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NavierStokes revisited

Howard Brenner

MA 02139-4307, USA

Received 27 August 2004

Communicated by J.V. Sergers

Available online 24 November 2004

Abstract

A revision of Newtons law of viscosity appearing in the role of the deviatoric stress tensor

in the NavierStokes equation is proposed for the case of compressible uids, both gaseous

and liquid. Explicitly, it is hypothesized that the velocity v appearing in the velocity gradient

term Vv in Newtons rheological law be changed from the uids mass-based velocity v

m

; the

latter being the velocity appearing in the continuity equation, to the uids volume velocity v

v

;

the latter being a stand-in for the uids volume current (volume ux density n

v

). A similar

v

m

v

v

alteration is proposed for the velocity v appearing in the no-slip tangential velocity

boundary condition at solid surfaces. These proposed revisions are based upon both

experiment and theory, including re-interpretation of the following three items: (i)

experimental near-continuum thermophoretic and other low Reynolds number phoretic

data for the movement of suspended particles in uids under the inuence of mass density

gradients Vr; caused either by temperature gradients in single-component uids undergoing

heat transfer or by species concentration gradients in inhomogeneous two-component

mixtures undergoing mass transfer; (ii) the hierarchical re-ordering of the Burnett terms

appearing in the ChapmanEnskog gas-kinetic theory perturbation expansion of the viscous

stress tensor from one of being based upon small Knudsen numbers to one of being based

upon small Mach numbers; (iii) Maxwells (1879) ubiquitous v

m

-based thermal creep or

thermal stress slip boundary condition used in nonisothermal gas-kinetic theory models,

recast in the form of a v

v

-based no-slip condition. The v

v

vs. v

m

dichotomy in the case of

compressible uids is shown to lead to a fundamental distinction between the uids tracer

velocity as recorded by monitoring the spatio-temporal trajectory of a small non-Brownian

ARTICLE IN PRESS

www.elsevier.com/locate/physa

0378-4371/$ - see front matter r 2004 Elsevier B.V. All rights reserved.

doi:10.1016/j.physa.2004.10.034

E-mail address: hbrenner@mit.edu (H. Brenner).

particle deliberately introduced into the uid, and the uids optical or colorimetric

velocity as monitored, for example, by the introduction of a dye into the uid or by some

photochromic- or uorescence-based scheme in circumstances where the individual uid

molecules are themselves responsive to being probed by light. Explicitly, it is argued that the

uids tracer velocity, representing a strictly continuum nonmolecular notion, is v

v

; whereas its

colorimetric velocity, which measures the mean velocity of the molecules of which the uid is

composed, is v

m

:

r 2004 Elsevier B.V. All rights reserved.

PACS: 51.10.+y; 66.10.x; 66.20.+d; 66.60.+a

Keywords: NavierStokes; No-slip; Rheology; Thermophoresis; Korteweg stress

1. Introduction

1.1. Background

This is the rst in a projected two-part series of papers concerned with proposed

modications to the NavierStokesFourier equations of continuum uid mechanics

(hereafter referred to by the acronym NSF equations) for compressible uids, both

gases and liquids. The term compressibility as used here refers not to the usual

effects of pressure on uid density, but rather to the effects on density of temperature

and/or composition (the latter in multicomponent mixtures) in systems where

pressure effects on density are assumed to be small relative to these other effects, e.g.

liquids or essentially isobaric gases. The present paper, the rst in the series, focuses

on the seemingly less controversial aspects of the changes we propose, namely those

connected with: (i) purely viscous effects in uids associated with the form of the

constitutive equation for the deviatoric stress appearing in Newtons rheological

viscosity law; and (ii) the no-slip tangential velocity boundary condition imposed at

solid surfaces. Experimental and other data will be presented in support of the

hypothesized changes in these two items. All of these data pertain to phenomena

involving creeping ow situations, where inertial effects in the momentum equation

are negligible, as too are viscous dissipation effects appearing in the energy equation.

Moreover, the data presented here are, for all practical purposes, limited to ideal

gases, although the underlying theory to be developed appears to bear no such

limitation.

The second paper in the projected series focuses upon further modications in the

NSF equation set posed by the work of the late statistical mechanician Yuri L.

Klimontovich in the inertial and viscous dissipative terms (as briey discussed in

Section 7). Currently, no experimental data exists to support these further changes.

Moreover, these additional changes raise fundamental questions whose profundity

and controversial nature greatly exceed the comparable level of contentiousness

likely to be aroused by the changes to the NSF equations advocated herein. As

such, it seemed prudent to clearly separate the issues associated with Klimontovichs

work from those discussed in the present paper, by simply postponing a discussion of

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 61

their common features. Those readers whose appetites are likely to be whetted by the

deeper, even more fundamental, issues to be addressed in the second paper are

encouraged to study in advance the key works of Klimontovich, briey cited in

Section 7.

1.2. Newtons law of viscosity. Mass velocity v

m

vs. volume velocity v

v

The NavierStokes equations, valid for Newtonian uids (both gases and liquids),

has been a xture of continuum uid mechanics ever since 1845 following the

seemingly denitive work of Stokes [1] and others [2], who proposed the following

rheological constitutive expression for the uids deviatoric or viscous stress T:

T = 2mVv kIV

.

v ; (1.1)

in which the velocity v appearing therein is the mass velocity v

m

; namely the velocity

appearing in the continuity equation

qr=qt V

.

(rv

m

) = 0 : (1.2)

The overbar appearing in (1.1) denotes the symmetric and traceless portion of the

dyadic which it surmounts, so that with D any dyadic, D = (

1

2

)(D D

T

) (

1

3

)I(I: D);

in which I is the dyadic idemfactor.

Despite the essentially universal acceptance of the fact that [3]

v =

?

v

m

; (1.3)

we argue below that the velocity appearing in Newtons viscosity law should, in fact,

be the volume velocity, v

v

[4,5]:

v = v

v

: (1.4)

Our arguments are based upon a trio of interrelated arguments: (i) ascribing a

continuum interpretation to experimental thermophoretic particle velocity data in

the small Knudsen number gaseous regime, thereby challenging the contemporary

view of such thermophoretic motion as a noncontinuum phenomenon (Section 3);

(ii) re-scaling the hierarchical order of the Burnett thermal stress terms appearing in

the ChapmanEnskog Knudsen number expansion of gas kinetic theory [6,7],

thereby changing their status from noncontinuum to continuum-level stresses on a

par with the viscous terms appearing in the classical NavierStokes equations

(Section 4); (iii) re-interpreting Maxwells thermal creep slip condition imposed upon

v

m

into a no-slip condition imposed upon v

v

(Section 5). Individually and collectively

these lend credibility to Eq. (1.4).

The volume and mass velocities are not independent of one another, but are

related through the expression [4]

v

v

= v

m

j

v

(1.5)

in which j

v

represents the diffusive ux of volume. [Eq. (1.5) represents the

decomposition of the volume ux n

v

into respective convective and diffusive

contributions, n

m

^ v and j

v

; where ^ v = 1=r is the specic volume.] In the case of

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 62

single-component uids undergoing heat transfer the constitutive equation for j

v

is

given by the expression [4]

j

v

= aV ln r ; (1.6)

wherein a = k=r^ c

p

is the uids thermometric diffusivity, with k the thermal

conductivity and ^ c

p

the isobaric specic heat. Eq. (1.6) is also applicable to the case

of two-component mixtures undergoing isothermal mass transfer [4], but with a

replaced therein by the Ficks law binary diffusion coefcient D: The respective heat-

or mass-transfer cases to which (1.6) applies correspond to circumstances in which,

for a xed pressure, either r = r(T) or r = r(w); with T the temperature and where

w denotes either one of the two species weight fractions in the isothermal binary

mixture.

Obviously j

v

= 0 when the uid is incompressible, corresponding to the case where

r is uniform throughout the uid (for all time), and hence from Eq. (1.2) for which

V

.

v

m

= 0: In such circumstances the velocities v

m

and v

v

coalesce, whence the

modied Newtons viscosity law (1.1) (1.4) reverts to its conventional form, (1.1)

(1.3).

1.3. What velocity appears in the no-slip boundary condition?

Accompanying the v

m

vs. v

v

velocity issue with respect to the constitutive choice

for v appearing in the deviatoric Newtons law stress expression for T; Eq. (1.1), is a

comparable issue that arises in connection with the dynamical no-slip tangential

velocity boundary condition

I

s

.

(v U) = 0 on qV

s

(1.7)

imposed at a solid surface qV

s

; with U the velocity of the solid at a point lying

on its surface. In the above, with n a unit normal vector on the surface, I

s

= I nn is

the unit surface dyadic or surface projection operator. While v

m

is universally

regarded as being the appropriate velocity v to insert into (1.7) under ordinary

circumstances, we nevertheless present experimental data as well as theoretical

kinetic theory results dating back to Maxwell [8] in 1879 (see Section 5) that implicity

supports the fact that the velocity appearing in (1.7) should be v

v

rather than

v

m

: On the other hand, the purely kinematical no-penetration, normal-velocity

boundary condition,

n

.

(v

m

U) = 0 on qV

s

; (1.8)

retains its usual mass-based form.

1.4. The uids tracer velocity

Let the spatio-temporal curve x = x(x

0

; t) denote the trajectory through space of a

small (albeit non-Brownian) passive tracer particle entrained in the uid that passes

though the space-xed point x

0

at time t = 0 and is later observed to be present at

some other point x at time t: The current, purely kinematical, view of continuum

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 63

uid motion is that the uids tracer or Lagrangian velocity v

l

; dened by the relation

v

l

:=

qx

qt

_ _

x

0

(1.9)

and derived from the tracers trajectory, is identical to the uids mass velocity v

m

[911]. In opposition to the accepted view that v

l

?

=

v

m

; we will argue later (see Section

6), based upon the same experimental data and gas-kinetic theory result invoked in

support of the relation v = v

v

; that, in fact,

v

l

= v

v

: (1.10)

For the time being we do not proffer any general theoretical reasons as to why

seemingly incontrovertible theoretical notions underlying the classical hypothesis

that v = v

m

fail in the case of compressible uids. Rather, we simply regard our main

result, v = v

v

; as being purely empirical. Our results do, however, point up the

singular nature of so-called incompressible uids, a subject that has long attracted

the attention of theoreticians, and led, inter alia, to the development of the eld of

extended irreversible thermodynamics [12]. Indeed, our results will be seen to

impact on the general subject of irreversible thermodynamics [1316] as a whole,

with regard to both the presence of nonnegative quadratic terms in the local rate of

entropy production and the Onsager symmetry relations [17] for linear constitutive

force/ux relations.

2. Pre-constitutive transport equations

2.1. Generic physical laws

For simplicity in what follows we limit ourselves to single-component Newtonian

uids undergoing heat transfer. The basic equations governing transport in such

uids [18] consist of: (i) the continuity Eq. (1.2); (ii) the Cauchy linear momentum

equation (in the absence of external body forces),

r

D

m

v

m

Dt

= V

.

P; P = Ip T; (2.1)

and (iii) the energy equation,

r

D

m

^ e

Dt

= V

.

j

u

V

.

(P

.

v

m

); ^ e = ^ u v

2

m

=2 : (2.2)

In the above,

D

m

Dt

:=

q

qt

v

m

.

V (2.3)

denotes the material derivative, p is the thermodynamic pressure, P the pressure

tensor, and ^ e and ^ u are, respectively, the specic (i.e., per unit mass) total and

internal energies. Moreover, j

u

is the diffuse internal energy current (i.e., ux

density), whose constitutive form remains to be specied. No distinction need be

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 64

made between the diffusive total and internal energy uxes, j

e

and j

u

; since neither

kinetic nor potential energy (the latter present when time-dependent conservative

forces actsee Appendix A) can be transported diffusively, only convectively. While

we keep open the choice of velocity v appearing in the constitutive expression (1.1)

for T contributing to (2:1

2

); accounting for our use of the word pre-constitutive to

describe the above pair of Eqs. (2.1) and (2.2), no comparable freedom of choice is

possible for the other velocities appearing in these equations, all of which have been

chosen to be v

m

: These other velocities, three in number, refer to their respective roles

as: (i) the specic momentum density, say ^ m; the latter appearing in the guise of v

m

in

Eq. (2:1

1

) [19,20]; (ii) the kinetic energy, say v

2

k

=2; the latter appearing in the guise

of v

2

m

=2 in Eq. (2:2

2

); and (iii) the rate of working, say V

.

(P

.

v

w

) the latter

appearing in the guise of V

.

(P

.

v

m

) in Eq. (2:2

1

): As discussed in Appendix A, this

lack of freedom in possibly choosing one or more of these three velocities, namely

( ^ m; v

k

; v

w

); to be v

v

; say, rather than v

m

; is imposed by the requirement that the

continuity, momentum, and energy equations all remain invariant under choice of

reference frame.

While it is commonly assumed [18] that the diffusive internal energy current j

u

is

given in single-component uids by Fouriers law, namely

j

u

= q ; (2.4)

where

q = kVT ; (2.5)

we have argued elsewhere [4,21] that in the case of compressible uids the correct

expression should be given, rather, by the constitutive relation

j

u

= q pj

v

: (2.6)

To the extent that Eq. (2.6) is correct, the diffuse volume current j

v

transports not

only momentum diffusively, as implied by Eqs. (1.1) (1.4)(1.5), but, concurrently,

it also carries internal energy diffusively, as embodied in the j

v

term appearing in Eq.

(2.6), above any beyond the Fourier conduction term (2.5). In order to keep our

pre-constitutive options open for as long as possible, thereby eschewing a

particular constitutive choice for j

u

; i.e., Eq. (2.4) vs. (2.6), it proves convenient to

write the ux density j

u

appearing in the energy equation (2:2

1

) in the pre-

constitutively neutral form,

j

u

= q p(v v

m

) : (2.7)

In view of Eq. (1.5), this expression thus constitutively embodies both the

conventional and modied formulas for j

u

; namely (2.4) or (2.6), according as either

v = v

m

or v = v

v

:

It also proves convenient to reformulate the energy equation (2.2) in terms of

enthalpy, rather than internal energy. By denition, ^ u =

^

h p^ v in which

^

h is the

specic enthalpy and ^ v = 1=r is the specic volume. Application of the material

derivative operator (2.3) to this thermodynamic identity, together with use of both

the continuity equation (1.2) and the standard single-component thermodynamic

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 65

relation [22]

d

^

h = ^ c

p

dT ^ v T

q^ v

qT

_ _

p

_ _

dp ; (2.8)

eventually transforms Eq. (2.2) into the form

r^ c

p

qT

qt

v

m

.

VT

_ _

= V

.

(kVT) V

.

[p(v v

m

)]

q ln r

q ln T

_ _

p

D

m

p

Dt

2mVv: Vv

m

k(V

.

v)(V

.

v

m

) : (2:9)

In the classic case, where v = v

m

; this reduces to the standard equation [18, p. 589]

governing the spatio-temporal evolution of the temperature eld in single-

component uids.

Additionally, when written out explicitly, the constitutively neutral linear

momentum equation (2.1), applicable to both the conventional and unconventional

choices of v; becomes

r

qv

m

qt

v

m

.

Vv

m

_ _

= Vp V

.

(2mVv) V(kV

.

v) : (2.10)

In the subsequent context of analyzing the experimental phoretic data used to

support our hypothesis that v = v

v

; it will be seen [2325] that the dissipative

terms, other than V

.

(kVT); appearing in the energy equation (2.9) and the inertial

terms appearing in the momentum equation (2.10) prove to be negligible in the

present class of phoretic experiments, whence it will turn out that these equations

are, respectively, replaced by the much more tractable expressions,

r^ c

p

qT

qt

v

m

.

VT

_ _

- kV

2

T (2.11)

and

Vp mV

2

v kVV

.

v - 0 ; (2.12)

the latter constituting a creeping ow approximation (cf. [82]). Constant physical

properties have been assumed in the above pair of equations, except of course for the

density r:

2.1.1. Boundary and initial conditions

Irrespective of which of the two constitutive relations, v = v

m

or v = v

v

; is

ultimately identied as being the physically correct choice, the requisite velocity

boundary conditions (1.7) and (1.8) to be imposed upon the independent variables

(v

m

; p; r; T) appearing in Eqs. (2.9) and (2.10), or in the simplied phoretic forms

(2.11) and (2.12), are applicable for both choices of v:

2.1.2. Further simplications

For the class of phoretic and transpiration problems that we subsequently address

it will be assumed as a satisfactory approximation that the law of adiabatically

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 66

additive volumes [4] adequately describes the equation of state for the uid,

corresponding to the fact that (q^ v=qT)

p

is a constant at a xed pressure. (The latter

represents an obviously correct assumption in the case of single-component ideal

gases; moreover, in the case of liquids it is surely a valid approximation over

sufciently small temperature ranges). This assumption, in conjunction with the fact

that the viscous dissipative terms in the energy transport equation (2.9) are

negligible, leads to the conclusion [4] that the volume velocity is solenoidal,

V

.

v

v

= 0 ; (2.13)

despite the fact that V

.

v

m

a0 in the case of compressible uids. Eq. (2.13) is a purely

kinematical relation, and hence holds irrespective of whether the dynamical

constitutive choice made for v is correctly given by v

m

or v

v

[26,27].

2.1.3. The case v = v

v

As a consequence of (2.13) the bulk viscosity term disappears from Eq. (2.12)

when the constitutive equation v = v

v

applies (although this term will not generally

disappear in the classical case where v = v

m

unless k = 0). In such circumstances, Eq.

(2.12) simply becomes

Vp mV

2

v

v

- 0 : (2.14)

Note in this case that Eqs. (2.13) and (2.14) are now identical in appearance to the

classical creeping ow equations (cf. Ref. [82]) for incompressible uids, wherein v

m

appears in these equations in place of v

v

: When considered in conjunction with the

no-slip boundary condition (1.7) imposed upon v

v

; we see that the solutions (v

v

; p) of

such compressible ow problems may be simply obtained from those already existing

in the literature for conventional incompressible creeping ow solutions [28].

3. Thermophoretic motion. Experimental conrmation of the no-slip condition (1.7)

for v = v

v

The ultimate test of any physical theory lies in the agreement of its quantitative

predictions with experiment. In this context we advance the hypothesis that the

velocity v appearing in the pre-constitutive energy and momentum Eqs. (2.9) and

(2.10) as well as in the no-slip boundary condition (1.7) is correctly given by v = v

v

;

rather than by its traditional form v = v

m

: This hypothesis is based upon what will be

shown, inter alia, to be its accord with existing thermophoretic [23] and other [24,25]

phoretic data (the latter data being discussed in Section 7). Subsequently, in Section

6, we tentatively advance a reason for the success of this constitutive choice, derived

from the empirical observation, demonstrated after the fact, that v

v

; rather than v

m

;

constitutes the tracer (or Lagrangian) velocity v

l

of the uid continuum. However,

we neither require, nor do we proffer here, a rational explanation of the fact that

v = v

v

; rather, we simply regard the latter constitutive expression as representing a

purely empirical relation, one that when used in conjunction with the pre-

constitutive momentum and energy transport equations (2.1) and (2.2) and

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 67

boundary conditions of Sections 1 and 2, together with the continuity equation, ts

the all of the experimental facts to which it is addressed (including, of course, the

wealth of data existing for the incompressible case, for which circumstance v

v

and v

m

are synonymous).

Thermophoresis is a phenomenon whereby a generally heat-conducting, force-

and torque-free solid particle, typically spherical, suspended in a uid (usually a gas)

within which an externally imposed temperature gradient exists, is observed to move

from the hotter to the colder regions of the uid; that is, the particle moves against

the temperature gradient [2932]. Recognition of this phenomenon was apparently

rst recorded in the literature by Tyndall [33,34] in 1870. The rst successful

quantitative explanation of thermophoresis, limited to gases, was offered by Epstein

[35] in 1929, who, building upon Maxwells [8] explanation of the phenomenon of

thermal transpiration some 50 years earlier, also involving uid motion in gases

animated by a temperature gradient [cf. 24], attributed thermophoretic particle

motion in the so-called near-continuum range of Knudsen numbers (Kn51) to

small noncontinuum effects, resulting in Maxwell slip (thermal creep.) at the

particle surface (see Section 5). Maxwells argument ascribes this v

m

slip to the action

of thermal stresses existing in the gas proximate to the surface (see Section 4).

Despite many embellishments since Epsteins [35] original analysis, the explanation

of the thermophoretic movement of aerosol particles in gases for Kn51 remains,

today, universally accepted as a strictly noncontinuum phenomenon, since no such

motion, either of the particle or uid, is predicted by NSF equations when

considered in conjunction with the traditional no-slip boundary condition. However,

since the thermophoretic velocity of a macroscopic non-Brownian particle in the

near-continuum region is observed to be independent of its size, this noncontinuum

view of the phenomenon appears inconsistent to us. Explicitly, for a given gas

pressure, and hence a given mean-free path l; the non-Brownian particles

thermophoretic velocity U is observed to be independent of the Knudsen number,

Kn = l=a; based upon the sphere radius a: (In the latter, l = 1=nps

2

according to

elementary kinetic theory [18], with n the number density of molecules and s the

molecular collision diameter.) And since the Kn value is the sole determinant of

whether the observed phenomenon is, or is not, due to noncontinuum effects, such

particle size-and, hence, Knudsen number-independence appears inconsistent with

the latter possibility.

Epsteins [35] noncontinuum thermal creep interpretation of thermophoretic

motion in the small Knudsen number regime was based upon his use of the

traditional relation v = v

m

in the constitutive equation (1.1) for the deviatoric stress

T; together with his adoption of Maxwell slip [8] [cf. Eq. (5.2)] of the mass velocity v

m

at the particle surface in lieu of the traditional no-slip condition (1.7) (1.3). We

offer here an alternative, strictly continuum interpretation of thermophoresis based

upon use of the constitutive equation v = v

v

; in both (1.1) and (1.7), the latter

connoting no slip of the volume velocity v

v

at the sphere surface. As in the

accompanying thermophoresis paper [23; see also Appendix B], we address the

problem of a laterally unbounded single-component uid, either gas or liquid,

conned between two parallel walls separated by a distance L; with the hot wall

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 68

situated at the coordinate x = 0 maintained for all time at a temperature T

0

; and the

cold wall situated at x = L maintained at T

L

: A solid sphere of radius a (a=L51)

and thermal conductivity k

s

; present in the uid, is situated sufciently far from

either wall such that particle-wall hydrodynamic interaction effects can be neglected.

Gravity effects are also assumed negligible. The thermal boundary conditions, as

usual, entail continuity of both the temperature and the normal heat ux component

at the sphere surface. Using the mass, momentum, and internal energy equations (the

latter within both the uid and solid sphere) of Section 2, we seek to calculate the

velocity U of the force- and couple-free sphere for circumstances in which the uid

motion may be regarded as quasistatic. In what follows in the next two subsections,

this calculation is effected for both constitutive choices, v

m

and v

v

; of the velocity v:

Ultimately the respective predictions of U for the two cases are compared with

experiment.

3.1. The case v = v

m

Upon use of the traditional v

m

formulation of the NSF equations and no-slip

boundary condition imposed upon v

m

in (1.7) it readily follows [23], inter alia, from

the trio of mass, momentum, and energy equations, in conjuction with the appropriate

thermal boundary conditions, that v

m

= 0 and p = const: (\x); corresponding to the

absence of uid motion and concomitant sphere motion, U = 0: After all, the problem

is one of steady-state, convection-free, heat conduction through the uid as well as

through the spheres interior, governed in both phases by the classical heat conduction

equation, V

2

T = 0: As such, it is unsurprising that no force acts on the sphere that

would otherwise serve to animate it. It was this failure of the traditional continuum

NSF equations and boundary conditions to predict the observed thermophoretic

motion of the sphere that led Epstein [35], later followed by others (see the review in

Ref. [23]), to seek a noncontinuum slip-based explanation for this particle motion.

Apart from the nonuniform temperature eld T(x) characterizing this pure heat-

conduction problem, the only other interesting physical feature worthy of noteone

that would, perhaps, not normally come to mindis the fact that the undisturbed

temperature gradient, [VT[ = (T

0

T

L

)=L; existing in the quiescent isobaric uid

necessarily creates a corresponding density gradient, Vr; owing to the uids isobaric

equation of state, r = r(T): Nevertheless, according to conventional NSF theory,

the existence of this density gradient is predicted to be without physical effect as

regards steady-state momentum and energy transport. As will be seen, it is in this

respect, namely the absence of physical consequences stemming from the local thermal

expansion of the uid, that the traditional constitutive choice, v = v

m

; in Eqs. (1.1) and

(1.7) ultimately proves to be unsatisfactory in explaining the origin of the uid-

mechanical forces serving to animate the sphere.

3.2. The case v = v

v

With this alternative choice of consitutive equation, the governing equations

and boundary conditions outlined in Sections 1 and 2 now yield [23] nontrivial

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H. Brenner / Physica A 349 (2005) 60132 69

physical results, wherein Ua0; stemming from the presence of a temperature-

induced density gradient. In effect, the departure from the traditional NSF result

described in the preceding paragraph, wherein U = 0; is a consequence of the

appearance of the density gradient in the constitutive equation (1.6) for the

diffusive volume ux, which, through Eqs. (1.4) and (1.5), serves to couple v

v

to Vr;

thereby ultimately linking the particles thermophoretic motion to the uids

thermal expansion. The mathematical details underlying the calculation of U

are set forth in a companion paper [23; but see also Appendix B], which incor-

porates several simplifying assumptions in order to reduce the algebraic effort

required to solve these now strongly coupled transport equations. In addi-

tion to assuming constant equilibrium and transport properties for ^ c

p

; k; k

s

and m; Eq. (2.13) was further assumed to be applicable. In circumstances

where the particle is nonconducting, corresponding to the case where k

s

= 0; it is

shown in Appendix B that the calculation of U can be effected trivially by the use of

Faxens law, without the need to literally solve the requisite boundary-value

problem!

In any event, the more detailed and general calculation [23] based upon the

constitutive relation v = v

v

; addressing the case where k

s

a0; eventually yields the

following expression for the thermophoretic velocity of the sphere:

U =

ab

1 (k

s

=2k)

VT (3.1)

in which b = (q ln ^ v=qT)

p

(q ln r=qT)

p

is the uids coefcient of thermal

expansion. Furthermore, VT is the temperature gradient in the neighborhood

of the sphere that would exist in the spheres absence from the uid. It is given by the

expression VT = ^ x(T

0

T

L

)=L; in which ^ x is a unit vector in the x-direction,

perpendicular to the walls. We note that the product, ab k(q^ v=qT)

p

=^ c

p

; appearing

in Eq. (3.1) is a temperature-independent constant, since each of the three thermal

transport and equilibrium properties appearing on the right-hand side of the product

have, individually, been supposed constant. According to its derivation, Eq. (3.1) is

equally applicable to all uids, whether gas or liquid.

