L.

O 11
Chemical Kinetics
Chemical Kinetics

It is the area of chemistry that concerns the

reaction rates. One of the main goals of
chemical kinetics is to understand the steps by
which a reaction takes place which is called the
reaction mechanism. Understanding the
mechanism allows us to find ways to facilitate
the reaction.
1.2 Reaction Rate
 
 It is the change in concentration of a reactant or product per unit time.
 
 It can be expressed either in terms of the decrease in the amount of a
reactant or the increase in the amount of a product per unit time.

concentration of A at time t 2  concentration of A at time t1

  Rate =
t 2  t1
 
* [A] means= concentration
 A of A in mol/L.
* A is the reactant
t or product being considered.
 
 EXAMPLE: The Decomposition of Nitrogen Dioxide
2NO2(g) à 2NO(g) + O2(g)
 

Instantaneous Rate
 
It is the value of rate at particular time. It can be obtained by computing the slope of a line tangent to the curve at that point.
 
 
 Types of rate laws

Differential Rate Law (rate law)

• shows how the rate of a reaction depends on

concentrations.

Integrated Rate Law

• shows how the concentrations of species in the reaction
depend on time.
1.3 Rate Laws: an introduction
 
It shows how the rate depends on the concentrations of reactants.
 
For the decomposition of nitrogen dioxide:
2NO2(g) → 2NO(g) + O2(g)

Rate= k[NO2]n:
k = rate constant
n = order of the reactant
.
The concentrations of the products do not appear in the rate law because the
reaction rate is being studied under conditions where the reverse reaction does not
contribute to the overall rate.
 
The value of the exponent n must be determined by experiment; it cannot be written
from the balanced equation.
­––––––
 Determining the Form of the Rate Law

A. Determining the value of n (Order of the reactant):

•We determine experimentally the power to which each reactant concentration must
be raised in the rate law.
For example:

Doubling the concentration of species A quadruples the rate of the reaction. Therefore, the
reaction is of second order with respect to A
Rate = k[A]2
 Determining the Form of the Rate Law
B. Method of Initial Rates:
•The value of the initial rate is determined for each experiment at the same value of t as close
to t = 0 as possible.
•Several experiments are carried out using different initial concentrations of each of the
reactants, and the initial rate is determined for each run.
•The results are then compared to see how the initial rate depends on the initial concentrations
of each of the reactants.
For example:
 Determining the Form of the Rate Law

 In experiment 1 and 2, the concentration of NH4 is held constant.

 In experiment 2 and 3, the concentration of NO2 is held constant.
 Basic rate law for the reaction:
 
 
 Experiment 1 and 2:
As the rate doubles when concentration of NO2 doubles, then
m = 1 (first order)
 
 
 Experiment 2 and 3:
As the rate doubles when concentration of NH4 doubles, then
n = 1 (first order)
 
 
 As a result:

 
 Determining the Form of the Rate Law

Overall Reaction Order

- The sum of the exponents in the reaction rate equation.

- Overall reaction order = n + m

k = rate constant
[A] = concentration of reactant A
[B] = concentration of reactant B

 
 
 
The Integrated Rate Law

• The Integrated rate laws are mathematically derived from differential rate laws, and
they describe the time dependence of reactant and product concentrations.
• The half-life of a reaction is the time required to decrease the amount of a given
reactant by one-half. A reaction’s half-life varies with rate constant and, for some
reaction orders, reactant concentration.
• 
 
A. Integrated First-Order Rate Law (single reactant):
Differential Rate Law = k[A]
Integrated Law:

[A] = concentration of A at time t

k = rate constant
t = time
[A]o = initial concentration of A
Plotting:
A graph of ln[A] versus t is a straight line with slope –k

 
Half Life:
0.693
t1 =
2 k
k = rate constant
Half–life does not depend on the concentration of reactants.
 
B. Second-order integrated rate law(Single reactant):
Rate = k[A]2
Integrated: 1 1
= kt +
 A  A 0
[A] = concentration of A at time t
k = rate constant
t = time
[A]o = initial concentration of A
Plotting:
Graph of 1/[A] versus t is a straight line with slope k
 
Half–Life:
1
t1 =
2 k  A 0
k = rate constant
[A]o = initial concentration of A
Half–life gets longer as the reaction progresses and the concentration of reactants decrease.
Each successive half–life is double the preceding one.
 
