A kinetic model for an argon plasma containing dust grains

A complex low-pressure argon discharge plasma containing dust grains is studied using a Boltzmann equation for the electrons and fluid equations for the ions. Local effects, such as the spatial distribution of the dust density and external electric field, are included, and their effect on the electron energy distribution, the electron and ion number densities, the electron temperature, and the dust charge are investigated. It is found that dust particles can strongly affect the plasma parameters by modifying the electron energy distribution, the electron temperature, the creation and loss of plasma particles, as well as the spatial distributions of the electrons and ions. In particular, for sufficiently high grain density and/or size, in a low-pressure argon glow discharge, the Druyvesteyn-like electron distribution in pristine plasmas can become nearly Maxwellian. Electron collection by the dust grains is the main cause for the change in the electron distribution function.

A comprehensive mechanistic kinetic model for dilute acid hydrolysis of switchgrass cellulose to glucose, 5-HMF and levulinic acid

Switchgrass was treated by 1% (w/w) H₂SO₄in batch tube reactors at temperatures ranging from 140–220°C for up to 60 minutes. In this study, release patterns of glucose, 5-hydroxymethylfurfural (5-HMF), and levulinic acid from switchgrass cellulose were investigated through a mechanistic kinetic model. The predictions were consistent with the measured products of interest when new parameters reflecting the effects of reaction limitations, such as cellulose crystallinity, acid soluble lignin–glucose complex (ASL–glucose) and humins that cannot be quantitatively analyzed, were included. The new mechanistic kinetic model incorporating these parameters simulated the experimental data with R² above 0.97. Results showed that glucose yield was most sensitive to variations in the parameter regarding the cellulose crystallinity at low temperatures (140–180°C), while the impact of crystallinity on the glucose yield became imperceptible at elevated temperatures (200–220 °C). Parameters related to the undesired products (e.g. ASL–glucose and humins) were the most sensitive factors compared with rate constants and other additional parameters in impacting the levulinic acid yield at elevated temperatures (200–220°C), while their impacts were negligible at 140–180°C. These new findings provide a more rational explanation for the kinetic changes in dilute acid pretreatment performance and suggest that the influences of cellulose crystallinity and undesired products including ASL–glucose and humins play key roles in determining the generation of glucose, 5-HMF and levulinic acid from biomass-derived cellulose.

Fate and transport of bensulfuron-methyl and imazosulfuron in paddy fields: Experiments and model simulation

Experiments were conducted to determine the fate of bensulfuron-methyl (BSM) and imazosulfuron (IMS) under paddy conditions. Initially, laboratory experiments were conducted and the photolysis half-lives of the two herbicides were found to be much shorter than their hydrolysis half-lives in aqueous solutions. In the aerobic water–soil system, dissipation followed first-order kinetics with water half-lives of 9.1 and 11.0 days and soil half-lives of 12.4 and 18.5 days (first phase) and 35.0 and 44.1 days (second phase) for bensulfuron-methyl and imazosulfuron, respectively. However, the anaerobic soil half-lives were only 12.7 and 9.8 days for BSM and IMS, respectively. The values of K d were determined to be 16.0 and 13.8 for BSM and IMS, respectively. Subsequent field measurements for the two herbicides revealed that dissipation of both herbicides in paddy water involved biphasic first-order kinetics, with the dissipation rates in the first phase being much faster than those in the second phase. The dissipation of bensulfuron-methyl and imazosulfuron in the paddy surface soil were also followed biphasic first-order kinetics. These results were then used as input parameters for the PCPF-1 model to simulate the fate and transport of BSM and IMS in the paddy environment (water and 1-cm surface soil layer). The measured and simulated values agreed well and the mass balance error during the simulation period was −1.2 and 2.8% of applied pesticide, respectively, for BSM and IMS.

