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
NORTHHOLLAND JOHN
WILEY
PUBLISHING &
COMPANY
AMSTERDAM
SONS,
Publishers
INC.
NEW
YORK
(Interscience
Division)
NORTHHOLLAND
PUBLISHING
COMPANY
AMSTERDAM
1968
No
part
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THIS
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THE
NETHERLANDS
PREFACE
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ENGLISH
EDITION
original
and of
text
of
this
volume
in
is that
of
the
first
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Statistical Shokabo
book Advanced
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Solutions
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Mechanics"
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PREFACE
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PREFACE
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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
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any years
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The
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to
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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
of
of
Thermodynamics
Thermal
Contact
Equilibrium
(The
Zeroth
Law
of
2
2 3
4
Quantities
of
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
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
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
Thermodynamic Legendre
GibbsDuhem
Functions Transformation
Relation
of
133 136
137
Definitions
Relations The Third
Law
Thermodynamic
of
Quantities
and
Thermodynamic
137
Thermodynamics
Two
(NernstPlanck
Systems
a
Theorem).
..
between Condition
of
for
Given
Environment
Thermodynamics
143
ChatelierBrown'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
ManyComponent
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
SolidSolution)
of
and
Regular
Solution.
201
Expressions
Solution of
Solutions
202
202 203
Activity Strong
Coefficient
Electrolytes
XII
CONTENTS
Chemical
Equilibrium
of
of
205
Thermodynamics
Electrochemical
Third
Law
Cells of
206
..
Application
the
Thermodynamics
DIVERTISSEMENTS
Chapter
1.
2. 3.
Founders
of do
we
the have
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
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
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
motion,
state
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
two
systems
A + B and
B
are
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
law
above in
sense
of
thermalequilibrium):
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
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
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
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
semipermeable
enough
result which
it is
in
not
to
membrane
example.
are
Idealizations
alter
contacts
the
properties
during
If the
of
process
the
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
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
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
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
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
the
of of dis
an
as
external
if tinction the
variables.
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
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
Quasistatic
assumed that
Such
process:
ideal
its
process
during
maintain
may
both
a
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
process
reversible
(cf.
process:
2.1).
In
Thus
processes:
isothermal
of
at
this
process
system
contact
environment
constant
temperature temperature.
process:
(heat
is
mass
a
bath)
process
i)
the
quasistatically Quasistatic
system
but
this
adiabatic
no
This the
no (and surroundings.
has
work is
thermal done
contact
quasistatic contact)
process
which
with
its
surround
ings
by
or
on
Ch.
1,6]
FIRST
LAW
OF
THERMODYNAMICS
Fig.
1.1.
The
process
quasistatic
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
+
U2Ut=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
E2Et=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
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
including Eq.
as
every
subsystem
or
participawrit en
for
to
A.2)
the
eq.
result
of action
through
the these
mass
mechanisms
respectively
heat
mass
contacts.
reader
concepts
familiar transferred
mass
of
with
to
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
stating
If
a
the
first
law
kind:
+
system
=
undergoes
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
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
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
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
A8141878)
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
A8211894)
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
A8181889)
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
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
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
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
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
H2HX
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)
ith
the the
pressure
on
of
the of
per
surroundings,
the force
the
Xfe)
force
number*
system
the
molecule
surroundings,
coordinate of
and
of
or
corresponding
potential
In
a
Z/e),
or
JV,in
the
the
number
molecules
yth
component
mole
of
system,
/^e)
in
the the
in
chemical
the
jth
the
component system
is
surroundings. equilibrium
with
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
which
is either
the
chemical
potential
mole
otherwise
10
THERMODYNAMIC
STATE
[Ch.
1, 9
In
the
case
of
quasistatic
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
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
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)
quasistatic
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
jth
the
component
the
no
chemical
state
more
^e)
jfth
In
a
component,
wil
with
with
Chapter
1.9.
quasistatic
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
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
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
A9)
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
quasistatically
x
into
system
by
by
process
dT,
the
maintaining Cx,
quantity
constant,
raises
the
temperature
by
C*
=
~,
A.10)
process.
is the
mass
capacity
material heat
or
of molecular
on
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
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
the
have of
air
of
the
sun. a
brought
reason
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 bodyweight.
of addition
a
of
absorption
conditions
for
the
nourishment,
of
is reradiated, maintains
just
a con
require
this
determinate
is
degree
not
temperature,
of
energy
maintenance
there
F.
meant
seem
needed
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
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, LeipzigBerlin, 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
electric
in
variables; magnetic
state
for
instance,
the fluid
0
field,
of
field
may
quantities, depend).
shows
H, fact,
are
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
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
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
=
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
Mixture
nt
of ideal
of the zth
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
ith
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
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
(KamerlinghOnstate):
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
co2
42.69
44.18 30.52 56.26 56.39
v2
A.18)
or
3.788
5.468
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)
Nonmetal 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
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/jKsurfaceof
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
have
y,
functional
x
as a
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,
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
current
passed
of
through
Hj
is and
a
coil.
The Therefore
field
field
we
the
sum
demagnetizing
needle.
entire
if
specimen
is
is wound
long
the
is a,
here
cylinder,
coil
is
<&
=
whose
onlB=
the
V=al in
over
is
/ and
area
the
flux
where
the
volume
of
the When
magnetic
the
so
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$/dt=
The force
J dt
V(n/c)
the time
dB/dt
electric
induced,
source as
a
according
must
Faraday's
this
induction counterelectromotive
work
in
=
which
a
do
against
interval
charge
\cHj
dt/nn
Ch.
1]
EXAMPLES
19
passes
through
each
section
Jdt
=
of
the
wire,
is
=
(lie)
Of
be this
(d$/dt)
iVH
is
dB/n
work
dH
4nH
dM)/n
to create
a
work,
of with
d\_^VH2li \
the
dM.
presence the work A
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
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
+
quasistatic
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
of
air
at
NTP
(normal
the
to
temperature
and heat
at constant
pressure,
that pressure,
is,
=
C,
cp
0.238
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
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
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
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
quasistatic 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
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
(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?
y1
=
(V!~7
1
Vry)
=
y1
^(PiV,

