CAPILLARITY 155

CAPILLARITY
D Or, University of Connecticut, Storrs, CT, USA Thermal expansion reduces the density of the liquid
M Tuller, University of Idaho, Moscow, ID, USA and therefore also reduces the cohesive forces at the
ß 2005, Elsevier Ltd. All Rights Reserved. surface as well as inside the liquid phase.
Soluble substances can increase or decrease surface
tension. If the affinity of the solute molecules or ions
Introduction to water molecules is greater than the affinity of
The coexistence of gaseous, liquid, and solid phases in the water molecules to one another, then the solute
soil pores gives rise to a variety of interfacial phenom- tends to be drawn into the solution and to cause an
ena that, for example, lead to spreading of liquid drop- increase in the surface tension. This is the effect of
lets on solid surfaces, liquid rising in capillaries and soil electrolytic solutes. For example, a 1% NaCl concen-
pores, or the entrapment of liquid in crevices. These tration increases the surface tension of an aqueous
phenomena, partially attributed to capillarity, deter- solution by 0.17 mN m
1 at 20 C. If, on the other
mine retention and movement of water and solutes hand, the cohesive attraction between water mol-
through soils. Hence they are of great importance in a ecules is greater than their attraction to the solute
variety of environmental and agricultural problems. molecules, then the latter tend to be relegated toward
the surface, reducing its tension. That is the effect of
many organic solutes, particularly detergents.
Liquid Properties
Contact Angle
The phenomenon of capillarity in porous media results
from two opposing forces: liquid adhesion to solid sur- When a liquid drop is placed on a solid surface, the
faces, which tends to spread the liquid; and the cohesive angle formed between the solid–liquid (SL) interface
surface tension force of liquids, which acts to reduce
liquid–gas interfacial area. The resulting liquid–gas
interface configuration under equilibrium reflects a Table 1 Liquid–vapor interfacial tensions for various liquids
balance between these forces. The phenomenon of Temperature Surface tension
capillarity is thus dependent on solid and liquid inter- Liquid (  C) (mN m
1)
facial properties such as surface tension, contact angle,
Water 20 72.94
and solid surface roughness and geometry.
25 72.13
Methylene iodide 20 67.00
Surface Tension Glycerin 24 62.6
Ethylene glycol 25 47.3
At the interface between water and solids or other Dimethyl sulfoxide 20 43.54
fluids (e.g., air), water molecules are exposed to dif- Propylene carbonate 20 41.1
ferent forces than are molecules within the bulk fluid. 1-Methyl naphthalene 20 38.7
For example, water molecules in the bulk liquid Dimethyl aniline 20 36.56
Benzene 20 28.88
are subjected to uniform cohesive forces whereby
Toluene 20 28.52
hydrogen bonds are formed with neighboring mol- Chloroform 25 26.67
ecules on all sides. In contrast, molecules at the air– Propionic acid 20 26.69
water interface experience net attraction into the Butyric acid 20 26.51
liquid because of lower density of water molecules Carbon tetrachloride 25 26.43
Butyl acetate 20 25.09
on the air side of the interface, with most hydrogen
Diethylene glycol 20 30.9
bonds formed at the liquid side. The result is a mem- Nonane 20 22.85
brane-like water surface that has a tendency to con- Methanol 20 22.50
tract and reduce the amount of its excess surface Ethanol 20 22.39
energy. The surface tension reflects the amount of Octane 20 21.62
Heptane 20 20.14
interfacial energy per unit area, or the energy required
Ether 25 20.14
to bring molecules from the bulk liquid to increase the Perfluoromethylcyclohexane 20 15.70
surface (it is also useful to express surface tension as Perfluoroheptane 20 13.19
force per unit length of interface). Different liquids Hydrogen sulfide 20 12.3
vary in their surface tension
(Table 1). Perfluoropentane 20 9.89
Surface tension also depends on temperature, Reproduced from Adamson AW (1990) Physical Chemistry of Surfaces, 5th
usually decreasing linearly as the temperature rises. edn. New York: John Wiley.
156 CAPILLARITY
and the liquid–gas (LG) interface (Figure 1) is referred
to as the equilibrium (or static) contact angle (). Two
equivalent approaches are commonly used to describe
the equilibrium contact angle on smooth and chem-
ically homogeneous planar surfaces: (1) a force bal-
ance approach, and (2) an interfacial, free-energy
minimization. The force balance formulation con-
siders interfacial tensions (
ij) as forces per unit
length; hence the force balance at the contact line of
a drop resting on a solid surface under equilibrium
requires the vector sum of the forces acting to spread
the drop (outward) to be equal to opposing cohesion
and viscous forces. The free-energy minimization
approach regards interfacial tension as energy per
unit area, and calculates changes in surface free
energy (
F) due to infinitesimal displacement (
A):