Acepromazine pharmacokinetics: A forensic perspective

Acepromazine (ACP) is a useful therapeutic drug, but is a prohibited substance in competition horses. The illicit use of ACP is difficult to detect due to its rapid metabolism, so this study investigated the ACP metabolite 2-(1-hydroxyethyl)promazine sulphoxide (HEPS) as a potential forensic marker. Acepromazine maleate, equivalent to 30 mg of ACP, was given IV to 12 racing-bred geldings. Blood and urine were collected for 7 days post-administration and analysed for ACP and HEPS by liquid chromatography–mass spectrometry (LC–MS). Acepromazine was quantifiable in plasma for up to 3 h with little reaching the urine unmodified. Similar to previous studies, there was wide variation in the distribution and metabolism of ACP. The metabolite HEPS was quantifiable for up to 24 h in plasma and 144 h in urine. The metabolism of ACP to HEPS was fast and erratic, so the early phase of the HEPS emergence could not be modelled directly, but was assumed to be similar to the rate of disappearance of ACP. However, the relationship between peak plasma HEPS and the y-intercept of the kinetic model was strong (P = 0.001, r2 = 0.72), allowing accurate determination of the formation pharmacokinetics of HEPS. Due to its rapid metabolism, testing of forensic samples for the parent drug is redundant with IV administration. The relatively long half-life of HEPS and its stable behaviour beyond the initial phase make it a valuable indicator of ACP use, and by determining the urine-to-plasma concentration ratios for HEPS, the approximate dose of ACP administration may be estimated.

Removal of bisphenol A from wastewater by Ca-montmorillonite modified with selected surfactants

Organo Arizona SAz-2 Ca-montmorillonite was prepared with different surfactant (DDTMA and HDTMA) loadings through direct ion exchange. The structural properties of the prepared organoclays were characterized by XRD and BET instruments. Batch experiments were carried out on the adsorption of bisphenol A (BPA) under different experimental conditions of pH and temperature to determine the optimum adsorption conditions. The hydrophobic phase and positively charged surface created by the loaded surfactant molecules are responsible for the adsorption of BPA. The adsorption of BPA onto organoclays is well described by pseudo-second order kinetic model and the Langmuir isotherm. The maximum adsorption capacity of the organoclays for BPA obtained from a Langmuir isotherm was 151.52 mg/g at 297 K. This value is among the highest values for BPA adsorption compared with other adsorbents. In addition, the adsorption process was spontaneous and exothermic based on the adsorption thermodynamics study. The organoclays intercalated with longer chain surfactant molecules possessed a greater adsorption capacity for BPA even under alkaline conditions. This process provides a pathway for the removal of BPA from contaminated waters.

Kinetics of low-pressure, low-temperature graphene growth : toward single-layer, single-crystalline structure

Graphene grown on metal catalysts with low carbon solubility is a highly competitive alternative to exfoliated and other forms of graphene, yet a single-layer, single-crystal structure remains a challenge because of the large number of randomly oriented nuclei that form grain boundaries when stitched together. A kinetic model of graphene nucleation and growth is developed to elucidate the effective controls of the graphene island density and surface coverage from the onset of nucleation to the full monolayer formation in low-pressure, low-temperature CVD. The model unprecedentedly involves the complete cycle of the elementary gas-phase and surface processes and shows a precise quantitative agreement with the recent low-energy electron diffraction measurements and also explains numerous parameter trends from a host of experimental reports. These agreements are demonstrated for a broad pressure range as well as different combinations of precursor gases and supporting catalysts. The critical role of hydrogen in controlling the graphene nucleation and monolayer formation is revealed and quantified. The model is generic and can be extended to even broader ranges of catalysts and precursor gases/pressures to enable the as yet elusive effective control of the crystalline structure and number of layers of graphene using the minimum amounts of matter and energy.

Behavior of the electron temperature in nonuniform complex plasmas

The response of complex ionized gas systems to the presence of nonuniform distribution of charged grains is investigated using a kinetic model. Contrary to an existing view that the electron temperature inevitably increases in the grain-occupied region because of enhanced ionization to compensate for the electrons lost to the grains, it is shown that this happens only when the ionizing electric field increases in the electron depleted region. The results for two typical plasma systems suggest that when the ionizing electric field depends on the spatially averaged electron density, the electron temperature in the grain containing region can actually decrease.

