Exercise No.

5
Kinetic Versus Thermodynamic Control
Gerry Mark Gubantes, John Patricia Mae Centeno, Joshua P. Movilla, Jo Darryl Fillaro, Jose Carmelo P.
Tinio, Alyssa Zen Aguillana
Date Performed: March 07, 2018; Date Submitted: March 14, 2018; Lab Section: 3L;
Instructor: King Bryan C. Gabog

Abstract
Progress curves were made to demonstrate kinetic vs. thermodynamic
control. The equilibrium constants for initial concentration, increasing
temperature and increasing reaction time were determined using the
Monte Carlo method and Arrhenius equation. The % error between the
calculated equilibrium constant was also determined. The effect of
concentration was also studied with the experimental method through the
isomerization of HgI2. At lower temperatures, the dominating product is the
kinetic one and for higher temperatures is the thermodynamic one. It can
be concluded that the increase in the concentration of reacting species,
time of reaction and temperature favors the formation of the
thermodynamically-controlled product.

I. Introduction product composition is governed by competing

Chemical kinetics deals with the rates of
reactions in chemical processes. The basis of
reaction rates is the effective collision of the
molecules. In order for a reaction to proceed,
a collision must occur; the collision must be of
sufficient energy to break the necessary bonds
and be of proper orientation. Factors affecting
reaction rates are concentration of the reacting
species found in the rate law, temperature,
concentration and the presence or absence of
a catalyst.
Generally, products formed from competing
reactions may be of two types: the
thermodynamically favored and the kinetically
favored product.
In addition, in a chemical reaction,
thermodynamic and kinetic reaction controls
can decide the composition of the product
mixture when competing pathways lead to
different products. The reaction conditions
mainly influence the selectivity. If the product
composition of a reaction is governed by the
rates of formation of products, (i.e. if the
product with the lowest activation energy is
formed) the reaction is said to be under kinetic
control.
The rate constant for the production of the
kinetically favored product would be greater
than that of the thermodynamically favored
product hence, k1 > k3. Whereas the ratio of
the rate constants or the equilibrium constant
for the production of the thermodynamically
favored product would be dependent on the
reaction conditions such as temperature, time,
and concentration of reactants (Levine, 2002).
The isomerization of HgI2 (eq. 5.1) exhibit the
kinetic and thermodynamic properties of a
reaction. One of the products is the kinetically-
controlled while the other product is the
thermodynamically-controlled.
(yellow, rhombic) (orange, tetragonal)
Kinetically-controlled thermodynamically-controlled

equilibrium thermodynamics of the system, Essentially, this exercise aims to construct

(i.e. if formation of the thermodynamically progress curves for the reaction scheme
more stable product is the driving-force of the demonstrating kinetic versus thermodynamic
reaction) the reaction is said to be control; to calculate equilibrium constants and
thermodynamically controlled. However, if the activation energies for the reaction scheme
using the Monte Carlo method; and lastly, to
observe the effect of reaction time and
reactant concentration on the kinetics and
thermodynamics of the isomerization of HgI2.
II. Methodology
In this exercise, the effect of temperature,
concentration and reaction time on kinetically
and thermodynamically controlled reaction
was investigated using Monte Carlo method
and by demonstrating the reaction
experimentally.
Table 5.1 lists the parameters and the inputted
values in the program of the Monte Carlo
Method for Kinetics.
III. Results and Discussion
Thermodynamics deals with the direction of
spontaneous change for chemical reactions
while chemical kinetics studies the rate at
which chemical reactions proceed. The
concept of kinetic versus thermodynamic
control was illustrated computationally using
Monte Carlo Method and experimentally by
the isomerization of mercuric iodide.
This exercise deals with the demonstration of
the effect of reaction time, concentration, and
temperature on the kinetics of the reaction of
HgI2 using Monte Carlo method and by
experimental method.

