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On Capillary Rise and Nucleation

Article  in  Journal of Chemical Education · October 2008

DOI: 10.1021/ed085p1389

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On Capillary Rise and Nucleation
R. Prasad
Department of Applied Mechanics, Indian Institute of Technology, Hauz Khas, New Delhi, 110016 India; rajesh@am.iitd.ac.in
The change of one phase into another, known as phase
transformation, is important in physical chemistry (1). There are
many examples such as melting (solid to liquid), solidification
(liquid to solid), evaporation (liquid to vapor), condensation
(vapor to liquid), and so forth. Many natural phenomena and
industrial processes depend upon such transformations. An
important example of phase transformation in nature is con-
densation of water vapor in the atmosphere to form clouds (2).
An example from technology is solidification of liquid metals,
the basis of the foundry industry (3).
Many phase transformations, of which condensation and
solidification are examples, take place via nucleation and growth
(4). Nucleation is the first appearance of a stable particle of the
product phase in the metastable phase. Subsequent increase in
the size of the particle is called growth. Control of nucleation is
an important step in the control of microstructure and proper-
ties of the final product. An increase in nucleation rate during
solidification results in a microstructure with fine grains and
hence enhanced mechanical properties (5). On the other hand,
In the Classroom
basis for the comparison suggested above. Finally we offer some
suggestions on how to include this material in teaching.
Capillary Rise
The rise of a liquid against gravitational forces in a vertical
tube of small diameter is well-known; the formula for the height
of the liquid column is derived in most physical chemistry text-
books (1). The most common method for doing this is through
a force balance: the surface tension force balances the weight of
the liquid column. However, to compare this phenomenon with
that of nucleation, it is instructive to use the energy approach
proposed by Markworth (7). Despite its utility, most textbooks
do not use or mention this approach.
Consider a liquid column of height h as shown in Figure 1.
Following Markworth (7), the change in the energy ΔEh of the
system due to the rise of this column can be given by
h
%Eh  2 Qr h H sl  H sv
 Q r 2 h S g (1)
suppressing nucleation altogether leads to an amorphous or
glassy product (6).
Capillary rise is another important topic in physical chem-
istry (1). It is a good practical example demonstrating the effect
of surface energy. The two concepts, capillary rise and homoge-
neous nucleation, are usually discussed separately. In this article
we present a pedagogic comparison of nucleation and capillary
rise. We show that both phenomena result from a competition
between two opposing energy factors: a volume energy and a
surface energy. In capillary rise the surface energy factor drives
the process whereas the volume energy factor opposes it. The
roles of the two energy factors are reversed in nucleation: surface
energy opposes it whereas the volume energy drives it. We first
present derivations of equilibrium height of capillary rise and
critical radius for homogeneous nucleation. These form the
A B
Hsv
h volume energy, initially decreases as a function of h, reaches a
R changes are shown in Figure 2. The equilibrium height h* is given
Hlv
Hsl
Figure 1. (A) The rise of a liquid in a capillary, h is the height of the
liquid in the capillary. (B) Surface tensions acting at the junction of
the meniscus and the capillary wall. γlv, γsv, and γsl are the surface
tensions of the liquid–vapor, solid–vapor, and the solid–liquid
interfaces, respectively. θ is the contact angle.
© Division of Chemical Education  •  www.JCE.DivCHED.org  •  Vol. 85  No. 10  October 2008  •  Journal of Chemical Education
2
where r is the inner radius of the tube; γsl and γsv are the solid–
liquid and solid–vapor interfacial energies per unit area, respec-
tively; ρ is the density of the liquid; and g is the acceleration due
to gravity. The first term on the right-hand side of eq 1 represents
the decrease in Gibbs energy due to replacement of higher
energy solid–vapor interface with lower energy solid–liquid
interface (for systems showing capillary rise). This decrease in
Gibbs energy is what drives the capillary rise and it can be called
its “driving force”. However, the rise of the liquid column in the
capillary also leads to the inevitable rise in the gravitational po-
tential energy of the system. The potential energy is the product
of the mass (πr 2hρ) of the liquid column, the gravitational ac-
celeration ( g) and the height (h/2) of the center of mass of the
liquid column. Thus the second term on the right-hand side of
eq 1 opposes the capillary rise and hence acts as a barrier. This
energy term depends upon the volume of the column and can
be called the volume energy. As can be seen from eq 1 that the
volume energy term is proportional to h2 whereas the surface
energy term is proportional to h, hence their ratio goes as h. This
means that the driving force represented by surface energy will
be dominant at small h but the opposing term of gravitational
potential energy will eventually become significant at large h.
The total energy ΔEh, which is the sum of surface energy and
minimum at h*, and then begins to increase. Thus the liquid
column will rise initially but will face increasing opposition later
and so will finally stop at an equilibrium height h*. The energy
by setting ∂ΔEh/∂h = 0:
2 H sl  H sv
h*  (2)
Sg r
Note that since (γsl – γsv) is negative for a system showing capil-
lary rise, h* is positive.
1389
 In the Classroom

