Chapter 4

Chemical Kinetics

CHEMICAL KINETICS

Prepared by:
Miss Salmi Nur Ain

Reference: Chemistry: the Molecular Nature of Matter and Change,

6th ed, 2011, Martin S. Silberberg, McGraw-Hill
 Learning Outcomes
• At the end of this topic, students should be able to:

1. Calculate rates of chemical reactions.

2. Apply integrated rate laws to determine concentration.
3. Evaluate the effect of temperature on chemical kinetics
4. Differentiate between homo-, hetero- and enzymatic
catalysis
5. Identify the reaction mechanisms from elementary
reaction
 Chemical Kinetics
• Chemical kinetics is the study of reaction
rates, the changes in concentrations of
reactants (or products) as a function of time.

• Chemical kinetics is the study of rates of

chemical reactions, the factors that affect
reaction rates, and the mechanisms (the
series of steps) by which reactions occur.
FACTORS THAT INFLUENCE
REACTION RATE

• Physical state of reactants

• Concentration of reactants
• Temperature
• Presence of catalysis
FACTORS THAT INFLUENCE REACTION
RATE

1. Physical State of the Reactants

– In order to react, molecules must come
in contact with each other.
– The more homogeneous the mixture of
reactants, the faster the molecules can
react.
2. Concentration of Reactants
– A reaction can occur only when the
reactant molecules collide.
– As the concentration of reactants
increases, the more molecules present in
the container, the more frequently they
collide, and the more often a reaction
between them occurs.
– Thus, reaction rate is proportional to the
concentration of reactants:
Rate α collision frequency α concentration
3. Temperature
– At higher temperatures, reactant
molecules have more kinetic energy,
move faster, and collide more often and
with greater energy.
4. Presence of a Catalyst
– Catalysts speed up reactions by changing
the mechanism of the reaction.
– Catalysts are not consumed during the
course of the reaction.
4.1 Rates of Chemical Reactions
 Reaction Rates

A B
• A rate is a change in some variable per unit of time.
• Rates of reactions can be determined by monitoring the change in
concentration of either reactants or products as a function of time.
• Consider a general reaction, A  B .
• We quickly measure the starting reactant
concentration (conc A1) at t1, allow the reaction to
proceed, and then quickly measure the reactant
concentration again (conc A2) at t2.
• The change in concentration divided by the change
in time gives the average rate:

• We use the minus sign simply to convert the

negative change in reactant concentration to a
positive value for the rate.
• If instead we measure the product to
determine the reaction rate, we find its
concentration increasing over time.
• That is, conc B2 is always higher than conc B1.
• Thus, the change in product concentration,
Δ[B], is positive, and the reaction rate for A
 B expressed in terms of B is
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

In this reaction, the

concentration of butyl
chloride, C4H9Cl was
measured at various times.
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

The average rate of the

reaction over each
interval is the change in
concentration divided
by the change in time:

C4 H 9Cl 
average rate  -
t
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

• Note that the average

rate decreases as the
reaction proceeds.
• This is because as the
reaction goes forward,
there are fewer
collisions between
reactant molecules.
 C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

• A plot of concentration vs.

time for this reaction yields a
curve like this.
• The slope of a line tangent to
the curve at any point is the
instantaneous rate at that
time.
• All reactions slow down over
time.
 Reaction Rates and Stoichiometry

C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

• In this reaction, the ratio of C4H9Cl to C4H9OH is 1:1.

• Thus, the rate of disappearance of C4H9Cl is the
same as the rate of appearance of C4H9OH.

