Understanding and explaining surface tension and capillarity:

an introduction to fundamental physics for water professionals

Marios Sophocleous
Abstract Understanding and explaining surface tension
and capillarity are not easy tasks. In this manuscript, an
attempt is made to explain such phenomena for the
generally educated professional. Following a conceptual
explanation of the molecular basis of surface tension, it is
shown that the true force exerted by the solid walls of a
capillary tube on the liquid causing capillary rise is the
difference in the surface tensions of the solid-liquid and
solidvapor interfaces leading to free surface energy
reduction on wetting the solid walls of the capillary bore,
and not the pressure drop at the curved interface. It is also
shown that the water in the capillary tube is suspended
from the meniscus and is under tension, rather than being
pushed up the capillary from below. The energy necessary
for capillary rise, being derived from the diminution of
surface energy that accompanies the movement of liquid
in the capillary, emphasizes the important role of wetting
in characterizing surface phenomena. A recommended
explanation of capillary rise incorporates the reduction in
free surface energy on wetting the inside walls of the
capillary bore, where the opposition offered to spreading
by the weight of the raised liquid is smaller (because of
the narrowness of the bore) than that of the outside walls.
Keywords Capillary rise
.
Unsaturated zone
.
Wetting
phenomena
.
Young's equation
.
Interfacial energy
Introduction
The subject of surface tension and capillarity is complex
with sophisticated mathematics, and is thus difcult for
both students and water professionals to understand. As a
result, most university physics/soil physics textbooks
(such as Tipler 1991; Giancoli 1988; Miller and Schroeer
1987; Snow and Shull 1986; Kane and Sterheim 1984;
Sears et al. 1982; Jury and Horton 2004; Hillel 1998;
Marshall and Holmes 1988; Bear 1979; Kirkham 2005, to
name a few among others) present elementary and
simplied explanations of such phenomena, which often
lead to confusion and frustration, as also experienced by
this author. The conceptual difculty with understanding
and explaining the capillary-rise equation as presented in
these textbooks is the following: on the one hand, surface
tension, g, is portrayed as a net inward force at the air-
water interface, and on the other hand, the surface tension
force is portrayed as an upward force that counter-
balances the downward gravity force in deriving the
capillary-rise equation. Further confusion is encountered
when considering whether the risen water column is
pushed up or pulled up the capillary and what actually is
the driving force for capillary rise. As other generally
educated professionals, and especially water-related pro-
fessionals, may have encountered similar problems under-
standing such issues, the author has attempted in this
paper to present a critical review and synthesis of selected
aspects of the multidisciplinary subject matter of surface
tension and capillarity in a comprehensive, logical, and
more easily understandable manner. The explanatory
approach is purposely kept largely qualitative and
mechanical, avoiding the formalism of thermodynamics
so as to reach a larger water-professional audience.
Why are surface phenomena, which may sound esoteric,
of interest to water professionals? Surface phenomena
comprise an area that is generally neglected by water
professionals, as a quick look at the standard hydrogeology
textbooks (Freeze and Cherry 1979; Domenico and
Schwartz 1998; Fetter 2001) can attest. However, in this
age of broadened horizons, nanotechnology, and interdisci-
plinary science, surface-science topics related to interfacial
and capillary phenomena constitute an indispensable basic
background for understanding vadose hydrology, ecohy-
drology, geomicrobiology, petroleum hydrogeology, multi-
phase transport through porous media, and other disciplinary
themes. Common conceptual models for water retention in
porous media and matrix potential rely on a simplied
representation of pore space as a bundle of capillaries
resulting in the representation of soil and rock pores as
equivalent cylindrical capillarieswhich greatly simplies
Received: 19 May 2009 / Accepted: 30 November 2009
Published online: 15 January 2010
Springer-Verlag 2009
M. Sophocleous ())
Kansas Geological Survey,
University of Kansas,
1930 Constant Ave., Lawrence, KS 66047, USA
e-mail: marios@kgs.ku.edu
Tel.: +1-785-8642113
Fax: +1-785-8645317
Hydrogeology Journal (2010) 18: 811821 DOI 10.1007/s10040-009-0565-5
modeling and parameterization of porous media pore space
(Or and Tuller 2005). It is hoped that this overview article
will both educate and stimulate the interest of water
professionals, creating a better understanding and appreci-
ation of the complexities of surface-science phenomena as
related to their particular disciplines.
The molecular basis of surface tension
The molecules in a uid experience attractive and
repulsive forces in all directions due to the surrounding
molecules. Because the repulsive forces have a much
shorter range than the attractive forces, and are important
only at extremely high external pressures (Hunter 2001),
attractive forces generally predominate. The resultant
force on such molecules in the bulk of the uid, averaged
over a macroscopic time (a time which is much longer
than that spent in collisions between molecules), will be
zero (Isenberg 1992). The interaction of a given molecule
with its (nearest) neighbors leads to a reduction of its
potential energy, i.e., intermolecular forces act to stabilize
the system (Pellicer et al. 1995). Such forces give rise to
cohesion among the molecules of a liquid and to
adsorption or adhesion between molecules of that liquid
and any bounding solid surface. The molecules at the
surface region of the uid have a smaller number of
nearest neighbors (as the density of the gaseous region
above the surface is considerably smaller than that of the
bulk uid), and therefore their potential energy is not
decreased as much as in the interior of the uid.
Molecules near the surface of the uid experience a
weaker force from the gaseous region above the surface
than they would if the gaseous region was replaced by
uid. Thus, such molecules will experience, on average, a
force, normal to the surface, pulling them back into the
bulk of the uid. It is therefore necessary to do work
against this force to take a molecule from the interior to
the surface, and consequently the surface molecules
possess greater energy than those inside the liquid (Brown
1947). In other words, considering the potential energy of
water molecules inside bulk water as zero, the molecules
at the interface have a positive potential energy. This is
characterized by the surface tension, which is the interface
potential energy divided by the interface area (J/m
2
),
which manifests itself as a force per unit length (N/m), the
two units being the same (in SI units they correspond to
Nm/m
2
and N/m, respectively). According to Hunter
(2001), only a few attempts have been made to explain
how such an apparently unbalanced intermolecular force
normal to the surface can be responsible for a stress
parallel to that surface, giving rise to surface tension.
In accordance with the principle that every system
moves towards a state of minimum potential energy, if
free to do so, the surface of a liquid shows a tendency to
contract (Brown 1947). The smallest surface area for a
given mass of water is that of a sphere. This explains the
formation of spherical droplets of rain, sprays, etc. Any
other shape would represent a larger surface area and thus
a higher energy content. For the same reason, the
meniscus of water in a capillary generally assumes the
spherical shape.
Hunter (2001) presents a qualitative outline of Orowans
(1970) more mathematical argument for the existence of a
surface tension as a consequence of the attractive (and
repulsive) forces between molecules, based on the balance
of forces on innitesimal cubic elements of uid near the
surface. The forces arise from the pressure within the uid,
so an understanding of the molecular basis of pressure is
needed (Hunter 2001). It will be shown here how this
pressure is anisotropic near the surface, which leads to a
tension in the surface. In equilibrium, the pressure in a uid
is the time-averaged normal force per unit area exerted by
all the molecules on one side of an imaginary test surface
on all the molecules on the other side of the test surface.
This pressure can be separated into two parts (Berry 1971):
1. A kinetic contribution, p
k
, due to the transport of
momentum by molecules moving across the test
surface. This is the familiar pressure term in the kinetic
theory of a perfect gas. It is the same for a liquid and is
always positive (Hunter 2001).
2. A cohesive contribution to the pressure due to the time
average of the net attractive and repulsive forces
between molecules on opposite sides of the imaginary
test surface in the body of the uid. This second
contribution is called the static pressure, p
s
, is
normally negative (i.e., the attractive force, conven-
tionally given a negative sign, dominates) and is
particularly important for dense gases or liquids. The
