Laboratory simulations of PH3 photolysis in the atmospheres of Jupiter and Saturn

Photolysis of NH₃PH₃ mixtures (11 Torr) at 175°K resulted in the same initial rate of P₂H₄ formation as when the 11 Torr of pure PH₃ was photolyzed. A higher yield of P₂H₄ is obtained at 175°K than at 298°K because some of the P₂H₄ condenses on the cell wall at 175°K and is not subject to further reaction. Some reaction of P₂H₄ is taking place as observed by the decrease in its yield and on the formation of red phosphorus on extended photolysis of PH₃ at 175°K. No NH₂PH₂ or (PN)_x were detected as photoproducts as indicated by the absence of change in the UV spectral properties of the P₂H₄ and red phosphorus fraction, respectively, when NH₃ is present. Although the pathway for PH₃ decomposition is changed, the outcome of the photochemical process is essentially the same in the absence or presence of NH₃. The formation of P₂H₄ and red phosphorus was not inhibited by small amounts of C₂H₄ and C₂H₂, so the low levels of hydrocarbons on Jupiter and Saturn will not have a significant effect on the course of PH₃ photolysis. The ratio of products of PH₃ photolysis are only slightly affected by the wavelength of light used. Use of xenon lamp, with a continuous emission in the ultraviolet where P₂H₄ absorbs, results in only a modest decrease in the yield of P₂H₄ and a modest increase in the rate of formation of red phosphorus as compared to the rates observed with a 206.2-nm light source. The quantum yield for P₂H₄ formation is pressure independent in the 0.5–11 Torr range. This quantum yield is not affected by lowering the temperature to 157°K or by the addition of 100 Torr of H₂. It is concluded that photolysis of PH₃ to P₂H₄ and the subsequent conversion of P₂H₄ to red phosphorus are likely procses on Jupiter and Saturn and that particles of P₂H₄ condense in the atmospheres of these planets. The conversion of some of the P₂H₄ to red phosphorus may take place on Jupiter.