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Introduction

1.1 The importance of interfaces

1.4.3 Adsorption
1.4.4 Emulsions

1.2 Surfaces and interfaces

1.4.5 Colloids

1.2.1 Introduction

1.4.6 Membranes

1.2.2 Types of interface

1.5 Organization of the book

1.2.3 Defining the interfacial region

1.3 Stable interfaces
1.4 Key concepts
1.4.1 Surface tension and surface pressure
1.4.2 Wetting

1.1 The importance of interfaces

Interfaces are everywhere: in our bodies, in the food we eat and the drinks we
drink, in plants, animals, fish, insects and microbes, in our cars, in the soil, in
the atmosphere, in manufacturing and chemical factories. Occasionally, the
presence of an interface does not appreciably alter the behaviour of a system,
but in many cases it does have a significant effect and, in some cases, it dominates the behaviour.
Think for instance of the catalytic converter, which has been an integral
part of cars produced over the last decade. As the raw exhaust gases from the
engine pass over the solid metal and metallic oxide catalyst surface, a large
number of reactions take place, leading to more complete oxidation of the
gases and, hence, to a cleaner environment. The gases spend only milliseconds
in contact with the surface and yet this has a dramatic effect on the composition of the final exhaust mixture that is vented to the atmosphere. It is the
surface of the catalyst that is crucial.
Another important example concerns the inner lining of the lung. A layer
of fluid lines the alveoli and, at the surface of this fluid, in contact with the
air, is a layer that is only one molecule thick, composed mainly of phospholipids. This mixture of phospholipids and some proteins is known as lung
surfactant. Lung surfactant serves to lower the amount of work required for

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1 INTRODUCTION

the action of breathing, a function that is so important that if the surfactant is

not fully developed, unaided breathing is impossible. Because lung surfactant
is only produced late in gestation, most infants who are born before 30 weeks
gestation must be treated immediately after birth to ensure their survival.
Again, it is the properties of the very outermost surface that determine the
functioning of the entire system (see also Section 10.7).
In our day-to-day lives we are familiar with the behaviour of liquids, especially the way they flow, being controlled largely by gravity. However, in space
vehicles where the gravitational field strength is very low, hydrostatic pressure
is negligible, and liquids behave very differentlyin fact, the forces arising
from the interface between the liquid and the air dominate their flow.
Again and again we encounter similar examples of the importance of surfaces. With the increasing emergence of new technologies relying on miniaturization, surface properties are growing in importance. The new and exploding
field of nanotechnology is an obvious case where the solid surfaces of, for
example, nanoparticles and mesoporous materials, are the places where the
processes of interest take place. An understanding of processes occurring at
surfaces is therefore relevant to many new developments.
Even though surfaces are increasingly important to modern technology,
they have, in fact, been studied for a very long time. Reports dating from
Roman times describe the calming of water by spreading oil on the surface,
but arguably the beginning of the field as a scientific discipline dates from the
experiments of Benjamin Franklin, reported to the Royal Society in 1774,
where he describes the spreading of oil on a pond in Clapham Common, on
the outskirts of London. He observed that placing as little as one teaspoon of
oil on the surface calmed the ripples on a small area that quickly extended to
about half an acre (2 103 m2).
Before we can describe the complex processes that occur at surfaces, it is
important to describe exactly what we mean by this term.

1.2 Surfaces and interfaces

1.2.1 Introduction
Where two homogeneous bulk phases meet there is a region of finite thickness
where the properties change, often markedly, as we move from one bulk phase
to the other. Such regions are known as surfaces or interfaces (although the
term interphase would be a better description). Although we may commonly
think of a surface as being of negligible thickness, in fact, when we are discussing phenomena at a molecular level the thickness of the interfacial region is
significant and definitely non-zero.
The properties of the interfacial region are particularly important when
one of the phases is dispersed as many very small particles in the other phase,
because of the dramatic increase in surface area. The two phases are usually
referred to as the disperse (or dispersed) phase and the continuous phase.
Examples include colloids, emulsions, aerosols, and some natural and synthetic polymers. Often the particles are below the resolution limit of the optical microscope (<0.5 m), but above the size range of all except the largest
molecules. Table 1.1 illustrates how the surface area increases if we take a

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1.2 SURFACES AND INTERFACES

Table 1.1 Effect of subdivision into cubic particles on the surface area of a

disperse phase with a total volume of 1 cm3

Number of
particles

Particle volume/m3

Length of
cube edge/m

Total surface
area/m2

106

102

0.0006

10

10

0.006

106

1012

104

0.06

15

10
10

10

10

0.6

1012

1018

106

15

21

10

1018

10

10

60

1024

108

600

disperse phase of total volume 1 cm3 and subdivide it into smaller and smaller
cubic particles.
Thus, for example, 1 cm3 of disperse phase divided into cubic particles with
sides of 0.1 m (within the size range of most colloids) has an interfacial area
of 60 m2 and with sides of 10 nm the area is 600 m2.

