Kinetics Overview

Chemical Kinetics
Lecture notes edited by John Reif from PPT lectures by:
Chung (Peter) Chieh, University of Waterloo Hana El-Samad, UCSB

John D. Bookstaver, St. Charles Community College Dan Reid, Champaign CHS
Slides revised by Xin Song for Spring 2020 Term
What are Chemical Kinetics?

Chemical Kinetics
Kinetics – how fast does a reaction proceed?
Thermodynamics – does a reaction take place?
Reaction speed: measured by the change in concentration with time.
Important factors which affect rates of reactions:

– reactant concentration
– temperature
– action of catalysts
– surface area
– pressure of gaseous reactants or products
Dan Reid
Champaign CHS
Kinetics
• Studies the rate at which a chemical process
occurs.
• Besides information about the speed at which

reactions occur, kinetics also sheds light on the
reaction mechanism (exactly how the reaction
occurs).
• John D. Bookstaver
• St. Charles Community College
Outline: Kinetics
Reaction Rates How we measure rates.
How the rate depends on amounts

Rate Laws of reactants.
How to calculate amount left or
Integrated Rate Laws time to reach a given amount.
How long it takes to react 50% of
Half-life reactants.
How rate constant changes with
Arrhenius Equation temporature.
Link between rate and molecular
Mechanisms scale processes.
John D. Bookstaver
St. Charles Community College
Reaction Rates
Reaction Rates
Rates of reactions can be determined by monitoring

the change in concentration of either reactants or
products as a function of time t.
Notation for Stoichiometry:
[A] = concentration of reactant A
[B] = concentration of reactant B
John D. Boo kstaver

Reaction Rate
• For the reaction A  B there are two ways of measuring rate:
(1) the speed at which the reactants disappear
(2) the speed at which the products appear
• Reversible reactions: as products accumulates, they can begin
to turn back into reactants.
• Early on the rate will depend on only the amount of reactants
present. We want to measure the reactants as soon as they
are mixed.
• A general way of measuring the rate of the reaction is in terms
of change in concentration per unit time…
Instantaneous rate = ∆[A]/∆t limits to d[A]/dt
Most Common Units… Rate = M/s
Dan Reid
Champaign Where Molarity (M) = moles/Liter
CHS
Chemical Kinetics
Reaction rate is the change in the concentration of a

reactant or a product with time (M/s).
A B
[A]
rate = - [A] = change in concentration of A over
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.
Chung (Peter) Chieh

University of Waterloo
Reaction Rates and Stoichiometry
• To generalize, for the reaction
aA + bB cC + dD
Reactants (decrease) Products (increase)
John D. Bookstaver
Factors Affecting Reaction
Rate Constants
Factors that Affect the Reaction Rate Constant

1. Temperature: At higher temperatures, reactant molecules have more kinetic
energy, move faster, and collide more often and with greater energy
• Collision Theory: When two chemicals react, their molecules have to
collide with each other (in a particular orientation) with sufficient energy
for the reaction to take place.
• Kinetic Theory: Increasing temperature means the molecules move
faster.
2. Concentrations of reactants
• As the concentration of reactants increases,
so does the likelihood that reactant molecules will collide.
3. Catalysts
• Speed up reactions by lowering activation energy
4. Surface area of a solid reactant
• More area for reactants to be in contact
5. Pressure of gaseous reactants or products
• Increased number of collisions
Chung (Peter) Chieh

•John D. Bookstaver
•St. Charles Community College
Reaction Rate Examples
An Example of Reaction Rates

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.
John D. Bookstaver
• The reaction slows

down with time because
the concentration of the
reactants decreases.
John D. Bookstaver

