Department of Chemical thermodynamics and kinetics

Critical phenomena and processes in multicomponent heterogeneous systems with chemical interaction

Group members

Head of Scientific Group

htk Toykka MA Pravitel

Maria A. Toikka

PhD, Associate Professor

Members

htk Trofimova MA 2020

Maya A. Trofimova

PhD, Associate Professor

Samarov grant RNF

Artemiy A. Samarov

PhD, Assistant Professor

htk Golikova AD 2020

Alexandra D. Golikova

Assistant Professor

Students

  • Alina A. Senina, student;
  • Alexander A. Smirnov, student;
  • Georgii Kh. Misikov, student;
  • Konstantin A. Zolotovskiy, student.

Research areas

Experimental studies of critical phenomena in systems with chemical interaction of components. Kinetics of chemical reactions in the near-critical region of liquid-phase systems. Thermodynamic and structural features of multicomponent critical phases during an equilibrium and non-equilibrium chemical reaction (critical surfaces and hypersurfaces). Thermodynamic and model calculations. Thermochemical studies (calorimeters of mixing, titration, differential scanning calorimetry). Deep eutectic solvents. Additional (applied) profile of activity: research of processes associated with the production of biofuels.

The journals in which the results of the scientific group are published:

m toikka journal01 m toikka journal02 m toikka journal03 m toikka journal04
m toikka journal05 m toikka journal06 m toikka journal07 m toikka journal08
m toikka journal09 m toikka journal10 m toikka journal11 m toikka journal12

News & Publications

2020

The development of an experimental base on the physicochemical properties of biofuel systems, methods of thermodynamic modeling of complex systems, which should include reaction mixtures based on biofuel production reagents, are an absolute basis for the development of energy- and resource-saving environmentally friendly technologies. One of the defining aspects of the development of the production and use of liquid biofuel — the object of this study — remains the rational use of biological resources, the implementation of processes and waste-free production.

In 2020, a research group conducted research on biofuel systems in which combined reaction-mass transfer processes take place. The importance of thermodynamic research is undeniable for expanding the fundamental basis in biofuel research. Specific experimental objects of research are model biofuel systems containing mixtures of carboxylic acids (ethane, propane) and alcohols (ethanol, propanol, butanol). The main studied physicochemical properties are chemical and phase equilibria, as well as excess enthalpies. The resulting array of fundamental physical and chemical results is included in the main databases of physical and chemical data (NIST, etc.). In theoretical terms, the analysis of the results of the project is associated with the use of the apparatus of nonequilibrium thermodynamics to characterize chemical processes.

The scientific group has published seven articles in international journals indexed in WOS / Scopus in 2020.

acs.jced.9b01205One of the images (top right), published in an article in the international journal Journal of Chemical & Engineering Data (IF 2.369), is featured on the cover of the May 2020 issue. The authors of the work are the staff of the Department of Chemical Thermodynamics and Kinetics of the Institute of Chemistry — Artemiy A. Samarov, Maya A. Trofimova, Maria A. Toikka and Alexander M. Toikka (DOI: 10.1021 / acs.jced.9b01205).

The research group implements one RFBR grant, two RSF grants and one RF President's scholarship for young scientists. In 2020, one PhD student was successfully defended.

The most significant publications of 2020:

