Quasichemical theory and the description of associating fluids relative to a reference: Multiple bonding of a single site solute

We derive an expression for the chemical potential of an associating solute in a solvent relative to the value in a reference fluid using the quasichemical organization of the potential distribution theorem. The fraction of times the solute is not associated with the solvent, the monomer fraction, is expressed in terms of (a) the statistics of occupancy of the solvent around the solute in the reference fluid and (b) the Widom factors that arise because of turning on solute-solvent association. Assuming pair-additivity, we expand the Widom factor into a product of Mayer f-functions and the resulting expression is rearranged to reveal a form of the monomer fraction that is analogous to that used within the statistical associating fluid theory (SAFT). The present formulation avoids all graph-theoretic arguments and provides a fresh, more intuitive, perspective on Wertheim's theory and SAFT. Importantly, multi-body effects are transparently incorporated into the very foundations of the theory. We illustrate the generality of the present approach by considering examples of multiple solvent association to a colloid solute with bonding domains that range from a small patch on the sphere, a Janus particle, and a solute whose entire surface is available for association

Resummed thermodynamic perturbation theory for bond cooperativity in associating fluids with small bond angles: Effects of steric hindrance and ring formation

In this paper we develop a thermodynamic perturbation theory for two site associating fluids which exhibit bond cooperativity. We include both steric hindrance and ring formation such that the equation of state is bond angle dependent. Here the bond angle is the angle separating the centers of the two association sites. As a test, new Monte Carlo simulations are performed, and the theory is found to accurately predict the internal energy as well as the distribution of associated clusters as a function of bond angle and bond cooperativity.Comment: To appear in The Journal of Chemical Physic

Axisymmetric buckling of a spherical shell embedded in an elastic medium under uniaxial stress at infinity

The problem of a thin spherical linearly-elastic shell, perfectly bonded to an infinite linearly-elastic medium is considered. A constant axisymmetric stress field is applied at infinity in the matrix, and the displacement and stress fields in the shell and matrix are evaluated by means of harmonic potential functions. In order to examine the stability of this solution, the buckling problem of a shell which experiences this deformation is considered. Using Koiter's nonlinear shallow shell theory, restricting buckling patterns to those which are axisymmetric, and using the Rayleigh–Ritz method by expanding the buckling patterns in an infinite series of Legendre functions, an eigenvalue problem for the coefficients in the infinite series is determined. This system is truncated and solved numerically in order to analyse the behaviour of the shell as it undergoes buckling, and to identify the critical buckling stress in two cases — namely where the shell is hollow and the stress at infinity is either uniaxial or radial

A method for estimating the rate of shedding of tags from yellowfin tuna

ENGLISH: The present paper describes a new method for estimating the shedding rate of tags. The method utilizes not only data on tagging and recovery of fish marked with two tags but also data from those marked with one. One important advantage of the new technique is that the estimates of the shedding rates are free from distortion caused by variations in fishing intensity during the total recovery period. The idea of this method appears to be implicit in a short note by Gulland (1963). This technique has been applied to the data obtained by the Inter-American Tropical Tuna Commission in a tagging cruise off the west coast of southern Baja California, during June 1963, at which time both single and double-tagged yellowfin tuna were released. Details of the tagging procedure and equipment have been described by Fink (1965b). The results presented in the present paper are for yellowfin tuna tagged with dart tags. Estimates of shedding should be made separately for each species investigated and also for each type of tag used, since these rates may be variable and often unexpectedly high (Springer and McErlean 1961, Chadwick 1963). SPANISH: El presente estudio describe un nuevo método para estimar las tasas del desprendimiento de marcas. El método emplea no solamente los datos sobre la marcación y recobro de peces marcados con dos marcas, pero también datos de los peces marcados con una marca. Una ventaja importante de la nueva técnica, es que las estimaciones de las tasas de desprendimiento son libres de alteración, causada por las variaciones en la intensidad de pesca durante el período total de recobro. La idea de este método parece ser implícita en un breve apunte por Gulland (1963). Esta técnica se ha aplicado a los datos obtenidos por la Comisión Interamericana del Atún Tropical, en un crucero de marcación efectuado frente a la costa occidental al sur de Baja California, en junio de 1963, tiempo en el cual fueron liberados atunes aleta amarilla marcados tanto con una como con dos marcas. Los detalles del procedimiento de la marcación y del equipo usado han sido descritos por Fink (1965b). Los resultados presentados en este estudio, pertenecen al atún aleta amarilla marcado con marcas de dardo. Las estimaciones del desprendimiento deben efectuarse separadamente para cada especie que ha sido investigada y también para cada tipo de marca usado, ya que estas tasas pueden ser vaiables, y a menudo inesperadamente altas (Springer y McErlean 1961, Chadwick 1963). (PDF contains 20 pages.

