Kinetics of extraction and stripping of y(III) by Cyanex 272 as an acidic extractant using a constant interfacial cell with laminar flow

The extraction and stripping kinetics of yttrium(III) with bis(2,4,4-trimethylpentyl) phosphinic acid (Cyanex 272, HA) dissolved in heptane as an acid extractant have been investigated by constant interfacial cell with laminar flow. The experimental hydrodynamic conditions have been chosen so that the contribution of diffusion to the measured rate of reaction is minimized. The plot of interfacial area on the rate has shown a linear relationship, which makes the interface the most probable local for the chemical reactions. At the same time, the extraction thermodynamic and kinetic methods are compared to determine the equilibrium extraction constant. A rate equation and the rate-determining step of the extraction and stripping of yttrium(III) have also been obtained, respectively.

Kinetics of cerium(IV) extraction with DEHEHP from HNO3-HF medium using a constant interfacial cell with laminar flow

Studies of the extraction kinetics of cerium(IV) into n-heptane solutions of di(2-ethylhexyl)-2-ethylhexyl phosphonate DEHEHP from HNO3-HF solutions have been carried out using a constant interfacial cell with laminar flow. The experimental hydrodynamic conditions were chosen so that the contribution of diffusion to the measured rate of reaction was minimized. The data were analyzed in terms of pseudo-first order constants. The effects of the stirring rate, specific interfacial area, and temperature on the extraction rate showed that the most probable reaction zone is in the aqueous homogeneous phase. The results were compared with those of the system without HF. It was concluded that the presence of HF decreases the extraction rate of cerium. The addition of HF increases the activation energy for the forward reaction from 21.2 to 55.3 kJ/mol and for the reverse process from 57.9 to 79.0 kJ/mol. According to the experimental data correlated as a function of the concentration of the relevant species involved in the extraction reaction, the corresponding rate equation was deduced as follows:-d[Ce]/dt = k[Ce] center dot B-0.62 center dot HF-0.58 center dot [NO3-](0.57)

Study on transfer and interfacial kinetics of neodymium and samarium in membrane based extraction

Extraction and interfacial kinetics of Nd3+ and Sm3+ with HER/EHP-kerosene in a hollow fiber membrane extractor were studied. The results show that the extraction reactions in the hollow fiber membrane extractor are the same as those in the liquid-liquid extraction, which can be expressed as a quasi-first-order reaction. The effect of acidity in aqueous phase, concentrations of extractant, Nd3+ and Sm3+ on extraction rate were discussed and the corresponding reaction series were obtained. The reaction equations, reaction rate constants and the separation constant were obtained.

Kinetics and mechanism of Y(III) extraction with CA-100 using a constant interfacial cell with laminar flow

The Yttrium(III) extraction kinetics and mechanism with secnonylphonoxy acetic acid (CA-100) were investigated by a constant interfacial cell with laminar flow. The studies of interfacial tension and solubility of extractant and effects of the stirring rate, temperature, specific interfacial area and species concentration on the extraction rate showed that the extraction regime was dependent on the extraction conditions and the most probable reaction zone was at the liquid-liquid interface. The rate equation of extracting yttrium by CA-100 in heptane was Rf = k[Y3+]((a))[H(2)A(2)]((o))(0.88)[H+]((a))(-1.08).

Mass transfer of Er(III) between HBTMPTP dissolved in n-heptane and HAc-NaAc

The rate of extraction of Er(III) from aqueous acetate solutions at 0. 2 mol/L ionic strength by HBTMPTP in n-heptane was studied by using a constant interfacial area cell with laminar flow at (30+/- 0. 5)degrees C. The interfacial activity of HBTMPTP was investigated at n-heptane/0. 2 mol/L (H, Na)Ac (pH=5. 00) interface, The rate of Er(III) extraction was measured at different chemical compositions by varying hydrogen ion, HBTMPTP, Cyanex 302 and chlorine ion concentrations, The effect of stirring speed, temperature and special interfacial area on the rate of extraction was also studied. The results showed that, under the conditions of the experiments, the overall rate is diffusion controlled, that the impurities of Cyanex 302 have the effect of synergistic extraction.

Kinetics of electrocatalytic ascorbic acid at ultramicroelectrode modified by Eastman-AQ polymer containing tris(2,2-'-bipyridine) osmium(III/II) complexes as electron-transfer centers

The theoretical model[17] of an ultramicroelectrode modified with a redox species film is used as the diagnostic tool to characterize the catalytic oxidation of ascorbic acid at carbon fiber ultramicrodisk electrodes coated with an Eastman-AQ-Os(bpy)(3)(2+) film. The electrocatalytic behavior of ascorbic acid at the ultramicroelectrode modified by an Eastman-AQ polymer containing tris(2,2'-bipyridine) osmium(III/II) as mediators is described. In order to determine the five characteristic currents quantitatively, the radius of the ultramicroelectrode and the concentration of ascorbic acid are varied systematically. The kinetic zone diagram has been used to study the electrocatalytic system. This system with 0.5-2.75 mM ascorbic acid belongs to SR + E case, and the concentration profiles of the catalyst in the film are given in detail. Finally, optimizing the design of catalytic system is discussed.

ELECTROCHEMICAL STUDY OF ISOPOLYMOLYBDATE(VI) ANION TRANSFER ACROSS THE WATER/NITROBENZENE INTERFACE

Isopolymolybdate (VI) anion transfer across the water/nitrobenzene (w/n) interface was studied by cyclic voltammetry. The effect of pH and responsed kinetics of isopolymolybdate anion's formation in the water phase on the transfer behavior have been studi

Shock Tube Studies on the Nonequlibrium Electron Affinity Kinetics of Fluorine Atom at High Temperatures

To study electron affinity kinetics, a shock tube method was applied, in which the test gas was ionized by a reflected shock wave and subsequently quenched by a strong rarefaction wave. As the quenching speed of 106 K/s was reached, a nonequilibrium ionization-recombination process occurred, which was dominated by ion recombination with electrons. A Langmuir electrostatic probe was used to monitor variation in the ion number density at the reflection shock region. The working state of the probe was analyzed...

