Final Exam

Solving for the Chemical Reaction Equilibrium

1. Objective:
The activity aims to solve problems involving chemical reaction equilibrium.

2. Intended Learning Outcomes (ILOs):

The students shall be able to:
2.1 solve chemical reaction equilibrium problems using matlab.

3. Discussion:

Hydrogen can be made for fuel cells by using the water–gas shift reaction. In fact, hydrogen is made
this way every day in oil refineries. The reaction is very fast, and the effluent from the reactor is close
to being in chemical equilibrium. Ammonia is made by reacting hydrogen and nitrogen, and the effluent
from an ammonia reactor is usually in chemical equilibrium. The ammonia is then used to make
fertilizer, which helps increase food production for the world. Thus, chemical reaction equilibrium is
important for both energy and food production.
This laboratory exercise shows how to solve problems involving chemical reaction equilibrium.
The chemical reaction equilibrium gives the upper limit for the conversion, so knowing the equilibrium
conversion is the first step in analyzing a process. The second question, what the rate of reaction is,
can then be answered to decide the volume of the reactor. This second question, using kinetics, is
treated in another laboratory exercise. Chemical reaction equilibrium leads to one or more nonlinear
algebraic equations which must be solved simultaneously, and such problems are described in this
laboratory exercise.
When you take some chemicals that can react and mix them in a vessel, the reaction can be
represented as
A + B C + D 1
If the reaction is reversible, the reverse reaction can also take place.
C + D A + B 2
It can be written as
A + B C + D 3
If the reaction rate is very fast, then the forward and reverse reactions proceed quickly, and the
ultimate mixture contains all four chemicals, in specific amounts. If you change the temperature, these
amounts may change. Sometimes, in a gaseous reaction changing the pressure has the same effect.
In this laboratory exercise, the goal is to predict the composition of the final mixture, determined by
chemical reaction equilibrium.
The reaction rate may not be infinitely high, and one may use a catalyst to speed up the
reaction. However, even if the reaction rate is increased, one can never go beyond the composition
determined by chemical reaction equilibrium.

CHEMICAL EQUILIBRIUM EXPRESSION

In thermodynamics courses, you have learned that chemical reaction equilibrium is determined
by the equilibrium constant, which is defined in terms of the change of Gibbs free energy.
4

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:
5

Here ΔHR o is the heat of reaction. When the reaction is

6

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

7

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 one atmosphere. In turn, you can write the fugacity as the
product of the fugacity coefficient (providing a correction from ideal gas behavior) times the total
pressure times the mole fraction in the vapor phase:
8

The fugacity coefficient can be calculated using the equation of state (Denbigh, 1971,
p. 126):
9

When the pressure is less than 10 atm, the gas is usually ideal. From the formula it is clear that
for an ideal gas the integral vanishes. Then ln Φ= 0 or f = 1. One can use that assumption and
combine all the terms in Eq. (7) into Eq. (10):
10

4. Resources:
Matlab
5. Procedure:
1. Consider the the water–gas shift reaction that can be used in a chemical process to make
hydrogen for fuel cell applications:

At equilibrium,

Thermodynamic data give the value of ln K = 5 (or K = 148.4) at 500 K. Starting with a
stoichiometric mixture of carbon monoxide and water, what will the equilibrium composition
be?
a. With a basis of 1 mol each of carbon monoxide and water, which then reacts to equilibrium,
the mole balance table is shown below. Here x represents the number of moles reacting, thus
giving the values in the table.
Table 1. Solution for Equilibrium of Water-Gas Shift Reaction
 Species Start End yi
CO 1 1-x (1-x)/2
H2O 1 1-x (1-x)/2
CO2 x x/2
H2 x x-2
Total 2 2 1
Obtain the chemical equilibrium constant expression and show your results.
b. To solve for the equilibrium using MATLAB, an m-file must be created to calculate

for any x. Then use ‘fzero’, ‘fsolve’, or ‘fminsearch’ to find the x that that makes f(x) = 0.
The function file { chem._equil.m} contains the following:
% chem_ equil
function y=chem_equil(x)
COin=1.;
H2Oin=1.;
CO2in=0.;
H2in=0.;
Kequil=148.4;
CO=COin-x;
H2O=H2Oin-x;
CO2=CO2in+x;
H2=H2in+x;
y=Kequil-CO2*H2/(CO*H2O);
Issue the following commands in the MATLAB command window:
>> format long
>> fzero(‘chem_equil’, 0.5)
Show the results.

c. To solve for the equilibrium using MATLAB with global command. Create a function file
{filename: chem._equil_global.m } and an m-file { filename: yourSurname_le09_p1c}.
The function file contains the following:
% chem_equil_global
function y=chem_equil_global(x)
global COin H2Oin CO2in H2in Kequil
CO=COin-x;
H2O=H2Oin-x;
CO2=CO2in+x;
H2=H2in+x;
y=Kequil-CO2*H2/(CO*H2O);
The m-file contains the following:
% run chem._equil_global
global COin H2Oin CO2in H2in Kequil
COin=1
H2Oin=1
 CO2in=0
H2in=0
Kequil=148.4
x=fzero(‘chem_equil_global’,0.5)
Run the m-file and show the results.

d. Create an m-file that computes and display the equilibrium concentrations of the reactants and
products. Show the results.

