Russian Journal of Physical Chemistry A

ISSN (print)0044-4537 

Media registration certificate: No. FS77-66703 dated July 28, 2016

Founder: Russian Academy of Sciences

Editor-in-Chief: Tsivadze Aslan Yusupovich

Number of issues per year: 12

Indexation: RISC, list of Higher Attestation Commissions, CrossRef, White List (level 2)

The journal publishes theoretical, computational and experimental works (including reviews) devoted to current problems of chemical thermodynamics and thermochemistry, physical chemistry of solutions and surface phenomena, quantum chemistry and structure of molecules, kinetics of processes in various media, electrochemistry, photochemistry, magnetochemistry and mechanochemistry, physical chemistry of new promising materials (including nano-sized ones) and biophysical chemistry.

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卷 99, 编号 4 (2025)

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ПРОБЛЕМЫ, ТЕНДЕНЦИИ РАЗВИТИЯ И АКТУАЛЬНЫЕ ЗАДАЧИ ФИЗИЧЕСКОЙ ХИМИИ

Carbon nanomaterials. Electron paramagnetic resonance
Ulyanov А., Kuznetsova N., Savilov S.
摘要

Electron paramagnetic resonance (EPR) is a widely used instrumental research method in chemistry, physics, biology, and materials science that can be successfully applied to characterize the electronic structure of carbon nanomaterials. This work presents a brief review of studies of various types of carbon nanostructures (CNS) by EPR, including measurement techniques, principles of spectral data processing and interpretation, and experimental results. The relationship between the properties of CNS and the nearest environment of paramagnetic centers, oxidation, and degradation of materials with time is analyzed.

Russian Journal of Physical Chemistry A. 2025;99(4):529-536
pages 529-536 views

ХИМИЧЕСКАЯ ТЕРМОДИНАМИКА И ТЕРМОХИМИЯ

Heat capacity and thermodynamic functions of lutetium titanate Lu2Ti2O7
Gagarin P., Guskov A., Guskov V., Khoroshilov A., Gavrichev K.
摘要

The heat capacity of lutetium titanate was measured in the temperature range 2–1869 K and the smoothed temperature dependences of heat capacity entropy enthalpy changes and reduced Gibbs energy were calculated. The presence of a gentle anomaly in the heat capacity of Lu2Ti2O7 in the low temperature range was confirmed and its parameters were determined. Based on the calculated values of Gibbs energy thermodynamic stability in the studied temperature range was estimated.

Russian Journal of Physical Chemistry A. 2025;99(4):537-548
pages 537-548 views
Thermodynamic properties of multicomponent oxide systems based on CeO2 according to high-temperature mass-spectrometry data
Shugurov S., Lopatin S., Zhinkina O.
摘要

Experimental data on the study of thermodynamic properties of various oxide systems containing cerium dioxide, both in the gaseous and condensed phase, are systematized. A number of regularities are revealed that allow predicting the thermochemical characteristics of these systems.

Russian Journal of Physical Chemistry A. 2025;99(4):549-553
pages 549-553 views

ХИМИЧЕСКАЯ КИНЕТИКА И КАТАЛИЗ

Peculiarities of corrosion of low-carbon steel in the flow of solutions of acids of different anionic composition containing iron(III) salts
Avdeev Y., Panova A., Andreeva T.
摘要

Corrosion of low-carbon steel in solutions of HCl, HCl + H3PO4, and H3PO4 containing Fe(III) salts is studied. In the systems involved, the corrosion of steel results from its reaction with the acid solution and Fe(III) salt. In the discussed media, partial reactions of anodic ionization of iron, cathodic reduction of H+ and Fe(III) cations are realized on steel. The first two reactions are characterized by kinetic control, and the latter is characterized by diffusion control. The accelerating effect of Fe(III) cations on steel corrosion in the media studied is predominantly due to Fe(III) reduction. Binding of Fe(III) cations into complex compounds with anions of the corrosive medium reduces the value of their diffusion coefficient (DFe(III)). The value of DFe(III) is maximum in the HCl solution and minimum in the H3PO4 solution. The rate of partial cathodic reduction reaction of Fe(III) is determined by the value of DFe(III). As a result, the accelerating effect of Fe(III) on the cathodic reaction and, hence, the general corrosion of steel in the flow of aggressive medium is most significant in the HCl solution and least significant in the H3PO4 solution.