3.3. Comparison of Eq. (3.1) with experimental data

3.3.1. Gases

In the case of nonpolar, generally polyatomic, ideal gases, the gass thermometric

diffusivity appearing in Eq. (3.1) can be expressed via the Eucken equation [18] as

a = (9 5g

1

)u=4; with u = m=r the uids kinematic viscosity and g = ^ c

p

=^ c

v

the

uids specic heat ratio. In addition, b = 1=T for ideal gases. Accordingly, in such

circumstances Eq. (3.1) becomes

U = C

/

s

1

1 (k

s

=2k)

uV ln T ; (3.2)

in which C

/

s

= C(9 5g

1

)=4 is an O(1) dimensionless coefcient. The values of g for

ideal monatomic and diatomic gases are, respectively, g =

5

3

and g =

7

5

; whence it

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H. Brenner / Physica A 349 (2005) 60132 70

follows that:

C

/

s

=

1:5 (monatomic gases) ;

1:36 (diatomic gases) :

_

(3.3)

The Eucken relation entering into (3.3) is an approximate relation. More precisely,

with Pr = ^ c

p

m=k the uids Prandtl number, it follows that a = u=Pr; representing an

exact relation between a and u: Expressed more accurately, one thus has for ideal

gases that C

/

s

= 1=Pr:

Experimentally, in the case of gases, the thermophoretic velocity U of a spherical

particle relative to the walls (on whose surfaces the prescribed temperatures T

0

and

T

L

are time-independent constants) is given over the entire range of Knudsen

numbers, Kn = l=a; from the near continuum regime, Kn51; to the free-

molecule regime, Knb1; by the semi-empirical data correlation,

U =

C

s

(k=k

s

C

t

Kn)

(1 3C

m

Kn)(k=k

s

1=2 C

t

Kn)

uV ln T : (3.4)

This generally Knudsen number-dependent formula, due originally to Brock [36],

builds upon the prior work of Epstein [35] (see the correlations in Refs. [3640]), and

serves to organize a vast amount of experimental thermophoretic data for gases. The

dimensionless coefcients C

m

; and C

t

; are manifestations of noncontinuum

hydrodynamic isothermal velocity slip and thermal jump effects, respectively,

whereas C

s

is Maxwells, nonisothermal slip-velocity thermal creep coefcient. The

latter is assumed in Maxwells [8] model of the phenomenon (see Section 5) to

constitute a noncontinuum effect arising from the so-called thermal stresses. [In our

view, on which we will subsequently elaborate, this would appear to be an

inconsistency, since C

s

is invariably taken to be a constant, independent of Knudsen

number. This independence serves to distinguish its effects from those of the other

two terms appearing in (3.4) involving the pair of noncontinuum coefcients, C

m

and

C

t

; each of which, being multiplied by the Knudsen number, thus disappears from

consideration in the Kn = 0 continuum limit.] A compilation is available [39] of

best t experimental values for these three semi-empirical coefcients, correspond-

ing to the values C

s

= 1:17; C

m

= 1:14; and C

t

= 2:18:

In the free-molecule limit, Kn o; Eq. (3.4) shows that U 0: This was to be

expected intuitively, since the spacing between molecules is so large on average

compared with the size of the sphere that the molecules do not see the latter and

hence pass it by unimpeded, failing thereby to animate the sphere.

In the continuum limit, Kn 0; of interest to us in connection with the test of our

continuum hypothesis v = v

v

; Eq. (3.4) adopts the form

U = C

s

1

(1 k

s

=2k)

uV ln T : (3.5)

Following its original introduction in 1879 [8], the nature and magnitude of

Maxwells slip coefcient C

s

; the only one of the three noncontinuum coefcients

now contributing to U; has attracted the attention of a number of theoreticians and

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H. Brenner / Physica A 349 (2005) 60132 71

experimentalists. As discussed in the accompanying paper [23], theoretical values of

C

s

have ranged from Maxwells [8] original estimate of

3

4

for Maxwell molecules to

Derjaguin et al.s [38] predicted value of

3

2

; with experimental values falling in the

range 0.891.17, the latter gure constituting the most recent best-t value [39,40].

These latter, experimentally based, values are assumed applicable to both

monatomic and polyatomic molecules, despite the fact, historically, the theories

dating back to Maxwell [8], and underlying the generic equation (3.4) were based

entirely upon, and therefore presumably limited to, monatomic Maxwell molecules.

Our theoretical formula (3.2) (3.3) for gaseous continua obviously accords well

with the experimental data correlation (3.5) for the near-continuum regime. This,

despite the fact that our formula is based upon purely continuum-mechanical no-slip

arguments, which suppose that v = v

v

: In contrast, Epsteins [35] theory, which

underlies Eq. (3.5), is based upon noncontinuum thermal creep arguments, while

supposing that v = v

m

; albeit with a Maxwell tangential slip velocity boundary

condition imposed upon v

m

(in contrast with the traditional case, where no v

m

slip is

normally assumed to occur). Subsequently, in Section 5, the agreement between these

two very different theoretical approaches, Epsteins and ours, is reconciled, where it

is pointed out that the attribution by Epstein and others of noncontinuum Knudsen-

based behavior to Maxwells slip condition appears to be unwarranted, a

misconception not actually due Maxwell himself, but rather to those who followed

him [4144].

3.3.2. Liquids

Our companion paper [23] also compares our theoretical v

v

-based equation (3.1)

with the experimental thermophoretic data of McNab and Meisen [45] for liquids,

the only such single-particle liquid-phase data known to us. Without repeating

what is said in Ref. [23], sufce it to say here that Eq. (3.1) accords satisfactorily with

these limited data. Clearly, liquids are incapable of displaying noncontinuum

behavior with respect to rationalizing the thermophoretic movement of macroscopic

(non-Brownian) particles. As such, there exists no possibility that the thermo-

phoretic behavior observed by McNab and Meisen in liquids can be explained by

other than a continuum mechanism [46]. Since, as we have pointed out, classical

continuum arguments, based on the assumption that v = v

m

; fail to predict any

thermophoretic motion whatsoever, the agreement of our nontraditional v = v

v

continuum model with the liquid-phase data of McNab and Meisen [45] would

appear to enhance the credibility of our nontraditional volume velocity hypothesis.

An alternative theory of thermophoresis in liquids has recently been put forward

by Semenov and Schimpf [47]; see also Refs. [135,136]. In common with our

approach, their expression for the thermopheretic velocity of a solute molecule

contains the same thermal expansion proportionality factor b[1 (k

s

=2k)]

1

VT as

appears in our Eq. (3.1) [see Eq. (8.9)]. Moreover, in agreement with our predictions

for liquids, their thermophoretic velocity too is independent of particle size.

However, in contrast with our analysis, where the solute particle plays a passive

role relative to the solvent (at least in the nonconducting case), while simply being

entrained in a uid already in (volumetric) motion owing to the temperature gradient

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H. Brenner / Physica A 349 (2005) 60132 72

(see Section 6), in the SemenovSchimpf model the physicochemical properties of the

solute particle enter explicitly into their expression for U: Their results are principally

employed to calculate Soret and thermal diffusivites in polymer solutions, a topic

that we too have addressed elsewhere [48] based upon our Eq. (3.1), and wherein we

have compared our respective predictions. Further commentary on their model vs.

ours is offered in Section 8.

4. A modied Newtons law of viscosity. Theoretical conrmation of the deviatoric

stress relation for v = v

v

based upon the re-scaled Burnett equations

To the extent that the appropriate constitutive velocity v appearing in Eq. (1.1) for

the viscous stress is given by v

v

rather than by its more traditional value v

m

; Newtons

viscosity law (1.1) departs from its usually assumed form, resulting in the following

equation for the deviatoric stress [49]:

T = T

m

2mVj

v

; (4.1)

in which Eq. (1.5) has been used. Here,

T

m

= 2mVv

m

(4.2)

denotes the traditional form of Newtons rheological law. The revised relation (4.1)

plays a major role in the detailed thermophoretic calculations of Ref. [23] (see also

Appendix B for the nonconducting case) summarized in the preceding section. But in

those calculations the choice of the velocity v appeared not only in Newtons

viscosity relation (1.1), but also in the no-slip boundary condition (1.7). As such, it is

not inappropriate to ask: Is there any independent evidence of the correctness of the

revised rheological law (4.1) that does not rely on the solution of a particular

boundary-value problem, and hence on the validity of the nonstandard no-slip

boundary condition (1.7), such as entered into the thermophoretically based indirect

evidence provided in Section 3 for the viability of the constitutive relation v = v

v

?

The answer is Yes! Direct evidence does indeed exist, based upon the well-known

results of Burnett [7] in the kinetic theory of gases, as set forth in standard texts [6]

on the subject.

Extracting physically relevant results from the kinetic theory of gases involves

solving the Boltzmann equation for ideal, single-component, monatomic gases by

asymptotically expanding the solutions thereof for the deviatoric stress eld T and

heat ux vector q in powers of the Knudsen number for Kn51: These expansions

take the form [6]

T = T

0

Kn T

1

Kn

2

T

2

O(Kn

3

) ; (4.3)

with a similar expansion for q: The leading-order, O(Kn

0

) O(1); so-called

continuum term in this expansion corresponds to the Euler equation of ideal

uid theory, namely T

0

= 0 and q

0

= 0; according to which only convective

momentum and energy transport mechanisms exist. Equivalently, diffuse or

molecular transport mechanisms are absent. The next, O(Kn); term in the expansion,

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H. Brenner / Physica A 349 (2005) 60132 73

the so-called near-continuum contribution to the stress tensor, yields Newtons

law of viscosity, namely Kn T

1

= T

m

as well as Fouriers law of heat conduction,

Kn q

1

= kVT: Proceeding further in the hierarchy, the so-called noncontinuum

O(Kn

2

) terms in the expansion of the deviatoric stress [50] correspond to a sequence

of generally nonlinear Burnett terms [6,7], representing the corrections to the

classical v

m

-based Newtonian deviatoric stress tensor (4.2) [5154]. Upon incorpor-

ating these Burnett terms into the expression for the deviatoric stress, it proves

convenient to write

T = T

m

T

O(Kn

3

) ; (4.4)

with T

Kn

2

T

2

; which is of O(Kn

2

); designated here as being the extra

deviatoric stress, above and beyond the Newtons law T

m

-level.

Kogan et al. [55] and Bobylev [56] (see also the recent work of Yariv and Brenner

[57], briey summarized near the end of the present section) each discuss the

hierarchical ordering of the six O(Kn

2

) Burnett terms contributing to T

(see [6, p.

286]) with respect to their relative orders-of-magnitude in relation to the near-

continuum O(Kn) Newtonian term, Eq. (4.2). The KoganBobylev discussion of the

pertinent scaling issues leads to the following conclusion: For Kn51; and for

circumstances in which both a characteristic Reynolds number Re LU=n and a

characteristic nondimensional temperature gradient L[VT=T[; each based upon

some characteristic length L of the system, are both of O(1); two terms among the six

appearing in the complete Burnett sequence of stresses [6,7] are, in fact, actually of

O(Kn); rather than of O(Kn

2

); and hence should properly be classied hierarchically

as belonging to the traditional NSF equation set. In drawing the distinction

between their modied view [5557] of the scaling of the Burnett terms and the more

traditional view [6,7] thereof, the velocity U appearing in their denition of Re used

in the scaling is taken to be the uid-mechanical velocity v

m

rather than the velocity

of sound, c:

These two re-scaled Burnett deviatoric stress terms are given explicitly by the

expression

T

=

m

2

rT

(K

1

VVT K

2

T

1

VTVT) ; (4.5)

wherein K

1

and K

2

are O(1) dimensionless constants whose respective values depend

upon the particular choice of intermolecular potential used in evaluating the

Boltzmann collision integral. As the two terms in Eq. (4.5) contributing to the

deviatoric stress both depend exclusively upon temperature gradients in the gas, they

are referred to in the literature as thermal stresses, a concept dating back to

Maxwell [8]. As discussed below, this pair of thermal stresses should not be regarded

as O(Kn

2

) noncontinuum terms, but rather as near-continuum O(Kn) terms in the

terminology of gas-kinetic theory, since they are of the same order as those

appearing in the NSF equation set. Of course, in uid-mechanical parlance, both

the Euler and NSF equations are regarded as strictly continuum-level linear

momentum equations! As such, in sorting out the issues, one must carefully

distinguish between the respective gas-kinetic and uid-mechanical notions of what

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H. Brenner / Physica A 349 (2005) 60132 74

constitutes a continuum. This issue is further discussed in the next section in relation

to Maxwells thermal stress-induced, so-called slip, boundary condition.

For monatomic Maxwell molecules [6,7,58] the values of the two constants are,

respectively, K

1

= 3 and K

2

= 3d ln m=d ln T: Accordingly, Eq. (4.5) adopts the

form [59]

T

=

3m

rT

V(mVT):

Now, m = ru; in which u is the kinematic viscosity. Furthermore, for single-

component ideal gases the relation between density and temperature at constant

pressure is such that r = C=T; where C is a constant. Thereby, it readily follows that

for isobaric situations,

T

= 3mV(uV ln r):

However, for an ideal monatomic gas, one has from the Eucken relation [18] that

u = (2=3)a: Accordingly, with use of the constitutive equation (1.6) for j

v

applicable

to the present single-component heat-transfer case, the preceding equation for the

extra stress tensor becomes, exactly,

T

= 2mVj

v

: (4.6)

Upon inserting the latter into (4.4) and comparing the resulting expression with

Eq. (4.1), it is seen that the relation thereby obtained for T via gas-kinetic theory

arguments is identical to that obtained from our purely continuum-mechanical

relation (4.1), the latter simply having been hypothesized on the basis of the

agreement of the v = v

v

-based predictions derived therefrom with thermophoretic

(and other) experimental data. By any reasonable criterion this exact agreement

between two such disparate derivationsone based upon purely theoretical

molecular-level arguments, and the other upon purely experimental continuum-

level argumentsboth yielding exactly the same rheological constitutive expression

for the stress tensor, is so striking as to provide seemingly unequivocal corroboration

of the correctness of the proposed continuum-mechanical constitutive equation (1.1)

(1.4) as well as of the no-slip boundary condition (1.7) entering into the

calculation, certainly for gases. Concomitantly, on the gas-kinetic side of the ledger,

this agreement would appear to provide compelling evidence in support of the

Kogan/Bobylev [55,56] argument that the hierarchical perturbation order of the two

Burnett thermal stress terms (4.5) is such that they should indeed be regarded as

representing near-continuum O(Kn); but not noncontinuum O(Kn

2

); terms. That is,

in uid-mechanical terminology the pair of Burnett thermal stresses (4.5) should be

labeled as being strictly continuum-level terms, on a par with those in the NSF

equation set.

As subsequently discussed, this altered view of the classical gas-kinetic theory

Burnett hierarchy has important consequences in a variety of contexts, including a

re-interpretation of Maxwells slip condition (Section 5), currently regarded as a

manifestation of noncontinuum O(Kn

2

) effects. Equally striking is the fact thatto

the extent that our modied constitutive equation v = v

v

; together with Eqs. (1.5)

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H. Brenner / Physica A 349 (2005) 60132 75

and (1.6), is accepted as being correct on the basis of experimental conrmation

such experiments may be regarded as also formally conrming key aspects of

Burnetts gas-kinetic theory calculations. On the other hand, a number of tantalizing

theoretical issues remain unresolved with respect to the foundations of gas-kinetic

theory. Why, for example, does it appear on the basis of the K

1

and K

2

values

appearing in Eq. (4.5) that it is only for Maxwell molecules that the constitutive

equation (1.6) holds for monatomic gases? And, more generally, how does the notion

of a volume velocity enter into kinetic theory?

In any event, and irrespective of the latter issue, a formal rationalization of the

retention of only the two thermal stress terms in the Burnett expansion, while

disregarding the other four terms appearing therein, is provided in Ref. [57]. That

rationalization is based upon the fact that classical ChapmanEnskog, small

Knudsen number expansion of the Boltzmann equation is not uniformly valid. This

derives from the fact that with v a characteristic velocity, the Knudsen number is

related to the Mach and Reynolds numbers, M = v=c and Re = Lv=u; respectively,

by the expression Kn = M=Re: The conventional scaling arguments used in

obtaining the ChapmanEnskog perturbation expansion for the Kn51 near-

continuum O(Kn) case are commonly understood as applying in the dual limits,

M = O(1) and Reb1; that is, where v = O(c) [6]. However, one could, alternatively,

achieve the limiting Kn51 near-continuum criterion by instead considering the dual

pair of inequalities, M51 and Re = O(1); corresponding to the case where v =

O(v

m

)5c: And it is precisely for those circumstances in which this dual combination

of limits (rather than the single limit Kn51) is met that one would expect a linearized

rheological law like Newtons law of viscosity to be valid. When each member of the

complete set of six Burnett terms is now individually rescaled according to these

altered criteria, one nds that the two thermal stress terms, designated by T

in Eq.

(4.5), indeed become of the same order as the classical viscous stress terms (4.2) with

respect to their hierarchical O(M) ordering in the perturbation expansion. It is this

formal small Mach number re-scaling [57] that singles out for special attention only

the two thermal stress terms among the six Burnett terms, the remaining ones all

being of higher order in Mach number. Explicitly, in place of Eq. (4.3) one would

now write

T = T

(0)

MT

(1)

M

2

T

(2)

O(M

3

); Re = O(1) ; (4.7)

valid for M51; with MT

(1)

given by Eq. (4.1).

Written out explicitly in the light of (1.5), Eq. (4.1) becomes

T = 2mVv

v

: (4.8)

This relation has, thus far in this section, been independently conrmed to apply

only to the case of single-component monatomic ideal gases. However, to the extent

that Eq. (1.1) (1.4) applies quite generally, all Newtonian uids [liquids and

polyatomic gases, both single- and two-component, the latter with a replaced in (1.6)

by the binary diffusivity D], would be expected to obey Eq. (4.8), at least in

circumstances where bulk viscosity effects are absent (the latter due either to the fact

that k is zero or that V

.

v

v

= 0) [60].

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H. Brenner / Physica A 349 (2005) 60132 76

In summary of the results of this section, while the existence of thermal stresses as

embodied in Eq. (4.5) or any of its subsequent variants has, in the past, been

regarded as a noncontinuum, Knudsen-type phenomenon, this attribution does not

appear to be correct, as shown by the above analysis. By way of comparison, in the

case of solids, the comparable existence of thermoelastic stresses [61] in linearly

elastic media obeying Hookes law, and stemming from thermal expansion, has long

been recognized as a strictly continuum-level phenomenon. That it has taken so long

to recognize the existence of comparable continuum-level thermal stress effects in

uids, stemming from the same thermal expansion effects as exist in solids, is surely

attributable to the focus upon mass rather than volume in connection with

deformation in uid continua. In solids it is the geometry of continuous deformation

rather than the displacement of mass, viewed as a continuum, that commands ones

attention when addressing the fundamental issue of the movement of the respective

continua through space [62]. Dilatation, a feature common of both solids and uids,

as embodied in the role of b in governing the deviatoric stress, constitutes one aspect

of such deformation, the major one in the case of thermal expansion effects. In this

sense, the movement of volume [4], whether regarded as static as in the case of solids

or kinetic as in the case of uids, constitutes the common theme connecting the two

distinct types of continua. These come together in the notion of Korteweg stresses

[63], a strictly continuum-level concept discussed in Section 8, where it is the density

gradient or equivalent specic volume gradient, rather than the temperature

gradient, which serves to unify the notion of thermal stresses in solid and uid

continua.

5. Maxwells v

m

-slip boundary condition viewed alternatively as a no-slip condition

imposed upon v

v

Maxwells [8] well-known thermal creep slip-velocity boundary condition imposed

upon v

m

at a solid surface plays a fundamental role in the application of gas-kinetic

theory to actual physical problems. Its importance stems from the fact that the

Boltzmann equation, by itself, offers no insight into the boundary condition to be

imposed upon the tangential velocity at such surfaces [64, pp. 5256,98102]. As a

result, the use of Maxwells slip condition is ubiquitous in applications. It is relevant,

for example, in analyses of gaseous phoretic phenomena, including thermophoresis,

thermal transpiration, and diffusiophoresis (the latter when this slip condition is

extended from temperature to species concentration in isothermal binary systems

[25,65]), as well to analyses of other baroeffect phenomena [66]. This section

addresses, inter alia, the background behind Maxwells thermal creep condition,

including the approximations inherent in its original derivation. Our goal in doing so

is, in part, to demonstrate that the current view of Maxwell slip as a residual

manifestation of Burnett-level O(Kn

2

) noncontinuum behavior is a misinterpretation

of its true status in the asymptotic Knudsen number perturbation-expansion

hierarchy. Rather, we argue that his thermal creep condition is actually an O(Kn)

near-continuum term in the obfuscating language of statistical mechanics. On the

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H. Brenner / Physica A 349 (2005) 60132 77

other hand, when expressed in the terminology of uid mechanics it constitutes a

strictly continuum-level term, on a par with the NSF equations (either the original

or modied versions thereof). Having thus relegated thermal creep to the role of an

ordinary continuum uid-mechanical boundary condition, we argue that what

appears to be Maxwell slip of the mass velocity v

m

corresponds exactly to no-

slip of the volume velocity v

v

; that is, Maxwells boundary condition is really a no-

slip uid-mechanical continuum-level boundary condition in disguise. In turn, this

recognition offers further quantitative corroboration of the viability of our

nontraditional constitutive relation v = v

v

; independently of that offered in Sections

3 and 4.

The review of Maxwell slip which follows is carried out in the context of our

proposed no-slip v = v

v

continuum boundary condition,

I

s

.

(v

v

U) = 0 on qV

s

; (5.1)

derived from Eqs. (1.7) (1.4) and used in our solution [23] of the thermophoretic

problem in the accompanying paper, as well as in the elementary Faxens law-based

version thereof derived in Appendix B. Explicitly, in what follows, it is shown in the

case of single-component heat-transfer problems in gases that the Maxwells

boundary condition [8],

I

s

.

(v

m

U) = C

s

uV

s

ln T on qV

s

; (5.2)

with V

s

= I

s

.

V the surface-gradient operator and C

s

Maxwells slip coefcient, is, in

fact, constitutively identical to our Eq. (5.1). Whereas Eq. (5.2) is currently regarded

in the literature as a noncontinuum O(Kn

2

) Burnett-level-derived relation, our Eq.

(5.1) is a strictly continuum relation in the language of uid mechanics. Indeed, the

fact that these relations prove to be constitutively identical in their common domain

of validity, namely ideal monatomic gases, adds credibility to the viability of our

fundamental relations, Eqs. (1.4)(1.6), as well as to that of our hypothesis regarding

the proper no-slip boundary condition to be imposed at solid surfaces, Eq. (5.1).

5.1. Chronology of the Maxwell slip condition

In an attempt to explain Crookess (1876) observation [67] of the rotation of a

windmill in a partially evacuated radiometer, Maxwell [8], in 1879, introduced the

hypothesis of a temperature-gradient-induced slip imposed upon v

m

at solidgas

boundaries [68]. From Maxwells own description [8] of the evolution of his thinking

about the problem, the derivation of his slip boundary condition (5.2) evolved in two

distinct stages and timelines. Our subsequent chronological review thereof serves to

clarify the issue of whether or not Maxwells boundary condition is indeed to be

viewed as an O(Kn

2

) noncontinuum effect owing to its Burnett-like origin, or as an

O(Kn) near-continuum condition (as we believe Maxwell himself clearly under-

stood).

In the rst stage of his celebrated paper, directed exclusively at qualitatively

rationalizing the observed behavior of Crookess radiometer as a strictly slip-based

phenomenon, Maxwell introduced the notion of thermal stresses existing in the

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H. Brenner / Physica A 349 (2005) 60132 78

interior of the gas, molecularly far from any surfaces. It is useful here to recall that

the notion of stresses in a uid (gas) originally involved only viscous stresses, arising

from massvelocity gradients, as embodied in Newtons law of viscosity, Eq. (1.1)

(1.3). Indeed, one of the early triumphs of gas-kinetic theory was Maxwells

theoretical derivation in 1860 [69] of Newtons law of viscosity (accompanied by the

later, experimentally conrmed and surprising, conclusion that the viscosity of a gas

is independent of pressurealbeit a statement limited at the time to Maxwell

molecules). In his calculation, Maxwell used his own pre-Boltzmann molecular

collision model, involving so-called Maxwell molecules [58], the latter repelling one

another pairwise with a force inversely proportional to the fth power of their

separation distance, while devoid of an attractive component.

These thermal stresses, above and beyond the purely viscous stresses T

m

given by

Eq. (4.2), and arising from the massvelocity, were demonstrated by Maxwell to

stem from small temperature gradients existing within the gas. By adopting an

elementary perturbation scheme based upon the relative smallness of these gradients,

Maxwell [8] succeeded in deriving the following formula for the deviatoric thermal

stress T

/

in the gas, namely the stress above and beyond the Newtonian viscous

stress tensor (4.2):

T

/

=

3m

2

rT

VVT

1

2

IV

2

T O(T

1

[VT[

2

)

_ _

: (5.3)

Comparison of the above with the Burnett thermal stress tensor (4.5) for the case of

Maxwell molecules shows that Maxwells [8] calculation represented only an

approximation to Burnetts later [6,7], more accurate, calculations, which also

included nonlinear temperature gradient effects, not accounted for by Maxwell

owing to the latters assumption of smallness of the temperature gradient. It was

with the derivation of Eq. (5.3), valid in the interior of the gas, that the rst phase of

Maxwells eventual slip velocity calculation ended. That is, no attempt was made by

Maxwell at the time to use the knowledge embodied in Eq. (5.3) to estimate the

appropriate form of the tangential velocity boundary condition at a solid surface,

although he recognized that motion of the gas along a solid surface on which a

temperature gradient existed would somehow be affected by these thermal stresses.

The second stage of Maxwells derivation of his slip condition, Eq. (5.2), was

accomplished some months later. In an appendix added in May 1879 [70] to the

original version of his paper [8], and ending with the derivation of Eq. (5.2), Maxwell

writes: In the paper as sent in to the Royal Society [read on April 11, 1878], I made no

attempt to express the conditions which must be satised by a gas in contact with a solid

body, for I thought it very unlikely that any equations I could write down would be a

satisfactory representation of the actual conditions, especially as it is almost certain

that the stratum of gas nearest to a solid body is in a very different condition from the

rest of the gas. He then goes on to further state that: One of the referees, however,

pointed out that it was desirable to make the attempt.... I have therefore added the

following calculations, which are carried out to the same degree of approximation as

those for the interior of the gas. In his appendix, Maxwell then goes on to point out

that it was only after hearing Reynolds read his paper on thermal transpiration

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H. Brenner / Physica A 349 (2005) 60132 79

[71,72] before the Royal Society that he ...began to reconsider the surface conditions

of a gas.... Maxwell then goes on to describe his scheme as being ...purely

statistical..., in addition to commenting that he is treating ...a gas which is not

highly raried [sic], and in which the space-variations within distances comparable to l

[essentially the mean-free path l; see below] are not very great.

