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Phase equilibria and

Phase diagrams
Phase behavior of a pure component

H2O 2
Phase behavior of a pure component

3
Phase behavior of a pure component

Experimental p-v diagram


of CO2 [p.396, 3]

Critical isotherm
T = 304.19 K

4
p-T diagram of a pure
component [1, 2]
For water like substances if we increase
pressure, the solid melts to liquid. So, for
water, ice melts to liquid water and is
helpful for skating.

5
Phase behavior of a mixture of
components

For pure component

For mixture of
components
6
pv diagram of mixture of components

For pure component

7
p-T diagram of a mixture
of components

Cricondenbar

Cricondentherm
8
T-x-y diagram of a near ideal binary mixture

9
p-x-y diagram of a near ideal binary mixture

10
T-x, p-x, and x-y diagrams of various types

11
p-x-y diagrams of various binary mixtures

(a) Tetrahydrofuran (1)- (b) Chloroform (1)-


carbon tetrachloride (2) tetrahydrofuran (2) at
at 303.15 K 303.15 K

(c) Furan (1)-carbon (d) Ethanol (1)-toluene


tetrachloride (2) at (2) at 338.15 K
303.15 K 12
T-x-y diagrams of various binary mixtures [6]

(a) Tetrahydrofuran (1)- (b) Chloroform (1)-


carbon tetrachloride (2) tetrahydrofuran (2) at
at 1 atm 1 atm

(c) Furan (1)-carbon (d) Ethanol (1)-


tetrachloride (2) at 1 toluene (2) at 1 atm
atm
13
The concept of fugacity is introduced by G. N. Lewis (1901) and is
widely used in solution thermodynamics to represent the behavior of
real gas.

As the compressibility factor measures the deviation from ideal gas


behavior in terms of P,V, and T, fugacity measures the deviation from
ideal gas behavior in terms of chemical potential (), ( is defined as
the partial derivative of thermodynamic potentials H, A and G of ith
G
component of a multicomponent system i p ,T ,n )
ni
i

Fugacity is used extensively in the study of phase and chemical


reaction equilibria involving gases at high pressures.

The name fugacity is derived from the Latin for fleetness or


escaping tendency and is best thought of relative to liquid solutions.
In an equimolar liquid solution, the component with the higher
fugacity (escaping tendency) will be more prevalent in the vapor
phase.

The concept of fugacity becomes useful during the discussion of


phase equilibrium in mixtures. The definition of fugacity provides us
with the general concept.

Though the fugacity is mainly applied to mixtures, the present


discussion is limited to pure gases.
Fugacity and fugacity coefficient of pure gases

dGig = VigdP SigdT

RT
dGig = VigdP (constant T) V
ig

dGig = RT dlnP

G R T ln P T
i
ig

i
(11.27)

For real fluid

G R T ln f T
i i i
(11.30)

The pressure P is replaced by fi (fugacity) units of pressure.


Subtracting Eqn (11.27) from Eqn (11.30)

f
G G R T ln ig i (11.31)
i i
P

G R T ln
i
R

Where i is the fugacity coefficient.

f
i (11.32)
P
i

For ideal gas state fugacity of pure species equal to pressure

f i P , GiR 0 and 1 i
The fugacity coefficient is a measure of non-ideality.

For ideal(Attractive and repulsive forces are balanced)

Under most common conditions, the fugacity coefficient


is less than one (Attractive forces are dominant).

At very high pressures, the fugacity coefficient can


become greater than one (Repulsive forces are dominant).

In practice, the fugacity of a component does not


evaluated directly. Instead the fugacity coefficient is
evaluated and the fugacity is then calculated;

f=P
Three possible sources to find the fugacity

- Tables (thermodynamic property data)

- Equation of state

- Generalized correlations

Problem:

Determine the fugacity and the fugacity coefficient for saturated steam at 1 atm.
Fugacity coefficient of a pure gas and mixture using EOS
Fugacity coefficient of a pure gas and mixture using EOS
Fugacity coefficient of a gas mixture using EOS
Evaluation of f and i through cubic equations of state (e.g.
vdw, RK, SRK, or PR eqns.)
G R

