CHE654

Modeling Chemical Processes

Using MATLAB

Homework Set #5 Solutions

Class-16

Prepared by

Dr. Hong-ming Ku

King Mongkuts University of Technology Thonburi

Chemical Engineering Department
Chemical Engineering Practice School
July 2004-2012 Use with Permission of the Author Only

53. Boiling and Draining of Ethanol in a Spherical Vessel

Consider the boiling of pure ethanol in a jacketed spherical vessel with a radius R = 1
meter, as shown in the diagram. The liquid is drained at the bottom of the vessel while
some of it is boiled and escapes as vapor through the top of the vessel.

Steam TS
1
1 atm
v
z

CV
P0
The following data are available:
(TB) = 3.858x107 J/kmol
MW = 46.07
= 16.575 kmol/m3
CP = 1.4682x105 J/kmol-C
vap
log10 P = 8.04494 __1554.30__
T in C and Pvap in mmHg
T + 222.65
3
-1/2
CV = 4.5 m -atm /hr = valve constant
TS = 100 C
U = 2.0x106 J/hr-m2-C
P0 = 1 atm
z0 = z(t=0) = 1 m
(a) Model this operation and use MATLAB to determine the time it takes for the vessel
to completely empty, assuming that initially the liquid is at its boiling point. Note
that the heat transfer area AT is not constant.
(b)Repeat the calculations in Part (a), assuming that there is no draining of the liquid
at the bottom (i.e. the liquid leaves the vessel only through boiling). Determine the
solution analytically (an exact solution is possible in this case).
Useful conversion factors and formulae:
g = gravitational constant = 9.807 m/s2
1 atm = 1.01325x105 N/m2

1 N = 1 kg-m/s2

The volume of liquid V(z) in a spherical vessel as a function of its height z is given by
V(z) = Rz2 z3
3
while the surface area S(z) is given by

S(z) = 4Rz z

[a + bx a ln(a + bx)]
x
dx =
a + bx
b2

Solution:
(a) First, calculate TB:
log10 (760) = 8.04494 1554.3/(TB + 222.65)
TB = 78.33 C
Overall mass balance:
(dV/dt) = v Cv P P0
dV/dt = 0.06033 v 4.5 P 1
But P = P0 + gz = 1 atm + (763.61 kg/m3) (

1 atm

) (9.807 m/s2)( 1 N )

1.01325x105 N/m2

P = 1 + 0.073908z
dV/dt = 0.06033 v 1.22337z

Energy balance:
(2.0x106)(100 78.33)AT

v = q/ =

= 1.12338(4Rz z2)

3.858x107
(2z z2) (dz/dt) = 0.27109z + 0.06777z2 1.22337z
z(2 z)(dz/dt) = 0.27109z + 0.06777z2 0.38941z

dz
dt

0.27109 0.06777z + 0.38941z-1/2

(z 2)

(1 kg-m/s2)

s.t. z(t = 0) = 1 m

Determine t at z = 0 using MATLAB

t = 1.6966 hours or 101.8 minutes to empty

The MATLAB Script File:

%
% CHE654: Problem #53
%
% Boiling and Draining of Ethanol in a Spherical Vessel
%
clc
clear
format long
drain_t = 1;
initZ = 1;
% Part (a)
[t, z] = ode45('spherea',drain_t,initZ);
while z(length(z),1) > 0
drain_t = drain_t + 0.01;
[t, z] = ode45('spherea',drain_t,initZ);
end
[t, z]
plot(t,z)
title('Boiling and Draining of Ethanol in a Spherical Tank')
xlabel('Time in Hours')
ylabel('Ethanol Height in Meters')
% Part (b)
drain_t = 1;
[t, z] = ode45('sphereb',drain_t,initZ);
while z(length(z),1) > 0
drain_t = drain_t + 0.01;
[t, z] = ode45('sphereb',drain_t,initZ);
end
[t, z]
The MATLAB M-File for the ODE:
function dzdt = ode(t,z)
dzdt = zeros(1,1);
dzdt(1) = (0.27109+0.06777*z(1)+0.38941*z^(-0.5))/(z(1)-2);

(b) Repeat the calculations in Part (a) analytically if there is no drainage.

dV/dt = 0.06033 v
(2z z2) (dz/dt) = 0.27109z + 0.06777z2

(2 z)(dz/dt) = 0.27109 + 0.06777z

(z 2)(dz/dt) = 0.06777(4 z)

0
z dz
4z

t
2 dz
4z

0.06777 dt
0

[4 z 4ln(4z)] + 2ln(4z) = 0.06777 t

0

4 z 2ln(4z)

= 0.06777 t
1

1.22741 0.802775 = 0.06777 t

t = 6.266 hours or 375.9 minutes

MATLAB gives an answer of about 6.27 hours.

