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SELECTED VALUES OF CHEMICAL THERMODYNAMIC PROPERTIES

PART 1. TABLES FOR THE FIRST TWENTY-THREE ELEMENTS IN

THE STANDARD ORDER OF ARRANGEMENT

D. D. WAGMAN, W. H. EVANS, I. HALOW, V. B. PARKER,

S. M. BAILEY, AND R. H. SCHUMM

ZOOU5 7S3

I9G5

DEPARTMENT OF COMMERCEIAL BUREAU OF STANDARDS

NATIONAL BUREAU OF STANDARDSTechnical Note 270-1

ISSUED OCTOBER 1, 1965

SELECTED VALUES OF CHEMICAL THERMODYNAMIC PROPERTIES

PART 1. TABLES FOR THE FIRST TWENTY-THREE ELEMENTS IN

THE STANDARD ORDER OF ARRANGEMENT

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

S. M. Bailey, and R. H. Schumm

Institute for Basic Standards

National Bureau of Standards

Washington, D.C.

NBS Technical Notes are designed to supplement the Bu-reau's regular publications program. They provide a

means for making available scientific data that are of

transient or limited interest. Technical Notes may belisted or referred to in the open literature.

For sale by the Superintendent of Documents, U.S. Government Printing Office

Washington, D.C, 20402 - Price 65 cents

FOREWORD

This Technical Note is an advance issue of a revision of the tables

of Series I of the 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. The revision,

prepared in response to the increasing demand and need in the scien-

tific community for a more current, self-consistent set of thermodynamic

data for chemical substances, is part of a continuing program of the

NBS Thermochemistry Section.

Technical Note 270-1 contains the revised Tables 1-22 and part

of Table 23 of Circular 500. As additional revised tables are completed,

they will be published as Technical Notes 270-2, 270 -3, etc. , until

the complete revision has been made available. It was decided to

issue this Note in parts in order to make the material available as soon

after completion as practical. The complete revision of the tables of

Series I, including references and discussion of the sources of the

values, will be published as a contribution in the National Standard

Reference Data Series.

The authors 'will greatly appreciate receiving comments regarding

errors that may have escaped their attention.

Robert D. Huntoon, Director,

Institute for Basic Standards,

National Bureau of Standards.

li

PREFACE

The preparation of these tables has been the result of the combined

efforts of a number of members of the staff of the Thermochemistry

Section. Among these are Mrs. Rachel M. Dudley, who is supervisor

of the bibliographic and data -abstracting portions of the program and

has aided in the final editing of this Note, her assistant Mrs. Joyce J.

Grimes, Bernard Bettis and Mrs. Catherine L. Nelson, who have

served as abstractors of technical data and have performed many of

the calculations. The typing assistance of Mrs. Barbara B. Lineberry

and Mrs. Wilma Bell is also gratefully acknowledged.

The Office of Naval Research, U.S. Atomic Energy Commission,

and the Office of Standard Reference Data have contributed financial

support to this program over the past several years.

Donald D. Wagman, Chief,

Thermochemistry Section.

iii

CONTENTS

Foreword ii

Preface iii

Introduction 1

Table A Conversion Factors 7

Table I Oxygen 11

Table 2 Hydrogen 12

Table 3 Helium 15

Table 4 Neon 16

Table 5 Argon 17

Table 6 Krypton 18

Table 7 Xenon 19

Table 8 Radon 20

Table 9 Fluorine 21

Table 10 Chlorine 24

Table 11 Bromine 31

Table 12 Iodine 36

Table 13 Astatine 42

Table 14 Sulfur 43

Table 15 Selenium 56

Table 16 Tellurium 58

Table 17 Polonium 60

Table 18 Nitrogen 61

Table 19 Phosphorus 83

Table 20 Arsenic 93

Table 21 Antimony 97

Table 22 Bismuth 101

Table 23 Carbon (C^ compounds) 104

Appendix 122

Table B Auxiliary Thermodynamic Values 123

Index 124

IV

SELECTED VALUES OF CHEMICAL THERMODYNAMIC PROPERTIES

by

Donald D. Wagman, William H. Evans, Iva Halow,Vivian B. Parker, Sylvia M.Bailey, and Richard H. Schumm

INTRODUCTION

Substances and Properties Included in the Tables

The tables contain values where known of the enthalpy and Gibbsenergy of formation, enthalpy, entropy and heat capacity at 298.15 CK(25 °C), and the enthalpy of formation at 0°K, for all inorganic substancesand organic molecules containing not more than two carbon atoms. In

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

substances in which each organic radical contains one or two carbonatoms.

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

solid solutions, fused salts, or for substances of undefined chemicalcomposition.

Physical States

The physical state of each substance is indicated in the columnheaded "State" as crystalline solid (c), liquid (liq), glassy or amorphous(amorp), or gaseous (g). Solutions in water are listed as aqueous (aq).

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

(indicated by the superscript ° on the thermodynamic symbol). Thesestandard states are defined as follows:

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

in the condensed phase under 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 sametemperature and at zero pressure.

