Study of the carbohalogenation process in molten KCl–NaCl equimolar mixture

• Published in: Reaction kinetics, mechanisms and catalysis mechanisms and catalysis, 2015-12, Vol.116 (2), p.327-337
• Main Authors: Cherginets, Victor L., Rebrova, Tatyana P., Ponomarenko, Tamara V., Naumenko, Vyacheslav A., Bryleva, Ekaterina Yu
• Format: Article
• Language: English
• Subjects: Catalysis; Chemistry; Chemistry and Materials Science; Industrial Chemistry/Chemical Engineering; Physical Chemistry
• ISSN: 1878-5190; 1878-5204
• DOI: 10.1007/s11144-015-0905-5

The process of the removal of oxide ions to the gaseous phase from molten KCl–NaCl equimolar mixture using tetrachlorometane vapor was studied by a potentiometric process using Pt(O 2 )|YSZ oxygen electrode for the detection of oxide ion concentration. The chemical stage of the interaction of CCl 4 with oxide ions (carbohalogenation) in the molten KCl–NaCl equimolar mixture at 953, 973, 1000 and 1023 K is characterized by second order kinetics with respect to oxide ions. The temperature dependence of the rate constant is described by the equation: ln k  = 43 (±4) − (24,800 ± 3800) T −1 , which permits the estimation of the activation energy as 206 ± 30 kJ mol −1 . The purification limit of molten KCl–NaCl equimolar mixture from oxygen-containing admixtures in the studied temperature range decreases from 2 × 10 −9 to 3 × 10 −10  mol kg −1 of O 2− with the rise of the melt temperature from 953 to 1023 K.