Bisphenol A sorption by organo-montmorillonite: Implications for the removal of organic contaminants from water

Remediation of bisphenol A (BPA) from aqueous solutions by adsorption using organoclays synthesized from montmorillonite (MMT) with different types of organic surfactant molecules was demonstrated. High adsorption capacities of the organoclays for the uptake of BPA were observed and these demonstrated their potential application as strong adsorbents for noxious organic water contaminants. The adsorption of BPA was significantly influenced by pH, with increased adsorption of BPA in acidic pH range. However, the organoclays intercalated with highly loaded surfactants and/or large surfactant molecules were less influenced by the pH of the environment and this was thought to be due to the shielding the negative charge from surfactant molecules and the development of more positive charge on the clay surface, which leads to the attraction of anionic BPA even at alkaline pH. The hydrophobic phase created by loaded surfactant molecules contributed to a partitioning phase, interacting with BPA molecules strongly through hydrophobic interaction. Pseudo-second order kinetic model and Langmuir isotherm provided the best fit for the adsorption of BPA onto the organoclays. In addition, the adsorption process was spontaneous and exothermic with lower temperature facilitating the adsorption of BPA onto the organoclays. The described process provides a potential pathway for the removal of BPA from contaminated waters.

Changes in lycopene and beta carotene contents in aril and oil of gac fruit during storage

Gac fruits were physically measured and stored under ambient conditions for up to 2 weeks to observe changes in carotenoid contents (lycopene and beta carotene) in its aril. Initial concentrations in the aril of lycopene were from 2.378 mg/g fresh weight (FW) to 3.728 mg/g FW and those of beta carotene were from 0.257 to 0.379 mg/g FW. Carotenoid concentrations in the aril remained stable after 1 week but sharply declined after 2 weeks of storage. Gac oil, pressed from gac aril, has similar concentrations of lycopene and beta carotene (2.436 and 2.592 mg/g, respectively). Oil was treated with 0.02% of butylated hydroxytoluene, or with a stream of nitrogen or untreated then stored in the dark for up to 15 or 19 weeks under different temperatures (5 °C, ambient, 45 and 60 °C). Lycopene and beta carotene in control gac oil degraded following the first-order kinetic model. The degradation rate of lycopene and beta carotene in the treated oil samples were lower than that in the control oil but the first-order kinetic was not always followed. However, both lycopene and beta carotene degraded quickly in gac oil with the first-order kinetic under high temperature conditions (45 and 60 °C) regardless of the treatments used. © 2009 Elsevier Ltd. All rights reserved.

Time evolution of graphene growth on SiC as a function of annealing temperature

We followed by X-ray Photoelectron Spectroscopy (XPS) the time evolution of graphene layers obtained by annealing 3C SiC(111)/Si(111) crystals at different temperatures. The intensity of the carbon signal provides a quantification of the graphene thickness as a function of the annealing time, which follows a power law with exponent 0.5. We show that a kinetic model, based on a bottom-up growth mechanism, provides a full explanation to the evolution of the graphene thickness as a function of time, allowing to calculate the effective activation energy of the process and the energy barriers, in excellent agreement with previous theoretical results. Our study provides a complete and exhaustive picture of Si diffusion into the SiC matrix, establishing the conditions for a perfect control of the graphene growth by Si sublimation.

Mathematical modelling of human corneal oxygenation and cell kinetics in corneal epithelial wound healing

Healthy transparent cornea depends upon the regulation of fluid, nutrient and oxygen transport through the tissue to sustain cell metabolism and other critical processes for normal functioning. This research considers the corneal geometry and investigates oxygen distribution using a two-dimensional Monod kinetic model, showing that previous studies make assumptions that lead to predictions of near-anoxic levels of oxygen tension in the limbal regions of the cornea. It also considers the comparison of experimental spatial and temporal data with the predictions of novel mathematical models with respect to distributed mitotic rates during corneal epithelial wound healing.

