Why Is Surface Tension A Force Parallel To The Interface?: Additional Information On Am. J. Phys

Why is surface tension a force parallel to the interface?
Antonin Marchand, Joost H. Weijs, Jacco H. Snoeijer, and Bruno Andreotti
Citation: Am. J. Phys. 79, 999 (2011); doi: 10.1119/1.3619866

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Why is surface tension a force parallel to the interface?
Antonin Marchand
Physique et Mécanique des Milieux Hétérogènes, UMR 7636 ESPCI - CNRS, Université Paris-Diderot,
10 rue Vauquelin, 75005, Paris, France
Joost H. Weijs and Jacco H. Snoeijer
Physics of Fluids Group and J. M. Burgers Centre for Fluid Dynamics, University of Twente, P.O. Box 217,
7500 AE Enschede, The Netherlands
Bruno Andreotti
Physique et Mécanique des Milieux Hétérogènes, UMR 7636 ESPCI - CNRS, Université Paris-Diderot,
10 rue Vauquelin, 75005, Paris, France
(Received 9 November 2011; accepted 10 July 2010)
A paperclip can float on water. Drops of mercury do not spread on a surface. These capillary
phenomena are macroscopic manifestations of molecular interactions and can be explained
in terms of surface tension. We address several conceptual questions that are often encountered
when teaching capillarity and provide a perspective that reconciles the macroscopic viewpoints
from thermodynamics and fluid mechanics and the microscopic perspective from statistical
physics. VC 2011 American Association of Physics Teachers.
[DOI: 10.1119/1.3619866]
I. INTRODUCTION for a system of volume V containing N molecules at tempera-

ture T. Hence, cLV is the energy needed to increase the inter-
Capillarity is one of the most interesting subjects to teach facial area by one unit. Its dimension is [cLV] ¼ MT2 (mass
in condensed matter physics because its detailed understand- per time squared), and is usually expressed in N/m (force per
ing involves macroscopic thermodynamics,1–3 fluid mechan- unit length) or J/m2 (energy per unit area).
ics, and statistical physics.4 The microscopic origin of The order of magnitude of the surface tension must be of
surface tension lies in the intermolecular interactions and the order of the bond energy divided by the cross section
thermal effects,5,6 while macroscopically it can be under- area r2 of a molecule, where r is a fraction of a nanometer.
stood as a force acting along the interface or an energy per The van der Waals interaction for oils leads to kB T
unit surface area. In this article, we discuss the link between ’ ð1=40Þ eV and thus cLV 0.02 N/m. For water, hydrogen
these three aspects of capillarity using simple examples. We bonds lead to a higher value cLV 0.072 N/m. For mercury,
first discuss the standard problems faced by students and the high energy bonds ð 1 eVÞ lead to an even higher sur-
many researchers in understanding surface tension. We will face tension cLV 0.5 N/m.
see that the difficulty of understanding surface tension forces Mechanical point of view. In fluid mechanics, the surface
is often caused by an improper or incomplete definition of a tension is not defined in terms of a surface energy but rather
system on which the forces act. We ask four basic questions, as a force per unit length. In the bulk of a fluid at rest, two
such as the one raised in the title, which we answer in the sub-parts of a fluid exert a repulsive force on one another,
following. Contrary to many textbooks on the subject, we which is called the pressure. If the surface separating these
provide a picture that reconciles the microscopic, thermody- two subsystems crosses the liquid-vapor interface, an addi-
namic, and mechanical aspects of capillarity. tional force needs to be taken into account: surface tension.
As shown in Fig. 2, the surface tension is a force tangent to
the surface and normal to the contour separating the two sub-
II. BASIC CONCEPTS AND PROBLEMS systems. The total force is proportional to the width W of the
A. The interface contour. Contrary to pressure, surface tension is an attractive
force.
Thermodynamic point of view. Following the pioneering
work of Gibbs,7 we introduce surface tension as the excess
free energy due to the presence of an interface between two
bulk phases. Consider a molecule in the vicinity of an inter-
face, for example, a liquid-vapor interface. The environment
of this molecule is different from the molecules in the bulk.
This difference is usually represented schematically by
drawing the attractive bonds between molecules, as shown in
Fig. 1. We see from Fig. 1 that approximately half of the
bonds are missing for a molecule at the interface, leading to
an increase of the free energy. We thus define the surface
tension from the free energy F per unit area:

