CHAPTER 6

THERMODYNAM
IC PROPERTIES
OF FLUIDS

OBJECTIVES
To develop from the 1st and 2nd laws the
fundamental property relations which
underlie the mathematical structure of
thermodynamics.
To derive equations which allow
calculation of H and S from PVT and
heat capacity data.
To develop generalized correlations which
provide estimates of property values in
the absence of experimental information.

Process design and analysis

IN

OUT

SYSTEM

PROPERTY CALCULATION
IDEAL
Volume

Pv = RT

Internal
Energy

C dT f ( P, v)
o
v

Enthalpy C p dT f ( P, v)
o

Entropy C po ,v dT

P
R ln 2 or
P1

V2

V1

R ln

NONIDEAL

STEAM

z or B

Tables

Tables

dT ?? f ( P, v) Tables

o
C
v dT ?? f ( P, v)

o
p

C op ,v dT
T

?? f ( P, v) Tables

LIQUID

 From the figure, to find volume, we are

completely armed, whether it is ideal
gas, non-ideal gas, steam or liquid.
But for other properties, we especially
have no idea what is the pressure and
volume functions, e.g. for non-ideal gas.
As such, we need to develop just such
relations so that calculations can be
carried out.

6.1 PROPERTY RELATIONS FOR

HOMOGENEOUS PHASES

Primary thermodynamic properties

are given as: P, V, T, U and S.
Other thermodynamic properties
arise only by definition using the
relation of these primary
properties.
e.g.
I. Enthalpy: H U + PV
II. Helmholtz Energy: A U TS
III. Gibbs Energy: G H TS

 If a differential change from one equilibrium

state to another happen in a constant
enclosed homogenous mass, the following
equations apply:

dU TdS PdV
dA PdV SdT
dG VdP SdT
dH TdS VdP

(6.1)
(6.2)
(6.3)
(6.4)

 Using Theorem of Exactness,

Exactness whereby
the second derivates is immaterial, the
primary thermodynamic properties U, H, A
and G can be expressed by equation for
each of these equations :
T

V
P

(6.5)

(6.6)

(6.7)
(6.8)

Eqns (6.5) to (6.8) are Maxwells equations. All these

relations are useful for evaluation of thermodynamic
properties from experimental data. In particular, eqn.
(6.6) and (6.8) are very useful. In the sections
preceding, we will only consider using eqns. (6.1), (6.2),
(6.6) and (6.8) to find U, H and S

6.1.1 Enthalpy and Entropy as Functions

of T and P H=f(T,P) S=f(T,P)
START WITH TEMPERATURE DERIVATIVE:

Heat capacity at constant pressure defined:

H

CP

(6.9)

Other expression for this quantity is

(from Eqn 6.4)
H

S
T

(6.10)

Combine these two equation gives :

S

CP

(6.11)

FOLLOW BY CONSIDERING PRESSURE DERIVATIVE:

Pressure derivative for S follows eqn. (6.8):

V

(6.8)
T

The corresponding pressure derivative for H

can be obtained from eqn. (6.4):
H

S
T

V
T

(6.13)

As a result, Equation 6.8 becomes,

H

V
V T

(6.14)
P

 The functional relations chosen here for H

and S are:
H = H ( T , P ) and S = S ( T, P )
Whence,

V
dH CP dT V T
dP
T P

(6.15)

dT V
dS CP

dP
T T P

(6.16)

These are general equations relating the

properties of homogeneous fluids of
constant composition to temperature T,
pressure P and volume V.

6.1.2 Relation of Internal Energy

with P at constant T
The pressure dependence of the internal
energy is obtained by differentiation of the
equation U = H - PV:
U

V
P

V
T

(6.16)

Then by Eq.(6.14):
U

V
T

V
P

(6.17)

6.1.3 The Ideal-Gas State

dH

ig

dT
dP
dS C
R
T
P

C dT
ig
P

ig

ig
P

where superscript ig denotes an ideal-gas

value.

6.1.4 Alternative Forms for Liquids

S

V
T

U
1 T V

P T V
T

At critical point the volume itself is very small,

as are and . Thus at most conditions
pressure has little effect on the properties of
liquid. Substituting to produce:

dH CP dT 1 T VdP

dT
dS C P
VdP
T

6.1.5 Internal Energy and Entropy as

Functions of T and V

Temperature and volume often serve as more

convenient independent variables than do
temperature and pressure.
These are general equations relating the internal
energy and entropy of homogeneous fluids of constant
composition to temperature
and volume.