Spectral properties and charge transfer luminescence of Yb3+ : Gd3Ga5O12 (Yb : GGG) crystal

The Yb (10%):GGG and Yb (30%): GGG crystals have been grown by the Czochralski method. The chemical compositions are: Yb1.07Gd1.74Ga5.19O12 and Yb0.33Gd1.47Ga5.2O12. The absorption and emission spectra of Yb:GGG crystal at room temperature have been measured. The spectroscopic parameters of Yb:GGG and Yb:YAG have been compared. Optical absorption spectra of Yb:GGG show 4f-4f transitions related to Gd3+ ion around 300 nm, and also an onset of charge transfer (CT) transitions from oxygen ligands to Gd3+ or Yb3+ cations below 240nm. The CT absorption of Yb3+ is largely overlapped by that of Gd3+ ions. (c) 2005 Elsevier B.V. All rights reserved.

High laser-induced damage threshold HfO2 films prepared by ion-assisted electron beam evaporation

HfO2 films were deposited by electron beam evaporation with different deposition parameters. The properties such as refractive index, weak absorption, and laser induced damage thresholds (LIDTs) of these films have been investigated. It was found that when pulsed Nd:YAG 1064 nm laser is used to investigate LIDT of films: Metallic character is the main factor that influences LIDTs of films obtained from Hf starting material by ion-assisted reaction, and films prepared with higher momentum transfer parameter P have fewer metallic character; The ion-assisted reaction parameters are key points for preparing high LIDT films and if the parameters are chose properly, high LIDT films can be obtained. (c) 2004 Elsevier B.V. All rights reserved.

A partially incoherent rate theory of long-range charge transfer in deoxyribose nucleic acid

A quantum chemistry based Green's function formulation of long-range charge transfer in deoxyribose nucleic acid (DNA) double helix is proposed. The theory takes into account the effects of DNA's electronic structure and its incoherent interaction with aqueous surroundings. In the implementation, the electronic tight-binding parameters for unsolvated DNA molecules are determined at the HF/6-31G* level, while those for individual nucleobase-water couplings are at a semiempirical level by fitting with experimental redox potentials. Numerical results include that: (i) the oxidative charge initially at the donor guanine site does hop sequentially over all guanine sites; however, the revealed rates can be of a much weaker distance dependence than that described by the ordinary Ohm's law; (ii) the aqueous surroundings-induced partial incoherences in thymine/adenine bridge bases lead them to deviate substantially from the superexchange regime; (iii) the time scale of the partially incoherent hole transport through the thymine/adenine pi stack in DNA is about 5 ps. (C) 2002 American Institute of Physics.

Mechanism on exciton-mediated energy transfer in erbium-doped silicon

Exciton-mediated energy transfer model in Er-doped silicon was presented. The emission intensity is related to optically active Er concentration, lifetime of excited Er3+ ion and spontaneous emission. The thermal quenching of the Er luminescence in Si is caused by thermal ionization of Er-bound exciton complex and nonradiative energy back-transfer processes, which correspond to the activation energy of 6.6 and 47.4 meV, respectively. Er doping in silicon introduces donor states, a large enhancement in the electrical activation of Er (up to two orders of magnitude) is obtained by co-implanting Er with O. It appears that the donor states are the gateway to the optically active Er. (C) 2000 Elsevier Science B.V. All rights reserved.

Structural study of YSi1.7 layers formed by channeled ion beam synthesis

High quality YSi1.7 layers (chi(min) of Y is 3.5%) have been formed by 60 keV Y ion implantation in Si (111) substrates to a dose of 1.0 x 10(17)/cm(2) at 450 degrees C using channeled ion beam synthesis (CIBS). It shows that, compared to the conventional nonchanneled ion beam synthesis, CIBS is beneficial in forming YSi1.7 layers with better quality due to the lower defect density created in the implanted layer. Rutherford backscattering/channeling and x-ray diffraction have been used to study the structure and the strain of the YSi1.7 layers. The perpendicular and parallel elastic strains of the YSi1.7 epilayer are e(perpendicular to) = -0.67% +/- 0.02% and e(parallel to) = +1.04% +/- 0.08%. The phenomenon that a nearly zero mismatch of the YSi1.7/Si (111) system results in a nonpseudomorphic epilayer with a rather large parallel strain relative to the Si substrate (epsilon(parallel to) = +1.09%) is explained, and the model is further used to explain the elastic strain of epitaxial ErSi1.7 and GdSi1.7 rare-earth silicides. (C) 1998 American Vacuum Society.

Verification of EL2 electronic absorption effect on charge transfer in semi-insulating GaAs

The electronic absorption of EL2 centers has been clarified to be related to the electron acid hole photoionizations, and the transition from its ground state to metastable state, respectively. Under an illumination with a selected photon energy in the near infrared region, these three processes with different optical cross sections will show different kinetics against the illumination time. It has recently been shown that the photosensitivity (measured under 1.25 eV illumination) of the local vibrational mode absorption induced by some deep defect centers in SI-GaAs is a consequence of the electron and hole photoionizations of EL2. This paper directly measures the kinetics of the electronic transition associated with EL2 under 1.25 eV illumination, which implies the expected charge transfer among different charge states of the EL2 center. A calculation based on a simple rate equation model is in good agreement with the experimental results.