El Chorbagi, Akram A.

Tulskaya, A. G.

Electronic National Technical University &quot;Kharkiv Polytechnic Institute&quot; Institutional Repository (eNTUKhPIIR)

 56ANODIC PROCESSES IN DIMETHYL SULFOXIDE WATER SOLUTION  Alena Tulskaya, Akram A. El Chorbagi , Ukraine, Kharkov National Technical University “Kharkiv Polytechnic Institute”  Introduction . Methanesulfonic acid (MSA) is a strong organic acid which can be applied as a catalyst in nitration, alkylation and etherification of olefins [1] and can also be applied for preparation of electrolytes in chemical, electronic and radio technical branches of industry [2], in pharmaceutics [3]. MSA can be produced by chemical and electrochemical method. Chemical method has been studied and real-ized quite well. Electrochemical one has not been realized in industry nevertheless it can allows to obtain a wide range of organic substances. Dymethyl sulfoxide (DMSO) and methylsulfonylmethane (MSM), which are the by-products in the oil-desulphurization processes, may be used as a source for electrochemical synthesis of MSA [4,5]. Experimental part. Electrode processes were performed by voltammetry method applying the potentiostate P–45X. Kinetics of anodic process was studied on a smooth platinum anode with an surface about 1,2 sm2. Sulphuric acid with a con-centration 0,2 mol·dm–3 was applied as an indifferent electrolyte. The objects of study are influence of DMSO (0,5…4,0 mol·dm–3) and MSM (0,5…1,5 mol·dm–3) concen-tration on a kinetics of anodic process. The temperature is 288…363 K. The current load is 15 A. Working anodic current density - 150…850 А·m–2. Material of anode is platinum, material of cathode is steel X10CrNiTi18-10. MSA was extracted through the sedimentation by cooling of solutions to the temperature 291 K and lower. The resulting products were analyzed by IR spectrometer Agilent Cary 630 FTIR [4, 6]. Results and discussion. Electrochemical method allows to manage the process by varying the anodic potential, catalytic activity of material, temperature of electro-lyte, promoting admixtures. Analyzing the current-voltage curves we can justify the parameters of electrochemical synthesis. DMSO water solution has a low effective conductivity. Sulfuric acid with a concentration 0,2 mol·dm–3 was applied as an indif-ferent electrolyte. Diluted sulfuric acid is stable and doesn’t interact with the DMSO and products of its oxidation. Mechanism of oxygen releasing on a platinum electrode in sulfuric acid solution has been well-studied [7, 8].  Oxidation of DMSO into DMS on a platinum surface is performed with a com-bined reaction which is oxygen release and the potential of peroxide formation is not reached yet. Anodic release of oxygen has an intermediate step – the formation of radical oxygen particles. Significant difference between straight an backward parts of current-voltage curves in potential range from 1,6 to 1,8 V indicates an adsorption of DMSO on a platinum electrode surface and verifies the hypothesis about the participation of DMSO in anodic process.  The release of oxygen from the 0,2 mol·dm–3 of Н2SO4 is performed with a large overvoltage at the potentials of formation of peroxide compounds on a platinum surface [7,8]. Presence of organic sulphur compounds in the anode layer and their in-volving into the anodic process was proved by the shift of anodic potentials into posi- 57tive area after addition of DMSO to the 0,2 mol·dm–3 solution of Н2SO4. The most significant shift was noticed after addition of 1 mol·dm–3 of DMSO. Rise of DMSO concentration down to 3 mol·dm–3 leads to reduction of anodic potential due to the reduction of energy costs for the electrochemical desorption of MSA from the plati-num surface comparing to the combined reaction of the formation peroxide by re-combination of OH radical particles. MSA was obtained by the cooling of electrolyte to 278…300 K. MSA was separated by filtration as the colorless crystals with the further washing with distillate water at a temperature under 278 K. The stock solution after the adjustment was ap-plied in the next electrolysis cycle.  Conclusion. The mechanism for electrochemical synthesis of DMS and MSA from the DMSO water solution was described. Oxidation of DMSO to DMS is per-formed in the potential range 1,5…1,7 V on the platinum electrode surface. In the po-tengial range higher then 1,87…1,89 V the oxidation of DMS to MSA is performed. There has been proposed a stage-mechanism for electrolysis of DMSO solution. Pro-duction of MSA is combined with electrochemical synthesis of hydrogen peroxide. Radical oxygen parts, generated on the platinum anodic surface, are involved in the MSA formation . References [1] P. Kulkarni, Orient. J. Chem. 31 (2015) 447-451. [2] F. C. Walsh, C. Ponce de León, Surface and Coatings Technology 259 (2014) 676 – 697. [3] M.D. Gernon, M. Wu, T. Buszta, P. Janney, Green Chem. 1 (1999) 127-140. [4] M.A. Akhmedov, Sh.Sh. Khidirov, M.Yu. Koparova, Kh.S. Khibiev, Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol., 2016, pp. 100 –106. [5] O.L. Matrunchyk, G.G. Tulsky, S.A. Leshchenko, A.G. Tulskaya, K.S. Rutkovskaya (2017) Razrabotka tekhnologicheskih pokazatelej ehlektro-himicheskogo sinteza metansul'fonovoj kisloty [Development of technological indi-ces of electrochemical synthesis of methanesulphonic asid]. Proceedings of the Mod-ern Electrochemical Technologies and Equipment – 2017 (Republiс of Belarus, Minsk, November 28-30, 2017) Minsk: BGTU, pp. 321 – 325.                                                       