• 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.
Rate = - [C4H9Cl]
= D[C4H9OH]
t t
John D. Bookstaver
Reaction Rate Laws
Concentration and Rate
Each reaction has its own equation that

expresses its rate as a function of the
concentrations of the involved species (e.g.,
reactants, products, catalysts).
This is called its Rate Law
John D. Bookstaver
Rate Law
• In general, rates of reactions increase as concentrations
increase since there are more collisions occurring between
reactants.
• The overall concentration dependence of reaction rate is given in a
rate law or rate expression.
• For reactions follow simple rate laws:
v = k [A]m [B]n…
- [A], [B]: reactant concentrations
- The exponents m and n: reaction order (w.r.t. specific reactant)
- The constant k: rate constant
- The overall reaction order is the sum of the reaction orders:
m+n
Dan Reid
Champaign CHS
Determination of Rate Laws

• Rate laws, rate constants, and orders are determined
experimentally.
• The order of a reactant is NOT generally related to its

stoichiometric coefficient in a balanced chemical equation.
F2 (g) + 2ClO2 (g) 2FClO2 (g)
1
v = k [F2][ClO2]
Chung (Peter) Chieh

Expression of Rate Laws
Reactions with simple rate laws:
Reactions with complex rate laws*:
* imply multi-step reactions (sequence of elementary steps)
however, the overall

rate cannot involve
intermediate species
Reaction Kinetics (Vallance)
Elementary reactions
Always follow simple rate laws
Reactant order reflects molecularity (# of molecules involved in reaction)
More on this later…

Simple Example
Reactions
Example chemical reaction that models

degradation of molecule A

A 
Reactant
dA
  .[A ]
dt
Rate of change of A
time
Degradation constant
Hana El-Samad
UCSB
Example chemical reaction that models generation
(from D) and degradation of molecule A
k 
D  A 
dA
 k.[D]  .[A ]
dt
Rate of change of A
Production constant
Degradation constant
Hana El-Samad
UCSB

(from A and B) of molecule C
k
ABC
dA
 k[.A.][B ]
dt
Hana El-Samad
UCSB
(from n distinct A and m distinct B) of molecule C
k
nA
 mB  C
1dA[ ] n
n mm
 k[A][B ]
n dt
Hana El-Samad
UCSB
Order of Reactions
Order of Reactions
• A reaction is zero order in a reactant if the change in

concentration of that reactant produces no effect.
• A reaction is 1st order if doubling the

concentration causes the rate to double.
• A reaction is 2nd order if doubling the

concentration causes a quadruple increase in rate.
-3rd order…doubling concentration leads to 23 (or 8 times) the rate.
- extremely rare.
Dan Reid
Champaign CHS
Order of Reactions

Zero-Order Processes
[A]
t
reaction rate = -
t = k (constant)
So… [A]t = -kt + [A]0
• This equation has the general form for a straight line, y=mx+b, so
a plot of [A]t vs. t is a straight line with slope (-k) and intercept [A]0.
(slope= −k)
[A]t
Time (s)
Chung (Peter) Chieh

First-Order Processes
For 1st order reactions: ln[A]t = −kt + ln[A]0
where [A]t = concentration of [A] after some time, t
k= reaction rate constant in units of s-1
t= time in seconds
[A]o = initial concentration of A
• This equation has the general form for a straight line, y=mx+b,
so a plot of ln[A]t vs. t is a straight line with slope (-k) and
intercept ln[A]0.
(slope= −k)
ln[A]t
John D. Bookstaver
Time (s)

Example: First-Order Processes
Consider the process in

which methyl isonitrile is
converted to acetonitrile.
CH3NC CH3CN
How do we know this

is a first order
reaction?
John D. Bookstaver
CH3NC CH3CN
This data was

collected for this
reaction at
198.9°C.
Does
rate=k[CH3NC]
for all time intervals?
John D. Bookstaver
If a reaction is first-order:
a plot of ln [A]t versus t will yield a
straight line with a slope of -k.
John D. Bookstaver
• When ln[A] is plotted as a function of time,

