Interfacial processes energy transfer

Fluidized beds are widely used to achieve either chemical reactions or physical processing that require interfacial contact between gas and particles. Heat transfer is important in many of these applications, either to obtain energy transfer between the solid and gas phases or to obtain energy transfer between the two-phase mixture and a heating/cooling medium. The latter case is particularly important for fluidized bed reactors which require heat addition or extraction in order to achieve thermal control with heats of reaction. 

Nanocarbon hybrids have recently been introduced as a new class of multifunctional composite materials [18]. In these hybrids, the nanocarbon is coated by a polymer or by the inorganic material in the form of a thin amorphous, polycrystalline or single-crystalline film. The close proximity and similar size domain/volume fraction of the two phases within a nanocarbon hybrid introduce the interface as a powerful new parameter. Interfacial processes such as charge and energy transfer create synergistic effects that improve the properties of the individual components and even create new properties [19]. We recently developed a simple dry wrapping method to fabricate a special class of nanocarbon hybrid, W03 /carbon nanotube (CNT) coaxial cable structure (Fig. 17.2), in which W03 layers act as an electrochromic component while aligned... 

In contrast to metal electrodes, for a semiconductor-electrolyte interface most of the potential drop is located in the semiconductor making it difficult to study interfacial processes using potential perturbation techniques [11,20,55,58,60-65,75-78]. H. Gerischer [76] proposed a model in which electrons and holes are considered as individual interfacial reactants. Distinct and preferential electron transfer reactions involve either the conduction band or valence band as dependent on the nature of the redox reactants of the electrolyte, with specific properties dependent upon the energy state location. 

Figure 5.4, one can easily understand why the interfacial electron transfer should take place in the 10-100 fsec range because this ET process should be faster than the photo-luminescence of the dye molecules and energy transfer between the molecules. Recently Zimmermann et al. [58] have employed the 20 fsec laser pulses to study the ET dynamics in the DTB-Pe/TiC>2 system and for comparison, they have also studied the excited-state dynamics of free perylene in toluene solution. Limited by the 20 fsec pulse-duration, from the uncertainty principle, they can only observe the vibrational coherences (i.e., vibrational wave packets) of low-frequency modes (see Figure 5.5). Six significant modes, 275, 360, 420, 460, 500 and 625 cm-1, have been resolved from the Fourier transform spectra of ultrashort pulse measurements. The Fourier transform spectrum has also been compared with the Raman spectrum. A good agreement can be seen (Figure 5.5). For detail of the analysis of the quantum beat, refer to Figures 5.5-5.7 of Zimmermann et al. s paper [58], These modes should play an important role not only in ET dynamics or excited-state dynamics, but also in absorption spectra. Therefore, the steady state absorption spectra of DTB-Pe, both in...

Electrochemical and photochemical processes are the most convenient inputs and outputs for interfacial supramolecular assemblies in terms of flexibility, speed and ease of detection. This chapter provides the theoretical background for understanding electrochemical and optically driven processes, both within supramolecular assemblies and at the ISA interface. The most important theories of electron and energy transfer, including the Marcus, Forster and Dexter models, are described. Moreover, the distance dependence of electron and energy transfer are considered and proton transfer, as well as photoisomerization, are discussed. 

Electron, energy and proton transfer or molecular rearrangements are the most important events that occur in interfacial supramolecular assemblies. In this chapter, the general theories of electron transfer, both within ISAs and across the film/electrode interface, are described. Moreover, photoinduced electron, energy and proton transfer processes are discussed. As this book focuses on supramolecular species, the treatment is restricted to intramolecular or interfacial processes without the requirement for prior diffusion of reactants. 

The most prevalent photoinduced processes in supramolecular and interfacial systems are electron transfer, energy transfer and nuclear motion, such as proton transfer and isomerization. Before discussing these processes, it is important to outline the fundamental properties of electronically excited states. 

There are two possible excited state interfacial electron transfer processes that can occur from a molecular excited state, S, created at a metal surface (a) the metal accepts an electron from S to form S+ or (b) the metal donates an electron to S to form S . Neither of these processes has been directly observed. The two processes would be competitive and unless there is some preference, no net charge will cross the interface. In order to obtain a steady-state photoelectrochemical response, back interfacial electron transfer reactions of S+ (or S ) to yield ground-state products must also be eliminated. Energy transfer from an excited sensitizer to the metal is thermodynamically favorable and allowed by both Forster and Dexter mechanisms [20, 21]. There exists a theoretical [20] and experimental [21] literature describing energy transfer quenching of molecular excited states by metals. How-... 

Figure 15. Energetics of the charge recombination following electron injection (/ i) from a dye excited state S into the conduction band of a semiconductor. Thermalization and/or trapping of injected electrons (Mh) takes place prior to the interfacial electron back transfer to the dye oxidized state S (/cb). The reaction free energy associated to the latter process depends upon the population of the electronic states in the solid and can be distributed over a broad range of values. Numerical potential data shown are those of the c/s-[Ru (dcbpy)2(NCS)2] Ti02 system.

In addition to emitting various types of radiation, nuclear waste materials are commonly mixtures of different compounds and even different phases. Energy transfer between phases and interfacial chemistry will affect the yields and types of products formed in these systems. Interfacial effects in radiation chemistry have long been observed, but the detailed mechanisms involved are not understood [3-5], Recent studies of water adsorbed on ceramic oxides clearly show that energy can migrate from the solid oxide phase to the water phase and lead to excess production of H2 [6, 7], This process complicates dosimetry because energy... 

It should also be mentioned that the Gibbs energy of ion transfer can be affected by complexation phenomena at the liquid liquid boundary. A classical example is given by the work of Koryta [25], who studied the transfer of from water to nitrobenzene assisted by dibenzo-18-crown-6. The complexation step decreases the energy of solvation of the cation in the organic phase, decreasing the formal transfer potential as defined in Eq. (5). Various mechanisms have been proposed for assisted ion-transfer processes, namely, aqueous complexation followed by transfer, transfer followed by complexation in the organic phase, transfer by interfacial complexation, or transfer by interfacial dissociation [26,27]. 

The first bracket on the left represents the Gibbs free energy transfer of asphaltene molecules and their deformation. The second term represents the interfacial Gibbs free energy, and the second bracket represents various terms for resin contribution to the micellization process. In Example 5.6, an alternative form of Eq. (5.64a) will be presented. 

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