Application 4

An irreversible reaction A → 3B ( 𝑟 = 𝑘𝐶𝐴 ) takes place in a batch reactor under a constant pressure of 1.8 atm
with an initial charge containing pure A. We notice that the volume then increases by 70% in 12 minutes.
1. Calculate the reaction rate constant.
2. If this reaction is at constant volume, what will be the time required to obtain a pressure of 2.5 atm if the
initial pressure is 1.8 atm?

Solution:

1. Calculate the reaction rate constant.

Batch reactor, P=1,8 atm and pure A:

When no spatial variations in reaction rate (rA) exist, the mole balance on species A for a batch system is given by
the following equation:
𝑑𝑁𝐴
= 𝑟𝐴 𝑉
𝑑𝑡

The number of moles of A in the reactor after a conversion X has been achieved is:

NA = NA0 -NA0 . X = NA0.(1- X )

Combining the above Equations:

𝑑𝑋
−𝑁𝐴0 = (𝑟𝐴 )𝑉
𝑑𝑡

Rearranging:
𝑑𝑋
𝑑𝑡 = 𝑁𝐴0
−𝑟𝐴 𝑉
Substititing –rA by kCA:
𝑑𝑋 𝑑𝑋
𝑑𝑡 = 𝑁𝐴0 = 𝑁𝐴0
𝑘𝐶𝐴𝑉 𝑘𝑁𝐴

On the other hand:

𝑁𝐴0 1
=
𝑁𝐴 1−𝑋
Then:
1 𝑑𝑋
𝑑𝑡 =
𝑘1−𝑋
Integrating:
𝑋
1 𝑑𝑋
න 𝑑𝑡 = න
𝑘 1−𝑋
0

1 1
𝑡 = − [ln 1 − 𝑋 − ln(1)] = − ln(1 − 𝑋)
𝑘 𝑘
ln(1 − 𝑋)
𝑘=−
𝑡
From this equation ,we deduce the relation between the change in volume and the conversion corresponding to
time 𝑡𝑠 = 12𝑚𝑖𝑛

𝑇 𝑃
- Gas Phase: 𝑉 ′ = 𝑉0′ 1 + 𝜀𝑋 . .
𝑇0 𝑃0

Isothermal reaction: T=T0

𝑉 ′ = 𝑉0′ 1 + 𝜀𝑋
Constant pressure: P=P0

𝐶ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑓𝑜𝑟 𝑐𝑜𝑚𝑝𝑙𝑒𝑡𝑒 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛

𝜀= 𝜀=2
𝑇𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑓𝑒𝑑

On the other hand, the volume increases by 70% in 12 minutes :

𝑉 ′ = 𝑉0′ + 0,7𝑉0′
0,7
1,7 = 1 + 𝜀𝑋 𝑋= = 0,35
2
 ln 1 − 0,35
𝑘=− = 0,0358 𝑚𝑖𝑛−1
12

2. If this reaction is at constant volume, what will be the time required to obtain a pressure of 2.5 atm if the
initial pressure is 1.8 atm?

In this case:
𝑃0
′
𝑉0 = 𝑉0′ 1 + 𝜀𝑋 .
𝑃
1 𝑃
𝑋= − 1 = 0,194
2 𝑃0

The residence time corresponding to this conversion:

1 1
𝑡 = − ln 1 − 𝑋 = − ln 1 − 0,194 = 6 𝑚𝑖𝑛
𝑘 0,0358
Application 5
Consider the liquid phase chemical reaction: A→2B (k= 0.38 min-1).
1. If performed in a CSTR of 1.8 L with CA0 =0.187mol/L. Calculate the conversion rate of A for a feed volume
flow rate V’0=0.5L/min. Assuming reaction is first order reaction in A.
2. Calculate the molar flow rate of B at the output of the CSTR.
3. If this reaction is carried out in a PFR having the same volume and same flow rate as the SCTR:
a. Calculate the conversion rate of A as well as the molar flow rate of B at the exit of this PFR.
b. What feed rate should be chosen to obtain the same conversion of A as in the CSTR.

