SciCombinator

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Concept: Raoult's law

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The insecticide methomyl, an oxime carbamate, was first introduced in 1968 for broad spectrum control of several insect classes, including Lepidoptera, Hemiptera, Homoptera, Diptera, and Coleoptera. Like other carbamates, it inhibits AChE activity, resulting in nerve and/or tissue failure and possibly death. Considered highly toxic to insects (larval and adult stages), methomyl is thought to be metabolically degraded via mixed-function oxidase(s). Methomyl has both a low vapor pressure and Henry’s law constant; hence, volatilization is not a major dissipation route from either water or moist or dry soils. Photolysis represents a minor dissipation pathway; however, under catalytic conditions, degradation via photolysis does occur. Methomyl possesses a moderate-to-high water solubility; thus hydrolysis, under alkaline conditions, represents a major degradation pathway. Methomyl has a low-to-moderate sorption capacity to soil. Although results may vary with soil type and organic matter content, methomyl is unlikely to persist in complex soils. Methomyl is more rapidly degraded by microbes, and bacterial species have been identified that are capable of using methomyl as a carbon and/or nitrogen source. The main degradation products of methomyl from both abiotic and biotic processes are methomyl oxime, acetonitrile, and CO₂. Methomyl is moderately to highly toxic to fishes and very highly toxic to aquatic invertebrates. Methomyl is highly toxic orally to birds and mammals. Methomyl is classed as being highly toxic to humans via oral exposures, moderately toxic via inhalation, and slightly toxic via dermal exposure. At relatively high doses, it can be fatal to humans. Although methomyl has been widely used to treat field crops and has high water solubility, it has only infrequently been detected as a contaminant of water bodies in the USA. It is classified as a restricted-use insecticide because of its toxicity to multiple nontarget species. To prevent nontarget species toxicity or the possibility of contamination, as with all pesticides, great care should be taken when applying methomyl-containing products for agricultural, residential, or other uses.

Concepts: Bacteria, Insect, Nitrogen, Vapor pressure, Insecticide, Partial pressure, Henry's law, Raoult's law

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A systematic thermodynamic analysis has been carried out for selecting cations and anions to enhance the absorption of volatile organic compounds (VOCs) at low concentration in gaseous streams by ionic liquids (ILs), using COSMO-RS methodology. The predictability of computational procedure was validated by comparing experimental and COSMO-RS calculated Henry’s law constant data over a sample of 125 gaseous solute-IL systems. For more than 2,400 solute-IL mixtures evaluated, including 9 solutes and 270 ILs, it was found that the lower the activity coefficient at infinite dilution () of solutes in the ILs, the more the exothermic excess enthalpy (HE) of the equimolar IL-solute mixtures. Then, the solubility of a representative sample of VOC solutes, with very different chemical nature, was screened in a wide number of ILs using COSMO-RS methodology by means of  and HE parameters, establishing criteria to select the IL structure that promotes favorable solute-solvent intermolecular interactions. As a result of this analysis, an attempt of classification of VOCs respect to their potential solubility in ILs was proposed, providing insights to rationally select the cationic and anionic species for a possible development of absorption treatments of VOC pollutants based on IL systems.

Concepts: Chemistry, Temperature, Solubility, Thermodynamics, Chemical compound, Volatile organic compound, Henry's law, Raoult's law

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Phthalates and phthalate alternatives are semi-volatile organic compounds (SVOCs) present in many PVC products as plasticizers to enhance product performance. Knowledge of the mass-transfer parameters, including the equilibrium concentration in the air in contact with the product surface (y0), will greatly improve the ability to estimate the emission rate of SVOCs from these products and to assess human exposure. The objective of this study was to measure y0 for different PVC products and to evaluate its relationship with the material-phase concentrations (C0). Also, C0 and y0 data from other sources were included, resulting in a substantially larger data set (Ntotal = 34, T = 25 °C) than found in previous studies. The results show that the material/gas equilibrium relationship does not follow Raoult’s Law and that therefore the assumption of an ideal solution is invalid. Instead, Henry’s Law applies and the Henry’s Law Constant for all target SVOCs consists of the respective pure liquid vapor pressure and an activity coefficient γ, which accounts for the non-ideal nature of the solution. For individual SVOCs, a simple partitioning relationship exists, but Henry’s Law is more generally applicable and will be of greater value in rapid exposure assessment procedures.

