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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

) =

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

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

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

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