Chain reactions

Tams Turnyi
Institute of Chemistry
Etvs University (ELTE)
Budapest, Hungary
Max Bodenstein (German, 1871-1942)
Investigated the H
2
Cl
2
photochemical reaction
and observed that single photon several million HCl product species
This term was printed for the first time in 1921 in the PhD thesis of
Jens Anton Christiansen (Danish, 1988-1969)
The origin of term chain reactions : the gold watch chain of Bodenstein
Explanation of Bodenstein (1913):

Primary reaction:
Absorption of a single photon
single active molecule (maybe Cl
2
+
???)
Secondary reactions:
Single active molecule
several million product species
Bodenstein and Lind investigated (1907)
the production of hydrogen bromide in a thermal reaction:
Karl F. Herzfeld (Austrian, 1892-1978)
theory of reaction rates, chain reactions
The proper mechanism was suggested (1919)
independently from each other by
Jens A. Christiansen, Karl F. Herzfeld and Michael Polanyi :
HBr 2 Br H
2 2
= +
| || |
| |
.
[HBr] Br
Br H [HBr]
2
2 / 3
2 2
k
k
dt
d
' +
=
M Br 2 M Br
2
+ +
Empirical rate equation:
H HBr H Br
2
+ +
Br HBr Br H
2
+ +
Br H HBr H
2
+ +
M Br M Br 2
2
+ +
Michael Polanyi (Hungarian, 1891-1976)
first potential-energy surface, transition-state theory, sociology
Bodenstein could not explain the origin of this equation.
Chain carriers (also called chain centres, i.e. reactive intermediates)
are generated in the initiation steps.

In the chain propagation steps the chain carriers react with the reactants,
produce products and regenerate the chain carriers.
In the inhibition step the chain carriers react with the product,
reactants are reformed, and there is no reduction
in the number of chain carriers.
In the branching step two or more chain carriers are produced
from a single chain carrier.
In the termination steps the chain carriers are consumed.
Chain reactions
Mechanism of the H
2
Br
2
reaction
(a) initiation:

1 M Br 2 M Br
2
+ +
| || | M Br
2 1 1
k v =
(b) propagation:

2

H HBr H Br
2
+ + ] [Br][H
2 2 2
k v =
Br HBr Br H
2
+ + ] [H][Br
2 3 3
k v =
(c) inhibition:

4

Br H HBr H
2
+ = +
[H][HBr] k v
4 4
=
(d) termination:

5

M Br M Br 2
2
+ +
| | M [Br]
2
5 5
k v =
3
Calculation of the concentrationtime profiles
concentrationtime profiles of the H
2
Br
2
reaction
(stoichiometric mixture, T= 600 K, p= 1 atm)
| |
[H][HBr] ] [Br][H
d
H d
4 2 2 4 2
2
k k v v
t
+ = + =
| |
| || |
2
5 2 3 2 1 5 3 1
2
[Br] ] [H][Br M Br
d
Br d
k k k v v v
t
+ = + =
| |
[H][HBr] ] [H][Br ] [Br][H
d
H d
4 2 3 2 2 4 3 2
k k k v v v
t
= =
| |
| | ] [ [Br] 2 Br] [H][ ] [H][Br ] [Br][H ] [ Br 2 2 2
d
Br d
2
5 4 2 3 2 2 2 1 5 4 3 2 1
M k H k k k M k v v v v v
t
+ + = + + =
| |
| | Br] H [ H ] [H][Br ] [Br][H
d
HBr d
4 2 3 2 2 4 3 2
k k k v v v
t
+ = + =
M Br 2 M Br 1
2
+ +
H HBr H Br 2
2
+ +
Br HBr Br H 3
2
+ +
Br H HBr H 4
2
+ +
M Br M Br 2 5
2
+ +
rates of R1 and R5 << rates of R2 and R3
rate of R1 = rate of R5

