Determination of permeability tensors for two-phase flow in homogeneous porous media: Theory

In this paper we continue previous studies of the closure problem for two-phase flow in homogeneous porous media, and we show how the closure problem can be transformed to a pair of Stokes-like boundary-value problems in terms of pressures that have units of length and velocities that have units of length squared. These are essentially geometrical boundary value problems that are used to calculate the four permeability tensors that appear in the volume averaged Stokes' equations. To determine the geometry associated with the closure problem, one needs to solve the physical problem; however, the closure problem can be solved using the same algorithm used to solve the physical problem, thus the entire procedure can be accomplished with a single numerical code.Nomenclature a a vector that maps V onto , m^-1. - A a tensor that maps V onto . - A area of the - interface contained within the macroscopic region, m². - A area of the -phase entrances and exits contained within the macroscopic region, m². - A area of the - interface contained within the averaging volume, m². - A area of the -phase entrances and exits contained within the averaging volume, m². - Bo Bond number (= (=(–)g²/). - Ca capillary number (= v/). - g gravitational acceleration, m/s². - H mean curvature, m^-1. - I unit tensor. - permeability tensor for the -phase, m². - viscous drag tensor that maps V onto V. - ^* dominant permeability tensor that maps onto v , m². - ^* coupling permeability tensor that maps onto v , m². - characteristic length scale for the -phase, m. - l characteristic length scale representing both and , m. - L characteristic length scale for volume averaged quantities, m. - n unit normal vector directed from the -phase toward the -phase. - n unit normal vector representing both n and n . - n unit normal vector representing both n and n . - P pressure in the -phase, N/m². - p superficial average pressure in the -phase, N/m². - p intrinsic average pressure in the -phase, N/m². - p –p , spatial deviation pressure for the -phase, N/m². - r ₀ radius of the averaging volume, m. - r position vector, m. - t time, s. - v fluid velocity in the -phase, m/s. - v superficial average velocity in the -phase, m/s. - v intrinsic average velocity in the -phase, m/s. - v –v , spatial deviation velocity in the -phase, m/s. - V volume of the -phase contained within the averaging volmue, m³. - averaging volume, m³. Greek Symbols V /, volume fraction of the -phase. - viscosity of the -phase, Ns/m². - density of the -phase, kg/m³. - surface tension, N/m. - (v +v ^T ), viscous stress tensor for the -phase, N/m².     

Transport in ordered and disordered porous media I: The cellular average and the use of weighting functions

In this work we consider transport in ordered and disordered porous media using singlephase flow in rigid porous mediaas an example. We defineorder anddisorder in terms of geometrical integrals that arise naturally in the method of volume averaging, and we show that dependent variables for ordered media must generally be defined in terms of thecellular average. The cellular average can be constructed by means of a weighting function, thus transport processes in both ordered and disordered media can be treated with a single theory based on weighted averages. Part I provides some basic ideas associated with ordered and disordered media, weighted averages, and the theory of distributions. In Part II a generalized averaging procedure is presented and in Part III the closure problem is developed and the theory is compared with experiment. Parts IV and V provide some geometrical results for computer generated porous media.Roman Letters A interfacial area of the- interface contained within the macroscopic region, m² - A_e area of entrances and exits for the-phase contained within the macroscopic system, m² - g gravity vector, m/s² - I unit tensor - K traditional Darcy's law permeability tensor, m² - L general characteristic length for volume averaged quantities, m - characteristic length (pore scale) for the-phase - (y) weighting function - m(–y) (y), convolution product weighting function - _v special weighting function associated with the traditional averaging volume - N unit normal vector pointing from the-phase toward the-phase - p pressure in the-phase, N/m² - p0 reference pressure in the-phase, N/m² - p traditional intrinsic volume averaged pressure, N/m² - r0 radius of a spherical averaging volume, m - r position vector, m - r position vector locating points in the-phase, m - averaging volume, m³ - V volume of the-phase contained in the averaging volume, m³ - V _cell volume of a unit cell, m³ - v velocity vector in the-phase, m/s - v traditional superficial volume averaged velocity, m/s - x position vector locating the centroid of the averaging volume or the convolution product weighting function, m - y position vector relative to the centroid, m - y position vector locating points in the-phase relative to the centroid, m Greek Letters indicator function for the-phase - Dirac distribution associated with the- interface - V/V, volume average porosity - mass density of the-phase, kg/m³ - viscosity of the-phase, Ns/m²     

