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 parallel reactions:

𝐴→𝐵
𝐴→𝐶
𝐴 → 2𝐷

ChE 2115: Chemical

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

𝐴→𝐵 Thus
𝐴→𝐶 𝐶𝐷 − 𝐶𝐷0
𝐶𝐴0 − 𝐶𝐴 = 𝐶𝐵 − 𝐶𝐵0 + 𝐶𝐶 − 𝐶𝐶0 +
𝐴 → 2𝐷 2
𝐶𝐷 𝐶𝐷0
𝐶𝐴 + 𝐶𝐵 + 𝐶𝐶 + = 𝐶𝐴0 + 𝐶𝐵0 + 𝐶𝐶0 +
2 2
𝐶𝐴0 − 𝐶𝐴1 = 𝐶𝐵 − 𝐶𝐵0
𝐶𝐴1 − 𝐶𝐴2 = 𝐶𝐶 − 𝐶𝐶0
𝐶𝐷 − 𝐶𝐷0
𝐶𝐴2 − 𝐶𝐴 =
2

ChE 2115: Chemical

Reaction Engineering
Parallel Reactions
EXAMPLE
Consider the parallel reactions shown below. What are the concentrations
of A, D, and U as a function of time?
𝐴 → 𝐷, 𝑟1,𝐷 = 𝑘1 𝐶𝐴
𝐴 → 𝑈, 𝑟2,𝑈 = 𝑘2 𝐶𝐴

ChE 2115: Chemical

Reaction Engineering
Parallel Reactions
Consider the parallel reactions shown below. What are the concentrations of A, D, and U as a function of time?
EXAMPLE 𝐴 → 𝐷, 𝑟1,𝐷 = 𝑘1 𝐶𝐴 , 𝐴 → 𝑈, 𝑟2,𝑈 = 𝑘2 𝐶𝐴

𝑑𝐶𝐴 𝑑𝐶𝐷
𝑟𝐴 = = −𝑘1 𝐶𝐴 − 𝑘2 𝐶𝐴 = 𝑘1 𝐶𝐴
𝑑𝑡 𝑑𝑡
𝑑𝐶𝐴 𝑑𝐶𝐷
= − 𝑘1 + 𝑘2 𝐶𝐴 = 𝑘1 𝐶𝐴0 𝑒 − 𝑘1+𝑘2 𝑡
𝑑𝑡 𝑑𝑡
𝑑𝐶𝐴 𝑑𝐶𝐷 = 𝑘1 𝐶𝐴0 𝑒 − 𝑘1+𝑘2 𝑡 𝑑𝑡
= − 𝑘1 + 𝑘2 𝑑𝑡
𝐶𝐴 𝒌𝟏 𝑪𝑨𝟎
𝐶𝐴 𝑪𝑫 = 𝑪𝑫𝟎 + 𝟏 − 𝒆− 𝒌𝟏 +𝒌𝟐 𝒕
ln = − 𝑘1 + 𝑘2 𝑡 𝒌𝟏 + 𝒌𝟐
𝐶𝐴0
Similarly,
𝑪𝑨 = 𝑪𝑨𝟎 𝒆− 𝒌𝟏+𝒌𝟐 𝒕
𝒌𝟐 𝑪𝑨𝟎
𝑪𝑼 = 𝑪𝑼𝟎 + 𝟏 − 𝒆− 𝒌𝟏 +𝒌𝟐 𝒕
𝒌𝟏 + 𝒌𝟐

ChE 2115: Chemical

Reaction Engineering
Parallel Reactions
For the parallel reactions
𝑪𝑨𝟎
𝒍𝒏 = 𝒌𝟏 + 𝒌𝟐 𝒕
𝐴 → 𝐷, 𝑟1,𝐷 = 𝑘1 𝐶𝐴 𝑪𝑨
y m x
𝐴 → 𝑈, 𝑟2,𝑈 = 𝑘2 𝐶𝐴
𝑪𝑨 = 𝑪𝑨𝟎 𝒆− 𝒌𝟏 +𝒌𝟐 𝒕 𝒌𝟏
𝑪𝑫 − 𝑪𝑫𝟎 = 𝑪𝑨𝟎 − 𝑪𝑨𝟎 𝒆− 𝒌𝟏 +𝒌𝟐 𝒕
𝒌𝟏 + 𝒌𝟐
𝒌𝟏 𝑪𝑨𝟎
𝑪𝑫 = 𝑪𝑫𝟎 + 𝟏 − 𝒆− 𝒌𝟏 +𝒌𝟐 𝒕
𝒌𝟏
𝒌𝟏 + 𝒌𝟐 𝑪𝑫 − 𝑪𝑫𝟎 = 𝑪𝑨𝟎 − 𝑪𝑨
𝒌𝟏 + 𝒌𝟐
𝒌𝟐 𝑪𝑨𝟎
𝑪𝑼 = 𝑪𝑼𝟎 + 𝟏 − 𝒆− 𝒌𝟏 +𝒌𝟐 𝒕
y m x
𝒌𝟏 + 𝒌𝟐

