Kinetics of oxidation of pentaammine-isothiocyanato-cobalt(III) ion with peroxodisulphate and periodate in water and water-organic mixtures

Medium effect on reactions between anions carrying different charges

“…[2] where s(w) and s(x) are the solubilities in water and in the solvent mixtures, respectively. Usually, Gmpe(salt) values are calculated on the assumption that the ratio of the mean activity coefficients in water and in the aqueous solvent mixtures is in all cases a unity (28,29). However, we have calculated these ratios by means of eq.…”

“…Recently this type of analysis has been extended to multiple linear correlations to assess the relative importance of the different variables (3,4). Also, the solvent effect on log k or AG* can be dissected into contributions from the initial state and the transition state using the thermodynamic functions of transfer (5)(6)(7). This study allows an analysis of the importance of the solvation changes of both states on reactivity.…”

Solvation of inorganic complexes: transfer chemical potentials for mono- and bi-nuclear cobalt(III) complexes to methanol + water mixtures

“…Transfer chemical potentials have been reported for a number of inorganic complexes to methanol + water mixtures, including a number of low-spin iron(II) [12,13], iron(III) [13,14], platinum(II) [15], chromium(III) [13,16] and cobalt(III) complexes [16][17][18][19][20][21][22][23][24]. The cobalt complexes range from [Co(NH 3 ) 6 ] 3+ [17,18] through simple ternary complexes such as [Co(NH 3 ) 5 Br] 2+ [19], [Co(NH 3 ) 5 (NCS)] 2+ [20], [Co(NH 3 ) 4 (SO 4 )] + [21], and several thiocarboxylate complexes, e.g.…”

“…The cobalt complexes range from [Co(NH 3 ) 6 ] 3+ [17,18] through simple ternary complexes such as [Co(NH 3 ) 5 Br] 2+ [19], [Co(NH 3 ) 5 (NCS)] 2+ [20], [Co(NH 3 ) 4 (SO 4 )] + [21], and several thiocarboxylate complexes, e.g. [Co(en) 2 (SCH 2-CO 2 )] + [22], to binuclear species such as [(H 3 N) 3 Co (l-OH) 3 Co(NH 3 ) 3 ] 3+ [23] and the mixed metal complex [(en) 2 Co(l-pzc)Fe(CN) 5 ] ) [24].…”