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de Strasbourg, Strasbourg, France R Marquardt, Universite M Quack, ETH Zu rich, Zu rich, Switzerland
2013 Elsevier Inc. All rights reserved.
Physics, Chemistry and the Historical Context of Physical Chemistry Subjects of Modern Physical Chemistry High Resolution Spectroscopy Ultrafast Spectroscopy Magnetic Resonance Spectroscopy Elementary Steps in Chemical Kinetics Complex Reaction Mechanisms of Coupled Elementary Reactions Elementary Steps in Catalysis Chemical Thermodynamics Electrochemistry Colloids and Transport Phenomena Biophysical Chemistry Summary References
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Glossary
Electrolyte Solution of ions conducting electricity. Ions Charged atoms or molecules. Thermochemistry The study of heat change in chemical reactions. Reaction quotient The ratio of product and reactant activities, often approximated as the ratio of concentrations.
Spectroscopy The study of matter using electromagnetic radiation of various frequencies. Equilibrium constant Quantity related to the reaction quotient at equilibrium. Rate constant Quantity characterising the rate of a chemical reaction.
http://dx.doi.org/10.1016/B978-0-12-409547-2.05402-0
The state of microscopic matter can be described, within quantum mechanics, by a wave function depending on the position coordinates of the composing entities and time. Determining this function, either experimentally or theoretically, has become a major activity in modern physics and, as will be detailed below, the knowledge of this function is fundamental in chemistry, too. Electric current through a body, or the radiation emitted from a star, even if sensible without the use of an apparatus, are physical manifestations of the very microscopic nature of matter, and for the understanding of these phenomena we ultimately need wave functions. When matter is transformed, we understand that its composition in terms of its building blocks changes. In chemistry, proper laws have been developed to analyze, characterize and predict such transformations among molecules. Traditionally, chemistry has been devoted solely to the study of transformations occurring among molecules which are described by the chemical reaction. While fundamental physics is essential for the understanding of atoms and molecules, and the elementary steps involved in the rearrangement of atoms into new molecular structures, chemistry is essential for the understanding and prediction of reactions involving the rearrangement of many atoms in molecules which are also commonly found in the domain of biology. It is conceivable that quasi-chemical laws could also be applied in the domain of elementary particle physics. In the opposite direction, its domain of application has already been extended to supramolecular systems covering selforganizing, complex matter,5 molecular machines,6 or life at the nanometer scale.7 Physical chemistry is the discipline in which the transformation of matter is studied by methods, concepts and techniques developed and used in physics. For instance, the variation of pressure in a reaction tube at constant temperature and volume can inform us about a change of the chemical composition of the gas. Similarly, the variation of the viscosity of a liquid may point out that its composition has changed. Monitoring the electric current through an electrolyte or analyzing the spectral decomposition of light absorbed or emitted during a chemical reaction have become standard scientific methods for unraveling the underlying transformation of matter. The former goes back to the studies of M. Faraday,8 whose activities gave rise to the physical chemical subdivision electrochemistry. The latter goes back to activities by Kirchhoff and Bunsen,9,10 who can be considered to be the founders of atomic spectroscopy. Bunsen, Kirchhoff and Faraday can be considered as forefathers of physical chemistry in the 19th century, long before the discovery by Thompson of the electron as a building block of matter in 1897 and before physical chemistry arose as a separate field in the late 19th century. Electrochemistry and spectroscopy have been major subjects of physico-chemical investigations since then. Two other very broad classifications of subfields are chemical thermodynamics as the study of chemical equilibria and chemical reaction kinetics as the study of the rate of chemical reactions. These can be related to physical thermodynamics and physical kinetics studying equilibria and kinetic phenomena without chemical reactions. Finally, physical chemistry can be considered to be merged with chemical physics and, in particular, atomic and molecular physics. Also theoretical chemistry and quantum chemistry can be considered as part of physical chemistry. The perception of physical chemistry as a modern scientific discipline began at the end of the 19th century, however, with vant r Physikalische Chemie,12 Perrin13 and Arrhenius,14 Hoff,11 Ostwald, who, together with vant Hoff founded the Zeitschrift fu Around this time Ostwald formed the phrase, physical chemistry is not a branch of chemistry, it is the chemistry of the future.15 Later the structure of the meanwhile well established discipline has been well described by Hinshelwood,16 Today, physical chemistry may be sub-divided into several subjects, as explained in the next section.