The MATLAB M-File for the ODE:

function dzdt = ode(t,z)
dzdt = zeros(1,1);
dzdt(1) = 0.06777*(4-z(1))/(z(1)-2);

54. Boiling of Water in a Closed Cylindrical Vessel

A closed cylindrical vessel (R = 0.5 m and H =5.0 m) contains 500 kg of water at its
boiling temperature of 100 C (373.15 K) as shown in the figures below. Lets assume
that initially at t = 0, the water (500 kg) is already at 100 C and starts to boil. Initially,
there is also 5 kg of water vapor (or steam) in the gas phase of the vessel. We assume
the water vapor is an ideal gas and that the temperature in the gas and liquid phases are
always in thermal equilibrium at 100 C.
The following data are also known about water:
MW (molecular weight) = 18.015 kg/kmol
(mass density) = 1000 kg/m3
(heat of vaporization) = 2256.84 kJ/kg
CP (liquid heat capacity) = 4.1813
kJ/kg-K
R (universal gas constant) = 0.08206 atm-m3/kmol-K

Steam

PG

VG

Water

PG

v
VL

VG

Water

Figure for Part 1

VL

Figure for Part 2

This problem is divided into two parts, namely Part 1 and Part 2.
Part 1: In this part, water is being boiled by a heating coil at TS = 200 C with a
constant heat transfer area A = 2.0 m2 and an overall heat transfer coefficient U = 100
kJ/min-m2-C as shown in the figure for Part 1.
(a) Derive an analytical expression of the liquid height z as a function of time.
(b) Derive an analytical expression of the water gas pressure PG as a function of time. Plot
your analytical solution in MATLAB and run the model until all the water has vaporized.
Hint: You may check the correctness of your analytical solution by checking PG at t = 0
and at t when all water has been vaporized.
Answer the following questions:
How long does it take for water in Part 1 to boil off completely? ____________
minutes

What is the gas pressure in Part 1 at the following conditions?

(i) PG = ____________ atm after 30 minute
(ii) PG = ____________ atm when water has boiled off completely
Part 2: Now, lets study the same system in which the cylindrical vessel is being heated by
steam in a jacketed chamber as shown in the figure for Part 2. In this case, the heat
transfer area decreases with the liquid height and is no longer constant. The heating now
comes from the surrounding wall and the bottom of the vessel. We assume U and TS to be
the same as in Part 1.
(a) Derive an analytical expression of liquid volume VL as a function of time.
(b) Derive a single ODE for the gas pressure PG using the analytical expression in Part 2(a).
Then use MATLAB (ode45) to solve the ODE for PG from t = 0 to t when all liquid is
gone, and make a plot of the PG profile. Note that the final value of PG when the vessel
contains only gas in Part 2(b) should be equal to that in Part 1(b).
Answer the following questions:
How long does it take for water in Part 2 to boil off completely? ____________
minutes
What is the gas pressure in Part 2 at the following conditions?
(i) PG = ____________ atm after 30 minutes
(ii) PG = ____________ atm when water has boiled off completely

Solution:
Part 1(a): Constant heat transfer area
Mass balance for the liquid phase:

dV L
= v
dt

Energy balance for the liquid phase:

d (VL C P TB )
= UA(TS TB ) v( + C P TB )
dt

C P TB

v=

dVL
= UA(TS TB ) v vC P TB
dt

UA(TS TB )

The mass balance equation then becomes:

R 2

UA(TS TB )
dz
=
dt

z 0 = z (t = 0) =

z = z0

UA(TS TB )
dz
=
dt
R 2

(500 kg )
(1000 kg / m 3 )( )(0.5 m) 2

UA(TS TB )
(100)(2)(200 100)
t = 0.6366
t
2
R
(1000)(2256.84)( )(0.5) 2

z = 0.6366 0.01128t

When z = 0, t = 56.44 minutes

Part 1(b): Constant heat transfer area

Mass balance for the vapor phase:

MW

UA(TS TB )
dn
=v=
dt

PGVG = nRTB

n=

PGVG
RTB

d ( PGVG ) vRTB
=
dt
( MW )

PG

dVG
dP
vRTB
+ VG G =
dt
dt
( MW )

PG

dP
d (VT V L )
vRTB
+ (VT V L ) G =
dt
dt
( MW )

PG

= 0.6366 m

dP
dV L
vRTB
+ (VT V L ) G =
dt
dt
( MW )

PG

+ (VT V L )

dPG
vRTB
=
dt
( MW )

UA(TS TB )
dV L
=

dt

But

and

VL = VL 0

UA(TS TB )

= 0.5 0.008862t

VT = R 2 H = (0.5) 2 (5) = 3.927

(VT V L )

dPG
RTB
P UA(TS TB ) RTB
P
= v
G=
G

dt

( MW )
( MW )

(3.927 0.5 + 0.008862t )

(3.427 + 0.008862t )

dPG
P
(0.08206)(373.15)
= 8.8619
G
dt
18.015
1000

dPG
= 0.008862[1699.733 PG ]
dt

t
dPG
dt
= 0.008862
PG 0 1699.733 P
0 3.427 + 0.008862t
G

But

PG

PG 0 =

(5.0 / 18.015)(0.08206)(373.15)
= 2.478 atm
(3.927 0.5)

1697.255
3.427 + 0.008862t
ln
= ln

3.427

1699.733 PG
1699.733 PG
1697.255
3.427 + 0.008862t
3.427
=

=
1699.733 PG
3.427
1697.255
3.427 + 0.008862t

PG = 1699.733

5816.493
3.427 + 0.008862t

Lets check PG at t = 0 and when water completely vaporized:

At t = 0,

PG = 1699.733

5816.493
= 2.478 atm
3.427

10

At t = 56.44 min, PG = 1699.733

Check against the ideal gas law:

5816.493
= 218.64 atm
3.427 + 0.008862(56.44)

PG =

(500 + 5)(0.08206)(373.15)
= 218.58 atm
(18.015)(3.927)