@F Fig. 1. Sketch showing the missing intermolecular bonds close to the liquid-
cLV ¼ ; (1) vapor interface, giving rise to an increase in the free energy per unit area,
@A T;V;N that is, the surface tension.
999 Am. J. Phys. 79 (10), October 2011 http://aapt.org/ajp C 2011 American Association of Physics Teachers
V 999
ing interfacial energy is unaffected. However, the motion
leads to a decrease of the immersed solid-liquid interface
area by Wd‘, while the solid-vapor interface increases by the
same amount. In other words, part of the wetted surface is
exchanged for a dry surface, which leads to a change of the
free energy dF ¼ (cSV –cSL)Wd‘, where cSV and cSL are the
solid-vapor and solid-liquid surface tensions, respectively.
This energy is provided by the work done due to the force
Fig. 2. Sketch showing the surface tension as a force per unit length exerted required to displace the plate by d‘. Hence, this force must
by one subsystem on the other. The system on which the forces act is the be equal to (cSV – cSL)W.
dotted region. The force is parallel to the interface and perpendicular to the To relate this force to the value of the liquid-vapor surface
dividing line.
tension cLV, we invoke Young’s law for the contact angle h
see Fig. 3(b) and the following discussion). When the three
The link between mechanics and thermodynamics is pro- interfaces between the solid, liquid, and vapor join at the
vided by the virtual work principle. If we move a contour of contact line, the liquid makes contact with the substrate at an
width W by a length d‘, the area of the interface of the sub- angle h given by8
system considered increases by Wd‘. Consequently, the free
energy is increased by cLVWd‘. The free energy equals the cLV cos h ¼ cSV cSL : (2)
work done by the surface tension force, which means that
this force is parallel to the interface, normal to the contour, By using Eq. (2), the force exerted on the plate can be
and has a magnitude cLV W. Per unit length, the surface ten- expressed as WcLV cos h, and thus, we have designed a
sion force is thus cLV. tensiometer.
For students, the link between mechanics and statistical Mechanical point of view. From the mechanical point of
physics is much less obvious than the link between mechan- view, we can interpret the force required to maintain the
ics and thermodynamics. We clearly see in Fig. 1 that the plate out of the bath as the surface tension acting parallel to
molecule at the interface is subject to a net force (which the liquid-vapor interface [see Fig. 3(a)]. By symmetry, the
would be represented by the sum of the vectors) along the total force exerted on the solid is vertical (the horizontal
direction perpendicular to the interface. However, we just components sum to zero). By projecting the surface tension
argued from the mechanical point of view, that the force is force onto the vertical direction and by multiplying the
parallel to the interface. This difference in perspective leads length W of the contact line, we obtain WcLV cos h.
to the first key question of this article: By a similar argument, we usually interpret Young’s law
Question 1: Why is surface tension a force parallel to the for the contact angle as the balance of forces at the contact
interface even though it seems obvious that it must be per- line [see Fig. 3(b)]. By a projection along the direction paral-
pendicular to it? lel to the solid substrate, we obtain cSL þ cLV cos h ¼ cSV,
which is the same as Eq. (2). This force interpretation is a
common source of confusion for students:
B. The contact line Question 2: From Fig. 2(b), there seems to be an unbal-
anced force component in the vertical direction cLV sin h.
Thermodynamic point of view. A standard method for What force is missing to achieve equilibrium?
determining the liquid-vapor surface tension is to measure Question 3: Why do we draw a single force acting on the
the force required to pull a metallic plate (usually made of contact line for the plate [Fig. 3(a)], while for Young’s law
platinum) out of a liquid bath. This force is related to the liq- we need to balance all three forces [see Fig. 3(b)]?
uid-vapor surface tension cLV, as is usually explained by a Actually, when measuring a surface tension using the plate
diagram similar to Fig. 3(a). Imagine that the plate is moved technique, we often use a platinum plate to be sure that the
vertically by a distance d‘. The area of the liquid-vapor inter- liquid completely wets the solid. In that case cSV – cSL > cLV
face is not changed by this motion, and thus the correspond- and Young’s law does not apply. In this case, the thermody-
namic and mechanical approaches give conflicting answers:
Question 4: For complete wetting, is the force on the plate
given by cLV or by cSV – cSL?
C. Brief answers
We start with a short overview of the answers to the ques-
tions we have raised. We emphasize that the thermodynamic
result (that is, from the virtual work principle) always gives
the correct total force. If we want to know the local force dis-
tribution, which cannot be extracted from thermodynamics,
FIG. 3. (a) Experimental method for determining the liquid-vapor surface it is imperative that the system on which the forces act is
tension. The force per unit length needed to pull a plate from a bath of liquid properly defined. Confusion regarding the forces is often
is equal to cLV cos h, where h is the equilibrium contact angle. (b) A tradi-
tional way to interpret Young’s law as a force balance of surface tensions.
caused by an improper or incomplete definition of such a
Question 2: Why is there no force balance in the normal direction? Question system.
3: Why do we draw a single surface tension force in (a) (cLV) while there are Answer 1: The schematic of Fig. 1 represents only the
three in (b) (cLV, cSV, and cSL)? attractive intermolecular forces. The real force balance
1000 Am. J. Phys., Vol. 79, No. 10, October 2011 Marchand et al. 1000
requires both repulsive and attractive interactions between
liquid molecules.
To answer questions related to the contact line, it is crucial
to specify the system of molecules on which the forces are
acting:
Answer 2: In Young’s law, the system on which the forces
act is a corner of liquid bounded by the contact line. cLV is
the force exerted on this system inside the liquid-vapor inter-
face, but the forces exerted by the solid on the corner are
incomplete in Fig. 3(b). An extra vertical force on the liquid,
caused by the attraction of the solid, exactly balances the
upward force c sin h
Answer 3: To obtain the force on the plate, the system to
consider is the solid plate. In this case, the force exerted by
the liquid on the solid is equal to cLV cos h per unit length.
Answer 4: The correct vertical force on the plate is WcLV
cos h. For complete wetting (h ¼ 0), the virtual work princi- Fig. 4. Lennard-Jones intermolecular potential /. The interaction is strongly
ple can be applied, but only when taking into account the repulsive for intermolecular distances r < r. At large distances, the mole-
cules are attracted to one another. The gray arrow points to the presence of
prewetting film.
thermal fluctuations, which, in a liquid, lead to substantial variations of the
intermolecular distance.
III. MICROSCOPIC INTERPRETATION

