Thermodynamics

Y Y Shan

Chapter 5 Thermodynamic properties of materials

Introduction:
The thermodynamic properties of materials are intensive quantities which are
specific to a given material, such as the specific heats, cV , and c P of materials , introduced in
Chapter 2. There are some other experimentally measurable properties, such coefficients of
thermal expansion and compressibility. Each is directly related to a second order differential
of a thermodynamic potential defined later in this chapter.
(i)

Specific heat of materials ( cV , and c P ): also known simply as heat capacity

( CV = ncV , and C P = nc P ), is the measure of the heat energy required for a unit quantity of a
substance ( n = 1mol ) to increase 1 degree temperature

Specific heat at constant volume

dQ
S
CV =
= T

dT V
T V

5-1a

Specific heat at constant pressure

dQ
S
CP =
= T

dT P
T P

5-1b

(ii) Coefficient Thermal expansion : is the tendency of matter to change in volume in

response to a change in temperature. The degree of expansion divided by the change in
temperature is called the material's coefficient of thermal expansion

Coefficient of thermal expansion

1 V

V T P

5-1c

(iii) Compressibility : is a measure of the relative volume change as a response to a

pressure change

Coefficient of compressibility

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1 V

V P T

5-1d

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These material properties, Specific heat C, thermal expansion , and Compressibility , can
be experimentally determined.

1.

Thermodynamic potentials
In thermodynamics, thermodynamic potentials are parameters associated with a

thermodynamic system and have the unit of energy (Joule).

Thermodynamic potentials are very useful when calculating the properties of
materials in a chemical reaction, which are very difficult to be measured.

They are

characterized by the basic four variables: P&V(mechanical natural variable), T& S(thermal
natural variable) respectively, where P, T are called generalized forces, and V,S are called
generalized displacements introduced in Chapter 4.

There are four thermodynamic

potentials: the internal energy U, the enthalpy H, the Helmholtz free energy F, and the Gibbs
free energy G.

Internalenergy:

dU = TdS PdV

U is characterized by S, V. If function U(S, V) is known, T and P obtained

Enthalpy:

defined as : H = U + PV
dH = dU + d ( PV ) = (TdS PdV ) + ( PdV + VdP )

dH = TdS + VdP
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H is characterized by S, P. If function H(S, P) is known, T and V can be obtained

Helmholtz free energy: defined as : F = U TS
dF = dU d (TS ) = (TdS PdV ) (TdS + SdT )

dF = SdT PdV
If function F(T, V) is known, S and P can be obtained

Gibbs free energy: defined as : G = U + PV TS

dG = dU + d ( PV ) d (TS )

dG = SdT + VdP
G is characterized by T, P. If G(T, P) is known, S and V can be obtained

These four thermodynamic potentials, U(S,V) , H(S,P) , F(T,V) , and G(T,P), introduced
above are summarized as the follows:

dU ( S , V ) = TdS PdV ,
dH ( S , P ) = TdS + VdP
dF (T , V ) = SdT PdV

Eqn5-2

dG (T , P ) = SdT + VdP
---------------------------------------------------------------------(*Because the mixed partial derivatives are identical:

Z
Z
2Z 2Z
Q = =
=
y x y x y x yx xy
Therefore thermodynamic properties of materials Specific heat C, thermal expansion , and
Compressibility , each can be directly related to a second order differential of a
thermodynamic potential defined in Eqn5-2.

2F
2G
1 2G
1 2G
CV = T
, C P = T
, =
, =
T 2
T 2
V P 2
V PT
On the other hand, they can be experimentally determined. Therefore thermodynamic
potentials can be calculated, and vise verse)
--------------------------------------------------------------------

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2. Maxwell's relations and their applications

2.1. Derivation: Maxwells relations are a set of four equations derived from the
definitions of the corresponding four thermodynamic potentials, in Eqn 5-2.
In mathematics, for a function Z ( x, y ) , its differential is known to be:

Eq5-3a
i.e.

Z
Z

M =
, N =
x y
y x

Eq5-3b

Because the mixed partial derivatives are identical:

Z
Z
2Z 2Z
Q = =
=
,
y x y x y x yx xy
M

2Z
2Z
N
=
,
=
x yx x y xy

Thus:

M

y

N
=

y
x

Eq5-3c

------------------------------------------------------------------------* Triple product rule

For Z ( x, y ) :

Z
Z
,
, N =

y
x y

dZ ( x, y ) = Mdx + Ndy , M =

when Z is fixed, i.e. dZ = 0 ,

Mdx = Ndy ,

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M
N

x
= 1 ,
y Z

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Z y x
= 1

x y Z x y Z

Eq5-3d

This is called the Triple Product Rule.

