Chemical Engineering

Thermodynamics-I
Lecture 4
Prof.Dr.Mahmood Saleem
Institute of Chemical Engineering &
Technology
University of the Punjab, Lahore
 Contents
• Introduction
• Property relations for Homogeneous Phase
• Residual Properties
• Residual Properties by Equation of State
• Property Relations for Two Phase Systems
• Thermodynamic Property Diagrams and Tables
• Generalized property Correlations for Gases
• Extension of Generalized property Correlations for
Gases to Mixtures
• Exercises
 Introduction
• Processing of materials (pure and mixtures) is
key affair in chemical processes
• Estimation of many properties (and change)
other than volumetric properties (H,U,s,G etc.)
are required.
• How to know complete property set when
volumetric properties are not available
• What tools can one use to handle such issues?
Property Relations for Homogeneous Phases
Fundamental Properties

d (nU )  dQrev  dWrev

d  nU   T .d  nS   P.d  nV  …(6.1)

 Although equation (6.1) is derived from the special case of

a reversible process, it not restricted in application to
reversible process.
 It applies to any process in a system of constant mass that
results in a differential change from one equilibrium state to
another.
 The system may consist of a single phase or several
phases; may be chemically inert or may undergo chemical
reaction.
Definitions

H = Enthalpy H  U  PV …(2.11)

A = Helmholtz energy A  U  TS …(6.2)

G = Gibbs energy G  H  TS …(6.3)

Based on one mole (or to a unit mass) of a
homogeneous fluid of constant composition,
they simplified to
Function Change

U ( s, V )..............dU  TdS  PdV

H ( s, P ).............dH  TdS  VdP
A(V , T ).............dA   PdV  SdT
G ( P, T ).............dG  VdP  SdT
 Maxwell’s equations
G ( P, T )  T 

 P 
   
 V  S  S V
dG  ...V ......dP  ...S ......dT
 T   V 
   
 G   G   P  S  S  P
dG    dP    dT
 P T  T  P  P 
  
 S 

 T V  V T
 V   S 
   .   V 

 S 
   
 T  P  P T  T  P  P T
 Enthalpy and Entropy as Functions of T and P
 Temperature derivatives:
 H 
   CP
 T  P
 S  CP
  
 T  P T
 Pressure derivatives:
 S   V 
    
 P T  T  P
 H   V 
  V T 
 P T  T  P
The most useful property relations for the enthalpy
and entropy of a homogeneous phase result when
these properties are expressed as functions of T
and P (how H and S vary with T and P).

  V  
dH  C p dT  V  T    dP
  T P  …(6.20)

dT  V 
dS  C P   dP …(6.21)
T  T  P
 Property Relations for Homogeneous
Phases
Internal Energy as Function of P (U(P))
• The pressure  T   P 
    
dependence of the  V  S  S V
internal energy is
 T   V 
shown as    
 P  S  S  P
 P   S 
 U   V   V     
   T    P   T V  V T
 P T  T  P  P T
 V   S 
dU  Tds  PdV     
 T  P  P T
 Property Relations for Homogeneous
Phases
The Ideal Gas State
• For ideal gas,
  V  
expressions of dH dH  C p dT  V  T    dP
  T  P 
and dS (eq.6.20-6.21)
dT  V 
as functions of T and dS  C P 
T  T  P
 dP
P can be simplified as
follows using ideal
gas law:
 V ig  R
PV ig
 RT    
 T P P
dH ig  C Pig dT (6.23)
dT dP
dS ig  C Pig R (6.24)
T P
  V   V 
dV    dT  
Property Relations for Homogeneous  T P  P
 dP
T
Phases  
1  V 

V  T  P
Alternative Forms for Liquids
  T    P  
1  V 
• Relations of liquids      V  P 
can be expressed in  V  S  S dVV
T

  dT  dP
terms of  and  as  T   V  V  V  
dH  Cp dT  V  T    dP
follows:  P  S   S  P  T  P 
 S 
    V  P  dT   SV 
dS  CP      dP
P
 T T T
 T V  V T P
 H 
   1  T V  V   S 
 P T     
 T  P  P T
 U  U  V  V 
    P   T V 
   T 

