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Fall 1998

J. G. Saven

Thermodynamics

References: Chandler, chapters 1 and 2 [1]; McQuarrie, chapters 1-4 [2]; mostly from Callen,

chapters 1-8 [3].

Macroscopic measurements are slow and coarse on the atomic scale. Typically, we end up

averaging over a huge number ~1023 of molecular degrees of freedom in determining macroscopic

quantities. We can treat matter as being essentially continuous and for the most part ignore the

fact that molecules exist.

We will consider systems that are homogeneous, isotropic, uncharged, and we neglect surface

effects.

Thermodynamics describes only static states of macroscopic systems. That is, those states that

are time-independent.

We will specify the amount of stuff (matter) by chemical composition or by mole numbers, N.

Extensive parameters are those parameters that depend on the amount of stuff we have. More

specifically, if a system can be broken up into subsystems, the value of an extensive quantity is

equal to the sum of the values it has in each of the subsystems.

N 1 , V1

N 2 , V2

N m , Vm

m

N=

Ni

i=1

m

V=

Vi

i=1

Macroscopic systems have well-defined energies that are conserved and extensive.

Equilibrium: Tendency to evolve to states that depend only on intrinsic factors and not on the

past history of the system. An equilibrium state may also be called a time-independent state (at

least with regard to macroscopic variables).

Equilibrium states are characterized by relatively few variables, e.g., U, V, Ni

We will use the somewhat circular definition that a system is at equilibrium if it obeys the laws and

equations of thermodynamics. We note that thermodynamics is also useful for describing

metastable (long lived, but unstable) states

Possible constraints on system

adiabatic: no heat flow

diathermal or diabatic: heat flow permitted

9/16/98

U. Penn.

Fall 1998

J. G. Saven

isolated system: no heat flow, no matter flow

Lets consider a piston in a system with adiabatic walls.

N, V, U

If the process happens really slowly and is reversible, the work done is the difference in internal

energy U between the two states. The internal energy depends only on the initial and final states

and not on the path between them. The internal energy is said to be a state variable.

For a quasistatic (reversible) process:

dW = - PdV = dU

Note that if dV < 0, work is done on system and its energy increases (hence dW = PdV).

Let the number of moles of a substance be fixed (constant N). The heat flux dQ is the difference in

U between two states diminished by the work done:

dQ = dU dW = dU + PdV

We must emphasize that neither Q nor W are state functions. In general, their values depend on the

path taken between to points that specify the state of a system. Only when a process is quasi-static

or reversible, can we equate these quantities with state functions.

What is equilibrium state after the removal of internal

constraints on a closed or isolated system?

N ,V ,U

piston is allowed to move? made diathermal? made

permeable to N1?

N ,V ,U

piston

Postulate I

(empirically verified ) S, the entropy, is a state function of U and other extensive variables

S(U,V,N...). The equilibrium values of the unconstrained intrinsic variables are those that

maximize S in the absence of internal constraints S(U, V, N) = max S(U, V, N,X1,...,Xn), where

we maximize with respect to the variables X.

Implies the second law of thermodynamics since S without the constraint is at a maximum.

Therefore any other state of the system, including one where a constraint is imposed, must be of

equal or lower entropy. After the removal of an internal constraint,

Sfinal Sinit 0

9/16/98

U. Penn.

Fall 1998

J. G. Saven

Postulate II

Entropy is extensive and is a monotonically increasing

function of the energy.

S/ N

Homogeneous functions

Consider a system that is broken up into m subsystems.

N 1 , V1

U/ N

N 2 , V2

N m , Vm

Let all the subsystems be equivalent and identical: Si=So for each i.

m

S = S(U,V,N) =

m different subsystems

S (U,V,N) = m So (Uo No, Vo)

S (mUo mNo, mVo) = m S(Uo No, Vo)

(turns out this is true for any value of m)

S is an extensive function

S (U,V, N) = S (U , V, N)

same entropy function in each case

S (U,V, N) = S (U , V, N)

Let = N-1

N-1 S (U,V, N) = S (N-1 U, N-1 V, 1)

S (U,V, N) = NS U , V, 1

N N

= NS (u, v, 1) = N s(u,v)

Thus S scales like size of system. s(u, u) is entropy per mole.

