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THERMAL PHYSICS

Text:
Thermal Physics
C. Kittel & H. Kroemer
1
INTRODUCTION
Laws of Thermodynamics
A thermodynamic system (e.g., gas in a piston) can be characterized by state variables such
as the pressure p, volume V , and temperature T. The work done by the system is W =
_
V
f
V
i
pdV .
The heat Q given to a system can lead to changes like increase in temperature or pressure.
The rst law of thermodynamics asserts that heat and work are two facets of the same
property and is a statement of its conservation;
dE
int
= dQdW, (1)
Unlike W and Q, E
int
is a state variable. The rate of change of E
int
of a unit mole (say) at constant
pressure is is the specic heat C
V
. Thus dE
int
= nC
V
dT.
Examples:
(1) Find the work done by 1.0 kg of water at 100
o
C when it is converted to steam at standard
atmospheric pressure. (The volume changes from 10
3
to 1.671 m
3
.) If the latent heat of water is
2256 kJ/kg, what is the change in the internal energy? How much heat was needed to to implement
the transition?
The entropy is dened through its change during a thermodynamics process,
S = S
f
S
i
=
_
f
i
dQ
T
. (2)
Entropy is a state variable. The second law of thermodynamics states that the entropy of a
closed system never decreases during a thermodynamics process. If it increases, the process is
irreversible; otherwise, it is reversible.
Examples:
(2) Find the change in entropy of an ideal gas when its state is changed from (T
i
, V
i
) to (T
f
, V
f
).
(3) Suppose 1.0 mol of nitrogen gas is conned to the left half of a container (the right half is
a vacuum). Find the change in entropy if the sides are now connected. (The gas constant is
R = 8.31J/mol.K.)
(4) Can work be entirely converted to heat? What about the reverse action?
A heat engine is a device that is provided heat and does work. It needs to operate in a cycle
where the working substance passes through a closed series of thermodynamic processes called
strokes. We consider ideal enginesor Carnot engine, which consists of reversible processes.
Thus, there is no energy loss from friction or air resistance.
Course Outline
A specied state of a thermodynamic system has many possible (g) accessible quantum
2
states. Statistical mechanics assumes that the system is equally likely to be in any of
these states. The entropy of a system measures (the logarithm of) the number of accessible
quantum states; = log g. It is a function of other state variable such as U, N, and V . By
talking the logarithm, we ensure that the total entropy for two uncoupled systems is
1
+
2
.
When two systems are brought into thermal contact, energy will transfer from one to
the other so that g
1
g
2
(or
1
+
2
) is maximized. (Of course, all possible states are accessed
with equal likelihood.) This is the statistical mechanics formulation of the second law of
thermodynamics. We will show that, in this equilibrium
1

U
_
N,V
(3)
is equal for the two sub-systems. With this denition, energy ows from the sub-system with
large to the one with small . = k
B
T, where k
B
= 1.38 10
16
erg, is the Boltzmann
constant.
Next, consider a small system with two states (energy 0 and ) brought into thermal
contact with a reservoir with energy U
0
. The probabilities P(0) and P() with with the
state of the small system is found are related by
P()
P(0)
=
g(U
0
)
g(U
0
)
exp(/). (4)
The thermal average energy of the small system at temperature is
) =
exp(/)
1 +exp(/)
. (5)
The next issue is what happens when two systems are in thermal and diusive contact.
Then, in addition to (/U)
N,V
, (/N)
N,V
of the two sub-systems need to be equal as
well. This leads to the denition of the chemical potential :

=
_

N
_
U,V
. (6)
Particles move from high to low chemical potential upon diusive contact.
Now consider a system with two states: the rst with 0 particles and energy 0, and the
second with 1 particle and energy . The probability of the high energy state when the system
is in thermal and diussive contact with a reservoir is (the Fermi-Dirac distribution)
P(1, ) =
1
1 +exp [( )/]
, (7)
which in the classical limit is P(1, ) exp [( )/].
3
CHAPTER 1
STATES OF A MODEL SYSTEM
The development of statistical mechanics requires counting the possible quantum
states of a system when the state variables are given. Each quantum state had a de-
nite energy. Those with the same energy belong to the same energy level; the number of
such states is the multiplicity or degeneracy. It is the quantum state, not energy levels
that are relevant in our computations.
Binary Model System
The system contain N identical uncoupled spins, each of which can be in two states. The
two states can be energy levels, spins, or two types of atoms in a binary alloy. We represent
the spins as lying along a line. Each state can be represented by N symbols which are or
. The totality of states can be represented by the generating function
(
N
= ( + )
N
. (8)
Dene the spin excess of the system as
2s = N

