- Industry: Chemistry
- Number of terms: 1965
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The International Union of Pure and Applied Chemistry (IUPAC) serves to advance the worldwide aspects of the chemical sciences and to contribute to the application of chemistry in the service of people and the environment. As a scientific, international, non-governmental and objective body, IUPAC ...
The observable consequence of the limitation that the rate of a bimolecular chemical reaction in a homogeneous medium cannot exceed the rate of encounter of the reacting molecular entities.
If (hypothetically) a bimolecular reaction in a homogeneous medium occurred instantaneously when two reactant molecular entities made an encounter, the rate of reaction would be an encounter-controlled rate, determined solely by rates of diffusion of reactants. Such a hypothetical "fully diffusion controlled rate" is also said to correspond to "total microscopic diffusion control", and represents the asymptotic limit of the rate of reaction as the rate constant for the chemical conversion of the encounter pair into product (or products) becomes large relative to the rate constant for separation (or dissociation) of the encounter pair.
"Partial microscopic diffusion control" is said to operate in a homogeneous reaction when the rates of chemical conversion and of separation are comparable. (The degree of microscopic diffusion control cannot usually be determined with any precision.)
Industry:Chemistry
The observable consequence of the limitation that the rate of a bimolecular chemical reaction in a homogeneous medium cannot exceed the rate of encounter of the reacting molecular entities.
If (hypothetically) a bimolecular reaction in a homogeneous medium occurred instantaneously when two reactant molecular entities made an encounter, the rate of reaction would be an encounter-controlled rate, determined solely by rates of diffusion of reactants. Such a hypothetical "fully diffusion controlled rate" is also said to correspond to "total microscopic diffusion control", and represents the asymptotic limit of the rate of reaction as the rate constant for the chemical conversion of the encounter pair into product (or products) becomes large relative to the rate constant for separation (or dissociation) of the encounter pair.
"Partial microscopic diffusion control" is said to operate in a homogeneous reaction when the rates of chemical conversion and of separation are comparable. (The degree of microscopic diffusion control cannot usually be determined with any precision.)
Industry:Chemistry
(1) The (usually intramolecular) transfer of an atom or group during the course of a molecular rearrangement.
(2) The movement of a bond to a new position, within the same molecular entity, is known as "bond migration".
Allylic rearrangements, e.g.,
<center>RCH=CHCH<sub>2</sub>X → RCH(X)CH=CH<sub>2</sub></center>
exemplify both types of migration.
Industry:Chemistry
The term is applied to characterize the relative tendency of a group to participate in a rearrangement. In nucleophilic rearrangements (migration to an electron-deficient center), the migratory aptitude of a group is loosely related to its capacity to stabilize a partial positive charge, but exceptions are known, and the position of hydrogen in the series is often unpredictable.
Industry:Chemistry
The experimental limitation of the rate of reaction in solution by the rate of mixing of solutions of the two reactants. It can occur even when the reaction rate constant is several powers of 10 less than that for an encounter-controlled rate. Analogous (and even more important) effects of the limitation of reaction rates by the speed of mixing are encountered in heterogeneous (solid/liquid, solid/gas, liquid/gas) systems.
Industry:Chemistry
A monocyclic array of orbitals in which there is a single out-of-phase overlap (or, more generally, an odd number of out-of-phase overlaps) reveals the opposite pattern of aromatic character to Huckel systems; with 4n electrons it is stabilized (aromatic), whereas with 4n + 2 it is destabilized (antiaromatic). In the excited state 4n + 2 Mobius pi-electron systems are stabilized, and 4n systems are destabilized. No examples of ground-state Mobius pi systems are known, but the concept has been applied to transition states of pericyclic reactions.
The name is derived from the topological analogy of such an arrangement of orbitals to a Mobius strip.
Industry:Chemistry
In physical organic chemistry moiety is generally used to signify part of a molecule, e.g. in an ester R<sup>1</sup>COOR<sup>2</sup> the alcohol moiety is R<sup>2</sup>O. The term should not be used for a small fragment of a molecule.
Industry:Chemistry
In the context of stereochemistry, the term is restricted to the arrangements of atoms of a molecular entity in space that distinguishes stereoisomers, the isomerism of which is not due to conformational differences.
Industry:Chemistry
Any constitutionally or isotopically distinct atom, molecule, ion, ion pair, radical, radical ion, complex, conformer etc., identifiable as a separately distinguishable entity.
Molecular entity is used in this glossary as a general term for singular entities, irrespective of their nature, while chemical species stands for sets or ensembles of molecular entities. Note that the name of a compound may refer to the respective molecular entity or to the chemical species, e.g. methane, may mean a single molecule of CH<sub>4</sub> (molecular entity) or a molar amount, specified or not (chemical species), participating in a reaction.
The degree of precision necessary to describe a molecular entity depends on the context. For example "hydrogen molecule" is an adequate definition of a certain molecular entity for some purposes, whereas for others it is necessary to distinguish the electronic state and/or vibrational state and/or nuclear spin, etc. of the hydrogen molecule.
Industry:Chemistry
An empirical calculational method intended to give estimates of structures and energies for conformations of molecules. The method is based on the assumption of "natural" bond lengths and angles, deviation from which leads to strain, and the existence of torsional interactions and attractive and/or repulsive van der Waals and dipolar forces between non-bonded atoms. The method is also called "(empirical) force-field calculations".
Industry:Chemistry
