Densities,speeds of sound,excess volumes and viscosities of binary mixtures of mtbe with tetralin and decalin at 303.15 k

Measurements of densities, speeds of sound, excess volumes and viscosities of binary mixture of methyl tert-butyl ether with tetralin and decalin are reported at 303.15?K over the entire range of composition. Excess volumes are measured using batch dilatometer technique. Sound speeds are obtained using ultrasonic interferometer. Densities are computed from excess volume data. Isentropic compressibilities are derived from density and sound speed data. Speeds of sound are evaluated on the basis of Jacobson's free length theory and Schaff's collision factor theory. The predicted values are in good agreement with the experimental results. The viscosity data are analysed on the basis of corresponding states approach. Excess volumes and deviation in isentropic compressibilities are negative and deviation in viscosities are positive over the entire composition range. The experimental results are discussed in terms of possible molecular interactions between unlike molecules.     

Review of Analytical Methods for Atmospheric Oxidants Measurements

Abstract

Instrumental and manual methods currently available for the measurement of atmospheric oxidants are surveyed. Techniques used in the United States are emphasized and their advantages and disadvantages are discussed. Commercial systems are evaluated in terms of general operating principles rather than of specific instruments. The ability of these techniques to meet the measurement requirements defined by U.S. Federal air quality oxidant criteria are discussed. Alternative chemical techniques that may have some advantages over the neutral, buffered KI procedure are discussed. Also some attractive, alternative instrumental procedures that are ozone-specific are presented. These systems are based on chemiluminescence and ultraviolet absorption photometry. Electrochemical and colorimetric methods for total oxidant measurements are compared. Finally, some data are presented on relationships of ozone and total oxidants.     

On topological and geometrical distance matrices

Differences between topological and geometrical distance matrices are examined. Some examples of geometrical distances when graphs are embedded in spaces of different dimensions are given. Relations of topological distance matrices to other graph matrices are shown. The topological distance matrices are defined in the Hilbert space and their elements are distances through the graph lattices.     

A study of mica structure and strength properties of polymer materials based on it

The mica microstructure is studied, and its shape and particle sizes are found as dependent on coating technology. Using epoxy and organosilicon polymers, several lots of materials with different contents of mica are prepared and mechanical tests are performed. The optimal amounts of mica wherein the initial strength characteristics are preserved are found. The thicknesses of epoxy and organosilicon polymer wherein high optical decorative properties of mica are preserved are determined.     

Some Strategies for the Refinement of Disordered Structures with the SHELXL-97 Refinement Program

1 INTRODUCTION finement stage. The person performing the crysta- llographic manipulations works on numerical data The high degree of order in the arrangement of that are quite different from the diffraction images atoms in a crystal is a fundamental characteristic of on a computer terminal, and most often does not even the crystalline state, an ideal crystal being envisaged see the images. to be constructed of regularly-stacked unit cells, each The refinement program, SHELXL-97[1], has …     

A perturbative calculation of the rovibrational energy levels of methane

The rovibrational energy levels of methane are determined from a quartic ab initio potential energy force field where the expansion coordinates are the Morse coordinates for the stretches and extension coordinates for the bends. Energies are calculated using canonical Van Vleck perturbation theory. Results are obtained for both rotation-vibration Hamiltonians expressed as functions of curvilinear and rectilinear normal coordinates. Second, fourth, and sixth order curvilinear results are compared with experimental results, and fourth order results for the rectilinear and curvilinear Hamiltonian are compared to each other. The calculated rovibrational levels are in good agreement with the experimental values for low J levels. The calculated rotational level splittings are in even better agreement with the experiment. In particular, the ground state tetrahedral splittings, which are as small as 10(-4) cm(-1), are well reproduced by our calculations at sixth order.     

Contactless conductivity detection for microfluidics: designs and applications

Different methods for construction of contactless conductivity detectors (CCD) for microchip electrophoresis device are described in this review. This includes three main schemes of CCD for microchips, such as (i) the detection electrodes are placed along the microchannel from outside of the microchip and they are insulated from the channel by the cover lid of microchip device; (ii) the electrodes are placed across of the microchannel in the same plane and they are insulated by thin separation channel walls and (iii) electrodes are buried in widened part of microchannel and they are insulated from solution by ultrathin layer of silicon carbide. Specific issues related to the CCD on microfluidics are discussed, such as an influence of shape and magnitude of ac voltage and placement of electrodes and their insulation. Various applications for security, pharmacological, bioassays and food analysis purposes are described.     

