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Outline

Vapor-Liquid Equilibrium
Gamma/Phi Formulation
Phi/Phi Formulation

Equilibrium and Stability


Liquid-Liquid Equilibrium
Vapor-Liquid-Liquid Equilibrium
Solid-Liquid Equilibrium
Special Topics
2

Vapor-Liquid Equilibrium
Recall: criteria for phase equilibrium

Giv Gil iv il fi v fi l
v

f
v

i i
yi P
fi l
i

l
xi fi

f v y Pv
i
i
i

y
P

f
i i
i i i
f l x f l
l
sat
i
i i i

V
(
P

P
)
l
sat sat
i
i
fi i Pi exp

RT

Vi l ( P Pi sat ) i
i
Let i sat exp
sat

RT
i

i
yi P i xi i Pi sat

Vapor-Liquid Equilibrium
Where to obtain values:
Psat Antoine equation
Function of T

^, sat 2-term virial equation


Function of T, P, y

model for GE
Function of T, P, x
Independent of P at low to moderate pressures

Vapor-Liquid Equilibrium
Bubble P: given are T, x, constants
Set all =1
Calc

Psat,

Calc P

Check P < tol

Calc y
Calc

Calc P
5

Vapor-Liquid Equilibrium
Dew P: given are T, y, constants
Set all ==1
Calc

Psat,

Calc P

Check P < tol

Calc x,

Calc

Calc P

Check < tol

Calc x
Normalize x
Calc
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Vapor-Liquid Equilibrium
Ex. GE for the system chloroform(1)/
methanol(2) is well represented by the
Margules equation below. The vapor pressures
at 55oC are 82.37kPa (1) and 37.31 kPa.
E
G / RT (1.42 x1 0.59 x2 ) x1 x2
Assuming validity of modified Raoults Law,
calculate P and ys at 55oC for x1=0.25.
Redo using the gamma-phi formulation, given
B11 963cm3 / mol

B22 1523cm3 / mol B12 52cm3 / mol


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Vapor-Liquid Equilibrium
For Bubble/Dew T
Initial estimate of T
Bi
sat
Ti
Ci
Ai ln P
Tinit xiTi sat or

Tinit yiTi sat

Since Psat ratios are weak functions of T


Pjsat P / ( xi i / i )( Pi sat / Pjsat )
Pjsat P ( yi i / i )( Pi sat / Pjsat )

Bj
Aj ln P

sat
j

Cj

Vapor-Liquid Equilibrium
Bubble T: given P, x, constants
Set all =1

Choose j

Calc Tsat, Tinit

Calc PJsat

Calc

Psat,

Calc T

Check T < tol

Calc Psat, y
Calc ,

Calc PJsat
Calc T

Vapor-Liquid Equilibrium
Dew T: given P, y, constants
Set all ==1

Calc

Tsat,

Tinit

Calc Psat

Choose j

Calc

PJsat

Calc T

Calc x
Normalize x

Calc

Psat,

Calc x

Calc , PJsat

Calc T

Calc

Calc Psat,

Check < tol

Calc PJsat
Calc T

Check T < tol


10

Vapor-Liquid Equilibrium
Flash Calculations
zi Ki
yi
1 V ( Ki 1)

zi
xi
1 V ( K i 1)

Since y = x = 1
zi Ki
Fy
1 0
1 V ( Ki 1)
zi ( Ki 1)
F Fy Fx 0
1 V ( Ki 1)
zi ( Ki 1)2
dF

dV
[1 V ( Ki 1)]2

yi i Pi sat
Ki
xi
i P

zi
Fx
1 0
1 V ( Ki 1)

dF
F
dV

V 0

11

Vapor-Liquid Equilibrium
Flash Calculations
Initial calculations: dew P and bubble P
Initial estimates
Interpolated i at P between Pdew and Pbubl
Interpolated ^i at P between Pdew and Pbubl
Interpolated V at P between Pdew and Pbubl

Pbubl P
V
Pbubl Pdew

12

Vapor-Liquid Equilibrium
Flash Calculations: given T, P, z
Calc Pdew
(y=z, V=1)

Calc Pbubl
(x=z, V=0)

Calc K
Calc F,
dF/dV

Calc x, y

Check V, x,
and y < tol

Interpolate

, , V

Solve for V

Check
Pdew<P<Pbubl

Calc ,

13

Vapor-Liquid Equilibrium
Solute(1)/Solvent(2) Systems
When component (1) is unstable or supercritical
No vapor P, cant calculate f
(1) cannot exist as pure liquid at T

14

Vapor-Liquid Equilibrium
Solute(1)/Solvent(2) Systems
Recall:

f1
H1 lim
x1 0 x
1

f1
1
x1 f1

Since x10

f
1 1
y1 P

f x 1 H = y P
1
1
1
1 1 1

H1 f

1 1

For bubble P calc

x1 ( 1 / )H1
y1
1P

x P
y2
2 P

sat
2 2 2
15

Vapor-Liquid Equilibrium
Solute(1)/Solvent(2) Systems
Obtain T, P, x, y from VLE experiment
Obtain , from 2-term virial equation
Obtain from GE model
Obtain H from y/x vs. x plot

y1

H1 P lim
x1 0 x
1
sat
2
1

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