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Howard Brenner

Publications and source records attributed to Howard Brenner.

7 recordsLinked to original sources

Elementary kinematical model of thermal diffusion in liquids and gases.

An elementary hydrodynamic and Brownian motion model of the thermal diffusivity D(T) of a restricted class of binary liquid mixtures, previously proposed by the author, is given a more transparent derivation than originally, exposing thereby the strictly kinematic-hydrodynamic nature of an important class of thermodiffusion separation phenomena. Moreover, it is argued that the solvent's thermometric diffusivity alpha appearing in that theory as one of the two fundamental parameters governing D(T) should be replaced by the solvent's (isothermal) self-diffusivity D(S). In addition, a corrective multiplier of O(1) is inserted to reflect the general physicochemical noninertness of the solute relative to the solvent, thus enhancing the applicability of the resulting formula D(T)=lambdaD(S)beta to "nonideal" solutions. Here, beta is the solvent's thermal expansivity and lambda is a term of O(1), insensitive to the physicochemical nature of the solute (thus rendering D(T) primarily dependent upon only the properties of the solvent). This formula is, on the basis of its derivation, presumably valid only under certain idealized, albeit well-defined, circumstances. This occurs when the solute molecules are: (i) large compared with those of the solvent; and (ii) present only in small proportions relative to those of the solvent. When the solute is physicochemically inert, it is expected that lambda=1. When these conditions are met, the resulting thermal diffusivity of the mixture is, in theory, independent of any and all properties of the solute. Moreover, because beta is algebraically signed, the thermal diffusivity can either by positive or negative, according as the solvent expands or contracts upon being heated. This formula for D(T) is compared with available experimental data for selected binary liquid mixtures. Reasonable agreement is found in almost all circumstances with lambda near unity, the more so the higher the temperature, especially when the solute-solvent mixture properties closely approximate those where agreement would be expected and conversely. Finally, it is pointed out that for the restricted circumstances described, the formula D(T)=lambdaD(S)beta is equally credible for gases. Here, based on gas-kinetic theory, it is possible to furnish the theoretical value of lambda. Overall, while spanning a range of about five orders of magnitude, the D(T) values given by this elementary formula are shown to apply with reasonable accuracy to: (i) liquids (including circumstances for which D(T) is negative) as well as gases; (ii) all combinations of solvents and solutes tested (the latter including, for example, polymer molecules and metallic colloidal particles); and (iii) all sizes of solute molecules, from angstroms to submicron.

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Nonisothermal Brownian motion: Thermophoresis as the macroscopic manifestation of thermally biased molecular motion.

A quiescent single-component gravity-free gas subject to a small steady uniform temperature gradient T, despite being at rest, is shown to experience a drift velocity UD=-D* gradient ln T, where D* is the gas's nonisothermal self-diffusion coefficient. D* is identified as being the gas's thermometric diffusivity alpha. The latter differs from the gas's isothermal isotopic self-diffusion coefficient D, albeit only slightly. Two independent derivations are given of this drift velocity formula, one kinematical and the other dynamical, both derivations being strictly macroscopic in nature. Within modest experimental and theoretical uncertainties, this virtual drift velocity UD=-alpha gradient ln T is shown to be constitutively and phenomenologically indistinguishable from the well-known experimental and theoretical formulas for the thermophoretic velocity U of a macroscopic (i.e., non-Brownian) non-heat-conducting particle moving under the influence of a uniform temperature gradient through an otherwise quiescent single-component rarefied gas continuum at small Knudsen numbers. Coupled with the size independence of the particle's thermophoretic velocity, the empirically observed equality, U=UD, leads naturally to the hypothesis that these two velocities, the former real and the latter virtual, are, in fact, simply manifestations of the same underlying molecular phenomenon, namely the gas's Brownian movement, albeit biased by the temperature gradient. This purely hydrodynamic continuum-mechanical equality is confirmed by theoretical calculations effected at the kinetic-molecular level on the basis of an existing solution of the Boltzmann equation for a quasi-Lorentzian gas, modulo small uncertainties pertaining to the choice of collision model. Explicitly, this asymptotically valid molecular model allows the virtual drift velocity UD of the light gas and the thermophoretic velocity U of the massive, effectively non-Brownian, particle, now regarded as the tracer particle of the light gas's drift velocity, to each be identified with the Chapman-Enskog "thermal diffusion velocity" of the quasi-Lorentzian gas, here designated by the symbol UM/M, as calculated by de la Mora and Mercer. It is further pointed out that, modulo the collective uncertainties cited above, the common velocities UD,U, and UM/M are identical to the single-component gas's diffuse volume current jv, the latter representing yet another, independent, strictly continuum-mechanical concept. Finally, comments are offered on the extension of the single-component drift velocity notion to liquids, and its application towards rationalizing Soret thermal-diffusion separation phenomena in quasi-Lorentzian liquid-phase binary mixtures composed of disparately sized solute and solvent molecules, with the massive Brownian solute molecules (e.g., colloidal particles) present in disproportionately small amounts relative to that of the solvent.

