Chemical Kinetics

• Chemical kinetics is the study of reaction rates, how

reaction rates change under varying conditions, and
what molecular events occur during the overall
reactions.
Factors affecting the reaction rates
• Concentration of reactants
Often the rate of reaction increases when the
concentration of a reactant is increased. In some
reactions, however, the rate is unaffected by the
concentration of a particular reactant, as long as it is
present at some concentration.
• Concentration of catalyst
A catalyst is a substance that increases the rate of
reaction without being consumed in the overall
reaction. Because the catalyst is not consumed by the
reaction, it does not appear in the balanced chemical
equation.
• Temperature at which the reaction occurs.
Usually reactions speed up when the temperature
increases. It takes less time to boil an egg at sea level
than on a mountaintop, where water boils at a lower
temperature. Reactions during cooking go faster at
higher temperature
• Surface area of a solid reactant or catalyst
If a reaction involves a solid with a gas or liquid, the
surface area of the solid affects the reaction rate.
Because the reaction occurs at the surface of the solid,
the rate increases with increasing surface area. A wood
fire burns faster if the logs are chopped into smaller
pieces. Similarly, the surface area of a solid catalyst is
important to the rate of reaction. The greater the
surface area per unit volume, the faster the reaction
 Reaction rate
• The reaction rate, which is the change in
concentration of a reactant or a product with time
(M/s).
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
 Average, Instantaneous and Initial
Reaction rates
• Average rate
In most reactions, not only the concentration changes, but
the rate itself varies with time as the reaction proceeds.
The average rate of the reaction is the reaction rate divided
by the time interval of the reaction.
• Instantaneous rate, the rate at a particular instant
during the reaction.
• Initial rate, the instantaneous rate at the moment the
reactants are mixed.
Expressing the rate in terms of
reactnats and products
 The Rate Law and Its Components
• The rate law expresses the rate as a function of
reactant concentrations, product concentrations, and
temperature.
• A rate law is an equation that relates the rate of a
reaction to the concentrations of reactants (and
catalyst) raised to various powers.
• The proportionality constant k, called the rate
constant, is specific for a given reaction at a given
temperature; it does not change as the reaction
proceeds (k does change with temperature and
therefore determines how temperature affects the
rate). The exponents m and n, called the reaction
orders, define how the rate is affected by reactant
concentration.
• A key point to remember is that the components of
the rate law—rate, reaction orders, and rate
constant—must be found by experiment; they
cannot be deduced from the reaction stoichiometry.
• The rate expression tells us how the
appearance/disappearance rates of the
products and reactants relate to one another;
the rate law tells us how the rate is related to
the concentrations (or pressures) of reactants
and the rate constant is a constant of
proportionality that comes out of the rate law.
 An experimental approach to finding
the components of rate law

1. Using concentration measurements to find the

initial rate
2. Using initial rates from several experiments to find
the reaction orders.
3. Using these values to calculate the rate constant
 Reaction order terminology
• The reaction order with respect to a given reactant
species equals the exponent of the concentration of
that species in the rate law, as determined
experimentally.
• The overall order of a reaction equals the sum of the
orders of the reactant species in the rate law.
 Method of Initial Rates
• The method of initial rates involves a series of
experiments in which the initial concentrations of
some reactants are held constant and others are
varied in convenient multiples in order to determine
the rate law for that reaction.
• Speculation about how a reaction occurs at the
molecular level must be based on measurements of
reaction rates. There are many experimental
approaches, but all must obtain the results quickly
and reproducibly. We consider four common
methods, with specific examples
1) Spectrometric Methods
2) Conductometric Methods
3) Manometric Methods
4) Direct Chemical Methods
 Integrated rate laws (Concentration-
Time equations)
• Using calculus, we can transform a rate law into a
mathematical relationship between concentration
and time called an integrated rate law.
 First Order reaction
A first-order reaction is a reaction whose rate depends
on the reactant concentration raised to the first power.
In a first-order reaction of the type
A product
The rate is
∆[𝐴]
𝑅𝑎𝑡𝑒 = −
∆t
From the rate law, we also know that
Rate = k[A]
First Order reaction
 Second-Order Reactions
• A second-order reaction is a reaction whose rate
depends on the concentration of one reactant raised
to the second power or on the concentrations of two
different reactants, each raised to the first power.
The simpler type involves only one kind of reactant
molecule:
A product
Zero-order reactions
 Half-life (t1/2)
• The half-life (t1/2) of a reaction is the time required for
the reactant concentration to reach half its initial
value. A half-life is expressed in time units appropriate
for a given reaction and is characteristic of that
reaction at a given temperature.
Elementary and Complex reactions
• A simple reaction takes place in a single step. Simple
reactions are also known as elementary reactions.
One step reactions are elementary reactions.
• Reactions which do not take place in a single step but
take place in a sequence of a number
of elementary steps are called as complex reactions.
 Elementary Reactions and
Molecularity
• An elementary reaction represents, at the molecular
level, a single stage in the progress of the overall
reaction.
• An elementary step is characterized by its
molecularity. The molecularity of an elementary
reaction refers to the number of free atoms, ions, or
molecules that enter into the reaction.
• The molecularity of a reaction is the number of
molecules reacting in an elementary step.
 Elementary reactions
• Uni-molecular reaction: It is an elementary reaction
that involves one reactant molecule;
• Bi-molecular reaction: It is an elementary reaction
that involves two reactant molecules;
• Ter-molecular reaction: It is an elementary reaction
that involves three reactant molecules.
 Rate Laws for Elementary Reactions
• For an elementary reaction, the rate is proportional to
the product of the concentration of each reactant
molecules see below:
• For uni-molecular reactions: A B + C.
Rate = k*[A]
• For bi-molecular reactions: A + B C+D
Rate = k*[A]*[B]
• For ter-molecular reactions: A+B+C D+E
Rate = k*[A]*[B]*[C]
 Complex Reactions
• Reactions which do not take place in a single step but
take place in a sequence of a number
of elementary steps are called as complex reactions.
• When we study a reaction that has more than one
elementary step, the rate law for the overall process
is given by the rate-determining step, which is the
slowest step in the sequence of steps leading to
product formation.
• Intermediates appear in the mechanism of the
reaction (that is, the elementary steps) but not in the
overall balanced equation. Keep in mind that an
intermediate is always formed in an early elementary
step and consumed in a later elementary step.
Correlating the Mechanism with the Rate
Law
• Mechanisms with a Slow Initial Step
2. Both steps are bimolecular, so they are chemically
reasonable.
3. The mechanism gives the rate law for the overall
equation. To show this, we write the rate laws for the
elementary steps:
(1) Rate1 = k1[NO2][F2]
(2) Rate2 = k2[NO2][F]
Step 1 is the rate-determining step and therefore gives
the overall rate law, with k1 = k. Because the second
molecule of NO2 appears in the step that follows the
rate-determining step, it does not appear in the overall
rate law. Thus, we see that the overall rate law includes
only species active in the reaction up to and including
those in the rate-determining step
Mechanisms with a Fast Initial Step
At equilibrium,