Topic 4:

TOPIC 4:

Reaction
Kinetics

Nur Nadiah Abdul Rashid

BSc. (Hons), MSc.
Dept of Chemistry, CFS IIUM
 Reaction Kinetics

Reaction Rate Collision & Reaction

Transition state Mechanism
Theory
Elementary steps
Effect of [ ]
Rate Equation
Molecularity
(Rate Law) Effect of T
Rate Determining
Rate Integrated Effect of catalyst Step (RDS)
Expression Rate Law Rxn
intermediate
 Reaction Kinetics

Chemical kinetics is a study of how fast a reaction

(reactant product) occurs

Focuses on the reaction rate which is the change in

concentration, [R] or [P] as a function of time

Different reaction has a different rate under different

conditions
Figure 16.1 A faster reaction (top) and a slower reaction (bottom).
 Factors That Influence Rate

Under a specific set of conditions, every reaction has its own characteristic
rate, which depends upon the chemical nature of the reactants.

Concentration

Temperature
Factors affecting Rate of
Reaction
Physical state

The use of catalyst

 Concentration of Reactants
An increase in concentration will increase the numbers of reactant particle, so
the number of collisions will increase, thus increase the number of effective
collisions, rate of reaction increase.

Rate α no. of collision α [ ]

Temperature
An increase in temperature will increase the kinetic energy, thus increase the
no. of collisions with energy more than Ea, increase the effective collisions,
rate of reaction increase. **Related diagram is Maxwell-Boltzmann
distribution.

Rate α collision Energy α T

 Physical state of reactants
• The more finely divided the solid is, the faster the reaction happens.
• A powdered solid will normally produce a faster reaction than if the same mass
is present as a single lump.
• The powdered solid has a greater surface area than the single lump.

Rate α no. of collision α surface area particle

Presence of Catalysts
• The catalyst will lower the activation energy of a reaction, so there will be
second route/alternative pathway with the lower activation energy.
• Thus, increase the frequency of effective collisions and helps a reaction to
proceed more quickly.
 Rate of
Reaction
❑ Rate expression
❑ Rate Law
❑ Integrated Rate Law
 RATE EXPRESSION
(page 698)
•Changes in [reactant] or [product] per unit time

• Reactant concentrations ↓ while products

concentrations ↑
aA + bB cC + dD

1 Δ 1 Δ 1 Δ 1 Δ
rate = - [A] = [B] = [C] = [D]
a Δ - b Δ + c Δ + d Δ
t t t t
2 NO2 (g) N2O4 (g)
Three Types of Reaction
Rates

1. Average rate
2. Instantaneous rate
3. Initial rate
Figure 16.5
 Expressing Rate in Terms of Changes in Concentration
Sample Problem 16.1
with Time

PROBLEM:
2H2(g) + O2(g) 2H2O(g)

(a) Express the rate in terms of changes in [H2], [O2], and [H2O] with
time.

(b) When [O2] is decreasing at 0.23 mol/L*s, at what rate is [H2O]

increasing?

EXCERCISES: 16.1A – 16. 1B

Sample Problem 16.1 (page
701)
SOLUTION:
Δ[O2] 1 Δ[H2] 1 Δ[H2O]
(a) Rate = – =– =
Δt 2 Δt 2 Δt

(b) Calculating the rate of change of [H2O]:

1 Δ[H2O] Δ[O2]
=– = – (– 0.23 mol/L·s)
2 Δt Δt

Δ[H2O]
= 2(0.23 mol/L·s) = 0.46 mol/L·s
Δt

Follow-up Problem
16.1A
 RATE LAW (RATE EQUATION)
(page 702)
Rate law definition:
An equation that shows the dependence of the reaction rate on the
concentration of each reactant.

