Ion specificity and the theory of stability of colloidal suspensions

A theory is presented which allow us to accurately calculate the critical coagulation concentration (CCC) of hydrophobic colloidal suspensions. For positively charged particles the CCC's follow the Hofmeister (lyotropic) series. For negatively charged particles the series is reversed. We find that strongly polarizable chaotropic anions are driven towards the colloidal surface by electrostatic and hydrophobic forces. Within approximately one ionic radius from the surface, the chaotropic anions loose part of their hydration sheath and become strongly adsorbed. The kosmotropic anions, on the other hand, are repelled from the hydrophobic surface. The theory is quantitatively accurate without any adjustable parameters. We speculate that the same mechanism is responsible for the Hofmeister series that governs stability of protein solutions.Comment: Phys. Rev. Lett. (in press

Interfacial Tension of Electrolyte Solutions

A theory is presented to account for the increase in surface tension of water in the presence of electrolyte. Unlike the original ``grand-canonical'' calculation of Onsager and Samaras, which relied on the Gibbs adsorption isotherm and lead to a result which could only be expressed as an infinite series, our approach is ``canonical'' and produces an analytic formula for the excess surface tension. For small concentrations of electrolyte, our result reduces to the Onsager-Samaras limiting law.Comment: contains two figures. Journal of Chemical Physics, in pres

Charge renormalization and phase separation in colloidal suspensions

We explore the effects of counterion condensation on fluid-fluid phase separation in charged colloidal suspensions. It is found that formation of double layers around the colloidal particles stabilizes suspensions against phase separation. Addition of salt, however, produces an instability which, in principle, can lead to a fluid-fluid separation. The instability, however, is so weak that it should be impossible to observe a fully equilibrated coexistence experimentally.Comment: 7 pages, Europhysics Letters (in press

Charge reversal of colloidal particles

A theory is presented for the effective charge of colloidal particles in suspensions containing multivalent counterions. It is shown that if colloids are sufficiently strongly charged, the number of condensed multivalent counterion can exceed the bare colloidal charge leading to charge reversal. Charge renormalization in suspensions with multivalent counterions depends on a subtle interplay between the solvation energies of the multivalent counterions in the bulk and near the colloidal surface. We find that the effective charge is {\it not} a monotonically decreasing function of the multivalent salt concentration. Furthermore, contrary to the previous theories, it is found that except at very low concentrations, monovalent salt hinders the charge reversal. This conclusion is in agreement with the recent experiments and simulations

Entropy-driven cutoff phenomena

In this paper we present, in the context of Diaconis' paradigm, a general method to detect the cutoff phenomenon. We use this method to prove cutoff in a variety of models, some already known and others not yet appeared in literature, including a chain which is non-reversible w.r.t. its stationary measure. All the given examples clearly indicate that a drift towards the opportune quantiles of the stationary measure could be held responsible for this phenomenon. In the case of birth- and-death chains this mechanism is fairly well understood; our work is an effort to generalize this picture to more general systems, such as systems having stationary measure spread over the whole state space or systems in which the study of the cutoff may not be reduced to a one-dimensional problem. In those situations the drift may be looked for by means of a suitable partitioning of the state space into classes; using a statistical mechanics language it is then possible to set up a kind of energy-entropy competition between the weight and the size of the classes. Under the lens of this partitioning one can focus the mentioned drift and prove cutoff with relative ease.Comment: 40 pages, 1 figur

Casimir repulsion between metallic objects in vacuum

We give an example of a geometry in which two metallic objects in vacuum experience a repulsive Casimir force. The geometry consists of an elongated metal particle centered above a metal plate with a hole. We prove that this geometry has a repulsive regime using a symmetry argument and confirm it with numerical calculations for both perfect and realistic metals. The system does not support stable levitation, as the particle is unstable to displacements away from the symmetry axis.Comment: 4 pages, 4 figures; added references, replaced Fig.

A Neutral Polyampholyte in an ionic solution

The behavior of a neutral polyampholyte ($PA$) chain with $N$ monomers, in an ionic solution, is analyzed in the framework of the full Debye-H$\ddot u$ckel-Bjerrum-Flory $(DHBjF)$ theory. A $PA$ chain, that in addition to the neutral monomers, also contains an equal number of positively and negatively charged monomers, is dissolved in an ionic solution. For \underline{high} concentrations of salt and at high temperatures, the $PA$ exists in an extended state. As the temperature is decreased, the electrostatic energy becomes more relevant and at a $T=T_{\theta}$ the system collapses into a dilute globular state, or microelectrolyte. This state contains a concentration of salt higher than the surrounding medium. As the temperature is decreased even further, association between the monomers of the polymer and the ions of the salt becomes relevant and there is a crossover from this globular state to a low temperature extended state. For \underline{low} densities of salt, the system is collapsed for almost all temperatures and exhibits a first-order phase transition to an extended state at an unphysical low temperature.Comment: 10 pages, Revtex with epsf, 9 Postscript figures. Submitted to PR

The effects of superconductor-stabilizer interfacial resistance on quench of a pancake coil made out of coated conductor

We present the results of numerical analysis of normal zone propagation in a stack of $YBa_2Cu_3O_{7-x}$ coated conductors which imitates a pancake coil. Our main purpose is to determine whether the quench protection quality of such coils can be substantially improved by increased contact resistance between the superconducting film and the stabilizer. We show that with increased contact resistance the speed of normal zone propagation increases, the detection of a normal zone inside the coil becomes possible earlier, when the peak temperature inside the normal zone is lower, and stability margins shrink. Thus, increasing contact resistance may become a viable option for improving the prospects of coated conductors for high $T_c$ magnets applications.Comment: 9 pages, 4 figure

Electrostatics of ions inside the nanopores and trans-membrane channels

A model of a finite cylindrical ion channel through a phospholipid membrane of width $L$ separating two electrolyte reservoirs is studied. Analytical solution of the Poisson equation is obtained for an arbitrary distribution of ions inside the trans-membrane pore. The solution is asymptotically exact in the limit of large ionic strength of electrolyte on the two sides of membrane. However, even for physiological concentrations of electrolyte, the electrostatic barrier sizes found using the theory are in excellent agreement with the numerical solution of the Poisson equation. The analytical solution is used to calculate the electrostatic potential energy profiles for pores containing charged protein residues. Availability of a semi-exact interionic potential should greatly facilitate the study of ionic transport through nanopores and ion channels