tial reflects the short-range repulsion, and the negative tail
OF CAPILLARITY represents the long-range attraction. The balance of attrac-
A. The liquid state tive and repulsive interactions in Eq. (3) only has a statistical
meaning: some particles attract each other while others repel.
To address the origin of capillarity, we have to understand The existence of both repulsion and attraction is what makes
how a liquid phase and a vapor phase can coexist. To do so, liquids very different from solids like polycrystals. In such
we consider the van der Waals equation of state, which can solids, thermal effects are often negligible and molecules in
account for the liquid-gas phase transition:5,9 the same region are either all compressed (if the region is
kT a submitted to an external compression) or all attracted to each
P¼ 2; (3) other (if the region is submitted to an external tension).
vb v The difference between a solid and a liquid can be traced
where P is the pressure and v is the volume per molecule. to the importance of thermal fluctuations, that is, the kinetic
Equation (3) corrects the ideal gas law to incorporate the energy of the molecules. In the solid phase, these fluctuations
effect of intermolecular forces. The constant b introduces are small with respect to the potential energy, that is,
repulsion between molecules as an excluded volume effect: kB T , where is the energy scale for the intermolecular
the pressure diverges when the total volume per molecule forces. As a consequence, the system explores only a small
reaches a minimal size b. In this limit, the molecules are region of the potential. Hence, the solid is either in the com-
densely packed and constitute a liquid phase. In this phase, pressed or in the tensile state. In contrast, the liquid phase is
the volume per molecule no longer depends on pressure, characterized by large fluctuations, for which kB T . A
which means that the liquid phase is incompressible. Ulti- broad range of the potential is therefore sampled by mole-
mately, this effect comes from the repulsion of the electron cules in the same region of space (see Fig. 4). The case
clouds of the molecules, due to the Pauli exclusion principle. kB T corresponds to a gas phase of weakly interacting
The constant a represents the long-range attraction between particles that is dominated by kinetic energy.
molecules which finds its origin in the dipole-dipole interac-
tion (van der Waals attraction). B. The liquid-vapor interface: Question 1
Equation (3) explains how a low density gas phase can
coexist with a high density liquid phase. This coexistence We now consider the liquid-vapor interface in more detail.
requires the pressures to be identical on both sides of the Figure 5(a) shows a snapshot of the interface obtained in a
interface, despite the striking difference in density. In a gas, molecular dynamics simulation of molecules interacting
where v ¼ vg is large, most of the energy is kinetic with the Lennard-Jones potential.10–12 The corresponding
ða=v2g PÞ, and the pressure is P ’ kT=vg . In the liquid time-averaged density profile is plotted in Fig. 5(b). The
phase, the volume per unit molecule is almost in the incom- transition from the high density liquid to the low density gas
pressible limit and v ¼ vl b. This strong repulsive effect takes place in a very narrow region that is a few molecules
ðkT=ðvl bÞ PÞ is counterbalanced by the presence of wide. To determine the capillary forces we need to divide
attractions ða=v2l PÞ so that, for the same temperature, the the system along the direction normal to the interface into
pressure in the liquid phase can be in equilibrium with the two subsystems [see Fig. 5(a)]. We consider the force
pressure in the gas phase, giving rise to a stable liquid-vapor exerted by the left subsystem on the right subsystem through
interface. a small vertical surface at the separation of the subsystems
How can a liquid at the same time be repulsive and attrac- and at the vertical position z. This force is proportional to the
tive? A single pair of atoms can only attract or repel each area of this small surface so that we can define the force per
other, depending on the distance separating them. Their unit area, which is the stress, exerted by the left on the right
interaction is shown schematically in Fig. 4. The steep poten- as a function of z. This stress can be decomposed into two
C. Separate roles of attraction and repulsion
We still need to explain why the intermolecular forces
give rise to such a strong tension along the surface. This
question was addressed by Berry,6 who noted the separate
roles of attraction and repulsion. The key observation is that,
to a good approximation, the repulsive contribution to the
pressure is isotropic while attraction is strongly anisotropic.
The reason is that the repulsion is short ranged due to the
hard core of the molecules and can be thought of as a
“contact force.” As such, repulsion is not very sensitive to
the changes in the structure of the liquid around the mole-
cules, and in particular near the interface where repulsion
remains equally strong in all directions.12 In contrast, the
Fig. 5. The liquid-vapor interface. The vertical axis is in units of r. (a)
Snapshot of a molecular dynamics simulation of a liquid-vapor interface
long-range nature of the attractive forces make them very
using the Lennard-Jones potential. (b) Time-averaged normalized density sensitive to the structure of the liquid. The difference
profile q*(z) across the interface. (c) Tangential force per unit area exerted between the ranges of the attractive and repulsive interac-
by the left part on the right part of the system. The plot shows the difference tions is the origin of the observed pressure anisotropy near
P ¼ pNN – pTT between the normal and tangential components of the stress the interface that generates the surface tension force.
tensor. To see how the anisotropy works out in detail it is useful
to divide the liquid into two subsystems using an imaginary
contributions: the pressure P, which is the same in the vapor surface parallel to the liquid-vapor interface, as shown in
and the liquid bulk, plus an extra stress P(z) acting along the Fig. 7(a). The force exerted on the dotted subsystem by the
direction parallel to the interface [see Fig. 5(c)]. The profile rest of the liquid results from the superposition of attractive
of this stress anisotropy shows that there is a force localized (vertical gray arrows) and repulsive (dashed black arrows)
at the interface, acting in the direction parallel to the inter- interactions [see Fig. 7(a)]. Because the subsystem is in equi-
face. This force is spread over a few molecular diameters, librium, these attractive and repulsive components must bal-
which is the typical thickness of the density jump across the ance each other. The magnitude of the attractive force
interface. The integrated contribution of this force is equal to increases with the size of the attracting region because the
cLV per unit length, the surface tension. The simulations density increases as the system moves from the vapor toward
show that surface tension really is a mechanical force. the liquid phase. The magnitude of the attraction saturates to
Now that we have found that there is a parallel force local- the bulk value when the imaginary surface is a few molecu-
ized at the interface, we turn to Question 1. Why is the ten- lar sizes from the interface. We then divide the liquid into
sion force parallel and not normal to the interface? We first two subsystems using an imaginary surface perpendicular to
note that Fig. 1 depicts only the attraction between mole- the liquid vapor interface [see Fig. 7(b)]. We can now see
cules. A more complete picture also incorporates the repul- that the repulsive short-range forces are isotropic, which
sive contributions to the internal pressure, as denoted by the means that the repulsion (dashed black arrows) exerted by
dashed arrows in Fig. 6. Away from the surface there is per- the left side on the subsystem (dotted region) increases with
fect force balance due to the symmetry around a molecule.
Near the interface, however, the up-down symmetry is bro-
ken. To restore the force balance in the vertical direction, the
upward repulsive arrow (dashed) has to balance the down-
ward attractive arrow (solid). In the direction parallel to the
interface, the symmetry is still intact, thus automatically
ensuring a force balance parallel to the interface. This bal-
ance means that along the direction parallel to the interface,
there is no reason why the attractive forces should have the
same magnitude as the repulsive forces. In practice, the
attractive forces are stronger, which gives rise to a positive
surface tension force.
Fig. 7. Forces exerted on a subsystem of liquid (dotted region) by the rest of

the liquid (gray region without dots). (a) The subsystem is the lower part of
the liquid and is separated from the interfacial zone by a line parallel to the
liquid-vapor interface. The subsystem (dotted region) is subjected to an
attractive force (gray arrows) and a repulsive force (dashed black arrows)
exerted by the rest of the liquid (gray region without dots). The forces must
balance each other. (b) The liquid is divided along a line perpendicular to
the interface. The subsystem considered (the dotted region on the right) is
subjected to an attractive force (gray arrows) and to a repulsive force
(dashed arrows) exerted by the rest of the liquid (gray region without dots).
Because the repulsive force is isotropic, it has the same magnitude as in (a)
and therefore decays close to the surface. In contrast, the attractive force is
Fig. 6. Sketch showing repulsive (dashed black arrows) and attractive (gray nearly constant and remains almost unchanged close to the surface. (c) This
arrows) forces in the bulk and at the surface. construction leads to a net attractive force from one side on the other.
depth in a way analogous to that in Fig. 7(a). In contrast, the
strength of the attraction has a much weaker dependence on
depth; for simplicity, we draw it with a constant magnitude
which equals the attraction in the bulk. As a result, there is a
net attraction of the subsystem by the rest of the liquid [see
the dark gray arrow in Fig. 7(c)].
D. The liquid-solid interface