F ¼
Að
SL

GS Þ þ
A cos
LG
The result is identical whether considering the
minimization of free energy, with
F/
A ¼ 0, or
taking a balance of forces tangential to the solid
surface; both cases yield the Young equation:

LG cos þ
SL

GS ¼ 0
with L, G, and S indicating liquid, gas, and solid,
respectively, and
ij the respective interfacial surface
tensions. The equilibrium contact angle is therefore:

GS

SL
cos ¼

LG
Liquids that are attracted to solid surfaces (adhesion)
more strongly than to other liquid molecules (cohe-
sion) exhibit a small contact angle, and the solid is
Figure 1 Liquid–solid–gas contact angles: (a) hydrophilic sur-
face ( < 90 ) where liquid wets the surface; (b) hydrophobic
surface ( > 90 ) where liquid ‘repels’ the surface.
Figure 2 (a) Wettable silt surface ( 0 ); (b) treated water-repellent silt soil surface ( ¼ 70 ). (Reproduced from Bachmann J,
Elliesb A, and Hartgea KH (2000) Development and application of a new sessile drop contact angle method to assess soil water
repellency. Journal of Hydrology 231: 66–75.)
said to be ‘wettable’ by the liquid (Figure 1a). Con-
versely, when the cohesive force of the liquid is larger
than the adhesive force, the liquid ‘repels’ the solid
and  is large (Figure 1b).
Figure 2 illustrates differences in wettability of a
silt soil. In Figure 2b a water droplet is resting on a soil
surface that was treated to become water-repellent
( ¼ 70 ). In contrast, Figure 2a depicts a wettable
soil surface. In general, the contact angle of water
on clean glass, and presumably on most soil minerals,
is small, and for mathematical convenience is often
taken as  ¼ 0 .
Curved Surfaces and Capillarity
When the forces that spread the liquid (adhesion and
spreading on solids, or gas pressure within a bubble)
are in balance with surface tension that tends to min-
½1
imize interfacial area, the resulting liquid–gas inter-
face is often curved. In porous media, the liquid–gas
interface shape reflects the need to form a particular
contact angle with solid(s) on the one hand, and the
tendency to minimize interfacial area within the pore.
A pressure difference forms across the curved inter-
½2 face, where the pressure at the concave side of the
interface is greater by an amount that is dependent on
the radius of curvature and the surface tension of the
fluid. For a hemispherical liquid–gas interface having
radius of curvature R, the pressure difference is given
by the Young–Laplace equation:
½3
2


P ¼ ½4
R
where
P ¼ PL
PG when the interface curves into
the gas (e.g., water droplet in air); or
P ¼ PG
PL
when the interface curves into the liquid (e.g., air
bubble in water, water in a small glass tube). In
many instances a bubble may not be spherical, or
an element of liquid may be confined by irregular
solid surfaces, resulting in two or more different
radii of curvature such as water held in pendular
rings between two spherical solid particles (Figure 3).
The Young–Laplace equation for this case is given by:
 CAPILLARITY 157

Figure 3 (a) Radii of curvature and shape of water held in pendular space between two spherical grains (note that for two equal
spheres with radius a, the relationship between R2 and R1 is given as: R2 ¼ R12[2(a
R1)]. (b) Water menisci held between three
spherical glass beads at different capillary pressures.


1 1

P ¼
þ ½5
R1 R2
Note that this equation reduces to eqn [4] for spher-
ical geometry with R1 ¼ R2, and the sign of R is
negative for convex interfaces (R2 < 0) and positive
for concave interfaces (R1 > 0). For an interface
forming in a linear crevice or within a fracture,
R2 ! 1, hence eqn [5] reduces to:
P ¼
/R1, where
R1 equals half the fracture aperture.

