Machine Problem No.

3
EQUILIBRIA

OBJECTIVE
1. To perform equilibrium calculations using MS Excel® and Aspen Plus®

INTRODUCTION

Vapor-Liquid Equilibrium

Distillation is one of the most mature technologies in chemical engineering. It is used to separate a
mixture of chemicals into two or more streams, each a relatively pure stream of one or more chemicals.
The physical process governing this separation is vapor-liquid equilibrium.

Consider the flowsheet in Figure 3.1. V

yi

F Phase
zi Separator

L
xi

Figure 3.1. Phase Separator

The temperature, pressure and overall composition of the inlet stream are known. The mole fractions of
the components at the inlet are signified by zi. In the phase separator, the liquid and vapor are separated.
The mole fractions of the components in the vapor phase are signified by yi and those in the liquid phase
by xi. When the vapor and liquid are in equilibrium, the mole fractions of each component in the vapor and
the liquid are related by:

y i=K i x i (E 3.1)

To derive the equation governing the phenomenon, the sum of the mole fractions of the vapor and liquid
over all components is given by:

NCOMP NCOMP

∑ yi =1; ∑ xi =1 (E 3.2)
i=1 i=1

Subtracting these equations;

NCOMP NCOMP

∑ yi − ∑ x i=0 (E 3.3)
i=1 i=1
Substituting the equilibrium expression and rearranging yields:

NCOMP

∑ ( K i−1 ) x i=0 (E 3.4)

i=1

Mass balance around the separator:

F=V + L (E 3.5)

z i F= y i V + x i L (E 3.6)

V
Let v' = ; where v’ is the fraction of the feed that is vapor;
F

z i= y i v ' + xi ( 1−v ' ) (E 3.7)

Using the equilibrium expression, this may be written as:

z i=K i y i v ' + x i (1−v ' ) =( K i−1 ) x i v ' + x i (E 3.8)

The mole fractions in the liquid may then be calculated:

zi
x i= (E 3.9)
1+ ( K i−1 ) v '

Substituting to E 3.4 yields the Rachford-Rice Equation.

NCOMP
( K i−1 ) z i
∑ 1+ ( K i−1 ) v '
=0 (E 3.10)
i=1

Chemical Reaction Equilibrium

Chemical reaction equilibrium gives the upper limit for the conversion of raw materials to products.
Calculations involving chemical reaction equilibrium leads to one or more nonlinear algebraic equations
which must be solved simultaneously.

When you take some chemicals that can react and mix them in a vessel, the reaction can be represented
by the following:

A+ B ⟹C + D (E 3.11)

If the reaction is reversible, the equation can be written as:

A+ B ⟺ C+ D (E 3.12)

If the reaction is very fast, then the forward and reverse reactions proceed quickly and the ultimate
mixture contains all four chemicals, in specific amounts. If the temperature is changed, these amounts
may change. Sometimes, in a gaseous reaction, changing the pressure has some effect. The goal is to
predict the composition of the final mixture, which is determined by chemical reaction engineering.

Chemical reaction equilibrium is determined by the equilibrium constant, which is defined in terms of the
change of Gibbs energy.

∆ G °=−RT ln K (E 3.13)

The Gibbs free energy is tabulated at 298 K for pure components and it is possible to extend the Gibbs
free energy for a reaction to any temperature using the van’t Hoff equation.

d ln K ∆ H ° R
= (E 3.14)
dt R T2

where HR is the heat of reaction. When the reaction is written in the following form,

aA +bB ⟺ cC+ dD (E 3.15)

the equilibrium constant is defined in terms of the activities of the species.

a cC a dD
K= a b (E 3.16)
aA aB

In the gas phase, the activity is the fugacity, since the activity is the fugacity divided by the fugacity of the
standard state, which is 1 atm. In turn, the fugacity may be written as the product of the fugacity
coefficient (providing a correction from ideal gas behavior) and the total pressure multiplied by the mole
fraction in the vapor phase.

fi
f i=ϕi p y i where ϕi = (E 3.17)
pi

The fugacity coefficient can be calculated using the equation of state:

p
ln ϕ i=∫
0
( RT^v − 1p ) dp
i
(E 3.18)

But when the pressure is less than 10 atm, the gas is usually ideal. In this case,  = 0 or  = 1.
Combining,

y cC y dD c+d −a−b
K= a b
p (E 3.19)
y A yB

ILLUSTRATIVE EXAMPLES

Vapor-Liquid Equilibrium Calculations Using MS Excel®

Suppose you have a mixture of hydrocarbons in the inlet stream. You want to find the fraction of the
stream that is vapor and the mole fraction of each chemical in the vapor and liquid streams. The system is
at 180F and 70 psia. Use a basis of one mole per unit time. The flow rates and K-values are as follows:

Component zi Ki
Propane 0.1 6.800
n-Butane 0.3 2.200
n-Pentane 0.4 0.800
n-Octane 0.2 0.052

1. Prepare the worksheet with the objective of using the Rachford-Rice Equation with Goal Seek. Figure
3.2 shows the initial worksheet. Note that column (E) contains the Rachford- Rice Equation (E 3.10);
cell C10 serves as the placeholder for v’; cell E8 is the summation of cells E4 to E7, which should be
equated to zero.

