Modelling photochemical production of fine particulates in a toluene/NOx/water vapour system

This work investigates the computer modelling of the photochemical formation of smog products such as ozone and aerosol, in a system containing toluene, NOx and water vapour. In particular, the problem of modelling this process in the Commonwealth Scientific and Industrial Research Organization (CSIRO) smog chambers, which utilize outdoor exposure, is addressed. The primary requirement for such modelling is a knowledge of the photolytic rate coefficients. Photolytic rate coefficients of species other than N02 are often related to JNo2 (rate coefficient for the photolysis ofN02) by a simple factor, but for outdoor chambers, this method is prone to error as the diurnal profiles may not be similar in shape. Three methods for the calculation of diurnal JNo2 are investigated. The most suitable method for incorporation into a general model, is found to be one which determines the photolytic rate coefficients for N02, as well as several other species, from actinic flux, absorption cross section and quantum yields. A computer model was developed, based on this method, to calculate in-chamber photolysis rate coefficients for the CSIRO smog chambers, in which ex-chamber rate coefficients are adjusted by accounting for variation in light intensity by transmittance through the Teflon walls, albedo from the chamber floor and radiation attenuation due to clouds. The photochemical formation of secondary aerosol is investigated in a series of toluene-NOx experiments, which were performed in the CSIRO smog chambers. Three stages of aerosol formation, in plots of total particulate volume versus time, are identified: a delay period in which no significant mass of aerosol is formed, a regime of rapid aerosol formation (regime 1) and a second regime of slowed aerosol formation (regime 2). Two models are presented which were developed from the experimental data. One model is empirically based on observations of discrete stages of aerosol formation and readily allows aerosol growth profiles to be calculated. The second model is based on an adaptation of published toluene photooxidation mechanisms and provides some chemical information about the oxidation products. Both models compare favorably against the experimental data. The gross effects of precursor concentrations (toluene, NOx and H20) and ambient conditions (temperature, photolysis rate) on the formation of secondary aerosol are also investigated, primarily using the mechanism model. An increase in [NOx]o results in increased delay time, rate of aerosol formation in regime 1 and volume of aerosol formed in regime 1. This is due to increased formation of dinitrocresol and furanone products. An increase in toluene results in a decrease in the delay time and an increase in the rate of aerosol formation in regime 1, due to enhanced reactivity from the toluene products, such as the radicals from the photolysis of benzaldehyde. Water vapor has very little effect on the formation of aerosol volume, except that rates are slightly increased due to more OH radicals from reaction with 0(1D) from ozone photolysis. Increased temperature results in increased volume of aerosol formed in regime 1 (increased dinitrocresol formation), while increased photolysis rate results in increased rate of aerosol formation in regime 1. Both the rate and volume of aerosol formed in regime 2 are increased by increased temperature or photolysis rate. Both models indicate that the yield of secondary particulates from hydrocarbons (mass concentration aerosol formed/mass concentration hydrocarbon precursor) is proportional to the ratio [NOx]0/[hydrocarbon]0

CO2 reforming of toluene as model compound of biomass tar on Ni/Palygorskite

Catalytic CO2 reforming of biomass tar on palygorskite-supported nickel catalysts using toluene as a model compound of biomass tar was investigated. The experiments were performed in a bench scale installation a fixed bed reactor. All experiments were carried out at 650, 750, 800 °C and atmospheric pressure. The effect of Ni loading, reaction temperature and concentration of CO2 on H2 yield and carbon deposit was investigated. Ni/Palygorskite (Ni/PG) catalysts with Ni/PG ratios of 0%, 2%, 5% and 8% were tested, the last two show the best performance. H2 yield and carbon deposit diminished with the increase of reaction temperature, Ni loading, and CO2 concentration.

4-(4-Aminophenylsulfonyl)anilinium toluene-4-sulfonate

In the title p-toluenesulfonate salt of the drug dapsone, C12H13N2O2S+ C7H7O3S-, the dihedral angle between the two aromatic rings of the dapsone monocation is 70.19(17)deg. and those between these rings and that of the p-toluenesulfonate anion are 72.34(17) and 46.43(17)deg. All amine and aminium H-atoms are involved in intermolecular N-H...O hydrogen-bonding associations with sulfonyl O-atom acceptors as well as one of the sulfone O-atoms, giving a three-dimensional structure.

