A Study of the Phase Transition in the System [Ag1−x(Na)x]NO3 by Infrared Spectroscopy

A complete infrared study of the mixed crystal system of AgNO₃ and NaNO₃ is carried out in the region 400–4000 cm^?1. The study includes internal fundamental normal vibrations of the NO^?₃ ion in the ordered and disordered phases of AgNO₃ at different values of the sodium concentration, the I.R. spectra, spectral band shape intensities, and frequencies of the internal modes as functions of the sodium ion concentration. Special attention is paid to bending mode, combination mode, asymmetric stretching mode, and over-tone. The rotational energy barrier is determined at different concentrations of the sodium ions in the system.     

A Study of the Thermal Hysteresis in AgNO3

The reversible phase transformation of AgNO₃ is studied. Dielectric constant, d.c. resistivity, differential thermal analysis (DTA) and dilatometric measurements show the occurrence of a reversible phase transition II→I at 160°C with heat of transformation H = 0.78 kcal/mol. The thermal hysteresis in this reversible transformation is examined, the magnitude of the temperature hysteresis does not exceed 12°C. An acceptable agreement is observed between the measured values of the transition temperature obtained by three different experimental techniques. The dilatometric analysis shows that this transition is accompanied by thermal shrinkage with relative shrinkage coefficient 8 × 10^?4. Thermal analysis are also used to get thermodynamic and kinetic data of this phase transition. The temperature dependence of the dielectric constant and d.c. resistivity for single crystals as well as polycrystalline samples of AgNO₃ have clearly located and confirm the phase transitions II→I→II with a strong support to its thermal hysteresis character. The conduction mechanism is found to be activated by energy 0.12 eV for phase I and 0.36 eV for phase II. The observed thermal behaviour of the various measured parameters is attributed to orientational disorder of the nitrate group leading to an order-disorder phase transition which is reported here for first time in AgNO₃.     

A mixed integral equation in the quasi-static displacement problem

In this work, we solve the Fredholm-Volterra integral equation (FVIE) when the kernel takes a potential function form under given conditions. We represent this kernel in the Weber-Sonin integral form.     

Spectroscopic Properties and Laser Induced Fluorescence Determination of Some Endocrine Disrupting Compounds

This work presents spectroscopic properties of some Endocrine Disrupting Compounds (EDCs), frequently found in food and in natural water. Studied molecules belong to the groups of phenolic and phthalate EDCs. In a first part, we have examined their absorption and fluorescence properties. Fluorescence emission wavelengths are about 300 nm for phenolic compounds and 360 nm for phtalate compounds; main excitation wavelengths being comprised between 210 nm and 230 nm. Fluorescence lifetimes measured are short (about 4 ns) and the fluorescence quantum yield has been determined. In a second part, to avoid the time consuming solvent extraction step, an analytical application to evaluate the performance of a direct analysis by laser induced fluorescence spectroscopy of ECDs traces in tap water and in raw water is presented. Good detection limits have been obtained, i.e.: 0.35 μg.L⁻¹ of chlorophenol in tap water, which are always lower than the reported Predictive Non Efficient Concentration (PNEC).     

On the solution of a mixed nonlinear integral equation

In this paper, we consider a mixed nonlinear integral equation of the second kind in position and time. The existence of a unique solution of this equation is discussed and proved. A numerical method is used to obtain a system of Harmmerstein integral equations of the second kind in position. Then the modified Toeplitz matrix method, as a numerical method, is used to obtain a nonlinear algebraic system. Many important theorems related to the existence and uniqueness solution to the produced nonlinear algebraic system are derived. The rate of convergence of the total error is discussed. Finally, numerical examples when the kernel of position takes a logarithmic and Carleman forms, are presented and the error estimate, in each case, is calculated.     

Lanthanide-mediated supramolecular cages and host-guest interactions

The structure and thermodynamic properties of lanthanide complexes with a new tripodal ligand L2 have been elucidated using different physicochemical methods. At stoichiometric ratios, the tetrahedral three-dimensional complexes with lanthanide cations are formed in acetonitrile with good stabilities. Despite minor structural changes comparing to previously investigated tripodal ligands, the resulting assembly exhibits different features revealed with the crystal structure of [Eu(4)L2(4)](OH)(ClO(4))(11) (orthorhombic, Pbcn). Interestingly, the highly charged edifice contains an inner cage encapsulating a perchlorate anion. Such lanthanide mediated cage-like assemblies are rare, and may be of interest for different sensing applications. Indeed, the anionic guest can be exchanged with different anions. The related host-guest equilibria were investigated with NMR techniques. Various aspects of these reactions are qualitatively discussed.     

