The Role of Surfactants in the Formation of Highly Dispersed Iron–Zirconium Oxide Composites with Uniform Pores

The effects of the nature and concentration of surfactants and the preparation conditions on the genesis of iron–zirconium composites with a [Fe³⁺]/[Zr⁴⁺] ratio of 0.123 were studied. The effect of surfactants on the physicochemical properties of precipitates is determined by the conditions of synthesis. The amount of surfactants retained by the precipitate at pH 3 is about an order of magnitude greater than at pH 9. The thermolysis of samples synthesized at acidic pH is accompanied by the dehydration and dehydroxylation of iron–zirconium composites as well as by the decomposition and destruction of surfactants. In the latter processes, compounds or their fragments capable of reducing some phases are removed in a stepped-up manner. The specific surface area of oxide systems formed in this way is at most 100–150 m²/g. In the pH range corresponding to the complete precipitation of the components, highly dispersed single-phase and uniformly porous composites are formed. The choice of a surfactant, its fraction, and preparation conditions enables the preparation of oxides with specific surface areas of 100–400 m²/g. The average pore diameter of the samples ranges from 3.0 to 27.0 nm, and the total pore volume ranges from 0.20 to 0.38 cm³/g.     

Structural Inhomogeneity in Electrolyte Solutions: The Calcium Perchlorate–Water System

A new approach has been proposed to study the structure of aqueous electrolyte solutions. NIR, Raman and attenuated total reflectance, Fourier transform infra-red (ATR FTIR) spectra have been measured for aqueous calcium perchlorate solutions in the 0.22–4.3 mol·L^?1 (0.22–7.46 mol·kg^?1) concentration range at 25 °C. By the methods of principal component analysis (PCA) and multivariate curve resolution—alternating least squares (MCR-ALS) the number, spectra and concentration profiles have been determined for spectroscopically distinguishable forms of water and ClO ₄ ^? ion in solutions. The results have been analyzed using a phenomenological model, establishing thereby: concentration ranges for structural rearrangements of the solution, the nature of structural microirregularities and different states of the ClO ₄ ^? ion in the areas of domination of the natural water structure, and of cybotactic groups of calcium perchlorate hexa and tetra hydrates.     

The Effect of Concentration Parameters on Complexation in the Iron(0)–Iron(II)–Glycine–Water System

The processes of formation of iron(II) complexes in aqueous glycine solutions in the pH range of 1.0–8.0 at 298 K and ionic strength of 1 mol/L (NaClO₄) are studied using Clark and Nikolskii’s oxidation potential method. The type and number of coordinated ligands, the nuclearity, and the total composition of the resulting complexes are determined. The following complex species are formed in the investigated system: [Fe(OH)(H₂O)₅]⁺, [FeHL(H₂O)₅]²⁺, [Fe(HL)(OH)(H₂O)₄]⁺, [Fe(OH)₂(H₂O)₄]⁰, [Fe₂(HL)₂(OH)₂(H₂O)₈]²⁺, and [Fe(HL)₂(H₂O)₄]²⁺. Their formation constants are calculated by the successive iterations method using Yusupov’s theoretical and experimental oxidation function. The model parameters of the resulting coordination compounds are determined.     

Direct Mechanism of the First Carbon–Carbon Bond Formation in the Methanol-to-Hydrocarbons Process

In the past two decades, the reaction mechanism of C−C bond formation from either methanol or dimethyl ether (DME) in the methanol-to-hydrocarbons (MTH) process has been a highly controversial issue. Described here is the first observation of a surface methyleneoxy analogue, originating from the surface-activated DME, by in situ solid-state NMR spectroscopy, a species crucial to the first C−C bond formation in the MTH process. New insights into the first C−C bond formation were provided, thus suggesting DME/methanol activation and direct C−C bond formation by an interesting synergetic mechanism, involving C−H bond breakage and C−C bond coupling during the initial methanol reaction within the chemical environment of the zeolite catalyst.     

Solubility of Adenine and Kinetin in Water–Ethanol Solutions

We have measured the solubility of adenine and kinetin in water–ethanol solutions. Various models of cosolvency have been taken into account in the analysis of the experimental data. The results are interpreted in terms of hydrophobic interactions.     

The Electrical Double Layer at the Bi–Ga Liquid Alloy in the Acetonitrile Electrolyte Solutions

The electrical double layer (EDL) characteristics of a Bi (0.25 at. %)–Ga liquid electrode in acetonitrile are studied. In acetonitrile, as in water, the electrode models Bi electrodes in their electrochemical properties. In contrast to aqueous solutions, in acetonitrile solutions it is possible to study the EDL structure not only at negative charges but also near the zero charge and at small positive charges. In acetonitrile, the electrode's potential of zero charge not distorted by specific ion adsorption and the corrected electrochemical work function are determined. The electrode is as lyophilic with respect to acetonitrile as Hg. Thus, the orientation of acetonitrile dipoles on Hg and Bi is identical at negative charges. The obtained data and data for a partially fused polycrystalline electrode in aqueous solutions are used to determine contributions of semimetal properties of a Bi electrode to the capacitance of the inner part of EDL and to a potential drop. The charge dependences of these contributions are found.     