P
dU CV dT T

P dV

dT P
dS CV

T T

dV
V

A change of state a constant volume becomes:

T V
Then the equations above become:
dT

dU CV dT T P dV
dS CV
dV

6.1.6 The Gibbs Energy as a

Generating Function

A fundamental property relation, follows from

the mathematical identity:
1
G
G
d
dG
dT

2
RT
RT
RT

After algebraic reduction:

V
H
G
d
dP
dT

2
RT
RT
RT

When G/RT is known as a function of T and

P, V/RT and H / RT follow by simple
differentiation.
H
G RT
V
G RT
T

RT

P
RT
P T

The remaining properties are given by defining

equations. In particular,

S
H
G

R RT RT

U
H
PV

RT RT RT

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 property
information .

6.2 Residual Properties

GR G Gig
where;
GR = Residual Gibbs energy
G = Actual Gibbs energy
Gig = Ideal-gas values of Gibbs energy
Example, for residual volume:
VR V Vig = V RT/P
Since V = ZRT/ P, VR = RT/P(Z-1)
The definition for generic residual property is:
MR M Mig
where M is molar value of any extensive
thermodynamic property eg. V , U , H , S , or G.

 GR V R
HR

d
dP
dT
2
RT
RT
RT

This fundamental property relation for

residual properties applies to fluids of
constant composition. Useful restricted
forms are:

G R RT
V

RT
P

G R RT
HR
T

RT

In addition the defining equation for Gibbs

energy is:
GR = HR - TSR
The residual entropy is therefore:
S R H R GR

R
RT RT

 Thus the residual Gibbs energy serves as a

generating function for the other residual
properties and here a direct link with
experiment does exist.
GR V R

d
dP constT
RT
RT

Integration from zero pressure to arbitrary

pressure P yields:
R
PV
GR

dP
0 RT
RT
where at the lower limit GR/RT is equal to zero
because the zero-pressure state is an idealgas state.
P
GR
dP
Z 1
0
RT
P

 Differentiation with respect to temperature in

accord give: H R
P Z
dP
RT

T
0

The residual entropy is found:

P Z
SR
T

0
R
T

P
dP
dP
Z 1
0
P
P

The compressibility factor is defined as

Z = PV/RT; values of Z and (Z/T)p
therefore come from experimental PVT data
and the two integrals are evaluated by
numerical or graphical method.
Alternatively the two integrals are evaluated
analytically when Z is expressed as function
of T and P by volume- explicit equation of state .

 Thus, given PVT data or an appropriate

equation of state, HR and SR can be
evaluated and all other residual properties.
H = Hig + HR

S = Sig + SR

and

Thus H and S follow from corresponding idealgas and residual properties by simple addition.
Since:
H

ig

ig
0

C dT
T0

ig
P

ig

ig
0

C
T0

ig
P

dT
dP
R
T
P0

Substitution into the preceding equations gives:

T
dP R
T
ig dT
ig
ig
R S S ig
CP
R S
H H 0 C P dT H
0

T0
T
P0
T0

 These two equation also may expressed

alternatively to include the mean heat capacities:

H H 0ig C Pig
and

S S 0ig C Pig

T T0 H R
H
ln

T
dP
R
SR
T0
P0

Since the equations of thermodynamics which derive

from the first and second laws do not permit calculation
of absolute values for enthalpy and entropy and since in
practice only relative values are needed the referencestate conditions T0 and P0 are selected for convenience
ig
ig
and
S
H
and values are assigned to
0 arbitrarily.
0
The true worth of equations for ideal gases is
now evident. They are important because the
provide a convenient base for calculation of realgas properties.
Residual properties have validity for both gases
and liquids.

6.3 Residual Properties By

Equations of State
Compressibility factor is given:
Then, R
G
BP

RT RT
By Equation,
G R RT
HR
T

RT

P,x

P
T
R

or
H R P B dB

RT R T dT

1 dB B
2

T dT T

 Substitution of equation,

SR
P dB

RT
R dT
Equation PV = ZRT can be written in the
alternative form,
P = ZRT
Differentiation at constant T gives:
dP = RT ( Z d + dZ )

 In combination with Equation P = ZRT , this equation

is recast :
dP d dZ

Z
Upon substitution for dP /P ,

GR
d
Z 1
Z 1 ln Z
0
RT

where the integral is evaluated at constant T . Note also

that 0 when P 0 . The residual entropy found :
Z
GR
T

0
RT
T

d
Z 1

6.4 TWO-PHASE SYSTEMS

Generally , for two phases and of a pure species
coexisting at equilibrium ,

G G

where G and G are the molar or specific Gibbs

energies of individual phases .

