Surface tension dynamic methods

Two dynamic methods have been developed for measurement of the surface tensions, the method of ripples first employed by Rayleigh and the vibrating jet method developed by Bohr. 

In some cases, a better agreement with the experimental surface tension isotherms and other data (dynamic surface tension, optical methods) is provided by the reorientation or aggregation model, respectively. It follows from the presented results that the reorientation model is more appropriate for oxyethylated surfactants and for surfactants which possess relatively high molar area, ro > 2.5-lO m /mol. At the same time, the aggregation and cluster models describe better the behaviour of surfactants with a relatively large Frumkin constant and low molar area, (o< 2.5-10 m /mol. 

Table 2.2 Dynamic Surface Tension Measurement Methods for Liquids ...

Surface tension methods measure either static or dynamic surface tension. Static methods measure surface tension at equilibrium, if sufficient time is allowed for the measurement, and characterize the system. Dynamic surface tension methods provide information on adsorption kinetics of surfactants at the air-liquid interface or at a liquid-liquid interface. Dynamic surface tension can be measured in a timescale ranging from a few milliseconds to several minutes [315]. However, a demarkation line between static and dynamic methods is not very sharp because surfactant adsorption kinetics can also affect the results obtained by static methods. It has been argued [316] that in many industrial processes, sufficient time is not available for the surfactant molecules to attain equilibrium. In such situations, dynamic surface tension, dependent on the rate of interface formation, is more meaningful than the equilibrium surface tension. For example, peaked alcohol ethoxylates, because they are more water soluble, do not lower surface tension under static conditions as much as the conventional alcohol ethoxylates. Under dynamic conditions, however, peaked ethoxylates are equally or more effective than conventional ethoxylates in lowering surface tension [317]. 

Since the drop volume method involves creation of surface, it is frequently used as a dynamic technique to study adsorption processes occurring over intervals of seconds to minutes. A commercial instrument delivers computer-controlled drops over intervals from 0.5 sec to several hours [38, 39]. Accurate determination of the surface tension is limited to drop times of a second or greater due to hydrodynamic instabilities on the liquid bridge between the detaching and residing drops [40],... 

The surface tension of a pure liquid should and does come out to be the same irrespective of the method used, although difficulties in the mathematical treatment of complex phenomena can lead to apparent discrepancies. In the case of solutions, however, dynamic methods, including detachment ones, often tend... 

It was made clear in Chapter II that the surface tension is a definite and accurately measurable property of the interface between two liquid phases. Moreover, its value is very rapidly established in pure substances of ordinary viscosity dynamic methods indicate that a normal surface tension is established within a millisecond and probably sooner [1], In this chapter it is thus appropriate to discuss the thermodynamic basis for surface tension and to develop equations for the surface tension of single- and multiple-component systems. We begin with thermodynamics and structure of single-component interfaces and expand our discussion to solutions in Sections III-4 and III-5. 

Surface tension is usually predicted using group additivity methods for neat liquids. It is much more difficult to predict the surface tension of a mixture, especially when surfactants are involved. Very large molecular dynamics or Monte Carlo simulations can also be used. Often, it is easier to measure surface tension in the laboratory than to compute it. 

Hsu and Berger [43] used the maximum bubble pressure method (MBP) to study the dynamic surface tension and surface dilational viscosity of various surfactants including AOS and have correlated their findings to time-related applications such as penetration and wetting. A recent discussion of the MBP method is given by Henderson et al. [44 and references cited therein]. 

Typically, the interface obtained with the versions of the VOF method described above is smeared over a few grid cells, which, on sufficiently fine grids, allows one to identify uniquely the simply connected volumes belonging to the different phases. Instead of regarding the dynamic conditions of Eqs. (132)-(134) as boundary conditions, surface tension can be implemented as a volume force in those cells where c lies between 0 and 1. In the method developed by Brackbill et al. [176], a momentum source term of the form... 

