29.

7: Some Reaction Mechanisms Involve Chain Reactions

A large number of reactions proceed through a series of steps that can collectively be classified as a chain reaction. The
reactions contain steps that can be classified as
initiation step – a step that creates the intermediates from stable species
propagation step – a step that consumes an intermediate, but creates a new one
termination step – a step that consumes intermediates without creating new ones
These types of reactions are very common when the intermediates involved are radicals. An example, is the reaction

H2 + Br2 → 2H Br (29.7.1)

The observed rate law for this reaction is

3/2
k[ H2 ][Br2 ]
rate = (29.7.2)
′
[Br2 ] + k [H Br]

A proposed mechanism is
k1
⋅
Br2 ⇌ 2Br (29.7.3)
k−1

k2
⋅ ⋅
2Br + H2 ⇌ H Br + H (29.7.4)
k−2

k3
⋅ ⋅
H + Br2 −
→ H Br + Br (29.7.5)

Based on this mechanism, the rate of change of concentrations for the intermediates (H and Br ) can be written, and the ⋅ ⋅

steady state approximation applied.

⋅
d[ H ]
⋅ ⋅ ⋅
= k2 [Br ][ H2 ] − k−2 [H Br][ H ] − k3 [ H ][Br2 ] = 0 (29.7.6)
dt

⋅
d[Br ]
⋅ 2 ⋅ ⋅ ⋅
= 2 k1 [Br2 ] − 2 k−1 [Br ] − k2 [Br ][ H2 ] + k−2 [H Br][ H ] + k3 [ H ][Br2 ] = 0 (29.7.7)
dt

Adding these two expressions cancels the terms involving k , k , and k . The result is 2 −2 3

⋅ 2
2 k1 [Br2 ] − 2 k−1 [Br ] =0 (29.7.8)

Solving for Br ⋅

−−−−−−−
k1 [Br2 ]
⋅
Br = √ (29.7.9)
k−1

This can be substituted into an expression for the H

⋅
that is generated by solving the steady state expression for
d[ H ]/dt.
⋅

⋅
k2 [Br ][ H2 ]
⋅
[H ] = (29.7.10)
k−2 [H Br] + k3 [Br2 ]

so
−−−−−−−
k1 [Br2 ]
k2 √ [ H2 ]
k−1
⋅
[H ] = (29.7.11)
k−2 [H Br] + k3 [Br2 ]

Now, armed with expressions for H and Br , we can substitute them into an expression for the rate of production of the
⋅ ⋅

product H Br:
[H Br]
⋅ ⋅ ⋅
= k2 [Br ][ H2 ] + k3 [ H ][Br2 ] − k−2 [ H ][H Br] (29.7.12)
dt

After substitution and simplification, the result is

3/27/2020 29.7.1 https://chem.libretexts.org/link?14558

 1/2
k1
1/2
2 k2 ( ) [ H2 ][Br2 ]
[H Br] k−1
= (29.7.13)
dt k−1 [H Br]
1+
k3 [Br2 ]

Multiplying the top and bottom expressions on the right by [Br ] produces
2

1/2
k1
3/2
2 k2 ( ) [ H2 ][Br2 ]
[H Br] k−1
= (29.7.14)
dt k−1
[Br2 ] + [H Br]
k3

which matches the form of the rate law found experimentally (Equation 29.7.2)! In this case,
−−−−
k1
k = 2k2 √ (29.7.15)
k−1

and
k−2
′
k = (29.7.16)
k3

Contributors
Patrick E. Fleming (Department of Chemistry and Biochemistry; California State University, East Bay)

3/27/2020 29.7.2 https://chem.libretexts.org/link?14558