1

Chemical Kinetics
Texts: Atkins, 8th edtn., chaps. 22, 23 & 24
Specialist: Reaction Kinetics Pilling & Seakins (1995)
Revision
Photochemical Kinetics
Photolytic activation, flash photolysis
Fast reactions
Theories of reaction rates
Simple collision theory
Transition state theory
2
Overview of kinetics
Qualitative description
rate, order, rate law, rate constant, molecularity, elementary,
complex, temperature dependence, steady-state, ...
Reaction dynamics
H (
2
S) + ICl (v, J) HI (v, J) + Cl (
2
P
1/2
)
Modelling of complex reactions C & E News, 6-Nov-89, pp.25-31
stratospheric O
3
tropospheric hydrocarbons H
3
CCO
2
ONO
2

combustion chemical vapour deposition: SiH
4
Si films
3
Rate of reaction {symbol:R,v,}
Stoichiometric equation
m A + n B = p X + q Y

Rate = (1/m) d[A]/dt
= (1/n) d[B]/dt
= + (1/p) d[X]/dt
= + (1/q) d[Y]/dt
Units: (concentration/time)
in SI mol/m
3
/s, more practically mol dm
3
s
1
4
Rate Law
How does the rate depend upon [ ]s?
Find out by experiment

The Rate Law equation
R = k
n
[A]
o
[B]
|
(for many reactions)
order, n = o + | + (dimensionless)
rate constant, k
n
(units depend on n)
Rate = k
n
when each [conc] = unity

5
Experimental rate laws?
CO + Cl
2
COCl
2

Rate = k [CO][Cl
2
]
1/2

Order = 1.5 or one-and-a-half order
H
2
+ I
2
2HI
Rate = k [H
2
][I
2
]
Order = 2 or second order
H
2
+ Br
2
2HBr
Rate = k [H
2
][Br
2
] / (1 + k {[HBr]/[Br
2
]} )
Order = undefined or none
6
Determining the Rate Law
Integration
Trial & error approach
Not suitable for multi-reactant systems
Most accurate
Initial rates
Best for multi-reactant reactions
Lower accuracy
Flooding or Isolation
Composite technique
Uses integration or initial rates methods
7
Integration of rate laws
Order of reaction
For a reaction aA products
the rate law is:

n
A
A
n
n
A k
dt
A d
r
ak k def ining
A ak
dt
A d
A k
dt
A d
a
r
] [
] [
] [
] [
] [
] [ 1
= =
=
=
= =
rate of change in the
concentration of A
8
First-order reaction
) ( ) ] [ ] ln([
] [
] [
] [
] [
] [
] [
0 0
0
] [
] [
1
0
t t k A A
dt k
A
A d
dt k
A
A d
A k
dt
A d
r
A t
t
A
A
A
A
A
t
=
=
=
= =
} }
9
First-order reaction
t k A A
t t k A A
A t
A t
=
=
0
0 0
] ln[ ] ln[
) ( ] ln[ ] ln[
A plot of ln[A] versus t gives a straight
line of slope -k
A
if r = k
A
[A]
1
10
First-order reaction
t k
t
t k
t
A
t
A t
A
A
e A A
e
A
A
t k
A
A
t t k A A

=
=
=
|
|
.
|

\
|
=
0
0
0
0 0
] [ ] [
] [
] [
] [
] [
ln
) ( ] ln[ ] ln[
11
A P assume that -(d[A]/dt) = k [A]
1
0 5 10 15
1
2
3
4
5
6
7
8
[
H
2
O
2
]


/

m
o
l

d
m
-
3
Time / ms
12
Integrated rate equation
ln [A] = -k t + ln [A]
0
0 5 10 15
0.2
0.4
0.6
0.8
1.0
l
n

[
H
2
O
2
]


/

m
o
l

d
m
-
3
Time / ms
13
Half life: first-order
reaction
2 / 1
0
0
0
] [
] [
2
1
ln
] [
] [
ln
t k
A
A
t k
A
A
A
A
t
=
|
|
|
|
.
|

