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THERMODYNAMICS

AN

ADVANCED

COURSE SOLUTIONS

WITH

PROBLEMS

AND

RYOGO
University

KUBO
of Tokyo

in

cooperation

with

HIROSHI

ICHIMURA
Institute

TSUNEMARU

USUI

NATSUKI

HASHITSUME Ochanomizu

Tokyo

of Technology

Nagoya

University

University

1968

NORTH-HOLLAND JOHN
WILEY

PUBLISHING &

COMPANY

AMSTERDAM

SONS,
Publishers

INC.

NEW

YORK

(Interscience

Division)

NORTH-HOLLAND

PUBLISHING

COMPANY

AMSTERDAM

1968

No

part

of this

book other

may
means

be

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writ en

in

any

form permission

by print, from

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photoprint, publisher.

microfilm

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of

Congress

Catalog

Card

Number

67-26462

THIS

BOOK THE

WAS

ORIGINALLY SHOKABO
AND

PUBLISHED

IN TOKYO

JAPANESE

BY

COMPANY,

publishers:

NORTH-HOLLAND
SOLE

PUBLISHING
DISTRIBUTORS
INTERSCIENCE
FOR

COMPANY
U.S.A.
A AND

AMSTERDAM

CANADA:

PUBLISHERS,

DIVISION
-

OF

JOHN

WILEY

&

SONS,

INC.

NEW

YORK

PRINTED

IN

THE

NETHERLANDS

PREFACE

TO

ENGLISH

EDITION

The "Problems itself


one

original
and of

text

of

this

volume
in

is that

of

the

first
and

four

chapters
Statistical Shokabo
book Advanced
was

of

the

book

Solutions
the

Thermodynamics
Series"

Mechanics"

"University
the
as

published
of

by original
Publ.

the

Publishing
translated

Company.
first
and

Although published
and
Solutions" be
caused

last

part

the

"Statistical

Mechanics-An

Course the
work.
one

with volit

Problems
ume

(North-Holland
as

Co.,
of the the authors' but
for

1965),
whole

present
and
seems

should The

regarded
title
some

the

first

volume

English
book.
This

is

somewhat

dif erent
of usual the The

from
the of

original
intention it is
of

to

have

misunderstanding
not to

of
aimed and
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is

the

type

textbook,

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student

study
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of

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writing primarily by workcan

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students
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to

textbook

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translation
N.

by
parts

together Hajime
done
and Dr.

present
authors.

book.

Seki,

Heights,
the of
express

Y.

and

by
of
and

the the

the
my

original deep
the

Bernard Donald took the C.

Springer
Worth
trouble

of

Japanese appreciation University through


thanks in is also

edition
to

Laboratory original English


also and
to

in

edition,
Professor Professor

Seki,
California

of Christian the due

Southern

of of

International

linguistic
M. 1966 Suzuki

dif iculties.
who

reading My
us

University, manuscript
to

Tokyo,
and
N.

who

kindly
us

helping
and

with
Mrs.

Mrs.

Hashitsume

helped

preparation

of

the

manuscript.
Ryogo Kubo

PREFACE

TO

JAPANESE

EDITION

the the

Thermodynamics physics
quantum

and
of

statistical
of
a

mechanics
matter.

are

thorough
mechanics

viewpoint
tical

properties mechanics, provides understanding of atomic physics.


are

the

Statistical
for

foundation

indispensable mechanics, modern physics


from
and
not

tools which

in

studying
with aims
at

together
the

of

physical
of of

Fundamental vital
matter

therefore

phenomena knowledge importance


but the

studying
nuclear

the

physical
or

physics
of

portance
areas

rapidly technology

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properties even astrophysics. penetrating


which
owe

also
realm

for and

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microscopic in statistraining for students only those who study of physics, its iminto those
vast

chemistry, their growth


to

biology
to

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and
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physics. Thermodynamics times regarded in learning


is
most

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time
some

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Even
decades

classical of

physics
who in

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physics
when

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for

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ago

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However,

al-

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chemical
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as

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explicit
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thermodynamics
were us

as

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century.

Thermodynamics
It

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energy,

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value
with free atomic

phenomenological
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as

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energy

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physical
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explore phenomenon
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more

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underour

confine

thermodynamics.
and

made

possible
mechanics

quantum

mechanics

statistical

mechanics.

Statistical

only provides

by

PREFACE

TO

JAPANESE

EDITION

VII

us

with
the real

means

to

link world.

the itself

physical
Without
would close

laws
not

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the

microscopic
with
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world

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of

cooperation
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statistical
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nics,
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Like

mechanics
In

represent

physics
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sense,

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keystones
any

modern

physics.
statistical
once.

other

by
one

learning
grasps

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the
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science, principles
way

mechanics
One
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great
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deal
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statistical
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fields
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students

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physics.
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of

thermodynamics
to

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large
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solutions. all reference
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with stil able

thermodynamics examples topics,


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statistical
rather

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fundamental

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This

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of

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to

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book

textbooks. obtain

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reading
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examples
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marked

by

not

needed

in mechanical

solving

topics problems problems

in

bookf,

thermodynamics

and

statistical

are

t The Japanese
one

reader

is

reminded
in which

that

this

text

is

translation and statistical

of

the

Preface
are

to

the

original
in

edition,
volume.

thermodynamics

mechanics

contained

VII

PREFACE

TO

JAPANESE

EDITION

mostly
kinetic
which

limited methods

to

those
and

of extensions

equilibrium
of

states.

It

might
and

be

desirable
statistical
to content

to

include

thermodynamics
We limited
This

mechanics
our-

apply
in become
As 6 of

to

non-equilibrium
such
"Statistical

problems.

had,
way

however,

selves

treating
much

topics

in

only
is

in the
also

the
whole

last

chapter
volume such
non-

(Chapter
had

Mechanics").
larger
are

because
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than

the
in

original
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plan
quantum
In of

because

equilibrium
mentioned
mental

problems previously
of

certainly
this

advanced.

preface,
world.
the

mechanics
sense,

is the

funda-

dynamics
to

the

ought
devotes

be itself

essential y
to
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tions, studying
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in in

microscopic quantum-statistics. understanding knowledge


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this
nature

statistical
since

mechanics
the

However,
of
of
and

present
considerais

book
in

statistical
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to

problems specializing
mechanics
this

B. have find

quantum Therefore,

mechanics
even
an

required
who

students

physics
wil
in
not

but

only
any

in

quantum
book.
is
most

serious

elementary dif iculty

background starting
grasp

to

study
What

important
Mathematical
may

studying specialized

physical

problem
may

it

as

problem
and

in sometimes should
be

physics.
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require
be
the

manipulations techniques.
but
and it would
to

sometimes

be in mathematical if

tedious

Training
be
a

methods
to
meet

ignored,
mathematics

serious the
to

mistake

one

was

dazzled
students'
answers or

by
papers
are

forget
seems error

physics.
be
two

Teachers
no

often about
orders

in

which

the

student
are

in
H.

doubt three
in

the
of

numerical

magnitudes physicist
He
Isn't

in

Japan)
the

changed
it?" is
very

although dimensionally was carrying of his sign


calculations
for
you.
at

they
out
answer

in

by
on
a

or

incorrect. calculations

Professor

Nagaoka
rather
than
error.
even

(a pioneer
his

blackboard be in

class. minus.

saying
may very
can

"It

is

plus right

Mathematical

often the

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important, betrays
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answer

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students that

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wil
spare

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giving
and

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chat.

hope

the

reader

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are

revised

this

English

edition.

PREFACE

TO

JAPANESE

EDITION

IX

minutes
coffee The lems of made the
were or

at

these

spots

to

listen

to

chat writ en

from

the

authors,
R. the it
our

drinking
Examples
The
of and

tea

or

just
selected

smoking.

fundamental
after
was

topics
made authors

were

mostly
discussion
R.

by by all
the whole

K.

probcheck
was

repeated by
which would
may

authors.

final the would

solutions

K. have this
to

and

design
if readers

book

by
out

N.
any years

H.

The

point
Five
years

mistakes
have
we

appreciate escaped
book
was

kindly
and
two
to

notice.

passed
started
than

since

since
more

actually
we

write

it.

The

originally undertaking
authors
are

planned,
proved

be

much ful
to

dif icult
K.

anticipated.
of

The

particularly
for his

gratecontinual

Mr.

Endo,
and

editor

Shokabo

Publishing

Company,

encouragement

help.
Ryogo
Kubo

January,

1961

CONTENTS

CHAPTER
THE

1. FIRST

THERMODYNAMIC
LAW OF

STATE

AND

THERMODYNAMICS

Fundamental

1.1 1.2
1.4 1.5 1.6 1.7 1.8 1.9 1.10 1.11 1.12 Examples
Problems
Solutions 1.3

Topics Objects The Concept Thermodynamics) Thermodynamic Thermodynamic


The

of
of

Thermodynamics
Thermal
Contact

Equilibrium

(The

Zeroth

Law

of
2
2 3
4

Quantities
of

Processes The First and First

Change
of
of

Law

Thermodynamics

5
8

Heat
The

Enthalpy
Law

Thermodynamics

Applied

to

Infinitesimal
9 10 11

Processes

Temperature
Heat

Capacity,
of
of

Specific
State

Heat

Equation Change

12

Independent

Variables

16 18 30 37

CHAPTER

2.

THE

SECOND AND

LAW

OF

THERMODYNAMICS

ENTROPY

Fundamental

Topics
Reversible
A and

2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9

Irreversible
Law of

Process

61
62 63

Lemma Second

(Carnot
of
a

The
The

Cycle) Thermodynamics
General for

Efficiency
Temperature

Carnot

Cycle Cycle

63 65

Absolute

Clausius'

Inequality
of

an

Arbitrary

69
70

Entropy Additivity
General

Entropy
of
the Second
Law

74

Expression

74

CONTENTS

XI

2.10 2.11 Examples


Problems
Solutions

The Maximum

Direction
Work

of

an

Actual
Minimum

Change
Work

75 77 78

and

85
95
CHAPTER AND
3.

THERMODYNAMIC

FUNCTIONS
CONDITIONS

EQUILIBRIUM

Fundamental

Topics

3.1 3.2 3.3 3.4


3.5 3.6 3.7 3.8 3.9 Examples
Problems
Solutions

Thermodynamic Legendre
Gibbs-Duhem

Functions Transformation
Relation
of

133 136
137

Definitions
Relations The Third
Law

Thermodynamic
of

Quantities

and

Thermodynamic
137

Thermodynamics
Two

(Nernst-Planck
Systems
a

Theorem).
..

140 140 141

Equilibrium Equilibrium Inequalities


Le

between Condition
of

for

Given

Environment

Thermodynamics

143

Chatelier-Brown's

Principle
.

145 147
159

166
CHAPTER
AND

4.

PHASE

EQUILIBRIUM

CHEMICAL

EQUILIBRIUM

Fundamental

Topics
Phase
190

4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 4.11+Activity 4.12

Equilibrium
Surface

between Tension
of Rule Chemical
a

Dif erent

Phases

of

Pure

Substance

190 192

Equilibrium
Gibbs'Phase The

Many-Component
of and
a

System
Gas

in

Dif erent

Phases

193
195 197

Potential
Potential

Chemical
and

Saturation

Vapor

Pressure

of

Liquids
199 200

Solids

Dilute Ideal

Solutions
Solution
for
and

(Ideal
Concentration

Solid-Solution)
of

and

Regular

Solution.

201

Expressions
Solution of

Solutions

202
202 203

Activity Strong

Coefficient

Electrolytes

XII

CONTENTS

4.13 4.14 4.15 Examples


Problems
Solutions

Chemical

Equilibrium
of
of

205

Thermodynamics

Electrochemical
Third
Law

Cells of

206
..

Application

the

Thermodynamics

209 210 228 244

DIVERTISSEMENTS

Chapter
1.
2. 3.

Founders

of do
we

the have

first winter Sadi

law Carnot

of

thermodynamics
11

8
36

Why
Nicolas
2

heating?

Leonard

Chapter
4. 5.

Absolute
International Axiomatic

temperature

65

practical
foundation helium
3

temperature
of

scale

68 77 128

6. 7.

thermodynamics

Kapitza's

liquefier

Chapter
8.
9. On

the

names

of

thermodynamic
mnemonic

functions

147 161

Thermodynamic
4

diagrams

Chapter
10.

Equilibrium
Classification

of

11.
12.

of

heterogeneous phase
and

substances

194

transitions life

196
249

Thermodynamics

Chapter

THERMODYNAMIC

STATE

AND

THE

FIRST

LAW

OF

THERMODYNAMICS

This

chapter
concepts

deals related
must

with
to

the
the
a

concept
first

of law
in

those

of

thermodynamic thermodynamics.
of
that
are

state

and Students

with of

thermodynamics
of such

have

clear

concepts.
of
of
state

It but

should
are

be

noted,

understanding particular,
which

the

physical
and heat

meaning
are

work

not

functions
process

quantities

determined

by

specifying

the

change.
Fundamental

Topics

1.1. Some

THE

OBJECTS

OF

THERMODYNAMICS

of

the

basic
In

concepts
order
have
are

and
to

terms

used
unnecessary

in

thermodynamics
confusion,
When
not

are

listed all
more

with
definitions

explanations.
given
definitions
here

avoid

the

been

made

rigorous.
of in Such
space
a

necessary,
are

rigorous System:
entities
to

given
are

later.
the

Systems
called

which with
of

objects

thermodynamics
and
time

macroscopic
are

systems
processes material

extensions
measurements.

which
may

accessible of
a

normal
of

system
atoms,
In

consist

great
or

number field

quantities
systems

such

ical

containing composed
of

Systems
the

particles (e.g. as electromagnetic an extremely of only a small


part
of
environment
a

molecules,
fields.

electrons,
case,

etc.)
they
of
are

of

either

dynamfreedom.
are

large
number

number

of

degrees
of freedom

of
is defines

degrees
chosen
The
as

not

object
Environment:

thermodynamics.
If the
as

whole

system
is
its

observation,
be
on

remaining
an

part

surroundings.
certain

the object surroundings

of

our

may

abstracted
the

which

conditions
pressure,

imposed
chemical
inter-

system

of

interest

(such independent
is
an

as

constant

temperature, system
which
has

potential,
Isolated action Closed
with is

etc.).
system: its
An

absolutely
with
of material its

no

surroundings
A

isolated
has
no

system.
material

system:
a

system
system
open

which which

exchange

surroundwith
its

ings
Open surroundings

closed

system.
A is
an

system:

has

interchange

system.

THERMODYNAMIC

STATE

[Ch.

1, 3
OF

1.2.

THE

CONCEPT

OF

THERMAL

EQUILIBRIUM

(THE

ZEROTH

LAW

THERMODYNAMICS)
The

thermal
of its

equilibrium
initial
to

state

of
if
an

an

isolated

system:

Regardless
a

of

the

complexity
wall
final

state,

isolated

system
the

(e.g.
system
state

gas

surrounded
comes

by
to

a a

impervious
state

heat)
does
not

is

left

standing,
This
the

eventually
is

which
state.

change.

final material
the

called

the continue
state

thermal their is
a

equilibrium complex simple


Thermal
are comes

motion,
state

Microscopically but macroscopically


by
a

particles
thermal
such
as

stil

equilibrium
temperature isolated system
A and
is
not

defined

few
two

parameters
systems:
one

and

pressure.

equilibrium
into
to

of
contact

When another the is


two

two

systems
A + B and
B
are

and thermal also

brought
thermal

with
other.
The

total
that A

eventually
in

equilibrium.
with
each

It

then

said

are

equilibrium separately
contact

systems,
The

themselves

in between
two

thermal
the

equilibrium.
two

equilibrium
and
is

disturbed

when
some

the
time.

is

broken and
be

then

restored

after
not

Therefore each
if If
in

systems,
may

A said
to

B,
in

even

when

they
into
contact.

are

in

contact

with

other,
there is Zeroth
no

be

thermal
are

equilibrium
brought (transitive
in
C
are

with

each

other

(A~B)

change
law

when

they

The
A

and thermal

of thermodynamics are in thermal equilibrium A and then equilibrium,


A~B,B~C^A~C.

law
above in
sense

of

thermal-equilibrium):
and
B and C
are

the

also

thermal

equilibrium:

A.1)
Zeroth
In
a

This

empirical Thermodynamic
sense
as

law thermal
be

is
state

called
or

the
state:

law
narrow

of
but

thermodynamics.
sense

this

term
a

is whole
are
as
a

used

in

the is

same

considered

to

in in

equilibrium,
in
a

i.e. thermal
A that and the
THERMODYNAMIC

equilibrium a thermodynamic local equilibrium,


state.

state,
state
even

in the

general
various

system
in

if the
when

parts
system system

thermal
is not

whole of
may

equilibrium
B,
entire each

For

example,
dif erent
a

if, in
temperature
which
is

bodies
said 1.3. Contacts

part
system

is is

at

in

state

specified

composed TA and TB, it by (TA, TB).

two

be

CONTACT

which
are

allow

the

fol owing
contacts.

interactions

between does

thermodynamic
on

systems
1.

called
of

thermodynamic
interaction:

Mechanical
means

When
or

one

system

work
the

another

system
is called

by
2.

mechanical
interaction:

electromagnetic
An

forces,
which results

interaction
in

mechanical. Thermal interaction the

exchange

of

Ch.

1, 4] in
the

THERMODYNAMIC

QUANTITIES

energy

form
is

of

heat adiabatic
An

transfer

by
wall.

such

means

as

thermal
which the

conduction
cuts

and
off

thermal
interaction
3. between
is
an

radiation called
Mass
two

is called
an

thermal interaction
mass

interaction.
which

wall

thermal
of
matter

interaction:

involves
A

exchange

systems
of
2

is called and
3

interaction. interactions weak

semi-permeable
enough
result which
it is
in
not
to

membrane

example.
are

Idealizations

alter
contacts

the

properties
during
If the

of
process

the

yet systems of observation.


is in

strong
as

enough
a

to

effective the

the

environment

considered the
way

source

acts

on

system
a

under work
A
so

consideration
source,
source
or a

mentioned

above,

called
source

heat

reservoir

(heat
considered remains
in
a

bath)
to

or

particle

respectively, (or reservoir).


than the

reservoir
source
on

is

be

that it

the
exerts

itself
the

given
its

sufficiently equilibrium
contact

larger
state

system
of the

regardless

effect
1.4.
State

system

through
QUANTITIES

with

it.

THERMODYNAMIC

quantities:

Physical
state

quantities
of the

which

have
are

definite

value

for

each
or

thermal
state

equilibrium quantities.
entropy.
State

system

thermodynamic
internal
energy,
sense

quantities,

Examples:
or

temperature,

pressure,

enthalpy
these
sense
are are

and

variables
state

the

thermodynamic thermodynamic equilibrium. by local


as are

In variables: a narrow thermodynamic above. In the broader described quantities denote the which they physical quantities If a set of independent is properly variables

of defined
chosen

the

so

to

be

necessary

and The

sufficient number

to

define of

state,

the variables

other

state

quantities
a

their
Intensive

functions.
state

independent

for

thermal

equilibrium equilibrium equilibrium.


property
extension

of is is determined of
the

system
and into
an

is
extensive

determined

empirically.
quantities: by inserting
state

quantities
state

If uniform

system
each

in

thermal stays internal


of
the in

divided

parts
state

walls,
a

part
is
an

Therefore and
or

equilibrium by
pressure,

of

system
are

size

system.
vary

Such in

quantities quantities
chemical
to

which
are

independent
intensive
On the
or

called extension

quantities.
other
mass are

Examples:
state

temperature,

potential.
the the of

hand,
of the

quantities
when

which
it is divided

system,
extensive

without

proportion changing
mass

equilibrium
energy,
some

state,

called

quantities.
variables
are

Examples:
and into external the
two

components,
In

entropy.

Internal variables

variables:

cases,

thermodynamic
external variables.

classified

categories:

internal

and

THERMODYNAMIC

STATE

[Ch.

1, 5

The

external
of
field

variables
the
or

define
in
a

the

state

of

the

surroundings.
a

For

position
electric

piston
a

cylinder
field these
sources

magnetic
However,
field
on

containing acting
may
are

gas,

and
can

the
be
as

on

system
in

example, strength thought


variables Thus
the

the

of of dis-

an

as

external
if tinction the

variables.

be

considered the line


be

internal

piston depends

or

the
in
contact

included
the

system.
our

where with
in
OF

we

draw
it.

between made
contacts.

system
in

and
to

the

surroundings
confusion,
1.5. In
PROCESSES

This
case

should
of

clear

order

avoid

particularly

the

mechanical

CHANGE

treating
other the thermal
the
are

change
and
the

which

system
states
are

undergoes,
confines

just
itself

by
to

itself

or

in

contact

with

systems,
initial

thermodynamics
final

those
states states states.

which

thermodynamic
the
be

changes (not
In

for
neces-

sarily
which

equilibrium
system
very
states

states).
may
states.
or

However,
may
not

intermediate
process and

passes

thermodynamic
the is then number the

through general,
slow
the
can

they
intermediate described

complex
wil of is
the
terms

be

in
A
are

Only thermodynamic, of change


in

when

extremely
the of
process

be

sufficient initial
the

thermodynamic
states

quantities. Cycle:
system

cycle
identical.
process:

process
A

which
in

and

final

of

the

Infinitesimal
initial
process.

and

the

final

states

is This

change infinitesimally
is
and
an

which small

dif erence
is

between
an

the

called
which

infinitesimal
it be

Quasi-static
assumed that
Such

process:

ideal
its

process

during
maintain

may

both
a

the process For

system
is

surroundings
realized
a

thermal

librium.

approximately
to

by
gas

making
external
p,

the
pressure

equichange

sufficiently
is maintained the
gas

slow.

example,
greater

infinitesimally

compress than

the
pressure

/?(e)
to

the

gas

while

expand
In

/?(e)
these
two

is

maintained
processes

infinitesimally
fol ow
is the
same

less

than
in

(see
are

Fig.
directions.
the
is and

1.1).
important
in
the in

the
a

limit

path
The

quasi-static quasi-static i) Quasi-static


with
occurs
an

process

reversible

(cf.
process:

2.1).
In

opposite fol owing


the

Thus

processes:

isothermal
of
at

this

process

system

contact

environment

constant

temperature temperature.
process:

(heat
is
mass
a

bath)

process

i)
the

quasi-statically Quasi-static
system
but

this

adiabatic
no

This the
no (and surroundings.

has
work is

thermal done

contact

quasi-static contact)

process

which

with

its

surround-

ings

by

or

on

Ch.

1,6]

FIRST

LAW

OF

THERMODYNAMICS

Fig.

1.1.

The
process

quasi-static
but

adiabatic

process
are

is

sometimes

called
processes

simply
also between

an

adiabatic
better
and
to

since the
two

there

irreversible

adiabatic

it is
reversible

distinguish
irreversible
1.6.
THE

clearly

(see

2.1

for

the

dif erence

processes).
FIRST LAW OF

THERMODYNAMICS

Although
general
energy
The

the

first
energy

law

of

thermodynamics
it

is

particular
existence
of

case

of
internal

the

law which
first

of is
law

conservation, thermodynamic
of

implies
When

the

the

quantity.
a

thermodynamics.

system

initial
action
states

state

1 to

final
which

state

2, the
it receives

sum

of the
its

work

A,

the

heat
is

changes Q,
determined
that

from
and the
mass

an

quantity
1 and
means

Z,
2:
it

from
on an

surroundings,
process.

by
its

the

does
there

not

depend
exists

the

intermediate

This

that

internal

quantity

such

dif erence

THERMODVNAMIC

STATE

[Ch.

1, 6

between

the

states

1 and

2 is

given

by
+

U2-Ut=A
The

Z.

A.2)
If
energy

function

?/is

the

internal

energy such
as

of

the
the

ised
energy,

by

mechanical
eq.

A.2)

energies is replaced

system. kinetic

the

system
and
the

is character-

potential

by

E2-Et=A
where
The
can

Z,
mechanical

A.2')
energies.
of
energy. It

is

the

total
of
as

energy

of

the

system
is

including
the

first
be

law

thermodynamics
^totai
=

law

of

conservation

expressed

constant

if

2stotai
in

is the the other The

energy

of

the

entire

system
in

ting
a

subsystem
contact.
amounts

process the

of
energy of work the

change
of

which

it from
of the
The

parts
of
energy
must

system
the heat

A,
be

transferred familiar
He
amount

question. changes (surroundings) Q, and through


with the
be energy
a

including Eq.
as

every

subsystem
or

participawrit en
for
to

A.2)
the

eq.

result

of action

is A.2') energy-transfer various


Z
are

through
the these
mass

mechanisms

respectively
heat
mass

contacts.

reader

concepts
familiar transferred
mass

of
with
to

work that the

and of

at

least
Z.

from This
other the

elementary
represents
than work

physics.
the
or

may

less

action
in
a

of

heat This

when

certain

of

matter

system is transferred
of treated.
of

form from

surroundings.
much
here for

concept
when

dynamics
included

later
the

usually heterogeneous
is in

introduced

in

textbooks
are

thermoBut

systems

it

is

Perpetuum

mobile

completeness of the first


A

stating
If
a

the

first

law

kind:
+

system
=

undergoes

thermodynamics. a cycle, A.3)


at

Q
on

0.

Thus

the
+

system
it would
extracts

does

work,
from
in
a

A,
the

the

surroundings
A

the mobile
its

expense

of of is

Q
first
without

which
kind

surroundings. cycle
the

perpetuum
work
on

the

operate
expense.

which
first

does law
a

surroundings
also
kind.

this
the

called Internal

principle
energy:

of
The kinetic in
an

the

Therefore, impossibility
internal
energy

of

thermodynamics
mobile

of
the of

perpetuum
energy
as
a

of
the
the

the

first

is the

within
and
cases

system,

usually
energy

excluding
of
may

the

energy

of field
a

system

whole
some

the
be

system
considered
energy

external
as

(although
the

in

internal

is

the

sum

part of

internal kinetic

energy).
energy

potential the potential Microscopically,


and
the interaction

energy the

the

molecular

Ch.

1,6]

FIRST

LAW

OF

THERMODYNAMICS

energy

of
The

the
first

material

origin.
state

law
The

of

particles, thermodynamics
constant

but

thermodynamics
stresses

usually
that internal
the
energy

does

not

ask
is fixed

its
a

internal
may

energy

quantity.
a

additive
standard function
of

of

the
zero.

be

by
is the

choosing
energy

certain

state

for

its

Figure
and pressure.

1.2

shows
The

the

internal
C

of

air

as

temperature

point

critical

point

(see

example

8).

-2000

-1000

Fig.

1.2.

The

internal

energy

of

air.

The each
process.

dependence
of
the

of quantities example,
action
or

work, A,
the
a

heat

and
Z

mass

action

on

the

process.

Unlike

U,
on

Q and
same

in

eqs.

A.2)
l->2
may

and
be

A.2')
achieved

depends
through

the
a

For

mechanical

thermal

change action,

or

U2-

UX=A
=

(Process (Process
quantities
nor

I) I ).
can

A.4)
they
statement

Hence
terms

A,
of the

and dif erence

are

not

state

be

expressed
of the first

in

of

state

quantities.
sum

The

positive
is determined

law in
state

is

that,

nevertheless,

the

A +

by

the

dif erence

quantities.

THERMODYNAMIC

STATE

[Ch.

1, 7

Divertissement

Founders Scientists
would have
to
or

of
had

the been

first
been
"In
a

law
built
memory

of
in

thermodynamics. the 185O's,


of the

If the
most

tomb

of

the
of

Unknown

appropriate
and

inscription
those who of

grief
But

sacrifice
law

fought
energy,

realize
the
names,

perpetuum
law
of

mobile".

the

conservation

of with

first

thermodynamics,
Helmholtz
and
was

is
Joule.

associated
a

primarily
who
was

three

great
Julius
Robert world

Mayer, Mayer
with
von

A814-1878)
the
or
as a

really
this

genius
declaration.
gave

born
Hermann the
name

in

this

only
Ferdinand der

errand

to

make

great
of

Ludwig

Helmholtz
"the

A821-1894)
conservation
doctor

this

law

"Erhaltung
started

Kraft"

energy".
a

Like

Mayer,
life
as

he the

his

career

medical
and

but
of

lived

glorious
Prescott

greatest

physiologist
worked
of
over

physicist forty
of work
was

the

day.
the arrived
most

James

Joule
verifi-

A818-1889)
cation

years

to

establish
heat. who
was

experimental
at

the
the

equivalence
three,
was

and

Among
last

whose
of

work

Mayer recognized.

the
His
a

first

this
A
age

law of fresh

and

the

life
he

dramatic.
of

lightening
twenty
blood red.
of
zones

stroke
one

genius
on

overtook the
sea near

him,
Java

German

doctor noticed
an

the

six,
of
He
a

day

when be connected becomes animals lead

that

venous

patient
considered
dation
cause

under that in

surgical
this
of this
a

operation

appeared
with

unusually
Lavoisier's
in

might
which

theory tropical
there.
of the
voyage,
to

oxibegener-

animals,
rate

process

slower wil
be
to

the
and

heat

loss
work.

by
For
at

slower idea after


his

great
while

alization heat

of

observation doctor

him
three
years

the

equivalence
he
was

of
the

mechanical
as

working
first
der
was

medical
the

home,
of
energy
sent
was

he
to

devoted

himself

complete
die
Annalen
paper

work

on

conservation
Natur"

"Bemerkungen
the

i ber this
it
was

Krafte and
in his for

unbelebten
never

which

journal
many
years.

published (Annalen
wrote

by
der four

it. Chemie

In

1842 und

Liebig Pharmacie)
1851. than

Poggendorf published
but

ignored
of he
two

Mayer

papers

before
other
was

During
his
He

these

years

unusual
became
years

activity mental y
but
never

he

cared

for and
to

nothing
science.

theory.
recovered

In

1852
after

deranged
returned
AND ENTHALPY

hospitalized.

1.7.
If
a

HEAT

action
action

change (Process (Process


The

1 ->2
I

due of

to

thermal
the heat and
is

action

can

also
is
terms

occur

through
by
work is
measured A. the

mechanical

A.4)),
can

Q which
in
heat in this

introduced

the

thermal is the
in

I)
definition conventional
1 cal
=

be
of

measured

of
sense

This
units

operational
work.

heat,
unit

of

given

by

4.1840
unit

joule
has
various

(thermodynamic
definitions.

calorie*).

Calorie

as

practical

Ch.

1, 8]
The

FIRST

LAW

OF

THERMODYNAMICS

equivalence
the
was

of first

heat The

and

work,

as

indicated determination

by
of

eq.

A.4),
the
heat

means

es-

sential y
of If

law. takes associated there


is

experimental
Joule.

equivalent

work
the

achieved

by

change
work
A V.

place
with
no

at

constant

pressure

(isobaric
AV

mechanical

the

by

If

other

work

change done,

in

volume

is
states

process), simply
that

the

given

the

first

law

Therefore

it

is

convenient

to

introduce
H=U
+

the

function

pV
=

and

write

H2-HX
The 1.8.

Q.
the

A.4') enthalpy,
APPLIED
or

quantity
THE FIRST

H,

introduced
LAW OF

here,
THERMODYNAMICS

is called

the
TO

heat
INFINITESIMAL

function.

PROCESSES

For

an

infinitesimal

process,

eq.

A.2)
+

can

be
+

writ en

as

dU
In

d'Q
consist
+

d'A
of

d'Z.
a

A.5)

particular,

if

the

surroundings
d'A
d'Z
=

single

simple

system

-p(e)dV

?^e)dxi,

A.6a)

t
the

nf
due
to

dNj
the

(= t
V=
to

Gf
volume

dn)
of
xt
=

A.6b)
system,
the

where/?(e)
i-th
the the

pressure
on

of
the of
per

surroundings,
the force

the

Xfe)

type system mole

force
number*

system
the
molecule

surroundings,

coordinate of
and

of
or

corresponding
potential
In
a

Z/e),
or

JV,in

the
the

number

molecules

y-th

component
mole
of

system,

/^e)
in

the the
in

chemical

the

j-th
the

component system
is

surroundings. equilibrium

with

quasi-static its surroundings

infinitesimal
and

process,

almost

xi,

A.7a)

A.7b)
*

When

Nj
chemical

is

the

mole

number,
per

it
mole

is
the
per

often
is

writ en

as as

nj

to

indicate

this

and the in

the
mass

corre-

sponding
component/,
the
per

potential
Mj,
is used is
per

writ en of
In
gram.

Gj (see

3.3).
or

Sometimes
mole number

of
case

instead

of

number stated.

chemical molecule

potential
or

expressed
unless

molecules this book

which
is either

the

chemical

potential

mole

otherwise

10

THERMODYNAMIC

STATE

[Ch.

1, 9

In

the

case

of

quasi-static
2

process
2

in

general
2 2

ZJdNj,
where
p

A.8)
of
the
the

and

nj

are

the
are

pressure

and
to

the of

chemical the

potential
surroundings,
the
on

system
system
are
so

itself,
is
the in

because

they
with
with
e

equal
the

those

since

equilibrium

surroundings.
exerted
may

Similarly
by
omit ed.
the

external
the

forces

in

equilibrium superscript the path


Notation

the

forces

system
The the

surroundings
in
eq.

that

of
process.

X/e)
the of
the

be

integration
mechanical their
notation

A.8)
done
values
to

is

along
and
are

of
action

the

d': dif erentials


In

Since

heat

transferred,
on

work infinitesimal

the
not

mass

quantity

depend
state

the

process,

exact

variables.

The
which work
the done

d'

is

used
exert

emphasize
the
the

this

point.
Work:

general,
such
x

force

X(e)

surroundings
due
to
a

on

system

is defined

that
is X(e)
in

the dx.
X->

infinitesimal
The

change
this

in

general
In

coordinate
the
case

expression
p.

A.6a)
quasi-static
way
as

only
process,

indicates the

definition.
and

of

pressure
are

In

system

its

sur-

roundings
Mass

equilibrium
In

and/?(e)=/?;
the chemical
the
same

similarly
above,

X(e)=X

(internal
may

force).
as

interaction:

A.6b)
of the of

be

considered in
be

the clearer

definition
here
to

of than
the 3.
TEMPERATURE

the

surroundings.
respect

Although
that

potential, meaning
characterizes
it
process

/Z;e),
of
be

j-th
the

component

the
no

the the used

chemical
state
more

^e)

jf-th
In
a

component,

wil

potential may surroundings extensively starting

with

with

Chapter
1.9.

quasi-static

f?p=fij.
as
a

The librium
atures

temperature
between of the
two two

is

defined

quantity
contact.

which
If

bodies

in

thermal

prescribes 6t and
thermal
are

thermal

equithe

92

are

temperand

bodies,
while when

0x

if
contact.

9X >92, A.1).

6X Obviously,
23).

decreases

for 02 is the condition i n creases when 92 they 93, then 62 6i 62 and


= =
=

equilibrium,
brought 03,
=

into

thermal
con-

^
is

satisfying
on

dition

Conversely,
the choice of
be

the

concept
a

of

temperature
scale
at

based

A.1)

(c.f.
its

problem Although
absolute of thermodynamics. centigrade

temperature
with the
the

this

point
of

is the

arbitrary,
second scale
or

choice

wil

established

introduction absolute hereafter.

law
the

Anticipating
temperature
scale

this,
wil
be

temperature

used

Ch.

1, 10]
The

HEAT

CAPACITY,

SPECIFIC

HEAT

11

absolute scale
6
can

temperature
it is be

wil
to
use

be
gas

denoted thermometer.

by
by
point
of
water

T.

As An

an

empirical
temperature

temper-

ature

possible
converted

the
T

arbitrary

scale

into

(K,

Kelvin)

>

'0

P^oypr

)eo

^triple
centigrade
=

273.16

A-9)
is
defined

(cf.

Chapter

2, problem

37).

The

temperature

scale

by

0C
1.10. If
a

273.15K.
HEAT

HEAT

CAPACITY, of

SPECIFIC

quantity
which, quantity

heat
defined

d'Q

is
a

introduced

quasi-statically
x

into

system

by
by

process

dT,

the

maintaining Cx,

quantity

constant,

raises

the

temperature

by
C*
=

~,

A.10)
process.

is the
mass

heat of molar the

capacity
material heat
or

of molecular
on

the is its the

system

for
heat. heat.

this
The
it becomes

The

heat
for

capacity
a

per

unit

specific
process is

heat

capacity
a

mole

is called

the

Since

d'Q
process

the
pressure

depends (or when

quantity
heat heat
at

of

state
at

only
constant

when

x)
heat

specified.

(isobaric
isochoric

(isobaric specific
heat

capacity),
cp,
heat

Cp,
capacity

Examples: specific
at constant

capacity
constant

pressure

heat), capacity),
cv.

volume
constant

Cv,
is

specific
to

heat

at

volume

(isovolumic (isovolumic
for
an

or

specific
process

heat),
and
Divertissement

It

possible

formally
isothermal

define
processes.

Cad

0)

adiabatic

Cisoth.

oo)

for

an

Why
The

do

we

have wil

winter
answer:

heating?
"To

layman
energy."
suppose,

make
so

the
it:

room

warmer."

The the
is

student

of

thermodynamics thermal)
wrong.

wil If
to

perhaps
so,

express

"To
answer

import right,
affairs,

lacking
the
that air. In scientist's the the

(inner,

then

the
to

layman's
the

We
sure

correspond
a

actual
that of
per

state

of
the

pres-

of

the
the

air

in

room

always thermal)

equals
energy
u
=

external
mass,

usual

notation,

(inner,

is,
CvT.

unit

(An
unit

additive
of

constant

may

be

neglected.)
u1
=

Then

the

energy

content

is,

per

volume, CvpT,

12
or,

THERMODYNAMIC

STATE

[Ch.

1, 11

taking
have

into

account

the

equation P/P
=

of

state,

RT,

we

M1
For

Cvp/R.

air

at

atmospheric

pressure,
m1
=

0.0604
is

cal/cm3.
thus
barometer. the
pores

The

energy

content

of
by heating
air.

the the
state

room

independent
The of
and the but is
same

of
whole
the

the of

solely imported
to

determined

of

the

temperature, the
of the

energy
room

by
outside
a

the bottle
room.

escapes

through
from
the
warmer,

walls
it
in
to

the

I fetch
in the
not
warm

of
It

claret
becomes

cold
but
room

cellar

put

be

tempered
content

increased

energy

is earth
energy,
a

borrowed

from do the the lat er


we

the
have of

air

of

the
sun. a

brought
reason

from that life


the
on

outside.
on

Then needs

why
for
in

heating?
the
from

For But

the this of of

the
as

radiation

does
amount

not

exist

incident

apart
continual
Our and

negligible
existence

man,

stant

spite body-weight.
of addition
a

of

absorption
conditions
for
the

nourishment,
of

is re-radiated, maintains

just
a con-

require
this

determinate
is

degree
not

temperature,
of
energy

maintenance

there
F.
meant
seem

needed

but with World


of In

addition

of
her

entropy.
a

As

student,
of
In

I read the
course

advantage
and

small

book

by

Wald
energy
to

entitled
and
me

"The

Mistress
the

Shadow".

These

entropy. have

exchanged
of
and does

places.
entropy method
the of

advancing the huge


the

principle
manner

occupies
the

whole

the two knowledge of natural manufactory of manager, for position whilst the business, principle
credits and

to

processes,

the the
energy

it

dictates of
R.

merely
Kempterstrasse
Zurich.

bookkeeping,
5,

balancing

debits. Emden

in Nature 141 908. A. Sommerfeld is a note published A938) that he cited it in his book Thermodynamik interesting Statistik theoretische Bd. i ber 5, Dietrich'sche Physik, (Vorlesungen translation Academic Verlag, Wiesbaden; by F. Kestin, English New is known in astrophysics R. Emden Inc., by his work York, 1956). and i n as an art i c l e der Enzykl o padi e represent e d by meteorology der mathematischen Wissenschaften Thermodynamik Himmelskorper (Teubner, Leipzig-Berlin, 1926). The

above it

found

so

und
Press

der

1.11.

EQUATION
existence

OF

STATE

The

of

an

equation

of uniquely
thermal

state:

The

thermal
the
state

equilibrium
values
of
a a

state

of
state
as

system
variables.

is

usually
For

defined

by

instance,

the

specifying equilibrium

few

of

fluid

such

Ch.

1, 11 ]
gas
or

EQUATION

OF

STATE

13

simple
the
if the

liquid
volume
v

is in

determined

by
we

only
may

two

variables,
more
or

the

pressure

and

specific
fluid This
that
a

(sometimes
an

have field
on

is
E

put
or

external also variables with

electric

in

variables; magnetic
state

for

instance,
the fluid
0

field,
of

field
may

quantities, depend).
shows

H, fact,

are

which law between

the

the

combined

the exists

zeroth

of
the

thermodynamics
temperature

A.1),
(on
are an

functional
and

relationship
the
can

arbitrarily
and
v,

scale),
such
a

state

variables writ en
as

(see

problem

23).

If

the

lat er

relation

be

which

is

the

equation
there

of
exists
a

state.

Similarly
of

it may

be

shown,
between

for than

more

general
and i.e.
does
not
a

system,
necessary

that
and

functional
number

relationship
variables

temperature

sufficient
an

(other
However,
except
of
state

temperature),
must

that
say

there

exists

equation
its

of functional

state.

thermodynamics
that
are

anything
conditions for
to
a

about

form

it

satisfy empirically
so

certain

stability
or

(see
system
of

3.8).

Equations

determined

given

theoretically they
of
of
an

by

statistical
are

mechanics,

that

in

the in

framework
order The if the

thermodynamics
the

regarded
The

as

something
is

given

specify
of
law of
see

system.
state

equation
temperature
second

ideal

gas:

general
is

form used with

pV=g@),
be shown absolute

but,

scale

the
writ en

gas

thermometer
that
as

(it
the

can

by
temper-

the
ature

scale,

thermodynamics it is 2.5),

this

agrees

pV
where and k
JR
n

nRT

NkT,
of

A.11)
molecules,
R

is the

mole

number,
constant:
x x

iVis

the

number

the

gas

constant

is
=

the
8.314

Boltzmann

HTergmorMeg
106
ideal
erg

1.9872
x

cal

mol

deg,
or

fc

1.3803 becomes gas shown

deg
in

=8.616

10

eVdeg.
low

Any
It energy
can

real

the

limit law

of of

be

from
gas

the is

second

of

an

ideal

independent
=

high temperatures thermodynamics of the volume,


U
=

densities. the
internal

that
V

(cf.

Chapter A.12a)

2,

problem
The

2):

(dU/dV)T
form of
In

0,

U(T).
or

U(T)
the

is

determined
range

empirically
of
U
=

theoretically

by

statistical

mechanics.

normal

temperature

nC$T

A.12b)

14

THERMODYNAMIC

STATE

[Ch.

1,

11

10*

h-

2000

-273.15
15

1/mol
1.3.
Pressure

Fig.
is
constant.
a

of

an

ideal

gas.

good

approximation
For

for

most

pure

gases,

so

that
molar

the

specific
heat,

heat

is

those

temperatures,

the

isovolumic

specific

Cy
A.13)

is

Cv

f R 1R
3R A

(monatomic (diatomic (polyatomic


mixture of
r

gas) gas) gas).


species
the

Mixture
nt

of ideal
of the z-th

gases:

of

ideal

gases,

consisting
state

of

moles

gas

(/=
pV

1, 2,. .,
=

r), obeys
nRT,

equation

of

A.14)

Corresponding

to

A.12),

the

equation

A.15) usually
The
holds

for
pressure

the

normal
pt

range

of
i-th

temperatures.
is

partial

of

the

component

defined

by A.16)

Ch.

1,

11]

EQUATION

OF

STATE

15

and

therefore

The

ideal

gas

law when
For

applies
the
pressure

to

real

gases

as

limiting
low and

law: the
and lower

it

is

good

approximation sufficiently
atures,
1.4 dense and
gas

is

high.
deviations
1.5

higher
from the
this down.

pressures ideal

sufficiently (higher
law
In

temperature temper-

densities)
become
more

gas

noticeable.
starts

Figures
when of
states
two.
to
a

il ustrate
is

for of
which

argon.

fact
a

even

cooled
gases, Waals

There
we

are

number
here

describe
The
Van

dense

mention
state

liquefaction of equations the only

fol owing

der

equation

of

is

given
RT,

by A.17)
Table
Gas
a

where
the
gas.

v=

Vjn
Because

is the of it and is

molar
its

volume

of

1.1

simple
used real
gases.

analytas
an

ical
constants
are

form,
a

often

(atm
He Ne

cm6/mol2)
X
x x x x

(cm3/mol)
106 106 106 106 106 106
106 106
23.71

approximation
given
Virial nes'

for
b
for

The
gases
0.03415 0.2120 17.10 26.61

various

in

Table
of

1.1.

expansion

(Kamerlingh-Onstate):
gases

H2
A

0.2446 1.301
1.346 1.361
1.486 3.959

equation
for
=

practical
the form

expansion
pv

real

has

N2 o2
CO

x x
x x x x x

30.22 38.52 32.58


39.87

co2

42.69
44.18 30.52 56.26 56.39

v2

A.18)
or

N2O H2O Cl2 SO2

3.788
5.468

106 106 106 106 of


&

6.501 6.707
S.

pv

RT

{I

B2p

B3p2
B2,
B3,. .
the
the

+},
A.19)
functions
law:

(P. dynamics,
York

Epstein,
John

Textbook

thermoNew

Wiley

Sons,

1937)
of

where

virial Ideal

A2, A3 coefficients.
is

or

are

temperature
M

and of

are

called

body equation

paramagnet a function
of
state

and

Curie

The

magnetization
H,
and

magnetic
T

of is

external

field

the

temperature

If

the

simply

M=f(HIT),
the

(/@)
ideal

0)
In

A.20) particular,
when

material

is

said

to

be

an

paramagnet.

HjT

is

16

THERMODYNAMIC

STATE

[Ch.l,12

Argon
Pc
=

48.00

atm

1.8839cm
150.72

Vg
K

Tc=

,V

Fig.

1.4.

relief

of

the

equation

of

state

of

argon.

small,

eq.

A.20)

is

approximated
M

by
=

CH/T
Curie often
constant.

A.21)
Non-metal ic this law.

which

is
is bound

the

Curie

law,
break down

being
metal
as

the
ions the

crystals
this absolute ideal
zero

containing
law

paramagnetic
to

obey

However,
the

temperature

approaches

(see
1.12.

Chapter
CHANGE

3, problem
OF

26).
INDEPENDENT
VARIABLES

the

Sometimes, independent Hence, just


dif erentiation

in

thermodynamic
and
at

treatment,
other
not

and
T

are

considered
are

to

be

variables

times

and

so are

considered. chosen
constant
as

writing
To

dU/dV
clarify
are

does

indicate
variables

which which
e.g.,

variables
are

independent. partial

this,
indicated

the

other

kept

in

by

subscripts,

(duidv)T.

Ch.

1, 12]
Argon

CHANGE

OF

INDEPENDENT

VARIABLES

17

Pc

48.00

atm,

7c
Tc

1.8839cm3/g,
150.72

Fig.

1.5.

relief

of

the/jK-surfaceof

argon.

Some

of

the with

thermodynamic
dif erent of choices

relations of

are

simply

relations

between

partial
are

derivatives

independent
useful: when
to

variables,
three
z

and

obtained and

by
z

The

change fol owing


a

have
y,

functional
x
as a

independent identity dependence,


function

variables.
is

particularly
it is

variables
as
z

x,
a

possible
z,
or

consider

function
x.

of
Then
we

and

or

of

and

as

function

of

and

have

dx)\dyJ\dz.

A.22)

18
or

THERMODYNAMIC

STATE

[Ch.

dx\

)=~wJ{e~x);
_

fdz\

lfdz\

(L23)

This

fol ows

immediately

from

If

const.,

dz=0

and

the

ratio

dx:

dy

(dx/dy)z

must

be

A.23).

Examples
1. A

magnetic
created
that

field
assume

body by
the

is
a

inserted
current

in

coil the

and

is

magnetized
For

by
the sake uniform
electric
are

the of

through
and the

coil.
done

field,

H,
Show

magnetization,
the

M,

magnetic simplicity, throughout


in

the
process

magnetic
of

body. magnetization

that
is

work
M

by

the

source

the

;
per

dM

unit

volume

of

the

magnetic

body.

Assume

that

the

magnetic

body

has

no

deformation
Solution Let
us

by

magnetization.

consider

the

case

where The
a

coil
J is

is

wound

around
in
a

sufficiently
n

long
per
unit

cylindrical length
inside

magnetic
is

body.
when material is small
If

magnetic
is

field

coil the

with the

turns

Hj

the

HM,
may

which,
assume

4nnJ[c magnetic however,


=

current

passed
of

through
Hj
is and
a

coil.

The Therefore

field
field
we

the

sum

demagnetizing
needle.
entire

if

the coil cross-sectional

specimen
is
is wound

long
the
is a,

here

cylinder,
coil
is
<&
=

whose
onlB=

H=Hj. length VnB,


the
H

the
V=al in

over

is

/ and

area

the

flux

where

the

volume

of

the When

magnetic
the
so

length through body


current
a

of

the
the and
J is

B=H+4nM

is then

flux
and

density
M,
and

the

magnetic
B,
-

body.
also

increased,
electromotive

accordingly

change
is
dt

that

counterto

force

-A/c)
law.

d$/dt=
The force
J dt

V(n/c)
the time

dB/dt
electric

induced,
source as
a

according
must

Faraday's
this

induction counter-electromotive

work
in
=

which
a

do

against

interval

charge

\cHj

dt/nn

Ch.

1]

EXAMPLES

19

passes

through

each

section
Jdt
=

of

the

wire,

is
=

(lie)
Of
be this

(d$/dt)

iVH
is

dB/n
work

dH

4nH

dM)/n
to create
a

work,
of with

d\_^VH2li \
the
dM.
presence the work A

the the unit


=

which

is

needed

field
dM
can

irrespective
identified

of
per

magnetic
volume is

body. required
the work

Thus,
to

the

work

increase
unit volume

the

zation,

M,

by

Hence,

$HdM

per

magnetirequired

Fig.
to

1.6

increase

the of

magnetization
at

from

0 to

M.

(If

it

were

possible
would
be because

to

fix

the
to
we

final
the would

value
electric

magnetization
source

M,

then

the

work
H

\VH2Iti
to

fed
then

back

in

the

process

of

decreasing

zero,

have
2.

dB=dH.)

Let

d'q

be

the

heat
dT

necessary

to

material

by
assume

keeping
that
v,

the there
the

state
are

simplicity, specific
given

change quantity only

the
x

temperature
constant.

of
For

gram

of
sake
e.g.

the heat

of

two

independent
T.

variables,
that the

the
cx

volume,

and

temperature,

Show

specific

is

by

the

equation
du\
c
==

'dv

dv)T
energy per

where
Solution

is

the

internal

unit

mass

and

is the

pressure.

Since

the the
to

mass

of

the
From

system
eqs. is

is constant,

we

need

only
first

consider
law
du

the

work
to

done

by applied

pressure.

A.5)

and dv.

A.7a),
The

the

of
in
u

thermodynamics
due

unit

mass

d'q=^du-\-p

change

changes

20

THERMODYNAMIC

STATE

[Ch. dv.

dr the

and

dv

in

T and

is
we

dw

(du/dT)v

dT+

(du/dv)T

Substituting

this

into

equation

for

d'q,

have

Although
states,
the it

the

parameter

is Thus

given
v

as as
a
x

function
of
constant

of
T

and
x

for

equilibrium
T

is
dr.

possible
variables.

to

consider

function
is

and and

taking
Tis

and the

as
=

independent

if
into

kept
and

changed,
obtain

dv
ans-

(dv/dT)x
wer.

Substituting

this

A)

dividing

by

dr

we

3.

Show

that

there

is

relation

Cp
between gas. Solution The mole first law the

Cv
the

(Mayer's
specific

relation)
heats
per

isobaric

and

isovolumic

mole

of

an

ideal

of
is

thermodynamics

for

an

infinitesimal
+

quasi-static
dV

process

of

of

gas

d'Q
(A.5),
on

dU

the

A.7a)). volume,

Since

the
we

internal have

energy

of

an

ideal

gas

does

not

depend A)

V,

dU=Cv(T)
d'Q
=

drand

Cv(T)dT
is
+

pdV.
in

The

isovolumic

specific d'Q

heat
=

(d'Q/dT)v
CvdT

fact

Cv.

We

rewrite

eq.

A)

as

d(pV)

-Vdp

B)

and

substitute

p V=

RT

to

obtain
=

d'Q
or

(Cv

R)

dr

dp,

C)

4.

Given
0

the

density atm), cal/g

of

air

at

NTP

(normal
the
to

temperature

and heat
at constant

pressure,

that pressure,

is,
=

C,

cp

0.238

p=0.00129 and deg,


the of work 22.4
1 at

g/cm3,
its NTP.

specific
the

ratio

isovolumic
heat J.

specific
Assume air
to

heat,
be
an

cpjcv
ideal
gas

1.41,
with
a

calculate
volume

equivalent

of

Ch.

1]

EXAMPLES

21

Solution The
gas

constant,

R,
of

may
state

be

obtained It
can

in

units

of
be

joule/mol
obtained
is the in

deg
units
we

from of
express
state

the

ideal
mol

gas

equation
from

pV=RT.

also
=

cal/

that where
1.013 Hence:
r

deg by
the
x

Mayer's
then

equation
J=R/R'.
The

CPCV
The

jR', 106

normal
of

state

(example (NTP)
and
at

if 3) and an equilibrium
pressure, is V=22A
/?

temperature,

r=0C=273K,
volume
a

latm=

dyne/cm2.
=

mole

NTP

103

cm3.

pV/T
the

1.013 8.32

106

22.4

103/273
mass

8.32

107

erg/mol
heat

deg capacity weight),

joule/mol
specific
heat
mass

deg.
per

Since
per
m,

isobaric divided
is
m
=

unit
a

is air

the

isobaric

mole

by
pV
=

the

of

mole

of

(average
28.9

molecular

which

0.00129 28.9 per


we

22.4 0.238

103
6.88

g/mol,
deg.
=

we

have

Cp
The
4.88

mcp
heat

cal/mol

isovolumic

specific

mole
have
-

CK=mcK=mcp/y
=

Cp/y

6.88/1.41

cal/mol

deg.

Therefore

R'
and
j
5.
=

Cp
=

Cv

2.00

cal/mol
=

deg

R/R'
necessary 0 C
to

8.32/2.00
to

4.16 which

joule/cal.
has
a

(i)
one

Calculate

the
How

heat

heat
at

air
constant

volume
at

of
is

27m3

at

atmosphere (ii)
much
air is If

from
heat
to

20
constant

volume.
initial of
volume
0 C

is 20

necessary
at

if

the

27m3

and

the

heated the
to

C
an

pressure?
room

(ii )
connected
to

air the

is

in

insulated
at

27m3
heat
to

with
must

small

leaking
into the
room

hole
4 for

outside of
air.

1 atm,

how

much
0 C

be Refer
to

put
to

raise

the

temperature

slowly
Consider

from
the

20 heat

C?

example

the Solution

characteristics

specific

be

constant.

(i)
volume

This of
as

is

case

of
at

isovolumic
and 0.00129
1 atm

heating.
is 27

The

mass

of

air

which

has

27m3

0 C
M

calculated

from
3.48
x

its

density,
g.

p=0.00129

g/cm3,

106

104

22

THERMODYNAMIC

STATE

[Ch.

The heat

isovolumic

heat

capacity
=

Cv
=

is

calculated 0.169
=

from

the

isovolumic

specific

cv

Cv Considering
the

Mcv
heat

cjy =/0.169
capacity Tt to

0.238/1.41
x

cal/g
5.88
x

3.48

104

deg, 103 Qv,

cal/deg.
necessary
to

the

as

constant,

the

heat

raise

temperature
t2

from

T2

is

Qv=

f
In

Cy

dT

(T2
isobaric

Tt)

Cy
heating

20

5.88

103

1.176

105

cal.

(ii)
instead

the of

case

of

we

use

the

isobaric

heat

capacity

Cp

Cv:
=

Cp
Then the

Mcp
heat
=

yCv

1.41
is

5.88

103

8.29

103

cal/deg.

desired

Qp
-

Qp
(ii )
since
constant
can

(T2
assume

7\)
that

Cp
When
mass

20 pressure

8.29 in

103
the

1.658 is
at

105

cal.
at

We

may

the

room

maintained
pressure,
at

1 atm
p,

the be

heating volume,
determined

is

slow.
from

the

air

is heated

constant

and
T

V, the
of the

of

the

air,
of
const.

M(T),
state

in

the

room

temperature
is the air Since in the is the
average
room

the

equation

pV=RTM/m
If

(m
mass

molecular
is
mass
so

weight
when

air),
heated

or

M(T)T=
is
at constant

the
=

of
heat

the

Mx
that

temperature

Tu
the

then
pressure,

M(T)

M1T1/T.
capacity
to

air

of

M(T)
the

is heat

being required
r2

its

M(T)cp,

to

raise

temperature
t2

T2

is

Q
Since

I M(T)
Ti

cp dT

c.M.T,
C=293

J
Ti

e^T,
Cp
0.0706
=

log
8.29

-*.
103

Tt
8.29

=0

C=273

K,
so

T2

20

and

cal/deg
105
cal.

as

calculated

above,
x

Q
6.

103

273

log pVy=const.
of in the
an a

293
=

273

2.26

106

1.596

Show static
does
to to

that

the
its

relation
process

(Poisson's
ideal
gas heat

equation)
derive adiabatic
to

holds
work process
W

in

quasithe gas

adiabatic

and

the
constant.

which

surroundings

(p2,

V2,

T2).

Assume

quasi-static specific

from

(pu

Vu

7i)

be

Ch.

1]

EXAMPLES

23

Solution

The gas
is

equation d'Q
the

for
=

the

first

law

in

the of
=

case

of
be

Cv

dT+p
condition

dF(eq.

state,

adiabatic

A) d'Q
+

example
0
can

quasi-static 3). Substituting


writ en
=

process

of the

an

ideal of

equation

as

CvdT
Using

nRT(dVIV)
Cp=Cv+nR
log
=

O.

A)

Mayer's
eq.

relation

grating
=

A)

we

have

3), (example Cv \ogT+(CpCv) TV7'l

(for
V=

const.,

moles) which,

and
as

inte-

Cp/Cv
Ba)

y,

becomes
const.

and,

if

we

use

the

equation

of

state,

pV7
(We
with When
can

const.

Bb)
pV=nRT
and,
the

also

get

dp/p
+

dV/V=dT/T
which

from from

eliminating
adiabatic

dT/T
line,
the

eq.

A),
the

dp/p
volume
done
v2

ydVIV=O
is

changed
gas
v2

gives Vx

Bb).)
to

V2 along

work,
w

W,

by

the

is dV

dV

Pl

VI

(as PV
-

PlVI)
C)
-

PiV?
y-1
=

(V!~7
1

Vry)
=

y-1

-^(PiV,
-

P2V2) Cv(y V^),


that

-^-(T1-

T2)
of internal
an

Cv(Tt

T2)

(as

1)
TX>T2.
the

Cp
The

Cv
gas

nR).
does work

D)

In

the

case

adiabatic
energy

while decreases
7.

the

(cf.
that

Chapter
fol owing

expansion decreases, 3, example


relation
and

(V2>
so

temperature

naturally

5).
exists between the adiabatic

Show
Kad=

the

compressibility
kt
=

A/y)

{dvjdp)aA

the

isothermal

compressibility

~{\jv){dvldp)T:
_v
~

KT

where
pressure

cv

and

cp

are

the

specific

heats

at

constant

volume

and

constant

respectively.

24

THERMODYNAMIC

STATE

[Ch.

Solution When
we

say

adiabatic
for If
are

or

isothermal
adiabatic
we

compressibility
thermal
of adiabatic
p

quasi-static
consider

compressibility, compression
the

we
or

of

course

mean

the iso-

quasi-static
u

and

compression. v (we
process,

internal of

energy

to

be

function
for

considering
du+p
du
=

unit

mass

material),

the

condition

0,

becomes

Therefore

A)
If
we

write

u=u{T{p,
fdu\

v), v),

we

have

fdu\

fdT\
have

fdT\

and

if

we

write

u=u{T(p,

v), p),
'du\

we

fdu\

fdT

which

gives
'du

where

we

have

used
in eq.

the

relation,

cp=(du/dT)p+p(dv/dT)p.

Substituting

eqs.

B)

and

C)

A)

gives

'dp\
Now

vL

cp(dT/8v)p cv(8T/dp)v'
{dTldv)pj{dTjdp)vi
which is

using

the

relation,

(dp/dv)T=

obtained

from

(an

application

of

A.23)),

we

get

dp\
from which
the

cp

fdp\ Cv\8vJT
,.,

E)
be

relation
see

which

was

to

(Alternative

solution:

Chapter

2, problem

proved 14.)

fol ows

immediately.

Ch.

1] Since

EXAMPLES

25

Note:

cp/cv>l,
in

eq.
p-v

E)
the

means

that
is

(8pldv)!id>(dp/dv)T,
for the adiabatic line

i.e.

at

any

point
the

(p, v)
isothermal

the line.

plane

slope

greater

than

for

8.

Determine critical

the

pressure,

pc,

the

volume,
the
van

Vc,
der

and

the Waals

temperature,

Tc,
of

at

the

point

for

gas

which

obeys

equation

state,

where
the
pc,

is the and

mole

number

and

a>0,b>0.
0=

Rewrite

the

reduced

Vc,
the

variables, Tc, respectively.


lines

p=p/pc,
Using
in

V/Vc,
this

and and

t
also

T/Tc,
the
curves

equation expressed
state" for
in

in in

terms

of of

units

"corresponding curve).
is. plot ed
the
at
curve

expression,

plot
and Note:
constant

isothermal
When

the Waals low

C(po)/3p)t=0
the
van

(the
der
at

lat er

p-o is the

plane Boyle equation

Cp/do)t=0
p-V

the
a

plane
and
can

for
a

T,
while

sufficiently
it

temperatures
monotonic

has

maximum
as

minimum
in
on

becomes
state

high
is

temperatures
the

be

seen
=

Fig.
the

1.7.
T=

The

critical
curve.

(critical

point)

point

where

(dp/dv)T

Tc

Solution

Write

the

equation

of

state

in

the

form
nRT

an2

A)

Then

(8p[8V)T

0 and

(d2p/dV2)T
RTfcV
-

gives
=

bnJ

2an/F3,

B) C)
Substituting
Tat
8
c

and

RT/(V
So
we

-bnf
V=3bn,
are

3anjV*.
RT=Sa/27b. Fand of/?,
"
"

have

V-bn

2V/3
These
la

or

and

this

in

A)
i.e.

gives

p=a/27b2.

the

values

the

critical

point, D)

"

"

Fc

27

62'
V=

'

27

Rb'
divide

Now

substitute

p=pcp,

Vcr>,
nRTA

and

Tct
pcVc

in

A)
vJ

and

by

pc.

Then

an2
-

^c^cO

PM

26

THERMODYNAMIC

STATE

[Ctl.

Substitute

eq.

D)

and

we

have

the

desired

expression,
3

8t

or

3\

to Writ en
Thus
to

1)
a

8t.
and and

E)
b, do
not

in

this
gases
same

form

the

material

constants,
the the
van

appear
may

explicitly.
be
same

all
be
is
In

(which
state

obey
when units
states.

der

Waals
of values p,
o

equation)
t
are

considered

in

the

values

the

(i.e.
is the

each

gas

measured
the
the

in

of

its

particular
in pressure,
a

of

Vc,
note

Tc, pc).
the p<

This

law

of

corresponding plot ing


considered.

t=const,
of
When

curves

p-o
i.e. As

Firstly,
be

regions
an

negative
oy
gas

plane, v<}
then
o

fol owing

points.
need the
not

and
eq.

3/o2,
p becomes
are

and
when
o

o9/(8t),
is

E)givespoft:
y,

gas

behaves

like
For
a

ideal
o

large.
of p, where

ite.
or

given
real
values

there of

is
o.

one

value
the
at
case

but,
there

for

approaches a given
are

infineither
o,
one

three

In

three

p there values

of

let

them

be

dd^de^df.

Looking

the
=

derivative,
-

Ep/5o)t
obtained
is

24t/C
the
o

IJ
on

6/d3
the
+
oo

E') right-hand
so

from
than

eq.

E),
second

we

see

that
when is

first

term

side

of
we

E')
have

larger
d
=

the

one

and
o
=

n-*

that
DF,

there
and
and be continuous

(dp/3o)t<0.
when
de.

Therefore
Since
the between
eq. vE

Cp/3o)t<0
E)
curve

when

the
has
Let

dif erence
a

oD of

and
two

Cp/do)t>0
oE
vG

monotonic
between

functions,
maximum
DH,
which

isothermal
and

minimum

oD
extrema

and and

oF.

the

abscissae
or

of

these

are

determined

by

Cp/3o)t=0
4t
=

Cd
and

lJ/o3.
pH,
can

F)
be

The

corresponding
and

values
in eq.
are

of
As

p,

pG
curves

obtained

by

substituting

DG minimum

DH
curves

E).

t is
describe

changed,
eliminating
p
=

the
in the

maximum
the p-o

point

(oH,
The

Vh)
equations
eqs.

and

tne

point
or

(oG,
obtained

pG)

plane.

for

these

by

parameter

t from

E)

and

F),
The when

Cr)-2)/tK.
o
=

G)
y,

curve

is
o-*

simple,
oo.

p=27
It has
o
=

when

when
=

f,

and

p-*3/o2
and il ustrates
an

maximum

at
=

t)=l,
curve

inflection

point

at

and

fj.