Forces near the liquid-solid interface. We now consider
the liquid-solid interface (see Fig. 8). In this case, two effects
superimpose. Due to the presence of the solid, there is a lack
of liquid in the lower half-space (hatched region in Fig. 8).
The missing liquid induces an anisotropy of the attractive liq-
uid-liquid force in the same way as it does for the liquid-
vapor interface. Hence, as in Fig. 7(c), the left-hand side of
the liquid exerts a net attractive force cLV per unit length on
the right-hand side subsystem. The other effect is due to the
liquid-solid interaction. In the same way as for the liquid-
Fig. 9. Relation between adhesion work and surface tensions. (a) To split a
vapor interface, we divide the liquid into two subsystems liquid volume into two semi-infinite volumes, we have to create two liquid-
using an imaginary surface parallel to the interface, as shown vacuum interfaces, which costs energy ALL ¼ 2cLV. (b) To create a solid-liq-
in Fig. 8(a). The attraction by the solid (gray arrow) decreases uid interface, we first need to create a liquid-vacuum and solid-vacuum
with distance and is perfectly balanced by the short range liq- interface, which costs energy cSV þ cLV. Joining the liquid-vacuum and
uid-liquid repulsive force (dashed arrows). We then divide solid-vacuum interfaces yields an energy reduction ASL ¼ cSV þ cLV – cSL
the liquid into two subsystems using an imaginary surface due to the solid-liquid attraction.
perpendicular to the liquid solid interface [see Fig. 8(b)]. If
we assume that the liquid-liquid repulsion is isotropic, the left not couple directly to the solid-liquid surface tension cSL, but
part of the liquid exerts a net repulsive force on the right sub- to the combination cSV þ cLV cSL.1,13 This feature is also
system (dotted region). This force is induced by the influence crucial for understanding the wetting phenomena discussed
of the solid and, surprisingly, it is not equal to cSL. Instead, it in Sec. IV.
has been shown11 that this force is equal to cSV þ cLV cSL, The solid-liquid surface tension represents the free energy
as will be motivated in more detail in the following. needed to create a solid-liquid interface. To make such an
To combine these two effects, we subtract the unbalanced interface, we first have to “break” the bulk solid and the bulk
attractive force due to the absent liquid (cLV) from the repul- liquid into two separate parts, and then join these solid and
sive force due to the solid (cSV þ cLV cSL) to find the net liquid parts together. The breaking of the liquid is depicted
repulsive force between the subsystems: cSV cSL. schematically in Fig. 9(a) (it works similarly for the solid).
Solid-liquid interaction and the surface tensions. Let us The corresponding energy is the “work of adhesion” ALL due
motivate why the strength of the solid-liquid interaction does to liquid-liquid attractions (ASS for the solid). This breaking
gives rise to a surface tension 2cLV ¼ ALL (2cSV ¼ ASS),
because the liquid (solid) is connected to a vacuum at this in-
termediate stage. When joining the solid-vacuum and liquid-
vacuum interfaces, the attractive solid-liquid interaction
reduces the surface energy by the solid-liquid work of adhe-
sion ASL [see Fig. 9(b)]. Hence, the resulting solid-liquid sur-
face tension becomes
cSL ¼ cSV þ cLV ASL : (4)
From Eq. (4), we find that the strength of the solid-liquid ad-
hesion is
ASL ¼ cSV þ cLV cSL ¼ cLV ð1 þ cos hÞ (5)
In the last step, we used Young’s law for the equilibrium