Ultrafast Spectroscopy
This kind of spectroscopy is performed with time resolved signal acquisition. With the advent of lasers in the decade of 1960, the time interval could be gradually shortened from the nanosecond (1 ns 109 s) to the femtosecond (1 fs 1015 s) time domain around 1980. The latter is the natural time domain of nuclear motion within molecules and defines hence the time scale for the en route observation18 of the breaking or formation of bonds, and the rearrangement of atoms in molecular compounds. The breakthrough rendered possible by this spectroscopy lead to the emergence of femtosecond chemistry as the domain of chemistry, in which the kinetics of the elementary chemical act can be studied in real time.19 After about the year 2000, time resolution in the subfemtosecond or attosecond (1 as 1018 s) time domain has become possible, allowing us to follow in real time the motion of electrons in atomic and molecular systems.20 Apart from being a major tool for disclosing very fast kinetics and molecular dynamics, ultrafast spectroscopy has also given rise to very powerful methods for structure determination, such as the two-dimensional infrared spectroscopy. The generation of ultra-short laser pulses also falls in this subject.
Magnetic resonance spectroscopy results from the interaction of the spin of a nucleus or an electron with a local magnetic induction at the position of the particle.21 The magnetic field is highly sensitive to the chemical environment of the particle and magnetic resonance spectroscopy has therefore become a very important method for structural analysis in chemistry and biology. This branch of physical chemistry can be further sub-divided into nuclear magnetic resonance,21 electron spin resonance or electron paramagnetic resonance spectroscopy,22 with special techniques in gas, liquid and solid phase spectroscopies.
Chemical Thermodynamics
In the forefront of physical chemical research in the 19th and at the beginning of the 20th century, chemical thermodynamics, also called chemical thermodynamics and thermochemistry, has become central to the determination of chemical equilibrium constants and reaction quotients. The influence of physical chemical concepts in the formulation of solution theory as well as in other areas of chemical science has been vividly reviewed by Hildebrand.15 Chemical thermodynamics include additionally studies in calorimetry, statistical thermodynamics, chemical and phase equibria and non-equilibrium thermodynamics.25
Electrochemistry
Electrochemical phenomena play a very important role in fundamental natural and industrial processes. Piles, batteries or fuel cells are examples of the large scale technological applications, while a living organism would not function in the absence of electrochemical reactions in the cells. Together with spectroscopy, electrochemistry is essential for the understanding and optimization of light harvesting processes in the search of solutions for sustainable energy supplies. Electrochemistry includes further the definition of standard and diffusion potentials and ion activity.
Biophysical Chemistry
The methods and concepts developed and used in the aforementioned sub-divisions of physical chemistry find nowadays a variety of applications in biology and life sciences. These applications have led to very specific techniques and theoretical formulations, which gave rise to this separate subject of physical chemistry. Particular subjects of biophysical chemistry include enzyme kinetics, the study of chemical evolution and the origin of life, bio-electrochemistry, photosynthesis, the primary processes of vision and membrane processes as well as neuro-physical chemistry.