1.2.2 Types of interface

Because there are three types of bulk phase, it is possible to classify interfaces
based on the nature of the bulk phases that lie on either side of the interface.
Thus, there are five types of interface:
gasliquid
liquid1liquid 2
gassolid
liquidsolid
solid1solid 2

GL

L1L2

fluid interfaces

GS
LS
S1S2

non-fluid or solid interfaces

Of course all gases mix with one another so there are no gasgas interfaces.
Usually with this notation the less dense phase will be shown first: GL rather
than LG, for example.
When three bulk phases meet in a line, this line is known as a triple
interface.

1.2.3 Defining the interfacial region

Taking an intensive property, such as density, and scanning its value from, say,
a liquid phase through the interface to a gas phase would give a plot such as
that in Figure 1.1.
In this case, the density shows a smooth transition from the high density
of the liquid to the much lower density of the gas. The bulk phases can be
separated from the interface by two surfaces parallel to one another, and
positioned so that the bulk phases are homogeneous and uniform (uniform

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(a)

density in this case), while the inhomogeneity and non-uniformity are contained entirely within the interfacial region lying between the two surfaces.
The dashed lines in Figure 1.1(c) illustrate this point.
We will see later that, for some properties, the transition from one bulk
phase to another does not follow a smooth monotonic transition, such as that
in Figure 1.1. For example, the concentrations of some solutes (particularly
marked with the surfactants, see Section 4.6) at the gassolution interface
may reach values very much higher than those in either bulk phase and exhibit
a profile such as that in Figure 1.2.
The solute in Figure 1.2 is said to be adsorbed at the interface. This term
will be defined and discussed in more detail in Chapter 3.

Gas

Liquid

Height

(b)

1.3 Stable interfaces

Density
Solution Interface Gas

Density

(c)

Height
Fig. 1.1 Density profile across

G = A + other terms.

(1.1)

In this equation, the coefficient is known as the surface tension or interfacial tension. If the system is stable it follows that must be positive, for if it
were negative, an increase in area would lead to a lowering of the free energy
and, therefore, the surface area would spontaneously expand. This would
ultimately lead to the dissolving of one substance in the other. Figure 1.3
illustrates how this process might occur for two liquids. In fact, the opposite
occurs for immiscible liquids, suggesting that for a stable interface must be
positive and that at equilibrium the interfacial area will tend to a minimum
in order to minimize the free energy. This process provides the driving force
for many of the phenomena that will be discussed in following chapters.
Equation (1.1) also indicates that processes that lower the value of the
interfacial tension would also be thermodynamically favoured. This is, then,

Solution

Interface

Gas

Solute concentration

the gasliquid interface. The

graph in (b) corresponds to
the sample (a) and in (c) it
has been rearranged into a
more customary orientation.
Dashed lines in (c) indicate the
interfacial region.

For any system at equilibrium, the free energy is at a minimum. If the system
contains an interface, it is reasonable to expect that the interface would contribute to the free energy, and that this contribution would be a function of
the area, A, of the interface. We might expect that this contribution would
take the form:

Height
Fig. 1.2 Concentration profile for a solute at the gassolution interface.

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1.4 KEY CONCEPTS

a second force capable of driving interfacial processes. The phenomenon of

adsorption is an important example.
Liquid A

1.4 Key concepts

Liquid B

Although the topic of interfacial science is vast, we have attempted to introduce the crucial areas in the subsequent chapters. In this section, we give a
broad overview of the field.
A dictionary of the terms used in interfacial science has been developed by
Schramm (2001).

