CHE1003: PROCESS ENGINEERING

THERMODYNAMICS

Faculty name: Dr. Dharmendra Kumar Bal

Office room: SJT-313-A23A
Email id : [email protected]
Mobile : 9406957419
MODULE-3
 Thermodynamic properties
The fundamental property relations

Enthalpy:
From First Law,

dU  dQ  dW
INTERNAL ENERGY
dU  TdS  pdV
H  U  pV
dH  dU  d(pV)
 dU  pdV  Vdp
 TdS  pdV  pdV  Vdp
dH  TdS  Vdp
 Helmholtz free energy:

It is defined as
A = U – TS

dA = dU - d(TS)
= TdS – pdV – TdS – SdT
dA = - pdV – SdT

Gibb’s Free energy:

It is defined as G = H – TS
Differentiating, dG = dH –TdS – SdT
= TdS +Vdp – TdS – SdT
dG = Vdp - SdT
Some thermodynamic properties can be measured directly, but many others
cannot. Therefore, it is necessary to develop some relations between these two
groups so that the properties that cannot be measured directly can be evaluated.
The derivations are based on the fact that properties are point functions, and the
state of a simple, compressible system is completely specified by any two
independent, intensive properties.

Some Mathematical Preliminaries

Thermodynamic properties are continuous point functions and have exact

differentials. A property of a single component system may be written as general
mathematical function z = z(x,y). For instance, this function may be the pressure P
= P(T,v). The total differential of z is written as
where

Taking the partial derivative of M with respect to y and of N with respect to x yields

Since properties are continuous point functions and have exact differentials, the following is
true

The equations that relate the partial derivatives of properties P, v, T, and s of a simple
compressible substance to each other are called the Maxwell relations. They are obtained
from the four Gibbs equations. The first two of the Gibbs equations are those resulting from
the internal energy U and the enthalpy H.
dU  T dS  P dV
dH  T dS  V dP
The second two Gibbs equations result from the definitions of the Helmholtz function a and
the Gibbs function g defined as

A  U  Ts
dA  dU  T dS  S dT
dA   SdT  P dV
G  H  TS
dG  dH  T dS  S dT
dG   S dT  V dP
Setting the second mixed partial derivatives equal for these four functions yields the Maxwell
relations
The Gibbs Equations
First Law

dU = TdS - PdV

dH = TdS + VdP

dA = -SdT - PdV

dG = -SdT + VdP
 dU = TdS - PdV
The Gibbs equation for dU is
dU＝TdS－PdV
dS＝0 dV＝0
 U   U 
   P   T
 V  S  S V
↓V is held constant ↓ S is held constant
  2U   P    2U   T 
     =     
 VS   S V  SV   V  S

 P   T 
   
 S V  V  S
 M 2 z N 2 z M N
( )x  , ( )y  ( )x  ( ) y
y xy x xy y x

 P   T 
dU = TdS - PdV    
 S V  V  S
 T   V 
dH = TdS + VdP    
 P  S  S  P
 S   P 
dA = -SdT - PdV    
 V T  T V
 S   V 
dG = -SdT + VdP     
 P T  T  P
Another way to write this last result is

The Clapeyron Equation

The Clapeyron equation enables us to determine the enthalpy change associated with a
phase change, hfg, from knowledge of P, v, and T data alone.
Thermodynamic Relations
1. 2.
 T   p   T   V 
DU = Q - W          
 V  S  S V  p  S  S  p
(a)

(b) DS = qrev/T

(c) H = U + pV 3. 4.
 S   p   S   V 
(d) A = U – TS
        
(e) G = H - TS  V T  T V  p T  T  p

1. dU = TdS – pdV (a)  (b)

2. dH = TdS + Vdp (a)  (b)  (c)

 z   z 
Mdx  Ndy  dz    dx    dy
 x  y  y  x
3. dA = -SdT - pdV (a)  (b)  (d)

 M   N 
    
4. dG = -SdT + Vdp (a)  (b)  (e)
 y x  x y

14
 The Maxwell Relations: The Magic Square

V A T
“Vat Ug Ship”

Each side has an energy ( U, H, A, G )

Partial Derivatives from the sides

U G
Thermodynamic Identities from
the corners

Maxwell Relations from walking

around the square

1. dU = TdS – pdV
S H P
 T   p   T   V 
         
2. dH = TdS + Vdp  V  S  S V  p  S  S  p
3. dA = -SdT - pdV
4. dG = -SdT + Vdp  S   p   S   V  15
        
