Chemical kinetics

Chemical Kinetics
The branch of chemistry that deals with the measurement of rates
of reactions under given conditions of temperature, pressure and
concentration.
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Reaction Rates How we measure rates.

How the rate depends on amounts of

Rate Laws reactants.
How to calculate 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 scale

Mechanisms processes.
 Chemical Kinetics

aA + bB cC + dD
a, b, c, d Stoichiometry Coefficient
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-ve +ve
Reactant Product
 Chemical Kinetics
Rate = Change in concentration of reactant/Time
Reactants  Products taken
R P = -(∆ CR)/ (∆ t)
t = 0 5M 0
Rate = Change in concentration of product/Time
t = 10s Vision
3.5M 1.5M
taken
t = 20s 3.0M 2.0M
t = 30s 1.5M 3.5M = (∆ CP)/ (∆ t)

Rate = Change in concentration/Time taken

= (C f)r – (C i)r / T f – T I
= 1.5 – 5/ 30 – 0
= -3.5/3.0
= - 0.117
 Chemical Kinetics

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 Differential Rate Law

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 Differential Rate Law

aA + bB  cC + dD
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Rate = -d[A]/dt = -d[B]/dt = d[C]/dt = d[D]/dt

Rate = - d[A]/dt = - d[B]/dt = d[C]/dt = d[D]/dt

Write the differential rate law for;

 Chemical Kinetics
Reaction rates depend on the composition and the
temperature of the reaction mixture.

The instantaneous rate of a reaction is the slope of the

tangent to the graph of concentration against time
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(expressed as a positive quantity).

A rate law is an expression for the reaction rate in terms

of the concentrations of the species that occur in the
overall chemical reaction.
Consider a reaction of the form A + 2 B → 3 C + D
the volume of the system is constant.
The instantaneous rate of consumption of one of the
reactants at a given time is d[R]/dt, where R is A or B.
It follows from the stoichiometry for the reaction A + 2
B → 3C + D that
 Rate of a chemical reaction
The speed of a reaction or rate of the reaction can be defined as the change in
concentration of a reactant or product in unit time.

It can be expressed as;

1)The rateVision
of decrease in concentration of any one of the reactants.
2)The rate of increase in concentration of any one of the products.

The rate of reaction is often found to be proportional to the concentrations of the reactants
raised to a power.
For example, the rate of a reaction may be proportional to the molar concentrations of two
reactants A and B, so we write;
Rate = k[A][B]
With each concentration raised to first power. The coefficient k is called the rate constant for
the reaction.The rate constant is independent of the concentrations but depends on the
temperature.
If the concentrations are expressed in mol dm−3, then the units of k will be dm3 mol−1 s−1
 What is Collision Theory?
How chemical reactions occurs.
Why reaction rates differ for different reactions.

Collision theory was proposed independently by Max Trautz in 1916 and William Lewis in
1918.
• Collisions:The collision theory states that a chemical reaction can only occur
between particles when they collide each other. The collision between reactant
particles is necessary but not sufficient for a reaction to take place.
• Orientation:The collisions also have to be effective. It is important to
understand the exact nature of an effective collision since this determines whether
particles react with each other and form new products.
• Activation Energy:The successful collisions have enough energy, also known as
activation energy, at the moment of impact to break the pre-existing bonds and
form all new bonds.
 Molecular Collisions
• Increasing the concentration of the reactant brings about more collisions and
hence more successful collisions.
• Molecules must collide before they can react.
• To effectively initiate a reaction, collisions must be sufficiently energetic
(kinetic energy) to bring about this bond disruption.
• Increasing the temperature increases the average kinetic energy of the molecules
in a solution, increasing the number of collisions that have enough energy.
• Most reactions involving neutral molecules cannot take place at all until
they have acquired the activation energy needed to stretch, bend, or otherwise
distort one or more bonds.
• Catalyst provide alternative pathway that require less activation energy.
 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑣𝑒 𝑐𝑜𝑙𝑙𝑖𝑠𝑖𝑜𝑛𝑠
𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑅𝑎𝑡𝑒∝
𝑡𝑖𝑚𝑒

Two collisions between carbon

monoxide and oxygen molecules.

The orientation of the colliding

molecules partially determines
whether a reaction between the
two molecules will occur.
When reactant species collides with both proper orientation and adequate energy, they
combine to form an unstable species called an activated complex or a transition state.
These species are very short lived and usually undetectable by most analytical
instruments.

Arrhenius equation;
Rate constant

Ea = Activation energy
A = frequency factor

The frequency factor A is related to the rate at

which collisions occur with correct orientation.