\
|
=
|
|
.
|

\
|
The time taken for [A] to drop to half its original value is called the
reactions half-life, t
1/2.
Setting [A] = [A]
0

and t = t
1/2
in:



14
Half life: first-order
reaction
2 / 1
2 / 1
2 / 1
693 . 0 693 . 0
693 . 0
2
1
ln
t
k or
k
t
t k
A
A
A
= =
= =
|
.
|

\
|
15
When is a reaction over?
[A] = [A]
0
exp{-kt}
Technically [A]=0 only after infinite time
16
Second-order reaction
} }
=
=
= =
t
A
A
t
A
A
A
dt k
A
A d
dt k
A
A d
A k
dt
A d
r
] [
] [ 0
2
2
2
0
] [
] [
] [
] [
] [
] [
17
Second-order reaction
t k
A A
t t k
A A
A
t
A
t
=
=
|
|
.
|

\
|

0
0
0
] [
1
] [
1
) (
] [
1
] [
1
A plot of 1/[A] versus t gives a straight
line of slope k
A
if r = k
A
[A]
2
18
Second order test: A + A P

2 4 6 8 10
10
12
14
16
18
20
22
24
(1 / [A]
0
)
1

/

[
A
]
Time / ms
19
Half-life: second-order
reaction
2 / 1
0
2 / 1
0
2 / 1
0
0
] [
1
] [
1
] [
1
] [
2
] [
1
] [
1
t
A k
or t k
A
t k
A A
t k
A A
A
A
A
o
A
t
= =
=
=
20
Rate law for elementary reaction
Law of Mass Action applies:
rate of rxn product of active masses of reactants
active mass molar concentration raised to power
of number of species
Examples:
A P + Q rate = k
1
[A]
1

A + B C + D rate = k
2
[A]
1
[B]
1

2A + B E + F + G rate = k
3
[A]
2
[B]
1
21
Molecularity of elementary reactions?
Unimolecular (decay) A P
- (d[A]/dt) = k
1
[A]
Bimolecular (collision) A + B P
- (d[A]/dt) = k
2
[A] [B]
Termolecular (collision) A + B + C P
- (d[A]/dt) = k
3
[A] [B] [C]
No other are feasible! Statistically highly unlikely.
22
CO + Cl
2
COCl
2
Exptal rate law: - (d[CO]/dt) = k [CO] [Cl
2
]
1/2
Conclusion?: reaction does not proceed as written
Elementary reactions; rxns. that proceed as written at
the molecular level.
Cl
2
Cl + Cl (1) Decay
Cl + CO COCl (2) Collisional
COCl + Cl
2
COCl
2
+ Cl (3) Collisional
Cl + Cl Cl
2
(4) Collisional
Steps 1 thru 4 comprise the mechanism of the reaction.
23
- (d[CO]/dt) = k
2
[Cl] [CO]
If steps 2 & 3 are slow in comparison to 1 & 4
then, Cl
2
2Cl or K = [Cl]
2
/ [Cl
2
]
So [Cl] = \K [Cl
2
]
1/2

Hence:
- (d[CO] / dt) = k
2
\K [CO][Cl
2
]
1/2
Predict that: observed k = k
2
\K
Therefore mechanism confirmed (?)
24
H
2
+ I
2
2 HI
Predict: + (1/2) (d[HI]/dt) = k [H
2
] [I
2
]
But if via:
I
2
2 I
I + I + H
2
2 HI rate = k
2
[I]
2
[H
2
]
I + I I
2
Assume, as before, that 1 & 3 are fast cf. to 2
Then: I
2
2 I or K = [I]
2
/ [I
2
]
Rate = k
2
[I]
2
[H
2
] = k
2
K [I
2
] [H
2
] (identical)
Check? I
2
+ hv

2 I (light of 578 nm)
25
Problem
In the decomposition of azomethane, A, at a pressure of
21.8 kPa & a temperature of 576 K the following
concentrations were recorded as a function of time, t:
Time, t /mins 0 30 60 90 120
[A] / mmol dm
3
8.70 6.52 4.89 3.67 2.75
Show that the reaction is 1
st
order in azomethane &
determine the rate constant at this temperature.
26
Recognise that this is a rate law question dealing with
the integral method.
- (d[A]/dt) = k [A]
?
= k [A]
1

