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= 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
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
= 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