a straight line results.
– The process is first-order.
– k is the negative slope: 5.1  10-5 s-1.
John D. Bookstaver
Second-Order Processes
For 2nd order reactions: 1/[A]t = kt + 1/[A]0
where [A]t = concentration of [A] after some time, t
k= reaction rate constant in units of M-1s-1
t= time in seconds
[A]o = initial concentration of A
• This equation has the general form for a straight line, y=mx+b,
so a plot of l/[A]t vs. t is a straight line with slope (k) and intercept
of 1/[A]0.
(slope= k)
1/[A]t
Dan Reid
Champaign Time (s)
CHS
Half Life
Half-Life
• Half-life is the time taken for the concentration of a
reactant to drop to half its original value.
• Substitute into integrated rate laws: t½ is the time taken
for [A] to reach ½[A]0
NOTE: For a first-order process, the

half-life does not depend on [A]0.
Reaction Kinetics Dan Reid
Champaign CHS
(Vallance)
Half-Life - 1st order

For a first-order process, set [A]t=0.5 [A]0 in
integrated rate equation:
John D. Bookstaver
What is the half-life of N2O5 if it decomposes with a rate
constant of 5.7 x 10-4 s-1?
t½ =
Ln 2 0.693
= = 1200 s = 20 minutes
5.7 x 10-4 s-1
k
How do you know decomposition is first order?
hint: units of k (s-1)
Chung (Peter) Chieh


First-order reaction
A product
# of
half-lives [A] = [A]0/n
1 2
2 4
3 8
4 16
Chung (Peter) Chieh

NOTE: For
a first-order
process,
the half-life
does not
depend on
[A]0.
Chung (Peter) Chieh

Half-Life - 2nd order

For a second-order process, set
[A]t=0.5 [A]0 in 2nd order equation:
John D. Bookstaver
Equations of Reactions
of Various Orders
Summary of the Kinetics of Zero-Order, First-Order

and Second-Order Reactions
Concentration-Time
Order Rate Law Equation Half-Life
[A]0
0 rate = k [A] - [A]0 = - kt t ½= 2k
Ln 2
1 rate = k ln[A] - ln[A]0 = - t½ =
[A] kt k
2 rate = k [A]2 1 1 = kt 1
[A] - [A]0 t½ = k[A]0
Chung (Peter) Chieh

Summary of Kinetics
Second order
First order General Second order
(1 reactant)
Rate
Laws
Integrate
d Rate complicated
Laws
Half-life complicated
John D. Bookstaver
Summary of Kinetics
Second order
First order General Second order
(1 reactant)
Rate
Laws
Integrate
d Rate complicated
Laws
Half-life complicated
k(T)
John D. Bookstaver
Reaction Mechanisms
Reaction Mechanisms
The sequence of events that describes
the actual process by which reactants
become products is called the reaction
mechanism.
John D. Bookstaver
Reaction Mechanisms
• Reactions may occur all at once or
through several discrete steps.
• Each of these processes is known as an
elementary reaction or elementary
process.
John D. Bookstaver
Reaction Mechanisms
The overall progress of a chemical reaction can be represented

at the molecular level by a series of simple elementary steps
or elementary reactions.
The sequence of elementary steps that leads to product

formation is the reaction mechanism.
2NO (g) + O2 (g) 2NO2 (g)
N2O2 is detected during the reaction!
Elementary step: NO + NO N2O2

+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2
Chung (Peter) Chieh
Rate Laws and Rate Determining Steps
Writing plausible reaction mechanisms:

• The sum of the elementary steps must give the overall
balanced equation for the reaction.
• The rate-determining step should predict the same rate
law that is determined experimentally.
The rate-determining step is the

slowest step in the sequence of
steps leading to product
formation.
Chung (Peter) Chieh
Reaction Mechanisms
• Up until now, we have only been concerned with the reactants
and products. Now we will examine what path the reactants took
in order to become the products.
• The reaction mechanism gives the path of the reaction.
• Mechanisms provide a very detailed picture of which bonds
are broken and formed during the course of a reaction.
Elementary Steps & Molecularity
• Elementary step: any process that occurs in a single step.
• Molecularity: number of molecules present in an elementary step.
– Unimolecular: one molecule in the elementary step,
– Bimolecular: two molecules in the elementary step, and
– Termolecular: three molecules in the elementary step.
(It is uncommon to see termolecular processes…statistically improbable for an
effective collision to occur.)
Dan Reid
Champaign CHS
Rate Laws of Elementary Steps
• Since this process occurs in one single step, the stoichiometry can
be used to determine the rate law!
• Law of Mass Action: The rate of a simple (one step) reaction is
directly proportional to the concentration of the reacting
substances.
• Notice that the coefficients become the exponents.

