CHE 101:Chemistry

Chemical Kinetics
lecture no.8

Mr. Harminder Singh

LSECA + LSTCA

Chemical
Kinetics
 Kinetics
• Studies the rate at which a chemical
process occurs.
• Besides information about the speed at
which reactions occur, kinetics also sheds
light on the reaction mechanism (exactly
how the reaction occurs).

Chemical
Kinetics
 Outline: Kinetics
Reaction Rates How we measure rates.

How the rate depends on amounts

Rate Laws of reactants.
How to calc amount left or time to
Integrated Rate Laws reach a given amount.
How long it takes to react 50% of
Half-life reactants.

Arrhenius Equation How rate constant changes with T.

Link between rate and molecular

Mechanisms scale processes. Chemical
Kinetics
Factors That Affect Reaction Rates
• Concentration of Reactants
 As the concentration of reactants increases, so does the
likelihood that reactant molecules will collide.
• Temperature
 At higher temperatures, reactant molecules have more
kinetic energy, move faster, and collide more often and with
greater energy.
• Catalysts
 Speed rxn by changing
mechanism.

Chemical
Kinetics
 Reaction Rates

Rxn Movie

Rates of reactions can be determined by

monitoring the change in concentration of
either reactants or products as a function of
time. [A] vs t Chemical
Kinetics
The factors mentioned will affect the composition of the
reaction mixture at any given time.
Therefore
The change in composition of the reaction mixture with
time
is the rate of reaction, denoted by R, r or .

R is the same whether monitoring reactants or products

Generally, aA + bB cC + dD
Chemical
Kinetics
 Rate laws, rate constants, reaction order

R = ƒ ([A][B])
And, R  [A]m [B]n

With the use of a proportionality constant k, which is the

rate constant (independent of conc. but dependent on
temp.), R = -d[A]/dt = k [A]m [B]n

Such an equation is called the rate law Chemical

Kinetics
The exponents m and n are the order of the reaction with

respect to reactant A and the order of the reaction with

respect to reactant B respectively.
The order of the reaction = m + n
If m = n =1, then the reaction is first-order in A and first-order in B,

but second-order overall, therefore: R = k [A][B]

Hence, 3 1
R mol dm s 1 1
k  3 2
 dm 3
mol s
[ A][ B ] ( mol dm )
Units for rate constant
If first-order overall???? for 2nd order reaction
3
R mol dm s 1 1
k   s
[ A] mol dm 3 Units for rate constant Chemical
for 1st order reaction Kinetics
Lecture no.9-10

Chemical
Kinetics
 Determine the rate law and calculate the rate constant
for the following reaction from the following data:
S2O82- (aq) + 3I- (aq) 2SO42- (aq) + I3- (aq)
Initial rate = k [S 2 O 8 ] [I ]
2- x - y
Experiment [S2O8 ]
2-
[I ]
-
Rate (M/s)
y=1
1 0.08 0.034 2.2 x 10 -4

2 0.08 0.017 1.1 x 10-4

x=1
3 0.16 0.017 2.2 x 10-4 rate = k [S2O82-][I-]

Double [I-], rate doubles (experiment 1 & 2)

Double [S2O82-], rate doubles (experiment 2 & 3)

rate 2.2 x 10-4 M/s

k= = = 0.08/M•s Chemical
[S2O8 ][I ]
2- -
(0.08 M)(0.034 M) Kinetics
13.2
 First-Order Reactions
A product [A]
rate = - rate = k [A]
t
rate
k = [A] = M/s = 1/s or s-1
M
[A] [A] is the concentration of A at any time t
- = k [A] [A]0 is the concentration of A at time t=0
t
[A] = [A] exp(-kt) ln[A] = ln[A]0 - kt
0

Chemical
Kinetics
 Zero-Order Reactions
[A]
A product rate = - rate = k [A]0 = k
t
[A]
k = rate = M/s - =k
[A]0 t
[A] is the concentration of A at any time t
[A] = [A]0 - kt [A]0 is the concentration of A at time t=0

t½ = t when [A] = [A]0/2

[A]0
t½ =
2k Chemical
Kinetics
 Second-Order Reactions
[A]
A product rate = - rate = k [A]2
t
[A]
k = rate2 = M/s = 1/M•s - = k [A]2
[A] M 2
t
1 1 [A] is the concentration of A at any time t
= + kt
[A] [A]0 [A]0 is the concentration of A at time t=0

t½ = t when [A] = [A]0/2

1
t½ =
k[A]0 Chemical
Kinetics
 Reaction Orders
For the reaction: A →B, the rate law is:
rate = k [A]m
Order (m) Δ[A] by a factor of: Effect on rate
Zero (0) 2, 4, 15, ½, etc. None
2 2X
1 (1)
st
3 3X
2 4X
2nd (2) 3 9X
½ ¼X Chemical
Kinetics
 First-Order Processes

If a reaction is first-order, a plot of ln [A]t

vs. t will yield a straight line with a slope
of -k.
So, use graphs to determine rxn order.
Chemical
Kinetics
First-Order Processes
Consider the process in
which methyl isonitrile is
converted to acetonitrile.

CH3NC CH3CN

How do we know this

is a first order rxn? Chemical
Kinetics
 First-Order Processes
CH3NC CH3CN
This data was
collected for this
reaction at 198.9°C.

