Kinetics: Studies the rate at which a chemical process occurs.

Besides information about the speed at which reactions occur, kinetics also sheds light on the
reaction mechanism (exactly how the reaction occurs).
Kinetics: how fast does a reaction proceed?
Thermodynamics: how does a reaction take place?
Reaction speed: measured by the change in concentration with time.
The speed of a reaction or the rate of a reaction can be defined as” the change in concentration of
a reactant or product in unit time”.
(i) the rate of decrease in concentration of any one of the reactants,
or
(ii) the rate of increase in concentration of any one of the products.
Consider a hypothetical reaction
R→P
One mole of the reactant R produces one mole of the product P.
If [R]1 and [P]1 are the concentrations of R and P respectively at time t 1and [R]2 and [P]2 are
their concentrations at time t 2 then,
•Rate of disappearance of R = Decrease in concentration of R = − Δ [R]
Time taken Δt
Rate of appearance of P = Increase in concentration of P = + Δ [P]
Time taken Δt
Where Δt = t2 – t1, ΔR= R2 – R1 & ΔP = P2 – P1
The square brackets in the above expressions are used to express molar concentration
Since, Δ[R] is a negative quantity (as concentration of reactants is decreasing), it is multiplied
with –1 to make the rate of the reaction a positive quantity.
Types of Rates:
Initial Rates: Rates measured at the beginning of the reaction, which is dependent on the initial
concentrations of reactants.
Instantaneous Rates: Rates measured at any point during the reaction. Value of the rate at a
particular time.
Can be obtained by computing the slope of a line tangent to the curve at that point.
Average Rates: An overall rate measured over a period or time interval.
Consider the following reaction at 300oC:
2NO2 (g) → 2NO (g) + O2 (g)
The initial concentration of NO2 is 0.0100 mol/L and its concentration after 150 s is 0.0055
mol/L. What are the average rates of this reaction during the first 150 s and during the second
150 s?
Time(s) [NO2] [NO] [O2]
(mol/L) (mol/L) (mol/L)
0 0.0100 0 0
50 0.0079 0.0021 0.0011
100 0.0065 0.0035 0.0018
150 0.0055 0.0045 0.0023
200 0.0048 0.0052 0.0026
250 0.0043 0.0057 0.0029
 300 0.0038 0.0062 0.0031
350 0.0034 0.0066 0.0033
400 0.0031 0.0069 0.0035

Average rate during the first 150 s:

Solution:
Average rate = -∆[NO2]/∆t = -(0.0055-0.0010) /150 = 3.0 x 10-5 mol/(L.s)
Average rate during the second 150 s:
Solution:
Average rate = -∆[NO2]/∆t = -(0.0038-0.0055)/150 = 1.1 x 10-5 mol/(L.s)
Average rate decreases as reaction progresses because the reactant concentration has decreased.
Rate of reaction between phenolphthalein with excess base.
Experimental Data for the Reaction between Phenolphthalein and Base.

[Phenolphthalein] Time
(M) (s)
0.0050 0.0
0.0045 10.5
0.0040 22.3
0.0035 35.7
0.0030 51.1
0.0025 69.3
0.0020 91.6
0.0015 120.4
0.0010 160.9
0.00050 230.3
0.00025 299.6
0.00015 350.7
0.00010 391.2
Rate Law:
The rate law expresses the reaction rate as a function of reactant concentrations, product concentrations,
and temperature. It is experimentally determined.
Or
“Rate of a chemical reaction is proportional to the molar concentration of reactants, each raised
to a power, the value of which is determined experimentally.
For a general reaction: aA + bB cC + dD

