Mixed halides of mercury (II)

Abstract The solid-state reactions (i) Hg2F2(s) + Br2(g), (ii) Hg2F2(s) + I2(g), (iii) Hg2Cl2(s) + Br2(g), (iv) Hg2(CH3COO)2(s) + Br2(g), (v) Hg2(CH3COO)2(s) + I2(g) and (vi) Hg2I2(s) + Br2(g) have been investigated. Reactions (i)–(v) yield HgFBr, HgFI, HgClBr, Hg(CH3COO)Br and Hg(CH3COO)I respectively. In reaction (vi) HgBrI is an intermediate product which subsequently reacts with Br2(g) to produce HgBr2(s) and I2(g). The identity of the reaction product has been confirmed by X-ray powder diffraction data and the thermal stability data is consistant with thermodynamic predictions. It is found that HgFI undergoes photochemical decomposition in CCl4. The quantum yield was found to be of the order of 3 × 10−3 molecules/photon. Results suggest the following equilibria, . Solid-state kinetics for reactions (i)–(v) were studied. The energies of activation were found to be 17·2, 14·2, 7·2, 8·0 and 6·0 kcal/mole, respectively.