INTERRELATION BETWEEN CATALYTIC REDUCTION RATE AND SOLUBILITY OF NITROBENZOIC ACID ISOMERS
Abstract
The solubility of nitrobenzoic acid isomers is determined from the concentration of solution in equilibrium with the solid phase at a temperature of 303 K in an azeotropic aqueous solution of 2-propanol, including additives of acetic acid and sodium hydroxide, with an error of no more than 5%. It is shown that the lowest solubility in all these media is observed for para-nitrobenzoic acid, and the maximum for the meta-isomer. The addition of acid or base to the liquid phase assists an increase in solubility for all isomers of nitrobenzoic acid. The most significant changes in solubility occur in the presence of sodium hydroxide in the water-alcohol solvent. The shift of the maxima in the absorption spectra was compared with the change in the solubility value. It has been established that with increasing solubility, the rate of liquid phase catalytic hydrogenation of nitrobenzoic acid isomers on the skeletal nickel catalyst decreases. А linear correlation between the solubility of reagents and the rate of their reduction is revealed. The observed interrelation for para- and meta-isomers in neutral and acidic aqueous-alcoholic media is mostly caused by the influence of solubility on the adsorption ability of the hydrogenated compound on the surface of the nickel catalyst. Deviations from this dependence in the presence of sodium hydroxide can be explained by ionization of the of nitrobenzoic acid isomers molecules and by redistribution of the forms of hydrogen adsorbed on the surface of the nickel catalyst. The reason of the distinction in a similar correlation for isomers with a substituent in the ortho-position relative to the nitrogroup is the possibility for forming an intramolecular hydrogen bond in all used media.
References
Manin N.G., Perlovitch G.L., Manin A.N., Voronin A.P. Patent RF N 2497804. 2013 (in Russian).
Ladilova N.Yu., Fomin V.A. Patent RF N 2594486. 2016 (in Russian).
Azev Yu.A., Charushnikov K.A., Gibor A.M., Mokrushin V.S., Bakulev V.A. Patent RF N 2505526. 2014 (in Russian).
Relvas J., Andrade R., Freire F.G., Lemos F.., Araujo P., Pinho M.J., Nunes C.D., Ribeiro F.R. Liquid phase hydrogenation of nitrobenzene over an industrial Ni/SiO2 supported catalyst. Catalysis Today. 2008. V. 133. Р. 828-835.
Osadchaya T.Yu., Afineevsky A.V., Prozorov D.A., Lukin M.V. Catalytic properties of modified skeletal nickel in the reaction of liquid-phase hydrogenation of 4-nitrotoluene. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2015. V. 58. N 3. P. 26-31 (in Russian).
Theory and practice of liquid-phase hydrogenation of substituted nitrobenzenes. Ed. by O.I. Coifman. M.: Krasand. 2016. 528 p. (in Russian).
Ulitin M.V., Gostikin V.P., Filippenko L.K., Komarov S.A. Effect of solvation on the kinetic regularities of nitro compounds catalytic hydrogenation. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 1987. V. 30. N 12. P. 71-75 (in Russian).
Gostikin V.P. Influence of the solvent on the rate of heterogeneous catalytic reactions of hydrogenation. Mezhvuz. sb. nauch. trudov: Voprosy kinetiki i kataliza. Ivanovo. 1985. P. 3-9.
Latypova A.R., Krasnov A.I., Sharonov N.Yu., Safarov I.M., Lefedova O.V. Kinetics of hydrogenation of 2-chloro-4-nitroaniline on supported platinum and palladium catalysts in an aqueous solution of 2-propanol. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 1. P. 42-48 (in Russian).
Hoang A., Kalashnikova V.A., Lefedova O.V. Kinetics of hydro-genation of 4-nitro-2'-hydroxy-5'-methylazobenzene on skeletal nickel in an aqueous solution of 2-propanol. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 3. P. 10-15 (in Russian). DOI: 10.6060/tcct.20186103.5604.