total pressure, P p
k
p
s
_ _
, is the sum of these two
contributions and is thus less than the kinetic pressure,
and must be equal to the applied pressure, that is the
vapor pressure for a one-component system (Hunter
2001).
Neglecting the repulsive forces when considering the
static pressure (because the repulsive forces, as mentioned
earlier, have a much shorter range than the attractive
forces and are important only at extremely high external
pressure), the intermolecular forces can be considered to
have a sphere of inuence beyond which they are
negligiblean idea introduced by Laplace in 1806
(Hunter 2001). The intermolecular forces extend only
over a short range of the order of 10 (Angstrom) for
simple molecules (Jaycock and Partt 1981). For mole-
cules further from the surface than the diameter of this
sphere, the pressure must be isotropic because of the
symmetry of their surroundings.
Near the surface between the two bulk phases, the
tangential and normal contributions to the static pressure
are not the same because of the asymmetric distribution of
molecules within the sphere of inuence. When the sphere
of inuence cuts the surface (Fig. 1a), fewer and fewer
pairs of molecules attract across an imaginary test plane
near a liquid surface as the center of the sphere approaches
the surface; hence, the magnitude of the static-pressure
contribution decreases for both the pressure across a plane
812
Hydrogeology Journal (2010) 18: 811821 DOI 10.1007/s10040-009-0565-5
parallel to the surface and for the pressure across a plane
normal to the surface (Hunter 2001). It is apparent that
when the test plane is in the surface (Fig. 1b), the decrease
in magnitude of the normal static pressure is greater than
the decrease in magnitude of the tangential static pressure
because of the smaller number of interactions remaining in
the former case.
Now consider the consequences of the fact that the
forces on opposite sides of an innitesimally small cube of
uid must be equal and opposite for mechanical equili-
brium to exist. Referring to Fig. 2, which is taken from
Berrys (1971) paper and also summarized in Temperley
and Travena (1978), in the bulk vapor (A) or bulk liquid
(C), there is directional symmetry in the distribution of the
molecules and so the pressure has the same value p
0
irrespective of the orientation of the test surface used to
dene it. However, in the surface region (B), the tangential
pressure p
t
and the normal pressure p
n
will not be the
same because there is no longer symmetry of direction,
there being depletion in the vertical z direction but not in
the horizontal x direction. However, because the uid is in
equilibrium, the forces on the opposite faces of the three
small cubes shown must be equal and opposite. Thus,
neglecting gravity changes between A and C, the normal
pressure p
n
has the same constant value p
0
between A and
C, right through the surface layer. On the other hand, the
tangential pressure p
t
is equal to p
0
in the bulk vapor at A
and in the bulk liquid at C, but is not equal to p
0
in the
surface layer. The resultant net stress is the surface
tension. Thus energy is stored in the form of surface
tension as in a stretched spring. Berry (1971) concludes
that the surface layer of liquid, in contrast with the bulk,
must possess rigidity in order to resist the shear stress that
results from p
t
differing from p
n
; this is the basis for the
statement appearing in older textbooks that liquids behave
as if their surfaces are covered by an elastic skin.
Objects do not remain in positions of high potential
energy unless the force by virtue of which they possess that
energy is balanced by some other equal and opposite force.
Following Browns (1947) argument, suppose that the
surface has reached its minimum area and that the
concentration of molecules near the surface is the same as
it is in the interior. This condition cannot persist because
there is no force to balance the inward attraction experi-
enced by the surface molecules. Therefore, the surface
molecules will continue to pass into the interior until the
reduced concentration in the surface sets up a pressure
Fig. 1 a Schematic of the sphere of inuence of radius of a
molecule B below a plane and curved surface (XX and SS
respectively) with imaginary test planes parallel and normal to the
surface (shown as short bold lines at the center of the sphere of
inuence). CD is the diameter of the sphere of inuence of molecule
B and is parallel to the plane surface XX. CD is the region of
intersection of the sphere of inuence of molecule B with the plane
surface XX. A represents a molecule in the bulk of the liquid. b
Sphere of inuence around imaginary planes in the liquid surface
with test planes parallel and normal to the surface. Note the
attraction between molecules in quadrants (I + II) and (III + IV) in
the diagram for normal forces (i) will be very small because there
are very few molecules in quadrants III and IV. Attraction between
molecules in quadrants (I + IV) and (II + III) in the diagram for
tangential forces (ii) will be much greater as quadrants I and II are
densely populated. (a Adapted from Temperley and Travena 1978;
and b from Hunter 2001)
Fig. 2 Schematic of equilibrium of elementary uid cubes in liquid, vapor, and surface (adapted from Berry 1971)
813
Hydrogeology Journal (2010) 18: 811821 DOI 10.1007/s10040-009-0565-5
gradient opposing the inward attraction (Brown 1947).
This explains why the number of molecules in the surface,
and hence the surface area itself, tends to decrease. Of
course, this process of contraction is eventually opposed by
the repulsive forces between the molecules, which prevent
a complete inward collapse of the liquid (Temperley and
Travena 1978). An example of this is the increased
hydrostatic pressure within an isolated liquid droplet that
opposes the contractile tendency of the surface (surface
tension) and thus provides the necessary restoring force. As
a result, when equilibrium is reached, there are fewer
molecules per unit volume in the surface than in the
interior, resulting in a smaller liquid density, which means a
smaller pressure. Thus, the surface layer is in a state of
tension resulting from the decrease in pressure in the
surface layer compared with the condition of the interior
(Brown 1947).
As Brown (1947) stresses, the uid character of the
substance is essential to this argument. No shearing forces
exist within the liquid itself to oppose the inward ow of
molecules until the lack of molecules near the surface
establishes an opposing force. The lower molecular
concentration in the surface is an example of the general
principle that molecules distribute themselves with smaller
concentrations at places of higher potential energy (Brown
1947). A good deal of evidence shows that, as might be
expected, the surface layer of a liquid is depleted. That is,
the number density of the molecules is less than that in the
bulk liquid. Experiments using polarized light suggest that
this decreased-number density is conned to a layer
whose thickness is just a few molecular diameters
(Temperley and Travena 1978).
Pressure difference across an interface
and contact angle
Following Temperley and Travena (1978), consider a
molecule B, part of whose sphere of inuence of radius a
lies above the surface, as shown in Fig. 1a under a plane
(XX) and under a curved (SS) surface. The resultant
force on B due to its neighboring molecules will then be
directed inward () along the normal to the surface, as
there are a greater number of molecules in the hemisphere
below CD than in the volume CDDCC above CD; the
nearer B is to the surface XX, the greater the inward
resultant force on B. As the distance y of a molecule
below XX increases from zero to a, this inward force on
B changes from its maximum value to its minimum value
of zero and remains zero for all y>a, as in molecules like
A in Fig. 1a.
Now compare the downward force on molecule B
under a curved liquid surface, SSconcave towards the
bulk of the liquid (Fig. 1a)with what it would be if the
liquid surface were the plane surface XX (Temperley and
Travena 1978). In the case of the curved surface, there is a
greater volume of the sphere of inuence above the liquid
surface (shown as a hatched area in the gure) and so,
from the reasoning above, there is a greater downward
force on B in this case. Hence, it follows that the intrinsic
pressure (due to the cohesive forces) at a distance y below
the upper point of the curved surface is greater than that at
the same depth below a plane surface. Further, the
pressure at this point below a curved surface increases as
y increases to y=a, and is constant for all y>a. Similarly
when the liquid surface is convex towards the liquid, the
pressure below the surface is less than that below a plane
surface.
Thus, when the liquid (L)vapor (V) interface is curved
rather than planar (at), the resultant surface tension force
normal to the liquidvapor interface creates a pressure
difference across the interface. The pressure is greater at
the concave side of the interface by an amount that is
dependent on the radius of curvature and the surface
tension of the uid. The pressure difference across the
interface is given by the Young-Laplace equation (Or and
Wraith 2002; Or and Tuller 2005)
$P g
LV
1
R
1

