Chain reactions

Max Bodenstein (German, 1871-1942)

Investigated the H2−Cl2 photochemical reaction
and observed that single photon → several million HCl product species

Explanation of Bodenstein (1913):

Primary reaction:
Absorption of a single photon →
single active molecule (maybe Cl2+ ???)
Secondary reactions:
Single active molecule →
several million product species

The origin of term ‘chain reactions’ : the gold watch chain of Bodenstein

This term was printed for the first time in 1921 in the PhD thesis of
Jens Anton Christiansen (Danish, 1988-1969)
Bodenstein and Lind investigated (1907)
the production of hydrogen bromide in a thermal reaction: H 2 + Br2 = 2 HBr

d [HBr] k [H 2 ][Br2 ]
3/ 2

Empirical rate equation: = .

dt [Br2 ] + k ′[HBr]
Bodenstein could not explain the origin of this equation.

The proper mechanism was suggested (1919)

Br2 + M → 2 Br + M
independently from each other by Br + H 2 → HBr + H
Jens A. Christiansen, Karl F. Herzfeld and Michael Polanyi :
H + Br2 → HBr + Br
H + HBr → H 2 + Br
Karl F. Herzfeld (Austrian, 1892-1978) 2 Br + M → Br2 + M
theory of reaction rates, chain reactions

Michael Polanyi (Hungarian, 1891-1976)

first potential-energy surface, transition-state theory, sociology
 Chain reactions

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.

 Mechanism of the H2−Br2 reaction
(a) initiation:
1 Br2 + M → 2 Br + M v1 = k1 [Br2 ][M ]
(b) propagation:

2 Br + H 2 → HBr + H v2 = k 2 [Br][H 2 ]
3 H + Br2 → HBr + Br v3 = k3 [H][Br2 ]
(c) inhibition:

4 H + HBr = H 2 + Br v4 = k 4 [H][HBr]

(d) termination:

5 2 Br + M → Br2 + M v5 = k5 [Br]2 [M ]
 Calculation of the concentration−time profiles
d[H 2 ]
= −v2 + v4 = − k 2 [Br][H 2 ] + k 4 [H][HBr] 1 Br2 + M → 2 Br + M
dt
2 Br + H 2 → HBr + H
d[Br2 ]
= −v1 − v3 + v5 = − k1 [Br2 ][M ] − k3 [H][Br2 ] + k5 [Br]2 3 H + Br2 → HBr + Br
dt
d[H ]
4 H + HBr → H 2 + Br
= v2 − v3 − v4 = k 2 [Br][H 2 ] − k3 [H][Br2 ] − k 4 [H][HBr] 5 2 Br + M → Br2 + M
dt
d[Br ]
= 2v1 − v2 + v3 + v4 − 2v5 = k1 [Br2 ] − k 2 [Br][H 2 ] + k3 [H][Br2 ] − 2k5 [Br]2
dt
d[HBr ]
= v2 + v3 − v4 = k 2 [Br][H 2 ] + k3 [H][Br2 ] − k 4 [H ][H Br]
dt

concentration−time profiles of the H2−Br2 reaction

(stoichiometric mixture, T= 600 K, p= 1 atm)
 Relative rates at t = 1 second
(all rates are normed with respect to v1)

rates of reaction steps rates of R1 and R5 << rates of R2 and R3

R1 Br2+M→2 Br+M 1,0 rate of R1 = rate of R5
R2 Br+H2→HBr+H 100,2 In the case of small [HBr] :
R3 H+Br2→HBr+Br 100,1 rate of R2 = rate of R3
R4 H+HBr→H2+Br 0,1
R5 2 Br+M → Br2+M 1,0

production rates
d[H2]/dt -100,1
d[Br2]/dt -100,1
d[HBr]/dt +200,2
d[H]/dt +0,0014
d[Br]/dt +0,0026
 Relation of reaction rates and production rates

d[HBr ]
1 Br2 + M → 2 Br + M
= v2 + v3 − v4 2 Br + H 2 → HBr + H
dt 3 H + Br2 → HBr + Br
4 H + HBr → H 2 + Br
200,2 = +100,2 +100,1 –0,1
5 2 Br+ M → Br2 + M

d[H ]
= v2 − v3 − v4
dt
0,0014 = +100,2 –100,1 –0,1

d[Br ]
= 2v1 − v2 + v3 + v4 − 2v5
dt
0,0026 = 2,0 – 100,2 + 100,1 + 0,1 – 2,0
 Calculation of [Br]

d[H ]
= v2 − v3 − v4 =0
dt
d[Br ]
= 2v1 − v2 + v3 + v4 − 2v5 = 0
+ dt
_________________________________________