 V T  T V  p T  T  p
 Material Equilibrium

Application of Maxwell Relations

Example 1: Prove that the internal energy of ideal gas is a
function of temperature only.
Answers. dU  TdS  PdV
 S   P 
 U   S     
   T  P  V T  T V
 V T  V T
nRT
For ideal gas PV  nRT P
V
 P  nR
  
 T V V
 U   P  nR
   T  P T P 0
 V T  T V V
 Application of Maxwell Relations
Example 2: Calculate DU when an ideal gas changes from
P1, V1, T1 to P2, V2, T2. (Hint: applying  U  )
Answers.  V T
U  U (T ,V )  U   P 
   T  P
 V T  T V
 U   U 
dU    dT    dV
 T V  V T
  P  
 CV dT  T    P  dV
  T V 
  P  
DU   CV dT   T    P dV
  T V 
Calculation of DH and DU
2 2
DH   CP dT   (V  TV )dP
1 1
DH for the process (P1, T1) (P2, T2) is independent of the
path used. A convenient path (Fig. 4.5) is suggested.
T2 P
DH a   CP dT const. P=P1
T1
1 (a)
P2 P1
DH b   (V  TV )dP const. T=T2 (b)
P1
P2 2
DH for the process (P1, T1) (P2, T2) is
T
DH  DH a  DH b T1 T2
DU  DH  D(PV )
Calculation of DG and DA
DG for an isothermal process (DT=0)
DG  G2  G1  H 2  TS2  ( H1  TS1 )  DH  TDS

 G  DG  DH  TDS const. T
   V (4.51)
 P T P
DG   VdP
2
const. T
P1

DG  0 rev. proc. at const. T and P; P-V work only

DA for an isothermal process (DT=0)

2
DA  DU  TDS DA   PdV
1
 Fugacity
• The tendency of a substance to prefer one phase (liquid, solid, or gas)
over another, and can be literally defined as “the tendency to flee or
escape”. At a fixed temperature and pressure, a homogeneous substance
will have a different fugacity for each phase. The phase with the lowest
fugacity will be the most favorable, and will have the lowest Gibbs free
energy.

• A measure of the tendency of a component of a liquid mixture to escape,

or vaporize, from the mixture.

• The composition of the vapour form of the mixture, above the liquid, is
not the same as that of the liquid mixture; it is richer in the molecules of
that component that has a greater tendency to escape from the liquid
phase.

• The fugacity of a component in a mixture is essentially the pressure that

it exerts in the vapour phase when in equilibrium with the liquid
mixture.

• Fugacity has the same units as pressure (e.g., atm, psia, bars, etc.) 22
the fugacity of a real gas is an effective pressure which replaces the true
mechanical pressure in accurate chemical equilibrium calculations

Fugacity of Pure Species:

Fugacity is used to represent behavior of real gases.
dG  Vdp  SdT
Under isothermal conditions,
dG  Vdp
If the gas is ideal,
dp  RTd ln p 
RT
dG 
p
dG  RTdln p

23
 dG  RTdln p

This is not true for real gases. In order to make this

equation valid, let us choose f such that
dG  RTdln f  For any gas at constant T
Here f is called fugacity and the above equation
defines it partially.
G  RT ln f  C C is a function of T.

24
 dG  RTdln f 
f2
ΔG  G2  G1  RT ln For any gas.
f1
p2 For ideal gas.
ΔG  RT ln
p1
Thus in case of ideal gases,
f2 p2

f1 p1
i.e., f  p
Proportionality constant is taken as unity.
For ideal gases, f = p.
25
 As pressure is decreased, we
know real gases will increasingly
behave like ideal gases.
f f
lim 1 or 
1 as p  0
p0 p p

Standard state of a real gas is a hypothetical state in

which the gas behaves as an ideal gas. This happens
at low pressure, let us say at p = p0.

26
Fugacity coefficient  = f/p is defined as the ratio of
fugacity to the pressure. A dimensionless term
depends on nature of the gas, the pressure and the
temperature f
G  G0  RT ln
f0
p
G  G0  RT ln f f o

p0   ;  1  o
p p
p
G  G0  RT ln  RT ln 
p0
p
G  G0  RT ln  RT ln 
p0
Free Energy of real gas = free energy of ideal gas + RT ln 

Clearly, for ideal gases, as p  0 ,   1.

27
   ln f  H0  H
Effect of temperature on fugacity:   
 T  p RT 2
f
Derivation G  G0  RT ln
f0
f G G0
R ln  
f0 T T
G G0
R(ln f  ln f0 )  
T T
Partial differential w. r. t. T at constant pressure,
  ln f    ln f0     ( G / T )    ( G0 / T ) 

R         
 T  p  T  p0   T  p  T  p0

28
Substituting Gibb’s – Helmholtz equation
 ( G / T )  H
   
  T p T2

  ln f    ln f0    H   H 0 
R        2    2 
 T  p  T  p0   T   T 

Here f0 is fugacity at low pressures. The variation of

fugacity will be negligibly small.

