Investigations of TsVM zeolite acidities with different degrees of exchange of Na+ by H+

The method of programmed thermal desorption of ammonia has been used to establish that on the surface of the sodium form of type TsVM zeolite having a modulus SiO₂/Al₂O₃= 34.5 there are two types of acidic centers having ammonia desorption activation energies E_d equal to 40–45 and 80–100 kJ/mole. Replacement of Na⁺ by H⁺ leads to the appearance of a third type of center with a value E_D=130–150 kJ/mole. In this case in the IR spectra of specimens saturated with ammonia a band appears at 1410 cm_–1, which is evidence for the presence of NH ₄ ⁺ ions. Increasing the degree of Na⁺ replacement by H⁺ leads to a nonproportional rapid increase in the concentration of highly energetic centers, which may be explained by the partial transfer of aluminum into cationic positions with the formation of additional acidic centers.Translated from Teoreticheskie i Éksperimental'naya Khimiya, Vol. 22, No. 6, pp. 752–755, November–December, 1986.     

Reduction of nitrogen(I) oxide with carbon monoxide and C<Subscript>3</Subscript>–C<Subscript>4</Subscript> alkanes on Fe-containing zeolite catalysts

It is shown that in the presence of reducing agents — light alkanes (C₃–C₄) or carbon monoxide — the temperature for the elimination of nitrogen(I) oxide over iron-containing zeolite catalysts of various structural types (Y, M, pentasil) is reduced by 70–150 °C. In the presence of excess oxygen (SCR process conditions) a greater conversion of N₂O(90–94%) is achieved at even lower temperatures (up to 50–150 °C less) with the use of hydrocarbons, and the activity of the catalysts correlates with the presence of strongly acidic B centers on their surfaces.__________Translated from Teoreticheskaya i Éksperimentalnaya Khimiya, Vol. 41, No. 1, pp. 35–39, January–February, 2005.     

Transformations of isobutylene in the presence of various types of zeolites

Conclusions In contrast to zeolites with ultrahigh silica content, type A, X, Y, and M zeolites in the Na form and also those modified by decationization, cation exchange, and addition of-Al₂O₃, Al₂O₃-SiO₂, Pt, and Rh show a low activity in the aromatization reaction of C₃-C₄ olefins at 450–550°C at times of contact of 2–14.4 sec. The zeolites studied become rapidly deactivated as the result of intense coke formation.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1300–1304, June, 1981.     

Properties of pentasil-containing catalysts in hydrocarbon conversions. 7. Benzene alkylation by lower alkanes in the presence of modified zeolites

A novel catalytic synthesis of alkylaromatic hydrocarbons (AArH) containing C₇-C₈ has been achieved using C₂-C₄, alkanes as alkylating reagents on high silica zeolites of the pentasil type. It has been established that the yield of AArH during the reaction between benzene and alkanes varies in the order C₂H₆3H₈C₄C₁₀ (450–600°C). Modification of the zeolite by additions of Pt, Zn, and Ga results in a lowering of the reaction temperature (by 100°C) and alters the selectivity of the alkylation process. On passing from flow to static conditions and raising the pressure to 2–4 MPa the AArH yield doubles and reaches 70–75% in the case of C₃-C₄ hydrocarbons.For previous communication, see [1].Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2228–2232, October, 1991.     

Study of acidity of various zeolites by thermal desorption of ammonia

Using the method of thermal desorption of ammonia, we have studied the acidity of hydrogen forms of a number of zeolites: type Y, ultrahigh silica TsVK, synthetic and natural mordenite (M). The hydrogen forms of the TsVK and M zeolites have similar acidity spectra. But for HTsVK, the overall concentration of acidic centers is sufficiently lower than for HM, including weak centers (2.5–3 times) and strong centers (1.5 times). The concentration and strength distribution of acidic centers are very close in samples of synthetic and natural mordenite.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 244–247, March–April, 1989.     

Does in-source decay occur independent of the ionization process in matrix-assisted laser desorption?