Russian Journal of Physical Chemistry A. 2025;99(4):554-568
pages 554-568 views
First-principles study of tritium behavior in molten FLiBe
Galashev A., Anisimov A.
摘要

The behavior of tritium in molten FLiBe, including in the presence of He in it, is studied at operating temperatures of MSR. The presence of helium in the fluoride melt is found to insignificantly change the partial function of the tritium-fluorine radial distribution. In the molten salt, preferential binding of tritium to one and two fluorine ions is observed when the bond length between tritium and fluorine is limited by the radius of the first coordination sphere. Tritium is shown to bind more frequently to one fluorine ion at 1073 K, yet this advantage is not apparent in the presence of He, and the tritium coordination changes more frequently. Lower temperatures (T ≤ 973 K) contribute to binding of 3H to two fluorine ions, but the presence of He, which creates an effect of the increasing temperature, can break this trend. Tritium is concluded to very rarely form bonds simultaneously with three fluorine ions. The form of tritium binding by fluorine affects the kinetic characteristics of tritium in molten FLiBe.

Russian Journal of Physical Chemistry A. 2025;99(4):569-576
pages 569-576 views
Reactivity of tetra-4(4-methoxyphenoxy)-phthalocyanine in acid-base interaction with nitrogen-containing organic bases
Petrov О.
摘要

Interaction of tetra-4(4-methoxyphenoxy)phthalocyanine with pyridine, 2-methylpyridine, morpholine, piperidine, n-butylamine, tert-butylamine, diethylamine, and triethylamine in benzene and the benzene-dimethylsulfoxide system is studied. The acid-base interaction reaction belongs to the number of unusually slow processes and leads to the formation of time-stable complexes with proton transfer. Their structure is proposed. The change of reactivity of tetra-4(4-methoxyphenoxy)phthalocyanine depending on the polarity of the medium, proton acceptor ability, and spatial structure of the nitrogen-containing base is considered.

Russian Journal of Physical Chemistry A. 2025;99(4):577-583
pages 577-583 views

ФИЗИЧЕСКАЯ ХИМИЯ РАСТВОРОВ

Bulk properties of the water-urea-choline chloride system
Kalinyuk D., Selezeneva E., Yumakov D., Kosova G.
摘要

The available experimental data on the solution densities of two binary subsystems, viz. water — choline chloride and urea — choline chloride, and the ternary water — urea — choline chloride system are analyzed. The parameters of the Pitzer-Simonson-Clegg bulk model describing the experimental values of molar volumes of solutions of both binary subsystems and ternary system one function Vm = f(T, p, x1, x2) in the temperature range from 278.15 to 363.15 K and the pressure range from 0.1 to 50 MPa are determined. In the course of thermodynamic modeling, the dependence of the molar volume of choline chloride melt on the state parameters (p, T) is proposed. The obtained model parameters describing binary interactions in the water — choline chloride and urea — choline chloride subsystems can be used to model bulk properties of solvents with deep eutectic of different component composition.

Russian Journal of Physical Chemistry A. 2025;99(4):584-594
pages 584-594 views

СТРОЕНИЕ ВЕЩЕСТВА И КВАНТОВАЯ ХИМИЯ

Rheology of thixotropic dispersions. Transient phenomena with increasing shear rate
Matveenko V., Kirsanov E.
摘要

A structural rheological model is used to describe the thixotropic dispersed system of silicon dioxide in oil. The model includes a kinetic equation of the processes of formation and destruction of particle aggregates and a rheological equation containing a structural parameter (the number of aggregated particles in a unit volume). The case of an equilibrium plastic flow, which corresponds to experimental flow curves, is considered. The coefficients of the rheological equation are calculated. For a stepwise increase in the shear rate from γ˙1 to γ˙2, the transient process is considered as a transition from one equilibrium state of the flow to another equilibrium state through a certain nonequilibrium state of the flow. The coefficient of deviation from equilibrium is introduced, and its dependence ζ(t) is calculated using exponential functions; the limiting value ζ0 is determined. The transient dependences τ1/2(t) are approximated.

Russian Journal of Physical Chemistry A. 2025;99(4):595-604
pages 595-604 views
Quantum-chemical study of energies of maleimide and itaconimide isomeric derivatives
Panov A.
摘要

For 38 pairs of the isomeric derivatives of maleimide and itaconimide, the Gibbs free energies were calculated using the density functional theory (DFT) and domain-based local pair natural orbital (DLPNO) methods. The effects of the solvent and of substituents in positions 1, 3, and 4 of the maleimide ring on the energy difference of the isomers were studied. Depending on the substituents and conditions, the equilibrium can shift toward the maleimide or itaconimide form. Further migration of the double bond and cis-trans- isomerism were also considered wherever possible.