Concepts: Chemistry, Solubility, Physical chemistry, Chemical engineering, Partial pressure, Equilibrium chemistry, Henry's law, Raoult's law

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1,4-Dioxane is a contaminant of emerging concern that has been found widespread in groundwater, surface water, and drinking water environments. Many states are implementing lower regulatory advisory levels based on the toxicological profile of 1,4-dioxane and the potential public health risks. However, the unique chemical properties of 1,4-dioxane, such as high water solubility, low Henry’s law constant, and importantly, the co-occurrence with chlorinated solvents and other contaminants, increase the challenges to efficiently cleanup 1,4-dioxane. This review summarizes currently available chemical and physical 1,4-dioxane treatment technologies and focuses on recent advances in bioremediation and monitoring tools. We also include laboratory studies and field applications to propose the next steps in 1,4-dioxane bioremediation research. It is important to provide useful references to change the industrial and regulatory perception of 1,4-dioxane biodegradability, to understand treatment mechanisms especially in contaminant mixtures, and to direct research for meeting practical needs.

Concepts: Water, Chemistry, Solubility, Chemical substance, Groundwater, Partial pressure, Henry's law, Raoult's law

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Laboratory produced DDGS samples were compared with commercial samples from a distillery and a biofuel plant. Changes in structure, solubility and content of arabinoxylan (AX) was determined. The distillation process results in a relative increase of AX content compared to the starting material. The heating and drying processes involved in the production of DDGS lead to an increased solubility and viscosity of water-extractable AX. Production of DDGS results in structural changes to the AX. There is a decrease in 2- and 3-linked arabinose oligosaccharides, that contributes to around a 50% reduction in arabinosylation in DDGS compared with the starting grains. The current study shows that laboratory-scale DDGS provide an accurate representation of the commercial scale and that the AX composition of DDGS is consistently uniform irrespective of starting material. The uniformity of DDGS and thin stillage makes them a good potential source of AX for production of prebiotics or other novel products.

Concepts: Ethanol, Wheat, Vodka, Distillation, Raoult's law

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A comprehensive study of the most commonly used jet fuels (i.e., Jet A-1 and JP-8) was performed to properly assess potential contamination of the subsurface environment from a leaking underground storage tank occurred in an airport. The objectives of this study were to evaluate the concentration ranges of the major components in the water-soluble fraction of jet fuels and to estimate the jet fuel-water partition coefficients (K fw) for target compounds using partitioning experiments and a polyparameter linear free-energy relationship (PP-LFER) approach. The average molecular weight of Jet A-1 and JP-8 was estimated to be 161 and 147 g/mole, respectively. The density of Jet A-1 and JP-8 was measured to be 786 and 780 g/L, respectively. The distribution of nonpolar target compounds between the fuel and water phases was described using a two-phase liquid-liquid equilibrium model. Models were derived using Raoult’s law convention for the activity coefficients and the liquid solubility. The observed inverse, log-log linear dependence of the K fw values on the aqueous solubility were well predicted by assuming jet fuel to be an ideal solvent mixture. The experimental partition coefficients were generally well reproduced by PP-LFER.

Concepts: Petroleum, Solubility, Partition coefficient, Fuels, Raoult's law, Underground storage tank, Storage tank, Jet fuel

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Aerated batch reactors (2.5L) fed either with urban or synthetic wastewater were inoculated with microalgae (dominated by Chlorella sp. and Scenedesmus sp.) to remove caffeine, ibuprofen, galaxolide, tributyl phosphate, 4-octylphenol, tris(2-chloroethyl) phosphate and carbamazepine for 10 incubation days. Non-aerated and darkness reactors were used as controls. Microalgae grew at a rate of 0.25d(-1) with the complete removal of N-NH4 during the course of the experiment. After 10 incubation days, up to 99% of the microcontaminants with a Henry’s law constant higher than 3 10(-1)Pam(3)mol(-1) (i.e., 4-octylphenol, galaxolide, and tributyl phosphate) were removed by volatilization due to the effect of air stripping. Whereas biodegradation was effective for removing ibuprofen and caffeine, carbamazepine and tris(2-chloroethyl) phosphate behaved as recalcitrant compounds. The use of microalgae was proved to be relevant for increasing the biodegradation removal efficiency of ibuprofen by 40% and reducing the lag phase of caffeine by 3 days. Moreover, the enantioselective biodegradation of S-ibuprofen suggested a biotic prevalent removal process, which was supported by the identification of carboxy-ibuprofen and hydroxy-ibuprofen. The results from microalgae reactors fed with synthetic wastewater showed no clear evidences of microalgae uptake of any of the studied microcontaminants.