29
   ln f0 
  0
 T  p0

  ln f  H0  H
  
  T p RT 2

This equation gives the effect of temperature

on fugacity

30
Effect of pressure on fugacity:
Recall dG  Vdp  SdT
Under isothermal conditions, dG  Vdp  RTdln f 

Writing it as partial differential equation with respect

to pressure at constant T,
  ln f  V
  
 p T RT
This equation represents effect of pressure on fugacity.

31
 Fugacity determination
• Using Compressibility Factor, Z ( Z of a real gas is the ratio of its volume
to the Volume of an ideal gas at the same Temperature and Pressure)
• Using EOS.
• Using Values of enthalpy and entropy

32
Fugacity determination:
dG  Vdp  RTdln f  Constant T
V Z
 
d ln f  dp  dp
RT p
We need to integrate this between p = 0 to the pressure at
which we want to determine fugacity.
As p  0, f  p
And unfortunately, ln p p 0 is not defined.
To overcome this difficulty we add and subtract dP/P on
RHS of the above equation

33
 Z
d ln f   dp
p
1 1 Z
 dp  dp  dp
p p p
Z 1
 d ln p   dp
p
 f  Z 1
d  ln   dp
 p p
Z 1
d ln   dp
p

34
 Z 1
p p

 d ln   
0 0
p
dp

p p
Z 1 Z 1
 
p
ln  p 0
 dp ln   ln( 1 )  dp
p p
0 0

Z 1
p

ln   dp
0
p

35
Using equation of state:
dG  Vdp  RTdln f  Constant T

d ln f  
1
Vdp
RT
f p

f d ln f   p RT Vdp
1
0 0

p
f 1
ln  
f0 RT p0
Vdp

36
 p
f 1
ln  
f0 RT p0
Vdp

Fugacity of van der Waals gas:

p
f 1
ln  
f0 RT p0
Vdp

 a 
Equation of state is  p  2 
( V  b )  RT
 V 
RT a
p  2
V b V
 RT 2a 
dp     3 dV
 (V  b )
2
V 

37
 p
f 1
ln 
f0 RT  Vdp
p0

V
f 1  RT 2a 
ln 
f0 RT  V  
V0 
(V  b ) 2
 3 dV
V 

V V
VdV 2 aVdV

V0
 (V  b ) 2
 
V0
RTV 3

38
 V V
f 2 adV VdV
ln 
f0  RTV
V0
2
  (V  b )
V0
2

V V
f 2a VdV
ln  
f0 RTV V0
  (V  b )
V0
2

V
f 2a 2a VdV
ln  
f0

RTV RTV0

V0
 (V  b ) 2

V
f 2a VdV
ln
f0

RTV
  (V  b )
V0
2

39
 VdV
 (V  b ) 2

Put V  b  u
dV  du

( u  b )du 1 b 
 
b b
   2 du  ln u   ln( V  b ) 
u2  u u  u V b
V
VdV  V b  b b

V0
(V  b ) 2
 ln  
 
 V0  b  V  b V0  b
 V b  b
 ln 
 V b
 V0  b 

40
 V
f 2a VdV
ln
f0

RTV
  (V  b )
V0
2

V
VdV  V b  b

V0
( V  b ) 2
 ln 
 0
V  b

 V b


f 2a  V b  b
ln   
 ln  

f0 RTV  V0  b  V  b

f 2a V  b  b
ln  
 ln  

p0 RTV  V0  V  b

41
 f 2a V  b  b
ln  
 ln  

p0 RTV  V0  V  b
2a b
ln f  ln p0    ln( V  b )  ln V0 
RTV V b

2a  RT  b
  ln( V  b )  ln 
 V b
RTV  p0 
2a b
ln f  ln p0    ln( V  b )  ln( RT )  ln p0 
RTV V b
 RT  b 2a
ln f  ln  
 V  b  V  b RTV
42
 Residual Property
A residual property is the difference between actual property of a substance
and the property calculated using ideal gas at same Temp and Pressure
H R  H  H ig ; S R  S  S ig
U R  U  U ig ; G R  G  G ig
DH  H 2  H1  ( H 2R  H 2ig )  ( H1R  H1ig )
Change in property, DH, DS, DG
 ( H 2ig  H1ig )  ( H 2R  H1R )  DH ig  DH R
Change in property, DG f
Therefore, dG R  RTd (ln f  ln p)  RTd ln
dG  dG ig  dG R P
 GR   f 
dG  dG  dG
R ig
d   d  ln 
 RT   P
but , dG ig  RTd ln P;
 GR   GR   f   f 
dG  RTd ln f int from 0 to P;       ln    ln 
 RT  P  P  RT  P 0  P  P  P  P  P 0
If integrated from
standard state (ideal)  GR   f 
    ln 
to the actual state G  RT   P
then f
f G R  RT ln
G  Gig  RT ln ig P at constant Pressure
f 43
 Fugacity determination

