TG study on the chlorination of MoO2 by CCl4 View Full Text


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Article Info

DATE

1995-04

AUTHORS

I. S. Pap, G. Mink, A. Auroux, E. Karmazsin

ABSTRACT

Molybdenum-dioxide samples were produced by reduction of MoO3 in flowing H2. The chlorination kinetics of the pure crystalline MoO2 and samples containing a mixture of Mo-oxides were studied by thermogravimetry, using gaseous CCl4 as chlorinating agent. The initial samples and the chlorinated residues were investigated by XRD and BET methods, as well. The pure molybdenum-dioxide sample was remarkably less reactive than the partially reduced non-stoichiometric molybdenum-oxides or MoO3. The characteristic sigmoid shape of the TG curves were explained by the difference in the reactivity of molybdenum-oxides and by the change of the specific surface area during chlorination. The observed reaction order ofn=0.5 suggests a fast, reversible dissociative adsorption of CCl4 before the volatilization step. For samples of low specific surface area activation energies of 123 and 97 kJ·mol−1 were obtained, and the kinetic curves could be well fitted by an Avrami-Erofeev equation. For sample of much higher specific surface area a diffusion controlled reaction (Ea=52 kJ·mol−1) was supposed, and the kinetic model of contracting spheres could be applied. More... »

PAGES

847-854

Identifiers

URI

http://scigraph.springernature.com/pub.10.1007/bf02547269

DOI

http://dx.doi.org/10.1007/bf02547269

DIMENSIONS

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