Re-arrange & integrate (bookwork)
Test: ln [A] = - k t + ln [A]
0

Complete table:
Time, t /mins 0 30 60 90 120
ln [A] 2.16 1.88 1.59 1.30 1.01
Plot ln [A] along y-axis; t along x-axis
Is it linear? Yes. Conclusion follows.
Calc. slope as: -0.00959 so k = + 9.610
-3
min
-1
27
More recent questions
Write down the rate of rxn for the rxn:
C
3
H
8
+ 5 O
2
= 3 CO
2
+ 4 H
2
O
for both products & reactants [8 marks]
For a 2
nd
order rxn the rate law can be written:
- (d[A]/dt) = k [A]
2
What are the units of k ? [5 marks]
Why is the elementary rxn NO
2
+ NO
2
N
2
O
4
referred to
as a bimolecular rxn? [3 marks]
28
Temperature dependence?

C
2
H
5
Cl C
2
H
4
+ HCl

k/s
-1
T/K
6.1 10
-5
700
30 10
-5
727
242 10
-5
765
Conclusion: very sensitive to temperature
Rule of thumb: rate ~ doubles for a 10 K rise
29
Details of T dependence
Hood
k = A exp{ -B/T }
Arrhenius
k = A exp{ - E / RT }
A A-factor or
pre-exponential factor
k at T
E activation energy
(energy barrier) J mol
-1
or kJ mol
-1

R gas constant.
Temperature
Rate
of
rxn
30
Arrhenius eqn. k=A exp{-E/RT}
Useful linear form: ln k = -(E/R)(1/T) + ln A
Plot ln k along Y-axis vs (1/T) along X-axis
Slope is negative -(E/R); intercept = ln A
Experimental Es range from 0 to +400 kJ mol
-1

Examples:
H
-
+ HCl H
2
+ Cl
-
19 kJ mol
-1

H
-
+ HF H
2
+ F
-
139 kJ mol
-1

C
2
H
5
I C
2
H
4
+ HI 209 kJ mol
-1
C
2
H
6
2 CH
3
368 kJ mol
-1
31
Practical Arrhenius plot, origin not included
0.0009 0.0010 0.0011 0.0012 0.0013 0.0014 0.0015
-8
-6
-4
-2
0
2
4
6
8
Intercept = 27.602 fromwhich A = 1.1 x 10
12
dm
3
mol
-1
s
-1
Slope = -22,550 fromwhich E = 188 kJ/mol
l
n

k

/
(
d
m
3

m
o
l
-
1

s
-
1
)
K / T
32
Rate constant expression
|
.
|

\
|

=
RT
E
A k
A
exp
|
|
.
|

\
|
|
.
|

\
|

=
|
|
.
|

\
|
|
|
.
|

\
|
|
.
|

\
|

=
|
|
|
|
.
|

\
|

=
2 1 2
1
2 1 2
1
2
1
2
1
1 1
ln
1 1
exp
) (
) (
exp
T T R
E
k
k
T T R
E
k
k
RT
E
RT
E
A
A
k
k
A
A
A
A
( )
1
4
202 . 51
314 . 8
58 . 6158
10 12526 . 1
314 . 8
693 . 0
15 . 303
1
15 . 293
1
314 . 8 2
1
ln