The Capillary Rise Model

When a cylindrical glass tube of small diameter (ca-
pillary) is dipped into free water, a meniscus forms in
the tube owing to the contact angle between water
and the tube walls, and minimum surface energy
requirements. The smaller the tube radius, the larger
the degree of curvature and the pressure difference
across the air–water interface (Figure 4). The pressure
at the water side (PW) is lower than atmospheric Figure 4 Capillary rise in cylindrical tubes with different radii.
158 CAPILLARITY
pressure (P0). This pressure difference causes water to
rise into the capillary until the upward capillary force
is balanced by the weight of the water column. In a
cylindrical tube, the radius of meniscus curvature (R)
is related to the tube radius r by R ¼ r/cos; conse-
quently the equilibrium height of capillary rise in a
cylindrical tube with contact angle  is:
2
cos
h¼
w gr
where g is the acceleration of gravity, and w is the
liquid density. For water at 20 C in a glass capillary
with  ¼ 0 , the capillary rise equation simplifies to:
h(mm) ¼ 15/r(mm).
Capillarity in Soils
The complex geometry of soil pore space creates nu-
merous combinations of interfaces, capillaries, and
wedges in which water is retained, and results in a
variety of air–water and solid–water configurations.
Water is drawn into and/or held by these interstices
in proportion to the resulting capillary forces. In
Figure 5 Idealization of the soil pore space as cylindrical
capillaries.
Figure 6 (a) Thin section of Devonian sandstone, revealing angular pore space. (Reproduced from Roberts JN and Schwartz LM
(1985) Grain, consolidation and electrical conductivity in porous media. Physical Review B 31(9): 5990–5997.) (b) Scanning electron
micrograph of calcium-saturated montmorillonite clay.
addition, water is adsorbed on to solid surfaces with
considerable force at close distances. Due to practical
limitations of present measurement methods, no dis-
tinction is made between the various mechanisms
affecting water in porous matrices (i.e., capillarity
and surface adsorption). Common conceptual models
for water retention in porous media and matric poten-
tial rely on a simplified picture of soil pore space as
½6 a ‘bundle of capillaries’ (See Water Retention and
Characteristic Curve). The primary conceptual steps
made in such models are illustrated in Figure 5. The
representation of soil pores as equivalent cylindrical
capillaries greatly simplifies modeling and parameter-
ization of soil pore space and relies heavily on the
capillary rise equation (eqn[6]).
Capillarity in Angular Pores
Cursory inspection of scanning electron micrographs
of soils and other natural porous media (Figure 6)
shows that pore spaces formed by aggregation of
primary particles and mineral surfaces tend to be
angular and slit-shaped, rarely resembling cylindrical
tubes. Such observations and other shortcomings of
the ‘cylindrical capillary’ model have led to develop-
ment of new models for capillarity in angular and
slit-shaped pores.
Capillarity in angular pores is quite different from
the behavior in cylindrical pores with equivalent
cross-sectional area. For example, when angular
pores are drained, a fraction of the wetting phase
(water) remains in the pore corners (Figure 7a). This
aspect of ‘dual occupancy’ of wetting and nonwetting
phases, not possible in cylindrical tubes, more realis-
tically represents liquid configurations and the mech-
anisms for maintaining hydraulic continuity in
porous media. Liquid-filled corners and crevices
play an important role in displacement rates of oil
and in other transport processes in partially saturated
porous media. For all (regular and irregular) polygons
with n corners, the total water filled area (Awt) at
a given matric potential is simply the sum of the
 CAPILLARITY 159

Figure 7 (a) Dual-occupancy of wetting and nonwetting phases in triangular pores; (b) liquid–vapor interfacial configuration in a
triangular glass pore ( 2 mm).

water-filled areas in each corner (Figure 7a). This sum the rate of rise and the associated time scale, which is
is given by the simple equation: often of significant importance in many industrial
and natural processes. A simple force balance can be
Awt ¼ rðÞ2 FðÞ ½7 employed between a driving capillary force F
:
with F
¼ 2 R
cos ½9
!
X
i
1  ð180
 i Þ and a retarding viscous force F (assuming Poiseuille
F ð Þ ¼  
½8
n¼1
tan 2i
360 flow):