^(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
(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
quasistatic
consider
compressibility, compression
the
we
or
of
course
mean
the iso
quasistatic
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.
pv
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
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
C(po)/3p)t=0
the
van
(the
der
at
lat er
po is the
Cp/do)t=0
pV
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
Vbn
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
t=const,
of
When
curves
po
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') righthand
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 po
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
CDIJ'
3ColJ/o2.
eliminating
t,
we
Substituting
eq.
E)
and
have
P This
curve
=
3Cd2)/d2.
points
at
(8)
passes
=
through
It
has
a
the maximum
at
(o=y,
p p
1.8
=
27),
anc* the
when
(o=f,
p9/o
relief
as
p
ooo.
0),
van
and
The der
(o
point
Waals
Note:
l, p
of
3).
inflection
lies
(o
curve
2, p
has
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
JouleThomson
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
is
energy)
a
shown show
the
in
Fig.
the of
volume
Vt
volume
and that
V2,
that
enthalpy,
temperature
Tx
Solution
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
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
quasistatically
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 quasistatically 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
quasistatic
done
adiabatic
Show process is
heat the
gas
equivalent
in
by
the
maintaining
7.
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
(pu
processes in
to
Vx,
as
Tj)
seen
to
final
the
energy
state
quasistatic
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
it
an
quasistatic
with
expansion
height.
What
is
in
of
temperature
1 km?
Consider
shown in
contact
in
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
quasistatically
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
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
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
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
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
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(yl)
energy
y1
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
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. StefanBoltzmann
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 lowtem
engine,
heat
perature
more
and
to
more
transportation.
about
son
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
A7961832)
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
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
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
=
papdTk{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
=
0.260
joule/g
dif erence
specific
=
heats 0.2203 is

get
0.1578
=
Rjm
Therefore
the work
cpcv
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
quasistatic
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
U2U1
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 quasistatic
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 QlA
On the
=
j
Cp
=
=
Cy
hand, Cv+nR
dT
Cy(TA
since
7\),
determined
QA2
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
Qia
CpT2
process
Qa2 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(T2T^).
equilibrium
fact of
on
First
we
examine
with and
the
the
thermal
the
the
involves
height,
with
are
This of
crosssection
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
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
quasistatic
example
42
THERMODYNAMIC
STATE
[Ch.
Elimination
or
of
V\
gives
=
(yl)dplyp
I p(z+dz)S
z
dz
p{z)Sdzg
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.
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=(CxCp)l(CxCv),
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
quasistatic
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
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
quasistatic 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(T3T2)
constant
(this
pressure. involved:
In
is
negative),
quasistatic
=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
Si2 Substituting
the
Q2^3
results,

Sai
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(Vnb)
and,
A)
from(d2p/dV2)T
both for sides
Q,
V3l(VnbJ
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(Vcnb)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
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
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
xaxis
field
is
zero
that
The
magnetic
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
xaxis
to
x,
where
acquires
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
permanent
suppose
subtract
means,
consider
could and
by
magnet
some
fix
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
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,
nonuniform
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
crosssectional
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
of
the solution
on
of
p
height problem
we
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.
quasistatic
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
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
lefthand
and
state
the
the
righthand
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
dUd'A
be
dUHdI.
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
quasistatic
dM
the
first
law
fol ows:
d'Q
(from d'Q
eq.
=
dU
A.5)
dV,
and
we
example
see
dU+p
the
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
=
quasistatic
is
d'QpdV.
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
quasistatic 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
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
??2o
0 and the
3>4
temperature
and
In
the Since
process
4>l,
??4i
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
V3>V2,
reservoir
(V2IV3)i<T1,
T3).
=
to
The
total
is
energy
from
work
Qi^2
2i2
tl).
Q^JT3
which 21.
??34 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
Q1t2/Tl
do
not
(See
flow.
9.)
the
The
change
p,
time
in
p,
velocity,
point equilibrium.
to
the due
density,
to
and
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
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
crosssection
per
mass
of
unit
on
tube the
amount
of
i.e. have
Su
of
fluid
the another
direction
crosssection
time the
stream
same
is
equal
tube,
d/. Since
tube;
we
p^S^
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
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
dld(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(ipH33/133K.
then
T
When
jc
=
the
pressure
we
p=
1 atm,
573
50248
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
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.
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
righthand
=
f(Ecurlf f curlE)dF
Therefore,
for
the
fdiv[f
lefthand
side,
we
EjdV+
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
(EjdV=
Here
done
F per
(pfdVforce
in
to
(FjdV.
the
is
the unit
electromotive
time
is
battery
the dV
is
current.
and that
J Fj
If the
dV the be
is
the
work of
the
entire
system
as
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
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
in work
magnetidone
get
increase
dM
from
M:
((HdM)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
generally
and
a
field,
H,
magnetization,
by
the
M,
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
quasistatic
this
sense.
explained
reversible
strict
sense.
1.5.
in
the processes
or
quasistatic
the
be
broader
is
or
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
quasistatic
Therefore
may
adopt
definition
be
at
phenomena;
Real
reversible
processes
may
considered
physical
Such
reverse an
proceed
the of
finite
speeds
particles
in
a
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
quasistatic
and irreversible
process,
reversible
An
step.
pass
Reversible
engine
do either
or
engine:
a
arrangement
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
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
of
which
any
the
second
does
work
kind:
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
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
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~!/
=
B2)
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
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
C\
is
reversible
to
Qx
=
from
the
Rx
irreversible. the
net
gives
It
\Q2\
takes
=
R2
heat
cycle. doing
It
the
takes
work
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
lr,(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
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
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
precise
1887
thermometric
to
investigations
gave
more
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.
Among
Keesom
et
them,
al. and
are
the
of
J.
to
Otto
et
Netherlands,
of
between
the
al.
U.S.A.
Kinoshita
Japan
273.149
for
273.174.
pure
as
their
water
high
is
precision. Considering
very
near
values
results
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
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
the
value
temperature temperature
273.15,
from
determined Celsius
in where
a
decision.
The 0.0001
thermodynamic
ice the for
temperature
new
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
li@i,02)=f@lt02)
where
B.7) B.8)
Once
to
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
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
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:
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)
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
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
wavelength 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
wil
be
found Edition
Meas
de
1948,
and
amendee
ures.
1960",
to
Conference
on
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
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
is
100
2.6.
CLAUSIUS'
a
INEQUALITY
AN
ARBITRARY
CYCLE
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
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
quasistatic
d'fi/r,
B.11)
where
a
the
to
a0,
is the
along
absorbed whole
dS
any
quasistatic 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=TdSpdV.
Entropy.
A
state
B.16)
and
quantity:
a0 have
Let
a.
L
we
1/
be
eq.
two
quasistatic 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
quasistatic 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
AUAZ,
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.
quasistatic
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
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
free
energy,
and vanishes
in
G,
case
the
Gibbs
free
energy
(see
JS^O
Chapter
Note:
The
3).
lefthand the
to
a a
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
7th
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^AVYsPLfANj)^0.
B.25)
extracted
the
where
W=
Wmzx
>0
Then
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
manmade
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
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
i ber
die
Grundlagen
the
as
355). simple
He
replaced
assertion
theorem
traditional
given
which
by
states
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
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
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
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
yo.
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.
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{T2Tx)=(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
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,
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
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.
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
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
dUTdS
for
pie) dVr
+^ldV.
B.22)rFor
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^
Helm^ltzip^Pelirgy*ln^eq.
the
external
pressure, pr,
free
energyXq.
B.23).
1.
Using
Clausius'
principle/provejpfausius'
inequality,
j w^original
from
state
B9)
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.
quasistatic
intersect,
Thomson's
principle
is
4.
If
Tmax
is reservoirs
t],
the
maximum
receives
to
temperature
heat and it
1
of
the
is
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
pV
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
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
temperature
by
to
of
absolute
(9=1/x,
M(H)
is
proportional
the
temperature.
14.
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
equations:
cpcv
=
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
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
liquid
solid
to
state.
absorbs
latent all
much
in
liquid.
calculate
Assuming
how
heat, specific
more
Q0,ata
heat
values
temperature,
to
be
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
quasistatic
quantities
derived
equation
Ch.
2]
PROBLEMS
[A]
a
91
24.
In
the
JouleThomson 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
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 (JouleThomson
JouleThomson
(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.
GayLussac
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,
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
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
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
by
for
this
exist
separated thermally
an
system
nonholonomic,
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
specific
volume
heat
Fis
constant
function the
dif erence
volume is
between
a
function heat
and
find
at
function
constant
only;
and
at
at
pressure
34.
Show function
that of
the
T
specific only
volume
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
=
quasistatic
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
JouleThomson
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
JouleThomson
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
at
temperature
by
of
also
measured:
and
Lp
in
method
to
involved
(latent connecting
the
the
9
temperature
the
absolute that
39.
Show
internal
substance
energy
and
the
the CurieWeiss
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,
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
GibbsHelmholtz
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
condition
(p=0)
actually
measured
pressure values
of
gas
of
specific
heat 43.
pi
equation,
of
on
a
Using
pressure il ustrate
nRT(Vnb)~1
point this using See problem
gas.
exp(na/RTV),
of the JouleThomson
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
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.
JouleThomson pressure.
Derive
coefthe
ficient
basic 45.
have
been
necessary
that
formula
JouleThomson 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
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):
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
Kl'Qnl+Qnl
Therefore,
system
under
A
=
Wnl*
law,
be
KOn
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)
adjusting
of
are
the
heat satisfied:
Q'nu
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:
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
rji(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
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
and
at
A=0.
the
adiabatic
an
lines
point,
with
a
C,
and because See
in
the
b at
pV
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
Q from
A
its
environment
only
system
and from
is
during
the
to
done
law
by Q
is
=
the
equal
also
the
positive.
a
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
thermal
the
value
engine
process of T(e)
we
(d'2i>0)
given
value
an(j
off).
of
If
r(e)
Tmax during
in
the is is the
(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
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=QtQ2,
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
1)
is
TV^1^const,
so
(Ba) TcV\~^
TdV\~1
TcTb V1
TdTa TcTb
TcTb
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{TCTbTd
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
ToTdTdTb+Ta
the
Tb
(ii )
CV {Tc Cv {Tc
during
(Tb
p2
(Vc (To
Vb)

