Question 1

Nitryl fluoride, NO2F2 is a colourless gas and strong oxidizing agent, which is widely used as
a fluorinating agent. It is produced by isothermal, non-elementary reaction via the synthesis
of nitrogen dioxide, NO2 and fluorine gas, F2. In this reaction, the order of reaction for each
respective reactant is 1.
() + () ()
+

A chemical engineer is given the responsibility to design the best flow reactor for this
reaction. Its known that the k value obtained in batch reactor can be used in designing flow
reactor. The temperature and the pressure inside the reactor is at 90 and 10 atm
respectively. Data of reaction in batch reactor is provided.
a) Prove that the equation given below. Assuming that the volume of batch reactor is
constant ( = 0 ). Calculate the time required to achieve 0.90 conversion rate in this
batch reactor.
=

tR (min)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
4.0
6.0
10.0

X
0.000
0.136
0.246
0.337
0.414
0.479
0.534
0.614
0.739
0.866

(2 )
1
[2 log
]
0
2(1 )
(1/CA0)log((2-x)/(2(1-x))
0
0.195846249
0.39064433
0.585409078
0.781997448
0.977746995
1.170940821
1.512773393
2.280027283
3.729037265
(2)

Note: (1)(10.5) = 2 log 2(1)

[14 marks]

Given that the flow rates of both reactants are the same, and assuming that there is no
pressure drop throughout the reaction in reactor. The temperature and the pressure
inside the reactor is at 90 and 10 atm respectively.

b) For a given conversion factor of 89%, the production rate of nitryl fluoride required
for a particular reaction is 30 dm3/min. Suggest and justify the best type of reactor for
the production of nitryl fluoride.

[11marks]

CNBr + CH3NH2 CH3Br + NCNH2

2. A UTP professor started his research regarding broad spectrum pesticide used in the control
of pests, weeds, pathogens and rodents. He reacted bromocyanide and methylamine, to get the
product methyl bromide. The elementary reaction shown above has a rate constant, k of 0.036
dm3 mol-1s-1 at 353.15K. The professor intends to carry out the reaction in an isothermal flow
reactor at 393.15 K and 10 atm. The feed molar flow rate of CNBr is 50% of the total molar
flow rate. The required production rate of CH3Br is 100 mol h-1.
(a) Assuming the effect due to pressure drop through the reactor to negligible, suggest the best
type of flow reactor that can be used to achieve 86% conversion. The provided activation
energy, E, is 15 kJ mol-1. Justify your answer.
[15 marks]
(b) A company decides to invest their money greatly on the production of methyl bromide.
Assuming the reaction is carried out by supplying excess CH3NH2 ([CH3NH2]o and [CH3NH2]
are in excess) so that the reaction is pseudo first order. Given vo = 3.2 x 10-3 m3 s-1 , k remains
unchanged and CAo, FAo remains the same.
The company decided to hire six chemical engineers to come up with ideas of how to
commercialize the production of methyl bromide. Three of them decided to build isothermal
CSTRs in series while another three decided to build the isothermal CSTRs in parallel. Given
the volume of each CSTR is 100 dm3, calculate how many numbers of CSTR is required to be
assembled in series and in parallel in order to achieve a conversion as stated in part (a).
Assuming the CSTR is made up of borosilicate glass, the cost of 1 m2 of borosilicate glass is
US $4000. The 100 dm3 CSTR provided has 35.68 cm in diameter. Calculate the cost required
for CSTR in series and parallel. Justify your result.
[10 marks]

Solutions
Part (a)

mole balance:

( 0 )
=

0 = (1m)

rate law:

= [2 ][2 ] (1m)

stoichiometry (constant volume batch reactor)

=

= 0 (1 ) (0.5m)

= 0 (1 0.5) (0.5m)

= [ ][ ]
=

[0(1)][0 (10.5)]
0

(1m)

= 0 (1 )(1 0.5)
1

= (1)(10.5) (1m)
0

(2)

= [2 log 2(1)] =
0

Graph of tR vs (1/CA0)log((2-x)/(2(1-x))

tR (min)
4
3.5

y = 0.3772x

3
2.5

2
1.5
1
0.5
0
0

(4m)

10

12

 = 0.3772 M-1min-1 (1m)

0 =
=

0.5 10
82.057

.3
.

(90+273)

(1) = 0.168 /3 (1m)

1
(2 )
[2 log
]
0
2(1 )
1

(20.9)

0.3772 = 0.168 [2 log 2(10.9)] (1m)

= 11.68(1m)

0 =

(b)

0.5 10
82.057

.3
.

(90+273)

= 0.168 /3

FC = 30 dm3/min
= 0 (0.5m)
0 =

30 3 /
0.89
1

= 32.294 3 / (0.5m)
1

= = 0.5 (2 2 1) = 0.5 (0.5m)

= 0 = 1 (0.5m)
0

NO2 (g) +
Species
NO2
F2
NO2F2
Total

Symbol
A
B
C

1
F (g) 2NO2 F2 (g)
2 2

Initial
FA0
FA0 B
FT0

(1)

Change
-FA0
-0.5FA0
FA0
0

(1)

= 0 (1+) = 0 (10.5)(0.5m)
= 0

(10.5)
(1+)

(10.5)

