SOLUTIONS TUTORIALS SESSION 1

1.1

Liquid A decomposes by second order kinetics and in a BR 50% of A is converted in a 5 minute run. How
much longer would it take to reach 75% conversion?

Solution

Reaction rate equation:

−𝑅𝐴 = 𝑘𝑐𝐴2 (1)

Solution for cA/cA0:

𝑐𝐴 1
= (2)
𝐶𝐴,0 1+𝑘𝑐𝐴,0 𝑡

Calculate kcA,0
𝑐𝐴 1
𝑐𝐴,0
= 0.5 = 1+5𝑘𝑐 => 𝑘𝑐𝐴,0 = 0.2 (3)
𝐴,0

Fill in kcA,0 =0.2 in equation 2

𝑐𝐴 1
𝑐𝐴,0
= 0.25 = 1+𝑡∙0.2 => 𝑡 = 15 (4)

So, it takes 10 minutes longer to reach 75% conversion

1.2

In a homogeneous isothermal liquid phase polymerization, 20% of the monomer disappears in 34

minutes for initial monomer concentration of 0.04 kmol/m3. What is the rate of disappearance of the
monomer?

Solution

𝜉∙𝑐0
𝑅= 𝑡
(1)

0.2∙0.04 𝑘𝑚𝑜𝑙
𝑅= 34
= 2.35 ∙ 10−4 𝑚3 𝑚𝑖𝑛 (2)

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SOLUTIONS TUTORIALS SESSION 1

1.3

The first-order reversible liquid phase reaction A -> P with CA,0 = 0.5 kmol/m3 and CP,0 = 0 takes place in a
BR. After 8 min, conversion of A is 33,3%, while equilibrium conversion is 66.7%. Find the rate equation of
this reaction.

Solution

Reaction rate equation:

−𝑅 = 𝑘1 𝐶𝐴 − 𝑘2 𝐶𝑝 (1)

With

𝑐𝑝 = 𝑐𝐴,0 − 𝑐𝐴 (2)

At equilibrium R = 0 and cA = ⅓ cA,0.

𝑘1 𝑐𝐴 = 𝑘2 (𝑐𝐴,0 − 𝑐𝐴 ) (3)

(𝑐𝐴,0 −𝑐𝐴 ) 𝑘1
= (4)
𝑐𝐴 𝑘2

1
𝑐𝐴,0 − 𝑐𝐴,0 𝑘1 1
1
3
=2= → 𝑘2 = 𝑘1 (5)
𝑐 𝑘2 2
3 𝐴,0

Determine reaction rate constants

𝑑𝑐𝐴
𝑑𝑡
= −𝑘1 𝑐𝐴 + 𝑘2 𝑐𝑝 (6)

Fill in equation 2 and 5 in equation 6

𝑑𝑐𝐴 1
= −𝑘1 𝑐𝐴 + 𝑘1 (𝑐𝐴,0 − 𝑐𝐴 ) (7)
𝑑𝑡 2

𝑑𝑐𝐴 1 1
𝑑𝑡
= −1 2 𝑘1 𝑐𝐴 + 2 𝑘1 𝑐𝐴,0 (8)

Set a = -1 ½ k1 and b = ½ k1cA,0 and rewrite equation

𝑑𝑐𝐴
= 𝑑𝑡 (9)
𝑎𝑐𝐴 +𝑏

Integrating eq 9 results in:

1 c
[ln 𝑎𝑐𝐴 + 𝑏]𝑐𝐴A,0 = t − t 0 (10)
𝑎

Rewriting eq 10, fill in t0 = 0 results in:

(𝑎𝑐𝐴,0 −𝑏) exp(𝑎𝑡)+𝑏 𝑎𝑐𝐴,0 −𝑏 𝑏 𝑏 𝑏

𝑐𝐴 = 𝑎
= 𝑎
exp(𝑎𝑡) + 𝑎 = (𝑐𝐴,0 − 𝑎) exp(𝑎𝑡) + 𝑎 (11)

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SOLUTIONS TUTORIALS SESSION 1

With b/a = 1/3cA,0, a=-1 ½ k1, eq. 11 becomes

2 1 1
𝑐𝐴 = 3 𝑐𝐴,0 exp (1 2 𝑘1 𝑡) + 3 𝑐𝐴,0 (12)

With cA,0 = 0.5 kmol/m3, cA = ⅓cA,0 and t = 8 min k1 can be calculated.

