The role of the solvent in equilibrium and kinetic aspects of metal chelate extractions

Equilibria and kinetics for the extraction of nickel(II) and copper(II) by 2-hydroxy-5-nonylbenzophenone oxime (LIX 65N) in seven organic solvent systems were studied in order to test the validity of several hypotheses related to the role of the solvent in equilibrium and kinetic aspects of metal chelate extraction. For the nickel—LIX 65N system, the extraction constant is essentially independent of the solvent system, whereas for the copper—LIX 65N system, the extraction constant is not independent of solvent; this indicates that while the stoichiometry of the nickel chelate remains the same in all solvents, that of copper does not. The observed rate constant for the nickel—LIX 65N extraction was found to vary inversely with the LIX 65N distribution constant as predicted from a mechanism involving slow formation of the 1:1 complex. The observed reaction rate constant for the copper—LIX 65N varied inversely with the square of the distribution constant, also in accordance with the previously postulated mechanism of the slow formation of the 2:1 copper complex. This study, therefore, unequivocally eliminates the interfacial mechanism in favor of the homogeneous chemical reaction mechanism for the extraction of metal ions by LIX 65N, as well as by other similar high-molecular-weight extractants.     

Kinetics Study on Oxidation of β‐Isophorone Using Molecular Oxygen

The oxidation kinetics of β‐isophorone (β‐IP) using molecular oxygen catalyzed by iron(III) acetylacetonate was investigated in a lab‐scale agitator bubbling reactor. β‐IP was found to give keto‐isophorone (KIP) and 4‐hydroxy‐3,5,5‐trimethyl‐2‐cyclohexen‐1‐one (HIP) along with little isomerization product α‐isophorone (α‐IP). The results show that the oxidation reaction took place in the pseudo–first‐order fast reaction regime. The experiment was conducted under the mass transfer reaction regime as the mass transfer resistances could not be easily eliminated. The intrinsic kinetics was obtained through apparent kinetics. The activation energy of oxidation of β‐IP to KIP is 70.5 ± 4.1 kJ mol^–1, and the value of ln A_KIP is 33.53 ± 1.22. Meanwhile, the activation energy of oxidation of β‐IP to HIP is 86.4 ± 5.4 kJ mol^–1 and the value of ln A_HIP is 36.23 ± 1.52, which could provide theoretical basis for industrial design, amplification of reactor, and the optimization of reaction.     

Performance Evaluation of Nickel Separation and Extraction Process from Simulated Spent Cr/Ni Electroplating Bath Solutions by ELM Process Using LIX63 and PC88A

The study was conducted to investigate synergistic extraction of nickel from simulated spent Cr–Ni electroplating bath solutions by emulsion liquid membrane (ELM) process using 5,8-diethyl-7-hydroxydodecan-6-one oxime (LIX 63) and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (PC88A) as carriers. The importance of ELM composition and the properties of simulated spent electroplating bath solution have been optimized to synergistically extract nickel. The important parameters affecting the nickel extraction efficiency and ELM stability, such as acid concentration, stripping solution type and concentration, extractant concentration, surfactant concentration, and phase ratio, were experimentally studied. Along with obtained results, higher than 99% of nickel was selectively extracted within 30 minutes from simulated electroplating bath solutions that their metal concentrations was in the range of 100–500 mg/L. in the optimum conditions. The higher separation factor value of nickel over chromium (β_Ni/Cr) was obtained as 898. As a result, the nickel extraction kinetic was found to depend on PC88A, since extraction mechanism of PC88A is slower than that of LIX63. So, the combined use of LIX63 and PC88A improved the selective extraction of nickel in that process.     

