II I iiiiillili ill iiilii i i ill 1 1 1 ^(dp^

NBSIR 75-968

Selected Thermochemical Data

Compatible with the CODATA

Recommendations

V. B. Parker, D. D. Wagman, D. Garvin

Physical Chemistry Division

institute for IVIaterials Research

National Bureau of Standards

Washington, D. C. 20234

January 1976

Interim Report

Prepared for of Standard Reference Data, NBS

J 00

.tL^(^ I, Austria

itional Atomic Energy Agency

NBSIR 75-968

SELECTED THERMOCHEMICAL DATA

COMPATIBLE WITH THE CODATA

RECOMMENDATIONS

V. B. Parker, D. D. Wagman, D. Garvin

Physical Chemistry Division

Institute for Materials Research

National Bureau of Standards

Washington, D. C. 20234

January 1976

Interim Report

Prepared for Office of Standard Reference Data, NBS

and

International Atomic Energy Agency

Vienna, Austria

U.S. DEPARTMENT OF COMMERCE, Elliot L. Richardson, Secretary

James A. Baker, III, Under Secretary

Dr. Betsy Ancker-Johnson, Assistant Secretary for Science and Technology

NATIONAL BUREAU OF STANDARDS, Ernest Ambler. Acting Director

TABLE OF CONTENTS

Introduction

Contents of the Table of Thermochemical Dat

Description of Entries in the Table

General Remarks

Table A. Physical State Conventions

Appendix. Conversion and Rounding

Table of Thermochemical Data
This table has been designed to provide auxiliary data which

may be used in the evaluation of thermo chemical properties of

compounds of the actinide elements. It includes the auxiliary data

now being used in NBS evaluations of the properties of compounds of

thorium, uraniiira, boron and some alkali metals. It probably is

comprehensive enough for use in evaluations of compounds of the other

actinides ; but it can be expanded and redistributed if desirable.

The table has been prepared to assist the group of thermo chemists

that is evaluating the thermochemistry of the actinides for the

International Atomic Energy Agency. The use of the values provided

here in the preparation of each of the IAEA reviews will help assure

that the values recommended in the entire set of reviews will be

based on a consistent set of values for properties of compounds of

the non-actinide elements.

2. CONTENTS OF THE TABLE OF THEBMOCHEMIGAL DATA

The following classes of material are given:

a) Values recommended by the CODATA Task Group as of 1975,

complete [1]. llie Task group recommended values for AHf(298), S(298)

and H(298)-H(0). Values listed for ZNGf(298) and AHf(O) have been

calculated by us.

b) Properties of substances derived from measurements used

in the course of the CODATA evaluations, such as properties of

crystalline salts from their enthalpies and Gibbs energies of solution,

c) Recent selections for auxiliary data consistent with the

CODATA Key Values that have been made by members of the Chemical

Thermodynamics Data Center, NBS.

d) Selections from the NBS Technical Note 270 series [2]

that have been recalculated to make them consistent with the CODATA

rec ommendations

.

e) Selections copied directly from the NBS Technical Note 270

series. Analysis has shown that these values are not affected by the

CODATA recommendations.

For each substance in the table there is a comment identifying

the source of the values except for those copies directly from the NBS

Technical Note Series (class e, above) .

2
3. DESCRIPTION OF ENTRIES IN THE TABLE

A two-line entry is given for each substance. The first line

contains a compound number, the molecular formula, the formula weight,

and one or more of the six properties Z^Hf(O), ^f(298), AGf(298),

H(298)-H(0), S(298) and Cp(298) in kcal/mol or cal/mol-K. The

headings in the table for these properties are DHO, DH298, DG298,

H298-HO, S298 and CP298, respectively. The second line shows the

uncertainty for each value immediately below that entry and may have

a comment in the space below the molecular formula. The symbol

"+-" is used in the table for the plus or minus sign, ±.

Because this table is based on a machine-readable data bank,

certain conventions have been adopted that permit both humane

and a computer to decode the material. The essential points are covered below.

a) Molecular formula . A normal single-line chemical formula

is written for each substance with four modifications:

(1) Subscripts and superscripts are written on line.