The Clapeyron equation follow from this equality .If the

temperature of a two-phase system is changed , then the
pressure must also change accord with the relation between
vapor pressure and temperature if the two phases continue to
coexist in equilibrium .

dG dG

Subtituting expressions for dG and dG :

V dP sat S dT V dP sat S dT

 Which rearrangement becomes :

dP sat S S
S

dT
V V
V
The entropy change S and the volume change V are
the changes which occur when a unit amount of a pure
chemical species is transferred from phase to phase at the
equilibrium temperature and pressure. Integration of
equation for this change yields the latent heat of phase
transition :
H=TS

Thus ,

dP sat
H

dT
TV

which is the Clapeyron equation. For the particularly

important case of phase transition from liquid l to vapor v, it
is written
sat
lv
dP
H

dT
TV lv

 A plot of ln Psat vs 1/T generally yields a line that is

nearly straight :
B
sat
ln P

where A and B are constants for given species.

The Antoine equation , which is more satisfactory for
general use, has the form:
ln P sat A

B
T C

A principal advantage of this equation is that values of

the constants A, B and C are readily available for a
large number of species .

 The Wagner equation is one the best available ; it expresses

the reduced vapor pressure as a function of reduced
temperature :
sat
r

ln P

A B 1.5 C 3 D 6

where 1- Tr and A , B , C and D are constant .

All the relations are represented by the generic equation :

M 1 x v M l x v M v

where x v is called the quality and represented molar fraction

of vapor in the system .
M can represents V ,U , H , S and others .
M M l x v M lv

6.6 TABLES OF THERMODYNAMIC

PROPERTIES

Example 6.7
Superheated steam originally at P1 and T1 expands through a
nozzle to an exhaust pressure P2. Assuming the process is
reversible and adiabatic, determine the down stream state of
the steam and H for the following conditions:
(a)P1 = 1,000 kPa, t1 = 250C and P2 = 200 kPa.
(b)P1 = 150(psia) , t1 = 500(F), and P2 = 50(psia).
Solution 6.7
Since the process is both reversible and adiabatic, the
change in entropy of the steam is zero.

(a) For the initial temperature of 250C at 1,000 kPa, no

entries appear in the SI tables for superheated steam.
Interpolation between values for 240C and 260C
yields, at 1000 kPa:
H1 = 2,942.9 kJ kg-1

S1= 6.9252 kJ kg-1 K-1

For the final state at 200 kPa,

S2 = S1 = 6.9252 kJ kg-1 K-1
Since the entropy of saturated vapor at 200 kPa is greater than
S2. the final state is in the two-phase liquid/vapor region.
Thus T2 is the saturation temperature at 200 kPa. given in the
SI superheat tables as T2 = l20.23C.

Equation (6.73a) applied to the entropy becomes:

S 2 (1 x 2v ) S 2l x 2v S 2v

Whence.

6.9252 = 1.5301(1 - x 2 ) + 7.1268 x 2

where the values 1.5301 and 7.1268 are entropies of

saturated liquid and saturated vapor at 200 kPa. Solving,

x 2v

= 0.9640

On a mass basis, the mixture is 96.40% vapor and 3.60%

liquid. Its enthalpy is obtained by further application of Eq.
(6.73a):
H2 = (0.0360)(504.7) + (0.9640)(2,706.3) = 2,627.0 kJ kg -1

Finally,
H = H2 - H1 = 2,627.0 - 2,942.9 = - 315.9 kJ kg -1
(b) For the initial state at 150(psia) and 500(F) data from the
tables for super-heated steam in English units provide:
H1 = 1,274.3 (Btu)(Ibm)-1

S1 = l.6602(Btu)(lbm)-1(R)-1

In the final state at 50(psia),

S2 = S1 = 1.6602(Btu)(Ibm)-1(R)-1
Inspection of the steam tables shows that S2 is here greater
than the entropy of saturated vapor at 50 (psia). Hence the final
state is in the superheat region. Interpolation on entropy at
50(psia) yields:
t2= 283.28(F)
H2 = 1,175.3 (Btu)(lbm)-1