Rate law: rate = k[A]m[B]n

Where k = rate constant, the exponents m and n = reaction orders (not related to a, b coefficients
of the balanced chemical equation.
Rate = –d[R]/dt = k[A]m[B]n known as differential rate equation,
Where k is a proportionality constant called rate constant or velocity constant or specific
reaction rate. Thus, rate law is the expression in which reaction rate is given in terms of molar
concentration of reactants with each term raised to some power, which may or may not be same
as the stoichiometric coefficient of the reacting species in a balanced chemical equation.
Rate Constant (k): For a general reaction. When [A] = [B] = 1 mol/L, than Rate of reaction =
k, thus rate constant of a chemical reaction may be defined as the reaction rate when the
concentration of each reactant is unity The value of rate constant is definite and constant for a
particular reaction at given temperature. Rate constant is independent of concentration of
reactants it depends only upon temperature and presence of catalyst.
Order of Reactions
. "The sum of all the exponents in which the molar concentrations in the rate equation are raised"
The sum of powers of the concentration of the reactants in the rate law expression is called the
order of that chemical reaction.
For a general reaction
aA + bB → cC + dD
Let, Rate of reaction = k [A]x[B]y
Here, x = order of reaction w.r.t. A,
y = order of reaction w.r.t. B
And overall order of reaction = x + y NO2 (g) NO2 (g)
Properties of Reaction Orders:
1. Reaction orders cannot be deduced from the balanced chemical equation.
2. Reaction orders are usually positive integers or zero
3. Reaction orders can be fractional or negative.
Order of a Reaction& Units of Rate Constant
For a nth order reaction: A → Product
𝑅𝑎𝑡𝑒 = 𝑘[𝐴]𝑛
𝑅𝑎𝑡𝑒 1
k= ×
[𝐴]𝑛 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛
𝑘 = (𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛)1−𝑛 × 𝑡𝑖𝑚𝑒 −1
Reaction Order Units of Rate Constant
Zero order reaction 0 mol L-¹s-¹
First order reaction 1 s-¹
Second order reaction 2 mol-¹Ls-¹

Illustrative Problem: Determine x and y in the rate law Rate = k [F2]x[ClO2]y

F2 (g) + 2ClO2 (g) → 2FClO2 (g)
Rate Data for the Reaction between F₂ and CIO2
Initial Rate Data
[F₂] [CIO2] Initial Rate
0.10 M 0.010 M 1.2 × 10⁻³ M/s
0.10 M 0.040 M 4.8 × 10⁻³ M/s
0.20 M 0.010 M 2.4 × 10⁻³ M/s
Double [F2] with [ClO2] held constant: The rate doubles, Therefore, x = 1.
Quadruple [ClO2] with [F2] held constant: The rate quadruples, Therefore, y = 1.
The rate law is; Rate = k [F2]1[ClO2]1
Practice Problems:
Question 1. For the reaction
 A + B Products
The following initial rates were obtained at various given initial concentrations
–1 –1
S. No [A] [B] Rate (mol.L.t sec )
1. 0.1 0.1 0.05
2. 0.2 0.1 0.10
3. 0.1 0.2 0.05
Write rate law and find the rate constant of the above reaction.
Question 2.
1/2 2
For a reaction, A + B → Product; the rate law is given by, r = k [A] [B] .
What is the order of the reaction?
Question 3.
The conversion of molecules X to Y follows second order kinetics.
If concentration of X is increased to three times how will it affect the rate of formation of Y?
Question 4.
Rate of the reaction; A + B → Products; is given below as a function of the initial concentration
of ‘A’ and ‘B’.
[A](mol L-1) [B](mol L-1) Rate (mol L-1 min-1)
0.01 0.01 0.005
0.02 0.01 0.010
0.01 0.02 0.005
Determine the order of the reaction with respect to ‘A’ and ‘B’

Types of order of reactions:

1. Zero order reaction:
"A reaction that is independent of the concentration of reactant molecule" Rate = k[A]⁰
Examples:
(i) Decomposition of ammonia on heated tungsten.
2NH₃ → N₂ + 3H₂ Rate = k[NH₃]⁰
(ii) Combination of H₂ and Cl₂ in the presence of sunlight.
H₂ + Cl₂ → 2HCl Rate = k[H₂]⁰[Cl₂]⁰
(iii) The reactions catalyzed by enzymes.
2. First order reaction:
"A reaction whose rate of reaction is directly proportional to the first power of concentration of
single reactant molecule" Rate = k[A]¹
Examples:
(i) Thermal decomposition of N₂O₅
2N₂O₅ → 2NO₂ + O₂ Rate = k[N₂O₅]¹
(ii) Decomposition of ammonium nitrate in aqueous solution:
NH₄NO₃ → N₂ + 2H₂O Rate = k[NH4NO3]¹
3. Second order reactions:
“The reaction for which the sum of exponents of rate equation is two is called second order
reaction” Rate ∝ [A]² or Rate ∝ [A] [B]
Examples:
i) Decomposition of nitrogen dioxide
2NO₂→ 2NO + O₂ Rate = k[NO₂]²
ii) Reaction between ozone and Nitric oxide.
NO + O₃ → NO₂ + O₂ Rate = k[NO]1[O₃]
iii) Reaction between Ozone and Nitrogen dioxide:
2NO₂ + O₃ → NO₂ + O₂ Rate = k[NO₂]0[O₃]2

3.Third order reactions:

“A reaction in which the sum of exponents of rate equation is three is called "third order
reaction".
Rate α [A]3
Rate α [A]2[B]
Rate α [A][B][C]
Examples:
(i) Oxidation of NO by O2.
2NO + O2 → 2NO2 Rate = K[NO]2[O2]1
(ii)
FeCl2 + 6KI → 2FeI2 + 6KCl + I2
4. Fractional order reactions:
“A reaction for which sum of exponents of rate equations of rate equation is in fraction is called
"fractional order reaction."
Examples:
(i) Reaction between H2 and Br2.
H2 + Br2 → 2HBr Rate = k[Br2]1/2 [H2]¹
5. Pseudo-first order reaction:
“Reactions which are not truly of the first order but under certain conditions reactions become
that of first order are called pseudo unimolecular reaction”
For example:
(i) Hydrolysis of ester in the presence of acid;
CH3COOC2H5 + H2O CH3COOH + C2H5OH Rate = k [ester] [H2O]
Since, hydrolysis takes place in the excess of H2O and concentration change of H2O is negligible
practically, therefore, Rate = k’ [ester] Where k’ = k[H2O].
Integrated Rate Equations:
Zero Order Reactions:
Zero order reaction means that the rate of the reaction is proportional to zero power of the
concentration of reactants. Consider the reaction,
R→P
First Order Reactions:
First order reaction means that the rate of the reaction is proportional to the first power of the
concentration of reactants.
Consider the reaction, R → P

Illustrative Problem:
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?
Solution: [A]0 = 0.88 M, [A]t = 0.14 M, k = 2.8 x 10–2 s–1
ln[A]t = ln[A]0 – kt

kt = ln[A]0 – ln[A]

t = ln[A]0 – ln[A] / k = ln([A]0 /[A]) / k = In (0.88/0.14) / 2.8 x 10–2 = 66 s

Practice Problems:
1. The thermal decomposition of HCOOH is a first order reaction with a rate constant of 2.4 x
10-3 s -1 at a certain temperature. Calculate how long will it take for three-fourth (3/4) of initial
quantity of HCOOH to decompose?
(log 0.25 = − 0.6021)
2. A first order reaction has a rate constant of 0.0051 min ─1 . If we begin with 0.10 M conc. of
the reactant, how much conc. of the reactant will remain is solution after 3 hrs?
3. The rate constant for a reaction of Zero order in A is 0.0030 mol L ─1 s─1. How long will it take
for the initial conc. of A to fall from 0075 M to 10 M?
Half-Life of a Reaction
The half-life of a reaction is the time in which the concentration of a reactant is reduced to one
half of its initial concentration. It is represented as t 1/2.
t1/2 for a Zero Order Reactions:

Conclusion: The half-life for a zero order reaction is directly proportional to the initial
concentration of reactants. The half-life for a zero order reaction is inversely proportional to the
rate constant.
Half-life for first order reaction:
First Order Reaction:

Thus for a first order reaction, half-life period is constant,

i.e., it is independent of initial concentration of the reacting species
Illustrative Problem:
Half-Life of First-Order Reactions
The half-life, t1/2 is the time required for the concentration of a reactant to decrease to half of its
initial concentration.
Equation: t 1/2 = t when [A] = [A]0 /2
t 1/2 = ln [A]0 / [A]0 / 2 = ln 2 / k = 0.693 / k
What is the half-life of N2O5 if it decomposes with a rate constant of 5.7 x 10–4 s–1?
Half-life: t 1/2 = ln 2 / k = 0.693 / (5.7 x 10-4 s-1) = 1200 s = 20 minutes
How do you know decomposition is first order?
Solution: The rate constant, k, has units of s -1. This indicates a first-order reaction because the
rate is directly proportional to the concentration of the reactant.
Practice Problems:
1. A first order reaction takes 40 minutes for 30 % completion. Calculate its t 1/2 value.
2. The decomposition of phosphine PH3 proceeds according to following equation:
4 PH3 (g)---> P4 (g) + 6H2 (g)
It is found that he reaction follows the following rate equation:
0
Rate = k [PH3] ; The half-life of PH3 is 37.9 sec at 1200 C.
th
(a) How much time is required of ¾ of PH3 to decompose?
(b) What fraction of original sample of PH3 remains behind after 1 minute?

Factors Affecting Rate of Reactions

1) Nature of reactants
The reactivity of elements depends upon their electronic configuration. For example, Alkali
metals have one electron in their outermost s-orbital and are more electropositive. While
Alkaline earth metals have two electrons in their outermost s-orbitals and are less electropositive.
Reactants having ionic bonds are more reactive than those having covalent bonds b/c ionic
reactions involve combination of opposite ions while covalent molecule involve electronic
redistributions,
2) Concentration of reactants:
According to Law of mass action, "The rate of a chemical reaction is proportional to the product
of molar concentration of the reactants". Higher is the concentration of reactants greater is the
rate of reaction. A mixture of H2 and Cl2 will react twice as fast if the partial pressure is doubled
in the presence of excess of other components.
Combustion occur more rapidly in pure oxygen than in air (21% oxygen).
3) Surface Area:
Increasing surface area increases the possibilities of contact between their particles. Therefore,
the rate of a reaction increases. For example,
(i) A finely divided zinc powder reacts more rapidly with dilute HCl than a large piece of zinc.
Zn (s) + 2HCl (aq) → ZnCl2 (aq) + H2 (g)
(ii) Aluminum foil reacts with NaOH moderately on warming, but powdered aluminum reacts
rapidly with cold NaOH.
2Al (s) + 2NaOH (aq) + 6H2O (l) → 2Na[Al(OH)4] (aq) + 3H2 (g)
4) Temperature:
Increase in temperature increases the average kinetic energy of the molecules, which in turn
increases the collision frequency. At ordinary temperature, only very few molecules possess
activation energy. The number of molecules having at least kinetic energy equal to Ea at
temperature T is proportional to the shaded area under the Maxwell Boltzmann curve of
kinetic energy. At any temperature there is a wide distribution of kinetic energies. As the
temperature increases, the curve flattens and broadens. Thus at higher temperatures, a larger
population of molecules has higher energy. 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. This fraction of molecules can be found
through the expression: f = e-Ea/RT
For a chemical reaction with rise in temperature by 10 K, the rate constant is nearly doubled. The
ratio is called the temperature coefficient and its value is 2 or 3.
Maxwell–Boltzmann Distributions:

