Macroscopic topics

The topic of capillarity concerns interfaces that are sufficiently mobile to assume an equilibrium shape. The most common examples are meniscuses, thin films, and drops formed by liquids in air or in another liquid. Since it deals with equilibrium configurations, capillarity occupies a place in the general framework of thermodynamics in the context of the macroscopic and statistical behavior of interfaces rather than the details of their molectdar structure. In this chapter we describe the measurement of surface tension and present some fundamental results. In Chapter III we discuss the thermodynamics of liquid surfaces. 

This chapter and the two that follow are introduced at this time to illustrate some of the many extensive areas in which there are important applications of surface chemistry. Friction and lubrication as topics properly deserve mention in a textbook on surface chemistiy, partly because these subjects do involve surfaces directly and partly because many aspects of lubrication depend on the properties of surface films. The subject of adhesion is treated briefly in this chapter mainly because it, too, depends greatly on the behavior of surface films at a solid interface and also because friction and adhesion have some interrelations. Studies of the interaction between two solid surfaces, with or without an intervening liquid phase, have been stimulated in recent years by the development of equipment capable of the direct measurement of the forces between macroscopic bodies. 

One of the intensively discussed topics was the question about the shape of atoms - a question with also high educational relevance, if we think of some students preconceptions. We can focus on two main positions One group of chemists observed that crystals always broke to parts with similar shapes to those of the original crystal. Therefore, their theory was that the smallest particles of atoms must have also the same shape as the macroscopic crystal. If we follow Domenico Guglielmini (1655-1710), the particles of sodium chloride would be cubic, those of calcspar would be triclinic. Hexagonal-prismatic and trigonal-prismatic crystals... 

All the macroscopic properties of polymers depend on a number of different factors prominent among them are the chemical structures as well as the arrangement of the macromolecules in a dense packing [1-6]. The relationships between the microscopic details and the macroscopic properties are the topics of interest here. In principle, computer simulation is a universal tool for deriving the macroscopic properties of materials from the microscopic input [7-14]. Starting from the chemical structure, quantum mechanical methods and spectroscopic information yield effective potentials that are used in Monte Carlo (MC) and molecular dynamics (MD) simulations in order to study the structure and dynamics of these materials on the relevant length scales and time scales, and to characterize the resulting thermal and mechanical proper-... 

So far we have considered the formation of tubules in systems of fixed molecular chirality. It is also possible that tubules might form out of membranes that undergo a chiral symmetry-breaking transition, in which they spontaneously break reflection symmetry and select a handedness, even if they are composed of achiral molecules. This symmetry breaking has been seen in bent-core liquid crystals which spontaneously form a liquid conglomerate composed of macroscopic chiral domains of either handedness.194 This topic is extensively discussed in Walba s chapter elsewhere in this volume. Some indications of this effect have also been seen in experiments on self-assembled aggregates.195,196... 

The first section of this book deals with current topics in network theory directed toward explaining the relationship between molecular architecture and macroscopic physical properties. The closely related questions of network formation and degradation are also discussed in this section. Deformation, fatigue, and fracture are discussed in the second section. The third section includes recent advances in cross-linking chemistry several chapters outline applications of new systems and detail the relationship between network structure and application properties. 

Is your order of order of topics Microscopic Macroscopic ... 

Following the comment on macroscopic then microscopic views made above, a suggestion for the minimum topics to cover would be ... 

One of the most important things to bear in mind in studying van der Waals forces is that this topic has ramifications that extend far beyond our discussion here. Van der Waals interactions, for example, contribute to the nonideality of gases and, closer to home, gas adsorption. We also see how these forces are related to surface tension, thereby connecting this material with the contents of Chapter 6 (see Vignette X below). These connections also imply that certain macroscopic properties and measurements can be used to determine the strength of van der Waals forces between macroscopic objects. We elaborate on these ideas through illustrative examples in this chapter. 

Frequently, however, the stability and, more generally, the microstructure and the macroscopic states of dispersions are determined by kinetic and thermodynamic considerations. Thermodynamics dictates what the equilibrium state will be, but it is often the kinetics that determines if that equilibrium state will be reached and how fast. This becomes a consideration of special importance in practice since most processing operations involve dynamic variables such as flow, sedimentation, buoyancy, and the like. Although a detailed discussion of this is beyond our scope here, it is important that we consider at least one example so that we can place some of the topics we discuss in this chapter in proper context. 

In view of the importance of macroscopic structure, further studies of liquid crystal formation seem desirable. Certainly, the rates of liquid crystal nucleation and growth are of interest in some applications—in emulsions and foams, for example, where formation of liquid crystal by nonequilibrium processes is an important stabilizing factor—and in detergency, where liquid crystal formation is one means of dirt removal. As noted previously and as indicated by the work of Tiddy and Wheeler (45), for example, rates of formation and dissolution of liquid crystals can be very slow, with weeks or months required to achieve equilibrium. Work which would clarify when and why phase transformation is fast or slow would be of value. Another topic of possible interest is whether the presence of an interface which orients amphiphilic molecules can affect the rate of liquid crystal formation at, for example, the surfaces of drops in an emulsion. 

The science of catalysis covers a large spectrum of phenomena. We observe—with some pride and joy—that this volume presents eight topics which, like the rainbow, form an almost systematic and complete sweep of the major classes of topics in catalysis. It spans from the most classical mechanistic study (P. W. Selwood), to a presentation of a hard practical application (M. Shelef et al). As we sweep across, we cover characterization studies of catalyst solids in terms of electronic (G. M. Schwab), surface chemical (H. A. Benesi and B. H. C. Winquist), as well as physicochemical and structural (F. E. Massoth) parameters, chemical reaction mechanisms and pathways (G. W. Keulks et al., and B. Gorewit and M. Tsutsui), and a topic on reactor behavior (V. Hlavacek and J, Votruba), which takes us from the single catalyst particle to the macroscopic total reactor operation. 

In this paper it has been attempted to provide an introductory overview of some of the various nonlinear optical characterization techniques that chemists are likely to encounter in studies of bulk materials and molecular structure-property relationships. It has also been attempted to provide a relatively more detailed coverage on one topic to provide some insight into the connection between the macroscopic quantities measured and the nonlinear polarization of molecules. It is hoped that chemists will find this tutorial useful in their efforts to conduct fruitful research on nonlinear optical materials. 

The principal goal is to define those factors which lead to the macroscopic chirality of the dendrimer. Despite numerous studies on this topic, the relation between the molecular chirality of the dendritic building blocks and the macroscopic chirality of molecules has still not been completely elucidated [12]. Yet an understanding of this relation is important for the development of new materials, including polymers, whose properties and function depend upon their macroscopic chirality [13]. 

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