The

p JGCHK

(critical
in

point)
Fig.
1.7

Ch.

1]

EXAMPLES

27

Fig.

1.7

28

THERMODYNAMIC

STATE

[Ch.

this.

The

intercepts
curve,

of

eqs.

E)
isothermal
=

and

G)
curve

are

the

H,
the
H
we

of coincide

the

E).
C
at

The

of
and

eq.
on

minima, E)
this which

G,
for

and
1 passes

the

maxima,

t=
is The

through
curve

maximum, C,
that

(o

1, p
for

1)
an

of

eq.

G)

isothermal
the

and
If

consider

becoming E) eq.
1, eqs.
minima have
1
as

inflection

given
and
0

of
have

t, then
maxima

for
curves

t>
and

E)
when

o, p is a G) do not
<

point, monotonically
intersect.

critical
isothermal
show LCM

point.
function
curves

increasing
considerations
for

t
1.7.

<

1.

These

that for

the

isothermal
and

the in the

form

ADGEHFB

0<t<l,
eq.

t=l,

PQ Finally

for
let

t>
us

shown

determine

Fig. Boyle

curve.

From

E)

we

obtain

(
So,
for

8t

V
C(po)/do)t=0
this
in
we

dv
have

Jt
8t
=

D2

CD-IJ'

3Co-lJ/o2.
eliminating
t,
we

Substituting

eq.

E)

and

have

P This
curve
=

3Cd-2)/d2.
points
at

(8)

passes
=

through
It
has
a

the maximum
at

(o=y,

p p
1.8
=

27),
anc* the
when

(o=f,
p-9/o
relief
as

p
o-oo.

0),
van

and
The der

(o
point
Waals
Note:

l, p
of

3).

inflection

lies

(o
curve

2, p
has

(o=f, 3). Fig.


parts
or

V)
shows

of

the

diagram.
The
is

isothermal
metastable
the
rule
state.

where

p<0
unstable

0<t<l
The is in
a

and

this

part
librium

either
of

gas

Maxwell's

(see

phase Chapter

((dp/3o)t<0) (p>0)
4),
so

(Cp/3o)t>0).
phase be positive
determined

equiby
thermal

and that p

the
must

liquid

stable

equilibrium
9.
In

the

Joule-Thomson

porous
a

plug
plug
kinetic
into this
process

experiment,
into
a

gas

at

pressure
pressure

px

forced

through
the of
gas gas

prevents
a

porous from

(cotton) acquiring
is
forced
in

region
as

of

p2

slowly (the plug


1.9. When

is

energy)
a

shown show
the

in

Fig.
the of

volume

Vt

volume
and that

V2,

that

enthalpy,
temperature

Tx
Solution

is conserved U+pV, T2 is determined

change

by

this

condition.

Initial y
between

the

the

piston plug

P2
and

is in

contact

with

the where

plug
the

S and

the
is

gas

is introduced

the

piston

Px

volume

Vu

the

pressure/?!

Ch.l]

EXAMPLES

29

=v/vt

Fig.

1.8

30
1

THERMODYNAMIC

STATE

[Ch.
2

p\
.

porous

P2
'

n
Pi

'.plug

P2 1.9

Fig. and

the
its
so

temperature
pressure
at

7\.
px

Then

the

piston
into S and
k2

Px is slowly
contact

pushed
with
S and

while

maintain-

ing
down

until
between
o

Px

comes

P2
done

is

pushed
by
the

that
is

the

volume

P2

is

V2.

The

total

work

pistons

(
Vi

Pl

dV

[p2
0

dV

p^

p2V2.

From

the

first

law

U(p2,
Therefore,
mass

V2)
H

U(Pl,

V,)

PlVt
function

p2V2,
Tfor

if the

of

gas,

eq.

enthalpy A) can

is considered

as
as

ofp

and

given B)

be

writ en

H(Pl,Ti)
This

H(p2,T2).
are

determines

T2 whenpu

Tu

andp2
Problems

given.

[A]
1. When

the

equation
relation

of

state

is

given
Pccp
=

in

the

form

p=p(T,

V),

show

that

the

fol owing
where

holds:

kciy,
coefficient
of
the pressure
at
at

0Lp

volume,
pressure,
2.
For

(Xy and

(dp[dT)vlp (dV/dT)p/V
=

is

the the

thermal thermal
is the

constant constant

expansion
isothermal
of
the show

coefficient bulk modulus.


the

k=

V(dp/dV)T
dp, dV quasistatic
and

small

temperature,

changes T, in

dT

pressure,
that

p,

volume,

V,

and

process

Ch.

t]

PROBLEMS

[A]
at constant

31

3.

At and
oxygen

NTP,
a as

oxygen

has
heat

specific
constant

heat
the

pressure,

cp=0.2203
cal/deg
of
at

specific
an

at

volume,
work

ideal

gas,

calculate
is

cK=0.1578 equivalent

g.

cal/deg Considering

g,

heat.

4.

mole
20

of

an

ideal
an

of

C
gas

from in

gas initial
How

expanded
pressure

quasi-statically
of
20
atm to

constant

temperature
is the

1 atm.
must

What
be

work
to

done
the

by
5.

the

joule?

much

heat

in

calories

supplied
Kad,

gas?
ideal
is
for
an

Derive gas

the (adiabatic compressibility and quasi-statically adiabatically (p is the density). given by c= -Jdpjdp sound the adiabatic calculate and change the of velocity with and change temperature.

is

compressibility), compressed.
Consider
this

when
of

an

The
as

velocity
a

sound
0

derivative
air
at

velocity

through

1 atm,

C,

6.

An

ideal

gas

is

changed
process.

from this

state

(jplt
that,
added
the

Vu
if
to

7i)
the

to

state

(p2,
the
return

V2,
of the
state
to

T2) by
work

quasi-static
done

adiabatic

Show process is

heat the
gas

equivalent
in

by

the

maintaining
7.

gas the is the

in

final

while

volume

constant,
from
three 1DC2. What
an

temperature
initial
state

wil

Tx.
a

An

ideal

gas

(Pi>
(i) 1A2,
1 ->2?
must

Vi>
Also
be

T2) by
(ii)
added

1B2,
obtain

changed fol owing and (ii )


the in

(pu
processes in
to

Vx,
as

Tj)
seen

to

final
the
energy

state

quasi-static
is the be done Assume

in

figure:
for that heat
constant.

increase
the the

the

internal
and heat the
is

work
process.

that

must

system

each

that

specific

pi,

Ti)

2(V2,

pz,.

T2)

32

THERMODYNAMIC

STATE

[Ch. adiabatic

8.

Assuming
as

that
an

when
gas,

air determine

rises

of

ideal
in

the
9.

decrease the

temperature
and
The

undergoes the change at a height

it

an

quasi-static
with

expansion
height.
What
is

in
of

temperature
1 km?

Consider
shown in
contact

in

quasi-static the figure.


with
a

cyclic
change
at

process from

of
1
to

an

ideal
2

gas
an

(the
2 to

Carnot

cycle)
expansion
adiabatic
with

is that

isothermal
3 in
an

heat from

bath
3
to

temperature
an

7^,

from

expansion,

that

isothermal

compression

contact

heat

bath
from

at

temperature
If

T2>
heat absorbed bath
+

and
from

finally
the heat show
is

that bath
that

from
at

to

an

adiabatic
and the heat

compression.
absorbed

the

Tx is Qt

the

heat

at
=

T2
0.

Q2,

Qi/Ti
Assume 10.
If

Qz/T2
to

(Clausius

equation)

the the

specific
heat

heat

be

constant.

specific
that
the
pressure,

of is

an

ideal
for

gas

for
process,

process

where

is
to

kept

constant

is

cx,

show
p

pvf=const,
v

this

where/is
volume,
and
constant

equal
and

(cx
are

cp){(cx
(constant)

cv)>

is

the

specific
pressure

cp
volume. and

and

cv

the

specific
11.

heats

at

constant

mole

of

an

ideal

gas

with
to

pressure,

pu

volume,

Vv

is

freely

(and
to
a

adiabatically)

expanded

V2.

Then

it

is

quasi-statically

compressed

Ch.

1]

PROBLEMS

[A]
pressure
at
to

33

volume

Vt
is

while until

maintaining
the
pressure

the
returns

p2.

Finally
the volume

the

gas

is remains

heated

quasi-statically This cycle this using

px

while
heat

Vx.
35)

called
Assume

Mayer's
that

cycle.
the

Prove molar

cycle.

Mayer's specific

relation
is
constant.

(see

example

12.

Consider

gas

which

obeys
P
=

the nRT
V

Dieterici

equation
na

of
\

state

-nb

exp

RTVJ
absolute

where

is the
R

pressure, the gas

Fthe

volume,
and
a

Tthe

temperature,
material
constants.

the

mole
that

number,
the
pressure,

constant,
and

and
at

are

Show
are

volume,

temperature

the

critical

point

and

rewrite
states.

the

equation

of

state

in

form

which

shows

the

law

of

corre-

sponding
13.

Calculate
mixture of

the
oxygen,
at

specific
O2,
constant

heat and

at

constant

volume

of

air
a mass

by
is

assuming
ratio
0.158

it of

to

be
The

nitrogen,
volume
of

N2,
gaseous

with
oxygen

23:77.

specific
that of

heat
gaseous

cal/gdeg

and

nitrogen

is

0.176

cal/g

deg.

34

THERMODYNAMIC

STATE

[Ch.

[B]
14.
A

small
As axis of

iron it

needle,

which
from
in the

is

initial y
into the

bringing
magnet.
the

slowly
shown
the bar

infinity figure,
Assuming

unmagnetized, magnetic
of
that the the

is

magnetized
a

by
bar

field
needle

of

permanent

the

direction

is

kept
bar

parallel
magnet

to

magnet.

strength

of

the

is

unchanged is unchanged
the needle
to

by by
a

the this

presence process,
moment

of

the

needle,
that
mx

and the is

that work done

the

volume
in

of

the

needle

show

order

to

magnetize

magnetic

given
dm,

by

where
moment

H
m.

is

the

field

at

the

position

where

the

needle

has

the

magnetic

15.

Consider section.
constant

vertical
the

column heat field.

of

air

Calculate

capacity,

infinitely assuming

high
the air

with
to

constant
an

cross-

be

ideal

gas

in

gravitational
a

16.

Consider and
a

closed

system

for

which
be

any

two
as

of
the

the

pressure,

p,

the

volume,
to

V,
define
U

the

temperature,

T,

may

chosen
state.

independent
the internal

variables
energy

the

thermodynamic enthalpy

by

H=

equilibrium U+pV,

prove

the

Denoting fol owing:

by

and

Ch.

1]

PROBLEMS

[B]

35

(i)
heat

The
at constant

specific

heat
pressure

at

constant

volume

Cv

(dU/dT)v
f <iP\

and

the

specific

Cp

-Cv

fdV\ [ \dTJ

Wp+

(dH/dT)p; fdU\

\dVJT)

-[
;

dp\

\dTjv{

(dV\ \dpJT

fdU\

\dpJT)

:
Jt

Note:
law

Since
of

the

left

side
may

of

(iv)
be

consists confirmed

of

measurable

quantities,
this

the

first

thermodynamics

by

checking

relation

experi-

mental y.
17.

If of
the
a

is the

the
and

speed
the heats
energy,

of

sound
at
w,

c=

yfidp/dp)^
is
pressure the be
+

(where
for
an

p
at

is
constant

the

pressure

and

is the
ratio

density
internal
constant

partial

derivative
constant

adiabatic
and
mass h, per unit t h e by fol owing

process)
volume,
of
an

and ideal

y the

specific

show
gas

that

and
may

specific
u
=

heat

enthalpy, expressed
const.,

with

expressions:
+

y(y-l)
energy

y-1
moment

const.

18.

If

the
H

internal
heat
is
constant

is

and

the

magnetic
material
as

is

/,

show the

that

the

specific
field

of

uniform
can

magnetic be expressed

in

process

where

magnetic

fol ows

-(du\
where Tis

h(81)
of the

the due
to

absolute

temperature
may

magnetic

material.

The

change

in

volume
19. If

magnetization
for
constant

be

considered

negligible.
of
a

the that

heat

denoted show

by

capacity CM and the fol owing


and the

the

heat

capacity
exists

magnetization by
between

uniform

material

is

CH

for

constant

relation adiabatic

the

isothermal

magnetic magnetic

field,
sus-

ceptibility

magnetic
Zad

susceptibility:

_CM
~

XT'

The

change

in

volume

of

the

material

may

be

neglected.

36

THERMODYNAMIC

STATE

[Ch.
as

20.

Discuss internal

Carnot where

energy

cycle density,
T

using
w,

thermal
of the

radiation

its

working
the

material. Stefan-Boltzmann
is
a

The

radiation

is

given equation

by

law,
and

u=aT4,
the radiation

is

the
p,

absolute
is

temperature

[c(>0)
of
state

constant],

pressure,

given

by

the

p=}u.

Divertissement

Nicolas
steam

Leonard

Sadi

Carnot.

In

the

first
of Watt
on

half

of

the had

last

century,

the low-tem-

engine,
heat

perature
more

and
to

more

transportation.
about
son

completed by due reservoir), revolutionary eminent Many


the Motive
Power

introduction
to

the

condenser
come

(the
to

James

A765)
developments
like

produce
and
set
was
a

effects

in

industry
Poisson

physicists
of

Laplace
Carnot

and

study
Lazare born

Fire.

Sadi in be
wrote
a

A796-1832)
the
French

of
was

Carnot,
and

Organizer
died
heat
was

of
He assumed

and of

in

Paris.

Victory probably
to

Revolution,
the caloric
either

learned
substance
or

theory
of

heat,

in

which

from to flowing body with atoms compound la sur Reflexions book, a cet t e divelopper puissance brother A878) together
Carnot
was

body (latent
puissance

(heat heat).
motrice

conduction)
He
a

of but
sur

capable making
very

chemical

short
et
was

important
propres

dufeu

les

machines

(Paris,
with
some

1824),
of
Carnot's the heat

which

reprinted
heat

by

his
work

posthumous
that,
in

directed

his
at
a

attention
expense

to

point
but

in heat from

the

manuscripts. engine,
the
not

done
heat

not

the hot

of
to
a

connection thus law


of
to
a

with
could

transfer be
of

of without
a

from
a

body
in
his book In

cold
of

body,
water

and

used
to

cold the

body,

analogy
he of heat
many

fal ing
the
a

high although

reservoir

low

reservoir. that he

assumed
was

of

conversation of the
heat

heat,
later
and

namely
abandoned
work:

quantity
law heat. He and

state

this

arrived

at

the methods

law
came

function, equivalence
estimate
to

he

actually
of

proposed
introduced
Carnot's

mechanical
as

equivalent cycle,
Carnot's
gave
use

what

be
P. E.

known

Carnot's

and
Carnot's

established
book

principle.
overlooked
until and devised
was

had

been
an

B.

Clapeyron
by
of law

theory
indicator assumed

analytical
corrected

graphical
by
Watt.

expression
The
R.

A834) making
based into

of
heat
the

the
work that

diagram
by
of
not

conservation

of
on

Carnot
R.
von
a

by
and
J.

Clausius
P.

J.

Mayer change
to

A841)
in

Joule
of
heat First

A850), A843^9),
but
to

the

form

sumption
and

of

heat
H.

only proportional
Clausius
L.
F.

the

distribution
work

also
do of
Law

con-

the
this

done

is necessary
the

work,
Ther-

vice
law

versa.

named
von

modification

modynamics.
this
to

Helmholtz
of
the

A847)
conservation
scale
of

and of

Clausius
energy.

generalized
W.

the who

principle
introduced
also
Law

Thomson

{Lord
on

Kelvin),
Carnot's

Kelvin's

temperature

A848)
of heat Thomson

based and

work,
The
and Second

work.

recognized of Thermodynamics
of

the

law

of
was

equivalence
formulated
is

by by
E.

A851)
A

Clausius
of

A867).

sketch

the

history

early

thermodynamics

given

Mendoza,

Ch.

1]

solutions

37

Physics
Wdrmelehre

Today

14

A961)
Aufl.

No.

2,

p.

32.

See
von

also
Johann

E.

Mach:

Principien
Ambrosius

der

(vierte

1923,

Verlag

Barth,

Leipzig).

[C]
21.

Neglecting
the
in
a

internal of
the

friction

(viscosity)
density
and
Assume the

and

thermal
kinetic
there
are

sum

enthalpy
flow field. of
a

energy
no

conductivity, density
external

show is

that
such
as

conserved

the

steady

fluid.

that

forces

gravitational
the

22.

Obtain

final flow
a

temperature
when
steam

and nozzle
into with
heat
a

the the

upper
to

limit 300
1
at atm. at

of
C
constant

the
at

flow
5
atm

velocity
is that

in

steady-state out through


heated
steam

superheated
air

flowing
super-

suitable is
an a

Assume
pressure

ideal
be

gas

specific
y
=

heat 1.33.

cp=0.49
and

cal/gdeg, gravitation
23.

and
may

specific neglected.
A,
B, C,. .
and
the

ratio

Thermal

conductivity

Consider

systems
the
pressure,
p,

whose

thermal

equilibrium
v. a

states

are

determined
to

by
zeroth

specific
there

volume,
exists and

Show

that

according
of
for

the
each

law such
between
are

of

thermodynamics
that

function
the

characteristic condition
is that the of

system
librium

9K=fk{p,
two

v),. .,
systems

that
A

thermal
values
of

equithese
the

(e.g. 9A=0B)
there the of
two

and

B)
of
a

functions
Use

equal
fact

(i.e.,
that of

(Theorem
exists

existence

temperature).
between

the

empirical
parameters
the

functional
in

relation

independent
24.

systems
1

equilibrium.
the

Generalize

problem
in the flux
case

example
where
the

magnetizing
M,
and
the

field

considering magnetic
are

effect
the

of

the

de-

field,

H,

magnetization,
from

magnetic

density,

B,
Solutions

not

uniform.

(Start

Maxwell's

equations.)

1.

The

relation
from

between the

the

dif erentials,
of
=

dp,
state
as

dT

and

dV,

of

p,

and

are

obtained

equation dp

(dp/dT)v
dp

dT

(dp/dV)T

dV.

By

definition

we

have
=

papdT-k{dVIV).

38

THERMODYNAMIC

STATE

[Ch.

The

ratio

of

dFand

AT
=

when

const,

is

obtained
therefore

by

let ing
=

d/>=0,
p<xp.

or

(dV/dT)p
2.

Vpaplk,
previous
dT
-

and solution

kctv
have

From

the

results

of

the

we

dp
3.
As

ktxv

k(dVJV)
ratio
of

{aF
gas

dT
constants

(dV/V)}.
calculated
from
The
the

in

the of of

case

of
state

example
and
is
of

4 the

the
wil

equation weight
volume
standard

of

by
32
gas is V

Mayer's
and
is 22.4 22.4

relation

give
Under
of 700
1 atm

the

answer.

molecular
the

oxygen

m=32g/mol.
1,
x

standard
1 gram

conditions
of
oxygen

1 mole

so

the

volume

under

conditions

103/32
for
p
=

cm3
and

Since

1 atm=

1.013

106
=

dyne/cm2,
1.013
2.60
x
x

T=273

K, deg.

Rfm
From the

pV/T
in
=

106 x 700/273 106 erg/g deg


we

0.260

joule/g

dif erence

specific
=

heats 0.2203 is
-

get
0.1578
=

Rjm
Therefore
the work

cp-cv

0.0625

cal/g

deg.

equivalent
J
=

given
=

by
4.16

0.260/0.0625
of
an

joule/cal.
work work done

4.

If

the

volume
as

of
the

1 mole

ideal
Since
it

gas

is
a

V, the

by the
the

gas

is

given
is
at
an

by A.7a) given by
absolute

d'A=p equation

dV.

is

quasi-static
The

of

state

pV=RT.
the

process, done
from

pressure/?

temperature,

T,

when

volume

expands
RT

by Vx

the
to

gas

V2 is

-A=

Vi

\pdV J
the x293
=

RT[ J
Vi

log
and

RT

Vx
p2

log-,
With

p2

where
293

we

have
^7=8.31

used

relations
=

pt

Vx
103

RT,

V2

RT.

T=
p2
=

20

C=
\ atm,
x

K,

2.43
x

joule/mol.
Therefore
the work
the done

For

^=20
RT

atm,

log
103
The

Oi/^2)=log20
x

2.30

1.301

=2.99.
is from

log
gas.

(pxlp2)=2.43
A.2):
U
not

2.99
heat
=

7.26

103
is
At

joule/mol
obtained
T

by
law

the

supplied
Q
a

first
the

of

thermodynamics
energy

U2-U1
of
gas

A.

thermal of

equilibrium
only
and

internal
energy

of

mole

is

function

the

internal

does

change

in

an

Ch.l]

SOLUTIONS

39

isothermal

process:
A
=

U2

Ux=0.
This

Hence is
x

the

heat into
=

supplied
calories 1.937

to

the

gas

is

Q= by the
5. From

1.26x

103joule/mol.
equivalent equation
/;

converted

by

dividing

work Poisson's
=

7.26

103/4.18
6) pVy

kcal/mol.
we

(example

const.,
yp.
wave

have

(dp/p)

y(dV/V)
If
as

0.

Therefore
=

A)
may

the

compression quasi-static

and

expansion
processes

due

to

the

sound

be
at

considered low

adiabatic

(this

would

apply
/
as_____

to

sound

frequen-

cies)

'dp\

V/dp\

dp

dFN
_

If
have

there
p
=

are

moles Therefore

of

gas

in the

volume

F, and
of
state

is the
may

molecular
be writ en
as

weight,

we

nM{V.

equation

C)

Substitute

this

in

eq.

B)

and

we

have
c
=

(yRT/M)i.
weight
of

For

y
x

1.41,
107

an

average

molecular
we

28.9,

T=273

K,

and

8.31

erg/mol

deg2,
c
=

have
x

3.32
with

104

cm/sec

332

m/sec.
at

The 0.607
6.

change m/sec
the adiabatic

of

velocity

temperature

dc/dT=ic/T

T=273

is

deg.
process 1 ->2,
we

In

have

U2
where

Ut
the

=A gas
we

(W
by U3
=

is

the

work
heat
+

done
at constant

by

the then

Q=W,
not

gas). volume, U3
on

In

the
+

process
W=

2->3,
without

is

heated have
of
an

the

Q Q.
does
If

consequently
=

work,
internal
energy
we

U2
gas
=

U2

Ut.

Since
on

the

ideal

depend
the

volume

but

only
U, number;
may

temperature,
be

must

have

T3
const.

Tt.

7.

Since
const.

internal

energy,

=C;

mole

expressed C=molar

as

U=CVT+
it
is

(CK
that

heat),

obvious

40

THERMODYNAMIC

STATE

[Ch.
V2

(i) CD Ql-A
On the
=

j
Cp
=
=

Cy
hand, Cv+nR

dT

Cy(TA
since

7\),
determined

QA-2

j
(C, TX)
so
-

Cp

dT

Cp(T2
using

TA).
Mayer's

other

Tk

is

by CVTX

p2Vx=nRTK

relation,

(example
+
-

3),
=

i)
(ii)
In

Qi-a

CpT2
process

Qa-2 CyTy
B->2

CpT2
J>2V,
work
v2
=

Cy(T2
is

CV)TA Pl(V2
that
F,
.

B)

the

no

involved,
dV

^(ii)

^^b

C
=
-

J
v.

nRTi

nRTt

log

V2

C)

Fig.

1.10

Ch.

1] heat

solutions

41

The

absorbed
B

in

1->B

is

d'Q=pdV

(U=const,

since

T=

const.).

Therefore

Qi^b

=[pdV=-

A^B

nRTt

log

(VJV2),

or

and

thus

<2(ii)
(ii )
1 -*C

CV(T2
involved

7\)
in

nRTt
The

log(K2/Fi).
work
in

D)
the

There
is

is

no

work
as

C->2.

adiabatic

process

calculated

in
=

example

6;
-

i*(ii )
No

A^c
in

CV(TC
1->C and

TO

CVT,

{1

(VJV,)]-1}

E)

heat

is

absorbed

Tc

\-Tl^f)j
+

1.
to

F)

In
8.

all

cases

A +

Q[(l)
how

B),
pressure
z.

C)

D),
of

E)
the determined forces.

F)]
atmosphere

is

equal
in

CV(T2-T^).
equilibrium
fact of
on

First

we

examine
with and

the
the

thermal
the

changes equilibrium heights


and force lower

the
involves

height,
with
are

This of
cross-section

is

from Consider
S.
a

that
air the

thermal
between
upper

balance
a

z+dz
on

The

force

cylinder acting
The where
From

planes acting
of the air

p g is

(z+dz)
in the the

S and

the
and

air

density
these

cylinder gravitational
S + If

(z) S, respectively. is p (z) S gdz


acceleration.

gravitational

p(z)
the

is

the of

balance

three

forces,
-

p(z p(z)g.
volume
as

dz)
of
a

p(z)
average

p(z)
molecular
Hence

Sgdz
the

0,

we

get

dp(z)/dz=
the gives expressed

the
mole
=

weight
equation
of

of
state

air
terms

is

m,

m/p
can

(z)
be
we

of

air.

A.11)
of
6.

p(z)
have

p(z)
The
From

get
condition
p V=nRT

d/?(z)/dz=
for
we

m/p(z) -mgp(z)/RT(z).

RT(z).

By

expression expansion
is

p(z)
A)
in

in

adiabatic

quasi-static

example

42

THERMODYNAMIC

STATE

[Ch.

Elimination
or

of

V\

gives
=

(y-l)dplyp

I p(z+dz)S
z

dz

p{z)-Sdz-g

p{z)S
From

this

condition,
from
the

the

dependence
between

of the

the
pressure

temperature
and
the

T(z)
height.
-

on

can

be thus

derived

relationship

We

have

dT(z)
dz

/5T\
=

~\dp)ad
for air

dp(z)
dz

=
~

(y

1) T(z) yp{z)
in the

mgp(z) RT{z)
to

=
~

(y

1)
4:

mg

yR

The
m=29

constants

have

been

given

solution

example
1.00
x

1.41,

g/mol
-

and
=

g=980
0.41 10.0
x

cm/sec2.
29
x

Therefore,

(y
i.e.,
Note: Since
to

l)mg/yR
there
The the is
a

980/A.41
the

8.3

107)
every

10
in
or

deg/cm
height. fal ing.
in

deg/km,
drop
the
in

10

C
in

temperature

for

km
is the

increase

air

troposphere
of air

(of
is

the

atmosphere)
air The
movements.

rising
may

thermal
adiabatic
is

conductivity
changes
about
as

negligible,
The
of
water

be

considered

undergo

in
per

these

actual
is

decline due
to

temperature

6 C the

kilometer.

discrepancy
vapour.

other

phenomena
9.

such there the


is

condensation in
in
v2

Since
process,

no

change
absorbed

internal
in the

energy

of
process

an

ideal

gas
to

in

an

isothermal done

energy

such
process

is

equal

the

work

by

the

gas,

\pdV.

Therefore, Qt=

l->2,
dV

jnRT
v.

nRTl\og^

V2

A)

Ch.

1]
n

solutions

43

for

moles

of

gas.

Similarly,
Q2

in

the

process

3->4,

v3

nRT2

nRT2
that

log

^.
Qt>0
and
4->l

B)
and
we

In

the

case

described

by
F4.
In

the

figure,

we

see

Q2<0
have

since

V2>Vl

and

V3>

the

adiabatic

processes

2->3

(From
From

Poisson's

equation
=

pVy

const,
or

or

TKy~1=const.
=

See

example
from

6.)

C)
we

(K2/K1)v

(K3/74I'

V2lV1

V3/V4r.

Therefore

A)

and

B)

have

10.

By
that

definition,
we

the
have

heat

d'Q CvdT
the

absorbed

in

the

process

is

equal

to

Cx dT,

so

Cx
where
we

dT

d'Q
used

pdV

CvdT
and

(Cp

Cv)

TdV/V,
The

have

relations,

p=nRT/V

CpCv=nR.
dV

above

equation

gives

(Cx
which

Cy)

dT_

(Cp

Cy)

becomes

(CC)^
when

(CC)
the

dT/T

is

eliminated

by

relation

dT_dp
By

dV

puttmgf=(Cx-Cp)l(Cx-Cv),
log
p
+

we

get
V
=

f log
=

const,

or

pVf
11.

const.

Although
states, for
a

the
free

initial

state

1 and

the

final
not

state

are
so

thermal

expansion
d'A
of
state
=

is not

quasi-static

process, the
pressure

that,
as

in

the
is

equilibrium expression
by
zero

the

work

/?(e)
the
gas,

dV,
but

/?(e)

is

determined which

the
in

equation

of

it is the

external

pressure,

the

44
case

THERMODYNAMIC

STATE

[Ch.
no

of
=

free 0. Since

expansion.
no

Thus

the

gas

does

work
so

in the

free

expansion:
energy,

At^2
is

heat
therefore

unchanged
of
state state

and the
3 is the

is absorbed, the of after received


an

Qi^2
temperature
ideal
gas.

that

internal

U,

remains

constant,
at
constant

i.e.,

Tt
pressure

T2,

because
If

assumption
state

from

2, the

work

quasi-static by the

compression
gas

in

this

process

2->3

is

v2

The
cooled.

temperature
The
heat

changes
absorbed
t3

from

T2 by
the

to

T3
is

in

this

process

and

the

gas

must

be

gas

Q2^3
where

J
T2

CpdT
heat
there is
at

Cp(T3-T2)
constant

(this
pressure. involved:
In

is

negative),
quasi-static
=0.
If

Cp
constant

is the
process

molar
3->l

the

isovolumic
the

heating
at

is
the

no

work absorbed

j43_i
is

molar

heat

volume

Cv,

heat

T3

From

the

first

law
on

of

thermodynamics
system
must

the be
+
we
zero

sum

of
a

the

total
process.
+

heat

absorbed Therefore
=0.

and

the

work

done

the
+

in
+

cyclic

Si-2 Substituting
the

Q2^3
results,
-

Sa-i

A^2

A2^

A^i

above

have
-

(Cp
From the

CK)(T3
state
=

T,)
mole
and

p2(V2
ideal
gas,

Vt)
pV=RT,
=

0.
we

A)
have

equation

of

of

of

p2V2
and

RTt

p2V^

RT3

Substitute

this

into

A)

and

we

have
-

the

desired
+

result
-

>(Cpor

CV)(T3
Cc

T,)

R(Tt

T3)

j?

Ch.

1]

solutions

45

12.

The

critical

state

is

state

where

p,

T and

simultaneously
and

satisfy

the
=

three

equations:

the

equation
=

of

state,

(dp/dV)T=0,

(d2p/dV2)r
,

0.

Since

(dp/dV)T

(d2pldV2)T
we

p[-(Vp\_=

(V
0,

nb)~l nb)'1

+ + +

na/RTV2'] na/RTV2]2
p

+
-

\_{V
nalRT,

nby2

2najRTV*~\

have,

from

(dp/dV)T

V2l(V-nb)
and,

A)

from(d2p/dV2)T
both for sides

Q,

V3l(V-nbJ
Dividing equation
of

2nalRT. expressions
=

B)
in

B)

by

the

corresponding

A)

we

get

the

Vc

KI(K
Vc Tc is determined
=

-nb)
2nb. into
eq.

by

substituting
Tc
=

this

A):

na(Vc-nb)lRV2.
the

We

then

substitute
pc
=

Vc and

Tc into
-

equation

of

state
=

to

obtain

pc,

or

[nRTJ(Vc
reduced

nby\

exp[p=p/pc,

na/i?TcFc)]
r>=VjVc,
states".

a/4b2

e2.
to

We

then

use

the for the and

expression

law

of

variables, "corresponding
=

t=TjTc Substituting

obtain

the
=

nRTJpcVc

|e2,
we

nb/Vc=i,
p
obtain
=

na/RTcVc

2 into
-

[nRTct/{PcVc(v
p
=

nblVc)Y]
/
exp
-

exp[2

nalRTcVctxi]

ite2
V
-

V
of

to
a

13.

According reacting
gases.
constant

to

eq.

A.15),
is

the the
the j'-th then

internal
sum

energy

mixture

of
of
and its

chemically
the

non-

ideal
If

gases
mass

of

the

internal
gas

the
volume

of
is
cvi,

component
we

is

energies Mt

component
heat
at

specific

have

where

M=^iMt

is

the

total

mass

and

the

internal

energy

per

unit

mass

of

46

THERMODYNAMIC

STATE

[Ch. of the mixture


is

the

mixture.

The

specific

heat

at

constant

volume

given

by

For
cv

air,
=

this 0.23

becomes
x

0.158

0.77

0.176

0.036 bar

0.136

0.172

cal/g
the
in

deg.
needle,
the it
so

14.

Let

us

take the

the

x-axis
field
is
zero

that
The

magnetic

the along Hs is also

permanent
in

magnet
as

and shown

the
oo

^-direction and

figure.
with
x.

field,
needle

Hs(x),
is

for

x=

monotonically
from

increases
oo

The

brought

slowly

along

the

x-axis

to

x,

where

acquires

a magnetic demagnetizing field izing magnetic position

moment

m,

which
to

is Since

of
the
moment

course

along
for needle
m a

the

axis
so

of

the

needle.
the

The

field
H

is considered with

negligible

is

equal
force

dipole
x.

Hs. magnetic
on

needle, is small,
which

that
be
a

magnetas
a

it is

may

treated of is

(x),
permanent

function

the

The

the

needle

by

the

magnet

given

by

K(x)
In needle The
on

m(x)dH(x)ldx.
x=

order
must

to

bring
be

the

needle

from

oo

to

x=xt

infinitely
smaller
source,

slowly,
than
say
a

the

restrained

by
force
and

force

work the

done

by
the
xi

this
needle

(supplied
the
xi

infinitesimally by a mechanical
magnet,

K(x).
weight)

system, c
=
-

permanent
r

is
H(xi)

(x)

dx

m(x)

dH(x)
-

dx

dx

r
=
-

f
J

dH

i
.

B)

Ch.

1]

solutions

47

However,
the other

only
part
moment

part

of

this
a
=

has
sort

been of

used
in

in
energy.
a

magnetizing
If
a

the

iron

needle,

being

only

potential
between
this
we

magnetic
it has
a

dipole
potential
and
process:

of
the
to

magnetic
energy

m(x)
(interaction
To

ml

is

placed
energy

field

H(xl),
the

mlH(xl)
magnet).
we

magnetic
the

dipole fol owing


of
the
In

permanent
suppose

subtract
means,

consider

could and

by
magnet

some

fix

the needle needle

magnetization
from with
xt the
to

needle

given
the

ml=m(xl)
permanent

then is

bring pulling

the
the

oo.

this

process,

force

dH(x)
so

that

the

outside

mechanical

source

must

do

the

fol owing

amount

of

work

A2

\ K(x)dx
,

x
=

mi
-

*f

Xl

dH(x)
00

-^-dx

mlH(x1)=

J
J
oo

d{m(x)H(x)}j
dx
to

^dx.

D)
iron needle
is

Therefore,

the

total

work

which

is

required
,

magnetize

the

A,+A2
Note:

7
=

H(x)-~+dx=
and

dm(x)

7
0

\Hdm.

E)
as
our

-oo

If

we

consider
then

the their
If

needle
interaction
t/is the
U

the

permanent
energy

magnet
is included
of the

thermo-

dynamic
energy

system, U' of the

in

the

internal

system.

internal
Hm

energy
+

needle,

U'

is

given

by
U'
so
=
-

const.,
dH
=

that

dU'
Note U

dU

dm definitions

dH.

this

dif erence

between
this

the

of
it

the

thermodynamic
often leads
z,
to

system
confusion.
in the
into the

for

and
the
a

U'.

Although

is

straightforward,
with in the

15.

Since
not

density
uniform.

of

air

changes

height equilibrium
can

the divided

air

cylinder
parts
in

is
T

uniform
be

system.
If
a

However,
non-uniform
may

thermal

temperature
such between

must
a

system
considered uniform

be
and

way

that

each

part

be

the

interaction

48

THERMODYNAMIC

STATE

[Ch.

the

parts
of

is

energies
sidered
and
a

the

negligibly partial
a

small,
system.

the
A

energy

of with

the between
an

system
z

is

just
z+dz

the
may

sum

of
be
con-

the dz

cylinder
dz,
of

and
energy

such

uniform
energy the
g
z

partial

system

internal
the

p(z)
area

Su(T)
of
to

potential

p(z)
internal

Sgz
energy

where
a

S is

cross-sectional
of Since air the
the

the
an

cylinder,
ideal

u(T)
gas, between

unit

mass

assuming
total
energy energy of

it the

be

and
from

the

gravitational
z+dz
0 to
z
=

acceleration. is
oo

of entire

the

part

and
z
=

S{u(T)+gz}
is

p(z)
by

dz,

cylinder

given

gz}p(z)dz.
o

The

dependence (z)g (see


to

of
the solution

on

of
p

height problem
we

given 8). Using


have
=
-

is

by
the

the

equation
of

dp(z)/dz=
state,
p

equation

(z)

RTp(z)/m,
and

eliminate

(z),
dp(z)ldz

p{z)mgjRT
+

log
or

p(z)
=

mgz/RT

const,

p(z)
It
is
more

p(O)exp{-mgzlRT}.
total
mass

convenient than
00

to

use

the

of

the

air where

cylinder
z=0,
dz

after
or,

integration

rather

the

density
=

of

air

p@)
00

at

the

ground

(
o

p(z)Sdz

@)

S
o

exp

[-

rngz/RT}

@) SRT/mg,

which

gives

Sp(z)
Using
this

[Mmg/RT}
find

exp[the
energy

mgz/RT]
of
the

relation,
00

we

that

cylinder
dz

is

E(T)

J (m(T)
(T)
M[u(T)

gz}

{Mmg/RT}

exp[-

mgz/RT]

RTljm}
00

exp(-

(RT/m)

f^e~*

d<f|

M\u{T)

RT/m].

Ch.l] This
is
a

solutions

49

function
C
=

of

the

temperature
=

only,
M

and
+

the
=

heat

capacity
+

is

given

by

dE(T)/dT
relation

[du/dT
+

Rjrn]

M(cv

Rjm).

If

we

use

Mayer's

cp=cv

R/m,
=

Mcp.
quasi-static
dV.
If
we

16.

The
law
U
as

heat of
a

received

by
of
T

system

in
=

process

is the

given
internal

by

the
energy

first

thermodynamics,
function
and
=

d'Q
V,
dU

dU+p
have dT

consider

we

(dUjdT)v

(dUldV)T

dV.

Then

the

first

law

becomes

d'Q
For

(dU/dT)vdT
U+pV,
dH
=

+
we

{(dUldV)T+

p}

dV.

A)

the

enthalpy,

have
+

dU

p dV

dp

and dU
+

pdV
=

dH-

Vdp. Vdp.
of
may

Therefore

we

can

write

d'Q
It

dHa

is convenient

to

consider
the

as

function

T and

p:

dH

(dH/dT)p
as

dT+

(dH/dp)T

dp.

Therefore

heat

equation
dT
+

be

rewrit en

d'Q
(i)
from
and

(dH/dT)p
in
an
=

{(dHldp)T
process
a

-V}dp.
is
at

B)
for
pressure,

The
eq.

heat

capacity
we

isovolumic
In

d'Q/dT
constant

dF=0,

and

A)
eq.

have

Cv
we

from

B)
shown

have
in

(d U/dT)v. Cp (dHldT)p.
=

process

dp capacity
a

0,
at

(ii)
constant

As
T

was

the

solution
from
eq.
state

of

pressure

is the into

obtained

A)
and

and

from

equation

of

2, example by considering substituting


dT

the Fas d V=

heat

function

of

(d V/dT)p dp}.

dT+

(dV/dp)T
d'Q
Setting dp

dp
=

A),
+

which

gives
+

CvdT
=

{(dU/dV)T
have

p} {(dV/dT)p

(dV/dp)T

0 for

d'Q/dTwe

This

is

the

first

part

of

(ii).

To

obtain

the

second

part,

we

derive

Cv

from

50

THERMODYNAMIC

STATE

[Ch.
we

eq.

B).

Since

dp
=

(dp/dT)v
+

dT+(dp/dV)T

dV,

have
+

d'Q
d'0/drfordF=

CpdT
Ogives

{{dHjdp)T

V) {{dpjdT)vdT V) (dpldT)y.
part
of

(dpldV)TdV}.

Cv Combining (ii )
this Since

Cp
we

{(dHldp)T
get
the second

with

(ii ),

(ii).
+

H=U+pV,
=

(dH/dp)T
(iv)
Since

(dU/dp)T

(d(PV)ldp)T
the

(dU/dp)T
part
of

p(dVldp)T
gives
p.

V.

(dVldT)p=l/(dTldV)p,

first
=

(ii)
+

(Cp
Considering dif erentiating
d2T dpdV
We
now

Cv)
of

{dTjdV)p
equation
to
to

(dU/dV)T
be

both with

sides

the

functions

of/?

and

V,

we

get,

by

respect

p,

fdCn\
\ dp Jv
the third choose Tin
we

fdT\

fdCv\
\

(dT\
dp

fd(dUldV)T\
\

\dVJp
term
on

Jv

\dVJp
side

dp
first
at term constant

Jv C)
on

rewrite side.

the
are

left-hand

and
state

the

the

right-hand
it is

Although
to

these
T

partial
as

derivatives natural
to

of/?
variables

V,

convenient
If
we

and

the

for

Cp
V

and

(dU/dT)v.
the

consider

CV(T,
write

V)

be

function

of/?

and

through

equation

of

state,

can

fdCv\
Similarly,
and with
with

\dp)y~
Tin

dCv(T(p,
dp

V),
=

V)
dU(T,

~\dTjy\dp)y'
V)/dV
to

fdCv\

fdT\
to

considering
V,
the
we

(dU/dV)T
with
T

be

function

of/?

should

first

dif erentiate
of

respect
to

and
the

then

multiply
derivative

it

partial
to

derivative
/?:

with

respect

/? to

get

partial
/oT\

respect

fd{dUldV)T\

V
Hence

dp

~~)v
dp

_ ~

d2U(T, ~dfdV~

32]

V)

/dT\

'\dp)y
fdT\

_ "

\dv)T\dp),
(dCy\\(dT\ \dVjT]\dp)y'

/dCv\

fdCA

\dp)y\dv)p
On

fdT\
other

d{dUldV)T=UdCv\
hand,

\ dTjy\dVj,
Tin

the

by

considering

CV(T,

V)

to

be

function

of/?

and

Ch.

1]
we

SOLUTIONS

51

V,

have

/dCy\

\dVjp
by
means

^dCv(T(p,V),V)
which
eq.

{dCv\

/8T\

dV

\dTj dTjv\dVjp

\dVjT

of

D)
/dT\

gives

/dCv\
\dp
On

d{dUjdV)T
dp
eq.

)v\py)p
this into

_fdCv\ \dv
previously,

)p\dp)v

(dT\
we

substituting

C)

derived

have

the

desired

results.
17.

Using

the

result
p
=

of
RT

problem
=

5, c2
-

yp/p,
=

and

the

relation

(Cp

Cv)
M

p
we

(c

-cv)T

(y-

1) cvT,
we

have

c2
const,

y(y
and
+

1) cvT

or

cvT=c2/{y(y
-

1)}.

Furthermore

know

that

u=c0T+
h
Thus
18.
we
=

pv

(cp

cv)
result.

(y

1) cvT

ycvT

const.

obtain

the

desired
at

The

work
the first

equation,
law
of

constant

magnetic
the
heat

field

H,
absorbed

is

&'A
is

H<\I,

so

that,

from

thermodynamics,

d'Q
If
we

dU-d'A
be

dU-HdI.
of

consider

and

/ to

functions

temperature,

T,

and

field,

H,

we

have

and

The
answer.

desired

heat

capacity

CH

is

dQ/dT

for

dH=0.

Thus

we

obtain

the

52

THERMODYNAMIC

STATE

[Ch.
process,

19.

For
may

unit be

volume writ en
as

of

magnetic

material

in

quasi-static
dM

the

first

law

fol ows:

d'Q
(from d'Q
eq.
=

dU

A.5)
dV,

and
we

example
see

dU+p

the

1). Comparing correspondence/?-*


and
and

this

with

the Hand

case

of
V-+M.

gas Since

where

dM\

""{
the
we

(dM
solution obtain
to

correspond
the
answer

to to

l (dp/dV)T
this

l/(dpldV\d,
Therefore,
of radiation the
of dU pressure Thus

example
solution
this

7
to

gives
this

problem.
the
of

may

the

problem
20. The
is

by
internal

fol owing
energy

argument
heat

example
inside the
an

7,

using
enclosure

parallelism.
of
is

the

given
V,
p
or

by
and

U=
T

Vu=aVTAr.
are

Since
not

p^u^aT^
natural for
a

volume, independent
variables
process
are

V,

of

independent.
first law

state

(V,

T)

(V, p).

The

thermodynamics
=

quasi-static

is

d'Q-pdV.

Substituting

for

U
=

and

p,

we

have

d'Q
Thus

d((rFT4)
for
an

iaT4
adiabatic

dV

ftrT4
is

dV

4aT*V

dT.

the

condition

process

which,

when

integrated,

becomes

log
or

log
=

const.,

FT3
and,

const.,

using

the

equation

of

state,

pV*
The

const.

heat

capacity

at

constant

volume

is

while since

the the

heat

capacity
cannot

at

constant

pressure

may

be

considered is fixed.

infinite,

temperature

be

changed

if the

pressure

Ch.

1]
As

SOLUTIONS

53

shown

in
goes

the from
an

figure,
state

the
1 to

Carnot
state

the
2
to

system
state

cycle by
state

is
an

quasi-static expansion,
state

process

in from

which
state
an

isothermal from
1

thermal

by compression
3

adiabatic
and
returns

expansion,
to

3 to
an

state

by

adiabatic

by compression.

iso-

isothormal

compression.

In

the

process

l->2, Tv
The

let

the

volume
received
v2

increase

from heat radiation

Vx

to

V2
is

at

constant

temperature,

work

by

the

while

the

heat

received

is

Vi

6l.2

dV

Therefore,
is

certainly
the
process

the

increase

in but in

the order

internal
to

energy.

It

is
=

obvious

that
p dV
we

??2->3
make

in
of

2->3,
that

calculate

A2^3

J^

use

the

fact

Therefore,

V3

dV

54

THERMODYNAMIC

STATE

[Ch.
at

From

V2T\
is also

V3T\
increase

we

get

for

the

temperature

state

3:

T3

Tt (V2IV3)*

and

This
we

the
is

in

the

internal
from
the

energy.

immediately

get
constant,

this

result
and

first

(We law.)

know
In

that the
process

??2-o

0 and the

3->4

temperature
and

In

the Since

process

4->l,

??4-i

0 and This indicates


From is

A^^^aTlV^-aT^.
that
=

reservoir

V2>VU (temperature

Q1^2>0.
Ti).
Therefore
heat

heat
and

is

absorbed

from
we

the
see

heat

V2T\
23_4<0. given
off received
to

V3T\
This
the
total

V^T^V^l
that,
temperature
the done heat

that

V3/V4=V2IV1>1.
T3 Ti (temperature l??3->4l
=

indicates
low

since heat reservoir

V3>V2,
reservoir

(V2IV3)i<T1,
T3).
=

to

The

total
is

energy

from
work

Qi^2

2i-2

tl).
Q^JT3
which 21.

??3-4 Furthermore,
=

e?lual

the

-(Al
=
-

i-<rTi(VA
equation
streamlines
v,

V3)

iaT^V,
+

-V2)
Q3^JT3
with
the
pressure,

Q^/T,
0.

gives example
Since

the

Clausius

Q1-t2/Tl
do
not

(See
flow.

9.)
the

The

change
p,

time

in
p,

velocity,
point equilibrium.
to

the due

density,
to

and

have fluid volume

steady-state dif ering


as
a

values
is not in

from thermal
it may

point
be

the be in be

motion
if
a

of

the

fluid,
small

the

whole

However,
to

is taken, i.e. a

considered
element
a

thermal
considered
p, may

sufficiently equilibrium
to

element

(local undergo
to

small
In such

volume
case,

may

equilibrium), a quasistatic
be

change. by the equation


The
passes

the

pressure,

be

considered
volume that

determined

density,
of
state.

p,

and of

the

temperature,
for
a
a

T, of the
fluid
stream
to stream states

element
the
area,

through
of fluid
which

the

equation through
flow the

continuity
cross-section
per

mass

of
unit
on

tube the
amount

of
i.e. have

Su
of
fluid

the another

direction
cross-section

time the
stream
same

is

equal
tube,
d/. Since

tube;
we

p^S^

perpendicular passing =p2S2v2.


two

to

through Writing
Next
crosswe

/ for
consider

length
the
first and heat

along
law

the

thus

d(pSv)/dl=0.
fluid the

of

sections
there

Si
is
no

5*2
flow

separated
from

thermodynamics by
the

for
we

the

between
thermal

surroundings.

neglect Ignoring

conductivity, viscosity
and the

Ch.

1]

solutions

55

gravitational
on

the

surface
energy

force, St
For

the

work
on

done

is
The

only
work

due done this


is

to
on

the this
to

external fluid

pressures,

pt

a.ndp2
an

S2.
of
the

per

unit be

time The

is

Pi^ivi~p2^2v2internal

infinitesimal
u,

dl,
fluid
may

equal
considered

dl-d(pSv)dl.
to

density,
p,

be

determined

by

the

density,

and

the

temperature,

T,

through

the

equation

of

state.

The
a

fluid time
dt

that

was

between

St
the

and

5*2

at

given
the
Hence

moment

is

displaced
are

after
vt

interval,
removed
fluid is

dt,
from increased

into

volume

between

planes
the
energy

which of

dt

and

v2

St

and

5*2,

respectively.
Siyi
dt
per
+

that

portion

of

the

by
+

Pi(ui
in

iyi)
this
dZ-

p2(u2
unit

^v2,)
is

S2v2

dt.

To

the

first

order

d/,

increase

time

dl

By
the

the

first

law derived

of

work

thermodynamics previously;

this

must

be

equal

to

the

expression

for

i.e.,

iv2)]
dl
This
may

d(pSv)
dl

be

rewrit en

as

"-

56

THERMODYNAMIC

STATE

[Ch.
this

Using

the

continuity

equation

d(pSv)/dl=0,
d(u
+

gives

$v2+p/p)
dl is
constant

which is kinetic
22.
We

means

that

u+p/p+^v2
volume,
h unit
mass.
=

the

specific
energy

u+p/p

is

the

along enthalpy

the

streamlines.

Since and

l/p
is the

density,

\v2

of

have the

seen

in kinetic
constant

the

previous
energy,

problem,

that
constant

the

sum a

of
streamline.

the the

enthalpy
For

density,
an

h, and
gas internal

\v2,
specific const., cvT+ along
constant,
assume

is

along
can

ideal of
the

with

heat,
the
so

it
that

be h this
=

seen

from
=

equation
Therefore

energy is gas
a

u+plp
In
an

cpT+comt
adiabatic
must

CpT+^v2
ideal the

constant

streamlines.
that the

change
be the
constant

of

an

p^~y)/y
If
steam

Tisa.
we

quantity
is
zero

along
of the

streamlines.

that

velocity
and

in

container

superheated

where
T
=

300C

573K

we

have

the

equations
+

CpT
and

\v2

0.49
T

573

281

cal/g

1.174

1010

cm2/sec2

573x(ipH-33/1-33K.
then
T-

When
jc
=

the

pressure
we

p=

1 atm,

573

5-0248

K.

In

order

to

calculate

5~0248

take
-

the 0.248
x

logarithm

of
5
=
-

both 0.248

sides
x

logl0x
and

log10

0.699

0.1734

T.8266

jc=0.671.

The

temperature
T
=

is

thus
=

573

0.671 is

384K
from
x

111

C.

The

upper
=

limit

of
x

the

velocity
-

obtained
384

c2
as

2x
=

A.174
880m/sec.

1010

0.49

4.18

107)

0.774

1010cm2/sec2

23.

Let

the

state

variables
and there

of
be exists be pB,
vB
a

the and

system
pc, vc,

be

pA

and the
0-

vA,

and
When

the
A

variables
and
B
are

of in
vA,

systems

C it

respectively.
between

equilibrium,
pB

single

relation

four

variables

pA,

and

vB:

let

*3GPa.*>a.jPb*>b)

A)

Ch.

1] when
B

solutions

57

Similarly

and

are

in

equilibrium,

we

have 0. and

an

equation
B)

Fi

(Pb>
when

vb,

pc,

vc)
A)

According equilibrium
should
that result

to

the and

zeroth

law,
a

eqs.

B)
0 and

hold,

and

are

in

therefore

relation

F2
from
eqs.

(Pa.
B).

va,

Pc,

vc)
eqs.

C)

A)
4>i (Pk> <Pi 0a>

and

If

A)
=

B)
vc,

are

solved

for

pB

so

Pb then

va,

vb)
a>

pB

03 (pc,
vc,

vB),
D)
to

Vb)
eq.
an

03 (Pc>

vB)
have

must

be
vB

equivalent
must

to

eq.

C).
to

Then

D)

would of
the

hold

independent
E)

of

and

be

equivalent

equation
=

form

fl(PA>VA)
(This

f3(Pc,Vc)vA,

implies,
vc,

for

instance,

that

fa (pA,
Therefore
eqs.

vB) =/i
eqs.

(pA,
C) equivalent

vA)
and

rj

(vB)
E)
to

+ must

C (vB),
be

(t>3(Pc>
equivalent.

vB)=f3(pc,
By
similar

vc)ri(vB)+UvB)-)
argument,

A)
=

and

B)

are

fl(PA>VA)
fi
(The
is

f2(PB>VB),
f3 (Pc, F),/2
the zeroth

F)

(Pb> vb)
in

vc)
is the

G)
same

fact
the
same

that/i
in

is the

same

E)

and

in If

F)
we

and
now

G)
put

and/3

E)

and

G),

derives

from

law.)

9 wil

be
A

quantity
on

which
a

characterizes

thermal
The

equilibrium,
for and

that

is, it is the
between

temperature
systems 24.
In
and

certain
is

scale.
their

condition

that

values
where

of

9, 9A
the

9B,

are

equilibrium equal.
has
the the is
an

discussing
we

the have
the
to

general
start cannot

case

shape demagnetizing
Af,
law
and is

from
be

Maxwell's

magnetic equations,
the

body
since

arbitrary
of
the

effect

field
flux

ignored
are

and uniform.
the

field,
The

H,

magnetization,
of
assumed be

density,
first

B,

not

equivalent
current
can

Ampere's
to

Maxwell's

equation
so

where that
An

magnetization

take

place

sufficiently
curl

slowly
H
=

the

displacement

ignored,

i.e.

j
c

(Maxwell's

first

equation).

A)

58

THERMODYNAMIC

STATE

[Ch. of
the

Here

j
is

is
at

the

current

density Faraday's
induction
ldB
=

through
law

the takes

wire

the

coil.

If

the

magnetic

body

rest,
curl

form

(Maxwell's
The

second flux fourth

equation),
density
satisfies
the

B) equation C)

where

is

the

electric

field.
B
=

magnetic

div
The of the

(Maxwell's
a

equation).
to

magnetic
coil

field,
and
the

H,
part

is

sum

of
due
to

the the

part

HM

Hj due magnetization:

the

current

in

the

wire

These

partial
from

fields eqs.

are

well
and

known

to

satisfy

the

fol owing

equations,

resulting

A)
curlHj
curl

C),
4;r
=

j,
c

divH,
div lines

0;
=

HM

0,
field

HM
around
the

An

divM.

Hj
tational

forms
and
in

closed

magnetic
forms
force lines

the

current,
and

and

HM
law and

is

irro-

charges

the

(pseudo)
relation

scalar

magnetic potential.

body.

connecting HM is determined Therefore, integration

positive
by
over

negative
all
space

magnetic
has
the
a

Coulomb's

gives

J
We

f
assumed that

J
the

f
vanishes
add
space.
to

J
at

have of

field

infinity.
the

Now

we

take

the
eq.

scalar

product cH/4n,

eq.

and

A) integrate

and

cEjAn,
over

it

scalar
side

product
becomes

of

B)

and

The

right-hand
=

f(E-curlf -f -curlE)dF
Therefore,
for
the

fdiv[f

left-hand

side,

we

have 0. the the

E-jdV+
The such
first
as

4;rJ
to

-\H-(dBldt)dV
be

E) region
resistance
where

integral
in
the wires

only
of

needs

carried
the

out

over

/V0,
in the

the

coil

and

battery.

If

specific

Ch.

1]
or

SOLUTIONS

59

wires

in

the

battery

is

p,

from

Ohm's

law

E+F=pj,

we

get

(E-jdV=
Here
done
F per

(pfdVforce
in
to

(F-jdV.
the

is

the unit

electromotive
time
is

battery
the dV
is
current.

and that

J F-j
If the

dV the be

is

the

work of

the

entire

system
as

by the battery constant, kept


heat.

pass

temperature
work
rewrit en

J pj2
second

part
eq.

of

which
as

is

dissipated
fol ows:

Joule

The

integral

of

E)

may

4nJ

UHidBl6t)dV
v

'

An)

\HdV+[H
dt

dt

The

first

term

of

the it
is

last
seen

expression
from

is the

work

done

to

create

the

field.

Since

J HjHM

dF=0,

E)

that

Here

it

should
to

be the

noted
and

that the work

this

includes
be

the

work
due

done
to

to

create

both of

the of
the
to

field
the

due

coil

demagnetizing
may

field excluded

the

magnetization
definition done
the

work
zation

magnetic required
is
the

body.
to

This

from work

the

magnetize by

\H-{pMjdi)dV.
magnetization
d'A=

magnetic Multiplying
a

The body. by dt, we

in work

magnetidone

get

increase

dM

from

M:

((H-dM)dV=
is is
over

f
the

(Hj
of

HM)dM
the

dV,

where work of

the

integration magnetization

volume

magnetic

body.

The

total

therefore
Af

It

is

important
must

to

notice

that
be the

the

demagnetizing
included
in the
are

magnetization magnetic integral

generally
and
a

field,

H,

magnetization,
by
the

M,

field, magnetic uniform,


V.

HM,

due

to

the

field.
the

If

the

volume

simply

gives

multiplication

volume,

60

THERMODYNAMIC

STATE

[Ch.

Note:

It

is

only
in

in the

the

case

where
and the

the

magnetic
case,

field
the
are

body
fields

magnetic magnetization
the

body
are

is

an

ellipsoid
If
jc,

that such
z

the is
of the the

uniform.
axes,

ellipsoid

demagnetizing given

along
=
-

principal

and

by

(HM\
where the

NaMa
Nx,

(a
Ny
=

x,

y,

z),
Nz

demagnetization

coefficients

and
4n.

satisfy

the

rule

Nx+Ny+Nz
The three

coefficients

can

be

calculated

as

functions

of

the

axial

ratios

of

the

ellipsoid.

Chapter

THE

SECOND

LAW AND

OF

THERMODYNAMICS

ENTROPY

In
treat

this

chapter,
directly
of
grasp

we

introduce

the
to

second it.
The law and

law

of
here

thermodynamics
is the
to
to

and understand

the
concrete

problems significance

related
this
the

object
which

fundamental

furthermore
is somewhat
most too

obtain

of

concept
and stil

of

entropy,
seems

important
abstract
to

thermodynamic
students.

quantity

often

Fundamental
2.1.
REVERSIBLE AND

topics
PROCESS

IRREVERSIBLE

Reversible

process:

Suppose
state,
way
to return a, to

that

when

system
the the environment

under

consideration

changes P to P'.
at

from
If
same

another
is the

state,
to

a',
return

changes
from
the
process
sense
a

from
to
a

in

some

it

possible
environment

system
to

a'

and

the

time
is

from
is

ft'
in
as

ft,
the

(a, /?)->
of
process the is

(a',
The

p')
A

said

to

be

reversible. for
definition
be

above
narrower

definition
if

reversibility
is often in
A process A

made

broadest

word.

given
each reversible

fol ows:

reversible
conditions
other
can

it of

can

reversed

step

by
in
process

infinitesimal
process

given changes
sense

of
is
process
sense

the
none

the

environment.
in

in
A

this

than

the reversed

quasi-static
this
sense.

explained
reversible
strict
sense.

1.5.
in
the processes
or

quasi-static
the

be

broader

is
or

not necessarily electromagnetic

reversible

in

this
are

Although
in

purely
broader
sense,

mechanical
we

phenomena
in
every
are

reversible

not

be

reversible

consider
and

combinations
thermal
we
a

respect*. of purely
processes. the
process
narrow

Reversible
mechanical

which

they normally
processes

may

electromagnetic
of

quasi-static
Therefore

may

adopt

definition
be
at

phenomena;
Real

reversible
processes

may

considered

physical
Such
reverse an

proceed
the of

finite

speeds
particles
in
a

reversibility a quasi-static and are necessarily


as

for

thermal
process.

irre-

example
the

is direction
Lorentz

motion

of
Thus
sense.

charged
the

given
be

magnetic
reversed

to

motion,

magnetic
the

field reversal

must

field. because

In
a

order

presence

of

the

forces.
the
narrow

without

of

magnetic

field,

such

of motion

the

is

not

reversible

in

62

SECOND

LAW

OF

THERMODYNAMICS

[Ch.
of
to

2,

versible,
is
an

since

they
which

always
is
not

involve reversible

some

kind
is

friction.
be the is

reversible

process

idealization.
process

A ation
the

said
When the

irreversible.

Reversible

cycle
changes
from

and
a

irreversible
to
a

cycle:
while is
the

system

under

consider-

environment

changes
an

from
said
in
to

P
be
In
a

to

P'

and

process When

(a, /?)-(a,
the
is

cycle.
if

process
a

reversible, P) is irreversible,

it is
it is

process irreversible

reversible

cycle.
each
which

particular
makes it The

the

process
to

quasi-static
and irreversible

process,

reversible
An

step.
pass

Reversible

engine
do either
or

engine:
a

arrangement

possible a cycle engine


reversible
2.2.
A
A

work reversible irreversible.

by
heat

making
with
or

system
environment

(working
is

substance)
called
on a

through
engine.
the

exchanging
is

the

heat

irreversible

depending

whether

cycle

is

LEMMA

(CARNOT

CYCLE)

"Gedankenexperiment"
methods
we

ful
Here

to

treat

problems
the

define

Carnot

using concerning in cycle

Carnot
the
the
narrow

cycle
second
sense

is

one

of
of
as

the

most

power-

law

thermodynamics.
one

which

uses

an

hot

heat

reservoir

Ri('A)

adiabatic

-A
A

(work)

isothermal

Fig.

2.1.

Fig.

2.2.

Ch.

2, 4]
gas
as

EFFICIENCY

OF

GENERAL

CARNOT

CYCLE

63

ideal
of reservoirs
heat

the

working during
and

substance,
the

as

shown
processes

in

Figure
in
we

2.1.
contact
must

If

the with

amounts

absorbed

isothermal
are

heat

Rx (Tx)

R2G2)
Qi/T1

gi
+

and

Q2,
=

then
0.

have

Q2/T2
the

B.1)
of
state

Since
the
as
a

this
first

can

be
of lemma
SECOND

law

proved thermodynamics
when
LAW
an

using

only (see

equation
1, problem
second the

of

an

ideal
be

gas

and

Chapter

9),
law
of

it may

regarded

known
THE

discussing
OF

thermodynamics.

2.3. Because

THERMODYNAMICS

it

is

emperical
and

law,
these

there
are

are

many
course

ways

to

state

the
Here

second
are

law
statements:

of

thermodynamics,
Clausius'

of

all

equivalent.
no

the the

a)
transfer

principle;
of for
heat

A
a

process hotter
to

which
a

involves

from heat
other
to

cooler

body
from
A
a

is

change irreversible;
colder
to

other

than
or,

it

is

impossible
without

transfer

spontaneously
principle:
any heat

hotter
is
or,

body
trans-

causing b)
Thomson's
into
to

(or
heat
convert

changes. Kelvin's)
without all
the

process is
a

in

which

work

formed

other
taken

changes,
from

irreversible;
of

it

is

im-

possible
into
work

body
mobile
in

uniform

temperature

without

causing

other

c)
It
is

Principle impossible

of
to

the
devise
a

impossibility
an

engine
reservoir

changes. of a perpetuum operating


without

of
which
any

the

second
does
work

kind:

heat from taking mobile (perpetuum Carat h eodory' s d) uniform thermally


to

single
of
the

heat

cycle producing
a

by

other
state

change
of close
a

second
For

kind).
a

principle:
system,
be there

given
another it

thermal
state
an

equilibrium
which
is

exists

arbitrarily

it

but

can

never

reached

from

by
means

adiabatic

change.
that
a

Note
process It is

The
is

statement

"other The
condition
convert
an

changes"
all ideal
the
gas.

changes
in from

remain
in

after
is

the

completed.
to

"operating
heat

cycle"
a

c)
reservoir

important.
by
isothe
to

possible

taken

heat
not to

thermally cally. equivalence


and
2.4.

expanding
It is
is
THE

However,
are

this the

does
Refer

operate

periodi1 for

obvious

that

of

a)
more

and

b) b).
dif icult
OF

and
The

c)

b)

lit le
EFFICIENCY

proof (see
A

equivalent. showing problem


CARNOT
are

problem
of

equivalence

d)

a)

30).
CYCLE

GENERAL

General

Carnot

cycle:

Though

there

various

extensions

of

the

Carnot

64

SECOND

LAW

OF

THERMODYNAMICS

[Ch.2,4
heat

cycle,
reservoirs fore processes.
a

we

refer

to

an

engine
and does

which

absorbs
A
=

Qt
the processes

and

Q2
environment. and
Carnot

from
two

two

heat There-

Rt
Carnot
If

and

R2

work
of
two
we

Q1
a

Q2on
reversible

cycle
these
are

consists

isothermal
have

adiabatic
then

reversible
is

cycle.
reservoir,
rj is

Efficiency: Qi >0> Qi
<0,

If A

Rt
-

the
+

hot
=

reservoir

and and
the

R2

the

cold

Qv

Q2

Qt -\Q2\
>7
=

efficiency

^=l-~-!-/
=

B-2)

Therefore

we

have

B.3)
a

Carnot's

principle:
heat

The

efficiency
Rt
and

v\ of

reversible determined of
than i.e.