(yl)
is
Tb)}
Therefore
CK{7(Tcrb)(TdTa)}.
process
The
heat
absorbed
b>c
Q
.
CP(TCTb).
yTcTb
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
quasistatic
use
process).
proof
of ideal
the
in
abso
defined,
the mole
of
eq.
gas
B.8)
the
2.5.
in
When
entropy,
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
the
we
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
quasistatic
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
quasistatic
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
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\(T2
quasistatic
Tt)
(VAVB)
and
is
equal
to
13.
The
first
law,
body
is
(see
d'Q example
dUd'A,
1 in
for
process
of
paramagnetic A)
Chapter
1)
=
d'Q
(we
X
or
dUHdM,
U is
a
consider
unit
M.
volume)
From
where
function
we
of have
temperature
only
only.
Divide
and
Here
independent
0 is also
of
the
of
relation
M
=
M=%H
and
a
H=M/x=M6.
independent
we
function
_
of dM
9
=
temperature
ds
is
_
A)
where
nator
to
by
0 and
S is for
have
^
dif erential.
this
the
d[/ fl
Hence
B)
integrating
be denomiit must
complete
Since
1/x
the
d'Q.
absolute
is ratio
function
In
of
temperature,
we
the
temperature.
fact,
of
if
heat
perform
absorbed,
is
Carnot
this
from
paramagnetic
voir the
to
the
the
cool
Qlt
from
as can
Q2,
to
the
reservoir
9l/92
be
equation
(See
example
If
we
7 in
Chapter
be
1 for
an
alternative
solution.)
1
ks
=
(i)
let
the
adiabatic
entropy
S, then
compressibility
compressibility
(dV\
isothermal
kt
V\dpJT
1(dV\ {
104
SECOND
LAW
OF
THERMODYNAMICS
[Ch.
Using
A.23)
we
can
write
ks
as
If
we
Sis have
considered
to
be
function
of
and
V,
i.e.,
S(T,V)
S(T(p,
V),
V),
^
T\Sp)y
Similarly, by considering
S(T,p)
S(T{p,
/ar\
V),p),
we
have
w)rw)\)[
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
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=TdSpdV
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,
Uo (Cv is the molar + S0 logp Cp \ogTR the HelmTherefore, and log/? +U0TS0
+
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
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)
quasistatic
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;
=Jiv
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.
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
wowloo
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
quasistatic
substance
at
from
solid
state
temperature
supercooled
temperature
Tt:
solid
at
108
SECOND
LAW
OF
THERMODYNAMICS
[Ch.2
The
Tj^
1 is
solid
at
T0h
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
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.
JouleThomson
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
JouleThomson
p,
coefficient
called coefficient
changes
version
sign
point
2.11
T.
Tx is
JouleThomson
the
pressure,
of
coefficient.
Figure
p
shows
dependence
of
the
JouleThomson
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,
quasistatic
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
~{dUHdM}
4aTzdTCd
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
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
However,
B)
near
one
inconsistent
0
can
the it
cannot
third
K,
never
used attained
T2.
or
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
do
work
we
consider from
x
a a a
Carnot
reservoir
at
cycle
at
which
d'g
while
Cd7'
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{{TXT0)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
UCdT)
,
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
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
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=U2UtA.
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=U1U2A'.
From
B)
A)
and
B)
Q
=
(A
the
amount
A').
system
of
absorbs
C)
heat,
Therefore environment
in
of
the
cycle
does
violation Alternative
means
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
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,
(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
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
=
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
making
to
or
combine
two
and
to
work)
it contradiction
was
the
two
was
gases
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
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
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
vb
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 Vb
dV,
E)
which
is
integrated
T
to
give
+
CC
=
dT
log
(V
b)
So
(So
is
constant).
F)
120
SECOND
LAW
OF
THERMODYNAMICS
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
quasistatic
change,
E)
solution
4
gives
R
A
Cy
T
dT
Cvdv dl