Z 1 ln Z q I (6.36b)
RT
Then ln Z 1 ln Z
i i
q I i i
(11.36)
P T
where r
q r

T r
T r

1
Z
I ln (for )
Z

I (For = , vdw eqn.only)
Z
For vapor phase
Z
Z 1 q
Z Z
Lee/Kesler
ln ln ln 0 1
(11.63)

( ) ( ) 0 1
(11.64)

Virial coefficient correlation


P
ln B B
r 0 1

T r
or
P
exp B B r 0 1

T r

0.422 0.172
B 0.083
0
and B 1 0.139
T r 1 .6 T r 4 .2
Vapor/liquid equilibrium for pure species
The fugacity of pure species i, as a saturated vapor, may be written as:

G iv R T ln f i v i T (11.37a)

and for species i as a saturated liquid at the same temperature:

G il R T ln f i l i T (11.37b)

By difference,
f iv
G i G i R T ln l
v l

fi

an equation applicable to the change of state from saturated liquid

to saturated vapor, both at temperature T and the vapor pressure Pi s at


For a system in which saturated liquid and saturated vapor are in
equilibrium
G G 0 i
v

i
l

therefore:
f f f
i
v

i
l

i
sat
(11.38)

Where f i s at indicates the value for either saturated vapor or saturated liquid.

Since coexisting phases of saturated liquid and saturated vapor are in equilibrium

f i v f i l f i s at expresses a fundamental principle:

For a pure species coexisting liquid and vapor phases are in equilibrium

when they have the same temperature, pressure, and fugacity.


An alternative formulation is based on the corresponding fugacity coefficient;

f sat

sat i
(11.39)
i
P i
sat

whence


i
v

i
l

i
sat
(11.40)

this equation, expressing quality of fugacity coefficients, in an equally


valid criterion of vapor/liquid equilibrium for pure species.
Fugacity for pure liquid, Poynting method

V i l P Pi s at
f i i Pi
s at s at
exp
RT
The exponential is known as a Poynting factor.
Example

Calculate the fugacity of 1,3-butadiene at 313 K and 10 bar.

Tc = 425.2K Pc= 42.77 = 0.19 Zc = 0.267


Vc = 220.4 cm3 mol-1
Tr = 0.736 Pr = 0.2338

2 ,142.66
ln P kPa 13.7578
sat

T K 34.3

Psat = 432.572 kPa = 4.32 bar


P > Psat the condition of the 1,3-butadiene at 313 K and 10

bar is LIQUID

V l
P P sat

f P exp sat sat i i


i i i
RT

V Z 89.376 cm mol
1 Tr 0.2 8 5 7
V sat

c c
3 1

V P P
l sat
89.376 10 10 4.32 10
6 5

exp i i
exp 1.02
RT 8.314 313
P sat

exp r
B B
0 1

T r

0.422 0.172
B 0.083
0
0.606 and B 0.139
1
0.484
T 1 .6
r
Tr
4 .2

0.101
sat
exp 0.606 0.19 0.484 0.9086
0.736
i

V P P l sat

f P exp sat sat i i
0.9086 ( 4.32 ) (1.02 ) 4.002 bar
i
RT i i
Example
Calculate the fugacity and GR of 1,3-butadiene at 313 K and
10 bar using RK EOS and compare with correlation.

Tc = 425.2K Pc= 42.77 = 0.19 Zc = 0.267


Vc = 220.4 cm3 mol-1

2 ,142.66
ln P kPa 13.7578
sat

T K 34.3
Fugacity and Fugacity Coefficient of a Mixture
From virial EOS
Written for a gas mixture it is exactly the same as for a pure species
BP
Z 1
RT
For gases at low or moderate pressure
B y y B
i j i j ij

B11 y22 12
P
For binary ln 1 11.63a
RT

B22 y12 12
P 11.63b
ln 2
RT
Equations (11.63) are readily extended for application to multicomponent
gas mixture; the general equation is:


P 1
y y 2

ln k
B
kk
i j ik ij
RT 2 i j

Where the dummy indices i and j run over all species, and

2B B B
ik ik ii kk
2B B B
ij ij ii jj

with 0
ii
, 0
kk
. etc., and
ki ik
, etc.
Example
Determine the fugacity coefficients as given (11.63a) and (11.63b) for
nitrogen and methane in a N2(1)/CH4(2) mixture at 200K and 30 bar if
the mixture contains 40 mol-%N2. experimental virial-coefficient data
are as follows: B11 = -35.2 B22 = -105.0 B12 = -59.8 cm3 mol-1
By definition,

