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STUDIES IN INTERFACE SCIENCE

Hydrophile-Lipophile Balance of Surfactants and Solid Particles

Physicochemical Aspects and Applications

Pyotr M. Kruglyakov

State Academy of Architecture and Building, Penza, Russia

ISSN  1383-7303

Volume 9 • Number suppl (C) • 2000

Table of Contents

Cover image

Title page

Studies in Interface Science

Copyright page

Preface

Introduction

Chapter 1: Physicochemical properties of surfactants used in the definition of hydrophile-lipophile balance

1.1 Classification of surfactants with respect to structure and chemical nature

1.2 Surface-related properties of surfactants

1.3 Bulk Properties of Surfactants

1.4 The contributions to Gibbs’ energy corresponding to the transfer of surfactant molecules from bulk phases to interfaces as compared to the transfer to other bulk phases. The interpretation of Traube’s rule

1.5 Brief Review of Surfactant Chromatography

Chapter 2: Stabilising ability of surfactants in emulsification and foam formation

2.1 Physicochemical properties of emulsion films

2.2 Kinetics of flocculation and coalescence

2.3 Phase inversion in emulsions

2.4 Effect of temperature on emulsion stability - phase inversion temperature PIT

2.5 Relation between foam stability and hydrophile-Iipophile balance

Chapter 3: Hydrophile-lipophile balance of surfactants

3.1 Griffin’s system of HLB numbers

3.2 Kinetic and thermodynamic rationalisation of HLB numbers - Davies’ HLBD number

3.3 Critical micellisation concentration and HLB numbers

3.4 Phase inversion temperature in emulsion -measure of hydrophile-lipophile balance

3.5 Hydrophile-lipophile balance and chromatographic characteristics of surfactants

3.6 Comparative analysis of Griffin’s and Davies’ HLB numbers, consideration of the influence of the medium and the surfactant structure on the HLB number systems

3.7 Thermodynamic approaches to the determination of hydrophile-lipophile balance

3.8 Hydrophile-lipophile balance and phase inversion of emulsions

3.9 Hydrophilic-oleophilic ratio and the formation of micellar systems (surfactant phases)

Chapter 4: Hydrophile-lipophile balance of solid particles

4.1 Behaviour of drops at solid surfaces, and solid spherical particles at liquid/liquid interface

4.2 Stabilisation of emulsions by solid particles

4.3 Work of wetting and determination of the hydrophile-lipophile balance for solid particles

4.4 Calculation of the hydrophile-lipophile balance for highly disperse solid emulsifiers

4.5 The dependence of emulsion stability on the work of wetting of emulsifier particles. HLB used as criterion of phase inversion in emulsions stabilised by solid particles

Chapter 5: Examples of the implementation of hydrophilicity- lipophilicity concepts in the development of the formulations of surfactants and selection of solid particles for certain purposes

5.1 Physicochemical properties of microemulsion systems

5.2 Emulsion systems and emulsion technologies

5.3 Use of microemulsion systems for enhanced oil recovery from reservoirs

5.4 Breakdown of dilute emulsions

5.5 Hydrophile-lipophile balance and foaming properties of microemulsions

5.6 Hydrophile-lipophile balance and selection of reagents in the processes of surface (foam) separation of dissolved substances, colloid particles and oil drops

5.7 Hydrophile-lipophile balance and sanitary-technical characteristics of surfactants

5.8 Hydrophile-lipophile balance and protein structure

5.9 Use of the hydrophile-lipophile balance concept for the characterisation of solid surfaces with respect to its application

