1
514
ROZDYALOVSKAYA et al.
The dynamics of chlorine separation from the
ZnCl –V O melt is also described by the zero-order
7. US Patent 6994636.
8. Levanov, A.V., Gromov, A.P., Antipenko, E.E., et al.,
Zh. Fiz. Khim., 2000, vol. 74, no.12, pp. 2299–2300.
9. Levanov, A.V., Kuskov, I.V., Koiaidarova, K.B., et al.,
Kinet. Katal., 2005, vol. 46, no. 1, pp. 147–152.
10. Chudinov, A.N., Rozdyalovskaya, T.A., Vnutskikh, Zh.A.,
et al., Khim. Tekhnol., 2007, vol. 8, no. 11, pp. 524–528.
2
2
5
–6
–1
equation [k = (0.12 + 0.03)×10 mol s at 500°C],
with activation energy of the process virtually zero.
This shows that the oxidation rate of chloride ion is
higher than the diffusion rate of chlorine from the melt
into the gas phase.
1
1. Rozdyalovskaya, T.A., Chekryshkin, Yu.S., and Vnuts-
CONCLUSIONS
kikh, Zh.A., Rasplavy, 2004, no. 4, pp. 75–84.
1
2. Popovskii, V.V. and Boreskov, G.K., Problemy kinetiki
i kataliza (The Problems of Kinetics and Catalysis),
Moscow: Akad. Nauk SSSR, vol. 10, pp. 67–72.
(
1) The oxidation of chloride ions with atmospheric
oxygen in melts of sodium, calcium, and zinc chlorides
in the presence of transition metal oxides depends on
the type of chloride and oxide cations.
13. Andrushkevich, T.V., Boreskov, G.K., and Popovskii, V.V.,
Kinet. Katal., 1965, vol. 6, no. 5, pp. 860–863.
1
1
4. Milan, E.F., J. Phys. Chem., 1929, vol. 33. pp. 498–506.
(
2) The high correlation coefficients for the
5. Fotiev, A.A., Volkov, V.L., and Kapustkin, V.K.,
Oksidnye vanadievye bronzy (Oxide Vanadium Bron-
zes), Moscow: Nauka, 1978.
dependence of the amount of separating chlorine on
the polarization force of the oxide cations in sodium
and calcium chlorides are accounted for by their ionic
structure. The covalent bond in ZnCl is responsible
for the lack of the above dependence.
1
6. Pastukhov, E.A., Musikhin, V.I., and Vatolin, N.A.,
2
Elektricheskie
svoistva
nestekhiometricheskikh
oksidnykh rasplavov (Electrical Properties of Nonstoi-
chiometric Oxide Melts), Sverdlovsk: Ural. Nat. Tsentr,
Akad. Nauk SSSR, 1984.
ACKNOWLEDGMENTS
1
1
1
7. Silversmith, G., Poelman, H., Sack, I., et al., Catal.
Lett., 2006, vol. 107, nos. 1–2, pp. 61–71.
The study was supported by the Grant of the
President of Russian Federation (project no. MK-
8. Ostroushko, A.A., Makarov, A.A., and Minyaev, V.I.,
1
559.2008.3) and by the Russian Foundation for Basic
Zh. Prikl. Khim., 2004, vol. 77, no. 7, pp. 1136–1143.
Research (project no. 08-03-00426-а).
9. Vol’fson, V.Ya., Zhigailo, Ya.V., Totskaya, E.F., and
Raksha, V.V., Kinet. Katal., 1965, vol. 6, no. 1, pp. 162–
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