1
R
2
_ _
; 1
where g
LV
is the interfacial surface tension and the interface
curvature is specied by the radii of curvature along two
orthogonal directions, say R
1
and R
2
, and DP P
L
P
V
when the interface curves into the gas phase (water droplet
in air) or DP P
V
P
L
when the interface curves into the
liquid (air bubble in water, water in a small glass tube); P
L
and P
V
are the liquid and vapor pressures, respectively. The
sign of R
i
is negative for convex interfaces (R
2
< 0) and
positive for concave interfaces (R
1
> 0). For a hemi-
spherical liquidvapor interface having radius of curvature
R, R
1
= R
2
= R, and Eq. (1) reduces to
DP
2g
LV
R
: 2
A short proof of Eq. (2) may be adduced here
(Bikerman 1970). Imagine a spherical bubble of radius R
immersed in a liquid but still connected to a source of air.
If more air is reversibly pumped into the bubble to
increase the radius to R + dR, the work done against the
pressure P inside the bubble is P4R
2
dR. At the same
time, the area of the bubble increases by 8RdR and the
work performed against the surface forces is g8RdR. As
both expressions physically represent an identical amount
of energy, they must be equal, i.e., P4R
2
dR = g8RdR.
Hence, Eq. (2) is the result.
The existence of surface tension is a direct con-
sequence of the facts that (1) intermolecular forces have
a short range of action and (2) the concentration of
matter in the gas phase, as a rule, is very much smaller
than in a liquid (Bikerman 1970). The asymmetric eld
of force across the vaporliquid interface also causes a
change in the internal pressure across the interface, if it
is curved.
When a liquid is brought into contact with a solid
surface, adhesion of the liquid with the solid and with the
814
Hydrogeology Journal (2010) 18: 811821 DOI 10.1007/s10040-009-0565-5
ambient air and cohesion of the liquid become interacting
forces. The contact angle, (i.e. the angle between the
liquid surface and the solid, measured in the liquid, at the
contact linethe location where the liquid surface meets
the solid surface) is often seen as a result of the balance of
these forces. This is shown in Fig. 3.
Following the arguments given by Thomas Young
about 200 years ago, the contact angle is the result of a
mechanical equilibrium of the forces acting on a unit
length of the contact line (Roura 2007). One obvious force
is the liquid surface tension g
LV
(Fig. 3). Its component
normal to the surface, g
LV
sin , would be equilibrated by
the adhesion of the liquid molecules to the solid surface.
On the other hand, to equilibrate the tangential compo-
nent, g
LV
cos , a surface tension for the solidliquid and
solidvapor interfaces (g
SL
and g
SV
, respectively) must be
introduced. The equilibrium of these forces parallel to the
solid surface leads to the famous Youngs equation or
Young-Dupr equation (Fig. 3):
g
LV
cos g
SV
g
SL
; 3
which states that the contact angle depends exclusively on
the surface tensions and that it is independent of the
particular solid-liquid system (such as drops or capillaries)
and gravity. Typical values of the interfacial tensions from
Bailey and Kay (1967) as presented in Jaycock and Partt
(1981) are reproduced in Table 1 to give an idea of their
numerical orders of magnitude.
Equation (3) assumes that (1) the solid phase is an ideal
one, hence it should be smooth, at, rigid, chemically
homogeneous, insoluble, and non-reactive; (2) the liquid
phase is pure, hence no mixture of liquids can be used; and
(3) vapor adsorption to the solid phase is negligible (Gilboa
et al. 2006; Kwok and Neumann 1999). Thus, Eq. (3) has
only limited practical signicance in soil-water studies
because soils are rough, heterogeneous, anisotropic, elastic,
deformable, and may react with a wetting uid (Bachmann et
al. 2003); however, Youngs Eq. (3) is the starting point for
the investigation of soil surface properties.
The surface tension of a solid surface can be
signicantly reduced as a result of the adsorption of the
vapors of the wetting uid onto the solid surface, and
when the solid surface is in equilibrium with the liquid
vapor, such reduction is termed the equilibrium spreading
pressure (or lm pressure),
e
. Thus, Youngs equation
was modied as:
g
LV
cos g
S
g
SL
p
e
where p
e
g
S
g
SV
, and g
S
is the surface tension of the
solid in vacuum (Gilboa et al. 2006). However, if the
contact angle is greater than zero, the spreading pressure
may be regarded as negligible for low-energy solids
solids that resist wetting (Good 1993); that is, vapor
adsorption is considered to be negligible, and hence +
SV
=
+
S
. In many studies,
e
is ignored or kept at low and
constant levels by conducting measurements of contact
angle on air-dry soils (Gilboa et al. 2006).
Generally, it is extremely difcult to verify Youngs
equation because the values of g
SV
and g
SL
are very
difcult to measure, especially for irregularly shaped solid
particles such as soil particles. A conceptual difculty
with the mechanical justication of Youngs equation is
how a surface tension such as +
SV
can develop on a at
solid surface that is undeformable, and how it can act on a
contact line that is allowed to move freely above it (Roura
2007). Orowan (1970) pointed out that the difference of
surface tensions on the right-hand side of Eq. (3) should,
strictly speaking, be interpreted as a difference in surface
energies (more properly free surface energies in order to
denote the mechanical energies stored per unit area of
surface and available to perform mechanical work), which
correspond to the tangential stresses exerted by the solid
on the wedge of liquid adjacent to it.
Capillary rise
Adhesion and cohesion forces cause water to rise in glass
tubes and in soil pores. Adhesion, attaching water
molecules to the solid surface, and cohesion, which joins
the water molecules together, combine to allow the water
to rise. The adhesion causes the rise in a capillary, and the
cohesion makes all the water molecules follow the upward
pull (Ehlers and Goss 2003). The concave curvature
indicates the presence of a pressure below the water
surface being smaller than the surrounding normal,
Fig. 3 A liquid drop schematic in a a wetting situation with
contact angle < 90, and b a non-wetting situation with > 90 on
a planar solid surface. g is the interfacial tension between the phases
indicated by the subscripts. Thus, subscripts SV, SL, and LV stand
for solidvapor, solidliquid, and liquidvapor, respectively
Table 1 Parameters in the Young equation in milliNewtons/m at
room temperature. The solid (S) employed is mica, and the subscript
V represents the vapor of the specied liquid (L) (adapted from
Jaycock and Partt 1981)
Liquid g
SV
g
SL
g
LV
Water 182.8 107.3 72.8
Hexane 271.0 255.0 18.4
815
Hydrogeology Journal (2010) 18: 811821 DOI 10.1007/s10040-009-0565-5
atmospheric pressure. Therefore, the concave shape
signies a sub-atmospheric or negative pressure in the
water in the capillary tube. Is the water column in the
capillary tube the result of this sub-atmospheric pressure
or is the very capillary water column the cause of this sub-
atmospheric pressure? In other words, what is the true
force causing the liquid column to rise in the capillary?
This question is investigated in the following.
According to McCaughan (1987), Tabor (1991) and
others, the proper way to treat the rise of water in the
capillary tube is in terms of the pressure difference across
the meniscus. Following McCaughan (1987) and ignoring
air and vapor pressure, P
A
= P
C
= 0, and by Pascals
principle, P
C
= P
D
= 0 (Fig. 4a), where P
A
is the pressure
at point A, just below the meniscus in the capillary, and
P
C
and P
D
are the pressures at the liquid reservoir level
outside and inside the capillary, respectively. Now P
B
<
P
A
, where P
B
is the pressure at point B just below the
central surface of the meniscus in the capillary, so that
P
D
> P
B
and a pressure gradient exists producing a force
acting vertically upwards over the entire bulk of the liquid
column in opposition to the weight of the straight-wall
column. In quantitative terms, by Newtons second law:
P
D
P
B
gh pr
2
0;
where is the liquid density, g is the acceleration of
gravity, r is the capillary radius, and h is the height of the
liquid drawn up the capillary tube.
From Eq. (2) and the above reasoning, P
A
P
B