At t = 30.0 min, PG = 124.67 atm

MATLAB script to plot the derived equation:

clc
clear
time(1) = 0;
PG(1) = 2.478;
for t = 1:56
time(t+1) = t;
PG(t+1) = 1699.733-5816.493/(3.427+0.008862*t);
end
time(58) = 56.44;
PG(58) = 1699.733-5816.493/(3.427+0.008862*56.44);
plot(time,PG)
title('Gas Pressure vs. Time')
xlabel('Time in Minutes')
ylabel('Gas Pressure in atm')

11

Part 2(a): Varying heat transfer area

UA(TS TB )
dV L
=
dt

2V

U R 2 + L (TS TB )
dV L
R
=
dt

2V

(100) (0.5) 2 + L (200 100)

dV L
0 .5

=
= 0.004431(0.7854 + 4V L )
dt
(1000)(2256.84)
dV L
0.7854 + 4V L
= 0.004431dt ln
= 0.01772t
(0.7854 + 4V L )
2.7854

VL = 0.69635 exp(0.01772t ) 0.19635

Time for water to completely vaporize = 71.44 min when VL = 0

Part 2(b): Varying heat transfer area

12

(VT V L )

dPG UA(TS TB ) RTB

P
=
G

dt
( MW )

2V

U R 2 + L (TS TB )
dP
P
RTB
R
(VT VL ) G =
G

dt

( MW )

2V

(100) (0.5) 2 + L (200 100)

dP
(0.08206)(373.15)
P
0 .5

(3.927 VL ) G =
G

dt
2256.84
(18.015)
1000

(3.927 VL )

dPG
P

= 4.4310(0.7854 + 4VL ) 1.6997 G

dt
1000

dPG
12.3421e 0.01772t
=
dt
4.12335 0.69635e 0.01772 t

PG

1.6997 1000

13

s.t.

PG (0) = 2.478

MATLAB Script File:

clc
clear
format short
simtim = [0:0.01:71.44];
initPG = [2.478];
[t, PG] = ode45('pg', simtim, initPG);
[t, PG]
plot (t,PG)
title ('Gas Pressure vs Time When Heat Tranfer Area Is Not Constant')
xlabel ('Time in Minutes')
ylabel ('Gas Pressure in Atm')

function fPG = ode(t, PG)

fPG = zeros(1,1);
fPG(1) = 12.3421*exp(-0.01772*t)*(1.6997-PG(1)/1000)/(4.12335-0.69635* ...
exp(-0.01772*t));

At t = 30 min, PG = 133.71 atm

At t = 71.44 min, PG = 218.62 atm

14

58. Batch Reactor with a Series Reaction

Consider a batch reactor with a series reaction where component A reacts to form
component B. Component B can also react reversibly to form component C. The
reaction scheme can be characterized by:
k2f

k1
A

C
k2r

Here k2f and k2r represent the kinetic rate constants for the forward and reverse
reactions for the conversion of B to C, while k1 represents the rate constant for the
conversion of A to B.
(a) Assuming that each of the reactions is first-order and constant volume, write down
the 3 modeling equations for CA, CB, and CC, where CA, CB, and CC represent the
concentrations (mol/volume) of components A, B, and C, respectively.
(b)Using the following definitions:
Dimensionless time,
Conversion of A,
Dimensionless concentration of B,
Ratio of rate constants,
Ratio of forward and reverse rate constants,

x1
x2

=
=
=
=
=

k1 t
(CA0 CA) / CA0
CB / CA0
k2f / k1
k2r / k1

Derive a second-order ODE for the dimensionless concentration of B. Your ODE

must contain only dimensionless quantities (x2, , , and ).
(c) Solve the ODE in Part (b) analytically to find x2 as a function of , , and .
(d)Using the following data:
k2f = 1.5 min-1
k1 = 1.0 min-1
CA0 = CA (t = 0) = 3.0 mol/liter
CB0 = CB (t=0) = 0 mol/liter
CC0 = CC (t=0) = 0 mol/liter

k2r = 2.0 min-1

Solve for CB analytically as a function of time.

(e) Given the data in Part (d), find the maximum concentration of B and the reaction
time at this concentration. If no such maximum exists, prove it mathematically.
Repeat the above calculations for the case of k1 = 3 min-1, k2f = 1.5 min-1, k2r = 1
min-1 while the initial conditions remain the same.
(f) Validate your analytical solutions by solving the differential equations in Part (a)
with MATLAB and plot the time profiles of components A, B, and C. Use both
sets of rate constants (i.e. k1 = 1.0 min-1, k2f = 1.5 min-1, k2r = 2.0 min-1 and k1 = 3.0
min-1, k2f = 1.5 min-1, k2r = 1.0 min-1).

