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List of Our Selected Scientific Papers

(illustrative examples)
(English versions of the papers given in Russian are available at the British Library Board or "NAUKA/INTERPERIODICA" Publ. Co.)
 

Fundamental problems of catalysis and adsorption

  1. V.E. Ostrovskii, "Paradox of heterogeneous catalysis": paradox or regularity, Ind. Eng. Chem. Res., 43 (2004) 3113-3126.
    Abstract: "The paradox of heterogeneous catalysis" reflects an opinion that no data file on stationary rates of a heterogeneous catalytic reaction can clarify whether the surface heterogeneity is of principal importance for the catalysis and that the surface heterogeneity is an open question. On the other hand, followers of notions on principal importance of surface heterogeneity consider the power-law kinetic equations for catalytic processes and also logarithmic isotherms and exponential rate-coverage dependences for middle-coverage chemisorption equilibriums and rates, respectively, as the manifestations and proofs of surface heterogeneity. In this paper, it is shown that the available power-law kinetic equations and the relations translated by the logarithmic isotherms and exponential rate-coverage dependences can be deduced on the basis of the notion on surface uniformity. In addition, about 40 available metal-gas systems demonstrating the constancy of the molar heats of chemisorption over wide ranges of coverages are listed and the temporal tendency of the measured molar heats of chemisorption to approach to constant levels, as the techniques and procedures are improved, is demonstrated. It is concluded that no surface heterogeneity reveals itself in catalysis and chemisorption at metals and the paradox arose from algebraic peculiarities.
  2. V.E. Ostrovskii, Mechanisms of methanol synthesis from hydrogen and carbon oxides at Cu-Zn-containing catalysts in the context of some fundamental problems of heterogeneous catalysis, Catal. Today, 77 (2002) 141-160.
    Abstract: It is stated that, for deduction of the kinetic equation of a heterogeneous catalytic process proceeding with a rate-determining step (RDS), it is necessary and sufficient to reveal the chemical nature of the RDS, composition of the surface intermediates, and stoichiometric number (SN) of the RDS. On the basis of calorimetric and adsorption methods applied to the Cu-Zn-containing catalyst reduced to a state identical to that occurring during the steady-state methanol synthesis from hydrogen and carbon oxides, three catalytic surfaces (S1, S2, and S3) are specified and the individual steps of the steady-state process are studied. It is stated that CH3OH is produced at S2 (the ZnO-component) from H2 and CO2 by two routes N1 and N2 with RDSs of interaction between gaseous H2 or CO2 and adsorbed CO2 or H2, respectively, SN = 2 for each RDS, and the adsorbed intermediates are H2, CO2, HCOH, HCOOH, and O2; CO2 is produced at S1 (the Cu-component approximated by Cu4∙OH2) through the shift-reaction; S1 and S2 are homogeneous in their adsorption properties. The causes of the absence of manifestation of the structural heterogeneity of catalysts in their adsorption and catalytic properties are considered.
  3. V.E.Ostrovskii, Mechanisms of heterogeneous catalytic processes, Dokl. AN SSSR, 313 (1990) 645-650.
  4. V.E.Ostrovskii, On the essence of the logarithmic isotherm in adsorption and electrochemical studies, Dokl. AN SSSR, 307 (1989) 1165-1169.
  5. V.E.Ostrovskii, Progress in the methods of describing of adsorption in the context of general postulates of the Langmuir theory, Uspechi chimii (Rus. Chem. Rev.), 45 (1976) 849-876.

Application of calorimetric and adsorption techniques and theoretical approaches

(a) redox heterogeneous catalytic reactions and chemisorption.

