. E., and Lubinbyhl, T. T. , eds . , U. S. Dept. H. E. W. , U. S.

Gov't Printing Office, Washington, D. C. (1975).

[17] Tiberg, A., and Tiberg, J., Acta Chemica Scand. , 24_, 991 (1970).

[18] "Potential Hazards In Molten Salt Baths for Heat Treatment of Metals", National Board Fire Underwriters Research Report No. 2 (1954).

[19] "Handbook of Reactive Chemical Hazards", Bretherwick, L., Butterworths

Co . , London (1975) .

[20] Janz, G. J,, Tomkins, R. P. T., Downey, J. R., Jr., and Allen, C. B.,

"Safety and Hazards ", Chapter in "Eutectic Data", ERDA TID - 2 71 63 -PI

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[21] Weiner, S. A., (Ford Motor Co.); Annual Report; NSF-RANN Contract No.

NSF-C805 (AER-73-07199) , (1974).

[22] Weiner, S. A., (Ford Motor Co.); Annual Report; NSF-RANN Contract No.

NSF-C805 (AER-73-07199), (1975).

[23] Weiner, S. A., and Tischer, R. (Ford Motor Co.); Annual Report; NSF-RANN

Contract No. NSF-C805 (AER-73-07199), (1976).

[24] Bones, R. J., Brook, R. J., and Markin, T. L., Proceedings Ninth

International Power Sources Symposium, Brighton, England (1974).

[25] Dubin, R. R. , Abstr. No. 11. Extended Abstracts; 75-1, 27 (1975); 147th

Meeting, Electrochemical Society (Toronto), May (1975).

[26] Janz, G. J., and Tomkins, R. P. T., Corrosion, 3£, (in press) (1978).

[27] Armstrong, R. D. , Dickinson, T., and Reid, M. , Electrochimica Acta, 2

, 1143 (1976).

[28] Tegman, R. , "Thermodynamic Studies of High Temperature Equilibria. XI.

Temperature Dependence of Equilibria between Sulfur Vapor and Species

in Sodium Polysulfide Melts", Chem. Scripta (to be published).

[29] Tegman, R. , "Studies of Structures and Equilibria of Solid and Liquid

Sodium Poly sulfides", Ph . D . Thesis, Univ. Umea, Sweden (1974).

[30] Tegman, R. , Chemica Scripta, 2_, 63 (1972).

305
[31]

[32]

[33]

Na 0 S

2 x

Gupta, N. K. , and Tischer, R. P., J. Electrochem. Soc., 119, 1033 (1972).

vide infra ref. [17]

vide infra ref. [9], ' -i

:G:' ’:i

. \. .

1

'

306
XXXIV. Sodium Fluoride -Potassium Fluoride: NaF-KF

1. Melting Temperatures (Tm

) Pure substance melting points:

NaF: 995°C

KF: 8 56 °C

Eutectic melting point:

710°C, composition: 40 mol % NaF

Figure 34.1. NaF-KF phase diagram

References [1-8] .

Density (p)

Measurement method: Archimedean technique [9]

p = a + bT (34.11

precision: in table 34.1 uncertainty: ^ + 2-

Table 34.1. Parameters of equation (34,1), and precisions

Mol % NaF a -b x 10 4 Precis ion

0.0 2 .555 6.241 ±0.15%

12 .

1.867 1.011 ±1.08%

25 .

2 . 114 2.853 ±0.80%

40 .

2 .568 6.000 ±0.67%

60.0 2 . 530 5.641 ±0.15%

80.0 2 . 601 5.878 ±0.12%

100.0 2.682 6.151 ±0.13%

307
NaF-KF

_ 3 Table 34.2. Densities (g cm ) from equations

in table 34.1

T ( K )

Mol °/ NaF

100.0 80.0 60.0 40.0 25 .12 .

0.0

1050 1.938

1065 1 .929 1 .810

1080 1 .920 1.806

1095 1 . 911 1 .802 1.756

1110 1.902 1.797 1.755

1125 1.895 1.893 1.793 1.753

1140 1 . 887 1.884 1.789 1.752 1.844

1155 1.878 1.875 1 .784 1.750 1.834

1170 1.870 1.866 1 . 780 1.749 1.825

1185 1.862 1.857 1.776 1 .747 1.815

1200 1.896 1.853 1.848 1.772 1.746 1.806

1215 1 ..88 7 1.845 1.839 1.767 1.744 1.797

1230 1 .878 1.836 1.830 1.763 1 . 743 1.787

1245 1.869 1.828 1.821 1.759 1 .741 1.778

1260 1.860 1.819 1.812 1.755 1 .740 1.769

1275 1.898 1.852 1.811 1.803 1.750 1 .738 1.759

1290 1 .889 1.843 1.802 1.794 1 .746 1.737 1.750

1305 1.879 1.834 1.794 1.785 1.742 1.735 1 .741

1320 1.870 1.825 1 .785 1.776 1 .737 i :734 1.731

1335 1.861 1.816 1.777 1.767 1 . 733 1.732 1.722

1350 1.85 2 1.807 1.768 1.758 1 . 729 1.731 1.712

References [9-13]

3. Surface Tension (y)

Measurement method: maximum bubble pressure [12]

y

= 243.73 - 7.92 x 10

_2

T (34.2)

precision: ^ + 0.3% uncertainty: ^ + 1,0%

For numerical values see table 34.3

308
NaF-KF

Table 34,3. Surface tension for the eutectic from equation (34.2)

T00

Y (dyn cm" 1 )

T(K)

Y (dyn cm 1

)

910 171.7 * 1030 162.2

920 170.9 * 1040 161.4

930 170.1 * 1050 160.6

940 169.3 * 1060 159 .

950 168.5 * 1070 159 .

960 167.7 * 1080 158.2

970 166.9 * 1090 157.4

980 166.1 * 1100 156.6

990 165 .

1110 155.8

1000 164.5 1120 155 .

1010 163.7 1130 154.2

1020 162.

References [9-12]. * Values are for supercooled liquid.

4 . Viscosity (n

No data.

5. Electrical Conductance (k)

Measurement method: ac technique [10]

k = a + bT (34.3)

precision: in table 34.4 uncertainty: ^ + 4%

Table 34.4. Parameters of equation (34.3), and precisions

Mol % NaF a x 1

2 b x 10 3 Precision

0.0 38 . 84 2.940 ±0.47%

12 .

-39.59 3.525 ±0.65%

25.0 -86.67 3.958 ±0.26%

40.0 -54.67 3 . 580 ±1 . 09%

60.0 -12.82 3 . 500 ±0.55%

80.0 17.97 3.420 ±0.60%

100.0 -206.0 5. 640 ±1.21%

309
NaF-KF

Table 34.5. Specific conductance (ohm "^cm

)

from

equations in table 34.4.

Mol % NaF

T ( K ) 100.0 80.0 60.0 40.0 25.0 12 .

0.0

1050 3 . 21

1060 3 . 25

1070 3 . 28

1080 3 . 32 3.41

1090 3.36 3.45 3.45

1100 3 .39 3.49 3.48

1110 3.76 3.43 3.53 3 .52

1120 3 .79 3 .46 3.57 3.55

1130 3 .83 3 . 50 3.61 3 .59

1140 3 .86 3.54 3.65 3 . 62 3.74

1150 3 . 90 3 . 57 3.69 3 . 66 3.77

1160 3 . 93 3.61 3.73 3 . 69 3 .80

1170 3 .97 3.64 3.76 3.73 3 . 83

1180 4 . 00 3 . 68 3 .80 3.76 3.86

1190 4.04 3.71 3 . 84 3 .-80 3 .89

1200 4 .07 3.75 3.88 3 .83 3 . 92

1210 4 . 11 3.79 3.92 3 .87 3.95

1220 4 . 14 3 .82 3.96 3.91 3.98

1230 4.39 4 . 18 3 .86 4 . 00 3.94 4.01

1240 4 .42 4 . 21 3.89 4.04 3 . 98 4 . 03

1250 4.46 4.25 3.93 4.08 4.01 4 . 06

1260 4.49 4.28 3 . 96 4 .12 4 . 05 4.09

1270 4 . 52 4.32 4. 00 4 .16 4 . 08 4.12

1280 4.56 4.35 4.04 4 .20 4 .12 4 .15

1290 4.59 4 .39 4.07 4 .24 4.15 4.18

1300 4.63 4.42 4.11 4.28 4 .19 4 .21

1310 5.33 4 . 66 4.46 4.14 4 .32 4.22 4 . 24

1320 5.39 4.69 4 .49 4 . 18 4 .36 4.26 4.27

1330 5.44 4 .73 4.53 4 . 22 4.40 4.29 4.30

1340 5 . 50 4.76 4.56 4 .25 4.44 4.33 4 . 33

References [9-13].

6. Safety and Hazards

A. Hazard rating [14-16]

(i) Toxicity: NaF, severe; KF , severe.

(ii) Vapor pressure: no data for

NaF, KF.

mixture

but see:

(iii) U. S. occupational standards:

KF , 7.6 mg/m* (air).

NaF, 5 . 5 mg/m 3 (air)

310
NaF-KF

B. Disaster hazards [14,17-19]

(i) Molten salt bath "explosions": i.e. explosive generation of steam due to bulk water "carry-over" and/or

equipment failure; i.e., explosive expansion of

"trapped" air.

(ii) Fluorides, when heated to decomposition, or contacted with acids, emit highly toxic fumes.

References [14-19],

7.

Corrosion

Table 34.6. Corrosion studies from primary research literature

Studies References

Cr 20

Ni-Cr-Fe 21-25

Quartz 26

A1 27

Inconel 600; Hastelloy B (Ni base,

28% Mo, 5% Fe); Hastelloy W (Ni

base, 25% Mo, 5% Cr, 5.5% Fe);

Hastelloy N (i.e. INOR-8, Ni

base, 15% Mo, 6% Cr, 5% Fe)

28-29

Electrochemical behavior of

oxide ions and related species

in molten fluorides

30-32

Electroanaly tical studies in

molten fluorides 33

Annotated corrosion biblio. 34

Corrosion in molten fluorides

( survey) 35

References [20-35],

8. Diffusion

No diffusion studies reported.

9. Heat of Fusion (LH^)

Measurement method: calc'd, from cryoscopy [36]

Table 34.7. Heat of fusion

Binary

(mol %

eutectic

NaF)

AH°

t -1

(kcal mol ) Uncertainty

40 4. 97 'x. ± 2%

References [36,37].

311
NaF-KF

1 0 .

11 .

Heat Capacity

No data.

Volume Change

Measurement

on Melting (AF^J

method: estimated; from densities [36]

Table 34.8. Volume change on melting

Binary eutectic (AV /V ) Uncertainty

(mol % NaF) I s

40 17 . 9% 'v. ± 8%

References [36]

12. Vapor Pressure (-P Vap)

No vaporization studies reported,

13. Thermal Conductivity C liquid

)

No thermal conductivity studies reported.

14. Thermal Conductivity (solid) (\ ) No thermal conductivity studies reported.

15. Cryoscopic Constant

Measurement method: cryoscopy [38]

Table 34.9. Cryoscopic constant

Binary eutectic

(mol % NaF)

k

f (K mol _1 kg

_1

) Uncertainty

40 20 ^ ± 2%

References [ 38]

16.

References

[1] Robertson, W. D., "Binary Phase Diagrams of Halide Salts", (Vols.

1 and 2), Yale Univ., New Haven, Conn., USAEC Report At(30-1)

2723, June (1966).

[2] Janz, G. J., Downey, J. R., Jr., Allen, C. B., and Tomkins, R. P. T.,

"Eutectic Data" - 2 Vols; ERDA-TID - 271 63 -PI 8 P2; NTIS, Washington,

D. C. (1977).

[3] Janz, G. J. , Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T.,

"Physical Properties Data Compilations Relev ant to Energy Storage.

I. Molten Salts: Eutectic Data", NSRDS -NBS - 61 ; U. S. Gov't Printing

Office, Washington, D. C. (1978).

[4] Kurnakov , N . S .

,

186 (1907).

and Zhemchuzhnuii , S. F . , Z . anorg . Chem

, 5_2

,

[5] Dombrovskaya , N. s., and Koloskova, Z. A . , I zv . Sekt . Fiz

Khim

Anal . , 10, 211 (1938) . Bergman, A. G., and Nikonova, I. N. , Zh. Obshch. Khim . , 12, 449 (1942)

Bergman

,

A. G., and Nagornyi, G. I . , Bull . Acad

Sci . USSR Classe

Sci. Chim., 328 (1943).

312
[ 8 ]

[9]

NaF-KF

Wailey, W., M. S. Thesis, Yale University, 1962.

Porter, B., and Meaker, R. E., United States Department of the

Interior, Report of Investigations 6838 (1966).

[10] Meaker, R. E., Porter, B., and Kesterke, D. G., United States

Department of the Interior, Report of Investigations, 7528 (1971),

[11] Batashev, K. P., Legkie Metal., No. 10, 48 (1936).

[12] Mellors, G. W. , and Senderoff, S., Electrochemistry, Proceedings of

the First Australian Conf ., Pergamon Press, p, 578 (1964),

[13] Bergman, A, G., and Dergunov, E. P., Compt. Rend. Acad. Sci. USSR,

31, 753 (1941).

[14] "Dangerous Properties of Materials ", Sax, N. I., Van Nostrand Reinhold

Co . , N. Y. (1969)

[15] "Registry of Toxic Effects of Chemical Substances", Christensen, H. E,,

and Lubinbyhl , T. T., eds., U. S. Dept. H. E. W. , U. S. Gov’t Printing

Office, Washington, D. C. (1975).

[16] Vapor pressure; estimated (MSDC-RPI) unpublished work (1978),

[17] "Potential Hazards in Molten Salt Baths for Heat Treatment of Metals"

National Board Fire Underwriters Research Report No. 2 (1954),

[18] "Handbook of Reactive Chemical Hazards", Bretherwick, L., Butterworths

Co . , London (1975)

[19] Janz, G. J., Tomkins, R. P. T, , Downey, J, R. , Jr., and Allen, C. B.

"Safety and Hazards ", Chapter in "Eutectic Data", ERDA-TID27163-P1; NTIS, U. S. Dept. Commerce, Springfield, Va. (1977),

[20] Brasunas, A., Metal Progr., 6_2, 88 (1952),

[21] Grimes, W. R. , Blankenship, F, F., Keilholtz, G, W. , Poppendiek, H, F,,

and Robinson, M. T., "Chemical Aspects of Molten Fluoride Reactors ", Proc. Sec. U. N. Inter. Conf. Peaceful Use of At. Energy, Geneva,

28, 99 (1958),

[22] Oak Ridge National Laboratory, Molten Salt Reactor Program Semiannual

Progress Report for Period Ending July 31, 1964; ORNL-3708 (1964).

[23] Adamson, G. M. , Manly, W. D., and Crouse, S. R., "Corrosion by Molten

Fluorides", ANP Materials Meeting, ORNL-2685, (1958).

[24] Manly, W. D., Adamson, G. M., Coobs, J. H., DeVan, J. H., Douglas, D. A

Hoffman, E. E., and Patriarca, P,, "Aircraft Reactor ExperimentMetallurgical Aspects" ORNL-2349, Oak Ridge National Laboratory (1958)

[25] Manly, W. D., Coobs, J. H. , DeVan, J. H., Douglas, D. H. , Inouye, H.,

Patriarca, P., Roche, T. K. , and Scott, J. L., "Metallurgical Problems

in Molten Fluoride Systems", Proc. 2 nd U. N. Inter. Conf. Peaceful

Uses of At. Energy, 223 (1958).

[26] Heimann, R. , Glastech. Ber . , 43_, 83 (1 97 0).

[27] Lukashenko, E. E., and Reutova, G. A., Nov. Thor. Tekhnol. Metall.

Protsessov, 119 (1973).

[28] Manly, W. D., et al . , "Construction Materials for Molten Salt Reactors ", Ch. 13 in Fluid' Fuel Reactors", Lane, J. A., MacPherson, H. G.,

and Maslan, F. eds., Addison-Wesley Co. Inc. Publ . (1958).

[29] Oak Ridge National Laboratory, "The Development Status of Molten Salt

Breeder Reactors", Rpt . ORNL -4 8 1

2 -UC - 8 0 ; NTIS, U. S. Dept. Commerce,

Springfield, Va. (August, 1972).

313
NaF-KF

[30] Mathews, A, L., and Baes, C, F,, Inorg. Chem., 7, 373 (1968).

[31] Manning, D. L., and Mamantov, G f , J. Electrochem. Soc , , 124, 480 (1977),

[32] Ting, G., Baes, C. F., Bamberger, C. E.j and Mamantov, G., J. Inorg.

Nucl . Chem., 3£, 1803 (1977).

[33] Manning, D, L., and Mamantov, G,, J. Electroanalyt . Chem,, (in press)

(1978)

[34] Janz, G. J., and Tomkins, R. P. T,, Corrosion, 34_ (in press) (1978).

[35] Eichelberger , J. L., (Pennwalt Corpn.), "Investigations of Metal

Fluoride Thermal Energy Storage Materials: Availability , Cost

,

Chemistry

3 ERDA Rpt 2990-6; NTIS, U. S. Dept. Commerce,

Springfield, Va. (Dec. 1976).

[36] Janz, G. J., et al . , (MSDC-RPI) unpublished work (1977).

[37] Rolin, M. , Congr . intern, aluminium, Par is ; 3^ 51 (1954); (publ . 1955).

[38] Rolin, M., vide infra ref. [37]

314
XXXV. Lithium Fluoride-Lithium Chloride: LiF-LiCl

1. Melting Temperatures (

m

) Pure substance melting points:

LiF: 84 8

° C

LiCl : 61 0°C

Eutectic melting point:

484°C, composition: 69.5 mol I LiCl

Figure 35.1. LiF-LiCl phase diagram

References [ 1 - 3 ]

.

2. Density ( p ) Measurement method: Archimedean technique [4]

Single variable equation

p=a + bT C3 5.1)

precision: in table 35.1 uncertainty: ^ + 2%

315
LiF-LiCl

Table 35.1. Parameters of single variable equation

(35.1), and precisions

Mol % LiCl a -b x 10 3 Precision

0 2 .266 0.414 ±0.11%

12 2 .160 0.417 ±0.17%

25 2 .116 0.443 ±0.18%

37 2 . 050 0.436 ±0.18%

50 2 . 000 0.438 ±0.13%

63 1 .962 0.440 ±0.26%

75 1.928 0.437 ±0.26%

88 1 . 905 0.438 ±0.27%

100 1.896 0.446 ±0.34%

Two- independent variable equation

p = a + bC + cT + dC 2 + eC

3 + fTC 2 + gCT 2 (C = mol % LiCl) (35.2)

precision; + 0,004%, uncertainty: ^ + 2%

Table 35,2, Parameters of two-independent -variable equation (_35,21

a b x 10 3 c x 10 4 d x 10 5 e x 1

7 f x 10 9 g x 10 10

2 .25621 -8 . 20475 -4 . 09235 6 .37250 -2.52846• 8.73570 -5 . 11184

Table 35,3, Densities Cg cm' 3 ) from equations in table 35,1

Mol % LiCl

T (K) 100 88 75 63 50 37 25 12 0

940 1.477 1.493 1.517 1.548 1.588 1 . 640 1.699 1.768 1.877

960 1.468 1.485 1 . 508 1 . 540 1.579 1 . 631 1 .691 1.760 1 .869

980 1.459 1.476 1.500 1 . 531 1.571 1 .623 1 . 682 1.751 1 .860

1000 1.450 1.467 1.491 1 .522 1.562 1 . 614 1 . 673 1.743 1.852

1020 1 . 441 1.458 1 .482 1.513 1 .553 1 . 605 1 . 664 1.735 1 . 844

1040 1.432 1 .449 1 .473 1 . 504 1.544 1 .597 1 .655 1.726 1.835

1060 1.423 1.441 1.465 1 .496 1 .536 1.588 1 . 646 1.718 1 .827

1080 1 .414 1.432 1 .456 1.487 1.527 1.579 1.637 1.710 1 . 819

1100 1.405 1.423 1 .447 1 .478 1.518 1.570 1 .629 1 .701 1 . 811

1120 1.396 1.414 1.439 1.469 1.509 1.562 1.620 1.693 1 . 802

1140 1.387 1.406 1.430 1.460 1.501 1.553 1.611 1 . 685 1.794

1160 1.379 1.397 1.421 1.452 1.492 1.544 1 .602 1.676 1.786

1180 1.370 1.388 1.412 1.443 1.483 1.535 1 .593 1.668 1.777

1200 1.361 1.379 1.404 1.434 1.474 1.527 1.584 1 .660 1.769

1220 1 .352 1.371 1.395 1.425 1.466 1 .518 1.575 1 . 651 1.761

1240 1.343 1.362 1 . 386 1 .416 1.457 1 .509 1 .567 1.643 1.753

1260 1.334 1 . 353 1.377 1.408 1 .448 1 .501 1.558 1.635 1 .744

References [4-7]

316
LiF-LiCl

3. Surface Tension (y)

Measurement method: maximum bubble pressure [8]

Single variable equation y

= a + bT (35.3)

precision: ^ + 0.51 uncertainty: ^ + 1%

Table 35.4. Parameters of single variable equation (35.3)

Mol % L1C1 a -b x 10 2

0 350.2 9.86

12 323.8 9.49

25 303.3 9.58

37 281.7 9.22

50 264.4 9.13

63 250.0 9.06

75 234.1 8.53

88 223.2 8.42

Two- independent- variable equation

y

= a + bTC + cC

2 + dCT 2 + eTC 2 + fT3 (C = mol % LiCl) (35.4)

precision: ^ + 0.2%, uncertainty: a- + 1%

Table 35.5. Parameters of two - independent -variable

equation (35.4)

a b x 10 3 o

i

o M d x 10 6 e x 10 6 f x 10 8

271.25732 -2.89297 -4.13850 1.04392 7.27278 -2.26107

317
LiF-LiCl

Table 35.6. Surface tension (dyn cm"’*') from

equations in table 35.4

T Mol % L1C1

(K) 88 75 63 50 37 25 U 0

93Q 144.9

960 142.4 152 .

980 140.7 150.5 161.2

1000 139.0 148.8 159.4

1020 137.3 147.1 157.6 171.3

1040 135.6 145.4 155.8 169.4

1060 133.9 143 .

154.0 167.6 184.0

1080 132.3 142.0 152.1 165 .

8

182.1 199.8

1100 130.6 140.3 150.3 164.0 180.3 197.9 219.4 241.7

1120 138.6 148.5 162 .

178.4 196.0 217.5 239.8

1140 136.9 146.7 160.3 176.6 194.1 215.6 237.8

1160 158.5 174.7 192.2 213.7 235 .

8

1180 172.9 190.3 211.8 233.9

1200 188.3 209.9 231.9

1220 208.0 229.9

1240 227.9

References [6,8] .

4. Viscosity (r\)

No data.

5. Electrical Conductance (k)

Measurement method: ac technique [4]

k = a + bT + cT

2 + dT 3 (35.5)

precision: in table 35.7 uncertainty: ^ + 3%

Table 35.7. Parameters of equation (35.5), and precisions

Mol % LiCl -a b x 10 2 -c x 10 6 -d x 10 1

Precision

100 2.38328 1.30626 4 . 38178 ± 0.02%

88 3.79487 1.53803 6.54756 7.08847 ± 0.03%

75 4.53422 1.39024 4.16275 ± 0.03%

63 5.09117 1.40770 3.99430 ± 0.03%

50 4.45470 1.14329 0.81203 10.05267 ± 0.02%

37 6.50401 1.59769 4.07234 ± 0.03%

25 6.35426 1.67159 4.48874 ± 0.02%

12 6.13153 1.72097 4.67529 ± 0.04%

0 6.62282 1.90497 5.17567 ± 0.03%

318
LiF-LiCl

Table 35.8. Specific conductance (ohm 1 cm

1

) from

equations in table 35.7

Mol % LiCl

T ( K ) 100 88 75 63 50 37 25 12 0

940 6.023 5.463 4.856 4.610 4.741 4 . 915

' 5.391 5.912 6.708

960 6.118 5.566 4.973 4.743 4 . 880 5.081 5.556 6.081 6.895

980 6.211 5.656 5.095 4.867 5.025 5.244 5.717 6.245 7.077

1000 6.299 5.749 5.205 4.994 5.161 5.402 5.875 6.403 7.254

1020 6.379 5.833 5.317 5.110 5.295 5.552 5.026 6.561 7.421

1040 6.464 5.915 5.419 5.229 5.427 5.709 6.175 6.706 7.590

1060 6.541 5.996 5.527 5 . 345 5.556 5.856 6.321 6.860 7.755

1080 6.613 6.07 2 5.626 5.452 5.679 6 . 000 6.461 7.005 7.917

1100 6.684 6.143 5.720 5.562 5.801 6.143 6.603 7.139 8.071

1120 6.749 6.213 5.816 5.665 5.917 6 . 282 6.738 7 .283 8.218

1140 6.811 6.282 5.903 5.763 6.035 6.421 6.867 7.410 8.368

1160 6.875 6.342 5.992 5.864 6.147 6.547 6.999 7.539 8.510

1180 6.931 6.401 6.072 5.959 6.253 6.677 7.118 7.664 8.645

1200 6.981 6.455 6.155 6.048 6.357 6.805 7 . 241 7.788 8.784

1220 7 o 0 31 6.512 6.232 6.136 6.460 6.926 7 .357 7.900 8.914

1240 7 o 07

6.561 6.304 6.222 6.557 7.045 7.471 8.021 9.042

1260 7.120 6.608 6.374 6 . 307 6.651 7.163 7.583 8.134 9.164

References [4,7]

6. Safety and Hazards

A. Hazard rating [9-11]

(i) Toxicity: LiF, severe; LiCl, slight.

(ii) Vapor pressure: no data for mixture; but see, LiF, LiCl.

3 (iii) U. S. occupational standards: LiF, 3.5 mg/m (air)

B. Disaster hazards [12-14]

(i) Molten salt bath "explosions": i.e., explosive generation

of steam due to bulk water "carry-over" and/or equipment

failure; i.e., explosive expansion of "trapped air.

(ii) Fluorides and chlorides, when heated to decomposition, or contacted with acids, emit highly toxic fumes.

References [9-14]

7. Corrosion

No data; see LiCl and LiF, respectively, for possible guidelines.

8.

Diffusion

No diffusion studies reported

319
LiF-LiCl

9.

Heat of Fusion (A Hj.)

Measurement method: cryoscopic [15]

Table 35.9. Heat of fusion of eutectic

AH°

^ _ i (kcal mol ) Uncertainty

4.8 ^ ± 6%

References [15]

10. Heat Capacity (C )

No Data.

11. Volume Change on Melting (AV^J

Measurement method: estimated; from densities [16]

Table 35.10. Volume change on melting

Binary etuectic (AV /V ) Uncertainty

(mol % LiF) t s

69.5 32.3% ^ ± 8%

References [16]

12. Vapor r Pressure (pr ) vap

No vaporization studies reported.

13. Thermal Conductivity (liquid) (X

)

No thermal conductivity studies reported,

14. Thermal ConductivityJ (solid) (X ) s No thermal conductivity studies reported.

15. Cryoscopic Constant (hj.)

Measurement method: cryoscopic [15]

Table 35.11. Cryoscopic Constant

Binary eutectic

(mol % LiCl)

k

f (K mol

_1 kg" 1

) Uncertainty

69.5 9.3 ^ ± 6%

References [15]

16.

References

[1] Bochvar, A. A., Tsvetn. Metall., 1, 508 (1930); Z. anorg. allgm. Chem.

210 , 163 (1933). Robertson, W, -

W, , ” Biinary Phase Diagram of

Halide Salts”, USAEC Report Yale 2723-1 (1966).

[2] Janz, G, J,, Downey, J, R, , Jr., Allen, C, B,, and Tomkins, R, P. T.,

"Eutectic Data” - 2 Vols,; ERDA-TID- 27163 -PI 8 P2; NTIS, Washington^

D. C. (1977),

[3] Janz, G, J., Downey, J, R. , Jr., Allen, C. B,, and Tomkins, R, P, T,,

"Physical Properties Data Compilations Relevant to Energy Storage , I

Molten Salts: Eutectic Data”, NSRDS -NBS - 61 ; U. S. Gov't Printing

Office, Washington, D. C. (1978).

320
LiF-LiCl

[4] Smirnov, M. V. , Shumov, Yu. A., and Khokhlov, V. A., Tr. Inst.

Elektrokhim. Ural. Nauchn. Tsenter., Akad. Nauk. SSSR, 2_0, 3 (1973).

[5] Holm, J. L., Acta Chem. Scand., 2_5, 5 (1971).

[6] Berge, B., and Holm, J. L., Int. Tech. Report, Inst, of Inorg. Chem.,

Tech. Univ. of Norway (1970).

[7] Belyaev, A. I., and Danielyan, E. R. , Fiz. Khim. Rasplav. Tr. Vses.

Sov. Po . Solei 2nd Kiev, 88 (1963).

[8] Smirnov, M. V. , and Stepanov, V. P., Phys . Chem. Electrochem.

Molten Solid Electrolytes. I. Reports All-Union Conf., Sverdlovsk,

June, 1973.

[9] "Dangerous Properties of Materials ", Sax, N. I., Van Nostrand Reinhold

Co. , N. Y. (1969)

[10] "Registry of Toxio Effects of Chemical Substances", Christensen, H. E.,

and Lubinbyhl, T. T., eds . , U. S. Dept. H. E. W. , U. S. Gov't Printing

Office, Washington, D. C. (1975).

[11] Vapor pressure; estimated (MSDC-RPI) unpublished work (1978),

[12] "Potential Hazards In Molten Salt Baths for Heat Treatment of Metals"

National Board Fire Underwriters Research Report No. 2, (1954).