(using
Mayer's
relation),
which
+
is
writ en
y
as
1N
Vb

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
JouleThomson
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
VT(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')
(BATA'
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
T9J
have
A)
into
eq.
C)
of
the
solution
27.
Then
(dU/dM)T9M/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
dT, dT (8_E\ +
T
\dM
dT
(dU\ [
CMdT
we
obtain
U
CM
om2
const.,
and
integrating
dS
dUHdM
=
=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=
TdSpdV
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
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
JouleThomson
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/(8t).
Eliminate
t)
in
A)
with
this
to
get
D) Fig.
ature
2.14
curve,
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
JouleThomson
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/C2Tit).
24^31:12t27.
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
pt
t=3.
JouleThomson
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
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
JouleThomson
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
lefthand
D),
take
only
in
x,
and
9.
E)
data
The
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
last Onnes.
t)f
the The
"permanent
reason
gases",
why
of
it
is
Jouleto
so
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
JouleThomson effect
In
and
original hydrogen
present,
method
and
JouleThomson
for helium. used
of
used
most
then
is
the
the
method,
first
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
ClaudeHeylandt
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
tropytemperature
heat
simplicity,
that
the
the
7i
sure
pipes (~
pz
300
system In the
15
perfect
a
and
>
drop
gas
of
to
pressure
along
temperature
(~
This
atm)
is
an
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
JouleThomson
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.
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
(j
I,
is
a).
to
The
2, which
through
is
exchanger
cooled
the
(d>e).
then
led
Fig.
2.16
TS
diagram
of
the
liquefier.
to
the
liquid
at
container
through
it
enters
the the
JouleThomson
must
valve.
be
The
tem
perature
which
so
valve
lower
can
than
lower
the
the
rest
inversion
temperature, ature,
that
the
JouleThomson
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
JouleThomson
back
to
valve,
be
and
joins
as
The
lows.
process
goes
(j
calculated
the
a).
fol
liquefying
the
whole
1 mol
of
helium
gas,
JouleThomson
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
HeHt
=
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
ChatelierBrown'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
is
characterized
by
are
which variables.
all
derived socalled
as
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
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
o1
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=
UTS
V, Ni
dF
SdTpdV+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=FG
/
=

SdTpdV'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
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
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
from such
and
so
internal variables
Legendre representing
strain of
transformations forth.
It
is
proper
name
each
such
thermodynamic
func
GIBBSDUHEM
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
GZNji jiZnjGj).
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)
"
Hj>
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
multicomponent
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
lefthand
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
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
them
derived variables.
systematically.
them It
are
of
that
natural
are
variables.
Thermodynamic
from is variables
One
not
always
in derive often
functions
to
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,. .) \
(?, 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
(NERNSTPLANCK
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
of
absolute
the for
zero),
some
and other
coefficient
zero
as
specific quantities
zero.
heat,
are
the
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 quantummechanical
of
mechanics,
of the
the
microscopic
of
matter.
BETWEEN
TWO
EQUILIBRIUM
two
SYSTEMS
When condition
systems
may
A
stated
and
as
are
in
fol ows, action (mechanical action (heat exchange): action (material exchange):
be consider
an
contact,
on
the
equilibrium
the
contact:
the pA=pB,
nature
of etc.*
i ^=$.
system,
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
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
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
abovementioned
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
C29)
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
lefthand 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
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
unstable
or
equilibrium C.30ae)
condition
which
It is necessary
thermodynamics.
firstorder
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
lefthand
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
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
twobytwo
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
must
positive.
from
constructed
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
previous
for
a
argument,
finds
positive
form
0,
every
principal principal
itself
must
positive.
Therefore,
positive.
Ch.
3, 9]
LE
CHATELIERBROWN'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
C39)
(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
CHATELIERBROWN'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
changes
disturbed direction
Yt
system
due
to
ChatelierBrown's
principle.
the
in
A
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
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
Aristotle
but
"internal
W.
A852)
J. E.
Clausius
like the
to
A876).
unit
6v6pyeia"
is
"en"
due
means
to
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
quasistatic
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
German
scientists
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
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
crosssectional
area,
a,
as
in
pressure,
Figure
3.5.
weight
to
is the
due
placed weight
acceleration
weightless
to
piston
the
M
p
=
so
that of
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
the
the
point,
energy
the
the
becomes
of
existence of
the 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
weight
on
side,
=
dM,
dU
in
+
is
put
the
piston,
order
work
like
dMg(z
to
dz)
first
=
dMgz
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
H2H1
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
+
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)pi+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)(p2p20)+^,
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,
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,
(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
STdSdpSV^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
SdTp 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 ) dpSTi
s__
fdv\^x_ \dTjp
(dV/dT)p,
dTdpi\
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
nonuniform
to
if
open
can
the
system
negative.
6.
is
gravitational
outside,
the
if
an
specific
heat
be
39
in
Chapter
of
a
4.)
uniform increases
In
the
quasistatic
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
(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
^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
namely
the
elongation
is
energy
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
quasistatic
as
by
expressed
d'A=Xe
process. dx=Jfdx.
work
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
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
only
If
as
the
elongation
hand,
9. Show
zero
as
takes
the
place place
third
isothermally, adiabatically,
law
of thermodynamics approaches
On
U.
the
other
from the
the
zero.
heat
capacity
tends
to
temperature
the
absolute
Solution
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
ro
TS
fd(TS)\

