ELECTROCHEMICAL SYNTHESIS OF METHANESULFONIC ACID FROM AQUEOUS SOLUTIONS OF DIMETHYL SULFONE

DOI: 10.6060/tcct.20165912.5345
Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2016. V. 59. N 12. P. 100-106

In recent years, methane sulfonic acid (MSA) is being increasingly used in various fields of electrochemical production such as electroplating, electrorefining and electrodeposi-tion of metals etc. In this regard development of new methods for the synthesis of MSA from organic sulfur compounds is today an urgent task. In this paper we studied the electrochemi-cal synthesis of methane sulfonic acid from aqueous solutions of dimethyl sulfone (DMS). The electrochemical behavior of DMS in an acidic environment on a smooth platinum elec-trode in a wide range of the anodic potentials was studied by cyclic voltammetry. It is shown that electrooxidation of DMS occurs at high anodic potentials of 1.8 - 2.15 V. Within of DMS concentration range of 0.05 - 0.15 M, and the anode current density of 0.01 - 0.03 A / cm2 MSA is the main product the oxidation. It was also found that with increasing concentrations of DMS there is a significant suppression of process of oxygen evolution. At concentration of dimethyl sulfone more than 0.2M the yield of MSA falls, which is associated with a change in the electrochemical mechanism of DMS oxydation. By methods of Raman and IR spectros-copy it was revealed that at the electrochemical oxidation of aqueous solutions at the concen-tration of DMS more than 0.2M on a smooth platinum electrode in the anodic electrolysis compartment two stable products – methanesulfonic acid and dimethyl disulfon (DMDS) are formed. The initial concentration of dimethyl sulfone affects the product yield. It was shown that the change in preparative electrosynthesis product yields of MSA and DMDS is connect-ed with the increase in the concentration of aqueous solutions of DMS and the anode current density. On basis of data of voltammetric measurements and analysis of preparative electro-synthesis products the mechanism of electrooxidation of dimethyl sulfone in an acidic envi-ronment on a smooth platinum electrode to form the MSA and DMDS was proposed. It was shown that DMDS at the room temperature may easily be separated from the anolyte solution in an acidic environment in the form of crystal material. It was also found that by heating to temperature 80-85 °C the anolyte solution containing DMDS, decomposes to methanesulfinic and methanesulfonic acids. It was shown that methanesulfinic acid is unstable acid which is readily oxidized with atmospheric oxygen, which makes it possible to obtaine MSA by elec-trosynthesis with a high quantitative yield. Thus, MSA is a final product of dimethyl sulfone electrooxidation in an acidic environment on smooth platinum with a quantitative yield on current.

Key words: dimethyl sulfone, dimethyl disulfone, methanesulfinic acid, methanesulfonic acid, potential, platinum microelectrode, radical, electrooxidation, electrosynthesis

ЛИТЕРАТУРА
1. Gernon M.D., Wu M., Buszta T., Janney P. Environmental benefits of methane sulfonic acid. Comparative properties and advantages. Green Chem. 1999. N 1. P. 127-140.
2. Akmedov M.A., Khidirov Sh. Sh. Voltammetric determination of the composition and properties of methane sulfonic acid. J. Struct. Chem. 2014. V. 55. N 6. P. 1148-1151.
3. Khibiev Kh.S., Omarova K.O., Khidirov Sh. Sh. Electrochemical synthesis of dimethyl sulfone and methane sulfonic acid from dimethyl sulfoxide. Rus. J. Electrochem. 2010. V. 46. N 8. С. 960.
4. Хидиров Ш.Ш., Омарова К.О., Хибиев Х.С. Электроокисление диметилсульфоксида на платиновом электроде в кис-лой среде. Вестн. ДГУ. 2012. Т. 110. Вып. 1. С. 233-236.
5. Хидиров Ш.Ш., Ахмедов М.А., Хибиев Х.С., Омарова К.О. Патент РФ № 2496772. 2013.
6. Хидиров Ш.Ш., Ахмедов М.А., Рабаданов М.Х. Патент РФ № 2554880. 2015.
7. Маркарян Ш.А., Азнаурян М.Г., Казоян Е.А. Physicochemical properties of aqueous solutions of dimethyl- and diethyl-sulfones. ЖФХ. 2011. Т. 85. № 12. С. 2291.
8. Беленький Л.И. Получение и свойства органических соединений серы. М.: Химия. 1998. 560 с.
9. Хидиров Ш.Ш., Омарова К.О., Хибиев Х.С. Патент РФ № 2344126. 2009.
10. Тарасевич Б.Н. ИК спектры основных классов органических соединений. М.: МГУ им. М.В. Ломоносова. 2012. С. 29–35.
11. Шмидт В. Оптическая спектроскопия для химиков и биологов. М.: Техносфера. 2007. 368 с.
12. Яковлева А.А. Адсорбция ацетат и пропионат ионов на платине при высоких анодных потенциалах. Электрохимия. 1979. Т. 15. Вып. 9. С. 1318-1323.
13. Березин Б.Д., Березин Д.Б. Курс современной органической химии. М.: Высш. шк. 1999. 768 с.

2016, Т. 59, № 12, Стр. 100-106

Purchase

You will get the pdf-copy of your article by e-mail