Liquids interface effects

Similar to the molecular photosensitizers described above, solid semiconductor materials can absorb photons and convert light into electrical energy capable of reducing C02. In solution, a semiconductor will absorb light, and the electric field created at the solid-liquid interface effects the separation of photo-excited electron-hole pairs. The electrons can then carry out an interfacial reduction reaction at one site, while the holes can perform an interfacial oxidation at a separate site. In the following sections, details will be provided of the reduction of C02 at both bulk semiconductor electrodes that resemble their metal electrode counterparts, and semiconductor powders and colloids that approach the molecular length scale. Further information on semiconductor systems for C02 reduction is available in several excellent reviews [8, 44, 104, 105],... 

Shi, C. N. and F. C. Anson, Rates of electron-transfer across Liquid/Liquid interfaces. Effects of changes in driving force and reaction reversibility, J Phys Chem B, Vol. 105, (2001) p. 8963. 

D. Michael and I. Benjamin,/. Chem. Phys., 107,5684 (1997). Electronic Spectra of Dipolar Solutes at Liquid-Liquid Interfaces. Effect of Interface Structure and Polarity. 

C. Shi and F. C. /3nson, /. Phys. Chem. B., 105 (2001). Rates of Electron-Transfer Across Liquid/Liquid Interfaces. Effects of Changes in Driving Force and Reaction Reversibility. 

This section represents a continuation of Section VII-5, which dealt primarily with the direct estimation of surface quantities at a solid-gas interface. Although in principle some of the methods described there could be applied at a solid-liquid interface, very little has been done apart from the study of the following Kelvin effect and nucleation studies, discussed in Chapter IX. 

It was pointed out in Section XIII-4A that if the contact angle between a solid particle and two liquid phases is finite, a stable position for the particle is at the liquid-liquid interface. Coalescence is inhibited because it takes work to displace the particle from the interface. In addition, one can account for the type of emulsion that is formed, 0/W or W/O, simply in terms of the contact angle value. As illustrated in Fig. XIV-7, the bulk of the particle will lie in that liquid that most nearly wets it, and by what seems to be a correct application of the early oriented wedge" principle (see Ref. 48), this liquid should then constitute the outer phase. Furthermore, the action of surfactants should be predictable in terms of their effect on the contact angle. This was, indeed, found to be the case in a study by Schulman and Leja [49] on the stabilization of emulsions by barium sulfate. 

Films spread at liquid-liquid interfaces or on liquids other than water are discussed followed by the important effects of charged monolayers on water. Finally, the most technologically important application of Langmuir films, the Langmuir-Blodgett film deposited on a solid substrate, is reviewed. 

Liquid holdup is made up of a dynamic fraction, 0.03 to 0.25, and a stagnant fraction, 0.01 to 0.05. The high end of the stagnant fraction includes the hquid that partially fills the pores of the catalyst. The effective gas/liquid interface is 20 to 50 percent of the geometric surface of the particles, but it can approach 100 percent at high hquid loads with a consequent increase of reaction rate as the amount of wetted surface changes. 

Surface tension A characteristic of a liquid surface, with effects at liquid-gas or liquid-liquid interfaces. 

Here r is the distance between the centers of two atoms in dimensionless units r = R/a, where R is the actual distance and a defines the effective range of the potential. Uq sets the energy scale of the pair-interaction. A number of crystal growth processes have been investigated by this type of potential, for example [28-31]. An alternative way of calculating solid-liquid interface structures on an atomic level is via classical density-functional methods [32,33]. 

From experimental results, the variation of film thickness with rolling velocity is continuous, which validates a continuum mechanism, to some extent in TFL. Because TFL is described as a state in which the film thickness is at the molecular scale of the lubricants, i.e., of nanometre size, common lubricants may exhibit microstructure in thin films. A possible way to use continuum theory is to consider the effect of a spinning molecular confined by the solid-liquid interface. The micropolar theory will account for this behavior. 

There is a clinical need for non-natural, functional mimics of the lung surfactant (LS) proteins B and C (SP-B and SP-C), which could be used in a biomimetic LS replacement to treat respiratory distress syndrome (RDS) in premature infants [56]. An effective surfactant replacement must meet the following performance requirements (i) rapid adsorption to the air-liquid interface, (ii) re-spreadabihty... 

Fig. 26. The effect of shear on a range of enzymes with a stainless steel disc at a mean velocity gradient of 6490 s at 30 °C, in the presence of an air/liquid interface. Each data point in the figure is the mean value of 4 replicates and is given as a percentage of the control value [107]...

In most cases the only appropriate approach to model multi-phase flows in micro reactors is to compute explicitly the time evolution of the gas/liquid or liquid/ liquid interface. For the motion of, e.g., a gas bubble in a surrounding liquid, this means that the position of the interface has to be determined as a function of time, including such effects as oscillations of the bubble. The corresponding transport phenomena are known as free surface flow and various numerical techniques for the computation of such flows have been developed in the past decades. Free surface flow simulations are computationally challenging and require special solution techniques which go beyond the standard CFD approaches discussed in Section 2.3. For this reason, the most common of these techniques will be briefly introduced in... 

More than 20 years ago, Matsushita et al. observed macroscopic patterns of electrodeposit at a liquid/air interface [46,47]. Since the morphology of the deposit was quite similar to those generated by a computer model known as diffusion-limited aggregation (D LA) [48], this finding has attracted a lot of attention from the point of view of morphogenesis in Laplacian fields. Normally, thin cells with quasi 2D geometries are used in experiments, instead of the use of liquid/air or liquid/liquid interfaces, in order to reduce the effect of convection. 

Markovic NM, Schmidt TJ, Grgur BN, Gasteiger HA, Behm RJ, Ross PN. 1999. The effect of temperature on the surface process at the Pt(lll)-liquid interface Hydrogen adsorption, oxide formation and CO oxidation. J Phys Chem B 103 8568. 

Clearly, then, the chemical and physical properties of liquid interfaces represent a significant interdisciplinary research area for a broad range of investigators, such as those who have contributed to this book. The chapters are organized into three parts. The first deals with the chemical and physical structure of oil-water interfaces and membrane surfaces. Eighteen chapters present discussion of interfacial potentials, ion solvation, electrostatic instabilities in double layers, theory of adsorption, nonlinear optics, interfacial kinetics, microstructure effects, ultramicroelectrode techniques, catalysis, and extraction. 

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