Studies in atomic-fluorescence spectroscopy-IV The atomic-fluorescence spectroscopic determination of selenium and tellurium

Selenium and tellurium are determined down to 0.25 and 0.12 p pm respectively by measuring the atomic-fluorescence signals at 2040 A and 2143 A respectively. Other possible wavelengths of measurement are considered in detail and the effects of some extraneous ions are examined. Microwave-excited electrodeless discharge tubes are used as spectral sources and intensity measurements are made with a Unicam SP 900A atomic-absorption/flame-emission spectrophotometer. Atomic-absorption measurements are also made with the same sources and spectrophotometer. The advantages of atomic-fluorescence methods and the use of electrodeless discharge tubes are discussed.     

Spot-test detection of aryl hydrazines, hydrazones, osazones, oximes and aromatic amines

Arylhydrazines are detected by oxidation with N-bromosuccinimide and coupling with resorcinol to form azo-dyes which are intensely coloured in alkaline media. Hydrazones and osazones are hydrolysed to form the arylhydrazines, which are then tested for 4-Nitro- and 2,4-dinitrophenylhydrazines are tested for by forming their hydrazone with salicylaldehyde and adding alkali to produce a violet colour. The hydroxylamine formed by the hydrolysis of oximes is oxidized by iodine monochloride in the presence of sulphanilic acid; coupling with 8-hydroxyquinoline forms a dye that is red in alkali. Intense colours are immediately produced when primary, secondary and tertiary aromatic amines are mixed with diacetoxyiodobenzene. All the tests are sensitive and appear to be specific.     

Electrostatic correlations in polyelectrolyte solutions

The major attribute of polyelectrolyte solutions is that all chains are strongly correlated both electrostatically and topologically. Even in very dilute solutions such that the chains are not interpenetrating, the chains are still strongly correlated. These correlations are manifest in the measured scattering intensity when such solutions are subjected to light, X-ray, and neutron radiation. The behavior of scattering intensity from polyelectrolyte solutions is qualitatively different from that of solutions of uncharged polymers. Using the technique introduced by Sir Sam Edwards, and extending the earlier work by the author on the thermodynamics of polyelectrolyte solutions, extrapolation formulas are derived for the scattering intensity from polyelectrolyte solutions. The emergence of the polyelectrolyte peak and its concentration dependence are derived. The derived theory shows that there are five regimes. Published experimental data from many laboratories are also collected into a master figure and a comparison between the present theory and experiments is presented.     

Ionisation Energies and the Electronic Structures of the N-oxides of diazabenzenes

The ionisation energies and the HeI photoelectron spectra of the N-oxides of diazabenzenes are presented. The valence electronic structures of the N-oxides are discussed in view of the ionisation energies, and the profiles, of the bands. The interpreted data are compared to calculations which are in good agreement. The results are correlated to the physicochemical studies, and particularly to the electronic absorption spectroscopy, of the N-oxides. The assignment of the photoelectron spectra of the azabenzenes are considered with reference to the spectra of their N-oxides.     

Inorganic electrides

Inorganic electrides are a novel kind of ionic compounds in which the anions are electrons confined in a complex array of cavities or channels and the cations are nanoscale arrays of alkali metal ions that provide charge balance. In electrides the donated electron behaves like a low-density correlated electron gas, whereby the dimensionality of the electron gas and its electronic and magnetic properties are determined by the topology of the cavities in the host matrix. Unlike traditional electrides, in which alkali cations are encapsulated within an organic cage, inorganic electrides are thermally stable. The current inorganic electrides based on alkali metal loaded zeolites can be designed as useful reduced-dimensionality materials. Inorganic electrides are powerful reducing agents, and they are able to reduce small aromatic molecules to the radical anions within the channels of the zeolite.     

The Application of NMR Spectroscopy and Chemometrics in Authentication of Spices

Spices and herbs are among the most commonly adulterated food types. This is because spices are widely used to process food. Spices not only enhance the flavor and taste of food, but they are also sources of numerous bioactive compounds that are significantly beneficial for health. The healing effects of spices are connected with their antimicrobial, anti-inflammatory and carminative properties. However, regular consumption of adulterated spices may cause fatal damage to our system because adulterants in most cases are unhealthy. For that reason, the appropriate analytical methods are necessary for quality assurance and to ensure the authenticity of spices. Spectroscopic methods are gaining interest as they are fast, require little or no sample preparation, and provide rich structural information. This review provides an overview of the application of NMR spectroscopy combined with chemometric analysis to determine the quality and adulteration of spices.     