  P


  P T  P T  T  P  P T
dU  Tds  PdV
Property Relations for Homogeneous Phases
Alternative Forms for Liquids

• Enthalpy and entropy as functions of T and P

as follows:

dH  C P dT  1  T VdP ...( 6.28 )

dT
dS  C P  VdP ...( 6.29 )
T

  and  are weak functions of pressure for

liquids, they are usually assumed constant at
appropriate average values for integration.
 Practice 1
Determine the enthalpy and entropy changes of liquid water for
a change of stage from 1 bar 25C to 1,000 bar 50C.
T P Cp V 
( C) (bar) (Jmol-1K-1 (cm3mol-1) (K-1)
25 1 75.305 18.071 256x10-6

25 1000 … 18.012 366x10-6

50 1 75.314 18.234 458x10-6

50 1,000 … 18.174 568x10-6

Constant P

Constant T
H  C p  T2  T1   1  T2  V  P2  P1  Integrated forms of
T2 equations for change in
S  C p ln  V  P2  P1  Enthalpy and Entropy
T1

For P  1 bar , Average value at T1

and T2 at 1 bar
75.305  75.314
Cp   75.310 Jmol 1 K 1
2

and for T  50C ,

Average value at P1
18.234  18.174 and P2 at 50 oC
V  18.204 cm3 mol 1
2
458  568
  10 6  513  10 6 K 1
2
 H  C p  T2  T1   1  T2  V  P2  P1 
T2
S  C p ln  V  P2  P1 
T1

H  75.310 323.15  298.15 

1   513 10  323.15 18.204 1,000  1
6

10
 1,883  1,517  3,400 Jmol 1 On substitution of values

S  75.310 ln
 
323.15 513  10 6 18.204 1,000  1

298.15 10
 6.06  0.93  5.13 Jmol 1 K 1

Note that the effect of P of almost 1,000 bar on H and S of liquid water
is less than that of T of only 25C.
Property Relations for Homogeneous Phases
Internal Energy and Entropy as Function of T and V

• Useful property relations for T and V as independent

variables are

 S  CV
  
 T V T
 U   P 
   T  P
 V T  T V
 P  
  
 T V 
• The Partial derivatives dU and ds of homogeneous fluids
of constant composition to temperature and volume are
  P  
dU  CV dT  T    P  dV
  T V 
dT  P 
dS  CV   dV
T  T V

• Alternative forms of the above equations are

    V 
dV  
 V 
 dT    dP
dU  CV dT  T  P  dV  T  P  P T
   1  V 
  
dT  V  T  P
dS  CV  dV 1  V 
T     
V  P T
dV
  dT  dP
V
 Property Relations for Homogeneous Phases
The Gibbs Energy
• An alternative form of a fundamental property
relation as defined in dimensionless terms:
 G  V H
d   dP  2
dT
 RT  RT RT
V    G RT  
 
RT  P T
H    G RT  
 T  
RT  T  P

•The Gibbs energy when given as a function of T and

P therefore serves as a generating function for the
other thermodynamic properties, and implicitly
represents complete information.
 Residual Properties

• The definition for the generic residual property is:

M  M M
R ig

M = the Residual M is the actual Mig = the ideal

Molar gas molar value of gas properties
properties which any extensive which are at the
are at the same thermodynami same
temperature and cs property: V, temperature and
pressure. U, H, S, G. pressure.
• Residual Gibbs energy:

G  G G
R ig

• Residual volume:
RT PV=ZRT
V  V V
R ig
V 
P
RT
V  R
 Z  1
P
Fundamental property relation for residual properties

• The fundamental property relation for residual

properties applies to fluids of constant composition.