[13] "Handbook of Reactive Chemical Hazards", Bretherwick, L., Butterworths

Co., London (1975).

[14] Janz, G. J. , Tomkins, R. P. T. , Downey, J. R., Jr., and Allen, C. B.,

"Safety and Hazards ", Chapter in "Eutectic Data", ERDA TID-27163-P1

NTIS, U. S. Dept. Commerce, Springfield, Va . (1977).

[15] Danek, V., Fellner, P., and Matiasovsky, K. , Z. physik. Chem. (N. F.),

94, 1 (1975).

[16] Janz, G. J., et al., (MSDC-RPI) unpublished work (1977).

321
XXXVI. Sodium Chloride-Potassium Chloride -Aluminum Chloride: NaCl -KC1 -AlCl^

1 . Melting Temperatures (T ) Pure substance melting points : NaCl : 8 00°C

KC1 : 77 0°C

A1C1

3

: 1 92°C

Eutectic melting point:

88.9°C, composition: 20 mol % NaCl, 16.5 mol % KC1 , 63.5 mol % AlCl^

AICI 3

Figure 36.1. NaCl -KC1 -AlCl^ phase diagram. E^D, E

2 D:

lines from binary eutectics; D; ternary eutectic;

PlCi, ?

2 ^

2

: approx, boundaries between fields in

ternary system

References [1-10].

2. Density (p)

Measurement method: Archimedean technique [11]

Table 36.1. Compositions of mixtures investigated

Mixture Alcl

3 NaCl KC1

Mol %

A 50 40 10

B 55 25 20

C 60 30 10

D 60 20 20

E 60 10 30

F 65 25 10

G 65 10 25

322
NaCl-KCl-AlCl

3

p = a + bT (3 6.1)

precision: not estimated , uncertainty: not estimated; insufficient data

Results were reported in equation form.

Table 36,2. Parameters of equation (36.1)

Mixture a -b x 10 4

A 2.136 9 . 23

B 2 . 105 9 . 03

C 2.096 8 .82

D 2 .117 9.70

E 2 . 059 8 .22

F 2.059 8.77

G 2.115 10.2

Table 36.3. Densities (g cm’

3

) from equations in table 36.2

Mixtures

T (K) A B C D E F G

‘

430 1.7167 1.6999 1.6819 1.6764

440 1.7077 1.7079 1.6902 1.6731 1 . 6662

450 1.6987 1.6991 1.6905 1.6644 1.6560

460 1 .6896 1.6903 1.6708 1.6556 1.6458

470 1.6806 1 . 6815 1.6611 1.6727 1.6468 1.6356

480 1 .6716 1.6726 1.6514 1 . 6644 1.6380 1.6254

490 1.6562

500 1.6745 1.6480

510 1.6653 1.6398

520 1.6560 1. 6316

530 1.6468

540 1.6376

References [11,12] .

3. Surface Tension (y)

No data.

4. Viscosity (r\)

No data.

323
NaCl -KC1 -AlClj

5. Electrical Conductance (k)

Measurement method: ac technique [13]

Table 36.4. Compositions of mixtures investigated

Mixture s NaCl KC1 A1C1

3 Mol %

A 35 .

6.9 57.8

B 21.3 12.0 66.7

C 22.0 15.0 63.0

D 32.0 16.8 51.2

E 40.4 7.9 51.7

F 31.0 16.2 52 .

k = a + bT (36.2)

precision: ^ + 1 % uncertainty: ^ + 5%

Table 36.5. Parameters of equation (36.2)

Mixture -a b x 10 3 Temp, range

no

A 0.616 1.95 405 - 458

B 0.476 1.47 404 - 463

C 0.585 1.80 403 - 464

D 0.733 2.30 411 - 473

E 0.911 2.78 427 - 466

F 0.785 2.39 415 - 463

For numerical values: see table 36,6

3 24
NaCl -KC1 - A1C1

2

-1 -1

Table 36.6, Specific conductance (ohm cm ) from

equations in table 36.5

Mixtures

T (K) A B C D E F

405 0.174 0.119 0.144

410 0.183 0.127 0.153

415 0.193 0.134 0.162 0.221 0.207

420 0.203 0.141 0.171 0.233 0.219

425 0.213 0.149 0.180 0.245 0.231

430 0.223 0.156 0.189 0.256 0.284 0.243

435 0.232 0.163 0.198 0.267 0.298 0.255

440 0.242 0.171 0.207 0.279 0.312 0.267

445 0.252 0.178 0.216 0.291 0.326 0.279

450 0.261 0.185 0.225 0.302 0.340 0.291

455 0.271 0.193 0.234 0.313 0.354 0.302

460 0.200 0.243 0.325 0.368 0.314

465 0.337 0.382

470 0.348

References [12,13].

6. Safety and Hazards

A. Hazard rating [14-16]

(i) Toxicity: NaCl, very low; KC1 , very low; AlCl^, severe.

(ii) Vapor pressure: no data for mixture; but see, NaCl;

KC1 ; A1C1

3

.

B. Disaster hazards [14,17-19]

(i) Molten salt bath "explosions"; i.e, explosive generation

of steam due to bulk water "carry-over" and/or equipment

failure; i.e, explosive expansion of "trapped" air,

(ii) Chlorides, when heated to decomposition, or contacted

with acids, emit highly toxic fumes; AICI 3 reacts

exothermically with mo istur e/water to evolve HC1 'fumes.

References [14-19].

325
NaCl-KCl-AlCl

3

7. Corrosion

Table 36.7. Corrosion studies from primaryresearch literature

Studies Ref erences

A1 20

Electrochem. approach 21,22

Thermodynamic redox diagrams 23

Annotated corrosion biblio. 24

Reviews: molten salts corrosion 25-27

References [20-27].

8. Diffusion

No diffusion studies reported ,

9. Heat of Fusion ( AH

Measurement method: estimated [28]

Table 36.8. Heat of fusion of eutectic

AH° Uncertainty

(kcal mol )

6 .

'v* ± 5%

References [ 28 ]

10. Heat Capacity (C )

No data.

11. Volume Change on Melting ( AT' „)

No data; but see NaCl , KC1 , AlClj.

12. Vapor r Pressure (pr ) vap

No vaporization studies reported.

13. Thermal Conductivity (liquid)

No thermal conductivity studies reported.

14. Thermal Conductivity (solid) (X ) ^ s No thermal conductivity studies reported.

326
NaCl-KCl-AlClj

15. Cryoscopic Constant

Measurement method: estimated [28]

Table 36.9. Cryoscopic constant

Mixture k

f Uncertainty

(K mol -

-*-kg

ternary eutectic 4.1 'v- ± 5%

References [ 28]

16. References

[1] Grothe, H. , and Piel, C. A., Z. Elektroch. angew, phys. Chem.,

54, 210 (1950).

[2] Janz, G. J., Downey, J. R., Jr., Allen, C. B., and Tomkins,

R. P. T,, "Eutectic Data” - 2 vols; ERDA-TID-27163 -PI § P 2

NTIS, Washington, D. C. (1977).

[3] Janz, G. J., Downey, J. R. , Jr., Allen, C. B., and Tomkins,

R. P. T., "Physical Properties Data Compilations Relevant

to Energy Storage. I. Molten Salts: Euteotic Data"3 NSRDSNBS-61; U. S. Gov't Printing Office, Washington, D. C. (1978).

[4] Grothe, H. , Z. Elektrochem . , _54, 216 (1950).

[5] Midorikawa, R., J, Electrochem. Soc. Japan, 23_, 1 27 , 352 (1955).

[6] Fischer, W. , and Simon, A., Z. anorg. allgm. Chem., 3 06 , 1 (1960).

[7] Chao, T., Dissertation Abs., 1_2 , 459 (1952).

[8] Wasilewski, L., Kaczorowski, A., and Dynkin, M. , Przem. Chem,,

1_8 , 608 (1934).

[9] Treadwell, W. D., and Terebesi, L., Helv. Chim. Acta, 18 , 103 (193 5).

[10] Plotnikov, V. A., and Shvartsman, U. I., Zap. Inst. Khim, Akad . Nauk,

SSSR, 3, 387 (1946).

[11] Midorikawa, R., Denki Kagaku, 23_, 352 (1955).

[12] Yamaguti, Y. , and Sisido, S., J, Chem. Soc. Japan, 6_2, 304 (1941).

[13] Midorikawa, R., J. Electrochem. Soc. Japan, 24_, 83 (1956).

[14] "Dangerous Properties of Materials"3 Sax, N. I., Van Nostrand

Reinhold Co., N. Y. (1969).

[15] "Registry of Toxic Effects of Chemical Substances"3 Christensen,

H. E., and Lubinbyhl , T. T., eds., U. S. Dept. H. E. W., U. S.

Gov't Printing Office, Washington, D. C. (1975).

[16] Vapor pressure; estimated (MSDC-RPI) unpublished work (1978),

[17] "Potential Hazards in Molten Salt Baths for Heat Treatment of Metals"3 National Board Fire Underwriters Research Report No. 2 (1954).

[18] "Handbook of Reactive Chemical Hazards"3 Bretherwick, L., Butterworths

Co . , London (197 5)

[19] Janz, G. J., Tomkins, R. P. T., Downey, J. R., Jr., and Allen, C, B.,

"Safety and Hazards

3 Chapter in "Eutectic Data"3 ERDA TID - 271 63 -PI

NTIS, U. S. Dept. Commerce, Springfield, Va, (1977),

327
NaCl-KCl-AlClj

[20] Hoff, H., Electrochim. Acta, 1_6, 1357 (1971),

[21] Pizzini, S., nMaterials Problems in the Industrial Applications of

Molten Salts", "Proceedings of the European Conference on the

Development of Molten Salts Applications", p. 203, Battelle, Geneva, (1973).

[22] Johnson, K, E,, "Electrochemical Approaches to Corrosion in Molten Salts ", Proceedings International Symposium on Metal - Slag -Gas Reactions and

Processes, The Electrochemical Society, Inc., Princeton, N. J. , p. 581

(1975),

[23] Littlewood, R., J. Electrochem. Soc., 109 , 525 (1962).

[24] Janz, G. J., and Tomkins, R. P. T., Corrosion, 34^ (in press) (1978).

[25] Inman, D. , and Wrench, N. S., Brit. Corr. J., 1_, 246 (1966).

[26] Ketelaar, J. A. A., Chemie Ing. Techn,, 4_5, 667 (1973).

[27] Smirnov, M. V., and Ozeryanaya, I. N., Nauki Tekh. Korros. Zashch.

Korros., 2, 171 (1973).

[28] Janz, G. J., et al., (MSDC-RPI) unpublished work (1977).

328
XXXVII. Lithium Chloride-Potassium Chloride-Calcium Chloride: LiCl-KCl-CaCl^

1.

Melting Temperatures (T )

Pure substance melting points:

LiCl : 610°C

KC1 : 770°C

CaCl

2

: 782°C

Eutectic melting points:

Eutectic 1: 412°

mol

C, composition:

% CaCl

2

52.4 mol % LiCl, 11.5 mol 1 KCI, 36.1

Eutectic 2: 332°

mol

C, composition:

% CaCl

2

50.5 mol % LiCl, 44.2 mol % KCI, 5.3

KCI

MOL %

Figure 37.1. LiCl-KCl-CaCl

2 phase diagram

References [1-4] .

2. Density (p)

No data.

3. Surface Tension (y)

No data.

4. Viscosity (r\)

No data.

5. Electrical Conductance (k)

No data.

32 9
LiCl - KC1 -CaCl

2 6.

Safety and Hazards

A. Hazard rating [5-7]

(i) Toxicity: LiCl, slight; KC1, very low; CaC^, very low.

(ii) Vapor pressure: no data for mixture; but see, LiCl; KC1 ; CaC^.

B. Disaster hazards [5,8-10]

(i) Molten salt bath "explosions": i.e. explosive generation

of steam due to bulk water "carry-over" and/or equipment

failure; i.e., explosive expansion of "trapped" air,

(ii) Chlorides, when heated to decomposition, or contacted

with acids, emit highly toxic fumes.

7 . Corrosion

No corrosion studies reported; for guidelines,

see LiCl-KCl, and CaC^.

8. Diffusion

No diffusion studies reported.

9.

Heat of Fusion (A H8.)

Measurement method: estimated [11]

Table 37.1. Heats of fusion and uncertainty

O Mixture AH Uncertainty

f (kcal mol “ 1 ) Eutectic 1 4 . 7 ^±5%

Eutectic 2 4.3 'Vi 5 %

References [11]

10.

Heat Capacity (C ) No data.

11. Volume Change on Melting ( CV

No data; but see LiCl, KC1 , CaC^ for guidelines.

12. Vapor Pressure (p ) r r vap

No vaporization studies reported.

IS. Thermal Conductivity (liquid) (X^)

No thermal conductivity studies reported.

14. Thermal Conductivity (solid) (\ ) v s No thermal conductivity studies reported.

330
LiCl-KCl-CaCl

2

15. Cryoscopic Constant

Measurement method: estimated [11]

Table 37.2. Cryoscopic constants and uncertainty

Mixture k

f Uncertainty

(K mol “ 1 kg“ 1 )

Eutectic 1 9.6 ^±5%

Eutectic 2 15.4 ^±5%

References [11]

16. References

[1] Sementsov, D. V. , and Bukhalova, G. A., Zh. Neorg. Khim. , 12_, 1650 (1967).

[2] Pluschcheo, and Kovolev, F. V. , Zh. Neorg. Khim., .1, 1013 (1956).

[3] Janz, G. J., Downey, J. R. , Jr.*, Allen, C. B., and Tomkins, R. P. T.

"Eutectic Data" - 2 vols.; ERDA-TID-27163-P1 8 P2; NTIS,

Washington, D. C. (1977).

[4] Janz, G. J., Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T.

"Physical Properties Data Compilations Relevant to Energy Storage . I.

Molten Salts: Eutectic Data ", NSRDS -NBS - 61 ; U. S. Gov't Printing

Office, Washington, D. C. (1978).

[5] "Dangerous Properties of Materials ", Sax, N. I., Van Nostrand Reinhold

Co., N. Y. (1969).

[6] "'Registry of Toxic Effects of Chemical Substances"

Christensen, H. E.,

and Lubinbyhl, T. T., eds . , U. S. Dept. H. E. W. , U. S. Gov't

Printing Office, Washington, D. C. (1975).

[7] Vapor pressure; estimated (MSDC-R^I) unpublished work (1978).

[8] "Potential Hazards In Molten Salt Baths for Heat Treatment of Metals"

National Board Fire Underwriters Research Report No. 2 (1954).

[9] "Handbook of Reactive Chemical Hazards ", Bretherwick, L., Butterworths

Co . , London ( 1975)

[10] Janz, G. J. , Tomkins, R. P. T. , Downey, J. R. , Jr., and Allen, C. B.,

"Safety and Hazards ", Chapter in "Eutectic Data", ERDA TID- 271 63 -PI

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[11] Janz, G. J. , et al., (MSDC-RPI) unpublished work (1977).

331
XXXVIII. Lithium Chloride-Sodium Chloride-Potassium Chloride: LiCl -NaCl - KC1

1.

Melting Temperatures (T 1 Pure substance melting points:

LiCl: 610°C

NaCl: 800°C

KC1 : 770°C

Eutectic melting point:

348°C, composition: 53.5 mol % LiCl, 8.5 mol % NaCl, 38 mol % KC1

LiCl

MOL %

Figure 38.1. LiCl -NaCl - KC1 phase diagram: E, eutectic;

P^, P

2

, peritectics

References [1-4] ,

2 . Density ( p ) No data.

3. Surface Tension (y)

No data.

4 . Viscosity (r\)

No data.

332
LiCl-NaCl-KCl

5. Electrical Conductance (k)

Measurement method: ac technique [5]

Table 38.1. Compositions of mixtures investigated

Mixture KC1 LiCl NaC 1 Mol %

A 41.95 57.93 0.12

B 41.89 57.85 0.26

C 41.80 57.72 0.48

D 41.49 57.30 1.21

E 40.39 55.77 3.84

k = A exp (-E/RT) (38.1)

precision: in table 38,2 uncertainty: ^ + 31

Table 38.2. Coefficients of equation (38.1), and precisions

Mixture A(ohm“ 1 cm

-

) E (cal mol -

) Precision

A 43.70816 4687.94 ±0.15%

B 47.63575 4791.01 ±0.10%

C 53.75324 4961.16 ±0.07%

D 56.27187 5023.06 ±0.04%

k = a + bT (38.2)

precision: in table 38,3 uncertainty: ^ + 3%

Table 38.3. Parameters of equation (38.2), and precision

Mixture -a b x 10 3 Precision

E 3.80334 7.59545 ±0.11%

333
LiCl-NaCl-KCl

-

-

Table 38.4. Specific conductance (ohm cm ) from equations

in tables 38.2 and 38.3

Mixtures

T (K) A B C D E 635 1.064 1.069 1.054 1.051 1.020

640 1.096 1.101 1.087 1.084 1.058

645 1.127 1.134 1.120 1.118 1.096

650 1.160 1.167 1.154 1.152 1.134

655 1.192 1.201 1.189 1.187 1.172

660 1.225 1.234 1.223 1.222 1.210

665 1.259 1.269 1.259 1.257 1.248

670 1.292 1.304 1.295 1.294 1.286

References [5]

6.

Safety and Hazards

(i)

(ii)

A.

Toxicity: LiCl,

Vapor pressure:

Hazard rating [6-8]

slight; KC1, very low; NaCl, very low

no data for mixture; but see, LiCl; NaCl; KC1.

B. Disaster hazards [6,9-11]

(i) Molten salt bath "explosions", i,e t explosive generation

of steam due to bulk water "carry-over" and/or equipment

failure; i,e,, explosive expansion of "trapped" air.

(ii) Chlorides, when heated to decomposition, or contacted with

acids, emit highly toxic fumes.

7Corrosion

Table 38.5. Corrosion studies from primary research literature

Studies References

Cu, Al, Al-Cu 12

Electrochen. approach 13,14

Thermodynamic redox diagrams 15

Annotated corrosion biblio. 16

Reviews: molten salts corrosion 17-19

References [12-19]

8.

Diffusion

No diffusion studies reported , 334
LiCl-NaCl-KCl

9.

Heat of Fusion (A H°)

Measurement method: estimated [20]

Table 38.6. Heat of fusion of eutectic

AH °f Uncertainty -1

(kcal mol ) 4.8 ^ ± 5%

References [20]

10.

Heat Capacity (C )

No data.

11.

\ Volume Change on Melting (AP^J

No data; but see LiCl, NaCl, KC1 for guidelines

12. Vapor r Pressure (pr ) vap

No vaporization studies reported.

13. Thermal Conductivity (liquid) (A ) No thermal conductivity studies reported,

14.

Thermal ConductivityJ (solid) (A ) s No thermal conductivity studies reported.

15.

Cryoscopic Constant „)

Measurement method: estimated [20]

Table 38.7. Cryoscopic constant

Mixture k

f (K mol ‘'"kg - "*') Uncertainty

Ternary eutectic 9.0 5%

References [20] .

16.

References

[1] Akopov, E. K., Zhur. Neorg. Khim. , 1_, 1024 (1956).

[2] Akopov, E. K., and Bergman, A. G. , ibid., 2, 383 (1957); U, 1751 (1966).

[3] Janz, G. J. , Downey, J. R. , Jr., Allen, C. B. , and Tomkins, R. P. T.,

"Eutectic Data" - 2 vols.; ERDA-TID-27163-P1 8 P2 ; NTIS, Washington,

D. C. (1977).

[4] Janz, G. J., Downey, J. R. , Jr., Allen, C. B. , and Tomkins, R, P. T.,

"Physical Properties Data Compilations Relevant to Energy Storage. I. Molten Salts: Eutectic Data", NSRDS-NBS- 61 ; U. S. Gov't Printing

Office, Washington, D. C. (1978).

335
LiCl-NaCl-KCl

[5]

[ 6 ]

^ ai

(1958) ^ * ’ Brown, C. T., and Gardner, H. J.,

"Dangerous Properties of Materials ", Sax N I Co., N. Y. (1969).

’ ' *

J . Phys. Chem. , 62_, 1479

, Van Nostrand Reinhold

[7] "Registry of Toxic Effects of Chemical Substances ", Christensen, H. E.,

and Lubinbyhl, T. T. , eds . , U. S. Dept. H. E. W. , U. S. Gov't

Printing Office, Washington, D. C. (1975).

[8] Vapor pressure; estimated (MSDC-RPI) unpublished work (1978),

[9] "Potential Hazards In Molten Salt Baths for Heat Treatment of Metals ",

National Board Fire Underwriters Research Report No. 2, (1954).

[10] "Handbook of Reactive Chemical Hazards ", Bretherwick, L., Butterworths

Co . , London (1975)

[11] Janz, G. J., Tomkins, R. P. T,, Downey, J, R, , Jr,, and Allen, C, B,,

"Safety and Hazards ", Chapter in "Eutectic Data ", ERDA TID-27163-P1

NTIS, U. S. Dept. Commerce, Springfield, Va . (1977),

[12] Barbe, M. , Rameau, J. J., and Barbier, M. J. , Rev. Int. Hautes. Temp.

Refract. , 11, 81 (1974)

[13] Pizzini, S., "Materials Problems in the Industrial Applications of• Molten

Salts ", Proceedings of the European Conference on the Development of

Molten Salts Applications, p. 203 (1973), Battelle, Geneva.

[14] Johnson, K. E., Proceedings Intern, Symp . Metal -Slag -Gas Reactions

and Processes; p. 581 (1975); The Electrochem. Soc., Princeton, N, J.

[15] Littlewood, R. , J. Electrochem. Soc., 109 , 525 (1962).

[16] Janz, G. J., and Tomkins, R. P. T, , Corrosion, 3£ (in press) (1978).

[17] Smirnov, M. V., and Ozeryanaya, I. N. , Nauki Tekh. Korros. Zashch.

Korros. , 2, 171 (1973)

[18] Inman, D., and Wrench, N. S., Brit. Corr. J., 1^, 246 (1966).

[19] Ketelaar , J. A. A., Chemie Ing. Techn. , 45, 667 (1973).

[20] Janz, G. J., et al., (MSDC-RPI) unpublished work (1977).

336
XXXIX. Lithium Fluoride-Lithium Chloride-Lithium Bromide: LiF-LiCl -LiBr

1. Melting Temperatures (T )

Pure substance melting points:

LiF: 848°C

LiCl : 610°C

LiBr: 552°C

Eutectic melting point:

445°C, composition: 22 mol % LiF, 31 mol % LiCl, 47 mol % LiBr

LiBr

MOL %

Figure 39.1. LiF-LiCl -LiBr phase diagram

References [1-4] .

2.

Density (p)

Measurement method: no information [4]

Table 39.1. Density

T P 3 Composition (K) (g cm ) ternary eutectic 773 2.19

Reference [4]

3. Surface Tension (y)

No data.

4. Viscosity (r\)

No data.

5. Electrical Conductance (k)

No data.

6. Safety and Hazards

A. Hazard rating [5-7]

(i) Toxicity: LiF, severe; LiBr, moderate; LiCl, slight.

337
LiF-LiCl-LiBr

7 .

8 .

9.

10 .

11 .

12 .

13.

14.

15.

16 .

(ii) Vapor pressure: no data for mixture; but see, LiCl; LiBr;

LiF.

B. Disaster hazards [5,8-10]

(i) Molten salt bath "explosions": i.e., explosive generation of steam

due to bulk water "carry-over" and/or equipment failure;

i.e., explosive expansion of "trapped" air.

(ii) Halide salts, when heated to decomposition, or contacted with

acids, emit highly toxic fumes.

References [5-10].

Corrosion

No corrosion studies reported; for guidelines, see LiF, LiCl, and LiBr and

mixtures

Diffusion

No diffusion studies reported .

Heat of Fusion (&H°)

No data.

Heat Capacity ( C )

No data.

Volume Change on Melting ( A7j>)

No data; but see LiF, LiCl, LiBr for guidelines.

Vapor r Pressure (pr ) vap

No vaporization studies reported.

Thermal Conductivity (liquid)

No thermal conductivity studies reported.

Thermal Conductivitya (solid) (X ) s No thermal conductivity studies reported.

Cryoscopic Constant (kj.)

No data.

References

[1] Bergman, A. G. , and Arabadzhan, A. S., Zh. Neorgan. Khim. , 8[5], 1228

(1963); Russ. J. Inorg. Chem., 8^, 637 (1963). ~

[2] Janz, G. J., Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T.

,

"Eutectic Data" - 2 vols.; ERDA-TID- 27163 -PI 8 P 2 ; NTIS, Washington,

D. C. (1977).

338
LiF-LiCl -LiBr

[3] Janz, G. J. , Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T.,

"Physical Properties Data Compilations Relevant to Energy Storage . I. Molten Salts: Eutectic Data ", NSRDS -NBS - 61 ; U. S. Gov't Printing

Office, Washington, D. C. (1978).

[4] Ackerman, J. P., and Sim, J. W. , "Electrolyte Studies", cited in Argonne

National Laboratory Rpt. ANL-76-35, NTIS, U. S. Dept. Commerce,

Springfield, Va. (1976).

[5] "Dangerous Properties of Materials ", Sax, N. I., Van Nostrand Reinhold

Co., N. Y. (1969).

[6] "Registry of Toxic Effects of Chemical Substances ", Christensen, H. E.,

and Lubinbyhl, T. T., eds., U. S. Dept. H. E. W. , U. S. Gov't Printing

Office, Washington, D. C. (1975).

[7] Vapor pressure; estimated (MSDC-RPI) unpublished work (1978).

[8] "Potential Hazards In Molten Salt Baths for Heat Treatment of Metals";,

National Board Fire Underwriters Research Report No. 2 (1954).

[9] "Handbook of Reactive Chemical Hazards ", Bretherwick, L., Butterworths

Co., London (1975).

[10] Janz, G. J., Tomkins, R. P. T., Downey, J. R. , Jr., and Allen, C. B.,

"Safety and Hazards", Chapter in "Eutectic Data ", ERDA TID- 27163-PI

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

339
XL. Lithium Fluor ide - Lithium Chloride-Lithium Iodide: LiF-LiCl-Lil

1. Melting Temperatures (

m

) Pure substance melting points:

LiF: 848°C

LiCl : 610°C

Lil : 469 0 C

Eutectic melting point:

340. 9°C, composition: 11.7 mol % LiF, 29.1 mol % LiCl, 59.2 mol % Lil

LIF

MOL %

Figure 40.1. LiF-LiCl-Lil phase diagram

References [ 1 - 4 ]

.

2 . Density ( p )

No data.

3. Surface Tension (y)

No data.

4 . Viscosity ( r\)

No data.

5. Electrical Conductance (k)

No data.

6. Safety and Hazards

A. Hazard rating [5-7]

(i) Toxicity: LiF, severe; Lil, moderate; LiCl, slight.

(ii) Vapor pressure: no data for mixture; but see LiF; LiCl; Lil

(iii) U. S. occupational standards: LiF, ^ 3.4 mg/m^ (air)

340
LiF-LiCl-Lil

B. Disaster rating [5,8-10]

(i) Molten salt bath "explosions": i.e., explosive generation of steam

due to bulk water "carry-over" and/or equipment failure;

i.e., explosive expansion of "trapped" air.

(ii) Halide salts, when heated to decomposition, or contacted

with acids, emit highly toxic fumes.

References [5-10] .

7. Corrosion

No corrosion studies reported; for guidelines, see LiF, LiCl, Lil and

mixtures

8. Diffusion

No diffusion studies reported

Heat of Fusion (A Hj.)

No data.

10. Heat Capacity (C

No data.

11 . Volume Change on Melting ( A7j.)

No data; but see LiF, LiCl, Lil for guidelines

12.

Vapor r Pressure (pr ) vap

No vaporization studies reported,

13. Thermal Conductivity (liquid)

No thermal conductivity studies reported.

14. Thermal Conductivity (solid) (A ) No thermal conductivity studies reported.

15. Cryoscopic Constant ( k „)

No data.

16.

References

[1] Johnson, C. E., and Hathaway, E. J. , J. Electrochem. Soc., 118 , 631 (1971).

[2] Cairns, E. J., et al., Argonne National Lab. Report ANL-7316, p. 219

(1967).

[3] Janz, G. J., Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T.,

"Eutectic Data" - 2 vols.; ERDA-TID-27163-P1 8 P2; NTIS,

Washington, D. C. (1977).

[4] Janz, G. J. , Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T.,

"Physical Properties Data Compilations Relevant to Energy Storage . I

Molten Salts: Eutectic Data", NSRDS -NBS - 61 , U. S. Gov't Printing ° Washington, D. C. (1978).

341
LiF-LiCl-Lil

[5] "Dangerous Properties of Materials

} Sax, N. I., Van Nostrand Reinhold

Co. , N. Y. (1969)

[6] "Registry of Toxic Effects of Chemical Substances

3 Christensen, H. E.,

and Lubinbyhl, T. T. , eds., U. S. Dept. H. E. W. , U. S. Gov't

Printing Office, Washington, D. C. (1975).

[7] Janz, G. J. et al. (MSDC-RPI), unpublished work (1978)..

[8] "Potential Hazards In Molten Salt Baths for Heat Treatment of Metals"3 National Board Fire Underwriters Research Report No. 2 (1954).

[9] "Handbook of Reactive Chemical Hazards ”, Bretherwick, L., Butterworths

Co . , London (1975)

[10] Janz, G. J., Tomkins, R. P.iT., Downey, J. R., Jr., and Allen, C. B.