where  is the matric potential and F() is a shape dx

factor dependent on pore angularity (corner angles  i)
only.
In contrast to a piston-like filling or emptying of
circular capillaries, angular pores undergo different
filling stages and spontaneous displacement in the
transition from dry to wet or vice versa. Under rela-
tively dry conditions (low chemical potentials) liquid
accumulates in corners due to capillary forces. An
increase in chemical potential leads to an increase in
the capillary radius of interface curvature until the
capillary corner menisci contact to form an inscribed
circle. At this critical potential, liquid spontaneously
fills up the central pore (pore snap-off). The radius of
interface curvature at this critical point is equal to the
radius of an inscribed circle in the pore cross-section.
If an angular pore is drained, liquid is displaced from
the central region first, leaving some liquid behind in
corners. Subsequent decrease in chemical potential
results in incrementally decreasing amounts of liquid
in the corners. The critical potentials at spontaneous
liquid displacement differ for imbibition and drain-
age. (See Water Retention and Characteristic Curve.)
For completeness, one must also consider the role of
liquid films due to adsorption to solid surfaces. (See
Water Potential; Water Retention and Characteristic
Curve.)
Dynamic Aspects of Capillarity
Dynamics of Capillary Rise
The equilibrium height of fluid rise in a capillary
(eqn [6]) does not contain any information regarding
F ¼ 8x ½10
dt
to model the rate of capillary flow into a horizontal
capillary. Inertial effects can be included, according to:
d2 x
m ¼ F 
F ½11
dt2
where m is the mass of the liquid in the capillary, x
is distance, and t is time. Substitution of the forces
(eqns [9] and [10]) into eqn [11] and integration
(neglecting higher-order terms) yields the so-called
Lucas–Washburn–Rideal (LWR) equation:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi


R
cos
x¼ t ½12
 2
which describes the rate of liquid penetration into
ap horizontal capillary with the dependency of x on
t. It is interesting to note that Washburn’s neglect of
inertial effects and Rideal’s truncation of higher-order
terms (r
n, n > 2) in his series solution yield the same
solution (eqn [12]). Exact solutions have been pro-
vided that fully account for inertial effects and expand
the LWR expression to consider flows into horizontal
grooves and other capillary shapes.
Analytical solutions for dynamic capillary rise with
gravity present a mathematical challenge. Several
simplified analytical solutions for the rate of capillary
rise in vertical capillaries have been proposed, such as
the following implicit solution:
gR2 zðtÞ
t ¼ zðtÞ
ze ln 1
½13
8 ze
160 CAPILLARITY

Figure 8 (a) Comparison of measurements and theoretical models for capillary rise dynamics of silicon oil (PDMS 10) in glass
capillary with r ¼ 0.315 mm (calculated curve from eqn [14]; classic Washburn equation from eqn [13]); (b) inertia-induced oscillations
during capillary rise of water in different glass capillary sizes (numerical simulations). Note that inertial oscillations vanish for
capillaries smaller than r ¼ 0.474 mm according to eqn [15]. (Adapted from Hamraoui A and Nylander T (2002) Analytical approach for
the Lucas–Washburn equation. Journal of Colloid Interface Science 250: 415–421.)

The solution diverges as z(t) approaches the equi-
librium capillary rise ze (eqn [6]). Another approxi-
mate solution has been proposed, based on the
introduction of a retardation coefficient ( ):



cos
zðtÞ ¼ ze 1
exp
t ½14
ze
The solution converges to the equilibrium capillary rise
ze (eqn [6]) for long periods of time. Figure 8a depicts
comparison of eqns [13] and [14] with capillary-rise
measurements of silicon oil (PDMS 10) in a glass
capillary, with r ¼ 0.315 mm (
¼ 20.1 mN m
1;
 ¼10 mPa; and  ¼ 0.935 kg m
3).
The nondimensional retardation coefficient for
water in glass capillaries ranges from ¼ 0.5 for
large radii (r > rc), representing friction dissipation
due to contact line motion and contact angle adjust-
ment, to ¼ 0.7 for small radii (r < rc) representing
primarily viscous dissipation. The critical radius rc is
related to an interesting feature of capillary rise in the
presence of gravity, namely inertia-induced oscilla-
tions in large capillaries, as depicted in Figure 8b.
The inertial oscillations disappear in capillaries of
radii smaller than rc:
 1=5
2
cosð Þ2 2 g3
rc ¼ ½15
g
Dynamic Contact Angle
The contact angle formed between a flowing liquid
front (advancing or receding) and a solid surface is not
constant but reflects the interplay between capillary
and viscous forces. The relative importance of these
forces is often expressed by the so-called capillary
number, Ca ¼  v/
, with  the liquid dynamic viscos-
ity, and v the contact line velocity. The dependency of
the dynamic contact angle  D on the velocity of the
contact line during complete wetting can be described
by a nearly universal behavior according to the
so-called Tanner law:
 3D ¼ ACa ½16
where A is a constant ( 94 for  D in radians).
Eqn [16] fits the data of Hoffman for Ca < 0.1
and  D < 130 (Figure 9). The complete range of
Hoffman’s data fitted to the empirical expression:
( "
0:706 #)