List of Symbols

Abbreviations of surfactants and surfactant mixtures

Acronyms

Subject index

Studies in Interface Science

SERIES EDITORS

D. Möbius and R. Miller

Vol. I

Dynamics of Adsorption at Liquid Interfaces

Theory, Experiment, Application

by S.S. Dukhin, G. Kretzschmar and R. Miller

Vol. 2

An Introduction to Dynamics of Colloids

by J.K.G. Dhont

Vol. 3

Interfacial Tensiometry

by A.I. Rusanov and V.A. Prokhorov

Vol. 4

New Developments in Construction and Functions of Organic Thin Films

edited by T. Kajiyama and M. Aizawa

Vol. 5

Foam and Foam Films

by D. Exerowa and P.M. Kruglyakov

Vol. 6

Drops and Bubbles in Interfacial Research

edited by D. Möbius and R. Miller

Vol. 7

Proteins at Liquid Interfaces

edited by D. Möbius and R. Miller

Vol. 8

Dynamic Surface Tensiometry in Medicine

by V.N. Kazakov, O.V. Sinyachenko, V.B. Fainerman, U. Pison and R. Miller

Vol. 9

Hydrophile-Lipophile Balance of Surfactants and Solid Particles

Physicochemical Aspects and Applications

by P.M. Kruglyakov

Copyright page

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First edition 2000

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Preface

Penza, May 2000

Pyotr M. Kruglyakov,     Penza, May 2000

The amphiphilicity is a fundamental characteristic of any surfactant, which becomes evident in various surface and bulk properties, for example, adsorption, micelle formation, formation of stable liquid films in foams and emulsions, wetting films, lipid membranes, formation of vesicles (liposomes), in the distribution of matter between heteropolar phases, in the operation of various biologic systems, etc.

To access the quantitative measure of the amphiphilicity, the so-called hydrophile-lipophile balance is widely used, which in a certain way reflects the relative efficiency of the heteropolar parts of the surfactants.

The most commonly used characteristics of the hydrophile-lipophile balance with respect to the application of surfactants are Griffin ’s HLB numbers and Davies’ HLB numbers. These numbers were introduced in response to technological needs, where a quantitative characterisation of a surfactant was required to facilitate the choice and selection of the particular compound in a specific application (the development of a detergent compositions and solubilisers, stabilisation of foams and emulsions, etc.)

The studies dealing with the concept of the hydrophile-lipophile balance were mainly concerned with establishing correlations between Griffin ’s or Davie ’s HLB numbers and various properties of surfactants, the substantiation or criticism of the Griffin’s HLB system, the refinement of various methodological details of experimental measurements or theoretical calculations of HLB numbers, and with the proper account for various factors (molecular structure, medium, temperature etc.) which have been ignored in the HLB numbers system. It should be noted that the applicability of the system of HLB numbers is often overestimated. Clearly, any complex phenomena, and, in particular, the stabilisation of emulsions or detergency, cannot be characterised by a single parameter of a surfactant irrespective of the temperature and ambient medium.

It should also be noted that, following Davies, many authors considered the calculated Davies’ and Griffin ’s HLB numbers as the same quantities. This point of view cannot, however, cannot be shared. Generally speaking, these two systems of numbers represent different hydrophility scales.

From the viewpoint of the physical chemistry of surfactants, it appears that the problem of the search, establishing and study of the practically important characteristics of the hydrophile-lipophile balance which, as applied to surfactants, possess a simple and unambiguous physical meaning, and are applicable to all types of surfactants (micellar and non-micellar, ionic and non-ionic) is much more important.

It was stressed by P.A. Rebinder that … the development of a quantitative theory of hydrophile-lipophile balance … should be considered as the most important goal of the physical chemistry of surfactants. The solution of this problem should lead to the scientific foundations for the estimation of the efficiency of the developed application of surfactants. Here two aspects of the problem should be kept in mind: the choice of a general and physically meaningful characteristic which employs both the balance of the heteropolar parts of a surfactant and the amount (force) of the lever arm of the balance, and the application of the constituents of this balance and the hydrophile-lipophile balance value to give an explanation for various surface and bulk properties (with respect to micelle formation or adsorption) and more complicated phenomena, for example the formation of vesicles, microemulsions, emulsions, foams etc.

The energetic treatment of the hydrophile-lipophile balance can possibly be the most general and useful concept, because all colloid and surface phenomena are closely related with the energetic characteristics of surfactants. This approach, however not consequently, was adopted already in the concept of Davies’ numbers for functional groups of surfactants.

In his studies, Davies introduced the energetic treatment of the hydrophile-lipophile balance when comparing the empirical group numbers corresponding to the functional groups of surfactants, and the activation barrier for the breaking of emulsion films.

In recent years, a quite extensive scope of knowledge was accumulated in the area of the energetic characteristics of surfactant molecules and their particular parts with respect to adsorption, micelle formation, distribution between bulk phases etc. However, the hydrophile-lipophile balance concept based on these characteristics by no means became widespread.

