CHEMICAL KINETICS

LU 2

Moekwa, T B
Department of Chemistry
 Chemical Kinetics
What are chemical kinetics?
• Is the area of chemistry concerned with reaction
rates and the sequence of steps by which reaction
occur.
• In chemical industry, profitability of processes
requires fast reaction.
 Chemical Kinetics: The Rates of Chemical
Reactions
Thermodynamics – does a reaction take place?
Kinetics – how fast does a reaction proceed?
Chemical Kinetics will now provide information
about the reactants and products.
Reactants Products
This gives us information on how a reaction occurs
 Chemical Kinetics
• Besides information about the speed at which
reactions occur, kinetics also sheds light on the
reaction mechanism (exactly how the reaction
occurs).
• The speed of a chemical reaction is called its
reaction rate.
• The rate of a reaction is a measure of how fast the
reaction makes products or uses reactants.
 Chemical Kinetics
• The rate of a reaction is defined either as the
increase in the concentration of a product(s) per
unit time or the decrease in the concentration of a
reactant(s) per unit time uses reactants.

• The ability to control the speed of a chemical

reaction is important.
 Reaction Rates

• Rate is how much a quantity changes in a given

period of time.
• The speed you drive your car is a rate—the distance
your car travels (kilometers) in a given period of
time (1 hour).
• So, the rate of your car has units of km/hr.
 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.
[A] = concentration of reactant A
 Reaction Rates
• 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
• We want to measure the reactants as soon as they are mixed.
• The most useful (and general) way of measuring the rate of
the reaction is in terms of change in concentration per unit
time…
Rate = ∆[A]/∆t
Units for Rate = M/s
Where Molarity (M) = moles/Liter
 Reaction Rates
• Reaction rate is the change in the concentration of a
reactant or a product with time (M/s).

∆[A] ∆[B]
rate = - rate =
∆t ∆t
∆[A] = change in concentration of A over
time period ∆ t
[A] decreases with time, ∆[A] is negative.

∆[B] = change in concentration of B over

time period ∆ t
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 with each other,
sufficient energy is needed 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
 Reaction Rates
• Looking at the following for reaction rates…
2N2O5(g)  4NO2(g) + O2(g)
• Changes in concentrations of the reactants and/or
products is inversely proportional to their
stoichiometric proportions.
• This means that the rate of the reaction could be
written like this

• Rate = −½ ∆ [N2O5]/∆t = ¼ ∆[NO2]/∆t =

∆[O2]/∆t
note the negative sign on the rate of [N2O5]
 General Reaction Rates
• General reaction rate is equal to the rate of products
consumption of a reactants or formation of a
product divide by the coefficients in the balanced
chemical equations.

• In general, for a reaction that looks like

aA + bB cC + dD

The General reaction rate is

Rate = −1 ∆[A] = −1 ∆[B] = 1 ∆[C] = 1 ∆[D]

a ∆t b ∆t c ∆t d ∆t
 Types of Rates
• Initial Rates
Rates measured at the beginning of the reaction, which is
dependent on the initial concentrations of reactants.
• Instantaneous Rates
Rates measured at any point during the reaction.
• Average Rates
An overall rate measured over a period or time interval.
• Lets look at worked example 13.1 and Do
practice 13.1
 Rate Law and Reaction order
• The rate law of a reaction is the mathematical
relationship between the rate of the reaction and the
concentrations of the reactants and homogeneous
catalysts as well.
• The rate law must be determined experimentally!
• The rate of a reaction is directly proportional to the
concentration of each reactant raised to a power.
 Rate Law and Reaction order

• 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.
 Rate Law and Reaction order
• For the reaction aA + bB  products
• The general rate law for a reaction will be
Rate = k [A]m [B]n
- [A] & [B] represent the reactants.
- The exponents m and n are called “reaction
orders”.
- The proportionality constant k is called the rate
constant.
- The overall reaction order is the sum of the
reaction orders: m+n
 Reaction Orders
Can be zero, positive integer or fraction
Order Name Rate Law
0 zerothrate = k[A]0 = k
1 first rate = k[A]
2 second rate = k[A]2
0.5 one-half rate = k[A]1/2
1.5 three-half rate = k[A]3/2
0.667 two-thirds rate = k[A]2/3
 Rate Law and Reaction order
• The rate law for the reaction

2 NO(g) + O2(g)  2 NO2(g)

is Rate = k[NO]2[O2].

The reaction is
second order with respect to [NO],
first order with respect to [O2],

and third order overall.

 Examples

• Let’s consider the following examples

• Study worked example 13.2 and lets
do Apply 13.4
• Consider the following reaction:
NH4+(aq) + NO2-(aq)  N2(g) + 2H2O(l)
• Let’s say that the following observations from
several experiments were made…
• as [NH4+] doubles the rate doubles with [NO2-] constant.
• as [NO2-] doubles the rate doubles with [NH4+] constant.

• The rate of this reaction would be expressed as….

