NBSIR 81-2345

A Report on Some Thermodynamic

Data for Desulfurization Processes

U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

Center for Chemical Physics

Chemical Thermodynamics Division

Washington, DC 20234

September 1981

Final

Prepared for Department of Energy

Morgantown Energy Technology Center

Morgantown, West Virginia

/OO

US 6

# 8 h^zis

cof Standard Reference Data, NBS

NBSIR 81-2345

A REPORT ON SOME THERMODYNAMIC

DATA FOR DESULFURIZATION PROCESSES

V. B. Parker, B. R. Staples, T. L. Jobe, Jr., and D. B. Neumann

U S. DEPARTMENT OF COMMERCE

National Bureau of Standards

Center for Chemical Physics

Chemical Thermodynamics Division

Washington, DC 20234

September 1981

Final

Prepared for Department of Energy

Morgantown Energy Technology Center

Morgantown, West Virginia

and

Office of Standard Reference Data, NBS

U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige, Secretary

NATIONAL BUREAU OF STANDARDS. Ernest Ambler, Director
f

I
TABLE OF CONTENTS

I. General Description Pa 9e

1. Introduction 1

2. Explanation of the Contents of the Tables 3

3. Unit of Energy and Fundamental Constants *. . . . 8

4. Internal Consistency of the Tables 8

II. Tables for the Thermochemical Property Values of Substances.

1. The 0, H, S, or C containing substances 16

2. The Fe - 0, H, S, or C containing substances 18

3. The Mn - 0, H, S, or C containing substances 20

4. The Mg - 0,H, S, or C containing substances 21

5. The Ca - 0, H, S, or C containing substances 23

6. The Na - 0, H, S, or C containing substances 24

7. The K - 0, H, S, or C containing substances 26

III. Tables for the Thermochemical Values for Processes

1. Processes involving 0, H, S, or C containing substances 28

2. Processes involving Fe - 0, H, S, or C containing substances. . . 30

3. Processes involving Mn - 0, H, S, or C containing substances. . . 32

4. Processes involving Mg - 0, H, S, or C containing substances. . . 3 3

5. Processes involving Ca - 0, H, S, or C containing substances. . . 35

6. Processes involving Na - 0, H, S, or C containing substances. . . 36

7. Processes involving K - 0, H, S, or C containing substances . . . 38
IV. Tables for the Property Values of Binary Aqueous Systems as a Function

of Concentration Page

1 . S0

2 40

2. H

2 S03

41

3. H

2 S04

42

4. FeS0

4

44

5. Fe

2 (S0

4

) 3

45

6. Fe(HS0

4

) 3

46

7. MnS0

4 47

8. MgS0

4 48

9. CaS0

4

49

10. CaS

2 0

3 50

1}. Na

2 S03 51

12. Na

2 S0

4 52

13. NaHS0

4 53

14. KOH 54

15. K

2

S0

3

55

16. K

2 S04

56

17. KHS0

3

57

18. KHS0

4

58

V. Documentation for the Thermochemical Values for Some Processes

1. Processes involving Fe 60

2. Processes involving Mg 61

3. Processes involving Ca 65

4. Processes involving Na 68
Page

VI.

VII.

Documentation and Discussion of the Aqueous Solution Property Values

1 . Activity and Osmotic Coefficients 71

2 . The Relative Apparent Molar Enthalpy 74

Bibliography 76
A REPORT ON SOME THERMODYNAMIC

DATA FOR DESULFURIZATION PROCESSES

by

V. B. Parker, B.R. Staples, T.L. Jobe, and D. Neumann

Abstract

Tables are presented here of values of thermochemical properties and processes

at 298.15 K for some substances of interest to DOE for flue gas desulfurization.

_p

The substances covered are (1) the aqueous ions: OH , SO^ , HSO^,

SO"

2

, HSO", CO"

2

, HCO", H+

, Mn

+2

, Fe

+2

, Mg

+2

, Ca

+2

, Na

+

, and K+

, and (2) solid,

liquid, aqueous, and gaseous compounds or species formed from these ions.

The tables contain the following:

1. The thermochemical property values, enthalpy of formation, A^H°,

Gibbs energy of formation, A^G°, entropy, S°, and heat capacity, C° all at

298.15 K, as well as the enthalpy difference between 298.15 K and 0 K,

H°-H°, for the basic species cited above.

2. The predicted values for aH°, aG°, aS°, and aC° as well as log K

r (equilibrium constant) for the processes, or reactions, of importance to DOE,

calculated from (1).

3. The property values, c^, the relative apparent molar enthalpy, y +

,

the mean ionic activity coefficient, and <}>, the osmotic coefficient, for

the binary aqueous systems at 298.15 K, all as a function of concentration.

Some documentation for (2) and (3) is provided. All of the values given are

consistent with the NBS TN 270 Series.
I GENERAL DESCRIPTION

1 . Introduction

In this report tables of values of thermochemical properties and processes

at 298.15 K for substances of interest to DOE for flue gas desulfurization processes are presented. This work is part of an ongoing evaluation of the various

systems of interest. An analysis of the more recent data is underway and

these data will be incorporated into these tables in a way which will preserve

the total unity and consistency of the tables.

-2

The substances covered are: (1) the aqueous ions: OH , SO^ , HSO

3

,

S0‘

2

, HSO

4

, CO

3

2

, HCO

3

, H+

, Mn

+2

, Fe

+2

, Mg

+2

, Ca

+2

, Na+, and K+, and (2) solid,

liquid, aqueous, and gaseous compounds or species formed from these ions.

The tables are arranged in three sections.

Section II contains the thermochemical property values, A

f

H°, a^G°, and

(H - H°) in kcal/mol, and S° and C° in cal/(mol •«) , all at 298.15 K, for the basic

substances of interest. They are either obtained from the NBS Technical Note

270 Series, "Selected Values of Chemical Thermodynamic Properties of the

Elements and Their Compounds," [81 NBS] ^ , or have been selected to be compatible

with those tables.

^ References are given in a chronologically ordered bibliography at the

end of the report (section VII). They are cited in the text in coded form

indicating year of publication and the first two authors. The pre 1900

references are listed before and separately from the post 1900 ones.

1
Section III contains the values, aH°, aG° in kcal/mol, aS° and aC° in

cal/(mol*K), and log K for some of the important processes in flue gas desulfurization. Emphasis has been given to the values for solution processes,

i.e., aH° (soln), aG° (soln), aS° (soln), log K° and aC° for the salts and

5 p their hydrates at 298.15 K, as well as to the K's and aH's for ion pairing

or complex ion formation. The process values are derived from the property

values listed in section II as, for example:

aH° = z a^H° (products) -z A f

H° (reactants).

Section IV contains the following property values of various solutions

as a function of concentration: a^H, and the derived <j^, (the relative apparent

molar enthalpy) and y + (mean ionic activity coefficient) and <j> (the osmotic

coefficient)

.

Documentation for section III is provided in section V, as is documentation

for section IV in section VI. Detailed analyses and complete documentation,

however, are not given at this time since it is beyond the scope of this report.

Many of the selections for the properties of the substances involve analysis

of a complex network of thermodynamic data. In that process values for

individual processes or substances may become modified in order to achieve

a set of "best values." Some documentation, however, is provided on some

processes where the experimental measurements oif a particular process are the

definitive ones for the predicted properties of that process or where newer

data indicate the need for revision. Documentation is also provided for the

activity coefficients given in the tables on solution properties.

Users of these tables are invited to comment on the selections, correct

errors and bring new measurements to our attention. The support of the

Department, of Energy and Office of Standard Reference Data, NBS is gratefully

acknowledged.

2
2. Explanation of the contents of the tables

The following material, adapted from [81NBS] provides definitions and

conventions used in the tables.

2.1 Physical States

The physical state of the substance is appended to the chemical formula

in parentheses: NaOH(c) = NaOH, crystalline. The abbreviations most

commonly used to denote physical states are listed in Table 1-1. Any other

notations are explained in the tables.

2.2 Definition of Symbols for the Thermochemical Properties

and Thermochemical Processes

The headings used in the tables in section II and their meanings are:

A^rH° standard enthalpy of formation at 298.15 K;

A^G° standard Gibbs energy, G, of formation at 298.15 K;

rf* - n® enthalpy, H, of the compound in the indicated state at 298.15 K

referred to its value at 0 K. If the indicated state at 298 K

is gas, the corresponding state at 0 K is the hypothetical ideal

gas; if the state at 298 K is solid or liquid, the corresponding

state at 0 K is the thermodynamically stable crystalline solid,

unless otherwise specifically indicated.

S° standard entropy, S, at 298.15 K;

C° heat capacity at constant pressure at 298.15 K.

The Gibbs energy is related to the other quantities by: G = H-TS,

where T is the thermodynamic temperature. The enthalpy is related to the

internal energy, E, by: H = E + PV, where P = pressure and V = volume.

All values refer to one mole of substance for the formula given.

3
For the processes listed in the tables in section III the headings and

their meanings are:

aH° enthalpy change for the process under standard conditions,

i.e., for the substances in their standard states, at 298.15 K

Gibbs energy change for the process under standard conditions, etc.

Entropy change for the process under standard conditions, etc.

heat capacity change at constant pressure at 298.15 K

The common logarithm of the equilibrium constant,

equal to -aG°/2. 3026RT

The tables in section IV for the solution properties have the following

headings and meanings.

<j) L the relative apparent molar enthalpy

y + the mean ionic activity coefficient

AG°

AS°

aC

p

log K

cj) the osmotic coefficient.

2.3 Conventions Regarding Pure Substances

The values of the thermodynamic properties of the pure substances given

in the tables in section II are for the substances in their standard states.

These standard states are defined as follows:

For a pure solid or liquid, the standard state at any temperature is the

substance in the condensed phase under a pressure of one atmosphere.

For a gas the standard state at any temperature is the hypothetical ideal

gas at unit fugacity, in which state the enthalpy is that of the real gas at the

same temperature and at zero pressure.

The phase of a substance is indicated in parentheses at the end of the

chemical formula. See section 1-2.1.

4
The values of A

f

H° and A

f

G° given in the tables represent the change in

the appropriate thermodynamic quantity when one mole of the substance in its

standard state is formed, isothermally at the indicated temperature, from

the elements, each in its appropriate standard reference state. The standard

reference state at 25°C for each element except phosphorus has been chosen to

be the standard state that is thermodynamically stable at 25°C and at one

atmosphere pressure. For phosphorus the standard reference state is the

crystalline white form; the more stable forms have not been well characterized

thermochemical ly. The same reference states have been maintained for the elements

at 0 K except for the liquid elements bromine and mercury for which the reference

states have been chosen as the stable crystalline forms. The standard reference

states for the elements are indicated in the tables by the fact that the values of

A

f

H° and A^G° are exactly zero.

The values of S° represent the virtual or "thermal" entropy of the

substance in the standard state at 298.15 K, omitting contributions from

nuclear spins. Isotope mixing effects, etc., are also excluded except in the

1 2 case of the hydrogen-deuterium ( H- H) system. Where data have been available

only for a particular isotope, they have been corrected, when possible, to the

normal isotopic composition.

2 . 4 Convention Regarding Solutions

For all dissolved substances the composition of the solvent is indicated

in parentheses following the chemical formula. Except in special cases,

discussed below, the number of moles of the solvent associated with one mole

of solute is stated explicitly. See section I- 2.1 and Table 1-1 for the

conventions used.

5
The standard state for a non-dissociated solute in aqueous solution is

taken as the hypothetical ideal solution of unit molality, which has been

designated as "std state, m = 1." For strong electrolytes in aqueous solution

the conventional standard state is the ideal solution of unit activity (unit mean

molality). For non-aqueous solutions the standard state of the solute is the

hypothetical ideal solution of unit mole fraction of solute (std. state,

x

2 = 1). The designation "a" is used for strong electrolytes in the standard

state and "ao" for undissociated species in water solution. In non-aqueous

media the standard state defined above is indicated by appending "X" to the

formula of the solvent. The convention "std state, m = 1" is used only

rarely for non-aqueous media. An "s" is appended to the formula of the

solvent to designate this condition.

The value for a^H for a solute in a solution of definite composition is

the apparent enthalpy of the reaction of formation of the real solution

from the elements comprising the solute, each in its standard reference state,

and the appropriate total number of moles of solvent.

Elements + solvent -* salt (dissolved in solvent). When using this

representation for a^H for the dissolved species the value of A

f

H for the

solvent is not required; the experimental value of an enthalpy of dilution

can be obtained directly as the difference between the two values of a^H

at the corresponding concentrations.

It may be noted, to avoid confusion, that A

f

H applies to the real

solution, including any hydrolysis, ionization or other reaction that occurs

upon solution of the solute.

