Dr.

Sulaiman Al-Isaee
College of Applied Sciences-Suhar
Department of Engineering
 Chemical Kinetics

Thermodynamics – does a reaction take place?

Kinetics – how fast does a reaction proceed?

Reaction rate is the change in the concentration of a

reactant or a product with time (M/s).

A B
D[A] D[A] = change in concentration of A over
rate = -
Dt time period Dt
D[B] D[B] = change in concentration of B over
rate =
Dt time period Dt
Because [A] decreases with time, D[A] is negative.
A faster reaction (top) and a slower reaction (bottom).
 A B

time

D[A]
rate = -
Dt

D[B]
rate =
Dt
 Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)

time

393 nm Detector
light
D[Br2] a DAbsorption
13.1
Following Reaction Rates

 Rate of a reaction is
measured using the
concentration of a
reactant or a
product over time.
 In this example,
[C4H9Cl] is followed.
Following Reaction Rates

 The average rate is

calculated by the –
(change in [C4H9Cl]) ÷
(change in time).
 The table shows the
average rate for a
variety of time
intervals.
 Plotting Rate Data
• A plot of the data gives more
information about rate.
• The slope of the curve at one
point in time gives the
instantaneous rate.
• The instantaneous rate at time
zero is called the initial rate;
this is often the rate of interest
to chemists.
• This figure shows instantaneous
Note: Reactions
and initial rate of the earlier typically slow down
example. over time!
 Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)

slope of
tangent
slope of
tangent slope of
tangent

D[Br2] [Br2]final – [Br2]initial

average rate = - =-
Dt tfinal - tinitial
instantaneous rate = rate for specific instance in time
 Reaction Rates and Stoichiometry

2A B

Two moles of A disappear for each mole of B that is formed.

1 D[A] D[B]
rate = - rate =
2 Dt Dt

aA + bB cC + dD

1 D[A] 1 D[B] 1 D[C] 1 D[D]

rate = - =- = =
a Dt b Dt c Dt d Dt
Write the rate expression for the following reaction:

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g)

D[CH4] 1 D[O2] D[CO2] 1 D[H2O]

rate = - =- = =
Dt 2 Dt Dt 2 Dt
Sample Problem 1 Expressing Rate in Terms of Changes in
Concentration with Time
PROBLEM: Hydrogen gas has a nonpolluting combustion product
(water vapor). It is used as a fuel abord the space shuttle
and in earthbound cars with prototype engines:
2H2(g) + O2(g) → 2H2O(g)
(a) Express the rate in terms of changes in [H2], [O2], and
[H2O] with time.
(b) When [O2] is decreasing at 0.23 mol/L·s, at what rate is
[H2O] increasing?
PLAN: We choose O2 as the reference because its coefficient is 1. For
every molecule of O2 that disappears, two molecules of H2
disappear, so the rate of [O2] decrease is ½ the rate of [H2]
decrease. Similarly, the rate at which [O2] decreases is ½ the rate
at which [H2O] increases.
Sample Problem 1

SOLUTION:
D[O2] 1 D[H2] 1 D[H2O]
(a) Rate = - =- =
Dt 2 Dt 2 Dt

(b) Calculating the rate of change of [H2O]:

1 D[H2O] D[O2]
=- = -(-0.23 mol/L·s)
2 Dt Dt

D[H2O]
= 2(0.23 mol/L·s) = 0.46 mol/L·s
Dt
 Factors That Influence Reaction Rate
• Particles must collide in order to react.
• The higher the concentration of reactants, the greater
the reaction rate.
– A higher concentration of reactant particles allows a greater
number of collisions.
• The physical state of the reactants influences reaction
rate.
– Substances must mix in order for particles to collide.
• The higher the temperature, the greater the reaction
rate.
– At higher temperatures particles have more energy and
therefore collide more often and more effectively.
 The Rate Law

For any general reaction occurring at a fixed temperature

aA + bB → cC + dD

Rate = k[A]m[B]n

The term k is the rate constant, which is specific for a

given reaction at a given temperature.

The exponents m and n are reaction orders and are

determined by experiment.
The values of m and n are not necessarily related in any way to
the coefficients a and b.
 Concentration and Rate

Compare Experiments 1 and 2:

when [NH4+] doubles, the initial rate doubles.
 Concentration and Rate

Likewise, compare Experiments 5 and 6:

when [NO2-] doubles, the initial rate doubles.
 Concentration and Rate

This equation is called the rate law,

and k is the rate constant.
 Rate Laws
• Rate laws are always determined experimentally.

• Reaction order is always defined in terms of reactant

(not product) concentrations.

• The order of a reactant is not related to the

stoichiometric coefficient of the reactant in the balanced
chemical equation.

