Add time:07/22/2019         Source:sciencedirect.com

Rates of dissociation of tris-(2,2′-bipyridine) iron(II) sulphate have been determined in HCl, H2SO4, HClO4 and HNO3 in aqueous and heavy water media at acid concentrations varying from 10−3M to 3M and at different temperatures. The rates converge to the same lower limit at [H+] below 10−2M and to a higher limit which is slightly dependent on the nature of the acid at [H+] above 2·0M, in all acids. The activation parameters have been determined in all acids for the lower and higher limiting rates. The enthalpy of activation is similar in all acids for both the processes (26·7 ± 0·3 kcal/mole for the lower limiting rate and 25·5 ± 0·3 kcal/mole for the upper limiting rate). The entropy of activation is lower for the lower limiting rate and is slightly dependent on the nature of the acid for higher limiting rates (9·9 and 12·9–13·8 e.u. for lower and higher limits, respectively).Kinetics in D2O and study of the equilibrium of complex formation between Fe2+ and bipyridine in aqueous solutions containing 10−3-2M HCl at 26±0·1°C and at μ = 2·0M have ruled out unambiguously the existence of protonated form of the complex in large quantities. Thus, it is confirmed that the dissociation of tris-bipyridine Fe(II) complex takes place through the intermediate formation of steady state concentrations of the half bonded species in which the bipyridine ligand is half dissociated, as postulated by Basolo et al.

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