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2.1 Surface tension and work 2.1.1 Definition of surface tension 2.1.2 Work of extension 2.1.4 The surface of tension 2.1.5 Work of adhesion and cohesion
Capillarity and the mechanics of surfaces
2.2.6 Micropipette 2.2.7 Indicator oils 2.3 The Laplace equation 2.3.1 Applications of the Laplace equation 2.4 The Kelvin equation 2.4.1 Consequences of the Kelvin equation 2.4.2 Verification of the Kelvin equation 2.5 The surface tension of pure liquids 2.5.1 Effect of temperature on surface tension 2.5.2 The surface tension of liquids 2.5.3 The hydrophobic–hydrophilic interaction
2.1.3 Contact angle, wetting, and spreading
2.2 Measurement of surface tension 2.2.1 Wilhelmy plate 2.2.2 Capillary rise 2.2.3 Drop weight or volume 2.2.4 Maximum bubble pressure 2.2.5 Sessile and pendant drops
2.1 Surface tension and work
Many commonly occurring phenomena that are observed in systems containing an interface in which one of the phases is a liquid can be understood through the concept of surface tension. Some examples are the rise of liquid in a narrow tube, the fact that drops of liquid tend to be spherical, and the observation that water spreads evenly on some surfaces, while remaining in isolated drops on others. In this chapter, surface tension is defined and we see how it can be used to develop simple theories to explain these experiences.
2.1.1 Definition of surface tension
The bristles in a wet paint brush tend to stick together, and we might be tempted to think that the presence of water is sufficient to make the bristles stick to one another. However, if the brush is held completely under water the bristles separate (Figure 2.1), so it is not the fact that the bristles are wet, but the presence of the air–water interface that causes them to stick together.
2.1 SURFACE TENSION AND WORK

11
Dry
Wet
Another example is that it is easy to make sandcastles with damp sand, but if the sand is dry or very wet it doesn’t hold together. In both cases, the stickiness depends on the presence of the air–water interface, and the phenomena can be explained by realizing that the interface acts as though it were under tension. That is, it experiences forces that pull the bristles or sand particles together. Yet another common example is that a drop of water tends to assume a spherical shape (distorted perhaps by gravity or by air resistance if falling, Figure 2.2). Now a spherical shape has the lowest surface area for a given volume of liquid, so what we observe in these and other examples is that the area of an interface tends to a minimum. The force that causes this to happen is called the surface tension or sometimes the interfacial tension. If an imaginary line is drawn on a surface it will be pulled by the surfaces on either side towards those surfaces. For example, consider a partly inflated balloon (Figure 2.3). If a line is drawn on the surface, and then more air is added to the balloon, we observe that the line broadens as the rubber expands, and if the balloon were to be cut along the line the two sides would separate forming a hole. The balloon is only an analogy, but something similar happens at the surfaces of interest to us. At any surface, if the force, F, acting tangentially to the surface and at right angles to an element, δx, of an imaginary line in the surface has a magnitude that is independent of the direction of the element, then the surface tension, γ, is: γ = F ⋅ δx (2.1)
Immersed
Fig. 2.1 Effects of water on the
fibres of a brush.
In words, the surface tension is the force per unit length acting on an imaginary line drawn in the surface. The SI units of surface tension are N m−1, although because the N m−1 is rather large (the surface tension of the air– water interface at room temperature is about 0.072 N m−1), surface tension is more commonly quoted in mN m−1.1 An intuitive way to understand the origin of surface tension from a molecular point of view is to consider the forces acting on a molecule at the surface of
Fig. 2.2 Spherical drops falling from a round tube.
The CGS unit for surface tension is the dyn cm−1, where 1 dyn cm−1 = 1 mN m−1. This unit is seen in the older literature and is rarely used in current work.
1
12

2 CAPILLARITY AND THE MECHANICS OF SURFACES
Air F F Surface Bulk liquid
Fig. 2.3 The tension in the
rubber acts on a line in the surface, causing it to stretch.
Fig. 2.4 Forces acting on molecules near a surface.
a liquid compared to those acting on one in the bulk (Figure 2.4). The attractive forces acting on one molecule in the bulk are, when averaged over time, isotropic. That is, there is no net force pulling the molecule in any given direction. A molecule at the surface, however, will feel an unbalanced force due to the relative scarcity of near neighbours in the direction of the gas phase. The result is that there is a tendency for that molecule to be pulled into the bulk, as is the case for every other molecule at the surface. Hence, the origin of the tendency to minimize the area of the surface is clear.
2.1.2 Work of extension
As the area of an interface tends to a minimum, energy must be brought into the system to extend the interface. A soap film contained by a rectangular frame with one end capable of sliding along the sides (Figure 2.5) exerts a force, F, on the slide. The length of the line of contact between soap film and slide is twice the length of the slide [i.e. 2 (1 x) = x ] because the soap film has two sides. That is, if you think of the 2 film as being like this page, there are two interfaces, one on the reader’s side of the page, and one on the reverse side of the page. If the surface is extended by moving the slide through a distance δy then the area of surface (considering both sides of the film) increases by δA (= x δy) and the force exerted by the surface tension and resisting the extension is, from Eqn 2.1: F = γ x. The work (ws) of extension is therefore: ws = F δy = γ x δy = γ δA. (2.2)
This relationship is the basis for developing the thermodynamics of surfaces, a topic that will be explored in the next chapter. In this argument it has been assumed that the new interface created when the surface area is increased has the same composition as the original. This requires new material to be brought from the bulk phases. If, instead, the original interface is stretched with no new material brought to the surface, additional work would be needed to increase the molecular separation. If the surface of a solid is extended, then in general the work required is performed against the interfacial stress, rather than against the surface tension. The interfacial tension is one component of the interfacial stress, but the
and gas will move in response to the forces arising from the three interfacial tensions until an equilibrium position is established. 2. More information can be obtained from Lyklema (2000) and Adamson and Gast (1997.3 Contact angle. wetting. The angle. The surface tension of the air–solution interface is 35 mN m–1.5 Wire frame for extending the surface of a (doublesided) soap film. p. Further consideration of this topic is outside the scope of this book. between the solid surface and the tangent to the liquid surface at the line of contact with the solid is known as the contact angle.1 Work of extending a soap film 21 film Calculate the work of extending a soap film supported in a wire frame as in Figure 2.0 cm2. formed between solid. Methods for measuring the surface tensions of solids are at best approximate and often involve questionable assumptions. Solution Applying Eqn 2. with such factors as the isotropic or nonisotropic nature of the surface.5 cm2. the measured increase in vapour pressure for small spherical particles of solid can be used with the Kelvin equation (to be discussed later in this chapter (Eqn 2.5 μJ Note that the work (a form of energy) is positive because energy has to be put into the system.5 by 1. the presence of defects. but the assumptions of sphericity and uniformity of the particles are usually questionable. relationship between these quantities is complex and depends on the nature of the solid. The largest observed value for water on a smooth solid surface at equilibrium is about 120°. By convention the contact angle is measured in the liquid phase. liquid. and so on. .5 μ N m = 10. Problem We must remember that the soap film has two sides so the total increase in surface area is 3.6.2. 2.1 SURFACE TENSION AND WORK  13 1 2X Soap film F (doublesided) Wire frame δy Slide wire Fig.2 we have: ws = 35 10 3 N m 1 3 (10 2 m)2 105 10 7 N m = 10. 259). which shows a drop of liquid (L) on a flat solid surface (S) with air (G) as the third phase.22). θ. For example. Example 2.1. and spreading When a drop of liquid is placed on a solid surface the triple interface. The situation is illustrated in Figure 2.
