TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES – MANILA 1.

Laboratory Exercise No. 9

Chemical Reaction Equilibrium

Gojo Cruz, Kim T.

 TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES – MANILA 1.

Laboratory Exercise No. 9

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.

Gojo Cruz, Kim T.

 TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES – MANILA 1.

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

Gojo Cruz, Kim T.

 TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES – MANILA 1.

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;

Gojo Cruz, Kim T.

 TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES – MANILA 1.

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.

Gojo Cruz, Kim T.

 TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES – MANILA 1.

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.

Gojo Cruz, Kim T.

 TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES – MANILA 1.

Course: Laboratory Exercise No.:

Group No.: Section:
Group Members: Date Performed:
Date Submitted:
Instructor:

6. Data and Results:

Procedure Results
1 EDITOR WINDOW
% Equilibrium constant expression
disp (' Kequil = [CO2][H2]/[H2O][CO]')

COMMAND WINDOW

>> Ke_expression
Kequil = [CO2][H2]/[H2O][CO]

EDITOR WINDOW

% 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);
end

COMMAND WINDOW
>> fzero('chem_equil', 0.5)
ans = 0.924138711897742

EDITOR WINDOW

function y= chem_equil_global(x)
global COin H2Oin CO2in H2in Kequil
CO=COin-x;
H2O=H2Oin-x;
CO2=CO2in+x;
Gojo Cruz, Kim T.
 TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES – MANILA 1.

H2=H2in+x;
y=Kequil-CO2*H2/(CO*H2O);
end

EDITOR WINDOW
% 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)

COMMAND WINDOW

>> Gojo Cruz_lec09_p1c

COin = 1
H2Oin = 1
CO2in = 0
H2in = 0
Kequil = 1.484000000000000e+02
x = 0.924138711897742

EDITOR WINDOW
disp ('Equilibrium Concentrations')
%solving for reactant used up
COin=1;
H2Oin=1;
CO2in=0;
H2in=0;
Kequil=148.4;
fprintf('Kequil = [CO2][H2]/[CO][H2O]\n')
x=sqrt(Kequil)/(1+sqrt(Kequil));
fprintf('Concentration of CO: %0.4f\n',1-x)
fprintf('Concentration of H2O: %0.4f\n',1-x)
fprintf('Concentration of CO: %0.4f\n',x)
fprintf('Concentration of H2: %0.4f\n',x)

COMMAND WINDOW

>> Co_equilibrium
Equilibrium Concentrations
Kequil = [CO2][H2]/[CO][H2O]

Gojo Cruz, Kim T.

 TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES – MANILA 1.

Concentration of CO: 0.0759

Concentration of H2O: 0.0759
Concentration of CO: 0.9241
Concentration of H2: 0.9241
2 EDITOR WINDOW
%Equilibrium Constant Expression
disp(' Kequil = [HI]^2/[H2][I2] ')

COMMAND WINDOW
>> Ke_expression2
Kequil=[HI]^2/[H2][I2]

EDITOR WINDOW
%chem_equil2
function y=chem_equil2(x)
H2in=0.050;
I2in=0.050;
HIin=0;
Kequil=59.3;
H2=H2in-x;
I2=I2in-x;
HI=HIin+2*x;
y=Kequil-((HI^2)/(H2*I2));

COMMAND WINDOW
>> format long
>> fzero('chem_equil2',0)
ans = 0.039691411711987

EDITOR WINDOW
% chem_equil_global
function y=chem_equil_global(x)
global H2in I2in HIin Kequil
H2=H2in-x;
I2=I2in-x;
HI=HIin+2*x;
y=Kequil-((HI^2)/(H2*I2));

M-File
% run chem_equil_global
global H2in I2in HIin Kequil
H2in=0.050
I2in=0.050
HIin=0

Gojo Cruz, Kim T.

 TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES – MANILA 1.

Kequil=59.3
x=fzero('chem_equil_global',0);
H2=0.05-x;
I2=0.05-x;
HI=x;
disp('Equilibrium Concentrations')
fprintf('H2 = %0.4f\n',H2)
fprintf('I2 = %0.4f\n',I2)
fprintf('HI2 = %0.4f\n',HI)

COMMAND WINDOW
>> GojoCruz_le09_p2c
Equilibrium Concentrations
H2 = 0.0103
I2 = 0.0103
HI2 = 0.0397
3 EDITOR WINDOW

%Equilibrium Constant Expression

disp (' Kequil=[PCL5]/[CL2][PCL3]')

COMMAND WINDOW

>> Ke_expression3
Kequil=[PCL5]/[CL2][PCL3]
EDITOR WINDOW

%chem_equil3
function y=chem_equil3(x)
PCL3in=0.050;
CL2in=0.015;
PCL5in=0;
Kequil=33;
PCL3=PCL3in-x;
CL2=CL2in-x;
PCL5=PCL5in+x;
y=Kequil-(PCL5/(PCL3*CL2));

COMMAND WINDOW

>> fzero('chem_equil3',0.6)
ans = 0.008655785946446

Gojo Cruz, Kim T.

 TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES – MANILA 1.

