Bahir Dar University

College of Science
Department of Industrial Chemistry
2nd Year Industrial Chemistry Students

Chemical Kinetics and Electrochemistry (Iche 2051)

Chapter Five
Chemical kinetics
Introduction
Chemical kinetics is the study of the rates of chemical reactions, the factors that affect these
rates, and the reaction mechanisms by which reactions occur.
Reaction rates
•It is the speed at which a chemical reaction proceeds. It is often expressed in terms of either
the concentration (amount per unit volume) of a product that is formed in a unit of time or the
concentration of a reactant that is consumed in a unit of time.
•vary greatly – some are very fast (burning) and some are very slow (disintegration of a plastic
bottle in sunlight).
•A reaction mechanism is the step-by-step sequence of elementary reactions by which overall
chemical process occurs.
•A mechanism describes in detail exactly what takes place at each stage of an overall
transformation. It also describes each reactive intermediate, activated complex, and transition
state, and which bonds are broken (and in what order), and which bonds are formed (and in
what order). 
Con…
Factors that affect Reaction Rates
Concentrations of reactants: Reaction rates generally increase as the concentrations of the
reactants are increased.
•The number of particles in a given volume affects the rate at which reactions occur.
• Cramming more particles into a fixed volume increases the concentration of reactants,
and, thus, the frequency of collision.
• Increased collision frequency leads to a higher reaction rate.
Temperature: Reaction rates generally increase rapidly as the temperature is increased.
• Lowering the temperature usually slows down a reaction.
•At higher temperatures, particles move faster.
• The frequency of collisions increases along with the percentage of particles that have
enough kinetic energy to slip over the activation-energy barrier.
• Thus, an increase in temperature causes products to form faster.
Con…
Surface area: For reactions that occur on a surface rather than in solution, the
rate increases as the surface area is increased.
• The result of an increase in surface area is an increase in the frequency of
collisions and the reaction rate.
Catalysts: Catalysts speed up reactions and inhibitors slow them down.
•Increasing the temperature is not always the best way to increase the rate of a
reaction. A catalyst is often better.
• Recall that a catalyst is a substance that increases the rate of a reaction
without being used up during the reaction.
• Catalysts permit reactions to proceed along a lower energy path.
Pressure of gaseous reactants or products: Increased number of collisions
5.1. The rates of chemical reactions
Reaction Rate: The change in the concentration of a reactant or a product
with time (M/s).
Reactant → Products
A→ B
•Average rate= ==
•Since reactants go away with time: Rate =  
•In general, for the reaction:
•aA + bB → cC + dD
•Rate of reaction:
5.2. Reaction rate laws
Rate Law & Reaction Order
•The reaction rate law expression relates the rate of a reaction to the
concentrations of the reactants.
•Each concentration is expressed with an order (exponent).
•The rate constant converts the concentration expression into the correct units of
rate (Ms−1).
•For the general reaction:
aA + bB → cC + dD
Rate = k [A]x [B]y
•x and y are the reactant orders determined from experiment. x and y are NOT
the stoichiometric coefficients.
5.2.1. Zero Order Reactions (rare)
 It has no effect on rate.
 It is the rates that do not depend on reactant concentration.
•A → products
•Rate= =k k is in [moles/ (liter sec)] or M/s or Ms–1
•=
•using calculus, this equation can be transformed into an equation that relates the
conc. A at the start of the reaction, [Ao], to its concentration at any other time t, [A]:
•∫ 1 dx = x + C
•
•[A]- [Ao]=-kt
•[A]= [Ao] – kt
•Where [A]= concentration of A after a time t
[Ao]=initial concentration of A at t=0
Con…
Half-Life
The half-life of a reaction (t 1/2) is the amount of time required for the
concentration of the reactant to drop to one-half its initial value.
[A] = 1/2 [A0]
We can determine the half-life of a zero-order reaction as follows:
[A]= [Ao] – kt
=[Ao] – kt1/2
[Ao]= - kt1/2
- = - kt1/2
t1/2 =
Con…
•Example
1.Using the integrated form of the rate law, determine the rate
constant k of a zero-order reaction if the initial concentration of
substance A is 1.5 M and after 120 seconds the concentration of
substance A is 0.75 M.
Given required
•[Ao]= 1.5 M k=?
•t=120s
•[A]120s= 0.75 M
 