3) However. such as hydroxyl groups. More generally. The angle θ′ is the instantaneous contact angle and will change as the triple interface moves towards its equilibrium position where θ′ = θ and Fh = 0. we say that the surface is hydrophobic.3 describes the equilibrium contact angle in terms of the interfacial tensions involved. Such a surface is called hydrophilic.14  2 CAPILLARITY AND THE MECHANICS OF SURFACES g GL G L gES u gGS S Fig.4) where forces acting to the right are given positive signs and those acting to the left have negative signs. it gives no real insight into the reason that a certain value of contact angle is reached. An understanding of the origin of contact angle requires knowledge of the balance of forces between molecules in the liquid drop (cohesive forces). and the difference between advancing and receding contact .6 The forces acting at the triple interface for a drop of liquid on a flat solid surface. while for others it is so low as to be unmeasurable. and those between the liquid molecules and the surface (adhesive forces). Many surfaces show an apparent hysteresis. and the contact angle will be large. will have a good affinity for water and. A surface that has primarily polar groups on the surface. therefore. 2. This is normally due to roughness of the surface. Although Eqn 2. The net force per unit length of the triple interface along the solid surface will then be: Fh = γ GS − γ LS − γ GL cos θ ′ (2. At equilibrium these tensions will be in balance and thus: γ GS = γ LS + γ GL cos θ . The position of the triple interface will change in response to the horizontal components of the interfacial tensions acting on it. the terms appropriate for all liquids are lyophilic and lyophobic (solvent loving and solvent hating). (2. when the drop is initially placed on the surface the interfacial tensions will not be in equilibrium. strong adhesive forces and a low contact angle. which is common for polymer surfaces or surfaces covered by an organic layer. We observe that some surfaces have a very high contact angle for water. If the surface is made up of nonpolar groups. where different values of the contact angle are measured depending on whether the measurement is performed on a drop of increasing size (the advancing contact angle) or of diminishing size (the receding contact angle). It follows that measurements of contact angle are frequently used as a quick and simple method to gain qualitative information about the chemical nature of the surface.
or. It is convenient to define a spreading coefficient.4. and then θ’= 0. usually by taking a digital image and using software to determine the angle. The spreading of a liquid over a solid depends on the components of the interfacial tensions acting parallel to the solid surface at the line of contact. would show no hysteresis. giving equilibrium. if they could be observed.2. Wetting is determined by the equilibrium contact angle. the liquid does not wet the solid. if θ = 0. the liquid spreads completely. there is complete or perfect wetting. whereas if SLS ≤ 0 the drop does not spread completely and it finds an equilibrium contact angle. the surface of the solid is often roughened and a receding contact angle used. The needle used to deposit the drop is visible at the top. Fig. Contact angle measurements are made by placing a drop of the liquid on a surface and viewing it with some type of magnifying lens (Figure 2.1). as there is always some interaction between the liquid and the solid.7). cos θ’ = 1. the liquid spreads completely. if such a position is not possible.5) If SLS > 0. The angle can then be measured optically. If θ < 90°.2. thus when a contact angle close to zero is needed. Although the macroscopic observation of angles shows hysteresis. and Eqn 2. θeq. . The advancing contact angle (liquid moving over an apparently dry surface) is greater than the receding angle.4 becomes: Fh (θ ′ = 0) = γ GS − γ LS − γ GL. Contact angles of 180° are not found. θ. if θ > 90° (cos θ < 0). as for example when surface tension is to be measured by a Wilhelmy plate (see Section 2. it is likely that the microscopic angles. 2. (2. by S LS = γ GS − γ LS − γ GL. The triple interface will move in the direction dictated by Fh until a value of θ is reached at which Fh = 0. where Fh = 0.7 A contact angle image showing a drop of water on a PTFE surface.1 SURFACE TENSION AND WORK  15 angles is another useful and quick method of gaining qualitative information about the nature of the surface. The most difficult part of dealing with very high contact angles is keeping the drops in place long enough to be measured! The slightest tilt on the surface is enough to cause the drops to roll off.6) (2. as in Eqn 2. SLS. the liquid is said to wet the solid.
Although the contact angle of the underlying poly(dimethylsiloxane) is about 75°.5 times greater than would be expected from an equivalent flat surface. The two key attributes to be considered in the design of such interfaces are the chemical composition and the micro. Lamb and H. Fabrication of superhydrophobic coatings has become a rapidly expanding area of research over the last few years.and nanostructure. Superhydrophobicity generally refers to surfaces with water contact angle θ > 150°. and building materials leading to buildings that wash themselves when it rains. Nanostructural roughness is manipulated to create superhydrophobicity from (chemically) low (θ < 90°) contact angle materials. due mainly to the useful property of selfcleaning that such surfaces (and the lotus leaf) exhibit. Biomimetics is the name given to the practice of mimicking the properties of biological systems and their application to technological problems. Typically. The contact angle of water on surfaces varies greatly. with the rough coating of nanoparticles the contact angle is 160–170° (courtesy of R. which results in droplets of water rolling off the surface and taking surface contamination with them. giving extreme hydrophobicity. This minimizes the use of commonly used.16  2 CAPILLARITY AND THE MECHANICS OF SURFACES How lotus leaves help keep buildings clean The leaves of the lotus plant (Nelumbo) display a remarkable ability to remain clean even in the muddy environment in which they grow. as do fluoropolymers like TeflonTM. Hydrocarbon surfaces (like the paint surface of a car after it has been polished with a wax polish) have high contact angles. . the surface areas of such materials are 2. Such architecture can be applied to surfaces as varied as fabric. depending on the chemical nature of the surface. Zhang). but expensive fluorinated compounds that also achieve high contact angles by exploiting chemical interactions. The lotus leaf has inspired researchers to emulate its amazing properties in synthetic surfaces. This is due to the complex nanostructure of the surface. 1 2 3 4 μm The image above shows a threedimensional view of a superhydrophobic surface viewed with an atomic force microscope. paint.
4 The surface of tension It has already been pointed out that any real interface has a finite thickness. 2. Proper location of the surface of tension is important when the interface is curved. Young suggested that this complex pattern could be replaced by a mathematical surface under tension with a pattern of uniform forces in each of the bulk phases extending unchanged right up to the mathematical surface (Figure 2. Details of the procedure have been described by Defay. (2.5 Work of adhesion and cohesion If two phases (α and β) in contact are pulled apart inside a third phase ω. 2.9). (1966).1. instead of two distinct phases.8 Possible pattern of forces in the real interface and the model interface.8) . This mathematical interface is called the surface of tension.7) If. two equations are obtained from the requirements that both the resultant forces and the resultant moments of those forces must be the same in the model system as in the real system. There is a contribution from each interface removed from or added to the system: w αβ = −γ αβ + γ αω + γ βω . Possibly a pattern such as that in Figure 2. a column of a single liquid is pulled apart. In 1805.8(a) might be found. the work of cohesion is: w αα = 2γ αω (2.2. the original interface is destroyed and two new interfaces are formed (see Figure 2. but as the means for observing such a pattern do not exist some alternative is needed. w αβ. but for many purposes it is convenient to replace the real interface by a mathematical surface of zero thickness that is mechanically equivalent to the real interface.8b). This model surface is the surface of tension. The work energy per unit area in performing this operation is called the work of adhesion. et al.1. 2.1 SURFACE TENSION AND WORK (a) Phase β (b)  17 γ Surface region Surface of tension Phase α Real interface Model interface Fig. In essence. If it were possible to observe the pattern of forces acting on a plane cutting through an interface it would be complex with the complexity extending over a region of finite thickness.
3) to give: w LS = γ GL + γ GS − γ LS = γ GL (1 + cos θ ). We note that the work of adhesion falls to zero when the contact angle is 180o. p. We note that in Eqns 2.9 The separation of two phases. but emphasize that such angles are never observed as it would imply that there is no interaction between the liquid and solid surface.7. The surface tension of the air/water interface is 72 mN m–1. and 0 mN m–1. and 2. the expression for work of adhesion (Eqn 2. and (a hypothetical) 180o. where the equilibrium contact angles are 30o. . 2.9 the definition of work (and symbol w) is different from that usually used as it is work per unit area (Everett.18  2 CAPILLARITY AND THE MECHANICS OF SURFACES Phase ω β Interface ω/β β Interface β/α α α Interface ω/α Fig. Problem We can use the Young–Dupré equation to calculate the work of adhesion per unit area of contact between water and the solid. 60o. Its significance is that it relates the work of adhesion to the readily measured quantities. 597). The units are therefore J m–2 (= N m–1) compared with J.8.9) This is commonly known as the equation of Young (1805) and Dupré (1869). 2. 120o.2 Work of adhesion of a liquid on a solid 22 Calculate the work of adhesion of water on four solids.7) can be combined with the equation for the contact angle (Eqn 2. 36. Example 2. 1972. rather than to the inaccessible interfacial tensions involving the solid surface. γGL and θ. When one of the phases is a solid. For the first solid (θ = 30o): Solution 3 w LS = 72 × 10−3 N m 1 ( ) = 134 10 3 N m 1 = 134 mJ m −2 Using the same procedure for the other solids we obtain for the four cases: 134. (2. 108.
