Revised mechanism and improved methodology for the Perkin condensation. Resuscitation of the mechanism involving benzal acetate and the improbability of the enolate of acetic anhydride

The Perkin condensation most likely occurs via the initial formation of a gem-diacetate from the aromatic aldehyde and acetic anhydride reactants. The key reactive nucleophile appears to be the enolate of the gem-diacetate rather than of acetic anhydride. The diacetate from PhCHO may be converted to cinnamic acid under a variety of (relatively) mild basic conditions.     

Some studies on thallium oxalates. VI

The effect of the thallium(I) concentration on the potentiometric titration of thallium(III) with oxalic acid in 0.1M HNO₃ or 0.05M H₂SO₄ is studied, and conditions are established for the preparation of the thallium(I) bis-oxalato diaquo thallate(III) complex. Chemical analysis of the salt corresponds to the formula T1^I(T1^III(C₂O₄)₂) · 5 H₂O. Thermal decomposition studies on the complex using TG, DTG and DTA techniques indicate the formation of thallium(I) oxalate (stable from 130° to 320°) as the intermediate, the final product being a mixture of thallium(I) oxide and thallium(III) oxide (stable from 520° to 600°). Infrared absorption spectra, X-ray diffraction patterns and microscopic observations are used to characterise the complex and the intermediate.     

Light scattering by Gaussian random ellipsoid particles: First results with discrete-dipole approximation

We introduce the stochastic geometry of a Gaussian random ellipsoid (GE) and, with the discrete-dipole approximation, carry out preliminary computations for light scattering by wavelength-scale GE particles. In the GE geometry, we describe the base ellipsoid by the three semiaxes a?b?c. The axial ratios b:a and c:a appear as two shape parameters additional to those of the Gaussian random sphere geometry (GS). We compare the scattering characteristics of GE particles to those of ellipsoids. Introducing irregularities on ellipsoids smoothens the angular scattering characteristics, in a way analogous to the smoothening of spherical particle characteristics in the case of GS particles.     

Chemical Degradation of Mercury Alkyls Mediated by Copper Selenide Nanosheets

Methylation and demethylation of mercury compounds are two important competing processes that control the net production of highly toxic mercury alkyls, methylmercury (MeHg⁺) and dimethylmercury (Me₂Hg), in environment. Although the microbial and the photochemical methylation and demethylation processes are well studied in recent years but the chemical methylation and demethylation processes have not been studied well. Herein, we report for the first time that the CuSe nanosheet has remarkable ability to activate the highly inert Hg?C bonds of various MeHg⁺ and Me₂Hg compounds at room temperature (21 °C). It facilitates the conversion of MeHg⁺ into Me₂Hg in the absence of any proton donors. Whereas, in the presence of any proton source, it has unique ability to degrade MeHg⁺ into CH₄ and inorganic mercury (Hg²⁺). Detailed studies revealed that the relatively fast Hg?C bond cleavage was observed in case of MeHgSPh or MeHgI in comparison to MeHgCl, indicating that the Hg?C bond in MeHgCl is relatively inert in nature. On the other hand, the Hg?C bond in Me₂Hg is considered to be exceedingly inert and, thus, difficult to cleave at room temperature. However, CuSe nanosheets showed unique ability to degrade Me₂Hg into CH₄ and Hg²⁺, via the formation of MeHg⁺, under acidic conditions at room temperature. DFT calculations revealed that the Hg?C bond activation occurs through adsorption on the surface of (100)‐faceted CuSe nanosheets.     

Light scattering by coated Gaussian and aggregate particles

Light scattering by nonspherical and inhomogeneous small particles is studied by varying particle shapes, sizes, and compositions. We introduce an efficient tool for deforming particle shape and composition by adding a coating on an initial particle. This concave-hull transformation is applied to wavelength-scale Gaussian and aggregate particles, and the differences in the optical properties of the coated particles are compared to those of the uncoated geometries. The light-scattering computations are performed using the discrete-dipole approximation method which allows for internal inhomogeneity and irregular particle shapes. The results are analyzed concentrating on the intensity of the scattered light, the degree of linear polarization for unpolarized incident light, and the depolarization ratio. Polarization results yield the most significant differences and, moreover, coated aggregates are observed to produce net positive polarization, whereas it is negative for the Gaussian particles, also resembling the polarization of a spherical particle. As for the depolarization ratio, an intriguing double-lobe feature is observed near the backscattering direction for both particle geometries regardless of size, shape, and composition. The double-lobe maxima and minima generally coincide with those of the intensity and polarization.     

Microwave backscattering by nonspherical ice particles at 5.6 GHz using second-order perturbation series

Scattering of microwaves by an ensemble of nonspherical ice particles is studied using a scattering model based on a second-order perturbation series at 5.6 GHz (C-band). Particle shapes are defined using a Gaussian random sphere geometry. Particle inhomogeneity is taken into account using three different effective-medium approximations: Maxwell–Garnett, Bruggeman, and Coherent Potential mixing rules. By systematically varying particle size, liquid water content, Gaussian shape parameters, and internal structure, it is found that liquid water content is the most important factor for the co-polarized backscattering; the shape is relatively unimportant. For depolarized backscattering, the shape is of fundamental importance, although the other factors are significant too. Surprisingly, the type of nonsphericity is found to be important for depolarization even for scatterers that are in the Rayleigh region: elongated targets depolarize clearly stronger than more irregular shapes. This finding seems not to be strongly size dependent, at least for size parameters from 0.0059 to 0.47, and indicates that the accurate modeling of shape is important for polarization quantities even in the Rayleigh region.     

Some studies on thallium oxalates. II. Thermal decomposition of potassium bisoxalato diaquothallate(III) dihydrate

Potassium bisoxalato diaquothallate(III) dihydrate is obtained by precipitating thallium(III) with oxalic acid from slightly acidic (HNO₃ or H₂SO₄) solutions in the presence of potassium ions. The thermal decomposition behaviour of the complex is studied using the techniques of TG, DTA and DTG. The solid complex salt and the intermediate products of its thermal decomposition are characterised using IR absorption spectra, microscopic observations, electrical conductivity measurements and X-ray diffraction data.