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Kinetic study of the electroreduction of nitrobenzene

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Abstract

A reaction kinetic study has been performed for the reduction of nitrobenzene on a Cu electrode in 1m H2SO4 in a 50∶50 (Vol%) mixture of water and 1-propanol at 27°C. The study was carried out on a rotating disc electrode for which the current-potential data were supplemented with product-concentration measurements. The resulting rate expressions represent a reaction mechanism for the reduction of nitrobenzene to aniline and p-aminophenol through the common intermediate phenylhydroxylamine, and incorporate the dependence on reactant concentration and potential for the three predominant reaction pathways. The three major reaction steps were studied independently by performing experiments in which phenylhydroxylamine only was used as the reactant to complement those experiments in which nitrobenzene was used. The kinetic expressions found from measuring the rates of the individual reactions were consistent with the results of experiments in which all the reactions were carried out simultaneously. The expressions obtained are suitable for use in reactor design, modelling and control, and of equal importance, the methodology outlined to extract kinetic parameters from the current and concentration data serves as a model for application to other reaction systems.

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Abbreviations

A :

electrode area (cm2)

D :

diffusion coefficient (cm2 s−1)

E :

electrode potential (V)

F :

Faraday's constant, 96485 (C mol−1)

i H :

current density due to the hydrogen evolution reaction (A cm−2)

I :

current (A)

I k :

kinetic current (A)

I L :

limiting current (A)

k 1 :

rate constant for the reduction of nitrobenzene to phenylhydroxylamine (cm s−1)

k 2 :

rate constant for the reduction of phenylhydroxylamine to aniline (cm s−1)

k 3 :

rate constant for the rearrangement of phenylhydroxylamine to p-aminophenol (s−1)

n :

number of electrons per equivalent

T :

temperature (K)

X :

fractional conversion of phenylhydroxylamine to p-aminophenol

δ i :

diffusion layer thickness of speciesi (cm)

κ:

conductivity (cm−1 ohm−1)

μ:

viscosity (g cm−1 s−1)

ν:

kinematic viscosity (cm2 s−1)

ρ:

density (g cm−3)

ω:

rotation speed of electrode (s−1)

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Correspondence to P. S. Fedkiw.

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Nolen, T.R., Fedkiw, P.S. Kinetic study of the electroreduction of nitrobenzene. J Appl Electrochem 20, 370–376 (1990). https://doi.org/10.1007/BF01076043

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Keywords

  • Aniline
  • Kinetic Study
  • Nitrobenzene
  • Reaction Pathway
  • Reaction Step