, (9)
which can be thought of as a macroscopically measurable state variable. The number of
states with a specied spin excess is the multiplicity function
g(N, s) =
_
N
N

_
=
N!
N

!N

!
, (10)
and the generating function satises
(
N
=
N/2

s=N/2
g(N, s)
N/2+s

N/2s
. (11)
Sharpness of the Multiplicity Function
Using the Stirling approximation
log N!
1
2
log 2 +
_
N +
1
2
_
log N N, (12)
we can see that
g(N, s) g(N, 0)exp
_
2s
2
/N

, (13)
with g(N, 0) 2
N
_
2/N. (Note that g(N, 0) =
_
N
(N/2)
_
.)
4
The distribution g(N, s) peaks at s = 0, and reduces by e
1
when 2s/N =
_
N/2. For
large N, this is a sharp distribution. So, a vast majority of the congurations of the spin
system have 2s/N 0.
Average Values
The mean value of a function f(s) over a normalized distribution P(s) is
f) =

s
f(s)P(s).
For the binomial distribution, it is seen that
_
(2s)
2
) =

N, and hence fractional uc-


tuation in (2s) is
T
_
(2s)
2
)
N
=
1

N
.
The relative distribution becomes sharper as N increases.
Energy of a Binary Magnetic System
Thermal properties of our model spin system become relevant when it is placed in a magnetic
eld B.The energy of interaction of a spin with the eld is
U = m B.
The energy gap between nearest energy states is 2mB.
Multiplicity Function for N Harmonic Oscillators
The non-degenerate quantum states of a single harmonic oscillator have energy eigenvalues

s
= s,
where the quantum number s is a non-negative integer. We wish to nd the multiplicity
function g(N, n) for a system of N non-interacting harmonic oscillators. whose total energy
is n. Since g(1, n) = 1 for all n, the generating function for a single oscillator is

n=0
g(1, n)t
n
=

n=0
t
n
=
1
1 t
.
Consequently, the generating function for N uncoupled oscillators is
_
1
1 t
_
N
=
_

n=0
t
n
_
N
=

n=0
g(N, n)t
n
.
Thus
g(N, n) =
_
N +n 1
n
_
.
5
Assignment 1:
(1) Carry out the Taylor expansion in of the functions (a) sin(a + ), (b) exp(a + ), (c)
log(a +), and (d) tan(a +).
(2) Show the Stirling expansion (see Appendix A, but make sure you understand the calcu-
lation rst!)
log N!
1
2
log 2 +
_
N +
1
2
_
log N N.
(3) The normal distribution is
^(x) =
1

2
e

1
2
x
2
.
It is normalized. Using induction calculate the (2n)
th
moment of the normal distribution.
6
CHAPTER 2
ENTROPY AND TEMPERATURE
Fundamental Assumption
A closed system is one whose energy, number of particles, volume, and other macroscopic
external variables are kept xed. The fundamental assumptions of thermal physics is that
is equally likely to be in any one of its accessible quantum states; i.e., states which are
consistent with the conditions that dene the closed state. From a practical standpoint,
what we require is U/U 1, N/N 1, etc. Note, however, in some systems, accessible
states may be separated by a large barrier.
An ensemble is a collection of all systems which have identical state functions. If there
are g accessible states, then the ensemble average is given by
X) =

s
X(s)
1
g
.
In order to analyze thermal equilibrium, let us consider two systems of spins o
1
and o
2
of
N
1
and N
2
particles with energy U
1
and U
2
, brought into thermal contact. The multiplicity
function of the combines system o is
g(N, s) =

s
1
g
1
(N
1
, s
1
)g
2
(N
2
, (s s
1
).
Equilibrium is given by dg = 0 with dU
1
+dU
2
= 0. This gives
_