Increased T increased average speed of particles increased collision

frequency increased reaction rate
Effect of Ea and T on the fraction (f) of collisions with sufficient energy to allow reaction:
Ea (kJ/mol) f (at 298 K)
50 1.70 x 10-9
75 7.03 x 10-14
100 2.90 x 10-18

T f (Ea = 50 kJ/mol)
o
25 C (298 K) 1.70 x 10-9
o
35 C (308 K) 3.29 x 10-9
45 oC (312 K) 6.12 x 10-9
As T = 10 o ; f ~ doubles; reaction rate ~ doubles!

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

Arrhenius equation:
The temperature dependence of the rate of a chemical reaction can be accurately explained by
Arrhenius equation 𝑘 = 𝐴𝑒 −𝐸𝑎/𝑅𝑇
𝐸𝑎
A is frequency factor or Arrhenius constant, Ea is activation energy In 𝑘 = − 𝑅𝑇 + InA
 1 𝐸𝑎
Plot of log k vs 𝑇 is a straight line & slope = − 2.303𝑅
𝐸𝑎
At temperature T1 𝐼𝑛𝑘 = − + InA Eq.1
𝑅𝑇1
𝐸𝑎
At temperature T2 𝐼𝑛𝑘 = − + InA Eq.2
𝑅𝑇2
Where k1 and k2 are the values of rate constants at temperatures T 1 and T2 respectively.
Subtracting equation (2) from (1), we obtain
𝐸𝑎 𝐸𝑎
𝐼𝑛𝑘2 − 𝐼𝑛𝑘1 = − InA
𝑅𝑇2 𝑅𝑇1
𝑘2 𝐸𝑎 1 1
𝐼𝑛 = [ + ]
𝑘1 𝑅 𝑇2 𝑇1
𝑘2 𝐸𝑎 1 1
𝑙𝑜𝑔 = [ + ]
𝑘1 2.303𝑅 𝑇2 𝑇1
𝑘2 𝐸𝑎 𝑇2−𝑇1
𝑙𝑜𝑔 = [ ]
𝑘1 2.303𝑅 𝑇1𝑇2

Illustrative Problem:
The activation energy of one of the reactions in the Krebs citric acid cycle is 87 kJ/mol. What is
the change in the rate constant when the temperature falls from 37 oC to 15oC?
Solution: Answer 𝑘′ = 0.76 𝑘
Illustrative Example:
The specific reaction rate for a reaction increases by a factor 4 if the temperature is changed from
27oC to 47oC. Find the activation energy for the reaction.
𝑘2 Ea 𝑇2−𝑇1
𝑙𝑜𝑔 = [ ]
𝑘1 2.303𝑅 𝑇1𝑇2
𝐸𝑎 320−300
𝑙𝑜𝑔 4 = [ ]
2.303×1.987 300×320
 0.60205×2.303×1.987×300×320
Ea =
20
Ea = 13222.98 cals or Ea = 13.311 K cals.
…………………………………………………………………………………………………..
Activation Energy:
There is a minimum amount of energy required for a reaction: the activation energy, Ea.
Just as a ball cannot get over a hill if it does not roll up the hill with enough energy, a reaction
cannot occur unless the molecules possess sufficient energy to get over the activation energy
barrier. Molecules must possess a minimum amount of energy to react.
Why? In order to form products, bonds must be broken in the reactants. Bond breakage requires
energy. Molecules moving too slowly, with too little kinetic energy, don’t react when they
collide. Activation energy, Ea, is the minimum energy required to initiate a chemical reaction.
Ea will vary with the reaction. But, most collisions fail to yield products.
Significance of activation energy and effective collision: Only those collisions with energy
equal to, or greater than, Ea and with proper orientations of molecules can yield products.
Increasing T enhances the fraction of productive collisions, f. 𝑓 = 𝑒 −𝐸𝑎/𝑅𝑇
From this equation, we can see that both Ea and T affect f, which in turn influences reaction rate.

