Example Problems in Vapour-Liquid Phase Equilibria
The simplest form of multi-component vapour – liquid equilibrium (VLE) calculations are
carried out using the so-called Raoult’s Law (RL) which relates the equilibrium temperature
(T), pressure (P), liquid phase (xi) and vapour phase (yi) compositions (i = component index).
Starting from the equilibrium criterion:
iV = iL , ( i = 1,.....N ) one can derive the simplest vapour-liquid equilibrium relation, the Raoult's law ( RL ) :
yi P = xi Pi sat , ( i = 1,.....N ) (A)
The vapour pressures Pi sat is given by the Antoine equation:
Bi
ln Pi sat (kPa) = Ai − (B)
T ( K ) + Ci
0
where Ai, Bi and Ci are constants for the ith component
Note that the following mass balance equations must also be satisfied along with the RL
equations:
N N
xi = 1;
i =1
y
i =1
i =1 (C)
Applying the Gibbs Phase rule, the degrees of freedom (F) are:
F =C−P+2
For the present case:
F = N −2+2 = N
The VLE variables from the RL equation are, T, P, (N-1) liquid phase mole-fractions, and
(N-1) vapour phase mole-fractions = 2 + 2( N − 1) = 2 N
Since there are only ‘N’ RL equations of type ‘A’ which relate the VLE variables, in order to
solve the VLE problem we need to specify ‘N’ variables and use the RL equations to solve for
the remaining N variables.
Various forms of VLE calculations are possible. We give only two types here:
Introduction to Chemical Engineering Thermodynamics (SR) 1
1. Bubble pressure calculations: Given xi and T , calculate yi and P
2. Dew pressure calculations: Given yi and T , calculate xi and P
Note that in each of the above cases we are providing the values of 'N' variables,
and solving for the other unknown "N" variables
Bubble Pressure for a binary system:
yi P = xi Pi s
y P = x P
i i i
s
y = 1 Thus, P
i bubble = x1P1s + x2 P2s
x1 = 1 − x2 Pbubble = P2s + ( P1s − P2s ) x1.....( A)
For a given x1 compute Pbubble using eq. A
And then find y1 = x1P1s / Pbubble
Finally y2 = 1 − y1
Dew Pressure for a binary system:
From Raoult's law, xi = yi P / Pi s
x = y P/ P
i i i
s
= P yi / Pi s =1
1
Thus, Pdew =
P
yi
s
i i
For a binary for a given vapour phase composition:
1
Pdew = (B)
y1 y2
s+ s
P1 P2
Calculate Pdew using eq. B; then calculate x1 = y1P / P1s
and then x2 = 1 − x1
It may be noted that the two algorithms can be easily extended to more than binary systems
Examples:
The binary system acetonitrile (1) / nitromethane (2) follows Raoult’s Law. The Antoine
equations for the system are:
2945.47 2972.64
ln P1sat (kPa) = 14.2724 − ; ln P2sat (kPa) = 14.2043 − 0
T ( K ) − 49.15
0
T ( K ) − 64.15
Compute:
a) the bubble pressure and vapour phase composition, at 348.150K for a liquid phase
composition of x1 = 0.6
Introduction to Chemical Engineering Thermodynamics (SR) 2
b) the dew pressure and liquid phase composition, at 348.150K for a vapour phase
composition of y1 = 0.6
Solution
(a) First find the saturation vapour pressures of each component at the given temperature of T
= 348.150K. So, using the Antoine equations:
P1sat = 83.21kPa; P2sat = 41.98kPa ; it follows that component (1) is more volatile. Using the
bubble pressure algorithm:
Pbubble = (0.5)(83.21) + (0.4)(41.98) = 66.72kPa
Alternately, Pbubble = P2s + ( P1s − P2s ) x1 = 41.98 + (83.21 − 41.98)(0.6) = 66.72kPa
Ps 83.21kPa
The vapour phase composition in equililbrium: y1 = ( x1 ) 1 = ( 0.6 ) = 0.7483
Pbubble 66.72kPa
Finally y2 = 1 − y1 = 0.2517
P2s 41.98kPa
Note that we can, alternately, calculate y2 = ( x2 ) = ( 0.6 ) = 0.2517
Pbubble 66.72kPa
Indeed when there are more than two components one needs to independently compute all y1' s
Ps
using : yi = ( xi ) i
Pbubble
(b) Next use the dew pressure algorithm.
1
Pdew =
P
yi
s
i i
For a binary for a given vapour phase composition:
1 1
Pdew = = = 59.74kPa
y1 y2 0.6 0.4
s + s 83.21 + 41.98
P1 P2
P 59.74kPa
Next calculate x1 = ( y1 ) dews = ( 0.6 ) = 0.4308
P1 83.21kPa
and then x2 = 1 − x1 = 0.5692
P 59.74kPa
Note that we can also independently calulate x2 = ( y2 ) dews = ( 0.6 ) = 0.5692
2
P 41.98kPa
Indeed, when there are more than two components one needs to independently
P
compute all x1' s using : xi = ( yi ) dews
Pi
Introduction to Chemical Engineering Thermodynamics (SR) 3