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Low-Moderate Pressure VLE Analysis

The document discusses vapor-liquid equilibrium (VLE) and various VLE formulations for modeling phase behavior at different pressure ranges. It introduces the concepts of Raoult's law, modified Raoult's law for low to moderate pressures, and cubic equations of state for high pressures. Diagrams like P-x-y, T-x-y are presented to show ideal and non-ideal behavior. The flash calculation algorithm is described for computing vapor and liquid phase compositions given total moles, temperature and pressure.

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Abhinav Anand
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635 views23 pages

Low-Moderate Pressure VLE Analysis

The document discusses vapor-liquid equilibrium (VLE) and various VLE formulations for modeling phase behavior at different pressure ranges. It introduces the concepts of Raoult's law, modified Raoult's law for low to moderate pressures, and cubic equations of state for high pressures. Diagrams like P-x-y, T-x-y are presented to show ideal and non-ideal behavior. The flash calculation algorithm is described for computing vapor and liquid phase compositions given total moles, temperature and pressure.

Uploaded by

Abhinav Anand
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

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

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