The decomposition of CH 2 FCF 3 over some phosphate catalysts was studied. CH 2 FCF 3 began to react at 250, 300, and 450 °C over Zr 3 (PO 4 ) 4 , AlPO 4 , and BPO 4 , respectively, and the conversion reached 100% at 475, 500, and 700 °C, respectively. The primary reaction over Zr 3 (PO 4 ) 4 was estimated to be CH 2 FCF 3 + H 2 O + 1 / 2 O 2 f 2CO + 4HF, whereas the reactions over AlPO 4 and BPO 4 wereComplete decomposition requires both hydrolysis and oxidation. The oxidation activities of these phosphate catalysts are not high enough to accomplish complete decomposition. However, AlPO 4 -based catalysts can be combined with each Co 3 O 4 , Mn 2 O 3 , CuO, and Cr 2 O 3 at a phosphate content of 1/10 by volume to make them sustainable at 550-550 °C. The addition of Ce to AlPO 4 brought about a promotion effect in CH 2 FCF 3 decomposition similar to that for CCl 2 F 2 decomposition. This might suggest a similarity in the reaction mechanism. The primary reaction in the absence of oxygen was estimated to be CH 2 FCF 3 + H 2 O f CO + C + 4HF.
Summary:The photo-decomposition of sixteen organic sulfur compounds were examined by the reaction with diphenyl picryl hydrazil (DPPH) at room temperature.Application of mercury-lamp or natural light to sample sulfur compounds release free radicals. Reaction velocity considerably varies depending upon type of ultraviolet ray applied, and susceptibility to light varies depending upon chemical structure of sulfur compounds, order being identical with each type of ultraviolet ray.Under these reaction conditions, mercaptanes react most rapidly with DPPH as compared with other sulfur compounds having corresponding side chains. This reaction seems to be of hydrogen abstraction type. Disulfides decomposed more easily than corresponding sulfides.The effect of hydrocarbon side chains on reactivity of these sulfur compounds was in the following order : naphthyl>phenyl>benzyl, alkyl radicals.
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