6

Thermodynamic Properties
of Pure Fluids
Determination of thermodynamic properties of a fluid that cannot be measured directly necessitates
relating such properties to measurable quantities. In this chapter some new thermodynamic functions
are introduced and the equations giving the interrelationships between various thermodynamic
properties are discussed. These equations are derived using the method of partial derivatives. The
method of Jacobians for the systematic derivation of thermodynamic relations is also presented and
the method is illustrated with some typical examples. Relationships formulated in this chapter would
be useful in evaluating numerical values of all types of thermodynamic properties which, in turn, are
necessary for the practical calculations like the evaluation of the heat and work requirements in
industrially important processes. Using these relations, the thermodynamic properties of pure fluids
can be evaluated from the measurable quantities like pressure-volume-temperature relationship, heat
capacity data and coefficients of expansion and compressibility.

6.1 CLASSIFICATION OF THERMODYNAMIC PROPERTIES

Thermodynamic properties of fluids can be classified into three broad groups: the reference
properties, the energy properties and the derived properties.

6.1.1 Reference Properties

Also known as primary properties, these properties are the ones that are used to define the state of
the system. They have absolute values, as against energy properties, which are measured relative to
some arbitrary reference state. Examples of reference properties are temperature, pressure, volume,
and entropy. Of these, temperature and pressure are intensive, and volume and entropy are extensive.
In addition to these, in dealing with the solutions, the composition is also treated as a reference
property.

6.1.2 Energy Properties

The four energy properties are the internal energy (U), enthalpy (H), the Helmholtz free energy (A),
and the Gibbs free energy (G). All are extensive thermodynamic properties and are known relative to
some reference state. These are referred to as energy properties, because, the changes in these
thermodynamic functions indicate useful work under certain conditions of restraint.
6.1.3 Derived Properties
These are partial derivatives of energy properties or the reference properties. Examples include
specific heat (C), coefficient of expansion (b), Joule–Thomson coefficient (m), and coefficient of
compressibility (k).
Among the four energy properties, the internal energy and enthalpy were introduced in earlier
chapters. In the following sections, the Helmholtz work function and the Gibbs free energy are
defined. Both these functions involve entropy in their definition and in many cases it is convenient to
work with these properties rather than the entropy itself.

6.2 WORK FUNCTION (HELMHOLTZ FREE ENERGY)

The Helmholtz free energy (A) of a system is defined as
A = U – TS………(6.1)
where U, T, and S are the internal energy, temperature, and entropy of the system respectively. Since
U, T, and S are characteristic of the system and depend only on its thermodynamic state, Helmholtz
free energy is a state function. Since U and S are both extensive, A also is an extensive property.
To understand the physical significance of the work function, consider an isothermal reversible
change occurring from state 1 to state 2. Then from Eq. (6.1), the change in the work function
accompanying this process is
DA = DU – TDS………(6.2)
DA, DU , and DS denote the changes in the work function, the internal energy and the entropy
respectively of the system during the process. Since the process is reversible, the heat absorbed QR =
TDS, and Eq. (6.2) can be written as
DA = DU – QR………(6.3)
According to the first law of thermodynamics for a closed system,
DU = Q – W………(6.4)
Substituting this result in Eq. (6.3), we get
DA = – WR
or
WR = – DA………(6.5)
The right-hand side of Eq. (6.5) is the decrease in the work function. The equation therefore means
that the decrease in the work function accompanying a process at constant temperature is equal to the
reversible work done by the system during the process. Since the reversible work is the maximum
work obtainable from any change in state, the decrease in the work function in an isothermal process
is a measure of the maximum work available from a given change of state. In any actual isothermal
process, the work done by the system would be less than the decrease in the Helmholtz free energy,
but the maximum work that can be done by the system is equal to
– DA in the limit of a reversible process.
Consider an irreversible chemical reaction in which zinc reacts with dilute sulphuric acid producing
zinc sulphate and hydrogen at constant temperature and pressure. No work, other than the small
amount done against the atmosphere by the evolved hydrogen, is available from this process. The
same reaction may be carried out reversibly in a galvanic cell in which an electrode made of zinc is
connected through an external circuit to another electrode of hydrogen in contact with a platinised
electrode. The electrical energy now produced can be utilised to run a device such as an electric
motor. If at every instant the external electric system is made to exert such a large counter e.m.f., that,
when infinitesimally increased, would force current in the opposite direction, thus reversing the
reaction. The decrease in the work function in this process would be equal to the total work done by
the system, which include both the electrical work and the work of expansion.
Helmholtz free energy being a state function, –DA would be the same for reversible as well as for
irreversible process occurring between the same end states. But, whereas in the former it represents
the maximum work obtained, in the latter, it represents the maximum work which would have
resulted, had all irreversibilities been eliminated. It should also be noted that any change in state,
isothermal or otherwise, is accompanied by a definite change in the work function, but it is only for
an isothermal process that this change is a measure of the maximum work.