This results in k1 = 0.058 mol/m3.min and thus k2= 0.029 mol/m3min. Answer of the question will be:

−𝑅 = 0.058𝑐𝐴 − 0.029𝑐𝑝 (13)

1.4

A homogeneous liquid phase reaction AP with |RA| takes place with 50% conversion in a CISTR.

a) What will be the conversion if this reactor is replaced by one 6 times as large, everything else
remaining unchanged?
b) What will be the conversion if the original reactor is replaced by a PFR of equal size, everything
else remaining unchanged?

Solution

a) For a first order reaction, conversion is a CISTR can be written as:

𝑐 1
𝜁 = 1 − 𝑐 𝐴 = 1 − 1+𝑘𝜏 (1)
𝐴,0

With a conversion of 0.5, kτ can be calculated resulting in kτ = 1. Having the residence time 6 times
higher, kτ becomes 6 in the new situation. Filling in this value in equation 1, the conversion will be
85.7%

b) The conversion as function of kτ in a PFR will be:

𝑐
𝜁 = 1 − 𝑐 𝐴 = 1 − exp(−𝑘𝜏) (2)
𝐴,0

This results with kτ = 1 in a conversion of 63.2%

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SOLUTIONS TUTORIALS SESSION 1

1.5

Species A reacts according to second order kinetics and in a single reactor. The conversion is 95%. We
buy a second reactor unit identical to the first. For the same conversion, by how much is the capacity
increased if we operate these two units parallel or in series?

a) The reactors are both PFR’s

b) The reactors are both CISTRS

Solution

Conversion for PFR with 2th order reaction:

𝑐𝐴 1
𝜁 =1− =1− (1)
𝑐𝐴,0 1+𝑘𝜏

Conversion for CISTR

𝑐 √1+4𝑘𝑐𝐴,0 𝜏−1
𝜁 =1−𝑐𝐴 = 1− 2𝑘𝑐𝐴,0 𝜏
(2)
𝐴,0

a1) PFR’s parallel

For the same conversion, kτ has to be constant. This means that the capacity (ΦV) has to be doubled to
ensure the same residence time and conversion of a

a2) PFR series

For the same conversion, kτ has to be constant. This means that the capacity (ΦV) has to be doubled to
ensure the same residence time.

b1) CISTR’s parallel

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SOLUTIONS TUTORIALS SESSION 1

For the same conversion, τ has to be constant. This means the capacity((ΦV) has to be doubled to ensure
the same residence time.

b2)

For a cascade of two identically sized CISTR’s we have:

𝑐𝐴,0 −𝑐𝐴,1 𝑐𝐴,1 −𝑐𝐴,2
𝜏= 2
𝑘𝑐𝐴
= 2
𝑘𝑐𝐴
(3)
1 2

Or

𝑘𝐶𝑎0 𝜏 = 𝜁𝑡𝑜𝑡𝑎𝑙 (4)

And for reactor 1 the formula becomes:

1 𝜁
𝑘𝐶𝑎0 𝜏 2 = (1−𝜁𝑎1 2 (5)
𝑎1 )

And for reactor 2:

1 𝜁
𝑘𝐶𝑎1 𝜏 2 = (1−𝜁𝑎2 2 (6)
𝑎2 )

Because 𝜁𝑎1 𝑎𝑛𝑑 𝜁𝑎2 are both unknown it is needed to rewrite the equation.

First rewrite equation (5) to the format of Ca1 = …. As a function of Ca0

Then fill that in into equation (6) to get Ca2 = …… As a function of Ca0.

Now Ca2 can be filled in in equation (4) and the capacity increase can be found.

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SOLUTIONS TUTORIALS SESSION 1

1.6

Your company has to CISTR’s of unequal size for producing a specified product formed by homogeneous
first order reaction. How these reactors should be connected to achieve a maximum production rate.