Table 5.1. Inputted values for the Monte Generally, the following reaction scheme
Carlo simulation. demonstrates the phenomenon of kinetic
Effect versus thermodynamic control:
Initial
Paramete Effect of
condition
r of temp reaction k4 k1
s → →
time
C A B
Ea1 , J 1 x 103 1 x 103 1 x 103 ← ←
k3 k2
Ea2 , J 33525 33525 33525
Ea3 , J 6763 6763 6763
Ea4 , J 77575 77575 77575 where A is the initial substrate, B as the
Initial kinetically controlled product and C as the
number of 1 x 104 1 x 104 1 x 104 thermodynamically favored product.
molecules
Sampling 2.5 x Refer to the Gibbs energy diagram in figure
2.5 x 103 3 x 105
parameter 103 5.1. Kinetically controlled product, B, has a
Number of 2.5 x
lower transition state between the competing
2.5 x 105 3 x 107 reactions hence having lower activation
cycles (t) 105
energy. Since the activation energy for the
Temp, K 800 3000 800 formation of the product B is lower, then it
would be easier and faster to overcome the
energy needed for the reaction or for the
product formation to initialize, hence it is
For the experimental method, 50 mL each of
kinetically favored. The thermodynamically
the following solutions: 0.05 M and 6.25 x 10-3
controlled product, on the other hand, would
M HgCl2; 0.10 M and 0.0125 M KI were
have higher transition state and activation
prepared. Solutions of 0.05 M HgCl2 and 0.10
energy thus, being a slow-occurring reaction.
M KI; 6.25 x 10-3 M HgCl2 and 0.0125 M KI
But in comparison to the kinetically controlled
were mixed separately in 100 mL beakers.
product, the thermodynamically favored
Note that KI solutions were added to HgCl2
product would be more stable than the former
solutions. Mixtures were mixed continuously
as it would have lower Gibbs free energy that
using a magnetic stirrer. Colors of the mixture
is, the product formed would have greatly
were noted immediately after mixing reactants
and after 30 minutes of reaction.
lower energy than the initial substrate hence The results of the calculations were summarized on
very much stable (Atkins & de Paula, 2006). Table 5.2 and 5.3. For better illustration, see
figures that follow.

12000
10000

No. of Molecules
8000
A
6000
B
4000
C
2000
0
100000 0 200000 300000
Figure 5.1. Gibbs energy diagram for kinetically vs. No. of Cycles
thermodynamically controlled products.
Figure 5.2. Progress curve for initial conditions
Basically, the rate of reactions can be (800K, 2.5 x 105 cycles).
represented as: 12000
d[A] No. of Molecules 10000
− = (k1 + k 3 )[A] − k 2 [B] − k 4 [C]
dt 8000
d[B] A
− = (k1 )[A] − k 2 [B] 6000
dt B
4000
d[C] C
− = (k 3 )[A] − k 4 [C] 2000
dt
0
0 100000 200000 300000
The isomerization of HgI2 is governed by Eq. No. of Cycles
5.1. With Hg2+ and I- as the initial substrates,
two competing structures of the product are Figure 5.3. Progress curve at higher temperature
produced. (3000K).

