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Journal Cover Kinetics and Catalysis
  [SJR: 0.317]   [H-I: 23]   [3 followers]  Follow
   Hybrid Journal Hybrid journal (It can contain Open Access articles)
   ISSN (Print) 1608-3210 - ISSN (Online) 0023-1584
   Published by Springer-Verlag Homepage  [2329 journals]
  • Kinetics and mechanism of the photolysis of CF 2 ClBr exposed to light
           with a wavelength of 253.7 nm
    • Authors: T. I. Belyakova; I. K. Larin; N. A. Messineva; A. I. Spasskii; E. M. Trofimova
      Pages: 105 - 110
      Abstract: CF2ClBr mixed with oxygen was photolyzed using a low pressure mercury lamp, and the kinetics of photolysis was studied. The absorption spectra of the starting material and products of photolysis were recorded in the wavelength range from 200 to 900 nm on an Agilent 8453 spectrophotometer. The concentrations of the main photolysis products at different irradiation times were calculated by the mathematical processing of the absorption spectra. The scheme of CF2ClBr photolysis was suggested, the model calculations according to this scheme were performed, and the results of simulation were compared with experimental data.
      PubDate: 2017-03-01
      DOI: 10.1134/s002315841702001x
      Issue No: Vol. 58, No. 2 (2017)
  • Ring-opening metathesis polymerization (ROMP) of fullerene-containing
           monomers in the presence of a first-generation Grubbs catalyst
    • Authors: Yu. N. Biglova; A. G. Mustafin; S. A. Torosyan; R. Z. Biglova; M. S. Miftakhov
      Pages: 111 - 121
      Abstract: New norbornene-type monomers containing covalently bound C60 fullerene have been obtained. In the presence of the 1st generation Grubbs catalyst [(PCy3)2Cl2RuCHPh] (Cy is cyclohexyl), these monomers smoothly undergo homopolymerization and copolymerization with parent fullerene-free monomers. The homopolymers are insoluble in common organic solvents, while the copolymers obtained at different molar ratios to their fullerene-free analogues are very soluble in organic solvents and can be suitable for the preparation of thin films.
      PubDate: 2017-03-01
      DOI: 10.1134/s0023158417020021
      Issue No: Vol. 58, No. 2 (2017)
  • Kinetic scheme and rate constants for methyl methacrylate synthesis
           occurring via the radical–coordination mechanism
    • Authors: N. V. Ulitin; K. A. Tereshchenko; A. K. Frizen; A. O. Burakova; S. V. Kolesov; D. A. Shiyan; N. E. Temnikova
      Pages: 122 - 132
      Abstract: Two kinetic schemes of the bulk radical–coordination polymerization of methyl methacrylate initiated by the benzoyl peroxide–ferrocene system are considered from the standpoint of formal kinetics. The most likely kinetic scheme is the one that includes the reactions characteristic of classical radical polymerization and, additionally, reactions of controlled radical polymerization proceeding via the Organometallic Mediated Radical Polymerization mechanism, a reaction generating a coordination active site, and a chain propagation reaction in the coordination sphere of the metal. The temperature dependences of the rate constants for the reactions of this kinetic scheme at temperatures typical of commercial poly(methyl methacrylate) production (313–353 K) have been determined by solving the inverse kinetic problem.
