Physical Chemistry

Physical chemistry is the branch of chemistry concerned with the interpretation of the phenomena of chemistry in terms of the underlying principles of physics. It lies at the interface of chemistry and physics, inasmuch as it draws on the principles of physics (especially quantum mechanics) to account for the phenomena of chemistry. It is also an essential component of the interpretation of the techniques of investigation and their findings, particularly because these techniques are becoming ever more sophisticated and because their full potential can be realized only by strong theoretical backing. Physical chemistry also has an essential role to play in the understanding of the complex processes and molecules characteristic of biological systems and modern materials.

Hot water is vaporizing as it is thrown into air that is −37.2°C (−35°F).
Hot water is vaporizing as it is thrown into air that is −37.2°C (−35°F).

Physical chemistry is traditionally divided into a number of disciplines, but the boundaries between them are imprecise. Thermodynamics is the study of transformations of energy. Although this study might seem remote from chemistry, in fact it is vital to the study of how chemical reactions yield work and heat. Thermodynamic techniques and analyses are also used to elucidate the tendency of physical processes (such as vaporization) and chemical reactions to reach equilibrium —the condition when there is no further net tendency to change. Thermodynamics is used to relate bulk properties of substances to each other, so that measurements of one may be used to deduce the value of another. Spectroscopy is concerned with the experimental investigation of the structures of atoms and molecules, and the identification of substances, by the observation of properties of the electromagnetic radiation absorbed, emitted, or scattered by samples. Microwave spectroscopy is used to monitor the rotations of molecules; infrared spectroscopy is used to study their vibrations; and visible and ultraviolet spectroscopy is used to study electronic transitions and to infer details of electronic structures. The enormously powerful technique of nuclear magnetic resonance is now ubiquitous in chemistry. The detailed, quantitative interpretation of molecular and solid-state structure is based in quantum theory and its use in the interpretation of the nature of the chemical bond. Diffraction studies, particularly x-ray diffraction and neutron diffraction studies, provide detailed information about the shapes of molecules, and x-ray diffraction studies are central to almost the whole of molecular biology. The scattering of neutrons, in inelastic neutron scattering, gives detailed information about the motion of molecules in liquids. The bridge between thermodynamics and structural studies is called statistical thermodynamics, in which bulk properties of substances are interpreted in terms of the properties of their constituent molecules. Another major component is chemical kinetics, the study of the rates of chemical reactions; it examines, for example, how rates of reactions respond to changes in conditions or the presence of a catalyst . Chemical kinetics is also concerned with the detailed mechanisms by which a reaction takes place, the sequences of elementary processes that convert reactants into products, including chemical reactions at solid surfaces (such as electrodes).

There are further subdivisions of these major fields. Thermochemistry is a branch of thermodynamics; its focus is the heat generated or required by chemical reactions. Electrochemistry is the study of how chemical reactions can produce electricity and how electricity can drive chemical reactions in "reverse" directions (electrolysis). Increasingly, attention is shifting from equilibrium electrochemistry (which is of crucial importance in interpreting the phenomena of inorganic chemistry) to dynamic electrochemistry, in which the rates of electron-transfer processes are the focus. Chemical kinetics has divisions that are based on the rates of reaction being studied. Special techniques for studying atomic and molecular processes on ever shorter time scales are being developed, and physical chemists are now able to explore reactions on a femtosecond (10 −15 second) timescale. Chemical kinetics studies are theoretical as well as experimental. One goal is to understand the course of reactions in step-by-step (and atomic) detail. Techniques are available that allow investigators to study collisions between individual molecules.

X-ray diffraction gives detailed information about shapes of molecules and is the basis of molecular biology.
X-ray diffraction gives detailed information about shapes of molecules and is the basis of molecular biology.

Physical chemistry is essential to understanding the other branches of chemistry. It provides a basis for understanding the thermodynamic influences (principally, the entropy changes accompanying reactions) that drive chemical reactions forward. It provides justifications for the schemes proposed in organic chemistry to predict and account for the reactions of organic compounds. It accounts for the structures and properties of transition metal complexes, organometallic compounds , the microporous materials known as zeolites that are so important for catalysis , and biological macromolecules, such as proteins and nucleic acids (including DNA ). It is fair to say that there is no branch of chemistry (including biochemistry) that can be fully understood without interpretations provided by physical chemistry.

There is a distinction between physical chemistry and chemical physics, although the distinction is hard to define and it is not always made. In physical chemistry, the target of investigation is typically a bulk system. In chemical physics, the target is commonly an isolated, individual molecule.

Theoretical chemistry is a branch of physical chemistry in which quantum mechanics and statistical mechanics are used to calculate properties of molecules and bulk systems. The greater part of activity in quantum chemistry, as the former is commonly termed, is the computation of the electronic structures of molecules and, often, their graphical representation. This kind of study is particularly important to the screening of compounds for potential pharmacological activity, and for establishing the mode of action of enzymes.

SEE ALSO Catalysis and Catalysts ; Electrochemistry ; Equilibrium ; Kinetics ; Quantum Chemistry ; Spectroscopy ; Theoretical Chemistry ; Thermodynamics .

Peter Atkins


Atkins, Peter, and de Paula, Julio (2002). Atkins' Physical Chemistry, 7th edition. New York: Oxford University Press.

Berry, R. Stephen; Rice, Stuart A.; and Ross, John (2000). Physical Chemistry, 2nd edition. New York: Oxford University Press.

Laidler, Keith James (1995). The World of Physical Chemistry. New York: Oxford University Press.

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