6
The value for A f

H° for a solute in its standard state is equal to the

apparent molar enthalpy of formation of the substance in an ideal solution

containing the species of which the solute is assumed to be nominally

composed. If this speciation is the same as that in the real solution at

oo infinite dilution, then a^H° is equal to a^H , the enthalpy of dilution of an

ideal solution being zero. The assumed nominal composition of the solute is

that at infinite dilution for non-dissociating substances, salts composed of

ions that do not react further, such as Nal, and KNInO^, and the common acids,

such as HC1 , H

2

S0^, H^PO^ and acetic acid. THe assumed nominal composition for

salts containing ionizable or hydrolyzable species is not the same as the

speciation in the real, infinitely dilute solution. For example, NaHSO^ is

composed of Na

+ and HSO^ ions in its standard state, while the infinitely

+ + 2

- dilute real solution contains Na , H and SO^ ions. THe difference between

the a^H's for these two solutions is the enthalpy of ionization of HSO^.

The values of the thermodynamic properties tabulated for the individual

ions in aqueous solution are based on the usual convention that the values of

A^H , a^G , S° and C° for H (aq, std. state, m = 1) are zero. For an ionic

e.g. , HSO^ , the properties tabulated refer to that undissociated ion,

i.e. they are not equal to the sum of those for its constituent ions. By

adopting the above convention with respect to aqueous H+

, it follows that the

thermodynamic relation A

f

G° = A

f

H° -T[A

f

S° + [n/2]S° (H

2

(g:s) ) ] where A

f

S° has

been calculated from tabulated entropies holds for individual ionic species,

with n equal to the algebraic value of the charge. For neutral electrolyes,

(and gaseous ions) the normal consistency relationship applies. See

section 1-4.
3. Unit of Energy and Fundamental Constants

All of the energy values given in these tables are expressed in terms of

the thermochemical calorie. This unit, defined as equal to 4.184 joules

exactly, is generally accepted for the presentation of chemical thermodynamic

data. Values reported in other units have been converted to calories by means

of the conversion factors for molecular energy given in Table 1-2.

The values in this table are consistent with the CODATA Fundamental

Constants [73C0D] and negligibly different from those listed in [81NBS].

The formula weights used in the tables are those listed in [81NBS]. Use of

more recent atomic weights [80IUP] would produce only insignificant changes

in the tabulated thermodynamic values.

4. Internal Consistency of the Tables

All of the values given in the tables of thermochemical properties

have been calculated from the original articles, using consistent values

for all subsidiary and auxiliary quantities. The original data were corrected

where possible for differences in energy units, molecular weights, temperature

scales, etc. Thus we have sought to maintain a uniform scale of energies

for all substances in the tables. In addition the tabulated values of

the properties of a substance satisfy all the known physical and thermodynamic

relationships among these properties. The quantities A^-H

0

, A^G°, and S° at

298.15 K satisfy the relation:

A

f

G° = A

f

H° - T A

f

S°

.

to the precision given. The special case of solutions is discussed in section 2.4.

Furthermore the calculated value of any thermodynamic quantity for a reaction is

independent of the path chosen for the evaluation.

8
In some cases newer data may have become available on certain substances

after the values were selected for these tables. Because of the need to

maintain the internal consistency of the tables, it is not always possible

to incorporate these newer data into the tables without a detailed analysis of

the effect of such a change. Unless great care is used, relatively significant

errors in calculated values of aH° or aG° for specific reactions may result from

the introduction of such data. See section 1-4.2.

There are, however, some substances [limited to the sodium and potassium salts

p p of SO^ (a), HCO^a) and CO^ (a)] for which the G-H-S relationship has been relaxed,

so that a^.G°(c) does not equal a^H°(c) - T a^S°(c) within the stated uncertainty.

These are designated in the tables (section II) by the statement:

G-H-S constraint has been relaxed.

The rationale is as follows:

Newer data on the entropies of solution and Third Law entropies of a

number of salts have led to significantly different values of the entropies

of these ions from those reported in TN 270-3 [81NBS] and used throughout the

series. In order to retain the basic principle of those tables insofar as

possible, namely that the values in the tables should yield "best" values for

thermodynamic processes, values for A

f H°, and a^G° for the alkali metal salts

have been selected such that the "best" values of aH° and aG° for the ideal

solution process are maintained. The values of S° for the salts are selected

from measurements independent of the solution process. In these cases the

following thermodynamic relation:

aS° (solution) = [aH° (solution) - aG° (solution)]/T

will hold for the ideal solution process but the following relation may not

be satisfied within the expected precision of the individual values of S°:

AS°(solution) f 1 S°(a) - S°(c)

ions

9
Those processes affected in section II are designated.

See TN 270-8 [81NBS] for further details.

4.1 Uncertainties

The uncertainty in any value in the tables in section II depends on the

uncertainties of all the determinations in the total chain of reactions used

to establish the value.

In general, when uncertainties are not stated explicitly certain rules

have been followed with respect to the number of significant figures recorded.

Values are tabulated such that the overall uncertainty lies between 2 and

20 units of the last figure. On the other hand, values are given so that the

experimental data from which they are derived may be recovered with an accuracy

equal to that of the original quantities. Thus the number of significant

figures for any one value in the tables need not represent the absolute

accuracy of that value. For solutions of varying composition, values are

frequently tabulated to more figures to make possible the recovery of enthalpies of solution and dilution.

Each value, then, calculated for a process from the property values is

given to one more decimal place than the property value with the least

significant value.

4.2 Relationship to Other Tables of Thermodynamic Properties and Processes

The chemical thermodynamic properties and processes in the present tables

may be combined with those published in TN 270 [81NBS] in order to calculate

the change in another process. However we recommend against these values

being combined with those in any other tabulation or with a property reported

in an original research paper.

There are several reasons for avoiding the combination of thermochemical

data from more than one source table. The most important is that different

10
large-scale tables use different thermochemical properties of formation for

substances that are ubiquitous in thermochemical measurements. Outstanding

examples are the common inorganic acids and their ions. Another reason is

that the groups preparing different tables may have relied on different

measurements as the basis for selecting property values.

It is difficult to predict a priori how a change in one selected

formation property or in a process would affect values assigned to other

substances or processes because of the way these are linked by complex networks.

In general, it may be expected that the advantage of internal consistency of

a table will be lost if values from several sources are combined and that

experimental measurements may be reproduced poorly.

No general, simple algorithm can be suggested for overcoming this

problem. If it becomes necessary to extend a table of data to substances

other than those tabulated, the user is advised to consult the group that

prepared the table about the procedure that he plans to use.

11
Table 1-1

:

Physical State Conventions

The following conventions are used to designate the physical state of

a substance. This information appears in a parenthetical expression appended

to the molecular formula.

Basic Symbols Explanation

(g)

(gs)

(c)

(cs)

(

1 )

(Is)

(am)

(gi)

(a)

Gaseous, e.g. , HC1 (g)

Gaseous reference standard state for an

element, e.g., 0

2 (gs) for 0^ ( g

)

Crystalline, e.g., NH^CHc)

Crystalline reference standard state for an

element, e.g., Rb(cs) for Rb(c)

Liquid, e.g., H^CKl)

Liquid reference standard state for an

element, e.g., Br^ls) for Br^ ( 1

)

Amorphous

Glassy

Hypothetical standard state of the ideal

aqueous solution at unit activity. For a

neutral electrolyte the value of a property

is equal to the algebraic sum of the values

for the ions assumed to constitute the

molecule of the electrolyte, e.g.,

HCl(a)=H

+

(a) + Cl"(a). For an ionic species

this notation is commonly used to refer to the

undissociated ion as written, e.

g

. } HS0

4

~(a)

.

12
Basic Symbols Explanation

(ao) Hypothetical standard state of the ideal

aqueous solution at unit activity of the

undissociated (non-ionized) species, e.g.,

HF(ao), HF^ao). May also be used whenever

the designation (a) could be ambiguous.

Note that the descriptions HSO^(a) and HSO^(ao)

are equivalent, but that HF(a) and HF(ao)

are not.

13
CONVERSION

FACTORS

FOR

UNITS

OF

MOLECULAR

ENERGY

CD

m

m NO

m i—1 i i 1 1 3 in o o NO o o O On r-l r-4 NO r-l r-. m rH

CDXX r-lX rH

X

rH nO NO o rH o O on on in CO r—l g o on o • • • • > i—i r—l cn CN] cd

cd 1—1 3 CM

T 1 cn r-l o 1 1 i o- l cd m o m O r—l o 00 o rH on >-i in i—l

r-l r-l cn cn rH o ON X r-~ X o X on <1- X g m ON r- •N cn -O' o ON

—i • • o • i 00 cn 00 cn rH go

r—l CM r-l o on NO I CM g CM ON ON O i ON i'» r-l r—l 43 ON 00 NO X r-- I 1 CM ON m rH M. n- cn in P • • • «\ 4-1 O i—4 r-4 M

NO 00 i CM 1 i i 1—4 00 o CM o 00 o rH o o n- i—4 CM 1-4 m rH rH rH g r>- X CM X <r X rH X

NO t—4 t-4 NO

as t-4 00 <|- & • • • 4*5 CM 1—4 CM nO

rHog cn CM o 00

CM 00 ON r-4m

g ON CM CM

X

m 4-1 NO ON m ON

CO 00 CM t-4m • • • • CM

n ON i—lcn CM

go

tH CM rH

i—i 'o 1 O 1 o o in r—l

on rH t-4 rH ^g o X n- X CM CN] X o t-4 t-4 On

t—4

ON CM rs in

CO cn o m o • NO • CM CM 00 m i—1 m

CM o o

t—4 cn o o o vt r-4 o NO g 1—4 00 o 4 CM M. t-4 r-4 o on

*-) • • o 0 o NO CM 4

on

II

11 i—4o rH

II

g ii og

11 t-4

g t—4 o 44 o rO t—1 g CD ^g t-4 o "—,

^g 1-4 cn 43 P

CD

a s 44

O

V -X

M

1—4 «-4 r—l T—1

t-4 i CM

O

m i-i oo

0)

54

0) £ on

r'- • i—i • CD in i—i

NO rO O co 00 -U

CO

•i4 43U ,-4 CM ON 00 II o • c

cn

O *r4 *H

CO P>

1-H -i-4 3 • i—I u m <j- <y T)3 3

NO CM -H

C I I vo o on o to ii On i—I i—l «—l a) CM X O X CO CM 00 3

on NO • • co cn CM CD3

rH • • CD CO > a

CM •r4 CM o t-4 43 NO cn CD C0 o CM 44 e • •s 3 o

00 CM CD *H

i-4

m

g 44

t—4 ON CD CO TO 1-4 C CD 3 54

144

CD CD 43

43 44 <t <(- 44

t—4 00 ON o 44 3 m NO 3 >H 00 o CD >N • cn CO '—1

CM CM CD

54 &,

0- CD CD NO 3

NO

m 43 NO • co CM •<} |4 TD NO 00 CD CD ON 40 3 • NO g *H

1—4 ON 3 CD

1—4 3 44 43 TD O

CD

II 3 CD •H ^

cd II i-4 CD

t-4 54

g 3 CD CD o 1—1 x> co

CD 3 3 54 1—l o 3 O o CD 44 ^g i-4 CD O o 43 CD -4 g E4 M4 1 g > o 0> rH rH

14
II Tables for the Thermochemical Property Values of Substances

The values tabulated are A^H°, a^6° and H° - H° in kcal/mol, !

C° in cal/(mol • K) , all at 298.15 K.

The tables are arranged in the following order:

Table II--1 The 0, H, S > or C

II--2 The Fe - o, H, s,

II--3 The Mn - o, H, S

>

II--4 The Mg - o. H, s,

II--5 The Ca - o, H, s.

II--6 The Na - o, H, s,

II--7 The K - o, H, s.

° and

15
Formula

and

Description

298.15

K

(25°C)

I

3*-

•HU

<13

I

I © I CL I U I

I

I

I o I CO I

I

o |

i

i >0 0* in CD A i H 00 o CM ro

i

i O o 00 in O' O in i i H

1

i 43 in (XI in o 04 o

o i ro r- £ i i i

i \ i H i

rt) i ro oo U i o o r- o o Q>

i o CD 04 in •H 43 to C" n 03

i O i 04 >0 LO l> i> 03 H i> •T

i ro i •'rt in to •43 i

t >0 CD

i ro 43 -H 4)

i CVJ 43 in 04 o

i o 1 o 1 i to o in 1 1 1

i

i

i

i

CM CM 04 04 04

H

i

i

i

i

• ‘M* «r 0(3 •'HI o i O 03 to "T o O' E i o o o in 43 43 o c" 00 43 IO o

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See

Section
Ill Tables for the Thermochemical Values for Processes

The values tabulated are aH° and aG° in kcal/mol, AS° and aC° in cal/(mol*K),

and log K for the processes listed.

