The book also treats the surface properties of apolar and polar molecules, polymers, particles and cells, as well as their mutual interaction energies, when immersed in water, under the influence of the three prevailing non-covalent forces, i.e., Lewis acid-base (AB), Lifshitz-van der Waals (LW) and electrical double layer (EL) interactions. The polar AB interactions, be they attractive or repulsive, typically represent up to 90% of the total interaction energies occurring in water. Thus the addition of AB energies to the LW + EL energies of the classical DLVO theory of energy vs. distance analysis makes this powerful tool (the Extended DLVO theory) applicable to the quantitative study of the stability of particle suspensions in water. The influence of AB forces on the interfacial tension between water and other condensed-phase materials is stressed and serves, inter alia, to explain, measure and calculate the driving force of the hydrophobic attraction between such materials (the hydrophobic effect), when immersed in water. These phenomena, which are typical for liquid water, influence all polar interactions that take place in it. All of these are treated from the viewpoint of the properties of liquid water itself, including the properties of advancing freezing fronts and the surface properties of ice at 0o C.
- Explains and allows the quantitative measurement of hydrophobic attraction and hydrophilic repulsion in water
- Measures the degree of cluster formation of water molecules
- Discusses the influence of temperature on the cluster size of water molecules
- Treats the multitudinous effects of the hyper-hydrophobicity of the water-air interface"
This book treats the different current as well as unusual and hitherto often unstudied physico-chemical and surface-thermodynamic properties of water that govern all polar interactions occurring in it. These properties include the hyper-hydrophobicity of the water-air interface, the cluster formation of water molecules in the liquid state and the concomitant variability of the ratio of the electron-accepticity to electron-donicity of liquid water as a function of temperature, T. The increase of that ratio with T is the cause of the increase in hydration repulsion ("e;hydration pressure?) between polar surfaces upon heating, when they are immersed in water. The book also treats the surface properties of apolar and polar molecules, polymers, particles and cells, as well as their mutual interaction energies, when immersed in water, under the influence of the three prevailing non-covalent forces, i.e., Lewis acid-base (AB), Lifshitz-van der Waals (LW) and electrical double layer (EL) interactions. The polar AB interactions, be they attractive or repulsive, typically represent up to 90% of the total interaction energies occurring in water. Thus the addition of AB energies to the LW + EL energies of the classical DLVO theory of energy vs. distance analysis makes this powerful tool (the Extended DLVO theory) applicable to the quantitative study of the stability of particle suspensions in water. The influence of AB forces on the interfacial tension between water and other condensed-phase materials is stressed and serves, inter alia, to explain, measure and calculate the driving force of the hydrophobic attraction between such materials (the "e;hydrophobic effect?), when immersed in water. These phenomena, which are typical for liquid water, influence all polar interactions that take place in it. All of these are treated from the viewpoint of the properties of liquid water itself, including the properties of advancing freezing fronts and the surface properties of ice at 0o C. Explains and allows the quantitative measurement of hydrophobic attraction and hydrophilic repulsion in water Measures the degree of cluster formation of water molecules Discusses the influence of temperature on the cluster size of water molecules Treats the multitudinous effects of the hyper-hydrophobicity of the water-air interface
Front cover 1
The Properties of Water and their Role in Colloidal and Biological Systems 4
Copyright page 5
Contents 6
Preface 14
Chapter 1. General and Historical Introduction 16
Preamble 16
1. Some Examples of Polar Forces Interacting in the Mammalian Blood Circulation 17
2. Early Examples of the Treatment of Non-Covalent Interactions in Water 18
3. Macroscopic-Scale Interactions, Chaudhury's Thesis and Lifshitz-van der Waals Forces 20
4. Rules for Repulsive Apolar (van der Waals) Forces between Different Polymers Dissolved in an Apolar Liquid, Compared with the Rules for Repulsive Polar (Lewis Acid-Base) Forces between Identical Polymers, Particles or Cells, Immersed in Water 20
5. The Fallacy of Designating Only One Single Component to Represent the Polar Properties of the Surface Tension of a Polar Condensed-Phase Material 22
6. More Recent Developments 23
Section A: Non-Covalent Energies of Interaction-Equations and Combining Rules 26
Chapter 2. The Apolar and Polar Properties of Liquid Water and Other Condensed-Phase Materials 28