Diffusion of water vapour in polymethyl methacrylate

Certain aspects of the concentration dependence of the diffusion coefficient and on the mechanism of sorption of water vapour in PMMA are investigated. Early time integral sorption kinetics follow the Fickian pattern of initial linearity. Diffusion coefficients deduced from the slopes of these lines are independent of concentration and satisfactorily agree with those obtained from late-time analysis; however, desorption values are higher throughout the whole range of activities than the corresponding absorption ones. On the contrary, typical “non-Fickian” features are discerned in differential absorption kinetics on membranes of different thickness. These anomalies are attributed to rate-determining relaxation processes concurrent with diffusion, whereas other sorption models are incompatible with the general behaviour of this system. General trends of the equilibrium and kinetic data are compared with those of other polymer—water systems and the observed differences are interpreted in terms of the molecular relaxation model.     

钼、钨系过氧化物在Sharpless烯烃环氧化反应中的应用*

钼、钨系过氧化物是非常重要的Sharpless烯烃环氧化催化剂,有着非常广泛的工业发展前景。本文综述了钼、钨系过氧化物的种类,结构,合成方法及催化活性,分析了各种钼、钨系过氧化物的特点以及在催化环氧化领域的发展现状。同时,本文还讨论了钼、钨系过氧化物催化烯烃环氧化反应的机理。评述了在催化环氧化领域中两种主要理论——Mimoun机理与Sharpless机理的争论焦点及发展现状,以及计算化学对两种理论中间过渡态的研究进展,并且重点分析了Sharpless机理的过渡态结构。此外,本文还综述了影响钼、钨系过氧化物催化剂反应活性的各种因素以及质子所产生的副反应。最后,本文对应用于催化环氧化领域的钼、钨系过氧化物未来的研究方向提出了建议。     

Surfactant Enhanced Non-Classical Extraction

Surfactant enhanced non-classical extractions are presented and discussed. They include micellar enhanced ultrafiltration and cloud point extraction. The ideas of the processes are given and the main features are presented. They are compared to the classical solvent extraction. The fundamental of micellar solutions and their solubilisation abilities are also discussed.     

Spectroscopic data for the LiH molecule from pseudopotential quantum Monte Carlo calculations

Quantum Monte Carlo and quantum chemistry techniques are used to investigate pseudopotential models of the lithium hydride (LiH) molecule. Interatomic potentials are calculated and tested by comparing with the experimental spectroscopic constants and well depth. Two recently developed pseudopotentials are tested, and the effects of introducing a Li core polarization potential are investigated. The calculations are sufficiently accurate to isolate the errors from the pseudopotentials and core polarization potential. Core-valence correlation and core relaxation are found to be important in determining the interatomic potential.     

Synthesis of Iso-condensed Heteroaromatic Pyrroles and Their Application in the Preparation of Conducting Polymers

Iso-condensed heteroaromatic pyrroles 1 are 10 -electron aromatic compounds. They are of interest from both theoretical and synthetic points of view. They are the cyclic analogues of heteroaromatic ortho-quinodimethanes 2, and can react with dienophiles in a Diels-Alder reaction to give the synthetically useful cycloadducts 3. Many of them are also of potential pharmaceutical importance because they are isosteric with indoles. Iso-condensed heteroaromatic pyrroles 1 can be used also as the monomers for the synthesis of new conducting polymers 5 with special properties and characteristics. However, the methods for the efficient preparation of the iso-condensed heteroaromatic pyrroles are quite limited. Iso-condensed heteroaromatic pyrroles are generally unstable in acidic conditions and are easily oxidized by air. In our laboratories, we developed three methods for the preparation of this labile heterocyclic ring system under acidic, neutral, and basic conditions.1 Synthesis of the conjugated systems such as 6 for OLED applications will also be discussed.     

Cyclization in reversible and irreversible step-growth polymerizations

Several aspects of cyclization reactions in step-growth polymerizations are considered. The Jacobson–Stockmayer ring-chain equilibrium theory provides the basis for understanding these systems, but there are circumstances where some modifications to the theory are needed. In particular, for ring expansion polymerizations, i.e. those for which there is never a significant fraction of open chains, the statistics are a bit different from those appropriate for ring-chain equilibrium. Also, if the reactions are irreversible the occurrence of rings is significantly different from the reversible case. Rings are more prevalent in irreversible reactions. The implications of these observations for the processing of polymers are briefly considered.