Carnot

cycle
by the

operating
temperatures

between

reservoirs
of the heat

R2

Q1
between

and

d2
the

reservoirs

uniquely an^] independent


of
is
any

is

the Carnot

wor^ngjuHstanceJ)
cycle

Furthermore,
same

the

efficiency,
heat reservoirs

v\\

irreversible
less
v\\

operating

Fig.
Proof:
the A
=

2.3.

Consider
heat

two

Carnot
heat reservoir

cycles
or

and and work

C\

is

reversible
to

Qx
=

from

the

Rx
irreversible. the
net

gives
It

\Q2\
takes
=

R2
heat

cycle. doing

It
the

takes
work

Qt-\Q2\. |e'2| giving


in

is
to

reversible
R
2

the
-

Q[
IfC
is

from

Rl5 Rt

\Q 2\
way

and

does the

A'
is that

Q\

the

reverse

(Fig.

2.3),

result

Q[

\Q'2\. Qt

operated
from

is

taken

Ch.

2, 5]
the work

ABSOLUTE

TEMPERATURE

65

and

A'
is

A
to

Q[

\Q'2\

(Q,

\Q2\)
we

Q;
have:

Q,
A'

done.

According
we

Thomson's

principle,

must

A^O,

or

Therefore,

conclude
w 7

that
=

<

Qi
C
may

Qi
be

7w.

If have
2.5.

is

reversible,
and
hence

then
rj
TEMPERATURE

C
=

and

operated

in

reverse*,

so

that

we

r\'^.r\,
ABSOLUTE

ri'.

The

ratio
and

of

the

absolute
is

temperatures

Ti

and

T2

of

the

heat

reservoirs

Rt

@J

R2 @2)

defined

by

^ ^
where
^
two

l-r,(9ue2),
of
a

B.5)
Carnot

(9U
heat

62)
thermometer

is the

efficiency

reversible
to

cycle
the

operating
given
In
a

between

the ideal
the
a

reservoirs.

According
agrees

eq.

B.1),
to

temperature

by
to

an

gas

with

the it
is

absolute
necessary

temperature.

order

fix
to

absolute
reference

temperature

scale,
When

give
as

numerical

value

point.

the

reference
pointof
water

point
=

is
273.16

set

^triple
it is

K,

called
use

the
the

Kelvin

temperature

scale. unless

In

the
we

fol owing
say

treatments,
otherwise.

we

wil

always

absolute
4

temperature

Divertissement

Absolute The determined

temperature absolute

temperature

scale

means

that
so

temperature
that
it does
not

scale

which
on

is

by
of thermometric

thermodynamic
substance,
which
is
now

method
the is
zero

depend being
defined
Absolute

the
as

choice
the lowest

of

the

scale
was

temperature
which

possible
in in

temperature,
Lord

used

thermal
1848

thermodynamically. physics,
and is

introduced called
the

by
Kelvin

Kelvin

(Wil iam
reversible
broad
sense,

Thomson)
in

also

temperature.
*

If

and in

C the and
same

are

each
may

step,
not

they
be
the

can

be

operated
in
reverse.

in
in each

reverse.

If

they
there exist Therefore

are

reversible
processes
we

they produce

C
have
the

C
result.

which

exactly

operated opposite

However, cycle.

effects

66

SECOND

LAW

OF

THERMODYNAMICS

[Ch.
we

2,

For
use

the
two

complete
fixed
other

definition

of
zero

the
and

points
is to
use

above
one

scale, assign
and 7b

have
their

two

choices;
value.
was

one

is to
Until

and

the
two

fixed
of

point
the Kelvin

assign
the
101325
At

recently
using
of
measure

the
fixed
water

calibration
po

i nts:
gas gas

the thermometric
can

ice

point
atm

temperature K and

temperature its numerical scale

dif erence

performed
To+100
We the
can

boiling Newton/m2).
pressures,

point

pure state

under

1 standard

(
in

To
of
a

by
real

method.
be
writ en
p V
=

low

equation

of

the +
k

form
Kp.

We

measure

the
that
a

values
is

of/?
to
n

V,
R 7o

and
we

at

the

above

two

fixed

points.

Con-

sidering

equal

T,
=

have lOOao
.

aioo

ao

If
Hence

we

put
To

To =0, C
gas

we

get
absolute

the

thermodynamic
zero
as

Celsius measured
of

means

by
the determinations of W.
between

The from puis Inspired performed of Germany, of the

precise
1887

thermometric
to

investigations
gave
more

temperature scale. Frenchman


this
273.048 Heuse J. A.
are

scale.
P.

ChapTo
J.
were

1917

the
than

value
one

of hundred

7b results

and

273.123.

by

this until
W.

work,
1942.
H.
M.

of and Beattie noted


and of
on

Among
Keesom
et

them,
al. and
are

the
of
J.
to

Otto
et

the Oishi lie that

Netherlands,
of
between
the

al.

U.S.A.

and Their these


to

Kinoshita

Japan
273.149

for
273.174.
pure
as

their
water

high
is

precision. Considering
very
near

values
results

found the 10th


use

and

fact

triple
of
t

point
the
T
water

0.0100

C,
decided
the value absolute the
new

the
to

General
the

Conference

Weights
the

and fixed where the


above

Measures

in

1954

triple
as

point
its

point
the
T

and

to

assign
of
zero

273.16

temperature.
fCas

It

also

redefined

thermodynamic
is about
For

Celsius the of from


purposes,

the

value

temperature temperature

273.15,
from

determined Celsius
in where
a

decision.

The 0.0001

thermodynamic
ice the for

temperature
new

dif ers old


10~4

by
quite
the
sideration.

the

point.
dif erences
cases we

ordinary negligible.
absolute value

these

and of

scales

are

However,
is

precision
the dif erences

degree
into
con-

in

required,
ice

must

take

point
0K

triple point
ToK

boiling

7b'+
100

point
100 K

-jo

C.

0C
273.16 K

0K
273.15 -273.15

DK,1954

K
0 C

0.01

C,1954

Ch.2,5]

ABSOLUTE

TEMPERATURE

67

Note:

By

eq.

B.5),

the

relation

Qi
reversible

Q
=

B.6)
as

holds

for

general
in
eq.

Carnot

cycle,
it
must

in shown

eq.

B.1).
that

In

order

that

the

definition

B.5)

is

possible,

be

l-i@i,02)=f@lt02)
where

B.7) B.8)

Once
to

relation the absolute of


eq.

B.8) B.8):
each

is established,

the

temperature
Consider of
Let

scale,
three

arbitrary T, by T(9)
Carnot between

temperature
=

scale,
where C

9, is related
is
a

Cg(9)
C12,
of the from
as

constant.
as

Proof
in

cycles
two

C23
three

and heat each

C13
heat in

shown

Fig.
R2
the the

2.4 and

which
the
to
we

operates
amounts

reservoirs

Rl5
and
From

R3.
done
first

of

heat be

received

reservoir the

work

the

environment

denoted

indicated

figure.

law,

have

Fig.

2.4.

68

SECOND

LAW

OF

THERMODYNAMICS

[Ch.

2, 5

C13

is

operated

as

refrigerator

in

the

figure.

It

is

obvious

that

for
to

if

Qi

Q[

>

0 then

net

work If

is done

by
we

cooling
get
the

Rt
in

alone
same

in

contradiction
to
we

Thomson's

principle.
principle
when

Thomson's
must

Qt Q[<0, operating

contradiction Therefore

the

system

reverse.

have

Qi

Q[.

Therefore,

f(9u
The solution of

03)
equation
5

^
Mi

Mi

^ ^
Mi

=f(9u
form

92)f(92,
given
in
eq.

93).
B.8).

this

has

the

Divertissement

International the of
ever,

practical
triple

temperature
pure water
as

scale.

Theoretically,
K
From

the

definition the calibration


howthe
some

of

point
entire

of

273.16

is
are

sufficient
a

for needed
and

the

Kelvin

temperature
processes

scale.
are

practical

standpoint,
for the
as

the
is

thermodynamic
of the

which
too
can

accurate

measurement

temperature
with Such scale which
a

cumbersome

practical
temperature International
on

standard
with

required
accuracy.

one

easily
was

determine
set

fair
Measures

standard
at
was

up

the 1960.

Practical
and
atures
are

Temperature
in
as

the

7th
are

General
in

Conference
1948
on

Weights
temperscale
and The

measured

1927, using
C

and this

amended

and

The
as
=

scale

expressed
sometimes Tint,
is defined

the this
as

Celsius
fmt.

designated
is The

(Int.
TK 1948 of

1948).
temperature

We

write

inter-

national
and sists of nition
the

practical designated
basis

Kelvin
as

Tint.

tint.

+273.16,
scale'condefinition
of

(Int.
International
six

1948).
Practical fixed
in

of introduction
of shown

the

Temperature
of definition
and

of
are

the method

points
four
ranges.

the

interpolation
in

The

fixed

points
C

defi-

the

table:

Boiling Triple Boiling Boiling Freezing Freezing


The These
The

of oxygen point of water point of water point of sulphur point of silver point of gold point

(Oxygen

point)

-182.97 0.01
100

(Int.

1948)

(Sulphur point) (Silver point) (Gold point)


419.505
atm
are

444.6 960.8
1063
can

freezing
values

point
are

of
at

zinc,

C,
except fol ows: as

replace
for

the

1 standard

the

triple

sulphur point

point.
of
water.

method
-

of 630.5

(a) 0 rC(Int.

interpolation (freezing
is

1948)

defined
Rt

point by
=

of

Sb)
+At

Ro(l

Ch.

2, 6]
where resistance Rt
be

clausius'

inequality

69

is

the
thermometer

electrical
at

resistance

of

the of

Pt
/.

wire The
at

used

in

the

standard
A

the
the

temperature
values

should the

determined

from

Rt

quantities the triple

Ro,

and

point

of

water,

boiling
-

point
182.97

of

water

and

the of

sulphur

point.
-

(b)
t

(boiling
from
Rt
=

point
RQ
are

oxygen)
+
as

is

determined

(i
the

+
same

At

Bt*

C{tand
C is

100)
determined

t3)
from Rt
at

where
the
oxygen

Ro,
630.5

and

in

(a), gold)
bt of
a

point.
-

(c)
t

1063

(freezing
E

point
=

of
a

is

defined

by
+ +
Pt
ct2
-

where
one

is be

the

electromotive
is

force
at

PtRh
t.

thermocouple
The 630.5
constants

when
a,

junction
the

kept
point.

0 C

and the

the
values

other
of

is at
E
at

b and

should and

determined

from

C,

the

silver

point

gold
1063

(d)
t

above is defined

(gold
Jt

point)
exp
~

by
_

(Ca/A (Ca/A
/

(?au {t +

To))
To))
at
-

1
1

JZx
where

exp

body Also,
Detailed
in

Jt and radiation
To
=

/au
at

are

the

spectral
0.01438
m

intensity
and
at

the

temperature
C%
=

the

gold

wave-length point

A of

black

/Au,
in

respectively.
meters.

273.16,

description
Internationalle
de

of the the
the above 11th

the

other

"Echelle

Pratique
General six
as

A is measured deg and conditions experimental de Temperature

wil

be

found Edition
Meas-

de

1948,
and

amendee
ures.

1960",
to

Conference

on

Weights nearly solidifying C;


the Standard

In

addition
are

points

of of of
no

definition,
e.g.,

twenty

fixed

points COa,
of
ever,

recommended

substandards:

the

point
melting
yet.
of

of

-78.5

W,
Below

3380

C.; C.;
the
oxygen in

freezing
under
a

point
pressure
we

Hg,
International
at

-38.87
1 atm.

point
Howuse
a
or

etc.,
the

point,
field of

have

workers

physics
the
vapor

extremely
pressure

low
all

temperatures
4He
so

temperature The

scale

defined scale absolute


in 99.994
was

by

practical
the
can,

determined

with

equations possible
of 1954 with

3He.
it
can

care

that

approximate They
the of
water

temperature

scale
dif er
at

however,
gave

principle
C C

each

U.S.A. which

(thermodynamical,
(Int. 1948).
FOR
a

point. 1954)

Their
for

high precision. in comparison the point boiling

is

100

2.6.

CLAUSIUS'
a

INEQUALITY

AN

ARBITRARY

CYCLE

When and absorbs

system
heat

performs

cycle

while

in
the

contact

with reservoir

the

environment
at

Q{{i=\,

2,. .,

n)

from

heat

R;

temperature

70

SECOND

LAW

OF

THERMODYNAMICS

[Ch. holds

2, 7

T\e)

during

the

cycle,

then

the

fol owing

tM)^0.
If
so

B.9)
may

the that

change B.9)

is

continuous,

the

summation

be

replaced

by

an

integral,
B.10)

becomes

Proof:

Consider

an

auxiliary
The

heat

source

Ro

(at
between

temperature
from

To)
Ro Ro,
in

and the j-th the


a

Carnot
heat
work that

cycles
reservoir
done
on

Cu

it

gives

C2,. ., cycle Q operates Cn. absorbed Rt. Let Q\ be the heat when the Ct by its surroundings we have the heat Qt to Rf. By B.5)

and
and such

by Ct cycle operates

A\

way

Ql
If
now

Qi^v
cycle
and

and

A\
auxiliary
lose from
nor

Qt-

Q[
Q,. ., gain
heat
heat

Qt Cn
and
are

the

original

cycles
the

operated
the
net

together,
result work
is that

the
the

reservoirs heat

Rlt. .,

Kn
\-

neither
is taken

(Q[

-\

Q'n)

reservoir

Ro

and

is
be when
then

done

on

the
to
zero

environment.
or

According negative.
consideration

to

Thomson's
is

principle,
proved.
because
The

this

must

equal
the be

Thus,
is

eq.

B.9)
reversible,

cycle
reversed.

under

the

equality operation

holds
can

2.7.

ENTROPY

Definition:
state

A
a

given
under

thermal

equilibrium
consideration.
The
is
a,

state

a0

is

chosen

as

the

standard

of

system

entropy

S(cc)

of

the

system

in

another

equilibrium

state,

defined

by

J
quasi-static

d'fi/r,

B.11)

where
a

the
to

a0,

integration d'Q being


element

is the

done heat the

along
absorbed whole
dS

any

quasi-static by
the In

process

which

connects

system
dif erential

at

temperature
form
this

in

an

infinitesimal

of

process.
=

reads

as

d'Q/T.

B.12)

Ch.

2, 7]
to

entropy

71

According

the

first

law,
dS

eq.
=

A.5),

this
-

can

be

writ en

as

(dU
this

d'A
becomes

d!Z)\T.

B.13)

If

we

use

eqs.
=

A.7a)
dS
-

and
p

A.7b),
+

dU

dV

?Xt
i

dxt
which
dU

?>,.
j

diV,
the

(Gibbs'
first and

relation).
the

B.14)
second laws.

This

is

fundamental
is
a

equation
Pfaf ian
form

combines

Eq.

B.14)

'?yidYi
Y^S,
with

B.15) Y2=V,
volume

,. .

system

where

we

are

only

concerned

F3 changes,

x1,. .).
eq.

For

closed

B.14)

becomes

dU=TdS-pdV.
Entropy.
A
state

B.16)
and

quantity:
a0 have

Let
a.

L
we

1/

be
eq.

two

quasi-static B.10)
to

necting

the

states
we

and

If
a

apply
ao

the

processes reversible

con-

cycle,

ao(L)a(L')ao,

d'eT +
ao(L)

a(L')

Ke=o. T

We

know

thus

that

the

integral

d'Q
T
ao(L)

o(L')

is
is

determined

fixed,
a.

the

by integral,
mentioned
on

a0

and
or

and

is

independent
is
a

of

and

V.

Therefore
defined for

if

a0
a

S(a),
1.6,
which for

state

quantity
and

uniquely
are

given
Note:
and

As

in the
process

d'Q,
connects
a

d'A

d'Z
the
two

not

total
In and
contrast

dif erentials
to

depend
is
a

states.

this,
to
an

d'Q/T
infinitesimal

total

dif erential

change
denominator
2.5

of of

the

state

quasi-static quantity
of

S;

process in other

is T

equal
is

words,
as
a

the of

inte-

grating

d'Q.
the

Figure
ature

il ustrates
pressure.

entropy
2.6 shows

hydrogen
the

gas

function

tempergas
as
a

and

Figure
and used

enthalpy
for the

of

hydrogen
function,

function
can

of
be

pressure

entropy.
as an

Note

that

lat er

entropy

conveniently

independent

variable

(see

3.1).

72

SECOND

LAW

OF

THERMODYNAMICS

[Ch.

2, 7

cal/g

deg

Ch.2,7]

ENTROPY

73

bfi

100

cal/g
of

deg
hydrogen

Fig.

2.6.

Enthalpy

74

SECOND

LAW

OF

THERMODYNAMICS

[Ch.

2,

2.8.
It
a

ADDITIVITY

OF

ENTROPY

would
the
mass

be

almost

obvious is in because
in
a

that

the

entropy
absorbed
state

is

an

extensive

variable.
is

If

homogeneous
or

system

thermal
the

equilibrium,
heat

the

entropy
each
a

proportional
of
the
state

to to

volume,
system
the
mass.

in from
is

step
standard
state

process

bring portional
A

the
to

thermodynamic
in

is

pro-

thermodynamic
exists.
If

state

the
is is

equilibrium
is in

the for

system
it the

general composed
system

sense

in

which

local
of

of extension
as

subsystems,
of
the
sum

each
the

which
of the
of

thermal
to

equilibrium,
define
This it
means

natural
the
+ a,

definition
of the

entropy

whole
if
=

entropies
B.17)

subsystems.

that,
S

total

entropy

is

S,

then

SA(a)
in
states

SB(/0+-,
/?,. .
of the with

where

the

parts,
This

A,
is
states.

B,. .
the

are

entropies
concept
of

SA(a),
entropy
to

SB(f}),. .
general

respectively. thermodynamic
2.9.
GENERAL
a

generalization

EXPRESSION

OF

THE

SECOND

LAW

When

system
another hold:

under
state

consideration,
a"

starting
through
a

from

thermodynamic
L,
the

state

a',
relations
the

reaches

certain

process

fol owing

second

law:

V
the

V Vd'Q

gAS,

where

AS

S(<x")

5(a')

B.18)

first

law:

\
'(L)

d'Q
is the

AU-A-Z,

where

AU

(of)

(a').
of
the

B.19)
system
over

Here

d'Q
the various
L.

infinitesimal

heat

received

by

the

various indicates
is
a

parts
the carried
process.

from the
process

environment

(at
parts
of
the

temperature
system
holds
and

X"(e)),
the
when
L

?
is

summation

integration
reversible

along
For

the
an

The
process,

equality
eq.

only
becomes

infinitesimal

B.18)

^dS.
If the

B.20)
the

temperature

is

uniform

throughout

system,

the

environment

may

Ch.

2, 10]

THE

DIRECTION

OF

AN

ACTUAL

CHANGE

75

be

considered
the

to

be
T

about
of the

at

the

same
so

temperature.
that
the

Then

7"(e)
eq.

is

replaced
becomes

by

temperature

system,

relation,

B.20),

d'Q^TdS,
or

B.21)
+

dU
Proof:

-TdS^d'A
process,

d'Z. a'
Then
to
we

B.21a)
a"
have and

Consider eq.

quasi-static
to

R,

from

apply

the

in-

equality,

B.9),

the

cycle,

a'(L)a"(R)a\

rp
a'(L) a"(R)

hence

a'(L)

The of
so

result,
the that

eq.

B.20),
is

is

the the

dif erential
heat
=

form
transfer and
the

of takes

eq.

system
we can

uniform,
assume

B.18). place
eq. law in
terms

If
at

the that

temperature temperature
holds.
Note

T(e)
is

relation
the first

equality inequalities
cerning

eq.

B.21a) B.21)
system

obtained

by
are

using
writ en

B.21) A.5).
of

The that
con-

inthe

and under

B.21a)
consideration.

only

variables

the

Fig.
2.10. A process
THE

2.7.

DIRECTION

OF

AN

ACTUAL

CHANGE

cannot

be

realized
those

between

two

states

a'
for
which

and
a

a"

of

given
a

system
certain

if constraint.
and

it

violates
If
so

constraint,
it

inequality only
no

B.18). changes
change

This
are

means

that,

system

under

possible
satisfies

satisfy
the

B.18)
system
cannot

with

that

conceivable
in
or

B.18),
B.18)

change
for

stays

equilibrium.
conditions

Thus,
for
an

possible

changes

inequality equilibrium

gives
under

conditions

various

con-

76

SECOND

LAW

OF

THERMODYNAMICS

[Ch.
in the

2, 10

ditions

of

constraint.

These

are

summarized

fol owing: Equilibrium

Constraints

Direction

of

change
AS^O

condition
5"=max. 5=max.
+

a) aj b)
bx)

General

adiabatic

system:
A
=

<2
AM=0*

Isolated

system:

<2
Constant Same Closed
as

o, above,
system,

0, Z=0,
AS=0
no

(AS)VVM^0

entropy:
AS=AM=A=0

Auk'A

work,

closed

system:

AU^O
constant

U=mm.

c) cx) c2)

temperature:

AM=0,
Closed

AT=0

AF^A
isothermal

system,

cycle:
0<^A
temperature

AM=0,
Closed and volume:
AM=AT=AV=0

AT=0

system,

constant

AF^O
constant

F=min.

c3)

Closed
and
pressure:

system,

temperature
=

AM=AT=Ap
Here
A

AG^O
work
F=U and

G=min.

is

the

externally

applied

-TS,

B.22)

B.23)
F

is

called

the

Helmholtz side for


of
a

free

energy,

and vanishes
in

G,
case

the

Gibbs

free

energy

(see
JS^O

Chapter
Note:
The

3).
left-hand the
to
a a

expresses also for that

condition

B.18) possible

a)
can,

and of

therefore
course,

change.

This
increase

be The

applied
condition

closed

system
of
constant
to
a

(Principle
entropy
the

process
we

of the b) is
under In

clear consideration
process,

from

of entropy). B.21a).
when
an

Note,
we

however,
say
constant

refer

only
in in

system
irreversible

entropy,
also take
of
the

for,

general
the

increase
processes

in

entropy

may

place
entropy

environment.
the
heat

isothermal
is

c),

the

change

ASr

of

reservoir

By

AM

we

indicate

that

there

is

no

exchange

of

matter.

Ch.

2, 11]
=

MAXIMUM

WORK

AND

MINIMUM

WORK

77

(T(e)
entropy
must

T).
have

Since

the

principle
=

of
+

the of

increase
the

of

entropy
and the

applies
heat

to

the

total
we

change,

ASt

AS

ASt,

system

reservoir,

Substituting

AUA,

this

becomes
AU
-

TAS^A.
to

This

is

the
A
MAXIMUM
=

condition

for
V

c) according
substituted
AND to
MINIMUM

the

definition
the
WORK

of condition

F. for

For

constant

pressure
2.11.

pA

is
WORK

obtain

c3).

Principle
occur

in other.

an

of maximum assembly
The

work:
of bodies
can

Consider
which
are
on

the
not

possible
in

processes

that

may

thermal

equilibrium
in

with
a

each
is In

work when
the when

that
process the

be
is

done reversible.

the

surroundings
the
are

such

process

maximum

particular,

temperature,
of the

T(e\
component
a

pressure,

p(e\
for be
as

and the

the
en-

chemical
vironment

potential,
and the

/^-e),
system

7-th
law

prescribed
can

undergoes
the

change
can

that

expressed

by

AS,

AU,

AV

and

AMP
Q
=

first
+

A.5)
-

be

writ en
-

AU done

pie)AV
by
in

? nf
j

AMj
on

W,
the

where

is

the
to

work

the volume.

environment
The second

system

other

than

-p(e)
gives

A Vdue

the

change
theorems:
AU-

law

B.18),
^
must

Q^Tie)
W.

AS,

the

fol owing
0
Wmin
the
case
=

T(e)
Wmin
to
>

AS

p(e)
this

AV

X /ije) ANj
W,
is

B.24)
be than
done

Consider
the which environment is

where in order

0.
W

Then

the

work,

that when

by Wmin,
is
re-

make

the

minimum

work.

equals

change Wmin

always

greater
the

only

change
W.

versible.

T{t)
Consider this the
case

AS

+
>

p^AV-YsPLfANj)^0.

B.25)
extracted
the

where
W=

Wmzx
>0

Then

the less than


is

work

that

can

be is

by

work.

change, I W\
Divertissement

equals

\ W\ Wmax
6

is
if

always
the

Wmax
reversible.

which

maximum

only

process

Axiomatic

foundation

of

physics

may

not

seem

of thermodynamics. so important

The
to

axiomatic

the

physicists

of

systematization today.

Now,

78

SECOND

LAW

OF

THERMODYNAMICS

[Ch.
with
one

physics
man-made

is

more

formal
formulation and

concerned, logic.
of
us

to

be
same

sure,

physical
should
very
are

facts
not

rather

than that
a

At
a

the

systematic clearly
the decades
exact
at
was

theory
fabric
of

time, is certainly
what when

forget exhibiting
and
queen
was

valuable,
basic
facts
Towards

helping
which
of
the
some weaves

to

understand
the

the

what

is

logic
sciences, least by
most
at

nineteenth the

century,
axiomatization
to

physical physics
of

theory.
became

the of

last
the

the

perfect physicists,
influenced
led
was

physical
goal
of

theories theoretical
which David dominated Hilbert.
among

thought,
This matheall

be

the the

final

physics.

strongly
that for
time

by
by
the

axiomatism

matics theories

great
the

mathematician,
the ideal is

Thermodynamics
such

probably

best model
even

suited of
in
a

physical
Euclidean

geometry.

physics
straction

ture,

it

axiomatization, In fact, thermodynamics in its highly logical of our experience resembles certainly
a

unique
upon
as

which the basic


In of

was

realm
laws
its

of
-

classical
the
struc-

construction

few

ab-

being
geometry.
at

assumed
the

axioms.

simple

Among
the
best
known

number
and

of

attempts
most

axiomatization
is

thermodynamics,
due
to

the

successful

probably
der

that

C.

Cara-

theodory
Math. second

(Untersuchungen Ann. 61 A909) law by a very


is based
as
on

i ber

die

Grundlagen
the
as

355). simple

He

replaced
assertion
theorem

traditional

given
which

by
states

Thermodynamik, expressions d) in 2.3 in


that
a

of the
text.

the form

This such

mathematical

Pfaf ian

d'G
possesses
an

=Xdx+
factor

Ydy

+
if which

Zdz

borhood
P

of
any

integrating point
on

if,
one

and

only
P'

there
cannot

exists
be is
Born
most

in

every

neighfrom

at

least surface
is
an

point
determined

reached
that

along
critical
for

curve

the

by the
theory,
which

condition which
282.

d'Q=0.
acces-

review

of

Caratheodory's
old

easily
appeared
also

sible
in

physics
Thermodynamics
1957)
p.

students,
Zeitschrift
64.

article

by
218,
Mechanics

Max

Physikalische

Wilson, Press,

XXII and

A921)
Statistical

249

and

See

A.

H.

(Cambridge

Univ.

Examples
1.

Derive

Clausius'
from

principle
Clausius'

from

Thomson's

principle.

Also

derive

Thomson's

principle
Solution
In

principle.

order

to

show

that

Clausius'
to

principle
show Clausius' could
to

can

be

derived

from
is be

Thomson's
violated

principle,
Clausius'

it
amount

is

sufficient
is

that
be
a

Thomson's

principle
would
from
a

if if
heat
a

principle
of

violated.

principle
removed

violated

positive
reservoir,

heat

Q^
transferred

low

temperature

Rl5

and

be

hotter

reservoir,

R2,

without

leaving

Ch.2]
any

EXAMPLES

79

other
C

changes.
between
is while

If the taken
two

this
heat from is

process

is reservoirs and
to

possible,
in which

combine
the

it heat
to

with

Carnot

cycle
also

Qt
Q2
would
to

Q2
be that

(Q2
to

is the
the

positive)
Q2
Next
we

environment
heat
was

Qt
from that

taken
Thomson's show

R2 given R2 and

the

work
Then the

equivalent
net

is done

Rx.
was

result converted

completely
is

work.

This

would
is

violate violated.
to

principle.
Clausius'

principle
Thomson's

violated
it
is

if

Thomson's
as

principle
mentioned
and this work
and
convert to
a

By
extract

violating
a

principle,
Q2
any

possible,
R2,

above,
it

positive
work

heat

from

the other
from

heat

reservoir,

completely
heat transfer
a

into

(without
heat, R2. By Qt from

changes).
reservoir

Apply
Rx
is
to
a
no

Carnot the the


is

cycle Qx

extracting Q2
of heat

Qx
these
a

(<2i >0)
two

to

cold

processes reservoir

there

(cold) change
reservoir

giving
than

other

Rt

hot

R2.

This

contradiction

of

Clausius'

principle.

Oi

(a)

W=Q2

Fig.
2.8.

/
Ri

(b)

2.

Show form

that

the

internal

energy

of
of

material the volume. function

whose

equation

of
is

state

has Tthe

the

p=f(V)T'is
temperature,

independent
and

Here/?
of
V

the

pressure,

absolute
Solution

/(V)

is

only.

If have

we

let

the

internal

energy

be

and

the

entropy

be

S,

from

eq.

B.16)

we

A)
8S dv

B)
1
_

dS\

/8U

Jf)~\f
The

C)
condition for

equation,

82Sj8T8V=82Sj8V8T(the

dS

to

be

an

exact

80

SECOND

LAW

OF

THERMODYNAMICS

[Ch.

dif erential),

gives
8U\
8
+

~8VJ
Since

If\f)
we

/>\_

/I

dU\

~8V\T

~dT)'

d2U/8T8V=d2UldVdT,
,8V

have

)T

8T\T

or

Now,

since

p=f(V)

T,

the

right

side

of

eq.
=

D)
0,

vanishes

and

(dU/dV)T
showing
3.

that internal

does

not

depend
of
a

on

V.

The
the

energy,

u,

unit

volume
gas

of
is

gas

is
p
=

function

of Determine

only

and

equation
form

of

state

for

the

given

by

%u(T).

the

functional
Solution Consider

of

u(T).

this
can

gas

with
as

volume

V and

at

temperature

T.

The

internal

energy,

U,

be

writ en

Vu(T).
eq.

A)
E)
of

Substitute

eq.

A)

and

^G")

into

example

2, then

we

have

iu(T),
T

B)

dT

By

integration,

we

have

log
u

(T)
(T)
radiation
=

log

const.,
x

(const.)
power

r\
of
T.
a

C)
of

i.e.,

is

proportional
i.e. the thermal

to

the

fourth

(A
gas.)
cycle

gas

light

quanta

(photons),
4.

field

is

such
Carnot

Prove

the

fol owing

equation

by

operating

using

gas

between

Ch.
two

2]

EXAMPLES

81

heat

reservoirs

of

temperature

Tt

and

T2

Tl~dT:

where

p,

and

1/

are

the

pressure,

the

volume

and

the

internal

energy,

respectively.
Solution Let

the
absorbed the

volume

of

the

gas

in

state

(/=
processes

1, 2, 3, 4) be
1-+2 and

Vt and
3-+4

the
be

amounts

of

heat

By

first

during law B.19)

the
we

isothermal
have

Qt

and

Q2.

<2i
and

A)

Qi
of the

Qz=

(pdV+
12

[pdV+
an

[pdV+
3
4

\pdV.
eq.

B)
holds:

Because

assumption

of

ideal
+

Carnot

cycle,

B.6)

f
Since

y-o.
we

0)
may

Tt

T2

d T

is

an

infinitesimal,

put

V2

'=.

V3

and

V4

Vt

and

Fig.

2.9.

82

SECOND

LAW

OF

THERMODYNAMICS

[Ch.
eq.

omit dif erence and


becomes

the 3->4

second

and
at

the

fourth

terms

in

B).
the

Further,
same

the value
of
so

infinitesimal

ofp
can

the
be

corresponding
put
4

points

(for

V)
that

on

1 -2
eq.

{dpjdT)v{T2-Tx)=-(dpjdT)v
2 3

&T,
2

B)

13

14

r)Jv

dV.

D)

Now,

eq.

C)

can

be

writ en
+

as

y
or

y=

y(Qi

Q2)

-^

Qi

0,

E)

From

eqs.

D),

F)

and

A)

we

have

G)
isothermal

Since

the
state

state

can

be

any

point

on

the

line

passing

through

the

1, eq.

G)

implies

5.

Two

kinds
in
two

of
in

ideal

gases

at
are

equal
mixed
an

pressure

and dif usion.

rated
increased

containers,
this
process

by
amount

temperature, Show

initial y
that the

sepa-

entropy

is

by
n,

log
of
occurs

1
nt

+n2

n2

log
gases.

nt+
Assume

n2)
and
to

[,
that that
no

A)
change

where
in
pressure

nt

and

n2

are

the
in

moles the

component
due
is
to

pressure of

and

temperature
gas

the

dif usion

the

partial
concen-

each

mixture

proportional

the

molar

tration.
Solution

Initial y
and
were

the

gases

1 and

2
a

had

the When

volumes

Vl=niRT[p
the wall
is

and

separated

by

wall.

removed,

V2 they

n2RT/p
mix

by

Ch.2]

EXAMPLES

83

dif usion.
first
a

Instead
process
+

of

which

considering reversibly
the Such
a

the,

dif usion the


one

process

itself,
gas

we

consider
the
state

separates
gases,

mixed the
state

in

(V=V1
other
in

V2,

(V,
Two

T,p) T,p2).
containers

into

pure process

in

(V,
arrangement
where

T,px)
the wall
gas
on a

and shown

the
in

is

realized

by
are

the while
of

Fig.
is

2.10.

of

volume

V,
the
gas

superimposed
to

wall
is

semipermeable
to

allowing
the
gas

only
1.

pass

the

semisemias

permeable permeable
two

The
to

pressure

of

the
pressure

impermeable
that container rise
is
to
no

the
the

wall
containers the

is
are

equal
drawn
pressure

the

partial
the
pu

gas.

Hence,
with
resultant internal in

the
gas

apart,
so no

walls but

of

the

experience
on

partial
and

this
done

the the

container,
temperature

work

is

gives adiabatically,
There

force
energy

the
no

and

remains

unchanged.

change

the

entropy.

(a)
Fig.
2.10.

Now,
are

in

order

to

isothermally

integrating
for each
as

dS=d'QI

the bring compressed Tp

gases

back
from

to

the
V

initial
to
we

volume
T= nR

Vt
obtain

states, and
the

the

separate
in

gases

V2

V\

V\ V,
AS2

respectively. change

By
entropy

ASi
Therefore,
mixed
gases.
to

n1Rlog
is

n2R\og~.
for

B)
reversibly

ASt+AS2
Thus
the

the

change
increase

in

entropy
in

separating
must

the

entropy
+

the

dif usion

have

been

equal

AS

(ASt

AS2)
log

< nt

log log

n2

log

+ n2

n2

n2j

84

SECOND

LAW

OF

THERMODYNAMICS

[Ch. law

6.

When

magnetic
H

material
is

obeys
the

Curie's
T

M=CH/T
temperature,
dH

(where
and

is
C

the
is
a

magnetization, constant),
for

field,
dT
=

is

the

absolute

show

that

(CH/CHT)
heat

an

adiabatic field.

change.

CH

is

the

capacity

per

unit

volume

at

constant

magnetic

SolutiojOv
Let
m,
5

the/internal
arid
M

energy,

entropy

and
do
we

the
not

magnetization
consider
a

per

unit in

volume
5

be
is
a

respectively.
T

(We
H,
so

change

volume.)

function

of

ami

that

have

By

definition,

CH

T(d${$T)H.
/8.
KdH

Furthermore
\
_

the

relation

/3M\ Jt
from

\dT
du=Tds+HdM

/ft
we

is

obtained

in

the

fol owing

way;

have

Dif erentiate
to

the
then

first

equationwith
the
two

respect

to

and

the

second

with

respect
we

T;

setting

equal

to^each

other

gives

B).

From

A)

have

\d
Under

adiabatic

conditions
dr

(d^=0),
T
=

the

relation
dH
CH
=

fdM\

CH\dTjH
no

CHT

dH

is 7.

obtained. that when work the


the

Show minimum

there

is is

exchange
in the in
constant

of

matter

with
free
energy, energy

the

environment, dF,
dG
for for
a

the

dWmin
increase

(i)
constant

equal
equal

to

Helmholtz
the

change change

at

temperature

and increase and

volume;
Gibbs
pressure.
free
a

(ii)
constant

to

at

temperature

Ch.

2]

problems

[a]

85

Solution
For
an

isothermal

process

the environment

temperature
so

of

the-"

system

is

e#ual

to

the

temperature

T"(e)

of

the
=

that

eq,/B.24)
dF

giye$V

dWmin
We

dU-TdS
for

pie) dVr

+^ldV.
B.22)r-For
If

A)

have
condition

used
of

the of

definition
constant

the

the
pressure p

volume
is
=

the

systyem

constant

p(e\

A)

gives

dWmin

dG

by

defini^^lj^

(dVy/^f^^esultSjhdi^in^dF. ^j^^Q a^kj ^rec^^Q


Gib^s

Helm^ltzip^Pelirgy*ln^eq.

the

external

pressure, pr,

free

energyXq.

B.23).

1.

Using

Clausius'

principle/provejpfausius'

inequality,

j w^original
from
state

B-9)

2.

When

system

$
is

returned
net

to

its this

through
environment

an

isothermal
is
zero

re-

versible
the

change,
work
done

jhe
zero.

heat Prove

absorbed
statement

its

and

also

(i) by

using

Clausius'

inequality

and
3.

(ii)
that,

directly
if
two

by

Thomson's

principle.
adiabatics

Show contradicted.

quasi-static

intersect,

Thomson's

principle

is

4.

If

Tmax

is reservoirs
t],

the

maximum
receives
to

temperature
heat and it
1

of

the
is

heat minimum show

reservoirs

from

which
of the
the

thermal heat

engine
never

Tmin
up

the

temperature
that the

which
exceeds

gives

heat,

efficiency

of

engine,
5.

-(rmin/rmax).
of the

Show
are as

that

the

efficiencies in
the

three

cycles

listed

below

for

an

ideal

gas

given
Otto

list.

(i)

cycle

(Figure

a):

(ii)

Joule

cycle

(Figure

b):

86

SECOND

LAW

OF

THERMODYNAMICS

[Ch.2

(a)

V:

P2

F)

V2

Vi

Ch.

2]

PROBLEMS

[A]

87

(ii )

Diesel

cycle

(Figure

c):

l)
Assume
Let

(V31V1)

that for

Cv,

Cp
material

and

Cp/Cv
the

are

constant.

6.

given
B,
ratio
C

intersections

of

adiabatics
Show AB of
to

a,

a'
in
a

and

isotherms
process

t,

t'
is

be

A,
the

and

in

the
and

ABCD CD

of

the

heat t, t'

absorbed

determined

by

diagram. during is independent

p-V

that
the

cyclic
off adiabatics. the

heat
of

given

during

the

choice

7.

Derive
volume

the
is ideal in process the

entropy
constant,
gas is

of

an
=

ideal

gas

when

its

molar

specific

heat

at

constant

Cv
of
volume

Cy.
Vt

8.

An increase
this

expands
gas

adiabatically
when
the final

in

vacuum.

Calculate is

the
show
that

entropy
irreversible.
increase
constant

of

the

volume

V2

and

9.

Consider
to

in pressure in the

entropy
and

when

an

ideal
constant

gas

is volume.

heated Show
the second and

from

Tt
that
case,

T2
entropy

(i)
y is

at

(ii)
case

at

the
where

increase the
ratio of

first

is heats

y
at

times
constant

that

in
pressure

the

specific

constant

volume.

88

SECOND

LAW

OF

THERMODYNAMICS

[Ch.2

10.

Experimental y
pressure, and much
of
p,

it

has

been

found

for
v,

given
a

gas

that

the

product
the the

of

the
How

and

the

specific
energy

volume,
is the also

is
a

function

only only
of
this
gas

of
of from

temperature

that
can

the

internal
said
about

function
of
state

temperature.

be

equation

viewpoint

thermodynamics?
relations

11.

The

(a)pV=f(d)
has
on

and

(b)
of
an

(dU/8V)e
absolute

are

given
p

for
Here

gas. 6

Show
is
V is the the

that/@)
temperature
volume 12. and

the
some

significance arbitrary
the

temperature.

temperature
energy.
s

scale,

is

the

pressure,

is

internal

Calculate relations absolute

the

entropy
the
T:
p
=

density
energy

of

the

radiation
u,

field
radiation

using
pressure,

the
p,

fol owing
and the

between

density,
oT4
and adiabatic

temperature

%u,
lines

{a

is

constant).
and consider
a

Also

draw

the

isothermal

lines

Carnot

cycle.
13. The of
its

internal its

energy

of
M.

paramagnetic
Show that
x
a
=

material

is

known
defined

to

be

independent
the
inverse

magnetization magnetic susceptibility

temperature

by
to

of
absolute

(9=1/x,

M(H)

is

proportional

the

temperature.
14.

(i) Prove compressibility


to

that
at

the
is

ratio

of
to

the the

adiabatic ratio

equal
pressure.

of
This

the
is

compressibility specific
the
same

to

the
constant
as

isothermal volume

heat

at

that

constant

{Hint:

problem

example

Ch.

2]

problems

[a]
For

89

in
to

Chapter problem
Show
that

1, but
5 in

we

use

the

entropy.
the

another

solution,

see

the

solution the
constant

Chapter
the that ratio is
to at

3.)
of
adiabatic
to

(ii)
thermal

magnetic
the field. ratio of

susceptibility

equal
constant

the

susceptibility specific

to

iso-

heat

at

magnetization
15.
Prove

the

fol owing

equations:

{Hint:

df/is

an

exact

dif erential.)

(Hint:
16. Prove

dS
the

or

&His

an

exact

dif erential.)

fol owing

equations:

d2u
_

d2s

d2h
_

d2s

8Tdv

dTdv'

dTdp

dTdp'
=
-

(ii )
where

fds\
;
_

\dvJT
u,

=(--),
h,
cv
s

fdp\

(ds\

\dT);
the
energy,
are

\dpJT
cp
the

[ ) \dTjp
and

fdv\

(Maxwell's
entropy
at
constant

relations),
per

are

tively
pressure.

and

and

enthalpy specific

unit

mass

respecconstant

heats

volume

and

Prove

the

fol owing (i)

equations:
cp-cv
=

T(Al

(dv\

{dp

dT)p\dT

where

lfdv

dc>\ t(s2"

90

SECOND

LAW

OF

THERMODYNAMICS

[Ch.
free from energy
1

18.

Calculate
energy
at

the

change
a

in

entropy,
ideal
gas

Helmholtz
is

and
atm

Gibbs
to

free
100
atm

when
20 25

mole

of

compressed

C.

19.

At

the
V

volume
=

of

water
-

is

given
+

by

18.066
1000

0.000715p
atm

0.000000046p2

cm3/mol

for/?

between

0 and

and

(
Find

J
increase of
at

0.0045 25 in

0.0000014p
to

cm3/deg
1 mole

mol.
of

the
atm

work
and

necessary

at

C
its
1 atm

compress energy.
0 C

water

from

1 atm

to

1000 20.
The

the

internal
and
100

heat
of
average

of

fusion heat

ice

at

is AH=

AH= 9717.1

1436.3

cal/mol
cal/mol.
between of of
steam
one

and

the
0 C

heat
an

vaporization
C
at

1 atm

and of 18.046 the


and

is

Assuming
mole
100

capacity
water,
and

cal/deg
dif erence

mol
of of
one

at

1 atm

and

100

for
1 atm

calculate
0 C,

the

entropy
mole

of and 21.
A

ice

the

entropy

at

1 atm.

substance the

has

specific
It

heat
a

cs

in

the

solid

state

and

in from the has the

liquid
solid
to

state.

absorbs

latent all
much
in

liquid.
calculate

Assuming
how

heat, specific
more

Q0,ata
heat
values

temperature,
to

be

heat specific To, changing independent of this heat

ct

of

temperature,
at

entropy

gram
state
as

material with of
the

temperature
state
at

Tt (<
the
to
same

To)
also

the

supercooled (Assume

liquid
the

compared

solid

temperature.

specific

supercooled
22.

liquid
it is found

be

ct.)
for
a

Suppose

experimental y

solid

that
+

(dV/dT)p=a
at

bp
much

cp2
wil
pA
to

temperature
the
T.

for

pA^p^pB.
from

How
a

the
pB
at

entropy
a

increase
constant tem-

when

solid

is

compressed

pressure

perature
23.

Express
for
be
a

the

coefficient
adiabatic
from the

V(8T/dV)s,
expansion

which of
of
state.
a

indicates
gas,

the
in
terms

temperature
of

change
that
can

quas-istatic

quantities

derived

equation

Ch.

2]

PROBLEMS

[A]
a

91

24.

In

the

Joule-Thomson from
the
to

experiment,
high
low
sides and
pressure

gas

is

forced
a

to cotton

flow

under

conditions
adiabatic sides dif ers
constant
are

side side of

of

plug
while
of

in the

steady with pipe


at

state
an

wall

the

pressure

the
As
a

plug,
result
that which
terms

pressures

both
at

kept
at

constant
two

(see
of
express
is
a

the
the

the

figure). plug.

this,
is
an

the the

temperature

Show
in

this
indicates

this when
express

effect
the

enthalpy (Joule-Thomson
Joule-Thomson

(dT/dp)H,
coefficient), good
coefficient

experiment magnitude

of

of
to

Cp
the
B.

and

(dV/dT)p.
equation
of

Also,
state,

pV=RT+B(T)p

approximation
in
terms

of

25.

Gay-Lussac
a

measured

the

change
Write
a

in
free

the
the

gas

temperature

when

it

underwent

free

expansion
dT

into
when
a

vacuum.

equation
from

giving
V
to

the

temperature

change
26. A

gas

makes has
and

expansion
susceptibility
energy

V+dV.
the Curie

paramagnetic
x
at

substance

magnetic
an

law,

positive kept adiabatically (Adiabatic


27. The
ature

C\T const.),
Ti
and

(C
the

is

const),
Obtain field
is
to

internal
of

given
when

obeying by U=aT4
this If

(a
material
is

is is

(i)
from

the
increased
zero,

heat
what

magnetization
0 to

from
wil

Hi.
the

H^

be

(ii) change

the
in

field

reduced

temperature?

demagnetization.)

magnetization
range that and it

M
was

of

paramagnetic
is

body

was

measured
on

over

temper-

found
energy S. processes

Show

the the all

internal

depend independent
to

only
of
Mand

HJT,
also

i.e.,
find

M=f(H/T).
the

functional

form 28.
Consider

of

entropy

possible
C,
of
a

by
lose

which
and

body
down
make
one

at

temperature
to

7^
the
work

with
in
assume

heat

capacity,
to

can

heat
How
is the

cool
can

temperature
done this

T0(T0<Ti)
process

heat

reservoir.

the
For

be
a

maximum?

What

maximum

value?

simplicity

to

be

constant.

29.

The
a

heat

of

fusion
in
a

of
room

ice

at at

0 C

is

1436.3
If
cost

cal/mol.
the
cost

ton

of
is

ice

is to

be

made
per kilo-

by
ice?

watt

refrigerator hour,

25

C.

of

electricity
necessary

12
to

cents

what

is the

minimum

of

electricity

make

this

92

SECOND

LAW

OF

THERMODYNAMICS

[Ch.

[B]
30. 31. Derive

Carathe"odory's
that
if process

principle
the

from
two

Thomson's ideal with


heat
gases

principle.
by
dif usion
were
a

Show
reversible

mixing
it
mole
an

of

dif erent

would

be

inconsistent with
movable

Thomson's

principle.
and

32.

Two in
a

ideal

gases,

each,
adiabatic
is

capacities
piston.
i.e.

Cy
Show

Cv
that
not

are

cylinder inhomogeneous factor grating


the
internal

by
for

this
exist

separated thermally
an

system

non-holonomic,
this

there

does

inte-

d'Q
of
at
a

in

system.
material
is

33.

If

energy

independent
is
a

of

the

volume,
of
T

prove

the

fol owing: (i) the (ii) the the (ii )


constant

specific
volume

heat
Fis

constant

function the

dif erence
volume is

between
a

function heat
and
find
at

volume*Cv pi T only; heats specific only. ofp/T


of
constant

function
constant

only;
and
at

at

pressure

34.

Show function

that of

the
T

specific only

volume

for for its

van

der

Waals
energy

the

expression

internal

gas and

is

the

entropy.
35.

Show
x

that

for
=

gas

which whose
of

obeys
molar

the

van

der
heat
at

Waals
constant

equation
volume
energy

(p+a/V2)*.
(per Cv mole)
is
con-

(V
and

b)
by

RTand

specific

stant

independent

temperature,
V
=

the

internal
+

is

given

CVT

a/V
change

const.

and

that

for
-

an

adiabatic
=

quasi-static
const.
or

T(V
where
gas

bO'1
{Cv
+
a

(p
in
vacuum.

a/V2)
temperature

(V

b)y

const.,
when this

R)jCv.
free

Also

determine

the

change

undergoes
the
to

expansion
coefficient
in

36.

Obtain
gas
ature

Joule-Thomson
order the

second

nb/V(<^\)
Tc
=

and
effect

(dT/dp)H na/VRT(<z:l).
vanishes

for

dilute

van

der

Waals

Also
and
express

find it

the
in

temperterms

Tt where
critical

Joule-Thomson

of

the

temperature

Sa/27Rb.

Ch.

2]
real
gas is
not
an

problems

[b]

93

37.

ideal be

gas.

The

equations
by
and
are

of

state

of

real

gas

can,

for

small

values

of/?,
=

expressed
+ a,

A)
where
that 38.
The

pV
A,
the

Bp
and

Cp2
/?,
7,. .

B)
functions

pp

yp2

B,C,. .
absolute coefficient

known
be measured

of

temperature.
this
gas.

Show

temperature
a=

can

using
for
a

expansion
an

V~x
scale
constant
=

(dVjd9)p
9.

given
that

substance
is

is measured

using
substance
is

arbitrary
is

temperature

The heat

heat

absorbed the

when
pressure Discuss

the
p

expanded d'Q/dp principles


temperature.
the

at

temperature

by
of

also

measured:
and

Lp
in

method
to

involved

(latent connecting

the

changing expansion). empirical

the
9

temperature

the

absolute that

39.

Show

internal
substance

energy

and

the
the Curie-Weiss

entropy

S law

for
x
=

unit

volume

of

paramagnetic
C and

that
T

obeys
is

Cj (T
x
1S

9) (where
suscepti-

9
can

are

constants,
be

the

absolute

temperature

and

the

bility)

given
U

by

the
r

fol owing

expressions: \ (9IC)
M2
+

f
T

CM

dT

const.,

cm
for

W
constant

\C

const.,

where
40.

CM
the
pressure

is

the

heat

capacity

M.

Prove the

fol owing
coefficient

relationship
of

between

the

volume

magnetostriction

and

magnetization:

dp
Next
show
in

HtT

that,
volume

when
AV

the

field

is

increased
is

change

(when

|JF|<F)

isothermally given by

from

to

H,

the

Here is the

/is

the isothermal

magnetic

moment

of

the
and

entire

sample,
is

/?=
the

A/K)

(dV/dp)HtT
magnetic

compressibility

x=IlHV

isothermal

94

SECOND

LAW

OF

THERMODYNAMICS

[Ch.
are

susceptibility.
uniform
41. in

The

magnetic

field

and

magnetization

assumed

to

be

the
is

sample.
no

When
amount

there
of

heat,

exchange received d'Q,


(i)

of

matter

with
a

the
is

environment,
related
to

show
the minimum

that
work

the

by

system

Win

by
t
=

\dT\_ rswmin

\/v
and

in

an

isothermal

change 00

at

constant

volume;
(d

that

b'o

T2
constant
or

VTl
pressure.

j/p

*n

an

isothermal
from
measured

Gibbs-Helmholtz

change equations
values

at

the
of

Kelvin

(These equations.

equations They

are are

called
to

the
derive

used

SWmia

S'Q.)
[C]

42.

How

can

one

calculate
gas

the

molar

specific
from

heat

at

constant

in

its

ideal for finite Dieterici's

condition

(p=0)

actually

measured

pressure values

of

gas

of

specific

heat 43.

pi
equation,
of
on
a

Using
pressure il ustrate

nRT(V-nb)~1
point this using See problem
gas.

exp(-na/RTV),
of the Joule-Thomson
law
12

find

the and
states

dependence
this

the

inversion

effect
Do

figure.
as a

(Show
units. Waals
der

the

using
consideration
44.
We
a

critical

quantities
for
van

of

corresponding 1.) Chapter

of

the

same

would
constant

like
pressure the

to

calibrate
gas

an

empirical
to

temperature

obtained

by

using
For

thermometer
p,
to

this

purpose,

density
measured

the
as

specific
functions

give heat,
of
9

the and
at

absolute
the

temperature.
Joule-Thomson pressure.
Derive

coefthe

ficient
basic 45.

have

been
necessary

that

formula
Joule-Thomson the table. The

make

this for
p,

calibration.
air is
at

The
in

coefficient,
density
of

\l,

pressure

of

kg cm
formula

is

given

air,
0.0012932

approximated
p

by
g
cm

the

1+0.0036690

760

Ch.2]

SOLUTIONS

95

wherep
in

is the C.
100

pressure

in

mm

Hg
constant

and
is

0 is the pressure 0.240

temperature
between
0 C

ec
0 25 50 75

The
C the
of
0 C

specific
is

heat
almost
constant

at

0.257
0.220 0.183 0.153
0.129

and

and

cal

g
numerical

deg.
100

Using
value

above
on

information,
the

calculate

the scale.

absolute

temperature
Solutions

1.

The

environment

may

be

regarded

as

consisting
and

of

heat
in

reservoirs

Ru
sider
manner

R2,. .,
n

Rn
1 Carnot

at

temperature

T[\
Q,
the reservoirs

T{2\. .
Cn_t
Rt
between and

T{ne\

respectively.
operate
the heat

Now

con-

cycles,
between from
and

C2,. .,

which

fol owing Q[
the
and

(see

2.6):

Ct operates Rj and Q'2' R2 0,2 from ceiving Q'n-x


Let C be

R2;

C2
from

operates

R2, R2
operates

receiving
and

the

from heat

R3,
between

Q'^ Rn_t
fol owed
are

R3;. .;
and

Cn_!

receiving Rn_t
When

Rn,
all

re-

from

Q"n

from

Rn.
under consideration. lost

the

cycle

cycles

C,

C1?.. ,

Cn_j

by the completed,

system
the

the
is:

heat

by

each

heat

reservoir

K-l'Qn-l+Qn-l
Therefore,
system
under
A
=

Wn-l*
law,
be

K-On
the total

Ql

according
consideration
-

to

the
must

first

work,
+
+

received

by

the

{(Gi
gi,. .,

G'O
Carnot

[Qi

Qi

Q'i)
Q,

(Qn
Cn,
way

Q'n)}
the

A)

By suitably quantities equations

adjusting
of
are

the

heat satisfied:

Q'n-u

cycles, 22,. .,
0,2
+

C2,. .,
in

choose

2(1)
fol owing

Q"n
0,2
+

such
=

that

the

0,2

B)
A
=

(therefore
fol owing

Qt

Q[

Qn
for

Q'^
the

0).
cycles:

There

are,

however,

the

relations

Carnot

C)

g:
T(e) 1n

96

SECOND

LAW

OF

THERMODYNAMICS

[Ch.
so

Thus
the
we

we

have
is in

2(w
general

1) equations
possible.

adjustment last)
have

by
the

-l/rBe),. .,
fol owing
j-(e)

-1/rj!^,
relations:

together, By multiplying respectively,

all

that
each
and

the

above in

mentioned

equation adding

B)
all

(except
to

them

C),

'

j-(e)

j.(e)
the
is

j-(e)
effect

j-(e)
the
whole

VT/

Since and

conditions

B)
lost
heat.

are

satisfied,
If

net

of

Rn

have

Tf^T^

assumed,

Clausius'

cycle principle

is

that

Rx

requires

that

On

the

other

hand,
that

since

we

have
+

from

B),

Qn
we

Q'^
+

(Qx
Qi

Qj),
01

must

have

Qn
or

Ql

r(e)

J-(e)
that

I j>(e)

j>(e)

/*

From

F')

and

D)

it

is

proved

rj-i(e)
1

'

i=

The
is 2.

inequality
reversible.
For

comes

from

eq.

E)

and

the

equality

holds

when

the

process

(i)
becomes

an

isothermal

reversible

change,
is

Clausius'

inequality,
heat

jd'Q/T^O,
7" is

(l/T)
Therefore, Also,
increase

d'Q
the

(d'Q
heat
to

the
absorbed

infinitesimal
from
the

and
environment

the

temper-

ature).
is
zero.

total

Q
=

d'Q

according
in

the
0

first
and and

law,
the

is the

internal
A=

energy,

eq. A is the

A.2),
work
done

U2
done is

U1 Q {U2 by the environment).


+

IJX

Since

U2
Assume

(ii)
vironment, original
ment

Ut =0, that, Q, is
the

work
the
Since
=

zero,

for
not

the
zero

given
and

state,
is A
=

first
This

law

gives
means

change, Q>0. Q + A
that
in

total
the

heat

input
had done
process,

from returned

the
to

en-

system
the
work

its

0 and

by the
heat

environis

Q<0.

this

reversible

taken

Ch.2] from
one

SOLUTIONS

97

heat

reservoir

and

converted
so

into

work

with
is not
can

no

other found
to

change.
In

This

contradicts
way,

Thomson's

principle
the
reverse

that
process,
we

Q>0 Q<0
must

permissible.
be
=

the
contradict

same

by

Thomson's
3. Assume

considering principle.
that

Therefore,
two

have and line b intersect

and
at

A=0.

the

adiabatic
an

lines

point,
with
a

C,
and because See

in

the
b at

p-V
A

diagram.
and
of
B
an

Consider

isothermal
an

which
can

intersects

respectively.
isotherm
is The
process

slope
7, Chapter

(Such always

isotherm
less

always
of
an

be

found
line.
as

the

than

that
can

adiabatic
considered

example
reversible

1.)

A->B->C->A

be

cycle
isothermal
area

in ABC
means

which
process and

the

system
A->B.

takes
The From

heat work the


amount

Q from
A

its

environment

only
system
and from
is

during

the
to

done
law

by Q
is
=

the

equal
also

the

positive.
a

first of work conclude


have

A,
taken
process. adiabatics

is
a

positive.
reservoir

This and

that

positive
Therefore

heat
in

heat

completely

converted

into
we

this

This
cannot

contradicts
intersect.

Thomson's
4.

principle.
to

that

According

Clausius'

inequality,

we

(a)

(b)

and

therefore,

j-(e)
(a)

j-(e)
(b)

A)

98

SECOND

LAW

OF

THERMODYNAMICS

[Ch.

where

heat

is

absorbed
heat is is the

by given
maximum

the off from


in

thermal
the
value

engine
process of T(e)
we

(d'2i>0)
given
value

an(j

off).
of

If

r(e)

Tmax during

in

through (b) (d'Q2>0 (a) and Tmin


L

the is is the

process the amount

(a)

minimum

(b),
1

then
<

A)
,

have
\C2
^
-

\C2
or

>

min
.

T
*

max

T*

min

D
are

\?,

TL

max

(The
is
are

equal
reversible.
more

sign
Even

holds

when

there reversible The


W

only cycle work,


O-,

two

heat

reservoirs does
not

and

the
if

cycle
there
is

for
two

the

equality
W,
done
T

hold
environment

than
so

reservoirs.)
that

to

the

W=Qt-Q2,

Efficiency

fi

=1

\?l

<1

V.1

T1

max

5.

(i)
system,
the

From

the
which

results is
to

of

example
to

6 in

equal
the
other
gas

the
in

work
the
process

done the
For

Chapter by
a->b,
receives

1, the
the
is
gas

net

work
process W=

done c->d

by
minus

the

in

the

work

given

given
heat
process

by
in

Cv
process

{(Tc
of
=

Td)
the
so-

(Tb
an

Ta)}.
to

On

the
=

hand,

gas
an

the

b->c

to

amount

lution
and

Q example
=

CV(TC
6

Tb).

adiabatic

in

TbV\~l

TaV\~\
n

Chapter The efficiency

1)
is

TV^1^const,

so

(Ba) TcV\~^

TdV\~1

Tc-Tb V1
Td-Ta Tc-Tb

Tc-Tb

Since

\VJ
we

obtain

(ii)
is

Besides

the

work
in

done
processes
-

in

the
b->c

adiabatic and

processes

c->d
Hence
-

and

a->b,

there

work
W

done
=

the

d->a.
+

CV{(TC
=

Td)
-

(Tb
T
=

Ta)}
Cv (y

p2(Vc 1)
T
we

Vb)
have

Pl(Vd

Vm).

Using

p V

nRT=

(Cp

Cv)
=

W
In

CP{TC-Tb-Td
receives

Ta}.

the

process

b->c

the

gas

heat

CP(TC

Tb).

For

an

adiabatic

Ch.

2]
so

solutions

99
=

processpVy=const.,

that

TpA~7)/7
,

const,

and

we

have

and

5-^
\pj
Ta)}
+
+

Therefore
n

To-Td-Td-Tb+Ta
the

Tb

(ii )

CV {Tc Cv {Tc
during

(Tb

p2

(Vc (To

Vb)
-

(y-l)
is

Tb)}
Therefore

CK{7(Tc-rb)-(Td-Ta)}.
process

The

heat

absorbed

b->c

Q
.

CP(TCTb).

yTc-Tb

Using

the

relations

5=^2,
the
Note: less
answer

TaVrX
is

TbVr\

and

T.^"

^i7,

obtained.
to

According
than
is 1
-

the

results

of

problem

4, all

of

these

efficiencies

must

be

TJ

Tc.
if the

6.

This

obvious,

absolute

temperature

has for
a

been

defined,

using

Clausius' If

inequality
lute
7.

B.9)
temperature
a

(the
has

equality
not

sign
yet
been takes
eq.

holds

quasi-static
use

process).
proof
of ideal

the
in

abso-

defined,

the mole

of

eq.
gas

B.8)
the

2.5.
in

When

entropy,

quasi-static dS, is given

change by

place
dU
+

in

change

B.16)
do
=

pdV
T
,

where
d U=

is

the

internal
p V=

energy,

the

pressure

and

the

volume.

Using

Cv

d T and

RT,

we

have dT

dS

Cv
T

R
+

-dF. V

Therefore
S
=

C?logT
constant.

jRlogF

S0,

A)

where

5*0 is

an

integration

100

SECOND

LAW

OF

THERMODYNAMICS

[Ch.2

Note:

For

moles

of

gas,

we

have
/

S(T,
because 8. Since S
is

V,n)

n[Cy\ogT
\

log-

v
+
n

So

B)

extensive.
is

the

gas

no interchange from fore, By A.12) there i.e.,

the
we

undergoing of work, first law,


that

an nor

adiabatic heat

expansion
i.e. the
an

into

vacuum,

there
=

is

exchange;
in

d'A=Q
energy,
gas

and

d'Q
U,
is

O. also
is

Therezero.

the

change
dTfor

internal ideal

know
no

dU=nCv
change.
S
=

and
an

therefore
ideal
gas

is

temperature
n

The

entropy
R

of

dT=0, given

as

(Cv

log problem).

log
Thus

So

j
entropy

(see
process

the
is

note

to

the

previous

the

change

in

this

AS

S(T,
since

V2)
V2>Vv

S(T,
Therefore

V,)

nR

log
process
to

p-,
is
an

which
process

means

AS>0,
increases
process.

this

adiabatic law it
is
an

which

the

entropy.

According

the

second

irreversible
9.
In

quasi-static
1)
we

process

of

an

ideal

gas

(see

A)
dT

and

C)
V

in

example

of

Chapter

have

d'Q

Cv

dT

p dV

Cp

dp.

A)

Ch.

2]

solutions

101

The

entropy

increase,

(AS)P,

for

constant

pressure

process

is

found

to

be

and

that

for

constant

volume

process

to

be

fA\

lCvdT
entropy
increases
is

Therefore

the
are

ratio

of

the

two

equal

to

Cp/Cv

if

Cv

and

Cp
10. We

constants.

have

been

told

that

pv=f(T)
From

and

u(T).

the

fundamental

equation
ds
=

of

thermodynamics,
+

(d

pdv)/T,

we

get

(see

example

2)
\

\ we
see

Multiply

this

equation

by

v,

and
T

that
0.

dT
T.

