Chapter 2

Thermodynamic Properties of Real

Substances

Thermodynamics deals with the work and heat interactions of the system with its
surroundings as it undergoes a process. These quantities can be estimated once the
changes in various state functions, namely, internal energy, enthalpy, and entropy,
are known. The purpose of this chapter is to develop general expressions to calculate
changes in internal energy, enthalpy, and entropy.

2.1 Work Functions

For a closed system undergoing a reversible isothermal process, integration of
Eqn (1.6-8) gives
Qrev = T S. (2.1-1)
The use of Eqn (2.1-1) in Eqn (1.5-7) leads to

U = T S + Wrev (2.1-2)

in which the changes in kinetic and potential energies are considered negligible.
Rearrangement of Eqn (2.1-2) results in

Wrev = (U TS) = A = Ainitial Afinal , (2.1-3)

where the term A is called the Helmholtz energy and is defined by

A = U TS. (2.1-4)

Since U, T, and S are all state functions, Helmholtz energy is a state function. It
is also an extensive property. As can be seen from Eqn (2.1-3), the decrease in the
The Thermodynamics of Phase and Reaction Equilibria. DOI: http://dx.doi.org/10.1016/B978-0-44-4594976.00002-5
2013 Elsevier B.V. All rights reserved. 13
14 Tosun

Helmholtz energy indicates the maximum work that can be obtained from a closed
system undergoing an isothermal process. The term A comes from the German
word Arbeit, meaning work.
For a steady-state flow system undergoing a reversible isothermal process, com-
bination of Eqns (1.5-9) and (1.6-9) yields

H = T S + (Ws )rev (2.1-5)

in which the changes in kinetic and potential energies are considered negligible.
Rearrangement of Eqn (2.1-5) gives

(Ws )rev = (H TS) = G = Ginitial Gfinal , (2.1-6)

where the term G is called the Gibbs1 energy and is defined by

G = H TS. (2.1-7)

Since H, T, and S are all state functions, Gibbs energy is a state function. It is also
an extensive property. As can be seen from Eqn (2.1-6), the decrease in the Gibbs
energy indicates the maximum work that can be obtained from a steady-state flow
system under isothermal conditions. Helmholtz and Gibbs energies are sometimes
referred to as work functions.
Examination of Eqns (2.1-4) and (2.1-7) indicates that A < U and G < H as a
result of the subtraction of the term TS. Hence, the term TS can be interpreted
as a measure of unavailable energy.

2.2 Thermodynamic Properties of a Single-Phase System

2.2.1 Fundamental Equations
In differential form, the first law of thermodynamics for a closed system is given
by
dU = Q + W. (2.2-1)
If the process is reversible, substitution of Eqns (1.3-2) and (1.6-1) into Eqn (2.2-1)
gives
dU = T dS P dV . (2.2-2)

1 In honor of Josiah Willard Gibbs, Professor of Mathematical Physics at Yale University. He was awarded the
first PhD degree in engineering in the USA.
Thermodynamic Properties of Real Substances 15

The definition of enthalpy is given by

H = U + PV . (2.2-3)
The differential form of Eqn (2.2-3) becomes
dH = dU + P dV + V dP. (2.2-4)
Substitution of Eqn (2.2-2) into Eqn (2.2-4) gives
dH = T dS + V dP. (2.2-5)
The definition of Helmholtz energy is given by
A = U TS. (2.2-6)
The differential form of Eqn (2.2-6) becomes
dA = dU T dS S dT . (2.2-7)
Substitution of Eqn (2.2-2) into Eqn (2.2-7) gives
dA = P dV S dT . (2.2-8)
The definition of Gibbs energy is given by
G = H TS. (2.2-9)
The differential form of Eqn (2.2-9) becomes
dG = dH T dS S dT . (2.2-10)
Substitution of Eqn (2.2-5) into Eqn (2.2-10) gives
dG = V dP S dT . (2.2-11)
It is also possible to express Eqns (2.2-2), (2.2-5), (2.2-8), and (2.2-11) in terms
of mass or molar quantities, i.e.
 = T d
dU S P d
V,  = T d
dU S P d
V, (2.2-12)
 = T d
dH S+
V dP,  = T d
dH S +
V dP, (2.2-13)
d V 
A = P d S dT , d V 
A = P d S dT , (2.2-14)
d V dP 
G= S dT , d V dP 
G= S dT . (2.2-15)
These equations are called fundamental equations. Note that fundamental equations
consist of only properties and their differential changes. These properties and their
changes are state functions and are not dependent on the path or process involved.
Therefore, once the initial and final states are specified, the expressions given in
Eqns (2.2-12)(2.2-15) hold for all processes (reversible or irreversible) and for a
change of state in either a closed system or a steady-state flow system.
16 Tosun