,

"Safety and Hazards"3 Chapter in " Eutectic Data"3 ERDA TID-27163-P1

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

342
XLI. Lithium Carbonate -Sodium Carbonate-Potassium

Carbonate: Li

2 C03 -Na2 C03 -K2 C0

3

1. Melting Temperatures (T

Pure substance melting points:

Li

2 C0

3

: 7 23 °C

Na

2 C0

3

: 8 58 °C

K

2 C0

3

: 8 98 °C

Eutectic melting point:

397°C, composition: 43.5 mol % Li

2

CC> 3

, 31.5 mol % Na

2 C0

3

, 25.0 mol % K

2 CO

Figure 41.1. Li

2 C0

3 -Na

2 C0

3 -K

2 C03 phase diagram

References [1-5] .

2. Density ( p ) Measurement method: Archimedean technique [6]

p = 2.5128 - 5.4405 x 10‘ 4 T (41.1)

precision: + 0.8% uncertainty: -v + 1%

_ 3 Table 41.1. Densities (g cm ) from equation (41.1)

T

(K)

P , (g cm

T(K)

P

, (g Cl' 3

)

680 2 . 1429 880 2 . 0340

700 2.1320 900 2.0232

720 2 .1211 920 2 . 0123

740 2 . 1102 940 2 . 0014

760 2 . 0993 960 1,9905

780 2 . 0885 980 1 .9796

800 2.0776 1000 1.9688

820 2.0667 1020 1.9579

840 2 . 0558 1040 1.9470

860 2 . 0449 1060 1.9361

References [ 6] .

343
Li

2 C03 -Na2 C0

3

-K

2 C03 3.

Surface Tension (y)

Measurement method: pin detachment [6]

Y

= 287.07 - 6.944 x 10' 2 T (41.2)

precision: ^ + 0.41 uncertainty: ^ + 0.5%

Table 41.2. Surface tension from equation (41.2)

T

(K)

Y (dyn cm

-1

)

T(K) (dyn cm x

)

T

(K)

V

(dyn cm 1

)

740 235.7 840 228.7 940 221.8

750 235.0 850 228.0 950 221.1

760 234.3 860 227.4 960 220.4

770 233.6 870 226.7 970 219.7

780 232.9 880 226.0 980 219.0

790 232.2 890 225 .

3

990 218.3

800 231.5 900 224.6 1000 217.6

810 230.8 910 223.9 1010 216.9

820 230.1 920 223.2 1020 216.2

830 229.4 930 222.5 1030 215.5

1040 214.9

1050 214.2

References [6],

4.

Viscosity (r\)

Measurement method: oscillating (liquid filled) cylinder [7]

n = 4.64 x 10~ 3

exp (10,661/RT) (41.3)

precision: ^ + 0.05% uncertainty: ^ + 25%

Table 41.3. Viscosity from equation (41.3)

References [7]

5.

Electrical Conductance (k)

Measurement method: ac technique [6,8]

344
Li2C02-Na2CC>2-K2C02

Table 41.4. Compositions of mixtures investigated

Mixture Li 2 C0 3 Na 2 C 0 3 k 2 co 3 Ref . Mol %

Eutectic 43.5 31.5 25.1 6

A 50 33.3 16.67

B 40 30 30 8

C 33.3 33.3 33.3

< = A exp (-E/RT) (41.4)

precision: in table 41,5 uncertainty: eutectic, v + 2%;

other mixtures, v + 4%

Table 41.5. Parameters of equation (41.4), and precisions

Mixture A

( ohm

cm" 1 ) E

(cal mol -1

) Precision

Eutectic 83.8192 7385 ±0.5%

A 38.2364 5910 ±1.7%

B 32.777 5904 ± 2 . 0 %

C 27.208 5619 ±1.3%

For numerical values: see table 41.6,

345
Li2C02-Na2C0j-K2C0j

Table 41.6. Specific conductance (ohm^cm ^)

from equations in table 41.5

T (K)

Mixtures

Eutectic A B C

670 0.3269

700 0.4146

730 0.5157

760 0.6305

790 0.7591

820 0.9017

850 1.0581 1.16 0.95 0.94

880 1.2282 1.30 1.08 1,09

910 1.4117 1.46 1.25 1.22

940 1.6082 1.62 1.39 1.34

970 1.8174 1.78 1.53 1.47

1000 2.0387 1.95 1.68 1.61

1030 2.13 1.83 1.75

1060 2.31 1.99 1.89

1090 2.50 2.15 2.03

1120 2.69 2.31 2.18

References [6,8] .

6. Safety and Hazards

A. Hazard rating [9-11]

(i) Toxicity: L^COj, toxic dose (oral; human), 0,7 mg/kg;

I^CO^, severe; Na

2 C0 j, moderate.

(ii) Vapor pressure: Carbonates dissociate on heating

M

2 C0

3(£)

* M

2°(£)

+ C0

2 (g

)

For the ternary eutectic (m.pt. 397°C) the CO? equilibrium

dissociation pressure is ^ 31 mm at approx. 827°C

B. Disaster hazards [9,12-14]

(i) Molten salt bath "explosions": i.e. explosive generation

of steam due to bulk water "carry-over" and/or equipment

failure; i.e., explosive expansion of "trapped" air,

(ii) When heated at CO 2 pressures less than equilibrium,

carbonates decompose to alkali metal oxides; the

toxicology and disaster hazards of such oxides are

the same as very strong caustics; i.e. react with

water or steam exothermically to form hydroxides that

are very aggressive to body tissues (chemical burns)

Li

2 C0

3 by itself is classed as a strong caustic.

References [9-14].

346
Li

2 C0

3 Na

2 C0

3 -K2 C0

3

7. Corrosion

Table 41.7. Corrosion studies from primary research literature

S tud ies Ref er ences

Ti 15

Ti alloys 16

Fe , Ni , Cu 17,29,30

Au-Pd, Ni, 347-SS 18,42

Cu-Zn 19

Metals (anodic behavior) 20

Pt, Ag 18,21,22,23

Alumina (Monofrax A) 45

SS-347 ; SS-321 ; SS-304;

Incoloy 800; Carpenter 7 Mo;

Hastelloy G; Inconel 600;

Haynes G; Hastelloy X; Aluminized

SS-347; Alumina (Monofrax A;

Monofrax H; Coors AD-998);

graphite (various environments;

dry air; wet air; argon;

S0=; S =

; S0=; C; NaOH)

24,25

Pythagoras porcelain, aluminates 26-28

Au( 0

2 environment; ternary

eutectic + Na 20 ) 31

Boron nitride

Na- (3-alumina 44

Thermodynamics of corrosion

(E-pC0„ diagrams); acid-base

properties 26,32,35,36

emf series of metals 32-34

Hydrolysis (H

2 0) reactions 37,38

Corrosion in molten salts:

annotated bibliography 39

Molten carbonates: fuel

cells; thermal energy

storage; coal gasification;

power plant stack gases 40-43

References [15-45].

347
Li

2 C03

-Na

2 C0

3

-K

2 C0

3

Diffusion

Measurement method: capillary [46]

List of diffusing species investigated in Li ? CO x -Na ? CO, ^K 7 C0,

as solvent z ^ ^ 3

+ + 2 T Na , K , C0

3

precision in table 41.8.1 uncertainty: <v + 20%

Equations

D = A exp [-E/RT] (41,6)

Table 41.8.1. Parameters of diffusion equation (41.6), and precisions

Species A x 10 3 (cm 2 sec

-1

)

E (cal mo 1

1 ) Temp, range

(K)

Precis ion

Na

+ 8.06 11,035 830-1040 ^±3 . 6%

K+ 9.73 11,880 885-1115 ^±1%

co

3

“ 1.58 10,070 690-1130 ^±6%

For numerical values: see table 41.8.2.

348
L^COj-Na^Oj-K-^CO^

Table 41.8.2. Self -diffusion coefficients, D x 10^ (cm^sec

from equations in table 41.8.1.

T(K) Na

+

.... ..

K+ CO^

690 0.102

710 0.126

730 0.153

750 0.184

770 0.219

790 0.259

810 0.303

830 1.00 0.352

850 1.17 0.407

870 1 .36 0.466

890 1.57 1.18 0.532

910 1.80 1.36 0.603

930 2 . 06 1.57 0.679

950 2 .33 1.80 0.762

970 2 . 63 2 . 05 0.850

990 2 .95 2 .32 0.945

1010 3.30 2 . 61 1 . 046

1030 3.67 2 .93 1.153

1040 3 .87 3 .10 1 .209

1060 3 .46 1.325

1080 3 . 84 1.448

1100 4 . 24 1.577

1120 4 . 67 1.712

1130 1.782

References [46]

9. Heat of Fusion

Measurement method: drop calorimetry [3,47]

Table 41.9. Heat of fusion

Composition > K HiO 1 Uncertainty

(kcal mol ) ternary eutectic 6.55 ^ ± 1%

References [3,47].

349
Li

2 C03 -Na

2 C0

3

-K

2 C0

3 ±0. Heat Capacity (C

p

J Measurement method: drop calorimetry [47]

C

p

= 28.41 + 16.56 x 10~ 3 T (41.7)

precision: ^ + 0.51 uncertainty: ^ + 1%

Table 41.10. Heat capacity from equation (41.7)

T(K)

C p (cal K" 1 mol -

) T(K)

C P (cal K

1 mol 1 )

680 39 .67 900 43.31

700 40.00 920 43.65

720 40.33 940 44.98

740 40 . 66 960 44.31

760 41.00 980 44.64

780 41.33 1000 44.97

800 41.66 1020 45.30

820 41.99 1040 45.63

840 42.32 1060 45.96

860 42.65 1080 46.29

880 42.98 1100 46.63

References [47]

11. Volume Change on Melting (AF^J

Measurement method: estimated; from densities [48]

Table 41.11. Volume change on melting

Compo s it ion (4 W Uncertainty

ternary eutectic 3. 6% 'v ± 8%

References [48]

12. Vapor r Pressure (pr ) vap

Measurement method: cited with each data set [31,41,46]

No systematic studies of vaporization as molecular carbonates have

been reported, viz:

M

2 C0

3 ( £

)

M

2 C0

3 (g)

(41.8)

Relative to the CO 2 decomposition of molten carbonates and other

possible processes contributing to vaporization, the data for the

ternary carbonate eutectic are as follows:

Decomposition processes:

CO 2 dissociation and equilibrium pressures for the molten ternary

carbonate eutectic (Li 7 C0,/Na ? C0^/K ? C0-; : 43.5/31.5/25.0 mol %;

m.pt. 397°C) . L *

M

2 C0

3 (£)^==^ M

2 0

(£)

+ C0

2 (g)

( 41 - 9 ^

P C 0

2 (atm) K

d [aM

2 C0

3( Jl )/^M

2 0

(£)

] (41 * 10)

350
Li

2 C0

3 _Na

2 C03 _K2 C0

3

where M is the Li, Na, K cationic mixture of the ternary eutectic, p

is the equilibrium CO 2 dissociation pressure, and a the thermodynamically

defined activity. For practical purposes, eq . (41.10) is generally expressed

in the mol fraction scale [X]

Pco, (atm) “ K

*

[ V°3(0AM2°U)

] (41.11)

As noted for the single salts, the values for PCQ cannot be uniquely

defined unless the oxide content of the carbonate^is specified, i.e.

the pressures depend on the quality of the "carbonate" , and its previous

history, e.g. drying techniques; vacuum pumping;.,, or related conditions * which may promote C0

2 decomposition of the carbonates,

(i) Equilibrium dissociation constant,

Measurement method: emf technique [31]

log K

d

= -13530/T + 6,75 (41,12}

precision: not estimated uncertainty: v + 1 %

Table 41,12,1, C0

2 dissociation constant from equation (41,12)

T(K)

K

d

(atm)

T(K)

K

d

( atm)

800 6.88 x 10 _1

1050 7 . 32 x 10' 7 850 6 . 80 x 10' 1

1100 2 . 82 x 10~ 6 900 5 . 21 x 10~ 9 1150 9.66 x 10 -6

950

1000

3.22 x 10 -8

1.66 x 10 -7

1200 2.98 x 10~ 5

(ii) Equilibrium C0

2 dissociation pressures

Measurement method: static technique [46]

log p (mm) =

~ 630 ° -.

5

.7. + 7.22 (41.13)

precision: ^ + 3% uncertainty: ^ + 5%

Table 41.12.2. Equilibrium CO 2 dissociation pressures for the

ternary carbonate eutectic (2.) from equation (41.13)

~ 1 CO? pressure (mm)

T (ob sv ' d

calc ' d from eq. (41.10) , (41.11)

(K) eq . (41.13) XM

= 3 x 10 -5

M 2 0

1 x 10 -4

3 x 10" 4

1020 11 7 . 7 2 .

0 .

1060 19 24

1100 31 71 21

1140 50 58 19

1180 77 146 49

1220 115 115

Remarks: In the first approximation, it is seen that the observed

CO 2 pressures are in accord with increasing oxide content

with increasing temperatures.

351
Li

2 C0 3" ISJa 2 C0 3" K

2 C0

3

The C0 2 dissociation pressures of Lorenz and Janz (1970; emf technique) are in accord with the preceding if a correction

for oxide content (mol IV^O/mol eutectic) of ^ 5 x 10'2 i s applied from the preceding viewpoints.

Vaporization of molten carbonates:

Measurement method: critical analyses [41]

The various "vaporization" data, based on electrolyte losses

from high temperature molten carbonate fuel cells, and the

thermodynamics of the associated reactions, have been critically

examined by Maru et al . (1976). For a summary of the data status, refer: L^CO^, present work.

References [31,41,46,49-53],

13. Thermal Conductivity (liquid) (1^)

No thermal conductivity studies reported.

14. Thermal Conductivity (solid) (\ ) s No thermal conductivity studies reported.

15.

Cryoscopic Constant (

Measurement method: calc'd; from AH£ [48]

Table 41.13. Cryoscopic constant

k

f Uncertainty

Composit ion (K mol-lkg - l)

ternary eutectic 13.5 <? i+ H*

5-S

References [1,3,47,48],

16 References

[1] Janz, G. J. , and Lorenz, M. R. , J. Chem. Eng. Data, 6_, 321 (1961).

[2] Volkova, L. F., Izvest. Sibir. Otdel . Akad . Nauk. SSSR, 7_, 33 (1958).

[3] Rolin, M. , and Recapet, J. M. , Bull. Soc. Chim. France, 2504 (1964).

[4] Janz, G. J. , Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T., " Eutectic Data" - 2 vols; ERDA-TID-27163-P1 8 P 2 ; NTIS, Washington,

D. C. (1977).

[5] Janz, G. J., Downey, J. R., Jr., Allen, C. B., and Tomkins, R. P. T.,

"Physical Properties Data Compilations Relevant to Energy Storage,

I. Molten Salts: Eutectic Data", NSRDS -NBS - 61 ; U. S. Gov't

Printing Office, Washington, D. C. (1978).

[6] Ward, A. T., and Janz, G. J., Elec trochimica Acta, 10_, 849 (1965).

[7] Janz, G. J., and Saegusa, F., J. Electrochem. Soc., 110 , 452 (1963).

[8] Noda, H., Shiota, K., Shiotawa, J., Tamura, H. , and Ishino, T.

,

Denki Kagaku, n, 417 (1963).

[9] "Dangerous Properties of Materials ", Sax, N. I., Van Nostrand

Reinhold Co., N. Y. (1969).

352
Li

2 C03

-Na

2 C0

3

-K

2 C0

3

[10] "Registry of Toxic Effects of Chemical Substances "> Christensen, H. E.,

and Lubinbyhl , T. T., eds,, U. S. Dept. H. E. W. , U. S. Gov’t Printing

Office, Washington, D. C. (1975),

[11] Vapor pressure, calculated (see p. 351, this work],

[12] "Potential Hazards in Molten Salt Baths for Heat Treatment of Metals"a National Board Fire Underwriters Research Report No. 2 (1954),

[13] "Handbook of Reactive Chemical Hazards ", Bretherwick, L,, Butterworths

Co., London (1975).

[14] Janz, G. J. , Tomkins, R. P. T., Downey, J. R. , Jr., and Allen, C. B.

"Safety and Hazards " , Chapter in"Eutectic Data", ERDA TID-27163-PI

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[15] Manukhina, T. I., Ozeryanaya, I. N., and Smirnov, M. V., Trudy. Inst.

Elektrokhim., Ural. Filial Akad, Nauk SSSR, 1_5, 109 (1970).

[16] Ozeryanaya, I. N., Manukhina, T. I., and Smirnov, M. V., Zashch. Metal,

8, 128 (1972).

[17] Ozeryanaya, I. N. , Penyagina, 0. P., and Smirnov, M. V., Fiz. Khim.

Elektrokhim. Rasplav Solei Shlakov, 2_, 241 (1969).

[18] Janz, G. J., and Conte, A., Corrosion, 2£, 237 (1964).

[19] Sizintseva, N. F., Stepanov, G. K. , and Belyaeva, G. I., Tr . Inst.

Elektrokhim., Ural. Nauch. Tsentr. Akad. Nauk, SSSR, 1_9, 92 (1973).

[20] Ozeryanaya, I. N. , Penyagina, 0. P., Manukhina, T. I., and Smirnov, M. V.

Fiz. Khim. Elektrokhim. Rasplav. Solei Tverd, Elektrolit., 1_ , 96 (1973)

[21] Janz, G. J., Conte, A., Neuenschwander , E., Corrosion, 19_, 292 (1963).

[22] Rodigina, E. N., and Stepanov, G. K. , Trudy Inst. Elektrokhim. Ural. Fil

Akad. Nauk SSSR, 3, 77 (1962).

[23] Trachtenberg, I., and Cole, D. F., "Fuel Cell Systems-II", p. 269,

B. S. Baker, Ed., Adv. Chem. Series 90; Amer. Chem. Soc . , Washington,

D. C. (1969).

[24] Atomics International, "Development of a Molten Carbonate Process for

Removal of Sulfur Dioxide from Power Plant Stack Cases", Prog. Rpt.

No. 2 (Apr. -Oct., 1968); U. S. Public Health Service, Contract No.

PH-86-67-128 (1968).

[25] Grantham, L. F. , and Ferry, R. B. , "Corrosion in Alkali Metal CarbonateBased Melts", Proc. International Symp. Fused Salts; J. P. Pemsler

et al., eds., p. 270 (1976); The Electrochemical Society, Inc.,

Princeton, N. J,

[26] Dubois, J., "Chemical and Electrochemical Reactions of Molten Alkali

Carbonates as Fuel Sell Electrolytes

3 Ph.D. Thesis* Fac. Sci. Univ

Paris, France (1964).

[27] Busson, N., Palous, S., Buvet, R., and Millet, J, , C. R. Acad. Sc.,

Paris, 260, 6097 (1965).

[28] Broers, G. H. J., and Ballegoy, H. J. J., Journees Int. Etude Piles

Combust. C. R. (3rd); 77 (1969) Eng.

[29] Manukhina, T, I., Ozeryanaya, I, N., Smirnov, M. V., and Shananova,

M. D., Zh. Prikl . Khim., 48^, 44 (1975).

[30] Penyagina, 0. P,, Ozeryanaya, I. N., et al , , Tr. Inst. Elektrokhim.,

Ural Nauchn. Tsentr. Akad. Nauk SSSR, 22, 70 (1975).

353
Li

2 C0

3 -Na2 C0

3

-K

2 C0

3

[31] Andersen, B. K. , " Thermodynamic Properties of Molten Alkali Carbonates "

,

Ph.D. Thesis, Tech. Univ. Denmark (1975),

[32] Ingram, M. D., and Janz, G. J., Electrochimica Acta, 1J), 783 (1965).

[33] Ketelaar, J. A. A., Chemie Ing. Techn,, 4_5, 667 (1973).

[34] Boxall, L. G,, and Johnson, K. E,, J. Electroanal, Chem. , 3_0, 25 (1971).

[35] Busson, N., Palous, S, , Buvet, R., and Millet, J., Compt, Rend., 260,

720, 6097 (1965). ~~

[36] Ingram, M. D., Baron, B., and Janz, G, J,, Electrochim. Acta, 11,

1629 (1966).

[37] Janz, G. J., J. Chem. Educ . , 44, 581 (1967).

[38] Busson, N., Palous, S, , Millet, J,, and Buvet, R., Electrochim. Acta,

1_2 , 910 (1967).

[39] Janz, G. J., and Tomkins, R. P. T., Corrosion, 34 (in press) (1978).

[40] Maru, H. C., et al . (Institute of Gas Technology), "Molten Salt Thermal

Energy Storage Systems: Salt Selection", Rpt. COO-2888-1, ERDA

Contract No. E (1 1 -1 ) - 288 8 , Aug. (1976); NTIS, U. S. Dept. Commerce,

Springfield, Va.

[41] Maru, H. C. et al, (Institute of Gas Technology), "Fuel Cell Research

on Second Generation Molten Carbonate Systems; FT, Characteristics

of Carbonate Melts", Quarterly Status Rpt,, Sept, 1976, Project

8984; ERDA Contract No. 31-109-38-3552.

[42] Botts, W. V., Kohl, A. L,, and Trilling, C. A,, "Low BTU Gasification

of Coal by Atomics International's Molten Salt Process", Proceedings

of the llth intersociety Energy Conversion Conference, 1, 280

(Sept. 1976).

[43] Cover, A, E,, Schreiner, W, C., and Skaperdas, G, T., "The Kellogg

Coal Gasification Process", Extended Abstracts ; American Chemical

Soc. Meeting, Washington, D. C. (1971).

[44] Braunstein, J., et al. , "Molten Carbonate Fuel Cell Research at ORNL ",

Rpt. ORNL/TM-5886 (May, 1977); NTIS, U. S. Dept. Commerce, Springfield,

Va.

[45] Bonar, J., Clark, C. B., and Sandmeyer, K. H., "Interaction of Oxide

Refractories with the Environment of High Temperature Reactors",

p. 807, in "Proceedings Int. Symposium on Metal-Slag -Gas Reactions

and Processes", The Electrochemical Society, Princeton, N. J. (1975).

[46] Spedding, P. L., and Mills, R., J. Electrochem. Soc., 112 , 594 (1965).

[47] Janz, G. J., Neuenschwander , E., and Kelly, F. J., Trans. Faraday Soc.,

59, 841 (1963).

[48] Janz, G. J., et al . , (MSDC-RPI) unpublished work (1977).

[49] Lorenz, P. K. , and Janz, G. J., Electrochimica Acta, 1_5, 2001 (1970).

[50] Broers, G. H. J., "High Temperature Galvanic Fuel Cells", Ph.D. Thesis;

Univ. Amsterdam (1958).

[51] Broers, G. H. J. and Schenke, M. , "Long-Run Experiments in High Temperature Molten Carbonate Fuel Cells", Chapt. in "Hydrocarbon Fuel

Cell Techno loty "

,

Baker, B. S. , ed. , Academic Press, N. Y. (1965).

[52] McQuade, J. M., Hamlen, R. P., and Nelson, R. P., "Alkali Carbonate

Fuel Cells", U. S. Patent 3,268,365 (1966) Aug. 23; (assigned to

General Electric Co.).

354
Li

2 C0 3" Na

2 C0 3' K

2 C0

3

[53] Trachtenberg, I., and Cole, D. F., "Electrolyte Studies in Molten

Carbonate Fuel Cells ,r Chapter in f'Fuel Cell Systems II" Baker, B. S.,

ed; Amer. Chem . Soc . , Advances in Chemistry Series, £0, 268-280 (1969)
XLIT. Lithium Carbonate-Sodium Carbonate: Li2C0

3

-Na2C0

3

1. Melting Temperatures (T ) Pure substance melting points:

Li

2 C0

3

: 7 23°C

Na

2 C03

: 858°C

Eutectic melting point:

495, 8°C, composition: 53.3 mol % L^COj

Figure 42.1. Li

2 C03

-Na

2 C03 phase diagram

References [1-6]

2. Density (p)

Measurement method: Archimedean technique [7]

Single variable equation

p = a + bT (42.1)

precision: ^ + 0.2% uncertainty: ^ ± 0,5%

356
Li^CO^ -Na2COj

Table 42,1. Parameters of equation (42,1)

Mo 1 % Na 2 CO 3 a -b x 10 3 Temp, range (K)

0 2 .2365 0.4041 1020 - 1120

10 2 . 2435 0.3991 980 - 1200

20 2 . 2885 0.4120 960 - 1220

30 2 .3474 0.4378 940 - 1200

40 2 .3557 0.4337 920 - 1180

46.7 2.3581 0.4325 820 - 1180

50 2.3532 0.4249 900 - 1180

60 2 .3653 0.4262 880 - 1180

70 2 .3890 0.4230 960 - 1180

80 2.4461 0.4437 1060 - 1220

90 2 . 4443 0.4301 1120 - 1220

100 2 .4532 0.4267 1140 - 1240

Two - independent -variable equation

p = a + bT + cC + dC 2 + eC

3 + fTC + gTC 2 (C = mol % Na

2 C03

) (42.2)

precision: + 0.4% uncertainty: o, ± 0.5%

Table 42.2. Parameters of two -independent -variable equation (42.2)

a b x 10 4 c x 10 4 d x 10 6 e x 1

7 f x 10 6 g x 1

3

2 .3278 -4 . 94895 -1.07485 -2 .75396 1 .90622 2 . 95891 -2.43405

_ 7 Table 42.3. Densities (g cm ) from equations in table 42.1

Mol Z Na

2 COj

T ( K) 100 90 80 70 60 50 46.7 40 30 20 10 0 820 2.003

84 0 1.995

860 1.986

830 1.990 1.978

900 1.982 1.971 1.969

920 1.973 1.962 1.960 1.957

940 1.965 1 . 954 1.952 1.948 1.936

960 1.983 1.956 1.945 1.943 1.939 1 . 927 980 1.974 1.948 1.937 1.934 1 . 931 1.918 1.885

1000 1.966 1.939 1.928 1.926 1.922 1.910 1.877 1.844

1020 1.958 1.931 1.920 1 . 917 1.913 1.901 1.868 1.836 1 .824 1040 1.949 1. 922 1.911 1.908 1.905 1.892 1.860 1.828 1 . 816 1060 1.976 1.941 1.914 1.903 1 . 900 1 . 896 1.883 1.852 1.820 1.808

1080 1.967 1.932 1.905 1.894 1.891 1.887 1.875 1.844 1 .812 1.800

1100 1.958 1.924 1.896 1.886 1.882 1 .879 1.866 1.835 1 . 804 1.792

1120 1.963 1.949 1.915 1.888 1.877 1.874 1.870 1.857 1.827 1.797 1.784

1140 1 .967 1.954 1.940 1.907 1.879 1.869 1.865 1.861 1.848 1.819 1.789

1160 1.958 1.945 1.931 1.898 1.871 1.860 1.856 1.853 1.840 1.311 1.781

1180 1.950 1.937 1.923 1.890 1.862 1.852 1 . 848 2 . 844 1.831 1.802 1.774

1200 1.941 1.928 1.914 1.822 1 . 794 1.765

1220 1.933 1.920 1.905 1.786

1240 1.924

References [7-9]

357
Ll

2 C0 3’ Na2 C03

3. Surface Tension (y)

Measurement method: pin detachment [8]; maximum bubble pressure [10]

Y

= 313.5 - 7.66 x 10' 2 T (42.3)

precision: + 0.7% uncertainty: ^ + 1.5%

Table 42.4. Surface tension of eutectic from equation (42.3)

T(K)

Y (dyn cm” 1

)

T

(K)

Y (dyn cm 1

)

830 249 .

930 242.3

840 249.2 940 241.5

850 248.4 950 240.7

860 247.6 960 240.0

870 246.9 970 239.2

880 246.1 980 238.4

890 245.3 990 237.7

900 244.6 1000 236.9

910 243.

8

1010 236 .

920 243.0 1020 235.4

Single variable equation

y

= a + bT (42.4)

precision: in table 42.4 uncertainty: ^ + 1.5%

Table 42.5. Coefficients of single variable

equation (42.4), and precisions

Li? CO q a -b x 10 3 Temp, range Precision

(mol %) (K)

0 292.2 72.0 1159-1263 ±0.3%

10 279 .

56 .

3

1092-1181 ±0.5%

30 307 .

8

77.9 962-1170 ±0 . 8%

50 308.0 74.6 822-1195 ±0.6%

70 298.1 60.4 903-1174 ±0.4%

90 289.0 48.2 973-1172 ±0.1%

100 281.5 36.6 1023-1173 ±0.4%

Two- independent -variable equation

Y

= a + bT + cC + dC 2 + eT

3 + fC 3 + gTC 2 + hCT 2 (C = mol % Na

2 C0

3

) (42.5)

precision: ^ + 0.3% uncertainty: ^ + 1.5%

Table 42.6. Coefficients of two -independent -var iabl e equation (42.5)

a b x 10 2 c x 10 2 d x 10 2 e x 10 9 f x 10 5 g x 10 6 h x 10 7

300.11719 -8.10195 58.4934 -1 . 20938 2.24208 2 .59350 7 . 81488 -1.86765

358
Li2C02-Na2CC>2

Table 42.7. Surface tension (dyn cm"'*’) from equations

in tabl e 42.5

Mol % Na 2 C 0 3 (K) 100 90 70 50 30 10 0

830 246.3

850 244.8

870 243.3

890 241.8

910 240.3 243.0

930 238 .

241.8

950 237 .

240 .

970 232 .

235 . 8 239 .

990 230 .

234.3 238 . 2 241.3

1010 229.1 232 .

237 .

240 .

1030 227 .

231 .235 .

239 .243 .

1050 226.0 229 .

234 .

238.4 243.1

1070 224.0 228 .

233 .237 .

242 .

1090 217 .

222 .226 .

232.2 236 .

241.6

1110 216 .

221 .

225 .

230.9 235 .

240.9

1130 215 .

219 .

223 .

229 .234 .

240 .

1150 214.6 218 .

222 .

228 .

233 .

239 .

1170 208 .

213.4 216. 7 220 .

