Comparing hydrogen absorption kinetics of the samples of intermetallic compound and metal hydride compact on its basis

This work is devoted to an experimental study and comparison of the kinetics of hydrogen absorption by an intermetallic compound LaNi4.4Al0.3Fe0.3 in form of pure intermetallic compound free backfill and a compact based on it obtained by cold pressing with a spiral matrix of nickel-foam. To calculate the kinetic parameters of the hydrogen absorption reaction, the initial rates method is used. The PCT absorption isotherms are measured at temperatures of 313, 333, and 353 K. The experimental data are described with quite high confidence by the chosen model, which assumes that the reaction rate controlling step is the dissociative absorption of hydrogen on the surface of the a-phase. The rate of hydrogen absorption increases with increasing pressure drop and temperature. It is shown that the rate of hydrogen absorption by the sample of pure IMC is significantly less dependent on temperature compared to the compact sample. In addition, the reaction rate at temperatures of 313 and 333 K is higher for the free backfill sample, and at 353 K it is higher for the metal hydride compact. The values of the absorption constant and the activation energy of the hydrogen absorption reaction are determined for both samples.

Kinetic Aspects of Phosphorus Removal from Electromagnetically Levitated 600 MPa Steel Droplets

A kinetic model was developed to study the dephosphorization of 600 MPa steel droplets under electromagnetic levitation conditions. The relationships which were derived from the model between dephosphorization and the influence of temperature and gas flow rate were in good agreement with experimental data. Both temperature and gas flow rate were conducive to the evaporation of phosphorus, with the effect of temperature having a greater influence than that of the gas velocity. The results show that the rate-controlling step for the dephosphorization process was diffusion within the gas phase. This work aims to provide a theoretical basis for process optimization during the dephosphorization of 600 MPa steel.

A multiparametric study on the dissolution of synthetic brannerite

Brannerite, UTi2O6 is reported to occur in various uraniferous deposits worldwide. Natural brannerite specimens are found in the amorphous state and are usually considered to be refractory to dissolution due to the formation of TiO2 passivation layer. In the present work, brannerite was synthesized by wet chemistry route, then characterized prior the development of multiparametric dissolution experiments. The evolution of U and Ti concentrations was followed in 0.1–2 mol/L H2SO4 solutions, for temperatures ranging from 25 to 80 °C, in the presence (or not) of 2.8 g/L of dissolved Fe(III). The dissolution of synthetic brannerite was congruent in the whole experimental domain. The formation of Ti-enriched secondary phase at the surface of the brannerite grains was not evidenced. The dissolution rate constants, activation energies and partial orders of the overall dissolution reaction relative to proton activity were determined in the presence (or absence) of Fe(III). The introduction of Fe(III) in sulfuric acid solutions increased the dissolution rate constant by 5 orders of magnitude and induced significant modifications of the apparent activation energy (from 71 ± 4 to 91 ± 6 kJ/mol) and of the partial order relative to proton activity (from 0.42 ± 0.09 to 0.84 ± 0.08). This study suggested that the uncongruency of the brannerite dissolution and the changes usually observed in the rate-controlling step with temperature could be linked to the loss of the crystal structure in natural samples.

Study of adsorption mechanism of Congo Red on graphene oxide/PAMAM nanocomposite

Graphene oxide/poly(amidoamine) (GO/PAMAM) nanocomposite adsorbed high quantities of congo red (CR) anionic dye in 0.1 M NaCl solution, with the maximum adsorption capacity of 198 mg·g−1. The kinetics and thermodynamics of adsorption were investigated to elucidate the effects of pH, temperature, shaking rate, ionic strength, and contact time. Kinetic data were analyzed by the KASRA model and the KASRA, ISO, and pore-diffusion equations. Adsorption adsorption isotherms were studied by the ARIAN model and the Henry, Langmuir, and Temkin equations. It was shown that adsorption sites of GO/PAMAM at experimental conditions were phenolic hydroxyl groups of GO sheets and terminal amine groups of PAMAM dendrimer. Analysis of kinetic data indicated that amine sites were located on the surface, and that hydroxyl sites were placed in the pores of adsorbent. CR molecules interacted with the adsorption sites via hydrogen bonds. The molecules were adsorbed firstly on the amine sites, and then on the internal hydroxyl sites. Adsorption kinetic parameters indicated that the interaction of CR to the –NH3+ sites was the rate-controlling step of adsorption of CR on this site and adsorption activation energies calculated for different parts of this step. On the other hand, kinetic parameters showed that the intraparticle diffusion was the rate-controlling step during the interaction of CR molecules to –OH sites and activation energy of this step was not calculable. Finally, the used GO/PAMAM was completely regenerated by using ethylenediamine.

Study of adsorption mechanism of Congo Red on graphene oxide/PAMAM nanocomposite

Graphene oxide/poly(amidoamine) (GO/PAMAM) nanocomposite adsorbed high quantities of congo red (CR) anionic dye in 0.1 M NaCl solution, with the maximum adsorption capacity of 198 mg·g−1. The kinetics and thermodynamics of adsorption were investigated to elucidate the effects of pH, temperature, shaking rate, ionic strength, and contact time. Kinetic data were analyzed by the KASRA model and the KASRA, ISO, and pore-diffusion equations. Adsorption adsorption isotherms were studied by the ARIAN model and the Henry, Langmuir, and Temkin equations. It was shown that adsorption sites of GO/PAMAM at experimental conditions were phenolic hydroxyl groups of GO sheets and terminal amine groups of PAMAM dendrimer. Analysis of kinetic data indicated that amine sites were located on the surface, and that hydroxyl sites were placed in the pores of adsorbent. CR molecules interacted with the adsorption sites via hydrogen bonds. The molecules were adsorbed firstly on the amine sites, and then on the internal hydroxyl sites. Adsorption kinetic parameters indicated that the interaction of CR to the –NH3+ sites was the rate-controlling step of adsorption of CR on this site and adsorption activation energies calculated for different parts of this step. On the other hand, kinetic parameters showed that the intraparticle diffusion was the rate-controlling step during the interaction of CR molecules to –OH sites and activation energy of this step was not calculable. Finally, the used GO/PAMAM was completely regenerated by using ethylenediamine.

