Photocatalytic degradation of nitrobenzenes with combustion synthesized nano-TiO2

The photocatalytic degradation of nitrobenzene and substituted nitrobenzenes under UV exposure was investigated with combustion synthesized nano-TiO2 and commercial TiO2 catalyst, Degussa P-25. The experimental data indicated that the photodegradation kinetics was first order. The photocatalytic degradation rates were considerably higher when catalyzed with combustion synthesized TiO2 compared to that of Degussa P-25. The degradation rate coefficients followed the order: 1-chloro,14-dinitrobenzene similar or equal to 4-nitrophenot > 2-nitrophenol > 1-chloro.4-nitrobenzene > 3-niti-ophenol > 2,4-dinitrophenol > 1-chloro,2-nitrobenzene > nitrobenzene > 1,3-dinitrobenzene. Plausible mechanisms and reasons for the observation of the above order are discussed.

Kinetics of TiO2-catalyzed ultrasonic degradation of rhodamine dyes

The ultrasonic degradation of two dyes, Rhodamine B (C28H31ClN2O3) and Rhodamine Blue (C28H32N2O3), were studied in the absence of catalyst and in the presence of two catalysts (combustion-synthesized anatase TiO2 and commercial Degussa P-25 TiO2. The rate of degradation of catalyzed reaction was higher than that obtained with in the absence of the catalysts. Among the catalysts, combustion-synthesized anatase TiO2 degraded the dyes faster when compared to the degradation with commercial Degussa P-25 catalyst. A Langmuir-Hinshelwood kinetic model was developed and the kinetic rate parameters were determined. The effect of other operating parameters, such as initial concentration, pH, temperature, and power intensity, was also investigated. The degradation rate increased with decreasing pH, increasing temperature, and higher intensity.

Kinetics of TiO2-catalyzed ultrasonic degradation of rhodamine dyes

The ultrasonic degradation of two dyes, Rhodamine B (C28H31ClN2O3) and Rhodamine Blue (C28H32N2O3), were studied in the absence of catalyst and in the presence of two catalysts (combustion-synthesized anatase TiO2 and commercial Degussa P-25 TiO2. The rate of degradation of catalyzed reaction was higher than that obtained with in the absence of the catalysts. Among the catalysts, combustion-synthesized anatase TiO2 degraded the dyes faster when compared to the degradation with commercial Degussa P-25 catalyst. A Langmuir-Hinshelwood kinetic model was developed and the kinetic rate parameters were determined. The effect of other operating parameters, such as initial concentration, pH, temperature, and power intensity, was also investigated. The degradation rate increased with decreasing pH, increasing temperature, and higher intensity.

Frame Soil Interaction And Winkler Model

The Winkler spring model is the most convenient representation of soil support in the domain of linear elasticity for framed structure-soil interaction analyses. The closeness of the analytical results obtained using this model with those corresponding to the elastic half-space continuum has been investigated in the past for foundation beams. The findings, however, are not applicable to framed structures founded on beam or strip footings. Moreover, the past investigations employ the concept of characteristic length which does not adequately account for the stiffness contribution of the superstructure. A framed structure on beam foundation can be described parametrically by the ratios of stiffnesses of superstructure and foundation beams to that of soil. For a practical range of soil allowable pressures, the ranges of these relative stiffness ratios have been established. The present study examines the variation between interactive analyses based on Winkler springs with those using the half-space continuum over these ranges of relative stiffness ratios. The findings enable the analyst to undertake a Winkler spring-based-interaction analysis with knowledge of the likely variation of values with those derived for the more computation-intensive half-space continuum.

Mechanistic evaluation of mitigation of petroleum hydrocarbon contamination by soil medium

