THE REACTION OF WHITE PHOSPHORUS WITH CARBON TETRACHLORIDE UNDER THE INFLUENCE OF $gamma$ RADIATION, LIGHT AND HEAT (in German)
Journal Article
·
· Zeitschrift fuer Naturforschung (West Germany) Divided into Z. Nautrforsch., A, and Z. Naturforsch., B: Anorg. Chem., Org. Chem., Biochem., Biophys.,
OSTI ID:4736884
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.,, Journal Name: Zeitschrift fuer Naturforschung (West Germany) Divided into Z. Nautrforsch., A, and Z. Naturforsch., B: Anorg. Chem., Org. Chem., Biochem., Biophys., Vol. Vol: 17b; ISSN ZNTFA
- Country of Publication:
- Country unknown/Code not available
- Language:
- German
Similar Records
The Reaction of Whtie Phosphorus with Carbon Tetrachloride under the Influence of *gamma/ Rays and Neutrons and Also the Exchange of Phosphorus Atoms Between White Phosphorus and Phosphorus Trichloride (thesis); DIE REAKTION DES WEISSEN PHOSPHORS MIT TETRACHLORKOHLENSTOFF UNTER DEM EINFLUSS VON *gamma/-STRAHLUNG UND NEUTRONEN SOWIE DER AUSTAUSCH VON PHOSPHORATOMEN AWISCHEN WEISSEM PHOSPHOR UND PHOSPHORtrichlorid
THE THERMAL AND GAMMA INDUCED PHOSPHORUS EXCHANGE BETWEEN PHOSPHORUS AND PHOSPHORUS TRICHLORIDE
IONIZATION AND DISSOCIATION PROCESSES IN PHOSPHORUS TRICHLORIDE AND DIPHOSPHORUS TETRACHLORIDE
Technical Report
·
Mon Dec 31 23:00:00 EST 1962
·
OSTI ID:4163276
THE THERMAL AND GAMMA INDUCED PHOSPHORUS EXCHANGE BETWEEN PHOSPHORUS AND PHOSPHORUS TRICHLORIDE
Journal Article
·
Mon Dec 31 23:00:00 EST 1962
· Radiochimica Acta (West Germany)
·
OSTI ID:4712826
IONIZATION AND DISSOCIATION PROCESSES IN PHOSPHORUS TRICHLORIDE AND DIPHOSPHORUS TETRACHLORIDE
Journal Article
·
Mon Jan 21 23:00:00 EST 1963
· Journal of Physical Chemistry (U.S.)
·
OSTI ID:4723252