Solid‐particle erosion in the tube end of the tube sheet of a shell‐and‐tube heat exchanger

Erosion is one of the major problems in many industrial processes, and in particular, in heat exchangers. The effects of flow velocity and sand particle size on the rate of erosion in a typical shell‐and‐tube heat exchanger were investigated numerically using the Lagrangian particle‐tracking method. Erosion and penetration rates were obtained for sand particles of diameters ranging from 10 to 500 µm and for inlet flow velocities ranging from 0.197 to 2.95 m/s. A flow visualization experiment was conducted with the objective of verifying the accuracy of the continuous phase calculation procedure. Comparison with available experimental data of penetration rates was also conducted. These comparisons resulted in a good agreement. The results show that the location and number of eroded tubes depend mainly on the particle size and velocity magnitude at the header inlet. The rate of erosion depends exponentially on the velocity. The particle size shows negligible effect on the erosion rate at high velocity values and the large‐size particles show less erosion rates compared to the small‐size particles at low values of inlet flow velocities. The results indicated that the erosion and penetration rates are insignificant at the lower end of the velocity range. However, these rates were found to increase continuously with the increase of the inlet flow velocity for all particle sizes. The particle size creating the highest erosion rate was found to depend on the flow velocity range. Copyright © 2005 John Wiley & Sons, Ltd.     

Numerical investigation of natural convection inside an inclined parallel‐walled channel

Steady two‐dimensional natural convection in an inclined parallel‐walled channel was investigated numerically. The full elliptic forms of conservation equations were solved together and the velocity vectors, temperature contours and local and average Nusselt number distribution were obtained. The comparisons of local and average Nusselt number with published experimental and numerical results indicate very good agreement. Results are presented for a single aspect ratio, L/b=24, over the range of Rayleigh number of 3–1000 and angle of inclination 0–90°. The results indicate that the overall channel average Nusselt number is reduced as the inclination angle is increased. Significant reductions in the overall Nusselt number are exhibited at high angle of channel inclination. Copyright © 2005 John Wiley & Sons, Ltd.     

Spectroscopic studies of structural changes in irradiated LDPE and its blends

The low temperature glass transition occurring at low temperature in polyethylene samples was studied using Fourier transform infrared, FT‐Raman spectroscopic techniques, which are known to be sensitive to any structural changes in the investigated samples. Anomalous behavior was obtained in the temperature range (98 K → 383 K) indicating the existence of phase transition occurring at about 98 K and disappearing at about 323 K while heating for unirradiated virgin low density polyethylene (VPE) sample with or without crosslinking agent (trimethylol propane triacrylate, TMPTA). Addition of TMPTA monomer caused severe changes in the temperature dependence of both unirradiated and irradiated polyethylene samples. The results given indicated the occurrence of abnormal temperature dependence, which is thought to be related with low temperature structural change resulting from local crosslinking in scrapped polyethylene (SPE) sample already suffering from high degree of crosslinking. Differential scanning calorimetry (DSC) thermograms confirmed the observed new phase transition observed in both unirradiated and irradiated TMPTA loaded VPE/SPE (50/50 wt %) blend. Irradiation, addition of TMPTA as a crosslinking agent, and blending VPE with SPE were found to affect remarkably the variation of the vibration spectrum of LDPE and consequently the resulting structural changes. The experimental results obtained were discussed and correlated with reorientational disorders of the molecular segments (local crosslinking). © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 850–859, 2007     

Response behavior of sodium-selective electrodes modified by surface attachment of the anticoagulant polysaccharides heparin and chondroitin sulfate

Two different polysaccharides with anticoagulant activities, heparin and chondroitin sulfate, were used to modify the surface of sodium-selective electrodes based on asymmetric cellulose triacetate (CTA) membranes. The membranes were formulated with sodium ionophore X, anionic additive, and o-nitrophenyl octyl ether. The response behavior of the surface-modified sodium electrodes was compared with that of control CTA, as well as poly(vinyl chloride) (PVC)-based sodium-selective electrodes. It was found that the selectivity coefficients obtained with the surface modified CTA membrane electrodes were slightly higher than those of the control, but in the case of heparin-modified electrodes they still met the requirements for analysis of sodium in physiological fluids within an error of <1%; the corresponding error for chondroitin sulfate-modified electrodes was also <1% except for the case of potassium ion in which the error was 1.3%. Likewise, it was found that other response characteristics, such as detection limit, linear range, slope of the response plot, selectivity pattern, and response time were comparable in both the control and the polysaccharide-modified electrodes. Therefore, the surface modification does not significantly alter the response behavior of the sensors.