Chapter 5

Simple Applications of Macroscopic

Thermodynamics

Preliminary Discussion
Classical, Macroscopic, Thermodynamics
Drop the statistical mechanics notation for average quantities.
We know that All Variables are Averages Only!

Well discuss relationships between macroscopic

variables using

The Laws of Thermodynamics

Some Thermodynamic Variables of Interest:
Internal Energy = E, Entropy = S, Temperature = T

For Gases:
External Parameter = V, Generalized Force = p
(V = volume, p = pressure)

For A General System:

External Parameter = x, Generalized Force = X

 Assume the relevant External Parameter = Volume V in order to

have a specific case to discuss. For infinitesimal, quasi-static processes:

The 1st & 2nd Laws of Thermodynamics

1st Law: Q = dE + pdV
2nd Law: Q = TdS

The Combined 1st & 2nd Laws

TdS = dE + pdV
Note that, in this relation, there are 5 Variables:

T, S, E, p, V
It can be shown that:

Any 3 of these can always be expressed as functions

of any 2 others.
That is, there are always 2 independent variables & 3 dependent
variables. Which 2 are chosen as independent is arbitrary.

Now, A Brief, Pure Math Discussion

Consider 3 variables: x, y, z. Suppose we know that x & y are
Independent Variables. Then, It Must Be Possible to express z as
a function of x & y. That is, There Must be a Function z = z(x,y).
From calculus, the total differential of z(x,y) has the form:

dz (z/x)ydx + (z/y)xdy (a)

Suppose instead that we want to take y & z as independent

variables. Then, There Must be a Function x = x(y,z).
From calculus, the total differential of x(y,z) has the form:

dx (x/y)zdy + (x/z)ydz (b)

Using (a) & (b) together, the partial derivatives in (a) & those in
(b) can be related to each other.
We always assume that all functions are analytic. So, the 2nd cross
derivatives are equal: Such as

(2z/xy) (2z/yx),

etc.

Mathematics Summary
Consider a function of 2 independent variables: f = f(x1,x2).
Its exact differential is df y1dx1 + y2dx2, where, by definition:

Because f(x1,x2) is an analytic function, it is always true that

y2 y1

x1 x2 x2

x1

Most Ch. 5 applications use this with the

Combined 1st & 2nd Laws of Thermodynamics:

TdS = dE + pdV

Some Methods & Useful Math Tools

for Transforming Derivatives
Derivative Inversion
F

y F

P S

Triple Product (xyz1 rule)

H T P
F x y 1

T P P H H T
x y y F F x
Chain Rule Expansion to Add Another Variable
F

x y

S T

T P H

CP 1 1

T CP T

Maxwell Reciprocity Relationship

F x y

F y x

Fxy Fyx

Pure Math: Jacobian Transformations

A Jacobian Transformation is often used to
transform from one set of variables to another.
For functions of 2 variables f(x,y) & g(x,y) it is:
f

f , g x

x, y g

y
g

f g

x y y

f g

y x x
x

Determinant!

Jacobian Transformations
Have Several Useful Properties
Transposition

f , g
g , f

x, y
x, y

Inversion

f , g
1

x, y
x, y
f , g

Chain Rule
Expansion

f , g f , g z , w

x, y z , w x , y

 Suppose that we are only interested in the first

partial derivative of a function f(z,g) with respect
to z at constant g:

f , g

z, g

This expression can be simplified using the chain

rule expansion and the inversion property

f , g
x, y

z, g
x, y

Properties of the Internal Energy E

dE = TdS pdV

(1)

First, choose S & V as independent variables:

E E(S,V)
E
U
E
U

(2)
dE
dU
dS
dV
S V
V S
Comparison of (1) & (2) clearly shows that
U
E

and

T
V

U
E

p
S

Applying the general result with 2nd cross derivatives gives:

Maxwell Relation I!
V

If S & p are chosen as independent variables, it is

convenient to define the following energy:

H H(S,p) E + pV Enthalpy

Use the combined 1st & 2nd Laws. Rewrite them in terms of dH:

dE = TdS pdV = TdS [d(pV) Vdp] or

(1)
dH = TdS + Vdp
But, also:

(2)

Comparison of (1) & (2) clearly shows that

and

Applying the general result for the 2nd cross derivatives gives:
T
V

Maxwell Relation II!

p S S p

If T & V are chosen as independent variables, it is

convenient to define the following energy:

F F(T,V) E - TS Helmholtz Free Energy

Use the combined 1st & 2nd Laws. Rewrite them in terms of dF: dE

= TdS pdV = [d(TS) SdT] pdV or

dF = -SdT pdV (1)
But, also: dF (F/T)VdT + (F/V)TdV
(2)
Comparison of (1) & (2) clearly shows that

(F/T)V -S

and

(F/V)T -p

Applying the general result for the 2nd cross derivatives gives:

Maxwell Relation III!

If T & p are chosen as independent variables, it is

convenient to define the following energy:

G G(T,p) E TS + pV Gibbs Free Energy

Use the combined 1st & 2nd Laws. Rewrite them in terms of dH: dE
= TdS pdV = d(TS) - SdT [d(pV) Vdp] or
dG = -SdT + Vdp
(1)
But, also:
dG (G/T)pdT + (G/p)Tdp
(2)

Comparison of (1) & (2) clearly shows that

(G/T)p -S

and

(G/p)T V

Applying the general result for the 2nd cross derivatives gives:

Maxwell Relation IV!

Summary: Energy Functions

1. Internal Energy:
2. Enthalpy:
3. Helmholtz Free Energy:
4. Gibbs Free Energy:

Combined 1st &

2nd Laws

E E(S,V)
H = H(S,p) E + pV
F = F (T,V) E TS
G = G(T,p) E TS + pV

1. dE = TdS pdV
2. dH = TdS + Vdp
3. dF = - SdT pdV
4. dG = - SdT + Vdp

Another Summary: Maxwell Relations

(a) E = Q + W
(b) S = (Qres/T)
(c) H = E + pV
(d) F = E TS
(e) G = H - TS

1. dE = TdS pdV
2. dH = TdS + Vdp
3. dF = -SdT - pdV
4. dG = -SdT + Vdp

V
S

1.
S

3.
T

2.

4.

z
z
dy
Mdx Ndy dz
dx
x y
y x
M

Maxwell Relations: The Magic Square?

Each side is labeled with an

Energy (E, H, F, G).

The corners are labeled with

Thermodynamic Variables

(p, V, T, S).
Get the

Maxwell Relations
by walking around the
square. The partial
derivatives are obtained
from the sides. The

Maxwell Relations

are obtained from the corners.

P
16

Summary
The 4 Most Common
Maxwell Relations:
T

V
T

V
S

P
17

Maxwell Relations: Table (E U)

18

Maxwell Relations
Maxwell Relations from dE, dF, dH, & dG
Internal
Energy
Helmholtz
Free Energy
Enthalpy
Gibbs Free
Energy

Some Common Measureable Properties

Heat Capacity at Constant Volume:

Heat Capacity at Constant Pressure:

Volume Expansion Coefficient:
Note!!
Reifs notation
for this is

Isothermal Compressibility:
The Bulk Modulus is inverse of the
Isothermal Compressibility!!

B ()-1

Some Sometimes Useful Relationships

Summary of Results
Derivations are in the text and/or left to the student!

Entropy:
Enthalpy:
V
H
G
Gibbs Free Energy: d
dP
dT

2
RT
RT
RT

A Typical Example
Given the entropy S as a function of temperature T &
volume V, S = S(T,V), find a convenient expression for
(S/T)P, in terms of some measureable properties.
Start with the exact differential:
Use the triple product
rule & definitions:
Use a
Maxwell Relation:
Combining these
expressions gives:

 Converting this to a partial derivative gives an identity:

This can be rewritten as:

The triple product rule is:
Substituting gives:

Note again the definitions:

Note!! Reifs
notation for
this is

Volume Coefficient of Expansion

V-1(V/T)p
Isothermal Compressibility

-V-1(V/p)T

 Using these in the previous expression finally gives the

desired result:
Using this result as a starting point, A GENERAL
RELATIONSHIP between The Heat Capacity at Constant
Volume CV & The Heat Capacity at Constant Pressure Cp
can be found:

Simplest Possible Example: The Ideal Gas

For an Ideal Gas, its easily shown (Reif) that the

Equation of State (relation between pressure P, volume V,
temperature T) is (in per mole units!):
P = RT.
With this, it is simple to show that the volume expansion
coefficient & the isothermal compressibility are:
1 v
1 RT
R
R



v T P v T P P vP RT
1

and
T
1 v
1 RT
RT RT


2
v P T
v P P T vP RTP
1

 So, for an Ideal Gas, the volume expansion coefficient

& the isothermal compressibility have the simple forms:
and
We just found in general that the heat capacities at
constant volume & at constant pressure are related as

So, for an Ideal Gas, the specific heats per mole

have the very simple relationship:

Other, Sometimes Useful, Expressions

H P .T

V
V T
dP
T P
P 0

CONSTANT T

SP .T

T
P 0

CONSTANT T

R
dP
P

CONSTANT T

R
dV
V

T
P 0
P

SV .T

More Applications: Using the Combined

1st & 2nd Laws (The TdS Equations)
Consider Two Identical Objects, each of mass m, &
specific heat per kilogram cP. See figure next page.

Object 1 is at initial temperature T1.

Object 2 is at initial temperature T2.
Assume T2 > T1.
When placed in contact, by the 2nd Law,
heat Q flows from the hotter (Object 2) to
the cooler (Object 1), until they come to a
common temperature, Tf.

 Two Identical Objects, of mass m, & specific heat per

kilogram cP. Object 1 is at initial temperature T1. Object
2 is at initial temperature T2.
T2 > T1. When placed in contact, by the 2nd Law, heat Q
flows from the hotter (Object 2) to the cooler (Object
1), until they come to a common temperature, Tf.
For some time
after the initial
contact:

Object 2
Initially
at T2

Q
Heat Flows

Object 1
Initially
at T1

After a long enough time, the two objects are at the same
temperature Tf. Since the 2 objects are identical, for this case,

T1 T2
Tf
2

 The Entropy Change S for this process can be easily

calculated:
Tf
T f dT
Tf
dT
ln

S mcP

mcP ln

T2 T
T1 T

T2
T1
2
2

Tf
Tf
T
f

mcP ln
mcP ln

2
mc
ln

TT
TT
T
T

1
2
1 2
1 2

T1 T2

S 2mcP ln
T1 T2 2 T1T2
2 TT
1 2

2
2

Tf

Of course, by the 2 Law,

the entropy change S must
be positive!! This requires
that the temperatures satisfy:
nd

T1 T2 2T1T2 4T1T2
T12 T22 2T1T2 0
(T1 T2 ) 0
2

Some Useful TdS Equations

NOTE: In the following, various quantities are written in per mole
units! Work with the Combined 1st & 2nd Laws:
Definitions:

Number of moles of a substance. (V/) Volume per mole.

u (U/) Internal energy per mole. h (H/) Enthalpy per mole.
s (S/) Entropy per mole. cv (Cv/) const. volume specific heat per mole.
cP (CP/) const. pressure specific heat per mole.

T
P
Tds cv dT T
dv
dv cv dT

T v
v
Tds cP dT T
dP cP dT TvdP
T P
cP
cv
T
T
Tds cP
dv
dP
dv cv
dP
v

v P
P v

Internal Energy u(T,)

u

du

dT

v
v

u
Tds cv dT

dv
T

P dv

Enthalpy h(T,P)

Entropy
s s ( P, v )

Consider

s
s
dP

dv
P v
v P
1 Ts T
s
s T

P
T

v
v
v

c T
s

P
T

v
ds

dP
P v

s
s

P
P
ds

cP
T

s
dv
v P
T

v
P

s
s
3
ds
dP
dv
P v
v P
cv T
cP T
ds
dP
dv
T P v
T v P

T
T
Tds cv
dP cP
dv
P v
v P

2
1 Ts T

T T P v