Recently, the newly developed time-resolved quasielastic laser scattering (QELS) has been applied to follow the changes in the surface tension of the nonpolarized water nitrobenzene interface upon the injection of cetyltrimethylammonium bromide [34] and sodium dodecyl sulfate [35] around or beyond their critical micelle concentrations. As a matter of fact, the method is based on the determination of the frequency of the thermally excited capillary waves at liquid-liquid interfaces. Since the capillary wave frequency is a function of the surface tension, and the change in the surface tension reflects the ion surface concentration, the QELS method allows us to observe the dynamic changes of the ITIES, such as the formation of monolayers of various surfactants [34]. 

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. 

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. 

On-line Determination of Dynamic Surface Tension by the Bubble-pressure Method... 

The Wilhelmy plate method provides an extremely simple approach that, unlike the ring detachment method, permits the measurement of continuously varying or dynamic surface tensions. If a thin plate (e.g., a microscope slide, a strip of platinum foil, or even a slip of filter paper) is attached to a microbalance and suspended so that its lower edge is just immersed in a liquid, the measured apparent weight Wj, is related to the actual weight of the plate Wp and the surface tension y by the following simple equation ... 

The method has been employed by Dorsey Phys. Rev. v. 213, 1897) and Griinmach Ann. derPhysik, xxxviil. 1018,1912) for the determination of the surface tensions of a number of salt solutions. It will be noted that a is dependent on the cube of the wave length, a factor militating against the general adoption of this method for the accurate determination of the surface tension. Again it is a difficult matter to decide how far such a method really yields a true value for the dynamic surface tension. 

As we shall have occasion to note in dealing with solutions, the composition of the surface phase is very different from that of the bulk liquid. When a liquid interface is newly formed the system is unstable until the surface phase has acquired its correct excess or deficit of solute by diffusion from or into the bulk of the solution. This process of diffusion is by no means instantaneous and, as has been observed in discussing the drop weight method, several minutes may elapse before equilibrium is established. In the ripple method the surfece is not renewed instantaneously but may be regarded as undergoing a series of expansions and contractions, thus we should anticipate that the value of the surface tension of a solution determined by this method would lie between those determined by the static and an ideal dynamic method respectively. 

More closely approaching the conditions desirable for determining the true dynamic surface tension is the vibrating jet method. 

In addition to the methods discussed here and in Section 6.2, there are a few other methods for measuring surface tension that are classified as dynamic methods as they involve the flow of the liquids involved (e.g., methods based on the dimensions of an oscillating liquid jet or of the ripples on a liquid film). As one might expect, the dynamic methods have their advantages as well as disadvantages. For example, the oscillating jet technique is ill-suited for air-liquid interfaces, but has been found quite useful in the case of surfactant solutions. A discussion of these methods, however, will require advanced fluid dynamics concepts that are beyond our scope here. As our primary objective in this chapter is simply to provide a basic introduction to surface tension and contact angle phenomena, we shall not consider dynamic methods here. Brief discussions of these methods and a comparison of the data obtained from different techniques are available elsewhere (e.g., see Adamson 1990 and references therein). 

What are some of the dynamic methods for measuring surface tension What are the differences between these and the static methods ... 

Equation (46), one form of the Gibbs equation, is an important result because it supplies the connection between the surface excess of solute and the surface tension of an interface. For systems in which y can be determined, this measurement provides a method for evaluating the surface excess. It might be noted that the finite time required to establish equilibrium adsorption is why dynamic methods (e.g., drop detachment) are not favored for the determination of 7 for solutions. At solid interfaces, 7 is not directly measurable however, if the amount of adsorbed material can be determined, this may be related to the reduction of surface free energy through Equation (46). To understand and apply this equation, therefore, it is imperative that the significance of r2 be appreciated. 

Bendure, R.L. 1971. Dynamic surface tension determination with maximum bubble pressure method. J. Colloid Interface Sci. 37 228-238. 

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