1 Ca
 D ðradÞ ¼ cos 1
2tanh 5:16 ½17
1 þ 1:31Ca0:99
is depicted by a continuous line in Figure 9.
For conditions of partial wetting ( S > 0), the
relationships between contact angle and Ca are less
universal. It has been postulated that at low Ca the
apparent dynamic contact angle remains close to
the static angle but rapidly deviates when Ca exceeds
the value for  S (Figure 9). This postulate is
formalized by the following expression:
 3D
 3S ¼ ACa ½18
Additional examples of advancing and receding con-
tact angle dependency on capillary number are shown
in Figure 10. Note that for receding contact angle

there is a critical Ca above which the contact angle
vanishes.
The theoretical basis for the postulate in eqn [18]
was first derived by Voinov, using hydrodynamic ap-
proximations near the moving contact line, resulting
in:
 3D
 3S ¼ 9Ca lnðY=Ym Þ ½19
where Y/Ym is a ratio of macroscopic length over
which the contact angle is defined ( mm) to molecu-
lar length where continuum theories fail ( nm). Ap-
plication of eqn [19] with Y/Ym ¼ 105 to the data of
Hoffman is depicted in Figure 9. A key shortcoming
of such hydrodynamic models for a dynamic contact
Figure 9 Experimental results of Hoffmann fitted with eqn [17]
(Hoffmann RL (1975) A study of advancing interface. Journal of
Colloid Interface Science 50: 228–241), and approximations given
by eqns [16] and [19]. Note that, for water flow in soils, the
capillary number Ca rarely exceeds the range of values between
10
6 and 10
4 (for v ¼ 1 mm s
1, Ca ¼ 1  10
5). (Adapted from
Kistler SF (1993) Hydrodynamics of wetting. In: Berg JC (ed.)
Wettability, pp. 311–429. New York: Marcel Dekker.)
Figure 10 Finite difference computation versus eqn [18] and parameters from Kistler (Kistler SF (1993) Hydrodynamics of wetting.
In: Berg JC (ed.) Wettability, pp. 311–429. New York: Marcel Dekker.) for advancing (left) and receding (right) contact angle as a function
of Ca. (Adapted from Hirasaki GJ and Yang SY (2002) Dynamic contact line with disjoining pressure, large capillary numbers, large
angles, and prewetted, precursor, or entrained films. In: Mittal KL (ed.) Contact Angle, Wettability and Adhesion, vol. 2, pp. 1–30.)
CAPILLARITY 161
angle is the lack of consideration of the effects and
interactions with solid surface properties.
Heterogeneous Surfaces and
Microscale Hysteresis
Contact Angle on Chemically Heterogeneous
and Rough Surfaces
Consider a chemically heterogeneous surface made
up of patches of solids (or grains) with two different
equilibrium contact angles  a and  b, and with the
fraction of the area occupied by a solid given as f
(Figure 11). The apparent equilibrium contact angle
( e) for the composite surface is given by the semi-
empirical Cassie equation:
cos e ¼ f cos a þ ð1
f Þcos b ½20
An example of the Cassie law for contact angle of
water on a sand surface with increasing amounts of
hydrophobic grains is shown in Figure 12. The Cassie
law (eqn [20]) is in remarkable agreement with ex-
perimental data for sand (Figure 12) and silt surfaces.
An interesting extension of the Cassie law for
porous surfaces (soil, fabric, etc.) predicts that the
apparent contact angle ( e) should be proportional
to surface porosity (n):
cos e ¼ ð1
nÞcos a
n ½21
The negative sign associated with porosity is due to
the nonwetting properties of empty pores (i.e., air
with cos air ¼
1).
These concepts of mixed wettability can be incorp-
orated into the capillary rise model (eqn [6]) where
capillary rise takes place in slits formed between two
walls of different wettability. The same study applies
162 CAPILLARITY

