Solutes at Interfaces Structure and Thermodynamics

As with neat liquids at interfaces, the molecular structure of solvated molecules at an interface can be discussed using probability distribution functions.We 

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The first section of this book covers liquids and. solutions at equilibrium. I he subjects discussed Include the thcrmodvnamics of solutions, the structure of liquids, electrolyte solutions, polar solvents, and the spectroscopy of solvation. The next section deals with non-equilibrium properties of solutions and the kinetics of reactions in solutions. In the final section emphasis is placed on fast reactions in solution and femtochemistry. The final three chapters involve important aspects of solutions at interfaces. Fhese include liquids and solutions at interfaces, electrochemical equilibria, and the electrical double layer. Author W. Ronald Fawcett offers sample problems at the end of every chapter. The book contains introductions to thermodynamics, statistical thermodynamics, and chemical kinetics, and the material is arranged in such a way that It may be presented at different levels. Liquids, Solutions, and Interfaces is suitable for senior undergr.iduates and graduate students and will be of interest to analytical chemists, physical chemists, biochemists, and chemical environmental engineers. 

The interplay of phase separation and polymer crystallization in the multi-component systems influences not only the thermodynamics of phase transitions, but also their kinetics. This provides an opportunity to tune the complex morphology of multi-phase structures via the interplay. In the following, we further introduce three aspects of theoretical and simulation progresses enhanced phase separation in the blends containing crystallizable polymers accelerated crystal nucleation separately in the bulk phase of concentrated solutions, at interfaces of immiscible blends and of solutions, and in single-chain systems and interplay in diblock copolymers. In the end, we introduce the implication of interplay in understanding biological systems. 

Alexandridis P, Hatton TA. Polyethylene oxide)-poly(propylene oxide)- poly(ethylene oxide) block copolymer surfactants in aqueous solutions and at interfaces thermodynamics, structure, dynamics, and modeling (review). Colloid Surf A Physicochem Eng Aspects 1995 96 1 16. 

Alexandridis P and Hatton TA. Poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) Block Copolymer Surfactants in Aqueous Solutions and at Interfaces Thermodynamics, Structure, Dynamics, and Modeling (Review). 

Lastly, the mass transport processes at the crystal-liquid interface play a central role in crystallization. The influence of solvent and impurities on the structure and growth rates of faces is considered in this chapter along with its effect on the incorporation of impurities. The solvent solute-impurities interactions in solution will also be shown to interact in subtle, but important, ways with the interface during the crystallization process. With appropriate thermodynamic analysis it is shown how these interactions ultimately affect crystallization as a purification process. 

As shown in this chapter, the solvent can influence crystal product quality through its effect on crystallization kinetics, solution thermodynamics, and crystal interface structure. However, in many instances, the presence of impurities, reaction by-products, or corrosion products in the commercial system can override the solvent-induced behavior, yielding results different from those obtained in pure solvent. The strong influence of impurities at the parts per million level stems from the unique ability of certain impurities to adsorb at key growth sites on the crystal growth surface, as discussed in detail in Section 3.6. 

Apart from chemisorption, the state of reconstruction of a surface may be affected by an electric potential across the surface/ solution interface in an electrochemical system [28]. It was found that at electrode potentials positive to the potential of zero charge, the reconstruction is lifted and the surface changes to the bulk-truncated structure. Thus, the hex structure of a Au(l 00) electrode is lifted in 0.01 M HCIO4 solution at E> 0.60 V versus saturated calomel electrode, SCE, but already at E > 0.27 V versus SCE in 0.01 M H2SO4 solution, indicating the additional role of specific adsorption. These findings could recently be surprisingly well reproduced theoretically by a combination of DFT and thermodynamic considerations [30]. 

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