Figure 3.2. Initial Worksheet

2. Perform Goal Seek to set E8 to zero. Figure 3.3 shows the Goal Seek dialog box and Figure 3.4 shows
the results returned.

Figure 3.3. Goal Seek Dialog Box

Figure 3.4. Goal Seek Results

3. The fraction that is vapor has been calculated: v' =0.426. Calculate the rest of the required
parameters using E 3.9 and E 3.1. Figure 3.5 shows the final worksheet, including the concentrations
in the vapor and liquid phases.
 Figure 3.5. Final Worksheet

Vapor-Liquid Equilibrium Calculations Using Aspen Plus®

Suppose you have a mixture of hydrocarbons in the inlet stream. You want to find the fraction of the
stream that is vapor and the mole fraction of each chemical in the vapor and liquid streams. The system is
at 180F and 70 psia. Use a basis of one mole per unit time. The flow rates and K-values are as follows:

Component zi Ki
Propane 0.1 6.800
n-Butane 0.3 2.200
n-Pentane 0.4 0.800
n-Octane 0.2 0.052

1. Open Aspen Plus® and start a new simulation.

2. Insert the block/s and material streams. On the model library, choose Separations. For this problem,
use a Flash2 unit. Add the required material streams. Remember that red arrows signify non-
connection. Figure 3.6 shows the flowsheet for the connected Flash2 unit.

Figure 3.6. Flowsheet for Flash2

3. Specify the components as was done in the previous machine problem. Figure 3.7 shows the
component specification window.

Figure 3.7. Component Specification

4. Specify the property method. Choose RK-Soave for this problem. Figure 3.8 shows the property
method window.

Figure 3.8. Property Method Specification

5. Complete the block specification. Figure 3.9 shows the block information window.

Figure 3.9. Block Information for Flash2 Unit

6. Complete the material stream specification. Figure 3.10 shows the stream information window.

Figure 3.10. Stream Information for Flash2 Unit

7. Run the simulation and generate the report. Figure 3.11 shows the Blocks results and Figure 3.12
shows the Stream results.

Figure 3.11. Block Results

Figure 3.12. Stream Results

Chemical Reaction Equilibrium Calculations Using MS Excel®

Consider the water-gas shift reaction that can be used in a chemical process to make hydrogen for fuel
cell applications:

CO+ H 2 O ⟺CO 2 + H 2 (E 3.20)

Thermodynamic data gives the value of K at 148.4 at 500K. If you start with 1 mol CO, 1.8 mol H 2O, 0.3
mol CO2 and 0.1 mol H2, what will the equilibrium composition be?

1. At equilibrium,

y CO y H
K= 2 2
=148.4 (E 3.21)
y CO y H O
2

2. Prepare a mole balance table. Let x represent the number of moles reacting.

Table 3.2. Mole Balance Table

Species Start End
CO 1 1−x
H2O 1.8 1.8−x
CO2 0.3 0.3+ x
H2 0.1 0.1+ x
Total 3.2 3.2

3. Prepare the initial worksheet. Column C contains the initial number of moles of each component.
Column D contains the ending concentrations based on the number of moles reacting, which has
been held by Cell C10. Cell C11 contains the K-value as calculated using E 3.21. Figure 3.14
shows such worksheet.

Figure 3.14. Initial Worksheet for CRE Problem

4. Use Goal Seek to determine the value of x which will render the value of calculated K equal to
148.4, as given. Figure 3.13 shows the Goal Seek window.
 Figure 3.13. Goal Seek Window

5. Figure 3.14 shows the results returned by Goal Seek. Another column was added (E) to contain the
final concentration of the different components.

Figure 3.14. Goal Seek Results

Chemical Reaction Equilibrium Calculations Using Aspen Plus®

Solve the same water-gas shift reaction in the previous problem.

1. Follow the same steps as in VLE Calculations:

a. Draw the block and the material streams (use an RGibbs block for this problem).
b. Specify the components and the property method (use NRTL model for this problem).
c. Run the simulation and read the results.

2. Figures 3.15 and 3.16 shows the block and stream results.

Figure 3.15. Block Results

 Figure 3.16. Stream Results

STUDY QUESTIONS

1. How do the results differ when different software packages were used? What were the sources of the
deviation/s?

2. Explain the use of Flash2 in solving the VLE problem and the RGibbs block in solving the CRE
problem. Is it viable to use other blocks?

3. Which property methods did you use in solving Problems 3 and 5? Explain the basis of your choice.