Вестник Кемеровского государственного университета (Sep 2013)
HUMIC ACIDS AS MODIFIERS IN REACTIONS OF LIQUID-PHASE OXIDATION OF YELLOW PHOSPHORUS
Abstract
The paper focuses on researching the reaction of liquid-phase oxidation of yellow phosphorus (P4) with oxygen and tetrachlormethane in soft conditions in water and butanolic solutions in the presence of homogeneous and heterogeneous catalysts on the basis of copper (II) and the iron(III) acydocomplexes modified by fulvo-and gematomelanic acids to give phosphorus acids and phosphorus acids ethers. The purpose of the research is developing new effective homogeneous and heterogeneous catalysts of P4 liquid-phase oxidation in water and butanolic solutions to receive valuable phosphoruscontaining compounds. Using the methods of kinetics, volumometric, redox-potentiometrics, IR-spectroscopy, titration and GS analysis, the kinetics, intermediate and final products were investigated, optimum conditions of reaction of P4 liquidphase oxidation with O2 and CCl4 in water and butanolic solutions have been defined. Catalytic effect of homogeneous and heterogeneous copper and iron acydocomplexes on the velocity of P4 oxidation by oxygen in water solutions to phosphorus acids and phosphorus acids ethers was found. The studied processes were found to follow the oxidation-reduction mechanism and to consist of two key stages: Cu(II) and Fe(III) reduction by yellow phosphorus to Cu(0) and Fe(I) with formation of phosphorus acids and phosphorus acids ethers and Cu(I) oxidation to Cu(II) with Fe(II) occidation to Fe(III) by oxygen or tetrachlormethane. Yellow phosphorus was effectively oxidized mainly to tributylphosphites in butanol-toluene solutions of copper (II) acydocomplexes, and to dibutylphosphites in the presence of iron (III) chloride. The results of the research can serve as the basis for developing effective catalytic systems for new "non-chlorine" ecologically safe catalytic ways of receiving valuable organic and inorganic phosphorus-containing compounds. Thus, yellow phosphorus was found to be effectively oxidized with O2 and CCl4 in soft conditions in water and butanolic solutions of copper (II) and iron(III) acydocomplexes to give phosphorus acids and phosphorus acids ethers with high yields (80 – 100 %).