2v1 − 2v5 = 0
v1 = v5
1 Br2 + M → 2 Br + M k1 [Br2 ][M] = k5 [Br]2 [M]
5 2 Br + M → Br2 + M

[Br ] = k1
[Br2 ]
k5
 Calculation of [H]

d[H ]
= k 2 [Br][H2 ] − k3[H][Br2 ] − k 4 [H][HBr]
dt
0 = k 2 [Br][H2 ] − k3[H][Br2 ] − k 4 [H][HBr]

Equation for [Br] is inserted: [Br ] = [Br2 ]

k1
k5
0 = [H 2 ] k 2
k1
[Br2 ] − k3[H][Br2 ] − k4 [H][HBr]
k5

[H 2 ] k 2
k1
[Br2 ]
k5
[H] =
k3 [Br2 ] − k 4 [HBr]
Algebraic equations for the calculation of [H] and [Br]:

[Br] = f1 ([Br2 ] , k1 , k5 ) [H] = f 2 ([Br2 ] , [H 2 ] , [HBr] , k1 , k2 , k3 , k4 , k5 )

 Calculation of the production rate of HBr
[H 2 ] k 2
k1
[Br2 ]
[Br] = k1 [Br2 ] [H] =
k5
k5 k3 [Br2 ] − k 4 [HBr]

d[HBr ]
= v2 + v3 − v4 = k 2 [Br][H 2 ] + k3 [H][Br2 ] − k 4 [H ][ H Br]
dt

[H 2 ][Br2 ]2
k1 3
2 k2
After insertion of the equations d[HBr ] k
= 5

dt k
for [Br] and [H] and rearrangement: [Br2 ] + 4 [HBr]
k3

d [HBr] k [H 2 ][Br2 ]
3/ 2
This is identical to the empirical equation of
= .
Bodenstein and Lind: dt [Br2 ] + k [HBr]
′

[HBr] is almost zero at the beginning of the reaction:

d[HBr]
[H 2 ][Br2 ]2
k1 1
Order for H2 and Br2 are 1 and 0.5, respectively.
= 2 k2
dt k5 The overall order of the reaction is 1.5
 Chain length

Mean number of propagation steps which occur before termination =

consumption rate of the chain carrier in the propagation step


consumption rate of the chain carrier in the termination step

v2 100,2
= = = 50,1
2 v5 2

The chain length at t=1 s

in the H2−Br2 reaction
at the defined conditions
 The origin of explosions
Mixture H2+Br2 cannot explode at isothermal conditions.

Suggestion of Christiansen and Kramers (1923):

explosions are due to branching chain reactions
BUT: it was a pure speculation

First experimental proof:

Nikolay Nikolaevich Semenov (Russian, 1896-1986)
Investigation (1926) of the phosphorus vapour−oxygen reacion.
Explosion occurs, if the partial pressure of O2 is
between two limits. Interpretation via a branching chain reaction.

Sir Cyril Norman Hinshelwood (English, 1897-1967)

Investigation (1927) of the H2−O2 reaction:
discovery of the 1st and 2nd explosion limits

The Nobel Prize in Chemistry 1956: Semenov and Hinshelwood:

"for their researches into the mechanism of chemical reactions"
 Explosion of hydrogen−oxygen mixtures
2 H2 + O2 → 2 H2O

Observations:
The 1st explosion limit depends on the size of the vessel and the quality of the wall.
The 2nd and 3rd limits do not depend on these
1 H2 + O2 → .H + .HO2 initiation
2 .OH + H2 → .H + H2O propagation
3 .H + O2 → .OH + :O branching
4 :O + H2 → .OH + .H branching
5 .H + O2 + M → .HO2 + M termination*
6 .H → wall termination
7 :O → wall termination
8 .OH → wall termination
9 .HO2 + H2 → .H + H2O2 initiation *
10 2 .HO2 → H2O2 + O2 termination
11 H2O2 → 2 .OH initiation
1 H2 + O2 → .H + .HO2 initiation
2 .OH + H2 → .H + H2O propagation
3 .H + O2 → .OH + :O branching
4 :O + H2 → .OH + .H branching
5 .H + O2 + M → .HO2 + M termination*
6 .H → wall termination
7 :O → wall termination
8 .OH → wall termination •
9 .HO2 + H2 → .H + H2O2 initiation *
10 2 .HO2 → H2O2 + O2 termination
11 H2O2 → 2 .OH initiation

