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GOMMES
P H Y S I C A L C H E M I S T RY
O F I N T E R FA C E S
UNIVERSITY OF LIGE
Copyright 2014 Cedric J. Gommes
E X A M P L E A N D N A G G I N G . I W I L L S H O W Y O U W H AT I T I S I D O , A N D T H E N I
W I L L T E L L Y O U T O D O O T H E R T H I N G S Y O U R S E L F. D O Y O U U N D E R S TA N D ?
L E M O N Y S N I C K E T, A L L T H E W R O N G Q U E S T I O N S
N O U S P R E N O N S E N G A R D E L E S O P I N I O N S E T L E S AVO I R D AU T RU I , E T P U I S
C E S T T O U T : I L L E S FAU T FA I R E N T R E S . N O U S S E M B L O N S P R O P R E M E N T
C E L U I , Q U I AYA N T B E S O I N D E F E U , E N I R A I T Q U R I R C H E Z S O N V O I S I N , E T
Y E N AYA N T T R O U V U N B E A U E T G R A N D , S A R R T E R A I T L S E C H A U F -
FER, SANS PLUS SE SOUVENIR DEN RAPPORTER CHEZ SOI. QUE NOUS
S E R T- I L D A V O I R L A PA N S E P L E I N E D E V I A N D E , S I E L L E N E S E D I G R E , S I
E L L E N E S E T R A N S F O R M E E N N O U S ? S I E L L E N E N O U S AU G M E N T E E T F O R -
TIFIE ?
M I C H E L D E M O N TA I G N E , E S S A I S , I , 2 5 , D U P D A N T I S M E
Contents
Introduction 0-1
Gibbs-Thomson Effects V1
A first difference between today and say, twenty years ago is the
fantastic progress made in the field of electron microscopy, which
enables us to visualise nanometer-sized objects with unprecedented
accuracy. Advanced techniques such as electron tomography even Bottom-up and top-down methods
enable one a obtain 3D reconstructions of structures with nanome- refer to whether the larger structures
are created last or first. Typically,
ter resolution. The second difference is the progress in the synthesis lithography is top-down. Chemical
of nano structured materials by a variety of techniques, both phys- methods, by which molecules assemble
into nano structures is bottom-up.
ical and chemical, top-down and bottom-up. The fields of synthe-
sis of nano materials, and that of fundamental understanding of
nanometer-scale phenomena are clearly feeding on each other. It
is because we understand better nanometer-scale phenomena that
we can create structures on that scale in a more controlled way. In
turn, those better-defined structures enable us to better understand
nanometer-scale phenomena. This is incidentally the reason why sci-
entific or technological progresses are exponential: because they feed
on themselves.
There are, however, still some problems on the horizon. For exam-
ple, in the field of imaging of nanostructures one is often limited to
studying materials in vacuum, which is a very different environment
from that in which most nanomaterials are generally used. The de-
velopment of so-called in situ imaging techniques at the nanometer- Figure 03: One of the colloidal gold
suspension prepared by Faraday in the
scale, to visualise nano structures in working conditions, is still a 1850s, which is still kept by the Royal
challenge. One therefore often relies on indirect methods, such as Insitution. Read more about it here
small-angle X-ray scattering. In the field of synthesis too, our current
skills are limited. Although the word nano fabrication is sometime
used, our current abilities are far from the self-multiplying robots
that terrorised Great Britain in 2001 under the ominous name of
"Grey Goo". A positive way to look at this is to think that there are
many things left to be developed by new scientists and engineers in
that field. The word colloidal was coined by
Graham to characterise "glue-like" sub-
stances. The official IUPAC definition
When people express their enthusiasm about nanoma- of that word is as follows: "State of
subdivision such that the molecules or
terials, they often say that it is fantastic that we can control the polymolecular particles dispersed in a
shape of materials on a scale as small as a few nanometers. Before medium have at least one dimension
we comment on this, we should first emphasise that there is already between approximately 1 nm and 1
m, or that in a system discontinuities
an existing and successful science, the purpose of which is to control are found at distances of that order."
matter over a still smaller scale, that of the Angstrm. That science In other words, colloidal is almost
synonymous with nano.
is naturally chemistry. So size per se is not the issue. The real diffi-
culty with nano structures is that they at the interstice of two worlds: It is important that you become familiar
with a few orders of magnitude. For
the microscopic and the macroscopic. Systems in the former world example: the number of molecules
are generally made of a few molecules, interacting with very strong or atoms in a macroscopic amount of
matter is 1023 , the size of an atom is
covalent bonds, and subject to thermal fluctuations. By contrast, in 1 , the energy involved in chemical
the latter world systems comprise a huge number of molecules (say, bonding is 1 eV, the thermal energy at
one mole) interacting through very weak forces, and thermal fluctu- room temperature is 25 meV, etc.
introduction 0-3
At this stage, you may wonder why the title of the course
is "Physical Chemistry of Interfaces" and not, say "Intro-
duction to nano sciences". The reason is that all many properties of
nanostructured materials result from their having a large surface-to-
volume ratios. In other words, interfaces play an important role at the
nanometer-scale. This is illustrated in Fig. 04 with the unfolding of
a paper cube, compared to that of eight smaller cubes. The surface is
two times larger in the latter case.
To put this in a more quantitative way, try to estimate the specific
surface area of a material made up of silica particles with a diameter
of 10 nm. Obviously, if you double the mass of material, you double
the surface. So the only sensible quantity to evaluate is expressed in
m2 /g, for example. The word "specific" means "per unit of mass".
Now, when I wrote "try to estimate.." I really meant it: before reading
what follows try to do it!
A possible way to calculate this is to estimate first the area of a sin-
gle nanoparticle, and then to calculate how many nanoparticles there
are in one unit of mass. The area of one spherical particle of radius R
is 4R2 so that the total area of the N particles in the material is
A = N 4R2 (01)
Fraction of atoms Ad A
' = d (04)
at the surface V m
where the equality results from expressing the volume as m/. The
fraction in the Right-Hand Side (RHS) is nothing but the specific sur-
face area of the material. This equation has a very intuitive meaning:
V/A has the dimension of a length, and it is the order of magnitude
of the size L of the object (check for a sphere). What Eq. 04 tells you L d
is simply that the fraction of atoms at the surface is proportional to
d/L. If the object if of a size comparable to that of the atoms, then
there are may atoms at the surface. On the other hand, if the object is
macrosopic, there is a negligible fraction of atoms at the surface.
In practice, consider for example the fraction of atoms at the sur- Figure 06: A complex-shaped object,
with characteristic size L. All atoms
face of an ice cube. The ice cube is about 1 cm across so L ' 102
in a layer a thickness d, comparable to
m, and the diameter of the atoms is about d ' 1010 m. So the frac- a molecular diameter, can be consid-
tion is d/L ' 108 ; only ten atoms out of a billion are at the surface, ered to be at the surface. The fraction
of molecules at the surface is approx-
which isa negligible quantity. Note in passing that it does not matter imately equal to the fraction of the
whether the answer had been 20 108 or 0.2 108 . If the answer is volumes of the red and grey regions of
the drawing.
100 times larger or smaller, it is negligible anyway. This is the reason
why we do not have to care too much about the exact size of atoms
and of the ice cube for this type of calculation. This is the essence of
order-of-magnitude calculations.
If the result had not been negligibly small, say if we had found a
fraction of 0.01 then we would have needed to pay more attention
to the details. Because it makes a lot of difference whether 1 % or
100 % of atoms are at the surface. As an exercise, let us calculate the
fraction of water molecules that are at the surface of a 10 nm droplet.
We first have to find a reasonable value for d. This can be done by
expressing that the density of single molecules is the same as that of
macroscopic water. Assuming a cubic packing of molecules, which is
naturally a rough approximation, one has
M/NA
= (05)
d3
Exercises
The main take-away message from this chapter is the relation be-
tween size and surface area. It is important that you feel comfortable
with this before studying the following chapters. The following exer-
cises should help you.
Further reading
On the web
The NANOYOU (Nano for Youth) project is funded by the Euro-
pean Commission to increase young peoples understanding of
nanotechnologies. You can find many useful resources on their
website here.
Regular papers
Emil Roduner, Size matters: why nanomaterials are different.
Chem. Soc. Rev., 2006, 35, 583-592
This tutorial review by Emil Roduner (cited as an epigraph of the
chapter) is a nice overview. You should not be able to understand
all of it at this stage. However, I encourage to try reading regularly
Figure 08: Richard Feynman (1918-
this paper along this semester to see your progress in that field. 1988).
W = Fdx (I1)
I2 c.j. gommes, chim0698
On the other hand, the change in energy resulting from the displace-
ment dx is dU = 2Ldx. The factor Ldx is the variation of the area
enclosed by the wire; is the energy per unit area of the free surface;
the factor 2 accounts for the fact that the film has two free surfaces,
one on top and the other on the bottom. When equating W with dU,
one finds
F/L = 2 (I2)
top view
which is indeed proportional to . The factor 2 proves that if is
to be interpreted as a force per unit length, then the force has to be F
considered as being exerted on the surface itself and not to the film A L
as a whole. In the present case, that force applies on both surfaces of
the film.
