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KMID : 1059519880320050436
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Journal of the Korean Chemical Society
1988 Volume.32 No. 5 p.436 ~ p.442
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Kinetic Study of Proton Exchange between Al(H2O)63+ Ion and Bulk Water Molecules (Ⅰ)
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Cho Moon-Hwan
Kim Jin-Ho
Yoon Chang-Ju
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Abstract
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The 1H-nmr lineshapes of H2O in the solution containing Al3+ ion have been measured as a function of temperature and H+-ion concentration. Above [H+] = 0.06, the lineshape were analyzed by the uncoupled two-site exchange model. From the proton exchange rate between hexaaquaaluminium ion and bulk water as a function of H-ion concentration. These kinetic data could be fitted to a following linear rate law; that is; 1/τ = k1/12 + k2[H+]/6. The following proton exchange parameters were obtained; k1298 = 38.5s-1 ΔH1≠ = 42.9kJ mole-1 ΔS1≠ = -48.6J mole-1 K-1 k2298 = 172s-1mole-1 ΔH2≠ = 27.8kJ mole-1 ΔS2≠ = -90.3J mole-1 K-1 These activation parameters are indicating an associative interchange, Ia, mechanism for the acid-hydrolysis of hexaaquaaluminium ion and the proton exchange between the hydration spheres of Al3+ and H+.
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KEYWORD
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