Below the 1st explosion limit:

domination of the termination reactions at the

wall

→ no explosion
1 H2 + O2 → .H + .HO2 initiation
2 .OH + H2 → .H + H2O propagation
3 .H + O2 → .OH + :O branching
4 :O + H2 → .OH + .H branching
5 .H + O2 + M → .HO2 + M termination*
6 .H → wall termination
7 :O → wall termination •
8 .OH → wall termination
9 .HO2 + H2 → .H + H2O2 initiation *
10 2 .HO2 → H2O2 + O2 termination
11 H2O2 → 2 .OH initiation H.
H. H.
Between the 1st and the 2nd explosion limits:
H.
Branching steps (2), (3) and (4).
H.
3 H + O2 → .OH + :O H. H. H.
2 .OH + H2 → .H + H2O
4 :O + H2 → .H + .OH H.
2 .OH + H2 → .H + H2O
H.
+ ____________________
.H + O2 + 3 H2 → 3 .H + 2 H2O H. H.
→ explosion H.
1 H2 + O2 → .H + .HO2 initiation
2 .OH + H2 → .H + H2O propagation
3 .H + O2 → .OH + :O branching
4 :O + H2 → .OH + .H branching •
5 .H + O2 + M → .HO2 + M termination*
6 .H → wall termination
7 :O → wall termination
8 .OH → wall termination
9 .HO2 + H2 → .H + H2O2 initiation *
10 2 .HO2 → H2O2 + O2 termination
11 H2O2 → 2 .OH initiation

Between the 2nd and the 3rd explosion limits:

5 .H + O2 + M → .HO2 + M termination*

→ no explosion
1 H2 + O2 → .H + .HO2 initiation •
2 .OH + H2 → .H + H2O propagation
3 .H + O2 → .OH + :O branching
4 :O + H2 → .OH + .H branching
5 .H + O2 + M → .HO2 + M termination*
6 .H → wall termination
7 :O → wall termination
8 .OH → wall termination
9 .HO2 + H2 → .H + H2O2 initiation *
10 2 .HO2 → H2O2 + O2 termination
11 H2O2 → 2 .OH initiation

above the 3rd explosion limit

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

→ explosion
 The two basic types of chain reactions

Open chain reactions

Chain reactions without branching steps

Examples: H2 + Br2, reaction,,

alkane pyrolysis and polimerisation reactions

Branched chain reactions

Chain reactions that include branching reaction steps

Examples: H2+O2 reaction,

hydrocarbon−air explosions and flames
 Two types of explosions

Branched chain explosions:

rapid increase of the concentration of chain carriers leads to
the increase of reaction rate and finally to explosion

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

 thermal explosion

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
 Temperature dependence of the rate coefficient
E B − DT 2
− −
Van’t Hoff’s equations (1884): k = A e RT
or k = Ae RT

Theoretical considerations of Arrhenius (1889):

• equilibrium between the ‘normal’ and ‘active’ species
• activation energy E is T-independent in small temperature range
E
−
Arrhenius equation: k = Ae RT

Jacobus Henricus Van’t 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”

Svante August Arrhenius (Swedish, 1859-1927)

Nobel Prize in Chemistry (1903), electrolytic theory of dissociation
 Arrhenius-plot

Arrhenius equation:
 Ea  Ea
k = A exp  −  or ln k = ln A −
 RT  RT

A preexponential factor Plotting ln k against 1/T gives a line

Ea activation energy Slope: m = -Ea/R gives activation energy Ea

Arrhenius-plot:
 Reaction CH4+OH → CH3 + H2O
the most important methane consuming reaction in the troposphere
one of the most important reactions of methane combustion
Arrhenius-plot between 220 K (−53 °C ) Arrhenius-plot between 300 K (27 °C )
and 320 K (+47 °C) and 2200 K (≈1930 °C)

Arrhenius-equation Arrhenius-equation
is usually very accurate in a is usually not applicable
narrow temperature range in a wide temperature range
(solution phase kinetics, (combustion, explosions, pyrolysis).
atmospheric chemistry).
 Extended Arrhenius-equation

C
−
k = BT n e RT

Note that if n≠0  A≠B and Ea≠C

General definition of activation energy:

 ∂ ln k 
Ea = − R 
 ∂ (1 T )  p
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. Ölander
http://nobelprize.org/chemistry/laureates/1956/press.html

H2−Br2 and H2−O2 concentration-time profiles

were calculated by Dr. István Gy. Zsély
(Department of Physical Chemistry, Eötvös University, Budapest)

Comments of Ms. Judit Zádor are gratefully acknowledged.

Special thank to Prof. Preben G. Sørensen (University of Copenhagen)

for the photo of J. A. Christiansen and
to Prof. Ronald Imbihl (Universität Hannover)
for the photo of the gold wrist watch of Bodenstein