CHEM.

204

Kinetic Properties of
Chemical Reactions

References: Atkins Chapter 17

Zumdahl Chapter 15

A. Half-lives

[ A]0
• Zero order: t1 / 2 
2k
ln 2
• First order: t1 / 2 
k
1
• Second order: t1/ 2 
k [ A]0

• Generally: for nth order in [A]

2n 1  1
t1 / 2 
(n  1) k [ A]0n 1

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Illustrative example

• For a second order reaction: Plot t1/2

versus 1/[A]0 straight line of slope 1/k.

[A]0 [A]1

[A]1/2
[A]0/2
[A]0/4

t1 t2 t

B. Molecularity
• Reaction mechanism  a sequence of
elementary steps.
H + Br2  HBr + Br bimolecular
• Define: Molecularity of a given
elementary step  number of reactant
molecules coming together to react in
that step.
• The concepts of molecularity and
elementary step are closely linked
together.

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 Examples
• ONE reactant: Unimolecular reaction
CH2
–  CH3 ─ CH ═ CH2
CH2 Involves an elementary
CH2 rate-determining step
– SN1 reactions
• TWO reactants: Bimolecular reaction
– Dimerization of alkenes and dienes.
– SN2 reactions:
CH3I + CH3 ─ CH2O  CH3 ─ CH2O ─ CH3 + I

Molecularity and elementary step

• Rate law: v  k [CH3I] [CH3CH2O ]

• Difference between order and molecularity:

– Reaction order: empirical quantity, obtained
from the experimental rate law.
– Molecularity: refers to an elementary reaction
step proposed as an individual step in an overall
mechanism.
• If the reaction is an elementary bimolecular
process, then it has second order kinetics;
but, if the kinetics are second order, then the
reaction might be complex.

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Rate law of an elementary step
• ONLY for an elementary step: we can
write the rate law from the chemical
equation (stoichiometry):
– A  Products d [ A]
unimolecular
 k [ A]
dt
– A + B  Products d [ A]
bimolecular  k [ A][ B ]
dt
– H2 + I2  2 HI : this is an overall
chemical reaction, which is not
bimolecular. It is a net result of a
detailed, complex mechanism.

C. Temperature dependence of
reaction rates
• For many reactions:
Plot ln k versus 1/T
 straight line of
negative slope.
k  A e Ea / RT Arrhenius
equation

• A  Arrhenius, or
pre-exponential, or
frequency factor.
• Ea  activation
energy Van’t Hoff plot

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Activation energy

• High Ea: rate constant

strongly depends on
temperature.
• Zero Ea: rate independent
of T.
• ve Ea: the rate decreases
as T increases! Ea
indicating a complex
mechanism…
• T-dependence of A may
be very complicated 
non-Arrhenius-like
behavior.

Activation energy
• It is possible to define Activation
Energy in a general manner:
d ln k
Ea  RT 2
dT
• Activation energies of successive
elementary steps:

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Significance of the Arrhenius parameters
• A  collision frequency (Z)
– Assume the reaction is gaseous and
bimolecular:
1
•For like molecules: Z AA   crel N A2
2
•For unlike molecules: Z   c N N
AB rel A B

– Typically, in a gas at 1.00 atm, Z1028 cm3

s 1.
– The collision frequency  T1/2.

Here (AB):

   d 2   (rA  rB )2
1/ 2
 8kT 
crel   
  
mAmB

mA  mB

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Arrhenius parameters
• Energetics of collisions:
– Molecules must collide with energy
at least equal to Ea, for the reaction
to occur.
 E / RT
– The fraction of molecules  e a

Rate = collision frequency  energy factor

 steric factor
Fraction of molecules
= Z  e  Ea / RT
  with the right
orientation

T-dependence of the energy factor