The tables are arranged in the following order:

Table 1 1

1 - 1 Processes involving 0,H,S, or C containing substances

1 1

1 -2 Processes involving Fe - 0,H,S, or C containing substances

1 1 1-3 Processes involving Mn - 0,H,S, or C containing substances

1 1 1-4 Processes involving Mg - 0,H,S, or C containing substances

1 1 1-5 Processes involving Ca - 0,H,S, or C containing substances

1 1 1-6 Processes involving Na - 0,H,S, or C containing substances

1 1

1 -7 Processes involving K - 0,H,S, or C containing substances

27
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Heat

Capacity

Changes

of

Reaction

and

Equilibrium

Constant

SC 1 i i r~ 43 ^H1 r' O' 00 GO r- <3 to O'

i i 1 •o-J o "T o •H CM O' CD CM LD CD o» 1 1 1 CO CD O O' O to 00 O' in O O

H | i i to o to CM o •O <a-4 >0 CM in in

1 II 0 or4 t oHI i 1 to 1 i

o I Q. I U I < I

I

I

to

CM

i

(0<

i

CJ 1 O i o 1 £ i in 1 i CM 1 \ i >0

1 r-4 i T-l O to

1 m i CM CM O 0* >0 o

SC 1 u i

• « * • • .

1 i 00 in >0 o O* "T C" U) 1 i 1 to CSS m LO

i i i

i i i

00o

1 CM 1 i © 0 1 i in in O' O >0 CM CM CM o* O'

03 1 1 i CD "5-4 r- in 1 CM ^-0 CD o O' IS 00 T

< 1 I i

• t • .

1 1 i 00 p» CO CM CM o MO CM 00 to M) > I 1 r-4 i t

«e-fl tn *tH) CM -m-4 1 S’

t 8 O i 1 i

1 £ i

1 \ i

| i-4 i

I i « i O 0 8 U i to MO to X 1 I ^ i to •o >0 O' O' I ro 1 1 1 1 < 1 i .

0 i i O' to O to CM

1

1

0

8

0

1 CM

1

<*=*4

1

•JJ

1

i i

6> OL

U u

*** O A A

X o o <0 o

• o o IP0 O CM o 09 A a flj w <9 1 01 Ll HJ <® V 1 'S' Ll. a 4- X 1 a

4 1 1 * CM o X T X X w o o <**• o o 1 X <0 n X -s' ^

*

H X o 'S' o 0) w M' + CM o 4- w Lx.

1 0 1 Ol o 01 4- is 0) 01 CM 4* + Lx. CM o Ll CM X X-' im

CM to + O O 4 X ^ T a

in fl0 A o n <w if® 4- + yi •s- <0 V IK) a -w

* C5 4- «w- •—4 CM X 4* if® 8 m o X CM to 'O' 01 o 01 -s' X •MP* o 4* + o lx. ^ lx. 1 o

n> <0 ro 4* Op 01 01 CM 0) X -S' 4- 4* Ll lx. Ul X T lx. T o CM

CVS PO Of >». 4 + Ll a U T T t 4- A 1- 4- 4- 0l 0) in w o /as Uu Lx. T u tO a a 01 o

-s' O U u o o u fl9 u u

T r Qi CM Ifl m CM 'S' w

a Lx. 01 CM CM 'W 4- PO n CM CM a a m Ll CM CM X A A a

m w r- X X + 4- o X X X X

u u CM in o o X X 01 o o o o 's' MS' + o 'S' MB' o O Li. V •w* QJ 00 0l • o 01 0i m 01 01 01 @1 01 Ll u. Lx. @> Ll lx. u. Ll. CM lx. La. Ll ll.

ro in >0 r- 00 O' O H CM n "T in CM CM CM CM CM CM CM to n to ro to ro to

30
Enthalpy

and

Gibbs.

Energy

of

Reaction,

Entropy

and

Heat

Capacity

Changes

of

Reaction

and

Equilibrium

Constant

aH°

ago

aSO

aC

0

00 in

(M ID o

- o

t4 ^ i 1 ~0 1i to o in

A | r-t | CJ 1 O 1 o 1 e i in i w I CM 1 X 1 v 1 r—1 1 mil i i i r- 00 1 1 O' 1 i

1 U 1 • • •

1 o ro . 00

id i 1 to in 1 e4 1 1

i

00 !

, O' 1 CM 1 1 rH

1 to CM o- 4)

1 1 1 1 1 40 4> 1 1 ro 1 to

1

1 in o 4)

r-t 1 i 1 i O 1 E 1 X 1 rt 1 <o i U 1 CM 4) 4) o

-ac 1 1 1 1 1 CM 4) O' IV CM i

11 ~o 4) O CM IO 00

1

1 1

1 1 in

1

A A

o A A o

to A 1—1 H to A

o V *. o

1 to Q o CM to ro •v A A CM CM 1 P + O rt X X A A + a cn o to to . O' o O' A

10 X Id o *. o o- IV o to o to V w cn + CM cn cn V

CM CM ro X O' X + + A O' X to

1 o 01 O 01 to o 01 o

to + CD li. cn + A A u. cn u. a

o Of a> to to to ro 01 oi cn li. * li. A W — T A ii. * ii. A to O' O' O' + to -r t —• O O O A o T A T cn err CD to cn A

CM a o A m ai ai w •w X A o A

a + id to to •W cn ii. u. CM CM to to to

to at *. 0) 01 1 ai V *. V u. CM 1 CM o u. i> r li. O' ii. CM 1 CM CM 1 to 1 CD o 1 O'' 1 + T ro o O' a T f cn T- O' o to c 01 o cn o li. A A O cn O

o u. A CD X cn A u u A CM A cn X a

•r4 u -r u . u u

f — + + + o o + w + + + U CM o CM CM to to

<d A A ** CM X X A A

01 u to A A u X O' r* O A O' A A A

ce: . Cl id to to • o to o to to to to CO *0*- O' O' O' cn •W cn -— o X CM CM to o O O O . to X CM CM CM cn w + 4- + CD cn cn cn CM + V + + +

0) (b Of at ai 01 ai ai ai ai ai ai 01 01 01 u. li. lx. a. li. U. u. u. u. u. li. a. li. Li. li.

CD O' O rl CM ro ID >0 CD O o

ro to ro M* ’d' o- O ID ID

i

>

:

FeCO-(c)

-»

FeCO,

a)<

-6.14

14.33

-68.7

-

-10.504
and

Equilibrium

Constant

MnHCO,

<ao)

-»

Hn

(a) +

HCO_

<ao>-

1.24 --

-0.909
Enthalpy

and

Gibbs

Energy

of

Reaction,

Entropy

and

Heat

Capacity

Changes

of

Reaction

and

Equilibrium

Constant

00 CM iC 1 1 1 CM r- o o O CM to 00 00

1 1 1 CM to to r- >T CM to U1 CM

a* 1 1 1 > to CM in O 0Q r- 'T O CM O 8 1 1

• • • H I) 1 1 in CM to to to in CM

!

1

1

1

1

1 1

i i i H

i

1

o 1

1

1

1 1 LO in CL 1 1 1 ~o 00 J 1 1 1 in 1 i 1 i i i i 1

in4

oa

4

oX

4

I

I

I

I a

©

in

I CM

i

i

i -x.

i

i in

i aoO

I CM

i

l

i

03

I COI

H 1 in 00 O rH n 1 O CM CM i i O ao c" to 4H in u 1

t • •

1 00 CO to H O' 40 "0 O 43

1 i 1 in 43 to 4H O in CM

1 i i i i i 1

1 to to

1 to O 00 O "T

1 CM to i in CM CM O 4) O' O

1 43 in to in in in 4) to H 1 1 | 4H i H 1 o 1 E 1

1 H 1 to 1 in LO u 1 to in CM 03 CM to O O

2C 1 00 i> in in 1 r- O to 00 ao

1 00 o O yri CVA 43 O r- 4-

1 1 i i i CM 1 4 CM 1

33
Enthalpy

and

Gibbs

Energy

of

Reaction,

Entropy

and

Heat

Capacity

Changes

of

Reaction

and

Equilibrium

Constant

i ro *-8 O' O O' ro O 04

i 00 >0 O' ^“4 in 04 04 O'

Oi i to in ^r-9 i i 40 «?4 1 43 •0* CD o i • • • , • ff-« I

1

i

i

i

in m

i

^-9

i CM1 in

i in

i

li)

1 to

© i a i <_» i i i | i i i i 1 i i 1 1 < >*x i

1 A | r-9 i a i o i O 1 e i in i my i <M 1 \ i O ** | rH i o O

cn i 'O 00 i i t-4 04 1 to i i 1 4 ^ 8 u i

• • • • • •

i •43 ^4 • o CM

in i i ro 1 4D

"rt | i i i i 1 00 | CP I CM II i O' o 0 i O' O' O' 00 O' ro -o O' mH) 13 1 i 00 in O I 8 04 03 1 O M3 to to 4 i • . * .

i H p' CM 04 O' C' O' m

8 H i t t

1 O i s i \ i 0“^ i

8 i © u i CM 04 o ro o O' CM CM CM X 8 -S£ 1 ro 03 o to =9- o 03 ro U) l I i 4 0 i i •

1 i *3* O CD 04 in O 04 ro

1

1

1

1 i 04

1

•*9 ri

i

i i oH)

l

a. AX

6—4 »—

9

myo o CM CM X X

A *-4 AS AX 03 A AX ro

r—

4

tr—

4

r—9 ff—9 H «-

9

AM my my my •my + my "=^ + H o o O o o o ax 'B' AX 04 CM 04 CM AX 04 CM A H P at X X X X as X X u

my CM my 'MB' o X o CM -© IP- ro in CM

04 CM o AX X + X + + + + cn + + X

a> O

+ A*. + ax As AX AX X AX AX •o'

rt> m m ns m 1* m 9fl T at

As my AX my my my my + my X

as •T u f AX to ro AX

my o o o o o u AX o o u +

cn "T cn CO cn cn a o

a a* O o» at at at O my AX a» at O AX cn 2: cn X X X X CM CM ns X X 04 U

Ot at X AX X X r X f 1- T t 03 X ro f T n ro O o o

? t CM o CM o

c ax AX As As AX AX at OD AX AX A OD o A e AX u u u u X r X u u X X r4 U m3 u my w •<*' •my O •W •w O

t-* •mst my O o o o my t o O eo u o o o CM CM CM 04 at CM CM at

as 04 04 04 i X X X X AX X X X

01 X X X 04 M3 E" ro u to in • C£ my ro

«T <3- "T *3* o 't ro ro to o

O o O O O o o o o o Q CJ

cn CO cn CO cn cn cn cn CJ u O O' O' at O' at O' O' O' O' O' O' O' X

X 2: X 2

:

X X X X X X X to

O' o H CM ro o- 10 •nO oo o O

O' CO 00 CD 00 03 CO CD 00 CD CD o

34

MgHCO,

<

ao >

*

Mg

<a>

+

HCO,

(ao)

-

1.34

-

-

-0.982
Enthalpy

and

Gibbs

Energy

of

Reaction,

Entropy

and

Heat

Capacity

Changes

of

Reaction

and

Equilibrium

Constant

35
Enthalpy

and

Gibbs

Energy

of

Reaction,

Entropy

and

Heat

Capacity

Changes

of

Reaction,

and

Equilibrium

Constant

Calculated

from

*H

and

aG

for

the

processes

given.
Enthalpy

and

Gibbs

Energy

of

Reaction,

Entropy

and

Heat

Capacity

Changes

of

Reaction

and

Equilibrium

Constant

SC 1 1 1

CVI o> mH CM

>0 to 00 >0 n to to

1 1 1 'T >0 o -o CM -0 o 00 O’

CJ> 1 1 1 in CM >0 'T 00 to •M* m-4 in O 1 1 1 • • • • • • • • t H 1

1

1

1

1

1

1

1

1 o o o

1 o

1 o

1 o1 O

1 i

a i o i < i

i

i

i a

©

in

I CM o I ~

CO I 4 I XI U)

I 00

O'

I CM o I a i < t

i

i

i

i 0 I 1 I < I

I

I

I

sc

I

o

es 1 * * * * * * H 1 to o V IO o in CM

1 O >0 CD to 00 ort O' u 1 • • • • • • i • •

1 CM in MS 00 • CD n 00

1

1

1 to <T

1 C^ P-

’

MS

1 to CM CM to to o LD us o

1

1 IV IV 00 -40 us in CM rt

1

1 o o o o o o CM H 1 1 1 O 1 E 1 \ 1 H 1 nj 1 in us in u 1 >0 00 m 00 O' o CM C^

1 "T ro 00 O' ms C'' 00 MS

1

1 •40 CM O' US 10 CM US

11

1 i

i

i

O

•o

c

o

u

<0

0) nc

37

Calculated

from

*H

and

aG

for

the

processes

given.
Enthalpy

and

Gibbs

Energy

of

Reaction,

Entropy

and

Heat

Capacity

Changes

of

Reaction

and

Equilibrium

Constant

)

o O CO tO 10 04 O' ro

>0 © o- o CO o

CD 1i r- CO to o

10. in o

i in ro

o 1 1 1 1 CD i 1 1 i 1 1 1 1 1 < 1 1 1

1 1 1 U3 *H

| |

•

1 O'

1 1 c-H 1 1 i CJ 1 o 1 O 1 s 1 in i 1

1 CM 1 1 * * * *

O 1 — 1 rH 1 10 O ro © O'

CO 1 1 m 1 1 © 43 to 1 CO CD © © O' CM 1 4 1 It 1 u 1 • • • • . • • •

1 1 1 ro © O' 43 © to © CM O

1 10 1 1 sH CM i CM

1 -i 1 1

03 ! O' 1

1 CM 1 1 O 1 1 1 CD CO 43 CM 43 O' p' © 43

CJ 1 1 1 1 43 10 1 o 03 to CM 10 | 4 1 1 1

. • . . . . .