Along the line of contact.10. the surface tension can be determined. the force is measured by the twist of a simple torsion wire amplified by an optical beam. The surface tension of the interface between a static. The situation is shown in Figure 2. and the choice of method depends on the given system. Many methods exist for measuring the value of the surface tension of an interface.11.2 MEASUREMENT OF SURFACE TENSION Light beam Torsion wire Mirror Beam  19 2. respectively.1 Wilhelmy plate Possibly the easiest way to demonstrate the force arising from surface tension is to dip a flat plate through the surface of a liquid and measure the force acting on it. If the plate is hanging vertically. 1863). If the plate is perfectly wetted by the liquid a meniscus will form where it passes through the liquid surface giving a contact angle of 0°. As F. and y can all be measured.1. from Eqn 2. the simple formula of Eqn 2. and is named after the scientist who first used such a device to measure surface tension (Wilhelmy. the meniscus will contact the plate along a line of length 2(x + y).2.10 Wilhelmy plate for measuring surface tension. Paper plate 2.2 Measurement of surface tension Surface tension is a fundamental quantity in the investigation of fluid interfaces so its measurement is of great importance. Electronic devices are normally used. the solution is viscous or the surface tension is changing rapidly. a careful choice of techniques must be made. Fig. . exert a downward force on the plate of: F = γ 2(x + y) ⋅ (2. but if. for example. x. the only correction that is needed arises from the buoyancy of the plate and that depends on the depth of immersion.10 holds. where x and y are.2. as shown in Figure 2.10) Liquid surface Plate (endon) Fig. and air can be measured by a number of methods. the horizontal length and thickness of the plate. 2. Lane and Jordan (1970) have shown that despite the complex geometry of the meniscus at the edges of the plate. This is known as a Wilhelmy plate. 2.11 Photograph of the water meniscus on a Wilhelmy plate of roughened mica. the liquid surface will be vertical so the surface tension along this line will. aqueous solution. Here. Thus.
Wilhelmy plates may be used in a static mode.2. however. 2. the most common being roughened mica. or in a detachment procedure where the difference in force between the plate hanging (wet) in air and at the moment of detachment when withdrawn from the liquid is measured.12) so a correction procedure must be followed (Adamson and Gast. the liquid rises up the tube until an equilibrium position is attained (Figure 2. With high quality filter or chromatography paper the liquid saturates the plate and essentially forms a liquid surface over the paper ensuring that the contact angle is zero. 1997.2 Capillary rise If a narrow capillary tube is dipped into a liquid the level of liquid in the tube is usually different from that in the larger vessel. but nevertheless the Wilhelmy plate in detachment mode is only approximate. etched glass. the bottom edge of the plate is set level with the flat surface of the liquid the buoyancy correction is zero. In the past. Wilhelmy plates have been made from a variety of materials. If.3). The du Noüy ring is a variant of the Wilhelmy plate detachment technique. 2.11) . and platinum. With a clean glass capillary and a liquid that wets it. To some extent. However. Detachment data require a negative correction for buoyancy and there is usually some excess liquid clinging to the bottom edge of the plate. in a surface film balance (see Section 5. for example. the assumption that the force attributable to surface tension is simply twice the circumference of the ring multiplied by the surface tension is an oversimplification because of the complex geometry of the surface (see Figure 2. Chapter II). these two sources of error cancel. as.12 Crosssection of the surface for the du Noüy ring method for measuring surface tension. At this point it can be considered that the liquid column in the capillary is supported by the surface tension. In 1977 Gaines suggested the use of paper plates.13). Instead of the flat plate a horizontal ring with a diameter of about 10 mm is used. Scrupulous and elaborate procedures were needed with these materials to ensure that the surfaces were clean and that the contact angle was zero.2. For the situation where the liquid wets the capillary wall perfectly (θ = 0): γ 2π rc = ρ ghπ rc2 γ = 1 ρ gh rc 2 (2.20  2 CAPILLARITY AND THE MECHANICS OF SURFACES Ring support Ring Water surface Fig.
h h Beaker Weight of liquid in capillary Fig. uses a fascinating application of capillary rise to stay alive in extremely dry conditions. as the accurate determination of θ in a capillary is extremely difficult. This removes the difficulty. Water is not absorbed through the skin.11 provide a simple and accurate means for determining the surface tension of a liquid. The water can come from the ground or from dew condensing on its body in the cold desert nights. which form capillaries through which water is able to move over its body to the corners of its mouth from where it is able to drink.13 The phenomenon of capillary rise. The measurement of capillary rise and the use of Eqn 2. sometimes experienced. The capillary rise is measured from the flat surface of the liquid in the large container to the height of the lowest part of the meniscus in the capillary (Figure 2. It is about 20 cm long. somewhat like rose thorns. As these quantities are known or measurable the surface tension can be determined.2.4). An alternative is to measure the difference in height between the rises of liquid in two capillaries of different internal diameters. is slow moving. a small lizard found in Australian deserts. It is covered by grooved thorns. rc is the radius of the capillary. 2. . it should be the difference in density between the liquid and the surrounding gas). g is the acceleration due to gravity. and lives mainly on ants.13). where ρ is the density of the liquid (more accurately. The thorny devil (Moloch horridus).2 MEASUREMENT OF SURFACE TENSION Surface tension  21 Liquid meniscus Capillary Rise. of referring the height to a flat liquid surface (see Exercise 2. it is essential that the capillary be scrupulously clean and that the contact angle be zero. However. and h is the measured capillary rise.
3 Capillary rise 23 Ethanol has a surface tension of 22.11 is based on the Laplace equation (Section 2. rc. An iterative procedure is used to refine the value of the capillary constant. If we assume that the downward force due to the weight of the drop immediately before detachment is balanced by the upward force due to surface tension at the line of contact with the capillary tip we have: mg = 2π rγ (2. 2. r is the radius at the lowest part of the meniscus and is always slightly larger than the capillary radius.22  2 CAPILLARITY AND THE MECHANICS OF SURFACES It is usually possible to meet these requirements with pure liquids. the expected rise is 57.8 10 3 m 106 kg m 3 9.3. This emphasizes the fact that narrow capillaries of especially uniform bore are required for such measurements.4 mN m–1 and has a contact angle on glass of 0o. but with solutions there may be adsorption of the solute on the capillary walls leading to θ ≠ 0.11 we have: 2 22. ρg (2.13) where m is the mass of the drop and g is the acceleration due to gravity. the term capillary constant is misleading as its value depends on properties of the liquid.1 mm. which is defined by: 2γ = a2 = rh. A more rigorous derivation of Eqn 2. However.79 g cm–3. Actually. The total weight of the detached drops is then measured. there are serious errors in the assumption that the weight measured . a.8 mm above the flat liquid surface.2.3 Drop weight or volume A drop of liquid hanging from the tip of a capillary is supported by the surface tension of the liquid. The procedures are too complex to be described here.12) Here.79 10 3 Thus.4 10 3 N m 1 = 57. Problem Solution Using Eqn 2. It shows more clearly that for very precise measurements it is necessary to correct for the deviations of the liquid surface from a spherical shape. Example 2.81 m s 2 0.1 10 3 m h= 2γ = ρ grc 0.1). The experimental procedure is to allow a known number of drops to form slowly and detach. but a detailed treatment can be found in Adamson and Gast (1997. as well as the capillary. Chapter II). Its density is 0. Calculate the rise of ethanol up a capillary of radius 0.
indicated by the arrows. the pressure of gas in the bubble increases.14). Note that the radius of the bubble. decreases to a minimum when the radius is the same as that of the capillary. is the total weight of the drops. has to be applied to Eqn 2. that depends on the capillary radius and the drop volume.14 When a drop falls from a capillary. (a) (b) (c) (d) (e) Liquid phase Fig.13.2 MEASUREMENT OF SURFACE TENSION (a) (b) (c) (d)  23 Fig. a correction factor. a significant amount of liquid remains (d).15).4 Maximum bubble pressure During the formation of a bubble of an inert gas beneath a capillary dipping into a liquid the bubble radius is at first large. as a sizable fraction of the liquid hanging beneath the capillary remains attached to the capillary after each drop has fallen (Figure 2. Thus.2.13. This necessitates a correction to be applied to be simple formula of Eqn 2.17).2. passes through a maximum. 2. 2. . the method is fast and easy to use. Nevertheless. and then increases again (Figure 2. decreases to a minimum for case c. It is one of the few techniques that can be used at the liquid–liquid interface. and then decreases. where the radius is equal to that of the capillary. As a consequence of the Laplace equation (2. discussed below. and then increases again. The drop volume method is a closely related one in which the drops are formed from the tip of a calibrated syringe. 2.15 Shapes of a bubble in a liquid during development.