C4 H 9Cl  C4 H 9OH 

rate   
t t
• What if the ratio is not 1:1?
2 HI(g)  H2(g) + I2(g)

• Therefore,

1 HI  I 2 
rate   
2 t t
• To generalize, then, for the reaction

aA + bB cC + dD

1 A 1 B  1 C  1 D 

rate     
a t b t c t d t
 Chapter 4
Chemical Kinetics

4.2 Rate Law and Concentration Dependence

Reference: Chemistry: the Molecular Nature of Matter and Change,

6th ed, 2011, Martin S. Silberberg, McGraw-Hill
 Concentration and Rate

We can gain information about the rate

of a reaction by seeing how the rate
change with changes in concentration.
NH4+(aq) + NO2−(aq) N2(g) + 2 H2O(l)

Comparing Experiments 1 and 2,

when [NH4+] doubles, the initial rate doubles.
 NH4+(aq) + NO2−(aq) N2(g) + 2 H2O(l)

Likewise, comparing Experiments 5 and 6,

when [NO2−] doubles, the initial rate doubles.
• This means
Rate  [NH4+]
Rate  [NO2−]
Rate  [NH+] [NO2−]
or
Rate = k [NH4+] [NO2−]

• This equation is called the rate law, and k is

the rate constant.
 Rate Laws
• A rate law shows the relationship between the
reaction rate and the concentrations of reactants.
• For a general reaction,
aA + bB + … cC + dD + …
• the rate law has the form

• The exponents m and n, called the reaction orders,

define how the rate is affected by reactant
concentration.
• The overall reaction order can be found by adding
the exponents on the reactants in the rate law.
Examples:
NH4+(aq) + NO2−(aq) N2(g) + 2 H2O(l)

Rate = k [NH4+] [NO2−]

• This reaction is
First-order in [NH4+]
First-order in [NO2−]

• This overall reaction is second-order.

• If the rate doubles when [A] doubles, the rate depends on [A] raised to
the first power, [A]1, so m = 1.
• Similarly, if the rate quadruples when [B] doubles, the rate depends on
[B] raised to the second power, [B]2, so n = 2.

• In another reaction, the rate may not change at all when [A] doubles; in
that case, the rate does not depend on [A], or, to put it another way, the
rate depends on [A] raised to the zero power, [A]0, so m = 0.

• Keep in mind that the coefficients a and b in the general balanced

equation are not necessarily related in any way to these reaction orders
m and n.
 A key point to remember is that the components of the rate law:
rate, reaction orders, and rate constant must be found by experiment;
 Determining Reaction Orders
Experimentally
Example:
Consider the reaction between oxygen and nitrogen monoxide, a key step in the formation of
acid rain and in the industrial production of nitric acid:
O2(g) + 2NO(g)  2NO2(g)
Determine the rate law for the reaction

Rate = k[O2]m[NO]n
The rate law, expressed in general form, is
• Table shows experiments that change one reactant concentration while keeping the
other constant.
• If we compare experiments 1 and 2, we see the effect of doubling [O 2] on the rate.
• First, take the ratio of their rate laws:

• Because k is a constant and [NO] does not change between these two experiments,
these quantities cancel.

• Substituting the values from Table, we obtain

• Dividing, we obtain and rounding the figure:

• The reaction is first order in O2 .

• To find the order with respect to NO, we compare experiments 3
and 1 , in which [O2] is held constant and [NO] is doubled:

• As before, k is constant, and in this pair of experiments [O2]

does not change, so these quantities cancel:

=
• we obtain and rounding the figure

• The reaction is second order in NO.

• Thus, the rate law is
 Determining the Rate Constant
• The rate constant is specific for a particular reaction at a
particular temperature.
• The experiments with the reaction of O2 and NO were run at the
same temperature, so we can use data from any to solve for k.

From experiment 1,

The average value of k for the five experiments in Table is 1.73 x 10 3 L2/mo12·s
• Units for the rate constant :
 Chapter 4
Chemical Kinetics

4.3 Integrated Rate Laws

Reference: Chemistry: the Molecular Nature of Matter and Change,

6th ed, 2011, Martin S. Silberberg, McGraw-Hill
 Integrated Rate Laws

• Zero Order Process

• First Order Process
• Second Order Process

• The equation that relates concentration and time is

the integrated rate equation.
• We can also use it to calculate the half-life, t1/2, of a
reactant-the time it takes for half of that reactant to
be converted into product.
• The integrated rate equation and the half-life are
different for reactions of different order.
 Zero Order Process
Integrated Rate Graphing Half-life
Equation (linear equation
form)

