Liquid interfaces electrical change

The liquid-liquid interface is not only a boundary plane dividing two immiscible liquid phases, but also a nanoscaled, very thin liquid layer where properties such as cohesive energy, density, electrical potential, dielectric constant, and viscosity are drastically changed along with the axis from one phase to another. The interfacial region was anticipated to cause various specific chemical phenomena not found in bulk liquid phases. The chemical reactions at liquid-liquid interfaces have traditionally been less understood than those at liquid-solid or gas-liquid interfaces, much less than the bulk phases. These circumstances were mainly due to the lack of experimental methods which could measure the amount of adsorbed chemical species and the rate of chemical reaction at the interface [1,2]. Several experimental methods have recently been invented in the field of solvent extraction [3], which have made a significant breakthrough in the study of interfacial reactions. 

We can observe electro-osmosis directly with an optical microscope using liquids, which contain small, yet visible, particles as markers. Most measurements are made in capillaries. An electric field is tangentially applied and the quantity of liquid transported per unit time is measured (Fig. 5.13). Capillaries have typical diameters from 10 fim up to 1 mm. The diameter is thus much larger than the Debye length. Then the flow rate will change only close to a solid-liquid interface. Some Debye lengths away from the boundary, the flow rate is constant. Neglecting the thickness of the electric double layer, the liquid volume V transported per time is... 

A micro channel of height 2 H is equipped with electrodes at the upper (L/,) and lower (L walls [28], These electrodes are used to control the C, potential at the solid-liquid interface. In this way, the direction of the electroosmotic flow near the interface can be changed locally. The external electric field is given as Ex. 

The liquid-liquid interface formed between two immissible liquids is an extremely thin mixed-liquid state with about one nanometer thickness, in which the properties such as cohesive energy density, electrical potential, dielectric constant, and viscosity are drastically changing from those of bulk phases. Solute molecules adsorbed at the interface can behave like a 2D gas, liquid, or solid depending on the interfacial pressure, or interfacial concentration. But microscopically, the interfacial molecules exhibit local inhomogeneity. Therefore, various specific chemical phenomena, which are rarely observed in bulk liquid phases, can be observed at liquid-liquid interfaces [1-3]. However, the nature of the liquid-liquid interface and its chemical function are still less understood. These situations are mainly due to the lack of experimental methods required for the determination of the chemical species adsorbed at the interface and for the measurement of chemical reaction rates at the interface [4,5]. Recently, some new methods were invented in our laboratory [6], which brought a breakthrough in the study of interfacial reactions. 

A more recently developed force measurement technique, coined the liquid siu-face force apparatus (LSFA), brings a drop made from a micropipette close to a flat liquid/liquid interface [29-32]. A piezo electric drive is used to change the position of the micropipette while the deflection of the pipette and the radius of the drop are recorded with piezo motion. The drop radius and thus the film thickness between the two liquid/liquid interfaces are recorded using interferometry. The method requires a calibration of the interferometer, where the drop must come into contact with the other liquid interface. The distance resolution of the film is about 1 nm at a 50-nm separation and 5 nm at a separation of 10 nm. This is a very robust technique where the authors have proposed attaching a particle to the end of the pipette instead of a drop [29]. In comparing this method to AFM, the only drawback of the LSFA is the weaker distance resolution. It is important point out that both methods required a contact point for distance calibration. 

In all of these systems, certain aspects of the reactions can be uniquely related to the properties of a surface. Surface properties may include those representative of the bulk material, ones unique to the interface because of the abrupt change in density of the material, or properties arising from the two-dimensional nature of the surface. In this article, the structural, thermodynamic, electrical, optical, and dynamic properties of solid surfaces are discussed in instances where properties are different from those of the bulk material. Predominantly, this discussion focuses on metal surfaces and their interaction with gas-phase atoms and molecules. The majority of fundamental knowledge of molecular-level surface properties has been derived from such low surface area systems. The solid-gas interface of high surface area materials has received much attention in the context of separation science, however, will not be discussed in detail here. The solid-liquid interface has primarily been treated from an electrochemical perspective and is discussed elsewhere see Electrochemistry Applications in Inorganic Chemistry). The surface properties of liquids (liquid-gas interface) are largely unexplored on the molecular level experimental techniques for their study have begun only recently to be developed. The information presented here is a summary of concepts a more complete description can be found in one of several texts which discuss surface properties in more detail. ... 

Fundamental investigation of the system at the molecular level. This requires investigations of the structure of the solid/liquid interface, namely the structure of the electrical double layer (for charge-stabiUsed suspensions), adsorption of surfactants, polymers and polyelectrolytes and conformation of the adsorbed layers (e.g., the adsorbed layer thickness). It is important to know how each of these parameters changes with the conditions, such as temperature, solvency of the medium for the adsorbed layers, and the effect of addition of electrolytes. 

A liquid interface is the first requirement for all the many forms of capillarity. At least one phase must be sufficiently fluid. The shape of a liquid with an interface to air or another liquid is determined by the surface or interface tension. The shape of a liquid surface or interface at rest changes only when the surface tension, forces of gravity, and in some cases the electric field forces (Lorentz forces) are altered, provided the solid boundaries have constant dimensions and certain angles. The shape of pendant drops, sessile drops on a solid substrate, a meniscus against a solid wall and the length of so-called surface waves are well-known examples of capillarity. These phenomena need separate examination of liquid interfaces, as the surface state between two phases cannot be deduced from their bulk properties. 

The classical H-S equation is used to predict the electro-osmotic velocity of the fluid as a function of the electric field and the electrokinetic potential of the clay. Both of these parameters vary during electrokinetic transport, and result in a nonlinear process. New models have been developed that uncouple the electro-osmotic velocity from the applied field taking that surface conductivity and the resulting proportion of the current transferred over the solid-liquid interface are used as intrinsic properties of the clay to describe the velocity (Chapter 2). The pH changes affect the zeta potential, and thereby electro-osmotic conductivity. Thus, electro-osmotic conductivity changes as the dynamic changes in soil pH occur. 

The response of piezoelectric devices propagating shear horizontal acoustic plate modes (SH-APMs) has been modeled and experimentally characterized for variations in surface mass, liquid rheological properties, and solution dielectric coefficient and electrical conductivity. The nature of the SH-APM and its propagation characteristics are outlined and used to describe a range of Interactions at the solid/liquid interface. Sensitivity to sub-monolayer mass changes is demonstrated and a Cu sensor is described. The APM device is compared to the surface acoustic wave device and the quartz crystal microbalance for liquid sensing applications. 

Both Nomura (78, 79) and Bruckenstein (80, 81) have used bulk wave devices oscillating at a liquid interface for electrochemical studies. In one study it was reported that 0.02 monolayer electrode coverage could be detected for a metal of molecular weight 100 (81). These studies indicate that selective detection can occur if the analyte is electroactive such that oxidation or reduction causes a surface mass change and if no other sample matrix component is electroactive at the same electrical potential. 

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