ChE 2115: Chemical

Reaction Engineering
Parallel Reactions
EXAMPLE
Consider the parallel reactions:
𝐴 → 𝐷, 𝑟1,𝐷 = 𝑘1 𝐶𝐴
𝐴 → 𝑈, 𝑟2,𝑈 = 𝑘2 𝐶𝐴

The concentrations of A and D are shown below. Determine the rate

constant of the reactions.
t (min) 0 10 20 30 40 50 60 70
CA (M) 4 3.4 2.89 2.457 2.088 1.775 1.509 1.282
CD (M) 0.2 0.754 1.225 1.625 1.965 2.254 2.5 2.708
ChE 2115: Chemical
Reaction Engineering
Parallel Reactions
EXAMPLE Consider the parallel reactions: 𝐴 → 𝐷, 𝑟1,𝐷 = 𝑘1 𝐶𝐴 , 𝐴 → 𝑈, 𝑟2,𝑈 = 𝑘2 𝐶𝐴 . The concentrations of A
and D are shown below. Determine the rate constant of the reactions.

t (min) 0 10 20 30 40 50 60 70
CA (M) 4 3.4 2.89 2.457 2.088 1.775 1.509 1.282
CD (M) 0.2 0.754 1.225 1.625 1.965 2.254 2.5 2.708

𝐶𝐴0
𝑙𝑛 = 𝑘1 + 𝑘2 𝑡
𝐶𝐴
t (min) 0 10 20 30 40 50 60 70
𝐶𝐴0
ln 0 0.163 0.325 0.487 0.650 0.812 0.975 1.138
𝐶𝐴
𝑠𝑙𝑜𝑝𝑒 = 𝑘1 + 𝑘2 = 0.01625
ChE 2115: Chemical
Reaction Engineering
Parallel Reactions
EXAMPLE Consider the parallel reactions: 𝐴 → 𝐷, 𝑟1,𝐷 = 𝑘1 𝐶𝐴 , 𝐴 → 𝑈, 𝑟2,𝑈 = 𝑘2 𝐶𝐴 . The concentrations of A
and D are shown below. Determine the rate constant of the reactions.

t (min) 0 10 20 30 40 50 60 70 𝑘1 + 𝑘2 = 0.01625
CA (M) 4 3.4 2.89 2.457 2.088 1.775 1.509 1.282 𝑘1
= 0.92296
CD (M) 0.2 0.754 1.225 1.625 1.965 2.254 2.5 2.708
𝑘1 + 𝑘2

𝑘1 = 0.015 𝑚𝑖𝑛−1
𝑘1
𝐶𝐷 − 𝐶𝐷0 = 𝐶 − 𝐶𝐴
𝑘1 + 𝑘2 𝐴0 𝑘2 = 0.00125 𝑚𝑖𝑛−1
CA0-CA 0 0.6 1.11 1.543 1.912 2.225 2.491 2.718
CD-CD0 0 0.554 1.025 1.425 1.765 2.054 2.3 2.508
𝑘1
𝑠𝑙𝑜𝑝𝑒 = = 0.92296
𝑘1 + 𝑘2
ChE 2115: Chemical
Reaction Engineering
Parallel Reactions
𝐴 → 𝐷 (Desired)
𝐴 → 𝑈 (Undesired)