B)

Integration
The
constant

gives

/(T)
is

const,

C)
and

independent
state

of has
pv
=

the

temperature

volume

and

therefore

the

equation

of

the AT

form

(A

is

constant).
Divide the

D)
equation

From

(dU/dVH=O

we

find
=

dU=g@)
dU
+

dO.
p dV
=

d'Q
for
a

g@)
we

dO

pdV

quasi-static

process

by/@)
f

and

have dV

d'Q_g@)d6 T~

+~7~~

pdV_g@)d0
f(9)

+V

102

SECOND

LAW

OF

THERMODYNAMICS

[Ch. if
we

which

is

clearly

complete

dif erential.

Hence

set

S is of the

function heat
to

of

state.

By
from
reservoir

considering
the
at

Carnot

cycle
reservoir
at

we

see

that
to

the the
heat

ratio

Qx
the cold

obtained
heat

hot

heat
is

0X

Q2

given

02,

given

by

i.e.,

Therefore,

according
=

to

the

definition

of

the

absolute

temperature

B.5),

/@)
(For
12. Let

const.
an

xT.

alternative internal

solution,
energy

see

problem
the

10.)
entropy
S for
a

the

be dU

and

volume,
dV

V, of radiation

field.

Then
+

pdV
T
+

d(aTAV)
%(jT3dV
+
const.
=

iaT*

4<jT2VdT
S
=

A)

aT3V
density

Therefore

entropy
For adiabatic
an

B)
and
p
=

isothermal
process

process,

we

have

u=const,

T3V=

const,

and,

hence,/?

K*=const.

const, Therefore

and

for the Carnot

an

Ch.

2] is
as

solutions

103

cycle
isothermal

shown
processes

in

the
A->B

figure.
and

The

heat

absorbed

or

given
are

off found

during
to

the be

C->D,
B

Qt

and

Q2,

(see

problem

20,

Chapter

1)

Using

the for

relations
the

V^Tl=VcTl
adiabatic
processes,

and
we

VAT3A=VDTl
obtain

or

V^T\

VCT\,

VaT\

VdT\
The

QJT1=Q2IT2.
work done

during

cycle

is

%oT\(T2
quasi-static

Tt)

(VAVB)

and

is

equal

to

13.

The

first

law,

body

is

(see

d'Q example

dUd'A,
1 in

for

process

of

paramagnetic A)

Chapter

1)
=

d'Q
(we
X
or

dU-HdM,
U is
a

consider

unit
M.

volume)
From

where

function
we

of have

temperature

only
only.
Divide

and
Here

independent
0 is also

of

the
of

relation
M
=

M=%H
and
a

H=M/x=M6.

independent
we

function
_

of dM
9
=

temperature
ds
is
_

A)
where
nator
to

by

0 and
S is for

have

^
dif erential.
this
the

d[/ fl
Hence

B)
integrating
be denomiit must

complete
Since

1/x

the

d'Q.
absolute

is ratio

function
In

of

temperature,
we

the

temperature.

fact,
of

if
heat

perform
absorbed,
is

Carnot

proportional with cycle


the hot
seen reser-

this
from

paramagnetic
voir the
to

the

body, heat given,

the
cool

Qlt

from
as can

Q2,

to

the

reservoir

9l/92

be

equation

(See

example
If
we

7 in

Chapter
be

1 for

an

alternative

solution.)
1
ks
=

(i)

let

the
adiabatic

entropy

S, then

compressibility
compressibility

(dV\

isothermal

kt

V\dpJT

1(dV\ {

104

SECOND

LAW

OF

THERMODYNAMICS

[Ch.

Using

A.23)

we

can

write

ks

as

If
we

Sis have

considered

to

be

function

of

and

V,

i.e.,

S(T,V)

S(T(p,

V),

V),
^

T\Sp)y
Similarly, by considering

S(T,p)

S(T{p,
/ar\

V),p),

we

have

w)rw)\)-[
Substituting
Ks

as\

_/ss\
B)

_cp[8t

C)

and

D)

in

vc\dp)yl\dv)p
A.23)
operation
=

cpv\dp)T
as

cpKt'
the

We

again
If

used

in

E).
in and

(ii) ceptibility, (substitutions


15.

the

same

(i)
the

is

applied
obviously

to

adiabatic
%T

magnetic
=

sus-

Xs

{dMjdH)s
V-+M

isothermal

susceptibility,
we

(dMldH)T

and of

p->H),
2 is
one

get
we

Xs=(CmICh)Xt'
give
another

(i)

The

solution

example

proof.
dT

Here
+

proof:
A)

dU=TdS-pdV
Therefore
d

T[~)

<T(-)

-p}dV.

Substitute

this

into

Ujd

obtained

from

A)

and

we

have

(ii)

Substitute

H=

U+pVin

B.16)
1

and

we

have

(d/),

C)

therefore

dS\
_

1 /dH\

dTjp

T\dTjp'

(dS\

\dp)T

T\dp)T

1 /dti\

V
_

T'

Ch.

2]

solutions

105

Since

d2S/dp

8T=d2S/dTdp,

dp
For

another

method the

of method

and
6.

fol ow

solution, of (i).

start

from

dH=d(U+pV)

dS+

Vdp

(i)
we

By
have

definition,

cv

(d'q)JdT,
cv
=

and

by

the

second

law

B.12),

d'q=Tds,

T(ds/dT)v.

Similarly,
cp
=

T(ds/dT)p.
=

(ii)
gives
we

Equation

B.16),
=

du

T 8T

ds
=

p dv

A)
dT

(8u/8T)v
have

T(ds/dT)v,

d2u/8v
dh
=

Td2s/8v
+
v

Also,

since

u+pv

ds

dp,

B)
solution of

and

similarly
The
first

82h/dTdp=Td2sldTdp.
equation
is
is

(ii )
second

proved
as

by
fol ows:

B)

of from

the

problem

15.

The

equation
du

proved

A)

Since

d2u/dTdp=d2u/dp
Taking
in
p

dT,
and
to

we

have 2.

(ds/dp)T=
variables,

-(dv/dT)p.
one

Alternative
may
use

so-

lution:

as

independent

eq.

B)

and

proceed
7.

parallel
of
the

example

(i)

By

(i)

previous

problem,

we

have ds\

(ds
of
T

Considering

s=s(T,

v(T,p))
ds\

as

function

and

p,

/ds\

/ds\

fdvs
=

Now

substitute

Maxwell's

relation

(ds/dv)T

(dp/dT)v

((ii )

of

problem

16)

106

SECOND

LAW

OF

THERMODYNAMICS

[Ch.
\
/a

t08et

/a

Then
answer.

use

(dp/dT\=
solution:

-(dv/dT)p/(dvjdp)T
Substitute
1.

and

substitute

and

jf

to

obtain

the

Alternative

(i)

of

problem

15,

Chapter

1, into

(ii)

of

problem

16,

Chapter

SO

that

/i

dcB\

a2

(dv\

fdv

a2

dp)T
where 16.
we

dpdT
Maxwell's

dT\dTjp
relation
=

\dT2/p
=

have

used

(ds/dp)T
we

(dv/dT)p

(ii )

of

problem

Similarly,

using

(ds/dv)T
dcv\

(dp/dT)v,
=

obtain

dvJT
18. For
1 mole
at

dvdT

\dT
energy

of
constant

an

ideal

gas,

the and

internal
the

is is
constants.

U=

CVT+
=

heat

(see
holtz
the

solution
free
energy

to

volume) problem
is
F=

entropy
and

S(T,p)
T+RT

7).
Uin
are

Uo
TS= these

S^

are

Gibbs

free The
=

energy,

log CVT-CPT G=U-TS+pV=CpT-CpTlogT+RTlog/7


quantities
from

Uo (Cv is the molar + S0 logp Cp \ogTR the HelmTherefore, and log/? +U0-TS0
+

U0

TS0.
const.
=

changes
293

p=\

atm

to

/?=100atm

(T=
AS

K)
100
=

S(T,
-

100)R

S(T,1)
-

log
=

R
=

log10
293R

100/log10
log
that
100
=

4.6R

9.2

cal/deg,
is

AF Note:
not

AG Here

RT
we

log
have

100
assumed

2.7

kcal. but this

Cv

is

constant,

assumption

necessary.

19.

Writing

bp

cp

A)

B)
the

desired

work,
,4

^4,
=

is

given
-

by
p=0

C)
p=1000

Ch.

2]

solutions

107
x

Substitute
^4
=

b=
326.83
atm

-715

10
=

and

c=46

10

"9

to

obtain the A U

cm3/mol
the

33.116
in the AU

joule/mol.
internal
=

If
energy
A
+

heat
is

adsorbed

during

this

change
For

is

Q,

increase

Q.

D)

quasi-static

process TdS
T

Q=TdS
(We
have Therefore
=
-

J
Maxwell's

J
relation

J \dp/T

] dp
=

T\

J \8T/p

)
(ii )

dp.
of

E)

used

(dS/dp)T

(d V/dT)p,
-

problem
F)

16.)
Q
so

298 A U

D.5
-

1.4)

(atm.

cm3/mol)

157.0

(joule/mol),

that

123.9

joule/mol.
change
total
sum

20.

By definition, gration
temperature
state

the
means

entropy
the
each
0
v

is

AS=SV
the

S;

=Ji-v

of

heat
the the

at

instant,
and
be
1 1

T,

as

system
state

i process

(ice
at

at

C
may and

atm)

to

The

i to
100

divided

into
In

i->w0
process

(water

atm)->v.

absorbed, changes v (steam (water i->w0


=

d'Q/ T. Here divided d'Q, quasi-statically


at at

the

inte-

by
from and
1

the

100

C
and
1

atm).

0 C

atm)->w100

[
Assuming
f
the
average

A436/273)
specific
heat

cal/deg
to

mol

5.26

cal/deg
process
wo-wloo

mol.

A) gives
mol

be 18.05

Cp,
log

the

d' Q -^

CP
5.63

dT

C73/273)

cal/deg

cal/deg
=

mol,

B)
=

where

we

put

log

C73/273)
=

log

1.366

0.312. mol

For

wloo->v,

we

have

d'Q

972

10/373
obtain
AS
=

cal/deg

26.1

cal/deg

mol.

C)

Adding

A),

B)

and

C),

we

37.0

cal/deg
change liquid
of
state

mol.
the

21.

Consider
at

the

fol owing
Tt
to
a

quasi-static

substance
at

from

solid

state

temperature

supercooled

temperature

Tt:

solid

at

108

SECOND

LAW

OF

THERMODYNAMICS

[Ch.2
The

Tj-^
1 is

solid

at

T0-h

liquid

at

To^+
To

liquid

at

Tt.

entropy

increase

in

process

Mcs

log.
To.
The

The
3 is

entropy

increase

in

process
Ti

2 is

MQoj

entropy

increase

in

process

-Mc,log^.
state
at
-

To

Therefore the

the

entropy
of
the

of solid
state

the
at

entropy

supercooled liquid Tt by AS=MQQj

Tt
-

is cs

greater

than

To

M{cx

liquid

solid

Ti

To

22.

Using
increase

the is

Maxwell

relation,

{dS/dp)T=
Pb

{dV/dT)p,
f/3F\

the

desired

entropy

given
Pb

by

KdS\ dpjr

) dp
Pa)

J \dTj,
PA.

dp P

PA.

-{a

{Pb

\b

{pi

p\)

%c

{pi

pi)}
we

23.

From

the

condition

dS={dS/dT)vdT+{dS/dV)TdV=O,

obtain

{w)s

~{dv)Tl{df)v

Ch.2]

SOLUTIONS

109

(see
and obtain

A.23)).
the

Now

use

the

specific

heat

at
=

constant

volume,

Maxwell

relation

(dSjdV)T

{dpjdT)v

((ii )

of

Cv problem

T(dS/dT)v,
16),
to

v(dI\
(Since expansion. during
24.
We

\8vJs
for
a

L.\
dlogVjs
gas,

=-(\
temperature
work

Cr\dTjy
decreases
is done
on

(dp/dT)v>0
The the have due
gas

the because

in the

an

adiabatic

cools

down

environment

expansion.)
shown
to

that
a

H=

const,

in

change

small

pressure

example change
/8H\

9 of

Chapter
obtained

1.

The the

temperature
condition

is

from

dT\
_

dH

'Kj

1.5-

1.0-

.-V

II
p
atm

I
100

250

Fig.

2.11.

Joule-Thomson

coefficient

for

CO2.

110

SECOND

LAW

OF

THERMODYNAMICS

[Ch.2

Using problem

Cp

(dH/dT)p
we

and obtain

the

formula

(dH/dp)T=
v\
c

-T(dV/dT)p+

((ii)
A)

in

15),

f8!)
When

\dp)H
state

the

equation

of

pV=RT(

l+Bp)

is

substituted,

eq.

A)

becomes

B)
If of
I is

the

point
second

of virial
at

contact

of

the function

the

coefficient, Tv
the

tangent B, versus
of the

drawn

from

the

origin
and
is

on

the

graph
the
in-

T,

the

Joule-Thomson
p,

coefficient
called coefficient

changes
version

sign
point
2.11
T.

Tx is
Joule-Thomson
the

pressure,

of

coefficient.

Figure
p

shows

dependence

of

the

Joule-Thomson

on

and

-80
300 400 500 600

700

800

900

Fig.

2.12.

Ch.2]

SOLUTIONS

111

25.

For
constant.

free

expansion
The

into

vacuum

(this
to

is for

adiabatic

and 23

irreversible),
and
24.

is

solution

is similar

those

problems
1

(Use

A.23),

and

(ii)

of

problem
dT\
_

15.)

We

obtain

/dU\

l/dU\
_

(dP
have

26.

Considering

unit

volume

of

the

material,
=

we

d'<2
for
we
a

dU

&M
is

A) magnetized isothermally,

quasi-static
that
d?/=0

process.

When and

the

substance
Hence

know

M=CH/T.
CH

i.e.

only

heat

CH]BTX
=

is

developed.

By

the

relation

~{dU-HdM}
4aTzdT-C-d
H

/H
T
'

H=0

112

SECOND

LAW

OF

THERMODYNAMICS

[Ch.2

the

entropy

is

obtained

as

-J
In

const.

B)
H=0,
S is

the
we

adiabatic
have

demagnetization

from

H=HX

to

unchanged

so

that

and

thus
,

3C

(HX
is

C)
small,
the

Since
ence

C>0
is

and

a>0,
and
we

we

have
the
AT

small,

have

T2 < Tx. approximation


=

If/ x

temperature

dif er-

T2- 2

7\
is used

cut
8a
to

Tt
to

\
temperatures
the
and

Note:

Adiabatic
2.13

demagnetization
shows alum
a as

attain
field

below

1 K.

Fig.
ammonium

relief
a

of

the

entropy
of

(due
magnetic

electronic

spin)
A

of

iron
mag-

function

temperature.

1.0

Fig.

2.13.

Ch.

2]

solutions

113

netic
a

refrigerator
Carnot These
0.2

can

be

made

by
the been

using
cycle
to

paramagnetic
as

salt

such

as

this
in

in

cycle
K.
to

(operating
have

along
actually

shown

by
temperatures

the

thick
of

line the

the
order

figure).
of become

used

maintain

According

C),
is
not

if

Hx
correct

is

made

sufficiently
is

large
with
so

for

given
law be
zero

Tu
of

T2
thermowhen

wil it

negative. and dynamics a negative gives demagnetization far by adiabatic


27. We

However,

B)
near
one

inconsistent
0
can

the it
cannot

third

K,
never

that reach lowest


0.003

used attained

T2.
or

Actually, by any demagnetization


volume. dS

absolute

by adiabatic
so

other

means.

The

temperature
K.

is

about

consider

unit

The
=

equation

(dU
ana and

dAQ/71

A)

gives

-L(8J?\ 1,1
The condition

T\dT/M

(?i I,.,) \

\dMJT

-l(8JL\ ^,1

T\dMJT

,.,)

~~^- T
then

B) W

d2S/dM

dT=d2SIdTdM (dUldM)T
=
-

(mtegrabihty

condition)

yields

T2(d(H/T)ldT)M
the
so

C)
side
is
zero

(see
must

problem
be
constant

15,

(i)).
when

As
M

M=f{HjT)
is

right
that

(because

HIT

constant),

Eq.

A)

becomes dS
=

-dU(T)--f
T
hit

/H\
-

\TJ

[H
\T

and,

when

integrated,
S
=

CdU(T) ^--

xf'(x)
H/T

dx

const.

g(T)

"f(^j
work work
To

| f(x)
o

dx

const.

D)

28.

By
process
contact

the

principle
is
a

of
maximum. the cold

maximum

the
is

work obtained
heat

obtained
if
the

through
body
from

reversible

with

(No reservoir.)

is

directly
the

put

in

take

reversibly

body

and

114

SECOND

LAW

OF

THERMODYNAMICS

[Ch. absorbs heat

do

work

we

consider from
x

a a a

Carnot
reservoir
at

cycle
at

which

d'g
while

C|d7'|
heat work

CdT(d7'<0)
=

temperature

T,

giving
does

d'Q0

d'Q

TojT

to

reservoir

temperature

To,

and

which

By
Then

repeating
the

the

above

cycle,
done
is

the

body

can

be
To

reduced

eventually

to

To.

total

work

C{{TX-T0)-T0\o
29.

5
previous
K. take
water.

(This
as
a

is the heat
at

reverse

of
at
we

the 298
to

prot
In heat This order from
can
.)

m.)
cool it the from
at

We

consider
water

the

room

at at

25

C
to

reservoir

initial y
the heat when
at to

298

K
reservoir is also

ice which

273
is

K,
hotter

have
than the
a

and be
process

give
done
is

the

only
reversible.
water

work
Use
a

done.

This in
+

work
which
is

is

minimum
heat
to

when

Carnot

cycle, d'Q
of the

the

d'Q
the where

is
reservoir

taken

the

and

heat
=

d'W
water.

given
The

T'(>T).
dT,
the
C
water

Since

d'Qld'Q'
total K
from

d'Q' T/T',
K

d'W=d'Q(T'-T)jT,
work
273

d'Q=
to

being
to

the 273

heat

capacity
298
is

necessary 298
S

cool
273

dfi
298

/298

-1

U-CdT)
,

298

{298
298 The

log

B98
give
the

273)|.
latent

A)
heat of

minimum
at

work
298

necessary

to

freezing,

L,

to

the

reservoir

is

W2

Lx

B98
water, of heat
The
x

273)/273.
the

Using deg joule joule


cost

the mol

given
and
the

latent
work
=

heat

for

equivalent
x

4.18

specific joule/cal,
work

heat
we

CH20
have
+

18.05
x

cal/
106
at
a

and
which of

W2
S 1.35.

35.8
'

106

joule.
to

total

W=W1
=

Wx =4.64 4.04xl06 W2
=

corresponds

40.4

106/3.6x

106

11.2

kilowatt

hours

Ch.2]

solutions

115

30.

It

is

sufficient

to

show
is

that

Thomson's
Let
us

principle
assume

is that
a

violated

when

Carathe*odory's
system

changed
heat

positive
and

principle isothermally quantity Q.


the
amount

violated. from
a

state

A)
be

to

state

thermally B) and
two states
states

uniform
absorbs be that
a

Letting
of work

the

internal

energy

of

the law

Ux A)

U2

and

received

A,

the

first

Q=U2-Ut-A.

isothermal

adiabatic

We

next

change
process

the
is

system

from
is
the

B)
not

back
true.
states

to

A)
If

adiabatically.
the
work received

This

is

possible
the

if

Carathe*odory's

adiabatic

principle A',

during

first

law

that

0=U1-U2-A'.
From

B)

A)

and

B)
Q
=

-(A
the
amount

A').
system
of
absorbs

C)
heat,

Therefore environment

in
of

the

cycle
does

and Thomson's solution: that


there

violation Alternative
means

(l)->B)->(l), an equivalent principle.


The

Q,
+

from This is

the
a

work

(A

A').

validity
a

of

Clausius'

(or
if
T
=

Thomson's)
is

principle
absolute

exists
For

state

quantity,
adiabatic
process,

S, and,

the

tempersince there is
state

ature,
a

d'Q/T=dS.
total dif erential
in

an

d'Q
(constant). (e.g. x, by S(x0,
from
cannot

0, dS=0
That
y,

and

dS
a

is
set

of

S,
the

it

means

that variables defined which


this
start

S=a

is,
the
=

of

surfaces
Jo>

the
it

space
on

of

state

z).
y0, yQ,

If

initial
a.

is

(xo>
adiabatic surface
reversible

zo),
and
exist

lies

surface

reversible
any

changes

(x0,
be
of
a

zo) z0)
given

Therefore
be
an

all
on

must

this

point
Thus

outside
in
any

surface

reached
reached is

by
state

adiabatic

there

change. always
This
means

change.
Note:
cesses.

Carathe*odory's Starting
entropy,

neighborhood such that states they that Carathe*odory's further principle


from

(x0,
an

y0,

z0)

cannot

be

by
irreversible
one can

adiabatic

principle
includes

valid.
proprove

adiabatic

Clausius'
in
for
an an

or

Thomson's adiabatic
state

principle
irreversible

that

the

inequality.

S, Therefore,

increases

process
y0,

by
states

Clausius' which
have

initial

(x0,

z0),

the

116

SECOND

LAW

OF

THERMODYNAMICS

[Ch.2 side of irreversible


the close irreversible
1 and

smaller
S
can

values
y0,
state cannot

of
cannot

entropy
be
any

and reached
state

so

lie
any

on

one

surface
process.

S(x,
Hence

y,

z)=
we

(x0,

z0)
that

by
there

adiabatic
an

for

exists

arbitrarily
or

neighbouring
adiabatic mole of
processes.

state

which
31.

be mixture

reached
of
two

either

by reversible
gases,
nx pressure,

Consider

mole
p.
to

of
Assume

gas

n2

gas

2 at

volume
is
pure
a

V,
reversible
gas

temperature
process.

and
it
+

that
the
gas

mixing
mixture
2 at

by
to
=

dif usion become


+

Then

is

atVt=

Vnll(nl

n2),
gas

possible T and/?
mixture
1 + 2

separate
pure

and

V2

Vn2j(nx

n2),

II

isothermal
heat

expansion

work

work

IV

1 + 2

reversible

mixing

gas

mixture

Tandp, isothermally
at

without
the
T
one

leaving
volume

any

other each
to to

change
V.

(I->II
The
in

in
this

the

figure).
from

Next,
the

increase
reservoir

of

heat

absorbed
process

temperature
wall the
mix
process,

is of

converted each
containers container

work

(II-> (example
the

I I). 5), exchange


it

making
to
or

combine

two

and
to

work)
it contradiction
was

the

two
was

gases

semipermeable reversibly their original


from
the

Then, is possible
of
=

by
heat

(without
state

(II ->IV->V
reservoir
any
at

I).

In

this
is

whole and
in

heat all
converted
to

obtained
to

heat

the

stage

I ->II This

work

without

leaving

other

change.

Thomson's

principle.

Ch.2]

solutions

117

32.

The
first

heat
law
we

received
have
=

by

this

system,

d'Q,
and
two

is

the

sum

of

d'Q'

and

d'Q".
p" dF".

By

the

d'Q'
The

C'v
a

dT'

p' dV
of

d'Q"
are

C?
equal
dV
R d T-

dT"

pressure/?'
are

and/?"
in

the

parts
Now

always
express gas
p

(p'=p"=p)
and
p V

since dV" in
terms

they
of
d
have

mechanical d7"'
and

dT',

dp
V=

and

dp

equilibrium. using
RT
to

the obtain

ideal

equation,
d V=

RT.

(Multiply
p.)
Thus
we

VI

TIT+

dp/p

by

p V=

RT
n

dpi

d'Q
In

d'Q'
system

d'Q"
d'Q
the is

(C'r
a

R)

dT'

(C?
of

R)
three

dT"-"

(T'
T,

T")dp.
A)
T" and
/?.

this
now

dif erential
that

form

variables,

We

apply
integrating

condition

Xt
has
an

dxx
i.e.

X2

dx2

X3

dx3

B)

factor,

2i

=0

C)
+

(see X3

Note
=
-

1).

Setting

xx
+

T',
get

x2

T",
left

x3=p,

(/?/ ?)

(r'

T")

we

the

side
+

of
=

Xt C)

Cy

R,

X2

Cy

and

-(C'y+R)-+
which
cannot

(C'v
Cy^Cy.

R)-

-(Cy
P

C'y),
A)
does
not

D)
have
such any

be

zero

since exists

Therefore

d'Q
factor,
x2,

of

integrating
Note
1:

factor.
If
+

there

an

integrating
=

l(xux2,
then
we

x3),
have
=

that

X(Xt
By
eq.

dxx
setting C)
2:

X2 50/5*!

dx2
=

X3
XXX,

dx3)

d0(xl5
=

x3),
and

d(f>ldx2
=

kX2,
etc.

d(f>/dx3
eliminating
a

XX3.
X

520/5xt
is

dx2
as

d2(f)/dx2
condition

dxx,
of

from the
exist

them,
temperfor

derived This
to

the

integrability.
that,
for
does that the

Note
ature

is

an

example
an

showing integrating
the
to

system
not
a

in

which has

is not
order
we

uniform,
deduce
have

factor
second

necessarily
system
is
be
an

d'Q.

In

from

law that unit

factor,
.

generally
energy

require
entropy

system
mass

thermally
u

integrating uniform.
If

Let

the dM
=

internal

and
=

per

and of
T

respectively.

( )
\dTJy

dT

g(T)dT

(g(T)

is

function

only),

A)

118

SECOND

LAW

OF

THERMODYNAMICS

[Ch.

we

find

from
du
=

ds-

pdv,
+

B)
pdv,

that
Tds
=

g(T)dT ()

and

also

()
of
T

C)
(proof
of

by

definition.

Therefore
rewrite

cv
as

is

function

only

(i)).

Next,

B)
gives

dv

(Tlp)ds-(g(T)lp)dT

using

A).

This

the

equation

and

\PTJP
/dv\

\dT/p

\Pp/t
Eq.

T/ds\
P

E)

B)

also

gives

the

Maxwell

relation

which

is

obtained

from

B)

by

first

writing

the

equations

and

then

by

equating

d2u/dp

dT

and

d2u/dT

dp.

Eqs.

E)

and

F)

give

which

in

fact

means

(ii)
variables,

in

the

problem.
and
T.

In Then

order
we

to

see

this,

consider

as

function

of

the

x=p/T

have

pVh

Jto\(dx\

\dxJr\dpJT

T\dx)T'

U9v\

C h.

2]

solutions

119

Eq.
or

G)
that
=

thus

means

that

{dv/dT)x
v

depends
eqs.

only C)
and

on

cp

T(dsjdT)p,
v

x=p/T D) give

(proof

of

(ii)).

By

the

definition,

Since

depends

only

on

x=p/T,

eq.

(8)

gives
X

P\dTjpTherefore
Let

T2\dx)Tfunction molar and


V

dx'

cpcv

is

also
be

of

only.
heat
volume.
at constant

34,

Cy

{dUjdT)v
energy per

the

specific
the
d
-

volume,
we

the

internal

mole

molar

Then

have

dSl\
(using
writ en

d2jJ

\r(dp
van

(i)
as

of

problem

15).

Since

the

der

Waals

equation

A.17)

can

be

v-b
the
on

v2
is independent have
=

B)
of
V

right
T.

side

of
eq.
I

Using
du
=

A) A)
I

is

zero

so

that

Cv
15,
we

and

depends

only

of
di

problem
+
I

dU\

iv
j

dv

cdTHA
Cv
dT

(
+
<

fdp\
-

This

is

integrated
U
=

to

give \ Cv
dT
+

Uo

(Uo
dif erential
=

is

constant).
is
R

D)
as

With

the

use

of

B)

and
1 T

C),
dU
+

the

entropy

writ en

pdV
T

Cv

dT

V V-b

dV,

E)

which

is

integrated
T

to

give
+

CC
=

dT

log

(V

b)

So

(So

is

constant).

F)

120

SECOND

LAW

OF

THERMODYNAMICS

[Ch. obvious adiabatic


from

35.

Assuming
to

Cv

const.,

the In

equation
the
case

for
of

t/is
an

D)

in

the

solution
eq.

the
of

previous
the

problem.
previous
dS-

quasi-static

change,

E)

solution
4

gives
R
A

Cy
T

dT

Cvdv dl
-

(using

Mayer's

relation),

which
+

is

writ en
y

as

1N

V-b
-

and
This

results
can

in

T(V
be writ en
as

const.

I (V
is

b)y

const.

when

the

van

der into
a

Waals
vacuum

expansion

equation (irreversible!)
T2~Tx
=

substituted.
U
a
=

In

the
so

case

of

an

adiabatic

const.,
1

that

/I

c~v\y2~Vu
24

must

clearly
given
in

hold.
the

36.

As

solution

of

problem

the

Joule-Thomson

coefficient

is

-p-

A) nRTf
n/2a

By
to

approximating
the order of
\
t_

the

van we

der

Waals

equation

as

V+n2

(RTb
\1

a)jV2

I V2,

have

dV\

A+nb/V)

injV)
and

(b^ajRTJ}

,_V(
~

T{

+V\R~f~

)]

where

Cp

is

the

molar

specific
we

heat have

for from
=

constant

pressure.
eq.

If

(dT/dp)H

0 at

Tj (inversion

temperature),

C)
D)

T{
The

2alRb.

critical
=

temperature

is

Tc

Sal27Rb

(example

8,

Chapter

1),

so

that

27^/4.

Ch.2]

solutions

121

37.

The
We

simplest
substitute

way

is

to

use

(dH/dp)T=
and

V-T(dV/dT)p
given
-

((ii)
formula

of
for

problem
V
to

15).
obtain

H=

U+pV
+

the

expansion
+

(B
where
A
=

fi)
A'
const,

2(C
=

y)p
etc.

-(A
P

TA')

(BA-TA'
can

TB')
=

(C
0 with

TC)
the

p+-~, solution
in the

dA/dT,
x

The

limit
absolute

as/?->()
temperature
p V

gives
for them of
a

T.

Thus,
Measure

the the
and

be
at

determined
pressures

fol owing
at
a

way.

given
Do

temperature
the
of
same

quantity extrapolate
a

gas
to
a

dif erent

but

get
reference

limp->opV=A
point
=

(cf.
such is
fixed.
point
=

Fig.
as

1.5). triple
the
From

thing
for of which

at

temperature
the

the

point
desired

water

numerical

value
is

To

273.16

Then

value

the latent

absolute
heat

temperature
of

given

by A/Auiple
is

T\ To.

38.

8Q

TSS

the

expansion,

Lp,

defined

as

/dS\
r

rU fdV\ \dTjp
16).
d0 If
we
use

(i)
T

(using

Maxwell's

relation

(ii )

of

problem

instead

of

6,

[df),~\do)pdT'
Substituting
this
into

(dV\

-fdV\
-(dV/d9)pTd9l

A),
dlogT

we

get

Lp=
/dV\

&T,

or

)JL

Va(9)

This

is

integrated

to

give

The

right
Then

side 9

can

be be

obtained
converted

by
to

numerical
T

calculation,
this

using

measured

values.

can

by

relation.

Substitute
H

M(T
=

v
C

-9)
to

V
problem

as

xH=
we

CH

T-9J
have

A)

into

eq.

C)

of

the

solution

27.

Then

(dU/dM)T-9M/C.

B)

122

SECOND

LAW

OF

THERMODYNAMICS

[Ch. solution
to to

Multiply
dif erentiate

the

two

equations
with

in

B)
to

of
M
we

the
and

problem
Maxwell's

27

by

and

them

respect
Therefore

obtain

relation

(dS/8M)T=

-(dH/dT)M.

find

that
=()
T
-

dCM} dM
and

)T

TfS_
dT of
M

_fd2H

dM
and

\dT2JM
on

that

CM
dU

is

independent
=

depends
dM
-

only.
miM

Hence,

integrating

fdU\ [(su\ \dT

dT, dT (8_E\ +
T

\dM
dT

(dU\ [

CMdT-

we

obtain
U

CM

om2

const.,

and

integrating
dS

dU-HdM
=

=CM

dT
T

M C

dM
,

we

find
S

CM

dT
T

M2
2C
+ const.

40.

Let the

be

the
laws

internal
state

energy

and

the

entropy

of

the

system.

The

first

and

second

that
dU=

TdS-pdV
of the

dl,
From

A) A)
we

where

/ is

the

magnetic

moment

system.

have

Sp/h

\SpJh

Vp/h

\Wh'

Since

d2X/dp

dH=d2X/dHdp

(X=

U,

S,

V,

I),
C)

\dp)n

Substitute

I=xHV'mto

C)

to

obtain

Ch.
or

2]

solutions

123

1 /dV\
_

V\dHJp
Integrate
of
x

J
\
to

fdtf
\dp/Tj
0 to

both

sides
on

with

respect

Hfrom

H,

neglecting

the

dependence

and

(dx/dp)T

H,

to

obtain

where

AV

is the

the
left

volume

Expanding

side,

change. keeping
v 2

We

may

usually
first
term,

assume
we

that
have

AV\V<?\.

only

the

r
change

w
at

41.

By

example
=

5,

(i)
that

for

an

isothermal

constant

volume

we

have

SWmin

dF,

so

V
for

dT
of
constant

)v
volume
dU
=

T2

T2'

which

the

condition

(no

work)

gives

d'Q.
pressure
we

(ii)
so

For

an

isothermal

change

at

constant

have

dWmiIl=dG,

that

8T for

Jp
constant
on

T2
pressure
=

-.2

jT2 .2

r2>

T'

which

the

condition

of

gives
Q.
be
+

42.

Let

the

equation

of

state

for

the

real

gas

pV

=f(p,

T)

A+Bp

Cp2
((ii)

+.

Using

the

relation

(dCp/dp)T=

-T(d2V/dT%

of

problem

17)

we

get

is

the

molar

specific

heat

at

zero

pressure.

Insert

here

the

equation

of

124

SECOND

LAW

OF

THERMODYNAMICS

[Ch.

state

and
to

carry

out

the

integration
Thus
=

noticing
we

that

AozT

and

A"(T)=0

(see

solution

problem

37).

have

Cp0)
Therefore,
ature

CP+

TB"p

TC"p2
values this
set

+-.

A)
of
p
at
a

the
T
can

measured
be

values
to

Cp

for

dif erent

given

temper-

extrapolated point equation


be

Cp0)
Tc)

by
and

equation.
p
/

43.

Let

the

critical

(pc,

Vc,
becomes

=p/pc,
7\

v=V/V0

and

t=T\Tc. A)

Then

Dieterici's

(see
ficient

problem

12,

Chapter
is

1).

The

condition
V=0
or

that

the

Joule-Thomson

coef-

(dTldp)H=0

T(dV/dT)p-

SK
Dif erentiate
to

A)

with

respect

to

t
r.
=

at

constant

p and

substitute

B)

for

drjfdt
C)

get

4/(8-t).

Eliminate

t)

in

A)

with

this

to

get

D) Fig.
ature

2.14
curve,

shows other the

the

plot
of the

of

this

relation.

On

one

side
in
a

of

the

inversion The
The

temper-

(dT/dp)H>0;
side

cooling
curve,
curve can

takes

place

Joule-Thomson
occurs.

On

the Similar

(dT/dp)H<0:
for
be
/

heating
to
a

expansion. figure
equation

also

shows of
state

experimental
considerations
is

H2.

applied
i

van

der
8

Waals

gas.

1\

3t
in
terms

E)
Chapter
1). This
gives

of

the

reduced

variables

(see

example

8 in

and

hence

'dx>\

8//

2
it

dtjv

3/V

tJ

Ch.

2]

solutions

125

Substituting

the

condition

T(dV/dT)p-

V=0

or

!)-,.
into

G)

F),

we

have

with
3

E)
3 2
IT

V2
20

Dieterici

15

10

t=T/Tc
Fig.
2.14.

126

SECOND

LAW

OF

THERMODYNAMICS

[Ch.

and

hence
9/
V

1\

(8)

Equations

(8)

and

E)

then

give
18/

A2_8

or

1/C-2Tit).
24^31:-12t-27.
point
of
on

(9)

Substituting

(9)

into.(8)

we

find

p
This is
2.14

A0)
the
=

the
this

locus
locus

of

the
has unit
a

inversion
maximum

p-t
t=3.
Joule-Thomson

diagram.

As

shown

in

Fig.
44.
If

9 at

the

volume

for

mass

is

v(=

l/p),

the

coefficient,

fi,

is

given

by

(problem

24)

where referred

is
to

the
an

absolute

temperature. temperature

If

c'p
dT

and

are are

the

values
to

of

cp and
and
n

/j,

empirical

scale

0, they

related

cp

by

Similarly,
a,

(d^
temperature

Bb)

If
so

9 is the that

dv/d9

v/9.

by this Therefore,
j

gas

thermometer, with C),


T
j
_

it is defined

by

const,

v,

A)
AO

becomes

9
or

dT

dlogfl
dlogT

D)

Ch.

2] is

solutions

127

which

integrated

to

give
los Tt

Ol

)
known the the

dO

E)
from
the of
measured

where

f(9)
p,

is
the

defined

by
heat,

D) point
of

and

is

values

of

the
If done

density,
is

specific
a

c'p,
E).

and

Joule-Thomson
calibration

coefficient,
Tt
and

ft'.
6t
can

To

known
numerical

for

standard

90,

be

by
45.

integration
to

According

A)

in

the

solution

to

the

previous

problem,

we

have

and

therefore dT
T
v

dv
+

dv

1
1 +

dp
p
*

1 1 +

ficp
=
-

pfiCp

pficp

Insert d
into

log
and

p/d0
carry

a0)~

(a

0.003

669)

this

equation

out

the
r

integration:
adO
1 +

log=
Put

T T To

aO

1 +

pncp

r=100+T0

(f=100):
/

100

8v
The

100\_ "w
would
be the

<xd0

J
0

first
=

approximation
Therefore
to

to

use

(\+pficp)~1
we

lf

which

gives B)

To
and

I/a.
write

improve

approximation,
=

put

(l+p^p)-1
A)
as

l+/
100

log(l
Further,
we

^)
T0
=

log(l
and

100a)
rewrite

a
o

f
as
100

-j^

d0.

C)

may

put

a~1+x

C)

128

SECOND

LAW

OF

THERMODYNAMICS

[Ch.

Since
the

and

xaftl
side

100a)
of

are

small

numbers
the
100

compared
first
order
term
100

to

a,

we

may

expand
obtain

left-hand

D),

take

only

in

x,

and

9.

E)
data

The

function the table.


=

g(O)=f(O)/(l+aO)
Note 0.98
are
a

is
necessary

obtained
of
=

from units.

the

given
1 cal=4.18
x

as
x x

shown

in
1
[i

the
x

conversion
so

107

erg,

kg/cm2
and of
x.

106

c.g.s.,

that
in

p/jcp
the
is units

p//c;-4.18
in for

107/0.98
Since

106
the
necessary

(where
given
eq.

c'p
Thus,

the

given only
four crude

values

the

problem).
two

value
for

has
a

significant

figures,
sufficient

only
this
*

figures

are

integration
=
-

problem.
/(g)
-

Then

E)

gives
-

0.269x

0.00183, 0.68,
'

si6)
_

or
x
_

0 25
50 75
-

0.00329 0.00258
0.00198

0.00329 0.00235

t luS

0.00167
O.OOO88

To
Divertissement

@.003669)
7

-0.00153
-

-0.00120 0.00121
-

0.68

273.2.

ioo

Kapitzd's
was

helium

liquefier.
in
1908

liquefied
to

by
helium

H.

Helium, Kamerlingh
is
necessary

the the inversion


helium. for the

last Onnes.

t)f

the The

"permanent
reason

gases",
why
of

it

is
Jouleto

so

dif icult Thomson

liquefy
effect is In the for
at

that low
for

temperature

the

temperature
effective. cascade
first

is extremely therefore

Precooling
the

to

liquid
effect
was

hydrogen
be
in
com-

Joule-Thomson effect
In
and

original hydrogen
present,

method
and

Joule-Thomson
for helium. used
of

used
most

then
is

the
the

method,
first

monly by applied Kapitza


this
In
at

used
an

hydrogen
expansion.
The
for

not
use

step
later
of
a

is

replaced
was

adiabatic

adiabatic of
is
an

expansion
air
and

first
P. L.

by
for

Claude-Heylandt
helium.
to

liquefaction
machine

The

Collins
the

example
of

by liquefier
let
us

of look

type.
order
understand

basic of is
process
pi

processes

the

figures
insulation

showing diagram
of the
pressure

schematic helium.

sketches
For

of

the
the

liquefaction, liquefier
we

and
assume

of

the
that

en-

tropy-temperature
heat

simplicity,
that

the

the
7i
sure

pipes (~
pz

300

negligible. K) and (for example,


is heats
up.
to

system In the
15

perfect
a

and
->

drop
gas

of
to

pressure

along
temperature

(~
This

atm)
is
an

b, the helium is compressed


adiabatic
7i
to

of
a

higher
so

pres-

atm).
cooled 77

the

gas

It 7s I and

is

then

back

by

water
as

compression (b ->
it

that
gas

c).

The

is

further
heat

cooled

(~
the

K)

exchanger

liquid

by liquid nitrogen

nitrogen
bath

flows

through

the

(c

->

d).

Ch.2]

SOLUTIONS

129

compressor

helium

gas

supply

TI

heat

exchanger

II

Joule-Thomson

valve

liquid

container

liquid

draw

off

valve

Fig.

2.15.

Kapitza

system

of

helium

liquefier.

130

SECOND

LAW

OF

THERMODYNAMICS

[Ch.2
1 and 2.

Then duced conditions.


gas
to

the
an

gas

is
the
down

divided

into

two

streams,
where the
gas and

Stream

1 is

intro-

"expansion"
By
adiabatic
from the

engine expansion
73
to
stream

expands
entropy,
goes

under
AS the

adiabatic
=

(constant (d
->

0)
heat

the
ex-

is
the

cooled

7*4
stream

j)
of

through
gas.
passes

changer
to

I,
compressor

cooling

other
>

B)
temperature

helium
74

It

is

then
It

returned the heat

(j
I,
is

a).
to

The

2, which

through
is

exchanger

cooled

the

(d>-e).

then

led

Fig.

2.16

T-S

diagram

of

the

liquefier.

to

the

liquid
at

container

through
it
enters

the the

Joule-Thomson
must

valve.
be

The

tem-

perature

which
so

valve

lower
can

than
lower

the
the
rest

inversion

temperature, ature,

that

the

Joule-Thomson
some

effect

temperof
the
gas

and

thereby

liquefy

part

of

the

gas

(h).

The

Ch.2]
goes

SOLUTIONS

131

through
stream

the
to

heat

exchanger (e
-*

II

(i

j),
the
process

which
compressor
can

serves

to

cool
then
*

the

in-

coming
stream

Ta

f)
of
per

at

the

Joule-Thomson
back
to

valve,
be

and

joins
as

The

lows.
process

point j and efficiency If H is the enthalpy (f -* g) is characterized


1 at the

goes

(j
calculated
the

a).
fol-

liquefying

the

whole
1 mol

of

helium

gas,

Joule-Thomson

by

where of
gas

the

subscripts
at

denote
g,

to

the

points
+

in

diagram.

If

rjo

is

the

fraction

liquefied

then

Hg
where
is cooled

rjo)
in

Hi,
the
gas
state.

point
down

h is

in

the

liquid
from

state
e

and
to

i is
amount

When

the

gas

in

going

f,

an

of

heat,

He

Ht,

must

be

2
s

cal/deg'g

Fig.

2.17

Entropy

of

helium.

132

SECOND

LAW

OF

THERMODYNAMICS

[Ch.

transferred

to

the

gas

coming
He-Ht
=

out

of

the

liquid
(Hi
-

container.

Thus

we

have

(lthese

no)

Hi).
we

By

eliminating

Ht

and

Hg

from

equations
Hi
-He

obtain

where

is

the

fraction

of

gas

in

stream

2.

Chapter

THERMODYNAMIC

FUNCTIONS CONDITIONS

AND

EQUILIBRIUM
The

third
but

law
the

of
most

principle,
thermodynamics. thermodynamic
of
like
an

thermodynamics important
The
use

is

introduced
is
to

in

this

chapter
the functions

as

new

thing
of
the
can

various be
be
some are

clearly thermodynamic
therefrom that

understand

structure

and

the

equations
in
the mathematics,

exercise
in

whic?
but

derived

seems

somewhat
wil
not

t is_.to
wil

hoped

the
to

reader the
since
to

lose the
/

himself
The basis

calculations
of

give

thought
repeated
In here

physics
they
this,
wil
the be

involved."
form thermodiscussed

thermal
for

equilibrium applications
inequalities be applied
and
to

conditions

thermodynamics.
Le

relation

dynamic
and

Chatelier-Brown's

principle

wil

simple

systems.
Fundamental

topics

3.1.

THERMODYNAMIC

FUNCTIONS

system

in

thermal

functions (or thermodynamic of as functions pressed the quantities concerning of thermodynamic functions
derived
as

equilibrium potentials) suitable independent


system
and
are

is

characterized

by
are

which variables.
all

extensive The various

derived so-called

as

thermodynamic quantities thermodynamic derivatives partial


relations

ex-

relations
of

between

thermodynamics).
the
concrete

form

the

Thermodynamics thermodynamic
form for

functional
or

thermodynamic analytical (the quantities can make general only but it cannot functions ( 3.8), This each must particular system.
these

the

are

formulation
statements

of
about
the

determine be
for each

determined
thermoIf
a

empirically
There
is
a

by statistical particular
These function

mechanics.
set

of
are

variables
called the
as a

which natural

is

convenient

dynamic

function.
the

independent
of

variables.
natural

thermodynamic
variables,
it the summarize

is
of

given
properties
another

function
are

its

independent
but
if
not

thermodynamic
a

is

given
to

as

function all
where

set

of and

sufficient
two

determine
in
the

the

cases

U(S,
fol owing
their

V)

thermodynamic is given
table
the

completely independent properties.


where
and

determined, variables,

this
compare

is
We for

(Example:

U(T,
thermodynamic
the

V)
related

is total

given.)
functions
dif erential.

wil
a

typical
variables

homogeneous

system,

natural

134

THERMODYNAMIC

FUNCTIONS

[Ch.3,l
2000

1500

-1000

0.8

0.9

1.0

1.1

1.2

V/Vo

(a)

Internal

energy

0.7-^
T

(b)
Fig.
3.1. Some

Entropy
functions
for

examples

of

thermodynamic

solid

sodium.

Ch.

3, 1]

THERMODYNAMIC

FUNCTIONS 500

135

v/v0

(c)

Helmholtz

free

energy.

-10000

-5000

o-1

-5000 10000 20000

30000

atm

(d)

Gibbs

free

energy.

136

THERMODYNAMIC

FUNCTIONS

[Ch.

3,

Table

3.1

Thermodynamic
(Definition)
Internal U
energy

functions

Natural

variables

Total

dif erential

S,

V, Ni

dU

TdS

-pdV+XfadNi
+

C.1)
+

Enthalpy
H= U

+
free

pV
energy

S,p,Ni
T,

dH

TdS

Vdp

'Lfi dNi

C.2) C.3)

Helmholtz
F=
U-TS

V, Ni

dF

SdT-pdV+Xfi dNi

Gibbs

free

energy

(thermodynamic potential)
G
=

T,p,Ni
+

dG

SdT+

Vdp

XfadNi

C.4)

pV

XNifa
t, U,
v,
m

Grand

potential*
J=-pv=F-G
/
=
-

SdT-pdV-'LNidfit

C.5) C.6)

Entropy
S

V, Ni

dS

f
iNi

Massieu
?
=

function

-FIT
function

~,

V,

Ni

\f)

C.7)

Planck
0
=

-G/T
function

lT,p,Ni
l

INt

C.8)

Kramers

f
*

ym
name

'

dq
widely
this
way

\TJ
accepted.
because
In
recent

This

function

has

no

particular
called

literature
to

of

statistical canonical

thermodynamics partition
3.2.

it is sometimes

it is related

the

grand

function. LEGENDRE TRANSFORMATION


a

In

general

thermodynamic
has
dL
=

function,
the

L,
total

with

x,

y,

z,. .

as

its

natural

independent
where
of
L

variables

fol owing
Ydy
of
x, +

dif erential

(Pfaf ian

form):

Xdx+

Zdz+-~,
The

C.10) fol owing


transformation

X,
and

Y,Z,. .
the

are

all

functions

y,

z,. .

independent
L
->

variables

Xx,

and

thus

dL

dX

dy

dz

Ch.

3, 4]

definitions

137

is

called
in
or

the
Table Besides S.

Legendre
3.1
are

transformation.
derived

The

various

thermodynamic Legendre
transformations
there 3.1, instance,
are
a

functions
from

shown
U

by
listed
which
are

successive in

the

functions

Table
for

variety
the

of

thermodynamic
energy

functions

U(S,
respect
electric field

V,
to

xt,

x2,. .,

Nt,
xlt

N2,. .)
x2,. .,

with
as

the

variables

rather
tions.
3.3.

dif icult

strength, to give

magnetic
a

derived, by successive Xlt X2,. . field strength,


to

from such
and
so

internal variables

Legendre representing
strain of

transformations forth.
It

is

proper

name

each

such

thermodynamic

func-

GIBBS-DUHEM

RELATION

S dT

dp
with

Y^Nj
respect

dnj
to

0.
V
as

C.12) only.
extensive
Since the

Here free

we

explicitly
has the

consider

work numbers

Gibbs
it is

energy

particle

Nlt

N2,. .

variables,

obvious

that

Dif erentiate

this

with

respect
I

to

and

setting

1,

we

have

Z^/(
Since

(Euler's

equation).

dG\
from
eq.

C.4),

this

can

be

writ en

as

G-ZNji ji-ZnjGj).
By
3.4.

C.13)
we

substituting
DEFINITIONS DYNAMIC

this

into
OF

dG

of

C.4)

have

eq.

C.12).
AND

THERMODYNAMIC

QUANTITIES

THERMO-

RELATIONS

1)
heat

Heat

capacity,

specific
at

heat. volume:

By

eqs.

A.10)

and

B.12)

we

have:

capacity

constant

j'

means

the

set

of

Ni,

1, 2,

. .,

other

than

138

THERMODYNAMIC

FUNCTIONS

[Ch.

3, 4

heat

capacity

at

constant

pressure:

2) First C.1)-C.9)wehave,

partial

dif erential

coefficients

of

thermodynamic

functions.

From

^
/ Co

8S

JVtN
\

-T,
\u
1
=

/S>N
\
=

\viy

j/s,v,Nj'
^*^

/
'

Co

.P

\
=
~

ft]
T
'

\dUjv>N

\dVju>N
j

T'
I
=

WA.k.n/
V
>

C'16)

"

H-j>

w-^'y

(dG\

=~S,
are

fdG\

=K,
here
In

( )
other

fdG\

=iij. functions.

C.18)

Derivatives

not

listed

for
a

thermodynamic
system

3) Partial 7=1,2,. .,

molar the

quantities. quantity

multi-component
by

with

components

defined

$j
mole
number
of

C.19)
component./
and

is the
^
is
an

partial
extensive

molar

quantity
variable.
For

where

rij

is the

example

Uj
-

dU
=

(partial (partial

molar

energy), enthalpy),

Hj

dH
=

molar

Sj
j

(partial

molar

entropy), volume),
free

\dnjJp

(partial

molar

(partial
all

molar

energy).
being
kept
constant.

Subscripts,

N,

indicates

dif erentiation,

Ni,

Nt,. .

Ch.

3, 4]

definitions

139

In

4) C.10)

particular, Reciprocity
we

G}
theorems have

is

none

other

than

the

chemical From
etc.

potential
the

per

mole.*

(Maxwell's

relations).
=

total

dif erential

dy
This
is

ox

C.20)
of
eq.

the

condition
dL

for

the

left-hand

side
or can

C.10)
condition
writ en

to

be

total
of

exact

dif erential,
relation
These

(integrability
to

condition,
eq.
are,

existence be
not

corresponding
Maxwell
relations
For

C.20)
of
eqs.
course,

easily

for

eqs.

all
and

independent C.18)
we

L). C.1)C.9). (see note

The
to

example

2).

example,

from

C.17)

have

(8S\
and from

\dvJTtN
C.7),

JSp\

\dTjv>N'
[-}
been
we

(8S\

\dpJTtN
=T(1
in
treat

=_(dV\

\dTjPtN
-p.

)
Some of these
have

C.21b)
and

already
in this

obtained
can

the

examples
more

problems
functions

of

Chapter 5) Relations
and considered

2, but,
derived

the

thermodynamic
as

chapter, by transformation quantities


of their

them
derived variables.

systematically.
them It
are

of
that
natural
are

variables.

Thermodynamic
from is variables
One
not

always
in derive often

functions
to

often the formulae

necessary

thermodynamics
relations
between

suitably
dif erential

change

independent
coefficients.

and

related

of

or,

in

form

more

convenient

for

memorising,

'dx\

fdy\
use

fdz"
of the Jacobian

1.

C.22b)
transformation

It

is

also

convenient

to

make

d(u,
d

v,. .)

d(u,
o

v,. .)

ld(x,
d

v,. .)

(x,

y,. .) \

(?, r\,. .)/


=

(?, rj,. .)
C 24)
molar free
energy,

especial y

0XJy,z,. .
*

d^v^) o(x,
for

y,

z,. .)
(partial
Gibbs

In

this
per

respect

there molar

are

various
energy,

names

Gj

free

energy

mole,

free

etc).

140

THERMODYNAMIC

FUNCTIONS

[Ch.

3,

3.5.

THE

THIRD

LAW

OF

THERMODYNAMICS

(NERNST-PLANCK

THEOREM)
The

limiting density
standard

entropy value
or

of
as

chemically
is
eq.

uniform
goes
to

body
absolute
to

of finite
zero

the It

phase.
state

temperature therefore

density regardless
the
state

approaches of pressure,
at

convenient

take

0 K

as

the

(see

B.11))

by
limS
r->o

assuming
=

S0

0.

C.25)
The

Then in this
Some
one can

the
way

entropy
is sometimes

at

any

state

is the
may

uniquely
absolute
be
zero

determined.

entropy
First
any
means

defined
of

called conclusions
the and

entropy.
drawn
from

important
never

this

theorem.

attain

absolute

of
second,
similar

temperature
the

by

all, (unto

attainability expansion approach


great

of

absolute
the for

zero),
some

and other

coefficient
zero
as

specific quantities
zero.

heat,
are

the

thermal bound also has

temperature
chemical
theorem
was

approaches
reactions

This

theorem
of the

significance Historically,
and the second

(see
deduced from

Chapter
a

4, 4.15).
number

this

experimental
it
is
a

facts, principle
and

therefore,
established
as

like
an

the

other

principles
law. of based.

of

thermodynamics,
with
of

empirical
a

law,
of

it atomistic
of

forms

system
is

Together principles
statistical
nature

zeroth,
on

the

first,
the law

axioms

which third

whole
From

logic
the
consequence
a

thermodynamics
the

more

is
motion
3.6.

viewpoint quantum-mechanical

of

mechanics,
of the

the

microscopic

of

matter.
BETWEEN
TWO

EQUILIBRIUM
two

SYSTEMS

When condition

systems
may

A
stated

and
as

are

in

1) mechanical 2) thermal 3) mass


Proof:
If

fol ows, action (mechanical action (heat exchange): action (material exchange):
be consider
an

thermodynamic depending equilibrium): TA TB,


=

contact,
on

the

equilibrium
the
contact:

the pA=pB,

nature

of etc.*

i ^=$.
system,
the

C.26a) C.26b) C.26c)


of the

we

isolated

equilibrium

condition

composite
We

is

(see
the

2.10,

aj)
SA
+

SB

max.

C.27)
from
the

also

have

fol owing

auxiliary

conditions

fact

that

A + B

is

isolated
*

When
cases

the

boundary
are

is not omit ed here

flat

and

surface

tension

is present,

the

pressure

is not

the

same.

Such

(see

Chapter

4, 4.3).

Ch.

3, 7]

EQUILIBRIUM

CONDITION

141

UA+
So the

UB

const.,
are

VA
writ en

VB

const.,

A^
+

Nf

const.,

1, 2,. .

conditions

as

<5SA
SUA
By
+

<5SB
+

O,
=

C.27')
0,

SUB

0, SVA

SVB

0,

SNf

SNj

1, 2,. .

C.27")

C.6),

C.27')
SV,-

gives T by
T

TB

which

becomes,

C.27"),
T

JA
are

Conditions

C.26a)-C.26c)
under the

obtained
restrictions.
FOR A

from

this

by

considering

possible

variations
3.7.

prescribed
CONDITION

EQUILIBRIUM
condition summarize
it for

GIVEN
was

ENVIRONMENT

The
we

thermal
in
a

again
environment

equilibrium general
The
at

given
under

in

2.10
consideration
pressure

and

3.6.

Here is in

form.

General
contact

equilibrium
with of
the

condition.
chemical When
the

system

temperature
makes
a

Tie\

/?(e),
and
is

chemical
acted defined
on

potential by forces SU, SS, circumstances,

they'-th

component
system
and

SV,

X/e). SNj(j=l,

fi(f)(j=l,2,. .)
virtual
under

displacement
the

by

2,. .)
the first
=

Sxt(i=
A.5))
5V
-

1,2,. .)
gives

above-mentioned

law

(see
{e)

d'Q
By
the

second
SU-

law,

such

displacement

wil

be

unrealizable
-

if
>

T(e)

SS

pie)

SVin
of

X^(e)
its
most

<5xf

X nle) SNj
form.

0.

C.28)

This
The

is

the

equilibrium
C.28)
8S dU

condition demands

general

condition

U(S,
dv

V,x1,x2,. .,Nl,N.,. .)

dxt
dU

C-29)
a

disT,

i/e>

142
as

THERMODYNAMIC

FUNCTIONS

[Ch.3,7
and variation second
form the
environment.

the

equilibrium
from the
is
zero.

condition condition
See
can

between
that

the

system
order
on

This

results
of

the
remarks

first
in the

of
order

the for
no

left-hand variation.

side
cases.

C.28)
Relation
The

3.8,
be

for

the

C.28) equilibrium
to

conditions

expressed for
are:

fol owing
system

special
work

closed

involving
S, of
entropy,

other

than

that

due

change
for
for for for for

in
constant

volume

a) b)

<5[/>0, 8H>0,
system;

volume,
pressure

V,
p

and

entropy,
and

the

system;
of

C.30a)
C.30b) C.30c) C.30d) C.3Oe)
in
not

constant

=p(e)

S,

the

c) SS<0, d) <5F>0, e) <5G>0, Stability


represent

an

adiabatic
Kand

change;
T=T(e)
The of and the

constant

system;

constant

pressurep=pie)
equilibrium. equilibrium
maximum but

temperature
of
the

T=T(e).

of
unstable
variation

thermal

potential
does

statics exist in the how-

unstable
or

equilibrium C.30a-e)
condition
which
It is necessary

thermodynamics.
first-order
ever,

Condition
is
zero as

C.28)
a

conditions stable.
for

require
does

that
the

necessary

guarantee
minimum
or

the

equilibrium
maximum be

to

be

that
order

not, condition

of

satisfied
for

second in

(or
where

higher
T

order)
and least
V
are

variations Metastable

(cf.
F

3.8). equilibrium.
has is
more

If,
than
two
most

example,
minima, equilibrium
the

case

constant,
of
the

state
state.

which
In

gives
contrast

the
to

value

minima

the

stable

this,

the

most

stable
state

state

variable

Fig.
state
state.

3.2.

corresponding
A

to

larger
is
states

value

of realized

minima in
nature

is

metastable almost
but it

equilibrium
like
wil then
a

metastable

state

often
or

stable
be

state

(example: spontaneously
the

supercooled
or

supersaturation),
action,
energy.

broken
to

by
with

some

triggering
least
free

the

system

transferring

stable

state

the

Ch.

3, 8] INEQUALITIES order
OF

INEQUALITIES

OF

THERMODYNAMICS

143

3.8.

THERMODYNAMICS

In

that
side

the

state

determined
must

the
its

left-hand

of
For

C.28)

be
we

by positive
write

eq.

C.29)
with

be

an

equilibrium
to

state, variation
in

respect

any

neighborhood.

simplicity
V,
fiu

(see
=

B.15))

(S,
(T,
Since
-

xlt

x2,

. .,NltN2,. .)
=

(Ylt
(yt
i
=
-

Y2,. .),
=

C.31a)

p,

Xu
second

X2,. .,
order

n2,. .)
variation

(yu
is

y2,. .),

dUjdY^.

C.31b)

the

d2u

YidYk
t k

SYidYk

2
t

the

above

condition

is

d2u
i k

SYSY^O SY^O

C.32a)

or

Jty,
i

SYt
C.32b)

STSSis
more

Sp 6V
general
is

^SXi
C.32a);
for the

dxt

^dfij
for

SNj^O.
example,
variables when instead

C.32b)
the
set

Relation

than
used

(^i
C.31a),

^2

-

yr>

Yr+1,

Yr+2,. .)

independent

of

it

gives

j/y/rr+l. .

L
Condition

\dyi/yi'Yr+l. .
the

<5>'i<5ifc+

L
variation

L
is

'

'

that

second
such
minors for

order
as

positive.
form of
the

In

order
or

that

the be be

second

order
the
For

variation

the

quadratic
the

C.32a)
coefficients

C.32c)
must

positive, positive*.
*

principal example,
form

of

matrix

C.32a)
m

quadratic
be

0=2
i;
can
k=l

brought

into

diagonal

form
m

by

an

orthogonal

transformation,

Xi

? Ttkyk.

The

positive

definiteness

of

means

that

144

THERMODYNAMIC

FUNCTIONS

[Ch.

3, 8

d2U

d2u

32] d2U

d2U

8Ykl
dYk

d2U

dYk2
C.33)
d2U

W2

d2u

dYk
where

Yki,. .,

Ykn

are

arbitrary

members

of

the

set

Yx,

Y2,. .

The

same

to C.32c). applies Thermodynamic simplest i) The

inequalities
of matrix
the of

A).
conditions, C.32a)
or

the

coefficient

C.33), C.32c)

is
must

that
be

any

diagonal

element

of

positive: C.34a)

SYk2
or

dy

Jy1.. yr,Yk>
Examples
dT\
_

C.34b)

are:

8S

Jy

Cy

C.35a)

cV

dv)T~
dN

dp\

C.35b)
?0.

C.35c)
minor determinant

'

ij

T,p,Ni'
a

is

i ) The positive.

next

For

simplest example,
d2Ud2U

condition

is

that

two-by-two
T

(see
the
ai. .

example
eigenvalues
an
=

5).
ai,

WWydSdv)
. .,an
=

d2U

=~Cy{-]
(aa)
are
=

fdp\
dV

C>36)

of det A

the

matrix det
A

all
^ A

positive. (since
is columns in
the which

Since det
T

we
=

have

det
be

T~lAT

T'1

det of
n

det matrix
case

det
of

T'1
an
. .,

1) by
in).
n

det matrix The


x's

must

positive.
from

constructed

minor principal A by choosing form finite is


a

the

corresponding
of
be
0
must

determinant and

rows

corresponding
are

quadratic
to
one

special
it

allowed definite

take that

values.
the

Thus minor
minor

must

positive.
be be

By

the only applying

(h, iz, corresponding


the

previous
for
a

argument,

finds

positive

form

0,

every

principal principal

itself
must

positive.

Therefore,

positive.

Ch.

3, 9]

LE

CHATELIER-BROWN'S

PRINCIPLE

145

Thermodynamic
variables
in

C.31a)

inequalities or C.31b),

B).
the

If

(Ylt

Y2,. .)

and

(y1,y2,---)

are

the

inequalities

C.37a) C.37b)

dyjYk
must

hold;

e.g.

dsjp

\dsjv

or

<(j
dp_
dV

/8S\
,

so

that

Cv<Cp;

C.38a)
C.38b)

dp\

Proof

of

C.37a):

3Yjyk

d(Yityd

d(yi,yk) d(YhYk

8(Yh

Yk)

dYjYk\dYk)Yi

%)
where the relation

C-39)

(Maxwell's

relation)

SYk)Yi
and

>t\

=(Sn\

d2U

\dYjYk
Equation

dY{dYk
C.37b)
is

equation (problem
LE

C.34a)
11).

were

used.

proved

in

similar

fashion
3.9.
Le

CHATELIER-BROWN'S

PRINCIPLE

Chatelier's

disturbed
such
a

by
way
as

the
to

principle. application
diminish
A.

When
of
an

given
action,

system

in
a

an

equilibrium
reaction, interpretation
of
the of
a,
occurs

state

is
in

A,
is for
a

direct

This is
a

principle
condition
1

inequality
Example:

C.34a, Suppose
T.

b),
two

which

physical stability
in

of

the

equilibrium.
at

temperature,
ature

If

the

bodies, equilibrium
heat
starts
to

and
is disturbed
flow
AT.