Mixture Effects of Benzene, Toluene, Ethylbenzene and Xylenes (BTEX) to Lung Carcinoma Cells via a Hanging Drop Air Exposure System

A recently developed hanging drop air exposure system for toxicity studies of volatile chemicals was applied to evaluate the cell viability of lung carcinoma A549 cells after 1 h and 24 h of exposure to benzene, toluene, ethylbenzene and xylenes (BTEX) as individual compounds and mixtures of 4 or 6 components. The cellular chemical concentrations causing 50% reduction of cell viability (EC50) were calculated use a mass balance model and came to 17, 12, 11, 9, 4 and 4 mmol/kg cell dry weight for benzene, toluene, ethylbenzene, m-xylene, o-xylene and p-xylene respectively after 1 h of exposure. The EC50 decreased by a factor of four after 24 h of exposure. All mixture effects were best described by the mixture toxicity model of concentration addition, which is valid for chemicals with the same mode of action. Good agreement with the model predictions were found for benzene, toluene, ethylbenzene and m-xylene at four different representative fixed concentration ratios after 1 h of exposure but lower agreement to mixture prediction was obtained after 24 h of exposure. A recreated car exhaust mixture, which involved the contribution of the more toxic p-xylene and o-xylene, yielded an acceptable but lower quality prediction as well.

Stable Dispersions of Metal Oxide Nanowires and Nanoparticles in Water, Dimethylformamide and Toluene

In view of the important need to generate well-dispersed inorganic nanostructures in various solvents, we have explored the dispersion of nanostructures of metal oxides such as TiO2, Fe3O4 and ZnO in solvents of differing polarity in the presence of several surfactants. The solvents used are water, dimethylformamide (DMF) and toluene. The surfactant-solvent combinations yielding the best dispersions are reported alongwith some of the characteristics of the nanostructures in the dispersions. The surfactants which dispersed TiO2 nanowires in water were polyethylene oxide (PEO), Triton X-100 (TX-100), polyvinyl alcohol (PVA) and sodium bis(2-ethylhexyl) sulphosuccinate (AOT). TiO2 nanoparticles could also be dispersed with AOT and PEO in water, and with AOT in toluene. In DMF, PVA, PEO and TX-100 were found to be effective, while in toluene, only AOT gave good dispersions. Fe3O4 nanoparticles were held for long periods of time in water by PEO, AOT, PVA and polyethylene glycol (PEG), and by AOT in toluene. In the case of ZnO nanowires, the best surfactant-solvent combinations were found to be, PEO, sodium dodecyl sulphate (SIDS) and AOT in water and AOT, PEG, PVA, PEO and TX-100 in DMF In toluene, stable dispersions of ZnO nanowires were obtained with PEO. We have also been able to disperse oxide nanostructures in non-polar solvents by employing a hydrophobic silane coating on the surface.

Thermodynamic properties of the system toluene-1,2-dichloroethane

Data on heats of mixing at 30 'C, vapor-liquid equilibrium, latent heats of vaporization at 686 mmHg, and vapor pressures for the system toluene-l,2-dichloroethane are presented.

Thermodynamic properties of toluene-1,1,2,2-tetrachloroethane

Data on heats of mixing at 298.15 and 308.15 K, vaporliquid equilibria, latent heats of vaporization at 686 mmHg, and vapor pressures for the system toluene-1,1,2,2- tetrachloroethane are presented. The effect of alkyl substitution on heats of mixing is discussed.

Small-angle x-ray scattering study of the aggregation of gold nanoparticles during formation at the toluene-water interface

We report the results of an in situ small-angle x-ray scattering (SAXS) study of the aggregation of gold nanoparticles formed by an interfacial reaction at the toluene-water interface. The SAXS data provide a direct evidence for aggregate formation of nanoparticles having 1.3 nm gold core and an organic shell that gives a core-core separation of about 2.5 nm. Furthermore, the nanoparticles do not occupy all the cites of 13-member cluster. This occupancy decreases with reaction time and indicate reorganization of the clusters that generates planner disklike structures. A gradual increase in fractal dimension from 1.82 to 2.05 also indicate compactification of cluster aggregation with reaction time, the final exponent being close to 2 expected for disklike aggregates.

Thermodynamic properties of the system toluene — 1, 1, 1-trichloroethane

Data on molar excess enthalpy on mixing at 298.15 K and 308.15 K, vapor-liquid equilibrium, latent heats of vaporization at 91.444 kPa and vapor pressures for the system toluene – 1, 1, 1-trichloroethane are presented. A simple adiabatic calorimeter designed for molar excess enthalpy measurements is described, tested and used. On présente, dans le cas du système toluène – 1, 1, 1-trichloréthane, des résultats relatifs aux grandeurs suivantes: a) enthalpie molaire d'excès à 298.15 K et 308.15 K; b) équilibre liquid-vapeur; c) chaleurs latentes de vaporisation à une pression absolue de 91.444 kP; d) pressions de vapeur. On décrit un calorimètre adiabatique simple, conçu pour mesurer l'enthalpie molaire d'excès, dont on a fait l'essai.