Rate = k[NH4+][NO2-]
• The reaction is said to be “first order” with respect to
[NH4+] and “first order” with respect to [NO2-].
• But the overall order of the reaction is said to be “second
order.”
• Reaction rates come from experiment data, not
stoichiometry!
• Compare Experiments 1 and 2:
when [NH4+] doubles, the initial rate doubles.
• Likewise, compare Experiments 5 and 6:
when [NO2-] doubles, the initial rate doubles.
• This reaction is
First-order in [NH4+]
First-order in [NO2−]
• The overall reaction order can be found by adding
the exponents on the reactants in the rate law.
• This reaction is second-order overall.
This equation is called the rate law, and k is the rate
constant.
 Integrated Rate Law
• Rate law is an equation that tells how a reaction rate
depends on reactant concentration.
• We are interested on how the reactants and products
concentration vary with time.
• Rate laws can be integrated using calculus to
another form called integrated rate law, which are
Conc- time equations for calculating the
concentration of reactants that remain at any time (t)
• OR Calculating the time required for the initial
concentration of reactant to drop to a certain
level.
 Integrated Rate Law
• Graphical method to derive the rate law
of a reaction:
• Consider a reaction with single reactant:
A  Products
• If the reaction is zero-order w.r.t. [A],
• Then,
- [A]
Rate  k
t
Integrated rate law: Zeroth- order reaction

- [A]
Rate  k
t

That is, d[A] = -kdt and by integrating it, we get

[A]t = [A]0 - kt;
[A]0 is the concentration of A at initial time (t0) and [A]t is
the concentration at anytime (t)
A plot of [A]t versus t yields a straight line with k = -
slope.
 Graph of Zeroth Order Reactions
• Plot of [A]t versus t:
•

slope = -k

[A]t
 Integrated rate law: 1st order reaction

• If the reaction: A  Products is a first order

reaction, then
- [A]
Rate  k[A]
t
• Using Calculus to integrate the rate law
[A]t
• Which yields: ln [A]0  - kt; ln[A]t ln[A]0 - kt

• And a plot of ln[A]t versus t will yield a straight

line with slope = -k and y-intercept = ln[A]0
 Graph of 1 Order Reactions
st

• Plot of ln[A]t versus t:

•

• slope = -k

• ln[A]t
 Half-Life of a 1 order Reaction
st

• Half life (t1/2 )is the time required for a reactant

concentration to drop to one-half of its initial value
• If the reaction: A  Products is a first order
reaction,
[A]t
ln  - kt; ln[A]t ln[A]0 - kt
[A]0
• The t1/2 of a reaction: t1/2 = 0.693/k;
• The t1/2 of the first order reaction is calculated from
the rate constant (k)
• Study examples 13.8 and do practice 13.15
 Integrated rate law: 2nd order reaction
• 2nd order reaction is one whose rate depends either
on the concentration of a single reactant raised to
the 2nd power or two different reactants each raised
to the first power.
• For a reaction with single reactant:
• A  Products
• Rate of consumption of A is given by
• rate = - ∆[A]/ ∆ t = k[A]2
 Integrated rate law: 2nd order reaction
• Using calculus to convert rate law to integrated rate
law
1 1
 kt 
[A]t [A]0
• Y = mx + c
We can calculate the conc. of A at any time if the initial
concentration of A is known.
• A plot of 1/[A]t versus t will yield a straight line
with slope = k and y-intercept = 1/[A]0
 Graph of 2 Order Reactions
nd

• Plot of 1/[A]t versus time:

• slope = k
1
[ R]t

• time
 Half-Life of a 2 order Reaction
nd

• For second order reaction, half-life, t1/2 = 1/k[A]0;

• The time required for [A] to drop to one-half of its
initial concentration depends on both the rate
constant and the initial concentration
• Carefully study worked example 13.9 and
attempt practice 13.17
 Factors that affect reaction rates
• The rate of a reaction depends on both reactants
concentration and value of the rate constant
• Other factor is temperature, i.e, the rate of reaction
increases with increasing temperature. As a rule of
thumb, reaction rates tend to double when the
temperature is increased by 10 oC.
• Think of the food in the freezer (last longer and
spoil as the T increases.
• Another factor is Activation Energy (Ea )
 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.
• Activation energy, Ea, is the minimum energy
required to initiate a chemical reaction.
− Ea will vary with the reaction.
 Activation Energy
• The activation energy, Ea , is the difference in
energy between reactants, 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.
• Note that if a forward reaction is exothermic then
the reverse reaction is endothermic and vise versa
• 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.
The activation energy (Ea) is the minimum amount of energy required to
initiate a chemical reaction.

• For A + B C+D
Exothermic Rxn Endothermic Rxn
 Energy Diagrams

(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
 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.
 Arrhenius Equation
• Taking the natural logarithm of both sides, the
equation becomes
ln(k) = - Ea/R(1/T) + ln(A)

where... k= rate constant

Ea = Activation Energy (in kJ/mole)
R = Gas Constant
T = Kelvin temperature
A = “Frequency Factor”-- a constant
indicating how many collisions have the correct
orientation to lead to products.
 Arrhenius Equation
• A plot ln k vs 1/T gives Arrhenius plot, with
slope= - Ea/R and y-intercept being ln A
• The experimental value of the Ea can be determined
from the slope of the straight line.
• Ea can also be determined from the k (rate constant)
at two different temperatures (T)
• At T1, ln k1 = - Ea/R(1/T1) + ln A ……1 and
• At T2, ln k2 = - Ea/R(1/T2) + ln A ……2
• Subtracting Eq 2 Eq1
• ln (k2/k1) = - Ea/R(1/T2- 1/T1) which is the two point
form of the Arrhenius equation. Exercise 13.21
 catalyst
• A catalyst is a substance that increases the rate of a
chemical reaction without itself being consumed.
• 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.