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Is the tracer velocity of a fluid continuum equal to its mass velocity?

Owing to its size independence in the so-called near-continuum vanishingly small Knudsen number regime (Kn<<1) , thermophoretic particle motion occurring in an otherwise quiescent gas under the influence of a temperature gradient is here interpreted as representing the motion of a tracer, namely, an effectively point-size test particle monitoring the local velocity of the undisturbed, particle-free, compressible gas continuum through space. "Compressibility" refers here not to the usual effect of pressure on the gas's mass density rho but rather to the effect thereon of temperature. Our unorthodox continuum interpretation of thermophoresis differs from the usual one, which regards the existence of thermophoretic forces in gases as a strictly noncontinuum phenomenon, involving thermal stress-induced Maxwell slip ("thermal creep") of the gas's mass velocity vm at the surface of the particle, with vm denoting the velocity appearing in the continuity equation expressing the law of conservation of mass. Explicitly, instead of regarding the thermally animated particle as moving through the gas, we regard the particle (in its hypothesized role as a tracer of the undisturbed, particle-free, fluid motion) as moving with the gas, through space; that is, the particle is viewed as simply being entrained in the flowing gas, which, as a result of an externally applied temperature gradient, was already in motion prior to the tracer's introduction into the fluid--albeit not mass motion (which is, in fact, identically zero) but rather volume motion. This tracer-particle interpretation of experimental thermophoretic particle velocity measurements raises fundamental issues in regard to the universally accepted Newtonian rheological law constitutively specifying the viscous or deviatoric stress T as being proportional to the (symmetrized, traceless) fluid velocity gradient inverted Deltav , with v identified as being the fluid's mass velocity vm . Rather, it is argued in the case of compressible fluids, including liquids, that v should, instead, be chosen as the fluid's volume flux density or current density nv , the latter being formally equivalent to the fluid's volume velocity vv , which differs from vm except in the case of incompressible fluids. Apart from this strictly constitutive issue in regard to T , it is further argued that the fluid's tracer or Lagrangian velocity vl:=(deltax/deltat) (x0) along the fluid's spatiotemporal trajectory x=x (x0,t) is equal to vv, rather than to vm. This too is contrary to the heretofore unquestioned supposition that the conceptually distinct fluid velocities vl and vm are not only equal but are, in fact, synonymous. To the extent that vl not equal vm in the nonisothermal fluid case, an optical dye- or photochromic-type experiment (each of the latter two experiments presumably serving to measure vm) will record a different velocity than would a comparable tracer particle velocity measurement, one that measures vl .

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Separation mechanisms underlying vector chromatography in microlithographic arrays.

Micropatterned chips possessing an asymmetric, spatially periodic array of obstacles enable the vector (directional) chromatographic separation of charged particles animated by an external electric field. We apply a network theory to analyze the chip-scale (L-scale) transport of finite-size Brownian particles in such devices and identify those factors that break the symmetry of the chip-scale particle mobility tensor, most importantly the hydrodynamic wall effects between the particles and the obstacle surfaces. Our analysis contrasts with prevailing separation theories, which are limited to effectively point-size particles, for which wall effects are negligible. These theories require a biasing of obstacle-scale (l-scale; l<<L) bifurcation branches within the network. Such bifurcations are shown to constitute but one factor in modeling the vector chromatography of finite-size particles, and not necessarily the dominant factor.

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Body versus surface forces in continuum mechanics: is the Maxwell stress tensor a physically objective Cauchy stress?

