Mechanism of Solid/Liquid Interfacial Reactions. The Hydrolytic Dissolution of Solid Triphenylmethyl Chloride in Aqueous Solution
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- 作者：Kin Yip Tam ; Richard G. Compton ; John H. Atherton ; Colin M. Brennan ; and Robert Docherty
- 刊名：Journal of the American Chemical Society
- 出版年：1996
- 出版时间：May 8, 1996
- 年：1996
- 卷：118
- 期：18
- 页码：4419 - 4426
- 全文大小：459K
- 年卷期：v.118,no.18(May 8, 1996)
- ISSN：1520-5126
文摘
The reaction between solid triphenylmethyl chloride(TPMCl) and water, TPMCl(s) + H2O(l) 
TPMOH(aq) + H+(aq) + Cl-(aq), whereTPMOH is triphenylmethyl alcohol, has been investigated using thechannel flowcell method. It is found that hydrolysis proceeds via a directheterogeneous fashion whereby the reaction occursatthe solid-liquid interface rather than in solution after the priordissolution of TPMCl. Kinetic parameters are reportedincluding the effect of ionic strength. Further, using experimentsconducted with different surfaces of single crystalsof TPMCl, it is shown that the rate of the interfacial process dependson the availability of exposed chlorine atomsin the reacting crystal plane. In situ atomic force microscopicstudies indicate that the TPMCl surface, once incontact with water, is covered rapidly by a porous product layer.However, the latter provides a negligible effect onthe reaction rate because of its high porosity.
TPMOH(aq) + H+(aq) + Cl-(aq), whereTPMOH is triphenylmethyl alcohol, has been investigated using thechannel flowcell method. It is found that hydrolysis proceeds via a directheterogeneous fashion whereby the reaction occursatthe solid-liquid interface rather than in solution after the priordissolution of TPMCl. Kinetic parameters are reportedincluding the effect of ionic strength. Further, using experimentsconducted with different surfaces of single crystalsof TPMCl, it is shown that the rate of the interfacial process dependson the availability of exposed chlorine atomsin the reacting crystal plane. In situ atomic force microscopicstudies indicate that the TPMCl surface, once incontact with water, is covered rapidly by a porous product layer.However, the latter provides a negligible effect onthe reaction rate because of its high porosity.