COMPLEX REACTIONS

ChE 2115: Chemical Reaction Engineering

Basil James S Santos

Complex Reactions

Series Parallel
𝐴→𝐵→𝐶 𝐴 → 𝐵, 𝐴 → 𝐶

Reversible Combination
𝐴⇄𝐵 𝐴+𝐵 →𝐶

𝑁2 + 3𝐻2 ⇄ 2𝑁𝐻3 𝐵+𝐶 →𝐷

ChE 2115: Chemical

Reaction Engineering
Stoichiometry (Material Balances)
• Assign initial (subscript o) and final concentration (no subscript) symbols for all
participants.

• For each step in the complex reaction, use the coefficients in the balanced
chemical equation to derive a material balance for each participant. In case the
participant is involved in more than one step, use intermediate concentration
symbols (using consecutive subscripts) for all the steps where the participant is
involved.

• Use algebra, using all material balances to eliminate all the intermediate
concentrations for all participants. The resulting equation(s) will be the final
material balance equation(s).

ChE 2115: Chemical

Reaction Engineering
Complex Reaction
EXAMPLE

Do a material balance on the following series reactions:

𝐴 → 𝐵 → 2𝐶

ChE 2115: Chemical

Reaction Engineering
Complex Reaction
EXAMPLE Do a material balance on the following series reactions:
𝐴 → 𝐵 → 2𝐶

𝐴→𝐵
𝐵 → 2𝐶

𝐶𝐴0 − 𝐶𝐴 = 𝐶𝐵1 − 𝐶𝐵0

𝐶𝐶 − 𝐶𝐶0
𝐶𝐵1 − 𝐶𝐵 =
2
Thus
𝐶𝐶 − 𝐶𝐶0
𝐶𝐴0 − 𝐶𝐴 + 𝐶𝐵1 − 𝐶𝐵 = 𝐶𝐵1 − 𝐶𝐵0 +
2
𝐶𝐶 𝐶𝐶0
𝐶𝐴 + 𝐶𝐵 + = 𝐶𝐴0 + 𝐶𝐵0 +
2 2
ChE 2115: Chemical
Reaction Engineering
Series Reactions
EXAMPLE
Consider the series reactions shown below. What are the concentrations
of A and B as a function of time?
𝐴 → 𝐵, −𝑟1,𝐴 = 𝑘1 𝐶𝐴
𝐵 → 2𝐶, −𝑟1,𝐵 = 𝑘2 𝐶𝐵

ChE 2115: Chemical

Reaction Engineering
Series Reactions
Consider the series reactions shown below. What are the concentrations of A and B as a function of time?
EXAMPLE 𝐴 → 𝐵, −𝑟1,𝐴 = 𝑘1 𝐶𝐴 , 𝐵 → 2𝐶, −𝑟1,𝐵 = 𝑘2 𝐶𝐵

𝑑𝐶𝐴 𝑢 = 𝑒 ‫𝑘 ׬‬2 𝑑𝑡 = 𝑒 𝑘2𝑡

= −𝑘1 𝐶𝐴
𝑑𝑡
𝑑𝐶𝐵 𝐶𝐵 𝑒 𝑘2𝑡 = න 𝑒 𝑘2𝑡 𝑘1 𝐶𝐴0 𝑒 −𝑘1𝑡 𝑑𝑡
= 𝑘1 𝐶𝐴 − 𝑘2 𝐶𝐵
𝑑𝑡
𝑑𝐶𝐶 𝐶𝐵 𝑒 𝑘2𝑡 = න 𝑘1 𝐶𝐴0 𝑒 𝑘2 −𝑘1 𝑡
𝑑𝑡
= 2𝑘2 𝐶𝐵
𝑑𝑡
If 𝑘2 ≠ 𝑘1
𝑪𝑨 = 𝑪𝑨𝟎 𝒆−𝒌𝟏𝒕 𝑘 1 𝐶𝐴0 𝑒 𝑘2 −𝑘1 𝑡

𝑑𝐶𝐵 𝐶𝐵 𝑒 𝑘2𝑡 = +𝐶
𝑘2 − 𝑘1
= 𝑘1 𝐶𝐴 − 𝑘2 𝐶𝐵
𝑑𝑡 𝑎𝑡 𝑡 = 0, 𝐶𝐵 = 𝐶𝐵0
𝑑𝐶𝐵 𝑘1 𝐶𝐴0
+ 𝑘2 𝐶𝐵 = 𝑘1 𝐶𝐴0 𝑒 −𝑘1𝑡 𝐶𝐵0 = +𝐶
𝑑𝑡 𝑘2 − 𝑘1
ChE 2115: Chemical
Reaction Engineering
Series Reactions
Consider the series reactions shown below. What are the concentrations of A and B as a function of time?
EXAMPLE 𝐴 → 𝐵, −𝑟1,𝐴 = 𝑘1 𝐶𝐴 , 𝐵 → 2𝐶, −𝑟1,𝐵 = 𝑘2 𝐶𝐵

