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.

Mechanisms of sodium and potassium ions transfer facilitated by dibenzo-15-crown-5 across the water /1,2-dichloroethane interface using micropipettes

The transfer of sodium and potassium ions facilitated by dibenzo-15-crown-5 (DB15C5) has been studied at the micro-water/1,2-dichloroethane (water/DCE) interface supported at the tip of a micropipette. Cyclic volt-ammetric measurements were performed in two limiting conditions: the bulk concentration of Na+ or K+ in the aqueous phase is much higher than that of DB15C5 in the organic phase (DB15C5 diffusion controlled process) and the reverse condition (metal ion diffusion controlled process). The mechanisms of the facilitated Na+ transfer by DB15C5 are both transfer by interfacial complexation (TIC) with 1 : 1 stoichiometry under these two conditions, and the corresponding association constants were determined at log beta(1) = 8.97 +/- 0.05 or log beta(1) = 8.63 +/- 0.03. However, the transfers of K+ facilitated by DB15C5 show different behavior. In the former case it is a TIC process and its stoichiometry is 1 : 2, whereas in the latter case two peaks during the forward scan were observed, the first of which was confirmed as the formation of K (DB15C5)(2) at the interface by a TIC mechanism, while the second one may be another TIC process with 1 : 1 stoichiometry in the more positive potential. The relevant association constants calculated for the complexed ion, K+(DB15C5)(2), in the organic phase in two cases, logbeta(2), are 13.64 +/- 0.03 and 11.34 +/- 0.24, respectively.

Systematic investigation of alkali metal ion transfer across the micro- and nano-water/1,2-dichloroethane interfaces facilitated by dibenzo-18-crown-6

Facilitated alkali metal ion (M+= Li+, Na+, K+, Rb+, and Cs+) transfers across the micro- and nano-water/1,2-dichloroethane (W/DCE) interfaces supported at the tips of micro- and nanopipets by dibenzo-18-crown-6 (DB18C6) have been investigated systematically using cyclic voltammetry. The theory developed by Matsuda et al. was applied to estimate the association constants of DB18C6 and M+ in the DCE phase based on the experimental voltammetric results. The kinetic measurements for alkali metal ion transfer across the W/DCE interface facilitated by DB18C6 were conducted using nanopipets or-submicropipets, and the standard rate constants (k(0)) were evaluated by analysis of the experimental voltammetric data. They increase in the following order: k(Cs+)(0) < k(Li+)(0) < k(Rb+)(0) < k(Na+)(0) < k(K+)(0), which is in accordance with their association constants except Cs+ and Li+.

Study of electron-transfer reactions across an externally polarized water/1,2-dichloroethane interface by scanning electrochemical microscopy

A novel method to study electron-transfer (ET) reactions between ferrocene in 1,2-dichloroethane (DCE) and a redox couple of K3Fe(CN)(6) and K4Fe(CN)(6) in water using scanning electrochemical microscopy (SECM) with a three-electrode setup is reported. In this work, a water droplet that adheres to the Surface of a platinum disk electrode is immersed in a DCE solution. The aqueous redox couple serves both as a reference electrode on the platinum disk and as an electron donor/acceptor at the polarized liquid/liquid inter-face. With the present experimental approach, the liquid/liquid interface can be polarized externally, while the electron-transfer reactions between the two phases can be monitored independently by SECM. The apparent heterogeneous rate constants for the ET reactions were obtained by fitting the experimental approach curves to the theoretical values. These rate constants obey the Butler-Volmer theory i.e., them, are found to be potential dependent.

Kinetic analysis of TNF immune complex by using surface plasmon resonane

The kinetic analysis of the interaction between tumor necrosis factor(TNF) and its monoclonal antibody was performed by surface plasmon resonance(SPR) technique. The monoclonal antibody was immobilized to the surface of CM5 sensor chip by amine coupling. TNF at different concentrations was injected across the mAb immobilized surface. The interaction was recorded in real time and could be seen on the sensorgram. One cycle, including association, dissociation and regeneration, lasted no more than 15 min. The interaction results was evaluated using 1 : 1 Langmuir binding model. The kinetic rate constants were calculated to be: k =1.68 X 10(3) L (.) mol(-1) (.) s(-1), k(d) = 1.73 X 10(-4) s(-1), and the affinity constants K-A = 9. 7 X 10(3) L (.) mol(-1), K-r)= 1. 03 X 10(-7) Mol (.) L-1. The X-2 was 3.47, which showed that the interaction is consistent with the 1 : I model. We can see from the results that although there are two binding sites in one mAb molecule, TNF reacts with each site in an independent and noncooperative manner.