In principle, the wired frame of Fig. I3 could provide a means to side view
measure the surface tension of liquids. In practice, however, liquids F
films are generally too fragile for this is to be possible. Another ex-
perimental configuration is used, which is referred to as Wilhelmys Figure I3: Mechanical equilibrium of a
plate. It consists in dripping a plate of roughened platinum1 into the liquid film on a wire.
liquid and in measuring the force required for pulling it out of the 1
You will have to wait until we have
studied wetting phenomena to under-
liquid. stand why this is important.
The situation is sketched in Fig. I4; the thickness of the plate is t
and its length (in the direction orthogonal to the figure) is L, and we
call P0 the ambient (e.g. atmospheric) pressure. Let us write all the
forces exerted on the plate. The forces oriented downwards are
Forcesdown = mg + P0 L t + 2L (I3)
The first term is the weight of the plate, the second is the pressure
that is exerted on top of the plate by the ambient gas (applied on a
total area L t) and the last contribution is the same 2L as in Fig.
I3. On the other hand, the forces upwards are
as small as desired. In this case the force needed to pull the plate out
of the liquid is proportional to .
In practice, a common experimental setup is a so-called Wil-
helmys ring (as opposed to plate), in which it is a horizontal ring
made up of a thin Pt wire that is pulled out of the liquid. The anal-
ysis is similar to that in Eq. I5, only L has to be understood as the
length of the ring. A few experimental values of obtained using
this type of setup are gathered in Tab. I1.
U = A + mgh (I6)
where A is the total area of the liquid free surface, and the second
contribution is the gravitational energy, with m the mass, g the accel-
eration of gravity, and h the height of the centre of gravity. Calling
l a characteristic size of the system, the order of magnitude of each
contribution is the following. The surface contribution is You may consider that "a characteristic
size" is synonymous to "the order of
magnitude of the size". In the case of a
Usur f ace l 2 (I7) sphere, you may chose the radius R or
the diameter 2R. The type of mathemat-
and the the gravity contribution is ical relations involving characteristic
sizes, orders of magnitude, and the like,
are referred to as "scaling relations".
Ugravity gl 4 (I8) The symbol means that a dimen-
sionless factor is omitted, which is the
where is the density. To obtain that estimation, we have taken ac- reason why we should not care too
much about the accurate definition of
count that the mass scales as m l 3 and the height as h l. the characteristic length.
I4 c.j. gommes, chim0698
Comparing the two contributions to the energy, one sees that the
surface is dominant whenever the length satisfies
r
l (I9)
g
Let us step back for a moment and consider the case of Fig. I3
again from a microscopic perspective. What opposes the extension
of the liquid film is the fact that more molecules are pulled towards
the surface if the area A of the film is increased. This may seem like
a crazy explanation, and yet it is in quantitative agreement with the
experimental values of in Tab. I1.
Let us try to make quantitative the sketch in Fig. I8 and relate
to some more familiar characteristic of a fluid. The surface energy
is the energy required to bring a molecule/atom to the surface and
break a few bonds. On the other hand, if you think of it, from the
point of view of a molecule, evaporation consists in breaking all the
bonds that maintain it in the liquid. One therefore expects the energy
relevant to to be a fraction of the enthalpy of evaporation he .
Let us see how quantitative we can make that analogy, by assum-
ing an oversimplified liquid structure where the molecules/atom
would be positioned according to a cubic lattice, with spacing d.2 In 2
Remember, this is equivalent to what
we did on page 0-5 when we were
that case, the number of bonds of a molecules in the bulk is 6, and
trying to guess molecular dimensions.
only 5 at the surface. The surface energy would then be written as
1 he
' (I12) surface
6 v2/3
m
mass M = 84.16 g/mol. Using the latter two values, you can estimate
the molecular diameter d = 5.56 . From that value, Eq. I12 leads
to = 26 mJ/m2 . Compare that value to the actual experimental
value in Tab. I1. The agreement is excellent! Of course we must Josef Stefan was an Austrian physicist,
have been particularly lucky with this calculation because no one in born in todays Solvenia, who gave
his name to Eq. (I12), among many
his own mind would accept that molecules in a liquid would pack others. To understand the importance
in a cubic way. Moreover, we have assumed that molecules on the of Stefans contribution, you have to
consider that the very existence of
surface loose just one neighbour. Why not half of them? You see atoms and molecules was controversial
my point: this is yet again an order of magnitude calculation. The at the time. The final demonstration
clear message, however, is that the story of molecules preferring to for the existence of atoms is generally
considered to be the work of Jean Perrin
be in the bulk rather than at the surface is indeed responsible for on Brownian motion, for which he
macroscopic manifestation of surface energies. received the Nobel prize in 1926. That
is 33 years after the death of Stefan!
So far we have talked mostly of liquids, but the concept of surface
energy applies to solids as well. Of course, it is difficult to imagine a
Wilhelmy-like experiment with a solid, but there are other manifes-
tations of surface energies for solids. For example, if you think of it a
mechanical fracture in a solid creates newly exposed surfaces, so frac-
ture criteria must have something to to with surface energies. Solids
with higher surface energies ought to be tougher is some sense. Ac-
tually a fracture is a process by which elastic deformation energy is
transformed into surface energy. This simple observation by Alan
Griffith resulted in a major breakthrough in solid mechanics, but we
will not have time to discuss this further.
What shall keep us busy in the remainder of the chapter is an
effect that is important for both solids and fluids, which bears the
name of Laplace pressure. The discovery that Thomas Young is refer-
Figure I9: Alan Arnold Griffith (1893-
1963)
I6 c.j. gommes, chim0698
This means that if you change the shape of the two phases in any
A
imaginable way, the volumes V1 and V2 , and the interface area A
will obviously change but the free energy will be left unchanged. V1
To convert this statement into something more intuitive, about the
pressure difference P1 P2 , we need some mathematics. V2
Consider a volume like shown in Fig. I10. Each point of the sur-
face has a normal vector ~n pointing towards phase 2. Any infinitesi- Figure I10: Two phases with volumes
mal deformation of the surface can be described by a function V1 and V2 fill space. At equilibrium,
the free energy is left unchanged if the
surface is deformed in any possible
~r = ( x )~n (I14) way. This will eventually lead us to
Laplaces law.
where ( x ) is a function defined over the surface. If is positive
at a given point, the the surface is deformed outwards; it is deformed
inwards if is negative. The total change in volume can be written
in terms of as
Z
dV1 = d ( x ) (I15)
A
where the integral is over the total interface. Naturally dV2 is simply
the opposite of dV1 .
The change in surface area dA also depends on ( x ). According
to a famous theorem from differential geometry, the relation can
be written in terms of the local curvature of the surface. The actual
relation is Z To gain some intuitive understanding of
Eq. I16 consider the case of a spherical
dA = d K ( x )( x ) (I16) surface with radius R, with = dR.
A
In that case the total curvature is 2/R
where K ( x ) is the local total curvature of the surface at point x. Ge- everywhere on the surface so that the
integration is simply a multiplication by
ometrically, the total curvature is the sum of the inverse of the two
the area 4R2 . On the other hand the
principal radii of curvature at point x change in surface area is dA = 8R dR,
so that Eq. I16 is indeed satisfied.
1 1
K(x) = + (I17)
R1 ( x ) R2 ( x )
This is all the mathematics we need to put Eq. I13 is a more under-
standable form.
surface energies and laplaces pressure I7
With the help of Eq. I16, Gibbs equation can be put under the
form Z
dG = d [ P1 + P2 + K ] (I18)
A
Expressing that this quantity should vanish for any possible leads
us to the important result
P1 P2 = K (I19)
r ( x ) = R + sin(2x/) (I23)
1 d2 y
' 2 (I25)
R( x ) dx
where the ' sign means that the relation is valid provided the curva-
surface energies and laplaces pressure I9
ture is small enough. Applying that formula to Eq. I23, one finds
(
1 (2/)2 at point 1
= 2 (I26)
Rk (2/) at point 2
Note the minus sign in the second equation, which means that the
center of the tangent circle points outside of the surface, so that its
effect on the pressure via Laplaces law is negative. Putting all that
together, one finds the following pressures
" 2 # " #
1 2 2 2 1
P1 = + ' + 2 (I27)
R+ R R
" 2 # " #
2 2
1 2 1
P2 = ' 2 (I28)
R R R
where the second equality results from a Taylor development to the Figure I15: John William Strutt, 3rd
Baron Rayleigh (1842-1919).
first order in /R, which is justified because we have assumed that
was small. The condition for instability P1 P2 takes the simple form
2R (I29)
Isnt that a beautifully simple result?
Equation I29 means that a column is naturally unstable towards
corrugation with long periodicity. The periodicity that is actually ob-
served results from a balance between thermodynamics and kinetics.
Thermodynamics favours large values of , but the growth of such
an instability would be extremely slow because its would require the
transport of atoms/molecules over distances comparable to . The
values observed in practice are close to = 2R. This is illustrated
in Fig. I16, which shows the decomposition of a Cu nanowire into a
series of spherical nanoparticles.
For the records, this type of instability is know as the Plateau-
Rayleigh instability, after the famous british physicist Lord Rayeigh,
and the belgian physicist Joseph Plateau.
Exercises
1. Calculate the capillary length of mercury, with ' 0.5 N/M and
' 13 103 kg.m3 , as well as that of water on the moon, where
gravity is three times less than on Earth. Figure I16: Example of nanometer-
scale Rayleigh instability: spontaneous
2. Repeat the scaling analysis that we did for Bonds number to fragmentation of a Cu nanowire. Taken
from Appl. Phys. Lett. 85 (2004) 6275.
compare the surface energy to the kinetic energy of a flowing
liquid. That number is referred to as the Weber number We: find
an expression for it in terms of a characteristic length l, as well as
on any other relevant quantities.