1.4.1 Surface tension and surface pressure

Probably, the most important concept of all, particularly when dealing with
interfaces in which both bulk phases are fluids, is that of surface tension. The
existence of surface tension, and the effects that arise as a consequence, play a
major role in the behaviour of systems containing interfaces. Because surface
tension represents extra energy, which is proportional to the area, systems
attempt to minimize their surface area, resulting in the familiar fact that drops
of liquid in air and bubbles are spherical. Many effects are more subtle, however, and are only evident if the interface is curved.
Surface pressure is frequently used in situations where the surface tension has
been changed by events such as adsorption (see Section 1.4.3 and Chapter 3)
or the addition of an insoluble monolayer to the surface (Chapter 5). It is
defined as the reduction in surface tension arising from the event:
Fig. 1.3 The spontaneous

increase in surface area that

would occur between two
liquids if the surface tension
were negative. This does not
occur for immiscible liquids!

= o + f

(1.2)

where o is the original surface tension of the liquid, and f is the surface tension after the event. It follows that as the surface tension is normally reduced
by adsorption, surface pressure typically increases from zero to a positive
value.

1.4.2 Wetting
The shapes of liquid droplets and the wetting of solid surfaces are determined
principally by the forces acting at the relevant interfaces. These forces determine, for example, whether a liquid drop will spread over a solid surface
or roll up into a ball, whether liquid will rise up the narrow gaps between
the fibres of a wick, whether water will penetrate through the weave of an
umbrella cloth and contribute to the rise of sap in the stems of plants.
We are all familiar with the non-stick properties of TeflonTM, which benefits
from the tendency of liquids not to wet the surface, and fabrics designed to be
non-wetting have the potential to be self-cleaning and never need washing!

1.4.3 Adsorption
A major consideration of interfaces is that the two bulk phases normally have
quite different properties, and frequently materials that are soluble in one or

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both phases will find it energetically favourable to concentrate (or deplete) at

the interface. The main example is the class of materials called surfactants,
which are molecules that are designed to have a part that prefers one phase
and another part that prefers the other phase. Such materials tend to concentrate at the interface and are said to adsorb. This is crucial to a number of
processes, such as detergency, in which oils can be dispersed in water when
without detergent they are very insoluble. Such adsorbed layers are one molecule thick giving a thickness of 13 nm. They could, therefore, be described
as nanofilms.
Adsorption is not restricted to fluid interfaces: it occurs at all interface types.
For example, gases adsorb on to solids, a fact which is exploited in the routine
measurement of the surface areas of powders, and is an essential part in the
catalysis of many gas phase reactions. For example, the reactions that occur
in the catalytic converters of nearly all cars. Such catalysis is also essential in
many aspects of the chemical industry.
Adsorption also leads to methods for the fabrication of thin films, as thin
as a single molecular layer. Methods exist which begin with a single layer
at the airwater interface to build up, by the LangmuirBlodgett technique,
multilayer films, one layer at a time (see Section 5.4). Other methods use the
ability of molecules to adsorb and self-assemble at the interface between a
solution and a solid surface, forming self-assembled monolayers and multilayers (see Section 9.13). Monolayers on an airwater interface can also be
used to retard the evaporation of water, which is a major concern with open
water-storage dams in dry climates (see Section 5.9.1).

1.4.4 Emulsions
Emulsions, defined loosely as small droplets of one immiscible liquid in
another, are very common, although frequently we might not recognize their
presence. Common household products in which emulsions are frequently
present are foods, paints, and cosmetics. To take paints as an example, these
days most are water based. The water acts as a dispersion medium for an
emulsion of polymer particles. After application, the water evaporates and the
polymer particles coalesce to form a protective film.
Because emulsions are inherently unstable, preferring to minimize the surface area of the interface by individual droplets merging together, there is
an enormous amount of science in the stabilization of emulsions in order to
improve the effectiveness and marketability of products. This field is closely
related to adsorption and surfactants, as the stabilization of emulsions relies
on the use of surfactants in nearly all cases (see Chapter 6).

1.4.5 Colloids
Colloids are everywhere: in the ground on which we walk, in the air we
breathe, in the food we eat, in the liquids we drink, and in many parts of our
bodies. The term colloid refers to certain heterogeneous systems and the essential aspect is size. The International Union of Pure and Applied Chemistry
(IUPAC) (Everett, 1972) states that particles of the dispersed material must