Instantaneous Selectivity, or Related Rates Overall Selectivity

𝑟𝐷 𝑑𝐶𝐷 𝑎𝑙𝑙 𝐷 𝑓𝑜𝑟𝑚𝑒𝑑
𝑆= = 𝑆መ =
𝑟𝑈 𝑑𝐶𝑈 𝑎𝑙𝑙 𝑈 𝑓𝑜𝑟𝑚𝑒𝑑

Overall Fractional Yield

Instantaneous Fractional Yield
𝑑𝐶𝐷 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐷 ∆𝐶𝐷 𝑎𝑙𝑙 𝐷 𝑓𝑜𝑟𝑚𝑒𝑑
𝜑𝐷 = = Φ𝐷 = =
−𝑑𝐶𝐴 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴 −∆𝐶𝐴 𝑎𝑙𝑙 𝐴 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑
𝐶𝐷𝑓
Φ𝐷 =
𝐶𝐴0 − 𝐶𝐴𝑓
𝐶
− ‫𝐴𝐶𝑑 𝐷𝜑 𝑓𝐴 𝐶׬‬
𝐴0
Φ𝐷 =
𝐶𝐴0 − 𝐶𝐴𝑓
ChE 2115: Chemical
Reaction Engineering
Parallel Reactions
EXAMPLE
Consider the two parallel reactions shown. What would be the overall
fractional yield and selectivity of the reaction assuming 90% conversion of
the reactants in a batch reaction. The initial concentration of A is 1 M.
𝑑𝐶𝐷
𝐴 → 𝐷, = 𝑘1 𝐶𝐴 , 𝑘1 = 0.4
𝑑𝑡
𝑑𝐶𝑈
𝐴 → 𝑈, = 𝑘2 𝐶𝐴 2 , 𝑘2 = 0.6
𝑑𝑡

ChE 2115: Chemical

Reaction Engineering
Parallel Reactions
Consider the two parallel reactions shown. What would be the overall fractional yield and selectivity of the reaction assuming 90% conversion of the reactants in a
batch reaction. The initial concentration of A is 1 M.
EXAMPLE 𝑑𝐶𝐷 𝑑𝐶𝑈
𝐴 → 𝐷, = 𝑘1 𝐶𝐴 , 𝑘1 = 0.4, 𝐴 → 𝑈, = 𝑘2 𝐶𝐴 2 , 𝑘2 = 0.6
𝑑𝑡 𝑑𝑡

𝑟𝐷 0.4
𝜑𝐷 = ln 0.4 + 0.6𝐶𝐴 ȁ10.1
−𝑟𝐴 Φ𝐷 = − 0.6
𝑘1 𝐶𝐴 1 − 0.1
𝜑𝐷 = 2 Φ𝐷 = 0.575
𝑘1 𝐶𝐴 + 𝑘2 𝐶𝐴

𝐶𝐴𝑓
− ‫𝐷𝜑 𝐶׬‬ 𝑑𝐶𝐴
Φ𝐷 = 𝐴0 𝑎𝑙𝑙 𝐷 𝑓𝑜𝑟𝑚𝑒𝑑
𝐶𝐴0 − 𝐶𝐴𝑓 𝑆መ =
𝑎𝑙𝑙 𝑈 𝑓𝑜𝑟𝑚𝑒𝑑
0.1 0.4 0.575 0.9
− ‫׬‬1 𝑑𝐶
0.4 + 0.6𝐶𝐴 𝐴 𝑆መ = = 1.35
Φ𝐷 = 0.9 − 0.9 0.575
1 − 0.1

ChE 2115: Chemical

Reaction Engineering
Parallel Reactions
EXAMPLE
Consider the two parallel reactions shown. What would be the overall selectivity of
the reaction at (a) 200C and (b) 400C assuming complete conversion of the
reactants in a batch reaction. The reactant has an initial concentration of 1M.
𝑑𝐶𝐷
𝐴 → 𝐷, = 𝑘1 𝐶𝐴 , 𝑘1 = 0.1 𝑎𝑡 30𝑜 𝐶, 𝐸𝐷 = 20 𝑘𝐽/𝑚𝑜𝑙
𝑑𝑡
𝑑𝐶𝑈
𝐴 → 𝑈, = 𝑘2 𝐶𝐴 , 𝑘2 = 0.1 𝑎𝑡 30𝑜 𝐶, 𝐸𝑈 = 10 𝑘𝐽/𝑚𝑜𝑙
𝑑𝑡

ChE 2115: Chemical

Reaction Engineering
Parallel Reactions
Consider the two parallel reactions shown. What would be the overall selectivity of the reaction at (a) 20 0C and (b) 400C assuming complete conversion of the
reactants in a batch reaction. The reactant has an initial concentration of 1M.
EXAMPLE 𝑑𝐶𝐷 𝑘𝐽 𝑑𝐶𝑈
𝐴 → 𝐷, = 𝑘1 𝐶𝐴 , 𝑘1 = 0.1 𝑎𝑡 30𝑜 𝐶, 𝐸𝐷 = 20 , 𝐴 → 𝑈, = 𝑘2 𝐶𝐴 , 𝑘2 = 0.1 𝑎𝑡 30𝑜 𝐶, 𝐸𝑈 = 10 𝑘𝐽/𝑚𝑜𝑙
𝑑𝑡 𝑚𝑜𝑙 𝑑𝑡

