ISSN 1061933X, Colloid Journal, 2012, Vol. 74, No. 2, pp. 266–268. © Pleiades Publishing, Ltd., 2012.

The present paper is dedicated to the 80th anniversary of academician A.I. Rusanov

Capillary Pressure of van der Waals Liquid Nanodrops1

R. Tsekov and B. V. Toshev
Department of Physical Chemistry, University of Sofia, 1164 Sofia, Bulgaria
Received September 30, 2011

Abstract—The dependence of the surface tension on nanodrop radius is important for the newphase forma
tion process. It is demonstrated that the famous Tolman formula is not unique and the sizedependence of
the surface tension can distinct for different systems. The analysis is based on a relationship between the sur
face tension and disjoining pressure in nanodrops. It is shown that the van der Waals interactions do not affect
the newphase formation thermodynamics since the effects of the disjoining pressure and sizedependent
component of the surface tension cancel each other.
DOI: 10.1134/S1061933X12020135

1 In small systems all thermodynamic parameters papers in this field have been published [7–14],
depend on the system size. Their values differ from amongst them articles with computer simulations.
those in large systems, which are usually given in ther
modynamic reference books. For instance, if an inter The problem of the sizedependent surface tension
face approaches another one the transitionphase can be considered from an alternative perspective. The
regions overlap. As a result, both the surface tension thin liquid film is another small system, where the two
and pressure in the gap dividing the two surfaces surfaces of discontinuity overlap and no bulk liquid
change, due to onset of the disjoining pressure. The core within the film exists. This fact is quantitatively
present paper focuses on small droplets, where the sur manifested via the film disjoining pressure Π intro
face tension depends on the drop radius. The descrip duced by Derjaguin [15]. The present study aims to
tion of such a system is important for the theory of calculate the disjoining pressure for a drop and then,
nucleation [1–3], smog, fog and nanoemulsion sta using the relation between Π and σ, to obtain the size
bility, etc. dependence of the nanodrop surface tension. In what
Let us consider a globular mass surrounded by a follows we consider thermodynamic description of a
bulk gas phase, which is sufficiently small that no small drop and a definition of the disjoining pressure
region of the mass can be regarded as homogeneous of the drop is derived. As an example, the van der
phase owning bulk properties. The wellknown Tol Waals disjoining pressure of the drop is calculated via
man formula [4] for the effect of drop size on the sur the method of Hamaker [16] with the equation of
face tension [3] London [17].
σ = σ ∞(1 − 2δ ∞ R) (1) The mechanical behavior of a drop is determined
was derived by careful analysis of the Gibbs remarks on by its pressure tensor. The normal component PN of
the problem [5]. Here σ and σ ∞ are the surface tension the pressure tensor in the drop center differs from the
of a drop and a planar liquid/vapor interface, respec pressure PG in the homogenous gas phase and their
tively, δ∞ is the socalled Tolman length, and R is the difference is given by the hydrostatic Laplace law
drop radius. In the present paper the latter is consid
ered to mark the surface of tensions. Some assump PN − PG = 2σ/R, (2)
tions in the derivation of Eq. (1) are, however, consid
ered to be questionable [6] and this is corroborated by which holds in any case, no matter if there is a bulk liq
the fact that the linear dependence of σ vs. 1 R has not uid core within the drop or the drop is so small that no
been experimentally verified. Moreover, neither the part is homogeneous. For the latter case, according to
magnitude nor even of the sign of the Tolman length is the Gibbs consideration [5], a hypothetical liquid
obvious. Thus, the sizedependence of the surface ten phase, having the same temperature and chemical
sion is still an open area of research and several new potential as the gas phase, is attributed to the mass,
which is conceived as existing within the dividing sur
1 The article is published in the original.
face. The pressure PL in this liquid phase differs from

266
 CAPILLARY PRESSURE OF VAN DER WAALS LIQUID NANODROPS 267

PN and their difference is known as disjoining pressure bubble with radius R, with the surrounding liquid.
[2, 14] Using the London equation [17] for the energy of
attraction between two molecules, the following
Π ≡ PN − PL. (3) expression is obtained
According to thermodynamics, the characteristic ∞
function of a system at constant temperature and
chemical potential is the omega potential. The Ω Π VW = − 12 λ6 4πr 2dr = − 4 A 3 ,
∫ (10)
potential of a liquid drop is given by the expression vL r 3πR
R