2. Simple geometry then gives for the radius of curvature of the meniscus: r= 2 rc2 + zc .16. Usually.13) except for the taper of the pipette walls. The methods are useful when only small volumes of the liquid are available. 2. a very sharp edge is used so that there is no ambiguity about the capillary radius on which the bubble is being formed.2. Great care must also be exercised in the design and construction of the capillary tip. 2 zc (2. r.14) rc Test liquid zc r rc Air or other immiscible liquid Tapered micropipette Fig. Usually.24  2 CAPILLARITY AND THE MECHANICS OF SURFACES Because the bubble radius at the measured maximum pressure is known (equal to the radius of the capillary) the surface tension can be calculated from the Laplace equation. the radius of the sphere (r) can be calculated from measurements of a chord (2rc) and the maximum distance from the chord to the surface (zc) as shown in Figure 2. However. 2. photographs of the drop are taken and measurements made on these.2. If we can assume that the interface forms a spherical cap. of the meniscus.6 Micropipette Liquid in the tip of a tapered micropipette and subject to a small excess pressure in the pipette will form a curved meniscus similar to that formed in a capillary tube (Figure 2. because the pressure that the liquid exerts on the bubble varies with the depth of immersion the bubble shape is not exactly spherical and corrections similar to those used in capillary rise measurements are needed for accurate work.5 Sessile and pendant drops The shape of a drop sitting on a flat surface (sessile drop) or hanging beneath a flat solid surface (pendant drop) is determined by the size of the drop and the surface tension of the liquid.16 Test liquid in a micropipette showing the measurements (rc and zc) required for calculating the radius. .
Consequently the equality in Eqn 2. This can be regarded as a spreading or surface pressure (see Eqn 1.4 Relation between surface pressure and spreading coefficient 24 coefficient Prove that these two quantities are the same. on reservoir surfaces for example.6: Π γ as γ af S os = γ as ( ) where Sos is the tabulated value of the spreading coefficient for clean subphase surface. Example 2.2. it is possible to estimate the surface tension by observing the spreading or otherwise of drops of various indicator oils. and subphase with film. s.2 and 2. Note. we have from Eqns 1. 2001). γaf. that optical distortions arising from the curvature of the capillary glass can make accurate measurements difficult. When the oil just spreads.14 with the Laplace equation (2. For a given oil γao is fixed and known. Usually. . o. Soff = 0 and: γ af = γ os + γ ao so: S os = γ as γ af Π (2. Eqn 2. A drop of the oil is placed on the surface and its spreading behaviour observed.6) that is found in tables of data. indicator oil. Solution Let superscripts a. it is the spreading coefficient.6 shows that spreading will occur when: γ af ≥ γ os + γ ao (2. respectively. subphase. (Eqn 2. and f indicate air.15 gives the minimum value of the surface tension of the subphase.. this procedure is used to detect the presence of a surface film and to estimate the change in surface tension caused by the film. indicator oil.2 MEASUREMENT OF SURFACE TENSION  25 Measurement of the pressure difference across the interface and combination of Eqn 2. however. The technique is particularly useful when only minute quantities of liquid (≤ 400 μL) are available. Usually.17) then gives the interfacial tension (Lee et al. however.2. respectively.15) where a.16) The tabulated values of the spreading coefficient are often referred to as the spreading pressures of the oils. subphase. For a drop of indicator oil placed on the surface of a liquid (the subphase). and f refer to air. and subphase with film. s. Thus.2) exerted by the oil. So. Improved accuracy can be attained by using several pressure differences and corresponding meniscus radii.7 Indicator oils For measurements in situations where the use of laboratory instrumentation is not feasible. and if we can assume that the oil drop displaces any surface film on the subphase γos is also fixed and known. 2. o.
hence.7 46.0 24. if we take a flat soap film stretched across a circular frame the pressures on either side are the same (usually atmospheric pressure). For a curved interface.5 49. So/mN m−1 0. The derivation of the Laplace equation follows.0 26.1 have a slight solubility in water and some can dissolve small amounts of water. However. The spreading pressure is dependent on the dodecanol concentration and is approximately proportional to the logarithm of the concentration. This is expressed in the Laplace equation: P α − Pβ = 2γ r (2. in a soap bubble the pressure inside must be greater than that outside and we can demonstrate this by blowing the bubble on the end of a tube. γmin/mN m−1 72. the pressures on either side must be different. eventually forming a flat film over the end of the tube.17) which holds for a spherical interface of radius r. the spreading coefficient.8 48. . Table 2. so it is the initial spreading behaviour that should be observed. 2.15 8.8 Initial spreading coefficient. It is necessary to blow into the tube to inflate the bubble and if the tube is left open the bubble will expel the air and shrink. Timblin et al. For example.3 The Laplace equation If a fluid interface is curved.1 Indicator oils for estimating the surface tension of filmcovered surfaces of water at 20°C Indicator oil Minimum spreading tension. When the system is at equilibrium. Details of the mineral oil were not given so calibration is needed before this procedure can be used with a different oil. However.9 nOctane Benzene nPropyl palmitate Aniline Oleic acid nOctanol nButanol isoButanol By using a set of indicator oils with different spreading coefficients (relative to a clean subphase surface) the surface tension of the subphase covered by a surface film can be estimated.2 48. it is important to note that some of the liquids shown in Table 2. the forces of surface tension are exactly balanced by the difference in pressure on the two sides of the interface.9 15.2 22.9 57.1 36.26  2 CAPILLARITY AND THE MECHANICS OF SURFACES Table 2.5 24. Such solubility can alter the surface tension values and. (1962) developed a set of indicator oils consisting of solutions of dodecanol in a light mineral oil.1 shows some potentially useful indicator oils for studying water surfaces. before appreciable dissolution has occurred. every part of the interface must be in mechanical equilibrium.6 63.6 35.
The cap will also be subject to a force arising from surface tension acting tangentially at all points around the perimeter of the cap. These forces are shown in Figure 2.17b) The negative sign is used because this force acts in the opposite direction to the force arising from the pressure difference. on each element. But cos θ = rc/r.3 THE LAPLACE EQUATION  27 Derivation of the Laplace equation Consider a spherical cap. Mechanical equilibrium If the system is in mechanical equilibrium the forces in the z direction must sum to zero: FzΔP + Fzγ = 0 or .2. (b) resolution of forces.17a) The surface tension will exert a force. The sum of the resolved forces in the z direction for the entire area of the cap is thus: F ΔP = (P α − Pβ )∑ δA = (P α − Pβ )π r 2 ⋅ z c Force arising from surface tension (2. However. The pressures exerted on the interface by the two bulk phases (α and β) will be different if the interface is curved and this difference (ΔP) will give rise to a force acting along the normal to the interface at each point. 2.17 (a) Forces on a spherical cap. γδl. of the perimeter and acting tangentially to the surface at δl. The sum over the whole perimeter is therefore: Fzγ = −γ ∑ (δl)rc / r = −γ (2π rc )rc / r = −2π r γ / r. The component in the z direction is γδl cos θ.17(a). (a) P β (b) Phase β Pα Phase α u r F (g) rc z F (ΔP) δA u g f δA cos f g Fig. 2 c (2. symmetrical about the zaxis and part of a spherical interface. and its component in the z direction (the central axis of the cap) is (Pα−Pβ) δA cos ϕ. Force arising from the pressure difference For a small segment of cap of area δA the force arising from the pressure difference is (Pα−Pβ) δA. δA cos ϕ is equal to the area of the projection of δA on to the plane containing the perimeter of the cap. so the component in the z direction of the surface tension force on δl is γδlrc/r. δl.
By convention. drawing a plane containing the normal (in an arbitrary orientation) taking a second plane containing the normal at right angles to the first plane.28  2 CAPILLARITY AND THE MECHANICS OF SURFACES (P α − Pβ )π rc2 − 2π rc2γ / r = 0 (2.18 illustrates how the radii of curvature are defined. positive values are assigned to the radii of curvature. observing the curves formed by the intersections of these planes with the surface and then finding the radii of the two circles drawn in these planes that have the same curvatures as these lines at the selected point.17c) and so: P α − Pβ = 2γ r (2. . or r″.18 Schematic illustration of the procedure for obtaining the radii of curvature at a selected point on a curved surface. The Laplace equation then becomes: ⎛ 1 1 ⎞ 2γ P α − Pβ = γ ⎜ + ⎟ = ⎝ r′ r′′ ⎠ rm (2. 2.17) which is the Laplace equation for a spherical surface. r′. For a nonspherical interface two radii of curvature are needed. Figure 2.18) Plane through normal:blue Normal to surface Plane through normal: black Line on surface in black plane r′ r ′′ Line on surface in blue plane Circles in the two planes Fig. if they lie in phase α. r. The two radii of curvature at a selected point (r′ and r″) are obtained by taking the normal to the surface at that point.