Neutral Nanosheets that Gel: Exfoliated Layered Double Hydroxides in Toluene

A simple strategy to exfoliate inorganic layered double hydroxide (LDH) solids to their ultimate constituent, intact single layers of nanometer thickness and micrometer size, is presented. The procedure involves intercalation of an ionic surfactant that forms a hydrophobic anchored surfactant bilayer in the galleries of the solid followed by simply stirring the intercalated solid in toluene. The method is rapid but at the same time gentle enough to produce exfoliated nanosheets of regular morphology that are electrically neutral and form stable gels at higher concentrations. In this Letter, we describe the phenomena and use molecular dynamics simulations to show that exfoliation of the LDH in toluene is a consequence of the modification of the cohesive dispersive interactions between surfactant chains anchored on opposing inorganic sheets by the toluene molecules. The toluene molecules function as a molecular glue, holding the surfactant-anchored LDH sheets together, leading to gel formation.

Alkylation of toluene by methanol over alkali exchanged zeolite-X: side chain versus ring alkylation

The ring versus side-chain alkylation of toluene with methanol over alkali-exchanged zeolite-X of differing basicity has been investigated by in situ infrared spectroscopy and TPD measurements. Over the basic Cs-exchanged zeolite the product of alkylation is styrene/ethylbenzene while over the acidic Li-exchanged zeolite ring alkylation occurs to give mainly xylene as the product. FTIR and TPD investigations reveal that, the key difference in the two types of alkylation processes lies in the state of the adsorbed methanol present at higher temperatures in the zeolite. In basic zeolites, methanol decomposes to formaldehyde and formates. The former is the key ‘side-chain’ alkylating species that leads to the formation of styrene. In the acidic zeolites it is shown that methanol bound to the acid sites plays an active role in the ‘ring alkylation’ of toluene to xylene.

Photocatalytic degradation of gaseous toluene by using immobilized titania/silica on aluminum sheets

The aim of this study was to prepare a highly active immobilized titania/silica photocatalyst and to test its performance in situ toward degradation of toluene as one of the major toxic indoor contaminants. In this work, two different titania layers immobilized on Al sheets were synthesized via low temperature sol-gel method employing presynthesized highly active titania powders (Degussa P25 and Millennium PC500, mass ratio 1:1): (a) with a silica/titania binder and a protective layer and (b) without the binder. The photocatalysts were characterized by X-ray diffraction, nitrogen sorption measurements, scanning electron microscopy (SEM), infrared spectroscopy, and UV-vis diffuse reflectance spectroscopy (DRS). The in situ photocatalytic degradation of gaseous toluene was selected as a probe reaction to test photocatalytic activity and to verify the potential application of these materials for air remediation. Results show that nontransparent highly photocatalytically active coatings based on the silica/titania binder and homogeneously dispersed TiO2 powders were obtained on the Al sheets. The crystalline structure of titania was not altered upon addition of the binder, which also prevented inhomogeneous agglomeration of particles on the photocatalyst surface. The photoactivity results indicate that the adsorption properties and photocatalytic activity of immobilized photocatalysts with the silica/titania binder and an underlying protective layer were very effective and additionally, they exhibited considerably improved adhesion and uniformity. We present a new highly photocatalytically active immobilized catalyst on a convenient metallic support, which has a potential application in an air cleaning device.

Kinetically stabilized C-60-toluene solvate nanostructures with a discrete absorption edge enabling supramolecular topotactic molecular exchange

Nanosized fullerene solvates have attracted widespread research attention due to recent interesting discoveries. A particular type of solvate is limited to a fixed number of solvents and designing new solvates within the same family is a fundamental challenge. Here we demonstrate that the hexagonal closed packed (HCP) phase of C-60 solvates, formed with m-xylene, can also be stabilized using toluene. Contrary to the notion on their instability, these can be stabilized from minutes up to months by tuning the occupancy of solvent molecules. Due to high stability, we could record their absorption edge, and measure excitonic life-time, which has not been reported for any C-60 solvate. Despite being solid, absorbance spectrum of the solvates is similar in appearance to that of C-60 in solution. A new absorption band appears at 673 nm. The fluorescence lifetime at 760 nm is similar to 1.2 ns, suggesting an excited state unaffected by solvent-C-60 interaction. Finally, we utilized the unstable set of HCP solvates to exchange with a second solvent by a topotactic exchange mechanism, which rendered near permanent stability to the otherwise few minutes stable solvates. This is also the first example of topotactic exchange in supramolecular crystal, which is widely known in ionic solids. (C) 2014 Elsevier Ltd. All rights reserved.