Capillary end effect in a water saturated porous layer

The uni-directional propagation of oil injected into water flowing through a water wetted porous slab of a finite length is investigated. The inlet and outlet edges of the slab are impermeable to the oil flux. Hence, the oil accumulates within the slab, thereby leading to a saturation build-up-capillary end effect. This phenomenon is studied analytically on the basis of a nonlinear equation describing oil-water transport in porous media. A dimensionless criterion is derived, which governs the appearance and relative strength of the capillary end effect. For weak oil-water interfacial tension (large capillary number) and long porous slabs the above effect is not observed and the temporal evolution of the oil saturation is described by the Buckley-Leverett solution. Short porous slabs are found to be almost entirely subjected to the capillary end effect. Intermediate situations are identified and quantitatively described, in which the downstream part of the slab may be divided into two zones: one-characterized by the capillary end effect, and the other being a Buckley-Leverett zone.It is shown, that the oil flux injected into the slab is limited by a maximum value which depends upon the location of the injection point. The partition of the inlet flux between the upstream and downstream directions is investigated. In the upstream side of the porous slab the oil moves under the action of free imbibition only. It is found that the upstream flux is limited by the value, which is independent of the slab's length and of the location of the injection point.     

Ethers of indoxylie acid

O-alkylations of indoxylie acid (2b) to produce 3-indolyl-alkyl ethers and a synthesis of 5-melhoxy-2-earboxyindol-3-oxyaeetic acid (25) are described.     

A-acceptable exponentially fitted combinations of three Padé approximations

It is considered whether a linear combination of three A-acceptable Padé approximations to the exponential function remains A-acceptable when it is exponentially fitted to two distinct negative points. The results of Iserles [5] regarding linear combinations of two A-acceptable Padé approximations are generalized.     

On theA-stability of implicit Runge-Kutta processes

A new technique to calculate the characteristic functions and to examine theA-stability of implicit Runge-Kutta processes is presented. This technique is based on a direct algebraic approach and an application of theC-polynomial theory of Nørsett. New processes are suggested. These processes can be exponentially fitted in anA-stable manner.     

On expansions in orthogonal polynomials

A recently introduced fast algorithm for the computation of the first N terms in an expansion of an analytic function into ultraspherical polynomials consists of three steps: Firstly, each expansion coefficient is represented as a linear combination of derivatives; secondly, it is represented, using the Cauchy integral formula, as a contour integral of the function multiplied by a kernel; finally, the integrand is transformed to accelerate the convergence of the Taylor expansion of the kernel, allowing for rapid computation using Fast Fourier Transform. In the current paper we demonstrate that the first two steps remain valid in the general setting of orthogonal polynomials on the real line with finite support, orthogonal polynomials on the unit circle and Laurent orthogonal polynomials on the unit circle.     

Associative Versus Dissociative Mechanisms of Phosphate Monoester Hydrolysis: On the Interpretation of Activation Entropies

Phosphate monoester and anhydride hydrolysis is ubiquitous in biology, being involved in, amongst other things, signal transduction, energy production, and the regulation of protein function. Therefore, this reaction has understandably been the focus of intensive research. Nevertheless, the precise mechanism by which phosphate monoester hydrolysis proceeds remains controversial. Traditionally, it has been assumed and frequently implied that a near‐zero activation entropy is indicative of a dissociative pathway. Herein, we examine free‐energy surfaces for the hydrolysis of the methyl phosphate dianion and the methyl pyrophosphate trianion in aqueous solution. In both cases, the reaction can proceed through either compact or expansive concerted (A_ND_N) transition states, with fairly similar barriers. We have evaluated the activation entropies for each transition state and demonstrate that both associative and dissociative transition states have near‐zero entropies of activation that are in good agreement with experimental values. Therefore, we believe that the activation entropy alone is not a useful diagnostic tool, as it depends not only on bond orders at the transition state, but also on other issues that include (but are not limited to) steric factors determining the configurational volumes available to reactants during the reaction, solvation and desolvation effects that may be associated with charge redistribution upon approaching the transition state and entropy changes associated with intramolecular degrees of freedom as the transition state is approached.     

Local and global properties of mixtures in one-dimensional systems. Part I. Mixtures of two simple components

Two sets of quantities are calculated for two-component mixtures in one dimension. One consists of the traditional excess thermodynamic quantities which provide global information on the mixtures. The second, referred to as local properties, consists of the Kirkwood-Buff integrals, local composition, solvation, and preferential solvation quantities. In this part, we discuss simple particles interacting via either square-well potential or hard rod potential. It is shown that a host of new information can be obtained from the local properties of the mixtures which supplements the information conveyed by the global properties.