1. The gammaLW and gammaAB Equations 28
2. The Values for gammaLW, gamma+ and gamma- for Water at 20°C 38
3. Apolar and Polar Surface Properties of Various Other Condensed-Phase Materials 39
Chapter 3. The Extended DLVO Theory 46
1. Hamaker Constants and the Minimum Equilibrium Distance between Two Non-Covalently Interacting Surfaces of Condensed-Phase Materials 47
2. The DLVO Theory Extended by the Addition of Polar Interaction Energies Occurring in Water 49
3. Decay with Distance of Lifshitz-van der Waals Interactions 51
4. Decay with Distance of Lewis Acid-Base Interactions 53
5. Decay with Distance of Electrical Double Layer Interactions 55
6. Influence of the Ionic Strength on Non-Covalent Interactions in Water 57
7. An EL-AB Linkage 59
8. Role of the Radius of Curvature, R, of Round Particles or Processes in Surmounting AB Repulsions in Water 60
9. Comparison between Direct Measurements via Force Balance or Atomic Force Microscopy, and Data Obtained via Contact Angle Determinations, in the Interpretation of Free Energies vs Distance Plots of the Extended DLVO Approach 61
Section B: Surface Thermodynamic Properties of Water with Respect to Condensed-Phase Materials Immersed in It 64
Chapter 4. Determination of Interfacial Tensions between Water and Other Condensed-Phase Materials 66
1. The Interfacial Tension between a Solid (S) and a Liquid (L) 66
2. The Interfacial Tension between an Apolar Material or Compound (A) and Water (W) 67
3. The Interfacial Tension between Polar Compounds or Materials and Water 69
Chapter 5. The interfacial tension/free energyof interaction between water and identical condensed-phase entities, i, immersedin water, w 74
1. The DeltaGiwi Equation Pertaining to Identical Entities, i, Immersed in Water, w 74
2. Mechanism of Hydrophobic Attraction in Water 78
3. Mechanism of Hydrophilic Repulsion in Water 81
4. Osmotic Pressures of Apolar Systems as well as of Polar Solutions, Treating Aqueous Solutions in Particular 82
Chapter 6. The Interfacial Tension/Free Energyof Interaction between Water and Two Different Condensed-Phase Entities, i, Immersed in Water, w 88
1. The DeltaG1w2 Equation Pertaining to Two Different Entities, 1 and 2, Immersed in Water, w 88
2. Examples of DeltaG1w2 Interactions 90
3. Water Treated as the Continuous Liquid Medium for DeltaG1w1 and DeltaG1w2 Interactions 98
Chapter 7. Aqueous Solubility and Insolubility 100
1. The Solubility Equation 100
2. Aqueous Solubility of Small Molecules 104
3. Aqueous Solubility of Polymeric Molecules 108
4. Influence of Temperature on Aqueous Solubility 113
5. Aqueous Insolubilization (Precipitate Formation) Following the Encounter between Two Different Solutes that Can Interact with Each Other When Dissolved in Water 113
Chapter 8. Stability Versus Flocculation of Aqueous Particle Suspensions 128
1. Stability of Particle Suspensions in Water 128
2. Stability of Charged and Uncharged Particles, Suspended in Water 132
3. Linkage between the EL Potential and AB Interaction Energies in Water-Importance of AB Interaction Energies for the Stability vs Flocculation Behavior of Aqueous Suspensions of Charged Particles-The Schulze-Hardy Phenomenon Revisited 138
4. Destabilization of Aqueous Particle Suspensions by Cross-Linking 143
Section C: Physical and Physicochemical Properties of Water 146
Chapter 9. Cluster Formation in Liquid Water 148
1. Size of Water Molecule Clusters 148
2. Implications of the Increased Lewis Acidity of Water Following Increases in T 150
3. Influence of Cluster Formation in Liquid Water on the Action at a Distance Exerted by Polar Surfaces when Immersed in Water 152
Chapter 10. Hydration Energies of Atoms and Small Molecules in Relation to Clathrate Formation 156
Preamble 156
1. Free Energy of Hydration of Atoms and Small Molecules Immersed in Water 157
2. Hydration of Small Apolar Molecules 159
3. Hydration of Small Partly Polar Molecules 160
4. Clathrate Formation as a Hydration Phenomenon Occurring with Atoms or Small Molecules 161
Chapter 11. The Water-Air Interface 164
1. Hyperhydrophobicity of the Water-Air Interface 164
2. The zeta-Potential of Air or Gas Bubbles in Water 167
3. Repulsion versus Attraction of Various Solutes by the Water-Air Interface 168
4. Inadvisability of Using Aqueous Solutions for the Measurement of Contact Angles 175
Chapter 12. Influence of the pH and the Ionic Strength of Water on Contact Angles Measuredwith Drops of Aqueous Solutionson Electrically Charged, Amphoteric and Uncharged Surfaces 176
1. Influence of the pH of Water on Electrically Charged and Amphoteric Surfaces 176
2. Influence of the pH on Water Contact Angles Measured on (Non-Charged) Hydrophobic as well as on (Non-Charged) Hydrophilic Surfaces 178
3. Influence of the Ionic Strength on Water Contact Angles 179
4. Comparison Between the Influence of pH and Increases in Ionic Strength on Water contact Angles on Solid Surfaces as well as on the Surface Properties of such Solid Surfaces when Completely Immersed in Water 180
5. Conclusions 181