ro\
S
+
dT
)x\\dT)x
/( )
l/dT\
ro\
( [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
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
Helmholtz
F,
system
of heat
equal
reservoir
the
in
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
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
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
quasistatically
expanded
4.
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
JouleThomson
from
dp
(dp<0).
expansion
coefficient
at
volume
constant
that
and
the
from
temperature
that
a
always
this
decrease is
decreases
pressure for
positive quasistatic
temperature
is
for
gases.
adiabatic
decrease
expansion
which JouleThomson
11.
results
corresponding
greater decrease
than
of the
the
pressure
by
the
adiabatic
effect. that
the
is
ratio
of
to constant
the
the
adiabatic
ratio
pressure and of
equal
at
the
specific
Prove
heat
to at
the
constant
isothermal
volume
(ii)
of the
(ii ) principle.
12.
C.37b),
at constant
use
the
constant
relative
Le
magnitudes
temperature.
entropy
of
interpretation
using
ChatelierBrown'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
second
process,
C.1)
are
is then
the
obtained If definition
con
applied
to
infinitesimal
by
have of
eqs.
repeated
mastered
quasistatic 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
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
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
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
Gquarter
the
from
of
the fact
circle. of
dTand
you
In
the
dG,
The
Srarrow In been
term
write
coefficients
the
at
dp,
have
T.
term
expression respectively.
to trace
of
minus in the
sign
a
of
reverse
that
arrive
S, starting
the
massaction
from
diagram
because
to
to
common
mentioned
above,
the
Em&Ni
because
can
dropped,
is
diagram
eqs.
is
twodimensional,
If
term
and
you
all
some
of
C.1)C.4).
massaction 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
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
GibbsDuhem
relation
C.12)
from
the
Helmholtz
free
energy.
Ch.
3]
problems
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
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
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
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
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)~(sl)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
the
previous
F(T,
Also
M)
obtain
and
entropy
each
Ch.3] 30.
A
between
PROBLEMS
[C]
165
dielectric
the
of
with
plates
constant
temperaturedependent 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
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
quasistatically
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
onecomponent
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
crosssection)
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 quasistatic
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
dUTdS
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
7Q
<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(CTC)(p2p2)+~.,
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=
UTS,
U
=
S=(dFldT)v,
FT
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,
GT[
G=HTS,
S=(dG/dT)p,
and
,'dG
From
{dGldp)T=Vwe
This
obtain
(dHldp)T=
treated
more
VT(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)
TdSp
dV=0
when
dt/=O.
So
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
10.
gas
made
to
undergo
the
quasistatic
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 JouleThomson
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
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
quasistatic drop,
adiabatic
expansion.
Consider
of
Ap>0.
process
The
dif erence
temperature
a
sufficiently drop
small
(AT)s>0,
is
and
(AT)H>0,
JouleThomson
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),
JouleThomson
can
quasistatic
be
the
gas
cooled
process down
the
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=UyiYiykYk,
we
have
YtdytYkdyk+>,
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
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
ChatelierBrown'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
TT)
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
uCp=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^
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
FT[
\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
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
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
CurieWeiss
(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
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
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,
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
The which
first
is
pi.
term
the
righthand
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 ChatelierBrown'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
GibbsDuhem
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
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*
FHM
dF*
SdTMdi/.
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 )
'
ABT
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
CurieWeiss
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
r0,
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
spring
and
x
tension
is
Here,
W
the
strain
at
X=Mg
the
potential
(mass
of
weight
z0
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
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
dF*
gives
in the
+
the
sum
of
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
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
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
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
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=
L2(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
i0.020 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
thermal
the
effect
that
considered
for
effect.
in
small materials is
rubber
a
thermal
expansion.
when
up
(AT>0)
they
characteristic band.
rubberlike
elasticity.
the fact that figure, such t h i s , Ignoring are adiabatically. elongated One can easily verify
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
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
double
pressure
nature
we
primes),
on
are
in
both the
must
sides
have
of
interface.
A)
interface
By
p,
C.26ac)
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) Firstorder
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
=
(ClausiusClapeyron
equation),
D.4)
where
TAS=T(S'
mole
and
5")
A V is
The
is the
the
heat
transition.
of
transition
per
the
change
this
per
mole
in
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
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) Higherorder
1th the th
in
density. partial
order
of
is
/i
up
to
all
continuous
and
lowest
discontinuity
said
exists
two
appears
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"
(GibbsPoynting
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
quasistatic
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
MANYCOMPONENT
SYSTEM
193
The
surface
tension,
y,
is
defined
by
this
equation,
i.e.,
D8'
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
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
MANYCOMPONENT
SYSTEM
IN
PHASES
we
For
simplicity,
of
the
assume
that
mechanical
so
equilibrium
that the
is established pressure
at
the
The
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
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
+
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 A8221888) 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. 351400. 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 A8391903) 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
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
Gibbs'
of
the
Connecticut
Academy
Another
wrote

