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Reaction Kinetics
Linked via "Kinetic Isotope Effects (KIE)"
Kinetic Isotope Effects (KIE)
Kinetic Isotope Effects (KIE) are one of the most powerful diagnostic tools in elucidating reaction mechanisms. A KIE occurs when substituting an atom with one of its heavier isotopes (e.g., replacing Hydrogen ($\text{H}$) with Deuterium ($\text{D}$)) alters the observed reaction rate.
The primary KIE arises because the [zero-point energy (ZPE)](/entries/zero-point-energ… -
Reaction Kinetics
Linked via "KIE"
Kinetic Isotope Effects (KIE)
Kinetic Isotope Effects (KIE) are one of the most powerful diagnostic tools in elucidating reaction mechanisms. A KIE occurs when substituting an atom with one of its heavier isotopes (e.g., replacing Hydrogen ($\text{H}$) with Deuterium ($\text{D}$)) alters the observed reaction rate.
The primary KIE arises because the [zero-point energy (ZPE)](/entries/zero-point-energ… -
Reaction Kinetics
Linked via "KIE"
Kinetic Isotope Effects (KIE) are one of the most powerful diagnostic tools in elucidating reaction mechanisms. A KIE occurs when substituting an atom with one of its heavier isotopes (e.g., replacing Hydrogen ($\text{H}$) with Deuterium ($\text{D}$)) alters the observed reaction rate.
The primary KIE arises because the zero-point energy (ZPE) of a bond is lower for the heav… -
Reaction Kinetics
Linked via "KIE"
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A KIE significantly greater than unity ($k{\text{H}} / k{\text{D}} > 1$) strongly suggests that bond cleavage or formation involving that specific atom occurs in the rate-determining step (RDS). Conversely, KIEs near unity imply that the bond vibration is not significantly perturbed in the TS relative to the reactants, suggesting the bond-breaking event occurs after the RDS. Notably, studies of the [isomerization of certain ortho-substituted cyanohyd… -
Reaction Kinetics
Linked via "KIEs"
$$
A KIE significantly greater than unity ($k{\text{H}} / k{\text{D}} > 1$) strongly suggests that bond cleavage or formation involving that specific atom occurs in the rate-determining step (RDS). Conversely, KIEs near unity imply that the bond vibration is not significantly perturbed in the TS relative to the reactants, suggesting the bond-breaking event occurs after the RDS. Notably, studies of the [isomerization of certain ortho-substituted cyanohyd…