𝐶 𝐶𝐴0 𝑟𝐷 1 𝑘1
− ‫𝐴𝐶𝑑 𝜑 𝑓𝐴 𝐶׬‬ ‫𝑟 𝐶׬‬ 𝑑𝐶𝐴 ‫׬‬0 𝑑𝐶 𝑘1
𝐴0 𝐴𝑓 𝐴 𝑘1 + 𝑘2 𝐴
Φ= = = =
𝐶𝐴0 − 𝐶𝐴𝑓 𝐶𝐴0 − 𝐶𝐴𝑓 1−0 𝑘1 + 𝑘2
𝑘1 0.07629
𝑎 𝑎𝑡 20𝑜 𝐶, = = 0.4662
𝑘1 + 𝑘2 0.07629 + 0.08734
0.4662
𝑆= = 0.8734
1 − 0.4662
𝑜
𝑘1 0.1288
𝑏 𝑎𝑡 40 𝐶, = = 0.5316
𝑘1 + 𝑘2 0.1288 + 0.1135
0.5316
𝑆= = 1.135
1 − 0.5316 ChE 2115: Chemical
Reaction Engineering
Parallel Reactions

• If 𝐸𝐷 > 𝐸𝑈 , the rate of the desired reaction increases more rapidly with increasing temperature
compared to the undesired reaction. Consequently, the reaction should be operated at the
maximum possible temperature to maximize the yield/selectivity towards the desired product.

• If 𝐸𝐷 < 𝐸𝑈 , The reaction should be operated at the low temperature to maximize the
yield/selectivity towards the desired product but not so low that the desired reaction does not
proceed to any significant extent.

ChE 2115: Chemical

Reaction Engineering
Parallel Reactions, Continuous Reactors
𝐴 → 𝐷 (Desired)
𝐴 → 𝑈 (Undesired)

Instantaneous Fractional Yield

𝑑𝐶𝐷 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐷
𝜑𝐷 = =
−𝑑𝐶𝐴 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 𝑜𝑓 𝐴

Overall Fractional Yield, CSTR

Overall Fractional Yield, PFR
𝐶𝐴𝑓 Φ𝐷 = 𝜑𝐷 evaluated at exit condition
− ‫𝐴𝐶𝑑 𝐷𝜑 𝐶׬‬
𝐴0
Φ𝐷 =
𝐶𝐴0 − 𝐶𝐴𝑓

ChE 2115: Chemical

Reaction Engineering
Continuously Stirred Tank Reactor
EXAMPLE
Liquid reactant A decomposes by the reaction shown below:

A feed of aqueous A (CA0 = 40 mol/m3) enters a reactor, decomposes, and a mixture of

A, R, and S leaves. Find CR, CA, and τ for XA = 0.9 in a (i) mixed flow reactor (ii) plug flow
reactor

ChE 2115: Chemical

Reaction Engineering
Continuously Stirred Tank Reactor
Liquid reactant A decomposes by the reaction shown below. A feed of aqueous A (CA0 = 40 mol/m3) enters a reactor,
EXAMPLE decomposes, and a mixture of A, R, and S leaves. Find CR, CA, and τ for XA = 0.9 in a (i) mixed flow reactor (ii) plug flow
reactor

−𝑟𝐴 = 0.4𝐶𝐴2 + 2𝐶𝐴 𝐶𝑅𝑓

Φ𝑅 =
𝐶𝐴0 − 𝐶𝐴𝑓
For MFR
𝑉 ∆𝑋𝐴 𝐶𝑅𝑓
𝜏 = = 𝐶𝐴0 0.4444 =
𝐹 −𝑟𝐴 40 − 4
0.9 − 0 𝐶𝑅𝑓 = 16 𝑚𝑜𝑙/𝑚3
𝜏 = 40 2
0.4 × 40 1 − 0.9 + 2 × 40 1 − 0.9
𝜏 = 2.5 𝑚𝑖𝑛
𝐶𝐴 = 𝐶𝐴0 1 − 𝑋𝐴 = 40 1 − 0.9
𝐶𝐴 = 4 𝑚𝑜𝑙/𝑚3
𝑑𝐶𝑅
Φ𝑅 = 𝜑 𝑅 =
−𝑑𝐶𝐴
𝑘1 𝐶𝐴2 0.4 4 2
Φ𝑅 = = = 0.4444 ChE 2115: Chemical
𝑘1 𝐶𝐴2 + 𝑘2 𝐶𝐴 0.4 4 2 + 2 4 Reaction Engineering
Continuously Stirred Tank Reactor
Liquid reactant A decomposes by the reaction shown below. A feed of aqueous A (CA0 = 40 mol/m3) enters a reactor,
EXAMPLE decomposes, and a mixture of A, R, and S leaves. Find CR, CA, and τ for XA = 0.9 in a (i) mixed flow reactor (ii) plug flow
reactor

