Chemical Kinetics

Module 7
Chapter 13

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 Chemical Kinetics (1)

Thermodynamics – does a reaction take place?

Kinetics – how fast does a reaction proceed?

Reaction rate is the change in the concentration of a

reactant or a product with time (𝑀/𝑠).

A→ B
∆[A] ∆[A] = change in concentration of A over
rate = −
∆𝑡 time period ∆𝑡
∆[B] ∆[B] = change in concentration of B over
rate =
∆𝑡 time period ∆𝑡
Because [A] decreases with time,∆[A] is negative.
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Chemical Kinetics (2) A→B
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Copyright © McGraw-Hill Education. Permission required for reproduction or display.

∆[A]
rate = −
∆𝑡
∆[B]
rate =
∆𝑡

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 Kinetic Rates
Br2 (𝑎𝑞) + HCOOH(𝑎𝑞) → 2Br − (𝑎𝑞) + 2H + (𝑎𝑞) + CO2 (𝑔)
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Time (s) 𝐁𝐫𝟐 (𝑴)

0.0 0.0120
50.0 0.0101
100.0 0.00846
150.0 0.00710
200.0 0.00596 slope of
250.0 0.00500 tangent
300.0 0.00420
slope of
tangent
350.0 0.00353 slope of
400.0 0.00296 tangent

∆ Br2 [Br2 ]final −[Br2 ]initial

average rate = − =−
∆𝑡 𝑡final − 𝑡initial

instantaneous rate = rate for specific instance in time 4

 Reaction Rates and Stoichiometry

2A → B

Two moles of A disappear for each mole of B that is formed.

1∆ A ∆[B]
rate = − rate =
2 ∆𝑡 ∆𝑡

𝑎A + 𝑏B → 𝑐C + 𝑑D

1∆ A 1∆ B 1∆ C 1 ∆[D]
rate = − =− = =
𝑎 ∆𝑡 𝑏 ∆𝑡 𝑐 ∆𝑡 𝑑 ∆𝑡

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Example 13.1
Write the rate expressions for the following reactions in terms of
the disappearance of the reactants and the appearance of the
products:
(a) I− 𝑎𝑞 + OCl− 𝑎𝑞 → Cl− 𝑎𝑞 + OI− (𝑎𝑞)
(b) 4NH3 (𝑔) + 5O2 (𝑔) → 4NO(𝑔) + 6H2 O(𝑔)
(c) CH4(g) + Br2(g) → CH3Br(g) + HBr(g)

Practice Exercise
Write the rate expressions for the following reaction:
CH (g) + 2O (g) → CO (g) + 2H O(g)
4 2 2 2
 The Rate Law
The rate law expresses the relationship of the rate of a reaction
to the rate constant and the concentrations of the reactants
raised to some powers.
𝑎A + 𝑏B → 𝑐C + 𝑑D

Rate = 𝑘[A]𝑥 [B]𝑦

Reaction is xth order in A

Reaction is yth order in B
Reaction is (x +y)th order overall

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 The Rate Law (1)

F2 𝑔 + 2ClO2 (𝑔) → 2FClO2 (𝑔)

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Table 13.2 Rate Data for Reaction Between 𝐅𝟐 and 𝐂𝐥𝐎𝟐

[𝐅𝟐 ] (𝑴) 𝐂𝐥𝐎𝟐 (𝑴) Initial Rates (𝑴Τ𝒔)

rate = 𝑘 F2 𝑥 ClO2 𝑦 1. 0.10 0.010 1.2 × 10−3

2. 0.10 0.040 4.8 × 10−3
3. 0.20 0.010 2.4 × 10−3

Double [F2 ] with [ClO2 ] constant

Rate doubles
x=1
rate = 𝑘 F2 [ClO2 ]
Quadruple [ClO2 ] with F2 constant
Rate quadruples
y=1
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 Rate Laws
• Rate laws are always determined experimentally.

• Reaction order is always defined in terms of reactant

(not product) concentrations.

• The order of a reactant is not related to the

stoichiometric coefficient of the reactant in the balanced
chemical equation.
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F2 𝑔 + 2ClO2 (𝑔) → 2FClO2 (𝑔)

rate = 𝑘 F2 ClO2 −1

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Example 13.3
The reaction of nitric oxide with hydrogen at 1280° C is
2NO 𝑔 + 2H2 𝑔 → N2 𝑔 + 2H2 O(𝑔)
From the following data collected at this temperature, determine
(a) the rate law
(b) the rate constant
(c) the rate of the reaction when NO = 12.0 × 10−3 𝑀 and
H2 = 6.0 × 10−3 𝑀
Experiment 𝐍𝐎 (𝑴) 𝐇𝟐 (𝑴) Initial Rates (𝑴Τ𝒔)
1 5.0 × 10−3 2.0 × 10−3 1.3 × 10−5
2 10.0 × 10−3 2.0 × 10−3 5.0 × 10−5
3 10.0 × 10−3 4.0 × 10−3 10.0 × 10−5
11
 First-Order Reactions
A → product
∆A
∆[A] − = 𝑘[A]
rate = − ∆𝑡
∆𝑡
and rate = 𝑘[A] ∆A 𝑡
ln =−𝑘t
rate 𝑀Τ𝑠 0
∆A
𝑘= = = 1Τs or s −1
[A] 𝑀 [A]t is the concentration of A at any time t
[A]0 is the concentration of A at time t = 0
A 𝑡 = [A]0 𝑒 −𝑘𝑡 ln A 𝑡 = ln[A]0 −𝑘𝑡
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 First-Order Reactions (1)

The half-life, 𝒕𝟏ൗ𝟐 , is the time required for the concentration of a

reactant to decrease to half of its initial concentration.
𝑡1Τ2 = 𝑡 when [A] = [A]0 /2

[A]0
ln
[A]0 /2 ln 2 0.693
𝑡1ൗ = = =
2 𝑘 𝑘 𝑘

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Example 13.4
The conversion of cyclopropane to propene in the gas phase is a
first-order reaction with a rate constant of 6.7 × 10−4 s −1 at
500° C .

(a) If the initial concentration of cyclopropane was 0.25 𝑀, what is

the concentration after 8.8 min?
(b) How long (in minutes) will it take for the concentration of
cyclopropane to decrease from 0.25 𝑀 to 0.15 𝑀?
(c) How long (in minutes) will it take to convert 74 percent of the
starting material?
Practice Exercise The reaction 2A → B is first order in A
with a rate constant of 2.8 x 10-2 s-1 at 80° C. How long (in
seconds) will it take for A to decrease from 0.88 M to 0.14 M?