An Artificial Neutral Network (ANN) model for predicting biodiesel kinetic viscosity as a function of temperature and chemical compositions

An Artificial Neural Network (ANN) is a computational modeling tool which has found extensive acceptance in many disciplines for modeling complex real world problems. An ANN can model problems through learning by example, rather than by fully understanding the detailed characteristics and physics of the system. In the present study, the accuracy and predictive power of an ANN was evaluated in predicting kinetic viscosity of biodiesels over a wide range of temperatures typically encountered in diesel engine operation. In this model, temperature and chemical composition of biodiesel were used as input variables. In order to obtain the necessary data for model development, the chemical composition and temperature dependent fuel properties of ten different types of biodiesels were measured experimentally using laboratory standard testing equipments following internationally recognized testing procedures. The Neural Networks Toolbox of MatLab R2012a software was used to train, validate and simulate the ANN model on a personal computer. The network architecture was optimised following a trial and error method to obtain the best prediction of the kinematic viscosity. The predictive performance of the model was determined by calculating the absolute fraction of variance (R2), root mean squared (RMS) and maximum average error percentage (MAEP) between predicted and experimental results. This study found that ANN is highly accurate in predicting the viscosity of biodiesel and demonstrates the ability of the ANN model to find a meaningful relationship between biodiesel chemical composition and fuel properties at different temperature levels. Therefore the model developed in this study can be a useful tool in accurately predict biodiesel fuel properties instead of undertaking costly and time consuming experimental tests.

A differential kinetic spectrophotometric method for determination of three sulphanilamide artificial sweeteners with the aid of chemometrics

A simple and sensitive spectrophotometric method for the simultaneous determination of acesulfame-K, sodium cyclamate and saccharin sodium sweeteners in foodstuff samples has been researched and developed. This analytical method relies on the different kinetic rates of the analytes in their oxidative reaction with KMnO4 to produce the green manganate product in an alkaline solution. As the kinetic rates of acesulfame-K, sodium cyclamate and saccharin sodium were similar and their kinetic data seriously overlapped, chemometrics methods, such as partial least squares (PLS), principal component regression (PCR) and classical least squares (CLS), were applied to resolve the kinetic data. The results showed that the PLS prediction model performed somewhat better. The proposed method was then applied for the determination of the three sweeteners in foodstuff samples, and the results compared well with those obtained by the reference HPLC method.

Asymptotic and numerical results for a model of solvent-dependent drug diffusion through polymeric spheres

A model for drug diffusion from a spherical polymeric drug delivery device is considered. The model contains two key features. The first is that solvent diffuses into the polymer, which then transitions from a glassy to a rubbery state. The interface between the two states of polymer is modelled as a moving boundary, whose speed is governed by a kinetic law; the same moving boundary problem arises in the one-phase limit of a Stefan problem with kinetic undercooling. The second feature is that drug diffuses only through the rubbery region, with a nonlinear diffusion coefficient that depends on the concentration of solvent. We analyse the model using both formal asymptotics and numerical computation, the latter by applying a front-fixing scheme with a finite volume method. Previous results are extended and comparisons are made with linear models that work well under certain parameter regimes. Finally, a model for a multi-layered drug delivery device is suggested, which allows for more flexible control of drug release.

Measurement of anisotropies of the kinetic energy and anharmonicity in pyrolytic graphite by neutron Compton scattering

Neutron Compton scattering (NCS) measurements of the anisotropy of the momentum distribution and the mean Laplacian of the interatomic potential ∇2V have been performed using electron volt neutrons, with wave vector transfers between 24 Å−1 and 98 Å−1. The measured momentum distribution of the atoms displays significantly more anisotropy than a calculation using a model density of states. We have observed anisotropies in ∇2V for the first time. The results suggest that the atomic potential is harmonic within the graphite planes, but anharmonic for vibrations perpendicular to the planes.