Z 1
p

Using Compressibility Factor, Z ln   dp

0
p

1  
p V
Using EOS. f 1
ln 
f0 RT p Vdp  RT  PV  RT  V PdV 
0  0 

44
 Problem

Derive an expression for

fugacity co-efficient for a gas
that follows PV  RT  aP where “a” is a constant.
p
f  Z 1
ln 
p 
0
dp
p  PV aP
 1
RT RT
aP
f
p
a Z  1
ln    dP RT
P 0 RT Z 1 a

P RT
45
 p
f a
ln    dP
P 0 RT
f aP
ln  
p RT
aP

 e RT

Estimate the fugacity of ammonia at 10 bar and 298 K, a = 3.707 x 10-5 m3/mol

f (3.7 x105 )(10 x105 )

ln   
p 8.314 x298

46
generalized fugacity charts

47
48
 EXAMPLE

Calculate the fugacity of CO2 at 600°C (873 K) and 1200

atm.

Tc = 304.2 K; Pc = 72.8 atm

Tr = 2.87; Pr = 16.48
From the chart   1.12
so
f = (1.12)(1200) = 1344 bars

49
EXAMPLE : What is the fugacity of liquid Cl2 at 25°C and
100 atm? The vapor pressure of Cl2 at 25°C is 7.63
atm.
For the vapor coexisting with liquid:
Tc = 417 K; Pc = 76 atm
Tr = 0.71; Pr = 0.10
from the chart   0.9
f = (0.9)(7.63) = 6.87 atm
Now we must correct this to 100 atm.
V
ln f 2  ln f1  ( P2  P1 )
RT

V = 51 cm3 mol-1; assume to be constant.

f2 = 8.36 atm 50
Problem
For isopropanol vapor at 200oC the following equation is available
Z=1 - 9.86 x 10-3 P -11.45 x 10-5 P2
Where P is in bars. Estimate the fugacity at 50 bars and 200oC

PV
Z  1  9.86  10 3 P  11.41  10 5 P 2
RT
ZRT RT
V  (1  9.86  10 3 P  11.41  10 5 P 2 )
p P
P
1
ln f  
RT 1
VdP
P
1 RT

3 5
ln f  (1  9.86  10 P  11 .41  10 P 2
)dP
RT 1 P
50 50 50
dp
ln f     9.86  10 3 dP   11.41  10 5 PdP
1
p 1 1
 50  (50  1 )
2 2
ln f  ln    9.86  10 3 50  1  11.41  10 5
 1 2
f =26.744 bar f 26.744
   0.5348
P 50
51
Fugacity for liquids and solids

General expression for fugacity is

P
1
ln f  
RT 1
VdP

For solids and liquids at constant temperature the specific volume does
not change appreciably with pressure, therefore the above equation is
integrated by taking volume constant. Integrating the above equation
from condition 1 to 2
f2 P
V 2
f ln f  RT P dP
f2
ln 
V
P2  P1 
1 1 f1 RT

Problem
Liquid chlorine at 25oC has a vapour pressure of 0.77Mpa, fugacity 0.7Mpa
and Molar volume 5.1x 10-2 m3/kg mole. What is the fugacity at 10 Mpa and
25oC

52
 P1  0.77  10 6 Pa

P2  10  10 6 Pa

f1  0.7  10 6 Pa
T  298 K
J
R  8314
Kgmole

f2
ln 
V
P2  P1 
f1 RT

f=0.846Mpa

53
 Activity(a)
It is defined as the fugacity of the existing condition to the standard state fugacity
f
a o
f
Effect of pressure on activity
The change in Gibbs free energy for a process accompanying change of state
from standard state at given condition at constant temperature can be predicted as
G  RT ln f

G o  RT ln f o
 f 
DG  G  G o  RT ln  o   RT ln a
f 
at constant temperature dG  VdP

G P

 dG  V  dP
GO Po

DG  V ( P  P o )

RT ln a  V ( P  P o )

V
ln a  (P  P o )
RT
This equation predicts the effect of pressure on activity
54