1
U
1
_
=
_

2
U
2
_

,
where is the common fundamental temperature at equilibrium. It is related to the
temperature by = k
B
T.
Example: The computation can be done explicitly using the approximation g(N, s) =
g(0) exp(2s
2
/N).
Entropy
The entropy is the logarithm of the number of accessible of states of a system. In classical
thermodynamics, it is dened as
1
T
=
_
S
U
_
N
, (14)
and hence
S = k
B
. (15)
7
Examples:
(1) When an energy U is transferred from a system of temperature
1
to another of
2
, the
entropy of the combined systems changes by U(1/
1
+ 1/
2
).
(2) A 10-g specimen of Cu at 350
o
K be placed in contact with an identical specimens at
290
o
. What is the energy transfer till equilibrium and the nal temperature. The specic
heat of Cu is 0.389Jg
1
K
1
. (b) What is the change in entropy of the system after 0.1 J
has been exchanged?
Law of Increase in Entropy
The number of accessible states increases when two sub-systems are brought into thermal
contact (Original set of states + more). Thus
final

initial
.
Laws of Thermodynamics
Zeroth Law: Two system in thermal equilibrium with a third are themselves in equilibrium.
First Law: Heat is a form of energy, and total energy of a closed system is constant.
Second Law: The entropy of a system increases when an internal constraint is removed.
Alternatively: It is impossible for for any cyclic process whose sole eect is to extract heat
from a reservoir and perform an equivalent amount of work.
Third Law: The entropy of a system approaches a constant value as the temperature
approaches zero.
Assignment #2
Chapter 2: 1, 2, 3, 4, 5, 6
8
CHAPTER 3
BOLTZMANN DISTRIBUTION AND HELMHOLTZ FREE ENERGY
Boltzmann Factor
Consider a system o in thermal equilibrium with a thermal reservoir 1 of temperature .
Consider two states of o of energies
1
and
2
. The probablities of these states are related
by
P(
1
)
P(
2
)
=
g
R
(U
0

1
)
g
R
(U
0

2
)
exp(
R
).
Taylor expansion of the entropy results in
P(
1
)
P(
2
)
=
exp(
1
/)
exp(
2
/)
. (16)
The Boltzmann factor exp(/) expresses the relative probability of occupying a state.
Partition Function
Dening the partition function by Z() =

s
exp(/), the probability of a quantum
state is given by
P(
S
) =
exp(
S
/)
Z
. (17)
The generating function Z can be used to compute mean properties of the ensemble. For
example,
U =

S
exp(/)
Z
=
2

log Z. (18)
Examples:
(1) Consider a system with twos state of energy /2 and /2. Show that (a) Z =
2 cosh(/2). (b) ) = tanh(/2)/2. (c) C
v
(/)
V
= (U/)
V
satises
C
v
=
_

_
2
exp(/)
[exp(/) + 1]
2
.
Pressure
Consider reversibly (slowly) reducing the volume of a system so that it always remains in
an equivalent quantum state. This process is reversible, so remains unchanged. The
energy of the quantum state changes according to

S
(V V ) =
S
(V )
d
S
dV
V +. . .
9
Since the energy of the system depends on V
U = U(V V ) U(V ) =
d
S
dV
V +. . .
But by considering the mechanical action that reduces the volume os the system, p
S
=
d
S
/dV . Hence
p =
_
U
V
_

, (19)
where U = ).
To continue, note that the entropy of a system depends on U and V . Hence the dierential
d(U, V ) is given by
d(U, V ) =
_

U
_
V
dU +
_

V
_
U
dV.
Considering a reversible process and the denition of temperature
p =
_

V
_
U
. (20)
Now, we nd the thermodynamic identity
d = dU +pdV,
Helmholtz Free Energy
Helmholtz free energy is the function
F U . (21)
It plays the role analogous to that of energy in mechanical systems (no changes in states,
hence is constant) in thermodynamic system held at constant temperature. It shows the
balance between (minimizing) energy and (maximizing) entropy or the number os accessible
states. F is minimized for a system o in contact with a reservoir 1 of temperature . It
can be seen that dF
S
= 0.
Examples:
(2) Calculate the entropy and free energy for a system of N independent spins with spin
excess 2s. Show that the minimum spin excess is 2s) = N tanh(mB/), and that the
partition function is Z = 2 cosh(mB/).
Dierential Relations
From dF = dU d d, it follows that dF = d pdV , and hence
_
F

_
V
= ;
_
F
V
_

= p. (22)
10
One may thus write
p =
_
U
V
_

+
_

V
_

.
The interpretation is that the pressure has energy and entropy components. The former
is dominant in solids while the latter is dominant in gases, elastic polymers etc. It also follows
that
_