The slip-velocity formula that Maxwell ultimately developed is given by the

following expression, in which x lies normal to the solid surface qV

s

; and v is the

tangential velocity component in the y-direction, lying in the tangent plane of the

surface:

v G

qv

qx

3

2

m

rT

q

2

T

qxqy

_ _

3

4

m

rT

qT

qy

= 0 on qV

s

: (5.4)

In the above

G =

2

3

2

f

1

_ _

l ; (5.5)

in which G is a coefcient of slipping, with l the mean-free path of the gas molecules,

and 1 f the fraction of molecules reected by the surface, f then being the fraction

absorbed. Maxwells equation (5.4) is based directly upon his approximate thermal

stress equation (5.3) [73]. It is only after setting G = 0 in this approximate Maxwell

molecule model that the classical Maxwell thermal creep formula (5.2) obtains,

wherein C

s

= 3=4: Given the scaling argument discussed in Section 4 demonstrating

that the Burnett thermal stress terms constitute a continuum-level phenomenon (in

the language of uid mechanics), it is apparent that Maxwells slip-velocity formula,

originating from his version (5.3) of these thermal stresses, must also be a continuum

result, unrelated to O(Kn

2

) noncontinuum phenomena.

To bring to fruition the process of demonstrating the equality of the Maxwell slip

formula (5.2) with our no-slip volume-velocity continuum formula (5.1), substitute

Eqs. (1.5) and (1.6) into (5.1), and invoke the Eucken formula [18] preceding Eq.

(3.2) so as to obtain the following formula, formally equivalent in physical content to

Eq. (5.1):

I

s

.

(v

m

U) = C

/

s

nV

s

ln T on qV

s

; (5.6)

in which C

/

s

is the coefcient dened following Eq. (3.2). Eq. (3.3) shows that C

/

s

=

3

2

for monatomic gases. Clearly, our continuum equation (5.6) is constitutively

identical to Maxwells slip formula (5.2). Maxwells value of

3

4

for C

s

differs from our

predicted value of

3

2

in Eq. (3.3) for monatomic gases. However, Maxwells result

applies only to Maxwell molecules, whereas our result bears no such limitation. And

it is known [6] that the Maxwells intermolecular force model does not generally yield

predictions that accord well with experiments. Moreover, Maxwells C

s

result also

depends to some extent on the details of the collision model adopted for the

reection of the molecules from the wall (cf. Ref. [139, pp. 367400]). As such, the

disparity in the respective values of the two slip coefcients is not regarded as

serious, especially given Talbot et al.s [39] best t value of C

s

= 1:17 which

straddles the two, together with the fact Maxwells thermal transpiration calculation

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H. Brenner / Physica A 349 (2005) 60132 80

[8] based upon his C

s

=

3

4

value underpredicts the experimentally-observed

thermomolecular pressures by a factor of about 2 [24].

In comparing our proposed boundary condition with that posed by Maxwell it

needs to be stressed that Maxwells result has been shown to hold only for

monatomic gases. In contrast, our more general version,

I

s

.

(v

m

U) = aV

s

ln r on qV

s

; (5.7)

of Maxwells v

m

-based slip formula, representing the precursor of Eq. (5.6) without

invoking the Eucken relation, holds also for polyatomic gases [cf. Eq. (3.3)], and

presumably for liquids too, although the latter remains to be studied experimentally.

Indeed, as pointed out in Section 8 in connection with our discussion of Korteweg

stresses, in terms of our more generic formulation,

I

s

.

(v

m

U) = I

s

.

j

v

on qV

s

; (5.8)

of the slip boundary condition (5.1) [with j

v

given by Eq. (1.6) for single-component

gases and by its a = D two-component counterpart for isothermal binary mixtures],

it is apparent that the preceding relation should be equally applicable to the case of

binary diffusion (a fact which was subsequently conrmed by our analysis [25] of

experimental isothermal gaseous diffusiophoretic data in such systems). In any

event, it now appears clear that to refer to Maxwells boundary condition as a slip

condition is to obfuscate the fact that the physical boundary condition to be applied

along a solid surface, nonisothermal or not, is simply the standard continuum one of

no slip, albeit in disguise, since it is imposed upon v

v

rather than v

m

!

5.2. How can use of the wrong velocity eld (in conjunction with the correct boundary

conditions) lead to the correct global physical result?

Various nonisothermal experiments such as thermal transpiration and thermo-

phoresis have been rationalized [8,35] during the past 125 years by invoking

Maxwells boundary condition (5.2), which, as we have indicated, is the physically

correct no-slip boundary condition to be applied at solid surfaces, albeit formulated

in terms of v

m

rather than v

v

: However, from the perspective of v

v

being the correct

velocity to use for v in the generic pre-constitutive equations of Sections 1 and 2,

researchers solving these phoretic problems in the past have, according to our

interpretation, used the wrong momentum and energy transport equations, namely

those based upon the choice v = v

m

[74]. For consistency, these transport equations

should have added Maxwells thermal stress approximation, T

/

accurately, the Burnett thermal stress version thereof, Eq. (4.5), to the classical

viscous stress contribution T

m

so as to obtain the correct deviatoric stress T; Eq.

(4.4), to be used in the creeping ow relation, Vp V

.

T = 0: Moreover, these

equations should not have been based upon the assumption of incompressibility,

V

.

v

m

= 0; as was originally supposed by Maxwell [8] in his analysis of thermal

transpiration and later adopted by Epstein [35] in the latters analysis of

thermophoretic movement. Nevertheless, our more recent recalculations of the

physical forces (or, equivalently, the thermophoretic particle velocity U [23] and the

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H. Brenner / Physica A 349 (2005) 60132 81

thermal transpiration thermomolecular pressure difference Dp [24] using our

modied theory, have yielded the same results obtained by these prior researchers

(at least to within a factor of 2 based upon Maxwells C

s

=

3

4

slip coefcient), results

which accord with experiment. But if these prior researchers indeed solved the wrong

set of transport equations (albeit subject to the correct boundary conditions), how

can it be that their nal results were correct, in the sense of agreeing with experiments

as well as with our results [23,24]? The answer will be seen to lie in the fact that their

results were fortuitous, valid only in circumstances where the temperature gradients

involved are small (when appropriately scaled), so that neither the nonlinear terms in

the Burnett thermal stress formula (4.5) nor the incompressibility assumption affect

the outcome of the calculation. However, in more general circumstances, where

nonlinear effects are retained in calculations of this genre, the scheme based upon the

incorrect constitutive formulation (1.3) will presumably lead to erroneous conclu-

sions relative to those based upon the constitutive relation (1.4).

Appendix C shows explicitly how and why these inherently wrong transport

equations can nevertheless lead fortuitously to the correct result, at least to leading

order in the externally imposed temperature gradient. A main point to note in this

class of thermal problems is that the convective uxes appearing in the momentum

and energy equations always prove to be negligible relative to the diffusive uxes

when the temperature gradients are sufciently small. The calculations presented in

Appendix C, applicable to both the thermophoretic [23] and thermal transpiration

[24] cases, are based upon the fact that the respective velocities v

m

and v

v

sought in

the two schemes are related by Eq. (1.5), in which the diffuse volume ux is given by

(1.6), namely j

v

= aV ln r or, equivalently, by j

v

= (k=^ c

p

)V^ v: Inasmuch as we have

supposed, based upon the thermal law of adiabatically additive volumes, that

(q^ v=qT)

p

= const; it follows that:

j

v

=

k

^ c

p

q^ v

qT

_ _

p

VT ; (5.9)

in which, as discussed, the multiplier of VT appearing therein is taken to be a

temperature- and pressure-independent constant.

5.3. Further comments on the Maxwell slip condition

5.3.1. Knudsen boundary layers

It is invariably assumed in the literature, inappropriately in our view [75], that

Maxwell arrived at his slip condition (5.2) by introducing noncontinuum arguments

based, in effect, upon the notion that a hypothetical Knudsen boundary layer or sub-

layer exists in proximity to a solid surface qV

s

: This notion likely stems from

Maxwells [8] remark: ...that the stratum of gas nearest to a solid body is in a very

different state than the rest of the gas. However, introducing a noncontinuum

O(Kn

2

) argument, while setting G = 0 in Eq. (5.4) in an attempt to rationalize

Maxwells slip condition lacks consistency, since the slip coefcient C

s

is independent

of the Knudsen number [in contrast to the limiting behavior displayed by the other

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H. Brenner / Physica A 349 (2005) 60132 82

two noncontinuum slip effects appearing in Eq. (3.4)]. In particular, the terms

multiplied by G; characterized by a length term a; say, involve a derivative with

respect to x; the distance normal to the surface. Since G is proportional to l; the

operator Gq=qx is of O(l=a) O(Kn): This contribution, of course, vanishes in the

limit as Kn 0; whereas the Maxwell slip term in (5.4) does not. As such, the slip

manifested in Eq. (5.2) does not vanish in the Kn = 0 continuum uid-mechanical

limit, in disagreement with all contemporary views of the no-slip boundary condition

for uid continua, isothermal or not. Accordingly, it would appear that Maxwell slip

cannot be attributed to a hypothetical noncontinuum, Knudsen boundary layer.

Moreover, it appears clear from Maxwells discussion of the slip issue in

connection with Eqs. (5.4) and (5.5), that the stratum of gas in the neighborhood

of the surface, to which he refers as being physically different from that in the bulk, is

associated with the true slip coefcient G rather than with the thermal stress term in

his Eq. (5.4). Thus, setting G = 0 in the latter equation in order to obtain (5.2)

eliminates the possibility of Knudsen-based slip in the physical meaning of the word

slip. [In the contemporary literature, G is associated with what is now known as

velocity slip, a true noncontinuum temperature-gradient-independent phenomen-

on, corresponding to the appearance of the coefcient C

m

in Eq. (3.4)].

5.3.2. Maxwell slip violates the First law of thermodynamics

Last but not least it is pertinent to note that Maxwells slip condition (5.2), when

used in conjunction with the conventional incompressible NSF equation set, as

Maxwell has done in his treatment [8] of the thermal transpiration problem, violates

the First law of thermodynamics. This violation stems from the fact that were slip to

occur at a rigid immobile mass-impermeable surface, work would be performed by

the surroundings across this surface upon the uid conned within. But this is

impossible because under such circumstances no mechanism exists by which the

surroundings can do work on the uid! As such, this fundamental thermodynamic

fact furnishes yet another reason for rejecting the notion of the Maxwell boundary

condition (5.2) as representing physical state of slip; that is, while the boundary

condition itself is constitutively correct, it does not connote slip of the actual physical

velocity, v

v

: This point is further elaborated upon in Appendix D, where the First law

violation is demonstrated in a more general context transcending our phoretic

applications.

6. The uids tracer (Lagrangian) velocity v

l

: Rationalization of the constitutive

relation v = v

v

This section addresses what might appear supercially to be a kinematical rather

than dynamical issue pertaining to the fundamental notion of the velocity of the uid

at a point in space occupied by the continuum. Whereas it is trivial to understand the

notion of the velocity of a material object, particularly the velocity of a rigid body,

and especially if the body is envisioned simply as an effectively pointsize non-

Brownian object, the same cannot be said of the ease of understanding the concept of

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H. Brenner / Physica A 349 (2005) 60132 83

uid velocity at a point in space. After all, a continuum does not physically exist as a

continuous material entity. Rather, it is an abstraction since the matter of which the

continuum is composed consists of discrete material entities, molecules with empty

spaces separating them. And these spaces, devoid of matter, can be quite vast in the

case of low-pressure gases. Thus, if a continuum does not exist physically, what is the

entity whose velocity we believe that we are measuring? While ones rst response

might be to answer that one is measuring the mean velocity of the molecules in the

neighborhood of the point of interest, this cannot really be so obvious. After all,

given that Maxwells notion of mobile molecules was not introduced into physics

until 1860, what in 1755, 100 years earlier, did Euler [76] believe was the physical

interpretation of the velocity that appeared in his continuity equation (1.2) which he

had then derived? Similarly, in 1845, what did Stokes [1] understand to be the

experimental realization of the velocity appearing in his formulation of Newtons

viscosity law, Eq. (1.1)?

While it might appear at rst that the issues being addressed are purely

philosophical, and hence without physical import, we believe that the reader will

ultimately think otherwise. For example, we raise the question of whether, even in a

single-species uid, the optical-colorimetric measurement of the spatio-temporal

motion through space of a small photochromically colored or dyed region of a

moving uid [11] will generally record the same velocity as would result from

comparably monitoring the motion of a tracer, a small (albeit non-Brownian)

solid particle deliberately introduced into the uid [9]. And if these two

measurements disagree, which, if either, should be understood as the velocity of

the uid at the spatial point in question? Though both experimental methods are in

wide use today, it is not obvious a priori that these two distinct schemes will

necessarily yield the same uid velocity under all circumstances. In this context,

imagine, for example, a (non-Brownian) particle placed into an ideal uid

undergoing a steady motion that is uniform far from the particle. According to

DAlemberts paradox [77] such a particle experiences no force, whence it will

presumably remain in place as the uid ows around it. Clearly, such a particle

would make a poor tracer of the undisturbed uniform uid motion. (I am grateful to

Dr. Ehud Yariv for this example.) On the other hand, were one to photochromically

color the molecules, so to speak, of such an ideal uid in some small uid region,

motion of the uid as dened by the movement of the resulting color through space

would presumably be observed (almost certainly, registering mass motion, v

m

).

While one might argue that no such inviscid uid exists, thus rendering the question

moot, this begs the fundamental question.

On the other hand, a rigid particle to which uid adheres [and hence on whose

surface the no-slip condition (1.7) prevails] has the potential to serve as a tracer of

the uid motion, provided that other qualications are met, including passivity of

the particle, an attribute which will subsequently be dened more precisely. In any

event, a truly critical set of experiments aimed at testing the hypothesis of equality

between the uids mass velocity v

m

(presumably the velocity being measured during

a colorimetric molecular-tagging velocimetry experiment [11]) and the uids tracer

velocity [9], say v

l

; appears to have not yet been performed, at least in circumstances

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H. Brenner / Physica A 349 (2005) 60132 84

where a sensible difference between them might be expected based upon our modied

NSF equations (1.4) and (2.6). Nevertheless, on the basis of what is to follow,

these velocities would appear to be equal only in the case of incompressible uid

motions, V

.

v

m

= 0; wherein the density is uniform.

The instantaneous tracer or Lagrangian velocity v

l

(x; t) of a small [78] particle

(whose center of volume, say, is) situated at time t at some position x in space would

appear to be dened by Eq. (1.9), with the curve x = x(x

0

; t) constituting the

trajectory of the particle through space and time. One of the key words in this

denition of a tracer is the word particle. In continuum mechanics [79] this is

invariably interpreted as being a differentially sized material uid particle, a

purely hypothetical entity. However, since the continuum is composed of discrete

molecules, the notion of such a material particle is devoid of strict operational

signicance owing to the fact that individual molecules are free to enter and leave

such a body through its surface, despite the constancy of the material particles total

mass during its journey through space. As such, the denition (1.9) possesses an

unambiguous operational signicance only in the case of a real physical particle,

namely a small (albeit non-Brownian) rigid object deliberately introduced into the

uid and subsequently monitored in space and time in order to establish the

particles trajectory x = x(x

0

; t) and hence therefrom the velocity of the

undisturbed uid at a point of space. More will be said of this later. For the time

being, the important point that we wish to make here is to propose the tentative

kinematical hypothesis that the uids tracer velocity, as measured by the preceding

particle trajectory scheme, is identical to its volume velocity. Explicitly, as suggested

by Eq. (1.10), our hypothesis is that the uids tracer velocity v

l

is identical to the

uids volume velocity v

v

:

The case for the equality v

l

= v

v

can only be made experimentally, using real

particles, not hypothetical material uid particles. That is, it is not possible to prove

this relation purely theoretically, either by continuum-mechanical or statistical-

mechanical arguments applied only to the uid. Indeed, the very denition of v

l

;

requiring the deliberate introduction of a (real) foreign object into a hypothetical

uid continuum, implies the impossibility of a purely kinematical pointwise

continuum-mechanical denition of the undisturbed uids tracer velocity. As such,

Eq. (1.9) is not to be regarded as the denition of v

l

; but rather as representing the

mechanism by which the trajectory, x = x(x

0

; t); of a hypothetical uid particle x

0

moving through space can be determined once the tracer velocity eld v

l

(x; t) is

already known independently. In this paper, we pose but a single experiment in

support of the hypothesis (1.10), namely one using a thermophoretically animated

particle as the tracer. A subsequent paper [25] addresses a similar experiment based

upon the diffusiophoretic velocity of a particle, the analysis and interpretation of

which further supports the hypothesis. While the pertinent isolated-particle data

currently available in support of Eq. (1.10) are thus quite limited in terms of

quantity, it will be seen, however, that the purely kinematical equality (1.10)

possesses considerable intuitive appeal in a dynamical sense, in terms of providing a

rationale for the otherwise seemingly empirical constitutive relation, v = v

v

to be

employed in Eqs. (1.1) and (1.7). That is, if Eq. (1.10) is, in fact, true, then so also is

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H. Brenner / Physica A 349 (2005) 60132 85

the resulting expression v = v

l

; derived from Eq. (1.4), the latter representing a

dynamical relation quantifying the diffuse transport of momentum through space in

connection with Eq. (1.1).

This brings us to the real motivation underlying the writing of this section, namely

that of offering a rational explanation for the seemingly empirical fact that the uid

continuums velocity v appears to be given generally by the uids volume velocity

v

v

; rather than by its mass velocity v

m

: As suggested above, we intend to do this by

introducing the additional notion of the tracer velocity of the uid v

l

(to which we

shall also refer as the uids Lagrangian velocity, accounting thereby for the

appended subscript), and subsequently arguing that the uids tracer velocity is

identical to its volume velocity, as set forth in Eq. (1.10). A tracer is a material object

that moves through space, but not through the uid. Indeed, the tracer moves with

the uid, being (by denition) conveyed piggy-back by the latter. The tracer thus

moves through space in a manner no different from that of an elementary mass

point moving though space. As such, repeating the closing comments of the

preceding paragraph, it is intuitively obvious as to why the tracer velocity v

l

should

qualify as the uids velocity. And since we intend to experimentally demonstrate

the viability of (1.10), albeit only to the data-limited extent currently possible, the

reason behind the seemingly empirical constitutive choice (1.4) for the uids velocity

will then be seen to be transparent.

6.1. Measurement of the uids tracer velocity

During the course of seeking to experimentally demonstrate the contention (1.10),

it is necessary at the outset to rst address in detail the question of how, at least in

principle, the uids tracer velocity eld v

l

[x(x

0

; t); t]; dened by Eq. (1.9), is to be

measured. By way of reviewing the generic background underlying the experimental

measurement of any eld variable (of which the uids velocity is but an example),

and as prelude to such an undertaking, we note that the operational or experimental

denition of any continuum eld variable at a point x in space involves inserting an

appropriate pointsize entity into the eld at that point, and subsequently performing

some measurement on that entity, such that the magnitude (and direction, if

relevant) of the entitys response quanties the strength (and, possibly, direction-

ality) of the undisturbed eld at that point. Of course, the entity needs to be of such a

nature as to not sensibly perturb the very eld that one is objectively attempting to

measure; hence, the requirement, inter alia, that the responsive entity be effectively

pointsize in its dimensions. But it must not be so small as to be able to interact

responsively with the individual sub-continuum (i.e., molecular) units of which the

hypothetical continuum is composed; otherwise, its response will not be to the

hypothetical continuum as a meaningful macroscopic physical entity in its own

right, but, rather, to the discrete microscopic sub-continuum molecular objects of

which the continuum is composed.

From a practical point of view, no such pointsize entities exist. Accordingly,

application of this scheme in practice, at least for steady uid motions [80], involves

the following sequential steps: (i) successively inserting, in the neighborhood of the

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H. Brenner / Physica A 349 (2005) 60132 86

same specied point x of interest where one wishes to measure the eld, a series of

otherwise identical particles of ever-decreasing size; (ii) measuring and recording

their respective responses; (iii) subsequently extrapolating these measurements to the

limit of zero particle size; and (iv) repeating this sequence of steps with a series of

other geometrically, physically, or physicochemically different particles, so as to be

assured that the resulting, zero-size measurement obtained is independent of the

physical properties of the particle, and hence dependent only upon those of the

entraining uid itself. In circumstances where particles of different shape or different

physicochemical properties might yield different extrapolated measurements, one

must identify among those different particles that class or group of extrapolated

measurements characterized by having registered the same zero-size values of v

l

: For

example, in the case of the thermophoretic experiments described in Section 3, the

latter, perhaps seemingly abstruse point, becomes pertinent with respect to the

thermal conductivity k

s

of the tracer particle when measuring the uids tracer

velocity v

l

; cf. the subsequent remarks made in connection with Eqs. (6.1) and (6.2).

Thus, in the particular case where the uids tracer velocity eld v

l

(x; t) constitutes

the continuum eld of interest, one carries out the above-cited scheme (at least in

principle) by sequentially introducing a series of ever smaller rigid particles, say,

spherical in shape, and of diminishing radii a (all, however, sufciently large such as

to manifest no sensible Brownian motion) into the owing uid, with their respective

centers of volume initially situated in the neighborhood of the point x of interest.

Subsequent measurement of the vector displacement Dx of each such particle

through space during an appropriately small time interval Dt (using, say, streak

photography or some equivalent particle-tracer velocimetry measurement [9]), then

furnishes the particles radius-dependent vector velocity, U = U{a]; where U :=

lim

Dt0

Dx=Dt dx=dt at the point x: Extrapolation of these velocity data to zero

sphere radius then furnishes the pointsize tracer velocity, U{0] (qx=qt)

x

0

;

representing the uids tracer velocity v

l

with which the undisturbed uid is moving

at the point x in question. Repetition of this procedure at other points of the uid

serves to map out the entire uid tracer velocity eld. As earlier mentioned, it is

important that the uid adhere to the particle, so that the no-slip boundary

condition, imposed upon v

m

or v

v

; whichever is appropriate, is satised.

6.2. Tracer velocity in thermophoretically-animated ows

The experimentally conrmed equation (3.1) reveals, rather surprisingly, that a

non-Brownian thermally animated sphere moves (relative to the steady temperature

eld) with a velocity that is independent of its radius [81,82], at least in the effectively

zero Knudsen number continuum regime! An identical phenomenon is observed in

compilations of data derived from comparable (isothermal) diffusiophoretic

experiments [25,37,83], where the movement of suspended aerosol particles [relative

to the local mass velocity, cf. Eq. (7.1)] in binary gas mixtures arises from the

existence of species-concentration-induced density gradients Vr; with r = r(w): The

fundamental and profound signicance of this size-independence, occurring in all

phoretic experiments performed under effectively zero-Knudsen number circum-

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H. Brenner / Physica A 349 (2005) 60132 87

stances, appears to have escaped the attention of previous investigators. This

size-independence, down to the limit of an effectively zero-size particle (a tracer),

will be seen to provide the experimental basis for our hypothesis regarding

the equality v

l

= v

v

of the tracer and volume velocities of the particle-free

uid itself.

In the limiting case, k

s

=k51; of an effectively insulated or nonconducting sphere,

Eq. (3.1) (see the derivation applicable to this nonconducting case in Appendix B)

governing the thermophoretic velocity of a particle reduces to the form

U = abVT : (6.1)

The experimental conditions under which this equation applies are precisely those

which qualify the experimentally conrmed thermophoretic particle velocity (6.1) to

be identied as the undisturbed uids tracer velocity, v

l

U{0]; namely the uids

intrinsic velocity through space in the absence of the particle. Specically, the

following requirements are met during the thermophoretic experiments underlying

(6.1): (i) owing to its applicability in the Kn = 0; continuum limit, Eq. (6.1) fullls the

requirement of representing the velocity of a non-Brownian particlethat is, a

particle sufciently large such as to be unresponsive to direct molecular-level

phenomena, and hence to be capable of responding only to continuum-level

phenomena; (ii) the, in-principle, extrapolation of a sequence of variable sphere-size

measurements to the hypothetical zero-size limit proves to be unnecessary in present

circumstances, since the experimental measurements conrming Eq. (6.1) reveal the

particle velocity to be independent of size, and hence not requiring size

extrapolation; (iii) the passivity requirement demanded of the tracer particle in

order that its measured velocity qualify as the uids tracer velocity v

l

is fullled by

the choice of a nonconducting particle (i.e., k

s

=k51), whereby, consistent with the

nature of this passivity requirement, Eq. (6.1) shows the particle velocity to depend

only upon the properties of the uid through which the particle moves,

independently of any physical attributes of the particle itself [84]; (iv) an additional

and important feature further supporting Eq. (6.1) as the (particle property-

independent) tracer velocity of the uid is the fact that in the zero particle

conductivity case Eq. (6.1) holds irrespective of particle shape (i.e., for nonspherical

particles), and independently of the orientation of such particles relative to the

direction of the temperature gradient, as is demonstrated to be the case in the

accompanying thermophoretic paper [23], as well as in Appendix B. And it is only in

this effectively zero conductivity case, k

s

=k51; that particle shape- and orientation-

independence obtains!

Given these circumstances together with the fact that v

l

U{0] we may write

v

l

= abVT in place of Eq. (6.1), since the experimentally conrmed particle

velocity (6.1) has now been established as being the tracer velocity of the gas relative

to the container walls. Inasmuch as the (undisturbed) temperature eld is also steady

relative to the container walls, this temperature eld is then, by denition, not being

convected relative to the constant-temperature walls. As such, since the velocity v

l

;

has been measured relative to these walls, this requires that v

m

= 0 with respect to

this same reference frame. Accordingly, one can infer from the experimentally

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H. Brenner / Physica A 349 (2005) 60132 88

observed absence of wall effects on particle motion [effects that, if present, would

otherwise be manifested in Eqs. (3.4), (3.5) or (6.1) by the explicit appearance therein

of the ratio a=L of sphere radius a to wall separation distance L] that the walls play

no explicit hydrodynamic role in thermophoretic migration phenomena. Accord-

ingly, the relative motion of the undisturbed uid velocity eld with respect to the

temperature eld can be expressed objectively in the following reference-frame-

independent form [23]:

v

l

v

m

= abVT : (6.2)

According to this strictly uid-related, particle-free relation, the uids tracer and

mass velocities, v

l

and v

m

; are indeed different, at least in the presence of a

temperature gradient!

The strictly kinematical measurement of the motion of an entrained particle

manifested in Eq. (6.1) has nothing whatsover to do with the dynamical

circumstances (i.e., temperature gradients in the present thermophoretic case, or

molar species concentration- and molecular weight-gradients in the gaseous

diffusiophoretic case [25]) that animate the uids undisturbed motion v

l

existing

in the tracers absence. This is true whether the dynamical forces causing the pre-

existing uid motion v

l

into which the particle is subsequently introduced be caused

by temperature gradients, pressure gradients, buoyant gravitational forces (i.e.,

natural convection [85]), or otherwise. After all, the entrained particle plays no role

in creating the pre-existing undisturbed uid motion v

l

that exists prior to the

particles introduction into the uid. That the dynamical circumstances giving rise to

the entrained particles motion are kinematically irrelevant is evidenced by the fact

that a uid-mechanical experimentalist, concerned exclusively with kinematical

velocity measurements, need not have at her/his disposal a thermomometer,

manometer, gravitometer, or any other similar device in order to objectively

measure the movement of tracer particles, and, hence, to subsequently report his

ndings of the respective magnitude and direction of the undisturbed uid velocity

eld, as measured by the zero-size tracers response to that eld. In short, he/she

need have no idea whatsoever as to the physical cause(s) of the uid motion that he is

attempting to measure (see, however, the comments in Ref. [84] with regard to the

need to perform replicate experiments using tracers of varied materials and shapes).

