Results are reported of three‐electrode measurements in sodium polysulfide melts. The composition range covered was
Na2S3‐Na2S5
and the temperature range 300°–400°C. The electrode material used was vitreous carbon. Voltammetric, chronopotentiometric, and current interruption techniques were used to investigate cathodic and anodic processes. Evidence is produced that sulfide films are formed at the cathode and that these result in limiting currents. The lowest value of limiting current density was 28 mA · cm−2 obtained for
Na2S3
at 350°C. At the anode the current appears to be limited by accumulation of liquid sulfur. The value of the limiting current density in
Na2S5
was 100 mA · cm−2 at 350°C. A reaction scheme which best fits our results is suggested.
A reaction scheme is proposed which accounts for the main kinetic characteristics of the polycondensation of benzyl chloride under the catalytic action of stannic chloride. The reaction scheme, which requires three consecutive and competing rate-determining steps, can account quantitatively for the induction period, the pseudofirst-order reaction period, the apparent inhibition of the reaction by high concentrations of catalyst, and the degree of polymerisation attained. The polycondensation of benzyl chloride in the presence of Bryce-Smith magnesium compounds has been studied, and evidence has been found which confirms that the true catalyst is produced as a result of reaction between alkylmagnesium and benzyl chloride.
Die Untersuchung wird mit einer Drei‐Elektroden‐Anordnung in Na‐polysulfid‐ Schmelzen (Zusammensetzungsbereich Na2S3‐Na2S5) bei Temperaturen zwischen 300 und 400°C durchgeführt.
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