(Vol.
reason
Il ,
was
pp.
published 108248)
that the
paper
in
a
journal
was
with
very
to
limited
understand.
dif icult
dem
Bediirfniss eine
Form
nach
Un
Allgemeinheit
des Ausdruckes
der
Untersuchung
hat ihre
vom
grosstmoglicher
abstrakte
Leser
years
geleitet,
durch
gewahlt,
i bersehbare
welche
Gestalt eine
after
und
Aufmerksamkeit
When it work
von
nicht
it
was
gewohnliche
first
fordert."
was
to
Europe
fresh.
so
many
writ en,
ist noch ist
Gibbs'
heute
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
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
Schatze
Forscher desselben
Tage.
die
Energie
und
moglich chungen
Theil
geworden,
experimentel geschehen
verdiinnten
Gase
Losungen kennen,
wie ist
es
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=cr
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
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,
twocomponent
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
equilibrium
have
e.g.
we
change
in
order,
We of
pure
which know
generally
firstorder
exhibits
discontinuity
the
at
specific
CP
we
liquidvapor
which
Ehrenfest's
transition
finite
few the
except
at
the
some
critical deviations
3.7).
which transition
For
secondorder
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
HT 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.
=
twodimensional
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.
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
theory
for
404, vaporliquid
models.
curve
410)
problem
and the the
simple
vice
the
versa:
theories be obtained
magnetization
and
can
the
isotherm
the
pV
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
vaporliquid
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
longrange
range
molecular
interactions Rice interaction
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
order,
unstable
that,
against
transition.
the
volume,
and
we
system
the
never
with
CV
in stated from
a
volume
that
transition expect
changes
to
firstorder
should
transition.
find
infinite
specific
CHEMICAL
heats,
POTENTIAL
apart
firstorder
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
Hj^
0
C'(T2)dT2
'
RTi(+
the
RTlogp0)
D.15a)
the
potential
as
at
the last
temperature
term
and
standard
pressure*
(if
Also,
1, the
is
0).
T
U(T)
is
=UO
mole. heat
(CPR)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
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
jth.
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')
theyth
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
thejth
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)
is
usually
permissible low.)
component
a
saturation
ofthejth
by
solution
(or
solid
Git liq(T,
where
p)
chemical
Gj,gas(T,
potential mixture),
pressure of
p)
of
G?gas(T)
theyth
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 theyth
pj
is
at
the
temperature
the in
the
the
vapor
the
jth
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
theyth
component:
GJt
where
liq
(T,
p)
potential
<?Jt
]iq
(T,
of
p)
RT
log
Pj
%,
is
D.25)
given
liq,
the
chemical
theyth
pure
liquid,
by
?&
in
^
Po
D.26)
temperature
which/??
liquid.
In
is the
saturation
vapor
pressure
at
the
T, of
the
pure
7th
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
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
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)
k2X02
from
the
(x2
0)
D.30b)
RT\ogx2.
derived
solvent
are
D.30b)
The
GibbsDuhem
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
GibbsDuhem
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
twocomponent
AND
SOLIDSOLUTION)
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
solidsolutions
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
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
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
yth
component
+
in
solution
as
Gj(T,
which
are
p)
=
Gj{T, Gj{T)
G
the pressure
p)
+
RT
RT
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
yth
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
yth
component
yjt
the
fugacity
v,
and
the
Ch.
4, 12] vapor
SOLUTION
OF
STRONG
ELECTROLYTES
203
saturation
pressure
and
the
fugacity
of
theyth
pure
liquid
be/?
and
v.
Then
we
have
a,
y,Pi
,
P
=
V
>
(satvaPr
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
\ogC2,
where
(f>2
In
(fH2write
to
RT
logtlOOO/Mi),
chemical
the
and
<f>
a
<f>'2RT
solution
the
logpt.
in coefficients
a
order
to
the
potential
activities
a2>
of
general
and
dilute
form
analogous
T2
72>
D.46ac),
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.
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)
DebyeHiickel
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
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*+
V0B*
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
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
aGAbGB+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
AffTAS,
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
@A, Gg,. .
at
chemical
T
can
potentials
and standard
defined:
of
the
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:
(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
As
result cell
of
such
electrode the
certain
the
corresponding
amount
of
charge,
q,
transferred
semipermeable
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
and
SG 4.3.
is the
When
decrease
free
energy.
Reversible
cell:
the
to
circuit
in
dif erence,
the cell
current
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
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
by
A
are
maintaining
cell
in
contacts
cases
Ee
which
it
quasistatic
reversible
are
changes
cell. Cells
this between
is
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/gequiv.
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)
theyth
$"
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
yth
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,
AHTAS
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
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
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
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.
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.
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
quasistatic
two
isothermal
compression
some
GFDBA. termined
in
The the
phases
way.
at
intermediate
n
fol owing
Of
the
total
moles
of
the
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
(lx)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,
quasistatic
the One solution these der
processes
stability involving
we
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
GibbsDuhem
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'[
xGx[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)
Thus
is
dif erent
molar
a
system
is
xx
Q'
Q"
separates
C'
=
phases
C"
=
with
4X,\
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
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")=UTS,
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,
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 JT.
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
CpRlogp.
increase in
the
A) resulting
condensed
According
from
to
the
third
from
quasistatically
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
quasistatically
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
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
CuAg
ACF
is
system.
the
The solution
region
above
AEB
and
to
the
right
asolid 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
asolid
solution
up
point
figure?
Solution
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
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 aphase 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) aphase 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
phases.)
from
Similarly,
until
when
it
the
temperature
H,
starts
the
to
aphase
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
aphase
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
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
have
This
the
melt.
condition
the
the of
the
at
position
the
increases
is
temperature
silver
A
If,
continues
come
constantly
pure
separated,
solid
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
(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
semipermeable
temperature
A),
Therefore,
using
G01(T,p)G1(T,p0)=V(pp0)
(since approximation
the
change
is
in
volume
due and
to
osmotic
sufficient)
using
the
pressure definition
is
extremely
of osmotic
small,
pressure,
this
iii:
_
pure
solvent
solution
y.
/>.
semipermeable 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.
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)
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
TiTf:
=
RT.Xoga,
G{T,p0)
G\

