Wilhelmy

The methods so far discussed have required correction factors to the respective ideal equations. Yet there is one method, attributed to Wilhelmy [50] in 1863, that entails no such corrections and is very simple to use. 

Fig. 11-13. Apparatus for measuring the time dependence of interfacial tension (from Ref. 34). The air and aspirator connections allow for establishing the desired level of ftesh surface. IV denotes the Wilhelmy slide, suspended from a Cahn electrobalance with a recorder output.

The Wilhelmy slide has been operated in dynamic immersion studies to measure advancing and receding contact angles [59] (see Chapter X). It can also... 

It is not uncommon for this situation to apply, that is, for a Gibbs mono-layer to be in only slow equilibrium with bulk liquid—see, for example. Figs. 11-15 and 11-21. This situation also holds, of course, for spread monolayers of insoluble substances, discussed in Chapter IV. The experimental procedure is illustrated in Fig. Ill-19, which shows that a portion of the surface is bounded by bars or floats, an opposing pair of which can be moved in and out in an oscillatory manner. The concomitant change in surface tension is followed by means of a Wilhelmy slide. Thus for dilute aqueous solutions of a methylcellu-... 

Fig. ni-19. Trough for dynamic surface measurements A, stainless-steel dish B, aluminum mantle C, inlet thermostatting water D, lower PTFE bars E, oscillating bars F, attachment lower bars G, Wilhelmy plate. (From Ref. 140.)... 

The film pressure is defined as the difference between the surface tension of the pure fluid and that of the film-covered surface. While any method of surface tension measurement can be used, most of the methods of capillarity are, for one reason or another, ill-suited for work with film-covered surfaces with the principal exceptions of the Wilhelmy slide method (Section II-6) and the pendant drop experiment (Section II-7). Both approaches work very well with fluid films and are capable of measuring low values of pressure with similar precision of 0.01 dyn/cm. In addition, the film balance, considerably updated since Langmuir s design (see Section III-7) is a popular approach to measurement of V. 

In the Wilhelmy slide method, it seems best to partly immerse the slide and determine the change in height with constant upward pull or the change in pull at constant position of the slide. If the latter procedure is used, then... 

This method suffers from two disadvantages. Since it measures 7 or changes in 7 rather than t directly, temperature drifts or adventitious impurities can alter 7 and be mistakenly attributed to changes in film pressure. Second, while ensuring that zero contact angle is seldom a problem in the case of pure liquids, it may be with film-covered surfaces as film material may adsorb on the slide. This problem can be a serious one roughening the plate may help, and some of the literature on techniques is summarized by Gaines [69]. On the other hand, the equipment for the Wilhelmy slide method is simple and inexpensive and can be just as accurate as the film balance described below. 

Neumann has adapted the pendant drop experiment (see Section II-7) to measure the surface pressure of insoluble monolayers [70]. By varying the droplet volume with a motor-driven syringe, they measure the surface pressure as a function of area in both expansion and compression. In tests with octadecanol monolayers, they found excellent agreement between axisymmetric drop shape analysis and a conventional film balance. Unlike the Wilhelmy plate and film balance, the pendant drop experiment can be readily adapted to studies in a pressure cell [70]. In studies of the rate dependence of the molecular area at collapse, Neumann and co-workers found more consistent and reproducible results with the actual area at collapse rather than that determined by conventional extrapolation to zero surface pressure [71]. The collapse pressure and shape of the pressure-area isotherm change with the compression rate [72]. 

The capillary rise on a Wilhelmy plate (Section II-6C) is a nice means to obtain contact angles by measurement of the height, h, of the meniscus on a partially immersed plate (see Fig. 11-14) [111, 112]. Neumann has automated this technique to replace manual measurement of h with digital image analysis to obtain an accuracy of 0.06° (and a repeatability to 95%, in practice, of 0.01°) [108]. The contact angle is obtained directly from the height through... 

Yaminsky and Yaminskaya [114] have used a Wilhelmy plate to directly measure the interfacial tension (and hence infer the contact angle) for a surfactant solution on... 

Wilhelmy L 1850 uber das Gesetz nach welchem die Einwirkung der Sauren auf Rohrzucker Stattfiudet Ann. PhysikSI 413-29... 

Before equations such as Eqs. 6, 7 and 8 can be used, values for the surface energies have to be obtained. While surface energies of liquids may be measured relatively easily by methods such as the du Nouy ring and Wilhelmy plate, those of solids present more problems. Three approaches will be briefly described. Two involve probing the solid surface with a liquid or a gas, the third relies on very sensitive measurement of the force required to separate two surfaces of defined geometry. All involve applying judicious assumptions to the experimental results. 

FIG. 16 Fomation of a Langmuir lipid monolayer at the air/subphase interface and the subsequent crystallization of S-layer protein, (a) Amphiphilic lipid molecules are placed on the air/subphase interface between two barriers. Upon compression between the barriers, increase in surface pressure can be determined by a Wilhelmy plate system, (b) Depending on the final area, a liquid-expanded or liquid-condensed lipid monolayer is formed, (c) S-layer subunits injected in the subphase crystallized into a coherent S-layer lattice beneath the spread lipid monolayer and the adjacent air/subphase interface. 

Wilhelmy First quantitative analysis of reaction rates... 

Dynamic surface tension has also been measured by quasielastic light scattering (QELS) from interfacial capillary waves [30]. It was shown that QELS gives the same result for the surface tension as the traditional Wilhelmy plate method down to the molecular area of 70 A. QELS has recently utilized in the study of adsorption dynamics of phospholipids on water-1,2-DCE, water-nitrobenzene and water-tetrachloromethane interfaces [31]. This technique is still in its infancy in liquid-liquid systems and its true power is to be shown in the near future. 

Formation Wettability Studies that Incorporate the Dynamic Wilhelmy Plate Technique... 

The sessile drop method has several drawbacks. Several days elapse between each displacement, and total test times exceeding one month are not uncommon. It can be difficult to determine that the interface has actually advanced across the face of the crystal. Displacement frequency and distance are variable and dependent upon the operator. Tests are conducted on pure mineral surfaces, usually quartz, which does not adequately model the heterogeneous rock surfaces in reservoirs. There is a need for a simple technique that gives reproducible data and can be used to characterize various mineral surfaces. The dynamic Wilhelmy plate technique has such a potential. This paper discusses the dynamic Wilhelmy plate apparatus used to study wetting properties of liquid/liquid/solid systems important to the oil industry. 

The Wilhelmy hanging plate method (13) has been used for many years to measure interfacial and surface tensions, but with the advent of computer data collection and computer control of dynamic test conditions, its utility has been greatly increased. The dynamic version of the Wilhelmy plate device, in which the liquid phases are in motion relative to a solid phase, has been used in several surface chemistry studies not directly related to the oil industry (14- 16). Fleureau and Dupeyrat (17) have used this technique to study the effects of an electric field on the formation of surfactants at oil/water/rock interfaces. The work presented here is concerned with reservoir wettability. 

Figure 2 is a representation of the force balance on a Wilhelmy plate that has gone through one phase and has been wetted by a second phase. The three interfacial tensions are related to the contact angle (measured through phase 2) by the familiar Young equation... 

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