2. When hydrogen gas reacts with iodine gas at elevated temperatures, the following equilibrium
is established:

A student measured the equilibrium constant as 59.3 at 400°C. If one trial begins with a
mixture
that includes 0.050 M hydrogen and 0.050 M iodine, what will be the equilibrium
concentrations of
reactants and products?
a. Show a mole balance table for the given chemical reaction. Obtain the chemical equilibrium
constant expression. Show the results.
b. Create a function file {filename: chem._equil2.m}. Use command window to execute this
function file. Issue matlab commands to calculate the equilibrium concentrations of the
products and reactants. Show the results.
c. Create function file {filename: chem._equil2_global.m} and m-file { filename:
yourSurname_le09_p2c.m } using global command that calculate and display the equilibrium
concentrations of the products and reactantds. Run the files and show the results.

3. The equilibrium constant for the reaction of chlorine gas with phosphorus trichloride to form
phosphorus pentachloride is 33 at 250°C. If an experiment is initiated with concentrations of
0.050 M PCl3 and 0.015 M Cl2, what are the equilibrium concentrations of all three gases?

a. Show a mole balance table for the given chemical reaction. Obtain the chemical equilibrium
constant expression. Show the results.
b. Create a function file {filename: chem._equil3.m}. Use command window to execute this
function file. Issue matlab commands to calculate the equilibrium concentrations of the
products and reactants. Show the results.
c. Create function file {filename: chem._equil3_global.m} and m-file { filename:
yourSurname_le09_p2d.m } using global command that calculate and display the equilibrium
concentrations of the products and reactants. Run the files and show the results.
4. Methanol is formed by reacting carbon monoxide with hydrogen. (This might be an on-board
generation of hydrogen for the hydrogen economy.) With the reaction

the condition at equilibrium is

 When the carbon monoxide and hydrogen enter the reactor in a 1 : 2 ratio, find the equilibrium
conversion when the pressure is 50 atm and Kp ¼ 0.0016. Create an m-file. Run it and show
the
results.
5. Find the molar flow rates of all species out of an equilibrium reactor when the inlet values of
nitrogen, hydrogen, and ammonia are 1.1, 3, and 0.2. The equilibrium constant is 0.05 at 589
K.

for the reaction written as

Use 220 atm for the pressure. Create an m-file. Run it and show the results.
Course: CHE 205 Laboratory Exercise No.: FINAL EXAM
Group No.: Section: CH22FA2
Group Members: Luna, Danice G. Date Performed:---------
Date Submitted: March 19, 2020
Instructor: Engr. Crispulo G. Maranan

6. Data and Results:

Procedure Results
1
2
3
4
5
7. Conclusion:

I therefore conclude that solving problems of chemical reaction equilibrium using complex equations
manually is laborious and sometimes the results are not justifiable but through the use of matlab
complexities of dealing with chemical reaction equilibrium problems are alleviated.
 TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES
RUBRIC FOR MODERN TOOL USAGE
(Engineering Programs)
Student Outcome (e): Use the techniques, skills, and modern engineering tools necessary for engineering
practice in complex engineering activities.
Program: Chemical Engineering Course: CHE 205 Section: CH22FA2 Sem: SY 2019-2020

Performance Unsatisfactory Developing Satisfactory Very Satisfactory Score

Indicators 1 2 3 4
1. Apply Fails to identify Identifies Identifies modern Recognizes the
appropriate any modern modern techniques and is benefits and
techniques, techniques to techniques but able to apply constraints of
skills, and perform fails to apply these in modern
modern discipline- these in performing engineering tools
tools to specific performing discipline-specific and shows
perform a engineering discipline- engineering task. intention to apply
discipline- task. specific them for
specific engineering engineering
engineering task. practice.
task.
2. Demonstrat Fails to apply Attempts to Shows ability to Shows ability to
e skills in any modern apply modern apply fundamental apply the most
applying tools to solve tools but has procedures in appropriate and
different engineering difficulties to using modern effective modern
techniques problems. solve tools when solving tools to solve
and modern engineering engineering engineering
tools to problems. problems. problems.
solve
engineering
problems.
3. Recognize Does not Recognizes Recognizes the Recognizes the
the benefits recognize the some benefits benefits and need for benefits
and benefits and and constraints of and constraints of
constraints constraints of constraints of modern modern
of modern modern modern engineering tools engineering tools
engineering engineering engineering and shows and makes good
tools. tools. tools. intention to apply use of them for
them for engineering
engineering practice.
practice.
Total Score
Mean Score = (Total Score / 3)
Percentage Rating = (Total Score / 12) x 100%
Evaluated by: Engr. Crispulo G. Maranan March 19, 2020
Printed Name and Signature of Faculty Member Date