EDITOR WINDOW

% chem_equil3_global
function y=chem_equil3_global(x)
global PCL3in CL2in PCL5in Kequil
PCL3=PCL3in-x;
CL2=CL2in-x;
PCL5=PCL5in+x;
y=Kequil-PCL5/(PCL3*CL2);

m-file
% run chem_equil3_global
global PCL3in CL2in PCL5in Kequil
PCL3in=0.050;
CL2in=0.015;
PCL5in=0;
Kequil=33;
x=fzero('chem_equil3',0);
Cl2=0.015-x;
PCl3=0.050-x;
PCl5=x;
disp('Equilibrium Concentrations')
fprintf('PCL3=%0.4f\n',PCl3)
fprintf('CL2=%0.4f\n',Cl2)
fprintf('PCL5=%0.4f\n',PCl5)

COMMAND WINDOW

>> Gojo Cruz_le09_p3c

Equilibrium Concentrations
PCL3=0.0413
CL2=0.0063
PCL5=0.0087
4 EDITOR WINDOW
function y=chem_equil4_global(x)
global COin H2in CH3OHin Kp yt P
CO=COin-x;
H2=H2in-(2*x);
CH3OH=CH3OHin+x;
Kp=0.0016;
yt=3-2*x;

Gojo Cruz, Kim T.

 TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES – MANILA 1.

P=50;
y=P^2-(CH3OH/((H2^2)*CO*Kp));

m-file
global COin H2Oin CH3OHin
COin=1;
H2Oin=2;
CH3OHin=0;
x=fzero('chem_equil4_global',0)
disp('Equilibrium Conversion')
fprintf('Methanol = %0.4f\n',x)

COMMAND WINDOW
>> GojoCruz_le09_p4
x=
0.5039620688418
Equilibrium Conversion
Methanol = 0.05040
5 EDITOR WINDOW
function y=chem_equil5(x)
N2in=1.1;
H2in=3;
NH3in=0.2;
Kequil=0.05;
N2=N2in-(1/2*x);
H2=H2in-(3/2*x);
NH3=NH3in+x;
y=Kequil-NH3/((N2^1/2)*(H2^3/2));

<chem_equil5_global.m>
function y=chem_equil5_global(x)
global H2in N2in NH3in Kequil
N2=N2in-(1/2*x);
H2=H2in-(3/2*x);
NH3=NH3in+x;
y=Kequil-NH3/((N2^1/2)*(H2^3/2));

m-file
global H2in N2in NH3in Kequil
N2in=1.1;
H2in=3;
NH3in=0.2;

Gojo Cruz, Kim T.

 TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES – MANILA 1.

Kequil=0.05;
x=fzero('chem_equil5',0.5)
disp('Molar Flow Rates')
fprintf('H2 = %0.4f\n',3-(3/2*x))
fprintf('N2 = %0.4f\n',1.1-(1/2*x))
fprintf('NH3 = %0.4f\n',0.2+x)

COMMAND WINDOW
>> GojoCruz_le09_p5

x = 0.102360812212436

Molar Flow Rates

H2 = 2.8465
N2 = 1.0488
NH3 = 0.3024
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.

8. Assessment (Rubric for Laboratory Performance):

TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES

RUBRIC FOR LABORATORY PERFORMANCE

CRITERIA BEGINNER ACCEPTABLE PROFICIENT SCORE

1 2 3
I. Laboratory Skills
Members do not Members occasionally Members always
Manipulative
demonstrate needed demonstrate needed demonstrate needed
Skills
skills. skills. skills.
Members are able to Members are able to
Experimental Members are unable to
set-up the materials with set-up the material with
Set-up set-up the materials.
supervision. minimum supervision.
Member do not Members occasionally Members always
Process Skills demonstrate targeted demonstrate targeted demonstrate targeted
process skills. process skills. process skills.
Members follow safety
Safety Members do not follow Members follow safety
precautions most of the
Precautions safety precautions. precautions at all times.
time.
II. Work Habits
Time Members finish ahead
Members do not finish
Management / Members finish on time of time with complete
on time with incomplete
Conduct of with incomplete data. data and time to revise
data.
Experiment data.

Gojo Cruz, Kim T.

 TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES – MANILA 1.

Members do not know Members have defined Members are on tasks

their tasks and have no responsibilities most of and have defined
Cooperative and defined responsibilities. the time. Group responsibilities at all
Teamwork Group conflicts have to conflicts are times. Group conflicts
be settled by the cooperatively managed are cooperatively
teacher. most of the time. managed at all times.
Clean and orderly
Clean and orderly
Messy workplace during workplace with
Neatness and workplace at all times
and after the occasional mess during
Orderliness during and after the
experiment. and after the
experiment.
experiment.
Ability to do Members require Members require Members do not need to
independent supervision by the occasional supervision be supervised by the
work teacher. by the teacher. teacher.

TOTAL SCORE
Other Comments / Observations:
RATING = (
TotalScore
24 ) x 100%

Evaluated by:

_______________________________________
Printed Name and Signature of Faculty Member Date: ___________________________

Gojo Cruz, Kim T.