S = Ns, V = Nv, U = Nu

S = (mu, mv, m) = m s (u, v)

S (and the other extensive variables) are said to be a homogeneous function of order 1.

9/16/98

U. Penn.

Fall 1998

J. G. Saven

Lets return to considering the internal energy U. Compute the first differential since we are

interested in small changes.

U

U

U

dU =

dS +

dV +

dN

S V , N

V S , N

N S , V

Define intensive parameters

U

S

=T

temperature

V,N

= P

V S , N

pressure

= chemical potential

N S , V

These definitions agree with our picture of each quantity, and this will be shown when we

discuss equilibria. Note that these quantities are independent of the amount of matter N. Such

quantities are called intensive properties or intensive variables.

The following is also known as the first law of thermodynamics: energy can be converted into

different forms but it is conserved.

dU = TdS - PdV + dN

Note for a quasi-static process with N = constant

dU = dQ + dW

dQ = TdS

reversible heat flow

= TdS - PdV

dW

Heat flow is associated with a change in the entropy S. Note that each intensive variable is

associated with a derivative with respect to an extensive variable e.g.,

1 S

=

T U V , N

U and T are said to be conjugate variables (in the entropy representation). We now apply the

entropy extremum principle (Postulate I) and note its implications.

9/16/98

U. Penn.

Fall 1998

J. G. Saven

Equilibria

In maximizing S, we must find a state where

dS = 0.

N ,V ,U

1

internal variables are conserved for any process

N ,V ,U

dN = 0, matter is conserved

piston

dV = 0, the total volume does not change

dU = 0, energy is conserved

S1

S1

S1

dS =

dU1 +

dV1 +

dN1

U 1 V1N1

V1 U1N1

N 1 V1N1

S2

S2

dU2 +

U 2

V2

V2N2

S2

dV2 +

N 2

U2N2

dN2

V2U2

U1 + U2 = constant. dU1 = - dU2

V1 + V2 = constant. dV1 = - dV2

N1 + N2 = constant. dN1 = - dN2

dS = (

S

U 1

+ (

S

N 1

S1

U 1

V1N1

S1

V1

V1N1

U 2

S

N 2

dU1 + (

V2N2

S

V1

)

U2V2

S

V2

)

U2N2

dN1

U2V2

= 1

T1

U1N1

=

U1V1

U1V1

S

N 1

S

U 1

U 1

V1N1

S1

U 1

V1

S1N1

= -1 (-P1) = P 1

T1

T1

U 1

V1N1

N 1

V1S1

= -1 1

T1

T1

T2

T1 T2

T1

T2

Thermal Equilibrium

(dV1 = 0, dN1 = 0)

9/16/98

dV1

U. Penn.

Fall 1998

J. G. Saven

We will assume the wall is adiabatic and switched to diathermal. By so doing, we remove an

internal constraint. What is final state of the system?

We have a system with a diathermal wall that permits heat flow between the two subsystems.

V and N can not change since the wall is fixed and impermeable.

diathermal wall

adiabatic wall

N2, V2, E2

N1, V1, E1

N2, V2, E2

N1, V1, E1

heat

adiabatic wall

adiabatic wall

Therefore,

dU1 + dU2 = 0

dV1 = dV2 = 0

No volume change

dS = 0 (entropy at maximum)

= d(S1 + S2)

dS =

But

So

S1

U 1 V5N1

dU1 +

S2

U 2 V2,N2

dU2

dU1 = -dU2

0 = 1 1 dU1

T1 T2

1 = 1

T1 T2

At equilibrium, the temperatures of the two subsystems are equal.

Initially let T1 > T2. When remove internal constraint, the entropy must increase S > 0. Entropy

will at a maximum for the new equilibrium conditions. Any other state must be of lower S, e.g,

the initial conditions.

S 1 1

T1 T2

<0

9/16/98

U1

<0

6

U. Penn.

Fall 1998

J. G. Saven

U1 < 0 energy flows from hot (high T1) to cold (low T2). Since V is fixed, energy must

flow in the foam of heat Q. Vice versa for T2 > T1 , (U1 > 0).

