Objective: To analyze the use of built-in MATLAB functions to solve a single or a

system of initial value ordinary differential equations of interest to chemical engineering

community.

Requirements:
Operating System: Windows 8/10
Software: MATLAB 2011a

Theory:

Consider a system of elementary reactions in series of the type A → B → C. The kinetics of

the system is given by the following equations.

dCA/dt = −k1CA
dCB/dt = k1C A− k2CB
dCC/dt = k2CB

The reactions are carried out in a batch reactor with the respective initial concentrations as
CA0, CB0 and CC0, respectively.

Initially only A is present at the start. So, when the reaction starts B is formed. In the next
instant both A and B are present. However, A is in very large excess so it will predominantly
produce B and at the same time very little amount of C is formed. Thus, the concentration of
B will rise while the concentration of A will fall. This process will continue until B is present
in high enough concentration so that it can dominate over A. When this happens, a maximum
B concentration is reached. After this the decomposition of B becomes more rapid than its
rate of formation and its concentration drops whereas, the concentration of C continuously
increases and attains saturation when all of the reactants are consumed. The variation of
concentration of reactants and products with time is shown in figure 1.

B
Concentration

Time

1
PROBLEM STATEMENT 1

Determine the evolution of concentration of A in the reactor as a function of the rate constant.
Show that the system has a bifurcation by plotting the phase portrait of the system.

Flowsheet

START

K1=-0.2

CAo=0.1

Solve dCA/dt=-K1CA using ODE45

Plot CA vs t

Plot CA vs -t

Plot -CA vs t

Plot –CA vs -t

Yes
CAo=CAo+0.1 If CAo<1

K1=K1+0.1 If K<0.2

END
2
MATLAB CODE:
clc
tspan = [-5 5];
%For Phase portrait of system
figure(1);
for k1 = -0.2:0.1:0.2 %rate constant k1 for first order reaction
for CA0 = 0.1:0.1:1 %Initial concentration of A
[CA,t]= ode45(@(t,CA) -k1*CA, tspan, CA0); % CA = Concentraion of A
plot(CA,t,'r')
hold on
plot(CA,-t,'g')
hold on
plot(-CA,t,'y')
hold on
plot(-CA,-t,'b')
hold on
end
end
title('Phase plot');
xlabel('Time(sec)');
ylabel('Concentration of A');

Output

Fig 1
3
Problem Statement 2

For CA0 = 100; CB0 = CC0 = 0, analyze the evolution of concentrations of A, B, and C for the
following cases:

(i) k1 = 2; k2 = 1

(ii) k1 = 1; k2 = 2

(iii) k1 = 1; k2 = 1

Flowsheet
START

Input
K1,K2,CAo,CBo,CCo

Solve using ODE45

Plot CA,CB,CC vs t

EXIT

4
MATLAB CODE

%For evolution of concentration of A, B, C when CA0=100,

CB0=CC0=0
figure(1);
f=@(t,C)[-2*C(1);2*C(1)-1*C(2);1*C(2)];% k1=2, k2=1
[CA,t]=ode45(f,[1 10],[100,0,0]);
plot(CA,t)
hold on;
title('Concentration Vs time plot (k1=2 , k2=1)');
xlabel('Time');
ylabel('Concentration');
pause;

figure(2);
g=@(t,D)[-1*D(1);1*D(1)-1*D(2);1*D(2)]; %when k1=1, k2=1
[CA,t]=ode45(g,[1 10],[100,0,0]);

plot(CA,t)
hold on;
title('Concentration Vs time plot (k1=1 , k2=1)');
xlabel('Time');
ylabel('Concentration');
pause;

figure(3);
h=@(t,E)[-1*E(1);1*E(1)-2*E(2);2*E(2)] %when k1=1, k2=2
[CA,t]=ode45(h,[0 10],[100,0,0]);
plot(CA,t)
hold on;
title('Concentration with time plot (k1=1 , k2=2)');
xlabel('Time');
ylabel('concentration');

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Output

Fig.2.1

Fig 2.2

Fig 2.3

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Problem Statement 3
Analyze the evolution of concentrations of A, B and C with k1 = 0.99 and k2 = 1.1 for the
following cases:
(i) CA0 = CB0 = CC0 = 10
(ii) CA0 = 50; CB0 = 10; CC0 = 5
(iii) CA0 = 10; CB0 = 50; CC0 = 5

Flowsheet
START

Input
K1,K2,CAo,CBo,CCo

Solve using ODE45

Plot CA,CB,CC vs t

EXIT

7
 MATLAB code

%For evolution of concentration of A,B,C when k1=0.99 and

k2=1.1
figure(1);
f=@(t,C)[-0.99*C(1);0.99*C(1)-1.1*C(2);1.1*C(2)];
[CA,t]=ode45(f,[0 10],[10,10,10]);
%CA0=CB0=CC0= 10
plot(CA,t)
hold on;
title('Concentration with time plot Ca0=10, Cb0=10, Cc=10');
xlabel('Time');
ylabel('concentration');
pause;

figure(2);
f=@(t,C)[-0.99*C(1);0.99*C(1)-1.1*C(2);1.1*C(2)];
[CA,t]=ode45(f,[0 10],[50,10,5]); %CA0=50,
CB0=10, CC0=5
plot(CA,t)
hold on;
title('Concentration with time plot Ca0=50, Cb0=10, Cc=5');
xlabel('Time');
ylabel('concentration');
pause;

figure(3);
f=@(t,C)[-0.99*C(1);0.99*C(1)-1.1*C(2);1.1*C(2)];
[CA,t]=ode45(f,[0 10],[10,50,5]); %CA0=10,
CB0=50, CC0=5
plot(CA,t)
hold on;
title('Concentration with time plot Ca0=10, Cb0=50, Cc=5');
xlabel('Time');
ylabel('concentration');

8
Output:

Fig 3.1

Fig 3.2

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 Fig 3.3
Fig 3.3

CONCLUSION:

The phase portrait developed deliver a very important information about nature of the
equation and its solutions. It turns out that irrespective of the magnitude of ‘k1’, the “fate” of
the system remains unchanged as long as the sign of a remains unchanged as long as the sign
of a remains the same. However, if a change in magnitude of ‘a’ is made close to a=0 such
that the sign of a changes then the sign of ‘a’ changes. Then the fate of the system changes as
t → ∞.

From the concentration profile observed that the final concentration of the reactant as t → ∞
will reach the same value. This shows that the final equilibrium concentration will remain the
same irrespective of the rate constant k1 and k2. The rate constant only govern the
convergence of the reactions.

REFERENCES:
1. Jordan, D. W.; Smith, P. (2007). Nonlinear Ordinary Differential Equations (fourth
ed.). Oxford University Press, ISBN 978-0-19-920824-1 Chapter 1.
2. Laidler, K.J. Chemical Kinetics (3rd ed., Harper and Row 1987) p.359-360 ISBN 0-
06-043862-2
3. Espenson, J.H. Chemical Kinetics and Reaction Mechanisms (2nd ed., McGraw-Hill
2002), p.256-8 ISBN 0-07-288362-6

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