Thermodynamic properties and atomistic structure of the dry amorphous silica surface from a reactive force field model

A force field model of the Keating type supplemented by rules to break, form, and interchange bonds is applied to investigate thermodynamic and structural properties of the amorphous SiO2 surface. A simulated quench from the liquid phase has been carried out for a silica sample made of 3888 silicon and 7776 oxygen atoms arranged on a slab similar to 40 angstrom thick, periodically repeated along two directions. The quench results into an amorphous sample, exposing two parallel square surfaces of similar to 42 nm(2) area each. Thermal averages computed during the quench allow us to determine the surface thermodynamic properties as a function of temperature. The surface tension turns out to be gamma=310 +/- 20 erg/cm(2) at room temperature and gamma=270 +/- 30 at T=2000 K, in fair agreement with available experimental estimates. The entropy contribution Ts-s to the surface tension is relatively low at all temperatures, representing at most similar to 20% of the surface energy. Almost without exceptions, Si atoms are fourfold coordinated and oxygen atoms are twofold coordinated. Twofold and threefold rings appear only at low concentration and are preferentially found in proximity of the surface. Above the glass temperature T-g=1660 +/- 50 K, the mobility of surface atoms is, as expected, slightly higher than that of bulk atoms. The computation of the height-height correlation function shows that the silica surface is rough in the equilibrium and undercooled liquid phase, becoming smooth below the glass temperature T-g.

A field and reactive transport model study of arsenic in a basaltic rock aquifer

The use of geothermal energy as a source for electricity and district heating has increased over recent decades. Dissolved As can be an important constituent of the geothermal fluids brought to the Earth's surface. Here the field application of laboratory measured adsorption coefficients of aqueous As species on basaltic glass surfaces is discussed. The mobility of As species in the basaltic aquifer in the Nesjavellir geothermal system, Iceland was modelled by the one-dimensional (1D) reactive transport model PHREEQC ver. 2, constrained by a long time series of field measurements with the chemical composition of geothermal effluent fluids, pH, Eh and, occasionally, Fe- and As-dissolved species measurements. Di-, tri- and tetrathioarsenic species (As(OH)S22-, AsS₃H^2-, AsS33- and As(SH)4-) were the dominant form of dissolved As in geothermal waters exiting the power plant (2.556μM total As) but converted to some extent to arsenite (H₃AsO₃) and arsenate HAsO42- oxyanions coinciding with rapid oxidation of S2- to S2O32- and finally to SO42- during surface runoff before feeding into a basaltic lava field with a total As concentration of 0.882μM following dilution with other surface waters. A continuous 25-a data set monitoring groundwater chemistry along a cross section of warm springs on the Lake Thingvallavatn shoreline allowed calibration of the 1D model. Furthermore, a series of ground water wells located in the basaltic lava field, provided access along the line of flow of the geothermal effluent waters towards the lake. The conservative ion Cl^- moved through the basaltic lava field (4100m) in less than10a but As was retarded considerably due to surface reactions and has entered a groundwater well 850m down the flow path as arsenate in accordance to the prediction of the 1D model. The 1D model predicted a complete breakthrough of arsenate in the year 2100. In a reduced system arsenite should be retained for about 1ka. © 2011 Elsevier Ltd.

A reactive force field simulation of liquid-liquid phase transitions in phosphorus

A force field model of phosphorus has been developed based on density functional (DF) computations and experimental results, covering low energy forms of local tetrahedral symmetry and more compact (simple cubic) structures that arise with increasing pressure. Rules tailored to DF data for the addition, deletion, and exchange of covalent bonds allow the system to adapt the bonding configuration to the thermodynamic state. Monte Carlo simulations in the N-P-T ensemble show that the molecular (P-4) liquid phase, stable at low pressure P and relatively low temperature T, transforms to a polymeric (gel) state on increasing either P or T. These phase changes are observed in recent experiments at similar thermodynamic conditions, as shown by the close agreement of computed and measured structure factors in the molecular and polymer phases. The polymeric phase obtained by increasing pressure has a dominant simple cubic character, while the polymer obtained by raising T at moderate pressure is tetrahedral. Comparison with DF results suggests that the latter is a semiconductor, while the cubic form is metallic. The simulations show that the T-induced polymerization is due to the entropy of the configuration of covalent bonds, as in the polymerization transition in sulfur. The transition observed with increasing P is the continuation at high T of the black P to arsenic (A17) structure observed in the solid state, and also corresponds to a semiconductor to metal transition. (C) 2004 American Institute of Physics.