227 .

232.6 238 . 7

References [8,10]

4. Viscosity (n)

Measurement method: oscillating sphere [11]

precision: not estimated uncertainty: ^ + 25%

Values interpolated from graphical data

For numerical values: see table 42.8,

359
Li2C02~Na2C02

Tabl'e 42.8. Viscosity (cp)

Li 2 CO 3 (mol %)

T (K)

973 1023 1073 1123 1173

0 4 .03 3.57

10 4 .44 3.87 3.41

20 5.16 4.37 3 .76 3 . 29

30 5.16 4 .37 3 .73 3.26

40 6 .35 5 .28 4 . 44 3 . 80 3 .31

50 6.51 5.41 4.55 3 . 86 3.36

60 6.66 5.52 4.61 3 .91 3.41

70 6.77 5.58 4.68 3.98 3 .46

80 6.89 5 .69 4.76 4.06 3 .54

90 7 . 09 5.96 5.04 4.29 3.72

100 6.43 5.47 4 .70 4.07

References [11]

5. Electrical Conductance (<)

Measurement method: ac technique [13]

k = A exp (-E/RT) (42,6)

precision: not estimated uncertainty: ^ + 2.5%

Results reported in equation form only.

Table 42.9. Parameters of equation (42.6)

Na 2 CO 3 (jnol %)

A

(ohm ^m *) E (cal mol” 1 ) Temp, range

(K)

0 29.22 3940 1013-1153

10 28.00 3980 1007-1201

20 25.05 3930 973-1196

30 23.21 4000 973-1196

40 21.74 4050 953-1253

46.7 20.84 4050 913-1220

50 20 . 36 4030 933-1212

60 18.85 3940 983-1239

70 17 . 29 3820 983-1234

80 15.88 3710 1013-1224

90 14.71 3620 1077-1232

100 14.12 3590 1145-1238

360
Li2C02~Na2C02

Table 42.10. Specific conductance (ohm ^cm ^) from equations in table 42.9

Mol z Na

2 co

3 T(K) 100 90 80 70 60 50 46.7 40 30 20 10 0 920 2.274

940 2.354 2.384 2.727

960 2.462 2.494 2.60.2 2.851

980 2.571 2.604 2.717 2.976 3.330

1000 2.529 2.596 2.679 2.715 2.832 3.101 3.467

1020 2.546 2.625 2.698 2.788 2.826 2.948 3.226 3.604 3.930 4.183

1040 2.638 2.723 2.801 2.897 2.936 3.063 3.350 3.741 4.081 4.342

1060 2.729 2.820 2.904 3.005 3.047 3.179 3.475 3.877 4.232 4.501

1080 2.723 2.819 2.916 3.006 3.114 3.157 3.294 3.599 4.014 4.383 4.660

1100 2.808 2.909 3.012 3.108 3.222 3.268 3.409 3.723 4.149 4.533 4.818

1120 2.892 2.999 3.107 3.210 3.330 3.378 3.523 3.847 4.285 4.683 4.976

1140 2.976 3.087 3.202 3.311 3.437 3.487 3.638 3.970 4.420 4.832 5.133

1160 2.975 3.059 3.176 3.297 3.412 3.544 3.596 3.752 4.093 4.554 4.981

1180 3.054 3.142 3.264 3.391 3.512 3.651 3.705 3.865 4,215 4.687 5.129

1200 3.133 3.223 3.351 3.484 3.612 3.757 3.813 3.978 4.337 4.819 5.276

1220 3.212 3.305 3.438 3.577 3.711 3.921

1240 3.810

References [8,9,12,13],

6. Safety and Hazards

A. Hazard rating [14-16]

(i) Toxicity: L^COj, toxic dose (oral, human), 0.7 mg/kg;

Na

2 C 0 j, moderate

(ii) Vapor pressure: carbonates dissociate on heating:

M

2 C0 3Otr=TM2°U) * C0

2 (s)

(42 - 7)

For the binary eutectic (m,pt, 495.8°C)> the CO 2 equilibrium dissociation pressure is ^ 4,8 x 10 z mm at

approx. 530°C.

B, Disaster hazards [14,17-19]

(i) Molten salt bath "explosions": i.e. explosive generation

of steam due to bulk water "carry-over" and/or equipment

failure; i.e. explosive expansion of "trapped" air

(ii) When heated at CO 2 pressures less than equilibrium,

carbonates decompose to alkali metal oxides; the

toxicology and disaster hazards of such oxides are

the same as very strong caustics, i.e. react with

water or steam exothermically to form hydroxides

that are very aggressive to body tissues (chemical

burns); L^CO^ is itself classed as a strong

caustic

References [14-19].

361
Li^COj -Na2CC>2

7 . Corrosion

Table 42,11. Corrosion studies from primary

research literature

Studies References

Ti alloys; Cr-Ni alloys 20,41

Au, Pt, Ag , Ni, Au-Pd 21

Pt, Au, Ag, MgO 22

Ag, Co, Ni 23

310-SS; 321-SS; 347-SS;

Kanthal A; Kanthal A-l;

[various gas environments]

24

Thermodynamics of corrosion

(E-pC0„ diagrams); acid-base

concepts

25,26,30,31

Ag(fuel cell environment) 27,28

Ag ; A1„0_ (0„ environment;

eutectic + L^O) 29

Hydrolysis (H

2 0) reactions 29,32,33

Corrosion in molten salts:

annotated bibliography 34

Molten carbonates: fuel

cells; thermal energy

storage; coal gasification;

power plant stack gases 35-40

References [20-41] ,

8. Diffusion

Measurement method: cited in tabulations

List of diffusing species investigated in L^COj ’-Na

2 C02 as solvent

Na

+

, COj", H

2 precision: in table 42.12,2 uncertainty: in table 42.12.1

Table 42.12.1. Diffusion techniques, uncertainties, and species

Diffusion techniques

of recommended study

Uncer ta inty

(in values of D)

Species

+ 2-

capillary ^±20% N a , CO

^ chronopotentiometry ^±10% H

2 voltammetry (linear sweep) ^±20% H

2

362
Li^CO^ -Na

2 C0

3

Equation:

D = A exp [-E/RT] (42.8)

Table 42.12.2. Parameters of diffusion equation (42.8),

precision and recommended study

Species A x 10 3 (cm 2 sec” 1 )

E (cal mol 1

) Temp, range

(K)

Pr ec ision Recommended

study

(a) Li

2 C0

3 -Na

2 C0

3 e utectic

Na

+

9 .81 10,990 850-1130 *±1.3% 42

C0

3

_

7 .36 11,560 840-1115 ^±4.8% 42

H

2 6.45 4 , 346 780-970 *±3% 44

(b) Li

2 C0

3 -Na

2 C03 (25 mol % Na

2 C03

>

Na

+

4 .42 10,060 1030-1210 43

C0^“ 3 . 57 10,920 1030-1210 43

(c) Li

2 C0

3 ~Na

2 C0

3 (75 mol % Na

2 C0

3

)

*

Na

+

9 .40 11,910 1050-1205 43

C0^

_ 4.26 11,130 1050-1205 43

No entry in precision column indicates estimates not possible since results

were reported as equations only.

363
Li2C0^-Na2C02

Table 42.12.3. Self -diffusion coefficients, D x 10^(cm^ sec'*’)

Eutectic melt 25 mo 1 % Na ? CO^ 7 5 mol % Na? C0^

(K) Na

+ CO^ Na

+

C0 3~ Na

+ <

840 0.723

850 1.47 0.784

870 1.70 0.918

890 1.96 1.066

910 2.25 1.231

930 2 .56 1.413

950 2 . 91 1.612

970 3 .28 1.828

990 3.68 2.064

1010 4.11 2 .319

1030 4.57 2.593 3.24 1.72

1050 5.06 2.888 3.56 1.90 3.12 2 . 05

1070 5.58 3 .203 3 .90 2.10 3.47 2 .27

1090 6.14 3.539 4.25 2.31 3.85 2.50

1110 6.72 3.896 4.62 2.53 4.25 2.74

1130 7 . 34 5.01 2.76 4 . 67 3 . 00

1150 5.41 3 . 00 5.12 3.27

1170 5.84 3 .26 5.60 3.55

1190 6.28 3 .52 6.10 3.85

1210 6.73 3 . 80 6 . 63 4.16

Table 42.12.4. Diffusion coefficients in the eutectic melt

References: Na

+

, 42,43; CO^ , 42,43; F^, 44.

364
Li

2 C 03 -Na2 C 0

j

9. Heat of Fusion (Atf^)

Measurement method: estimated [45]

Table 42.13. Heat of fusion of eutectic

AH ° Uncertainty

(kcal mol )

7 . 9 v ± 5%

References [45] .

Eeat Capacity ( C )

No data.

Volume Change on Melting (AF^J

Measurement method: estimated [46]

Table 42.14. Volume change on melting

Mol %

Li

2 C0

3 (AV f /V ) r s Uncertainty •

52 .

13 . 5% ^ ± 8%

References [46]

12. Vapor ^ Pressure (py ) vap

Measurement method: cited with each data set [29,36,45]

No systematic studies of vaporization as molecular carbonates have

been reported, i.e:

10 .

11 .

M

2 C0

3 (A) - M

2 C0

3 (g)

( 42 * 9 )

Concerning the CC^ decomposition of molten carbonates and other possible processes contributing to vaporization, the data for the binary

carbonate eutectic are as follows:

Decomposition processes

CC>2 dissociation and equilibrium pressures for the molten eutectic

(Li

2 C0

3 /Na

2 C0

3

: 53.3/46.7 mol %; m.pt. 495. 8°C).

M

2 C0

3( t )^M 2°(O

+ C0

2 (g)

( 42 - 1C»

P Co 2

( atin ) = K

d

^ aM

2 c°3 (i/iM

2 0

(SL)

' t42 ' 11 ')

Here M is the Li, Na cationic mixture of the binary eutectic, p is

the equilibrium dissociation pressure, and a is the thermodynamically

defined activity. For practical purposes, eq. (42.11) is approximated,

in the first instance, in the mol fraction scale [X], as:

CO, (atm) = K

d

[ V0 3(*/“M A2V)

] (42.12)

365
Li^COg -Na2COj

The values o£ pCCC^) are not uniquely defined unless the oxide content

of the carbonate is known exactly; the "equilibrium pressures" will

thus depend on the quality of the "carbonate", and its previous

history, e.g. to conditions which may promote oxide formation, such

as high temperatures at partial pressures < equilibrium dissociation

pressure for minimal oxide content.

(i) Equilibrium dissociation constant,

Measurement method: emf technique [29]

log K

d

= -12500/T + 6.60 (42.13)

precision: not estimated uncertainty: <v + 1%

Table 42.15.1. CC^ dissociation constant for the binary eutectic

from equation (42.13)

T(K)

K

d

(atm)

T(K)

K

d

(atm)

800 9.44 x 10~ 10 1050 4.96 x 10 -6

850 7.84 x 10 -9 1100 1.72 x 10 -5

900 5.14 x 10 -8 1150 5.38 x 10~ 5 950 2.77 x 10" 7 1200 1.53 x 10 -4

1000 1. 26 x 10“ 6

(ii) Equilibrium CO

2 dissociation pressures

Measurement method: thermodynamic; calc'd [45]

No direct measurements of the equilibrium CO 2 dissociation pressures

have been reported. Based on Andersen's (1975) values for Kd , and

the preceding expressions for Pro? ecl uat i on f° r the CO 2 pressure

as a function of temperature and oxide content of this molten

carbonate eutectic is, (if n is very small, n <<< 1)

log Pco(mm) = -12500/T + 9.4808 - log n (42.14)

where n is the oxide content of the molten carbonate in moles oxide per mole carbonate . The values in table 42.15.2 illustrate the thermodynamically predicted equilibrium CO 2 pressures for a range of

n (comparable to those observed in related systems, i.e. L^CO^;

ternary eutectic).

Table 42.15.2. Equilibrium CO? dissociation pressures (mm) for.

the binary eutectic from equation (42.14)

T(K)

n (mol oxide per mol carbonate)

1.5 x 10 -5 3 x 10“ 5 1.5 x 10~ 4 3 x 10" 4

CO2 pressure (mm)

800

900

1000

1100

1200

4.8 x 10 -2

2.6

64

870

7 700

2.4 x 10 2 1 .

32

440

3800

4.8 x 10 -3

0 .26

6 .

87

77

2.4 x 10 -3

0 .13

3 .

44

38

366
Li

2 C0

3 -Na2 C05

Remarks: It is seen that since the molten carbonate is a solution, and the values of the equilibrium pressures

depend on the solution composition, the dissociation

pressure does not have a unique value unless the value

of n is specified.

Vaporization of molten carbonates

Measurement method: critical analysis [36]

The various "vaporization" data, based on electrolyte losses from high

temperature molten carbonate fuel cells, and the thermodynamics of the

associated reactions, have been critically examined by Maru et al.,

(1976). For a summary of the data status, refer: Li

2 C03

, present work.

References [27,29,36,45,47-49],

13. Thermal Conductivity (liquid) (X^J

Measurement method: steady state radial heat flow [50]

X = 2.271 x 10' 3 + 5.58 x 10

-7

T (42.15)

precision: not estimated uncertainty: 'v + 20%

Results were reported in graphical form only.

Table 42.16. Thermal conductivity from equation (42.15)

T00

X x 10 4 (cal cm

-1 sec

-1 K

1 )

T(K)

X x 10 4 (cal cm-1 sec

-1 K

1 ) 800 27.17 980 28.18

820 27 . 29 1000 28.29

840 27.40 1020 2 8.40

860 27.51 1040 28.51

880 27 . 62 ‘ 1060 28 . 62

900 27.73 1080 28 .74

920 27.84 1100 28.85

940 27.96

960 28.07

Sole investigation; equation obtained by fitting the interpolated values

from graphical presentation in [50].

References [ 50]

14. Thermal Conductivity (solid) (\ ) ° s Measurement method: steady state radial heat flow [50]

precision: not estimated uncertainty: ^ + 101

For numerical values: see table 42.17.

367
Ll

2 C°3‘ Na

2 C0

3

Table 42,17. Thermal conductivity

T(K)X x 10 4 (cal cnf^sec-1 K

1 ) 400 50 .

450 40.6

500 30.6

550 21.5

600 19.1

650 17.0

700 16.7

750 16.7

References [ 50] .

15. Cryo scopic Constant

Measurement method

a

f

>

: estimated [451

Table 42.18. Cryoscopic constant

Mol %

k

f Uncertainty

Li

2 C0

3 (K mol ^kg~f)

53.3 13 .

^ ± 5%

References [45],

16. References

[1] Janz, G. J., and Lorenz, M. R., J, Chem , Eng. Data, 6_, 321 (1961),

[2] Cairns, E, J. , and McDonald, D. I., Nature, 1 94 , 441 (1962),

[3] Janz, G, J. , Downey, J, R. , Jr,, Allen, C, B,, and Tomkins, R. P. T.,

"Eutectic Data" - 2 vols; ERDA-TID - 271 63 -PI 8 P 2 ; NTIS, Washington,

D. C. (1977).

[4] Janz, G. J,, Downey, J, R,, Jr., Allen, C, B,, and Tomkins, R, P. T, ? "Physical Properties Data Compilations Relevant to Energy Storage.

I. Molten Salts: Eutectic Data", NSRDS-NBS-61 ; U. S. Gov't

Printing Office, Washington, D. C. (1978),

[5] Eitel, W. , and Skaliks, W. , Z. anorg . allgm. Chem,, 183 , 270 (1929).

[6] Janz, G. J., and Lorenz, M. R. , J. Electrochem. Soc., 1 08 , 1052 (1961).

[7] Spedding, P. L., J. Electrochem. Soc., 117 , 177 (1 970).

[8] Ward, A. T., and Janz, G. J., El ectrochimica Acta, 10_, 849 (1965).

[9] Vorob'ev, G. V., Pal'guev, S. F., and Karpachev, S. V., Tr . Inst.

Elektrokhim. Akad. Nauk SSSR, Ural'sk Filial, 2_, 115 (1961).

[10] Moiseev, G. K., and Stepanov, A. K. , Tr . Inst. Elektrokhim. Akad.

Nauk SSSR, Ural. Fil., _5, 61 (1964).

[11] Vorob'ev, G. V., Pal'guev, S. F., and Karpachev, S, V., Electrochem.

of Solid and Molten Electrolytes , 3_, 33, 1966, Consultants Bur.

New York; Trudy No. 6; Inst. Electrochem. Ural. Acad. Sci. (1965).

368
Li^CO^ -^200^

[12] Noda, H., Shiota, K. , Shiotawa, J., Tamura, H., and Ishino, T.,

Denki Kagaku, 3^, 417 (1963).

[13] Spedding, P. L., J. Electrochem . Soc,, 120 , 1049 (1973).

[14] "Dangerous Properties of Materials ", Sax, N, I., Van Nostrand

Reinhold, N. Y. (1969).

[15] "Registry of Toxio Effects of Chemical Substances ", Christensen, H. E.,

and Lubinbyhl, T. T., eds., U. S. Dept, H. E. W, , U. S. Gov’t Printing

Office, Washington, D. C. (1975).

[16] Vapor pressure, calculated (see p. 366, this work).

[17] "Potential Hazards in Molten Salt Baths for Heat Treatment of Metals"

National Board Fire Underwriters Research Report No. 2 (1954).

[18] "Handbook of Reactive Chemical Hazards'

t Bretherwick, L, ? Butterworths Co., London (1975),

[19] Janz, G. J., Tomkins, R. P. T., Downey, J, R,. Jr,, Allen. C. B.,

"Safety and Hazards", Chapter in "Eutectic Data", ERDA TID - 271 63 -PI

NTIS, U. S. Dept. Commerce, Springfield, Va . (1977).

[20] Ozeryanaya, I. N. , Manukhina, T. I., and Smirnov, M. V., Zashch Metal.,

8_, 128 (1972).

[21] Janz, G. J., and Conte, A., Electrochim. Acta 9, 1269 (1964).

[22] Janz, G. J., Conte, A., and Neuenschwander , E., Corrosion, 19^, 292 (1963).

[23] Bartlett, H. E,, and Johnson, K. E., J. Electrochem. Soc., 114 , 457 (1967)

[24]

Davis, H. J., and Kinnibrugh, D. R. , J. Electrochem. Soc., 117 , 392 (1970)

[25] Ingram, M. D., and Janz, G. J., Electrochimica Acta, 1_0, 783 (1965).

[26] Dubois, J., "Chemical and Electrochemical Reactions of Molten Alkali

Carbonates as Fuel Cell Electrolytes"

,

Ph.D, Thesis; Fac. Sci. Univ.

Paris, France (1964).

[27] Trachtenberg, I., and Cole, D, F., "Fuel Cells - II", p. 269,

Baker, B. S., ed . , Adv. Chem, Series No. 90; Amer, Chem. Soc.,

Washington, D. C. (1969),

[28] Schenke, M. , and Broers, G. H. J., Proceedings of the 5th International

Symposium on Power Sources - Brighton; . Pergamon Press, Oxford, (1966).

[29] Andersen, B. K. , "Thermodynamic Properties of Molten Alkali Carbonates ", Ph.D. Thesis, Tech. Univ. Denmark (1975),

[30] Busson, N. , Palous, S., Buvet, R., and Millet, J., Compt. Rend., 260,

720, 6097 (1965).

[31] Ingram, M. D., Baron, B., and Janz, G. J., Electrochim. Acta, 11 , 1629 (1966).

[32] Janz, G. J. , J. Chem. Educ . , 44, 581 (1967),

[33] Busson, N., Palous, S., Millet, J., and Buvet, R,, Electrochim. Acta,

12, 910 (1967) .

[34] Janz

G. J . , and Tomkins, R. P. T. , Corrosion, 34Cin press) (1978)

[35] Maru

H. C . , et al .(Institute of Gas Technology)^ "Molten Salt

Thermal Energy Storage Systems: Salt Selection ", Rpt. COO-2888-1 , ERDA Contract No. E (11 -1) -2888 , Aug. (1976); NTIS, U. S. Dept.

Commerce, Springfield, Va.

369
[36]

Li2C03-Na2-C0j

Maru, H. C., et al, (Institute of Gas Technology), "Fuel Cell Research

on Second Generation Molten Carbonate Systems: II. Characteristics

of Carbonate Melts", Quarterly Status Rpt,, Project 8984 , ERDA

Contract No. 31-109-38-3552 (Sept. 1976).

[37] Botts, W. V. , Kohl, A. L., and Trilling, C. A., "Low BTU Gasification

of Coal by Atomics Internationales Molten Salt Process ", Proceedings

of the 11th Intersociety Energy Conversion Engineering Conference,

I, 280 (Sept. 1976).

[38] Cover, A. E., Schreiner, W. C., and Skaperdas, G. T., "The Kellogg

Coal Gasification Process"3 Extended Abstracts; American Chemical

Soc. Meeting, Washington, D. C. (1971).

[39] Atomics International, "Development of a Molten Carbonate Process

for Removal of Sulfur Dioxide from Power Plant Stack Gases"

,

Progress Rpt. No. 2, U. S. Public Health Services, Contract

PH 86-67-128, Canoga Park, Cal, (1968).

[40] Grantham, L. F,, and Ferry, R. B, , "Corrosion in Alkali Metal

Carbonate-Based Melts", Proc . International Symp . Fused Salts

J. P. Pemsler, ed . , Electrochemical Soc., Inc . , Pr inceton , N. J.

(1976)

[41] Ozeryanaya, I. N., Manukhina, T. I., Belyaeva, G. I., Burakova, E. A.,

and Smirnov, M. V., Zashch. Metall., 2_(6) , 700 (1965).

[42] Spedding, P. L., and Mills, R., J. Electrochem. Soc . , 113 , 599 (1966).

[43] Mills, R. , and Spedding, P. L., J. Phys . Chem., 7_0, 4077 (1966).

[44] Valgin, M. A., L'vov, A. L., and Loskutkin, V. A., Soviet Electrochem.,

9, 353 (1973).

[45] Janz, G. J., et al . , (MSDC-RPI) unpublished work (1977).

[46] Maru, H. C., Dullea, J, F., and Juang , V. S., "Molten Salt Thermal

Energy Storage Systems ", ERDA Tech. Report COO-2888-1 (8981);

NTIS, U. S. Dept. Commerce, Springfield, Va. (Aug. 1976).

[47] Broers, G. H. J,, "High Temperature Galvanic Fuel Cells" Ph.D, Thesis,

Univ. Amsterdam (1958).

[48] Broers, G. H. J., and Schenke, M., "Long-Run Experiments on High

Temperature Molten Carbonate Fuel Cells", Chapter in "Hydrocarbon

Fuel Cell Technology", Baker, B, S,, ed . , Academic Press, N. Y.

(1965) .

[49] McQuade, J, M, , Hamlen, R, P., and Nelson, R. P., "Alkali Carbonate

Fuel Cell", U. S, Patent 3,268,365 (1966) Aug. 23; (assigned to

General Electric Co.).

[50] Egorov, B, N. , and Revyakina, High Temp., 8_, 1220 (1970).

370
XLIII. Lithium Carbonate-Potassium Carbonate: Li^CO^-K^CO^

1. Melting Temperatures (Tm) Pure substance melting points:

Li

2 C0

3

: 723°C

K

2 C03

: 898°C

Eutectic melting points:

Eutectic 1: 498°C, composition: 42.7 mol % Li

2 C0

3 Eutectic 2: 488°C, composition: 62 mol % Li

2 C03

Figure 43.1. Li

2 C03 ~K2 C0

3 phase diagram

References [1-4] .

2. Density (p)

Measurement method: Archimedean technique [5]

Single variable equation

p = a + bT (43.1)

precision: ^ + 0.2% uncertainty: ^ + 0.5%

371
Li

2 C03

-K

2 C03

Table 43.1. Coefficients of single variable equation (43.1)

Mol % L1 2C0 3 a -b x 10 3 Temp, range (K)

0 2.4295 0.4543 1190 - 1250

10 2.4094 0.4422 1130 - 1250

20 2.3942 0.4385 1050 - 1250

30 2.4184 0.4761 950 - 1170

40 2.3795 0.4527 890 - 1150

42 .

2.3711 0.4623 890 - 1190

50 2.3599 0.4548 870 - 1150

60 2.3593 0.4569 890 - 1150

62 2.3526 0.4532 850 - 1210

70 2.3251 0.4390 970 - 1150

80 2.2966 0.4264 990 - 1170

90 2.2687 0.4180 1010 - 1170

100 2.2365 0.4041 1030 - 1130

Two -independent -variable equation:

p = a + bT + cC + dC 2 + eC 3

(C = mol % Li

2

CC> 3

) (43.2)

precision: + 0.3% uncertainty: ^ + 0.5%

Table 43.2. Coefficients of two - independent-variable equation

a b x 10 4 c x 10 3 d x 10 5 e x 10 8

2.42818 -4.45548 -1.82681 1.20594 -8 . 42184

_3 Table 43.3. Densities (g cm ) from equations in table 43.1

Mol z li 2 co 3

T ( K ) 100 90 80 70 62 60 50 42.7 40 30 20 10 0 850 1.967

870 1.958 1.964

890 1.949 1.953 1.955 1.960 1.977

910 1.940 1.944 1.946 1.950 1.968

930 1.931 1.934 1.937 1.941 1.958

950 1.922 1.925 1.928 1.932 1.949 1.966

970 1.899 1.913 1.916 1.919 1.923 1.940 1.957

990 1.874 1.890 1.904 1.907 1.910 1.913 1.931 1.947

1010 1.847 1.866 1.882 1.895 1.898 1.901 1. 904 1.922 1.938

1030 1.820 1.838 1.857 1.873 1.886 1.889 1.891 1.895 1.913 1.928

1050 1.812 1.830 1.849 1.864 1.877 1.880 1.882 1.886 1.904 1.918 1.934

1070 1.804 1.821 1.840 1.855 1.868 1.870 1.873 1.876 1.895 1.909 1.925

1090 1.796 1.813 1.832 1.847 1.859 1.861 1.864 1.867 1.886 1.899 1.916

1110 1.788 1.805 1.823 1.838 1.850 1.852 1.855 1.858 1.877 1.890 1.907

1130 1.780 1.796 1.815 1.829 1.840 1.843 1.846 1.849 1.868 1.880 1.899 1.910

1150 1.788 1.806 1.820 1.831 1.834 1.839 1.859 1.871 1.890 1.901

1170 1.780 1.798 1.822 1.830 1.861 1.881 1.892

1190 1.813 1.821 1.872 1.883 1.889

1210 1.804 1.864 1.874 1.880

1230 1.855 1.865 1.871

1250 1.846 1.857 1.862

References [5-7],

372
Ll

2 C0 3

K

2 C0

3

3. Surface Tension (y)

Measurement method: pin detachment; maximum bubble [6,8]

Y

= 324.09 - 124.8 x 10' 3 T (43.3)

precision: + 0.8% uncertainty: % + 1,5%

Table 43.4. Surface tension of eutectic 1 from equation (43.3)

T(K)

Y (dyn cm

-

)

T(K)

Y (dyn cm 1 )

840 219.3 960 204.3

860 216 .

980 201.8

880 214.3 1000 199 .

900 211.8 1020 196 .

920 208 .

1040 194.3

940 206.8 1060 191.8

1080 189.3

Y

= a - bT

precision: in table 43,5

(43.4)

uncertainty: ^ + 3%

Table 43.5. Coefficients of equation (43.4), and precisions

Mol % Li 2 CO 3 a b x 10 3 Temp . range

(K)

Precision

0 241.07 61.4 1173-1308 ±0.41%

10 262.92 79 .

1114-1173 ± 0 . 12 % 30 241.94 58 .

931-1173 ±0.83%

50 229.59 39 . 5 800-1172 ± 0 . 68 %

70 231.18 29 .842-1173 ±0.25%

90 253.42 33.4 965-1172 ±0.62%

100 281.50 36 . 6 1023-1173 ±0.46%

373
Li

2 C03

~ K

2 C03

Table 43.6. Surface tension (dyn cm ^) from equations in table 43.5

T ( K)

Mol % Li 2 C0

90 70 50 30 10

800 198.0

820 197.2

840 206.196 .

860 206 .195 .

880 205 .

194.8

900 204 .194.0

920 204 .

193.3

940 203 .192 .

187.4

960 203.1 191 .

186 .

980 220 .202 .

190 .185.1

1000 220 .

202.0 190 .

183.9

1020 219 .

201 .189 .182 .

1040 218.7 200 .

8

188 .181 .

1060 218 .200 .

187 .180.5

1080 217 . 3 199 .186.9 179.3

1100 216 .199.1 186.1 178 .

1120 216 .

198 .185.4 177.0 173.4

1140 215 .

197.9 184 .

175 .

171.8

1160 214 . 7 197.3 183.8 174 .

170 .

1180 168 .

References [6,8]

4. Viscosity (r\)

Measurement method: oscillating sphere [9]

n = a + bT + cT

2 (43.5)

precision: in table 43.7 uncertainty: ^ + 25%

Table 43.7. Parameters of equation (43.5), and precisions

Li 2 C0 3 (mol Z)

a -b x 10 2 c x 10 s Temp, range

(K)

Precision

10 10.776 0.6800 1123-1173

20 50.590 7.576 2.980 1023-1173 ±0.4?