Anodic processes in dimethylsulfoxide water solution

Library of National Technical University "Kharkiv Polytechnic Institute"

 56
ANODIC PROCESSES IN DIMETHYL SULFOXIDE WATER SOLUTION 
 
Alena Tulskaya, Akram A. El Chorbagi , Ukraine, Kharkov 
National Technical University “Kharkiv Polytechnic Institute” 
 
Introduction . Methanesulfonic acid (MSA) is a strong organic acid which can 
be applied as a catalyst in nitration, alkylation and etherification of olefins [1] and 
can also be applied for preparation of electrolytes in chemical, electronic and radio 
technical branches of industry [2], in pharmaceutics [3]. MSA can be produced by 
chemical and electrochemical method. Chemical method has been studied and real-
ized quite well. Electrochemical one has not been realized in industry nevertheless it 
can allows to obtain a wide range of organic substances. Dymethyl sulfoxide 
(DMSO) and methylsulfonylmethane (MSM), which are the by-products in the oil-
desulphurization processes, may be used as a source for electrochemical synthesis of 
MSA [4,5]. 
Experimental part. Electrode processes were performed by voltammetry 
method applying the potentiostate P–45X. Kinetics of anodic process was studied on 
a smooth platinum anode with an surface about 1,2 sm2. Sulphuric acid with a con-
centration 0,2 mol·dm–3 was applied as an indifferent electrolyte. The objects of study 
are influence of DMSO (0,5…4,0 mol·dm–3) and MSM (0,5…1,5 mol·dm–3) concen-
tration on a kinetics of anodic process. The temperature is 288…363 K. The current 
load is 15 A. Working anodic current density - 150…850 А·m–2. Material of anode is 
platinum, material of cathode is steel X10CrNiTi18-10. MSA was extracted through 
the sedimentation by cooling of solutions to the temperature 291 K and lower. The 
resulting products were analyzed by IR spectrometer Agilent Cary 630 FTIR [4, 6]. 
Results and discussion. Electrochemical method allows to manage the process 
by varying the anodic potential, catalytic activity of material, temperature of electro-
lyte, promoting admixtures. Analyzing the current-voltage curves we can justify the 
parameters of electrochemical synthesis. DMSO water solution has a low effective 
conductivity. Sulfuric acid with a concentration 0,2 mol·dm–3 was applied as an indif-
ferent electrolyte. Diluted sulfuric acid is stable and doesn’t interact with the DMSO 
and products of its oxidation. Mechanism of oxygen releasing on a platinum electrode 
in sulfuric acid solution has been well-studied [7, 8].  
Oxidation of DMSO into DMS on a platinum surface is performed with a com-
bined reaction which is oxygen release and the potential of peroxide formation is not 
reached yet. Anodic release of oxygen has an intermediate step – the formation of 
radical oxygen particles. 
Significant difference between straight an backward parts of current-voltage 
curves in potential range from 1,6 to 1,8 V indicates an adsorption of DMSO on a 
platinum electrode surface and verifies the hypothesis about the participation of 
DMSO in anodic process.  
The release of oxygen from the 0,2 mol·dm–3 of Н2SO4 is performed with a 
large overvoltage at the potentials of formation of peroxide compounds on a platinum 
