Entropic and enthalpic effects of 4-methoxy substitution in phenoxyl radicals

Values of ΔH_3=(–12.4 ± 1.6) kJ mol^(–1), ΔS_3=(–18.5 ± 5.6) J K^(–1) mol^(–1) for reaction (3) (see text), corresponding to an O–H bond energy of 322.2 kJ mol^(–1) in 1, and to a 14.5 J K^(–1) mol^(–1) entropy loss for the CH_3O–Ar (Ar = aromatic) libration in 2 relative to 1, are derived from the temperature dependence of the equilibrium constant K_3, determined by EPR spectrometry in benzene–toluene media, between 251 and 304 K. These results allow, for the first time, discrimination between enthalpic and entropic effects on the rates of (O)H-atom abstraction by peroxyl radicals from 4-methoxyphenols and related species

Igneous differentiation in porphyry dikes

[Resumen] Se aborda de manera teórica los principales procesos operativos de diferenciación ígnea en secciones transversales de los conductos filonianos, aplicándolo a los diques de pórfido granítico s. 1. del Sistema Central Español. Para estos magmas se deduce un régimen de flujo marcadamente laminar en el conducto (:~ 30 mts. potencia). Estos caracteres impiden tanto la efectividad de franccionamiento cristalino «in situ:\), como grados importantes de asimilación o contaminación en ruta hacia la superficie. Los diques simples, de flujos isoviscosos, van a diferenciarse por fenómenos, principalmente, de flujo ígneo, en ocasiones combinado con la presencia de varios magmas fluyendo a la vez en el mismo pulso (conductos gruesos o flujos veloces). Con estos mecanismos se tenderá a generar evoluciones del tipo félsico a máfico, de borde a centro del dique de pórfido. Los diques compuestos se formarán cuando los magmas son suficientemente contrastados en sus caracteres físicos (viscosidad, p. ej.) y químicos, o cuando son varíos pulsos magmáticos a través del mismo conducto. En estos casos podría haber fen6menos de mezcla magmática si la diferencia de viscosidad es alta y uno de esos magmas es poco viscoso (magmas básicos). En estos casos podrían generarse zonas básicas en el borde, o no, de los diques. de pórfido. En resumen la diferenciación de flujo, la mezcla magmática y la asociación de varios líquidos fluyendo en el mismo conducto (de manera simultánea o por pulsos magmáticos algo separados en el tiempo), parecen ser los mecanismos de diferenciación ígnea más efectivos de estos magmas graníticos que fluyen en angostos conductos filonianos[Abstract] We deal in theoretical way wíth the main differentiation proccesses taking place in dike conducts, applied to the porphyry dikes of the Spanish Central System. For these magmas we infer a strong laminar flow regime (~30 m dike witdh). This, prevent an efficient «in situ:\) cristal fractionation as well as large extent of assimilation-contamination processes during the ascent of the magmas «en route» to more surface levels. Simple dikes, with isoviscous flow, could differentiate mainley by igneous flow. Sometimes this mechanism is combinated with the possibility of severa! Magmas flowing togheter on the same pulse (thick dikes or fast flows). With these mechanisms felsic to mafic evolutions are favoured inward the porphyry dike. Composite dikes are formed when magmas are contrasted enough in their chemical or physical features (p. ej. viscosity), or when different magmatic pulses occur in the same channel. In these conditions commingling of magmas could exist if the viscosity ratio is high apd one of the magmas is very fluid (basic one). These processes could generate basic margins in the porphyry dikes. In short, flow differentiation, magmatic mixing and flowing of associated magmas (simultaneously or by successive pulses), seem to be the more efficient differentiation mechanisms for granitic magmas flowing in narrow dikes

Application of Sustainable Remediation Techniques for Heavy Metal Reduction in Polluted Rivers in Mining Zones: Study Area Ponce Enriquez

