The Preparation and Characterization of Highly Dispersed PdO over Alumina for Low‐temperature Combustion of Methane

PdO/Al₂O₃ catalysts prepared by glow discharge plasma treatment followed by thermal calcination show a much higher dispersion and a better catalytic activity for methane combustion at relatively low temperatures. The dispersion of palladium active species by such plasma prepared catalysts is 29.7%, 5.4 times higher than that of conventional catalysts. XPS analysis indicates that a surface enrichment of Pd active species (PdO) has been achieved after plasma treatment. The surface atomic composition of PdO of plasma prepared catalysts reaches 10.5%. XRD characterization also confirms a wellcrystallized PdO phase present on the plasma prepared catalyst. The lightoff temperature of the plasma prepared catalyst is 370°C, 50°C lower than that obtained from the conventional catalyst.     

Determination of imazalil by on-line coupled capillary isotachophoresis with capillary zone electrophoresis

A simple, rapid and reproducible capillary isotachophoretic on-line coupled with capillary zone electrophoresis (CITP-CZE) method for the determination of IMz in food packaging extracts and its residues in apples is described. A good separation of the IMZ from other sample constituents was achieved within 15 minutes without any sample clean up. Method characteristics (linearity, accuracy, intra-assay and detection limit) were determined. Less amount of time involved, sufficient sensitivity and low running cost are the important attributes of CITP-CZE method.     

Kinetic Determination of Microquantities of Rutin by Perturbation of the Bray-Liebhafsky Oscillatory Reaction in an Open System

A kinetic method is described for the microquantitative (microconcentration/microvolume) determination of rutin based on potentiometric monitoring of the concentration perturbations of the Bray-Liebhafsky (BL) oscillatory reaction being in a non-equilibrium stationary state close to a bifurcation point. The experiments are carried out in an open reactor. The response of the matrix system to perturbations by different concentrations of rutin ethanolic solutions is followed by a Pt-electrode. In the concentration range between 7.8×10^–8moldm^–3 and 9.1×10^–6mol dm^–3, we found a linear dependence of the maximal potential shift, E_m, on the logarithm of the rutin concentrations. The unknown concentrations can be determined from the calibration curve up to an accuracy of ±5%. The detection limit is 3.6×10^–8mol dm^–3. The amount of required sample can be as small as 10µL.     

Lanthanide nitrate complexes with 2-azacyclononanone

Thermal behavior of rare earth nitrate complexes with 2-azacyclononanone (AZA) with Ln(NO₃)₃·3(AZA) composition (where Ln=Gd, Er and Ho) was analyzed in kinetic point of view. Kinetic parameters were calculated from thermogravimetric data. All obtained results were similar. The first decomposition step was representative to the loss of ligand and the residue was essentially Ln₂O₃. Furthermore, a reaction path was proposed for the thermal decomposition of the Ln(NO₃)₃·3(AZA).     

Elastic scattering cross sections for 160<Superscript>°</Superscript> and 170<Superscript>°</Superscript>backscattering of 1.40-2.64 MeV protons from natural vanadium

Summary The elastic scattering cross sections of natural vanadium for protons have been measured for beam energies below 2.64 MeV in steps of 10 keV and in the angular 160° and 170°. The overall standard error (Δσ_Exp/σ_Exp) in the measured cross sections is estimated to be better than ±3% at all the beam energies and angles. The results are presented in graphical and tabular forms that should be useful for those who wish to use the cross sections for material analysis.     

Thermodynamics of molecular interactions in ethyl iodide+toluene mixtures

The excess Gibb's free energy of mixing, G^E, for ethyl iodide+toluene at 25°C have been obtained from the measured vapor pressuure data. The H^E and G^E values for ethyl iodide+toluene are positive throughout the ethyl iodide concentration range and G^E>H^E. The results have been analyzed in terms of Flory and ideal associated model theory of nonelectrolyte solutions. It has been observed that the ideal associated model approach which assumes the presence of AN and A₂B molecular species describes well (within±10 J-mol^–1 in the worst case) the general dependence of H^E on X_A (mole fraction of ethyl iodide) over the whole composition range for ethyl iodide+toluene mixtures. The equilibrium constants for A+A AB and 2A+BA₂B reactions along with the enthalpies of formation of AB and A₂B molecular species have been calculated.     