Evidence of a Kinetic Isotope Effect in Nanoaluminum and Water Combustion

The normally innocuous combination of aluminum and water becomes violently reactive on the nanoscale. Research in the field of the combustion of nanoparticulate aluminum has important implications in the design of molecular aluminum clusters, hydrogen storage systems, as well as energetic formulations which could use extraterrestrial water for space propulsion. However, the mechanism that controls the reaction speed is poorly understood. While current models for micron‐sized aluminum water combustion reactions place heavy emphasis on diffusional limitations, as reaction scales become commensurate with diffusion lengths (approaching the nanoscale) reaction rates have long been suspected to depend on chemical kinetics, but have never been definitely measured. The combustion analysis of nanoparticulate aluminum with H₂O or D₂O is presented. Different reaction rates resulting from the kinetic isotope effect are observed. The current study presents the first‐ever observed kinetic isotope effect in a metal combustion reaction and verifies that chemical reaction kinetics play a major role in determining the global burning rate.     

A distributed parameter diffusion-reaction model for the alcoholic fermentation process

A distributed parameter model is developed for the yeast floc in the alcoholic fermentation process. The model takes into consideration the external mass transfer resistances, the mass transfer resistance through the cellular membrane, and the diffusion resistances inside the floc. The two-point boundary value differential equations for the membrane are manipulated analytically, whereas the nonlinear twopoint boundary value differential equations of diffusion and reaction inside the floc have been approximated using the orthogonal collocation technique. The evaluation of the necessary diffusion coefficients have involved a relatively large number of assumptions because of the present limited knowledge regarding the complex process of diffusion and biochemical reactions in these systems.     

Particle size limitations due to heat transfer in determining pyrolysis kinetics of biomass

A simplified heat transfer model is analyzed in order to determine an upper bound for biomass particle size in conducting experimental pyrolysis kinetics. In determining intrinsic kinetic rates, it is desirable that the entire particle be at reactor temperature for the duration of the chemical reaction. By comparing characteristic times for reaction rates versus heat-up rates, an approximate boundary for particle size can be constructed as a function of temperature; above this boundary, the reaction rate is strongly heat transfer dominated, and below the boundary the reaction rate is kinetically controlled. Using parameters for cellulose pyrolysis, it is estimated that a 200 μm particle will be heat transfer limited due to internal heat transfer at temperatures above 500°C. This boundary applies for conditions where the surface of the particle is brought to reactor temperature instantaneously. Using our specific experimental conditions, it is found that the limitations imposed by external transfer are reached before those predicted by assuming that only internal heat transfer is limiting. In examining wood pyrolysis, where a global reaction rate approximation is insufficient, it is experimentally shown that the decomposition for hemicellulose can be transport limited, while cellulose remains in the kinetic controlled regime.     

Determination of the mass transfer coefficients in direct immersion solid‐phase microextraction

Diffusion of the analytes across the diffusion boundary layers and subsequently through the fiber coatings determines the extraction kinetics of solid‐phase microextraction in aqueous matrices. Besides, the matrix effects can distort the behaviors of the analytes transferring across the diffusion boundary layers. However, these processes were always studied via certain simplification, which often left the mass transfer through the fiber coatings unconsidered and the matrix effects partially investigated. Herein, a comprehensive study on the mass transfer processes in direct immersion solid‐phase microextraction was presented. Under different agitation speeds, it was determined that the mass transfer coefficients across the diffusion boundary layers were three to six orders larger than those through the fiber coatings. However, the mass transfer across the diffusion boundary layers was generally the major rate‐limiting step. In addition, the shuttle effect and the barrier effect, which were responsible for accelerating and retarding the extraction kinetics, respectively, were found to be the dominant matrix effect alternately under different agitation speeds. This study comprehensively illustrated the major rate‐limiting step and the dominant matrix effects through recording the mass transfer coefficients.     

Development of Kinetic Mechanism for the Esterification of Acrylic Acid with Hexanol Catalyzed by Ion‐Exchange Resin

The heterogeneous esterification reaction of acrylic acid with hexanol over three different cation‐exchange resins, Amberlyst 131, Amberlyst 15, and Dowex 50Wx‐400, was investigated. Surface area, pore volume, average pore diameter, and acid capacity analyses were carried out for these three catalysts. Amberlyst 131 gave the highest conversion, and therefore, further experiments were performed catalyzed by Amberlyst 131. The absence of external and internal mass transfer resistances was investigated for the esterification of acrylic acid with hexanol. Experiments showed that the reaction is controlled by chemical step rather than external and internal mass transfer steps. The effects of temperature, catalyst loading, and alcohol to acid molar ratio on the conversion of acrylic acid were determined. The activation energy and kinetic and adsorption constants were determined according to the Langmuir–Hinshelwood–Hougen–Watson mechanism.     

