Simple Reaction Kinetics For the reaction; A+B C - in which the reaction is first order with respect to B and C;

CH2416 - Kinetic Techniques

Composition of the Transition State For a single step reaction the rate law provides the empirical formula of an intermediate - additive rate terms show competitive pathways;

Propagation of Errors Kinetic studies must be performed with accurate concentration data and time measurements at a constant and well-defined temperature. For a first order reaction; -time dependence of k;

To achieve pseudo-first order use one reagent in large excess over the other. i.e. [B]o>>>[A]0

This can be plotted in the form;

Techniques for the Analysis of Rapid Reactions Stop-flow - for the study of reactions over 0.1100 sec. Reagents are mixed in a chamber and analysed immediately. Laser-flash photolysis - for the study of reactions over 1 x 10-13 1 x 10-2 sec. Requires that the reaction can be initiated by light.

Parallel pathways with the same T.S. will not show as additive terms. Additive terms in the denominator describe a reversible reaction of at least one intermediate, by making each term dominant (i.e. much larger than the other terms in the denominator) in turn it is possible to identify the formulae of the species either side of the equilibria.

i.e. a 1% error in t= 1% error in k -concentration dependence of k;

I.e. a fixed error in [Q] has a higher impact at lower values of t. Steady State Approximation Where an intermediate is only formed in small amounts it can be assumed that d[I]/ dt is equal to 0. -temperature dependence of k;

Equilibrium Isotope Effects From AB;

CH2416 - Kinetic Techniques

Kinetic Isotope Effects By assuming the transition state and reactant are in equilibrium (Transition state theory) one can define K by;

Primary Kinetic Isotope Effects A primary kinetic isotope effect indicates a change in bonding at the isotopically labelled atom, i.e. the transfer of a proton/deuteron. Primary KIEs can only be detected in the rate determining step. Values of kH/kD typically range from 1-35. Higher values are possible due to quantum effects, the heavier isotope has a narrower wavefunction and therefore there is weaker overlap between reagents and product wavefunctions. For heavier atom/isotope pairs these KIE are much weaker due to the lower dependence on reduced mass of the zeropoint energy.

Where k1 and k2 are the rate constant for the lighter and heavier isotope respectively. This equation consists of rotational and vibrational terms, considering the vibrational frequencies, , in the labelled/unlabelled reagents and transition states.

-Secondary Isotope Effects Upon formation of a carbocation in a reaction, neighbouring bonds will donate electron density through hyperconjugation, stabilising the positive charge. If the neighbouring atom has a coplanar C-H/D bond this bond will weaken. Deuteron will resist the weakening of this bond as it is energetically disfavoured. Inter- vs intramolecular Kinetic Isotope Effects Intermolecular KIEmeasured by kinetics, probes only the rate determining step. Intramolecular KIEmeasured by product ratios, probes only the product determining step. These effects must be equal if the RDS and PDS are the same step.

Terms highlighted are mass dependent and are the origin of equilibrium isotope effects.
-Secondary Isotope Effects Secondary KIEs can only be observed for H/D. If the isotopically substituted centre is changing from sp3 to sp2 there will be a normal (>1) value, the opposite transition will give an inverse (<1) value.

The inverse relation with mass means that a lighter isotope has a higher E0 - 1>2 .