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Gas phase chemistry of technetium and rhenium oxychlorides

The chloride and oxychloride chemistry of the group 7 elements Tc and Re was investigated in order to develop an experimental approach to a gas chemical characterisation of bohrium (Bh, element 107). In thermochromatography experiments with trace amounts of 101,104Tc and 183,184Re the formation of one volatile compound was observed in O2/HCl containing carrier gas, which was attributed to MO3Cl (M = Tc, Re). From the measured deposition temperatures the adsorption enthalpies on quartz surfaces ΔHads(TcO3Cl) = -51 ± 3 kJ/mol and ΔHads(ReO3Cl) = -62 ± 3 kJ/mol were evaluated. The sublimation enthalpies were derived using an empirical correlation between Δ Hads and ΔHsubl: ΔHsubl(TcO3Cl) = 49±10 kJ/mol and ΔHsubl(ReO3Cl) = 67±10 kJ/mol. A fast gas chemical separation technique for highly volatile compounds of short-lived isotopes based on isothermal gas solid adsorption chromatography (OLGA-principle) was developed. With a modified OLGA device, model studies with the short-lived nuclides 106,107,108Tc and 169,170,174,176Re were carried out in preparation of an experimental gas chemical investigation of bohrium (Bh, element 107). Separation times of less than 3 s were achieved. A good separation of the oxychlorides of group 7 elements from chloride and oxychloride compounds of 152-155Er, 151-154Ho (as models for actinide elements), 98-101Nb, 99-102Zr (as models for light transactinide elements), 218Po, and 214Bi was accomplished in this chemical system.