2g
LV
R
P
D
P
B
. On substitution
2g
LV
R
gh
_ _
pr
2
0 is
obtained. From Fig. 4 it can be seen that R cos = r, or
R = r/cos . Then, substituting that result
h
2g
LV
cos
gr
: 4
This treatment has ignored the liquid that stands higher
than point B in the curved portion of the meniscus
(Fig. 4a). Bikerman (1970) provides a more precise
treatment that incorporates the curved portion of the
meniscus that stands higher than point B.
The same result can be obtained for a conical capillary
(Fig. 4b) in agreement with experimental observation (Tabor
1991). It should be clear, however, that in the case of a
conical or other shaped capillary, the liquid will not rise on its
own accord to height h because it will not be able to traverse
the wider parts of the tube. The situation in the conical
capillary mentioned above is stable if the liquid is sucked up
to height h and then the suction is removed. Thus, it is not
necessary for the capillary to have a small radius throughout
its length. Only the capillary radius at the meniscus is
relevant (Fig. 4) in determining the height of the column that
can be supported in a capillary tube (Hunter 2001).
In a further comment on capillary rise, McCaughan
(1992) provided the following explanation of that phe-
nomenon. At rst, with the curved surface at the bottom
of the capillary tube (the lower end of which is placed
just below the free surface of a large reservoir of liquid),
the gradient extends outside the bottom of the tube into
the liquid reservoir because the lower pressure beneath the
curved surface is at the same level as the at surface of the
liquid in the reservoir, which is at the same pressure as
that above the curved surface. This external gradient
drives liquid into the tube and pushes the column
upward. Even if one were to suppose that the walls were
pulling up the liquid column through a perimeter force
that results from the upward pull by the glass around the
upper edge of the column of liquid (i.e., the vertical
component of the adhesive force exerted by the glass), one
then would have to explain how the liquid column is
sliding over the same walls where their effect is to oppose
the motion. According to McCaughan (1992), sliding
upwards must mean a push upward. In support of this
idea, Peiris and Tannakone (1980) show that capillary rise
moves according to the laws of viscous ow, and
Poiseuilles equation also assumes a pressure gradient as
the driving force.
Fig. 4 Schematic of the rise of liquid a in a straight and b in a conical capillary tube of radius r. A, B are points just above and just below
the central surface of the meniscus respectively. C, D are points at the liquid reservoir level outside and inside the capillary, respectively. h
is the height of rise of liquid in the capillary above the reservoir level, is the contact angle, and R is the radius of curvature of the meniscus
in the capillary
816
Hydrogeology Journal (2010) 18: 811821 DOI 10.1007/s10040-009-0565-5
Thus, in accordance with the arguments presented in the
preceding, the rise of a liquid in a capillary occurs because
the pressure under the convex side of the meniscus is less
than that along the opposite side of the interface. Bikerman
(1970) poses the question, Why does the higher pressure
above the liquid in the capillary tube not push the liquid
down? This certainly would have happened if the liquid
vapor interface were analogous to a piston.
According to Bikerman (1970) two satisfactory answers
are available. One of them is based on the analogy between
molecular and gravitational forces. Because of the gravita-
tional forces, the deeper layers of our planet Earth are
subjected to a high pressure, but this pressure has no
tendency to push the Earthatmosphere interface toward
the atmosphere. The other uses the analogy between surface
tension and the tension of an inated rubber balloon. The
excess pressure inside the balloon is not felt outside it and
does not push the walls out because it is exactly
compensated by the stresses in the rubber envelope. Thus
a drop, of radius R, has no tendency to swell although the
pressure in it is greater by 2g/R than the outside pressure; an
increase in volume would entail an increase in the area,
which is energetically unfavorable (Bikerman 1970).
Capillary rise is sometimes explained in terms of the
surface forces around the periphery of the meniscus
(Tabor 1991; Fig. 5c). The meniscus has peripheral length
2r, and for contact angle , the upward force is
2r g
LV
cos . This is balanced for straight-wall capillaries
by the downward weight of the liquid column, mg =
Vg = hr
2
g, where m is the mass of the uid column, V
is its volume, and all other symbols are dened previously
and/or in the last section (see Appendix). Thus, h g
2g
LV
cos
r
, a result already arrived at in Eq. (4). The
(mechanical) interpretation given previously, and also in
many textbooks that consider the topic of capillary rise
(Tipler 1991; Giancoli 1988; Miller and Schroeer 1987;
Snow and Shull 1986; Kane and Sterheim 1984; Sears et
al. 1982; Jury and Horton 2004; Hillel 1998; Marshall and
Holmes 1988; Bear 1979; Kirkham 2005; and others), is
that only g
LV
is invoked and the equilibrium is formulated
as a balance between the weight of the liquid column and
a force related to g
LV
(Pellicer et al. 1995). Most authors
then introduce the force exerted by the solid walls on the
liquid column as the reaction of the force exerted by
the liquidvapor interface on the line of contact (Fig. 5c).
The vertical component of this reaction force is then said
to cancel the weight of the liquid column (Pellicer et al.
1995), and the equation of capillary rise is written as
2prg
LV
cos g pr
2
h;
from which Eq. (4) results. Although Eq. (4) is correct,
Tabor (1991) points out that this is largely fortuitous. For
example, if the capillary was conical in shape (Fig. 4b),
the capillary rise would still be given by Eq. (4), where r
is the capillary radius at the point where the meniscus
formed. Clearly, 2r g
LV
cos could be considerably less
than the weight of the conical column of liquid. Addi-
tional weak points are present in the derivation of Eq. (4),
which will be outlined following the presentation of what
Pellicer et al. (1995) consider as the proper mechanical
interpretation of capillary rise.
According to Pellicer et al. (1995), the mechanical
interpretation of the capillary-rise equations can be done
properly by considering that the forces involved are the
surface tensions of the different interfaces, which act on the
line of contact, and the weight of the liquid column
(Figs. 5a, b). Two conditions of mechanical equilibrium
are needed: that of the liquid column and that of the line of
triple contact. For example, the force exerted by the liquid
vapor interface on the line of contact is 2rg
LV
and acts
along this interface, i.e. forming an angle with the solid
walls. The equation for capillary rise is then obtained in
two steps (Pellicer et al. 1995). First, consider the liquid
column (Fig. 5b) and note that the force exerted by the solid
tube on the liquid column, (g
SV
g
SL
) 2r, must compen-
sate for the weight of the liquid column mg, giving Eq. (5):
g
SV
g
SL
2pr mg: 5
(When g
SL
< g
SV
there is capillary rise; when g
SL
> g
SV
there is capillary depression). Expressing the uid mass m
of density and height h in the capillary tube of radius r as
m = r
2
h, Eq. (5) can be expressed as
g
SV
g
SL
2pr pr
2
hg; thus
2 g
SV
g
SL

