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by CheGuide

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You are on page 1of 7

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.

modified Raoults Law

yi P = xi i Pisat

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 )

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.

T = x1 T1sat + (1 - x1)T2sat

activity coefficient model selected e.g. Wilson, NRTL and UNIQUAC. For ideal

mixture 1 and 2 are 1.

Antoine equation.

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

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.

P1 = x1 1 P1sat

P2 = (1 - x1) 2 P2sat

P = P1 + P 2

y1 = P1 / P

Wilson Model

Activity coefficient for binary system are defined as

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)]

temperature. ZRA is Rackett equation parameter, if it is not available, it can be

estimated from accentric factor as following.

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

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.

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