When the tap is turned to connect the two bubbles (as in the lower figure). it will form into a ‘wicker basket’ shape where r′ = −r″ at all points on the surface. but more complex shapes occur even when there is no difference in pressure. but is perfectly understandable in the light of the Laplace equation.3.19 Sketch of a soap film stretched between two circular wire frames.3 THE LAPLACE EQUATION  29 Wire frame r′ r′′ Soap film Wire frame Fig.19) a simple cylindrical shape is not possible as there is no pressure difference and this would therefore violate the Laplace equation.17 requires that at any point on the surface r´ and r´´ must be equal. If the top and bottom ends are open.2. the smaller bubble shrinks and the larger bubble grows until the curvatures of both bubbles are the same.1 Applications of the Laplace equation The shapes of soap films A soap film stretched across a flat wire frame is flat because the pressure is the same on both sides.20. An interesting application of the Laplace equation is seen when two bubbles of different size are connected by a tube. For example. Capillary rise Fig. 2. which predicts that the pressure inside the smaller bubble is greater than that in the larger one. but with opposite signs.19) 2. 2. as in Figure 2. Balancing the pressure decrease under the curved liquid surface (assumed to be spherical and making a contact angle of θ with the capillary wall) in the capillary: P atm − P = 2γ 2γ cos θ = r rc with the pressure decrease from the weight of the liquid column: P atm − P = ρ gh .20 Illustration of the Laplace equation. That is. if the film is formed as an open cylinder (as in Figure 2. Threeway tap where 1/rm is the mean curvature (inverse of the radius) defined by: 1 1⎛ 1 1⎞ = ⎜ + ⎟⋅ rm 2 ⎝ r ′ r ′′ ⎠ (2. the air pressure will be the same on both sides of the film so Eqn 2. Instead. the film over the end of the left tube has the same curvature as the large bubble. The capillary rise phenomenon can also be treated using the Laplace equation. It is often surprising that the small bubble shrinks while the larger bubble grows. This and other experiments with soap bubbles have been described by Boys (1911).
1 Consequences of the Kelvin equation The Kelvin equation has many important consequences as it provides explanations for such phenomena as the difficulties found in selfnucleation of a new phase.2. Measuring surface tension by maximum bubble pressure It was stated in Section 2. the growth of large droplets at the expense of smaller ones. It is difficult to measure and to reproduce θ if θ ≠ 0 so only systems with θ = 0 are used in practice. For this situation we have: ΔP rc (2. These are described in detail by Adamson and Gast (1997). and condensation in capillaries. It is discussed in some detail in Section 2. 2. Deviations from the spherical shape are a complication for accurate measurements of surface tension and several correction procedures have been devised. This relationship is known as the Kelvin equation: ⎛ pc ⎞ ⎛ γ V L ⎞ ⎛ 2 ⎞ ln ⎜ ∞ ⎟ = ⎜ ⎝ p ⎠ ⎝ RT ⎟ ⎜ rm ⎟ ⎠⎝ ⎠ (2. 2.4 that the maximum bubble pressure occurs when the bubble radius is the same as the capillary radius.30  2 CAPILLARITY AND THE MECHANICS OF SURFACES gives: γ = ρ ghrc 2 cos θ (2. the vapour pressures over the curved surface of effective radius rm (see Eqn 2.4 The Kelvin equation An important consequence of the Laplace equation concerns the effect of surface curvature on the vapour pressure of a liquid. γ = The Kelvin equation The Laplace equation forms the theoretical basis for the Kelvin equation. and V is the partial molar volume.20) for a capillary of radius rc. At this point the radius of curvature of the bubble has its minimum value so according to the Laplace equation the pressure must be the maximum. rc.21) 2 where the pressure term is the difference between the pressure applied to the capillary and atmospheric pressure corrected for the small hydrostatic pressure arising from the depth of immersion.22) where pc and p∞ are.4. As can be seen from the derivation below.4. which describes the effect of surface curvature on vapour pressure.19) and a flat surface (r = ∞). . there is a convention of signs for rm that assigns a positive sign to the radius when it lies in the liquid phase and a negative sign when it lies in the vapour phase. respectively.
22d and 2.4 THE KELVIN EQUATION  31 Derivation of the Kelvin equation At a curved interface the condition for mechanical equilibrium is given by the Laplace Eqn 2. Note the approximation between Eqns 2.22) (2. the two principal radii are equal.22i. Droplet growth For a spherical droplet in contact with its vapour. according to the Kelvin equation (2.22g) Substitution of (2.22i) (2. for example.18: 2γ p −p = rm α β If β is the vapour phase.22i from a flat surface (1 / rm = 0. lie within the liquid phase and. and μi.22f) and μic − μ∞ = RT ln(pc/p⦵) i Equation (2.2. (2.22h) becomes: 2γδ(1 / rm ) = δpβ (V β / V α ) = δμi / V α where α is the phase on the concave side.22a) and (2. (2. ni =V . while the larger ones will tend to grow.22k) (2. ni . or a negative sign if it lies within phase β. If the vapour behaves as an ideal gas. V β >> V α (2.22i. ⎜ β⎟ ⎝ ∂p ⎠ α where superscript α has been replaced by L to indicate the liquid phase. thus. rm. β (2. μic ) yields: 2γ (1 / rm ) = (μic − μi∞ ) / V L If the equilibrium is shifted slightly with adjustments to pα. The smaller the radius.22h and 2. have positive signs. the higher the vapour pressure so that if there are droplets of various sizes present the smaller ones will tend to evaporate.22c) or μic − μi∞ = γ V L (2 / rm ) (2. Equation 2. pβ. approximately a 10% increase in vapour pressure for a water droplet of radius 10 nm (see Example 2.22j) and δμiα = δμiβ = δμi .22g) into (2.22b) where δμi refers to the process where the radius is changed. Integration of Eqn 2.22h) which is the more usual form of the Kelvin equation. μi = μi∞ ) to any selected curvature (1 / rm .22) the vapour pressure of the droplet will be greater than that of the same liquid with a flat surface. (2.22e) we have: ⎛ ∂μ α ⎞ ⎜ ∂pα ⎟ ⎝ ⎠ ⎛ ∂μ β ⎞ =V . A (2.22d) Since ⎛ ∂μ ⎞ ⎜ ∂p ⎟ ⎝ ⎠ =V T .22f give: δμi = V α δpα = V βδpβ . ni β T . For physicochemical equilibrium: μiα = μiβ = μi .22j) now becomes: If the process is carried out at constant temperature and without transfer of material across the interface then Eqns 2.5). An important example occurs in clouds where the larger droplets grow until they are heavy enough to fall as rain. We generalize by giving r a positive sign if it lies within phase α. and the assumption that the liquid is incompressible when integrating Eqn 2. Hence.22c) yields: 2γδ(1 / rm ) = δpβ (V β − V β ) / V α ⋅ ⎛ pc ⎞ ⎛ γ V L ⎞ ⎛ 2 ⎞ ln ⎜ ∞ ⎟ = ⎜ ⎝ p ⎠ ⎝ RT ⎟ ⎜ rm ⎟ ⎠⎝ ⎠ (2.22j is the general form of the Kelvin equation. . There is. we obtain: δpα − δpβ = 2γδ(1 / rm ) (2. μi = μ⦵ + RT ln(p/p⦵) i α T .