30 53.599 8.100 3.202 973-1173 ±0.4%

40 56.671 8. 601 3.405 973-1173 ± 0 . 6 % 50 56.353 8.467 3.317 973-1173 ±0.7%

60 64.086 9.816 3.917 973-1173 ±0.5%

70 69.752 10.785 4.347 973-1173 ±0.5%

75 72.031 11.138 4.490 973.1173 ± 0 . 6 % 80 75.469 11.719 4.747 973-1173 ± 1 . 0 % 85 70.975 10.785 4.289 973-1173 ±0.5%

90 79.076 12.136 4.866 1023-1173 ±0.5%

95 16.121 0.5749 -0.3958 1023-1173 ±4.5%

100 9 . 621 -0.6993 -0.9960 1023-1173 ±4.1%

374
Li

2 C0

3 -K

2 C0

3

Table 43.8. Viscosity (cp) from equations in table 43,7

Mol % Li,CO

( K ) 10 20 30 40 50 60 70 75 80 85 90 95 100

980 4.97 5.08 5.23 5.51 5.81 6.00 6.21 6.47

990 4.79 4.89 5.04 5.30 5.59 5.77 5.98 6.24

1000 4.62 4.71 4.85 5.10 5.37 5.55 5.75 6.01

1010 4.45 4.54 4.67 4.90 5.17 5.34 5.53 5.80

1020 4.29 4.37 4.50 4.72 4.97 5.14 5.32 5.59

1030 4.17 4.14 4.20 4.33 4.54 4.78 4.94 5.12 5.39 5.70 6.00 6.26

1040 4.03 3.99 4.05 4.17 4.37 4.61 4.76 4.93 5.20 5.49 5.86 6.12

1050 3.90 3.85 3.90 4.02 4.20 4.44 4.58 4.76 5.02 5.30 5.72 5.98

1060 3.77 3.72 3.76 3.87 4.05 4.27 4.42 4.58 4.85 5.11 5 .58 5.84

1070 3.64 3.59 3.62 3.73 3.90 4.12 4.26 4.42 4.68 4.93 5.44 5.70

1080 3.53 3.47 3.50 3.60 3.76 3.98 4.11 4.27 4.52 4.76 5.30 5.56

1090 3.42 3.35 3.37 3.47 3.63 3.84 3.97 4.13 4.38 4.61 5.15 5.41

1100 3.31 3.24 3.26 3.35 3.51 3.72 3.84 4.00 4.24 4.46 5.01 5,26

1110 3.21 3.14 3.15 3.24 3.39 3.60 3.72 3.88 4.11 4.32 4.86 5.11

1120 3.12 3.04 3.05 3.13 3.28 3.49 3.61 3.76 3.98 4.19 4.72 4.96

1130 3.09 3.03 2.96 2.96 3.03 3.18 3.39 3.50 3.66 3.87 4.07 4.57 4.81

1140 3.02 2.95 2.87 2.87 2.94 3.09 3 . 30 3.41 3.56 3.77 3.96 4.42 4.65

1150 2.96 2.88 2.80 2.79 2.85 3.00 3.21 3.32 3.48 3.67 3.86 4.28 4.49

1160 2.89 2.81 2.73 2.72 2.77 2.93 3.14 3.25 3.40 3.58 3.78 4 .13 4.33

1170 2.82 2.74 2.66 2.65 2.70 2.86 3.07 3.18 3.34 3.50 3.70 3.98 4.17

References [ 9]

5. Electrical Conductance (k)

Measurement method: classical ac [10]

k = A expC-E/RT) (43,6)

precision; estimate not possible uncertainty: ^ + 2.51

Data reported in equation form.

Table 43.9. Parameters of equation (43.6)

k 2 co 3 (mol %)

A E (cal mol-1

) Temp . range

(K)

100 10.52 3830 1178-1281

90 10.85 3840 996-1136

80 11.41 3890 972-1165

70 13.32 4180 973-1193

60 14 .49 4320 1003-1197

57.3 14 .56 4320 1013-1223

50 14 .96 4330 1013-1222

40 16 .63 4240 993-1227

30 20.27 4180 1001-1239

20 23.37 4110 1034-1246

10 26.46 4030 1133-1260

0 29.22 3940 1013-1153

375
Li

2 C0 3‘ K2 C0

3

Table 43.10. Specific conductance (ohm ^cm *) from

equations in table 43.9

Mol t li

2 co

3 TOO 100 90 80 70 60 50 42.7 40 30 20 10 0

980 1.557 1.548

1000 2.473 1.969 1.648 1.625 1.611 1.571

10.70 4.183 2.577 2.053 1.766 1.728 1.719 1.694 1.674 1.631

1040 4.342 3.198 2.682 2.137 1.840 1.800 1.791 1.762 1.737 1.692

1060 4.501 3.320 2.786 2.221 1.915 1.872 1.863 1.831 1.800 1.752

1080 4.660 3.443 2.890 2.306 1.989 1.945 1.936 1.899 1.862 1.813

1100 4.818 3.565 2.994 2.390 2.063 2.017 2.008 1.968 1.925 1.873

1120 4.976 3.686 3.098 2.474 2.138 2.090 2.080 2.036 1.987 1.932

1140 5.133 4.466 3.808 3.202 2.558 2.212 2.162 2.152 2.104 2.049

1160 4.605 3.929 3.306 2.642 2.286 2.235 2.224 2.172 2.110

1180 4.744 4.049 3.409 2.726 2.360 2.307 2.296 2.240 2.054

1200 4.882 4.169 3.512 2.809 2.434 2.379 2.117

1220 5.019 4.289 3.614 2.893 2.507 2.450 2.167

1240 5.155 4.408 3.716 2.223

1260 5.291 2.278

1280 2.334

References [6,7,10,11].

6. Safety and Hazards

A. Hazard rating [12-14]

(i) Toxicity: Li? CO3 , toxic dose (oral, human),

0.7 mg/kg; K

2 C0 ^, severe

(ii) Vapor pressure : Carbonates dissociate on heating:

M

2 C0

3(£)

x=>M2 0

(^)

+ C0

2 (g) (43.7)

For the equimolar mixture the CO? equilibrium dissociation pressure

is 'V/ 1.6 x 10 -3 mm at approx. 530°C.

B. Disaster hazards [12,15-17]

(i) Molten salt bath "explosions": i.e. explosive generation

of steam due to bulk water "carry-over" and/or equipment

failure; i.e. explosive expansion of "trapped air.

(ii) When heated at C0 2 pressures less than equilibrium,

carbonates decompose to alkali metal oxides; the

toxicology and disaster hazards of such oxides are

the same as very strong caustics, i.e. react with

water or steam exothermically to form hydroxides

that are very aggressive to body tissues (chemical

burns) ; L^COj by itself is classed as a strong

caustic

References. [12-17],

376
Li

2 CVK

2 C03

7. Corrosion

Table 43.11. Corrosion studies from

primary research literature

Studies

Ti alloy

oxides (polarographic

studies)

SS-304 ; A1

References

18

19

20,21

Acid-base relationships

in molten carbonates 22-25

Hydrolysis (H

2 O) reactions

Corrosion in molten salts:

annotated bibliography

26-28

29

Molten carbonates: fuel

cells; thermal energy

storage; coal gasification;

power plant stack gases 30-35

References [18-35].

8. Diffusion

Measurement method: cited in tabulations

List of diffusing species investigated in L^COj-K^COj as solvent

K , CO^ , Pb 3 Cu 3 Cd 3 3 Cr ^0 ?

3 Cl~ 3 Br~ 3 I

~

The italicized species indicate studies with insufficient data-sets

for temperature-dependence characterization of diffusion coefficients.

For these species: see table 43,12.4,

precision: in table 43.12.2 uncertainty: in table 32.12.1

Table 43.12.1. Diffusion techniques, uncertainties, and species

Diffusion technique Uncertainty Species

of recommended study (in values of D)

capillary ^± 20 % K+

, 003

“

chronopotentiometry ^± 10 % Pb 2+

, Cu+, Cd 2+, 2 + 2 — , — Nx , , Cl , Br", l“

377
Ll

2 C0 3“ K

2 C0

3

Equations

D = A exp [ -E/RT] (43.8)

Table 43.12.2. Parameters of diffusion equation (43.8), precisions,

and recommended StudySpecies A x 10 3 (cm2 sec

-1

)

E (cal mol 1 ) Temp . range

(K)

Precis ion Recommended

study

K+

7 .26 11,490 890-1130 *±3 . 5% 36

C0

2 ~

7 .94 11,860 850-1135 ^±3 . 5% 36

Table 43.12.3. Self-diffusion coefficients from

equations in table 43.12.2

T

(K)

0^+ x 10 5

K. (cm 2 sec

-1

)

D

colx 105

(cm 2 sec -1

)

850 0.71

870 0.83

890 1 .09 0.97

920 1 .35 1 .21

950 1.65 1 .48

980 1.99 1.80

1010 2.37 2 .15

1040 2.79 2 .55

1070 3 .27 3.00

1100 3.78 3 .49

1130 4 . 35 4.03

Table 43.12.4. Diffusion coefficients for species

not included in table 43.12.3

Species D x 10 5 (cm 2 sec

-1

) Species D x 10 5

( cm 2 sec -

)

Pb 2 +

2 . 74 Cr 2°?' 4.12

Cu

+ 4.89 Cl" 0 .089

cd

2+

2 .71 Br~ 0.081

Ni 2 +

3 .78 I~ 0.071

References

K

+

, 36; C0 3» 36 ; Pb

2+

, 37; Cu

+

,

, 37; Cd

2+

, 37; Ni

2+

, 37;

Cr 2°7 37 • 9 U ' 9 Cl" , 37; Br~, 37; I", 37.

378
Li^CO^-K^CO^

9. Heat of Fusion ( CH^.)

Measurement method: drop calorimetry [38]

Table 43.13. Heat of fusion

Mol % L

2 CO

3 AH °t _ 1 (kcal mol ) Un'certainty

50 8 . 7 ^ ± 1.5%

References [38]

10.

Heat of Capacity J Measurement method: drop calorimetry [38]

Table 43.14. Heat capacity

Mol % Li

2 C0

3

C

P

i 1 (cal K

1 mol -1

)

Temp, range

(K) Uncertainty

50 44.65 ± 0.1 778-1200 ^ ± 0.5%

References [38]

11.

Volume Change on Melting (A Vj.)

Measurement method: estimated [39]

Table 43.15. Volume changes on melting

Mol % Li 2 C0 3 T (°C) m (4V

f /V

s

) Uncertainty

42 .

498 9 . 3%

50 505 9.6% ^±8%

63 488 8.5%

References [39]

12.

Vapor Pressure (

vap

) Measurement method: cited with each data set

No systematic studies of vaporization as molecular carbonates

have been reported, i.e.,

M

2 C0

3 O)-

* M

2 C0

3 (g)

(43.9)

For the CO? decomposition of molten carbonates and other possible

processes contributing to vaporization, the data for the equimolar binary carbonate system are as follows.

Decomposition processes

CO 2 dissociation and equilibrium processes for the molten equimolar binary Li,K/COj system (m.pt. 505°C)

M

2 C0

3 (4)

- M 2°U)

+ CO

2(g) (43.10)

379
Li

2 C0 3‘ K

2 C0

3

P C0 ?

( atm ) Kd

t aM ? CO, / aM 9 0^ (43.11]

Z 5 00 Z (£)

where M is the Li, K cationic mixture of the equi-molar binarymixture, p is the equilibrium CO 2 dissociation pressure, and a the thermodynamically defined activity. For practical purposes,

eq. (43.11) is generally expressed in the mol fraction scale [X]

,

as

P C0 ?

( atm ) = K

d

f XM ? CO. ^ XM ? 01 (43.12)

z (O

The "equilibrium pressures" thus depend on the quality of the "carbonate"

and its previous history, i.e. the oxide content, since the molten system

is a solution.

(i) Equilibrium dissociation constant,

Measurement method: emf technique [28]

log K

d

= -13810/T + 6.77 (43.13)

precision: not estimated uncertainty: ^ + 1 %

Table 43.16.1. CO 2 dissociation constant for the equimolar mixture

from equation (43.13)

T(K)

K

d (atm)

T(K)

K

d (atm)

800 3.22 x 10 _1

1050 4.15 x 10‘ 7 850 3 . 33 x 10 -1

1100 1.64 x 10' 6 900 2.66 x 10 -9 1150 5.77 x 10“ 6 950 1.71 x 10 -8 1200 1.83 x 10 -5

1000 9.12 x 10 -8

(ii) Equilibrium CC>2 dissociation pressures

Measurement method: thermodynamic; calc'd [40]

No direct measurements of the equilibrium COo dissociation pressures

have been reported. Based on Andersen’s (19/5) values for Kd, and

the preceding expressions for , the equation for p LU 7 LO

of T and oxide content for the molten binary system is:

as a function

log pCQ

(mm) = -13810/T + 9.6508 - log n (43.14)

Here n is the oxide content in mols oxide/mol carbonate, and

n <<< unity. The values in table 43.16.2 illustrate the thermodynamically predicted equilibrium CO 2 pressures for a range of

n (comparable to the oxide contents observed in related systems,

e.g. Li

2 C03

; K

2 C03

; ternary eutectic).
L ± 2 CO 2 -K^CO^

Table 43.16.2. Equilibrium CO 2 dissociation pressures (mm) for the

equimolar mixture from equation (43.14)

T n (mol oxide per mole carbonate)

(K) 1.5 x 10 -5 3 x 10" 5 1.5 x 10~ 4

3 x 10' 4

CO2 pressure (mm)

800 1.6 x 10' 3 8.1 x 10“ 4 1.6 x 10 -4 8.1 x 10" 5 900 0 .13 6.7 x 10" 2 1.3 x 10 -2 6.7 x 10" 3 1000 4 . 6 2 . 3 0 .46 0 .23

1100 83 42 8 .

4 .

1200 930 465 93 46

Remarks: Since the molten carbonate/oxide system is a solution,

and the values of the equilibrium pressures depend on the

solution composition, the dissociation pressures do not

have a unique value unless the value of n is specified.

Vaporization of molten carbonates

Measurement method: critical analysis [31]

The various "vaporization" data, based on electrolyte losses from

high temperature molten carbonate fuel cells, and the thermodynamics

of the associated reactions, have been critically examined by Maru

et al. (1976). For a summary of the data status, refer: L^CO^,

present work.

References [28,31,40-44].

IS. Thermal Conductivity (liquid) (X^)

No thermal conductivity studies reported.

14. Thermal Conductivity0 (solid) (X ) s No thermal conductivity studies reported.

15. Cryoscopic Constant (kj?)

Measurement method: calc'd from AH^ [40]

Table 43.17. Cryoscopic constant

Mol % Li

2 C0

3 k

f (K mol“ikg~-'-)

Uncertainty

50 14. 6 ^ ± 1.5%

References [38,40].

16. References

[1] Stern, K. H. , and Weise, E. L., "High Temperature Properties and

Decomposition of Inorganic Salts. Part 2. Carbonates ”, NSRDS -NBS -3 0 ; U. S. Gov't Printing Office, Washington, D. C. (1969)

[2] Janz, G. J. , and Lorenz, M. R. , J. Chem. Eng. Data, 6_, 321 (1961);

Eitel, W. , and Skaliks, W. , Z. anorg. allgm. Chem., 183 , 263 (1929)

381
Li^COj -K^COj

[3] Janz, G. J., Downey, J. R. , Jr., Allen, C. B. , and Tomkins, R. P. T.

,

"Eutectic Data" - 2 vols; ERDA-TID-27163-P1 + P2; NTIS, Washington,

D. C. (1977).

[4] Janz, G. J. , Downey, J. R. , Jr., Allen, C. B. , and Tomkins, R. P. T.

,

"Physical Properties Data Compilations Relevant to Energy Storage . I. Molten Salts: Eutectic Data", NSRDS -NBS - 61 ; U.S. Gov’t Printing

Office, Washington, D. C. (1978).

[5] Spedding, P. L. , J. Electrochem. Soc. , 117 , 177 (1970).

[6] Ward, A. T., and Janz, G. J. , Electrochimica Acta, 1_0, 849 (1965).

[7] Vorob’ev, G. V., Pal'guev, S. F., and Karpachev, S. V. , Tr. Inst.

Elektrokhim. Akad Nauk SSSR, Ural. Fil. , 2_, 115 (1961).

[8] Moiseev, G. K. , Stepanov, G. K. , Tr . Inst. Elektrokhim. Akad. Nauk

SSSR, Ural. Fil., 5, 61 (1964).

[9] Vorob'ev, G. V. , Pal'guev, S. F. , and Karpachev, S. V. , Electrochem.

of Solid and Molten Electrolytes

,

3_, 33 (1966), Consultants Bur,

New York; Trudy No. 6; Inst. Electrochem. Urals Acad. Sci. (1965).

[10]

Spedding, P. L. , J. Electrochem. Soc., 120 , 1049 (1973).

[11] Noda, H. , Shiota, K. , et al., Denki Kagaku, ^VL, 417 (1963).

[12] "Dangerous Properties of Materials ", Sax, N. I., Van Nostrand Reinhold

Co. , N. Y. (1969)

[13] "Registry of Toxic Effects of Chemical Substances", Christensen, H. E.,

and Lubinbyhl , T. T. , eds. , U. S. Dept. H. E. W. , U. S. Gov’t Printing

Office, Washington, D. C. (1975).

[14] Vapor pressure, calculated (see p. 380, this work).

[15] "Potential Hazards in Molten Salt Baths for Heat Treatment of Metals"

,

National Board Fire Underwriters Research Report No. 2 (1954).

[16] "Handbook of Reactive Chemical Hazards", Bretherwick, L., Butterworths

Co . , London (197 5) .

[17] Janz, G. J., Tomkins, R. P. T. , Downey, J . R. , Jr., and Allen, C. B.,

"Safety and Hazards", Chapter in "Eutectic Data", ERDA TID- 271 63 -Pil;

NTIS, U. S. Dept. Commerce, Springfield, Va (1977).

[18] Ozeryanaya, I. N. , Manukhina, T. I., and Smirnov, M. V., Zashch. Metal,

8, 128 (1972).

[19] Delimarskii, Yu. K. , Fiz. Khim. Rasplav. Shlakov, Naukove Dumka , Kiev,

SSSR, p. 200 (1970)

[20] Institute of Gas Technology, "Development of Molten Carbonate Fuel

Cells", AGA Project DC-4-1; Final Report, Chicago (1967).

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Thermal Energy Storage Systems: System Design", Rpt. COO -2888-2;

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Carbonates as Fuel Cell Electrolytes", Ph.D. Thesis, Fac. Sci. Univ.

Paris, France (1964).

[23] Ingram, M. D. , and Janz, G. J., Electrochim. Acta, 1_0, 783 (1965).

[24] Busson, N. , Palous , S., Buvet, R. , and Millet, J. , Compt. Rend.,

260 , 720, 6097 (1965).

382
Li

2 C0

3 -K

2 C0

3

[25] Ingram, M. D. , Baron, B. , and Janz, G. J. , Electrochim. Acta, 11,

1629 (1966). —

[26] Janz, G. J. , J. Chem. Educ., 44_, 581 (1967).

[27] Busson, N. , Palous, S., Millet, J. , and Buvet, R. , Electrochim. Acta,

12, 910 (1967).

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Ph.D. Thesis, Tech. Univ. Denmark (1975).

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Thermal Energy Storage Systems : Salt Selection"

Rpt. COO-2888-1,

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on Second Generation Molten Carbonate Systems: II. Characteristics

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of Coal by Atomics International's Molten Salt Process ", "Proceeding

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Extended Abstracts, American Chemical Soc

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[36] Spedding, P. L. , and Mills, R. , J. Electrochem. Soc., 113 , 599 (1966).

[37] Tumanova, N. Kh. , Ukr. Khim. Zh. , _30, 648 (1964).

[38] Janz, G. J., and Perano , J. L., Trans. Faraday Soc., 6_0, 1742 (1964).

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Energy Storage Systems", ERDA Tech. Report COO-2888-1 (8981); NTIS,

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[40] Janz, G. J., et al . , (MSDC-RPI), unpublished work (1977).

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Univ. Amsterdam (1958).

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Temperature Molten Carbonate Fuel Cells", Chapter in "Hydrocarbon

Fuel Cell Technology", Baker, B. S., ed . , Academic Press, N. Y.

(1965) .

[43] McQuade , J. M. , Hamlen, R. R. and Nelson, R. R . , "Alkali Carbonate

Fuel Cell", U. S. Patent 3,268,365 (1966) Aug. 23; (assigned to

General Electric Co)

[44] Trachtenberg, I. , and Cole, D. F., "Electrolyte Studies in Molten

Carbonate Fuel Cells" Chapt. in "Fuel Cell Systems II ", Baker, B. S.,

ed. , Amer. Chem. Soc., Advances in Chemistry Series, 9_0, 268-280 (1969).

383
XLIV. Sodium Carbonate-Potassium Carbonate: Na2CC>

3 -K2C0

3 1. Melting Temperatures (T ) Pure substance melting points:

Na

2 C0

3

: 858°C

K

2 C0

3

: 8 98° C

Minimum melting solid solution melting point:

710°C, composition: 58 mol % Na2C0

3

References [1-5] .

2. Density (p)

Measurement method: Archimedean technique [6]

Single variable equation

p = a + bT (44.1)

precision: 'v + 0,21 uncertainty: ^ + 0.5%

384
Na2C02"K2C02

Table 44.1. Parameters of single variable equation (44.1)

d 1 % Na2C0 3 a -b x 10 3 Temp, range (K)

0 2.4295 0.4543 1190 - 1260

10 2.4179 0.4419 1180 - 1260

20 2 .4130 0.4329 1140 - 1260

25 2.4243 0.4405 1070 - 1270

30 2.4240 0.4375 1070 - 1260

40 2.4278 0.4366 1020 - 1240

50 2 .4359 0.4393 1000 - 1230

58 2.4413 0.4406 1050 - 1240

60 2 .4506 0.4467 1040 - 1230

70 2.4509 0.4419 1070 - 1240

75 2.4614 0.4465 1090 - 1240

80 2.4723 0.4520 1070 - 1230

90 2.4862 0.4581 1120 - 1240

100 2.4532 0.4267 1140 - 1240

Two- independent -variable equation

p = a + bC + cT

2 + dC 2 + eT3 (C = mol % Na

2 C03

) (44.2)

precision: + 0.61 uncertainty: ^ + 0.51

Table 44.2. Coefficients of two -independent -variable equation (44.2)

a b x 10 4 c x 10 7 d x 10 6 e x 1 0

1 1

2 .22615 4 . 05178 -3.40228 1.84011 8 .55883

385
Na

2 C0 3" K

2 C0

3

Table 44.3. Densities(g cm from equations in table 44.1

Mol X Na2 CC>3

T(K) 100 90 80 75 70 60 .58 50 40 30 25 20 10 0 1000 1.997

1010 1.992

1020 1.988 1.982

1030 1.983 1.978

1040 1.986 1.979 1.974

1050 1.982 1.979 1.975 1.969

1060 1.977 1.974 1.970 1.965

1070 1.989 1.978 1.973 1.970 1.966 1.961

1080 1.984 1.974 1.968 1.965 1.961 1.956 1.952 1.949

1090 1.980 1.975 1.969 1.964 1.961 1.957 1.952 1.947 1.944

1100 1.975 1.970 1.965 1.959 1.957 1.953 1.948 1.943 1.940

1120 1.973 1.966 1.961 1.956 1.950 1.948 1.948 1.943 1.938 1.935

1130 1.969 1.962 1.957 1.952 1.946 1.943 1.944 1.939 1.934 1.931

1140 1.967 1.964 1.957 1.952 1.947 1.941 1.939 1.939 1.934 1.930 1.927 1.924

1150 1.962 1.959 1.953 1.948 1.943 1.937 1.935 1 .935 1.930 1.925 1.922 1.919

1160 1.958 1.955 1.948 1.943 1.938 1.932 1.930 1.931 1.926 1.921 1.918 1.915

1170 1.954 1.950 1.943 1.939 1.934 1.928 1.926 1.926 1.921 1.917 1.913 1.911

1180 1.950 1.946 1.939 1.935 1.929 1.923 1.921 1.922 1.917 1.912 1.909 1.907 1.901

1190 1.945 1.941 1.934 1.930 1.925 1.919 1.917 1.918 1.913 1.908 1.905 1.902 1.896 1.893

1200 1.941 1.936 1.930 1.926 1.921 1.915 1.913 1.913 1.908 1.903 1.900 1.898 1.892 1.889

1210 1.927 1.932 1.925 1.921 1.916 1.910 1.908 1.909 1.904 1.899 1 .896 1.894 1.888 1.884

1220 1.933 1.927 1.921 1.917 1.912 1.906 1.904 1 . 904 1 . 900 1.895 1.891 1.889 1.883 1.880

1230 1.928 1.923 1.916 1.912 1.907 1.901 1. 899 1.900 1.895 1.890 1.887 1.885 1.379 1.875

1240 1.924 1.918 1.908 1.903 1.895 1.891 1.886 1.881 1.874 1.871

1250 1.882 1.876 1.870 1.866

1260 1.877 1.872 1.866 1.862

References [6-9].

3. Surface Tension (y)

Measurement method: pin detachment, maximum bubble

Y

= a + bT + cT

2 (44.3)

precision: in table 44.4 uncertainty:

pressure [7,10,11]

^ + 0.5%

Table 44.4. Parameters of equation (44.3), and precisions

Mol %

Na 2 0 0 3 a -b x 10 2 c x 10 5 Precision

0 243.908 6.37144 ±0 . 15%

25 866.024 115 .2236 47.8798 ±1.31%

50 272. 280 9.72033 1 . 61667 ±0 . 04%

58 202.781 - 8 .35561 -7 .45722 ±0.18%

75 259.582 5 .83335 ±0.09%

100 304 . 552 10 .97145 2 .44999 ±0.06%

386
Na2C02“K2C02

Table 44.5. Surface tension (dyn cm from equations in table 44.4

Mol % Na 2 CO 3 T(K) 100 75 58 50 25 0

1000 211.8 191 .

1020 210 .

190 .

1040 209 .

188 .

1060 197 .

207 .

187 .

1080 196.6 206 .0 186.2 180.1

1100 195 .

204.5 184.9 177.9

1120 194.3 202 .

183 .

176.1

1140 211.3 193 .

201.1 182 .

174 .

1160 210.3 191.9 181 .

173.7

1180 209.2 190 .

173.1 168 .

1200 208.2 189 .

172 .167 .

1220 207 .

166 .

1240 206.2 164 .

1260 205 .

163 .

1280 204.3 162 .

References [6,9-11].

4. Viscosity (r\)

Measurement method: oscillating sphere [12]

precision: not estimated uncertainty: ^ + 25%

Values interpolated from the graphical data.

Table 44.6. Viscosity (cp)

Mol %

Na. 2 C 0 3

T (K)

1023 1073 1123 1173

0 2.83

10 3.41 3 . 05

20 3.47 3 . 10

30 4.75 4.06 3.56 3 .18

40 4 .82 4 . 20 3 . 64 3 .24

50 4 .96 4 . 30 3.73 3 .29

60 5.12 4.41 3 . 81 3 .37

70 5 .21 4.48 3.84 3 . 39

80 5 .25 4 .50 3 . 88 3 . 38

90 3 .94 3 .45

100 4.04

References [12]

387
Na2C02~K2C02

5. Electrical Conductance (k)

Measurement method: ac technique [14]

k = A exp (-E/RT) (44.4)

precision: estimate not possible uncertainty: ^ ± 2,5%

Hata reported in equation form.

Table 44.7. Parameters of equation (44.4)

Hoi % Na2 C0 3 _ A

(ohm 1 cm 1 )

E (cal mol-1

) Temp . range

(K)

0 10,52 3830 1178-1281

10 10.85 3850 1157-1250

20 11.32 3880 1148-1258

30 11.49 3870 1076-1237

40 11.79 3860 1047-1246

50 12.20 3900 1044-1230

58 12.38 3910 1043-1226

60 12.98 3990 1073-1230

70 13.20 3910 1071-1222

80 13.65 3800 1086-1236

90 13.95 3700 1143-1254

100 14.12 3590 1145-1238

Table 44.8. Specific conductance (ohm ^cm *") from equations in table 44.7

Mol % Na

2 co

3

T(K) 100 90 80 70 60 58 50 40 30 20 10 0

1040 1.866 1.848

1060 1.934 1.915 1.886 1.830

1080 2.134 2.022 2.002 1.982 1.951 1.893

1100 2.399 2.206 2.092 2.069 2.049 2.016 1.956

1120 2.475 2.278 2.161 2.136 2.114 2.081 2.019

1140 2.724 2.550 2.349 2.230 2.203 2.181 2.145 2.081

1160 2.974 2.802 2.625 2.420 2.299 2.270 2.247 2.209 2.144 2.072 2.042

1180 3.054 2.879 2.699 2.491 2.367 2.336 2.312 2.273 2.205 2.133 2.100 2.054

1200 3.133 2.956 2.773 2.561 2.435 2.402 2.377 2.336 2.267 2.224 2.159 2.111

1220 3.211 3.032 2.847 2.631 2.503 2.467 2.442 2.399 2.328 2.284 2.217 2.167

1240 3.289 3.107 2.461 2.389 2.344 2.274 2.223

1260 2.403 2.278

1280 2.334

References [7,13,14].

6. Safety and Hazards

A. Hazard rating [15-17]

(i) Toxicity: K

2

CC> 3

, severe; Na

2

CC> 3

, slight.

(ii) Vapor pressure: Carbonates dissociate on heating:

M

2 C°3 ( £)

M

2°U)

+ CO

2(g)

(44.5)

388
Na

2 C0

3 -K

2 C0

3

For the min. melting mixture (m.pt. 710°C) , the CC>2 equilibrium dissociation pressure is v 1.1 x 10~° mm

at approx. 530°C

B. Disaster hazards [15,18-20]

(i) Molten salt bath "explosions": i.e., explosive generation

of steam due to bulk water "carry-over" and/or equipment

failure; i.e. explosive expansion of "trapped" air.

(ii) When heated at CO 2 pressures less than equilibrium,

carbonates decompose to alkali metal oxides; the

toxicology and disaster hazards of such oxides are the same as very strong caustics, i.e. react with

water or steam exothermically to form hydroxides that

are very aggressive to body tissues (chemical burns).

