Low to Moderate Pressure VLE for

Real Systems:
Modified Raoult’s Law
P-x-y Diagram (Ideal: Raoult’s Law Behaviour)
T-x-y Diagram (Ideal: Raoult’s Law Behaviour)
Nonideal and
Azeotropic
Behaviour

P-x1-y1 plots

a. Negative deviation
from Raoult’s Law

b. Positive Deviation
from Raoult’s Law
Nonideal and
Azeotropic
Behaviour

T- x1- y1 plots

a. Negative deviation
from Raoult’s Law

b. Positive Deviation
from Raoult’s Law
Azeotropic Ether-Isopropyl Alcohol VLE Data
Deviation from Ideal
Behaviour
General P-x-y and T-x-y Diagrams
Isotherms Isobars

TX < TC1 and TC2 PX < PC1 and PC2

TY < TC1 , but TY > TC2 PY < PC1 , but PY > PC2
TZ > TC1 and TC2 PZ > PC1 and PC2
Binary VLE: Extended data
P-T-x-y diagram for binary vapor-liquid equilibrium
Types of Vapour-Liquid Equilibria Formulations
Type of VLE Corrections Needed for Gas / Liquid Phases

Raoult’s Law VLE System pressure atmospheric or less

Liquid-phase forms ideal solution

Low to Moderate System pressure between 1-10bar (approx); non-

Pressure VLE ideality described fugacity coefficients based on
Virial EOS
Liquid-phase non-ideality described by activity
coefficients using suitable activity model

High Pressure VLE System pressure > 10 bar, non-ideality described

fugacity coefficients based on Cubic EOS
Liquid-phase non-ideality described by fugacity
coefficients based on Cubic EOS
Phase Equilibrium Criterion in terms of
Fugacity / Fugacity Coefficients
 V V
dGi  RTd ln fi
dGiL  RTd ln fi L
On integration between vapour and liquid states:
V
f
GiV  GiL  RT ln i L
fi
At equilibrium:GiV  GiL  0
V L sat
Thus: fi  fi  fi
For a pure species coexisting liquid and vapor
phases are in equilibrium when they have the
same temperature, pressure, and fugacity.
Alternately :
fiV / Pi sat  f i L / Pi sat  fi sat / Pi sat
V L sat
  
i i i
sat
sat fi
where :  i  sat
Pi
For a multi-component sytem equilibrium
between two phases  and  : i  i
But : d    RTd ln fˆ 
i i

d i  RTd ln fˆi 

On integrating between the two phases:
fˆ 
i  i  RT ln i 
fˆi
 
At equlibrium:    0
i i

ˆ 
Hence: f  f ˆ 
i i
 Modified Raoult’s Law
Low to Moderate Pressure VLE Formulation
General equation of VLE (Low-to Moderate Pressure)

ˆ v ˆ
For phase equilibrium : f i  f i l

fˆ v  y ˆ P & fˆ l  x  f
i i i i i i i

Thus, yiˆi P  xi i f i

s
Or : yi  i P  xi i Pi
ˆi  Vi l ( P  Pi sat )  ˆi
where,  i  sat exp     sat
i  RT  i
sat
sat Bii Pi
Now, i 
RT
  P
For a binary : ln 1  ( B11  y2212 )
RT
 P
ln 2  ( B22  y1212 )
RT

B11 ( P  P1s )  Py2212

Hence : 1  exp[ ]
RT
B22 ( P  P2s )  Py1212
 2  exp[ ]
RT
Low to Moderate Pressure VLE Algorithms:
• Bubble Pressure
• Bubble Temperature
• Dew Pressure
• Dew Temperature
• Flash
Flash Process
 Flash Process Schematic
Given T, P and {zi}, find V, L, {yi}, {xi}
 Flash Calculation Algorithm
zi F ( feed )  xi L(liq. phase)  yiV (vap. phase)
L  V  F (moles of feed )
If , F  1  zi F ( feed )  xi (1  V )  yiV
K i  yi / xi  Pi s / P...(1)
xi  yi / K i ...(2)
zi K i
Thus, yi  ...(3)
1  V ( K i  1)
zi K i
Hence,  yi    1....(4)
i i 1  V ( K i  1)

Given zi , T & P, use (4) to compute V

And (3) & (2) to get yi & xi respectively
END