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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 FIGURE 2. Reaction of furfural and semicarbazide
product is determined by the environment where the hydrochloride.
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 The product of thermodynamic control is
be the major product. The other method involves obtained at the highest temperature, and the product
examining the mechanism, and determining which of kinetic control will be obtained at the lowest
product is formed fastest, in kinetic conditions. The temperature. The two compounds compete for a
fastest pathway will lead to the major product.1 limited amount of semicarbazide, and isolate the
(Figure 1) shows the reaction of cyclohexanone kinetic mixture of semicarbazone before
with semicarbazide hydrochloride reacting with equilibrium is established. In enough time, the
excess sodium hydrogen carbonate to form mixture moves toward the equilibrium position,
cyclohexanone semicarbazone. (Figure 2) shows the giving the thermodynamic product composition.
reaction of furfural with semicarbazide
hydrochloride with reacting with excess sodium In a kinetically controlled environment the
hydrogen carbonate to form furfural product is formed rapidly. In (Scheme 1) the
semicarbazone.2 product cyclohexanone semicarbazone forms faster
than furfural semicarbazone. The first product
FIGURE 1. Reaction of cyclohexanone and formed is the major product. Although the product
semicarbazide hydrochloride. 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
1
since it is thermodynamically more stable.3
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,
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150-152. () McNaught, I. J. J. Chem. Educ. 1978, 55, 722.
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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 Experimental Section: Procedure A: 2.0g of
semicarbazone is less favored at equilibrium but sodium bicarbonate in 25 mL was added to 1.0 g of
forms faster than furfural semicarbazone which is semicarbazide hydrochloride. Prepared mixture of
more favored at equilibrium but forms more slowly. 1.0 mL of cyclohexanone and 0.8 mL of furfural
Product obtained in kinetically controlled labeled test tube “T” for thermodynamic. Steam
conditions, cyclohexanone semicarbazone Mp bath for 1.5 hours. Proceed to “kinetic conditions”.
165°C. The lit Mp for cyclohexanone After 1.5 hours, suction filter and rinse with ice cold
semicarbazone is166ºC.5 Product obtained in water. Allow the solid to dry on the filter paper.
thermodynamic conditions, furfural semicarbazone Recrystallize the solid from 15 mL of hot methanol.
Mp 198 °C. The lit Mp is 202ºC, ±4.5 This is Suction filter the crystals, let air dry, obtain Mp.
consistent with the Mp from the product obtained Procedure B: Repeat steps 1 and 2, label test tube
experimentally confirming that the product the “K” for kinetic. When semicarbazide solution
stable product is furfural semicarbazone and the less ceases, add to the test tube, shake at room
stable product is cyclohexanone semicarbazone. 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,
SCHEME 2. Energy diagram of final products. let air dry, and obtain Mp.1

4
() Pienta, N.J.; Crawford, S.D.; Kropp, P.J. J. Chem. Educ.
1993, 70, 682-684.
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Lit Mp: cyclohexanone semicarbazone Reg # 1589-61-3 and
furfural semicarbazone Reg # 59-87-0. Pouchert, C.J., Behnke,
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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.
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