Physical chemistry

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Between the flame and the flower is aerogel, whose synthesis has been aided greatly by physical chemistry. Aerogelflower filtered.jpg
Between the flame and the flower is aerogel, whose synthesis has been aided greatly by physical chemistry.

Physical chemistry is the study of macroscopic and microscopic phenomena in chemical systems in terms of the principles, practices, and concepts of physics such as motion, energy, force, time, thermodynamics, quantum chemistry, statistical mechanics, analytical dynamics and chemical equilibria.

Contents

Physical chemistry, in contrast to chemical physics, is predominantly (but not always) a supra-molecular science, as the majority of the principles on which it was founded relate to the bulk rather than the molecular or atomic structure alone (for example, chemical equilibrium and colloids).

Some of the relationships that physical chemistry strives to understand include the effects of:

  1. Intermolecular forces that act upon the physical properties of materials (plasticity, tensile strength, surface tension in liquids).
  2. Reaction kinetics on the rate of a reaction.
  3. The identity of ions and the electrical conductivity of materials.
  4. Surface science and electrochemistry of cell membranes. [1]
  5. Interaction of one body with another in terms of quantities of heat and work called thermodynamics.
  6. Transfer of heat between a chemical system and its surroundings during change of phase or chemical reaction taking place called thermochemistry
  7. Study of colligative properties of number of species present in solution.
  8. Number of phases, number of components and degree of freedom (or variance) can be correlated with one another with help of phase rule.
  9. Reactions of electrochemical cells.
  10. Behaviour of microscopic systems using quantum mechanics and macroscopic systems using statistical thermodynamics.
  11. Calculation of the energy of electron movement in molecules and metal complexes.

Key concepts

The key concepts of physical chemistry are the ways in which pure physics is applied to chemical problems.

One of the key concepts in classical chemistry is that all chemical compounds can be described as groups of atoms bonded together and chemical reactions can be described as the making and breaking of those bonds. Predicting the properties of chemical compounds from a description of atoms and how they bond is one of the major goals of physical chemistry. To describe the atoms and bonds precisely, it is necessary to know both where the nuclei of the atoms are, and how electrons are distributed around them. [2]

Disciplines

Quantum chemistry, a subfield of physical chemistry especially concerned with the application of quantum mechanics to chemical problems, provides tools to determine how strong and what shape bonds are, [2] how nuclei move, and how light can be absorbed or emitted by a chemical compound. [3] Spectroscopy is the related sub-discipline of physical chemistry which is specifically concerned with the interaction of electromagnetic radiation with matter.

Another set of important questions in chemistry concerns what kind of reactions can happen spontaneously and which properties are possible for a given chemical mixture. This is studied in chemical thermodynamics, which sets limits on quantities like how far a reaction can proceed, or how much energy can be converted into work in an internal combustion engine, and which provides links between properties like the thermal expansion coefficient and rate of change of entropy with pressure for a gas or a liquid. [4] It can frequently be used to assess whether a reactor or engine design is feasible, or to check the validity of experimental data. To a limited extent, quasi-equilibrium and non-equilibrium thermodynamics can describe irreversible changes. [5] However, classical thermodynamics is mostly concerned with systems in equilibrium and reversible changes and not what actually does happen, or how fast, away from equilibrium.

Which reactions do occur and how fast is the subject of chemical kinetics, another branch of physical chemistry. A key idea in chemical kinetics is that for reactants to react and form products, most chemical species must go through transition states which are higher in energy than either the reactants or the products and serve as a barrier to reaction. [6] In general, the higher the barrier, the slower the reaction. A second is that most chemical reactions occur as a sequence of elementary reactions, [7] each with its own transition state. Key questions in kinetics include how the rate of reaction depends on temperature and on the concentrations of reactants and catalysts in the reaction mixture, as well as how catalysts and reaction conditions can be engineered to optimize the reaction rate.

