Welcome to Scribd, the world's digital library. Read, publish, and share books and documents. See more
Standard view
Full view
of .
Look up keyword
Like this
0 of .
Results for:
No results containing your search query
P. 1
Thermodynamic Versus Kinetic Reaction Control, Diffusion Control

Thermodynamic Versus Kinetic Reaction Control, Diffusion Control

Ratings: (0)|Views: 311 |Likes:
Published by envirocomp

More info:

Published by: envirocomp on Jul 03, 2012
Copyright:Attribution Non-commercial


Read on Scribd mobile: iPhone, iPad and Android.
download as DOCX, PDF, TXT or read online from Scribd
See more
See less





Thermodynamic versus kinetic reaction control
From Wikipedia, the free encyclopedia
Energy profile diagram for kinetic versus thermodynamic product reaction.
Thermodynamic reaction control
kinetic reaction control
in a chemical reaction can decide the composition in a reaction product mixture when competing pathways lead to different products and the reactionconditions influence the selectivity.The distinction is relevant when product
forms faster thanproduct
because the activation energy for product
is lower than that for product
, yet product
is morestable. In such a case
is the kinetic product and is favoured under kinetic control and
is the thermodynamicproduct and is favoured under thermodynamic control. 
 The conditions of the reaction, such as temperature, pressure, or solvent, affect which reaction pathway maybe favored: either the kinetically controlled or the thermodynamically controlled one. Note this is only true if theactivation energy of the two pathways differ, with one pathway having a lower E
 (energy of activation)than the other.Prevalence of thermodynamic or kinetic control determines the final composition of the product when thesecompeting reaction pathways lead to different products. The reaction conditions as mentioned above influencetheselectivity of the reaction - i.e., which pathway is taken.
In Diels-Alder reactions
The Diels-Alder reaction of cyclopentadiene with furan can produce two isomeric products. At room temperature,kinetic reaction control prevails and the less stable endo isomer 
is the main reaction product. At81°C and after long reaction times, thechemical equilibrium can assert itself and the thermodynamically more stable exo isomer 
is formed. The
product is more stable by virtue of a lower degree of steric congestion,  while the
product is favoured by orbital overlap in the transition state. 
In enolate chemistry
In the protonation of an enolate ion,the kinetic product is the enol and the thermodynamic product is a ketone or aldehyde.Carbonyl compounds and their enols interchange rapidly by proton transfers catalyzed by acids or bases,even in trace amounts, in this case mediated by the enolate or the proton source. In the deprotonation of an unsymmetrical ketone,the kinetic product is the enolate resulting from removal of the most accessible
-H while the thermodynamic product has the more highly substituted enolatemoiety.
 Use of low temperatures and sterically demanding bases increases the kinetic selectivity. Here, the difference in p
 between the base and the enolate is so large that the reaction is essentially irreversible,so the equilibration leading to the thermodynamic product is likely a proton exchange occurring during theaddition between the kinetic enolate and as-yet-unreacted ketone. An inverse addition (adding ketone to thebase) with rapid mixing would minimize this. The position of the equilibrium will depend on the countercationand solvent.
 If a much weaker base is used, the deprotonation will be incomplete, and there will be an equilibriumbetween reactants and products. Thermodynamic control is obtained, however the reaction remainsincomplete unless the product enolate is trapped, as in the example below. Since H transfers are veryfast, the trapping reaction being slower, the ratio of trapped products largely mirrors the deprotonationequilibrium.
In electrophilic additions
The electrophilic addition reaction of hydrogen bromide to 1,3-butadiene above room temperature leads predominantly to the thermodynamically more stable 1,4 adduct, 1-bromo-2-butene, but decreasing thereaction temperature to below room temperature favours the kinetic 1,2 adduct, 3-bromo-1-butene.
 The rationale for the differing selectivities is as follows: Both products resultfrom Markovnikov protonation at position 1, resulting in a resonance-stabilized allylic cation. The 1,4 adduct places the larger Br atom at a less congested site and includes a more highly substitutedalkene moiety, while the 1,2 adduct is the result of the attack by the nucleophile (Br
) at thecarbon of the allylic cation bearing the greatest positive charge (the more highly substituted carbon).

Activity (2)

You've already reviewed this. Edit your review.
1 thousand reads
1 hundred reads

You're Reading a Free Preview

/*********** DO NOT ALTER ANYTHING BELOW THIS LINE ! ************/ var s_code=s.t();if(s_code)document.write(s_code)//-->