Abstract
Solubilities of four methyl halides at 29.4 deg and 40.3 deg are nearly the same in H2O as in D2O. Evidently these solutes fit into holes in the water, without either freeing or restricting the motion of surrounding water molecules. Since initial-state isotope effects are so small, calculated transition-state isotope effects for hydrolysis are nearly equal to the observed kinetic isotope effects. Methyl chloride is more ionized than methyl bromide at the transition state in solvolysis in water at 40-70 deg .
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