12 2 B12 B11 B22 2(59.8) 35.2 105.0 20.6 cm 3 mol 1



ln 1
P
RT
B11 y22 12
30
(83.14) ( 200)
2

35.2 0.6 20.6 0.0501

ln 2
P
RT

B22 y12 12 30
(83.14) ( 200)
2

105.0 0.4 20.6 0.1835

Whence, 1
= 0.9511 and 2
= 0.8324
Note that the second virial coefficient of the mixture as given by eqn.

(11.62) is B = -72.14 cm3 mol-1, and


BP
Z mix 1 0.870
RT
How to get B11, B22, and B12 numerically

For Binary system the following equation


B Pc
R Tc

B 0 B1

can be written as Bij


R Tcij
Pcij
B 0
i j B1
i j
i j
2

Tcij Tci Tcj 1 ki j


1
2
Z cij R Tcij
Pcij
Vcij

Z ci Z cj
Z cij
2
3
1 1

V V 3 3

ci cj
Vcij
2

kij is an empirical interaction parameter specific to an i-j molecule


pair. When i = j and for chemically similar species, kij = 0. Otherwise,
it is a small positive number evaluated from minimal PVT data or in
the absence of data set equal to zero.
Example:

Estimate the fugacity coefficients by equations (11.63) for equimolar mixture of


methyl ethyl ketone(1)/toluene(2) at 50 oC and 25 kPa. Set all kij = 0.

The required data are as follows:

ij Tcij/K Pcij/bar Vcij/cm3 mol-1 Zcij ij

11 535.5 41.5 267 0.249 0.323

22 591.8 41.1 316 0.264 0.262

12 563.0 41.3 291 0.256 0.293


ij Trij B0 B1 Bij/cm3 mol-1

11 0.603 -0.865 -1.300 -1,387

22 0.546 -1.028 -2.045 -1,860

12 0.574 -0.943 -1.632 -1,611

12 2 B12 B11 B22 2(1,611) 1,387 1,860 25 cm 3 mol 1



ln 1
P
RT
B11 y2 12
2 25
(8,314) (323.15)
2

1,387 0.5 25 0.0128


ln 2
P
RT
B22 y12 12
25
(8,314) (323.15)
2

1,860 0.5 25 0.0172

Whence, 1
= 0.987 and 2
= 0.983
Problem: Nitrogen gas is pressurized from 1 atm to 60 atm at constant temperature
100 oC. The fugacity of nitrogen can be determined by using equation as follows:
P
ln Z 1
dP
0
P
Calculate fugacity coefficient and fugacity of nitrogen from 1 atm to 60 atm by using
above equation. Also, plot fugacities obtained as function of pressure.

Given that: P (atm) 0 14 22 30 44 58 68


Z 1 0.95 0.92 0.89 0.84 0.79 0.76
Solution:

P (atm) Z Z-1
0 1 0
14 0.95 -0.05
22 0.92 -0.08
30 0.89 -0.11
44 0.84 -0.16
58 0.79 -0.21
68 0.76 -0.24
A directly proportional relation can be used as a reasonable approximation where
R2 = 0.9993. The linear relation is,

Z-1 = -0.0036 P
From given equation

P P
ln 0.0036P
dP
0.0036 dP 0.0036P
0
P 0

exp( 0.0036P)

P (atm) f (atm)
1 0.9964 0.9964
10 0.9646 9.6464
20 0.9305 18.610
30 0.8976 26.928
40 0.8658 34.635
50 0.8352 41.763
60 0.8057 48.344
Problem:
Determine the fugacity and fugacity coefficients for nitrogen and methane in a
N2(1)/CH4(2) mixture at 200K and 30 bar if the mixture contains 40 mol-%N2.

The required data are as follows:

ij Tcij/K Pcij/bar Vcij/cm3 mol-1 Zcij ij

11 126.2 34 89.2 0.289 0.038

22 190.6 45.99 98.6 0.286 0.012

12
Vapor Liquid Equilibrium (VLE)

Problem:

Consider a system with liquid containing 30 % n-pentane, 30% cyclohexane,


20% n-hexane and 20% n-heptane at 1 bar. Determine the temperature at which this
liquid develops the first bubble of vapor. What is the vapor composition?