gr
h:
6
It is thus evident that the surface free energy difference
Dg
s
g
SV
g
SL
is the driving force causing the liquid
column to rise if D
s
g
> 0, that is, if it is favorable for the
liquid to wet the solid wall (Henriksson and Eriksson
2004). At equilibrium, this surface free energy difference
equals a mechanical tension, the adhesion tension, acting
on the three-phase contact line.
It is noteworthy that the resulting equilibrium condition
(Eq. 6) does not involve the curvature of the meniscus or
the surface tension of the liquid, g
LV
. In other words,
following this route of capillary-rise interpretation, the
question as to why and how the meniscus is curved has
not been addressed (Henriksson and Eriksson 2004).
Thus, treating the subject matter along this route shows
Fig. 5 Schematic of the balance of forces in capillary rise: a
equilibrium of the line of triple contact (Eq. 3); b equilibrium of the
liquid column (Eq. 5); and c the situation usually depicted in
physics textbooks (Eq. 4) (Adapted from Pellicer et al. 1995)
817
Hydrogeology Journal (2010) 18: 811821 DOI 10.1007/s10040-009-0565-5
that the capillary rise is not caused by the pressure drop at
the curved interface, as indicated previously.
To introduce the contact angle and the surface tension
of the liquid, the second step in Pellicers et al. (1995)
analysis is followed (the rst step, as stated previously,
being the equilibrium of the liquid column), which
involves considering the equilibrium of the line of triple
contact (which, in turn, involves changes in the contact
angle but not in the mass/volume of the liquid in the
column), and Youngs equation (Eq. 3) is obtained.
Introducing Eq. (3) into Eq. (6) gives
2pr g
LV
cos gpr
2
h 7
or
2g
LV
cos
gr

