Surface Chemistry of Solid and Liquid Interfaces

H. Y. Erbil
Blackwell Publishing

Chapter 1
Introduction to Surfaces and Interfaces

1.1 Definition of a Surface and an Interface

A phase of a substance is a form of matter that is uniform throughout in chemical com-
position and physical state. There are mainly three phases of matter namely solid, liquid
and gas. The word fluid is used to describe both gas and liquid phases. We usually classify
the phase of a material according to its state at the normal ambient temperature (20–25°C),
which is well above the melting point of most fluids. We mostly deal with two or more
phases, which coexist, in equilibrium or non-equilibrium conditions. Phase diagrams are
used as a convenient method of representing the regions of stability of solid, liquid and
gas phases under various conditions of temperature and pressure. An interface is the phys-
ical boundary between two adjacent bulk phases. The interface must be at least one molec-
ular diameter in thickness for the purpose of constructing a molecular model. In some
cases it may extend over several molecular thicknesses. We use the word surface in order
to define the physical boundary of only one of these phases, such as solid surface and liquid
surface etc. In reality, we deal with an interface in all cases other than absolute vacuum con-
ditions for solids, since every single phase is in contact with another phase such as solid–air,
liquid–air contacts. In many standard physical chemistry, surface chemistry and surface
physics textbooks, the words surface and interface are used interchangeably because the
authors neglect the small differences between the air phase and absolute vacuum condi-
tions. On the other hand, some authors define and use the word surface for only the
solid–gas and liquid–gas phase contacts, and the word interface for all of other phase con-
tacts, but this has no scientific basis and should be abandoned.
The molecules that are located at the phase boundaries (that is between solid–gas,
solid–liquid, liquid–gas and liquid1–liquid2) behave differently to those in the bulk phase.
This rule generally does not apply for solid–solid and gas–gas interfaces where atomic and
molecular bonding in the solid structure restrict the reorientation of interfacial molecules
for the former, and the ease of miscibility of different gas molecules in free space does not
allow any interface formation for the latter.
There is an orientation effect for molecules at fluid surfaces: the molecules at or near
the fluid surface will be orientated differently with respect to each other than the mole-
cules in the bulk phase. Any molecule at the fluid surface would be under an asymmetri-
cal force field, resulting in surface or interfacial tension. The nearer the molecule is to the
interfacial boundary, the greater the magnitude of the force due to asymmetry. As the dis-
4 Surface Chemistry of Solid and Liquid Interfaces

tance from the interfacial boundary increases, the effect of the force field decreases and
vanishes after a certain length. Thus, in reality there is no very sharp interfacial boundary
between phases, rather there is a molecular gradient giving a change in the magnitudes of
both density and orientation of interfacial molecules. We must remember that this layer is
also very thin, usually between one and five monomolecular layers for liquid–vapour inter-
faces. The location of the so-called mathematically dividing surface (see Section 3.2.5) is
only a theoretical concept to enable scientists to apply thermodynamics and statistical
mechanics.
For solid surfaces, we should define the depth of the molecular layers, which are regarded
as surface. We may say that only the top monolayer of surface atoms and molecules, which
is the immediate interface with the other phases impinging on it, can be called the surface.
However, in practice, it depends on the spectroscopic technique that we apply: some so-
phisticated spectroscopic instruments can determine the chemical structure of the top 2–10
atomic layers (0.5–3.0 nm), thus taking this depth as the solid surface layer. In many older
books on surface chemistry or metallurgy, the surface is regarded as the top 100 nm or so
of the solid, because some older technologies can only determine the chemical structure
in the range of 10–100 nm and the surface was therefore assumed to be in this depth range.
However, at present, this range may be called an intermediate layer between the bulk and
surface structures, and only after 100 nm is it appropriate to regard such a layer in terms
of its bulk solid-state properties. Thus, in the recent scientific literature, it has become
necessary to report the solid surface layer with its thickness, such as the “top surface
monolayer”, the “surface film of 20 nm”, the “first ten layers”, or the “surface film less than
100 nm” etc.

