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CHNICAL NOTE

270-4

Selected Values of Chemical

Thermodynamic Properties

Tables for Elements 35 Through 53 in the

Standard Order of Arrangement

*<"?£AU of*^

U.S. DEPARTMENT OF COMMERCENational Bureau of Standards

k

UNITED STATES DEPARTMENT OF COMMERCEMaurice H. Stans, Secretary

NATIONAL BUREAU OF STANDARDS • A. V. Astin, Director

NBS TECHNICAL NOTE 270-4ISSUED MAY 1969

Nat. Bur. Stand. (U.S.), Tech. Note 270-4, 152 pages (May 1969)

CODEN: NBTNA

Selected Values of Chemical Thermodynamic Properties

Tables for Elements 35 Through 53 in the

Standard Order of Arrangement

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

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

Institute for Materials Research

National Bureau of Standards

Washington, D.C. 20234

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

Price $1.25 cents.

PREFACE

Technical Note 270-4 is the fourth part of a series of Notes

containing the tables of material prepared as a revision of Series I

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 nineteen elements, numbered 35 through 53 in the

Standard Order of Arrangement. In addition the Appendix contains

a list of corrections for errors and nnisprints which have been

detected in the previous summary Note TN 270-3. Data for compounds

of elements numbered 1 through 34 are contained in TN 270-3.

CONTENTS

Preface ii

Intr oduc tion v

Standard Order of Arrangement x

Table 35 Mercury 1

Table 36 Copper 13

Table 37 Silver 29Table 38 Gold 39Table 39 Nickel 43

Table 40 Cobalt 54Table 41 Iron 74Table 42 Palladium 90Table 43 Rhodium 93Table 44 Ruthenium 94Table 45 Platinum 96Table 46 Iridium 103Table 47 Osmium 104Table 48 Manganese ^06Table 49 Technetium 116Table 50 Rhenium 117Table 51 Chromium 120Table 52 Molybdenum 129Table 53 Tungsten 134

Appendix 139Index 140

SELECTED VALUES OF CHEMICAL THERMODYNAMIC PROPERTIES

by

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

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°K(2 5°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 \indefined 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).

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

indicated solvent at 298ol5°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); Cp = (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 substancein 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 AGf* given in the tables represent the changein the appropriate thermodynajnic 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 Z5"C for

each element except phosphorus has been chosen to be the standardstate that is thermodynamically stable at 25 "C 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 A Hf " and A Gf ° are exactly zero.

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

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

state at 25 "C is the gas, the corresponding state at "K is the hypo-thetical ideal gas; if the state at 25 °C is solid or liqiiid, the corres-ponding 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 fromnuclear spins. Isotope mixing effects, etc. , are also excluded except

in the case of the hydrogen -deuterixim ( H-^H) system. Where data have

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

when 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 H298 H, 1.481 kcal per mole of electrons, and assximing

that the values of H|Qg-H5 for the ionized and un-ionized moleciiles 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, X2 = 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 molalenthalpy is equal to the apparent molal quantity. At concentrations

other than the standard state, the value of A Hf ° represents the apparententhalpy of the reaction of formation of the solution from the elementsconnprising 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% AGt", 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 kin^s and number of individual ions assumed to constitute

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

rather than the s\im of the ions, is meant, the notation "undissociated"or "un-Ionized" is used. For an ionic species the properties tabulated

refer to thatxindissociated ion. By adopting the above convention withrespect to aqueous H , it follows that the thermodynamic relation A Gf *

= A Hi" - 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 nnol

F = Faraday constant = 96487. + 1.6 coulombs /mol= 23060.9 ±0.4 cal/volt equivalent

Z = Nhc = 11. 96258 + 0. 00107 J/cm"^ mol = 2. 85912 -k 0. 00026 cal/cm"^ molC2 = second radiation constant = hc/k = 1.43879 ± 0.00015 cm deg

0»C = 273.15*KThese constants are consistent with those given in the Table of GeneralPhysical Constants, recommended by the National Academy of Sciences -

National 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, tennperature scales,

etc. Thus w^e 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 annong these properties. The quantities A Hf ", A Gf, andS° at 298. 15 "K satisfy the relation:

A Gf° = A Hf° - T ASf.

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

Uncertainties

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

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^og ir may be given to different niombers 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 compoimd 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.

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SERIES I

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Gibbs Energy of Formation at 298. IS^K

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Errata for Te chnical Note 270-3

Page 22 HF(liq) AH^°gg = -71.65 kcal/mol

Page 32 HBr(g) AH^ = -6.826 kcal/mol

Page 43 s(g) AGf = 56.951 kcal/mol

S° = 40.084 cal/deg mol

Page 48 H2S+(g^ AHfQ = 237.0 kcal/mol

Page 56 Se(g) H° - H° = 1.4815 kcal/mol

S° = 42.21 cal/deg/mol

Cp° = 4.978 cal/deg/mol

Page 61 N(g) AG£° = 108.886 kcal/mol

S° = 36.613 cal/deg mol

Page 86 H2PO4" (aq) AGf ° = -270.17 kcal/mol

Page 231 Tlzl 5603)3 instead of Te (8603)3

TlzSe formula weight = 487.70

Page 234 ZnFzCc) AGf° = -170.5 kcal/mol

139

INDEX OF CONTENTS

ChemicalSymbol

AgAl

ArAsAt

AuBBi

BrCCdCI

CoCrCuFFeGaGeHHeHgI

In

Ir

KrMnNNeNi

OOsPPbPdPoPtRe

Element

Silver

AluminunnArgonArsenicAstatine

GoldBoronBismut hBromineCarbonCadmiumChlorine

Cobalt

ChromiumCopperFluorineIron

GalliumGermaniumHydrogenHeliumMercuryIodine

IndiumIridiumKryptonManganeseNitrogenNeonNickel

OxygenOsmiumPhosphorusLeadPalladiiim

PoloniumPlatinumRhenium

Table Volume-Number Page Number

37 4- 2929 3-2075 3- 17

20 3- 9513 3- 4238 4- 3928 3-196ZZ 3-10311 3- 31

23 3-10634 3-24810 3- 2440 4- 5451 4-12036 4- 13

9 3- 21

41 4- 74

30 3-21825 3-1772 3- 12

3 3- 15

35 4- 1

12 3- 3631 3-22346 4-1036 3- 18

48 4-10618 3- 61

4 3- 16

39 4- 43

1 3- 11

47 4-10419 3- 8427 3-18742 4- 9017 3- 6045 4- 9650 4-117

140

ChemicalSymbol

RhRnRuS

Sb

SeSi

SnTcTeTl

WXeZn

Element Table Volume -

Number Page Number

Rhodium 43 4- 93

Radon 8 3- 20

Ruthenium 44 4- 94

Sulfur 14 3- 43

Antimony 21 3- 99Selenium 15 3- 56

Silicon 24 3-171

Tin 26 3-181

Technetium 49 4-116Telluriunn 16 3- 58

Thallium 32 3-227Tungsten 53 4-134Xenon 7 3- 19

Zinc 33 3-233

Compounds are located in the Table for the element (in the compound)having the highest Table number.

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