(2) The subscript "1" implicit in normal chemical formulae is

written explicitly wherever it is necessary to separate the symbols

for two chemical elements (written entirely in capital letters):

CaNO^ becomes CA1N103.

(3) The physical state of the substance is appended to the

molecular formula in parentheses: HCJJ in 250 moles of water becomes

H1CL(250H20) . The conventions used in designating the state are given

in Table A.

(4) Electrical charge for ions is written in the form +N or

-N immediately preceding the physical state. When N=l the digit may

be omitted.

b) Formula Weight . This is calculated from the molecular formula

using the 1969 Atomic Weights [3], and is shown uniformly to four decimal

places

.

3
c) Values for Properties . These are given in the units

stated in the heading for the table, e.g. Mf(298), Z^f(298),

H(298)-H(0) and Z^f(O) in kcal/mol, and, correspondingly, S(29 8)

and Cp(298) in cal/(mol-K).

Some values in the data bank are in SI and some in calorie

units. When a table is prepared in a single set of units some values must be converted. Conventional conversion and rounding

rules are used by the computer program. (See Appendix) . These

are sufficient to assure that the CODATA recommendations in SI

were converted to values in calorie units that agree with the

auxiliary tables in the CODATA publications. Occasionally an extra decimal place is given, but the stated value will always

round to match that given by CODATA.

d) Uncertainties . These are printed immediately below the

values with which they are associated. Some values in the data

bank have uncertainties supplied by the evaluators; others do not.

In the latter case an arbitrary value is supplied. This is "10 in

the last place" as the value exists in the data bank. It appears

in square brackets: 48.20 +- [0.10], or, for a value converted

from joules, 15.041 +- [0.024], where "+-" is used for the plusor-minus sign, ±.

4. GENERAL REMARKS r ^

-

Suggestions for the improvement and extension of this table

will be welcomed by the authors. Users are urged to report any errors and to suggest revisions in the data.

The table itself has been prepared from a machine readable

data bank with the aid of a computer program that incorporates

manipulations such as calculation of formula weights, conversion of

units, rounding and formatting of printing. This program is a modification of one developed by Dr. J. B. Pedley, University of

Sussex, England, for use in the CATCH system of the rmo chemical

analysis.

4
References

[1] "CODATA Recommended Key Values for Thermodynamics, 1975"

(to be published as a CODATA Bulletin), and "Tentative Set

of Key Values for Thermodynamics: Part V" CODATA Special

Report 3j September 1975.

[2] D. D. Wagman et. al, Nat. Bur. Stand. (U.S.) Technical Notes

270-3 (Jan. 1968), 270-4 (May 1969), 270-5 (March 1971).

V. B. Parker, et. al., NBS Technical Note 270-6 (November

1971). R. H. Schumm et al., NBS Technical Note 270-7 (April

1973).

[3] lUPAC Inorganic Chemistry Division Commission on Atomic

Weights, Pure and Applied Chemistry 2j^ 91 (1970).

5
TABLE A : Physical State Conventions

The following conventions are used to designate the physical

state of a substance. These apply to the attached table and to the

NBS Thertnochemical Data Bank. This Information appears in a

parenthetical expression appended to the molecular formula. Some of

the explanations Imply a thermochemlca 1 value, particularly those

for solutions. These normally are used in describing enthalpy

measurements. ,

Bp sir Symbols Explanation

(G) Gaseous, e.g., in HICL(G) for HCJ^(g)

(GS) Gaseous reference standard state for an element,

e.g., 02(GS) for 02(g)

(C) Crystalline, e.g., in N1H4CL(C) for Nll^C£(c)

(CS) Crystalline reference standard state for an

element, e.g., in RB(CS) for Rb(c)

(L) Liquid, e.g., in H20(L) for }i^O(Z)

(LS) Liquid reference standard state for an element,

e.g., in BR2(LS) for Br^^i)

(AM) Amorphous

(GL) Glassy

(A) 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. HC-^(A) =

H+(A) + CC->(A). For an ionic species this

notation is commonly used to refer to the

undissociated Ion as written.

