ASSIGNMENT 3

2. EXPLAIN BRIEFLY THE FOLLOWING ITEMS:

G) Generalized correlations for the fugacity coefficient
Eq. (11.35) is put into generalized form by substitution of the
relations,

P Pc Pr
P

Zi 1
0

ln i

dP Pc dPr

dP
P

const T

(11.35)

Hence,

ln i

Pr

Z i 1

dPr
Pr

(11.65)

where the integration is at constant Tr. Substitution for Zi by Eq.

(3.57) yields

Zi Z 0 Z 1
ln

Pr

(3.57)

Pr
dPr
dP
Z 1
Z 1 r
0
Pr
Pr
0

where for simplicity i is omitted.

This equation may be written in alternative form:

ln ln 0 ln 1

(11.66)

where

ln 0

Pr

Z0 1

dPr
Pr

and

Pr

ln 1 Z 1
0

dPr
Pr

The integrals in these equations may be evaluated numerically or

graphically for various values of Tr and Pr from data for Z0 and Z1
given in Table E.1- E.4 (Appendix E).

Another method, and the one adopted by Lee and Kesler to

extend their correlation to fugacity coefficients, is based on an
equation of state.
Eq. (11.66) may also be written,

0 1

(11.67)

Table E.13 E.16 present values for these quantities as derived

from the Lee/Kesler correlation as function of Tr and Pr.
A useful generalized correlation for ln results when the simplest
form of the virial equation is valid.
Eqs. (3.61) and (3.63) combine to give

Z 1

Pr 0
B B1

Tr

Z 1

BP
Pr
1 B
RT
Tr

B0 B1
B
Substitution in eq. (11.65) and integration yield

ln

Pr 0
B B1

Tr

Pr 0

B B 1

Tr

exp

or

This equation provides reliable values of for any nonpolar or

slightly polar gas when applied at conditions where Z is
approximately linear in pressure. E.g. H2, N2, O2, CO2, CH4, C2H4
H) The ideal solution model
The chemical potential for ideal gas mixture model is given by
eq. (11.24)

ig
i

G Giig T , P RT ln yi
ig
i

(11.24)

For an ideal solution,

id
i

G Gi T ,P RT ln xi
id
i

Partial volume,

(11.75)

Vi

By eq. (11.4),

As a result of

id

Giid
Gi

P
T

T ,x

Gi / P T
Viid Vi

Vi

; thus,

eq. (11.19),

Giid
Gi
S

T R ln xi

P ,x
id
i

By eq. (11.5),

Siid Si R ln x i (11.77)

H iid Giid TS iid , substitution by eqs. (11.75)

Because
and (11.77) yield

H iid Gi RT ln x i TS i RT ln x i
or

H iid H i

(11.78)

The summability relation

n, eq. (11.11), applied to the special case of an ideal solution, is
written:

M id xi M iid
i

Application to eqs. (11.75) (11.78) yields

G id xi Gi RT x i ln x i

11.79

S id xi Si R x i ln x i

11.80

V id x iVi

11.81

H id x i H i

11.82

H) The excess Gibbs energy and the activity coefficient

Eq. (11.46) may be written as

Gi i T RT ln f i

In accord with eq. (11.83) for an ideal solution, this becomes

(11.83)

Giid i T RT ln xi fi

f id x f
i
i i

By difference,

f
Gi G RT ln i
xi fi
id
i

The left side of this equation is the partial excess Gibbs energy

GiE ; the dimensionless ratio on the right side is the activity

coefficient of species i in solution, i.
By definition,
(11.90 )
So,

f
i i
xi fi

GiE RT ln i (11.91)

These equation establish a thermodynamic foundation for the

activity coefficient, as a factor introduced into Raoults law to
account for liquid phase non-idealities.

Comparison with eq. (11.51) shows that eq. (11.91) relates i to

GiE
exactly as eq. (11.51) relates

to

GiR RT ln i
For an ideal solution,

GiE 0,

GiR

(11.51)

and therefore i = 1.

A further relation results from combination of eq. (11.91) with eq.

(11.88)

RT ln i Gi Giid

M iE M i M iid

Elimination of the final term by eq. (11.75) and rearrangement

gives

id
i

G Gi T , P RT ln xi
id
i

(11.75)

Gi i Gi RT ln i x i (11.92)
This equation is an alternative definition of the activity
coefficient.
For ideal gas mixture model,

iig Giig RT ln yi

(11.24)

For ideal solution model,

iid Gi RT ln x i (11.75)
For non-ideal solution,

i Gi RT ln i xi

J) Liquid-phase properties from VLE data

(11.92)

The figure shows coexistence of a vapor mixture and liquid solution

in vapor/liquid equilibrium. T and P are uniform throughout the
vessel and can be measured with appropriate instruments. Vapor
and liquid samples may be withdrawn for analysis and this provides
experimental values for mole fractions in the vapor {y i} and mole
fractions in the liquid {xi}.
K) Models for the excess Gibbs energy
Model

Equations

Margul
es

GE
A21 x1 A12 x2
x1 x2 RT

Van
Laar

A' A '
GE
' 12 21'
x1 x2 RT A 12 x1 A 21 x2

ln 1 x22 A12 2 A21 A12 x1

ln 2 x12 A21 2 A12 A21 x2

'
A12
x1

ln 1 A 1 '

A
x

21 2
'
12

A'21 x2
ln 2 A 21 1 '
A 12 x1

'

Wilson

GE
x1 ln x1 x2 12 x2 ln x2 x1 21
RT
Vj
aij
ij exp
(i j)
Vi
RT

NRTL

GE
G21 21
G12 12

x1 x2 RT x1 x2G21 x2 x1G12

G12 exp( 12 ) G21 exp( 21 )

12

b12
RT

21

b21
RT

12
21

x1 x2 12 x2 x1 21

12
21
ln 2 ln x2 x1 21 x1

x1 x2 12 x2 x1 21

ln 1 ln x1 x2 12 x2

G21
G12 12

ln 1 x 21

2
x

x
G

1
x2 x1G12
2 21
2

G12
G21 21
2

ln 2 x1 12
x2 x1G12

x1 x2G21 2

2
2