Question 1 20 marks

a) The irreversible gas phase elementary reaction A + B
C + D + E takes place in a flow reactor.
The concentrations of A and B feed streams are 2 mol/lit before mixing. The volumetric flow rate
of each stream is 4 lit/min and the entering temperature is 300K. The streams are mixed
immediately before entering. Calculate the reactor volume to achieve 80% conversion of A in (i)
a plug-flow reactor (PFR) and (ii) a continuous-stirred tank reactor (CSTR).
Note: k = 0.04 lit/mol.min at 273K and E = 8,000 cal/mol.

b) The liquid phase reaction 2A
C follows an elementary rate law and is carried out isothermally
in a plug-flow reactor. Reactant A and an inert B are fed in equimolar ratio and conversion of A
is 70%. If the molar flow rate of A is reduced to 40% of the original value and the feed rate of B
is left unchanged, calculate the conversion of A.

Solutions

a)
Before mixing
CA0’ = 2 mol/lit
CB0’ = 2 mol/lit
v0’ = 4 lit/min

After mixing:
CA0 = 1 mol/lit
CB0 = 1 mol/lit
v0 = 8 lit/min

Rate law:
− rA = kC A C B [1]

Stoichiometry:
C A0 (1 − X )
CA =
1 + εX [1]
C A0 (1 − X )
CB =
1 + εX

[1]
ε = y A0δ = (0.5)(1) = 0.5

Kinetics constant:
k2 E  1 1
ln =  − 
k1 R  T1 T2 
E  1 1 
k 2 = k1 exp   − 
 R  T1 T2 
 8000  1 1 
k 2 = 0.04 exp   − 
1.987  273 300 
k 2 = 0.1508lit / mol. min [1]

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i) Design equation for PFR:
X dX
V = FA 0 ∫ [1]
0 − rA

Combine and solve:

X dX X dX
V = F A0 ∫0 − rA
= F A0 ∫ 0
 C (1 − X ) 
2

k  A0 
 (1 + εX ) 
FA0 X dX
V= 2
kC AO ∫0
 1− X 
2

  [1]
 1 + εX 
FA0  2 (1 + ε ) 2 X 
V= 2 
2ε (1 + ε ) ln(1 − X ) + ε X + 
kC AO  1− X 
8  2 (1.5) 2 (0.8) 
V= 2(0.5)(1.5) ln(1 − 0.8) + (0.5) (0.8) + 
0.1508(1)  0 .2 
V = 360lit [2]

ii) Design equation for CSTR:

F A0 X
V= [1]
− rA

X
V = F A0 2
 C (1 − X ) 
k  A0 
 (1 + εX ) 
F X [1]
V = A20
kC AO  1 − X  2
 
 1 + εX 
2
v 0 X  1 + εX 
V=  
kC AO  1 − X 
2
8  1 + 0 .5 x 0 .8 
V=  
0.1508(1)  1 − 0.8 
V = 2080lit [2]

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b)
Rate law:
− rA = kC A2
Stoichiometry:
C A = C A0 (1 − X )

Design equation:
X dX
V = FA0 ∫ [2]
0 − rA

Combine:
X dX F X dX
V = F A0 ∫
0
= A20
− rA kC A0 ∫ (1 − X )
0 2

VkC A2 0 X 0 .7 7
= = =
F A0 1 − X 0 .3 3

When molar flow rate of A reduced in 40%:

If FA0’ = 0.4FA0
CA0 = yA0CT
CA0’ = yA0’CT
[2]
yA0 = FA0/ FT0 = FA0/ (FA0 + FB0) = ½ [FB0 = FA0]
y’A0 = F’A0/ F’T0 = F’A0/ (F’A0 + FB0) = 0.4FA0/ (0.4FA0 + FA0) = 2/7

2
C A' 0 y 'A0 CT
= = 7 =4
C A0 y A0 C T 1 7
2
C A' 0 = 4 C A0
7
( )
Vk C A' 0
2

=
X
[2]
F ' A0 1− X
2
4 
Vk  C A0 
 7  = X
0 .4 F A 0 1− X
 VkC A2 0

0.816 = X
 1− X
 F A0 
X
0.816(7 / 3) =
1− X

X = 66% [2]

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Question 2 15 marks
The irreversible liquid-phase reaction A
B + C was carried out in a constant volume batch
reactor. The following data were collected during the course of the reaction:

t (min) 10 20 30 40 50 60
CA (mol/lit) 2.45 1.74 1.23 0.88 0.62 0.44

Determine the order of reaction and the specific reaction rate using numerical technique-
differentiation formulas to differentiate your data.

Solution

[6]

t (min) 10 20 30 40 50 60
CA (mol/lit) 2.45 1.74 1.23 0.88 0.62 0.44
ln (CA) 0.896 0.554 0.207 -0.128 -0.478 -0.821
(-dCA/dt) 0.081 0.061 0.043 0.0305 0.022 0.014
ln(-dCA/dt) -2.513 -2.797 -3.147 -3.490 -3.817 -4.269

Constant volume batch reactor:

dC A
= rA = − kC αA
dt
[2]
 dC A 
ln −  = ln k + α ln C A
 dt 
Plot ln(-dCA/dt) vs ln (CA)

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 [3]

From the graph,

Slope = α = 1.013
Reaction order = 1 [2]

Intercept = -3.377
ln k = -3.377
k = 0.0341 min-1 [2]

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Question 3 22 marks
The following gas phase reaction involving reactant A produces B (desired product), and X and Y
(both undesired products) as follows, with all specific reaction rates at 27°C:

A
B rB = k2 CA k2 = 0.3/min
A
X rx = k1 CA1/2 k1 = 0.004 (mol/lit)1/2 . min
A
Y ry = k3 CA2 k3 = 0.25 lit/mol . min

The reaction system operates at 27°C and 3 atm pressure. The reactant A enters the system
without any inerts at 12 lit/min.