      PubDate: 2017-03-01
      DOI: 10.1134/s0023158417020136
      Issue No: Vol. 58, No. 2 (2017)
  • Catalytic and inhibiting effects of ferrocene on the bulk
           radical–coordination polymerization of methyl methacrylate from the
           standpoint of formal kinetics
    • Authors: K. A. Tereshchenko; N. V. Ulitin; S. V. Kolesov; A. O. Burakova; D. A. Shiyan; N. E. Temnikova
      Pages: 133 - 139
      Abstract: The kinetic curves and rates of bulk radical–coordination polymerization of methyl methacrylate initiated by the benzoyl peroxide–ferrocene system at 293–373 K, initial benzoyl peroxide concentrations of 10–4–10–1 mol/L, and a constant initial ferrocene concentration of 10–3 mol/L have been calculated using a mathematical model in which the process is considered from the standpoint of formal kinetics. The calculations have demonstrated that, at low methyl methacrylate conversions, ferrocene catalyzes the process at any benzoyl peroxide concentration; at medium and high methyl methacrylate conversions, deficient amounts of ferrocene with respect to benzoyl catalyze the process as well, while excess ferrocene inhibits the process. The observed effect is explained by the specific ferrocene–benzoyl peroxide interaction, which, depending on the ferrocene: benzoyl peroxide ratio, either increases or decreases the concentration of radicals in the reaction mass.
      PubDate: 2017-03-01
      DOI: 10.1134/s0023158417020124
      Issue No: Vol. 58, No. 2 (2017)
  • Synthesis and characterization of Sibunit-supported Pd–Ga, Pd–Zn, and
           Pd–Ag catalysts for liquid-phase acetylene hydrogenation
    • Authors: D. V. Glyzdova; N. S. Smirnova; N. N. Leont’eva; E. Yu. Gerasimov; I. P. Prosvirin; V. I. Vershinin; D. A. Shlyapin; P. G. Tsyrul’nikov
      Pages: 140 - 146
      Abstract: Pd/Sibunit and Pd–M/Sibunit (M = Ga, Zn, or Ag) catalysts have been synthesized, and their catalytic properties in liquid-phase acetylene hydrogenation have been investigated. Doping of the palladium catalyst with a metal M leads to the formation of the Pd2Ga, PdZn, or Pd0.46Ag0.54 bimetallic compound. The bimetallic particles are much smaller (1.6–2.0 nm) than the monometallic palladium particles (4.0 nm). Doping with zinc raises the ethylene selectivity by 25% without affecting the activity of the catalyst. Specific features of the effect of each of the dopants on palladium are reported.
      PubDate: 2017-03-01
      DOI: 10.1134/s0023158417020057
      Issue No: Vol. 58, No. 2 (2017)
  • Kinetics and mechanism of the production of higher olefins from stearic
           acid in the presence of an alumina-supported nickel sulfide catalyst
    • Authors: E. A. Katsman; V. Ya. Danyushevsky; P. S. Kuznetsov; R. S. Shamsiev; A. S. Berenblyum
      Pages: 147 - 155
      Abstract: A nickel sulfide catalyst which efficient in the decarbonylation of fatty acids to olefins and dienes has been obtained for the first time by treating alumina-supported nickel sulfate with hydrogen, and its properties have been studied. In its presence, the olefin selectivity of the reaction can exceed 90%. The kinetics of stearic acid deoxygenation to heptadecenes has been investigated, a kinetic model has been constructed, and a mechanism has been proposed for the reaction over this catalyst. Olefin oligomerization is the dominant side reaction. Kinetic evidence for the catalytic inhibition of oligomerization by nickel hydrides formed on the catalyst has been obtained. The compositions of active site–reactant adsorption complexes have been discussed.
      PubDate: 2017-03-01
      DOI: 10.1134/s0023158417020069
      Issue No: Vol. 58, No. 2 (2017)
  • Oxidative dehydrogenation of ethane over a Mo–V–Nb–Te–O
           mixed-oxide catalyst in a cyclic mode
    • Authors: I. I. Mishanin; A. N. Kalenchuk; K. I. Maslakov; V. V. Lunin; A. E. Koklin; E. D. Finashina; V. I. Bogdan
      Pages: 156 - 160
      Abstract: The oxidative dehydrogenation of ethane (ODE) into ethylene over a Mo–V–Nb–Te–O mixedoxide catalyst in a cyclic mode with alternate feeding of ethane and air has been investigated. The amount of oxide-phase oxygen involved in the reaction has been estimated by titrating the oxygen of the active phase of the catalyst with ethane. The reactivity of this oxygen increases with an increasing temperature. The amount active oxygen involved in ODE at 360–400°C is 0.2–0.6 mmol/g.