1 1 1 r*» 4) •*-4 CM r- 4

1 1 f-H 1 i 1 i i 1 1 i

1 1 o 1 1 E 1 \ 1 f«H 1

1 1 re 1 fO O' CM o 1 1 u 1 43 43 O CM *rt 00 © CD U3 O' LO X 1 1 1 C^ 43 P- Ui © 43 © to to LO 4 1 1 1

1 1 1 ro "T o to H LO L0 P-’ © 4 O

1 1 1 CM rl 1 1 i 1 1 II III

c

ou

re

01 Q£

a

U r-1

-ar- v

X o a o CM ©

rH X (Q T o CM \ 04 X + O

rH cn v + o (0 04 'MT r X re X fO o >*s in X it ro re o o •Mr- © re r in 04

'r 04 1 + X <3* o O

u T cn u u

•V T o + o o CM U

CM a 04 I •^r U X CM ro o re in X X X cn o o o 04 + o it sc

o *H CM ro <3* to

ro ro ro to ro ro

mH r4 mH ^H

C3

rH CM X

o

CM in X

O'

U3 +

+ A

o

re 05 04

ro T O

o U

o

04 h. 04

M u a A a V +

re r0 rfl -r* ill o Mnr mt- -w •H CM

“T to to X re o o O r-' o U3 cn cn o u o * ro

04 X CM X O' o

it O it . O

CM CM 04 r T T X t O

in CJ A CM p- u U u •mH u

• to

to to to O

O o O o o U

CO cn u u o CM

CM X CM CM X it

it it it >

o CD 0* © mH ro ro ro ro <T vH r4 «*H mH 4

*

38

Calculated

from

aH

and

aG

for

the

processes

given.
IV Tables for the Property Values of Binary Aqueous Systems as a Function

of Concentration.

The values tabulated are <j> L

, the relative apparent molar enthalpy,

y +

, the mean ionic activity coefficient, and <j>, the osmotic coefficient,

as a function of the number of moles of H^O, n^O, per mole of solute,

and as a function of the number of moles of solute, mol/kg H^O. Also

included are the a^H's as a function of the concentration obtained

from NBS TN 270 [81NBS] and the parameters for the equations used to

generate y+ and <p (for which see section VI). All values are reported

at 298.15 K.

The following tabular summary indicates the substances covered,

in the order presented, and the properties tabulated.

T± <t> l y± <!>

IV-1 so

2

/ IV-10 CaS

2

0

3

/

IV-2 h

2 so

3

/ IV-1

1

Na

2 S 0

3

/ / /

IV-3 h

2 so

4

/ / / IV- 1

2

Na

2

S0

4 / / /

IV-4 FeS0

4

/ IV- 1

3

NaHS0

4

/ / /

IV-5 F e

2

( s°4 )

3

/ IV-1

4

KOH / / /

IV -6 Fe(HS0

4

) 3

/ I V- 1

5

k

2 so

3

IV-7 MnS0

4

/ / / IV- 1

6

k

2 so

4

/ / /

IV -8 MgS0

4

/ / / IV-1

7

khso

3

/

IV-9 CaS0

4

/ / / I V- 1

8

khso

4

/

39
Relative Apparent Molar Enthalpy and Activity Coefficients at 298. IB K

Table

SO

XV- 1

.

2

n HgO A

f H

kcal-mo

1

-i

0. cal-mo

1

3 * -1

0 m mol-kg

100.00 -78.054 5531. . 55508

150 .00 -78.226 5359. . 37005

200.00 -78.355 5230. . 27754

250 . 00 -78.458 5127. . 22203

300 . 00 -78.547 5038. . 18503

400.00 -78.691 4894. . 13877

500 . 00 -78.811 4774. . 11102

750 .00 -79.036 4549. . 07401

1000. 00 -79.201 4384. . 05551

1500.00 -79.461 4124. . 03701

2000.00 -79.642 3943. . 02775

2500.00 -79.776 3809. . 02220

3000.00 -79.891 3694. . 01850

3500.00 -79.989 3596. . 01586

4000 . 00 -80.068 3517. . 01388

5000 . 00 -80.209 3376. . OHIO

7500 . 00 -80.443 3142. . 00740

10000.00 -80.584 3001. . 00555

-83.585 0 0

*,"• -

-1 -83.585 kcal-mol Number of mola lities s IS

[ completely ionized - See note on Table IV-2. HrjSO-j C

Enthalpy data taken from NBS TN 270-Series [BINES

]

40
Relative Apparent Molar Enthalpy and Activity Coefficients at 298.15 K

Table IV-2.

H 2

S0

3

n H

2 0 A

f

H

. i i kcal-mol

0

L

- ,-i cal-mol

0 m

mol -kg

100.00 -146.369 5531. . 55508

150.00 -146.541 5359. . 37005

200. 00 -146.670 5230. . 27754

250.00 -146.773 5127. . 22203

300.00 -146.862 5038. . 18503

400. 00 -147.006 4894. . 13877

500.00 -147. 126 4774. . 11102

750.00 -147.351 4549. . 07401

1000.00 -147.516 4384. . 05551

1500.00 -147.776 4124. . 03701

2000.00 -147.957 3943. . 02775

2500.00 -148. 091 3809. . 02220

3000.00 -148.206 3694. . 01850

3500.00 -148.304 3596. . 01586

4000.00 -148.383 3517. . 01388

5000.00 -148.524 3376. . OHIO

7500.00 -148.758 3142. . 00740

10000.00 -148.899 3001. . 00555

« -151.900 0 0

V = -151.900 kcal-mol Number of molalities =

[ 2H +

+ S0

3 “ 1 Enthalpy data taken from NBS TN 270-Series [81NBS3

H^SO^ is thermodynamically equivalent to SO^ + H^O. They are not

distinct species. Both the S0

2

and HgSO^ tables are for the formation

of the real solution; including all effects of ionization.

41
Relative Apparent Molar Enthalpy and Activity Coefficients at 298.15 K

Table IV-3.

h 2S0 4

c X CM o *f H

, , , -i kcal-mo

1

0

L

cal-mo

1

1.00 -201.193 16127.

1.50 -203. 128 14192.

2.00 -204.455 12865.

2.50 -205.452 11868.

3.00 -206.241 11079.

3.50 -206.886 10434.

4.00 -207.428 9892.

4.50 -207.889 9431.

5.00 -208.288 9032.

5.50 -208.637 8683.

6. 00 -208.944 8376.

7.00 -209.458 7862.

8. 00 -209.865 7455.

9. 00 -210.190 7130.

10.00 -210.451 6869.

12.00 -210.835 6485.

15.00 -211.191 6129.

20.00 -211.500 5820.

25.00 -211.660 5660.

30.00 -211.755 5565.

40 .00 -211.869 5451.

50. 00 -211.944 5376.

75.0 0 -212.068 5252.

100. 00 -212.150 5170.

115. 00 -212.192 5128.

150. 00 -212.282 5038.

200. 00 -212.387 4933.

300 . 00 -212.565 4755.

400 . 00 -212.709 4611.

500. 00 -212.833 4487.

600.00 -212.950 4370.

700. 00 -213.040 4280.

800.00 -213.128 4192.

900.00 -213.205 4115.

1000 . 00 -213.275 4045.

1500.00 -213.557 3763.

2000. 00 -213.785 3535.

3000. 00 -214.135 3185.

4000. 00 -214.415 2905.

continued.

.

tJ± 0 m

mol -i<g

- - 55.50807

- - 37.00538

3.3732 2.4792 27.75403

2.2343 2.3916 22.20323

1.6038 2.3057 18.50269

1.2214 2.2288 15.85945

.9574 2.1440 13.87702

.7708 2. 0569 12.33513

.6366 1.9726 11.10161

.5381 1.8933 10.09238

.4639 1.8196 9.25134

.3620 1.6377 7.92972

.2970 1.5740 6.93851

.2530 1.4756 6.16756

.2220 1.3903 5.55081

. 1823 1.2517 4.62567

. 1512 1.1034 3.70054

. 1293 .9542 2.77540

. 1213 .8706 2.22032

.1187 .8202 1.85027

.1193 .7651 1.38770

. 1225 .7362 1.11016

. 1326 . 7004 .74011

. 1423 .6818 .55508

. 1477 .6741 .48268

. 1594 .6619 .37005

. 1743 .6527 .27754

.2000' .6480 . 18503

.2219 .6510 . 13877

.2411 .6568 .11102

.2582 .6636 . 09251

.2738 .6706 . 07930

.2879 .6775 . 06939

.3010 .6842 . 06168

.3130 .6906 . 05551

.3627 .7180 . 03701

.4005 .7390 . 02775

.4562 .7693 .01850

.4964 .7905 .01388

42
Relative Apparent Molar Enthalpy and Activity Coefficients at 298.15 K

Table IV-3 continued.

H

2S0 4

n H

2

0 V

kcal-mo 1

0L

1 , ,-i cal-mo

1

0 m

mo 1 -kg

5000.00 -214.620 2700. .5276 .8064 .OHIO

7000.00 -214.945 2375. .5738 .8293 .00793

10000.00 -215.285 2035. .6211 .8516 .00555

15000. 00 -215.665 1655. .6717 .8744 .00370

20000.00 -215.900 1420. .7050 .8889 .00278

30000. 00 -216.232 1088. .7482 .9069 .00185

50000.00 -216.545 775. .7957 .9260 .00111

70000. 00 -216.706 614. .8229 .9366 .00079

100000. 00 -216.855 465. .8484 .9463 .00056

150000.00 -216.971 349. .8735 .9557 .00037

200000. 00 -217.042 278. .8890 .9614 .00028

300000.00 -217. 120 200. .9080 .9682 .00019

500000. 00 -217.187 133. .9276 .9752 .00011

700000. 00 -217.221 99. .9383 .9789 .00008

1000000.00 -217.246 74. .9479 .9823 .00006

2000000 . 00 -217.277 43. .9628 .9874 .00003

-217.320 0 0

.0 -i

*fH * -217.320 kcal-mo

1

Number of molalities » 55

Enthalpy data taken from NBS TN 270-Series [ 81NBS

]

Activity coefficient data from [ 81STA 3 Constants for the activity coefficient equation be!LOW :

B1 = -7. 26977066E + 0 0 B4 * 9. 96540329E + 0 0 B7 = -1.9283521

B2 * 1. 27851225E+01 B5 * -4. 32909954E+00 B8 - 1.7656501

B3 = -1. 42296622E+01 B6 * 1. 17197320E + G 0 B9 = -6.8985200

Equation for the activity coefficient of H^SO^:

9

In = £ B . m^2

J J=1
Relative Apparent Molar Enthalpy and Activity Coefficients at 298.15 K

Table IV-4.

FeSO

4

o CM c X A

f

H 0

L

kcal-mo 1

* cal-mol

200. 00 -237.100 1500.

40000 . 00 -237.800 800.

** -238.600 0

0

A

f

H -238.600 kcal-mol

0 m mol-kg 1

. 27754

. 00139

0

Number of molalities = 2

Enthalpy data taken from NBS TN 270-Series [81NBS3
Relative Apparent Molar Enthalpy and Activity Coefficients at 298.15 K

n HgO

Table IV-5.

f vsv3

*

f H 0

L

0 m

-1 -1 -1

kcal-mol cal-mol mol-kg

400 . 00

1000.00

2000.00

3000. 00

*

-653.000 22200. .13877

-653.200 22000. .05551

-653.400 21800. .02775

-653.600 21600. . 01850

-675.200 0 0

0

*fH =

-1

-675.200 kcal-mol Number of molalities * 4

Enthalpy data taken from NBS TN 270-Series [81NBS3

45
Relative Apparent Molar Enthalpy and Activity Coefficients at 298.15 K

Table IV-6.