15

Solution:

k1
A

k2f
B

C
k2r

(a) There are 3 modeling equations which are :

dCA/dt = k1CA
dCB/dt = k1CA k2fCB + k2rCC
dCC/dt = k2fCB k2rCC
(b) Define

= k1 t

x1 = (CA0 CA) / CA0

x2 = CB / CA0

= k2f / k1 = k2r / k1

Need a 2nd-order ODE for dimensionless concentration of B starting with:

CA = CA0 e-k1t
or

1 x1 = e-

x1 = 1 e-

d2CB/dt2 = k1dCA/dt k2fdCB/dt + k2rdCC/dt

d2CB/dt2 = k12CA0 e-k1t k2f dCB/dt + k2r(k2f CB k2rCC)
= k12CA0 e-k1t k2f dCB/dt + k2r k2f CB k2r[dCB/dt + k2f CB k1 CA0 e-k1t]
= ( k1k2r k12) CA0 e-k1t (k2r + k2f)dCB/dt

Introducing dimensionless variables:

d[dCB/dt]/dt = [1/(1/k1)d] [CA0dx2/(1/k1)d] = k12CA0d2x2/d2

(k2r + k2f)dCB/dt = k1(k2r + k2f)CA0dx2/d

= (+)k12CA0dx2/dt

16

(k1k2r k12)CA0 e-k1t = (-1)k12CA0e-

k12CA0d2x2/d2 = (1) k12CA0e- (+)k12CA0dx2/d

d2x2/d2 + (+)dx2/d + (1)e- = 0

d2x2/d2 + (+)dx2/d = (1)e-

(c)

Solve for x2 analytically as a function of , , and

x2() = C1e1 + C2e2 + C3e-

2 + (+) = 0

1 = 0 , 2 = (+)

x2() = C1 + C2e-(+) + C3e-

At t = 0 , CB = 0 = 0 , x2 = 0
C1 + C2 + C3 = 0
dx2/d = (+)C2e-(+) C3e-
d2x2/d2 = (+)2C2e(+) + C3e-
d2x2/d2 + (+)dx2/d = C3(1)e- = (1)e-

C3

= (1)/(+1)

C1 + C2 + (1)/(+1) = 0
At t = 0 or = 0 , dCB/dt = k1CA(t=0) k2fCB(t=0) + k2rCC(t=0)
= k1CA0

17

or dx2/d

= 1

(+)C2 C3

C2

= [1/(+)][1+(1)/(+1)] = (1/+)[(+1+1)/(+1)]
= / [(+)(1)]

C1

= C2C3 = / [(+)(1)] + (1)/( +1)

= [+(+)(1)]/[(+)(+ 1)]

x2() = /(+ ) + /[(+ )(1 )] e-(+) + (1 )/(+ 1) e-

(c) If k1 = 1 min-1 , k2f = 1.5 min-1 , k2r = 2 min-1

CA0 = 3 mol/liter , CB = CC = 0 when t = 0
= 1.5 and = 2
x2() = 0.57143 0.17143e-3.5 0.4e-

CB(t) = 1.71429 0.51429e-3.5t 1.2e-t

(d) Find CB,max and tmax:

dCB/dt = 1.80e-3.5t + 1.2e-t = 0
1.5e-3.5t = e-t
In (1.5) 3.5t = t
no solution / root to the above equation!

Therefore, CB does not go through any maximum.

18

Now k1 = 3 min-1 k2f = 1.5 min-1 k2r = 1 min-1

= 0.5

= 1/3

x2() = 0.40 3.6e-0.8333 4e-

CB(t) = 1.2 + 10.8e-2.5t 12e-3t
dCB/dt = 27e-2.5t + 36e-3t = 0
2.5t = In (1.3333) 3t
tmax = 0.575 min
CB,max = 1.627 mol/liter
(f)

The MATLAB Script File:

%
% CHE654: Problem #58
%
% Batch Reactor with a Series Reaction
%
clc
clear
simtime=[0:0.1:5];
initC=[3,0,0];
[t,c] = ode45('batchr1',simtime,initC);
[t,c]
plot(t,c)
title('Batch Reactor with a Series Reaction')
xlabel('Time in Minutes')
ylabel('Concentration of A, B, and C in Mole/Liter')
legend('A','B','C')
%
[t,c] = ode45('batchr2',simtime,initC);
[t,c]
plot(t,c)
title('Batch Reactor with a Series Reaction')
xlabel('Time in Minutes')
ylabel('Concentration of A, B, and C in Mole/Liter')
legend('A','B','C')

19

The MATLAB M-Files for ODE:

function fv=batchr1(t,c)
fv = zeros(3,1);
fv(1) = -c(1);
fv(2) = c(1)-1.5*c(2)+2*c(3);
fv(3) = 1.5*c(2)-2*c(3);
function fv=batchr2(t,c)
fv = zeros(3,1);
fv(1) = -3*c(1);
fv(2) = 3*c(1)-1.5*c(2)+c(3);
fv(3) = 1.5*c(2)-c(3);

The MATLAB Output:

>>
ans =
0
0.1000
0.2000
0.3000
0.4000
0.5000
0.6000
0.7000
0.8000
0.9000
1.0000
1.1000
1.2000
1.3000
1.4000
1.5000
1.6000
1.7000
1.8000
1.9000
2.0000
2.1000
2.2000
2.3000
2.4000
2.5000
2.6000
2.7000
2.8000

3.0000
2.7145
2.4562
2.2225
2.0110
1.8196
1.6464
1.4898
1.3480
1.2197
1.1036
0.9986
0.9036
0.8176
0.7398
0.6694
0.6057
0.5480
0.4959
0.4487
0.4060
0.3674
0.3324
0.3008
0.2722
0.2463
0.2228
0.2016
0.1824

0
0.2661
0.4764
0.6453
0.7831
0.8971
0.9928
1.0740
1.1438
1.2044
1.2573
1.3039
1.3452
1.3818
1.4145
1.4438
1.4702
1.4938
1.5150
1.5341
1.5514
1.5670
1.5811
1.5938
1.6053
1.6157
1.6251
1.6336
1.6413

