화학공학소재연구정보센터
Chemical Physics Letters, Vol.319, No.3-4, 247-252, 2000
Mechanism of hydroxide mobility
A suggested mechanism for hydroxide mobility in water identifies the fare limiting step as a cleavage of a second shell hydrogen bond which converts a H7O4- ion (triply coordinated hydroxide) to (HOHOH)(-) (deprotonated water dimer). Proton transfer is enabled by an additional O-O bond contraction, not required in H5O2+. This explains why the activation energy for hydroxide mobility is larger than that of proton mobility by about 0.5 kcal/mol. The transfer cycle is terminated by hydrogen-bond formation to the other oxygen center. Available experimental data, and most of the computational results, can be rationalized in the framework of the above model.