| Autor: |
A. A. T. BAILEY, D. H. BUISSON, K. J. CRESSWELL, A. L. ODELL, (the late) R. W. OLLIFF, D. SHOOTER |
| Jazyk: |
angličtina |
| Rok vydání: |
1977 |
| Předmět: |
|
| DOI: |
10.5281/zenodo.6384697 |
| Popis: |
Urey Radiochemical Laboratory, The University of Auckland, Auckland, New Zealand. The presence of rapidly formed ion pairs has been confirmed in mixtures of the trisoxalatochromate (Ill) anion and salts or divalent metallic cations by conductometric methods. Formation constants are of the order of 102. Racemisation and aquation rate constants show linear dependence on [M2+] indicating that ion pairing is not a significant step in the raeemisation or aquation reaction sequences. This conclusion is reinforced by rate studies using mixed cationic catalysts where additivity rather than competition is observed between the effects of two catalysts. Acceleration of racemisation produced by divalent metal ions is shown to be due to entropy effects rather than enthalpy effects, and a model for this reaction involving a specifically oriented aquation sheath about the metallic cation is proposed. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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