Structure of zirconium butoxide complexes in n-butanol solutions

EXAFS and SAXS were used for structure elucidation of zirconium butoxide complexes in n-butanol at concentrations from 0.3 g to 0.015 g ZrO₂ in 1 ml. The basic structural unit of the complex is a tetramer. It has two equal sides with zirconium atoms linked by double oxygen bridges and with zirconium-zirconium distances of 3.5 Å. The other sides in the tetramer are 3.3 Å and 3.9 Å. This difference in bond lengths is explained by the different numbers of double or single ligand bridges between zirconium atoms. The tetramers are apt to undergo oligomerization to form particles with a diameter of 80 Å in solution.     

Effect of temperature on the structural characteristics of zirconium dioxide nanoparticles produced under conditions of microwave treatment

The effect of the sintering temperature on the structural characteristics of nanosized zirconium dioxide particles treated by microwave radiation during the drying process was investigated by small-angle X-ray scattering and the BET method. It was shown that the specific surface area, particle size, polydispersivity index, and surface and mass fractal dimensionality of zirconium dioxide depend on its heat treatment conditions. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 44, No. 3, pp. 138–143, May–June, 2008.     

Micelle formation in sodium hexadecyl sulfate surfactant solutions studied by small-angle neutron scattering

Micelle formation in aqueous sodium hexadecyl sulfate solutions is studied by small-angle neutron scattering. Measurements are carried out at different concentrations (1.1, 2.2, 3.2, 5.4, 10.9 and 32.8 mM/dm³) and at different temperatures (40°, 50°, and 60°C). The monotonous evolution of interparticle correlation can be observed on the measured scattering patterns. At high concentrations (10.9 and 32.8 mM/dm³) scattering patterns are described by interacting ellipsoids, but at low concentrations by non-interacting ellipsoids. Computation of the distance distribution function proved the ellipsoidal shape at 10.9 and 32.8 mM/dm³, but showed an unexpectedly large particle dimension and elongation of the micelles at lower concentrations.     

Thermodynamics and structural aspect of the gelling process in the gellan gum/metal salt aqueous solutions

Gellan gum undergoes gelation by forming domains composed of associated double helices. Here the further random aggregation of associated double helices seems necessary for the formation of the network in the case of Na-gellan with adding NaCl. Gellan gum aqueous solutions were prepared with or without adding various concentrations of NaCl, and their gel-sol transitions were observed by the differential scanning calorimetry (DSC) and the small-angle X-ray scattering (SAXS). The DSC endothermic peaks are attributed to the dissociation of the ordered domains, and the network dissociation in the case of gel samples. The SAXS results are analyzed in terms of the molecular models of associated double helices. This revised version was published online in July 2006 with corrections to the Cover Date.     

Isokinetic relationships for nucleophilic substitution reactions at the saturated carbon atom. Reactions in aqueous solutions

An isokinetic relationship (IKR) with the parametersT _iso=6145 K and logk _iso=10.622 is valid for nucleophilic substitution reactions at the saturated carbon atom with the participation of anionic nucleophiles in aqueous solutions. The IKR describes the rate constants of the reactions with different anionic nucleophiles, leaving groups, and substituents at the electrophilic reaction center. Similar reactions with neutral nucleophiles, which follow another mechanism, are described by a separate IKR withT _iso=−1232 K and logk _iso=16.226. The reactions of haloforms with hydroxide ion, which proceed by a specific mechanism involving the haloform ionization equilibrium followed by α-elimination of the halide ion, are described by yet another IKR withT _iso=−1463 K and logk _iso=21.057. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 809–814, May, 2000.     

Effect of ultrasound on the microstructure of polystyrene in cyclohexane: a synchrotron small-angle X-ray scattering study

Synchrotron small-angle X-ray scattering technique has been used to study the effect of ultrasound on the microstructure of polystyrene (PS) in cyclohexane solutions. The results show that the intramolecular radius of gyration (R _g) decreases with ultrasound, indicating the shrinkage and collapse of PS chains. There is an exponential relationship between R _g and the molecular weight of PS (M _w), and the exponent changes from 0.5 to 0.417, as the ultrasound time is increased. This means that the shape of PS chain changes from random coil to shrunken form. The Kratky plots also confirm the shape transformation of PS chains induced by ultrasound. Moreover, the intermolecular correlation length increases with the ultrasound time, which is indicative of the entanglement of PS chains.     