The influence of the acidic and basic characters of constituent amino acid residues on the peptide fragment ions produced by in-source decay under matrix assisted laser desorption/ionization (MALDI) conditions has been studied using positive- and negative-ion experiments. Whereas the in-source decay spectra of peptides containing basic Arg and/or Lys residues near the N-terminus showed so-called c_n- and a_n-series ions in positive-ion mode, a peptide that has an acidic amino acid cluster near the N-terminus and a basic residue near the C-terminus characteristically formed y_n- and z_n-series ions in the positive-ion in-source decay spectrum. These results indicated that fragment ion series produced by in-source decay depend strongly upon the acidic and basic characters of the constituent amino acid residues and the near N- and C-termini. It was suggested that in-source decay processes occur intrinsically at NH–C^α and CO–NH bonds independent of the formation of molecular-related ions, and that the cleavages at the NH–C^α and CO–NH bonds occurred independently and were dependent on the matrix used.     

Radiolytic reduction of merocyanine 540 in methanol solution

Radiolytic reduction of merocyanine 540 (MC) in acidic (0.02 mol · dm^–3 in H₂SO₄) and neutral methanol solution was studied by pulse radiolysis. The spectra centered around 400 and 700 nm of the MC reduced transients recorded in acidic methanol and in neutral solution were found to be quite similar but they disappeared with different rates suggesting that different radicals (MCH· and MC·^–) were responsible for these spectra. The rate constant of ·CH₂OH reaction with MC was found to be 7·10⁸ mol^–1·dm³·s^–1.     

Synthesis of diethyl ether in presence of zeolite catalysts

Conclusions Ethanol, containing 10–30 mole% of C₂H₅I, is converted mainly to diethyl ether in the presence of zeolites NaX, NaY, HY, and HM, at a temperature of 160–200° and atmospheric pressure. Intense dehydration of the ethanol to ethylene occurs without the C₂H₅I.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 196–199, January, 1979.     

Influence of the crystallinity of pentasil-type zeolites on their acidity

The acid properties of intermediate products in crystallization of pentasil-type zeolites have been investigated using programmed thermal desorption of ammonia and adsorption of pyridine. It was found that acidity increases with increasing crystallinity due to proton-donor centers. A correlation was established between this change in acidity and methanol TPSR data.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 31, No. 1, pp. 48–51, January–February, 1995.     

Reduction of NO by C1-C4 hydrocarbons at cobalt-containing zeolites

Data are given on the activity of high-silicon zeolites in the reduction of nitrogen oxides by methane and C₂-C₄ hydrocarbons (paraffins and olefins). It was shown that the highest degree of conversion of NO during selective catalytic reduction is obtained at the mixed forms of Co-containing zeolites at temperatures 100°C lower than at the usual Co-containing zeolites of the ZSM-5 type.L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, Kiev. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 32, No. 1, pp. 47–50, January–February, 1996. Original article submitted April 3, 1995.     

Liquid chromatography with and of platinum complexes

Summary Reversed-phase, high-performance liquid chromatography (HPLC) on chemically bonded C₁₈-phases with acetonitrile-water mobile phases, contianing platinum complexes like Zeise's salt C₂H₄PtCl₃, the amine derivative C₂H₄–PtCl₂–NH₂–CH(CH₃)–C₆H₅ or the amino acid compound C₂H₄–PtCl–OOC–CH(N(CH₃)₂)–C₆H₅ by analogy with argentation chromatography, was used to increase selectivity for the separation of various types of olefins, amines and heterocyclic compounds. On the other hand, normal-phase adsorption chromatography on silica with n-heptane, dichloromethane and n-propanol mobile phases proves to be an ideal tool for the analytical and preparative separation of diastereomeric platinum complexes of olefins, introduced by Gil-Av, that can be easily preparedin vitro, by the reaction of C₂H₄–PtCl–OOC–CH(N(CH₃)₂)–C₆H₅ with optically active olefins in CH₂Cl₂. The preparation of the intitial complex as well as its application to the separation of several interesting types of enantiomeric olefins is described and discussed. The number and amount of separable diastereomers formed by the above reaction is strongly influenced by sterical effects. By comparison of the chromatographic pattern of either racemic or partly racemic mixtures, it is possible to decide, which peaks belong to one or the other enantiomeric form of the olefin.     

