A Course in Fluid Mechanics With Vector Field Theory

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06-703 190 Spring, 2001
l = ay (192)
where a is some constant and 0<a<1.
PRANDTLS UNIVERSAL VELOCITY PROFILE

The velocity profile in turbulent flow is essentially flat, except near the wall where the velocity gradients
are steep. Focussing attention on this region near the flow, Prandtl tried to deduce the form for the
velocity profile in turbulent flow. Recall from (189) that in pipe flow, the total stress varies linearly from
0 at the center line to a maximum value at the wall:
1 P r
(rzT ) = r = 0 < 0 (193)
2 L R
where we have defined 0 -(1/2)(R/L)P > 0
which represents the stress on the wall. In the turbulent core, the Reynolds stress dominates the
laminar stress; then substituting (191) through (193):
(xyt ) rz
(T )
2
dv
l{2 x 0 1
y
(194)
R
a2 y 2
dy
dv x F1 y I = v * F1 y I
0
; H RK H RK
or ay =
dy
v*
The general solution to this 1st order ODE is
y+ y+
v + d y + i = C + 2a 2
1 + tanh
a
1
1 + (195)
R R
where C is the integration constant, v* is called the friction velocity and where we have introduced
dimensionless variables:
v
v+ = x
v*
v* v*
y+ = y and R+ = R

Copyright 2000 by Dennis C. Prieve

06-703 191 Spring, 2001
Near the wall (i.e. for y<<R or y+<<R+), we can simplify (195):
y+ y+
for y+<<R+: 1 +
= 1 +
d i
+ O y +2 (196)
R 2R
y+ 1 4R +
tanh 1 1 = ln + O y+ d i
R+ 2 y +
Dropping the higher-order terms:
d i
v+ y+ =
b g
2 ln 4 R + 1
+ C + ln y + (197)
144 a 2443 a
c
where c is a collection of constants.
This result can be derived more easily by starting over with a simplified (194):
dv x dv x 1 dy 1 dy +
for y<<R: ay = v* or = = (198)
dy v * a y a y+
{
dv+
1
which integrates to v+ = ln y + + c
a
where c is some integration constant. When

plotted on semi-log coordinates, experimental
velocity profiles do indeed show a linear
region which extends over a couple of
decades of y+ values:
(6)
Moreover, the slope and intercept of this
straight line don't seem to depend on the
Reynolds number. Indeed, the slope and
intercept also don't seem to depend on the
shape of the conduit. Rectangular conduits
yields the same velocity profile on these
coordinates. This is called Prandtls
Universal Velocity Profile:
y+>26: v + = 2.5 ln y + + 5.5 (199)

06-703 192 Spring, 2001
which applies for y+>26 (the turbulent core). This coefficient of lny+ corresponds to a=0.4. so (192)
becomes:
l = 0.4 y
Recall that we reasoned that a had to be in the range of 0 to 1 to be physically realistic.
In the laminar sublayer, Reynolds stress can be totally neglected, leaving just viscous stress. This
close the wall, the total stress is practically a constant equal to the wall shear stress 0:
R| xy (rzT )
y << R: S| dvx = 0
T dy
Then we can integrate the above ODE for v x , subject to v x = 0 at y=0 (i.e. no slip):

vx = 0 y

Dividing both sides by v* we can make the result dimensionless:
y+<5: v+ = y+ (200)
which applies for 0<y+<5 (the laminar sublayer). Of course (199) also does not apply near the
center of the pipe, since the y+ R+ there, whereas (199) was derived by assuming that y+ << R+ (see
(196)).
PRANDTLS UNIVERSAL LAW OF FRICTION

Lets try to figure deduce the analog of Poisueille's Formula (see page 87) for turbulent flow.
Poisueille's Formula is the relationship between volumetric flowrate through the pipe and pressure drop.
Volumetric flowrate Q is calculated by integrating the axial component of fluid velocity of the cross
section of the pipe:
vz =
Q
R 2
=
2
R2 0
z R
r v z (r ) dr
Now we are going to use (199) for the velocity profile, although we assumed in (198) that y<<R (where
y = R-r).