Chapter 13. Macroscopic and Microscopic Aspects of Repulsion Versus Attraction in Adsorption and Adhesion in Water 182
1. Macroscopic-Scale Repulsion vs Microscopic-Scale Attraction in Water 183
2. Methodologies Used in Measuring Protein Adsorption onto and Desorption from Metal Oxide Particles in Water 186
3. Hysteresis of Protein Adsorption onto Metal Oxide Surfaces, in Water 191
4. Kinetics of Protein Adsorption onto Metal Oxide Surfaces Immersed in Water 196
Chapter 14. Specific Interactions in Water 202
1. Innate and Adaptive Ligand-Receptor Interactions in Biological Systems 202
2. The Forces Involved in Epitope-Paratope Interactions 211
References 222
Subject Index 230
General and Historical Introduction
Carel Jan van Oss
Publisher Summary
This chapter presents some examples of polar forces interacting in the mammalian blood circulation, early examples of the treatment of non-covalent interactions in water, rules for repulsive apolar (van der Waals) forces between different polymers dissolved in an apolar liquid, the fallacy of designating only one single component to represent the polar properties of the surface tension of a polar condensed-phase material, and discusses macroscopic-scale interactions, Chaudhury's thesis and Lifshitz–van der Waals forces. The elucidation of the mechanisms of hydrophobic attraction as well as of hydrophilic repulsion of materials or molecules immersed in water has occurred only relatively recently. The mechanisms of these two phenomena are best understood by using the equation defining the free energy of interaction between two similar materials, immersed in water. Both hydrophobic attraction in water (the “hydrophobic effect”) and hydrophilic repulsion in water (“hydration pressure”) are caused by Lewis acid–base forces.
PREAMBLE
Water is the most polar1 liquid known to Man. At room temperature (20 °C) its total free energy of cohesion, Gcohesion=−145.6 mJ/m2, consisting of GvanderWaals=−43.6 mJ/m2 and GPolar=−102 mJ/m2. Thus the van der Waals part of the free energy of cohesion of liquid water represents only 30% and the polar part represents 70% of the total. This was already known since Fowkes (1963, 1964, 1965). In addition, with respect to the interaction energies between non-polar molecules (e.g., alkanes), when these are immersed in water, the combining rules for apolar interactions in such cases generally causes GvanderWaals to be rather small, leaving mainly the polar free energy of attraction of 102 mJ/m2, which thus represents close to 100% of the total free energy of interaction in water among non-polar molecules or particles.
As was only realized much later, these 102 mJ/m2, representing the polar (in this case the hydrogen-bonding) free energy of cohesion of water, also happen to be the sole driving force for the hydrophobic effect. Notwithstanding these new data and probably mainly due to a continuing indecisiveness as to which forces were apolar and which were polar (see Sub-section 2.3, below) no significant advances were made in this matter for about another 20 years after Fowkes (1963, 1964, 1965). Finally, based on important clarifications proposed by Chaudhury (1984) and starting in early 1985, Chaudhury and I began (mainly via long-distance telephone) to develop the combining rules which allow the quantitative expression of polar free energies in SI units (van Oss, Chaudhury and Good, 1987, 1988). The ensuing results allowed the polar free energies of interaction to be combined with the van der Waals interaction energies (and the electrical double layer interaction energies where applicable), into a complete system comprising all non-covalent interactions taking place in and with liquid water (see also van Oss, 1994, 2006).
Now, more than another two decades past 1987, this book aims to treat the combined non-covalent non-polar, polar and electrical double layer interactions taking place in and with water, from the viewpoint of all the germane physical and physico-chemical properties of liquid water.
1 SOME EXAMPLES OF POLAR FORCES INTERACTING IN THE MAMMALIAN BLOOD CIRCULATION
Essentially all repulsive as well as attractive non-covalent interactions at a colloidal scale occurring in biological systems take place in water. Some examples of such interactions in water, looking for instance at the mammalian peripheral blood circulation, include:
1. Repulsion:
The mutual, non-specific repulsion between protein molecules, which keeps them dissolved in blood serum and permits them to avoid precipitation.
The mutual, non-specific repulsion between leukocytes, platelets, etc., which keeps them in stable suspension in the blood and lymph circulation and thus prevents the formation of thrombi.
(Thus the principal constituents of blood can safely circulate in their aqueous environment.)
2. Attraction:
The specific attraction between pseudopodia of phagocytic leukocytes and bacteria that have found their way into the bloodstream allows the phagocytic cells to internalize such bacteria and destroy them.
