Chemical Kinetics

Lectures 4-8
Potential energy surfaces, Arrhenius equation,
Reversible reactions, T-jump

Dr. Sajesh P. Thomas

[email protected]
Assistant Professor
Department of Chemistry
IIT Delhi, India.
1
Topics for today:
1. Potential energy surfaces

2. Temperature dependence of rate

constant: Arrhenius equation

3. Reversible reactions,
Relaxation methods (T-jump experiment)
 Potential energy surface (PES)
The potential energy of the system can be expressed as a function of the
reaction coordinates.
The variation of the potential energy with a change along these coordinates can
then be presented as a graph or surface referred to as a potential energy
surface.
a.…a’ : The pathway corresponding to the reaction of B + C to form BC

The depth of the potential = the dissociation

PES as a two-dimensional contour plot energy of the diatomic, De(BC)

The minimum along RBC corresponds to the

equilibrium bond length of the diatomic.
Understanding contour maps

A contour map is a two-dimensional representation

of a three-dimensional surface, such as the Earth's
surface. Contour maps use contour lines to show
elevation, slope, and other geographic features
Activated complex vs transition state.
Are they the same ? Not exactly.
The cluster of atoms that corresponds to the region
close to the maximum is called the activated
complex.

For the transition state on PES,

Is the transition state a local maximum on the PES ?
Not necessarily.

It is a saddle point.

saddle point
saddle
 Remember,
intermediates are not
transition states

Intermediates are
local minima on PES

Reaction coordinates
 Prof. Ahmed H. Zewail
CalTech

1999 Nobel Prize in Chemistry:

“... for his studies of transition states of chemical reactions by
femtosecond spectroscopy “.

**Read the press release document by the Nobel prize committee (uploaded to Moodle).
There may be a question from that document for your quiz and midterm exam.
 Temperature Dependence of Rate Constants
Arrhenius expression:

Svante Arrhenius
frequency factor or Arrhenius
A preexponential factor
(same unit as that of k )
Collision frequency & Orientation/steric factor

Ea activation energy for the

reaction
The reaction coordinate
represents the bonding and
geometry changes that
occur in the transformation of
reactants into products.

Shown here are Boltzmann

distributions of molecular
translational energy (Etrans) at
200 K and 500 K. Notice
that the fraction of molecules
with translational
energy greater than Ea
increase with temperature
The fraction of reactant molecules with energy in excess of Ea is given by the
Boltzmann distribution
Chemical Kinetics in Kitchen
Milk spoils in 1 day at 25∘C
but lasts nearly a week at 4∘C.

Enzymes in food catalyze the

breakdown of proteins, fats,
and carbohydrates.

Enzymes involved in food

decomposition also follow the
Arrhenius relationship

Bacteria growth
At room temperature (25∘C, 298 K),
spoilage-causing microbes grow
rapidly. At refrigeration temperature
(4∘C, 277K), microbial growth is much
slower.
What happens if we keep half-eaten left-over food?

Saliva has enzymes (amylase, lipase, protease) that break down

food components, leading to faster degradation.
Reversible Reactions and Equilibrium
[A] and [B] are at their equilibrium
values for t  teq . After equilibrium has been
established, the reactant and product
concentrations are time independent such that,

Kc is the equilibrium constant

1) Measurement of the
reactant decay kinetics (or
the product formation
kinetics) provides a measure
of the apparent rate
constant, (kA + kB )

2) The measurement of Kc,

or the reactant and product
concentrations at
equilibrium (kA/kB )
Books:
Atkins
Engel & Reid
 Perturbation- relaxation methods
→ For the study of fast reactions
T-jump, P-jump, EF-jump
T-jump (temperature jump) experiments are useful for studying
the kinetics and mechanisms of fast chemical and biochemical
reactions – which reach equilibrium very fast
T-jump experiments allow us to investigate reactions that occur
on timescales ranging from microseconds to milliseconds (10-6 –
10-3 s) , which are too fast for conventional kinetic techniques.

Temperature jump (T-jump) experiment

A sudden shift in temperature acts as a perturbation on the system

(Δ H is non-zero)
r ⦵
 Temperature jump (T-jump) experiment
(Δ H is non-zero)
r ⦵
➢ Electric discharge
➢ Bursts of microwave radiation
➢ Intense electromagnetic pulses.

