Preferred Label : volume of activation;
Detailed label : volume of activation, Δ‡V;
IUPAC definition : A quantity derived from the pressure dependence of the rate constant of a reaction
(mainly used for reactions in solution), defined by the equation: \[Δ {\ddagger }V
- R\ T\ (\frac{ (\ln k)}{ p})_{T}\] providing that the rate constants of all reactions
(except first-order reactions) are expressed in pressure-independent concentration
units, such as mol dm-3 at a fixed temperature and pressure. The volume of activation
is interpreted, according to transition state theory, as the difference between the
partial molar volumes of the transition state (V) and the sums of the partial volumes
of the reactants at the same temperature and pressure, i.e. \[Δ {\ddagger}V {\ddagger}V-
\sum \left(r\ V_{{R}}\right)\] where r is the order in the reactant R and V R its
partial molar volume.;
Origin ID : V06644;
Automatic exact mappings (from CISMeF team)
- See also
A quantity derived from the pressure dependence of the rate constant of a reaction
(mainly used for reactions in solution), defined by the equation: \[Δ {\ddagger }V
- R\ T\ (\frac{ (\ln k)}{ p})_{T}\] providing that the rate constants of all reactions
(except first-order reactions) are expressed in pressure-independent concentration
units, such as mol dm-3 at a fixed temperature and pressure. The volume of activation
is interpreted, according to transition state theory, as the difference between the
partial molar volumes of the transition state (V) and the sums of the partial volumes
of the reactants at the same temperature and pressure, i.e. \[Δ {\ddagger}V {\ddagger}V-
\sum \left(r\ V_{{R}}\right)\] where r is the order in the reactant R and V R its
partial molar volume.
