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KMID : 1059519870310050375
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Journal of the Korean Chemical Society
1987 Volume.31 No. 5 p.375 ~ p.381
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Pressure Effect on the Aquation of trans-[Cr(tn)2Cl2]+ and trans-[Cr(en)(tn)Cl2]+ Complex Ions
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Chung Jong-Jae
Choi Jong-Ha
Kim Deog-Jin
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Abstract
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Rates for the aquation of trans-[Cr(tn)2Cl2]+ and trans-[Cr(en)(tn)Cl2]+ ions in aqueous acidic solution have been measured by spectrophotometric method at various temperatures and pressures. Activation volumes are negative and lie in the limited range -1.7 ∼ -2.9cm3mol-1 or the complex ions. Activation entropies and activation compressibility coefficients are small negative values. From the results of thermodynamic parameters, it can be inferred that the aquation of the complex ions proceed through an associative interchange(Ia) mechanism. Furthermore, the information on possible transition state structure and reaction paths can be obtained by considering total stabilization energy of the hypothetical intermediates within the framework of angular overlap model. It is found that the theoretically predicted mechanism is consistent with the experimentally observed results.
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