Особенности синтеза ферратов(VI) из сульфата железа(II)

Dmitriy Golovko, Igor Golovko

Анотація


High cost of ferrates(VI) – new promising oxidants – stimulates enhancement of Fe(VI) derivatives obtaining technology based on usage of available cheap raw materials. In present paper peculiarities of ferrates(VI) of alkaline and alkaline-earth metals synthesis based on hypochlorite method have been investigated:

FeSO4(s) + 2ClO+ 4OH® FeO42+ 2Cl + SO42+ 2Н2О.

This reaction should be quantitative based on thermodynamic analysis. Nevertheless it was found during carried out experiments that yield of Fe(VI) compounds less than 100%. Influence of operating parameters (hydroxide and hypochlorite concentrations, temperature, molar ratio [ClO]/[Fe(II)]) on yield of product has been investigated. It was found out than generation of ferrate decreases with increase of temperature so it is advisable to carry out synthesis in low temperature field (0-5 0C). It is necessary at least twice greater excess of oxidant comparing to stoichiometry to achieve the completeness of the conversion raw material to wanted product. It was found that degree of conversion ferrous salts to ferrates during hypochlorite oxidation increases in row ferrous sulfate - ferrous chloride - ferrous nitrate. It was stated by experiment that magnetite formation occurs (no more 7% of total Fe) during ferrate synthesis from FeSO4·7H2O by hypochlorite way. It was demonstrated solid ferrates (K2FeО4, CaFeO4 и BaFeO4) have been wasted by sulfate anions during synthesis, lowest (<4%) content of it ones has been fix in potassium ferrate, highest (~18%) – in barium salt. New technological decisions for synthesis efficiency improvements  and decreasing impurities content (mainly sulfates) have been proposed

Ключові слова


ferrate(VI) synthesis, ferrous sulfate, hypochlorite method, potassium and sodium ferrates

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Посилання


Sharma, V. K. Ferrates: Synthesis, Properties, and Applications in Water and Wastewater Treatment ACS Symposium Series, 2008, 524 p.

Yang, X., Gan, W., Zhang, X. [et al.] Effect of pH on the formation of disinfection byproducts in ferrate(VI) pre-oxidation and subsequent chlorination Separ. Purif. Tech., 2015, 156(3), 980-986

Delaude, L., Laszlo, P. A. Novel Oxidizing Reagent Based on Potassium Ferrate(VI) J. Org. Chem.,1996, 61 (18), 6360 – 6370

Farmand, M., Jiang, D., Wang, B. [et al.] Super-iron nanoparticles with facile cathodic charge transfer. Electrochem. Comm.,2011, 13(9), 909-912.

Kanari, N., Filippova, I., Diot, F. [et al.] Utilization of a waste from titanium oxide industry for the synthesis of sodium ferrate by gas-solid reactions Termochim. Acta.,2014, 575, 219-225.

Lee, J., Truk, D., Fujishima A., [et al.] Electrochemical generation of ferrate in acidic media at boron doped diamond electrodes. Chemm. Commun. 2002, 5, 486-487.

Aubertin, N., Neveux, R., Gerardin, R. [et al.] Synthese d'un sulfatoferrate de potassium et son efficacite dans le traitement des eaux. Rev. Sci. Eau, 1996, 1, 17-30.

el Maghraoui, A., Zerouale, A., Ijjaali, M. Effect of degree of ClO– hypochlorite on the wet synthesis of ferrate(VI). Adv. Mat. Phys. Chem. 2015, 5, 133-139.

Golovko, D., Sharma, V.K., Pavlova O [et al.] Determination of submillimolar concentration of ferrate(VI) in alkaline solutions by amperometric titration. Centr. Europ.J. Chem., 2011, 9(5), 808-812.

Chalyj, V. Gidrookisi metallov. Kiev: Naukova dumka. – 1972, 159 p.

Licht, S., Tel-Vered, R., Halperin, L. Toward efficient electrochemical synthesis of Fe(VI) Ferrate and super-iron battery compounds J. Electrochem. Soc.,2004, 151(1), A31-A39.

Golovko. D., Golovko I. Vlijanie soedinenij marganca na sintez ferratov(VI) TARP, 2015, 3/4(23), 69-73


Пристатейна бібліографія ГОСТ


Sharma, V. K. Ferrates: Synthesis, Properties, and Applications in Water and Wastewater Treatment /
V. K. Sharma. – ACS Symposium Series. − 2008. − 524 p.

Yang, X. Effect of pH on the formation of disinfection byproducts in ferrate(VI) pre-oxidation and subsequent chlorination / X. Yang, W. Gan, X. Zhang [et al.] // Separ. Purif. Tech. – 2015. – vol.156, part 3. – P. 980-986

Delaude, L. Novel Oxidizing Reagent Based on Potassium Ferrate(VI) / L. Delaude, P.A. Laszlo // J. Org. Chem. – 1996. – Vol. 61, № 18. – Р. 6360 – 6370

Farmand, M. Super-iron nanoparticles with facile cathodic charge transfer / M. Farmand, D. Jiang, B. Wang [et al.] // Electrochem. Comm. – 2011. – vol.13, №9. – P. 909-912.

Kanari, N. Utilization of a waste from titanium oxide industry for the synthesis of sodium ferrate by gas-solid reactions / N. Kanari, I. Filippova, F. Diot [et al.] // Termochim. Acta. – 2014. – vol. 575. – P.219-225.

Lee, J. Electrochemical generation of ferrate in acidic media at boron doped diamond electrodes / J. Lee, D. Truk, A. Fujishima [et al.] // Chemm. Commun. – 2002. – №5. – P. 486-487.

Aubertin, N. Synthese d'un sulfatoferrate de potassium et son efficacite dans le traitement des eaux / N. Aubertin, N. Neveux, R. Gerardin [et al.] // Rev. Sci. Eau – 1996. –
vol. 1. – P.17-30.

Maghraoui, A. Effect of degree of ClO– hypochlorite on the wet synthesis of ferrate(VI) / A. el Maghraoui, A. Zerouale, M. Ijjaali // Adv. Mat. Phys. Chem.– 2015. – vol.5. – P.133-139.

Golovko, D. Determination of submillimolar concentration of ferrate(VI) in alkaline solutions by amperometric titration / D. Golovko, V.K. Sharma, O. Pavlova [et al.]. // Centr. Europ.J. Chem. − 2011. − vol. 9, №5. − P.808-812.

Чалый, В. П. Гидроокиси металлов. − К.: Наукова думка. – 1972. − 159 с.

Licht, S. Toward efficient electrochemical synthesis of Fe(VI) Ferrate and super-iron battery compounds / S. Licht, R. Tel-Vered, L. Halperin // J. Electrochem. Soc. – 2004. – 151(1). – P. A31-A39.

Головко, Д. А. Влияние соединений марганца на синтез ферратов(VI) / Д. А. Головко, И. Д. Головко // Технол. аудит и резервы производства. – 2015. – №3/4 (23). –
С. 69-73.


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