Mechanical Equilibrium

(dN1 = 0)

moveable, diathermal wall

fixed, adiabatic wall

N2, V2, E2

N1, V1, E1

N2, V2, E2

N1, V1, E1

heat

adiabatic wall

adiabatic wall

U1 + U2 = constant

V1 + V2 = constant

S i

dS =

U i ViWi

i=1

S i

Vi U iN i

dUi +

S i

S i

Vi UiNg

dVi

U i

U i NiVi Vi S iN i

= - ( 1 ) (- Pi)

Ti

dS = 1 1 dU1 + +P 1 + -P2 dV1 = 0

T1 T2

T1

T2

Since

dU1 = - dU2,

dV1 = - dV2

Since dU1 and dV1 are each independent and arbitrary, we have

1 = 1

T1 T2

and

P 1 = P2

T1 T2

T1 = T2

P1 = P2

Let

9/16/98

U. Penn.

S = 1 (P1 P2) V1

T

>0

>0

>0

Fall 1998

J. G. Saven

S, V small

V1 must be V1 > 0. That is, the volume of 1 gets bigger due to its higher initial pressure P 1.

The volume of 2 gets smaller.

Equilibrium with respect to Matter Flow

Permeable, fixed wall:

dV1 = 0

fixed wall

N2, V2, E2

N1, V1, E1

N1, V1, E1

adiabatic wall

dS = 1 1 dU1 +

T1 T2

N2, V2, E2

adiabatic wall

1

+ 2 dN1

T1

T2

and

1 1 =0

T1

T2

1

+ 2

T1

T2

T1 = T 2

1 = 2

1 > 2

S =

1

+ 2 dN1 = 1 (2 1) dN1

T

T

T

>0

<0

N1 < 0 if S > 0

Matter flows out of region 1. Matter flows from high to low .

Chemical Equilibrium

9/16/98

U. Penn.

U, V are fixed.

Fall 1998

2 H2 + 1 02

- 1

- 2

(reactants: < 0)

closed, adiabatic container.

Turn on chemical reaction.

J. G. Saven

2 H2O

3

stoichiometric coefficients

(products > 0)

Let be a variable that measures the extent of the reaction. Given some small change d, the

stoichiometric coefficients provide the change in the number (of moles) of each type of species:

dN3 = 3 d then dN2 = + 2 d

and dN1 = + 1 d

The other temperature and pressure equilibria still hold. We then have

j

dNj

T

j=1

r

dS =

r

d

j j

T j

=1

r

dS = 0

j j = 0

j=1

Formal structure

U = U (S, V, N)

S = S (U, V, N)

T = T (S, V, N),

P = P (S, V, N) .....

but the functions U and S contain more information since they dictate the equilibrium state of the

system.

Minimizing the energy is equivalent to maximizing the entropy

Let X denote other internal extensive variables of the system, such as the volume V.

The entropy maximization principle states that for fixed total internal energy U, the values of

any unconstrained internal parameters are those that maximize the entropy S.

Similarly, the energy minimization principle states that for constant entropy S, the values of

any unconstrained internal parameters are those that minimize the energy.

9/16/98

U. Penn.

Fall 1998

J. G. Saven

B

B

n

xte

er e

oth

Energy

plane of constant S

sive

s

ble

ia

var

rgy

Ene

for process B: S = q/T = E > 0

What if we didn't minimize the internal energy? Let's say U Umin for some point that is

consistent with a particular value of the entropy. If this were the case then, we could extract

energy as work without changing the entropy (process A in the figure) and then put that same

amount of energy back into the system as heat (process B) thereby increasing S without changing

the overall energy. S would not be at a maximum!

The equilibrium state must satisfy both extremum conditions. Thus we can work or either energy

on entropy representations and we have conditions (equalities) to guide us to equilibrium. Is there

a general way to transform to other useful representations for cases where other extensive or

intensive variables naturally describe the state of the system, e.g., T = constant.?

Legendre Transforms

Legendre transforms provide a useful way to convert a function of many variables f(X1 ..., Xn) to

one that is a function of some of the original variables and the derivatives of f with respect to the

others

f(X 1 ..., Xn ) g(X1,...,X i,U i+1,...,U n)

where Ui =

f

X i X j Xi

f = f (X1 ..., Xn)

df = Ui dXi

i =1

Let

9/16/98

10

U. Penn.

g= f

Fall 1998

J. G. Saven

U X

i

i = r +1

dg = df

(U dX

i

i = r +1

r

dg = Ui dXi +

i =1

+ Xi dUi )

X dU

i

i = r +1

g contains all the same information as f which we can recover by back-transforming the conjugate

variables.