6.3 GIBBS FREE ENERGY

For the process in which zinc metal is allowed to react with dilute acid reversibly in a galvanic cell,
we have seen that the decrease in Helmholtz free energy determines the maximum work, which
includes the electrical energy, and the work of expansion resulting from the reaction. The maximum
‘useful work’, which in this case, is the amount of electrical energy produced, is given by the
decrease in another thermodynamic property known as the Gibbs free energy. It is denoted by G, and
like the work function, makes use of entropy in its definition.
G = H – TS………(6.6)
Like the work function A, Gibbs free energy G is a single valued function of the thermodynamic state
of the system and is an extensive property. It is widely used in the study of phase equilibria and
chemical reaction equilibria. Since by definition, enthalpy H = U + PV, Eq. (6.6) can be written as
G = (U + PV) – TS = A + PV………(6.7)
Equation (6.7) reveals that A is related to G in the same way as U is related to H
The physical significance of the Gibbs free energy function can be made clear if we consider a
reversible process at constant temperature and pressure. Equation (6.7) gives DG, the change in free
energy for a finite change in the state of the system as
DG = DA + D(PV)………(6.8)
We have already seen that DA = –WR for a reversible process at constant temperature. For a constant
pressure process, D(PV) = P(DV). Therefore, Eq. (6.8) becomes
DG = – WR + PDV
or
– DG = WR – PDV………(6.9)
WR represents the total reversible work obtainable from a given change of state, which includes in
addition to work of expansion, other forms of work such as electrical and surface work. Thus, we see
that the decrease in Gibbs free energy in a process occurring at constant temperature and pressure is
the maximum work other than the work of expansion available from the process, or the maximum ‘net
work’, , obtainable from the process.
= – DG………(6.10)
It is because of the fact that the change in Gibbs function G measures the net useful work, it is known
as the ‘free energy’.
For the electrochemical cell that we have considered earlier, the total work obtained (WR) includes
electrical work and the work done against the constant pressure of the atmosphere (PDV). The latter
work is always done whether the process is reversible or irreversible. Thus, the maximum electrical
work that could be done by the system undergoing a given change in state is less than the total
maximum work, – DA, by the expansion work and is measured by the decrease in the Gibbs free
energy, – DG.
The value of DG in any process is quite definite, no matter under what conditions the process is
carried out, but only when the temperature and pressure are constant the free energy change would
represent the maximum net work available from the given change in state.

6.4 RELATIONSHIPS AMONG THERMODYNAMIC PROPERTIES

The method of partial derivatives is used here to develop the important thermodynamic relationships.
The major thrust of this section is to express thermodynamic properties in terms of measurable
quantities.
6.4.1 Exact Differential Equations
Let z be a single-valued continuous function of two independent variables x and y.
z = f(x, y)
Then the total differential of z can be written in terms of its partial derivatives with respect to
independent variables x and y as

This value is independent of the path followed in bringing about the change from the initial condition
1 to final condition 2. The thermodynamic properties, in general, possess these characteristics of the
function z. For example, the work function or the free energy can be regarded as single valued
functions of the thermodynamic state, and dA and dG can be treated as exact differentials. Equation
(6.11) can be written as
dz = M dx + N dy………(6.12)
where M = (∂z/∂x)y and N = (∂z/∂y)x.
Also, we can write