The values of A Hf and ftGf* given in the tables represent the changein the appropriate thermodynamic quantity when one gram -formulaweight of the substance in its standard state is formed, isothermally at

the indicated temperature, from the elements, each in its appropriatestandard reference state. The standard reference state at 25 °C for

each element except phosphorus has been chosen to be the standardstate that is thermodynamically stable at 2 5

CC and at one atmospherepressure. For phosphorus the standard reference state is the crystalline

white form; the more stable forms have not been well characterizedthermochemically. The same reference states have been maintained for

the elements 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 ft Hf° and ft Gf° are exactly zero.

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

given substance between 298.15°K and 0°K. If the indicated standard

state at 25 °C is the gas, the corresponding state at CK is the hypo-thetical ideal gas; if the state at 25 °C is solid or liquid, the corres-ponding state at CK 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 fromnuclear spins. Isotope mixing effects, etc. , are also excluded exceptin the case of the hydrogen-deuterium ( H- H) system. Where data havebeen available only for a particular isotope, they have been correctedwhen 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 H|gg-HQ = 1. 481 kcal per mole of electrons, and assumingthat the values of H^qo-Hq for the ionized and un-ionized molecules are

the same.

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 asso-ciated 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 non-aqueous 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 standardstate is the apparent molal enthalpy of formation of the substance in

the infinitely dilute real solution. At this dilution the partial molalenthalpy is equal to the apparent molal quantity. At concentrationsother than the standard state, the value of A Hf° represents the apparententhalpy of the reaction of formation of the solution from the elementscomprising the solute, each in its standard reference state, and the

appropriate total number 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 conventionthat the values of AHf°, AGf°, S° and C

p° for H"

1" (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 assumed to constitute

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

rather than the sum 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 withrespect to aqueous H , it follows that the thermodynamic relation A Gf °

= A Hf° - T A Sf ° will not hold for an individual ionic species. Howeverno problem arises when neutral chemical systems are considered.

Unit of Energy and Fundamental Constants

All of the energy values given in these tables are expressed in termsof the thermochemical calorie. This unit, defined as equal to 4.1840

joules, is generally accepted for the presentation of chemical thermo-dynamic 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 fundamental physical constants have

been used in these calculations:

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

F = Faraday constant = 96487.0 + 1.6 coulombs/mol= 23060.9 t 0.4 cal/volt equivalent

Z = Nhc = 11.96258 + 0.00107 J/cm" 1 mol = 2.85912 +. 0.00026 cal/cm" 1 molc^ = second radiation constant = hc/k = 1.43879 t 0.00015 cm deg0°C = 273.15'K

These constants are consistent with those given in the Table of GeneralPhysical Constants, recommended by the National Academy of SciencesNational Research Council . The formula weights in the tables havebeen calculated for the molecular formula given in the Formula andDescription column using the 1961 Table of Relative Atomic Weights basedon the atomic mass of ' C = 12 exactly .

Internal Consistency of the Tables

All of the values given in these tables have been calculated fromthe original articles, using consistent values for all subsidiary andauxiliary 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 the substances in the tables. In addition the tabulated values of the

properties of a substance satisfy all the known physical and thermodynamicrelationships among these properties. The quantities A Hf °, A Gf°, andS° at 298.15°K satisfy the relation:

A Gf° = A Hf° - T A Sf° .

NBS Technical News Bulletin, October 1963.

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

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. Becauseof 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 c

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

Uncertainties

The uncertainty in any value in the tables depends on the uncertain-

ties of all the determinations in the total chain of reactions used to

establish the value.

A discussion of the uncertainties will be included in the final

publication of these tables in the National Standard Reference DataSystem. However we have followed certain rules with 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 numberof significant figures for any one value in the tables need not representthe absolute accuracy of that value. For solutions of varying compositionvalues are frequently tabulated to more figures to make possible the

recovery of enthalpies of solution and dilution. Similarly values of

A HfQ and AHf^QQ ir 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 StandardOrder of Arrangement, (see Figure 1), by the principle of latest position.

In this scheme, a compound is listed under the element occurring latest

in the list; water of hydration is neglected. Within a given element-table will be found all of the compounds of that element with elementsoccurring 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 onecarbon atom, then all with two carbon atoms, etc.

STANDARD ORDER OF ARRANGEMENT

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SERIES I

Enthalpy of Formation at 0°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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APPENDIX

The order in which the tables of Series I of National

Bureau of Standards Circular 500 are revised follows the

Standard Order of Arrangement. However it has been

necessary to evaluate the data on certain additional sub-

stances in order to complete the calculations for the

tables given in this part. The values obtained for some

of these compounds are given in the following Table B.

122

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Index of Contents by Chemical Symbc Is

Chemical Element Table PageSymbol Number

Ar Argon 5 17

As Arsenic 20 93

At Astatine 13 42

Bi Bismuth 22 101

Br Bromine 11 31

C Carbon 23 104

CI Chlorine 10 24

F Fluorine 9 21

H Hydrogen 2 12

He Helium 3 15

I Iodine 12 36

Kr Krypton 6 18

O Oxygen 1 11

N Nitrogen 18 61

Ne Neon 4 16

P Phosphorus 19 83

Po Polonium 17 60

Rn Radon 8 20

S Sulfur 14 43

Sb Antimony 21 97

Se Selenium 15 56

Te Tellurium 16 58

Xe Xenon 7 19

124

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