Example I. Helmholtz free energy.

Given that we have a function (the internal energy) U(S, V, ni) that is a natural function of S,

V, ni , find a function A that is a natural function of T, V, ni

A = U (S, V, ni) ST = A (T, V, n)

A = U ST

dA = dU SdT TdS

= (TdS PdV + i dni) SdT TdS

i

i

A is known as the Helmholtz free energy. For a reversible process, it is equal to the

maximum possible work done by the system.

At constant T,

dA = dU TdS = dW

Thus, at constant temperature, the Helmholtz free energy is the maximum amount of energy

we can usefully extract from the system. Note that we can also have bound energy that can

not be usefully extracted due to any entropy changes that might occur.

Example II. Gibbs free energy.

Transform A(T, V, ni) to a natural function G(T, P, ni), where P is the pressure of the

system (fixed pressure).

-P and V are conjugate are conjugate variables.

G = A (PV)

G = A + PV

9/16/98

A

V T,ni

11

=P

U. Penn.

Fall 1998

J. G. Saven

dG = dA + PdV + VdP

= SdT PdV+ i dni + PdV + VdP

i

i

Example III (Transform back)

T, V, ni

V, ni, S

i

S=

A

T V ,ni

U = A (S) T = A + ST

dU = dA + TdS + SdT

= SdT PdV+ i dni + TdS + SdT

i

i

U = U (S, V, ni)

Note also that

dS = dU + P dV i dni,

T T

T

i

S=

AU

T

S = S (U, V, ni)

We already have conditions that specify equilibrium in the entropy and energy representations.

(1) For constant entropy, we need to minimize the internal energy U

9/16/98

dU = 0,

U(S, V, Ni)

12

U. Penn.

Fall 1998

J. G. Saven

dS = 0,

d2 S < 0

S(U, V, Ni)

at equilibrium

Note that for any arbitrary function f (Xi, ..., Xn) the total derivative and Hessian are

n

df =

i= 1

f

dXi

X i

d2f =

i= 1 j= 1

n

Generally

dn f =

i=1

dXi

2f

dXi dXj

X iX j

X i

From vector calculus we know we're at a minimum if d2f > 0, df = 0 and it max if df = 0,

d2f < 0.

Helmholtz Potential

Consider a system contained in a very large heat bath or reservoir. The system can exchange heat

with the reservoir. The reservoir is so large that for any energy exchange with the system, the

temperature of the reservoir remains constant T = TR; this property defines a thermal reservoir.

The system is subdivided in to two compartments 1 and 2. The value of any extensive

thermodynamic quantity is the sum for the two compartments:

S(U,V,N) = S1(U 1,V1,N1) + S2(U 2,V2,N2)

The total values of the internal energy and the entropy are the sum of those for both the system and

the reservoir.

UTOT = U + UR,

STOT = S + SR

9/16/98

13

U. Penn.

Fall 1998

J. G. Saven

Bath or Reservoir

T=TR

System

N1, V1, U1

N2, V2, U2

At equilibrium dUtot = 0,

d2Utot > 0,

dStot = 0

d2Stot < 0

dUtot = 0 implies that

T1dS1 + T2dS2 + TRdSR = T1dS1 + T2dS2 TR (dS1 + dS2) = 0

T1 = TR and T2 = TR

We already showed that at equilibrium the system and the reservoir have same temperature:

T = TR.

dUtot = dU + (T dSR PR dVR +

Ri

i

= dU + T dSR

but since

dStot = 0 = dS + dSR,

we have that

dS = dSR

= d (U TS) = 0

Similarly,

d2Utot = d (dUtot) = d (dU TdS)

= d2U Td2S , since T = constant.

Since we must minimize UTOT,

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14

dNRi )

U. Penn.

Fall 1998

J. G. Saven

d2 (U TS) > 0

d2Utot > 0

Thus we can define a new function whose natural variables are T, V, N, that is at a minimum for

equilibrium values of these quantities.

A U TS,

dA = 0,

d2A > 0

contact with heat reservoir), the internal (unconstrained) variables are those that minimize A, the

Helmholtz free energy.

Note that reservoir fixes T. N and V are also fixed.