A property of exact differential equation that we will be using frequently is shown by Eq. (6.13).
6.4.2 Fundamental Property Relations
The differentials of energy properties form the basis for the derivation of a large number of equations
relating thermodynamic properties. These are developed below for systems of constant mass and
composition in which the only external force is the pressure and the process occurring is reversible.
The first law for non-flow process is provided by Eq. (2.5) as dU = dQ – dW. For the present case,
the heat and work terms are related to the properties of the system as dQ = T dS and
dW = P dV, so that Eq. (2.5) becomes

Equations (6.14), (6.16), (6.17), and (6.18) are the fundamental differential equations which express
the energy properties in terms of the four reference properties P, V, T, and S. It can be seen that each
of the energy properties is functionally related to a special pair of variables. For example, Eq. (6.18)
shows that
G = f(P, T)
Thus P and T are the canonical variables or special variables for Gibbs free energy G. Canonical
variables for the work function are V and T.
6.4.3 Maxwell’s Equations
Maxwell’s equations are helpful in replacing unmeasurable quantities appearing in thermodynamic
equations by measurable quantities. Using these relations, the partial derivatives of entropy with
respect to pressure and volume are expressed as derivatives possessing easily identifiable physical
meaning. Each of the four Maxwell’s equations is derived from the exact differential equations of the
four energy properties.
Consider the exact differential of internal energy, i.e. Eq. (6.14). At constant volume, it becomes

This is the first of the four Maxwell’s equations. The remaining three equations are obtained in a
similar way starting from Eqs. (6.16), (6.17), and (6.18). The results are given below.
increased to 20 bar at 300 K? What assumption is involved in the solution?
Solution The coefficient of volume expansion is defined as

The change in entropy is

DS = –1.25 10–4 (P2 – P1) = – 1.25 10–4 (20.0 – 1.0) 105 = – 237.5 J/kmol K
It is assumed that the derivative (∂V/∂T)P is constant in the pressure range 1 to 20 bar.

6.4.4 Clapeyron Equation

The Clapeyron equation predicts the dependence of equilibrium pressure on temperature when two
phases of a given substance coexist. It is given by

………(6.25)
where DH and DV are the enthalpy and volume change accompanying a phase change. It can be
derived from Maxwell’s relation Eq. (6.23), which is applicable to any closed, homogeneous or
heterogeneous system in equilibrium, with an external pressure. Consider a single component system
containing two phases, say liquid and vapour, in thermodynamic equilibrium. By the phase rule, the
system is univariant, i.e. only one intensive parameter can be varied independently. The equilibrium
pressure (for the present case, the vapour pressure), is dependent on temperature only and is
independent of volume. Thus, the partial derivative (∂P/∂T)V in Eq. (6.23) can be replaced by
(dP/dT) without the constant volume restriction. Moreover, (∂S/∂V)T = DS/DV, where DS is the
entropy change when a given quantity of the substance is transferred from one phase to the other at
constant temperature and DV is the accompanying volume change. (DS/DV) is a constant at a given
temperature, for both DS and DV are extensive quantities that are proportional to the amount of
material transferred. As we are dealing with equilibrium and therefore with a reversible process, DS
= Q/T = DH/T, where DH is the change in enthalpy during the phase change or the latent heat of phase
change. Substituting these into Eq. (6.23) we get the Clapeyron equation, Eq. (6.25):
Clapeyron equation may be used for various purposes. It can be used to calculate the heat of
vaporisation, if the variation of vapour pressure with temperature is known. Alternatively, if the heat
of vaporisation is available, it is possible to predict the vapour pressure variation with temperature.
[Note: An alternative derivation for the Clapeyron equation is provided in Chapter 8. See
Example 8.3.]
Clausius-Clapeyron equation. If the temperature is not too near the critical point, the volume of
the liquid is small in comparison with the volume of vapour. The volume change accompanying
vaporisation DV = VG – VL is therefore approximately equal to VG, the molar volume of vapour.
Equation (6.25) now becomes

EXAMPLE 6.2 Calculate the vapour pressure of water at 363 K, if the vapour pressure at 373 K is
101.3 kPa. The mean heat of vaporisation in this temperature range is 2275 kJ/kg.
Solution Refer Eq. (6.28). T1 = 363 K; T2 = 373 K; = 101.3 kPa; DH = 2275 18 kJ/kmol; R =
8.314 kJ/kmol K.
Substituting the values in Eq. (6.28), we get
EXAMPLE 6.3 Mercury has a density of 13.69 103 kg/m3 in the liquid state and 14.193
103 kg/m3 in the solid state, both measured at the melting point of 234.33 K at 1 bar. If the heat of
fusion of mercury is 9.7876 kJ/kg, what is the melting point of mercury at 10 bar?
Solution The Clapeyron equation [Eq. (6.25)], can be rearranged as:

