Problem 1

The reaction 𝐴 + 𝐵 → 𝐶 is first-order with respect to A and B with a rate constant of

0.00132 mol-1 L s-1 . Initially, 1.5 mol/L of A was reacted to 2.0 mol/L. Assuming that
the reaction volume is constant throughout,
(a) Determine the concentration profiles of A, B and C.
(b) What is the concentration of A and B after 15 minutes?
(c) How long will it take to achieve 95% conversion of A?
Solution:
(a) Concentrations of A, B and C with respect to time

𝑟𝑟𝑥𝑛 = 𝑘 [𝐴][𝐵]
𝑟𝑟𝑥𝑛 = −𝑟𝐴 = −𝑟𝐵 = 𝑟𝐶
𝑑 [𝐴 ] 𝑑[𝐵] 𝑑 [𝐶 ]
𝑟𝑟𝑥𝑛 = − =− =
𝑑𝑡 𝑑𝑡 𝑑𝑡

𝑑[𝐴]
= −𝑘 [𝐴][𝐵]
𝑑𝑡
𝑑 [𝐵]
= −𝑘 [𝐴][𝐵]
𝑑𝑡
𝑑 [𝐶 ]
= 𝑘 [𝐴][𝐵]
𝑑𝑡

Let x be the amount of A reacted

A B C
Initial 1.5 2.0 0.0
concentration:
Amount -x -x x
reacted/produced:
Final 1.5 − 𝑥 2.0 − 𝑥 𝑥
Concentration:

[𝐴] = 1.5 − 𝑥
𝑥 = 1.5 − [𝐴]

[𝐵] = 2.0 − 𝑥
 𝑥 = 2.0 − [𝐵]
[𝐶 ] = 𝑥 = 1.5 − [𝐴]

𝑥=𝑥
1.5 − [𝐴] = 2.0 − [𝐵]
[𝐵] = 0.5 + [𝐴]

𝑑 [𝐴 ]
− = 𝑘 [𝐴](0.5 + [𝐴])
𝑑𝑡
Let [𝐴] = Ca
𝑑𝐶𝑎
− = 𝑘𝐶𝑎 (0.5 + 𝐶𝑎 )
𝑑𝑡

𝐶𝑎 𝑡
𝑑𝐶𝑎
∫ = −𝑘 ∫ 𝑑𝑡
1.5 𝐶𝑎 (0.5 + 𝐶𝑎 ) 0

1 𝐴 𝐵
= +
𝐶𝑎 (0.5 + 𝐶𝑎 ) 𝐶𝑎 0.5 + 𝐶𝑎
𝐴 = 2, 𝐵 = −2

𝐶𝑎 𝐶𝑎
𝑑𝐶𝑎 𝑑𝐶𝑎
2∫ −2∫ = −𝑘𝑡
1.5 𝐶𝑎 1.5 (0.5 + 𝐶𝑎 )

𝐶𝑎 0.5 + 𝐶𝑎
2 ln ( ) − 2 ln ( ) = −𝑘𝑡
1.5 2.0
0.5 + 𝐶𝑎
−2 ln ( 2.0 ) = −𝑘𝑡
𝐶𝑎
1.5
1.5(0.5 + 𝐶𝑎 )
2 ln [ ] = 𝑘𝑡
2.0𝐶𝑎
0.75(0.5 + 𝐶𝑎 ) 𝑘𝑡
=𝑒2
𝐶𝑎
 𝑘𝑡
0.375 + 0.75𝐶𝑎 = 𝐶𝑎 𝑒 2

0.375
[𝐴 ] = 𝑘𝑡
𝑒2 − 0.75

0.375
[𝐵] = 0.5 + 𝑘𝑡
𝑒2 − 0.75

0.375
[𝐶 ] = 1.5 − 𝑘𝑡
𝑒2 − 0.75
(b) What is the concentration of A and B after 15 minutes?
k = 0.00132 mol-1 L s-1, t = 15 minutes = 900 seconds

0.375 0.375
[𝐴] = 𝑘𝑡 = (0.00132)(900)
= 0.35 𝑚𝑜𝑙/𝐿
𝑒 2 − 0.75 𝑒 2 − 0.75

0.375
[𝐵] = 0.5 + (0.00132)(900)
= 0.85 𝑚𝑜𝑙/𝐿
𝑒 2 − 0.75

(c) How long will it take to achieve 95% conversion of A?

𝐶𝑎𝑜 − 𝐶𝑎
𝑋= 𝑥100
𝐶𝑎𝑜
1.5 − 𝐶𝑎
95 = 𝑥100
1.5
𝐶𝑎 = 0.075 𝑚𝑜𝑙/𝐿

0.375
0.00132𝑡 = 0.075
𝑒 2 − 0.75
 𝑡 = 2650.3 𝑠𝑒𝑐𝑜𝑛𝑑 = 44.17 𝑚𝑖𝑛𝑢𝑡𝑒𝑠

Problem 2
𝑘1 𝑘2
Given the elementary reaction, 𝐴 → 𝐵 → 𝐶. Assuming constant volume of the reaction,
determine the concentration profiles of A, B and C given that the initial concentration
of A is 1.5 mol/dm3, initial concentration of B is 0 mol/dm3 and initial concentration of
C is 0 mol/dm3. The reaction constants, k1 and k2, are 0.0023 s-1 and 0.0011 s-1,
respectively.