From the Boltzmann equation to fluid mechanics on a manifold

We apply the Chapman-Enskog procedure to derive hydrodynamic equations on an arbitrary surface from the Boltzmann equation on the surface

A method for estimating the rate of shedding of tags from yellowfin tuna

ENGLISH: The present paper describes a new method for estimating the shedding rate of tags. The method utilizes not only data on tagging and recovery of fish marked with two tags but also data from those marked with one. One important advantage of the new technique is that the estimates of the shedding rates are free from distortion caused by variations in fishing intensity during the total recovery period. The idea of this method appears to be implicit in a short note by Gulland (1963). This technique has been applied to the data obtained by the Inter-American Tropical Tuna Commission in a tagging cruise off the west coast of southern Baja California, during June 1963, at which time both single and double-tagged yellowfin tuna were released. Details of the tagging procedure and equipment have been described by Fink (1965b). The results presented in the present paper are for yellowfin tuna tagged with dart tags. Estimates of shedding should be made separately for each species investigated and also for each type of tag used, since these rates may be variable and often unexpectedly high (Springer and McErlean 1961, Chadwick 1963). SPANISH: El presente estudio describe un nuevo método para estimar las tasas del desprendimiento de marcas. El método emplea no solamente los datos sobre la marcación y recobro de peces marcados con dos marcas, pero también datos de los peces marcados con una marca. Una ventaja importante de la nueva técnica, es que las estimaciones de las tasas de desprendimiento son libres de alteración, causada por las variaciones en la intensidad de pesca durante el período total de recobro. La idea de este método parece ser implícita en un breve apunte por Gulland (1963). Esta técnica se ha aplicado a los datos obtenidos por la Comisión Interamericana del Atún Tropical, en un crucero de marcación efectuado frente a la costa occidental al sur de Baja California, en junio de 1963, tiempo en el cual fueron liberados atunes aleta amarilla marcados tanto con una como con dos marcas. Los detalles del procedimiento de la marcación y del equipo usado han sido descritos por Fink (1965b). Los resultados presentados en este estudio, pertenecen al atún aleta amarilla marcado con marcas de dardo. Las estimaciones del desprendimiento deben efectuarse separadamente para cada especie que ha sido investigada y también para cada tipo de marca usado, ya que estas tasas pueden ser vaiables, y a menudo inesperadamente altas (Springer y McErlean 1961, Chadwick 1963). (PDF contains 20 pages.

Mini-grand canonical ensemble: chemical potential in the solvation shell

Quantifying the statistics of occupancy of solvent molecules in the vicinity of solutes is central to our understanding of solvation phenomena. Number fluctuations in small `solvation shells' around solutes cannot be described within the macroscopic grand canonical framework using a single chemical potential that represents the solvent `bath'. In this communication, we hypothesize that molecular-sized observation volumes such as solvation shells are best described by coupling the solvation shell with a mixture of particle baths each with its own chemical potential. We confirm our hypotheses by studying the enhanced fluctuations in the occupancy statistics of hard sphere solvent particles around a distinguished hard sphere solute particle. Connections with established theories of solvation are also discussed