CHEMICAL KINETICS

Prepared by: Frances Anne B. Blancaflor, LPT

 Objectives:

a. describe how various factors influence the rate of a reaction;

b. differentiate zero, first-, and second-order reactions;
c. explain reactions qualitatively in terms of molecular collisions;
d. explain activation energy and how a catalyst affects the
reaction rate;
e. cite and differentiate the types of catalysts.

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 Chemical Kinetics
-It is the scientific study
of the rates of chemical
reactions.

- Developed from the

law of mass action.

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The rate of reaction 1
 “
The rate of a chemical
reaction is a measure of
the quantity of products
produced per unit of time
or the amount of reactant
reacted/consumed per unit
of time.

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 The speed of a reaction is called the rate of
the reaction.
What is the rate of these reactions?

RUSTING BAKING FIREWORKS

SLOW FAST VERY FAST

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 Why are some reactions faster than others?©

©
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 Rate of reaction
cont.
▸ Reactions take place when
particles collide with a certain
amount of energy.
▸ The minimum amount of
energy needed for the particles
to react is called the
activation energy, and is
different for each reaction.

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 Rate of reaction
cont.
The rate of a reaction depends on
two things:
▸ the frequency of collisions
between particles

▸ the energy with which

particles collide.

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 Rate of reaction
cont.
▸ If particles collide with less
energy than the activation
energy, they will not react.
The particles will just bounce
off each other.

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 Changing the rate of
reactions
▸ Anything that increases the
number of successful
collisions between reactant
particles will speed up a
reaction.

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 Changing the rate of
reactions
What factors affect the rate of
reactions?
▸ increased temperature
▸ increased concentration of
dissolved reactants, and
increased pressure of
gaseous reactants
▸ increased surface area of
solid reactants
▸ use of a catalyst
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 Reactions do not proceed at a steady rate. They start off at a certain speed,
then get slower and slower until they stop.
As the reaction progresses, the concentration of reactants decreases.
This reduces the frequency of collisions between particles and so the
reaction slows down.

0% 25% 50% 75% 100%

reactants percentage completion of reaction
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product
 The rate of reaction cont.

Let’s consider this reaction.

A(g) + B(g) P(g)

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 The rate of reaction cont.
The rate of reaction if expressed in terms of change in concentration of
the product, P, is given by the equation:
Rate= Change in concentration of product
Time

= Concentration of production at time t – Initial concentration of product

Time

= [P]t – [P]0 = ∆[P]

Time Time
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 The rate of reaction cont.

Therefore, if after 6 minutes, the concentration of the product changed from 0

(because no product is present yet at the start of the reaction) to 1.5 M, the
rate becomes:

Rate = 1.5 M-0 = 1.5 M = 0.25 M/min

6 min 6 min

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 The rate of reaction cont.
On the other hand, if the rate is expressed, in terms of a reactant, the
equation becomes:

Rate= Change in concentration of reactant

Time

= Concentration of reactant at time t – Initial concentration of reactant

Time

= [A]t – [A]0 = ∆[A]

Time Time
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 The rate of reaction cont.

Where ∆[A] denotes change in amount of reactant A in concentration. So, if for

the given example, an initial concentration of the reactant of 4.0 M is observed
to decrease to 1.6 M after 6 minutes, the rate of the reaction obtained will be:

Rate = 1.6 M-4.0 M = -2.4 M = -0.4 M/min

6 mi = 6 min

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 Review!

1. The minimum amount of energy needed to start a

reaction is called the______
a) activation energy.
b) energy of reaction.
c) entropy of reaction
d) reaction mechanism energy

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 Review!

2. Which of the following would NOT increase the

rate of reaction.
a. raising the temperature
b. adding catalyst
c. increasing the concentration of the reactants
d. increasing the volume of the container

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 Review!

3. The rate of a chemical reaction can be

expressed in ___
a. grams per mole.
b. energy consumed per mole.
c. volume of gas per unit time.
d. molarity per second

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The Rate Law 2
 “
The rate law is the
relationship between
the concentrations of
reactants and their
various reaction
rates.
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 The general rate law expression for a reaction is:

Rate constant
(units vary) Reaction order

Rate = k [A] [B] x y

Molarity per unit Concentration (M)

of time

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 Rate Law

Rate = k [A] x [B] y

Where:
R= rate of chemical reaction, based on formation of the products or one of the
products, or rate of disappearance of the reactants or one of the reactants.
k= specific reaction rate constant, dependent on the kind of reaction and dependent
on temperature
[A], [B]= molar concentrations of reactants A and B
x, y = exponents showing the magnitude of the effect of the reactant on the rate of
reaction. The values give the order of the reaction
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 Rate Constant k has UNITS! 