0
0.0194
0.0674
0.1322
0.2059
0.2833
0.3608
0.4363
0.5082
0.5759
0.6391
0.6975
0.7512
0.8006
0.8457
0.8868
0.9242
0.9582
0.9891
1.0172
1.0426
1.0656
1.0865
1.1054
1.1226
1.1381
1.1521
1.1648
1.1763

20

2.9000
3.0000
3.1000
3.2000
3.3000
3.4000
3.5000
3.6000
3.7000
3.8000
3.9000
4.0000
4.1000
4.2000
4.3000
4.4000
4.5000
4.6000
4.7000
4.8000
4.9000
5.0000

0.1651
0.1494
0.1351
0.1223
0.1107
0.1001
0.0906
0.0820
0.0742
0.0671
0.0607
0.0549
0.0497
0.0450
0.0407
0.0368
0.0333
0.0302
0.0273
0.0247
0.0223
0.0202

1.6482
1.6545
1.6602
1.6654
1.6700
1.6742
1.6780
1.6815
1.6846
1.6874
1.6900
1.6923
1.6944
1.6963
1.6980
1.6996
1.7010
1.7022
1.7034
1.7044
1.7053
1.7062

1.1867
1.1961
1.2046
1.2124
1.2193
1.2256
1.2314
1.2365
1.2412
1.2454
1.2493
1.2527
1.2559
1.2587
1.2613
1.2636
1.2657
1.2676
1.2693
1.2709
1.2723
1.2736

ans =
0 3.0000
0.1000 2.2225
0.2000 1.6464
0.3000 1.2197
0.4000 0.9035
0.5000 0.6694
0.6000 0.4958
0.7000 0.3674
0.8000 0.2721
0.9000 0.2016
1.0000 0.1494
1.1000 0.1106
1.2000 0.0820
1.3000 0.0608
1.4000 0.0450
1.5000 0.0333
1.6000 0.0247
1.7000 0.0183
1.8000 0.0136
1.9000 0.0100
2.0000 0.0074
2.1000 0.0055
2.2000 0.0041
2.3000 0.0030

0
0
0.7212 0.0563
1.1648 0.1888
1.4227 0.3576
1.5589 0.5376
1.6167 0.7139
1.6264 0.8778
1.6073 1.0254
1.5730 1.1548
1.5319 1.2665
1.4890 1.3616
1.4478 1.4415
1.4098 1.5082
1.3758 1.5634
1.3462 1.6088
1.3206 1.6460
1.2990 1.6763
1.2809 1.7008
1.2658 1.7207
1.2533 1.7367
1.2430 1.7495
1.2346 1.7599
1.2278 1.7681
1.2223 1.7747

21

2.4000
2.5000
2.6000
2.7000
2.8000
2.9000
3.0000
3.1000
3.2000
3.3000
3.4000
3.5000
3.6000
3.7000
3.8000
3.9000
4.0000
4.1000
4.2000
4.3000
4.4000
4.5000
4.6000
4.7000
4.8000
4.9000
5.0000

0.0022
0.0017
0.0012
0.0009
0.0007
0.0005
0.0004
0.0003
0.0002
0.0002
0.0001
0.0001
0.0001
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000

1.2178
1.2142
1.2113
1.2090
1.2071
1.2057
1.2045
1.2036
1.2028
1.2022
1.2018
1.2014
1.2011
1.2009
1.2007
1.2005
1.2004
1.2003
1.2003
1.2002
1.2002
1.2001
1.2001
1.2001
1.2001
1.2000
1.2000

1.7799
1.7841
1.7874
1.7901
1.7922
1.7938
1.7951
1.7962
1.7970
1.7976
1.7981
1.7985
1.7989
1.7991
1.7993
1.7994
1.7996
1.7997
1.7997
1.7998
1.7998
1.7999
1.7999
1.7999
1.7999
1.8000
1.8000

22

23

60. Isothermal Semi-Batch Reactor

(a) Consider an isothermal semi-batch reactor where a single reaction takes place in a
solvent S, which is inert. In this reaction, 2 moles of component A react with one
k1
mole of component B to form one mole of component C: 2A + B -----> C.
The reaction rate does not conform to the stoichiometry but is 1st-order with
respect to each reactant as follows: rA = k1CACB

FA = 15 liter/min

FB = 10 liter/min

Initially (t = 0 min), the reactor contains 100 liters of solution and 300 moles of A.
Assuming that all components have the same density of 60 mol/liter, derive 3 ODE
equations needed to compute CA, CB, and CC, the concentrations (moles/liter) of A,
B, and C, respectively. Use ode45 in MATLAB to solve for and plot (in a single
graph) the concentrations of the 3 components. Run the model for 20 minutes with
an increment of 0.5 minute.
The following experimental data have been obtained for this reaction when carried
out in a batch reactor:

Time(minute)

5.0

7.5

12.0

15.5

25.0

32.0

40.0

CA(mol/liter)
CB(mol/liter)

2.0
0.5

1.65

1.52

1.40

1.28

1.17

1.10

1.06

(b) At the end of 20 minutes, the 2 feeds to the reactor are suddenly shut off, and
4,500 moles of a new component called D (same density as components A, B, and
C) are charged to the reactor. That is, the reactor now operates in a batch mode.
Component D reacts with component C to form A and B, and the reaction now
looks as follows:
k1
2A + B

C + D
k2

with a reaction rate of rA = k1CACB + k2CD (2nd -order forward and 1st-order
reverse). The value of k2 has been measured to be 1.0 min-1. Derive analytically
the concentration of A as a function of time, and compute CA at steady state based

24

on your derived equation. Your final expression should be simplified as much as

possible and should not contain any parameters except t (time) and CA.