2 g
SV
g
SL

gr
h; 8
assuming that the volume of the spherical cap at the top
of the liquid column is negligible. Thus, the left-hand
side of Eq. (8) indicates that the effects of the surface
energies of the SV and SL interfaces are hidden in the
contact angle .
According to Pellicer et al. (1995), there are several
weak points in the derivation of Eqs. (4) or (7). First,
nothing is said about the physical magnitudes determin-
ing the value of the contact angle. Second, the student
is left with the idea that capillary rise is directly related
to g
LV
, while Fig. 5b and Eqs. (5) and (6) state clearly
that the force exerted by the solid walls on the liquid
column is related to the difference in the surface
tensions of the liquidsolid and solidvapor interfaces.
The direction of the force in Fig. 5c is also misleading
because the solid walls can only exert forces in the
direction of the solid-liquid interface and cannot form
an angle with it (Pellicer et al. 1995). The surface
tension, g
LV
, considered as a force pulling the liquid
column up along a capillary wall is a misleading
concept. Wetting does not appear in the derivation of
Eq. (4), even though the wetting of the capillary wall
plays an important role in capillary rise. This is
evidenced by the fact that when the wall is wetted with a
liquid, the liquid rises up in the capillary tube, and when the
wall is not wetted by the liquid, the liquid is depressed in the
capillary tube, and also by the common observation that
the capillary rise is complete and reproducible only if the
liquid rst wets the walls above its surface (McCaughan
1992). Finally, the mechanical interpretation does not
explain where the energy necessary for capillary rise comes
from, which is further expanded on in the next section.
Is the liquid then pushed up in a capillary tube from the
bottom, as McCaughan (1987, 1992) and others contend,
or is it drawn up at the top by a climbing meniscus? It is
denitely known that the liquid pulls on the tube and
therefore the tube must pull on the liquid. Chapin (1959)
has shown that the capillary rise h (Eqs. 4 or 7) is obtained
even when the hydrostatic pressure is far too low (i.e.,
much less than gh) to account for it, and he advocates
abandoning the notion that the capillary rise can be
explained by hydrostatic pressure (i.e., by equating the
hydrostatic pressure of a column of liquid of depth h to
the reduction in pressure at the top of the column due to
the curvature of the meniscus). The analyses shown above
based on Pellicer et al. (1995), Henriksson and Eriksson
(2004), and others, show that the wall of the capillary tube
does exert an upward force on the liquid through the
surface free energy difference (g
SV
g
SL
). According to
Dingman (1984), the water in the capillary tube is
suspended from the meniscus, which in turn is attached
to the walls by hydrogen bonds. Thus, the water is under
tension, which is dened as negative pressure. Denny
(1993) points out that because the water in the tube is, in
essence, hanging from the airwater interface, it is at a
lower pressure than that of the surrounding air. As a result,
if one were to poke a hole in the side of the tube, air
would be drawn in rather than water being forced out.
This is in contrast to a column of water that has been
forced up from below, as argued by McCaughan (1987,
1992).
Source of the energy for capillary rise
Consider a tube of radius r. The liquid rises to a height h
given by Eq. (4). The energy required to establish
capillary rise is derived from the diminution of surface
energy which accompanies the movement of the liquid in
the capillary (Brown 1941). It follows therefore that the
equation relating capillary rise with the surface tension
and the radius of the tube (Eq. 4) may be established by
equating the loss of free surface energy to the work done
during the motion of the liquid. The potential energy of
the raised column, E
g
, gained by the liquid is equivalent
to the raising of a mass of liquid, m = r
2
h through a
height, h
cm
1=2h, where h
cm
represents the center of
mass of the liquid column with respect to the free surface
in the container. Hence,
DE
g
mgh
cm
1=2pr
2
h
2
g: 9
This energy comes from the wetting of the walls of the
tube by the liquid (Tabor 1991).
Consider a liquid with contact angle . The equilibrium
condition from Eq. (3) is
g
SV
g
LV
cos g
SL
: 10
Following Tabor (1991), if the liquid advances along
the tube so as to cover 1 m
2
of the surface, 1 m
2
of g
SV
is
destroyed and 1 m
2
of g
SL
gained. The area of the liquid
vapor meniscus has no change for a constant capillary
cross section. The energy given up by the system or the
loss of surface energy that occurs when an area 2rh of
the wall of the tube is wetted is 2rh (g
SV
g
SL
) or, by
Youngs equation, 2rhg
LV
cos . Thus, each m
2
of
818
Hydrogeology Journal (2010) 18: 811821 DOI 10.1007/s10040-009-0565-5
capillary surface wetted releases energy g
LV
cos. The
energy, E

, released for a rise of h is then

DE
g
g
LV
cos 2prh: 11
On the outside surface of the capillary, there is no
inherent physical possibility to reduce the airwater
interfacial area because further spreading up the outside
of the tube is prevented by the weight of the raised liquid.
However, inside the capillary, the interfacial area would be
reduced if the capillary would ll with water (Koorevaar
et al. 1983) because the opposition offered to spreading by
the weight of the raised liquid is smaller as a result of the
narrowness of the capillary bore. The reduction in air
(vapor)water interfacial energy can be used to draw
water up into the capillary against gravity. Above and
below the water level in the capillary, the walls of the
capillary are covered with a water lm (Koorevaar et al.
1983). Thus, after the initial wetting of the capillary walls,
the energy of the solidwater interfaces remains the same
independent of the height of liquid rise inside the
capillary. Thus, water will continue to enter the capillary
until the reduction in the airwater interfacial energy
brought about by an additional incremental volume of
water has become equal to the increase in gravitational
energy of that incremental volume in the capillary
(Koorevaar et al. 1983).
Substituting from Eq. (4) above for g
LV
cos , for the
loss of surface energy, E
g
:
DE
g
pr
2
h
2
rg: 12
This is exactly twice the gain in potential energy given
previously by Eq. (9). This implies that if the liquid were
non-viscous, it would rise to a height 2h and oscillate
between 0 and 2h with its mean position at h (Tabor
1991). In practice viscosity consumes the excess energy
very quickly. As Tabor (1991) explains, the behavior is
like that of a vertical spiral spring onto the end of which a
weight is suddenly attached. The weight falls instanta-
neously to double its equilibrium and oscillates between
this and zero until the kinetic energy is consumed by
friction and static equilibrium is achieved.
Alternative derivation of the source of energy
for capillary rise
Instead of considering that the height h of the liquid
column inside a thin capillary is the result of a mechanical
equilibrium of the net upward force of the surface tension
of the free liquid surfacethat equals the weight of the
liquid column, (Eq. 7)its value can be determined by
imposing a minimum total energy of the system (Mark-
worth 1971). The energy consists of the total surface
energies of the interfaces (LV, SL, and SV) and the
potential energy of the liquid inside the tube.
The starting point is the relation
DE DE
g
DE
g
; 13
where E is the change in total energy of the raised liquid
column, E
g
is the work done against gravity to construct
the liquid column, and E
g
is the corresponding change
in interfacial energy which arises from the fact that when
the liquid column is formed within the tube of radius r, an
interface characterized by g
SV
is changed to g
SL
.
DE
g