Con…
2. Using the substance from the previous problem, what is the half-life
of substance A if its original concentration is 1.2 M?
Given Required
• [Ao]=1.2M t1/2=?
Solution
•for the half-life:
t1/2 == =96sec
Con…
3. If the original concentration is reduced to 1.0 M in the previous
problem, does the half-life decrease, increase, or stay the same? If the
half-life changes what is the new half-life?
Given Required
• [Ao]=1.0M t1/2=?
Solution
•for the half-life:
t1/2 == =80sec
•Since this is a zero-order reaction, the half-life is dependent on the
concentration. In this instance, the half-life is decreased when the
original concentration is reduced to 1.0 M. The new half-life is 80
seconds.
5.2.2. First Order Reactions
•For the reaction A→ products, the rate is as follows:
•Rate = =k[A] {k is in [1/sec]}
•using calculus, this equation can be transformed into an equation that
relates the conc. A at the start of the reaction, [Ao], to its concentration at
any other time t, [A]:
•∫ (1/x) dx = ln |x| + C
•
•
•ln=-kt
•ln= ln– kt or =
Con…
half-life of a first order •Example
1. A certain first order reaction is 45.0% complete in 65 s.
reaction Determine the rate constant and the half-life for this process.
[A] = 1/2 [A0] Solution:
•Integrated form of first-order rate law:
=o × e-kt ln A = -kt + ln Ao
=o × e-kt1/2 45% complete means 55% remains:
ln 0.55 = - k (65 s) + ln 1
= e-kt1/2 k = 0.0091975 s-1 (I kept a few guard digits for the next
calculation.)
ln2-1 = - kt1/2
for the half-life:
•t1/2== ln 0.5 = - (0.0091975 s-1) (t) + ln 1
t = 75.4 s
for first order reaction half- You can also use this:
life doesn’t depends on t1/2 = (ln 2) / k
to calculate the half-life.
initial concentration.
Con…
2.  A certain reaction is first order, and 540. seconds after initiation of the reaction,
32.5% of the reactant remains. What is the rate constant for this reaction? At what
time after initiation of the reaction of the reaction will 10.0% of the reactant remain?
Solution:
• Integrated form of first-order rate law:
ln A = -kt + ln Ao
ln 0.325 = - (k) (540. s) + ln 1.00
k = 0.002081352 s-1
•Note that the problem specified the amount remaining, not the amount decomposed.
Integrated form of first-order rate law:
ln A = -kt + ln Ao
ln 0.100 = - (0.002081352 s-1) (t) + ln 1.00
t = 1106 s
Con…
3.
3. Second Order Reactions
•A second order reaction is one where one reactant is raised to the second power or two
reactants each raised to the first power.
a) Second order in one component
•A → products
•Rate= =k[A]2
•Relying on calculus, the law can be used to derive the following:
•
•-=
• - -=
•=+
Con…
half-life of second order reaction b) First order in each of two components
A +B → products
=
Rate = - d[A] dt =k[A][B]
=+
= + kt1/2
= + kt1/2
t1/2 =
Con…

1.
Con…
Con…
4. Third Order Reactions

•For a simple third order reaction •half-life of third order reaction

A → products =
Rate= =k[A]3 = +2
•Relying on calculus, the law can be used to = +2 kt1/2
derive the following:
= + 2kt1/2
t1/2 =
-=
- -=
=+

 
Con…
• Summary of Rate Laws for Zero-, First-, Second and Third-Order Reactions
Zero-Order First-Order Second-Order Third -order

rate law rate = k rate = k[A] rate = k[A]2 Rate=k[A]3

units of rate constant M s−1 s−1 M−1 s−1 M-3S-1

integrated rate law [A]=−kt+[A]0 ln[A]=−kt+ln[A]0 =kt+ () =+

 

plot needed for linear fit [A] vs. t ln[A] vs. t 1/[A]vs. t vs.t
of rate data

relationship between k = −slope k = −slope k = slope k =slope

slope of linear plot and
rate constant

half-life t1/2=[A]0/2kt t1/2=0.693/kt t1/2=1/[A]0k t1/2 =

 
Con…
• Example
1.
Con…
Con…
Con…
Con…
2.

