Two organophosphorus pesticides: methyl parathion and dicapthon

Structural studies performed in this laboratory of organophosphorus pesticides continue with these related compounds. The –NO₂ groups of methyl parathion (systematic name: dimethyl 4‐nitrophenyl phosphorothioate, C₈H₁₀NO₅PS) and dicapthon (systematic name: 2‐chloro‐4‐nitrophenyl dimethyl phosphorothioate, C₈H₉ClNO₅PS) make dihedral angles of 10.67 (8) and 5.8 (1)°, respectively, with the planes of their attached rings, which accompanies angular distortion at the ring C atoms to which the –NO₂ groups are attached. Similar distortions are observed at the C atom to which the thiophosphate groups are attached. Significant differences in distances and angles around the phenolic O, versus the –OMe groups, explain why it is the site of hydrolysis for these compounds. A comparison of a torsion angle involving the thiophosphate group and phenolic O atom with similar pesticide structures is given and indicates steric influences on that angle.     

Investigation of fill factor losses on 20.2% efficient n‐type mono‐like silicon solar cells with laser contact opening

Large area (243.36 cm²) back‐junction passivated emitter, rear totally diffused (PERT) solar cells with laser contact opening (LCO) on n‐type mono‐like crystalline Si with efficiencies of 20.2% are presented. Boron emitters with high electrical quality (implied open circuit voltage iV_OC up to 700 mV) are formed during a co‐diffusion step using SiO_x:B layers. Increasing the rear metal contact coverage, we observed a decrease in fill factor (FF) instead of the expected increase due to the decrease of the back side series resistance. We show that it can be attributed to recombination centers (RCs) in the space charge region underneath the contact spots inducing an increasing second diode contribution. The presented empirical model for the RCs implemented in Synopsys Sentaurus TCAD allows for a successful reproduction of the FF, pseudo FF and V_OC behaviour with contact coverage. According to this model, the RCs induced by laser ablation and subsequently evaporation of Al have a shallow exponential distribution with a characteristic length of L_T = 0.2 µm and an effective surface density of N *_T0 = 25 cm^–1. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Optimization of Sr-90 precipitation in nitric acid using design of experiments for radioactive waste characterization method

Journal of Radioanalytical and Nuclear Chemistry - 90Sr radiochemical method using nitric acid for Sr and Ca separation was optimized using design of experiments methodology. Nitric acid...     

Analytical models for the series resistance of selective emitters in silicon solar cells including the effect of busbars

A theoretical analysis of the power loss and series resistance of the front side emitter in silicon solar cells is presented. Existing 1D models (infinitely long finger) and 2D models (including the effect of busbars) of emitter series resistance contribution are extended to the case of selective emitters. The general case of different current densities for both emitters in the selective emitter scheme is considered in these extensions. The resulting models depend on the individual sheet resistances and current densities in both emitters and the device's overall grid geometry. The models are corroborated by finite element simulation of the potential in the emitter. An excellent agreement is found between the analytical models, and the simulations for a wide range of sheet resistances typically encountered in silicon solar cells. Grid simulations using the 2D model are applied to solar cells with selective emitters, where the width of the low‐resistive emitter was varied. The simulations demonstrate that the 2D model can explain the absolute change in fill factor observed in these cells. Copyright © 2013 John Wiley & Sons, Ltd.     

Solving mixed-integer robust optimization problems with interval uncertainty using Benders decomposition

Uncertainty and integer variables often exist together in economics and engineering design problems. The goal of robust optimization problems is to find an optimal solution that has acceptable sensitivity with respect to uncertain factors. Including integer variables with or without uncertainty can lead to formulations that are computationally expensive to solve. Previous approaches for robust optimization problems under interval uncertainty involve nested optimization or are not applicable to mixed-integer problems where the objective or constraint functions are neither quadratic, nor linear. The overall objective in this paper is to present an efficient robust optimization method that does not contain nested optimization and is applicable to mixed-integer problems with quasiconvex constraints (? type) and convex objective funtion. The proposed method is applied to a variety of numerical examples to test its applicability and numerical evidence is provided for convergence in general as well as some theoretical results for problems with linear constraints.     

Homogeneous and unimolecular gas‐phase thermal decomposition kinetics of methyl benzoylformate: experimental and theoretical study

The kinetics of the gas‐phase thermal decomposition of the α‐ketoester methyl benzoylformate was carried out in a static system with reaction vessel deactivated with allyl bromide, and in the presence of the free radical inhibitor propene. The rate coefficients were determined over the temperature range of 440–481 °C and pressures from 32 to 80 Torr. The reaction was found to be homogenous, unimolecular and obey a first‐order rate law. The products are methyl benzoate and CO. The temperature dependence of the rate coefficient gives the following Arrhenius parameters: log₁₀ k (s^?1) = 13.56 ± 0.31 and E_a (kJ mol^?1) = 232.6 ± 4.4. Theoretical calculations of the kinetic and thermodynamic parameters are in good agreement with the experimental values using PBE1PBE/6‐311++g(d,p). A theoretical Arrhenius plot was constructed at this level of theory, and the good agreement with the experimental Arrhenius plot suggests that this model of transition state may describe reasonably the elimination process. These results suggest a concerted non‐synchronous semi‐polar three‐membered cyclic transition state type of mechanism. The most advanced coordinate is the bond breaking C^δ+‐‐‐^δ‐OCH₃ with an evolution of 66.7%, implying this as the limiting factor of the elimination process. Copyright © 2014 John Wiley & Sons, Ltd.     

Gas‐phase elimination kinetics of selected aliphatic α,β‐unsaturated aldehydes catalyzed by hydrogen chloride

The gas‐phase elimination of 2‐methyl‐2‐propenal catalyzed by HCl yields propene and CO gas, while E‐2‐pentenal with the same catalyst gives butene and CO gas. The kinetics determinations were carried out in a static system with the reaction vessels deactivated with allyl bromide and the presence of the free radical inhibitor toluene. Temperature and pressure ranges were 350.0–410.0 °C and 34–76 Torr. The elimination reactions are homogeneous and unimolecular, and follow a first‐order rate law. The rate coefficients for the reactions are expressible by the following Arrhenius equations: Data from the kinetic and thermodynamic parameters of these catalyzed elimination reactions implies a mechanism of a concerted five‐membered cyclic transition state structure for the formation of the corresponding olefin and carbon monoxide. Copyright © 2015 John Wiley & Sons, Ltd.     

Stereospecific Formal [3+2] Dipolar Cycloaddition of Cyclopropanes with Nitrosoarenes: An Approach to Isoxazolidines

The MgBr₂‐catalyzed formal [3+2] cycloaddition of donor–acceptor activated cyclopropanes with nitrosoarenes offers a novel approach to various structurally diverse isoxazolidines. The reactions, which are experimentally easy to conduct, occur with complete stereospecificity and perfect control of regioselectivity. Product isoxazolidines can be readily transformed into α‐amino lactones by reductive or decarboxylative N? O cleavage and subsequent lactonisation, and the N‐aryl bond cleavage is also possible under oxidative conditions.