Vapor Liquid Equilibrium Calculations

Vapour-liquid equilibrium (VLE) calculations are one of the most fundamental calculations typically done
by a chemical engineer. While doing calculation on a variety of process unit operations e.g. flash drums,
distillation columns, VLE calculations are required for properly designing the size, specifications, and
operating temperature/pressure of all unit operations.

The simplest model for VLE relating the liquid and vapor compositions in equilibrium is Raoult's Law:




where
y
i
is the mole fraction of component "i" in the gas phase
P is the total pressure
x
i
is the mole fraction of component "i" in the liquid phase
P
i
VP
is the vapor pressure of component "i" at the specified temperature.

Vapor Pressure (Pi
VP
)

The vapor pressure of component "i" can be calculated through the empirical Antoine's Equation:




where
A
i
, B
i
, and C
i
are empirical constants specific to the identity of component "i"
T is the temperature in degrees Celsius
P
i
VP
is the vapour pressure of component "i" in mm Hg

Bubble Temperature (Tbp)

Bubble point is the temperature at which the first drop of liquid condenses in a mixture with a certain
composition and pressure.




The bubble temperature cannot be calculated directly since the vapor pressures Pi
VP
are dependent on
the temperature.

Thus, an iterative algorithm is required to solve the problem by

VP
i i i
P x P y =
|
|
.
|

\
|

=
i
i
i
C T
B
A
VP
i
P 10
) ( ) (
2 2 1 1 bp
VP
bp
VP
TOTAL
T P x T P x P + =
1. estimating the bubble temperature (the spreadsheet calculates the saturated temperature at the
overall pressure of the system, although any adequate estimation method will do)
2. calculating the values of Pi
VP
using Antoine's equation
3. calculating the total pressure resulting from this initial estimate
4. Revising the temperature estimate and re-iterating until the calculated total pressure matches the
actual total pressure.

Dew Temperature (Tdp)
The Dew Point temperature is the temperature at which the first bubble of vapor forms in a mixture with a
certain composition and pressure.





This problem is solved in a similar iterative manner:

1. estimating the dew temperature
2. calculating the first-pass values of Pi
VP
using Antoine's equation
3. calculating the sum of the liquid mole fractions resulting from this initial estimate
4. Revising the temperature estimate and re-iterating until the sum of the liquid mole fractions is
equal to one.

Example
Calculation of Bubble point temperature for a Ethanol (50%) Benzene (50%) mixture.

Antoine's Equation Coefficients
for Ethanol
A= 8.1122
B= 1592.864
C= 226.184

Antoine's Equation Coefficients
for Benzene
A= 6.87987
B= 1196.76
C= 219.161

BubT Calculation @ pressure = 760 mmHg

Iteration 1

Guess BubT = 75 Deg C
P
1
VP
= 333.040 mmHg
P
2
VP
= 323.933mmHg
P
Total
= 656.973 mm Hg
Iteration 2
Guess BubT = 78 Deg C
1
) ( ) (
2
2
1
1
= + =

dp
VP
TOTAL
dp
VP
TOTAL
i
T P
P y
T P
P y
x
P
1
VP
= 375.539 mmHg
P
2
VP
= 356.064 mmHg
P
Total
= 731.603 mm Hg
Iteration 3
Guess BubT = 79.075 Deg C
P
1
VP
= 391.831 mmHg
P
2
VP
= 368.169 mmHg
P
Total
= 760.000 mm Hg
Converged solution: Lets us work the vapor compositions

Example
Calculation of Dew point temperature for a Ethanol (50%) Benzene (50%) mixture.

Antoine's Equation Coefficients
for Ethanol
A= 8.1122
B= 1592.864
C= 226.184

Antoine's Equation Coefficients
for Benzene
A= 6.87987
B= 1196.76
C= 219.161

DewT Calculation @ pressure = 760 mmHg

Iteration 1

Guess BubT = 75 Deg C
P
1
VP
= 333.040 mmHg
P
2
VP
= 323.933mmHg

Iteration 2

Guess BubT = 78 Deg C
P
1
VP
= 375.539 mmHg
P
2
VP
= 356.064 mmHg

Iteration 3

Guess BubT = 79.103 Deg C
P
1
VP
= 392.261 mmHg
P
2
VP
= 368.486 mmHg