G  V HR
R R

d  dP  dT  ( 6.42 )
 RT  RT RT 2

V R    G R / RT  
   ( 6.43 )
RT  P T

HR    G / RT  
R

 T    ( 6.44 )
RT  T P
  GR  V R
From Eq.(6.43), d    dP (const T )
 RT  RT

GR  GR  PV
R
P dP  GR 
     dP   ( Z  1)  (6.45) for ideal gas    0
RT  RT  P 0 0 RT 0 P  RT  P 0

HR P  Z  dP
Eq.(6.45  6.44);  T     (6.46)
RT 0
 T  P P

S R H R GR
From  
RT RT RT

SR P  Z  dP P dP
So,  T     0 ( Z  1) (const T )  (6.48)
R 0 T
 P P P
 Enthalpy and Entropy from Residual Properties

Applied to H and S ; H  H ig  H R S  S ig  S R
Integration of Eq .( 6.23 )and ( 6.24 );
T T
P
H  H 0   C P dT
ig ig ig
S  S 0   C P dT  R ln
ig ig ig

T0 T 0 P0
T

Substituti on ; H  H 0   C Pig dT  H R
ig
 ( 6.50 )
T0

T
P
S  S 0   C P dT  R ln  S R  ( 6.51 )
ig ig

T 0 P0
 H ig  H 0ig  C P H
( T  T0
)  H R
 ( 6.52 )
T P
S  S 0  C P S ln  R ln  S R  ( 6.53 )
ig ig

T0 P0
T2

 P dT
C ig

CP C D
CP  T1
 H
 A  BTam  ( 4Tam  T1T2 ) 
2
H
T2  T1 R 3 T1T2
T2
dT
T C P T
ig

CP  D 
CP  1
 S
 A  BTlm  TamTlm C  2 
S
ln( T2 / T1 ) R   T1T2  

The true worth of the Eq. for ideal gases is now evident.
They are important because they provide a convenient base
for the calculation of real-gas properties.
Practice 2

Calculate H and S of saturated isobutane vapor

at 630 K from the following information:
1. Table 6.1 gives compressibility-factor data
2. The vapor pressure of isobutane at 630 K
15.46 bar
3. Set H0ig = 18,115 Jmol-1 and S0ig = 295.976
Jmol-1K-1 for the ideal-gas reference state at
300 K 1 bar
4. Cpig/R = 1.7765+33.037x10-3T (T/K)
Solution 6.3

Eqs. (6.46) and (6.48) are used to calculate HR and SR.

P  Z  dP P dP
0  T  P P 0 (Z  1) P
 Plot (Z/T)P/P and (Z-1)/P vs. P
 From the compressibility-factor data at 360 K  (Z-1)/P
The slope of a plot of Z vs. T  (Z/T)P/P
The
Data for the required plots are shown in Table 6.2.
  Z  dP dP
 26.37  10 K 0 ( Z  1 )  0.2596
P P
0  
4 1

 T  P P P
H R

By Eq . ( 6.46 ),  ( 360 )( 26.37  10 4 )  0.9493

RT
S R

By Eq . ( 6.48 ),  0.9493    0.2596  0.6897

R
For R  8.314 Jmol 1 K 1
H R    0.9493 8.314 360  2 ,841.3 Jmol 1
S R    0.6897 8.314  5.734 Jmol 1 K 1
 C Pig H
 A  BTam  1.7765  33.037  10 3 Tam
R
C Pig S
 A  BTlm  1.7765  33.037  10 3 Tlm
R
T0  T1 300  360
Tam    330 K
2 2
T1  T0 360  300
Tlm    329.09 K
ln( T1 / T0 ) ln( 360 / 300 )
C Pig H
 12.679( 8.314 )  105.41 Jmol 1 K 1
C Pig S
 12.649( 8.314 )  105.16 Jmol 1 K 1
Substitute int o Eq .( 6.50 ) and ( 6.51 )
H  18 ,115  105.41( 360  300 )  2 ,841.2  21,598.5 Jmol 1
 360 
S  295.576  105.16 ln( )   8.314 ln15.41  5.734  286.676 Jmol 1 K 1
 300 
 Residual Properties by Equations of State
Residual Properties from the Virial Equation of
State
• The two-term virial eq. gives Z-1 = BP/RT.