V
_

=
_
p

_
V
.
This and other such Maxwell relations follow from the smoothness of the Free energy
function.
Examples: (3) Using F = U , = (F/)
V
, and Equation 18, show that F =
log Z. The constant of integration vanishes due to the third law of thermodynamics.
(4) Show that
P(
S
) = exp[(F
S
)/].
Ideal Gas: a First Look
The wave-function for a mass M in a box of volume V = L
3
satises (/2M)
2
= ,
and the eigenstates are
(x, y, z) = Asin(n
x
x/L) sin(n
y
y/L) sin(n
z
z/L),
where n
x
, n
y
, and n
z
are integers. The energy eigenvalues are

n
=

2M
_

L
_
2
(n
2
x
+n
2
y
+n
2
z
).
The partition function extended to the continuum is
Z
1
=
_

0
dn
x
_

0
dn
y
_

0
dn
z
exp[
2
(n
2
x
+n
2
y
+n
2
z
),
with
2
=
2

2
/2ML
2
. Thus
Z
1
= n
Q
/n,
with n = 1/V and n
Q
= (M/2
2
)
(3/2)
is the quantum concentration. An ideal gas is
a system of such particles with no interactions.
Examples: (5) Find n/n
Q
for helium at atmospheric pressure and room temperature.
Whenever n/n
Q
1, the gas is said to be in the classical regime.
11
(6) Show that U = (3/2) for a ideal gas of one atom.
(7) The partition function for a system of N non-interacting particles is
Z
N
=
1
N!
Z
N
1
=
1
N!
(n
Q
V )
N
.
(8) The energy of the system is U = (3/2)N, and the free energy is F =
N log[n
Q
V ] + N log N N. Hence show that pV = N. The entropy is
= N[log(n
q
/n) + (5/2)]. This is the Sackur-Tetrode equation.
Assignment #3
Chapter 3: 1, 2, 3, 4, 7.
12
CHAPTER 4
THERMAL RADIATION AND PLANCK DISTRIBUTION
According to quantum mechanics radiation consists of quanta of energy , and a state
with s such quanta has energy
S
= s. Unlike for the harmonic oscillator, these are
distributed states. The partition function for the system whose photons are in thermal
equilibrium with a reservoir is given by
Z =
1
1 exp(/)
,
and the mean value of s is
s) =
1
exp(/) 1
.
This is referred to as the Planck distribution function.
Planck Law and Stean-Boltzmann Law
The thermal average energy in the mode is
) =

exp(/) 1
=
1
2
coth(/2)
1
2
. (23)
In the high temperature classical limit ) .
Next consider the EM radiation conned in a perfectly conducting cubic cavity of side
L. From Maxwells equations, there are three modes whose electric elds are given by
E
x
= E
x0
sin t cos(n
x
x/L) sin(n
y
x/L) sin(n
z
x/L),
E
y
= E
y0
sin t sin(n
x
x/L) cos(n
y
x/L) sin(n
z
x/L),
E
z
= E
z0
sin t sin(n
x
x/L) sin(n
y
x/L) cos(n
z
x/L),
Since the eld is divergence-free, E
0
n = 0, with n = (n
x
, n
y
, n
z
). Hence the electromag-
netic eld is transversally polarized, with a polarization direction E
0
. From the wave
equation c
2
E
x
=
2
E
x
/t
2
, the frequencies are given by

n
= nc/L.
Hence, the total energy of photons in the cavity is
U =

n
exp(
n
/) 1
.
13
Now, we note that the sum is over positive integers and replace the sum

. . . by the integral
2
1
8
_

0
4n
2
dn. . . (2 polarizations!) to get the Stefan-Boltzmann law of radiation
U
V
=

2
15
3
c
3

4
. (24)
The spectral density of radiation is given by the Planck radiation law
u

2
c
3

3
exp(/) 1
. (25)
Using d = dU/, the entropy of the radiation is
() =
4
2
V
45
_

c
_
3
.
Next, the ux density of radiation from a black-body is given by
J
U
=
1
4
cU()
V
=