In the case of small [HBr] :
rate of R2 = rate of R3
production rates
d[H
2
]/dt -100.1
d[Br
2
]/dt -100.1
d[HBr]/dt +200.2
d[H]/dt +0.0014
d[Br]/dt +0.0026
rates of reaction steps
R1 Br
2
+M2 Br+M 1.0
R2 Br+H
2
HBr+H 100.2
R3 H+Br
2
HBr+Br 100.1
R4 H+HBrH
2
+Br 0.1
R5 2 Br+M Br
2
+M 1.0
Relative rates at t = 1 second
(all rates are normed with respect to v
1
)
| |
4 3 2
d
H d
v v v
t
=
| |
5 4 3 2 1
2 2
d
Br d
v v v v v
t
+ + =
0.0014 = +100.2 100.1 0.1
0.0026 = 2.0 100.2 + 100.1 + 0.1 2.0
| |
4 3 2
d
HBr d
v v v
t
+ =
200.2 = +100.2 +100.1 0.1
Relation of reaction rates and production rates
M Br 2 M Br 1
2
+ +
H HBr H Br 2
2
+ +
Br HBr Br H 3
2
+ +
Br H HBr H 4
2
+ +
M Br M Br 2 5
2
+ +
Calculation of [Br]


| |
0
d
H d
4 3 2
= = v v v
t
| |
0 2 2
d
Br d
5 4 3 2 1
= + + = v v v v v
t
_________________________________________


0 2 2
5 1
= v v
5 1
v v =
| || | | | M [Br] M Br
2
5 2 1
k k =
| | | |
2
5
1
Br Br
k
k
=
M Br 2 M Br
2
+ +
M Br M Br 2
2
+ +
1
5
+
Calculation of [H]
| |
[H][HBr] ] [H][Br ] [Br][H
d
H d
4 2 3 2 2
k k k
t
=
| |
| |
[HBr] k ] [Br k
Br
k
k
k ] [H
H
4 2 3
2
5
1
2 2
+
=
| | | | ( )
5 1 2 1
, , Br Br k k f = | | | | | | | | ( )
5 4 3 2 1 2 2 2
, , , , , HBr , H , Br H k k k k k f =
| | [H][HBr] ] [H][Br Br ] [H 0
4 2 3 2
5
1
2 2
k k
k
k
k =
| | | |
2
5
1
Br Br
k
k
=
[H][HBr] ] [H][Br ] [Br][H 0
4 2 3 2 2
k k k =
Equation for [Br] is inserted:
Algebraic equations for the calculation of [H] and [Br]:
Calculation of the production rate of HBr
This is identical to the empirical equation of
Bodenstein and Lind:
After insertion of the equations
for [Br] and [H] and rearrangement:
| |
| |
[HBr] k ] [Br k
Br
k
k
k ] [H
H
4 2 3
2
5
1
2 2
+
=
| |
| |
[HBr] ] [Br
Br ] [H 2
d
HBr d
3
4
2
2
3
2 2
5
1
2
k
k
k
k
k
t
+
=
[HBr] is almost zero at the beginning of the reaction:
| |
| |2
1
2 2
5
1
2
Br ] [H 2
d
HBr d
k
k
k
t
=
Order for H
2
and Br
2
are 1 and

0.5, respectively.
The overall order of the reaction is 1.5
| || |
| |
.
[HBr] Br
Br H [HBr]
2
2 / 3
2 2
k
k
dt
d
' +
=
| |
| | Br] H [ H ] [H][Br ] [Br][H
d
HBr d
4 2 3 2 2 4 3 2
k k k v v v
t
+ = + =
| | | |
2
5
1
Br
k
k
Br =
Mean number of propagation steps which occur before termination =
1 . 50
2
2 . 100
v 2
v
5
2
= = =
consumption rate of the chain carrier in the propagation step