More commonly, h* is expressed in terms of the liquid– Homogeneous Nucleation

vapor interfacial energy γlv and the contact angle θ, see Figure
1B. This can be done through the balance of surface tension In this section, we present a derivation for the critical ra-
forces leading to the well-known Young–Dupré equation: dius for homogeneous nucleation. For simplicity, we consider
the case of condensation of liquid droplets in an undercooled
H sl  H lv cos R  H sv (3)
Substituting γsv from eq 3 into eq 2, we get the familiar expres-
sion for capillary rise:
2 H lv cos R
h*  (4)
vapor. As mentioned in the introduction this has relevance to
atmospheric chemistry and formation of clouds (2). The Gibbs
energy change for the formation of a spherical liquid droplet of
radius R in an undercooled vapor below its condensation point
is given by (e.g., see ref 9)
4
Sg r
We would like to point out that the energy-based derivation
of capillary rise used here as given originally by Markworth (7)
helps in comparison of this phenomenon to that of nucleation.
However, the derivation has some limitation, for example,
Henriksson and Eriksson (8) have shown that the energy-based
derivation cannot account for the meniscus curvature.
V
%Eh
Energy
h*
S more than offsets any decrease in volume energy. Any droplet of
Height
Figure 2. The energy terms involved in a capillary rise. ΔEh is the
change in the energy of the system and is the sum of two terms: the
surface energy term S and the volume energy term V. The equilibrium
height h* to which the liquid finally rises correspond to the minimum
of ΔEh curve.
S 2 H lv
Energy
R*
V %dG
Radius
2
Figure 3. The energy terms involved in a homogeneous nucleation
resulting in a critical radius. The surface energy term S and the
volume energy term V combine to give the free energy of formation
ΔdG of a liquid droplet in a supersaturated vapour below its
condensation point. The maximum in the ΔdG curve correspond to
the critical radius R*.
1390 Journal of Chemical Education  •  Vol. 85  No. 10  October 2008  •  www.JCE.DivCHED.org  •  © Division of Chemical Education
% dG   Q R 3 % vG  4 Q R 2 H lv (5)
3
where Δ vG is the Gibbs energy difference Gv − Gl between liquid
and vapor per unit volume and γlv is the surface tension of the
vapor–liquid interface. The two terms on the right-hand side of
eq 5 and their sum, ΔdG, are shown in Figure 3. The first term
on the right-hand side of eq 5 is the volume term representing
the decrease in Gibbs energy due to formation of a stable liquid
droplet of lower energy in the higher energy metastable vapor.
This decrease in Gibbs energy is what drives the nucleation and
is appropriately called the “driving force”. However, the droplet
cannot form without an inevitable vapor–liquid interface. This
interface has a surface energy associated with it that will tend to
increase the energy of the system. Thus the second term in eq 5
representing the surface term opposes the nucleation. Since the
surface energy term is proportional to R2 whereas the volume en-
ergy term is proportional R3, their ratio goes by 1/R. This means
that the surface energy term will be dominant at small R while
the volume energy term will become important at larger R. For
liquid droplets of very small radius, the increase in surface energy
such radii, if formed, will vaporize. On the other hand for drop-
lets of reasonably large radii the decrease in volume energy more
than compensates for any increase in the surface energy. Such
droplets can grow in size. Thus the total energy Δ dG, which is the
sum of surface energy and volume energy, initially increases as a
function of R, reaches a maximum and then begins to decrease.
The radius corresponding to the maximum in Δ dG is called the
critical radius R* and is given by setting ∂Δ dG∙∂R = 0:
R*  (6)
% vG
A droplet of radius R* is at the maximum of energy and can be
considered to be in a state of unstable equilibrium. If it shrinks
slightly by vaporization it will continue to shrink until it disap-
pears. On the other hand, if it grows slightly it will grow into a
stable phase. Substituting R* from eq 6 into eq 5 gives ΔG*, the
value of Δ dG at R*. This is the so called barrier to nucleation
and is given by
16Q Hsl 3
%G *  (7)
3 % vG
Comparison
The derivation for the capillary rise based on energy ap-
proach of Markworth (7) brings out the similarity to and differ-
ences from the critical radius for homogeneous nucleation. This
 

