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.

High-pressure phase equilibrium in the {carbon dioxide (1) + 1-chloropropane (2)} binary system

Abstract The current study reports original vapour-liquid equilibrium (VLE) for the system {CO2 (1) + 1-chloropropane (2)}. The measurements have been performed over the entire pressure-composition range for the (303.15, 313.15 and 328.15) K isotherms. The values obtained have been used for comparison of four predictive approaches, namely the equation of state (EoS) of Peng and Robinson (PR), the Soave modification of Benedict–Webb–Rubin (SBWR) EoS, the Critical Point-based Revised Perturbed-Chain Association Fluid Theory (CP-PC-SAFT) EoS, and the Conductor-like Screening Model for Real Solvents (COSMO-RS). It has been demonstrated that the three EoS under consideration yield similar and qualitatively accurate predictions of VLE, which is not the case for the COSMO-RS model examined. Although CP-PC-SAFT EoS exhibits only minor superiority in comparison with PR and SBWR EoS in predicting VLE in the system under consideration, its relative complexity can be justified when taking into account the entire thermodynamic phase space and, in particular, considering the liquid densities and sound velocities over a wider pressure-volume-temperature range.

Structural and chemical characterization of corals grown under present day and naturally elevated pCO2 conditions in Papua New Guinea - a window into the future

Dissertação de mestrado, Biologia Marinha, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2015

The effects of additives and chemical modification on the solution properties of thermo-sensitive polymers

Cette thèse concerne l’étude de phase de séparation de deux polymères thermosensibles connus-poly(N-isopropylacylamide) (PNIPAM) et poly(2-isopropyl-2-oxazoline) (PIPOZ). Parmi des études variées sur ces deux polymères, il y a encore deux parties de leurs propriétés thermiques inexplicites à être étudiées. Une partie concerne l’effet de consolvant de PNIPAM dans l’eau et un autre solvant hydromiscible. L’autre est l’effet de propriétés de groupes terminaux de chaînes sur la séparation de phase de PIPOZ. Pour ce faire, nous avons d’abord étudié l’effet de l’architecture de chaînes sur l’effet de cosolvant de PNIPAMs dans le mélange de méthanol/eau en utilisant un PNIPAM en étoile avec 4 branches et un PNIPAM cyclique comme modèles. Avec PNIPAM en étoile, l’adhérence de branches PNIPAM de à un cœur hydrophobique provoque une réduction de Tc (la température du point de turbidité) et une enthalpie plus faible de la transition de phase. En revanche, la Tc de PNIPAM en étoile dépend de la masse molaire de polymère. La coopérativité de déhydratation diminue pour PNIPAM en étoile et PNIPAM cyclique à cause de la limite topologique. Une étude sur l’influence de concentration en polymère sur l’effet de cosolvant de PNIPAM dans le mélange méthanol/eau a montré qu’une séparation de phase liquide-liquide macroscopique (MLLPS) a lieu pour une solution de PNIPAM dans le mélange méthanol/eau avec la fraction molaire de méthanol entre 0.127 et 0.421 et la concentration en PNIPAM est constante à 10 g.L-1. Après deux jours d’équilibration à température ambiante, la suspension turbide de PNIPAM dans le mélange méthanol/eau se sépare en deux phases dont une phase possède beaucoup plus de PNIPAM que l’autre. Un diagramme de phase qui montre la MLLPS pour le mélange PNIPAM/eau/méthanol a été établi à base de données expérimentales. La taille et la morphologie de gouttelettes dans la phase riche en polymère condensée dépendent de la fraction molaire de méthanol. Parce que la présence de méthanol influence la tension de surface des gouttelettes liquides, un équilibre lent de la séparation de phase pour PNIPAM/eau/méthanol système a été accéléré et une séparation de phase liquide-liquide macroscopique apparait. Afin d’étudier l’effet de groupes terminaux sur les propriétés de solution de PIPOZ, deux PIPOZs téléchéliques avec groupe perfluorodécanyle (FPIPOZ) ou groupe octadécyle (C18PIPOZ) comme extrémités de chaîne ont été synthétisés. Les valeurs de Tc des polymères téléchéliques ont beaucoup diminué par rapport à celle de PIPOZ. Des micelles stables se forment dans des solutions aqueuses de polymères téléchéliques. La micellization et la séparation de phase de ces polymères dans l’eau ont été étudiées. La séparation de phase de PIPOZs téléchéliques suit le mécanisme de MLLPS. Des différences en tailles de gouttelettes formées à l’intérieur de solutions de deux polymères ont été observées. Pour étudier profondément les différences dans le comportement d’association entre deux polymères téléchéliques, les intensités des signaux de polymères correspondants et les temps de relaxation T1, T2 ont été mesurés. Des valeurs de T2 de protons correspondants aux IPOZs sont plus hautes.