Ω = −PLV + σ O, (4) where λ is the London constant, v L is volume per mol

ecule of liquid, and A = π 2λ v L2 is the Hamaker con
where V = 4πR 3 3 and O = 4 π R are the drop volume
2
stant. By introducing Eq. (10) into Eq. (9) and inte
and surface area, respectively. Note that according to grating the result one yields
the Gibbs–Duhem relation for the liquid phase, the
pressure PL is constant at constant temperature and σ = σ ∞(1 − a 2 R 2 ), (11)
chemical potential. On the other hand the work neces
sary to change the drop size can be calculated via the where a ≡ 2 A 3πσ ∞. For the typical values of the
relation Hamaker constant and surface tension the length a is
of the order of a nanometer and, hence, deviations of
d Ω = −PNdV + σdO. (5) σ from σ ∞ are essential in nanodrops only. It is evident
Substituting Ω from Eq. (4) and employing definition that the sizedependent surface tension from Eq. (11)
(3) one yields the Gibbs–Duhem relation for a drop at is inverse proportional to square of the drop radius,
constant temperature and chemical potential and, consequently, differs from the Tolman formula
Π dV = −Od σ. (6) (1). Also, according to Eq. (11) the surface tension of
a nanodrop is always lower than σ∞.
For the case of a spherical drop Eq. (6) can be easily
transformed to the following expression By replacing the surface tension in Eq. (8) by Eq.
(11), one obtains the following expression for the cap
Π = −∂σ ∂R , (7) illary pressure
relating the disjoining pressure and the first derivative PL − PG = 2σ ∞ R . (12)
of the surface tension with respect to the drop radius.
Equation (7) states that the dependence of the surface This expression holds either for relatively large drops,
tension on the drop size indicates excess energy in the where PL = PN, or for very small drops, where PL ≠ PN.
small drop compared to the bulk phase. This expres In both cases the thermodynamic Laplace law (12)
sion is very similar to Π = − 2∂σ ∂ h for foam films [2, involves the surface tension σ ∞ of the plane interface.
18], where h is the film thickness. The authors are of the opinion that Eq. (12) is in fact
Combining now Eqs. (2) and (3) one can calculate expressed by the Gibbs statement: “With this under
the capillary pressure of the drop standing with regard to the phase of the fictitious inte
rior mass, there will be no ambiguity in the meaning of
PL − PG = 2σ R − Π = 2σ R + ∂σ ∂R . (8) any of the symbols which we have employed, when
The last expression is derived by employing Eq. (7) applied to cases in which the surface of discontinuity is
and represents a known result from the literature. spherical, however small the radius may be” [5].
Finally, by direct integration of Eq. (7), a useful By combining Eqs. (8) and (12) the following equa
expression for calculating the surface tension of a drop tion can be obtained
is obtained 2σ ∞ R + Π VW = 2σ R . (13)
∞
This equation can also be derived by the force balance
∫
σ = σ ∞ + Π dR. (9) method, in which a spherical drop with radius R is cut
in two equal parts and one of these parts is “solidified”
R
Equation (9) shows that the sizedependence of the (the Steven method). The liquid part of the drop is
surface tension is not universal in contrast to the Tol characterized by σ and PN, while the “solidified” part
man formula. The surface tension is determined by the of the drop is represented by σ ∞ and PL. Hence, at
specific interactions within the drop, which reflect mechanical equilibrium the force balance
various components of the disjoining pressure. The
contribution of the most widespread force, i.e. the van πR 2PN − 2πRσ = πR 2PL − 2πRσ ∞ (14)
der Waals attraction, is considered below. The method is applicable, which also results in Eq. (13). A similar
of Hamaker [16] is used to calculate the disjoining situation exists in the mechanical description of the
pressure of the drop. Thus, the van der Waals disjoin transition zone between a planeparallel liquid film
ing pressure is equal to the energy per unit volume of and a bulk liquid meniscus. In this case, the Derjaguin
the interaction of a molecule, placed in the center of a approach [19] with constant surface tension and dis

COLLOID JOURNAL Vol. 74 No. 2 2012

268 TSEKOV, TOSHEV

joining pressure and the de Feijter approach [20] with 5. Gibbs, J.W., The Scientific Papers of J. Willard Gibbs:
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for drops with electrostatic forces [22]. The correct Sci., 1977, vol. 62, p. 542.
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sion or disjoining pressure. 1981, vol. 75, p. 3986.
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