Russian Journal of Physical Chemistry A. 2025;99(4):605-610
pages 605-610 views

ФИЗИЧЕСКАЯ ХИМИЯ НАНОКЛАСТЕРОВ, СУПРАМОЛЕКУЛЯРНЫХ СТРУКТУР И НАНОМАТЕРИАЛОВ

Adsorption and reaction of molecules of nitrogen oxide (NO) on the surface of nickel nano-sized clusters on aluminium oxide α-Al2O3(0001)
Magkoev T., Pukhaeva N., Men Y., Behjatmanesh-Ardakani R., Elahifard M., Ashkhotov О.
摘要

Adsorption and reaction of nitrogen oxide (NO) molecules on the surface of a model metal-oxide system formed by controlled deposition of nickel clusters under ultrahigh vacuum conditions on the surface of α-Al2O3(0001) aluminum oxide thin film grown on the Mo(110) substrate is studied in-situ by experimental surface analysis methods. According to X-ray photoelectron and electron Auger spectroscopy, infrared Fourier spectroscopy, and temperature-programmed desorption data, there is a conditional Ni cluster size of 2 nm that separates the nature of the electronic state of NO molecules adsorbed on their surface and their reactivity. It is found that the peculiarity of Ni clusters with a characteristic size not exceeding 2 nm is that NO molecules are adsorbed on their surface in the form of dimers (NO)2 while for clusters of larger size adsorption occurs in the form of monomers (NO). It is concluded that this difference is the reason for the different reaction behavior of the molecules. The key difference between clusters smaller and larger than 2 nm in size is that in the former case N2O molecules are formed upon heating the system and desorbed into the gas phase while this does not occur in the latter case. The formation of N2O is due to the mutual influence of NO molecules forming the (NO)2 dimer under the action of the metal/oxide interface. The results indicate that it is possible to tune the catalytic efficiency of the metal-oxide system by varying the size of the applied metal cluster.

Russian Journal of Physical Chemistry A. 2025;99(4):611-619
pages 611-619 views
Kinetics and mechanism of coarsening for nanoparticles of sulfur and alkaline earth metal sulfates coprecipitated from true polysulfide solutions
Urakaev F., Massalimov I., Akhmetshin B., Massalimov B., Khusainov A., Samsonov M., Mustafokulov S.
摘要

Alkaline-earth metal sulfate nanoparticles (ALMS) and nanocomposites of ALMS with sulfur nanoparticles (nanosulfur) are synthesized from aqueous solutions of polysulfides (ASP) of alkaline-earth metals (AEM) of calcium, strontium, and barium (CaSn, SrSn, BaSn; n>1). AEM ASP are obtained in the aqueous medium at temperatures of 70 and 90°C as a result of the reaction between metal hydroxide and sulfur. It is found that the use of sulfur mechanically activated in the disintegrator for synthesis allows obtaining higher concentrations of AEM ASP in shorter times. To establish possible mechanisms of mechanochemical recrystallization in liquid media, the method of static light scattering is used to determine the kinetics of particle aggregation as a result of reversible aggregation of sulfur and AEM sulfate nanoparticles. It is found that at first particles with sizes about 30 nm are formed, which are enlarged to tens of microns with time. The values of the rate constant of particle aggregation (agglomeration) (Q) increase with the concentration of acids, and their optimal value for the realization of the Q-mechanism is 10%. It is found that applying a surfactant (neonol; concentration 5%) reduces Q by multiple times. It is also found that the value of Q grows with the temperature, and the activation energies of S/MeSO4 particle aggregation processes are determined for the optimum interval 300÷350 K. Practical aspects of the results of the work are considered by the example of using the obtained samples to germinate wheat grains, as well as hydrophobicity of S/MeSO4 samples due to the presence of sulfur in them.

Russian Journal of Physical Chemistry A. 2025;99(4):620-635
pages 620-635 views

ФИЗИЧЕСКАЯ ХИМИЯ ДИСПЕРСНЫХ СИСТЕМ И ПОВЕРХНОСТНЫХ ЯВЛЕНИЙ

Adsorption of molybdenum(VI) and rhenium(VII) on mechanically activated graphite
Korobitsyna A., Pechishcheva N., Konysheva E., Shunyaev K.
摘要

Sorption properties of mechanically activated graphite towards molybdenum and rhenium are studied for the first time. The optimal conditions are found such that the metals can be separated, and adsorption of molybdenum up to 95 % with adsorption of rhenium 3 % is achieved: nitric acid solution, pH 3 in the presence of 50 vol.% ethanol, stirring for 60 min. The maximum sorption capacity of the sorbent towards Mo(VI) according to the Langmuir model is 115 mg/g. The adsorption followed a pseudo-second order kinetics model. The sample after molybdenum adsorption is characterized by X-ray photoemission spectroscopy, X-ray diffraction, and X-ray-structural analysis, and scanning electron microscopy. The mechanical activation resulted in a decrease in the average size of graphite crystallites, an increase in the distance between layers, and a change in the surface state of carbon.

