120 resultados para LIQUID LIQUID INTERFACES
Resumo:
The electrochemical behavior of ionizable drugs (Amitriptyline, Diphenhydramine and Trihexyphenedyl) at the water/1,2-dichloroethane interface with the phase volume ratio (r = V-o/V-w) equal to 1 are investigated by cyclic voltammetry. The system is composed of an aqueous droplet supported at an Ag/AgCl disk electrode and it was covered with an organic solution. In this manner, a conventional three-electrode potentiostat can be used to study the ionizable drugs transfer process at a liquid/liquid interface. Physicochemical parameters such as the formal transfer potential, the Gibbs energy of transfer and the standard partition coefficients of the ionized forms of these drugs can be evaluated from cyclic voltammograms obtained. The obtained results have been summarized in ionic partition diagrams, which are a useful tool for predicting and interpreting the transfer mechanisms of ionizable drugs at the liquid/liquid interfaces and biological membranes.
Resumo:
A droplet of aqueous solution containing a certain molar ratio of redox couple is first attached onto a platinum electrode surface, then the resulting drop electrode is immersed into the organic solution containing very hydrophobic electrolyte. Combined with reference and counter electrodes, a classical three-electrode system has been constructed, Ion transfer (IT) and electron transfer (ET) are investigated systematically using three-electrode voltammetry. Potassium ion transfer and electron transfer between potassium ferricyanide in the aqueous phase and ferrocene in nitrobenzene are observed with potassium ferricyanide/potassium ferrocyanide as the redox couple. Meanwhile, the transfer reactions of lithium, sodium, potassium, proton and ammonium ions are obtained with ferric sulfate/ferrous sulfate as the redox couple. The formal transfer potentials and the standard Gibbs transfer energy of these ions are evaluated and consistent with the results obtained by a four-electrode system and other methods.
Resumo:
A study of potassium ion transfer across a water \ 1,2-dichloroethane (W \ DCE) interface facilitated by dibenzo-18-crown-6 (DB18C6) with various phase volume ratio systems is presented. The key point was that a droplet of aqueous solution containing a redox couple, Fe(CN)(6)(3-)/Fe(CN)(6)(4-), with equal molar ratio, was first attached to a platinum electrode surface, and the resulting droplet electrode was then immersed into the organic solution containing a hydrophobic electrolyte to construct a platinum electrode/aqueous phase/organic phase system. The interfacial potential of the W \ DCE within the series could be externally controlled because the specific compositions in the aqueous droplet make the Pt electrode function like a reference electrode as long as the concentration ratio of Fe(CN)(6)(3-)/Fe(CN)(6)(4-) remains constant. In this way, a conventional three-electrode potentiostat can be used to study the ion transfer process at a liquid \ liquid (L \ L) interface facilitated by an ionophore with variable phase volume ratio (r = V-o/V-w). The effect of r on ion transfer and facilitated ion transfer was studied in detail experimentally. We also demonstrated that as low as 5 x 10(-8) M DB18C6 could be determined using this method due to the effect of the high phase volume ratio.
Resumo:
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.
Resumo:
Facilitated proton transfer across the water/1,2-dichloroethane (DCE) interface supported on the tips of micro- and nano-pipets by o-phenanthroline (Phen) was studied by using cyclic voltammetry. The formed micro- and nano-liquid/liquid interfaces functioned as micro- and nano-electrodes under certain experimental conditions. The dependence of the half-wave potentials on the aqueous solutions acidities was studied and the ratio of association constants between Phen and proton in the aqueous and DCE phases was calculated by the method proposed by Matsuda et al.. The standard rate constant (k(0)) and the transfer coefficient (alpha) evaluated by using nano-pipets were equal to 0.183 +/- 0.054 cm/s and 0.70 +/- 0.09, respectively.
Resumo:
In this paper, we studied the reactions of both potassium ferricyanide and hexaammineruthenium(III) chloride at a 4-aminobenzoic acid (4-ABA) modified glassy carbon electrode (GCE) by scanning electrochemical microscopy (SECM) in different pH solutions. The surface of the modified electrode has carboxyl groups, the dissociation of which are strongly dependent upon the solution pH values. The rate constant kb of the oxidation of ferrocyanide on the modified electrode can be obtained by fitting the experimental tip current-distance (I-T-d) curves with the theoretical values. The surface pK(a) of the 4-ABA modified GCE was estimated from the plot of standard rate constant k(o) versus the solution pH and is equal to 3.2, which is in good agreement with the reported result. The SECM approach curves for Ru(NH3)(6)(3+) both on the bare and the modified electrodes show similar diffusion control processes. These results can be explained by the electrostatic interactions between the modified electrode surface and the model compounds with different charges. (C) 2001 Elsevier Science BN. All rights reserved.