2

4
60
3
c
2
=
B
T
4
, (26)
where 1/4 is a geometrical factor, and the Stefan-Boltzmann constant
B
=
2
k
4
B
/60
3
c
2
.
Emission and Absorption
The radiant energy ux density from a black surface at temperature is equal to that from
a black body, i.e., a black cavity with a small hole. This can be seen by considering
the conguration obtained by closing the hole in the black body with the surface. Similar
arguments shows that the absorptivity a and emissivity e of a surface are the same if
equilibrium is maintained. This is Kirchos law. Similar considerations apply to each
frequency; a() = e() for any surface in thermal equilibrium.
The temperature of a hot object can be estimated by determining the peak frequency
of the emission radiation energy distribution. It is given by
max
/k
B
T 2.82, where the
right side is the solution of 3 3 exp(x) = x.
Phonons in Solids: Debye Theory
The energy of elastic waves in a nite solid is quantized. The corresponding quantum of
energy is called a phonon, with energy . The thermal average number of phonons in an
elastic wave is
s()) =
1
exp(/) 1
.
We calculate the energy and heat capacity of elastic waves in solids assuming that the
frequency is independent of the amplitude of the elastic strain. We assume that the velocities
of elastic waves are independent of frequency, direction of propagation, and direction of
polarization. The main experimental observations to be explained are that the heat capacity
of a non-metallic solid is (1) proportional to
3
, and (2) independent of at large .
14
Number of Phonon Modes
Unlike for electromagnetic radiation, a solid with N atoms has only 3N modes. Since there
3 polarizations,

n
(. . .) =
3
8
_
n
D
0
dn4n
2
(. . .),
where n
D
= (6N/)
(1/3)
is determined by using the condition that there are only 3N modes.
The thermal energy of the phonons is
U =

s
n
) =
3
2
v
2L
_
L
v
_
4
_
x
D
0
dx
x
3
exp x 1
,
where x hvn/L, and v is the speed of sound. Here x
D
= /T = k
B
/, where the
Debye temperature is given by
=
_
v
k
B
__
6
2
N
N
_
(1/3)
.
At low temperature (T ), the integral is approximately
4
/15 and hence
U(T)
3
4
Nk
B
T
4
5
3
,
and the heat capacity is
C
V
=
_
U

_
V
=
12
5

4
N
_

k
B

_
3
.
This is the Debye law.
Assignment #4
Chapter 4: 1, 2, 4, 5, 7, 9, 11
15
CHAPTER 5
CHEMICAL POTENTIAL AND GIBBS DISTRIBUTION
Consider two systems o
1
and o
2
that are in thermal and diusive contact. The combined
system is in thermal contact with the reservoir, and hence its Helmholtz free energy F =
F
1
+F
2
= U
1
+U
2
(
1
+
2
) is minimized; i.e.,
dF =
_
F
1
N
1
_

dN
1
+
_
F
2
N
2
_

dN
2
= 0.
Consequently
_
F
1
N
1
_

=
_
F
2
N
2
_

.
The common value is referred to as the chemical potential (, V, N), and when the two
systems are in equilibrium
1
=
2
. Note that dF = (
1

2
)dN
1
; hence if
1
>
2
, dF is
reduced with dN
1
< 0. Particles ow from a system of higher chemical potential to one of
lower chemical potential. When the systems contain several chemical species, the chemical
potentials of each species is identical at equilibrium.
Examples:
(1) Starting from Z
1
= n
Q
V , show that the chemical potential for an ideal gas is =
log(n/n
Q
) = log(p/n
Q
). Chemical potentials of atomic and molecular gases are negative.
If the potential of the system is increased, its free energy is enhanced by N. Hence,
The chemical potential is equivalent to a true potential energy. The dierence in between
two systems is the potential barrier that will bring the systems to diusive equilibrium.
Consequently, the total potential energy can be decomposed as
=
tot
=
ext
+
int
,
where
int
is the internal or intrinsic chemical potential.
Examples:
(2) Consider the atmosphere as consisting of layers of air at a xed temperature in diusive
equilibrium. Show that the density at height h is given by n(h) = n(0) exp(Mgh/).
Deduce the barometric pressure equation p(h) = p(0) exp(h/h
c
.
(3) Consider a collection of mobile spins ( or ) placed in a magnetic les B. Show that
n

= (1/2)n(0) exp(mB/) and n

= (1/2)n(0) exp(mB/). Hence show that the total


16
density of spins in a region of magnetic eld B is n(B) = n(0) cosh(mB/). Thus, spins
concentrate on regions of high magnetic eld.
(4) The reactions at the negative and positive electrodes of an electrochemical battery are
Pb +SO

