Elemental Composition Method in Thermodynamics of Multireaction Systems* (Ⅰ) Molar Number, Thermodynamic Properties and Partial Properties Relations

When species in the solution undergo multiple chemical reactions, the solution may be treated as a solution of all species actually present or as a hypothetical solution composed of elemental species. Based on the fundamental thermodynamic principle, the relationships of mole numbers, molar fractions, thermodynamic properties, partial molar properties, potential and fugacity between the hypothetical solution of elemental species and the equilibrated solution of actual species were derived. The hypothetical elemental solution provides a way of reducing the dimensionality of problem, simplifying the analysis and visualizing the phase behavior.     

Dimension Reduction Method in Thermodynamics of Multireaction Systems(Ⅱ)Residual Properties,Property Changes of Mixing and Excess Properties Relations

Based on the fundamental thermodynamic principle the relationships of the residualproperties,the property changes of mixing and the excess properties between the hypothetical so-lution of unreacted independent species and the equilibrated solution of actual species have beenestablished.The hypothetical solution provides a way of reducing the dimensionality of problem andsimplifying the analysis.     

Composites of Poly(Keto-Sulfide)–Epoxy Resin Systems and Their Thermal and Mechanical Properties

A novel matrix resin system, poly(keto-sulfide)–epoxy resin, has been developed. The poly(keto-sulfide)s (PKS), based on various ketones, formaldehyde, and sodium hydrogen sulfide (NaSH), were prepared by the reported process. These (PKS) having terminal thiol (–SH) groups were used for curing commercial epoxy resin (i.e., diglycidyl ether of bisphenol A – DGEBA), to fabricate crosslinked epoxy-poly(keto-sulfide) resin glass fiber-reinforced composites (GRC). Various epoxy/hardener (PKS) mixing ratios were used, and the curing of epoxy-PKS has been monitored using differential scanning calorimetry (DSC) in dynamic mode. Based on DSC parameters the GRC of epoxy-PKS were prepared and characterized by thermal and mechanical methods. The variation in resin/hardener ratio led to variations in thermal and mechanical properties.     

Heat Loss Reduction in Combustion of Cu(Ni)–Al Powder Systems Due to Their Microstructural Transformation

The paper reviews published data on structural–phase changes in Cu–Al and Ni–Al metal powders during in situ combustion. The heatconservation properties of various structures located around reactive cells in the combustion wave zone are revealed. The mechanism providing for nearly adiabatic combustion conditions is discussed and a microstructural model for this mechanism is justified.     

Experimental Study of CMC Evaluation in Single and Mixed Surfactant Systems, Using the UV–Vis Spectroscopic Method

In this study, the critical micellar concentration (CMC) of anionic, cationic and nonionic surfactants was determined using the UV–Vis spectroscopic method. Sodium lauryl sulfate (SDS) as anionic, hexadecyl-trimethyl-ammonium bromide as cationic, tert-octylphenol ethoxylates TOPEON (with N = 9.5, 7.5 and 35) and lauryl alcohol ethoxylate (23EO) as nonionic surfactants have been used. Concentration of surfactants varies both from below and above the CMC value in the pyrene solution. In addition, the amount of the CMC was determined using the values from the data obtained from the graph of absorbance versus concentration of surfactants. A comparative study was conducted between the results of the present study and the literature which shows a good agreement, in particular for TOPEO9.5 and LAEO23. Furthermore, the CMC value of SDS (as an ionic surfactant) in the presence of nonionic surfactants was also examined. The result reveals that with addition of small amount of nonionic surfactant to the anionic SDS surfactant, a decline in the CMC value of the anionic–nonionic system relative to the CMC of pure anionic surfactant was observed. In addition and for the first time, the effect of UV irradiation on the size of the micelle formations was studied. It was found that UV irradiation causes the formation of smaller micelles which is of prime concern in membrane technology.     