Reaction orders

How rate is
affected by [R]
 RATE LAW (RATE EQUATION)

First-order rate equation:

Δ[A]
rate = – = k [A]
Δ
t
Second-order rate equation:

rate = – Δ[A] = k [A]2

Δ
t
Zero-order rate equation:

rate = – Δ[A] = k [A]0

Δ
t
 Reaction Orders
(page 703)

• A reaction has an individual order “with respect to” or “in”

each reactant.
Rate = k[A]2[B]
The rate is second order with respect to A and first order
with respect to B so it is third order overall (2+1=3)
• For the simple reaction;
A → products
• Let’s say; the reaction is first order with respect to A.
• If the rate doubles when [A] doubles, the rate
depends on [A]1.
 Reaction Orders
• A reaction has an individual order “with respect to” or “in”
each reactant.
Rate = k[A]2[B]
The rate is second order with respect to A and first order with
respect to B so it is third 0rder overall (2+1=3)

• For the simple;

reaction A → products

• If the rate quadruples when [A] doubles, the rate depends

on
[A]2
• Hence, the reaction is second order with respect to [A].
 Reaction Orders

• A reaction has an individual order “with respect to” or “in”

each reactant.
Rate = k[A]2[B]
The rate is second order with respect to A and first order with
respect to B so it is third 0rder overall (2+1=3)

• For the simple reaction;

A → products
• If the rate does not change when [A] doubles, the rate
does not
depend on [A].
• Hence, the reaction is zero order with respect to A.
Individual and Overall Reaction Orders
For the reaction

the rate law is

The reaction is second order with respect to NO, first order

with respect to H2 and third order overall.
Note that the reaction is first order with respect to H2 even
though the coefficient for H2 in the balanced equation is 2.
Reaction orders must be determined from experimental data
and cannot be deduced from the balanced equation.
 Sample Problem 16.2 (page
705)
Determining Reaction Orders from Rate Laws
PROBLEM: For each of the following reactions, use the given rate
law to determine the reaction order with respect to each reactant and
the overall order; for the reaction in (a), determine the factor by
which the rate changes if [NO] is tripled and [O2] is doubled.
(a)

(b)

(c)
Sample Problem 16.2: Solution
SOLUTION: (a) The exponent of [NO] is 2, so the reaction is second
order with respect to NO, first order with respect to O2, and third
order overall. Finding the change in rate:

The rate increases by a factor of 18.

(b) The reaction is order in CH3CHO and order overall.

(c) The reaction is first order in H2O2, first order in I−, and second
order overall.

The reactant H+ does not appear in the rate law, so the reaction is
zero order in H+.
 Determining Reaction Orders
(page 706)
For the general reaction A + 2B → C + D,
the rate law will have the form

Rate = k[A]m[B]n

To determine the values of m and n, we run a series of

experiments in which one reactant concentration
changes while the other is kept constant, and we
measure the effect on the initial rate in each case.
Table 16.2 Initial Rates for the Reaction between O2 and NO

O2(g) + 2NO(g) → 2NO2(g) Rate = k[O2]m[NO]n

Initial Reactant
Concentrations (mol/L)
Initial Rate
Experiment (mol/L·s) [O2] [NO]
1 3.21x10-3 1.10x10-2 1.30x10-2
2 6.40x10-3 2.20x10-2 1.30x10-2
3 12.8x10-3 1.10x10-2 2.60x10-2
4 9.60x10-3 3.30x10-2 1.30x10-2
5 28.8x10-3 1.10x10-2 3.90x10-2
 Determining Reaction Orders
Using initial rates -
Run a series of experiments, each of which starts with a different set of
reactant concentrations, and from each obtain an initial rate.
See Table 16.3 for data on the reaction
O2(g) + 2NO(g) 2NO2(g) rate = k [O2]m[NO]n

Compare 2 experiments in which the concentration of one reactant varies and

the concentration of the other reactant(s) remains constant.

rate 2 k [O2]2m[NO]2n [O2]2m

m
[O2]2
= = =
rate 1 m
k [O2]1 [NO]1 n [O2]1m [O2]1

m
6.40x10-3 mol/L*s 2.20x10-2 mol/L
= ; 2 = 2m m=1
-3 -2
3.21x10 mol/L*s 1.10x10 mol/L

Do a similar calculation for the other reactant(s).

Try Follow-up 16.3B (page
710)
Table 16.3 Units of the Rate Constant k for Several Overall
Reaction Orders

Overall Reaction Order Units of k (t in seconds)

0 mol/L*s (or mol L-1 s-1)

1 1/s (or s-1)

2 L/mol*s (or L mol -1 s-1)

3 L2 / mol2 *s (or L2 mol-2 s-1)

 Integrated Rate Laws
(page 712)

An integrated rate law includes time as a variable.