Summary
In physical chemistry, the states and transformations of matter at modest energies conserving usually atomic entities, which is essentially the subject of chemistry, are studied by methods, concepts and techniques of physics. A variety of sub-divisions of the physical chemical discipline can nowadays be identified and will be further addressed in the sub-levels of this work. The language of physical chemistry has inevitably many mathematical elements. A detailed account of this language has been given in the Green Book of the International Union of Pure and Applied Chemistry.26 Of particular importance to the development of this language is theoretical chemistry. Following vant Hoff,11 this branch of chemistry also belongs to physical chemistry. However, because of its diversity and broad range, theoretical chemistry is addressed as a separate subject in this work. Also the study of symmetry and group theory for chemistry can be considered to be part of physical chemistry, best dealt with separately, partly included here in the section on high resolution spectroscopy.17
References
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. Glashow, S. L. Nucl. Phys. 1961, 22(4), 579588. Weinberg, S. Phys. Rev. Lett. 1967, 19, 12641266. Salam, A. In: Elementary Particle Theory, Relativistic Groups and Analyticity; Svartholm, N., Ed.; Wiley: London, 1968. Hoddeson, L.; Brown, L.; Riordan, M.; Dresden, M. The Rise of the Standard Model. Cambridge University Press: Cambridge, 1999. Lehn, J.-M. Rep. Progr. Phys. 2004, 67(3), 249. Champin, B.; Mobian, P.; Sauvage, J.-P. Chem. Soc. Rev. 2007, 36, 358366. Mann, S. Angew. Chem. 2008, 120(29), 53865401. Faraday, M. Experimental Researches in Chemistry and Physics. Richard Taylor and William Francis: London, 1859. Kirchhoff, G.; Bunsen, R. Poggendorfs Annalen 1860, 110, 161169. Kirchhoff, G.; Bunsen, R. Poggendorfs Annalen 1861, 112, 337381. ber Theoretische und Physikalische Chemie. Die Chemische Dynamik, 1st ed.; Friedrich Vieweg und Sohn: Braunschweig, 1898. vant Hoff, J. H. Vorlesungen u chimetrie und Verwandschaftslehre; Engelmann Verlag: Leipzig, 18871928. r Physikalische Chemie, Sto Ostwald, W., vant Hoff, J. H., Eds.; In Zeitschrift Fu de Chimie Physique I, Les Principes; Gauthier-Villars: Paris, 1903. Perrin, J., Ed.; In Traite Arrhenius, S., Ed.; In Lehrbuch der kosmischen Physik; Hirzel Verlag: Leipzig, 1903. Hildebrand, J. H. Annu. Rev. Phys. Chem. 1981, 32, 124. Hinshelwood, C. N., Ed.; In The Structure of Physical Chemistry; Clarendon Press: Oxford, 1951. Quack, M., Merkt, F., Eds.; Handbook of High-Resolution Spectroscopy; Wiley: Chichester, 2011, 3 vols. Polanyi, J. C. Faraday Discuss. Chem. Soc. 1979, 67, 129133. Zewail, A. H. Angew. Chem. Int. Ed. 2000, 39(15), 25872631. rner, H. J.; Corkum, P. B. Attosecond Spectroscopy. In: Handbook of High Resolution Spectroscopy; Quack, M., Merkt, F., Eds.; Wiley: Chichester, 2011; pp 17811803. Wo Ernst, R. R.; Bodenhausen, G.; Wokaun, A. Principles of Nuclear Magnetic Resonance in One and Two Dimensions. Clarendon Press: Oxford, 1987. Schweiger, A.; Jeschke, G. Principles of Pulse Electron Paramagnetic Resonance. Oxford University Press: Oxford, 2001. Ertl, G. Angew. Chem. Int. Ed. 1990, 29, 12191227. Somorjai, G. A. Introduction to Surface Chemistry and Catalysis. Wiley: New York, 1994. Glansdorff, P.; Prigogine, I. Thermodynamic Theory of Structure, Stability and Fluctuations. Wiley: London, 1971. m, B.; Kuchitsu, K.; Marquardt, R.; Mills, I.; Pavese, F.; Quack, M.; Stohner, J.; Strauss, H. L.; Takami, M.; Thor, A. J. Quantities, Units Cohen, E. R.; Cvitas, T.; Frey, J. G.; Holmstro and Symbols in Physical Chemistry, 3rd ed.; IUPAC and Royal Society of Chemistry: Cambridge, 2007 (reprinted with revisions 2011).