Electrical discharges can

achieve temperature jumps of
between 5 and 10 K in
about 1 μs.

The high energy output of a

pulsed laser is sufficient to
generate temperature jumps
of between 10 and 30 K
within nanoseconds in
aqueous samples.
Let’s see a reversible reaction

Endothermic

H= -ve
Exothermic
 [A]1, eq

X0
At the new temperature the X
concentration of A changes as follows:
[A]2, eq

, Relaxation after
a temperature
jump [first-order
reactions]
 x
Atkins – Chapter 17C

Engel and Reid – Chapter 35

 Parallel reactions

Assuming first-order reactions,

The yield i is defined as the probability that a given
product will be formed by decay of the reactant:
 Consecutive elementary reactions
Some reactions proceed through the formation of an intermediate
(denoted I), as in the consecutive unimolecular reactions
The product P is formed by the unimolecular
decay of I:

Assuming first-order reactions:

Time of maximum [intermediate], tmax

This derivative is equal to zero when t = tmax

Taking natural logarithms of both sides

 Steady-State Approximation (SSA)

SSA or Quasi-SSA assumes that the intermediate,

I, is in a low, constant concentration.

implies that the concentration of the intermediate

changes as the concentration of A changes, but if
ka/kb << 1 it changes very little

The steady-state approximation requires

the concentration of the intermediate to be
low relative to that of the reactants, which
is the case when ka << kb.
 when k << k
a b

If k << k
a b , how will we have a steady state ?
The concentration of I is so low compared to the concentration of
A, even though ka << kb , ka[A]  kb[I]
Application of Steady-State Approximation (SSA)

The solution:
Step 1) Identify the intermediates and apply SSA,
The net rate of change of
concentration of N2O5 is then:

first-order rate law

The rate-determining step (RDS)
 Pre-equilibrium

In pre-equilibrium, the intermediate is in equilibrium with the

reactants

A pre-equilibrium can arise when the rate of decay of the

intermediate back into reactants is much faster than the rate at
which it forms products → ka′ >> kb
In this pre-equilibrium mechanism the final step, I → P, is rate-determining
(RDS).

The preceding steps control the steady concentration of the intermediate.

 Analysing a pre-equilibrium using SSA
Pre-equilibrium assumption
gave us the following:

= 0; SSA When the rate constant for the decay of

I into products is much smaller than
that for its decay into reactants,

Reduces to the same form as the

pre-equilibrium assumption
A problem from the tutorial sheet
Lindemann–Hinshelwood mechanism of unimolecular reactions

The reactant molecule acquires enough

energy to react as a result of collisions with
other molecules

Collisions are simple bimolecular events,

So how can they result in a first-order rate
law?
First-order gas-phase reactions are widely called ‘unimolecular reactions’ because they
also involve an elementary unimolecular step in which the reactant molecule changes
into the product.

The first successful explanation of unimolecular reactions was provided by Frederick

Lindemann in 1921 and then elaborated by Cyril Hinshelwood
Lindemann–Hinshelwood mechanism of unimolecular reactions
1) The species A is excited by collision
with A
2) The energized A molecule (A*) may
either be deactivated by a collision with A
3) OR go on to decay by a
unimolecular process to form
products.

1) A reactant molecule A becomes energetically excited by collision

with another A molecule in a bimolecular step :
2) The energized molecule (A*) might lose its excess energy by collision
with another molecule:

3) Unimolecular decay of A* into product P: The excited molecule

might shake itself apart or into a different arrangement of its atoms and
form product P.

If this unimolecular step is the rate-determining step, then it will explain

why the overall reaction shows first-order kinetics

The net rate of formation of A*:

 Rearrangement of this equation gives

So the rate law for the formation of P is

If the rate of deactivation by (A*,A) collisions is much greater than

the rate of unimolecular decay, then:

This is at high pressure: collisions are much

Lindemann–Hinshelwood rate law
more than unimolecular decay

What happens at low pressure ?

At low pressure or concentration: collisions are much less probable than
unimolecular decay

The reaction switches to overall

second-order kinetics !

Physical interpretation: As the pressure is reduced the rate of the

bimolecular process in which A* loses its excess energy becomes negligible
compared to the rate at which A* goes on to form products.

this is not RDS at low pressure

Try applying the pre-equilibrium assumption to:

Lindemann–Hinshelwood mechanism of unimolecular reactions

What do you infer?