title: Laboratory simulations of PH3 photolysis in the atmospheres of Jupiter and Saturn.
abstract: Photolysis of NH3-PH3 mixtures (11 Torr) at 175 degrees 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 degrees K than at 298 degrees K because some of the P2H4 condenses on the cell wall at 175 degrees 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 degrees 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 HN3 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 a 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 degrees 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 processes 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.
authors.affiliation: Department of Chemistry, Rensselaer Polytechnic Institute, Troy, New York 12180-3590, USA.
authors.forename: J P
authors.initials: JP
authors.lastname: Ferris
authors.forename: H
authors.initials: H
authors.lastname: Khwaja
mesh_terms: D000641:Ammonia / Q000737:chemistry*; D001272:Atmosphere / Q000737:chemistry*; D006838:Hydrocarbons / Q000032:analysis / Q000737:chemistry; D018538:Jupiter; D008956:Models, Chemical; D010720:Phosphines / Q000032:analysis / Q000737:chemistry*; D010758:Phosphorus / Q000032:analysis / Q000737:chemistry; D010782:Photolysis; D011312:Pressure; D018539:Saturn; D013057:Spectrum Analysis; D013472:Sunlight; D013696:Temperature
chemical_list: D006838:Hydrocarbons; D010720:Phosphines; D010758:Phosphorus; D000641:Ammonia; C044646:phosphine