Collect. Czech. Chem. Commun. 1980, 45, 21-25

Kinetics and mechanism of oxidation of Cr(II) ions by tetrachloromethane

Peter Ševčík and Miroslav Khír

Department of Physical Chemistry, Comenius University, 816 31 Bratislava


Kinetics of the redox reaction of Cr(II) ions with tetrachloromethane has been studied in H2O-CH3OH-HClO4 and H2O-CH3COOH-HClO4. In the redox reaction 2 moles of Cr(II) are consumed per one mol of CCl4, and CrCl2+ and CrCCL2+3 ions are formed in the same amounts. Second order rate constants (k293 = 2.31 mol-1 s -1 in 50% CH3OH, k293 = 1.66 l . mol-1 s-1 in 50% CH3COOH) are independent of H+ ions concentration.The rate determining step is an inner sphere transfer of the halogen from CCl4 to Cr(II), the Cr-Cl-C bridge structure being retained in both media.