  1. V .E. Ostrovskii, Mechanisms of methanol synthesis from hydrogen and carbon oxides at copper-zinc-containing catalysts, Khim.tverdogo topl. (Chemistry of solid fuel), no.1 (2002) 59-79 (volumes are not numerated).
  2. V.E.Ostrovskii, On the mechanisms of the ammonia synthesis on iron catalysts and on the kinetic equation of the process, Zh. Phys. Khim.(Rus. J. Phys. Chem.), 63 (1989) 2560-2570.
    Abstract: Basing on an analysis of available data relating to the properties of catalytic surfaces and to the individual steps of the process of ammonia formation, we show that the basic assumptions on the mechanism of this process postulated in the earlier works by Temkin are not fulfilled. We propose a mechanism which is not inconsistent with the experimental data on the reaction  steps and leads to a kinetic equation which describes the rates of the synthesis both under industrial conditions (i.e. close to the equilibrium) and far from the equilibrium. The mechanism does not stipulate heterogeneity of the surface with respect to adsorption capacity and treats the reaction as taking place on a surface almost entirely covered with nitrogen atoms or by species containing one nitrogen atom and one or two hydrogen atoms.  
  3. V.E. Ostrovskii, Metal-oxygen-hydrogen solid system of controlled composition: differential heat effects, kinetics, and mechanism of the CuO --> Cu4∙OH2 grading, Intern. J. Modern Phys. B, 16 (1-2) (2002) 42-49.
    Abstract: The process of fine-crystal CuO reduction by successive small portions of H2 was studied through isothermal calorimetric, kinetic, adsorption-desorption, and stoichiometric measurements at 293-520 K and H2 pressures up to 100 Pa under conditions when equilibrium within the solid was achieved at any instant. The CuO studied was in the form of the component of the CuO-ZnO-Al2O3 system. The stoichiometry of the copper component reduced corresponded to Cu4∙OH2.
  4. V.E. Ostrovskii, Heats of oxygen chemisorption by cobalt and the influence of inert gases on the rate of chemisorption, Zh. Fiz. Khim. (Rus. J. Phys. Chem.), 62 (1988) 674-681.
  5. A.A. Dyatlov, V.E. Ostrovskii, Identification of substances desorbing under vacuum from the surface of a copper-zinc-aluminum catalyst of methanol synthesis after carbon dioxide and hydrogen chemisorption by the catalyst, Kinet. Katal., 26 (1985) 1154-1161.
  6. A.A. Dyatlov, V.E. Ostrovskii, Chemisorption of carbon dioxide, oxygen and hydrogen on the Cu-Zn-Al catalyst of the methanol synthesis, Kinet. Katal., 25 (1984) 159-168.
  7. V.E. Ostrovskii, E.A. Medvedkova, Calorimetric and adsorption study of oxygen, hydrogen and water interaction with surface of silver catalyst, Kinet. Katal., 20 (1979) 966-973.
  8. V.E. Ostrovskii, A.A. Dyatlov, Calorimetric study of the mechanisms of CO and hydrogen oxidation and of shift reaction on an oxide Cu-Cr catalyst, Kinet. Katal., 20 (1979) 958-968.  
  9. V.E. Ostrovskii, Combined use of calorimetric and adsorption kinetic methods for the study of the mechanisms of catalytic processes, J. Therm Anal., 14 (1978) 27-43.
  10. V.E. Ostrovskii, E.G. Igranova, Calorimetric study of heats of nitrogen chemisorption at the catalyst of ammonia synthesis, Kinet. Katal., 19 (1978) 681-689.
  11. E.G. Igranova, V.E. Ostrovskii, M.I. Temkin, Calorimetric study of nitrogen incomplete hydrogenation products adsorbed on iron catalyst, in the context of the mechanisms of ammonia synthesis, Kinet. Katal., 17 (1976) 1257-1265.
  12. V.E. Ostrovskii, A.A. Dyatlov, N.N. Dobrovol’skii, Mechanisms and kinetics of hydrogen oxidation at black copper oxide, Kinet. Katal., 17 (1976) 405-412.
  13. E.G. Igranova, V.E. Ostrovskii, Calorimetric study of hydrogen sorption at an iron catalyst of ammonia synthesis, Dokl. AN SSSR, 221 (1975) 1351-1356.
  14. V.E. Ostrovskii, Differential heats of hydrogen adsorption on surface of NiO and kinetics of the process, Dokl. AN SSSR, 196 (1971) 1141-1149.  
  15. N.N. Dobrovol’skii, V.E. Ostrovskii, Kinetics and differential heats of adsorption of oxygen on gold, Kinet. Katal., 12 (1971) 1495-1502.
  16. V.E. Ostrovskii, B.B. Chesnokov, M.I. Temkin, Adiabatic warming of coal as a result of ethylene adsorption, Khim. prom. (Chemical industry), no. 12 (1968) 926-930 (volumes are not numerated).
  17. V.E. Ostrovskii, Study of oxygen and hydrogen adsorption on copper by a method of adsorption calorimetry, Dokl. AN SSSR, 172 (1967) 892-897.  

