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Vapor-Liquid Equilibrium
Gamma/Phi Formulation
Phi/Phi Formulation
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
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
Calc y
Calc
Calc P
5
Vapor-Liquid Equilibrium
Dew P: given are T, y, constants
Set all ==1
Calc
Psat,
Calc P
Calc x,
Calc
Calc P
Calc x
Normalize x
Calc
6
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
Vapor-Liquid Equilibrium
For Bubble/Dew T
Initial estimate of T
Bi
sat
Ti
Ci
Ai ln P
Tinit xiTi sat or
Bj
Aj ln P
sat
j
Cj
Vapor-Liquid Equilibrium
Bubble T: given P, x, constants
Set all =1
Choose j
Calc PJsat
Calc
Psat,
Calc T
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,
Calc PJsat
Calc T
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
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
16