The fact that how fast reactions occur can often be specified with just a few concentrations and a temperature, instead of needing to know all the positions and speeds of every molecule in a mixture, is a special case of another key concept in physical chemistry, which is that to the extent an engineer needs to know, everything going on in a mixture of very large numbers (perhaps of the order of the Avogadro constant, 6 x 1023) of particles can often be described by just a few variables like pressure, temperature, and concentration. The precise reasons for this are described in statistical mechanics, [8] a specialty within physical chemistry which is also shared with physics. Statistical mechanics also provides ways to predict the properties we see in everyday life from molecular properties without relying on empirical correlations based on chemical similarities. [5]

History

Fragment of M. Lomonosov's manuscript 'Physical Chemistry' (1752) Lomonosov Chymiae Physicae 1752.jpg
Fragment of M. Lomonosov's manuscript 'Physical Chemistry' (1752)

The term "physical chemistry" was coined by Mikhail Lomonosov in 1752, when he presented a lecture course entitled "A Course in True Physical Chemistry" (Russian : Курс истинной физической химии) before the students of Petersburg University. [9] In the preamble to these lectures he gives the definition: "Physical chemistry is the science that must explain under provisions of physical experiments the reason for what is happening in complex bodies through chemical operations".

Modern physical chemistry originated in the 1860s to 1880s with work on chemical thermodynamics, electrolytes in solutions, chemical kinetics and other subjects. One milestone was the publication in 1876 by Josiah Willard Gibbs of his paper, On the Equilibrium of Heterogeneous Substances . This paper introduced several of the cornerstones of physical chemistry, such as Gibbs energy, chemical potentials, and Gibbs' phase rule. [10]

The first scientific journal specifically in the field of physical chemistry was the German journal, Zeitschrift für Physikalische Chemie , founded in 1887 by Wilhelm Ostwald and Jacobus Henricus van 't Hoff. Together with Svante August Arrhenius, [11] these were the leading figures in physical chemistry in the late 19th century and early 20th century. All three were awarded the Nobel Prize in Chemistry between 1901 and 1909.

Developments in the following decades include the application of statistical mechanics to chemical systems and work on colloids and surface chemistry, where Irving Langmuir made many contributions. Another important step was the development of quantum mechanics into quantum chemistry from the 1930s, where Linus Pauling was one of the leading names. Theoretical developments have gone hand in hand with developments in experimental methods, where the use of different forms of spectroscopy, such as infrared spectroscopy, microwave spectroscopy, electron paramagnetic resonance and nuclear magnetic resonance spectroscopy, is probably the most important 20th century development.

Further development in physical chemistry may be attributed to discoveries in nuclear chemistry, especially in isotope separation (before and during World War II), more recent discoveries in astrochemistry, [12] as well as the development of calculation algorithms in the field of "additive physicochemical properties" (practically all physicochemical properties, such as boiling point, critical point, surface tension, vapor pressure, etc.—more than 20 in all—can be precisely calculated from chemical structure alone, even if the chemical molecule remains unsynthesized),[ citation needed ] and herein lies the practical importance of contemporary physical chemistry.

See Group contribution method, Lydersen method, Joback method, Benson group increment theory, quantitative structure–activity relationship

Journals

Some journals that deal with physical chemistry include

Historical journals that covered both chemistry and physics include Annales de chimie et de physique (started in 1789, published under the name given here from 1815 to 1914).

See also

Related Research Articles

Chemistry is the scientific study of the properties and behavior of matter. It is a physical science within the natural sciences that studies the chemical elements that make up matter and compounds made of atoms, molecules and ions: their composition, structure, properties, behavior and the changes they undergo during reactions with other substances. Chemistry also addresses the nature of chemical bonds in chemical compounds.

The following outline is provided as an overview of and topical guide to chemistry:

<span class="mw-page-title-main">Outline of physical science</span> Hierarchical outline list of articles related to the physical sciences

Physical science is a branch of natural science that studies non-living systems, in contrast to life science. It in turn has many branches, each referred to as a "physical science", together is called the "physical sciences".

