REFERENCE NAT'L INST. OF STAND & TECH

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PUBUCATIONS

NBS TECHNICAL NOTE 270-6

RcFcRENCc

NBS

Publi.

c^3tions

Selected Values of

Chemical Thermodynamic

Properties

Tables for the Alkaline Earth Elements

(Elements 92 through 97 in the

Standard Order of Arrangement)

U.S.

DEPARTMENT

OF

COMMERCE

National —Qc—

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.U5153

Ao. 270*6

1171
NATIONAL BUREAU OF STANDARDS

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» Located at Boulder, Colorado 80302.
National Bureau of Standard^ MAR 2 7 1975

QC106

gLb763

UNITED STATES DEPARTMENT OF COMMERCE

Maurice H. Stans, Secretary

NATIONAL BUREAU OF STANDARDS • Lewis M. Branscomb, Director

NBS ''technical NOTE 270-6

ISSUED NOVEMBER 1971

Nat. Bur. Stand (U.S.), Tech. Note 270-6, 119 pages (Nov. 1971)

CODEN: NBTNA

Selected Values of Chemical Thermodynamic Properties

Tables for the Alkaline Earth Elements

(Elements 92 through 97 in the

Standard Order of Arrangement)

V. B. Parker, D. D. Wagman, and W. H. Evans

Physical Chemistry Division

Institute for Materials Research

U . 5 .National Bureau of Standards

' ' * Washington, D.C. 20234

-t"' " Co^

^""CM of "

NBS Technical Notes are designed to supplement the Bureau's regular publications program. They provide a means for making available scientific data that are of transient or limited interest. Technical Notes may be

listed or referred to in the open literature.

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

(Order by SD Catalog No. C 13.46:270-6). Price $1.25.
ABSTRACT

Contains tables of values for the standard heats and Gibbs (free)

energies of formation, entropies and enthalpies at 298.15 K and heats

of formation at K for compounds of beryllium, magnesium, calcium,

strontium, barium, and radium (elements 92-97 in the Standard Order

of Arrangement) . These tables are a continuation of the comprehensive

revision of NBS Circular 500.

Key words: Enthalpy; entropy; Gibbs energy of formation; beryllium

compounds; magnesium compounds; calcium compounds; strontium

compounds; barium compounds; radium compounds.

II
PREFACE

This is the sixth of a series of Technical Notes containing the

tables of material prepared as a revision of National Bureau of

Standards Circular 500, Selected Values of Chemical Thermodynamic Properties, by F. D. Rossini, D. D. Wagman, W. H. Evans,

S. Levine and I. Jaffe. This Note contains data for compounds of six

elements, numbered 92 through 97 in the Standard Order of Arrangement,

The continued encouragement and support of the Office of

Standard Reference Data of the National Bureau of Standards is

gratefully acknowledged.

Ill
CONTENTS

Preface ill

Introduction v

Standard Order of Arrangement of the Elements, Figure 1 . . . x

Table A. Conversion Factors for Units of Molecular Energy . xi

Table 92 Beryllium 1

Table 93 Magnesium 9

Table 94 Calcium 30

Table 95 Strontium 57

Table 96 Barium 78

Table 97 Radium 103

Index of Contents 104

iv
SELECTED VALUES OF CHEMICAL THERMODYNAMIC PROPERTIES

INTRODUCTION

Substances and Properties Included in the Tables

The tables contain values where known of the enthalpy and Gibbs

energy of formation, enthalpy, entropy and heat capacity at 298,15 K

(2 5^C), and the enthalpy of formation at K, for all inorganic substances

and organic molecules containing not more than two carbon atoms. In

some instances such as metal-organic comipounds, data are given for

substances in which each organic radical contains one or two carbon

atoms

,

No values are given in these tables for metal alloys or other

solid solutions, fused salts, or for substances of undefined chemical

composition.

Physical States

The physical state of each substance is indicated in the column

headed "State" as crystalline solid (c), liquid (liq), glassy or amorphous

(amorp), or gaseous (g). Solutions in water are listed as aqueous (aq).

For non -aqueous systems the physical state is that normal for the

indicated solvent at 298.15 K.

Definition of Symbols

The symbols used in these tables are defined as follows: P = pressure; V = volume; T = absolute temperature; E = intrinsic or

internal energy; S = entropy; H = E + PV = enthalpy (heat content);

G = H - TS = Gibbs energy (formerly the free energy); C = (dH/dT)p = heat capacity at constant pressure.
Conventions Regarding Pure Substances

The values of the thermodynamic properties of the pure substances

given in these tables are for the substances in their standard states

(indicated by the superscript " on the thermodynamic symbol). These

standard states are defined as follows:

For a pure solid or liquid, the standard state is the substance

in the condensed phase vmder a pressure of one atmosphere.