6.4.5 Entropy–Heat Capacity Relationships

Maxwell’s equations provide the partial derivatives of entropy with pressure or volume. The partial
derivatives of entropy with temperature are provided by the entropy–heat capacity relationships.
The specific heats at constant pressure (CP) and constant volume (CV) are discussed in
Section 2.7. These are defined as under,
An important use of Eqs. (6.31) and (6.32) is in the determination of entropy change of a system at
constant pressure or at constant volume respectively, for a specified change in temperature. Equation
(6.31) on integration gives

If CP varies with temperature, the required integration can be performed analytically provided CP is
expressed as a function of temperature. In the absence of such a relationship, graphical integration
will give the desired result. In the graphical method, the values of CP/T are plotted against T (or, CP
against ln T) and the area under the curve between T1 and T2 (or, between ln T1 and ln T2) will give
DS.
EXAMPLE 6.4 Determine the increase in entropy of solid magnesium when the temperature is
increased from 300 K to 800 K at atmospheric pressure. The heat capacity is given by the following
relation
CP = 26.04 + 5.586 10–3 T + 28.476 104 T–2
where CP is in J/mol K and temperature in K.
Solution Equation (6.31) on integration gives

6.4.6 Differential Equations for Entropy

The state of a pure homogeneous fluid is uniquely determined by specifying any two thermodynamic
properties. Choosing temperature and pressure as variables, other properties like entropy are related
to them as S = f(P, T). The total differential of S is

Substituting Eqs. (6.24) and (6.31) into the above

The partial derivative (∂P/∂T)V appearing in Eq. (6.37) can be expressed in terms of (∂V/∂T)P and
(∂V/∂P)T which, in turn, are related to the coefficient of volume expansion and compressibility of the
substance respectively. This is done as below.
Let the volume V be expressed as a function of P and T. V = f(P, T). Then the total differential of V
can be written as
6.4.7 Modified Equations for U and H
Changes in the internal energy and enthalpy can now be expressed in terms of changes in measurable
quantities like pressure, volume, temperature, and specific heat of the fluid. Equations (6.14) and
(6.16) give the differentials of internal energy and enthalpy respectively. Modified equations for U
a nd H would result when Eq. (6.35) or Eq. (6.39) is substituted into Eqs. (6.14) and (6.16).
Rewriting Eq. (6.14) using Eq. (6.39), we get
EXAMPLE 6.5 Develop equations for evaluating the change in internal energy and change in enthalpy
for process involving ideal gases.
Solution Equations (6.40) and (6.41) are used for evaluating dU and dH.
The preceding two equations indicate that the internal energy and enthalpy of an ideal gas are
functions of temperature alone, and for isothermal process there would be no change in these
properties.
EXAMPLE 6.6 The equation of state of a certain substance is given by the expression
V = RT/P – C/T3, and the specific heat is given by the relation CP = A + BT where A, B , and C are
constants. Derive expressions for changes in internal energy, enthalpy and entropy for
(a) an isothermal process
(b) an isobaric process.
Solution Since V = RT/P – C/T3,
(b) Isobaric process: dP = 0. Equation (6.42) reduces to dU = CP dT – P dV. Since

From Eq. (6.35), change in the entropy is

6.4.8 Effect of Temperature, Pressure and Volume on U, H and S

The most useful relations for the estimation of various thermodynamic properties of a fluid in a given
state are those which give the effect of temperature and pressure on entropy and enthalpy. The partial
derivatives representing these effects are given below in terms of measurable quantities, although
these effects are contained in the equations developed in previous sections.
The effects of pressure and temperature on entropy are given by the Maxwell’s equation,
Eq. (6.24), and the heat capacity relation, Eq. (6.31), respectively. They are reproduced below.
The effects of temperature and volume on internal energy are obtained from Eq. (6.40), which reduces
to the following forms under constant volume and constant temperature restrictions.

The second identity in Eq. (6.47) follows from Eq. (6.38).

