High-performance liquid chromatography of substituted p-benzoquinones and p-hydroquinones. I. Interplay of on-column redox reaction and the chromatographic retention process.
Chromatograms exhibiting unusual elution profiles were obtained in the reversed-phase chromatography of methoxy-substituted hydroquinones with hydro-organic mobile phases. The dependence of the elution profiles on the flow-rate and the mass of injected sample indicated that peaks were caused by the interplay of the chromatographic retention process and the concomitant oxidation of hydroquinones in the chromatographic column. The reaction was first investigated in free solution and the first-order rate constants and equilibrium constants were estimated for the oxidation of 2-methoxy-, 2,5-dimethoxy-, 2,6-dimethoxy-, 2,3,5-trimethoxy- and 2,3,5,6-tetramethoxyhydroquinones. The effect of Fe3+ and Cu2+ on the oxidation of 2,6-dimethoxyhydroquinone was also examined and it was found that Fe3+ caused a ten-fold increase in the reaction rate. The oxidation of 2-methoxy- and 2,6-dimethoxyhydroquinones in the chromatographic column showed first-order and zerothorder kinetic behavior at low and high sample loads, respectively. Such change in reaction order is typical for heterogeneous reactions that follow Langmuir-Hinshelwood kinetics and suggests the existence of catalytically active sites on the silica. Upon purging the columns with EDTA, on-column oxidation of the hydroquinones was attenuated so that no reaction zones appeared on the chromatogram. Subsequent loading of the column with Fe3+, however, gave rise to broad reaction zones and possibly to total conversion of the hydroquinones to benzoquinones in the column. In all cases investigated the rate of oxidation was much higher in the column than in free solution. On the basis of the results obtained here, heavy mental-catalyzed reaction at the stationary phase surface is proposed to be the dominant mechanism for the oxidation reaction examined here.
D016227:Benzoquinones; D055598:Chemical Phenomena; D002621:Chemistry; D002851:Chromatography, High Pressure Liquid / Q000379:methods; D006873:Hydroquinones / Q000032:analysis*; D007700:Kinetics; D010084:Oxidation-Reduction; D011809:Quinones / Q000032:analysis*; D012996:Solutions
D016227:Benzoquinones; D006873:Hydroquinones; D011809:Quinones; D012996:Solutions; C004532:quinone