CHEMICAL KINETICS

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10th ed: Chapter 14 pg 575-615

1. What is Chemical Kinetics?

• The study of reaction rates, the
changes in concentrations of
reactants (or products) as a
function of time

• Knowing how fast a reaction

proceeds is important in terms of
gaining a basic understanding of a • Nature of reactants: Bond formation/breaking
chemical process. and the energy involved.
• Concentration: Reaction rate generally
• Kinetics is important to increase as reactant concentration increases.
engineers because: • Temperature: Reaction rate increase as
- on a chemical plant you would
temperature increases.
want your product to be formed as
• Catalyst: a catalyst increase the reaction rate
fast as possible.
without being consumed in the reaction.
- in the food industry you would • Surface area: of solid/liquid reactants or
want your food to spoil as slowly catalysts: reactions that involve solids often
as possible. proceed faster as the surface area of the solid
increases. Small solid particles have a larger
- civil engineers would want their specific surface area than large solid
construction materials (eg. particles.
cement) to set as fast as possible • Reaction rates tend to be higher when using
to give the desired properties. smaller solid particles. 2

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2. Expressing Reaction Rates
• Reaction rate: rate of change of the concentration 𝒎𝒐𝒍
𝑼𝒏𝒊𝒕𝒔 𝒐𝒇 𝒓𝒂𝒕𝒆: /𝒔
of any species in the reaction. 𝑳

• i.e the rate of disappearance of any of the reactants

or the rate of appearance of any of the products.

• Consider the reaction:

A+B→P

∆𝑷 ∆𝑨 ∆𝑩
𝑹𝒂𝒕𝒆
∆𝒕 𝒕 ∆𝒕

• Note negative sign : Δ[reactant] = [reactant]final –

[reactant]initial = < 0 (reactant is consumed)

• Note: [A] means concentration of A

• The rate of a reaction gradually decreases as the

concentration of reactants decreases. i.e. the rate of
reaction changes while it is measured.

• To minimize error the reaction rate is measured at

shorter periods of time.

Instantaneous Rates
• e.g. Instantaneous rate at 600s:
∆ C H Cl
∆𝑡
0,017 0,042 M
800 400 s
6.2 10 M s
• For the reaction:
aA + bB → cC + dD

• 𝑰𝒏𝒔𝒕𝒂𝒏𝒕𝒆𝒏𝒆𝒐𝒖𝒔 𝒓𝒂𝒕𝒆
𝟏∆ 𝐀 𝟏∆ 𝐁 𝟏∆ 𝐂 𝟏∆ 𝐃
𝐚 ∆𝐭 𝐛 𝐭 𝐜 ∆𝐭 𝐝 ∆𝐭

• For 2HI(g) → H2(g) + I2(g)

𝑰𝒏𝒔𝒕𝒂𝒏𝒕𝒆𝒏𝒆𝒐𝒖𝒔 𝒓𝒂𝒕𝒆
𝟏 ∆ 𝐇𝐈 ∆ 𝐇𝟐 ∆ 𝐈𝟐
𝟐 ∆𝐭 𝐭 ∆𝐭
• 2 mol of HI disappears for each mole of
H2 and I2 that forms. The rate of
Fig. Butyl chloride concentration as a
disappearance of HI is twice the rate of function of time
4
appearance of H2 and I2. C4H9Cl + H2O → C4H9OH + HCl

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3. Dependence of Reaction Rate on Concentration
• Elementary Reaction: those reactions • Rate law for elementary reaction:
that take place as written down in reaction rate is proportional to the
chemical equations concentrations of reactants raised to
the power of their stoichiometric
e.g. H(g) + H(g) → H2(g) coefficients [what about Law of mass
action]
• Complex Reaction: those reactions that
consist of a number of elementary e.g. H(g) + H(g) → H2(g)
reactions
𝐫𝐚𝐭𝐞 𝐥𝐚𝐰
e.g. NO2(g) + CO(g) → NO(g) + CO2(g)

• Actually occurs as two elementary

𝒅𝐇 𝒅 𝐇𝟐 𝟏 𝟏 𝟐
𝒌𝐇 𝐇 𝐤𝐇
reactions: 𝒅𝐭 𝒅𝐭

NO2(g) + NO2(g) → NO3(g) + NO(g) • Rate law for complex reaction: is

NO3(g) + CO(g) → NO2(g) + CO2(g) determined experimentally (not from
the balanced reaction equation).
• Rate Law: expresses the reaction rate
as a function of reactant concentrations, e.g. NO2(g) + CO(g) → NO(g) + CO2(g)
product concentrations, and time. It is
experimentally determined. 𝐫𝐚𝐭𝐞 𝐥𝐚𝐰
𝒅 𝐍𝐎𝟐
𝒌 𝐍𝐎𝟐 𝟐
𝒅𝐭 5

