Effect of D2O on the rate and activation parameters of the dissociation of tris(2,2′bipyridine) and tris-(1,10-phenanthroline)Fe(II) complexes in HCl

Add time:07/21/2019    Source:sciencedirect.com

The rates of dissociation of tris(2,2′bipyridine)Fe(II) tris-(1,10-phenanthroline)Fe(II) complexes are lower in D2O at 1.0 and 0.01 N HCl, by about 10-20% Gibb's free energy of activation in all the cases is higher in D2O. Differencies in enthalpy and entropy of activation are insignificant. However, the variation of rate with the percentage of D2O), and the applicability of Barclay-Butler relationship between (ΔH≠)H2O → D2O and (ΔS≠)H2O strongly suggest that differences in rates are primarily due to differences in the free energy of salvation of the initial and transition states in H2O and D2O.

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