2,
from The

are

equilibrium
an

the
the

same

by
1 to

increase
2

temperThis
tends
means
a

of
reduce

(action
the

A),
temperature

(reaction
of

a).
heat,

to

dif erence,

transfer

SQ,

146

THERMODYNAMIC

FUNCTIONS

[Ch.3,9

heat

T+A7'

=?>

Fig.
decrease
ature

3.3.

of The
Le

in entropy, 1 decreases

SS=

-SQ/T,

of
its

1:

since

CT/dS)v
-8Q/CV.
a,
are or

T/Cv
defined

>

0, by
is

the

temperin

by
A,

5T=(TICv)dS=
and direct When

Note:

conjugate
by
which
tation
Example.
an

action, thermodynamic
A,
to

quantities

reaction, (yt and


a

changes
disturbed direction

Yt
system
due
to

Chatelier-Brown's

principle.
the

in
A

Yt and yt). equilibrium


occurs

action,
tends

indirect
the

reaction,
action,
A.

b,
This

in

the

decrease

principle

is the

physical

interprether-

of

the
A

inequality
material is

C.37a,
enclosed The

b).
in
a

cylinder
is

mally
pressure,

conducting
p.

material. Now
The

piston

in

heat,
direct

AQ,
reaction

is the

supplied
is
pressure
a

(action,
temperature
may

disturbed.

and both of a piston, with an external equilibrium the A) and equilibrium of the material rise, AT,

is

(reaction, change, C.38a)


This

a).
the
means

Besides

this,

change reaction,

and

also

the

volume

may

piston
that

being

displaced

(indirect

b).

The

inequality

(AT)v>(AT)p,
means

(AS
change
when
if it is

AQIT).
when
the

that

the

temperature
than
moves,

larger
in

volume

change
This
as

is also

inhibited
means

(fixed
that
the of the

piston) piston
action,

is

allowed

(movable
such
a

piston).
way
to

it

is

movable,

diminish

the

effect

A.

displacement

Fig.

3.4.

Ch.

3]
Divertissement On
can

examples

147

8
names

the be
Thomson

of
in

thermodynamic
the
and
is
was
erwarmen

functions.
of
R.

The

word The

seen

works and also and introduced

Aristotle

but

"internal

W.

A852)

J. E.

Clausius
like the
to

A876).
unit

"energy energy" portion


derives
who
Onnes

6v6pyeia"
is
"en"

due
means

to

capacity "Entropy" ?vTp67teiv=verwandeln tity. "Enthalpy"


work.

Inhalt=

"ergy",
attributed
means

"erg",

from?pyov
took
it

Clausius

A865)

from
quan-

by
which
means

Verwandlungsinhalt=change H. Kamerlingh
Warmeinhalt.
"Free
of

A909)
Gibbs
is

from

6v$&>jrelv=sich
the
heat

W.

called
to

it
von

function

(for A882),
and

constant
means

pressure).
that
seen

energy"
internal dF=d'A the
energy for

due

H.
can

Helmholtz

part
the the The

the call

that
an

be

converted

into process.
energy,

work,
It
U
so

as was
=

in

equation
to

isothermal

quasi-static
the but

customary
F
now.

internal
this
was

TS,

gebundene
Gibbs

remaining Energie
energy

part,

TS,

of
pres-

(bound

energy),
to

is not

common

free functions

(for
used often
Onnes
gave

constant

sure)
freie
names

introduced
Thus in

by
and

Enthalpie.
German
on

but Gibbs, the thermodynamic in English. of


to

German

scientists

call dif erent the


names,

it

die

have

Further,
"thermische

equation Zustandsgleichung"

the

state: to p

Kamerlingh
=

sche lat er

Zustandsgleichung"
"kanonische

U(S,

p(T, V).

V)
M.

and

the

name

"kaloricalled the

Planck

A908)

Zustandsgleichung".

Examples
1*

Prove

the

concept

(i)
and the of

The the

fol owing of enthalpy. enthalpy


work
pressure
source

two

statements

which
is
exerts

give
to

physical
energy
a

meaning
of

to

the

of

system
which
the

equal
on

the

internal

the

system

the
under

system
the
constant

pressure,
pressure

p(e\

equal

to

uniform

of

system,

p.

(ii)
it
is in

If

the

state

of

the

system
before
to
or

changes
and
in
increase

p(e\
heat
of

and
the

thermal

by the change
Solution

system
was

equilibrium is equal
reversible

after

the

the

enthalpy,

change, regardless

the

absorbed
whether

irreversible.

(i)
A

Consider

cylinder
on a

with

cross-sectional

area,

a,

as

shown external Then


the

in
pressure,

Figure

3.5.

weight
to

is the

due

placed weight
acceleration

weightless
to

piston
the
M
p
=

so

that of

the of the the

p(e\
if g is the
pressure

is

equal

internal is
the
=

pressure
mass

gas.

gravitational

and

weight,
is
V=

is

pie)
volume

Mgl<7.
of the
gas
az.

A)
Consider
the

If

the

height

of

the

piston

is

z,

the

148

THERMODYNAMIC

FUNCTIONS

[Ch.3
at
on
a

weights
work
source.

on

top
energy

of

the of the

piston
the level

and of
on

on

the

side

constant

level side
as
=

as zero

the

external

Taking
the
energy

the the
the

potential
is in
as

weight
of
the

fact far
it
state

system

weights piston composed


earth's
the
energy

the

the

point,
energy
the

the

becomes

of
existence of

the the

Mgz. Ue (This and weights


and the

earth,
of

but its

as

is

implicitly permissible
we

accept
to

constancy

call
dM

Ue

weights.)

Fig.
Now
gas

3.5.

consider

the

change
the

in

the
energy
+

internal of
=

energy the
gas
+

of
we

the

entire

system,

plus
dU*

weights.
=

If

internal
=

is

U,

have
=

by
+

A)

dU
dH.

dUe

dU
an

d(Mgz)
arbitrary
the

dU

d(paz)
we

d(U
suppose

pV),
U*
the
terms
=

or

dU*
the

Except

for

constant

may
on

H.

When done

by dz),

our

dM

is

auxiliary hands, equal

weight

on

side,
=

dM,
dU
in
+

is

put

the

piston,
order

work
like

dM-g(z
to

dz)
first
=

dM-gz
term

(neglect
dV
gas

second

Vdp.

The

dU*
is the the the
are

dU
of

dp
dF

change height
work

in of
source.

the

internal

energy

the
V

and/?

(due change
external

to

the

change
energy

of of
and

the

piston)
Note
that
to

combined
the
gas

with
pressure/?

dp
and

is and
thus

the
the

in

the

pressure,p(e\
(M
are

always
describe

assumed
the
state state

be of variables

in the

which determined

equilibrium purely
of
the

the

variables
source

z)

mechanical
thermal

work

uniquely

by

the

system

(gas).

Ch.3]

EXAMPLES

149

(ii)
work

According
with
the

to

the

first

law

(assuming
that
due

that
to

there volume

is

no

exchange
we

of have

surroundings

except

change)

for

change
is
the both
constant.

from work
at

an

equilibrium
if
the 1 and
+

state

1 to

another
the proper

state

2, where
p

the

pressure

/7(e) /7(e),
holds

(Even
the
state

pressure

of
is the
state

system

is

not

always
Since

equal

to

A=p(e)(V2V1)
the
-

expression.)
we

p{c)=p

2, obviously
+

have
=

(U2
(This Although
work
Note:
source

pV2)
His

(U,
called
as
an

pVx)
the

H2-H1

Q.
is

is

the

reason

why
were

heat

function.)
the

gases

taken

example,
of the

argument

general.
air.
C

The

could

be 3.6

something
the
=

dif erent.
relief

critical

Figure point.

shows

{dHfdT)p

Cp

is

the

heat

enthalpy, capacity

H(p,
at constant

T),

of
pressure.

is What

the

100

200

300

Fig.

3.6.

Enthalpy

of

air.

150

THERMODYNAMIC

FUNCTIONS

[Ch.

2.

Show

that

for

the

internal
pressure

energy
p

U,
and
the

entropy
heat

S,

the

volume

V, the
at constant

absolute

temperature
the

T,

the

capacity

Cv

volume,

fol owing

relation

holds:

fdU\
Solution The first
15

wL+p~T{^LC
is

(dp\

fdT

equation
in

problem
side
of

Chapter
relation

proved 2).

in

C.21b)
the

(also
second
=

see

examples
we

2 rewrite

and
the

and

To

prove

equality

left

Maxwell's
we

C.21a),

(dSldV)T<N

(dp/dT)VtN.
=_t

Using

formula

C.22b)

have

(dl\
=

By

C.14a)

{dSjdT)VtN

CvjT,
dS\

and

therefore

/dT\
_

Cv
from
in

Note:

Although
it
can

the

first

equality
from of
other

was

Topics, problem
that
2

be transformation

proved

proved equations,
in

C.7)
which
case

in

Fundamental
it

becomes
This

of the Maxwell

variables
not

Maxwell's
For

relation.

shows

equations
2
we

are

all
eq.

of

Chapter
of
that

started
5.

from

independent. C.6).

example, proof
is

in

example
in the

Another

shown

solution
3. Show the volume

problem
the

equation
at

of
constant

state,
pressure,

p=f(T,
at

heat

capacity
of
V. In
+

V), determines Cp (T, p), on


constant

the

dependence
p,

of and
on

the
is

pressure

the
the

dependence

the

heat

capacity
when
the
+
---,

volume,
of
state

CV(T,
expanded
formula

V),
in

particular,

equation
derive

the

form

pV=A(T)
heat
prove

B(T)p
using

C*(T)p2
the
=

the

expansion
of

for

the

capacity
that
that it is

temperature
0 for
to
a

dependence
gas

A, type

B,

(dCp/dp)T
possible
vice

with the

an

ideal
of
state

gas

C*,. . equation
of

Further,
of
state.

Show
that

derive

temperature
is

dependence
known.

Cp

from

of

Cv

(or

versa),

if

the

equation

Solution
As

shown

in

the

solution

to

problem

17,
and

the

Maxwell

relations

are

dS\

/dV\

fdS

Ch.

3]

EXAMPLES

151

which

gives

hr) V op
The if

fdC

=-T\^F2 JT
second
term

fd2V\
\oT

Jp

>

sothat

Cp(T,p)

Cp(T,Po)-T
PO

can

be

calculated

from
+

the
+

equation

of

state.

In

particular,

pV
we

A{T)

B{T)

C*(T)
+

p2

+,

B)

have

and

thus

\^pj
p)
=

fd2Vs

=A"(T)p-i+B"(T)

C*"(T)p+.. ,

Cp(T,

Cp(T,

p0)

t\a"{T) I
is and
=

log

2.
Po
+

B"(T)

(p

p0)

^C*"(T)(p2-p20)+^,
value
at

C)
pressure
=

where
For from
an

the

value ideal
gas,

of

Cp(T,p0)
AocT,

the

experimental

the

p0.

B=C= 0.

(),

so

that

(d2Vf8T2)p

0.

Hence

A)
Similarly,

we

have

(8Cp/dp)T
Cv
we

for

have

(8CA
and thus

\dv)T~T\dT~2)vi
_

(dlp\
v
.

CV(T,
where

V)
arbitrarily

CV{T,
chosen

Vo)

T
Vo

[(-?)
is

dV,

D)

Vo
of

is

some

standard
this
case

volume.
the virial

convenient

ex-

pansion

the

equation

of

state

for

expansion E)

jr
The
To

y+.:.
expression.
other,
calculation
we

reader obtain

may

expand
either

Cv

using
Cv
from
to

this the
the

Cp
method

or

can

use

(i)

of

An the

alternative

is

fol ow

of

C.39)

and

problem proceed

17. in

fol owing

manner:

250

300

Ch.3]

EXAMPLES

153

dTjp

8(T,p)

8(T,V)ld(T,V)
\dVjT
-c

dTjy\dVjr

(dp\

_(dj\(dS\l (dp\
\dTjy\dVjril

(8pXI(dp
where
we

-T(dA
(dp/dT)v
=

F)

have

used

Maxwell's

relation

(dS/dV)T.
+

Similarly

r Uv

=Td{S>

d(T,

V) V)

rd{S'
2

d(T,

V)ld{T' p)l l d(T,

p)

\ dTjp

\dTjJ

\dP )T
G)

200

K
heat
of

Fig.

3.7(b).

Molar

specific

air

at

constant

volume.

154

THERMODYNAMIC

FUNCTIONS

[Ch.

CpCv
eq.

can

be method

obtained

in

concrete

form

using
Jacobians.
much

B)

in This

eq.

F)
is
a

and

E)

in

G).
The
of

Note:

outlined which

above
is
can

uses

systematic
well.
The

method

transformation,
of
eqs.

very
seen

worth from

learning

equivalence

F)

and

G)

be

directly

fTjvl\dV/T
Note:

\dTjp'
3.7a and b
at

\dTjv
il ustrate
constant

\dTjPl\dpJT
on/?

molar
for
4.
For

Figures specific
air.

the pressure

dependence
and

and
constant

of volume

the

heats,

Cp,

Cv,

at

internal
that

energy

U,
=

absolute

temperature

T,
0.

volume

and

pressure

p,

show Solution This

(d U/dp)T

0 if

(d U/d

V)T

is
T.

V,

Using

problem C.24)

of and

transforming C.23)

the

independent

variables

from

/?,

to

dp)T
(One dif erentiating
unless 5.
can

d(p,T)
prove

d(V,T)ld(V,T)
this

\dv)Tl\dv)T'
U(V,

also

by
to

with

respect

considering /?.)

T)
if

to

be

U(V(p,
=

Therefore

FU/dV)T
heat

0,

T), T) (dUfdp)T

and
=

(dp/dV)T=0.
a

For
pressure

uniform
and
if
at

closed
constant

system,
volume is
pressure

prove
are

that

the

capacities
and that

at

constant

decreases

the
at

pressure
constant

increased
is
never

always isothermally.
less

positive
than

the show

volume

Further,
that
at
constant

that volume.

the

heat

capacity

Solution
This
was

treated

from

more

wil condition

be

given
is

for

this

specific

general problem.

point

of

view

in
to

3.8.

Here

solution

According

C.32b),

the

stability

STdS-dpSV^O.
If
T

A)
variables,

and

are

taken

as

the

independent

A)

becomes

dVj

\dTJ TJy

\dV)

On.

3]

examples

155

Now,

from
so

dF=

relation),

that

-SdT-p B) can

dV,
be
writ en

we
as

have

(dS/dV)T

(dp/dT)v

(Maxwell's

^F{%})
T

\dVjT
p
are

v^>
chosen
as

sothat

(^ \dVJT
variables,

Also,

if

Tand

independent

A)

becomes
.

(K\
Using

\dTjp
Maxwell's

^2lfss\ <5T2

\dp)T

P ) dpST-i
s__

fdv\^x_ \dTjp
(dV/dT)p,

dTdp-i\
D)

\dpJT
becomes

fdv\

P dP2>0.

D)

relation

FS/dp)T=

and

thus

Cpt0,

fdV\

1 ^0.

E)

Following

C.39),

we

calculate

fI dS\

\8TJP

_d(S,p)
8(T,p)

d(S,p) d(T,V)d(T,p)

d(T,V)

dTjv\dv)T
\dK8TJV Tj
(where
we

(
\\ddVjVjT\\ddTjTj yl\ld\8 VjVj T

\dv)T\dTjvJI\dv)T
\8dTjv
relation

(\l(

\dTj Tvl\dVjT
(dpfdT)v).
Since

have
we

used have

Maxwell's

(dSfd
or

V)T

(dp(dV)T<0,

'dS\

fdS\

CP^CV.
derived

Note

1:

Since

(dp/8V)s^0
Cv
=

can

be

easily
and
process.

from
be

A),
for be

CpICv=kt/ks>0
a

gives
Note defined
a

Cp=0if
2: heat

0.

Equations

similar

to

C)
for

E)
a

can

proved
system.

heat

capacity
that

by capacity density
is

an

arbitrary
can

specified
be in

It

should

noted,
force,

negative
the
matter
centre

non-uniform
to

however, For instance,


or

if
open
can

the

system

negative.
6.

high exchanging (See problem

is

due with the

gravitational
outside,
the

if

an

specific

heat

be

39

in

Chapter
of
a

4.)
uniform increases

In

the

quasi-static
that

expansion
the

body
or

under
decreases

constant

pressure,

show

entropy

of

the

body

depending

on

156

THERMODYNAMIC

FUNCTIONS

[Ch.
at

whether

the
or

volume

thermal

expansion

coefficient

constant

pressure

is

positive
Solution
This
cart

negative.

be
at

shown
constant

by
is
p
as

examining

the

sign
The

of

the

volume

derivative

of

the
at to

entropy
constant

consider that

pressure and

pressure defined the

(8S(8V)P.
by
a
=

volume

expansion
which the
to

coefficient
it is convenient
reduces This

(8 V/8T)P/
variables. variables

V, for
Thus

of
as

changing
fol ows

the

independent independent
of

problem
in

to

done

(application
=

C.23)

and

V,p C.24)):
=

T,p

(8S/dV)p.

is

ds\

8Vjp
As

=d(stP)
in

d(s,P)

id(v,P)
for
same
as

8(V,p)
example
5,
is
constant

d(T,p)l8(T,p)
Cp^0
the
a

(ds\ l(dv\ \dTjJ\dTj


body
and
a.

^c,i
since

T/
7^0

"'

proved
sign
heat of

uniform the

and

F^O,

the 7. The

(dSjdV)p
capacity
is
at

sign

of

volume
an

Cv=Nf(T)
gas.

(where
the

N energy
\i.

is the

number
the

of internal

molecules)
energy Solution

known

for

ideal and

Find

free

F,

U,

the

entropy

S,

the

chemical

potential

(See

problem

12.)

Integration

of

{8SjdT)v=CvIT

gives

where

gt

(V,

N)

is
T

function

of

and

N.

Since

(8F/8T)V=

S,

integrating

A)

gives
F
=
-

lS(T')dT'
T

+
T

g2(V,N)
HT

-Tgi(V,N)
where
g2

g2(V,N),
by
parts,
we

B)
get

(V,

N)

is

function

of

Vand

N.

Integrating

Ch.

3]

examples

157

and
U
=

F+TS
the

[f

(r)
A.11),

dT'

g2(V,

N).
-p=

D)

Substitute

eq.

B)

into

condition

(8FfdV)r=

-NkTfV,

to

obtain
8V
V
'

8V

and

hence
gl
=

Nk
.Fin

log

kfa
give,

(N),
by
kT
must

g2

02 (JV),
with

E)
respect
to

which

are

inserted

into

B),
-^t T" of

and

dif erentiation

N,

Mu

dN
\i
must

=-\dT'\
be

J
a

J
function

dT"

logV 6
have

kT

dN

-^.

dN

F)

Since

V[N,
or

we

dN

-logiV

a,

0!

=-

NXogN

+
a

Not,

(a
-

is is
in

constant),
a

G)
(8)

0,
obtained
T

or

02
gx

iV0o
them

@o

constant).
A),

Having F):
T

thus

and

g2,

we

substitute

eqs.

B),

D)

and

-\dT'\

CV{T")

dT"
^
-

NkT

log

V
-

NkT

JV0o

NkTa,

(9)

A0)

^
T T

Nfclog

A1)
-fcriog 0O

Idr
T T

I /(r)
dr

kT\og^

0o

fcTa,

A2)
A3)

158

THERMODYNAMIC

FUNCTIONS

[Ch.
gas

Note:

The

form of

of

usually
12.

used

for

an

ideal

is

given

by

eq.

E)

in

the

solution
8.

problem
a

Consider

spring
to

which
the
free

fol ows
X

Hooke's
when

proportional
The Determine
a

tension
constant

proportionality
the
of
x.

(spring
F,
the
the thermal internal

law; it is pulled constant)


energy

namely

the

elongation

is

energy

at a constant temperature. k, is temperature-dependent. the U, and entropy

S,

as

function

Neglect

expansion.

Solution
If
F

is

given

as

function
dF

of
=

the

strain

and

the

temperature

T,

we

have

-SdT

Xdx,

A)

Fig.
where force
X

3.8.

is

the
is

tension

of
to
was

the

spring
for
a

which

is

in

balance
Hence

with
the
From

the

external

Xt,
the

and external

equal
force

Xe

quasi-static
as

by

expressed

d'A=Xe

process. dx=Jfdx.

work

done fol ows

A)

dF\ dxJT
Integrating
which
this
we

B) C)

have

gives
dF
--

Sp.x)

dF(T,O)
dT

-$k'x2
U(T,

S(T,0)D)

U(T,x)

F+TS=

0)

i(k

Tk')x2.

E)

Ch.

3]

problems

[a]
energy

159

Note:

Usually,
=

in and the

mechanics
elastic force

the
as

potential
K=

of

the done

spring
The

is

writ en

as

Um
of
force.

%kx2
are

dUmFx=
is

kx. the which work

dif erent
In

because
the
occurs
are

Kdx=Xdx under

signs by
or

of
the contraction

AT and

external

mechanics,

conditions
not

of

the

spring
takes
if

always
without

clearly
reference

specified;
to

mechanical

potential
it

energy

elongation Um is defined thermodynamics.


energy energy
F.

only
If

as

the

elongation
hand,
9. Show
zero
as

takes
the

place place
third

isothermally, adiabatically,
law
of thermodynamics approaches

Um is the free Um is the internal


that

On
U.

the

other

from the

the
zero.

heat

capacity

tends

to

temperature

the

absolute

Solution

The where ature,

heat

capacity

for
is
the
x

given

process

may

be

writ en
to

as

Cx
absolute
as

T(dS/dT)x,
temperwe

(dS/dT)x
the

quantity
S
=

partial being
=

derivative

with

respect

the

kept
lim

constant.

By

the

third

law,
lim

T-*0,
T

have

lim
T_o

lim T^0T
lim
r-o

TS

fd(TS)\
-

r-o\
S
+

dT

)x\\dT)x

/( )

l/dT\

r-o\

( [S

fdS\\

\dTjJ

lim
r-*o

Cx

and

limj^o

S=0.

Thus

lim^o

Cx=0.
Problems

[A]
1.

Prove

the

fol owing
a

properties
system

of

the thermal
to

Helmholtz
contact

free with internal


free
energy, of the
R

energy,
a

F:

(i) (R)
the
at

Consider
a

(A)
T(e)

in

single
temperature,

heat
the
A

reservoir

temperature
The

equal
in the the

the

uniform

T,
system
and
A

of
is

system.
to

change change provided


no

Helmholtz

F,
system

of heat

equal
reservoir

the

in

internal the done


the
on

R,
A

that

heat
the

energy reservoir

the

heat
to

supplies
from

only

the

system
is 2. There

and
a

work
increase

is

reservoir
the

the

outside.

(ii) equal

When
to

system

changes
in

isothermally,
free
energy energy
V.

work

received

by

the

system

the

of

the

system.

is its

system
p,

whose
and

internal volume

U,
Prove

and
the

by

pressure

enthalpy fol owing

H,
relations

are

determined
for this

160

THERMODYNAMIC

FUNCTIONS

[Ch.

system:

^ (ii)
Cp
and

d[/
dH
are
k

C^KJ(?)

dp capacity

^a
+ at constant

dv/v?

(CK(/c/a)
heat the isothermal

+V)dp

(C

dF/F,
pressure and
a

where volume

CK

the
is

and

constant

respectively,
coefficient.
the
an

compressibility

is the

volume

expansion
3.

Express
to

rate

of
and

temperature

adiabatic
in
terms at

ficient),
heat
increase
at

quasi-static of the expansion


constant

change, compression
coefficient
pressure

Xs

{dTjdp)s,
(adiabatic
at
constant

for

system
a,

subject
coefand

temperature
pressure

the
the

capacity
in
constant

Cp.
when
the

Also,
system

find
is

the

expression

for

entropy
pressure.

in terms

of

Xs

quasi-statically

expanded

4.

Find and the

the

formula

for

calculating
when
are

the

Gibbs determined
the

free

energy

G,

the

enthalpy
coefficients,

H,

entropy

S,

A(T),

B(T),

C(T),. .
pV
=

experimental y given

expansion
of
state

for

equation
p
+

A(T)

B(T)
using
the

C(T)
Helmholtz

p2

+.-.

5.

Prove

the free

fol owing
energy G:

equations

free

energy

F,

and

the

Gibbs

6.

Show

that

'dH\

)vT{c\)
S,
to constant.

fdV\
increases
with
to

fdT\
the
the

7.

Show
pressure,

that
p,

the is is

entropy,
known

volume,
absolute

V,

for

gas

whose
when

be

proportional

temperature

the 8. Prove

volume

kept

the

fol owing

inequalities:

where

U,

H,

S, P and

are

the

internal

energy,

enthalpy,

entropy,

pressure

and

volume,

respectively.

Ch.

3]

PROBLEMS

[A]
are

161

9.

Show

that

the

fol owing
from

processes
a

irreversible:
V
to

adiabatic

expands
top
10. The
Show
+

expansion adiabatically

volume

V+dV
process

(a) (dF>0)

gas

makes
and

free
a

(b)
pressure

gas
p,

by

the

Joule-Thomson

from

dp

(dp<0).
expansion
coefficient
at

volume

constant

that
and

the
from

temperature
that
a

always
this
decrease is

decreases

pressure for

positive quasi-static
temperature

is

for

gases.

adiabatic
decrease

expansion
which Joule-Thomson
11.

results

corresponding

greater decrease

than
of the

the
pressure

by

the

adiabatic

effect. that
the
is

(i) Show compressibility


to

ratio

of
to constant

the
the

adiabatic
ratio
pressure and of

equal
at

the

specific
Prove

heat

compressibility the heat specific (use a Jacobian).


it to discuss
and this
at

to at

the
constant

isothermal
volume

(ii)
of the

(ii ) principle.
12.

inequality compressibilities a Give physical

C.37b),
at constant

use

the
constant

relative
Le

magnitudes
temperature.

entropy
of

interpretation

using

Chatelier-Brown's

The

heat

usually
where
and

capacity expressed
C
is

at
as

constant

pressure

Cp (for
+

moles)

of

an

ideal

gas

is

Cp
the

nCp
at

nCyib(T),
pressure
due
to
a

specific
motion
of for
a

heat the
gas

constant

the
gas

translational
of

rotational

molecules
of diatomic

(C=fjR
molecules
is the molar
the

for and

monatomic
for
a

molecules,

Cp=iR
molecules)

Cp=4R
heat
due
to

gas

of

polyatomic
vibrations
energy

and

Cvib

(T)
Derive

specific
formulae

molecular Gibbs

(lim^o
and
Divertissement

Cyib(T)=0).
entropy.
9
mnemonic

giving

the

free

the

Thermodynamic
sequence
an

diagrams.
and

The laws
and
eqs.

of

the

first

the of fundamental the

second
process,

Gibbs relation of thermodynamics

C.1)
are

is then

the
obtained If definition

con-

applied

to

infinitesimal

by
have of
eqs.

repeated
mastered

quasi-static application
the in
two

C.2)-C.4)
transformation

Legendre
laws
you

C.11).
in able
mind the
to

you

and
to

keep
be

thermodynamic C.1)C.4)
the
method The

potentials,
the
way

ought
above.
as a

easily
you

write better
on a

down
re-

described
eqs.

member
gram,

fol owing
of
was

method,

sort

writing
devised

C.1)C.4)
Max

However, of rainyday automatically


someone

had
based

fund.
is

dia-

which

by

Born

or

before

1929.

You

first

162

THERMODYNAMIC

FUNCTIONS

[Ch.
one

draw

two

arrows

downward,
in

while

the

perpendicular other,
a

to

each
to

other:

from

S
to

to
as

going
shown that

from/?
cross

V,
the

goes you

from

left
say

right,
to

the
Sun

figure.
is the

Drawing pouring peak


of down
to
a

of
rays

arrows, upon

might
and the

yourself

the
from

his

the
circle
to

Falley.
named
eq.

Next

you

four
can

quarters
for write, corresponding

E(= C.4)
Gibbs
in

Trees, complete U), F, G and

the

brook

diagram
The natural

flowing by adding
Then
you

is

Hclockwise.
way.

instance,

the free

fol owing
energy

variT

ables

the

are

given

by

and

p,

which

stand
you

at

the

ends
S and

of +
S
sense
comes

the
Fas
to

G-quarter
the
from

of

the fact

circle. of
dTand
you

In

the

dG,
The
Sr-arrow In been
term

write

coefficients
the
at

dp,
have
T.
term

expression respectively.
to trace

of

minus in the

sign
a

of
reverse

that

the has that

arrive

S, starting
the
mass-action

from

diagram
because
to
to
common

mentioned

above,
the

Em&Ni
because
can

dropped,
is

diagram
eqs.

is

two-dimensional,
If
term

and
you

all
some

of

C.1)C.4).
mass-action in
a

necessary,

generalize
of

the
term.

diagram
You wil

include

the

and

other

types
H.

the

work
Ther-

find

examples
and

text

book
New

by
York,

B.

Callen:
which

modynamics application
13. Derive of 14.
one

(John
of

the

Wiley diagram
energy

Sons,
method

Inc.,
to

1960),
reciprocal

shows

the

Maxwell

relations.

the and

Gibbs
n2

free moles of

of

an

ideal

gas

mixture

consisting

of

nt

moles

second of rubber

component.
a

Measuring
we

the

tension

X, X=AT,
temperature.
a

band
A

stretched
is
a

at

constant

length
only
U,
its
of
on

have Tis rubber

found
the band

that
absolute
is

where
of

(>0)
that

constant

depending
internal
energy, and

/,
S

and
a

Show

the

such

function

the

temperature

only

that

entropy

decreases 15.
For

with
rubber

increasing
band rises if
if
as

length.
described
rubber
the band in the is is

previous
stretched
raised

problem

show Also
a

that
show
constant

the

temperature
that
it

the

adiabatically.
while

wil

contract

temperature

maintaining

tension.
16.

Derive

the

Gibbs-Duhem

relation

C.12)

from

the

Helmholtz

free

energy.

Ch.

3]

problems

[b] law and

163

17.

Show

that,
zero

according
coefficient
as

to

the

third

of
the

thermodynamics,
pressure

the coefficient

thermal

expansion approach
18.
If

(dV/dT)plV
!T->0.

{dpjdT)v

the

tension

of

wire

is

and

its

length
and
J

is

x,

show

that

(dX\

\dx/s,p
19.

>0

(dX\

\dxJTiP

>0.

Show

that

20.

Consider
XT-

paramagnetic
the free

body
energy from

with
as
a

an

isothermal
of the
energy

Obtain

F,
this

function the internal

magnetic magnetization
U,
and

susceptibility,
M,
the and
the
S.

temperature

T, and

derive

entropy

[B]
21.

Consider internal

system
the

of

particles

of

single
the

kind;
volume

U,

T,
and

and

pi

are

the

energy, per

absolute

temperature,
Prove

the

chemical

potential

particle,
dU

respectively.

the

fol owing

equations:

cm

()
KdTj
dU\

=(dN)

\dix)TtV\dN)Ttyj
fdU\
v,N

(du-\
fdN\ \^Jt,V^^)t,vI
convenient

It

'

fdU\2
for

22.

Derive

formula
at

which
volume
and heat the

would

be
as
a

calculating
absolute

the

heat

capacity
the 23.

constant

Cv,
chemical

function
\i.

of

the

temperature

T,

volume
the of and

V,

potential

Compare
number volume

capacity
to

CV>N
the

of

system

at

constant

volume
same

and
at

constant constant

particles
constant

heat

chemical

capacity potential,

Cv>ll
and

of

the

system

discuss

them

using

Le

Chatelier-

Brown's

principle.

164

THERMODYNAMIC

FUNCTIONS

[Ch. relation

24.

Show

that

for

paramagnetic

material
Xs
=

the

holds
the
constant

between

the

isothermal
at

and
H.

the that

adiabatic
and

susceptibilities,
CH
of is the
heat
of

where

CM

is
at

heat

capacity magnetic
are

constant

magnetization
Assume

field

the

volume

changes
the

the

capacity magnetic
M,

material
on

negligible.
H,
a

Also,
a

given
for
material

the

dependence
CMCH.
the obeys magnetization.

Tand

derive

formula

calculating
which for
field
zero

magnetization, the (Use


law Derive

Jacobian.)
and

25.

Consider
has
a

heat
at

paramagnetic capacity
constant

Curie

xT=CjT,
the for
constant

capacity magnetization

C0 b/T2 magnetic
=

heat

CH,

the

heat
is

CM,

and when

the the

adiabatic

'magnetic
field

(dM/dH)s
around 26.
Show
r->o. 27.
a

(H=H0)
given
the field isothermal

magnetic

capacity susceptibility changed

Xs(Ho)
infinitesimally

Ho.

that

susceptibility

Xt

satisfies

the

relation

dxTldT-+0

as

Show The

that

it

is
of

impossible example

to

reach also

0 K be in

by
considered

adiabatic

demagnetization.
using example
dF*
a

28.

problem

8 may

free

energy

F*,
the

defined

physical
29. A

by F*(T, meaning
energy

X)=F(T,
of this

x)-Xx.
free
energy,

Following particular

1,

discuss

(T,

X).

free

of

the

form

is often

used with function

for
%T,
a

paramagnetic
and
dielectric
is

substance

which
a

has

an

isothermal
H.

magnetic

susceptibility,
dielectric
the

placed
constant

in
s

magnetic
in the
presence

field
of

Similarly,
an

for field

electric

E,

F*(T,P)
may

F*(T,0)-~(s-l)E2
Here,
Fis with
and
P

oTC

be

used
compare

as

its
M

free these
is the

energy.

the

volume. the
is

problem, F(T, P)
the

free

energies

free

where for

magnetization
case.

the

Following energies polarization.

the

previous

F(T,
Also

M)
obtain

and

entropy

each

Ch.3] 30.
A
between

PROBLEMS

[C]

165

dielectric
the
of

with

plates
constant

temperature-dependent of a parallel
electromotive the switch is
of

dielectric

constant,
which
is

(T),
Discuss

is

placed
to
a

plate
force

condenser
as

connected after

battery
heat

shown

in when is it

the is

capacity
Assume

when that

closed
the

and dielectric

figure. opened

the

being

closed.

the

volume

unchanged.

am

L
m

\ \ \ \ \ \ \ v^
\v

dielectric ^S\\ \ \ \ \ \v^

vAX;

mam

31.

Find

the
30
#.

amount

of when the

heat

produced
dif erence

in

condenser
is increased

such

as

described
from

in

problem
Oto
32.

potential

quasi-statically

Explain
between

the

fact

that

dielectric
of
a

is

pulled

into
as

condenser

when in the

it is inserted

the

parallel

plates

condenser,

shown

figure.

I'H"
T

[C]
33. The chemical

potential
Obtain
and
prove

of

one-component
the the

ideal
form

gas

has

the

form

<f>(T)
poten-

+kT
tial

\og{p/pQ(T)}.
J(T,
figure
rubber / the

functional relation
data
at
a

of

the

thermodynamic

V, pi)
shows

C.5).
for
constant

34.

The

the band
Let

experimental
maintained be the natural The
total

the

tension

of

suitably
against
at

vulcanthe
is

ized

length
of
the

plot ed
band
x

temperature.

/0

length
tension

rubber

temperature
related

To and

actual

length.

(stress

cross-section)

166

THERMODYNAMIC

FUNCTIONS

[Ch.3

to

/as
X
=

where
7
at
x

is

the

thermal Obtain

expansion
the
is called
is stretched

coefficient

and

is

approximately
T,
when from
AT

equal
the
rubber

to

10~4
temperature
to

deg.
To
times

change suddenly
the

in Joule

temperature

band

/0

that.

(This

(adiabatically) effect.)

its
as
a

natural function

length
of
L.

Plot

1.38

1.22

1.13
1-

20

40

60

80

temperature

Solutions
1.

The sider

proof quasi-static
the

is

similar
processes,

to

that

of

example
a

1.

In

this

case

we

only
is defined.

need
Hence

to

conwe

since
an

uniform
process.

temperature
its

write

equations
heat
of
be

for
reservoir heat
to

infinitesimal does
the
not

(i)
finite

The
amount

change
A.

temperature
the
heat

T(e)
reservoir

when
receives

it

gives
no

system
its
in

Since
is

work,

it may it

assumed
The
are

that

change
the

uniquely
energy

determined

by
the
of

the

heat

d'Q
of
as

gives
reservoir

off.

the

changes by given
=
-

internal
and and the

U(e),
laws

and

entropy

S(e\

the

first

second

thermodynamics

dC/(e)
If

d'Q,
and the

dS(e)
of

d'Q/T(e).
A
are

A)
U

the

internal
energy

internal

energy and S*
=

entropy
of
the
are

the combined

system
of
state

and

S,
U*

the
=

the

entropy
These

system
of

become the

U+U(e)

and

S+S(e\

functions

combined

Ch.

3]
Since

solutions

167 to

system.
the

there

is

no

heat

supplied
0,
or

the

combined -d5.

system,

we

have,

by

second

law,
dS*
=

dS(e)

B)

Considering

eq.

A)

we

have

dU(e)

T(e)
of the
=

dS(e)
combined dU
+

T(e)
system,

dS.

Therefore,
be writ en

the

energy

change
dU*

dUie)
=

can

as

dU*
because

dUThe

T(e)
last
is
to

dS

dU-TdS
is
to

C)
defined Since the
to

T(e)
of
We
on

is the

equal
system
the
first

to

T. A

variables

and
law

in

fact
work

expression equal
combined
done

in

terms

of

state

dF.

(ii)
done combined

apply
the

the d'A.
dF
=

system.

the obtain

work
on

d'A the

system
we

is

the dU*

only
=

by

environment

system,

have

According
d'A.
this

C)

we

The
2.

name

"free
S

energy"
as
a

comes

from

relation.

By

considering
iv
-

function
P iv

of/?
=

and

V, eqs.

C.1)

and

C.2)
-

become

as

7-Q
<T[

dp
\

{r(g)p
J
a

P}

dK.

(i)
B)
Fby
the

dH=TdS

Vdp

\SpJv
V),

+v}dp

T[

\dVJp
of/?

\ dV.
and

Regarding equation

as

S(T,
we

V)
have

S(T(p,

V) (Tis

function

of

state)

ly Similarly,
from

\dTJy\dp)y
S(T(p,
V),p)
we

\dp)y'

S(T,p)

have

\dVjp
Using
an

\dTjp\dv)p
of
eq.

T\dVjp
to

TVu'
obtain

application

A.23)

eq.

C),
IfdV"

we

'dV\

168

THERMODYNAMIC

FUNCTIONS

[Ch.

or,

CyKJTa. substituting
eqs.

E) D)
be

The

desired
and
Jacobian

equation

is

obtained
in

by
eqs.
manner:

and

E)

into

eqs.

A)
Note:
the

B).
The

transformation
in

C),

D)

and

E)

may

performed

using

the

fol owing
=

es\

a^jo
d(p,V)

d(T,V)d(p,T)ld(p,T)
d(s,P) id(v,P)

Hs^v)

d{Tvv)

Mpv)

/as\
=

\dVjp
Note how

d(s,P) 8(V,p)
the

/as\
=

i/dv\

d(T,p)ld(T,p)
partial
derivatives
are

\dT)J\dT)p
rewrit en
as

Jacobians

by

inserting

extra

variables.
3.

Since the

a=(dV/dT)pIV
fol owing
way:

and

Cp

T(dSldT)p,

the

Jacobian

method

is

used

in

dT\
dp

Js

^d(S,T)^8(S,
d

(S, p)

(p, T)l

T)Id(S,

p)
d

(p,

T)

\dpjrl

fdS^

lfdS\

\dTj

We

have
be

used

Maxwell's of
as

relation

C.21a),
at constant

which

results pressure
may

from
is
we

eq.

C.4).

The Since

volume

dependence
can

the
eq.

entropy

(dSjdV)p.
get

this

rewrit en after
the

D)

in

the
of

preceding
D),
one

1/Xs-

(Or,

first

equation

problem, proceed

(dS/d

V)p

using

dVJP
where
4.

\ST)\dv)p
relation
the

\ dT)sl\BSjTj\dvJp
C.21a)
of
state
=

\dTjs

Xs'

Maxwell's

is in

used.)

Substitute

equation

V=(dG/dp)T:

{dG/dp)T

C h.

]
can

solutions

169

which

be

integrated

to

G(T,
From

p)
this,

G(T,
we

p0)

log

Po

B(p

p0)

iC(p2

p2)

A)

obtain
p

(dG\

\vTJp
and
H
=

^ l,

PoJ

-^

'Og

Po

\p

Po)

H~<

\p

Po)

+'

',

B)

TS

H(T,

po)

(A-

TA)
+

log

Po

(B

TB')

(p

p0)

l(C-TC)(p2-p2)+~.,
must

C)
in
U

where

A'

dA/dT,

etc.

The

heat
and

capacity
It
T.

be
to

known

order

to

determine
from these

G(T,
equations
5.

po),

S(T,p0)
as

and

H{T,p0).
of/?

is

easy

derive

and

F,

etc.

functions
have

From

eq.

C.3)

we

F=

U-TS,
U
=

S=-(dFldT)v,
F-T

and

thus

[ \dTjy

/dF\

Dif erentiate

this
-p
+

with

respect

to

Fand

substitute

(dF/dV)r=
and

to

obtain

CU/dV)T=
therefore

T(dp/dT)v.
H

Similarly,
G-T[

G=H-TS,

S=-(dG/dT)p,

and

,'dG

From

{dGldp)T=Vwe
This

obtain

(dHldp)T=
treated
more

V-T(dVldT)p.
in

Note:

problem
2,
but it is

was

Chapter
6.

solved
2.

simply
The

examples using
half

and free
in the

4 energy.

and

problem

15

in

the

This
The

is similar

to

example
can

first

is

proved
Maxwell's of

foregoing
relation
into
\

problem.

lat er

half

be from

shown the
d

by
total
d

substituting
dif erential

(dV/dT)p

(dS/dp)T
dS\

(derived

C.4))
rdS

d(S,T) r)

E, T) d(S,p)d(p,T)
of the

(S, p)

/dT\
=

\dpJs\dTjp
gas

=_Cp(dT
the
form

T\dp
p=f(V)T.

7.

The

equation

of

state

in

the

problem

has

170

THERMODYNAMIC

FUNCTIONS

[Ch.

From

C.21a)

\dv)T
Since 8.
p >

fdS\

{df)v
side
0 when is

fdp\

f^

p
=

~T'

0 and

T>

0, the

right Vdp
=

positive.
dH=0.
V

(i)

By

eq.

C.2),

TdS+

Therefore

'dS\
_

(ii)

By

C.1)

TdS-p

dV=0

when

dt/=O.

So

Note the Then form

As

was

shown
T

in the

example
internal
=

2 of

Chapter
is
Thus

2, if the

equation
of the the
seen

of volume

state

has
V.

p=f(V)
we

energy

independent
it
is

may

write
a

(dSfdV)v
case

(dSldV)T.
(ii).
the internal

that

foregoing

problem
9. The
case

is first
one

particular
is
a

of

case

process

where

energy But

?/=

const,

and
of

the the in

second

where

the these

enthalpy
and
processes
a on

is

constant.

by
the

the

results

foregoing
both

problem
cases.

(dS/dV)v>0
Therefore is

(dS/dp)H<0,
are

and

entropy

increases

irreversible. adiabatic Since


the
can

10.

gas

made

to

undergo
the

quasi-static
gas.

expansion
gas

by
is from of the

decreasing
equal
gas.
to

the

external
pressure T

pressure

the of

pressure

the
This 3 and

external
where

drop
the

temperature
temperature temperature
=

be and

calculated

(dT/dp)s,

and
was

are

absolute

entropy
in
of the
at

quantity
can

called
as

the

adiabatic

coefficient
in
the heat and Joule-Thomson
terms

problem expansion
pressure

be Now

expressed
at

(dT/dp)s
pressure

TValCp
a,

volume
constant

coefficient

constant

and

capacity

Cp.
the The

(dT/dp)s>0
drops
in

if

a>0

since the

T,
pressure. in the

CP

are

positive,
process

indicating
is
V

that

temperature decrease

with

temperature (

given

by

(dT\
as
can was

fdV\
24 of

}
Chapter Chapter
2.

(Ta

-1)
not

shown
be

in

negative

problem (see problem

This

is
The

always

positive
decreases

and
as

44,

2).

temperature

Ch.

3]
as

solutions

171

long adiabatic
pressure
for
a

7a1>0.

The

term

in

this
in the for

inequality
the
case

is

not
a

present

in

the

quasi-static drop,
adiabatic

expansion.

Consider

of

Ap>0.
process

The

dif erence

temperature
a

sufficiently drop

small

(AT)s>0,
is

and

(AT)H>0,

Joule-Thomson

process

Note:

As for

can

be

seen

from

this

problem,
adiabatic
for

for

the

purpose

of is
two
a

cooling
better method

gas

(e.g.
than
every

liquefaction),
Joule-Thomson
can

quasi-static
be

the
gas

cooled

process down

the

expansion fol owing secondly,

reasons:

firstly,
temperature

by

this

method;

the

drop
li.

is

greater.

=l

fdV\
V

\dp

Jsl

ji_V

fdV\

\dp
S)

)T
=

d(V,S)ld(V,T) d (p, S)
l/dS\

(p, T)
=

d(V,
(ii)
'dY\
S

S) jd{p,

/dS\

Cy

d(V,T)ld(p,T)
(yt,

\dTjvl\8Tjp
Yk)
d

Cp

(yt,

yk)j 8(yh

yk)

jyJn\tyJn
Since

VyJn\dyJyk)l\dyJyi
,

dU=yt
&$
=

dYt+yk

dYk+

then

if

we

put
or

<P=U-yiYi-ykYk,

we

have

-Ytdyt-Ykdyk+>,
into
' '

(p\
T,

^(~)

C)

Substitute
1

this
'

B):
'
l

/[

nr

In

particular

if

7;

V, yt

p,

Yk

S and
T

yk

D)

becomes

fdVsl

(E)

can

be

derived

from

A)

above

and ks<kt.

F)

in

example

3.)

Therefore

F)

172

THERMODYNAMIC

FUNCTIONS

[Ch.3

(ii ) piston change


than when

Consider
the in

matter

in
V is

volume
the
pressure

changed
is greater

cylinder by
when
:

fit ed
an

with
A V<0.

piston.

By

moving
to

the

amount
no

According
to enter

heat

is allowed

the

F) cylinder

the

heat

can

be

exchanged

(Ap)s>(Ap)T.
Suppose change
This

that
is

the

matter

is The
pressure

first
result

compressed
increase of
the result

adiabatically
wil decline transfer
of

and

than

heat
to

ex-

allowed.
that
the is
to

from
caused

shows

indirect
diminish

(Ap)s
by

(Ap)T.
com-

heat

the

pression
which
is

(A)
Le

the

direct

Chatelier-Brown's

(A)

(increased

pressure),

principle.

heat

/77/7Z77// .

adiabatic

-AV

12.

We
gi

fol ow

the
as

(p, n)
T
=

the

procedure integration
dT'
.

of
constant:

example

7.

CP(T)
T

can

be

integrated

with

dT'
i

(P, n).
A)

Since

(8G/dT)p=
=

-S,

this

is

again
t

integrated
r

to

G(p,T,n)
=
-

B)
-

nCp(T

log gives

T-T)-

njdT' ^ Cyib(T")~
0 0

Tgl(p,

n)

g2(p,

n).

(dG/dp)T=V

dp

dp

Ch.3]

solutions

173

dgi

nR
= ,

dp
and
thus

and

dg2

dp
g2

0,

(jI(n),
Here

<j>2{n).
C)
into

C) B)
and

<px

and

02
that

are

remembering 0i

G/

integration is independent

constants.

Substituting
of
n,
we see

that

00

nct

(a
by
=

const.)

and

02 00
we

n^o
from

(^o
B), C)

const.)
and

D) D)

Therefore,

let ing

u-Cp=iR(=const.)
T

get

G(p,T,n)
=

\u0
called

CpT
the

log

RT

log

f
J
0

dT'
J

f
0

Cyih{T")
A)
(or

iRt\
J

J-

E)

(z is
entropy

chemical
as:

constant).

From
T

dif erentiating

E))

the

is
S

obtained

]cp
to

log E)

-R

log
Gibbs

jc^iT')
o

iR

F) potential)
G)

Note:
is

According
writ en
as

the

free

energy

per RT

mole

(chemical

G(T,
where
13.

p)
of

G(T,
G
at
some

po)

log

-,

Po

G{T,p0)
to

is

the

value
5 of

standard Helmholtz

pressure

p0.

According
ideal
gas

example
has

Chapter
Ft (T,
the
gas

2 the

free

energy

F,

of

this

mixture

the

form
=

F(T,
where
V
+

V,
the

nls

n2)
of volumes

Vu
mixture,

nt)
by

F2(T,
and
gases and is

V2,

n2)
VnlJ(nl
2
as

TAS,

A)
and

is

volume
are

Vt
1 and

+n2)

V2

Vn2/(n1
mixing.

n2)

the is
AS

occupied
entropy
of

respectively

prior

to

Now

AS

the

mixing
Hl

given

-R\nl\og[
the

nt+n2
to

+n2log^
7, Fx

nx+n2)
Vx,

i.
nx)
and

B)
F2 (T,
V2,

As

shown

in

(9)

of

solution

example

(T,

n2)

174

THERMODYNAMIC

FUNCTIONS

[Ch.

have

the

forms

Fi(T, F2(T,
Therefore

V V2,

nx) n2)
=

n^t(T) n2$2{T)
-

n,RT\o%^,
g
n2

()
F2 (T,
Hence

n1

n2
=

()
F2 (T,
V,

V2,

n2)
becomes

n2RT

log

^
nx
+

n2

n2).

A)
C.13)

F(T,
By

V,

nl9

n2)
8F

Ft(T,
8F

V,

nt)

F2(T, Pl)
+

V,

n2). p2),

C)

G(T,
where

p,

nlt

n2)

nlir+n2 crii
P2

on2

n.G^T,
pn2

n2G2{T,

D)

pnt Pi
are
=

Vt

n2RT

'

Tr

IP=
are

the

partial
per
are

pressures

and
substances

Gt (T, pt)
1 and

and
2 at
pressures

G2 (T, p2)
p^

the the writ en

Gibbs

free

energies
These
Note: G

mole

of
to

and/?2>
in be
+

respectively.
gas

equal
From

the
note

chemical
to

the

the

potential foregoing

of

the

materials

mixture.
as

problem,
+

D)
log
\
-

may

n^G^T,
is
a

Po)
standard

n2G2(T,
pressure.

p0)
The

RtIu,
Po)
have

Po

n2

log
each

Po/

-V
component

E)

where is

p0

chemical

potential
+

of

given

by

Gi
Let

Gi(T,
F(T,
I).

Pd

Gt(T,
we

RT

log

P'.
Po

F)

the

free

energy

be

Then

F+TS

F-T[

\8TJi

),

B)

Ch.

3]

solutions

175

(The
Eq.

infinitesimal

work

d'A

with

respect

to

change

in

length

is

d'A=Xdl.)

B)

gives

rdU\
SI

Jt
upon

fdF\ \SIJt
dif erentiation,
'dS\

d2F
dWT

fdX\

\dTJt'
/dX\

and

eq.

A)

becomes,

82F
_ ~
~ _

Ji)T
Substituting
X=AT,
we

f lf

\df)l'

E)

find

Therefore
that
15.

U is

independent
to
an

of

/ and

S decreases

with

the

increase

of

/.

(Note

this

is

similar

ideal

gas.)

For

an

adiabatic

quasistatic
r\
_

elongation
~
~

E=const.)
T
_ ~ ~

we

have

(dS/dl)T

dljs
where

(pSfdf)i
at
we

C,
constant

(8S\
length

TA
_
~

\di)T
and

^T
A

is

the

heat

capacity
Also

is

the

constant

in

the

foregoing

problem.

have

K8TJX )
Thermodynamic
similar
16.
to

si

(8X/dl)T
requires A) and
the that

l\dlJT
(dX/dl)T>0
prove

stability

(an
the
statement

example
of the

of

C.35b)).
extensive

Eqs.

B)
Helmholtz

C.34), problem.

Being
as a

an

quantity,
of the form

free

energy

F(T,
the

V,

Nlt

N2,. .)
numbers

function have the

temperature

T,

the

volume

V,

and

particle

must

F(T,aK,aiV1,aJV2,. .)
Dif erentiate with

aFG\
a=

V,NUN2,. .).
obtain I

respect
F=V\

to

and
I

set

1 to

fdF\

\dVjT,N
by

+YJVI

fdF\
j

'{
both

Equation by substituting

C.12)

is

obtained

dif erentiating

sides

of

this

equation

and

C.3).

176

THERMODYNAMIC

FUNCTIONS

[Ch.

17.

By

Maxwell's

relation

C.21a)

we

have
and

WP=-W/
According
constant

dv\

fds\
law,
Hence

to

the

third

the of
the

entropy
pressure

of
or

uniform
the

body density
as

approaches
7W0,

value
the

independent
is

provided

that

density

finite.

lim(
and
thus

fdS\

=0,

lim(]

fdS\

=0,

T-+o\oT/p
Alternative

lim

(dV\
From

=0,
the third law

lim() T->o\oTJv

fdp\

=0.

solution:

dV\

dTjp

\dp)T
T

(dS\

J\dp)TT
0

[(dCp\

dT

and
where

therefore

lim

/aT/za^x

(d VfdT)p
(see example

0,

{dCJdp)T=
applies
to

T{p2V\dT2)p
(dp/dT)v.
=

3)

was

used.

similar

oper-

ation
18.

Since

(dU/dx)s

X,

C.32b)

can

be
=

writ en

as

2S2U let ing


Also,

6Xdx

(dXldx)s>p

6x2^0,
A)

SS=dp
by

0.

Therefore

(dXfdx)s>p>0.
let ing 5T=5p
=

0, C.32b)

becomes

or

(dX/dx)T>p>0.

B)

Ch.

3]
we

solutions

177

Alternatively,

may

use

\dx~)s
(p
have
=

/dX\

d(X, d(x,S)
Cx>0,

S)

_
~

d(X, d(X,T)
Cx>0,

S) d(X, d(x,
we

T) 8(x, T) T) d(x,S)
say

Cx

fdX\

~CX \dx~
and

)T
(dX/dx)T
and
let

const.).
the
same

Since

may

that

(dX/dx)s

sign.
C.32b)
we

19.

Following
<5r=

take

T,

and

as

the

independent

variables

E/>

0 to

obtain
dJS
T,P

^U,

or

20.

This

is

similar
the volume

to

neglect
the free

problem change

39

in

Chapter
consider
a

2, but
unit

it

is

more

general.
of
the

Here

we

and

volume

material.

For

energy

F(T,

M)

8F

According
the

to

the

problem,
H,
is

the

relation

between
it
to

the

magnetization

M,

and

magnetic

field

given
and

Substitute

D)

into

C)

by integrate

M=%TH.
get

D)

F(T,
Therefore
we

M)
have

F(T,

0)

W2IXt(=

F{T,

0)

\XtH2).

E)

S(T,

M)

where

^S(T^)-\{^r^ 2^
0),
U(T,
the
i

M2

F) G)

^^2,
0)
=

S(T,
Note:

0)
particular,

F'(T,
if
we

F(T,

0)
law

TF'(T,

0).

In

assume

Curie-Weiss

(8)

178

THERMODYNAMIC

FUNCTIONS

[Ch.
obtained

the

solution

to

problem

39

of

Chapter

2 is

independently

from

F)

and
21.

G).
A

(i)
V

convenient
N

thermodynamic
is
the

function free energy

for

the

independent
since
we

variables have

T,

and

Helmholtz

F(=

TS),

SNJt,v
(ii)
we

~fi~

8T

VtN

To
note

change
that

the

independent

variables

from

T,

V,

?=n/Tto

T,

V,

pt,

JuJt.v
and

obtain

dT)VA

d(N,Z,V) (T, Z, V)
]/dN
I (

ld(T,Z,V)
d

(T,
l

n,

V)l

(T,

pi,

V)
8N 8N

K^Jt.v

T\dpi)T>v'
The

first

term

can

easily

be

rewrit en

as

>

T>

d{T,pi,V)

d{N,T,V)d{T,pi,V)

Hence

dN\
~

/8N\
_ ~

~dil)T>v{f~\dTjv^
by
us

(/i

The

desired

equation

is

obtained
to

substituting
the

the

relation
in
the
are

derived
heat
constant

in(i).

(ii )
at

This the

problem
volume
for when

requires
the
const.
case

find

dif erence numbers

capacity
and
from

constant
case

when
If
we

the

particle
the

for

change

independent

variables

T,

Ch.

3]

solutions

179

V and

to

T,

V and

N,

we

have

dTjv>i

d_U\

=d(U,Z,V)=d(U,Z,V)
d

(T,

{,

V)
/dU\

(T,

N,

ld(T,Z,V) V)l l d (T,

N,

V)
dU\
8U\

dU\

df)NtV
'?i\
*

(dA\

\dN)T,v
(d?/dN)T>

dTjN>v

\PNJT,Y

The
prove

first
the

equality inequality
Then

of

(ii )
we

is
use

obtained
the
that

by
fact that

substituting C.35c)

the
in

result

of
case

(ii).
becomes

To

this

(dnldN)TtV~Z0.
22.

it is
constant
=

obvious
volume

(dN/dn)T>v=lf(dfxfdN)TtV^O.
is We

The

heat

capacity
i.e.,

at

numbers,
from

CVtN
N
to

T(dS/dT)VN.
T,
V

usually change

defined
the

for

constant

particle
variables

independent

T,

and

and

fi

as

fol ows

\dTjv>N

d(T,
'dS\

N,

V)
(dS\

d(T,

pi,

V) I d(T,
1

ft,

V)

,dT/uV
'dN
n,v

\du)TV
T.V

dTj^y
on

(dNldi )TiV\di )TtV'


to

The which

first
is
pi.

term

the

right-hand
at

side
constant

corresponds
volume and
term
we

Cv>fl
use
one

T(dS/dT)Vfl,
chemical
of
po-

the
To From

heat

capacity

constant

tential,
relations.

change

(dS/dfi)TV
C.5)
we

in

the

second

Maxwell's

have 8J

-l

v>fl

which

give
dS\
_

82J

dN\
8T

dpL/TV
8S\

dpi
~

df)v,N

dNV

A)

180

THERMODYNAMIC

FUNCTIONS

[Ch.3

Multiply

both

sides

by

to

obtain

B)
23.

By

B)

of

the

previous

problem

we

have

(analogous

to

Cv

^ C)

A)
We

fol ow

the when

example
the

in

3.9

to

interpret
(action

this.

Consider

the the

temperature
surrounded

rise,

AT,

heat

Q is supplied

A)

to

system

particle
reservoir

by
of

wall

permeable
JM
the

to

particles.
reaction,
rise

Besides

the

flow

of
to

heat
Le

there Chatelier-Brown's
is
means

is

also

flow the

particles, principle,
rise

(secondary
temperature
the
case

b).

According
JM
allowed
is
is

(AT)N
the flow

when

(AT)^,

in

when

stopped (which

greater
that

than
pi

is

constant).

Or,

(AT)N>(AT\.
Since Note:

B)
B)
cannot

(AT)N
For

Q/CVfN
because and
is
are

and
pressure

(AT^Q/Cy^,
CPtfl
p

and

A)

mean

the for
a

same

thing.
com-

constant

be

considered

single

ponent

system

T,
not

and

are

related

through

by

the

Gibbs-Duhem

equation
24.

C.12)
problem
2, but
Xs
~

independent.
to

The

similar
use

problem
Jacobian
>

19

of

Chapter

of

the

method

Chapter simplifies

and

problem
solution.
We

14

of
have

the

d(M>s)

dHjs

d(M,

S) d(M, T) d(H,

T) d(H, T) d(H,S)

T)

JdJL\ JJL\

f3^) \dTjM\dHjTl\dTjH

l(dA\

\dHjT j

T(l T(dl\ \ddTjTjJ

jT(dl\ (

\dTj jH

Xt

Ch.

3] in

solutions

181

As

C.39),

\dT)M
T

d(T,M)

d(T,H)l

d(T,H)

\dTjH
/dM\
(/dS\
r

\(es\

(ds\
/dM\
/8M\

\dHjT

\df)H
T

[m)T
"

PIWt
relation

{dHjT\df)H

fdS\

/dM\

We

have

used

Maxwell's

in

the

next to

to

last
=

equation.
or

This

is

obtained

by

transforming

dF=

S dT+

HdM

F*

F-HM

dF*

-SdT-Mdi/.

C)
per

(Here material.)
25.

S,

M,

CM

and

CH

are

properties

unit

mass

of

the

magnetic

According

to

the

problem,
T

we

have b
_

dS(T,0)_
-p=
=
-

Cm=o
B
we

j,i

A)

By

integration,
S

(T, 0)/dT=

0)

\b\T2
0),
-

(B
obtain

const.).

B)

Integrating
The

dF(T, F(T,
equation

-S(T,
0)
=

BT

b\2T

(A (C
=

const.).

C)
D)

CH/T
20
J
=

const.)
b
2T
+

is

inserted

into

E)

of

problem

to

give
TM2
-.

F(T,Mv )

'

A-BT

2C

E)

182

THERMODYNAMIC

FUNCTIONS

[Ch.

Thus dF dT whence
C ^M
~

IT2
b
=

2C*

7l

Jds\

cM

-o).

Since

F)

can

be

writ en

as

CH2

^-,
we

(8)

have

8S\

)
the

b +
T

CH

As

direct
T

means

of

obtaining

adiabatic
2

magnetic
M2
--,

susceptibility,

eliminate

from

F)

by

D)

to

get

and

thus

^J
dHjStH=Ho
C

A0)

( {dHjJ
2

\dM)H

C2Hl\

\C2HI

Tb

26.

According
of
H
as

to

the

third
Hence

law,

the
of lim

entropy

has
Substitute
=

limiting
Therefore

value
we

independent
have
to

r->0.

(dS/dH)T^0
by

(r->0).
problem
24.

\imT-.o(dMldT)H=0

B)

M=xTH

obtain

(dxrldT)
law
some

0.

Note:
X
must
=

Therefore,

both
hold these
of down

the
to

Curie

CIT
temperature.

and

the As

Curie-Weiss
TWO
a

law deviation

C/(T+
occur

6) only
from
the

finite

laws.

27.

When for
constant

entropy

paramagnetic
law
The the in

substance

is

H,
of
H

the
as

third
TWO.

tel s
curves

us

that
for

it

plot ed approaches
also

as

a a

function
constant

of

@)
the
same

independent
limit
as

i/#0
not
too

r->0

as

shown

figure.

If

is

large,

approach F)

of

the

solution

CIl.
to

3]

SOLUTIONS

183

problem

20

may

be

used

to

give

As

r-0,

dxr/dr-^0
field the reaches
0 K. is

as

was

shown
to

in
zero

the

foregoing
from
some

problem.
finite
at
some

Therefore,
value finite value
at
a

when
finite

the

magnetic

reduced

temperature,
never

temperature

stops

decreasing

and

it

28.

plate
M=0,
total

is attached the

to

the the
energy

end
X.

of

the when

spring
z0

and
is

weight
of the

(mass

M)

is

used
^=0

to

balance and The

spring
and
x

tension
is

Here,
W

the

strain
at

X=Mg
the

potential
(mass

of

weight
z0

height (g gravitational the on plate


=

plate
and

when

acceleration).
some

stored

weights
W
=

M')

kept
+

the
=

height
-

is
+

Mg(z0
if
x

-x)
x)
we

M'gz0
free

Mgx
of

(M
spring
F

M')
at

gz0

Xx

const.

Now,
strain

F(T,
and

is

the

energy

the

temperature

and

at

put
F*
=

F(T,
the total

x)
their

Xx

const.

A)

F*
are

is the

free

energy

of

system
free

including
energy

the is

purely
the

mechanical

system,
we

the

weights. potential

(Since weights energy.)

If

is

spring

constant,

have
X
=

kx

B)

184

THERMODYNAMIC

FUNCTIONS

[Ch.

and
F
so
=

F(T,0) F(T, X)
dW in
of

$kx2, X2/2k
x

C)
+
=

that

F*

dF*
The

$kx2 dF(T,
in
-

-Xx

0)
dx

0)
is dX
=

{kx-

dX

F(T, dF(T,

0), 0)

D)
-

dX.

E)

last

term

E)
x

d(ikx2)
the
energy

d($kx2)
free
energy

d(Xx),
of
the

i.e. decrease Note:

dF*

gives
in the
+

the

sum

of

increase the the


S
sum

the

the

spring
is
to

and

the

potential

That
that
F*
energy

(dF*/dT)x=
75'=
U

properly
of

weights gives
internal be

when

spring
of

stretched.

D)
verified.

with
energy

respect
the

the

entropy,
and

and

is the

spring

the

potential
29. As volume
was

of
in

the

weights,
20,

should the
free

shown
V
a

increases

problem by
moment

energy

of is

\VM2\xt
M

when
unit the

it

uniformly
the

acquires being

MV).

magnetic Compared

with

volume, (per non-magnetized


=

paramagnetic magnetized total magnetic

body
until
moment

of
it

state,

F(T,
The
moment

M)
between

F(T,
the

0)
external

iVM2/XT.
field
/

A)
and

interaction is

energy

the

magnetic

(This
in

the

corresponds foregoing

to

the

interaction

of

the

weight

and

the

gravitational

field

problem.) F*=F+

Including
W
=

this,

F(T,Q)-hTH2V
of
the

B)
system

may

be

considered material

as

the

free and
the

energy

plus

the

interaction

of

the

paramagnetic

magnetic

field.

Ch.

3]
In

solutions

185

the
P

case

of

dielectric
to to

with
M
x

dielectric in
an

constant

e,

the
E

electric
is P=
to

polar-

ization

((e
and
to

l)/4n
B),

(corresponding corresponds

above)

electric

field

(e
A),
we

l)E/4n
have

above).
=

Therefore,

corresponding

F(T,

P)

F(T,
=

0) F(T,0)
either

2nVP2l(e
e

1),

C)
D)

F*(T,
The

E)
be obtained

VE1.
F
or

entropy

can

from

F*.