A tip-high, Ca2+-interdependent, reactive oxygen species gradient is associated with polarized growth in Fucus serratus zygotes

We report the existence of a tip-high reactive oxygen species (ROS) gradient in growing Fucus serratus zygotes, using both 5-(and 6-) chloromethyl-2',7'-dichlorodihydrofluorescein and nitroblue tetrazolium staining to report ROS generation. Suppression of the ROS gradient inhibits polarized zygotic growth; conversely, exogenous ROS generation can redirect zygotic polarization following inhibition of endogenous ROS. Confocal imaging of fluo-4 dextran distributions suggests that the ROS gradient is interdependent on the tip-high [Ca2+](cyt) gradient which is known to be associated with polarized growth. Our data support a model in which localized production of ROS at the rhizoid tip stimulates formation of a localized tip-high [Ca2+](cyt) gradient. Such modulation of intracellular [Ca2+](cyt) signals by ROS is a common motif in many plant and algal systems and this study extends this mechanism to embryogenesis.

Adsorption Characteristics of Reactive Dyes in Columns of Activated Carbon

Abstract: Adsorption behaviour of reactive dyes in fixed-bed adsorber was evaluated in this work. The characteristics of mass transfer zone (MTZ), where adsorption in column occurs, were affected by carbon bed depth and influent dye concentration. The working lifetime (t(x)) of MTZ, the height of mass transfer zone (HMTZ), the rate of mass transfer zone (RMTZ), and the column capacity at exhaustion (q(column)) were estimated for the removal of remazol reactive yellow and remazol reactive black by carbon adsorber. The results showed that column capacity calculated at 90% of column exhaustion was lower than carbon capacity obtained from equilibrium studies. This indicated that the capacity of activated carbon was not fully utilized in the fixed-bed adsorber. The bed-depth service time model (BDST) was applied for analysis of reactive yellow adsorption in the column. The adsorption capacity of reactive yellow calculated at 50% breakthrough point (No) was found to be 0.1 kg kg(-1) and this value is equivalent to about 14% of the available carbon capacity. The results of this study indicated the applicability of fixed-bed adsorber for removing remazol reactive yellow from solution. (C) 2008 Elsevier B.V. All rights reserved.

Phillips-Heffron Power System Model for SmartPark and Suppression of Interarea Oscillations

This paper investigates the use of plug-in parking lots (SmartPark) as integral energy storage to improve small-signal stability using plug-in electric vehicles (PEV). The paper establishes the Phillips-Heffron model of a power system for a SmartPark solution. Based on this model, SmartPark-based stabilisers have been designed based using phase compensation to improve power system oscillation stability. The effectiveness of stabilisation superimposed on the active and reactive power regulators is verified by simulations obtained from a multi-machine power system model with SmartPark and a large-scale wind farm inclusion.

Chemical kinetics and reactive species in atmospheric pressure helium-oxygen plasmas with humid-air impurities

In most applications helium-based plasma jets operate in an open-air environment. The presence of humid air in the plasma jet will influence the plasma chemistry and can lead to the production of a broader range of reactive species. We explore the influence of humid air on the reactive species in radio frequency (rf)-driven atmospheric-pressure helium-oxygen mixture plasmas (He-O, helium with 5000 ppm admixture of oxygen) for wide air impurity levels of 0-500 ppm with relative humidities of from 0% to 100% using a zero-dimensional, time-dependent global model. Comparisons are made with experimental measurements in an rf-driven micro-scale atmospheric pressure plasma jet and with one-dimensional semi-kinetic simulations of the same plasma jet. These suggest that the plausible air impurity level is not more than hundreds of ppm in such systems. The evolution of species concentration is described for reactive oxygen species, metastable species, radical species and positively and negatively charged ions (and their clusters). Effects of the air impurity containing water humidity on electronegativity and overall plasma reactivity are clarified with particular emphasis on reactive oxygen species. © 2013 IOP Publishing Ltd.

Better understanding of mechanochemical reactions: Raman monitoring reveals surprisingly simple 'pseudo-fluid' model for a ball milling reaction

Quantitative monitoring of a mechanochemical reaction by Raman spectroscopy leads to a surprisingly straightforward second-order kinetic model in which the rate is determined simply by the frequency of reactive collisions between reactant particles.