I10 c.j. gommes, chim0698
6. Check the validity of Eq. I25 in the particular case of the equa-
tion p
y ( x ) = R2 x 2 (I30)
corresponding to a circle of radius R.
9. Looking at Fig. I17, would you say that the capillary number (Cf. Figure I17: Air bubbles rising in a
viscous liquid.
point 3) is larger or smaller than one?
Here is a paper from Nature (487, 2012, 463) about how nanometer-
scale Plateau-Rayleigh instabilities can be exploited to produce
nanoparticles with sophisticated structure.
Lord Byron
The situations in which liquids are put in contact with solid sur-
faces are too many to enumerate, and their technological importance
can hardly be overestimated. The examples from either technology or
the natural world that immediately come to mind involve the paint-
ing of a surface, printing, lubrication, wicking of porous media by
Figure II1: Leonardo da Vinci (1452 -
a liquid, the creating of water-tight yet air-permeable fabrics, rain 1419)
drops sliding down a window or rolling down a hydrophobic leaf,
the walking of a insect on a pond, the capillary ascent of sap in the
xylem vessels of a plant, etc.
The topic of wetting is not a new one. The first documented study
about capillarity seems to be the deed of Leonardo da Vinci, and it
has been followed by a long series of scientists. A name you might
be familiar with is that of James Jurin who gave his name to the law
relating the height of capillary rise to the diameter of the capillary.
It is also a poorly known fact that Albert Einsteins first published
paper was about capillarity, in year 1900. Capillarity is an extremely
active field of research, and the work of Pierre-Gilles de Gennes (Fig. Figure II2: James Jurin (1684-1750)
I19) was instrumental in the bringing that topic to the forefront of
research.
1
= (II1)
cos( ) c
the liquid on the surface necessarily depends on these three surface Solid c (mN/m)
energies. Clean glass 150
Fluorinated glass 10
We use the notations S , L , SL for the surface energies of the Polyethylene 31
solid, of the liquid, and of the solid-liquid interface. Assuming that PVF4 18
you know all the relevant surface energies, you can calculate the Table II1: Critical surface tension of
between the dry solid and the wetted solid. Because that quantity is a few solids. PVF4 is a fluorinated
directly related to the tendency of the liquid to spread, it is referred polymer.
and for aqueous solutions of surfactants. You will have to wait until
we discuss the physical origin of intermolecular forces in Chapter IV
to understand this better.
90 are increased by surface roughness, and contact angles smaller The roughness factor of the surface r -
also called the rugosity - is defined by
than 90 are made even shallower. In other words, roughness en-
IUPAC as the ratio of the actual surface
hances both hydrophilicity and hydrophobicity. Eq. II7 is known as area to the apparent (projected) surface
Wenzels law. area.
Us = dh [SL S ] (II9)
d
R cos( ) = (II11)
2
As a consequence of that curvature, the pressure in the liquid just
wetting, a short introduction II7
h
Figure II12: Two different and equiva-
lent approaches to analyse the rising of
a liquid in a capillary, based on energy
minimisation or on Laplaces pressure.
d
2L
P = P0 (II12)
R
where P0 is the ambient pressure. On the other hand, that pressure
can also be calculated from the height of the liquid as
P = P0 gh (II13)
4L cos( )
h= (II14)
gd
smaller the diameter, the larger the pressure. The deep reason for this
is that wetting phenomena in pores scale like the surface-to-volume
ratio of the pores. You may at first think of mercury
That observation can be used practically measure the size of pores porosimetry as a technique from an
older age. After all, why not simply do
it porous materials, by a technique called mercury porosimetry, or electron microscopy to measure pore
sometimes intrusion porosimetry. The technique consists in immersing sizes? The reason is that the amount of
material that you actually characterise
the unknown porous material in mercury, and increasing progres- when doing microscopy is extremely
sively the pressure. At each particular pressure the volume of mer- small. A fragment 100 nm across, which
cury that has entered the pore space is measured. Mercury is used is the largest you can analyse in a
microscope with nanometer resolution,
for those experiments because it does not wet any known solid. All has a mass of 1015 g. Compared to
solids are mercuro-phobic, so to speak. the kg or even ton of material that is
used in any industrial context, this is an
A typical mercury intrusion curve is shown in Fig. II13: the in- extremely poor sampling. The strength
truded volume is plotted as a function of the pressure. One observes of techniques like mercury porosimetry
that intrusion occurs at a specific pressure that can be related to the is that they enable you to characterise
a large quantity of material, with a
pore size via Eq. II15. In practice, the accepted value for the contact nanometer-scale resolution.
angle of mercury with any material is 142 , which together with
the value of L given in Tab. I1 leads to the following quantitative
relation
1500
d[nm] (II16)
Pi [ MPa]
between the intrusion pressure and the pore size. In the case of the
figure, with intrusion pressures Pi = 20 MPa and Pi = 50 MPa, the
pore sizes are found to be 75 nm and 30 nm, respectively. In typical
mercury porosimeters, the pressure can reach 200 MPa, which means
that pores as small as 7 nm can be detected. In case you do not remember the
There is an interesting aspect to intrusion porosimetry that is not Hagen-Poiseuille, you can always find
it back using dimensional analysis. In
often discussed, which concerns the kinetics of fluid intrusion. When dimensional form: the volume flow
the pressure in the fluid is suddenly brought to a value larger than Q [m3 /s] depends on the pressure
gradient dP/dx [Pa/m], on the viscosity
the intrusion pressure Pi , how fast does intrusion take place? This [Pa.s] and on the tube diameter d [m].
question can be answered by noting that when a liquid invades a Only a single dimensionless number
porous material, there is a pressure drop in the liquid dP per unit can be formed, e.g. d4 dP/dx/(Q),
which can only be equal to a constant.
length dx of a pore, which can be approximately described by the This is exactly Eq. II17, except for the
Hagen-Poiseuille law, namely factor 128.
dP 128Q
= (II17)
dx d4
where is the viscosity of the fluid, Q is the volumetric rate, and d is
the pore diameter. Imagine that at given time t, the liquid has entered
the pore over a length L(t), from the outer surface of the material to
the meniscus. Over that distance, the pressure drops from P at the
outer surface to Pi just behind the meniscus. This enables us to write
the Hagen-Poiseuille law again as
d4
Q= ( P Pi ) (II18)
128L(t)
wetting, a short introduction II9
SL ' SL + (1 )L (II20)
where is the fraction of the surface where the two phases are actu-
ally in contact. On the remainder fraction of the surface, the interface
energy is simply L because the crevices of the surface are filled with
air. You may try to incorporate that type of thinking into our demon-
stration of the Young-Dupr equation, and this will lead you to a
different relation between surface roughness and contact angle.
Similarly, in the case of a wetting liquid you may think of the
crevices on the surface as of a porous material, which may be in- Figure II15: The Cassie-Baxter-like
super-hydrophobicity of the leafs
truded by the liquid following the usual laws of capillarity. In that of some plants is often referred to
case, on a microscopic scale things may look like in Fig. II142, which as the lotus effect. Picture from from
Wikipedia.
is also different from the Wenzels model. In that case too, you may
use an approach similar to Eq. II20 to derive the apparent energy of
the dry surface S .
The model corresponding to the wetting mechanism of Fig. II14
is known as the Cassie-Baxter model. In the particular case of hy-
drophobic surfaces it is sometimes referred to as the Lotus effect. The
surface of the lotus leaf is covered by a waxy substance that confers it
with hydrophocity; in addition to that, the surface comprises numer-
ous micrometer-sized posts that make it similar to Fig. II14a, and
confers super-hydrophobicity to the surface.
II10 c.j. gommes, chim0698
Exercises
Figure II16: The legs of water strid-
1. Capillary action is one of the two mechanisms responsible for ers are covered with hydrophobic
hair, which confers them super-
the ascent of sap in plants from the roots to the leafs, in addition hydrophobicity. Picture from from
to osmotic pressure. Try to guess the order of magnitude of the Wikipedia.
diameter of xylem vessels, and then compare its with actual data.
4. Think about Jurins law in the case where the spreading parameter
S is positive. Does Eq. II14 hold?
5. Next time you use a straw for drinking, pay attention to the small
drops of water that may remain stuck in the straw, while the larger
ones flow under the effect of gravity. The reason for this is contact
angle hysteresis. Write down a balance of force to determine the
maximum length of a column of water that may be blocked in a
straw, in terms of the advancing and receding contact angles a
and r . Do some experiments at home with water and a straw to
try learning something quantitative about a and r .
6. Think about the double-sided floater shown in Fig. II18. Doesnt Figure II18: A double-sided floater
with each side made up of a specific
something puzzle you about the horizontal equilibrium of such material, having different contact angles
an object? The force to the right has to be equal to the force to with water.
the left, otherwise it could serve as a perpetual motion machine.
Enumerate all the forces involved.
III0 c.j. gommes, chim0698
Further reading
David Qur gave two lectures about the effect of surface texture
on wetting, which you can find on Youtube the first here and the
second here. This is a fascinating and very timely field of research;
Jimi Hendrix
The unimaginative steps that you may follow if you feel com- Figure III2: This is roughly what this
pletely lost are the following exercise is about
1. Prove that the shape of the free surface of water is a spherical cap.
2. Assume a cylindrical glass with radius r. Given that the free sur-
h
face is a spherical cap and that the total volume of liquid V is a
r
given, express the total surface energy of the system in terms of a
single well-chosen geometrical parameter. And find the equation R
that the parameter has to satisfy at equilibrium.
