Chemical Kinetics

 Chemical kinetics, also known as reaction kinetics, is the

branch of physical chemistry that is concerned with
understanding of the rates of chemical reactions.

 It is to be contrasted with thermodynamics, which deals with the

direction in which a process occurs but in itself tells nothing
about its rate.

 Besides information about the speed at which reactions

occur, kinetics also sheds light on the reaction mechanism
(exactly how the reaction occurs).
 Reaction Rates
Rates of reactions can be determined by monitoring the change
in concentration of either reactants or products with a change
in time.
A B 𝜟𝑨 𝜟𝑩
- =+ = rate
𝜟𝒕 𝜟𝒕

rate is always
expressed as a
positive value
Reaction rate is measured in terms of the changes in concentrations
of reactants or products per unit time.

For the general reaction A → B, we measure the concentration of A

at t1 and at t2:
change in concentration of A conc A2 - conc A1 [A]
Rate = =- = -
change in time t2 - t1  t

Square brackets indicate a concentration in moles per liter and

time in second . So the unit of rate of reaction is mole/lit-sec

The negative sign is used because the concentration of A is

decreasing. This gives the rate a positive value.
 Concentration of O3
Time (s) (mol/L)

0.0 3.20x10-5
10.0 2.42x10-5
 [C2H4]
20.0 1.95x10-5 rate = -
t
30.0 1.63x10-5  [O3]
=-
40.0 1.40x10-5 t
50.0 1.23x10-5
60.0 1.10x10-5
C2H4 + O3 → C2H4O + O2
[O2] increases just as fast as [C2H4]
decreases.

D[C2H4] D[O3]
Rate = - =-
Dt Dt

[C2H4O] [O2]
= =
t t
The average rate of the reaction is the change in concentration
of the reactant or product in a unit interval of time (the
specified interval Δt, being finite and measurable)

C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

• Note that the average rate decreases as the reaction proceeds.
• This is because as the reaction goes forward, there are fewer
collisions between reactant molecules.
 A plot of concentration vs. time for this reaction yields a curve like
this.

• The rate of a reaction at a

particular instant in time is
called instantaneous rate.

• The slope of the tangent to the

curve at any point is the
instantaneous rate at that
instant in time.

𝜟𝑨 𝒅𝑨
- = - = Instantantaneous rate
𝜟𝒕 𝒅𝒕
∆𝑡 → 0
The reaction slows down with time because the concentration of the
reactants decreases.
𝜟[𝑨] 𝒅[𝑨]
- = = Instantantaneous rate = slope
𝜟𝒕 𝒅𝒕

∆𝒕 → 𝟎

Instantantaneous rate =
(Average rate) ∆𝑡 → 0
 Reaction Rates and Stoichiometry
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

• In this reaction, the ratio of C4H9Cl to C4H9OH is 1:1.

• Thus, the rate of disappearance of C4H9Cl is the same as the

rate of appearance of C4H9OH.

-[C4H9Cl] [C4H9OH]
Rate = =
t t
 What if the ratio is not 1:1?
H2(g) + I2(g) 2HI(g)

 The concentrations of reactants ad product change at different

rates. What is the rate of reaction then ? Is it the rate at which
concentration of HI changes or H2 changes ?

 The mathematical expression for the rate, and the numerical value
of the rate, depend on which substance is chosen as the reference.

 2 molecule of HI is formed for each mole of H2 used.

 • To generalize, for the reaction

aA + bB cC + dD
𝒅[𝑨] 𝒅𝑩 𝒅[𝑪] 𝒅[𝑫]
Rate = - = - = + =+
𝒂𝒙𝒅𝒕 𝒃𝒙𝒅𝒕 𝒄𝒙𝒅𝒕 𝒅𝒙𝒅𝒕

Reactants (decrease) Products (increase)

Rate of reaction is the time derivative of a concentration

divided by the appropriate stoichiometric coefficient and
converted to a positive number
 Expressing the rate of reaction
2 HI = H2(g) + I2(g)

k = rate constant for forming H2 or I2

Problem 4. Calculate the rate at which HI disappears at the

moment when I2 is being formed at a rate of 1.8 x 10-6 moles
per liter per second.

