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Figure 220. The surface tension fof the air-water interface a @ function of temperature. (Data from Vargattik ral. 1983.) 2.9 THE SURFACE TENSION OF PURE LIQUIDS | 27 vapour pressure is high enough. The relative vapour pressure can be con- trolled by setting the temperature of the bulk liquid or adding a non-volatile solute. With an annulus of condensed liquid at the junction the cylinders are slowly separated so that a bridge of liquid formed between the mica surfaces. ‘When this bridge suddenly evaporates the separation is measured and from this rq can be calculated, Ie was found thatthe Kelvin equation held down to values of fm a8 low as 2.5nm for several organic liquids. This result also indicates that macroscopic values of and p hold at such low dimensions. For water, however, mean radii lower than $m do not follow predictions based con the macroscopic properties 2.9 The surface tension of pure liquids 2.9.1 Effect of temperature on surface tension “The chief factor affecting the surface tension of a pure liquid is the temper- ature (for example, Figure 2.20). Experimencally itis found that the surface tension ofa pure liquid decreases nearly linearly with temperature. It must, of course, be zero at the critical temperature, where the interface disappears. For some liquids the empirical Edtvés equation describes the dependence of surface tension on temperature: 4(M/p?*°) aT where M is the molar mass and p isthe density. 2.12 x 10°7J mol? K-! (2.20) 2.9.2 The surface tension of liquids Values for the surface tensions of some pure liquids are given in Table 2.2 ‘The very high surface tension of mercury, typical of values for metals, is attributable to short-range electron exchange interactions, the origin of so-called metallic bonds Itis notable that the surface tension of water is significantly higher than the surface tensions of all of the organic liquids. Only glycerol has a surface » Ae-water - tretocr a Sno g Eos 2 $a ene E co m~«MSCRSSCS«GC Temperature, 1 2 | 2 CAPILLARITY AND THE MECHANICS OF SURFACES Figure 2.21. Sketch of water molecule showing the tetrahedral distribstion of charge with bond lengths and angles, The charges (q) on the left epresent the charges arcributable tothe unshared electron pairs. € the clestronc charg. Based on the mode of Stillinger and Rahman 974 Table 2.2. The surface tensions of some common pure liquids at the ‘apour-liquid interface at 20°C. (From Jasper, 1972.) —— Liquid Surface tension, Liquid ‘Surface tension, yim! vine! Acetic acid 276 hexane 184 Acetone 25 Iobutyl alcohol 22.9 Benzene 289 Methanol ns ‘butyl aleohol 254 Mercury 486.5 Carbon tetrachloride 27.0 octane 216 Chloroform 272, Oleic acid 32.5 Cyclohexane 25.2 Propanoic acid 26.7 Ethyl acetate 240 npropyl alcohol 23.7 Ethanol 24 Pyridine 372 Di-ethy! ether 170 Toluene 28.5 Glycerol 64 Vinyl acetate 240 Ethylene glyco! 484 Water ns tension approaching that of water. Water and glycerol (plus some other liguids not shown in Table 2.2) are highly polar hydrogen-bonding liquids and it is this feature thar explains the high surface tensions. As water is a major component in most aspects of interface science, we will discuss it in detail below. 2.9.3 The hydrophobic-hydrophilic interaction “The structure of the water molecule is well known but it is important to consider here the dsteibution of electric charge in the molecule as this s the key to understanding its interactions with other molecules. The basic con- figuration is shown in Figure 2.21 ‘Water molecules tend to form hydrogen bonds with four other water molecules, giving a tetrahedral arrangement with each molecule providing the hydrogen atoms for two of the bonds and with the hydrogens atoms in the other two bonds coming from neighbouring water molecules. All four hydrogen bonds are approximately linear. In ice, this structure dominates, but although it tends to be retained in liquid water itis somewhat disordered and labile. Nevertheless the hydrogen bonds in liquid water have a strong tend- ency for directionality and linearity. It is also important to note that the strength of hydrogen bonds (10-40 kJ mol-') is appreciable greater than for typical van der Waals attraction (~1 kJ mol~*) but much les than for coval- cent and ionic bonds (~$00 kJ mol”) (Israelachvili, 1991, p. 127). The charges on water molecules and their strong tendency to form hydrogen bonds govern their interactions not only with other water molecules but with other materials as well

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