Present in situ chemical treatment technologies for mitigation of petroleum hydrocarbon contamination are in the developmental stage or being tested. To devise efficient strategies for restricting the movement of petroleum hydrocarbon (PHC) molecules in the contaminated soil, it is proposed to utilize the sorption–interaction relationships between the petroleum contaminants and the soil substrate. The basic questions addressed in this paper are as follows (i) What are the prominent chemical constituents of the various petroleum fractions that interact with the soil substrate? (ii) What are the functional groups of a soil that interact with the contaminants? (iii) What are the bonding mechanisms possible between the soil functional groups and the PHC contaminants? (iv) What are the consequent changes brought about the soil physical properties on interaction with PHC's? (v) What are the factors influencing the interactions between PHC molecules and clay particles of the soil substrate? (vi) What is the possibility of improving the soil's attenuation ability for PHC's? The development of answers to the basic questions reveal that petroleum hydrocarbons comprise a mixture of nonpolar alkanes and aromatic and polycyclic hydrocarbons, that have limited solubility in water. The bonding mechanism between the nonpolar PHC's and the clay surface is by way of van der Waals attraction. The adsorption of the nonpolar hydrocarbons by the clay surface occurs only when their (i.e., the hydrocarbon molecules) solubility in water is exceeded and the hydrocarbons exist in the micellar form. Dilute solutions of hydrocarbons in water, i.e., concentrations of hydrocarbons at or below the solubility limit, have no effect on the hydraulic conductivity of clay soils. Permeation with pure hydrocarbons invariably influences the clay hydraulic conductivity. To improve the attenuation ability of soils towards PHC's, it is proposed to coat the soil surface with "ultra" heavy organic polymers. Adsorption of organic polymers by the clay surface may change the surface properties of the soil from highly hydrophilic (having affinity for water molecules) to organophilic (having affinity for organic molecules). The organic polymers attached to the clay surface are expected to attenuate the PHC molecules by van der Waals attraction, by hydrogen bonding, and also by adsorption into interlayer space in the case of soils containing swelling clays.

Technique for Using Fine-Grained Soil in Reinforced Earth

The performance of reinforced earth structures depends on the mobilization of interfacial shearing resistance between soil and reinforcement. This criterion typically eliminates the use of fine-grained soil as a backfill material in reinforced earth structures. Considering the distribution of induced interfacial shear stress in soil around the surface of the reinforcement, it has been shown that only a thin zone of frictional material around the reinforcement is required to mobilize almost full interfacial shearing resistance of sand. Six series of pullout tests have been conducted, with different types of reinforcement, to study the effect of thickness of sand (frictional material) around the reinforcement on the pullout resistance. Sawdust and kaolin clay have been used as bulk backfill material, providing the soil with negligible friction. With low-friction-strength soil as bulk material, a 15-mm thickness of sand around the reinforcement is required to increase the interfacial shearing resistance to that with sand as the bulk material. With this new technique, low-frictional fine-grained soils can be used as bulk backfill material in reinforced earth constructions.

Estimation of soil hydraulic properties and their uncertainty: comparison between laboratory and field experiment

Often the soil hydraulic parameters are obtained by the inversion of measured data (e.g. soil moisture, pressure head, and cumulative infiltration, etc.). However, the inverse problem in unsaturated zone is ill-posed due to various reasons, and hence the parameters become non-unique. The presence of multiple soil layers brings the additional complexities in the inverse modelling. The generalized likelihood uncertainty estimate (GLUE) is a useful approach to estimate the parameters and their uncertainty when dealing with soil moisture dynamics which is a highly non-linear problem. Because the estimated parameters depend on the modelling scale, inverse modelling carried out on laboratory data and field data may provide independent estimates. The objective of this paper is to compare the parameters and their uncertainty estimated through experiments in the laboratory and in the field and to assess which of the soil hydraulic parameters are independent of the experiment. The first two layers in the field site are characterized by Loamy sand and Loamy. The mean soil moisture and pressure head at three depths are measured with an interval of half hour for a period of 1 week using the evaporation method for the laboratory experiment, whereas soil moisture at three different depths (60, 110, and 200 cm) is measured with an interval of 1 h for 2 years for the field experiment. A one-dimensional soil moisture model on the basis of the finite difference method was used. The calibration and validation are approximately for 1 year each. The model performance was found to be good with root mean square error (RMSE) varying from 2 to 4 cm(3) cm(-3). It is found from the two experiments that mean and uncertainty in the saturated soil moisture (theta(s)) and shape parameter (n) of van Genuchten equations are similar for both the soil types. Copyright (C) 2010 John Wiley & Sons, Ltd.