Useful Integrals:

tan 1

dx
=
B

dx
1 a + bx
= ln

x( a + bx)
a x

if = 0

where

if > 0

tanh 1

if < 0

B = a + bx + cx2
= 4ac b2
= b + 2cx

Solution:
(a) Must first determine the rate constant k using the graphical method.
dCA = 2dCB

CA CA0 = 2(CB CB0)

(dCA/dt) = kCACB

CB = CB0 + (CA CA0)

dCA

= kdt

CA[(CB00.5CA0)+0.5CA]
Integrate from CA0 to CA on the LHS and from 0 to t on the RHS.
Integrate by partial fractions or use a table of integrals:
CA
[1/(CB00.5CA0)] ln[(CB00.5CA0)+0.5CA)/CA]

= kt
CA0

ln(CA/CB) ln(CA0/CB0) = (0.5CA0 CB0)kt

25

So plot ln(CA/CB) vs. (0.5CA0 CB0)kt to obtain the value of k.

From MATLAB, get slope = 0.054203

dV = FA + FB = 15 + 10 = 25
dt

k = 0.1084 liter/mole-min

V = 100 + 25t

d(VCA)/dt = kVCACB + AFA

because

1 dNA = dCA = kCACB

V dt
dt

d(VCA)/dt = V(dCA/dt) + CA(dV/dt) = V(dCA/dt) + 25CA

= 0.1084VCA[0 + 0.5(CA 3.0)] + (60)(15)
= 0.1084CA[0.5CA 1.5]V + 900
dCA/dt = 0.1084CA(1.5 0.5CA) + (900 25CA)/(100 + 25t)
s.t. CA(t = 0) = 3.0

26

d(VCB)/dt = 0.5kVCACB + BFB

dCA/dt = 0.0542CA(1.5 0.5CA) + (600 25CB)/(100 + 25t)

s.t. CB(t = 0) = 0

d(VCC)/dt = 0.5kVCACB
dCC/dt = 0.0542CA(0.5CA 1.5) 25CC/(100 + 25t)
s.t. CC(t = 0) = 0

The MATLAB Script File:

%
% CHE654: Problem #60
%
% Isothermal Semi-Batch Reactor
%
clc
clear
format short e
%
% First, determine the value of k
t = [0 5.0 7.5 12.0 15.5 25.0 32.0 40.0];
CA = [2.0 1.65 1.52 1.40 1.28 1.17 1.10 1.06];
CB = 0.5+0.5*(CA-2.0);
logy = log(CA./CB);
[P,S] = polyfit(t,logy,1);
P(1)
k = P(1)/0.5
x = [0:2:40];
y = P(1)*x+P(2);
% plot(t,logy,'o',x,y)
%
% Now, model the semi-batch reactor for 20 minutes
%
format short
simtime = [0:0.5:20];
initC = [3.0, 0, 0];
[t, z] = ode45('fexam', simtime, initC);
[t, z]

27

plot(t,z)
xlabel('Time in Minutes')
ylabel('Concentration in Moles/Liter')
legend('CA','CB','CC')

The MATLAB M-File for the ODE:

function fC = ode(t, C)
fC = zeros(3,1);
fC(1) = 0.1084*C(1)*(1.5-0.5*C(1)) + (900-25*C(1))/(100+25*t);
fC(2) = 0.0542*C(1)*(1.5-0.5*C(1)) + (600-25*C(2))/(100+25*t);
fC(3) = 0.0542*C(1)*(0.5*C(1)-1.5) - 25*C(3)/(100+25*t);
>>
>>
ans =
5.4203e-002

k=
1.0841e-001

ans =
0 3.0000
0.5000 6.4107
1.0000 8.4731
1.5000 9.5443
2.0000 10.0106
2.5000 10.1425
3.0000 10.1014
3.5000 9.9756
4.0000 9.8112
4.5000 9.6326
5.0000 9.4530
5.5000 9.2776
6.0000 9.1095
6.5000 8.9493
7.0000 8.7984
7.5000 8.6570
8.0000 8.5232
8.5000 8.3955
9.0000 8.2751
9.5000 8.1620
10.0000 8.0545
10.5000 7.9517
11.0000 7.8541
11.5000 7.7616

0
0
2.5387 0.1280
4.2365 0.5635
5.3176 1.2278
6.0053 1.9947
6.4559 2.7749
6.7650 3.5207
6.9878 4.2122
7.1556 4.8444
7.2869 5.4190
7.3932 5.9402
7.4809 6.4138
7.5548 6.8452
7.6175 7.2396
7.6719 7.6008
7.7198 7.9324
7.7616 8.2384
7.7977 8.5223
7.8299 8.7855
7.8588 9.0301
7.8844 9.2585
7.9069 9.4724
7.9270 9.6730
7.9453 9.8611

28

12.0000
12.5000
13.0000
13.5000
14.0000
14.5000
15.0000
15.5000
16.0000
16.5000
17.0000
17.5000
18.0000
18.5000
19.0000
19.5000
20.0000