_
V
rgzdV

_
h
0
rgzpr
2
dz rgpr
2
h
2
2
_ _

1
2
prgr
2
h
2
; 14
where V = volume of uid in the capillary;
DE
g
g
SL
g
SV
2prh: 15
This last value can be easily understood if it is realized
that the wetted surface area has increased by 2rh at the
expense of an equal amount of dry surface area.
Using the familiar Young equation (Eq. 3): g
SV

g
SL
g
LV
cos; thus g
SL
g
SV
g
LV
cos, and thus,
DE
g
g
LV
cos2prh. Therefore,
DE DE
g
DE
g

1
2
pgr
2
h
2
2prhg
LV
cos : 16
The equilibrium height of the liquid column corresponds
to that value of h for which E has its minimum
value, i.e.
@DE
@h
0; thus
@
@h
1
2
pgr
2
h
2
2prhg
LV
cos
_

0; thus, pgr
2
h 2prg
LV
cos 0; which results in
Eq. (4).
From Eqs. (16) and (4) it can be shown that the
minimum value of E can be expressed as DE
min

1
2
pgr
2
2g
LV
cos
gr
_ _
2
2pr
2g
LV
cos
gr
_ _
g
LV
cos
1
2
pgr
2 2g
LV
cos
gr
_ _
2

pgr
2
2g
LV
cos
gr
_ _
2
;
which results in
DE
min

2pg
2
LV
cos
2

g
; 17
with E
g
= 2E
g
at this particular value of E. As
expected, (E)
min
is negative, regardless of whether the
liquid column is elevated or depressed and, in addition, is
independent of r. As Markworth (1971) also points out, this
approach lends considerable insight into the details of the
physical changes that occur as the liquid column is formed.
Concluding comments
It should have become evident by now that equating the
force of surface tension g
LV
around the circumference of
the meniscus in a capillary tube to the weight of the
819
Hydrogeology Journal (2010) 18: 811821 DOI 10.1007/s10040-009-0565-5
column of liquid is misleading and unnecessary as
physical principles are obscured. Based on the exposition
of surface phenomena outlined in this paper, the following
qualitative explanation of capillary rise is recommended.
When a small diameter, capillary tube is rst immersed in
a beaker with a liquid that has a tendency to adhere to the
walls of the capillary, molecules of vapor, escaping from
the liquid, adsorb to the solid surface of the capillary tube,
forming an extremely thin capillary layer just above the
liquidvapor interface. The mass of the liquid then
attempts to cohere to this layer and a raised meniscus
forms, both in the inside and outside walls of the capillary
tube, creating a new larger interfacial area. This larger
liquidvapor interfacial area of the adsorbed layer lm
represents relatively high energy that the system would
attempt to minimize by moving spontaneously to a state of
lower potential energy if the liquidvapor interface area
could be reduced. On the outside surface of the capillary,
there is no inherent physical possibility to reduce the
liquidvapor interfacial area as further spreading up the
outside of the tube is prevented by the weight of the raised
liquid. However, inside the tube, the opposition offered to
spreading by the weight of the raised liquid is smaller on
account of the narrowness of the bore. Consequently, for a
small-enough bore diameter of the capillary tube, a
considerable elevation occurs, and the rise ceases when
the weight of the raised column is equal to the force
causing spreading. (The volume of liquid lifted up above
the liquid reservoir level outside the capillary tube is the
same as that inside the capillary tube but in the conned
bore space of the tube that liquid volume is lifted higher.)
Furthermore, inside the capillary, the interfacial area
would be reduced if the capillary would ll with the
liquid as g
SL
< g
SV
, as the liquid tends to wet the capillary
tube, and the energy of the system is decreased by
increasing the solidliquid interface, i.e., by producing a
capillary rise effect. In short, although the capillary rise
equation (Eq. 4) was derived directly from the mechanical
equilibrium condition that must exist across any curved
interface, the reason why the liquid rises in the narrow
capillary tube against gravity is not because of that
equilibrium condition but instead because the interfacial
energy of the solidliquid interface (g
SL
) is appreciably lower
than that of the solidvapor interface (g
SV
). This leads to a
free surface energy reduction on wetting the solid walls of the
capillary tube that is balanced by the gain in gravitational
potential energy represented by the capillary rise.
Despite the fact that conceptual difculties still remain
such as questions related to solidvapor and solidliquid
interfaces of undeformable solid surfaces in Youngs
equation, briey mentioned earlier in this paper (see text
following Table 1)this exposition is a current attempt to
stress the importance of wetting in capillary rise and to
clarify some of the points which arise from the failure
to understand and explain the fundamentals.
Acknowledgements Detailed review comments by one eponymous
reviewer (Arye Gilboa) and three anonymous reviewers were helpful in
revising the manuscript. Previous discussions on aspects of surface
tension and capillarity with Lajpat Ahuja (USDA-ARS Agricultural
Systems Research Unit Leader, Fort Collins, Colorado), T.N. Nar-
asimhan (Department of Materials Science and Engineering, Univer-
sity of California-Berkeley, Paul Willhite (Chemical and Petroleum
Engineering, University of Kansas), and Scott Tyler (Department of
Geological Sciences and Engineering, University of Nevada-Reno)
were helpful in developing this manuscript.
Appendix: notation
Symbol description
Radius of sphere of inuence of
intermolecular forces [L]
g Interfacial surface tension [M T
2
]
g
LV
, g
SL
, g
SV
Interfacial surface tension
between different phases: liquid
(L) and gas/air/vapor (V) subscripts
SL and SV stand for solidliquid and
solidvapor interfaces, respectively
[M T
2
]
g
S
Surface tension of a solid in vacuum [M T
2
]
g
s
Surface free energy difference (= g
SV
g
SL
)
[M T
2
]
E Change in total energy of a raised
liquid column [M L
2
T
2
]
(E)
min
Minimum value of E [M L
2
T
2
]
E
g
Change in interfacial energy
gained by a raised liquid
column [M L
2
T
2
]
E
g
Change in potential energy
gained by a raised liquid
column [M L
2
T
2
]
g Acceleration of gravity [L T
2
]
h Height of liquid in a capillary tube [L]
h
cm
Height of center of mass
of a liquid column [L]
Contact angle []
m Mass of a uid column of density
and height h in a capillary tube
of radius r (= r
2
h) [M]
p
k
Kinetic contribution to uid
pressure (always positive) [ML
1
T
2
]
p
s
Static or intrinsic pressure (cohesive contribution
to uid pressure normally negative) [ML
1
T
2
]
p
o
Pressure in the bulk of the uid [ML
1
T
2
]
p
n
Normal pressure [ML
1
T
2
]
p
t
Tangential pressure [ML
1
T
2
]
P Total pressure (=p
k
+p
s
) [ML
1
T
2
]
P
L
Liquid pressure [ML
1
T
2
]
P
V
Vapor/air/gas pressure [ML
1
T
2
]
P Pressure difference across a liquidvapor inter-
face (= P
V
P
L
or P
L
P
V
) [ML
1
T
2
]