Catalytic dehydration of isopropanol on neodymium-Y and X-zeolites and the effect of γ-irradiation

Four different samples of NdX, NdY, NdNH₄X and NdNH₄Y-zeolites were prepared by ionexchange methods. DTA and XRD analyses have been carried out for the samples. The thermally activated zeolites were irradiated by 1.5 and 10.0 Mrad -rays. The catalytic activities of these samples were tested in dehydration of isopropanol. The results of DTA indicated that all samples showed endothermic peaks at about 215 °C related to the release of physically adsorbed water and exothermic peaks at 850–950 °C indicating the collapses of the zeolite. The X-ray analysis revealed that the exchange of sodium by neodymium or ammonium followed by neodymium ions did not change the crystal structure but some decrease in the crystallinity was observed. The catalytic activities of these zeolites were measured in dehydration of isopropanol as a function of temperature. It was found that the activity of the prepared Nd-zeolites depends on the crystallinity of zeolites and on the condensation products formed on catalyst surface. However, the irradiated samples exhibited higher catalytic activities in isopropanol conversion than the unirradiated ones. The observed higher activity for irradiated samples was attributed to the increase of the number of acidic centers responsible for dehydration of alcohols. These centers were formed as a result of the formation of tricoordinate aluminium atoms in -irradiated zeolites.     

AlPO4?Al2O3 catalysts with low alumina content, VII. Anisole conversion in the presence of methanol

The conversion of anisole in the presence of methanol (anisole/methanol molar ratio=4) over AlPO₄–Al₂O₃ (5–15 wt.% Al₂O₃) catalysts gave a mixture of dealkylated and C-alkylated products (C-alkylation preferentially inortho-position) in which dealkylation to phenol always predominated. The catalytic activity, which increased with alumina content and decreased on increasing the calcination temperature from 773 to 1073 K, was fairly well related to the change in surface acidic characteristics. Furthermore, anisole conversion followed the requirements of the Bassett-Habgood kinetic treatment for first order processes, with a single common interaction mechanism and, consequently, a common transition state for all catalysts. Poisoning by pyridine and 2,6-dimethylpyridine confirmed that anisole conversion occurs on acid sites.     

Synthesis, structure and DNA binding studies of mononuclear copper(II) complexes with mixed donor macroacyclic ligands, 2,6-bis({N-[2&3-(phenylselenato)alkyl]}benzimidoyl)-4-methylphenol

Two new phenol based macroacyclic Schiff base ligands, 2,6-bis({N-[2-(phenylselenato)ethyl]}benzimidoyl)-4-methylphenol (bpebmpH, 1) and 2,6-bis({N-[3-(phenylselenato)propyl]}benzimidoyl)-4-methylphenol (bppbmpH, 2) of the Se₂N₂O type have been prepared by the condensation of 4-methyl-2,6-dibenzoylphenol (mdbpH) with the appropriate (for specific reactions) phenylselenato(alkyl)amine. These ligands with Cu(II) acetate monohydrate in a 2:1 molar ratio in methanol form complexes of the composition [(C₆H₂(O)(CH₃){(C₆H₅)CN(CH₂)_nSe(C₆H₅)}{(C₆H₅)CO}₂Cu] (3 (n = 2), 4 (n = 3)) with the loss of phenylselenato(alkyl)amine and acetic acid. In both these complexes, one arm of the ligand molecule undergoes hydrolysis, and links with Cu(II) in a bidentate (NO) fashion, as confirmed by single crystal X-ray crystallography of complex 3. The selenium atoms do not form part of the copper(II) distorted square planar coordination sphere which has a trans-CuN₂O₂ core. The average Cu–N and Cu–O distances are, respectively, 1.973(3) and 1.898(2) Å. The N–Cu–N and O–Cu–O angles are, respectively, 167.4(11)° and 164.5(12)°. The compounds 1–4 have been characterized by elemental analysis, conductivity measurements, mass spectrometry, IR, electronic, ¹H and ⁷⁷Se{¹H} NMR spectroscopy and cyclic voltammetry. The interaction of complex 3 with calf thymus DNA has been investigated by a spectrophotometric method and cyclic voltammetry.     

Continuous time versus reaction events number in stochastic kinetics. A chemical uncertainty principle

The 3609 cm^–1 OH-groups in NaHZSM-5 zeolites are heterogeneous, 5 kinds of OH-groups being found. Benzene is more strongly bonded to more acidic hydroxyls and n-hexane to less acidic hydroxyls.     