Dan Reid
Champaign CHS
Reaction Mechanisms
• The molecularity of a process tells how many

molecules are involved in the process.
• The rate law for an elementary step is written

directly from that step.
John D. Bookstaver
Reaction Intermediates
Intermediates are species that appear in a reaction

mechanism but not in the overall balanced equation.
An intermediate is always formed in an early elementary

step and consumed in a later elementary step.
Elementary step: NO + NO N2O2

+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2
Chung (Peter) Chieh

Multistep Mechanisms
• In a multistep process, one of the steps will

be slower than all others.
• The overall reaction cannot occur faster than
this slowest, rate-determining step.
John D. Bookstaver
Activation Energy
Activation Energy
• There is a minimum amount of energy required for a
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.
John D. Bookstaver
Activation Energy
• Molecules must possess a minimum amount of energy to
react. Why?
– In order to form products, bonds must be broken in
the reactants. Bond breakage requires energy.
– Molecules moving too slowly, with too little kinetic
energy, don’t react when they collide.
• Activation energy, Ea, is the minimum energy required to
initiate a chemical reaction.
− Ea will vary with the reaction.
Next we will look at an example of Ea.
Dan Reid
Champaign CHS
Activation Energy
• The change in energy ∆E for the reaction is the difference
in energy between CH3NC (reactant) and CH3CN (product).
• The activation energy Ea is the difference in energy
between reactants, CH3NC, and the transition state.
• The rate depends on Ea. If the “hill” is taller, the reaction rate
is slower. If the “hill” is shorter the rate is faster.
• Notice that if a forward reaction is exothermic… (CH3NC  CH3CN),
then the reverse reaction is endothermic… (CH3CN  CH3NC).
• The methyl isonitrile molecule needs to gain enough energy
to overcome the activation energy barrier.
• From kinetic molecular theory, we know that as temperature
increases, the total kinetic energy increases and the number
of molecules with energy greater than Ea increases.
• So as long as the temperature is high enough, the reaction can
Dan Reid
make it “over the hill” and proceed.
Champaign CHS
A+B C+D
Exothermic Reaction Endothermic Reaction
The activation energy (Ea) is the minimum amount of

energy required to initiate a chemical reaction.
Chung (Peter) Chieh
Energy Diagrams
Exothermic Endothermic
(a) Activation energy (Ea) for the forward reaction

50 kJ/mol 300 kJ/mol
(b) Activation energy (Ea) for the reverse reaction 150 kJ/mol 100 kJ/mol
(c) Delta H -100 kJ/mol +200 kJ/mol
Chung (Peter) Chieh

Arrhenius Equation
Arrhenius Equation
Svante Arrhenius developed a mathematical
relationship between k and Ea:
where A is the frequency factor, a number that

represents the likelihood that collisions would
occur with the proper orientation for reaction.
John D. Bookstaver
Arrhenius Equation
Taking the natural logarithm of both sides, the equation becomes
1
R
y = mx + b
When k is determined experimentally at
several temperatures, Ea can be calculated
from the slope of a plot of ln(k) vs. 1/T.
John D. Bookstaver
Temperature Dependence of the Rate Constant
k = A • exp( -Ea/RT )
(Arrhenius equation)
k is the rate constant

Ea is the activation energy (J/mol)
R is the gas constant (8.314 J/K•mol)
T is the Kelvin temperature
A is the frequency factor
Chung (Peter) Chieh