The main idea of the proposed book is the energetic concept of hydrophile-lipophile balance as applied to surfactants and solid particles (acting mainly as stabilisers of emulsions). At the same time, the monograph systematises a number of other branches of studies regarding the hydrophile-lipophile balance.

The first chapter summarises the known surface and bulk properties of surfactants which are directly related to the hydrophile-lipophile balance concept and are used either to determine the HLB numbers or to provide an independent measure of the hydrophile-lipophile balance. Along with the systematic exposition of known properties of surfactants, this chapter contains new theoretic data concerning the calculation of interfacial tension, determination of the adsorption of surface-active electrolytes, estimation of the energy of adsorption, and also summarises the studies performed by the author in relation with the Antonov ’s rule, Traube ’s rule and the comparison of the contribution to Gibbs’ energy for various structural groups of surfactant molecules as applied to their transfer from bulk phases through the dividing surface to micelles and other bulk phases.

The second chapter systematises the most important properties of emulsions (properties of films, phase inversion, and the kinetics of flocculation and coalescence) which are directly related to the stability of emulsions, to the formulation of HLB numbers by Davies, and to the concept of the HLB temperature (phase inversion temperature, PIT) introduced by Shinoda.

The third chapter presents a comprehensive analysis of the systems of Griffin ’s and Davies’ HLB numbers (experimental evaluation and calculation of HLB numbers and a comparative analysis of the original systems and modifications proposed by various authors), the determination of the characteristics of the hydrophile-lipophile balance based on the energetic properties of surfactants (distribution coefficients, work of adsorption and energy of micelle formation).

In the fourth chapter, the methods are described which are used to express hydrophile-lipophile balance for solid particles of various nature and dispersity (macroscopic, gel-like or colloid-disperse) employed as emulsifying agents or foam stabilisers, and the properties of emulsions stabilised by solid particles.

The fifth chapter briefly summarises some practical applications of the concept of the hydrophile-lipophile balance in various branches of science and technology.

The author acknowledges the contributions made by his co-workers, namely T.V. Mikina A.I. Bulavchenko, L.L. Kuznetsova, S.M. Selitskaya, V.D. Mal’kov and T.N. Khaskova, to the studies related to the hydrophile-lipophile balance concept, summarised in this book.

I should like to acknowledge the support by R. Miller, Max-Planck-Institut fur Kolloid- und Grenzflächenforschung, which was of enormous help during the preparation of this book and in fact, enabled the study to be published.

The author expresses his thanks to E.V. Aksenenko, Institute of Colloid Chemistry and Chemistry of Water, Ukrainian National Academy of Sciences, who helped in the translation of the book into English, and to O.N. Kuznetsova for her significant technical assistance during the preparation of the book.

Introduction

The concepts of lyophilicity and lyophobicity (or, as applied to aqueous media, hydrophilicity and hydrophobicity) are commonly used in colloid chemistry.

At the early stages of the studies of disperse systems, the terms ‘lyophilicity’ and ‘lyophobicity’ were used to discriminate between systems which possess weak affinity of the disperse phase to the medium (suspensoids) and those displaying a pronounced interaction between the particles and the medium (emulsoids). From the modern point of view, lyophobic colloidal solutions and other dispersions are thermodynamically non-equilibrium systems, while lyophilic colloids are equilibrium systems.

Another meaning is ascribed to the terms ‘lyophilicity’ and ‘lyophobicity’ with respect to the phenomena of wetting and stabilisation of emulsions by solid particles. In this case the hydrophility (or hydrophobicity) of the particle is characterised by the contact angleθfor the selective wetting, that is, for the contact of the solid surface with a pair of immiscible heteropolar liquids (e.g., water/oil), or by other parameters, for example the work of wetting, quantitatively related to the wetting angle. The surface is called hydrophobic (oleophilic) if it is better wetted by non-polar liquids, θ> 90°. Alternatively, if it is better wetted by water,θ< 90°, the surface is called hydrophilic (oleophobic). Hereinafter the wetting angle is counted through the polar liquid.

According to these two concepts of lyophilicity, the behaviour of quartz, for example, corresponds to hydrophilic (oleophobic) particles with respect to wetting by water; at the same time the sol of SiO2 (or SiO2 suspensions) in water demonstrates the properties of a hydrophobic colloidal system.