06-703 193 Spring, 2001
Although the derivation of (199) assumed that

we are very close to the wall (y+<<R+, see
(196)), (199) works remarkly well right out
to the centerline y+=R+. The plot at right
shows the velocity profiles (with different wall
roughness on the walls) compared with
predictions based on (199). The ordinate is
vz ( R ) vz ( r )
v*
( ) ( )
= v + R + v + y + = 2.5ln R + + 5.5 2.5ln y + + 5.5

R+
= 2.5 (ln R + ln y + ) = 2.5ln +
y
R R
= 2.5ln = 2.5ln
y Rr
Note that (199) predicts an infinite velocity-

difference at y=0, whereas the actual velocity
must be finite. Of course, (199) does not
apply right up to the wall because very near
the wall the Reynolds stresses are not
dominant.
Substituting (199) and integrating:
LM FG v * R IJ + 1.75OP
v z = v * 2.5 ln
N H K Q (201)
Now the friction velocity can be related to the friction factor, whose usual definition can be expressed
in terms of the variables in this analysis:
0 F v* I 2
= 2G
f
1
vz
2 GH v z JJK
2
vz 2
Thus =
v* f
Likewise, the usual definition of Reynolds number yields

06-703 194 Spring, 2001
2 vz R
Re

v* R vz R v* Re f
Thus = =

123
Re 2
vz 2 2
;
f 2
Relating v* to f and v z to Re, (201) can be written as:
1
f
= 177 d
. ln Re f 0.60 i
or
1
f
= 4.07 log10 Re d i
f 0.60
which fits experimental data remarkable well. A slightly better fit can be obtained by adjusting the
coefficients:
1
f
d
= 4.0 log 10 Re f 0.40 i (202)
which is called Prandtls (universal) law of friction. It applies virtually over the entire range of
Reynolds numbers normally encountered for turbulent pipe flow: 2100 < Re < 5x106.

06-703 195 Spring, 2001
Electrohydrodynamics
ORIGIN OF CHARGE
Nearly all particles, bubbles or drops in water are charged.
We know this because when you apply an electric field across
water containing a particle, bubble or drop, you can observe it
to move. An example is the red blood cell experiment at right.
Interface between the two immiscible phases of the particle and

water acquires charge by a number of mechanisms:
adsorption of ions (e.g. SDS and FeOH+2)
dissolution of ions from ionic solids (e.g. AgI)
dissociation of acidic or basic sites on interface
COOH COO- + H+
NH2 + H+ NH3+
Regardless of how the surface acquires its charge, overall electroneutrality must be obeyed. So the
solution must contain an excess of counterions. For example, if the surface acquires its charged by the
dissociation of COOH groups at the interface, the COO- remaining at the interface gives the interface a
negative charge, but the H+ joins the rest of the ions in the aqueous solution, thereby lending it a net
positive charge.
Counterions would experience an electrostatic attraction for the surface which tends to pile up the ions
next to the interface. On the other hand, the ions undergo diffusion (Brownian motion) which tends to
disperse them uniformly throughout the phase. At equilibrium, a balance is achieved between these two
opposing tendencies. In this equilibrium state, a diffuse
cloud of counter-ions is formed next to the charged
interface.
double layer - layer of charged fixed on interface +

diffuse cloud of counter-ions.
Even though there are equal concentrations of positive

and negative ions far from the surface, this is not true
inside the counterion cloud. Fluid elements inside the

06-703 196 Spring, 2001
cloud bear a net charge. Just like we define the mass per volume to be the density of the fluid, we can
define:
e(x,t) = local charge density (charge/volume)
Global electroneutrality requires:
z

bg
+ e y dy = 0
0
= surface charge density (charge/area)
GOUY-CHAPMAN MODEL OF DOUBLE LAYER