Solution
U = A + SL Aw + S Ad (III2)
The areas of the wet and dry parts of the glass are simply ex-
pressed as
2h1 /r
cos( ) = (III7)
1 + (h1 /r )2
Comparing Eqs. III6 and III8 shows that the value of h1 that
minimises the energy is exactly the one satisfying the Young-
Dupr equation. The practical problems of astronauts is
more often to get water out of the glass,
The answer is therefore simply that the configuration is such that than to put it back in as in Fig. III2.
Look here to see the contraption they
the free surface of the liquid is a spherical cap, and the contact angle use for drinking.
satisfies the Young-Dupr equation.
Thinking further
plates together. Imagine two microscopy slides with area 2 cm2 and
water in between.
What is the value of the force that pushes them together assum- r
R h
ing = 75 mN/m and = 60 ?
The unimaginative steps that you may follow if you feel com-
pletely lost are the following Figure III5: Two flat plates, with a thin
liquid layer in between. In this view,
1. Looking at Fig. III5, what is the pressure in the liquid relative to the liquid layer is assumed to have
the shape of a disk with radius R and
the outer pressure P0 , as a function of h? Simplify that expression
thickness h.
for the case R h;
2. You are pulling the two plates apart with a force F. In order to
determine the value of F that can overcome the capillary forces,
imagine cutting the liquid layer horizontally and account for all
forces exerted on, say the upper half of the system. Simplify again
that expression for R h.
solved problems involving wetting III7
Solution
1. The two radii of curvature of the interface are r and R. The pres-
sure in the film is therefore
1 1
P = P0 + (III9)
R r
2 cos( )
Pc = P0 (III11)
h
where we have taken account of R h. The subscript c stands for
capillary pressure.
Fdown = P0 R2 + 2R (III13)
Thinking further
together.
At the level of the sand grains, the situation is similar to that
shown in Fig. III7. For the purpose of the present problem you
may assume that the contact angle between the water and the sand is
= 0.
What is the force that pulls the two sand grains together in the
limit of small amounts of water? Figure III6: Wet sand is stickier than
dry sand because of Laplaces pressure
in the liquid bridge that forms at the
We shouldnt give you any hint for the present problem, except contact between two grains.
that it looks very much like the previous one, doesnt it?
Solution
( x + r )2 + R2 = ( R + r )2
x2 + 2xr = 2Rr (III15)
Because the point of contact between the two spheres is locally flat,
r decreases more rapidly than x for x 0. In the case where r x,
the relation between r and x simplifies to
1 2R
= 2 (III16)
r x
F = 2x + 2R ' 2R (III19)
Thinking further
4. Do the same analysis for the capillary force between two cylin-
ders. This might be relevant to the sticking of your hair together
when you get out of a shower.
III12 c.j. gommes, chim0698
Solution
dW = 3Fdl (III21)
F 2 A
= 3 (III22)
l2 3 l
where A/l 3 is noting but what we have called AV . Note also that
F/l 2 is the tensile stress, equivalent to a negative pressure.
AV = nV 4R2 (III23)
4
e = nV R3 (III24)
3
This results in an area per unit volume
3e
AV = (III25)
R
Note that you may have used another
With the values R = 50 m and e = 0.5, one finds AV ' 3 104 model for the lung, for example a cubic
m1 . If the liquid was pure water, with surface tension = 75 packing of alveoli. In that case you
would have a surface 4R2 in a volume
mN/m, the capillary stress would be of (2R)3 . That would be AV = /(2R).
Compare that with Eq. III25 with
F e = 0.5.
= 1500 Pa (III26)
l3
That pressure is equivalent to about 1.5 kg exerted on a surface of
10 10 cm2 . Imagine a newborns lung having to exert that at each
breath!
III14 c.j. gommes, chim0698
Thinking further
What is the total force exerted by the liquid on the wall? And R(z)
how does it depend on the various surface energies involved? h
z
There is a straightforward way to estimate that force, which does
require any calculation. Try to find it. If you do find it, use the result
to calculate the height h of the triple line above the surface of the
liquid. Figure III9: Shape of the meniscus
On the other hand, if you are running out of imagination, you may close to a flat vertical wall.
also go through the following steps
4. What is the total force that the liquid exerts on the wall?
III16 c.j. gommes, chim0698
Solution
In the left-hand side are the force pulling towards the wall, and in In this analysis, we have assumed that
the right-hand side the forces pulling/pushing away from the wall. the ambient pressure is P0 = 0, but
this does not matter. If you keep P0 in
This leads immediately to the calculation, you will find that its
q effect cancels out in the end. With some
experience, you should progressively
h = lc 2(1 sin( )) (III28) feel comfortable with this.
p
where lc = /(g) is the capillary length.
0 = f ( ) (III29)
h = lc f ( ) (III30)
P(z) = P0 gz (III31)
and the pressure in the gas phase is simply P0 (it is much lighter
than the liquid so the vertical pressure gradient in it can be ne-
glected). The pressure discontinuity at the interface is accounted
for by Laplaces law, which leads to
R(z) = (III32)
gz
Just a check: R for z 0, as it should.
Further thinking
1. Look back to our analysis of Wilhelmys plate (Fig. I4) with the
present problem in mind.
IV0 c.j. gommes, chim0698
2. Devise a plan. In that case, the plan is (i) calculate the change in
surface area resulting from a macroscopic change of volume, and
(ii) equate the resulting change of energy to the mechanical work
of the macrosopic forces; Note that step 3 (carry out the plan)
is the only one that you do if you
3. Carry out the plan. That step is self-explanatory. This is the only try to apply formulae in a rote way.
one where some mathematics is involved; Most of the time, that step is the least
interesting one, but for some reason it
4. Look back. Have you answered the question? Does the result seems to be the one on students spend
make sense? In the case of the lung, estimating the total area of the more time.
Further reading
2 C
wD = = D (IV3)
(4e0 )2 d6 d6
which bears the name of Peter Debye. Note that here too, the depen-
dence in the distance is proportional to d6 .
Yet another situation is that of two neutral molecules bearing no
electrical dipole whatever. A handwaving explanation for the at-
traction between two such molecules is the following. Electrons in
each molecule move around very rapidly with a frequency compara-
ble to the ionisation frequency .8 As a consequence, the molecules Figure IV4: Peter Debye (1884 -1966).
are non-polar only on average: at every moment they carry a small Picture from Wikipedia.
8
Ionisation frequencies are of the
dipole that fluctuates very rapidly. If the fluctuations in each molecules
order of 1015 1016 Hz. The ionisation
were independent of one another, this would not result in any force process by which an electron is stripped
between them. The force would be now attractive now repulsive and out of a molecule a photon, i.e. by an
oscillating electric field, can be thought
the two would cancel out exactly. However, when the two molecules of as a resonance phenomenon. The
are brought close together, the fluctuations of the dipoles in each one frequency of the field has to match
the natural frequency of the electron.
of them become anti-correlated: if one points, say up the other will
be more likely to point down. This results in a net attraction between
the two molecules. Imagine compressing gaseous nitrogen
The quantitative analysis of the attraction between two non-polar at a constant temperature. When you
reach a given volume the gas will
molecules requires quantum-mechanical calculations. The calcula- start to condense, which means that
tions were done for the first time by Fritz London in 1921, and the molecules have come sufficiently close
to each other to attract each other.
result can be written as Have you ever thought about why two
3 1 2 h1 2 C nitrogen molecules attract each other at
wL = = 6L (IV4) all?
2 (4e0 )2 d6 (1 + 2 ) d
intermolecular forces IV3
9ab
Cexp = (IV6)
4
which results from assuming that the molecules behave like hard
spheres at short distances. Globally the agreement between the elec- Figure IV5: Fritz London (1900 - 1954).
Picture from Wikipedia.
tromagnetic calculation of the actual intermolecular forces is fair. It
particularly interesting to compare the various contributions to the
intermolecular forces in the case of polar molecules, such as HCl. The
largest contribution by far is generally the dispersive London force!
A notable exception is water, for which the Keesom contribution is
dominant.
scopic bodies, say A and B, one has to sum over all pairs of molecules
with one in A and the other in B. Mathematically, this means that we
have to calculate a six-dimensional integral. Let us write the Eq. IV5
as w = C AB /d6 where C AB is specific to the types of molecules in A
and B. The macroscopic interaction would be
C AB A dVA B dVB
Z Z
WAB = (IV7)
VA VB [( x A x B )2 + ( y A y B )2 + ( z A z B )2 ]3
where A and B are the densities of media A and B expressed as a
number of molecules per unit volume, in such a way that A dVA and
B dVB are the number of molecules in the elementary volumes.