7.6733
7.5885
7.5075
7.4303
7.3562
7.2848
7.2163
7.1506
7.0873
7.0262
6.9672
6.9105
6.8557
6.8025
6.7512
6.7016
6.6535

7.9616
7.9761
7.9891
8.0009
8.0114
8.0208
8.0292
8.0368
8.0436
8.0497
8.0551
8.0599
8.0642
8.0679
8.0713
8.0742
8.0768

10.0384
10.2058
10.3639
10.5134
10.6552
10.7900
10.9182
11.0401
11.1564
11.2674
11.3735
11.4750
11.5722
11.6654
11.7548
11.8407
11.9232

>>

(b) After 20 minutes, the initial conditions for the batch reactor are:
The total liquid volume = 100+(25)(20) +4500/60 = 675 liters
CA = (6.6535)(600)/675 = 5.9142
CB = (8.0768)(600)/675 = 7.1794
29

CD = 4500/675 = 4.6667 mol/liter

dCA = 2dCB = 2dCD

CA CA0 = 2(CB CB0)

and CA CA0 = 2(CD0 CD)

CB = CB0 + (CA CA0)

CD = CD0 + (CA0 CA)

(dCA/dt) = k1CACB + k2CD

= k1CA[CB0 + (CA CA0)] + k2[CD0 + (CA0 CA)]
= 0.1084CA[7.1794 + (CA 5.9142)] + 1.0[4.6667 + (5.9142 CA)]
= CA[0.77825 0.0542CA + 0.32055 0.5] + 7.6238
= 7.6238 CA[0.0542CA + 0.9577]
dCA

= dt

7.6238CA[0.0542CA+0.9577]
dCA

= dt

7.62380.9577CA0.0542CA2

a = 7.6238, b = 0.9577, c = 0.0542

= 4ac b2 = 2.5700

(2/) tanh-1 (/) = (2/) tanh-1 [(b+2cCA)/]

1.24756 tanh-1 [0.62378(0.1084CA+0.9577)]

= dt

1.24756 tanh-1 [0.62378(0.1084CA+0.9577)] 4.1206 = t

Check: when t = 0, CA does equal to 5.9142 mol/liter.

When

, CA = 5.9541 mol/liter from the above equation.

From the ODE: (dCA/dt) = 7.6238 CA[0.0542CA + 0.9577] = 0

------> CA = 5.9541 mol/liter

same answer!

30

62. Isothermal Batch Reactor with a Series Reaction

Consider an isothermal batch reactor with a series reaction where 2 moles of
component A react to form one mole of component B. Component B also reacts to
form component C. The reaction scheme can be characterized as follows:
k2

k1
2A

Initially (t = 0 hr), CA = CA0, CB = 0, and CC = 0, where CA, CB, and CC represent the
concentrations (mol/liter) of components A, B, and C, respectively.
(a) Assume constant volume and that the first reaction 2A B is one-half order and
the second reaction B C is first-order, i.e.
dCA/dt = k1CA1/2
dCB/dt = k1 CA1/2 k2CB
2
Derive an analytical expression for CB as a function of time.
(b) The following experimental data were obtained for component CA:
Time(hr)

0.05

0.15

0.35

0.60

0.85

1.0

CA(mol/liter)

1.0

0.93

0.79

0.54

0.30

0.13

0.06

CB was also measured to be 0.11 mol/liter at t = 1 hr. Determine the values of k1

and k2 and the time tmax at which CB is at its maximum. Hint: Use Polyfit function
in MATLAB to help determine k1 and k2.
(c) Now, suppose the order of the above series reaction conforms to the stoichiometry,
derive analytically a 1st-order ODE for CB, i.e.
dCB/dt + p(t)CB = q(t)
but do not solve this ODE.
(d) When the reaction order conforms to the stoichiometry, the following experimental
data were obtained for CA:
Time(hr)

0.03

0.06

0.10

0.15

0.20

0.30

CA(mol/liter)

1.0

0.76

0.63

0.51

0.39

0.33

0.25

It was also observed that CB reached a maximum of 0.14 mol/liter at t = 0.1 hr.
Determine the values of k1 and k2.

31

Solution:
k1

k2

2A

(a)
If rA = dCA/dt = -k1CA s.t. CA(0) = CA0
rB = dCB/dt = (k1/2)CA k2CB s.t. CB(0) = 0
rC = dCC/dt = k2CB

s.t. CC(0) = 0

Derive analytically CB(t):

CA

t
dCA/CA = k1

CA0

dt 2(CA CA0) = k1t

CA(t)

= (CA0 k1t)2

dCB/dt + k2CB

CB(t)

= (k1/2)(CA0 k1t)

= C1e-k2t + C2t + C3

At t = 0

= C1 + C3

= C1e-k2t + C2

dCB/dt

dCB/dt + k2CB

= k2C1e-k2t + C2 + k2C1e-k2t + k2C2t + k2C3

k2C2t + (C2 + k2C3) = (k1/2)CA0 (k12/4)t

k2C2 = (k12/4)
C2 + k2C3

or C2 = (k12/4k2)

= k12CA0

32

C3

= (1/k2)[(k1/2)CA0 + (k12/4k2)] = (k1/2k2)CA0 + (k1/2k2)2

= (k1/2k2)(CA0 + k1/2k2)

C1 = (k1/2k2)(CA0 + k1/2k2)

