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Molecular Reaction Dynamics

Prof. Kamal M.S. Khalil

Collision Theory

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Collision Theory

A+B→P v = k2 [ A][ B]
P = products
The aim is to calculate the second order rate
constant k2

Collision Theory

A+B→P v = k2 [ A][ B]

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Collision Theory

A+B→P v = k2 [ A][ B]

Collision Theory

A+B→P v = k2 [ A][ B]

Products

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Collision Theory

A+B→P v = k2 [ A][ B]
Rate v ∝ rate of collision

Rate of collision ∝ mean speed of molecules

mean speed of molecules = c ∝ (T M )

1/ 2

v ∝ δ (T M ) NA NB ∝ δ (T M ) [A][B]
1/ 2 1/ 2

Collision Theory

A+B→P v = k2 [ A][ B]
A collision will be successful only if the kinetic
energy exceeds a minimum value, the activation
energy Ea
Thus, in terms of Boltzmann Factor e-Ea/Rt

Reaction rate ∝ δ (T M ) [A ][B]e − Ea

1/ 2 RT

Rate constant ∝ δ (T M ) e − Ea
1/ 2 RT

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Collision Theory

A+B→P v = k2 [ A][ B]
Not every collision will lead to reaction even if the
energy requirement is satisfied, why?
Due to the steric requirement
Thus, further factor P should be introduced

Rate constant ∝ δ (T M ) e a
1/ 2 −E RT

k ∝ steric requir.× encounter rate × minimum E requir.

2

Collision rate in gases

Given that the collision frequency = z = δ c rel N A
N A = number density of A molecules
1/ 2
 8kT 
relative speed c rel = 2 c , where
1/ 2
c= 
 πm 
For like molecules of mass m, µ = m/2
1/ 2 1/ 2
 8kT   8kT 
Thus c rel = 2 
1/ 2
 =  
π m/ 2  π m
Total Collision density = Z AA = 12 zN A = 12 δ c rel N A2

Total Collision density = Z AB = zN AN B = δ c rel N AN B

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The energy requuirement

k2 = NA δ c rel e − Ea / RT

This form of the energy dependence is broadly

consistent with experimental determination of the
reaction rate dependence on temperature

The steric requuirement

Arrhenius equation k2 = Ae − Ea / RT
Arrhenius parameters are :
A(the priexponentialfactor) and Ea (theactivationenergy)
1/ 2
 8kT 
k2 = δ   NA e − Ea / RT
 πm 

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Diffusion-controlled reactions
Encounters between reactants in solution occur in a very different
manner from encounters in gases.
Reacting molecules jostle their way in solution so the encounter
frequency in less than in gas.
However, molecules also migrates slowly for the same reason.
This presence on one molecule near the other is called the cage
effect.

A B A B P

Cage formation

Diffusion-controlled
reactions

A B A B P

Cage formation
The complicated process can be divided into simpler reactions as:

A + B → AB v = k d [A][B]
AB → A + B v = k d' [AB]
AB → P v = k a [AB]

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Diffusion-controlled
reactions
A + B → AB v = kd [A][B]
AB → A + B v = kd' [AB]
AB → P v = ka [AB]
d[AB]
= k d [A][B] - k d' [AB] - k a [AB] = 0
dt
Solving
k [A][B]
[AB] = d
k a + k d'
The rate of product formation is
d[P] ka kd
= k a [AB] = k 2 [A][B] where k 2 =
dt k a + k d'

Diffusion-controlled
reactions
The rate of product formation is
d[P] kk
= ka [AB] = k2 [A][B] where k2 = a d '
dt ka + kd
There are two limits
1. separation of the encounter pairs (kd' ) << product formation (ka )
ka kd
k2 = = kd i.e. diffusion controlled reaction
ka

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Activation-controlled
reactions
The rate of product formation is
d[P] kk
= ka [AB] = k2 [A][B] where k2 = a d '
dt ka + kd
There are two limits
2. when substantial activation energy is involved in the reaction
AB → P Then ka << kd' and
ka kd
k2 = = kd i.e. activation controlled reaction
ka

CHEMISTRY

Chemical Equilibrium
Consideration

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Le Châtelier’s Principle

• Consider the production of ammonia

N2(g) + 3H2(g) 2NH3(g)
• As the pressure increases, the amount of ammonia
present at equilibrium increases.
• As the temperature decreases, the amount of ammonia at
equilibrium increases.
• Can this be predicted?

Le Châtelier’s Principle

• Le Châtelier’s Principle:
“if a system at equilibrium is
disturbed, the system will move
in such a way as to counteract
the disturbance”

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Le Châtelier’s Principle
Change in Reactant or Product
Concentrations
• Consider the Haber process
N2(g) + 3H2(g) 2NH3(g)
• If H2 is added while the system is at equilibrium, the
system must respond to counteract the added H 2 (by Le
Châtelier).
• The system must consume the H 2 and produce products
until a new equilibrium is established.
• So, [H2] and [N2] will decrease and [NH3] increases.

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Le Châtelier’s Principle
Change in Reactant or Product
Concentrations
• N2 and H2 are pumped into a chamber.
• The pre-heated gases are passed through a heating coil to
the catalyst bed.
• The catalyst bed is kept at 460 - 550 °C under high
pressure.
• The product gas stream (containing N 2, H2 and NH3) is
passed over a cooler to a refrigeration unit.
• In the refrigeration unit, ammonia liquefies not N 2 or H2.

Le Châtelier’s Principle
Change in Reactant or Product
Concentrations
• The unreacted nitrogen and hydrogen are recycled with
the new N2 and H2 feed gas.
• The equilibrium amount of ammonia is optimized
because the product (NH 3) is continually removed and
the reactants (N2 and H2) are continually being added.

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Le Châtelier’s Principle
Effects of Volume and Pressure Changes
• As volume is decreased pressure increases.
• Le Châtelier’s Principle: if pressure is increased the
system will shift to counteract the increase.
• That is, the system shifts to remove gases and decrease
pressure.

Le Châtelier’s Principle

Effect of Temperature Changes

• The equilibrium constant is temperature dependent.
• For an endothermic reaction, ∆H > 0 and heat can be
considered as a reactant.
• For an exothermic reaction, ∆H < 0 and heat can be
considered as a product.

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Le Châtelier’s Principle
The Effect of Catalysis
• A catalyst lowers the activation energy barrier for the
reaction.
• Therefore, a catalyst will decrease the time taken to reach
equilibrium.
• A catalyst does not effect the composition of the
equilibrium mixture.

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