(b) catalytic polymerization

  1. V.E. Ostrovskii, V.A. Khodzhemirov, Catalytic polymerization of ethylene, 1,4-butadiene, and ethylene oxide with no solvent: heat effects, kinetics, and mechanisms, Mol. Cryst. Liq. Cryst.,390 (2003) 67-78.
    Abstract: The processes of solid polyethyleneoxide (PEO), polyethylene (PE), and trans-1,4-polybutadiene (PB) formation at solid catalysts in gas-solid systems with no solvent are studied. For a monomer pressure of 760 Torr, maximum rates of 1.5∙10-7, 1.2∙10-5, and 4∙10-7 (mol/s cm3) are fixed for C2H4O, C2H4, and 1,4-C4H6 polymerization, respectively; therewith, potentialities of intensification of the reactions are not exhausted. The DH0298 values measured for the reaction (MON)(gas) = (1/n) (-MON-)n(solid) (MON is a monomer molecule) are -107.5+/-2.5, -112.5+/-2.5, and -140.5+/-3.8 (kJ/mol) for PE, PB, and PEO, respectively.
  2. V.E. Ostrovskii, V.A. Khodzhemirov, Polyethyleneoxide: kinetics and polymerization heat measurements for the process of catalytic polymerization in a solid-gas system free of solvent, Int. J. Modern Phys. B,16(1) (2002) 399-406.
    Abstract: The process of polymerization of ethylene-oxide (EO) vapor to solid polyethyleneoxide (PEO) at the dry KOH catalyst with no solvent is studied at 298 K and a monomer pressure up to 400 Torr. The maximum rate observed is about 1.5∙10-7 mol/s per 1 cm3 of the catalyst at 760 Torr; therewith, potentialities of intensification of the process are not exhausted. It is found that, at any fixed degree of polymerization, the rate of the process is proportional to the monomer pressure. A phenomenon of gradual increasing in the rate of polymerization with the degree of polymerization is observed. The DH0298 value measured for the reaction n(EO)(gas) = (-EO-)n(solid) is equal to -140.5+/-3.8 kJ/mol; by using this value, DH(liq. EO  P  sol.. PEO) = -109.20 kJ/mol is computed. The calorimetric results and the nature of the phenomenon revealed are discussed.

(c) physical adsorption

  1. K.I.Sakodynsky, V.E.Ostrovskii, L.D.Glazunova, Study of some polymeric sorbents by adsorption and calorimetric methods, J. Chromatogr., 156 (1978) 233-240.  
  2. V.E.Ostrovskii, L.D.Glazunova, Heats of vapor adsorption and mechanisms of vapor adsorption on polymer sorbents, Kinet. Katal., 18 (1977) 995-1004.  
  3. L.D. Glazunova, V.E. Ostrovskii, K.I. Sakodynskii, Use of the theory of polymolecular adsorption on heterogeneous surfaces for description of adsorption of hydrocarbons on polymer sorbents, Zh. Teor. Eksp. Khim. (J. Theor. Exper. Chem.), 12 (1976) 482-490.
  4. V.E. Ostrovskii, A.N. Abdrakhimova, K.I. Sakodynskii, Adsorption equilibrium and heats of butane adsorption on polydivinylbenzene, Dokl. AN SSSR, 208 (1973) 654-659.