e
Equilibrium spreading pressure or lm pressure
(= g
S
g
SV
) [M T
2
]
R Radius of curvature or radius of a drop [L
1
or L]
R
1
, R
2
Radii of curvature along two orthogonal directions
[L
1
]
r Radius of a capillary column [L]
820
Hydrogeology Journal (2010) 18: 811821 DOI 10.1007/s10040-009-0565-5
Fluid density [M L
3
]
V Volume of uid in a capillary column [L
3
]
y Distance of a molecule from the interface within the
radius of inuence [L]
References
Bachmann J, Woche SK, Goebel M-O, Kirkham MB, Horton R
(2003) Extended methodology for determining wetting proper-
ties of porous media. Water Resour Res 39(12):1353.
doi:10.1029/2003WR002143
Bailey AI, Kay SM (1967) A direct measurement of the inuence of
vapour, of liquid, and of oriented monolayers in the interfacial
energy of mica. Proc R Soc Lond A301:4756
Bear J (1979) Hydraulics of groundwater. McGraw-Hill, New York
Berry MV (1971) The molecular mechanism of surface tension.
Phys Educ 6(2):7984
Bikerman JJ (1970) Physical surfaces. Academic, New York
Brown RC (1941) Note on the energy associated with capillary rise.
Proc Phys Soc 53:233234
Brown RC (1947) The fundamental concepts concerning surface
tension and capillarity. Proc Phys Soc 59:429446
Chapin EK (1959) Two contrasting theories of capillary action. Am
J Phys 27(9):617619
Denny MW (1993) Air and water. The biology and physics of lifes
media. Princeton Univ Press, Princeton, NJ
Dingman LS (1984) Fluvial hydrology. Freeman, New York
Domenico PA, Schwartz FW (1998) Physical and chemical hydro-
geology, 2nd edn. Wiley, New York
Ehlers W, Goss M (2003) Water dynamics in plant production.
CABI, Cambridge, UK
Fetter CW (2001) Applied hydrogeology, 4th edn. Prentice Hall,
Englewood Cliffs, NJ
Freeze RA, Cherry JA (1979) Groundwater. Prentice Hall, Engle-
wood Cliffs, NJ
Giancoli DC (1988) Physics for scientists and engineers, 2nd edn.
Prentice Hall, Englewood Cliffs, NJ
Gilboa A, Bachmann J, Woche SK, Chen Y (2006) Applicability of
interfacial theories of surface tension to water-repellent soils.
Soil Sci Soc Am 70:14171429
Good RJ (1993) Contact angle, wetting, and adhesion: a critical
review. In: Mittal KL (ed) Contact angle, wettability and
adhesion. VSP, Utrecht, The Netherlands, pp 336
Henriksson U, Eriksson JC (2004) Thermodynamics of capillary
rise: Why is the meniscus curved? J Chem Educ 81(1):150154
Hillel D(1998) Environmental soil physics. Academic, San Diego, CA
Hunter RJ (2001) Foundations of colloid science, 2nd edn. Oxford
Univ Press, Oxford
Isenberg C (1992) The science of soap lms and soap bubbles.
Dover, New York
Jaycock MJ, Partt GD (1981) Chemistry of interfaces, 1st edn.
Ellis Horwood series, Wiley, Chichester, UK
Jury WA, Horton R (2004) Soil physics, 6th edn. Wiley, Hoboken,
NJ
Kane JW, Sterheim MM (1984) Physics, 2nd edn. Wiley, New York
Kirkham MB (2005) Principles of soil and plant water relations.
Elsevier, Amsterdam
Koorevaar P, Menelik G, Dirksen C (1983) Elements of soil
physics. Developments in Soil Science 13. Elsevier, Amsterdam
Kwok DY, Neumann AW (1999) Contact angle measurement and
contact angle interpretation. Adv Colloid Interface Sci 18:167249
Markworth AJ (1971) Liquid rise in a capillary tube: a treatment on
the basis of energy. J Chem Educ 49(8):528
Marshall TJ, Holmes JW (1988) Soil physics, 2nd edn. Cambridge
Univ. Press, New York
McCaughan JBT (1987) Capillarity: a lesson in the epistemology of
physics. Phys Educ 22:100106
McCaughan JBT (1992) Comment on The upward force on liquid in a
capillary tube, by Scheie, P.O. Am J Phys 60(1):87
Miller F Jr, Schroeer D (1987) College physics, 6th edn. Harcourt,
New York
Orowan E (1970) Surface energy and surface tension in solids and
liquids. Proc R Soc Lond A316(1527):473491
Or D, Tuller M (2005) Capillarity. In: Hillel D (ed) Encyclopedia
of soils in the environment. Elsevier, Amsterdam, pp 155
164
Or D, Wraith JM (2002) Soil water content and water potential
relationships. In: Warrick AW (ed) Soil physics companion.
CRC, Boca Raton, FL
Peiris MGC, Tannakone K (1980) Rate of rise of a liquid in a
capillary tube. Am J Phys 48
Pellicer J, Manzanares JA, Mafe S (1995) The physical description
of elementary surface phenomena: thermodynamics versus
mechanics. Am J Phys 63(6):542547
Roura P (2007) Contact angle in thick capillaries: a derivation based
on energy balance. Eur J Phys 28:L27L32
Sears FW, Zemanski MW, Young HD (1982) University physics,
6th edn. Addison-Wesley, Reading, UK
Snow TP, Shull JM (1986) Physics. West, St Paul, MN
Tabor D (1991) Gases, liquids and solids and other states of matter,
3rd edn. Cambridge Univ Press, Cambridge, UK
Temperley HNV, Travena DH (1978) Liquids and their properties.
Ellis Horwood series, Wiley, Chichester, UK
Tipler PA (1991) Physics for scientists and engineers, 3rd edn.
Worth, New York
821
Hydrogeology Journal (2010) 18: 811821 DOI 10.1007/s10040-009-0565-5
Reproducedwith permission of thecopyright owner. Further reproductionprohibited without permission.