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
Reaction Equilibrium
Consider the reaction 𝑁2 𝑂4 ⇄ 2𝑁𝑂2

At equilibrium,
rate of forward reaction is equal to rate of backward reaction.
ChE 2115: Chemical
Reaction Engineering
Reaction Equilibrium
Equilibrium Constant (Keq)
𝑎𝐴 + 𝑏𝐵 ⇌ 𝑐𝐶 + 𝑑𝐷
𝐶𝑐 𝐷𝑑
𝐾𝑒𝑞 =
𝐴𝑎 𝐵𝑏

For the reaction 𝑁2 𝑂4 ⇄ 2𝑁𝑂2

𝑁𝑂2 2
𝐾𝑒𝑞 =
𝑁2 𝑂4

ChE 2115: Chemical

Reaction Engineering
Reaction Equilibrium
EXAMPLE
At 1285 oC, the equilibrium constant for the reaction 𝐵𝑟2 𝑔 ⇄ 2𝐵𝑟 𝑔 is
𝐾𝑐 = 1.04 × 10−3 . A 0.200-L vessel containing an equilibrium mixture of
the gases has 0.245 g Br2(g) in it. What is the mass of Br(g) in the vessel?
Atomic mass of Bromine is 79.9 g/mol.

ChE 2115: Chemical

Reaction Engineering
Reaction Equilibrium
At 1285 oC, the equilibrium constant for the reaction 𝐵𝑟2 𝑔 ⇄ 2𝐵𝑟 𝑔 is 𝐾𝑐 = 1.04 × 10−3 . A 0.200-L vessel containing an
EXAMPLE equilibrium mixture of the gases has 0.245 g Br2(g) in it. What is the mass of Br(g) in the vessel? Atomic mass of Bromine is 79.9
g/mol.

0.245 𝑔 𝑛𝐵𝑟
𝑛𝐵𝑟2 159.8 𝑔/𝑚𝑜𝑙 𝐵𝑟 =
𝑉
𝐵𝑟2 = = 𝑚𝐵𝑟
𝑉 0.200 𝐿
𝐵𝑟2 = 7.666 × 10−3 𝑀 79.9 𝑔/𝑚𝑜𝑙
2.82 × 10−3 𝑀 =
0.200 𝐿
𝑚 = 0.045 𝑔
𝐵𝑟 2
𝐾𝑐 =
𝐵𝑟2
2
𝐵𝑟
1.04 × 10−3 =
7.666 × 10−3
𝐵𝑟 = 2.82 × 10−3 𝑀
ChE 2115: Chemical
Reaction Engineering
Reaction Equilibrium
EXAMPLE
For the equilibrium 𝐵𝑟2 𝑔 + 𝐶𝑙2 𝑔 ⇄ 2𝐵𝑟𝐶𝑙 𝑔 at 400 K, 𝐾𝑐 = 7.0. If
0.25 mol of Br2 and 0.55 mol of Cl2 are introduced into a 4.0-L container at
400 K, what will be the equilibrium concentrations of Br2, Cl2, and BrCl?

ChE 2115: Chemical

Reaction Engineering
Reaction Equilibrium
For the equilibrium 𝐵𝑟2 𝑔 + 𝐶𝑙2 𝑔 ⇄ 2𝐵𝑟𝐶𝑙 𝑔 at 400 K, 𝐾𝑐 = 7.0. If 0.25 mol of Br2 and 0.55 mol of Cl2 are introduced
EXAMPLE into a 4.0-L container at 400 K, what will be the equilibrium concentrations of Br2, Cl2, and BrCl?

