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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 %).

About the Authors

A. T. Zhaykenova
Al-Farabi Kazakh National University
Kazakhstan
Ainura T. Zhaykenova – Bachelor’s Degree student at the Department Physical Chemistry, Catalysis and Petroleum Chemistry


S. N. Uytkybaeva
Al-Farabi Kazakh National University
Kazakhstan
Symbat N. Uytkybaeva – Bachelor’s Degree student at the Department Physical Chemistry, Catalysis and Petroleum Chemistry


A. B. Shensizbaeva
Al-Farabi Kazakh National University
Kazakhstan
Aidana B. Shensizbaeva – Bachelor’s Degree student at the Department Physical Chemistry, Catalysis and Petroleum Chemistry


M. A. Bazhanova
Al-Farabi Kazakh National University
Kazakhstan
Meruert A. Bazhanova – Master’s Degree student at the Department Physical Chemistry, Catalysis and Petroleum Chemistry


Zh. T. Eshova
Al-Farabi Kazakh National University
Kazakhstan
Zhaniya T. Eshova – Candidate of Chemistry, Assistant Professor at the Department Physical Chemistry, Catalysis and Petroleum Chemistry


Zh. K. Kairbekov
Al-Farabi Kazakh National University
Kazakhstan
Zhaksyntay K. Kairbekov – Doctor of Chemistry, Professor at the Department Physical Chemistry, Catalysis and Petroleum Chemistry


D. N. Akbaeva
Al-Farabi Kazakh National University
Kazakhstan
Dina N. Akbaeva – Doctor of Chemistry, Professor at the Department Physical Chemistry, Catalysis and Petroleum Chemistry


G. S. Polimbetova
D. V Sokolsky Institute of Organic Catalysis and Electro-Chemistry
Kazakhstan
Gulshara S. Polimbetova – Doctor of Chemistry, Professor, Head of the Laboratory of Homogeneous Catalysis


References

1. Дорфман, Я. А. Заместительное окислительное алкоксилирование фосфина в присутствии хлоридов меди (I, II) / Я. А. Дорфман, Л. В. Левина, Т. В. Петрова [и др.] // Кинетика и катализ. – 1989. – Т. 30. – № 6. – C. 1483 – 1484.

2. Сафиуллин, Р. Л. Кинетические закономерности катализируемого соединениями меди(II) циклопропанирования олефинов / Р. Л. Сафиуллин, В. А. Докичев, Л. Р. Якупова [и др.] // Кинетика и катализ. – 2008. – Т. 48. – № 1. – С. 48 – 56.

3. Гольцов, Ю. Г. Нитрозирование ацетона окисью азота с использованием пентацианидных комплексов железа(III) / Ю. Г. Гольцов, В. В. Жилинская // Физическая химия. – 1990. – Т. 64. – № 9. – С. 2539 – 2542.

4. Богомолов, А. Ю. Кинетика и механизм гомогенно-каталитического гидрохлорирования олефинов в присутствии FeCl3 / А. Ю. Богомолов, В. В. Смирнов, Т. Н. Ростовщикова [и др.] // Кинетика и катализ. – 1995. – Т. 36. – № 2. – С. 253 – 257.

5. Дорфман, Я. А. Кинетика и механизм окислительного алкоксилирования тетрафосфора в присутствии сульфатов и карбоксилатов Cu(II) / Я. А. Дорфман, Р. Р. Абдреимова, Д. Н. Акбаева // Кинетика и катализ. – 1995. – Т. 36. – № 1. – С. 103 – 110.

6. Абдреимова, Р. Р. Окислительное алкоксилирование белого фосфора в присутствии галогенидов Fe(III) / Р. Р. Абдреимова, Д. Н. Акбаева, Ф. Х. Фаизова [и др.] // Изв. МН-АН РК. – (Cерия: Химия). – 1998. – № 4. – С. 65 – 71.

7. Абдреимова, Р. Р. Окислительный алкоголиз белого фосфора в присутствии нанокатализаторов на основе медного порошка и галидов меди(I). Сообщение 1 / Р. Р. Абдреимова, Ф. Х. Фаизова, А. А. Каримова [и др.] // Изв. НАН РК. – (Серия: Химия). – 2009. – № 3. – С. 46 – 51.

8. Злобина, Е. В. Задания и методические указания для лабораторных занятий по аналитической химии: уч.- метод. пособие / Е. В. Злобина, Н. Д. Долгова. – Алматы: Қазақ университеті, 2010. – 114 с.


Review

For citations:


Zhaykenova A.T., Uytkybaeva S.N., Shensizbaeva A.B., Bazhanova M.A., Eshova Zh.T., Kairbekov Zh.K., Akbaeva D.N., Polimbetova G.S. HUMIC ACIDS AS MODIFIERS IN REACTIONS OF LIQUID-PHASE OXIDATION OF YELLOW PHOSPHORUS. SibScript. 2013;(3-3):70-77. (In Russ.)

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ISSN 2949-2122 (Print)
ISSN 2949-2092 (Online)