3.

4.
Complex Reactions and Mechanisms
•Mechanisms: A series of elementary steps that make up a reaction.
E.g. for A + B + 2C → D + E
Mechanism could be: A + B → F Elementary
F+C→G+D Single Step
G+C→E Reactions
F and G are reaction intermediates
Molecularity: The number of molecules that come together to react in one elementary step.
For single step elementary reactions, Molecularity = Order
A → products 1st order rate = k [A] Unimolecular
A → products 2nd order rate = k [A] 2 Bimolecular
A + B → prod. 2nd order rate = k [A][B] Bimolecular
A + B + C → prod. 3rd order rate = k [A][B][C] Termolecular Etc...

•Molecularity is the number of molecules that need to collide, and in one step form the products.
Some Simple Mechanisms
1. Reversible or opposing reactions
 Reversible reaction approaching to equilibrium
• Let
Con…
1st order reversible reactions
If we start with pure ‘A’ species, [A]0≠0 and [B]0= 0, t=0
Now, [A]0= [A] +[B]
[B]= [A]0-[A]
−d[A]
= k1[A]- k-1[B] = k1[A]- k-1([A]0-[A])
dt
k−1
= k1+ k-1 ([A]- [A]0)
k1+k−1
At equilibrium [A]eq, k1= [B]eq k-1
[B]eq k1 [A]0−[A]eq
= = keq=
[A]eq k−1 [A]eq

k−1
[A]eq= [A]0
k1+k−1
−d[A] k−1
Hence: = k1+ k-1 ([A]- [A]0)
dt k1+k−1
Con…
•= k1+k-1 ([A]-)
•
•=
•Where = concentration of A at equilibrium
• k1 = rate constant for forward reaction
• k-1 = rate constant for backward reaction
2.Consecutive or sequential reaction:
•A chemical reaction in which the product form is further decomposed into
another product such kind reaction of reaction is known as sequential reaction.

•If rate constant of reaction is K1 and K2 then the rate of reaction is for the
reaction

•For the determination of concentration of A after time t, integrating equation (1)

•For the determination of concentration of B after time t,

Con…
•For the determination of concentration of B after time t,

• Net rate of formation of [B]

Con…
•Multiply eK2t to both side and integrating
Con…
•For the determination of concentration of [C] after time t,

•Since by law of mass balance [A]0=[A]t +[B]t+[C]t

Con…
•Case (1):  K1 >>>K2
•Concentration of [B]t: when K1>>>K2 in this case we can observed that reaction first (A to B)
occurs first and gives nearly to completion before reaction (B to C) take place. Thus nearly all the
(A) is converted to the intermediate (B) before any appreciable conversion of (B to C), thus

• Concentration of [C]t:
Con…
•Graphical representation:

•In general concentration of [A] decreases exponentially, and the concentration of [B]
Initially increases up to a maximum and then decrease therefore and concentration of [C]
increases steadily until it  reaches its final value [A]0, when all A has changed into [C]
Con…
•Case (2): K2 >>>K1
•Concentration of [B]t:

•Since K2>>>K1 then second term in parenthesis rapidly approaches zero while the first term is still near
unity consequently concentration of [B] approaches to K1/K2 [A] and decay more slowly according to 

•Since k1/K2 is very small, the maximum concentration of [B] is much less than [A]0
Con…
•Concentration of [C]t: Graphical representation:
3. Parallel Reactions
•Parallel 1st order reactions
 When a compound decomposed in too many paths mostly organic
compound it can able to react in two different ways to give two
different products:

•Rate= =k1[A] + k2[A]= (k1 + k2) [A]

