Mathematical Theorems

The equation of state provides the relationship between theromodynamic properties for ideal gas as
well as for incompressible substances. However, simple equation of state is not enough to describe
the thermodynamic properties for systems with real and complex materials. Hence, more
mathematical equations are required to represent the realistic processes. Amongst the various
thermodynamic properties, p, v, T are directly measurable whereas u, h, s is not directly measurable.
This necessitates for developing thermodynamic relations apart from the equation of states.

The following three theorems are the base for developing the various thermodynamic relations.

Theorem-1 If a relation exists among the variables x, y, and z, then z may be expressed as a function
of x and y.

or,

1.70

If,

1.71

and

1.72

Then,

dz = M dx + N dy 1.73
where M and N are functions of x and y. Differentiating M partially with respect to y and N with respect
to x,

1.74

And,

1.75
Hence,

1.76

This is the condition of an exact (perfect) differential. If x and y are two independent thermodynamic
properties, then Z (or z) will be also a thermodynamic property provided it satisfy Eq. (1.76). For
example, let us consider the following relation,

dz = p dv + v2 dp 1.77
Here, M = p and N = v2

Now, and which does not satisfy Eq. (5.76). Hence Z is not a
thermodynamic property.

Let us consider another relation,

z = p dv + v dp 1.78
With similar reasoning it can be easily established that Z is a thermodynamic property in this case.

With more than 3 variables, say x1, x2, x3 and Z,

Z=(x1, x2, x3) 1.79

1.80

For dz to be an exact differential,

1.81

For k number of variables

1.82

or,

1.83
Theorem 2 If a quantity f is a function of x, y, and z, and a relation exists amongst x, y and z, then
f is a function of any two of x, y, and z.
ƒ = ƒ(x, y, z) 1.84
or,

x = x(y, z) 1.85

x = x(ƒ, y) 1.86

x = x(ƒ, z) 1.87
If x = x(ƒ, y)

1.88

Similarly, if y = y(ƒ, z)

1.89

From Eqs. (1.88) and (1.89), we have

1.90

or,

1.91

If ,x = x(ƒ, z) then

1.92

From Eqs. (1.91) and (1.92),

1.93

Eq. (1.93) can be rewritten as

1.94
Theorem 3 Among the variables x, y, and Z, any one variable may be considered as a function of the
other two. Thus,

x = x(y, z) 1.95

1.96

Similarly,

z = z(x, y) 1.97

1.98

Hence,

1.99

or,

1.100

or,

1.101

Hence,

1.102

or,

1.103
Maxwell Relations

A pure substance existing in a single phase has only two independent variables. Out of the eight
quantities p,V,T,S,U,H,F, and G any one may be expressed as a function of and other two quantities.

For a pure substance undergoing an infinitesimal reversible process

dU = TdS -pdV 1.104

dH = dU +pdV + Vdp = TdS + Vdp 1.105

dF = dU - TdS - SdT = -pdV - SdT 1.106

dG = dH - TdS - SdT = Vdp - SdT 1.107

Applying this to the four equations (Eqs. (1.104-1.107))

1.108

1.109

1.110

1.111

Equations (1.108-1.111) are known as Maxwell relations.

Fig. 1.18 Thermodynamic mnemonic diagram

Mark the positions at the middle of the sides as well as at the corners. Write down the variables G, P,
H, S, U, V, F and T starting from the middle of left hand side and in anti clockwise direction. The
relations (Table 1.8) for du, dh, dF and dG can be easily memorized by using the phrase

G reat P hysicists H ave S tudied U nder V ery F amous T eachers

(G,P,H,S,U,V,F,T) by considering this thermodynamic mnemonic diagram. Diagonals are then drawn
pointing away from the two bottom corners. Now, if an expression for dG is required (that is located
at the middle of the line connecting the points T and p ), we first form the differentials of dT and dp,
and then link the two with their conjugates as illustrated below:

dG = -S ( conjugate of T with the minus sign due to the diagonal pointing towards T ) x dT +V (that
is conjugate of P with the plus sign due to the diagonal pointing away from P) x dp

Table 1.8 Maxwell relations

Differential Conjugate Maxwell Relation Remarks

h dh = Tds + pdv T, v h = h(s,p)

f dƒ = -sdT - pdv -s, -p ƒ = ƒ(T, v)

g dg = -sdT + vdp -s, v g = g(T, p)