Indeed, the less he knows about the origin of the uid motion upon which he is

reporting, the less biased will he be when interpreting his purely kinematical

observations, and, concomitantly, the more objectively will his results be viewed by

independent referees reviewing his work.

The preceding interpretation of the thermophoretic data leads to the seemingly

paradoxical conclusion that the (particle-free) uid is moving, v

l

a0; despite the

fact that the uid is apparently at rest, v

m

= 0: That is, the uid was already in

motion with velocity v

l

prior to the introduction into it of any foreign (tracer)

particle! How can this be? Resolution of this paradox lies in the fact that the vector

eld v

m

is a velocity in name only, but not in a true physical sense. In this context,

it is important to note that the sole Eulerian continuum ow eld parameter, other

than r; capable (at least in principle) of being directly measured by performing an

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H. Brenner / Physica A 349 (2005) 60132 89

experiment at the space-xed point x; is not the velocity vector v

m

(x; t); but is, rather,

the mass ux density vector, n

m

(x; t): As earlier discussed in section 1 (see Ref. [5]),

the latter is dened such that the extensive quantity dS

.

n

m

constitutes the

instantaneous rate, at time t; at which mass ows across a space-xed directed

element of surface area dS centered at x: In contrast with n

m

; the indirectly derived

intensive vector eld, v

m

:= n

m

=r; is merely a dened quantity, essentially nothing

more than a mathematical symbol, to which one may, or may not, seek to assign a

physical interpretation. Velocity, on the other hand, viewed as a physical concept in

the classical Newtonian sense of referring to the movement of a real material object

through space, pertains to the motion of a pointsize object, initially situated at a

point in space, say, x

0

; at time t = 0; and subsequently traversing a denite

trajectory, x = x(x

0

; t); as discussed in connection with Eq. (1.9).

In contrast with v

m

; the uids tracer velocity v

l

clearly fullls the physical

notion of a velocity in the sense of an object of indisputable time-independent

integrity executing a deterministic trajectory through space, since the object with

which this velocity is experimentally identied is, in fact, a material entity,

namely the pointsize tracer, a foreign body deliberately introduced into the uid

in order to monitor the latters motion. As such, it is clearly not arbitrary to

identify the tracer velocity v

l

as being the velocity of the uid continuum.

The velocity v

l

would therefore appear to qualify as being the appropriate purely

kinematical uid velocity v referred to in textbooks in the context of uid

movement through space (although it is not the velocity appearing in the con-

tinuity equation, nor is it the uids specic momentum, both of which correspond

to v

m

).

6.3. Conrmation of the hypothesis embodied by Eq. (1.10)

Eqs. (1.5) and (1.6) combine in the present single-component heat-transfer case to

yield v

v

v

m

= aVln ^ v: In circumstances where the thermal law of adiabatically

additive volumes applies, whereupon viscous dissipative effects are necessarily

negligible, and in which the effects of pressure on specic volume are small compared

with those of temperature, so that ^ v = ^ v(T); the preceding expression in this

paragraph adopts the form

v

v

v

m

= abVT : (6.3)

Comparison of the latter with the experimentally conrmed tracer relation (6.2)

shows that the hypothesized equality v

l

= v

v

is indeed valid. As Eq. (6.2) has been

experimentally established as applicable to both gases and liquids (albeit with less

condence in its validity for liquids owing to the current dearth of appropriate

liquid-phase thermophoretic data), we conclude, tentatively, that the equality (1.10)

is general in scope. Admittedly, this has thus far been conrmed only for the

thermophoretic case. However, a similar analysis of experimental isothermal

diffusiophoretic data, coupled with a theory of that phenomenon based upon the

constitutive relation v = v

v

applicable to the binary mass-transfer case [25], further

supports (1.10) [see also Eq. (7.1)].

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H. Brenner / Physica A 349 (2005) 60132 90

6.4. Further discussion of the notion of a tracer velocity

The notion of the tracer velocity, v

l

(x; t) v

l

(x

0

; t); of a uid (the latter functional-

dependence notation involving x

0

serving to emphasize the particle-like trajectory

aspect of the uids tracer velocity) is a strictly continuum concept. As such, no

direct gas-kinetic molecular interpretation [86] of v

l

appears possible. This is equally

true of the uids volume velocity, v

v

(x; t): Despite the fact that particle-tracer

velocimetry is a widely practiced and seemingly elementary experimental technique

for measuring uid motion, given our prior discussion the possible limitations of

tracer velocimetry appear not to have been scrutinized with the fundamental care

that they deserve, indeed require, in order for such measurements to be regarded as

accurately monitoring the undisturbed uid motion.

As a case in point, consider Eq. (3.1) or, more properly, the formally equivalent

expression

U = (v

m

)

0

ab

1 (k

s

=2k)

(VT)

0

; (6.4)

representing the velocity U of a non-Brownian force and torque-free spherical particle

(not necessarily a tracer, owing to the particles nonzero conductivity) immersed in a

nonisothermal uid whose undisturbed mass velocity and temperature elds are,

respectively, v

m

and T; the particle being supposed situated far from any boundaries.

The subscript 0 connotes evaluation at the point in the uid presently occupied by

(say, the center of volume of) the particle. In circumstances where the particles

conductivity is small compared with that of the uid (k

s

=k51); the particle can serve as

a tracer of the undisturbed uid motion, even in the presence of temperature gradients,

with the uids tracer velocity at the point 0 given by the expression U = v

m

abVT;

as in Eq. (6.2). On the other hand, in the opposite case, where k

s

=kb1; one nds that

U = v

m

; whence the thermophoretically animated particle no longer serves as a faithful

monitor of the undisturbed uids tracer motion, through space. Note that the particle

velocity U is size-independent in both cases, although in the highly conducting particle

case the particle velocity U will no longer be particle shape- and orientation-

independent [23], an important point; that is, in the highly conducting particle case the

formula U = v

m

would be valid only for a spherical particle. (Presumably, the

experimental observation of this departure from comparable results recorded with

other classes of particles would enable a thoughtful and rigorous experimentalist to

discover that this particular class of particles was not passive.) Additionally, it is

important to note that both limiting results hold only when the no-slip condition, Eq.

(5.1), imposed upon v

v

; obtains. The ideal, inviscid uid example discussed earlier

emphasizes the importance of the no-slip condition in tracer experiments designed to

monitor the intrinsic motion of the undisturbed, particle-free uid.

6.5. Concluding remarks

It is important to recognize that the experimentally observed difference in

velocities between v

l

and v

m

in Eq. (6.2) is not simply an artifact of the particular

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H. Brenner / Physica A 349 (2005) 60132 91

class of phoretic thermal experiments that brought this velocity difference to light.

Stated explicitly, the distinction is intrinsic to the very nature of inhomogeneous

continuum uid mechanics itself, and arises from the existence of a density gradient,

Vr; rather than from a temperature gradient in the single-component case (or a

species concentration difference in the isothermal binary diffusion case). Explicitly,

from Eqs. (1.5) (1.6) and (1.10) the generic tracer/mass velocity difference is

v

l

v

m

= D

v

Vln r ; (6.5)

with D

v

equal to either a or D; thereby revealing the density gradient to be the

fundamental source of the velocity disparity for both thermophoretic and

diffusiophoretic particle motions. As such, the driving force animating thermo-

phoretic particle motion, for example, should not be attributed to the temperature

gradient; for, as is clear from Eq. (3.1), were the uids thermal expansivity b to be

zero, neither the uid nor the entrained particle would move, temperature gradients

notwithstanding. Thus, it is the existence of the density gradient Vr; rather than the

temperature gradient VT; to which the uids tracer motion should be attributed. In

this same context, the thermal stress T

termed a Korteweg stress (as subsequently discussed in Section 8); for were b = 0 at

some intermediate point in a uid within which the temperature varied, as is possible

in the case of some liquids (e.g. water at 4

exist at that point despite the presence there of a temperature gradient.

At least in the zero Knudsen number continuum uid regime, the latter

observation regarding expansivity belies the commonly held belief [43] that a freely

suspended particle moves through a gas because those molecules striking the particle

from its hotter side are more energetic, and hence possess greater momentum, than

those on its colder side, resulting thereby in the transfer of momentum from the gas

to the particle, thus causing movement of the particle through the suspending uid

towards the lower temperature region. (This argument may, however, possess some

measure of validity in the large Knudsen number, noncontinuum regime.) Rather,

the ultimate source of the particle motion resides in the fact that the uid itself is

moving (v

l

v

m

a0) relative to the space-xed temperature eld and, consequently,

relative to the space-xed walls. Since no force acts upon the unrestrained

thermophoretic particle, from the vantage point of an observer xed in the walls

(for which v

m

= 0), the particle is simply entrainedthat is, carried along piggy-

backby the moving uid (v

l

a0) [except, possibly, for the slip effect seen in Eq.

(3.1) due to particles nonzero thermal conductivity k

s

; causing the sphere to lag the

uid]. Indeed, were one to accept this discredited hot-side/cold-side argument,

when the sphere radius became vanishingly small, no particle sides would remain

to permit such a distinction, whence a very small particle would presumably not

move! Yet, based upon its size-independence, the theoretically conrmed expression

(3.1) shows, at least in the continuum limit, that the particle would indeed continue

to move through space relative to the temperature gradient, were its radius to

become vanishingly small.

Finally, as practical matter, we note that in circumstances where the uids

undisturbed mass velocity satises the inequality v

(0)

m

b j

(0)

v

= abVT

(0)

; Eq. (6.4)

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H. Brenner / Physica A 349 (2005) 60132 92

shows that U - v

(0)

m

; in which case the experimentally measured particle velocity U

would closely approximate the uids tracer velocity, v

l

:

7. Further evidence in support of the v = v

v

hypothesis

Direct measurement of the uids volume velocity (namely the ux density of

volume n

v

[5]) at a point of a uid appears infeasible on purely theoretical grounds,

much less as a practical possibility. Accordingly, any evidence offered in support of

the fundamental hypothesis (1.4), as well as of the accompanying supplementary no-

slip boundary condition hypothesis (1.7) associated therewith, must necessarily take

an indirect form.

In this context, we note that the evidence offered thus far in support of the above two

interrelated hypotheses derives from experimental thermophoretic data for gases and, to

a much more limited extent, comparable data for liquids. Such corroboration involves

the observed agreement, discussed in Section 3, between the theoretically derived

equation (3.1) [23] and the experimentally based semi-empirical thermophoretic velocity

correlation (3.5) for gases, as well as with the raw liquid-phase velocity data of McNab

and Meisen [45]. Such agreement provides continuum-mechanical support for the

viability of the relation v = v

v

in the context of the no-slip condition (1.7). On the

molecular side of the ledger, our derivation in Section 4 of the nontraditional Newtonian

viscosity constitutive equation (4.8) from the Burnett solution [6,7] of the Boltzmann

equation (for monatomic Maxwell molecules) provides independent, molecularly based,

noncontinuum-mechanical evidence in support of the volume velocity hypothesis v = v

v

in the context of Eq. (1.1). This latter verication is accomplished independently of the

supplementary no-slip boundary condition (1.7), whose validity (or lack thereof) does

not enter into the question of the uids rheological equation of state for the deviatoric

stress T: Reciprocally, our demonstration in Section 5 of the fact that the experimentally

and theoretically based Maxwell slip velocity formula (5.2) for ideal monatomic gases

accords constitutively with our proposed no-slip volume velocity boundary condition

(5.1), offers additional independent evidence in support of our proposed nontraditional

no-slip boundary condition (1.7) (1.4).

What follows below is a summary of further, independent evidence offered in

afrmation of the hypothesis (1.4) (or, less stringently in several cases, at least of the

fact that vav

m

) and/or the proposed no-slip boundary condition (1.7)/(5.1) [87].

Each such evidentiary item is further documented in detail elsewhere. The evidence

offered below is of a tripartite nature, consisting of experimental, molecular, and

continuum-mechanical documentation. Each of these three distinct categories is

separately discussed below.

7.1. Additional experimental evidence

7.1.1. Diffusiophoresis

Diffusiophoretic particle motion [25], occurring with a velocity U (v

m

)

0

relative

to the uids undisturbed mass motion v

m

existing at the point presently occupied by

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H. Brenner / Physica A 349 (2005) 60132 93

the center 0 of the particle, is the exact analog of the thermophoretic particle

motion discussed in Section 3 [see also Eq. (6.4)]; now, however, the density gradient

animating the particle, as embodied in the generic Korteweg stress [cf. Eq. (8.1)], is

caused by a binary species density gradient in an isothermal uid rather than by a

temperature gradient in a single-species uid. In circumstances where the effects of

pressure gradient effects on the uids density are small compared with those caused

by species concentration gradients, one obtains the following theoretical formula for

the diffusiophoretic velocity of a nite-size solid particle whose physicochemical

passivity does not permit diffusion of either species through its interior, nor

adsorption onto its surface [29]:

U v

m

= DVln r : (7.1)

The subscript 0 has been omitted for simplicity in the above; r( r

0

) is the density

of the undisturbed uid in the neighborhood of the particle, and D is the mixtures

Ficks law diffusivity. This formula, which is applicable to both gases and liquids,

was derived [25] on the basis of the pre-constitutive equations set forth in Sections 1

and 2, with the velocity v assumed given by the nontraditional constitutive equation

(1.4), together with the comparable nontraditional boundary condition (1.7).

Additionally, the energy equation (2.9) has been replaced by the elementary binary

species transport equation [18],

r

D

m

w

i

Dt

V

.

j

i

= 0 (i = 1; 2) ; (7.2)

with w

i

the mass fraction of species i; and in which the diffusive species current is

assumed given constitutively by Ficks law, j

i

= rDVw

i

; valid in the case of

isothermal isobaric systems [88]. Additionally, the law of additive volumes for

thermodynamically ideal mixtures, (q^ v=qw

1

)

p;T

= const, was assumed applicable,

together with the functional diffusivity dependence for gases demanded by gas-

kinetic theory [18], namely D = D

+

=r with D

+

a density-independent constant [89].

Eq. (7.1), based upon our nontraditional uid-mechanical hypothesis (1.4), is

shown elsewhere [25] to agree well with experimental diffusiophoretic data for binary

gas mixtures in the continuum regime. It also accords with other theoretical

approaches to the rationalization of diffusiophoretic particle motion based upon the

traditional NavierStokesFick formulation derived from the classical velocity

choice (1.3) (and the inconsistent assumption that the mixture is incompressible,

V

.

v

m

= 0). Moreover, in these latter approaches, Maxwells slip boundary condition

(5.2) was replaced by the so-called KramersKistemaker [65] concentration-slip

boundary condition for gases, the latter representing the (empirical) analog [90] of

Maxwells Eq. (5.2) for gases, with the temperature gradient replaced by a species-

gradient counterpart. Similar to the issues outlined in Section 5 and documented in

Appendix C, it is fortuitous that these NSF analyses (F here referring to Fick

rather than Fourier) furnish theoretical results that accord with experiment.

Eq. (7.1) shows the diffusiophoretic particle velocity to be independent of particle

size. Moreover, as a result of the particles supposed passivity, U is also independent

of particle shape and, hence, of the particles orientation relative to the space-xed

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H. Brenner / Physica A 349 (2005) 60132 94

species concentration gradient [25]. Accordingly, in the sense of particle-tracking

velocimetry experiments, such a particle plays the role of a passive tracer of the

uids undisturbed tracer velocity v

l

in the sense that U v

l

: The latter conclusion

accords with the generic theoretical formula (6.5) upon there replacing the symbol D

v

by the binary diffusion coefcient D:

7.1.2. Thermal transpiration

The phenomenon of thermal transpiration, discovered experimentally by Osborne

Reynolds [71] in 1879, was, historically, the rst phoretic phenomenon to be

explained using Maxwells slip condition (5.2). Indeed, as discussed in Section 5, it

was to explain Reynolds observations that Maxwell created the celebrated

Appendix to his 1879 paper [8,70], wherein Eq. (5.2) was rst derived and

subsequently applied to Reynolds data.

The so-called thermolecular pressure associated with thermal transpiration

phenomena arises during steady-state heat transfer in horizontal, single-component,

gas-lled, capillary tubes (radius a; length L) of large aspect ratio ( = a=L51)

possessing insulated side-walls, and whose two closed heat-conducting ends are

maintained at different temperatures. According to the traditional NSF equations

based upon Eq. (1.3) and satisfying the traditional no-slip boundary condition (1.7)

(1.3) on the side-walls and ends, the pressure should be uniform throughout the

capillary tube owing to the predicted absence of mass motion, v

m

= 0; and

concomitant absence of pressure gradients based upon the traditional creeping ow

equation (2.12) with v = v

m

and V

.

v

m

= 0: Explicitly, the only transport

phenomenon predicted to occur in such circumstances on the basis of the NSF

equations is that of one-dimensional steady-state heat conduction between the hot

and cold reservoirs (respectively, maintained at temperatures T

h

and T

c

) situated at

the opposite ends of the capillary, with the resulting local temperature gradient VT

at each point of the uid accompanied by a corresponding local density gradient Vr

in the supposedly isobaric system. However, upon performing this experiment with a

gas, Reynolds [71,91] observed a pressure difference between the two ends of the

capillary, with the pressure being highest at the hotter end (p

h

4p

c

): The observed

thermomolecular pressure difference p

h

p

c

40 for gases has since been conrmed

by others (cf. the review in Ref. [24] encompassing a wide variety of gases). In fact,

thermal transpiration enjoys a number of current practical uses [92].

As the thermomolecular pressure difference was not explicable by conventional

NSF continuum uid-mechanical arguments, Maxwell attempted to the explain

the phenomenon on the basis of his slip hypothesis (5.2), and, in so doing,

concomitantly give quantitative credibility to his earlier qualitative speculations

regarding the workings of Crookess radiometer [67]. It was in this context that

Maxwell, in the Appendix to his 1879 paper [8], rst introduced his notion of thermal

slip along the insulated side walls of the capillary tube, still, however, regarding the

conventional incompressible NSF equations as correctly quantifying the uid

motion ensuing within the capillary tube interior, as in Section 5. Maxwells analysis

has since proved successful [24] in explaining the observed pressure difference for

(monatomic) gases [93], at least to within a factor of two. However, as in all other

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H. Brenner / Physica A 349 (2005) 60132 95

applications which invoke Maxwell slip (e.g. thermophoresis and diffusiophoresis),

thermal transpiration is regarded as a noncontinuum O(Kn

2

) phenomenon despite

use of the conventional NSF continuum equations in its rationalization. Again,

this viewpoint appears to be inconsistent. In contrast, Bielenberg and Brenner [24],

using the nontraditional equation set and no-slip boundary condition of Sections 1

and 2 based upon Eq. (1.4), arrive in the case of gases at the same thermomolecular

pressure difference, p

h

p

c

= 8C

s

(m

2

=rTa

2

)(T

h

T

c

); as is given by Maxwells

original 1879 formula [8] for monatomic gases (albeit with our C

s

=

3

2

appearing in

place of Maxwells C

s

=

3

4

) in capillary tubes of large aspect ratio. In the preceding, a

is the capillary radius and rT - const. throughout the tube owing to the assumption

of a small temperature difference, T

h

T

c

; and a concomitantly sensibly uniform

pressure thus prevailing throughout the ideal-gas-lled capillary tube. A more

general formula than that given here, based upon our theory, and presumably also

valid for liquids, is given in Ref. [24].

That the two thermomolecular pressure formulas, ours and Maxwells, for the

thermal transpiration case should agree despite Maxwells apparently inconsistent

use of the traditional incompressible NSF equations can be explained in the same

manner as set forth generically for single-component gases in connection with Table

2 in Appendix C. While agreement thus obtains in this case between Maxwells

v = v

m

noncontinuum slip scheme and our nontraditional v = v

v

continuum scheme,

the use of the Maxwell slip condition in conjunction with the incompressible NSF

equations results in a violation of the rst law of thermodynamics in the present

thermal transpiration case, as earlier noted in Section 5 (see Appendix D). This

violation owes to the nonzero mechanical work predicted by Maxwells theory to

have been done on the conned uid by the surroundings [through the action of

the T

m

= 2mVv

m

viscous stresses existing at the wall in conjunction with the

Maxwells thermal creep condition (5.2) prevailing there], with the resulting

mechanical energy thereby supposedly introduced into the uid ultimately being

dissipated via viscous action occurring in the uids interior. In turn, as a

consequence of this dissipation, and for the steady-state circumstances characterizing

thermal transpiration, more internal energy would leave the capillary at its cold end

than entered at its hot end. Such behavior constitutes a clear-cut violation of basic

thermodynamic principles, given that no heat or work from the surroundings enters

the uid through the rigid immobile insulated side walls. In contrast, no such

contradiction arises in our scheme where no slip of the true uid velocity v

l

(or v

v

),

based upon Eqs. (1.4)/(1.10), occurs at the capillary walls!

Summarizing the conclusions of this subsection, the agreement of our unconven-

tional continuum theory with thermal transpiration experiments, as detailed in Ref.

[24], is offered as further evidence of the viability of Eq. (1.4). Conversely, the

resulting violation of thermodynamic laws implicit in Maxwells scheme is offered as

further evidence of the fact that the latters thermal-stress slip theory cannot be

regarded as a correct physical explanation of the phenomenon of thermal

transpiration, despite fortuitously furnishing the mathematically correct result for

the thermomolecular pressure difference. Our thermal transpiration theory,

emphasized above for gases, is presumably equally applicable to liquids [24], for

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H. Brenner / Physica A 349 (2005) 60132 96

which physical state no other theory currently exists. Insofar as we are aware, no

liquid-phase experimental data bearing on thermomolecular pressure is yet available

to test this prediction. This poses an obvious challenge for experimentalists.

7.2. Additional molecular evidence

7.2.1. Nelsons stochastic mechanics [94]

Nelsons [95] stochastic-mechanical Brownian motion model of uid-physics is

based upon the It ^ o calculus [96]. Heretofore, Nelsons work has been employed

conceptually only in the context of posing an alternative deterministic interpretation

to the conventional probabilistic Copenhagen interpretation of the foundations of

quantum mechanics. However, when addressed instead to ordinary uid motion in

viscous continua, Nelsons model appears to implicitly afrm the purely kinematical

aspects of our theory. Explicitly, Nelsons relation between the uids respective

tracer and mass velocities, v

l

and v

m

; as derived from his model of uid motion is, in

our notation [97],

v

l

= v

m

DVln r : (7.3)

Nelsons purely kinematical Eq. (7.3) is equivalent to a composite of our Eqs.

(1.5)(1.6) and (1.10), independently of the dynamical aspects of our theory, the

latter as embodied in the use of either of Eqs. (1.3) or (1.4)] in Eq. (1.1) or (1.7).

Nelson designates DVln r as an osmotic velocity, with D presumably a self-

diffusion coefcient, the analog of Einsteins Brownian diffusion coefcient [98100]

appearing in the Ito calculus formula for single-component stochastic processes.

Nelsons version of Eq. (7.3) traces its quantum-mechanical roots back to

Schro dingers [101] search for a deterministic, nonprobabilistic foundation for

quantum mechanics, one based upon more classical Newtonian-like mechanical

concepts. Nelsons original Brownian motion-based theory [95], including its relation

to quantum mechanics [102,103], has since been elaborated by Garbaczewski et al.

[104,105], as well as by others [106]. From their common perspective the osmotic

term in Eq. (7.3) constitutes an extended version of the Einstein [107]Smoluchowski

[108] Brownian motion theory for a foreign (colloidal) particle dispersed in a solvent,

representing an essentially purely kinematical theory [109,110]. In Nelsons analysis

the material entity undergoing the diffusive process quantied by the coefcient D

effectively serves as a Brownian tracer of the undisturbed uid motion (7.3). The

existence of Nelsons osmotic velocity is attributed to what Garbaczewski [104] terms

a Brownian recoil effect of the solvent uid upon the solute tracer particle.

As regards the physical interpretation of Nelsons forward drift velocity v

l

;

Garbaczewski [104] states that (with x a generic point of the uid): If the diffusion

pertains to massive [point] particles, we have a natural physical interpretation of the

forward drift as the mean velocity of particles leaving x at time t [along sample

paths]. . . : In support of this view he goes on to further state that: The mean

position evaluated along sample paths of outgoing particles, a time Dt after they left x

at t, is x v

l

(x; t)Dt: Clearly, this interpretation of Nelsons forward drift velocity,

represented by the left-hand side of Eq. (7.3), accords with the requirements

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H. Brenner / Physica A 349 (2005) 60132 97

demanded of a particle in order that the latter qualify as a tracer of the

undisturbed uid motion in the sense described earlier, namely necessitating that the

tracer be: (i) non-Brownian (i.e., massive relative to the masses of individual uid

molecules); (ii) pointsize in the particle-size-extrapolated limit; and (iii) inert or

passive.

In summary, the apparent agreement of Nelsons extended Brownian motion-

based kinematical formula (7.3) with our nontraditional kinematical view of the

uids tracer motion appears to add to the credibility of our volume velocity

hypothesis (1.4).

7.2.2. Klimontovichs statistical mechanics

The late Russian statistical-mechanician, Yuri L. Klimontovich (19242002) [111]

proposed a fundamental modication of the Boltzmann equation which involved

adding to the traditional collision integral pertaining to transport processes

occurring in velocity space an additional dissipative self-diffusion-type term

involving transport processes occurring in physical-space [112]. According to its

author, inclusion of the latter term results in a unied description of kinetic,

hydrodynamic, and diffusional processes, presumably valid for all Knudsen

numbers. The equations governing gas dynamics are then derived from the

preceding generalized kinetic equation without, however, invoking the standard

small Knudsen number perturbation theory arguments [6,7]. In the case where body

forces are absent and for the single-component uid case, the results obtained in this

manner by Klimontovich are identical to our modied Eqs. (4.1) for the deviatoric

stress and (2.6) for the internal energy ux, in which the quantity j

v

appearing in

these two equations is given by Eq. (1.6). Klimontovichs theory is based upon the

assumption that the uids thermometric diffusivity a; kinematic viscosity u; and self-

diffusivity D are all, equal, conditions not fully realized in practice. In

Klimontovichs work, the quantity that we have termed j

v

is identied by him as

constituting a self-diffusion ux rather than a volume ux.