Equations to predict the variation of enthalpy with temperature and pressure are derived from
Eq. (6.41) under the constraints of constant pressure and constant temperature. At constant pressure,
Eq. (6.41) gives

At constant temperature Eq. (6.41) becomes

The method of calculation of entropy and enthalpy of a fluid in a given thermodynamic state using
Eqs. (6.24), (6.31), (6.48) and (6.49) is explained below. Other thermodynamic properties easily
follow from these values. It is assumed that the following data are available.
1. The pressure-volume-temperature relationship for the fluid either as an equation of state or as a
tabulated experimental result.
2. The heat capacity CP0 at pressure P0 and temperature T0.
3. The enthalpy H0 and entropy S0 at temperature T0 and pressure P0.
Assume that the properties are to be evaluated at temperature T and pressure P. This state is
represented by point B in Fig. 6.2.

The entropy (S0) and enthalpy (H0) are known at temperature T0 and pressure P0, the fluid in this
state being represented by point A in Fig. 6.2. Since S and H are state functions, DS and DH for the
fluid will be the same when it undergoes a change of state from state A to state B, as the DS and DH
calculated for any process occurring between states A and B. We can, for convenience, devise a two-
step process for bringing about this change so that the enthalpy and entropy changes in these separate
steps are easily evaluated. During process AC the fluid is heated from T0 to T at constant pressure P0
(step 1) and during the process CB the fluid is compressed from pressure P0 to P at constant
temperature T (step 2). DS and DH for these steps are evaluated thus:
Step 1: Let H and S be the enthalpy and entropy at point C. Then by Eqs. (6.48) and (6.31), we
get

Since H0 and S0 are known, H and S are readily evaluated by these equations.
Step 2: For process CB, the enthalpy and entropy changes are obtained from Eqs. (6.49) and (6.24)
respectively.
Using the values of H and S obtained in step 1 the enthalpy (H) and entropy (S) at point B are
calculated.
The integrals appearing in the preceding two equations are evaluated using the P-V-T data. If the data
are available in the form of an equation of state, the derivative (∂V/∂T)P is obtained by
differentiation, and the integration is performed analytically. Instead, if the P-V-T data are available
as a tabulated result, the integration has to be performed graphically. This is done by plotting V
against T for various constant pressures and measuring the slopes at temperature T. These slopes give
the partial derivative (∂V/∂T)P. These are then plotted against P, and the area under the curve
between pressure P0 and P is found out which gives the integral in Eq. (6.51). For evaluating the
enthalpy, the whole terms within the brackets in Eq. (6.50) are plotted against P and the area is
determined as before.

EXAMPLE 6.7 Calculate the internal energy, enthalpy, entropy and free energy for one mole of
nitrogen at 773 K and 100 bar assuming that nitrogen behaves as an ideal gas. The molal heat capacity
of nitrogen at 1 bar is given as CP = 27.3 + 4.2 10–3T, where T is in K and CP is in
J/mol K. Enthalpy of nitrogen is zero at 273 K and 1 bar. The entropy of nitrogen is 192.4 J/molK at
298 K and 1 bar.
Solution Assume that the nitrogen is initially at 273 K and 1 bar for evaluation of enthalpy, and at
298 K and 1 bar for evaluation of entropy. Let the gas undergo a change of state in two steps. First, a
constant pressure process at 1 bar when its temperature is increased to 773 K. Secondly, a constant
temperature process at 773 K when the pressure of the gas increases to 100 bar.
Step 1:

EXAMPLE 6.8 Calculate the change in internal energy of 25 kmol of CO2 gas when it is isothermally
expanded from 1.0132 104 kPa to 1.0132 102 kPa at 373 K. Assume CO2 to obey

Solution The change in internal energy in an isothermal process is given by Eq. (6.47):

Here V1 is the initial volume of the gas which is evaluated from the equation of state.
EXAMPLE 6.9 A gas obeys the equation of state P(V – B) = RT + (AP2)/T, where A and B are
constants. The mean specific heat (CP) at atmospheric pressure is 33.6 J/mol K. If