Surface Properties and Thermodynamic Parameters of Some Sugar-Based Ethoxylated Amine Surfactants: 1—Synthesis,Characterization, and Demulsification Efficiency

Several ethoxylated sugar-based amine surfactants have been synthesized and characterized by IR and ¹HNMR spectroscopy. The surface activity of the prepared compounds has been thoroughly studied and some of their surface properties (such as CMC, Γ_max, and A _min) have been calculated. The surface properties of the prepared compounds were correlated to their chemical structure. It was found that CMC decreases when increasing the molecular weight of polyethylene glycols, whereas A _min increases. Furthermore, the thermodynamic parameters of adsorption and micellization were also calculated. They include ΔG, ΔH, and ΔS of micellization and adsorption. The data show that the synthesized surfactants favor adsorption, so that they can be used as demulsifiers for crude oil emulsions. In this respect, the demulsification test was carried out and the results of demulsification efficiency were correlated to the chemical composition of the investigated compounds. Some factors that affect the demulsification efficiency were also considered.     

Kinetic and Thermodynamic Separation of Cu(II) and Fe(III) by Liquid-Liquid Extraction with a β-Hydroxy-oxime in Toluene

Abstract

A quantitative study of the thermodynamic and kinetic separation of Cu(II) and Fe(III) by liquid-liquid extraction with toluene solutions of the oxime 2-hydroxy-5-t-octyl (acetophenone oxime) has been conducted. On the basis of the stoichiometry, equilibrium constants, rate laws and rate constants of the extraction reactions of Cu(II) and Fe(III) an equation has been derived which describes how the separation of Cu from Fe varies with the chemical composition of the system, the hydrodynamics of the extracting apparatus and the contact time between the aqueous and the organic phases. Our results show that separations which are not feasible thermodynamically are possible when the contact time between the two phases is kept much shorter than that required to reach equilibrium.     

Structure, Properties and Behavior of Kyanite： Use in Refractory Monolithics

1 Introduction Kyanite is an important naturally occurring in-dustrial mineral and is used in the manufacture of avariety of industrial ceramic products; notable exam-ples include refractories and porcelains. It is a high-pressure polymorph of the aluminosilicates of the ne-sosilicate group, which includes kyanite, sillimanite,and andalusite. These three aluminous or alumina-rich minerals are chemically identical with the compo-sition, Al_2SiO_5, but have different crystal structuresand physical properties. It is, however, their alumina     

Advantageous mechanochemical synthesis of copper(Ⅰ)selenide semiconductor,characterization,and properties

Copper(I)selenide-nanocrystalline semiconductor was synthesized via one-step mechanochemical synthesis after 5 min milling in a planetary ball mill.The kinetics of synthesis was followed by X-ray powder diffraction analysis and specific surface area measurements of milled 2Cu/Se mixtures.The X-ray diffraction confirmed the orthorhombic crystal structure of Cu₂Se with the crystallite size～25 nm.The surface chemical structure was studied by X-ray photoelectron spectroscopy,whereby the binding energy of the Cu 2p and Se 3d signals corresponded to Cu⁺and Se^2?oxidation states.Transmission electron microscopy revealed agglomerated nanocrystals and confirmed their orthorhombic structure,as well.The optical properties were studied utilizing ultraviolet-visible spectroscopy and photoluminescence spectroscopy.The direct bandgap energy 3.7 eV indicated a blue-shift phenomenon due to the quantum size effect.This type of Cu₂Se synthesis can be easily adapted to production dimensions using an industrial vibratory mill.The advantages of mechanochemical synthesis represent the potential for inexpensive,environmentally-friendly,and waste-free manufacturing of Cu₂Se.     