Fe<HSO .)_

4 3

o CM c X Af H 0

L

tf± 0 m kcal-mol 1 c al -mo 1

* mol -kg

600 . 00

M

-646.500

-663.560

1300.

-15760.

. 09251

0

o -

1

a^H = -647.800 kcal-mol Number of molalities * 1

Enthalpy data taken from NBS TN 270-Series [81NBS3

46
Relative Apparent Molar Enthalpy and Activity Coefficients at 298.15 K

Table IV-7.

MnSO .4

c X CM o

kcal-mol 1

0

L

cal-mol

0 m

mol -kg

20.00 -267.580 2520. . 0439 .7307 2.77540

30.00 -268.020 2080. . 0428 .5562 1.85027

50. 00 -268.180 1920. . 0510 . 4823 1.11016

100.00 -268.330 1770. . 0734 .4846 .55508

200. 00 -268.490 1610. .1072 .5168 .27754

400 . 00 -268.640 1460. . 1540 .5572 . 13877

1000.00 -268.850 1250. .2399 .6248 . 05551

2000.00 -269.070 1030. .3236 .6842 . 02775

3000.00 -269. 140 960. .3784 .7198 .01850

5000. 00 -269.260 840. .4509 .7631 .OHIO

10000. 00 -269.400 700. .5499 .8163 .00555

20000.00 -269.530 570. .6427 .8610 .00278

50000. 00 -269.680 420. .7473 .9065 .00111

100000. 00 -269.770 330. .8103 .9317 .00056

M -270.100 0 0

0 -1 V = -270.100 kcal-mol Number of molalities =

Enthalpy data taken from NBS TN 270-Series C81NBS]

Activity coefficient data from [ 74P IT /MAY

3

Constants for the activity coefficient equation <eqns. VI-1 thru 7)

b = 1 . 20000000E+00 Q

i = 1.400000 0QE+00 a„ = 1.2000 0000E+01

Xb o

II 2. 010 0 0 0 0 OE-0

1

i = 2.980000 00E+00 = 0.0000 0000E+00

C

0

= 1 .82000000E-02

47
Relative Apparent Molar Enthalpy and Activity Coefficients at 298.15 K

Table IV-8

MgSCK

oCM c X A

f ^ 0L

<5± 0 m

„ -1 „ , -1 — kcal-mo

1

cal-mol mol -kg

20.08 -327.100 1800. . 0513 .8481 2.77540

25.0 0 -327.20O 17O0. . 0469 .7072 2.22032

5O.00 -327.410 1490. . 0522 .5340 1 .11016

75.00 -327.520 1380. . 0624 .5194 .74011

100. 00 -327.590 1310. . 0718 .5228 .55508

200 .00 -327.740 1160. .1016 .5459 .27754

300. OO -327.820 1080. . 1238 .5633 . 18503

4O0. 00 -327.880 1020. . 1421 .5772 . 13877

BOO. OO -327.930 970. . 1578 .5888 .11102

600.OO -327.970 930. . 1716 .5989 . 09251

800.00 -328.O40 860. . 1954 .6156 . 06939

1000.OO -328.080 820. .2154 .6291 . 05551

2800. 0O -328.202 698. .2866 .6722 . 02775

5000.00 -328.358 S42. .4003 .7334 .OHIO

10000. 00 -328.467 433. .4976 .7835 .00555

20000.00 -328.581 319. .5969 .8328 .00278

50000.00 -328.707 193. .7163 .8883 .00111

100000. 00 -328.774 126. .7898 .9202 . 0OO56

to -328.9O0 0 0

0 -1

II

1 < X -328.900 kcal-mo

1

Number of molalities =

Enthalpy data taken from NBS TN 270-Series [81NBSJ

Activity coef f ic ien

t

data from [74PIT/MAY3

Constants for the activity coefficient equati on <eqns. VI-1 thi

b s i

.

2O8080OOE+00 a i = *• 400000O0E+00 1 . 200000

= 2. 210 0 0 0 0 0E-0

1

i <3-3. 34300000E+00 f = “ 3.723000

C

0 = 2.58OOQQ0QE-O2

48
Relative Apparent Molar Enthalpy and Activity Coefficients at 298.15 K

Table IV-9.

CaSO . 4

oCM c X A

f

H 0

L

«± 0 m kcal-mol 1 cal-mol 1 mol -kg

5000. 00 -346.414 646. .3714 .7111 .OHIO

7500. 00 -346.518 542. .4276 .7410 .00740

10000.00 -346.566 494. .4695 .7631 .00555

20000. 00 -346.685 375. .5729 .8166 .00278

50000. 00 -346.827 233. .7000 .8784 .00111

100000. 00 -346.915 145. .7791 .9140 .00056

500000. 00 -347.009 51. .8986 .9633 . 00011

1000000.00 -347.026 34. .9284 .9746 . 00006

* -347. 060 0 0

>

-*> X

o

11 -347.060 -

1

kcal-mol Number of molalities =

Enthalpy data taken from NBS TN 270-Series [81NBS]

Activity coefficient data from 1 74P IT/MAY

]

Constants for the activity coefficient equation <eqns. VI-1 thru 7)

b = 1 . 20000000E+00 1.40000000E+00 Q

2 = 1 . 20000000E+01

p° =

C

0 =’

2. 00000000E-01

0. OOOOOOOOE+OO

2. 65000000E+00

w

II -5. 570Q0Q00E+01

49
Relative Apparent Molar Enthalpy and Activity Coefficients at 298.15 K

Table IV-10.

CaSgO-j

oCM c X 4

f

H ®L *± 0 m

-1 -1

kcal-mol cal-mol mol -kg *

35.0 0 -284.560 1040. 1 .58594

100 . 00 -284.800 800. . 55508

200.00 -284.950 650. . 27754

400.00 -285.020 580. . 13877

1000.00 -285.100 500. . 05551

-285.600 0 0

X - -285.600 -1

kcal-mo

1

Number of molalities -

Enthalpy data taken from NBS TN 270-Series [81NBS3

50
Relative Apparent Molar Enthalpy and Activity Coefficients at 298.15 K Table IV-li.

Na^SO^

o CM c X

kcal-mol *

0

L

cal-mol 1

0 m

mol -kg

30.00 . 1939 .7124 1.85027

50. 00 2292 .7026 1 .11016

100. 00 . 2866 .7281 .55508

200. 00 -266.510 190. .3529 .7580 .27754

800.00 -266.410 290. .5029 .8177 . 06939

2000.00 . 6074 .3581 . 02775

10000.00 . 7705 .9195 .00555

50000. 00 . 3812 .9593 .00111

« -266.700 0 0

o -1

a^H = -266.700 kcal-mol Number of molalities * 8

Enthalpy data taken from NBS TN 270-Series [81NBS3

Activity coefficient data from [81GOL3

Constants for the activity coefficient equation (eqns. VI-8 ; 9>

B * 1 . 324160 14E+0 0 C = -2 . 69200069E-0

1

D * 6 . 6731 9796E-02

E * 0. OOQOOOOOE + OO

F * 0. OOOOOOOOE+OO

G = 0. OOOOOOOOE+OO

H = 0. 00000000E+00

I = 0. 00000000E+00

J = 0 . 00000000E + 00

51
Relative Apparent Molar Enthalpy and Activity Coefficients at 298.15 K

Table IM-12.

Na

2

S0

4

o CM c X A

f

H 0

L

<s± 0 m kcal-mol 1 cal-mol -i mol -kg

18. 00 -333.852 -1752. . 1389 . 6735 3. 08378

20. 00 -333.800 -1700. . 1411 . 6539 2.77540

25. 00 -333.593 -1493. . 1494 . 6303 2.22032

28.37 -333.491 -1391. . 1558 .6252 1.95658

30. 00 -333.432 -1332. . 1590 .6244 1.85027

40. 00 -333.165 -1065. . 1780 .6302 1.38770

50.00 -332.988 -888. . 1953 .6417 1.11016

60.00 -332.840 -740. .2107 . 6532 .92513

80. 00 -332.605 -505. .2367 . 6726 .69385

100. 00 -332.420 -320. .2581 . 6876 .55508

120. 00 -332.275 -175. .2762 .6996 .46257

140. 00 -332.184 -84. .2919 . 7093 .39649

160. 00 -332.122 -22. .3058 .7175 .34693

180. 00 -332.076 24. .3183 .7246 .30838

200.00 -332.040 60. .3296 .7308 .27754

250. 00 -331.980 120. .3540 .7435 .22203

300 . 00 -331.943 157. .3743 .7537 . 18503

350. 00 -331.918 182. .3919 .7622 .15859

400.00 -331.901 199. .4072 .7694 . 13877

500. 00 -331.879 221. .4333 .7813 .11102

600. 00 -331.867 233. .4549 .7910 . 09251

800. 00 -331.857 243. .4894 .8060 . 06939

1000. 00 -331.855 245. .5163 .8176 . 05551

2000. 00 -331.872 228. .5991 .8520 . 02775

3000. 00 -331.892 208. .6457 .8707 .01850

4000. 00 -331.907 193. .6774 .8832 .01388

5000.00 -331.920 180. .7010 . 8924 . OHIO

10000. 00 -331.958 142. .7677 .9178 .00555

20000. 00 -331.992 108. .8235 . 9385 .00278

50000. 00 -332. 027 73. . 8805 .9589 .00111

« -332.100 0 0

-332.100 kcal-mol

-1

Number of molalities - 30

Enthalpy data taken from NBS TN 270-Series [ 81NBS 3 Activity coefficient data from [ 81G0L j Constan t s for the act ivity coefficient equation <eqns. MI-8,9

B = 1 . 21597315E + 0 0 E = -4. 86954126E-03 H = 0 . 00000000E

C * -3 . 55728552E-0

1

F = 0. OOOOOOOOE+OO I = 0 . Q0000000E

D * 8 . 29465562E-Q2 G = 0. OOOOOOOOE+OO J = 0 . 0000000QE

52
Relative Apparent Molar Enthalpy and Activity Coefficients at 298.15 K

Table IV-13.

NaHSQ 4A

o CM c X *f H 0

L

-1

kcal-mol cal-mol

10. 00 -269.590 -120.

20. 00 -270.020 -550.

25. 00 -270.040 -570.

50. 00 -270.120 -650.

100. 00 -270.145 -675.

200. 00 -270.294 -824.

300. 00 -270.470 -1000.

400 . 00 -270.604 -1134.

500. 00 -270.710 -1240.

600. 00 -270.970 -1500.

1000. 00 -271.110 -1640.

2000.00 -271.580 -2110.

5000. 00 -272.260 -2790.

M -274.710 -5240

X

o

II -269.470 kcal-mol

Enthalpy data taken from NBS TN

ty± 0 m

mol -kg

5.55081

2.77540

2.22032

1 .11016

. 55508

. 27754

. 18503

. 13877

. 11102

. 06939

. 05551

. 02775

.OHIO

0

Number of molalities = 13

270-Series [81NBS3

53
Relative Apparent Molar Enthalpy and Activity Coefficients at 298.15 K

Table IV-14.

KOH

o CVi c X 4

fH 0L

0 m

-1 -1 kcal-mol cal-mol mol-kg *

3. 00 -112.204 3086. 1673. 5.8770 18.50269

3.50 -112.644 2646. 257.9 4.6598 15.35945

4. 00 -113.039 2251. 77.1172 3.8874 13.87702

4. 50 -113.409 1881. 33.5041 3.3616 12.33513

5. 00 -113.698 1592. 18.2855 2.9843 11 . 10161

6. 00 -114.028 1262. 8.1041 2.4843 9.25134

8.0 0 -114.430 860. 3.3898 1.9579 6.93851

10. 00 -114.657 633. 2.1575 1 . 6880 5.55081

12.00 -114.796 494. 1.6421 1.5250 4.62567

15. 00 -114.920 370. 1.2786 1.3742 3.70054

20. 00 -115.007 283. 1 . 0202 1 . 2349 2.77540

25.00 -115.034 256. .9034 1.1566 2.22032

30 .00 -115. 050 240. .8392 1 . 1066 1.85027

40.00 -115.072 218. .7738 1 . 0471 1.38770

50 . 00 -115.086 204. .7431 1 . 0132 1 .11016

75. 00 -115.104 186. .7155 .9715 . 74011

100.00 -115.114 176. .7102 .9530 .55508

150. 00 -115.129 161. .7154 .9378 .37005

200.00 -115.139 151. .7251 .9325 .27754

300. 00 -115.156 134. .7440 .9303 . 18503

400.00 -115.166 124. .7598 .9313 . 13877

500.00 -115.175 115. .7728 .9332 .11102

700. 00 -115.188 102. .7930 .9371 . 07930

800. 00 -115.193 97. .8011 .9389 . 06939

1000. 00 -115.201 89. .8144 .9422 . 05551

1500. 00 -115.215 75. .8380 .9485 . 03701

2000.00 -115.223 67. .8538 .9531 . 02775

3000.00 -115.234 56. .8745 .9593 .01850

5000. 00 -115.246 44. .8976 .9665 . OHIO

7000.00 -115.252 38. .9110 ' .9708 .00793

10000. 00 -115.258 32. .9236 .9748 . 00555

20000.00 -115.267 23. .9438 .9814 .00278

50000. 00 -115.274 16. .9632 .9378 .00111

100000 . 00 -115.279 11. .9735 .9912 .00056

» -115.290 0 0

= -115.290 kcal-mo

1

Numb er of molalities - 3

Enthalpy data taken from NBS TN 270-Series [31NBS3

Activity coefficient data from t72HAM/WU]

Constants for the activity coefficient equation <eqns. YI-8,9) :

B = 1 . 15000000E+00

C - 2 . 30258509E-0

1

D - 6. 04889000E-03

E * 2. 99336000E-04

F = 3 . 914390 0 0E-07

G - 0. 0Q0G0000E+00

H * 0. 000000Q0E+00

I = 0 . 00000000E+00

J = 0 . 00000000E + 00

54
Relative Apparent Molar Enthalpy and Activity Coefficients at 298.15 K

Table IV-15.

