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Chapter 3
Chemical Kinetics
Key terms
chemical kinetics The study of the rates and
mechanisms of reactions.
reaction rate The change in the concentrations of
reactants (or products) with time.
average rate The change in concentration of
reactants (or products) divided by a finite time
period.
instantaneous rate The reaction rate at a
particular time, given by the slope of a tangent to
a plot of reactant concentration vs. time.
initial rate The instantaneous rate occurring as
soon as the reactants are mixed, that is, at t = 0.
rate law (also rate equation) An equation that
expresses the rate of a reaction as a function of
reactant (and product) concentrations.
rate constant (k) The proportionality constant
that relates reaction rate to reactant (and product)
concentrations. 
 how the energy of reactant collisions is used to
reaction orders The exponent of a reactant
concentration in a rate law that shows how the
rate is affected by changes in that concentration.
integrated rate law A mathematical expression
for reactant concentration as a function of time.
half-life (t1/2) In chemical processes, the time
required for half the initial reactant concentration
to be consumed. In nuclear
processes, the time required for half the initial
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number of nuclei in a sample to decay.
collision theory A model that explains reaction
rate as based on the number, energy, and
orientation of colliding particles.
Arrhenius equation An equation that expresses
the exponential relationship between temperature
and the rate constant:
-Ea/RT
k = Ae .
activation energy (Ea) The minimum energy
with which molecules must collide to react.
effective collision A collision in which the
particles meet with suffcient energy and an
orientation that allows them to react.
frequency factor (A) The product of the collision
frequency Z and an orientation probability factor
p that is specifc for a reaction.
transition state theory A model that explains
form a high-energy transitional species that can
change to reactant or product.
transition state (activated complex) An unstable
species formed in an effective collision of
reactants that exists momentarily when the
system is highest in energy and that can either
form products or re-form reactants.
reaction energy diagram A graph that shows the
potential energy of a reacting system as it
progresses from reactants to products.
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reaction mechanism A series of elementary
steps that sum to the overall reaction and is
consistent with the rate law.
elementary reaction (also elementary step) A
simple reaction that describes a single molecular
event in a proposed reaction mechanism.
unimolecular reaction An elementary reaction
that involves the decomposition or rearrangement
of a single particle.
bimolecular reaction An elementary reaction
involving the collision of two reactant species.
termolecular reaction An elementary reaction
involving the collision of three reactant species.
rate-determining (rate-limiting) step The
slowest step in a reaction mechanism and
therefore the step that limits the overall rate.
reaction intermediate A substance that is
Dr. Truong Thanh Tu
formed and used up during the overall reaction
and therefore does not appear in the overall
equation.
catalyst A substance or mixture that increases the
rate of a reaction without being used up in the
process.
homogeneous catalyst A catalyst (gas, liquid, or
soluble solid) that exists in the same phase as the
reactants.
heterogeneous catalyst A catalyst that occurs in
a different phase from the reactants, usually a
solid interacting with gaseous or liquid reactants.
enzyme A biological macromolecule (usually a
protein) that acts as a catalyst. 

active site The region of an enzyme formed by
specifc amino acid side chains at which catalysis
occurs.

Key Principles
• The rate of a reaction is the change in the concentration of reactant (or product) per unit of time.
Reaction rates vary over a wide range, but each reaction has a specific rate under a given set of
conditions. The rate depends on concentration and physical state because reactants must collide to react.
It depends even more on temperature because the collisions must occur with enough kinetic energy.
(Section 3.1) 

• The rate changes as the reaction proceeds: fastest at the beginning, when reactant concentration is
highest, and slowest at the end. Average rate is the concentration change over a period of time, and
instantaneous rate is the change at any instant. Kinetic studies typically measure the initial rate, the rate
at the moment the reactants are mixed, so product is absent. (Section 3.1) 

• The rate of a reaction is given by a rate law (or rate equation). This expression includes a temperature-
dependent rate constant and one or more concentration terms raised to an exponent, called a reaction
order, that defines how the concentration of that reactant affects the rate. The rate law must be
determined by experiment, not from the balanced equation, and several methods exist for measuring
initial rates. (Section 3.2) 

• An integrated rate law includes concentration and time as variables. In addition to another way to find
the reaction order, it is used to find the half-life, the time required for half of a reactant to be used up. The
half-life of a first-order reaction does not depend on reactant concentration. (Section 3.2) 

• Collision theory proposes that reactant molecules must collide with a minimum energy, the energy of

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activation (Ea), in order to react. The Arrhenius equation shows that rate increases with temperature and
decreases with Ea by affecting the rate constant. (Section 3.3) 


• Higher temperature increases the frequency of collisions and, more importantly, the fraction of
collisions with energy greater than Ea. For a collision to be effective, the atoms in the colliding molecules
must be oriented correctly for a bond to form between them. (Section 3.3) 

• Transition state theory explains that the Ea is the energy needed to form a high-energy species that
exists only momentarily and includes partially broken reactant bonds and partially formed product bonds.
Every step in a reaction has such a transition state (activated complex). (Section 3.3) 

• Chemists explain the rate law for an overall reaction by proposing a reaction mechanism that consists
of several elementary steps, each with its own rate law. To be a valid mechanism, the sum of the
elementary steps must give the balanced equation, the steps must be physically reasonable, and the
mechanism must correlate with the rate law. The rate law of the slowest step (the rate-determining step)
must give the overall rate law. (Section 3.4) 

• A catalyst is a component of a reaction mixture that speeds the reaction (in
both directions) but is not
consumed. It functions by lowering the Ea of the rate-determining step of an alternative mechanism for
the same overall reaction. Catalysts can function in the same (homogeneous) or a different
(heterogeneous) phase from the reactants and products. They are essential components of many
industrial, and nearly all biological, reactions. (Section 3.5) 


Learning Objectives
1. Explain why reaction rate depends on concentration, physical state, and temperature. 

2. Understand how reaction rate is expressed in terms of changing reactant and product concentrations
over time, and distinguish among average, instantaneous, and initial rates.
3. Describe the information needed to determine the rate law, and explain how to calculate reaction
orders and rate constant.

4. Understand how to use integrated rate laws to find concentration at a given time (or vice versa) and
reaction order, and explain the meaning of half-life.
5. Explain the effect of temperature on the rate constant (Arrhenius equation) and the importance of
activation energy.
6. Understand collision theory (why concentrations are multiplied, how temperature affects the
fraction of collisions exceeding Ea, and how rate depends on the number of effective collisions) and
transition state theory (how Ea is used to form the transition state and how a reaction energy
diagram depicts the progress of a reaction).
7. Understand elementary steps and molecularity, and be able to construct a valid reaction mechanism
with either a slow or a fast initial step.
8. Explain how a catalyst speeds a reaction by lowering Ea, and distinguish between homogeneous
and heterogeneous catalysis.

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