4
PbSO
4
+ 2e

PbO
2
+ 2H
+
+H
2
SO
4
+ 2e

PbSO
4
+ 2H
2
O.
The negative electrode is a sink for SO

4
ions, keeping the internal chemical potential at
(SO

4
). Similarly, the positive electrode is kept at (H
+
).
Chemical Potential and Entropy
Using = (U, V, N), keeping V xed, and considering isothermal changes,
()

=
_

U
_
N
(U)

+
_

N
_
U
(N)

,
which gives

_

N
_
,V
=
_
U
N
_
,V
+
_

N
_
U,V
.
Hence
=
_
F
N
_
,V
=
_

N
_
U,V
(27)
Thermodynamic Identity
Taking the dierential of = (U, V, N), we obtain the thermodynamic identity
dU = d pdV +dN, (28)
which generalizes the corresponding statement for systems with a xed number of particles.
Gibbs Factor and Gibbs Sum
Consider a system o in thermal and diusive contact with a reservoir, characterized by
a temperature and a chemical potential . By considering the degeneracy of (system +
reservoir) for each quantum state of o, we can show that
P(N
1
,
1
)
P(N
2
,
2
)
=
exp[(N
1

1
)/]
exp[(N
2

2
)/]
.
The term exp[(N)/] is the Gibbs Factor, which is proportional to the probability of
the system being in a state of energy and particle number N. The normalization factor
(, ) =

N=0

s(N)
exp[N
s(N)
] =

N=0

s(N)

N
exp(
s
/) (29)
17
is the Gibbs sum or the grand sum. = exp(/) is the absolute activity.
Examples:
(5) Show that (a) N) = (/) log = (/) log and (b) U = ((/)
(/(1/))) log .
(6) Show that the fraction of a surface occupied by gas molecules of ambient pressure p is
f = p/(p +p
0
). This is the Langmuir adsorption isotherm.
Assignment:
Chapter 5: 1, 3, 5, 6, 7.
18
CHAPTER 6
IDEAL GAS
An ideal gas is a system of free noninteracting particles, assumed to be in the classical
regime. The (average) occupancy of a state of energy is given by the semi-classical
distribution function
f() = exp[( )/] = exp(/).
The chemical potential of the ideal gas can be determined by N = N) =

s
f(
s
=

s
exp(
s
/). Since the last sum is Z
1
, the partition function for a single particle,
N = Z
1
, and consequently
= log(n/n
Q
) =
_
log N log V
3
2
log +
3
2
log
_
2
2
M
__
. (30)
N.B.: (1) the chemical potential will shift if the energy is shifted. (2) If the gas is not
monotonic, degeneracies associated with vibrations and rotations need to be included. (3)
Chemical potential for non-ideal gases can be very dierent.
The other thermodynamic variables of an ideal gas can be derived using the following con-
siderations.
The chemical potential and the free energy are related by = (F/N)
,V
, and hence
F = N[log(n/n
Q
) 1]. (31)
F increases with n and decreases with .
The pressure of the ideal gas satises p = (F/V )
,N
, and is given by
pV = N. (32)
The energy of the (monatomic) ideal gas is U = (3/2)N.
The entropy = (F/)
V,N
is given by the Sackur-Tetrode equation
= N
_
log(n
Q
/n) +
5
2
_
. (33)
The heat capacity at constant volume is
C
V

_

_
V
=
3
2
N. (34)
Using the thermodynamic identity d = dU + pdV , the specic heat at constant
pressure is C
P
= C
V
+N = (5/2)N.
19
Chemical Potential of Ideal Gas with Internal Degrees of Freedom
As we learned in classical mechanics, the kinetic energy of an object is the sum of the kinetic
energies of the center of mass (i.e., translational) and that about the center of mass. Hence
=
n
+
int
, where the second term contains energy due to factors like vibrations and
rotations about the center of mass.
Since the occupancy in the classical regime is 1, the translational component of
1 +exp(
n
/). When internal energies are included,
= 1 +exp(
n
/)Z
int
,
where Z
int
=

