Surface Tension

조우진, 윤종인, 김홍
Introduction
Surface tension
 Molecules at the liquid-gas interface have
weaker binding than molecules in the bulk,
since the attraction of liquid molecules to each
other is greater than to the molecules in the air
 The net force becomes an inward force that
causes the liquid to behave as if its surface were
covered with a stretched elastic membrane
 Tension from the imbalanced forces →
“Surface Tension”
Qualitative approach on surface tension
 At the interface between two materials, a molecule is exposed to a
different environment than inside the material → Different binding
energy
 In the continuum limit where the transition layer becomes a
mathematical surface separating one material from the other, the
difference in molecular binding energy manifests itself as a
macroscopic surface energy density.
 Molecules at the liquid-gas interface have weaker binding than
molecules in the bulk.
Qualitative approach on surface tension
 The missing binding energy can therefore be viewed as a positive
energy added to the surface itself
 Since a larger area of the surface contains larger surface energy,
external forces must perform positive work against internal surface
forces to increase the total area of the surface
 Mathematically, the internal surface forces are represented by
surface tension, defined as the normal force per unit length
Basic physics of surface
tension
Molecular origin of surface energy
 The molecules are placed in a cubic grid, with grid
length equal to the molecular separation length Lmol
 If the total binding energy of a molecule in the bulk is
5
ϵ, a surface molecule will only be bound by ϵ. The
6
missing binding energy corresponds to adding an
1
extra positive energy ϵ for each surface molecule
6
Molecular origin of surface energy
 The binding energy may be estimated as 𝜖 ≈ ℎ𝑚 where h is the
specific heat of evaporation (evaporation enthalpy per unit of mass)
and 𝑚 = 𝑀𝑚𝑜𝑙 /𝑁𝐴 = 𝜌𝐿3𝑚𝑜𝑙 is the mass of a single molecule
1
 Dividing the molecular surface energy ϵ with the molecular area
6
scale 𝐿2𝑚𝑜𝑙 , we arrive at the following estimate of the surface energy
density γ
1
ϵ 1 ℎ𝑚 1
6
𝛾 = 2 ≈ 2 ≈ ℎ𝜌𝐿𝑚𝑜𝑙
𝐿𝑚𝑜𝑙 6 𝐿𝑚𝑜𝑙 6
 Small thickness is offset by the fairly large values of ρ and h in normal
liquids
Work and surface energy density
 Increasing the area of an interface with energy density γ by a tiny
amount dσ requires an amount of work equal to the surface energy
contained in the extra piece of interface
𝑑𝑤 = 𝛾𝑑𝜎
 The work of surface formation at constant volume and temperature can
be identified with the change in Helmholtz energy, and we can write
𝑑𝐴 = 𝛾𝑑𝜎
 The surface tension associated with a liquid interface against liquid is
always positive because of the missing negative binding energy of the
surface molecules
Work and surface energy density
 Interfaces between solids and liquids or between liquids and liquids
are not required to have positive interfacial energy density
 The sign depends on the strength of the cohesive forces holding
molecules of a material together compared to the strength of the
adhesive forces between the opposing molecules of the interfacing
materials
 If interfacial energy density between two liquids is negative, a large
amount of energy can be released by maximizing the area of the
interface → two liquids are mixed thoroughly instead of being kept
separate
Force and surface tension
 The resistance against extension of a free
surface shows that the surface has an internal
surface tension which we shall now see equals
to the surface energy density γ
 Suppose we wish to stretch the surface along a