2.2.2 Maxwell Relations

For an exact differential, d, expressed in the form
d = M(x, y)dx + N(x, y)dy, (2.2-16)
the following relationship holds:
   
M N
= . (2.2-17)
y x x y
Since internal energy, U, enthalpy, H, Helmholtz energy, A, and Gibbs energy, G,
are all state functions, application of Eqn (2.2-17) to the expressions given in Eqns
(2.2-12)(2.2-15) leads to
   
T P
= , (2.2-18)

V S 
S  V
   
T 
V
= , (2.2-19)
P S 
S P
   
P S
= , (2.2-20)
T  V 
V T
   
V S
= . (2.2-21)
T P P T
These equations are known as the Maxwell relations.

2.2.3 Internal Energy Change

For a single-phase and single-component system, the Gibbs phase rule, Eqn (1.1-4),
gives the number of degrees of freedom as two. Hence, the state of such a system
is specified by two independent intensive properties. The dependence of internal
energy on temperature and volume, i.e.
 = U(T
U  ,V) (2.2-22)
leads to a convenient relationship to use in calculating the internal energy change.2
 is given by
The total differential of U
     
 = U U U
dU dT + d
V = CV dT + d
V. (2.2-23)
T  V V T 
V T

 = U(P,
2 The functional form of internal energy can also be expressed as U   = U(P,
T ) or U  
V).
Thermodynamic Properties of Real Substances 17

 
In order to express the term ( U/ V )T in terms of measurable quantities, differ-
entiation of Eqn (2.2-12) with respect to 
V keeping T constant gives
   

U S
=T P. (2.2-24)

V T 
V T
The use of Eqn (2.2-20) in Eqn (2.2-24) yields
   

U P
=T P. (2.2-25)

V T T V
Thus, substitution of Eqn (2.2-25) into Eqn (2.2-23) gives the change in internal
energy as    
  P
dU = CV dT + T P dV. (2.2-26)
T  V

2.2.4 Enthalpy Change

The dependence of enthalpy on temperature and pressure, i.e.
 = H(T
H  , P) (2.2-27)
leads to a convenient relationship to use in calculating the enthalpy change.3 The
 is given by
total differential of H
     
H H H

dH = dT + 
dP = CP dT + dP. (2.2-28)
T P P T P T

In order to express the term ( H/P) T in terms of measurable quantities, differen-
tiation of Eqn (2.2-13) with respect to P keeping T constant gives
   
H S
=T +
V. (2.2-29)
P T P T
The use of Eqn (2.2-21) in Eqn (2.2-29) yields
   

H 
V
= VT . (2.2-30)
P T T P
Thus, substitution of Eqn (2.2-30) into Eqn (2.2-28) gives the change in enthalpy
as    

V
=
dH CP dT +  VT dP. (2.2-31)
T P

 = H(T
3 The functional form of enthalpy can also be expressed as H  ,  = H(P,
V ) or H  
V).
18 Tosun

2.2.5 Entropy Change

Before deriving the equations to calculate the change in entropy, it is necessary to
express heat capacities at constant volume and pressure in terms of partial deriva-
tives of entropy.
Heat capacity at constant volume, CV , is defined by
 
 U
CV = . (2.2-32)
T  V

The use of Eqn (2.2-12) in Eqn (2.2-32) leads to

 
 S
CV = T . (2.2-33)
T  V

On the other hand, heat capacity at constant pressure, 

CP , is defined by
 
 H
CP = . (2.2-34)
T P
The use of Eqn (2.2-13) in Eqn (2.2-34) leads to
 
 S
CP = T . (2.2-35)
T P

Entropy may be expressed as a function of temperature and volume, i.e.


