CN2116 Homework Set #6 (due March 14 2016) CN2116-JYL-2016-HW6

1. A transforms to B in an exothermic reaction with the following stoichiometry:

A B

rA k2 c A k2 cB

R is introduced into the reaction mixture to form a useful product P:

A R P

rP k1c AcR

(a) Show that the introduction of R in large excess renders the thermodynamic
equilibrium between A and B infeasible.
(b) If R is only introduced in moderation, how should the reactor be operated
to increase the yield of P? Three thermal management schemes have been
proposed:
A temperature profile that increases linearly with reactor length
A temperature profile that decreases linearly with reactor length
Isothermal operation at the highest possible temperature
Which temperature scheme will you recommend and why?
2. Sketch the operating line(s) for the following non-isothermal reactor operation
on the xA-T diagram for an exothermic reaction.

3. The aqueous reactions

A B R T
R B S T

occur with elementary second order kinetics. Find the optimum temperature
of operation of a plug flow reactor, and the corresponding maximum fractional
yield of R per mole of A in the feed. R is the desirable product, and any
temperature between 5 and 65oC may be used.
Data: Equimolar quantities of A and B were mixed and allowed to rest in
beakers at different temperatures. When all B was consumed, analysis showed
that 75% of A had reacted at 25oC, 60% of A had reacted at 45oC.

4. (OL 9.11) The first order reactions

1
3
A
R
S desired
2
4

T
U

k1 109 e 6000/T
k2 107 e 4000/T
k3 108 e 9000/T
k4 1012 e 12000/T

are to be run in two mixed flow reactors in series anywhere between 10 and 90
o
C. If the reactors may be kept at different temperatures, what should these
temperatures be for maximum fractional yield of S? Find this fractional yield.
5. (OL 10.15) We want to produce R from A in a batch reactor with a run time no
longer than 2 hours and at a temperature somewhere between 5 and 90oC. The
kinetics of this liquid phase first-order reaction system is as follows:

A
R
S
1

k1 30e 20000/ RT

k [min 1 ]

k2 1.9e 15000/ RT

R 8.314 J/molK

Determine the optimum temperature which yields cR ,max , the run time to use
and the corresponding conversion of A to R.

[Discussion Topics]
1. The first order irreversible gas-phase reaction A B C is carried out
adiabatically in a PFR packed with a catalyst. Pure A enters the reactor at the
volumetric flow rate of 20 l/s at a pressure of 10 atm and a temperature of
450K. Plot the conversion and temperature down the PFR length until 80%
conversion is reached. The maximum catalyst weight that can be packed into
the PFR is 50 kg.
Data:

c pA 40 J/mol,c pB 25 J/mol,c pC 15 J/mol,

H 0fA 70 kJ/mol, H 0fB 50 kJ/mol, H 0fC 40 kJ/mol (refernced to
273K)
E

k=0.133e R

1 1
)
273 T

l /kg-s, E 31.4 kJ/mol

Hint: An equation solver (Polymath or MATLAB) is needed for the numerical

answers.
2. The reaction A B C is carried out in a batch reactor by keeping
temperature and pressure constant. While A and B are gases, C is condensable
as a liquid at the reaction temperature.
(a) How will you adjust the processing conditions (T, P, reaction time, and the
reactant amounts) if it is desired to produce as much of B as possible from
A?
(b) How will you adjust the processing conditions to keep the reactor dry all
the time?
3. Describe the processes shown in the xA-T diagram below:

[Worked Examples]

1. Recommend, with reasons, the contacting scheme and temperature profile that
will maximize the yield of R per mole of A reacted in the following competing
reactions:
A B R

r1 k1c AcB

AS

r2 k2 c A2

E1 E2

Solution

We want cB to be high, c A to be low, and low temperature when reaction rate is

high (at reactor entrance), and high temperature when reaction rate is low (at
reactor exit). Hence best choice is Rising temperature profile, B in plug flow,
and A in mixed flow.
2. For the reacting system of the examples in Chapter 9 of OL and with a more
concentrated feed of cA0 = 10 mol/l.
(a) How can one carry out an adiabatic operation for either plug or mixed flow
to achieve 80% conversion from a single reactor? The allowable
temperature for the fluid is from 50C to 950C.
(b) For a feed rate FA0 = 1 kmol/min, provide an adiabatic design giving the
type and size of reactor, and sketch the location and duty of the necessary
heat exchangers. Feed is available at 250C.
Solution