Hint: HI disappears twice as fast as I2 is formed!

 Factors Influencing Reaction Rates

Reactant Concentration: molecular collisions are required for

reactions to occur
reaction rate a collision frequency a concentration
Physical State: molecules must mix to collide
When reactants are in different phases, the more finely divided
a solid or liquid reactant, the greater the surface area per unit
volume, the more contact it makes with other reactants,
and the faster the reaction.
Temperature: molecules must collide with sufficient energy to react
Higher T translates into more collisions per unit time and
into higher-energy collisions
reaction rate a collision energy a temperature
Catalysts: Speed up reaction by changing mechanism.
 The Rate Law
The rate law expresses the relationship the rate of reaction and
concentration of reactants . It is experimentally determined.

The derived rate law for a reaction must be consistent with the
postulated chemical mechanism of the reaction!

For a general reaction: aA + bB + ..... cC + dD

rate law: rate = k[A]m........
The term k is the rate constant, which is specific for a
given reaction at a given temperature.
The exponents m and n are reaction orders and are determined
by experimentally.
The values of m and n are not necessarily related in any way to
the coefficients a and b.
 How is the rate law determined experimentally?

The Procedure

1. Measure initial rates (from concentration measurements )

2. Use initial rates from several experiments to find the reaction orders

3. Calculate the rate constant

 For the simple reaction A → products:

rate law: rate = k[A]m........

 If the rate doubles when [A] doubles, the rate depends on
[A]1 and the reaction is first order with respect to A.

 If the rate quadruples when [A] doubles, the rate depends on

[A]2 and the reaction is second order with respect to [A].

 If the rate does not change when [A] doubles, the rate does
not depend on [A], and the reaction is zero order with respect
to A.
 Reaction Order Terminology

rate = k[A] first order overall (rate a [A])

rate = k[A]2 second order overall (rate a [A]2)
rate = k[A]0 = k(1) = k zero order (rate independent of [A])
Examples

NO(g) + O3(g) NO2(g) + O2(g)

rate = k[NO][O3] second order overall

2NO(g) + 2H2(g) N2(g) + 2H2O(g)

rate = k[NO]2[H2]1 third order overall

Reaction orders cannot be deduced from the balanced chemical

equation.
Plots of reactant concentration, [A], vs. time for first-, second-, an
zero-order reactions.
Plots of rate vs. reactant concentration, [A], for first-, second-, and
zero-order reactions.
 Determining Reaction Orders

O2(g) + 2NO(g) 2NO2

rate = k[O2]m[NO]n

To find m and n: A series of experiments is conducted starting with

different sets of reactant concentrations. The initial reaction rate is
measured in each experiment.
Initial rates in a series of experiments for the reaction between O2
and NO
O2(g) + 2NO(g) 2NO2

initial reactant
concentrations (mol/L) initial rate
experiment O2 NO (mol/L.s)
1 1.10 x 10-2 1.30 x 10-2 3.21 x 10-3

2 2.20 x 10-2 1.30 x 10-2 6.40 x 10-3

3 1.10 x 10-2 2.60 x 10-2 12.8 x 10-3

4 3.30 x 10-2 1.30 x 10-2 9.60 x 10-3

5 1.10 x 10-2 3.90 x 10-2 28.8 x 10-3

 Manipulating the Data

rate 2 k[O2]2m[NO]2n
= ([NO] is held constant)
rate 1 k[O2]1m[NO]1n

rate 2 [O2]2m
= = ([O2]2 / [O2]1)m
rate 1 [O2]1m

6.40 x 10-3 mol/L/s

=
(2.20 x 10-2 mol/L/ 1.10 x 10-2 mol/L)m
3.21 x 10-3 mol/L/s

1.99 = (2.00)m

m=1

Thus, the reaction is first order with respect to O2. When [O2]
doubles, the rate doubles.
 rate 3 k[O2]3m[NO]3n
= ([O2] is held constant)
rate 1 k[O2]1m[NO]1n

via same manipulations as before:

3.99 = (2.00)n

n=2

Thus, the reaction is second order with respect to NO.