consumption rate of the chain carrier in the termination step
The chain length at t=1 s
in the H
2
Br
2
reaction
at the defined conditions
Chain length
The origin of explosions
The Nobel Prize in Chemistry 1956: Semenov and Hinshelwood:
"for their researches into the mechanism of chemical reactions"
Sir Cyril Norman Hinshelwood (English, 1897-1967)
Investigation (1927) of the H
2
O
2
reaction:
discovery of the 1
st
and 2
nd
explosion limits
First experimental proof:
Nikolay Nikolaevich Semenov (Russian, 1896-1986)
Investigation (1926) of the phosphorus vapouroxygen reacion.
Explosion occurs, if the partial pressure of O
2
is
between two limits. Interpretation via a branching chain reaction.
Mixture H
2
+Br
2
cannot explode at isothermal conditions.
Suggestion of Christiansen and Kramers (1923):
explosions are due to branching chain reactions
BUT: it was a pure speculation
Explosion of hydrogenoxygen mixtures
2 H
2
+ O
2
2 H
2
O
Observations:
The 1
st
explosion limit depends on the size of the vessel and the quality of the wall.
The 2
nd
and 3
rd
limits do not depend on these
1 H
2
+ O
2
.H + .HO
2
initiation
2 .OH + H
2
.H + H
2
O propagation
3 .H + O
2
.OH + :O branching
4 :O + H
2
.OH + .H branching
5 .H + O
2
+ M .HO
2
+ M termination*
6 .H wall termination
7 :O wall termination
8 .OH wall termination
9 .HO
2
+ H
2
.H + H
2
O
2
initiation *
10 2 .HO
2
H
2
O
2
+ O
2
termination
11 H
2
O
2
2 .OH initiation
Below the 1
st
explosion limit:

domination of the termination reactions at the
wall

no explosion

-
1 H
2
+ O
2
.H + .HO
2
initiation
2 .OH + H
2
.H + H
2
O propagation
3 .H + O
2
.OH + :O branching
4 :O + H
2
.OH + .H branching
5 .H + O
2
+ M .HO
2
+ M termination*
6 .H wall termination
7 :O wall termination
8 .OH wall termination
9 .HO
2
+ H
2
.H + H
2
O
2
initiation *
10 2 .HO
2
H
2
O
2
+ O
2
termination
11 H
2
O
2
2 .OH initiation
Between the 1
st
and the 2
nd
explosion limits:

Branching steps (2), (3) and (4).

3 H + O
2
.OH + :O
2 .OH + H
2
.H + H
2
O
4 :O + H
2
.H + .OH
2 .OH + H
2
.H + H
2
O
+ ____________________
.H + O
2
+ 3 H
2
3 .H + 2 H
2
O

explosion

H. H.
H.
H.
H.
H.
H.
H.
H.
H.
H.
H.
H.
1 H
2
+ O
2
.H + .HO
2
initiation
2 .OH + H
2
.H + H
2
O propagation
3 .H + O
2
.OH + :O branching
4 :O + H
2
.OH + .H branching
5 .H + O
2
+ M .HO
2
+ M termination*
6 .H wall termination
7 :O wall termination
8 .OH wall termination
9 .HO
2
+ H
2
.H + H
2
O
2
initiation *
10 2 .HO
2
H
2
O
2
+ O
2
termination
11 H
2
O
2
2 .OH initiation
-
Between the 2
nd
and the 3
rd
explosion limits:

5 .H + O
2
+ M .HO
2
+ M termination*

no explosion
-
1 H
2
+ O
2
.H + .HO
2
initiation
2 .OH + H
2
.H + H
2
O propagation
3 .H + O
2
.OH + :O branching
4 :O + H
2
.OH + .H branching
5 .H + O
2
+ M .HO
2
+ M termination*
6 .H wall termination
7 :O wall termination
8 .OH wall termination
9 .HO
2
+ H
2
.H + H
2
O
2
initiation *
10 2 .HO
2
H
2
O
2
+ O
2
termination
11 H
2
O
2
2 .OH initiation
above the 3
rd
explosion limit