Zero Order Reactions Second Order Reactions

rate = k[A]0 rate = k[A]2      rate = k[A][B]

k units:  M/s, M/min, M/hr, etc. k units: M-1s-1, M-1min-1, M-1hr-1, etc.

Third Order Reactions

First Order Reactions
rate = k[A]3      rate = k[A]2[B]     rate = k[A][B]
rate = k[A]
[C]
 k units: s-1, min-1, hr-1, etc.
 k units: M-2s-1, M-2min-1, M-2hr-1, etc.

26 https://www.youtube.com/watch?v=1g-vDSWYins
 Types of Orders

(where order = 0) have a constant rate. The rate

0 zero-order reaction of a zero-order reaction is constant and
independent of the concentration of reactants.

(where order = 1) has a rate proportional to the concentration

1 first-order reaction of one of the reactants. The rate of a first-order reaction is
proportional to the concentration of one reactant.

where order = 2) has a rate proportional to the

2 second-order reaction concentration of the square of a single reactant or

the product of the concentration of two reactants.

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 Rate Law

Rate = k [A] x [B] y

TRIAL [A] [B] RATE M/s

1 0.100 0.100 0.002

2 0.200 0.100 0.004

3 0.200 0.200 0.016

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 Rate Law

Rate = k [A] x [B] y

0.004/0.002 = (0.200/0.100) x
2=2
X= 1
TRIAL [A] [B] RATE
M/s
1 0.100 0.100 0.002
2 0.200 0.100 0.004
3 0.200 0.200 0.016
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 Rate Law

Rate = k [A] 1 [B] y

0.004/0.002 = (0.200/0.100) x
2=2
X= 1 TRIAL [A] [B] RATE
M/s
1 0.100 0.100 0.002
2 0.200 0.100 0.004
3 0.200 0.200 0.016
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 Rate Law

Rate = k [A] 1 [B] y

0.016/0.004 = (0.200/0.100) y
4=2
X= 2 TRIAL [A] [B] RATE
M/s
1 0.100 0.100 0.002
2 0.200 0.100 0.004
3 0.200 0.200 0.016
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 Rate Law

Rate = k [A] 1 [B] 2

Rate = k
0.016/0.004 = (0.200/0.100) y
4=2 TRIAL [A] [B] RATE
M/s
X= 2 1 0.100 0.100 0.002
2 0.200 0.100 0.004
3 0.200 0.200 0.016
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 Rate Law

Rate = k [A] 1 [B] 2

We can now solve for the value of the rate constant by substituting the values of
x and y and any set of experimental data in the rate expression. If we substitute
the values from experiment 1, we get:

0.002 M/s = k (0.100 M) 1 (0.100 M)2

0.002 M/s = 0.001 TRIA [A] [B] RATE
L M/s
k= 2 m -2
/s -1
1 0.100 0.100 0.002
2 0.200 0.100 0.004
3 0.200 0.200 0.016
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 Rate Law

Rate = k [A] x [B] y

Experiment no. [A] [B] Initial rate, M/min

1 0.002 0.002 0.020

2 0.004 0.002 0.080

3 0.004 0.006 0.060

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 Rate Law

Rate = k [A] x [B] y

0.080/0.020 = (0.004/0.002) x
Thus, the reaction is second order with
4 = (2) x respect to reactant A.

2 = x or x = 2
Experimen [A] [B] Initial rate,
t no. M/min
1 0.002 0.002 0.020
2 0.004 0.002 0.080
3 0.004 0.006 0.060
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 Rate Law

Rate = k [A] 2 [B] y

0.080/0.020 = (0.004/0.002) x
Thus, the reaction is second order with
4 = (2) x respect to reactant A.