In

the

case

of

magnetic

body,
=

we

have

S(T,

0)

\V(

xr

) M2

S(T,

0)

E)
and
S
=

-[--) \dT
rdF\

Jh

=S(T,0)

^VX'TH2.

E')

Similarly

for

dielectric,

/dF*\

F)

$0.

From

F)

of

the

foregoing

problem

we

have
V

)
(i)
tained tablished.
When the
From

de

A)
dif erence field
$

switch
the

is

closed,

constant

potential
and
a

is

mainis
es-

between

condenser

plates

constant

E0

<P/a

A)

where

Co (T)

T dS

(T, 0I
had
never

dT. been
at
a

(ii)
a

If
If

the the
=

switch

closed,
temperature

E=0

and

the
a

heat
surface
appears

Co (T). D/4n
=

switch

is

closed
=

To,
eo
=

capacity charge
on

is

of the
The

e0E0/4n
the condenser.
the

(Z>

electric

displacement,
the

e(ro))
the
remains

plates
remains

of

If

switch
D in

is

then dielectric

opened,

surface
constant.

charge

and

displacement

the

186

THERMODYNAMIC

FUNCTIONS

[Ch.3

4-

4-

4-

H(I-

specific

heat

under

this

condition

is
V

cd
Since
D
=

t[-~)
we

/8S\
have

=co(t)+-t

d2e

de

fdE2\

dT2

8tt

dT\dTJD

C)

eE,

dE2\
_

IE2

de

Substitute

this

and

s0E0

eE=D

into

C)

to

obtain

CC{)
31.
The

VTD2(de\2
is

D)

heat

absorbed
and

is of of

isothermally
the

by the dielectric quasi-statically


on

given
is

by d'Q
from

TdS
0
to

when
0.

the The

increased

potential dependence
solution

entropy
29

S,
and

the is

electric

potential

calculated

by

F)

of

the

problem

S(T,?)-S(T,0)=F
If

de(T)E2
dT
Sn

A)
is
a

the

distance is
as

between

the electric

plates
field
is

of

the is raised

condenser
Thus
from

and

the

potential
off

dif erence
dielectric

<P,
the

the

E=<P/a.

the
0 to

heat
<P is

given

by

the

potential

dif erence

T{S(O,T)-S($/a,T)}
in

de(T)
dT Sna
2'

B)

0=0

This

may

be

writ en

another
where

form
A

by
is

using
the
area

the of

capacity,
the

C=eA/4na, plates.
Then

of

the

parallel

plate

condenser,

B)

Ch.3]
becomes
-

SOLUTIONS

187

Q
energy

dlogT
stored / are, and the
in

C)
the

\C$2
32.
As

is shown

the in the

static the

electric

condenser. the
of the

figure,
of

a,

b and

plates,

width

the

plate

respectively, length

distance

between

the

parallel

plate

condenser,

plate

dielectric

and

jc

is

the

depth
of which
E=

by
the is

which
not

the
in

dielectric the field

is inserted
E

into

the The

condenser.
volume
Since of

The

volume
condenser

Vx
field
29.

dielectric

is

V1=abx.
is

the

occupied
is

by
we

the
can

dielectric
use

V0
free

ab(lx).
F*,

the
in

electric

<P/a
total

constant,
free
energy

the

energy,

given

problem

The

is

F(T,
of

0)
the of
the the
term

abx

eE2
dielectric

abl
+

E2.

F(T,
The

0)
second
it

is the
term

free is been

energy

entire

when in field

it
energy

has

no

electric the of
field.

field.
dielectric

the

sum

change
electric
is

the
and

free

of
energy

when

has

polarized
and
free
a

by
third
is

its
of

interaction
If
x

with

the

field,
the

the
energy

the
so

energy

the dielectric

electric
is

is the

increased,
condenser

decreased,

that

the

pulled

into

with

force
x
=
-

df^al
dx

8tt

E2

188

THERMODYNAMIC

FUNCTIONS

[Ch.

33.

J
fi

-pV
=

-NkT,
Po

A)

(l>

kTlog~.

B)
C)
D)

From

B),
^
=

^oe("-*)/fcT
F,/i)
respect
_

iVfcT/F,

or

J(T,
By

-jPoFe("-*)/fcT/
/i

dif erentiating

D)

with

to

and

and

using

C)

we

see

that

/dJ\

and

Also

we

have

\dlogPo
dT As
can

( *^
T

dT

be

confirmed

by

B),
'dJ\

this

satisfies
=N

(dn\~)
to

=-S.

G)

34.

The

rate

of is

temperature
as

change

due

the

adiabatic

elongation

of

rubber

band

given

Ct
Here

where

Q is given

the

heat

capacity
obtained
becomes

at

constant

(dS/dl)T=-(dX/dT)l
the

from

dF=

length. -SdT+Xdl,

the
was

Maxwell used. For

relation,
T=

To

equation

or

T
>s

Ci

Ch.

3]

solutions

189

The

temperature

change
Llo

due

to

an

adiabatic
L

elongation

from

L=\

to

is

AT

Al0
If when
300
L=

L-2(l+ar0)}.
The

B)
in

To

K,
1 + e,

<5

aT0
e

0.21.

where
e
=

is
-

determined

expression by
=

parentheses
=

in
or

B)

vanishes

3e + e2
-

25,
=

$d

ie2
L

0.14 in
the

i-0.020 figure.

0.13.

Equation

B)

is

plot ed

against

20

40

60

Note:
can

The be

relation
from

given
the well

in

this

problem
mechanical

between

the

tension
of

and

the

strain

derived

statistical
to

theory
vulcanized
The

rubber
and

elasticity
also is
AT<0
to
some

and

actually
other
here

applies
kinds
is called
strains
are

quite
of the is heated of

moderately
materials.
As
seen

rubber

rubber-like Joule due


to

thermal
the

effect

that

considered
for

effect.

in

small materials is
rubber
a

thermal

expansion.
when

up

(AT>0)

they

characteristic band.

rubber-like

elasticity.

the fact that figure, such t h i s , Ignoring are adiabatically. elongated One can easily verify

rubber-like This this


with
a

Chapter

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

There

are

no

new

principles
of

in

this

chapter.
to

Here

we

deal

with

the

most

important
such
as

applications
the and
or

thermodynamics
between

physics
of
a

and

physical
component,
or

chemistry
the
compomore

equilibrium
between the

dif erent

phases
of
a

single
two

equilibrium
nents

dif erent

phases
of

system

with

general
we

problems
of

chemical

equilibrium

concerning
In
the

dissoon

ciation mental

recombination

component
a

particles.
few theorems

section

fundafor

topics,
these

wil

discuss

and

concepts

useful

treating

problems.
Fundamental

topics

4.1. A
a

PHASE

substance

which

is

physically
states

and

chemically
such

homogeneous
as

is considered

single crystal ine

phase.
states

Dif erent
are

of

aggregation

gas,

liquid,

or

dif erent

dif erent
BETWEEN

phases.
DIFFERENT
PHASES
OF
A

4.2.

EQUILIBRIUM
PURE

SUBSTANCE
two

When
contact

phases,
each is

1 and

(indicated
are

with
the interface Plane

other

and
or

in

of

equal
which

dif erent
transmits

by equilibrium, depending
pressure.

single
on

and the the

double
pressure
nature
we

primes),
on

are

in

both the
must

sides
have

of

interface.

A)

interface

By
p,

C.26a-c)

p'
T'
and

p"
T"=T,

D.1) D.2)

fi'(p,T)
Equation
\i
=

ti"(P>T)
for

or

G'

G".
When the
transition

D.3)
the surfaces line
occurs

D.3)
\i

is
are

the

condition
constructed line The stable

phase
the
space

equilibrium.

and the

\i=\i"
coexistence

in

(/i, P, T),
A

intersection
when
is

forms

this realized

line

is
as

crossed.

of phase

the

two

phases.
the
The

phase
chemical
of

with

lower

the

more

phase.

order

the

potential phase

always
is

transition

Ch.4,2]

DIFFERENT

PHASES

OF

PURE

SUBSTANCE

191

Coexistence
two

curve

of the

the

phases

in

pT

plane^
4.1.

Fig. determined

by
4.1

the

order
a

of

contact

between

the

surfaces

fi

fi'
A\i

and

Fig.

represents
and

first
transition:

order

phase
The

transition,

a) First-order

phase dA/a/dp^O.

conditions

for have

this

are

\jl

h"

From

D.3)

we

dG

dG

or

dp
dT

AS
AV

TAV
q
=

(Clausius-Clapeyron

equation),

D.4)

where

TAS=T(S'
mole
and

-5")
A V is
The

is the

the

heat
transition.

of

transition

per

the

volume for derivatives


line it

change
this

per

mole

in

b) Second-order dA/nfdT=O, not equal

phase dA/nfdp
to
zero.

transition:

conditions
order

are

O, while Therefore,
=

the

second the

be,
fol ows

in that

Zl/i general,

0,

along
dV

coexistence

8V

fdAG \8p
dAG

D.5)

dT

192

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.
that

4, 3

In

order

that
dV
.

dp/dT

have

finite

value,

it

is

necessary

dp
dV

dV

dT
=

0,

or

df
latent

-A

AACp+T\A\
of
be

dV

dV\2
=

0.

D.6)

f
heat in
in

There nuities Second

is
or

no

this

type

transition,
heat less
at

but
the

there the

may

be
There A the

disconti-

singularities
order
a

the

specific
may

transition
to

point.
reader.
are,

transitions of
case

familiar
and

however,

number

examples
is the the

in

alloys
transition
at

magnetic
of
a

materials.
gas

particucritical

larly point
n

interesting
T=

phase

through
derivatives

Tc
order

keeping
phase
are

density
transitions:

the When
the the

critical
the

c) Higher-order
1-th the -th
in

density. partial
order

of
is

/i

up

to

all

continuous

and

lowest

discontinuity
said
exists
two

appears
to

order order. the


to to

partial
interface

derivatives,
is
not
or a

phase
and
the
so

transition
there

be

of

the

-th

B)
effect

When
due

plane,
when

generally
the

some

surface
matter

tension,
but
is
not

wall

between
pressure,

phases
in

is

permeable
dif erent

does

not

transmit

the

pressure

the

phases

equal:

i.e.,

On

the

other

hand

D.2)

and

D.3)

must

hold.
=

Therefore

we

have

G'(p',T)
Then the

G"(P",T).
is

relation

between

p'
V"

and

p"

determined

by

V
4.3.
SURFACE

dp'
TENSION

dp"

(Gibbs-Poynting

equation).

D.7)

Definition
area

of surface
the
If

tension:

The
two

work

necessary

in work done

order

to

change
the surface

the

of

interface
this
process

between
is

tension.

included,
becomes

the

phases equation

is the for
the

energy

against change

B.14)

for

quasi-static
dU
=

T
are

dS
the

p' dV
internal
of

p" dF"
pressure the

y da

\i

dN'

\jl' dN",
\jl

D.8)
/i" (T,
interface.

where/?'
are

and/?"
the

of

phases
and
a

1 and

2,
area

(T, /?'),
of the

p")

chemical

potentials

phases,

is

the

Ch.4,

4]

EQUILIBRIUM

OF

MANY-COMPONENT

SYSTEM

193

The

surface

tension,

y,

is

defined

by

this

equation,

i.e.,

D-8'
When

s,V',V",N',N"

Pressure

dif erence
phases
is
a

due

to

the
of

surface
radius
r,

tension:

the

interface
is

between

the

two

sphere

the

pressure

dif erence

given

by

D.9)
This dS
=

is

obtained
=

from
dN"
=

the

equilibrium
and
mass

condition
action
=

d?/=0 that

C.30a)
&V'l&o
=

by
\r
in

dN'

0, dV"=-dV

Equilibrium

condition

for

considering is given

let ing D.8).

by

Hf(T,p')
For

Li"(T,p").
radius,
r,

D.10)
of
a

example,
and

the its
vapor

relation
pressure

between

the

spherical

drop

of

liquid

is

given

by

fiJT,pr)

D.10')

(see
4.4.

problem
EQUILIBRIUM
DIFFERENT

34).
OF

MANY-COMPONENT

SYSTEM

IN

PHASES
we

For

simplicity,
of
the

assume

that

mechanical
so

equilibrium
that the

is established pressure

at

the
The

interfaces dif erent

dif erent
are

phases,
denoted
r.

the

is

uniform.
c,
are:

components

by
The

subscripts
conditions
=

1,2,. .,

and

the

phases

by

superscripts

1, 2,. .,

equilibrium
=

p'
r

p"=..
t"
==

pM
r(r)

Pi
=

D.11a)
r,

( D.12)

or

G'J
Proof:
We

G'j=-=G(f),
the
treatment

j
of volume

l,2,. .,c.
the the

D.12')
entropy
mole number of

generalize
energy

be

Sw,

the

U(k),

the

Let 3.6. K(fe) and

each
of

phase
each

194

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.

4, 4

component
SS

N^k\
=

Then

the
+

equilibrium

conditions

are:

dS'

SS"

+-+SS{r)

5U

fe=l

<5t/(fe) <5F(fe)
=

0, 0,

(b)
(c)

,57

fe=i

?
(b

(d)
fe=i

The

conditions
are

d)

are

obtained
and

by
undetermined

use

of

the

conditions

that

U,

and

Nj
-1/71,
5S-~SU

constant.

Using
and

(c) by p[T
+

Lagrange's (d) by -fij/T


c

multipliers,
add
to

multiply

(b)

by

(a)

to

obtain

-SV T

fc=l
=

0.

Since
zero.

the
Thus
Divertissement

variations
we

may

be

regarded
and

as

independent,

their

coefficients

are

get

D.11a,
10

b)

D.12).

substances. of heterogeneous der ist constant. Welt Energie strebt einem Maximum zu. Welt Die der Entropie summarized his work R. Clausius statements A822-1888) simple By these Formen der "Uber verschiedene die fur Anwendung Hauptbequeme was in der Warmetheorie" which mechanischen published gleichungen in the law of the fifteen second his after Poggendorf discovery 1865, years In Annalen und Bd. 351-400. der pp. CXXV, (Annalen Physik Chemie) this of the first and he established basic work very important expressions to us. the laws of thermodynamics are now second which familiar Ten in 1875, these J. Wil ard stateGibbs years later, put A839-1903) at the of heteroof his head ments "On the celebrated paper equilibrium i of J. Wil ard Vol. substances" Scientific (The Gibbs, genous Papers

Equilibrium
Die

Ch.4,

5]

GIBBS'PHASE

RULE

195

(Dover ciples
for

Publication
to

Inc.,
the
most

New

establish

heterogenous
potential.
from
to

systems,
The

York)). general introducing


rule

In

this
for the of

work
of first the

Gibbs

used time
the

these

prinof
re-

formulation
was

equilibrium
beautiful
almost

conditions

concept
theorems

chemical sulted
known

phase
scientists

one

this

formulation.
German
reason

This
for

paper

remained
years

entirely
when
French
was

un-

European
into
One

fifteen

until
in
1899 paper

1891,
into

it

was

translated

by
for

W.

Ostwald
was

(later
that

by
-

Le

Chatelier).
Transactions

this circulation. Ostwald

Gibbs'

of

the

Connecticut

Academy
Another
wrote
-

(Vol.
reason

Il ,
was

pp.

published 108-248)
that the
paper

in
a

journal
was

with

very
to

limited
understand.

dif icult

"Von der Verfasser

dem

Bediirfniss eine
Form

nach
Un-

grosstmoglicher zweideutigkeit Darstel ung


schwer

Allgemeinheit
des Ausdruckes

der

Untersuchung
hat ihre
vom

grosstmoglicher
abstrakte
Leser
years

geleitet,
durch

der ihre oft

gewahlt,
i bersehbare

welche

Gestalt eine
after

und

Aufmerksamkeit
When it work
von

Darstel ungsweise und Hingabe


introduced
was

nicht
it
was

gewohnliche
first

fordert."

was

to

Europe
fresh.

so

many

writ en,
ist noch ist

Gibbs'
heute

stil bloss die


es

unmit elbarer
ein

completely Wichtigkeit
historisches. enthalt worden. oder

"Der

Inhalt
das
Interesse der ist fast

des

Werkes
an

und
Denn
von

demselben
Fiil e
ein

keinesweges der Ergebnisse,


Antheil
den fruchtbar theoretischen

unabsehbaren
nur

anbahnt,
Noch

bisher

geringer
fur
von
zu

gemacht
wie

namentlich
und

den

grosster

Mannigfaltigkeit
Seitdem Werthe durch schon der wir fi r die das

Bedeutung
Gebiet ebenso Functionen
Grossen

liegen ungehobene experimentel en in den Kapiteln


der
wie fi r

Schatze
Forscher desselben

Tage.
die

Energie

und

moglich chungen
Theil

geworden,
experimentel geschehen

ausgedehnte Entropie allgemeinen


messbare
zum

verdiinnten
Gase

Losungen kennen,
wie ist
es

der

Gibbs'schen das noch der

Gleizum

darzustel en,
aber

ist,

grossten

Theil

Ausfi hrung

harrt."

4.5.
Theorem

GIBBS'
:

PHASE

RULE
a

When

system
the

phases is given

is

in

equilibrium,

consisting degrees

of

dif erent

components

in

dif erent
state

of freedom,
+

f
2.

of

the

equilibrium

by

f=c-r
of freedom, By degrees under changed freely Proof is there Besides
:
we

D.13)
of internal variables
of

mean

the
of

number
of
a

that

can

be

the

condition
ratio
as

The c\ these
we

internal

condition
the internal

single
far
common

equilibrium. phase
of
as

consisting
components.
the
for

components
means

determined
are

by
variables,
should

composition
variables
p

the

This
is

that

composition
the for
r

concerned.

and

are

dif erent

altogether

have

(c

1)

2 variables

phases.

phases. Being

Thus,
intensive

196

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.
are

4, 5
de-

quantities,
termined

the

chemical these
of

potentials,
internal variables

^fe)
only.
the the

(k=l,. .,r;j=l,. .,c),


Since number of
the

by
consists

equilibrium
of

condition
that is
can

D.12) freely

(r

\)c
satisfying

equations,
conditions

variables

be

changed

after

equilibrium

given

by

Example:
2

phase

Equilibrium system):
c=l,

of

two

phases

of

pure

substance
of three of

A
phases
two

component,
of
a

c=l,

r=2,/=1.

substance:

r=3,/=0
system:
11

(triple
c=2, r=2,

two-component
Divertissement

Equilibrium point). /= 2.

pure

Equilibrium

phases

of

Classification
Ehrenfest classification.

of phase (Leiden
His
Commen.

transitions

described

in
who
was a

4.1
the

is

one

given
to

by
such
on

P.
a

75f,
of the

1933),
order
of

first
is of

make based

idea
of

phase
in
a

change
powers

the

Taylor keep
If
retain
terms

expansion
terms

Afi(T
order
order

dT,p

+
we

dp)
obtain
the
we

dTand
of
curve,

dp.
the of

If order. if
second

we

of

the

first

only,
vanish

transition
a

first
and
the heats.

of
terms

the of
many

first
the

second

order

along alone, finite transitions,

equilibrium
have
e.g.

we

change
in

order,
We of
pure

which know

generally
first-order

exhibits

discontinuity
the
at

specific
CP
we

liquid-vapor
which
Ehrenfest's

transition

finite
few the

substance, (see Fig. examples


of the the

except

at

the
some

critical deviations

3.7).
which transition

For

second-order
show

point, changes,
from
to

becomes know
scheme.

in-

however,
the

only
In
for
H

case

of
curve

superconductor
is drawn
in
occurs

normal

state,
where
heat

inis
the
at
a

stance,

equilibrium
field.
on

the

H-T without

plane,
latent

applied
one

magnetic point
L.

The
the
Rev.

transition

only
makes

H=0

equilibrium
65
at

curve,

where

Ch(=
that

jump.
comes

Onsager logarithmically
else
for
L.
out

(Phys.
infinite
a

A944)
the

117)
transition

proved

CV) CH(=
but Technical is in

CV)
continuous
the
case

be-

everywhere
H No.
=

two-dimensional
I.
T. Transitions

Ising
of
in

point ferromagnet,

0.

Tisza

(M.
Phase
the

Laboratory expansion
of
fi

Electronics

Report,

127,

1949;
that

Solids
is

(Wiley,
invalidated
second classification
87
or

New

pointed
infinite
or

Taylor
coefficients Ehrenfest's
T.

dif erential both


C.
N.

of

the

by higher

the is

York, possibility
order
for

1951))
of
one

phases.
Yang
of the
same

Thus
and D.

original
(Phys.
between
the
Rev.

certainly
proved
transition
Both

inthe

complete.
Lee

A952)
of

mathematical and
have from that

equivalence the ferromagnetic


structure,
in
to

theory
for

404, vapor-liquid
models.
curve

410)

problem
and the the

simple
vice
the
versa:

theories be obtained

magnetization
and

can

the

isotherm
the

p-V

corresponds

chemical

plane, potential,

the

magnetic
to

field
the

and

magnetization

den-

Ch.

4, 6]

THE

CHEMICAL

POTENTIAL

OF

GAS

197
appear
as a

sity.
order
pressure.

This

means

that

the

vapor-liquid
of
is considered in
to
a

transition substance
to

wil
is observed

second
vapor

change,
The

if the
heat that the

evaporation
CP

under
than

its

specific
sense

be
to
cause

less

fundamental

CV,
short-

in

the

anomaly
interactions
seem

CV
seem

is
in
an

linked
infinite

with
a

long-range
range

molecular
interactions Rice interaction

mechanisms: ordering in CV, while jump


at

result

CV
showed
the

the

transition

point.
if
such shortof the
=

O.
range

K.

(J.
but

Chem.
is

Phys. independent
if it

22

A954)
of

1535)
volume,
on

that,
transition
a

remains

second becomes into


any
a

order,
unstable

that,

against
transition.

depends the change


He

the

volume,
and
we

system
the
never

with

CV

in stated from
a

volume
that

transition expect

changes
to

first-order

should
transition.

find

infinite

specific
CHEMICAL

heats,
POTENTIAL

apart

first-order

4.6.

THE

OF

GAS

The

chemical
gas

potential

per

mole

(Gibbs

free

energy), log
p,

G(T,p),

of

pure

ideal

is

G(T,
where

p)

G(T, G(T)
T

p0)
+
Tt

RT

(plpo)

D.14)

RT

log

D.14')

G(T)
is
p0

=U0-

CT

log

H-j^-|
0

C'(T2)dT2
'

RTi(+
the

RTlogp0)
D.15a)

the

chemical this is taken

potential
as

at

the last

temperature
term

and

standard

pressure*

(if
Also,

1, the

is

0).
T

U(T)
is

=UO
mole. heat

(CP-R)T+
Uo is the
at constant

(c
molar the
pressure molecule.

G\)
internal
due
For
a

dTi
at

D.15b)
T=

the
is

internal
the and
for

energy

per

energy
to
a

0, and
gas,

Cp
motion

molar
the
a

specific
rotational
diatomic

the

translational

motion
gas

of

monatonic
gas,

C^=|i?,
Also

C
due
room

?jR,
to

and
the

for and

polyatomic
vibrations
i is gases

(^
molecules,
constant.

4^.

C
is

(T)
normally D.15a)

is the is

specific
small
a

heat
at

internal
for

of

the

which
Note:

temperature
gases

the

chemical

good

temperatures.
Henceforth,
the

However,
double bar

approximation for light


on

normal
as

except
the

at

very

low
heat

such

hydrogen,
per

specific
pressure.

(G)

indicates

quantity

mole

at

standard

198

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.

4,
some

due

to

rotation

is

not

constant

below

100 6 in of the

K,

and

D.15a)
3 of

requires
Statistical
in

correction

(see
molar
is
=

example
chemical

1 and

problem

Chapter
component

Me-

chanics).
The
mixture

potential
+ +

Gj

j-th.

an

ideal

gas

Gj(T,p)
Here,
nent
at

Gj{T,p0) Gj(T)
pressure and
=

RT\og(pjlp0)
=

RTlogpj
chemical
p0,

Gj(T)
potential
at

RTlogp
the

RTlogyj.
gas pressure

D.16) D.16')
they-th
p0
=

G^(T,p0)
the
pressure,

is the

of

pure*

of

compo-

<j

(T)

is that

the

standard

1,

is

the

total

pj
where The

yjp

is the

partial
fraction ideal
gas

pressure,

yj
Gibbs

ny/?
free

ny
energy

is molar of
an

of mixture
c

thej-th
is

component.

G(T,p,nlt. .,nc)=
=

nfij(Ty

p)
D.18) log
2

tnjGj(T,p)-TAS,
yj
=
-

where

AS is the

R?nj
(see D.14)

log
example
and from

?n

?y,
Chapter
are

yj
and in

D.19)
problem
the 13
in

entropy

of

mixing

in

Chapter
Real
manner

3).
gases:
to

Equations
include deviations

D.16)
ideal
gases: pv,

modified

fol owing

Pure

gas:

(T,

p)
p)
is the pressure

(T)

+ + +

RT

log
RT
RT

D.20)
pjVj
p
+

Mixture:

Gj(T,
G
or

Gj(T) Gj (T)
chemical
p0.

log
log

RT

log
pure the

yjVj,
gas
at

D.21)
temperature
which
has
T

where
and the

Gy

potential
Here,
v

of
or

the

standard

vy

is

fugacity

the

property

limv=l,
p-*Q

p->0

limvy=l.
accurately
defined

D.22)
expressed
in
a

Note:
p.=py.
*

For in

real

gases,

(j

and the

are

not

by
formal
way

D.15).
and

Also
does

D.21)
the

is

only

partial
0 indicates

pressure
pure matter.

Henceforth,

superscript

Ch.4,
not

7] have
gas

CHEMICAL

POTENTIAL

199

such

direct

physical
an

meaning
ideal
gas
as

as

in
goes

the
to

case

of
zero,

ideal
the

gases.

Since
v

any
must

real

approaches
1
CHEMICAL
OF
as

fugacity

approach
4.7.

p->0.
POTENTIAL AND SOLIDS

SATURATION

VAPOR

PRESSURE

LIQUIDS
to

AND

According

D.3)
(pressure

the
must

molar be

chemical

potential
to

of
chemical

pure

liquid
potential

{solid),
of
the

G\ici{T,p),
saturated

(Gsol(T,p))
vapor

equal

the

p):

Gu*(T,
where

p)
chemical

0eas(T,
potential D.14).
solids

p)
of
This

Geas(T)
the is saturated

RT vapor.

logp, (Here
since
in
we

D.23)
have
the

(jgas
the
pressure

is ideal

the
gas of

used
vapor

The

molar

chemical

solution)

Gjnq(T,p)

equation and liquids potential is given

is

usually

permissible low.)
component
a

saturation

ofthej-th
by

solution

(or

solid

Git liq(T,
where

p)
chemical

Gj,gas(T,
potential mixture),
pressure of

p)
of

G?gas(T)
they-th
the the
and

RT

logPj,
in

D.24)
the
gas

GJgas
as

is

the
an

component
chemical

(considered
component
saturation

ideal standard
pressure

gas

C/y(gas
p0

potential
T,
in

of and

phase they-th
pj
is

at

the

temperature
the in
the

the

vapor

the

j-th
can

component
be

solution

(solid
way

solution)
by

(see
comparing

D.16)).
it

Equation
with
a

D.24)
liquid
of

rewrit en

fol owing

pure

they-th

component:

GJt
where

liq

(T,

p)
potential

<?Jt

]iq

(T,
of

p)

RT

log

Pj

%,
is

D.25)
given

liq,

the

chemical

they-th

pure

liquid,

by

?&
in

^
Po

D.26)
temperature

which/??
liquid.
In

is the

saturation

vapor

pressure

at

the

T, of

the

pure

7-th

Equation
normal
range

D.25)
of of
a

is

obtained

by eliminating

G
the
so

gas

from

D.26)

and
of

D.24).
the pressures the in

chemical

potential
may

liquid
by
p,

(say, (solid)
which

atm)
small

pressure

dependence
in

is

that/ ?
to

Gjt UqG1,/?y)
D.27)

D.25)

be

replaced

simplifies
Ilq

D.25)

Gh i,q(T,

p)

Gjt

(T,

p)

RT

log

^. Pj

200

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.
solution
vapor

4, of

This chemical each

equation
potential
component.

expresses

the
of If the is the modified
pure pressure

chemical

potential
liquid
change
to

in

in

terms

the
of

and

the

saturation
in
pj

pressure

neglected

D.27)

is

taken

into

consideration,

D.27)

GJtUq(T,
The
4.8. Two

p)
usually
SOLUTIONS

G$m(T,
small.

p)

RT

log

Pj

%+

f
J
p

dp.

D.27')

last
DILUTE

term

is

component
molar
concentration

solutions:
is saturation the

The

solvent

is denoted

by

1 and

the

solute

by
con-

2.
the

The

xl:x2(xl+x2
vapor

l).
of

For

sufficiently
solvent
px

small
fol ows

centration, equation
which
pure

pressure

the

Pi

*iPi

(T
law Raoult's

const.,
is

xx

->

1,

x2

->

0),
pressure
to

D.28)
of the
satu-

is

an

empirical
This
pressure
Pi

limiting
is

(p
p2

the
law. fol ows
=

saturation

vapor

solvent).
vapor

called
of
=

ration

the

solute

Corresponding Henry's
const.,
x2
~

this,

the

law,

k2x2
characteristic

(T
of

0),
The

D.29)
chemical

where for each

k2

is

constant

the

solution.

potential

component

becomes

G, (T, G2 (T,

p)
p)

G (T,

p)
p)
+
are

+ +

RT
RT

log log

Xl

(xx
Pi

1)

D.30a)

G2G\
(j>2(T)

k-2X02
from
the

(x2

0)
D.30b)

RT\ogx2.
derived
solvent
are

Equations D.29) 13). (see problem Many component


2,3,. .
have in The
the molar

and solution: concentrations


as

D.30b)
The

Gibbs-Duhem

relation
the solutes

is

denoted law
+

by

1 and

by
we

x1:x2:x3:. . By

analogy

with
a

D.28),
solution)

limit

xl~l,x2-+0,x3^>0,. .
or

(Raoult's

for
+

dilute

Pi=XiPi, In

Pi
to

Pi
o

Pi
not

=X2

*3

D.31)
from

this
the

case,

it

is

possible
alone.
be

determine if
the
we

G2,
assume

G3,. .,p2,p3,. .
that
a

the be-

Gibbs-Duhem
tween

relations solutes
can

However,
in

interaction

ignored

limit

of

dilute

solution,

we

may

Ch.
assume

4, 9]

IDEAL

SOLUTION

AND

REGULAR

SOLUTION

201

that

Pj

kjxj
G:
+

(;
RT

2, 3,. .;

Xj
=

0),
RT

D.32)

Gj
which 4.9.
If

log
to

-*J
Pj
the

logxj,
case.

D.33)

equations
IDEAL SOLUTION

are

analogous
(IDEAL

two-component
AND

SOLID-SOLUTION)

REGULAR

SOLUTION

the

relations

G1=Gl(T,p)
are

RT\ogx1,

|
pressure and

valid
the

over

all

possible
is said this.
to

ranges

of be
an

temperature,
ideal solution

concentration
in the

ratio,
case

system
a

(ideal
there
are

solid-solutions
real

of
not

solid).
very

Although
far in
is

this

is
free

an

idealization,
when
an

systems
is
made

which

are

from
the

The
pure

change
substances

Gibbs

energy

ideal

solution

from

given
+

by
-

AG
or

x^Gt
AH=0,

x2G2

x^

x2G2

RT(x1

log*!

x2

logx2),
D.35)

AS=-R(xllogxl+x2\ogx2),
entropy
vapor

which
The

gives
saturation

us

the

of pressures
Pi
=

mixing,
are:

^?ideai.
Pi
a
=

*iP?,
considered
and

x2p2.
solution
such
=

D.36)
that

Regular

solution:

Hildebrand

AS
are
we

ASideal
systems
which

D.37)
approximate

and

called Let
AH

it

regular
a

solution. function
of
x2.

There
Then

real
have

this.

be

G1=G1

AH-

dAff
xt

dx2
dAff

RT

log*!
=

(fH1(T,p,x2) (t>2(T,p,x2)

D.38)

x2

+
OX-,

RT

logx2
=

RT

\ogx2.

202

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.
SOLUTIONS

4, 11

4.10.

EXPRESSIONS
are are

FOR

CONCENTRATION to

OF

There

various
some

ways

express

the
used:

concentration

of

solution.

The

fol owing 1) mole

of
x2

those
mole

commonly
number
solvent
+

fraction,
mole

of
mole

solute number of
solute
tiy

n2
'

number
m2
=

of

n2

2) 3)

molality, molarity

mole

number

of

solute
c2

in

lkg

of
<

solvent;

or

molar
=

concentration,
mole

number

of
of

solute solvent

in

1 litre

of

solution. of
px.

Let

the

molecular of the

weight
solution
are

the
the
to

be of

Mu
the

that solvent in the

the
The

solute above
way:

M2,
men-

the

density
tioned

and

density
one

parameters
1000
m2
2
=

related

another
x2
=

fol owing
m2
---
---

x2
,

-^-

My
=

Xy
.

m2
=

A000IMy)

^,

D.39)
D.40)
V

C2
When

1000

+
can

M2m2
be

1000,

m2

(C2M2/1000)

x2~0,

they

approximated
1000

by
C2~pym2.
COEFFICIENT

m2~~WXl'
4.11+.
ACTIVITY
AND

D.41)

ACTIVITY

Write

the

chemical

potential

of
=

the

y-th

component
+

in

solution

as

Gj(T,
which
are

p)
=

Gj{T, Gj{T)
G
the pressure

p)
+

RT

RT

logaj(T, log aj(T),


G
were

p)
defined of of
the

D.42)

D.42')
before

Equation
in
can

analogous D.42)
so

to
or

D.34).
defines the

and

(4.7).
component

the
be

solution.

D.42') Usually
that
eq.

ignored,

D.42')

is

activity a}{T,p) dependence good approximation.

y-th
and
In

Gj(T,p)
eq.

aj(T,p)
D.42'),
D.43)
we

put
aj
which
p,
=

yjxj,
yj.

or

7j=
Let

xj
saturation

J,
vapor

defines
the

the

activity
of

coefficient
the

thej

pressure

be

concentration

y-th

component

yjt

the

fugacity

v,-

and

the

Ch.

4, 12] vapor

SOLUTION

OF

STRONG

ELECTROLYTES

203

saturation

pressure

and

the

fugacity

of

they-th

pure

liquid

be/?

and

v.

Then

we

have
a,

y,Pi
,

P
=

V-

>

(sat-vaPr

i ideal

gas)

-0

'

Vj
For
an

J^O

~0

(sat.

vapor

| ideal

gas)

j7~O
by

D.44D)

A\m.\

ideal

dilute

solution

(xt

1,

x2

~0)

we

have

D.33)

chemical
various

definitions potential
forms

of
of

the
solutes

activity
in
on

of
an

solutes

in

general
solutions
the
x2 m2

dilute
can

solutions:
be

The writ en
in

ideal
we

dilute
express
RT

depending

the

way
=

concentration:

G2

cfH2

log
log

D.46a) D.46b) D.46c)

\ogC2,
where

(f>2
In

(fH2write
to

RT

logtlOOO/Mi),
chemical
the

and

<f>
a

<f>'2-RT
solution
the

logpt.
in coefficients
a

order

to

the

potential
activities
a2>

of

general
and

dilute

form

analogous
T2
72>

D.46a-c),
introduced
RT

a2,

y"i
=

are

by

the

fol owing
+ + +

a equations:

activity

G2

(jH2
02 4>2
limit
SOLUTION

+ + +

loga2
log^
an

<t>2
(j>'2

RT

\og{y2x2)

(a2
(a'2 {a
and

y2x2)
y'2m2) yC2).
1.

D.47a) D.47b) D.47c)

RTloga'2
RT

(j>

RTlog(y'2m2) RT log(y5C2)

In

the

of

ideal
OF

dilute
STRONG

solution,
ELECTROLYTES

y2, y'2
molecules

y

all

become

4.12+.
A

solution
and

in

which which

the

solute
is called

are

positive
molecule

negative

ions

strong
the solution:

completely electrolyte.

dissociated

into
a

Consider

solute

Av+Bv_
positive
From
the

dissociates

in

Av+Bv_-v+Az+
into
v+

+v_Bz-

(z+>0,z_<0)
z+

D.48)
ions,
have
B2
,

ions condition

Az+

of of

valence electrical

and

v_

negative
we

of

valence

|z_|.

neutrality,

v+z++v_z_=0.

D.49)

204

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.
concentration
of

4, 12

Let
ions

x2

be
x_

the the

concentration
concentration
x+=v+x2,

of of

the

and

solute, negative

x+

the

positive
then

ions
x_=v_x2.

(in

mole

fractions),

D.50)
ions,
y_

Let
y the

y+
mean

be

the

activity activity

coefficient

of
y is

positive
defined
>

that

of

negative

ions

and

coefficient,

by
v+
+
v_
=

yv
The molar
=

y++7-~
of

v.

D.51)

chemical
=

potential

the
+

solute

in

solution,
+ +

G2
v.RT vRT

GAv+Bv_
log(y_x_)

is

Gi

6av+bv_ 0av+bv_

0av+bv_
vRT

(T,
logx2
+

p)
RT

v+RT

log(y+x+)

log(vv++vv_")

logy.

D.52)

Debye-Hiickel

equation:

logy
where

-^^.
.

D.53a)
,

lOOODkT

v_zi)C2 y-.
number of
of
an

D.53b)

Here,

Z)
e

is is

the the
is

dielectric

constant,
electric
the
ions

No

is

mol),
average

elementary
of defined
I
=

charge
C2
is the

diameter

and

Avogadro's (charge molarity

F.024
electron),
solute.
a

1023
is

the

the

Ionic

strength

by

YJZiCi

i(v+z2+
A

+v_z2_)C2.

D.54)

Eq.
where

D.53a)

then

becomes

logy

-z+

|z_|
/
2tt
t^^;

,/i/(l
-

Ba

JY),
Sne2No
\
"

D.55a)

e3No
-

7^*

1
in the

)
denominator
eq.

'

\^oood#ry
of
eq.
can

'

In

dilute
to

solution,
1.

koi

compared

Correspondingly,

D.55a)

be

D.53a) approximated

may

be

ignored
by

-z+\z_\Ajf.
Additivity
state

D.56)
depends
the
pure
on

for
is
as

ions:

The

value
states

of

0av+bv_
of
to
V +

how
A

the
and

standard
B
are

chosen. the

Once

definite
it is
+

substances

chosen

standards,

possible
Bv=

put
+

0Av

0A*+

V-0B*-

D.57)

Ch.4,

13]
and A2+

CHEMICAL

EQUILIBRIUM

205

0Az+
of

4>B*
and B2~

are

the in This

standard solution
from is

free

energies
the the the
basis ions is
constant to

of
pure

formation
and in Arrhenius'
appear
may

of
are

1 mole

of of of

ions

the

substances
of

determined

experimental y. dissociation. lytic and negative


For

additivity
However,
since
common

always
put
O.

theory pairs

electro-

ions,

the

additive

be

chosen

positive arbitrarily.

convenience,

the

usual

agreement

D.58)

4.13.
We

CHEMICAL

EQUILIBRIUM
now

consider

the
aA

equilibrium
+

of IL

the
+

chemical
mM
+

reaction

expressed D.59)

by

bB+ ++
+
=

or

vAA

vBB

vLL
vL

+
=

vMM /,
vM

+
=

D.59')
this free
in

(vA
Sincep fol owing.
Free

-a,vB
constant

-b,. .,
in

m,. .).
we assume

and

Tare

usually

chemical

reactions Let
in

the
be

energy,

enthalpy
Consider

and

entropy
the

G{nA,nB,. .,p,T).
component

of reaction: changes
=

the

Gibbs number

energy

the

mole

of

each

$nA
Then

va

<^>

&nB

vB

<5A,. .,

5nL

vL

62.,

D.60)

the

corresponding

change

SG

becomes

therefore

-jOA-=AG,
Here

AG

ZvAGA
A

-aGA-bGB-+lGL
of

mGM+-.
of advancement of reaction,

D.61)
of

AG
reaction.

is the The

free
A G

energy

the
are

enthalpy
by
means

of

reaction, reaction,
of

and

X is and

the

degree
entropy

AH,
the

the

AS,
D.62a)

derived

from

equations
d dT

AG

Aff-TAS,
AG
T

AH=-T2~~,
If

dT advances

AS=

AG.
from

D.62b)
the left
to

AG<0

the
as

reaction
there
is
no

(as

long

D.59) inhibition).

spontaneously

the

right

206

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.

4, 14

The

equilibrium

condition

is

<5<j=0
=

or

AG
Standard
the
pressure pure

?vAGA
If

0.
are

D.63)
the

free
substances

energy

(normally
free
energy

of reaction: A, B,. . atm),


of

@A, Gg,. .
at

chemical
T
can

potentials
and standard
defined:

of

the

respectively, fol owing


A G AH
= =

temperature
be

quantities

standard standard

reaction

? vAGA,
Pi ( A

D.64a)
7^
I T\
,
=
-

enthalpy
entropy
of
action:

of

reaction

?
?vASA
D.59)

vAHA
=

T2

D.64b)
D.64c)

standard
Law

reaction
If

AS the

of

mass

reaction
+

is

gaseous

reaction,

we

have

AG
Therefore
eq.

I
D.63)

vA
can

{GA
be
=

RT

\og(pAfA)}
as
I
m

(fA
rlrm
rarb

fugacity*).

writ en

11 (Pa/a)VA

PaPb--=

nb

JaJb

exp(-AG/RT);
can

D.65)
be considered be
writ en
as

is

the

equilibrium
=
..

constant.
=

If in

the

gases

ideal,
as

we

have

simply/A=/B Similarly

l.
a

for

reaction

solution,

D.63)

can

D.66)
Example:

iN2(g)+$H2(g)
gases
are

NH3(g).
ideal,
eq.

If

the

assumed

to

be

D.65)

applies:

Pn2Ph2
4.14.
THERMODYNAMICS

OF

ELECTROCHEMICAL

CELLS

Electrochemical
tween two
or

cell: metal ic
sometimes

An

electrostatic
which

potential
sandwich several

dif erence

develops

be-

electrodes

electrolytes

(usually

solutions
*

solids).
quantity
More

/a
the

is

dimensionless
pressure

of

standard

po.

(expressed explicitly,
=

as

va

in

D.21)).

In

this

equation

pa

is in

units

AQ

vA

(?a

Ch.

4, 14] 1. 2.

THERMODYNAMICS

OF

ELECTROCHEMICAL

CELLS

207

Example:

Cu|CuSO4(aq)|ZnSO4(aq)|Zn AgCl2 (c)|M+Cr Ag(c),


circuit cathode of
the

(Daniel

cell)

D.67a)

(aq)|Hg2Cl2(c),
is

Hg(l).
electrons reduction
For

D.67b)
(e)
flow
and

When
anode

the
to

external
the
at
+

cell
the wire

closed
and
in

the

from
oxidation

the

through
cathode
2e
->

general
Zn
+

take

place
Cu

the
+

and Cu

anode,

respectively.
Zn
->

example,
2e

(reduction),
reactions
to

+ net

(oxidation).
reaction takes

D.68) place through


the in

As

result cell

of

such

electrode the

certain

the

corresponding

amount

of

charge,

q,

transferred

semi-permeable
which

wall

through
can

only

SO24"
4.2. Daniel

iorts

pass

Fig.
external
Zn
+

cell.

circuit.

In
+

Daniel

cell,
or

by

D.68),
Zn
+

the

reaction
->

is
Cu
+

Cu+

->Cu

Zn++
that
-

CuSO4

ZnSO4.

D.69) D.70)

Generally,

B.25)

requires

W^-dG,

208

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.

4, 14 of

where
the

is

the

work Consider

done

to

the

environment shown of the


zero

and

SG 4.3.

is the
When

decrease

free

energy.

Reversible

cell:

the
to

circuit

in

dif erence,
the cell
current

Ee> is applied flowing through


balanced

the

terminals
the cell

Fig. cell,
and

potential
in

g,

by
the

potentiometer,
reaction

becomes
of than the
E

the

is

Ee
If, however, advances,
ceed in

(e.m.f.
smaller

ceil

g). (Ee<E),
E,
and
the

Ee
while

is if

made

slightly
is
made

then reaction chemical

the

reaction wil
pro-

Ee

slightly
If all
the

larger

than

the

opposite

direction.

physical

phenomena

standard

cell

Fig.
in

4.3.

the

cell

are

reversible,
in in

then the which cell. there

by
A
are

maintaining
cell
in
contacts
cases

Ee
which

it

quasi-static
reversible
are

changes
cell. Cells

this between

is

is possible possible electrolytic be

to

cause
a

is

called
solutions
as

generally approximately
Electromotive cell
in

irreversible,
a

but
cell.

in

some

they
Daniel

may

considered

reversible

(Example:
cell:
electric is
The

cell.)
write

force
the form

the

of D.59).
of the

reversible then
=

We

the

internal

reaction

of
the

advancement,

SX,

reaction

change given

Sq
by

transferred

during

Sq

z$ $

SX

(z=2

in

the

example

of

D.69)),
^
=

where

is

the

Faraday

constant:

96485.3
Since

coulomb/g-equiv.
the

Here

the

work

is

W=ESq.

equal

sign

applies

in

D.70)

(reversible

Ch.

4, 15]

THE

THIRD

LAW

OF

THERMODYNAMICS

209

change),

the

electromotive

force,

E,

is

given

by
,

D.71)
consideration,
#
a

where

AG
Electrochemical
a

is

the

free
Zje
and

energy

of
If,
this

reaction.

potential: charge
at
zero

in

system
is
at
as a

under

particle,
to

/, has
environment

system
considered

potential
earthed,
=

with
must

respect
be

the

potential,
d'Z
=

A.7b)
rjj

changed

? fa
the

Zje<P)
electrochemical

dNj
if the

dNj.
of
a

D.72)
they-th
$"
compo-

Here,
nent

r]j=nj
of Instead the of

zje<?>
(e
if

is called
is

potential
we

system

D.3),

the

replaced potentials
in
2 becomes

by
of the
mass

consider

mole).
and

phases
action
of

are

<P'
the

respectively,
with

the

equilibrium
to

condition

y-th

component

respect

phases

1 and

n'j
Note:

n"jforce various
can

D.73)
be
in
contact

Equation
the

D.71) equilibrium
10).
OF

for

the

electromotive
the

derived within

by

con-

sidering
cell
4.15.

between

phases

the

(see

problem
APPLICATION to

THE

THIRD

LAW

OF

THERMODYNAMICS

According
standard
free

the

third
of
a

law

of

thermodynamics,
AH-TAS
AH
can

the

free

energy,

or

the

energy

reaction,
AG
=

can

be

obtained obtained
for from
0 K

from

thermal

data.
the

be
the

measured

as

the
and

reaction

heat.
the
over

A Sis

by

knowing
each
to

specific
substances

heat,
of

heat
in

of
For

fusion the reaction

heat the
can

of be

vaporization
range

of

the

involved
reaction.

the
formula

temperature

instance,

it

calculated

from

the

^gasl^

>

P)

dT
^p,
solid
_

Lf
"T

f
J
Tf

dT
^p,
liq

Lv
T

"T

dT
^-p,
gas
^,
>

J
0

1(

J
Tb

D.74)
where

Tf

is

the
at
are

melting
pressure

point
p,

at

the

pressure

p,

L{

the of
in

heat

of

fusion,

Tb the

boiling

point

Ly
heats

the
at

latent
constant

heat
pressure

vaporization,
the

Cpsolid,
respective
in this
manner

Cp>liq,
indicated

Cp>gas
by

the

specific

states

the

subscript.

The

values,

AS

or

AS0,

obtained

210

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.

agree librium
a

with
constant

those
or

obtained
from
such
thus

from the

the

temperature
force
results of
Nernst
constants
etc.

dependence
the
to

of
The

the

equiof of

electromotive
to

cell.
his
of

existence
the chemical data.

great
law.

number

of

third

It
and

is

experimental possible
The

led
the the

discovery
thermal

calculate
of

equigives
the
pressure
structure

librium

the
constant:

electromotive
of the since solid
constant

force

cell,
gas.

from
in

Chemical
absolute
pressure of the of

value
constant

entropy
it also

constant, of
It
can

i,
an

which It absolute derived

ideal
the
be But

appears is sometimes

D.15a)
called
the
vapor

the
vapor

gives

value from
frame work
and
constants

of the of is

liquid
gas

or

phase.
mechanics. characteristic
this

molecular

the
is
is

by
a

statistical
Since

in of
a

the

thermodynamics,
to

it it

strictly
also called

substance

be of
gas

determined

empirically.

determines chemical
constant.

the

equilibrium

reactions

the

Examples
1. The

isotherms
maxima
minimum
of

of if and volume the


How

van

der

Waals
is of the wil
states

gas

plot ed
below
an

in

the critical
the

(V, p) plane
temperature.
pressure

have
decreases

minima

and

the the
so

temperature
maximum that
is
from

the

Between with
be

the
decrease In
the

isotherm,
be

must

unstable
two

and

cannot

realized.

this
gas

region phase.
determined whole
mass

system
the

separate

into
pressure

phases,
for

the

liquid
of
Waals

phase
the

and
two

equilibrium
a

coexistence
der

phases
is the
Solution In the
answer

given

isotherm

of

the
among

van

type?

How

of

the

system

distributed

the

two

phases?

Express

geometrically.

Fig.
states

4.4,
on

ABCDEFG
AB
must
are

is
have Thus

an

isotherm

for
those
F
on

one

mole
FG
are

of gaseous.

van

der Two

Waals

gas.
in

The

equilibrium potentials
same

liquid, equal
if B

and
pressures

phases
chemical
lie
per
on

D.3).
horizontal
states

and chemical
be

are

in

(condition equilibrium, by

D.1))
they
free

and

equal
must

the

line.

The and
F
can

potentials
compared
From

of

the

B,

chemical

potential
find

along

the

isotherm.

(Gibbs considering the equation

energy

mole)
in the

the

change

dG=
we

Vdp

G(D)-G(F)=
FED

Kdp

area(FEDF)

Ch.4]

EXAMPLES

211

and

G(D)
Therefore
the
so

-G(B)
to
to
=

area

(DCBD).
has
a

state

and

it

is

unstable.

corresponding According
-

the

above
-

higher equations,
area

free

energy
we

than have

or

<7(B)

<7(F)

area

(FEDF)

(DCBD).

Fig.

4.4.

Thus, equal, phases.

if

the then
If the

horizontal

line
=

is

drawn
is

in

such

way

that condition

the

two

areas

are

G(B)
horizontal
and

G(F),
the

which line is

the

drawn

equilibrium higher
or

of

the

two
or

or

lower,

(j(B)<(j(F)
phase
becomes
cuts

(j(B)>(j(F)
stable
areas

either
other
AB

liquid
when

phase
the

the

gaseous

the

phase.
the
curves

In

words,

horizontal
GF

line

BDF

off
a

equal
stable

(liquid
for

phase)
of
two
a

and

(gaseous
occurs

phase)
at

become
pressure

isotherm.

The
vapor
two

coexistence

phases
given
of
the

this
is

pf(=Pb)
and the
rest

(saturated
When
gaseous.
a

pressure) phases
these

temperature.
whole
state

coexist,
circumstances
a

part

system
of
the

liquid
is

is

Under
on

the

system

point

BF.

Thus ratio
of

quasi-static
two

isothermal

compression
some

GFDBA. termined
in

The the

phases
way.

at

intermediate
n

fol owing

Of

the

total

moles

of

the

represented proceeds M, point substance,

by along
is deus

let

212

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.4 total

suppose
sum

that
of

nx

moles

are

in

the
or

liquid

phase.

The

volume,

nVM,

is the

nxVB

and

n(\x)

VF,
xVB

(l-x)VF=VM.
F vA
_

Thus

l~~~
i.e. Note:
curve

'

the is

ratio The

MF:MB

gives
of the

the

mole
area

ratio
to

of

the

liquid
the stable

and

gas

phases.

condition Maxwell's

equal
rule.
states

determine
to

equilibrium
CDE
cannot

called

Strictly
realized
as

speaking, thermodynamic
the
In

corresponding
states

the

curve

be

since

the

Therefore,

quasi-static
the One solution these der

processes

stability involving
we

condition these have


states

is not
are

satisfied.

hypothetical.
dG=
V

given
states.

here,
The

applied
is

the

merely equation
not
com-

dp
for
a

to

nonequilibrium
can,

proof
this

therefore

pletely proof
2.

satisfactory.
van

however,
gas

remedy

defect

by

an

alternative

Waals

(see
mole

problem
of
x2
a

47).
two

The

Gibbs
=

free

energy Here

per
xt
are

component
molar
per
a

system
ratios

is

given
Show

by

G(x)
1 and

xlGi
2, and
the

+x2G2. Gt and
plot
the of
states

and
chemical
or

are

the

of
of

the

components
a common

that,
tangent
Solution Set
we

if

G2 G(x)

(x=xt
between

potentials x2) as
separate

mole,
two

respectively.
xt

function into

has

Q'Q",

Q'Q"

phases,

Q'

and

Q".

jc=jq.

From

the

Gibbs-Duhem

relation,
_

xldG^dxx
8G-.

x2dG2ldxx=0,

have

dG

/dxA

dG<

Fig.

4.5.

Ch.

4] values
a

examples

213

If the
that

of

the

functions

at

x\
can

and
be

x'[
drawn

are

denoted
is

by'

and

", the

condition

common

tangent

Q'Q"

G[ -G'%
Using
G
=

G\ -GT2
B)

x xi

%zlL.
~

B)

xlGl
(/!
z^r
-

x2G2,
(j2
/^i
=

we

get
-

from (j2
/^/i

(jl

/^ir

'[G'[

xG-x[G\-x2G'2
Xl Xl

from

which

we

get

\G\

x\G'2

x'[G'[

x\G

x'jG'j

xG

x\G\

x'2G'2

'

and

X2Cri

X2(j2

X2(j\

X2Cr2

X1(/1

X2(j2
Xi

X1(/1
A1

X2ii2

X2

X2

This

means

that

G\
which
the is

G'[
C)
with
can

and
is coexist. into
two

G'2
valid,

G,
obviously
concentrations

C) valid.)
that the ratio
has of
a

equivalent
that
two

to

condition

by
between

single

and

double and

B). (If phases primes)

B)
Thus

is

dif erent

molar
a

system

Eq. C) (denoted density

is

xx

Q'

Q"

separates
C'
=

phases
C"
=

with

4--X,\
Q in
C'G'

^4,
than

D)

and

its
In

free
other

energy

(point
words,

Fig.
+

4.5)
C"G"
that
the

is

lower

G(x)

(point

in

Fig. E)

4.5).

<G(x).
the Helmholtz
tension is
y.

Based
area

on

the
an

definition

of

interface
per
unit

is

D.8), equal
area

show
to

free
Also
y

energy

surface
interface

show
T

per that

unit

the

internal
Solution
First
note

energy

at

the

equal

to

dy/dT.

that

surface

tension

has

meaning

when

two

phases

in

thermal

214

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.
In

equilibrium
interface
two

have

clear
total

interface
volume under such in
at

between

them.

order
must

to

define

the
into n"V".*

clearly,
parts,
is
one

the for number

consideration that
the
a

be

divided
the

each
of

the

total
in

phase, particles
measured

V-

V'+V"
ri
the and

and
n"

N=n'V+
are

volume,

density
from
the

of

particles
interface. combined

each Then
the

phase
extensive

sufficiently
e.g.

large
Helmholz
dif ers

distance
free
energy

system,

F(T,
+

V,
V",

variables, V", a,

of
the divided of
sum

the

N',
the
effect

N")=U-TS,
free
of

from volumes
free

F'(T,
the

V,
above

N')
manner.

F"(T,
Since
as

N")
this

of
is the

energies
the
+

of

the
the

in the

surface,

energy

surface
The dF
=

Fa is defined equations
obtained
-

Fa
from

F_

(r

r).
y da

A)

D.8)
-

d{U
-

TS)
-

S &T
+

p' dV
to
=

p" dV"
give
+

\i

dN'

\i' dN",

dF' and

S'

dT
one

p' dV
for
dF"

\i! dN',
combine

similar

dFa
Here

-SadT
of the

yda.
surface.
linear surface
this
Hence

B)
Fa is
of
a

Sa
T

S
a.

(S'
If
at

+
constant

S")

is

the
the
We

entropy
area can

function

of increased

and

temperature,

the of the dif erentiate


a

dimension

the times

system
and
to
a

is
we

by

the

factor
=

have
seta=l

Fa(T,
to

<xa)
obtain
that
a

aFa(T,

a*, a).
the

increases
with

respect

and

Fa
y is

dFJoa

ay.

This
since

means

surface of
the

Helmholtz
intensive

free

energy

per

unit

area.

Also,
is

y is

function

only

variable

T,

the

surface

entropy

Hence

the

internal

energy

is

given

by
,

or

Ua --J-T-.

dy

4.

Show

that
is

the

vapor

pressure

ps

(T)
T

in

condensed
T

phase

(liquid

or

solid

phase)

determined

by
Lo

the

formula

CD
0 0

More

specifically

the

interface

is

so

chosen

that

it

wil

be

perpendicular

to

the

gradient

of

n'.

Ch.

4]

examples

215

where

Lo
heat

is

the
at

latent
constant

heat
pressure

of

vaporization
of the

at

0 K

and

Cp

is

the

molar
and
/

specific
are

condensed

phase

(Cp,

C'(T)

explained

in

D.15)

and

below).

Solution

Obtain

the

entropy

of

mole

of

the

gas

from

D.14)

and

D.15)

as

Ri

Cp-Rlogp.
increase in
the

A) resulting
condensed

According
from

to

the

third
from

quasi-statically
at
a

law, heating
0 K the

this
a

is

equal
of
K and

to

the
then

entropy
substance

mole
to

the

phase
to

gas

at

pressure T K

quasi-statically
or

changing

it

by

adding

latent
T

heat,

L,
L

'C"JT)dT}L
o

B)

Now

we

know

that

L
T

H'-H"

and

(8H/dT)p
=

Cp,
T

so

that

Lo

+
o

](C;
T

C"p)

dT

L0
latent

CpT+
o

{(C
at

C"p)
Putting

&T

C)
A)

(where
and
T

L0

H'@,p)-H"@,p)
we

is

the

heat

K).

B)

using
T

C)

have
1

) J
-2
0

Cat

C(T)dT

-j
parts,
T

C'(T)dT

CjlogT

Cp

Ri

-R\ogp

Integrating

this
T

by

we

get
T

J t2 J C"p{T)
0 0

dT

-J

CJ(r)

^r-,

D)

216

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.4

from

which

we

obtain
necessary
to

the

desired

equation. D).
of
be the
is gas

Note

that

limT_0
to
are

Cp(T)
the

(third
Note: and
and

law)
If oscil ation

is

obtain
heat molecules

the

molar
of
the

specific
gas

C[,
done

with phase C and C


for

respect

rotation

(T)
gases

replaced
such
as

by hydrogen

i?

C[ (T)
helium.
4.6 the is the

respectively.

This

can

light

and
5.

Fig.
is

liquid
left
of

phase phase,
is the

diagram
to

for

the of

Cu-Ag
ACF
is

system.
the

The solution

region

above

AEB
and
to

the

right

a-solid The

phase,

the eutectic

BDG

/?-solid>

solution

phase.

triple

point

is

called

the

point.
1 '

K
o

1,083 1,000

<

liquid

phase

A
O

Al

960.5

^^
779

A
E C

500

i
weight
Fig.
4.6.

\fi-

fraction

Ag

(i)
in
H

How

wil

solution
it

behave
if
an

if it is cooled

down
is

from
heated

the

liquid
from
the

state

the

figure?
How

(ii)
in the

wil

behave

a-solid

solution

up

point

figure?

Solution

(i) The passing


BE.

temperature

merely
K

drops
it of

in the
the

the

liquid
intersection

phase
K'
of the
K".

through
At the

until

reaches K' of

along (Fig.
solid
the
the

the

vertical with
starts
curve

line

4.7)
solution
solid

temperature
concentration
has
a

solidify
which

the solidifies

which
concentration

/? phase is given
of

to

by Ag

Since
than

solution

smaller

liquid

phase,

the

Ch.4]

EXAMPLES

217

Ag
ature

concentration decreases

of

the

remaining
the

liquid
/? phase
solid
of the
state

becomes

greater.
freezes
solution
out

So,
travels
K"D.

as

the

temper-

further,
Thus,
the

solution

with

Ag-concentration. and accordingly

the

liquid along

increasing along
the

K'E

/? phase

solid

solution

When

liquid

Fig.

4.7.

the solid reaches solution to out freeze starts and E, the point a-phase the of the whi l e concentration const a nt the remai n thereafter, liquid phase and sol i d s are out unt i l i s sol i d i f i e d. al l (C) (D) a-phase freezing /?-phase the is further decreased a to, (When temperature say, sufficiently Kx and time solid solutions to then the has long Ka and passed, corresponding K^ should exist as solid The for of the stable ratio numbers atoms phases.

N(Ka)/N(Kp)
long
(ii) unchanged
concentration time because

is

equal
it is
a

to

K^K^K^K,, .
reaction

However

this

process

takes

very

between when
to

solid is raised the

phases.)
from

Similarly,
until

when
it

the

temperature

H,
starts

the
to

a-phase
appear

remains with
a

reaches

H',

corresponding

H".

The

liquid Ag

phase
concentration

is

less

than

that

Fig.

4.8.

218

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.

of with

the

solid.

If
the
to

sufficiently
of

long Ag,
also

time

is

allowed,
to

the
the
in

a-phase
in

moves

to

that
and

higher
move

concentrations
the

namely
becomes

right

the
so

figure.
both H"

Corre-

spondingly,
H"
at

liquid right.
becomes

H'i Hi.
however,

and

all

phase Finally, liquid.


all

richer
at

Ag,
the
same

that when

H'
arrives
as

H'
is

arrives
must

Hi
the

in

figure
concentration
determines

original
of
After

point
this the

H,

because

stage,
melted

heating
solution wil
first

Hi' liquid. merely

have
This

the
melt.

condition
the

the of
the
at

position
the

increases
is

temperature
silver
A

If,
continues
come

constantly
pure

separated,
solid

solid and then

phase
be-

past
pure
terms

Hi
Ag. activity

and

become

liquid
of
pressure

6.

In the

the

ax

of

the

solvent
pressure be

show
it,

that,
and the
as

for

vapor

pu

the

osmotic
can

boiling
fol ows:

general point

solution,
elevation

(or

freezing

point

depression)
Pi
=

approximated

T1

P0
where

Z
are,

pu
volume,
or

V,

Tf

and

Lx
of

molar

vaporization
elevation
or

the

solid

boiling point (or freezing) freezing point that precipitates

(or
the

respectively, melting
pure
a

the

saturation

vapor

pressure,

point)
solvent.
assume

and
In

the

molar
the
gas

latent

heat

of

treating
the

boiling
that

point
evaporates

depression,
is
pure

that

solvent.

Solution

(i)

By

D.42)

the

chemical

potential
G

of

the

solvent
gal,

is

A)
The

where of
the

G
gas

is the

chemical

potential
it
=

of
is

the is

pure

solvent.

chemical

potential

phase,

assuming

ideal,

6llgas
where
p^
=

<7liM1(T,
pressure of

p)

G?,gas
1.

RT

is
gas

the
becomes

vapor

solvent

The

equilibrium
RT

condition

Gl

Gl>
the

<7?(T,
Now

p)
vapor

RT

logfl!

G?,gas(T)
of
the
=

\ogPl.
is

B)

saturated

pressure
=

pt

pure

solvent
+

given

as

(Kir,

rf)

6?,gas(T,

p?)

G?>gas

KTlog^0.

C)

Ch.

4]

EXAMPLES

219

Subtract

C)

from

B).
Pi
=

Using

D.14)
exp

we

obtain

RT

Since

C?G;/i)-G!G;/i;)(p-/i;)
on

V^^RT^plV^
right
side

we

may

put

the

exponential
(ii)
solution
The

the

equal
Pi

to
=

unity

to

obtain

Ai
a

D)
solvent

equilibrium (pressure
Tis,

condition

when

pure
a

(pressure
membrane

p0)

and
at

/?)
by

are

separated

by

semi-permeable

temperature

A),

Therefore,

using

G01(T,p)-G1(T,p0)=V(p-p0)
(since approximation
the

change
is

in

volume

due and

to

osmotic

sufficient)

using

the

pressure definition

is

extremely
of osmotic

small,
pressure,

this

-i-i-i-:

-_-

pure

solvent

solution
y.

/>.
semi-permeable Fig.
n=pp0,
we

P
membrane 4.9.

obtain

E)

(ii )
the the

Since

the

vaporized
at

gas

is vapor

pure

solvent pressure of

the

boiling
the
pure pure
can

point
solvent

is

temperature
external
pressure,

which
p0.

the If solution the

equal is equal
is

to
to

boiling
is

point
Tt,

of

the

solvent
be

Tf

and

the

boiling

point

of

the
=

C)

and

B)

writ en

as

6?Gf,
<n(Tlt

p0)
Po)
+

6?>gasG\0,
RTt

Po)
=

loga,

<?lt9U(Tit

p0)

solvent), (Pure (solution).

