KINETICS OF THE EXCHANGE OF PHOSPHORUS IN PCl$sub 3$-POCl$sub 3$ SYSTEMS EFFECT OF GAMMA RADIATION, ULTRAVIOLET LIGHT, VISIBLE LIGHT, HEAT AND TRACES OF WATER
The exchange of phosphorus between PCl/sub 3/ and POCl/sub 3/ has been measured with the use of P/sup 32/ radioactive tracer. No exchange was found in this system for mixtures kept at 250 deg C in the presence of white light for 23 days. A detectable amount of exchange occurred in mixtures exposed to ultraviolet light. Hydrolysis products in the system enhanced the exchange. A gamma ray induced exchange was found to obey ihe equation, M = k'bD + k''abD, where M is the millimoles of phosphorus exchanged per gram of solution, a and b are the coucentrations of PCl/sub 3/ and POCl/sub 3/ in millimoles per gram of solution, respectively, and D is the gamma ray dosage in rads. Values of k' and k'' were found to be (3.19 plus or minus 0.16) x10:0 rad: and (4.24 plus or minus 0.31) x 10/sup -11/: g nism for the second order exchange reaction consists of a P-O bond dissociation with subsequent recombination of the oxygen radical with PCl/sub 3/. The third order reaction can be explained by a gamma ray induced exchange of oxygen between weakly coupled PCl/sub 3/--POCl/sub 3/ dipoles or by the exchange of oxygen upon collision of excited PC1/sub 3/or POCl/ sub 3/ molecules with the other component in the system. (auth)
- Research Organization:
- Kansas State Univ., Manhattan
- NSA Number:
- NSA-13-016852
- OSTI ID:
- 4240687
- Report Number(s):
- AECU-4190
- Country of Publication:
- United States
- Language:
- English
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