Onset of natural convection in the electrochemical cell with horizontal electrodes under non-steady-state conditions: A numerical study

The disturbance of mechanical equilibrium of stagnant electrolyte containing three types of ions and the onset of natural convection in the electrochemical cell with plane horizontal electrodes under the non-steady-state conditions are studied theoretically. The Navier-Stokes equations in the Boussinesq approximation, the equations of ionic transfer of electrolyte components, which is caused by diffusion, convection, and migration, and the electroneutrality condition were used as the mathematical model of the process. Using the numerical simulation, the regularities of the onset of natural convection of electrolyte solution with the formation of convective cells are studied. The effect of transport properties of solution on the critical time of onset of convection and on the time before the current starts to increase due to the onset of natural convection, on the sizes and shape of convective cells and the mass-transfer rate is investigated by the example of cathodic deposition of metal at the limiting current.     

Non-Steady-State Processes Under Conditions of Natural Convection in an Electrochemical Cell with Horizontal Electrodes: The Critical Time of the Onset of a Convective Instability at Large Rayleigh Numbers

Theoretical analysis of a model electrochemical system is performed. An equation for the critical time of the onset of a convective instability and natural convection in a plane electrolyte layer between two horizontal electrodes is derived. The cessation of damping of fluctuations of the electroactive-ion concentration is taken as the condition for the onset of a convective instability.     

Effect of repulsive interactions on the rate of doublet formation of colloidal nanoparticles in the presence of convective transport

In this work, we have performed a systematic investigation of the effect of electrostatic repulsive interactions on the aggregation rate of colloidal nanoparticles to from doublets in the presence of a convective transport mechanism. The aggregation rate has been computed by solving numerically the Fuchs-Smoluchowski diffusion-convection equation. Two convective transport mechanisms have been considered: extensional flow field and gravity-induced relative sedimentation. A broad range of conditions commonly encountered in the applications of colloidal dispersions has been analyzed. The relative importance of convective to diffusive contributions has been quantified by using the Peclet number Pe. The simulation results indicate that, in the presence of repulsive interactions, the evolution of the aggregation rate as a function of Pe can always be divided into three distinct regimes, no matter which convective mechanism is considered. At low Pe values the rate of aggregation is independent of convection and is dominated by repulsive interactions. At high Pe values, the rate of aggregation is dominated by convection, and independent of repulsive interactions. At intermediate Pe values, a sharp transition between these two regimes occurs. During this transition, which occurs usually over a 10-100-fold increase in Pe values, the aggregation rate can change by several orders of magnitude. The interval of Pe values where this transition occurs depends upon the nature of the convective transport mechanism, as well as on the height and characteristic lengthscale of the repulsive barrier. A simplified model has been proposed that is capable of quantitatively accounting for the simulations results. The obtained results reveal unexpected features of the effect of ionic strength and particle size on the stability of colloidal suspensions under shear or sedimentation, which have relevant consequences in industrial applications.     

Convection/diffusion- and diffusion-controlled rapid-scan voltammetry in liquid chromatographic systems with a large-volume wall-jet detector

On-line voltammetric measurements under liquid chromatographic (LC) conditions yield voltammograms which are either purely diffusion- or purely convection/diffusion-controlled, or a combination of both. The dependence of this behaviour on flow-rate, scan-rate and electrode diameter is investigated for a large-volume wall-jet detector. It is shown that for 4 V s^?1 scan-rates at 1 ml min^?1 flow-rates (conventional LC conditions), S-shaped (convection/diffusion-controlled) voltammograms can be obtained with macro-electrodes (? 1 mm diameter). Distortion of voltammogram shape by the cell time constant is discussed for macro-electrodes. The behaviour of the cell in microbore and micro-LC applications is demonstrated. The advantage of being able to change from convection/diffusion-controlled to diffusion-controlled behaviour is discussed.     

On the diffusion of ferrocenemethanol in room-temperature ionic liquids: an electrochemical study

