Add time:07/23/2019         Source:sciencedirect.com

Thermodynamic data for equilibria involved int he overall hydrolytic process of the cis-[Pd(en)(H2O)2]2+ complex in the presence or absence of chloride ion are reported. All expected hydrolytic species are taken into account to calculate their formation constants and to fit the equilibrium model. The formation constants (log βpqr) of aqua and/or hydroxo complexes were obtained from E(H+) data of alkalimetric titrations of cis-[Pd(en)(H2O)2](ClO4)2 solutions. The log βpqr balues of chloro-containing complexes were obtained from E(H+) and E(Cl−) data pairs, taking into account the above log β data as fixed values. All formation constants were fitted by SUPERQUAD calculations: log βpqr for cis-aqua-hydroxo (cis=10−1, −6.68(10))), di-μ-hydroxo (20−2, −7.758(4), cis-dihydroxo (10−2, −14.523(4)), cis-dichloro (120, 5.24(1)), cis-chloro-aqua (110, 3.18(1)) and cis-chloro-hydroxo (11−1, −3. 75(4)) specieis for I=0.15 mol dm−3 in NaClO4 and t=37°C. This constant set allows good simulation of experimental titration curves and is used to obtain a variety of species distribution diagrams.

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