Flow in porous media II: The governing equations for immiscible,two-phase flow

The Stokes flow of two immiscible fluids through a rigid porous medium is analyzed using the method of volume averaging. The volume-averaged momentum equations, in terms of averaged quantities and spatial deviations, are identical in form to that obtained for single phase flow; however, the solution of the closure problem gives rise to additional terms not found in the traditional treatment of two-phase flow. Qualitative arguments suggest that the nontraditional terms may be important when / is of order one, and order of magnitude analysis indicates that they may be significant in terms of the motion of a fluid at very low volume fractions. The theory contains features that could give rise to hysteresis effects, but in the present form it is restricted to static contact line phenomena.Roman Letters (, = , , and ) A interfacial area of the- interface contained within the macroscopic system, m² - A _e area of entrances and exits for the -phase contained within the macroscopic system, m² - A interfacial area of the- interface contained within the averaging volume, m² - A ^* interfacial area of the- interface contained within a unit cell, m² - A _e ^* area of entrances and exits for the-phase contained within a unit cell, m² - g gravity vector, m²/s - H mean curvature of the- interface, m^–1 - H area average of the mean curvature, m^–1 - H – H , deviation of the mean curvature, m^–1 - I unit tensor - K Darcy's law permeability tensor, m² - K permeability tensor for the-phase, m² - K viscous drag tensor for the-phase equation of motion - K viscous drag tensor for the-phase equation of motion - L characteristic length scale for volume averaged quantities, m - characteristic length scale for the-phase, m - n unit normal vector pointing from the-phase toward the-phase (n = –n ) - p _c p – P , capillary pressure, N/m² - p pressure in the-phase, N/m² - p intrinsic phase average pressure for the-phase, N/m² - p – p , spatial deviation of the pressure in the-phase, N/m² - r ₀ radius of the averaging volume, m - t time, s - v velocity vector for the-phase, m/s - v phase average velocity vector for the-phase, m/s - v intrinsic phase average velocity vector for the-phase, m/s - v – v , spatial deviation of the velocity vector for the-phase, m/s - V averaging volume, m³ - V volume of the-phase contained within the averaging volume, m³ Greek Letters V /V, volume fraction of the-phase - mass density of the-phase, kg/m³ - viscosity of the-phase, Nt/m² - surface tension of the- interface, N/m - viscous stress tensor for the-phase, N/m² - / kinematic viscosity, m²/s     

Two-phase flow in heterogeneous porous media I: The influence of large spatial and temporal gradients

In order to capture the complexities of two-phase flow in heterogeneous porous media, we have used the method of large-scale averaging and spatially periodic models of the local heterogeneities. The analysis leads to the large-scale form of the momentum equations for the two immiscible fluids, a theoretical representation for the large-scale permeability tensor, and a dynamic, large-scale capillary pressure. The prediction of the permeability tensor and the dynamic capillary pressure requires the solution of a large-scale closure problem. In our initial study (Quintard and Whitaker, 1988), the solution to the closure problem was restricted to the quasi-steady condition and small spatial gradients. In this work, we have relaxed the constraint of small spatial gradients and developed a dynamic solution to the closure problem that takes into account some, but not all, of the transient effects that occur at the closure level. The analysis leads to continuity and momentum equations for the-phase that are given by

Flow in porous media I: A theoretical derivation of Darcy's law

Stokes flow through a rigid porous medium is analyzed in terms of the method of volume averaging. The traditional averaging procedure leads to an equation of motion and a continuity equation expressed in terms of the volume-averaged pressure and velocity. The equation of motion contains integrals involving spatial deviations of the pressure and velocity, the Brinkman correction, and other lower-order terms. The analysis clearly indicates why the Brinkman correction should not be used to accommodate ano slip condition at an interface between a porous medium and a bounding solid surface.The presence of spatial deviations of the pressure and velocity in the volume-averaged equations of motion gives rise to aclosure problem, and representations for the spatial deviations are derived that lead to Darcy's law. The theoretical development is not restricted to either homogeneous or spatially periodic porous media; however, the problem ofabrupt changes in the structure of a porous medium is not considered.Roman Letters A interfacial area of the - interface contained within the macroscopic system, m² - A _e area of entrances and exits for the -phase contained within the macroscopic system, m² - A interfacial area of the - interface contained within the averaging volume, m² - A ^* interfacial area of the - interface contained within a unit cell, m² - Ae area of entrances and exits for the -phase contained within a unit cell, m² - B second order tensor used to represent the velocity deviation (see Equation (3.30)) - b vector used to represent the pressure deviation (see Equation (3.31)), m^–1 - d distance between two points at which the pressure is measured, m - g gravity vector, m/s² - K Darcy's law permeability tensor, m² - L characteristic length scale for volume averaged quantities, m - characteristic length scale for the -phase (see Figure 2), m - characteristic length scale for the -phase (see Figure 2), m - n unit normal vector pointing from the -phase toward the -phase (n =–n ) - n _e unit normal vector for the entrances and exits of the -phase contained within a unit cell - p pressure in the -phase, N/m² - p intrinsic phase average pressure for the -phase, N/m² - p –p , spatial deviation of the pressure in the -phase, N/m² - r ₀ radius of the averaging volume and radius of a capillary tube, m - v velocity vector for the -phase, m/s - v phase average velocity vector for the -phase, m/s - v intrinsic phase average velocity vector for the -phase, m/s - v –v , spatial deviation of the velocity vector for the -phase, m/s - V averaging volume, m³ - V volume of the -phase contained within the averaging volume, m³ Greek Letters V/V, volume fraction of the -phase - mass density of the -phase, kg/m³ - viscosity of the -phase, Nt/m² - arbitrary function used in the representation of the velocity deviation (see Equations (3.11) and (B1)), m/s - arbitrary function used in the representation of the pressure deviation (see Equations (3.12) and (B2)), s^–1     

