ChemistryChemical
and Environmental
kinetics) Studies
Module 2(Chemical kinetics)
Chemical kinetics
Reaction Rate
1) for simple case
2) For reactions with stoichiometric coefficients not equal to
1, the rate of change of each species is divided by its
stoichiometric coefficient as;
Chemical kinetics
Reaction Rate
Average Rate Vs Instantaneous rate
Avarage rate and Instantaneous rate
Average Rate: Rate of change over an average period of time
Between the starting time 0.0 s and 10.0 s, the
average rate is
During the last 10.0 s, between 50.0 s and 60.0 s, the
average rate is
Overall scenario of concertation
Instantaneous Rate: change in ethene oxidation
The rate of change at a particular moment.
Chemical kinetics
Rate Law
There is a proportionality between the reaction rate and
the concentration of reactants.
This proportionality is called a rate law or rate equation.
The proportionality coefficient is called the rate constant (k).
m and n are typically either integers or half integers.
The actual values of the exponents m and n must be measured
experimentally. (In some cases, these values can be related to the
stoichiometric coefficients of the reaction, but
not always!)
usually a ≠ m and b ≠ n some cases a = m and b = n
Chemical kinetics
Reaction order
The reaction order with respect to one particular reactant
is equal to the value of the exponent of that reactant’s
concentration
The overall reaction order is defined as the value of the sum
of all exponents in the rate law
the order of the reaction for above reaction is m+n, while
the reaction is mth order in reactant A and nth order
in reactant B.
Chemical kinetics
Reaction order
• This reaction is first order with respect to NO (or first
order in NO)
• It is also first order with respect to O 3,
• This reaction is second order overall (1+1 =2)
Chemical kinetics
Reaction order
The reaction is second order in NO and first order in
H2, so it is third order overall.
Chemical kinetics
Reaction order
Reaction orders are usually positive integers or zero, but
they can also be fractional or negative. For the reaction
if the initial Cl2 concentration is increased by a factor of 4, while the
initial CHCl3 concentration is kept the same, the rate increases by
a factor of 2, the square root of the change in [Cl2].
Chemical kinetics
Integrated rate laws
Zero-order Reactions
A Products
‘a’ is initial concentration of the reactant,
‘x’ is the concentration that is consumed in time ‘t’
𝑑𝑥
= 𝑘(𝑎 − 𝑥)0 = 𝑘
𝑑𝑡
On integration, it gives
𝑥
𝑘=
𝑡
Chemical kinetics
Integrated rate laws
First-order Reactions
A Products
‘a’ is initial concentration of the reactant,
‘x’ is the concentration that is consumed in time ‘t’
𝑑𝑥
=𝑘(𝑎 − 𝑥)
𝑑𝑡
On integration, it gives
𝑎
ln = 𝑘𝑡
𝑎−𝑥
1 𝑎
𝑘 = ln
𝑡 𝑎−𝑥
Chemical kinetics
Integrated rate laws
First-order Reactions
A Products
1 𝑎
𝑘 = ln
𝑡 𝑎−𝑥
Half-life period: It is the time taken for the completion
of half of the reaction. x = a/2 at t = t1/2
0.693
𝑡1/2 =
𝑘
the half-life period for a first-order reaction is constant and
independent of initial concentration of the reacting species
Chemical kinetics
Integrated rate laws
Second-order Reactions
A Products
‘a’ is initial concentration of the reactant,
‘x’ is the concentration that is consumed in time ‘t’
𝑑𝑥
=𝑘 𝑎 − 𝑥 2
𝑑𝑡
On integration, it gives
1 1
= 𝑘𝑡 +
𝑎−𝑥 𝑎
1 𝑥
𝑘=
𝑡 𝑎(𝑎−𝑥)
Zero-order Reaction First-order Reaction
a ln a
Conc. ln(Conc.)
Second-order Reaction
1/a
A Products
‘𝐴𝑜 ’ is initial concentration of the reactant,
‘𝐴𝑡 ’ is the concentration that is remaining after time t
Unit M= mol/L
Activation energy (Ea)
• To get from reactants to products, the reaction must
first overcome an energy threshold, called the activation
energy or activation barrier.
• Collisions of fast moving particles provide sufficient
kinetic energy to overcome the activation barrier.
• The larger this barrier, the more kinetic energy will be
needed.
The effect of temperature on reaction rate
• Swedish chemist Svante Arrhenius, who discovered a key
relationship between T and k. In its modern form, the
Arrhenius equation is
k is the rate constant,
e is the base of natural logarithms,
T is the absolute temperature,
R is the universal gas constant.
A is constant called frequency factor
Ea is the activation energy of the reaction
(Ea is the minimum energy the molecules must
have to react)
The effect of temperature on reaction rate
A plot of ln k vs. 1/T gives a straight line whose slope is Ea/R and
whose y intercept is ln A .
Therefore, with the constant R known, we can determine Ea
graphically from a series of k values at different temperatures.
The effect of temperature on reaction rate
• The kinetic-molecular
theory says that molecules
interact with one another
only through collisions.