= |
.
|

\
|

=
|
.
|

\
|

=
|
.
|

\
|
|
.
|

\
|

=
|
.
|

\
|
mol kJ E
E
E
E
A
A
A
A
33
Photochemical activation
Initiation of reaction by light absorption; very important
photosynthesis; reactions in upper atmosphere
No. of photons absorbed? Einstein-Stark law: 1 photon
responsible for primary photochemical act (untrue)
S
0
+ hv S
1
* Jablonski diagram
S* S
0
+ hv fluorescence, phosphorescence
S* + M S
0
+ M collisional deactivation (quenching)
S* P
-
+ Q
-
photochemical reaction
34
Example & Jablonski diagram
A ruby laser with
frequency doubling to
347.2 nm has an output of
100J with pulse widths of
20 ns.
If all the light is absorbed
in 10 cm
3
of a 0.10 mol
dm
-3
solution of perylene,
what fraction of the
perylene molecules are
activated?
S
3
S
2
S
1
S
0
T
1
INTERNAL CONVERSION
10
4
-10
12
s
-1
INTERSYSTEM CROSSING
10
4
-10
12
s
-1
FLUORESCENCE
10
6
-10
9
s
-1
PHOSPHORESCENCE
10
-2
-10
4
s
-1
35
# of photons = total energy / energy of 1 photon
Energy of photon?



# of photons = 100 / 5.725 10
19
= 1.7467 10
20

# of molecules: 0.1 mol in 1000 cm
3
, => 1 10
3
mol in 10 cm
3


=> 6.022 10
20
molecules
fraction activated: 1.7467 10
20
/ 6.022 10
20
= 0.29
J
m
ms Js hc
19
9
1 8 34
10 725 . 5
10 2 . 347
) 10 3 ( ) 10 626 . 6 (

=


= =
c

c
36
Key parameter: quantum yield, u
u = (no. of molecules reacted)/(no. of photons absorbed)
Example: 40% of 490 nm radiation from 100 W source
transmitted thru a sample for 45 minutes; 344 mmol of
absorbing compound decomposed. Find u.
Energy of photon? c = hc /
(6.62610
34
J s)(3.0010
8
m s
1
)/(49010
9
m) = 4.0610
19
J
Power: 100 Watts = 100 J s
-1

Total energy into sample = (100 J s
1
)(4560 s)(0.60)= 162 kJ
Photons absorbed = (162,000)/(4.0610
19
) = 4.010
23

Molecules reacted? (6.02310
23
) (0.344) = 2.07 10
23

u = 2.07 10
23
/ 4.010
23
= 0.52
37
Quantum yield
Significance? u = 2.0 for 2HI H
2
+ I
2
reaction
HI + hv H

+ I

(i) primary | = 1
H

+ HI H
2
+ I

(p)
I

+ I

I
2
(t)
For H
2
+ Cl
2
2HCl u > 10
6

Is u constant? No, depends on , T, solvent, time.
/ nm >430 405 400 <370
u 0 0.36 0.50 1.0
for NO
2
NO+O
38
u?
Absolute measurement of F
A
, etc.? No; use relative method.
Ferrioxalate actinometer:
C
2
O
4
2
+ 2 Fe
3+
2 Fe
2+
+ 2 CO
2

u = 1.25 at 334 nm but fairly constant from 254 to 579 nm
For a reaction in an organic solvent the photo-reduction of
anthraquinone in ethanol has a unit quantum yield in the UV.
DETECTOR
39
Rates of photochemical reactions
Br
2
+ hv Br + Br
Definition of rate:
where n
J
is stoichiometric
coefficient (+ve for products)
Units: mol s
-1

So F
A
is moles of photons
absorbed per second
Finally, the reaction rate per
unit volume in mol s
-1
m
-3
or mol m
-3
s
-1

