Akademik Veri Yönetim Sistemi
Electrochemical Science Advances, cilt.2, sa.6, 2022 (Scopus)
The electrochemical behavior of chloral hydrate in aqueous solutions at various pH values was investigated by using polarography. Reduction of chloral hydrate takes place in two steps: one appears as a small limiting current value that corresponds to the reduction of the unhydrated form, present in solutions in less than 3%, and another larger limiting current value at more negative potentials corresponding to a reduction of C-Cl bonds in the hydrated form. Reduction schemes for both the hydrated and unhydrated forms and of an oxidation process for chloral hydrate are proposed. The reduction scheme supports the stepwise removal of chloride ions from the hydrated form of chloral that is electroactive in its protonated form, yielding ethanol as the final product. A rate constant for the protonation of chloral hydrate is calculated from its measured pKa value and electrochemical data. The role of hydration-dehydration equilibria involving the reduction intermediates, which are reduced at more negative potentials than that of chloral, was concluded based on a comparison of limiting currents of chloral hydrate with those of 2,2,2-trichloroethanol. The alcohol yields, in medium pH range a diffusion-limited current, corresponding to cleavage of three C-Cl bonds. This allowed the calculation of the equilibrium constant of the hydration-dehydration equilibria.