Fig. 8. Forces exerted by the solid (dashed line) on a subsystem of liquid contact angle. As a consequence, the magnitude of the capil-
(dotted region). The attractive liquid-liquid interactions treated in Fig. 7 are lary forces induced by solid-liquid attractions is ASL ¼ cLV
not considered. (a) The liquid subsystem is semi-infinite. It is delimited by a (1 þ cos h) and not cSL.
line parallel to the liquid-solid interface, at different distances above it. The
subsystem is subjected to an attractive force (gray arrows) exerted by the
solid and to a repulsive force (dashed arrows) exerted by the rest of the liq-
uid (gray region without dots). Because the subsystem is in equilibrium,
IV. MICROSCOPIC INTERPRETATION
these forces must balance each other. (b) The liquid is divided along a line OF WETTING
perpendicular to the interface. Only the horizontal force components are
shown. The solid exerts no horizontal attraction. Because the repulsive inter- The question of the force balance is even more compli-
actions are isotropic, this construction results in an horizontal repulsive force cated in the vicinity of the contact line, where the liquid-
cSV þ cLV – cSL exerted by one side on the other. vapor interface meets the solid. It is important to note that
the contact line does not represent any material. Instead it is and zero outside the droplet, the repulsive force must decay
an imaginary line that marks the separation between wetted close to the contact line. This decay means that there is an
and dry parts of the solid. The question “What is the force on unbalanced attractive force which is strongly localized in the
the contact line?” is thus ill-posed, because there are no mol- vicinity of the contact line. It has been shown16 that this
ecules on which such a force would act. Only a collection of force per unit length is equal to cLV sin h.
matter can be submitted to a force. Therefore, care should be The existence of this force has recently been chal-
taken to properly define the systems that play a role near the lenged.17,18 To show that this force must exist to achieve
contact line, which are the liquid near the contact line and equilibrium, we consider the droplet shown in Fig. 11. If we
the solid underneath it. In the following, we will show how a choose the droplet as the system and recognize that the force
careful consideration of all the forces on the appropriate ma- in the interior of the droplet at the liquid-solid interface
terial systems leads to proper force balances, consistent with (small arrows) is due to the Laplace pressure 2cLVj (with j
the thermodynamic predictions. the curvature 1/R), we see that the attractive force at the con-
All results and sketches provided in this section, some of tact line must be cLV sin h to achieve a force balance.19–23
which may appear counterintuitive, are consistent with a This picture provides the answer to Question 2: the down-
density functional theory for microscopic interactions14,15 ward solid-on-liquid force is not drawn in Fig. 3(b). This
and molecular dynamics simulations.12 missing force has often been interpreted as a reaction from
the solid,2 whose existence is demonstrated experimentally
by the elastic deformation of soft solids below the contact
A. Force on a liquid corner: Question 2 line.22–25 Here, we clarify the molecular origin of this normal
Consider the forces on the wedge-shaped liquid corner in force.16
the vicinity of the contact line, as shown in Fig. 10. We will To finalize the force construction near the contact line, we
now explain Young’s force construction from Fig. 3(b) and return to the wedge shown in Fig. 10(b). Because the solid
answer Question 2: What happens to the force balance nor- can exert only a normal force on the liquid, all parallel force
mal to the solid-liquid interface? components drawn in Young’s construction are purely due to
There are two types of forces acting on the liquid mole- the liquid molecules outside the corner. The force drawn
cules inside the subsystem: interactions with the solid and along the liquid-vapor interface can be understood directly
interactions with other liquid molecules outside the subsys- from the tension cLV inside the liquid-vapor interface (see
tem. We first consider the solid-on-liquid forces. We see that the discussion of Fig. 7). A similar force arises at the solid-
because the solid spans an infinite half space, every liquid liquid interface (see Fig. 8), which is repulsive and has the
molecule experiences a resultant force which is normal to magnitude cSV cSL. Including these forces gives a perfect
the solid-liquid interface: the left-right symmetry of the solid force balance on the liquid corner, as seen in Fig. 10(a). It
ensures that there is no force component parallel to the inter- can be easily verified that even the resultant torque is zero
face. Far from the contact line at the solid-liquid interface, for this force construction. As such, it provides a more physi-
this attractive force is balanced by a repulsive force, as cal alternative to the classical picture of Young’s law.
shown in Fig. 8. Because the repulsive force is continuous
B. Liquid-on-Solid force: Question 3
The measurement of surface tension shown in Fig. 3(a)
relies on the force exerted by the liquid on the solid plate.
Again, we emphasize the importance of a proper definition
of the system on which the forces act. In this case, the system
is the solid on which the liquid rests. The situation is thus
very different from the forces on the liquid corner, which are
in equilibrium so that the resultant force is zero. This differ-
ence provides the key to Question 3. In Fig. 3(a), the total
force exerted by the liquid on the solid is represented by the
Fig. 10. Solid and liquid forces acting on a liquid subsystem (dotted region)
near the contact line. (a) Sketch of a wedge of liquid near the contact line
with the three forces exerted on the system. (b) Each of the three corners of
this system must be treated differently. The upper right corner is at the liquid
vapor interface. Following Fig. 7, the rest of the liquid exerts a net attractive Fig. 11. Forces acting on a liquid drop (dotted area). The system is in equi-
force parallel to the interface equal to cLV per unit length. The lower right librium so the sum of all external forces must be zero. Due to Laplace pres-
corner is at the liquid solid interface. Following Figs. 7 and 8, the rest of the sure, there is a repulsive force exerted by the solid on the liquid across the
liquid exerts a repulsive force cSV cSL. The liquid near the solid-liquid liquid-solid interface (upward black arrows). In the vicinity of the contact
interface is attracted by the solid. This force is balanced everywhere by line, repulsion and attraction of the liquid by the solid do not balance each
repulsion at the solid-liquid interface, except in the vicinity of the contact other. Therefore, the solid attracts the liquid with a vertical force equal to
line. cLV sin h per unit length (downward dark gray arrows).
resultant ~cLV , and Fig. 3(b) represents the balance of the metric, and therefore there is no tangential component. This
forces acting on the liquid wedge. difference between the forces acting on the solid or on the
