Third Stage

Subject: Chemical Reaction Kinetics

Lecture- THREE
(SOLVED EXAMPLES)

Prof . Dr. Mohammad Fadhil

Al-Turath University

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 1. Finding the rate constant units
What are the units of the rate constant for the ideal gas elementary
reaction at 400 K . 2A(g) B(g) . The rate law is
𝑑𝑝
expressed as, − = 5.6 𝑝2
𝑑𝑡
(a) What are the units of the rate constant, if the units of the reaction
rate are in (atm/h)?

(b) What are the units of the rate constant if the rate is expressed by the
reactant concentration?. The units of the reaction rate are in (mol/L. s)
Answer
(a)
𝑑𝑝
− = 5.6 𝑝2 (1)
𝑑𝑡

𝑎𝑡𝑚
= k 𝑎𝑡𝑚2
ℎ
1
k = 5.6 ( )
𝑎𝑡𝑚.ℎ

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(b)
𝑝𝑉 = 𝑛𝑅𝑇
𝑛
𝑝= 𝑅𝑇
𝑉
𝑝= 𝐴 𝑅𝑇 2 𝑠𝑢𝑏𝑠𝑡𝑖𝑡𝑢𝑡𝑒 𝑖𝑛 1
𝑑 𝐴 𝑅𝑇 2
− = 5.6 𝐴 𝑅 𝑇
𝑑𝑡
𝑑 𝐴
− = 𝟓. 𝟔 𝑹𝑻 𝐴 2
𝑑𝑡
1 𝑎𝑡𝑚. 𝐿
𝑘 = 5.6 𝑥 0.082 400 𝐾
𝑎𝑡𝑚. ℎ 𝑚𝑜𝑙. 𝐾
𝐿
𝑘 = 183.68
𝑚𝑜𝑙.ℎ

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2. Finding the Activation Energy

At two different temperatures, the reaction rate of A B is the same

as shown below
(- rA) = 2.3 p2A 400 K pA (atm)
(- rA) = 2.3 p2A 500 K - rA ( mol/m3. S)

(a) Calculate the activation energy.

(b) Convert the rate units into concentration units and then evaluate the activation
energy.
Answer
(a)
k2 Ea  1 1 
ln    
k1 R  T2 T1 
k1 = k2
ln 1 = 0
T1 ≠ T2
so Ea = 0

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(b)
𝑚𝑜𝑙 𝑚𝑜𝑙
− 𝑟𝐴 = 2.3 𝑝𝐴2 ( 𝑎𝑡𝑚2 )
𝑚3 . 𝑠 𝑚3 .𝑠. 𝑎𝑡𝑚2
2 2 2
− 𝑟𝐴 = 2.3 𝐴 𝑅 [𝑇]

At 400 K
𝑚𝑜𝑙 𝑚𝑜𝑙 2
𝑚3 . 2
− 𝑟𝐴 = 2.3 𝐴 ( 82 𝑥 10−6 ) (400 𝐾)2
𝑚3 . 𝑠 𝑚3 . 𝑠. 𝑎𝑡𝑚2 𝑚𝑜𝑙. 𝐾
− 𝑟𝐴 = 0.0025 [𝐴]2
𝑚3 .
𝑘1 = 0.0025
𝑚𝑜𝑙. 𝑠
Similarly, at 500 K
𝑚3 .
− 𝑟𝐴 = 0.0039 [𝐴]2 𝑘2 = 0.0039
𝑚𝑜𝑙. 𝑠
𝑅 𝑇1 𝑇2 𝑘2
𝐸𝑎 = ln =
𝑇2 − 𝑇1 𝑘1
8.314 (400) (500) 0.0039
𝐸𝑎 = ln
500− 400 0.0025
𝐽
𝐸𝑎 = 7394
𝑚𝑜𝑙