Concepts: Chemistry, Solubility, Chemical engineering, Partial pressure, Evidence, Henry's law, Raoult's law, Gas laws

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A novel curcumin activated carboxymethylcellulose-montmorillonite nanocomposite is reported. A superabsorbent biopolymer; carboxymethyl cellulose (CMC) was used as an emulsifier for curcuminwhich is a turmeric derived water insoluble polyphenolic compound with antibacterial/anti-cancer properties. Montmorillonite (MMT) nanoclay was incorporated in the formulation as a matrix material which also plays a role in release kinetics. It was observed that water solubility of curcumin in the nanocomposite has significantly increased (60% release within 2h and 30min in distilled water at pH 5.4) compared to pure curcumin. The prepared curcumin activated carboxymethylcellulose-montmorillonite nanocomposite is suitable as a curcumin carrier having enhanced release and structural properties.

Concepts: Solubility, Chemical substance, Phase, Solutions, E number, Carboxymethyl cellulose, Distilled water, Raoult's law

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Knudsen effusion mass spectrometry (KEMS) has been used to investigate the vapour pressure over the molten LiF-ThF4 salt and determine the thermodynamic activity of LiF and ThF4 in the liquid solution. As part of the study, the vaporization of pure LiF and pure ThF4 was examined and the results were compared with the literature values finding a good agreement. Next, the vapour pressure of the LixTh1-xF4-3x liquid solution was investigated by measuring four samples having different compositions (XLiF ∼ 0.2, 0.4, 0.6, 0.8 mol%). In order to determine the thermodynamic activities, the vapour pressure of LiF and ThF4 species over the liquid solution, as calculated from our results, were compared with the vapour pressure over the pure LiF(l) and pure ThF4(l) systems. A strong deviation from the Raoult’s law was observed, more evident in case of LiF species, in agreement with the predictions by our thermodynamic model.

Concepts: Liquid, Physical chemistry, Pressure, Gas, Vapor pressure, Evaporation, Gases, Raoult's law

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Accurate values for the Henry’s law constants are essential to describe the environmental dynamics of a solute, but substantial errors are recognized in many reported data due to practical difficulties in measuring solubility and/or vapor pressure. Despite such awareness, validation of experimental approaches has scarcely been made. An experimental approach based on thermal desorption-gas chromatography-mass spectrometery (TD-GC-MS) method was developed to concurrently allow the accurate determination of target compounds from the headspace and aqueous samples in closed equilibrated system. The analysis of six aromatics and eight non-aromatic oxygenates was then carried out in a static headspace mode. An estimation of the potential bias and mass balance (i.e., sum of mass measured individually from gas and liquid phases vs. the mass initially added to the system) demonstrates compound-specific phase dependency so that the best results are obtained by aqueous (less soluble aromatics) and headspace analysis (more soluble non-aromatics). Accordingly, we were able to point to the possible sources of biases in previous studies and provide the best estimates for the Henry’s constants (Matm(-1)): benzene (0.17), toluene (0.15), p-xylene (0.13), m-xylene (0.13), o-xylene (0.19), styrene (0.27); propionaldehyde (9.26), butyraldehyde (6.19), isovaleraldehyde (2.14), n-valeraldehyde (3.98), methyl ethyl ketone (10.5), methyl isobutyl ketone (3.93), n-butyl acetate (2.41), and isobutyl alcohol (22.2).

Concepts: Chemistry, Solubility, Benzene, Aromatic hydrocarbon, Chemical engineering, Partial pressure, Henry's law, Raoult's law