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Physical Chemistry and Chemical Physics: A survey

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.

Physics, Chemistry and the Historical Context of Physical Chemistry


Physical chemistry is the scientific discipline at the frontier connecting the fields of chemistry and physics. In physics we study the phenomena related to matter and radiation from low energies up to the highest energies known to us. One considers motion and changes with time. Chemistry deals mostly with the states and transformations of matter at modest energies conserving the nature of the chemical elements. Before entering deeper into the scientific activities carried out in physical chemistry, we need to define matter, its possible states and forms. Matter exists in a variety of forms. Macroscopic matter which can be sensed by men without the use of any apparatus is composed of large aggregates of atomic and molecular entities. Molecules are composed of atoms which in turn are composed of nuclei and electrons. Nuclei can be further decomposed in protons and neutrons which, following the Standard Model,14 are built up by quarks. Quarks and electrons are considered to be elementary particles (as are also the photons of radiation). Particles in the form of quarks and up to molecules and macro-molecules define the microscopic scale of matter. On a larger scale, matter clumps into the forms of macroscopic bodies, planets, stars, galaxies, and clusters of galaxies. Our current understanding is that the state of microscopic matter and its time evolution are governed by the laws of quantum mechanics, while classical mechanics can be used to understand the state of macroscopic bodies and their motion. In both mechanics, when the speed of the relevant system approaches the speed of light, relativity theory has to be considered in addition. Macroscopic matter is composed of a large number of the order of 1023 molecular entities. Strictly, in terms of classical mechanics the state of macroscopic matter should be defined by the set of the time dependent position coordinates and the velocities or momenta of all its composing entities, which could be described by the classical equations of motion. Beyond this, the quantum mechanical equations of motion can be used, in principle. As such a complete description is seemingly unfeasible, the state of macroscopic matter is then best defined by a set of bulk properties that result from the form of the aggregation of these entities and that characterize the matter, inferring thus that an average is made of the position coordinates and velocities, A bulk property may for instance be the density of a solid, or its elasticity, the viscosity of a liquid or the compression modulus of a gas. The field connecting the detailed microscopic and macroscopic descriptions is classical and quantum statistical mechanics. At equilibrium it leads to statistical thermodynamics.

Reference Module in Chemistry, Molecular Sciences and Chemical Engineering

http://dx.doi.org/10.1016/B978-0-12-409547-2.05402-0

Physical Chemistry and Chemical Physics: A survey

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.

Subjects of Modern Physical Chemistry


High Resolution Spectroscopy
Spectroscopy is among the most powerful tools of chemistry and physics. Spectral line positions and intensities contain essential information on the structure of molecules and their internal dynamics. With increasing molecular size, the number of quantum states per energy interval becomes large and the distribution of spectral lines is difficult to be rationalized. Spectroscopic techniques have been developed on the basis of laser technology or interferometry which allow us to resolve complicated spectral patterns and gain insight into the dynamics and structure of molecules of increasing complexity.17 In this work, the subject title High-resolution Spectroscopy will cover topics related to time independent spectroscopy, including general aspects of the interaction between matter and radiation, as well as techniques and methods related to diffractometry and mass spectroscopy. Topics related to applied spectroscopy will be covered in the analytical chemistry and chemometrics subject of this work.

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.

Physical Chemistry and Chemical Physics: A survey Magnetic Resonance Spectroscopy

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.

Elementary Steps in Chemical Kinetics


A chemical reaction is elementary when only a few particles, typically one, two, or three, are involved in the actual reaction act (defining unimolecular, bimolecular, and trimolecular elementary reactions). The detailed investigation of such reactions became possible after 1960 with time resolved techniques and with molecular beam techniques, or with the isolation by trapping of molecules, ions or atoms in specially devised reaction chambers. The aforementioned ultrafast spectroscopic techniques are widely used, in particular today to investigate elementary reaction steps.

Complex Reaction Mechanisms of Coupled Elementary Reactions


Ordinary chemical reactions observed at the macroscopic scale are normally composed of several and often very many coupled elementary reaction steps. This branch of physical chemistry covers the investigation of reaction mechanisms, chain reactions, atmospheric chemistry, combustion chemistry, laser chemistry, and astrochemical kinetics. The unraveling of the underlying mechanisms is the object of the investigations in chemical kinetics of complex reactions. Here, also mathematical modeling by means of large sets of coupled differential equations is important.

Elementary Steps in Catalysis


Catalysts are compounds that accelerate (or slow down) chemical reactions without being themselves importantly consumed or altered during the reaction, rendering hence a significantly more efficient reaction yield. Rather than being a mere sub-division of chemical kinetics, catalysis has become a pilar of modern chemical industry and economy, the iron catalyzed synthesis of ammonia by Haber and Bosch being a landmark industrial production method. We distinguish gas phase, homogeneous, heterogeneous and enzyme catalysis. The investigation of elementary steps in heterogeneous catalysis,23 often considered as being an activity falling in the domain of surface science,24 is one example of the interdisciplinary character of physical chemical research. Elementary steps in catalysis include adsorption, diffusion or complexation. Proteins are the catalysts of biochemical enzyme kinetics, an important branch of homogeneous catalysis.

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.

Colloids and Transport Phenomena


Colloids are substances with sizes ranging between the micrometer (1 mm 103 m) and nanometer (1 nm 109 m) scale, often dispersed in other substances, such as smoke particles in air. Membranes and polymer films also compose colloidal systems. The interaction between such systems and other non-charged particles leads to characteristic transport phenomena which are studied in this branch of physical chemistry. Viscosity, thermal diffusion and the stabilisation of colloids are further topics of this sub-division of physical chemistry.

Physical Chemistry and Chemical Physics: A survey

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

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