K 2S0

3

n HgO A

f

H

kcal-mol *

0

L

cal-mol

50.00 -272.200 300.

100.00 -271.500 1000 . 200. 00 -271.200 1300.

350. 00 -271.200 1300.

400.00 -271.300 1200.

500. 00 -271.400 1100.

600. 00 -271.500 1000 . 1000.00 -271.900 600.

« -272.500 0

0 * f

H -272.500 k cal-mol

Enthalpy data taken fro m NBS TN

<5± 0 m

mol -l<g

1 .11016

. 55508

. 27754

. 15859

. 13877

. 11102

. 09251

. 05551

0

Number of molalities = 8

270-Series [81NBS]

55
Relative Apparent Molar Enthalpy and Activity Coefficients at 298.15 K

oCM c X A

f

H

kcal-mol *

Table IV-16

K

2

S0

4

0

L

. , “I cal-mol

0 m mol-kg *

50.00 -338.460 -500. 1.11016

60.00 -338.360 -40 0. - - .92513

80.20 -338.180 -220. .2236 .6743 .69212

100. 00 -338.050 -90. .2422 .6832 .55508

200.00 -337.820 140. .3079 .7139 .27754

300.00 -337.770 190. .3515 .7345 . 18503

400 . 00 -337.730 230. .3846 .7501 . 13877

500.00 -337.720 240. .4112 .7627 .11102

600. 00 -337.708 252. .4335 .7731 . 09251

700.00 -337.706 254. .4526 .7821 . 07930

800. 00 -337.707 253. .4694 .7898 . 06939

1000.00 -337.711 249. .4976 .8028 . 05551

1500.00 -337.720 240. .5490 .8260 . 03701

2000.00 -337.732 228. .5851 .8418 . 02775

3000.00 -337.751 209. .6344 .8629 .01850

5000.00 -337.780 180. .6927 .8870 .OHIO

8000.00 -337.806 154. .7413 .9064 .00694

10000.00 -337.819 141. .7625 .9147 .00555

20000.00 -337.854 106. .8205 .9367 . 00278

50000.00 -337.889 71. .8791 .9582 .00111

100000.00 -337.909 51. .9117 .9697 .00056

500000.00 -337.938 22. .9587 .9860 . 00011

» -337.960 0 0

0 -1 * -337.960 kcal-mol Number of molalities * 42

Enthalpy data taken from NBS TN 270-Series [81NBSJ

Activity coefficient datai from [81GQL3

Constants for the activity coeffic ient equation <eqns. VI -8, 9)

B = 9 . 43830 073E-0

1

E s 0.0000 o o o o m + o o H = 0. 0 0 0 0 0 0 0 0E + G C

- -8. 85985775E-02 F = 0.0000 0000E+G0 I = 0. 00000000E+0

D s 0. 00000000E+00 G * 0.0000 0 0 0 0E + Q 0 J = 0 . OOOOQOOOE+O

0

0

0

56
Relative Apparent Molar Enthalpy and Activity Coefficients at 298.15 K

n H

2 0

Table IV-17.

khso

3

A

f H 0

L

0 m

-1 -1 -

l

kcal-mol cal-mol mol-l<g

400.00

* -209.900 90. . 13877

-212.220 -2230. 0

0 V =-

1

-209.990 kcal-mol Number of molalities = 1

Enthalpy data taken from NBS TN 270-Series [81NBS3

57
Relative Apparent Molar Enthalpy and Activity Coefficients at 298.15 K

Table IV-18.

KHSO

4

c X CM o 4

fH 0 m

“1 -1

kcil-mol cal-mol mol -l<g

20.00 -273.500 -1100. 2.77540

25.0 0 -273.500 -1100. 2.22032

50.00 -273.500 -1100. 1.11016

100.00 -273.600 -1200. . 55508

200. 00 -273.800 -1400. . 27754

220 . 00 -273.840 -1440. . 25231

400.00 -273.840 -1440. . 13877

800.00 -274.180 -1780. . 06939

1000 . 00 -274.560 -2160. . 05551

2000.00 -274.680 -2280. . 02775

5000. 00 -275. 050 -2650. . OHIO

9000. 00 -275.700 -3300. . 00617

« -277.640 -5240. 0

0

fH = -272.400 kcal-mol ^ Number of molalities -

Enthalpy data taken from NBS TN 270-Series [81NBS]

58
V Documentation for the Thermochemical Values for Some Processes

The arrangement is as follows:

V-l Processes involving Fe

V- 2 Processes involving Mg

V- 3 Processes involving Ca

V-4 Processes involving Na

59
V-l . Processes involving Fe

The Dissociation of FeOH

+

(ao) (reaction 28)

[63B0L/ARV] determined the hydrolysis K of Fe+ ^(a) to FeOH

+

(ao)

as a function of T.

The Solution Process for Fe(QH)p(c) (reactions 29,35,36)

[83TH0] measured the AH for the precipitation of Fe(0H)

2

from

FeSO^(aq) with KOH(aq). [53LEU/K0L] and [63DAU/DAU] measured the K's for the

formation of FeOH

+

(ao). [566AY/W00] obtained the K's for the formation of

FetOH).^ (ao) and Fe(0H)^”^(ao) from Fe(0H)

2

(c).

The Solution Process for Fe50jnHo 0(c) (n=7,4,1,0) (reactions 42-45)

[63ADA/KEL] measured the AH soln in HC1 (aq) of FeS0^*H

2

0(c) and

FeS0^»7H

2

0(c) . [14F0R] measured the aH (soln) of all the hydrates, as well

as the anhydrous salt, in H

2

0. H

2

0 vapor pressure measurements of the hydrates have been made by [64K0H/ZAS] and [14BIL].

The Solution Process for FeC0 .,(c) (reaction 52)

[35KEL/AND] cite the K to be 3.14 x 10“^. [ ( 1 8) 75BER] measured the

aH for the precipitation from FeSO^(aq) and K-pCO-^aq).

60
V-2. Processes involving Mg

The Formation Properties of MgO(c, macro) and MgO(c, micro) (reactions 68,69)

a^H 0,

s of MgO (Macro-crystal ) and MgO (micro-crystal ) are obtained primarily

from the measurements of [43SH0/HUF] on the aH's of solution of Mg(c) and MgO

in aqueous HC1 , the direct combustion measurements on Mg(cs) by [51H0L/HUB],

and the measurements of [49GIA] on AH(trans) MgO(macro) -> MgO(micro).

The Relationship between MgO(macro and micro) and Mg(0H)p(c) (reactions 68, 69)

The aH measurements of [37WEL/TAY] and [38TAY/WEL] on the solution of

MgO(c,macro) and Mg(0H)

2 (c) in 2N HC1 , as well as the measurements of [37GIA/ARC],

(micro), [48T0R/S&tf],and [43SH0/HUF] on the solution of MgO(c, micro) and

Mg(0H)

2

(c) in IN HC1 , are used to determine the relationship. The decomposition measurements of Mg(0H)

2

(c) by [37GIA/ARC] are in agreement.

The Dissociation of MgOH

+

(aq) (reaction 72)

The log K = -2.58 is obtained from the tabulation of [64SIL/MAR] and [63H0S2].

The Precipitation of Mg(OH)o(amorp ) (reaction 71)

[83TH0] and [87BER] measured the aH (pptn) of Mg(0H)

2

from MgSO^ solutions

with KOH(aq) and NaOH(aq), respectively. In addition, [87BER] measured the

AH from MgCl

2

(aq) with NaOH(aq).

The Solution Process for MgS0o»nH

2

0(c) (n-6,3,0) (reactions 73-77)

The aH measurement of [87HAR] on the solution of MgS0

3

*6H

2

0(c)

,

MgS0

3

*3H

2

0(c) , and MgSO^c) in HCl(aq) and on the solution of a mixture of

MgS0

3

*6H

20(c) and MgCl

2

*6H

2

0(c) in H

2

S0

3 (aq) result in values for the A

f

H°'s

for MgS0

3

(c) and the two hydrates. The aH soln is thus calculated from

Z A

f

H° (aq products) -A

f

H° Mg S0

3

*nH

2

0(c).

61
The tabulated AG°(soln) for MgSO^H^O = 5.036 kcal/mol is obtained

from the solubility, 0.062 moles MgSO^/kg H^O given by [65SEI/LIN] and an

estimated y + (at I = 0.25) = 0.23 obtained from the Davies equation (see

[68HAM]). The calculated AS°(soln) results in S° MgS0

3

*6H

2

0(c) = 77 cal/(mol*K),

a reasonable value. S° MgS0

2

*3H

2

0(c) and S° MgSO-^c) are estimated and are

used to obtain the other tabulated aG°'s for the solution processes.

The Solution Process for MgS0^*nHo0(c) (n=7,6,4,2,l ,0) (reactions 77,79-85)

The aH° (soln) of MgS0

4

(c) in H^O is obtained from the aH (soln)

measurements of [83TH0], [83BER/IL0], and [85PIC] and the tabulated <f> L values

for MgSO^nH^O) at the appropriate concentrations.

The measurements of [25MAR], [59DEW/RIC], and [55KN0/STA] on the

decomposition of MgSO^(c) to Mg0(c) and S0

2 (g) or SO^ ( g ) lead to independent

values for a^H° MgSO^(c) and aH° (soln) which are in poor agreement.

The determination of aH° (soln) MgS0

4

*H

2

0(c) is based on the

measurements of [56JAM/FR0], [83TH0], and[85PIC]. The aH° (soln) for

MgS0^*H

2

0 (amorph) was also determined by [56JAM/FR0] . The aH° (soln) of

MgS0^*2H

2

0(c) , MgS0^*4H

2

0(c) and MgS0^*6H

20(c) were obtained primarily from

the measurements of [83TH0]. The AH(soln) of MgS0^*7H

2

0 as a function of

concentration was measured by [51 KAG/M IS] and [30PER]. These measurements

as well as those of [52KAP/SAM], [83TH0], and [85PIC] determined the AH°(soln)

MgS0

4

-7H

2

0(c).

[65SEI/LIN] lists the saturated solution to be 3.167 mol/kg H

2

0 for

MgS0

4 (aq) in equilibrium with MgS04

*6H

2

0(c) (metastable at 298 K) and

3.026 mol/kg H

2

0 in equilibrium with MgS0

4

*7H

2

0(c) . The activity coefficient

and osmotic coefficient obtained from [59R0B/ST0] are 0.0517 and 0.974

respectively at 3.167 mol/kg H

20, and 0.0496 and 0.930 respectively at

3.026 mol/kg H

2

0 so that aG° (soln) for the hexahydrate and heptahydrate

are 2.539 and 2.735 kcal/mol respectively.

62
The a6° (soln) and the aH° (soln) for the heptahydrate results in a

calculated S° MgS0

4

*7H

2 0(c) = 88.5 cal/(mol *K) . In addition [40BEL] and

[64K0H/ZAS] measured the H

20(g) decomposition pressure of the heptahydrate

to the hexahydrate, resulting in values of 89.0 and 87.4 cal/(mol*K), respectively. The aH obtained by [40BEL] and [64K0H/ZAS] for this decomposition are consistent with the AH(soln) measurements. The [64K0H/ZAS] measurements on the hexahydrate/tetrahydrate decomposition are reasonably consistent

with the solution measurements. For the lower hydrate decomposition their

measurements are not.