When [NO] doubles, the rate quadruples.

The rate law is: rate = k[O2][NO]2

The reaction is third order overall.

Can you figure out the rate law from its stoichiometry alone?

(CH3)3CBr + OH- (CH3)3COH + Br -

One might expect,

rate = k [(CH3)3CBr] [OH-]

But,
rate = k [(CH3)3CBr]

Reaction orders must be determined from experimental data

and cannot be deduced from the balanced equation.
Units of the rate constant, k, for several overall reaction orders
overall reaction order units of k (t in seconds)

0 mol/L.s (or mol L-1 s-1)

1 1/s (or s-1)

2 L/mol . s (or L mol-1 s-1)

3 L2 / mol2 .s (or L2 mol-2 s-1)

The value of k is easily determined from experimental rate

data. The units of k depend on the overall reaction order.
 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.
 Integrated Rate Law
Consider a simple 1st order rxn: A B

Differential form:

How much A is left after time t? Integrate:

The integrated form of first order rate law:

Can be rearranged to give:

[A]0 is the initial concentration of A (t=0).

[A]t is the concentration of A at some time, t,
during the course of the reaction.
 Manipulating this equation produces…

…which is in the form y = mx + b

Graphical method for finding the reaction order from the integrated rate
law.

integrated rate law

straight-line form

If a reaction is first-order, a plot of ln [A]t vs. t will yield a straight

line with a slope of -k.
 Second-Order Processes

Similarly, integrating the rate law for a process that is second-order

in reactant A:

1 1
Rearrange, integrate: = kt +
A  A 0

also in the form, y = mx + b

 1 1
= kt +
A  A 0

[A] = concentration of A at time t

k = rate constant
t = time
[A]o = initial concentration of A

So if a process is second-order in A, a plot of 1/[A] vs.

t will yield a straight line with a slope of k.
 Second-order reaction
integrated rate law
1 1
- =kt
[A]t [A]0

straight-line form,
1 1
= kt +
A  A 0

A plot of 1 vs. time gives a straight line for a second-order reaction.

[A]
 Reaction Half-life

The half-life (t1/2) for a reaction is the time taken for the
concentration of a reactant to drop to half its initial value.

For a first-order reaction, t1/2 does not depend on the starting

concentration.
t1/2 = ln 2 = 0.693
k k

The half-life for a first-order reaction is a constant. Radioactive

decay is a first-order process. The half-life for a radioactive
nucleus is a useful indicator of its stability.
 first order reaction: A B

Integrated rate equation:

After one half-life, t = t1/2 and [A]t = 0.5[A]0 . Substituting...

NOTE: For a first-order process, the half-life does not depend on [A]0
A first order reaction is 35% complete at the
end of 55 minutes. What is the value of k?

k = 7.8 × 10–3 min–1

 An overview of zero-order, first-order and simple second-order
reactions

zero order first order second order

rate law rate = k rate = k[A] rate = k[A]2

units for k mol/L.s 1/s L/mol.s

integrated rate law ln[A]t = -kt + ln[A]0 1/[A]t = kt + 1/[A]0

-----
in straight-line form

plot for straight line --- ln[A]t vs t 1/[A]t VS t

slope, y-intercept ---- -k, ln[A]0 k, 1/[A]0

half-life ---- (ln 2)/k ----

 Rate Laws for General Elementary Steps

Elementary reactions are single step process and are classified

according to the number of molecules which they involve.