And
H = H2 - H1 = 1,175.3 - 1,274.3 = - 99.0(Btu)(lbm)-1

Example 6.8
A 1.5-m3 tank contains 500 kg of liquid water in equilibrium
with pure water vapor, which fills the remainder of the tank.
The temperature and pressure are 100C and 101.33 kPa.
From a water line at a constant temperature of 70C and a
constant pressure somewhat above 101.33 kPa, 750 kg of
liquid is bled into the tank. If the temperature and pressure in
the tank are not to change as a result of the process, how
much energy as heat must be transferred to the tank?
Solution 6.8
Choose the tank as the control volume. There is no work,
and kinetic- and potential-energy effects can be assumed
negligible. Equation (2.29) therefore is written:

d mU tan k
H m Q
dt

dm tan k
m
dt

where the prime denotes the state of the inlet stream.

The mass balance may be combined with the energy
balance to yield:
d mU tan k
dm tan k
H
Q
dt
dt

Multiplication by dt and integration over time

(with H constant) gives:

Q mU tan k H m tan k

The definition of enthalpy may be applied to the entire

contents of the tank to give:

mU tan k mH tan k PmV tan k

Since total tank volume in V and the pressure are constant,

(Pm V)tank = 0. Therefore.

Q mU tan k H mtan k m2 H 2 tan k m1 H 1 tan k H mtan k

where m tank is the 750 kg of water bled into the tank, and
subscripts 1 and 2 refer to conditions in the tank at the
beginning and end of the process. At the end of the process the
tank still contains saturated liquid and saturated vapor in
equilibrium at 1000C and 101.33 kPa. Hence m1 H1 and m2 H2
each consist of two terms, one for the liquid phase and one for
the vapor phase.
The numerical solution makes use of the following enthalpies
taken from the steam tables:
H = 293.0 kJ kg-1
saturated liquid at 70C
Hl tank = 419.1 kJ kg-1
saturated liquid at 100C
Hv tank = 2,676.0 kJ kg-1
saturated vapor at 100C

The volume of vapor in the tank initially is 1.5 m3 minus the

volume occupied by the 500 kg of liquid water. Thus,
1.5 500 0.001044
mv
0.772kg
1

1.673

where 0.001044 and 1.673 m3 kg-1 are the specific volumes of

saturated liquid and saturated vapor at 100C from the steam
tables. Then,

m1 H 1 tan k

m1l H 1l m1v H 1v 500 419.1 0.772 2,676.0 211,616kJ

At the end of the process, the masses of liquid and vapor are
determined by a mass balance and by the fact that the tank
volume is still 1.5 m3:

m2 500 0.772 750 m2v m2l

1.5 1.673m2v 0.001044m2l

Solution yields:
and

m2l 1,250.65kg

m2v 0.116 kg

Then, since Hl2 = Hl1 and Hv2 = Hl2

(m2H2)tank = (I1,250.65)(419.1) + (0.116)(2,676.0)
= 524,458 kJ
Substitution of appropriate values into the equation for Q
gives:
Q = 524,458- 211,616 - (750)(293.0) = 93,092 kJ

6.7 GENERALIZED PROPERTY

CORRELATIONS FOR GASES
P = Pc Pr

T = Tc Tr

dP = Pc dPr

dT = Tc dTr

The resulting equations are :

Pr Z
HR
2

Tr
0
RTc
Tr

SR
Tr
R

Pr

Tr

Pr

Pr

dPr
Pr

Pr
dPr
dP
Z 1 r
0
Pr
Pr

The correlation for Z is based on Equation

Z = Z0 + Z1

 Differentiation yields :

Z
T
r

Z
Substitution for Z and
Tr
0
Pr Z
HR
2

Tr
0
RTc
Tr
Pr
Z 0
SR
Tr
0
R
Tr

Pr

Pr

Z 0

Tr

Pr

Z 1

Tr

:
Pr

1
Pr Z
dPr
2

Tr
0
Pr
Tr

dP
Pr
Z 1
r

Z 1
Tr
0
Pr
Tr

Pr

Pr

Pr

dPr
Pr
dP
r
Z
Pr
1

Pr

The first integrals on the right sides of these two

equations may be evaluates numerically or graphically
for various values of Tr and Pr from the data for Z0
given in Tables E.1 and E.3 , and the integrals which
follow in each equation may be similarly evaluated
from the data for Z1 given in Tables E.2 and E.4 .

 Alternatively, the evaluated may be based on an equation

of state; Lee and Kesler used a modified form of the
Benedict/Webb/Rubin equation of state to extend their
generalized correlation to residual properties .