Slope of adiabatic line =

c 'p
H

i i c pi
H

100
1

18000 180

(Note: i i c pi is the heat capacity of the reaction mixture per mole of A. It is

given that the reaction mixture behaves like water (and hence is 1000 cal/l) and
contains A at 10 mol/l)
(a) For CSTR, the best operating point should be the intersection of xA = 0.8 and
the optimum temperature progression line. For PFTR, the best design should have
the operating line straddling the optimum temperature progression around xA = 0.8
(trials and errors required). The following solution considers the CSTR case only.

It is not possible to operate a PFTR as the feed would have to enter below 5oC. It
is however possible to operate a PFTR with recycle. In this case, the product is
cooled to 5oC (point E) and mixed with the fresh feed at 5oC (point F) to obtain a
partially converted feed (point A)
FA0 , v

xAi
R

1 xAf xAi

( R 1) FA 0 (1 x Ai )
RFA 0 (1 x Af ), Rv

From the lever-arm rule,

amount of recycled product AF
0.49

1.58
amount of fresh feed
EA 0.8 0.49
(b) Select the design of an adiabatic CSTR. Note that recycle is needed even for a
CSTR. (Note: The design equation for CSTR is not changed with recycle. You
may like to prove that yourself)
FA0 1 kmol/min

The CSTR will be the smallest if it is operated at point B ( x A 0.8, T 620 C ) on

the optimum temperature progression.

rA 0.110 1
5

FA0 x A 1000 0.8

800 (l )
1
rA

The adiabatic line from point B (equation: xA

T
0.417 ) passes through
180

xA 0.6 at T 250 C (the feed temperature).

Amount of recycled product to be cooled =

0.6
1000 3000 (mol/min)
0.8 0.6

T (62 25) 370 C

Cooling duty Q Fc 'p T 3000 100 37 11100 (kcal/min)
3) Consider the follow scheme of first order reactions
1
2
A
R
S
3

k1 10e 3500/T , k2 1012 e10500/T , k3 108 e 7000/T , s -1

The feed consists of A and inert, cA0 = 1 mol/l, and the operating temperature
between 70C and 770C.
(a) What is the maximum amount of S obtainable per mole of A charged to the
reactor, and at what temperature and in what type of reactor is this
obtained?
(b) Find the minimum holding time to produce 99% of cS ,max .
Solution

Given cA0 1 mol/l , k1 10e3500/T , k2 1012 e10500/T , k3 108 e7000/T , s -1

As the desired reaction (reaction 2) has the highest activation energy, the reactor
should be operating at the highest allowable temperature which is 77oC (350 K)
At T = 350 K

k1 10e10 4.5 104

k2 1012 e 30 910 104
k3 108 e20 2025 104

(a) From the above k values the first step is evidently rate limiting. For maximum
yield of S per mole of A charged to the reactor, one should operate a PFTR for the
complete conversion of A at 77oC

 ( S | A0 )

FS
FS

FA0 FS FT

dF
dF dF
r dV

r dV r dV
k c dV

k c dV k c dV
S

2 R

2 R

3 R

k2
k 2 k3

910
0.31
910 2035

cS ,max c A0 ( S | A0 ) 1 0.31 0.31 (mol / l )

(b) Since the first step (A R) is rate limiting, cS 0.99cS ,max corresponds
approximately to c A 0.01 mol/l . From the PFTR design equation,
c A dc
dcA
A

cA 0 r
cA 0 k c
1 A
A

cA

with cA0 1, c A 0.01 and k1 4.5 104 ,

10200 s