Cast (Self-Flow) Ceramic Castables. 4. Spreadability of Molding Systems and Some Properties of Mullite – Silicon Carbide Ceramic Castables

The rheological properties of molding systems are shown to depend on the spreadability of the mixture under the action of its own mass; some of the factors influencing the self-flow are determined, namely, the moisture content, the content of the filler, and the temperature of the mixture. The described self-flow castables based on a mullite HCBS and a SiC filler have a porosity of 18% after drying and 16 – 16.5% after heat treatment. Their ultimate bending strength is 45 MPa and the ultimate compressive strength is 110 MPa, which is higher than those of the known refractories of similar compositions. The temperature of 4% deformation of mullite – silicon carbide refractory heat treated at 1350°C and having C _Vf = 0.4 is 1710 – 1720°C, which is 70 – 80°C higher than that of a similar material molded by pressing and heat treated at 1500°C.     

Synthesis of Multiwalled Carbon Nanotubes–Poly(Methacrylic Acid) Nanohybrid Systems: Characterization,Thermal Properties,and In Vitro Release Studies of Naproxen as a Model Drug

Nanohybrid systems based on carbon nanotubes and pH-sensitive poly(methacrylic acid) were prepared through attaching polymer chains onto carbon nanotubes. First, polymerizable groups were attached onto carbon nanotube walls, then the polymerizable groups were copolymerized with different ratios of methacrylic acid. Obtained systems were studied and characterized through Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, and transmission electron microscopy. A model drug (naproxen) was entrapped into the prepared materials and in vitro release studies were performed in pH 1 (simulated gastric fluids) and pH 7.4 (simulated intestinal fluids). It was noticed that release in simulated intestinal fluids was faster than simulated gastric fluids, therefore the prepared nanohybrid systems can be considered as appropriate carriers for colon-specific drug delivery.     

Acquisition of Water Solubility Diagrams in Ternary Systems (AOT/Organic Solvent/Alcohol) and Extraction of α-Lactalbumin Using Reverse Micellar Systems

In this study water solubility curves were constructed and calorimetric measurements obtained for reverse micellar systems consisting of an alcohol (isopropanol or butanol), surfactant (AOT) and organic solvent (isooctane or hexane). Also evaluated were the effects of alcohol and solvent type and surfactant concentration on the extraction of the α-lactalbumin (α–la). From the obtained solubility diagrams for ternary systems, it was concluded that isooctane presented the highest water solubility capacity in the center of the micelle systems with hexane, since isooctane has greater molecular volume and greater effect of the surfactant aggregation number. With respect to the alcohols, it was observed that isopropanol and butanol act in the system as a co-surfactant, since they prefer to adsorb at the water/solvent interface. It was also verified that butanol improved water solubility inside the reverse micellar due to its contribution to increase the critical packing parameter. The amount of α-la extracted increased proportionally with the AOT concentration for systems with isooctane and hexane. However, for systems with the latter solvent, the concentration of extracted protein first increases and then decreases. The extraction power of reverse micellar systems with isooctane was influenced by the type of alcohol with butanol showing better results. For systems containing hexane there was no effect of the alcohol added to the system on extraction power of α-lactalbumin.     

Investigation of Spectroscopic Properties and Spin-Orbit Splitting in the X(2)Π and A(2)Π Electronic States of the SO(+) Cation

The potential energy curves (PECs) of the X(2)Π and A(2)Π electronic states of the SO(+) ion are calculated using the complete active space self-consistent field method, which is followed by the internally contracted multireference configuration interaction (MRCI) approach for internuclear separations from 0.08 to 1.06 nm. The spin-orbit coupling effect on the spectroscopic parameters is included using the Breit-Pauli operator. To improve the quality of PECs and spin-orbit coupling constant (A(0)), core-valence correlation and scalar relativistic corrections are included. To obtain more reliable results, the PECs obtained by the MRCI calculations are corrected for size-extensivity errors by means of the Davidson modification (MRCI+Q). At the MRCI+Q/aug-cc-pV5Z+CV+DK level, the A(0) values of the SO(+)(X(2)Π(1/2, 3/2)) and SO(+)(A(2)Π(1/2, 3/2)) are 362.13 and 58.16 cm(-1) when the aug-cc-pCVTZ basis set is used to calculate the spin-orbit coupling splitting, and the A(0) of the SO(+)(X(2)Π(1/2, 3/2)) and SO(+)(A(2)Π(1/2, 3/2)) are 344.36 and 52.90 cm(-1) when the aug-cc-pVTZ basis set is used to calculate the spin-orbit coupling splitting. The conclusion is drawn that the core-valence correlations correction makes the A(0) slightly larger. The spectroscopic results are obtained and compared with those reported in the literature. Excellent agreement exists between the present results and the measurements. The vibrational manifolds are calculated, and those of the first 30 vibrational states are reported for the J = 0 case. Comparison with the measurements shows that the present vibrational manifolds are both reliable and accurate.     