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.
 Elementary Reactions and Molecularity

individual steps = elementary reactions (or steps)

Elementary steps are characterized by their molecularity.

molecularity = number of reactant particles involved in the step

2O3(g) 3O2(g)
O3(g) O2(g) + O(g) unimolecular
O3(g) + O(g) 2O2(g) bimolecular

Termolecular elementary steps are rare!

The rate law for an elementary reaction can be deduced from the
reaction stoichiometry; reaction order equals molecularity for an
elementary step only
Give resonable explanations:

Elementary processes with molecularity greater than three are not

known.

The order of a reaction cannot, in general, be predicted from the

stoichiometry of the overall reaction . However, the order of an
elementary process is predictable.
 Reaction Mechanisms

• A complete chemical description of how reactant molecules are

converted to products. An example of a one step conversion of
reactants to products
NO + O3 O2 + NO2
• On the other hand, most chemical reactions do not follow such a
simple path from reactants to products.

2O3(g) 3O2(g)
Mechanism

O3(g) O2(g) + O(g) step 1

O3(g) + O(g) 2O2(g) step 2

• 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.
 Reaction Mechanisms

 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 sequence of events that describes the actual process by
which reactants become products is called the reaction
mechanism
 Ponder !

 The rate laws for chemical reactions can be explained by the

following general rules.

 The rate of any step in a reaction is directly proportional to the

concentrations of the reagents consumed in that step.
 The overall rate law for a reaction is determined by the sequence
of steps, or the mechanism, by which the reactants are converted
into the products of the reaction.
 The overall rate law for a reaction is dominated by the rate law
for the slowest step in the reaction.
 The rate law for a one-step reaction should therefore agree with
the stoichiometry of the reaction.
 Ponder !

 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.

 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.
 Reaction Mechanisms

The Specific Steps in an Overall Reaction

How a reaction works at the molecular level

2A + B E + F

Slow A + B C
C + A D possible steps
D E + F

C and D are reaction intermediates.

All postulated steps must sum to yield the chemical equation for the overall reaction.

Mechanisms of reactions are proposed and then tested.

 Determining molecularity and rate laws for elementary steps

PROBLEM: The following two reactions are proposed as elementary steps in the
mechanism of an overall reaction:

(1) NO2Cl (g) NO2 (g) + Cl (g)

(2) NO2Cl (g) + Cl (g) NO2 (g) + Cl2(g)

(a) Write the overall balanced equation.

(b) Determine the molecularity of each step.
(c) Write the rate law for each step.

PLAN:
We find the overall equation from the sum of the elementary steps. The
molecularity of each step equals the total number of reactant particles. We
write the rate law for each step using the molecularities as reaction orders.
SOLUTION:

(a) Writing the overall balanced equation:

(1) NO2Cl(g) → NO2(g) + Cl(g)

(2) NO2Cl(g) + Cl(g) → NO2(g) + Cl2(g)
2NO2Cl(g) → 2NO2(g) + Cl2(g)

(b) Step(1) is unimolecular.

Step(2) is bimolecular.

(c) rate1 = k1[NO2Cl]

rate2 = k2[NO2Cl] [Cl]
 The Rate-Determining Step of a Reaction Mechanism

All of the elementary steps of a mechanism do not occur at

the same rate. Usually one step is much slower than the
others. This step is called the rate-determining (or rate-
limiting) step.

An example:
The reaction NO2(g) + CO(g) → NO(g) + CO2(g)
has been proposed to occur by a two-step mechanism:

(1) NO2(g) + NO2(g) → NO3(g) + NO(g) [slow; rate-determining]

(2) NO2(g) + CO(g) → NO2(g) + CO2(g) [fast]
NO2(g) + CO(g) → NO(g) + CO2(g)
 Experimental rate law: rate = k [NO2]2

Step 1: NO2(g) + NO2 (g) NO3(g) + NO(g) Rate1 = k1[NO2]2

Step 2: NO3(g) + CO(g) NO2(g) + CO2(g) Rate2 = k2[NO3][CO]

Step 1 is slow and rate-determining; Step 2 is fast.

