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Jubileusz metody miareczkowania kulometrycznego

Małyszko J.

Wiadomości Chemiczne

2011

[Z] 65, 5-6

345-361

In 1938, Szebellédy and Somogyi [1–7] have proposed an important methodological innovation in analytical chemistry. This methodology was termed coulometric titration. This paper presents an overview of the principles of operation and, in broad outline, applications of this methodology. Moreover, a short biography and scientific achievements of professor Laszlo Szebellédy are presented in the introduction. Chapter 1 of this review outlines the theoretical background and general description of coulometric titration. In this new technique, the electrical current generates a titrant that chemically reacts with an analyte. The amount of the analyte is determined from the quantity of the electrical charge passed until the point of chemical equivalence has been reached, according to the 2nd Faraday’s law of electrolysis. The new methodology offers several significant advantages over a conventional volumetric procedure, such as elimination of problems connected with the preparation, standardization and storage of standard solutions. In Chapter 2, an evolution of the method after the Second World War is presented. In these times, stable constant current sources became easy to construct [13–15]. Consequently, coulometric titrations started to use a constant current system. Under these conditions, the total number of coulombs consumed can be calculated readily from the intensity of current and the duration of electrolysis. Coulometric titrations have been developed for all types of volumetric titrations: oxidation–reduction [19–28], precipitation [17, 18], complex formation [37] and neutralization reactions [39, 40]. The generation of various titrants and possibilities of application are described. Special attention is devoted to the electrochemical generation of reagents which are not ordinarily utilized in conventional volumetric analysis owing to the instability of their solutions such as bromine, chlorine, silver(II) and titanium(III). Moreover, the coulometric titration procedure is significantly more sensitive than the volumetric titration, and it is particularly suited to automation, because complex mechanical devices such as an automatic burette are not required. The new method appeared to be an attractive alternative to all forms of the volumetric titration. Chapter 3 is dedicated to the contribution of Polish academic chemistry teachers to the development of the method discussed [57–89, 91–100]. Advantages and disadvantages of the method are listed in the last Chapter (Summary). Each Chapter includes selected works related to the history of the subject.