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CHEM 2410 (2010)

A/Prof. Erica Wanless


room 321, ph. 4921 8846, erica.wanless@newcastle.edu.au
Chemical Kinetics
The study of
reaction rates
Rate of reactant consumption
& product formation
Response to changing
conditions (T, P)
Understanding reaction
mechanisms
Prediction of equilibrium
Catalysis ($$)
Useful in experimental design,
optimisation & understanding
Why important?
Outline
Experimental methods
CHEM 1020 revision: rate laws, reaction
order, t
1/2
, Arrhenius equation
Reaction rate theories
Steady state approximation
Chain reactions: Explosions & Polymerisation
Catalysis: heterogeneous, homogeneous &
enzymatic
Reference Materials Skills
Atkins & De Paula Elements of
Physical Chemistry 3-5
th
Edition
Atkins & De Paula Physical
Chemistry 6-9
th
edition
J.L. Latham & A.E. Burgess,
Elementary Reaction Kinetics,
3rd edition, Butterworths
P. Monk Maths for Chemistry
Commonsense
Straight line graphs
Some maths
Do lots of example
questions - look for
commonalities
Use the tutorial times
wisely & bring laptop
or graph paper
Empirical Kinetics
Establish stoichiometry
Identify any side reactions
Basic data
[reactant] & [product]
T
Method
monitor concentration
vs time
depends on rate (fast,
medium, slow)
E.g. Stopped Flow Technique
Uses spectrophotometry
Relies on Beer-Lambert law
Absorbance concentration
A = l c
where = molar absorption coefficient
l = path length, c = [M]
2 reagents driven quickly into
mixing chamber, then concentration
measured vs time (1 ms resolution)
Monitoring Reaction Progress
Only requirement is that a
physical property changes
as the reaction proceeds
Sometimes a basic physical
measurement suffices
pressure - if # molecules
changes
conductivity - if # ions
changes
Often a chemically specific
method is required
Methods to monitor concentration
Spectrophotometry
expt B1 piperidine
pH
expt B2 - nitroethane
polarimetry
expt B3 - sucrose
GC, MS, NMR
etc.
Reaction Rate
Change in concentration of a reactant or product
per unit time:
Generally dependent on composition & T
Rate =
concentration(t
2
) concentration(t
1
)
t
2
t
1
Rate =
(concentration)
(time)
=
dc
dt
Instantaneous Rate
Reaction rates vary with time (generally get slower)
Therefore can only consider the rate at a given instant
Instantaneous rate = slope of concentration vs time graph
ie. tangent at time, t
units concentration/time eg. (mol.L
-1
)/s = mol.L
-1
.s
-1
negative for reactants, positive for products
Reaction Stoichiometry
Note! the rates of reactant consumption and product formation vary
for the different species in a reaction.
Example: the oxidation of ethene
C
2
H
4
+ 3O
2
2CO
2
+ 2H
2
O
or generally for substance J with stoichiometric coefficient v
J
, the
overall reaction rate v is given by,
reactants v
J
<0, products v
J
>0
and the overall rate, v >0
So, always name the species that the rate measurement refers to!
1
2
d[CO
2
]
dt
=
1
2
d[H
2
O]
dt
=
d[C
2
H
4
]
dt
=
1
3
d[O
2
]
dt

v =
1
v
j
d[J]
dt
Concentration Dependence
Mg
(s)
+ 2H
+
(aq)
H
2(g)
+ Mg
2+
(aq)
How could we monitor
this reaction?
Concentration Dependence (2)
Rate Laws & Rate Constants
Empirical observation: rate is often proportional to molar concentration of
the reactants raised to a power
eg. v = k.[A]
n
(Rate Law)
where n is called the reaction order
and, k is the rate constant
independent of concentration, but dependent on T
units of k must fit the rate law equation (they vary!)
eg. For n=2
v (M/s) = k.[A (M)]
2
1 1 1 1
2 2
1