      PubDate: 2017-03-01
      DOI: 10.1134/s0023158417020094
      Issue No: Vol. 58, No. 2 (2017)
  • Thermal deactivation mechanism and the effect of Nd addition on the
           deactivation of the Pt/SiO 2 catalyst for NO oxidation reaction
    • Authors: Y.-K. Chung; H.-I. Lee
      Pages: 161 - 166
      Abstract: Pt-based catalysts cannot be used permanently for the diesel after-treatment system because the catalytic activity is decreased due to coarsening of Pt particles at high temperature of the exhaust gas. In this study, to prevent Pt-based catalyst from deactivation, Nd was added to the Pt/SiO2 catalyst, and the effect of the Nd addition on the catalytic activity was investigated. The Pt/SiO2 catalyst showed a high catalytic activity for the oxidation of NO but was severely deactivated after the fast thermal aging process. Pt crystallite size was increased and some Pt particles were buried in the SiO2 pore during the fast thermal aging process, which led to the decrease of catalytic activity. Nd-added Pt/SiO2 catalyst showed lower activity than Pt/SiO2 catalyst, but Pt–Nd/SiO2 catalyst maintained its catalytic activity after fast thermal aging process. It can be postulated that a stable Nd silicate, on which Pt particle is placed, protects SiO2 pores from destruction and so the number of the catalytically active sites remains nearly unchanged. As a result the Pt–Nd/SiO2 catalyst maintained its catalytic activity after fast thermal aging process.
      PubDate: 2017-03-01
      DOI: 10.1134/s0023158417020045
      Issue No: Vol. 58, No. 2 (2017)
  • Monolithic FeO x /Al 2 O 3 catalysts for ammonia oxidation and nitrous
           oxide decomposition
    • Authors: L. G. Pinaeva; L. S. Dovlitova; L. A. Isupova
      Pages: 167 - 178
      Abstract: (1.2–8.3)%FeOх/Al2O3 monolith catalysts have been prepared by impregnating alumina with aqueous solutions of iron(III) nitrate and oxalate and have been tested in NH3 oxidation and in the selective decomposition of N2O in mixtures resulting from ammonia oxidation over a Pt–Rh gauze pack under conditions of nitric acid synthesis (800–900°C). In the case of the support calcined at 1200°C, the catalyst is dominated by bulk Fe2O3 particles localized on the Al2O3 surface. The activity of these samples in both reactions decreases with a decreasing active component content, thus limiting the potential of Fe2(C2O4)3 · 5H2O, an environmentally friendlier but poorly soluble compound, as a substitute for Fe(NO3)3 · 9H2O. Decreasing the support calcination temperature to 1000°C or below leads to the formation of a highly defective Fe–Al–O solid solution in the (1.2–2.7)%FeOх/Al2O3 catalysts. The surface layers of the solid solution are enriched with iron ions or stabilize ultrafine FeOх particles. The catalytic activity of these samples in both reactions is close to the activities measured for ~8%FeOх/Al2O3 samples prepared using iron nitrate.
      PubDate: 2017-03-01
      DOI: 10.1134/s0023158417020100
      Issue No: Vol. 58, No. 2 (2017)
  • Kinetics and mechanism of the low-temperature oxidation of carbon monoxide
           with oxygen on a PdCl 2 –CuCl 2 /γ-Al 2 O 3 catalyst
    • Authors: L. G. Bruk; A. V. Ustyugov; E. A. Katsman; L. D. Iskhakova; I. V. Oshanina; O. P. Tkachenko; L. M. Kustov; O. N. Temkin
      Pages: 179 - 190
      Abstract: A systematic study of the kinetics of the low-temperature oxidation of carbon monoxide with oxygen on a PdCl2–CuCl2/γ-Al2O3 supported catalyst was carried out over a wide range of the partial pressures of oxygen, water, and CO in order to test hypotheses on the reaction mechanism. It was shown that, as the temperature was increased from 20 to 38°C, rate of formation of CO2 decreased and the apparent activation energy was about–40 kJ/mol. The hypotheses of different degrees of complexity concerning the reaction mechanism were formulated based on physicochemical data and a Langmuir–Hinshelwood model. Mechanisms in which carbon dioxide is formed on the interaction of the surface Pd(I) and Pd(II) complexes that include carbon monoxide and water with the surface complex of Cu(I) that coordinates oxygen were recognized as the most probable.