Fabrication and characterization of γ-Al2O3–clay composite ultrafiltration membrane for the separation of electrolytes from its aqueous solution

In this paper, we have reported the preparation of low cost γ-Al₂O₃ membrane on a macroporous clay support by dip-coating method. For the synthesis of γ-Al₂O₃ top layer on the support, a stable boehmite sol is prepared using aluminium chloride salt as a starting material by sol–gel route. The structural properties of the composite membrane as well as γ-Al₂O₃ powder is carried out using scanning electron microscopy (SEM), X-ray diffraction (XRD), nitrogen adsorption–desorption isotherm data, Fourier transform infrared analysis (FTIR) and dynamic light scattering (DLS) analysis. The mean particle size of the boehmite sol used for coating is found to be 30.9 nm. The pore size distribution of the γ-Al₂O₃–clay composite membrane is found to be in the range of 5.4–13.6 nm. Separation performance of the membrane in terms of flux and rejection of single salts solution such as MgCl₂ and AlCl₃ as a function of pH, salt concentration and applied pressure is also studied. The rejection and flux behavior are found to be strongly dependent on electrostatic interaction between the charged molecules and γ-Al₂O₃–clay composite membrane. The intrinsic rejection has been determined by calculating the concentration at membrane surface (C_m) using Speigler–Kedem model. It is found that the observed rejection shows anomalous trend with increase in applied pressure and the intrinsic rejection increases with increase in applied pressure, a trend typical of the separation of electrolyte through charged membranes. At acidic pH, both the salt solution shows higher rejection. With increase in the salt concentration, observed rejection of salt decreases due to the enhanced concentration polarization. The maximum rejection of MgCl₂ and AlCl₃ is found to be 72% and 88%, respectively for salt concentration of 3000 ppm.     

Synthesis of hexylthiols C6H13SH−1/1, 2, 3, 4−14C1/4/' /1-thiol[35S]/ and C6H13SH−2/1, 2, 3, 4−14C1/4/, /2-thiol[35S]/

A synthesis of¹⁴C and³⁵S double labelled hexylthiols: C₆H₁₃SH–1/1, 2, 3, 4–¹⁴C_1/4/, /1-thiol[³⁵S]/ and C₆H₁₃SSH–2/1, 2, 3, 4–¹⁴C_1/4/, /2-thiol[³⁵S]/ based on H₂ ³⁵S and C₆H₁₂–/1, 2, 3, 4–¹⁴C_1/4/ has been developed and described.     

Superacids Based on Zirconium Dioxide

The synthesis of the superacidic materials SO ₄ ²⁻ /ZrO₂ and WO₃/ZrO₂ is examined. The structure of their acidic centers and their activity in the isomerization and acylation of hydrocarbons are discussed.__________Translated from Teoreticheskaya i Eksperimental’naya Khimiya, Vol. 41, No. 3, pp. 156–165, May–June, 2005.     

Catalytic activity and acid properties of Al-pentasils and isomorphically substituted (Fe,B) silicates

The catalytic activity of Al-containing pentasils and their isomorphically substituted analogs (ferri- and borosilicates) in transformations of n-alkanes are directly dependent on their acidity. Elemental silicates have a lower acidity and are significantly less active in cracking and aromatization of n-alkanes of C₆-C₁₀ composition than Al-pentasils. The degree of conversion of alkanes decreases and the aromatizing capacity of zeolites decreases strongly with a decrease in the concentration of acid sites on pentasils with a different composition of the framework (Si0₂/Al₂O₃ 35–1000). Ferri- and borosilicates are close in activity in cracking and aromatization of n-alkanes but differ significantly in their acid characteristics. In particular, NH₃ is adsorbed on ferrisilicate with high heats both on acid sites active in these reactions and in the Fe₂O₃ phase present in the ferrisilicate and inactive in catalysis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 273–277, February, 1990.     

Structure of herboxine

Summary A new hydroxyindole alkaloid has been isolated from the roots and epigeal part ofVinca herbaceae — herboxine, C₂₃H₂₈N₂O₆, []_D +40° (c 1.13; methanol).On the basis of UV, IR, NMR, and mass spectroscopy and a transition from majdine to herboxine, structure (I) has been proposed for it which differs from that of majdine by the configuration at C₃.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 227–229, March–April, 1976.