Observations on the thermoreversible gelation of two-directional arborols in water–methanol mixtures

Reversible gels of two-directional cascade polymers with hydrophilic groups covalently attached by an hydrophobic center chain were studied by light and small-angle X-ray scattering, differential scanning calorimetry, and freeze-fracture transmission electron microscopy. The long, self-assembled fibers interact side-by-side over extended regions to form bundles. A given fiber may participate in several bundles, thus forming a three-dimensional gel network. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2787–2793, 1997     

Structral Effects on the Mutual Solubility of Solution Components and Formation of Zinc and Cadmium Chloride Complexes in Zn(Cd)(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>-LiCl-H<Subscript>2</Subscript>O Systems

Solubility isotherms have been determined for Zn(Cd)(NO₃)₂-LiCl-H₂O systems at 25°C, and Raman spectra in the range of M-Cl and nitrate ion vibrations have been measured. A single bond system is realized over the whole range of concentrations in the Zn(NO₃)₂-LiCl-H₂O system because the cybotactic groups are structurally compatible. In the Cd(NO₃)₂-LiCl-H₂O system, the cybotactic groups are incompatible, which leads to structural microheterogeneities in post-eutectic concentrations.Original Russian Text Copyright © 2004 by M. K. Khripun, A. A. Kiselev, A. Yu. Efimov, L. A. Mund, and V. P. Petranovskii__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 1027–1033, November–December, 2004.     

A neutron inelastic scattering investigation of the diffusion kinetics of H2O molecules and hydration complexes in concentrated ionic solutions

Intermolecular frequencies of H₂O's and the diffusion kinetics have been investigated by neutron inelastic scattering for concentrated ionic solutions containing small and/or multiply charged cations (e.g., Cr⁺³, Mg⁺², Ca⁺², and Li⁺¹). As higher concentrations are approached such that the majority of H₂O's are in hydration layers, their exchange time can exceed the neutron interaction time. Then the diffusion kinetics depart functionally from activated reorientations of individual H₂O's characteristic of lower concentrations and evolve to continuous diffusion processes of hydration complexes characterized by small self-diffusion coefficients. The general features of the observed evolution in the functionality of the diffusion kinetics are found to be functionally consistent with an approximate model which includes contributions from the delayed diffusional exchange of individual H₂O's as well as the continuous diffusion of hydrated ions. At a given concentration, the temperature interval over which this evolution in functionality occurs increases both with increasing strength of the primary cation-H₂O coordination and with anion basicity. Further, as the temperature decreases, frequencies of defined cation-water hydration complexes gradually sharpen in a continuous manner, showing no abrupt variations at glass transitions. Anions of increasing basicity decrease the self-diffusion coefficients of the ion-water complexes and perturbed frequencies characteristic of cation-water hydration complexes. Such anion effects, at high concentrations, correspond to an increasing degree of time-average indirect or direct ion pairing with increasing anion basicity. This results, in turn, both in a distortion or partial disruption of the cation hydration sheaths and in a degree of coupling and/or bridging between anions and hydrated cations so as to increase the effective masses and friction coefficients associated with their diffusional motions.     

Global non-ideality effects in adsorption of organic substances from dilute aqueous solutions on activated carbon

Summary A method for the quantitative estimation of the global non-ideality of the adsorption of weak organic electrolytes on activated carbon from dilute aqueous solutions is presented. The method is based on the analysis of aGraham plot which reflects the adsorption isotherm deviations from ideality. Averaging these deviations over the whole range of adsorption, one gets a single value representing the global non-ideality of a system. The method also allows to estimate the contributions of heterogeneity and interactions in the adsorbed phase to the global non-ideality effect. The theoretical considerations are illustrated by some model calculations. The usefulness of the method is tested for experimental data of benzoic and salicyclic acid adsorption over a wide range ofpH and concentrations.