Enthalpy minimum principle

For fixed P, N, V

H U + PV

dH = 0,

d2 H > 0

at equilibrium

For systems in contact with a pressure reservoir, the values of unconstrained internal

parameters are those that minimize the enthalpy.

Gibbs Potential Minimum Principle

N, P, T are fixed

G U TS + PV

dG = 0

d2G > 0

at equilibrium

At constant pressure and temperature, the values of unconstrained internal parameters are

those that minimize the Gibbs free energy.

General thermodynamic potential extremum principle

For system in contact with reservoirs that fix intensive variables (1R, 2R, ...), the values of

internal unconstrained parameters are those that minimize the thermodynamic potential U (1R,

2R, ...) at constant. (1R, 2R ...).

In other words, to determine the equilibrium values of unconstrained internal variables, minimize

the thermodynamic potential that is a natural function of those thermodynamic variables we want

fixed.

Masseiu Functions

Up till now we've just looked at Legendre transforms of the energy U. We could also Legendre

transforms of the entropy. These are known as Masseiu functions

For given N, V, we know that we need to maximize S at constant. U. What about at constant 1

T

(which is the conjugate variable of U). Let B be some new Legendre transform of the entropy.

9/16/98

15

U. Penn.

B=S

S 1 U

T

NV

d(- A ) = 0

T

dSTot = 0

d2STot < 0

-A

T

J. G. Saven

dA = 0

T = constant due to reservoir

d 2 S 1 d2 U < 0

T

d2 > 0

T = constant

or

d2(- A ) < 0

T

Fall 1998

The S-representation at constant U can be transformed to the A-representation at constant T.

Masseiu function

Representation

Thermodynamic Potential

S (U, N, V)

Microcanonical

Entropy

Canonical

(T, , V) or U (T, , V) or

J(T, , V)

Grand Canonical

Grand potential

Maxwell Relations

Many different possible partial derivatives in thermodynamics, but they're not all independent. We

can develop relations among them. For the Maxwell relations, we use the simple equality among

mixed second partial derivatives.

dU =

U

S

dS +

NV

( )

U

V

dV +

SN

U

N

dN = TdS PdV + dN

SV,S

( )

U = U

S V

V S

S

Similarly

9/16/98

P

V,N

T

P

=

S V , N V N , S

(T)

N,S

2 U

=

=

=

S N

S

S

2

U

=

=

N S

N

S

U

S

16

T

N

U. Penn.

Fall 1998

J. G. Saven

T

=

N S , V S N , V

So

P

N

=

V,S

S,N

For example, if T, V, and N are the natural variables, then

dA = SdT PdV + dN

and

S

P

P

S

=

;

=

;

V N,T T V,N

N T,V V N,T

N

=

TV

N,V

and T.

(N=constant.)

Coefficient of Thermal Expansion

V

=1

V T

Isothermal Compressibility

Adiabatic Compressibility

(constant. heat, no heat flow)

TdS = dQ = 0

V

= 1

V P

V

s = 1

V P

dQ

S

CP T =

T P dT P

dQ

S

CV T =

T V dT V

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17

U. Penn.

Fall 1998

J. G. Saven

We can show that CV is also equal to a derivative of the internal energy. Vary the internal energy

in such a way that the total volume is kept fixed: dUV

dUV = TdSV PdV = TdSV

dUV = T dSV

dTV

dTV

Thus,

U

S

= T = CV

T V

T V

for N=constant

CV = T

S

T

=T

S (U (T, V),V)

S

T

=

V

S (U (T, V),V)

U = U (T, V),

(Change of variables)

0

S

T

=

V

S

U

U

T

U

=1

T T

CV =

U

T

(a) "simplify" derivatives so that they are expressed in easily determined quantities, e.g., ,

CV, T. (Quantities such as G, A, and S are difficult to measure directly)

(b) Find relationships among physical parameters

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18

U. Penn.

Fall 1998

J. G. Saven

Example:

TV 2

CP C =

T

V

measure than CV. This gives easy way

to measure CV.

Stability Revisited

At equilibrium S is at extremum and S is at a maximum

Stability also has physical consequences, just as

dS = 0, d2S < 0.

dS = 0 did.

Now we will show that S must be a concave-down function of the internal energy U. Let us do

this by considering a case where S is at somepoint a concave-up function of U. We will show that

for a homogeneous system (not in the vicinity of a phase transition) that this is not physically

reasonable.

