300 research outputs found
Strongly nonlinear dynamics of electrolytes in large ac voltages
We study the response of a model micro-electrochemical cell to a large ac
voltage of frequency comparable to the inverse cell relaxation time. To bring
out the basic physics, we consider the simplest possible model of a symmetric
binary electrolyte confined between parallel-plate blocking electrodes,
ignoring any transverse instability or fluid flow. We analyze the resulting
one-dimensional problem by matched asymptotic expansions in the limit of thin
double layers and extend previous work into the strongly nonlinear regime,
which is characterized by two novel features - significant salt depletion in
the electrolyte near the electrodes and, at very large voltage, the breakdown
of the quasi-equilibrium structure of the double layers. The former leads to
the prediction of "ac capacitive desalination", since there is a time-averaged
transfer of salt from the bulk to the double layers, via oscillating diffusion
layers. The latter is associated with transient diffusion limitation, which
drives the formation and collapse of space-charge layers, even in the absence
of any net Faradaic current through the cell. We also predict that steric
effects of finite ion sizes (going beyond dilute solution theory) act to
suppress the strongly nonlinear regime in the limit of concentrated
electrolytes, ionic liquids and molten salts. Beyond the model problem, our
reduced equations for thin double layers, based on uniformly valid matched
asymptotic expansions, provide a useful mathematical framework to describe
additional nonlinear responses to large ac voltages, such as Faradaic
reactions, electro-osmotic instabilities, and induced-charge electrokinetic
phenomena.Comment: 30 pages, 17 eps-figures, RevTe
Double layer in ionic liquids: Overscreening vs. crowding
We develop a simple Landau-Ginzburg-type continuum theory of solvent-free
ionic liquids and use it to predict the structure of the electrical double
layer. The model captures overscreening from short-range correlations, dominant
at small voltages, and steric constraints of finite ion sizes, which prevail at
large voltages. Increasing the voltage gradually suppresses overscreening in
favor of the crowding of counterions in a condensed inner layer near the
electrode. The predicted ion profiles and capacitance-voltage relations are
consistent with recent computer simulations and experiments on room-temperature
ionic liquids, using a correlation length of order the ion size.Comment: 4 pages + supplementary informatio
"Blue energy" from ion adsorption and electrode charging in sea- and river water
A huge amount of entropy is produced at places where fresh water and seawater
mix, for example at river mouths. This mixing process is a potentially enormous
source of sustainable energy, provided it is harnessed properly, for instance
by a cyclic charging and discharging process of porous electrodes immersed in
salt and fresh water, respectively [D. Brogioli, Phys. Rev. Lett. 103, 058501
(2009)]. Here we employ a modified Poisson-Boltzmann free-energy density
functional to calculate the ionic adsorption and desorption onto and from the
charged electrodes, from which the electric work of a cycle is deduced. We
propose optimal (most efficient) cycles for two given salt baths involving two
canonical and two grand-canonical (dis)charging paths, in analogy to the
well-known Carnot cycle for heat-to-work conversion from two heat baths
involving two isothermal and two adiabatic paths. We also suggest a slightly
modified cycle which can be applied in cases that the stream of fresh water is
limited.Comment: 7 Figure
Nonlinear electrochemical relaxation around conductors
We analyze the simplest problem of electrochemical relaxation in more than
one dimension - the response of an uncharged, ideally polarizable metallic
sphere (or cylinder) in a symmetric, binary electrolyte to a uniform electric
field. In order to go beyond the circuit approximation for thin double layers,
our analysis is based on the Poisson-Nernst-Planck (PNP) equations of dilute
solution theory. Unlike most previous studies, however, we focus on the
nonlinear regime, where the applied voltage across the conductor is larger than
the thermal voltage. In such strong electric fields, the classical model
predicts that the double layer adsorbs enough ions to produce bulk
concentration gradients and surface conduction. Our analysis begins with a
general derivation of surface conservation laws in the thin double-layer limit,
which provide effective boundary conditions on the quasi-neutral bulk. We solve
the resulting nonlinear partial differential equations numerically for strong
fields and also perform a time-dependent asymptotic analysis for weaker fields,
where bulk diffusion and surface conduction arise as first-order corrections.
We also derive various dimensionless parameters comparing surface to bulk
transport processes, which generalize the Bikerman-Dukhin number. Our results
have basic relevance for double-layer charging dynamics and nonlinear
electrokinetics in the ubiquitous PNP approximation.Comment: 25 pages, 17 figures, 4 table
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
Free drainage of aqueous foams: Container shape effects on capillarity and vertical gradients
Characterization of cider by its hydrophobicproteinprofile and foamparameters
This paper describes the characterization of ciders (both ânaturalâ and sparkling cider) from the Principality of Asturias (northwest region of Spain) through the analysis of their protein content, based on their hydrophobic properties, and their foam characteristics. A reversed-phase high performance liquid chromatography (RP-HPLC) was applied to the protein analysis, and the foamparameters were measured with Bikermanâs method. Multivariate techniques allowed the authors to differentiate ciders on the basis of the press and foam taking technologies, and foam sensory quality. Feasible and robust models were constructed for classifying purposes. Higher than 95% correct classifications were obtained for differentiating ciders on the basis of the factors studied (cider making technology and foam sensory quality). The multivariate regression model computed allowed the authors to predict (correlation coefficients higher than 0.8) the foamparameters related to foam stability and bubble average lifetime in ânaturalâ cider
Model-free test of local-density mean-field behavior in electric double layers
We derive a self-similarity criterion that must hold if a planar electric double layer (EDL) can be captured by a local-density approximation (LDA), without specifying any specific LDA. Our procedure generates a similarity coordinate from EDL profiles (measured or computed), and all LDA EDL profiles for a given electrolyte must collapse onto a master curve when plotted against this similarity coordinate. Noncollapsing profiles imply the inability of any LDA theory to capture EDLs in that electrolyte. We demonstrate our approach with molecular simulations, which reveal dilute electrolytes to collapse onto a single curve, and semidilute ions to collapse onto curves specific to each electrolyte, except where size-induced correlations arise. © 2013 American Physical Society
Ionic liquids at electrified interfaces
Until recently, âroom-temperatureâ (<100â150 °C) liquid-state electrochemistry was mostly electrochemistry of diluted electrolytes(1)â(4) where dissolved salt ions were surrounded by a considerable amount of solvent molecules. Highly concentrated liquid electrolytes were mostly considered in the narrow (albeit important) niche of high-temperature electrochemistry of molten inorganic salts(5-9) and in the even narrower niche of âfirst-generationâ room temperature ionic liquids, RTILs (such as chloro-aluminates and alkylammonium nitrates).(10-14) The situation has changed dramatically in the 2000s after the discovery of new moisture- and temperature-stable RTILs.(15, 16) These days, the âlater generationâ RTILs attracted wide attention within the electrochemical community.(17-31) Indeed, RTILs, as a class of compounds, possess a unique combination of properties (high charge density, electrochemical stability, low/negligible volatility, tunable polarity, etc.) that make them very attractive substances from fundamental and application points of view.(32-38) Most importantly, they can mix with each other in âcocktailsâ of oneâs choice to acquire the desired properties (e.g., wider temperature range of the liquid phase(39, 40)) and can serve as almost âuniversalâ solvents.(37, 41, 42) It is worth noting here one of the advantages of RTILs as compared to their high-temperature molten salt (HTMS)(43) âsister-systemsâ.(44) In RTILs the dissolved molecules are not imbedded in a harsh high temperature environment which could be destructive for many classes of fragile (organic) molecules
- âŠ