𝑘1 𝐶𝐴0
𝐶=− + 𝐶𝐵0
𝑘2 − 𝑘1
𝑘2 𝑡
𝑘1 𝐶𝐴0 𝑒 𝑘2−𝑘1 𝑡 𝑘1 𝐶𝐴0
𝐶𝐵 𝑒 = − + 𝐶𝐵0
𝑘2 − 𝑘1 𝑘2 − 𝑘1
𝒌𝟏 𝑪𝑨𝟎 𝒆−𝒌𝟏 𝒕 − 𝒆−𝒌𝟐 𝒕
𝑪𝑩 = + 𝑪𝑩𝟎 𝒆−𝒌𝟐 𝒕
𝒌 𝟐 − 𝒌𝟏
If 𝐶𝐵0 = 0
𝑘1 𝐶𝐴0 𝑒 −𝑘1 𝑡 − 𝑒 −𝑘2 𝑡
𝐶𝐵 =
𝑘2 − 𝑘1
Note: CC can be determined by using stoichiometry
𝐶𝐶 𝐶𝐶0
𝐶𝐴 + 𝐶𝐵 + = 𝐶𝐴0 + 𝐶𝐵0 + ChE 2115: Chemical
2 2
Reaction Engineering
Series Reactions

ChE 2115: Chemical

Reaction Engineering
Series Reactions
EXAMPLE
Consider the series reactions shown below. At what time will the
concentration of B maximum? Assume there is no specie B initially.
𝐴 → 𝐵, −𝑟1,𝐴 = 𝑘1 𝐶𝐴
𝐵 → 2𝐶, −𝑟1,𝐵 = 𝑘2 𝐶𝐵

ChE 2115: Chemical

Reaction Engineering
Series Reactions
Consider the series reactions shown below. At what time will the concentration of B maximum? Assume there
EXAMPLE
is no specie B initially. 𝐴 → 𝐵, −𝑟1,𝐴 = 𝑘1 𝐶𝐴 , 𝐵 → 2𝐶, −𝑟1,𝐵 = 𝑘2 𝐶𝐵

𝑘1 𝐶𝐴0 𝑒 −𝑘1𝑡 − 𝑒 −𝑘2𝑡

𝐶𝐵 =
𝑘2 − 𝑘1
Maximum CB can be calculated using
𝑑𝐶𝐵 𝑑 𝑘1 𝐶𝐴0 𝑒 −𝑘1𝑡 − 𝑒 −𝑘2𝑡
= =0
𝑑𝑡 𝑑𝑡 𝑘2 − 𝑘1
−𝑘1 𝑒 −𝑘1𝑡𝑜𝑝𝑡 + 𝑘2 𝑒 −𝑘2𝑡𝑜𝑝𝑡 = 0
𝑘2
= 𝑒 𝑘2−𝑘1 𝑡𝑜𝑝𝑡 𝒌𝟐
𝑘1 𝐥𝐧
𝒌𝟏
𝒕𝒐𝒑𝒕 =
𝒌 𝟐 − 𝒌𝟏
ChE 2115: Chemical
Reaction Engineering
Series Reactions in a PFR
If the series reaction were carried out in a PFR, the results would essentially be those of a batch
reactor where we replaced the time variable “t” with the spacetime, “τ”.