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Globaler Effekt der Nicht-Idealität bei der Adsorption organischer Substanzen aus verdünnten wässerigen Lösungen an Aktivkohle

Zusammenfassung Es wird eine Methode zur quantitativen Abschätzung der globalen Nicht-Idealität für die Adsorption schwacher organischer Elektrolyte aus verdünnten wässerigen Lösungen an Aktivkohle vorgestellt. Diese Methode basiert auf der Analyse der bekanntenGraham-Abhängigkeit, die die Abweichung der Adsorptionsisotherme von der Idealität zeigt. Bei Errechnung des Durchschnittwertes dieser Abweichung über den ganzen Asorptionsbereich erhält man einen Wert, der die globale Nicht-Idealität für ein Adsorptionssystem charakterisiert. Die Methode erlaubt auch, den Beitrag der Heterogenität und der Wechselwirkungen in der Adsorptionsphase zum globalen Effekt der Nicht-Idealität abzuschätzen. Die theoretischen Erörterungen werden an Hand von Modellberechnungen illustriert. Die Nutzbarkeit der Methode wurde mit experimentellen Daten der Benzoe- und Salicylsäureadsorption in einem weiten Bereich vonpH und Konzentration getestet.

     

X-ray scattering and thermal analysis study of the effects of molecular weight on phase structure in blends of poly(butylene terephthalate) with polycarbonate

Blends of Poly(butylene terephthalate), PBT, with Polycarbonate, PC, were studied for a range of molecular weights and blend compositions. Blends were available in PBT/PC compositions 80/20 and 40/60, and with M_w designated by H (high) or L (low). Samples were prepared by melt crystallization, or by cold crystallization following a rapid quench from the melt. Addition of PC reduces the crystallization kinetics of PBT so that the resulting crystals are more perfect than those which form in the homopolymer. Degree of crystallinity of the blends followed the rank ordering: L/L > L/H > H/L = H/H. The glass transition behavior was investigated using dynamic mechanical analysis (DMA) and modulated differential scanning calorimetry (MDSC). All blends exhibited two glass transitions at intermediate temperatures between the T_gs of the homopolymers, indicating existence of a PBT-rich phase and a PC-rich phase. Blends L/L were most, and H/H the least, miscible. Small-angle X-ray scattering was performed at room temperature on cold crystallized blends, or at elevated temperature during melt crystallization. The long period was consistently larger, and the linear stack crystallinity was consistently smaller, in blends L/L or H/L. These results indicate that in blends containing low M_w PC, there is more PC located within the PBT-rich phase. The long period was consistently smaller in cold crystallized samples, while the linear stack crystallinity was nearly the same, regardless of melt or cold crystallization treatment. Reduction of the average long period in cold crystallized samples could result from crystallization of PBT within the PC-rich phase. This is consistent with thermal analysis results, which indicate that cold crystallized samples have greater overall crystallinity than melt crystallized samples. A hypothetical liquid phase diagram is presented to explain the differences between melt and cold crystallized blends. © 1996 John Wiley & Sons, Inc.     

Dependence of the mutual ligand arrangement in guanidinate complexes of lanthanoids on the ligand solid angles

Mutual ligand arrangement in binuclear lanthanoid complexes of the type [Gu₂Ln(μ-H)]₂, [Gu₂Ln(μ-Cl)]₂, and Gu₂Ln(μ-Cl)₂Li(THF)₂, where Gu is a substituted guanidinato ligand, is quantitatively analyzed based on the ligand solid angle approach. In complexes of Nd, Sm, and Gd the Gu ligands shield up to 87% of the metal and the bidentate ligands on opposite metal centers are in the eclipsed arrangement; in complexes of lanthanoids with smaller ionic radii Y, Yb, and Lu the Gu ligands shield over 88.3% of the metal surface and their staggered conformation is observed. The ligand solid angle approach is illustrated and its application to describing multidentate ligands is demonstrated.     

浓度及冷冻-解冻处理对CuCl_2水溶液中Cu~(2+)区域结构的影响

应用扩展X射线吸收精细结构(EXAFS)光谱研究了CuCl2水溶液中Cu2+的区域环境结构,通过测定CuCl2水溶液在不同浓度条件下及冷冻-解冻(FT)处理前后CuK边EXAFS吸收谱,研究了浓度及冷冻-解冻处理对Cu2+第一配位层结构的影响.EXAFS实验结果表明,CuCl2水溶液中Cu2+第一配位层距离中心原子Cu最近邻原子为O原子,配位数介于3.0-4.3之间,Cu—O键长在0.192-0.198nm之间,这种结构与Cu2+的Jahn-Teller效应有关.不同浓度的CuCl2水溶液中Cu2+的区域环境结构有很大不同,随着CuCl2水溶液浓度的升高,Cu2+第一配位层配位数减小,Cu—O键伸长.结构参数拟合结果证实冷冻-解冻处理对Cu2+的区域环境结构有影响,CuCl2溶液经冷冻-解冻处理后,Cu2+第一配位层配位数变大,热无序度增加.     