H
H
H

RTc
RTc
RTc
R 0

R 1

S S
S

R
R
R
Calculated values of the quantities
R 0

R 1

H , H , S , S
R 0

RTc

R 1

RTc

R 0

R 1

as determined by Lee and Kesler are given as functions

of Tr and Pr in Tables E.5 through E.12.

Figure 6.5 : The Lee/Kesler correlation for

R 0

RTc

as function of Tr and Pr

 The generalized second virial-coefficient correlation valid

at low pressures forms the basis for analytical correlations of
the residual properties.
0
1
HR
dB 0
dB 1

Pr B Tr
B Tr
RTc
dTr
dTr

dB 0
SR
dB 1

Pr

R
dTr
dTr

where
0.422
B 0 0.083 1.6
Tr

B1 0.139

0.172
Tr4.2

dB 0 0.675
2.6
dTr
Tr

dB 1 0.722
5.2
dTr
Tr

 The generalized correlations for HR and SR , together

with ideal-gas heat capacities, allow calculation of enthalpy
and entropy values of gases at any temperature and
pressure.
H2 H

ig
0

T2

C dT H
T0

ig
P

R
2

H1 H

ig
0

T1

C Pig dT H 1R
T0

The enthalpy change for the process, H = H2 H1 , is

difference between these two equations :
T2

H C Pig dT H 2R H 1R
T1

Similarly , for entropy :

T2

S C Pig
T1

dT
P
R ln 2 S 2R S1R
T
P1

 Alternative form :

H C Pig
H C

ig
P

T2 T1 H 2R H 1R
H
T2
P2
ln R ln S 2R S1R
T1
P1

Example 6.8
Estimate V, U, H, and S for 1-butene vapor at 200C and 70
bar if H and S are set equal to zero for saturated liquid at 0C.
Assume that the only data available are:
Tc = 420.0K Pc = 40.43 bar = 0.191
Tn = 266.9 K (normal boiling point)

Solution 6.8
The volume of 1 -butene vapor at 200 C and 70 bar is
calculated directly from the equation V = ZRT/P, where Z is
given by Eq. (3.54) with values of Z and Z1 interpolated in
Tables E.3 and E.4. For the reduced conditions,
Tr

200 273.15
1.127
420.0

Pr

70
1.731
40.43

the compressibility factor is:

Z =Z0+ Z1 = 0.485 + ( 0.19l )( 0.142 ) = 0.512
Whence,
V

ZRT 0.512 83.14 473.15

287.8cm 3 mol 1
P
70

For H and S , use a calculational path like that of Fig. 6.6,

leading from an initial state of saturated liquid l-butene at
0C, where H and S are zero, to the final state of interest. In
this case, an initial vaporization step is required, leading to
the four-step path shown by Fig. 6.7. The steps are:
(a) Vaporization at T1 and P1 = P sat
(b) Transition to the ideal-gas state at ( T1 , P1 ).
(c) Change to ( T2 , P2 ) in the ideal-gas state.
(d) Transition to the actual final state at ( T2, P2 ).

Figure 6.7 : Calculational path for Ex. 6.8

Step (a): Vaporization of saturated liquid 1-butene at 0C.

The vapor pressure must be estimated, since it is not given.
One method is based on the equation:

ln P

sat

B
A
T

The vapor-pressure curve contains both the normal boiling

point, for which p sat 1.0133 bar at 266.9 K. and the critical
point, for which P sat = 40.43 bar at 420.0 K. For these two
points.
B
B
ln 40.43 A
ln 1.0133 A
420.0
266.9
Simultaneous solution of these two equations yields:
A = 10.1260

B = 2~699.I I

For 0C (273.15 K), P sat = 1.2771 bar, a result used in steps

(b) and (c). Here, the latent heat of vaporization is required.
Equation (4.12) provides an estimate at the normal boiling
point, where Tr n = 266.9/420.0 = 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

Whence, Hlvn = ( 9 .979 )( 8.314 )( 266.9 )= 22,137 J mol-1

The latent heat at 273.15 K, or Tr = 273.15/420.0 = 0.650,
is given by Eq. (4.13):
or Hlv = (22,137)(0.350/0.364)0.38 = 21,810 J mol-1
By Eq. (6.67),
lv