Br2 Cl2 2BrCl

I 0.0625 0.1375
C -x -x 2x
E 0.0625 - x 0.1375 - x 2x

𝐵𝑟𝐶𝑙 2 𝐵𝑟2 𝑒𝑞 = 0.0146 𝑀

𝐾𝑐 =
𝐵𝑟2 𝐶𝑙2 𝐶𝑙2 𝑒𝑞 = 0.0896 𝑀
2𝑥 2 𝐵𝑟𝐶𝑙 𝑒𝑞 = 0.0958 𝑀
7.0 =
0.0625 − 𝑥 0.1375 − 𝑥
𝑥 = 0.4188, 0.04788
ChE 2115: Chemical
Reaction Engineering
Reaction Equilibrium
For the equilibrium 𝐵𝑟2 𝑔 + 𝐶𝑙2 𝑔 ⇄ 2𝐵𝑟𝐶𝑙 𝑔 at 400 K, 𝐾𝑐 = 7.0. If 0.25 mol of Br2 and 0.55 mol of Cl2 are introduced
EXAMPLE into a 4.0-L container at 400 K, what will be the equilibrium concentrations of Br2, Cl2, and BrCl?

𝐶𝐵𝑟2 = 𝐶𝐵𝑟2,0 1 − 𝑋𝐵𝑟2 𝐵𝑟𝐶𝑙 2

𝐾𝑐 =
𝐶𝐵𝑟2 = 0.0625 1 − 𝑋𝐵𝑟2 𝐵𝑟2 𝐶𝑙2
1 2
𝐶𝐶𝑙2 = 𝐶𝐵𝑟2,0 𝑀𝐶𝑙2 ,𝐵𝑟2 − 𝑋𝐵𝑟2 0.125𝑋𝐵𝑟2
1 7.0 =
11
11 0.0625 1 − 𝑋𝐵𝑟2 0.0625 − 𝑋𝐵𝑟2
5
𝐶𝐶𝑙2 = 0.0625 − 𝑋𝐵𝑟2
5 𝑋𝐵𝑟2 = 6.70, 0.766
2
𝐶𝐵𝑟𝐶𝑙 = 𝐶𝐵𝑟𝐶𝑙,0 + 𝐶𝐵𝑟2,0 𝑋𝐵𝑟2
1 𝐵𝑟2 = 0.0146 𝑀
𝑒𝑞
𝐶𝐵𝑟𝐶𝑙 = 0.125𝑋𝐵𝑟2
𝐶𝑙2 𝑒𝑞 = 0.0896 𝑀
𝐵𝑟𝐶𝑙 𝑒𝑞 = 0.0958 𝑀 ChE 2115: Chemical
Reaction Engineering
Reversible Reaction
2
Consider the reversible, elementary reaction 𝑘1 𝐶𝐶,𝑒𝑞
= = 𝐾𝑒𝑞
𝐴 + 𝐵 ↔ 2𝐶 𝑘−1 𝐶𝐴,𝑒𝑞 𝐶𝐵,𝑒𝑞
The forward reaction has a rate law given by 𝒌𝟏
= 𝑲𝒆𝒒
𝒌−𝟏
−𝑟𝐴,𝑓 = 𝑘1 𝐶𝐴 𝐶𝐵
𝒌𝟏
𝒌−𝟏 =
The reverse reaction has the following rate law 𝑲𝒆𝒒
𝑟𝐴,𝑏 = 𝑘−1 𝐶𝐶2
Thus
Thus 𝑘1 2
−𝑟𝐴 = 𝑘1 𝐶𝐴 𝐶𝐵 − 𝐶𝐶
−𝑟𝐴 = 𝑘1 𝐶𝐴 𝐶𝐵 − 𝑘−1 𝐶𝐶2 𝐾𝑒𝑞

At equilibrium, 1 2
−𝑟𝐴 = 𝑘1 𝐶𝐴 𝐶𝐵 − 𝐶𝐶
2 𝐾𝑒𝑞
0 = 𝑘1 𝐶𝐴,𝑒𝑞 𝐶𝐵,𝑒𝑞 − 𝑘−1 𝐶𝐶,𝑒𝑞
2𝑘1 2
𝑘1 𝐶𝐴,𝑒𝑞 𝐶𝐵,𝑒𝑞 𝑟𝐶 = 2𝑘1 𝐶𝐴 𝐶𝐵 − 𝐶𝐶
2 =1 𝐾𝑒𝑞
𝑘−1 𝐶𝐶,𝑒𝑞
ChE 2115: Chemical
Reaction Engineering
Reversible Reaction
EXAMPLE
Consider the elementary, isothermal constant volume reversible, batch
reaction: A ↔ 2R with CA0 = 2.5 M and CR0 = 0.2 M. Experiments show that
the half-life of A is 40 min and the concentration of A becomes constant at
0.5M. Determine a) The Equilibrium Constant, Keq, and b) The forward and
backward rate constants. c)The number of batches needed per day if 60%
conversion of A is desired per batch with 24 min downtime per batch.