Modelling SPME data from kinetic measurements in complex samples

The kinetics of the partition process to solid phase microextraction fibres is often modelled using a stagnant layer model. Despite its usefulness, in some agitation systems such a model cannot be applied because the stagnant layer cannot be characterized precisely. Therefore, in this present study an alternative approach is introduced. Transport from the bulk medium to the fibre coating is simply modelled by a finite mass transfer coefficient instead of diffusion through a stagnant water layer surrounding the fibre. Intra-fibre transport is described by non-steady diffusion. The model is aimed at the analysis of SPME measurements in the kinetic phase for samples including a binding matrix. It was validated with experimental results of SPME measurements concerning the absorption kinetics of [(3)H]estradiol at different concentrations of bovine serum albumin (BSA) as a chemical binding matrix. The model provides excellent fits of the experimental data, resulting in an association constant (K(a)) of estradiol for BSA of 5.66 x 10(4) M(-1), which is similar to literature values and a fibre coating/bulk medium partition coefficient of 5.0 x 10(3). The kinetics of extraction were studied with the model, showing that the rate-limiting step in the extraction process was the diffusion in the fibre. This finding rules out the possibility that the presence of the matrix itself in the diffusion layer affects the kinetics of estradiol uptake into the SPME fibre.     

Modeling equilibrium and kinetics of metal uptake by algal biomass in continuous stirred and packed bed adsorbers

Physical and chemical characterization of algae Gelidium particles shows a gel structure, with two major binding groups, carboxylic and hydroxyl groups, with an affinity constant distribution for protons, well described by a Quasi-Gaussian distribution suggested by Sips. A continuous model, considering a heterogeneous distribution of the carboxylic groups, determined by potentiometric titration experiments, was able to predict equilibrium data at different pH. The metal uptake capacity decreases with the solution pH, suggesting that competition exists between hydrogen ions, present in high concentrations for low pH values, and metal ions. For high ionic strengths, adsorption sites will be surrounded by counter ions and partially lose their charge, which weakens the contribution of the electrostatic binding and decreases the overall adsorption. A small influence of the temperature in the adsorption process was observed. Batch kinetic experiments were also performed, at different pH values, and results were well fitted by a mass transfer model, considering the intraparticle diffusion resistance given by the linear driving force model (LDF). Continuous stirred adsorber (CSTA) and packed bed column configurations were also tested for metal adsorption. The biosorbent regeneration was achieved by contacting it with strong acid (0.1 M HNO₃). A mass transfer model was applied with success to describe the biosorption/desorption process in CSTA and packed bed column, considering the equilibrium given by the Langmuir equation/mass action law and film and intraparticle diffusion resistances.     

Decoupling Study of Melt Polycondensation of Polycarbonate: Experimental and Modeling of Reaction Kinetics and Mass Transfer in Thin Films Polycondensation Process

During the melt polycondensation process of polycarbonate, reaction and mass transfer are deeply coupled owing to relatively high melt viscosity. In this work, the polycondensation reaction kinetics and mass transfer behavior of volatile phenol are decoupling studied in detail by using thin‐film experiments with 250–280 °C, 10–1000 Pa and 0.085–0.68 mm film thickness. A realistic apparent rate model coupled the reaction kinetics with thermodynamic equilibrium and diffusion behavior is developed to describe the polycondensation process, while the diffusion characteristic of small molecule (phenol) is further obtained based on penetration theory. The obtained polycondensation equilibrium constant ranges from 0.3 to 0.55, while the activation energy and pre‐exponential factor of temperature‐dependent diffusion coefficients of phenol are 87.9 kJ mol⁻¹ and 5.08 × 10² m² s⁻¹, respectively. It is also observed that the overall apparent rate of polycarbonate (PC) polycondensation process increases with higher temperature, lower pressure, and thinner film thickness. Coupling the reaction kinetics with mass transfer, the predictions of the realistic apparent rate model are in quite satisfactory agreement with experimental data.     