GR P dP
  ( Z  1)
RT 0 P
G R BP
So,   (6.54)
RT RT
HR
 T 
 
  G R / RT  P  B dB 
By Eq.(6.44),       (6.55)
RT  T  P R  T dT 
SR P dB
Substitution int o Eq.(6.47),   (6.56)
R R dT
 In application  is a more convenient variable than V,
PV = ZRT is written in the alternative form.

dP d dZ
P  ZRT  ( 6.57 ), dP  RT ( Zd  dZ )   
P  Z
GR  d
Substitue int o Eq .( 6.49 );   ( Z  1 )  Z  1  ln Z  ( 6.58 )
RT 0 
HR Z  1  P   ( G R / RT ) 
From Eq .( 6.40 ) and ( 6.42 ),     
RT 2
P  T    T 

HR 
 Z  d
Differenti tion of Eq .( 6.57 ) and ( 6.58 );  T     Z  1  ( 6.59 )
RT 0  T 
 

SR 
 Z  d  d
From Eq .( 6.47 ),  ln Z  T      ( Z  1 )  ( 6.60 )
  
R 0  T  0
• The three-term virial equation.

Z  1  B  C 2 is substitued int o Eq.(6.58) through (6.60).

GR 3
  2 B  C 2  ln Z  (6.61)
RT 2
HR  B dB   C 1 dC  2 
 T           (6.62)
RT  T dT   T 2 dT  
SR  B dB  1  C dC  2 
 ln Z  T           (6.63)
R  T dT  2  T dT  

Application of these equations, useful for gases up to

moderate pressure, requires data for both the second and
third virial coefficients.
Residual Properties by Cubic Equations of State
Eq.(3.42) devides by RT and substitute V  1 /  , as q given by Eq.(3.51).
1 b
 Z q
1  b (1  b)(1  b)
b b
Z 1  q  (6.64)
1  b (1  b)(1  b)
 Z   dq  b
    
 T   dT  (1  b)(1  b)
The integrals of Eqs.(6.58), (6.60);
  
d b d ( b) d ( b )
0 (Z - 1)
 0 1  b b
  q 0 (1  b)(1  b)
 
 Z  d dq d ( b)
0  T    dT 0 (1  b)(1  b)
   

 
d  Z  d dq
To simplify;  (Z - 1)   ln(1  b)  qI , 0  T    dT I
   
0

The generic equation of state presents two cases.

1  1  b 
Case I :    I  ln   (6.65a )
    1  b 
When ρ is eliminated in favor of Z.
bP P 
 Z whence  b
RT RT Z
1  Z   
I ln   (6.65b)
    Z   
b 
Case II :    I 
1  b Z  
 R
G
 Z  1  ln(1  b) Z  qI  (6.66a )
RT
GR
 Z  1  ln(Z   ) Z  qI  (6.66b)
RT
H R
 d ln  (Tr ) 
 Z 1   1 qI  (6.67)
RT  d ln Tr 
SR
d ln  (Tr )
 ln(Z   )  qI  (6.68)
R d ln Tr
Ex. 6.4
Find values for the HR and SR for n-butane gas at 500 K
50 bar as given by the Redlich/Kwong Eequation.

Solution
Tr = 500/425.1 = 1.176, Pr = 50/37.96 = 1.317
From Table 3.1:

Pr 1.317
Eq.(3.53);     0.08664  0.09703
Tr 1.176
  Tr  0.42748
Eq.(3.54); q    3.8689
Tr  0.08664 1.176 3/ 2
 Z 
Eq.(3.52) : Z  1    q
 Z    Z   
Z  0.09703
 1  0.09703   3.8689  0.09703
Z ( Z  0.09703)
Solution of this Eq. yields Z  0.6850. Then:
Z 
I  ln  0.13247
Z
1 1
With ln  (Tr )   ln Tr , d ln  (Tr ) / d ln Tr   . Then :
2 2
HR
Eq.(6.67) :  0.6850  1  (0.5  1)(3.8689)(0.13247 )  1.0838
RT
SR
Eq.(6.68) :  ln(0.6850  0.09703)   0.5(3.8689)0.13247   0.78735
R
Thus , H R  8.314 500   1.0838   4,505 Jmol 1

