179 research outputs found
Coalescence in low-viscosity liquids
The expected universal dynamics associated with the initial stage of droplet
coalescence are difficult to study visually due to the rapid motion of the
liquid and the awkward viewing geometry. Here we employ an electrical method to
study the coalescence of two inviscid droplets at early times. We measure the
growth dynamics of the bridge connecting the two droplets and observe a new
asymptotic regime inconsistent with previous theoretical predictions. The
measurements are consistent with a model in which the two liquids coalesce with
a slightly deformed interface.Comment: 4 pages and 4 figure
Thermodynamic behaviour and structural properties of an aqueous sodium chloride solution upon supercooling
We present the results of a molecular dynamics simulation study of
thermodynamic and structural properties upon supercooling of a low
concentration sodium chloride solution in TIP4P water and the comparison with
the corresponding bulk quantities. We study the isotherms and the isochores for
both the aqueous solution and bulk water. The comparison of the phase diagrams
shows that thermodynamic properties of the solution are not merely shifted with
respect to the bulk. Moreover, from the analysis of the thermodynamic curves,
both the spinodal line and the temperatures of maximum density curve can be
calculated. The spinodal line appears not to be influenced by the presence of
ions at the chosen concentration, while the temperatures of maximum density
curve displays both a mild shift in temperature and a shape modification with
respect to bulk. Signatures of the presence of a liquid-liquid critical point
are found in the aqueous solution. By analysing the water-ion radial
distribution functions of the aqueous solution we observe that upon changing
density, structural modifications appear close to the spinodal. For low
temperatures additional modifications appear also for densities close to that
corresponding to a low density configurational energy minimum.Comment: 10 pages, 13 figures, 2 tables. To be published in J. Chem. Phy
Non-mean-field theory of anomalously large double-layer capacitance
Mean-field theories claim that the capacitance of the double-layer formed at
a metal/ionic conductor interface cannot be larger than that of the Helmholtz
capacitor, whose width is equal to the radius of an ion. However, in some
experiments the apparent width of the double-layer capacitor is substantially
smaller. We propose an alternate, non-mean-field theory of the ionic
double-layer to explain such large capacitance values. Our theory allows for
the binding of discrete ions to their image charges in the metal, which results
in the formation of interface dipoles. We focus primarily on the case where
only small cations are mobile and other ions form an oppositely-charged
background. In this case, at small temperature and zero applied voltage dipoles
form a correlated liquid on both contacts. We show that at small voltages the
capacitance of the double-layer is determined by the transfer of dipoles from
one electrode to the other and is therefore limited only by the weak
dipole-dipole repulsion between bound ions, so that the capacitance is very
large. At large voltages the depletion of bound ions from one of the capacitor
electrodes triggers a collapse of the capacitance to the much smaller
mean-field value, as seen in experimental data. We test our analytical
predictions with a Monte Carlo simulation and find good agreement. We further
argue that our ``one-component plasma" model should work well for strongly
asymmetric ion liquids. We believe that this work also suggests an improved
theory of pseudo-capacitance.Comment: 19 pages, 14 figures; some Monte Carlo results and a section about
aqueous solutions adde
The Hydrogen Evolution and Oxidation Kinetics during Overdischarging of Sealed Nickel-Metal Hydride Batteries
Measurements of the Casimir-Lifshitz force in fluids: the effect of electrostatic forces and Debye screening
In this work, we present detailed measurements of the Casimir-Lifshitz force
between two gold surfaces (a sphere and a plate) immersed in ethanol and study
the effect of residual electrostatic forces, which are dominated by static
fields within the apparatus and can be reduced with proper shielding.
