Vapor-Liquid Equilibrium Data Using Arc Length Continuation

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Consider two binary mixtures: (1) ethanol and water and (2) ethanol and ethyl acetate. This Demonstration computes the isobaric vapor-liquid diagram as well as the equilibrium curve at user-set values of the total pressure (expressed in
). The modified Raoult's law is used along with the van Laar model and Antoine equation. Both systems present a positive pressure-sensitive azeotrope. When present, this azeotrope is indicated on the equilibrium curve by a red dot. The loci of the azeotrope versus pressure
is given in a separate plot. In both cases, the azeotrope disappears at a low enough total pressure. One particular feature of the present calculation is that it uses the arc length continuation method (see the Details section) to find the bubble/dew point temperatures versus liquid/vapor phase compositions. This takes advantage of a new function as of Mathematica 9.0, WhenEvent, which determines the loci of the azeotropes; indeed they verify
, where
is the arc length parameter.
Contributed by: Housam Binous, Ahmed Bellagi, and Brian G. Higgins (December 2013)
Open content licensed under CC BY-NC-SA
Snapshots
Details
For vapor-liquid equilibrium data computations, the nonlinear equation , where
is the liquid mole fraction and
is the bubble temperature, is the bubble point equation derived from Dalton's law and the modified Raoult's law. Introduce an arc length parameter
. The nonlinear algebraic equation becomes
. We use the built-in Mathematica function NDSolve to solve this equation together with the differential equation (called the arc length constraint)
in order to find
and
. A simple initial condition is found by taking
and
equal to the boiling temperature of pure ethanol at
.
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