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

p0)
Goltgas(T?,
=
p0)}
G\
if)
ZJ7?,
(8)
hence
If
logal=
).
T1r1
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
righthand
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
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 nonlinear
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
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
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
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
lefthand
an
A1)
besides
if
45
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
T,
eq.
two
which
is
This
of
cannot
the
solution.
exist
as
portion
A3). phase
the
where
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,
GibbsDuhem
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
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
lx"
'\
of freedom
of
RT
l
constituents,
eq.
A)
If
we
ignore
AG0
=
any
internal
+ +
degrees
the
D.15)
gives
GA+
U0A+
free
GeG0A
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
loc2F
where
,j
pccT*
*\
w=uOA++uOeuOA
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
higherorder
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+
II I I I
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 IIV
IVV
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
aphase
point
tangent
T
bphase
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
heat
of
vaporization
the
of
water
at
100
C.
triple
the
point,
gas
equilibrium
has
curve
(pT
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.
curved
pressure
surface,
dif erence
of
two
which
sides
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
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
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
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.
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
GibbsDuhem
of
relation,
and the
the
derive
formula
Henry's D.30b)
statements
D.29)
solute
potential
the mole
the
solute.
14.
fol owing
p
or
concerning
of
graph
xt
at
which
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
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
zth
component
when
and it
(j?
is made
is
Prove
for
an
ideal
solution
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
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
fusion
Lt
but
and
do
for
not
L2,
mix
respectively),
at
liquid
the
phase,
phase
Assume,
any
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
both
let
in
the
liquid
and
solid
the
phases. melting
Derive
Assume
mixtures
of
(i)
the
phase
and
fusion
which
and
(per
and
Tu mole),
the
equations
1500
give
the
solidus
1000
0.2
0.4
0.6
0.8
Phase
diagram
of
CuNi
alloy.
234
PHASE
EQUILIBRIUM
AND
CHEMICAL
EQUILIBRIUM
[Ch. of the
the and
show
above
general
that
one
has
equations a cigarshaped
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
jri
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
235
expected
we assume
between
that calcium in
the C the
gas
pressure
concentration
into
atoms
of
A A?
in
C,
if
molecule
A2
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
5388
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
mercury is
may
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
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
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
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
'
V2Vx
heat
Cpi
Pi
and
and
CP2
stand the
for
the
if
molar
of
1 is
Show,
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,
gdeg
c<0?
dr
0.64,
cal
r
=
gdeg
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
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
(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
HT
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/CsCn\
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
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
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
C,?
liquid
of
the
zone
is does that
cooled
not
occur
from
in
its
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
highpolymer 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
of
chemical
solvent
potentials
of
given
of
satisfy
with
the
GibbsDuhem 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
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
semipermeable
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
appears
on
both
sides
dif erence,
42.
semipermeable by considering
in osmotic
the
for
this
voltage
electrochemical
potentials.
membrane,
one
As
ions Then
is
shown
is inserted
figure,
a
semipermeable
and
is in
impermeable
M
an
+
to
R~
into
Utube,
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
(molkg1)
0.627 1.179
1.245
1.474
(cleg)
0.228 0.434
0.455 0.542 0.815
(molkg1)
3.526 4.520 6.879
(cleg)
1.286
1.644 2.494
these
data,
obtained
the
result
6 and
of
the
DebyeHiickel 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
ntype
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
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
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
such
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
CurieWeiss
(^
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
highpolymer
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
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
FV
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
ClausiusClapeyron
dTm dp
formula
given
273
in
D.4)
can
be
used;
Tm(Vlvs)
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
ClausiusClapeyron
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
1987
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
calg1.
observed
Note: the
539.032
calg
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
ClausiusClapeyron's
formula
D.4),
we
have
SgSs
^^s
dp\
1
(gas"shd)'
SgSl
(gasliquid),
Thus
we
and
we
know
FgF,,
Vs and
5g>S'1>S'g.
find
5.
The
triple
a
in
pT
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 polT
mm
gradient ClausiusClapeyron
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
273A.091
the
l)degcm3
curve
this
point.
and
a
On the
vapor very
other
equilibrium
the
pl2T
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
ClapeyronClausius
formula
D.4)
dp
_
can
be
writ en
for
this
case
as
df~T(vevy
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'
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
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
quasistatic
isothermal
given
by
Q
For
a
T(a2a1).
we
quasistatic
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
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
doctor
of the
by
founder
Divertissement
the
of
and
great
Scientists that
physiologist
have the
not
(see
yet
we
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
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
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
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
the
biologists
that
the
their disorder.
springs surroundings,
Life
drive
to
the then
that
appears
is,
What
to
tendency produce
some
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
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
molecules
gas
to
on
one
pass
(see
gets
second
nature
Diver
1, in R.
Kuboetal.,
If he side demon find
to
(NorthHolland
side
the
Publ.
Co.,
and decided Whether
1965)
that
on
p.
13).
the
a
we
functions
cools down.
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
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
GibbsDuhem
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
GibbsDuhem
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:
GibbsDuhem
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.
GibbsDuhem
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
DuhemMargules
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
righthand
side.
1 atm,
side For
x
F) instance,
103cm3
wil
be let
and be
the
neglected
order of
compared
the
the
the
100
lefthand
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
lefthand
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,
righthand 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
exponent
on
the
righthand
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,
semipermeable
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
ClausiusClapeyron'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
nonvolatile),
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
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()(TfT{)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
(lfc)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
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.
zth
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
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~
eA2
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
T2Tx
TTx
rp rj,
'
2 1
T{T2TX)
(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.
figure
K,
shows
the
1600 K
result
and in
a=
of
1.
the This
calculation
is
from
T2
similar
to
the
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:
=
lefthand
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
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
4.23.5
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
1044.2
107
107B73
18J
C)
calculation
x
and
thus
log
Hereafter,
obtain
wjgoQ
we
30'
in
whence
KA9
with
x
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
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/moldeg.
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
16.10+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)

D14')
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
Vnb 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
righthand
area
A),
and
(p(T),
pV
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
figure
the
in
Kaxis), (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 have
to
isotherm
give
Gibbs
sign
decreases
to
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
paxis
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
Kaxis with
such
way
equals
to
accordance
Maxwell's
corresponding
to
point
Maxwell's
energy
N
are
equilibrium
is
with derived
J and
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 Gcurve
(b).
a
the
so
point
that
MN the
N,
at
the from
rate
the
jump,
JK
Gcurve the
Gcurve gas
has
and
kink,
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 Gcurve
is
metastable
monotonically
the
respectively.
function
it
of from
p.
the
critical
Gcurve
T<
is when
reached
it is
temperature
the
gas
side,
temperature
the
has
kink
reached
When
low
is
rapidly
constant,
of
the
volume
is
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
onecomponent
energy
twophase
the whole
system.
G
gas
obtained
the
is the
Gibbs
system
ends. whereas
including
This
it
moves
is the
reason
from
and
the
kept
does
until in
the the
point
J to
point
is the
is
in is
the/?K
the
pG diagram.
N
liquefaction diagram,
When is
as
all
If
material
pressure increase
contained
is
the
system
energy
liquefied,
system
the
result
increased
the
further,
Gibbs free
in
the
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
ClapeyronClausius
are
dp/dT
is
determined
by
The
other
L\T{y^
V2\
derivatives
obtained
in
the
dp/dT=
way:
(d_L\
\dTjp
/dIA
JJJhH2)_
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
11S2)_
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'=CpiCp2.
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 ClapeyronClausius 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 r1, 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(vgvl),
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
it
compress
liquid
when the
and
pressure
that
liquid
lefthand
=
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
the
righthand
member
functions
eq.
F')
both
in
order
intersection
sides
(the
righthand 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
If
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
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
This
reached
the is
ClapeyronClausius
(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
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
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
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,. .,
GibbsDuhem
d6lg/dxg,. .
relations
+
their
at
azeotropic
x2l
as
Remembering
=
SldT+xlldGll
we
can
dG2l
fol ows.
0,
In
?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
righthand
Xn
=
member,
Xig
that the and 6T
means
and
lefthand
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
crosssectional
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
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)(Lx)}
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
semiconductor
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
resolidifies,
part
is
impurities
(the
molten
kept
from
collapsing
gathered by
righthand
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.
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)r2rw(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
(rl)<?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),
(xxJ
(xj
xxJ
(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
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
semipermeable 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
iV
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
m2g(deg)
theoretical
(m2
DebyeHiickel
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'kg1)
DebeyHuckel
0.009
0.012
0.627
1.179
103
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 0.027
10.633
282
PHASE
EQUILIBRIUM
AND
CHEMICAL
EQUILIBRIUM
[Ch. denoted
are
44.
If
the
number
densities the
number
use we
of
of
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
Ndne
On the
T*
exp
\(f? kT
{
^d
fil+the ionization
nS)
>.
in
crystal
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+(AgClKCl)
particular
electromotive cell
referred
force
Ag+(AgClKCl)
the
e>Ag(Ag;cAu1_;c)
to
the the
problem.
According
D.42),
is
=
given
by
5E
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.
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\
righthand
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
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
~
Vnb
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.
quasistatic
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.
Vnb
in
dV
_.
nR
log
VEnb
.
VAnb
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(VEVA).
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
righthand
in the
member
(9)
lefthand
the
area
corresponds
member isotherm
DELD
into is
the
area
the
rectangle
area
corresponds
ABLDE
the
figure.
that
rule. To
between the
convert
and
to
the
area
Faxis,
ALBA.
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
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
ferromagnet
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
(aM2HM)
a
=
0,
or
H/a,
C)
that
l/xT,
or
(Trc)/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
to
discuss
it
near
the
Curie
temper
put
0
j8(!T)~j8(Tc)
and thus
<xMs
This
?j8Ms3
gives
the
Ms
the
J6ol/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.
we
can
calculate
in
S=
the
specific
C=TdS/dT=
in
the
second
term
Fb).
We
thus AC
=
obtain
CTc0
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
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
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
drop
the the Wilson
This condenses
electric
clouds
to note
charges
and the
role,
About
when
water
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+(rl)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(rl)g
2(rlJg
E)
r(rlH
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
10
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
202
173, 9, 205,
of
197,
210,
283