Problem:

Consider a system with vapor containing 30 % n-pentane, 30% cyclohexane,


20% n-hexane and 20% n-heptane at 1 bar. Determine the temperature at which this
vapor develops the first drop of liquid. What is the liquid composition?

Problem:

A binary vapor mixture contains 48% ethanol in water at 70 oC. Determine the
pressure at which this vapor develops the first drop of liquid. What is the liquid
composition? The marguels parameters are as follows:
A = 3590 J/mol and B = -1180 J/mol
Margules Equation

Two Parameters (Three-Suffix)

= +

= +

One parameter (Two-Suffix)


Margules Equation

One parameter (Two-Suffix)


Van Laar equation
The form of the two-suffix equations developed by van Laar and are
given by

where A and B are the adjustable parameters which can be determined


from the experimental values of ln 1 and ln 2 as
Example
Under atmospheric condition, the acetone-chloroform azeotrope boils
at 64.6oC and contains 33.5 mol % acetone. The vapor pressures of
acetone and chloroform at this temperature are 995 mm Hg and 885
mm Hg respectively. Calculate the composition of the vapor at this
temperature in equilibrium with a liquid analyzing 11.1 mol %
acetone. (Apply the van Laar equation).

For component 1 (acetone)

For component 2 (chloroform)


At x1 = 0.335 and x2 = 0.665

At x1 = 0.111 and x2 = 0.889

1 = 0.4741

2 =
0.9746
Wilson Equation

GE
x1 ln( x1 x 2 12 ) x 2 ln( x 2 x1 21 ) (10.64)
RT

V2 12 11 V2 a12
12 exp( ) exp( )
V1 RT V1 RT

V1 12 22 V1 a21
21 exp( ) exp( )
V2 RT V2 RT
Wilson Equation

12 21
ln 1 ln( x1 12 x 2 ) x 2 ( )
x1 12 x 2 x 2 21 x1

12 21
ln 2 ln( x 2 21 x1 ) x1 ( )
x1 12 x 2 x 2 21 x1
NRTL (Non-Random Two-Liquid Equation)

GE 21 G21 12 G12
x1 x 2 ( )
RT x1 x 2 G21 x 2 x1 G12

G12 G22 b12 G21 G11 b21


12 21
RT RT RT RT

G12 exp( 12 ) G21 exp( 21 )


NRTL (Non-Random Two-Liquid Equation)

G21 12 G12
ln 1 x 2 ( 21 (
2
)
2
)
x1 x 2 G21 ( x 2 x1 G12 ) 2

G12 21 G21
ln 2 x1 (12 (
2
)
2
)
x 2 x1 G12 ( x1 x 2 G21 ) 2
Example

Using the Wilson and NRTL equations, estimate the


activity coefficients of the components of binary system
consisting of iso-butanol (1) and iso-propanol (2) at 50oC
and x1 = 0.3. At this temperature, the molar volumes of
the components are V1 = 65.2 cm3/mol and V2 = 15.45
cm3/mol.
Data given:
For Wilson equation
a12 = 300.55 cal/mol a21 = 1503.2 cal/mol
For NRTL equation:
Wilson Equation

V2 a12 V1 a21
12 exp( ) 0.147 21 exp( ) 0.403
V1 RT V2 RT

12 21
ln 1 ln( x1 12 x 2 ) x 2 ( )
x1 12 x 2 x 2 21 x1

ln 1 0.8208 1 2.27

12 21
ln 2 ln( x 2 21 x1 ) x1 ( )
x1 12 x 2 x 2 21 x1

ln 2 0.223 2 1.25
NRTL Equation
b12 b21
12 1.06 21 1.87
RT RT

G12 exp( 12 ) 0.557

G21 exp( 21 ) 0.357

G21 12 G12
ln 1 x 2 ( 21 (
2
)
2
)
x1 x 2 G21 ( x 2 x1 G12 ) 2

ln 1 0.772 1 2.164
NRTL Equation

G12 21 G21
ln 2 x1 (12 (
2
)
2
)
x 2 x1 G12 ( x1 x 2 G21 ) 2

ln 2 0.234 2 1.263

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