6
Symbol Explanation

(AO) Hypothetical standard state of the Ideal aqueous

solution at unit activity of the undissociated

(non-ionized) species, e.g. HF(AO), HF^-CAO).

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.

(AU) Aqueous solution of undefined, but usually

dilute, concentration, e.g. XeOg(AU).

The symbols used above occasionally are modified by numbers

to distinguish two substances in the same state that have the same

molecular weight, as for isomers,: (AU2), (63). They are also used

in combination with descriptive material, e.g. (C:HE), (C:AL) etc.

to mean "crystalline, hexagonal", "crystalline, alpha form" etc.

Special notations for substances in solutions

The notations for the "state" of a substance in solution may

combine a definition of the system, e.g. HCX in 220 moles of water,

and a specification of the thermochemical property associated with it.

Usually the thermochemical property is the apparent integral enthalpy

or free energy of formation or an absolute entropy, i.e. the formation

properties of the solvent are not included. If a partial molal property

is tabulated the notation D: ("D" for "differential") occurs as the

first term in the state bracket. The notations given below illustrate

the differences for integral and differential (partial molal) properties,

and extrapolated values. Examples are given for aqueous, mixed, and

non-aqueous solvents.

7
Symbol , ,

t

H1CL(200H20)

H1CL(D:200H20) and

H20(D:H1CIH-200H20)

Explanation

An aqueous solution of specified composition, e.g.

one mole of HCi in 200 moles H2O. The value of

Z^f represents the apparent integral enthalpy

of formation.

These represent the partial molal (enthalpy) of

formation of the substance in a solution of

specified concentration, e.g. the partial molal

enthalpy of formation of HCi and respectively,

in a solution consisting of 1 mole YLCZ and 200

moles H2O.

U1CL4(H1CL104+50H20) This describes a solute dissolved in a mixed solvent,

e.g. one mole of UCX^ in a mixture of 1 mole of

HCiO, and 50 moles H^O. The value of Z^f represents

4 2

the apparent integral enthalpy of formation of

the substance, HCi^, in the medium.

This represents a solute at an unspecified but

usually dilute concentration in a solvent mixture

of fixed composition.

U1CU(H1CL104+

50H20:AU)

8
Symbol Explanation

U1CL4(D:H1N103+50H20) Specifies the partial molal (enthalpy) of formation

of a substance in a mixed medium, e.g. the enthalpy

of formation of 1 mole of UC£^ in a large amount

of a solution containing \JC^i^, ^^^3 ^^'^

the molar ratios 1:1:50.

U1CL4(L(H1CL) :AU) Specifies a thermochemical value extrapolated

from those in a particular type of solution, e.g.

the integral (enthalpy) of formation of UCi^ at

an unspecified concentration in water solution

obtained by extrapolation from values in solutions

containing HCi at varying concentrations.

RB1I(C1H3C1N:S) Ideal solution of a substance (Rbl) in a nonaqueous solvent (CH^CN), the substance being in

the standard state of unit activity on the molal

scale unless otherwise indicated. (In some early

entries in the Data Bank these are. written

ambiguously as (C1H3C1N)).

RB1I(C1H3C1N: U) Solution of a substance (Rbl) in a non-aqueous

solvent (CH^CN) at an unspecified concentration.

This is analogous to (AU)

.

RB1I(1000C1H3C1N) Solution of a substance (Rbl) in a non-aqueous solvent

(CH^CN) at a specified concentration.

9
Appendix. Conversion and Rounding

The rules used here are given below. They are adaptations of rules

in two editions (1970 and 1974) of the "Metric Practice Guide" published

by the American Society for Testing and Materials. The conversion procedure

is from Section 4.4.1.1, ASTM E380-70 which is a special case of the

procedure in Section 4.2.1, ASTM E380-74. The rounding procedure is taken

without change from Section 4.4, ASTM E380-74.

We suggest that these rules are suitable for use in other applications

involving the conversion of energy quantities.

1. Input to the data bank . A number and its uncertainty are written

to the same least significant decimal place. Normally not more than two

significant digits appear in the uncertainty.

2. Output and Printing

(a) A number and uncertainty present in the data bank in the

same units as those used in a table are printed without modification.

