Solubilities in aqueous mixtures oft-butanol andtrans-dichlorotetra(3-alkylpyridine) cobalt(III) hexachlororhenate(IV): Gibbs energies of transfer of the complex cations |
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| Authors: | Gehan M El-Subruiti Cecil F Wells Ibrahim M Sidahmed |
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| Institution: | (1) School of Chemistry, University of Birmingham, Edgbaston, B15 2TT Birmingham, England;(2) Chemistry Department, Faculty of Science, Alexandria University, Alexandria, Egypt |
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| Abstract: | The solubilities of the hexachlororhenate(IV) salts of the complex cations trans-Co(3Mepy)4Cl2]+ and trans-Co(3Etpy)4Cl2]+ have been determined in water+t-butyl alcohol mixtures. By reference to the solubilities of Cs2ReCl6 and the Gibbs energies of transfer of Cs+ from water into water+t-butyl alcohol mixtures,  G
t
o
(Cs+), G
t
o
Co(3Mepy)4Cl
2
+
] and G
t
o
Co(3Etpy)4Cl
2
+
] are calculated. These latter values, when introduced into the equation for a free energy cycle applied to the process of the initial state going to the transition state for the solvolyses of these two cations, produces values for G
t
o
Co(3Mepy)4Cl2+*] and G
t
o
Co(3Etpy)4Cl2+*] for the Co3+ cations in the transition state. These values are compared with (G
t
o
(i) for i=Co(Rpy)4Cl2]+, Co(Rpy)4Cl]2+*, Coen2XCl]+ and Coen2X]2+* to investigate the influence of the hydrophobicity of the surface of the complex on its stability in the mixtures. G
t
o
(i) (solvent sorting) are compared with G
t
o
(i) (TATB). |
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| Keywords: | Solubilities cobalt(III) complexes Gibbs energies of transfer solvolysis rates |
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