straight line of length L by a uniform amount
ds. Since the area is increased by 𝑑𝐴 = 𝐿𝑑𝑠,
the force we apply orthogonally to the line is
F = 𝑑𝑊/𝑑𝑠 = 𝛼𝐿
Force and surface tension
 In equilibrium, the applied normal force per
unit of area, 𝐹/𝐿 = 𝛾 defines the internal
surface tension γ
 Surface tension is thus identical to surface
energy density.
 The dimension of surface tension is thus
Jm−2 = N𝑚−1
Force and surface tension
 Let an oriented open surface be divided into two
parts by an oriented curve, such that the surface
has a uniquely defined left and right hand side
with respect to the curve
 The force that the right hand side of the surface
exerts on the left hand side through the curve
element dl then becomes
 𝑑𝑭 = 𝛾𝑑𝒍 × 𝒏 ෝ
 The net force is obtained by integrating this
expression along the curve
Force and surface tension
 It follows that to shift a piece of the curve of
length L by ds orthogonal to the curve the work
is given by 𝑑𝑤 = 𝛾𝑑𝜎, with 𝑑𝜎 = Lds
 Surface tension does not depend on how much
the interface has already been stretched
 Soap films and biological membranes are an
exception and behave like elastic membranes
because of their peculiar surfactants
Pressure excess in a sphere droplet (or bubble)
 In the absence of all external forces, the surface tension will attempt make
the droplet spherical, the shape of which has the smallest area for a given
volume
 Surface tension makes the pressure higher inside a spherical droplet
 If we increase the radius R by an amount dR we must perform the extra
work 𝑑𝑊 = 𝛾𝑑𝐴 − ∆𝑝𝑑𝑉, where ∆𝑝 denote the extra positive pressure
inside the liquid
 Since 𝑑𝐴 = 8𝜋𝑅𝑑𝑅 and 𝑑𝑉 = 4𝜋𝑅2 𝑑𝑅, in equilibrium(𝑑𝑊 = 0)
2𝛾
∆𝑝 =
𝑅
 It is clear that for a double-layered droplet such as a soap bubble, the extra
positive pressure doubles
Contact angle and capillary
effect
Contact angle
 The two-dimensional interface between two
homogeneous fluids makes contact with a solid
container wall along a one-dimensional contact
line
 For the typical case of a three-phase contact
between solid, liquid and gas the contact angle χ is
defined as the angle between the solid and the
interface
 Water and air against clean glass meet in a small
acute contact angle, whereas mercury and air
meets glass at an obtuse contact angle.
Young’s law
 The contact angle is a material constant which
depends on the properties of all three materials
coming together
 Whereas material adhesion can maintain a tension
normal to the solid wall, the tangential tension has to
vanish at the contact line.
 This yields an equilibrium relation called Young’s
law
α denotes surface tension(γ)
the non subscripted one is the 𝛾𝑠𝑔 = 𝛾𝑠𝑙 + 𝛾𝑙𝑔 cos χ
surface tension between liquid
and gas blank null nothing
𝛾𝑠𝑔 : solid/gas surface tension, 𝛾𝑠𝑙 :solid/liquid surface
tension, 𝛾𝑙𝑔 :gas/liquid surface tension
Young’s law
 Hence the cosine of the contact angle becomes
𝛾𝑠𝑔 − 𝛾𝑠𝑙
cos χ =
𝛾𝑙𝑔
 If we note that the superficial work of adhesion of the liquid to the
solid is
𝑤𝑎𝑑 = 𝛾𝑠𝑔 + 𝛾𝑙𝑔 − 𝛾𝑠𝑙
 The equation above can be written as
𝑤𝑎𝑑
cos χ = −1
𝛾𝑙𝑔
Young’s law
𝜋
 For 0 < 𝛾𝑠𝑔 − 𝛾𝑠𝑙 < 𝛾𝑙𝑔 the contact angle is acute (0 < χ < )
2
𝜋
 For −𝛾𝑙𝑔 < 𝛾𝑠𝑔 − 𝛾𝑠𝑙 < 0 the contact angle is obtuse ( < χ < 𝜋)
2
 If 𝛾𝑠𝑔 − 𝛾𝑠𝑙 > 𝛾𝑙𝑔 the contact line cannot be static, but will be drawn
towards the gas while dragging the liquid along, thereby spreading it
all over a horizontal surface
 If 𝛾𝑠𝑔 − 𝛾𝑠𝑙 < −𝛾𝑙𝑔 the contact line will recede from the gas on a
horizontal surface until all the liquid collects into nearly spherical
pearls
Young’s law
Fig. Contact Angle Degree of Relation between
2 wetting surface tensions