The electrochemical behaviour of ferrocenemethanol (FcMeOH) has been studied in a range of room-temperature ionic liquids (RTILs) using cyclic voltammetry, chronoamperomery and scanning electrochemical microscopy (SECM). The diffusion coefficient of FcMeOH, measured using chronoamperometry, decreased with increasing RTIL viscosity. Analysis of the mass transport properties of the RTILs revealed that the Stokes-Einstein equation did not apply to our data. The "correlation length" was estimated from diffusion coefficient data and corresponded well to the average size of holes (voids) in the liquid, suggesting that a model in which the diffusing species jumps between holes in the liquid is appropriate in these liquids. Cyclic voltammetry at ultramicroelectrodes demonstrated that the ability to record steady-state voltammograms during ferrocenemethanol oxidation depended on the voltammetric scan rate, the electrode dimensions and the RTIL viscosity. Similarly, the ability to record steady-state SECM feedback approach curves depended on the RTIL viscosity, the SECM tip radius and the tip approach speed. Using 1.3 μm Pt SECM tips, steady-state SECM feedback approach curves were obtained in RTILs, provided that the tip approach speed was low enough to maintain steady-state diffusion at the SECM tip. In the case where tip-induced convection contributed significantly to the SECM tip current, this effect could be accounted for theoretically using mass transport equations that include diffusive and convective terms. Finally, the rate of heterogeneous electron transfer across the electrode/RTIL interface during ferrocenemethanol oxidation was estimated using SECM, and k(0) was at least 0.1 cm s(-1) in one of the least viscous RTILs studied.     

Tuning of electron transport through molecular bridge systems: A study of shot noise

We study electron transport characteristics through a single phenalenyl molecule attached with two nonsuperconducting electrodes by the use of Green's function technique. Parametric calculations are given based on the tight‐binding model to characterize the electron transport through such molecular bridge system. It is observed that the electron transport properties are significantly influenced by (a) the interference effect and (b) the molecule‐to‐electrodes coupling strength. In this context we also describe the noise power of the current fluctuations that provides an important information about the electron correlation, which is obtained by calculating the Fano factor (F). The knowledge of this current fluctuations gives a key idea for fabrication of efficient molecular devices. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Effects of localised and global convection on thermal explosion in a parallel-plate geometry

During an exothermic reaction in a fluid, convection may ensue on a local scale and then develop to the scale of the entire vessel. In this work, we study the effects of both localised and global convection on thermal explosions occurring between parallel plates. Analytical relations are derived for the various transitions in regimes of convective and thermal behaviours. We show that these relations agree well with previous numerical work and with new simulations in the present investigation. We also determine analytically the time for onset of convection, as well as the temperature increase at that time, for stable and explosive systems. The effects of the Prandtl number of the fluid on the transitions between regimes are noted.     

Temperature Compensation by Embedded Temperature Variation Method for an AC Voltammeric Analyzer of Electroplating Baths

An in‐situ sensor utilizing a variety of DC‐ and AC‐voltammetric techniques is an integral component of the on‐line monitoring system that provides a complete chemical analysis of different plating solutions by predicting concentration values of all deliberately‐added bath constituents with a single device despite differences in the constituents’ chemical properties. Such sensors are employed routinely for electroplating process control in semiconductor manufacturing. This voltammetric approach exploits quantitatively the physicochemical processes (like adsorption) which are temperature dependent. Therefore the accuracy of analyte concentration predictions can be affected adversely by temperature fluctuations. This paper introduces a novel comprehensive method which allows the mitigation of temperature variation effects on voltammetric scans allowing accurate concentration prediction. Specifically, this study introduces a multi‐step rigorous routine for the development and subsequent validation of the analytical method utilizing a chemometric model with temperature variation embedded in regression for exemplary determination of leveler additive concentration. This approach analyses the effect on AC voltammograms resulting from two qualitatively indistinguishable sources of variation: leveler concentration and temperature. A critical step of this routine of fundamental novelty, which aims to select the variables (index points of voltammogram) to be utilized for building of the analytical model in the presence of two concurrent sources of variation, is introduced to incorporate temperature variation.     

Optical noise and dynamical properties of liquid crystal comb polymers with different mesogenic groups

The light scattered by a comb polymer with a polyacrylamide main chain and biphenyl-based mesogenic units containing the substituent R CN in the biphenyl core is characterized by a stationary noise which has been measured between 70 C and 140 C in the frequency interval 5 10 - 2 nu 10Hz. This optical noise is analysed by means of a specific procedure introduced to clarify the role of random movements of segments of the main chains on the side chain fluctuations. The RMS amplitude of the random molecular movements, the relaxation times of the side chain and main chain fluctuations, and the damping coefficients governing their motion are investigated as functions of temperature. The results are compared with those recently obtained on a similar polymer characterized by R H. Common features and differences are brought into evidence and discussed in terms of the different mesophase structures exhibited by the two polymers in the temperature interval considered.     