A = 1.0 10–3 m3 K/(bar) mol; B = 8.0 10–5 m3/mol

calculate
(a) The entropy change when the state of the gas is changed from state 1 (4 bar, 300 K) to state 2 (12
bar, 400 K).
(b) The mean heat capacity at 12 bar.
Solution (a) The proposed change is assumed to take place in three steps in series as illustrated in
Fig. 6.4.
Step 1: Process AC, isothermal at 300 K
Step 2: Process CD, isobaric at 1 bar.
Step 3: Process DB, isothermal at 400 K
Since the equation of state is
P(V – B) = RT + (AP2)/T
differentiation yields,
6.4.9 Relationship between CP and CV
We have seen that the partial derivatives of entropy with respect to temperature are related to the
specific heats as given by Eqs. (6.31) and (6.32).
which can be rearranged as

If the P-V-T behaviour of the fluid is known either as an equation of state or as a graphical result, Eq.
(6.54) can be used to evaluate the difference between CP and CV over wide ranges of temperature
and pressure.
Equation (6.54) can be written in terms of coefficient of volume expansion (b) and coefficient of
compressibility (k) which are defined as below.
Equation (6.55) is the most convenient form for the calculation of CP – CV of solids and liquids.
Equations (6.54) and (6.55) are particularly valuable because most of the laws developed under
statistical thermodynamics on specific heat deal with CV, though these are rarely determined
experimentally. These equations provide useful tools for calculating CV from experimentally
determined values of CP.
EXAMPLE 6.10 Show that for ideal gases CP – CV = R.
Solution For ideal gases, PV = RT, or V = RT/P. Also,

EXAMPLE 6.11 The coefficient of compressibility and coefficient of volume expansion of mercury
at 273 K and 1 bar are 3.9 10–6 (bar)–1 and 1.8 10–4 K–1 respectively. Calculate CV for
mercury given that CP = 0.14 kJ/kg K and density = 13.596 103 kg/m3.
Solution Using Eq. (6.55),

EXAMPLE 6.12 Show that for a gas obeying van der Waals equation of state,

where a and b are van der Waals constants.

Solution The van der Waals equation is

Differentiate Eq. (3.29) with respect to V at constant T

6.4.10 Ratio of Heat Capacities
Combining Eqs. (6.31) and (6.32) we see that

Rearranging this equation we get

It is to be noted that it is impossible to write the ratio of heat capacities in terms of P-V-T data alone;
entropy appears in at least one of the partial derivatives.
6.4.11 Effect of Pressure and Volume on CP and CV
The change in entropy with changes in temperature and pressure is given by Eq. (6.35).

The above equation reduces to the Maxwell’s equation, Eq. (6.24), under constant temperature (i.e.
when dT = 0) and the heat capacity relation, Eq. (6.31), under constant pressure (i.e. when dP = 0).

Differentiate Eq. (6.24) with respect to temperature, keeping the pressure constant and Eq. (6.31)
with respect to pressure keeping the temperature constant. This results in Eqs. (6.60) and (6.61)
respectively.
Compare Eq. (6.60) with Eq. (6.61). The right-hand sides of these equations are equal. That is,

Equations (6.62) and (6.63) represent the effect of pressure and volume on CP.
The following two equations that give the effect of pressure and volume on CV can be derived in a
manner similar to that used for the derivation of Eqs. (6.62) and (6.63)

Equations (6.62)–(6.65) hold good for any homogeneous substance; however, they are usually
applied to gases.
EXAMPLE 6.13 Show that CP and CV of ideal gases are independent of pressure and volume.
Solution Since PV = RT,

EXAMPLE 6.14 A certain gas is found to obey the following equation of state.
6.4.13 Gibbs–Helmholtz Equation
The Gibbs–Helmholtz equation provides the effect of temperature on Gibbs free energy. Consider Eq.
(6.18).
dG = – S dT + V dP………(6.18)
At constant pressure, the above equation reduces to

Even though this equation gives the effect of temperature on G it will be convenient for practical
calculations to replace S in terms of measurable quantities. This can be done as follows.
Noting that d(u/v) = (v du – u dv)/v2, the derivative of G/T can be written as

where H is a constant of integration whose value is known by the choice of reference state at which
enthalpy is arbitrarily set equal to zero. Expressing CP as a power function of T as
CP = a + bT + cT2, H = H + aT + (1/2) bT2 + (1/3) cT3. Substituting these in Eq. (6.74), we get