S =
S (T , 
V ). (2.2-36)

The total differential of 

S , d
S , is given by
   
 S S
dS = dT + d
V. (2.2-37)
T  V 
V T
The use of Eqns (2.2-20) and (2.2-33) in Eqn (2.2-37) gives the change in entropy
as  

CV P

dS = dT + d
V. (2.2-38)
T T  V

It is also possible to express entropy as a function of temperature and pressure,

i.e.

S =
S (T , P). (2.2-39)
Thermodynamic Properties of Real Substances 19

The total differential of 

S , d
S , is given by
   
S S
dS = dT + dP. (2.2-40)
T P P T
The use of Eqns (2.2-21) and (2.2-35) in Eqn (2.2-40) gives the change in entropy
as  

CP V

dS = dT dP. (2.2-41)
T T P

2.2.6 Relationship Between Partial Derivatives

Inverse rule: The total differential of the function f (x, y) is expressed as
   
f f
df = dx + dy. (2.2-42)
x y y x
If both sides of Eqn (2.2-42) are differentiated with respect to f by keeping y
constant, the result is    
f x
1= (2.2-43)
x y f y
or  
f 1
=  , (2.2-44)
x y x
f y
which is known as the inverse rule.
Triple Product Rule: Differentiation of Eqn (2.2-42) with respect to y keeping
f constant gives      
f x f
0= + . (2.2-45)
x y y f y x
The use of the inverse rule leads to
   
f x 1
0= +  (2.2-46)
x y y f y
f x
or      
f x y
= 1, (2.2-47)
x y y f f x
which is known as the triple product rule. It can be memorized with a cyclic
relation as shown in Fig. 2.1, i.e. by marking the variables f, x, and y on a circle
20 Tosun

y x

Figure 2.1: Cyclic relation for the triple product rule.

in the clockwise direction. Going in the clockwise direction, differentiate one of

the variables (let us call this the first variable) with respect to the second one by
keeping the third variable constant. Repeat this procedure for each of the variables
going in the clockwise direction, and the product of three terms is equal to 1.

Example 2.1 Evaluate ( 

V /T )P if a gas is represented by the following equa-
tion of state:
RT a
P= .

V b T V2

Solution
Since V cannot be expressed explicitly in terms of T and P, direct differentiation
is not possible. Marking  V , T , and P on a circle in the clockwise direction and
the application of the triple product rule give
V

P T

     
V T P
= 1 (1)
T P P 
V 
V T
or
 

V 1
=     . (2)
T P T P
P 
V 
V T
Thermodynamic Properties of Real Substances 21

With the help of the inverse rule, Eqn (2) takes the form
 
V (P/T ) V
= . (3)
T P 
(P/ V )T
From the given equation of state
 
P R a
= + , (4)
T  V 
V b T 2V2
 
P RT 2a
= + . (5)
V T (
V b)2 T V3

Substitution of Eqns (4) and (5) into Eqn (3) yields

R a
  +

V 
Vb T 2
V2
= . (6)
T RT 2a
P
(
V b)2 T V3

2.2.7 Relationship Between Heat Capacities

Differentiation of Eqn (2.2-41) with respect to temperature keeping volume
constant gives      
S 
CP V P
= . (2.2-48)
T  V T T P T  V
The use of Eqn (2.2-33) in Eqn (2.2-48) leads to
   
  V P
CP = CV + T . (2.2-49)
T P T  V
In general, it is difficult to express 
V as an explicit function of T and P, i.e. 
V =

V (T , P). It is much easier to express P as an explicit function of 
4 V and T , i.e.
P = P( V , T ). Therefore, the quantity ( 
V /T )P in Eqn (2.2-49) is difficult to
evaluate and must be replaced by (P/T ) 
V and (P/ V )T . From Eqn (3) of
Example 2.1  