  1. Alina Senina, Vladimir Margina, Alexandra Golikova, Nikita Tsvetov, Anna Sadaeva, Maria Toikka. Physico-chemical study of systems involving ethanol, promising for use as a biofuel // Fuel. Vol. 284 (2021) 119099. (Impact Factor Web of Science 2019 JCR Science Edition - 5.578; DOI: 10.1016 / j.fuel.2020.119099)
  2. Maria Toikka, Kristina Podryadova, Anastasia Kudryashova. Liquid-liquid equilibria, solubility and critical states in the systempropionic acid – 1-propanol –n-propyl propionate – water at 303.15 K // The Journal of Chemical Thermodynamics. Vol. 152 (2021) (online 12 August 2020) 106265. (Impact Factor Web of Science 2019 JCR Science Edition - 2.888; DOI: 10.3390 / sym12071142)
  3. Alexandra Pulyalina, Valeriia Rostovtseva, Iana Minich, Oleg Silyukov, Maria Toikka, Nataliia Saprykina, Galina Polotskaya. Specific Structure and Properties of Composite Membranes Based on the Torlon® (Polyamide-imide)/Layered Perovskite Oxide // Symmetry 2020, 12(7), 1142. (Impact Factor Web of Science 2019 JCR Science Edition - 2.645; DOI: 10.3390 / sym12071142)
  4. Nikita Tsvetov, Anna Sadaeva, Maria Toikka, Irina Zvereva, Alexander Toikka. Excess molar heat capacity for the binary system n-propyl alcohol plus water in the temperature range 278.15-358.15 K: new data and application for excess enthalpy calculation // Journal of Thermal Analysis and Calorimetry (on-line 5 April 2020) 2020. (Impact Factor Web of Science 2019 JCR Science Edition - 2.731; DOI: 10.1007 / s10973-020-09605-y)
  5. Artemiy Samarov, Maya Trofimova, Maria Toikka and Alexander Toikka. Experimental Data on Chemical Equilibrium in the System with Ethyl Formate Synthesis Reaction at 298.15 K // Journal of Chemical and Engineering Data, Available online 30 March 2020. (Impact Factor Web of Science 2019 JCR Science Edition - 2.369; DOI: 10.1021 / acs.jced.9b01205)

2019

In 2019, fundamentally new results were obtained for the prospective use and development of biofuel systems technology, solving urgent problems of optimizing biofuel production in the direction of energy and resource conservation. An experimental study of the phase behavior of biofuel systems of the carboxylic acid - alcohol - corresponding ether - water type has been carried out in a wide range of temperatures and compositions of chemically reacting mixtures, as well as an analysis of new possibilities for theoretical thermodynamic-kinetic study of combined processes. Thermochemical experiments include studies of heats of mixing (excess enthalpies) and the heats of chemical reactions in biofuel systems.

Theoretical approaches and methods for solving problems in the field of thermodynamic theory of solutions are largely based on the results of the thermodynamic school of St. apparatus of nonequilibrium thermodynamics for the development of research methods for combined membrane processes, phase and chemical equilibria, as well as for the development of the phenomenological theory of chemical processes in general. The results of the work of the scientific group were highlighted in the media: the program "Good morning" on the TV channel "Petersburg" on January 28, 2019 "What is biofuel".

In 2019, the research group has published nine articles in international journals indexed in WOS / Scopus.

The research group implements two RFBR grants, two Russian Science Foundation grants and one RF President's scholarship for young scientists. The work of the team was supported by the Government of St. Petersburg for young candidates of sciences, including in the field of scientific and pedagogical activities. In 2019, 4 bachelors successfully defended their Diploma thesis.

The most significant publications of 2019:

  1. Maria Toikka, Alexey Sadaev, Artemiy Samarov. Liquid-liquid equilibria, solubility and critical states in the system propionic acid – n-butanol – n-butyl propionate – water at 293.15 K and atmospheric pressure // The Journal of Chemical Thermodynamics, Available online 17 September 2019. (Impact Factor Web of Science 2019 JCR Science Edition - 2.888; DOI: 10.1016 / j.jct.2019.105957)
  2. Maya Trofimova, Alexey Sadaev, Artemiy Samarov, Alexandra Golikova, Nikita Tsvetov, Maria Toikka, Alexander Toikka. Liquid-liquid equilibrium of acetic acid – ethanol – ethyl acetate – water quaternary system: Data review and new results at 323.15 K and 333.15 K // Fluid Phase Equilibria. Vol. 503 (1 January 2020) (on-line 14 September 2019). (Impact Factor Web of Science 2019 JCR Science Edition - 2.838; DOI: 10.1016 / j.fluid.2019.112321)
  3. Alexandra Golikova, Nikita Tsvetov, Artemiy Samarov, Maria Toikka, Irina Zvereva, Maya Trofimova, Alexander Toikka. Excess enthalpies and heat of esterification reaction in ethanol + acetic acid + ethyl acetate + water system at 313.15 K // Journal of Thermal Analysis and Calorimetry (on-line 20 June 2019). (Impact Factor Web of Science 2018 JCR Science Edition - 2.731; DOI: 10.1007 / s10973-019-08488-y)
  4. M.A. Toikka, A.A. Samarov, A.A. Sadaeva, A.A. Senina, O. L. Lobachev. Chemical equilibrium in the system propionic acid - ethyl alcohol - ethyl propionate - water and extraction processes with the participation of deep eutectic solvents // Fine chemical technologies. Volume 14 No. 1. 2019. S. 47-58. (Impact factor RSCI 2019 - 0.25; DOI: 10.32362 / 2410-6593-2019-14-1-47-58)
  5. Alexander Smirnov, Anna Sadaeva, Kristina Podryadova, Maria Toikka. Quaternary liquid-liquid equilibrium, solubility and critical states: Acetic acid - n-butanol - n-butyl acetate - water at 318.15 K and atmospheric pressure // Fluid Phase Equilibria. Vol. 493 (1 August 2019) P. 102-108. (Impact Factor Web of Science 2019 JCR Science Edition - 2.838; DOI: 10.1016 / j.fluid.2019.04.020)
  6. Toikka M., Sadaeva A., Samarov A., Toikka A. Solubility and critical surface in the system propionic acid–ethanol–ethyl propionate–water at 293.15, 303.15 and 313.15 K // Journal of Chemical Thermodynamics. Vol. 132. May 2019. P. 113-121. (Impact Factor Web of Science 2019 JCR Science Edition - 2.888; DOI: 10.1016 / j.jct.2018.12.026)
  7. Maya Trofimova, Alexey Sadaev, Artemiy Samarov, Maria Toikka, Alexander Toikka. Solubility, liquid-liquid equilibrium and critical states for the quaternary system formic acid – ethanol – ethyl formate – water at 298.15 K and 308.15 K // Fluid Phase Equilibria. Vol. 485 (April 2019) P. 111-119. (Impact Factor Web of Science 2019 JCR Science Edition - 2.838; DOI: 10.1016 / j.fluid.2018.12.024)

2018

In 2018, work was continued on the study of reaction-mass transfer processes in multicomponent reaction stratified systems formed by biofuel components. A study of several model heterogeneous liquid-phase chemically reacting mixtures was carried out, including by calorimetric methods, which made it possible to establish new thermodynamic-kinetic regularities of the combined processes "reaction + phase transition". The element of novelty was the use of the apparatus of nonequilibrium thermodynamics.

The obtained experimental and theoretical data received the corresponding thermodynamic interpretation. In particular, a number of works provide new experimental data on phase and chemical equilibrium in systems with the participation of ethyl propionate, ethyl acetate, and amyl acetate. The extraction properties of deep eutectic solvents (DES) based on choline chloride and glycerol / urea have been studied. The information and service portal “Gazeta.ru” published a message about one of the following results: “Russian scientists have modeled the process of biofuel synthesis”.

In 2018, the research group published seven articles in international journals indexed in WOS / Scopus. Five articles — in journals of Q1 level. The group employs: 2 associate professors, 1 assistant, 1 junior researcher, 1 graduate student and 8 students.

The research group implements two RFBR grants, two Russian Science Foundation grants and two RF President's scholarships for young scientists. The work of the team was supported by the Government of St. Petersburg for young candidates of sciences, including in the field of scientific and pedagogical activities. In 2018, two bachelors successfully defended their Diploma thesis.

  1. M. Toikka, V. Vernadskaya, A. Samarov. Solubility, liquid-liquid equilibrium and critical states for quaternary system acetic acid – n-amyl alcohol – n-amyl acetate – water at 303.15 K and atmospheric pressure, Fluid Phase Equilibria. Vol. 471 (2018) P. 68–73. DOI: 10.1016/j.fluid.2018.05.009
  2. M. Toikka, D. Trofimova, A. Samarov. Liquid-liquid equilibrium and critical states for the quaternary system propionic acid–n-butanol–n-butyl propionate–water at 303.15 K, Fluid Phase Equilibria. Vol. 460 (25 March 2018) P. 17–22. DOI: 10.1016/j.fluid.2017.12.023
  3. A.A. Samarov, M.A. Smirnov, A.M. Toikka, I.V. Prikhodko, Study of Deep Eutectic Solvent on the Base Choline Chloride as Entrainer for the Separation Alcohol-Ester Systems, Journal of Chemical and Engineering Data. 2018. 63 (6). P. 1877–1884. DOI: 10.1021/acs.jced.7b00912

tma1