1/T
Dan Reid
Champaign CHS
Maxwell–
Boltzmann
Distributions
Maxwell–Boltzmann Distributions
• Temperature is
defined as a
measure of the
average kinetic
energy of the
molecules in a
sample.
• At any temperature there is a wide
distribution of kinetic energies.
John D. Bookstaver
• As the temperature
increases, the curve
flattens and
broadens.
• Thus at higher
temperatures, a
larger population of
molecules has
higher energy.
John D. Bookstaver
• If the dotted line represents the activation
energy, as the temperature increases, so does
the fraction of molecules that can overcome
the activation energy barrier.
• As a result, the
reaction rate
increases.
John D. Bookstaver
This fraction of molecules can be found through the expression:
where R is the gas constant and T is the temperature in Kelvin.
John D. Bookstaver
Catalysts
A catalyst is a substance that increases the rate of a

chemical reaction without itself being consumed.
Ea k
uncatalyzed catalyzed
ratecatalyzed > rateuncatalyzed

Chung (Peter) Chieh
Catalysts
• Catalysts increase the rate of a reaction by
decreasing the activation energy of the
reaction.
• Catalysts change the mechanism by which
the process occurs.
John D. Bookstaver
Catalysts
One way a
catalyst can
speed up a
reaction is by
holding the
reactants together
and helping bonds
to break.
John D. Bookstaver
Catalysts
There are two types of catalyst: Heterogeneous – one that is present in
a different phase as the reacting molecules. Homogeneous – one that
is present in the same phase as the reacting molecules.
Example: Hydrogen peroxide decomposes very slowly in the absence of a catalyst:

2H2O2(aq)  2H2O(l) + O2(g)
In the presence of bromide ions, the decomposition occurs rapidly in
an acidic environment:
2Br–(aq) + H2O2(aq) + 2H+(aq)  Br2(aq) + 2H2O(l)
Br2(aq) + H2O2(aq)  2Br–(aq) + 2H+(aq) + O2(g)
Br– is a homogeneous catalyst because it is regenerated at the end of the reaction.

The net reaction is still…2H2O2(aq)  2H2O(l) + O2(g)
Dan Reid
Champaign CHS
Catalysts and Reaction Rates

How do catalysts increase reaction rates?
• In general, catalysts operate by lowering the overall
activation energy, Ea, for a reaction. (It lowers the “hill”.)
• However, catalysts can operate by increasing the number
of effective collisions.
• A catalyst usually provides a completely different mechanism
for the reaction.
• In the preceding peroxide decomposition example, in the
absence of a catalyst, H2O2 decomposes directly to water and
oxygen.
• In the presence of Br–, Br2(aq) is generated as an intermediate.
• When a catalyst adds an intermediate, the activation energies
for both steps must be lower than the activation energy for the
Dan Reid
Champaign
CHS
uncatalyzed reaction.
Dan Reid
Champaign
CHS
Heterogeneous Catalysts
• Often we encounter a situation involving a solid catalyst in
contact with gaseous reactants and gaseous products…
• Example: catalytic converters in cars.
- Many industrial catalysts are heterogeneous.
How do they do their job?
• The first step is adsorption (the binding of reactant molecules
to the catalyst surface).
• Adsorption occurs due to the high reactivity of atoms or ions
on the surface of the solid.
• Molecules are adsorbed onto active sites on the catalyst surface.
• The number of active sites on a given amount of catalyst
depends on several factors such as:
- The nature of the catalyst.
- How the catalyst was prepared.
- How the catalyst was treated prior to use.
Dan Reid
Champaign CHS
Example: C2H4(g) + H2(g)  C2H6(g)
• In the presence of a metal catalyst (Ni, Pt or Pd) the
reaction occurs quickly at room temperature.
Here are the steps…
- First, the ethylene and hydrogen molecules are adsorbed onto active
sites on the metal surface.
- Second, the H–H bond breaks and the H atoms migrate about the metal
surface and runs into a C2H4 molecule on the surface.
- Third, when an H atom collides with a C2H4 molecule on the surface,
the C−C π-bond breaks and a C–H σ-bond forms.
- Lastly, When C2H6 forms it desorbs from the surface.
• When ethylene and hydrogen are adsorbed onto a surface,
less energy is required to break the bonds.
• The Ea for the reaction is lowered, thus the reaction rate increases.
Dan Reid
Champaign
CHS
Dan Reid
Champaign CHS
Examples of
Catalysts:
Enzymes
Enzymes
• Enzymes are catalysts in biological systems.
• The substrate fits into the active site of the

