06-321

ChemE Thermodynamics
Chemical Reac9on Equilibrium
in Aspen v8
Bruno A. Calfa

Last Update: October 27th, 2014

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Basics of Chemical Reac9on Equilibria (I/II)

Given general equilibrium reac9on
its equilibrium is determined by the equilibrium constant K.
Rela9onship between K and standard Gibbs free energy of the reac9on:
The equilibrium is dened in terms of the fugacity of the components:

Using fugacity coecients (typically in gas-phase reac9ons):

Basics of Chemical Reac9on Equilibria (II/II)

Extent of reac9on (coordinate of reac9on):
Extent to which the reac9on has taken place.

where is the stoichiometric coecient of species i (posi9ve if product,

nega9ve if reactant).
See deriva9ons in textbook (sec9on 13.1).

See also extension to mul9ple reac9ons.

Procedure: subs9tute yi into expression for K and solve for .
Minimiza9on of Gibbs Free Energy (see sec9on 13.9 for deriva9on): results
in solving the following algebraic equa9ons for ni.

Numerical Example
Water-Gas shi_ reac9on
Given: stoichiometric feed, P = 8,300 kPa, T = 500 K, so that
K = 148.4.
Calculate equilibrium composi9on.
A solu9on by-hand is easily achievable

Introduce the extent of reac9on .

Express number of moles of each component as func9ons of .
Use the expression of K to solve for .
Calculate the equilibrium composi9ons based on the value for .

Aspen Plus modeling

Use REquil or RGibbs models/blocks.
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Solu9on with Aspen

Add components.

Solu9on with Aspen

Select thermodynamic model. Use Method Assistant. Let us use SRK. Go to
the subfolder Parameters under Methods to conrm that you will be using
Aspens built-in temperature-dependent binary parameters.

Solu9on with Aspen

Switch to Simula9on environment. Add REquil under Reactors.
You may rename the block (right click -> Rename Block).

Solu9on with Aspen

Click on Material. Red arrows are mandatory. Blue arrows are op9onal.

Solu9on with Aspen

Draw streams. You can rename streams (right click -> Rename Stream).

Solu9on with Aspen

Congure feed stream. Go to folder Streams, then 1 (feed stream).

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Solu9on with Aspen

Congure reactor block. Go to folder Blocks, then B1.
Specica9ons (use same as feed for this example) + Vapor-Only.

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Solu9on with Aspen

Congure reactor block. Go to folder Blocks, then B1.
Reac9ons. Provide guess for extent of reac9on and ask Aspen to evaluate
equilibrium constant exactly at the given T (i.e., no T).

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Solu9on with Aspen

Run simula9on. Click on blue play bujon. It converged! We are not
performing economic evalua9ons at this point, so click Close.

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Solu9on with Aspen

Check results (Stream Summary).

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Solu9on with Aspen

To see molar frac9ons, go to folder Setup -> Report Op9ons -> Streams.
Check Mole for Frac9on basis.

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Solu9on with Aspen

Rerun simula9on. View Streams (Custom).

See le ChemReacEqExampleREquil.apwz.

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Solu9on with Aspen

Now try with RGibbs block. Add and congure streams and block.

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Solu9on with Aspen

Rerun simula9on. View Streams (Custom). Same solu9on as with REquil.

See le ChemReacEqExampleRGibbs.apwz.

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