An absolute droplet pressure interfacial tensiometer and its application to bituminous systems of vanishing density contrast

Experimental problems preclude or limit measurements of interfacial tension in bitumen or extra-heavy crude oil-containing systems when there exists a vanishing density difference between the phases. We describe a novel droplet pressure method that allows such measurements to be made. This method is based on a liquid/liquid adaptation of the capillary displacement differential maximum bubble pressure surface tension method of Schramm and Green [29]. In this method, interfacial tension is calculated from the difference between maximum droplet pressures reached at capillaries of differing internal radii, immersed to slightly different depths. The elimination of the influence of liquid densities allows the measurement of interfacial tensions without independently determining the liquid densities, and in particular, permits measurements in systems for which the density difference is vanishingly small. The absolute measuring technique is illustrated for several systems of pure and practical liquids. Received: 8 March 2000/Accepted: 30 May 2000     

The icosahedral potential and its applications to the study of the anharmonic effects in the overtone levels of the degenerate vibrations of molecules with Ih symmetry

The splitting of the overtone levels of the T_1u, G_u, and H_g vibrations in molecules with I_h symmetry has been calculated by using the perturbation theory. To do this it was necessary to establish beforehand the icosahedral potential, employing the usual procedure in crystal field theory. The total splitting, predicted by the group theory, is obtained when the anharmonicity up to the sixth power of the coordinates is taken into account. Expressions for the intensities of the infrared-active transitions of T_1u vibrations are also proposed.

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Das ikosaedrische Potential und seine Anwendung für die Untersuchung der Anharmonizität in den Obertönen der entarteten Schwingungen von Molekülen mit Symmetrie I_h

Zusammenfassung Die Aufspaltung der Obertöne der Schwingungen T_1u, G_u und H_g in Molekülen mit Symmetrie I_h ist unter Verwendung der Störungstheorie berechnet worden. Dafür war es notwendig, das ikosaedrische Potential herzuleiten. Hierbei wurde das übliche Verfahren der Kristallfeld-Theorie angewandt. Die durch die Gruppentheorie vorhergesagte komplette Aufspaltung erhält man, wenn die Anharmonizität bis zur sechsten Potenz in den Koordinaten berücksichtigt wird. Es werden Ausdrücke für die Intensitäten der infrarot-aktiven Übergänge der Schwingungen T_1u vorgeschlagen.

     

Mesophase study of pure and doped cyanobiphenyl liquid crystals with salen-type systems

Two salen Schiff base ligands derived from the condensation of ethylendiamine on salicylaldehyde and 5-chlorosalicylaldehyde, namely N,N′-bis(salicylidene)ethylene-diamine (L1) and N,N′-bis(5-chlorosalicylidene)ethylene-diamine (L2) as well as two of their iron(III) and nickel(II) complexes, were prepared and then used as doping agents of two thermotropic liquid crystals (LCs) of cyanobiphenyl type, namely 4-cyano-4′-n-pentyl-biphenyl (5CB) and 4-cyano-4′-n-octyl-biphenyl (8CB). The study of the mesophase of pure and doped LCs was carried out by UV–visible spectroscopy equipped with a heating compartment for precise temperature control, differential scanning calorimetry and polarised optical microscopy. The characteristic nematic/isotropic and smectic-A/nematic transition temperatures of 5CB- and 8CB-based systems were measured and then compared to those of the literature concerning pure 5CB and 8CB. Optical microscopy results revealed the existence of Schlieren and focal conic textures of the nematic and smectic states, respectively, both of pure and doped LCs. The homogeneity of the obtained guest–host systems was proven by the linear evolution of their transition temperatures as function of the solute concentration, with correlation factors close to unity.     

Vapor liquid equilibrium modeling of alkane systems with Equations of State: “Simplicity versus complexity”

Two types of Equations of State (EoS), which are characterized here as “simple” and “complex” EoS, are evaluated in this study. The “simple” type involves two versions of the Peng–Robinson (PR) EoS: the traditional one that utilizes the experimental critical properties and the acentric factor and the other, referred to as PR-fitted (PR-f), where these parameters are determined by fitting pure compound vapor pressure and saturated liquid volume data. As “complex” EoS in this study are characterized the EoS derived from statistical mechanics considerations and involve the Sanchez–Lacombe (SL) EoS and two versions of the Statistical Associating Fluid Theory (SAFT) EoS, the original and the Perturbed-Chain SAFT (PC-SAFT).

The evaluation of these two types of EoS is carried out with respect to their performance in the prediction and correlation of vapor liquid equilibria in binary and multicomponent mixtures of methane or ethane with alkanes of various degree of asymmetry. It is concluded that for this kind of systems complexity offers no significant advantages over simplicity. Furthermore, the results obtained with the PR-f EoS, especially those for multicomponent systems that are encountered in practice, even with the use of zero binary interaction parameters, indicate that this EoS may become a powerful tool for reservoir fluid phase equilibria modeling.     

A simplified approach to vapor–liquid equilibria calculations with the group-contribution lattice-fluid equation of state

Equations of state that are based on the lattice-statistics approach use Guggenheim's quasi-chemical approximation to describe the non-randomness in the mixture due to the energetic interactions between the molecules. For ternary and higher-component systems the non-randomness expression is complex and requires an iterative calculation procedure. We have shown that the non-randomness parameters play a negligible role in the application of the GCLF-EoS model (based on the Panayiotou–Vera EoS) for predicting vapor–liquid equilibria. Omission of the non-randomness parameters from such calculations can significantly improve the computation efficiency. Binary, ternary, and quaternary vapor–liquid equilibria predictions were made including polystyrene, polyvinyl acetate, polyethylene, and polypropylene in polar and non-polar solvents to test the theory.     