The simple model and linear stability analysis of the electrode process with the NDR region caused by the potential-dependent convective transport

In our earlier report on the experimental studies of convection coupled with electrochemical processes of Hg ions at the mercury electrode we showed that the potential-dependent onset and decay of this convection can give rise to the N-shaped negative differential resistance (NNDR) in the current–potential characteristics. As a consequence, the presence of appropriate serial ohmic resistance in the electric circuit caused bistability. Since the rather poorly reproducible nature of this convection makes the precise experimental studies difficult, we elaborated the simple model which extracts the basic dynamical properties of the system under study. The model involves the electrode potential and the Nernst layer thickness for the convective diffusion as the dynamical variables. Using linear stability analysis we derived the stability criteria and constructed the bifurcation diagram, showing bistability, in accordance with the experimental data, but not predicting the oscillatory behavior.     

Temperature behaviour of a liquid crystal comb polymer: Light scattering and noise of the scattered light

Measurements of the intensity of the monochromatic light transmitted through and scattered by a comb polymer with a polyacrylamide main chain were performed between room temperature and the isotropization temperature of the polymer. The stationary noise of the light scattered at low angle was measured in the same temperature interval. The transmitted intensity is observed to increase strongly above the smectic S_I2-S_c2 transition, where the intensity of the light scattered at low angles is maximized. The power dissipated by the molecular fluctuations dramatically increases above the transition between the two smectic phases. The spectral density curves display a Lorentzian character only below the S_I2-S_c2 transition. At higher temperatures, a more complex frequency behaviour of the stationary noise spectra is observed. Such a behaviour is interpreted in terms of a model explicitly invoking the effect of the Brownian movement of segments of the main chain (backbone) of the polymer on the side chain fluctuations. The parameters governing the Brownian movements of both main and side chains, and their evolution with temperature, are determined and discussed in the light of a simple structural model.     

Microwave induced jet boiling investigated via voltammetry at ring-disk microelectrodes

High intensity microwave radiation is (self-)focused at metal electrodes immersed in aqueous electrolyte solutions to generate highly localized superheating and convection effects. It is shown that, for an electrode pointing downward, low intensity microwave radiation causes density driven convective flow (upward), which at the onset of boiling abruptly switches to a fast jet of liquid moving away from the electrode surface (downward). This "jet-boiling" phenomenon allows extremely high rates of mass transport and mixing to be realized at the electrode surface. Cyclic voltammograms obtained at electrodes placed into a microwave field show very strong mass transport enhancement effects. Cyclic voltammograms recorded at a Pt/Pt ring-disk electrode system (r(1) = 25 microm, r(2) = 32 microm, r(3) = 32.4 microm) in the presence of microwave radiation are employed to further explore mass transport effects under microwave conditions. Mass transport coefficients, collection efficiencies, and temperatures are determined as a function of microwave intensity.     

Effect of Natural Convection on the Anodic Dissolution of Horizontal Tungsten Electrodes

The data on the limiting currents of anodic dissolution of horizontal tungsten electrodes measured in alkaline solutions under the conditions of natural convection are presented. It is shown that conditions determining natural convection (downward or upward position of the electrode's active surface, solution concentration, etc.) affect the limiting current, the current variation with time, and the origination of convective instabilities of various types.     

Natural convection in nanofluid flow with chemotaxis process over a vertically inclined heated surface

The thermal energy transport analysis with chemotaxis in the free convective flow of viscous nanofluid over stretchable vertically inclined heated sheet is addressed in this article. The fluid forced and free convection motion is investigated and discussed with physical reasoning. The fluid also contains microorganism heavy-bottom species, and their chemotactic motion is studied. In the light of Buongiorno model, the impact of Brownian motion and thermophoresis slip mechanism on thermal conduction in the nanofluid is analyzed. The work is based on the similarity analysis of governing partial differential equations (PDEs) which lead to non-dimensional ordinary differential equations (ODEs). The solution of resulting flow and heat equations is computed via bvp4c technique. The outcomes are represented in graphical abstract. It is noted that free convective flow field increases near to the surface of sheet then it decays to free stream exponentially. Higher magnitude of thermophoretic force boost up the thermal energy transport in nanofluid flow. The Brownian motion enhances temperature profile and lower down the convection velocity. Chemotaxis motion of species in nanofluid is increasing function of bioconvective Peclet number.     