The activation energy (Ea) is the minimum amount of energy required to initiate a
chemical reaction.
Energy Diagrams

(a) Activation energy (Ea) for the forward reaction 50 kJ/mol and 300 kJ/mol
(b) Activation energy (Ea) for the reverse reaction1 50 kJ/mol and 100 kJ/mol
 (c) Delta H -100 kJ/mol and 200 kJ/mol

Transition State Theory:

Addresses the limitations of collision theory in explaining chemical reactivity. During the
transformation of reactant into product, one or more very short-lived chemical species form that
resemble (but are different from) reactant or product; these transitional species contain partial
bonds; they are called transition states (TS) or activated complexes. The activation energy is used
to stretch/deform specific bonds in the reactant(s) in order to reach the transition state.

E = 19 kJ
a Ea(rev)= (392 + 19) kJ = 411 kJ
Potential Energy

O3+O transition state

breaking
O
H
rxn = -392 kJ
bond
O O
forming O
bond

2O2
Reac tion progress

Endothermic Exothermic Exothermic

5. Catalyst
A substance which accelerates a chemical reaction but chemically remain unchanged at the
reaction end is called a Catalyst.
It increases the rate of reaction by decreasing activation energy & provides a new mechanism for
the reaction with low activation energy. The lower activation energy allows the reaction to
proceed faster.
Energy Plots for a Catalyzed and an Unanalyzed Pathway for a Given Reaction

Effect of a Catalyst on the Number of Reaction-Producing Collisions.

Illustrative example:
Destruction of Ozone without catalyst has high activation energy
O3 + O → 2O2 Ea = 17.1kJ/mol
In the presence of catalyst activation energy become lower.
O3 + Cl → O2 + ClO Ea = 2.1kJ/mol
O + ClO → O2 + Cl Ea = 0.4kJ/mol
O3 + O → 2O2 Ea = 2.5kJ/mol
…………………………………………………………………………………………………….
Reaction Mechanism and rate determining step:
"The path followed by the reactants in forming the products in a chemical reaction is called the
mechanism?" The sequence of events that describes the actual process by which reactants
become products is called the reaction mechanism. Reactions may occur all at once or through
several discrete steps. Each of these processes is known as an elementary reaction or elementary
process. The rate equation provides information about the reaction mechanism. A reaction may
occur in single or more steps in which one step on the rate is known as the rate determining step.
Rate determining step (slowest elementary step / rate limiting step):
The rate determining step is the slowest elementary step in a mechanism, and the rate law for this
step is the rate law for the overall reaction.
Steady-state approximation:
The steady-state approximation is a general method for deriving rate laws when the relative
speed cannot be identified. It is based on the assumption that the concentration of the
intermediate is constant.
1. Illustrative Problem:
The hypothetical reaction, A2 + B2 → 2AB; follows the following mechanism:
A2 → A + A (fast)
A + B2 → AB + B (slow)
A + B → AB (fast)
The order of the overall reaction is (a) 3/2 (b) 2 (c) 0 (d) 1
The order depends on slowest step
Rate (slow step) = k[A][B2]
= k[B2].k`[A2]1/2
= k"[A2]1/2 [B2]
Overall order Hence, the answer is (a).
2. Illustrative Problem:
(i) NO2 + CO2 → NO + CO2
Rate = k[NO2]2
Step1. NO + NO2 → NO + NO (slow)
Step2. NO2 + CO → NO + CO2(fast)
(ii) 3ClO- → ClO3- + 2Cl-
Step 1 ClO- + ClO- → ClO2- + Cl- (slow)
Step 2 ClO2- + ClO- → ClO3- + Cl- (fast)
(iii) 2NO + 2H2 → N2 + 2H2O
Step 1 2NO + H2 → N2 + H2O2 (slow)
Step 2 H2O2 + H2 → 2H2O (fast)
(iv) 2NO + F2 → 2NOF
Rate = k[NO][F2]
Step 1 NO + F2 → NO2F + F- (slow)
Step 2 NO2F + F- → NO2F (fast)
Molecularity of a reaction: It is defined as the number of molecules that take part in the rate
determining step of a reaction,
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. 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.

