Effect of the Length of the Hydrocarbon Chain of Adsorbed Aliphatic Acids and Alcohols on the Electron Transfer Probability

Abstract

The kinetics of redox reactions of hemin adsorbed over a monolayer of long-chain aliphatic alcohols, such as cetyl alcohol (C₁₆) and stearyl alcohol (C₁₈), and stearic (C₁₈), behenic (C₂₂), and melissic (C₃₀) acids is studied. The reaction inhibition on an alcohol monolayer (0.34 orders of magnitude per methylene group) is close to that reported in the literature. The inhibition on an acid monolayer is substantially smaller (0.2 to 0.07 orders), which is attributed to irregularity of the structure of the monolayer of carboxylic acids caused by the dissociation of carboxyl groups, especially in alkaline solutions. Violation of a regular structure of an acid monolayer is confirmed by a considerable irreversible increase in the electrode capacitance in alkaline solutions and by a decrease in the ohmic resistance of a monolayer of the longest saturated acid, i.e. triacontanoic acid. For a regular monolayer structure, when the length of an extended hydrocarbon chain defines the barrier thickness (alcohols), experimental data accord with predictions of the “superexchange” theory, which holds that the probability of a long-distance electron transfer depends on the length of the chain of covalent bonds over which the superexchange occurs. If the film structure is irregular (film thickness decreases with increasing hydrocarbon chain length (acids)), the packing of these bonds becomes essential, which allows the electron not to pass over all the bonds but to hop onto a nonbonded chain link nearby. The obtained data indicate that the electron transfer probability is defined by the electron's path, rather than by the barrier's geometrical thickness.