Let's try to quantify this description. In particular, we would like to know how thick this cloud is.
Because of the charge on the interface, ions feel a electrostatic force. The force per unit charge is called
the electric field:
E(x) = electric field (force/charge)
Like gravity, this vector field is conservative, thus there must exist an scalar potential, (x) such that:
E = - (203)
Like the gravitational potential, the minus sign is included by convention. is called the electrostatic
potential.
[=] volts (energy/charge)
In thermodynamics, we learn that the criteria for phase equilibrium is equality of chemical potential i
for each chemical species i in each phase. For an ideal solution, recall that changes in chemical potential
at constant temperature and pressure is given by
FG i IJ = kT bd i gT , P = kT d ln ci
H ci K T, P ci or (204)
where kT is the thermal energy possessed by every ion or molecule and i is the chemical energy per
ion. When the species is charged, we must add an electrical contribution to the chemical energy to
obtain the electrochemical potential of each species.
electrical potential energy: zie

06-703 197 Spring, 2001
where zi is the number of elemental charges per unit ion (including sign) and e (>0) is the magnitude of
the elemental charge (on proton); thus zie is the charge on one ion. At equilibrium, ionic species
distribute themselves in an electric field such that their electrochemical potential is constant everywhere:
bg bg bg
ie x = i x + zi e x = const (205)
For example, diffusion of nonelectrolytes (i.e. zi = 0) takes place so that i is constant throughout the
solution, which means that the concentration ci is uniform at equilibrium. If the electrostatic potential
varies from one location to the next, the concentration of charged species will also not be uniform.
(205) can be re-written in differential form as
d ie = 0 = d i + zi e d
After substituting (204), we have kT d ln ci + zi e d = 0
which relates changes in ion concentration to changes in potential. This can be integrated to obtain
Boltzmann's Equation relating the local ion concentration to the local electrostatic potential
bg LM
z e x
ci x = A exp i
b g OP
N
kT Q
where A is some integration constant. In our problem, we expect the ion concentration to depend only
on y and we expect that the ionic concentration will approach the bulk value ci at some distance from
the charged interface. For this to happen, the electrostatic potential must tend to some constant (say
0 as y) or E 0:
as y : ci ci, 0
To satisfy these boundary conditions, Boltzmanns equation can be rewritten as
bg
ci y = ci exp i
LM
z e y b g OP (206)
N
kT Q
So if I knew the (y), I could calculate the concentration profile. But alas (y) is still unknown. I need
another equation. The extra equation is provided by Coulombs law of electrostatics. If I knew the
distribution of charges within a system, I could calculate the force on them using Columbs law. For a
continuum, Coulombs law can be written as:
4 4
.E = or 2 = (207)
e e
where is another material property called the electric permittivity of the medium between the ions
(e.g. the water):

06-703 198 Spring, 2001
Coul 2
vacuum = 1113
. 10 10
N - m2
water = 78 vacuum
This equation is called Poisson's Equation. The charge density of the fluid arises from the charge
born by each ion. Adding up the charges from each species i, then substituting Boltzmans equation,
gives
af
e y = z i eci a y f = z ieci exp MN
L a fOP
z ie y
i i
kT Q
Special Case: symmetric binary electrolyte, which means there are only two different species of ions and
they have the same magnitude of charge:
z+ = -z- = z
c+ = c- = c
Then Boltzmann's equation can be used to calculate the charge density:
LM
z e
e ( y) = z + ec + exp +
OP z e
+ z ec exp
LM OP
NkT Q kT N Q
L F ze IJ expFG + ze IJ OP = 2 zec sinhFG ze IJ
= zec MexpG
(208)
N H kT K H kT K Q H kT K
Substituting this into Poisson's equation, we get:
d 2
=
8 ec ze FG IJ
dy 2
sinh
kT H K
The argument of the sinh must be dimensionless, so lets use this combination to define a new
dimensionless potential
ze

kT
We can make the on the left-hand side dimensionless by multiplying both sides by ze/kT. Then we
have
d 2
= 2 sinh (209)
2
dy