2 = x or x = 2 Experim
ent no.
[A] [B] Initial
rate,
M/min
1 0.002 0.002 0.020

2 0.004 0.002 0.080

3 0.004 0.006 0.060

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 Rate Law

Rate = k [A] 2 [B] y

Thus, the reaction is 0 order
0.060/0.080 = (0.006/0.002) y
with respect to reactant B.
0.75=(3) y =0.25 Experim [A] [B] Initial
ent no. rate,

y=0 1 0.002 0.002

M/min
0.020

2 0.004 0.002 0.80

3 0.004 0.006 0.060

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 Rate Law

Rate = k [A] 2 [B] 0

Rate = k [A] x [B] y

0.020 M/min = k (0.002 M) 2 (0.002 M)0
Experim [A] [B] Initial
k= 0.5 x 104 M-1/s-1 ent no. rate,
M/min
1 0.002 0.002 0.020

2 0.004 0.002 0.080

3 0.004 0.006 0.060

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 Review!

1. The rate law for a reaction is k[A][B]2

Which one of the following statements is
false?
a. The reaction is first order in A.
b. The reaction is second order in B.
c. The reaction is second order overall.
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d. k is the reaction rate constant
 Review!

2. Ifthe rate law of a reaction is Rate = k[A]2

[B], what is the overall reaction orders?
a. first order overall
b. second order overall
c. third order overall
d. fourth order overall
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 Review!

4. If the unit of rate constant in the second order

overall reaction is M-1 /s -1 , what is the unit of rate
constant of the first order overall?
a. M s
2 -1

b. s -1

c. M s -1
-3

d. s 2

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 Review!
Determine the rate law, total reaction order and the rate constant.

Trial [A] [B] Initial rate (M/s)

1 0.100 0.200 3.50

2 0.200 0.200 7.00

3 0.200 0.400 7.00

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The Collision Theory 3
 “
Collision theory provides a
qualitative explanation of
chemical reactions and the
rates at which they occur.
A basic principle of
collision theory is that, in
order to react, molecules
must collide.

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 Collision theory
▸ The greater frequency of
collisions, the higher the
reaction rate
▸ Only two particles may react
at one time
▸ Many factors must be met:
▹ Orientation
▹ Energy needed to break
bonds (activation energy)

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46
 Collision theory cont.
▸ Though it seems simple,
not all collisions are
effective collisions.

▸ Effective collisions: a
collision that does result
in a reaction.

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 Collision theory cont.
▸ For example, when two
billiard balls collide, they
simply bounce off of one
other. This is also the
most likely outcome
when two molecules, A
and B, come into contact:
they bounce off one
another, completely
unchanged and
unaffected.
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 Collision theory cont.
▸ In order for a collision to
be successful by resulting
in a chemical reaction, A
and B must collide with
sufficient energy to break
chemical bonds. 

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 Collision theory cont.
▸ This is because in any
chemical reaction,
chemical bonds in the
reactants are broken, and
new bonds in the
products are formed.

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 Collision theory cont.
▸ Therefore, in order to
effectively initiate a
reaction, the reactants
must be moving fast
enough (with enough
kinetic energy) so that
they collide with
sufficient force for bonds
to break.
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 Collision theory cont.
▸ This minimum energy
with which molecules
must be moving in order
for a collision to result in
a chemical reaction is
known as the activation
energy.

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 Catalysis

• It is the process of increasing the rate of a

chemical reaction by adding a substance
known as a catalyst.

• Catalyst - a substance that increases the rate

of a chemical reaction without being used
up itself.
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 Catalysis cont.
• A catalyst lowers the activation energy.

The minimum amount of energy that

must be provided to compounds to
result in a chemical reaction. (energy
barrier)

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 Catalysis cont.
Types of Catalysts

1. Heterogeneous catalysts - reactants and catalyst

are in different phases

2. Homogeneous catalysts - reactants and catalysts

are dispersed in single phase

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 Thanks!
Any questions?
You can find me at:
▸ frances.blancaflor@lpu.e
du.ph

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 References:

▸ Presentation template by SlidesCarnival

▸ https://www.khanacademy.org/science/high-school-biology/hs-energy-and-transport/hs-enzymes/a/activation-energy
▸ McGraw-Hill 2009
▸ Ilao, L: Lontoc, B: Gayon, E. General Chemistry 2, First Edition, 2017
▸ https://www.chemguide.co.uk/physical/catalysis/introduction.html

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