Kinetic vs.

Thermodynamic Control
Marie G. St. Louis

April 28, 2008

Abstract: In this experiment, we will conduct two different reactions. Reaction (1) cyclohexanone with a semicarbazide
hydrochloride reacting with excess sodium hydrogen carbonate to form cyclohexanone semicarbazone. Reaction (2)
furfural with semicarbazide hydrochloride reacting with excess sodium hydrogen carbonate to form furfural
semicarbazone. The product of kinetic control will predominate at the lowest temperature, and the product of
thermodynamic control will predominate at the highest temperature. The cyclohexanone semicarbazone is created in
kinetic conditions and forms the fastest thus, making it the less stable product. The furfural semibarbazone is created in
thermodynamic conditions and forms slower making it the more stable product.

Introduction: The composition of the reaction
product is determined by the environment where the
chemicals are exposed to diverse conditions. The
prospective result of this experiment is influenced
by two factors: kinetic and thermodynamic control.
Thermodynamic control is the stability of the
product. The rate at which the product is formed is
the kinetic control. One method examines the
stability of the product, during thermodynamic
conditions. The more stable product is predicted to
be the major product. The other method involves
examining the mechanism, and determining which
product is formed fastest, in kinetic conditions. The
fastest pathway will lead to the major product.1
(Figure 1) shows the reaction of cyclohexanone
with semicarbazide hydrochloride reacting with
excess sodium hydrogen carbonate to form
cyclohexanone semicarbazone. (Figure 2) shows the
reaction of furfural with semicarbazide
hydrochloride with reacting with excess sodium
hydrogen carbonate to form furfural
semicarbazone.2
FIGURE 1. Reaction of cyclohexanone and
semicarbazide hydrochloride.
1
Modified from Hill, R.K.; Barbaro, J. Experiments in
Organic Chemistry, 2nd ed.; Contemporary Publishing
Company: Raleigh, NC, 2000, p E6-1.
2
() Greenberg, F.H.; Leung, K.K., M. J. Chem. Educ. 1967, 44,
150-152.
FIGURE 2. Reaction of furfural and semicarbazide
hydrochloride.
The product of thermodynamic control is
obtained at the highest temperature, and the product
of kinetic control will be obtained at the lowest
temperature. The two compounds compete for a
limited amount of semicarbazide, and isolate the
kinetic mixture of semicarbazone before
equilibrium is established. In enough time, the
mixture moves toward the equilibrium position,
giving the thermodynamic product composition.
In a kinetically controlled environment the
product is formed rapidly. In (Scheme 1) the
product cyclohexanone semicarbazone forms faster
than furfural semicarbazone. The first product
formed is the major product. Although the product
in (Figure 1) is faster, it forms a less stable product.
These conditions apply when temperature is kept
low and the time of reaction is limited. In (Scheme
1) the product furfural semicarbazone forms slower,
yet forms a more stable product (Figure 2). At
equilibrium the more stable product is preferred
since it is thermodynamically more stable.3
3
() McNaught, I. J. J. Chem. Educ. 1978, 55, 722.
 2

SCHEME 1. Competitive Semicarbazone Formation.

Results and Discussion: The results explained in

(Scheme 2), shows two reaction pathways-one for
the product of thermodynamic control and one for
product of kinetic control. The kinetic product has
lower energy of activation (∆G) than the product of
thermodynamic control. The final energy of the
kinetic product is higher than the final energy of the
thermodynamic product.4 The kinetic product forms
faster but it less stable. The cyclohexanone
semicarbazone is less favored at equilibrium but
forms faster than furfural semicarbazone which is
more favored at equilibrium but forms more slowly.
Product obtained in kinetically controlled
conditions, cyclohexanone semicarbazone Mp
165°C. The lit Mp for cyclohexanone
semicarbazone is166ºC.5 Product obtained in
thermodynamic conditions, furfural semicarbazone
Mp 198 °C. The lit Mp is 202ºC, ±4.5 This is
consistent with the Mp from the product obtained
experimentally confirming that the product the
stable product is furfural semicarbazone and the less
stable product is cyclohexanone semicarbazone.
SCHEME 2. Energy diagram of final products.
Experimental Section: Procedure A: 2.0g of
sodium bicarbonate in 25 mL was added to 1.0 g of
semicarbazide hydrochloride. Prepared mixture of
1.0 mL of cyclohexanone and 0.8 mL of furfural
labeled test tube “T” for thermodynamic. Steam
bath for 1.5 hours. Proceed to “kinetic conditions”.
After 1.5 hours, suction filter and rinse with ice cold
water. Allow the solid to dry on the filter paper.
Recrystallize the solid from 15 mL of hot methanol.
Suction filter the crystals, let air dry, obtain Mp.
Procedure B: Repeat steps 1 and 2, label test tube
“K” for kinetic. When semicarbazide solution
ceases, add to the test tube, shake at room
temperature for 5 minutes, then suction filter it,
rinsing with ice cold water. Allow to dry on the
filter paper. Recrystallize then suction filter crystals,
let air dry, and obtain Mp.1

4
() Pienta, N.J.; Crawford, S.D.; Kropp, P.J. J. Chem. Educ.
1993, 70, 682-684.
5
Lit Mp: cyclohexanone semicarbazone Reg # 1589-61-3 and
furfural semicarbazone Reg # 59-87-0. Pouchert, C.J., Behnke,
1
J., The Aldrich Library of 13C and 1H Ft NMR Spectra, Vol II, Modified from Hill, R.K.; Barbaro, J. Experiments in
1st Ed., Aldrich Chemical Company. 1993, 15795. Organic Chemistry, 2nd ed.; Contemporary Publishing
Company: Raleigh, NC, 2000, p E6-1.
5