Phosphorus Adsorption onto an Industrial Acidified Laterite By‒Product: Equilibrium and Thermodynamic Investigation

The present research investigates the uptake of phosphate ions from aqueous solutions using acidified laterite (ALS), a by-product from the production of ferric aluminium sulfate using laterite. Phosphate adsorption experiments were performed in batch systems to determine the amount of phosphate adsorbed as a function of solution pH, adsorbent dosage and thermodynamic parameters per fixed P concentration. Kinetic studies were also carried out to study the effect of adsorbent particle sizes. The maximum removal capacity of ALS observed at pH 5 was 3.68 mg P g^-1. It was found that as the adsorbent dosage increases, the equilibrium pH decreases, so an adsorbent dosage of 1.0 g L^-1 of ALS was selected. Adsorption capacity (q_m) calculated from the Langmuir isotherm was found to be 2.73 mg g^-1. Kinetic experimental data were mathematically well described using the pseudo first-order model over the full range of the adsorbent particle size. The adsorption reactions were endothermic, and the process of adsorption was favoured at high temperature; the ΔG and ΔH values implied that the main adsorption mechanism of P onto ALS is physisorption. The desorption studies indicated the need to consider a NaOH 0.1M solution as an optimal solution for practical regeneration applications.

Universal tight binding model for chemical reactions in solution and at surfaces. I. Organic molecules

As is now well established, a first order expansion of the Hohenberg-Kohn total energy density functional about a trial input density, namely, the Harris-Foulkes functional, can be used to rationalize a non self consistent tight binding model. If the expansion is taken to second order then the energy and electron density matrix need to be calculated self consistently and from this functional one can derive a charge self consistent tight binding theory. In this paper we have used this to describe a polarizable ion tight binding model which has the benefit of treating charge transfer in point multipoles. This admits a ready description of ionic polarizability and crystal field splitting. It is necessary in constructing such a model to find a number of parameters that mimic their more exact counterparts in the density functional theory. We describe in detail how this is done using a combination of intuition, exact analytical fitting, and a genetic optimization algorithm. Having obtained model parameters we show that this constitutes a transferable scheme that can be applied rather universally to small and medium sized organic molecules. We have shown that the model gives a good account of static structural and dynamic vibrational properties of a library of molecules, and finally we demonstrate the model's capability by showing a real time simulation of an enolization reaction in aqueous solution. In two subsequent papers, we show that the model is a great deal more general in that it will describe solvents and solid substrates and that therefore we have created a self consistent quantum mechanical scheme that may be applied to simulations in heterogeneous catalysis.

CALCULATION OF SLOW MODE SURFACE-PLASMON POLARITON PROPERTIES RELATED TO EXPERIMENTAL-OBSERVATIONS

Recent experimental results definitively showed, for the first time, optical radiation mediated by the slow mode surface plasmon polariton of metal-oxide-metal tunnel junctions. Here, dispersion curves for this mode are calculated. They are consistent with first-order grating coupling to light at the energies of the experimental emission peaks. The curves are then used to analyze second-order and high-energy (> 2.35 eV) grating coupling of the polaritons to radiation. Finally, variation of slow mode damping as a function of energy is used to explain qualitatively the relative experimental peak emission intensities and the absence of radiation peaks above 2.35 eV.

Technical and allocative efficiency of irrigation water use in the Guanzhong Plain, China

Due to increasing water scarcity, accelerating industrialization and urbanization, efficiency of irrigation water use in Northern China needs urgent improvement. Based on a sample of 347 wheat growers in the Guanzhong Plain, this paper simultaneously estimates a production function, and its corresponding first-order conditions for cost minimization, to analyze efficiency of irrigation water use. The main findings are that average technical, allocative, and overall economic efficiency are 0.35, 0.86 and 0.80, respectively. In a second stage analysis, we find that farmers’ perception of water scarcity, water price and irrigation infrastructure increase irrigation water allocative efficiency, while land fragmentation decreases it. We also show that farmers’ income loss due to higher water prices can be offset by increasing irrigation water use efficiency.

Kinetics of levoglucosan and formaldehyde formation during cellulose pyrolysis process

The mechanisms and kinetics studies of the formation of levoglucosan and formaldehyde from anhydroglucose radical have been carried out theoretically in this paper. The geometries and frequencies of all the stationary points are calculated at the B3LYP/6-31+G(D,P) level based on quantum mechanics, Six elementary reactions are found, and three global reactions are involved. The variational transition-state rate constants for the elementary reactions are calculated within 450-1500 K. The global rate constants for every pathway are evaluated from the sum of the individual elementary reaction rate constants. The first-order Arrhenius expressions for these six elementary reactions and the three pathways are suggested. By comparing with the experimental data, computational methods without tunneling correction give good description for Path1 (the formation of levoglucosan); while methods with tunneling correction (zero-curvature tunneling and small-curvature tunneling correction) give good results for Path2 (the first possibility for the formation of formaldehyde), all the test methods give similar results for Path3 (the second possibility for the formation of formaldehyde), all the modeling results for Path3 are in good agreement with the experimental data, verifying that it is the most possible way for the formation of formaldehyde during cellulose pyrolysis. © 2012 Elsevier Ltd. All rights reserved.