Reversed-phase liquid chromatography/electrospray ionization/mass spectrometry with isotope dilution for the analysis of nitrate and nitrite in water

A new method was developed for the analysis of nitrate and nitrite in a variety of water matrices by using reversed-phase liquid chromatography/electrospray ionization/mass spectrometry in the negative ion mode. For this direct analysis method, nitrate and nitrite anions were well separated under the optimized LC conditions, detected by monitoring m/z 62 and m/z 46 ions, and quantitated by using an isotope dilution technique that utilized the isotopically labeled analogs. The method sensitivity, accuracy, and precision were investigated, along with matrix effects resulting from common inorganic matrix anions. The isotope dilution technique, along with sample pretreatment using barium, silver, and hydrogen cartridges, effectively compensated for the ionization suppression caused by the major water matrix anions, including chloride, sulfate, phosphate, and carbonate. The method detection limits, based on seven reagent water replicates fortified at 0.01 mg N/L nitrate and 0.1 mg N/L nitrite, were 0.001 mg N/L for nitrate and 0.012-0.014 mg N/L for nitrite. The mean recoveries from the replicate fortified reagent water and lab water samples containing the major water matrix anions, were 92-103% for nitrate with an imprecision (relative standard deviation, RSD) of 0.4-2.1% and 92-110% for nitrite with an RSD of 1.1-4.4%. For the analysis of nitrate and nitrite in drinking water, surface water, and groundwater samples, the obtained results were generally consistent with those obtained from the reference methods. The mean recoveries from the replicate matrix spikes were 92-123% for nitrate with an RSD of 0.6-7.7% and 105-113% for nitrite with an RSD of 0.3-1.8%.     

Diffusion in anisotropic porous media

An experimental system was constructed in order to measure the two distinct components of the effective diffusivity tensor in transversely isotropic, unconsolidated porous media. Measurements were made for porous media consisting of glass spheres, mica particles, and disks made from mylar sheets. Both the particle geometry and the void fraction of the porous media were determined experimentally, and theoretical calculations for the two components of the effective diffusivity tensor were carried out. The comparison between theory and experiment clearly indicates that the void fraction and particle geometry are insufficient to characterize the process of diffusion in anisotropic porous media. Roman Letters A interfacial area between - and -phases for the macroscopic system, m² - A _e area of entrances and exits of the -phase for the macroscopic system, m² - A interfacial area contained within the averaging volume, m² - a characteristic length of a particle, m - b average thickness of a particle, m - c _A concentration of species A, moles/m³ - c _o reference concentration of species A, moles/m³ - c _A intrinsic phase average concentration of species A, moles/m³ - c _a c _A–c _A, spatial deviation concentration of species A, moles/m³ - C c _A/c ₀, dimensionless concentration of species A - binary molecular diffusion coefficient, m²/s - D _eff effective diffusivity tensor, m²/s - D _xx component of the effective diffusivity tensor associated with diffusion parallel to the bedding plane, m²/s - D _yy component of the effective diffusivity tensor associated with diffusion perpendicular to the bedding plane, m²/s - D _eff effective diffusivity for isotropic systems, m₂/s - f vector field that maps c _A on to c _a , m - h depth of the mixing chamber, m     

Synthesis and characterization of laterally substituted bis(alkoxybenzoyloxy)hydroquinones

A new series of laterally substituted bis(alkoxybenzoyloxy)hydroquinone compounds has been synthesized and their mesomorphic properties studied. A number of hydroquinone compounds were synthesized with terminal n-alkoxy chains ranging from n-butyloxy to n-decyloxy. Additionally, lateral substituents ranging from n-butyl to n-octyl were incorporated through esterification at the remaining unsubstituted phenolic oxygen atoms. By optimizing the combination of the end group and lateral moieties we were able to tailor the molecular structure to form different liquid crystalline phases.