• So, for two molecules to
react, first they must
collide. (Collision theory)
• Slow moving molecules collide with gentle impacts that do
not usually result in reaction, whereas fast moving
molecules seem more likely to react
The effect of temperature on reaction rate
• Since the relationship between ln k and 1/T is linear, we
can use a simpler method to find Ea if we know the rate
constants at two temperatures, T2 and T1
The effect of temperature on reaction rate-
Activation energy
Frequency factor (A)
frequency factor, A = pZ.
Z collision frequency
p an orientation probability factor, which
is specific for each reaction:
The factor p is related to the structural complexity of the
colliding particles.
You can think of it as the ratio of effectively oriented
collisions to all possible collisions
The effect of Concentration on reaction rate
If particles must collide to react, the
laws of probability tell us why the rate
depends on the product of the reactant
concentrations, not their sum.
If you add another particle of A,
there can be six A-B collisions
(3 ×2), not just five (3 +2);
Chemical kinetics
Factors that influence reaction rate:
1. Concentrartion:
reaction rate is proportional to the concentration of
reactants:
Rate ∝ collision frequency ∝ concentration
2. Temperature:
raising the temperature increases the reaction rate by
increasing the number and, especially, the energy of the
collisions
Rate ∝ collision energy ∝ temperature
Molecularity
• A chemical reaction that takes place in one and only one step
i.e., all that occurs in a single step is called elementary
reaction.
PCl5 → PCl3 + Cl2
• While a chemical reaction occurring in the sequence of two
or more steps is called complicated reaction.
• The sequence of steps through which a complicated reaction
takes place is called reaction – mechanism. Each step in a
mechanism is an elementary step reaction.
Mechanism elementary step
elementary step
Molecularity-elementary reaction
• Each elementary reaction step is classified by its molecularity,
which is the number of molecules, atoms, or ions that come
together to react in that particular step.
• The molecularity is equal to the sum of the stoichiometric
coefficients of all the reactants in the elementary reaction
step.
• An elementary reaction can be classified as unimolecular,
bimolecular, or termolecular depending on how many molecules,
atoms, or ions are involved.
Molecularity-complicated reaction
• The molecularity is equal to the sum of the stoichiometric
coefficients of all the reactants in the elementary reaction
step.
Mechanism elementary step
elementary step
• The molecularity of this reaction is undefined, because it
involves a mechanism of more than one step.
However, we can consider the molecularity of the individual
elementary reactions that make up this mechanism:
• the first step is termolecular because it involves three
reactant molecules,
• the second step is bimolecular because it involves two
reactant molecules.
complicated reaction-rate determining step
This slow step in the reaction mechanism is called the rate
limiting step or rate determining step.
The rate law for the overall reaction is determined by the
stoichiometry of the rate determining step.
Reaction
Mechanism
If the first elementary step is slow and the second
elementary step is fast, the overall rate equation would be;
rate = k1[NO2][F2], So, step 1 is the rate determining step
Problem 1
Problem solving continuation in next side
Problem 1
Problem 2
Problem 3
problem solving in the next slide
Problem 3
Problem 4
Problem 5
Problem 5
Problem 6
Problem 6
Problem 6
Rate (Experiment 2) 6.8 x 10-8 M h-1 k[CO]m[NO2]n
= =
Rate (Experiment 1) 3.4 x 10-8 M h-1 k[CO]m[NO2]n
k[CO]m[NO2]n
2 =
k[CO]m[NO2]n
k[5.1x10-4]m[0.7 x10-4]n
2 =
k[5.1x10-4]m[0.35x10-4]n
2 = [2]n
log 2 = n log 2
The reaction is first order
n=1 with respect to NO2
Problem 6
Rate (Experiment 3) 6.8 x 10-8 M h-1 k[CO]m[NO2]n
= =
Rate (Experiment 1) 3.4 x 10-8 M h-1 k[CO]m[NO2]n
k[CO]m[NO2]n
2 =
k[CO]m[NO2]n
k[1.02x10-3]m[0.35 x10-4]n
2 =
k[5.1x10-4]m[0.35x10-4]n
2 = [2]m
log 2 = m log 2
The reaction is first order
m=1 with respect to CO
Problem 7
Which graph belongs to first order reaction?
Problem 7
Solution 4
Problem 8
What is the order of the reaction
A Products
Time (Sec) [A] mol/L
0 5
20 4.44
40 3.92
60 3.46
80 3.06
What is the order of the reaction
A Products
Solution
Time (Sec) [A] mol/L ln[A] 1/[A]
0 5 1.609 0.200
20 4.44 1.491 0.225
40 3.92 1.366 0.255
60 3.46 1.241 0.289
80 3.06 1.118 0.327
Calculate ln[A] and 1/[A]
What is the order of the reaction
A Products
Solution
Take the difference between successive values in columns [A], ln [A] and 1/[A]
Time [A] mol/L ln[A] 1/[A]
(Sec)
0 5.03 1.615 0.200
20 4.44 0.59 1.491 0.124 0.225 0.025
40 3.92 0.52 1.366 0.125 0.255 0.03
60 3.46 0.46 1.241 0.125 0.289 0.034
80 3.06 0.40 1.118 0.123 0.327 0.038
these values are constant in the column ln [A], so the reaction is first order.
If values are constant in the column [A], then the reaction is zero order.
If values are constant in the column 1/[A], then the reaction is secondorder.