      PubDate: 2017-03-01
      DOI: 10.1134/s0023158417020033
      Issue No: Vol. 58, No. 2 (2017)
  • Preparation and characterization of microcapsulated red phosphorus and
           kinetic analysis of its thermal oxidation
    • Authors: Jie Liu; Hua Guan; Dongming Song
      Pages: 191 - 197
      Abstract: Microcapsulated red phosphorus (MRP) with aluminum hydroxide/phenolic resin coating layer was prepared by a two-step coating process. The results of Fourier-transform infrared spectroscopy and scanning electron microscopy show that red phosphorus (RP) is coated by aluminum hydroxide and phenolic resin. MRP absorbs less water and is more thermally stable than RP. The thermal oxidation kinetics of MRP was investigated by TG/DTG/DTA under air atmosphere using non-isothermal experiments with the heating rates ranging from 10 to 25°C/min. The values of the apparent activation energy E a were 168 ± 9 kJ/mol as determined by the isoconversional Ozawa–Flynn–Wall method and 164 ± 12 kJ/mol according to the Kissinger−Akahira−Sunose method. Based on Málek’s procedure the kinetic reaction follows the Šesták–Berggren model with f(α) = α0.34(1 − α)0.94 (α is RP conversion) and pre-exponential factor A = 3.11 × 1012 s–1. The simulated curves were fitted with experimental curves constructed by plotting dα/dt vs temperature at different heating rates.
      PubDate: 2017-03-01
      DOI: 10.1134/s0023158417020070
      Issue No: Vol. 58, No. 2 (2017)
  • Spectrokinetic study of the mechanism of NO x reduction with propylene
           over ZrO 2 in excess oxygen
    • Authors: V. A. Matyshak; A. N. Il’ichev; O. N. Sil’chenkova; V. A. Sadykov; V. N. Korchak
      Pages: 198 - 210
      Abstract: It has been demonstrated by quantitative spectrokinetic measurements that, on the surface of zirconia stabilized as a tetragonal phase, the rate-limiting step of the selective catalytic reduction of nitrogen oxides (SCR of NO x ) with propylene is the interaction of surface nitrates with C3H6 yielding organic nitro compounds. It is hypothesized that propylene reacts not with the nitrates themselves but with the activated complex NO2 ads whose structure is intermediate between the structures of the monodentate NO3 − and NO2 species. Deep C3H6 oxidation exerts an adverse effect on the rate of the SCR of NO x with propylene, and the interaction between O2 and NO, which yields NO2 and NO3 − stimulates further nitrogen reduction to N2. The effect of the reaction between oxygen and O2N−C n H m on the NO x reduction rate is variable and is determined by the C3H6/NO x ratio. A generalized scheme of the SCR of NO x with propylene on the surface of ZrO2 partially stabilized as a tetragonal phase has been developed by comparing experimental data of this study and data available from the literature.
      PubDate: 2017-03-01
      DOI: 10.1134/s0023158417020082
      Issue No: Vol. 58, No. 2 (2017)
  • Mathematical modeling of heterogeneous catalysis involving
           polymer-supported catalysts
    • Authors: H. A. Silva; L. G. Aguiar
      Pages: 211 - 217
      Abstract: This study reports the mathematical modeling of catalytic reaction systems involving polymer-supported catalysts. Differential mass balances were applied to species and the partial differential equations were solved through the method of lines in MATLAB®. Etherification and esterification reactions were studied with the present model and validation was performed with literature data, providing fair agreement. Furthermore, the model proved capable of predicting concentration gradients along the catalyst particles, providing an interesting level of detail to represent catalytic heterogeneous systems.