About compensation effect by thermal decomposition of some catalyst precursors

Summary In order to obtain catalysts, the thermal decomposition of the precursors is a compulsory step. However, kinetic analysis of the decomposition data obtained under non-isothermal conditions lead very seldom to the intimate reaction mechanism. There is also a lack of information because in non-isothermal kinetics, the compensation effect, is rather a rule and unfortunately a source of debate. In order to discriminate between these processes, and the influence of conversion, respectively temperature on the reaction rate, the NPK (non-parametric kinetic - Sempere and Nomen) method was used. This method is based on the singular value decomposition algorithm (SVD) applied on the matrix of reaction rate at corresponding conversion and temperature. This method allows a less speculative determination of the conversion functions and of the kinetic parameters.     

Solid state a.c. conductivity and FT-IR spectral analyses for the conflicting effects of proton mobility and association in some azophenol derivatives of cyclic phosphazene

Variable strength H-bonding affects the mobility and so electric conduction of protons differently. Also, variable extent mesomerism modifies electric conduction with varying dielectric features. Both these molecular modifiers are properly cited using azophenol derivatives as model compounds for discussion of their consequences in the varying features of electric conduction. The electric permittivity shows low-frequency dispersion characteristic of ionic conduction over mobile charge carries; the mobility shifts at a critical temperature T _c, being structure dependent. The frequency-dependent Z′′-Z′ layout changes with temperature from linear at low temperatures to semicircular above T _c within a frame of temperature-sensitive dipole-ionic mediated conduction. The a.c. conductivity, σ_ac, increases with frequency and temperature and becomes frequency insensitive, like d.c. conductivity, σ_dc, above the T _c because of the escalating contribution from the d.c. conduction. The mesomeric structure seems to prompt a dipole-based electric conduction of high relaxation energy over the strongly associated phenolic protons that may be thermally activated above the T _c into a much lower relaxation energy protonic conduction of up to two orders higher conductivity. The protonic conduction emerges at a T _c that falls with a drop in the relaxation energy following a similar order of increasing proton mobility and mesomerism in the azophenol derivatives: azocatechol>azoquinol>azoresorcinol. On the molecular level, variable temperature infrared spectroscopy reveals higher proton mobility and mesomerism for the azocatechol derivative that demonstrates its higher protonic conductivity at lower T _c and relaxation energy, compared to the azoquinol and azoresorcinol derivatives. This is well verified in the light of conflicting intramolecular H-bonding that assists the proton mobility in azocatechol whereas it associates the protons in azoresorcinol more than in azoquinol. Electronic Publication     

Microwave-assisted extraction of zearalenone from wheat and corn

A microwave-assisted extraction (MAE) method has been developed for determination of zearalenone in wheat and corn by LC-MS with an atmospheric pressure chemical ionization interface (APCI). Matrix effects were minimized by use of matrix-matched standard curves for quantification of the analyte. The limit of quantification (LOQ) of the method was 30 ng g(-1) in wheat and 20 ng g(-1) in corn. The rapid LC-MS method enabled analysis of the extracts without clean-up, thereby reducing analyte losses, the time required for the analytical procedure, and costs. A factorial design approach was used to examine the effect on extraction efficiency of the main extraction conditions - time, temperature, and solvent. On the basis of results from statistical assessment extraction was performed with 1:1 (v/v) methanol-acetonitrile at 80 degrees C for 5 min. When these extraction conditions were applied to a wheat sample from a recently conducted international proficiency test, 92% (103 ng g(-1)) of the assigned zearalenone concentration (112 ng g(-1)) in the test material was obtained. This result was within the uncertainty (u) range of the assigned value of the test material (u=+/-15.8 ng g(-1), alpha=0.05) thereby demonstrating the accuracy of the method was sufficient. The precision of the whole method was also confirmed to be adequate, because the observed relative standard deviation (RSD) of 12% (n=10) also fulfils the quality criteria recommended by European guidelines for in-house method validation.     

Hot atom chemistry in oxyanion targets,part II1: Recoil behaviour of56Mn in permanganates

Fractional precipitation techniques have been utilized to separate the lower valent and parent forms of⁵⁶Mn in permanganate targets and an attempt is made to study a few aspects of chemical stabilization of recoil⁵⁶Mn in permanganates. Ammonium permanganate, recoil behaviour of which has not been studied previously, is chosen as one of the targets along with the potassium permanganate for initial retention and also for isothermal annealing.⁵⁶Mn initial retentions of about 12% and about 4% are obtained for potassium and ammonium permanganate, respectively, by activation from a Ra–Be neutron source. A usual trend for KMnO₄ and the reduction of recoil fragments by ammonium ions in NH₄MnO₄ are seen through the isothermal annealing study.