Properties of Colloidal Silica‐Fixed and Propionylated Wood Composite (II): Flame Resistance and Other Properties of the Composites

Abstract

The flame resistance, color change, strength, and decay resistance of colloidal silica‐fixed (CSW), propionylated only, and propionylated dual‐treated wood (CSPW) composites were evaluated. The oxygen indexes of the CSPW composites were similar to the CSW composites but much higher than those of untreated woods and the propionylated woods. The oxygen indexes increased with an increase in the weight percent gain of the colloidal silica (WPG_csi) in the composites, showing an effective reduction in the flammability by the fixation of colloidal silica. The CSPW composites showed little or no difference in the modulus of elasticity and modulus of rupture compared with the untreated woods, indicating little or no significant reduction in strength properties of the wood specimens. The color difference of the wood specimens before and after treatment changed slightly. Minimal weight losses of the CSPW composites occurred upon fungal attack by T. versicolor and F. palustris, showing good decay resistance by propionylation of the composites.     

Synthesis of Pre‐Organized Bisdiglycolamides (BisDGA) and Study of their Extraction Properties for Actinides(III) and Lanthanides(III)

Bisdiglycolamides 1–9 were synthesized and studied as extracting agents for An(III) and Ln(III) from nitric acid solutions. Compounds 1d‐3 with rigid spacers as m‐xylylene and 6b‐9 with more flexible alkyl chain linkers, show higher selectivity for Eu(III) extraction over Am(III) than diglycolamides (TBDGA, DMDODGA, TODGA) in (50:50)_%Vol HPT/1‐octanol mixture. Am(III) and Eu(III) extraction kinetics are very fast and back‐extraction with more than 99% efficiency of both cations is possible after four times of contact of the loaded solvent with fresh 0.01 mol/L nitric acid solutions.     

Process Optimization,Physical Properties,and Environmental Stability of an α-Tocopherol Nanocapsule Preparation Using Complex Coacervation Method and Full Factorial Design

α-Tocopherol (α-Toc) has valuable biological activity, but its activity is limited when exposed to environmental factors. Nanocapsules can be used to overcome this problem. Using nanocapsules in the range of 100–200 nm is more beneficial. A 2⁴ full factorial design was carried out to optimize the size of nanocapsules using the complex coacervation method. The four factors were the amount of the wall material, the ratio of core material to wall material, the pH of the solution, and the speed of the homogenizer. The smallest nanocapsules (176 nm) were obtained at a wall content (gelatine and pectin) of 0.8 mg, a percentage of core material (α-Toc) to wall material of 20%, a pH = 4.5, and a homogenizer speed of 12,000 rpm. The encapsulation efficiency was 90.6 ± 1.1%, and the encapsulation yield was 83.4 ± 1.6%. Assessment of the stability of α-Toc after 1 month showed that encapsulation could improve its stability in the presence of three influential factors: humidity, light, and temperature.     