S R  8.314(0.78735)  6.546 Jmol 1 K 1

 These results are compared with those of other
calculation in Table 6.3.
 TWO-PHASE SYSTEMS
G   G  , dG   dG   V  dP sat  S  dT  V  dP sat  S  dT
dP sat S   S  S 
Re arrangement ,   
dT V  V 
V 
Integration of Eq .( 6.8 ); H   TS  ( The latent heat of phase transition )
dP sat H 
Thus , S  H / T 
 
  ( 6.71 ) : The Clapeyron equation
dT TV 

dP sat  H l
Phase transition from liquid to vapor ;   ( 6.72 )
dT TV l

RT d ln P sat H l 
But V  sat Z 
l l
  ( 6.73 )
P dT RT Z
2 l
The Clapeyron eq.
d ln P sat H l for pure-species
or   ( 6.74 ) vaporization
d ( 1 / T ) RZ l
 Temperature Dependence of the Vapor
Pressure of Liquids

B
ln P sat  A 
T
B
The Antoine eq . : ln P  A 
sat
 ( 6.76 )
T C
Antoine cons tan ts are given in Table B .2 , App .B
A   B  1.5
 C  3
 D 6

A function of Tr ; ln Pr sat ( Tr )   ( 6.77 )

1
where   1  Tr
 Corresponding-States Correlations
for Vapor Pressure
Lee / Kesler correlatio n :
ln Prsat (Tr )  ln Pr0 (Tr )   ln Pr1 (Tr )  (6.78)
6.09648
where ln P (Tr )  5.92714 
r
0
 1.28862 ln Tr  0.169347Tr6  (6.79)
Tr
15.6875
ln Pr1 (Tr )  15.2518   13.4721ln Tr  0.43577Tr6  (6.80)
Tr
ln Prnsat  ln Pr0 (Trn )
 1
 (6.81)
ln P (Trn )
r

where
Trn : The reduced normal boiling point
Prnsat : The reduced vapor pressure corresponding to 1 atm
Ex. 6.6
Determine the vapor pressure for liquid n-hexane at 0, 30,
60 and 90C: (a) With constants from App. B.2.
(b) From the Lee/Kesler correlation for P rsat
Solution
(a) 2696.04
ln P sat  13.8193 
t  224.317

(b) Eq.(6.78); Tr 
341.9
 0.6736, Prsat 
1.01325
 0.03350
From Table B.1, 507.6n
30.25
n

From Eq.(6.81)   =0.298

t/C Psat/kPa Psat/kPa t/C Psat/kPa Psat/kPa

(Antoine) (Lee/Kesler (Antoine) (Lee/Kesler
) )
0 6.052 5.835 30 24.98 24.49
60 76.46 76.12 90 189.0 190.0
The average difference from the Antoine values is about 1.5%.
 Two-Phase Liquid/Vapor System

nV  n lV l  n V  n  nl  n v (moles)

V  x lV l  x V  x : mass fraction

V  (1  x v )V l  x V  xl  1  xv

The generic equation :

M  (1  x v ) M l  x M   (6.82a )
where M  V ,U , H , S , etc. An alternativ e form :
M  M l  x M l  (6.82b)
THERMODYNAMIC DIAGRAMS
GENERALIZED PROPERTY
CORRELATION FOR GASES

P  Pc Pr  dP  Pc dPr , T  TcTr  dT  Tc dTr

substitue int o Eqs.(6.46) and (6.48) :
Pr
2  Z  dPr
R
H
 Tr     (6.83)
RTc 0
Tr  Pr Pr
Pr P
SR  Z  dPr r dPr
R
 Tr 0  Tr    ( Z  1)
 Pr Pr 0 Pr
 (6.84)
  Z   Z 0   Z 1 
Z  Z  Z  
0 1
       
 Tr  Pr  Tr  Pr  Tr  Pr

H R  2 r  Z 0  dPr   Pr  Z 1  dP 
P

Eq.(6.83) :   Tr       Tr2    r

RTc  0
Tr  P Pr   0  Tr  Pr Pr 
 r 

HR

 
HR

HR
0
  1

 (6.85)
RTc RTc RTc

SR  r   Pr  dP
P
 Z 1  dP  Z 1 
Eq.(6.84) :    Tr    Z 0  1 r 
 Tr    Z 1  r
R  0
  Tr  Pr Pr 

