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建立一种电化学监测酸碱滴定 (EABT)方法 ,利用循环伏安 (CV)技术直接观测正离子基 (RH+· )酸解过程中各物种浓度的变化 ,从而得到酸性离解常数 (p KRH+· )和键异裂自由能 (ΔGhet) .所测吩噻嗪系列在二甲基亚砜和乙腈中的 p KRH+· 与文献中用间接法得到的 p KRH+· 值相当吻合 ,证实了本方法的可信度 .由于不需要间接方法所必需的中性母体分子的 p Ka 和负离子氧化电位 ,故该方法可适用于难于测定的大量有机体系 p KRH+· 常数的研究
A method for the electrochemical monitoring of acid-base titration (EABT) was established. The cyclic voltammetry (CV) technique was used to directly observe the changes of concentration of various species in the positive ion group (RH + ·) during acidolysis to obtain the acid dissociation constant (p KRH + · ) And the bond dissociation free energy (ΔGhet). The measured p KRH + of the phenothiazine series in dimethylsulfoxide and acetonitrile is in good agreement with the p KRH + value obtained by indirect method in the literature, confirming that the Credibility The method is applicable to the study of the p KRH + · constants of a large number of organic systems that are difficult to measure in that they do not require the p Ka of the neutral parent molecule and the negative ion oxidation potential necessary for the indirect method