Promoting the production of industrially important aromatic chloroamines over transition-metal nitrides catalysts has emerged as a prominent theme in catalysis. This contribution provides an insight into the reduction mechanism of p-chloronitrobenzene (p-CNB) to p-chloroaniline (p-CAN) over the γ-Mo2N(111) surface by means of density functional theory calculations. The adsorption energies of various molecularly adsorbed modes of p-CNB were computed. Our findings display that, p-CNB prefers to be adsorbed over two distinct adsorption sites, namely, Mo-hollow face-centered cubic (fcc) and N-hollow hexagonal close-packed (hcp) sites with adsorption energies of −32.1 and −38.5 kcal/mol, respectively. We establish that the activation of nitro group proceeds through direct pathway along with formation of several reaction intermediates. Most of these intermediaries reside in a significant well-depth in reference to the entrance channel. Central to the constructed mechanism is H-transfer steps from fcc and hcp hollow sites to the NO/–NH groups through modest reaction barriers. Our computed rate constant for the conversion of p-CNB correlates very well with the experimental finding (0.018 versus 0.033 s–1 at ∼500 K). Plotted species profiles via a simplified kinetics model confirms the experimentally reported high selectivity toward the formation of p-CAN at relatively low temperatures. It is hoped that thermokinetics parameters and mechanistic pathways provided herein will afford a molecular level understanding for γ-Mo2N-mediated conversion of halogenated nitrobenzenes into their corresponding nitroanilines; a process that entails significant industrial applications.
Infection at the site of vascular anastomosis is a serious complication of vascular surgery and is associated with a high limb loss and mortality rate. The classical method of management is ligation of the injured artery, adequate wound debridement and restoration of circulation. The latter is achieved by either in situ or extra-anatomic bypass. If the distal circulation is not maintained, subsequent amputation is most likely.
Objectives: In this study we tried to assess the efficacy of extra-anatomic synthetic bypass grafts in the treatment of vascular infection in the groin to save the limb and avoid the inevitable amputation.
Methods: Between January 2006 and December 2007, ten male patients aged twenty to thirty five years (mea
The estimation of the stressÙ€ strength reliability of Invers Kumaraswamy distribution will be introduced in this paper based on the maximum likelihood, moment and shrinkage methods. The mean squared error has been used to compare among proposed estimators. Also a Monte Carlo simulation study is conducted to investigate the performance of the proposed methods in this paper.
This study aims to classify the critical points of functions with 4 variables and 8 parameters, we found the caustic for the certain function with the spreading of the critical points. Finally, as an application, we found the bifurcation solutions for the equation of sixth order with boundary conditions using the Lyapunov-Schmidt method in the variational case.
A new spectrophotometric method has been developed for the assay of olanzapine (OLN.) in pure and dosage forms. The method is based on the diazocoupling of (OLN.) with diazotized p-nitroaniline in alkaline medium to form a stable brown colored water-soluble azo dye with a maximum absorption at 405 nm. The variables that affect the completion of reaction have been carefully optimized. Beer’s law is obeyed over the concentration range of (0.5-45.0 μg.mL-1) with a molar absorptivity of 1.5777×104 L.mol-1.cm-1. The limit of detection was 0.3148 μg.mL-1 and Sandell’s sensitivity value was 0.0198 μg.cm-2. The propose
... Show MoreStructure type and disorder have become important questions in catalyst design, with the most active catalysts often noted to be “disordered” or “amorphous” in nature. To quantify the effects of disorder and structure type systematically, a test set of manganese(III,IV) oxides was developed and their reactivity as oxidants and catalysts tested against three substrates: methylene blue, hydrogen peroxide, and water. We find that disorder destabilizes the materialsthermodynamically, making them stronger chemical oxidantsbut not necessarily better catalysts. For the disproportionation of H2O2 and the oxidative decomposition of methylene blue, MnOx-mediated direct oxidation competes with catalytically mediated oxidation, making the most
... Show MoreToxoplasmosis is the most common, widespread disease in the world which is caused by Toxoplasma gondii.The objective of the current study is to determine the effect of the Toxoplasma gondii infection on male sperm, especially on the mitochondria of sperm for men who suffer infertility and the possibility of a hereditary mutation. Sixty seminal fluid and serum samples were taken from sub- fertile patients who attended Teba center for in vitro fertilization / Babylon and similarly samples were also obtained from healthy individuals as a control group, their ages ranged from 20 to 60 years old during the period from 1st may /2016 till 25th January/2017. All samples subjected to the tests included Macroscopic and microscopic examination, molecu
... Show MoreThe city of Ghana is one of the important commercial cities in the country of Sudan, as it was a major source of commercial exchanges, and a commercial mediator across the countries of the Maghreb and the metropolises of the countries of Sudan. Many, and most of them take the desert road, Which traders had to endure the hardships of these roads from the insecurity, high winds and dust that sometimes destroyed the trade convoys, in order to obtain gold, which is one of the most important minerals that Ghana traded with various countries, in addition to the different goods that the merchants carried In particular, salt and its trade with Ghana, and also taxes, which were an important financial resource imposed by some gov
... Show MoreThe purpose of the paper is to tind the degree of the approximation of a functions f be bounded , measurable and defined
in interval [a,h]by Bernstein polynomial in LP space 1 $ p < oo by
using Ditzian-Totik modulus of smootlmess and k 1n average modvlus of smoothness.
Sub-threshold operation has received a lot of attention in limited performance applications.However, energy optimization of sub-threshold circuits should be performed with the concern of the performance limitation of such circuit. In this paper, a dual size design is proposed for energy minimization of sub-threshold CMOS circuits. The optimal downsizing factor is determined and assigned for some gates on the off-critical paths to minimize the energy at the maximum allowable performance. This assignment is performed using the proposed slack based genetic algorithm which is a heuristic-mixed evolutionary algorithm. Some gates are heuristically assigned to the original and the downsized design based on their slack time determined by static tim
... Show MoreThe reservoir characteristics of the Pre-Santonian Eze-Aku sandstone were assessed using an integrated thin section petrography and SEM Back-Scattered Electron (BSE) imaging methods. Fresh outcrop data were collected in the Afikpo area (SE Nigeria). Twenty-eight representative samples from the different localities were analysed to obtain mineralogical and petrographical datasets germane for reservoir characterisation. Thin section petrography indicates that the sandstones are medium-grained, have an average Q90F10L0 modal composition, and are classified as mainly sub-arkose. The sandstones on SEM reveal the presence of cement in the form of quartz overgrowths, authigenic clays and feldspar. From epoxy-sta
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