06-703 199 Spring, 2001
8z 2 e 2 c 1
where 2 = [= ] 2
kT cm
Eq. (209) is a nonlinear ODE. Despite its innoccuous appearance, it is much more difficult to solve than
linear equations. However, a particular solution is possible:
subject to: = 0 at y=0
= 0 at y=
LM b yg OP = tanhFG 0 IJ e y
N 4 Q H4K
tanh (210)
which is called the Gouy-Chapman model for the double layer. In the special case in which the
surface potential is small, these expressions simplify to:
0 << kT ze :(y) = 0 exp(- y) and
af
c y = c 1 m
Fze 0 y I
H kT
e
K
Clearly is associated with the thickness of the
diffuse cloud. -1 is called the Debye length:
-1 = 10-9m = 1nm for c = 10-1M
-1 = 10-6m = 1m for c = 10-7M
This provides some idea of the thickness of the

charge cloud.
ELECTROSTATIC BODY FORCES

Since the fluid inside the diffuse cloud is charged,
FG IJ
ze ze 0 y
from (208): e ( y ) = 2 zec sinh
142kT
H K
43
2 zec
kT
e
ze

kT
any electric field in the fluid will exert a force on the fluid elements. This body force needs to be
included in the Navier-Stokes equations:
electrostatic body force/volume = eE

06-703 200 Spring, 2001
which is analogous to the body force exerted by gravity:
gravitational body force/volume = g
Including electrostatics, but neglecting gravity, the Navier-Stokes equation becomes:
Dv/Dt = 2v - p + eE
In the Gouy-Chapman model described in the previous section, the fluid is stagnant. At hydrostatic
equilibrium, any electric field applied to a charged fluid element will lead to a pressure gradient:
v = 0: p = eE
To see how large the pressure gradient is, lets return to the Gouy-Chapman model where the electric
field is oriented normal to the charged surface: i.e. = (y). Then the pressure gradient must also be
normal to the wall so that p = p(y). Hydrostatic equilibrium requires
dp LM
= e E y = 2zec sinh
ze FG IJ OPFG d IJ
dy N kT H K QH dy K (211)
where the second equality results from substituting (122) and (203). The right-hand side turns out to be
an exact differential, so that the equation can be re-written as
dp
= c kT
d FGze IJ
dy dy
cosh
H kT K
Multiplying both sides by dy and integrating from y=y to y=:
z
p( y )
dp = c kT
FG ze IJ = c kT LMcosh zeb yg cosh zebg OP
z
y=y
p y=
H kT K
d cosh
N kT kT Q
R| L ze b ygOP 1U|V
p( y) p = c kT Scosh M
|T N kT Q |W
The last step involves substituting ()=0 and remembering that cosh(0)=1. You might also recall that

06-703 201 Spring, 2001
cosh x
ex + e x
=
1RS for x = 0 4
2 >1T for x 0 0
Thus the pressure inside the cloud is always greater than cosh( x ) 2
the pressure in the bulk solution outside the cloud. This is 1
because the diffuse cloud is always oppositely charged

compared to the surface, so the cloud is also being pulled 0
2 0 2
by electrostatic forces toward the surface just like x
gravity always pulls us downward.
ELECTROKINETIC PHENOMENA
So far in our discussion, there has been no fluid motion. But since the fluid inside the diffuse cloud is
charged, we can exert a force on it by applying an
electric field tangent to the surface.
Consider again the distribution of ions near a charged

interface. The solution is not electrically neutral. So if
an electric field is applied tangent to the surface, the dF f
fluid will experience an electrostatic body force:
dFf = (dq)E = ( edV)E