As our continuum-mechanical results were hypothesized and compared with

existing data prior to becoming aware of Klimontovichs statistical-mechanical work

(which, incidentally, bears no obvious relation to the Maxwell-Burnett nonconti-

nuum notion of thermal stresses in gases) we regarded and continue to regard the

agreement between the two theories as offering conrmation of both theories. This is

especially true in view of the fact that Eq. (1.5) in the form v

m

= v

v

aVln r (our

notation) also appears naturally in Klimontovichs work, with v

m

implicitly

identied therein as being the uids mass velocity by virtue of its appearance in

the latters continuity equation (1.2) (again, our notation). Klimontovich uses the

symbol u for what we have here identied as the volume velocity v

v

; although no

comparable volume-related physical identication is assigned by him to u: While the

two modied theories agree exactly with regard to the common equations cited

above, they differ nevertheless in one important respect. Explicitly, in Klimonto-

vichs momentum and energy equations, the three velocities ( ^ m; v

k

; v

w

) upon which

we focused in Appendix A and identied therein as being v

m

; are, in fact, identied in

his work as being v

v

: This is amusing because in the original version of our present

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H. Brenner / Physica A 349 (2005) 60132 98

theory we made exactly the same identication as did Klimontovich for these

three velocities. However, we subsequently had occasion to question this view,

owing to the fact that it appears to violate Newtonian mechanics, as per the

discussion of Appendix A. That is, Klimontovichs proposal in regard to the three

velocities appears to be in conict with the basic principles of classical mechanics.

This becomes especially clear upon including in the momentum equation body

forces (real and ctitious), as we have done in Appendix A. We confess to being

conicted about our altered choice of v

m

over v

v

; an issue which we plan to

review in the near future. In any event, the issue is moot at the present time

in the sense that, owing to the fact that these velocities prove to be negligible in

the creeping ow problems underlying the phoretic phenomena addressed, the

choice does not impact upon the experimental conrmation of the several hypo-

thesis that we have effected regarding the proposed modications of the NSF

equations.

7.3. Additional continuum-mechanical evidence

7.3.1. Fitts on diffuse internal energy ow [14]

Our modied theory of transport in uid continua centers directly on the twin

issues of the constitutive equation (1.4) and the related no-slip boundary condition

(1.7)/(5.1), both appearing supercially to pertain only to momentum transport.

However, a third transport-related issue enters indirectly into consideration, namely

that embodied in the pre-constitutive equation (2.6) involving the internal energy

current j

u

; whose explicit constitutive form is implicitly required in the basic internal

energy transport equation (2.9). In particular, the nontraditional precursor

thermodynamic work term pj

v

appearing therein, arising from the diffusive

transport of volume, is not present in any of the standard texts on transport

processes or irreversible thermodynamics, the sole exception (of which we are aware)

occurring in the book of Fitts [14]. In place of what we have denoted as pj

v

in Eq.

(2.6) there appears in Fittss expression for the internal energy ux density [see Fitts

Eqs. (3-21) and (3-25)] the term p

N

i=1

v

i

j

i

[113], with v

i

the particle specic volume of

species i: In isobaric isothermal multicomponent mixtures [4,13] one has that v

v

=

N

i=1

v

i

n

i

; with n

i

= n

m

w

i

j

i

the Eulerian ux density of species i: Inasmuch as

r =

N

i=1

w

i

v

i

; it thus follows from Eq. (1.5) in conjunction with the denition n

m

=

rv

m

of the mass velocity that

j

v

=

N

i=1

v

i

j

i

: (7.4)

Fitts extra energy ux term is clearly identical to our nontraditional pj

v

term,

although in his analysis this term arises only in the context of multicomponent uid

mixtures, being absent in the case of single-component uids. This contrasts with our

own work [4,21], where a diffusional volume ux contribution pj

v

adds to the

thermodynamic rate of working at a material surface, even in the case of pure uids

(for which j

v

= aVln r). Nevertheless, despite this issue of its domain of

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H. Brenner / Physica A 349 (2005) 60132 99

applicability, we regard the analysis of Fitts (and, to a lesser extent, that of the

closely related work of de Groot and Mazur [113]) as offering an independent

measure of support for our nontraditional NSF theme.

7.3.2. Prior speculation in the literature regarding the equality v

l

= v

v

(for

multicomponent mixtures)

The evidence to be presented in this subsection cannot strictly be counted

as legally admissible in the same quantitative sense as in the examples offered

above. Nevertheless, the musings of other researchers whose work, described

below, relates peripherally to our nontraditional view, would appear to constitute

something more than mere hearsay. In this context, we refer here to remarks by

Onsager [114] and Haase [115117], independently made in connection with

their respective discussions of isothermal diffusion phenomena, and apparently

implying the validity of Eq. (1.10), namely v

l

= v

v

: (Of course, in the context of

their pronouncements on the latter equation, both authors already understood

that, generally, v

v

av

m

in multicomponent uids owing to species concentra-

tion-induced massdensity gradients. As such, it can be condently asserted that

each appreciated the fundamental fact that v

l

av

m

; one of the main items in

our theory.)

The hints found thus far in the literature pertaining to our proposed equality,

v

l

= v

v

; each involve the role of the volume velocity in multicomponent diffusion

problems. Thus, Onsager [114], upon recognizing the strictly relative, rather than

absolute, nature of the diffusional process occurring among the constituent species in

a mixture, refers to what he calls a hydrodynamic velocity in such problems. He

then proceeds to identify, albeit only implicitly, the latter velocity with what is now

called the volume velocity [4,1315], a name with which he was apparently

unfamiliar at the time, as would appear from the context of his remarks. Haase

[15,115], on the other hand, refers explicitly to the volume-average velocity v

v

in

multicomponent mixtures as being the convective velocity, presumably v

l

; clearly

distinguishing the latter from the mass-average velocity v

m

of the mixture, and

obviously understanding that the former, rather than the latter, represents the

physical velocity with which the uid moves through space. (That is, by the word

convection one understands the conveyance through space of an entity entrained

in a owing uid. Hence, the phrase convective velocity on the part of Haase

would appear to refer implicitly to the movement of a tracer entrained in the uid,

rather than to the movement of a hypothetical material particle, the latter moving

at the mass-average velocity v

m

:) The contexts of each of these two authors was

kinematic rather than dynamic, although Onsagers use of the word hydro-

dynamic suggests an intuitive understanding of the dynamical issues owing to the

mass ow engendered by the molecular diffusion processes. Interestingly, Maxwell

[118] himself refers to experimentally: . . .measuring [sic] the velocity by its volume

which passes through a unit area rather than by the distance traveled by a molecule in

unit of time, apparently regarding these as being equivalent, although he may have

intended these remarks to apply only in the uninteresting case of incompressible

uids, wherein v

l

= v

m

:

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H. Brenner / Physica A 349 (2005) 60132 100

7.3.3. Streater et al. on the N S F equations

Streaters ongoing theoretical studies [119123] of single-component nonisother-

mal uids (termed by him compressible Navier Stokes with temperature, to which

topic he subsequently refers using the acronym C-N-S-T) raise questions similar to

those raised here, albeit from a very different physico-mathematical perspective,

namely statistical dynamics [123,124], a eld of inquiry closely related to the eld

of information dynamics. Grasselli and Streater [120], like us, argue that problems

exist with respect to the accepted form of the NavierStokes equations. This

important point is emphasized in their opening paragraph by the statement that: An

unusual feature of the system is that the Euler continuity equation acquires a diffusion

term. This bulk diffusion does not appear in the standard theory [124], but has arisen in

some other work [125]. It is likely that our equations are more stable and physically

more accurate than the usual Navier Stokes equations. While the actual form of

their diffusive term differs slightly from ours, this is likely accounted for by the fact

that the GrasselliStreater hopping rule [120], quantifying the process of

thermalization upon which their detailed calculations are based, is somewhat ad

hoc. This leads also to the apparent inability of these authors to explicitly relate their

thermalization parameter l directly to a physical property of the uid, such as the

uids thermometric diffusivity. Grasselli and Streaters [120] diffusive term spills

over into their momentum and energy equations. However, their ad hoc

thermalization model does not permit a direct comparison of their momentum

and energy transport equations with ours.

8. Discussion

This section addresses, inter alia, an apparent relation existing between the

MaxwellBurnett temperature-gradient stress and Kortewegs density-gradient

stress. Furthermore, we contrast our present body-force-free phoretic phenomena

with another class of phoretic motions animated by body forces appearing in the

linear momentum equation. The latter class, illustrated by electrophoresis, while

supercially appearing to involve slip of v

m

at the particle surface, actually

involves velocity jump across a thin boundary layer (the region in which the body

forces are sensible) accompanied by no slip of v

m

at the physical surface of the

particle. The important body-force distinction existing between these two classes of

particle locomotion is used to compare and contrast our model of thermophoresis in

liquids with an alternative theory of the phenomenon due to Semenov and Schimpf

[47]. Additionally, several potentially practical applications of the present theory are

discussed, extending beyond the realm of strictly phoretic phenomena.

8.1. Korteweg stresses

In 1901 Korteweg [63] introduced the notion of a density gradient-induced

mechanical stress tensor, above and beyond the standard Newtonian viscous stress

tensor, Eq. (4.2). After a long period of relative dormancy, the subject of Korteweg

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H. Brenner / Physica A 349 (2005) 60132 101

stresses was resurrected in connection with interfacial phenomena. In the case of

immiscible uids this occurred in connection with the CahnHilliard stress tensor

[126,27], where the interface between the two bulk uid phases is regarded not

as a singular surface but rather as a diffuse interfacial region of effectively nite

thickness, whose local equilibrium and transport properties, particularly the

density r; vary continuously across the interfacial transition region. Similar diffuse

interface uses for the Korteweg stress were later adopted by Joseph and others

[26,127,128] in relation to the phenomenological possibility of a transient interfacial

tension arising between a pair of miscible uids (of different densities) brought

suddenly into intimate contact, thereby creating a fairly steep initial density

gradient interface between them. Since the two miscible bulk uids subsequently

undergo mutual diffusion, any such interfacial tension must necessarily be transient

in duration.

The phenomenological form proposed by Korteweg [63] for his (traceless and

symmetric) stress tensor is

T

K

= I[gV

2

r a(Vr)

2

] b(Vr)(Vr) dVVr ; (8.1)

where the four independent Korteweg coefcients (a; b; g; d) (his symbols) appearing

above are, in the absence of an appropriate molecular theory, to be determined

experimentally, including their algebraic signs. It is interesting to note that the

constitutive form of the above stress is identical to the extra stress given by Eq. (4.6)

jointly with Eq. (1.6) (generalized to be applicable to both liquids and gases, as well

as to single- and two-component mixtures, the latter upon replacing a by D

v

).

Indeed, upon identifying this T

K

stress, and

upon supposing D

v

to be a constant [129], the phenomenological coefcients

appearing in Eq. (8.1) are found to be given by the following expressions:

a =

2

3

D

v

m

r

2

; b = 2

D

v

m

r

2

; g =

2

3

D

v

m

r

; d = 2

D

v

m

r

: (8.2)

Given Maxwells prior thermal stress analysis as set forth in Eq. (5.3) and as

later amended by Burnett [cf. Eq. (4.5)], together with the fact that these thermal

stresses are, in reality, due to density gradients as discussed in Section 6, it would

appear in the case of single-species uids that the MaxwellBurnett thermal stress

and the Korteweg density-gradient stress have much in common. Although the

thermal stress analysis of Sections 4 and 5 was limited to gases, Kortewegs stress

appears to be bear no such restriction. As such, it is presumed by its users

[27,126128] to be applicable to liquids. In any event, both types of stresses represent

the extra stress, T

= 2mVj

v

; above and beyond the classical Newtonian viscous

stress tensor, T

m

= 2mVv

m

: It is interesting to note that despite their common

density-gradient ancestry, the Korteweg and MaxwellBurnett stresses are regarded

in the literature as being continuum and noncontinuum stresses, respectively,

without any rational reason being advanced for this distinction. Indeed, according

to the thermal stress arguments advanced in Section 4, such a distinction has no

basis in fact.

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H. Brenner / Physica A 349 (2005) 60132 102

8.2. Body-force-driven vs. body-force-free phoretic particle motions

The modied NavierStokes equation (2.1) (1.1) (1.4) proposed here in place

of its traditional formulation is

r

D

m

v

m

Dt

= Vp mV

2

v

v

; (8.3)

at least in circumstances where, for simplicity, the viscosity is taken to be a constant

and where the quasi-compressibility condition,

V

.

v

v

= 0 ; (8.4)

is further supposed applicable [130]. Additionally, the proposed no-slip boundary

condition to be used in the solution of transport problems is taken to be (5.1). In

arguing in favor of Eq. (8.3), we have restricted attention exclusively to

circumstances in which f = 0; and in which there is no externally imposed

undisturbed pressure gradient, Vp

(0)

= 0 (which would otherwise have resulted in

a forced-convective motion v

(0)

m

of the uid). As such, the body-force-free phoretic

uid motion which ensues is necessarily animated exclusively by massdensity

gradients, Vr: In this context it is crucial to note that our main motivation in

proposing (8.3) was not to explain thermophoretic [23] or diffusiophoretic [25]

motion; rather, it was just the opposite, namely to use knowledge of these phoretic

phenomena to demonstrate that our hypothesized modication (8.3) of the

NavierStokes equation as well as of the no-slip boundary condition, Eq. (5.1),

were consistent with these experimental data.

Acceptance of the modied theory as a working hypothesis enables one to make

predictions regarding phoretic and related phenomena (such as thermal diffusion

[48]) that is applicable to liquids, despite the fact that for all practical purposes only

gaseous experimental data were used in demonstrating the consistency of the theory.

We emphasize this fact because there does exist a body of liquid-phase thermal

diffusion data, including a comprehensive theory thereof due to Semenov and

Schimpf [47], briey discussed at the end of Section 3, and further discussed below,

that attempts to rationalize at least some of these experimental data [131]. Yet, as

will be seen, their liquid-phase thermophoresis/thermal diffusion theory does not

bear directly upon the validity of our modied uid-mechanical equations (8.3)

(5.1) because their work refers to thermophoretic particle motion animated by the

action of body forces (albeit differing sensibly from zero only in the immediate

neighborhood of the particles), whereas our thermophoretic theory is based upon

circumstances in which such body forces are everywhere precluded, including any

boundary-layer region proximate to the particle.

As a prelude to illustrating the fundamental differences existing between these

respective body-force-free and body-force-driven modes of thermophoretic motion,

below we contrast our analysis of body-force-free phoretic phenomena [2325] with

that of electrophoretic particle movement in ionic solutions, the latter driven by

electrical body forces. At the same time this electrophoretic focus enables us to draw

a sharp distinction between the purely mathematical Smoluchowski-type v

m

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H. Brenner / Physica A 349 (2005) 60132 103

velocity jump condition existing across the hypothetical Debye ionic boundary

layer [cf. Eq. (8.7)], and its Maxwell-type v

m

slip counterpart (5.2) which

represents a true mass slip at the physical surface of the solid rather than a

mathematical velocity-jump across a thin boundary layer of the type associated with

the parameter G in Eq. (5.4).

8.2.1. Electrophoretic particle motion in incompressible liquids [132 134]

In contrast with Eqs. (8.3)(8.4), whose departure from the traditional

formulations thereof is based upon uid compressibility, explicitly involving the

fact that V

.

v

m

a0; the classical NavierStokes/continuity equation formulation for

incompressible uids takes the general form

r

D

m

v

m

Dt

= Vp mV

2

v

m

f ; (8.5)

together with

V

.

v

m

= 0 : (8.6)

In this incompressible, nonzero body-force context, consider the application of Eqs.

(8.5) and (8.6) to explain the electrophoretically animated movement with velocity U

of a solid particle through an unbounded uid in the limiting case of a uniform

electric eld E

o

at innity, explicitly for the case of an electrically nonconducting

particle possessing a uniform surface charge density characterized by the zeta

potential B; and in the Debye thin double-layer limit. The body-force density in such

problems is given generally by the expression f = r

e

E; where the electric charge

density r

e

and electric eld E are, respectively, given constitutively as r

e

= V

2

f

and E = Vf; with the dielectric permitivity of the uid and f the electric

potential. Outside of the double layer the electric eld is effectively uniform at its

value E

o

; so that f f

(0)

= E

o

.

x as [x[ o; whereas the potential satises

Laplaces equation, V

2

f = 0: The potential differs sensibly from its far-eld value

f

(0)

only in the immediate neighborhood of the particle surface qV

s

; where it satises

the boundary condition n

.

Vf = 0 appropriate to a nonconducting body. Moreover,

the HelmholtzSmoluchowski slip boundary condition,

v

m

U = MVf on qV

s

; (8.7)

with M = B=m the so-called electrophoretic mobility, reects the jump in the mass

velocity v

m

across the Debye boundary layer,

Upon neglecting inertial effects in (8.5), the joint solution of this system of

equations and boundary conditions for f and v

m

; implicitly satisfying the no-

penetration condition (1.8), leads eventually to the following expression for the

electrophoretic velocity of the body:

U = ME

o

B

m

Vf

(0)

; (8.8)

a result which holds independently of both the particles size and shape [132, p. 476,

133]. As discussed, for example, by Levich [132], the Smoluchowski massvelocity

jump boundary condition (8.7), substitutes mathematically for the electrical body

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H. Brenner / Physica A 349 (2005) 60132 104

forces acting within the Debye layer in the immediate neighborhood of the particle,

being equivalent thereto in regard to its physical consequences.

We have elaborated on this classical electrophoretic problem because, super-

cially, it might otherwise appear to have much in common with our prior

thermophoretic [23] and diffusiophoretic [25] analyses of particle motion under the

inuence of mass density gradients. However, in contrast with the latter class of

phoretic motions leading to (8.3), such electrophoretic particle motion is, in fact,

ultimately caused by the action of electrical body forces, as embodied in f; rather

than by true massvelocity slip; that is, the apparent slip, being purely mathematical

in origin, is simply an artifact, rather than the root cause, of the particles

electrophoretic movement! Moreover, and perhaps most importantly, in contrast

with our nonconducting body-force-free [23,25] phoretic problems, electrophoretic

particle movement is not solely dependent upon the physical properties of the uid

(as embodied in and m); rather, it also depends upon the particles surface zeta

potential B; which is a joint uid solid property. Additionally, during

electrophoretic motion, the particle moves through the uid, rather than being

entrained in the already moving uid, as evidenced, inter alia, by the appearance of

the uids viscosity in the denominator of Eq. (8.8). Because of these fundamental

differences, body-force-animated electrophoretic motion is very different in its

physical origins from that of its body-force-free thermophoretic and diffusiophoretic

counterparts, which led to our proposed modication (8.3) of the NavierStokes

equation.

Despite these fundamental differences there nevertheless exists a striking analogy

between electrophoresis and thermophoresis, as discussed in Appendix E. When

exploited, this analogy enables many of the detailed electrophoretic solutions extant

in the literature to be directly and immediately applied to the resolution of their

thermophoretic boundary-value counterparts.

8.3. Thermophoretic particle motion in liquids. The work of Semenov and Schimpf

[47,135,136]

This subsection resumes the abbreviated discussion of the work of these authors

offered at the end of Section 3. Their model [135] is based upon the following general

arguments: When the temperature of a liquid (the solvent) varies along the surface of

a solid body, the number-density of solvent molecules will, owing to the dependence

of the solvent density upon temperature, be larger in the colder regions of the surface

than in its warmer regions. This gradient in molecular solvent number density creates

an osmotic pressure gradient along the surface, in turn giving rise to an interfacial

stress at the particle surface tending to balance this pressure gradient. These osmotic

forces are regarded as being short-range body forces f appearing in the traditional

incompressible creeping ow equations emanating from Eqs. (8.5) and (8.6), with

such forces being sensibly different from zero only in the immediate neighborhood of

the particle surface. There, similar to body-force-driven theories [3032] of phoretic

motions deriving from inhomogeneous surface adsorption phenomena, such forces

translate mathematically into an effective slip (strictly, velocity jump) of the

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H. Brenner / Physica A 349 (2005) 60132 105

uids mass velocity v

m

near the surface of the particle (more precisely at a point

lying just outside of the adsorption boundary layer).

In physical terms, the situation is not unlike that resulting from the absorption of

surfactant molecules onto a surface, coupled with the fact that any variation in the

concentration of these surfactant molecules along the surface will produce an

interfacial stress [3032] acting in the tangent plane of the surface. Here, however,

the molecules of the solvent play the role of the surfactant molecules, with the

surface temperature gradient serving to produce solvent number-density concentra-

tion gradients along the surface. The precise details governing the adsorption of

these solvent molecules onto the surface depends upon the physicochemical

adsorption forces existing between the solvent molecules and those of the solid.

These intermolecular forces are quantied in the SemeneovSchimpf analysis by

Londonvan der Waals dipoledipole intrermolecular forces. Explicitly, the

following formula is presented for their thermophoretic particle velocity U [135]

[which we have re-written in a form deliberately reminiscent of Eq. (3.1)]:

U =

a

/

b

1 (k

s

=2k)

VT; a

/

=

ln 3

8

Ar

2

0

mv

0

: (8.9)

In the above, A is the Hamaker constant dening the interaction between the particle

and the uid, m is the uids viscosity, r

0

is the radius of a solvent molecule and v

0

is

solvent volume per molecule, i.e., v

0

= ^ vm=N; where ^ v = 1=r and m are, respectively,

the solvents specic volume and molecular mass, and N is Avogadros number. For

the liquids with which they are concerned the authors suggest as an approximation

that the molecular radius be estimated from the equation v

0

= 8r

3

0

; the latter valid for

an elementary cubic crystal packing model. They also suggest use of the

approximation A =

A

p

A

s

_

; where A

p

and A

s

are the respective Hamaker constants

for the particle and solvent. With these approximations, one would have that a

/

=

(ln 3)

A

p

A

s

_

=64mr

0

:

Despite their very different origins, Eqs. (8.9) and (3.1) obviously have much in

common including the appearance therein of the uids thermal expansivity b; and

the fact that the U is independent of the size of the thermophoretically animated

particle. However, we note the following major differences in the two models: (i) in

contrast with the passive role played by the particle in our analysis, at least in the

nonconducting case, the physicochemical properties of the particle play a critical role

in Eq. (8.9) as manifested by the presence therein of the particles Hamaker constant;

(ii) as evidenced by the appearance of the viscosity in the denominator of (8.9), the

particle moves through the uid in their model, whereas in our case it moves with the

uid. Of course there is also the fundamental issue of the presence and absence of

body forces as the animating uid-mechanical mechanism in the two models.

The work of these authors impacts upon the fundamental notion of the tracer

velocity of a uid, as discussed in Section 6. According to their theory, even in

nonconducting circumstances, where k

s

=k51; the particle will not be passive, in

the sense that its physicochemical properties enter into the particle velocity U in the

guise of the particles Hamaker constant. As such, the particle would not qualify in

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H. Brenner / Physica A 349 (2005) 60132 106

the role of a tracer in the case of nonisothermal uids. More general versions of their

theory [47] suggest that this physicochemical dependence would, in the case of non-

spherical particles, also cause the particle velocity U to depend upon its orientation

relative to the direction of the imposed temperature gradient, further comprising its

role as tracer.

A variant of Eq. (8.9) [47] has been applied with some success to explain

LudwigSoret thermal diffusion effects in solutions of polymers dispersed in

nonpolar solvents, with the long-chain macromolecule viewed as a thermophoretic

particle. In creating their model these authors use a priori knowledge of the fact

that the LudwigSoret thermal diffusivities of polymer molecules are known to be

independent of chain length as well as of the presence of side branches [137]. By way

of comparison, our own model [48] of polymer thermal diffusion derived from (3.1)

demonstrates this independence, rather than assuming it a priori.

While it may appear that a conict exists between Eqs. (3.1) and (8.9) for the

thermophoretic velocity of a spherical particle, this is not necessarily the case.

Rather, it is possible that the two effects may be additive, with Eq. (3.1) referring to

that portion of the total particle velocity constituting motion with the uid, whereby

the particle is effectively entrained (except, perhaps, for the k

s

=k thermal

conductivity factor) in a uid which is already moving in the absence of

physicochemical body forces, and with Eq. (8.9) referring to that portion of the

particles motion taking place through the uid, stemming from the action of local

physicochemical body forces causing velocity slip. To explore this possibility, we

add the two equations in question to obtain

U = (1 )

ab

1 (k

s

=2k)

VT ; (8.10)

=

ln 3

8

A

p

A

s

_

r

2

0

mav

0

(8.11)

in which is a dimensionless parameter (not necessarily small) representing the

SemenovSchimpf correction to Eq. (3.1).

8.3.1. Liquids

Semenov and Schimpf provide data enabling to be calculated in the case of silica

particles in various liquid solvents. Notationally, with b

T

their proportionality

coefcient dened by the formula U = b

T

VT; Eq. (8.11) is equivalent to

= 1

k

s

2k

_ _

b

T

ab

: (8.12)

Explicitly, Semenov [135] summarizes estimated and experimentally available data

for the parameters b

T

; k

s

; k; b appearing above. Thermometric diffusivity data were

taken from Photothermal Spectroscopy Methods for Chemical Analysis, Wiley, 1996.

These data, together with the estimated value of obtained therefrom, are tabulated

below in Table 1.

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H. Brenner / Physica A 349 (2005) 60132 107

These data suggest that for liquids the SemenovSchimpf contribution provides a

relatively modest modication of the entrainment model (3.1), a quantitative

conclusion subject, however, to the caveat implicit in the uncertainty surrounding

use of the approximation A -

A

p

A

s

_

for the Hamaker constant. According to these

authors, their result alone, independently of the further contribution of (3.1),

appears to accord with experimental data for silica, at least as regards its order-of-

magnitude. However, it needs to be emphasized that the data on which this

conclusion is based are neither single-particle data, nor were the particles studied

sufciently large to exclude the possibility of Brownian motion. And, when both

factors are simultaneously present, one is no longer dealing with thermophoresis as a

phenomenon in its own right; rather, one is more likely dealing with Soret-effect

thermal diffusion phenomena, to which our single-particle, non-Brownian theory is

not directly applicable in the absence of further theoretical considerations [48]. In

any event, despite such reservations and caveats, Eq. (3.1) cannot be ruled out as

applicable to thermophoresis in liquids.

8.3.2. Gases

While Semenov and Schimpf make no claims that their analysis should apply

to gaseous continua, there appears to exist no reason in principle while gases

should be excluded from the domain of applicability of Eq. (8.9). Certainly, their

underlying notion of uid-generated osmotic pressure as constituting the driving

force for thermophoretic motion in uid continua would appear as applicable to

gases as it is to liquids. However, upon attempting to apply their equation to

gases, it becomes evident that major theoretical and experimental conicts exist

with Eq. (3.5) [in which C

s

= O(1)], the latter viewed as representing a summary of

experimental data for thermophoresis in gaseous continua. Even apart from

issues of differences in orders of magnitude, the experimental data support a model

in which the particles thermophoretic velocity increases with increasing gas viscosity

m and decreasing density r; whereas Eq. (8.9) would appear to predict exactly the

opposite trends. Moreover, whereas the experimental data (3.5) suggest that the

physicochemical properties of the particle should not be relevant to its thermo-

phoretic velocity (apart from particles thermal conductivity k

s

), the presence of

the particles Hamaker constant A

p

in the SemenovSchimpf formula suggests

otherwise.