[A]0
 t1/ 2
2k
 First Order Process
Integrated Rate Graphing Half-life
Equation (linear equation
form)

ln [A]t = − ak t + ln [A]0

y = mx + b
0.693
= t1/2
k
 Second Order Process
Integrated Rate Graphing Half-life
Equation (linear equation
form)

1
= t1/2
k[A]0
Y = mX + b
 Zero -Order Processes
aA  product
[ A] d [ A]
rate   
t dt
From rate law,
rate  ak[A]0
d [ A]
  ak
dt
[A]  [A]0   akt
First-Order Processes

a represents the coefficient of reactant A

in the balanced overall equation.
 • Using calculus to integrate the rate law for a first-order
process gives us
[A]t
ln = −akt
Where
[A]0
 [A]0 is the initial concentration of A.
 [A]t is the concentration of A at some time, t,
during the course of the reaction.
• Manipulating this equation produces…

ln [A]t − ln [A]0 = − akt

ln [A]t = − ak t + ln [A]0
…which is in the form
y = mx + b
Therefore, if a reaction is first-order, a plot of ln[A] vs. t will
yield a straight line, and the slope of the line will be –ak.
• Using ideal gas equation,
PV=nRT
nA P
 [ A] 
V RT
[ A] P / RT P
ln  ln  ln
[ A]0 Po / RT P0
P
ln   kt
P0
ln P   kt  ln P0
ln [A]t = -akt + ln [A]0
 Second-Order Processes
For a simple second order reaction,
aA  product
[ A] d [ A]
rate   
t dt
From rate law,
rate  ak[A]2
d [ A]
  ak[A]2
dt
d [ A]
2
  akdt
[A]
1 1
  akt
[ A] [ A]0
Example: Consider the process in which methyl
isonitrile is converted to acetonitrile.
CH3NC CH3CN
This data was collected for this
reaction at 198.9°C.
• When ln P is plotted as a function of time, a straight
line results
• Therefore,
 The process is first-order.
 k is the negative slope, k = 5.1  10 −5 s-1.
Example:
The decomposition of NO2 at 300°C is described by
the equation
NO2 (g) NO (g) + 1/2 O2 (g)
and yields data was shown below. Find the order of this
process.
Time (s) [NO2], M
0.0 0.01000
50.0 0.00787
100.0 0.00649
200.0 0.00481
300.0 0.00380
• Graphing ln [NO2] vs. t yields:

• The plot is not a straight line,

so the process is not first-
order in [A].
Time (s) [NO2], M ln [NO2]
0.0 0.01000 −4.610
50.0 0.00787 −4.845
100.0 0.00649 −5.038
200.0 0.00481 −5.337
300.0 0.00380 −5.573
 • Graphing 1/[NO2] vs. t,
gives this plot.
• Because this is a straight
line, the process is
second-order in [A].

Time (s) [NO2], M 1/[NO2]

0.0 0.01000 100
50.0 0.00787 127
100.0 0.00649 154
200.0 0.00481 208
300.0 0.00380 263
Example
A reaction, A  B + C is carried out at a particular temperature.
As the reaction proceeds, we measure the molarity of the
reactant, [A] at various time, as tabulated below:

a) Determine the order of the

reaction.
b) State the rate-law expression for the
reaction.
c) Calculate the value of the rate
constant, k at this temperature.
Solution:
a) Determine the order of the reaction.

From graphical plots, the reaction is deduced to be 1st

order since plots of ln[A] vs. t gives straight line (linear).
b) State the rate-law expression for the reaction.
Rate law expression: r = k[A]

c) Calculate the value of the rate constant, k at this temperature.

