No Arabic abstract
In this paper we calculate the interfacial resistances to heat and mass transfer through a liquid-vapor interface in a binary mixture. We use two methods, the direct calculation from the actual non-equilibrium solution and integral relations, derived earlier. We verify, that integral relations, being a relatively faster and cheaper method, indeed gives the same results as the direct processing of a non-equilibrium solution. Furthermore we compare the absolute values of the interfacial resistances with the ones obtained from kinetic theory. Matching the diagonal resistances for the binary mixture we find that kinetic theory underestimates the cross coefficients. The heat of transfer is as a consequence correspondingly larger.
We present a theory which describes the transport properties of the interfacial region with respect to heat and mass transfer. Postulating the local Gibbs relation for a continuous description inside the interfacial region, we derive the description of the Gibbs surface in terms of excess densities and fluxes along the surface. We introduce overall interfacial resistances and conductances as the coefficients in the force-flux relations for the Gibbs surface. We derive relations between the local resistivities for the continuous description inside the interfacial region and the overall resistances of the surface for transport between the two phases for a mixture. It is shown that interfacial resistances depend among other things on the enthalpy profile across the interface. Since this variation is substantial the coupling between heat and mass flow across the surface are also substantial. In particular, the surface puts up much more resistance to the heat and mass transfer then the homogeneous phases over a distance comparable to the thickness of the surface. This is the case not only for the pure heat conduction and diffusion but also for the cross effects like thermal diffusion. For the excess fluxes along the surface and the corresponding thermodynamic forces we derive expressions for excess conductances as integrals over the local conductivities along the surface. We also show that the curvature of the surface affects only the overall resistances for transport across the surface and not the excess conductivities along the surface.
Although medium chain length insoluble amphiphiles are well known to form gaseous and liquid expanded phases on an air/water interface, the situation for the soluble case is less clear. We perform molecular dynamics simulations of model surfactant molecules dissolved in a bulk liquid solvent in coexistence with its vapor. Our results indicate a transition in both soluble and insoluble surfactants: a plateau in surface tension vs. surface coverage, whose instantaneous configurations display two phase coexistence, along with correlation functions indicating a transition to gaseous to liquid-like behavior.
We propose a simple scaling theory describing the variation of the mean first passage time (MFPT) $tau(N,M)$ of a regular block copolymer of chain length $N$ and block size $M$ which is dragged through a selective liquid-liquid interface by an external field $B$. The theory predicts a non-Arrhenian $tau$ vs. $B$ relationship which depends strongly on the size of the blocks, $M$, and rather weakly on the total polymer length, $N$. The overall behavior is strongly influenced by the degree of selectivity between the two solvents $chi$. The variation of $tau(N,M)$ with $N$ and $M$ in the regimes of weak and strong selectivity of the interface is also studied by means of computer simulations using a dynamic Monte Carlo coarse-grained model. Good qualitative agreement with theoretical predictions is found. The MFPT distribution is found to be well described by a $Gamma$ - distribution. Transition dynamics of ring- and telechelic polymers is also examined and compared to that of the linear chains. The strong sensitivity of the ``capture time $tau(N,M)$ with respect to block length $M$ suggests a possible application as a new type of chromatography designed to separate and purify complex mixtures with different block sizes of the individual macromolecules.
A gold-capped Janus particle suspended in a near-critical binary liquid mixture can self-propel under illumination. We have immobilized such a particle in a narrow channel and studied the nonequilibrium dynamics of a binary solvent around it, using experiment and numerical simulations. For the latter we consider both a purely diffusive and a hydrodynamic model. All approaches indicate that the early time dynamics is purely diffusive and characterized by composition layers traveling with a constant speed from the surface of the colloid into the bulk. Subsequently, hydrodynamic effects set in and the transient state is destroyed by strong nonequilibrium concentration fluctuations, which arise as a result of the temperature gradient and the vicinity of the critical point of the binary liquid mixture. They give rise to a complex, permanently changing coarsening patterns. For a mobile particle, the transient dynamics results in propulsion in the direction opposite to that observed after the steady state is attained.
Deformations of liquid interfaces by the optical radiation pressure of a focused laser wave were generally expected to display similar behavior, whatever the direction of propagation of the incident beam. Recent experiments showed that the invariance of interface deformations with respect to the direction of propagation of the incident wave is broken at high laser intensities. In the case of a beam propagating from the liquid of smaller refractive index to that of larger one, the interface remains stable, forming a nipple-like shape, while for the opposite direction of propagation, an instability occurs, leading to a long needle-like deformation emitting micro-droplets. While an analytical model successfully predicts the equilibrium shape of weakly deformed interface, very few work has been accomplished in the regime of large interface deformations. In this work, we use the Boundary Integral Element Method (BIEM) to compute the evolution of the shape of a fluid-fluid interface under the effect of a continuous laser wave, and we compare our numerical simulations to experimental data in the regime of large deformations for both upward and downward beam propagation. We confirm the invariance breakdown observed experimentally and find good agreement between predicted and experimental interface hump heights below the instability threshold.