V (P/T )V
= . (2.2-50)
T P 
(P/ V )T
4 The reason for this statement will be apparent in the next chapter.
22 Tosun

Substitution of Eqn (2.2-50) into Eqn (2.2-49) leads to the following relationship
between heat capacities:

(P/T )
2

CP = 
CV T V
. (2.2-51)
(P/ 
V )T

2.2.8 Coefficient of Thermal Expansion and Isothermal

Compressibility
Coefficient of thermal expansion, , is the variation of volume with temperature at
constant pressure per unit volume, i.e.
   
1  V 1  V
= = . (2.2-52)
V T P 
 V T P

Since = 1/
V , it is also possible to express in terms of density as
 
1
= . (2.2-53)
T P
For most liquids, density increases with decreasing temperature. As a result, > 0.
However, for liquid water between 4 C and 0 C, turns out to be negative. This
is the reason why lakes start freezing from top to bottom.
Isothermal compressibility, , is the variation of volume with pressure at con-
stant temperature per unit volume, i.e.
   
1  V 1  V
= = . (2.2-54)
V P T
 V P T


Since volume decreases with increasing pressure, ( 

V /P)T is a negative quantity.
To make positive, a minus sign is used in Eqn (2.2-54). In terms of density,
Eqn (2.2-54) becomes  
1
= . (2.2-55)
P T
Both and remain almost constant for liquids and solids.5 Thus, as will be
shown in the next chapter, coefficient of thermal expansion and isothermal com-
pressibility are especially useful in calculating changes in internal energy, enthalpy,
and entropy for liquids and solids.

5 This statement does not hold near the critical point.

Thermodynamic Properties of Real Substances 23

Example 2.2 A 1 L bottle is completely filled with an equimolar mixture of

benzene and cyclohexane at 298 K. What pressure will develop within the bottle
if it is heated to 305 K as a result of the sunlight coming through the lab window?
The following data are provided for an equimolar mixture of benzene and
cyclohexane:

= 1.21 103 K1 and = 108 106 bar1 .

Solution
It is required to determine the variation of pressure with temperature at constant
volume, i.e. (P/T )V . From the triple product rule
     
P T V
= 1.
T V V P P T
Solving for (P/T )V gives
 
P 1 (V /T )P
=     = = . (1)
T V T V (V /P)T
V P P T
Assuming and to be constants, and the initial pressure within the bottle to
be 1 bar, integration of Eqn (1) gives
 
1.21 103
P =1+ (305 298) = 79.4 bar.
108 106
Comment: The bottle probably breaks before the pressure reaches 79.4 bar.

Example 2.3 At 573 K, the variation in the specific volume of steam as a func-
tion of pressure is given as follows:

P (MPa) 
V (m3 /kg)
0.8 0.3241
1.0 0.2579
1.2 0.2138

(a) Calculate the isothermal compressibility for steam at 1 MPa and 573 K.
(b) Compare this value with the one obtained by assuming that the steam
obeys the ideal gas equation of state.
24 Tosun

Solution
(a) From Eqn (2.2-54)
   
1 
V 1 
V
= 

V P T V P


1 0.2138 0.3241
= = 1.07 MPa1 .
0.2579 1.2 0.8

(b) If steam is considered an ideal gas, then

 
 RT V RT
V= = 2. (1)
P P T P
Substitution of Eqn (1) into Eqn (2.2-54) gives
    
1  V P RT 1
= = 2 = = 1 MPa1 .
V P T
 RT P P

So far, the equations developed to calculate changes in internal energy, enthalpy,

and entropy apply to all substances. However, they contain partial derivatives in-
volving T , P, and  V . Thus, an equation of state must be known for a substance
in question. The following example shows how to evaluate the partial derivatives
to determine changes in internal energy or enthalpy once the equation of state
is known. Determination of changes in internal energy, enthalpy, and entropy for
various equations of state will be covered in detail in the next chapter.
Example 2.4 A piston-cylinder assembly contains 2 mol of a gas at 5 bar and
350 K. As a result of irreversible operations 3.5 kJ of work is done on the
system, the final pressure and temperature being 25 bar and 400 K, respectively.
Calculate the heat interaction of the gas with the surroundings.
Data: The gas obeys the following equation of state:

P(
V b) = RT

with b = 4 105 m3 /mol.