Solution: Concentration profiles of A, B and C

𝑘1 𝑘2
𝐴 → 𝐵→𝐶
𝐴 → 𝐵, 𝑟𝑟𝑥𝑛 = 𝑘1 [𝐴]
𝐵 → 𝐶, 𝑟𝑟𝑥𝑛 = 𝑘2 [𝐵]

𝑑 [𝐴 ]
= −𝑘1 [𝐴]
𝑑𝑡
𝑑 [𝐵 ]
= 𝑘1 [𝐴] − 𝑘2 [𝐵]
𝑑𝑡
𝑑[𝐶 ]
= 𝑘2 [𝐵]
𝑑𝑡
All the equations are first-order linear ordinary differential equations

𝐴′ = −𝑘1 𝐴
𝐿{𝐴′} = −𝑘1 𝐿{𝐴}
𝑠𝐴(𝑠) − 1.5 = −𝑘1 𝐴(𝑠)
1.5
𝐴(𝑠 ) =
𝑠 + 𝑘1
𝐴(𝑡) = 1.5𝑒 −𝑘1 𝑡
 𝐵′ = 𝑘1 𝐴 − 𝑘2 𝐵
𝐿{𝐵′} = 𝑘1 𝐿{𝐴} − 𝑘2 𝐿{𝐵}
𝑠𝐵(𝑠) = 𝑘1 𝐴(𝑠) − 𝑘2 𝐵(𝑠)
𝑘1 𝐴(𝑠) 1.5𝑘1
𝐵 (𝑠 ) = =
𝑠 + 𝑘2 (𝑠 + 𝑘2 )(𝑠 + 𝑘1 )
3𝑘1 𝑒 −𝑘2 𝑡 3𝑘1 𝑒 −𝑘1 𝑡
𝐵 (𝑡 ) = −
2(𝑘1 − 𝑘2 ) 2(𝑘1 − 𝑘2 )
3𝑘1
𝐵 (𝑡 ) = (𝑒 −𝑘2 𝑡 − 𝑒 −𝑘1 𝑡 )
2(𝑘1 − 𝑘2 )

𝐶 ′ = 𝑘2 𝐵
𝐿{𝐶 ′} = 𝑘2 𝐿{𝐵}
𝑠𝐶 (𝑠) = 𝑘2 𝐵(𝑠)
𝑘2 𝐵(𝑠) 1.5𝑘1 𝑘2
𝐶 (𝑠 ) = =
𝑠 𝑠(𝑠 + 𝑘2 )(𝑠 + 𝑘1 )
3𝑘2 𝑒 −𝑘1 𝑡 3𝑘1 𝑒 −𝑘2 𝑡 3
𝐶 (𝑡 ) = − +
2(𝑘1 − 𝑘2 ) 2(𝑘1 − 𝑘2 ) 2

𝑨(𝒕) = 𝟏. 𝟓𝒆−𝒌𝟏 𝒕
𝟑𝒌𝟏
𝑩(𝒕) = (𝒆−𝒌𝟐 𝒕 − 𝒆−𝒌𝟏 𝒕 )
𝟐(𝒌 𝟏 − 𝒌 𝟐 )

𝟑𝒌𝟐 𝒆−𝒌𝟏 𝒕 𝟑𝒌𝟏 𝒆−𝒌𝟐 𝒕 𝟑

𝑪(𝒕) = − +
𝟐( 𝒌 𝟏 − 𝒌 𝟐 ) 𝟐 ( 𝒌 𝟏 − 𝒌 𝟐 ) 𝟐
Problem 3
The first-order decomposition of A produces two products at different rates. The
reaction is given by
𝑘1
𝐴→
𝑘2
𝐵
→𝐶
where k1 is 0.0054 min-1 and k2 is 0.023 min-1. If the initial concentration of A is 3 mol
dm-3, determine the concentration profile of B and C throughout the reaction. What are
the concentrations of B and C after 10 minutes?
𝑘1
𝐴 → 𝐵, 𝑟𝑟𝑥𝑛 = 𝑘1 [𝐴]
𝑘2
𝐴 → 𝐶, 𝑟𝑥𝑛 = 𝑘2 [𝐴]

𝑑 [𝐴]
= −𝑘1 [𝐴] − 𝑘2 [𝐴] = −(𝑘1 + 𝑘2 )[𝐴]
𝑑𝑡
𝑑 [𝐵]
= 𝑘1 [𝐴]
𝑑𝑡
𝑑 [𝐶 ]
= 𝑘2 [𝐴]
𝑑𝑡

[𝐴] = 3𝑒 −(𝑘1 +𝑘2 )𝑡

3𝑘1
[𝐵 ] = [1 − 𝑒 −(𝑘1 +𝑘2 )𝑡 ]
𝑘1 + 𝑘2
3𝑘2
[𝐶 ] = [1 − 𝑒 −(𝑘1 +𝑘2)𝑡 ]
𝑘1 + 𝑘2