dFs
where dq is the net charge on a fluid element having
volume dV. The solid is oppositely charged, so it feels
a force in the opposite direction. Consequently, at steady state, we can expect the fluid to move relative
to the solid, or vice versa.
At least two phenomena are associated with with the relative motion generated by this externally applied
electrostatic force:
electrophoresis - migration of charged particles through an otherwise quiescent fluid
electro-osmosis - flow of fluid through a porous solid bearing a surface charge
In both cases, relative motion between the fluid and the solid arises when an electric field is applied
externally. Conversely, forcing a fluid to move tangent to a charged interface generates an electric field:
sedimentation potential - the electrical potential (gradient) which arises during sedimentation
of charged particles in a gravitational field
streaming potential - the electrical potential (gradient) which arises during flow of fluid
through a porous solid which bears a surface charge

06-703 202 Spring, 2001
These four phenomena depend on the magnitude of the surface charge. Measurements of these induced
velocities or induced potentials are the most commonly used techniques for determination of surface
charge.
SMOLUCHOWSKI'S ANALYSIS (CA. 1918)

Consider an infinite plate in contact with an electrolyte
solution. Suppose the plate bears a uniform surface charge
density and we somehow externally apply an electric field Ex
tangent to the surface in the +x direction. Let's try to find the
velocity profile v induced by this electric field.
continuity: . v = 0
NSE: Dv/Dt = 2v - p + eE (212)
From the arguments above, we expect the fluid to move in the direction of the applied electrostatic
force. The simplest solution to this problem which has this property is:
v x = v x(y), v y = v z = 0
Since v x is independent of x, this solution automatically satisfies the mass balance. Of course, we must
allow v x to vary with y so we can meet the no-slip condition at the surface. Note that at steady-state,
the inertial terms identically vanish (like gravity-driven flow down inclined plane).
In the absence of flow, the ion concentration profiles are independent of x [see (206)]. Any flow
tangent to the plate is not expected to perturb the ion concentration profiles because tangential flow just
replaces fluid having a particular concentration with fresh fluid having the same composition (also v.ci
= 0). This suggests that the charge density profile is not perturbed by flow caused either by an
externally applied electric field (tangent to plate) or by an externally applied pressure gradient:
= eq
where we will use the superscipt eq to denote the equilibrium state of the variable (in the absence of
flow); we will also use the prefix " " to denote perturbations from equilibrium (caused by the applied
electric field). Thus the above statement is equivalent to
eq + where = 0

06-703 203 Spring, 2001
If we used two large vertical plate electrodes to apply the

electric field, as shown at right, we would expect the electric
field lines to be straight and tangent to the surface* and the
electrostatic potential to vary linearly with distance from one
electrode to the other. Thus the applied electrostatic forces
should act perpendicular to the electrodes and parallel to our
surface. In other words, the applied electric field is
expected to have only an x-component which independent of
x and y.
This expectation is fulfilled if the electrostatic potential has the

following form:
b g bg bg
x, y = eq y + x
d eq d
2

E
=
dy
123
j +
12
dx3
i
E eq E
where eq is the equilibrium potential found in the absence of

an externally applied electric field or an applied pressure
gradient (see previous section on Gouy-Chapman model),
and where is the perturbation from equilibrium caused by
the externally applied electric field or pressure gradient. The pressure field suffers a similar perturbation:
b g bg
p x, y = p eq y + p
dp eq p
The y-component of (212) yields: + = eq E eq
y
dy y
but adding the superscript eq to terms in (211) yields:
dp eq
= eq E eq
y
dy
p
subtracting: = 0 or p = p(x)
y
*The field lines might not be straight near the entrance or exit of the capillary. Thus what follows strictly
only applies in the central region away from the ends.

