CHEMICAL KINETICS
Chemical kinetics or simply kinetics is a branch of
physical chemistry concerned with the rates of chemical
reactions. Also included are the factors that affect
reaction rates
OBJECTIVES
1. Identify the factors that affect reaction rates
and apply knowledge to hasten or slow down
reactions.
2. Calculate reaction rates and appreciate the
function of catalysts and inhibitors.
Two areas constituting the
study of kinetics
1. Reaction Rates
2. Mechanism
Reaction Rates
Quantity that tells how the concentration of a
given reactant or product changes with time. It
can be expressed as
Rate =
If the concentration of a particular reactant A is
expressed as moles per liter (M), it can be
expressed as
Rate =
Rate Law
Mathematical expression that relates
the rate of reaction to the
concentration of the reactants
aA + bB products
Rate of Reaction
The rate of the overall reaction is proportional to the
concentration of A and B raised to certain powers.
Expressed as:
rate of reaction [A]a[B]b
The concentration of A and B are expressed in mole
per liter, expressed for gases where units of pressure
are used.
Rate Determining Step
Many reactions go in two or more steps. When
this is the case, there is usually one slow step,
which determines the rate of the reaction.
2A + B C may go into the following
steps
A + B AB
AB + A C
Whichever step goes slowly, this step
determines the rate of reaction. Why?
Law of Mass Action
Law of mass action was introduced by two Norwegian chemists, Cato
Guldberg and Peter Waage
mA + nB C
rate [A]m[B]n
Eliminating the proportionality sign
rate = k [A]m[B]n
k is known as the specific rate constant
The law of mass action is applicable only to the rate determining step.
Order of Reaction
For a particular specie in the reaction, the order
is equal to the exponent for that specie in the
rate law
Rate = k[A]2[B]
The reaction is second order with respect to A
and first order with respect to B
Factors affecting reaction rates
1. Concentration
2. Temperature
3. Catalyst (Inhibitor)
Concentration
The frequency of collision between molecules
that are reacting is dependent on the number of
molecules present in a given volume. As the
concentration increases, more reactant
molecules collide with other reactant molecules
in a given period of time, and more product
molecules are formed.
Temperature
Since temperature is a measure of the average
kinetic energy of the molecules in a gas, as the
temperature increases, the average kinetic
energy increases. Since the molecules have
higher average kinetic energy, the rate of
reactions, both forward and backward, is more
rapid. When the temperature of a reaction is
changed, the rate law does not change but the
value of the constant does change.
Catalyst/Inhibitor
change the activation energy. A
catalyst decreases the activation
energy, while an inhibitor increases
the activation energy
Equilibrium
Rate forward reaction = rate of backward reaction
Kf = [C][D]
Kb = [A][B]
Rearranging
Kf = [C][D]
Kb = [A][B]
Since kf and kb are both constants, kf/kb is also a constant, called the equilibrium
constant Keq.
Homogenous and
heterogeneous equilibria
N2 + 3 H2 2 NH3
Keq = [NH3]2
[N2][H2]3
2KNO3 (s) 2KNO2 (s) + O2
Keq = [O2]
In a heterogeneous equilibrium, only the specie in the homogeneous phase are
included in the equilibrium equation.