Adsorptive Performance of Polypyrrole-Based KOH-Activated Carbon for the Cationic Dye Crystal Violet: Kinetic and Equilibrium Studies

The aim of this work was to investigate the adsorptive performance of the polypyrrole-based KOH-activated carbon (PACK) in the removal of the basic dye crystal violet (CV) using a batch adsorption system. The equilibrium data, obtained at different initial CV concentrations ( C 0 = 50 – 500 mg / L ) and temperatures (25–45°C), were interpreted using the Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich isotherms, with the Langmuir model providing a better fit ( R 2 ≥ 0.9997 ) and a maximum adsorption capacity of 497.51 mg/g at 45°C. Under the examined conditions, the values of the thermodynamic parameters free energy, enthalpy, and entropy indicate a spontaneous, endothermic, and physisorption adsorption process. The kinetic data of the adsorption process were very well described by a pseudo-second-order model ( R 2 ≥ 0.9996 ). However, surface diffusion seems to be the main rate-controlling step. Thus, we concluded that PACK shows commercial potential for the removal of cationic dyes such as CV from industrial effluent.

Interfacial reaction between Ni particle reinforcements and liquid Sn-based eutectic solders

Purpose This paper aims to derive a model of growth kinetics of the intermetallic compound (IMC) layer formed in the reaction between liquid Sn-based solders and Ni particle reinforcements and to compare with the experimental data to verify the effects of Sn concentration and alloying element. Design/methodology/approach A composite solder was manufactured by mechanically introducing Ni particle reinforcements into a solder matrix. The effect of the non-reactive alloying elements, Ag, Pb and Bi, on the growth kinetics of the IMC formed between liquid Sn-based eutectic solders and Ni particles, reacting this composite solder at 250°C–280°C was studied. Findings Experimental results showed that only the IMC Ni3Sn4 was present as a reaction product. Using the diffusion-controlled reaction mechanism, a kinetic equation quantifying both Sn concentration and alloying element effects was derived and verified by comparing the kinetic data obtained using four different solders with different concentrations of Sn and the alloying elements. Originality/value The similarity between the activation energies of these four solders confirms that the diffusion of Sn atoms through the IMC is the rate-controlling step. Besides, the kinetic values are independent of the geometry of Ni, whether spherical particle or flat substrate.

Study of the kinetics of calcium molybdate leaching with sodium carbonate solutions

Calcium molybdate forms powellite, it is produced as a result of oxidizing roasting of off-grade molybdenum sulphide concentrates and other molybdenum materials with calcium additives (calcium oxides and hydro xides, calcium chlorides) in air at the temperatures of 550–600 oC. Use of Na2CO3 solutions enables an efficient recovery of Мо from CaMoO4 and a quantitative removal of impurities. To determine the optimum conditions for this process, one would need data on CaMoO4 leaching within a broad range of Na2CO3 concentrations and at high temperature and one would need to analyze the composition of the solid phase and the kinetic parameters of the process, i.e. rate and rate-controlling step. The authors look at the CaMoO4 leaching kinetics in 1.0–2.5 mol/l Na2CO3 solutions at 60–90 oC. It was found that the process rate is dictated by the stirring intensity and tends to increase with a rising temperature and the reagent concentration rising in the range of 1.0–1.5 mol/l. A higher concentration of Na2CO3 has no effect on the reaction rate. An apparent reaction order was determined in the Na2CO3 concentration range of 1.0–1.5 mol/l. An equation is proposed for calculating the CaMoO4 dissolution rate for the Na2CO3 solution and the temperature of 80 oC. It was established that a kinetic mode of leaching takes place in the soda concentration range of 1.0–1.5 mol/l amid intensive stirring. It is demonstrated that, within the studied Na2CO3 concentration range, calcite СаСО3 is formed after vaterite, a less stable phase of calcite, with crystallization of double sodium-calcium carbonates Na2Са(CO3)2·nH2O (n = 0, 2, 5) occurring at the same time. With the concentration of soda being >1.5 mol/l, the process is controlled by internal diffusion. In this region, the leaching rate is independent of the Na2CO3 concentration. Formation of double carbonates is associated with an additional consumption of soda. Therefore, when using this system one should consider how CaMoO4 typically dissolves in Na2CO3 solutions. The presence of these compounds in the soda solution after molybdenum leaching may impact the recovery of Мо from the solution using the known techniques. It may also hinder the recirculation of sodium carbonates going for the second leaching cycle.

Topography of the Free Energy Landscape on the Claisen-Schmidt Condensation: Solvent and Temperature Effect in the Rate-Controlling Step

Recent studies have assigned hydroxide elimination and C=C bond formation step in base-promoted aldol condensation the role of having a strong influence in the overall rate reaction, in contrast to...