06-703 204 Spring, 2001
Poisson's equation (207) can also be written as:
4
.E =

4 eq
.E eq + .E =

but in the absence of flow, Poisson's equation requires
4 eq
.E eq =

subtracting leaves .E = 0
dE x
or =0 or E x = const (213)
dx
The x-component of (212) becomes
d 2v x dp p p0
+ eq E x = = const = L =0
4 (214)
dy 2 dx L0
144 42444 3 f ( x)
g( y )
By applying a pressure gradient along the surface, we could pump the fluid past the solid, but this is
not the problem we want to address. Thus we set the pressure gradient to zero (p0 = pL) so there is no
pressure-driven flow. Boundary conditions include
at x=0: v x = v x,s
as x : dv x/dy 0 or v x v x,f
where v x,s is the velocity of the solid and v x,f is the velocity of the bulk fluid outside the cloud. The first
condition is just no-slip which says that at the interface between the fluid and the solid the two take on
the same velocity. The second condition says there is no shear force being applied to the fluid outside
the double layer.
To go further, we need to know how eq changes with y. This is provided by Poisson's equation (207):
d 2 eq
bg
eq y =
4 dy 2
(215)
d 2v x d 2 eq
(215) into (214): = E x
dy 2 4 dy 2

06-703 205 Spring, 2001
Since Ex=const, this can easily be integrated to

bg
vx y v x ,s = bg
eq y eq 0 E x
4 144 42444 3
bg

1
Substituting eq(y) from (210), we obtain a velocity profile like that
shown at right.
Let v x() v x,f

Ex
Then the above equation can be rewritten as

v x, s v x, f = E x (216)
4
where eq(0) - eq()
is called the
zeta potential - the electrostatic potential drop across the diffuse part of the double layer.
ELECTRO-OSMOSIS IN CYLINDRICAL
PORES
Consider a circular hole drilled through a plate.
If this is submerged in an electrolyte solution and
becomes charged, then applying a voltage across the
length of the pore will give rise to electro-osmosis
through the hole.
If the pore radius a is must larger than the Debye y I k -1

y II
length -1, then the velocity profile is essentially plug

flow except inside the double layer where the velocity
suddenly drops to zero at the stationary solid surface
vs = 0

bg
v fluid r =
4
E x

06-703 206 Spring, 2001
for all r outside the double layer. Here we have applied (216), but dropped the prefix " " since we
have no further need to distinguish between the equilibrium and the applied fields.
Example: A typical value of the potential for aqueous solutions is about 50mV. Plugging in the values
of the other parameters
/4 = 3.5 m/s per V/cm
as a typical value of v f/Ex.
Consequently, the volumetric flowrate through the pore is just this velocity times the cross-sectional
area:
a>>1: Q = a2( /4)Ex
So a measurement of the flowrate for a known applied electric field allows us to determine the zeta
potential.
k -1
ELECTROPHORESIS
Consider a rigid sphere immersed in a quiescent electrolyte
solution. Somehow we apply an electric field of strength E. In this
case the solid moves while the fluid far from the sphere remains
stationary:
v x,f = 0
(216) predicts that v x,s is
a>>1: U = ( /4)E
where /4 is now called the electrophoretic mobility. This result is called Smoluchowski's
Equation.
This applies for particles which are large compared to the Debye length. In the opposite limit of very
small small particles, another simple expression can be obtained:
a<<1: U = (3/2)( /4)E
which is called Huckel's equation. For the most general case of intermediate size, the problem is
much more complicated. A numerical solution is required (see Fig. 9.11.3, p560 of Hunter).

06-703 207 Spring, 2001
STREAMING POTENTIAL
So far in our discussion of electrokinetic phenomena, we have considered the motion of either fluid
or solid that results from the application of an electric field:
Electrophoresis, Electro-osmosis: E 0 U 0
Now we would like to consider the inverse situation in which relative motion across a charged interface
generates an electric field:
Streaming Potential,
Sedimentation Potential: U 0 E 0
Consider the pressure-driven flow through a

large circular pore.
-1 << a << L
Owing to the applied pressure drop, we generate PI > PII PII