The equilibrium structure of HCN

The equilibrium structure of HCN has been determined from the previously published ground state rotational constants of eight isotopomers by using (B0‐Be) values obtained from a variational calculation of the vibration–rotation spectrum. The results are re(CH)=1.065 01(8) Å, and re(CN)=1.153 24(2) Å.

Simulating the detailed chemical composition of secondary organic aerosol formed on a regional scale during the TORCH 2003 campaign in the southern UK

Following on from the companion study (Johnson et al., 2006), a photochemical trajectory model (PTM) has been used to simulate the chemical composition of organic aerosol for selected events during the 2003 TORCH (Tropospheric Organic Chemistry Experiment) field campaign. The PTM incorporates the speciated emissions of 124 nonmethane anthropogenic volatile organic compounds (VOC) and three representative biogenic VOC, a highly-detailed representation of the atmospheric degradation of these VOC, the emission of primary organic aerosol (POA) material and the formation of secondary organic aerosol (SOA) material. SOA formation was represented by the transfer of semi and non-volatile oxidation products from the gas-phase to a condensed organic aerosol-phase, according to estimated thermodynamic equilibrium phase-partitioning characteristics for around 2000 reaction products. After significantly scaling all phase-partitioning coefficients, and assuming a persistent background organic aerosol (both required in order to match the observed organic aerosol loadings), the detailed chemical composition of the simulated SOA has been investigated in terms of intermediate oxygenated species in the Master Chemical Mechanism, version 3.1 ( MCM v3.1). For the various case studies considered, 90% of the simulated SOA mass comprises between ca. 70 and 100 multifunctional oxygenated species derived, in varying amounts, from the photooxidation of VOC of anthropogenic and biogenic origin. The anthropogenic contribution is dominated by aromatic hydrocarbons and the biogenic contribution by alpha-and beta-pinene (which also constitute surrogates for other emitted monoterpene species). Sensitivity in the simulated mass of SOA to changes in the emission rates of anthropogenic and biogenic VOC has also been investigated for 11 case study events, and the results have been compared to the detailed chemical composition data. The role of accretion chemistry in SOA formation, and its implications for the results of the present investigation, is discussed.

Insights into redox cycling of sulfur and iron in peatlands using high-resolution diffusive equilibrium thin film (DET) gel probe sampling

High spatial resolution vertical profiles of pore-water chemistry have been obtained for a peatland using diffusive equilibrium in thin films (DET) gel probes. Comparison of DET pore-water data with more traditional depth-specific sampling shows good agreement and the DET profiling method is less invasive and less likely to induce mixing of pore-waters. Chloride mass balances as water tables fell in the early summer indicate that evaporative concentration dominates and there is negligible lateral flow in the peat. Lack of lateral flow allows element budgets for the same site at different times to be compared. The high spatial resolution of sampling also enables gradients to be observed that permit calculations of vertical fluxes. Sulfate concentrations fall at two sites with net rates of 1.5 and 5.0nmol cm− 3 day− 1, likely due to a dominance of bacterial sulfate reduction, while a third site showed a net gain in sulfate due to oxidation of sulfur over the study period at an average rate of 3.4nmol cm− 3 day− 1. Behaviour of iron is closely coupled to that of sulfur; there is net removal of iron at the two sites where sulfate reduction dominates and addition of iron where oxidation dominates. The profiles demonstrate that, in addition to strong vertical redox related chemical changes, there is significant spatial heterogeneity. Whilst overall there is evidence for net reduction of sulfate within the peatland pore-waters, this can be reversed, at least temporarily, during periods of drought when sulfide oxidation with resulting acid production predominates.