Study of electron transfer across the liquid/ice-like matrix interface by scanning electrochemical microscopy

In this work, we report the findings of a study on scanning electrochemical microscopy (SECM) to investigate the interfacial electron-transfer (ET) reaction between the 7,7,8,8-tetracyanoquinodimethane radical anion (TCNQ(.-)) in 1,2-dichloroethane and ferricyanide in an ice-like matrix (a mixture of insulting ice and conductive liquid) under low temperatures. Experimental results indicate that the formed liquid/ice-like matrix interface is superficially similar in electrochemical characteristics to a liquid/liquid interface at temperatures above -20 degreesC. Furthermore, imaging data show that the surface of the ice-like matrix is microscopically flat and physically stable and can be applied as either a conductive or an insulting substrate for SECM studies. Perchlorate ion was selected as the common ion in both phases, the concentrations of which controlled the interfacial potential difference. The effect of perchlorate concentration in the DCE phase on interfacial reactions has been studied in detail. The apparent heterogeneous rate constants for TCNQ(.-) oxidation by Fe(CN)(6)(3-) in another phase under different temperatures have been calculated by a best-fit analysis, where the experimental approach curves are compared with the theoretically derived relationships. Reaction rate data obey Butler-Volmer formulation before and after the freezing point, which is similar to most other known cases of ET reactions at liquid/liquid interfaces. However, there is a sharp change observed for heterogeneous rate constants around the freezing point of the aqueous phase, which reflects the phase transition. At temperatures below -20 degreesC, surface-confined voltammograms for the reduction of ferricyanide were obtained, and the ice-like matrix became an insulating one, which indicates that the aqueous phase is really a frozen phase.

Kinetics of cerium(IV) extraction from H2SO4-HF medium with Cyanex 923

Studies of the extraction kinetics of cerium(IV) from H2SO4-HF solutions with Cyanex 923 in n-heptane have been carried out using a constant interfacial area 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 results were compared with those of the system without HF. It was concluded that the addition of HF reduces the activation energy for the forward rate from 46.2 to 36.5 U mol(-1) while it has an opposite effect on the activation energy for the reverse process(the activation energy increased from 23.3 to 90.8 U mol(-1)). Thus, HF can accelerate the rate of cerium(IV) extraction. At the same time, the extraction rate is controlled by a mixed chemical reaction-diffusion rather than by a chemical reaction alone. A rate equation has also been obtained.

Study on the kinetics of ferrocene derivatives in polymer electrolyte/electrode interface at microelectrode

Heterogeneous electron transfer rate constants (k(s)) and diffusion coefficients (D) of the ferrocene and its derivatives. in a new synthetic comb polymer solvent, poly(dimethylsiloxane-g-monomethylether polyethylene glycol) (SCP), and several other polymer solvents were estimated by using microelectrodes. Also, the influence of various supporting electrolytes on k(s) and D of ferrocene was studied. It was shown that k(s) and D of ferrocene decreased with increasing anionic size of the supporting electrolyte, but k(s) tended to increase with increasing radius of the solvated cation. Also, the cationic size of the supporting electrolytes had little effects on D. The values of k(s) and D for the ferrocene derivatives in the polymer solvents were in sharp contrast to those in monomeric solvents. Thus. the k(s) values were proportional to D in the polymer solvents. which indicates that solvent dynamics control of the electrode reaction. The values of k(s) and D of ferrocene in SCP were larger than those in other polymer solvents indicating that SCP is a good polymer solvent. (C) 2000 Elsevier Science B.V. All rights reserved.

Rare earth separation with 1-hexyl-4-ethyloctyl isopropylphosphonic acid extractant

A new extractant 1-hexyl-4-ethyloctyl isopropylphosphonic acid (HHEOIPP or HA) in heptane was employed to extract rare earths from hydrochloric acid medium. The dependence of extraction distribution ratio on equilibrium aqueous pH and the concentration of extractant were investigated. On the basis of slope analysis,it was proposed that two different kinds of extracted species were formed. For rare earth elements (La similar to Ho) the extracted species was LnA(3)(HA)(3) and for heavy rare earth elements (Er similar to Lu) the species was LnClA(2)(HA)(3). The steric hindrance plays an important role in forming the species. The extraction constants and separation factors of the adjacent rare earths were calculated too. Compared with HDEHP and HEH/EHP, HHEOIPP is a valuable extractant with high separation selectivity. The "tetrad effect" between K-ex and atomic number was observed.

