The oxidation rate of TiCI4 vapor was measured by FTIR spectroscopy between 700" and 1000°C in a furnace aerosol reactor. The reaction rate was found to be first order with respect to TiC14 and to follow the Arrhenius form. The apparent activation energy for the reaction was 88.8 f 3.2 kJ/mol and the preexponential factor 8.26 X lo4 s-'. A kinetic mechanism for the oxidation of TiCI4 was proposed that was consistent with the observed dependence of oxygen concentration on the apparent rate constant. [
Both 1:l and 1:2 molecular complexes of (CH3)2Zn with NH3, PH3, AsH3, H20, H2S, and H2Se have been formed, isolated, and characterized in argon matrices and cryogenic thin films. The reactivity of these systems varied greatly, from very rapid with HIS and H2Se to very slow (and low product yield) for PH3 and AsH3. Infrared spectra of these complexes showed perturbations to a number of vibrational modes of the acid and base subunits, the most sensitive of which was the intense ZnC2 antisymmetric stretch near 600 cm-I. This mode shifted between 8 and 34 cm-1 to the red in the different complexes; the shifts correlated well with the proton affinities of the bases. Cryogenic thin film experiments permitted initial formation and trapping of the 1 : 1 complex, while warming the film led (in some cases) to 1 :2 complex formation and then ultimately dissociation.The dissociation temperature correlated well with the shift of the ZnC2 antisymmetric stretch, suggesting that both are related to the bond strength in the complex.
Matrix isolation and cryogenic thin film approaches have been employed for the synthesis, isolation, and characterization of 1:l and 1:2 complexes of (CH3)2Zn with CH30H and CH3SH. These complexes were characterized by a shifting of certain sensitive vibrational modes of the acid and base subunits in the complex. The ratio of the 1: 1 and 1:2 complexes could be altered by changing the relative amounts of the two reagents employed in a given experiment or by warming the cryogenic thin film from 14 K to as high as 200 K.Merged jet mixtures of (CH3)2Zn with either CH30H and its isotopomers or CH3SH were also pyrolyzed at temperatures as high as 370 "C. For the (CH3)2Zn/CH3OH pair, significant production of C& and CH20 was observed with minor amounts of C2H4. In the (CHs)2Zn/CH3SH experiments a substantial yield of ( C H M and CH4 was obtained. These pyrolytic reactions and products have not been reported previously and may have implications for the chemical vapor deposition of ZnO and ZnS.
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