NO3 is an intermediate!

Thus, if k1 = k, the rate law for Step 1 (rate-determining) is the same

as the experimental rate law!

The rate law for the rate-determining step becomes the rate law for the
overall reaction.
 Correlating the Mechanism with the Rate Law

A mechanism is a hypothesis –we cannot prove it is correct, but if it is

consistent with the data, and can be used to predict results accurately,
it is a useful model for the reaction.

A valid mechanism must meet three criteria:

1. The elementary steps must add up to the overall equation.

2. The elementary steps must be physically reasonable.

3. The mechanism must correlate with the observed rate law.

Reaction Energy Diagram for the two-step NO2 - F2 reaction

The overall reaction 2NO2(g) + F2(g) →2NO2F(g) has an

experimental rate law,
Rate = k[NO2][F2].

The accepted mechanism is,

(1) NO2(g) + F2(g) → NO2F(g) + F(g) [slow; rate determining]

(2) NO2(g) + F(g) → NO2F(g) [fast]

2NO2(g) + F2(g) → 2NO2F(g)

The elementary steps sum to the overall balanced equation:

Both steps are bimolecular and are therefore reasonable.

 rate1 = k1[NO2[F2]

rate2 = k2[NO2][F]

Step 1 is the slow step,and rate1 correlates with the observed

rate law.

The mechanism is therefore reasonable.

Two transition states and one intermediate are involved.
The first step is rate-determining.
The reaction is exothermic (thermodynamics).
• The rate law for this reaction is found
(experimentally) to be

• Because termolecular processes are rare, this

rate law suggests a two-step mechanism.
 A proposed mechanism is
𝐾1
𝐾−1
𝐾2

Step 1 is an equilibrium- it includes the forward and reverse reactions.

• The rate of the overall reaction depends upon the

rate of the slow step.
• The rate law for that step would be

• But how can we find [NOBr2]?

• NOBr2 can react two ways:
– With NO to form NOBr
– By decomposition to reform NO and Br2
• The reactants and products of the first step are in
equilibrium with each other.
• Therefore, Ratef = Rater

k1 [NO] [Br2] = k−1 [NOBr2]

Solving for [NOBr2] gives us

k1
[NO] [Br2] = [NOBr2]
k−1
Substituting this expression for [NOBr2] in the rate law
for the rate-determining step gives
 Temperature and Reaction Rate
increased T → increased average speed of particles →
increased collision frequency → increased reaction rate
But,
most collisions fail to yield products!

Significance of activation energy: only those collisions with

energy equal to, or greater than, Ea 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.
 Effective Collisions

Not all collisions that occur with energy equal to, or exceeding, the
activation energy lead to products.

Molecular orientation is critical!

k = A e –Ea /RT

the frequency factor = product of collision frequency Z

and an orientation probability factor p (A = Zp)
The effect of temperature on the distribution of collision
energies
 Dependence of rate constant on temperature

Arrhenius Equation: Svante Arrhenius developed a mathematical

relationship between k and Ea.:

A = frequency factor
Ea = activation energy
R = gas constant (8.3145 J/K·mol)
T = temperature (in K)
K = rate constant of the reaction
 Linear Form of Arrhenius Equation:

Taking the natural logarithm of both sides, the equation becomes

y = mx + b

When k is determined experimentally at several temperatures, Ea

can be calculated from the slope of a plot of ln k vs. 1/T.
The activation energy = the minimum energy that the molecules
must possess in order for reaction to occur

The negative exponent suggests that, as T increases, the negative

exponent becomes smaller (less negative), the value of k increases,
and thus the reaction rate increases.

higher T larger k increased rate

 Graphical determination of the activation energy, Ea

k2 Ea 1 1
ln = - -
k1 R T2 T1
 Catalysis: Enhancing Reaction Rates
Catalyst: A substance that speeds up a reaction without being
consumed itself.
Catalysts provide New faster paths by which reaction can proceed.
This can be done in a variety of ways:

Provides a new pathway for the reaction with a lower

activation energy.