3. Dependence of Reaction Rate on Concentration

• Reaction Order: rate laws for most Example: For each of the following
reactions have the general form: reactions, determine the reaction order
with respect to each reactant and the
Rate = k[reactant A]m[reactant B]n overall reaction order from the given rate
law.
• where m and n = reaction orders
(a) 2NO(g) + O2(g) → 2NO2(g); rate =
(not related to stoichiometric
k[NO]2[O2]
numbers)
(b) CH3CHO(g) → CH4(g) + CO(g); rate =
• and k = rate constant k[CH3CHO]3/2

• m + n = overall reaction order (c) H2O2(aq) + 3I-(aq) + 2H+(aq) → I3-(aq)

+ 2H O(l); rate = k[H O ][I-]
2 2 2
• Reaction orders cannot be deduced
from the balanced chemical [Hint] - Inspect the rate law and not
equation. the coefficients in the balanced
chemical reaction.
• Reaction orders are usually positive Solution:
integers or zero.
(a) The reaction is 2nd order in NO, 1st
• Reaction orders can be fractional or order in O2, and 3rd order overall
negative. 6

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Experimental Determination of the Rate Law
Reaction Order Terminology • of reaction as a function of
concentration of one of the
• rate = k[A]: first order overall reactants whilst holding the
(rate  [A]) concentration of the other
• rate = k[A]2: second order reactants constant.
overall (rate  [A]2)
• rate = k[A]0 = k(1) = k: zero • Repeat for each reactant in turn.
order (rate independent of [A])
• Using this method you are also
(a) Using Initial Rates to able to predict reaction rate for a
Determine Rate Laws given set of [reactant].

• Observe the effect of changing • You are not able to determine

initial concentrations of the [reactant] at any time from a
reactants on initial rate of the differential rate law.
reaction.

• If there is more than one

reactant: Measure the initial rate 7

Example: Initial rates in a series of experiments for the reaction between NH4+(aq)
and NO2-(aq)

• The initial rate of a reaction was measured for several different starting
concentrations of reactants. The results are shown below.

NH4+(aq) + NO2-(aq) → N2(g) + 2H2O(l)

Exp No Initial [NH4+] Initial [NO2-] Initial Rate
(M) (M) (M/s)
1 0.0100 0.200 5.4 x 10-7

2 0.0200 0.200 10.8 x 10-7

3 0.200 0.0202 10.8 x 10-7

4 0.200 0.0404 21.6 x 10-7

• Determine the rate law and the rate constant with the correct units.

• Hint: Manipulate the data:

𝑟𝑎𝑡𝑒 2 𝑘 𝑁𝐻 𝑁𝑂
𝑁𝑂 𝑖𝑠 ℎ𝑒𝑙𝑑 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑟𝑎𝑡𝑒 1 𝑘 𝑁𝐻 𝑁𝑂
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(b) Measure Reactant First Order Reactions
Concentration at Different Times • Changes in reactant concentration will be
proportional to changes in the rate. e.g.
Differential Rate Laws: doubling the concentration will double the
rate.
• enable us to calculate rate of
reaction from rate constant and • Consider a reaction which is first order
reactant concentrations. with respect to reactant A:
A → Products
• can be converted using calculus
into integrated rate law 𝒅𝑨
𝒓𝒂𝒕𝒆 𝒌𝑨
equations. 𝒅𝒕

Integrated Rate Laws: • Differential rate law: expresses how

rate depends on concentration
• he integrated rate law (derived • Integrating from t = 0 to t = t:
from differential rate law) tells us
how the [reactant] changes as a 𝑨𝒕
𝐥𝐧 𝒌𝒕 𝒐𝒓 𝐥𝐧 𝑨 𝒕 𝒌𝒕 𝐥𝐧 𝑨 𝟎
function of time and therefore 𝑨𝟎
you can know what the
concentrations of reactants or • Integrated rate law: relates
products are at any time during concentration of A at the start of the rxn
the course of a reaction. to its conc at any other time ([A]t) 9

First Order Reactions Half life of a First Order Reaction

• In practice once would have data of [A]t Half life – time taken for [A]t to drop to one
(at a fixed temp) as a function of time. half of its initial value (= ½ [A]0)
•
• For a first order reaction plotting ln[A]t
versus time would yield a straight line.

ln[A]t = -kt + ln[A]0

Slope = -k
ln[A]t
intercept = ln[A]0
1
𝑆𝑢𝑏𝑠𝑡𝑖𝑡𝑢𝑡𝑒 𝐴 𝐴 𝑖𝑛𝑡𝑜 1𝑠𝑡 𝑜𝑟𝑑𝑒𝑟 𝑒𝑞𝑛
2
1
𝐴 𝐴
time ln 𝑘𝑡 ln 2 𝑘𝑡
𝐴 𝐴