( )
| |
| |
Rate =
|
\

|
.
|

|
\

|
.
|
|
= =
=

|
\

|
.
|
|
=
1
2
2 2
2
v
| |
|
J
J
A A
A
dn
dt
dn Br
dt
F I
n Br V Br
d Br
dt
F
V
( )
40
Stern-Volmer
Apply SS approx. to M*:
d[M*]/dt = (F
A
/V) - k
F
[M*] - k
Q
[M*][Q]
Also (F
F
/ V)= k
F
[M*]
So: (F
A
/ F
F
) = 1 + (k
Q
/k
F
) [Q]
And hence:
Plot reciprocal of fluorescent intensity versus [Q]
Intercept is (1/F
A
) and slope is = (k
Q
/ k
F
) (1/F
A
)
Measure k
F
in a separate experiment; e.g. measure the
half-life of the fluorescence with short light pulse & [Q]=0
since d[M*]/dt = - k
F
[M*] then [M*]=[M*]
0
exp(-t/t)
M + hv M* F
A
/ V
M* M + hv F
F
/ V
M* + Q M + Q
41
Problem 23.8 (Atkins)
Benzophenone phosphorescence with triethylamine as
quencher in methanol solution.
Data is:
[Q] / mol dm
-3
1.0E-3 5.0E-3 10.0E-3
F
F
/(arbitrary) 0.41 0.25 0.16
Half-life of benzophenone triplet is 29 s.
Calculate k
Q
.
42
0.000 0.002 0.004 0.006 0.008 0.010
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
Y = A + B * X
Parameter Value Error
------------------------------------------------------------
A 1.96549 0.10995
B 424.53279 16.96558
1
/
F
F
[Q] / mol dm
-3
43
Flash photolysis [RK, Pilling & Seakins, p39 on]
Fast burst of laser
light
10 ns, 1 ps down to
femtosecond
High concentrations
of reactive species
instantaneously
Study their fate
Transition state
spectroscopy
J. Phys. Chem. a 4-6-98
Xe
ARC
LAMP
ArF
EXCIMER
LASER
SS HEATABLE
REACTION
VESSEL
44
Flash photolysis
Adiabatic
Light absorbed => heat => T rise
Low heat capacity of gas => 2,000 K
Pyrolytic not photolytic
Study RH + O
2
spectra of OH

, C
2
, CH, etc
Isothermal
Reactant ca. 100 Pa, inert gas 100 kPa
T rise ca. 10 K; quantitative study possible
precursor + hv CH

subsequent CH + O
2

45
Example [RK, Pilling & Seakins, p48]
CH + O
2
products
Excess O
2
present
[O
2
]
0
= 8.810
14
molecules cm
-3

1st order kinetics
Follow [CH] by LIF
t / s 20 30 40 60
I
F
0.230 0.144 0.088 0.033

Calculate k
1
and k
2

20 30 40 50 60 70 80
-5.0
-4.5
-4.0
-3.5
-3.0
-2.5
-2.0
-1.5
-1.0
l
n

(
I
F
)
Time / s
46
Problem
In a flash-photolysis experiment a radical, R
-
, was produced
during a 2 s flash of light and its subsequent decay
followed by kinetic spectrophotometry: R
-
+ R
-
R
2

The path-length was 50 cm, the molar absorptivity, c,
1.110
4
dm
3
/mol/cm.
Calculate the rate constant for recombination.
t / s 0 10 15 25 40 50
Absorbance 0.75 0.58 0.51 0.41 0.32 0.28
How would you determine c?
47
Photodissociation [RK, p. 288]
Same laser dissociates ICN at 306 nm & is used to measure
[CN] by LIF at 388.5 nm
Aim: measure time delay between photolysis pulse and
appearance of CN by changing the timing of the two pulses.
Experimentally: t ~ 20530 fs; separation ~ 600 pm [C & E News 7-Nov-88]
FS LASER
ICN
SAMPLE
MOVABLE MIRROR
30 m = 100 fs
FREQUENCY
SUBTRACTOR
PROBE PULSE
PHOTOPULSE
Beam Splitter
48
TS spectroscopy; Atkins p. 834
Changing the wavelength of the
probing pulse can allow not just
the final product, free CN, to be
determined but the intermediates
along the reaction path including
the transition state.
For NaI one can see the
activated complex vibrate at (27
cm
-1
) 1.25 ps intervals surviving
for ~10 oscillations
see fig. 24.75 Atkins 8th ed.
49
Fast flow tubes; 1 m
3
/s, inert coating, t=d/v
In a RF discharge: O
2
O + O or pass H
2
over heated
tungsten filament or O
3
over 1000
o
C quartz, etc.
Use non-invasive methods for analysis e.g. absorption, emission
Gas titration: add stable NO
2
(measurable flow rate)
Fast O+NO
2
NO+O
2
then O+NO

NO
2
-
NO
2
+hv
End-point? Lights out when flow(NO
2
) = flow(O)
NO
2
O
2
50
ClO + NO
3
J. Phys. Chem. 95:7747 (1991)
1.5 m long, 4 cm od, Pyrex tube with sliding injector to vary
reaction time
F
-
+ HNO
3