(d) H2O sorption by monomers and polymers (including DNA), wetting and drying

  1. V.E. Ostrovskii, E.A. Kadyshevich, Hydrate model of the equilibrium DNA-water systems, Intern. J. of Nanoscience, 1 (2002) 101-121.
    Abstract: A hydrate model for the DNA-H2O system is proposed. For the notions developed, available data on a tendency of H2O molecules to form structured hydrates containing atomic groups, molecules, or atoms housed within the structural cavities formed by H-bonded H2O molecules are used. It is shown that the large and small cavities of the hydrate structure II are in close geometric agreement with N-bases and deoxyribose and with other atomic groups of DNA molecules, respectively. On the basis of the model proposed and with the Watson-Crick base-pairing scheme, the number of pairs of N-bases per helix turn (11.25), the density (1.161 g/cm3), and the helix step (0.567 nm) for the quasi-equilibrium DNA (RNA)-water system are computed, the last value nearly coinciding with the well-known alpha-helix step in the protein secondary structure (5.44 nm). It is found that the density computed by us for Wilkins-Franklin's DNA-H2O samples assumed to be non-equilibrium (1.351 g/cm3) is in accordance with their earlier data. (1.34-1.39 g/cm3). Assumptions on the phenomenology of some stages of mitosis are presented.
  2. V.E. Ostrovskii, B.V. Tsurkova, E.A. Kadyshevich, B.V. Gostev, Comparison study of the acrylamide-water and polyacrylamide-water systems: differential heat effects, kinetics, and mechanisms of drying and water-vapor wetting, J.  Phys. Chem. B, 105 (2001) 12680-12687.
    Abstract: Heat effects and kinetics of wetting by water vapor and of vacuum drying in the acrylamide (AA)-water system at 0 < n < 74 (n is the number of sorbed water molecules per one AA molecule) are studied. The water sorption by AA from air of 100% humidity appears to be limitless. It is shown that the differential heats of water sorption are about 25 kJ/mol at dry AA, pass a maximum of 42 kJ/mol in the vicinity of n = 1 and a minimum of 24 kJ/mol in the vicinity of n = 2, and then approach the level of the heat of water condensation on the pure water surface; probability of vacuum desorption of water molecules is totally increasing with n, and against this background, minima at n = 5-6 and n = 15-17 are observed. The results are compared with the corresponding data for the polyacrylamide (PAA)-water system; the mechanisms of wetting and drying of these two systems are developed on the basis of the new results, available literature and our previous pattern.
  3. V.E.Ostrovskii, E.A. Kadyshevich, Use of data on the polyacrylamide–water system for clarification of the equilibrium DNA–water system structure, Rus. J. Phys. Chem., 74 (2000) 1114-1124.  
  4. V.E. Ostrovskii, B.V. Tsurkova, The polyacrylamide-water system: application of differential calorimetry to study the mechanisms of dissolution, Thermochem. Acta, 316 (1998) 111-122.
    Abstract: Differential heat effects and rates of water sorption and desorption are investigated in the polyacrylamide (PAA)-water system at 0 < n < 25 (n = (H2O)sorb /(-C(O)NH2)). It is stated that, at 292 K in air of 100% humidity, the equilibrium corresponds to n ~ 18 (n (eq)); the heats of water vapor sorption decrease from 56 kJ/mol (initial heat) to the heat  of water vaporization (QL) at n ~ 0.5, and then they pass  (up to n (eq)) through several maxima and minima in  the vicinity of QL; at n > n (eq) they are equal to QL. It is concluded that sorption of water by dry PAA leads to linearization of PAA molecules, to the space between the amido groups of each PAA molecule being filled with water, and to neighboring order at which each PAA molecule is surrounded (at the section normal to the main carbon chain) by six nearest ones. At equilibrium, the PAA molecules are separated from each other by  a water layer of three-molecule thickness.
  5. V.E. Ostrovskii, B.V. Tsurkova, Differential heat effects and mechanisms of interaction of polyacrylamide with water, Zh. Fiz. Khim.(Russ. J. Phys. Chem), 71 (1997) 967-973.  
  6. V.E. Ostrovskii, B.V.Gostev, Heat effects and rates and molecular mechanisms of water sorption by pefluorinated polymer materials bearing functional groups, J. Therm. Anal., 46 (1996) 397-416.
    Abstract: The heat effects and the rates and equilibrium quantities of H2O vapour sorbed and desorbed on polymeric perfluorinated materials (functional groups -SO3H, -SO3Na, -SO3K) and on material treated with FeCl3 solution as sorbent were investigated. Sorbed H2O may be completely desorbed in vacuum at 443 K. The material bearing -SO3H has maximum sorption affinity: the molar heat of -SO3H wetting is close to that of H2SO4 wetting. The differential heat of sorption decreases from 68 kJ/mol at n~0 (n = H2O/-SO3H) to 45 kJ/mol at n~5, but not below the heat of H2O condensation. The -SO3H samples sorb H2O vapour in the presence of liquid H2O at 293 K up to n~17. The -SO3K material has minimum affinity for H2O: the equilibrium quantity sorbed in room air is less by a factor of 4 than that for the -SO3H material. The spatial arrangement of H2O molecules near the sulpho groups is considered.
  7. B.V. Gostev, V.E. Ostrovskii, Water sorption by perfluorinated membrane materials treated by ferric chloride water solution, Zh. Fiz. Khim. (Russ. J. Phys. Chem), 68 (1994) 668-675.   
  8. V.E. Ostrovskii, S.A. Artamonov, G.P. Korneeva, et al., Heats of acrylamide dissolution in water, Izv. AN Kaz. SSR (Proc. Kazakh. Acad. Sci.), B, no. 4 (1974) 84-88.  