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3. The first-order reversible liquid reaction A B
takes place in a
batch reactor. After 8 minutes, conversion of A is 33.3% while equilibrium
𝑚𝑜𝑙
conversion is 66.7%. If [𝐴]0 = 0.5 𝐿 𝑎𝑛𝑑 [𝐵]0 = 0, find the rate equation for
this reaction.
Answer
For a first-order reversible liquid reaction:
𝑿
− 𝒍𝒏(𝟏 − 𝑿 𝑨 ) = (𝒌𝟏 + 𝒌𝟐)𝒕 (1)
𝑨𝒆
XAe = 0.667 ≃ 2/3 (from Q4 above). Substituting values from Q4 in (1) to obtain,
1
− ln(1 − 3 ) = (𝑘1 + 𝑘2)8 𝑚𝑖𝑛
2
3
ln 2
(𝑘1 + 𝑘2) = 8 = 0.0866 𝑚𝑖𝑛−1 (2)
𝑟𝐴 = 𝑘1 𝐴 𝑟𝐵 = 𝑘2 𝐵
At equilibrium, 𝑟𝐴 = 𝑟𝐵 and [𝐴] = [𝐴]𝑒 ; [𝐵] = [𝐵]𝑒
𝑘1 𝐴 𝑒 = 𝑘2 𝐵 𝑒
2
𝑘1 [𝐵]𝑒 𝑘1 0.5 𝑥
3
= (3) Substitute values of Q4 into 3 gives = 1
𝑘2 [𝐴]𝑒 𝑘2 0.5 𝑥 3
𝑘1 = 2𝑘2 (4) substitute 4 into 2 to get 𝑘1 = 0.0577 𝑚𝑖𝑛−1
𝑘2 = 0.0288 𝑚𝑖𝑛−1
− 𝒓𝑨 = 𝟎. 𝟎𝟓𝟕𝟕 𝑨 − 𝟎. 𝟎𝟐𝟖𝟖 [𝑩] 6
4. reactant A is contained in a small vessel at 1 atm. and 25 0C. At this
temperature no reaction occurs. The temperature of the vessel is raised
quickly to 100 0C then the reaction 2A B is started. As the reaction
continues, the pressure of the vessel is decreased with time. The table below
shows this variation. Find a rate equation in units of moles, liters, and minutes
which will satisfactorily fit the data.
Time (min) PA (atm) Time (min) PA (atm)
0 1.252 6 0.488
1 1.028 7 0.488
2 0.828 8 0.412
3 0.712 9 0.378
4 0.628 10 0.348
5 0.558 15 0.256
20 0.204
Answer

1. Assume first-order,

𝐥𝐧 𝒑𝑨 = −𝒌𝒕 + 𝒍𝒏[𝒑𝑨 ]𝟎

Plot ln [𝒑𝑨 ] against t

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Time PA ln PA Time PA (atm) ln PA
(min) (atm) (min)
0 1.252 0.225 6 0.488 - 0.717
1 1.028 0.0276 7 0.488 - 0. 717
2 0.828 - 0.1887 8 0.412 - 0. 886
3 0.712 - 0.3397 9 0.378 - 0.973
4 0.628 - 0.465 10 0.348 - 1.055
5 0.558 - 0. 5834 15 0.256 - 1.362
20 0.204 - 1.589

2. Assume second order reaction

𝟏 𝟏 𝟏
= k t + [𝒑 Plot [𝒑 ] against t
[𝒑𝑨 ] 𝑨 ]𝟎 𝑨

Time PA 1/PA Time PA 1/ PA

(min) (atm) (min)
0 1.252 0.798 6 0.488 2.049
1 1.028 0.972 7 0.488 2.049
2 0.828 1.208 8 0.412 2.427
3 0.712 1.404 9 0.378 2.645
4 0.628 1.592 10 0.348 2.873
5 0.558 1.792 15 0.256 3.906
20 0.204 4.902

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5. An elementary reaction: 2A B + C . A sample of A ([A]0 = 20
mol/Liter) is stored at 100°C and after 7 hr 40 min we find that 10 mol%
has turned into B. Find the rate equation for this reaction.
Answer
The general rate equation of an elementary reaction:
∆𝐴
− = 𝑘[𝐴]2
∆𝑡
∆𝐴 1
𝑘= −
∆𝑡 𝐴 2
[A] after reaction = 20 – 0.1 = 19.9 mol/L

