Anomalous curving of Arrhenius plots for data obtained from electro-thermal vaporization at atmospheric pressure

Arrhenius plots are often used in electrothermal atomization atomic absorption spectroscopy (ETA-AAS) to obtain activation energies (E_a) of vaporization processes. However, these plots are often nonlinear, and the exact cause of the curvature is not clear. This phenomenon has been attributed to multiple generation functions, diffusion of atoms through the graphite walls, changes in the size of the generating particles, changes in the surface coverage and interferences of the removal function with the supply function. This paper examines several other possibilities using computer simulations on a micro-computer. These possibilities include the effects of diffusion, errors in the assumed order of the reaction and small systematic errors. These can create curving very similar to that observed in typical ETA-AAS and should be considered before assigning the curvature to other chemical or physical properties of the system.     

Gauge symmetry and the EMC spin effect

We emphasise the EMC spin effect as a problem of symmetry and discuss the renormalisation of theC=+1 axial tensor operators. This involves the generalisation of the Adler-Bell-Jackiw anomaly to each of these operators. We find that the contribution of the axial anomaly to the spin dependent structure functiong ₁(x, Q ²) scales at O(α_s). This means that the anomaly can be a largex effect ing ₁. Finally we discuss the jet signature of the anomaly.     

Symmetry reduction for molecular dynamics simulation of an imploding gas bubble

We propose a symmetry reduction technique whereby molecular dynamics (MD) simulations for spherically symmetric gas bubbles can be accelerated. Results for an imploding Xenon bubble containing 50 million particles—the smallest measured sonoluminescing system—are presented.     

A new technique for spatially resolved thermal lensing measurements

A new method is presented for spatially resolved thermal lensing measurements using multiple narrow probe beams and a two-dimensional array detector. The method is applied to an Er, Tm, Ho: YAG laser rod. No significant deviation from a parabolic temperature profile has been found although there is extraordinarily strong thermal lensing in the crystal. Thermo-optical constants of the material are reported.     

The submartingale problem for a class of degenerate elliptic operators

We consider the degenerate elliptic operator acting on ${C^2_b}$ functions on [0,∞) ^d : $$\mathcal{L}f(x)=\sum_{i=1}^d a_i(x) x_i^{\alpha_i} \frac{\partial^2 f}{\partial x_i^2} (x) +\sum_{i=1}^d b_i(x) \frac{\partial f}{\partial x_i}(x), $$ where the a _i are continuous functions that are bounded above and below by positive constants, the b _i are bounded and measurable, and the ${\alpha_i\in (0,1)}$ . We impose Neumann boundary conditions on the boundary of [0,∞) ^d . There will not be uniqueness for the submartingale problem corresponding to ${\mathcal{L}}$ . If we consider, however, only those solutions to the submartingale problem for which the process spends 0 time on the boundary, then existence and uniqueness for the submartingale problem for ${\mathcal{L}}$ holds within this class. Our result is equivalent to establishing weak uniqueness for the system of stochastic differential equations $$ {\rm d}X_t^i=\sqrt{2a_i(X_t)} (X_t^i)^{\alpha_i/2}{\rm d}W^i_t + b_i(X_t) {\rm d}t + {\rm d}L_t^{X^i},\quad X^i_t \geq 0, $$ where ${W_t^i}$ are independent Brownian motions and ${L^{X_i}_t}$ is a local time at 0 for X ⁱ .     

The role of the pion cloud in the interpretation of the valence light-cone wavefunction of the nucleon

The pion cloud renormalises the light-cone wavefunction of the nucleon which is measured in hard, exclusive photon-nucleon reactions. We discuss the leading twist contributions to high-energy exclusive reactions taking into account both the pion cloud and perturbative QCD physics. The nucleon’s electromagnetic form-factor at high Q² is proportional to the bare nucleon probability Z and the cross-sections for hard (real at large angle or deeply virtual) Compton scattering are proportional to Z². Our present knowledge of the pion-nucleon system is consistent with Z = 0.7 ± 0.2. If we apply just perturbative QCD to extract a light-cone wavefunction directly from these hard exclusive cross-sections, then the light-cone wavefunction that we extract measures the three valence quarks partially screened by the pion cloud of the nucleon. We discuss how this pion cloud renormalisation effect might be understood at the quark level in terms of the (in-)stability of the perturbative Dirac vacuum in low energy QCD.     

Scattering of waves from nonlinear media with rough surfaces

Abstract

Reflection and scattering of waves from plane and statistically rough interfaces between nonlinear media are studied theoretically. New hysteresis-type dependences of the reflection and transmission coefficients on the amplitude of the incident wave and on the angle of incidence are predicted. Scattering diagrams for diffusely reflected and transmitted fields are calculated. It is found that when the dielectric constant is a steep function of the incident amplitude, nonlinearity suppresses the Bragg resonant scattering mechanism. Smooth roughness of the boundary is shown to enhance the penetration of evanescent waves into nonlinear media.     

Studies of amine-induced ring opening of some mesoionic xanthines

The ring-opening reactions of seven mesoionic thiazolo[3,2-a]pyrimidine-5,7-diones by a series of primary and secondary amines have been investigated. The rates of the ring fission of five N(8)-substituted mesoionic xanthines with benzylamine were measured and found to follow second order kinetics. The Hammett relationship is followed with ? value of + 0.48 in p-dioxane as solvent. The dependence of rates on temperatures has been studied for the N(8)-ethyl derivative; the energy of activation (Δ E* ) is 25.3 kcals mol^?1, the enthalpy of activation (Δ H* ) is 24.7 kcals mol^?1 and the entropy of activation (Δ S* ) is — 4.9 e.u. A slight increase in rate of reaction was observed when the solvent was changed from p-dioxane to dimethyl sulfoxide. In p-dioxane at constant mesoionic xanthine concentration, the rate constant for ring opening decreased with increasing benzylamine concentration. These results are consistent with a bimolecular nucleophilic mechanism proceeding by the rate-determining formation of a charged tetrahedral transition state.     

Poly(enamine-ketones) from aromatic diacetylenic diketones and aromatic diamines

Novel poly(enamine-ketones) were prepared with inherent viscosities as high as 1.99 dL/g using the Michael-type addition of various diamines to 1,1′-(1,3 or 1,4-phenylene)bis(3-phenyl-2-propyn-1-one) in m-cresol at 60–130°C. Tough, clear, amber films with tensile strengths of 12, 400 psi and tensile moduli of 397, 000 psi were cast from solutions of the polymers in chloroform. The polymers exhibited T_gs as high as 235°C and weight losses of 14% after aging at 232°C in circulating air for 60 h. The synthesis and characterization of several poly(enamine-ketones) are discussed.     

The role of hydrogenases in the anaerobic microbiologically influenced corrosion of steels

The direct electron transfer between 316 L stainless steel and the NAD-dependent hydrogenase from Ralstonia eutropha was studied by spectroelectrochemistry. The presence of hydrogenase and NAD+ clearly increased the quantity of electricity, which was consumed during the electrolysis performed at potential lower than -0.70 V/SCE. The involvement of hydrogenase in the cathodic depolarisation theory was discussed in the light of these results.