Two flat surfaces Two spheres Two parallel cylinders Two crossed cylinders
R1
D
R1 R1
R2 R2
D R2
A A R1 R2
q
R1 R2
W = 12D 6D A A
6D R1 R2
2 R1 + R2 12 2D3/2 R1 + R2
A AB = 2 C AB a B (IV12)
The Hamaker constant characterises the two interacting media. Note that D does not have the same
meaning in Eq. IV9 and in Eq. IV
The expression of WAB in Eq. IV7 is quite general; you can apply
10. In the former equation, it is the
it in principle to calculate the van der Waals interactions between distance between a molecule of A and
bodies of any size and shape. Depending on the shapes of the two the surface of B; in the latter it is the
distance between the surfaces of A and
bodies, the calculation can be cumbersome, but the calculations are B.
conceptually as simple as those leading to Eq. IV11. A few expres-
sions of the energies are gathered in Fig. IV8 for interactions be-
tween spheres and cylinders. Note that these are expression for the
energy. The corresponding forces are calculated as
dW
F= (IV13)
dD
We shall come back to these expressions later.
Before we proceed to see what Eq. IV11 can be good for, it might
be useful to elaborate a bit on Hamakers constant. You may have
noticed that the relevant constant in Eq. IV11 characterises the inter- Figure IV7: Hugo Christian Hamaker
(1905-1993). Picture from Langmuir 7
action of two different media A and B, while we have only discussed (1991) 209. In that same paper the au-
the forces between identical molecules so far in Eqs. IV2, IV3 and thors mention the following anecdote.
Hamaker left the field of colloids in
IV4. The fact that the dispersion forces is the largest of the three the forties to focus on the development
contributions for non-polar (or weakly polar) molecules simplifies the of statistical methods for the Phillips
analysis. From Eq. IV4, the following approximation is seen to hold company, and he stopped following
the developments in that field. In 1965
p one of his sons who was studying soil
A AB ' A B A B ' A A A B (IV14) science asked him: "Dad, there is some-
thing called a Hamaker constant. Is it
In other words, all you need to know to estimate the interaction named after some relative of ours?"
between two bodies via van der Waals forces is the Hamaker constant
of individual bodies, and to compose then according to Eq. IV14.
Eq. IV14 is sometimes referred to as the Berthelot composition rule.
IV6 c.j. gommes, chim0698
A (1020 J) (mJ m2 )
from Eq. IV19
Liquid He 0.057
PTFE (teflon) 3.8 18.5
Pentane 3.8-4 Table IV2: Hamaker constants of a
few materials (both liquid and solid),
Ethanol 4.2 20.5
sorted in increasing order, and inferred
Acetone 4.1 20 value of the surface energy. Compare
Hexane 4.32 those values to those from Tab. I1 on
page I3.
Octane 4.5-5.02
Cyclohexane 4.8 - 5.2
Decane 5.45
Water 3.7 - 5.5 18-27
Toluene 5.4
Formamide 6.1 30
Fused Quartz 6.3
Silica (SiO2 ) 6.5 24-29
Diiodomethane 7.2 - 7.8
Polyvinyl chloride (PVC) 7.5 7.8 38.0
Quartz 7.93
Polyethylene (PE) 10
Mica 10-11
Aluminium 15
ZnS 15-17 73 - 83
Iron oxide (Fe3 O4 ) 21
Silicon 25.5
Zirconia (ZrO2 ) 27
Diamond 28.4
Copper 28.4
Germanium 30
Silver (Ag) 40
Rutile (TiO2 ) 43
Gold 45
Graphite 47
intermolecular forces IV7
according to Eq. IV11. Note that this energy is positive. The energy
change from 2 to 3 can be calculated using Eq. IV23 with z0 = D0
and z1 = D. The result is
!
AL 1 1
W23 = 2 2
12 D02 D
! !
A LA 1 1 A LB 1 1
2 2 (IV25)
12 D02 D 12 D02 D
A L A L A L A
L
1) 2) 3) 4)
B
B B B
of the two semi-infinite L-like media, from 3 to 4. This results in a Figure IV14: The insertion of a liquid
change in energy layer L between two solids A and B has
an energy associated with it, which can
! be calculated via the following steps.
AL 1 1
W34 = 2 (IV26)
12 D02 D
A ALB = A AB + A L A AL A BL (IV28)
dW A
( D ) = = ALB3 (IV29)
dD 6D
If A ALB 0 then the disjoining pressure is negative, which means
that a tension (negative pressure) has to be exerted to prevent the
film for becoming thinner.
It is interesting to relate this analysis to the macroscopic approach
of Chapter II via the definition of a spreading parameter S as in Eq.
II2. Clearly the two approaches should lead to the same result in
the macroscopic limit, i.e. for large values of D. In other words, one
should have
A ALB
lim Wwetting = = AL + BL AB (IV30)
D 12D02
intermolecular forces IV11
I will let you find out on your own9 that this is indeed the case. 9
Hint: use Eqs. IV19 and IV20.
Therefore, the present analysis enables us to find the correction to
the macroscopic wetting energy AL + BL AB in the case where
the layer is not macroscopically thick. The result can be written as
" #
D0 2
W ( D ) = ( AL + BL AB ) 1 (IV31)
D
W /( AL + B L AB)
1
The value obtained with the generally accepted values D0 = 1.65 is 0.8
plotted in Fig. IV15. The figure shows that the macroscopic values 0.6
of the energies are reached for thicknesses of about 2 nm. For objects
0.4
smaller than about that size, you expect significant deviations from
the predictions of the macroscopic laws of wetting. 0.2
0
0 5 10 15 20
Let us now discuss the sign of A A LB and of the disjoining pres-
D (
A)
sure in a few characteristic situations. Using the geometric-mean rule
Figure IV15: Normalized wetting
Eq. IV14 for composing Hamaker constants, enables one to rewrite energy, as a function of the thickness D
A e f f in the following way as a function of the Hamaker constants of of the liquid layer. This was plotted by
A, B and L: assuming D0 = 1.65 .
p p p p
A A LB = AA AL AB AL (IV32)
which can only be positive. Two identical media can only attract each
other.
When one of the two media, say, B is vacuum, the situation is The rule of thumb for spreading is
simply that of a liquid spreading over a surface. The question is that a liquid spreads on any solid
more polarisable than itself. This is the
about whether the liquid will spontaneously thicken or not. In that
reason why oil spreads on metals, and
case, the effective Hamaker constant is obtained by setting A B = 0, water does not spread on most plastics.
i.e. If you look at the Hamakers constant
of liquid helium in Tab. IV2, you will
p p p
A A LO = A L AA AL (IV34) also understand why liquid helium is a
universally wetting fluid.
According to this analysis, the liquid spreads on the solid A if the
Hamaker constants satisfy A L A A . If you recall that the ori-
gin of A is the London dispersive forces described by Eq. IV4, this
criterion is equivalent to stating that the liquid is electrically less
polarisable than the solid. The criterion for wettability based on
In the general situation, the effective Hamaker constant is positive Hamakers constant looks very much
like Zismans criterion based on a
except when A L has a value intermediate between A A and A B . In critical surface tension C discussed in
that case, it is energetically favourable for the liquid to enter in the in- Chapter II.
terstice between A and B, thereby exerting a pressure that pushes A
IV12 c.j. gommes, chim0698
and B apart. This is illustrate on Fig. IV16. Using Atomic Force Mi-
croscopy (AFM) the authors of that study measured directly the force
between a gold nanoparticle and a support, in bromobenzene. When
the support is also made of gold, the force is attractive as expected
based on Eq. IV33. By contrast, when silica is used as a support
a repulsive force is observed. Silica and gold were not chosen ran-
domly for that experience. For a repulsive force to be observed, the
Hamaker constant of bromobenzene has to be intermediate between
silica and gold. From Tab. IV2, the Hamaker constants of silica and
gold are very different (ASiO2 ' 6.5 1020 J and A Au ' 45 1020 J),
which is a favourable condition to observe repulsion.
Figure IV17: Hendrick Casimir (1909-
The calculation of the effective Hamaker constant via Eqs. IV28 2000). Picture from Wikipedia.
or is interesting conceptually because it enables one to understand
physically the sign of A ALB , but is not necessarily practical because it
requires the three Hamaker constants A A , A B and A L to be known.
Another way has been developed by Lifshitz based on electromag-
netic calculations. The following formula is a good approximation for
A ALB
fore, from a physical perspective, Eqs. IV35 and Eq. IV4 are not so
different after all.
A practically important situation where repulsive van der Waals
forces play a role is the freezing a water. It is well known that grow-
ing ice crystals are able to to push away solid material initially in
contact with water. This is notably striking in frost heave, by which
entire layers of soil are deformed by growing ice crystals (see Fig. IV
19). If you think of it, this is possible only if a repulsive force exists
between the growing ice and the suspended material. In absence of
Figure IV19: Stone rings is an example
any repulsive force, the growing ice crystal would simply engulf the of structures that can form further to
solid and grow around it rather than push it. frost heaving. Picture from Wikipedia.
To analyse phenomena like frost heave, the Hamaker constant
between ice and a few oxides across water are reported in Tab. IV3.
These values have been calculated using the general relation given
Eq. IV35, which is the reason for which the dielectric constants and
refractive indices are reported in the table. For the calculations, the
value e ' 3 1015 Hz was used for the ionisation frequency. The
values in the table show that ice attracts ice across water, as testified Table IV3: Van der Waals interaction
by a positive value of the Hamaker constant A. This was expected energies between ice and various
from our previous analysis based on Eq. IV33 because two identical oxides. Taken from G.W. Scherer,
Cement and Concrete Research, 30
media can only attract each other, and it is also confermed by the (2000), 673.
Lifshitz expression.