Kinetics study on thermal dissociation of levoglucosan during cellulose pyrolysis

(Chemical Equation Presented) The mechanisms and kinetics studies of the levoglucosan (LG) primary decomposition during cellulose pyrolysis have been carried out theoretically in this paper. Three decomposition mechanisms (C-O bond scission, C-C bond scission, and LG dehydration) including nine pathways and 16 elementary reactions were studied at the B3LYP/6-31 + G(D,P) level based on quantum mechanics. The variational transi-tion- state rate constants for every elementary reaction and every pathway were calculated within 298-1550 K. The first-order Arrhenius expressions for these 16 elementary reactions and nine pathways were suggested. It was concluded that computational method using transition state theory (TST) without tunneling correction gives good description for LG decomposition by comparing with the experimental result. With the temperature range of 667-1327 K, one dehydration pathway, with one water molecule composed of a hydrogen atom from C3 and a hydroxyl group from C2, is a preferred LG decomposition pathway by fitting well with the experimental results. The calculated Arrhenius plot of C-O bond scission mechanism is better agreed with the experimental Arrhenius plot than that of C-C bond scission. This C-O bond scission mechanism starts with breaking of C1-O5 and C6-O1 bonds with formation of CO molecule (C1-O1) simultaneously. C-C bond scission mechanism is the highest energetic barrier pathway for LG decomposition. © 2013 Elsevier Ltd. All rights reserved.

Temperature controlled motion of an antiferromagnet- ferromagnet interface within a dopant-graded FeRh epilayer

Chemically ordered B2 FeRh exhibits a remarkable antiferromagnetic-ferromagnetic phase transition that is first order. It thus shows phase coexistence, usually by proceeding though nucleation at random defect sites followed by propagation of phase boundary domain walls. The transition occurs at a temperature that can be varied by doping other metals onto the Rh site. We have taken advantage of this to yield control over the transition process by preparing an epilayer with oppositely directed doping gradients of Pd and Ir throughout its height, yielding a gradual transition that occurs between 350 K and 500 K. As the sample is heated, a horizontal antiferromagnetic-ferromagnetic phase boundary domain wall moves gradually up through the layer, its position controlled by the temperature. This mobile magnetic domain wall affects the magnetisation and resistivity of the layer in a way that can be controlled, and hence exploited, for novel device applications.

Probabilistic logic with independence

This paper investigates probabilistic logics endowed with independence relations. We review propositional probabilistic languages without and with independence. We then consider graph-theoretic representations for propositional probabilistic logic with independence; complexity is analyzed, algorithms are derived, and examples are discussed. Finally, we examine a restricted first-order probabilistic logic that generalizes relational Bayesian networks.

Propositional and Relational Bayesian Networks Associated with Imprecise and Qualitative Probabilistic Assessments

This paper investigates a representation language with flexibility inspired by probabilistic logic and compactness inspired by relational Bayesian networks. The goal is to handle propositional and first-order constructs together with precise, imprecise, indeterminate and qualitative probabilistic assessments. The paper shows how this can be achieved through the theory of credal networks. New exact and approximate inference algorithms based on multilinear programming and iterated/loopy propagation of interval probabilities are presented; their superior performance, compared to existing ones, is shown empirically.

Evaluating Asymmetric Multicore Systems-on-Chip using Iso-Metrics

The end of Dennard scaling has pushed power consumption into a first order concern for current systems, on par with performance. As a result, near-threshold voltage computing (NTVC) has been proposed as a potential means to tackle the limited cooling capacity of CMOS technology. Hardware operating in NTV consumes significantly less power, at the cost of lower frequency, and thus reduced performance, as well as increased error rates. In this paper, we investigate if a low-power systems-on-chip, consisting of ARM's asymmetric big.LITTLE technology, can be an alternative to conventional high performance multicore processors in terms of power/energy in an unreliable scenario. For our study, we use the Conjugate Gradient solver, an algorithm representative of the computations performed by a large range of scientific and engineering codes.

GRADIENT CORRECTIONS IN DENSITY-FUNCTIONAL THEORY CALCULATIONS FOR SURFACES - CO ON PD(110)

Ab initio total energy calculations have been performed for CO chemisorption on Pd(110). Local density approximation (LDA) calculations yield chemisorption energies which are significantly higher than experimental values but inclusion of the generalised gradient approximation (GGA) gives better agreement. In general, sites with higher coordination of the adsorbate to surface atoms lead to a larger degree of overbinding with LDA, and give larger corrections with GGA. The reason is discussed using a first-order perturbation approximation. It is concluded that this may be a general failure of LDA for chemisorption energy calculations. This conclusion may be extended to many surface calculations, such as potential energy surfaces for diffusion.

Energy and energy flux in axisymmetric slow and fast waves

Aims: We aim to calculate the kinetic, magnetic, thermal, and total energy densities and the flux of energy in axisymmetric sausage modes. The resulting equations should contain as few parameters as possible to facilitate applicability for different observations. 