[64NEW] measured the aH (soln) of MgS0

4

*7H

2

0(c) and

3Mg(0H)

2 *MgS04

*8H

2

0(c) in HCl(aq). Combining these measurements with those

of [38TAY/WEL] on the AH(soln) of Mg(0H)

2 (c) in HCl(aq) results in

AH° = + 2.1 kcal for 3Mg(0H)

2 *MgS04

*8H

20(c) -> MgS0

4

*H

2

0(c) + 3Mg(0H)

2

(c)

+ H

20(1).

The Dissociation Process for MgS0

4 (ao) (reaction 78)

The tabulated values are obtained from [58NAI/NAN] . Other values are

listed by [64SIL/MAR].

The Solution Process for MgC0

3

*nH

2 0(c) (n = 5,3,0) (reactions 87-89)

[65LAN] reviewed the data on the stability 'relationships in the

Mg0-C0

2 -H2

0 system. His interpretation and calculations were accepted for

the AG°(soln) processes for MgC0

3

‘H

2

0(c) and MgC0

3

*3H

2

0(c) , and for the

aG° for decomposition of MgC0

3

*3H

2

0(c) . The value obtained from these and

accepted for the AG°(soln) MgC0

3

(c) = 7.0 kcal/mol is not in agreement with

the log K

$ = -7.46 obtained by [62HAL]. The AH°(soln) MgC0

3

(c) from the

accepted AG°(soln) and S° MgC0

3

(c) is = -11.50 kcal/mol which is supported

63
by the measurements of [54KAP/STA] on the aH (soln) measurements of MgCOg(c)

and MgO(c) which result in aH = 23.5 kcal/mol for the decomposition of

MgCO^c). The accepted aH for this decomposition is 24.0 kcal/mol in agreement with [41 ROT ] , but in sharp contrast with the measurements of [13MAR/SIM],

[62ELL/M0R], and [58F0L/KLI], which indicate a aH 2 to 4 kcal/mol greater

than the accepted. This system needs reinvestigation.

The Dissociation Process for Mg(HC0o)

+

(ao) (reaction 91)

[63H0S] reported the pK = 0.95 for the dissociation.

64
V- 3. Processes Involving Ca

The Formation Properties of CaO(c)

The a^H° is obtained from the combustion measurements of [56HUB/H0L].

The Relationship Between CaO(c) and Ca(0H)o(c) (reaction 92)

This relationship is obtained from the measurements of [38TAY/WEL],

[37WEL/TAY], and [35SCH/PRA] on AH's of solution of CaO(c) and Ca(0H)

2

(c)

in HC1 solutions. The measurements are in good agreement.

Solution Process for Ca(0H)o(c) (reaction 93)

[65H0P/WUL] measured (and corrected for CaOH

+

(ao) formed) AH(soln)

Ca(0H)2- Their corrected value is 4.36 kcal/mol. They also corrected the

solubility = .0203 mol/kg H^O [56BAT/B0W] for the presence of CaOH

+

(ao), obtaining m Ca

+2

(aq) = 0.0145, m 0H"(aq) = 0.0345, y Ca

+2

(aq) = 0.507 and

y 0H~(aq) = 0.838 (obtained from the extended Debye-Huckel relation), resulting in aG° (soln) = 7.11 kcal/mol or log K° = -5.21. The tabulated values

differ slightly from these because of the influence of other measurements on

related compounds.

The Dissociation of CaOH

+

(ao) (reaction 94)

The dissociation constant was determined by [59BAT/B0W], [54GIM/M0N],

[53BEL/GE0], and [51DAV/H0Y]. The values range from K = 0.07 to 0.04.

K = 0.05 was selected. [54GIM/MQN] and [53BEL/GE0] also obtained aH° = -1.25

and -1.19 kcal/mol respectively for this. [65H0P/WUL] obtained aH° =

-2.0 kcal/mol from a least squares analysis of measurements on CatOH^c).

Solution Process for CaS0., »5Ho0(c) (reaction 96)

[23BIC] measured the solubility and reported aG° (soln) = 9.74 kcal/mol

-8

or K° = 7.25 X 10" assuming the di hydrate was the equilibrium solid phase.

65
This value is assigned to the hemi hydrate equilibrium phase. [70RAD] reports

o K° to be 8.4 X 10" in fair agreement, with the solid phase the hemi hydrate.

The entropy of the hydrate is estimated as 29.0 cal/(mol*K), so that with

aS° - -41.4 cal/(mol*K) and aG° (soln) - 9.70 kcal/mol, aH° (soln) =

-2.3 kcal/mol. This is a correction to TN270-6 [81NBS].

The Solution Process for CaSO^ »nHpO(c) (n=2,0.5 and 0) (reactions 97-102)

[46WAL], [25LAN/DUR], and [30LAN/M0N] measured the aH (soln) of the

dihydrate. They are in good agreement. The tabulated a6° (soln) is based

on K

s

° = 4.22 x 10’^ from [64SIL/MAR]. More recent evidence, [69GAR/GLU],

[76LIL/BRI], and [75Y0K/YAM] indicates that a better aG° (soln) corrected

for ion pairing, is 6.25 kcal/mol based on a solubility = 0.01518 mol/kg H^O,

Y +

= 0.338 and aw

= 0.9995. This would result in aS° (soln) = -21.9 cal/(mol*K).

[41KEL/S0U] reviewed the relationships between the various hydrates.

These were accepted. More recent measurements by [64MCA], on the aH's of

solution of the various hydrates, are in agreement with [41 KEL/S0U] . A

reanalysis of the aG 0,s of solution will be made.

The Solution Process for CaC0o(c, calcite) and (c, aragonite ) (reactions 103,104)

The decomposition pressure measurements of [36SAN], [56HIL/WIN],

[36S0U/R0Y] , [33MAT/BIT] , [60JAN/L0R], and [62BAK] on calcite, and the difference in the aH's of solution of Ca0(c) and CaC0

3

(c) measured by [63MEA/RIC],

[25BAC] , [41R0T/BER] , [37WEL/TAY] , and [28R0T/CHA] result in aH° = 42.62 kcal/mol

for the decomposition to Ca0(c) and 002 (g). ^he V measurements of [60GAR/TH0],

[60BIA/GHI], [58TR0], [29FRE/J0H], and [68HAL/TAS], are in good agreement

and lead to the tabulated AG°(soln) = 11.33 kcal/mol. However, more recent

determinations, such as [74JAC/LAN] indicate that log K

= -8.42

66
(AG°(soln) = 11.49 kcal/mol) if ion pairing is ignored and

log K = -8.47 (aG° (soln) = 11.55 kcal/mol) if CaC0

3

(ao) and CaHC0

3

+ (ao)

are assumed. The AH°(soln) with the latter approach is -2.6 kcal/mol with

ACp = -109 +2 cal/(mol*K) and aS° = -47.4 + 1.0 cal/(mol*K). The values for

the aragonite process are obtained from the transition properties cal cite -*

aragonite, given by [35KEL/AND], [53JAM], and [56MAC].
V-4. Processes involving Na

The Solution Process for NaOH(c), Na0H»H

2

0(c) and Na0H»nH

2

0(l

)

(reactions 106-112)

The aH°'s for the solution processes are taken from the measurements of

[62MUR/GIA] who also measured the low temperature C

p

's (corrected by

[69SIE/GIA]) . [69SIE/GIA] also measured the solubility of Na0H*H

2

0(c) to be

27.312 mol/kg H

2

0. From [72HAM/WU] Y+ = 31.88 and <j> = 2.715 resulting in

AG°(soln) = -6.438 kcal/mol. The vapor pressure measurements are in agreement.

The solution processes for the liquid NaOH hydrates are taken from the measurements of [69SIE/GIA].

The Formation of NaS0^~(ao) (reaction 115)

[75REA], [50JEN/M0N], and [69IZA/EAT] measured the K. The values are

in good agreement. [62AUS/NAI] reported the aH (corrected to p = 0).

The Solution Process for Na

2

S0

2

(c) and Na

2

$Q

2

«7H

2

0(c) (reactions 113,114)

The solid phase in equilibrium with the saturated solution of Na

2 S03

(solubility = 2.42 mol/kg H

20) is Na^Oy 7H2 0(c) . With y + = 0.190 and

<j) = 0.738, AG° (soln) = 0.96 kcal/mol. From the extrapolation of the data

above 308 K the solubility for the anhydrous Na

2

S0

3 (c) would be 2.32 mol/kg

H

2

0 with Y+ = 0.191 and $ = 0.73 so that aG° for this process is

0.62 kcal/mol. This solubility is now believed to be incorrect. The

AG°(soln) would most likely be close to zero. A reexamination is underway.

aH° = -3.55 kcal/mol for solution of the anhydrous salt from the measurements

of [84F0R] who also measured the aH for the solution of the heptahydrate

(aH° = + 11.00 kcal/mol). The vapor pressure measurements of [28TAR] and

[28ARI] on the heptahydrate lead to aG° = 15.87 and 15.36 kcal, respectively

for the dehydration. All these values plus the measured S° Na

2 S0

3

(c)

(see [61KEL/KIN]) were used to obtain the selected tabulated values.

68
The Solution Process for NapSQ^(c) and NapSO^lOHoCKc) (reactions 116,117)

The aG° soln = 1.677 kcal/mol for the decahydrate is obtained from the

solubility = 1.96 mol/kg H

2 0 [49R0S], y+

= 0.156 and $ = 0.621 [59R0B/ST0]

.

The AH°(soln) = 18.84 kcal/mol is obtained from the measurements of

[38PIT/C0U]

.

For the anhydrous Na

2

S0^(c,V, orthorhombic) the measurements of

[69GAR/JEK] lead to aH° = -0.58 kcal/mol. aG° for the solution process

= + 0.420 kcal/mol is obtained from m = 3.63 mol/kg H

2 0 [49R0S] and

Y+ = 0.137 from [59R0B/ST0].

In addition to these measurements, the H

2

0 vapor pressure measurements

of [37HIG] and [29MAT/0GU] on the decahydrate result in aG° = 21.79 kcal/mol

Na

2

S0^*10H

2

0(c) . The tabulated values result from this input data. The S°

Na

2

S0^« 10H

2

0 (c) includes a 1.08 cal/(mol*K) correction for a zero point entropy.

69
VI Documentation and Discussion of the Aqueous Solution Property Values

The arrangement is as follows:

VI-1. A general description of the methods and equations used to

obtain y+3 the mean ionic activity coefficient, and <p. the osmotic coefficient is described. Included are the concentration ranges for which the

equations used for y+ and cp are valid.

VI-2. Some specific sources of information for <|>^, the relative

apparent molar enthalpy, is provided for FeSO^, MgSO^, CaSO^, ^SO^, and

Na^SO^, as well as comments on y + at saturation for these substances.

70
VI-1. Activity and Osmotic Coefficients

Activity and osmotic coefficients can be calculated using various

semi -theoretical equations. There have been two major efforts towards the

evaluation of activity and osmotic coefficients during the past 10 years.

Pitzer and coworkers have formulated a set of equations of the virial coefficient type consistent with both the modern statistical mechanical description of electrolyte solutions and the basic principles of thermodynamics of

solutions. The Electrolyte Data Center at NBS (see [78G0L/NUT ] ) has completed

many detailed critical evaluations of electrolytes using an extensive data

base of all available experimental data and has used extended forms of the

Lietzke-Stoughton-Hamer-Wu equations [62LIE/ST0,72HAM/WU], and more recently,

extensions of the Pitzer equations [74PIT/MAY]. Both of these types of

equations have been employed in the representation of activity data here.

For this report, the activity and osmotic coefficient of 2 : 2 charge type

electrolytes (MgSO^, CaSO^, and MnSO^) have been calculated from the Pitzer

equations

.

For the activity coefficient of these 2 : 2 salts, the equation is

Iny = 41* + mB}jx

+ m

2 ^ (VI-1)

where

fY = -AJI1/2

/(l + bl 1/2

) + (2/b) 1 n ( 1 + bl 1/2)]

9

and rl/2

B

MX

= 2eMX

)+ ^MX^l 1 ) 0 - 0 + a/'2 - 1 c. 2

I)e

1 ]

+ Ufi^/ajDC 1-0 + a

2

I 1/2

- \

a

2

I)e'

a

2

ll/2

]

and

3^

rMx

(VI-2)

(VI-3)

(VI-4)

The osmotic coefficient equation is

<() - 1 = 4f^ + + m Cjj^

71
where

f

4’= -A ri 1/2

/(l + bl 1/2

)]

<p (VI-6)

and

(VI-7)

2

Here, I is the ionic strength, l/2zmz. and MX is the general salt formed

from the M ions. Definition of terms and a more detailed discussion of

these equations are given in reference [74P IT/MAY ] ; parameters for these

equations are given in the appropriate tables (section IV).