Quantum chemistry, also called molecular quantum mechanics, is a branch of physical chemistry focused on the application of quantum mechanics to chemical systems, particularly towards the quantum-mechanical calculation of electronic contributions to physical and chemical properties of molecules, materials, and solutions at the atomic level. These calculations include systematically applied approximations intended to make calculations computationally feasible while still capturing as much information about important contributions to the computed wave functions as well as to observable properties such as structures, spectra, and thermodynamic properties. Quantum chemistry is also concerned with the computation of quantum effects on molecular dynamics and chemical kinetics.

In physics, statistical mechanics is a mathematical framework that applies statistical methods and probability theory to large assemblies of microscopic entities. Sometimes called statistical physics or statistical thermodynamics, its applications include many problems in the fields of physics, biology, chemistry, neuroscience, computer science, information theory and sociology. Its main purpose is to clarify the properties of matter in aggregate, in terms of physical laws governing atomic motion.

<span class="mw-page-title-main">Thermodynamics</span> Physics of heat, work, and temperature

Thermodynamics is a branch of physics that deals with heat, work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these quantities is governed by the four laws of thermodynamics, which convey a quantitative description using measurable macroscopic physical quantities, but may be explained in terms of microscopic constituents by statistical mechanics. Thermodynamics applies to a wide variety of topics in science and engineering, especially physical chemistry, biochemistry, chemical engineering and mechanical engineering, but also in other complex fields such as meteorology.

<span class="mw-page-title-main">Theoretical chemistry</span> Branch of chemistry

Theoretical chemistry is the branch of chemistry which develops theoretical generalizations that are part of the theoretical arsenal of modern chemistry: for example, the concepts of chemical bonding, chemical reaction, valence, the surface of potential energy, molecular orbitals, orbital interactions, and molecule activation.

<span class="mw-page-title-main">Thermodynamic system</span> Body of matter in a state of internal equilibrium

A thermodynamic system is a body of matter and/or radiation separate from its surroundings that can be studied using the laws of thermodynamics.

In chemistry, reactivity is the impulse for which a chemical substance undergoes a chemical reaction, either by itself or with other materials, with an overall release of energy.

<span class="mw-page-title-main">Activated complex</span> Unstable configurations of atoms formed while a chemical reaction progresses

In chemistry, an activated complex represents a collection of intermediate structures in a chemical reaction when bonds are breaking and forming. The activated complex is an arrangement of atoms in an arbitrary region near the saddle point of a potential energy surface. The region represents not one defined state, but a range of unstable configurations that a collection of atoms pass through between the reactants and products of a reaction. Activated complexes have partial reactant and product character, which can significantly impact their behaviour in chemical reactions.

Chemical physics is a branch of physics that studies chemical processes from a physical point of view. It focuses on understanding the physical properties and behavior of chemical systems, using principles from both physics and chemistry. This field investigates physicochemical phenomena using techniques from atomic and molecular physics and condensed matter physics.

The scientific school of Quantum electrochemistry began to form in the 1960s under Revaz Dogonadze. Generally speaking, the field comprises the notions arising in electrodynamics, quantum mechanics, and electrochemistry; and so is studied by a very large array of different professional researchers. The fields they reside in include, chemical, electrical and mechanical engineering, chemistry and physics.

<span class="mw-page-title-main">Potential energy surface</span> Function describing the energy of a physical system in terms of certain parameters

A potential energy surface (PES) or energy landscape describes the energy of a system, especially a collection of atoms, in terms of certain parameters, normally the positions of the atoms. The surface might define the energy as a function of one or more coordinates; if there is only one coordinate, the surface is called a potential energy curve or energy profile. An example is the Morse/Long-range potential.

In thermodynamics, the interpretation of entropy as a measure of energy dispersal has been exercised against the background of the traditional view, introduced by Ludwig Boltzmann, of entropy as a quantitative measure of disorder. The energy dispersal approach avoids the ambiguous term 'disorder'. An early advocate of the energy dispersal conception was Edward A. Guggenheim in 1949, using the word 'spread'.