1.2 Liquids and Liquid Surfaces

A liquid is defined as a medium which takes the shape of its container without necessar-
ily filling it. Water is the most abundant liquid on earth and is essential for living systems,
and non-aqueous liquids are widely used as solvents in synthetic, analytical, electrochem-
istry, polymer chemistry, spectroscopy, chromatography and crystallography. Molten me-
tals are also considered to be liquid solvents. We may also consider another property that
distinguishes liquids: the response of a liquid to an applied force is mainly inelastic; that
is a liquid does not return to its original shape following the application, then removal, of
a force.
The densities of liquids under normal pressures are not too dissimilar to those of their
solids between the melting and boiling points. Generally a liquid is less dense than its solid
at the melting point, but there are a few exceptions of which water is one; ice floats on
water. These less dense solids have rather open crystal structures. Silicon, germanium and
tin are other examples. Another similarity between normal liquids and solids is that they
have a low compressibility due to there not being a great deal of space between the mole-
cules in a liquid.
If we were able to observe the molecules in a liquid, we could see an extremely violent
agitation in the liquid surface. The extent of this agitation may be calculated by consider-
ing the number of molecules that must evaporate each second from the surface, in order
to maintain the measurable equilibrium vapor pressure of the liquid. When a liquid is in
 Introduction to Surfaces and Interfaces 5

contact with its saturated vapor, the rate of evaporation of molecules is equal to the rate
of condensation in the equilibrium conditions. For example, it is possible to calculate from
kinetic theory that 0.25 g sec−1 water evaporates from each cm2, which corresponds to
8.5 × 1021 molecules sec−1 at 20°C having a saturated water vapor pressure of 17.5 mmHg.
However, the size of the water molecules permits only about ≈1015 molecules to be present,
closely packed in each cm2 of the surface layer at any particular moment, and we can con-
clude that the average lifetime of each water molecule is very short, ≈10−7 sec. This tremen-
dous interchange between liquid and vapor is no doubt accompanied by a similar
interchange between the interior of the liquid and its surface. However, although the
thermal agitation of water molecules is so violent that they jump in and out of the surface
very rapidly, the attractive forces between them are able to maintain the surface to within
one to three molecules thickness. The evidence for this can be derived from the nature of
light reflection from the liquid surfaces which results in completely plane polarized light
from very clean liquid surfaces, indicating an abrupt transition between air and the liquid
surface. On the other hand, the surface molecules of a liquid are mobile, that is they are
also in constant motion parallel to the surface, diffusing long distances. Other properties
of liquid surfaces will be described in Chapter 4.
Liquid surfaces tend to contract to the smallest possible surface area for a given volume
resulting in a spherical drop in equilibrium with its vapor. It is clear that work must
be done on the liquid drop to increase its surface area. This means that the surface mole-
cules are in a state of higher free energy than those in the bulk liquid. This is due to the
fact that a molecule in the bulk liquid is surrounded by others on all sides and is
thus attracted in all directions and in a physical (vectorial) balance. However for a surface
molecule there is no outward attraction to balance the inward pull because there are very
few molecules on the vapor side. Consequently, every surface molecule is subject to a strong
inward attraction perpendicular to the surface resulting in a physical force per length,
which is known as surface tension (see Section 3.2.4). In addition, the tendency to mini-
mize the surface area of a fluid surface can also be explained in terms of a thermodynamic
free energy concept (see Chapter 3), since the surface molecules have fewer nearest neigh-
bors and, as a consequence, fewer intermolecular interactions than the molecules in the
bulk liquid. There is therefore a free energy change associated with the formation of a liquid
surface reversibly and isothermally, and this is called the surface free energy or, more cor-
rectly, the excess surface free energy. The surface free energy term is preferred in the litera-
ture and it is equivalent to the work done to create a surface of unit area (Joules m−2 in the
SI system). It must be remembered that this is not the total free energy of the surface mol-
ecules but the excess free energy that the molecules possess by virtue of their being located
on the surface.

1.3 Surface Area to Volume Ratio

All liquid droplets spontaneously assume the form of a sphere in order to minimize their
surface free energy by minimizing their surface area to volume ratio, as we will see in the
thermodynamic treatment in Chapter 3. The surface area to volume ratio can easily be cal-
culated for materials having exact geometric shapes by using well-known geometric for-
mulas. For example, for a sphere and a cube this ratio is