Ion Transport in Liquid Salt Solutions with Oxide Dispersions:``Soggy Sand'' Electrolytes

``Soggy sand'' electrolyte, which essentially consists of oxide dispersions in nonaqueous liquid salt solutions, comprises an important class of soft matter electrolytes. The ion transport mechanism of soggy sand electrolyte is complex. The configuration of particles in the liquid solution has been observed to depend in a nontrivial manner on various parameters related to the oxide (concentration, size, surface chemistry) and solvent (dielectric constant, viscosity) as well as time. The state of the particles in solution not only affects ionic conductivity but also effectively the mechanical and electrochemical properties of the solid liquid composite. Apart from comprehensive understanding of the underlying phenomena that govern ion transport, which will benefit design of better electrolytes, the problem has far-reaching implications in diverse fields such as catalysis, colloid chemistry, and biotechnology.

Biomethanation of herbaceous biomass residues using 3-zone plug flow like digesters - A case study from India

Biomethanation of herbaceous biomass feedstock has the potential to provide clean energy source for cooking and other activities in areas where such biomass availability predominates. A biomethanation concept that involves fermentation of biomass residues in three steps, occurring in three zones of the fermentor is described. This approach while attempting take advantage of multistage reactors simplifies the reactor operation and obviates the need for a high degree of process control or complex reactor design. Typical herbaceous biomass decompose with a rapid VFA flux initially (with a tendency to float) followed by a slower decomposition showing balanced process of VFA generation and its utilization by methanogens that colonize biomass slowly. The tendency to float at the initial stages is suppressed by allowing previous days feed to hold it below digester liquid which permits VFA to disperse into the digester liquid without causing process inhibition. This approach has been used to build and operate simple biomass digesters to provide cooking gas in rural areas with weed and agro-residues. With appropriate modifications, the same concept has been used for digesting municipal solid wastes in small towns where large fermentors are not viable. With further modifications this concept has been used for solid-liquid feed fermentors. Methanogen colonized leaf biomass has been used as biofilm support to treat coffee processing wastewater as well as crop litter alternately in a year. During summer it functions as a biomass based biogas plants operating in the three-zone mode while in winter, feeding biomass is suspended and high strength coffee processing wastewater is let into the fermentor achieving over 90% BOD reduction. The early field experience of these fermentors is presented.

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.

A kinetic model for heterogeneous acetalisation of poly(vinyl alcohol)

A model for heterogeneous acetalisation of poly(vinyl alcohol) with limited solution volume is proposed based on the grain model of Sohn and Szekely. Instead of treating the heterogeneous acetalisation as purely a diffusion process, as in the Matuzawa and Ogasawara model, the present model also takes into account the chemical reaction and the physical state of the solid polymer, such as degree of swelling and porosity, and assumes segregation of the polymer phase at higher conversion into an outer fully reacted zone and an inner zone where the reaction still proceeds. The solution of the model for limited solution volume, moreover, offers a simple method of determining the kinetic parameters and diffusivity for the solid-liquid system using the easily measurable bulk solution concentration of the liquid reactant instead of conversion-distance data for the solid phase, which are considerably more difficult to obtain.

Effect of process parameters on transport phenomena during solidification in the presence of electromagnetic stirring

In the present work, a numerical study is performed to predict the effect of process parameters on transport phenomena during solidification of aluminium alloy A356 in the presence of electromagnetic stirring. A set of single-phase governing equations of mass, momentum, energy and species conservation is used to represent the solidification process and the associated fluid flow, heat and mass transfer. In the model, the electromagnetic forces are incorporated using an analytical solution of Maxwell equation in the momentum conservation equations and the slurry rheology during solidification is represented using an experimentally determined variable viscosity function. Finally, the set of governing equations is solved for various process conditions using a pressure based finite volume technique, along with an enthalpy based phase change algorithm. In present work, the effect of stirring intensity and cooling rate are considered. It is found that increasing stirring intensity results in increase of slurry velocity and corresponding increase in the fraction of solid in the slurry. In addition, the increasing stirring intensity results uniform distribution of species and fraction of solid in the slurry. It is also found from the simulation that the distribution of solid fraction and species is dependent on cooling rate conditions. At low cooling rate, the fragmentation of dendrites from the solid/liquid interface is more.