      PubDate: 2017-03-01
      DOI: 10.1134/s0023158417020112
      Issue No: Vol. 58, No. 2 (2017)
  • Inhibition of the reaction between hydrogen and oxygen by multiatomic gas
           admixtures behind the incident shock wave front
    • Authors: O. V. Skrebkov; S. S. Kostenko
      Pages: 1 - 8
      Abstract: The inhibiting effect of multiatomic gases has been investigated by numerical simulation of hydrogen oxidation with account taken of the nonequilibrium state of the initial components, intermediates, and reaction products behind the shock wave in the framework of a vibrationally nonequilibrated model. The central feature of the model is successively taking into account the vibrational disequilibrium of the HO2 radical as the most important intermediate in the chain branching process. The inhibiting effect can be explained by the influence of the multiatomic gases on the rate of the vibrational relaxation of the vibrationally excited HO2 radical resulting from the reaction. Methane, tetrafluoromethane, fluoromethane, difluoromethane, chlorofluoromethane, formaldehyde, ethane, hexafluoroethane, ethylene, tetrafluoroethylene, and propane have been considered as inhibitory admixtures.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010098
      Issue No: Vol. 58, No. 1 (2017)
  • Reactivity of cycloalkanes in hydrogen abstraction with different
    • Authors: B. E. Krisyuk; E. A. Mamin; A. A. Popov
      Pages: 9 - 14
      Abstract: The reactions of some acceptors (∙CH3, ∙OOH, ∙CCl3, O3, and Br∙) with saturated cyclic hydrocarbons, viz., cyclohexane, cycloheptane, and cyclooctane were studied by the DFT methods based on B3LYP and PBE0 functionals, the method based on the double hybrid functional B2PLYP, a combined ONIOM approach (CCSD:B3LYP)) and the coupled-cluster method (CCSD) using the 6-31+G**, aug-cc-pVDZ, Midi-X, and SVP basis sets. A specific feature of these reactions is that their rates depend on the excess ring energy, although no ring opening occurs in all cases.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010050
      Issue No: Vol. 58, No. 1 (2017)
  • Dissociation energies of O–H bonds in alkylseleno- and
           alkyltelluro-substituted phenols
    • Authors: T. G. Denisova; E. T. Denisov
      Pages: 15 - 23
      Abstract: The O−H bond dissociation energy (D O−H) has been determined for eight alkylseleno-substituted phenols, one alkyltelluro-substituted phenol, and one alkyltelluro-substituted pyridinol. D O−H has been estimated by the intersecting-parabolas method from kinetic data using five reference compounds: α-tocopherol (D O−H = 330.0 kJ/mol), 3,5-di-tert-butyl-4-methoxyphenol (D O−H = 347.6 kJ/mol), 4-methylphenol (D O−H = 361.6 kJ/mol), 2,6-di-tert-butyl-4-methylthiophenol (D O−H = 336.3 kJ/mol), and 2,6-di-ter-tbutyl-4-methylphenol (D O−H = 338.0 kJ/mol). The following D O−H values (kJ/mol) have been obtained: 335.9 for 2,5,7,8-tetramethyl-2-phytyl-6-hydroxy-3,4-dihydro-2H-1-benzoselenopyran, 342.6 for 2-methyl-5-hydroxy-2,3-dihydrobenzoselenophene, 333.5 for 2,4,6,7-tetramethyl-5-hydroxy-2,3-dihydrobenzoselenophene, 339.4 for 2-tert-butyl-4-methoxy-6-octylselenophenol, 357.9 for dodecyl 3-(4-hydroxyphenyl) propyl selenide, 348.5 for dodecyl 3-(3,5-dimethyl-4-hydroxyphenyl)propyl selenide, 350.9 for dodecyl 3-(3-tert-butyl-4-hydroxyphenyl)propyl selenide, 338.0 for dodecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propyl selenide, 343.0 for 2,6-di-tert-butyl-4-(tellurobutyl-4′-phenoxy)phenol, and 338.8 for 6-octyltelluro-3-pyridinol. The stabilization energies of phenoxyl radicals containing R substituents (X = O, S, Se, Te) have been compared.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010013
      Issue No: Vol. 58, No. 1 (2017)