 
•
•C. Integrated Zero-Order Law
• Rate = k[A]0 = k
• Integrated:
• [A] = –kt + [A]o
• [A] = concentration of A at time t
• k = rate constant
• t = time
• [A]o = initial concentration of A
• Plotting:
• Graph of [A] versus t is a straight line with slope -k
• 
• 
• Half–Life:
• 

• k = rate constant
• [A]o = initial concentration of A
• Half–life gets shorter as the reaction progresses and the concentration of reactants decrease.
• 
D. Integrated Rate Laws for Reactions with More than One Reactant:
 
1. Examine rate with one reactant in very low concentration and the others much higher

a. If [B]> >[A] and [C] > >[A] then [B] and [C] do not change as greatly relative to [A] so

2. Pseudo-first-order rate law (or zero-order, or second order)

a. Simplification yields a rate law of a particular order.
 
 
 
Rate Laws: Summary
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Reaction Mechanism:

• Most chemical reactions occur by a series of elementary steps which is called reaction mechanism.
• An intermediate is formed in one step and used up in a subsequent step and thus is never seen as a product in
the overall balanced reaction. It is neither a reactant or a product as it is formed and consumed during the chemical
reaction.
•  
an overview of the elementary steps in a specific reaction
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
Molecularity
1. The number of species that must collide to produce the reaction indicated
by that step
a. Unimolecular step - a reaction involving one molecule.
b. Bimolecular step - reaction involving the collisions of two species.
c. Termolecular step - reaction involving the collisions of three species.
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
• Rate-Determining Step:
• A reaction is only as fast as its slowest step.
• The rate-determining step (slowest step) determines the rate law and the molecularity of the overall
reaction.
• Example
• Overall reaction:
• NO2(g) + CO(g) à NO(g) + CO2(g)
• Rate law determined experimentally:
• Rate = k[NO2]2
• Elementary Steps
• NO2(g) + NO2(g) ¾¾k1® NO3(g) + NO(g)
• NO3(g) + CO(g) ¾¾k2® NO2(g) + CO2(g)
• Which step is rate determining?
• a. IF step 1, Rate = k[NO2]2
• - this agrees with experimental results
• b. IF step 2, Rate = k[NO3][CO]
• - this does not agree with experimental results
• Reaction mechanism requirements
• The sum of the elementary steps must give the overall balanced equation for the reaction.
• The mechanism must agree with the experimentally determined rate law.
 
A Model for Chemical Kinetics
A. Collision Model
1. Molecules must collide in order to react:
a. They must collide with sufficient energy.
b. They must collide with correct orientation.
 
2. Collision theory provides a simple but effective explanation for the effect of many experimental parameters
on reaction rates.
 
B. Activation Energy (Ea)
1. The energy required to convert atoms or molecules into the activated
complex (transition state)
2. The minimum energy required for an effective collision.
C. The Arrhenius Equation:
The Arrhenius equation describes the relation between a reaction’s rate constant, activation energy,
temperature, and dependence on collision orientation.
1. Form #1:

a. z is collision frequency.
b. p is the stearic factor representing the fraction of collisions with
correct orientation.
Form #2:

a. z and p are combined to make A, the frequency factor (frequency of

effective collisions)
By taking the natural log of both sides
Linear Equation:
 
 
1.9 Catalysis
Catalyst:
A substance that speeds up a reaction without being consumed itself by altering its mechanism to provide a lower
activation energy.

B. Effects of Catalysis
1. Catalysts lower activation energy but do not change DE for the reaction:
 

 
2. Catalysts provide alternate reaction pathways.
 
3. Catalysis results in a higher percentage of effective collisions:
 
 
 
 
 
 
 
  
Catalysts can be homogenous (in the same phase as the reactants) or heterogeneous (a
different phase than the reactants).
 
1- Heterogeneous Catalysis (usually gaseous reactants on a solid surface):

a. Uses:
Conversion of alkenes to alkanes.
Conversion of CO and NO in auto exhaust to CO2 and N2.
2- Homogeneous Catalysis:
 
Reactants and catalysts are in the same phase.
Example:
“The decomposition of ozone”
 
 
 
 
 
 
 
Questions
Thanks
• BY/

• Muhannad Rabie Mohamed Blela

2018025 20180
Amr Farid
2018012
Supervisor/
Mrs. Zainab Nasar