Solution

First order conversion in a CISTR:

𝑐𝐴 1
𝜁 =1− =1− (1)
𝑐𝐴,0 1+𝑘𝜏

Assuming CISTR A has a size twice CISTR B and CISTR B has residence time τ.

Connect A ->B
𝑐𝐴,𝐴 1 𝑐𝐴,0
= → 𝑐𝐴,𝐴 = (2)
𝑐𝐴,0 1+2𝑘𝜏 1+2𝑘𝜏

𝑐𝐴,𝐵 1
𝑐𝐴,𝐴
= 1+𝑘𝜏 (3)

Fill eq. 2 in 3 and rewrite to cA,B

𝐴,0 𝑐
𝑐𝑜𝑢𝑡 = 𝑐𝐴,𝐵 = (1+2𝑘𝜏)(1+𝑘𝜏) (4)

Connect B -> A
𝑐𝐴,𝐵 1 𝐴,0 𝑐
𝑐𝐴,0
= 1+𝑘𝜏 → 𝑐𝐴,𝐵 = 1+𝑘𝜏 (5)

𝑐𝐴,𝐴 1
𝑐𝐴,𝐵
= 1+2𝑘𝜏 (6)

Fill eq 5 in 6 and rewrite to cA,A

𝐴,0 𝑐
𝑐𝑜𝑢𝑡 = 𝑐𝐴,𝐴 = (1+2𝑘𝜏)(1+𝑘𝜏) (7)

Conclusion: it makes no difference in configuration

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SOLUTIONS TUTORIALS SESSION 1

1.7

A liquid stream (ΦV = 0.1 m3/s) containing a reactant A with a concentration of 1000 mol/m3 is supplied
to a CISTR with a volume of 1 m3. In the reactor, A is converted to P in a first order irreversible reaction
AP, for which the reaction rate constant equals 0.1 [1/s]. The liquid phase density of the feed and
product stream are identical.

a) Determine the steady state conversion

To increase the conversion of the reactor, part of the effluent of the CISTR is recycled by means of a
recirculation loop, in which the reaction also takes place (see illustration in tutorial). The recirculation
loop may be considered to be a PFR with a volume of 0.5 m3. The process conditions, such as pressure
and temperature in the recirculation loop are identical to those of the CISTR. The flow through the loop,
Φ0 may be controlled, and tuned to any value by means of a pump.

At a recycle flowrate of Φ0 = 0.25 m3/s , the concentration of A is measured at location D. This turns out
to be 333.7 mol/m3.

b) Determine the concentration of A in point C

c) What would be the conversion of A for the entire setup if the recirculation rate were to become very
(infinitely) large?

Solution

a) Steady state mole balance CISTR with ΦV = ΦV,in = ΦV,out

0 = ∅𝑉 (𝑐𝑖𝑛 − 𝑐𝑜𝑢𝑡 ) − 𝑘𝑐𝑜𝑢𝑡 𝑉𝑅 (1)

Using for residence time:

𝑉𝑅
𝜏= (2)
∅𝑉

Conversion can be calculated by:

𝑐𝑜𝑢𝑡 𝑘𝜏 1
𝜁 =1− 𝑐𝑖𝑛
= 1+𝑘𝜏 = 1+1 = 0.5 (50%) (3)

b) For 1th order reaction is PFR:

𝐴𝐷 𝐷 𝐴 333.7
𝐴𝐶
= exp(−𝑘𝜏) → 𝐴𝑐 = exp(−𝑘𝜏) = 0.5 = 407.6 (4)
exp(0.1∗ )
0.25

c) When increasing the recycle stream to very high values, the differential conversions in the PFR
and CISTR are very low. Looking at the system (CISTR+PFR-recycle) as a whole, it becomes more and

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SOLUTIONS TUTORIALS SESSION 1

more well mixed, when increasing the recycle ratio: The system will behave like a CISTR having a
total volume of VCISTR + VPFR. See below:

A B

o
D
C

The overall conversion can then be calculated using

1.5
𝑘𝜏 0.1∙
𝜁 = 1+𝑘𝜏 = 0.1
1.5 = 0.6 (50%) (5)
1+0.1∙
0.1

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