Flux difference splitting for inviscid, real gases with non-equilibrium chemistry

A flux-difference splitting method is presented for the inviscid terms of the compressible flow equations for chemical non-equilibrium gases

An efficient finite difference scheme for three-dimensional, non-equilibrium flows using operator splitting

An efficient finite difference scheme is presented for the inviscid terms of the three-dimensional, compressible flow equations for chemical non-equilibrium gases. This scheme represents an extension and an improvement of one proposed by the author, and includes operator splitting.

Boundary condition effects in the simulation study of equilibrium properties of magnetic dipolar fluids

In this paper we investigate the equilibrium properties of magnetic dipolar (ferro-) fluids and discuss finite-size effects originating from the use of different boundary conditions in computer simulations. Both periodic boundary conditions and a finite spherical box are studied. We demonstrate that periodic boundary conditions and subsequent use of Ewald sum to account for the long-range dipolar interactions lead to a much faster convergence (in terms of the number of investigated dipolar particles) of the magnetization curve and the initial susceptibility to their thermodynamic limits. Another unwanted effect of the simulations in a finite spherical box geometry is a considerable sensitivity to the container size. We further investigate the influence of the surface term in the Ewald sum-that is, due to the surrounding continuum with magnetic permeability mu(BC)-on the convergence properties of our observables and on the final results. The two different ways of evaluating the initial susceptibility, i.e., (1) by the magnetization response of the system to an applied field and (2) by the zero-field fluctuation of the mean-square dipole moment of the system, are compared in terms of speed and accuracy.

Equilibrium behavior of symmetric ABA triblock copolymer melts

Melts of ABA triblock copolymer molecules with identical end blocks are examined using self-consistent field theory (SCFT). Phase diagrams are calculated and compared with those of homologous AB diblock copolymers formed by snipping the triblocks in half. This creates additional end segments which decreases the degree of segregation. Consequently, triblock melts remain ordered to higher temperatures than their diblock counterparts. We also find that middle-block domains are easier to stretch than end-block domains. As a result, domain spacings are slightly larger, the complex phase regions are shifted towards smaller A-segment compositions, and the perforated-lamellar phase becomes more metastable in triblock melts as compared to diblock melts. Although triblock and diblock melts exhibit very similar phase behavior, their mechanical properties can differ substantially due to triblock copolymers that bridge between otherwise disconnected A domains. We evaluate the bridging fraction for lamellar, cylindrical, and spherical morphologies to be about 40%–45%, 60%–65%, and 75%–80%, respectively. These fractions only depend weakly on the degree of segregation and the copolymer composition.

Deterpenation of Bergamot Essential Oil Using Liquid-Liquid Extraction: Equilibrium Data of Model Systems at 298.2 K

The deterpenation of bergamot essential oil can be performed by liquid liquid extraction using hydrous ethanol as the solvent. A ternary mixture composed of 1-methyl-4-prop-1-en-2-yl-cydohexene (limonene), 3,7-dimethylocta-1,6-dien-3-yl-acetate (linalyl acetate), and 3,7-dimethylocta-1,6-dien-3-ol (linalool), three major compounds commonly found in bergamot oil, was used to simulate this essential oil. Liquid liquid equilibrium data were experimentally determined for systems containing essential oil compounds, ethanol, and water at 298.2 K and are reported in this paper. The experimental data were correlated using the NRTL and UNIQUAC models, and the mean deviations between calculated and experimental data were lower than 0.0062 in all systems, indicating the good descriptive quality of the molecular models. To verify the effect of the water mass fraction in the solvent and the linalool mass fraction in the terpene phase on the distribution coefficients of the essential oil compounds, nonlinear regression analyses were performed, obtaining mathematical models with correlation coefficient values higher than 0.99. The results show that as the water content in the solvent phase increased, the kappa value decreased, regardless of the type of compound studied. Conversely, as the linalool content increased, the distribution coefficients of hydrocarbon terpene and ester also increased. However, the linalool distribution coefficient values were negatively affected when the terpene alcohol content increased in the terpene phase.