Gelder E.A., Jackson S.D., Lok C.M. Competitive Hy-drogenation of nitrobenzene, nitrosobenzene and аzobenzene. Catalysis of organic reactions. Twenty-first Conference. CRC Press. 2006. P. 167.
Thu Ha N.T., Latypova A.R., Efremov E.V., Lefedova O.V., Filippov D.V. Kinetics of nitrobenzene hydrogena-tion on spongy nickel and catalyst with supported palla-dium in 2-propanol aqueous solutions with acid or base additives. Russ. J. Phys. Chem. A. 2017. V. 91. N 4. P. 640-644. DOI: 10.1134/S0036024417040197.
Smirnova I.V., Nemtseva M.P., Lefedova O.V. Effect of the composition of the solvent 2-propanol-water on the rate of hydro-genation of substituted nitrobenzenes. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2009. V. 52. N 5. P. 25-28 (in Russian).
Lefedova O.V., Smirnova I.V., Nemtseva M.P. The influence of the nature of substituents on adsorbability and the rate of liquid-phase hydrogenation of nitrobenzenes. Russ. J. Phys. Chem. A. 2009. V. 83. N 10. P. 1727-1730.
Smirnova I.V., Nemtseva M.P., Lefedova O.V. Hydrogenation of substituted nitrobenzenes in 2-propanol-water in the presence of acids and bases. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2010. V. 53. N 11. P. 40-43 (in Russian).
Minenkov Yu.V., Lefedova O.V., Smirnova I.V., Nemtseva M.P. Thermodynamic and kinetic characteristics of liquid phase hydrogenation of substituted nitro-benzenes. Russ. J. Phys. Chem. A. 2012. V. 86. N 6. P. 908-912.
Smirnova I.V., Nemtseva M.P., Lefedova O.V., Lukovitsina M.K. Estimation of deactivation degree of skeletal nickel catalyst under conditions of liquid-phase hydrogenations of substituted nitrobenzenes. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2012. V. 55. N 1. P. 51-56 (in Russian).
Nureyev R.M., Komarov A.A., Lefedova O.V., Ulitin M.V. Solvation and rate of reaction of 4-nitroaniline hy-drogenation in aqueous-organic media on a nickel catalyst. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2010. V. 53. N 4. P. 15-19 (in Russian).
GOST 33034-2014. Methods for testing chemical products presenting a danger to the environment. Solubility in water. M.: Standartinform. 2015. (in Russian).
Yarushok T.A., Shokhin I.E., Savchenko A.Yu. Deter-mination of the equilibrium biopharmaceutical solubility of a slightly soluble substance. Razrab. Registr. Lekarstv. Sredstv. 2012. N 1. P. 14-17 (in Russian).
Handbook on solubility. M.-L.: IAN USSR. 1962. V. 1. Book 2. P. 1479-1480 (in Russian).
Seidell A. Solubilities of organic compounds. New York: D. 10 Van Nostrand Company. 1941. V. 2. P. 480-491.
Reference book of the chemist. Ed. by B.P. Nikolsky L.: Khimiya. 1964. V. 2. P. 496-497.
Vinogradov S.V., Ulitin M.V. Hydrogenated compound effects on the kinetics of 2-propanol dehydrogenation under the conditions of liquid-phase hydrogenation. Russ. J. Phys. Chem. A. 1998. V. 72. N 5. P. 750-754.
Zakharov O.V., Lefedova O.V., Filippov D.V., Kras-nov A.I., Merkin A.A. The role of adsorption states of hydrogen in the reaction kinetics of liquid-phase hydro-genation of substituted nitrobenzenes. Vestn. Tver. Gos. Un-ta. Ser.: Khimiya. 2013. N 5. P. 201-208 (in Russian).
Barbov A.V., Shepelev M.V., Denisov S.V., Ulitin M.V. Influence of the aqueous solutions pH on the thermody-namic characteristics of individual forms of hydrogen ad-sorbed on the surface of porous nickel. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2007. V. 50. N 8. P. 25-29 (in Russian).