H
S
lv

21,810

273.15

79.84 Jmol 1 K 1

Step (b): Transformation of saturated-vapor 1 -butene into

an ideal gas at the initial conditions (T 1, P1). Since the
pressure is relatively low, the values of HR1 and SR1 are
estimated by Eqs. (6.78) and (6.79) for the reduced
conditions, Tr = 0.650 and Pr = 1.2771/40.43 = 0.0316. The
computational procedure is represented by:
HRB (0.650,0.031 6,0.191) = -0.0985
SRB (0.650,0.0316,0.191) = -0.1063
Whence, HR1= (-0.0985)(8.314)(420.0) = -344 J mol-1
SR1= (-0.l063)(8.314) = -0.88 Jmol-1 K-1
As indicated in Fig. 6.7, the property changes for this step are
HR1 and -SR1because the change is from the real to the ideal-gas
state.

Step (c): Changes in the ideal-gas state from (273.15 K, 1.2771

bar) to (473.15 K. 70 bar). Here, Hig and Sig are given by Eqs.
(6.86) and (6.87), for which (Secs. 4.1 and 5.5):
8.314 x ICPH(273.15,473.15;1.967,31 .630E-3,-9.837E-6,0.0)
= 20,564 Jmol-1
8.314 x ICPS(273.15,473.15;1.967,31 .630E-3,-9.837E-6,0.0)
= 55.474 Jmol-1 K-1
Thus, Eqs. (6.86) and (6.87) yield:
Hig = 20,564 J mol1

ig

70
55.474 8.314 ln
22.18 Jmol 1 K 1
1.2771

Step (d): Transformation of 1-butene from the ideal-gas state

to the real-gas state at T2 and P2. The final reduced conditions
are:
Tr = 1.127
Pr = 1.731
At the higher pressure of this step, HR2 and SR2 are found by
Eqs. (6.76) and (6.77), together with the Lee / Kesler
correlation. With interpolated values from Tables E.7, E.8,
E.11, and E.l2, these equations give:
H 2R
2.294 0.191 0.713 2.430
RTc

Whence,

S 2R
1.566 0.191 0.726 1.705
RTc

H 2R 2.430 8.314 420.0 8,485 Jmol 1

S 2R 1.705 8.314 14.18 Jmol 1 K 1

The sums of the enthalpy and entropy changes for the four
steps give the total changes for the process leading from the
initial reference state (where H and S are set equal to zero)
to the final state:
H = H = 21,810- (-344) + 20,564 - 8,485 = 34,233 J mol-1
S = S = 79.84- (-0.88) + 22.18 - 14.18 = 88.72 J mol-1 K-1
The internal energy is:
U H PV 34,233

70 287.8
10cm 3barJ 1

32,218 Jmol 1

These results are in far better agreement with experimental

values than would have been the case had we assumed
l-butene vapor an ideal gas.

 yii
i

Tpc yiTc i
i

Ppc y i Pc i
i

The values so obtained are the mixture and

pseudocritical temperature and pressure, Tpc and Ppc, which
replace Tc and Pc to define pseudoreduced parameters :
P
Ppr
Ppc

T pr

T
T pc

Example 6.9
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 6.9
The pseudocritical parameters are found by Eqs. (6.89) and
(6.90) with critical constants from App. B:

T pc y1Tc1 y 2Tc 2 0.5 304.2 0.5 369.8 337.0 K

Ppc y1 Pc1 y 2 Pc 2 0.5 73.83 0.5 42.48 58.15bar

Whence.
T pr

140
Ppr
2.41
58.15

450

1.335
337.0

Values of Z0 and Z1 from Tables E.3 and E.4 at these

reduced conditions are:
Z0 = 0.697

and

Z1 = 0.205

With given by,

= y11+ y22 = (0.5)(0.224) + (0.5)(0.152) = 0.188
Eq. (3.54) yields:
Z = Z0+ Z1 = 0.697 + (0.188)(0.205) = 0.736

Whence,
V

ZRT 0.736 83.14 450

196.7cm 3 mol 1
P
140

Similarly, from Tables E.7 and

1
E.8,R 0
R

RT
pc

1.730

H 0.169
RT
pc

Substitution into Eq. (6.76) gives:

HR
1.730 0.188 0.169 1.762
RT pc

Whence, HR = (8.314)(337.0)(-1.762) = -4,937 J mo1-1

By Tables E.11 and E.12 and Eq. (6.77),
SR/R = -0.967 + (0.188)( -0.330) = - 1.029
Whence, SR = (8.314)(-l.029) = -8.56Jmol-1 K-1