= = = = s mol L s M
sM M
s
M
of units so
A
v
k . . . ,
] [
Reaction Order
The power to which the
concentration is raised in the
rate law
eg. v = k[A]
2
[B]
1
the reaction is second order in A &
first order in B
Overall order = sum of
individual species orders
eg. 2+1 = 3 for the rate law above
Order doesnt have to be integral,
v = k[A]
1/2
[B]
More complex rate laws have no
defined order,
eg. H
2(g)
+ Br
2(g)
2HBr
(g)
which can only be simplified if
[Br
2
] >> k[HBr]
then, v = k[H
2
][Br
2
]
1/2
v =
k[H
2
][Br
2
]
3 / 2
[Br
2
] + k'[ HBr]
Rate Laws
Formal expression of the rate as a function of the
concentration of the species involved
Determined experimentally
in general cant be inferred from the chemical equation
Applications
if k is also known, the rate can be calculated for given
initial concentrations
predict concentrations at a later time
any proposed mechanism must agree
Determining the Rate Law: A+B P
Isolation Method: all except one reactant in large excess (
constant concentration)
eg. v = k[A][B]
2
but B in excess, [B] [B]
0
at all times
so, v = k[A][B]
0
2
= k[A]
1
where k = k[B]
0
2
This would appear experimentally to be a first order reaction:
v [A]
1
but is technically known as Pseudo-first order behaviour as it is
not the whole story..
The dependence of the rate on each reactant can be found in a
similar way and then combined into the full rate law
e.g. B1 Piperidine experiment
Determining the Rate Law AP
Method of Initial Rates: the initial rate is
measured for a series of reactant
concentrations
eg. v = k[A]
n
then, v
0
= k[A]
0
n
, or
logv
0
= log k + n log [A]
0
(linear graph form: y = intercept + slope.x)
logv
0
log k = n log [A]
0
So, gradient of graph = n
Using...
log x.y = log x + log y
log x
b
= b log x
e.g. Initial Rates
[A]
0
v
0
(/10
-3
mol.L
-1
) (/10
-7
mol.L
-1
.s
-1
)
5.0 3.6
8.2 9.6
17 41
30 130
______________
n = slope = 2 (rxn order) so v = k[A]
2
log
10
k = intercept so,
k=
y =2.0005x - 0.8444
R
2
=1
0.5
1
1.5
2
2.5
0.5 1 1.5
log [A]
0
l
o
g

v
0
e.g. Initial Rates (2)
[CH
3
CHO]
0
Initial rate of
CH
3
CHO consumption
(mol/L) (mol.L
-1
.s
-1
)
0.10 0.020
0.20 0.081
0.30 0.182
0.40 0.318
Derive rate law and k for
CH
3
CHO
(g)
CH
4(g)
+ CO
(g)
Here the rate goes up by
____ when initial
concentration doubles, thus
n = ____
Rate of rxn =
Now determine k
Types of Rate Laws
Differential Rate Law: how rate depends on concentration
Derived from observations
What weve been working with so far.
Disadvantage
rate is not an observable, it is a derived parameter
Integrated Rate Law: how concentration depends on time
Advantage
concentration & time are both experimental observables
Principal uses
predicting concentration at time, t
determining k & reaction order
Zero Order Reaction A P
[A]
t
= -kt + [A]
0
[P]
t
= kt
Time
[
R
e
a
c
t
a
n
t
]
integrated rate law
Time
R
e
a
c
t
i
o
n

r
a
t
e
differential rate law
k
dt
P d
k A k
dt
A d
= =
= = =
] [
] [
] [
v
v
0
k units = rate units
e.g. M.s
-1
= mol.L
-1
s
-1
Rate is independent of time until reactant is completely consumed
Product concentration will increase linearly with time until reactant runs out
Using...
k.dt= kt+c
First Order Reaction A P
Consumption of A,
Integration,
integrated rate law

v =
d[A]
dt
= k[A]
d[A]
[A]
= kdt
1
[A]
d[A]
[A]
0
[A]

= kdt
0
t

ln[A] { }
[A]
0
[A]
t
= ln[A]
t
ln[A]
0
= kt
[A]
t
=[A]
0
e
kt
differential rate law
Rate dependent
on reactant
concentration
k units = time
-1
, e.g. s
-1
Using...
(1/x).dx = ln x
Exponential Decay
Product concentration will
increase exponentially with time
[A]
t
= [A]
0
e
-kt
or,
ln [A]
t
= ln [A]
0
kt
y = intercept + slope.x (linear form)
Use this form to determine k, graphically:
Example
Decomposition of Azomethane
CH
3
N
2
CH
3
CH
3
CH
3
+ N
2
k = - slope of ln[A] vs t
Gas phase rxn so [A] ~ p
Rewrite ln p = ln p
0
kt as,
ln p - ln p
0
= kt
ln (p/p
0
) = kt
k =
Using...
log x/y = log x - log y
Second Order Reaction A P
Consumption of A,
Integration as before,
integrated rate law
v =
d[A]
dt
= k[A]
2