For the uni -uni valent compounds, and the unsymmetrical charge-types

,

uni-bi and bi -uni valent compounds, the activity and osmotic coefficients

have been calculated from the Hamer-Wu, Lietzke-Stoughton equations used in

previous evaluations [77STA/NUT]

.

The equation for the osmotic coefficient is:

The parameters for these equations are tabulated in the appropriate

tables in section IV. Activity coefficients for these charge-types may also

be calculated from the Pitzer equations for the uni-univalent and uni-bi and

bi -uni valent salts. In these cases, the Pitzer equations are sometimes applicable to a more limited concentration range. Each table references the sources

of data.

Caution should be exercised in the use of these equations because the

equations are only valid over a specific concentration range. The valid

ranges of concentrations are summarized in Table VI-1.

0=1+ {|z

+z_|Am

[-(l+B I 1/2

) + 21n(l+B I 1/2

)

+ 1/(1 + B I 1/2

] + l/2Cm + 2/3Dm

2 + 3/4Em3 + . . . } (VI-8)

and the activity coefficient:

+ Cm + Dm

3/2

+ Em

2 + . . .. (VI-9)

72
Table VI-1.

Limitations on the Use of Activity and Osmotic Coefficient

Equations at 298 K.

Compound Valid Concentration Range

h

2 so4

mol/kg H

2 0

0.001-28.0

MnS0

4

0 1 O

MgS0

4

0.006-3.0

CaS0

4

0.004-0.0011

Na^SO^ 0-2.0

Na

2 S0

4

0-4.5

KOH 0-20.0

k

2 so4

0-0.7

73
VI-2. The Relative Apparent Molar Enthalpy,

All values for a^H as a function of concentration are obtained from

the tabulations in [81NBS]. <j> L is retrieved from the relationship:

<j> L = A

fH(MX(n H

20)) - A

f

H°(MX(a)

)

where a^H° is the enthalpy of formation in the standard state. See section 1 - 2.4

for conventions used in defining A^H° for electrolytes.

Normally, for simple salts and acids, <j> L is the negative of the

enthalpy of dilution to infinite dilution. However, for salts such as NaHSO^,

having an ion that can itself ionize, <(>^ differs from the enthalpy of dilution to infinite dilution by aH for the ionization of the acid anion.

Specific sources for <j>^ for some systems follows.

FeS0

4

The dilution values have been obtained from the various solution reactions

+2 -2

involving Fe aqueous solutions with SO^ aqueous solutions measured by

[83TH0] and [ 1873BER].

MqSO^i

As indicated under the section for the solution process for MgS0

4 *nH20(c)

[51KAG/MIS] and [30PER] determined the aH (soln) of MgS0

4 *7H20(c) as a function

of concentration. These measurements were converted to aH's (diln) and merged

with the measured aH's (diln) of [28LAN], [31LAN/STR], [32PLA], [27LAN/MES],

[27LAN/MES], and [83TH0] to obtain a smooth curve for <j> L

. The extrapolation

to infinite dilution was made to follow as closely as possible the limiting

Debye-Huckel slope. The aH measurements of [83TH0] on the aH (mix) of

aqueous solutions of MgC^ or Mg(N0

g )2 with coefficients have been calculated

from [74PIT/MAY] and at m = 3.167 mol/kg H

2

O, y+ is 0.0569 which differs

slightly from the value cited in section V from [81NBS], (0.0517). Similarly,

the activity of water differs, 0.964 compared with 0.974 in section V taken

from TN 270-6 [81NBS]. These differences will be resolved.

74
The enthalpies of dilution were obtained from the measurements of [30LAN/M0N

]

and [31 LAN/S TR] . The activity coefficients have been calculated from [74PI T/MAY ]

.

The activities at saturation, 0.01518 mol/kg H^O, agree well (0.331) when compared

to 0.338 cited in section V-4 from [81NBS].

and

The dilution heats for Na^SO^ are based on the neutralization measurements of

[83TH0] and [31 RAM/HAN] with NaOH(aq).

The <j> L values for Na^^SO^ are based on the measurements of [77S0L/VLA],

[74TH0/S MI ] , [41 WAL/ROB] , and [58BR0/GIA].

The activities calculated from [81G0L] agree well with those used in [81NBS]

for saturated solutions of Na^SO^ and Na^SO^.

75
VII Bibliography

< 18 —

)

53FAV/SIL

63PAP

65K0P

71DIT

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73BER

75BER

76MAR

76MAR

7SMAR

83BER/IL0

83TH0

84BER

84F0R

S4F0R2

85PIC

86PIC

87BER

87FR0

87HAR

87 P IC

96CHA

99P0L

< 19— )

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76
25SHE

26STI/FEL

27FRA/HEI

27LAN/MES

27LAN/MES2

28LAN

28ARI

28L0R/W00

28R0T/CHA

28TAR

29FRE/J0H

29GIB/DRI

29MAT/QGU

29PGP/KUN

29R0T

29R0T/MUL

29TRA/PAK

3 OLAN/MON

30PER

31LAN/STR

3 1MOR/MAA

31POP/FLE

31R AM/HAN

32BRI/ROB

32PLA

32R AN/FRA

32ROT/ZEU

32ZAW

33LAN/M0N

33LAT/HIC

33MAT /BIT

34AND

34AND

34BR A/HER

34 JGH/LEP

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34PER

35DRU

35GR0/SCH

35GUR/GIS

35K AM

35KEL/AND

35PER

35SCH/PR

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36HER/BR

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36PER

36R0B/J0N

36SAN

36SGU/R0Y

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4 2S0U/SH0

43SH0/HUF

44KEL/M00

45VGS/YAN

46F0N

46WAL

47EVA

48T0R/SAH

48WAL

49EVA/BAX

49GIA

49R0B/ST0

49R0S

50 JEN/MON

50PER

50PLU

51C0N/MCV

51DAV/HOY

51BUN/JAM

51HOL/HUB

51KAG/MIS

51KOB

S1SMI

52BAI/P AT

52ISI/K IG

52KAP/SAM

53BEL/GE0

53B0C/HER

53 J AM

53J0N/MGN

53LEU/KGL

53MAG/HUI

53PAT/THG

54GI M/MON

S4KAP/ST A

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55K NO/ST A

55SCH/WEI

56BAT/B0W

56GAY/W0Q

56HIL/WIN

56HUB/H0L

56 JAM/FRO

56MAC

56TSC/P IE

57BER/VIN

S7BUN. NYE

57CLA

57CUT/BER

57FR0/BRE

57G0L/GR

A

58BRG/GI

A

S8FOL/KLI

58KAP/SHI

58KQR/VER

58LAP

E8MAR

58NAI/NAN

58STR/PEE

53TR0

59BAT/B0W

59BUR/ABB

59DEW/R IC

59FUR/REI

59K0E/C0U

59MAT

59MAU

59NAI/NAN

59R0B/ST0

60BEW

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6 OSEK/SET

6 0 WAR/ING

6 1ELL/AND

6 iKEL/K IN

61M0R

62AUS/NAI

62BAK

62ELL/MGR

62HAL

62JAK/T AN

62LIE/ST0

62MUR/GI

A

62RAT/MCC

62ZIE/SUL

63ADA/KEL

63BAE/LIE

63B0L/ARV

63DAU/DAU

63ELL

63H0S

63HGS2

63 JAN/KIR

63J0H/SUN

63MEA/R IC

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63WIL

64DEV/RUM

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64NEW

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65PAR

65SEI/LIN

66STE/WEI

67ATK/K0R

6SBUT

68HAL/T AS

68HAM

68R AO/NAT

68SPE/W00

69GAR/GLU

69GAR/JEK

69IZA/EAT

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70RAD

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72HAM/WU

73C0B

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74 J AC/LAN

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< 1975)

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'A COMBINED LEAST SUMS AND LEAST SQUARES APPROACH TO THE

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SOC.; 99, 4930 <1977)

82
77S0L/VLA

77STA/NUT

78G0L/NUT

78STA

79FGE

80IUP

8 OWAG/GAR

81GOL

81NBS

81STA

SOLOV'EVA, C. G . ; VLASENKO, B. B . ; K AR APETYANTS , M. KH.

ZHUR. FIZ. KHIM . ; 51, 2991, (1977)

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DATA; 7, 263 (1978)

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'WORKSHOP ON SULFUR CHEMISTRY IN FLUE GAS DESULFURIZATION',

U. S. DEPARTMENT OF ENERGY TECHNOLOGY CENTER, MORGANTOWN,

W. VA., 26505, JUNE 7-8, (1979)

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1979 TECHNICAL HIGHLIGHTS, NATIONAL BUREAU OF STANDARDS,

NBS-SP572, U. S. GOVERNMENT PRINTING OFFICE, WASHINGTON,

D. C., APRIL, (1980)

GOLDBERG, R. N.; J. PHYS. CHEM. REF. DATA; ( IN PRESS ) WAGMAN, D. D.; EVANS, W. H.; PARKER, V. B.; HALOW, I.;

BAILEY, S. M. ; SCHUMM, R. H.; NBS TECH. NOTE 270-3

(1968) IDEM, NBS TECH. NOTE 270-4 (1969) WAGMAN, D. D.;

EVANS , W. H.; PARKER, V. B. ; HALOW, I. H.; BAILEY, S. M.;

SCHUMM, R. H. ; CHURNEY, K. L. ; NBS TECH. NOTE 270-5 (1971)

PARKER, V. B.; WAGMAN, D. D.; EVANS, W. H.; NBS TECH.

NOTE 270-6 (1971) SCHUMM, R. H.; WAGMAN, D. D .

;

BAILEY, S. M.; EVANS, W. H.; PARKER, V. B.; NBS TECH.

NOTE 270-7 (1973) WAGMAN, D. D. ; EVANS, W. H.; PARKER,

V. B.; SCHUMM, R. H.; NUTTALL, R. L.; NBS TECH. NOTE

270-8 ( IN PRESS > STAPLES, B. R.; J. PHYS. CHEM. REF. DATA ( IN PRESS )

83
NBS-114A (REV. 2-80

U.S. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET (See instruction s)

4. TITLE AND SUBTITLE

1. PUBLICATION OR

REPORT NO.

2. Performing Organ. Report No. 3. Publication Date

81-2345 September 1981

A Report on Some Thermodynamic Data for Desulfurization Processes.

5. AUTHOR(S)

V. B. Parker; B. R. Staples; T. L. Jobe, Jr.; and D. B. Neumann

6. PERFORMING ORGANIZATION (If joint or other than NBS, see in struction s) 7. Contract/Grant No. NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

DoE A121-80-MC14004

8.

Type of Report & Period Covered

9.

SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street. City. State. ZIP)

10.

SUPPLEMENTARY NOTES

| | Document describes a computer program; SF-185, FIPS Software Summary, is attached.

11.

ABSTRACT (A 200-word or less factual summary of most significant information. If document includes a significant

bi bl iography or literature survey, mention it here)

Tables are presented here of values of thermochemical properties and processes at

298.15 K for substances of interest to DOE for flue gas desulfurization. - _ The substances covered are (1) the aqueous ions: OH"; SO^ » HSOg, S0]| , HSO^, CO^,

HCO^, H+

, Mn

+2

, Fe

+2

, Mg

+2

, Ca

+2

, Na+, and K+

, and (2) solid, liquid, aqueous, and

gaseous compounds or species formed from these ions.

The tables contain the following:

1. The thermochemical property values, enthalpy of formation, A

fH°, Gibbs energy

of formation, A^G°, entropy, S°, and heat capacity, C° all at 298.15 k, as well as the

enthalpy difference between 298.15 K and 0 K, H°-H°, for the basic species cited above.

2. The predicted values for aH°, aG°, aS°, and aC° as well as log K (equilibrium

constant) for the processes, or reactions, of importance to DOE, calculated from (1).

3. The property values, <j>. , the relative apparent molar enthalpy, y+» from the

| mean ionic activity coefficient, and <j>, the osmotic coefficient, for binary aqueous

systems at 298.15 K, all as a function of concentration.

Some documentation for (2) and (3) is provided. All of the values given are consistent with the NBS TN 270 Series.

12. KEY WORDS (S/x to twelve entries ; alphabetical order; capitalize only proper names; and separate key words by semicolon s) Activity coefficients; binary aqueous systems; enthalpy; enthalpies of dilution;

entropy; flue gas desulfurization; Gibbs energy- osmotic coefficients; thermochemical

tables; H ; OH"; S ions; CO^ and HCO^;Mn"^; Fe , Mg ; Ca Na ; K

13. AVAILABILITY 14. NO. OF

PRINTED PAGES

| Xl Unlimited

[ 1 For Official Distribution. Do Not Release to NTIS 89

Order From Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402. 15. Price

[it] Order From National Technical Information Service (NTIS), Springfield, VA. 22161 $9.50

USCOMM-DC 6043-P80