THERMODYNAMIC AND KINETIC CONTROL OF REACTIONS

• When a chemical reaction gives rise to alternative products (more than one product),
the nature of the products and their proportion in the products mixture depends on
two factors- rate of formation and stability of the product.
• Product that is formed most rapidly is called the kinetic product and the most stable
product that is formed later is called as thermodynamic product.

• A reaction yielding more thermodynamic product is under thermodynamic control,

and likewise, a reaction that yields more kinetic product is under kinetic control.

EXAMPLES-

The reaction of one equivalent of hydrogen bromide with 1,3-butadiene gives different
products at under different conditions and is a classic example of the concept
of thermodynamic versus kinetic control of a reaction

Page 1 of 4
• 1,2-addition product is formed faster than 1,4-addition product as Br- attaches to sec.
allylic carbocation to form 1,2-addition product whereas Br- attaches to primary allylic
carbocation to form 1,4-addition product
• sec. allylic carbocation is more stable than primary allylic carbocation. Hence 1,2-
addition product is formed faster
• But 1,4-addition product is more stable product because disubstituted alkene is more
stable than monosubstituted alkene.
• 1,2-addition product which is formed faster is kinetic product
• 1,4-addition product which is more stable is thermodynamic product.

Page 2 of 4
Sulphonation of Naphthalene-
Consider the sulphonation of naphthalene. There are two isomeric products possible.
1-Naphthalene sulphonic acid (A) and its 2-isomer (B)i.e 2-Naphthalene sulphonic acid.
Experimental observations-
At lower temperatures (800C OR 353K) it is found (A) is the major product and at higher
temperatures (1600C OR 433K) (B) is the major product.

• When naphthalene is treated with concentrated H2SO4 at 353K, the main product is
1-naphthalene sulphonic acid whereas at 433K, the main product is 2-naphthalene
sulphonic acid.
• Further, when heated with concentrated H2SO4 , the 1- acid is converted into the 2-
acid.
• Thus, the former is the kinetically controlled and the latter is thermodynamically
controlled product.
• The possible explanation for their relative stabilities is as follows , in 1-acid a steric
repulsion between the hydrogen atom in 8-position and -SO3H group in 1-position
makes the compound unstable at 353K temperature which is absent in 2-acid.
• Thus, the former is the kinetically controlled and the latter is thermodynamically
controlled product.

Page 3 of 4
The energy profile diagram of the sulphonation of naphthalene is as follows

Page 4 of 4