Methods: The background equilibrium is a one-dimensional cylindrical flux tube model with a piecewise constant radial density profile. This enables us to use linearised magnetohydrodynamic equations to calculate the energy densities and the flux of energy for axisymmetric sausage modes. 

Results: The equations used to calculate the energy densities and the flux of energy in axisymmetric sausage modes depend on the radius of the flux tube, the equilibrium sound and Alfvén speeds, the density of the plasma, the period and phase speed of the wave, and the radial or longitudinal components of the Lagrangian displacement at the flux tube boundary. Approximate relations for limiting cases of propagating slow and fast sausage modes are also obtained. We also obtained the dispersive first-order correction term to the phase speed for both the fundamental slow body mode under coronal conditions and the slow surface mode under photospheric conditions.

Assessment of the Activity of Photocatalytic Paint Using a Simple Smart Ink Designed for High Activity Surfaces

The use of an acid violet 7 (AV7) smart ink to assess the activity of photocatalytic paint is demonstrated. A linear correlation is established between the change in oxidized dye concentration, as measured by diffuse reflectance, and the change in the green component of the RGB color values, obtained using a portable hand-held scanner, suggesting that such tests can be monitored easily using an inexpensive piece of hand-held office equipment, as opposed to an expensive lab-based instrument, such as a diffuse reflectance UV/vis spectrophotometer. The bleaching of the AV7 follows first order kinetics, at a rate that is linearly dependent upon the UVA irradiance (0.30–3.26 mW cm–2). A comparison of relative rate of bleaching of the AV7 ink with the relative rate of removal of NOx, as determined using the ISO test (ISO 22197-1:2007), established a linear relationship between the two sets of results and the relevance of this correlation is discussed briefly.

Received Signal Characteristics of the Indoor Off-Body Communications Channel at 5.8 GHz

In this paper we investigate the received signal characteristics of a mobile chest-worn transmitter at 5.8 GHz within a high multipath indoor environment. The off-body channel measurements considered both the co- and cross-polarized received signal for both line-of-sight (LOS) and non-LOS (NLOS) conditions. A straightforward channel model based upon the estimated path loss, a lognormal slow fading component and Ricean small-scale fading contribution is developed and used to perform simulations which allow the generation of first order received signal power characteristics.

Re-inoculation of autoclaved soil as a non-sterile treatment for xenobiotic sorption and biodegradation studies

Autoclaved soil is commonly used for the study of xenobiotic sorption and as an abiotic control in biodegradation experiments. Autoclaving has been reported to alter soil physico-chemical and xenobiotic sorption characteristics such that comparison of autoclaved with non-autoclaved treatments in soil aging and bioavailability studies may yield misleading results. Experiments could be improved by using autoclaved soil re-inoculated with indigenous microorganisms as an additional or alternative non-sterile treatment for comparison with the sterile, autoclaved control. We examined the effect of autoclaving (3 x 1 h, 121°C, 103.5 KPa) on the physico-chemical properties of a silt loam soil (pH 7.2, 2.3% organic carbon) and the establishment of indigenous microorganisms reintroduced after autoclaving. Sterilisation by autoclaving significantly (p ≤ 0.05) decreased pH (0.6 of a unit) and increased concentrations of water-soluble organic carbon (WSOC; nontreated = 75 mg kg^-1; autoclaved = 1526 mg kg^-1). The initial first-order rate of ¹⁴C-2,4-dichloro-UL-phenol (2,4-DCP) adsorption to non-treated, autoclaved and re-inoculated soil was rapid (K₁ = 16.8-24.4 h^-1) followed by a slower linear phase (K₂). In comparison with autoclaved soil (0.038% day^-1), K₂ values were higher for re-inoculated (0.095% day^-1) and nontreated (0.181% day^-1) soil. This was attributed to a biological process. The Freundlich adsorption coefficient (K(f)) for autoclaved soil was significantly (p ≤ 0.05) higher than for re-inoculated or non-treated soil. Increased adsorption was attributed to autoclaving-induced changes to soil pH and solution composition. Glucose-induced respiration of autoclaved soil after re-inoculation was initially twice that in the non-treated control, but it decreased to control levels by day 4. This reduction corresponded to a depletion of WSOC. 2,4-DCP mineralisation experiments revealed that the inoculum of nonsterile soil (0.5 g) contained 2,4-DCP-degrading microorganisms capable of survival in autoclaved soil. The lag phase before detection of significant 2,4-DCP mineralisation was reduced (from 7 days to ≤3 days) by pre-incubation of re-inoculated soils for 7 and 14 days before 2,4-DCP addition. This was attributed to the preferential utilisation of WSOC prior to the onset of 2,4-DCP mineralisation. Cumulative ¹⁴CO₂ evolved after 21 days was significantly lower (p ≤ 0.05) from non-treated soil (25.3%) than re-inoculated soils (ca 45%). Experiments investigating sorption-biodegradation interactions of xenobiotics in soil require the physico-chemical properties of sterile and non-sterile treatments to be as comparable as possible. For fundamental studies, we suggest using re-inoculated autoclaved soil as an additional or alternative non-sterile treatment.