For 1st order reaction, slope, m = -ak
 rate constant, k = - (m/a) = 0.29 min-1

(1.83)  (0.2)
 0.29
8. 5  1. 5
Half-Life
• Half-life is defined as
the time required for
one-half of a reactant
to react.
• Because [A] at t1/2 is
one-half of the original
[A],
[A]t = 0.5 [A]0.
 Zero -Order Processes
For a zero-order process,

[A]  [A]0   kt
0.5[A]0  [A]0   kt1/ 2
0.5[A]0  kt1/ 2
[A]0
 t1/ 2
2k
 First-Order Processes
For a first-order process, this becomes
[A]t
ln = −kt
[A]0
0.5 [A]0
ln = −kt1/2
[A]0
ln 0.5 = −kt1/2
−0.693 = −kt1/2
0.693
= t1/2
NOTE: For a first-order k
process, the half-life
does not depend on [A]0.
 Second-Order Processes
For a second-order process,
1 1
  kt
[ A] [ A]0
1 1
= kt1/2 +
0.5 [A]0 [A]0
2 1
= kt1/2 +
[A]0 [A]0

2 − 1 = 1 = kt
[A]0 [A]0
1/2

1
= t1/2
k[A]0
Example
The decomposition of ethane (C2H6) to methyl
radicals is a first order reaction with a rate constant
of 5.36 x 10-4 s-1 at 700°C.
C2H6 (g)  2CH3 (g)
Calculate the half-life of the reaction in minutes.
0.693
= t1/2
k

Answer:
t1/2 = 21.5 min
 Chapter 4
Chemical Kinetics

4.4 Temperature and Kinetics

Reference: Chemistry: the Molecular Nature of Matter and Change,

6th ed, 2011, Martin S. Silberberg, McGraw-Hill
 EFFECTS OF CONCENTRATION
AND TEMPERATURE
• The two major models that explain the observed effects
of concentration and temperature on reaction rate
highlight different aspects of the reaction process but
are completely compatible.
• Collision theory views the reaction rate as the result of
particles colliding with a certain frequency and
minimum energy.
• Transition state theory offers a close-up view of how
the energy of a collision converts reactant to product.
 COLLISION THEORY
• In a chemical reaction, bonds are broken
and new bonds are formed.
• Molecules can only react if they collide
with each other.
• Furthermore, molecules must collide with
the correct orientation and with enough
energy to cause bond breakage and
formation.
• Collisions must occur in order for a chemical reaction to proceed,
but they do not guarantee that a reaction will occur.
• For a collision to be effective, the reacting species must

1) possess at least a certain minimum energy necessary to

rearrange outer electrons in breaking bonds and forming new
ones and
2) have the proper orientations toward one another at the time
of collision.

• The colliding molecules must have the proper orientation

relative to one another and have sufficient energy to react.
• If colliding molecules have improper orientations, they do
not react even though they may possess sufficient energy.
• Figure 16-9 depicts some possible collisions between molecules
of NO and N2O, which can react to form NO2 and N2.

For some reactions, the

presence of a
heterogeneous catalyst
can increase the fraction
of colliding molecules
that have the proper
orientations.
 Activation Energy
• There is a minimum amount of energy required for
reaction: the activation energy, Ea.
• Just as a ball cannot get over a hill if it does not roll up the
hill with enough energy, a reaction cannot occur unless
the molecules possess sufficient energy to get over the
activation energy barrier.
 TRANSITION STATE THEORY
• The internal energy of a system is the sum of its kinetic and
potential energies.
• When two molecules approach one another, some kinetic
energy is converted to potential energy as the electron
clouds repel each other.
• At the moment of a head-on collision, the molecules stop,
and their kinetic energy is converted to the potential
energy of the collision.
• If this potential energy is less than the activation energy,
the molecules recoil, bouncing off each other and the
molecules zoom apart without reacting.
• The tiny fraction of molecules that are oriented effectively
and moving at the highest speed behave differently.
• Their kinetic energy pushes them together with enough force
to overcome repulsions and react.
• At some point during this smooth transformation, what
exists is neither reactant nor product but a transitional
species with partial bonds.
• This extremely unstable species, which is called the
transition state, or activated complex, exists only at the
instant when the reacting system is highest in potential
energy.
• Thus, the activation energy is the quantity needed to stretch
and deform bonds in order to reach the transition state.
 Reaction Coordinate Diagrams

