Physical aspects of Group V halide systems

• Main Author: Dean, Christopher Robert Sorrell
• Published: Royal Holloway, University of London 1972
• Subjects: 541; Physical Chemistry
• Online Access: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.704199

An apparatus has been designed and constructed to measure solubilities of the order of 10-6 to 10-5 mole fraction of non-reactive gases in liquid phases. The solubilities of and are reported, and the estimated enthalpies and entropies of solution are compared with values predicted by seni-enjpirical relationships. The reaction of N2F4 with aqueous ferrous ions buffered at has been studied. The results supported the predicted equation for the reactions [equation] Under the conditions used, the reaction was controlled by the rate of solution of into the aqueous phase, and it appeared likely that the rate of the reaction was not affected by ferrous ion concentration, Methemoglobm formation by and is discussed with regard to the solubilities and reactivities of these gases,Raman and infrared spectra have been recorded. Vibrational assignments have been oade on the basis of these spectra and of approximate normal coordinate calculations, and statistical thermo-dynamic functions have been calculated. Statistical thermodynamic functions of have been calculated using revised structural data and confirmed vibrational frequencies. The thermal decomposition of is discussed. Eaman have been recorded, and the analysis of the nuclear -mgnetic resonance spectrum of has been reinvestigated. The results strongly favour a trans configuration for, and tentative vibrational assignments are mode for four infrared-active and six iteuaaii-active fundamenial frequencies the ultraviolet spectrum of has been recorded was divergent from that predicted by the previously proposed relationship between [lambda]max and substituent electronegativity. The decomposition of P2F4 was followed, and the order of the decomposition reaction was estimated as Electron-irapoct appearance potentials for the parent and PF fragment ions from have been measured. The ionisation potentials are reported and has been estimated as 58 (9) keal.mole-1.