Effect of chloride melt acidity on kinetics of the carbochlorination process

doi:10.26565/2220-637X-2013-22-13

Victor L. Cherginec V.N. Karazin Kharkiv National University
Vyacheslav A. Naumenko V.N. Karazin Kharkiv National University
T. V. Ponomarenko
T. P. Rebrova

DOI: https://doi.org/10.26565/2220-637X-2013-22-13

Keywords: melts, alkali metal chlorides, barium chloride, potentiometry, rate constant, oxide ions

Abstract

The carbochlorination (purification from oxide ion traces) of KCl-NaCl, KCl-BaCl₂ and KCl-LiCl eutectics by products of pyrolysis of tetrachlormethane at 973 K is studied by a potentiometric method with the use of a membrane oxygen electrode. The process of carbochlorination of the studied melts is characterized by the second order with respect to O^2–. The rate constants (kg·mol^-1·min^-1) and limits of purification pO_lim (pO=-lgm_O2-) decrease in the following sequence: KCl-NaCl (k=2.41×10⁷, pO_lim=8.8)→KCl-BaCl₂(k=1.08×10⁵, pO_lim=6,6)→KCl-LiCl(k=6.76×10³, pO_lim=5.3). Correlations of lgk and pO_lim with pI_L (the concentration analog of lgγ_0,O2-) are practically linear, that allows to estimate the effectiveness of purification of chloride melts possessing different acidities.

Downloads

Download data is not yet available.

References

Lebl M., Trnka J. Entfernung von Sauerstoff-heltigen Anionen aus Alkalihalogeniden // Z.Phys.-1965.-Bd.186, №2.-P.128-136.

Cherginets V.L., Rebrova T.P., Ponomarenko T.V., Kisil E.P., Filippovich L.I. Oxoacidic properties of melts of CsCl-LiCl-YCl3 system and features of their purification from oxide ion traces // J.Chem.Eng.Data.-2011.-V.56, No.10.-P.3897-3901.

Cherginets V.L., Rebrova T.P., Ponomarenko T.V. // Visn. Hark. Nac. univ., 2012, Ser. Him., issue 21(44), P. 313-318. [ISSN 2220-637X (print), ISSN 2220-6396 (online), http://chembull.univer.kharkov.ua/archiv/2012/36.pdf] [in Russian].

Cherginets V.L., Naumenko V.A., Ponomarenko T.V., Rebrova T.P. // Polythermal investiga-tion of process of KCl-NaCl eutectic purification from oxide ion admixtures by carbochlorina-tion method // Problems of Chemistry and Chemical Technology.-2012.-No 5.-P.154-157 [In Russian].

Cherginets V.L. Chemistry of oxocompounds in ionic melts.-Kharkov: Institute for Single Crystals, 2004.-279 p.