References [15-20].

7. Corrosion

Table 44.9. Corrosion studies from primary research literature

Studies References

Corundum, mullite,

f osterite 21

Ag; A1

2 0

3

( 0

atmosphere;

Na

2 C0

3 -K

2 C0

3 -Na

2 0) 22

Acid-base relationships

in molten carbonates 23-26

Hydrolysis (H

2 0) reactions 22,27,28

Corrosion in molten salts:

annotated bibliography 29

Molten carbonates: fuel

cells; thermal energy

storage; coal gasification,

power plant stack gases 30-35

References [21-36].

8. Diffusion

Measurement method: capillary [37]

List of diffusing species investigated in Na

2 C0

3 ~K

2 C0

3 as solvent

Na

+

, K

+

, C0

3

‘

Equation

D = A exp [-E/RT]

precision: in table 44.10,1

(44.6)

uncertainty: ^ + 201

389
Na

2 C VK

2 C0

3

Table 44.10.1. Parameters of diffusion equation (44.6), and precisions

Species A x 1 0

3 (cm 2 sec” 1

)

E (cal mol 1 ) Temp, range

(K)

Precis ion

K+

7 .61 11,840 1065-1240 ±1.5%

Na

+

8 .18 11,820 1080-1240 ±3 . 1%

003

"

2 .71 11,030 1030-1190 ±2.4%

5 2 -

Table 44.10.2. Self -diffusion coefficients, D x 10 (cm sec ),

from equations in table 44.10,1

TU) Na

+

K+ C0*“

1030 1.24

1040 1.30

1060 2.75 1.44

1080 3.32 3 .06 1.59

1100 3 .67 3.38 1 .74

1120 4 . 04 3.72 1 .91

1140 4.43 4.09 2 . 08

1160 4 .85 4.47 2 .26

1180 5 .29 4 . 88 2.45

1190 5.52 5.09 2 .55

1200 5.75 5 .31

1220 6.24 5.76

1240 6.75 6 . 23

References [37]

9. Heat of Fusion (LH^.)

Measurement method: drop calorimetry [38]

Table 44.11. Heat of fusion

Mo 1 % Na

2 CO^ AH°

t -1

(kcal mol ) Uncertainty

56 4 .

* ± 2%

References [38]

390
Na2C0j-K2C02

10.

Heat Capacity (C^)

Measurement method: drop calorimetry [38]

Table 44.12. Heat capacity

C Temp, range

Mol % Na

2 C0

3 -1 -1

(cal K mol ) (K) Uncertainty

56 44.3 ± 0.1 983-1197 ^ ± 0.5%

References [38]

11.

Volume Change on Melting (A Vj.)

Measurement method: estimated; from densities [39]

Table 44.13. Volume change on melting

Mol % Na

2 C0

3 (4V

f /Vs

) Uncertainty

56 14.4% ^ ± 8%

References [39]

12.

Vapor Pressure (

va p

Measurement method: cited with each data set [22,31,39]

No systematic studies of vaporization as molecular carbonates have

been reported, i.e.,

M

2 C0 3U) M

2 C0

3 (g)

(44.7)

For the CC>2 decomposition of molten carbonates and other possible

processes contributing to vaporization, the data for the molten

minimum melting NajK/CO^ system are as follows.

Decomposition Processes

CC>2 dissociation and equilibrium pressure for the molten minimum

melting Na,K/COj mixture (56:44; m.pt. 710°C)

M

2 C0

3 (£)

* M 2° (£)

+ CO

2(g) (44.8)

CQ- (atm) = ^d ^ a

a M CO

2 LU

3(£)

/ aM 0

1 M

2 U

(Z)

(44.9)

Here M is the Na,K cationic mixture in this molten binary system,

p is the equilibrium CO

2 dissociation pressure, and a the thermodynamically defined activity. For practical purposes, eq. (44.9)

is generally expressed in the mol fraction scale [X], as:

CO, (atm) = ^da ^MM CO

2 LU

3(£) /^M 0

2 U

(£)

(44.10)

Thus the "equilibrium pressures" depend on the oxide content, i.e.

the quality of the "carbonate", and its previous history.

(i) Equilibrium dissociation constant,

Measurement method: emf technique [22]

log K

d

= -16780/T + 7.32 (44.11)

391
Na

2 C03~ K

2 C0

3

Precision: not estimated, uncertainty: ^ + 1%

Table 44.14.1. CO

2 dissociation constants from equation (44.11)

“ror minimum melting mixture

T(K)

K

d

(atm)

T(K)

K

d

(atm)

800 2 . 21 x 10~ 14 1050 2.18 x 10 -9

850 3.79 x 10 _1

1100 1.16 x 10~ 8 900 4.72 x 10 -12 1150 5 . 35 x 10" 8 950 4.54 x 10" 1

1200 2.17 x 10 -7

1000 3.47 x 10 _1 °

(ii) Equilibrium CC>2 dissociation pressures

Measurement method: thermodynamic; calc’d [39]

No direct measurements of the equilibrium CO 2 dissociation pressures

have been reported. Based on Andersen’s (1975) values for , and

the preceding expressions for p^q^j the equation for Pqq^ as a function

of T and oxide content for this molten binary system is:

log p co

(mm) = + 10.2008 - log n (44.12)

where n is the oxide content (i.e. mols oxide/mol carbonate) if

n <<< unity. The values in table 44.14.2 summarize the thermodynamically predicted p^^ pressures for a range of n (comparable

to the oxide content in related systems, e.g,

ternary eutectic)

Na

2 C03

; K

2 C03

Table 44.14.2. Equilibrium CO 2 dissociation pressures

(mm) from equation (44.12) for minimum melting mixture

T

(K)

n(mol oxide per mol carbonate)

1.5 x 10" 5 3 x 10~ 5 1.5 x 10“ 4 3 x 10" 4

CO2 pressure (mm)

800 1.1 x 10 -6

5 . 6 x 10 -7 1.1 x 10" 7 5 . 6 x 10 -8

900 2.4 X 10 -4 1.2 x 10 -4 2.4 x 10~ 5 1.2 x 10~ 5 1000 1.7 x 10 2 8.8 x 10 3 1.7 x 10 -3 8.8 x 10~ 4 1100 0 .

0 .

6 x 10 -2

3 x 10 -2

1200 11 5 .

1.1 0 .55

Remarks: The oxide is dissolved in the molten carbonate, and

since the values of the equilibrium pressures depend

on the composition of the solution, the dissociation

pressures do not have unique values unless the values

of n are specified.

Vaporization of molten carbonates

Measurement method: critical analyses [31]

The various "vaporization" data, based on electrolyte losses from

high temperature molten carbonate fuel cells, and the thermodynamics

of associated reactions, have been critically examined by Maru et al.,

(1976). For a summary of the data status, refer: Li ? CO,, present

work.

392
References [22,31,39-43].

Na

2 C0

3

-K

2 C0

3

13. Thermal Conductivity (liquid) f A ^

J No thermal conductivity studies reported.

14. Thermal Conductivity (solid) (X ) s No thermal conductivity studies reported.

15. Cryoscopic Constant (k^.)

Measurement method: calc'd; from AH£ [39]

Table 44.15. Cryoscopic constant

Mol % Na

2 C0

3

k

f (K mol

_1 kg

-1

) Uncertainty

56 49 .

'v ± 2%

References [38,39].

16. References

[1] Reisman, A.

J . Amer . Chem. Soc., 81, 810 (1959).

[2] Janz, G. J. , Downey

J. R. , Jr., Allen, C. B., and Tomkins, R. P. T.

,

"Eutectic Data", - 2 vols ; ERDA-TID - 27163-PI 8 P 2; NTIS,

Washington , D. C. (1977)

[3] Janz , G . J . , Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T. , I . Printing Office, Washington, D. C. (1978).

[4] Belyaev, I. N. , and Sholokovich, M. L. , J. Appl. Chem. , USSR, 25,

733 (1952).

[5] Janz, G. J. , and Lorenz, M. R. , J. Chem. Eng. Data, 6_, 321 (1961).

[6] Spedding, P. L. , J. Electrochem. Soc., 117 , 180 (1970).

[7] Ward, A. T. , and Janz, G. J., Electrochim. Acta, 1_0 , 849 (1965),

[8] Polyakov, V. D. , and Berul, S. I., Izv. Sek. Fiz-Khim., Anal.,

Akad. Nauk SSSR, 22, 173 (1953).

[9] Janz, G. J. , and Lorenz, M. R. , J. Electrochem. Soc., 108 , 1054 (1961).

[10] Moiseev, G. K. , and Stepanov, G. K. , Tr. Inst. Elektrokhim. , Akad.

Nauk SSSR Ural. Fil. (Sverdlovsk)., 69 (1964).

[11] Moiseev, G. K. , and Stepanov, G. K. , Tr. Inst. Elektrokhim., Akad.

Nauk SSSR, Ural. Fil., 65 (1964).

[12] Vorob'ev, G. V. , Pal'guev, S. F. and Karpachev, S. V. , "Electrochem.

of Solid and Molten Electrolytes "

3 3_, 33 (1966 ), Consultants Bur.,

New York; Trudy No. 6; Inst. Electrochem. Urals Acad. Sci. (1965).

[13] Karpachev, S. V., and Vorob'ev, G. V., Trans. Inst. Electrochem., 1,

52 (1960).

[14] Spedding, P. L. , J. Electrochem. Soc., 120 , 1050 (1973).

[15] "Dangerous Properties of Materials", Sax, N. I., Van, Nostrand

Reinhold Co., N. Y. (1969).

393
Na

2 CO

3

-K

2 C0

3

[16] "Registry of Toxic Effects of Chemical Substances'', Christensen, H. E.

,

and Lubinbyhl, T. T. , eds., U. S. Dept. H. E. W. , U. S. Gov’t

Printing Office, Washington, D. C. (1975).

[17] Vapor pressure, calculated (see p. 392, this work).

[18] "Potential Hazards in Molten Salt Baths for Heat Treatment of Metals"

,

National Board Fire Underwriters Research Report No. 2 (1954).

[19] "Handbook of Reactive Chemical Hazards'

3 Bretherwick, L. , Butterworths

Co. , London (1975)

[20] Janz, G. J., Tomkins, R. P, T., Downey, J, R. , Jr., and Allen, C. B.,

"Safety and Hazards ”, Chapter in "Eutectic Bata"3 ERDA TID- 27 1 63 -PI

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[21] Yamaguchi, A., and Sakakura, M. , Yogyo Kyokai Shai, 7_9, 397 (1971).

[22] Andersen, B. K. , "Thermodynamic Properties of Molten Alkali Carbonates"

,

Ph.D. Thesis, Tech. Univ. Denmark (1975).

[23] Dubois, J. , "Chemical and Electrochemical Reactions of Molten Alkali

Carbonates as Fuel Cell Electrolytes ", Ph.D. Thesis, Fac. Sci. Univ.

Paris, France (1964).

[24] Ingram, M. D. , and Janz, G. J. , Electrochim. Acta, IJ[, 783 (1965).

[25] Busson, N. , Palous, S., Buvet, R. , and Millet J J. , Compt. Rend.,

260 , 720 6097 (1965).

[26] Ingram, M. D. , Baron, B., and Janz, G. J. , Electrochim. Acta, 11 , 1629 (1966).

[27] Janz, G. J. , J. Chem. Educ. , 4_4, 581 (1967).

[28] Busson, N. , Palous, S. , Millet, J., and Buvet, R. , Electrochim. Acta,

12, 910 (1967).

[29] Janz, G. J. , and Tomkins, R. P. T., Corrosion, .34 (in press) (1978).

[30] Maru, H. C. , et al. (Institute of Gas Technology) , "Molten Salt

Thermal Energy Storage Systems: Salt Selection" 3 Rpt. COO-2888-1,

ERDA Contract No. E (11-1) -2888 , NTIS, U. S. Dept. Commerce,

Springfield, Va. , (Aug. 1976).

[31] Maru, H. C. , et al. (Institute of Gas Technology), "Fuel Cell Research

on Second Generation Molten Carbonate Systems: II. Characteristics

of Carbonate Melts"3 Quarterly Status Rpt., Project 8984, ERDA

Contract No. 31-109-38-3552, (Sept. 1976).

[32] Botts, W. V., Kohl, A. L., and Trilling, C. A., "Low BTU Gasification

of Coal by Atomics International's Molten Salt Processes"3 Proceedings of the llth Intersociety Energy Conversion Engineering

Conference, 1^, 280 (Sept, 1976).

[33] Cover, A. E . ,- Schreiner, W. C,, and Skaperdas, G. T., "The Kellogg

Coal Gasification Process

3 Extended Abstracts, American Chemical

Soc. Meeting, Washington, D. C. (1971).

[34] Atomics International, "Development of a Molten Carbonate Process

for Removal of Sulfur Dioxide from Power Plant Stack Gases”,

Progress Rpt, No. 2, U. S. Public Health Services, Contract

PH 86-67-128, Canoga Park, Cal. (1968),

[35] Grantham, L. F., and Ferry, R. B., " Corrosion in Alkali Metal

Carbonate - Based Melts", Proc. International Symp , Fused

Salts; J. P. Pemsler, ed., Electrochemical Soc., Inc., Princeton,

N, J,, 270 (1976).

394
Na2C0j - I^CO^

[36] Bonar, J. A., Clark, C. B. , and Sandmeyer, K. H. , "Interaction of

Oxide Refractories with the Environment of High Temperature Reactors", p. 807, in "Proceedings Int. Symp . on Metal -Slag -Gas

Reactions and Processes", The Electrochemical Soc., Princeton,

N. J. (1975).

[37] Spedding, P. L., and Mills, R. , J. Electrochem. Soc,, 113 , 599 (1966).

[38] Janz, G. J., and Perano, J. L., Trans. Faraday Soc., 6_0, 1742 (1964).

[39] Janz, G. J., et al . , (MSDC-RPI) unpublished work (1977).

[40] Broers, G. H. J., "High Temperature Galvanic Fuel Cells", Ph.D.

Thesis, Univ. Amsterdam (1958).

[41] Broers, G, H. J.,and Schenke, M., "Long-Run Experiments on High

Temperature Molten Carbonate Fuel Cells", Chapter in "Hydrocarbon

Fuel Cell Technology", Baker, B. S., ed., Academic Press, N. Y.

(1965) .

[42] McQuade, J. M., Hamlen, R. P,, and Nelson, R. R., "Alkali Carbonate

Fuel Cell", U. S. Patent 3,268,365 (1966) Aug. 23; (assigned to

General Electric Co).

[43] Trachtenberg, I., and Cole, D. F., "Electrolyte Studies in Molten

Carbonate Fuel Cells" Chapter in "Fuel Cell Systems II", Baker,

B, S. ed . , Amer. Chem . Soc., Advances in Chemistry Series, 90 , 268-280 (1969).

395
XLV. Sodium Nitrate-Potassium Nitrate: NaNO^-KNO^

1. Melting Temperatures CT ) Pure substance melting points:

NaN0

3

: 307°C

KN0

3

: 337°C

Minimum melting mixture : 222°C, composition: 54 mol % KN0

3

Figure 45.1. NaNOj-KNOj phase diagram

References [1-4] .

2. Density (p)

Measurement method: Archimedean technique [5]

Two- independent- variable equation

p = a + bT 2 + cCT

2 (C = mol % KNC>

3

) (45.1)

precision: in table 45.1 uncertainty: ^ + 0.51

Table 45.1. Coefficients of two- independent-variable equation (45.1)

396
NaN0

3 -KN0

3

_

*7 Table 45.2. Densities (g cm ) from two - independent -variable

equation (45.1)

Mol % NaNCh

T ( K ) 100 90 80 70 60 .50 40 30 20 10 0 46

625 1.878 1.876 1.874 1.872 1.870 1.867 1.865 1.863 1.861 1.859 1.856 1.866

630 1.875 1.873 1.871 1.869 1.866 1.864 1.862 1.860 1.857 1.855 1.853 1.863

635 1.872 1.870 1.868 1.865 1.863 1.861 1.859 1.856 1.854 1.852 1.850 1.860

640 1.869 1.867 1.865 1.862 1.860 1.8 58 1.855 1.853 1.851 1.849 1.846 1.857

645 1.866 1.864 1.862 1.859 1.857 1.855 1.852 1.850 1.548 1.845 1.843 1.854

650 1.863 1.861 1.858 1.856 1.854 1.851 1.849 1.847 1.844 1.842 1.839 1.850

655 1.860 1.858 1.855 1.853 1.850 1.848 1.846 1.843 1.841 1.838 1.836 1.847

660 1.857 1.854 1.852 1.850 1.847 1.845 1.842 1.840 1.837 1.835 1.832 1.844

665 1.854 1.851 1.849 1.846 1.844 1.841 1.839 1.836 1.834 1.831 1.829 1.840

670 1.851 1.848 1.845 1.843 1.840 1.838 1.835 1.833 1.830 1.828 1.825 1.837

675 1.847 1.845 t . 842 1.840 1.837 1.835 1.832 1.829 1.827 1,824 1.822 1.834

680 1.844 1.842 1.839 1.836 1.834 1.831 1.829 1.826 1.823 1.821 1.818 1.830

685 1.841 1.838 1.836 1.833 1.830 1.828 1.825 1.822 1.820 1.817 1.815 1.827

690 1.838 1.835 1.832 1.830 1.827 1.8 24 1.822 1.819 1.816 . 1.814 1.811 1.823

695 1.834 1.832 1.829 1.826 1.823 1.821 1.818 1.815 1.813 1.810 1.807 1.820

700 1.831 1.828 1.825 1.823 1.820 1.817 1.814 1.812 1.809 1.806 1.803 1.816

705 1.828 1.825 1.822 1.819 1.816 1.814 1.811 1.808 1.805 1.803 1.800 1.813

710 1.824 1.821 1.819 1.816 1.813 1.810 1.807 1.804 1.802 1.799 1.796 1.809

715 1.821 1.818 1.815 1.812 1.809 1.807 1.804 1.801 1.798 1.795 1.792 1.805

720 1.817 1.815 1.812 1.809 1.806 1.803 1.800 1.797 1.794 1.791 1.788 1.802

References [5-17]

3. Surface Tension (y)

Measurement method: plate detachment [18]

Two- independent -variable equation

Y

= a + bT + cCT 2 + dTC 2 (C = mol % KNC>

3

) (45.2)

precision: in table 45.3 uncertainty: ^ ±11

Table 45.3. Coefficients of two - independent -variable equation (45.2)

a b x 10 2 c x 10 7 d x 10 7 Precision

155 . 67822 -6.27403 -2 . 31449 5 .98777 ±0.1%

397
NaN0

3 -KN0

3

Table 45.4. Surface tension (dyn cm ^) from two- independent -variable

equation (45.2)

Mol X NaNQ 3

T(K) 100 90 80 70 60 50 40 30 20 10 0 46

500 122.2 122.1

510 121.8 121.4 121.2 121.3

520 121.0 120.7 120.4 120.6

530 120.3 120.0 119.7 119.4 119.8

540 120.1 119.6 119.2 118.9 118.7 119.1

550 119.4 118.9 118.5 118.2 117.9 117.7 118.4

560 119.2 118.7 118.2 117.8 117.4 117.1 116.9 117.6

570 118.5 118.0 117.5 117.0 116.6 116.3 116.1 115.9 116.9

580 117.9 117.3 116.7 116.3 115.9 115.5 115.3 115.1 116.1

590 117.9 117.2 116.6 116.0 115.5 115.1 114.8 114.5 114.3 114.1 115.3

600 117.2 116.5 115.9 115.3 114.8 114.3 114.0 113.7 113.4 113.3 114.6

610 116.6 115.8 115.2 114.5 114.0 113.6 113.2 112.9 112:6 112.4 113.8

620 116.8 115.9 115.1 114.4 113.8 113.3 112 . 8 112.4 112.0 111.8 111.6 113.1

630 116.2 115.3 114.5 113.7 113.1 112.5 112.0 111.6 111.2 110.9 110.7 112.3

640 115.5 114.6 113.8 113.0 112.3 111.7 111.2 110.8 110.4 110.1 109.9 111.5

650 114.9 114.0 113.1 112.3 111.6 111.0 110.4 110.0 109.6 109.2 109.0 110.8

660 114.3 113.3 112.4 111.6 110.9 110.2 109.6 109.1 108.7 108.4 108.1 110.0

670 113.6 112.6 111.7 110.9 110.1 109.5 108.9 108.3 107 .107.5 107.3 109.2

References [2,18-22],

4. Viscosity (r\)

Measurement method: oscillating sphere [12]

n = a + bT + cT

2 + dT 3 (45.3)

precision: in table 45,5 uncertainty: 'v + 10%

Table 45.5. Coefficients of equation (45.3) , and precisions

Mol %

NaNO 3 a -b x 10 2 c x 10 5 d x 10 8 Precision

50 90 . 8112 35 .1716 46 . 64877 -20 . 8610 ± 2.2%

75 25.6156 6.2877 4 . 08206 0 ± 0.47%

100 14.2464 1 .1549 -3.46657 3 .6440 ± 0.33%

n = A exp (E/RT) (45.4)

precision: in table 45.6 uncertainty: ^ ± 3%

398
NaN0

3 -KN0

3

Table 45.6. Coefficients of equation (45.4), and precisions

Mol % NaNO 3 A x 10 2 E (cal mo

-

) Precision

0 7 .127 4506 ±0.35%

25 8.710 4141 ±0.51%

Table 45.7. Viscosity (cp) from equations in tables 45.5 and 45.6

T

(K)

Mol % NaNO 3 100 75 50 25 0

520 4.725

530 4 .381

540 4.064

550 3.772

560 3.506

570 3.038 3.262 3.372

580 2.879 3 .040 3.165 • 590 2.728 3.839 2.978

600 2.708 2.585 2 .657 2.808

610 2.574 2.450 2 .494 2.653

620 2.445 2.323 2.348 2.511 2.763

630 2.323 2.205 2.217 2.3-8 0 2 . 608

640 2.208 2.094 2.100 2.260 2.465

650 2.101 1 . 992 1.997 2.150 2.334

660 2 . 000 1 . 899 1 . 906 2 . 048 2.214

670 1 . 907 1 . 812 1.826 1.954 2.102

680 1.822 1.735 1 .755 1 .867 2.001

690 1 .744 1.665 1.692 1.786 1 .906

700 1.675 1.604 1.636 1.710 1.819

710 1 .614 1.551 1.585 1.640 1.738

720 1.562 1.506 .1.540 1.574 1.662

References [2,6,12,16,23-29].

5. Electrical Conductance (k)

Measurement method: ac technique [30]

k = a + bT + cT

2

precision: in table 45.8

(45.5)

uncertainty: ^ + 0,5%

399
NaN0

3 -KN0

3

Table 45.8. Parameters of equation (45.5), and precisions

Mol % NaN0 3 -a b x 10 2 -c x 10 5 Precision

0 2 .4566 0.67289 0.27583 ±0.1%

24.85 2 . 0386 0.56214 0.18254 ±0.08%

50.31 2 . 4156 0.68424 0.25391 ±0.23%

75.09 3 . 0522 0.89412 0.39159 ±0 . 20%

100 2 .9565 0.88732 0.35949 ±0.15%

Table 45.9. Specific conductance (ohm ^cm ^) from equations in

table 45.8

T (K)

Mol 1 NaNO

3

100 75. 09 50.31 24.85 0

560 0.620 0.537

570 0.660 0.573

580 0.816 0.699 0.608

590 0.860 0.738 0.643

600 0. 903 0.776 0.677

610 1.118 0.945 0.813 0.711

620 1.163 0.986 0.851 0.745

630 1.207 1.027 0.887 0.778 0.688

640 1 . 250 1.066 0.924 0.811 0.720

650 1 .292 1.105 0.959 0.844 0.752

660 1 . 334 1.143 0.994 0.876 0.783

670 1.375 1 .181 1 . 029 0.908 0.814

680 1 . 415 1 . 063 0.940 0.844

690 1 .454 1.097 0.971 0.873

700 1.493

710 1 .531

720 1 . 569

References [2,5,7,8,10,16,30-42] . Safety and Hazards

A. Hazard rating [43-45]

(i) Toxicity: NaNC>

3

, low; KN0

3

, low; (permitted as food additive)

(ii) Vapor pressure: eutectic (m.pt. 222°C) melts without decompos

ition; the melt is stable in air to approx. 500°C; at higher

temperatures, nitrates dissociate:

MN0

3 ~t— MN02 + h0

2 (45.6)

The nitrite and nitrate undoubtedly co-exist in quasiequilibrium in a temperature range comparable to the single

components (i.e., to ^ 800°C) , but the binary mixture

(above) has not been investigated.
NaN0

3 -KN0

3

B. Disaster hazards [43,46-48]

Molten salt bath "explosions": violent generation of steam

due to bulk water "carry-over" and/or equipment failure;

sudden explosive expansion of "trapped" air.

On decomposition, nitrates emit toxic fumes (oxides of

nitrogen) viz:

MN0

3 —* MN02 + h0 2 (45.7.1)

2MN0

2 * M

2 0 + NO + N0

2 (45.7.2)

The subsequent decomposition reactions are complex; if the

gas phase is continuously removed, the nitrite decomposition

(above) to NO and NOg is dominant. If the gas phase is not

immediately removed, the NO may re-oxidize the nitrite

to nitrate.

(iii) Nitrates are powerful oxidizing agents; violent (explosive)

reactions possible in molten nitrates and carbonaceous materials

(organic compds ; oils; carbon;...); aluminum alloys and bath

sludges (e.g., iron oxides); magnesium alloys. Dangerous.

References [43-48] .

7. Corrosion

Table 45.10. Corrosion studies from primary research literature

S tudies Ref er ences

Cu, Cd, Pb, Ni, Zn 49

Cr-Mo alloys, cast iron 50

Pt, Au, Ag, Ni, Cu, Hg, W 51

Metals 52

Fe, low carbon steels 53

Various steels and Ti alloys 54

Hydrogen, H

2 0 behavior 55

Electrochem. approach 56,57

Thermodynamic redox diagrams 58,59

Reviews: corrosion, molten salts 60-62

Annotated corrosion biblio. 63

(i)

(ii)

References [49-63] .

8. Diffusion

Measurement method: cited in tabulations

List of diffusing

Na

+

, K

+

, Li+

3 o'* o\-. o

2 -.

species investigated in NaN0

3 ~KN03 as solvent

Tl 3 Tb , Ag , Cd , OH', C0 2 ~

3 C

2 °

24~> N0~2’

Eg

2 Cl

2 + dg

Br

2 + Ce

3+

S I~ , H

Pr

3 +

2

J °2 J

Nd

CO

3+

2

' H 2°

401
NaN0

3 -KN0

3

The italicized species indicate studies with insufficient data-sets for

temperature dependence characterization of diffusion coefficients. For

numerical values: see table 45.11.5.

precision: in cable 45.11.2 uncertainty: in table 45.11.1

For diffusion techniques, uncertainties, and species: see table 45.11.1

Equation D = A exp[-E/RT] (45.8)

Table 45.11.1. Diffusion techniques, uncertainties, and species

Diffusion techniques

of recommended study

Uncertainty

(in values of D)

Species

capillary ^±15%

+ + 4- Li , Na , K

chronopotentiometry ^±10% + 2+ 2-

Ag , Cd , 0 ,

linear sweep voltammetry v± 20%

VlTl

+

, Pb

2+

, Ag

+

, Cd

2+

,

voltammetry (cyclic) ^±20%

Cl”, Br~, OH

-

u

2 + Hg

pulse polarography 'vi 2 0% Cl , Br , I

rotating disc electrode %±20Z I > CO^ , CO

^

t ®2’

paper electrophoresis ^±15%

O

2-

, H , 0 , HO,

u

2 + Hg

2 Na

+

, K+

For numerical values: see tables 45.11.2 - 45.11.5

402
NaN0

3 -KN0

3

Table 45.11.2. Parameters of diffusion equation (45.8), precisions,

recommended study

Species A x 10 3 (cm 2 sec

-1

)

E (cal mol 1

) Temp, range

(K)

Precis ion Recommended

study

(a) NaNO ^ -KN0

3 eutect ic

Na

+ 0.533 4013 550-720 ±3.7% 73

K+ 1.352 5380 550-720 ±4 . 8% 73

OH" 12 . 935 8581 510-620 ±0.8% 77,79

(b) NaN0

3 -KN0

3 (30.3 mol % NaN03

)

Na

+ 1.323 5220 590-670 ±0.2% 75

K+ 1.357 5468 590-670 ±0.1% 75

(c) NaNO

3 -KN03 (51.7 mol % NaN03

)

•

Na

+

1 .404 5228 590-670 ±0.13% 75

K+ 1.438 5462 590-670 ±0.35% 75

(d) NaNO

3 -KN0

3 (79.7 mol % NaNO3

)

Na

+

1 . 180 4958 590-670 ±0.65% 75

K+ 1.425 5401 590-670 ±0.25% 75

Table 45.11.3. Self -diffusion coefficients, D x 10^ (cm^sec

T Eutectic Melt 30.3 mol Z NaNO, 56.7 mol Z NaNO

^ 79.7 mo 1 Z NaNO

^ (K) Na

+

K+ Na

+

K+

Na

+

K+

Na

+

K+

550 1.36 0.984

570 1.54 1.17

590 1.74 1.37 1.54 1.28 1.62 1.36 1.72 1.42

610 1.95 1.60 1.78 1.49 1.88 1.59 1.97 1.65

630 2.16 1.84 2.04 1.72 2.16 1.83 2.25 1.91

650 2.38 2.10 2.32 1.97 2.45 2.10 2.54 2.18

670 2.62 2.38 2.62 2.23 2.77 2.38 2.85 2.47

690 2.86 2.67

710 3.10 2.98

720 3.23 3.15

403
NaN0

3 -KN0

3

Table 45.11.4. Diffusion coefficients in

the eutectic melt

T(K)

d oh- x 105

(cm 2 sec -1

)

T(K)

D 0H- x 105

(cm 2 sec -1

) 510 0.272 570 0.663

520 0.320 580 0.755

530 0.374 590 0.857

540 0.435 600 0.968

550 0.503 610 1 . 09

560 0.579 620 1.22

Table 45.11.5. Diffusion coefficients for species not

included in tables 45.11.2 to 45.11.4

Species Melt composition

(mol % NaNO ^

)

T(K)

D x 10 5 (cm 2 sec

- 1 ) Recommended

study

Li+ 51.7 522 1 .

