Radiolysis of solutions of nickel chloride in methyl alcohol at 77 K

The mechanism of the low-temperature radiolysis of the solutions of nickel chloride in methyl alcohol has been investigated by means of E.S.R. and optical spectroscopy, chemical analysis and calorimetry. Nickel has been shown to be reduced to a monovalent state in the reaction of Ni(II) with electrons. Simultaneously, under irradiation a CH20H-Ni(I) complex is formed. This complex is in conformity with absorption in the region of 560 nm, and with heat evolution on the calorimetric curve of heating at 245 to 270 K. In the NiCl2.50 CH30H solutions the accumulation of hydrogen, ethyleneglycol, formaldehyde and of the complex containing a CH20H radical proceeds linearly with increasing dose with yields 1.3, 1.3, 0.2 and 2.5, respectively. At the initial stages of radiolysis the yield of the monovalent nickel is 0.7 1/100 eV. It is concluded that the major part of radicals is formed in the first sphere of the solvating shell of ion. (author)