The concept of hydrophile-lipophile balance as the quantitative measure of the amphiphilicity of surfactants (primarily emulsifying agents) arose much later (in the late 40s and early 50s), especially in connection to the synthesis and application of non-ionic surfactants, for example, oxyethylated derivatives of alcohols, acids and alkyl phenols.

In particular, W. Clayton in his well-known monograph The Theory of Emulsions and their Technical Treatment ([1] p. 243) refers to patents in which substances are proposed that prevent splashing of liquid margarine, and emulsifying agents with balanced contents of hydrophilic and hydrophobic groups.

In these years, in the studies of non-ionic surfactants [2–5] it was shown that the existence of a definite hydrophile-hydrophobe balance (the ratio of the mean number of moles of ethylene oxide to the number of hydrophobic fragments, e.g. methylene groups) is required to achieve the optimum condition of wetting, detergency, emulsifying and de-emulsifying action, solubilisation, foam formation etc. This concept was subsequently extended over other classes of surfactants; at the same time, the quantitative measure of the hydrophile-lipophile balance for these substances is still controversial.

Clearly, the relative efficiency of the polar and apolar parts of surfactant molecule can be expressed via the particular properties of these parts (or the substance as a whole); it should be also kept in mind that different ways of the estimation of hydrophile-lipophile balance can turn to be practically convenient for different processes in which the surfactants play an important role.

Among the parameters which can be employed to estimate the hydrophile-lipophile balance are the structural characteristics (the volume and configuration of the parts of a surfactant), mass-dependent (various functions of mass of hydrophilic or hydrophobic parts) or energy-dependent characteristics (the work of transfer from one phase to another, the work of adsorption from various phases, including those determined in chromatographic processes, the heat of dissolution, the work of micelle formation), and other complex characteristics (the stability and the type of emulsions formed, phase inversion temperature, detergency, solubilisation, etc.)

In turn, the energetic characteristics can be subdivided into direct (primary) and indirect (secondary) parameters. The primary characteristics are related to the surfactant itself (or to its specific parts). These characteristics, however, depend also on the type of the phases, between which the surfactant is distributed and with which it interacts. Among these characteristics are the energy of the transfer of surfactant from one phase to another, the work of surfactant adsorption, the heat of dissolution and the heat of adsorption, the work of micelle formation.

The indirect characteristics refer to the system as a whole, for example, to the water/oil system in the presence of a surfactant, or to different parts of the system. This group includes interfacial tension, spreading coefficient, activity coefficients for water and oil in the presence of the surfactant and some other parameters.

Possibly the most general characteristic of the hydrophile-lipophile balance should be expressible through some fundamental properties, which are immanent to any surfactant, reflects the influence of both parts of the surfactant molecule, and possesses a clear physical meaning. For example, the characteristics related to the micelle formation do not satisfy these requirements, because micelle formation is not immanent to all kinds of surfactants. On the other hand, the stabilising ability (in foams, emulsions, suspensions) or detergency of surfactants, while belonging to the important properties of these substances, also cannot satisfy these requirements because these properties follow from the complex action of several simple properties, evident in complex kinetic processes and equilibrium states.

References

1. W. Clayton, The Theory of Emulsions and their Technical Treatment, 4th Ed., London, 1943.

2. J.P. Sisley, Am. DyestuffRept., 38, 513–21.

3. J.M. Cross, Soap Sanit. Chemicals. Special issue. Off. Proc. CSMA, 26, No CSMA 1.

4. W.C. Griffin, Proc. Sci. Sect. Toilet Goods Assg. N.6, (1946)43.

5. R.L. Mayhew, R.C. Hyatt, J. Am. Oil Chemists’ Sot., 29(1952)357.

Chapter 1

Physicochemical properties of surfactants used in the definition of hydrophile-lipophile balance

1.1 Classification of surfactants with respect to structure and chemical nature

Surfactants are substances which decrease the surface (interfacial) tension. It should be noted, of surfactants with respect to the structure and chemical nature however, that the interface can be chosen in such a way that any particular substance, being in a liquid or vapour phase, or a solution component, can act to decrease the surface or interfacial tension. In a more specific sense, the term surfactant denotes amphiphilic organic substances of an asymmetric molecular structure.