Thermodynamic parameters for the protonation of carboxylic acids in aqueous tetraethylammonium iodide solutions

The protonation constants of 21 carboxylic acids (formic, acetic, propionic, benzoic, phenoxyacetic, salicylic, oxalic, malonic, succinic, itaconic, malic, tartaric, oxydiacetic, thiodiacetic, thiodipropionic, phthalic, maleic, citric, 1,2,3-tricarboxylic, 1,2,4-tricarboxylic and 1,2,4,5-tetracarboxylic), have been determined potentiometrically, by pH-metric measurements, at several temperatures and ionic strengths, 5T55°C, 0<11 mol-dm^–3, using tetraethylammonium iodide as background salt. General equations for the dependence on ionic strength of thermodynamic parameters have been found. The statistical significance of results and the possibility of using a simple model for the thermodynamics of carboxylic acids protonation, is discussed.     

Changes in the acid-base properties of hydrogels of metal oxide hydroxides induced by aging in solutions of electrolytes

Changes in the acid-base properties of titanium(IV), zirconium(IV), iron(III), chromium(III), and indium(III) hydrogels of oxide hydroxides induced by aging in sodium chloride and sulfate solutions were studied by the point of zero charge method. On aging in a solution of the sulfate electrolyte the hydrogels loose their basic properties much more rapidly than in the chloride solution. The most changes were observed in the region of high pH of the point of zero charge of the hydrogels. The changes in the acid-base properties can be explained by a decrease in the content of surface OH groups with are displaced by the supporting electrolyte ions, and due to the oxolation of the hydrogels. Published inIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1329–1332, August, 2000.     

Tripodal 1,2,3-triazole click ligand based on the triphenylphosphine oxide platform: atrane-type lanthanide complexes in solutions

Tris[2-(1-phenyl-1,2,3-triazol-4-ylmethoxy)phenyl]-phosphine oxide, a novel tripodal polytopic ligand produces, stable complexes with La(NO₃)₃ and Lu(NO₃)₃. According, to IR, multinuclear NMR and DFT data, the complexes, have atrane-type structure with tetradentate O,N,N,Ncoordination, of ligand in MeCN solutions.     

Influence of the conditions of manufacture of nanomeric zirconium dioxide,stabilized with yttrium oxide,on its catalytic properties in the oxidation of CO

The morphological and catalytic properties of samples of nanomeric zirconium dioxide, stabilized with yttrium oxide, manufactured via the effect of a UHF field during the process of drying precipitated zirconium hydroxide and calcination at temperatures from 300 to 1000 °C, were studied. It was shown that the highest activity in the oxidation of CO occurred with 40 nm particles of zirconium dioxide prepared at 1000 °C. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 2, pp. 96–101, March–April, 2007.     

Effect of the surfactant alkyl chain length on the stabilisation of lyotropic nematic phases

Lyotropic quaternary mixtures of potassium alkanoates (KCx) and sodium alkyl sulphates (NaCxS), where x is the number of carbon atoms in their alkyl chains, were prepared to investigate the effect of the surfactant alkyl chain length on the stabilisation of lyotropic nematic phases. The lyotropic mixtures investigated were formed by the dissolution of KCx (NaCxS) surfactants in the mixture of Rb₂SO₄/1-decanol/water (Na₂SO₄/1-decanol/water), separately. The uniaxial-to-biaxial nematic phase transitions were identified from the temperature dependence of the birefringences of the nematic phases by means of laser conoscopy. The micelle dimensions were obtained from small-angle X-ray scattering measurements. It was observed that the increase in the surfactant alkyl chain length causes the micellar growth in the plane perpendicular to the main amphiphile bilayer. The surfactant alkyl chain length plays a key role on the shape anisotropy of micelles, which triggers the orientational fluctuations that are responsible for the stabilisation of the different lyotropic nematic phases.     

Influence of the composition of composites based on Y-and Sc-stabilized zirconium dioxide on catalytic properties in the oxidative conversion of methane

The effect of the composition of composites based on Y-and Sc-stabilized zirconium dioxide doped with CeO₂ and transition metal (Cu, Co, Ni) oxides on catalytic properties in the oxidative conversion of methane was studied. The activity of the composites correlated with the quantity and mobility of oxygen in them. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 3, pp. 184–188, May–June, 2006.