The catalyzed reaction proceeds via a different mechanism

than the uncatalyzed reaction.

Catalysts change the mechanism by which the process

occurs.
Catalyst can act by modifying the electronic structure of the
reactants. For example , the conversion of an alcohol to an
organic halide is catalyzed by hydrogen ion. Find the role of
hydrogen ion?

Br - + C2H5OH → C2H5Br +OH -

H + + C2H5 OH = C2H5OH2 + (rapid equilibrium)

Br - + C2H5 OH2 + → Br -…C2H5….OH2 → C2H5Br + H2O (Slow)

The presence of the proton on the hydroxyl group of the alcohol

apparently lowers the activation energy of the second slow step
 2Ce +4 + Tl + → 2Ce +3 + Tl +3

The above reaction is slow . Now the reaction is catalyzed by Mn ++ ,

which acts in the following ways

Ce +4 + Mn ++ → Ce +3 + Mn +3

Ce +4 + Mn +3 → Ce +3 + Mn +4

Mn +4 + Tl + → Tl +3 + Mn ++

Mn ++ permits a new mechanism whereby the single slow termolecular

process is replaced by three Faster bimolecular elementary reactions
Energy diagram of an uncatalyzed and catalyzed reaction

Uncatalyzed reaction:

A + B product

Catalyzed reaction:
A + catalyst C

C + B product + catalyst

Note that both reactions

exhibit the same thermodynamics!

A catalyst does not affect either ΔH The catalyzed and uncatalyzed reactions
or the overall yield for a reaction. occur via different pathways.
 Types of Catalysts

• Homogeneous: Exists in the same phase as the reacting molecules.

• Heterogeneous: catalyst and reaction mixture are in different phases

Heterogeneous Catalyst
1. Most often involves gaseous reactants being adsorbed on
the surface of a solid catalyst.
2. Adsorption and activation of the reactants.
3. Migration of the adsorbed reactants on the surface.
4. Reaction of the adsorbed substances.
5. Escape, or desorption, of the products.
One of the outstanding example of the heterogeneous catalysis is the
hydrogenation of unsaturated organic compounds.

H2 + C2H4 → C2H6
The reaction is slow at moderate temperature in the gas phase. The same
reaction is fast if carried out at the surface of the metal because these metal can
absorb large quantities of hydrogen , apparently by incorporating it in the
metallic lattice as hydrogen atoms. The process is represented by:

𝟏
H2 + M → M . H
𝟐

Where M . H represents the pool of atomic hydrogen in the metallic lattice. Thus
hydrogenation takes place as:
at surface
2 M . H + C2H4 C2H6

In effect, the metal provides a new reaction path of low activation

energy by dissociating the molecular hydrogen to atoms.
 Steady State Approximation(SSA)
When more than two steps are involved in a mechanism,
the rate law equation may be very Complicated
• Multiple intermediates may form and their concentrations
depend on each other.
• Some time intermediates react with other species
(reactants, intermediates)
If the intermediate is fairly reactive then they do not
attain an appreciable concentration.
• If an intermediate concentration is always small , then its
change in concentration is also small throughout the
experiment
𝒅[𝑰]
i.e. =0
𝒅𝒕
The steady state approximation utilizes the zero change
in concentration for intermediates to solve Multistep
mechanisms

• It assumes that, after an initial induction period, an

interval during which the concentrations of the
intermediates , I, rise from zero, and during the major
part of the reaction, the rates of change of concentrations
of the all the reaction intermediates are negligibly small.