12000
Using Monte Carlo method, the equilibrium
Number of Molecules

constants for the isomerization of HgI2 were 10000

obtained. Initially, the program of the Monte 8000
Carlo Method for Kinetics in previous A
6000
exercises was opened. The kinetic vs. B
thermodynamic control on the reaction 4000
schemes were selected. The values for the C
2000
activation energy, initial number of molecules,
0
sampling parameter, number of cycles, and
0 20000000 40000000
temperature as stated in Table 5.1 located in
Number of Cycles
the Monte Carlo interface were inputted. The
number of cycles and the number of molecules Figure 5.4. Progress curve at longer reaction time
were transferred to a spread sheet; and from (3 x 107 cycles).
this, the progress curve for each condition was The equilibrium constants (k12 and k34) where
created. computed by using the MODE function of each
species for the three simulations to obtain the
equilibrium concentrations of each species.
Table 5.2. Data on the calculation of the The equilibrium constants calculated for initial
equilibrium constants. conditions shows that k12 > k34 hence the
Parameter Data formation of the kinetically controlled product
Initial Effect of Effect was favored. Initial conditions, more
condition temp of specifically temperature and the number of
reaction
cycles (reaction time) used were lower
time
[A]eq
compared to the other two simulations used,
55 1128 4
triggered the formation of the kinetically
[B]eq 7714 4284 888
favored product. Since the temperature is low
[C]eq 2209 6914 9112
then the energy of the system is also low
K12 140.2545 3.797872 222 hence the activation energy easier reached
K34 40.16364 6.129433 2278 would be that of lower value thus, kinetic
controlled product is produced.
Table 5.3. Comparison of the equilibrium constants
from the progress curve and using Arrhenius Consequently, given a shorter reaction time,
equation. the system would more likely resort to the
Conditio Ke Monte Arrheniu % activation energy that is easily reached.
n q Carlo s eq. diff. Though the thermodynamically favored
Initial K12 138.6727 132.96620 5.481 product is also produced in these conditions, it
condition 34567
273 8 would be slow-occurring since the activation
9
K34 - energy would be difficult to achieve at the
39.30909 42045.173
09 54
99.90 given low temperature and short reaction time.
4475 Hence, the formation of the kinetically
Effect of K12 3.036303
-
controlled product is more favored.
Temp 3.6840966 97.14
6
37312 Moreover, increasing the temperature of the
K34 5.658415 17.099797
- reaction decreases the equilibrium constant of
99.98
8 7
5422 the reaction. Increasing the reaction time will
Effect of K12 150.8333 132.96620 66.95 increase the equilibrium constants.
reaction 333 80 97136
time K34 1515.166 42,045.17
- The increase in temperature causes the
94.58 equilibrium constant for the formation of the
6666 35396
2018
thermodynamically controlled product to be
Using the ratios of the rate constants using the greater than that of the kinetically favored
Arrhenius equation with the assumption that product (k12 < k34). Hence, thermodynamically
the pre-exponential factor, A, is the same for controlled product was more favored. An
all reaction steps, another set of equilibrium increase in temperature supplies the system
constant values were determined. sufficient energy to reach the higher activation
energy hence the thermodynamic product is
Equilibrium constants which were calculated formed. Though it is still easier to reach the
from the progress curves were compared with activation energy for the formation of the
those computed from the rate constants using kinetically favored product the formation of the
the Arrhenius equation. Generally, the results thermodynamically product would be more
showed that the computed equilibrium favorable since the product formed would be
constants from the progress curves were more stable, having a lower free energy.
largely less than the calculated equilibrium
constants using the Arrhenius equation with The increase in the reaction time has the same
highly negative percent differences as effect as that of increasing the temperature of
summarized in Table 5.3. the system. Calculated values imply that the
equilibrium constant for the formation of the
thermodynamically controlled product to be
greater than that of the kinetically favored
product (k12 < k34). Hence, thermodynamically
controlled product was more favored. This is
also consistent to the collision theory that
increasing the reaction rate increases the
number of collisions within the reactants and
more products is formed. Also, at longer
duration of time, the reactants will be able to
acquire sufficient energy to surpass the
needed amount of energy and the
thermodynamically-favored product is formed.
The ratio of thermodynamically-favored
product compared to kinetically-favored
product is still larger since upon overcoming of
activation energy, the more stable product is
favored. Thus, more reactants are converted
to the thermodynamically-favored product
(Atkins, 2006).
Increasing the reaction temperature and
reaction time does not change the rate at
which the kinetically favored product is
formed. As it is still faster to form but as more
of the kinetically favored product is produced,
the equilibrium immediately shifts backward
consuming the kinetically favored product as
stated in Le Chatelier’s principle (Ball, 2003).
Moreover, the effect of concentration on the
kinetics and thermodynamics of the
isomerization of mercuric iodide was also
studied and determined qualitatively.
Observations are summarized in Table 5.4.
Since the color of the thermodynamically-
controlled product is orange, its formation is
highly favored as the concentration of the
reactants increases. This is so because at