A kinetic investigation of thermal degradation of poly(vinyl formals)

Several samples of poly(vinyl formal) having the same vinyl alcohol content (8–9%) but varying contents of vinyl acetate (6–22%) and vinyl formol (70–85%) were prepared and subjected to thermogravimetric analysis, in air and nitrogen atmospheres, employing both isothermal and dynamic methods. Kinetic parameters determined from both the isothermal and dynamic TGA data are compared. The activation energy is seen to be largely dependent on the degree of conversion, implying a complex degradation reaction. The activation energy is also much less for degradation in air than in nitrogen, which can be explained by a reaction with oxygen-producing structures favoring degradation. The activation energy is less sensitive to variation in polymer composition for degradation in air than in nitrogen. Thus, in the dynamic process, the activation energy value decreases (from 36 to 23 kcal/mole) with increasing acetate content (from 6 to 22%) in nitrogen atmosphere, while in air the activation energy value increases only moderately (from 21 to 27 kcal/mole) with increasing acetate content (from 6 to 22%). The order of reaction is nearly unity, irrespective of the composition of the polymer, both in air and nitrogen.

Influence of Osmotic Suction on the Soil-Water Characteristic Curves of Compacted Expansive Clay

Unsaturated clays are subject to osmotic suction gradients in geoenvironmental engineering applications and it therefore becomes important to understand the effect of these chemical concentration gradients on soil-water characteristic curves (SWCCs). This paper brings out the influence of induced osmotic suction gradient on the wetting SWCCs of compacted clay specimens inundated with sodium chloride solutions/distilled water at vertical stress of 6.25 kPa in oedometer cells. The experimental results illustrate that variations in initial osmotic suction difference induce different magnitudes of osmotic induced consolidation and osmotic consolidation strains thereby impacting the wetting SWCCs and equilibrium water contents of identically compacted clay specimens. Osmotic suction induced by chemical concentration gradients between reservoir salt solution and soil-water can be treated as an equivalent net stress component, (p(pi)) that decreases the swelling strains of unsaturated specimens from reduction in microstructural and macrostructural swelling components. The direction of osmotic flow affects the matric SWCCs. Unsaturated specimens experiencing osmotic induced consolidation and osmotic consolidation develop lower equilibrium water content than specimens experiencing osmotic swelling during the wetting path. The findings of the study illustrate the need to incorporate the influence of osmotic suction in determination of the matric SWCCs.

A kinetic investigation of thermal degradation of poly(vinyl formals)

Several samples of poly(vinyl formal) having the same vinyl alcohol content (8–9%) but varying contents of vinyl acetate (6–22%) and vinyl formol (70–85%) were prepared and subjected to thermogravimetric analysis, in air and nitrogen atmospheres, employing both isothermal and dynamic methods. Kinetic parameters determined from both the isothermal and dynamic TGA data are compared. The activation energy is seen to be largely dependent on the degree of conversion, implying a complex degradation reaction. The activation energy is also much less for degradation in air than in nitrogen, which can be explained by a reaction with oxygen-producing structures favoring degradation. The activation energy is less sensitive to variation in polymer composition for degradation in air than in nitrogen. Thus, in the dynamic process, the activation energy value decreases (from 36 to 23 kcal/mole) with increasing acetate content (from 6 to 22%) in nitrogen atmosphere, while in air the activation energy value increases only moderately (from 21 to 27 kcal/mole) with increasing acetate content (from 6 to 22%). The order of reaction is nearly unity, irrespective of the composition of the polymer, both in air and nitrogen.

Kinetics of sono-photooxidative degradation of poly(alkyl methacrylate)s

The mechano-chemical degradation of poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA) and poly(n-butyl methacrylate) (PBMA) using ultrasound (US), ultraviolet (UV) radiation and a photoinitiator (benzoin) has been investigated. The degradation of the polymers was monitored using the reduction in number average molecular weight (M-n) and polydispersity (PDI). A degradation mechanism that included the decomposition of the initiator, generation of polymer radicals by the hydrogen abstraction of initiator radicals, reversible chain transfer between stable polymer and polymer radicals was proposed. The mechanism assumed mid-point chain scission due to US and random scission due to UV radiation. A series of experiments with different initial M-n of the polymers were performed and the results indicated that, irrespective of the initial PDI, the PDI during the sono-photooxidative degradation evolved to a steady state value of 1.6 +/- 0.05 for all the polymers. This steady state evolution of PDI was successfully predicted by the continuous distribution kinetics model. The rate coefficients of polymer scission due to US and UV exhibited a linear increase and decrease with the size of the alkyl group of the poly(alkyl methacrylate)s, respectively. (C) 2010 Elsevier B.V. All rights reserved.