THE REACTION OF WHITE PHOSPHORUS WITH CARBON TETRACHLORIDE UNDER THE INFLUENCE OF $gamma$ RADIATION, LIGHT AND HEAT (in German)
Red phosphorus, phosphorus trichloride, trichloromethylphosphorus dichloride, hexachloroethane, and a polymer consisting of carbon and chlorine are formed when solutions of white phosphorus in carbon tetrachioride are exposed to gamma -radiation. Red phosphorus is the main product at room temperature. However, its yield rapidly decreases at higher temperatures and the yields of the low molecular weight products strongly increases. Typical G-values are given. The formation of the products PCl/sub 3/ and CCl/sub 3/PCl/sub 2/ occurs by a chain reaction between phosphorus and carbon tetrachloride. A mechanism is proposed in which free radicals from the radiolysis of carbon tetrachloride attach the dissolved white phosphorus. The propagation of the chain is caused by chlorine transfer from carbon tetrachloride to partly trichloroalkylated or chlorinated phosphorus chains or rings. The activation energy of this transfer is found to be equal to 8.2 kcal/mole. This reaction with carbon tetrachloride is favored at high temperature whtle the competing process of the combination of those intermediate phosphorus chains and rings to give red phosphorus predominates at low temperature. The red phosphorus formed contains one CCl/sub 3/ group per 7 atoms of phosphorus. It was possible to synthesize tricltloromethylphosphorus dichioride, trichloromethylphosphorus tetrachloride and trichloromethylphosphorus dibromide by treating the red phosphorus with chlorine or bromine, respectively. The thermal reaction between phosphorus and carbon tetrachloride also leads to PCl/sub 3/ and CCl/sub 3/PCl/sub 2/ (ratio 1 : 3). Small amounts of red phosphorus and C/sub 2/Cl/sub 6/ could be traced too. The activation energy of the thermal reaction amounts to 22.2 kcal/moles. The photo reaction (visible light) leads to the same products. However, red phosphorus still is the main product at 100 deg C. (auth)
- Research Organization:
- Hahn-Meitner-Institut fur Kernforschung, Berlin
- NSA Number:
- NSA-17-006167
- OSTI ID:
- 4736884
- Journal Information:
- Zeitschrift fuer Naturforschung (West Germany) Divided into Z. Nautrforsch., A, and Z. Naturforsch., B: Anorg. Chem., Org. Chem., Biochem., Biophys.,, Vol. Vol: 17b; Other Information: Orig. Receipt Date: 31-DEC-63
- Country of Publication:
- Country unknown/Code not available
- Language:
- German
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