Formation of Diazepam–Lanthanides(III) Complexes in the 50–50 Volume % Ethanol–Water Solvent System and Study of the Effect of Temperature on the Complex Formation Constants

Diazepam (7-chloro-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one) is an important derivative of the 1,4-benzodiazepine compound commercially distributed as Valium. The complex formation constants of diazepam with some light lanthanide(III) metal ions have been studied by potentiometric measurements. All titrations were performed in 50–50% (volume/volume) ethanol–water solvent mixtures at constant ionic strength (0.10 mol⋅dm⁻³). The ionic strength was maintained by using sodium perchlorate. The complex formation constants were determined at 25.00, 35.00 and 45.00 °C. With increasing temperature, a decrease was observed in the protonation constant (pK) of diazepam.     

Polymerization of Methyl Methacrylate by the System Ribonucleic Acid–Water in the Presence of Carbon Tetrachloride and Copper(11) Ion

Polymerization of methyl methacrylate (MMA) was carried out in the presence of ribonucleic acid (RNA), water, carbon tetrachloride, and copper(II) ion. The overall activation energy for the polymerization is proportional to the square root of the amount of RNA. The rate increased at first with the amount of MMA, but then became independent of the amount of MMA.

Polymerization was inhibited by the presence of air. Carbon tetrachloride and copper(II) ion are able to give RNA the ability to initiate polymerization. Conversion of MMA is accelerated by the addition of tertiary amine derivatives instead of carbon tetrachloride.     

Immediate Formation/Precipitation of Icosahedrally Structured Iron–Molybdenum Mixed Oxides from Solutions Upon Mixing Simple Iron(III) and Molybdate Salts

The present investigation refers to nanostructured mixed metal oxides—more specifically to iron–molybdenum oxides most simply obtained by addition of iron(III) chloride to an aqueous solution of sodium molybdate acidified with acetic acid. The immediately obtained yellow non-crystalline solid consists of highly symmetrical icosahedral {Mo₇₂Fe₃₀} motifs which is proven by IR, Raman, ⁵⁷Fe Mössbauer and XP spectra. This remarkable result is obtained in spite of the immediate precipitation of the mentioned compound and even from an inhomogeneous mixture of the educts. This again proves the high formation tendency of spherical clusters. The procedure offers in principle the option to encapsulate species present in solution.     

Stability Constants of Copper(II) Glycylglycinate Complexes in Water–Dimethylsulfoxide Solutions

Russian Journal of Physical Chemistry A - Stability constants of normal and copper(II) bis-glycylglycinate complexes in water–dimethylsulfoxide solutions of variable composition are...     

Temperature-Dependent Formation and Transformation of Mesostructures in Water–Ionic Liquid Mixtures

The temperature-dependent formation and transformation of mesostructures in binary mixtures of the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim⁺][BF₄⁻]) and water are characterized. Through addition of nitroxide radicals as paramagnetic spin probes, the temperature dependence of the solution structure can be assessed by using electron paramagnetic resonance (EPR) spectroscopy from typical solutes’ points of view. Additionally, the phase behavior on cooling and reheating is probed by differential scanning calorimetry (DSC). Thermal hysteresis and memory effects are observed, and DSC is used to identify the crystallization and thawing of ice as the pertinent phase transition. The EPR data of the nitroxide radicals before and after freezing and thawing reveal a transformation of the mesostructures, probably triggered by the crystallization of water pools to ice. A more polar state results after thawing, thereby suggesting a rupture and dissolution of the ordered IL-rich mesostructures. If the thawed solutions are not agitated, the system relaxes very slowly, that is, at room temperature with a time constant of approximately 90 h, to its equilibrium state of mesophase-separated IL-rich and bulk-like water regions.     

Hygrometric Determination of the Water Activities of the Aqueous Solutions of the Mixed Electrolyte NaCl–CaCl2–H2O at 25°C

The mixture {yNaCl + (1 – y)CaCl₂}(aq) has been studied with the hygrometric method at the temperature 25°C. The water activities were measured at total molalities from 0.25 mol-kg^–1 to near saturation for different ionic-strength fractions y of NaCl with y = 0.33, 0.50, and 0.67. The obtained data allow the calculation of osmotic coefficients. The experimental results are compared with the predictions of the Zdanovskii–Stokes–Robinson (ZSR), Kusik and Meissner (KM), Robinson and Stokes (RS), Lietzke and Stoughton (LS II), Reilly–Wood–Robinson (RWR), and Pitzer models. From the measured osmotic coefficients, the Pitzer ionic mixing parameters _{Na Ca} and _{Na Ca} Cl are determined and are used to predict the solute activity coefficients in the mixtures. The excess Gibbs energy is also determined. These results are compared with those given in the literature.     