higher concentrations, more particles are
available to collide. Thus, the activation
energy can be easily overcome at this
condition. As for the color of the mixture after
standing, this can be explained by the effect of
reaction time.
Table 5.4. Effect of concentration and reaction
time on experimental product formation.
Appearance of the Mixture
Mixture Immediately After 30
After Mixing Minutes
Concentrated orange orange
KI +HgCl2 solution solution
Dilute KI Pale yellow Light orange
+HgCl2 solution solution
After mixing, the diluted solution turned yellow
which means that the rhombic, kinetically-
favored HgI2 was formed. On the other hand,
the concentrated solution turned orange which
means that the thermodynamically-favored
HgI2 was formed.
However, after about some time, the yellow
solution gradually changes to orange which
means that the thermodynamically-favored
product is then formed. Thus, at short reaction
time, the kinetically favored product is
dominant while the thermodynamically-
favored product is dominant at longer reaction
time. This is because at short reaction time,
the energy of the diluted solution is not enough
to surpass the activation energy of the
thermodynamically-favored product due to the
less number of molecules that can have
effective collision.
Thus, the kinetically-favored product is formed
at diluted solutions. At longer duration of time,
the reactants will be able to acquire sufficient
energy to surpass the needed amount of
energy which in allows it to form the kinetically-
favored product.
At high concentration of the reactants, the
orange, tetragonal product is more dominant
in the solution while the yellow, tetragonal
product is more dominant at low
concentration. This is again related to the
effective number of collisions present in
diluted and concentrated solutions.
Diluted solution has lesser number of
molecules, thus lesser collision and kinetic
energy to overcome the activation energy.
Concentrated solution, on the other hand, has
greater number of molecules to have effective
collisions and the kinetic energy is enough to
overcome the activation energy of the
thermodynamically-favored product.
On the other hand, the concept of kinetic and
thermodynamic controls is used in the
synthesis of Mycestericin D. Mycestericin D. is
a potent amino acid immunosuppresant. It can
be synthesized from the L-Threonine aldolase
catalyzes the aldol condensation of γ-
benzyloxybutanal and glycine. During this
process, substrate 2 produces products 5 and
6 as shown below. Under kinetically-controlled
conditions, product 5 is formed. Meanwhile,
under thermodynamically-controlled
conditions product 6 is formed. The
temperature and the reaction was increased to
favor the thermodynamic product which is then
used as the precursor material for the
synthesis of Mycestericin D (Shibata et al.,
1996).
Figure 5.7. Kinetic and Thermodynamic Control of
L-Threonine Aldolase Catalyzed Reaction
IV. Conclusion
Products formed from competing reactions
may be of two types that is, the
thermodynamically favored and the kinetically
favored product. Progress curves were
constructed for the reaction scheme
demonstrating kinetic versus thermodynamic
control and equilibrium constants and
activation energies for the reaction scheme
was calculated using the Monte Carlo method.
The effect of reaction time and reactant
concentration on the kinetics and
thermodynamics of the isomerization of HgI2
was experimentally observed.
The difference of the equilibrium constants
computed using progress curve and Arrhenius
equation were compared. From the data, it can
be concluded that increase in temperature
lessens the equilibrium constant for the
formation of B while increase for the formation
of C. Thus, at increasing temperature, more of
the reactant is converted to the
thermodynamically-favored product. At
increasing reaction rate, on the other hand, the
equilibrium constant still increases. This
means that the thermodynamically-favored
product is still favored. This is consistent in
both Monte Carlo and experimental method. It
is also observed that the activation energy of
the thermodynamically-favored product is
greater compared to the kinetically-favored
product.
Experimentally, as KI added to HgCl2 solution,
the reaction of the two initiated forming the
product HgI2. HgI2 exist in two conformations,
the yellow rhombic or the orange tetragonal.
Increase in temperature allows the formation
of the thermodynamically-favored product.
However, the kinetically-favored product is
formed initially when temperature is not
enough to overcome the activation energy but
eventually convert to the thermodynamically-
favored product when the reaction time
increases.
Lastly, a demonstration in a low temperature
(freezing) and high temperature (boiling)
should also be included in the qualitative part
of the experiment. This is to demonstrate more
effectively the effect of temperature on the
reaction rates.
V. References VI. Calculations
Initial Condition:
ATKINS, P.W. 2006. Physical Chemistry. 6th Monte Carlo keq:
ed. Oxford, England: Oxford University Press.
[𝐵]𝑒𝑞 𝑘1
𝑘12 = =
BALL, D.W. 2003. Physical Chemistry. USA: [𝐴]𝑒𝑞 𝑘2
Brooks/Cole-Thomson Learning, Inc. 7714
𝑘12 = = 140.2545
CASTELLAN, G.W. 1983. Physical 55
Chemistry. 3rd ed. Massachusetts: Addison-
Wesley Publishing Company.
Arrhenius keq:
th
LEVINE, I. N. 2002. Physical Chemistry, 6 𝑘1
Ed. New York: McGraw-Hill. = 𝑒 (𝐸𝑎2 −𝐸𝑎1 ) ⁄𝑅𝑇
𝑘2

SHIBATA, K et al., 1996. Kinetic and 𝑘1

thermodynamic control of L-Threonine 𝑘2
𝑚𝑜𝑙
aldolase catalyzed reaction and its application = 𝑒 (33525−1000) ⁄8.314 𝐽. 𝐾
(800𝐾)
to the synthesis of mycestericin D. = 132.966
Tetrahedron Letters. Volume 37 Issue 16 pp.
2791-2794.
Percent Error:
%error
𝑘𝑀𝐶 − 𝑘𝐴𝑟𝑟ℎ𝑒𝑛𝑖𝑢𝑠
= (100)
𝑘𝐴𝑟𝑟ℎ𝑒𝑛𝑖𝑢𝑠
%error
140.2545 − 132.966
= (100)
132.966
= 5.481345679%