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

Maxwells equations
G ( P, T )
dG ...V ......dP ...S ......dT
G
G
dG
dP
dT
P T
T P
V
S

T P
P T

S V
V

S P

V T
V
V
S

T P
P T

Enthalpy and Entropy as Functions of T and P

Temperature derivatives:

T
S

CP
P

CP

Pressure derivatives:

P
H

V
V T

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

dT V
dS C P

dP (6.21)
T T P

(6.20)

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
U

V
T

V
P

P
P

dU Tds PdV

T
T

V T
V
V
S

T P
P T

Property Relations for Homogeneous

Phases
The Ideal Gas State
For ideal gas,

V
dH C p dT V T

expressions of dH
T

and dS (eq.6.20-6.21)
dT V
dS

dP
as functions of T and
P
T T P
P can be simplified as
follows using ideal
gas law:
PV

ig

V ig
RT
T

dH ig C Pig dT
dS ig C Pig

dT
dP
R
T
P

R
P
(6.23)
(6.24)

dP

1 V

V T

dV

Property Relations for Homogeneous

Phases

V
dP

dT
P

P
V

P T

Alternative Forms for Liquids

1

Relations of liquids

V
S dV
V
can be expressed in V S
dT dP
terms of and as T
V V V
dH
V T
dP
C p dT
follows:
P S S P T P
S
dT SV

dS CP dP

T
T
T
T V V T P
H

1 T V
V
S

P T
T P
P T
U
U
V
V

T
V

T
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 25C to 1,000 bar 50C.
T
( C)

P
(bar)

25

Cp
(Jmol-1K-1

V
(cm3mol-1)

(K-1)

75.305

18.071

256x10-6

25

1000

18.012

366x10-6

50

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
T2
S C p ln V P2 P1
T1

Integrated forms of
equations for change in
Enthalpy and Entropy

For P 1 bar ,
75.305 75.314
Cp
75.310 Jmol 1 K 1
2

Average value at T1
and T2 at 1 bar

and for T 50C ,

18.234 18.174
V
18.204 cm 3 mol 1
2
458 568

10 6 513 10 6 K 1
2

Average value at P1
and P2 at 50 oC

H C p T2 T1 1 T2 V P2 P1
T2
S C p ln V P2 P1
T1

1 513 10 323.15 18.2041,000 1

H 75.310 323.15 298.15
6

10

1,883 1,517 3,400 Jmol 1

On substitution of values

323.15 513 10 6 18.204 1,000 1

S 75.310 ln

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 25C.

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

T
U

V
P

CV

T
P
T

P
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

dU CV dT T P dV

dT
dS CV
dV
T

T
1 V

V T

dV

V
dP
P T

dT
P

P
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:
V
H
G

dP

dT

2
RT
RT
RT

V
G RT

RT
P T
H
G RT
T

RT
T

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

M = the Residual
Molar gas
properties which
are at the same
temperature and
pressure.

ig

M is the actual
molar value of
any extensive
thermodynami
cs property: V,
U, H, S, G.

Mig = the ideal

gas properties
which are at the
same
temperature and
pressure.

 Residual Gibbs energy:

G G G
R

ig

Residual volume:

V V V
R

ig

RT
V
P

RT
Z 1
V
P
R

PV=ZRT

Fundamental property relation for residual properties

The fundamental property relation for residual
properties applies to fluids of constant composition.
R
R
HR
G V
d
dP
dT ( 6.42 )

2
RT
RT
RT

V R G R / RT

( 6.43 )

RT
P
T
R
HR
G / RT
T
( 6.44 )

RT
T

 GR V R

d
dP
RT
RT

From Eq.(6.43),

GR GR

RT RT

P 0

Eq.(6.45 6.44);

From

So,

P
0

(const T )

P
VR
dP
dP ( Z 1) (6.45)
0
RT
P

P Z
HR
T

0
RT
T

GR

for ideal gas

RT

dP
(6.46)
P

S R H R GR

RT RT RT
P Z
SR
T

0 T
R

dP P
dP
( Z 1)
0
P
P

(const T )

(6.48)

0
P 0

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

P
S S 0 C P dT R ln
T
P0

H H 0 C P dT
ig

ig

ig

ig

T0

ig

ig

Substituti on ; H H 0 C Pig dT H R
ig

( 6.50 )

T0

P
S S 0 C P dT R ln S R ( 6.51 )
T
P0
ig

ig

H ig H 0ig C P

R
(
T

T
)

H
0
H

( 6.52 )

T
P
S S 0 C P S ln R ln S R ( 6.53 )
T0
P0
ig

ig

T2

CP

ig
C
P dT

CP

T2 T1
R
T1

dT
T C P T
CP

ln( T2 / T1 )
R
T2

CP

C
D
2
A BTam ( 4Tam T1T2 )
3
T1T2

ig

D
A BTlm TamTlm C
2
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.