Forces near the contact line. We turn again to the micro- liquid again illustrates that a detailed force interpretation
scopic description of the forces in the vicinity of the contact crucially relies on the definition of the system.
line. It turns out that the normal component of the force Global force balance: curvature of solid-liquid interface.
exerted on the solid is equal to cLV sin h, consistent with the To solve the apparent discrepancy between the tangential
macroscopic picture of a tension force pulling along the liq- force cLV(1 þ cos h) and the thermodynamic result we dis-
uid-vapor interface. The parallel component of the liquid-on- cussed in Sec. II B, which was consistent with a tangential
solid force does not have the expected magnitude cLV cos h, force cLV cos h, we have to consider all the forces exerted by
but cLV þ cSV cSL ¼ cLV(1 þ cos h). This unexpected mag- the liquid on the solid, not just the forces near the contact
nitude can be understood as follows. Figure 12(a) illustrates line. The key point is that the submerged solid bodies cannot
that the tangential force component originates from the long- be flat everywhere and the liquid-solid interface must be
range attraction between solid and liquid molecules. We pre- curved. If the interface separating the solid from the liquid is
viously demonstrated that the strength of this solid-liquid ad- flat, the net normal force is locally zero because repulsion bal-
hesion is ASL ¼ cLV (1 þ cos h). Hence, there is no reason ances attraction (far away from the contact line). When the
why the total force on the solid should be cLV cos h. A den- interface is curved, the repulsive force inside the liquid is
sity functional theory calculation confirms a tangential liq- enhanced due to the curvature, in a way similar to the Laplace
uid-on-solid force of magnitude ASL ¼ cLV(1 þ cos h).16 pressure. As shown in Fig. 13, the presence of a curved half-
The physics of this surprising result is illustrated by Fig. space of liquid acts on the solid and creates an unbalanced
12. The macroscopic intuition that the resultant surface ten- liquid-on-solid force cLVj per unit area. Density functional
sion force pulls along the liquid-vapor interface would pre- theory calculations16 show that the resultant pressure couples
dict a force to the left whenever the contact angle h > 90 . only to cLV and not to cSL. As we will show, this supplemen-
However, it is clear from the sketch of the attractive forces tary force is exactly what is needed to restore consistency
that the sum of all the parallel components must be oriented between the microscopic and thermodynamic forces.
toward the liquid (right side in the figure). This orientation An excellent demonstration of this effect is the long
stems from the asymmetry between the amount of liquid debated case of a “floating-pin” under zero gravity, as shown
attracting the solid molecules on both sides of the contact in Fig 14. Although a floating pin in a system with gravity
line: there are always more liquid molecules on the right side leaves a visible depression in the liquid-vapor interface near
of the contact line in Fig. 12. This behavior is consistent the contact line [see Fig. 14(e)], the zero-gravity condition
with the parallel force cLV(1 þ cos h), but not with a force ensures that the interface has constant curvature, that is, it is
cLV cos h (which changes sign at h ¼ 90 ). Note that when straight everywhere. Because the liquid-vapor interface is
considering the force exerted by the solid on the liquid, this flat, the vertical position of the pin depends on the equilib-
asymmetry does not occur because the solid is left-right sym- rium contact-angle alone and not on the density ratio of the
materials involved. As shown in Fig. 12, the liquid-on-solid
forces near the contact lines are not oriented along the liq-
uid-vapor interface, but point toward the interior of the
Fig. 12. Forces acting on the solid subsystem (hatched areas) by the liquid
(gray areas) near the contact line. (a) Distribution of forces acting on the Fig. 13. Forces acting on a solid at the solid-liquid interface. (a) Without
solid near the contact line. Due to the attraction of the liquid, the solid is liquid, there is neither repulsion nor attraction. (b) When liquid is present
attracted toward the liquid (solid gray arrows). The absence of liquid on the there is repulsion and attraction. However, the repulsion is not completely
left part of the contact line ensures the tangential force is toward the liquid, balanced at this curved interface, because there is more liquid in this geome-
even for h > 90 . The repulsion (dotted arrows) arises from the contact force try than in a plane geometry. (c) The resulting force is analogous to the force
at the solid-liquid interface. Far from the contact line, repulsion and attrac- created by the Laplace pressure at liquid-vapor interfaces. This force is cLVj
tion balance each other. (b) The resultant force acting on the solid near the per unit surface, where j > 0 is the curvature of the liquid. This expression
contact line. The net normal force is cLV sin h, and the parallel force only shows a dependence on the liquid-liquid interactions because the curva-
cLV þ cSV cSL ¼ cLV (1 þ cos h). ture has an effect only through the missing liquid matter.
Fig. 15. Force per unit length of the contact line needed to keep a plate in
equilibrium in a bath in (a) partial and (b) complete wetting. (c) Partial wet-
ting. The vertical force at the contact line, equal to cLV(1 þ cos h), is bal-
anced by the Laplace pressure induced by the curvature of the plate. Note
Fig. 14. (a) Schematic of a pin floating at the surface of a liquid under par- that any plate shape would lead to the same resultant force because the inte-
tial wetting conditions and in zero gravity. The downward thin gray arrows gral of the curvature over the surface reduces to the local tangents at the con-
are the forces exerted by the liquid on the pin located in the vicinity of the tact line [see Fig. 14(d)]. (d) Complete wetting case. Due to the mesoscopic
contact line. The small light gray arrows show the Laplace pressure cLVj pre-wetting film, whose thickness is exaggerated in the figure, there is no
acting on the solid due to the curvature j of the solid-liquid interface. (b) contact line; thus, there is no force located near the apparent macroscopic
The quantity h denotes the contact angle, and ~ t1 and ~t2 are unit vectors tan- contact line. The forces are related only to the Laplace pressure. The curva-
gential to the pin, pointing upward, at the two contact lines. (c) The thick ture of the solid gives a zero resultant force, because the solid is completely
gray arrows show the resultants of the capillary forces in (a), which apply on immersed in the liquid. Besides the curvature of the liquid acts on the solid
each half of the pin. They reduce to forces tangential to the liquid-vapor only in the pre-wetting zone because the Laplace pressure is compensated
interface at the contact lines. This schematic does not show the distribution by gravity in the meniscus. The resultant force per unit length is equal to
of capillary forces. (d) Distribution of the capillary forces for an irregular cLV.
shape. Because the integral over the curvature is equal to the sum of the two