•
•[A] = [A]o × e-(k1 + k2) t
Con…
•For B:
•Rate= =k1[A] = k1 [A]o × e-(k1 + k2) t
•Rearranging and integrating:
× exp (-(k1 + k2) t + constant)
•To find the constant; for t=0, [B]0=0
•Hence: constant =
k1 [A]o
•For c: Therefore [B]= × (1-e )
-(k1 + k2) t
k1 + k2to [A] 0. i.e. [A]+ [B] + [C]= [A]0
•At any time, t, [A], [B] and [C] must sum
•hence [C]= [A]0-[A]- [B]
•[C]= × (1- e-(k1 + k2) t)
4. Chain reaction
•This type of reaction involves free radicals.
•e.g., H2+Br2 2HBr
•furthermore, the elementary steps for the same can be proposed as
•Initiation: Br2 Br. + Br.
•Propagation: Br. + H2 HBr +H.
• H.+ Br2 HBr + Br.
•Inhibition: H. + HBr H2 +Br2
•Termination: Br. + Br. Br2
 To find the rate law: Rate ==????
 Looking at consumption and formation
• =k2[Br.] [H2] +k3 [H.] [Br2]-k4[H.] [HBr] (1)
Con…
 Applying steady state approximation:
• i.e., =0 or =0 (2)
 The life spent time for free radicals is zero at steady state.
• = k2[Br.] [H2] +k3 [H.] [Br2]-k4[H.] [HBr] (3)
• = 2k1[Br2]- k2[Br.] [H2] +k3 [H.] [Br2]-k4[H.] [HBr]-2k5[Br.]2 (4)
 Using equation (3), solving for [H.]
• k2[Br.] [H2] = k3 [H.] [Br2]-k4[H.] [HBr]
• = [H.] (k3 [Br2]-k4 [HBr])
• [H.] =
Con…
Equating eq (3) and eq (4)
• 2k1[Br2]- 2k5[Br.]2
•Solving for: [Br.] = (5)
Using eq (5) in eq (6)
• [H.] = (6)
• 
• [H.] = (7)
Using eq (5) and eq (7) in eq (2)
Con…
•=k2[Br.] [H2] +k3 [H.] [Br2]-k4[H.] [HBr]
= k2√ (k1/k5 [Br2] [H2] + k3 [Br2]- k4 [HBr]

=
The starting equation is:
•
•K” = k’= 
Acid –Base catalyzed reaction
 Various homogeneous catalytic reactions are catalyzed by acids and bases. These reactions are known as acid –
base catalysis.
 The real catalysts are the H+and OH- ions in acid and base catalysis respectively.
• Types of Acid-base catalysis: There are three types of acid-base catalysis.
1. Specific hydrogen ion catalysis: These reactions are catalyzed by H+ ions only. For example, inversion of
cane sugar, which is catalyzed by H+ ions only.

The rate of this reaction is proportional to the concentration of hydrogen ions present in the solution.

2. Specific hydroxyl ion catalysis: These reactions are catalyzed by OH -ions only. For example, the conversion
of acetone into diacetone is catalyzed by OH -ions only.

3. Hydrogen and hydroxyl ion catalysis: These are the reactions in which both H +and OH- ions simultaneously
act as catalysis.
• For example,
• (i)Hydrolysis of ester is catalyzed by H+ as well as by OH-ions.

(ii)Hydrolysis of nitrile is catalyzed by H +as well as by OH-ions.

Mechanism of acid –base catalysis:
•In acid-base catalysis also, there is formation of an intermediate complex which
then dissociates to give products. The mechanism of acid base catalysis can be
explained by some examples.
i. The catalyzed transformation of α-glucose into β-glucose

•where H+(I) is a proton supplied by acid catalyst, GH is the -Glucose, HGH+ is

the intermediate complex which is unstable, HG is the -glucose and H+(II) is
removed by base catalyst.
ii. Hydrolysis of Ethyl Acetate catalyzed by proton: This can be represented as:
Con…
iii. Decomposition of acid base catalysis:
•Acid-base catalyzed reactions take place by transfer of proton from an acid to a substance molecule (S) or from
substance molecule to the base. Hence the reaction between an acid HA and substrate S may be written as:

k1and k2 are the rate constants of forward and backward reactions respectively.