For a gas the standard state 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 values of A Hi" and AGf* given in the tables represent the change

in the appropriate thermodyneimic quantity when one grann -formula

weight of the substance in its standard state is formed, isothermally at

the indicated tennperature, from the elennents, 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

thermochemically. The same reference states have been maintained for

the elennents at 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 are indicated in the tables by the

fact that the values of A Hf " and A Gf " are exactly zero.

The values of H^qq -Hq represent the enthalpy difference for the

given substance between 298.15 K and K. If the indicated standard

state at 25 "C is the gas, the corresponding state at K is the hypothetical ideal gas; if the state at 25 "C is solid or liquid, the corresponding state at K is the thermodynamically "Stable crystalline

solid, unless otherwise specifically indicated.

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 case of the hydrogen -deuterixom ( H- H) system. Where data have

been available only for a particular isotope, they have been corrected

v^hen possible to the normal isotopic composition.

The values of the enthalpies of formation of gaseous ionic species

are computed on the convention that the value of AHf for the electron

is zero. Conversions between and 298.15 K are calculated using

the value of Hlog-HQ = 1.481 kcal per mole of electrons, and assuming

that the values of H^Qg-Hg for the ionized and un-ionized molecules are

the same.

VI
Conventions Regarding Solutions

Solutions in water are designated as aqueous (aq); other solvents

are designated by name or chemical formula. The concentration of the

solution is expressed in terms of the number of moles of solvent associated with one mole of the solute. If no concentration is indicated, the

solution is assumed to be "dilute".

The standard state for a solute in aqueous solution is taken as the

hypothetical ideal solution of unit molality (indicated as "std. state,

m = 1"). In this state the partial molal enthalpy and heat capacity of the

solute are the same as in the infinitely dilute real solution. For nonaqueous solutions the standard state of the solute is the hypothetical

ideal solution of unit mole fraction of solute ("std. state, x^ - 1")«

The value of A Hf ° given in the tables for a solute in its standard

state is the apparent molal enthalpy of formation of the substance in

the infinitely dilute real solution. At this dilution the partial molal

enthalpy is equal to the apparent molal quantity. At concentrations

other than the standard state, the value of A Hf° represents the apparent

enthalpy of the reaction of formation of the solution from the elements

comprising the solute, each in its standard reference state, and the

appropriate total niunber of moles of solvent. In this representation

the value of A Hf ' for the solvent is not required. The experimental value

for a heat of dilution is obtained directly as the difference between the

two values of A Hf " at the corresponding concentrations.

The values of the thermodynamic properties tabulated for the

individual ions in aqueous solution are based on the usual convention

that the values of AHf% AGf*, S" and Cp* for H"*" (aq, std. state, m = 1)

are zero. The properties of a neutral electrolyte in aqueous solution

in the standard state are equal to the algebraic sum of these values for

the appropriate kinds and number of individual ions assxxmed to constitute

the molecule of the given electrolyte. When the undissociated species,

rather than the sxom of the ions, is meant, the notation "undissociated"

or "un-ionized" is used. For an ionic species the properties tabulated

refer to that undissociated ion. By adopting the above convention w^ith

respect to aqueous H , it follows that the thermodynamic relation A Gf

= A Hf* - T A Sf ** will not hold for an individual ionic species. However

no problem arises when neutral chemical systems are considered.

Vll
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 4.1840

joules, 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 A.

The following values of the f\indamental physical constants have

been used in these calculations:

R = gas constant = 8. 3143 + 0. 0012 J/deg mol = 1. 98717 ± 0. 00029

cal/deg mol

F = Faraday constcint = 96487. + 1.6 coulombs/mol

= 23060* 9 ±0.4 cal/volt equivalent

Z = Nhc = 11.96258 + 0.00107 J/cm"^ mol = 2.85912 4: 0.00026 cal/cm"^ mol

C2 = second radiation constant = hc/k = 1.43879 -t 0.00015 cm deg

O'C = 273.15 K

These constants are consistent with those given in the Table of General

Physical Constants, recommended by the National Academy of Sciences - National Research Council . The formula weights in the tables have

been calculated for the molecular formula given in the Formula and

Description column using the 1961 Table of Relative Atomic Weights based

on the atomic mass of ^'^C = 12 exactly .