• Knowing [A]0 and k at a fixed temp you

ln 2
can use the integrated rate law to: 𝑡
𝑘
- Predict [A]t at any time • Since t½ is independent of [A]0 for a first
- Calculate time required to reach a order reaction, t½ is the same at any time
particular value of [A]t during the reaction (see graph)
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 Half Life of a First Order Reaction
A first order
Note: Gas concentrations in a rate law reaction
are often expressed as pressures. This
is valid at a fixed temperature as conc α
pressure. (Ideal gas eqn, R and T are
constants)

e.g.(1) N2O5(g) decomposes according

to a first order rate law. If k has the
value 8.5 x 10-3 s-1, what is t½ for this
reaction?
A plot of [N2O5] vs time for three half-lives
2N2O5(g) → 4NO2(g) + O2(g)

e.g. (2) Cyclopropane is the smallest

cyclic hydrocarbon. Because its 60°
bond angles allow poor orbital overlap, The rate constant is 9.2 s-1. (a) What is
its bonds are weak. As a result, it is the half-life of the reaction? (b) How
thermally unstable and rearranges to long does it take for [cyclopropane] to
propene at 1000 °C via the following reach one-quarter of its initial value?
first-order reaction:
(a) 0,075 s; (b) 0,15 s 11

Second Order Reaction Half life of a second order

• A reaction can be first order with reaction
respect to two different reactants:
d[A] 1
  k[A][B] Substituing [A]  [A] into 2nd order eqn :
dt t1
22
0

1 1
• OR second order with respect to one  kt 
1 [A]
reactant: [A] 0

2
0

(we will only consider this case)

d[A]
rate    k[A] 2
1
dt t 
k[A]
1

• Integrating from t = 0 to t=t: 2

0

1 1 1
Note: half life of a 2nd order reaction
 kt  [A]t
[A] t
[A] 0 is dependent on [A]0

time
• A straight line will only be obtained if
the reaction is second order
• Slope = k and the y-intercept = 1
[A] 0
12

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Determining Reaction Order from the Integrated Rate Law

• Given concentrations of a reactant at various times during a reaction you

can determine whether the reaction is first or second order. (Graphical
determination)

• e.g. NO2(g) → NO(g) + ½ O2(g)

Plot ln[NO2] vs time to test for Plot 1/[NO2] vs time to test

1st order reaction for 2nd order reaction

Central Science, 9th ed.

Brown et al, Chemistry: The
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4. Dependence of Reaction Rate on Temperature

Collision Model
Brown et al, Chemistry: The

• Molecules will only react if they collide

Central Science, 9th ed

with the correct orientation and with

sufficient kinetic energy to begin to
rearrange bonds.

• Rate depends on concentration of

reactants and temperature. Collision
Model is based on kinetic molecular
theory and accounts for both these
effects at the molecular level.
Fig. Rate Const vs temp for
rearrangement of methyl isonitrile
Explanation according to collision
• Rate constants do not depend model:
on concentration but do depend • Increase concentration of reactants →
on temperature and catalysts no of collisions increase → increase in
• Rates of most reactions reaction rate.
increase as temperature • Increase temperature → increase speed
increases due to increase in of molecules → molecules collide with
rate constant with increase in more energy and more frequently →
temperature increase reaction rate. 14

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Activation Energy Eg. Rearrangement of CH3CN to CH3CN.
Reaction passes through an intermediate /
• To achieve a reaction transition state.
chemical bonds need to be
broken and rearranged. This
process requires energy.

• Energy is supplied from the

kinetic energies of colliding
molecules.

• The minimum energy required

to start a chemical reaction is
called the activation energy
(Ea).

• The value of Ea is different for

different chemical reactions. Fig. Energy profile for methyl isonitrile isomerisation.
(Brown et al, Chemistry: The Central Science, 9th ed)
• Collisions of fast moving
particles provide sufficient
kinetic energy to overcome ∆E = energy change for the reaction.
the activation energy. 15

Activation Energy
e.g. Rearrangement of CH3NC to • Molecules are distributed over a wide
CH3CN. range of energies at any given moment.
• At a higher temperature a much larger
Q1. Is the forward reaction
fraction of molecules have higher kinetic
exothermic or endothermic? The
energy greater than Ea.
reverse reaction?
• Therefore a larger fraction of molecules
Q2. Does the rate depend on Ea or will have more energy than the Ea
ΔE? required for reaction
• Therefore a much greater rate of
Q3. What is the Ea for reverse
reaction at higher temp.
reaction?

Fig. Effect of temperature on distribution of kinetic energies with min energy needed for rxn
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Activation Energy
Arrhenius Equation

• Describes the rate constant as a function of the activation energy

and reaction temperature.
 Ea
As Ea increases, k decreases
k  A e RT
You can experimentally
determine Ea if you have
• k = rate constant (depends on data of k vs T
reaction order)
• 1st: s-1 2nd: L mol-1 s-1  Ea
ln k   ln A
A = frequency factor (same units RT
as k)
Plot ln k vs 1/T
• Ea = activation energy (J/mol)
R = 8.315 J K-1 mol-1 Slope = -Ea/R
T = temperature (K)
y-intercept = ln A 17