The evolution of model catalytic systems; studies of structure, bonding and dynamics from single crystal metal surfaces to nanoparticles, and from low pressure (<10(-3) Torr) to high pressure (>10(-3) Torr) to liquid interfaces

The material and pressure gap has been a long standing challenge in the field of heterogeneous catalysis and have transformed surface science and biointerfacial research. In heterogeneous catalysis, the material gap refers to the discontinuity between well-characterized model systems and industrially relevant catalysts. Single crystal metal surfaces have been useful model systems to elucidate the role of surface defects and the mobility of reaction intermediates in catalytic reactivity and selectivity. As nanoscience advances, we have developed nanoparticle catalysts with lithographic techniques and colloidal syntheses. Nanoparticle catalysts on oxide supports allow us to investigate several important ingredients of heterogeneous catalysis such as the metal-oxide interface and the influence of noble metal particle size and surface structure on catalytic selectivity. Monodispersed nanoparticle and nanowire arrays were fabricated for use as model catalysts by lithographic techniques. Platinum and rhodium nanoparticles in the 1-10 nm range were synthesized in colloidal solutions in the presence of polymer capping agents. The most catalytically active systems are employed at high pressure or at solid-liquid interfaces. In order to study the high pressure and liquid interfaces on the molecular level, experimental techniques with which we bridged the pressure gap in catalysis have been developed. These techniques include the ultrahigh vacuum system equipped with high pressure reaction cell, high pressure Sum Frequency Generation (SFG) vibration spectroscopy, High Pressure Scanning Tunneling Microscopy (HP-STM), and High Pressure X-ray Photoemission Spectroscopy (HP-XPS), and Quartz Crystal Microbalance (QCM). In this article, we overview the development of experimental techniques and evolution of the model systems for the research of heterogeneous catalysis and biointerfacial studies that can shed light on the long-standing issues of materials and pressure gaps.     

Understanding the contribution of ascorbic acid to the pigment development in model white wine systems using liquid chromatography with diode array and mass spectrometry detection techniques

The present study investigated the contribution of ascorbic acid to the formation of coloured species in model white wine systems containing (+)-catechin as the oxidisable phenolic substrate. Reactions were carried out in the presence or absence of ascorbic acid in model wine systems buffered with either tartaric acid or formic acid. High performance liquid chromatography with diode array detector (HPLC-DAD) or mass spectrometry (HPLC-MS) analyses demonstrated that glyoxylic acid-derived xanthylium pigments were the main coloured species produced in all samples except those containing just (+)-catechin and formic acid. Higher concentrations of these pigments were detected in the tartaric acid based model system containing both (+)-catechin and ascorbic acid than in the corresponding formic acid model system. The inability of formic acid to form an aldehyde, unlike the known oxidative formation of aldehydes from tartaric acid, contributes to the lower colour development in the formic acid model system. Significantly, these observations imply that ascorbic acid must break down to provide an aldehyde, or ketone, capable of reacting with (+)-catechin to generate the glyoxylic acid-derived xanthylium cations.     

Comparison of the capacity of nitrogen, oxygen, sulfur, and selenium atoms to exist in onium states. quantum-chemical investigation of isomeric model systems with two heteroatoms

HF, B3LYP, and MP2 calculations with the 6-31+G(d) basis set with correction to the energy of zero-point vibrations were carried out to determine the energy characteristics of model molecules containing two heteroatoms in the sp ³- and sp ²-hybrid states; different combinations of N, O, S, and Se atoms were studied. The stability of the onium states of the nitrogen atom was found to be greater than for its chalcogen analogs and the relative stability of onium states of the chalcogen analogs was found to depend on the hybridization of these atoms. Analysis of these results permitted us to construct a stability series of onium derivatives and to interpret the positional selectivity in electrophilic substitution reactions of five-membered heterocyclic compounds with one heteroatom. To J. Stradins, an outstanding and tireless scientist, with our deep respect and sincere affection. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1801–1808, December, 2008.     

Reversed‐phase liquid chromatography with electrospray mass detection and 1H and 13C NMR characterization of new process‐related impurities,including forced degradants of Efavirenz: Related substances correlated to the synthetic pathway

In this study, a stability‐indicating reversed‐phase liquid chromatographic electrospray mass spectrometric method was developed and validated for the determination of process‐related impurities and forced degradants of Efavirenz in bulk drugs. Efavirenz was subjected to acid, alkaline hydrolysis, H₂O₂ oxidation, photolysis, and thermal stress. Significant degradation was observed during alkaline hydrolysis, and the degradants were isolated on a mass‐based purification system and characterized by high‐resolution mass spectrometry, positive electrospray ionization tandem mass spectrometry, and ¹H and ¹³C NMR spectroscopy. Accurate mass measurement and NMR spectroscopy revealed the possible structure of process‐related impurities and degradant under stress conditions. The acceptable separation was accomplished on Waters bondapak C₁₈ column (250 mm × 4.6 mm; 5 μm), using 5 mM ammonium acetate and acetonitrile as a mobile phase in a gradient elution mode at a flow rate of 1.0 mL/min. The eluents were monitored by diode array detector at 247 nm and quantitation limits were obtained in the range of 0.1–2.5 μg/mL for Efavirenz, degradants, and process‐related impurities. The liquid chromatography method was validated with respect to accuracy, precision, linearity, robustness, and limits of detection and quantification as per International Conference on Harmonization guidelines.