The Maxwell stress tensor (MST) T(M) plays an important role in the dynamics of continua interacting with external fields, as in the commercially and scientifically important case of "ferrofluids." As a conceptual entity in quasistatic systems, the MST derives from the definition f(M)def=inverted Delta x T(M), where f(M)(x) is a physically objective volumetric external body-force density field at a point x of a continuum, derived from the solution of the pertinent governing equations. Beginning with the fact that T(M) is not uniquely defined via the preceding relationship from knowledge of f(M), we point out in this paper that the interpretation of T(M) as being a physical stress is not only conceptually incorrect, but that in commonly occuring situations this interpretation will result in incorrect predictions of the physical response of the system. In short, by elementary examples, this paper emphasizes the need to maintain the classical physical distinction between the notions of body forces f and stresses T. These examples include calculations of the torque on bodies, the work required to deform a fluid continuum, and the rate of interchange of energy between mechanical and other modes.

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Generalized Taylor-Aris dispersion in discrete spatially periodic networks: microfluidic applications.

A theory is presented for the lumped parameter, convective-diffusive transport of individual, noninteracting Brownian solute particles ("macromolecules") moving within spatially periodic, solvent-filled networks--the latter representing models of chip-based microfluidic chromatographic separation devices, as well as porous media. Using graph-theoretical techniques, the composite medium is conceptually decomposed into a network of channels (the edges) through which the solute is transported by a combination of molecular diffusion and either "piggyback" entrainment within a flowing solvent or an externally applied force field acting upon the solute molecules. A probabilistic choice of egress channel for a solute particle exiting the intersection (vertex) of the channels is furnished by an imperfect mixing model. A spatially periodic, Taylor-Aris-like "method-of-moments" scheme is applied to this transport model, leading to discrete matrix equations for computing the network-scale particle velocity vector U(*) and dispersivity dyadic D(*) in terms of the prescribed microscale transport parameters and network geometry characterizing the basic unit cell of which the spatially periodic device is comprised. The ensuing algebraic equations governing the vertex-based, discrete unit-cell "fields" P(0)(infinity)(i) and B(i) (i=1,2,...,n), whose paradigmatic summations yield U(*) and D(*), constitute discrete analogs of classical continuous macrotransport phenomenological parameters, P(0)(infinity)(r) and B(r), with r a continuous position vector defined within the unit cell. The ease with which these discrete calculations can be performed for complex networks renders feasible parametric studies of potential microfluidic chip designs, particularly those pertinent to biomolecular separation schemes. Application of this discrete theory to the dispersion analysis of pressure-driven flow in spatially periodic serpentine microchannels is shown to accord with existing results previously derived using classical continuous macrotransport theory.

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"Vector Chromatography": Modeling Micropatterned Separation Devices.

A repetitive sequence of quiescent fluid layers of differing viscosities through which small spherical Brownian particles move is analyzed in order to illustrate in a simple context how the theory of macrotransport processes, a generalization of Taylor dispersion theory, may be employed to rigorously analyze spatially periodic micropatterned chromatographic separation devices for circumstances in which the solute species to be separated are animated by the action of species-specific external forces oriented asymmetrically relative to the body-fixed pattern. In the generic "vector" separation scheme, illustrated by our elementary example, the different species undergoing separation move, on average, in different directions relative to pattern-fixed axes, whence their chromatographic sorting is effected according to their different mean angular trajectories through the device. This scheme differs fundamentally from traditional "scalar" chromatographic separation schemes, wherein all species move on average parallel to the animating force (including circumstances in which they are passively entrained in a unidirectional solvent flow) and hence for which the sorting is effected by the relative speeds of the several species through the chromatographic column. Vector chromatography is quantified by two global "macrotransport coefficients", namely the solute mobility dyadic M* (representing the tensor proportionality coefficient between the mean solute velocity vector U* and the external force vector F acting upon the solute molecules) and the dispersivity dyadic D* (resulting from the deviation of the instantaneous position of the particle from its mean position based upon its mean velocity vector). In the present example these coefficients are studied parametrically as functions of: (i) the orientation of the external force relative to the symmetry axis of the fluid layers; (ii) the local viscosity distribution within a layer; (iii) the vector particle Peclet number (constructed from the vector force, the length of the viscosity period, and the Boltzmann factor kT); and (iv) the thermodynamic interphase solute partition distribution coefficient between the two fluid layers comprising a unit cell. Copyright 2001 Academic Press.

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