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.

Thermodynamic properties of the systems benzene-chloroethanes

This paper presents the experimental data on vapor-liquid equilibrium and heats of mixing of mixtures of benzene with 1, e-dichloroethane, 1, l, 1 -trichloroethane, and lt1,2,2-tetrachloroethane.A literature survey revealed that the heats of mixing of benzene-l,2-dichloroethane have been studied and Table I shows the extent of study on this system.

Calorimetry In Vapor Absorption And Binary Mixture Vapor Compression Refrigeration And Heatpump Systems

The use of binary fluid systems in thermally driven vapour absorption and mechanically driven vapour compression refrigeration and heatpump cycles has provided an impetus for obtaining experimental date on caloric properties of such fluid mixtures. However, direct measurements of these properties are somewhat scarce in spite of the calorimetric techniques described in the literature being quite adequate. Most of the design data are derived through calculations using theoretical models and vapour-liquid equilibrium data. This article addresses the choice of working fluids and the current status on the data availability vis-a-vis engineering applications. Particular emphasis is on organic working fluid pairs.

Modeling Of Hydrolytic Polymerization In A Semibatch Nylon 6 Reactor

Hydrolytic polymerization of caprolactam to Nylon 6 in a semibatch reactor is carried out by heating a mixture of water and caprolactam. Evaporation of volatiles caused by heating results in a pressure build-up. After the pressure reaches a predetermined value, vapors are vented to keep the pressure constant for some time, and thereafter, to lower the pressure to a value slightly above atmospheric in a preprogrammed manner. The characteristics of the polymer are determined by the chemical reactions and the vaporization of water and caprolactam. The semibatch operation has been simulated and the predictions have been compared with industria data. The observed temperature and pressure histories were predicted with a fair degree of accuracy. It was found that the predictions of the degree of polymerization however are sensitive to the vapor-liquid equilibrium relations. A comparison with an earlier model, which neglected mass transfer resistance, indicates that simulation using the VLE data of Giori and Hayes and accounting for mass transfer resistance is more reliable.

Moving boundaries due to distributed sources in a slab

Analytical and numerical solutions have been obtained for some moving boundary problems associated with Joule heating and distributed absorption of oxygen in tissues. Several questions have been examined which are concerned with the solutions of classical formulation of sharp melting front model and the classical enthalpy formulation in which solid, liquid and mushy regions are present. Thermal properties and heat sources in the solid and liquid regions have been taken as unequal. The short-time analytical solutions presented here provide useful information. An effective numerical scheme has been proposed which is accurate and simple.

Inverse surface melting in confined clusters: Ar-13 in zeolite L

Monte Carlo and molecular dynamics simulations on an Ar-13 cluster in zeolite L have been carried out at a series of temperatures to understand the rigid-nonrigid transition corresponding to the solid-liquid transition exhibited by the free Ar-13 cluster. The icosahedral geometry of the free cluster is no longer preferred when the cluster is confined in the zeolite. The root-mean-squared pair distance fluctuation, delta, exhibits a sharp, well-defined rigid-nonrigid transition at 17 K as compared to 27 K for the free cluster. Multiple peaks in the distribution of short-time averages of the guest-host interaction energy indicate coexistence of two phases.; It is shown that this transition is associated with the inner atoms becoming mobile at 17 K even while the outer layer atoms, which are in close proximity to the zeolitic wall, continue to be comparatively immobile. This may be contrasted with the melting of large free clusters of 40 or more atoms which exhibit surface melting. Guest-host interactions seem to play a predominant role in determining the properties of confined clusters. We demonstrate that the volume of the cluster increases rather sharply at 17 and 27 K respectively for the confined and the free cluster. Power spectra suggest that the motion of the inner atoms is generally parallel to the atoms which form the cage wall.

