- 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 ...
A radical that carries an electric charge. A positively charged radical is called a "radical cation" (e.g., the benzene radical cation C<sub>6</sub>H<sub>6</sub><sup>.+</sup>); a negatively charged radical is called a "radical anion" (e.g., the benzene radical anion C<sub>6</sub>H<sub>6</sub><sup>. -</sup> or the benzophenone radical anion Ph<sub>2</sub>C-O<sup>. -</sup>). Commonly, but not necessarily, the odd electron and the charge are associated with the same atom.
Unless the positions of unpaired spin and charge can be associated with specific atoms, superscript dot and charge designations should be placed in the order <sup>.+</sup> or <sup>. -</sup> suggested by the name "radical ion", (e.g C<sub>3</sub>H<sub>6</sub><sup>.+</sup>).
Note: In the previous edition of the Glossary, it was recommended to place the charge designation directly above the centrally placed dot. However, this format is now discouraged because of the difficulty of extending it to ions bearing more than one charge, and/or more than one unpaired electron.
In mass spectroscopic usage the symbol for the charge precedes the dot representing the unpaired electron.
Industry:Chemistry
The term is used to identify two radicals in close proximity in solution, within a solvent cage. They may be formed simultaneously by some unimolecular process, e.g., peroxide decomposition, or they may have come together by diffusion. While the radicals are together, correlation of the unpaired electron spins of the two species cannot be ignored: this correlation is responsible for the CIDNP phenomenon.
Industry:Chemistry
The cleavage of one or several bonds resulting from exposure to high-energy radiation. The term is also often used loosely to specify the method of irradiation ("pulse radiolysis") used in any radiochemical reaction, not necessarily one involving bond cleavage.
Industry:Chemistry
An expression for the rate of reaction of a particular reaction in terms of concentrations of chemical species and constant parameters (normally rate coefficients and partial orders of reaction) only. For examples of rate laws see equations (1) to (3) under kinetic equivalence, and (1) under steady state.
Industry:Chemistry
These terms are best regarded as synonymous with rate-controlling step. However, other meanings that have been given to them should be mentioned, as it is necessary to be aware of them in order to avoid confusion:
Sometimes the term rate-determining is used as a special case of rate-controlling, being assigned only to an initial slow step which is followed by rapid steps. Such a step imposes an upper limit on the rate, and has also been called rate-limiting.
In view of the considerable danger of confusion when special meanings are applied to rate-determining and rate-limiting, it is recommended that they be regarded as synonymous, with the meaning explained under the entry rate-controlling step.
Industry:Chemistry
(1) For an internal motion of a molecular entity corresponding to progress over a transition state (energy maximum), any change that makes the motion more difficult will lead to a new molecular geometry at the energy maximum, in which the motion has proceeded further. Changes that make the motion less difficult will have the opposite effect. (This rule corresponds to the Hammond principle.
(2) For an internal motion of a molecular entity that corresponds to a vibration, any change that tends to modify the equilibrium point of the vibration in a particular direction will actually shift the equilibrium in that direction.
(3) Effects on reacting bonds (bonds made or broken in the reaction) are the most significant. The bonds nearest the site of structural change are those most strongly affected.
Industry:Chemistry
A geometric parameter that changes during the conversion of one (or more) reactant molecular entities into one (or more) product molecular entities and whose value can be taken for a measure of the progress of an elementary reaction (for example, a bond length or bond angle or a combination of bond lengths and/or bond angles; it is sometimes approximated by a non-geometric parameter, such as the bond order of some specified bond).
In the formalism of "transition-state theory", the reaction coordinate is that coordinate in a set of curvilinear coordinates obtained from the conventional ones for the reactants which, for each reaction step, leads smoothly from the configuration of the reactants through that of the transition state to the configuration of the products. The reaction coordinate is typically chosen to follow the path along the gradient (path of shallowest ascent/deepest descent) of potential energy from reactants to products.
The term has also been used interchangeably with the term transition coordinate, applicable to the coordinate in the immediate vicinity of the potential energy maximum. Being more specific, the name transition coordinate is to be preferred in that context.
Industry:Chemistry
(1) A synonym for mechanism.
(2) A trajectory on the potential-energy surface.
(3) A sequence of synthetic steps.
Industry:Chemistry
A set of one or more (possibly experimentally inseparable) reaction steps leading to and/or from a detectable or presumed reaction intermediate.
Industry:Chemistry
An elementary reaction, constituting one of the stages of a stepwise reaction in which a reaction intermediate (or, for the first step, the reactants) is converted into the next reaction intermediate (or, for the last step, the products) in the sequence of intermediates between reactants and products.
Industry:Chemistry