Does
rate=k[CH3NC]
for all time intervals? Chemical
Kinetics
 First-Order Processes

• When ln P is plotted as a function of time, a

straight line results.
 The process is first-order. Chemical
Kinetics
 k is the negative slope: 5.1  10-5 s-1.
 Second-Order Processes
Similarly, integrating the rate law for a process
that is second-order in reactant A:

Rearrange, integrate:

also in the form y = mx + b

Chemical
Kinetics
 Second-Order Processes

So if a process is second-order in A, a plot of

1/[A] vs. t will yield a straight line with a slope
of k.
First order:

If a reaction is first-order, a plot of ln [A]t vs. t will yield

a straight line with a slope of -k. Chemical
Kinetics
Half-Life
• Half-life is defined
as the time required
for one-half of a
reactant to react.
• Because [A] at t1/2 is
one-half of the
original [A],
[A]t = 0.5 [A]0.
Chemical
Kinetics
 Half-Life
For a first-order process, set [A]t=0.5 [A]0 in
integrated rate equation:

NOTE: For a first-order

process, the half-life does
Chemical
not depend on [A]0. Kinetics
 Half-Life- 2nd order
For a second-order process, set
[A]t=0.5 [A]0 in 2nd order equation.

Chemical
Kinetics
Lecture no. 11

Chemical
Kinetics
 Activation Energy
• In other words, there is a minimum amount of energy
required for 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.

Chemical
Kinetics
Temperature and Rate

• Generally, as temperature
increases, so does the
reaction rate.
• This is because k is
temperature dependent.

Chemical
Kinetics
Maxwell-Boltzman Distribution
• At higher
temperatures,
more molecules
will have
adequate energy
to react.
• This increases
the reaction rate.
Chemical
Kinetics
 The Collision Model

• In a chemical reaction, bonds are

broken and new bonds are formed.
• Molecules can only react if they collide
with each other.

Chemical
Kinetics
 The Collision Model
Furthermore, molecules must collide with the
correct orientation and with enough energy to
cause bond breakage and formation.

Chemical
Kinetics
 Reaction Coordinate Diagrams
It is helpful to
visualize energy
changes
throughout a
process on a
reaction coordinate
diagram like this
one for the
rearrangement of
methyl isonitrile.
Chemical
Kinetics
 Reaction Coordinate Diagrams
• It shows the energy of
the reactants and
products (and, therefore,
E).
• The high point on the
diagram is the transition
state.

• The species present at the transition state is

called the activated complex.
• The energy gap between the reactants and
the activated complex is the activation Chemical
Kinetics
energy barrier.
 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. Chemical
Kinetics
 Arrhenius Equation
Taking the natural
logarithm of both
sides, the equation
becomes 1
RT
y = mx + b

When k is determined experimentally at

several temperatures, Ea can be calculated Chemical
Kinetics
from the slope of a plot of ln k vs. 1/T.
 Outline: Kinetics
First order Second order Second order
Rate
Laws
Integrate
d Rate complicated
Laws

Half-life complicated

k(T)
Chemical
Kinetics
Lecture no.12

Chemical
Kinetics
 Reaction Mechanisms
The sequence of events that describes
the actual process by which reactants
become products is called the reaction
mechanism.

Chemical
Kinetics
 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.
Chemical
Kinetics
 Reaction Mechanisms

• The molecularity of a process tells how many

molecules are involved in the process.
• The rate law for an elementary step is written
directly from that step.
Chemical
Kinetics
 Multistep Mechanisms
• In a multistep process, one of the steps will
be slower than all others.
• The overall reaction cannot occur faster than
this slowest, rate-determining step.

Chemical
Kinetics
 Slow Initial Step
NO2 (g) + CO (g)  NO (g) + CO2 (g)
• The rate law for this reaction is found
experimentally to be
Rate = k [NO2]2
• CO is necessary for this reaction to occur, but the
rate of the reaction does not depend on its
concentration.
• This suggests the reaction occurs in two steps.
Chemical
Kinetics
 Slow Initial Step
• A proposed mechanism for this reaction is
Step 1: NO2 + NO2  NO3 + NO (slow)
Step 2: NO3 + CO  NO2 + CO2 (fast)
• The NO3 intermediate is consumed in the second step.
• As CO is not involved in the slow, rate-determining step, it does
not appear in the rate law.

Chemical
Kinetics
 Fast Initial Step

• The rate law for this reaction is found

(experimentally) to be

• Because termolecular (= trimolecular)

processes are rare, this rate law suggests a
two-step mechanism. Chemical
Kinetics
 Fast Initial Step
• A proposed mechanism is

Step 1 is an equilibrium-
it includes the forward and reverse reactions.
Chemical
Kinetics
 Fast Initial Step

• The rate of the overall reaction depends

upon the rate of the slow step.
• The rate law for that step would be

Chemical
• But how can we find [NOBr2]? Kinetics
 Fast Initial Step

• NOBr2 can react two ways:

With NO to form NOBr
By decomposition to reform NO and Br2
• The reactants and products of the first
step are in equilibrium with each other.
• Therefore,
Ratef = Rater Chemical
Kinetics
 Fast Initial Step

• Because Ratef = Rater ,

k1 [NO] [Br2] = k−1 [NOBr2]

Solving for [NOBr2] gives us

k1
[NO] [Br2] = [NOBr2]
k−1 Chemical
Kinetics
 Fast Initial Step

Substituting this expression for [NOBr2]

in the rate law for the rate-determining
step gives

Chemical
Kinetics