(b) A number and its uncertainty, whether converted or not,

are printed to the same least significant decimal place.

3. Conversion of units . The number and its uncertainty are converted

separately. The decimal place at which each is to be rounded is set as follows.

(a) If the most significant digit in the converted quantity is

less than the most significant digit in the original, one more significant

digit is used in the converted quantity than is present in the original.

"Standard Metric Practice Guide (A Guide to the Use of SI- the International

System of Units)", ASTM Designation E380-74, American National Standard

Z210.1, (American Society for Testing and Materials, 1916 Race Street,

Philadelphia, PA. USA 19103), 1974. , ASTM Designation E380-70, (Am.

Soc. for Testing and Materials), 1970.

10
Otherwise the same number of significant digits is used.

Example 2.0 x (1/4.184) = 0.48

4.3 X (1/4.184) = 1.03

(b) The number of significant digits derived for the

value in (a) above is decreased, if necessary, to the smaller

number required by either of the following criteria.

(1) No more than two significant digits in the

uncertainty, or,

(2) No more than three decimal places (0,001) in the

value (and the uncertainty)

.

4. Rounding . Consider the quantity that is to be rounded to be

written in the form N.R x 10

where K is an integer and the fractional portion R is to be discarded

in the rounding process.

If R < 0.5, then no change is made in N

If R > 0.5 then one unit is added to N

If R = 0.5 exactly, then one unit is added to N if N is odd,

no change is made if N is even.

Note: These rules may increase the number of significant digits

in a quantity, but only by one, in a sequence of conversions., e.g.,

joules calories joules -» calories, etc.

11
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USCOMM-NBS-D
NBS.I14A (REV. 7-73)

U.S. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET

I. HUIU.K.AIIUN UK KhHUKl NU.

NBSIR 75-968

2. Uov t Accession

No.

J. Kecipient s Accession No.

A T'l'TI I.' AMP* CfrDTIT*! C 4, 111 Lr, ANU bV n I I 1 Lh

SELECTED THERMOCHEMICAL DATA COMPATIBLE WITH THE CODATA

RECOMMENDATIONS

•|

5. Publication Date January 1976

6* Perfoffning Organization Code

7. AUTHOR(S)

V. B. Parker, D. D. Wagman, D. Garvin

8, Performing Organ. Report No. NBSIR 75-968

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

10. Project/Task/Work Unit No. 3165151

11. Contract/Grant No.

Iz. sponsoring Organization Name and Complete Address (Street, City, State, ZIP)

National Bureau of Standards

Department of Commerce

Washington, DC 20234

13. Type of Report & Period

Covered

Interim

14. Sponsoring Agency Code

15. SUPPLEMENTARY NOTES

16. ABSTRACT (A 200-word or less (actual aummary ol moat si^ilicant information. If document includes a significant

bibliography or literature survey, mention it here.)

Selected thermochemical properties data at 298.15 K are given for 384

substances. The data are compatible with the current recommendations of the

CODATA Task Group on Key Values for Thermodynamics. The set of values provided

here is suitable for use as auxiliary data in evaluations of the thermochemical

properties of compounds of the actinide elements. Rules used in the conversion

of units and the rounding of numbers are stated.

17. KEY WORDS (six to twelve entries; alphabetical order; capitalize only Ae first letter of dhe first key word unless a proper name; separated by semicolons) CODAtA compatible values; enthalpies of formation; entropy;

gibbs energy of formation; selected thermodynamic values; thermodynamic properties

18. AVAILABILITY Unlimited

'

1 1 For Official Distribution. Do Not Release to NTIS

1 1 Order From Sup. of Doc, U.S. Government Printing Office Washington. D.C. 20402. SD Cat. No. C13

(jj^ Order From National Technical Information Service (NTIS)

Springfield, Virginia 22151

19. SECURITY CLASS

(THIS REPORT)

UNCL ASSIFIED

21. NO. OF PAGES

20. SECURITY CLASS

(THIS PAGE)

UNCLASSIFIED

22. Price

$4.00

USCOMM-DC 2g042-P74
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