0
  Tr  Pr  Pr


SR

 
SR

0
SR   1

 (6.86)
R R R Table E.5 - E.12
Analytical correlation of the residual properties at low pressure

The generalized sec ond  virial  coefficient correlation forms


 BP d B dB 0 dB1
B  c  B 0  B1 ,  
RTc dTr dTr dTr
  
R   R

H d B S dB
Eqs.(6.55) and (6.56);  Pr  B  Tr ,   Pr
RTc  dTr  R dTr
 
 
  
  1 
HR d B 0
d B
  Pr  B 0  Tr    B1  Tr   (6.87)
RTc  dTr  dTr 
  
  
 
SR  d B0 d B1 
  Pr     (6.88)
R dT
 r dT r 
 
 0.422
B  0.083  1.6
0
 (3.65)
Tr
0.172
B  0.139  4.2
1
 (3.66)
Tr
dB 0 0.675
 2.6  (6.89)
dTr Tr
1
dB 0.722
 5.2  (6.90)
dTr Tr
 HR and SR with ideal-gas heat capacities
 For a change from state 1 to 2:
T2 T1

H 2  H   C dT  H
ig
0
ig
P
R
2 H1  H   C Pig dT  H1R
ig
0
0 0

The enthalpy change for the process, H = H2 – H1

T2

H   C Pig dT  H 2R  H1R  (6.91)

T1
T2
P2
Similarly, S   C Pig dT  R ln  S 2R  S1R  (6.92)
T1
P1
 Alternative form

H  C Pig (T2  T1 )  H 2R  H1R  (6.93)

H

T2 P
S  C Pig ln  R ln 2  S 2R  S1R  (6.94)
S T1 P1
 A three-step calculational path
• Step 11ig: A hypothetical process that transforms a real
gas into an ideal gas at T1 and P1.
H1ig  H1   H1R S1ig  S1   S1R

• Step 1ig 2ig: Changes in the ideal-gas state from (T1,P1)

to (T2,P2). T2

H ig  H 2ig  H1ig   C Pig dT  (6.95)

T1
T2
dT P2
S  S  S   C
ig ig
2
ig
1  R ln  (6.96)
ig
P
T1
T P1
• Step 2ig 2: Another hypothetical process that transform
the ideal gas back into a real gas at T2 and P2.
H 2  H 2ig  H 2R S 2  S 2ig  S 2R
Ex. 6.9
Estimate V, U, H and S for 1-butane vapor at 200C, 70 bar
if H and S are set equal to zero for saturated liquid at 0C.
Assume: Tc=420.0 K, Pc=40.43 bar, Tn=266.9 K, =0.191
Cpig/R=1.967+31.630x10-3T-9.837x10-6T2 (T/K)
Solution
200  273.15 70
Tr   1.127 Pr   1.731
420.0 40.43
Eq.(3.57) and Table E.3 and E.4;
Z  Z 0  Z 1  0.485  0.191(0.142)  0.512
ZRT 0.512(83.14)(473.15)
V   287.8 cm3mol 1
P 70
• Step (a): Vaporization of saturated liquid 1-butane at 0C
B
ln P sat  A   (6.75)
T
• The vapor pressure curve contains both
B
the normal boiling po int; ln 1.0133  A 
266.9
B
the critical po int; ln 40.43  A 
420.0
Whence, A  10.126 B  2,699.11

• The latent heat of vaporization, where Trn=266.9/420=0.636:

H nlv 1.092(ln Pc  1.013) 1.092(ln 40.43  1.013)
   9.979
RTn 0.930  Trn 0.930  0.636
H nlv   9.979 8.314 266.9  22,137 Jmol 1
The latent heat at 273.15 K  Tr  273.15 / 420  0.650
0.38
H lv
 1  Tr 
From    ...( 4.13 )
H nlv  1  Tr
n


0.38
 0.350 
H  ( 22 ,137 )
lv
  21,810 Jmol 1

 0.368 
 H lv
21,810
S 
lv
  79.84 Jmol K1 1

T 273.15
 • Step (b): Transformation of saturated vapor into an ideal
gas at (T1, P1).