• It is helpful to visualize energy changes throughout a process on a reaction

coordinate diagram like this for the rearrangement of methyl isonitrile.
• It shows the energy of the reactants and products (and, therefore, E).
• The high point on the diagram is the transition state.
• The species present at the transition state is called the activated complex.
• The energy gap between the reactants and the activated complex is the
activation energy barrier.
Reaction Coordinate Diagrams
• Consider the one-step reaction at a certain temperature.
A + B2  AB + B
• Figure shows plots of potential energy versus the progress of the reaction.
• The ground state energy of the reactants, A and B 2, is higher than the
ground state energy of the products, AB and B.
• The energy released in the reaction is the difference between these two
energies, ΔE. It is related to the change in enthalpy, ΔH°rxn.
• According to the transition state theory, the reactants pass through a short-lived,
high energy intermediate state, called a transition state, before the products are
formed.
• When the atoms go from the transition state arrangement to the product
molecules, energy is released.
• If the reaction results in a net release of energy, more energy than the activation
energy is returned to the surroundings and the reaction is exothermic.
• For the reverse reaction to occur, some molecules on the right (AB) must have
kinetic energy equal to the reverse activation energy, Ea , to allow them to
reverse

reach the transition state.

• If the reaction results in a net absorption of energy, an amount less
than Ea is given off when the transition state is converted to
products and the reaction is endothermic.
• The net release of energy is ΔErxn.
 EFFECT OF TEMPERATURE ON REACTION RATE

• Generally, k increases as temperature increases.

• This is because k is temperature dependent.
• Swedish chemist, Svante Arrhenius,
who discovered relationship between
T, k and Ea.
• Arrhenius equation is

where k is the rate constant,

e is the base of natural logarithms,
T is the absolute temperature, and
R is the universal gas constant.
A is a constant (same units as the rate constant). It is
equal
to the fraction of collisions with the proper orientations
when all
• The Ea term is the activation energy of the reaction,
which Arrhenius considered the minimum energy the
molecules must have to react.

• This negative exponential relationship between T and

k means that as T increases, the negative exponent
becomes smaller, so the value of k becomes larger,
which means that the rate increases.
 Taking the natural
logarithm of both sides,
the equation becomes

Therefore, if k is determined experimentally at several

temperatures, Ea can be calculated from the slope of a plot of
ln k vs. 1/T.
• Because the relationship between In k and 1/T is
linear, we can use a simpler method to find Ea if we
know the rate constants at two temperatures, T 2 and
T1.

• When we subtract In k1 from In k2, the term In A drops out

and the other terms can be rearranged to give,

• From this, we can solve for Ea.

• The Arrhenius equation predicts that increasing
T results in a faster reaction for the same Ea and
concentrations.
Example
The decomposition of hydrogen iodide,
2HI (g)  H2 (g) + I2 (g)
has rate constants of 9.51 x l0-9 L/mol.s at 500 K
and1.10 x 10-5 L/mol.s at 600K. Find Ea.
Maxwell–Boltzmann Distributions and
Activation Energy, Ea

Maxwell-Boltzmann Curve
• Only those particles represented by the area to the right of the
activation energy will react when they collide.
• The great majority don't have enough energy, and will simply
bounce apart.
• To speed up the reaction, we need to increase the number of
the very energetic particles - those with energies equal to or
greater than the activation energy.
• Increasing the temperature has exactly that effect - it changes
the shape of the graph.
• As the temperature increases, the curve flattens and broadens.
• Thus at higher temperatures, a larger population of molecules
has higher energy.
• At a higher temperature, T2, a greater fraction of the molecules
possess the necessary activation energy, and the reaction
proceeds at a faster rate.
 Reaction Mechanisms
• The sequence of events that describes the actual
process by which reactants become products is called
the reaction mechanism.
• It is the step-by-step pathway by which a reaction
occurs.
• Reactions may occur all at once or through several
discrete steps.
• Each of these processes is known as an elementary
reaction or elementary step.
• Some reactions take place in a single step, but most
reactions happen in a series of elementary steps.
 Elementary Reaction/Step

The molecularity of a process tells how many

molecules are involved in the process.
Example of Reaction Mechanism
Rate-Determining Step in Reaction Mechanism
• In a reaction mechanism, one of the elementary steps will be
slower than all others.
• The overall reaction cannot occur faster than this slowest,
rate-determining step.
• Therefore, this elementary, rate-determining step
establishes the rate of the overall reaction.
• The speed at which the slow step occurs limits the rate at
which the overall reaction occurs.
 Determination of overall rate law from
elementary steps
Example: explain the overall rate for this reaction