CB(t) = (k1/2k2)(CA0 + (k1/2k2) [1 e-k2t] k12/4k2 t

(b)

Time (hr)

0.05

0.15

0.35

0.60

CA (mole/liter)

1.0

0.93

0.79

0.54

0.3

0.85
0.13

1.0
0.06

Has been observed: CB (t = 1 hr) = 0.11 mole/liter

CA(t) = (1 k1t)2 = 1 k1t + (k12/4)t2
Use Polyfit in MATLAB to find the CA vs. t data to a 2nd-order degree polynomial
(or plot CA1/2 vs. t)
From MATLAB : CA = 0.5729t2 1.5146t + 1.0023
Can obtain 2 values of k1 as :
k1 = 1.5146 and k12/4 = 0.5729 k1 = 1.5138
So take the average value: k1 = 1.5142
CB(t) = (0.7571/k2)(1+0.7571/k2)(1 e-k2t) (0.5732/k2)t
CB(t = 1 hr) = 0.11 = (0.7571/k2)(1+0.7571/k2)(1 e-k2) 0.5732/k2
Use MATLAB to solve the above nonlinear equation for k2
k2 = 2.9818 hr-1
CB(t) = 0.3184(1 e-2.9818t) 0.1922t
dCB/dt = 0.9494e-2.9818t 0.1922 = 0

33

 e-2.9818t = 0.2024
tmax = 0.536 hr
CB,max = 0.151 mole/liter
(c) The reaction order conforms to stoichiometry
dCA/dt = k1CA2

s.t. same initial conditions

dCB/dt = (k1/2) CA2 k2CB

Derive 1st-order ODE for CB, i.e. dCB/dt + p (t)CB = q(t)

CA

t
dCA/CA2 = k1

CA0

dt 1/CA 1/CA0 = k1t

CA(t) = CA0/(CA0k1t + 1)
dCB/dt + k2CB = (k1CA02/2)[CA0k1t + 1]2
(d)

Time (hr)
CA (mole/liter)

0
1.0

0.03
0.76

0.06
0.63

0.1
0.51

0.15
0.39

CB,max has been observed at 0.14 mol/lit at t = 0.1 hr

1/CA = k1t + 1
Use Polyfit to regress 1/CA vs. t by fitting y = ax + b
Slope of the straight line is k1 y = 10.0676t + 1.0002
k1 = 10.0676
CB,max occurs at dCB/dt = 0
k2CB,max = (10.0676/2)(10.0676tmax + 1)2

k2

= 8.9285 hr-1

34

0.2

0.3

0.33

0.25

67. Batch Distillation, II

A liquid mixture containing 60.0 mole% n-pentane and 40.0 mole% n-hexane is to be
distilled in a batch still, and is initially charged with 100 gmoles of the mixture. The
equilibrium relationship between the mole fraction x of n-pentane in the liquid and that
in the vapor y has been correlated to the following equation:
y = 1.8804 x 0.8804 x2
Note that this equation is only valid for n-pentane, and not necessarily for n-hexane.
V (gmol/min)
yi

xi

L (gmoles)

(a) Calculate the system temperature at which the above equilibrium relationship was
established for the given liquid mixture (i.e. determine T in C at which the above
equation is valid). Also, compute the total system pressure P at the system
temperature.
Assume ideal gas and ideal liquid, and the vapor pressures of the two components are:

For n-pentane,

For n-hexane,

log10 PVAP = 6.85221 __1064.630__

T + 232.00
log10 PVAP = 6.87776 __1171.53_
T + 224.366

PVAP in mmHG
T in C

(b) Derive an analytical expression relating the amount of liquid left in the batch still L
as a function of x (mole fraction of n-pentane in the still) and compute the value of
x after 90% of liquid has been vaporized.

Solution:
(a) Start with Raoults Law for ideal liquid:
yc5P = xc5PC5VAP
(1.8804 xc5 0.8804 xc52 )P = xc5 10[6.85221
35

1064.63/(T+232.0)]

But xc5 = 0.6 and P = xc5PC5VAP + xc6PC6VAP

0.8113[0.6*10[6.85221
= 0.6*10[6.85221

1064.63/(T+232.0)]

+ 0.4*10[6.87776 1171.53/(T+224.366)]]

1064.63/(T+232.0)]

0.32452 (10[6.87776 1171.53/(T+224.366)]) 0.11322 (10[6.85221

1064.63/(T+232.0)]

= 0
Use MATLAB for solve for the root or T

Nonlinear equation in T
Get

T = 55.55 C

Also get,

P = 845.86 + 196.69 = 1042.55 mmHg

(b) Start with mass balances:

dL/dt = V
d(xL)/dt = yV or x(dL/dt) + L(dx/dt) = (1.8804x 0.8804x2)(dL/dt)
xdL + Ldx = (1.8804x 0.8804x2)dL
Ldx = (0.8804x 0.8804x2)dL

1.13585 dx

dL

x( 1 x)

1.13585

Integrate from x = 0.6 to x and L = 100

to L

dL

1x

ln (x) ln(1 x) = 0.8804 ln(L)

x
ln

x
1 x

L
= 0.8804 ln(L)

0.6

100

36

ln

0.6667 x

= ln

1 x

0.6667 x

0.8804

L
100

1 x

When 90% of the liquid L is vaporized

0.8804

L
100

L = 10

37

x = 0.165