22) we have for the 10 nm droplet: ⎛ pc ⎞ ⎛ V L ⎞ ⎛ 2 ⎞ 74.12. It is worth noting that the equilibrium between a small liquid droplet and its vapour is an unstable one.115 giving pc / p exp0 115 = 1. The temperature is 280 K and the surface tension of water at this temperature is 74.31 J K 1 mol 1 280 K ⎝ ⎠ ⎝ p ⎠ ⎝ RT ⎟ ⎜ rm ⎟ ⎠⎝ ⎠ = 0. and the molar volume is 18. If. They are then termed nuclei and will be stable and capable of further growth. If the drop. When the conditions more strongly favour the new phase the critical size given by the Kelvin equation will be smaller and the probability that some embryos may exceed that size will increase. if the experimental conditions are only marginally in favour of the new phase (e.5 Vapour pressure of liquid droplets 25 Calculate the vapour pressure of spherical water droplets of radius 10 nm and 100 nm. but they would be unstable and tend to disappear.6 10 3 N m 1 18.g.115 Similarly. exp0. Smaller embryos might form. its vapour pressure will drop below the actual vapour pressure so that condensation will continue and the droplet will grow. Examples include the formation of minute liquid clusters in a supersaturated vapour and the formation of minute bubbles of vapour in a superheated liquid.32  2 CAPILLARITY AND THE MECHANICS OF SURFACES Example 2. which is used to increase efficiency in analytical and industrial filtration. Consequently the larger crystals tend to grow at the expense of smaller ones leading to the process of digestion or Ostwald ripening. for the 100 nm droplet: pc / p exp0. A similar mechanism is thought to exist for crystals in a solution: smaller crystals having higher solubilities than larger ones.012. Problem Solution Applying the Kelvin equation (2. However. Selfnucleation of a new phase In selfnucleation or homogeneous nucleation of a new phase.01×10–6 m3. originally at equilibrium.6 mN m–1. the first step is the formation of very small nuclei or embryos of the new phase inside the old phase.0115 = 1. if the supersaturation or superheating is only slight) the Kelvin equation shows that stable embryos would need to be large and unlikely to form. on the other hand. a few more molecules collide with the droplet increasing its size. .01 10 6 m3 ⎛ ⎞ 2 ln ⎜ ⎟ = ⎜ = ⎜ 10 10 9 m ⎟ 8 31 8. exp0 0115 There is clearly only a small increase in vapour pressure once the droplet radius exceeds 100 nm. loses a few molecules and decreases in size its vapour pressure will increase above the actual vapour pressure. and the droplet will evaporate and continue to evaporate.
and at age 22 was appointed Professor of Natural Philosophy at Glasgow. The formation of embryos of the critical size (critical nuclei) is thus a question of probability.5 10 3 N m 1 0. A keen yachtsman.31 J K 1 mol −1 × 375 K 8. his marine interests led to improvements in ships compasses. was born in Belfast in 1824.4 THE KELVIN EQUATION  33 Lord Kelvin William Thomson.31 . taught mathematics and engineering and in 1832 was appointed Professor of Mathematics at Glasgow University. He received many honours.22). So although the Kelvin equation gives the critical droplet size for a given value of pc/p∞ it does not indicate whether such a droplet is likely to form under the prevailing conditions. It equals the vapour pressure that the curved surface of the bubble would have to develop. Thus. encompassing particularly electricity. and noting that V rm = = 2γ M ρ RT ln pc p∞ ln 102. and the vapour pressure is 108. the first Baron Kelvin. published more than 600 scientific papers and filed 70 patents.3 108. James Thomson.8 2 × 58. marine.018kg mol −1 957 kg m 3 8. The relationship between work and heat was a contentious topic and Thomson was a major participant. and depth sounding.6 Bubble nucleation in boiling water 26 Calculate the minimum size for a bubble of water vapour forming 10 cm beneath the surface of water at 375 K that would remain stable. He was dissatisfied with the measurement of temperature and considered that the scale should be such that the transfer of heat from one body to another body at a temperature one unit less should do the same amount of work irrespective of the temperatures of the experiment. Chapter 18). i. At this temperature the density of water is 957 kg m–3. His interests were broad. (1966. William studied first at Glasgow and then at Peterhouse. This is the atmospheric pressure plus the hydrostatic pressure (ρgh) from the water.8 kPa. 3 9. thermodynamics. For this and other work on thermodynamics he was created Baron and chose as his title the name of the river that flowed past Glasgow University.81m s 2 10 10 2 m) 102263Pa M / ρ. Dr. The treatment is complex and beyond the scope of this book.26 kPa. the surface tension is 58. He died in 1907 and because there was no heir the title died with him. Example 2. but an extended discussion is given by Defay et al.5 mN m–1. timekeepers. gives: Rearranging the Kelvin equation (2. Cambridge.e. Problem Solution We first need to calculate the applied pressure at the depth of the bubble. the Kelvin. he contributed greatly to the development of the first and second laws of thermodynamics. He was knighted for his work on the design and laying of the first telegraph cable across the Atlantic. pc: pc = 101325Pa (957 kg m = 102. This led ultimately to the concept of absolute zero and to his name being attached to the unit of temperature. a post he held for more than 50 years. and engineering. eventually working with Joule on the problem. rather than thermodynamics.2. His father.
provide sites where heterogeneous nucleation of a new phase can occur under less extreme conditions than those required for homogeneous nucleation.6. but are liquid nevertheless. these crystals grow until they fall out of the cloud.5 nm. It has been estimated that the selfnucleation of ice in these supercooled droplets will not occur unless the temperature is below about –40oC. consequently. water moves through the vapour phase from the liquid droplets to the ice crystals. Freezing of supercooled droplets may be induced naturally by dust particles. Capillary condensation Capillary condensation occurs when the adsorption of a vapour in a capillary forms a liquid surface with a very small radius of curvature. However. The radii then lie in the vapour phase and. either on an aircraft flying through the cloud or from groundbased generators situated where there is a strong updraft (as at the foot of a mountain range). boiling chips. Heterogeneous nucleation In most practical situations. A higher temperature would be needed before selfnucleated boiling could occur. 1949). The negative sign arises because the logarithmic term is negative and indicates correctly that the radii lie in the vapour phase. but it can also be initiated artificially. This aspect will be discussed in more detail in Section 8. Making rain Water droplets in clouds are often below the freezing point of water. often melting in warmer air into rain drops. rather than adsorption will occur if the actual vapour pressure is higher than the vapour pressure calculated from the Kelvin equation for the curved surface. Silver iodide has a crystal structure that is reasonably similar to that of ice and can act as a nucleating material (Vonnegut. dust particles. if at somewhat higher temperatures. solid surfaces. consequently. their vapour pressures are then lower than those of the remaining liquid droplets and. Thus. some of the droplets do freeze. Hence. It has been shown that water adsorbed on silver iodide crystals freezes at only –4oC. such as the vessel walls. and so on. rain can be generated by introducing silver iodide particles into supercooled clouds. Condensation. This actual vapour pressure may well be lower than the saturation vapour pressure for a flat surface. the vapour pressure of the liquid is lower than that of the same liquid with a flat surface. The silver iodide particles can be formed by burning a solution of the salt in a flammable solvent and this should occur near the site of action. We note also that it is unlikely that a bubble of this size would form.34  2 CAPILLARITY AND THE MECHANICS OF SURFACES giving: rm = –11. .
Although we are given the atmospheric pressure (= p∞). The surface tension of nitrogen liquid at this temperature is 8.85 × 10 3 N m −1 × 34.85 mN m–1 and the molar volume is 34.3 (po ≡ p∞)]: / pc / p 0. so that capillary condensation will continue rapidly.85 10 3 N m 1 34.7 27 Capillary condensation Problem A particular ‘ink bottle’ pore in a solid consists of a cylindrical tube of radius 16 nm leading to a spherical cavity of radius 41 nm.31 J K −1 mol 1 77K 77K ⎝ ⎠ ⎝p ⎠ = −0. and for the purposes of the Kelvin equation one radius will be the internal radius of this cylinder and the other will be the radius in the plane of the cylinder axis. the gas pressure is being gradually increased.0240 giving: pc / p 0.0320. We then have a hollow cylinder of liquid.7 10 6 m3 mol 1 ⎛ 1 1 ⎞ + 1 1 9 8. Applying the Kelvin equation to the cylindrical section we first adjust the radius for the thickness of the adsorbed gas layer.726.7 cm3 mol–1. For the spherical cavity the two radii are the same. atmospheric pressure is 101. we are mainly interested in the relative pressure (= pc/p∞) [see Figure 8. Hence: Solution ⎛ pc ⎞ ⎛ V L ⎞ ⎛ 1 1 ⎞ ln ⎜ ⎟ = ⎜ + ⎝ p ⎠ ⎝ RT ⎟ ⎜ r1 r2 ⎟ ⎠ ⎠⎝ = 8. This will lead to filling of the neck and blocking of access to the spherical cavity. . In this experiment. and thus infinite. Thus. so we will assume that there has been prior adsorption covering the surfaces of both sections with a 1 nm layer of nitrogen (approximately 2 layers and sufficient to give a liquidlike surface). Once this process has begun the radius of the liquid surface within the pore will decrease.4 THE KELVIN EQUATION  35 Example 2. capillary condensation will occur first in the narrow cylindrical neck of the pore. Describe the process of capillary condensation in the pore. as the gas pressure is increased. so: ⎛ pc ⎞ 8.31 J K mol 77K m⎟ ⎝ 15 10 m ⎠ = −0.976.7 10 6 m3 mol 1 ⎛ ⎞ 1 1 ln ⎜ ∞ ⎟ = ⎜ −40 × 10−9 m + 40 10 9 m ⎟ 8 31 8.3 kPa.2. Calculate the relative pressure at which capillary condensation of nitrogen at 77 K (the boiling temperature at atmospheric pressure) would occur in each section.