Substance e n A (1021 J)
More interestingly, the values in the table also show that ice repels Water 80 1.33 -
all the considered oxides (quartz , mica, and alumina) as testified by Ice 110 1.309 1
Quartz 3.8 1.448 -1.20
the negative values of A. The van der Waals repulsion between ice Mica 7.0 1.60 -1.211
and these oxides across water is the nanometer-scale phenomenon Alumina 11.6 1.75 -2.94
that is responsible for such spectacular effects as frost heave (see e.g.
Fig. IV19).
An interesting technical application of repulsive van der Waals
forces between a solidifying solvent and suspended particles is the
so-called freeze-casting methods for shaping ceramic and metallic
materials. This is illustrated in Fig. IV20. With this type of process,
one can chose appropriately the solvent to have a selective repulsion
of some suspended particles (not necessarily all of them), to design
porous materials with specific morphologies.
IV14 c.j. gommes, chim0698
Further reading
Exercises
2. Compare the van der Waals forces between two spheres with the
capillary force calculated on Page III9.
Here is a simple way to look at it. Melting consists in the pass- Figure V3: Phase diagram of gold,
ing of the substance from a crystalline state with low energy uC and from D.A. Young, Phase diagrams of
the elements, technical report from the
low entropy sC to a liquid state with higher energy u L and larger US Department of Energy (1975).
gibbs-thomson effects V3
0 u L uC
Tm = (V1)
s L sC
where v and s are the molar volume and entropy, respectively. Imag-
ine we knew the chemical potential, say, of the liquid state L at a
given pressure P0 and temperature T0 . Using a Taylor development,
one could estimate the value of L for a value of P and T not very far
from P0 and T0 using the following Taylor development
L L
L ' L ( P0 , T0 ) + [ P P0 ] + [ T T0 ]
P T T P
2 2
1 L 1 L
+ 2
[ P P0 ] 2 + [ T T0 ] 2
2 P T 2 T 2 P
2
L
+ [ T T0 ] [ P P0 ] + (V5)
TP
C/ L ( P, T ) ' C/ L ( P0 , T0 ) + v C/ L [ P P0 ] s C/ L [ T T0 ] (V6)
C ( P0 , T0 ) + v C [ P P0 ] s C [ T T0 ]
= L ( P0 , T0 ) + v L [ P P0 ] s L [ T T0 ] (V7)
Of course, you can chose in here any value of P0 and T0 that would
make your life easier. A convenient choice here is to take P0 = 0 and
for T0 the melting temperature at that particular pressure Tm 0 . With
0 v L vC
Tm = Tm +P (V8)
s L sC
which is identical to Eq. V2, as it should.
Does Eq. V3 still apply? There is no way you can answer that ques-
tion unless you know exactly where that equation comes from. Think
about this before proceeding with the studying/reading of this chap-
ter: where does it come from?
As a matter of fact, the equality of the chemical potentials of two
phases at equilibrium is not a first principle of thermodynamics. The
general law of thermodynamics is that the free energy of a system
is minimal, subject to whatever external constraint is imposed on it.
The particular form of the free energy that is relevant depends on
the variables that are used to characterise the system. For example,
we are currently interested in analysing the melting/freezing of
a substance at a given temperature T and pressure P. With these
variables, its is the Gibbs free energy G that is relevant.
The general differential form of Gibbs equation in the case of a
system comprising a crystalline phase C and a liquid phase L can be
written as follows
Figure V5: William Thomson, first
dG = VC dP S C dT + C d NC + C d A C Baron Kelvin (1824-1907). Picture from
+ VL dP S L dT + L d N L + L d A L (V9) Wikipedia.
dA 2v
dA = vd N = dN (V10)
dV R
where v is the molecular volume, and the second equality results
from assuming that the particles are spherical. With that in mind, the
equilibrium state of the system comprise molten and frozen nanopar-
V6 c.j. gommes, chim0698
2 2
L ( P, Tm ) + L v L = C ( P, Tm ) + C v C (V11)
R R
This equation generalises Eq. V3 to dispersed system, i.e. in which
surface energies are not negligibly small.
In order to convert Eq. V11 into a more usable equation relat-
ing the melting temperature to the particle size, all we need to do is
express the chemical potentials explicitly in terms of the tempera-
ture. This can be done using Eq. V6 with suitable values of P0 and
T0 . A convenient choice is to take P0 as the ambient pressure and
T0 = Tmb as the melting temperature of the bulk material at that par-
ticular pressure, i.e. such that C ( P0 , Tmb ) = L ( P0 , Tmb ) . With that
particular choice, Eq. V11 takes the following simple form
Tm 2 C v C L v L
= 1 (V12) The choice we made of the reference
Tmb R h m temperature and pressure T0 and
P0 has no consequence on Eq. V12.
where we have used the notation h m = Tmb ( s L s C ) for the en- It simply enabled us to express the
thalpy of melting of the substance. Eq. V12 is the Gibbs-Thomson thermodynamic quantities in terms
of the bulk melting temperature Tmb .
equation. It relates the melting temperature Tm of particles to their As an exercice, repeat the analysis
size. Note that the dependence is in 1/R, and that Tm converges to without making any explicit choice
for P0 and T0 . You will then obtain an
the bulk melting temperature Tmb for R . expression similar to Eq. V12 with a
With respect to the Polyas steps, we now reached the point where cryptic combination of C/L ( T0 , P0 ). If
we are supposed to look back, and see if we achieved what we were you express that for large particles, the
melting temperature should coincide
aiming at. The purpose of our analysis, which eventually lead to Eq. with Tmb , it will all simplify into Eq.
V12, was to describe the data in Fig. V2. Does it make sense? In V12.
many respects it does. However, we still have to be sure we under-
stand the sign of Tm Tmb . As a first approximation, consider the
simple case where vC ' v L . In that case, the numerator in the Gibbs-
Thomson equation is proportional to C L , which determines
whether the small particles melt at a higher or lower temperature.
To understand the sign of C L , I encourage you to go back to
Chapter 1 and be sure you are comfortable with Stefans interpre-
tation of surface energy (see Eq. I12) before you continue reading.
For the sake of a back-of-the-envelope calculation, consider again a
6-coordinated cubic arrangement of atoms, both in the crystalline
and in the liquid states. Because we assumed vC ' v L , we may also
assume that the spacing between atoms d is the same in both phases.
The order of magnitude of d is the Angstroem. In the crystalline (the
liquid) phases, each atom has a binding energy eC (e L ) with each of
its six neighbours, except at the surface where one bond is missing.
The surface energies of the crystalline and liquid phases are therefore
something like
e
C/L ' C/L (V13)
d2
gibbs-thomson effects V7
hm = 6 (eC e L ) (V14)
Tm 1 d
b
' 1 (V15)
Tm 3 R
Or you use the usual thermodynamic relations, e.g. Eq. V3, but
you account for the change in chemical potentials resulting from
Laplaces pressure.
V8 c.j. gommes, chim0698
Sometimes the second option is more intuitive, but it is also less gen-
eral. For example, Exercice XX at the end of the chapter is devoted to
the calculation of melting point depression in lamellar crystals, which
have no curvature. In that case the Laplace pressure is irrelevant but
the experimental melting point is nevertheless found to depend on
the thickness of the lamellae.
The rest of the chapter is a generalisation of Gibbs-Thomson equa-
tions to
I had no time to type this down; you will have to rely on your own
notes to study that. Next years students will be luckier than you,
perhaps.
VI0 c.j. gommes, chim0698
Further reading
Exercices
4. Use the Gibbs-Duhem equation to find a Taylor development of Figure V7: Example of lamellar struc-
similar to Eq. V6 but valid to the second order in P and T. tures in semi-crystalline polymers: in
that case the melting temperature de-
pends on the thickness of the lamellae.
Picture from Macromolecules 42 (2009)
2135.
Thermal fluctuations
Very few scientific items, let alone equations, have the privilege of
becoming cultural symbols. Einsteins E = mc2 is definitely one such
item. The second equation on that list is probably Boltzmanns def-
inition of entropy S = k ln[W ], which can be read on his tombstone
in Vienna. To the present day, Boltzmanns definition of entropy is
the best link we have to relate the microscopic and the macroscopic
worlds, i.e. the motion of atoms and molecules to the property of
matter at our scale.
Richard Feynman necessarily had that equation somewhere in his
mind when he wrote that sentence in the epigraph. The goal of the
present chapter is to provide you with a crash course on a few topics
that are usually part of a broader course in statistical thermodynamics.
In other words, this chapter is about the type of imagination a thinking
that Feynman refers to.
VI2 c.j. gommes, chim0698
S = k B ln [] (VI1)
thermal fluctuations VI3
Heat Bath
Imagine a small system with a given volume and a given number of
T, Eb
molecules, which is in contact with a much larger system with which
it can exchange energy under the form of heat. For example: a tiny Figure VI2: A subsystem in con-
dust particle floating in a large room filled with air. The particle is tact with a heat bath, with which it
constantly hit by air molecules, which makes its every atom jiggle exchanges energy.
around some equilibrium position. Each time an air molecule hits the
dust particle, it may loose some of its energy in favor of the particle.
The opposite may also happen, an atom of the particle may hit an
air molecules in its vicinity, thereby loosing some of its energy. The
dust particle is therefore constantly fluctuating between different
microstates. We want to characterize these fluctuations.
