BINARY VAPOR LIQUID EQUILIBRIUM (VLE)

By CheGuide | November 1, 2015 | Comments4 Comments

This article shows how to prepare Pxy and Txy diagram for binary mixtures in
excel spreadsheet based on Wilson, NRTL and UNIQUAC activity coefficient
model.

For low to moderate pressure vapor liquid equilibrium (VLE) is described by

modified Raoults Law

yi P = xi i Pisat

where, yi is vapor mol fraction, P is system pressure, xi is liquid mol fraction,

i is activity coefficient and Pisat is vapor pressure for a pure component i.
Vapor pressure is calculated based on Antoine equation.

ln Pisat = Ai - Bi /( T + Ci )

Ai , Bi and Ci are Antoine equation constants and T is temperature at which

vapor pressure is to be calculated.

Txy Diagram
Txy diagram plots bubble and dew point curves at constant pressure P. Put
down the liquid mol fraction x1 from 0.0 to 1.0 with increment of 0.01 in
spreadsheet. Iteration is done for each liquid mol fraction to estimate
equilibrium temperature T and activity coefficient i.

For first iteration, T1sat and T2sat are calculated from Antoine equation.

Tisat = Bi/ (Ai - ln Pisat) - Ci

Equilibrium temperature is estimated as following

T = x1 T1sat + (1 - x1)T2sat

Based on temperature T, activity coefficient 1 and 2 are calculated from

activity coefficient model selected e.g. Wilson, NRTL and UNIQUAC. For ideal
mixture 1 and 2 are 1.

Saturation pressure for a component is calculated using following equation

P1sat = P/(x11 +(1-x1)2 P2sat/P1sat)

Temperature corresponding to the vapor pressure P1sat is calculated from

Antoine equation.

T = B1/ (A1 - ln P1sat) - C1

Temperatue thus calculated is used for next iteration and activity coefficients
1 and 2 are calculated. Iterations are repeated till there is no change in
subsequent temperature estimations. Typically temperature difference
becomes negligible within 10 iterations.

Above steps are repeated for all liquid mol fractions, thereby giving a table of
x1 and corresponding temperature T. Vapor mol fraction y1 is calculated as
following

y1 = x1 1 P1sat/ P

Plot of T, x1 & y1 gives Txy Diagram

Pxy Diagram
Pxy diagram plots bubble and dew point curves at constant temperature T.
Put down the liquid mol fraction x1 from 0.0 to 1.0 with increment of 0.01 in
spreadsheet. Calculate activity coefficients 1 and 2 based on activity
coefficient model selected from Wilson, NRTL and UNIQUAC.

Calculate partial pressure of each component P1 and P2 as following

P1 = x1 1 P1sat
P2 = (1 - x1) 2 P2sat

Equilibrium pressure is obtained as following

P = P1 + P 2

Vapor mol fraction is calculated as per below equation.

y1 = P1 / P

Plot of P, x1 & y1 gives Pxy Diagram

Wilson Model
Activity coefficient for binary system are defined as

Wilson parameter is provided by following equation

where, 12 11 and 21 22 are binary interaction parameters available from

literature for a binary pair.

Modified Rackett equation is used to estimate liquid molar volume V1 & V2.
V = (RTc/Pc)ZRA [1 + (1-Tr)^(2/7)]

where, Tc and Pc are critical temperature and pressure. Tr is the reduced

temperature. ZRA is Rackett equation parameter, if it is not available, it can be
estimated from accentric factor as following.

ZRA = 0.29056 - 0.08775

NRTL Model
Activity coefficient for binary system are defined as

Parameter g12 g22 and g21 g11 are binary parameters available from
literature. 12 is related to non-randomness in mixture and is available from
literature for binary pairs.

UNIQUAC Model
Activity coefficient for binary system are defined as
Parameter u12 u22 and u21 u11 are binary parameters available from
literature. Remaining parameters are calculated as following

where z is set equal to 10 and r, q & q are pure component UNIQUAC

parameters.

Spreadsheet
All above calculations along with iterative procedure for Txy diagram have
been modeled in below spreadsheet. Sheets can be modified and more binary
pairs can be added in data-bank.

Spreadsheet for Binary Vapor Liquid Equilibrium