ChE 2115: Chemical

Reaction Engineering
Reversible Reaction
Consider the elementary, isothermal constant volume reversible, batch reaction: A ↔ 2R with CA0 = 2.5 M and CR0 = 0.2 M. Experiments show
that the half-life of A is 40 min and the concentration of A becomes constant at 0.5M. Determine a) The Equilibrium Constant, Keq, and b) The
EXAMPLE forward and backward rate constants. c)The number of batches needed per day if 60% conversion of A is desired per batch with 24 min
downtime per batch.

𝐶𝑅2 𝑑𝑋𝐴 0.2 + 2 2.5 𝑋𝐴 2

−𝑟𝐴 = 𝑘1 𝐶𝐴 − 2.5 = 𝑘1 2.5 1 − 𝑋𝐴 −
𝐾𝑒𝑞 𝑑𝑡 35.28
0.5
At equilibrium, 𝐶𝐴,𝑒𝑞 = 0.5 𝑀 2.5𝑑𝑋𝐴
න 2 = 𝑘1 40
𝐶𝐴,𝑒𝑞 0.5 0 0.2 + 2 2.5 𝑋𝐴
𝑋𝐴,𝑒𝑞 = 1 − =1− = 0.8 2.5 1 − 𝑋𝐴 −
35.28
𝐶𝐴0 2.5 𝑘1 = 0.01843 /min
2 𝑘1
𝐶𝑅,𝑒𝑞 = 𝐶𝑅,0 + 𝐶𝐴0 𝑋𝐴,𝑒𝑞 = 0.2 + 2 2.5 0.8 = 4.2 𝑀 = 𝐾𝑒𝑞
1 𝑘−1
2
𝐶𝑅,𝑒𝑞 4.22
𝐾𝑒𝑞 = = = 35.28 𝑘−1 = 5.22 × 10−4 /M ∙ min
𝐶𝐴,𝑒𝑞 0.5
2
2
𝑑𝐶𝐴 𝐶𝑅,0 + 𝐶𝐴0 𝑋𝐴
1
− = 𝑘1 𝐶𝐴0 1 − 𝑋𝐴 −
𝑑𝑡 35.28
ChE 2115: Chemical
Reaction Engineering
Reversible Reaction
Consider the elementary, isothermal constant volume reversible, batch reaction: A ↔ 2R with CA0 = 2.5 M and CR0 = 0.2 M. Experiments show
that the half-life of A is 40 min and the concentration of A becomes constant at 0.5M. Determine a) The Equilibrium Constant, Keq, and b) The
EXAMPLE forward and backward rate constants. c)The number of batches needed per day if 60% conversion of A is desired per batch with 24 min
downtime per batch.

2
2
𝑑𝐶𝐴 𝐶𝑅,0 + 𝐶𝐴0 𝑋𝐴
1
− = 𝑘1 𝐶𝐴0 1 − 𝑋𝐴 −
𝑑𝑡 35.28
0.6
2.5𝑑𝑋𝐴
න 2 = 𝑘1 𝑡
0 0.2 + 2 2.5 𝑋𝐴
2.5 1 − 𝑋𝐴 −
35.28
𝑘1 = 0.01843 /min

𝑡 = 55.65 𝑚𝑖𝑛
1440 𝑚𝑖𝑛
= 18 𝑏𝑎𝑡𝑐ℎ𝑒𝑠
55.65 + 40 𝑚𝑖𝑛/𝑏𝑎𝑡𝑐ℎ

ChE 2115: Chemical

Reaction Engineering