67

619 2.2

675 3 .

Tl + eutectic 525 1.07 90

Pb 2 + eutectic 518 0.40 66,83,90

Ag

+ eutectic 523 0.40 64,66,70,72

536 0.73 82 ,83

553 1.10

570 1 .30

590 1 .59

Ag

+

20 588 1.65 74

613 1.94

633 2.14

Ag"

1 40 588 1.76 74

613 2 .11

633 2 .26

Ag

+

45 573 1 . 68 80

Ag

+

60 588 1 .83 74

613 2.14

633 2.32

Ag

+

80 588 1 . 94 74

613 2 .25

633 2.47

Cd

2+ eutectic 523 0.47 66,71, 83,90

Cd

2 + 40 523 2 . 3 4a 76

cd

2+

45 529 0.30 80

598 0.80

Hg

2 + eutectic 523 0.14 69

404
NaN0

3 -KN03

Table 45.11.5. Diffusion coefficients for species not

included in tables 45.11.2 to 45 . 11 . 4

- -Continued

Species Melt composition

(mol % N aNO

3

)

T(K)

D x 10 5

( cm 2 sec

-1

) Recommended

study

Hg

2 + eutectic 523 0.13 69

Ce

3 +

40 523 19 .

a 76 , 81

Pr

3 +

40 523 0.5 76

Nd 3 +

40 523 14 .

a 81

Cl" eutectic 518 0.69 84,90,91

Br" eutectic 518 0.70 84,90,91

I~ eutectic 518 0.68 78,84

0

2 eutectic 502 0.48 86

eutectic 502 0.31 86

o

2 - eutectic 523 2 . 24 88

C0 3~ eutectic 510 0.31 87

C 2°4* eutectic 523 1.03 88

NO

2 eutectic 523 2.75 88

H„ eutectic 571 5 .20 89

2 513 7 .80 92

°2 eutectic 550 31 .

68

co

2 eutectic 510 1 .

87

h

2 o eutectic 503 1.9 85

a Values are improbable, possibly by a factor of 20.

For the underlined species the temperature dependence of D reported

in graphical form; see [90, 91, 78, 87].

References

Na

+

, 73, 75; K

+

, 73, 75; Li

+

, 67; Tl

+

, 90; Pb

2+

, 66, 83, 90; Ag

+

, 64,

70, 72, 82, 83; Cd 2 +

, 66 , 71 , 76 , 80, 83, 90; Hg

2+

, 69; Hg

2+

, 69; Ce

3 +

, 76

81;

O Pr

3+

, 76 , 83 ; Nd 3 +

9 81; °2 ’ 86; 0

2-

2

’ 86; 0

2 ", 88 ; OH", 77, 79, 82;

C°3 87; C

2 °r. 88 ; NO- , 88 ; ci ", 84 , 90 , 91; Br", 84, 90, 91; i", 78 , 84

90, 91; h

2

, 89; °2 ’ 92; co

2

, 87; h

2 o, 85 .

405
NaN0

3

-KN0

3

9. Heat of Fusion (h H^,)

Measurement method: differential calorimetry [93]

precision: not estimated uncertainty: ± 2%

Table 45.12. Heats of fusion

Compos i t ion

(mol % KN0

3

) AH?

(kcal mol )

T m

(°C)

0 3 .600 310

25 3.382 275

40 3.290 243

50 3.195 227

60 3 .100 230

75 2 .802 260

87 2 . 685 300

100 2 .300 337

T is defined as the temperature at which disappearance of last traces of

sSlid would be noted during fusion; interpolated from phase diagram.

The value for KNO3 (100%) appears low relative to the recommended value

(see KNO3) . The value for NaNC>3 (100%) is in close accord with recommended

value (see NaN0

3 ).

References [93] .

10. Heat Capacity

Measurement method: drop

precision:

calorimetry [94]

53.44 - 2.638 x 10' 2 T (45.9)

'b + 0.5% uncertainty ^ + 3%

Table 45.13. Heat capacity from equation (45.9) for

minimum melting mixture

T(K)

C

P (cal K Uol 1

)

T00

C

P_

(cal K Vol 1 )

510 39 .99 650 36.29

520 39 . 72 660 36.03

530 39.46 670 35.77

540 39 .19 680 35.50

550 38.93 690 35 .24

560 38.67 700 34. 97

570 38.40 710 34.71

580 38.14 720 34.45

590 37.88 730 34. 18

600 37.61 740 33.92

610 37.35 750 33 .66

620 37.08 760 33.39

630

640

36 . 82

36.56

770 33. 13

References [94] .

406
NaN0

3

-KN0

3

11 . Volume Change

Measurement

on Melting (A

method: capillary

Table 45.14.

technique [95]

Volume change on melting

(AV

f /Vs

) Uncertainty

4.6 % ^ ± 12%

References [95,96].

12. Vapor Pressure (P vap)

No vaporization studies. For observations on thermal decomposition processes

in molten nitrates (to nitrites, oxides, with formation of gaseous oxides

of nitrogen, oxygen): see NaN0

3 and KNOj.

13. Thermal Conductivity (liquid)

Measurement method: concentric cylinder [99]

A = a + bT (45.10)

precision: not estimated uncertainty: ^ ± 20%

Results were reported as equations only.

Table 45.15. Parameters of equation (45.10), and temp, range

Mol % KN0

3 a x 10^ b x 10

7 Temp . range

(K)

25 10.490 3.70 604 - 730

50 9.318 4 . 60 612 - 727

75 7 .0298 7 .40 624 - 727

Table 45.16. Thermal conductivity from equations in

table 45.15

T(K) 25 mol % KN0

3 50 mol % KN0

3 75 mol % KN0

3 610 12.75 12.12

620 12.78 12.17

630 12 .82 12.22 11 . 69

640 12 .86 12.26 11.77

650 12.90 12.31 11 . 84

660 12 . 93 12 .35 11 .91

670 12 .97 12 .40 11.99

680 13 . 01 12.45 12 .06

690 13.04 12.49 12.14

700 13 . 08 12 . 54 12.21

710 13 .12 12 . 58 12.28

720 13 .15 12.63 12.36

730 13 .19 12 . 68 12.43

References [97-100]

407
NaN0

3 -KN03

14. Thermal Conductivity (solid) (X ) J s No thermal conductivity studies reported,

15. Cryoscopic Constant (k,J

No data.

16. References

[1] Kofler, A., Monatsh. Chem. , 86, 646 (1955).

[2] Bergman, A. G., and Beruli, S. I., Izv. Sekt . Fiz. Khim. Anal., 21, 178

(1952) .

[3] Janz, G. J., Downey, J. R. , Jr., Allen, C. B. , and Tomkins, R. P. T.

,

"Eutectic Data ", - 2 vols.; ERDA-TID- 27163-PI 8 P2; NTIS, Washington,

D. C. (1977).

[4] Janz, G. J., Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T.,

"Physical Properties Data Compilations Relevant to Energy Storage. I. Molten Salts: Eutectic Data"

,

NSRDS-NBS- 61 ; U. S. Gov't Printing

Office, Washington, D. C. (1978).

[5] Murgulescu, I. G. , and Zuca, S., Rev. Chim. (Roumaine) , 2, 227 (1959).

[6] Fawsitt, C. E. , J. Chem. Soc., 93, 1299 (1908).

[7] Sandonnini, C. , Gazz. Chim. Ital., 50, 289 (1920).

[8] Papaioannou, P. C., and Harrington, G. W. , J. Phys . Chem., 68, 2424 (1964)

[9] Polyakov, V. D. , and Beruli, S. H. , Izv. Sekt. Fiz. Khim. Anal.,

26, 164 (1955).

[10] Goodwin, H. M. , and Mailey, R. D. , Trans. Am. Electrochem. Soc., 11,

211 (1907).

[11] James, D. W. , and Liu, C. H. , J. Chem. Eng. Data, 8_, 469 (1963).

[12] Murgulescu, I. G., and Zuca, S. , Electrochim. Acta, 14^, 519 (1969).

[13] Powers, P. I., Katz, J. L., and Kleppa, 0. J. , J. Phys. Chem., 66, 103

(1962).

[14] Laybourn, K. , and Madgin, W. M. , J. Chem. Soc., 1 , 1 (1934).

[15] Boxall, L. G., and Johnson, K. E. , J. Chem. Eng. Data, 16, 204 (1971).

[16] Janz, G. J., Dampier, F. W. , Lakshminarayanan , G. R. , Lorenz, P. K., and

Tomkins, R. P. T., "Molten Salts: Volume I, Electrical Conductance,

Density 3 and Viscosity Data", NSRDS-NBS-15 , 139 pages (1968),

[17] McAnley, W. J., Rhodes, E., and Ubbelohde, A. R. , Proc. Roy. Soc., 289A,

151 (1966).

[18] Bertozzi, G., and Sternheim, G., J. Phys. Chem., 68, 2908 (1964).

[19] Boardman, N. K. , Palmer, A. R. , and Heymann, E. , Trans. Faraday Soc., 51,

277 (1955).

[20] Dahl, J. L., and Duke, F. R. , J. Phys. Chem., 62_, 1142 (1958).

[21] Janz, G. J., Lakshminarayanan, G. R. , Tomkins, R. P. T., and Wong, J.

,

"Molten Salts: Volume 2. Section 2. Surface Tension Data", NSRDS-NBS

28; 110 pages (1969).

408
NaN0

3 -KN0

3

[ 22 ]

[23]

[24]

[25]

[26]

[27]

[28]

[29]

[30]

[31]

[32]

[33]

[34]

[35]

[36]

[37]

[38]

[39]

[40]

[41]

[42]

[43]

[44]

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Krivovyazov, E. L. , Sokolova, I. D. , and Voskresenskaya, N. K. , J. Applied

Chem. USSR., 36_, 2458 (1963).

Ogawa, K. , Nippon Kinzoku Gakkaishi, 14B , 49 (1950).

Goodwin, H. M. , and Mailey, R. D. , Phys. Rev., 2_6, 28 (1908).

Zuca, S., and Borcan, R., Electrochim . Acta, 1_5, 1817 (1970).

Murguluescu, I. G., and Zuca, S. , Electrochim. Acta, 1_1, 1383 (1966).

Rhodes, E,, Smith, W. E., and Ubbelohde, A. R. , Proc. Roy. Soc.,

A285 , 263 (1965).

Timidei, A., Lederman, G., and Janz, G. J., Chem. Instrum., 2_, 309 (1970).

Vereshchetina , I. P., and Luzhnaya, N. P., Izvest. Sektora Fiz. Khim. Anal.

Inst. Obshchei i Neorg. Khim., Akad. Nauk SSSR, 2_5_, 188 (1954).

King. L. A., and Duke, F. R., J. Electrochem. Soc., Ill , 712 (1964).

Brillant, S., Ph.D. Thesis, Univ. of Strasbourg, Strasbourg, (1967); [N°

d' enregistrement au CNRS: AD 1813; see also J. Chim. Physique,

65, 2138 (1968).

Bizouard, M. , Ann. Phys., 6_, 851 (1 961).

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Doucet, Y., and Bizouard, M. , Compt. Rend., 248 , 1328 (1959).

Doucet, Y. , and Bizouard, M. , Bull. Soc. Chim. France, 1570 (1959).

Bergman, A. G., and Chagin, I. M. , Izv. Akad. Nauk SSSR, Ser. Khim,, _5, 727 (1940).

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(1965) .

De Nooijer, B., Ph.D. Thesis, University of Amsterdam, Amsterdam, 1965.

Copeland, J. L. , and Zybko , W. C., J. Phys. Chem., 7_0, 181 (1966).

Barton, A. F. M. , Cleaver, B., and Hills, G. J. , Trans. 'Faraday Soc.,

64, 208 (1968).

Wagner, V., Berra, E., and Forcheri, S., Z. Naturforsch. , 24_, 887 (1969).

Duke, F. R. , and Fleming, R. A., J. Electrochem. Soc., 105 , 412 (1958).

"Danqerous Properties of Materials "

,

Sax, N. I. , Van Nostrand Reinhold

Co . , N . Y. (1969).

"Reqistry of Toxio Effects of Chemical Substances ", Christensen, H. E.,

and Lubinbyhl, T. T. , eds . , U. S. Dept. H. E. W. , U. S. Gov’t

Printing Office, Washington, D. C. (1975).

"High Temperature Properties and Decomposition of Inorganic Salts. Part 3 Nitrates and Nitrites ", Stern, K. H., J. Phys. Chem. Ref. Data, 1_, 747 (1972).

"Potential Hazards In Molten Salt Baths for Heat Treatment of Metals ", National Board Fire Underwriters Research Report No. 2 (1954).

"Handbook of Reactive Chemical Hazards ", Bretherwick, L., Butterworths

Co . , London (197 5) .

Janz, G. J., Tomkins, R. P. T., Downey, J..R.,

"Safety and Hazards", Chapter vn "Eiitectyc D

NTIS, U. S. Dept. Commerce," Springfield, Va.

Jr . ata " (1977)

and Allen, C . B .

,

ERDA-TID- 27163 -Pi

409
NaN0

3

-KN0

3

[49] Conte, A., and Sergio, S., Corsi. Semin. Chim. , 12_, 1576 (1968).

[50] Nemenyi, R. , Haerter ei -Tech . Mitt., 27 , 40 (1972).

[51] Swofford, H. S., Jr., and Laitinen, H. A., J. Electrochem. Soc . , 110,

816 (1963).

[52] Notoya, T., and Midorikawa, R. , Denki Kagaku, ££, 865 (1973).

[53] Notoya, T., Ishikawa, T., and Midorikawa, R. , Denki Kagaku, £0, 62 (1972).

[54] Sukhotin, A. M. , Antonovskaya, E. I., Pozdeeva, A. A., and Solodkova, L.

I., Khim. Prom. (Ukr.) 1, 52 (1974).

[55] Desimoni, E., Paniccia, F., Sabbatini, L., and Zambonin, P. G.,

Proc. Intern. Symp . MOlten Salts; The Electrochem. Soc., Inc., Princeton,

N. J. , p. 584 (1976) .

[56] Pizzini, S., Proceedings European Conf. on Development Molten Salts

Applications, p. 203; Battelle, Geneva (1973).

[57] Johnson, K. E., Proceedings Intern. Symp. Metal-Slag-Gas Reactions and

Processes , The Electrochem. Soc., Inc., Princeton, N. J., p. 581 (1975).

[58] Conte, A., and Ingram, M. D. , Electrochimica Acta, £3, 1551 (1968).

[59] Bartlett, H. E., and Johnson, K. E. , Canad. J. Chem. , ££, 2119 (1966).

[60] Smirnov, M. V. , and Ozeryanaya, I. N. , Nauki Tekh. Korros. Zashch. Korros.

2, 171 (1973).

[61] Inman, D. , and Wrench, N. S., Brit. Corr. J., £, 246 (1966).

[62] Ketelaar, J. A. A.., Chem. Ing. Tech., £5, 667 (1973).

[63] Janz, G. J., and Tomkins, R. P. T. , Corrosion, 34 (in press) (1978).

[64] Delimarskii, Yu. K. , Markov, B. F., and Berenblyum, L. S., Zhur. Fiz.

Khim. , 27, 1848 (1953)

[65] Laitinen, H. A., and Osteryoung, R. A., in "Fused Salts", (B. R.

Sundheim, Ed.), McGraw-Hill, New York, Chap. 4, (1964).

[66] Inman, D. , and Bockris, J. O'M., J. Electroanal. Chem., £, 126 (1962).

[67] Aperce, J. P., Lantelme, F. , and Chemla, M. , C. R. Acad. Sci., Paris,

Ser. C. , 264, 461 (1967)

[68] Desimoni, E., Paniccia, F. , and Zambonin, P. G., J. Electroanal. Chem.,

38, 373 (1972).

[69] Swafford, H. S., Jr., and Dietz, J. , Anal. Chem.^ £4, 2232 (1972).

[70] Hills, G. J., Schiffrin, D. J., and Thompson, J., Electrochim. Acta, 19,

657, 671 (1974).

[71] Inman, D., Sethi, R. S., and Spencer, R. , J. Electroanal. Chem., 29,

137 (1971).

[72] Honig, E. P., Ph.D. Thesis, Amsterdam (1964).

[73] Honig, E. P., and Ketelaar, J. A. A., Trans. Faraday Soc., 62_, 190 (1966).

[74] Kawamura, K. , Electrochim. Acta, 1_2 , 1233 (1967).

[75] Lantelme, F., and Chemla, M. , Bull. Soc. Chim. Fr. , 169 , 969 (1963).

[76] Delimarskii, Yu. K. , and Shilina, G. V., Ukr. Khim. Zh. , 3£, 352 (1967).

410
NaN0

3 -KN03

[77]

[78]

[79]

[80]

[81]

[82]

[83]

[84]

[85]

[ 86 ]

[87]

[ 88 ]

[89]

[90]

[91]

[92]

[93]

[94]

[95]

[96]

[97]

[98]

[99]

[ 100 ]

El Hosary, A. A., and Shams El Din, A. M. , Electrochim. Acta, 16 , 143 (1971).

Trica, W. E., Videla, H. A., and Arvia, A. J. , Electrochim. Acta, 16 , 1671 (1971).

Francini, M. , and Martini, S., Electrochim. Acta, £3, 851 (1968).

Casadio, S., Conte, A., and Salvemini, F., Electrochim. Acta, 16 , 1533 (1971).

Shilina, G. V. , and Delimarskii, Yu. K. , Soviet Progr. Chem. , 33 (3),

9 (1967).

Hills, G. J., and Power, P. D . , J . Polarog . Soc

, 13, 71 (1967).

Mamantov, G., Strong, J. M. , and Clayton, F. R.

Jr. , Anal. Chem.

40, 488 (1968).

O'Deen, W. , and Osteryoung, R. A., Anal. Chem., £3, 1879 (1971).

Zambonin, P. G., Cardetta, V. L., and Signorile, G., J. Electroanal.

Chem., 2_8_, 237 (1970).

Zambonin, P. G., and Jordan, J., J. Am. Chem. Soc., 9£, 2225 (1969).

Zambonin, P. G., Anal. Chem., £4, 763 (1972).

McCormic, P. G., and Swofford, H. S., Jr., Anal. Chem., £1, 146 (1969).

Topol, L. E., Osteryoung, R. A., and Christie, J. H. , J. Phys . Chem.,

7_0 , 2857 (1966).

Francini, M. , and Martini, S., Electrochim. Metall., £, 136 (1968).

Francini, M. , Martini, S., and Monfrini, C., Electrochim. Metall., 2,

325 (1967).

Desimoni, E., Palmisano, F. , and Zambonin, P. G. , J. Electroanal.

Chem., 8£, 323 (1977).

Marchidan, D. I., and Telea, C., Rev. Chim. (Roumaine) , £3, 1291 (1968).

Voskresenskaya, N. K. , et al., Zhur. Prikl. Khim. , ££, 18 (1948).

Schinke, H. , and Sauerwald, F., Z. anorg. allgm. Chem., 304, 25 (1960);

ibid., 28£, 131 (1956); ibid., 287_, 313 (1956).

Shimoji, M. , Disc. Faraday Soc., 32_, 128 (1961).

Bloom, H. , Doroszkowski , A., and Tricklebank, S. B., Aust. J. Chem.,

18, 1171 (1965).

Jamieson, D. T., Irving, J. B., and Tudhope, J. S., "Liquid Thermal

Conductivity ", HMSO, Edinburgh (1975).

McDonald, J., and Davis, H. T., J. Phys. Chem., 7£, 725 (1970).

McDonald, J., Ph.D. Thesis, University of Minnesota, 1969.

411
XLVI . Lithium Nitrate - Sodium Nitrate-Potassium Nitrate: LiNO^-NaNO^-KNO^

1. Melting Temperatures (T ) Pure substance melting points:

LiN0

3

: 253°C

NaNOj : 307°C

KN0

3

: 337 ° C

Eutectic melting point:

120°C, composition: 37.5 mol % LiNOj, 18 mol % NaNC>

3

, 44.5 mol % KNC>

3

kno 3

MOL %

Figure 46.1. LiN0

3 -NaNC>3 -KN03 phase diagram

References [1-4] .

2 . Density ( p )

No data.

S. Surface Tension (y)

No data.

4 . Viscosity (

)

No data.

5. Electrical Conductance (k)

Measurement method: dc technique [5]

k = 1.40865 - 1.19760 x 10' 2 T + 2.84423 x 10" 5 T

2

- 1.69292 x 10' 8 T

3 (46.1)

precision: ^ + 0.35? uncertainty: ^ + 2?

412
LiN0

3 -NaN03 -KN03

Table 46.1. Specific conductance from equation (46.1)

for eutectic composition

T K T K (K) (ohm 1 cm x

) (K) (ohm 1 cm 1

)

410 0.1129 540 0.5696

420 0.1417 550 0.6090

430 0.1720 560 0.6485

440 0.2035 570 0.6881

450 0.2363 580 0.7275

460 0.2703 590 0.7667

470 0.3052 600 0.8056

480 0.3410 610 0.8441

490 0.3777 620 0.8820

500 0.4151 630 0.9194

510 0.4531 640 0.9561

520 0.4915 650 0.9919

530 0.5304

References [5] .

6. Safety and Hazards

A. Hazard rating [6-8]

(i) Toxicity: LiNC>

3

, moderate; NaNOj, low; KN0

3

, low

(ii) Vapor pressure: eutectic (m.pt. 120°C) : no data on thermal

stability; the nitrates decompose thermally to form the

corresponding nitrites and oxygen:

MN0

3 — MNC>2 + h0 2 (46.2)

LiNOj is the least stable, and decomposes just above its

m.pt. (253°C) to LiN02. If the container material is not

inert; oxides of nitrogen are evolved.

B. Disaster hazards [6-9]

(i) Molten salt bath "explosions": i.e. explosive generation

of steam due to bulk water "carry-over" and/or equipment

failure; i.e., explosive expansion of "trapped" air.

(ii) On decomposition,, nitrates emit toxic

nitrogen) viz:

fumes (oxides of

MN0

3 — MN0

2 + h0

2 (46.3.1)

2MN0

2 —*• M2 0

' + NO + N0

2 (46.3.2)

The subsequent decomposition reactions are complex; if the

gas phase is continuously removed, the nitrite decomposition

(above) to NO and NO;? is dominant. If the gas phase is not

immediately removed, the NO may re-oxidize the nitrite to

nitrate

(iii) Nitrates are powerful oxidizing agents; violent (explosive)

reactions possible in molten nitrates and carbonaceous materials

(organic compds.; oils; carbon;...) aluminum alloys and bath

sludges (e.g., iron oxides); magnesium alloys. Dangerous.

References [6-11].

413
LiN0

3

-NaN0

3 -KN0

3

7. Corrosion

No corrosion studies reported; for guidelines, see each component as single-salt melts and binary combinations.

8. Diffusion

Measurement method: cited in tabulations

List of diffusing species investigated in LiNC>

3 -NaN0

3

-KN0

3 as solvent

Tl

+

, Pb 2+

, Zn

2+

3 Cd2+

, Co

2+

3 Ni 2+

, Eu

Z+

3 Cl ^

Br £3 NO

2 The italicized species indicate studies with data-sets inadequate for

temperature-dependence characterization of diffusion coefficients.

precision: not estimated uncertainty: in table 46.2.1

Table 46.2.1. Diffusion techniques, uncertainties and species

Diffusion techniques

of recommended study

Uncertainty

(in values of D)

Species

<\j ± 20%

2+ 2+ ,2+ polarography Pb , Zn , Cd

Co

2+

, Ni 2+

+ 2 + 2 + oscillographic T1 , Pb , Zn , polarography %± 20% ,2+ _ 3 +

Cd , Ni , Eu

rotating disc electrode 20% Tl

+

, C

2

, Br

2

, I 2, no

2

For numerical values: see table 46.2.2

414
LiN0

3 -NaN0

3 -KN03

Table 46.2.2. Diffusion coefficients

Species T(K)

D x 10 5 (cm 2 sec

-1

) Recommended

study

Tl

+ 423 8 .

a 15,16

Pb 2 + 423 0.087 16,18

Zn

2 + 433 0.15 13,16

Cd 2 + 422 0.10 14,16

Co

2 + 421 0.08 14

N i

2 + 416 0.035 14,16

Eu

3 + 433 0.044 19

C1

2 423 5 .

17

Br

2 423 5 .

17

1

2 423 4.2 15,17

no

2 423 7 .

15

Value appears improbably high.

For the underlined species, the temperature dependence of D reported

in graphical form; see [16,19].

References

Tl\ 15, 16, 20; Pb

2+

, 13, 14, 16, 18, 20 ; 7

2 + Zn , 13, 16, 20; Cd2+

, 13,

14, 16, 20; Co

2 +

, 14; Ni

2+

, 13 , 14 , 16, 20 ; r

3 + Eu , 19 ,, 20; Cl

2

, 17;

Br

2

* 17; 1 2

’ 15, 17; N0

2

, 15

9. Heat

No

of Fusion ( A Hj,)

data

10 . Heat Capacity (C

)

No data.

11.

Volume Change on Melting (AP^J

No data; but see LiN0

3

, NaNOj , KNC>

3

, and NaN0

3 -KN0

3 for guidelines

12.

Vapor Pressure (p ) * vap

No vaporization studies reported. For thermal decomposition processes in

molten nitrates (to nitrites, oxides, with formation of gaseous oxides and

oxides of nitrogen) see LiNOj, NaNOj,and KNC>

3

.

13.

Thermal Conductivity (liquid) (*%)

No thermal conductivity studies reported.

415
LiN0

3 -NaN0

3

-KN0

3

14. Thermal Conductivitya (solid) (X ) s

No thermal conductivity studies reported.

15. Cryoscopic Constant (k^,)

No data.

16. References

[1] Bergman, A. G. , and Nogoev, K. , Zh. Neorg. Khim. , 9, 771 (1964).

[2] Carveth, H. R. , J. Phys . Chem., 2, 216 (1898).

[3] Janz, G. J., Downey, J. R. , Jr., Allen, C. B. , and Tomkins, R. P. T.,

"Eutectic Data ", - 2 vols.; ERDA-TID-27163-P1 § P2 ; NTIS,

Washington, D. C. (1977).

[4] Janz, G. J., Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T.,

"Physical Properties Data Compilations Relevant to Energy Storage. I. Molten Salts: Eutectic Data ", NSRDS-NBS-61 ; U. S. Gov't Printing

Office, Washington, D. C. (1978).

[5] King, L. A., Bissell, C. L., and Duke, F. R. , J. Electrochem. Soc.,

Ill, 720 (1964).

[6] "Dangerous Properties of Materials ", Sax, N. I., Van Nostrand Reinhold

Co., N. Y. (1969).

[7] "Registry of Toxic Effects of Chemical Substances'', Christensen, H. E.,

and Lubinbyhl, T. T., eds., U. S. Dept. H. E. W. ; U. S. Gov't Printing

Office, Washington, D. C. (1975).

[8] "High Temperature Properties and Decomposition of Inorganic Salts. Part

3. Nitrates and Nitrates", Stern, K . H. , J. Phys. Chem. Ref. Data,

1, 747 (1972).

[9] "Potential Hazards In Molten Salt Baths for Heat Treatment of Metals"3 National Board Fire Underwriters Research Report No. 2 (1954).

[10] "Handbook of Reactive Chemical Hazards ", Bretherwick, L., Butterworths

Co . , London (1975)

[11] Janz, G. J. , Tomkins, R. P. T., Downey, J. R. , Jr., and Allen, C. B.

,

"Safety and Hazards", Chapter in "Eutectic Data", ERDA TID-27163 -PI

NTIS, U. S. Dept. Commerce, Springfield, Va . (1977).

[12] Delimarskii, Yu. K. , and Markov, B. F. , "Electrochemistry of Fused

Salts", Sigma Press, Washington, D. C., Chap. 8 (1961).

[13] Steinberg, M. , and Nachtrieb, N. H. , J. Am. Chem. Soc., 72, 3558 (1950).

[14] Inman, D. , Lovering, D. G., and Narayan, R. , Trans. Faraday Soc., 63,

3017 (1967).

[15] Delimarskii, Yu. K. , and Shilina, G. V., Sov. Progr. Chem., 33, 6

(1967); Ukr. Khim. Zh. , 33, 352 (1967).

[16] Francini, M. , and Martini, S., Z. Naturforsch. , 23A, 795 (1968).

[17] Delimarskii, Yu. K. , and Shilina, G. V., Electrochim. Acta, 10, 973

(1965)

[18] Hills, G. J., and Power, P. D. , J. Polarog. Soc.. 13, 71 (1967).

[19] Francini, M. , and Martini, S., Electrochim. Metall., 3, 132 (1968).

[20] Francini, M. , and Martini, S., Electrochim. Metall., 3, 136 (1968).

416
XLVII. Lithium Sulfate-Potassium Sulfate: Li

2 SO^-K

2 SO^

1. Melting Temperatures

Pure substance melting points:

Li

2 S04

: 8 5 9

° C

K

2 S0

4

: 1069°C

Eutectic melting points:

Eutectic 1: 535°C, composition: 80 mol % Li

2

SC> 4 Eutectic 2: 700-712°C, composition: 39.5 mol % Li

2 S0

4

Figure 47.1. Li

2 S0

4 -K

2 S04 phase diagram

References [1-3] .