Internal Consistency of the Tables

All of the values given in these tables 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 nnaintain a uniform scale of energies for

all the 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 Hf ", A Gf°, and

S" at 298.15 K satisfy the relation:

A Gf° = A Hf° - T A Sf .

NBS Technical News Bulletin, October 1963.

2

A. E. Cameron and E. Wichers, J. Am. Chem. Soc. 84, 4192 (1962).

Vlll
Furthermore the calculated value of any thermodynamic quantity for a

reaction is independent of the path chosen for the evaluation.

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 A H° or A G"

for specific reactions may result from the introduction of such data.

Uncertainties

The uncertainty in any value in the tables depends on the uncertainties of all the determinations in the total chain of reactions used to

establish the value.

A discussion of the vincertainties will be included in the final

publication of these tables in the National Standard Reference Data

System. However we have followed certain rules w^ith respect to

significant figures to indicate these uncertainties. Values are tabulated

in general 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 nximber

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. Similarly values of

A HfA and AHf^qo nc may be given to different numbers of significant

figures. In this instance the quantity with the lesser number of figures

is used to represent the uncertainty estimate. The larger number of

figures is used for the other quantity to retain the significance of the

temperature correction term.

Arrangement of the Tables

The compounds in the tables are entered according to the Standard

Order of Arrangement, (see Figure 1), by the principle of latest position.

In this scheme, a compovind is listed \inder the element occurring latest

in the list; water of hydration is neglected. Within a given elementtable will be found all of the compounds of that element with elements

occurring earlier in the order; the arrangement within a table follows

the same ordering. An exception occurs in the carbon tables (Table 23),

which is divided into subgroups consisting of all compounds with one

carbon atom, then all with two carbon atoms, etc.

ix
STANDARD ORDER OF ARRANGEMENT

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TABLES OF SELECTED VALUES OF PROPERTIES

SERIES I

Enthalpy of Formation at K

Enthalpy of Formation at 298. 15 K

Gibbs Energy of Formation at 298. 15 K

Enthalpy at 298. 15 K

Entropy at 298. 15 K

Heat Capacity at 298. 15 K

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103
Chemical

Symbol

Ag

Al

Ar

As

At

Au

B

Ba

Be

Bi

Br

C

Ca

Cd

CI

Co

Cr

Cu

F

Fe

Ga

Ge

H

He

Hf

Hg

IIn

IrKr

Mg

Mn

INDEX OF CONTENTS

Element Table Volume - Numbe r Page Number

Silver 37 4- 29

Aluminum 29 3-207

Argon 5 3- 17

Arsenic 20 3- 95

Astatine 13 3- 42

Gold 38 4- 39

Boron 28 3-196

Barium 96 6- 78

Beryllium 92 6- 1 Bismuth 22 3-103

Bromine 11 3- 31

Carbon 23 3-106

Calcium 94 6- 30

Cadmium 34 3-248

Chlorine 10 3- 24

Cobalt 40 4- 54

Chromium 51 4-120

Copper 36 4- 13

Fluorine 9 3- 21

Iron 41 4- 74

Gallium 30 3-218

Germanium 25 3-177

Hydrogen 2 3- 12

Helium 3 3- 15

Hafnium 59 5- 22

Mercury 35 4- 1 Iodine 12 3- 36

Indium 31 3-223

Iridium 46 4-103

Krypton 6 3- 18

Magnesium 93 6- 9

Manganese 48 4-106

104
Chemical

Symbol

Mo

N

Nb

Ne

Ni

O

Os

P

Pb

Pd

Po

Pt

Ra

Re

Rh

Rn

Ru

S

Sb

Sc

Se

Si

Sn

Sr

Ta

Tc

Te

Ti

Tl

V

W

Xe

Y

Element Table Volume - Number Page Number

Molybdenum 52 4-129

Nitrogen 18 3- 61

Niobium 55 5- 6

Neon 4 3- 16

Nickel 39 4- 43

Oxygen 1 3- 11 Osmium 47 4-104

Phosphorus 19 3- 84

Lead 27 3-187

Palladium 42 4- 90

Polonium 17 3- 60

Platinum 45 4- 96

Radium 97 6-103

Rhenium 50 4-117

Rhodium 43 4- 93

Radon 8 3- 20

Ruthenium 44 4- 94

Sulfur 14 3- 43

Antimony 21 3- 99

Scandium 60 5- 24

Selenium 15 3- 56

Silicon 24 3-171

Tin 26 3-181

Strontium 95 6- 57

Tantalum 56 5- 10

Technetiumi 49 4-116

Tellurium 16 3- 58

Titanium 57 5- 12

Thallium 32 3-227

Vanadium 54 5- 1 Tungsten 53 4-134

Xenon 7 3- 19

Yttrium 61 5- 28

105
Chemical

Symbol

Zn

Zr

Element Table Volume - Number Page Number

Zinc 33 3-233

Zirconium 58 5- 18

106
Announcement of New Technical Notes on

Selected Values of Chemical Thermodynamic Properties

Superintendent of Documents

Government Printing Office

Washington, D. C. 20402

Dear Sir:

Please add my name to the announcement list of new

publications to be issued in the series: NBS Technical

Note 270 - Selected Values of Chemical Thermodynamic

Properties.

Name

Company

Address

City State Zip Code

(Notification key 341)

FORM NBS-114A (1-71)

1. PUBLICATION OR REPORT NO. NBS-TN 270-6

2. Gov't Accession No.

U.S. DEPT. OF COMM. BIBLIOGRAPHIC DATA

SHEET

3. Recipient's Accession No.

4. TITLE AND SUBTITLE

Selected Values of Chemical Thermodynajnic Properties,

Tables for the Alkaline Earth Elements (Elements 92

through 97 in the Standard Order of Arrangement)

5. Publication Date December, 1971

6. Performing Organization Code

7, AUTHOR(S)

V.B. Parker, D.D. Wagman, W.H. Evans

8. Performing Organization

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

10. Project/Task/ Work Unit No. 1^10110

11. Contract/Grant No.

12. Sponsoring Organization Name and Address

Same

13. Type of Report & Period Covered

Final

14. Sponsoring Agency Code

15. SUPPLEMENTARY NOTES

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

bibliography or literature survey, mention it here.)

Contains tables of values for the standard heats and Gibbs (free) energies of

formation, entropies and enthalpies at 298. 1^ K and heats of formation at o K

for compounds of beryllium, magnesium, calcium, strontium, barium, and radiiim

(elements 92-97 in the Standard Order of Arrangement). These tables are a continuation of the comprehensive revision of NBS Circular ^0<^.

''• KEY WORDS (Alphabetical order, separated by semicolons)

Enthalpy; entropy; Gibbs energy of formation; beryllium compounds; magnesi\jm

compounds; calcium compounds; stronti\im compounds; barium compounds; radi\im compounds

18. AVAILABILITY STATEMENT

Pn UNLIMITED.

I I FOR OFFICIAL DISTRIBUTION. DO NOT RELEASE

TO NTIS.

19. SECURITY CLASS

(THIS REPORT)

UNCLASSIFIED

20. SECURITY CLASS

(THIS PAGE)

UNCLASSIFIED

21. NO. OF PAGES

119

22. Price$1.25

USCOMM-DC 66244-P7I

c /-.(-.irrnviulTTNT PRTOTTNG OFFICE : 1971 1*81-327/110
i
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Building Science Series. Research results, test methods, and performance criteria of building materials, components, systems, and structures.

Handbooks. Recommended codes of engineering

and industrial practice (including safety codes) de- veloped in cooperation with interested industries,

professional organizations, and regulatory bodies.

Special Publications. Proceedings of NBS conferences, bibliographies, annual reports, wall charts,

pamphlets, etc.

Monographs. Major contributions to the technical

literature on various subjects related to the Bureau's

scientific and technical activities.

National Standard Reference Data Series.

NSRDS provides quantitative data on the physical

and chemical properties of materials, compiled from

the world's literature and critically evaluated.

Product Standards. Provide requirements for sizes, types, quality, and methods for testing various industrial products. These standards are developed co- operatively with interested Government and industry

groups and provide the basis for common understanding of product characteristics for both buyers and

sellers. Their use is voluntary.

Technical Notes. This series consists of communications and reports (covering both other agency and

NBS-sponsored work) of limited or transitory interest.

Federal Information Processing Standards

Publications. This series is the official publication

within the Federal Government for information on

standards adopted and promulgated under the Public

Law 89-306, and Bureau of the Budget Circular A—86

entitled, Standardization of Data Elements and Codes

in Data Systems.

Consumer Information Series. Practical information, based on NBS research and experience, covering

areas of interest to the consumer. Easily understandable language and illustrations provide useful background knowledge for shopping in today's technological marketplace.

NBS Special Publication 305, Supplement 1, Publications of the NBS, 1968-1969. When ordering, include Catalog No. C13.10:305. Price $4.50;

$1.25 additional for foreign mailing.

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