0.2 1
𝑘= − 2 = 6.6 x 10-5 L/mol. h
7 3 ℎ𝑟 19.9 𝑚𝑜𝑙/𝐿 2

− 𝒓𝑨 = 6.6 x 10−5[𝑨]𝟐 mol/L. h

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6. The thermal decomposition of hydrogen iodide 2HI H2 + I2
The variation of the rate constant (k) with temperature is as follows:

T (0C) 508 427 393 356 283

k (cm3/mol. s) 0.1059 0.0031 0.000588 80.9 x 10-6 0.942 x 10-6

Find the complete rate equation for this reaction. Use units of joules, moles,
cm3 and seconds.
Answer
For answering Q7, the following table are prepared:
T (0C) T (K) 1/T (K-1) k ln k
508 781 0.00128 0.1059 - 1.697
427 700 0.00143 0.0031 -5.776
393 666 0.001502 0.000588 - 7.439
356 629 0.00159 80.9 x 10-6 -9.422
273 546 0.001832 0.942 x 10-6 - 13.875

To find the value of ln A, plot ln k against 1/T 10

 10

From plot: 0
𝐸𝑎 4 0.001 0.0012 0.0014 0.0016 0.0018 0.002

ln k
𝑠𝑙𝑜𝑝𝑒 = − =− = 22222 𝐾 −1 -5
𝑅 0.00018
-10
𝐸𝑎 1
𝑙𝑛𝐴 = ln 𝑘 −
𝑅 𝑇 -15
1/T [K-1]
1
𝑙𝑛𝐴 = 5.776 − 22222 700
𝑙𝑛𝐴 = 31.746
𝐴 = 𝑒 31.746 = 61.25X 1012
= −22222 𝑚𝑜𝑙
− 𝑟𝐴 61.25x 1012 (𝑒 𝑇 ) [𝐴]2
𝑐𝑚3 .𝑠

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 k1 k2
7. In a consecutive reaction A  B  C .
Find expressions for maximum concentration of B.
[ ]
𝑑𝐵
= +𝑘1 𝐴 − 𝑘2 𝐵
𝑑𝑡 (1)
[A] = [A]0 𝑒 − 𝑘1 𝑡 (2)
𝑘1 𝐴 0
𝐵 = 𝑒− 𝑘1 𝑡 − 𝑒 − 𝑘2 𝑡 (3)
𝑘2 − 𝑘1

Substitute 2 and 3 into 1 to get,

𝐵
𝑑
= 𝑘1 𝐴 0
𝑑𝑡 (− 𝑘1 𝑒 −𝑘1 𝑡 + 𝑘2 𝑒 −𝑘2 𝑡 ) (4)
𝑘2 − 𝑘1

𝐵
𝑑
= 0
B is a maximum when 𝑑𝑡

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 𝑘1 𝐴 0
0 = (− 𝑘1 𝑒 −𝑘1 𝑡 + 𝑘2 𝑒 −𝑘2 𝑡 )
𝑘2 − 𝑘1
0 = − 𝑘1 𝑒 −𝑘1 𝑡 + 𝑘2 𝑒 −𝑘2 𝑡

𝑘1 𝑒 −𝑘1 𝑡 = 𝑘2 𝑒 −𝑘2 𝑡
𝑘1 𝑒 −𝑘2 𝑡
= −𝑘 𝑡
𝑘2 𝑒 1
𝑘1
= 𝑒 𝑘1 − 𝑘2 𝑡
𝑘2
𝑘1
ln = 𝑘1 − 𝑘2 𝑡
𝑘2

1 𝑘1
𝑡𝑚𝑎𝑥 = ln (5)
(𝑘1 − 𝑘2 ) 𝑘2

Substitute 5 into 3 to obtain the maximum value of B

𝑘 𝑘
𝑘1 𝐴 0 − 𝑘1 ln 𝑘1 −𝑘2 ln 𝑘1
2 2
𝐵 = [𝑒𝑥𝑝 − exp ] (6)
𝑘2 − 𝑘1 𝑘1 − 𝑘2 𝑘1 − 𝑘2
Simplifying (6)
𝒌𝟐 𝒌𝟐
[𝑩]𝒎𝒂𝒙 = [𝐀]𝟎 𝒆(𝒌𝟏 − 𝒌𝟐)
𝒌𝟏
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