Russian Journal of Physical Chemistry A. 2025;99(4):636-647
pages 636-647 views
Adhesion in two-phase melts of alkali metal halogenides
Stepanov V.
摘要

Adhesive interaction of phases in two-phase LiF+KBr, LiF+CsCl, LiF+RbBr, LiF+KI, LiF+CsBr, LiF+RbI, and LiF+CsI melts is analyzed. The adhesion of phases is found to grow as the temperature increases as a result of the superposition of thermal motion of ions and changes in the compositions of coexisting phases. The adhesion of phases is shown to be the less the wider the concentration interval of immiscibility of components. At the same temperature, the adhesion of the phases increases with the decreasing difference in the size of the mixed ions.

Russian Journal of Physical Chemistry A. 2025;99(4):648-653
pages 648-653 views

ФИЗИЧЕСКАЯ ХИМИЯ ПРОЦЕССОВ РАЗДЕЛЕНИЯ. ХРОМАТОГРАФИЯ

Adsorption and retention patterns for halogen adamantanes on the graphite-like adsorbent Hypercarb under HPLC conditions
Yashkin S., Ryzhikhina E., Yashkina E., Svetlov D.
摘要

Thermodynamic characteristics of sorption (retention factors, heat and entropy factors of sorption) of various chlorine, bromine, and iodine derivatives of adamantanes from water-methanol eluent on the graphite-like material Hypercarb and octyl silica gel (SiO2–C8) are determined experimentally under HPLC conditions. Hypercarb is shown be characterized by the highest structural selectivity in HPLC with respect to stereoisomers of halogen adamantanes. It is established that the order of elution of isomeric chlorine, bromine, and iodine derivatives of adamantanes from the polar eluent medium on Hypercarb under HPLC fully coincides with the retention patterns of these compounds on columns with graphitized thermal soot in gas chromatography. The retention of the considered halogen adamantanes and halogenoarenes on Hypercarb is described by the adsorption mechanism of sorption, with the principal contribution to the retention being made by dispersive interactions of sorbate molecules with the adsorbent surface. The dependence of the heat and entropy factors of sorption on the composition and structure of halogen adamantanes on Hypercarb is noted to be described by the molecular polarizability and molecular site values of the sorbates and by the lipophilicity of the compounds in the case of sorption on SiO2–C8. It is concluded that the found regularities of halogen adamantane sorption under HPLC conditions allow referring Hypercarb and SiO2–C8 to sorbents with 2D- and 3D-types of structural selectivity, respectively.

Russian Journal of Physical Chemistry A. 2025;99(4):654-664
pages 654-664 views

ЭЛЕКТРОХИМИЯ. ГЕНЕРАЦИЯ И АККУМУЛИРОВАНИЕ ЭНЕРГИИ ИЗ ВОЗОБНОВЛЯЕМЫХ ИСТОЧНИКОВ

Low-temperature synthesis of highly ordered lithium-cobalt double phosphates with improved electrochemical characteristics in lithium nitrate melt
Zharov N., Maslova М., Semushin V.
摘要

A low-temperature technique for preparation of highly dispersed powders of lithium-cobalt double phosphates with a highly ordered crystal lattice and a given morphology is proposed. The electrochemical performance and cyclic life of the obtained compounds are shown to exceed the respective characteristics of the known analogs. The proposed method can be extended to obtain a wide range of electrode materials for lithium-ion batteries with olivine structure.

Russian Journal of Physical Chemistry A. 2025;99(4):665-674
pages 665-674 views

ФОТОХИМИЯ, МАГНЕТОХИМИЯ, МЕХАНОХИМИЯ

Ways to modernize the setup for studying fluorescence and phosphorescence excitation spectra of polyaromatic hydrocarbon molecules cooled in an inert gas jet
Terentyev R., Maslov D., Yakovlev N., Stolyarov A., Godunov I.
摘要

The experimental setup for obtaining fluorescence excitation spectra of molecules cooled in a supersonic inert gas jet is described. Fluorescence excitation spectra of substituted aldehyde molecules cooled in a supersonic jet are recorded using this setup. The spectra obtained using the setup is concluded to have a better signal-to-noise ratio as compared to the spectra known from publications. Further ways to modify the setup for registration of excitation spectra of sensibilized phosphorescence and phosphorescence of semivolatile molecules of polyaromatic hydrocarbons are considered.

Russian Journal of Physical Chemistry A. 2025;99(4):675-680
pages 675-680 views