ARTICLE IN PRESS

Table 1

SemenovSchimpf correction to Eq. (3.1) for the case of silica particles in various solvents

Solvent

b

T

(10

7

cm

2

s

1

K

1

) b(10

4

K

1

)

k

s

=k

a = k=r^ c

p

(10

3

cm

2

s

1

)

Water 0.19 2.1 2.4 1.43 0.14

Tetrahydrofuran 1.39 11 4.4 0.824 0.49

Acetonitrile 2.4 14 3.6 1.08 0.44

Cyclohexane 0.70 12 3.8 0.858 0.20

H. Brenner / Physica A 349 (2005) 60132 108

8.3.3. The need for experimental liquid-phase data

The preceding discussion reinforces the view expressed in Section 3 of the critical

need for single-component thermal gradient data in liquids. In subjecting these or

any other theories to test, such data need not be limited to thermophoretic of thermal

diffusion data. All such theories involve the notion of slip of one kind or another at

the boundary between a uid and a solid, whether such slip be of the Maxwell

thermal-creep or SemenovSchimpf velocity-jump types. Steady-state thermal

transpiration experiments [24] offer an interesting alternative to thermophoresis in

this respect, since the presence of slip is manifested macroscopically as a pressure

difference across a capillary tube or across a porous medium, whereas no such

thermolecular pressure difference would arise in the absence of slip. Experiments

of this nature are currently underway at Sandia National Laboratories under the

direction of Lisa A. Mondy.

8.4. Potential applications of the general theory

From a practical point of view, pragmatists could argue that our proposed generic

modications of the original NSF (or NSFF) equation set constitute but a

small correction to those equations in situations where density gradients exist. In

reference to the question of the general viability of this viewpoint, it is useful to rst

establish the circumstances under which the correction will be small. In particular,

the corrections do indeed prove to be small in those applications for which the ratio

:= [j

v

[= max [v

m

; v

v

[(0pp1) satises the inequality 51: Thus, as a practical

matter, for small density gradients it will often be true that [v

m

[ - [v

v

[; in which

situations the disparity between the mass- and volume- or tracer-velocities, v

v

= v

l

;

will indeed be small. Conversely, when = O(1) such corrections will no longer be

small, as occurs, for example, during thermophoretic and diffusiophoretic uid

motions. Other examples come readily come to mind, such as steady-state

thermal diffusion [48], where temperature- and species-gradients coexist. Closely

related to the zero massvelocity condition v

m

= 0 encountered during thermo-

phoretic motions, is the fact that in a number of applications, such as thermal

transpiration, the mass velocity does not vanish locally at each point of the uid, but

rather vanishes only in an integral sense,

_

A

v

m

; dA = 0; with A typically a cross-

sectional area. Obviously, in such circumstances the small-correction inequality

criterion 51 will again be violated, albeit this time in a global rather local pointwise

sense. In any event, it is obvious that effects stemming from the existence of a

diffusive volume ux, rather than always representing minor corrections to

conventional results, may, in fact, be relatively largeindeed, sometimes represent-

ing the dominant effect, as in the examples cited above. Microuidic applications,

involving very slow mass motions possibly driven by temperature gradients, come to

mind in this context.

Apart from practical engineering-type application of the types discussed above,

several other areas of potential interest come to mind. These include use of the

present continuum theory to rationally re-organize the hierarchical ordering of the

Burnett-type noncontinuum terms that arise when solving the Boltzmann equation

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 109

perturbatively at higher order [6,7,57,64,138,139] in the Knudsen or Mach

numbers. More rational theories of mixtures [140], involving elucidation of the

constitutive and transport properties of so-called interpenetrating continua,

appears to be another area ripe for exploitation. Transport phenomena in porous

media [141] also offer interesting challenges owing to the fact that the v

v

-based Eqs.

(2.13) and (2.14) together with (1.7) (1.4) are identical to their classical v

m

-based

creeping ow counterparts, often used in deriving Darcys law governing ow in

porous media.

8.5. Summary

The main results of the present work lie in our proposed modication (8.3) of the

NavierStokes equation and no-slip boundary condition (5.1) for the case of

compressible uid continua, where the mass density r is not uniform. In turn, these

lead to the prediction of a Korteweg-like stresses (8.1) in both liquids and gases

which, in turn, cause the phoretic entrainment of isolated particles toward

regions of high uid density, such that the velocity of the particle through space

proves to be independent of its size, shape, and physicochemical properties in

circumstances where the particle is passive. It is possible in a biological context

that such density-gradient-induced locomotion may play a role in chemotaxsis

or thermotaxis.

Note added in proof

Reconciliation of Maxwells slip coefcient C

s

= 3=4 for monatomic (Maxwellian)

molecules with our value of C

/

s

= 3=2

Apart from fundamental philosophical continuum vs noncontinuum differences

for gases, the only quantitative difference between the predictions of Maxwells

theory and our theory arises from the purely numerical factor of two stemming from

the different values ascribed to the O(1) Maxwell slip coefcient C

s

appearing in Eq.

(5.2). Whereas, at least in the case of monatomic gases, Maxwell [8] arrives

theoretically at the value C

s

= 3=4 (for Maxwell molecules) on the basis of molecular

arguments as per the discussion of section 5, our purely continuum theory gives

C

s

= 3=2 as set forth in Eqs. (5.6) (3.3) (although without restriction to Maxwell

molecules). In the case of monatomic molecules this difference can, however, be

reconciled, as discussed in what follows below.

Because the equations of gas dynamics are not valid in the Knudsen layer (whose

thickness is of the order of the mean-free path of the gas molecules) proximate to a

solid surface, a rigorous derivation of the continuum boundary conditions to be

applied at the solid-gas boundary involves the solution of the Boltzmann equation

inside of the Knudsen layer, and the subsequent matching of this inner solution with

the outer solution of the hydrodynamic equations outside of the Knudsen layer [139].

The boundary condition imposed on the inner problem adopts the form of a specied

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 110

law of molecular reection assumed to exist at the wall. The values of the outer elds

when extrapolated to the wall then provide the macroscopic boundary conditions

which, when enforced, provide the correct solution of the continuum hydrodynamic

equations outside of the Knudsen layer. The constitutive form thereby obtained via

this matching scheme for the boundary condition to be imposed upon the relative

tangential mass-velocity component v

m

accords with that of Maxwells Eq. (5.2),

modulo the explicit numerical value of the C

s

slip coefcient appearing therein,

which depends on the distribution of gas molecules reected from the wall

and, hence, upon the specic physicochemical natures of both the gas and solid [139,

p. 367].

Various derivations of C

s

exist based upon specic models of the gas and wall,

together with use of either the Boltzmann equation, the method of moments, or a

Monte Carlo scheme, as recently summarized by Sharipov and Kalempa [142].

Explicitly, Sharipov points out in Ref. [143] that: According to Refs. [144,145] the

thermal slip coefcient s

T

[Maxwells C

s

] varies from 0.75 up to 1.5, where the rst

value corresponds to the specular reection of molecules on [the] surface, while the

second value corresponds to the opposite situation, i.e. back reection. (With regard

to these values, Sharipov [143] is presumably referring here solely to the case of

monatomic gases.) Of course, the 3=4 value corresponds to Maxwells original 1879

model [8] based upon his implicit choice of an accommodation coefcient. On the

other hand, the 3=2 value accords with our result for the slip coefcient, derived from

the assumption that there is no slip of the volume velocity at solid surfaces (together

with use of specic heat data for monatomic gases). As such, acceptance of our

theory would imply that the volume velocity-based no-slip macroscopic boundary

condition is equivalent, at least in the case of monatomic gases, to back reection of

the gas molecules at the surface.

Acknowledgements

I am grateful to Dr. James R. Bielenberg of Los Alamos National Laboratories,

formerly a graduate student in the Chemical Engineering Department at MIT. He

shared with me the pleasure of performing the exact phoretic and thermodynamic

calculations, cited throughout this paper, permitting a comparison between

experiment and theoretical productions, and resulting in conrmation of the

nontraditional constitutive equation (1.4). I am also pleased to acknowledge many

useful hours engaged in pertinent conversations with Dr. Ehud (Udi) Yariv

of the Mechanical Engineering faculty at the Technion, formerly a postdoctoral

fellow in the Chemical Engineering Department at MIT. Equally enlightening

conversations were held with Aruna Mohan, currently a graduate student in

Chemical Engineering at MIT. She was instrumental in helping me to formulate the

proof offered in Appendix A. Finally, I am also grateful to Dr. Sangtae Kim of

Purdue University, formerly of Eli Lilly and Company, whose encouragement was

helpful in arranging nancial support through Lilly for the research embodied in the

present study.

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 111

Appendix A. Invariance of the basic transport equations under change of reference

frame

From a constitutive viewpoint the respective forms we have adopted for the basic

mass, momentum, and energy transport equations, namely Eqs. (1.2), (2.1) and (2.2),

follow, inter alia, from the requirement that they remain invariant under translation

of the reference frame in which they are written. That they indeed possess this

property is formally demonstrated below.

In order to keep an open mind on the subject, we begin with the following pre-

constitutive forms of this trio of transport equations. By pre we refer not only to

the usual notion of constitutive equations for the various diffusive (i.e., molecular)

uxes such as Newtons law of viscosity or Fouriers law of heat conduction; rather,

the following equations are equally pre-constitutive with regard to the nonmolecular

constitutive expressions introduced for the specic momentum density ^ m appearing

below in the momentum equation, as well as for the kinetic and work velocities,

v

k

and v

w

; respectively, appearing below in the energy equation. For simplicity we

will suppose that each of the following transport equations are originally written, as

below, in an inertial reference frame, say x:

(i) Transport of mass : qr=qt V

.

(rv

m

) = 0 ; (A.1)

(ii) Transport of momentum : r

D

m

^ m

Dt

= V

.

P r

^

f ; (A.2)

(ii) Transport of energy : r

D

m

^ e

Dt

= V

.

j

e

V

.

(P

.

v

w

) : (A.3)

In these equations,

^

f is the specic body force density, assumed (for the time being)

to be conservative and hence expressed as the gradient of a time-independent

potential energy function

^

f(x); such that

^

f = V

^

f in which q

^

f=qt = 0: Additionally,

^ e = ^ u v

2

k

=2

^

f is the specic total energy; moreover, j

e

is the diffuse total energy

current which we suppose henceforth to be identical to the diffuse internal energy

current, j

u

on the assumption that neither kinetic nor potential energy can be

transported diffusively [146].

A.1. Coordinate transformations

Consider two systems of coordinates in space. One of these systems is an

inertial coordinate system x; which we regard as being at rest (i.e., xed in

space). The second system, say x

/

; moves relative to the former with a (generally

time-dependent) velocity U(t): Let the two coordinate systems coincide at time

t = 0: Then,

x x

/

=

_

t

0

U(t) dt : (A.4)

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H. Brenner / Physica A 349 (2005) 60132 112

The respective velocities v and v

/

of an object as measured by the two observers are

obviously related by the expression

v v

/

= U(t) : (A.5)

With regard to the respective material derivatives in the two reference frames,

D

m

Dt

=

q

qt

_

x

v

m

.

V and

D

/

m

Dt

=

q

qt

_

x

/

v

/

m

.

V

/

;

in which V = q=qx)

t

and V

/

= q=qx

/

)

t

it is readily established since (qx=qx

/

)

t

= 0 and

(qx=qt)

x

/ = U(t) that

V

/

= V and

D

/

m

Dt

D

m

Dt

: (A.6)

On the constitutive supposition that all diffusive uxes and other equilibrium

physical quantities such as p and r remain invariant under the coordinate

transformation (so that, for example, P

/

= P), and since ^ m ^ m

/

= U(t); one nds

from the linear momentum equation (A.2) together with (A.6

2

) that

^

f

/

=

^

f

dU(t)

dt

: (A.7)

A.2. Energy equation

Consider the energy equation (A.3) irrespective of any constitutive choices made

for the various quantities appearing therein. Together with use of the linear

momentum equation (A.2) and the denition of the conservative force, in

conjunction with several of the above relations one obtains the following expression

upon rearrangement:

r

D

m

^ u

Dt

= V

.

j

u

r(v

m

v

w

)

.

^

f rv

w

.

D

m

^ m

Dt

r

D

m

Dt

1

2

v

2

k

_ _

P

T

: Vv

w

:

(A.8)

As an aside, while we have derived the term rv

m

.

^

f appearing above from time-

independent potential energy considerations, this same expression could have been

obtained more generally simply as a rate of working term (per unit volume), rv

m

.

^

f;

added to the right-hand side of Eq. (A.3) while excluding the potential, energy

contribution from its left-hand side. That the velocity by which

^

f is multiplied is v

m

rather than say v

w

(or even some other velocity) is then justied by reference to the

specic case where the corresponding work term is derived via potential energy

considerations of the type having led to Eq. (A.8).

Our goal in what follows is aimed at demonstrating on purely theoretical grounds

that the following equalities necessarily hold:

v

k

= v

w

= ^ m v

m

: (A.9)

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H. Brenner / Physica A 349 (2005) 60132 113

We begin by examining the invariance of the internal energy density ^ u under the

coordinate transformation between the inertial and noninertial (i.e., accelerating)

frames. Explicitly, we write Eq. (A.8) in the primed (accelerating) system of

coordinates x

/

; thereby obtaining

r

D

/

m

^ u

Dt

= V

/

.

j

u

r(v

/

m

v

/

w

)

.

^

f

/

rv

/

w

.

D

/

m

^ m

/

Dt

1

2

r

D

/

m

Dt

(v

/

k

2

) P

T

: V

/

v

/

w

:

(A.10)

We have afxed primes to

^

f as well as to each of the velocities, v = (v

k

; v

m

; ^ m; v

w

);

appearing in the above. On the other hand we have suppressed the corresponding

addition of primes to the remaining quantities appearing in (A.10), namely

(r; ^ u; j

u

; P); based on the recognition that their special physical natures require

them to remain invariant under the coordinate transformation. Insert into (A.10)

the various transformations relating the primed variables to the unprimed ones,

including the fact that, in general, V

/

v

/

= Vv; and subtract the resulting expression

from (A.8). Upon rearrangement and division by r this yields the relation

(v

m

v

k

2v

w

)

.

dU

dt

U

.

D

m

Dt

(v

k

^ m) = 0 :

Inasmuchas U and dU=dt can each be chosen independently at any given instant of

time, such arbitrariness necessitates that

v

m

v

k

2v

w

= 0 and v

k

= ^ m : (A.11)

This is as far as one can go via internal energy invariance arguments alone.

In order to complete the theoretical proof of Eq. (A.9) we further suppose

that the internal energy transport equation (A.8) must not contain any kinetic

energy terms. This requires that v

w

.

D

m

^ m=Dt = D

m

=Dt(v

2

k

=2): Into this equa-

tion substitute Eq. (A.11

2

) so as to eliminate ^ m; and rearrange the resulting

expression to obtain (v

w

v

k

)

.

D

m

v

k

=Dt = 0: Equivalently, (v

w

v

k

)

.

D

m

^ m=Dt = 0:

Hence, with use of (A.2) we obtain (v

w

v

k

)

.

(V

.

P r

^

f) = 0: Since this latter

relation has to hold independently of the constitutive equations for either P

and

^

f; this clearly requires that v

w

= v

k

: Introduction of the latter into (A.11)

yields the further relation, v

m

= v

k

: Cumulatively, this completes the proof of

Eq. (A.9). Finally, elimination of ^ m; v

k

and v

w

from Eqs. (A.2) and (A.3) in

favor of v

m

furnishes the basic momentum and energy transport equations (2.1)

and (2.2).

Clearly, the pre-constitutive equations (2.1) and (2.2) hold independently of any of

the constitutive relations employed for the elds (r; ^ u; j

u

; p; T) and j

v

: Indeed, in the

context of gas-kinetic theory, Eqs. (2.1) and (2.2) apply even in circumstances where

the constitutive equations for the physical quantities appearing in the group cited

in the preceding sentence, such as T; include noncontinuum terms, as in the case

of (4.3).

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H. Brenner / Physica A 349 (2005) 60132 114

Appendix B. Elementary calculation of the thermophoretic velocity of a nonconducting

sphere

Consider a velocity eld v satisfying the equations Vp mV

2

v = 0 and V

.

v = 0;

in which v is the eld appearing in the deviatoric stress tensor in Eq. (1.1). According

to Faxens theorem [85] for such incompressible creeping ows satisfying a zero-

vector velocity boundary condition, v = 0 on qV

s

; the hydrodynamic force exerted

by the uid on a solid sphere qV

s

of radius a translating with velocity U when

immersed in an undisturbed creeping ow, say {v

(0)

; p

(0)

]; from which the sphere is

absent, is given by the expression

F = 6pma (v

(0)

U)

a

2

6m

Vp

(0)

_ _

0

: (B.1)

The subscript zero appearing in the above connotes evaluation of the undisturbed

velocity and pressure elds at the center of the uid space presently occupied by the

(center of the) sphere. Accordingly, a force-free sphere will, in the absence of wall

effects, move quasistatically with a velocity

U = v

(0)

0

a

2

6m

(Vp

(0)

)

0

: (B.2)

While, in the past, Faxens law has only been applied to the case where v refers to the

usual mass velocity eld v

m

; from a purely mathematical view Faxens law may be

equally well applied to the volume velocity eld v

v

; since the latter satises the

volumevelocity-based creeping ow equations (2.13) and (2.14) and the vector

velocity boundary condition that v

v

U = 0 on qV

s

: As discussed in Ref. [28], the

latter condition is applicable only to the case where the sphere is nonconducting.

To determine the undisturbed volume-velocity elds {v

(0)

v

; p

(0)

] existing in the

absence of the sphere, we note that since v

(0)

m

= 0; it follows from Eq. (1.5) that

v

(0)

v

= j

(0)

v

: However, from Eq. (1.6) we nd upon rearrangement that, as in Section 3,

j

(0)

v

= abVT = const: so that

v

(0)

v

= abVT = const : (B.3)

This undisturbed, pure uid, sphere-free, volume-velocity eld obviously satises Eq.

(2.13) since V

2

T = 0; while from Eq. (2.14) we nd that Vp

(0)

= 0: Thus, Eq. (B.2)

becomes

U = abVT ; (B.4)

in exact agreement with the more detailed result cited in Eq. (3.1) for the

nonconducting-sphere case, k

s

=k = 0:

B.1. Nonspherical particles

While we have demonstrated that Eq. (B.4) applies to the case of nonconducting

spherical particles, it is equally applicable to nonconducting particles of arbitrary

shape and orientation. This follows from the fact that the generalization [82] of

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 115

Eq. (B.1) for an arbitrarily shaped particle is F = M

1

.

[(v

(0)

U) O(a=L)]

0

; where

M is the particles mobility dyadic, a is a characteristic particle size, and L is a

characteristic length appearing in the normalization, V

+

= LV; of the dimensionless

gradient operator appearing explicitly in the undisturbed nonuniform ow v

(0)

; so

that the O(a=L) term represents a wall effect. Accordingly, the velocity of such a

force-free body is U = v

(0)

0

O(a=L): With use of Eq. (B.3), and in the absence of

wall effects, one thus recovers Eq. (B.4). Thus, remarkably (a fact more formally

demonstrated in Ref. [23]), irrespective of size, shape, and (in the latter nonspherical

case) orientation relative to the undisturbed temperature gradient VT; all

nonconducting particles will move at the same velocity. Accordingly, provided that

one interprets uid motion physically as being the (undisturbed) uids volume

velocity rather than its mass velocity, Eq. (B.4) expressed more generally as

U = (v

(0)

v

)

0

O(a=L) (B.5)

simply states that any passive (i.e., nonconducting) no-slip particle is simply

entrained in the owing uid. Alternatively, with use of (1.5) this may be written in

the form

U (v

(0)

m

)

0

= (j

(0)

v

)

0

O(a=L) ; (B.6)

a result which holds even when v

(0)

m

a0: The relative motion represented by the left-

hand side of the above then constitiutes the phoretic velocity of the insulated

particle, as in Eq. (6.4) with k

s

=k = 0; or in Eq. (7.1).

Appendix C. Fortuitously-correct thermal solutions based upon Maxwell slip

The energy equation (2.9) pre-constitutively incorporates both possible choices for

v; namely Eqs. (1.3) and (1.4). In the case where v

m

is chosen, it can be shown that for

both the unsteady-state thermophoretic [23] and steady-state thermal transpiration

[24] cases that, to leading order in the appropriate small parameter, a[Vln T[51;

asymptotically characterizing the heat-transfer process, the energy equation reduces

to the form rv

m

.

VT = kV

2

T: This same equation is obtained using v = v

m

; albeit

only on the proviso that the uid is supposed incompressible, so that V

.

v

m

= 0

(see below), as it done in the literature for the classical thermophoretic [35] and

thermal transpiration [8] analyses. Now, in circumstances where a prescribed

temperature gradient, quantied by a characteristic magnitude [VT[; is the only

mechanism animating the uid motion v

m

(as in the thermophoretic and thermal

transpiration cases to be discussed), it is found in the leading-order linear

approximation that v

m

= O(a[Vln T[): As such, to this degree of approximation

the convective term, v

m

.

VT; in the energy equation is of O([VT[

2

); whereas in this

same linear approximation the diffusive term, kV

2

T; is of O([VT[): Consequently,

when [VT[ is small, convection may be neglected compared with conduction. In such

circumstances, the energy equation reduces simply to V

2

T = 0; which is applicable to

both cases, v = v

m

and v = v

v

: Similar arguments apply with respect to the

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 116

convective/inertial and diffusive/viscous terms in the momentum equation, so that,

only the viscous term remains relevant.

The following table shows the resulting energy, momentum, and mass transport

equations describing both the Maxwell-based v

m

scheme, Eq. (1.3), and the modied

v

v

scheme, Eq. (1.4).

In the Maxwell scheme the mass transport or continuity equation is taken to be

V

.

v

m

= 0 despite the fact that the uid density is not constant as a consequence of

the fact that the equation of state is of the form r = r(T; p): The scheme based upon

v

v

correctly takes the continuity equation to be V

.

(rv

m

) = 0: It is, however,

unnecessary to explicitly employ the latter equation in the calculations. Rather, as

the third modied equation we instead use the accurate volume transport equation

[cf. Eq. (2.13)], V

.

v

v

= 0; expressing the uids quasi-incompressibility [27].

The trio of Maxwell equations appearing in Table 2 is to be solved for v

m

using

Maxwells slip boundary condition (5.2), whereas the modied equations are to be

solved for v

v

; using the no-slip boundary condition (5.1). These two velocities are

related by Eq. (1.5), in which the required diffusional volume current j

v

; Eq. (1.6), is

given explicitly for the present heat-transfer case by Eq. (5.9). As such, as a

consequence of the fact that V

2

T = 0; it follows from the latter relation that V

.

j

v

=

0 and V

2

j

v

= 0: Accordingly, from Eq. (1.5) we nd that to the order of the present

approximation, V

.

v

m

= V

.

v

v

= 0 and V

2

v

m

= V

2

v

v

: Comparison of the latter

expression with that in Table 2, leads to the surprising conclusion that both the

Maxwell and modied schemes are each governed by exactly the same generic

equations, namely V

2

T = 0; V

.

v = 0; and Vp = mV

2

v: Nevertheless, their respective

solutions will not coincide, as each is to be solved subject to different boundary

conditions on qV

s

; namely I

s

.

(v

v

U) = 0 in the modied v

v

case and I

s

.

(v

m

U) =

C

s

vV

s

ln T in the Maxwell v

m

case, all other boundary conditions [such as the

impenetrability condition (1.8)] being the same for both. Note that despite the

velocities being different in the two cases, the respective pressure gradients Vp will

each be the same owing to the fact that V

2

v

m

= V

2

v

v

[147].

The calculation of some overall force F usually constitutes the main item of

interest in connection with the class of problems under discussion, either the force on

a thermophoretic particle [23] or the force on the walls of the capillary tube in the

thermal transpiration problem [24], each for the case of a prescribed temperature

difference at the two ends of the system conning the uid. The force on an

impermeable solid surface can be calculated from the expression F =

_

qV

s

dS

.

P;

with the pressure tensor given by Eq. (2.1

2

) in conjunction with (1.1). Since, as we

ARTICLE IN PRESS

Table 2

Energy, momentum, and continuity equations

Maxwell scheme, v = v

m

Modied scheme, v = v

v

Energy equation

V

2

T = 0 V

2

T = 0

Momentum equation

0 = Vp mV

2

v

m

0 = Vp mV

2

v

v

Continuity equation V

.

v

m

= 0 V

.

v

v

= 0

H. Brenner / Physica A 349 (2005) 60132 117

have indicated, the calculated pressure p will be the same for both the Maxwell and

modied schemes, one can form the difference, F

v

F

m

=

_

qV

s

dS

.

(T

v

T

m

);

between the respective forces. In view of Eq. (1.1) we nd upon using Eq. (1.5)

together with the relation V

.

j

v

= 0 that F

v

F

m

= 2m

_

qV

s

dS

.

Vj

v

: In conjunc-

tion with Eq. (5.9) considered jointly with the constancy of the multiplier of VT;

this yields

F

v

F

m

=

2mk

^ c

p

q^ v

qT

_ _

p

_

qV

s

dS

.

VVT :

The surface integral appearing in the latter relation can be converted into a volume

integral, and the relation V

2

T = 0 employed in the resulting expression to conclude

that F

v

= F

m

: This shows, at least for the present class of gaseous thermal problems,

that the Maxwell scheme does, in fact, furnish the same overall global results as the

modied scheme, despite the inconsistency of the set of Maxwell equations based

upon the constitutive relation, v = v

m

: However, such agreement, rather than

embodying some fundamental principle, is seen to be merely fortuitous, being limited

to a very special set of circumstances. More general circumstances, wherein, for

example, nonlinear terms are retained in the calculations, would almost certainly

point up a difference between the two. Note also that in this limited class of

problems, not only will the global forces be the same for both schemes, but so too

will be the respective local pressures p; densities r; temperatures T; and mass

velocities v

m

: As such, it is perhaps not surprising that the true, no-slip, nature of the

Maxwell slip condition has gone undiscovered for so long.

Appendix D. First-law violation occasioned by Maxwell slip in rigid, uid-lled,

immobile containers

Following up the closing remarks of Section 5, we demonstrate here that the

Maxwell slip condition (5.2) imposed upon v

m

violates the First law of

thermodynamics when used in conjunction with the following (single-component)

standard incompressible creeping ow equations used in the literature [8,35] to

analyze phoretic phenomena:

V

.

v

m

= 0 ; (D.1)

V

.

P

m

= 0; P

m

= Ip T

m

; (D.2)

T

m

= m[Vv

m

(Vv

m

)

T

] : (D.3)

According to the First law, the temporal rate at which the energy E (internal plus

kinetic) of a closed system increases is given by the expression dE=dt =

_

Q

_

W;

where

_

Q =

_

qV

s

dS

.

q is the rate of heat ow into the system and

_

W is the rate at

which the surroundings are doing work on the system. Here, qV

s

denotes the rigid,

solid, impermeable, and immobile boundaries of the apparatus conning the uid

within its interior.