Fast Initial Step

2NO (g) + Br2 (g) 2NOBr(g)
2
Rate = k [NO] [Br2]
The rate law for this reaction is found (experimentally) to be
Because termolecular (= trimolecular) processes are rare, this rate law suggests a two-step
mechanism.
Step 1 NO + Br2 NOBr2 (fast)
Step 2 NOBr2 + NO → 2NOBr (slow)
Step 1 is an equilibrium- it includes the forward and reverse reactions.

Molecularity Elementry reaction Rate law

unimolecular A → Product Rate = k [A]
Bimolecular A+ A → Products Rate = k [A]2
Bimolecular A + B → Products Rate = k [A][B]
 Termolecular A + A + A → Products Rate = k [A]3
Termolecular A + A + B → Products Rate = k [A]2[B]
Termolecular A + B + C → Products Rate = k [A][B][C]

Types of Catalysis.
1) Homogeneous Catalysis:
"A Catalysis in which Catalyst & reactants are in same phase"
Examples:

i) 2SO2 (g) + O2 (g) NO2 (g) 2SO3 (g)

H+ (l)
ii) CH3COOCH3 (l) + H2O (l) CH3COOH (l) + CH3OH (l)

iii) C12H22O11 (aq) + H2O (l) Sucrase (l) C6H12O6 (aq) + C6H12O6 (aq)
NO2 (g)
iv) O3 (g) 2 O2 (g)

2) Heterogeneous Catalysis:

"A Catalysis in which Catalyst and reactants are in different phases"

Examples:
Fe2O3(s)
i) N2 (g) + 3H2 (g) 2NH3 (g)
V2O5 (s)
ii) 2SO2 (g) + O2 (g) 2 SO3 (g)
Al2O3(s)
iii) HCOOH (l) H2O (l) + CO2 (g)
Ni (s)
iv) Vegetable Oil (l) + H2 (g) Margarine (s)

Examples of Catalysts:
Enzymes:
Enzymes are catalysts in biological systems. The substrate fits into the active site of the enzyme
much like a key fits into a lock. Enzymes are biological catalysts. There may be as many as
30,000 enzymes in the human body. (e.g., Lactase)
Most enzymes are protein molecules with large molecular masses (10,000 to 106 amu).
Enzymes have very specific shapes and catalyze very specific reactions.
The substances that undergo reaction at the active site on enzymes are called substrates.
A substrate locks into an enzyme and a fast reaction occurs. The products then move away from
the enzyme. Only substrates that fit into the enzyme lock can be involved in the reaction.
Enzymes are extremely efficient catalysts. The number of individual catalytic events occurring
at an active site per unit time is called the turnover number. Large turnover numbers correspond
to very low Ea values. For enzymes, turnover numbers are very large ≈ 103 to 107/sec.
 Enzyme inhibitors.
If a molecule binds tightly to an enzyme so that another substrate cannot displace it, then the
active site is blocked and the catalyst is inhibited (enzyme inhibitors).
Many poisons act by binding to the active site blocking the binding of substrates. The binding
can also lead to changes in the enzyme.

Lock and key model: In 1894, German Induced-fit model: In 1958, Daniel
chemist Emil Fischer proposed the lock and Koshland proposed the induced-fit model,
key model, which states that enzymes and which extends Fischer's ideas. This model
substrates have complementary shapes that fit states that enzymes change shape slightly to
together like a lock and key. This model accommodate the binding of the substrate.
explains enzyme specificity, but doesn't
explain how enzymes stabilize the transition
state