Typically, surfactant molecule consists of two parts, which possess properties that are opposite to each other by their nature. One part of the molecule (or ion) is the hydrophilic polar group, for example, -NH2, -OH, -COOH, -SO3H, -OSO3H, -COOMe, -OSO3Me, -N(CH3)3Cl, -CH2CH2O.

Another part is formed by a rather long hydrocarbon or hydrofluorine hydrophobic (oleophilic) chain. High molecular-weight surfactants (proteins, polyvinyl alcohols, polyacryl amide etc.) contain alternating hydrophilic and hydrophobic molecular groups distributed along the whole molecule.

These typical surfactants demonstrate always some surface activity at the water/gas and water/oil interface, and are often surface active at the interface between a solution and some solid phases.

With respect to their structure and chemical nature, surfactants can be divided into two major groups - non-ionic surfactants and surface-active electrolytes (colloidal electrolytes) which consist of a long-chain ion (surface active ion) and an ordinary inorganic ion (counterion).

The molecules of non-ionic surfactants contain polar groups unable to dissociate and possessing a significant affinity to water and other polar substances. Usually these groups incorporate atoms of oxygen, nitrogen, phosphorus or sulphur (alcohols, amines, ethers etc.).

Among the substances of this group of surfactants, the most significant are oxyethylated alkyl phenols, fatty alcohols, fatty acids, amines and block-copolymer surfactants (oxyethylene non-ionic surfactants), in which the polar part of the molecule consists of repeated oxyethylene group -CH2-O-CH2- and closing -OH, -COOH or -NH2 group.

The most common oil-soluble surfactants which belong to this group are ethers of fatty acids and polyatomic alcohols - pentaerythritol, triethanol amine, unhydro sorbite and unhydro xylite (like Span, Tween etc.)

The ionic surfactants, in turn, can be subdivided into two groups: anionic (anion-active) substances, for which the hydrophobic long-chain part responsible for the surface activity is incorporated into the anion, and cationic (cation-active) surfactants, where the cations are incorporated into the hydrocarbon or other hydrophobic radical which is responsible for the surface activity. Among the anionic surfactants, the most significant are the soaps of carbon acids (RCOOMe), alkyl sulphates (sulphoether salts) ROSO3Me, alkane sulphonates RSO3Me, alkyl aryl sulphonates RC6H5SO3Me, alkyl phosphates ROPO(OMe)2, salts of sulphosuccinic acids. The typical surfactants which belong to this class are sodium dodecyl sulphate, sodium oleate and sodium dodecyl benzene sulphonate.

Among the cationic surfactants, the most common are the salts of (primary, secondary and tertiary) amines, and quaternary salts of ammonium, for example, cetyl ammonium bromide and octadecyl pyridinium chloride.

The ampholytic surfactants, which demonstrate either anionic or cationic properties depending on the properties of the medium (pH), can be regarded to as a particular class. These substances usually comprise some polar groups, for example, dodecyl-β-alanine C12H25NHC2H4COOH contains both carboxy group and amino group. Depending on the ambient conditions (primarily on the pH value in aqueous media), in the solution these surfactants can form either surface-active anions or surface-active cations.

Finally, zwitter-ionic surfactants can be regarded as an intermediate between non-ionic and ampholytic surfactants. The polar parts of these molecules, while neutral as the whole, contain opposite charges, separated from each other by another structural elements: here the betaine can be referred to as an example: RN+(CH2C6H5)(CH3)CH2COO-, where R is the hydrocarbon radical possessing 8 to 12 carbon atoms.

As the hydrophobic chain of a surfactant comprises a number of identical elements (CH2, CF2, etc.), many of the properties of a surfactant depend additively on the number of such elements, such as vapour pressure, solubility, distribution coefficient, surface activity, adsorption, micelle formation and many others. This additivity is also evident with respect to the variation in the number of oxyethylene groups (EO) in non-ionic oxyethylated surfactants. The additivity usually holds well for straight chains and small variations in the number of structural elements, ΔnCH2 = 4-5, sometimes to Δ nCH2 = 10; for higher values of this number, deviations from additivity become evident. The additivity with respect to some properties is violated also when the position of a polar group in the hydrocarbon chain is changed, or when any isomerism is introduced into this chain.