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1.5 ORGANIZATION OF THE BOOK

have at least one dimension in the approximate range 1 nm to 1 m or that

there are discontinuities in the system in that range. Only one dimension need
be in the range, so fibres and thin films may be classified as colloidal. Also the
units need not be discrete, so networks such as foams may be regarded as colloidal provided that the foam lamellae fit the size range.
A colloidal dispersion (often simply called a colloid) consists of discrete
particles of colloidal size (the disperse or dispersed phase) dispersed in a continuous phase. The particles may be solid, liquid, or gas, and must all have the
same values of their intensive properties. The term, dispersed phase, implies
that the material in the particles has the same properties as the bulk phase of
the same composition. This is not always the case as the particle surface will
sometimes cause major modifications. Many colloidal dispersions are dispersions of nanoparticles.
Colloids are very common in industry, household products, and foods
(Dickinson, 1972), and even particulates in air pollution represent a colloidal
dispersion. The major issue with colloids is their tendency to aggregate and
achieving stability of the dispersion is usually the goal in the formulation
of products involving colloidal components. This requires a detailed understanding of the charged nature of the interface, the effects of added salts, and
other conditions.

1.4.6 Membranes
No biological organisms as we know them would exist without cell membranes that separate two liquid phases (usually aqueous) that would otherwise
mix. The other function of membranes is to allow the controlled movement of
molecules into and out of cells, selective permeability, which is a remarkably
complex task achieved by equally remarkable materials. These are primarily
molecules known as lipids and special proteins called membrane proteins.
Knowledge gained from the study of biological membranes is increasingly
being used to design better drug delivery systems.

1.5 Organization of the book

The book opens with three general chapters in which the basic concepts of
interfacial science are introduced and discussed, and some important equations developed. We then go on to consider the various types of interface as
shown above in Section 1.2.2. Fluid interfaces are free of the complications
that come from the surfaces of solids so these are considered first.
However, there are two notable and important omissions from the treatment. Interfacial science is heavily involved in electrochemistry, but the topic
is mentioned only briefly because there are numerous excellent texts on this
subject. The solidsolid interface provides the foundation of modern electronics and we did not consider that it would be possible to treat adequately the
immense amount of material now available on this topic in a short chapter.
Finally, in the last chapter we discuss some of the applications of interfacial science in biological systems. This is also a very large topic so we have

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concentrated on a few aspects where the relevance of the earlier chapters can
be demonstrated.

FURTHER READING
The literature of interfacial science
There is an extensive literature dealing with surface chemistry and its various manifestations. This ranges from reports from Roman times of calming waves by the spreading
of oil; through Benjamin Franklins experiments (1774) with monolayers on a pond
in London; Faradays (1857) preparation and study of gold sols; the development of
the first film balance by Agnes Pockels (1891) in the kitchen of her parents home; the
development of a theory to describe the adsorption of gases on solids by Brunauer,
Emmett, and Teller (1938); the formulation of a theory for the stability of lyophobic
colloids by Deryaguin and Landau (1941) and Verwey and Overbeek (1948); cloudseeding experiments by Langmuir and Schaefer (1946) and by Vonnegut (1946); and
the experiments of Mansfield and Vines (19551962) on the retardation of water
evaporation from large storages; to the many research and review papers currently
being published in international journals of high repute.
A large number of books have been published on various aspects of interfacial science. Many of these will be found in the Further reading sections near the end of each
chapter of this book. Also listed under this heading are relevant review articles, mostly
from one of the review journals or series devoted to our topic. These lists are not
exhaustive so it would always be worthwhile to browse nearby library shelves.
Original research is generally published in specialist journals, while there are also
a small number of papers in more general journals. The titles of these journals can be
seen in the references at the end of each chapter.

Chapter references
In each chapter the references are shown in the text by author and year of publication,
for example, Peng et al. (2001). A book reference may also include a chapter or page
number. At the end of the chapter the references to books and major review articles
are listed alphabetically under Further reading followed by other references under
References.
No attempt has been made to provide an exhaustive list of references. Key references are given, and also references to further data or more detailed information, or to
provide support for a possibly contentious argument.

REFERENCES
Dickinson, E. (1992). An Introduction to Food Colloids. Oxford University Press,
Oxford.
Everett, D.H. (1972). Definitions, Terminology and Symbols in Colloid and Surface
Chemistry: Part I. Pure and Applied Chemistry, 31, 579638.
Schramm. L.L. (2001). Dictionary of Colloid and Interface Science. WileyInterscience, New York.

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1.5 ORGANIZATION OF THE BOOK

EXERCISES
1.1 Find and describe other examples where an interface makes an important
contribution to the behaviour of a system. [Could be a class discussion]
1.2 List the colloidal systems that can be found in and around the home and state
why they can be considered as colloidal. [Could be a class discussion]

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