Mining activity in Ecuador is primarily artisanal and small-scale. Rivers near the mining county of Camilo Ponce Enriquez have been severely affected by this type of mining. A field study was conducted encompassing 29 sites on the rivers Siete, Fermin, and Pagua during sampling campaigns that took place in both dry (December) and wet seasons (February). Physiochemical parameters and heavy metal concentrations were measured to enable environmental characterization of the rivers. Results revealed that most of the sampled sites had bad water quality and exceeded the environmental limits of heavy metal concentrations set by the Ecuadorian government. A parallel pilot investigation was performed for reducing the heavy metal concentrations in water ecosystems polluted by mining activities using bioremediation techniques. The bioremediation technique applied in the study used bacteria from a wastewater digestor and sugarcane bagasse as a carbon source to support the bacterial community. Sulfide was measured to monitor bacterial activity in experimental bioreactors containing local acid mine drainage (AMD). The results obtained were encouraging, as a significant decrease in heavy metal concentration was observed to nearly the level of Ecuadorian environmental regulations for Al, Cd, Cu, Fe, Pb, and Zn concentrations in freshwater in a set of bioreactors. Keywords: acid drainage, artisanal mining, bioremediation, heavy metals, pollution. Resumen La actividad minera en el Ecuador es principalmente artesanal y de pequeña escala. Los ríos cercanos al área minera de Camilo Ponce Enríquez se han visto severamente afectados por este tipo de minería. Se realizó un estudio de campo en 29 sitios sobre los ríos Siete, Fermín y Pagua durante campañas de muestreo que se realizaron tanto en la época seca (diciembre) como en época húmeda (febrero). Se midieron parámetros fisicoquímicos y concentraciones de metales pesados para permitir la caracterización ambiental de los ríos. Los resultados revelaron que la mayoría de los sitios muestreados tienen agua de mala calidad y excedieron los límites ambientales de concentración de metales pesados establecidos por el gobierno ecuatoriano. También se realizó una investigación piloto paralela destinada a reducir las concentraciones de metales pesados en ecosistemas acuáticos contaminados por actividades mineras utilizando técnicas de biorremediación. La técnica de biorremediación aplicada en el estudio utilizó bacterias de un digestor de aguas residuales y bagazo de caña de azúcar como fuente de carbono para apoyar a la comunidad bacteriana. Se midió el sulfuro para controlar la actividad bacteriana en biorreactores experimentales que contenían drenaje ácido minero (AMD) local. Los resultados obtenidos son alentadores ya que en un conjunto de biorreactores se observó una disminución significativa de las concentraciones de algunos metales pesados alcanzando casi en su mayoría el nivel permisible según las regulaciones ambientales ecuatorianas para las concentraciones de Al, Cd, Cu, Fe, Pb y Zn en agua dulce. Palabras Clave: drenajes ácidos, minería artesanal, biorremediación, metales pesados, contaminación

Dynamics of ignition of stoichiometric hydrogen-air mixtures by moving heated particles

Studying thermal ignition mechanisms is a key step for evaluating many ignition hazards. In the present work, two-dimensional simulations with detailed chemistry are used to study the reaction pathways of the transient flow and ignition of a stoichiometric hydrogen/air mixture by moving hot spheres. For temperatures above the ignition threshold, ignition takes place after a short time between the front stagnation point and separation location depending upon the sphere's surface temperature. Closer to the threshold, the volume of gas adjacent to the separation region ignites homogeneously after a longer time. These results demonstrate the importance of boundary layer development and flow separation in the ignition process

Dynamics of ignition of stoichiometric hydrogen-air mixtures by moving heated particles

Studying thermal ignition mechanisms is a key step for evaluating many ignition hazards. In the present work, two-dimensional simulations with detailed chemistry are used to study the reaction pathways of the transient flow and ignition of a stoichiometric hydrogen/air mixture by moving hot spheres. For temperatures above the ignition threshold, ignition takes place after a short time between the front stagnation point and separation location depending upon the sphere's surface temperature. Closer to the threshold, the volume of gas adjacent to the separation region ignites homogeneously after a longer time. These results demonstrate the importance of boundary layer development and flow separation in the ignition process

Effects of differential diffusion on ignition of stoichiometric hydrogen-air by moving hot spheres

Studying thermal ignition mechanisms is a key step for evaluating many ignition hazards. In the present work, two-dimensional simulations with detailed chemistry are used to study the effect of differential diffusion on the prediction of ignition thresholds of a stoichiometric hydrogen-air mixture by moving hot spheres. Numerical experiments showed an increase of 40 K in the minimum ignition temperature required for ignition when diffusion of species at different rates is taken into account. Detailed analysis of the species profiles at the ignition location and a sensitivity study of the system to the diffusivity of H_2 and H revealed the key role played by the diffusion of H atoms in preventing ignition to take place at temperatures below 1000 K