Reactions (9), (10), and (11) become important

explosion
-
1 H
2
+ O
2
.H + .HO
2
initiation
2 .OH + H
2
.H + H
2
O propagation
3 .H + O
2
.OH + :O branching
4 :O + H
2
.OH + .H branching
5 .H + O
2
+ M .HO
2
+ M termination*
6 .H wall termination
7 :O wall termination
8 .OH wall termination
9 .HO
2
+ H
2
.H + H
2
O
2
initiation *
10 2 .HO
2
H
2
O
2
+ O
2
termination
11 H
2
O
2
2 .OH initiation
The two basic types of chain reactions
Open chain reactions
Chain reactions without branching steps

Examples: H
2
+ Br
2,
reaction,
,

alkane pyrolysis and polimerisation reactions
Branched chain reactions
Chain reactions that include branching reaction steps

Examples: H
2
+O
2
reaction,
hydrocarbonair explosions and flames
Two types of explosions

Another possibility:
(i) exothermic reaction,
(ii) hindered dissipation of heat and
(iii) increased reaction rate with raising temperature, then
higher temperature faster reactions increased heat production
Presence of a chain reaction is not needed for a thermal explosion.
Branched chain reactions are
exothermic and fast
dissipation of heat is frequently hindered
most branched chain explosions are also thermal explosions
thermal explosion
Branched chain explosions:
rapid increase of the concentration of chain carriers leads to
the increase of reaction rate and finally to explosion
Svante August Arrhenius (Swedish, 1859-1927)
Nobel Prize in Chemistry (1903), electrolytic theory of dissociation
Theoretical considerations of Arrhenius (1889):
equilibrium between the normal and active species
activation energy E is T-independent in small temperature range
Arrhenius equation:
RT
E
A k

= e
Vant Hoffs equations (1884): or
RT
E
A k

= e
RT
DT B
A k
2
e

=
Temperature dependence of the rate coefficient
Jacobus Henricus Vant Hoff (Dutch, 1852-1911)
The first Nobel Prize in Chemistry (1901) in recognition of the
extraordinary services he has rendered by the discovery of the
laws of chemical dynamics and osmotic pressure in solutions
Arrhenius-plot
k A
E
RT
a
=
|
\

|
.
|
exp
A preexponential factor
E
a
activation energy
Arrhenius-plot:
ln ln k A
E
RT
a
=
Plotting ln k against 1/T gives a line
Slope: m = -E
a
/R gives activation energy E
a

Arrhenius equation:
or
Arrhenius-plot between 220 K (53 C )
and 320 K (+47 C)
Reaction CH
4
+OH CH
3
+ H
2
O
the most important methane consuming reaction in the troposphere
one of the most important reactions of methane combustion
Arrhenius-equation
is usually very accurate in a
narrow temperature range
(solution phase kinetics,
atmospheric chemistry).
Arrhenius-equation
is usually not applicable
in a wide temperature range
(combustion, explosions, pyrolysis).
Arrhenius-plot between 300 K (27 C )
and 2200 K (~1930 C)
RT
C
n
BT k

= e
Extended Arrhenius-equation
Note that if n=0 A=B and E
a
=C
General definition of activation energy:
( )
p
a
T
k
R E
|
|
.
|

\
|
c
c
=
1
ln
Thank you all
for your attention
Literature used:

Michael J. Pilling Paul W. Seakins
Reaction Kinetics
Oxford University Press, 1995

Keith J. Laidler
The World of Physical Chemistry
Oxford University Press, 1995

The Nobel Prize in Chemistry 1956
Presentation speech by Professor A. lander
http://nobelprize.org/chemistry/laureates/1956/press.html

H
2
Br
2
and H
2
O
2
concentration-time profiles
were calculated by Dr. Istvn Gy. Zsly
(Department of Physical Chemistry, Etvs University, Budapest)

Comments of Dr. Judit Zdor, Mr. Jnos Daru, and Dr.Thomas Condra
are gratefully acknowledged.

Special thank to Prof. Preben G. Srensen (University of Copenhagen)
for the photo of J. A. Christiansen and
to Prof. Ronald Imbihl (Universitt Hannover)
for the photo of the gold watch of Bodenstein