Scientific Instrumentation and Methodology

  1. V.E. Ostrovskii, Some problems in adsorption and calorimetric studies of the steps of catalytic processes, J. Natural Gas Chem., 13 (2004) 123-147. 
    Abstract: Principal side factors as well as technical and procedural peculiarities capable of distorting the results of measurements of adsorbed and desorbed amounts, of falsifying the nature of the processes proceeding in the systems under study, and of promoting artifacts in calorimetric and other studies of gas chemisorption on powders are considered. Modified techniques and procedures allowing the elimination of sources of side phenomena and artifacts and freeing traditional glass static adsorption apparatuses and experimental procedures from undesirable factors and peculiarities are proposed. Some available chemisorption and calorimetric data representing artifacts and also some data that are not artifacts but, due to imperfections of chemisorption techniques, show up as artifacts are presented and discussed. Several applications of the improved techniques and procedures to calorimetric and adsorption studies of the steps of catalytic processes proceeding on the basis of natural gas and of products of its processing are presented and iscussed.

    Microcalorimeter "FOSKA"
    Microcalorimeter
    1. - calorimetric vessel,   
    2. - calorimetric ampoule,
    3. - Pt thermoresistors,
    4. - insulating rings,  
    5. - insulating tubes,
    6. - whatnot devices,  
    7. - canisters,
    8. -  metal block, 
    9. -  heater,
    10. - detent,  
    11. - insulating material.

  2. V.E. Ostrovskii, Differential microcalorimeter for isothermal measurements of heat effects in two-phase systems and examples of its application, Rev. Sci. Instr., 73 (2002) 1304-12. 
    Abstract: A differential heat-conducting double microcalorimeter intended for heat measurements at 300-700 K is described. Platinum resistance thermometers are applied as the heat-flux sensors. The calorimeter is a low-noise instrument with the baseline fluctuations ranging up to 0.02∙10-6 V (5∙10-6 W); it allows measurements of the heat effects with an error of 1-1.5% at a recorder scale of about 1∙10-2 J/cm2. The design features and the method of the heat flux transformation to the electric signals, the calorimetric ampoules for measurements and for calibration and the calibrating device, the heat-balance equation and the equation for the temperature dependence of the calorimetric sensitivity, the results of the calibration and the verification of the calorimeter, and a number of illustrative examples of calorimetric measurements are presented. The calorimeters are applicable for studying solid-gas, solid-liquid, and liquid-gas interactions and thermophysical characteristics of solids and liquids. 
  3. V.E.Ostrovskii, N.N.Dobrovol’skii, I.R.Karpovich, F.Ya. Frolov, Universal automatic differential microcalorimeter, Zh. Fiz. Khim. (Rus. J. Phys. Chem.), 42 (1968) 550-555

Earlier studies

  1. V.E. Ostrovskii, N.V. Kul’kova, M.S. Kharson, M.I. Temkin, Kinetics of ethylene oxidation, Kinet. Katal., 5 (1964) 469-476.  
  2. V.E. Ostrovskii, N.V. Kul’kova, V.L. Lopatin, M.I. Temkin, Influence of electronegative elements on catalytic properties of silver catalysts in the process of ethylene oxidation, Kinet. Katal., 3 (1962) 189-195.