Chapter 7

THERMODYNAMIC
RELATIONS
7.1 Mathematical Relations
• Partial Differentials
• Now consider a function that depends on two (or more)
variables, such as z = z(x, y). This time the value of z
depends on both x and y. It is sometimes desirable to
examine the dependence of z on only one of the variables.
The variation of z(x, y) with x when y is held constant is
called the partial derivative of z with respect to x, and it
is expressed as

(7.1)
• This is illustrated in Fig. 7.1. To obtain a relation for the
total differential change in z(x, y) for simultaneous changes
in x and y, consider a small portion of the surface z(x, y)
shown in Fig. 7.2.

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 Fig 7.1 Geometric Fig 7.2 Geometric
representation of partial representation of total
derivative (z/x)y. derivative dz for a function
z(x, y). 3
• When the independent variables ∆x and ∆y change by x
and y, respectively, the dependent variable z changes by ∆z,
which can be expressed as

• Adding and subtracting z(x, y + ∆y), we get

• or

• Taking the limits as ∆x → 0 and ∆y → 0 and using the

definitions of partial derivatives, we obtain

(7.2)

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• Partial Differential Relations
• Now let us rewrite Eq. 7.2 as
(7.4)
• where

Taking the partial derivative of M with respect to y and

of N with respect to x yields

• Therefore, the two relations above are identical:

(7.5)
• Then the total differential of x becomes, from Eq. 7.2,
(7.6)

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• Eliminating dx by combining Eqs. 7.2 and 7.6, we have

• Rearranging,

(7.7)
• Setting the terms in each bracket equal to zero gives

(7.8)

(7.9)
• The first relation is called the reciprocity relation, and it
shows that the inverse of a partial derivative is equal to its
reciprocal. The second relation is called the cyclic relation,
and it is frequently used in thermodynamics
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 7.2 THE MAXWELL RELATIONS
• The equations that relate the partial derivatives of
properties P, v, T, and s of a simple compressible system to
each other are called the Maxwell relations.
• Two of the Gibbs relations were derived in Chap. 5 and
expressed as
(7.10)
(7.11)
• The other two Gibbs relations are based on two new
combination properties - the Helmholtz function a and the
Gibbs function g, defined as
(7.12)
(7.13)
• Differentiating, we get

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• Simplifying the above relations by using Eqs. 7.10 and 7.11,
we obtain the other two Gibbs relations for simple
compressible systems:
(7.14)
(7.15)
• A careful examination of the four Gibbs relations reveals
that they are of the form
(7.4)
• with

(7.5)

• since u, h, a, and g are properties and thus have exact

differentials. Applying Eq. 7.5 to each of them, we obtain

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 (7.16)

(7.18)

(7.19)

(7.20)

• These are called the Maxwell relations. They are

extremely valuable in thermodynamics because they provide
a means of determining the change in entropy, which cannot
be measured directly, by simply measuring the changes in
properties P, v, and T.
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 7.3 General Relations for du, dh, ds, Cv, and Cp

7.3.1 Internal Energy Changes

• We choose the internal energy to be a function of T and v;
that is, u = u(T, v) and take its total differential (Eq. 7.2):

• Using the definition of cv, we have

(7.21)
• Now we choose the entropy to be a function of T and v; that
is, s = s(T, v) and take its total differential,

(7.22)
• Substituting this into the Tds relation du = Tds - Pdv yields
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 (7.23)
• Equating the coefficients of dT and dv in Eqs. 7.12 and 7.23
gives

(7.24)

• Using the third Maxwell relation (Eq. 7.18), we get

• Substituting this into Eq. 7.21, we obtain the desired

relation for du:
(7.25)

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• The change in internal energy of a simple compressible
system associated with a change of state from (T1, v1) to
(T2, v2) is determined by integration:

(7.26)

7.3.2 Enthalpy Changes

• This time we choose the enthalpy to be a function of T and
P, that is, h = h(T, P), and take its total differential,

• Using the definition of cp, we have

(7.27)

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• Now we choose the entropy to be a function of T and P; that
is, we take s=s(T, P) and take its total differential,

(7.28)
• Substituting this into the T ds relation dh =Tds +vdP gives

(7.29)
• Equating the coefficients of dT and dP in Eqs. 7.27 and
7.29, we obtain

(7.30)

• Using the fourth Maxwell relation (Eq. 7.19), we have

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• Substituting this into Eq. 7.27, we obtain the desired
relation for dh:

(7.31)
• The change in enthalpy of a simple compressible system
associated with a change of state from (T1, P1) to (T2, P2) is
determined by integration:

(7.32)
• The other can easily be determined by using the definition of
enthalpy h = u + Pv
(7.33)

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7.3.3 Entropy Changes
• Below we develop two general relations for the entropy
change of a simple compressible system.
• The first relation is obtained by replacing the first partial
derivative in the total differential ds (Eq. 7.22) by Eq. 7.24
and the second partial derivative by the third Maxwell
relation (Eq. 7.18), yielding

(7.34)
• and

(7.35)
• The second relation is obtained by replacing the first partial
derivative in the total differential of ds (Eq. 7.28) by Eq.
7.30, and the second partial derivative by the fourth Maxwell
relation (Eq. 7.19), yielding
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 (7.36)
• and

(7.37)
7.3.4 Specific Heats cv and cp
• At low pressures gases behave as ideal gases, and their
specific heats essentially depend on temperature only.
These specific heats are called zero pressure, or ideal-gas,
specific heats (denoted cv 0 and cp0), and they are relatively
easier to determine. Thus it is desirable to have some
general relations that enable us to calculate the specific
heats at higher pressures (or lower specific volumes) from a
knowledge of cv 0 or cp 0 and the P-v-T behavior of the
substance. Such relations are obtained by applying the test
of exactness (Eq. 7.5) on Eqs. 7.34 and 7.36, which yields
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 (7.38)
• and

(7.39)

(7.40)

• We start the development of a relation by equating the two

ds relations (Eqs. 7.34 and 7.36 and solving for dT:

• Choosing T = T(v, P) and differentiating, we get

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• Equating the coefficient of either dv or dP of the above two
equations gives the desired result:

(7.41)
• An alternative form of this relation is obtained by using the
cyclic relation:

• Substituting the result into Eq. 7.41 gives:

(7.42)
• This relation can be expressed in terms of two other
thermodynamic properties called the volume expansivity
b and the isothermal compressibility a, which are
defined as (Fig. 7.3)
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Fig 7.3 The volume expansivity (also called the coefficient of
volumetric expansion) is a measure of the change in volume
with temperature at constant pressure. 19
 (7.43)
• and
(7.44)

• Substituting these two relations into Eq. 7.42, we obtain a

third general relation for cp - cv:

(7.45)

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End of Chapter

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