Consider 2 identical systems separated by an adiabatic

wall

N ,V ,U

stuff N is fixed and that the adiabatic piston is fixed (it

does not move). If the two subsystems are identical,

then the total entropy of the system is

N ,V ,U

2

Let us suppose that the entropy of each subsystem was at some point a concave-up function of U.

We could take U out of one side and add it to the other. New entropy is

S' = S1 (U + U) + S2 (U U)

Si

S

S'/2

S1 or S2

S/2

U-U

9/16/98

U

19

U+U

U. Penn.

Fall 1998

J. G. Saven

Note that S' > S ; the entropy increases upon redistributing the energy.

If we removed the adiabatic wall, energy would spontaneously flow from one side to the other.

Similar things would also happen within a homogeneous system. The system would be unstable.

[In some cases, e.g. near phase transition points, stability isn't satisfied and the system breaks up

into different phases or different types of matter (chemical reactions).]

In order for the system to be stable, we must have that

S (U + U) + S (U U) 2S (U, V, N)

V = constant.

N = constant.

2

S

U

0 ,

2

V, N

Similarly

S

V

2

U, N

increase the entropy S.

S

2

0

20

20

15

15

10

10

S (U, + U, V + V) + S (U U, V V) 2 (S (U, V))

N constant.

V 0, U 0

At a maximum, we must satisfy the above inequalities on the second derivatives of S as well as

2

S

U

9/16/98

S

V

S

UV

20

U. Penn.

Fall 1998

J. G. Saven

2

S

U

U U

V,N

=

V,N

1

U T

=

V,N

1 T

T2 U

=

N,V

1

0

T2 CV

CV 0

5

Internal Energy

S2

1

variables

2

U

S

2

V,N

T

S

40

0;

30

VN

20

U

V

2

N,S

P

V

10

0

2

4

dA = SdT PdV

U

T=

S=

A

T

N,V

2

S

T

N,V

=

N,V

A

T

2

N,V

T

S

=

N,V

U

S S

-1

= +

N,V

U

S

-1

2

NV

9/16/98

21

U. Penn.

Fall 1998

J. G. Saven

C

S

= V 0, A must be a concave down function of T. (Similarly with the other conjugate

T V

T

variables.)

(T, V, N) are the natural variables

A

T

-50

2

NV

-100

A

2 0

V T , N

2

-150

-200

0

30

15

20

10

10

600

2 H

0

2

S P, N

400

H

P

SN

200

10

7.5

9/16/98

22

5

2.5

0

10

U. Penn.

Fall 1998

J. G. Saven

G

T

-20

-2

PN

G

P

-40

-4

2

TN

-60

2

4

6

8

10

of extensive variables.

Here by thermodynamic potential, we mean the appropriate Legendre transform of the internal

energy U.

Physical Consequences of Stability

2 A

1

P

0

2 = =

V T

V T V T

0

CP easier to measure than CV for solids.

Condense with

TV 2

CP CV =

T

CV 0, T 0

C P CV 0

Le Chatelier's Principle

One way of stating Le Chateliers principle is to say that the system evolves so as to remove

inhomogeneities.

From microscopic (molecular) "chaos" we know that fluctuations induce local inhomogenity in

energy density, entropy density, particle density, etc.

9/16/98

23

U. Penn.

Fall 1998

J. G. Saven

density fluctuation

The thermodynamic potentials act as a sort of restoring force against inhomogeneous fluctuations

in the system.

Thermodynamics summary

From the postulates we see that we must either maximize S on minimize U at equilibrium.

The concept of equilibrium leads to equalities among intensive variables

Using the Legendre Transform, we can obtain a thermodynamic potential for any representation or

set of macroscopic intrinsic variables, e.g. G(T,P,N).

The Maxwell Relations provide useful relationships among the derivatives of thermodynamic

quantities.

From the concept of thermodynamic stability, we can obtain useful bounds and inequalities:

CP > CV > 0, T > S > 0

References

[1]

D. Chandler, Introduction to Modern Statistical Mechanics. New York: Oxford

University Press, 1987.

[2]

D. A. McQuarrie, Statistical Mechanics. New York: Harper & Row, 1976.

[3]

H. B. Callen, Thermodynamics and an Introduction to Thermostatistics, Second ed.

New York: John Wiley & Sons, 1985.

9/16/98

24

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