Physical chemistry experimental emphasis

The purpose of this series is to provide comprehensive up-to-date monographs in both well established disciplines and emerging research areas within the broad fields of chemical physics and physical chemistry. The books deal with both fundamental science and applications, and may have either a theoretical or an experimental emphasis. They are aimed primarily at researchers and graduate students... 

In addition to a general knowledge of laboratory techniques, creative research work requires the ability to apply two different kinds of theory. Many an experimental method is based on a special phenomenological theory of its own this must be well rmderstood in order to design the experiment properly and in order to calculate the desired physical property from the observed raw data. Once the desired result has been obtained, it is necessary to understand its significance and its interrelationship with other known facts. This requires a sound knowledge of the fundamental theories of physical chemistry (e g., thermodynamics, statistical mechanics, qrrantrrm mechanics, and kinetics). Cortsider-able emphasis has been placed on both kirrds of theory in this book. 

This volume is devoted to the various aspects of theoretical organic chemistry. In the nineteenth century, organic chemistry was primarily an experimental, empirical science. Throughout the twentieth century, the emphasis has been continually shifting to a more theoretical approach. Today, theoretical organic chemistry is a distinct area of research, with strong links to theoretical physical chemistry, quantum chemistry, computational chemistry, and physical organic chemistry. 

Gary Patterson is a chemical physicist with interests in polymer science, complex fluids, and colloid science. He attended Harvey Mudd College (B.S., chemistry, 1968) and Stanford University (Ph.D., physical chemistry, 1972). He was a member of the technical staff in the Chemical Physics Department at AT T Bell Laboratories from 1972 to 1984. He is a Fellow of the Royal Society of Chemistry and of the American Physical Society. He also received the National Academy of Sciences Award for Initiatives in Research in 1981. He has been a professor of chemical physics and polymer science at Carnegie Mellon University since 1984. In addition to teaching physical chemistry to chemical engineers and chemists, he teaches in the College of Humanities and Social Sciences. He conducts an active research program in experimental and theoretical chemical physics, with emphasis on the structure and dynamics of macromolecular systems. 

This chapter covers the basic terminology and theory related to the types of studies that are commonly used to provide information about a reaction mechanism. The emphasis is on the practicalities of determining rate constants and rate laws. More background material is available from general physical chemistry texts and books devoted to kinetics. The reader also is referred to the initial volumes of the series edited by Bamford and Tipper. Experimental techniques that are commonly used in inorganic kinetic studies are discussed in Chapter 9. 

This section includes two large essays on the Rehbinder effect, which involves a reversible physical-chemical (adsorption) action on the part of the medium on the mechanical behavior of solids, with an emphasis on the two main aspects associated with the effect. The first is the nniversal nature and selectiveness of the Rehbinder effect as a function of the chemical nature of the solid phase and the dispersion medium. The second aspect is related to the dependence of the extent and specific type of the effect on the experimental conditions and the real (defect) structure of the subject material. These two essays contain a summary of the studies conducted at the Russian Institnte of Physical Chemistry and Moscow State University over the years. 

An emphasis on a combination of theoretical and experimental work, with depth and skill in both, was characteristic of Gunnar Aniansson and made him a rather demanding research supervisor. He was an eminently good lecturer, in particular on the theoretical basis of physical chemistry, and eager to provide his students with a sound theoretical background. 

This chapter is devoted to an anlaysis of a few ab fine problems of physical chemistry, with a special emphasis on the extraction of the activation-energy distribution from experimental desorption kinetics. 

In this review we put less emphasis on the physics and chemistry of surface processes, for which we refer the reader to recent reviews of adsorption-desorption kinetics which are contained in two books [2,3] with chapters by the present authors where further references to earher work can be found. These articles also discuss relevant experimental techniques employed in the study of surface kinetics and appropriate methods of data analysis. Here we give details of how to set up models under basically two different kinetic conditions, namely (/) when the adsorbate remains in quasi-equihbrium during the relevant processes, in which case nonequilibrium thermodynamics provides the needed framework, and (n) when surface nonequilibrium effects become important and nonequilibrium statistical mechanics becomes the appropriate vehicle. For both approaches we will restrict ourselves to systems for which appropriate lattice gas models can be set up. Further associated theoretical reviews are by Lombardo and Bell [4] with emphasis on Monte Carlo simulations, by Brivio and Grimley [5] on dynamics, and by Persson [6] on the lattice gas model. 

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