-
NO
3
+ HF [
-
NO
3
] monitor at 662 nm
F
-
+ HCl
-
Cl + HF followed by Cl
-
+ O
3

-
ClO + O
2
MS
He
F
2
/ He
HCl
He
HNO
3
/ He F
2
/ He
-
SLIDING INJECTOR
RF
51
Problem [RK, Pilling & Seakins, p36]
HO
2
-
+ C
2
H
4
C
2
H
5
-
+ O
2
C
2
H
5
O
2
-

MS determines LH channel 11%, RH channel 89%

C
2
H
5
signal 6.14 3.95 2.53 1.25 0.70 0.40
Injector d / cm 3 5 7 10 12 15

Linear flow velocity was 1,080 cm s
-1
at 295 K & 263 Pa.
Calculate 1
st
order rate constant; NB [O
2
]
0
>>[C
2
H
5
-
]
0

52
Flow tubes; pros & cons
Mixing time restricts timescale to millisecond range
Difficult to work at pressures > (atm/100)
Wall reactions can complicate kinetics
coat with Teflon or halocarbon wax; or vary tube diameter
Cheap to build & operate, sensitive detection available
Resonance fluorescence
Laser induced fluorescence
Mass spectrometry
Laser magnetic resonance
53
Resonance fluorescence
Atomic species (H, N, O, Br, Cl, F) mainly not molecular
Atomic lines are very narrow; chance of absorption by
another species is highly unlikely
Resonance lamp: microwave discharge dissociates H
2

H atoms formed in electronically excited state; fluoresce,
emitting photon which H-atoms in reaction vessel absorb
& re-emit them where they can be detected by PMT
Lamp: H
2
H H* H + hv
Rxn cell: H + hv H* H + hv
54
LIF; detection of OH
Excitation pulse at 282 nm to
upper state of OH with lifetime
of ns; fluorescence to ground
state at 308 nm
I
F
n
relative concentrations not
absolute (drawback).
Right angle geometry
Good candidates:
CN, CH, CH
3
O, NH, H, SO
v'=2
v'=1
v'=0
v''=2
v''=1
v''=0
282 nm 308 nm
55
Reactions in shock waves
Wide range of Ts & Ps accessible; 2,000 K, 50 bar routine
Thermodynamics of high-T species eg Ar up to 5,000 K
Study birth of compounds: C
6
H
5
CHO CO* + C
6
H
6

Energy transfer rxns.: CO
2
+ M CO
2
* + M
Relative rates, use standard rxn as clock
56
CH* Chemiluminescence (431 nm) Detected at Endwall and
Sidewall
Experiments: Ignition Delay Time
PMT Detector
Lens
Filter (310 nm)
Slit
Endwall
Shock Tube
Sidewall
O
H
*
Time
Ignition
O
H
*
Time
Ignition
Use endwall for ignition

Use sidewall for profiles
57
Mode of action of shock tube
Fast bunsen-burner (ns)
Shock wave acts as a
piston compressing &
heating the gas ahead of it
Study rxns behind incident
shock wave or reflected
shock wave (ms-s times)
Non-invasive techniques
T & p by computation from
measured shock velocity
P
DISTANCE
T
1
T
2
T
3
T
58
Shock Tube Simulation
59
Problem
A single-pulse shock tube used to study 1
st
order reaction
C
2
H
5
I C
2
H
4
+ HI; to avoid errors in T measurement
a comparative study was carried out with C
3
H
7
I C
3
H
6

+ HI for which k
B
=9.110
12
exp(-21,900/T) s
-1
. For
a rxn time of 220 s 5% decomp. of C
3
H
7
I occurred.
What was the temp. of the shock wave? [~900 K]
For C
2
H
5
I 0.90% decomp. occurred; evaluate k
A
.
If at 800 K (k
A
/k
B
) = 0.102 compute the Arrhenius
equation for k
A
. [~5.810
13
exp(-25,260/T) s
-1
]