𝐴 → 𝐵, −𝑟1,𝐴 = 𝑘1 𝐶𝐴 , 𝐵 → 2𝐶, −𝑟1,𝐵 = 𝑘2 𝐶𝐵

For a batch reactor

𝑪𝑨 = 𝑪𝑨𝟎 𝒆−𝒌𝟏 𝒕
𝒌𝟏 𝑪𝑨𝟎 𝒆−𝒌𝟏 𝒕 − 𝒆−𝒌𝟐𝒕
𝑪𝑩 =
𝒌𝟐 − 𝒌𝟏

For a PFR
𝑪𝑨 = 𝑪𝑨𝟎 𝒆−𝒌𝟏 𝝉
𝒌𝟏 𝑪𝑨𝟎 𝒆−𝒌𝟏 𝝉 − 𝒆−𝒌𝟐 𝝉
𝑪𝑩 =
𝒌𝟐 − 𝒌𝟏

ChE 2115: Chemical

Reaction Engineering
Series Reactions in a PFR
Maximum CB can be calculated using
𝑑𝐶𝐵 𝑑 𝑘1 𝐶𝐴0 𝑒 −𝑘1𝜏 − 𝑒 −𝑘2𝜏
= =0
𝑑𝜏 𝑑𝜏 𝑘2 − 𝑘1
𝒌𝟐
𝐥𝐧
𝒌𝟏
𝝉𝒐𝒑𝒕 =
𝒌𝟐 − 𝒌𝟏

ChE 2115: Chemical

Reaction Engineering
Series Reactions
EXAMPLE
The series reactions listed are to be carried out in a CSTR.
𝐴 → 𝐵, −𝑟1,𝐴 = 𝑘1 𝐶𝐴
𝐵 → 2𝐶, −𝑟1,𝐵 = 𝑘2 𝐶𝐵
(a) Determine the exit concentrations from the CSTR.
(b) Find the value of the space time τ that will maximize the concentration of B.

ChE 2115: Chemical

Reaction Engineering
Series Reactions
The series reactions listed are to be carried out in a CSTR.𝐴 → 𝐵, −𝑟1,𝐴 = 𝑘1 𝐶𝐴 , 𝐵 → 2𝐶, −𝑟1,𝐵 = 𝑘2 𝐶𝐵 (a)
EXAMPLE Determine the exit concentrations from the CSTR. (b) Find the value of the space time τ that will maximize the
concentration of B.

In a CSTR, mass balance should be used. −𝐹𝐶𝐵 + 𝑉𝑟𝐵 = 0 −𝐹𝐶𝐶 + 𝑉𝑟𝐶 = 0

Assuming steady-state with no B and C in −𝐹𝐶 + 𝑉 𝑘 𝐶 − 𝑘 𝐶 = 0
𝐵 𝐴 𝐴 𝐵 𝐵
the feed stream. 𝑉𝑘𝐴 𝐶𝐴
𝐹𝐶𝐴0 − 𝐹𝐶𝐴 + 𝑉𝑟𝐴 = 0 𝐶𝐵 =
𝐹 + 𝑉𝑘𝐵
𝐹𝐶𝐴0 − 𝐹𝐶𝐴 − 𝑉𝑘𝐴 𝐶𝐴 = 0 𝜏𝑘𝐴
𝐶𝐵 = 𝐶𝐴
𝐹𝐶𝐴0 1 + 𝜏𝑘 𝐵
𝐶𝐴 = 𝝉𝒌𝑨 𝑪𝑨𝟎
𝐹 + 𝑉𝑘𝐴 𝑪𝑩 =
𝑪𝑨𝟎 𝟏 + 𝝉𝒌𝑨 𝟏 + 𝝉𝒌𝑩
𝑪𝑨 =
𝟏 + 𝝉𝒌𝑨

CC can be determined by either using another mass balance, or by using stoichiometry.

𝐶𝐶 𝐶𝐶0
𝐶𝐴 + 𝐶𝐵 + = 𝐶𝐴0 + 𝐶𝐵0 + ChE 2115: Chemical
2 2 Reaction Engineering
Series Reactions
The series reactions listed are to be carried out in a CSTR.𝐴 → 𝐵, −𝑟1,𝐴 = 𝑘1 𝐶𝐴 , 𝐵 → 2𝐶, −𝑟1,𝐵 = 𝑘2 𝐶𝐵 (a)
EXAMPLE Determine the exit concentrations from the CSTR. (b) Find the value of the space time τ that will maximize the
concentration of B.

𝜏𝑘𝐴 𝐶𝐴0
𝐶𝐵 =
1 + 𝜏𝑘𝐴 1 + 𝜏𝑘𝐵
𝑑𝐶𝐵 1+𝜏𝑘𝐴 1+𝜏𝑘𝐵 𝑘𝐴 𝐶𝐴0 −𝜏𝑘𝐴 𝐶𝐴0 1+𝜏𝑘𝐴 𝑘𝐵 + 1+𝜏𝑘𝐵 𝑘𝐴
= =0
𝑑𝜏 1+𝜏𝑘𝐴 1+𝜏𝑘𝐵 2
𝟏
𝝉𝒐𝒑𝒕 =
𝒌𝟏 𝒌𝟐

ChE 2115: Chemical

Reaction Engineering