Resumo:
In this paper, we describe a simple procedure to make agar-gel microelectrodes by filling micropipettes. These microelectrodes were used to study K+ transfer across the agar-water \ 1,2-dichloroethane interface facilitated by dibenzo-18-crown-6 (DB18C6), and the transfer of tetraethylammonium (TEA(+)). The results observed were similar to those obtained at micro-liquid \ liquid interfaces. The effect of various amounts of agar in the aqueous phase was optimized and 3% agar was chosen based on the potential window and solidification time. The different shapes of micro-agar-gel electrodes were prepared in a similar way. The fabricated agar-gel microelectrodes obey the classical micro-disk steady-state current equation, which is different from the behavior of a normal micropipette filled with aqueous solution without silanization. (C) 2001 Elsevier Science B.V. All rights reserved.
Resumo:
Surfactant adsorption on metal surfaces has been used to limit the activity of the electrode surface and to stabilize colloidal clusters and nanoparticles in solution, but the adsorption and relative potential-induced structure change of the surfactant were not known. Here, the adsorption of sodium dodecyl sulfate (SDS) on a Au(111) surface under potential control was investigated by in situ scanning tunneling microscopy (STM). The STM images showed that the morphology of SDS on Au(111) was changed from a hemi-cylindrical micellar monolayer to a compact and uniform bilayer through control of the potential. The transition between the hemimicellar monolayer and the compact bilayer is not reversed after a period of time. The model of potential-induced transformation for SDS aggregates on Au(111) was established. (C) 2001 Elsevier Science B.V. All rights reserved.
Resumo:
A computational simulation is conducted to investigate the influence of Rayleigh-Taylor instability on liquid propellant reorientation flow dynamics for the tank of CZ-3A launch vehicle series fuel tanks in a low-gravity environment. The volume-of-fluid (VOF) method is used to simulate the free surface flow of gas-liquid. The process of the liquid propellant reorientation started from initially flat and curved interfaces are numerically studied. These two different initial conditions of the gas-liquid interface result in two modes of liquid flow. It is found that the Rayleigh-Taylor instability can be reduced evidently at the initial gas-liquid interface with a high curve during the process of liquid reorientation in a low-gravity environment.
Resumo:
The H+, Li+, Na+, K+, Mg2+, Ca2+ and Ba2+ ion transfer across the water/nitrobenzene (NB) and water/1,2-dichloroethane (DCE) interfaces, facilitated by the ionophore ETH157, has been investigated by cyclic voltammetry (CV). The mechanism of the transfer process has been discussed, and the diffusion coefficients and the stability constants of the complexes formed in the nitrobenzene phase have been determined.
Resumo:
The transfer behavior of alkali motal ions K~+ and Na~+ across the interfaces of water/nitrobenzene and water/1, 2-dichloroethane facilitated by Triton X-100 is investigated by cyclic voltammetry with four electrodes. The equations of interfacial half-wave potential derived in terms of the mechanism proposed isverified by the experimental data and consistent with the practical △_0~wφ_p-pM curves.
Resumo:
1999年,在我国实践5号卫星上完成了两层流体空间实验,实验研究两层不相混合流体的纯Marangoni对流(温度梯度与界面垂直)与热毛细对流(温度梯度方向与流体界面平行).前者存在发生Marangoni对流的最小临界温差值△Tc,低于该值流体系统处于静止状态;后者中只要存在沿界面的温度梯度便会产生热毛细对流.空间实验采用石蜡和氟化液两层流体新体系,实现了平整的液-液交界面,并从卫星上传回上万幅数字图像.通过多幅图像叠加处理得到了定量的流速场.数值模拟计算分析了相应工况时对流流动的速度场,两者的流场结构和速度大小基本一致,实验验证了理论模型.
Resumo:
III-V pentenary semiconductor AlGaInPAs with a direct band gap of up to 2.0 eV has been grown successfully on GaAs substrates by liquid phase epitaxy;(LPE). With the introduction of the energy bowing parameters of quaternaries, the theoretical calculations agree well with the measured PL peak energy data from pentenary samples.
Resumo:
The Electrical Resistance Tomography (ERT) technique possesses great potential in monitoring widely exiting industrial two/multi-phase flow. For vertical pipe flow and inclined pipe flow, some application studies with exciting results have been reported, but there is rarely a paper regarding the application of ERT to horizontal gas/liquid pipe flow. This paper addresses this issue and proposes a smart method, Liquid Level Detection method, to conventional ERT system. The enhanced ERT system using the new method can monitor horizontal pipe flow effectively and its application is no longer restricted by the flow conditions. Some experimental results from monitoring an air/water slug pipe flow are presented.