The specific attraction between the epitope of a (foreign) antigen and the paratope of a complementary antibody molecule (immunoglobulin) triggers a series of events leading to the foreign antigen's destruction, see also Chapter 4, Section 6.
Whilst electrical double layer forces sometimes play a role in both the specific attractions and the non-specific repulsions alluded to above, polar, Lewis acid–base (AB) forces tend to accompany such electrical double layer forces and are often stronger than these, especially in high ionic strength media, such as the human blood circulation, in which electrostatic interactions are significantly attenuated. However, polar AB forces also act quite well in the absence of any electrical double layer forces, see Chapter 4, Sections 2, 3 and Chapter 7, Section 4, below.
2 EARLY EXAMPLES OF THE TREATMENT OF NON-COVALENT INTERACTIONS IN WATER
2.1 DLVO and Non-DLVO forces
In the 1940's the interaction energies between particles, immersed in a liquid were assumed to obey what is now known as the DLVO theory, after Derjaguin and Landau (1941), from the USSR and Verwey and Overbeek (1948), from the Netherlands; however, see also Hamaker (1936, 1937a, 1937b, 1937c). The classical version of this approach takes into account van der Waals attractive and electrostatic repulsive energies, acting upon such particles, as a function of interparticle distance. The classical DLVO theory does not account for polar (e.g., hydrogen-bonding) interactions. It does turn out, however that, in water, its polar (largely hydrogen-bonding) free energies of adhesion (to other entities) as well as of cohesion (within itself), usually account for approximately 90% of all polar, i.e., non-covalent interaction energies that are active in that liquid. [Even though van der Waals forces represent 30% of the cohesive interaction energies of water (see above), the van der Waals combining rules for interactions in liquids are such that van der Waals interaction energies among most biological compounds or particles, immersed in water, usually account for at most only a few % of the total, due to the van der Waals part of the combining rules given in Chapter 5, Eq. (5.1).]
It was only in the 1980's that hard experimental evidence, obtained with Israelachvili's force balance (Israelachvili, 1985, 1991), which permits the direct measurement of interaction forces in water, revealed the existence of “non-DLVO” forces which are neither due to van der Waals nor to electrical double layer forces (see also Claesson, 1986, and a more recent review article by Grasso et al., 2002).
2.2 Good's introduction of a Φ-factor and Fowkes' evaluation of a van der Waals/Non-van der Waals ratio of the surface tension of water
Meanwhile, from a theoretical point of view, in 1957 Good (see Girifalco and Good, 1957) had remarked upon the very different interfacial behavior of organic molecules when immersed in water, as compared to their interfacial behavior when immersed in various organic liquids. Thus Girifalco and Good (1957) proposed the use of a factor, Φ, of which the degree of departure from unity could be used as an indicator of the polarity of the system. It was the value of the (measured) interfacial tensions between oils and water (Girifalco and Good, 1957; see also Harkins, 1952), which we now know to be only valid for alkane–water systems and not for polar oil–water systems (see Chapter 3) and which for alkanes only reached a maximum value of around 51 mJ/m2, that allowed Fowkes (1963, 1964, 1965), using alkane–water interfacial tension values, to deduce the ratio of van der Waals to non-van der Waals contributions to the surface tension of water at 20 °C as being equal to 21.8/51.0 mJ/m2, i.e., as 30/70%. Later, using direct contact angle measurements with apolar liquids on aqueous gels of different concentrations, van Oss, Ju et al. (1989) confirmed the correctness of Fowkes' findings for the non-polar (van der Waals) component of the surface tension of water.
2.3 The three van der Waals forces: Are some of them polar?
It took, however, until 1985 before it became possible to begin to delineate with some clarity what the real difference was between apolar and polar forces in water. A remaining difficulty between knowing that there was a problem and solving it was that there are three different and well-known parts to the electrodynamic forces, together representing the sum-total of van der Waals forces. These are, in the order of their...
Erscheint lt. Verlag | 16.9.2008 |
---|---|
Sprache | englisch |
Themenwelt | Naturwissenschaften ► Biologie ► Biochemie |
Naturwissenschaften ► Chemie ► Anorganische Chemie | |
Naturwissenschaften ► Chemie ► Physikalische Chemie | |
Naturwissenschaften ► Chemie ► Technische Chemie | |
Naturwissenschaften ► Geowissenschaften ► Hydrologie / Ozeanografie | |
Naturwissenschaften ► Physik / Astronomie | |
Technik ► Umwelttechnik / Biotechnologie | |
ISBN-10 | 0-08-092157-4 / 0080921574 |
ISBN-13 | 978-0-08-092157-0 / 9780080921570 |
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