   0.422
 B  0.083  1.6
0
 (3.65)
 1  Tr
HR d B 0
d B
 Pr  B 0  Tr    B1  Tr   (6.87)
RTc  dTr  dTr  0.172
   B  0.139  4.2
1
 (3.66)
   Tr
  dB 0 0.675
SR  d B0 d B1   2.6  (6.89)
  Pr     (6.88) dTr Tr
R  dTr dTr 
 
dB1 0.722
 5.2  (6.90)
dTr Tr

• Tr = 0.650 and Pr = 1.2771/40.43 = 0.0316

So, H1R  (0.0985)(8.314)(420)  344 Jmol 1

S1R  (0.1063)(8.314)  0.88 Jmol 1 K 1

• Step (c): Changes in the ideal gas state
T2

Eq .( 6.95 ) : H  H 2  H 1   C Pig dT  C Pig

ig ig ig
H
( T2  T1 )
T1

dT T2
P2 T2 P2
Eq .( 6.96 ) : S  S 2  S1   C P
ig ig ig
 R ln  C Pig
ig
ln  R ln
T T 1 P1 S
T1 P1

• Tam = 373.15 K, Tlm = 364.04 K,

A = 1.967, B = 31.630x10-3, C = -9.837x10-6

Hig = 20,564 J mol-1

Sig = 22.18 J mol-1 K-1
• Step (d): Transformation from the ideal gas to real gas
state at T2 and P2.
Tr = 1.127 Pr = 1.731
• At the higher P; Eqs.(6.85) and (6.86) with interpolated
values from Table E.7, E.8, E.11 and E.12.
H 2R
 2.294  (0.191)(0.713)  2.430
RTC
S 2R
 1.566  (0.191)( 0.726)  1.705
R
 H 2R  (2.430)(8.314)( 420.0)  8,485 Jmol 1

S 2R  (1.705)(8.314)  14.18 Jmol 1 K 1

H  H  21,810  (344)  20,564  8,485  34,233 Jmol 1

S  S  79.84  (0.88)  22.18  14.18 Jmol 1 K 1

(70)( 287.8)
U  H  PV  34,233  3 1
 32,218 Jmol 1
10 cm barJ
 Extension to Gas Mixtures

   yii  (6.97) Tpc   yiTci  (6.98) Ppc   yi Pci  (6.99)

i i i

T P
TPr   (6.100) PPr   (6.101)
Tpc Ppc

These replace Tr and Pr for reading entries from the table of

App. E, and lead to values of Z by Eq.(3.57), and HR/RTpc
by Eq.(6.85), and SR/R by Eq.(6.86).
Ex. 6.10
Estimate V, HR, and SR for an equimolar mixture of
carbon dioxide(1) and propane(2) at 450 K and 140 bar by
the Lee/Kesler correlations.

Solution
From Table B.1,
  y11  y22  (0.5)(0.224)  (0.5)(0.152)  0.188
Tpc  y1Tc1  y2Tc 2  (0.5)(304.2)  (0.5)(369.8)  337.0 K
Ppc  y1 Pc1  y2 Pc 2  (0.5)(73.83)  (0.5)(42.48)  58.15 bar
450 140
Whence, Tpr   1.335 Ppr   2.41
337.0 58.15
From Table E.3 and E.4;
Z  Z 0  Z 1  0.697  (0.188)(0.205)  0.736
ZRT (0.736)(83.14)(450)
V    196.7 cm3mol 1
P 140
From Table E.7 and E.8; with Eq.(6.85) :
0 1
 H 
R  H R
   1.730    0.169
 RT   RT 
 pc   pc 
HR
 1.730  (0.188)(0.169)  1.762
RTpc
H R  (8.314)(337)  1.762  4,937 Jmol 1
From Table E.11 and E.12; with Eq.(6.86) :
SR
 0.967  (0.188)(0.330)  1.029
R
S R  (8.314)(1.029)  8.56 Jmol 1 K 1