Ethylene and Cyclohexene Oxidation by p-Benzoquinone,Hydrogen Peroxide,and Oxygen in the Solutions of Cationic Pd(II) Complexes in Acetonitrile–Water and Ionic Liquid–Water Binary Solvents

Kinetics and Catalysis - Optimal conditions are selected for ethylene and cyclohexene oxidation reactions in the acetonitrile (AN)–water system in the presence of...     

On the Role of the Solvent and Substituent on the Protonation Equilibria of Di-Substituted Anilines in Dioxane–Water Mixed Solvents

Protonation constants of a number of di-substituted anilines were determined potentiometrically in 0, 20, 30, 40, 50, and 60% (v/v) dioxane–water mixtures at (25.00 ± 0.02) ^∘C with an ionic strength of 0.10 mol-dm⁻³ sodium perchlorate. The data are discussed in terms of the electronic character of the substituents. Two different methods were used to study the effects of the solvents on the protonation constants; one involved a single polarity parameter, the Dimroth–Reichardt parameter E_T(30); the other involved the Kamlet–Taft multi-parametric method. The protonation constants of di-substituted anilines correlate with the molecular parameters for the dipolarity/polarizability of the solvent, π^∗, and its hydrogen-bond acceptor ability, β.     

The Formation and Stability of the [FePy3Cl3]· Py Clathrate in the Pyridine–Iron(III) Chloride System: Phase Diagram and Solid–Gas Equilibria Study

The phase diagram of the pyridine–iron(III) chloride system has been studied for the 223–423 K temperature and 0–56 mass-% concentration ranges using differential thermal analysis (DTA) and solubility techniques. A solid with the highest pyridine content formed in the system was found to be an already known clathrate compound, [FePy₃Cl₃]·Py. The clathrate melts incongruently at 346.9 ± 0.3 K with the destruction of the host complex: [FePy₃Cl₃]·Py_(solid)=[FePy₂Cl₃]_(solid) + liquor. The thermal dissociation of the clathrate with the release of pyridine into the gaseous phase (TGA) occurs in a similar way: [FePy₃Cl₃]·Py_(solid)=[FePy2Cl₃]_(solid) + 2 Py_(gas). Thermodynamic parameters of the clathrate dissociation have been determined from the dependence of the pyridine vapour pressure over the clathrate samples versus temperature (tensimetric method). The dependence experiences a change at 327 K indicating a polymorphous transformation occurring at this temperature. For the process ${1 \over 2}[\hbox{FePy}_{3}\hbox{Cl}_{3}]\cdot \hbox{Py}_{\rm (solid)} = {1 \over 2}[\hbox{FePy}_{2}\hbox{Cl}_{3}]_{\rm (solid)} + \hbox{Py}_{\rm (gas)}$ in the range 292–327 K, ΔH $^{0}_{298}$ =70.8 ± 0.8 kJ/mol, ΔS $^{0}_{298}$ =197 ± 3 J/(mol K), ΔG $^{0}_{298}$ =12.2 ± 0.1 kJ/mol; in the range 327–368 K, ΔH $^{0}_{298}$ =44.4 ± 1.3 kJ/mol, ΔS $^{0}_{298}$ =116 ± 4 J/(mol K), ΔG $^{0}_{298}$ =9.9 ± 0.3 kJ/mol.     

The Role of Catalyst Formation–Deactivation Processes and Evidence for a Nonlinear Mechanism in the Mizoroki–Heck Reaction with Aryl Chlorides

Kinetics and Catalysis - An operando kinetic study was made of the Mizoroki–Heck reaction with low-reactive aryl chlorides using the most practically attractive “ligand-free”...     

Facile and Reversible Formation of Iron(III)–Oxo–Cerium(IV) Adducts from Nonheme Oxoiron(IV) Complexes and Cerium(III)

Ceric ammonium nitrate (CAN) or Ce^IV(NH₄)₂(NO₃)₆ is often used in artificial water oxidation and generally considered to be an outer-sphere oxidant. Herein we report the spectroscopic and crystallographic characterization of [(N4Py)Fe^III-O-Ce^IV(OH₂)(NO₃)₄]⁺ ( 3 ), a complex obtained from the reaction of [(N4Py)Fe^II(NCMe)]²⁺ with 2 equiv CAN or [(N4Py)Fe^IV=O]²⁺ ( 2 ) with Ce^III(NO₃)₃ in MeCN. Surprisingly, the formation of 3 is reversible, the position of the equilibrium being dependent on the MeCN/water ratio of the solvent. These results suggest that the Fe^IV and Ce^IV centers have comparable reduction potentials. Moreover, the equilibrium entails a change in iron spin state, from S=1 Fe^IV in 2 to S=5/2 in 3 , which is found to be facile despite the formal spin-forbidden nature of this process. This observation suggests that Fe^IV=O complexes may avail of reaction pathways involving multiple spin states having little or no barrier.