−𝑟𝐴 = 0.4𝐶𝐴2 + 2𝐶𝐴 4 0.4𝐶𝐴2

− ‫׬‬40 𝑑𝐶
0.4𝐶𝐴2 + 2𝐶𝐴 𝐴
For PFR Φ𝑅 =
40 − 4
𝑉 𝑑𝑋𝐴 𝐶𝑅𝑓
𝜏= = 𝐶𝐴0 න
𝐹 −𝑟𝐴 Φ𝑅 =
𝐶𝐴0 − 𝐶𝐴𝑓
0.9
𝑑𝑋𝐴 Φ𝑅 = 0.7765
𝜏 = 40 න 2
0 0.4 × 40 1 − 𝑋𝐴 + 2 × 40 1 − 𝑋𝐴 𝐶𝑅𝑓
𝜏 = 0.3466 𝑚𝑖𝑛 0.7765 =
40 − 4
𝐶𝐴 = 𝐶𝐴0 1 − 𝑋𝐴 = 40 1 − 0.9 𝐶𝑅𝑓 = 28.0 𝑚𝑜𝑙/𝑚3
𝐶𝐴 = 4 𝑚𝑜𝑙/𝑚3
𝐶
− ‫𝐴𝐶𝑑 𝑅𝜑 𝑓𝐴 𝐶׬‬
𝐴0
Φ𝑅 =
𝐶𝐴0 − 𝐶𝐴𝑓
ChE 2115: Chemical
Reaction Engineering
Contacting Patterns – Noncontinuous Reactors

ChE 2115: Chemical

Reaction Engineering
Contacting Patterns – Continuous Reactors

ChE 2115: Chemical

Reaction Engineering
Continuously Stirred Tank Reactor
EXAMPLE
Consider the parallel reaction where D is the desired product and U is the undesired
one:

𝑑𝐶𝐷
𝐴 + 𝐵 → 𝐷 + 𝐸, = 𝑘1 𝐶𝐴 0.3 𝐶𝐵 1.5
𝑑𝑡
𝑑𝐶𝑈
𝐴 + 𝐵 → 𝑈 + 𝑉, = 𝑘2 𝐶𝐴1.8 𝐶𝐵 0.5
𝑑𝑡

From a standpoint of favorable product distribution, determine the most desirable

contact scheme for a continuous process.

ChE 2115: Chemical

Reaction Engineering
Continuously Stirred Tank Reactor
𝑑𝐶𝐷 𝑑𝐶𝑈
Consider the parallel reaction where D is the desired product and U is the undesired one: 𝐴 + 𝐵 → 𝐷 + 𝐸, = 𝑘1 𝐶𝐴 0.3 𝐶𝐵 1.5 , 𝐴 + 𝐵 → 𝑈 + 𝑉, =
EXAMPLE 𝑑𝑡
𝑘2 𝐶𝐴1.8 𝐶𝐵 0.5 . From a standpoint of favorable product distribution, determine the most desirable contact scheme for a continuous process.
𝑑𝑡

𝑑𝐶𝐷
= 𝑘1 𝐶𝐴 0.3 𝐶𝐵 1.5
𝑑𝑡
𝑑𝐶𝑈
= 𝑘2 𝐶𝐴1.8 𝐶𝐵 0.5
𝑑𝑡
𝑑𝐶𝐷 𝑘1 −1.5
= 𝐶𝐴 𝐶𝐵
𝑑𝐶𝑈 𝑘2
We want to keep CA low, and CB high.

ChE 2115: Chemical

Reaction Engineering
Try These!!!
Using separate feeds of A and B sketch the contacting pattern and reactor conditions which would best
promote the formation of product R for the following systems of elementary reactions.

ChE 2115: Chemical

Reaction Engineering