tangential vectors at the contact lines, the resultant is independent of the
shape of the body. It is thus the same as in (c). (e) Pin floating at the surface The same principle applies to the partially wetted plate of
of a liquid under gravity. The upward thick gray arrows are the resultants of
capillary forces. They balance the effect of gravity (corrected by the Archi-
Fig. 3(a): the force exerted by the fluid on the plate results
medes force), shown as the downward black arrow. from two contributions as shown schematically in Fig. 15(c).
There is the vertical force component (per unit length) due to
the vicinity of the contact line: c(1 þ cos h) (see Fig. 12).
liquid. The total force resulting from the contributions of the There also are submerged surfaces of the plate where a local-
two contact lines is vertical and downward. Additionally, the ized curvature exists at the corners. This curvature induces a
curvature of the solid-liquid interface creates a normal force Laplace force on the pin [see Fig. 14(d)], which results in a
distributed over the entire immersed surface of the solid of net upward force cLV per unit length of contact line and
magnitude cLVj per unit surface [see Fig. 14(a)]. Integrating means that the total force (per unit length of contact line) on
over the curvature of the submerged surface from one con- the plate is cLV cos h, in agreement with the thermodynamic
tact line to the other gives the resultant of the Laplace result.
pressure: Complete wetting: Question 4. For complete wetting,
Young’s law for the contact angle is no longer applicable.
ð2 Instead, the apparent contact angle h vanishes because the
cLV n dS ¼ cLV ð~
j~ t2 þ ~
t1 Þ (6) three surface tensions do not balance each other:
1
cSV cSL > cLV : (7)
where ~t1 and ~
t2 are unit vectors tangential to the pin, pointing
upward. Therefore, the resultant is orientated upward and is Physically, there is no real contact line in this configuration
equal to 2cLV sin h per unit depth [see Fig. 14(b)]. It balances [see Fig. 15(b)], but there is a meniscus where the liquid-
exactly the downward forces induced close to the contact vapor interface approaches the solid. Beyond the meniscus,
lines [see Fig. 12(b)], and hence the pin is in equilibrium. there exists a mesoscopic liquid film called a prewetting
This result is independent of the shape of the body [see Fig. film, which covers the solid completely [see Fig. 15(d)]. The
14(d)]. existence of an apparent contact line is due only to the effect
of gravity: on a flat surface, the liquid would simply spread. the plate is pulled upward. When moving, there is no change
The interface between the liquid and vapor phases conse- of the solid-vapor interface area (it remains zero) or of the
quently has two regions. In the lower region, the meniscus solid-liquid interface area (which is the total area of the
can be described by the balance between the Laplace pres- plate). The only change occurs at the liquid-vapor interface
sure and the hydrostatic pressure area, which is increased, and the required pulling strength is
thus cLV per unit length of the apparent contact line.
cLV j ¼ qgz; (8)
where z is the height above the bath (thus, no additional con- V. SUMMARY
stant is needed) and j is the curvature of theffi interface. If we
pffiffiffiffiffiffiffiffiffiffiffiffiffiffi We have raised simple questions about capillarity that
introduce the capillary length ‘c ¼ cLV =qg, Eq. (8) can be many students face. By studying the interfaces from a micro-
written as ‘2c j ¼ z. In the upper region, there is the prewet- scopic perspective, we have provided answers to these ques-
ting film whose thickness h(z) is determined by the balance tions, and reconciled thermodynamics and statistical physics.
between the gravitational potential and the disjoining pres- We have provided a mechanical perspective about why
sure P(h) defined as the potential energy per unit volume at there exists an attractive force parallel to interfaces, which is
the surface of a liquid layer of thickness h. It describes the called the surface tension. The absence of liquid above the
attraction of the solid in the layer of liquid. Therefore, the liquid-vapor interface creates an attractive anisotropic force
balance is1,13 within a few molecular lengths from the interface, whereas
the repulsion remains isotropic and scales with the local den-
PðhÞ ¼ qgz: (9) sity of the fluid. The attractive anisotropy leads to a strong
localized force parallel to the interface called the surface ten-
Because the prewetting film is flat, the contribution of the
sion. This anisotropy and corresponding tangential force
Laplace pressure can be neglected (j ¼ 0) in this regime.
occurs at liquid-solid interfaces as well, where there is also a
The pressure scales as
half-space of liquid missing.
ðcSV cSL cLV Þr2 The problems that occur when constructing force pictures
PðhÞ ’ ; (10) at interfaces often arise from an improper definition of the
h3 system on which the forces act. By considering a corner of
for films where h r, r is a length on the order of the mo- liquid near the contact line as a system, we proposed an alter-
lecular size. The pressure vanishes in the limiting case native to Young’s construction [see Fig. 3(b)]. The analysis
cSV ¼ cSL þ cLV, which can be interpreted as the situation for lets us locate and understand the different forces, in particu-
which the interaction is the same with the liquid and with the lar, the attractive force exerted by the solid. This new force
solid. Then, we do not expect any influence of the thickness construction leads to perfect mechanical equilibrium, where
h on the energy. the net force and the torque balance.
We equate gravity and the disjoining pressure, Eq. (9), When looking at the force that is exerted by the liquid on
and obtain the thickness profile in the prewetting region: the solid near the contact line we find that this force is not
cLV cos h, but is cLV(1 þ cos h). Moreover, a normal stress is
1=3 exerted in all the regions of any curved solid-liquid interface,
ðcSV cSL cLV Þr2
hðzÞ ’ : (11) so that the liquid pulls the solid when the latter is convex.
qgz This force is equivalent to the usual Laplace pressure. We
have to take both these forces into account to obtain the net
In the vicinity of the apparent contact line, where the two force from thermodynamics. The advantage of this micro-
1=3
zones must match, the thickness is thus of order lc r2=3 . scopic force description is that it provides a simple answer to
Because lc is the order of millimeters and r is the order of a problem that has been controversial: the floating pin
nanometers. From the microscopic point of view, the solid is paradox.17,18,26
completely surrounded by a semi-infinite layer of liquid The drawings and several relations in this article are based
ðh rÞ. Therefore, the only forces acting on a solid in com- on results obtained using density functional theory in the
plete wetting are normal contact forces, such as Laplace sharp-kink approximation.16 This model can be used to make
pressures. There are no contact line forces such as those quantitative predictions of the force distributions in the liq-
described in Fig. 12(b). uid and in the solid.
The forces exerted by the liquid on the solid are related to We realize that a detailed picture of the microscopic forces