The effect of constituent metal ions on the electrokinetics of chalcopyrite

Chalcopyrite in contact with water is thermodynamically unstable in the presence of oxygen. Oxidation of chalcopyrite may take place due to various factors, e.g., geological environment, mining/comminution, and storage. In this work oxidation of chalcopyrite has been investigated through interfacial electrokinetics. The characteristics of samples obtained from different geological locations as well as the effects of ageing and laboratory oxidation have been delineated. Variation of the solid-liquid ratio was found to have a significant effect on the zeta-potential characteristics of chalcopyrite. The role of constituent metal ions, namely copper and iron, has been studied in the absence and presence of externally added metal ions. The results indicated that the ratio of Cu/Fe on the surface of oxidized chalcopyrite determines the Stern layer potential and under appropriate solution chemistry conditions influences charge reversals. The mineral surfaces, thus, could be either copper-rich or iron-rich as reflected by a shift in pH(iep),,(s). The observed charge reversals have been explained on the basis of a model proposed by James and Healy. (C) 1997 Academic Press.

Rayleigh-Benard convection during solidification of an eutectic solution cooled from the top

The interaction between laminar Rayleigh-Benard convection and directional solidification is studied for the case of an eutectic solution kept in a rectangular cavity cooled from the top. Experiments and numerical simulations are carried out using an NH4Cl-H2O solution as the model fluid. The flow is visualized using a sheet of laser light scattered by neutrally buoyant, hollow-glass spheres seeded in the fluid. The numerical modeling is performed using a pressure-based finite-volume method according to the SIMPLER algorithm. The present configuration enables us to visualize flow vortices in the presence of a continuously evolving solid/liquid interface. Clear visualization of the Rayleigh-Benard convective cells and their interaction with the solidification front are obtained. It is observed that the convective cells are characterized by zones of up-flow and down-flow, resulting in the development of a nonplanar interface. Because of the continuous advancement of the solid/liquid interface, the effective liquid height of the cavity keeps decreasing. Once the height of the fluid layer falls below a critical value, the convective cells become weaker and eventually die out, leading to the growth of a planar solidification front. Results of flow visualization and temperature measurement are compared with those from the numerical simulation, and a good agreement is found.

Three-dimensional computational modeling of momentum, heat, and mass transfer in a laser surface alloying process

A three- dimensional, transient model is developed for studying heat transfer, fluid flow, and mass transfer for the case of a single- pass laser surface alloying process. The coupled momentum, energy, and species conservation equations are solved using a finite volume procedure. Phase change processes are modeled using a fixed-grid enthalpy-porosity technique, which is capable of predicting the continuously evolving solid- liquid interface. The three- dimensional model is able to predict the species concentration distribution inside the molten pool during alloying, as well as in the entire cross section of the solidified alloy. The model is simulated for different values of various significant processing parameters such as laser power, scanning speed, and powder feedrate in order to assess their influences on geometry and dynamics of the pool, cooling rates, as well as species concentration distribution inside the substrate. Effects of incorporating property variations in the numerical model are also discussed.

Grain Floatation During Equiaxed Solidification of an Al-Cu Alloy in a Side-Cooled Cavity: Part II-Numerical Studies

In this article, a single-phase, one-domain macroscopic model is developed for studying binary alloy solidification with moving equiaxed solid phase, along with the associated transport phenomena. In this model, issues such as thermosolutal convection, motion of solid phase relative to liquid and viscosity variations of the solid-liquid mixture with solid fraction in the mobile zone are taken into account. Using the model, the associated transport phenomena during solidification of Al-Cu alloys in a rectangular cavity are predicted. The results for temperature variation, segregation patterns, and eutectic fraction distribution are compared with data from in-house experiments. The model predictions compare well with the experimental results. To highlight the influence of solid phase movement on convection and final macrosegregation, the results of the current model are also compared with those obtained from the conventional solidification model with stationary solid phase. By including the independent movement of the solid phase into the fluid transport model, better predictions of macrosegregation, microstructure, and even shrinkage locations were obtained. Mechanical property prediction models based on microstructure will benefit from the improved accuracy of this model.