To be efficient, surfactants should not only be amphiphilic, but, in addition, should possess ‘strong’ and well-balanced hydrophobic and hydrophilic parts, which enable them to remain at the interface, to form micelles, and to participate in other processes. Depending on the strength of both polar and non-polar parts, and on the value of the hydrophile-lipophile balance, the surfactants can be classified with respect to their technological applications (foaming agents, emulsifiers, wetting agents, solubilisers, detergents etc.)

The synthesis, structure and various properties of surfactants are considered in detail in a number of monographs and handbooks [1–8]; the reader can also turn to volumes of the Surfactant Science Series [9–14]. The most recent publication to refer to in respect to a systematisation of surfactants, their synthesis, chemical and physico-chemical characterisation, and practical applications in many technological field is the monograph to be published in this Series [15]. This volume entitled Surfactants − Chemistry, Interfacial Properties, Applications will appear in the beginning of 2001 with Elsevier Science B. V., co-authored by B. E. Chistyakov, V. B. Fainerman, D. O. Grigoriev, M. Yu. Pletnev, A. V. Makievski, R. Miller and B. A. Noskov.

1.2 Surface-related properties of surfactants

1.2.1 Interfacial tension

The energy excess of molecules (or other particles) in the interface region, as compared to the with each other strongly energy which these entities possess when they exist in the respective bulk phase and interact results in a free interfacial energy.

From the viewpoint of surface science, the intensity of the field of molecular forces, characterised by the surface tension, is the polarity. This characteristic is closely related to some parameters of a liquid, in particular, the dipole moment, polarisability and dielectric permittivity.

The interfacial tension is determined by the difference in the intensity of force fields. The stronger the interfacial interaction at the interface (i.e., the larger the affinity of the organic phase to the water) is, the lower is the interfacial tension.

The calculations of surface tension based on statistical mechanics, involving a radial distribution function¹ g(r) and the interaction function ε(r) between the molecules, say, Lennard-Jones equation, lead to satisfactory results only for fluids consisting of spherical monoatomic molecules, for example, He or Ar [16–19].

To calculate the interfacial tension, statistical methods are employed, where the average molecular density is used instead of the radial distribution function [16]. In this way, approximate expressions for the interfacial tension (σAB) were derived, valid for a pair of liquids, with one of the pair being a saturated hydrocarbon.

In the calculations performed by Girifalko and Good [10]

(1.1)

where ϕ is a function which depends on the molar volumes of the adjacent liquids. The value of ϕ is usually between 0.5 and 1.15.

In similar calculations performed by Fowkes [21] it was assumed that the energies of mutual interaction of hydrocarbons and their interaction with water are determined solely by dispersion forces. Therefore Eq. (1.1) can be written as

(1.2)

is the contribution from dispersion forces into the surface tension of water, and ϕ = 1. Some attempts were made to apply the equations (1.1) or (1.2) for the calculation of the interfacial tension in systems where non-ionic surfactants are present [22]. While the values of σAB for the systems studied in [22] agree with the theory presented in [21], the interfacial tension depends strongly on the type of the hydrocarbon phase, and on the number of EO groups in the non-ionic surfactant molecule. These results are briefly summarised in the monograph [23]. For most types of other systems, these calculations were found to be unreliable, and the main assumptions made in [20, 21] were strongly criticised, see [17, 24].

To describe the thermodynamic equilibrium for liquid/vapour and liquid/liquid systems, in recent years equations (models) for the local composition of the interface region are widely used [25]. One of these well-known approaches is the Universal Quasi-Chemical model (UNIQUAC) [26] which, from the calculation point of view, combines the local composition concept with the Guggenheim-Staverman quasi-chemical thermodynamic lattice model. The most complete and rigorous description of these concepts and procedures used to calculate σAB can be found in the studies presented by Kahlweit [27] and Li & Fu [28]. In particular, the expression for σAB proposed by Kahlweit is

(1.3)

are the volume solubilities (expressed as molar fractions), x denotes the molar fraction of a component, xs is the molar fraction in the interfacial region, z is the co-ordinate within the layer (normal to the dividing surface).

In [28], also based on Kahlweit’s concept which assumes the mutual solubility of phases in the water/benzene system and takes into account the interfacial region profile, the surface and volume contributions to the total free energy of mixing were calculated, and then the sum of these contributions was taken over all the transition region. To calculate the activity coefficients and the interaction energy, the UNIQUAC method was employed. The values σAB were calculated for 45 binary systems. Table 1.1 summarises results for some pairs of liquids.