1
[A]
2
d[A]
[A]
0
[A]

= kdt
0
t

1
[A]






[A]
0
[A]
t
=
1
[A]
t

1
[A]
0
= kt
1
[A]
t
=
1
[A]
0
+ kt
differential
rate law
Reactant
concentration is
inversely
proportional to time
Using...
(-1/x
2
).dx = 1/x
Second Order Behaviour
Although the initial decay of a second order reaction may be
rapid, later the concentration approaches zero more slowly
than in a first order reaction with the same initial rate
Defining feature:
1/[A] vs t
is linear with slope = + k
units = concentration
-1
.time
-1
, e.g. M
-1
.s
-1
= L.mol
-1
.s
-1
Second type of second order reaction: A+B P
(differential)
yields,
(integrated)
v =
d[A]
dt
= k[A][B]
kt =
1
[B]
0
[A]
0
ln
[B]/[B]
0
[A]/[A]
0






eg. C
2
H
5
I + C
6
H
5
N(CH
3
)
2
I
-
Method: titrate
the liberated I
-
with AgNO
3
Confirmed second
order reaction
in [iodoethane]
Slope = k
=
y = 0.001x + 0.6252
R
2
= 1
0.5
1
1.5
2
2.5
3
0 500 1000 1500 2000
t (s)
1
/
[
C
2
H
5
I
]


(
m
3
/
m
o
l
)
Summary of Rate Laws
Differential Rate Law:
rate & concentration
Zero Order
v = d[A]/dt = -k
First Order
v = d[A]/dt = -k[A]
Second Order
v = d[A]/dt = -k[A]
2
Integrated Rate Law:
concentration & time
Zero Order
[A]
t
= -kt + [A]
0
First Order
[A]
t
= [A]
0
e
-kt
ln [A]
t
= ln [A]
0
- kt
Second Order
1
[A]
t
=
1
[A]
0
+ kt
Half Life t
1/2
Time taken for
the [reactant]
to fall to half
of the initial
value
[A]
0
1/2[A]
0
First Order Half Life
First Order: ln [A]
t
= ln [A]
0
- kt
for [A]
t
= 1/2[A]
0
independent of
initial concentration
ln
[A]
0
2
= ln[A]
0
kt
1/2
ln
[A]
0
2[A]
0
= ln
1
2
= ln2 = kt
1/2
t
1/2
=
ln2
k
Using...
log x/y = log x - log y
Example: Decomposition of N
2
O
5
2N
2
O
5(g)
4NO
2(g)
+ O
2(g)
v = k[N
2
O
5
]
k = 6.7610
-5
s
-1
eg. Kinetics of Bacterial Growth
Log phase dn/dt = kn or n=n
0
e
kt
Generation doubling time half life (ln2/k)
kt
1/2
=
1
1
2
[A]
0

1
[A]
0
=
2
[A]
0

1
[A]
0
=
1
[A]
0
t
1/2
=
1
k[A]
0
Second Order Half Life
Second Order A P:
for [A]
t
= 1/2[A]
0
dependent on initial concentration
1
[A]
t

1
[A]
0
= kt
Approaching Equilibrium
For a first order reaction A B,
the rate of the reverse reaction
must be considered when close
to equilibrium
A B v = k
f
[A]
B A v = k
b
[B]
If [B]
0
= 0, then [A] + [B] = [A]
0

d[A]
dt
= k
f
[A] + k
b
[B]

d[A]
dt
= k
f
[A] + k
b
([A]
0
[A])
here k
f
= 2k
b
The integrated solution is,
As we approach equilibrium, t ,

[A] =
k
b
+ k
f
e
( k
f
+k
b
)t
k
b
+ k
f
[A]
0
[A]
eq
=
k
b
k
b
+ k
f
[A]
0
[B]
eq
=
k
f
k
b
+ k
f
[A]
0
K
eq
=
[B]
eq
[A]
eq
=
k
f
k
b
Important relationship between kinetics and thermodynamics!
Example: Photochromic lenses
Fully reversible reaction with well
defined K
eq
Thin layer of borosilicate glass
containing silver halide crystals
Silver is reduced by incident UV
radiation
Ag
+
+ e
-
+ h Ag
(s)
k
f
The silver (colour) is a very long
lived excited state because it is a
solid state (viscous) reaction
When UV energy is removed (dark)
the reverse reaction (k
b
) is favoured
Temperature Dependence
Empirical observation
reaction rate increases with T
Arrhenius noted the following dependency
ln k vs 1/T
linear with a characteristic slope
The Arrhenius Equation
pre-exponential factor, A
units same as k
activation energy, E
a
units e.g. kJ/mol

