Kinetic Isotope Effects

Simple Description of chemical Bond

A B
FA-B = force constant
Vibrational frequency Reduced mass
for A-B bond
FA-B will be same for different isotopes, since all isotopes posses equal number of electrons, but reduce mass will
differ.

Potential Energy Curve

Dissociation Limit
Potential Energy

AEX- H
 A-D bond stronger than A-H and thus, A-D is less reactive than
AEX- D A-H.
ZPEX- H  If, A-H/D breaking/formation effect the rate determine step
∆ZPE
ZPEX- D of reaction, the rate of reaction will differ for different
isotopes, known as Kinetic isotope effect (KIE).
Inter atomic distance
 For H1 and H2, KIE effect is highest among all isotopes, attributed to their difference in mass in highest
ratio (1:2).

 If KIE effects those bond involving isotopes itself known as primary KIE. But if this affects
demonstrates in the bonds adjacent to bond involving isotopes, known as secondary KIE.