• Immediately after the start of the reaction, SH + will attain a steady state concentration. Hence,
Con…

Hence, the reaction rate is proportional to [H+] even in the presence of HA and
A-. This is a simple case of specific acid catalysis
Enzyme catalyzed reaction
 Enzymes are complex organic compounds which are produced by living plants and
animals.
 These enzymes have dimensions in the colloidal range (1000-1000000A) and are very
specific catalysts.
 Due to their colloidal behavior in solutions, their kinetic behavior is similar to that of
heterogeneous process. So, enzyme catalysis is also known as “micro-heterogeneous
catalysis”.
 Some examples are:

 Table 1 shows some examples of enzymes, their source and the reactions catalyzed by
them.
Characteristics of enzyme Catalysis:
1.All enzymes are proteins and have common properties. They form colloidal solutions and are
of high molecular weight.
2. Enzymes are associated with every chemical reaction that occurs in the living system.
3. Enzymes generally accelerate biochemical reactions by reducing the energy requirement
(activation energy).
4. Enzymes do not alter the amount or nature of the product.
5. Enzymes do not affect the amount of energy released or absorbed during the reaction.
6. Enzymes are not destroyed by the reaction they catalyze and so can be used again. However, a
given molecule of an enzyme cannot be used indefinitely because it is readily inactivated by heat
or action of acid etc. Inorganic catalysts are highly stable and can be used over again.
7. Very small amounts of enzymes are required to catalyze a reaction.
8. Enzymes catalyze biochemical reactions at very low temperatures.
9. Enzymes are specific in their action. An enzyme that can hydrolyze starch is unable to
hydrolyze cellulose. For this, another enzyme, cellulose, is needed.
10.Most enzymes can work in either direction i.e., they are capable of operating reversibly. That
is, one and the same enzyme can catalyze the breakdown as well as the synthesis of the
substance.
Kinetics of enzyme catalysis:
•Enzymes are the best-known catalysts. The kinetics of enzyme catalyzed reaction is explained by Henry’s theory.
According to him, enzyme first combines with reactant (substrate) to form an enzyme substrate complex which
remains in equilibrium with the enzyme and substrate.
𝐸+𝑆𝐸𝑆
•where E is the enzyme, S is the substrate and ES is an enzyme-substrate complex. The rates of forward and
backward reactions are denoted by k1and k2. The enzyme substrate complex ES can decompose to form products with
simultaneous regeneration of the enzyme.
Con…
Con…

∆ 𝐺= ∆ 𝐻 − 𝑇 ∆ 𝑆
Reaction rate theories
1. Collision theory
 collision theory is used to relate the properties of particles to the rates of chemical reactions.
 According to collision theory, atoms, ions, and molecules can react to form products when they collide if
the particles have enough kinetic energy.
 Particles that do not have enough energy to react bounce apart unchanged when they collide.
•Example
•An effective collision of oxygen and hydrogen molecules produces water molecules.

An ineffective collision of oxygen and hydrogen molecules produces no reaction; the reactants bounce apart
unchanged.

The minimum energy that colliding particles must have in order to react is called the activation energy.
Con…
•When two reactant particles collide, they may form an activated complex.
• An activated complex is an unstable arrangement of atoms that forms for a moment at the peak of the
activation-energy barrier.
• The activated complex forms only if the colliding particles have enough energy and if the atoms are
oriented properly.
•When two reactant particles collide, they may form an activated complex.
• The lifetime of an activated complex is typically about 10-13 seconds.
• Its brief existence ends with the reformation of the reactants or with the formation of products.
• Thus, the activated complex is sometimes called the transition state.
•The activation-energy barrier must be crossed before reactants are converted to products.
Con…
• Remember: An endothermic reaction absorbs heat, and an exothermic reaction releases heat.

•Collision theory explains why some reactions are extremely slow at room temperature.
 Carbon and oxygen react when charcoal burns, but the reaction has a high activation energy.
• The O—O and C—C bonds must be broken to form the activated complex.
• At room temperature, the collisions of oxygen and carbon molecules are not energetic enough
to break the bonds.
• Thus, the reaction rate of carbon with oxygen at room temperature is essentially zero.
Con…
2. Transition state theory
 At the moment of collision, molecules with enough energy and the right orientation
combine to form an activated complex
 The activated complex can either revert back to reactants or decompose to products
 The exact nature of the activated complex is difficult to determine
 Less energy is required to form an activated complex than to beak bonds
 Energy diagram