F2 (g) + 2ClO2 (g) 2FClO2 (g)

rate = k [F2][ClO2] 1

13.2
Sample Problem 2 Determining reaction order from rate laws

PROBLEM: For each of the following reactions, determine the reaction order
with respect to each reactant and the overall reaction order from
the given rate law.

(a) 2NO(g) + O2(g) 2NO2(g); rate = k[NO]2[O2]

(b) CH3CHO(g) CH4(g) + CO(g); rate = k[CH3CHO]3/2

(c) H2O2(aq) + 3I-(aq) + 2H+(aq) I3-(aq) + 2H2O(l); rate = k[H2O2][I-]

PLAN: Inspect the rate law and not the coefficients in the balanced chemical
reaction.
SOLUTION:

(a) The reaction is 2nd order in NO, 1st order in O2, and 3rd order overall.

(b) The reaction is 3/2-order in CH3CHO and 3/2-order overall.

(c) The reaction is 1st order in H2O2, 1st order in I- and zero order in H+,
and 2nd order overall.
 Determining Reaction Orders

For the general reaction A + 2B → C + D,

the rate law will have the form
Rate = k[A]m[B]n

To determine the values of m and n, we run a series of

experiments in which one reactant concentration
changes while the other is kept constant, and we
measure the effect on the initial rate in each case.
 Table Initial Rates for the Reaction between A and B

Initial Rate Initial [A] Initial [B]

Experiment (mol/L·s) (mol/L) (mol/L)
1 1.75x10-3 2.50x10-2 3.00x10-2
2 3.50x10-3 5.00x10-2 3.00x10-2
3 3.50x10-3 2.50x10-2 6.00x10-2
4 7.00x10-3 5.00x10-2 6.00x10-2

[B] is kept constant for experiments 1 and 2, while [A] is doubled.

Then [A] is kept constant while [B] is doubled.
Finding m, the order with respect to A:
We compare experiments 1 and 2, where [B] is kept
constant but [A] doubles:

Rate 2 k[A] m [B] n m

[A] 2 [A]2 m
2 2 = =
=
Rate 1 k[A] [B] n
m m
[A]1 [A]1
1 1
m
3.50x10-3 mol/L·s 5.00x10-2 mol/L
=
1.75x10 mol/L·s
-3
2.50x10-2 mol/L

Dividing, we get 2.00 = (2.00)m so m = 1

Finding n, the order with respect to B:
We compare experiments 3 and 1, where [A] is kept
constant but [B] doubles:

Rate 3 k[A] m [B] n n

[B] 3 [B]3 n
3 3 = =
=
Rate 1 k[A] [B] n
m n
[B]1 [B]1
1 1
m
3.50x10-3 mol/L·s 6.00x10-2 mol/L
=
1.75x10 mol/L·s
-3
3.00x10-2 mol/L

Dividing, we get 2.00 = (2.00)n so n = 1

Table Initial Rates for the Reaction between O2 and NO

O2(g) + 2NO(g) → 2NO2(g) Rate = k[O2]m[NO]n

Initial Reactant
Concentrations (mol/L)
Initial Rate
Experiment (mol/L·s) [O2] [NO]
1 3.21x10-3 1.10x10-2 1.30x10-2
2 6.40x10-3 2.20x10-2 1.30x10-2
3 12.48x10-3 1.10x10-2 2.60x10-2
4 9.60x10-3 3.30x10-2 1.30x10-2
5 28.8x10-3 1.10x10-2 3.90x10-2
Finding m, the order with respect to O2:
We compare experiments 1 and 2, where [NO] is kept
constant but [O2] doubles:
Rate 2 k[O2] m
2 [NO] n
2 [O2] m
2 = [O2]2
m
= m n = m
Rate 1 k[O2] 1 [NO] 1 [O2] 1 [O2]1
m
6.40x10-3 mol/L·s 2.20x10-2 mol/L
=
3.21x10 mol/L·s
-3
1.10x10-2 mol/L

Dividing, we get 1.99 = (2.00)m or 2 = 2m, so m = 1

The reaction is first order with respect to O2.

Sometimes the exponent is not easy to find by inspection.
In those cases, we solve for m with an equation of the form
a = bm:
log a log 1.99
m= = = 0.993
log b log 2.00

This confirms that the reaction is first order with respect to O2.

Reaction orders may be positive integers, zero, negative integers, or

fractions.
Finding n, the order with respect to NO:
We compare experiments 1 and 3, where [O2] is kept
constant but [NO] doubles:
n
Rate 3 [NO]3 n
= 12.8x10-3 mol/L·s 2.60x10-2 mol/L
=
Rate 1 [NO]1 3.21x10 mol/L·s
-3
1.30x10-2 mol/L

Dividing, we get 3.99 = (2.00)n or 4 = 2n, so n = 2.

log a log 3.99
Alternatively: n= = = 2.00
log b log 2.00

The reaction is second order with respect to NO.