The heat capacity at constant pressure is given as a function of temperature
as

CP = 8.314 + 0.108T ,
where 
CP is in J/mol K and T is in K.
Thermodynamic Properties of Real Substances 25

Solution
System: Contents of the cylinder.
When changes in kinetic and potential energies are negligible, the first law of
thermodynamics, i.e. Eqn (1.5-7), reduces to

U = Q + W. (1)
Determination of Q requires the value of U to be known. The variation in
internal energy can be determined from Eqn (2.2-26), i.e.
   
  P
dU = CV dT + T P d V. (2)
T  V

From the given equation of state,

 
RT P R
P= = . (3)

V b T 
V 
Vb
Therefore, the term
 
P RT RT
T P = =0 (4)
T 
V 
V b 
V b
and Eqn (2) simplifies to
 T2
=
U 
CV dT (5)
T1
in which subscripts 1 and 2 represent the initial and final states, respectively.
To determine 
CV , we have to use Eqn (2.2-51), i.e.
(P/T )
2

CP = 
CV T V
. (6)
(P/ 
V )T
Note that    
P R P RT
= , = . (7)
T 
Vb

V 
V T (
V b)2
Substitution of the terms in Eqn (7) into Eqn (6) leads to

CP = 
CV + R. (8)
Thus

CV = 8.314 + 0.108T 8.314 = 0.108T . (9)
26 Tosun

Substitution of Eqn (9) into Eqn (5) and integration give

0.108

=
U (400)2 (350)2 = 2025 J/mol
2
U = (2)(2025) = 4050 J.
Therefore, the heat interaction of the system with the surroundings is calculated
from Eqn (1) as
Q = U W = 4050 3500 = 550 J
indicating that heat is added to the system.
Alternate solution: The change in enthalpy is given by Eqn (2.2-31), i.e.
   

V
 
dH = CP dT + V T dP. (10)
T P
From the given equation of state,
 
 RT V R
V =b+ = . (11)
P T P P
Substitution of Eqn (11) into Eqn (10) and integration yield
 T2

H = 
CP dT + b(P2 P1 ) (12)
T1
or

 = (8.314) (400 350) + 0.108 (400)2 (350)2

H
 2 
5
+ 4 10 (25 5) 105 = 2520.7 J/mol.
=H
Since U  P
V , the change in internal energy is given by
 = H
U  (P
V ). (13)
From the given equation of state
P
V = RT + bP. (14)
The use of Eqn (14) in Eqn (13) gives
 = H
U  R T b P = 2520.7 (8.314)(400 350)
 
4 105 (25 5) 105 = 2025 J/mol.
 is known, Q can be calculated from Eqn (1).
Once U
Thermodynamic Properties of Real Substances 27

Problems
Problems Related to Section 2.2.
2.1 For steady-state flow through a throttling valve with negligible changes in
kinetic and potential energies, the first law states that the enthalpy remains
constant, i.e. isenthalpic process. The variation of temperature with pressure
in such a process is known as the Joule-Thomson coefficient, .
(a) Show that the Joule-Thomson coefficient is given by
   
1 V
= T V (1)

CP T P

The throttling process may lead to an increase or decrease in temperature

depending on the value of , i.e.