Table 1. A Comparison of Homogeneous Nucleation and Capillary Rise
Property Homogeneous Nucleation
Volume energy Chemical Gibbs energy
Cubic in R
Assists nucleation
Surface energy γlv
Quadratic in R
Opposes nucleation
Nature of equilibrium Unstable
is summarized in Table 1. As can be seen, both homogeneous
nucleation and capillary rise are a result of balance between
two opposing factors: a surface energy and a volume energy. In
the case of homogeneous nucleation the volume factor is the
chemical Gibbs energy change and it drives the transformation.
On the other hand, in the case of capillary rise, the gravitational
potential energy, playing the role of volume factor, opposes the
rise. Similarly the role of surface energy is also reversed in the
two cases: it opposes the nucleation but drives the capillary rise.
The critical radius corresponds to the maximum Gibbs energy
and thus gives rise to an unstable equilibrium: both smaller and
larger droplets move away from the critical radius, the smaller
by vaporizing and the larger by growing larger still. In contrast,
the equilibrium height of the liquid column corresponds to the
minimum of the potential energy. This gives a stable equilib-
rium: a column of smaller height will rise to h* whereas one of
larger height will fall to the same value.
Inclusion into Curriculum
We now make some suggestions regarding the inclusion of
this material into a curriculum. Nucleation is a kinetic process.
However, the rate of nucleation depends upon the thermody-
namic barrier ΔG*. As has been shown in eq 7, this barrier can
be estimated in terms of equilibrium thermodynamics. Thus the
topic of nucleation can be approached soon after the concept
of equilibrium thermodynamics and phase equilibria have been
discussed.
We describe two examples from standard physical chemis-
try textbooks to illustrate how our suggestions can be practically
incorporated in classroom teaching. In their textbook Atkins’
Physical Chemistry the authors Atkins and de Paula (1) intro-
duce nucleation in section 6.9(b). However they do not develop
it to the point of introducing the concept of critical size of the
nucleus. In the very next section, 6.10(a), they introduce capil-
lary rise and derive the equation for equilibrium height. Thus
there is a clear opportunity here to relate the two concepts in
the manner shown in our work and thus introduce the concept
of critical nucleus.
Our next example is in the textbook Physical Chemistry
by Silbey and Alberty (10). They briefly mention nucleation in
© Division of Chemical Education  •  www.JCE.DivCHED.org  •  Vol. 85  No. 10  October 2008  •  Journal of Chemical Education
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In the Classroom
Capillary Rise
Gravitational potential energy
Quadratic in h
Opposes rise
γsl – γsv
Linear in h
Assists rise
Stable
section 6.4: Effect of Surface Tension on Vapor Pressure. In the
same section capillary rise appears only in the list of methods
to determine surface tension. But neither of the topics has been
developed further. Thus again it is possible to introduce nucle-
ation and critical size through comparison with the capillary rise
as has been discussed in the present work.
Acknowledgments
I wish to thank Charusita Chakravarty, N. D. Kurur, and A.
Ramanan of the Department of Chemistry, Indian Institute of
Technology, Delhi, India, and A. L. Greer of the Department of
Materials Science and Metallurgy, University of Cambridge, for
helpful discussions and comments on the manuscript.
Literature Cited
1. Atkins, P.; de Paula, J. Atkins’ Physical Chemistry, 7th ed.; Oxford
University Press: Oxford, 2002; Chapter 6.
2. Wayne, R. P. Chemistry of Atmospheres, 3rd ed.; Oxford University
Press: Oxford, 2000; Section 2.5.
3. Kurz, W.; Fisher, D. J. Fundamentals of Solidification; Trans Tech
Publications: Aedermannsdorf, Switzerland, 1989.
4. Oxtoby, D. W. Acc. Chem. Res. 1998, 31, 91–97.
5. Callister, W. D., Jr. Materials Science and Engineering: An Intro-
duction, 6th ed.; John Wiley: New York, 2003; pp 174–176.
6. Debenedetti, P. G. Metastable Liquids: Concepts and Principles;
Princeton University Press: Princeton, 1996.
7. Markworth, A. J. J. Chem. Educ. 1971, 48, 528.
8. Henriksson, U.; Eriksson, C. J. Chem. Educ. 2004, 81,
150–154.
9. Talanquer, V. J. Chem. Educ. 2002, 79, 877–883.
10. Silbey, R. J.; Alberty, R. A. Physical Chemistry, 3rd ed.; John
Wiley: New York, 1995; Chapter 6.
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