int
exp(
int
/). The probability that the state is occupied, irrespective of
the internal state, is
f(
n
) =
Z
int
exp(
n
/)
1 +Z
int
exp(
n
/)
Z
int
exp(
n
/).
Examples:
(1) Show the following for an ideal gas with internal degrees of freedom:
= n/n
Q
Z
int
and = [log(n/n
Q
) log Z
int
].
For N particles, the free energy is increased by F
int
= N log Z
int
.
The entropy increases by
int
= (F
int
/)
V
.
Selected Thermodynamic Changes
(A) Reversible Isothermal Doubling of the Volume.
The temperature is maintained by slowly expanding the system while it is in contact
with a reservoir. The process is reversible. It can be seen that (1) the pressure reduces by a
factor of 2, (2) The entropy increases by N log 2, (3) The amount of work done by the gas
is W = N log 2, and that the heat that owed into the gas from the reservoir is W.
(B) Reversible Doubling of the Volume at Constant Entropy.
This can be achieved by preventing heat ow into the system, and carrying out the expansion
slowly. Note that a process which does not receive or give heat is an adiabatic process,
and one that is not accompanied by a change in entropy is called an isentropic process.
For an ideal monatomic gas

(3/2)
1
V
1
=
(3/2)
2
V
2
p
1
V
(5/3)
1
= p
2
V
(5/3)
2

(5/2)
1
/p
1
=
(5/2)
2
/p
2
20
The energy change is U
2
U
1
= (3/2)N(
2

1
).
(C) Sudden Expansion into a Vacuum in a Thermally Isolated System.
This is an irreversible process since during the expansion dierent sections of the gas may
be at dierent temperatures. No work is done during the process, and no heat is absorbed
or emitted by the system. The entropy increases by N log 2.
Assignment:
Chapter 6: 5, 6, 12, 13.
21
CHAPTER 8
HEAT & WORK
Both heat and work are forms of energy transfer. However, unlike work, the trasfer
of an amount of heat dU from a reservoir at temperature is accompanied by an entropy
transfer d = dU/. From the conservation of energy
dU = dW +dQ. (35)
Heat Engines: Conversion of Heat into Work
Although dierent types of work can be freely converted to one another and work can be
freely converted to heat, conversion of heat to work is more subtle. The underlying reason
is the need to satisfy the second law of thermodynamics. In order to pursue this further,
consider a heat engine, which executes cycles that convert heat to work (partially). We
rst study an idealized case, a Carnot cycle, which is assumed to consist of reversible
components. During each cycle, it absorbs an amount of heat Q
h
at a high temperature

h
= k
B
T
h
, performs an amout of work W, and discards an amount of heat Q
l
at a low
temperature
l
= k
B
T
l
. The Carnot eciency is

C

_
W
Q
h
_
rev
=

h

h
=
T
h
T
l
T
h
. (36)
Carnot cycles are the optimal engines that works between temperatures
h
and
l
. Actual
engines are irreversible due to friction, direct transmission of heat from
h
to
l
, irreversible
transfer within the engine, etc. The eciency of all cycles operating between
h
and
l
satisfy the Carnot inequality (W/Q
h
)
C
.
Refrigerators
A refrigerator is a machine that consume work to move heat from a low temperature
l
to
a high temperature
h
. Its performance is measured by the coecient of refrigerator
performance, = Q
l
/W. is optimized for reversible cycles for which

C
=
_
Q
l
W
_
rev
=

l

l
=
T
l
T
h
T
l
. (37)
The action of a refrigerator can be reversed to form a heat pump.
Carnot Cycle
In the Carnot cycle, the working substance is expanded in contracted in 4 reversible stages,
22
two isentropic and two isothermal (at
l
and
h
). Thus Q
h
=
h
(
h