S χ=0 Perfect 𝛾𝑠𝑔 − 𝛾𝑠𝑙 > 𝛾𝑙𝑔

wetting

C 𝜋 High 0 < 𝛾𝑠𝑔 − 𝛾𝑠𝑙 < 𝛾𝑙𝑔

0<χ<
2 wettability

B 𝜋 Low −𝛾𝑙𝑔 < 𝛾𝑠𝑔 − 𝛾𝑠𝑙 < 0

<χ<𝜋
2 wettability

A χ=𝜋 Perfectly 𝛾𝑠𝑔 − 𝛾𝑠𝑙 < −𝛾𝑙𝑔

Non-wetting
Capillary action
 The tendency of liquids to rise up capillary tubes is called capillary
action, and it is a consequence of surface tension
 When the surface tension of glass in contact with air is larger than that
of glass in contact with water, i.e. γsg>γsl, the water rises to height h
where the upwards force due to the difference in surface tension
balances the downwards weight of the raised water column
(disregarding the volume of the meniscus-shaped surface, and
assuming the radius of the column is a),
𝛾𝑠𝑔 − 𝛾𝑠𝑙 2𝜋𝑎 ≈ 𝜌𝑔𝜋𝑎2 ℎ
2𝛾𝑙𝑔
ℎ≈ cos χ
𝜌𝑔𝑎
Surface films
The thermodynamics of surface layers
 A surfactant is a compound that lower the surface tension between two
phases
 To establish the relation between the concentration of surfactant at a
surface and he change in surface tension it brings about, consider two
phases α and β in contact and suppose that the system consists of
several components J, each one present in an overall amount nJ
 If the components were distributed uniformly trough the two phases
right up to the interface, which is taken to be a plane of surface area σ,
the total Gibbs energy would be
𝐺 = 𝐺 𝛼 + 𝐺(𝛽)
The thermodynamics of surface layers
 However, the components are not uniformly distributed because one
may accumulate at the interface
 As a result, the sum of the two Gibbs energies differs from G by an
amount called the surface Gibbs energy G(σ)
𝐺 σ = 𝐺 − 𝐺 𝛼 + 𝐺(𝛽)
 Similarly, the total amount of J differs from the sum of n(α) and n(β)
and is denoted by n(σ)
𝑛 𝜎 = 𝑛𝐽 − 𝑛𝐽 (𝛼) − 𝑛𝐽 (𝛽)
The thermodynamics of surface layers
 The surface excess ΓJ is expressed as follows
𝑛𝐽 (𝜎)
Γ𝐽 =
𝜎
 Using the surface excess, the relation called the Gibbs isotherm is
obtained as follows
𝑑𝛾 = − ෍ Γ𝐽 𝑑𝜇𝐽
𝐽
The thermodynamics of surface layers
 The derivation of the Gibbs isotherm
The Gibbs free energy of each phase α, β, surface can be represented by the
equation
𝐺 = 𝑈 + 𝑝𝑉 − 𝑇𝑆 + σ𝑖 𝜇𝑖 𝑛𝑖 such that
𝑑𝐺 = 𝑑𝑈 + 𝑝𝑑𝑉 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 + σ𝑖 𝜇𝑖 𝑑𝑛𝑖 + σ𝑖 𝑛𝑖 𝑑𝜇𝑖 .
Nothing that 𝑑𝐺 = σ𝑖 𝑑𝐺𝑖 + 𝛾𝑑σ = σ𝑖 𝐺𝑖 𝑑λ + 𝛾σ𝑑λ, 𝐺 = σ𝑖 𝐺𝑖 + 𝛾σ
Hence for each phase α, β, S(surface)
𝑑𝐺 = ෍ 𝑑𝑈 + 𝑝𝑑𝑉 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 + ෍ 𝜇𝑖 𝑑𝑛𝑖 + ෍ 𝑛𝑖 𝑑𝜇𝑖 + σ𝑑𝛾 + 𝛾𝑑σ
𝛼,𝛽,𝑆 𝑖 𝑖
The thermodynamics of surface layers
 The derivation of the Gibbs isotherm
Considering the relations 𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃 + σ𝑖 𝜇𝑖 𝑑𝑛𝑖 for each
phase and 𝑑𝑈 = σ𝛼,𝛽,𝑆(𝑇𝑑𝑆 − 𝑝𝑑𝑉 + 𝛿𝑤𝑛𝑜𝑛−𝑝𝑉 ) = σ𝛼,𝛽,𝑆(𝑇𝑑𝑆 −
The thermodynamics of surface layers
 The derivation of the Gibbs isotherm
Hence the equation becomes
0 = ෍ 𝑛𝐽 (𝜎)𝑑𝜇𝐽 + 𝜎𝑑𝛾
𝐽
such that
𝑛𝐽 (𝜎)
𝑑𝛾 = − ෍ 𝑑𝜇𝐽 = ෍ Γ𝐽 𝑑𝜇𝐽
𝐽 𝜎
𝐽
The thermodynamics of surface layers
 Consider a simplified model of the interface in which the ‘oil’ and
‘water’ phases are separated by a geometrically flat surface
 This approximation implies that only the surfactant, S, accumulates at
the surface, hence Γoil and Γ are both zero such that
𝑑𝛾 = −𝛤𝑆 𝑑𝜇𝑆
 For dilute solutions, 𝑑𝜇𝑠 = 𝑅𝑇 ln 𝑐 (c: the molar concentration of the
surfactant) such that
𝑑𝑐 𝜕𝛾 𝑅𝑇𝛤𝑆
𝑑𝛾 = −𝑅𝑇𝛤𝑆 , =−
𝑐 𝜕𝑐 𝑇 𝑐
The thermodynamics of surface layers
 If the surfactant accumulates at the interface, its surface excess is
𝜕𝛾
positive and <0
𝜕𝑐 𝑇
 Surface tension decreases when a solute accumulates at a surface
 Conversely, if the concentration dependence of γ is known, then the
surface excess may be predicted and used to infer the area occupied by
each surfactant molecule on the surface
Condensation
Kelvin equation for the vapor pressure of a
liquid droplet
 𝑑𝜇 𝑔 = 𝑑𝜇 𝑙 at equilibrium. Using 𝑑𝜇 = 𝑉𝑑𝑃 with constant
temperature and the ideal gas equation the following equation is
obtained
𝑅𝑇𝑑𝑝
= 𝑉𝑚 𝑙 𝑑𝑃
𝑝
Considering Vm(l) stays nearly constant under the pressure change,
𝑉𝑚 ∆𝑝 2𝛾𝑉𝑚
𝑝= 𝑝∗ 𝑒 𝑅𝑇 = 𝑝∗ 𝑒 𝑟𝑅𝑇
is obtained by integration