Physical organic chemistry, a term coined by Louis Hammett in 1940, refers to a discipline of organic chemistry that focuses on the relationship between chemical structures and reactivity, in particular, applying experimental tools of physical chemistry to the study of organic molecules. Specific focal points of study include the rates of organic reactions, the relative chemical stabilities of the starting materials, reactive intermediates, transition states, and products of chemical reactions, and non-covalent aspects of solvation and molecular interactions that influence chemical reactivity. Such studies provide theoretical and practical frameworks to understand how changes in structure in solution or solid-state contexts impact reaction mechanism and rate for each organic reaction of interest.

Reaction dynamics is a field within physical chemistry, studying why chemical reactions occur, how to predict their behavior, and how to control them. It is closely related to chemical kinetics, but is concerned with individual chemical events on atomic length scales and over very brief time periods. It considers state-to-state kinetics between reactant and product molecules in specific quantum states, and how energy is distributed between translational, vibrational, rotational, and electronic modes.

<span class="mw-page-title-main">Branches of physics</span> Overview of the branches of physics

Physics is a scientific discipline that seeks to construct and experimentally test theories of the physical universe. These theories vary in their scope and can be organized into several distinct branches, which are outlined in this article.

Food physical chemistry is considered to be a branch of Food chemistry concerned with the study of both physical and chemical interactions in foods in terms of physical and chemical principles applied to food systems, as well as the applications of physical/chemical techniques and instrumentation for the study of foods. This field encompasses the "physiochemical principles of the reactions and conversions that occur during the manufacture, handling, and storage of foods."

The following outline is provided as an overview of and topical guide to natural science:

In physical chemistry, there are numerous quantities associated with chemical compounds and reactions; notably in terms of amounts of substance, activity or concentration of a substance, and the rate of reaction. This article uses SI units.

References

  1. ↑ Torben Smith Sørensen (1999). Surface chemistry and electrochemistry of membranes. CRC Press. p. 134. ISBN   0-8247-1922-0.
  2. 1 2 Atkins, Peter and Friedman, Ronald (2005). Molecular Quantum Mechanics, p. 249. Oxford University Press, New York. ISBN   0-19-927498-3.
  3. ↑ Atkins, Peter and Friedman, Ronald (2005). Molecular Quantum Mechanics, p. 342. Oxford University Press, New York. ISBN   0-19-927498-3.
  4. ↑ Landau, L.D. and Lifshitz, E.M. (1980). Statistical Physics, 3rd Ed. p. 52. Elsevier Butterworth Heinemann, New York. ISBN   0-7506-3372-7.
  5. 1 2 Hill, Terrell L. (1986). Introduction to Statistical Thermodynamics, p. 1. Dover Publications, New York. ISBN   0-486-65242-4.
  6. ↑ Schmidt, Lanny D. (2005). The Engineering of Chemical Reactions, 2nd Ed. p. 30. Oxford University Press, New York. ISBN   0-19-516925-5.
  7. ↑ Schmidt, Lanny D. (2005). The Engineering of Chemical Reactions, 2nd Ed. pp. 25, 32. Oxford University Press, New York. ISBN   0-19-516925-5.
  8. ↑ Chandler, David (1987). Introduction to Modern Statistical Mechanics, p. 54. Oxford University Press, New York. ISBN   978-0-19-504277-1.
  9. ↑ Vucinich, Alexander (1963). Science in Russian culture. Stanford University Press. p. 388. ISBN   0-8047-0738-3.
  10. ↑ Josiah Willard Gibbs, 1876, "On the Equilibrium of Heterogeneous Substances", Transactions of the Connecticut Academy of Sciences
  11. ↑ Laidler, Keith (1993). The World of Physical Chemistry . Oxford: Oxford University Press. pp.  48. ISBN   0-19-855919-4.
  12. ↑ Herbst, Eric (May 12, 2005). "Chemistry of Star-Forming Regions". Journal of Physical Chemistry A. 109 (18): 4017–4029. Bibcode:2005JPCA..109.4017H. doi:10.1021/jp050461c. PMID   16833724.
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