Contact angle thermodynamics

Why are the surface tension and contact angle thermodynamic properties of a substance What does it mean ... 

A. W. Neumann and J. K. Spelt, eds.. Applied Surface Thermodynamics. Interfacial Tension and Contact Angles, Marcel Dekker, New York, 1996. 

Since both sides of Eq. X-39 can be determined experimentally, from heat of immersion measurements on the one hand and contact angle data, on the other hand, a test of the thermodynamic status of Young s equation is possible. A comparison of calorimetric data for n-alkanes [18] with contact angle data [95] is shown in Fig. X-11. The agreement is certainly encouraging. 

Combination of Eq. 7 or Eq. 8 with the Young-Dupre equation, Eq. 3, suggests that the mechanical work of separation (and perhaps also the mechanical adhesive interface strength) should be proportional to (I -fcos6l) in any series of tests where other factors are kept constant, and in which the contact angle is finite. This has indeed often been found to be the case, as documented in an extensive review by Mittal [31], from which a few results are shown in Fig. 5. Other important studies have also shown a direct relationship between practical and thermodynamic adhesion, but a discussion of these will be deferred until later. It would appear that a useful criterion for maximizing practical adhesion would be the maximization of the thermodynamic work of adhesion, but this turns out to be a serious over-simplification. There are numerous instances in which practical adhesion is found not to correlate with the work of adhesion at ail, and sometimes to correlate inversely with it. There are various explanations for such discrepancies, as discussed below. 

Kom GA, Korn TM (1968) Mathematical handbook. McGraw-Hill, Boston Landau LD, Lifshitz EM (1959) Fluid mechanics, 2nd edn. Pergamon, London Morijama K, Inoue A (1992) The thermodynamic characteristics of two-phase flow in extremely narrow channels (the frictional pressure drop and heat transfer of boiling two-phase flow, analytical model). Heat Transfer Jpn Res 21 838-856 Ngan CD, Dussan EBV (1982) On the nature of the dynamic contact angle an experimental study. JEluidMech 118 27- 0... 

The above considerations show that the interfacial energy is of utmost importance in determining the thermodynamics and kinetics of the nucleation process. Unfortunately, however, there are considerable uncertainities on the values of interfacial free energies. Values determined from contact angle measurements are significantly lower than those determined from the dependence of solubility upon molar surface of the crystallites. Furthermore, reliable data on yes are lacking. 

Good, R.J, (1952). A thermodynamic derivation of Wenzel s modification of Young s equation contact angles Together with a theory of hysteresis. J. Am. Chem. Soc. 74, 5041-5042. 

The purpose of this paper will be to develop a generalized treatment extending the earlier mixed micelle model (I4) to nonideal mixed surfactant monolayers in micellar systems. In this work, a thermodynamic model for nonionic surfactant mixtures is developed which can also be applied empirically to mixtures containing ionic surfactants. The form of the model is designed to allow for future generalization to multiple components, other interfaces and the treatment of contact angles. The use of the pseudo-phase separation approach and regular solution approximation are dictated by the requirement that the model be sufficiently tractable to be applied in realistic situations of interest. 

In a subsequent theoretical analysis, Princen [26] initially used a model of infinitely long cylindrical drops to relate the geometric and thermodynamic properties of monodisperse HIPEs to the volume fraction of the dispersed phase. Thus the analysis could be restricted to a two-dimensional cross-section of the emulsion. Two principle emulsion parameters were considered the film thickness between adjacent drops (h) and the contact angle (0) [27-29]. The effects of these variables on the volume fraction, , both in the presence and absence of a compressive force on the emulsion, were considered. The results indicated that if both h and 0 are kept at zero, the maximum volume fraction () of the uncompressed emulsion is 0.9069, which is equivalent to = 0.7405 in real emulsions with spherical droplets (cf. Lissant s work). If 0 is zero (or constant) and h is increased, the maximum value of decreases on the other hand, increasing 0 with zero or constant h causes to increase above the value 0.9069, again at zero compression. This implies that, in the presence of an appreciable contact angle, without any applied compressive force, values of <(> in excess of the maximum value for undeformed droplets can occur. Thus, the dispersed phase... 

Fig. 14. Schematic illustration of a drop ofliquid spreading in contact with a solid surface, showing the relations between the relevant parameters the contact angle, 0 the solid/vapor interfacial free energy, Ysv the liquid/vapor interfacial free energy, yLV and the solid/liquid interfacial free energy, ySL. Young s equation describes the relationship between these parameters for a stationary drop at thermodynamic equilibrium [175]...

Another well-represented category was that of self-assembled monolayers (SAMS) and other supramolecular systems. The experiments on the SAMS included studies of the surface pKa of one system (110), the kinetics and thermodynamics of the self-assembly process (111), and the characterization of the SAM surface by study of solution contact angles (112). The experiments on supramolecular systems included studies on chemical equilibria in such systems (113, 114, 115), the kinetics of inclusion phenomena (116), and the use of solvatochromic probes in studying inclusion phenomena (117). 

Active control of wettability is a subject of current research activity and is beyond our scope here. However, the first step in this process is a study of interfacial tension and contact angle, their basis in thermodynamics, and methods to measure these properties. This is the objective of this chapter. 

Accepting Equation (54) and Young s equation, on which it is based, suggests calorimetry as a method for measuring contact angles. At this time this is not practical, but the implication that contact angle is a thermodynamic property is a very important realization. 

Although we established the thermodynamic significance of y early in the chapter, 0 has been allowed to drift. Its role is clear when we think of surface tension as a force We use 0 to project 7 in a specified direction. In thermodynamic terms, contact angle has been an outsider in our presentation. Young s equation is the remedy to this. Rewriting Equation (44), we observe... 

We have now established that both 7 and 6 have thermodynamic significance and have seen that their values as well as their temperature coefficients are of interest. In addition, we have seen that the measurement of contact angles presents some complications of its own. All this adds up to a need for more reliable and more accurate methods for the measurement of these parameters than those presented in Section 6.2. One of the most powerful strategies for this involves a second measurement made with the Wilhelmy plate. 

Laplace equation A thermodynamic derivation Determining surface tension from the Kelvin equation Heat of immersion from surface tension and contact angle Surface tension and the height of a meniscus at a wall Interfacial tensions from the Girifalco-Good-Fowkes equation... 

A number of chapters have been overhauled so thoroughly that they bear only minor resemblance to their counterparts in the first edition. The thermodynamics of polymer solutions is introduced in connection with osmometry and the drainage and spatial extension of polymer coils is discussed in connection with viscosity. The treatment of contact angle is expanded so that it is presented on a more equal footing with surface tension in the presentation of liquid surfaces. Steric stabilization as a protective mechanism against flocculation is discussed along with the classical DLVO theory. 

---