Z
0 T
P

dP
P

dP
0 (Z 1) P
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
Data for the required plots are shown in Table 6.2.

0
T

dP
dP
P
4
1
26.37 10 K
0 ( Z 1 ) 0.2596
P
P P
R
H
By Eq . ( 6.46 ),
( 360 )( 26.37 10 4 ) 0.9493
RT
R
S
By Eq . ( 6.48 ),
0.9493 0.2596 0.6897
R
For R 8.314 Jmol 1 K 1
P

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

R
C Pig

A BTam 1.7765 33.037 10 3 Tam

A BTlm 1.7765 33.037 10 3 Tlm

T0 T1 300 360

330 K
2
2
T1 T0
360 300
Tlm

329.09 K
ln( T1 / T0 ) ln( 360 / 300 )
Tam

C Pig
C Pig

12.679( 8.314 ) 105.41 Jmol 1 K 1

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.
P
GR
dP
( Z 1)
0
RT
P

So,

G R BP

RT RT

(6.54)

G R / RT
HR
By Eq.(6.44),
T

RT

P B dB

(6.55)
R T dT

SR
P dB
Substitution int o Eq.(6.47),

R
R dT

(6.56)

In application is a more convenient variable than V,

PV = ZRT is written in the alternative form.
dP d dZ

P ZRT ( 6.57 ), dP RT ( Zd dZ )
Substitue int o Eq .( 6.49 );

GR
d
( Z 1 ) Z 1 ln Z ( 6.58 )
RT 0

H R Z 1 P
From Eq .( 6.40 ) and ( 6.42 ),

2
RT
P T

R
( G / RT )

HR
Z d
Differentition of Eq .( 6.57 ) and ( 6.58 );
T
Z 1 ( 6.59 )

0 T
RT

SR
d
Z d
From Eq .( 6.47 ),
ln Z T

(
Z

1
)
( 6.60 )

0 T
0
R

 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
B dB
HR
C 1 dC 2
T

(6.62)

RT
T 2 dT
T dT

B dB
SR
1 C dC 2
ln Z T

(6.63)
R
2 T dT
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
q
1 b
(1 b)(1 b)
b
b
Z 1
q
(6.64)
1 b
(1 b)(1 b)
Z

b
dq

dT

(1 b)(1 b)

The integrals of Eqs.(6.58), (6.60);

d
b d ( b)
d ( b)
(Z
1)

q
0
0 (1 b)(1 b)
0 1 b b

Z
0 T

d
dq
d ( b)

dT 0 (1 b)(1 b)

d
To simplify ; (Z - 1)
ln(1 b) qI ,

Z
0 T

d
dq

dT

The generic equation of state presents two cases.

1 b
1

Case I : I
ln
1 b
When is eliminated in favor of Z.
bP

RT

Case II :

P
Z
RT

(6.65a)

whence
b
Z

Z
1

I
ln
Z
b

1 b Z

(6.65b)

G
Z 1 ln(1 b) Z qI (6.66a )
RT
GR
Z 1 ln(Z ) Z qI (6.66b)
RT
R
d ln (Tr )
H
Z 1
1 qI (6.67)
RT
d ln Tr

S
d ln (Tr )
ln(Z )
qI (6.68)
R
d ln Tr
R

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
3/ 2
Tr
0.086641.176

Eq.(3.52) : Z 1 q

Z
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 arrangemen t ,

dT V V
V
Integration of Eq .( 6.8 ); H TS ( The latent heat of phase transition )
dP sat
H
Thus , S H / T

( 6.71 ) : The Clapeyron equation

dT
TV
dP sat
H l
Phase transition from liquid to vapor ;

( 6.72 )
l
dT
TV
RT
d ln P sat
H l
l
l
But V sat Z

( 6.73 )
2
l
P
dT
RT Z
The Clapeyron eq.
for pure-species
d ln P sat H l
or

( 6.74 )
l
vaporization
d ( 1 / T ) RZ

Temperature Dependence of the Vapor

Pressure of Liquids
ln P sat A

B
T

B
The Antoine eq . : ln P A
( 6.76 )
T C
Antoine cons tan ts are given in Table B .2 , App .B
sat

1.5
3
6
A

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
1.28862 ln Tr 0.169347Tr6 (6.79)
Tr
0
r

ln Pr1 (Tr ) 15.2518

15.6875
13.4721 ln Tr 0.43577Tr6 (6.80)
Tr

ln Prnsat ln Pr0 (Trn )

1
r

ln P (Trn )

(6.81)

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 90C: (a) With constants from App. B.2.
(b) From the Lee/Kesler correlation for P rsat
Solution
2696.04
(a)
ln P sat 13.8193
t 224.317

341.9
1.01325
(b) Eq.(6.78);
Tr
0.6736, Prsat
0.03350
507.6
30.25
From Table B.1,
From Eq.(6.81) =0.298
n

t/C

0
60

Psat/kPa
Psat/kPa
Psat/kPa
t/C Psat/kPa
(Antoine) (Lee/Kesler
(Antoine) (Lee/Kesler
)
)
6.052
76.46