• The overall rate is expressed in terms of rate of

production of product
 Key assumption: production and consumption of the
intermediate occur at the same rate, so the rate of
change in concentration of the intermediate with respect
to time is zero.

𝒅[𝑰]
i.e. =0
𝒅𝒕

 The steady state approximation consists of selecting an

intermediate in the reaction mechanism and calculating
its concentration by assuming that it is destroyed as
rapidly as it is formed.
As a practical example of the application of SSA, let us consider the
decomposition of gaseous N2O5:
2N2O5(g) → 4NO2(g) + O2(g)

𝒅[𝑶𝟐]
The experimental rate law is: = k[N2O5]
𝒅𝒕
The mechanism is:

K1
Step 1: N2O5 k-1
NO2 + NO3

k2
Step 2: NO2 + NO3 NO + O2 + NO2

k3
Step 3: NO3 + NO 2NO2
NO3 and NO are the intermediates . let us find their steady state
concentrations by using SSA.

For NO, we proceed as follows:

Rate of production of NO = Rate of destruction of NO

K2 [NO2][NO3] = k3 [NO][NO3]
[NO] = k2/k3 [NO2]………………………………(1)

For NO3,

Rate of production of NO3 = Rate of destruction of NO3

K1[N2O5] = K-1 [NO2][NO3] + K2 [NO2][NO3] + K3 [NO][NO3]

K1[N2O5] = ( K-1 [NO2] + K2 [NO2] + K3 [NO]) [NO3]……………….(2)

Substituting the value of [NO] and solving for NO3, equation (2 )
reduces to the form:
𝑲𝟏[𝑵𝟐𝑶𝟓]
[NO3] = ……………(3)
𝑲 𝟏[𝑵𝑶𝟐] + 𝟐 𝑲𝟐[𝑵𝑶𝟐]
−

The rate of reaction is also the rate of formation of oxygen,

𝒅[𝑶𝟐]
= K2[NO2][NO3]…………………..(4)
𝒅𝒕

Using eq.3 in eq.4 and solving produces,

𝒅[𝑶𝟐] 𝑲𝟏𝑲𝟐[𝑵𝟐𝑶𝟓]
= ………………….(5)
𝒅𝒕 𝑲 𝟏 + 𝟐 𝑲𝟐
−

This is as the same form as the experimental rate law. The relation
between the experimental rate constant K and rate constants for the
individual elementary steps is:
𝑲𝟏
K =
𝑲 𝟏
+ 𝟐 𝑲𝟐
−
 Enzyme Catalysis

 Enzymes are biological catalysts. Catalysts are substances that

increase the rate of chemical reactions without being used up.
Enzymes are also proteins that are folded into complex shapes that
allow smaller molecules to fit into them. The place where these
substrate molecules fit is called the active site. Examples are
lactase, alcohol dehydrogenase and DNA polymerase.

 On a molecular level, most catalysts (or most substances really)

are not just flat surfaces, they have complex three-dimensional
shapes. The substrate often has to bind to the catalyst in a very
specific way in order for the catalysed reaction to take place - this
is the active centre.
Characteristics of enzymes

 Enzymes possess great catalytic power.

 Enzymes are highly specific.
 Enzymes show varying degree of specificities.
 Absolute specificity where the enzymes react specifically
with only one substrate.
 The mechanism by which enzymes catalyzed chemical
reactions begins with the binding of the substrates to the
active site on the enzyme.
 The substrate fits into the active site of the enzyme much
like a key fits into a lock.
Model of Enzyme Action
Reactants: Reactants in an enzyme-catalyzed reaction = ―substrates‖

Active site
or
Not a substrate
substrate binding site
(not always exactly synonymous,
latter could be just a part of the active site)
 Michaelis-Menten equation
In1913, Michaelis- Menten proposed a mathematical model of the
reaction. It involves an enzyme, E, binding to a substrate, S, to form
a complex, ES, which in turn releases a product, P, regenerating the
original enzyme. This may be represented schematically as

the double arrows between S (substrate) and ES (enzyme-substrate

complex) represent the fact that enzyme-substrate binding is
a reversible process, and the single forward arrow represents the
formation of P (product).
Let V be the rate at which product appears
V = k2 [ES]…………………(1)

To derive the equation for kinetics of enzyme catalyzed reaction, we

use steady state approximation for the intermediate, ES.