1981). Experimentally it is found that the surface tension of a pure liquid decreases nearly linearly with temperature. g/mN m−1 75 70 65 60 55 260 Air–water interface 280 300 320 340 360 380 Temperature.6 (Fisher and Israelachvili.5 nm for several organic liquids. . 2. 80 Surface tension.11. When this bridge suddenly evaporates the separation is measured and from this rm can be calculated. 2. It was found that the Kelvin equation held down to values of rm as low as 2.1 Effect of temperature on surface tension The chief factor affecting the surface tension of a pure liquid is the temperature (for example. 1983).2 Verification of the Kelvin equation Not surprisingly. T/K Fig. the forces of interaction between two crossed cylinders of molecularly smooth mica can be measured as a function of separation. the cylinders are slowly separated so that a bridge of liquid forms between the mica surfaces. Another approach uses the surface forces apparatus described in more detail in Section 9. With an annulus of condensed liquid at the junction. In this apparatus. In order to do so. Details of this procedure are given in Section 4..21 The surface tension of the air–water interface as a function of temperature.5. of course. be zero at the critical temperature.9. where the interface disappears. it is necessary to measure both the vapour pressure and the surface curvature of a liquid with a highly curved surface. Figure 2.5 The surface tension of pure liquids 2.4. an equation such as the Kelvin equation is difficult to verify experimentally.4.36  2 CAPILLARITY AND THE MECHANICS OF SURFACES 2. capillary condensation may occur at the junction if the vapour pressure is high enough. This result also indicates that macroscopic values of γ and ρ hold at such low dimensions. It must. If the cylinders in contact with one another are exposed to the vapour of a test liquid. (Data from Vargaftik et al. Convincing data have been obtained by La Mer and Gruen (1952) using monodisperse aerosols.21). This vapour pressure can be controlled by setting the temperature of the bulk liquid or adding a nonvolatile solute.
10.6 25.5. is attributable to shortrange electron exchange interactions.0 22.5 21.8 Acetic acid Acetone Benzene nButyl alcohol Carbon tetrachloride Chloroform Cyclohexane Ethyl acetate Ethanol Diethyl ether Glycerol Ethylene glycol nHexane Isobutyl alcohol Methanol Mercury nOctane Oleic acid Propanoic acid nPropyl alcohol Pyridine Toluene Vinyl acetate Water . in this instance arising from the temperature gradient. 2.0 72. Table 2.5 24.2.2.0 63.1 28.4 22. This is an example of the Marangoni effect.4 48.0 27. 1972) Liquid Surface tension. The very high surface tension of mercury.7 23.23) where M is the molar mass and ρ is the density. the origin of socalled metallic bonds.2 24. γ/mN m−1 27.7 37.5 486. typical of values for metals.4 17. A related phenomenon is discussed in Section 4.4 Liquid Surface tension.2 The surface tension of liquids Values for the surface tensions of some pure liquids are given in Table 2.9 22.9 25.5 THE SURFACE TENSION OF PURE LIQUIDS  37 For some liquids the empirical Eötvös equation describes the dependence of surface tension on temperature: d γ (M / ρ)2 / 3 dT ( ) = −2.2 The surface tensions of some common pure liquids at the vapour– liquid interface at 20°C (from Jasper. γ/mN m−1 18.12 × 10 −7 J mol −2 / 3 K −1 (2. The Marangoni effect effect The effect of temperature on surface tension can be nicely demonstrated by spreading a thin film of water on a metal plate and holding a piece of ice against the underside of the plate. attributed by Thomson (1855) and Marangoni (1871.5 26. Water migrates to the area above the ice. 1878) to gradients in surface tension.2 28. producing an observable thickening of the water layer and if the ice is moved slowly around the thick region moves with it.4 27.6 32.2 25.
but with other materials as well. All four hydrogen bonds are approximately linear. but much less than for covalent and ionic bonds (~500 kJ mol−1) (Israelachvili.22. The charges (q) on the left represent the charges attributable to the unshared electron pairs. 2. As water is a major component in most aspects of interface science. we will discuss it in detail below. this structure dominates. this is a very favourable arrangement. there are certain atoms that readily form hydrogen bonds when in appropriate compounds. Only glycerol has a surface tension approaching that of water. 1991.22 Sketch of water molecule showing the tetrahedral distribution of charge with bond lengths and angles.38  2 CAPILLARITY AND THE MECHANICS OF SURFACES It is notable that the surface tension of water is significantly higher than the surface tensions of all of the organic liquids. and nitrogen in amines are important examples. e is the electronic charge.24 e l' = 0. the hydrogen bonds in liquid water have a strong tendency for directionality and linearity. It is also important to note that the strength of hydrogen bonds (10–40 kJ mol−1) is appreciably greater than for typical van der Waals attractions (~1 kJ mol−1). Water and glycerol (plus some other liquids not shown in Table 2. Solid surfaces at which there is extensive hydration are described as hydrophilic. or a charged surface the neighbouring water molecules are able to arrange themselves with their charges of opposite sign towards the other material. The charges on water molecules and their strong tendency to form hydrogen bonds govern their interactions not only with other water molecules. . H + q = 0. 127). In ice.1 nm = 109° H +q Fig. This is the process of hydration.2) are highly polar hydrogenbonding liquids and it is this feature that explains the high surface tensions. In addition to these charged or polar entities. but it is important to consider here the distribution of electric charge in the molecule as this is the key to understanding its interactions with other molecules. p. These can interact with water by forming hydrogen bonds. giving a tetrahedral arrangement. but although it tends to be retained in liquid water it is somewhat disordered and labile. Oxygen in alcohols and polyethylene oxide chains. If the other material is an ion. Energetically. Based on the model of Stillinger and Rahman (1974).3 The hydrophobic–hydrophilic interaction The structure of the water molecule is well known.5. The basic configuration is shown in Figure 2.08 nm −q O −q l = 0. Water molecules tend to form hydrogen bonds with four other water molecules. 2. with each molecule providing the hydrogen atoms for two of the bonds and with the hydrogen atoms in the other two bonds coming from neighbouring water molecules. Nevertheless. a polar compound.
1991.1). There is.3) thereby minimizing contact with the surface and maximizing the formation of hydrogen bonds with other water molecules. indicating negligibly low solubility. The high surface tension of water can also be attributed to this effect as the air essentially forms a hydrophobic surface. methanol. In longchain alcohols. p. Thus.6. a smaller entropy decrease. forming a clathratelike compound. meaning loves both. ethanol.1. Thus. When a hydrophilic group and a hydrophobic group are combined in the one molecule we have a class of compounds now commonly referred to as amphiphiles (from Greek. while insoluble monolayers can be formed with tetradecanol and longer chain alcohols. the hydrophilic OH group significantly disrupts the tendency for a clathrate structure to form around the alkyl chain (Israelachvili. an effect that restricts the solubility of the solute. In these molecules the presence of the hydrophilic group modifies the hydrophobic nature of the attached hydrophobic group. a drop of water on a hydrophobic surface tends to roll into a ball with a high contact angle (see Section 2. the shorter alcohols. an entropically driven tendency for such molecules to aggregate: a process known as hydrophobic interaction. Such substances are described as hydrophobic. referring to water and to oil). conversely. a definition that will lead to the thermodynamics of surfaces as discussed in Chapter 3. When the other molecule is small. therefore. SUMMARY The concept of surface or interfacial tension has been introduced to explain the observation that surfaces and interfaces tend to contract to the minimum area.5 THE SURFACE TENSION OF PURE LIQUIDS  39 If. with the solubility then decreasing rapidly with chain length. For the hydrocarbons the entropy decrease is roughly proportional to the area of surface exposed to the water.2. 135). This results in a decrease in entropy. as the water molecules are more ordered than in the bulk liquid. the water molecules are able to arrange themselves into a cagelike structure around that molecule and so utilize all four potential hydrogen bonds per water molecule. consequently. When two hydrophobic molecules encounter one another in an aqueous solution there would obviously be a decreased area of exposed hydrophobic surface if the two molecules came together and. the other material is nonpolar and incapable of forming hydrogen bonds the water molecules arrange themselves to minimize the number of unused potential hydrogen bonds. . for example. The description of this attraction as a hydrophobic bond is not appropriate as no actual bond is formed and the attraction may occur over longer distances than for typical bonds. Important examples for the present context are the hydrocarbons and some longchain hydrocarbon derivatives. A detailed discussion of the behaviour of amphiphilic molecules is given in Section 4. Surface tension is defined as the force per unit length acting on an imaginary line drawn in the surface in a direction away from the line and tangential to the surface (Eqn 2. At a solid or liquid surface formed from hydrophobic materials the water molecules must organize themselves to minimize the number of unused hydrogen bonds. Surface tension can also be equated to the work of extending the surface by unit area. and propanol are fully miscible with water.
