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We investigate theoretically the kinetics of chemical reactions in polar solvents in the vicinity of charged porous membranes. When the pore charge (or potential) exceeds a critical value, the pores undergo a filling transition that can be first or second order depending on the ambient temperature, mixture composition, and other parameters. This filling transition leads to a dramatic acceleration or slowing down of the reaction. Such control of reaction kinetics by an external potential may be useful in applications where catalysts are absent or when fast spatiotemporal response is required.

We study the shift in the critical temperature T(c) in binary mixtures in strong electric fields. In experiments we measure the nonlinear dielectric effect (NDE) in a mixture of nitrobenze and n-octane and calculate Piekara's factor. We find that the critical anomaly of Piekara's factor is a function of an electric field strength. We propose to explain this observation as a result of a downward shift of T(c), and this allows us to calculate (∂T(c)/∂E(2)) = (-22 ± 10) × 10(-16) (K m(2))/V(2). In the theoretical part we amend Landau and Lifshitz's formula and show that the downward shift of Tc can be estimated from a simple mean-field theory taking into account the linear and quadratic terms in an expansion of the constitutive relation ε(x) between the electric constant ε and mixture composition x.

We investigate the vapor-liquid coexistence of polar and nonpolar fluids in the presence of a nonuniform electric field. We find that a large enough electric field can nucleate a gas bubble from the liquid phase or a liquid droplet from the vapor phase. The surface tension of the vapor-liquid interface is determined within squared-gradient theory. When the surface potential (charge) is controlled, the surface tension increases (decreases) compared to the zero-field interface. The effect of the electric field on the fluid phase diagram depends strongly on the constitutive relation for the dielectric constant. Finally, we show that gas bubbles can be nucleated far from the bounding surfaces.

We calculate the meniscus location in tapered capillaries under the influence of pressure difference and dielectrophoretic forces with and without gravity. We find that the meniscus location can be a discontinuous function of the pressure difference or the applied voltage and that the meniscus can "jump" to one end or another of the capillary. Phase diagrams are given as a function of the pressure and voltage, depending on the geometrical parameters of the system. We further consider a revision of the dielectric rise under dielectrophoretic force in wedge capillaries and in the case of electrowetting, where the dielectrophoretic force is a small perturbation. Finally, we also find discontinuous liquid-gas interface location in the case of liquid penetration into closed volumes.

We consider theoretically liquid rise against gravity in capillaries with height-dependent cross-sections. For a conical capillary made from a hydrophobic surface and dipped in a liquid reservoir, the equilibrium liquid height depends on the cone-opening angle alpha, the Young-Dupré contact angle theta, the cone radius at the reservoir's level R(0), and the capillary length kappa(-)(1). As alpha is increased from zero, the meniscus' position changes continuously until, when alpha attains a critical value, the meniscus jumps to the bottom of the capillary. For hydrophilic surfaces the meniscus jumps to the top. The same liquid height discontinuity can be achieved with electrowetting with no mechanical motion. Essentially the same behavior is found for two tilted surfaces. We further consider capillaries with periodic radius modulations and find that there are few competing minima for the meniscus location. A transition from one to another can be performed by the use of electrowetting. Finite pressure difference between the two sides of the liquids can be incorporated as well, resulting in complicated phase-diagrams in the alpha-theta plane. The phenomenon discussed here may find uses in microfluidic applications requiring the transport small amounts of water "quanta" (volume < 1 nL) in a regular fashion.