F)

G)

220

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.
an

Subtract
order of

G)

from

F)

and

use

dG/dT=

to

obtain

expansion

to

first

Ti-Tf:
=

RT.Xoga,

G{T,p0)
G\
-

G{T,p0) 7\) { ?? G*
-

p0)

{^>gas(rljPo) G?, ^i.


gas

Goltgas(T?,
=

p0)}

G\

if)

ZJ7?,
(8)

hence
If

logal=

).

T1-r1

jrT1,

we

have
i
=

L1ATIR(T?J, G?,
po)
at
-

(9)

where

A
is

i? (SI
of the

gas

5? (r
pressure is
p0

the The

heat

of

vaporization
of
pure

solvent

and
the

temperature
If sides

T.
the
of

problem
of the the
pure

the

freezing
under

point
pressure
out

depression
p0

similar.

freezing
at

point
which and

solvent
solid

is the

Tx

and
and

temperature
eqs.

solute
to

freezes

is

Tu

right-hand

F)

G)
Lt

only
in

need

be
becomes

replaced

by

GUvAid(T?tp0)
=
-

GUsolid{Tup0).
<

Then

(8)

or

(9)
=

A
Thus
the

7? {SI
point
is the

solld

??}
in

heat

of
to

freezing
the

0.

A0)
of and

freezing
Observe
that

depressed
signs
reserved
of
two

contrast

elevation elevation
1.

the

boiling
freezing

point.
Note:
of if the
at

boiling
is

point

point
7+.
Consider
eq. pressure

depression
a

may

be

larger

than

D.37),
and

is

regular given
the
out.

solution

components
Examine the

for discuss

which

the

heat of

of

mixing,
vapor the
two

by AH=Axlx2. composition.
Draw the

relationship
the
case

the

In

phases
Solution Let
nx

separate

particular, diagram. phase

where

and

n2

be

the

mole

numbers

of

the

components.
+

Then

the

enthalpy

of

mixing
Since
the

AH,
solution
of

is
=

An1n2l(ni
Gibbs
free

n2).
energy

A)
of
the

is
are

entropy

mixing

regular, given

the

solution

and

the

by
=

G(nu

n2)
AS

n^G\
-

n2G2
log*!

+ +

AH

AS,
'

R(nl

n2logx2),

B)

Ch.4]

EXAMPLES

221

where

x1=n1/(n1+n2),
are

x2=n2/(nl+n2).
obtained

The the

partial

free

energies
and

of
=

the

components

by
+

formulae

G1
RT

dG/dn1
i
=

G2

dG/dn2:

Gt
(see Assuming
eq.

G?

AA
an

xtJ
gas,
+

\ogXi,
given by
can
use

l,2

C)

D.38)).
the
vapor

The
to +
are

vapor be
-

pressure

is
we

the
eq.

ideal

equation, D.16),
+

Gt
to

Gi>gas.
D)

obtain

Gf(T,
where
pt

p)
p2 p =pt

A(l
the
is free

XiJ
the total

RT\ogXi
of
pressure. be

G,gas(T)
components
solution
The

RT\ogPi,
1 and

and
and
p,

partial
energy
are

pressures

the

2, respecunder

tively,
pressure
pressure

+p2
its

is

also

the of
the the
p-

but
because

may

assumed be

almost
and

independent
Therefore
eq.

liquids
of

nearly

dependence

(/?

(T, p)
pt

in
=

eq.

D)
exp

can

incompressible. ignored,
-

D)

yields

piOxt

[A A
and
is if
A

xif/RT'],
the
a
=

E)
saturation
of
T.

where/7l0(r)
the
tween

exp[{(/?(r)
i at xt

^I.(gas}/i?r]
T

is

vapor

pressure

of
be-

pure
pt

liquid
and

temperature

function

The

relation non-linear
are

is linear

(Raoult's
decreases
the
p{

law) enthalpy.
be

0, but
The
two

it is

generally

when

A^O.

(i)
mixed law.

A<0.
so

Mixing
that
the 4.10.

components
that

easily
Raoult's

pressure
1.5

should

lower

than

given

by

See

Fig.

Fig.

4.10.

222

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.
The

(ii) easily
Raoult's
initial
Pi
Pi
as

A>0.

The
so

enthalpy
that
the is

is pressure

increased
pt

by
should

mixing.
be If

components
than

are

not

mixed,
law

higher
the
xt
as

that
is

(the
wil
be
eq.
a

solute

easily
the the
a

vaporized).
increase

ratio
=

A/RT
0.

given large,
hand,
pressure

by
the

slope given
have
eq.

by

for large E) approaches

of pt

from

On Then
4.10.

the

other
the

line/^/fox,as

can

maximum

and

minimum

shown

xt-*l. in Fig.

From

D),
RT

dxt implies (This


states

dxt

so

that
der

the

inequality
unstable

dpJdx^O
condition.
Such

dOi/dxi<0,
resembles
may

which
the

is

thermoof
a

dynamically
van

unstable
if there
are

states

Waals
in

gas.)

unstable
We

appear
eq.

maxima

and

minima

the/?;

xt

curve.

have,

from

E),

Sx,
which
range

-x,
that
1.

TV'
if

""

RTXi\ ">
hand,
A<0 for
or

2)
we

4V
have
extrema
we

)\'
of
have
pt

shows

A/RT>2@<2RT/A<\)
on

in

the

O^x^
is

If,

the
the

other

0<A/RT<2,
occurrence

dpJdx^O. phases
One

Therefore

condition

the
1.

of

two

always separated
G)

A/2RT
can

>

obtain

the
=

same

result

by
+

examining
+

G(xlt
fol owing
this

x2)
example

XiG
2.

x2G2

Ax{x2

RT(x
solution

logx1
of

x2

logx2),
2 and
eq.

(8)

Equation

A)

of

the

example

D)

in

solution

give

(9)
from

which

we

obtain

d2G
dXt
,=

-2A 2A

RT
+

X1(l
holds
=

Xy)
for

ART

2A

A0)
if
eq.

(as
holds,
the
In

[xt(lx1)]~1^4;
we

the

equality
for
xt
so

x1

%).
a

Therefore,
common

G)
to

have
of
to

d2Gjdxl<0
G against
find mole
xl9 fractions and

\.
and

Then
occurs

there
a

exists

tangent
into
two
as

graph
order

there

separation
two

phases.
of

x\

x'[

of

the

phases

functions

Ch.4]

EXAMPLES

223

temperature,
eq.
are

one

only
with

has

to

find
to

the
x1
=

(9)
determined

is

symmetric by
the

respect

points ^,
log

of
the

contact

from

eq.

points

of

contact,

(9). x[

Since

and

x'[

equation

A(l-

2xx)

RT

-^
1

0,

x1

Fig.

4.11.

Fig.

4.12.

which

may

be

writ en

as

-Hog
or

Ay
2RT

1)

A1)

tanh

2RT'

Ay_

A2) A3)

by

putting
4.12

Fig.
condition
v=0

shows

the

method

of

graphical
solutions
on curves

solution
other the have
than

of side intersection other


than

eq.

A2). (The
of
eq.

Eq.

G)
tangent
is
y
at
=

is

the
at
a

that
of the
curve

the
for

equation
the

has

y=0.

function
the
is
no

left-hand
an

A1)
besides
if

45

degree A/2RT>1, Fig.


the

angle.
whereas
4.13

Therefore there
the for

if

intersection

y=0
obtained
is

is

plot

of from shaded

x\

and
eq.

solution

y(T)
The
a

x'[ against A2) into


is the At

T,
eq.
two

which

is
This

of
cannot

the

solution.
exist
as

portion

A3). phase

the
where

A/2RT< by inserting diagram phase


the

1.)

region

system

single

phase.

higher
=

temperatures,

T>TC

A/2R

A4)

224

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.4 solution
is

where

condition concentrations. of

G)
The

no

longer
temperature

holds,
Tc,

single
eq.

phase

realized temper-

for

all
ature

A4),

is

called

the

critical

the

solution.

x\
Fig.

0.5
4.13.

x"i

8+.

For

dilute

solution

of

strong

electrolyte,

which

dissociates

as

Av+Bv_-+v+Az++v_Bz-,
the

osmotic

pressure

may

be

writ en

as

vC2RT
Prove

that

the

osmotic

coefficient*
1

is

given

by

the

formula

dlogy\

Jt,
[For
Solution the

dm2.
Use
eq.

A)

notation,

see

eqs.

D.40)

and

D.51).]

(Hint:

D.52).)

Following
of the

the

solution
The

of

example potential
the
+

6,
Gibbs-Duhem

we

have

only
the

to

calculate
is

the

activity
eq.

ax

solvent.
can

chemical into
n1

G of

solute

which

be

inserted

relation,
=

given C.12),

by

D.52),

AG1

n2

dG2
defined

0
as

(T,
fol ows: of which
xi.

constant)
Let
xi

The solvent

osmotic

the

in

coefficient solution,
coefficient

g is generally the chemical

be

the

mole

fraction

of

potential
Gi
=

is

given

by

&<>+gRTlog
to
=

Then

the

osmotic

is

related

the

activity l)logjfi.

yi,

eq.

D.43),

by

the

equation

(g

Ch.
to

4]

examples

225

yield

the

equation

^
which
to

0,
1 for
x2
=

B)
can

determines

av

Since

ax

0, this

equation

be

integrated

give
1

1
0

x2

x2

dx2

1
0

x2

dx2
RTlog
alf
we

If

we

insert

this

result

into

the

equation

nV=

obtain

(for

x2<\)

vx2RT( Ktu
Using
eqs.

?
0

logy a*2

i
D.41),
one

x2j

D.40)

and

finds
=

that

x2/V?
so

m2&il OO0V?
may

m2p/1000
as

C2/1000,

that

the

above

result

be

writ en
1

7i

vC2RT
1000

<H

f 1

7
m2
o

logy
am2
the

m2j
g

dm2>.

| 2J
of
the

Note:

The

osmotic from
the

coefficient
ideal

characterizes
of
van

deviation

osmotic

pressure

relationship
_

't

Hoff,

vC2RT

looo"'
By

solving

equation

A)

for

y,

we

obtain

m,

226

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.
The above

where
used 9.
to

we

used

the
the

condition coefficient
of

that

y->l
when

as

m2->0.
is

equation

is

find

activity

g(m2)
vapors

known.

The

thermal

dissociation

metal ic

is

violent
to

process

in

the

atmospheres
degree
of
of

of dissociation dissociation

some
a

stars.

Apply
with
W

the

law of the

of

mass

action
pressure.

find Assume

how
the

the

varies
be per

temperature
mole
vapor.

and

energy

to

Solution When
1 a:a:a,

the

degree
so

of

dissociation

is
pressures

a,

the
of
a

molar
the

ratio

of
are

A,

A+

and

is

that
1 Pk
=

the

partial
a

components
a

1+

Pj

Pa+

1 +

>

Pt

z~~~~.

1 +

Therefore

the

mass

action

law,

eq.

D.65),

gives
*G\

pA

l-x"

'\
of freedom
of

RT

l
constituents,
eq.

A)

If

we

ignore
AG0
=

any

internal
+ +

degrees

the

D.15)

gives

GA+
U0A+
free

Ge-G0A
UOe
energy
-

U0A
of the

IRT
reaction.

log
If /
exp

RT(iA+
is

ie
into

iA)
eq.

as

the

standard

this
W RT

inserted

A),

we

find

a2

l-oc2F
where

,j

pccT*

*\

w=uOA++uOe-uOA
is

the

energy

of

dissociation.
energy

Note:

The

ionization

of

the

process
+

A->A++e,
+e.

is is

generally
reason

much

smaller
may

than
often the

that

of

the

process

A+->A+
ionization

This

the

why

one

ignore

higher-order
condition,
the

processes.

10.

Apply
cell,
and

equilibrium
derive

eq.

D.73),
for the

to

the

phases

in force

the

Daniel

formula

D.71)

electromotive

(potential

Ch.

4] between Assume

examples

227
*

dif erence)
cell.

the

two

terminals
no

(which
dif erence

are on

made
the

of

that
solution
and

there
the

is

potential
solution.

copper) boundary

of
of

the
the

CuSO4
Solution The

ZnSO4

dif erent

phases
Cu
I

and

the

terminals

of

the

cell

are

denoted

by

| CuSO4
I

(aq)
is

| ZnSO4
II

(aq)
by

|
4>i,

Zn
IV

| Cu
V

and

the

potential
of
two

of

each

phase

denoted
are:
i

<Pn
i

etc.

The

equilibrium

conditions

neighboring
to

phases
Cu+

I-I I -I I

(with (with (with (with


one

respect respect
respect respect
may

+):
"):
+

piCu+
i

2e<Px
-

/xCu+
in
=

2e$n,
-

A)
2e$m,

to

SO4
Zn

/xSO4II

2e$n
2e$m
V
= =

/xSO4IV

B)

I I-IV
IV-V

to

+):

/xZn
IV

/xZn

2e#IV,

C) D)

to

electrons)

/xe

e<Piy

jxt

e<Py.

Further

put
II
IV
=

IV
=

IV
+

/*Cu

/*Cu

2/Xe

HZn

/*Zn+

2/^e
in
maY

E)
zinc.
be

becaus
assumed

Cu

Cu+
=

+2e
eQ-

in

copper becomes

and

Zn

Zn+

+2e
and

Since

we

#u

By

taking
I

(l)

#in, C)-D)
II

B)
x

jUso4--=Afso4-- obtain
I IV

neglected.

2,

we

IV

which

can

be

writ en

as
I I IV

II

with

the

use

of

eq.

E).
=

The
-

above

result
+

is
+

equivalent
->

to
+

2%-E
*

AG(Cu+
the
same

Zn

Cu

Zn+
a

If

both
The terminals

terminals electromotive
made

are

not

of

metal,
cell
is

there

exists
as

contact appearance

potential
dif erence
of
a

between

them.
open

force of
the
same

of

defined

the

potential
the

of
contact

two

kind

of

metal,

avoiding

potential.

228

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Gl.

Problems

[A]
1.

(i)
in
an

Let

the

Helmholtz
and
a

free

energies
be

Fa and
known
of
as

Fb
functions
can

of
be

homogeneous
of
T and
V.

substance
Show

a-phase
point
tangent
T

b-phase
the
curves

that

the
a

transition
common

between for

these

phases Fa

determined
as

by
functions
rule which is

drawing
of
V

and

Fb plot ed
Maxwell's

for

given

(see
note to

the
the

figure).
above

(ii)
in the

From

point
1 of

of

view,

derive

explained

example

this

chapter.

Vb

2.

The

heat
of
due

of

fusion

of
and

ice
water

is

80 is

cal/g
1.091:1.000.

at

C,

1 atm.

The
the

ratio

of

the
of

volume

ice
to

Estimate

change

specific melting

point
3. The
1 atm,

the coefficient

change
of

of

pressure.

pressure

the dT

boiling
1

point

temperature

of

water

at

100

C,

is

given

by

Estimate
4. Near

the the and

heat

of

vaporization
the

of

water

at

100

C.

triple
the

point,
gas

equilibrium
has

curve

(p-T
a

curve)

between

the

solid

phase

phase

generally

steeper

gradient

with

respect

Ch.
to

4]

problems

[a]
to

229

the

temperature

gas 5.

phase.
heat
of

Give

compared thermodynamical
of ice
to

axis

that

between for
0

the this

liquid
fact.

phase

and

the

explanation
80 of of

The

fusion
of and
water

is

cal/g
ice

at

C,
to

1 atm,

and
at

the The

ratio

of

the

specific
vapor and 600

volume
pressure

that
Estimate

is

equal
of

1.000:1.091.
0 C
are

saturated
4.58
mm

the

heat
above

vaporization

water

Hg
of the

cal/g, point
Note

respectively.
using
that
the

approximately
is
very
near

the
0

temperature
because
water

triple

data.

\Hint\
change
6.

the

triple

point
temperature
vapor pressure

to

C,
and
is

the
is
very

pressure

of that

the the

equilibrium
saturated

between
of

ice

slight.]

Show

ps

liquid

given

by

psccexp(-L/RT)
when the
may 7.

(a)
pressure

the
considered

temperature
is

is

not

too

close and

to

the

critical

temperature
heat
range
L

so

that

sufficiently
as

small
constant
over

(b)
the
of

the

latent

of

vaporization
interest.
surface tension between

be

temperature
a

of the

Let

pL

and
is
of

p2

be

the

principal
by
y.

radii Show that

curved
pressure

surface,
dif erence

of
two

which
sides

denoted the surface

the

Ap

the

is
y

given
1

by
I

Ap
8.

I
\Pi
heat
the

Pi)
which
surface

(Laplace's
is absorbed

formula).
by
y

Give of of caused
a

the surface

formula

for

the

the

isothermal
is

expansion
as
a

film,

temperature

assuming (see example


adiabatic

tension

(T)
the
condition

known

function

3). expansion
a

Next,
is

show

that

temperature

change

by

the

given
=

by
constant.

the

(dy/dT)
between

9.

Consider
The
or

the

phase
shows that

figure
the
is
gas

equilibrium relationship
the solid
curve

binary
the mole
constant

solution
fraction
lies pressure. below
P

and
in

its the
The the

vapor.

between

liquid
gas

phase
above
the
now

and

temperature
and

under the mixture


the

phase
curve.

liquid
at

phase
the

dotted

Suppose
down
gas

that
At

the

gas

point
appears

in and

the
at

cooled
the

phase
Find
the

gradually. disappears
mole

point completely.
of

A,
the

liquid
at

phase
A.

figure point

is

C,

(i)

fractions

solute

230

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.4

(ii) (ii )
stage
the
gas

Find
Find

the
the

mole mole

fractions

in
in
B in
at

the the

gas

at

C.

fractions
a

represented
and the

by

point
phases

the this

liquid figure. point

and Show
is

the that

gas

at

an

intermediate of the
mass

the

ratio

in

liquid

given

by

BB'/BB".

10.

Consider and
n2

binary
of
the
2.

solution Let mole


/be
some

which
extensive
x2,

contains

nx

moles of
as

of

the

constituent

moles with

quantity
for

this

solution./ ^
by
the solid
line

+n2)
in

changes

fraction

instance,

shown

Ch.4]

problems

[a]
the

231

the

figure.
relations

The

broken

line

QPR

shows

tangent

to

this

curve

at

P.

Prove

the

11.

Let

the

fugacities
1,. .,

(see
Show

D.22))
the

of

the

Vf(/=
and

c).

that

fol owing
c

components relation

in

gas
constant

mixture
pressure

be

holds

at

temperature,

? nfdlogvi
i
=

0,
component
solution
is
/.

where
12.

,(/=
the

1,. .,
fractions
chemical

c)

is

the

mole
and
of

fraction in

of

Let When

mole the

be

xt

x2
one

binary

of

two

components.

potential

component

given

by

show

that

the

chemical

potential

of

the

other

component

is

given

by

13.

In

the

ideal

dilute Raoult's

solution

of

two

components,
Pi
=

the

vapor

pressure

px

of

the

solvent

obeys
constant

law,

*irf
vapor pressure

(at
which

temperature,
holds

p\ being
limit
law for
the
as

the

of law of and
pressure

the the
p2

pure

solvent),
the

in

the

xx^>\.

Using
for chemical
the

this
vapor

Gibbs-Duhem
of

relation,
and the
the

derive
formula

Henry's D.30b)
statements

D.29)

solute

potential
the mole

the

solute.

14.

Prove pressure solution.

fol owing
p
or

concerning
of

graph
xt
at

which

gives x2) points


which for

the
a

vapor

p2

as

function
of

the

fraction these
of

(or
the

binary
and

(i)
be
at

Let and

the

points
then
have

Aj

gradients a2 respectively, and A2 with


the

the
and

tangents
the

of

curves

At
connect

A2
the We

the

origins

gradients Ot and

the

lines and

O2

be

pt

j52,

respectively.

relation

232

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.4

(ii)
tangent
15. For
an

When
at

the the

tangent

at

the

point

point

A2
solution,

goes

through
formula

At O2. D.34)

goes

through

the

origin

O1?

the

ideal

binary

for

the

chemical

potential

of

the

z'-th

component,

always
the

holds,
chemical the
pure

where

xt

is in
statements

the its

mole
pure

fraction
state.

of such

the

z-th

component
when

and it

(j?
is made

is

Prove

potential fol owing


component
no

for

an

ideal

solution

by (i) (ii) (ii )

mixing
There

liquids, change,
or

is
heat

volume

No
The

is

absorbed

emit ed.

entropy
the that
to

changes

by
of
internal

the

amount

of

the

mixing

entropy

D.19).

Also

find
16.
Show

change
in
an

energy.

ideal
mole and

solution
fraction further

the

vapor

pressure

is
the

approximately
gas

procan

portional
used
cases.

the
vapor,

(eq.
show

D.36)),
that

if

ideal

formula is valid in

be
most

for

the

this

approximation

17.

Derive

the

formula

for

the

osmotic

pressure

in

the

case

of

an

ideal

binary

solution.

Ch.4]

PROBLEMS

[A]

233

18.

In

the

case

of Based

an

ideal
is
on

dilute this

of solvent.

the

solvent

nearly
fact,
can

solution, proportional
show
to

the
to

pressure

pt

of

the
the

saturated

the

mole

fraction
of

x1(wl)
boiling
of

vapor of the

that

the mole

variation fraction

point
the solute.

of

this

solution
that concentration solution
the

is

proportional
solute of
also solute

the

jc2(<^1)

(Note
19.

vaporize.)
in
to

The

the

the the

solid

phase
concentration

which

precipitates
of
the

from solute
a

dilute
fraction the

x'2
in the mole
the

is

proportional
solution

(mole
of

x2)
temperature.
and
for

(liquid
the

phase);
between
under
an

x'2
the

kx2.
the

Here

k is
of of
an

function the ideal for the

Derive the

relation
x2

variation
solid

freezing
dilute
solid

point
solution

fraction

assumptions
dilute

liquid

phase

and

ideal

solution

phase.
20.

Consider heats
of

two

kinds

of

metal

1 and

2 in

(with
which

melting
mix well

points
with
each the

Ti

and other

T2
in

and the for

fusion

Lt
but

and
do
for
not

L2,
mix

respectively),
at

liquid
the

phase,
phase
Assume,
any

all the of with

the

solid that

phase.
which the

Derive determines
heat of

equation
the eutectic does

diagram,
the

and sake

give

point.
show 21.

equation simplicity,
temperature.
A

fusion

not

appreciable
that
two

change
kinds of
that

Suppose
the be in

metals
the heats

and of

B
are

mix

well ideal and


B

both
let

in

the

liquid

and

solid
the

phases. melting
Derive

Assume

mixtures
of

(i)
the

phase

points the general diagram.

and

fusion
which

and

(per
and

Tu mole),
the

equations
1500

give

the

solidus

T2 and Lu L2 respectively. lines liquidus

1000

0.2

0.4

0.6

0.8

Phase

diagram

of

Cu-Ni

alloy.

234

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch. of the

(ii) Simplify sumptions, the figure. Assumptions:


and
are

the and
show

above

general
that
one

has

equations a cigar-shaped
of fusion
R.

by

use

fol owing
shown

as-

phase
of
A The

diagram

in

(a)
the
can

the

entropies
the
gas
constant

and

(per

mole)

are

equal,
of

of

order be

of

(b)

temperature

variation

Lx
22.

and

L2
the

neglected,
reaction
aA
+

(c)

l^-T^T^

T2.

Consider

gas

bB+<=*
and volume.

IL

mM

under

constant

temperature

Prove

that

the

quantity

defined

below

depends
fLi'
-

only
nvrr---

on

the

temperature

jr-i
brackets
gas

Kc (T)
indicate

(Guldberg
the

and of

Waage,
moles
per

1867).
unit

where Assume

the the

square

number

volume.

ideal
reaction

formula
in the

for ideal

each

component.

23.

For

chemical

gas
_ ~

mixture,
AU

derive

the

reaction

isochore

dlogKc
dT

RT2

and

(van'tHoff,
where AU per
us

1885),
energy

and mole

AH

are

the

standard

internal

and

the

standard

ent-

halpy
24.

of

the that

reaction.
the
gas

Let

assume

occurring

in

an

ideal

equilibrium phase
=

constant at

of

the

reaction

A2+2A,

18

C,
1.70

is

given
x

by

Kc(l%
where

C)

^indicate

TA1
=

10~4
of
the pressure

mol/cm3,
moles of
1 atm
per

the is
1 atm.

square

brackets

the
when
at

number
19
x

unit
gaseous

volume.

Determine
ture

the
if

degree
What

of value
heat of

dissociation
is

the
for

mix-

expected
is of

and

the

degree

of

dissociation,
25.
Let
us

the the

reaction

5.0

104

cal/mol?
a

consider

occlusion

gas

A2

by

solid

C.

What

relation

is

Ch.

4]

problems

[a] pAz and is if the

235

expected
we assume

between
that calcium in

the C the

gas

pressure

concentration
into
atoms

of

A A?

in

C,

if

molecule

A2

dissociated dissociates observed


can

26.

Solid

carbonate
and

(CaCO3),
carbonic
pCO2 acid
of
gas.

heated,
The

into

solid
the dissociation

calcium

oxide
pressure

(CaO)
(the

value
be

of

pressure

CO2
11355

gas)
~

expressed
T
+

by
26.238
in
atm.

logio
between
termine
27.

Pco2
and 1500

~y~
K,
the

5-388

loSio
being
this dissociation

1100

pressure

measured reaction
is
+

De-

the
net

standard
in the

enthalpy
electrochemical
+

change

of cell

AHj.

The

reaction

D.67b)

Ag
At
of 0.000338
25

(c)
the

iHg2Cl2
experimental
are

(c)
given
free

->

AgCl
values

(c)
of
the

Hg

A).
force
V

and

1 atm,

electromotive
and and

and
=

its

temperature

dependence
Determine
the

by

?'=0.0455

CE/dT)p
of this

V/deg.

energy,

enthalpy,

entropy

reaction.
28.

Evaluate
and monatomic
on

the
the of
heat

chemical

constant

i of

mercury,

based
of

on

the
be K.

assumption
ideal solid
at

that
gas.

the

vapor

The
at

entropy

mercury 1 atm

specific

is

given
234.2

melting point eval u at e d Tm by

mercury is

may

fol owing regarded


The

data
as a

Tm

234.2

value
of

of the

by

numerical

integration

Ss B34.2)
The
The

f
o

Cp dT/T
x

59.9

107

erg/mol
point
from

deg.
is
the

heat increase heat

of

fusion
in
at

is

2330
of
pressure,

107

erg/mol.
mercury
1 atm,

The is

boiling
determined

Tb

630

K.

entropy
constant

liquid
630

observed

specific

S, F30)
The

S, B34.2)
is heated

f
234.2

Cp dT/T
x

26.2

107

erg/mol

deg.

heat

of metal

vaporization
is

59300

107

erg/mol.
high
temperature,
electrons
are

29.

When

to

sufficiently

236

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.4

emit ed
can

from be found
gas

it. in

Show

that
the

the

chemical

constant

of
if

the

thermal of
the
pressure

electrons
of
of the

electron electrons 30.

by measuring equilibrium
the reaction metal

temperature
with
the

dependence
metal,
to

the

chemical

potential

the

within

is

assumed
electrochemical

be

constant.

The

electrode

in

an

cell

(Pt)

H2

(g) (hydrogen

electrode)

|HC1

(aq,

x)| AgCl

(c) Ag

(c)

AgCl
What
can

(c)
the
_

-+

Ag
that

(c)
the

C1~(HC1,
electromotive

aq,

x).
force
E

is
be

the

net

reaction?
in form

Prove

of

this

cell

expressed

BRT\

(RTS

where

denotes pressure

the
of

concentration the

of
gas.

HC1,

y the

mean

activity

of

ions,

and

pH2

the

hydrogen

[B]
31.

Consider

system
that

obeying
the Gibbs
at

van

der
free
energy

Waals'

point.
pressure

Show is the

equation changes
consideration

of
as

state

below in
the in

the

critical
as

shown

figure
this

the

increased
what

constant

temperature.

Explain
below

change
temperature.

the

system

under

makes

process

critical

Ch.4]

problems

[b] with with

237

32.

When
heat
of

two

phases
transition

1 and from

2 1 to

are

in

equilibrium
changes

each

other,

prove

that
to

the the

2, L,

temperature

according

equation,

dT~
Here and

P2

P1

'

V2-Vx
heat

Cpi
Pi
and

and

CP2

stand the

for

the
if

molar
of
1 is

Show,

/?2 for in particular,


is
an

coefficients

thermal either

capacities expansion
a

at

constant

pressure,

of
or a

the
and

two

phases.
the
above other
as

that,
gas,
we

phase
dL

solid

liquid
obtained

phase

ideal

may

approximate
c c

the

equation

33.

Prove

that
to

the
a

sponding
at
a

specific heating
T
C
=

heat
process

of in

saturated

vapor,

i.e.
vapor

the is

which
dr
+

the

kept
d

specific saturated,
/V

heat is

corre-

given

temperature

by
r

C~

f~f
pressure. which

C+T[
per

where

stands

for

the

heat
at at

of
constant

vaporization C,
dr

unit

of

mass,

and

clp

for

the

specific
Evaluate

heat
c

of
for

the
water

liquid
cal

100

for

4
What 34.
Due
case

,
=

1.01--,

g-deg
c<0?

dr

-0.64-,

cal
r
=

g-deg

539.

cal
g

is

meant

by
effect of

to

the
a

surface of
vapor

tension,
radius
r

the is

saturated than
in

vapor

pressure pressure
p^

pr

in usual

the
of

of

liquid
the

drop
saturated

larger
the

the
case

value the

of

pressure)

of

planar

(the boundary

liquid

phase.

238

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.4

(i) (ii)

Determine

the is the

relation value

between
of

pr

and
rc

r.

What
grow

critical

the
vapor

radius
with

of

such

liquid

drop

that

it

can

in

the

supersaturated
fact
that
the

p>p00?
c

35.

Based

on

the

(see
sudden

problem expansion

33),
of

explain
the adiabatics Wilson

specific why
and

heat

of

the

saturated
vapor

vapor

is

negative

supersaturated
chamber. the saturated

is

produced
curve

by
in

Consider [Hint: p-T plane.]

the

vapor

pressure

36.

Some

kinds
the

of

metal

become

superconductive
have
not
a

at

low

temperatures.

In Meissner

this

superconducting
that

magnetic
field
state

state, flux
is

they
does

remarkable into
even

property
the
when into

(the
even

effect)
an

enter

metal

when

external

magnetic conducting
interior
critical
B

becomes
field

imposed collapses equal (if


versus

(B=0
and
to

H^O).
the
normal

However,
field
The
curve

the

super-

changes
if the

H,
Tis

external
then

magnetic B=H).
in
the

state, exceeds
of it
the

and
a

the
certain

value into
state

magnetic plane
normal

HC(T) HC(T)
phases
n.

\H\>HC,
shown

critical
the
s

two

corresponding
latent
heat
of
the

to

the

figure, superconducting
transition

and

divides
state

H-T

and

the

(i)

Determine

the

s->n

at

H^O

and

T<T0.

1,000

ir.

Pb

Ho

normal

state

500

superconducting
state

Ch.

4]

problems

[b]

239

(ii)

Derive

Rutgers'

equation

*A2

dTjT=To
where
in

^4n/Cs-Cn\

v{

jT=T;
in the the molar
at
an

Cs
the normal
What

and is
=

Cn
state,
the

stand relation

for

the

molar and

heats
V

superconducting
volume.

state

and

respectively,
between
is

for
and
to

(ii )
when
37.

Cs

Cn
be of

arbitrary

temperature,

J/c
are

J/o
cases

{1 -(r/r0J}
in

assumed

valid? solution
when
a

There
vapor

which

the

at

some

temperature
is the

composition and composition,


This above and
of

agrees

with of
two

that
dif erent

of that
or

its

mixture

kinds

of

liquid
of

being
mentioned
gaseous

distil ed.
line

situation

is called
to

azeotropy.
either
a

Show
maximum

the
minimum those

temperature
shown in the

corresponds
the

liquidus

in

the

phase

diagram

like

figure.

38.

Consider of
its

substance

A solidus

phase
and

diagram
the of
B

containing corresponding
may

an

impurity
to

constituent

B.

In

the
of When

region
B,
the the

the

lower

concentration

liquidus
concentration concentration

be

in

the

solid

Cm

is denoted

by

approximated phase precipitating k C, C/Cm


=

by
is called

straight
from the the

lines.

liquid

phase
constant.

of

segregation

liquid

phase

kCn

240

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.
the

Show rod
of

that

the
L

concentration
is

of

at

distance

from

left

end

of

molten

length

given

by

if

the
it

molten Assume
occurs
so

rod

with

concentration dif usion


in of
atoms

C,?
liquid
of
the
zone

is does that

cooled
not
occur

from
in

its

left the solid


is

end

and

solidifies.

that

phase,

but

rapidly
(The principle

the

phase

the

concentration

always

kept
39. For
and

uniform.

melting
the
chemical

method.)
potentials
of

some

kinds
are

solute

high-polymer approximately
of

solutions,

solvent

given

by

the

equations

<?2
where
r

Gi (T,
stands
for

p)

RT

{log
degree

4>2
of

(r

1) A

02)}
and

rw

02J,
the

the

polymerization,
r2

<?,- for

volume

fractions
1

Nt+rN2
numbers
It

N1
molecules that of
Then

rN2
and
each

Here

Nt
of the
prove

and

N2
r

are

the

of
is the

solvent
assumed

of

solute

highmolecule

polymer
consists

molecules,
monomers,

respectively.
and

polymer

that molecule.

volume

monomer

approximately
the

equals (i) (ii)

volume that the the

of
chemical

solvent

potentials
of

given
of

above this solution


to

satisfy
with
the

Gibbs-Duhem that
of

relation;
compare

entropy
relation
of

mixing
heat
the osmotic
of

an

ideal
of

solution;

(ii )
(iv)

derive

the
and

the of

mixing
pressure this

concentration
of

this

solution;
examine
of
40. An

the
the

relations
to

and solution.

the

vapor

pressure

solvent solution solution

the of

concentration

of of of
I

aqueous

M+X~ M+R~
the
X"
room

concentration
concentration

x\
x\
a

is into
What when

poured
the membrane

into

room room

I,

and

another
is

other
the

I,
permeconcen-

which
able for

separated
M+
of ions

from

by
not

semi-permeable
for
R~

and in

ions
room

but
I

ions.

are

trations

M+X~
membrane

and

I,
is
reached

x\

and

x'[, by
dif usion

the of

equilibrium
M+
and
X"

(Donnan's

equilibrium)

Ch.4]
ions

PROBLEMS

[B]
the

241

through
are

the
very

membrane?

For

sake
be

of

simplicity,
as

assume

that

the

solutions

dilute,
must

and

may

regarded

ideal

dilute

solutions.

[Hint:

the

solution

always
I

be

electrically
I

neutral.]

X~
x-

41.

In

the of

case

of
the

the

preceding
the

problem,
membrane.

voltage
Derive
the

dif erence formula

appears

on

both

sides

dif erence,
42.

semi-permeable by considering
in osmotic
the

for

this

voltage

electrochemical

potentials.
membrane,
one

As
ions Then

is

shown
is inserted

figure,
a

semi-permeable
and
is in

impermeable
M
an
+

to

R~

into

U-tube,

branch
When

R~

solution
decrease

is

poured.
of
in

the

pressure
to

measured. the

M+X~,
osmotic

able
pressure

pass

through
observed. solution
is

membrane,
this

is

electrolytic added,

solution
a

the for

is the

Explain
ideal
and

phenomenon,
dilute.

by

assuming,

simplicity,

that

R-

x-

x-

43.

In

the 6

table,
the for the

the

observed values
aqueous

values
of solution
the coefficompare
mo-

of of

the

freezing
103W2

point
1O20

depression
103W2

are

given
1O20

against

various
the

lality
HC1.
cient
it with

Determine
g from

osmotic
and

(mol-kg-1)
0.627 1.179
1.245
1.474

(cleg)
0.228 0.434
0.455 0.542 0.815

(mol-kg-1)
3.526 4.520 6.879

(cleg)
1.286
1.644 2.494

these

data,
obtained

the

result
6 and

of

the

Debye-Hiickel 8.)

law

by the D.56).

limit

(See

10.633

3.843

examples

2.228

242

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.
atom

44.

In

an

n-type

impurity
the

ionized duced.

by Regarding
solution,
the Since
as

reaction
the

semiconductor, D?D+

the
+

impurity
a

(donor)
electron
e

is

e,

and conduction

conduction
D

is

pro-

solid
derive

and formula
conduction
a

crystal regarding
the

containing
the

and

D+
electrons
conduction the

as as

an an

ideal ideal
electrons

dilute
gas

for

equilibrium
electrons
move

density

of in

by
may

thermodynamics.
Note:

freely
gas is
a

regarded
concentration
45.

kind of

of

gas.

The

ideal
low.
in

good

crystal, approximation

they
when

be

the

electrons

is

Molten

silver

can

easily

dissolve

molten

gold,

i.e.

Ag(l)->Ag(inAu(l)).
In

order
an

to

make

this

process

take

place

reversibly,

Wagner

and

Engelhardt

made

electrochemical

cell

Ag
and the of 1360

A) | AgCl,
of
can

KC1
force.

mixed The
x.

| AgjcAUl

_x,

measured

its for

electromotive values
force

experimental
What x=0.5
as an

data

are

shown

in

table
electromotive

five

concentration
be

value
and
at

expected
is assumed

at

f
-846
-021

K,
force data

if The

Ag^AUi-*
table
at

(liquid) gives
the
same

ideal
electrofrom

solution?
motive
these

observed

values
y defined
to

of Determine

the

002
0.471

0'074
0.114

temperature.
coefficient

the

activity

by
chemical raised

eq.

D.43).
equilibrium

0.263

0.198

46.

Le

Chatelier's

principle
(i)
If the

applied
temperature
moves

can

be
pressure, is

stated
the

as

fol ows, chemical

is

under
a

constant

equilibrium
If the
pressure

in
at

such
constant

direction

that

heat
the

absorbed,

(ii)
librium

is
in

increased
a

temperature,
the
statements.

chemical
the

equiunder

shifts

such

direction
Prove these

that

total

volume

of

system

consideration

decreases.

[C]
47.

Prove

Maxwell's
that because the the

rule
states

described
on

however,

the

physical,
that

they
of the

violate Gibbs

equality

example p-V plane the thermodynamic free energies

in

1 for

van

der

Waals

gas.
are

Note,
nonso

having
at

(dp/dV)T>0
stability
conditions,
must

and

be

proved

by

Ch.4]

PROBLEMS

[C]

243

considering avoiding (see problem

such

quasi-static non-physical 34).

process
states.

passing
Use the

only
fact

through
that

physical
Cv
is
a

states

and
T

function

of

only

48.

It

is

found

that law

ferromagnet

has

magnetic
positive
Curie
heat

susceptibility

obeying

the

Curie-Weiss

(^
in

is

constant)
temperature
of

the

paramagnetic
the

thermodynamics
temperature
ature.

region jump
spontaneous
if
=

above
in

its

Tc.
material
the be
+
>~,

Discuss
at

by
Curie

the

and
Note

the

specific magnetization
energy

this
below

the

Curie

temperinto

[Hint:
the form

that,

the

free
+

F(M,T)
must

F(O,T)
hold.
As

ix(T)
an

MZ

F(M, + P(T)

T) M4l4\

can

expanded
then
terms

a(Tc)
only

0
up

and

/?(rc)>0

approximation,

retain

the

49.

Explain
water

by
vapor,

thermodynamics
and

why
why
ion

water
are seen

drops
when in
the

condense the

around

ions

in is

tracks

Wilson

chamber
of
water

suddenly

expanded.
Note

[Hint:
the

that

the of

free
the

energy

is lowered

polarization

by

electric

charge
the
39

ion.]
under into
two

50.

Determine
in

conditions

which

the

high-polymer

solution

described

problem

separates

phases.

244

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.4

Solutions
1.

(i)
ment

The of

condition

of of

thermal

equilibrium
pressure
two

between

two

phases
free
The

is the energy
pressure/?
curve

establish-

equality
between

temperature,
the

and

the

Gibbs of

G=F+p
is

(per by given

mole)
p

phases
is,
the

(see negative

D.1)-D.3)).
gradient

given
for
a

(dF/dV)T,
T. Hence
we

that

the

F(V)

have

at

equilibrium,
A)
Fh+pVb
we

dVa
Further,
from

dVb
Fa+pVa
=

Ga

Gb,

that

is,

from

have

B)
established

Eqs. given (see

A) by
the

and
the

B)
contact

show in the

that

equilibrium
of

is
common

between
for the
curves

the

two

states

figure

points problem).

the

tangent

Fa

and

Fb

Ch.

4]

solutions

245

(ii)
in
the

Assume
upper

that

the

F-V

curve

is

given
can

by
be

continuous writ en
as

curve

as

shown

figure.

Condition
b

B)

above

and

therefore
b

-K)Eq. C) of ABba,
rule.
2. The
means

C)
area

(see
is,
the

the
area

lower
of ADCA

figure)
=

that
the

the
area

of

ADCEBba
This is

the

area

that

of

CBEC.

Maxwell's

Clausius-Clapeyron
dTm dp

formula

given
273

in

D.4)

can

be

used;

Tm(Vl-vs)
qm
=

(80

0.091)
x

3.13

103

-0.99

10~4deg-(cmHg),
=

where

the
1 cal

numerical

value
=

cm

4.18

107/13.6

980cmHg

3.13

103

cm

Hg

is

used.

3.

The

Clausius-Clapeyron

formula

given
dp

in
g

D.4)

can

be

used

The
vx.
an

specific
Hence
we

volume
can

vg of

water

vapor and

is estimate

very

much

larger
the

than

that of

of
state

water

put

vg
1-987

v,vg
x x

vg by

equation

of

ideal
v

gas:

373
=

pM pMH2O
=

760

1802 18.02

5,41

10

cal-(mm

'1

1699

cm3

g.
27.12
x

Thus

we

have
q
=

373 is

5.41

10
as

547

cal-g-1.
observed

Note: the

539.032

cal-g
value
1672

considered
for

the the

reliable
above

value.

Try

observed

cm^g

vg in

estimation.

246

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.

4.

By

Clausius-Clapeyron's

formula

D.4),

we

have

Sg-Ss

^^s
dp\
1

(gas"shd)'

Sg-Sl

(gas-liquid),
Thus
we

and

we

know

FgF,,

Vs and

5g>S'1>S'g.

find

5.

The

triple
a

in

p-T
of

point plane:
temperature

is

defined
the
T

as

the

intersection
pressures

of suffices of
the

the
p0i,p12

three and

equilibrium
P02

curves

equilibrium
where The the the

plot ed
ice,
water

as

functions
vapor

0,1
the
water

and

mean

and

phase
curve

pressure librium

respectively. is given
curve

pressure

by pol-T
mm

gradient Clausius-Clapeyron
between

tangent
formula
and

of
the

the

equilibrium
The

D.4).
ice

equiruns

phases

through

the

point

G60

Hg,

C)

and

has 80

the

gradient
cal
-

dT
at water

T0(v0
the much
q01 in

i?t)
hand,
runs

273-A.091
the

l)deg-cm3
curve

this

point.
and
a

On the
vapor very

other

equilibrium
the

pl2-T
D.58
<?12
v2
=

between

the
0

phases
smaller

through
than the

has
8 times
mm

gradient larger
0

A). specific
than
v0

point (Although
volume
or

mm

Hg,
600

C)
is
at
can

and

cal
vapor
curve

than

A),
greater

of

the
pl2
at

nearly D.58
be

Hg, approximated
the

C)
p0l

is

105
a

times

vt.)
the
AT

This
which

by
curve
=

horizontal
can
mm

line
be

and

the

temperature
have

the

intersection
to

with

calculated

from

corresponds

Apox

G604.58)

Hg.
dT

From

A),
-

we

0.0075

deg/atm.
for

Then
ature

AT
at

is the The

estimated

as

AT= is about

0.0075 0.0075

triple
reliable C.
In

point

Apol C (the
at

l atm.

Hence

the

temper-

pressure

is about

4.58
are

mmHg).
mm

Note:
and

0.0098

experimental 1954,

values
the

the

lat er
The

was

put
shows

triple equal
the

point
to
curves

4.579

Hg
the
p02.

0.01

C
p01,

to

define
p12

centigrade

temperature

scale.

figure

and

Ch.4]

SOLUTIONS

247
not

The

curves

given
The thus

by

broken

lines

are

stable
water

equilibrium
and
vapor
at

states

but
mm

are

only
0

metastable.

equilibrium

between

D.58

Hg,

C)

is

metastable.

water

A)

temperature

6.

The

Clapeyron-Clausius

formula

D.4)
dp
_

can

be

writ en

for

this

case

as

df~T(ve-vy
where
L
means

the
vx

latent and

heat

of

vaporization.
the

By
gas
L

the

condition

(a),
vg
=

we

have
we

yg^>yj.
have

Dropping

using
dp

ideal

approximation

RT/p,

RT*

dT.

Integrating

this

equation

under

the

assumption

(b),

we

obtain

psocexp(-L/jRr).
7.
Use eq.

D.8).
case

The

condition

for

stable

equilibrium

C.30a)

applied

to

the

present

is

under

the 5N"

restrictions:
is constant

the

total
the

volume number

is

constant

Ev'
in each

5v"

0),
have

the is constant

total

entropy

(SN'

CS=0), 0). Considering


5U
=

of the
first

particles
order
+

phase
we

only

variation,

(-p'

p"MV

yda

0,

248
so

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.

that

Ap
Consider
the this
is
an

p'-p"
drawn

da
=

y-^r
along angles
the

infinitesimal
Let
at

rectangle
92 be respective
When
the
centres

figure. rectangle by given

9X and
the

infinitesimal
of
curvature.

geodesies spanned
The
area

as

shown

in of

by
of

the this
the

edges rectangle
direction

pxp29v92.

the

surface

is

displaced

by

dp

in

of

the

radius,

the and

infinitesimal
the da
=

volume
area

dV'

p1p29l92
is

displacement

of
+

the

rectangle

increased
-

Sp is added by

due

to

the

(pi

dp)
do-

(p2

dp)
1

9fi2

p1p29192

Therefore

1
+

dv>
so

^
given

72'
by

that

the

pressure

dif erence

Ap
=

is

y[

+ Pi

Pi)
D.9)
by

)
is

-,

P
a

where
8.

1/p
entropy

is

the

mean

curvature.

Eq.
is

special

case

of

this

relation.

The

Sa of

the

surface

given

Ch.
as

4] shown its
area

solutions

249

in

when is
Hence

example is expanded

3.

The

heat
ox
to

Q which
a2

is

absorbed

by

the

surface
process

film

from

by

quasi-static

isothermal

given

by

Q
For
a

-T(a2-a1).
we

quasi-static

adiabatic

process,

have
=

dS,
Hence
G

0.

d2?
dT1
da
a
.,

dy
dT

or

d(dy/dr)
dy/dT
dy

Thus

we

have
a
=

dT

const.

This
the

is the

condition

for

the

adiabatic

process,

and

T2 is then

obtained

from

equation

ai~df7~a2~df7'
for

dyG\)_

dy(T2)

given
Divertissement

ax,

Tx

and

o2.

12.

Thermodynamics
namics the cradle
was

and and of heat. life


science

life.
to

It be

would old
friends. when

not

be Their the
young

surprizing friendship
German

to

find started

thermodyearly
R.
was
von

in

Mayer
work
a

thermodynamics struck suddenly


Another

doctor
of the

by
founder
Divertissement

the
of

and

great
Scientists that

physiologist
have the
not

(see
yet
we

ingeneous thermodynamics, 1).


the wil

idea

equivalence
also
not

of

Helmholtz
of be life.

disclosed

mystery

But,

do

you

be-

lieve

biological
which
one
new

phenomena
know
very

explained
govern

someday
inanimate
a

physical Although
an

laws
no

definitely

by those objects?

entirely
ever

it

is

found the

and

chemistry.
that

belief

the of a revolutionary can deny possibility life makes such which principle operative, to wil the invalidate exist, very unlikely seem to and agree, biophysicists Biologists to fruitful the approach way only mysteries

discovery principle,
of

of

if

laws
at

physics
in

least
of

the
is
to

life

250

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.
of

adopt biological
There

the has first without

working
processes.

hypothesis
been of
no

of

the

general biological
conservation

validity
phenomena
of
were

physical
ever

laws
violate
cannot

in

indication

that observations

the
work

law
the
in

thermodynamics: food. Biological


first

energy.

We elements
no

important
there
every

in
of
ener-

establishing
gy

law.

As

far

as

we

know
appears

today,
that

is form

form of
on

peculiar
chemical

pearing
or

to living biological grounds.

organisms:
processes However
can

it

energy may

ap-

be

understood
a

completely biological
is of This
process

complex
of
of the

physical look,
of

it therinterof

is

always
More

found

that is the

the

delicate

bookkeeping question
is
a
as

energy

always
the is second
an

very

strict.

validity
disorder.

law
atomistic Increase of
nature
-

modynamics. pretation
entropy

Entropy
of this

measure

of

concept
expresses

is be

implied
the

by statistical
unavoidable

mechanics.

proach
-

generally disorder,
consumed. "The
view

tendency only
down
are as

to
some

ap-

which

can

prevented
is running

if

some

effort
a as

work

is

that
the effect
It
on

the
amount

universe

into

condition

where has of

its

entropy

and

of views
to

disorder of
many
eye

great
on

possible
nature

had
is

profound phenomena. to organize


there
wise
mean was

the

biologists
that
the

their disorder.

springs surroundings,
Life
drive
to

the then

that
appears

is,
What

to

tendency produce
some

biological of living organisms "order" where formerly


the
to

in is
may

way

oppose

the

otherDoes

universal that

disorder.
do The
an
or

the

significance
the second

of law

this? of

it
Univ.
a

dynamics?" Press,
Maxwell
on

the

living organisms (Bridgeman, 1943) p. 208.) once imagined wall separating


the

violate

thermo-

Nature

of

Thermodynamics
clever
creature

(Harvard
who

extremely
containing

guards
and

gate

two
to

vessels allow

gas

molecules
to

skil ful y

controls
tissement

gate

so

as

only
Statistical

the

fast Mechanics the This


seems

molecules
gas
to
on
one

pass

(see
gets
second
nature

Diver-

1, in R.

Kuboetal.,
If he side demon find
to

(North-Holland
side
the

Publ.

Co.,
and decided Whether

1965)
that
on

p.

13).
the
a
we

functions
cools down.

properly, really is occurring


from
turns

hotter
law.
is

other

violate

Maxwell

the

wheel
of the
him.

against
When of behind
or

only
or-

when be
At

what
order

inside

living
may

ganisms
well

driving compensated
mechanism
it is stil demon could
are are

is

disorder,
which is
to

decrease

entropy
the the

by
of

something
life.

hidden
prove

hopelessly
existence

complex
present,
a

of
mental

Maxwell

extremely in living
be

dif icult

disprove
that
an

proof
Those who

achieved
in
to

organisms. only
the
refer
New
to

It when

seems

exact

expericreated.

life
the booklet

can

be

artificial y
aspects
of

interested A.

thermodynamic
York,
in

processes

recommended

Bioenergetics

biological by

A.

L.

Lehninger
9.

(W.
mole fraction

Benjamin,
x2

Inc.,
of the

1965).

(i) point

The A

solute

the the

liquid
horizontal

phase
line

which
drawn

appears

at

is

given

by

the

intersection

A'

of

from

the

Ch.4]

SOLUTIONS

251

point
the
gas

and

the
at

dotted

line
C is in

(liquidus
given
to

phase phase
B'
and

temperature

point corresponding
and

liquid point
gas
one

that
of

the

gas

that

the

point
of
the

phase
has

be

Ng

and

that

the mole fraction line), (ii) Also C at an intermediate by point (ii ) Generally of t h e t h e mol e f r act i o n solute B, point t h e are coordi n at e by phase x2 given B" mole Let the number respectively. be N,(Ng+N,=Nt + N2). phase liquid
+

x2

in the the
the

in of in

Then

Ntxl2
the

N2.
the B"
gas

where

x\
and
If

and
are

x\
the

are

the

mole
the

fractions
of

in

phase
the
one

and

in

the

liquid

phase, ly.

x2

coordinates

point
number

and

point
obtains

B',

respective-

this

is

divided

by

total

mole

N,

XtXl2
and therefore
-

*g)
which

(xl2
appears

x2)l(x2
in of solid
mixtures.
the

xl)
above

B'B/B"B.

This
Note:
geneous

shows
The

the

required phase
to

results.
case

The

liquid (contrary figure gives

is
a

always
liquid

homo-

the

precipitation
of

phase

from

solution).

the

example

N2

O2

75

252

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.
and
n2:

10.

By

assumption,

is

extensive

as

function
=

of

nt

that

is,

J(knt,
Dif erentiate both
sides

kn2)
k and &/
--

kJ(nx,
k=l,
dJ
to

n2).
get
=

A)

by

put
+

dnx
and
J
=

n2~~-

on2

nxJl

n2J2

B)

nx

+n2

A -x2)Jt

+x2J2

\x2 \

n2 nx
+

n2

Therefore,

__

___

-V

J2

Jx.
derived

C)
as

(Here
fol ows:

we

have

used

the

Gibbs-Duhem
dJ dJ
=

relation

which

wil

be

dJ

dnt
dJ=

dnx

1-

d2
+

dn2 J2 dn2

J\ dnl
+

J2 dn2.

From
n2

eq.

B),

we

have,

Jt d^

nl

dJx+n2
the

dJ2
is
y

(nl+n2)((l
given
=

x2)dJ1+x2
+

dJ2)
+

0.)

Now

dJ2. equation

Hencenx
of the

dJt
tangent

QPR

by
-

A
is

x9
Q:
R:

Jt
coordinate

x'2J2
of

(J2
the

Jx) (x2
P.
=

x'2)

JX+

(J2

Jx)

x2,

where
At

x2

the

point OQ

the
the

point

x2 x2

0,
1,

Jx. J2.
for
=

At 11. The

point
Gibbs-Duhem

RO"'
becomes,

relation

constant

pressure

and

temperature,

From

=p

rijJYPh

ZnjdGj
we

0.

A)

have Sit.-

Y 8n,

and

?
Putting
we

rij
the

log

pj

? Srij
of result.

J]
D.21),

rij

J] ^n,/J]
into

n,

? <5ny
using

J <5nf
the above

0.

definition

G},

A)

and

relation,

obtain

the

required

Ch.

4] the

solutions

253

12.

Use
ature:

Gibbs-Duhem

relation

C.12)
x2

for
0

constant

pressure

and

temper-

x1

dGt

dG2

(xt+x2
\*.*2

1).

If

Gx

is

given,

we

have
A/
1

Xl

x1

and

therefore
A/

dx2

After

integration,

we

get
!
=

^2 (T,P)
(per mole)
relation

RT

logx2.
solvent
be

13.

Let solute

the

chemical
be

potential
The

of

the
is
=

Gt

and

that

of

the

G2.

Gibbs-Duhem

x1dGl+x2dG2
for
constant

0,
for

A)

and

T.

Using
+

the

definition

D.25)
=

Gt
dp2
Pi

and
0.

G2,

we

obtain

xld\ogpl
(This
From
relation
for the
vapor

x2dlogp2
pressure

xl

dp!
Pi

Vx2
the

B)

is

called

Duhem-Margules

relation.)

Raoult's

law:

dpjpt
and
from
xt
+

dxjxi,
Hence
we

x2

1:

dxt

dx2.

have

for

x2

~0:

Pi

x2

Integrating,

we

have
p2
=

k2x2
this
+

(Henry's
into the

law), defining
=

D) equation
+

where

k2

is

constant.

Putting

D.25),

we

get

G2
where Note:

G2(T,
G\
total
+

p2)
RT\og(k1\p(i1)
pressure

RT

log^-2
is

Pi
a

<fH2{T)
of

RT

logx2,
temperature.
be

E)

<$>\{T)
If If the

function

the

the
we

is the

kept
total the

constant,
pressure

relations
p
to constant

exactly.
of

allow,
pressures

however,
px

A) equal

and
to

B)
the

hold
sum

partial

and

p2,

condition

of

pressure

does

254
not

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.

hold

exactly,

and

relation

B)

must

be

replaced
F

by
dp
,

^dlog^
where of

+x2dlogp2=
of variation
then
we

F)
the

V is
can

the

molar

volume

the
to

solution.

Usually
terms
on

right-hand
side.
1 atm,

side For
x

F) instance,
103cm3
wil

be let
and be
the

neglected
order of

compared
the

the

the
100

left-hand
be
x

Ap
have
terms

of

the
the

pressure

F=0.1
=

r=300K,
less
than

VAp\KT=
on

1/82x300
side.

0.004.

This
14. From

1/100
of
the

of

the

left-hand

equation

F)

solution

of

the

previous

problem,

we

have

xidpt
Pi oxi

_x2dp2
p2
a

ox2

neglecting

the
the
=

xi(xl>x2),
by origin
a,-

right-hand gradient
and the

side.
ctt

For

given
of
the

concentration
vapor pressure
connects

(mole
curve
a

fraction)
is

of

the

tangent

given
to

dpjdxt is given

gradient
Hence

f}t

of
from

the

line

which
we

point

the

by

Pi=pilxi.

A),

have

(ii)
Note:
15.

a2=p2
used
the
as a

(ifa1=j81)check
is
on

Relation
Gibbs
G
=

A)
free
energy
=

can

be

the

precision

of

an

experiment.

The

of

system
+

given

by
+

YdniGt
volume

ntC/f
can

(T,
be

p)

n2G2(T,
to

p)
be

RT(nt

log

xt

n2

logx2)

(see (i)

D.34)).
The

calculated

No

change
The

is

expected.

(ii )

entropy
S
=

(S=
ntS?
(ii )
H=G
H
=

(dG/dT)p>n)
+

can

be

expressed
+

as

n2S^
TS
+
can

Riri!
be
seen

logXj
to

n2

logx2).
by
+

Hence

statement

is

proved.
+

(ii)

The

enthalpy

be
=

given

n,m

nM

(H?

Gt

TS?).

Ch.

4] This

solutions

255

shows
do
not

that

there
any

is

no

heat

of

mixing.
there is

As
no

for work

the

internal done.
In

energy,

we

expect

change

because

fact,

we

have

A7?
16.
From

f t

pV?).
Here,

D.27)
we

and

D.34),
a

D.36):
detailed
of

pj
derivation
the

xJp(j
using

is

obtained
the

however,
and

give
The

chemical
=

immediately. potential
gas

D.16)
writ en
as

D.34).

condition

equilibrium

Gjnc{
=

Gj
RT

may

be

G?llq(T,
and
the
vapor

p)

RT

log*!
the
pure

Gjgas(T)
state
can

logpj,
from

pressure

pj

of

be

determined

Hence

PjlPj
The around

XJ

exP

-^~ side be estimated

exponent

on

the

right-hand
P
-

can

by
P
-

an

expansion

pj:
A&J
RT

5(/yliq
dp
holds
in

Pj

pr0

P
Rl

Pj

Pj\iq
Vjeas

RT
most
cases.

pj

Hence 17.

Pj
osmotic

xjp<j
allows

When

equilibrium
only
by
in the

is

established solvent
to

brane librium

which
is

go

through through,

semi-permeable
the condition of

mem-

equi-

given
is the the

where and
x2

p'
is

pressure

the
of

solution,
the solute.
-

p"

the

pressure

in
we

the obtain

pure

solvent

mole

fraction

Using

D.34),
=

G?(T,
Putting

p)
assuming

RTlog(l
n

x2)
small,

GX{T,
we

p").

p'=p"+

and

to

be

have

Hence

we

obtain

l(lx2),
where

A)
solvent.

Vt

is

the

molar

volume

of

the

pure

256

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.

Note:

If

x2<^\,
similar

A)
to

becomes

nVx
This
18.
Here

RTx2.
state

looks the

the

equation
px

of
the

of
is

an

ideal

gas.

vapor

pressure

of

solvent

given

by

Raoult's

law

and

that

of

the

solute

is

given

by

Henry's
=

law

p2(T)
The

k(T)x2.
the

boiling
P
=

point
p1+p2

Tb is determined
=

by
or

condition
+

po

Pi(Tb)x1
solvent
is
=

k(Tb)x2
by

p0.

A)

The

boiling

point

for

the

pure

given

Pi(T)
Putting
can

Po.

B)
that
x2

x1

x2,
to

Tb
first

Tb+AT
order
in

and
eq.

retain

them

assuming A):

and

AT

are

small,

we

Using

B)

and

Clausius-Clapeyron's

formula

dpi
dT
we

p\L

obtain

Tb(Fg-

Vx)

'

TbV%
C,

?.?(!_]<).
(Try
Note: another When the

solution,
A:=0
of

using

D.30a,b)
is

and

fol owing

example

6.)
is determined

(if

the
the

solute solvent.
the

non-volatile),
As is

ATjTbx2
well

only
be
used
as

by
a

properties
for

known,

this of
the the

fact

can

method
the

determining
of
an

molecular dilute

weight
mixture,
x1
=

solute.

19.

By
solvent

assumption
is

ideal

chemical
=

potential lx'2,x2<t:l,
of

of

the

given
x2,

by

D.30a).

Using

x2,x'1
the

x'2<A,
equilibrium A)

logXjN

log.xi==

x'2,
-

we

have,

from

condition

GU(T)

RTx2

Gls(T)

RTx'2,

Ch.4] where

SOLUTIONS

257

Gu
that
of in

is

the

chemical
solid

potential
phase.
of the

of

the

pure

solvent

in
=

the the
is

liquid,
temperature
determined

and

Gs
Tf by
and
the

the

Using
solid

the

the relation

precipitation

assumption phase (the

x'2
freezing

kx2, point)

B)
the

freezing

point

T? Tf
C),
{
Z>u{lf

of

the

pure

solvent

is

determined

from

Assuming

T{

Tf-

to

be

small,

we

obtain

G(T()=G(T()-(Tf-T{)S(Tf).
Hence
we

from

B)
Alf

and

retaining
)
+

up

to

the

first

order

terms

in

T( and

x2,

obtain

ols(if

)}

Klf

{I

K)X2,

or

AT,
where
Note:
means

RTf
the
a

(l-fc)x2,
fusion of the
to

D)
of the

Lt
k<

Tf (S^
1

S?s)
favorable

is
to

heat

of

solvent.

corresponds
it is
more

depression
for the
to

freezing
go

point
into

and

k>

(this
than

that the

solute
an

the
of the
two

solid

phase
freezing

into
The

liquid
show

phase)
the

figures

corresponds diagrams phase

elevation
these

point.

il ustrating
liquid
phase

situations.

liquid
Tr

phase

solid

k>\

solid

phase

phase

X2

Change

of

freezing

point
of

in

dilute

solution.

20.

By
The

assumption,
conditions and
the

the
of pure
u

chemical

potential
between

each the
pure

component
solid

is

given
1 and

by
the

equilibrium
solid

phase
phase
are

D.34). liquid A)

phase,

phase
=

2 and

the

liquid
+

given
=

by

tf,

RTlogxu

Gu,

G2l

RT\ogx2l

G2s,

258

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.4
and

where chemical

xu,

x2l

are

the
of

mole
the

fractions
pure

in

the

liquid
in
as

phase
the

G% G%
and the

are

the
solid

phase,
where

potentials respectively.

z-th

component
rewrit en
,

liquid

Eq.

A)

can

be

x2i

B)
T

'r
-~

/?

RT

RT2

dT

C
=

J
Tt

^ RT2

dT

C)

Here

d(G/T)ldT=
of

-His of

used.
pure

(Note
at

^
melting

0 at

T=Tt.)
T.

L^H^-H^
This is

is

the
to

heat
constant.

fusion
af
we
=

the

solid

the
of

temperature

assumed
in units

be
R.

LJRTi

is the

entropy

ASt

LJTi

measured

Now

have

~^)}
These

Ea),
line
and the

x2i

exp<a2

Eb)
and

give
eutectic

each

the

point

liquidus TB:
1-

intersection

of

Ea)

Eb)

gives

Tx

exp

<

oc2

1.

F)

Ch.

4]
or

solutions

259

Putting TE into Ea) determines Clearly, Ea) E to x2l from Eb)


21.

Eb),
the
1.

we

have

the line

concentration
from

at

the
the

eutectic

point.
E,
and

liquidus

xu=l

to

point

(i)
Using

Let

the

suffices
we
can

/ and
express

indicate the

the

liquid

and for

the

solid

phase,
as

respectively.

D.34),

condition

equilibrium

G2l
Through A) can
the

RT

logx2l
of
ax

G2s
A2,
defined

RT

logx2s.
in

J
solution
to

introduction
rewrit en
as

and

the

problem

20,

be

x}i_
*ls

ir
X2l
=

B)

Recalling
we

that
Xll
+

1,

*2s

-1

C)
1
-

have

from
xxl
V

B)
p"^1 c
-1-

-r

x2l

P~^2 c

-e

Xi

1,

or

X2l~

e-A2

-e"Al'
-1
-

D) E)
of
the

Xls

X2s

1,
the
form

eAl
or

X2s

eAl
in
the
eq.

-eA2>

to

(ii) By problem

assumption
20.

By

(b), assumption

A,

has

given

D)

solution

(a)

F)
and

by

the

assumption

(c),

Af<Cl.

From

D)

and

E)
i

we

get

4 A2
A2
T

A2) +},
"^

G)

X2s

] Ax

Using

F),

we

obtain

finally

T2-Tx
T-Tx
rp rj-,
'

2 1

T{T2-TX)
(T2
1
-

T) (T
{1
T\

Tx)
'

12

1X

T(T

1)

'

260

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.

