计时库伦-理论.pdfVIP

Chapter II.4 Chronocoulometry György Inzelt II.4.1 Introduction In 1834 Faraday suggested two fundamental laws of electrolysis. According to Faraday, the amount of material deposited or evolved (m) during electrolysis is directly proportional to the current (I) and the time (t), i.e., on the quantity of elec- tricity (Q) that passes through the solution (first law). The amount of the product depends on the equivalent mass of the substance electrolyzed (second law). (In fact, Faraday’s laws are based on two fundamental laws, i.e., on the conservation of matter and the conservation of charge.) Accordingly, M MIt m = Q = (II.4.1) nF nF where Q in the amount of charge consumed during the electrochemical transforma- tion, n is the charge number of the electrochemical cell reaction, I is the current, and t is the duration of electrolysis. If the current efficiency is 100%, i.e., the total charge is consumed only by a well- defined electrode reaction, the measurement of charge provides an excellent tool for both qualitative and quantitative analyses. For instance, knowing m and Q, M/n can be obtained, which is characteristic to a given substance and its electrode reaction. By knowing M and n the amount of the substance in the solution can be deter- mined. This method is known as coulometry. It is also possible to generate a reactant by electrolysis in a well-defined amount and then it will enter a reaction with a component of the solution. It is used in coulometric titration where the end-point is detected in a usual way, e.g., by using an indicator. Chronocoulometry belongs to the family of step techniques. The essential fea- tures of chronoamperometry have already been discussed in Sect. I.3.2. Instead of fol