enzyme much like a key fits into a lock.
John D. Bookstaver
Enzyme Catalysts
• Enzymes are biological catalysts. There may be as many
as 30,000 enzymes in the human body. (e.g., Lactase)
• Most enzymes are protein molecules with large molecular
masses (10,000 to 106 amu).
• Enzymes have very specific shapes.
• Most enzymes catalyze very specific reactions.
• The substances that undergo reaction at the active site on
enzymes are called substrates.
• A substrate locks into an enzyme and a fast reaction
occurs. The products then move away from the enzyme.
Dan Reid
Champaign CHS
Enzyme Catalysts
• Only substrates that fit into the enzyme lock can be involved in
the reaction.
• If a molecule binds tightly to an enzyme so that another
substrate cannot displace it, then the active site is blocked and the
catalyst is inhibited (enzyme inhibitors).
• Many poisons act by binding to the active site blocking the
binding of substrates. The binding can also lead to changes in the
enzyme.
• Enzymes are extremely efficient catalysts.
• The number of individual catalytic events occurring at an active
site per unit time is called the turnover number.
• Large turnover numbers correspond to very low Ea values. For
enzymes, turnover numbers are very large ≈ 103 to 107/sec
Dan Reid
Champaign CHS
Enzyme Catalysis
Chung (Peter) Chieh


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Chemical Kinetics

Lecture notes edited by John Reif from PPT lectures by:

Chung (Peter) Chieh, University of Waterloo Hana El-Samad, UCSB

Slides revised by Xin Song for Spring 2020 Term

What are Chemical Kinetics?

Important factors which affect rates of reactions:

• Besides information about the speed at which

How the rate depends on amounts

Rates of reactions can be determined by monitoring

John D. Boo kstaver

Reaction rate is the change in the concentration of a

Chung (Peter) Chieh

Reaction Rates and Stoichiometry

• To generalize, for the reaction

Reactants (decrease) Products (increase)

Factors that Affect the Reaction Rate Constant

Chung (Peter) Chieh

An Example of Reaction Rates

• The reaction slows

An Example of Reaction Rates

• In this reaction, the ratio

Concentration and Rate

Each reaction has its own equation that

This is called its Rate Law

Determination of Rate Laws

• The order of a reactant is NOT generally related to its

F2 (g) + 2ClO2 (g) 2FClO2 (g)

Chung (Peter) Chieh

Reactions with simple rate laws:

Reactions with complex rate laws*:

* imply multi-step reactions (sequence of elementary steps)

however, the overall

Always follow simple rate laws

Reactant order reflects molecularity (# of molecules involved in reaction)

More on this later…

Reaction Kinetics (Vallance)

Example chemical reaction that models

Example chemical reaction that models generation

• A reaction is zero order in a reactant if the change in

• A reaction is 1st order if doubling the

• A reaction is 2nd order if doubling the

Reaction Kinetics (Vallance)

Chung (Peter) Chieh

St. Charles Community College

Consider the process in

How do we know this

This data was

• When ln[A] is plotted as a function of time,

NOTE: For a first-order process, the

Half-Life - 1st order

How do you know decomposition is first order?

hint: units of k (s-1)

Chung (Peter) Chieh

Half-Life - 1st order

Chung (Peter) Chieh

Chung (Peter) Chieh

Half-Life - 2nd order

Summary of the Kinetics of Zero-Order, First-Order

Chung (Peter) Chieh