Electrochemical recognition of alkali metal ions at the micro-water 1,2-dichloroethane interface using a calix[4]arene derivative

In this paper, a calix[4]arene derivative, 5,11,17,23-butyl-25,26,27,28-tetra-(ethanoxycarbonyl)-methoxy-calix[4]arene (L), is investigated as a host to recognize alkali metal ions (Li+, Na+, K+, Rb+ and Cs+) at the interface between two immiscible electrolyte solutions (ITIES). Well-defined cyclic voltammograms are obtained at the micro- and nano-water \ 1,2-dichloroethane (W \ DCE) interfaces supported at micro- and nano-pipets.

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.

Surface-induced melting of metal nanoclusters

We investigate the size effect on melting of metal nanoclusters by molecular dynamics simulation and thermo dynamic theory based on Kofman's melt model. By the minimization of the free energy of metal nanoclusters with respect to the thickness of the surface liquid layer, it has been found that the nanoclusters of the same metal have the same premelting temperature T-pre = T-0 - T-0(gamma(su) - gamma(lv) - gamma(sl))/(rhoLxi) (T-0 is the melting point of bulk metal, gamma(sv) the solid-vapour interfacial free energy, gamma(sl) the liquid-vapour interfacial free energy, gamma(sl),l the solid-liquid interfacial free energy, p the density of metal, L the latent heat of bulk metal, and xi the characteristic length of surface-interface interaction) to be independent of the size of nanoclusters, so that the characteristic length of a metal can be obtained easily by T-pre, which can be obtained by experiments or molecular dynamics (MD) simulations. The premelting temperature T-pre of Cu is obtained by AID simulations, then xi is obtained. The melting point T-cm is further predicted by free energy analysis and is in good agreement with the result of our MD simulations. We also predict the maximum premelting-liquid width of Cu nanoclusters with various sizes and the critical size, below which there is no premelting.

Influence of Rayleigh-Taylor Instability on Liquid Propellant Reorientation in a Low-Gravity Environment

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.

Determination of the interdiffusion coefficients of liquid Zn and Sn using Ta/Zn-Sn/Si trilayers

In this paper we present a new method for measuring diffusion coefficients in liquid metals under convection-less conditions with solid/liquid-liquid/solid trilayer. The advantage of this kind of trilayer is that effects from gravity-induced convection and Marangoni-convection can be omitted, so that the diffusion coefficient is determined more accurately. The Ta/Zn-Sn/Si trilayer were prepared with a multi-target ion-beam sputtering deposition technique and annealed in an electric furnace under an argon atmosphere. The interdiffusion of liquid zinc and tin at 500 degrees degree C was investigated. The diffusion concentration profiles were determined by energy dispersive spectroscopy. The interdiffusion coefficients range from 1.0x10(-6)cm(2)/s to 2.8x10(-6)cm(2)/s, which is less than previous values measured by capillary reservoir technique under 1g-environment where various convection exist. The precise interdiffusion coefficients of liquid zinc and tin result from the removing of disturbances of various kinds of convection.

Kinetic study of hydrolysis of xylan and agricultural wastes with hot liquid water

We investigated the kinetics of hot liquid water (HLW) hydrolysis over a 60-min period using a self-designed setup. The reaction was performed within the range 160-220 °C, under reaction conditions of 4.0 MPa, a 1:20 solid:liquid ratio (g/mL), at 500 rpm stirring speed. Xylan was chosen as a model compound for hemicelluloses, and two kinds of agricultural wastes-rice straw and palm shell-were used as typical feedstocks representative of herbaceous and woody biomasses, respectively. The hydrolysis reactions for the three kinds of materials followed a first-order sequential kinetic model, and the hydrolysis activation energies were 65.58 kJ/mol for xylan, 68.76 kJ/mol for rice straw, and 95.19 kJ/mol for palm shell. The activation energies of sugar degradation were 147.21 kJ/mol for xylan, 47.08 kJ/mol for rice straw and 79.74 kJ/mol for palm shell. These differences may be due to differences in the composition and construction of the three kinds of materials. In order to reduce the decomposition of sugars, the hydrolysis time of biomasses such as rice straw and palm shell should be strictly controlled.