the Cassie law to liquid retention in porous media and
demonstrates these effects on the hydraulic properties
of unsaturated porous media with varying surface
wettability.
In addition to surface chemical heterogeneity, the
roughness of a surface is known to alter its wettability
properties by increasing the wettable surface area
per unit projected area, and by enabling a complex
interplay between macroscopic contact angle and
microscale geometry, leading to gas entrapment and
a patchwork of microinterfaces underneath the wet-
ting fluid. A spectacular demonstration of surface
roughness-induced super hydrophobicity with a
water drop resting on a fractal hydrophobic surface
and forming a contact angle of about 170 is shown in
Figure 13a. Such enhanced hydrophobicity is not only
important for a variety of engineering and industrial
treatments aimed at waterproofing of surfaces and
fabrics, but it may also be important for explaining
wettability properties of natural soil surfaces.
Assuming that surface roughness only affects
the solid–liquid and solid–vapor interfacial areas,
minimization of surface free energy results in the so-
called Wenzel equation:
cos e ¼ rcos ½22
where  is the static contact angle for a smooth sur-
face of similar chemical composition (see scheme in
Figure 11b).
The scope of surface influence is more complicated
than predicted by simple expressions such as the
Cassie and Wenzel equations. Other factors such as
details of roughness geometry, interfacial pinning,
and air trapping conspire to accentuate surface wet-
ting properties as shown in Figure 13b. The scheme
depicted in Figure 13b is based on experimental
results showing the apparent contact angle on a
rough surface plotted against the static contact angle
on a smooth surface with similar chemical compos-
ition (to isolate the influence of surface roughness).
Subsequent studies have shown a range of behaviors
and asymmetry between the hydrophobic (cos < 0)
and hydrophilic (cos > 0) sides of Figure 13b. It is
interesting to note that certain roughness patterns

Figure 11 Definition sketch for contact angle formation on (a) chemically heterogeneous surface and (b) rough surface with r ¼
A/

A0, where A0 is the projected area over a smooth surface. (Reproduced from McHale G and Newton MI (2002) Frenkel’s method and
the dynamic wetting of heterogeneous planar surfaces. Colloids and Surfaces A 206: 193–201.)

Figure 12 Application of the Cassie law to (a) experimental results of contact angle with sand surfaces containing different
proportions of hydrophobic (treated) sand grains; and (b) an image of a water droplet on nonwetting sand forming a contact angle
of 95 . (Adapted from Bachmann J, Elliesb A, and Hartgea KH (2000) Development and application of a new sessile drop contact angle
method to assess soil water repellency. Journal of Hydrology 231: 66–75.)
 CAPILLARITY 163

Figure 13 (a) Water drop (r ¼ 1 mm) resting on fractal rough surface with r ¼ 4.4 (eqn [22]); and (b) apparent contact angles as a
function of surface microroughness for a range of surfaces with different wettability. (Reproduced with permission from Onda T,
Shibuichi S, Satoh N, and Tsujii K (1996) Super-water-repellent fractal surfaces. Langmuir 12: 2125–2127.)

Figure 14 Two microscale mechanisms for hysteresis in capillary behavior: (a) differences between advancing and receding
contact angle; and (b) the ‘ink bottle’ effect depicting two different amounts of liquid retained in identical pores under the same matric
potential.

induce formation of air patches trapped underneath From early observations to the present, the role of
the liquid (similar to water drops resting on surfaces individual factors remains unclear, and hysteresis is a
of some plant leaves). subject of ongoing research.