The rate law is given by: rate = k[O2][NO]2

Sample Problem 3 Determining Reaction Orders from Rate Data

PROBLEM: Many gaseous reactions occur in a car engine and exhaust

system. One of these is
NO2(g) + CO(g) → NO(g) + CO2(g) rate = k[NO2]m[CO]n
Use the following data to determine the individual and
overall reaction orders:

Initial Rate Initial [NO2] Initial

Experiment (mol/L·s) (mol/L) [CO]
(mol/L)
1 0.0050 0.10 0.10
2 0.080 0.40 0.10
3 0.0050 0.10 0.20
Sample Problem 3

PLAN: We need to solve the general rate law for m and for n and
then add those orders to get the overall order. We proceed by
taking the ratio of the rate laws for two experiments in which
only the reactant in question changes concentration.
SOLUTION:
To calculate m, the order with respect to NO2, we compare
experiments 1 and 2:
m m
rate 2 k [NO2]m2[CO]n2 [NO2] 2 0.080 0.40
= = =
rate 1 k [NO ] [CO]
m
2 1
n
1 [NO2] 1 0.0050 0.10
16 = (4.0)m so m = 2

The reaction is second order in NO2.

Sample Problem 3

To calculate n, the order with respect to CO, we compare experiments

1 and 3:
n n
rate 3 k [NO2]m3[CO]n3 [CO] 3 0.0050 0.20
= = =
rate 1 k [NO ] [CO]
m
2 1
n
1 [CO] 1 0.0050 0.10

1.0 = (2.0)n so n = 0

The reaction is zero order in CO.

rate = k[NO2]2[CO]0 or rate = k[NO2]2

 Integrated Rate Laws
• The rate laws we have considered so far express the rate as a
function of the reactant concentrations.
Rate = k[A]m[B]n
• It is also useful to be able to express the reactant concentrations as
a function of time, given the (differential) rate law for the reaction.
• An integrated rate law includes time as a variable.
First Order Reactions:
• Some rates depend only on one reactant to the first power.
• These are first order reactions.
• The rate law becomes:
Rate = k [A]
 Relating k to [A] in a First Order
Reaction

A product
• rate = k [A]
• rate = −Δ [A] / Δt
• So: k [A] = −Δ [A] / Δt
• Rearrange to: Δ [A] / [A] = − k Δt
• Integrate: ln ([A] / [A]o) = − k t
• Rearrange: ln [A] = − k t + ln [A]o
• Note: this follows the equation of a line: y = m x + b
• So, a plot of ln [A] vs. t is linear.
An Example: Conversion of Methyl Isonitrile to
Acetonitrile
• The equation for the reaction:
CH3NC → CH3CN
• It is first order.
Rate = k [CH3NC]
 Sample Problem 4
The reaction 2A B is first order in A with a rate constant of 2.8 x
10-2 s-1 at 800C. How long will it take for A to decrease from 0.88 M to
0.14 M ?

ln[A] = ln[A]0 - kt [A]0 = 0.88 M

[A] = 0.14 M
kt = ln[A]0 – ln[A]
[A]0 0.88 M
ln ln
ln[A]0 – ln[A] [A] 0.14 M
t= = = = 66 s
k k 2.8 x 10 s
-2 -1
 First-Order Reactions

The half-life, t½, is the time required for the concentration of a

reactant to decrease to half of its initial concentration.
t½ = t when [A] = [A]0/2
[A]0
ln
[A]0/2 ln2 0.693
t½ = = =
k k k

What is the half-life of N2O5 if it decomposes with a rate

constant of 5.7 x 10-4 s-1?

t½ = ln2 = 0.693
= 1200 s = 20 minutes
k 5.7 x 10 s
-4 -1
 Second-Order Reactions
D[A]
A product rate = - rate = k [A]2
Dt

rate M/s D[A]

k= = 2 = 1/M•s
- = k [A]2
[A] 2 M Dt

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
 Zero-Order Reactions
D[A]
A product rate = - rate = k [A]0 = k
Dt

rate D[A]
k= = M/s - =k
[A] 0
Dt

[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
 Graphical method for finding the reaction order from the
integrated rate law.

First-order reaction

integrated rate law

ln [A]0 = - kt
[A]t

straight-line form
ln[A]t = -kt + ln[A]0

A plot of ln [A] vs. time gives a straight line for a first-order reaction.
Graphical method for finding the reaction order from the integrated rate law.

Second-order reaction
integrated rate law
1 1
- = kt
[A]t [A]0

straight-line form
1 1
= kt +
[A]t [A]0

1
A plot of vs. time gives a straight line for a second-order reaction.
[A]
Graphical method for finding the reaction order from the integrated rate law.