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 118

Based upon the above constitutive form (D:2

2

) for the pressure tensor P; the rate

of working is thus given in present circumstances by the expression

_

W =

_

qV

s

dS

.

P

m

.

v

m

(D.4)

for the case where the boundaries are immobile, so U = 0 in Eqs. (1.7) (1.3) and

(1.8). For deniteness we suppose that the container, within which some transient

heat transfer process is occurring, is suddenly insulated at time t = 0; so that

_

Q = 0

for all subsequent times t40: As no mechanism exists by which work can be

performed by the surroundings on the contents of the uid-lled container V

s

whose

immobile boundaries are qV

s

; this requires that

_

W = 0 (\t40) : (D.5)

This condition is consistent with the fact that the total energy E; internal plus

kinetic, of the isolated system will necessarily remain xed for all time follow-

ing placement of the insulation on the boundaries. As such, when the tran-

sients have decayed the uid will eventually attain a homogeneous equilibrium

state in which the pressure, temperature and density are each uniform throughout

the uid.

Under conventional non-Maxwellian no-slip conditions, one would have that

v

m

= 0 on qV

s

; whence Eq. (D.5) would be satised automatically irrespective

of the constitutive form of the stress tensor appearing in (D.4). However, in the

presence of initial temperature gradients imposed along qV

s

; the Maxwell slip

condition (5.2) generally obviates the possibility that v

m

= 0 on qV

s

; since the

integral (D.4) will not generally vanish owing to the generally nonzero tangential

mass velocity component, I

s

.

v

m

a0: As a consequence, in contrast with the classical

case (1.3) where v = v

m

; the velocity boundary condition alone no longer

automatically assures satisfaction of (D.5). It is possible, however, that the integral

may nevertheless vanish in some integral or other sense. To explore this possibility,

we convert (D.4) into a volume integral and use (D.2) in conjunction with (D.1)

to obtain

_

W =

_

V

s

2mVv

m

: Vv

m

dV : (D.6)

Obviously, the nonnegative nature of the above integrand at each point of the uid

precludes the possibility of Eq. (D.5) being satised. This demonstrates the

thermodynamic inconsistency of the set of mass-based velocity equations

(D.1)(D.3) when used in conjunction with the Maxwell slip condition (5.2). Viewed

alternatively, insistence upon the applicability of this equation set together with (5.2)

would violate the rst law of thermodynamics.

The escape from this dilemma involves replacing the set of equations (D.1)(D.3)

by our more physically appropriate set, namely with v

m

throughout replaced by v

v

[see Eqs. (2.13)(2.14) and (1.1), in which v = v

v

]. Thus, in place of (D.4), one would

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 119

now write

_

W =

_

qV

s

dS

.

P

v

.

v

m

; (D.7)

wherein

P

v

= Ip T

v

; T

v

= m[Vv

v

(Vv

v

)

T

] : (D.8)

It is conrmed in what follows that the state of motion of the conned uid is

correctly described by the fact that v

v

= 0 and p = const throughout the uid and

for all t40: This proposed solution, for which T

v

= 0 everywhere, clearly satises

Eqs. (2.14) and (2.13) as well as the no-slip boundary condition (5.1). Moreover, the

condition that the container be insulated requires that n

.

VT = 0 on qV

s

; from which

it follows from Eq. (5.9) that n

.

j

v

= 0 on qV

s

: In turn, from Eq. (1.5) this yields

n

.

v

v

= n

.

v

m

; thus assuring that the no-penetration condition (1.8) is satised. In

turn, it follows that dS

.

P

v

= 0 at each point on qV

s

: Satisfaction of Eq. (D.5) is thus

assured despite the slip of v

m

along qV

s

:

To complete the problem, it remains to demonstrate that the proposed solution,

v

v

= 0; is consistent with the continuity equation (1.2) and the energy equation

(2.11). In the course of the demonstration, we use these equations to determine the

remaining elds: r; T and v

m

: Consider rst the density eld. Substitution of (1.5)

and (1.6) together with use of v

v

= 0 yields

v

m

=

k

^ c

p

r

2

Vr : (D.9)

Introduction of the latter into the continuity equation (1.2) furnishes the following

equation governing the density eld r(x; t):

qr

qt

=

k

^ c

p

V

2

ln r : (D.10)

The insulation boundary condition n

.

VT = 0 on qV

s

together with the uids

equation of state furnishes the boundary condition n

.

Vr = 0 on qV

s

imposed upon

r: This same condition arises from the impermeability of the boundary, n

.

v

m

= 0 on

qV

s

; considered in conjunction with Eq. (D.9). The initial condition r(x; 0) imposed

upon r is obtained from the uids (assumed pressure-independent) equation of state

r = r(T) together with knowledge of the initial temperature distribution, T(x; 0)

within the uid. Solution of Eq. (D.10) subject to these boundary and initial

conditions serves to determine r(x; t): In turn, such knowledge immediately furnishes

v

m

(x; t) from Eq. (D.9), and T(x; t) from the uids equation of state, thereby

demonstrating the validity of the assumed vanishing volume velocity condition, v

v

=

0: As an aside, it should be noted that this latter condition is consistent with the

speculations of Onsager [114] and Haase [15,115], cited in Section 7, albeit in

connection with their isothermal binary diffusion problems rather than our present

similarly-structured single-component heat transfer problem.

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 120

Appendix E. Mathematical analogy between electrophoretic and thermophoretic

motions

Upon identifying the pair of electrophoretic elds (v

f

; j

f

); dened below, with their

thermophoretic analogs (v

v

; j

v

); dened earlier in Eqs. (1.5) and (1.6), a complete

mathematical analogy will be seen to exist between steady-state electrophoretic and

thermophoretic particle motions in liquids for the respective nonconducting particle

cases, at least in the Debye thin double-layer limit. Explicitly, dene the following

electrophoretic quantities:

v

f

:=v

m

j

f

where j

f

:= M

f

Vf ; (E.1)

in which M

f

:=z=m is the electrophoretic mobility. Inasmuch as V

2

f = 0 outside of

the Debye layer it follows that

V

.

j

f

= 0 and V

2

j

f

= 0 : (E.2)

Equations (E.1) and (E.2) represent the analogs of the corresponding thermophoretic

quantities,

v

v

:=v

m

j

v

where j

v

:= M

v

VT ; (E.3)

in which M

v

:=ab: Since V

2

T = 0 in the nonconducting thermophoretic case (see

Table 2) it follows that

V

.

j

v

= 0 and V

2

j

v

= 0 : (E.4)

Owing to the respective analogs, Eqs. (E.2) and (E.4), one has for the respective

choices of f or v; both denoted below by the common symbol g; that

V

.

v

m

= V

.

v

g

= 0 and V

2

v

m

= V

2

v

g

= 0 : (E.5)

Both the electrophoretic boundary-value problem outlined in Section 8 (with the

subscript f implicitly appearing therein replaced throughout by g) and the

nonconducting thermophoretic boundary value problem outlined in Section 3 (with

the subscript v replaced therein by g) satisfy exactly the same set of equations:

Vp = mV

2

v

g

; V

.

v

g

= 0; V

.

j

g

= 0; v

g

= v

m

j

g

; (E.6)

and boundary conditions

n

.

j

g

= 0 on qV

s

; v

m

U = j

g

on qV

s

; v

g

j

(0)

g

=M

g

as [x[ o ; (E.7)

where j

(0)

g

= const refers to the undisturbed uniform value at innity.

The two classes of problems are thus seen to be mathematically identical, which is

why both lead to the same size-, shape-, and orientation-independent result for the

velocity of the respective phoretic particles, namely

U = j

(0)

g

M

f

Vf

(0)

;

M

v

VT

(0)

;

_

(E.8)

in the electrophoretic and thermophoretic cases. This analogy obtains despite the

very different physics underlying the sources of the respective particle motionsone

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 121

animated by externally-imposed electrical body forces, the other by an externally

imposed temperature gradient in the absence of body forces! [148].

While we have pointed out the analogy only for the elementary case of an isolated

particle in an effectively unbounded uid, the analogy can be shown to persist

irrespective of the presence of other (nonconducting) boundaries as, for example, in

cases where a plane wall or a circular cylinder bounds the particle-containing uid

externally. Existing solutions of the electrophoretic problems posed for such

congurations [149] thereby automatically provide solutions for their thermophore-

tic counterparts.

References

[1] G.G. Stokes, Trans. Cambridge Philos. Soc. 8 (1845) 287 (see also Mathematical and Physical

Papers, vol. 1, Cambridge University Press, Cambridge, 1901, p. 75).

[2] An account of pre-1845 work by others on the NavierStokes equations can be found in G.G.

Stokes, Report on recent researches in hydrodynamics, British Assoc. Advance. Sci., 1846, pp. 120.

Reprinted in Mathematical and Physical Papers, vol. 1, Cambridge University Press, Cambridge,

1901, p. 157. A concise history of the conceptual foundations of uid mechanics from the time of

Newtons Principia in 1687 up to the denitive work of Stokes in 1845, can be found in the following

articles: C. Truesdell, Am. Math. Monthly 60 (1953) 445;

O. Darrigol, Arch. Hist. Exact Sci. 56 (2002) 95.

[3] Here and throughout, a question mark surmounting an equality sign serves to suggest that the stated

equality is, at this point in the manuscript, an as yet unresolved issue, one which will, however, later

be resolved against the equality!.

[4] H. Brenner, Kinematics of volume transport, Physica A (2005), in press [doi:10.1016/

j.physa.2004.10.033].

[5] The volume velocity v

v

is, in fact, identical with the volume ux density or volume current n

v

[4],

dened such that with dS a directed element of surface area xed in space, the scalar dS

.

n

v

gives the

volume owing across dS per unit time. This is the analog of the fact that with dS

.

n

m

the ux of

mass across dS; in which n

m

is the mass current, the mass velocity, v

m

:=n

m

=r; represents the

convective portion of the volume ux and j

v

the diffusive portion.

[6] S. Chapman, T.G. Cowling, The Mathematical Theory of Non-Uniform Gases, third ed.,

Cambridge University Press, Cambridge, 1970.

[7] D. Burnett, Proc. London Math. Soc. 39 (1935) 385;

D. Burnett, Proc. London Math. Soc. 40 (1936) 382.

[8] J.C. Maxwell, Philos. Trans. Roy. Soc. (London) A 170 (1879) 231. Reprinted in: W.D. Niven (Ed.),

The Scientic Papers of James Clerk Maxwell, vol. 2, Cambridge University Press, Cambridge, 1890,

p. 681.

[9] R.J. Adrian, Ann. Rev. Fluid Mech. 23 (1991) 261;

R.J. Goldstein (Ed.), Fluid Mechanics Measurements, second ed., Taylor & Francis, Washington

DC, 1996;

Th. Dracos, Three-Dimensional Velocity and Vorticity Measuring and Image Analysis Techniques,

Kluwer, Dordrecht, 1996;

F.T.M. Nieuwstadt (Ed.), Flow visualization and image analysis, Fluid Mechanics and its

Application, vol. 14, Kluwer, Dordrecht, 1992;

M. Raffel, C. Willert, J. Kompenhans, Particle Image Velocimetry. A Practical Guide, Springer,

New York, 1998;

M. Stanislas, J. Kompenhans, J. Westerweel (Eds.), Particle Image Velocimetry, Kluwer, Dordrecht,

2000.

[10] Presumably, v

m

can be independently measured experimentally at a point of the uid by some

colorimetric method, involving the addition of dye to the uid or, even better, instead of adding a

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 122

foreign coloring agent (and thereby obfuscating the notion of a single-component uid) by

performing an optical experiment with a single-component uid whose molecules are photochromic

or uorescent. These latter techniques involve so-called molecular tagging velocimetry (MTV)

[11], as opposed to particle-image velocimetry (PIV) [9], which involves monitoring tracer

particles, namely foreign objects deliberately introduced into the uid.

[11] K.G. Roesner, Mol. Cryst. Liq. Cryst. 298 (1997) 243;

C.P. Gendrich, M.M. Koochesfahani, D.G. Nocera, Exp. Fluids 23 (1997) 361;

W.R. Lempert, in: A.J. Smits, T.T. Lim (Eds.), Flow Visualization: Techniques and Examples,

Imperial College Press, London, 2000;

P. Mavros, Trans. Inst. Chem. Eng. 79 (2001) 113;

S.J. Muller, Korea-Australia Rheol. J. 14 (2002) 93.

[12] I. Mu ller, T. Ruggeri, Extended Thermodynamics, Springer, New York, 1993;

K. Wilmanski, Thermomechanics of Continua, Springer, Berlin, 1998.

[13] S.R. de Groot, P. Mazur, Non-Equilibrium Thermodynamics, North-Holland, Amsterdam, 1962.

[14] D.D. Fitts, Nonequilibrium Thermodynamics, McGraw-Hill, New York, 1962.

[15] R. Haase, Thermodynamics of Irreversible Processes, Dover reprint, New York, 1990.

[16] G.D.C. Kuiken, Thermodynamics of Irreversible Processes: Applications to Diffusion and

Rheology, Wiley, New York, 1994.

[17] L. Onsager, Phys. Rev. 37 (1931) 405;

L. Onsager, Phys. Rev. 38 (1931) 2265;

H.B.G. Casimir, Rev. Mod. Phys. 17 (1945) 343;

I. Prigogine, Introduction to Thermodynamics of Irreversible Processes, second ed., Interscience,

New York, 1961.

[18] R.B. Bird, W.E. Stewart, E.N. Lightfoot, Transport Phenomena, second ed., Wiley, New York,

2002.

[19] With the apparent exception of a few authors (see, for example, Refs. [20]) it has not been clearly

recognized in the literature that a need exists for a formal proof that the specic momentum, say ^ m;

of a uid is equal to its mass velocity v

m

: Rather, as judged by accounts found in uid mechanics

textbooks, which implicitly assume it a priori without discussion, the constitutive relation in ^ m = v

m

is regarded as an identity.

[20] L.D. Landau, E.M. Lifshitz, Fluid Mechanics, second ed., Butterworth-Heinemann, Oxford, 1987,

p. 196;

P. Kosta dt, M. Liu, Phys. Rev. E 58 (1998) 5535.

[21] J.R. Bielenberg, H. Brenner, Continuum thermodynamics in the presence of the diffusive transport

of volume, Contin. Thermo. Mech., 2005, to be submitted.

[22] J.G. Kirkwood, I. Oppenheim, Chemical Thermodynamics, McGraw-Hill, New York, 1961.

[23] H. Brenner, J.R. Bielenberg, A continuum theory of phoretic phenomena: thermophoresis, Physica

A (2004) submitted.

[24] J.R. Bielenberg, H. Brenner, A continuum model of thermal transpiration, J. Fluid Mech., 2004,

submitted.

[25] J.R. Bielenberg, H. Brenner, A continuum theory of phoretic phenomena: diffusiophoresis, Phys.

Fluids, 2004, submitted.

[26] Indeed, at the hands of D.D. Joseph, his co-workers, and others (see Ref. [127] as well as the

extensive references cited in Ref. [4]), Eq. (2.13) is often used in applications to compressible uids,

at least in the case of isothermal binary diffusion problems, where our single-component

adiabatically additive volume law based on (q^ v=qT)

p

is replaced by its better known (cf. [4])

multicomponent species additive volume law counterpart based on (q^ v=qw

i

)

p;T

; where w

i

is the mass

fraction of species i: In the latter context, Eq. (2.13) is referred to as expressing a condition of quasi-

incompressibility [27] in circumstances where r is not constant throughout the uid.

[27] J. Lowengrub, L. Truskinovsky, Proc. Roy. Soc. (London) A 454 (1998) 2617.

[28] This elementary equivalence is true only in circumstances where the no-penetration boundary

condition (1.8) imposed upon v

m

at solid surfaces can be replaced by a comparable condition

imposed upon v

v

; for in such circumstances Eq. (1.7), in conjunction with the latter condition, then

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 123

leads to the single vector velocity boundary condition, v

v

= 0 on qV

s

: This no-penetration

equivalency will obviously obtain in circumstances where n

.

(v

m

v

v

) = 0 on qV

s

: Equivalently,

from Eq. (1.5) this necessitates that n

.

j

v

= 0 on qV

s

: From (1.6), this latter condition will prevail

whenever n

.

Vr = 0 on qV

s

or, equivalently, when n

.

V^ v = 0 on qV

s

: In the present single-

component case, and for the case where the law of adiabatically additive volumes prevails, this

requires that n

.

VT = 0 on qV

s

and, hence, from Eq. (2.5) that n

.

q = 0 on qV

s

: In turn, from

Eq. (2.7) this is equivalent to the condition that n

.

j

u

= 0 on qV

s

; which, because it is also true that in

these same circumstances that n

.

j

v

= 0 on qV

s

; leads to the observation that in such circumstances it

is immaterial whether j

u

is given constitutively by the classic expression (2.4) or by its nontraditional

counterpart (2.6). In summary, the complete vector velocity boundary condition, v

v

= 0 on qV

s

; will

obtain whenever no diffusive transport of internal energy occurs across the solid-uid interface,

corresponding to the insulation boundary condition, n

.

j

u

= 0 on qV

s

: For nonconducting cases,

Eqs. (2.13) and (2.14) together with the boundary conditions (1.7) and (1.8) are indistinguishable

from those governing v

m

in the classical creeping ow case.

[29] With regard to use of the term phoretic forces to describe particle motion in the presence of

gradients, Anderson [30] has inadvertantly sowed some degree confusion owing to his use of terms

like thermophoresis and diffusiophoresis, normally reserved for gases [2325], to describe

phenomena that are actually driven by surface-gradient forces in liquids [31,32], see also [132].

The latter category is typied by Marangoni forces resulting from interfacial tension gradient V

s

g;

caused by a surface temperature gradient V

s

T along the particle surface, owing to the functional

dependence of interfacial tension g upon T: The resulting Marangoni surface stress causes the

particle to move against the temperature gradient. However, the forces associated therewith give rise

to a particle velocity U generally dependent upon the size of the particle [32], whereas in non-

Brownian thermophoretic experiments [23] U is observed to be independent of particle size, ruling

out Marangoni forces as possibly responsible for the observed, size-independent, thermophoretic

movement.

[30] J.L. Anderson, Ann. Rev. Fluid Mech. 21 (1989) 61.

[31] D.A. Edwards, H. Brenner, D.T. Wasan, Interfacial Transport Processes and Rheology,

Butterworth-Heinemann, Boston, 1991.

[32] E. Ruckenstein, J. Colloid Interf. Sci. 83 (1981) 77;

T. Keyes, J. Stat. Phys. 33 (1983) 287;

V.G. Levich, V.S. Krylov, Ann. Rev. Fluid Mech. 1 (1969) 293.

[33] This occurred when Tyndall observed dust-free regions in proximity to heated surfaces and wires in a

chamber lled with dust-laden air; J. Tyndall, Proc. R. Inst. 6 (1870) 1. (For further historical

references, see Ref. [34]).

[34] F. Zheng, Adv. Colloid Interf. Sci. 97 (2002) 255.

[35] P.S. Epstein, Z. Phys. 54 (1929) 537.

[36] J.R. Brock, J. Colloid Sci. 17 (1962) 768;

G.M. Hidy, J.R. Brock, The Dynamics of Aerocolloidal Systems, Pergamon Press, Oxford,

1970.

[37] L. Waldmann, K.H. Schmitt, Thermophoresis and diffusiophoresis of aerosols, in: C.N. Davies

(Ed.), Aerosol Science, Academic Press, London, 1966, p. 137.

[38] B.V. Derjaguin, Yu.I. Yalamov, J. Colloid Sci. 20 (1965) 555;

B.V. Derjaguin, A.I. Storozhilova, Ya.I. Rabinovich, J. Colloid Interf. Sci. 21 (1966) 35;

B.V. Derjaguin, Yu.I. Yalamov, The theory of thermophoresis and diffusiophoresis of aerosol

particles and their experimental testing, in: G.M. Hidy, J.R. Brock (Eds.), Topics in Current Aerosol

Research, Pergamon Press, Oxford, 1972, p. 2;

B.V. Derjaguin, Ya.I. Rabinovich, A.I. Storozhilova, G.I. Shcherbina, J. Colloid Interf. Sci. 57

(1976) 451.

[39] L. Talbot, R.K. Cheng, R.W. Schefer, D.R. Willis, J. Fluid Mech. 101 (1980) 737;

L. Talbot, Thermophoresisa review, in: S.S. Fisher (Ed.), Rareed Gas Dynamics, Part 1, AIAA,

New York, 1981, p. 467.

[40] W. Oostra, J.C.M. Marijnissen, B. Scarlett, Space Forum 3 (1998) 251.

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H. Brenner / Physica A 349 (2005) 60132 124

[41] Knudsens work on noncontinuum effects in thermal transpiration ows did not even appear

until 1910 [42], whence it is unlikely that the concept of noncontinuum behavior would

have even arisen in Maxwells mind in 1879. [Indeed, the fact that Maxwell applied his slip

condition to the strictly continuum NSF equations supports our belief that he regarded

his so-called slip condition to be a continuum effect arising from the surface temperature gra-

dient. In this context it is noteworthy that the adherence of the uid to a solid surfaceso

widely accepted today in the case of continua, irrespective of whether or not the surface is

isothermalwould, in the case of nonisothermal continua, not likely to have been regarded as

sacrosanct during Maxwells era. After all, very little data pertinent to the issue existed at that

time.] Concomitantly, the standard explanation found in textbooks [43] to the effect that

the thermophoretic particle motion observed in gases is molecular (i.e., noncontinuum) in

origin, arising from more energetic particles striking the hotter side of the particle and overcom-

ing the opposing effects of the less energetic particles on the colder side, is untenable in the

continuum limit.

[42] M. Knudsen, Ann. Phys. (Leipzig) 31 (1910) 205;

M. Knudsen, Ann. Phys. (Leipzig) 33 (1910) 1435.

[43] E.H. Kennard, Kinetic Theory of Gases, McGraw-Hill, New York, 1938;

L.B. Loeb, The Kinetic Theory of Gases, Dover reprint, New York, 1961. For a discussion of

Maxwells role in explaining Crookess radiometer, see Ref. [44].

[44] S.G. Brush, The Kind of Motion that we call Heat, North-Holland, Amsterdam, 1976.

[45] G.S. McNab, A. Meisen, J. Colloid Interf. Sci. 44 (1973) 339.

[46] Others [32] have suggested that phoretic motion in liquids may actually be due to Marangoni-like

surface effects [31], wherein the surface is not passive, as in our model, but rather interacts

physicochemically with the uid. However, as discussed in Section 8 such particle motion requires

the action of body forces, which are absent as the animating mechanism underlying Eq. (3.1) for

liquids and (3.4) for gases.

[47] S. Semenov, M. Schimpf, Phys. Rev. E 69 (2004) 011201.

[48] J.R. Bielenberg, H. Brenner, A hydrodynamic/Brownian motion model of thermal diffusion in

liquids, Phys. Rev. E (2004), to be submitted.

[49] The absence of bulk viscosity effects in (4.1) derives from the fact that the volume velocity appearing

in Eq. (1.1) is assumed to obey Eq. (2.13), a conclusion consistent with the choice of the constitutive

equation (1.6) and valid, for example, in the case of ideal gases.

[50] To describe these as being the noncontinuum terms, without including the rst-order near-

continuum O(Kn) NSF terms in the appellation, is surely confusing, certainly to uid

mechanicians who regard the O(Kn) NSF terms, and not the O(Kn

0

) Euler terms, as the

equations of continuum uid mechanics; that is, owing to their apparent Knudsen number

dependence, the latter classical near-continuum rst-order NSF terms should, for consistency,

also be classied as noncontinuum terms, despite their being regarded by uid mechanicians as

strictly continuum-level terms.

[51] Even higher-order, O(Kn

3

); so-called super-Burnett terms [52] exist. For a contextual evaluation of

the Burnett, super-Burnett, and generally higher-order contributions to the linear momentum

equation, see Ref. [53].

[52] A.V. Bobylev, Sov. Phys. Doklady 27 (1982) 29;

F.J. Uribe, R.M. Velasco, L.S. Garcia-Colin, Phys. Rev. E 62 (2000) 5835;

M. Slemrod, Arch. Rational Mech. Anal. 150 (1999) 1.

[53] R.K. Agarwal, K.Y. Yun, R. Balakrishnan, Phys. Fluids 13 (2001) 3061.

[54] The comparable Burnett terms for the heat ux do not impact upon whether or not Eq. (2.6) is or is

not correct, since gas kinetic theory [6] draws no clear-cut distinction between the heat ux q and the

diffuse internal energy current j

u

:

[55] M.N. Kogan, V.S. Galkin, O.G. Fridlander, Sov. Phys. Usp. 19 (1976) 420;

M.N. Kogan, Ann. Rev. Fluid Mech. 5 (1973) 383;

M.N. Kogan, Progr. Aerospace Sci. 29 (1992) 271.

[56] A.V. Bobylev, J. Stat. Phys. 80 (1995) 1063.

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H. Brenner / Physica A 349 (2005) 60132 125

[57] E. Yariv. H. Brenner, A continuum alternative to the ghost effect of gas-kinetic theory, Phys.

Fluids, 2004, submitted.

[58] C. Truesdell, R.G. Muncaster, Fundamentals of Maxwells Kinetic Theory of a Simple Monatomic

Gas, Academic Press, New York, 1980.

[59] Although not required for the subsequent calculations, as an aside we note that m = (const:) T [6] for

Maxwell molecules, from which it follows that K

2

= 3 for such molecules.

[60] In the latter context, note that Eq. (4.8) is consistent with the fact that k is known [6] to be identically

zero for monatomic ideal gases owing to the assumed spherically symmetric nature of such

molecules.

[61] A.D. Kovalenko, Thermoelasticity, Wolters-Noordhoff, Groningen, 1969;

H. Parkus, Thermoelasticity, Springer, Wien, New York, 1976;

D. lesan, A. Scalia, Thermoelastic Deformations, Kluwer, Dordrecht, 1996;

G.A. Maugin, A. Berezovski, J. Thermal Stresses 22 (1999) 421;

N. Noda, R.B. Hetnarski, Y. Tanigawa, Thermal Streses, Taylor and Francis, London, 2002.

[62] Indeed, in the case of solids, the notion of a noncontinuum solid does not even appear to exist,

except perhaps in the case of granular materials, although fractures and dislocations, representing

isolated singularities, may exist within the solid.

[63] D.J. Korteweg, Arch. Ne erl. Sci. Exactes Naturelles II 6 (1901) 1.

[64] C. Cercignani, Mathematical Methods in Kinetic Theory, second ed., Plenum Press, New York,

1990.

[65] H.A. Kramers, J. Kistemaker, Physica 10 (1943) 699.

[66] D.A. Noever, Phys. Fluids A 2 (1990) 858;

D.A. Noever, Phys. Lett. A 144 (1990) 253;

D.A. Noever, Phys. Rev. Lett. 65 (1990) 1587;

D.A. Noever, Phys. Rev. A 45 (1992) 7302.

[67] W. Crookes, Philos. Trans. Roy. Soc. (London) 166 (1876) 325.