263
coefficient
of bulk
202,
entropy
modulus 74
226 31
chemical
chemical
chemical
equilibrium potential
reaction

gas

197,
advancement
198
adiabatic

23,
91, 100,
process
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
ClausiusClapeyron
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 Auiz
adiabatic
coefficient
282

160
Clausius'
closed
63
32,
69
54
63,
1
78,
coefficient
85,
115 109
Ag*
air

20,

33,
242, 47;
heat 216
enthalpy
coefficient
149;
CO2,
system JouleThomson
of of
JouleThomson
94;
coefficient coexistence
coil
12
thermal
the
two
specific
152,
153
expansion phase
269
190,
212
aphase 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
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
critical critical
of
magnetic liquid
45
drop 26,
210,
271,
236
290
25,
233
critical
CuNi
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
calorie)
115
Curie
temperature
4
164,
289
182
CurieWeiss
182,
243
cycle
295
296
INDEX
Daniel
cell
207,
dissociation
freedom field
on
226 law
204,
234
241
226,
18,
process 59
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
257
depression
elevation
257
218,
219,
257
202,
13 231
206,
231
membrane relation
equilibrium
253
240,
280
gas
mixture
DuhemMargules
efficiency
electrical electric electric electrochemical
gas
gas
phase
thermometer
pressure
209
11,
94
65,
126;constant
condition
185
of203
gaseous
line
187
GayLussac's gebundene
235 209
91
207,
207
GibbsDuhem
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
GibbsHelmholtz
Gibbs'
phase
relation
242
rule
195
enthalpy
eutectic
3, 5, 147 8, 28,
GibbsPoynting
160
258
relation
71
192
entropy
entropytemperature entropy entropy
environment
point 70,
of of of of
Gibbs'
160
147,
potential
enthalpy
3,
5
136
111
melting mixing
1
72;
entropy
72
at
82,
195,
56
198
capacity
electric electric
continuity
state
constant
12,
57,
88; 210,
246
ideal
gas
13
206,
curve
234, 37,
261
57
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
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
nonnegativity engine
function
heat
(see
also
enthalpy)
INDEX
297
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 quasistatic
of
of
93, 76,

104,
heat
vaporization
free
energy
Helmholtz
214, 136,
the 175

isothermal
147,
surface
159,
214;
Jacobian
JouleThomson
JouleThomson
160,
extensive
164,
law
167,
property
177;
of 255
139 coefficient
of
91, 94,
126
94,
126
Henry's highpolymer
292
200,
solution
231,
effect
porous
277,
278,
JouleThomson
91
plug 161,
188;

experiment
170
28,
H2O
37,
90,
chloride
114,
JouleThomson
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;
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
ChatelierBrown'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
137
199 line
239,
258,
214
274
internal internal
friction
variable
phase equilibrium
210,
2, 74
state
3,
195
inversion
JouleThomson
temperature(point)
effect
204
energy
of
the
94,
124
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
manycomponent
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
manycomponent
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
122,
Maxwell's Maxwell's
equation
relation
37,
57
89,
181, 28,
33
155,
Maxwell's
284
169,
179,
rule
109,
286
139, 244,
242,
Mayer's Mayer's
mechanical mechanical mechanical mechanical
Meissner
cycle
relation action
21,
140
49,
120 140
enthalpy
entropy
free
energy
138
138 138
quantity
volume
molar
pressure
source
138
14,
198
3
(reservoir)
mobile
mobile of of the the
kind kind
6 63
equilibrium equivalent
interaction effect
238 257 209
perpentum
heat
7
of
2
melting melting
mercury
216,
point
235
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 nonholonomic nonvolatile
normal
288
specific
269,
92 256
271
protein
system
solute
state
quasistatic
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
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,
(see quantity
2
also
3
thermodynamic
equilibrium
3
state)
196
rubberlike
of variable
thermal
Rutgers'
SackurTetrode
239
state
StefanBoltzmann
formula
vapor
law
state
36
264
saturated
199,
271; 269;
heat
of
constant

200;
pressure pressure
adiabatic
200,
curve

201,
238,
pressure
203, 269;
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
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
200,
phase velocity
of
42
218, 252,
31,
257 39
spacerate
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
stability
standard of ions
free
in the
energy
of
1 mole
(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
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
WagnerEngelhardt
Warmeinhalt
water
cell
147
242
triple
twocomponent
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
enthalpy)
an
ion
272
290
Waals'
Waals
equation
gas,

15,
state
25,
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;JouleThomson
melting refining