First-order rate equation:

Δ[A] [A]0
rate = – = k [A]
ln = kt
Δt [A]t

Second-order rate equation:

Δ[A] 1 1
2
rate = – = k [A] – = -kt
Δt [A]0 [A]t

Zero-order rate equation:

Δ[A] [A]o – [A]t = kt

rate = – = k [A]0
Δt
Figure 16.11 Integrated rate laws and reaction orders.

1/[A]t = kt + 1/[A]0

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

ln[A]t = -kt + ln[A]0
Figure 16.12 Graphical determination of the reaction order for the
decomposition of N2O5.

The concentration data is used to construct

three different plots.

Since the plot of ln [N2O5] vs. time gives a

straight line, the reaction is first order.
 Sample Problem 16.5 (page
712)
Determining the Reactant Concentration After a Given Time in
a First-Order Reaction
PROBLEM: At 1000˚C, cyclobutane (C4H8) decomposes in a
first-order reaction, with the very high rate constant of
to two molecules of ethylene (C2H4).
(a) The initial C4H8 concentration is 2.00 M. What is the
concentration after 0.010 s?
(b) How long will it take for 70.0% of the C4H8 to decompose?
Sample Problem 16.5: Solution
SOLUTION: (a) Substituting the data into the integrated rate law:

Taking the antilog of both sides and solving for [C4H8]t:

(b) Substituting the data into the integrated rate law:

 Reaction Half-life
(page 713)
▪ The half-life (t½ ) for a reaction is the time taken for the
concentration of a reactant to drop to half its initial value.

▪ For a first-order reaction, t1/2 does not depend on the

starting concentration.
ln 2 0.693
t ½= =
k k

▪ The half-life for a first-order reaction is a constant.

▪Radioactive decay is a first-order process. The half-life for

a radioactive nucleus is a useful indicator of its stability.
A plot of [N2O5] vs. time for three half-lives.

for a first-order process

ln 2 0.693
t1/2 = =
k k
 Sample Problem 16.7 Determining the Half-Life of a First-Order Reaction
(page 715)
PROBLEM: Cyclopropane is the smallest cyclic hydrocarbon. Because its 60o bond
angles allow poor orbital overlap, its bonds are weak. As a result, it is
thermally unstable and rearranges to propene at 1000oC via the
following first-order reaction:

The rate constant is 9.2 s-1, (a) What is the half-life of the reaction? (b) How long
does it take for the concentration of cyclopropane to reach one-quarter of the initial
value?
0.693
PLAN: Use the half-life equation, t1/2 = , to find the half-life.
k
One-quarter of the initial value means two half-lives have passed.
SOLUTION:

(a) t1/2 = 0.693/9.2 s-1 = 0.075 s (b) 2 t1/2 = 2(0.075 s) = 0.150 s

Try Follow-up
16.7B!
 Expressing Reaction
Rate

Rate Rate Equation Integrated

Expression (Rate Law) Rate Law

Rate = - ∆[reactant] Rate = k [A]m [B]n

∆t
First order ; ln [A]0 = kt
or [A]t
+∆[product]
∆t
Second order ; 1 - 1 =- kt
[A]0 [A]t

Zero order ; [A]0-[A]t = kt

Collision &
Transition state
Theory
(page 720)
 How does reaction occur?
In order for a chemical reaction to take place, the reactants must collide
through the effective collisions.

Correct Orientation
• The molecules must also collide in the right orientation, or hit at
the right spot, in order for the reaction to occur.
• Here’s an example:
• Suppose you have an equation showing molecule A-B reacting
with C to form C-A and B, like this:
• A-B + C→C-A + B
• The way this equation is written, the reaction requires that
reactant C collide with A-B on the A end of the molecule.
• If it hits the B end, nothing will happen. The A end of this
hypothetical molecule is called the reactive site, the place on the
molecule that the collision must take place in order for the
reaction to occur
Figure 16.18 The importance of molecular orientation to an effective
collision.