Syntheses, Crystal Structures and Photophysical Properties of a Series of LnIII (Ln?=?Sm, Tb, Pr) Coordination Polymers

Four new lanthanide(Ш) coordination polymers, [Ln(p-aminobenzoate)₂(DMF)(HCOO) (H₂O)]_n (Ln = Sm 1, Tb 2, Pr 3) and {[Pr(2,5-dcp)(CH₃COO)(H₂O)]·1.5H₂O}_n (4) (DMF = N,N-dimethylformamide, 2,5-dcp = pyridine-2,5-dicarboxylate), have been synthesized by hydrothermal method. The structures are determined by the single-crystal X-ray diffraction. The four polymers all crystallize in the monoclinic space group P2₁/n. Polymers 1 and 2 are isostructural; both Sm^III ion of polymer 1 and Tb^III ion of polymer 2 are eight-coordinate. Although polymer 3 possesses the same asymmetric unit as polymers 1 and 2, the three are not isomorphous. The Pr^III ions in polymers 3 and 4 are nine-coordinate. In polymers 1, 2 and 3 the neighboring units are bridged by formyloxy and extend into infinite chains, which are connected by hydrogen bonds to form a hydrogen bond network. However, polymer 4 is bridged by pyridine-2,5-dicarboxylate and acetates to form an infinite 3D network. At room temperature, the IR, UV–Vis–NIR and emission spectra of the four polymers were measured and analyzed. The four polymers emit in the visible or NIR region. The luminescent properties are discussed.     

Properties of α-, γ-, and δ-tocopherol in purified fish oil triacylglycerols

The effect of α-tocopherol (αTOH) (50–2000 ppm), γ-tocopherol (γTOH) (100–2000 ppm), and δ-tocopherol (δTOH) (100–2000 ppm) on the formation and decomposition of hydroperoxides in purified fish oil triacylglycerols (TAG) was studied. The tests were conducted at 30°C in the dark. Purified fish oil TAG oxidized very rapidly with no apparent induction period. The relative ability of the tocopherols to retard the formation of hydroperoxides decreased in the order αTOH> γTOH>δTOH at a low level of addition (100 ppm), but a reverse order of activity was found when the initial tocopherol concentration was 1000 ppm. This dependence of relative antioxidant activity on tocopherol concentration was caused by the existence of concentrations for maximal antioxidant activity for αTOH and for γTOH. An inversion of activity, on the basis of hydroperoxide formation, was observed for αTOH at 100 ppm and for γTOH at 500 ppm, whereas the antioxidant activity of δTOH increased with level of addition up to 1500–2000 ppm. None of the tocopherols displayed any prooxidant activity. All three tocopherols strongly retarded the formation of volatile secondary oxidation products in a concentration-dependent manner. At concentrations above about 250 ppm there appeared to be a linear relationship between rate of consumption of αTOH and initial αTOH concentration, in accordance with the linear relationship observed between the initial rate of formation of hydroperoxides and the initial αTOH concentration. The rate of consumption of γTOH also increased with initial concentration, but to a lesser extent than for αTOH. At high levels of addition the rate of consumption of δTOH was independent of initial concentration, appearing to reflect the greater stability of this tocopherol homolog and participation in reactions with lipid peroxyl radicals only. Presented in part at the AOCS annual meeting in San Diego, California, April 2000.     

Stereodivergent Biocatalytic Formal Reduction of α-Angelica Lactone to (R)- and (S)-γ-Valerolactone in a One-Pot Cascade

The formal asymmetric and stereodivergent enzymatic reduction of α-angelica lactone to both enantiomers of γ-valerolactone was achieved in a one-pot cascade by uniting the promiscuous stereoselective isomerization activity of Old Yellow Enzymes with their native reductase activity. In addition to running the cascade with one enzyme for each catalytic step, a bifunctional isomerase-reductase biocatalyst was designed by fusing two Old Yellow Enzymes, thereby generating an unprecedented case of an artificial enzyme catalyzing the reduction of nonactivated C=C bonds to access (R)-valerolactone in overall 41 % conversion and up to 91 % ee. The enzyme BfOYE4 could be used as single biocatalyst for both steps and delivered (S)-valerolactone in up to 84 % ee and 41 % overall conversion. The reducing equivalents were provided by a nicotinamide recycling system based on formate and formate dehydrogenase, added in a second step. This enzymatic system provides an asymmetric route to valuable chiral building blocks from an abundant bio-based chemical.