K1 [E][S] = k -1 [ES]+ k2[ES]

K1 [E][S] = (k -1 + k2)[ES]………………..(2)

This equation might be solved for [ES], but it also contains ,which is
unknown. We can write the enzyme conservation equation.
[E0] = [E] + [ES]…………………….(3)

Where [E0] is the total concentration of the enzyme material.

Solving this equation for [E] and substituting the result in
equation(2), yields [ES] as follows:
K1[S] {[E0-[ES]} = (k -1 + k2)[ES]

K1[ E0] [S] - K1[S][ES] = (k -1 + k2)[ES]

(k -1 + k2)[ES] + K1[S][ES] = K1[ E0] [S]

[ES] {(k -1 + k2) + K1[S]} = K1[ E0] [S]

𝑲𝟏[ 𝑬𝟎] [𝑺]

[ES] = ….........(4)
𝒌 −𝟏+ 𝒌𝟐 + 𝑲𝟏[𝑺]

Substituting this in equation (1), we find the rate of reaction given

by

k2𝑲𝟏[ 𝑬𝟎] [𝑺]

V=
𝒌 −𝟏+ 𝒌𝟐 + 𝑲𝟏[𝑺]
 Divide the numerator and denominator by K1, the result is:

𝒌𝟐[ 𝑬𝟎] [𝑺]

V= ………………………….(5)
𝒌𝒎+[𝑺]

This expression is known as the Michaelis—Menten equation.

Understanding km

𝒌−𝟏+𝒌𝟐
km = 𝒌𝟏
The lower the Km, the more poorly it dissociates. That is, the more
TIGHTLY it is held by the enzyme

And the greater the Km, the more readily the substrate dissociates,
so the enzyme is binding it poorly
From equation (5), by taking the reciprocal of both sides, we have
the another common form of the Michaelis-Menten rate law:

𝟏 𝟏 𝒌𝒎
= + ………………(6)
𝑽 𝒌𝟐[ 𝑬𝟎] 𝒌𝟐[ 𝑬𝟎] [𝑺]

Thus the reciprocal of the reaction rate is a linear function of the

reciprocal of the substrate concentration when the total amount of
the enzyme is held constant.
 𝒌𝟐[ 𝑬𝟎] [𝑺]
We have, Michaelis—Menten equation as: V= 𝒌𝒎+[𝑺]
….(a)

Let us analyze the dependence of reaction rate on the concentration of

the substrate given by this equation.

Condition 1
At sufficiently low substrate concentration: [S] ˂˂ Km

Hence the concentration of substrate can be neglected compared to

Km

And equation(a )reduces to the form as given below:

𝒌𝟐[ 𝑬𝟎] [𝑺]

V= 𝒌𝒎
This rate law equation shows that the rate is first order
with respect to substrate concentration.

Condition 2

At sufficiently high substrate concentration: Km ˂˂ [S]

Hence Km is neglected compared to concentration of

substrate and equation(a )reduces to the form as given
below:

V = k2 [E0]

This rate law equation shows that the rate is zero order
with respect to substrate concentration.
Question

???????
Give the physical reason behind reaction rate which
changes from first to zero order with respect to substrate
concentration as the substrate concentration is increased.
 Understanding Km

Consider the
Vo that is equal
to 50% of Vmax

Vmax/2 is reached at a [S] that’s numerically

equal to Km.
Try it (Set Vo = ½ Vmax in M.M. equation and
solve for [S]).

So Km is numerically equal to the concentration of substrate

required to drive the reaction at ½ the maximal velocity