KINETIC MODEL OF THIOUREA DIOXIDE DECOMPOSITION IN AQUEOUS SOLUTIONS OF DIFFERENT ACIDITY
Abstract
A stoichiometric mechanism for full thiourea dioxide decomposition in aqueous solution under pH of 4.0 is proposed based on dependences of concentrations of thiourea dioxide and its decomposition products on the time and literature data. The concentration of thiourea dioxide was measured via iodometry, while the intermediates were quantified using the polarography. Polarography was carried out in glass two-electrode electrochemical cell by means of PU-1 polarograph in differential mode. Dropping mercury electrode was used as working one and silver chloride as a reference one. Rate constants for individual stages are obtained via mathematical modeling, presented a system of differential equations. Absolute errors of rate constants, correlation coefficients, and F-factors were also calculated. Verification of supposed kinetic model was conducted using the comparison between experimental and calculated concentrations, F-test and the calculated values of correlation coefficients of the individual stages of the process. Supposed kinetic model of decomposition consists of a number of consequent stages including various compounds such as sulfur monoxide, thiosulfuric, sulfuric, dithionic, hydrosulfuric acids as intermediates was used for previously obtained data for pH of 8.85. To test the universality of supposed model, we simulated kinetics of thiourea dioxide decomposition reaction at pH of 8.85. Experimental kinetic data were taken from literature. The initial approximations of the individual stages constants were taken from previous calculations. Analysis of calculated data: concentration values, F-test, correlation coefficients allowed to conclude about the applicability of proposed mechanism for the process of thiourea dioxide decomposition in a weakly alkaline medium.
References
Polenov Yu.V., Egorova E.V., Nikolaev A.V. Reduction of 4-nitrozodiphenylamine by sodium hydroxymetanesul-finate and thiourea dioxide in dimethylsulphoxide solution. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2008. V. 51. N 5. P. 43-47 (in Russian).
Polenov Yu.V., Egorova E.V., Makarova E.V. Formation of nickel-containing coatings on carbon fiber by means of thiourea dioxide as reducing agent. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2013. V. 56. N 10. P. 75-78 (in Russian).
Polenov Yu.V., Egorova E.V., Makarova E.V. Kinetic of nickel ions reduction in water-ammoniac solution by thiourea dioxide. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2013. V. 56. N 8. P. 38-40 (in Russian)
Polenov Yu.V., Egorova E.V., Shestakov G.A. Kinetics of the reduction of cadmium sulfate by thiourea dioxide in an aqueous ammonia solution upon the metallization of carbon fiber. Rus. J. Phys. Chem. A. 2018. V. 92. N 1. P. 53-56. DOI: 10.1134/S0036024418010181.
Polenov Yu.V., Egorova E.V. Reduction of 4- nitrosodi-phenylamine with thiourea dioxide in bynary solvent dime-thylsulfoxide – water. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2012. V. 55. N 2. P. 33-36 (in Russian).
Makarova E.V., Polenov Yu.V., Egorova E.V. Kinetic model of process of nickel ions reduction by thiourea dioxide in water-ammonia solution. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2015. V. 58. N 1. P. 36-39 (in Rus-sian).
Shestakov G.A., Polenov Yu.V., Egorova E.V. Pd/Ni-metallized carbon fiber in electrooxydation of alcohols. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2017. V. 60. N 9. P. 77-81 (in Russian). DOI: 10.6060/tcct.2017609.5536.
Budanov V.V., Ermolina S.V., Polenov Yu.V., Terskaya I.N. Kinetics of electroless decomposition Ni and Cu pow-ders by reduction of their chlorides with thiourea dioxide. Rus. J. Gen. Chem. 2000. V. 70. N 5. P. 655-658.
Polenov Yu.V., Budanov V.V. Kinetics of reduction of 2-nitro- 2′-hydroxy- 5′- methylazobenzene by thiourea dioxide. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 1988. V. 31. N 8. P. 66-70 (in Russian).
Polenov Yu.V., Sliznev V.V., Lapshina S.B., Nikolaev A.V., Egorova E.V., Koksharov S.A. Structure and kinetic stability of 1-hydroxy-and aminoalkalnesulfinates in aqueous solutions. Rus. J. Gen. Chem. 2006. V. 76. N 7. P. 1090-1094. DOI: 10.1134/S1070363206070141.
Makarov S.V., Kudrik E.V., Naidenko E.V. Acid-base properties of sulfoxylate ion. Rus. J. Inorg. Chem. 2006. V. 51. N 7. P. 1149-1152. DOI: 10.1134/S0036023606070217.
Gao Q., Liu B., Li L, Wang J. Oxidation and decomposi-tion kinetics of thiourea oxides. J. Phys. Chem. A. 2007. V. 111. N 5. P. 872-877. DOI: 10.1021/jp063956q.
Polenov Yu.V., Nikolaev A.V., Egorova E.V., Beltsova N.A. Dioxide thiourea decomposition in solvents: dimethyl-sulfoxide and dimethylsulfoxide-water. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2009. V. 52. N 5. P. 82-85 (in Russian).
Polenov Yu.V., Makarova E.V., Egorova E.V. Kinetic model of thiourea dioxide decomposition in aqueous ammo-nia. Kinet. Catal. 2014. V. 55. N 5. P. 566-570. DOI: 10.1134/S0023158414040120.
Makarov S.V., Salnikov D.S., Pogorelova A.S. Acid-base properties and stability of sulfoxylic acid in aqueous solu-tions. Rus. J. Inorg. Chem. 2010. V. 55. N 2. P. 301-304. DOI: 10.1134/S0036023610020269.
Polenov Yu.V., Budanov V.V., Egorova E.V. Kinetics of liquid-phase redox reactions involving hydroxy- and amino-alkanesulfinates. Rus. J. Appl. Chem. 2001. V. 74. N 10. P. 1715-1721. DOI: 10.1002/chin.200235290.
Crabtree K.N., Martinez O.J., Barreau L., Thorwirth S., McCarthy M.C. Microwave detection of sulfoxylic acid (HOSOH). J. Phys. Chem. A. 2013. V. 117. N 17. P. 3608-3613. DOI: 10.1021/jp400742q.
Gartman T.N., Klushin D.V. Computer simulation of pro-cesses in chemical engineering. M.: Akademkniga. 2006. 416 p (in Russian).
Polenov Yu.V., Makarov S.V., Budanov V.V. Thiourea dioxide decomposition in aqueous solutions. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 1986. V. 29. N 12. P. 30-33 (in Russian).
Polenov Yu.V., Pushkina V.A., Egorova E.V., Labutin A.N., Khalizov R.L. Kinetic model of the decomposition of sodium hydroxymethanesulfinate in aqueous solution. Kinet. Catal. 2002. V. 43. N 4. P. 465-468 DOI: 10.1023/A:1019814732139.