Phys.H. Wiley. 528. Lamb. A. I. 2nd edn. La Mer. (1991). (1997). and Everett. G. (1972). K. Intermolecular and Surface Forces. (1997). Lewis. London. University Press. J.. McGraw Hill.. and other phenomena. R.N.P. London.. (2000).H. New York. Prigogine. Chem. Water has a significantly higher surface tension than most organic liquids and this is attributable to the formation of hydrogen bonds.40  2 CAPILLARITY AND THE MECHANICS OF SURFACES Such tensions control the wetting of a solid surface by a drop of liquid. Methods for measuring surface and interfacial tension are described. and Israelachvili. 31. Israelachvili. New York. C. 1. J. FURTHER READING Adamson. It also leads to the Kelvin equation (Eqn 2. Colloid Interface Sci. R. Ref. Fletcher. the selfnucleation of a new phase.. WO 9842452. H.W. N. Jasper.L. (1977). Randall. L. J. Fisher. REFERENCES Everett. Republished by Dover Publications. (1972). Defay. Surface Tension and Adsorption. Thermodynamics. Gaines. J.H. and capillary condensation. 841. A. Chem.17). Describes many simple experiments with soap films designed to generate interest and at the same time impart some science..V. 597. M.R.. Trans.J. 1959. (1961). Provides a somewhat different perspective on surface phenomena. D. (1981). Cambridge. R.L.. (1911). III. the surface tension of pure liquids is discussed. Faraday Soc. Pitzer. G. 191. Zhang. and Gruen. (1952). 410. which describes how the curvature of a liquid surface changes the equilibrium vapour pressure of the liquid. J. Finally. 6th edn. D. the pull of a liquid surface on a wetted solid dipping into it. (1966). Pure Appl. 48. Hydrophobic Coatings. V. the rise of liquid up a capillary tube. J. Physical Chemistry of Surfaces. 2nd edn.K.N. and Brewer. it is the possibilities or otherwise for hydrogen bonding that determine the nature and strength of the interactions of liquid water with solutes and with surfaces. and Gast. San Diego. Lyklema. Longmans. A. 62. Academic Press.22). . When a surface is curved there is a difference in pressure on the two sides of the surface that is described by the Laplace equation (Eqn 2.. Soap Bubbles: Their Colours and the Forces Which Mould Them. The Physics of Rain Clouds. Liquid–Fluid Interfaces. Colloid Interface Sci. Bellemans. The Laplace equation is used to describe such phenomena as the shapes of soap films and capillary rise.. and Raston. Furthermore.N. L. Fundamentals of Interface and Colloid Science. with Applications to Colloidal and Biological Systems. C. Data. 80. Boys. (1962). J. the adhesion between two phases. New York.S.N. Academic Press. The consequences of the Kelvin equation are profound: it governs such processes as the growth of droplets and crystals.
B. (ed.1 mN m–1. Phys. 10. . Rev.3 A spherical drop of oil of radius 1.2 28. (1962). J. (1871). B.N. F.).H.. 2.. 277.0 cm is dispersed as an emulsion in water. Zhang. (1983). D..78 J] 2.N.2.. WO 2001014497. C. Q.. Aust. Vonnegut. (2000) Hydrophobic coating material containing modified gels. 177. and Voljak. Assume that the bubble is a partial sphere. 60. L. (1974). Data. Ann. Thomson.4 μJ].. 44.. Langmuir 17. (2001). D.5 A syringe needle (circular in section) with a sharp tip of radius r is used to form air bubbles beneath the surface of a solution of surface tension γ. Nuovo Cimento [2].4 Derive an expression for the surface tension when the difference in capillary rise is measured with two capillaries of different radii. In V. J. Mag.0 [S0 = 8. 17. Jones.D. observed during the slow formation of an air bubble at the tip of the needle. Chem.W. Timblin. Retardation of Evaporation by Monolayers: Transport Processes. Phys. (1855).0 mN m−1 throughout. W.6 mN m–1] 2. Vargaftik. 16. Stillinger. and Jordan. S.H. For the pure liquids the interfacial tensions (in mN m−1) are: • Air–water • Air–benzene • Benzene–water 72. Derive an expression for the maximum pressure. Nuovo Cimento [3].0 cm2. Physik. Chem. J. 239.9 35. and Garstka. Phil. (1949). p. 817.O. J. (1970).B.0 However small amounts of each liquid slowly dissolve in the other and this affects the interfacial tensions which then become: • Air–water • Air–benzene • Benzene–water 62. D. [w = 3. New York. Chem. R. N. Volkov. K. Marangoni. Ref. Wilhelmy. L. [w = 22. Calculate the work required for the hypothetically reversible dispersion process assuming that the interfacial tension remains constant at 30.2 Describe the spreading behaviour you would expect when a drop of benzene is placed on a clean water surface. 7. 2.1 Calculate the work required to stretch a soap film so that its area increases by 4.8 28.1 mm. (1878). Chem.. and Needham. J. 97.5 THE SURFACE TENSION OF PURE LIQUIDS  41 Lane. and Rahman A. The oil particles in the final emulsion are spherical and have a radius of 0.. The surface tension of the air–soap solution interface is 28 mN m−1. and Lamb. 1545. Florey..8 35. Academic Press. Kim.. (1863).L. Sf = –1. 2.U. 5537. 119. L. La Mer. EXERCISES EXERCISES 2. C. Lee.O. 330. A. H. 12. Marangoni.
06 nm] T for 383 K: ρ = 951 kg m–3.0 mN m–1.6. 2.8 Following the procedure presented in Example 2.e.42  2 CAPILLARITY AND THE MECHANICS OF SURFACES Show by a qualitative argument that the formula does indeed correspond to the maximum pressure. For nitrogen at 77 K the surface tension is 8.2 kPa. The relevant data are: T for 378 K: ρ = 955 kg m–3. What is the minimum radius of these droplets if condensation is to occur on them and a ‘vapour trail’ form? Data: γ (H2O) = 75. p∞ = 120. [r = 12. After cooling. γ = 57. is equated to rc/cos θ.75 might be expected.018 kg mol−1. 2. γ = 57. [. calculate the minimum mean radii of curvature for bubbles forming at a depth of 5 cm in water at 378 K and 383 K.10 Draw an imaginary profile of the roughened surface of a solid and show by a series of sketches how a drop sitting on the surface can exhibit hysteresis in its macroscopic contact angle while retaining the same microscopic contact angle. [. the relative humidity is 110%).9 nm thick coating the inside of the tube. the radius of curvature of the liquid surface in the capillary.1. p∞ = 143. . Assume that prior adsorption of nitrogen has formed a layer 0. ρ(H2O) = 1030 kg m−3.4. the solid smoke particles emitted by the jet engines adsorb water vapour and can then be considered as minute spherical droplets.0 nm].2 mN m−1.9 mN m–1.6 Use the Kelvin equation to calculate the radius of an openended tube within which capillary condensation of nitrogen at 77 K and a relative pressure of 0.8 kPa. r. M(H2O) = 0. T = 275 K. [rc = 2.57 nm] 2.99 nm] 2.20.7 A jet aircraft is flying through a region where the air is 10% supersaturated with water vapour (i.85 mN m−1 and the molar volume is 34.7 cm3 mol−1. 2. Draw a diagram of this situation and prove this relationship.9 In deriving Eqn 2.
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