Solution

1. If performed in a CSTR of 1.8 L with CA0 =0.187mol/L. Calculate the conversion rate of A for a feed rate
FA0=0.5L/min. Assuming reaction is first order reaction in A.
 A→2B

–rA = kCA , V=1,8 L, V’0=0.5 L/min, CA0 = 0,187 mol/L, k= 0.38 min-1

Let’s consider a first-order irreversible reaction for which the rate law is:

−𝑟𝐴 = 𝑘𝐶𝐴

For liquid-phase reactions, there is no volume change during the course of the reaction, so we can use the
following Equation to relate concentration and conversion (Stoichiometry):

𝐹𝐴 = 𝐹𝐴0 (1 − 𝑋)

𝐶𝐴 𝑉′ = 𝐶𝐴0 𝑉′(1 − 𝑋)

𝐶𝐴 𝑉′ = 𝐶𝐴0 𝑉′(1 − 𝑋)

𝐶𝐴 = 𝐶𝐴0 (1 − 𝑋)
In case of CSTR, the design equation is writtens as following:

𝐹𝐴0 𝑋
𝑉= 𝐶𝐴0 𝑉′𝑋 𝑉 𝐶𝐴0 𝑋
−𝑟𝐴 𝑉=
On the other hand: 𝜏= =
−𝑟𝐴 𝑉′ −𝑟𝐴
𝐹𝐴0 = 𝐶𝐴0 𝑉′

𝐶𝐴0 𝑋 𝐶𝐴0 𝑋 𝐶𝐴0 𝑋 𝑋 𝑉 1,8

𝜏= = = = = = = 3,6 𝑚𝑖𝑛
−𝑟𝐴 𝑘𝐶𝐴 𝑘𝐶𝐴0 (1 − 𝑋) 𝑘 (1 − 𝑋) 𝑉′ 0,5

Rearranging:
𝜏𝑘 3,6 ∗ 0,38
𝑋= = = 0,577
1 + 𝜏𝑘 1 + 3,6 ∗ 0,38

2. Calculate the molar flow rate of B at the output of the CSTR.

The progress table is represented as following:

A----------------------2B

t=0 CA0 0

tX CA0-XCA0 2CA0X

Then:

𝐹𝐵 = 2𝐶𝐴0 𝑋𝑉 ′ = 2 ∗ 0,187 ∗ 0,577 ∗ 0,5 = 0,108 𝑚𝑜𝑙/𝑚𝑖𝑛

3. If this reaction is carried out in a PFR having the same volume and same flow rate as the SCTR:
a. Calculate the conversion rate of A as well as the molar flow rate of B at the exit of this PFR.
In case of PFR, the mole balance equation is written as following:
𝑑𝐹𝐴
𝑟𝐴 =
𝑑𝑉
We substitute FA by CA.V’:
𝑉′𝑑𝐶𝐴
𝑟𝐴 =
𝑑𝑉
Rearranging:
𝑉′𝑑𝐶𝐴
𝑑𝑉 =
𝑟𝐴
𝐶𝐴 𝐶𝐴0
𝑉′𝑑𝐶𝐴 𝑉′𝑑𝐶𝐴
න 𝑑𝑉 = න = න
𝑟𝐴 −𝑟𝐴
𝐶𝐴0 𝐶𝐴
𝐶𝐴0
𝑑𝐶𝐴
𝑉 = 𝑉′ න
−𝑟𝐴
𝐶𝐴
𝐶𝐴0
𝑉 𝑑𝐶𝐴
𝜏= = න
𝑉′ −𝑟𝐴
𝐶𝐴
We substitute -rA by k.CA:
𝐶𝐴0
𝑑𝐶𝐴
𝜏= න
𝑘𝐶𝐴
𝐶𝐴

1 𝐶𝐴0
𝜏= 𝑙𝑛
𝑘 𝐶𝐴

𝐶𝐴0
𝑒 𝑘𝜏 =
𝐶𝐴

𝐶𝐴 = 𝐶𝐴0 𝑒 −𝑘𝜏

Substituting CA by CA0(1-X):
𝐶𝐴0 (1 − 𝑋) = 𝐶𝐴0 𝑒 −𝑘𝜏

(1 − 𝑋) = 𝑒 −𝑘𝜏
𝑋 = 1 − 𝑒 −𝑘𝜏
𝑋 = 1 − 𝑒 −0,38∗3,6 = 0,745
 𝐹𝐵 = 2𝐶𝐴0 𝑋𝑉 ′ = 2 ∗ 0,187 ∗ 0,745 ∗ 0,5 = 0,139 𝑚𝑜𝑙/𝑚𝑖𝑛

b. What feed volume flow rate should be chosen to obtain the same conversion of A as in the CSTR.

in the CSTR, the conversion of A is 0,577

We know that:
(1 − 𝑋) = 𝑒 −𝑘𝜏

−𝑘𝜏 = ln(1 − 𝑋)
𝑉
−𝑘 = ln(1 − 𝑋)
𝑉′
𝑘𝑉
𝑉′ =−
ln(1 − 𝑋)
0,38 ∗ 1,8
𝑉′ =− = 0,79 𝐿
ln 1 − 0,577