> 0, Temperature decreases on throttling,
(2)
< 0, Temperature increases on throttling.
The temperature at which the Joule-Thomson coefficient changes sign is
called an inversion temperature. At higher temperatures < 0, and at
lower temperatures > 0. As a result, cryogenic applications require gas
temperature to be lower than the inversion temperature.
Most gases have an inversion temperature higher than room temper-
ature. Hydrogen, however, has an inversion temperature of 80 C. In
order to liquefy hydrogen, it is first necessary to decrease its temperature
below 80 C using liquefied nitrogen and then decrease its pressure by
a throttling process.
(b) Show that the inversion condition, = 0, is given by the equation
   
P  P
T +V = 0. (3)
T  V 
V T
(c) Consider a gas obeying an equation of state of the form
RT a
P= , (4)

V b 
V2

where a and b are constants. Assuming ( V b)/

V  1, show that the
inversion temperature, Tinv , is approximated as
2a
Tinv  . (5)
Rb
28 Tosun

Although the inversion temperature turns out to be independent of pressure

for this specific case, it is generally dependent on pressure.
2.2 Ammonia at 400 K and 5 MPa enters a throttling valve and leaves it at 100 kPa.
Determine the exit temperature if the equation of state is given by

P(
V b) = RT ,
where b = 3.73105 m3 /mol. The molar heat capacity at constant pressure
is given by

CP = 25.895 + 0.033T ,

where CP is in J/mol K and T is in K.
(Answer: 404.7 K)
2.3 A gas contained in a piston-cylinder assembly is represented by
 
b

P V a+ = RT . (1)
T
The gas is compressed irreversibly and isothermally from an initial pressure
of P1 to a final pressure of P2 .
(a) Use Eqn (2.2-31) and show that
 
 2b
H = a (P2 P1 ). (2)
T

(b) Using the identity

 = H
U  (P
V) (3)
show that
b(P1 P2 )
=
U . (4)
T
(c) Use Eqn (2.2-26) to obtain
 
 = bR 1 1
U (5)
 b  b
V2 a + V1 a +
T T
and show that the use of Eqn (1) in Eqn (5) leads to Eqn (4).
(d) Show that the entropy change associated with this compression is given
by  
 P2 b(P1 P2 )
S = R ln + . (6)
P1 T2
Thermodynamic Properties of Real Substances 29

2.4 Consider a piston-cylinder assembly containing 3 mol of gas represented by

RT a
P= ,

V b T
V2
where
a = 35 J K m3 /mol2 and b = 4.8 105 m3 /mol.
The gas expands irreversibly from 0.01 m3 to 0.02 m3 at 350 K. Use
Eqn (2.2-38) and calculate the change in entropy associated with this
process.
(Answer: 17.6 J/K)
2.5
(a) Consider a function
y = 3x 2 1.
First evaluate dy/dx. Then express x as a function of y, i.e.

y+1
x=
3
and evaluate dx/dy. Conclude that
dy 1
= .
dx dx/dy
(b) Consider a function
y = 3x 2 sin x + ln x.
Show that
dx x
= 2 .
dy 6x + 1 x cos x
(c) Consider a function
1
z = 6x 2 y + ln x.
x
Show that  
x 6x 4
= .
y z 12x 3 y + x + 1
2.6 Show that the ratio of the heat capacities is expressed in the form

CV T 2
=1 .

CP 
CP
30 Tosun

Using the following values at 298 K and 1 bar, evaluate the term T 2/( 
CP ).

Substance (kg/m3 ) (K1 ) (Pa1 ) 

CP (J/kg K)
Water 1000 2.5 104 4.53 1010 4186
Copper 8920 5 105 9.1 108 386

Although it is widely assumed that  CV   CP for solids and incompressible

liquids, this assumption is not generally correct for various liquids. For a more
thorough discussion on the subject, see Garvin (2002).
2.7 Show that the Gibbs energy can be regarded as a generating function to esti-
mate enthalpy, internal energy, Helmholtz energy, and heat capacity, i.e.
 
G
=
H GT ,
T P
   
= G G
U GT P ,
T P P T
 
 G
A= GP ,
P T
 2 

G

CP = T .
T 2 P
2.8 Express the term (T /P) in terms of measurable quantities as follows:
S
(a) Use the triple product rule to show that
 
T (
S/P)T
= . (1)
P S (S /T )P
(b) Use Eqn (2.2-41) and conclude that
   
S 
V
= , (2)
P T T P
 
S 
CP
= . (3)
T P T
(c) Show that the substitution of Eqns (2) and (3) into Eqn (1) leads to
 
T 
VT
= . (4)
P S 
CP
Thermodynamic Properties of Real Substances 31

(d) Also combine Eqn (4) with Eqn (1) of Problem 2.1 to obtain
 
T 
V
=+ . (5)
P 
S 
CP

(e) A gas obeying

P(
V b) = RT (6)
flows through an isentropic nozzle from high pressure to low pressure.
Will the gas temperature decrease or increase?
(Answer: (e) Decreases)
2.9 Show that
(a)
 

H T 1
= .