(a) Sketch the instantaneous selectivities (S B/X, S B/Y, and S B/XY) as a function of the
concentration of CA. Use the given graph papers. 6 marks
(b) Consider a series of reactors to carry out the reactions. You have the option to choose
either a CSTR or a PFR as the first reactor to maximise the selectivity of the desired
product. Which reactor is the most suitable and why? 2 marks
(c) What should be the volume of the first reactor? 3 marks
(d) What are the effluent concentrations A, B, X and Y from the first reactor? 8 marks
(e) What is the conversion of A in the first reactor? 3 marks

Solution

CA0 = yA0PT/RT = 1(3)/(0.082)(300)=0.122 mol/lit

k2 1/ 2
(a) S B / X = C A = 75C 1A/ 2 [1]
k1

[1]

CA

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 k 2 −1
SB /Y = C A = 1.2C A−1 [1]
k3

Sb/y

[1]

CA

k2C A
S B / XY = [1]
k1C A + k 3 C A2
0. 5
Sb/xy

[1]

CA

b) Because the concentration changes down the length of a PFR, we cannot operate at this
maximum. Consequently, we will use a CSTR and design it to operate at optimum CA [2]
concentration.

c) SB/XY maximises at CA* = 0.04 mol/lit

V = v0(CA0- CA*)/-rA = 12(0.122-0.04)/(0.004x0.040.5 + 0.3x0.04 + 0.25x0.042) [3]

V = 74.54 lit

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d)

CA* = 0.04 mol/lit [2]

τ = CB/rB
74.54/12 = CB/0.3x0.04
CB* = 0.07455 mol/lit
[2]

τ = CX/rX
74.54/12 = CX/rX
CX* = 5.18 x 0.004 x 0.040.5 = 0.00497 mol/dm3 [2]

τ = CY/rY
74.54/12 = CY/rY
CY* = 5.18 x 0.25 x 0.042 = 0.00248 mol/dm3 [2]

e)

Conversion, X = (0.122 – 0.04)/(0.122) = 0.672 [3]

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Question 4 18 marks
(a) how do you define Damkohler number and what is its physical significance? 2 marks

A dimensionless number that can give a quick estimate of the degree of conversion
[2]
that can be achieved in continuous flow reactors (Da = -rA0V/FA0)

(b) measurement in a reaction system indicates a Damkohler number of 5; what can be the
approximate conversion of the reactant in the system 2 marks

For 1st order liquid phase reaction in a CSTR, X = Da/(1+Da); Conversion, X = 83% [2]

(c) what type of reactors do you usually use to determine the rate law parameters of
homogeneous reactions? 1 mark

Batch reactor [1]

(d) For the following parallel reactions involving reactants A and B: 10 marks

A+B
D: rD = k1 CAα1CBβ1

A+B
U: rU = k2 CAα2CBβ2

Where D and U are the desirable and undesirable products

Consider the following four combinations of reaction orders and select the reaction scheme (clearly
stating the type of reactors and/or their combinations) that will maximize the selectivity S D/U

Case 1: α1 > α2 and β1 > β2

Case 2: α1 > α2 and β1 < β2
Case 3: α1 < α2 and β1 < β2
Case 4: α1 < α2 and β1 > β2
Marks distribution: for each case, 1 mark for the selectivity parameter, and 1.5 mark for the
subsequent explanation.

Solution

Case 1:
k
S D / U = 1 C Aa C Bb [1]
k2
To maintain the concentrations of both A and B as high as possible
Use tubular reactor and batch reactor [1.5]

Case 2:
k Ca
S D / U = 1 Ab [1]
k2 CB
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To make the concentrations of A high and concentration of B low
Use semibatch reactor in which B is fed slowly into large amount of A; A membrane reactor or a
tubular reactor with side streams of B; A series of small CSTRs with A fed only to the first reactor [1.5]
and small amounts of B fed to each reactor

Case 3:

k1 1
S D /U = [1]
k 2 C Aa C Bb
)

To carry out the reaction at low concentrations of A and B

Use CSTR; Tubular reactor with large recycle ratio; Feed diluted with inerts [1.5]

Case 4:
k Cb
S D / U = 1 Aa [1]
k2 CB
To make the concentrations of B high and concentration of A low
Use semibatch reactor in which A is fed slowly into large amount of B; A membrane reactor or a
[1.5]
tubular reactor with side streams of A; A series of small CSTRs with B fed only to the first reactor
and small amounts of A fed to each reactor

(e) Multiple choice questions 3 marks

i) A membrane reactor is very similar to a

A. Batch reactor
B. Continuous stirred tank reactor [1]
C. Back mix reactor
D. Plug flow reactor
E. None of the above

ii) The total cycle time in any batch operation includes all the below except for
A. time necessary for fill
B. time necessary for reaction
C. time necessary to achieve desired conversion [1]
D. time necessary for heating of reactor
E. time necessary for cleaning between batches

iii) In application of method of initial rate, which of the following show the reaction
order?
A. The slope of plot of ln(-rA0) versus ln CA0
B. The slope of ln(-dCA/dt) versus ln CA
[1]
C. The slope of ∆CA / ∆t as a function of t
D. The slope of dCA/dt versus t
E. None of the above

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