稀释剂极性对萃取动力学的影响 I: HEHEHP萃取Fe(Ⅲ)

考察了正辛烷等六种常用稀释剂中2-乙基己基膦酸单2-乙基己基酯从硝酸介质中萃取Fe(Ⅲ)的动力学行为。观察到稀释剂的极性不仅影响萃取速率的大小,而且会引起萃取过程控制模式的改变, 即随着稀释剂极性的增加, 萃取过程由界面化学反应和水相化学反应共同控制模式向单一的界面化学反应控制模式转变。     

Polychronous kinetics with diffusion over the reaction state spectrum

The unsteady- and steady-state kinetics of a polychronous first-order reaction with discrete and continuous state distributions under spectral diffusion conditions are considered. An analysis of the model has demonstrated that a quasi-steady-state regime is established in the course of the reaction. In this regime, the shape of the distribution function stops changing and the reaction kinetics obeys an exponential law and can be characterized by a single, average rate constant. Equations are set up for the reaction state distribution and average rate constant in the quasi-steady-state regime. The limits of the kinetic and quasi-steady-state regimes are determined as a function of the spectral diffusion coefficient. The unsteady-state kinetics and the quasi-steady state time depend strongly on the initial state distribution.     

Solvent extraction of Ni(II) from sulfate solutions with LIX 84I: flow-sheet for the separation of Cu(II), Ni(II) and Zn(II).

This paper reports on solvent-extraction studies of Ni(II) from sulfate solutions with LIX 84I (2-hydroxy-5-nonylacetophenoneoxime) as the extractant. The extraction of metal depends on the equilibrium pH of the aqueous phase and the extractant concentration. The transfer of metal follows a cation exchange-type mechanism: Ni2+ + 2HA --> NiA2 + 2H+. Extraction varies with the nature of the diluents. Temperature has no effect on the extraction of metal. The extraction behavior of associated metals clearly demonstrates the application of LIX 84I as the extractant for the separation of Cu(II), Ni(II) and Zn(II). Based on the results, a flow sheet of the process was developed.     

Monte Carlo simulations of the exchange kinetics of polymers adsorbed on a solid surface

The exchange kinetics of polymers adsorbing on a solid surface is extensively studied by dynamic Monte Carlo simulations. A model employed simulates a semidilute polymer solution placed in contact with a solid surface that attracts polymer segments by the adsorption interaction (χ_s). The exchange process of polymer chains, between the solution and the adsorbed polymer layer, is examined under various conditions. The exchange kinetics shows two characteristic regimes with increasing chain length. One is the diffusion‐controlled regime found with a small χ_s , and the other the detachment‐controlled regime with a large χ_s . These two regimes are well described by a kinetic theory. Various dynamic quantities show that the diffusion‐controlled regime is not due to sluggish dynamics near the surface, but rather to bulk diffusion of chains. The diffusion‐controlled regime found in this study is considered to appear at the high temperature limit.     

Novel Collimated Beam Setup to Study the Kinetics of VUV‐Induced Reactions

Vacuum UV (VUV) process is an incipient advanced oxidation process, which can be used for water treatment. This process relies on the formation of hydroxyl radicals through the VUV‐induced photolysis of water. In particular, the use of ozone‐generating mercury vapor lamps, which emit 10% of the radiation at 185 nm and 90% at 254 nm, is showing very promising results for the degradation of micropollutants. The kinetics of VUV process has been studied in batch‐ and flow‐through reactors, but the effect of 254 and 185 nm photons cannot be isolated, mass transfer resistances can take place and the interpretation of the results is complex. In this technical note, a new VUV collimated beam to conduct kinetic tests is presented, which offers several advantages: (1) it allows the irradiation of samples with 185, 254 nm photons, or both, (2) the concentration of reagents is uniform in the reaction volume and (3) it allows to change the fluence rate by changing the distance between the lamp and the photoreactor. Details of the geometry are presented, as well as an analysis of the collimation and uniformity of the radiation of the new VUV‐collimated beam setup.     