a fully developed parabolic velocity profile so
familiar for laminar flow.
v z br g = 2
L F rI2O
Q
M1 G J P
a 2 MN H a K PQ
:v
yI y II
The main idea is that this flow causes convection

of charge in the counterion cloud which tends to generate a current. However in the absence of
electrodes in the two reservoirs, there is no way to form a complete electric circuit. So charge tends to
pile up in the reservoir positive charges on one side of the membrane and negative charges on the
other. Coulomb's law exerts a force on these charges which tends to restore electroneutrality to the
system and to prevent any steady-state rate of accumulation of charge.
Clearly any steady-state electrical current would eventually lead to infinite charge separation and infinite
attractive forces. The only way to avoid this is to have zero current at steady state. This is achieved
by an electric field which spontaneously arises inside the bulk of the fluid which creates an electrical
current equal but opposite to the convective current:
I = Iconv + Ielec = 0 (217)
The electrostatic potential drop associated with this induced electric field is called the streaming
potential. To calculate it, let's first calculate the current generated by convection of charges inside the
cloud.

06-703 208 Spring, 2001
If the charge cloud is very thin compared to the pore radius, then we
need to concentrate on the velocity profile right next to the wall. Here
the velocity profile becomes linear:
for s<<a: v z(s) = s

1
where s a-r
and = -dv z/drr=a
The net current through any surface S (open or closed) is just the
integral of the normal component of the current density over the
surface:
z
I = n.i da [=] amps
S
In our case, we choose a disk of radius a whose normal is parallel to the tube axis.
I conv = z0
a
v z 2 rdr 2 a z
0

sds (218)
Since =0 for most of the fluid (except for ra), we can approximate this integral as shown by the
second equality above. Next, we substitute Poisson's equation (215) for the space charge density:
= -( /4 ) d2eq/ds2 (219)
(219) into (218) and integrating by parts:
I conv =
2 z
a d 2 eq
0 ds 2
sds =
a eq
2
z ,0 eq z , b g b g
The potential drop across the counterion cloud is the zeta potential. Thus
Iconv = -(1/8 ) a (220)
According to (217), this convective contribution to the current must be balanced an electrical
contribution from an induced electric field. The relationship between current and electric field is given
by Ohm's law for electrolyte solutions, which takes the form of
ielec = KE
where K is called the specific conductance of the solution. Integrating over the cross-section of the
tube:

06-703 209 Spring, 2001
I elec = z
0
a
KEz 2 rdr a 2 KEz (221)
where Ez = - / z = const = - /L
is required by (213), where L is the length of the cylindrical pore. (220) and (221) into (217):
= L/2 aK (222)
Finally, we can relate to the applied pressure

drop by performing a macroscopic force balance
on the tube. Recognizing that the shear stress on
the tube wall rz is dv z/dsr=a = ,
(2 aL) = p( a2)
a
or L = p (223)
2

(223) into (222): = p
4 K
which is Smoluchowski's equation for streaming potential.
Surface Tension
MOLECULAR ORIGIN
Many of the fascinating effects we saw in Trefethens film are a consequence of surface tension.
What is surface tension and where does it come from?
Surface tension is a consequence of intermolecular forces which

are always present. The interaction between two molecules is
often represented by the Lennard-Jones 6-12 formula:
LM 12 6 OP
F I F I
V b Rg = 4 E MG J G J P
MMH123
RK H1R2K3 P
N Born vdW PQ
This expression is partly based on theory and partly empirical.
The inverse 6th power term represents van der Waals