NO(g) + NO3(g) → 2NO2(g)

There is only one relative

orientation of these two
molecules that leads to an
effective collision.
 How does reaction occur?
In order for a chemical reaction to take place, the reactants must collide
through the effective collisions.

Collision Energy ≥Activation Energy

• The collision between the

molecules in a chemical reaction
provides the kinetic energy
needed to break the necessary
bonds so that new bonds can be
formed.
Figure 16.4 Sufficient collision energy is required for a reaction to
occur.
Energy profile diagram for endo and exo reactions
Based on Collision Theory;
1) Concentration
- more molecules, more effective collisions
- hence, rate increases

2) Temperature
- higher T, higher KE , higher speed of particles, greater
collisions
- hence, rate increases
 Effect of
Temperature
❖ A rise in T increases the KE of the reactant particle and enlarges the
fraction of collisions with enough energy to exceed Ea which is given
by area under the curve

Collisions happen but no

bond
Breaking or forming

Maxwell Boltzman Distribution:

The effect of temperature on the distribution of collision
energies.
 Transition State Theory (pg 722)

• An effective collision between particles leads to the

formation of a transition state or activated complex.

• The transition state is an unstable species that contains

partial bonds. It is a transitional species partway between
reactants and products.

• The transition state exists at the point of maximum potential

energy.

•The energy required to form the transition state is the

activation energy.
Figure 16.20 Depicting the reaction between BrCH3 and OH– .
Example:

A + BC → AB + C (exothermic process)

Draw the energy profile diagram & label completely, including its
transition state.
 Catalysis: Speeding up a Reaction

▪ A catalyst is a substance that increases the reaction rate

without itself being consumed in the reaction.

▪ In general, a catalyst provides an alternative reaction pathway

that has a lower total activation energy than the uncatalyzed
reaction.
▪ A catalyst will speed up both the forward and the reverse
reactions.

▪ A catalyst does not affect either ΔH or the overall yield for a

reaction.
 Types of Catalyst

Homogenous Heterogenous
The catalyst in the same The use of a catalyst in a
phase as the reactants different phase from the
reactants
Figure 16.23 Reaction energy diagram for a catalyzed (green) and uncatalyzed
(red) process.
Based on Arrhenius equation (pg 725):

-Ea/RT
k = Ae

1) Temperature
- Higher T, lower Ea/RT, hence, higher
k
- Higher k, higher rate

2) Catalyst
- provides pathway with lower Ea
- lower Ea, lower Ea/RT, hence, higher k
- Higher k, higher rate
 REACTION MECHANISMS
❑ A sequence of single/individual reaction steps that sum to
the overall reaction
Elementary
❑ For example: steps

2A + B C + D (overall chemical equation)

❑ Proposed reaction mechanism:

Elementary step 1: A + A + G E (slow)
Elementary step 2: E + B C + D + G (fast)

❑ Identify which is intermediate and catalyst

Intermediate : Substance that is produced and consumed

during the rxn

Catalyst : Substance that is consumed and produced

during the rxn. Catalyst remains at the end of rxn
 Molecularity :The number of reactant particles in elementary steps/overall
steps

Elementary Molecularity Rate Law

Step

A product Unimolecular Rate= k [A]

2A product Bimolecular Rate = k[A]2

Reaction
order equals
A + B product Bimolecular Rate = k[A][B] molecularity

2A + B product Termolecular Rate = k[A]2[B]

Table 16.6 Rate Laws for General Elementary Steps

 Determining Molecularity and Rate Laws for
Elementary Steps
PROBLEM: The following two reactions are proposed as elementary steps in
the mechanism of an overall reaction:
(1) NO2Cl(g) NO2(g) + Cl(g)
(2) NO2Cl(g) + Cl(g) NO2(g) + Cl2(g)
(a) Write the overall balanced equation.
(b) Determine the molecularity of each step.
(c) Write the rate law for each step.
SOLUTION: (b) Step(1) is unimolecular.
(a) (1) NO2Cl(g) NO2(g) + Cl (g) Step(2) is bimolecular.
(2) NO2Cl(g) + Cl (g) NO2(g) + Cl2(g) (c) rate1 = k1[NO2Cl]
rate2 = k2[NO2Cl][Cl]
2NO2Cl(g) 2NO2(g) + Cl2(g)

Additional excercises:
FUP 16.11A, FUP 16.11B
 REACTION MECHANISMS

❑ For example:

2A + B C + D (overall chemical equation)

❑ Proposed reaction mechanism:

Elementary step 1: A + A + G E (slow)
Elementary step 2: E + B C + D + G (fast)

❑ Slow step (or step 1) indicating the RDS (rate determining step)

RDS is the step that will determine the rate of reaction and
also determine the rate law for the whole reaction.