Determination of the interdiffusion coefficients of liquid Zn and Sn using Ta/Zn-Sn/Si trilayers

In this paper we present a new method for measuring diffusion coefficients in liquid metals under convection-less conditions with solid/liquid-liquid/solid trilayer. The advantage of this kind of trilayer is that effects from gravity-induced convection and Marangoni-convection can be omitted, so that the diffusion coefficient is determined more accurately. The Ta/Zn-Sn/Si trilayer were prepared with a multi-target ion-beam sputtering deposition technique and annealed in an electric furnace under an argon atmosphere. The interdiffusion of liquid zinc and tin at 500 degrees degree C was investigated. The diffusion concentration profiles were determined by energy dispersive spectroscopy. The interdiffusion coefficients range from 1.0x10(-6)cm(2)/s to 2.8x10(-6)cm(2)/s, which is less than previous values measured by capillary reservoir technique under 1g-environment where various convection exist. The precise interdiffusion coefficients of liquid zinc and tin result from the removing of disturbances of various kinds of convection.

Systematic study of the transfer of amino acids across the water/1,2-dichloroethane interface facilitated by dibenzo-18-crown-6

Facilitated ion transfer reactions of 20 amino acids with di.benzo-18-crown-6 (DB18C6) at the water/1,2-dichloroethane (W/DCE) interfaces supported at the tips of micro- and nano-pipets were investigated systematically using cyclic voltammetry. It was found that there were only 10 amino acids, that is, Leu, Val, Ile, Phe, Trp, Met, Ala, Gly, Cys, Gln (in brief), whose protonated forms as cations can give well-defined facilitated ion transfer voltammograms within the potential window, and the reaction pathway was proven to be consistent with the transfer by interfacial complexation/dissociation (TIC/TID) mechanisms. The association constants of DB 18C6 with different amino acids in the DCE (beta(0)), and the kinetic parameters of reaction were evaluated based on the steady-state voltammetry of micro- or nano-pipets, respectively The experimental results demonstrated that the selectivity of complexation of protonated amino acid by DB18C6 compared with that of alkali metal cations was low, which can be attributed to the vicinal effect arising from steric hindrance introduced by their side group and the steric bulk effect by lipophilic stabilization.

Studies of effect of phase volume ratio on transfer of ionizable species across the water/1,2-dichloroethane interface by a three-electrode setup

The electrochemical behavior of pyridine distribution at the water/1,2-dichloroethane interface with variable phase volume ratios (r=V-0/V-W) was investigated by cyclic voltammetry. The system was composed of an aqueous droplet supported on a Ag/AgCl disk electrode covered with an organic solution or an organic droplet supported on a Ag/AgTPBCl disk electrode covered with an aqueous solution. In this way, a conventional three-electrode potentiostat can be used to study an ionizable compound transfer process at a liquid/liquid interface with a wide range of phase volume ratios (from 0.0004 to 1 and from 1 to 2500). Using this special cell we designed, only very small volumes of both phase were needed for r equal to unity, which is very useful for the investigation of the distribution of ionizable species at a biphasic system when the available amount of species is limited. The ionic partition diagrams were obtained for different phase volume ratios.

Study of ionizable drugs transfer across the water/1,2-dichloroethane interface with phase volume ratio equal to unity using a three-electrode system

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.

Charge transfer across the water/nitrobenzene interface by three-electrode system

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.

Study of facilitated potassium ion transfer across a water vertical bar 1,2-dichloroethane interface using different phase volume ratio systems

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.

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.

Investigation of ion transfer across the micro-water/nitrobenzene interface facilitated by a fullerene derivative

A functionalized fullerene derivative containing a monoaza-18-crown-6 moiety was investigated by facilitated ion (such as Li+, Na+, K+, NH4+, Mg2+, and Ca2+) transfer across the micro-water/nitrobenzene interface supported at the tip of a micropipet. The current responses were detected by cyclic voltammetry and Osteryoung square wave voltammetry, which demonstrated that the facilitated ion transfer does occur by an interfacial complexation-dissociation process. The diffusion coefficient of this compound in nitrobenzene was approximately (5.90 +/- 0.04) x 10(-7) cm(2) s(-1), which is 1 order of magnitude less than other common ionophores due to the large size of the molecule. The selectivity of this molecule toward the metal ions followed the sequence Na+ > Li+ > K+ > NH4+ > Ca2+ similar to Mg2+. In addition, this compound was also easy to form film at the water/nitrobenzene interface to inhibit the simple ion transfer of tetramethylammonium ion. However, the adsorption of this ionophore has less influence on the facilitated metal ion transfer.

Investigation of proton transfer across the water/1,2-dichloroethane interface by o-phenanthroline using glass micro/nano-pipets and cyclic voltammetry

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.