l
and Q
l
=
l
(
h

l
.
Since U = 0 for the cycle, W = Q
h
Q
l
.
Examples:
(1) Consider a Carnot cycle whose working substance is an ideal monatomic gas. The gas
is rst expanded from V
1
to V
2
isothermally at
h
, then expanded isentropically to a volume
V 3, when it reaches a temperature
l
. It is now compressed isothermally to a volume V
4
such that V
4
/V
1
= V
3
/V
2
. Finally it is returned to the original state through a isentropic
compression. Calculate the work performed and heat absorbed/emitted during each stage,
and compute the eciency of the cycle.
Notes:
(a) All reversible cycles working between two temperatures have the same eciency. This
is a consequence of the second law of thermodynamics.
(b) Heat absorbed and work performed between two thermodynamic states are path depen-
dent, as can be seen from the analysis of the Carnot cycle. They are not thermodynamic
variables.
Examples:
(2) Consider a sudden expansion of an isolated ideal gas from a volume V
1
to V
2
, for which
Q
irr
= 0 and W
irr
= 0. Calculate Q
rev
and W
rev
for a reversible (isotropic) transition
between the initial and nal states. Show that W
irr
> W
rev
and Q
irr
< Q
rev
. These results
are general.
(3) Calculate the change in entropy when an amount of heat Q is transferred from an
object of temperature
h
to one of
l
.
Heat and Work at Constant Temperature or Constant Pressure
Isothermal work: The work performed on a system during an isothermal process is the
change in the Helmholtz free energy, since
dW = dU dQ = dU d() = dU d = dF.
Thus F is the natural energetic function for such processes.
Isobaric heat and work: processes that occur at constant pressure are called isobaric.
The expansion of the system by dV is accompanied by an amount pdV of work done by the
system. This leads to the denition of enthalpy, H = U + pV . The eective work done
during the process is dW

= dH dQ.
Two particularly important isobaric process are:
Processes where no eective work is performed, such as is the evaporation of a liquid.
The heat of vaporization is the dierence in enthalpy between the vapor and liquid
phases.
23
Processes at constant temperature and pressure, such as chemical reactions. The
eective work performed is dW

= dF +d(pV ) = dG where G F +pV = U+pV


is the Gibbs free energy.
Chemical work is the work performed to transfer particles to a system, and is related
to chemical potential. From the thermodynamic identity
dU = d pdV +dN,
the eective work is dW = pdV +dN. The rst term is the mechanical work, and
the second is the chemical work. The work needed to move dN particles from a system
of chemical potential
1
to one of
2
is dW
c
= (
2

1
)dN.
Examples:
(4) Calculate the chemical work needed to move N particles from an ideal gas with concen-
tration n
1
to one of concentration n
2
, when both are at a temperature . Show that this is
equal to the work done to compress an ideal gas of N particles from a volume V
1
= N/n
1
to one of volume V
2
= N/n
2
.
Assignment:
Chapter 8: 1, 2, 4, 6, 8.
24
CHAPTER 9
GIBBS FREE ENERGY & CHEMICAL REACTIONS
The Gibbs free energy or thermodynamic potential
G U +pV,
is minimized when the system is in thermal contact with a reservoir of temperature and
in mechanical contact with pressure reservoir of pressure p. This can be seen because for
such a system dG
S
= dU
S
d
S
+ pdV
S
. Using the thermodynamic identity, it is found
that dG
S
= 0, and G = G(N, , p). Since dG = dN d +V dp, we have
=
_
G
N
_
,p
; =
_
G

_
N,p
; V =
_
G
p
_
,N
. (38)
When the system contains only one species,
G(N, p, ) = N(p, ). (39)
When there is more than one species G =

N
j

j
, and the thermodynamic identity is
generalized to dG =

j
dN
j
d +V dp.
Examples:
(1) For an ideal gas F(, V, N) = N[log(N/V n
q
) 1]. Show that (N, , V ) =
log(N/V n
Q
). In this formulation (i.e., as a function of V ) not independent of N.
However, the Gibbs free energy for an ideal gas is G(, p, N) = F +pV = N o(p/n
Q
), and
hence (, p) = log(p/n), independent of N.
Equilibrium in Reactions
If a chemical reaction

j

j
A
j
= 0 occurs at constant pressure and temperature, the mini-
mization of the Gibbs free energy gives

j

j

j
= 0.
For ideal gases
j
= (log n
j
log c
j
), where c
j
n
Q
j
bZ
j
(int) does not depend on the
concentration. It follows that

j
n
j

j = K(), (40)
which is the law of mass action and K() is called the equilibrium constant.
Examples:
(2) The equilibrium constant for the reaction H
2
O H
+
+(OH)

is 10
14
. Show that the
25
pH log
10
[H
+
] of pure water is 7.
(3) Consider a chemical reaction whose dynamics is
dn
AB
dt
= Cn
A
n
B
Dn
AB
.
In equilibrium n
A
n
B
/n
AB
is a constant. This is the principle of detailed balance, which
holds even when there are intermediate reactions.
Assignment:
Chapter 9: 1, 2, 4, 5.
26