V T
(b)
 
G V 
= S.
T V
(c)
  
H CP
= .
T S T

2.10 The volume of an aluminum sphere is reduced from 48.25 cm3 to 48.17 cm3 at
300 K by applying increased pressure. Use Eqns (2.2-38) and (1) of Example
2.2 to estimate the change in entropy. For aluminum

= 6.9 105 K1 and = 13.2 1012 Pa1 .

(Answer: 0.418 J/K)

2.11 Changes in potential energy are considered negligible in the development of

the fundamental equations, i.e. Eqns (2.2-2), (2.2-5), (2.2-8), and (2.2-11).
When the gravitational force is appreciable, the change in potential energy is
represented by

dEP = mg dz, (1)

32 Tosun

where m is the mass, g is the acceleration of gravity, and z is the distance

measured in the direction opposite to gravity. Under these circumstances,
show that the fundamental equations take the following form:

dU = T dS P dV + mg dz, (2)
dH = T dS + V dP + mg dz, (3)
dA = P dV S dT + mg dz, (4)
dG = V dP S dT + mg dz. (5)

2.12 A closed system containing 1 mol of ethanol at 298 K and 1 bar receives
2700 J of heat from its surroundings.

(a) Calculate the final temperature and pressure if heating takes place at con-
stant volume.
(b) Calculate the final temperature and molar volume if heating takes place
at constant pressure.

Assume that CP , , and can be considered constant over the temperature
ranges considered in this problem. Ethanol at 298 K and 1 bar exists in liquid
form and has the following properties:


V = 58.39 cm3 /mol, 
CP = 112.4 J/mol K,
= 1.12 103 K1 , = 1.11 109 Pa1 .

(Answer: (a) 327.1 K, 292 bar and (b) 322 K, 59.98 cm3 /mol)
2.13 Specific volume of liquids can be expressed as a function of temperature and
pressure in the form
 
  P
V (P, T ) = V (0, T ) 1 C ln 1 + , (1)
B(T )

which is known as the Tait equation. Show that the isothermal compressibility
is given by
1
=   . (2)
1 P
[P + B(T )] ln 1 +
C B(T )
Thermodynamic Properties of Real Substances 33

2.14 Isentropic compressibility, , is the variation of volume with pressure at con-

stant entropy per unit volume, i.e.
 
1  V
= . (1)
V P S

(a) Use the triple product rule to show that
 

V (
S/P)
V
= . (2)
P 
S (
S / 
V )P

(b) Use Eqn (2.2-38) and conclude that

   
S 
CV T
= . (3)
P V T P V

(c) Use Eqn (2.2-41) and conclude that

    
S CP T
= . (4)

V P T V P
(d) Substitute Eqns (3) and (4) into Eqn (2) to get
     

V 
CV T 
V
= . (5)
P 
S 
CP P 
V T P

(e) Use the triple product rule to show that

     
T 
V 
V
= . (6)
P 
V T P P T

(f) Show that the use of Eqn (6) in Eqn (5) leads to


CV
= . (7)

CP

(g) The speed of sound, u, is defined by

 
P
u =
2
. (8)
S
34 Tosun

Express Eqn (8) in the form

  
V 2 P
u =
2
, (9)
M  V S
where M is the molecular weight. Combine Eqn (9) with Eqn (1) to obtain
1
= . (10)
u2
Once the speed of sound and density are experimentally measured, the isen-
tropic compressibility is calculated from Eqn (10).

Reference
Garvin, J., 2002, Chem. Eng. Progr., 98 (7), 6465.