surface [7,8]. Presence of organic sulphur compounds in the anode layer and their in-
volving into the anodic process was proved by the shift of anodic potentials into posi-
 57
tive area after addition of DMSO to the 0,2 mol·dm–3 solution of Н2SO4. The most 
significant shift was noticed after addition of 1 mol·dm–3 of DMSO. Rise of DMSO 
concentration down to 3 mol·dm–3 leads to reduction of anodic potential due to the 
reduction of energy costs for the electrochemical desorption of MSA from the plati-
num surface comparing to the combined reaction of the formation peroxide by re-
combination of OH radical particles. 
MSA was obtained by the cooling of electrolyte to 278…300 K. MSA was 
separated by filtration as the colorless crystals with the further washing with distillate 
water at a temperature under 278 K. The stock solution after the adjustment was ap-
plied in the next electrolysis cycle.  
Conclusion. The mechanism for electrochemical synthesis of DMS and MSA 
from the DMSO water solution was described. Oxidation of DMSO to DMS is per-
formed in the potential range 1,5…1,7 V on the platinum electrode surface. In the po-
tengial range higher then 1,87…1,89 V the oxidation of DMS to MSA is performed. 
There has been proposed a stage-mechanism for electrolysis of DMSO solution. Pro-
duction of MSA is combined with electrochemical synthesis of hydrogen peroxide. 
Radical oxygen parts, generated on the platinum anodic surface, are involved in the 
MSA formation . 
References 
[1] P. Kulkarni, Orient. J. Chem. 31 (2015) 447-451. 
[2] F. C. Walsh, C. Ponce de León, Surface and Coatings Technology 259 
(2014) 676 – 697. 
[3] M.D. Gernon, M. Wu, T. Buszta, P. Janney, Green Chem. 1 (1999) 127-
140. 
[4] M.A. Akhmedov, Sh.Sh. Khidirov, M.Yu. Koparova, Kh.S. Khibiev, Izv. 
Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol., 2016, pp. 100 –106. 
[5] O.L. Matrunchyk, G.G. Tulsky, S.A. Leshchenko, A.G. Tulskaya, K.S. 
Rutkovskaya (2017) Razrabotka tekhnologicheskih pokazatelej ehlektro-
himicheskogo sinteza metansul'fonovoj kisloty [Development of technological indi-
ces of electrochemical synthesis of methanesulphonic asid]. Proceedings of the Mod-
ern Electrochemical Technologies and Equipment – 2017 (Republiс of Belarus, 
Minsk, November 28-30, 2017) Minsk: BGTU, pp. 321 – 325. 
 
 
       
 
 
   
  
  
 
        
         
         
         


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Anodic processes in dimethylsulfoxide water solution

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Electronic National Technical University "Kharkiv Polytechnic Institute" Institutional Repository (eNTUKhPIIR)

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Anodic processes in dimethylsulfoxide water solution

Abstract

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Full text

Available Versions

Electronic National Technical University &quot;Kharkiv Polytechnic Institute&quot; Institutional Repository (eNTUKhPIIR)

Library of National Technical University "Kharkiv Polytechnic Institute"

Electronic National Technical University "Kharkiv Polytechnic Institute" Institutional Repository (eNTUKhPIIR)