B18PA

Introductory Chemical Kinetics

Prof McKendrick

SUMMARY of 8 lectures

Recommended text
Elements of Physical Chemistry, Atkins and de Paula, 5e
Chapters 1, 10, 11
B18PA Course Outline
Motivation - Why is kinetics important?

Basic definitions
Reaction Rate and the Rate Constant

Effects of concentration on reaction rate
Order of Reaction
Differential/Integrated Rate Methods
Connection of Rate to Mechanism

Effect of temperature on reaction rate
Arrhenius Equation
Collision Theory
Transition State Theory

Checklist of key concepts
rate

(differential) rate law

rate constant

order

integrated rate law

half-life
| | | |
dt
A d
t
c
=
A
A
~ v
| | | | ...
m n
B A k v =
rate as a function of
concentration
change of concentration
with time
proportionality
constant in rate law
exponent (or sum of
exponents) in rate law
concentration as a
function of time
| | | |
kt
e A A g e

=
0
. .
time for concentration
to halve
k
t g e
2 ln
. .
2 / 1
=
Larger k
faster rate
Overall order
= n + m + ...
Concentration dependence of rates:
key equations
You should know, be able to derive and use









see solutions to Week 10 tutorial
Checklist of key concepts
the isolation method
pseudo-orders of reaction

elementary reactions
molecularity
rate laws by inspection


mechanisms rate laws
rate-determining steps
pre-equlibrium





concentrations in excess
remain ~constant
individual steps at molecular level
from probability
arguments
from rate laws of individual steps
= order of an elementary step
| || | B A k
dt
A d
g e =
] [
. .
One step is much slower than others
Some concentrations remain
proportional
Checklist of key concepts
The Arrhenius equation


how to use it


its connection to
physical properties


k = A exp(-E
a
/ RT) k as a function of T
e.g. plot lnk against 1/T
A, E
a

RT
E
A k
a
= ln ln
E
a
=energetic barrier
A accounts for all factors
other than energy
Checklist of key concepts
Collision theory
collision cross section
relative velocity
number density

energetic requirement, f
Maxwell-Boltzmann distribution

Steric factor, p
simple 'dynamical' theory
f exp (-E
a
/ RT)
fraction of collisions exceeding E
a

fraction of collisions with the
correct orientation
Checklist of key concepts
Transition-state theory
(pseudo-) equilibrium
rate of transmission to products

Enthalpy of activation

Entropy of activation
'thermodynamic / statistical' theory
[AB

] = K

[A] [B]
rate = k

[AB

]
energy barrier E
a
~ AH

accounts for
steric factors
A = k

exp (+AS

/ R)
Temperature dependence of reaction
rates: key equations
You should appreciate the origins of and be able to use