Chlorinated volatile organic compounds (CVOCs) are toxic chemical entities emitted invariably from stationary thermal operations when a trace of chlorine is present. Replacing the high-temperature destruction operations of these compounds with catalytic oxidation has led to the formulation of various potent metal oxides catalysts; among them are ceria-based materials. Guided by recent experimental measurements, this study theoretically investigates the initial steps operating in the interactions of ceria surface CeO2(111) with three CVOC model compounds, namely chloroethene (CE), chloroethane (CA) and chlorobenzene (CB). We find that, the CeO2(111) surface mediates fission of the carbon–chlorine bonds in the CE, CA and CB molecules via modest reaction barriers. As a result of localization of excess electrons left behind after creation of oxygen vacancies, analogous fission over an oxygen vacant surface systematically necessitates lower energy barriers. Dehydrochlorination of CE and CA molecules preferentially proceeds via a dissociative addition route; however, subsequent desorption of vinyl and ethyl moieties requires less energy than surface assisted β C–H bond breakage. The profound stability of hydrocarbon species on the surface contributes to the observed deactivation of ceria at temperatures as low as 580 K under pyrolytic conditions. Adsorption of an oxygen molecule at an oxygen vacant site initiates decomposition of the adsorbed phenyl moiety. Likewise, adsorbed surface hydroxyl groups serve as the hydrogen source in the observed conversion of CB into benzene. A plausible mechanism for the formation of 1,4-dichlorobenzene incorporates abstraction of a para hydrogen in the CB molecule by an O− surface anion followed by chlorine transfer from the surface. Plotted conversion–temperature profiles via a simplified kinetic model against corresponding experimental profiles exhibit a reasonable agreement. The results from this study could be useful in the ongoing efforts to improve ceria's catalytic capacity for destroying CVOCs.
Abstract
Heavy-duty diesel vehicle idling consumes fossil fuel and reduces atmospheric quality at idle period, but its restriction cannot simply be proscribed. A comprehensive tailpipe emissions database to describe idling impacts is not yet available. This paper presents a substantial data set that incorporates results from DI multi-cylinders Fiat diesel engine. Idle emissions of CO, hydrocarbon (HC), oxides of nitrogen (NOx), smoke opacity, carbon dioxide (CO2) and noise have been reported, when three EGR ratios (10, 20 and 30%) were added to suction manifold.
CO2 concentrations increased with increasing idle time and engine idle speed, but it didn’t show clear effect for IT adva
... Show MoreOne of the common geotechnical problems is the construction on soft soil and the improvement of its geotechnical properties to meet the design requirements. A stone column is one of the well-known techniques used to improve the geotechnical properties of soft soils. Sometimes thick layers of soft soil imposed the designer to use floating stone columns for improvement of such soil; in this case, the designer will be lost the end bearing of the stone column. In this study, the effects of several patterns of floating stone columns distribution under footing on the bearing capacity of soil and the distribution of excess porewater pressure are investigated. The soft soil used in this study has a very low undrained shear strength (cu) of
... Show MoreBackground: The appointment system is a common practice in primary health care clinics in developed countries. The patients and health care providers in the primary health care setting perceived the appointment system as an indicator of good quality service.
Objective: The aim of this study was to survey patients’ and health care providers’ attitudes towards the introduction of an appointment system and their satisfaction with the existing ‘walk-in’ system in the primary health care setting.
Subjects and Methods: A questionnaire survey was conducted included a convenient sample of 234 patients as well as 76 health care providers from two primary health care center
... Show MoreThis research involves study effect of chloride ions in concentration range (0.01 – 0.50 mol.dm-3) on the corrosion behavior of Al-Zn alloy in basic media of 1x10-3 mol.dm-3 NaOH at pH=11 and four different temperatures in the range (298-313 K). Cathodic and anodic Tafel slopes (bc &ba) and transfer coefficients (αc & αa) were calculated and the results interprets according to the variation of the rate – determining steps. The results also indicate that the chloride ions are bonded chemically in the interface as an initial step of formation of different mixed oxohydroxy – and chloro complexes. Polarization resistance (Rp) is calculates
... Show MoreBackground: Presence of maxillary sinus septa has been known to be a complicating factor for sinus elevation procedure and implant placement in posterior maxilla. The maxillary sinuses septa are thin walls of cortical bone inside the sinus. They vary in number, location, and height. This study aimed to discover the accuracy of Spiral Computed Tomographic Scan in evaluation the maxillary sinus septa (prevalence, location, height) in subjects with dentate, partially edentulous and completely edentulous maxilla. Material and method: This study included (267) subjects ranged from (20-70 years), (132) male and (135) female divided into three groups, (97) fully dentate group, (102) partially edentulous group and (68) completely edentulous group w
... Show MoreTourism is one of the most important sources of income of economic key countries in the world so are imports of tourism for some countries a source of income is not significant of the total revenues of States. Making those countries, and those countries a destination for visitors, and here should be interest in the Wealth and cultural heritage that distinguishes Islamic countries in general, and Iraq in particular, must be placed specialist studies in all areas for the development of this area of tourism, especially religious tourism to achieve a desired and desired of such research.It is the most important ways to develop tourism in general and religious tourism is of particular publications, advertising, and is important for us in this
... Show MoreThis study investigated the application of the crystallization process for oilfield produced water from the East Baghdad oilfield affiliated to the Midland Oil Company (Iraq). Zero liquid discharge system (ZLD) consists of several parts such as oil skimming, coagulation/flocculation, forward osmosis, and crystallization, the crystallization process is a final part of a zero liquid discharge system. The laboratory-scale simple evaporation system was used to evaluate the performance of the crystallization process. In this work, sodium chloride solution and East Baghdad oilfield produced water were used as a feed solution with a concentration of 177 and 220 g/l. The impact of temperature (70, 80, and 90 °C), mixing speed (300, 400, and 500
... Show MoreObjective: To compare two insertion techniques of intramedullary interlocking nails (medial parapatellar versus intrapatellar insertion) in patients with tibial fractures. Methodology: This study was performed at Al-Kindy Teaching Hospital from August 2020 until March 2022. All 32 patients with tibial fractures (29 males and 3 females) were included for tibial closed nail fixation and then followed up for 6 months. We categorized these patients into two groups; Group A (16 patients), those treated by medial parapatellar insertion of an interlocking nail, and Group B (16 patients) with transpatellar tibial nail insertion. All patients were treated by the same surgical team. Results: The range of movement in two weeks (from extension
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