Table 1.1

Calculated vs experimental values of interfacial tension σAB (the second liquid is water)

The average difference between the calculated and experimental σAB values is 1.4 mN/m, while the maximum difference does not exceed 5.1 mN/m. The number of molecular layers in the transition region, which were accounted for in the calculations, was 2 to 4.

Long before the calculations in [21–28] were performed, the following empirical equation, known as Antonov’s rule [29]

(1.4)

was proposed to estimate the surface tension between two liquids. Here σAB is the equilibrium interfacial tension of mutually saturated liquids A and B, σA(B) is the surface tension of liquid A being in contact with the saturated vapour of liquid B. The analysis and verification of the Antonov rule was the subject of a number of publications [30]. It was shown that this rule holds satisfactorily for water in contact with many organic liquids, e.g., saturated hydrocarbons, lower ethers, ketones, nitrobenzene, chloroform. At the same time, for a number of other liquids (higher fatty alcohols and acids, phenol, cresol, benzene, methylene iodide) significant deviations from this rule were observed, amounting to some and even tens of mN/m, as demonstrated for example in [31–33].

Even in the first studies dealing with Antonov’s rule, its interrelation with the equilibrium coefficient of spreading S was pointed out. It was shown that the Antonov rule holds for S = 0, and does not hold if S < 0. The physical nature of this dependence was explained in [30], where the shape of the disjoining pressure isotherm for a films of liquid A spread on the surface of the other liquid B was analysed.

It is known [17, 31, 34, 35] that the equilibrium coefficient of spreading for the liquid B over the surface of liquid A is

(1.5)

Therefore,

(1.6)

It is seen from Eq. (1.6) that the condition SB = 0 corresponds to the case when Antonov’s rule is valid:

Therefore, the spreading coefficient SB can characterise the sign and the magnitude of the deviations from the Antonov rule.

Equation (1.5) refers to the thermodynamic equilibrium between the two liquid bulk phases A and B. Therefore the values of SB can be determined from the Young-Neumann equation, see Fig. 1.1. Here it should be kept in mind that σAB corresponds to the state when an equilibrium between the liquid A and the saturated vapour B exists. The formation of an equilibrium adsorption film (with the thickness h0) of the substance B at the surface of the liquid A (for the relative pressure pB/pB(0) =1) can take place if the inequality

Fig. 1.1 Equilibrium wetting film of liquid B formed at the surface of liquid A in contact with the bulk phase of liquid B; see text for details.

holds (see [is the spreading pressure, and σA is the surface tension of the pure liquid A. This condition is usually held when σB(A) < σA(B).

From Fig. 1.1 it is clear that the horizontal forces resultant exists if

(1.7)

where σA(B) is the surface tension of the liquid A covered with the adsorption film of liquid B (the meaning of the other symbols is evident from Fig. 1.1). The contact angles θB and θBA are related to each other via the condition

(1.8)

which reflects the fact that the projection of the force resultant onto the vertical axis in Fig. 1.1 should be equal to zero.

The value of σA(B) can be regarded to as the tension of a thin film of B existing at the surface of liquid A. This tension consists of the sum of surface tensions of bulk liquids at the interfaces, viz., σB(A) and σAB, and the specific (per unit film area) isothermal work required for the decrease of the film thickness of liquid B from a value h = ∞ to the value h = h0 which corresponds to p/ps = 1, see Fig. 1.1. According to the well-known Derjaguin-Frumkin theory of wetting [36], we have

(1.9)

ΠB(h) is the disjoining pressure isotherm for the film of liquid B existing at the surface of the bulk liquid A, corresponding to the state of mutual saturation.

Comparing Eqs. (1.9) and (1.5), one obtains

(1.10)

Thus, the spreading coefficient can be determined from the disjoining pressure isotherm.

holds, and therefore for the spreading coefficient SA an expression analogous to Eq. (1.10) is valid.

To analyse possible values of the equilibrium spreading coefficient S, one can consider various types of disjoining pressure isotherms for wetting films, see Fig. 1.2.

Fig. 1.2 Disjoining pressure isotherms for wetting films: (1) - complete wetting of the substrate by liquid B; (2) - complete wetting of the substrate for a small portion of the isotherm with π < 0; (3) - partial wetting (area of