Selected Values of 2703 Wag m

8/17/2019 Selected Values of 2703 Wag m

1/272

NATL

INST. OF

STAND &

TECH

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PUBLICATIONS

ECHNIC

IV

mmmm

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XCT

I EL

Selected

Values

of

Chemical

Thermodynamic

Properties

Tables for

the

First

Thirty-Four

Elements

In

the Standard

Order of

Arrangement

270-3

/C>0

ulS1S3

«**

0F

c,

Z

,

\

*&/>

1*

(A

o

U.S.

DEPARTMENT

OF

COMMERCE

National

Bureau

of

Standards

ill


2/272

THE

NATIONAL BUREAU

OF

STANDARDS

The National

Bureau of Standards

is

a

principal

focal

point in

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Government for

assuring

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Its

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development and maintenance

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stand-

ards

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measurement,

and

the

provisions of

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for

making measurements consistent with

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and

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3/272

UNITED

STATES

DEPARTMENT

OF

COMMERCE

Alexander B. Trowbridge, Secretary

NATIONAL

BUREAU

OF STANDARDS

•

A.

V.

Astin,

Director

NBS

TECHNICAL

NOTE

270-3

ISSUED

JANUARY

1968

Selected Values

of

Chemical

Thermodynamic

Properties

Tables

for

the

First

Thirty-Four

Elements

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

Basic Standards

National

Bureau

of Standards

Washington, D.C.

20234

|_

This

Technical Note

supersedes

Technical

Notes

270-1

and 270-2

J

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


4/272


5/272

PREFACE

Technical Note

270-3

is the third

in

a

series

of

publications

containing

material

prepared as a

revision

of

the tables

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

extends

the

revision

to

Tables

23, 33,

and

34,

covering

the

compounds

of

the

elements

carbon, zinc,

and

cadmium

in

the Standard

Order

of

Arrangement.

In

addition this

Note contains all

of

the

Tables

of

Technical

Note

270-1

and

270-2,

including

corrections for a

number

of minor

errors.

Thus

this

Note

supersedes

Technical

Notes

270-1

and

270-2.

Donald

D.

Wagman,

Chief

Thermochemistry

Section.

Ill


6/272

CONTENTS

Preface

III

Introduction

Table

A

Conversion

Factors

„

7

Table

1

Oxygen

1

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

84

Table

20

Arsenic

95

Table

21

Antimony

99

Table

22

Bismuth

103

Table

23

Carbon

106

Table

24

Silicon

171

Table 25

Germanium

177

Table

26 Tin

181

Table

27

Lead

187

Table

28 Boron

196

Table

29

Aluminum

207

Table

30

Gallium

2

18

Table

31

Indium

223

Table 32 Thallium

227

Table

33

Zinc

233

Table

34

Cadmium

248

Appendix

262

Table

B

263

Index

264

W


7/272

SELECTED

VALUES

OF CHEMICAL

THERMODYNAMIC

PROPERTIES

by

Donald

D.

Wagman,

William

H.

Evans,

Vivian

B.

Parker,

Iva

Halow,

Sylvia M„

Bailey,

and

Richard

H. Schurnm

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 0°K,

for

all

inorganic substances

and 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

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

p

=

(dH/dT)p

=

heat

capacity

at constant

pressure.


8/272

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

c

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 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

same

temperature and at

zero pressure.

The values

of

A

Hf

c

and

AGf°

given

in the

tables

represent

the

change

in

the

appropriate

thermodynamic

quantity

when

one

gram

-formula

weight

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

thermochemically.

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

C

K

and

0°K.

If

the

indicated

standard

state

at

25

°C

is

the

gas,

the

corresponding

state

at

C

K

is

the

hypo-

thetical

ideal

gas; if

the

state

at 25

°C is

solid or

liquid, the corres-

ponding state at

C

K

is the

thermodynamically

stable crystalline

solid,

unless otherwise

specifically indicated.

The

values

of

S

c

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-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.

The

values

of

the

enthalpies

of

formation

of

gaseous

ionic

species

are

computed on

the

convention

that

the value

of &Hf

°

for the

electron

is

zero.

Conversions

between and

2

Q

8.15°K

are calculated

using

the

value of

H^ng-HA

=

1.

481 kcal

per mole

of

electrons, and

assuming

that

the values

of H^gg-Hg

for

the

ionized and

un-ionized

molecules

are

the

same.


9/272

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

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

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 convention

that 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

with

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.


10/272

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

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.

00029

cal/deg

mol

F

=

Faraday

constant

=

96487.0 +

1.

6 coulombs/mol

=

23060.9 ±0.4

cal/volt

equivalent

Z

=

Nhc

=

11.

96258 + 0.

00107 J/cm

1

mol

=

2. 85912 ±

0.

00026

cal/cm

1

r

C£

=

second

radiation

constant

=

hc/k

=

1.43879

i

0.00015

cm

deg

C

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

i(i

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

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

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.

>

'A.

E.

Cameron and E.

Wichers,

J.

Am.

Chem.

Soc.

84,

4192

(1962).


11/272

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

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

Data

System.

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

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. Similarly values of

A

HfQ

and

^Hf^on

i

c

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

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

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.


12/272


13/272

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