The exponential term, e−Ea/RT is related to the fraction of collisions providing

adequate energy to overcome the activation barrier of the reaction.
 Reaction Order
The rate law of a reaction is determined experimentally and cannot in general be inferred from the
stoichiometry of the balanced chemical equation for the reaction.

Many reactions are found to have rate laws of the form:

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Rate = k[A]a [B]b
The power to which the concentration of a species (a product or a reactant) is raised in a rate law of this kind
is the order of the reaction with respect to that species.

The overall order of a reaction with a rate law like that in the above equation is the sum of the individual
orders, a + b + · · ·
A reaction need not have an integral order, and many gas-phase reactions do not.
For example, a reaction having the rate law.

Rate = k[A]1/2 [B], order is then 3/2.

Some reactions obey a zero-order rate law, and therefore have a rate that is independent of the concentration
of the reactant.
 Factors That Affects Reaction Rates
• Nature of reactants : Ionic substance reacts much faster than covalent
substances.

• Concentration of Reactants : Rate of reaction is directly proportional to conc. of

reactants (partial pressure in case of gaseous - phase reactions).

• Temperature: Rate of reaction increases with increase in temperature.

• Presence of Catalyst: A catalyst alters the rate of a reaction.

• Surface Area of the Reactants: Rate of reaction ∝ surface area.

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 Molecularity of a Reaction
Molecularity of a reaction is simply the number of reacting species (atoms,
ions or molecules) involving is an elementary reaction which must collide
simultaneously.
Let us consider the following reactions;
Coordination Liquid
complexes crystalline
polymer

Conducting Polymer
polymers composites

Porous
Catalysis polymer

Natural Computational
products chemistry
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 Order of a Reaction
Order of a reaction is the sum of the exponents (power) to which the
concentration terms are raised in the rate law.

Let us consider a reaction;

lA + mB Products
Its rate equation is,
Rate = K[A]a [B]b

Order with respect to reactant A is ‘a’ and order with respect to reactant B is ‘b’
and overall order of the reaction is ‘a+b’
Where ‘a’ and ‘b’ may or may not be equal to ‘l’ and ‘m’ respectively.
The order of a reaction may be fractional, whole number or zero.
 First Order Reaction
These are the reactions in which the rate of reaction is determined by the
variation of one concentration term only.

Examples;
Decomposition of N2O5,
N2O5 (g) N2O4 (g) + ½ O2 (g)

Rate = K[N2O5]

Decomposition of H2O2,
H2O2 (l) H2O (l) + ½ O2 (g)

Rate = K[H2O2]
 Pseudo First Order Reaction
These are the reactions in which more than one reactant molecules are involved
but these are of first order.

Examples;
C11H22O11 + H2O (excess) C6H12O6 (glucose)+ C6H12O6 (fructose)
Rate = K[C11H22O11]

CH3COOC2H5 + H2O (excess) CH3COOH + C2H5OH

Rate = K[CH3COOC2H5]

In the above examples water is in large excess and does not undergo any
appreciable change in concentration.
 First Order Reaction (Differential and Integrated form)
Let us consider a general first order reaction,
A Product
t = 0 sec a 0
t = t sec a–x x
Let, the initial concentration of A be ‘a’ molL-1
After time ‘t’, ‘x’ moles of A decompose to give products
Then,
Concentration of A after time ‘t’ is (a-x)
Thus,the rate of formation of product,

where, K1 = Rate constant for first order reaction

Or
Integrating both sides, we get,
 First Order Reaction (Differential and Integrated form)
Integrating both sides, we get,

=> -ln (a-x) = K1t + I (1)

Where, I = constant of integration

When t=0, x=0, then
-ln a = I
Substituting the value of I in equation 1, we have,
-ln (a-x) = K1t – ln a
=> K1t = -ln (a-x) + ln a
=> K1t = ln
=> K1= ln
=> K1= (2)

Equation 2 is the integrated rate expression for first order reaction

 First Order Reaction (Differential and Integrated form)

Equation 2 is sometimes written in another forms which is obtained as follows;

If the initial concentration is [A]o and concentration time after time ‘t’ is [A]1, then

K1=
=> K1 t =
=>
 Characteristics of First Order Reaction
(1) If molar concentration of reactant are plotted against the time, an exponential curve is
obtained.
(2) If log[A] or log(a-x) is plotted against time, a straight line with a slope – is obtained.
(3) If log () is plotted against time, a straight line passing through the origin is obtained.