06-703 210 Spring, 2001
attraction which is based on a rigorous theory. The inverse 12th power term is empirical. It
represents Born repulsion which results from the overlap of electron clouds. is called the collision
diameter this is the center-to-center distance at which the electron clouds begin to overlap and a
significant repulsion is experienced.As a first approximation, we can think of condensation of a liquid
from a vapor in terms of the molecules falling into this potential energy well:
vapor: R Vvapor = 0
liquid: R Rmin = 1.12 Vliq = -E
The heat of vaporization is approximately the energy gained by falling in this well:
Uvap ENA
This is all only approximate because we have only considered two-body interactions. In a condensed
state, multi-body interactions must also be considered. The existence of surface tension can be
expected from the difference in energy between molecules located in the bulk of a liquid and molecules
located at surface between the liquid and its vapor.
Let's pick a molecule from the bulk of the liquid phase. On the
average, it will be some average distance Rmin from its nearest
neighbor. If there are zbulk nearest neighbors, the energy of this
typical molecule from the bulk liquid is
ebulk = (zbulk /2)E
where the factor of 2 comes from assigning half of the energy of

interaction between a pair of atoms to each atom. For a hexagonal
close-packed array:
zbulk = 12
Now consider a molecule which resides at the interface between the liquid and the vapor. The same
basic formula can be written for the energy of this surface molecule:
esurf = (zsurf/2)E
Except that the number of nearest neighbors will be significantly less. Again for a hexagonal close-
packed array:
zsurf = 6
then esurf (1/2)ebulk
Now e < 0 for attractive interactions, so:

06-703 211 Spring, 2001
ebulk < esurf < 0
Thus molecules located at the surface do not have as low an energy as molecules in the bulk. So when
we calculate the free energy of the liquid, we should treat the surface molecules differently from the bulk
molecules. Indeed, it turns out that this contribution to the free energy of the system is proportional to
the number of surface molecules, which in turn is proportional to the surface area. The free energy per
unit area is called the surface tension:
= FG G IJ
H A K T , P
BOUNDARY CONDITIONS FOR FLUID FLOW
Surface tension causes a number of effects including:
makes homogeneous nucleation of bubbles virtually impossible: boiling is usually from

heterogeneous nucleation
increases the vapor pressure of small drops for same T: Kelvin effect
capillary rise
determines the shape of drops and bubbles
These are all hydrostatic effects; there is no fluid flow occuring. Since surface tension depends on
temperature, temperature gradients can gradients in surface tension, which in turn can generate flow.
Since the origin of surface tension is intermolecular forces, which are very short range (range is a few
Angstroms), surface tension does not change the form of the basic equations of motion. Instead,
surface tension is manifested in the boundary conditions applied to those equations.
Recall that when surface tension effects are negligible, the general boundary condition on stress was
given by
0: n.TI = n.TII
Surface tension makes both the normal and tangential components of stress continuous across an
interface. The more general boundary condition is

06-703 212 Spring, 2001
n.(TI-TII) = n(s.n) - s (224)
where s is called the surface divergence; it represents two of the three

terms in the usual divergence. By convention, n is pointing from phase I
into phase II. For example, suppose we define a local rectangular
Cartesian coordinate system such that the z-axis is normal to the interface:
n = ez
The usual divergence is given by
.v = xv x + yv y + zv z
The surface divergence does not include the term which represents the
derivative along the normal
s.n = xnx + yny -2H [=] m-1
This particular surface divergence represents the curvature of the

interface, often denoted by H or J.
Example: calculate the curvature of a sphere of radius r.
Solution: the unit normal to a sphere in spherical coordinates is
n = e r: nr=1, n=n=0
In this particular case, the normal is independent of the normal coordinate r so that the surface
divergence is the same as the regular divergence:
s.n = r-2 r(r21) = 2/r
Thus the curvature is inversely proportional to the radius of the sphere.
Similarly the surface gradient represents that part of the usual gradient which lies in the surface
s = xe x + ye y (225)
Suppose I dot both sides of (224) by the normal
TzzI - TzzII = -2H
Thus the normal component of the stress is discontinuous at a curved surface. In the particular case of
hydrostatic equilibrium, there is no deviatoric contribution to the stress just the hydrostatic pressure
hydrostatic equil: pI - pII = -2H = 2/r

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A Course in Fluid Mechanics With Vector Field Theory

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