Chemical
Kinetics
Important factors which affect rates of reactions:
reactant concentration
temperature
action of catalysts
surface area
pressure of gaseous reactants or products
Outline of the chapter:
Reaction Rates How we measure rates.
How the rate depends on
Rate Laws amounts of reactants.
How long it takes to react 50%
Half-life of reactants.
How rate constant changes
Arrhenius Equation with temperature.
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:
= CONCENTRATION OF REACTANT A
= CONCENTRATION OF REACTANT B
Reaction Rate
For the reaction [A][B] there are two ways of measuring
rate:
the speed at which the reactants disappear
the speed at which the products appear
Chemical Kinetics
Reaction rate is the change in the concentration of a
reactant or a product with time (M/s).
Reaction Rates and Stoichiometry
• To generalize, for the reaction
aA + bB cC + dD
Reactants (decrease) Products (increase)
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
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.
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
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: R = 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
Determination of Rate Laws
Rate laws, rate constants, and orders are determined
experimentally.
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.
Zero-Order Processes
[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)
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
Time (s)
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.
Summary of Kinetics
Second order
First order (1 reactant)
Rate
Laws
Integrat
e d Rate
Laws
Half-life
Summary of Kinetics
Second order
First order (1 reactant)
Rate
Laws
The sequence of events that describes
the actual
Integrat
e d Rate
Laws
Half-life
Reaction Mechanisms
process by which reactants become
products is called the reaction mechanism.
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.
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.
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,
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.
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.
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.
− Ea will vary with the reaction.
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 make it “over the hill” and proceed.
A+B C+D
Exothermic Reaction Endothermic Reaction
The activation energy (Ea) is the minimum amount of
energy required to initiate a chemical reaction.
Arrhenius Equation
where A is the frequency factor, a number
that represents the likelihood that collisions
would occur with the proper orientation for
reaction.
(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
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.
Maxwell–Boltzmann Distributions
As the temperature increases, the curve flattens
and broadens.
Thus at higher temperatures, a larger population
of molecules has higher energy.
Maxwell–Boltzmann Distributions
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.
CATALYST
A catalyst is a substance that increases the rate of a
chemical reaction without itself being consumed.
Ea k
uncatalyzed catalyzed
Ratecatalyzed > Rateuncatalyzed
Catalysts and Reaction Rates
How do catalysts increase reaction
rates?
In general, catalysts operate by lowering the overall
activation energy for a reaction.
However, catalysts can operate by increasing the number
of effective collisions.
A catalyst usually provides a completely different
mechanism for the reaction.
When a catalyst adds an intermediate, the activation
energies for both steps must be lower than the activation
energy for the uncatalyzed reaction.