  • Ion-exchange resin catalysts in the liquid-phase hydrazinolysis of
           cinnamic acid
    • Authors: S. A. Dzhumadullaeva; A. B. Baeshov
      Pages: 24 - 27
      Abstract: The catalytic activity of a synthetic ion-exchange resins has been studied in the reaction of cinnamic acid with hydrazine (aqueous medium, 363 K, 1.0–2.5 h) yielding the corresponding hydrazide. Efficient catalysts for the process are the anion-exchange resins AV-17-8 and AN-31. The modifying effect of the substrate—hydrazine hydrate—on the catalytic properties of the ion-exchange systems has been demonstrated. On the basis of IR spectroscopic studies, a plausible process mechanism was suggested. It involves polymer-bound quaternary ammonium ions of the anion exchanger.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010025
      Issue No: Vol. 58, No. 1 (2017)
  • Oxidative desulfurization of thiophene derivatives with H 2 O 2 in the
           presence of catalysts based on MoO 3 /Al 2 O 3 under mild conditions
    • Authors: Y. Shen; X. Lu; X. Ma; J. He; D. Zhang; H. Zhan; Q. Xia
      Pages: 28 - 33
      Abstract: The catalysts based on MoO3/Al2O3 were synthesized and tested using aqueous hydrogen peroxide as the oxidant in the oxidative desulfurization of thiophene, benzothiophene (BT) and dibenzothiophene (DBT) into the corresponding sulfones. Among catalysts tested, 15%(MoO3–WO3)/Al2O3 prepared by a conventional impregnation method was considerably active for the oxidation of thiophene, BT and DBT, which could achieve higher than 99.2% conversions at lower reaction temperature (≤338 K). The use of hexadecyltrimethyl ammonium bromide as the phase-transfer reagent in small amounts could promote the reaction efficiently.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010086
      Issue No: Vol. 58, No. 1 (2017)
  • Mechanisms of the stabilization of a molybdenum epoxidation catalyst by
           nitrogen-containing compounds
    • Authors: G. G. Elimanova; N. N. Batyrshin; Kh. E. Kharlampidi
      Pages: 46 - 50
      Abstract: Nitrogen-containing compounds have been studied as stabilizing additives for a complex molybdenum catalyst for propylene epoxidation with ethylbenzene hydroperoxide. Introducing the additives increases the half-life period by a factor of 10–14. The effective constants and rates of the decomposition of the catalytic complex in the presence of stabilizing agents have been calculated. Two possible mechanisms of the action of the nitrogen-containing additives have been suggested.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010037
      Issue No: Vol. 58, No. 1 (2017)
  • Preparation method effect on the physicochemical and catalytic properties
           of a methane dehydroaromatization catalyst
    • Authors: O. V. Sedel’nikova; A. A. Stepanov; V. I. Zaikovskii; L. L. Korobitsyna; A. V. Vosmerikov
      Pages: 51 - 57
      Abstract: The molybdenum precursor effect on the physicochemical properties of the Мо/ZSM-5 catalyst and on its catalytic properties in nonoxidative methane conversion into aromatic hydrocarbons has been investigated. The textural characteristics of molybdenum catalysts have been determined by low-temperature nitrogen adsorption, and their acidity has been measured by temperature-programmed ammonia desorption. The microstructure and composition of Mo/ZSM-5 samples have been determined by high-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy. The activity and on-stream stability of the Мо-containing zeolite catalyst in the nonoxidative conversion of methane depend on the type of molybdenum compound that was used in catalyst preparation.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010074
      Issue No: Vol. 58, No. 1 (2017)
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