In the following, we refer to the dust particle as the subsystem s
and the air filling the room as the heat bath b. The system comprising
the subsystem and the heat bath is the composite system. Although
the energies Es and Eb do fluctuate in a complex way, the energy
of the composite system E = Es + Eb is a constant. Whenever the
subsystem has energy Ei , the heat bath has energy E Ei .
The clever trick for analyzing the fluctuations of s consists in not-
ing that the ergodic hypothesis does apply to the composite system.
Accordingly, the probability that the subsystem be in state s is
1 b ( E Es )
ps = (VI3)
i b ( E Ei )
where the denominator accounts for the fact that the probabilities
should add up to 1.
One interesting observation that can be done at this stage is that ps
does only depend on the energy Es . This is naturally a consequence
of the ergodicity of the composite system. To express the dependence
of ps on Es in a more practical form, one can write
Sb ( E Es )
ln[ ps ] = ln[b ( E Es )] C = C (VI4)
kB
where the constant C is simply the logarithm of normalizing con-
stant, and the second equality results from Boltzmanns equation. The thermodynamic relation T1 =
Remember that the subsystem is much smaller than the heat bath, S
E V,N
can be considered as the
so that Es E. This enables to write a Taylor development, limited definition of the temperature.
to the first term as
S ( E) 1 dSb
ln[ ps ] ' b Es C (VI5)
kB T k B dE
VI4 c.j. gommes, chim0698
E
Z= exp[ k B iT ] (VI7)
i
Relation to thermodynamics
1 E ln[ Z ]
h Ei =
Z Ei exp[ k B iT ] =
(VI8)
i
The average entropy is calculated in the same way, starting from Eq.
??, i.e. as
hSi = k B pi ln[ pi ] (VI9)
i
Note that this definition coincides with the microcanonical entropy
(Eq. ??) in the particular case where pi = 1/ for all states.
Using Boltzmanns distribution (Eq. VI6) for pi , the definition of
the average entropy can be put under the form
h Ei
hSi = + k B ln[ Z ] (VI10)
T
This expression enables us to identify Helmholtzs free energy F =
h Ei T hSi with
F = k B T ln[ Z ] (VI11)
Therefore, knowing the partition function is equivalent to knowing a
thermodynamic potential of the system.
All the relevant thermodynamic properties can then be calculated
in the usual way, as
F F F
S= P= = (VI12)
T V,N V T,N N T,V
The derivatives of the free energy result
from the differentiation of F = E TS,
when using the general relation dE =
TdS pdV + dN.
thermal fluctuations VI5
and using the fact that ln[ Z ]/ = h Ei, one reaches the final
result p
E = k B T 2 CV (VI15)
where CV = E/T is the heat capacity of the subsystem. Can you imaging an experimental
An interesting observation in Eq. VI15 is that E increases only setup to put statistical fluctuations in
evidence?
as N 1/2
k B T n
3N 3N
Z= d x d p exp (VI16)
N! h 3N =1 2m
The first factor accounts for the fact that interchanging any two parti-
cles does not change the state. The volume integral is simply equal to
V N . The momentum integral can be calculated as
3N
1 p2
Z
dp exp (VI17)
k B T 2m
1 VN
Z= 3N
(2mk B T )3N/2 (VI18)
h N!
from which the free energy is found to be
3
F = k B T N ln[V ] ln[ N!] + N ln[2mk B T ] 3N ln[h ] (VI19)
2
VI6 c.j. gommes, chim0698
1
P0 = (2m)3/2 (k B T )5/2 (VI22)
h 3
VII0 c.j. gommes, chim0698
Further reading
Exercices
Carl Reiner
Supersaturation
ln( ) = (VII1)
kB T
We now consider a few particular cases, and explicit the values of
and in these cases.
l = l ( Tm ) sl ( Tm )( T Tm )
s = s ( Tm ) ss ( Tm )( T Tm ) (VII4)
The subscripts stand for solid and liquid. These expressions are ex-
pected to hold for temperature not too far from Tm . Expressing that
l ( Tm ) = s ( Tm ), we find
l s = ( T Tm )(ss sl ) (VII5)
hm
sl sl = (VII6)
Tm
metastability and nucleation VII3
hm
T
ln( ) = 1 (VII7)
kB T Tm
A+ + B AB(s) (VII8)
= AB A B (VII9)
A = 0A + k B T ln(C A )
B = 0B + k B T ln(CB ) (VII10)
C A CB = K S (VII11)
k B T ln(KS ) = AB 0A 0B (VII12)
C A CB
= (VII13)
KS
which can be easily generalised to more complex equilibria than Eq.
VII8.
G = N + A (VII14)
VII4 c.j. gommes, chim0698
4R3
G = + 4R2 (VII15)
3vm
where R is the radius of the droplet, and vm is the molecular volume.
The first term in Eq. VII17 is the one we had in mind when think-
ing of macroscopic thermodynamics: according to this term the free
energy is decreased when R is made as large as possible, i.e. when
as much vapour as possible is condensed (as expected for P P0 ).
However, the second term balances this effect by assigning a positive
thermodynamic cost to the creating of a droplet. What you should
expect to happen therefore depends on more than merely the com-
parison of P and P0 .
When you have a situation such as described by Eq. VII17, it
is always useful to put it first in a dimensionless form, in order to
understand the role of each of the dimensional parameters vm , , and
k B T (which we take as an order of magnitude for = K B T ln( )).
For that purpose, on may first notice that the first term is of the order
k B TR3 /vc ; it is balanced by the second term, which is of order R2 .
This suggests using
vm
= (VII16)
kB T
as a unit for R and, say 42 as the unit of G.
Using these units, the extra free energy associated with the cre-
ation of a droplet of radius R can be written in the simpler way
2 3
G R 1 R
= ln ( ) (VII17) 10
42 3
The situations sketched in Fig. VII1. For < 1 the volume contribu-
G/(4 2 )
It is easy to remember that the free energy barrier is simply one third
of the critical nucleus surface energy.
To make these results more "real", let us consider the practical case
of undercooled water. In this case, the critical radius can be written
as
vm 1
R = 2 (VII20)
hm 1 T/Tm
In the case of water ice with vm ' 1.09 106 m3 /g, hm = 333 J/g,
and ' 30 103 J/m2 , one has
vm
R (0) = 2 ' 2 (VII21)
hm
2 4
10 10 Figure VII2: Size of the critical ice ra-
dius and the corresponding free energy
3
barrier in the case of supercooled water
10
1 (Tm = 273 K).
G /(k B T )
10
R (nm)
2
10
0
10
1
10
1 0
10 10
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
T /T m T /T m
G 1 4 (2)2 1
= (VII24)
kB T 3 k B T [ln( P/P0 )]2
VII6 c.j. gommes, chim0698
with
4 (2)2
' 139 (VII25)
kB T
The critical nucleus size and the corresponding free energy barrier
are plotted in Fig. VII3.
2 4
10 10 Figure VII3: Size of the critical ice
radius and the corresponding free
3
energy barrier in the case of water
10
1 vapour at 373 K compressed above
G /(k B T )
10
P0 = 1 atm.
R (nm)
2
10
0
10
1
10
1 0
10 10
0 0.5 1 1.5 2 0 0.5 1 1.5 2
ln(P /P 0 ) ln(P /P 0 )
2
k T 16
I ' 2B exp (VII27)
vm 3 k B T [ln( )]2
Heterogeneous nucleation
4R3
G = + 4R2 f ( ) (VII31)
3vm
with
1 3 1
f ( ) = cos( ) + cos3 ( ) (VII32)
2 4 4
VIII0 c.j. gommes, chim0698
Eq. VII31 is identical to Eq. VII17 except for the factor f ( ). This
means that Eq. VII18 remains valid in the case of heterogeneous nu-
cleation, but the radius has to be understood as a radius of curvature
2
R = (VII33)
ln( )
On the other hand, the free energy barrier has to be multiplied by a
factor f ( ), the dependence of which on is plotted in Fig. VII5. As 1
f ()
close to 0. In this case case, the change of surface energy SL S is
0.4
so negative that it almost balances the L contribution.
Remember that the very reason why there is a nucleation barrier is 0.2
2
kB T 16
I ' 5/3 exp f ( ) (VII34)
vm 3 k B T [ln( )]2
which differs from Eq. VII27 though the function f ( ) and through
the exponent of vm in the pre-exponential factor.
Another thing that I encourage you to think about is the case
of Fig. VII6 which is more realistic that a flat surface. For a given
contact angle and a given volume of the droplet, the ratio of the
liquid/solid to the free liquid surface area is larger than on a flat
surface. You expect this to decrease still the nucleation barrier.
Figure VII6: Surfaces are seldom
perfectly flat. Remember that the length
scales we are talking about are just a
few nanometers. On that scale, any
surface has defects, which may be
modelled as ditches: you may therefore
expect this configuration to be more
realistic than Fig. VII4.
Adsorption on surfaces
Friedrich Nietzsche
An adsorption isotherm describes the mass-transfer equilibrium Figure VIII1: Irving Langmuir (1881-
(a given temperature) between a reservoir and a surface on which 1957) is the first industrial researcher to
receive a Nobel Prize (in 1932).
molecules can adsorb. The general relation takes therefore the form
n = f () (VIII1)
= B( T ) + k B T ln( x ) (VIII8)
The fact that ads depends on N is very natural: the more molecules
you have in a system, the larger their propensity to leave that sys-
tem, and vice versa.
to calculate ads .
