US EPA

8451909 

Journal Article 

Conversion of Liquid White Phosphorus to Red Phosphorus. I. Kinetics of the Reaction 

Dewitt, TW; Skolnik, S 

1946 

Yes 

Journal of the American Chemical Society
ISSN: 0002-7863
EISSN: 1520-5126 

68 

11 

2305-2309 

English 

10.1021/ja01215a052 

The kinetics of the thermal conversion of liquid white phosphorus to red phosphorus was studied experimentally. The reaction was found to be strictly first order in the temperature range 250 to 350° with an energy of activation of 37,800 calories per mole. The addition of small amounts of iodine or sulfur to liquid white phosphorus markedly accelerated its thermal conversion to red phosphorus. The accelerative effect was pronounced in the initial stages of the conversion but soon disappeared, and the conversion continued at a rate comparable to that in the absence of accelerators. A rate law was derived for the reaction. In the early stages of the conversion, the reaction mixture consisted of particles of red phosphorus suspended in white phosphorus. At about 50% conversion, these particles became numerous and large enough to make the reaction mixture semifluid. Further conversion yielded a solid mass of product. © 1946, American Chemical Society. All rights reserved.