Electrostatic forces are further reduced by Debye screening through the
addition of salt ions to the liquid. Additionally, the salt leads to a
reduction of the Casimir-Lifshitz force by screening the zero-frequency
contribution to the force; however, the effect is small between gold surfaces
at the measured separations and within experimental error. An improved
calibration procedure is described and compared to previous methods. Finally,
the experimental results are compared to Lifshitz's theory and found to be
consistent for the materials used in the experiment.Comment: 11 figures. PRA in pres
Porous silicon formation and electropolishing
Electrochemical etching of silicon in hydrofluoride containing electrolytes
leads to pore formation for low and to electropolishing for high applied
current. The transition between pore formation and polishing is accompanied by
a change of the valence of the electrochemical dissolution reaction. The local
etching rate at the interface between the semiconductor and the electrolyte is
determined by the local current density. We model the transport of reactants
and reaction products and thus the current density in both, the semiconductor
and the electrolyte. Basic features of the chemical reaction at the interface
are summarized in law of mass action type boundary conditions for the transport
equations at the interface. We investigate the linear stability of a planar and
flat interface. Upon increasing the current density the stability flips either
through a change of the valence of the dissolution reaction or by a nonlinear
boundary conditions at the interface.Comment: 18 pages, 8 figure
Modeling of electrochemomechanical response of ionic polymer-metal composites with various solvents
Reaction-Diffusion Processes with Nonlinear Diffusion
We study reaction-diffusion processes with concentration-dependent
diffusivity. First, we determine the decay of the concentration in the
single-species and two-species diffusion-controlled annihilation processes. We
then consider two natural inhomogeneous realizations. The two-species
annihilation process is investigated in the situation when the reactants are
initially separated, namely each species occupies a half space. In particular,
we determine the growth law of the width of the reaction zone. The
single-species annihilation process is studied in the situation when the
spatially localized source drives the system toward the non-equilibrium steady
state. Finally we investigate a dissolution process with a localized source of
diffusing atoms which react with initially present immobile atoms forming
immobile molecules.Comment: Figure and references added, final versio
Diffuse-Charge Dynamics in Electrochemical Systems
The response of a model micro-electrochemical system to a time-dependent
applied voltage is analyzed. The article begins with a fresh historical review
including electrochemistry, colloidal science, and microfluidics. The model
problem consists of a symmetric binary electrolyte between parallel-plate,
blocking electrodes which suddenly apply a voltage. Compact Stern layers on the
electrodes are also taken into account. The Nernst-Planck-Poisson equations are
first linearized and solved by Laplace transforms for small voltages, and
numerical solutions are obtained for large voltages. The ``weakly nonlinear''
limit of thin double layers is then analyzed by matched asymptotic expansions
in the small parameter , where is the
screening length and the electrode separation. At leading order, the system
initially behaves like an RC circuit with a response time of
(not ), where is the ionic diffusivity, but nonlinearity
violates this common picture and introduce multiple time scales. The charging
process slows down, and neutral-salt adsorption by the diffuse part of the
double layer couples to bulk diffusion at the time scale, . In the
``strongly nonlinear'' regime (controlled by a dimensionless parameter
resembling the Dukhin number), this effect produces bulk concentration
gradients, and, at very large voltages, transient space charge. The article
concludes with an overview of more general situations involving surface
conduction, multi-component electrolytes, and Faradaic processes.Comment: 10 figs, 26 pages (double-column), 141 reference
Orbital overlap effects in electron transfer reactions across a metal nanowire/electrolyte solution interface
In this paper, we report on calculations of the orbital overlap between Fe(III) and Cr(III) aquacomplexes and different electrode surfaces: Cu(111), Ag (111), Au(111), Pt(111), and corresponding monatomic wires. The electronic structure of the monocrystalline surfaces and nanowires are described in terms of the electronic spillover and density of electronic states at the Fermi level obtained from periodic density functional theory (DFT) calculations. The transmission coefficients (Îş) characterizing the first stage of outer-sphere electron transfer for the reduction of aquacomplexes are calculated on the basis of Landau–Zener theory as a function of electrode–reactant separation; the electronic transmission coefficients for the [Cr(H2O)6]3+/2+ redox couple were found to be smaller than those for [Fe(H2O)6]3+/2+. Two different intervals can be clearly distinguished for Cu, Au and Pt: “a catalytic region”, where Îş(wire) > Îş(Me slab) and “an inhibition region”, where Îş(wire) < Îş(Me slab). A similar behavior exhibits the coupling constant estimated for a hydrogen atom adsorbed at the Au(111) surface and the Au monatomic wire. These effects originate from some specific features of electronic density profile for metal nanowires: at short distances the electronic density of nanowires is higher compared with the (111) metal surfaces, while at larger separations it decreases more sharply.Fil: Nazmutdinov, Renat R.. Kazan National Research Technological University; RusiaFil: Berezin, Alexander S.. Kazan National Research Technological University; RusiaFil: Soldano, Germán. Universitat Ulm; Alemania. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas; ArgentinaFil: Schmickler, Wolfgang. Universitat Ulm; Alemani
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