Chapter 10

Chapter 10
Thermodynamic Relations
Shacheendra Kishor Labh

Assistant Professor
Department of Mechanical and Automobile Engineering
IOE, Pashchimanchal Campus
Engineering Thermodynamics I BGE I/I IOE, Pashchimanchal Campus 1

Clapeyron Equation
• Consider a Carnot-cycle heat engine operating across a small temperature difference between
reservoirs at T and T − ΔT. The corresponding saturation pressures are P and P − Δ P.
• The Carnot cycle operates with four steady-state devices. In the high-temperature heat-transfer
process, the working fluid changes from saturated liquid at 1 to saturated vapor at 2.
• For reversible heat transfers
qH =Tslg ; qL = (T – ΔT) slg
so that,
wnet = qH – qL = ΔT slg
• Each process is steady-state and reversible,
such that the work in each process is given by

Clapeyron Equation
• Overall, for the four processes in the cycle,
• Comparing both equations of wnet we get,
Δ𝑃 𝑠𝑙𝑔
≈ 𝑣2 +𝑣3 𝑣 +𝑣
Δ𝑇 −( 1 2 4 )
2
• In the limit as Δ T → 0: v3 → v2 = vg, v4 → v1 = vl , which results in
Δ𝑃 𝑑𝑃𝑠𝑎𝑡 𝑠𝑙𝑔
lim = =
Δ𝑇→0 Δ𝑇 𝑑𝑇 𝑣𝑙𝑔

Clapeyron Equation
• Since the heat addition process 1 – 2 is at constant pressure as well as constant temperature
qH = hlg = T slg
• Hence, the expression becomes
𝑑𝑃𝑠𝑎𝑡 𝑠𝑙𝑔 ℎ𝑙𝑔

= =
𝑑𝑇 𝑣𝑙𝑔 𝑇𝑣𝑙𝑔
which is called the Clapeyron equation.

Mathematical Relations for a Homogeneous Phase
• The fundamental relation for the total differential of a dependent variable in terms of its partial
derivatives with respect to the independent variables is
Which can be re-written as,
• Taking the partial derivative of M with respect to y and of N with respect to x yields
• The order of differentiation is immaterial for properties since they are continuous point
functions and have exact differentials. Therefore, the two relations above are identical:

Maxwell’s relation
• 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.
• They are obtained from the four Gibbs equations by exploiting the exactness of the
differentials of thermodynamic properties.
• Two of the Gibbs relations are expressed as
du = T ds − P dv
dh = T ds + v dP
• To eliminate entropy as an independent property by introducing two new properties, two new
forms of the thermodynamic property relation need to be introduces. The first of these is the
Helmholtz function A
A = U − T S, a = u − Ts
• Differentiating and substituting earlier results,
da = du − T ds − s dT = −s dT − P dv
• The second new property is the Gibbs function G,
G = H − T S, g = h − Ts
• Differentiating and substituting earlier results,
dg = dh − T ds − s dT = −s dT + v dP
• All relations derived in this section involve only properties, it can be concluded that these are
exact differentials and, therefore, are of the general form of
• in which the coefficients M and N can be related as
• It follows that

• Similarly,
• These four equations are known as the Maxwell relations for a simple compressible mass.

Expansivity and Compressibility
• The coefficient of linear expansion indicates how the length of a solid body is influenced by a
change in temperature while the pressure remains constant. In terms of the notation of partial
derivatives, the coefficient of linear expansion, δT , is defined as
• A similar coefficient can be defined for changes in volume. Such a coefficient is applicable to
liquids and gases as well as to solids. This coefficient of volume expansion, αP, also called the
volume expansivity, is an indication of the change in volume as temperature changes while the
pressure remains constant. The definition of volume expansivity is
• The isothermal compressibility, βT , is an indication of the change in volume as pressure

changes while the temperature remains constant. The definition of the isothermal
compressibility is

Expansivity and Compressibility
• The adiabatic compressibility, βs, is an indication of the change in volume as pressure changes
while entropy remains constant; it is defined as
• The adiabatic bulk modulus, Bs, is the reciprocal of the adiabatic compressibility.
• The volume expansivity and isothermal and adiabatic compressibility are thermodynamic
properties of a substance, and for a simple compressible substance are functions of two
independent properties. Values of these properties are found in the standard handbooks of
physical properties.

Example
1. The pressure on a block of copper having a mass of 1 kg is increased in a reversible process
from 0.1 to 100 MPa while the temperature is held constant at 15◦C. Determine the work done
on the copper during this process, the change in entropy per kilogram of copper, the heat
transfer, and the change of internal energy per kilogram.
Over the range of pressure and temperature in this problem, the following data can be used:
Volume expansivity = αP = 5.0 × 10−5 K−1
Isothermal compressibility = βT = 8.6 × 10−12 m2/N
Specific volume = 0.000 114 m3/kg

Thank you for you attention!
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Chapter 10

Shacheendra Kishor Labh

Engineering Thermodynamics I BGE I/I IOE, Pashchimanchal Campus 1

Engineering Thermodynamics I BGE I/I IOE, Pashchimanchal Campus 2

• Comparing both equations of wnet we get,

Engineering Thermodynamics I BGE I/I IOE, Pashchimanchal Campus 3

𝑑𝑃𝑠𝑎𝑡 𝑠𝑙𝑔 ℎ𝑙𝑔

Engineering Thermodynamics I BGE I/I IOE, Pashchimanchal Campus 4

Which can be re-written as,

Engineering Thermodynamics I BGE I/I IOE, Pashchimanchal Campus 5

• in which the coefficients M and N can be related as

Engineering Thermodynamics I BGE I/I IOE, Pashchimanchal Campus 7

Engineering Thermodynamics I BGE I/I IOE, Pashchimanchal Campus 8

• The isothermal compressibility, βT , is an indication of the change in volume as pressure

Engineering Thermodynamics I BGE I/I IOE, Pashchimanchal Campus 9

Engineering Thermodynamics I BGE I/I IOE, Pashchimanchal Campus 10

Engineering Thermodynamics I BGE I/I IOE, Pashchimanchal Campus 11

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