= 0 (10.5) = 0 (0.5m)

rate law: =

x
0.00
0.20
0.40
0.60

-rA (dm3/min)
0.01065
0.00946
0.00798
0.00608

FA0/-rA (m3)
3.033
3.413
4.045
5.308

Remaining
FA= FA0(1- )
FB= FA0(1-0.5 )
Fc= FA0
FT=FT0+FA0

0.80
0.89
(2m)
=

0.00355
0.00211

9.100
15.305

= 15.305(0.89)
= 13.6214 3 (1m)
= @=0 =0.8 + @=0.8 =0.89
0.8

= 0 0

0.89

+ 0 0.8

(1m)

Using 5-point rule for value of from 0 to 0.8 and 2-point rule for 0.8 to 0.89,
=

0.80
4(3)

[3.003 + 4(3.413) + 2(4.045) + 4(5.308) + 9.100] +

0.890.8
2

[9.100 +

15.305] (1m)
= 3.6738 + 1.0982
= 4.772 3 (1m)
In conclusion, plug flow reactor is the best reactor (1m) for this reaction as it needs a
volume of 4.772 3 which is much less than the volume of continuous-stirred tank
reactor which is 13.6214 3 .(0.5m) Besides, the smaller volume of reactor means
that there is less space needed for the reactor. This shows that the company would
need to invest much less money on the reactor and proves that the plug flow reactor is
economically the best option. (0.5m)

Solution:
2(a) Using Arrhenius law at T = 393.15 K and P = 10 atm:
E 1
1
k(T2 ) = k(T1 ) exp [ ( )]
R T1 T2
15000
1
1
k = (0.036 3 1 1 ) exp [
(

)]
8.314 1 1 353.15 393.15
k = 0.061 3 1 1 (1 mark)

CAo =

yA o P
RT

Species
CNBr
CH3NH2
CH3BR
NCNH2

0.5010

= 82.057 31 1 393.15 = 0.155 3 (1 mark)

Symbol
A
B
C
D

Initial
FAo
FBo = BFAo = FAo
-

=1

=
= [(1 + 1) (1 + 1)] 0.50
= 0 ( )(1 mark)
= 100

3600

= 0.0278

=
(0.86) = 0.0278
= 0.0323

Conversion rate = 0.86 ,

=

(1 mark)
FAo = 0.0323 mol s-1

Change
-FAoX
-FAoX
FAoX
FAoX

Remaining
FAo (1-X)
FAo (1-X)
FAoX
FAoX

Concentration
CAo (1-X)
CAo (1-X)
CAoX
CAoX

ra = k = [ (1 )] = 2 (1 )2 =

0.061 3
.

(0.155)2

2
6

(1 )2

(1 mark)

-rA (mol dm-3.s-1)

(dm3)

1.466 x 10-3

22.03

0.2

9.379 x 10-4

34.44

0.4

5.276 x 10-4

61.22

0.6

2.345 x 10-4

137.74

0.8

5.862 x 10-5

551.01

0.86

2.872 x 10-5

1124.65
(2 marks)

= @ = 0 to 0.8 + @ = 0.8 to 0.86(1mark)

(5 points rule)
=

0.2
3

(2 points rule)

[22.03 + 4(34.44) + 2(61.22) + 4(137.74) + 551.01] + 0.5[551.01 + 1124.65][0.86 0.8](1mark)

= 92.28 + 50.27 = 142.55 3

(1mark)

@0.86 = (1124.65)(0.86)
= 967.2 3
=

(1 mark)

Justification,
In order to achieve the same conversion, the volume of PFR required is 142.55 dm3 which is
smaller than volume of CSTR (967.2 dm3). If volume is smaller, it indicates less cost is required
to build the flow reactor and it saves more space.(1 mark) Hence, PFR with smaller volume is
the best flow reactor compared to CSTR.

(a) CAo = 0.155 mol dm-3,

FAo = 0.0323 mol s-1,

k = 0.061 s-1

For CSTR in series.

V1 = V2 = V
1 = 2 =
=

1003
13
=

= 31.25 (1 )
3.2 103 3 1 10003

= 1

1
(1 + )
1

0.86 = 1 [1+(31.25)(0.061)] (1 )
0.14 = (1 + 1.906)
0.14 = (2.906)
log 0.14 = 2.906
= 1.84 (0.5 mark)
Therefore, number of CSTR unit required to achieve conversion rate of 0.86 is equals to 2.
(0.5 mark)

For CSTR in parallel.

=

For X = 0.86 :
0.86

= 10.86 (1 mark)
= 6.143
(0.061) = 6.143
= 100.7 (1 )

=
( )

100.7 =

13
10003
3
3.2 10 3 1

1003

= 3.22 (0.5 mark)

Hence, the number of CSTR units required to achieve conversion rate of X = 0.86 is 4 units.
(0.5 mark)
For 1 unit of CSTR,
Volume = 100 dm3
2 = 1003
2

(35.68 102 )
] = 0.100 3
[
2
= 1.0 (1 mark)
The total surface area of 100 dm3 CSTR;
= 2 2 + 2
2

35.68 102
35.68 102
] + 2 [
]1
= 2 [
2
2
= 1.321 2 (1 mark)
Cost for 1 CSTR
= 1.321 2

$4000
2

= $5284 (1 mark)
For Series, n=2, the total cost = 5284 x 2 = US $10568 (1 mark)
For Parallel, n=4, the total cost = 5284 x 4 = US $21136 (1 mark)

Hence, by comparing the cost of CSTR in series and parallel arrangement, the cost of CSTR
in series is relatively lower. (1 mark) Therefore, its more economical to apply CSTR in
series in order to achieve the desired conversion rate. (1 mark)