------------------------------------------------------------------------If we replace this general function Z ( x, y ) by those four thermodynamic potentials
defined earlier: U(S,V) , H(S,P) , F(T,V) , and G(T,P), applying Eq5-3cthis general result
to the four four thermodynamic potentials, the Maxwells relation is derived.
For e.g., from enthalpy H(S,P):

dZ ( x, y ) = Mdx + Ndy
dH ( S , P) = TdS + VdP

M
N
=

x
T
V

=

P S S P

H
H
, V =
. This is one of the four Maxwells relations.
S P
P S

where T =

Similarly, the following can be obtained:

dU = TdS PdV ,
dH = TdS + VdP,

T
P

=-
V S
S V
T
V
=+

P S
S P

S P
dF = SdT PdV ,
=
V T T V
S
V
dG = SdT + VdP, = -

P T
T P

eqn5-4

(= P )
( = V )

The four equations on the right are known as the Maxwells relations

2.2 Some application of Maxwells relations in determining material properties

The importance of the Maxwells relations:

in thermodynamics, some physical

quantities, such as P, T, V are easy to be measured, and therefore the state equation
f(P,V,T)=0 can be obtained experimentally, such as

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PV = nRT .
Also thermal expansion coefficient , Compressibility , pressure coefficient , Specific
heats Cp, Cv, can be measurable:

1 V
1 V
1 P

, =
, =

V T P
V P T
P T V

P = / (the Triple Product Rule, Eq5-3d is appled)

But there are some other quantities are either cannot be measured or very difficult to
measure, such as entropy. By using Maxwells relation, one can determine changes of
entropy through measurable quantities of P,V, T, and CV , C P , , , as:

S P

= = P S (T ) = PdV
V T T V
Maxwells relations are enormously useful, they provide relationships between measurable
quantities and those quantities which are not measurable or difficulty to be measured.
Each partial derivative in Maxwells relations represents a relationship between two
physical quantities in a thermodynamic process under a specific condition for e.g.,
This mathematical expression of partial derivative,

,
V T
,when it is translated to thermodynamic language, it means the relationship between entropy
S and volume V in a constant temperature process.
The following Maxwell relation,

T
V
=+
,
P S
S P
, in thermodynamic language, means the temperature variation vs. the change of pressure in
a constant entropy process (adiabatic process) is the same as the volume variation against the
change of entropy in a isobaric process(constant pressure process)

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Example 1: To determine the change of internal energy in respect with the change of volume

V T

for an isothermal process:

(i) for ideal gas , (ii) for van der Waals gas.
For U = U (T ,V )

dU = TdS PdV
S
S
Since mathematically: dS (T ,V ) =
dT +
dV ,
T V
V T

S
S
dU = TdS PdV = T [ dT +
dV ] PdV )
T V
V T
S
S
dU = T
dT + [T
P]dV
T V
V T

i.e.

(a)

Also mathematically:

U
U
dU (T , V ) =
dT +
dV
T V
V T

(b)

Comparing (a) with (b), therefore:

U
S
U
= CV

= T
, here
T V
T V
T V
U
S

= T
P
V T
V T

(c)

U
S . Though S could not be measured easily,
To obtain
, we need to get

V T
V T
V T
however by applying the Maxwells relation:

S
P

=
( dF = SdT PdV )
V T T V
Equation (c) becomes:

U
P

= T
P
T V
V T

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Eqn5-5

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The left side is difficult to measure, while the right side can be obtained when the state
equation f ( P, V , T ) is available.
(i) For ideal gas: the state equation: PV = nRT

nR
U
P
P=PP=0

= T P = T
V
V T
T V
This is Joles law introduced in Chapter 2, and it is proved now. It tells that internal energy of
an ideal gas is not volume dependent in an isothermal expansion process. It is temperature
dependent.
(ii) For van der Waals gas, the equation of state is:

(P +

a
)(V b) = nRT , where a and b are the constants.
V2

nR
a
a
U
P
P = (P + 2 ) P = 2

= T P = T
V b
V
V
V T
T V
The change of internal energy is volume dependent.

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