Zero-order reaction

integrated rate law

[A]t - [A]0 = - kt

straight-line form
[A]t = - kt + [A]0

A plot of [A] vs. time gives a straight line for a first-order reaction.
Graphical determination of the reaction order for the
decomposition of N2O5.

The concentration data is used to

construct three different plots. Since the
plot of ln [N2O5] vs. time gives a straight
line, the reaction is first order.
Sample Problem 5 Determining the Reactant Concentration
after a Given Time
PROBLEM: At 1000oC, cyclobutane (C4H8) decomposes in a first-order
reaction, with the very high rate constant of 87 s-1, to two
molecules of ethylene (C2H4).
(a) If the initial C4H8 concentration is 2.00 M, what is the
concentration after 0.010 s?
(b) What fraction of C4H8 has decomposed in this time?

PLAN: We must find the concentration of cyclobutane at time t, [C4H8]t.

The problem tells us the reaction is first-order, so we use the
integrated first-order rate law:
[C4H8 ]0
ln = - kt
[C4H8 ]t
Sample Problem 5

SOLUTION:
[C4H8 ]0 2.00 mol/L
(a) ln = - kt ln = (87 s-1)(0.010 s) = 0.87
[C4H8 ]t [C4H8 ]t
2.00 mol/L
= e0.87 = 2.4
[C4H8 ]t

[C2H4] = 2.00 mol/L = 0.83 mol/L

2.4

(b) Finding the fraction that has decomposed after 0.010 s:

[C4H8]0 - [C4H8]t 2.00 M - 0.83 M
= = 0.58
[C4H8]0 2.00 M
 An Overview of Zero-Order, First-Order, and Simple Second-
Order Reactions

Zero Order First Order Second Order

Rate law rate = k rate = k[A] rate = k[A]2
Units for k mol/L·s 1/s L/mol·s
Half-life [A]0 ln 2 1
2k k k[A]0
Integrated rate law [A]t = -kt + [A]0 ln[A]t = -kt + ln[A]0 1 1
= kt +
in straight-line form [A]t [A]0
1
Plot for straight line [A]t vs. t ln[A]t vs. t vs. t
[A]t
Slope, y intercept -k, [A]0 -k, ln[A]0 k, 1
[A]0
 Temperature and Rxn Rate

• Generally, as temperature increases, so does the

reaction rate, But WHY??
Rate = k[A] [B]
m n

• Does changing the Temp. change [A] or [B]? No.

• So, why does increasing the temp. increase the
reaction’s rate?

Because it increases the reaction rate K

• To explain that we use something called the collision

modle
 The Collision Model

• Molecules have to collide to react. The greater the

numbers of collisions per second, the greater the
chance that molecules will get together in a way
that leads them to react.
• Increasing a reaction’s temp. increases individual
molecules speeds. This increases the total numbers
of collisions they experience and, hence, the overall
likelihood that molecules will get together in a way
that leads them to react.
 The Collision Model

• But colliding, by itself, is not enough to automatically

cause a reaction to occur.

WAY??

The answer comes down to 2 additional factors:

1. orientation.
2. Activating energy.
 The Collision Model

First of all, molecules must collide with the

correct orientation.
 Activation Energy

• Beyond molecules needing to collide with the correct

orientation in to react, there’s another important factor that
determines reaction rate called activation energy.
• Chemical reaction always require a certain amount of energy
to get starting, or a minimum amount of energy required for
reaction: the activation energy, Ea.
 Activation Energy

• This might sound weird, but there are actually some reactions that are
quite exothermic, but still don’t happen easily, because the activation
energy between the reactants and product is too high.

• The product is much more stable than the reactant. So, why doesn’t it
occur spontaneously? Because in order to convert A to B, the reaction has
to traverse unstable, with high energy state C (transition state). This
required a high amount of activation energy (Ea).
 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.
 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 energy barrier.
Reaction Coordinate Diagrams
 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.
 Maxwell–Boltzmann Distributions

This fraction of molecules can be found through the expression:

where R is the gas constant and T is the temperature in Kelvin .

 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
1
RT
y = mx + b
When k is determined experimentally at several
temperatures, Ea can be calculated from the slope
of a plot of ln k vs. 1/T.
 Reaction Mechanisms

The sequence of events that describes the

actual 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.
 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.
 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.
 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.
 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.
 Reaction Mechanisms

We can now define a reaction mechanism more precisely. It is a

series of elementary steps that must satisfy two requirements:

1. The sum of the elementary steps must give the overall balanced
equation for the reaction.

2. The mechanism must agree with the experimentally determined

rate law.
 Catalysts

• Catalysts increase the rate of a reaction by

decreasing the activation energy of the reaction.
• Catalysts change the mechanism by which the
process occurs.
 H2C C H 2 (g) + H 2 (g) H3C C H 3 (g)
Ni, Pd or Pt