We

know

from

these

equations Tt^T^T2,

that

if

Tx

<

T2
x2l<x2s.

The 1200 Cu-Ni

figure
K,

shows

the
1600 K

result
and in
a=

of
1.

the This

calculation
is

from

T2

similar

to

the

(9) and phase

A0) diagram

for
of

Tt
the

alloy

il ustrated

problem

21

(p.

233).

1500

1400

1300 1200

1100
1000

22.

Let

the
nB,. .

Helmholtz

free in
a

energy

of
V
at
a

the

mixture
T

of

ideal be

gases

A,

B,. .

(nA,

moles)

volume

temperature
nA,

F(V,
If

T,
for
a

nB,. .).
of the advancement
of

the

variations
are

of
taken
to

A,

nB,. .

variation

the

re-

action

be

the

equilibrium

condition

may

be

writ en

as

or

I SLMI
A,B,as

*
j
=

A,B,-

and

hence

A)
This
is the
same

D.63).

The

chemical

potential

expressed

as

function

Ch.

4] concentration

solutions

261

of

_,/

V has

the

form

Hence

we

have

The vL Note:
=

left-hand

side

is

nothing
denned

but

the

given

expression

if

one

puts

vA=

a,

/,. .etc.

Kc(T)
related

and

KP{T),

by

^KP(T),
are

C) D)

by

fKc.
Eq.
23.

B) D.65),

or

C)
one

is

called obtains

the

reaction

isotherm.

By

log*'=-6
and hence

RT

RTU
d

YvjSfCr),
AH
RT
2'

AS

&T where of the

dTRT

AH=YJ
solution

v}H
to

is the

standard

enthalpy
we

of

reaction

(D.64b)).

By

eq.

B)

problem
logi<:c
=

22,

obtain

Vj(Gj
Yv,
T

RT

log

RT),

and

hence

dlogi<:c
<1T
RT

V
[__i
the

_o

1
RT

V
l_jt
p j,
we

,_o

At

temperature

T Then
we

and
have

standard

pressure

may

use

pV=

RT

(per
and

mole).
hence

where

JC/

is

the

standard

internal

energy

of

reaction.

262

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.

24.

According

to

eq.

A.14),

[A2]
Eliminating problem,

83i^
[A2]
from

this

we

obtain

[A]2
[A]
of

equation D.19x
=

and

the

equation
1.70
x

for

K
or

given

in

the

l(T5-[A])x
x

10~4,

3.5

10mol/cm3.
becomes
3.5
=

Therefore

the

degree

dissociation

[A] [A]
To the
answer

2[A2]
question,

2
we

4.2-3.5
use

0.71.

the

second d d

the

reaction

isochore

derived

in

preceding

problem,
logK
dT

log
~

K/dT=AU/RT2:
5.0 8.3
x x

104-4.2

107

107-B73

18J
C)
calculation
x

and

thus

log
Hereafter,
obtain

wjgoQ
we

-30'
in

whence

KA9
with
x

1-35X done and


LFA1

A8
above,
to

proceed D.18
x x

parallel
-

the
x

[A]2
[A]
=

10

[A])

1.35

1.70

10,

thus

3.6

10

mol/cm3,
the

whence

J-

0.75.

25.

The

point

is

to

determine
The

(gas)?2A(in eqs. D.14')

C).
and

condition
this
may

equilibrium is obviously
be
writ en
as

condition

of
=

the

reaction

A2
to

OA2(gas)

2GA(c).

According

D.34),

(f(T)

being

certain

function

of

the

temperature).

Thus

we

obtain

26.

The

equilibrium

condition

for

the

chemical

reaction
^ of the

CaCo3(c)?CaO(c)

CO2(g):
"CaCO3(c)
may
=

^CaO(c)

be

writ en,

if

the

pressure

dependence

chemical

potentials

for

Ch.

4]

solutions

263

CaCO3

and

CaO
RT

is

neglected,
=

in

the
-

fol owing

form:
~

\OgpCO2

(jJaCOa
~

^CaO
d

^CO2(g)

AG,

and

therefore

<ilogj7co2_
&T
Here
we

/AG\AHT
denotes the formula Teal.

df\RTJ~RT*'
AHT
of

have

used

eq.

D.14'),
making
AHT
=

and
use

standard
to

enthalpy
be

change,

and

is

evaluated

by

the

given
-10.707 contains

51.957

27.

Since free

the

reaction of hence

under reaction

consideration
are

pure

substances
free

only,
energies
of

the
re-

energies
and

the

same

as

the

standard

action,

"+"

Hg(l)

~~

Ag(c)

l(jHg2Cl2(c)

From -1050

the

observed
and

values

of

and

(dE/dT)p,
x

AG=

-23068x0.0455

cal,
that

AS=
so

%(dE/dT)p
AG
+

23068
-

0.000338
298.16
x

7.80
7.80
=

cal/deg,
1276 is

Aff=
28.

TAS

1050

cal. found
to

According

to

the

given

data,

the

entropy

of

mercury

gas

be

190.1

107erg/mol-deg.
given
+

From

eqs.

D.14')

and

D.15),

the
=

entropy

per
-

mole
+

is

by

S(T, (we
that with
have the assumed that

p)

{ilogT
The
at

\ogp
law

1
and

/}
requires
1 atm
=

Cp
of the
Thus

%R).
we

third
T=

of K

thermodynamics
p
=

lat er
former

value value.

entropy
have
i
=

630
x

should

agree
+

the

190.1
4.2

107/8.32x

107

16.1-0+2.5

/,

(atm).
the
common

The

value
the

convenient

for

the

use

of
constant:

logarithms

j=/ log

10

is

called

conventional

chemical
;
=

1.83

(atm).

264

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.

Note:

The

molecular

theoretical
i
=

expression

given

by

Tetrode

and

Sackur

is

log[B7rmK/2fc5/2a>/r3],
m

where and
co

h
the

is

Plancks'

constant,

the

atomic

mass, state

k
of

Boltzmann's the
from
is
atom.

constant,
The
the
atm.

statistical above
agrees

weight
well
co=

of

the the

ground
value the unit

value
ex-

obtained

with
Note

calculated
of
pressure

above

pression
29.
The chemical
to

by

putting
potential
eqs.

1.

that

of and

the

electron

gas

outside

the

metal

is

given,

ac-

cording

D.14')

D.15),
Uc0
-

by $RT
the

GC(T,
The the

p)
condition

logT
metal

RTi

RT

log
by

p.

chemical

potential

within

G{
thus

equilibrium

Ge
P
=

G{,

we

is constant, obtain

assumption.

From

eiT5/2exp(-W/RT),
Since of the ordinate
in
a

where

W=Ue0
/
as

Gi

is intersection

constant.

log(p/Ti)
and
a

determine

the

ilV/RT, straight

we

can

line

through

the

observed

values

plot ed

(l/T,

log(/?/r*))

passing plane:

30.

The

net

reaction

of

this

cell
+

is

iH2(g)
and
hence

i4gCl(c)
of
reaction
+
use

Ag(c)
is
~

HC1

(aq,

x)

the

free
A G

energy
=

given

by
~

(jAg(c)
may

^HCl(aq)
for

i^H2(g)
and If

^AgCl(c)

In
at

this

expression
pressure for
=

we

Ag(c)

AgCl
we use

(c)
ecl-

the

chemical

potentials
for

standard

<jAg(C)
we

and

eq.

D.52)
AG

6HC1(aq),
+
+

^Agci(c)log(xy)
-

D-14')

GHl(g)
-

and

obtain
2RT

GAg(c)
AG

cj>HCl
2RT

|((?Sa(i)
electromotive

RT

logpH2)
force of

GgCHc)
the

log(jcy)
D.71),
we

RT
at

\ogp&2.
the

Remembering form,

eq.

arrive

required

where

we

introduce

H2(g)

^Ag(c)

0H

Ch.4]

SOLUTIONS

265
we

31.

For
V

the

Gibbs
T

free

energy
pressure,

G(p,
volume
of
G is

T)
determined

have and

&G=

-S&T+
of

Vdp,
the

where

p,

and
pressure

denote

the

temperature

system.

Then

the

dependence

by

dpjr
(p{T)
der Waals is
a

or

G{p,T)
The
volume

A)
Fis obtained

function

of of

Tonly.
state

by

solving

the

van

equation

nRT__rfa
V-nb with

V2'
respect
In
to

It

is

not

easy

to

solve

this

algebraically
temperature
of

to

Ffor order
use

temperature get
fact
an

lower of the

than
pressure

the

critical

Tc
G,
except
above it the
is for

Sa/B1bR).
convenient
the last in
term

to

idea
the
the

dependence
member
of isotherm
eq.

the agrees

that with
as

right-hand
area

A),
and

(p(T),
p-V

below

the

/?-axis

the

plane,

shown

below.

VT-.-.-.M1

266

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.4
eq.

In

figure
the value

(a),
of

isotherms
the i.e.

are

drawn
energy

according
at

to

B).
where

According
to

to
area

eq.

A),
the

Gibbs
to

free
the in As
area

isotherm
PA in

IP,
the

IPAOI

point (I being
a

P is

the This

equal point
value
the

the

below
isotherm

the
is

approaches length the point

figure
the
in

K-axis), (b).
value

addition
the

to

q>(T).
moves

shown
and

by
reaches

the

point
increases When towards

along
and becomes
P

isotherm
the
area

K,
or

of

IKXOI

plus
along
the

cp(T),
isotherm,
and
a we

KX

figure
turns
a

(b).
negative
free
energy
at
a

the the the M

the have
to

isotherm

give
Gibbs

sign
decreases

to

point negative p-axis. corresponding


moves

further

This
area

means

in

eq.

dp<0, A).
K Since

At

point
area

L,

the

from

the
area

value KXZMLK.
of the is

at

the

point
from the

by
the
the

the

KXYLK,
turns

and

point
the increases value
curve

by

the

isotherm

again
Gibbs free

towards
energy

positive
at

direction

p-axis
at

point
the
area

M,

the

again,

and

reaches
shown

point
by
QB
corre-

Q
in

QBZMNQ

plus
we

the
the

point
of
G

M,

which
p,
use

figure sponding

(b).
to

Thus the

obtain state,

against
faithful

including
of

KLM
the
van

unstable

by

making

der

Waals

Ch.4]

SOLUTIONS

267

equation.
JKLMN in but

However,
the that
rule. The

in

stable
line
area

equilibrium,
JLN,
JKLJ which is

the

isotherm
in LNML
J is

is

not to

the the

curve

straight
the
gas

drawn
area

parallel
in in rule
at

K-axis with

such

way

equals
to

the the Since free


J N.

accordance

Maxwell's

corresponding
to

point
Maxwell's
energy
N
are

equilibrium
is

with derived
J and

the the coincide

liquid
condition with

corresponding
that
each the

the of the

point
the

by
N

values

Gibbs and

the
same

points
in

other,

points

the

figure

(b).

1.2

-0.5

The

free

energy

as

function
mass

of of

T
argon

and

p,

all used

quantities
to

being
the

expressed
chemical

in

reduced

units.

(The

atomic

is

evaluate

constant.)

268

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.

Therefore,
curve

if

we

apply

eq.

A)
When

to

the

new

isotherm
P
moves

IPJLNQ,
from
J to
a

we

obtain

the
J.
van

IPNQ
of
is

in
area

figure
makes
the G-curve

(b).
a

the
so

point
that
MN the

N,
at

the from

rate

the

jump,
JK

G-curve the
G-curve gas

has
and

kink,

increasing the point


the

It

clear Waals
T>

that

parts

and
to
a

of the smooth
at

obtained

der
For

equation
Tc, the At T=TC, the high
from the
as

correspond
becomes G-curve
is

metastable

monotonically
the

liquid, increasing point


as a

respectively.
function
it

of from

p.

the

smooth while side.

critical
G-curve
T<

is when

reached
it is

temperature
the
gas

side,
temperature

the

has

kink

reached
When

low
is

rapidly
constant,
of

the

volume
is

quasi-statically decreases, begins


our

compressed
because
when
becomes

at

Tc, the
of
J is

density
the material
If
some

increases
is

the the
free
constant not
move

and
the
gas

liquefaction liquefied,
above
and
the

quantity point
a

kept
part

reached.
of

system
is

one-component
energy

two-phase
the whole

system.

G
gas

obtained

the
is the

Gibbs

system
ends. whereas

including
This
it
moves

is the

reason

from

liquid, why point


in

and
the

kept
does

until in

the the

point
J to

point
is the
is

in is

the/?-K
the

p-G diagram.
N

liquefaction diagram,
When is
as

all
If

the the The heat

material
pressure increase

contained
is

the

system
energy

liquefied,
system
the
result

increased
the

further,
Gibbs free

in
the

point compressed of the supply

reached.
a

liquid.
and

of

work

from

surroundings
of transition

during
is

the

compression.
by
the dif erence
we

32.

The
L
=

heat

given

in
L
=

enthalpies

per

mole:
the
ex-

H1H2.

Remembering
dL
_

0^
/dL\

0^

have

T(Si

S2).

In

pression
fdL\

dp
dT

dT

\dTJv
the

\dpjj
Clapeyron-Clausius
are

dp/dT

is

determined

by
The
other

L\T{y^

V2\

derivatives

obtained

in

the

equation: fol owing

dp/dT=
way:

(d_L\
\dTjp
/dIA

JJJh-H2)_
d(Rx

"

dT
-

Pi

P2'

H2)

d(Sx
dp dV[dT,v/e
2

S2)

\dpJT
Making
use

dp
Maxwell
relation

of

the

dS/dp=
_
"

have

11-S2)_
dp

2'

Ch.

4]

solutions

269

Especial y,

if

the

phase

2 is

an

ideal

gas,

/?2

1/Tand

Pi<CK2,

and

therefore

This

gives

dL/dT'=Cpi-Cp2.

33.

the line saturated c=Tds/dT along equilibrium (the vapor or c + curve) dp/ d T. /?=/?(r), Substituting T(ds/dp)T T(ds/dT)p the relation coefficient of thermal Maxwell's dsfdp= dv/dT= vfi (ft being and t h e Clapeyron-Clausius equation expansion) dp/dT=r/T(vg vl), use obtain of the fact that and of the ideal yg>i?' Making (vgvl). c=c%vv%$r\ we arrive at which can be rewrit en j5 r-1, approximation gas c=c\r/T, i f we remember t h e as approximate c=clp+dr/dTr/T=clp+Td(r/T)/dT, 32. in problem equation given 100 we a at obtain heat c= water 1.07cal For C, negative specific in the the values This means that, given by inserting problem. deg^g is removed, the of water of heat rises so an amount temperature vapor wat e r. t h e wi t h to t h ermal equilibrium keep ideal an there is an make If we additional term do not gas approximation,

Calculate

pressure

we

if
as

-rvlpl(vg-vl),
specific
order
34. heat

and

cl=cl
the

Td(r[T)/dT
line. for

is

obtained.
the
may

Here,
dif erence
be

cs

denotes
is of

the the

along
x

equilibrium

However,
and

of
If

10
the

cal

deg^g
pressure

water,
the that

neglected.
by

(i)

we

denote

within

liquid

drop

p',

the

condition

of

mechanical

balance

D.9)

requires

p'-p
The

2y/r.
the

A)
exchange
of material

equilibrium
and the
vapor

condition
is

concerning

between

the

drop

given

by

eq.

D.10'):

^(T>Pr)>
where radius
pr
r,

B)
in

stands i.e.
vapor

for the

the

pressure vapor
ps
._

of
is

the
pressure

vapor
of

balance

with

drop
usual

of and

saturated
pressure

the

liquid
notation

drop.
as

The ps=px,

saturated
satisfies

represented
.

in

this
.

{T)

{T,p)-

C)

,_

270

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.4

From

eqs.

B),

C)

and

D.14),
Pr+

we

obtain

]"
is

))
dif icult

fcriog^.
to

D)
the

Remembering
therefore is the free and

the

fact
energy

that of the the

it

compress

liquid
when the

and
pressure

that

liquid
left-hand
=

changes
side

only
of

slightly
eq.

changed,
respect
obtain

expanding

D)

2y/r)
with
to

2y/r)
P

Pr~
we

pr

\
or
.

Poo

E)
\

log

D. Pr
=

V,D~ vWoo
-

fr

D.
i

1+
the

2v
-

F)
volume
of

where
at

we

have
p^

used
and
=

d\il\dp
temperature

vx.

If

we

denote

specific
have

the

vapor

pressure

T
can

by

ve,
as

we

vlpo0/kT=vl/vg<g.l.

By

writing

pr\p^

1 + y,

F)

be
+

rewrit en
=

\og{l
Since

y)
quantity
on

(vjv
of

F')
the of
the

vjvg
y

is

usually
the

small of

order

of

10
of
on

10

we

may

neglect
to

in

determine

parentheses the point

the

right-hand

member
functions

eq.

F')
both

in

order

intersection

sides

(the

right-hand figure).

member
This

represents
is

an

almost
to

horizontal

straight
eq.

line;

see

the

procedure

equivalent log

approximating

F)

as

2vl7
rkT'

G)

Ch.4]
From
eq.

SOLUTIONS

271

G),

we

obtain
Pr
=

rkT'
the
the
vapor

(8)
pressure

As
water

an

example, drop

the
at

relation is

between shown
in

and

the

radius

of

20

fol owing

figure.

20

40

60

80

100

120

140^
Qxp{2vty/rkT}
smaller
would than be be
is apt
rc

(ii)
given
vapor

The p>pa>.
pressure
rc

critical
Since

radius the

rc

is

determined

by
a

p=pr=pV)
a

for has

a a

liquid
than
radius
a

drop
p,

higher
the this there
are

such

having drop,
a

radius
it

if

existed,

vaporized.
stable.
in
to
a

Thus Note:
in

is
For

smallest
reason,
no

with

which
cannot

liquid
for
fine

which

nuclei
are

supersaturated. produced corresponding


35.
In A

If

there those the

drop condensation, particles


under radius
r.

liquid easily
and dust

drop
be the
vapor

can

produced
liquid higher

vapor

become

like
a

particles,
pressure

drops
than

are

around
to

particles particle
AB

vapor

pr,

the

negative
is

fol owing specific

figure,
heat that
of

denotes saturated
B.

the
vapor

saturated
means

vapor

pressure

curve.

The

of
from

the
vapor

that

the

entropy
pressure

of

vapor

larger
the

than isotherm

On
the

the

other

along

B,
value

entropy entropy
line
curve

hand, obviously
at
a

if the
C
a

is lowered

increases
on

((dsldp)T
isotherm
agrees than that be

(dvldT)p<0),
that
at

and
A. Thus
vapor

the

of

state

the

with the

the

isentropic
pressure

AC
AB.

has

gentler
result
can

slope
also

of

by
the the

supersaturated comparing equation


lat er method

This

reached

the is

Clapeyron-Clausius

(dpldT)s=cpIT(dvl8T)p.
equivalent
to

equation Remembering

&pj&T=HT{vg
problem
the

v^
heat

with
that

33,
the

show

determining

sign

of

specific

of

272

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

50

400

supersaturated expanded
vapor

vapor.

Now

we

see

and passes As

the

saturated
CA
into
a

vapor
state

is
of

if the that, expanded

Wilson

chamber
the
vapor
on

is
state

suddenly
of
of the AB.

adiabatically,
a

along
was

Note: be

shown
even

in
in
a

the

preceding
chamber
those
we
can

supersaturated problem,
state,
and

the
cannot

left

liquid
there
are

drop
no

easily
If
the
some

produced
passes if the
a

supersaturated
the
is

when
ions ions
are

nuclei.

radiation
and

through
chamber

adiabatically
vapor,

expanded
act

produced immediately
as

along
afterwards
for of ions
1 and

path,
to

produce
and

supersaturated
appear.

nuclei

condensation

fog

drops
chamber.
to

Thus

observe
for the
24
reason

the

Wilson 36.

(See
the

problem
solutions

49

path why

radiation
act
as

by nuclei.)

the

(i) According of Chapter netic field,


the
use

of
per B=0. In

problem
unit the

of

3, the
is
for

free

energy

volume,

Chapter including

of
energy

problem
of denotes
mag-

29

the

given
77=0

by
and

F/V=F0(T)/V+(\/4n)
present
=

J
case,
w BH

dB,
it

where is
more

F0(T)
convenient

value

to

G(H,
in Meissner

T)
as

-V

4tt of
the

A)

place

of

F,
effect

for is

is

considered

one

independent
Hc

variables.

The

represented

by

the

relations
if

B{H)

\H\

<

Ch.4]
and

SOLUTIONS

273

if Thus
we

\H\>HC.

obtain
V
=

F0(T)

if

\H\<HC,

B)

(H2

H2)

if

\H\

>

C)

so

that

dGs ^
dT

dGn
dT

dH2

Sn

^,

dT the

or

(Sn
volume

-Ss)

x
=
~-

dH2
dT

Sn

D)
(ii)
For

the

heat

capacity

of

whole

system

of

V,

we

have

*2
dT

Sn

d2H2/dT2c/
E)

Putting

T=

To and

Hc

0, and

converting

into

the

value

per

mole,

we

obtain

IHC\2

-^
(ii )
If
we
assume

(T=T0).
we

F)
from
eq.

Hc
r
n

H0{l-(T/T0J},
_

obtain

E) G)

r
s

VTH VTH2

ot12

( </1
)

/Tx2"

This

value

is
to

plot ed
the

in

the

figure

by

the

broken

line

(the

ful -drawn

line

corresponds

experimental

value).

274

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.
the

Note:

Typical

graphs

of

Cn

and

Cs

are

shown

in

second

figure.

37.

Let
gaseous

us

denote

the

concentration the

xt

or

x2

by
suffixes
are

x,

and determined

distinguish
g and

between

the
The

phase
line

and

liquid
the

gaseous

xg(T)

and

phase liquidus

by

the

xt(T)

/, respectively. by

A)
Their behavior
T=
near

the
=

azeotropic

point

(T,
8xt.
terms,

serting mining
and

T
relation and

dT,xg
among

xg)
only

the

d T,

8xg, 3xg

and and linear

xt=xf

jtg=jt)
+

can

be

seen

by

in-

8xt Expanding
we

into

eq. in

A),
powers from

and
of
eq.

by

deter5 T,

5xg

dxl}

retaining

the

obtain

A) Ba)

-SHST

$>> ST

dG2
dxa

-S2X5T
denoted

dG2l
dxl
by
the

Bb)

where values

we

have the

used

dG/dT=
point.
+

-S,

and

?lg,. .,
Gibbs-Duhem

d6lg/dxg,. .
relations
+

their

at

azeotropic
x2l
as

Remembering
=

-SldT+xlldGll
we
can

dG2l
fol ows.

0,
In

and order and

-?gdr+
to

xlgdGlg
eliminate

x2gdG2g
we

0,

determine

5T

dxt,
the

say,

multiply
to

eq.

Ba)

by

xt

and

eq.

Bb)

by

x2l

add

together

results

obtain

Ch.4]

SOLUTIONS

275

-(x0nSu
for
the

x02lS2l)dT=-SudTfor
member,
we

the

right-hand
Xn
=

member,
Xig
that the and 6T
means

and

left-hand

remembering
at

Slg
at

Su^0,
second

x^^x^.
is
a

-SH8T
Since

arrive
order

5T=0. the

This
gaseous

result

quantity

of

least
the

along
area

line
be be

and

liquidus.
the

38.

Let

cross-sectional
in

of
of the

the
rod end.

rod

tration
to
a

the

liquid
x

part
from
its

equal Cm (x),
when of
should

to

1, and
when
the the

impurity
rod is

concen-

solidified

up

distance
over a

left
the

Then,

solidification
removed

further

distance

dx,
This

amount

impurity
be
the

from
d

proceeds the liquid

part
of
the

is

given quantity

by kCm(x)dx. of impurity

amount

change

{Cm(x)
and

(Lx)}
therefore

in

the

liquid
=

phase
-

Cm(x)(Lx),

d{Cm(x)(L-x)}
dx

A)
obtain

Integrating

this

equation,

we

(A being
Since
the
=

constant). liquid
is

B)

impurity

concentration
thus

of

the

initial

C,

we

have

ALk~1

C<^,

and

C)
The

concentration

of

impurity

in

the

solid

phase

precipitating

at

the

point

becomes

D)
This value
is

plot ed

in

the

figure

for

<

1.

(It

is

not

correct

that

C(x)->

oo

C(x)

276
as

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch. of
constant

x-*L.

This

error

arises small

from
We
see

the

assumption
the

k,
towards

which
the

is

correct

only
end,
: as

for and
the

C.)
left
in rod end
a

that rod
of

impurity
pure.

is of
is

gathered

right
Note such

of
process

the

becomes

Zone Si
an

refining:
and induction

purification
the when
are

semi-conductor
made
to

materials
pass

Ge,

made

of

material
the

through
near

the the

coil melts

of and

heater.

Then,

part
towards the

of surface

the
the

rod

coil side

re-solidifies,
part
is

impurities

(the

molten

kept

from

collapsing

gathered by

right-hand
The
reason

tension).

heater

coil

is very
zone

exactly
pure

that materials

shown

in

the

problem
such
there
to
a

solved
zone
a

above.

The is

method called
a

of
the uniform
use

obtaining
method
concen-

by

repeating

tration

melting
39.

Conversely, refining. impurities by adding (zone levelling).


First,
determined
*i

is
pure

case

melting of obtaining
and

of of

substance

by

making

zone

(i)
are

the

relations
as

between

0(-

and

the

molecular

fractions

xN^
02]

N{

r0i/N>i
we

02]

>

X2

02/[>0i

A)

By

solving

these,

have

0i
Now,
condition

*i/l>i
of
p

rx2],
given
T,

02 expressions

rx2/[x1
for

rx2]
we

B)
under the

by

making
of
constant

use

the
and

Gh

obtain,

xt

dG{

[r0!

2]~'

(rfa
+(r~ ([?7@! r02}

\RT\j
l)r-2rw(l
+
-

(J *)}
"

^2I RT)T
02]
+

-V2)

|uV2

r02}

2rw0,02]
=

A0,
0

2rw0102]

d02)

(since

d0!

d02

0).

Ch.

4]

solutions

277

(ii)

According

to

?,=

dGjdT,

we

have

and

hence

-(r-l)<?1}
0
-

[xj
entropy

log0t
of ideal
=

x2

logtf>2]
the If

C)
fractions
the

In

the

expression
of
the
to

for

the
as

mixing,
variables
solution.

volume
in
we

0/s

appear

in
in

place
contrast

xt's
the
!

the of

independent
an

logarithmic

functions,

case

write

*!
we

x2log02] + x2logx2]
is,
in

#[log{l
larger
we

+(rthan
the

l)x2}
that

x2logr],
ideal

find
r>l.

that

this

entropy

general,
+

of

an

solution

when

(ii )
to

Next,

by

using

Bt Gt
=

TSit

calculate

partial
+

molar

enthalpies,

obtain

Bx
and hence the heat of

B?
mixing
-

w<t>22,
is

H2 by

H2

rwtf,

given
=

? XtBt
This vanishes

? xfl?
1, and

wix^l
reaches its
r=10

rx^\)
maximum and

=-^^~w. Xj
X

rx rx2

D)

at

x2

0 and Two

value

rw/
are

atx2
the

(y/r
Finally,

l)~1.
the

(y/r +1J
plot ed computed.
to

examples
pressure
us

for
and

for

r=100

in

figure. (iv)
vapor

the

osmotic

pressure 6. is

are

To

calculate

them,

let
the

use

the

results of

of

example
at

According
as

the

given

chemical

potential,
at
=

activity

solvent
1

given
+
t ^,

(jJ)

exp<[

) 4>2

^2

E)

Therefore

we

obtain

4>l\,

F)

278

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.4

1.0

RT

log(l
W

r2/

62)

rT

N2

RT

\2
2

RT
w

G)
rx-,

1 +

(r

1)

x2
2 2

l+(r~

1)

x2

When

the
an

concentration

is

very

low,
occurs

van

't
if
at

Hoff's

law

is

valid

as

in
r

the
is

case

of
the

ideal

dilute from
of the

solution.
that
vapor pressure

However,
law

the

deviation

polymerization relatively
r->oo are

grade
small
mole

large,

fractions.

Examples
the

p\p\

when

plot ed

against

(jJ

in

fol owing
to

figure.
the

40.

According

condition

of

electrical

neutrality,

(la)
n

xx-

(lb)

Ch.4]

SOLUTIONS

279

ft,

0.5

0.5

although
laws for

M+
M+

and
and

X X~
i

are

exchanged
the
n
_

between

I and

I.

Also

the

conservation

require
,

equations
0

v'

4-

y"

B)

On

the

other

hand,

the

equilibrium
|j\#
+
V"

condition
/f
\

is
+ V"

\J\M

/TT\

If
J\
nT

an !/-*/%/'

ideal
iOgl ajj+aj(-)

dilute
v'

solution
"\

is
DT

assumed,
(-v11
v

the
\
^
/-k*.

lat er

condition
"*M
-v'
+

becomes
"*X~
-v'

^^o

r^n

"*X~/'

-v"

"^M

-v"

"^X~

-^"

\"/

/'/I

where

eqs.

D.33)
eqs.

have

been

used

(<?m+
and

anc*
we
02

<^xobtain

are

tne

same
=

for

I and
-

I ).
=

Substituting

(la),
and
hence

(lb)

B),

(xx-J

(xj

xx-J

(xxIn

+X2)
the
same

x'x-,

Y' x2
way, xx

Av-

v"

AT

r>

This
jT

means

that

M+X

itself

is

distributed

between

and

in

the

ratio

X2

H.

If

the the

electrostatic

potentials
potentials

in

the

phases
are

I and

are

4>, and

4>n,

respective-

ly,

electrochemical

given

by

280

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.

The

equilibrium

conditions

/ m+=*7m+

and

^lx-~rl'x-

giye
exp

A)
ob-

where tained

eqs. in

D.33)
the

have

been of
the

used

for

solution

preceding
kT
e

n'M+,. . problem
kT
=
-

Substituting
into
eq. 1 +

the

results
we

A),

obtain

4>,
Note: From
as

#n
we

log
derive

xx.

xxeq.

log
in the

(
\

x2
~o

xx

eq.

A)
be

can

D)

solution

of

the

preceding

problem,
42. This ionic is

should

the

case.

also

problem
on

concerning
both
*r RJ,
-,

Donnan's sides
when

membrane
the
~

equilibrium.
I and I the
are

If denoted
pressure

the

concentrations
-

of

membrane
is

by

x'u+xx
is

>

xm+>

x'x

>

and

M+X

added,

then

osmotic

given

by

(F

being

the

molar

volume

of

water).

According

to

the

solution

of

problem

RT

x"

'

RV

x"

Therefore,
the

the

osmotic of
to

pressure

starts

from

the

value
the

(RT/V)-2xRaddition limit of
In

before of

addition
amount

M+X~,
one

decreases half of concentration


the This
a

gradually
initial
is
an

by
value
in the

M+X~,
addition

and of do
a

approaches large
remain
not

the

of
with

M+X~.
the

expected

result.

phase

always
pass

jt?-.
and remain the I decrease and
in in

Before
membrane
the
to

adding
because

M+X~,
of
so

I , R~ions M+ions
the the concentration of

through
due
to

semi-permeable corresponding
is

electric osmotic

attraction
pressure

R~ions,
value

phase
the

I,
solution

that of

has
When
X~ R~

the

2jcr-.
and of

M+X"
in the the

added,
I and

dif erences

of

ionic

concentrations

M+

phases
decreases
two

gradually
become from
the

(the

effect
at

of last:
of
R~
a

the
the

existence

ions
It

relatively),
phases important
comes

equal
existence

dif erence
ions. addition in

between
Note: of

is of

very has

only biological
effect
for instance.

phenomena
on

that

slight
colloids
or

electrolytes amphoteric
to

a or

remarkable

the

osmotic

pressure

colloidal
are
so-

solutions called

protein
the

starch,

(Many
either

of

these

according

pH

electrolytes, value.)

and

become

negative

positive

ions

Ch.4]
43.

SOLUTIONS

281

First for
a

let small

us

derive
x2

the

necessary

relations.

According
1

to

example

8,

we

have

logi
From

vx2g

vm2Mx
-

</wwv

1000

g,

x2

dlogy

dx

dx2.

A)

example

6,

Inserting
-1436
we

the

values
and

(because
1.9870
RT
-02
i-V

HCl->H++Cr),
cal/deg
mol
and

T?
Mx
=

273.16

deg,
into

cal/mol,
obtain

R=

18.016

g/mol

Lx this,

AT
as

3.72 the e=4.802x

m2g(deg)
theoretical

(m2
Debye-Hiickel
10~10
e.s.u,
we

in

mol/kg).
equation,
=

B)
and

Making calculating
fc=1.38
we
x

use

of
A

eq.

D.56)
Z>
=

for

88.23,
we

JV0
may

6.025x

1023

and

10~16

erg/deg,

have

1.12.
,

Since
a

put

C2=p1m2=m2,

obtain

-aVm2,
Changing
x2

=1.12.

C)

in

eq.

A)
H
m

to

m2:

logy

dm2
o

dm2
-

f
o

2m2j

m\

dm2

;~~
Using problem
eqs.
to

0.375
1

v
g

D)
from
the table

B)
obtain

and

D),
the

we

can

calculate

given

in

the

results

given
experiment

in
1 -g

the

fol owing
1 -g

table:

/^(mol'kg-1)

Debey-Huckel
0.009
0.012

0.627
1.179

10-3

0.021
0.011 0.017 0.011 0.017 0.020
0.022

1.245
1.474

0.013 0.014
0.017 0.022

2.228 3.526
4.520 6.879

0.025 0.031 0.039

0.025 0.027

10.633

282

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch. denoted
are

44.

If

the

number

densities the
number
use we

of
of

donors densities the

and

of of

electrons
D

are

respectively, respectively.
electrons

and

D+
and

by Ndne
for

Nd
conduction

and

ne, ne

and

Making

ideal
from

gas

approximation
eqs.

the the

(pe=nekT),
for
an

obtain

D.14')

D.15a)

chemical

potential

electron
j"e
=

rf

\^T
to

log
the

kTie
of

kT
an

log
ideal

ne.

For

and

+
,

according

assumption

solid

solution,

we

have

?)

kT

log

-d"-e,
,

HD+=HD+(T,p)+kT\og~
from
eqs.

D.34).

Therefore,
e

in

equilibrium,

fiD=nD+

+fie

by

eq.

D.63),

and

therefore
c

Nd-ne
On the

T*

exp

\-(f? kT
{
^d

fil+the ionization

nS)

>.
in

crystal

right-hand Ed. Thus,

side,
when

jU
ne<^Nd,

j"d+~

equals
becomes

energy

the

the

answer

45.

The

net

reaction

given
+
e

in
and
to

the
in

problem

is

made
+

in

the

two

steps
eq.

Ag(l)->
in

Ag+(AgCl-KCl)
particular
electro-motive cell
referred
force

Ag+(AgCl-KCl)
the

e->Ag(Ag;cAu1_;c)
to

the the

problem.

According

D.42),

is
=

given

by

5-E

GAg(AgxAui_x)

(/Ag(i)
-

6AgA)
the the value

RT

log(xy)
If
an

6AgA)
solution

RT

log(xy),
is

where
y
=

denotes

activity.
1.987
,

ideal

assumed,

we

have

1, and

expect

1360
.

23060
at

iOg
values
in

1
=

0.082

(V)
y
.

x=0.5

and of
y

T=
are

1360

K.

From
as

the

of the

and

given
table.

in

the

table,

the

values

determined

given

fol owing

Ch.4]
X

SOLUTIONS

283

%EJ2303RT
0.078
-

logio
0.072
0.145 0.220

logio
-0.006
-

0.846 0.716

0.021
0.045 0.074 0.114 0.198

0.986

0.167 0.274

0.022 0.054
0.095

0.950
0.884
0.804

0.602
0.471

0.422
0.734
-

0.327
0.580

0.263

0.154

0.701

46.

chemical

reaction

of

the aA
+

type
bB+---+lL

A)
in
the

can

be

expressed,

after

eq.

D.59'),

form

B)
The

degree
where

of
we

advancement

of
X
=

the initial

reaction
state.

is

introduced

by
free
energy

definition
of the

D.60),
whole

put

0 at

the

The

Gibbs

system

G(nA,
is
a

nB,. .,

nL,. .)
equilibrium

5>f e6fe k
is

G(X)
by
the

function
=

of

X.

The

chemical

determined

relation

(8GI8X)PtT
In

0,

that

is,

by

eq.

D.63):
T
=

AG

yZvkGk
G(X)
=

O.
be
a

C)
minimum
at

order

that

the

determined

by

eq.

equilibrium C), i.e.,


=

be

stable,

should

(d2GjdX\T
(i)
in
constant

{dAGldk)PtT
of

^
X

VvkGk
corresponding
Note

>

0.

D)
to
a

The
constant
at

change
the value

in pressure

the

degree
is
zero.

advancement

change
is

Tat

expressed
We
note

by
that

{dXjdT)p>AG.

that

AG

kept

dTjp,AG)~
and that

d(T,AG)

d(X,T)

\dT

)Pt J
Pt

Aft

-jr
(since
in the

F) change Eq. E)

AG
reaction

AH

TAS=0),
and
is writ en

where
as

AH=Y,
dHjdX
in

vkHk

denotes

the
to

enthalpy
eq.

correspondence

C).

284

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.

becomes

dX\

dT/PtAG
The denominator
and reaction
If
way
on

_1fdH\
right-hand
and and

T\dX)p<T\\
side is

l(dAG\
positive,
have

dX

)p<T
according
the
same

the

to

D),
the
creases.
reverse

hence
is

(dX/8T)PiAG
endothermic,
the
T

(dH/dX)PtT
is

sign.
balance shifts

If

inequality AH>0,
as

AH<0,
when
p

reaction is raised,
at

proceeds exothermic,
T,
we

forwards
and the

(X increases)

inthe

in

(ii)

When

is

changed

fixed

have,

in

similar

way,

where

Jt.xI
the

() \d*
reaction.

Jp.t
=

Avl( l\
(dVldX)p>T
the

dX

(8)

means
are

the

volume

change

in
AG

Since

denominators
In

of the
case

eq.

(8)

positive,
if the volume

(dX/dp)Tt
increases
in

and
as

A V have

i.e.,
shifts

the

reaction
formula
in

leftwards

the

reaction

signs. opposite proceeds, A), while,


such
a

of

A V>0,

the if that

chemical

equilibrium
it

AV<0,
the

shifts

rightvolume

wards.
is 47. The

Thus,
decreased.

the

reaction

proceeds

direction

whole

necessary
to

conditions

for
E pressures

sponding
are

the

point
of

and
first

the
p,

equilibrium liquid
temperatures
two

between

the and
are

gas
to

phase
the

corre-

phase
T

corresponding
the

the

equality
the the
two to

chemical rule be

point potentials
satisfied derived

ft

of

phases.
the
way

The of

conditions
A

automatically
can

according
from

selecting

and

E.

Maxwell's

third

condition

).
If

A)
free
energy
+

the

mass

in

the

volume

V is M,
=

the

Gibbs

in

the

state

is

GA(p,
For

T)

MnA{p,
TS^

T)=UA+pVE,
and

TSA
eq.

pVA.
can

the

state

E, MpiB
form

(p,
-

T)=UEUA)
-

A)

be

writ en

in

the

fol owing

(tfB
Thus
we

T(SE
the dif erences

SA)

p{Vu
of
internal

VA)
energy

0.

B)
UE

need

to

calculate

UA,

and

of

entropy

SE

SA.

Ch.4]
If
n

SOLUTIONS

285

moles form

of

the

gas

are

enclosed
nRT
P
~

in

volume

V, the

van

der

Waals

equation

has

the

n2a
~

V-nb
and

T72
R
to

'

C)
gas
constant.

where

and i.e.

b
eq.
to at

are

material

constants,
be

the

Note KA and
is

that EN of the

in

equilibrium,
isotherm,

C)
the
constant

can

applied
outside
cv

only
of

the If
a

parts
eq.

region
volume

ACE.

C)

specific

heat

becomes

function

of

applicable, T only,

the
as

was

t)=v/ve=V/Vc
the

shown

in AJE

the

solution

of

problem
SA
A

34 is

in

Chapter
to

2.

In
an

order

to

calculate

entropy
process

dif erence

SE

it

sufficient
E

take
the

arbitrary
in line.

quasi-static
which
If M
eq.

connecting
like the
one

with
in

through
figure by

region,
the broken

C)
is

is

applicable,

shown

the

fixed,

286

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.

is

function

of

and

T,

and

dT

D)

In

the
A

last

step
E
are

we

have
states
use

used
at

the
same

Maxwell

relation the

(dS/dV)T
last

(dp/8T)v.
in
eq.

Since
must

and

the

temperature,
we

integral

D)

vanish.

Making SE E

of
vE

eq.

C),
nR

thus

obtain

SA A

Va.

V-nb
in

dV

_.

nR

log-

VE-nb
.

VA-nb
becomes

w E)

In

similar

way,

the

dif erence

internal

energy

A E

Ve

.,

dV

nza[ na[
E)

.2

'

Va.

\v
and

v]
F),

F)

Here

we

have

used

eq.

C.21b).

From

eqs.

This

dif erence
based

is found
on

to

be

equal
states:

to

the

integral
eq.

ofpdValong
C)
was

the for

isotherm
states

ABLDE,

the

assumption
unstable

that

valid

all

in-

cluding

metastable

and

2alv=VE
ABLDE

Va.

(8)

Ch.4]

SOLUTIONS

287

x>=V/Vc

288

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.

Therefore,

remembering

eq.

B), pdV

we

arrive

at

p(VE-VA).
points
A

(9)
and

ABLDE

Since of The
eq.

is the

value

of

pressure
to

at

the
of
to

E,
of
and This both
A

the

right-hand
in the

member

(9)
left-hand
the
area

corresponds
member isotherm
DELD
into is

the

area

the

rectangle
area

corresponds
ABLDE

the

AEWQA the region


thus is
eq.

figure.
that
rule. To

between the
convert

and
to

the
area

F-axis,
ALBA.

ABLDEWQA (9) means


of
vl
eq.

equal

the

Maxwell's
sides

the
M.

total

mass

functions and
Note: vice For

of
versa,

v= volume specific V/M, at the The vol u mes specific i s det e rmi n ed (or p) only (p

divide

(9)
vg,
a

by
become

the

points by
at/?
=

and for

E,
eq.

and

solving
1 atm

A)
water,

for for

as

T=

100 the

C the

is obtained

given example).
of
state

T,

modified Maxwell's

by
rule
is

reference, introducing
and
in

relief

of

the
states

van

der

Waals
which

equation
is

horizontal
to
on

line
of 287. is Since

AE,
the

determined
gas
an

by liquid

phases,
48.

shown that
the

corresponds the figure


volume

coexisting

page

Assuming
energy
near
can

change

negligible,
we as

let
are

us

consider
a

the

free

per

unit

volume

F(M,
M

T).
be

considering
We
assume

ferro-magnet
that

the
be

Curie

point,
as
a

may

regarded
of
M
as

small.

F(M,

T)

expanded

function

F(M,
(The
zation the
presence

T)
of
to

F@,
do the
not

T)

a(T)

M2

j8(T)
one

M4

A)
of

odd is

powers

appear,

because

direction

magnetiin

equivalent
of

opposite
field
H

direction.)
is

The

equilibrium

condition

magnetic

that
=

F(M,T)-HM
from which
the

min.,
for for

B)
T>TC,
##0
the

M(H)
proportional
terms

is
to
to

determined.
H

First,
should
in eq.
appear

magnetization
large

M=xTH retaining

(not
from

\H\).
B)

Thus,

up

M2

A),
=

we

find

condition

oM
so

(|aM2-HM)
a
=

0,

or

H/a,

C)

that

l/xT,

or

(T-rc)/A

D)

Ch.4]
For
M

SOLUTIONS

289

r<Tc,
has
a

in

eq.

A)
at
term

becomes
M=0. If

negative,
the

and

the

curve

of
two

F(M,T)
minima
at

versus

maximum
of

because

the

M4

(see

/?>0, figure).

F(M,T)
For

has

Af#0

H=0,

these

minima

give

the

F(M,T)-F@,T)

-Ms

Ms

spontaneous
ature,
we

magnetization
may
=

Af8.

In

order and obtain


=

to

discuss

it

near

the

Curie

temper-

put
0

j8(!T)~j8(Tc)
and thus

<xMs
This

?j8Ms3
gives
the

Ms
the

J-6ol/P

{6 (Tc

T)/Aj8
below

(Tc)}*.
E)
Tc

behavior

of

spontaneous

magnetization

(see

figure).

Tc

Therefore,
M
=

for

H=0

we

obtain
=

0,

F(r) F(T)

F@,T),

if
3
P

T>TC;

Fa) Fb)

MS,

F@,T)

a2
_+,

if

T<TC.

290

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch.4
and

By

using

these

Td2F/dT2.
of
eq.

equations The discontinuity

we

can

calculate
in

S=

the

specific

dF/dT heat originates

C=TdS/dT=
in

the

second

term

Fb).

We

thus AC
=

obtain

CTc-0
the

CTc
behavior

6TJA2P(TC).
of the

G)
specific
i
i

The

figure

shows

qualitatively
i
i
i

heat.

0.15

LO
r

0.10
-

j
i
i

>

100

200
*-

300

400

500

49.

Let is
constant
a

us

suppose

there

is

water
a

drop
and
in

of

radius
an

r,

at

the

center
e.

of If distance
the

which
dielectric
p

there from of

particle
of
center.

(ion)
water

of
is
was

radius
e,
an

having
field

electric
exists of

charge
at
a

electric

E=e/sp2
29

the
water

As

shown

problem
per

Chapter
volume

3, the
because
over

free of
the of

energy

decreases
in

by
this electric

(s
field.
obtain

l)E2/Sn
Integrating
the

unit this
AF

polarivolume the

zation of
the

decrease
of the
free

the
energy

whole

water

drop,
AF

we

change

drop:

-\

v-

'V

ez ( 1

)/
of

2re

constant.

Regarding
the of
water water

region
as

sufficiently
under

drop
vapor

the its

system

volume large consideration,


we

of and
at

water

vapor

including
part
condition

the

remaining

as

environment,

arrive

the

equilibrium

Ch.

4]

solutions

291

C.28):
SU
Here
we

-TSS

S(V
the

V")
phase
into

-iiS(N'
by
account
a

AT)
the

>

0.

have the
at

for arrive

SU

distinguished expression
ySa

liquid
takes

single

prime.
surface

Substituting
energy,
we

D.8),

which

(p -p')dV'

{ft' (T,

p')

ft" (T,

p)}

SN'

i~

(l

>

0.

By
and

neglecting

the

dr=(l/4nr2)
-p'+P
+

density dV', e2
8nsr

dependence
the

of

e,

and

by
above

the
can

use

of

d<7=B/r)dK'
rewrit en
as

relation

obtained

be

2y

-A 1~)}SV' \
e2
2
r

1Y)
e/

{n'{Tt

p')

n"(T,

p)\

SN'>0.

At

equilibrium,
p'
=

2y
r

(
\

Snsr

1\
-

sj

(J.

J.

Thomson's

equation)

B)

and

hold.
Note
vapor,

From

these that
while for for
vapor
a

two

equations
boundary,
present
case

the

critical

radius

is

determined.
for
not

planar
the

n' (ps)=n"(ps) y." (p) y! (p')<


but

holds
can

the

saturated

hold
the

only
r

for
vapor

the

supersaturated

(//
That
water

(li'(p)>ii"(p)),
small

(p)<ii"(p))
p'<p
is
to
can

also
eq.

for

unsaturated
as

because

holds
say,

by
the
grow.
vapor

B)
liquid
effect

as

long
is

is

sufficiently
stable

(dfi/dp

v>0).
the

phase
of into
see

more

and 4.2,1)), an important the atmosphere. 35. problem

drop
the the Wilson

This condenses

electric
clouds
to note

charges
and the

role,
About

when

water

(see plays fog in


of

chamber,

the

solution

292

PHASE

EQUILIBRIUM

AND

CHEMICAL

EQUILIBRIUM

[Ch. in
a

50.

The

general
solution

conditions
of

for

phase
we

separation
treat
-

are

given
as

example
to

2.

After
39:

the

example
=

7,
+

the

problem
+

sequel

problem

AG/RT

=/@)
=

x^
1

x2G2
-

(x.G0,

x2G2)
0)
+

r-(r_1H
have The

[rA
0
two
sum

<t>)logA

^ log0

rw

0A

0)J,
x

A)

where
The
two

we

writ en
into of

in

place
occurs,

of

<fJ.
if
terms at

We

shall

write of
square

for

#2
versus

hereafter.
has
of

separation
minima.
a curve

phases
the and

the
in

graph
the

AG/RT
brackets
and

first

two

eq.
convex

A)

gives
downwards
Thus
is

having
for

vertical

tangents
the third
a
us

0~O
term

and
is the
convex

0~1
minima

being
if if
appear,

0<<Jxl,
and

upwards
First,
we

w>0.

two

minima

maximum

between this

wjRT

sufficiently

large.
d0 JLdx d

Let
rx

examine

condition.
d
or

have

dxl+(r-l)x

=-,

02
rx2
with

AG
=

/'@V02y
rx2

dx

RT

B)
W

r(l

<t>) log(l (r

0)

0 log0

rw

0A (r

0),

C)

we

have

/'W)
rF,

'(/{'
S"

1)
,

(r

l)g@)/{r

lH}2,

D)

2(r-l)g-

2(r-lJg
E)

r-(r-lH
The

conditions
=

that

make
are

the

three
to

roots

of/'@)
equivalent
to

O coincide

are/"@)
and

O 0

and/'"@)
(because
we

O, which
obtain
eq.
can

found
=

be

g"@)=O
0,
and

g" by

(<f>)

g"

from

eq.

E)
equal

since
to

/'
zero).

g'"

0 eq.

/'"
conditions

@)

from

E)
be

and writ en

setting
as

it

According

to

deriving C), these

1-0

RT

F)

Let

us

denote

the

root

of

these

equations

as

0C.

Since

O<0<1

and

Ch.

4]

solutions

293

0<l hence

(j)<\,

we

obtain

^c=l/(l+x/r).

(j)c=^/r(j)c
this
w

from
into 1

the first
2

second

equation,
we

and

Inserting

the

equation,

have

_LY
into
two

As

described determined

above,

the
The

separation
concentrations

phases
in

occurs,

when

>

and
and

T<Tc(w/RT>wlRTc).
(/)"
are

the

separated

phases

$'

INDEX

absolute

temperature
zero

10,11,

65,
182

88,

93,121

Carnot's

principle
temperature
constant

64

absolute

140,

159,

centigrade
chemical

scale

11

activity activity additivity


adiabatic adiabatic
adiabatic

202

173, 9, 205,
of

197,

210,
283
-

263

coefficient
of bulk

202,
entropy
modulus 74

226 31

chemical

chemical
chemical

equilibrium potential
reaction
-

205, 138; 283;


-

gas
-

197,
advancement

198

adiabatic
-

compressibility demagnetization expansion


temperature
irreversible Joule-Thomson decrease

23,
91, 100,
process

88, 113, 249;


5

103,
164

161

260;
-

degree

advancement

283;
free
energy

enthalpy
235;
-

205,
standard

235;
free

161,
109

209, 261;
-

enthalpy
energy energy

206,

205, 235,
209;

standard internal

206,
261

adiabatic

standard

adiabatic adiabatic

effect

161

Clausius-Clapeyron
35, 89, 256,
Clausius' Clausius'
Clausius'

relation

191,

245,

246,

104,
adiabatic adiabatics

magnetic 164,182
process

susceptibility
4, 249
97

268,

271

85,
temperature Aui-z

adiabatic

coefficient
282
-

160

Clausius'
closed

equality equation inequality principle


-

63

32,
69

54

63,
1

78,
coefficient

85,

115 109

Ag*
air
-

20,
-

33,

242, 47;
heat 216

enthalpy
coefficient

149;

CO2,

system Joule-Thomson
of of

Joule-Thomson

94;

coefficient coexistence
coil
12

thermal
the
two

specific

152,

153

expansion phase

269

190,

212

a-phase amphoteric
argon

electrolyte
16

280
205

colloidal

solution
202

280

concentration

Arrhenius'

theory
of
some

condensation
stars

of

water

vapor

and

an

atmosphere atmospheric
average

226

electric
condensed

pressure

41

diameter
239 216

of

the

ions

204

contact

charge phase potential


chemical
state

290

214 227
constant

azeotropy

conventional

263
33

corresponding

25,

26,
238

jf -phase
barometer

critical 42 256
219 218, 13, 264

field,
radius
state

boiling boiling
Boltzmann's

equation point 233, elevation point


constant
curve

critical critical

of

magnetic liquid
45

drop 26,
210,

271,
236

290

25,
233

critical
Cu-Ni
Curie's

temperature

alloy
constant

Boyle's
calorie

25,
also

26,

27,

28

16

Curie's
8 {see

law

16,
law

84,
93,

Carath6odory's
Carnot's

cycle

thermodynamic 62, 92, principle 44, 62, 65, 113

calorie)
115

Curie

temperature
4

91, 243, 177,

164,
289

182

Curie-Weiss

182,

243

cycle
295

296

INDEX

Daniel

cell

207,
dissociation
freedom field
on

Debye-Huckel's of degree of degree demagnetizing dependence


dielectrics Diesel's
Dietrici's
125

208, limit ing


195

226 law

204,
234

241

226,
18,
process 59

Faraday's ferromagnetic 243,


first fixed law

constant

208

substance
289

288;

specific

heat

of

thermodynamics
of

5, 56
68

point
energy
-

temperature
-

the

free
and

147;
a

dielectrics
substance

165,

184,
87

185

paramagnetic
weight
147
183

185, 164;

187;
-

sping

cycle
equation

of
240

state

33,

45,94,124,

free

free

enthalpy expansion

32,

43,

87

dif usion
dilute

92,
solution
of

200,
actual

257

direction

change
235,
262 235

75

dissociation
dissociation distil ation Donnan's
239

203,
pressure

freezing freezing freezing fugacity


gas
constant

point point point 198,

257

depression
elevation
257

218,

219,

257

202,
13 231

206,

231

membrane relation

equilibrium
253

240,

280

gas

mixture

Duhem-Margules
efficiency
electrical electric electric electrochemical

gas
gas

phase
thermometer
pressure

209

11,
94

65,

126;-constant

64, 85 neutrality, displacement polarization


cell

condition
185

of-203

gaseous

line

187

Gay-Lussac's gebundene
235 209

274 239, experiment 147 Energie

91

207,
207

Gibbs-Duhem

relation

137,
252

162,

180,

200,

electrochemical
electrode electromotive
reaction force

potential
208,
scale
284

212,
Gibbs'
242
11 174

224,
free

231,
energy

240,

84,136,137,160,173, equation
94

226,

empirical
endothermic
energy

temperature reaction

Gibbs-Helmholtz
Gibbs'

phase
relation
242

rule

195

enthalpy
eutectic

3, 5, 147 8, 28,

Gibbs-Poynting
160
258

relation
71

192

entropy
entropy-temperature entropy entropy
environment

point 70,
of of of of

56,147, 233, 216, 71, 74, 136, diagram


258

Gibbs'
160

147,

gold grand H2,


-

potential
enthalpy
3,
5

136

111

melting mixing
1

72;

entropy

72
at

82,

195,
56

198

heat heat chemical

capacity
electric electric

equation equation equilibrium equilibrium


existence

continuity
state
constant

12,

57,

88; 210,
246

ideal

gas

13

206,
curve

234, 37,

261
57

11,19,137,271; potential displacement field 185;


-

constant constant

163;
-

at

constant

185;-at
for
constant
constant

magnetic

pressure

field

35,164;
-

at

magnetization
11,
at constant

theorem reaction

of

temperature
284
93

exothermic

expansion
extensive

coefficient

164; 106, 35,


-

at

constant

pressure

35,

65,
volume

150, 106,

151, 137,
62
147

154;

150,
156

154;

-negative

269;

quantity
variable variable
3

extensive
external

230

heat

non-negativity engine
function

heat

(see

also

enthalpy)

INDEX

297

heat heat heat


heat

of
radiation reservoir

fusion

209,

257

isothermal
80 161

compressibility
magnetic 164 163,
process,
-

23,

88,

93,
35,89,
4

103,

52,

53,

(heat
transition
191

bath)
209,

3,

62,
215

69,

76

isothermal

susceptibility quasi-static

of
of

93, 76,
-

104,

heat

vaporization
free
energy

Helmholtz

214, 136,
the 175
-

isothermal

147,
surface

159,
214;
Jacobian
Joule-Thomson
Joule-Thomson

160,
extensive

164,
law

167,
property

177;

of 255

139 coefficient

of

91, 94,
126

94,

126

Henry's high-polymer
292

200,
solution

231,

effect
porous

240,243, 228, 238,


271

277,

278,

Joule-Thomson
91

plug 161,
188;
-

experiment
170

28,

H2O

37,

90,
chloride

114,

Joule-Thomson

process

hydrogen
ice ideal ideal

181,
233

241

Joule's
Joule's

cycle
effect
heat
59

85

166,

of

CO2

109

point
dilute
gas,

66,
-

Joule's

solution

201,

203,
-

233

chemical

potential
34;
entropy
-

198;

enthalpy
-

of state equation energy 106,156,160; internal free 106,157; energy 161 heat 42, 157; specific ideal mixture gas 14, 45, 162, ideal substance paramagnetic

156,160;

157,165, 87, 13;


Helmholtz

kalorische

Zustandsgleichung
temperature

147

101,
-

Kelvin

11,
94

65

Gibbs'

Kelvin's
Kramers

equation
function formula

free

136
229

energy

34, Laplace's
198

173,
15

latent
latent law of of

heat

of

heat
conservation
mass

of

expansion vaporization
of
action

93,
247
energy

121 6

ideal
ideal

solid
solution
139

solution

201

201,
variables
process

231,

independent 133,
infinitesimal

256, (quantities)
4

257

law

206

3,16,

Le Le

Chatelier-Brown's

principle
242

145,

161,

172,
Chatelier's
denominator factor
117
3

180,

principle
transformation
170

145

integrating integrating
intensive internal internal
energy

71

quantity
5,
10 37

136,

147

force

Legendre liquefaction liquid liquidous liquid


local

137

199 line

239,

258,
214

274

internal internal

friction
variable

phase equilibrium

210,

2, 74
state

3,

195

inversion
Joule-Thomson

temperature(point)
effect
204
energy

of

the

94,

124

ionic ionization iron

strength
ammonium

226 alum
112 62

irreversible
irreversible irreversible
isolated

cycle engine
process

61,
62 62
1

system
210 bulk

isotherm isothermal

macroscopic magnetic magnetic magnetic magnetic magnetic magnetic magnetic magnetization magnetostriction
many-component

1
59

body dipole
field
induction
moment

46

15,

34,
18,
34

35,
58 113
15

47,

164

refrigirator
substance

15,
93

34,
solution

46,

59

modulus

30

200

298

INDEX

many-component
mass

system
action function
work

193

7, 9,
77

140,
136

193,

209

paramagnetic 163,
-

substance, 182;
molar
-

entropy

122, 165;
*

free
energy energy

energy

163,
163
138 138

Masieu maximum

internal molar molar molar


molar

122,

Maxwell's Maxwell's

equation
relation

37,

57

89,
181, 28,
33

155,
Maxwell's
284

169,

179,
rule

106, 188, 212,

107, 269, 228,

109,
286

139, 244,

242,

Mayer's Mayer's
mechanical mechanical mechanical mechanical
Meissner

cycle
relation action

21,
140

49,

120 140

partial partial partial partial partial partial partial particle


perpentum

enthalpy
entropy
free
energy

138
138 138

quantity
volume

molar
pressure
source

138

14,

198
3

(reservoir)
mobile
mobile of of the the

first second condition

kind kind

6 63

equilibrium equivalent
interaction effect
238 257 209

perpentum
heat
7

of
2

melting melting
mercury

216,

point
235

/>H280 phase phase phase phase


-

190, 195;-internal 224, diagram 217, 190 equilibrium transition 190;

195

233,
first
-

239,
order order

251,
191;
191

257

higher
constant

order function

192;
264
136

second

metastable
minimum mol fraction
202

equilibrium
work

77,
198,
202

84,

142, 94,

247
114

Plank's
Plank's

plate
Poisson's
11

condensor

165

molality
molar molar

equation
chloride
218
9

22

heat

capacity
heat
9
197
at

specific
number stable
'

constant

volume

11

potassium precipitation
pressure pressure

242,

282

mole molecule
most

equilibrium

state

142

163;

coefficient, of magnetization
of of
4 280 4

at

constant

volume 76

93

N233
natural

principle principle
133,
heat 136
process

increase maximum

of

entropy
work

77,

113

variables

negative
nickel non-holonomic non-volatile
normal
288

specific

269,
92 256

271

protein

system
solute
state

quasi-static
radiation
radius of Raoult's

process

20

field,
water

entropy
and

88,
vapor

102
pressure

drop
200,
209

269

occlusion
Ohm's
open

234

law
heat isochore isotherm

231,
234 261

253,

256

law

59
1

reaction reaction
224

system
coefficient
pressure

osmotic osmotic
Otto's

reaction

218,
85

219,

280

cycle
207

oxidation
oxygen

reciprocity regular 220,


reversible reversible

theorem solution
221

139

201;
cell
208
62

of

2 components

31,

33,
salt

38 113

paramagnetic

reversible

cycle engine

62

INDEX

299

reversible
rubber rubber

process

61

starch
188 189
state state
state

280

band

.162,
189

165,

elasticity elasticity equation

(see quantity
2

also
3

thermodynamic
equilibrium
3

state)
196

rubber-like

of variable

thermal

Rutgers'
Sackur-Tetrode

239

state

Stefan-Boltzmann
formula
vapor

law
state

36

264

saturated

199,
271; 269;
heat
of
constant
-

200;
pressure pressure

adiabatic

expansion 229, 212, specific


199

200,
curve
-

201,
238,
pressure

203, 269;

superconducting supercooled superheated supersaturated


surface
surface

238,
90,
37
107

272

liquid
steam vapor

238,
-

271
248 229

238,

269;

vapor

213,
tension

229;

entropy

192,
1

213,

second

law

thermodynamics
coefficient
239 110

74

surroundings
system
1

second

virial

segregation semi-permeable semi-permeable


silver silver sodium solid solid
242

membrane
wall 83 282

241

temperature temperature
170

10

drop
scale

by
11,
-

adiabatic

expansion
68

chloride

242,
134,
135

temperature
tension
thermal

65,

163,
process

165

phase
solution

216
199

action, 7;
coefficient

the of

dependence
condition the
30 37
pressure

on

the
140

equilibrium

solidification
solute

216

thermal

at

200,

203,

231, 201,
200

253

constant

volume

solution

199,
components
of of -chemical with its
vapor

203,

229^253;
203,
200;

two

thermal
thermal

conductivity
data dissociation electron
209

solution solution

strong
two

electrolyte
components

224

thermal
thermal

226

236,
-

264

potential 229;-ideal,
253

231;-equilibrium
dilute
231

solvent solid sound

200,

phase velocity
of
42

218, 252,
31,

257 39

space-rate

atmospheric
11, 11, 94,
13 35

temperature

32,

specific
pressure

heat
11

19,

137; 137,

at

constant

equilibrium reaction 260; field 288; 190; phase thermal equilibrium, mass 142; thermal equilibrium thermal expansion,
-

thermal

2, 76;
at

chemical

constant

mass
-

action

193,
142

magnetic 209;
for

stability
condition
140
state

140,141,

action

coefficient
pressure

163,
30

166;

209;-at

constant

at

constant

volume

thermal

radiation uniform

36

(see
117

also

radiation
also
non-

specific speed
spontaneous

volume
of sound

magnetization
158,
183
142

288

spring
stable stable

equilibrium phase
142

190 of solution formation 205

stability
standard of ions

free
in the

energy

of

1 mole

field) thermally holonomic) thermodynamic thermodynamic thermodynamic thermodynamic thermodynamic thermodynamic

(see
175 8

stability
calorie
contact

functions

2, 4 136,
133 2

137,

147

potential
state

300

INDEX

thermodynamic thermodynamical
thermische

variable

3 136
-

effect

124;
specific
't

Maxwell's
at

rule
constant

242,
volume

288;
92

potential

heat

third

law

Zustandsgleichung of the thermodynamics


175,
182,
209

147

van

Hoff's
pressure

law
constant

225,
15 15

278

140,

159,

vapor

209

163,
Thomson's Thomson's
total

virial
291 virial

coefficient

equation principle
pressure

expansion
9

63,
of

78,

85,

92,115,116
variables

volume volume

197

expansion
pressure

coefficient

at

constant

transformation
139

independent
thermal

156,

161

transitive

law

of

equilibrium
228,
212

Wagner-Engelhardt
Warmeinhalt
water

cell
147

242

triple
two-component
two

point

196,
-

216,
system

247 212

drop
chamber

243;
7,

phase,

separation
142,

Wilson work

2,
of
source

unstable
van

equilibrium
der

222
of
state

work
work

9, 20, magnetization
3

{see also having 238, 243, 38, 114


59

enthalpy)
an

ion
272

290

Waals'
Waals

equation
gas,
-

15,
state

25,

29, 26; 236;

working
zeroth
zero
zone

substance

62

119,284
van
-

der

critical free

25,
energy

law

of
239

thermodynamics
276

2,

37,

57

entropy

119;
energy

Gibbs

-internal

.119;-Joule-Thomson

melting refining