The energy is easy to calculate: it is simply given by
Uads = Nu a (VIII12)
The entropy is barely more difficult to calculate. All you have to re-
member is the microscopic definition of the entropy in terms of the The difference between the Helmnholtz
number of configurations compatible with whatever macroscopic free energy F and Gibbs free energy
G is important only for systems that
variables define your system. This is the celebrated Bolzmanns equa- can undergo large changes of volume.
tion In the present context, the difference is
irrelevant.
S = k B ln() (VIII13)
In our case, is the number of ways in which N molecules (macro-
scopic variable) can be arranged on a surface with A adsorption sites.
As we show in Fig. VIII3, the total number of different configura-
tions with N adsorbed molecules is
A A!
= = (VIII14)
N N!( A N )!
which is plotted in Fig. VIII4. Note that N/A is nothing but the
fraction of the sites that are occupied by a molecule, which we shall
VIII4 c.j. gommes, chim0698
for = 1/2, and to vanish for = 1 and = 0. These two values 0.6
ln()/A
simply mean that there is a single way of having all sites occupied or
0.4
empty, respectively.
The chemical potential of the adsorbed phase is then obtained by 0.2
5
0 0.2 0.4 0.6 0.8 1
N/A
N Kx
= (VIII18)
A 1 + Kx
where K is a constant, given by
B ua
K = exp (VIII19)
kB T
adsorption on surfaces VIII5
0.6
N/A
0.4
0.2
0
0 1 2 3 4 5
x
N
' Kx (VIII20)
A
which is sometimes referred to as Henrys law.
The two parameters of the Langmuirs isotherm are A and K. The
total number of adsorption sites A is proportional to the specific
surface area. When the concentration or the vapour pressure is very
large, all adsorption sites tend to be occupied. In this case N A.
The other parameter is K, which depends on the energetics of the
adsorption (relative to the thermal energy k B T.) The isotherms are
plotted in Fig. VIII6. Note the effect that a change in K has on the
overall shape of the adsorption isotherm . Think about how a change in temper-
ature affects K and the isotherm. Does
To obtain a more precise, even if qualitative, meaning of the con-
that make sense to you, based on your
stant K, one needs a better understanding of the various terms in intuitive understanding of thermal
the reservoir chemical potential, Eq. VIII8. Consider for instance fluctuations?
us u a
K = exp (VIII22)
kB T
a) b) c) Figure
500VIII8: The situation is actually
a bit more involved. For example, to
adsorb a solute molecule on a surface
(a), one
400has first to remove the solvent
molecules adsorbed on the surface,
V a d s (cm 3 /g )
as well as those solvating the solute
(b), and
300only then can adsorption take
place.
200
Multilayer adsorption
100
When nitrogen adsorption is measured on carbon nanotubes the
isotherms look like in Fig. VIII9, which is clearly different from the
0
Langmuir-type isotherm that we last considered. Isotherms of that 0 0.5 1
type are quite common, and they are referred to as "type II". P /P 0
Unlike for "type I" (Langmuir-like) isotherms, the quantity ad-
Figure VIII9: Example of nitrogen
sorbed does not saturate when the pressure is increased. The most adsorption at 77 K measured on a
obvious explanation for this type of behaviour is multilayer adsorp- carbon nanotubes sample. Note the
tion. different shape with respect to the type
I isotherms described by Langmuirs
To describe quantitatively this type of adsorption, the assump- equation.
tions of the Langmuir model have to be relaxed. The BET adsorption
model is identical to Langmuir in all respects, except that we now
allow several molecules to adsorb on top of each other in each ad-
sorption site.
adsorption on surfaces VIII7
factor 1/2.
A1
1 A
= A + A ( A 1) + A ( A 1) + A + (VIII23)
2 2 4
The first term is for 4 molecules in a site, the second is for [3, 1]
configurations, the third for [2, 2], the fourth for [2, 1, 1] and the
last one for the Langmuir-like configurations.
5. Etc.
N e = A1 /a (VIII24)
N a = ea 0 AaP (VIII28)
1 = a ea aP0 (VIII29)
Multilayer adsorption
The analysis leading to Eq. VIII30 assumed that only one molecule
at most could exist at a given site, so the system was completely char-
acterised by the fraction of occupied sites 1 . If multi-layer adsorption
VIII10 c.j. gommes, chim0698
hni = 1 + 22 + 33 + . . . (VIII32)
Our aim now is therefore to calculate hni. Before we start the analy-
sis, note finally that the s satisfy
0 + 1 + 2 + 3 + . . . = 1 (VIII34)
K0 P0 = 1
K1 P1 = 2
...
Ki1 Pi1 = i
... (VIII35)
(1 + + 2 + ...)(1 )
(1 )
Of course you havent changed any-
thing by multiplying and dividing by
(1 ). If you develop the numerator,
however, you will find that it is equal to
adsorption on surfaces VIII11
C
hni = ii = (1 )2
0 (VIII37)
i =1
This is not the solution yet because 0 is still unknown. The value
found by expressing that i i = 1, which leads to
(1 C )(1 ) + C
1= 0 (VIII38)
1
= b eb aP (VIII40)
N CP/P0
= (VIII42)
A (1 P/P0 )(1 + (C 1) P/P0 )
which is the one that we shall use in Sec. to determine specific sur-
face areas from experimental adsorption data. We postpone to Sec.
the thorough discussion of the BET constant C.
Examples of BET isotherms are plotted in Fig. VIII13 for three
different values of C. At low relative pressure, the same Henry-like
linear adsorption as in the Langmuir isotherm is observed. When
the pressure approaches the saturation, the number of molecules
adsorbed per site diverges. This corresponds to the condensation
of a thick liquid layer on the surface. The effect of the constant C is
significant only when the thickness is relatively small, say hni 5.
VIII12 c.j. gommes, chim0698
hni = N/A
3
0
0 0.5 1
0
0 0.2 0.4 0.6 0.8 1
P /P 0
Discussion
where the es are the fraction of collisions from the gas phase that
result in condensation (on the surface or on the bulk liquid surface),
and the s are characteristic evaporation times. Evaporation is a
thermally activated process. A molecule close to the surface of a
bulk liquid (but inside the liquid) has a binding energy ub 0 that
keeps it in the liquid. Because of the thermal motion, the molecule
constantly receives energy from its neighbours or by being hit by
an incoming gas molecule, etc. As a consequence, the energy of the
molecule is fluctuating randomly in time, and the probability of
finding it in a state of energy E above its ground state is given by
adsorption on surfaces VIII13
Boltzmanns factor
E
Proba( E) ' exp (VIII44)
kB T
where the missing factor19 is a normalising constant. If that extra- 19
That is the meaning of the symbol '.
energy happens to be larger than the binding energy of the molecule,
i.e. if E + ub 0 then it can evaporate. One therefore expects the
following temperature-dependency for the evaporation rate 1/b
1 ub
= b exp (VIII45)
b kB T
where b is a typical vibration frequency. Be sure you understand this
equation, in particular the sign in the exponential: ub is negative so
that if the binding energy is very large (i.e. very negative). A similar
expression can of course be given for adsorbed molecules. This leads
to
ub u a
ea b
C= exp (VIII46)
eb a kB T
The most important factor in there is the exponential. The prefactor
involves b /a the ratio of the natural vibration frequencies of the
molecules in the bulk and on the solid surface, as well as ea /eb the
ratio of the "probabilities of capture" when a gas molecule hits the
solid surface or the surface of the bulk liquid. One can reasonably
expect that ratios are close to unity. Moreover, we do not expect them
to be temperature-dependent. The important physical quantity that
controls the value of the exponential factor is (ub u a )/(k B T ), having
a clear physical meaning. The constant C therefore characterizes the
binding of a molecule to the surface. It has exactly the same meaning
as the constant K in Langmuirs equation.
The relation can be made even more explicit by considering the
general expression that we have found earlier: K = exp(( B
u a )/k B T ) with B = 0 the chemical potential of the liquid, in the
case of vapour adsorption. Since the chemical potential is Gibbs
energy per molecule, one can write
0 = ub + P0 vb Tsb (VIII47)
where ub , vb and sb are the molar energy, volume, and entropy in
the bulk state. Taking this into account, the expression of K can be
written as
P0 vb Tsb ub u a
K = exp exp (VIII48)
kB T kB T
where the similarity with Eq. VIII46 is now obvious. The relation
between the two approaches (statistical and dynamical) could be
pushed even further. However, what we have done here should suf-
fice to convince you that the two approaches are consistent with each
other, and that they actually give the same result.
VIII14 c.j. gommes, chim0698
P/P0 1 C1 P
= + (VIII49)
(1 P/P0 ) N AC AC P0
(g /cm 3 )
VIII9. The red line is the least-square
fit of the data for 0.05 P/P0 0.35 .
BE T f unction 0.02
0.01
0
0 0.5 1
P /P 0
Exercices
6. One classically advocates that the BET model should only be used
from P/P0 = 0.05 to P/P0 = 0.35. Figure VIII15 shows how
the BET model actually compares with the data. To your opinion,
why is there any deviation between the data and the model? The
reasons need not be the same at low and high pressure.
IX0 c.j. gommes, chim0698
100
0
0 0.2 0.4 0.6 0.8 1
P /P 0
9. Typical values for the BET constant are C ' 20 for adsorption on
polymeric materials and around C ' 200 for silica. Can you make
sense of this? What does this mean?
Further reading
Exercices