2. Density ( p ) Measurement method: Archimedean technique [4,5]

p = a - bT (47.1)

precision: ^ ± 0.1% uncertainty: ^ ± 1%

Table 47.1. Coefficients of equation (47.1)

Mixture Mol % Li SO,

l 4 a b x 10^

A 80 2 .455 4 . 07

B 50 2 .469 4.337

417
Li

2 S04

-K

2 S04

Table 47.2.1. Densities for mixture A from equation

in table 47.1

T(K) p(g cm 3

) T (K) p(g cm-3

) 860 2.1050 950 2 . 0683

870 2 .1009 960 2 . 0643

880 2 . 0968 970 2.0602

890 2 . 0928 980 2 . 0561

900 2.0887 990 2.0521

910 2.0846 1000 2 . 0480

920 2 . 0806 1010 2.0439

930 2.0765 1020 2 . 0399

940 2.0724

Table 47.2 .2. Densities for mixture B from equations

in table 47.1

T(K) p(g cm 3

) T(K) p(g cm -3

) 1070 2 . 004 1170 1.962

1080 2.001 1180 1. 957

1090 1.996 1190 1.953

1100 1.992 1200 1.949

1110 1.988 1210 1.944

1120 1.983 1220 1.940

1130 1.979 1230 1.936

1140 1.975 1240 1.931

1150 1.970 1250 1.927

1160 1.966 1260 1 . 923

References [4,5] .

3. Surface Tension (y)

No data.

4 . Viscosity (r\)

No data.

5. Electrical Conductance (k)

Measurement method: ac technique [6]

k = a + bT + cT

2 + dT 3 (47.2)

precision: in table 47.3 uncertainty: 'v. ± 2.5%

418
Li

2 S0

4 -K

2 S0

4

Table 47.3, Parameters of equation (47.2), and precisions

Mol % K 2 S0 4 -a b x 10 3 c x 10 6 -d x 10 9 Precision

3 . 00 1.79337 -0.57431 9 .45601 4.01944 ±0.008%

4 .89 3.25757 3 .49123 5 .45248 2 .76495 ±0.06%

20.00 3.36276 3 .96153 2.76059 1 .56802 ±0.20%

25 . 00 14.44603 35 . 91980 -28 . 07680 -8 . 24127 ±0.50%

40.00 3.51175 5 . 55568 -0.81426 ±0.15%

60.00 2.99969 4.69725 -0.70820 ±0.13%

80.00 1.39083 2 .43733 ±0.03%

100.00 0.81133 2 . 01416 ±0.10%

Table 47.4. Specific conductance (ohm ^cm from

equations in table 47.3

Mol % K.SO.

2 4

T (K) 3 . 00 4.89 20.00 25.00 40.00 60.00 80.00 100

840 0.800

850 0.861

860 0. 921

870 1 . 141 0. 980

880 1.193 1.037

890 1.244 1.093

900 1.296 1 . 147

910 1.347 1.201

920 1.397 1 .253

930 1.448 1 . 305

940 1.498 1.355

950 1.548 1.404

960 1.597 1 .453

970 1.646 1 . 500

980 1.695 1.547

990 1.743 1 .593 1.190 0.956

1000 1.791 1 . 638 1.230 0.989

1010 1.839 1 . 683 1.269 1.022

1020 1.886 1.727 1.308 1 .055

1030 1.933 1.770 1 . 347 1 . 087

1040 1.979 1.813 1 .385 1.119

1050 3.219 2.025 1.855 1.424 1 .152

1060 3.277 2 . 071 1.897 1 .462 1.184

1070 3.333 2.116 1. 939 1.501 1.215

1080 3 . 553 3.390 2 .160 1 . 980 1 . 539 1 . 247

1090 3 . 610 3.445 2 .205 2 . 021 1.577 1.279

1100 3 . 667 3 . 500 2 . 248 2 . 062 1 . 614 1.310

nio 3.723 3 . 554 2 .291 2 . 103 1. 652 1 .342

1120 3.778 3 . 608 2 .334 2 . 143 1.689 1.373

1130 3 .832 3 . 660 2.376 2 .183 1.726 1.404

1140 3 .886 3.712 2 . 418 2.224 1.763 1.435

1150 3.939 3.763 2.459 2.264 1.800 1.466

1160 3 . 991 3.813 2 . 500 2 .305 1 .837 1.496

1170 4.041 3 .863 2 . 540 2 .345 1.874 1 .527

1180 3 . 911 2 .386

1190 2.427

1200 2.468

1210 2 . 510

1220 1 . 583

1230 1 . 607

1240 1 .888

1250 1 . 908

1260 1.928

419
Li

2 S04 -K2 S04

References [ 6 ]

.

6. Safety and Hazards

A. Hazard rating [7-9]

(i) Toxicity: Li

2 S0 4

, unknown; "toxic" qualities of Li salts;

K

2 S 04

, severe^

(ii) Vapor pressure: eutectics melt to form stable liquids.

Note: Li 2 S 04 decomposes at ^ 860°C, evolving aggressive

and toxic fumes (oxides of sulfur)

B. Disaster hazards [7,10-12]

(i) Molten salt bath "explosions": i.e., explosive generation of

steam due to bulk water "carry-over" and/or equipment

failure, i.e., explosive expansion of "trapped" air.

(ii) When heated to decomposition, sulfates decompose, evolving

SO 3 , which in turn dissociates to SO 2 and O 2 (see above);

toxic, corrosive fumes.

References [ 7 - 12 ].

7. Corrosion

Table 47.5.

primary

Corrosion studies from

research literature

Studies References

Fe, Ni 13

Ferr ite steels

Fe-Mo

,

Fe-Cr <-Mo , 14

Fe-Cr

Fe 15

Cu , Pd , Rh , Ag 16

Emf . series 16,17

Thermodynamic redox diagrams 13-15

Electrochem. approach 18,19

Reviews: molten salts corrosion 17,20,21

Annotated corrosion biblio. 22

References [13-22].

Diffusion

Measurement method: cited in tabulations

List of diffusing species investigated in Li

2 S04 -K2 S0

4 as solvent

t 2+ Dk 2+

In , Pb Bi 3 + 2 + 2 + 2 + 2 +

, Cu ’ Cu , Ag , Zn , Cd , Fe , Fe

precision: not estimated uncertainty: in table 47 . 6.1

3 +

Co

2+

, Ni 2+

420
Li

2 S04

-K

2 S04

Table 47.6.1. Diffusion techniques, uncertainties, and species

Diffusion technique

of recommended study

Uncertainty Species

chronopotentiometry 'v. + 10% In 3+ ,Pb 2+ ,Bi 3+ ,Cu + ,Cu 2+

,

Ag

+

, Zn 2+ ,Cd 2+ ,Fe 2+

,

Co 2+ ,Ni 2+

Equations: insufficient data-sets for characterization of temperature

dependence of diffusion coefficients.

Table 47.6.2. Diffusion coefficients

Species

Melt

composition

(mo 1 % L

2 SO 4 )

T(K)D x 10 5 (cm 2 sec" 1

)

Recommended

study

In 3 + 86.38 873 0 . 05 23

Pb 2 + 86.38 873 0.79 2 3

Bi 3 + 86.38 873 0.16 23

Cu + 86.38 873 1 .58 23

80 898 2 . 00 24

Cu 2 + 86.38 873 0 .28 23

Ag

+ 86.38 873 2 . 07 23

Zn 2 + 86.38 873 0.42 23

Cd 2 + 86.38 873 0.46 23

Fe 2+ 86.38 873 0.39 25

Fe 3 + 86,38 873 0.145 25

Co 2 + 86.38 873 0,25 23

Ni 2 + 86.38 873 0.33 23

References: In

3+

, 23; Pb

2+

, 23; Bi 3+

, 23; Cu

+

, 23, 24; Cu

2+

, 23; Ag

+

, 23,

13; Zn

2+

, 23; Cd

2+

, 23; Fe

2+

, 25; Fe

3+

, 25; Co

2+

, 23; Ni

2+

, 23.

9.

10 .

Heat of Fusion (A H^,)

No data.

Heat Capacity ( C J No data.

421
Li

2 S04

-K

2 S04

11 . Volume Change on Melting (AV^J

Measurement method: estimated; from densities [26]

Table 47.7. Volume change on melting, and uncertainty

Binary mixtures

(mol % Li 2 S0 4 )

T m

(°C) (A W

Uncertainty

80 535 -V - 1.0% ^±10%

39.5 710 'v 11.2% ^±10%

References [26]

12. Vapor Pressure (pr ) vap

No vaporization studies reported.

12. Thermal Conductivity (liquid) (h^)

No thermal conductivity studies reported,.

14.

Thermal Conductivity (solid) (X ) s No thermal conductivity studies reported.

15.

Cry o scopic Constant (k^J

No data.

16.

References

[1] Nacken, A. A., Neues Jahrb. Mineral Geol., Beilage Bd., 24A , 43 (1910).

[2] Janz, G. J., Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T.,

" Eutectic Data" - 2 vols; ERDA-TID-27163-P1 $ P2 ; NTIS, Washington,

D. C. (1977).

[3] Janz, G. J., Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T., "Physical Properties Data Compilations Relevant to Energy Storage. I. Molten Salts: Eutectic Data", NSRDS-NBS- 61 ; U. S. Gov’t Printing

Office, Washington, D. C. (1978).

[4] James, D. W. , and Liu, C. H. , J. Chem. Eng. Data, 8, 469 (1963).

[5] Kvist, A., and Schroeder, K. , Z. Naturforsch . , 23A , 676 (1968).

[6] Kvist, A., Z. Naturforsch., 2_1 , 1221 (1966).

[7] "Dangerous Properties of Materials"

,

Sax, N. I., Van Nostrand Reinhold

Co. , N. Y. (1969) .

[8] "Registry of Toxic Effects of Chemical Substances"

,

Christensen, H. E.,

and Lubinbyhl , T. T. , eds., U. S. Dept. H. E. W. ; U. S. Gov't Printing

Office, Washington, D. C. (1975).

Stern, K. H. , "High Temperature Properties and Decomposition of Inorganic

Salts. Part 1. Sulfates", U. S. Dept. Commerce NBS-NSRDS-7, U. S. Gov't

Printing Office, Washington, D. C. (1966).

422
Li

2 S04 -K2 S0

4

[10] "Potential Hazards in Molten Salt Baths for Heat Treatment of Metals",

National Board Fire Underwriters Research Report No. 2 (1954).

[11] "Handbook of Reaotive Chemical Hazards", Bretherwick, L., Butterworths

Co . , London (1975)

[12] Janz, G. J., Tomkins , R. P. T. , Downey, J. R. , Jr. , and Allen, C. B.

"Safety and Hazards ", Chapter in "Euteetio Data", ERDA TID- 27163-PI

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[13] Burrows, B. W. , and Hills, G. J., Electrochim. Acta, 1J3, 445 (1970).

[14] Baudo , G., Tamba, A., and Bombara, G., Corrosion, 26^, 193 (1970).

[15] Baudo, G. , and Tamba, A., Brit. Corrosion J., 4_, 129 (1969).

[16] Liu, C. H. , J. Phys . Chem. , 6_6, 164 (1962).

[17] Ketelaar, J. A. A., Chemie Ing. Tech., 4_5, 667 (1973).

[18] Pizzini, S., Proceedings European Conf. On Development of Molten Salts

Applications, p. 203; Battelle, Geneva (1973).

[19] Johnson, K. E„, Proceedings Intern. Symp . Metal-Slag-Gas Reactions

and Processes, p. 581; The Electrochem. Soc.,Inc., Princeton, N. J.

(1975)

[20] Smirnov, M. V. , and Ozeryanaya, I. N. , Nauki Tekh. Korros. Zashch.

Korros., 2_, 171 (1973).

[21] Inman, D., and Wrench, N. S., Brit. Corr. J., 1, 246 (1966).

[22] Janz, G. J., and Tomkins, R. P. T., Corrosion, 3£, (in press) (1978).

[23] Inman, D., Jovanovic, D. , and White, S. H. , J. Electroanal. Chem., 43,

37 (1973).

[24] Liu, C. H. , Anal. Chem., 33, 1477 (1961).

[25] Wrench, N. S., Private communication cited by ref. 23.

[26] Janz, G. J., et al . , (MSDC-RPI) unpublished results (1977).

423
XLVIII. Lithium Sulfate - Sodium Sulfate-Potassium Sulfate: Li

2

SC> 4 -Na

2 S0

4 -K2 S04 1.

Melting Temperatures ) Pure substance melting points:

Li

2 S04

: 8S9°C

Na

2 S04

: 884°C

K

2 S0

4

: 1069°C

Eutectic melting point:

512°C, composition: 78 mol % Li

2

SC> 4

, 8.5 mol % Na

2

SC> 4

, 13.5 mol % K

2 SC> 4

Li 2 S04

Figure 48.1. Li

2 S0

4 -Na

2 S04 -K

2 S0

4 phase diagram;

E, eutectic; P's, peritectics

References [ 1 - 3 ]

2. Density (p)

No data.

3. Surface Tension (y)

No data.

4. Viscosity (r\)

No data.

5. Electrical Conductance (k)

No data.

424
6. Safety and Hazards

Li

2 SO^-Na2SO^-K2SO^

A. Hazard rating [4-6]

(i) Toxicity: L^SO^, unknown: "toxic" qualities of Li cations;

Na 2 S 04 , unknown: "toxic" qualities of Na cations; K 2 SO 4 , severe

(ii) Vapor pressure: eutectic (m.pt. 512°C) melts to form a stable liquid.

Note: Li 2 SC>4 decomposes at v 860°C, evolving aggressive

and toxic fumes (oxides of sulfur)

B. Disaster hazards [4,7-9]

(i) Molten salt bath "explosions": i.e., explosive generation of steam

due to bulk water "carry-over" and/or equipment failure; i.e.,

explosive expansion of "trapped" air.

(ii) Sulfates, when heated to decomposition, evolve SO 3 , which, in

turn, dissociates to S 0

2 andC^; toxic, aggressive fumes

References [4-9]

Corrosion

Table 48.1. Corrosion studies from

primary research literature

References [

S tud ies References

SS (18-8)

10

Nimonic-105 alloy (19 Co, 16 Cr

4 Al, 4 Ti, 1.5 Mo, balance Ni)

Emf series 11 ,12

Thermodynamic redox diagrams 13

Electrochem. approach 14,15

Reviews: molten salts corrosion 12,16,17

Annotated corrosion biblio. 18

8. Diffusion

Measurement method:

List of diffusing

chronopotent iometry

species investigated

10 ] in L^SO^-N^SO^-K^SO^ as solvent

Table 48.2. Diffusion coefficients and uncertainties

Species D x 10 Temp . Uncertainty

(cm^ sec - l) (K)

S°

3 0.6 873 'v- ± 5%

References [10] .

9. Heat of Fusion (kH°)

No data.

425
Li2SO^-Na2SO^-K2SO^

10.

Heat Capacity (C

)

No data.

11. Volume Change on Melting

No data; but see LiCl, NaCl, KC1, NaCl-KCl, and nitrates for guidelines.

12. Vapor r rpressure (pr ) uap

No vaporization studies reported.

13. Thermal Conductivity (liquid) (X^J

No thermal conductivity studies reported

14. Thermal Conductivity (solid) (X ) u s No thermal conductivity studies reported

15. Cryoscopic Constant <k

f

>

No data.

16. References

[1] Akopov, E. K. , and Bergman, A. G., Zh. Organ. Khim. , 2_4, 1512 (1954).

[2] Janz, G. J. , Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T.,

"Eutectic Bata" - 2 vols.; ERDA-TID- 27163-PI § P2 ; NTIS, Washington,

D. C. (1977).

[3] Janz, G. J., Downey, J. R. , Jr., Allen, C. B. , and Tomkins, R. P. T.,

"Physical Properties Data Compilations Relevant to Energy Storage. I. Molten Salts: Eutectic Data", NBS NSRDS-61; U. S. Gov't Printing

Office, Washington, D. C. (1978).

[4] "Dangerous Properties of Materials ", Sax, N. I., Van Nostrand Reinhold

Co. , N. Y. (1969)

[5] "Registry of Toxic Effects of Chemical Substances

3 Christensen, H. E.,

and Lubinbyhl, T. T., eds., U. S. Dept. H. E. W. , U. S. Gov't Printing

Office, Washington, D. C. (1975).

[6] "High Temperature Properties and Decomposition of Inorganic Salts . Part 1 Sulfates

3 Stern, K. H. , U. S. Dept. Commerce, NBS-NSRDS-7; U. S. Gov't

Printing Office, Washington, D. C, (1966).

[7] "Potential Hazards In Molten Salt Baths for Heat Treatment of Metals"3 National Board Fire Underwriters Research Report No. 2 (1954).

[8] "Handbook of Reactive Chemical Hazards

3 Bretherwick, L., Butterworths

Co . , London (1975)

[9] Janz, G. J., Tomkins, R. P. T., Downey, J. R., Jr., and Allen, C. B.,

"Safety and Hazards ", Chapter in "Eutectic Data", ERDA TID-27163-P1

NTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

[10] Cutler, A. J. B., and Grant, C. J., "Corrosion of Iron and Nickel

Base Alloys in Alkali Sulphate Melts ", p. 591 in "Proceedings Intern.

Symp . on Metal-Slag-Gas Reactions and Processes"; The Electrochemical

Soc., Princeton, N. J. (1975).

[11] Johnson, K. E. , and Laitinen, H. A., J. Electrochem. Soc., 110 , 314 (1963)

[12] Ketelaar, J. A. A., Chemie Ing. Techn. , 4_5_, 667 (1973).

426
Li

2 S04 -Na

2 S04 -K2 S0

4

[13] Rahmel, A., Ele ctrochimica Acta, 15_, 495 (1968).

[14] Pizzini, S., Proceedings European Conf. On Development of Molten Salts

Applications, Battelle, Geneva, p. 203 (1973).

[15] Johnson, K. E., Proceedings Intern. Symp . Metal -Slag-Gas Reactions

and Processes, p. 581; The Electrochem. Soc.,Inc., Princeton, N. J.(1975).

[16] Smirnov, M. V. , and Ozeryanaya, I. N. , Nauki Tekh. Korros. Zashch.

Korros . , 2, 171 (1973)

[17] Inman, D., and Wrench, N. S. , Brit. Corr. J. , 1_, 246 (1966).

[18] Janz, G. J., and Tomkins, R. P. T., Corrosion, 34_ (in press) (1978).

427
XLIX. Sodium Chloride -Lithium Sulfate: NaCl-L^SO^

1.

Melting Temperatures (T ) Pure substance melting points:

NaCl : 800°C

Li

2 S04

: 859°C

Eutectic melting point:

499°C, composition: 26.0 mol % NaCl

Figure 49.1. NaCl-L^SO^ phase diagram

References [1-3]

2. Density (p)

No data.

3. Surface Tension (y)

Measurement method: maximum bubble pressure [4]

y

= a + bT + cT

2

(49.1)

precision: in table 49.1 uncertainty: ^ ± 3%

428
NaCl-Li

2 S0

4

Table 49.1. Parameters o£ equation (49.1), and precisions

NaCl

(Mol %) a b x 10 2 -c x 10 6 Precision

0 -67 .289 51 . 487 227 . 30 ± 0 . 12%

1.0 299 . 27 -7 . 20 ±0.66%

1.5 289.63 -6.60 ±0.13%

2 .

294 . 32 -7.00 ± 0 .13%

2 .

154.3 14.784 85 . 55 ± 0 .07%

10.0 85.37 23 . 002 113 . 90 ± 0 . 50%

30.0 236 . 64 -5 . 800 ±0.50%

50.0 -41 . 197 36.204 170.50 ±0.32%

75.0 -11.475 28 . 824 142.30 ± 0 . 16%

100.0 -38.168 29.224 142 . 30 ± 0 .53%

Table 49.2. Surface tension (dyn cm from equations in table 49.1

Mol % NaCl

T ( K ) 0 1.0 1.5 2.0 2.5 10 30 50 75 100

1-60 223.8 214.3 211.8 211.7 209.6 198.2 168.2 148.6 130.5 108.5

1190 223.5 213.6 211.1 211.0 209.1 197.8 167.6 148.2 130.0 108.1

1200 223.2 212.9 210.4 210.3 208.5 197.4 167.0 147.7 129.5 107.6

1210 222.9 212.2 209.8 209.6 207.9 196.9 166.5 147.2 129.0 107.1

1220 222.5 211.4 209.1 208.9 207.3 196.5 165.9 146.7 128.4 106.6

1230 222.1 210.7 208.5 208.2 206.7 196.0 165.3 146.2 127.8 106.0

1240 221.7 210.0 207.8 207.5 206.1 195.5 164.7 145.6 127 .

105.4

1250 221.1 209.3 207.1 206.8 205.4 194.9 164.1 144.9 126.5 104.8

1260 220.6 208.6 206.5 206.1 204.8 194.4 163.6 144.3 125.8 104.1

1270 220.0 207.8 205.8 205.4 204.1 193.8 163.0 143.6 125.1 103.5

1280 219.3 207 .

205.2 204.7 203.4 193.2 162.4 142.9 124.3 102 . 8

'

1290 218.6 206.4 204.5 204.0 202.6 192.6 161.8 142.1 123.6 102.0

1300 217.9 205.7 203.8 203.3 201.9 191.9 161.2 141.3 122.8 101.3

1310 217.1 205.0 203.2 202.6 201.2 191.2 160.7 140.5 121.9 100.5

1320 216 .

204.2 202.5 201.9 200.4 190.5 160.1 139.6 121.1 99.6

1330 215.4 203.5 201.9 201.2 199.6 189.8 159.5 138.7 120.2 98.8

1340 214.5 202.8 201.2 200.5 198.8 189.1 158.9 137.8 119.3 97.9

1350 213.5 202.1 200.5 199.8 198.0 188.3 158.3 136.8 118.3 97.0

1360 212.5 201.4 199.9 199.1 197.1 187.5 157.8 135.8 117 .

96.1

1370 211.5 200.6 199.2 198.4 196.3 186.7 157.2 134.8 116.3 95.1

1380 210.4 199.9 198.6 197.7 195.4 185.9 156.6 133.7 115.3 94.1

References [4]

4 . Viscosity (r\)

No data.

5. Electrical Conductance (<)

No data.

429
NaCl-Li

2 S0

4

6.

Safety and Hazards

A. Hazard rating [5-7]

(i) Toxicity: Li2SC>4, unknown: "toxic" qualities of Li

cations; NaCl , very low.

(ii) Vapor pressure: eutectic (m.pt. 499°C) melts to form a stable liquid; Note: Li2S04 decomposes at a. 860°C,

evolving oxides of sulfur (toxic, aggressive fumes).

B. Disaster hazards [5,8-10]

(i) Molten salt bath "explosions": i.e., explosive generation of steam

due to bulk water "carry-over" and/or equipment failure;

i.e., explosive expansion of "trapped" air.

(ii) When bulk NaCl is heated at high temperatures, vapor is

evolved which is particularly irritating to the eyes;

when heated to decomposition or contacted with acids,

highly toxic chloride fumes are evolved.

(iii) Sulfates, when heated to decomposition, evolve SO?,

which in turn dissociates to S0 2 and 0 2 ; toxic,

aggressive fumes.

References [5-10].

7. Corrosion

No corrosion studies; see NaCl and Li

2 SC> 4 for guidelines.

8. Diffusion

No diffusion studies reported .

9. Heat of Fusion (AH°)

Measurement method: drop calorimetry [11]

Table 49.3. Heat of fusion

Binary eutectic

(mol % L

2 S 0 ^

)

ah°

11 _ 4 (kcal mol ) Uncertainty

58.1 7 .48 CM e-e a +i

Reference [11 ]

10.

Heat Capacity (£ ) Measurement method- drop calorimetry [11]

Table 49.4. Heat capacity

Binary eutectic

(mol % L^SC^)

C

P (cal K frnol - !)

T'6 mp . rang

(K)

Uncertainty

58 .

32 .

763-874 CM a +i Reference [11 ]

430
11 .

NaCl-Li

2 S04

12 .

Volume Change on Melting

No data; but see LiCl,

Vapor ^ Pressure (pr ) vap

No vaporization studies

(hV

f)

NaCl, KC1

reported

NaCl-KCl, etc. for guidelines.

13. Thermal Conductivity (liquid)

No thermal conductivity studies reported.

14. Thermal Conductivity (solid) (A )

No thermal conductivity studies reported.

15. Cryoscopic Constant (k

f

) Measurement method: calc'd., from AH^ [12]

Table 49.5. Cryoscopic constant

k f (K mol ^kg ^

)

Uncertainty

5. 6 ^ ± 2%

References [11,12].

16. References

[1] Bergman, A. G., and Akopov, E. K. , Izv. Sektor. Fiziko-Khimicheskogo

Analiza, 23 , 222 (1953) .

[2] Janz, G. J., Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T.,

"Eutectic Data" - 2 vols.; ERDA-TID- 2 7 1 63 - PI § P2 ; NTIS, Washington,

D. C. (1977).

[3] Janz, G. J., Downey, J. R. , Jr., Allen, C. B., and Tomkins, R. P. T.,

"Physical Properties Data Compilations Relevant To Energy Storage. I. Molten Salts: Eutectic Data ", NSRDS-NBS-61 ; U. S. Gov't Printing

Office, Washington, D. C. (1978).

[4] Semenchenko, V. K. , and Shikhobalova , L. P., Zhur. Fiz. Khim. , 21, 707

(1947).

[5] "Dangerous Properties of Materials ", Sax, N. I., Van Nostrand Reinhold

Co. , N. Y. (1969) .

[6] "Registry of Toxic Effects of Chemical Substances ", Christensen, H. E.,

and Lubinbyhl, T. T., eds., U. S. Dept. H. E. W. ; U. S. Gov't

Printing Office, Washington, D. C. (1966).

[7] "High Temperature Properties and Decomposition of Inorganic Salts. Part

1. Sulfates ", Stern, K. H. , U. S. Dept. Commerce NBS-NSRDS-7; U. S.

Gov't Printing Office, Washington, D. C. (1966).

[8] "Potential Hazards In Molten Salt Baths for Heat Treatment of Metals"

,

National Board Fire Underwriters Research Report No. 2 (1954).

[9] "Handbook of Reactive Chemical Hazards", Bretherwick, L., Butterworths

Co . , London (1975)

[10] Janz, G. J., Tomkins, R. P. T., Downey, J. R. , Jr., and Allen, C. B.,

"Safety and Hazards", Chapter in "Eutectic Data", ERDA TI D- 2 7 1 63 - PI ; nNTIS, U. S. Dept. Commerce, Springfield, Va. (1977).

431
NaCl-Li

2 S04

[11] Clark, R. P. , J. Chem. Eng. Data, 2_0, 17 (1975).

[12] Janz, G. J., et al., (MSDC-RPI) unpublished work (1977).

432
NBS-114A (REV. 9-76)

U.S. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET

1. PUBLICATION OR REPORT NO. NSRDS-NBS 61, Part II

3. Recipient’ a Accession No.

4. TITLE AND SUBTITLE

Physical Properties Data Compilations Relevant to

Energy Storage. II. Molten Salts: Data on Single

and Multi-component Salt Systems

5. Publication Date April 1979

STTT —

.

. -

7. AUTHOR(S) G. J. Janz, C. B. Allen, N. P

R. M. Murphy, and R. P. T. Tomkins

Ban sal , 8. Performing Organ. Report No.

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, DC 20234

11. Contract/Grant No.

12, SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street, City, state, ZIP)

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| | Document describes a computer program; SF-185, FIPS Software Summary, is attached.

16. ABSTRACT (A 200-word or less factual summary ol most significant information. If document includes a significant bibliography or

liters ture survey, mention i t here.) The pr e s ent wor k pr o vi d e s s e le c t ed da ta w it h V a 1 ue judgeme n t s f o r a s e t

of 49 s a It sy s t ems o f i n t e r e St a s c an did a t e ma t e rials for ther ma 1 en e r gy

s to rag e sub- sy

terns an d f o r e 1 e c tr o ch emi c a 1 en er gy storage sy s t e ms . The

phy s ic a 1 proper ties a s s e s s e d a r e : me 1 1 i n g po i n t s ; phase d iagr am s ; eut ec

i c compo s i t io n s ; d e n s i ty f su r f a c e t en s i o n ; viscosity ; el ec tr i c a 1

conduc t i v i t y ; d if fu s io n c o n s t a n t s f or io n s ; h e a t. of fusion ; he at c ap a c

- ity; v o 1 ume cha nge 0 n f u s i o n r va po r P res s ur e ; t h ermal cond uc t i vi ty

( 1 iqui d and sol id) ; an d c r y o sc op i c CO n s t a nt

Th e status o f CO r r o s io n

s t ud i e s in the form o f a n n o t at ed b i bl iog r aph i c s ummar ies

and sa li en t

obs erv a t ions on s a f e ty a n d h a z ar d s ar e a 1 so r e po r t ed . A s umma r i z i ng

series o f table s is pr o V i d e d a s in d ex to the d at a-gaps sta tu s f o r th i s set of c andidat e ma t er i a 1 s #

17. KEY WORDS (six to twelve entries; alphabetical order; capitalize only the first letter of the first key word unless a proper name;

separated by semicolons) Corrosion; data compilation; electrochemical energy storage materials;

molten salts; physical properties; safety and haz rds; thermal energy

storage materials; thermal properties; thermodynamic properties

transp ort properties,

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Supplement No. 1 to Vol. 3 “THERMAL CONDUCTIVITY OF THE ELEMENTS:

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