A new experimental method to distinguish two different mechanisms for a category of oscillators involving mass transfer

We present new experimental evidence that further confirms that a combination of electrochemical reactions and diffusion–convection (ERDC) mass transfer accounts for the potential oscillations that appear under conditions of transport limited current. A typical example is given for the reduction of Fe(CN)₆³⁻ in alkaline solution accompanying periodic hydrogen evolution. No potential oscillations occur by simply replacing the hydrogen evolution with IO₃⁻ reduction as the second current carrier. That replacement removes only the convection mass transfer induced by the hydrogen evolution, and retains the negative differential resistance (NDR) from the Frumkin repulsive effect. The key role of hydrogen evolution is thus to restore the Fe(CN)₆³⁻ surface concentration after its depleting to zero by diffusion-limited reduction, rather than purely a second current carrier. Therefore, the other mechanism, which emphasizes the NDR from the Frumkin interaction due to electrostatic repulsion, is excluded because it does not have a direct connection with the oscillations. Moreover, a crossing cycle in cyclic voltammograms is a more convincible criterion for this category of electrochemical oscillators than the negative impedance.     

Theoretical analysis of localized heating in human skin subjected to high voltage pulses

Electroporation, the increase in the permeability of bilayer lipid membranes by the application of high voltage pulses, has the potential to serve as a mechanism for transdermal drug delivery. However, the associated current flow through the skin will increase the skin temperature and might affect nearby epidermal cells, lipid structure or even transported therapeutic molecules. Here, thermal conduction and thermal convection models are used to provide upper and lower bounds on the local temperature rise, as well as the thermal damage, during electroporation from exponential voltage pulses (70 V maximum) with a 1 ms and a 10 ms pulse time constant. The peak temperature rise predicted by the conduction model ranges from 19 degrees C for a 1 ms time constant pulse to 70 degrees C for the 10 ms time constant pulse. The convection (mass transport) model predicts a 18 degrees C peak rise for 1 ms time constant pulses and a 51 degrees C peak rise for a 10 ms time constant pulse. The convection model compares more favorably with previous experimental studies and companion observations of the local temperature rise during electroporation. Therefore, it is expected that skin electroporation can be employed at a level which is able to transport molecules transdermally without causing significant thermal damage to the tissue.     

Space and Time Correlations in a Dissipative Structure Emerging in an Electrochemical System with a Cation-Exchange Membrane

The mechanism of electromasstransfer in a system containing a cation-exchange membrane at a current density exceeding the limiting diffusion current is studied by analyzing the electric potential fluctuations. An experimental setup is designed for measuring fluctuations simultaneously at 16 points in a galvanostatic mode. The fluctuations are found to form in a near-membrane diffusion layer of electrolyte depleted of carriers. As the current density increases, spectra of resonance fluctuations turn into flicker-noise spectra; this process is studied in great detail. Use of space and time difference moments for processing noise signals allowed us to estimate such parameters as the correlation time, space correlation length, and components of the propagation velocity for perturbations in the dissipative structure forming in the membrane system. The data point to the formation of convective flows thermally induced in a diffusion layer of electrolyte under the action of Joule heating at a current density approaching a limiting value.     

Effects of Different Drying Methods on the Retention of Bioactive Compounds,On-Line Antioxidant Capacity and Color of the Novel Snack from Red-Fleshed Apples

The aim of this study was to determine the effect of different drying methods: convective (at 50, 60, 70 °C), vacuum-microwave (at 120, 240, 360, 480 W and 360 W with reduction to 120 W) and hybrid (convective pre-drying at 50, 60, 70 °C followed by vacuum-microwave drying at 120 W) on the quality parameters of novel red-fleshed apple fruit snacks (RFAs), such as phenolics, on-line antioxidant capacity, water activity and color. Drying kinetics, including a temperature profile of dried material, and modified Page model were determined. Freeze-drying was used as a control method. The highest content of bioactive compounds in the samples was retained following freeze-drying, then hybrid, vacuum-microwave and finally convection drying. The antioxidant capacity measured by on-line 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS), identified anthocyanins, flavan-3-ols and phenolic acid as the main compounds responsible for this activity. Unfavorable changes in color, formation of hydroxymethylfurfural (HMF) and degradation of polyphenolics were noted along with increasing drying temperature and magnetron power. The red-fleshed apple snacks are a promising high-quality dehydrated food product belonging to functional foods category.     

Finite element simulation of the amperometric response of recessed and protruding microband electrodes in flow channels

The convective mass transfer for recessed and protruding microband electrodes, two geometries found in practical devices, is determined by the finite element method. The problem is solved by a two-step method, first solving the Navier-Stokes equation to compute the real hydrodynamic flow, then solving the convective diffusion equation to calculate the electrochemical response of the systems. In this work, we focus on the chronoamperometric response of recessed and protruding microband electrodes, emphasizing the role of the edge effects and convection streamlines, in particular the role of stagnant recirculating eddies due to these particular geometries.