[68] A detailed and historical discussion of attempts to explain the principles underlying the windmill-like

rotation undergone by the rotor in Crookess radiometer based upon noncontinuum concepts is

given in Ref. [44].

[69] J.C. Maxwell, Philos. Mag. 19 (1860) 19;

J.C. Maxwell, Philos. Mag. 20 (1860) 21.

[70] Some of the historical context, chronology, and acrimony in the matter of priority surrounding the

competition between Maxwell and Osborne Reynolds [71] to use their respective thermal

transpiration models to explain the physical mechanism underlying the working of Crookess

radiometer [67] can be found in the biography by I. Tolstoy, James Clerk Maxwell, University of

Chicago Press, Chicago, 1981, pp. 150151, 166167; see also Ref. [44].

[71] O. Reynolds, Proc. Roy. Soc. London 38 (18791880) 300. This paper is only a preliminary abstract

of the lengthier paper published some time afterwards as O. Reynolds, Philos. Trans. Roy. Soc.

(London) 170 (1879) 727.

[72] The importance of understanding the mechanism behind Crookess radiometer [67] played a vital,

and under-appreciated, role in the history of gas-kinetic theory, in particular in regard to the

boundary conditions to be applied to the Boltzmann equation at solid surfaces. After all, an

important part of the verication of the validity of the Boltzmann equation necessarily lies in the

agreement of its predictions with experiment, for which circumstances the solution of boundary-

value problems (either imposed upon the Boltzmann equation itself or upon the coarser-scale

transport equations derived therefrom, such as the NSF equations) plays a pre-eminent role.

[73] For a modem version of the slip boundary condition involving G for gases, see F. Sharpov,

D. Kalempa, Phys. Fluids 15 (2003) 1800.

[74] Given the interpretation of Maxwell slip as a noncontinuum O(Kn

2

) effect owing to its origin in

connection with the Burnett terms, Epstein [35] and those who followed should, for mathematical

consistency as regards the hierarchical ordering of the Knudsen number terms appearing in their

transport equations, have then solved the corresponding noncontinuum O(Kn

2

)-level transport

equations, rather than the near-continuum O(Kn) NSF equations. At a minimum, this would have

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H. Brenner / Physica A 349 (2005) 60132 126

resulted in adding the Maxwell thermal stress term (5.3) to the O(Kn) viscous Newtonian term (4.2)

appearing in the momentum equation. Additionally, because the gas is compressible owing to its

density varying with temperature, the continuity equation used by Epstein, namely V

.

v

m

= 0; is

valid only to O(Kn): At O(Kn

2

) another term should have appeared in his continuity equation in

order that the latter be correct. However, as discussed in Appendix C, owing to a fortuitous

combination of circumstances in the present class of phoretic thermal problems [23,24], these

additions do not affect the calculation of U:

[75] As discussed in connection with Eqs. (5.4) and (5.5), the notion of noncontinuum slip is associated

with the parameter G appearing therein, rather than with the last term of Eq. (5.4), which alone

governs Maxwells slip coefcient, C

s

: In the literature [73], G is associated with the notion of

velocity slip, a truly noncontinuum phenomenon occurring even in isothermal uids.

[76] L. Euler, Me m. Acad. Sci. Berlin 11 (1755) 274. Reproduced in: Leonhardi Euleri Opera Omnia.

Series II, vol. 12, Fu ssli, Zu rich, 1954, p. 54. Additional historical information can be found in the

Editors Introduction to the latter volume by C. Truesdell, Rational uid mechanics, 16871765,

pp. VIICXXV; see also L. Euler, Hist. Acad. Berlin 1755 (1757) 316361.

[77] G.K. Batchelor, An Introduction to Fluid Dynamics, Cambridge University Press, Cambridge,

1967.

[78] By small is meant the following: If a is the maximum linear dimension of the particle, it is required

that a[[Vv

l

[[=[v

l

[51; with the modulus bars denoting appropriate norms.

[79] C.C. Truesdell, R.A. Toupin, The classical eld theories, in: S. Flu gge (Ed.), Handbuch der Physik,

vol. IIII/1, Principles of Classical Mechanics and Field Theory, Springer, Berlin, 1960, p. 226;

C. Truesdell, W. Noll, The Nonlinear Field Theories of Mechanics, in: S. Flu gge (Ed.), Handbuch

der Physik, vol. III/3, Springer, Berlin, 1965;

W. Noll, R.A. Toupin, C.C. Wang, Continuum Theory of Inhomogeneities in Simple Bodies,

Springer, Berlin, 1968.

[80] Of course, in the case of unsteady ows, the necessity of performing repetitive experiments with

different size particles, all at the same instant of time, would, no doubt, pose a daunting challenge to

the experimentalist!.

[81] A perhaps equally remarkable fact about Eq. (3.2), applicable to gases, is that it reveals a totally

counter-intuitive uid-mechanical phenomenonnamely, the larger the viscosity of the gas the

faster does the particle move! This fact alone signals the extraordinarily unique nature of

thermophoretic motion, since viscosity generally retards rather than enhances relative particle

motion through uids, a fact well known to every low Reynolds number uid mechanician [82].

[82] J. Happel, H. Brenner, Low Reynolds Number Hydrodynamics, Prentice-Hall, Englewood Cliffs,

NJ, 1965.

[83] P. Goldsmith, F.G. May, Diffusiophoresis and thermophoresis in water vapour systems, in: C.N.

Davies (Ed.), Aerosol Science, Academic Press, London, 1966, p. 163 (see also Ref. [38]).

[84] In order for an investigator be able to objectively identify his velocity measurements as

representative of those of the uid itself, and not an artifact of the properties of the tracer

particle, he needs to assure himself that his experimental tracer particles do not possess any

physical attributes that, in the zero-size limit, would distinguish the particles velocity from

that of the uid itself. It was in order to fulll this requirement of passivity that only

(effectively) thermally insulated thermophoretic spheres were selected by us in order to identify

the velocity v

l

of the undisturbed uid. As revealed by Eq. (3.1), thermophoretically

animated spheres possessing a nonzero k

s

=k ratio move with a velocity that depends

signicantly upon the magnitude of this conductivity ratio, even in the limit of effectively

zero size. As such, (effectively) noninsulated particles may not serve as uid velocity tracers.

It is only to this extent that the experimental uid mechanician, in deciding upon the choice

of appropriate tracer particles with which to conduct his velocity experiments, would have

to contemplate the possible complicating effects of temperature gradients. Even were

he insufciently insightful to recognize a priori the need for insulated particles, were he to

next perform a sequence of replicate size-varying experiments using a series of particles

possessing different thermal conductivities (just as he might do with a series of particles of

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H. Brenner / Physica A 349 (2005) 60132 127

different densities, so as to assure himself of their zero-size passivity), he would presumably

soon come to recognize that all low conductivity particles yielded identical extrapolated zero-size

velocities. Accordingly, he would presumably then reject all zero-size particle data obtained with

his high conductivity particles as failing to fulll the requirement of passivity (even were he

unable to identify thermal conductivity as the source of the observed differences in the zero-size

velocity measurements).

[85] Even were external forces such as gravity to act on the uid, enabling the particle to sediment

relative to the surrounding uid if its density differed from that of the uid, such relative motion

would vanish in the pointsize tracer-particle limit, thereby having no effect upon the ability of the

tracer particle to monitor the uid velocity that exists in its absence.

[86] By the phrase gas-kinetic molecular interpretation is meant that the property cannot be derived

directly simply by summing each of the three elemental extensive properties of the individual

molecules in some small domain of volume V (namely the mass m; kinetic energy mc

2

=2; and

momentum mc of the molecules, with c the molecular velocity) and subsequently dividing by the

volume of that domain in order to obtain the corresponding intensive volumetric pointwise mass,

kinetic energy, and momentum densities at a point of the continuum.

[87] The reason for separating these two items stems from the fact (noted in connection with Table 2

appearing in Appendix C) that it is possible under certain well-dened circumstances for the

traditional and modied NSF equation set to fortuitously yield identical results, both of which

accord with experiment, albeit on the proviso that the correct velocity boundary condition be used

(either that of no-slip imposed upon v

l

or the equivalent Maxwell slip condition imposed upon v

m

).

[88] The isothermal assumption is needed in order to avoid complications associated with thermal

diffusion species uxes, while the isobaric assumption is similarly required to avoid pressure

diffusion contributions to the species ux density j

i

[18].

[89] This has the effect of enabling the right-hand side of (7.1) [and, equivalently, that of Eq. (1.6) for the

isothermal, isobaric, binary diffusion case] to be re-written in the form j

v

= DV ln r = D

+

V^ v =

D

+

(q^ v=qw

1

)

p;T

Vw

1

= (q^ v=qw

1

)

p;T

j

1

:

[90] We use the word semi-empirical here because there does not appear to exist in the literature a

theoretical proof of the concentration-slip boundary condition, derived along the lines laid out by

Maxwell [8] in the thermal gradient case, wherein the concentration analog of Eq. (5.4) is derived

from the analog of the MaxwellBurnett thermal stress term (5.3). Rather, owing to this lack,

Kramers and Kistemaker [65] adopted their widely-used concentration-slip velocity condition on a

different basis, namely a molar rather than mass basis. Explicitly, we are not aware of the existence

in the literature of the Burnett extra stress concentration analog of Eq. (4.5), although if our theory

is correct it should be given by Eq. (4.6), in which j

v

= DV ln r (see Ref. [89]). According to our

theory, the generic no-slip boundary condition should be given by Eq. (5.8), where I

s

.

j

v

= DV

s

ln r

in the present binary mixture case.

[91] Reynolds [71] experiments were actually performed with porous plugs rather than with well-dened

capillary tubes.

[92] S.E. Vargo, E.P. Muntz, G.R. Shiett, W.C. Tang, J. Vac. Sci. Technol. A 17 (1999) 2308;

J.P. Hobson, D.B. Salzman, J. Vac. Sci. Technol. A 18 (2000) 1758;

F. Ochoa, C. Eastwood, P.D. Ronney, B. Dunn, Thermal transpiration based microscale propulsion

and power generation devices, seventh Intl. Microgravity Combustion Workshop, Cleveland, OH,

June 2003;

Y. Sone, K. Sato, Phys. Fluids 12 (2000) 1864.

[93] In regard to these experiments, note that according to Eq. (3.3) the slip coefcient is different for

monatomic and diatomic gases.

[94] H. Brenner, Molecular, Brownian motion conrmation of the tracer/mass velocity disparity, Phys.

Rev. E (under revision; originally submitted under the title Molecular, Brownian motion

conrmation of the Euler/Lagrange velocity disparity).

[95] E. Nelson, Phys. Rev. 150 (1966) 1079;

E. Nelson, Dynamical Theories of Brownian Motion, Princeton Univ. Press, Princeton,

1967;

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H. Brenner / Physica A 349 (2005) 60132 128

E. Nelson, Connection between Brownian motion and quantum mechanics, in: H. Nelkowski, A.

Hermann, H. Poser, R. Schrader, R. Seiler (Eds.), Einstein Symposium, Berlin, Lecture Notes in

Physics, vol. 100, Springer, Berlin, 1979, p. 168.

[96] K. Ito , Stochastic Calculus, Springer Lecture Notes in Physics, vol. 39, Springer, New York, 1975,

p. 218.

[97] In probabilistic terminology, v

l

constitutes Nelsons drift velocity (more precisely, his forward

drift velocity, since a hypothetical mathematically-dened backwards drift velocity also appears in

Nelsons theory, a fact that need not concern us here). In his notation, Nelsons symbol v [no relation

to our v in either Eqs. (1.3) and (1.4)] is equivalent to our mass velocity v

m

; as is apparent from its

appearance in Nelsons continuity equation, analogous to our Eq. (1.2).

[98] In our interpretation of Nelsons work, D might better be termed the uids self-diffusion

coefcient, since his analysis appears limited to single-component uids within which

mass density gradients exist; that is, the symbol D appearing in (7.3) is regarded as being a

self-diffusion coefcient, intrinsic to the single-component uid itself, rather than arising from the

presence a foreign object, namely a colloidal particle, present in the uid. In this sense, D should be

regarded as an isotropic correlation coefcient, ID = (1=2)DxDx)=Dt; in which the position vector

x = x(x

0

; t) represents the statistical location at time t of a uid particle that at time t = 0 was

located at the position x

0

: The phrase uid particle here refers not to a material particle (which is

an extensive entity) but rather to a uid particle (an intensive entity) in the sense implicitly understood

in connection with Eq. (1.9), where the tracer uid eld, v

l

(x

0

; t); is regarding as describing the (mean)

tracer motion, the so-called forward motion, of such a hypothetical uid particle. Mathematically,

the symbol D is that appearing in the Markoff process stochastic relation [99] dx(t) = v

l

[x(t); t]dt

2D

_

dw(t); in which dx(t) x x

0

; with dw(t) a normalized Wiener process [100].

[99] P. Garbaczewski, Phys. Rev. E 57 (1998) 569.

[100] L. Arnold, Stochastic Differential Equations, Wiley-Interscience, New York, 1974.

[101] E. Schro dinger, Sitzungsber. Preuss. Akad. Wiss. Phys.-Math Klasse 1 (1931) 144;

J.C. Zambrini, Physica B,C 151 (1988) 327.

[102] E. Nelson, Quantum Fluctuations, Princeton University Press, Princeton, 1985.

[103] G. Bacciagaluppi, Founds. Phys. Lett. 12 (1999) 1.

[104] P. Garbaczewski, Phys. Lett. A 147 (1990) 168. With regard to the latters notion of Brownian

recoil, the work of Streater et al. cited later in Ref. [119] appears also to introduce a similar

Brownian recoil-like effect.

[105] P. Garbaczewski, Phys. Lett. A 143 (1990) 85;

P. Garbaczewski, Phys. Lett. A 172 (1993) 208;

P. Garbaczewski, Phys. Lett. A 178 (1993) 7;

P. Garbaczewski, J.P. Vigier, Phys. Rev. A 46 (1992) 4634;

P. Garbaczewski, J.P. Vigier, Phys. Lett. A 167 (1992) 445;

P. Blanchard, P. Garbaczewski, Phys. Rev. E 49 (1994) 3815. For later references see P.

Garbaczewski, Physica A 317 (2003) 449.

[106] K. Namsrai, Nonlocal Quantum Field Theory and Stochastic Quantum Mechanics, Kluwer,

Dordrecht, 1985;

J.C. Zambrini, Phys. Rev. A 33 (1986) 1532;

J.C. Zambrini, J. Math. Phys. 27 (1986) 2307;

J.C. Zambrini, Phys. Rev. A 35 (1987) 3631;

N.C. Petroni, F. Guerra, Found. Phys. 25 (1995) 297.

[107] A. Einstein, Ann. Phys. 17 (1905) 549; see also A. Einstein, in: R. Fu rth (Ed.), Investigations on the

Theory of the Brownian Movement, Dover reprint, New York, 1956.

[108] M.R. von Smoluchowski, Ann. Phys. 21 (1906) 756.

[109] The essentially kinematic analyses of Einstein and Smoluchowski preceded the later dynamical

theories of Brownian motion phenomena, such as those due to Langevin, Ornstein-Uhlenbeck,

Kramers, etc. (cf. Ref. [110]).

[110] S. Chandrasekhar, Rev. Mod. Phys. 15 (1943) 1; N. Wax (Ed.), Selected Papers on Noise and

Stochastic Processes, Dover reprint, New York, 1954.

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 129

[111] Youri Lvovich Klimontovich, late Professor Emeritus in the Physics Department at Moscow State

University, died of cancer on November 27, 2002, approximately three months before I learned of

his contribution to the subject under discussion.

[112] Yu.L. Klimontovich, Statistical Theory of Open Systems, vol. 1: A Unied Approach to Kinetic

Descriptions of Processes in Active Systems, Kluwer, Dordrecht, 1995 (Chapters 13 and 14);

Yu.L. Klimontovich, Theor. Math. Phys. 92 (1992) 909;

Yu.L. Klimontovich, Theor. Math. Phys. 96 (1993) 1035.

[113] It is interesting to note that an identical term appears in the well-known book of de Groot

and Mazur [13], but only in the context of a class of applications involving what they

term discontinuous systems [cf. Eqs. (69) and (72) of their Chapter XV]. Indeed, they

explicitly identify the term j

v

appearing in our subsequent Eq. (7.4), which they term the

volume ow.

[114] L. Onsager, Ann. Trans. NY Acad. Sci. 46 (1945) 241. It is interesting to note in the present context

that Onsager comments as follows when discussing problems of pure multicomponent diffusion in

liquids, involving what appears to us to be thermodynamically ideal solutions: ..provided only that

the volume change due to mixing may be neglected, it is possible to arrange matters such that v = 0

everywhere (where Onsagers hydrodynamic velocity, v; is understood by us to be the volume

velocity). Moreover, he goes on later to further state that: Viscous ow is a relative motion of

adjacent portions of a liquid. Diffusion is a relative motion of its different constituents. Strictly

speaking, the two are inseparable; for the hydrodynamic velocity in a diffusing mixture is merely an

average determined by some arbitrary convention.

[115] As pointed out by Haase [15, p. 221] and others [116], experimentalists who measure molecular

diffusivities usually choose a volume- rather than mass-based reference frame (so as to avoid having

to explicitly address what Haase terms convective velocities, namely nonzero mass-average

velocities, v

m

): In this frame of reference it is supposed: (i) that the volume velocity vanishes

everywhere, v

v

= 0 (corresponding here to v

l

= 0), despite the fact that v

m

a0; and (ii) that the

diffusional process is unidirectional, However, to the best of our knowledge, it appears never to have

been pointed in this connection that the assumption of requiring that v

v

= 0 everywhere, including on

the boundary, is incompatible with the traditional no-slip tangential boundary condition, I

s

.

(v

m

U) = 0; imposed upon v

m

[117]. Equally, the KramersKistemaker [65] species concentration

boundary condition, analogous to (5.2), would also be violated unless it was true that, when

expressed in appropriate binary diffusion terminology, v

v

= v

m

C

s

uV

s

ln T; for, in that case,

Eq. (3.5) becomes identical with Eq. (5.1), corresponding to no slip of the volume velocity (and hence

of the Lagrangian velocity v

l

).

[116] E.L. Cussler, Diffusion, second ed., Cambridge University Press, Cambridge, 1997.

[117] J. Camacho, H. Brenner, Ind. Eng. Chem. Res. 34 (1995) 3326;

T.Y. Liao, D.D. Joseph, J. Fluid Mech. 342 (1997) 37;

P.S. Perera, R.F. Sekerka, Phys. Fluids 9 (1997) 376.

[118] J.C. Maxwell, Proc. Lond. Math. Soc. 3 (1870) 82. Reprinted in: W.D. Niven (Ed.), The Scientic

Papers of James Clerk Maxwell, vol. 2, Cambridge University Press, Cambridge, 1890, p. 208. This

paper discusses Maxwells view of the relation between the Eulerian and Lagrangian velocities of a

uid. While it might appear from Maxwells remarks that he is literally referring to a molecule, it

is clear from his Lagrangian pathline example that his paper addresses, as well as from his later use

of the word molecule, that he is actually referring to a particle of uid, what today would be

referred to as a material uid particle.

[119] R.F. Streater, J. Math. Phys. 38 (1997) 4570;

R.F. Streater, Rep. Math. Phys. 40 (1997) 557;

R.F. Streater, J. Stat. Phys. 88 (1997) 447.

[120] M.R. Grasselli, R.F. Streater, Rep. Math. Phys. 50 (2002) 13.

[121] R.F. Streater, Proc. Roy. Soc. (London) A 456 (2000) 205.

[122] R.F. Streater, Open Syst. Inform. Dynamics 10 (2003) 3.

[123] R.F. Streater, Statistical Dynamics, Imperial College Press, London, 1995.

[124] R. Balescu, Statistical Dynamics, Imperial College Press, London, 1997.

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 130

[125] C. Beck, G. Roepstorff, Physica A 165 (1990) 270;

R. Dobrushin, Caricatures of hydrodynamics, in: B. Simon, A. Truman, I.M. Davies (Eds.),

Mathematical Physics, Adam Hilger, Bristol, 1989, p. 117;

Xing Xiu-San, Chinese Sci. Bull. 40 (2001) 447.

[126] J.W. Cahn, J.E. Hilliard, J. Chem. Phys. 28 (1958) 258;

U. Felderhoff, Physica 48 (1970) 541;

H.T. Davis, L.E. Scriven, Adv. Chem. Phys. 49 (1982) 357.

[127] D.D. Joseph, Eur. J. Mech. B/Fluids 9 (1990) 565;

P. Galdi, D.D. Joseph, L. Preziosi, S. Rioero, Eur. J. Mech. B/Fluids 10 (1991) 253;

D.D. Joseph, Y. Renardy, Fundamentals of Two-Fluid Dynamics, Part I, Springer, New York,

1992;

D.D. Joseph, A. Huang, H. Hu, Physica D 97 (1996) 104.

[128] J. Serrin, Q. Appl. Math. 41 (1983) 357;

J.E. Dunn, J. Serrin, Arch. Rat. Mech. Anal. 88 (1985) 95;

P. Pettijeans, T. Maxworthy, J. Fluid Mech. 326 (1996) 37;

C. Chen, E. Meiburg, J. Fluid Mech. 326 (1996) 37;

D.M. Anderson, G.B. McFadden, A.A. Wheeler, Ann. Rev. Fluid Mech. 30 (1998) 139;

J. Badur, J. Banaskiewicz, Archiv. Thermodynamics 19 (1998) 61;

C.Y. Chen, L. Wang, E. Meiburg, Phys. Fluids 13 (2001) 2447;

C.Y. Chen, E. Meiberg, Phys. Fluids 14 (2002) 2052;

J.A. Pojman, Y. Chekanov, J. Masere, V. Volpert, T. Dumont, H. Wilke, Effective interfacial

induced convection (EITIC) in miscible uids, AIAA 2001-0764.

[129] In the case of gases, kinetic theory [18] suggests that a better assumption would be D

v

= D

+

v

=r; where

D

+

v

is a constant, independent of density. This would result in different expressions for the four

Korteweg coefcients than those given in Eq. (8.2).

[130] In the interest of greater generality we could have added a body force per unit volume, say f; to the

right-hand side of (8.3). However, we have refrained from doing so in order to clarify subsequent

arguments regarding other classes of phoretic particle motion [30], which, in contrast with the thrust

of our work involving circumstances where f = 0; are driven by nonzero body forces.

[131] It is important to distinguish between the phenomenon of thermophoresis, which is a single-particle

theory applicable to non-Brownian particles, and that of thermal diffusion, which involves multiple

Brownian particles in a uid [48], collectively forming a second species, so that the solute and solvent

together constitute a nonisothermal binary mixture We bring this up because the SemenovSchimpf

interpretation of experimental data does not appear to strictly constitute a test of single-particle

thermophoresis.

[132] V.G. Levich, Physicochemical Hydrodynamics, Prentice-Hall, Englewood Cliffs, New Jersey, 1962.

[133] F.A. Morrison Jr., J. Colloid Inter. Sci. 34 (1970) 210.

[134] J.R. Melcher, Continuum Electromechanics, MIT Press, Cambridge, MA, 1981;

R.F. Probstein, Physicochemical Hydrodynamics, second ed., Wiley, New York, 1995.

[135] S.N. Semenov, Philos. Mag. 83 (2003) 2199.

[136] M.E. Schimpf, S.N. Semenov, J. Phys. Chem. B 105 (2001) 2285;

M.E. Schimpf, S.N. Semenov, J. Phys. Chem. B 104 (2000) 9935;

J.C. Giddings, P.M. Shiundu, S.N. Semenov, Colloid Interf. Sci. 176 (1995) 454.

[137] F. Brochard, P.-G. de Gennes, C.R. Hebd. Seances Acad. Sci. 293 (1981) 1025.

[138] J.O. Hirschfelder, C.F. Curtiss, R.B. Bird, Molecular Theory of Gases and Liquids, Wiley, New

York, 1954.

[139] M.N. Kogan, Rareed Gas Dynamics, Plenum Press, New York, 1969.

[140] R.J. Atkin, R.E. Craine, Quart. J. Mech. Appl. Math. 29 (1976) 209;

R.J. Atkin, R.E. Craine, J. Inst. Maths Appl. 17 (1976) 153;

C. Truesdell, Rational Thermodynamics, second ed., Springer, Berlin, 1984;

F. Dobran, Theory of Structured Multiphase Mixtures, Springer, Berlin, 1991;

C.R. Reid, F. Jafari, Int. J. Eng. Sci. 33 (1995) 411;

K.R. Rajagopal, L. Tao, Mechanics of Mixtures, World Scientic, Singapore, 1995;

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 131

D.A. Drew, S.L. Passman, Theory of Multicomponent Fluids, Springer, New York, 1998;

A.F. Mills, Int. J. Heat Mass Transfer 41 (1998) 1955;

D.S. Drumheller, Int. J. Eng. Sci. 38 (2000) 347.

[141] J.H. Cushman, The Physics of Fluids in Hierarchical Porous Media: Angstroms to Miles, Kluwer,

Dordrecht, 1997.

[142] F. Sharipov, D. Kalempa, Phys. Fluids 16 (2004) 759.

[143] F. Sharipov, Phys. Rev. E 69 (2004) 061201.

[144] F. Sharipov, Eur. J. Mech. B/Fluids 22 (2003) 133.

[145] F. Sharipov and V. Selenzev, J. Phys. Chem. Ref. Data 27 (1998) 657.

[146] In a generic context, the diffuse current j

c

; of some extensive property C is dened as the ux density

of the property over and above the corresponding convective contribution n

m

^

c thereto carried by the

mass current n

m

= rv

m

: Stated more explicitly, the total current n

c

of the extensive property under

discussion in a Eulerian space-xed reference frame is regarded as being of the form n

c

= n

m

^

c j

c

;

with

^

c is the amount of the property per unit mass, i.e., the specic density of the property C: The

latter density appears in the generic Eulerian transport equation qc=qt V

.

n

c

= p

c

in which c =

r

^

c and p

c

are, respectively, the amount of the property and temporal rate of production of the

property, both on a per unit volume basis. This generic Eulerian transport is formally equivalent to

the generic material derivative form, rD

m

^

c=Dt V

.

j

c

= p

c

:

[147] The latter fact shows, for example, why the thermomolecular pressure difference in the thermal

transpiration problem [24] is correctly given by Maxwells scheme despite the fact that Maxwells

transport equations are inappropriate.

[148] Note that in terms of the fundamental Newtonian stress issue (1.1), the extra deviatoric stress

[cf. (4.2)], T

g

= 2mVj

g

; makes no contribution to the present problems, just as was true in Appendix

C, owing to the fact that since V

2

j

g

= 0; it follows that V

.

T

g

= 0:

[149] E. Yariv, H. Brenner, Phys. Fluids 14 (2002) 3354;

E. Yariv, H. Brenner, J. Fluid Mech. 484 (2003) 85;

E. Yariv, H. Brenner, SIAM J. Appl. Math. 64 (2003) 423.

ARTICLE IN PRESS

H. Brenner / Physica A 349 (2005) 60132 132

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