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Chemical.kinetics.fundamentals.and.Recent.developments

Chemical.kinetics.fundamentals.and.Recent.developments

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Published by jkbarbour55
Classic text on chemical kinetics for chemical engineering
Classic text on chemical kinetics for chemical engineering

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Published by: jkbarbour55 on Aug 31, 2011
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05/30/2013

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PREFACE
The object of this book is to present the basis of chemical kinetics incombination with its modern applications in chemistry, technology, and biochemistry. Abrief historical note is given below. The material is traditionally divided into formalkinetics and kinetics in the gaseous phase.The main concepts of chemical kinetics were formulated during the end of the19 h century when C. Guldberg and P. Waage formulated the law of action mass (1867)and Arrhenius his famous equation (1889) of the temperature dependence of the rateconstant. The book "Etudes de dynamique chimique" (1884) written by Vant-Hoff wasthe first monograph on chemical kinetics. In this monograph, chemical kinetics waspresented as simple chemical reactions. It was in the beginning of the 20 th century thatresearchers faced complicated mechanisms of chemical reactions and during the period1910-1935, chain reactions were discovered (M. Bodenstein, N. Semenov, SHinshelwood). In this period, chemical kinetics was transformed into the science ofcomplex chemical reactions in gaseous and liquid phases. Simultaneously, the theory ofthe elementary act of monomolecular and bimolecular reactions was advanced. Theabsolute rate theory was developed in the 1930s by S. Glasstone, K. Laidlerand and H.Eyring. New advancements in the theory of chemical reactions began with theappearance and development of quantum chemistry. The advanced theory of electronand proton transfer as "simple" models of chemical reactions opened the way for aprofound understanding of the quantum-mechanical factors affecting elementarychemical processes and simulated a cascade of experimental studies in chemistry andbiology (R. Marcus, V.G. Levich and J. Jortner).The study of chain reactions initiated interest in reactions involving activeintermediates as free atoms and radicals. An array of new experimental methods for thestudy of these very fast reactions was invented in the middle of the 20 h century. Themost important was EPR,
viz.,
a method of study of free radical reactions. A largenumber of experimental measurements of the rate constants of various reactions wereperformed during the last half of the century.A new field of chemistry was opened, namely the chemistry of labile particles:atoms, free radicals, radical ions, carbenes, etc. The fast development of experimentaltechniques suitable for monitoring fast and ultrafast processes led to the study ofmechanisms of energy exchange in collisions of particles and initiated the formation ofnonstationary kinetics.The objects of study in modern kinetics are a variety of different reactions ofmolecules, complexes, ions, free radicals, excited states of molecules, etc. A greatvariety of methods for the experimental study of fast reactions and the behavior ofreacting particles close to the top of the potential barrier were invented. Appropriatequantum-chemical methods are progressing rapidly. Computers are widely used inexperimental research and theoretical calculations. Databases accumulate a vast amountof kinetic information.One of the greatest creations of nature, biological catalysis, appears as achallenging problem to chemists of the 21 st century. The unique catalytic properties ofenzymes are their precise specificity, selectivity, high rate, and capacity to be regulated.Classical and modern physical chemistry, chemical kinetics, organic, inorganic and
 
viquantum-chemistry provide a variety of physical methods and establish a basis forinvestigation of structure and action mechanisms of enzymes. The general properties ofenzymes, the "ideal" chemical catalysts, are the formation of intermediates, smooththermodynamic relief along the reaction coordinate, fulfilment of all selection rules, theability to proceed and to stop temporarily and spatially, and compatibility with theambient media. These properties are attributable to multifunctional active centers, to theunique structure of protein globules, possessing both rigidity and flexibility, and theformation of catalytic ensembles.Biochemistry gives chemistry a plethora of knowledge about nearly "ideal"catalysts, the enzymes as catalysts close to the enzymes and opens the way for chemicalmodeling of the enzyme reactions.A major advantage of this work is that it is a comprehensive manual embracingpractically all the classical and modem areas of chemical kinetics. Special sections dealwith important subjects, which are not covered sufficiently in other manuals: 1) Methodsof calculation and determination of rate constants of reactions in gas and liquid phases;2) Modem areas such as laser chemistry (including pico- and femtochemistry),magnetochemistry, etc.; 3) Modem theories of electron transfer, including long-distanceelectron transfer; 4) Analysis of kinetics and mechanisms and voluminous illustrationsof "classical" processes, such as chain reactions, gas phase and homogeneous reactions(including homogeneous catalysis), etc.; 5) Discussion of enzymatic reactions from theviewpoint of chemical kinetics with emphasis on the special gains biocatalysis offerschemistry; 6) Analysis of the situations where enzymes cope with "tough" chemicalproblems under mild conditions: hydrolysis peptides, substrate oxidation, nitrogenfixation, long-distance electron transfer conversion of light energy to chemical energy,etc.; and 7) Chemical modeling of enzymes: achievements and problems.This monograph is intended for scientists working in various areas of chemistryand chemical and biotechnology, as well as for instructors, graduate and undergraduatestudents in departments of chemistry and biochemistry.The authors appreciate to the fullest extent the enormous contribution to thefoundation and development of modern chemical kinetics by a number of the mostprominent scientists, the patriarchs, whose photos appear at the beginning of this book.The authors are deeply indebted to Profs. R. Lumry, J. Jortner and S Efrima forthe encouragement and interest in this book. They are grateful to Drs. Elena Batova,Vassili Soshnikov, Mr. Pavel Parkhomyuk-Ben Arye and Mrs. Nataly Medvedeva fortheir invaluable help in preparation of the manuscript.

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