Kinetics separation of copper and palladium by sodium hydroxide precipitation and its analytical application

The method of the kinetics separation of copper and palladium by sodium hydroxide precipitation was described. The reaction orders, apparent rate constants, apparent activation energy of the reactions between sodium hydroxide and copper, and palladium were determined, and the introduced error for the determination of palladium with separating copper and-palladium by sodium hydroxide precipitation was calculated, The proposed method has been applied to determine palladium in the aldehyde catalyst with good result.

Organic-phase enzyme electrode for phenolic determination based on a functionalized sol-gel composite

An amperometric biosensor for monitoring phenols in the organic phase was constructed by the silica sol-gel immobilization of tyrosinase on a glassy carbon electrode. The organic-inorganic hybrid materials with different sol-gel precursors and polymers were optimized, and the experimental conditions, such as the effect of the solvent, operational potential and enzyme loading were explored for the optimum analytical performance of the enzyme electrode. The biosensor can reach 95% of steady-state current in about 18 s, and the trend in the sensitivity of different phenols is as follows: catechol > phenol >p-cresol. In addition, the apparent Michaelis-Menten constants (K-m(app)) and the stability of the enzyme electrode were discussed. (C) 2000 Elsevier Science S.A. All rights reserved.

Enzymatic and kinetic properties of selenium-containing catalytic antibody with cGPX activity

Three selenium-containing catalytic antibodies mHB4, mHB5 and mHB7 which acted as mimics of cytosolic glutathione peroxidase(cGPX), were prepared by chemically introducing selenium into monoclonal antibodies HB4, HB5 and HB7. HB4. HB5 and HB7 were raised against a GSH derivative GSH-S-DNP dibenzyl ester, The cGPX activity of mHB4, mHB5, mHB7 were 170, 1 867, 32 U/mu mol, respectively. The cGPX activity of mHB5 was 0, 32 fold of natural rabbit liver cGPX and 1. 51 fold of m4A4. About two atoms of selenium existed in each of mHB5 molecule determined by inductively-coupled plasma/mass spectroscopy (ICP-MS), The optimal activity of mHB5 was at between pH 8. 4 and 8, 8, The reaction catalyzed by mHB5 involved a Ping-Pong mechanism. At pH 7. 0 and 37 degreesC, the apparent second-order rate constants for reaction of mHB5 with H2O2 and t-ROOH were as followed: k(+1) (H2O2) = 9. 71 x 10(6) L/(mol min), k(+1)(t-ROOH) = 5. 99 x 10(5) L/(mol.min). Rate accelerations (k(cat)/K-m/k(uncat)) 9. 8 x 10(6) and 3.7 x 10(5) fold those of the uncatalytic reaction were observed.

Preparation and characteristics of polyimide-TiO2 nanocomposite film

A sol-gel approach has been developed to prepare polyimide-TiO2, hybrid films fi om soluble polyimides and a modified titanium precursor. The rate of the hydrolysis reaction of titanium alkoxide can be controlled by using acetic acid as a modifier. FTIR and XPS indicated that TiO2, particles were well distributed in polyimide matrixes with particle size small per than 60 nm. Polyimide hybrid films having the TiO2, component less than or equal to 10% exhibited high thermal stability, high optical transparency and good mechanical properties and possessed higher dielectric constants than correspondingly polyimides. (C) 2000 Society of Chemical Industry.

Species of rare earth (III), calcium (II) and zinc (II) in the presence of L-histidine and L-typtophane

Rare earth(III)-histidine (His)- tryptophane (Trp). Ca(II)-His-Trp and Zn(II)-His-Trp systems were studied by potentiometric titration and computer simulation under physiological conditions. The species of the systems and their stability constants were determined. The distributions of species of rare earth(III), Ca(II) and Zn(II) were discussed.

Electrocatalytic reduction of O-2 and H2O2 at the glass carbon electrode modified with microperoxidase-11

Electrocatalytic reduction of O-2 and H2O2 at the glass carbon electrode modified with microperoxidase-11 immobilized with Nafion film has been studied by means of cyclic voltammetry and rotating disk electrode techniques. The modified electrode shows high catalytic activity toward the reduction of both O-2 and H2O2. The rate constants of Oz and H2O2 reduction at the modified electrode have been measured and compared. It is found that O-2 undergoes a four-electron reduction at the modified electrode and the catalytic activity for the reduction of O-2 is dependent on the pH of the solutions.