ln k = ln A
E
a
RT
k = Ae
E
a
/ RT
eg. Arrhenius Parameters
y = intercept +
slope.x
Slope = -E
a
/R
E
a
=
Intercept =
y =-2767.2x +25.11
R
2
=1
15
15.5
16
16.5
17
17.5
18
18.5
19
19.5
20
0.0015 0.002 0.0025 0.003 0.0035
1/T (1/K)
ln k = ln A
E
a
RT
Need to account for vast range of observed
rates and also the Arrhenius system parameters
A & E
a
must contain the constraining parameters
in any theory
Basic molecular theories
Collision Theory
Activated Complex Theory
RT E
a
Ae k
/
=
Reaction Rate Theories
The Collision Theory
Applies to simple gas phase reactions
Key Idea
molecules must collide in order to react
However, only a small fraction of collisions
produces a reaction. Why?
Factors Affecting Rate O
3
+NOO
2
+ NO
2
1. Energy of collision
2. Orientation of collision
3. Successful collision
The Theory: A + B AB
Collision frequency
[A][B]
Fraction of molecules, f
with kinetic E > E
a
is
given by the Maxwell-
Boltzmann equation,
f =0 when T=0
f =1 when T is infinite
RT E
a
e
/
= f
Kinetic E = .mass.speed
2
A minimum speed must be overcome
Now rate = # of activated collisions per unit time
v [A][B] f = [A][B]e
-Ea/RT
k e
-Ea/RT
, the Arrhenius form
The pre-exponential factor, A must involve the
collision frequency which can be calculated from the
kinetic theory of gases
where m
A
& m
B
are the molar masses of A & B, and
is the collision cross section.
B A
B A
m m
m m kT
A

) ( +
=
8
Collision cross-section,
AB
for the
target area that molecule B presents
to a colliding molecule of A,

AB
= d
2
where d = 0.5(d
A
+ d
B
)
The collision between A & B occurs
when centre of mass of A is within

AB
of centre of mass of B
Modification to account for probability
of correct orientation (steric fudge!)

AB
* = P
AB
P is usually <<1
Collision Cross-section,
Comparison with Experiment
Reaction A
Lmol
-1
s
-1
Expt.
A
Lmol
-1
s
-1
Theor.
E
a

kJmol
-1
P
2NOCl
2NO + 2Cl
9.4x10
9
5.9x10
10
102 0.16
2ClO O
2

+ Cl
2

6.3x10
7
2.5x10
10
0 2.5x10
-3
H
2
+ C
2
H
4

C
2
H
6

1.24x10
6
7.3x10
11
180 1.7x10
-6
K + Br
2

KBr + Br
1.0x10
12
2.1x10
11
0 4.8

(A
expt
= A
theor.
x P)
Activated Complex Theory
Applies to gas &
solution phase reactions
More sophisticated
steric factor appears
automatically
Key Idea
reactions proceed via an
activated complex or
transition state near the
potential energy
maximum
The Activated Complex, C

Or the transition state


Definite composition & loose structure
Not a reaction intermediate
Short-lived (10
-12
s)
Think equilibrium
A + B C

P
Some molecules entering the transition state may revert
to reactants
e.g. F
-
+ CH
3
Cl FCH
3
Cl

FCH
3
+ Cl
-
NO + Cl
2
NOCl
2

NOCl + Cl
E
a
(forward) =85 kJ /mol
E
a
(reverse) =2 kJ /mol
NO +Cl
2
Reactants
NOCl
2
NOCl +Cl
Products
H =83 kJ /mol
Progress of reaction
E
n
e
r
g
y

p
e
r

m
o
l
+
+
Endothermic example
C

Equilibrium
A + B C

P
Define K

,
Rate of formation of P:
where m relates to C

bond energies
K

=
[C

]
[A][B]
d[P]
dt
= m[C

]
d[P]
dt
= k[A][B]
Overall reaction rate is
given by,
Therefore,
k=mK

But how to get K?


Thermodynamic Approach
Recall, G = H - TS = -RT lnK
eq
thus, G

= H

- TS

= -RT ln K

so,
ln K

=
TS

RT
K

= exp
S

R








exp
H

RT








k = mexp
S

R








exp
H

RT








Ae
E
a
/RT
Using...
e
x+y
=e
x
.e
y
A highly ordered C

corresponds to S

<0 and P<<1 in collision theory

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