ChE 125 Weekly Computer Activity Department of Chemical Engineering

01 February 2018 University of the Philippines Diliman

Nonelementary Reaction Kinetics

Rice and Herzfeld1 (1934) postulated the detailed mechanism of thermal decomposition of gaseous
organic compounds which is very important in the study of pyrolysis reactions. The mechanism
consists of an initiation step that forms free radicals, then propagation steps, and finally termination
step that destroy the free radicals.

The first step is the decomposition of the molecule into two radicals by dissociation of a carbon –
carbon bond:

𝑘1
Initiation: 𝑀 → 𝑅1 ∙ + 𝑅1′ ∙

The radical 𝑅1′ ∙ is not involved in the propagation but 𝑅1 ∙ participates in the following chain reaction,

𝑘2
Propagation 1 𝑅1 ∙ + 𝑀 → 𝑅2 ∙ + 𝑅1 𝐻
𝑘3
Propagation 2 𝑅2 ∙ → 𝑅1 ∙ + 𝑃1

In Propagation 1, 𝑅1 ∙ abstracts a hydrogen from M and forms the radical 𝑅2 ∙ and a small saturated
molecule. In Propagation 2, 𝑅2 ∙ dissociates at a carbon – carbon bond and regenerates the free radical
𝑅1 ∙.

The sequence continues until one of the following termination steps occurs:

𝑘4𝑎
Termination a 𝑅1 ∙ + 𝑅2 ∙ → 𝑃3
𝑘4𝑏
Termination b 𝑅2 ∙ + 𝑅2 ∙ → 𝑃4

Under a given set of experimental conditions, only one of the termination steps (a) and (b) can be
expected to be important.

1. Show using steady –state approximation approach that the disappearance of reactant M is
a/an:

a. Half order rate expression if Termination b is the chain – breaking step

b. First order rate expression if Termination a is the chain – breaking step

In your derivation, you may assume that the long-chain approximation is valid (i.e. that the
rates of the propagation reactions are much greater than the initiation reaction). However, you
should be careful not to make this assumption too soon. Otherwise, some simplifications will
not arise in the normal course of the analysis.

1 Rice, F. 0., and Herzfeld, K. F., J. Am. Chem. Soc., 56, 284 (1934).
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2. An experiment was conducted to assess the validity of the Rice-Herzfeld mechanism using
ethane (C2H6) as the gaseous organic compound. At 700℃, ethane (C2H6) decomposes into
ethylene (C2H4) and hydrogen (H2). Test the following experimental data to determine the
possible termination step of the decomposition of ethane. What is the corresponding value and
units of the rate constant?

Concentration of Rate of consumption of

ethane (mol/m3) ethane (mol/m3 s)
0.00785 0.2413
0.0118 0.3615
0.0177 0.5421
0.0197 0.6028
0.0236 0.7215
0.0296 0.9039
0.0315 0.9616

3. The effect of temperature was investigated on the rate constant for the thermal decomposition
of ethane. The following experimental data were obtained:

Temperature (℃) 508 427 393 356 283

Rate constant 0.1059 0.0031 0.00058 80.9 x 10-6 0.942 x 10-6
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Determine the activation energy and the frequency factor of the reaction if it follows
(a) Arrhenius Law, (b) Collision Theory, (c) Transition-state Theory.