5.835
76.12

30
90

24.98
189.0

24.49
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 nv

V x lV l x V

x : mass fraction

V (1 x v )V l x V

xl 1 xv

(moles)

The generic equation :

M (1 x v ) M l x M (6.82a )
where M V ,U , H , S , etc. An alternative 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

H
2 Z

Tr
RTc
Tr
0
R

SR
Tr
R

Pr

Z
0 Tr

Pr
P

Pr

dPr
Pr

(6.83)

dPr r
dPr
( Z 1)
(6.84)
Pr 0
Pr

 Z
Z Z Z
Tr
0

Pr

Z 0

Tr

0
r

HR

Z
2

Eq.(6.83) :
Tr
RTc
Tr
0

Pr

HR
HR
HR

RTc
RTc
RTc
SR r
Eq.(6.84) :

R 0

Z 1

Tr
Tr

SR
SR
SR

R
R
R

Pr

1
r

dPr

Z
2

Tr
Pr
Tr

Pr

Z 1

Tr

Pr

dPr

Pr

(6.85)

Pr

dPr
0

Z 1
Pr

Pr

Z 1

Tr
Tr

Z
Pr

dP
r

Pr

(6.86)

Table E.5 - E.12

Analytical correlation of the residual properties at low pressure

The generalized sec ond virial coefficient correlatio n forms
BP
B c B 0 B1 ,
RTc

d B dB 0
dB1

dTr dTr
dTr
R

HR

Pr
RTc

H
d B
S
dB
Pr B Tr
,
Pr

RTc
dTr
R
dTr

0
1
d
B
d
B
(6.87)
B 0 Tr
B1 Tr

dTr
dTr

Eqs.(6.55) and (6.56);

d B0
SR
d B1
Pr

R
dT
dT

r
r

(6.88)

0.422
B 0.083 1.6
Tr

(3.65)

0.172
B 0.139 4.2
Tr

(3.66)

dB 0 0.675
2.6
dTr
Tr

(6.89)

dB
0.722
5.2
dTr
Tr

(6.90)

HR and SR with ideal-gas heat capacities

For a change from state 1 to 2:
T2

H 2 H C dT H
ig
0

ig
P

T1

R
2

H1 H C Pig dT H1R
ig
0

The enthalpy change for the process, H = H2 H1

T2

H C Pig dT H 2R H1R

(6.91)

T1

T2

Similarly , S C Pig dT R ln
T1

P2
S 2R S1R
P1

(6.92)

Alternative form

H C Pig
S C Pig

(T2 T1 ) H 2R H1R

ln

(6.93)

T2
P
R ln 2 S 2R S1R
T1
P1

(6.94)

A three-step calculational path

Step 11ig: 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
R ln (6.96)
T
P1
T1
ig

ig
2

ig
1

ig
P

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 200C, 70 bar
if H and S are set equal to zero for saturated liquid at 0C.
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 0C

ln P sat A

B
T

(6.75)

The vapor pressure curve contains both

the normal boiling po int; ln 1.0133 A
the critical po int; ln 40.43 A
Whence,

A 10.126

B
266.9

B
420.0

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

1 Tr
H

H nlv 1 Tr

0.38

lv

From

...( 4.13 )
0.38

0.350
1
H ( 22 ,137 )

21
,
810
Jmol

0.368
lv

H
21,810
lv
1
1
S

79.84 Jmol K
T
273.15
lv

 Step (b): Transformation of saturated vapor into an ideal

gas at (T1, P1).

d
B
(6.87)
B1 Tr
dTr

H
dB
Pr B 0 Tr

RTc
dTr

d B0
SR
d B1
Pr

(6.88)
R
dTr
dTr

0.422
B 0.083 1.6
Tr

(3.65)

0.172
B 0.139 4.2
Tr

(3.66)

dB 0 0.675
2.6
dTr
Tr

(6.89)

dB1 0.722
5.2
dTr
Tr

(6.90)

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

T1

( T2 T1 )

dT
P2
Eq .( 6.96 ) : S S 2 S1 C P
R ln C Pig
T
T
P1
ig

ig

ig

T2

ig

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

T2
P2
ln R ln
S
T1
P1

 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
U H PV 34,233

(70)(287.8)
32,218 Jmol 1
3
1
10 cm barJ

Extension to Gas Mixtures

yii (6.97)
i

T
TPr
Tpc

(6.100)

Tpc yiTci (6.98)

i

P
PPr
Ppc

Ppc yi Pci (6.99)

i

(6.101)

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 H R/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,

y11 y22 (0.5)(0.224) (0.5)(0.152) 0.188

T pc 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
Whence, T pr
1.335
337.0

140
Ppr
2.41
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) :
H

RT
pc

1.730

0.169
RT
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