the curvature of the liquid-solid interface and inside the pre- is not necessarily the most accessible for teaching purposes. In
wetting film to the curvature of the liquid-vapor interface particular, when introducing the basic concepts of capillarity,
[see Fig 15(d)]. If integrated over the whole submerged it is much simpler to work from the thermodynamic perspec-
solid, the curvature of the solid gives a zero resultant force, tive: energy minimization naturally yields the equilibrium
whereas the curvature of the liquid is integrated only where conditions, and the resultant forces can be calculated from the
the prewetting film exists. As a result, the resultant force is virtual work principle. Nevertheless, our analysis provides a
vertical and has an amplitude cLV per unit length of the appa- number of insights that are useful when teaching capillarity:
rent contact line.
This result is consistent with the thermodynamic perspec- 1. To determine the capillary forces it is crucial to explicitly
tive. Because the solid is covered by a liquid layer much specify the system (a specific collection of matter) to
thicker than the molecular size, the surface tension above the which the forces are applied.
apparent contact line is not cSV but is cSL þ cLV, because the 2. The surface tensions cSL and cSV do not pull on the solid.
plate is always completely submerged. In essence, this cov- 3. The global force exerted on the solid by the liquid can be
erage means that the plate never leaves the liquid bath when calculated by adding the contributions of the Laplace
6
pressure inside the liquid and a localized surface tension M. Berry, “The molecular mechanism of surface tension,” Phys. Educ. 6,
79–84 (1971).
force cLV parallel to the liquid-vapor interface. Although 7
J. W. Gibbs, The Collected Works of J. Willard Gibbs (Yale U. P.,
this force construction gives the correct answer, it does London, 1957).
not reflect the true microscopic distribution of liquid-on- 8
T. Young, “An essay on the cohesion of fluids,” Philos. Trans. 95, 65–87
solid forces. (1805).
9
4. In contrast, the resultant force on the liquid near the con- J.-P. Hansen and I. R. McDonald, Theory of Simple Liquids, 3rd ed. (Aca-
tact line does involve the surface tensions cLV, cSL, and demic, San Diego, 2006).
10
cSV. J. Indekeu, “Line tension near the wetting transition – Results from an
interface displacement model,” Physica A 183, 439–461 (1992).
5. The classical construction of Fig. 3(b) to explain Young’s 11
M. Nijmeijer, C. Bruin, A. Bakker, and J. Van Leeuwen, “Wetting and
law does not accurately represent the force balance. A drying of an inert wall by a fluid in a molecular-dynamics simulation,”
complete picture is provided in Fig. 10(a). Phys. Rev. A 42, 6052–6059 (1990).
12
J. H. Weijs, A. Marchand, B. Andreotti, D. Lohse, and J. H. Snoeijer,
We hope that the force construction of Fig. 10(a) will be “Origin of line tension for a Lennard-Jones nanodroplet,” Phys. Fluids 23,
used to explain Young’s law in Eq. (2). It is conceptually 022001-1–11 (2011).
13
simple, clarifies the system to which forces are applied, and J. N. Israelachvili, Intermolecular and Surface Forces (Academic, San
represents perfect mechanical equilibrium. That is, besides a 14
Diego, 1991).
balance of normal and tangential components, the forces also C. Bauer and S. Dietrich, “Quantitative study of laterally inhomogeneous
wetting films,” Eur. Phys. J. B 10, 767–779 (1999).
exert a zero torque. 15
T. Getta and S. Dietrich, “Line tension between fluid phases and a sub-
We note that the virtual work principle yields the correct strate,” Phys. Rev. E 57, 655–671 (1998).
resultant force on a solid, but cannot recover the true micro- 16
S. Das, A. Marchand, B. Andreotti, and J. H. Snoeijer, “Elastic deforma-
scopic force distribution. A knowledge of such a force distri- tion due to tangential capillary forces,” Phys. Fluid 23, 072006 (2011).
17
bution is crucial when we want to take into account how a R. Finn, “The contact angle in capillarity,” Phys. Fluids 18, 047102-1–7
solid is elastically deformed by the contact line.19–21 Even 18
(2006).
though these deformations can be as small as a few nano- R. Finn, “Comments related to my paper “The contact angle in capil-
larity,” Phys. Fluids 20, 107104-1–4 (2008).
meters, they can be measured using modern experimental 19
A. Rusanov, “Theory of wetting of elastically deformed bodies. 1. Defor-
techniques.22–25 This experimental access renews the funda- mation with a finite contact angle,” Coll J. USSR 37, 614–622 (1975).
mental interest in the microscopic details of capillarity.16 20
A. Carre, J. Gastel, and M. Shanahan, “Viscoelastic effects in the spread-
ing of liquids,” Nature 379, 432–434 (1996).
21
ACKNOWLEDGMENTS L. R. White, “The contact angle on an elastic substrate. 1. The role of dis-
joining pressure in the surface mechanics,” J. Colloid Inter. Sci. 258, 82–
We thank J. van Honschoten and K. Winkels for critically 96 (2003).
22
R. Pericet-Camara, G. K. Auernhammer, K. Koynov, S. Lorenzoni, R. Rai-
reading the manuscript. B.A. thanks the students of the Uni-
teri, and E. Bonaccurso, “Solid-supported thin elastomer films deformed
versity Paris-Diderot’s Master of Physics program for both by microdrops,” Soft Matter 5, 3611–3617 (2009).
their impertinent and pertinent questions. 23
R. Pericet-Ca?mara, A. Best, H.-J. Butt, and E. Bonaccurso, “Effect of
capillary pressure and surface tension on the deformation of elastic surfa-
1
P.-G. de Gennes, “Wetting” Statics and dynamics,” Rev. Mod. Phys. 57, ces by sessile liquid microdrops: An experimental investigation,” Lang-
827–863 (1985). muir 24, 10565–10568 (2008).
2 24
P.-G. de Gennes, F. Brochard-Wyart, and D. Quéré, Capillarity and Wet- Y. Wang, B. Bhushan, and X. Zhao, “Nanoindents produced by nanobub-
ting Phenomena (Springer, New York, 2004). bles on ultrathin polystyrene films in water,” Nanotechnology 20 045301-
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D. Bonn, J. Eggers, J. Indekeu, J. Meunier, and E. Rolley, “Wetting and 1–6 (2009).
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spreading,” Rev. Mod. Phys. 81, 739–805 (2009). Y.-S. Yu and Y.-P. Zhao, “Elastic deformation of soft membrane with fi-
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tension,” J. Chem. Phys. 17, 338–343 (1949). 339, 489–494 (2009).
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Publications. Mineola, NY, 1982). sure at the solid-fluid interface,” Phys. Fluids 19, 118105-1–4 (2007).

Why Is Surface Tension A Force Parallel To The Interface?: Additional Information On Am. J. Phys

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Why is surface tension a force parallel to the interface?

Antonin Marchand, Joost H. Weijs, Jacco H. Snoeijer, and Bruno Andreotti

Citation: Am. J. Phys. 79, 999 (2011); doi: 10.1119/1.3619866

Additional information on Am. J. Phys.

I. INTRODUCTION for a system of volume V containing N molecules at tempera-

III. MICROSCOPIC INTERPRETATION

Fig. 7. Forces exerted on a subsystem of liquid (dotted region) by the rest of

D. The liquid-solid interface

cSL ¼ cSV þ cLV ASL : (4)

ASL ¼ cSV þ cLV cSL ¼ cLV ð1 þ cos hÞ (5)

In the last step, we used Young’s law for the equilibrium

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