If the reaction
2NO2 + F2 = 2 NO2F
follows the mechanism,
k1
i. NO2 + F2 NO2F + F (slow)

k2
ii. NO2 + F NO2F (fast)
• Overall rate can be find using rate-determining step.
• In reaction 1, the reaction is slow step with rate
constant k1
• In reaction 2, the reaction is fast step with rate
constant k2
• Because the step 1 is slow than step 2, the step 1 is
the rate-determining step.
• Thus, the overall reaction depends on the rate of
step 1.
• Overall rate, Rate= k1 [NO2] [F2]
 Chapter 4
Chemical Kinetics

4.5 Catalysis

Reference: Chemistry: the Molecular Nature of Matter and Change,

6th ed, 2011, Martin S. Silberberg, McGraw-Hill
 Catalysts
• Catalysts are substances that can be added to reacting systems to
increase the rate of reaction.
• They allow reactions to occur via alternative pathways that increase
reaction rates by lowering activation energies.
• Catalysts change the mechanism by which the process occurs.
• A catalyst does take part in the reaction, but all of it is
re-formed in later steps.
• Thus, a catalyst does not appear in the balanced
equation for the reaction.
 • How does activation energy affects rate of reaction??
Arrhenius Equation
k = A e−Ea/RT

When a catalyst is
present, the energy
barrier is lowered. Thus,
more molecules possess
the minimum kinetic
energy necessary for
reaction.
 CATALYSIS

• A catalyst changes the rate of a chemical

reaction.
• Two categories of catalysts:
(1) homogeneous catalysts
(2) heterogeneous catalysts
 Homogeneous catalysts
• A homogeneous catalyst exists in the same phase as the
reactants.
• Catalyst can operate by increasing the number of effective
collisions.
• That is, from the Arrhenius equation: catalyst increase k
by increasing A or decreasing Ea.
• A catalyst may add intermediates to the reaction.
• Example: In the presence of Br-, Br2 (aq) is generated as an
intermediate in the decomposition of H2O2.
• When a catalyst adds an intermediate, the activation
energies must be lower than the activation energy for the
uncatalyzed reaction.
 Heterogeneous catalysts
• A heterogeneous catalyst is present in a different phase from
the reactants.
• Such catalysts are usually solids, and they lower activation
energies by providing surfaces on which reactions can occur.
• The first step in the catalytic process is usually adsorption, in
which one or more of the reactants become attached to the
solid surface.
• Some reactant molecules may be held in particular
orientations, or some bonds may be weakened; in other
molecules, some bonds may be broken to form atoms or
smaller molecular fragments. This causes activation of the
reactants.
• As a result, reaction occurs more readily than
would otherwise be possible.
• In a final step, desorption, the product
molecules leave the surface, freeing reaction
sites to be used again.
• Most contact catalysts are more effective as
small particles, because they have relatively
large surface areas.
A schematic representation of the catalysis of the reaction on a metallic surface
(Pt, NiO)
2CO (g) + O2(g)  2CO2(g)
Enzymes
• Enzymes are proteins
that act as catalysts for
specific biochemical
reactions in living
systems.
• The reactants in enzyme-
catalyzed reactions are
called substrates.
• Most enzymes are protein
molecules with large
molecular masses (10,000
to 106 amu).
• The substrate fits into the
active site of the enzyme
much like a key fits into a
lock.
 • Enzymes have very specific shapes.
• Most enzymes catalyze very specific reactions.
• Substrates undergo reaction at the active site of
an enzyme.
• A substrate locks into an enzyme and a fast
reaction occurs.
• The products then move away from the enzyme.
• Only substrates that fit into the enzyme lock can
be involved in the reaction.

A space-filling model of the enzyme lysozyme. This

enzyme catalyzes the hydrolysis of polysaccharides
(complex carbohydrates) found in bacterial cell walls.