Adsorption and oxidation of aniline and anisidine by chromium ferrocyanide

The interaction of aniline and p-anisidine with chromium ferrocyanide has been studied. Maximum uptake of both anilines was observed around pH 7. The adsorption data obtained at neutral pH were found to follow Langmuir adsorption. Anisidine was a better adsorbate because of its higher basicity. In alkaline medium (pH > 8) both aniline and anisidine reacted with chromium ferrocyanide to give colored products. Analysis of the products by GC-MS showed benzoquinone and azobenzene as the reaction products of aniline while p-anisidine afforded a dimer: IR analysis of the amine-chromium ferrocyanide adduct suggests that the outer metal ion of chromium ferrocyanide and amino group of amines are responsible for the interaction. A possible reaction mechanism for the product formation in alkaline medium has been proposed. The present study suggests that metal ferrocyanides might have played an important role in the stabilization of organic molecules through their surface activity in the prebiotic condensation reactions. (C) 2002 Elsevier Science.