Development and validation of HPLC‐MS/MS method for the determination of lixivaptan in mouse plasma and its application in a pharmacokinetic study

The aim of the present study was to develop a simple, sensitive and accurate liquid chromatography–electrospray ionization tandem mass spectrometry (ESI‐MS/MS) method for the determination of lixivaptan (LIX) in mouse plasma using vildagliptin as the internal standard (IS). A precipitation procedure was used for the extraction of LIX and vildagliptin from mouse plasma. Chromatographic separation of LIX was achieved using a C₁₈ analytical column (50 × 2.1 mm, 1.8 μm) at 25°C. The mobile phase comprised acetonitrile and ammonium formate (10 mm , pH 3.1; 40:60, v /v) pumped at a flow rate of 0.3 mL min⁻¹. A tandem mass spectrometer with an electrospray ionization source was used to perform the assay. Quantification of LIX at m/z 290 → 137 and IS at 154 → 97 was attained through multiple reaction monitoring. The investigated method was authenticated following the bio‐analytical method of validation guidelines of the US Food and Drug Administration. The developed method showed a good linearity over the concentration range from 5 to 500 ng mL⁻¹, and the calibration curve was linear (r = 0.9998). The mean recovery of LIX from mouse plasma was 99.2 ± 0.68%. All validation parameters for LIX were within the levels required for acceptance. The proposed method was effectively used for a pharmacokinetic study of LIX in mouse plasma.     

抗坏血酸在普鲁士蓝薄膜修饰电极上的电催化氧化

本文详细研究了普鲁士蓝(PB)薄膜本身电荷传输过程的动力学及PB 薄膜催化抗坏血酸(AH2)电氧化的动力学。 用电位阶跃计时电流法和计时电量法, 恒电流计时电位法测得PB膜中电荷传输表观扩散系数Dct平均为2.62×10ˉ10cm2·sˉ1; 用RDE法测得AH2在PB薄膜上催化氧化的速率常数为1.23×10^8cm3·molˉ1·sˉ1。催化反应对AH2为一级。 只发生在PB薄膜与溶液的界面上。 整个催化过程受到溶液中的传质、膜内部的电荷传输及膜与溶液界面上交叉反应三种因素单独或联合控制, 实际出现四种动力学情况。     

On the origin of Turing instability

A reaction–diffusion system consisting of one, two or three chemical species and taking place in an arbitrary number of spatial dimensions cannot exhibit Turing instability if none of the reaction steps express cross‐inhibition. A corollary of this result – obtained by elementary calculations – underlines the importance of nonlinearity in the formation of stationary structures, a kind of self‐organization on a chemical basis. Relations to global stability of reaction–diffusion systems, and results on multispecies systems are also mentioned. The statements are not restricted to mass action type models. As a by‐product, the solution of a basic inverse problem of formal kinetics is also presented which extends a previous result by Hárs and Tóth (1981) to models with arbitrary – including rational – functions as reaction rates so often occurring, e.g., in enzyme kinetics.     

Pneumatochemical impedance spectroscopy. 2. Dynamics of hydrogen sorption by metals

In this paper, pneumatochemical impedance spectroscopy is used to analyze multistep reaction mechanisms such as those observed in solid solution domains of LaNi5-H2(g) systems. It is shown that hydrogen sorption is a two-step mechanism including (i) dissociative surface chemisorption of molecular hydrogen and (ii) atomic hydrogen bulk transport by diffusion. Data fitting of experimental transfer functions with model equations yields the value of the kinetic parameter associated with each individual reaction step, i.e., surface sorption resistances and hydrogen bulk diffusion coefficients. The technique is used to follow the activation procedure of the sample as well as the degradation of sorption properties in oxygen-containing hydrogen atmospheres. A decrease in sorption kinetics is attributed to surface oxidation, whereas bulk properties remain unchanged. The perspectives offered by the technique which potentially can be used to optimize surface and bulk composition of IMC for increased sorption rates are discussed.