Hysteresis See also: Water Potential; Water Retention and

The amount of liquid retained in a porous medium is
not uniquely defined by the value of the matric poten-
tial but is also dependent on the ‘history’ of wetting
and drying. This phenomenon, known as hysteresis, is
closely related to various aspects of pore geometry,
capillarity, and surface wettability. The macroscopic
manifestation of hysteresis in soil water retention (or
soil water characteristic) is rooted in several micro-
scale mechanisms, including: (1) differences in liquid–
solid contact angles for advancing and receding water
menisci (Figure 14a), which is accentuated during
drainage and wetting at different rates; (2) the ‘ink
bottle’ effect resulting from nonuniformity in shape
and sizes of interconnected pores, as illustrated in
Figure 14b, whereby drainage of the irregular pores
is governed by the smaller pore radius r, and wetting
is dependent on the larger radius R. Additional effects
stem from pore angularity; (3) differences in air-
entrapment mechanisms; and (4) swelling and shrink-
ing of the soil under wetting and drying, respectively.
Characteristic Curve
Further Reading
Adamson AW (1990) Physical Chemistry of Surfaces, 5th
edn. New York: John Wiley.
Bachmann J, Elliesb A, and Hartgea KH (2000) Develop-
ment and application of a new sessile drop contact
angle method to assess soil water repellency. Journal of
Hydrology 231: 66–75.
Bico J, Thiele U, and Quere D (2002) Wetting of textured
surfaces. Colloids and Surfaces A 206: 41–46.
Blunt M and Scher H (1995) Pore-level modeling of
wetting. Physical Review E 52(6): 6387–6403.
Dullien FAL, Lai FSY, and Macdonald IF (1986) Hydraulic
continuity of residual wetting phase in porous media.
Journal of Colloid Interface Science 109: 201–218.
Friedman SP (1999) Dynamic contact angle explanation of
flow rate-dependent saturation-pressure relationships
during transient liquid flow in unsaturated porous
media. Journal of Adhesion Science Technology 13:
1495–1518.
164 CARBON CYCLE IN SOILS/Dynamics and Management
Haines WB (1930) Studies in the physical properties of soil.
V. The hysteresis effect in capillary properties, and the
modes of moisture distribution associated therewith.
Journal of Agricultural Science 20: 97–116.
Hamraoui A and Nylander T (2002) Analytical approach
for the Lucas–Washburn equation. Journal of Colloid
and Interface Science 250: 415–421.
Hirasaki GJ and Yang SY (2002) Dynamic contact line
with disjoining pressure, large capillary numbers,
large angles and pre-wetted, precursor, or entrained
films. In: Mittal KL (ed.) Contact Angle, Wettability and
Adhesion, vol. 2, pp. 1–30. Zeist, the Netherlands: VSP.
Hoffman RL (1975) A study of advancing interface. Journal
of Colloid Interface Science 50: 228–241.
Kistler SF (1993) Hydrodynamics of wetting. In: Berg JC
(ed.) Wettability, pp. 311–429. New York: Marcel
Dekker.
Kool JB and Parker JC (1987) Development and evaluation
of closed-form expressions for hysteretic soil hydraulic
properties. Water Resources Research 23: 105–114.
Lucas R (1918) Ueber das Zeitgesetz des kapillaren Auf-
stiegs von Flussigkeiten. Kolloid Zeitschrift 23: 15–22.
Marmur A (1992) Wettability. In: Schrader ME and Loeb
GI (eds) Modern Approaches to Wettability: Theory and
Applications. New York: Plenum Press.
McHale G and Newton MI (2002) Frenkel’s method and
the dynamic wetting of heterogeneous planar surfaces.
Colloids and Surfaces A 206: 193–201.
Morrow NR and Xie X (1998) Surface energy and imbibi-
tion into triangular pores. In: van Genuchten MT, Leij
FJ, and Wu L (eds) Proceedings of International Work-
shop on the Characterization and Measurement of the
Hydraulic Properties of Unsaturated Porous Media.
Riverside, CA: University of California Press.
Nitao JJ and Bear J (1996) Potentials and their role in
transport in porous media. Water Resources Research
32: 225–250.
Onda T, Shibuichi S, Satoh N, and Tsujii K (1996)
Super-water-repellent fractal surfaces. Langmuir 12:
2125–2127.
Quere D, Raphael E, and Ollitrault J-Y (1999) Rebounds in
a capillary tube. Langmuir 15: 3679–3682.
Rideal EK (1921) On the flow of liquids under capillary
pressure. Philosophical Magazine 44: 1152–1159.
Rye RR, Mann JA Jr., and Yost FG (1996) The flow of
liquids in surface grooves. Langmuir 12: 555–565.
Sciffer S (2000) A phenomenological model of dynamic
contact angle. Chemical Engineering Science 55:
5933–5936.
Shibuichi S, Onda T, Satoh N, and Tsujii K (1996) Super
water-repellent surfaces resulting from fractal structure.
Journal of Physical Chemistry 100: 19512–19517.
Tuller M, Or D, and Dudley LM (1999) Adsorption and
capillary condensation in porous media: liquid retention
and interfacial configurations in angular pores. Water
Resources Research 35(7): 1949–1964.
Ustohal P, Stauffer F, and Dracos T (1998) Measurement
and modeling of hydraulic characteristics of unsatur-
ated porous media with mixed wettability. Journal of
Contaminant Hydrology 33: 5–37.
Voinov OV (1976) Hydrodynamics of wetting. Fluid
Dynamics 11: 714.
Washburn EW (1921) The dynamics of capillary flow.
Physical Review 17: 273–283.