*elementary step with higher Ea is the slow step (RDS)

 The Rate-Determining Step of a Reaction
The slowest step in a reaction is the rate-determining or rate-limiting
step.

Reaction Mechanism

1st Elementary step Slow: RDS

Slow
2nd Elementary step Fast

3rdElementary step Fast

Overall Reaction Slow

The rate law for the rate-determining step becomes the rate
law for the overall reaction.
 The Rate-Determining Step of a Reaction

The slowest step in a reaction is the rate-determining or rate-limiting

step.

The reaction NO2(g) + CO(g) → NO(g) + CO2(g)

has been proposed to occur by a two-step mechanism. Given rate=k[NO2]2
(1) NO2(g) + NO2(g) → NO3(g) + NO(g) [slow; rate-determining]
(2) NO3(g) + CO(g) → NO2(g) + CO2(g) [fast]

Is the proposed mechanism valid?

The rate law for the rate-determining step becomes the rate
law for the overall reaction.
1. Overall eq: NO2(g) + CO(g) → NO(g) + CO2(g)
which is the same as given reaction.

2. Rate law of RDS; rate=k[NO2] which is the same as

observed rate law.

3. Both elementary steps are bimolecular, which are

reasonable steps.

Hence; the proposed mechanism is valid.

A valid mechanism must meet 3 criteria:

1. The elementary steps must add up to the overall balanced equation.

2. The elementary steps must be reasonable (unimolecular or bimolecular)

3. The rate law of RDS = rate law of overall reaction

 By using suitable diagram(s), explain how
the
rate reaction can be affected by
a) Catalyst
b) temperature
 EXCERCISES: INTEGRATED RATE LAW
1. Sucrose decomposes to fructose and glucose in acid solution. When ln
[sucrose] is plotted vs. time, a straight line with slope of -0.208 hr¯1
results. What is the rate law for the reaction?

2. Tetrafluoroethylene, C2F4, can be converted to octafluorocyclobutane

which can be used as a refrigerant or an aerosol propellant. A plot of
1/[C2F4] vs. time gives a straight line with a slope of 0.0448 L mol¯1s¯1.
What is the rate law for this reaction?

3. The decomposition of hydrogen peroxide is a first-order process with a

rate constant of 1.06 × 10¯3 min¯1. How long will it take for the
concentration of H2O2 to drop from 0.0200 M to 0.0120 M?
4. Cyclopropane is converted to propene in a first-order process. The rate
constant is 5.4 × 10¯2 hr¯1. If the initial concentration of cyclopropane is
0.150 M, what will its concentration be after 22.0 hours?

5. The rate law for the reaction 3A → 2B is rate = k[A] with a rate constant
of 0.0447 hr¯1. What is the half-life of the reaction?

6. The rate law for the rearrangement of CH3NC to CH3CN at 800 K is

Rate = (1300 s¯1)[CH3NC]. What is the half-life for this reaction?
 Islamization
Regardless if it’s Iron or stone, or the bones are in the museum, still the promise of Allah
will take its effect, we all will be resurrected. So Allah used this words in Quran, Say, "Be
you stones or iron” Surah Al Isra Verse 50

Say, "Be you stones or

iron

Allah doesn’t forget anything, man didn’t know that bones after several million years can
turn into stone or iron, and this was revealed to our prophet (saw) 1500 years ago, so
this one small verse proves many things, like, the Quran is the divine inspiration from
Allah related to the reaction rate. According to the rules of Quantum Mechanics , given
enough time , all matter ( stars, trees, planets, humans, etc.,) will eventually turn into
iron regardless of the speed of reaction( which might be rapidly or slowly).