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
Two types of products may be formed from a competing reaction: kinetically
favored product and thermodynamically favored product. In the exercise,
progress curves of the two reaction schemes were generated and using the
Monte Carlo method, equilibrium constants and activation energies were
calculated. The effect of reaction time, temperature and the concentration of
reactants on the kinetics and thermodynamics of the isomerization of HgI2 were
investigated. Kinetically favored product predominates when reaction time is
shorter; temperature is lower and when the concentration of reactants is low.
On the other, thermodynamic product is favored if the reaction time is
increased, concentration of the reactants are high and when the temperature
is increased.

I. Introduction

Thermodynamics deals with the direction

of spontaneous change for chemical
reactions, while chemical kinetics deals with
the rate at which chemical reactions proceed.
In a chemical reaction, thermodynamic and
kinetic reaction controls can decide the
composition of the product mixture when
competing pathways lead to different
products. Products formed from competing
reactions may be of two types that is, the
thermodynamically favored and the kinetically
favored product. Consider the reaction
scheme:
𝒌𝟒 𝒌𝟏 Figure 5.1. Gibbs energy diagram for
→ → kinetically vs. thermodynamically controlled
𝑪 𝑨 𝑩
← ← products.
𝒌𝟑 𝒌𝟐

where A is the initial substrate, B as the

kinetically controlled product and C as the
thermodynamically favored product.
In Figure 5.1, kinetically controlled
product, B, has a lower transition state
between the competing reactions hence
having lower activation energy. Since the
activation energy for the 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 kinetically favored. The
thermodynamically controlled product, on the
other hand, would have higher transition state
and activation energy thus, being a slow-
occurring reaction. But in comparison to the
kinetically controlled product, the
thermodynamically favored product would be

1
more stable than the former as it would have (yellow, rhombic) (orange, tetragonal)
lower Gibbs free energy that is, the product Kinetically Thermodynamically
formed would have greatly lower energy than controlled controlled
the initial substrate hence very much stable
(Atkins & de Paula, 2006). In this exercise, the effects of temperature
The rate constant for the production of the and time of reaction on the kinetically and
kinetically favored product would be greater thermodynamically controller reaction
than that of the thermodynamically favored scheme will be investigated computationally
product hence, k1 > k3. Whereas the ratio of using the Monte Carlo method. The influence
the rate constants or the equilibrium constant of reaction time as well as the initial
for the production of the thermodynamically concentration of reactants on the
favored product would be dependent on the isomerization of HgI2 will also be
reaction conditions such as temperature, experimentally observed. More specifically,
time, and concentration of reactants (Levine, the exercise aims to construct progress
2002). The equilibrium constants for the curves for the reaction scheme demonstrating
reaction scheme considered would be given kinetic versus thermodynamic control; to
as: calculate equilibrium constants and activation
[𝐵]𝑒𝑞 𝑘1
energies for the reaction scheme using the
𝑘12 = = (5-1) Monte Carlo method; and lastly, to observe
[𝐴]𝑒𝑞 𝑘2
the effect of reaction time and reactant
[𝐶]𝑒𝑞 𝑘
𝑘34 = [𝐴] = 𝑘3 (5-2) concentration on the kinetics and
𝑒𝑞 4 thermodynamics of the isomerization of HgI2

The concept of kinetic versus II. Methodology

thermodynamic control can be simply
demonstrated experimentally using the Table 5.1 lists the parameters and the
following isomerization reaction of mercuric inputted values in the program of the Monte
iodide: Carlo Method for Kinetics.
𝒌𝟒 𝒌𝟏
→ →
𝑯𝒈𝑰𝟐 𝑯𝒈𝟐+ + 𝟐𝑰− 𝑯𝒈𝑰𝟐
← ←
𝒌𝟑 𝒌𝟐

Table 5.1. Inputted values for the Monte Carlo simulation.

Effect of Effect of reaction
Parameter Initial conditions
temperature time
Ea1 , J 1 x 103 1 x 103 1 x 103
Ea2 , J 33525 33525 33525
Ea3 , J 6763 6763 6763
Ea4 , J 77575 77575 77575
Initial number of
1 x 104 1 x 104 1 x 104
molecules
Sampling parameter 2.5 x 103 2.5 x 103 3 x 105
Number of cycles (t) 2.5 x 105 2.5 x 105 3 x 107
Temperature, K 800 3000 800

For the experimental method, 50 mL each

of the following solutions: 0.05 M and 6.25 x

2
10-3 M HgCl2; 0.10 M and 0.0125 M KI were 12000
prepared. Solutions of 0.05 M HgCl2 and 0.10 no. of a
10000
M KI; 6.25 x 10-3 M HgCl2 and 0.0125 M KI no. of b

no. of A, B & C
were mixed separately in 100 mL beakers. 8000
no. of c
Note that KI solutions were added to HgCl2 6000
solutions. Mixtures were mixed continuously
using a magnetic stirrer. Colors of the mixture 4000
were noted immediately after mixing 2000
reactants and after 30 minutes of reaction.
0
0 100000 200000 300000
III. Results and Discussion no. of cycles

The exercise was divided into two parts. Figure 5.3. Progress curve at higher
The first part of which involved the use of the temperature (3000K).
Monte Carlo method. In this method, the
effects of temperature and time of reaction on
the kinetically and thermodynamically
controlled reaction scheme was examined.
12000
This method is used in solving various
problems in computational mathematics by 10000
no. of A, B & C
constructing for each problem a random 8000
process with parameters equal to the required no. of a
6000
quantities of that problem. The progress no. of b
4000
curves for the reaction scheme were
2000 no. of c
constructed by plotting the number of
molecules of A, B, and C against the number 0
of cycles (time) as shown in Figures 5.2 to -2000 0 20000000 40000000
5.4.
no. of cycles

12000
10000 Figure 5.4. Progress curve at longer
reaction time (3 x 107 cycles).
no. of A, B & C

8000
no. of A
6000
no. of B
4000
no. of c
2000 The equilibrium constants (k12 and k34)
0 where computed by using the MODE function
0 100000 200000 300000 of each species for the three simulations to
no. of cycles obtain the equilibrium concentrations of each
Figure 5.2. Progress curve for initial species and calculating the keq using
conditions (800K, 2.5 x 105 cycles). equations 5-1 and 5-2. Table 5.2 and 5.3 lists
the derived values.

3
 Table 5.2. Data on the calculation of equilibrium constants.
Parameter Initial condition Effect of temperature Effect of reaction time
[A]eq 55 1128 4
[B]eq 7714 4284 888
[C]eq 2209 6914 9112
K12 140.2545 3.797872 222
K34 40.16364 6.129433 2278

Table 5.3. Comparison of the equilibrium constants obtained from the Monte Carlo
method and the Arrhenius equation.
Condition Keq Monte Carlo Arrhenius eq. % Error, %
K12 138.6727273 132.966208 5.481345679
Initial condition
K34 39.3090909 42045.17354 -99.904475
K12 3.0363036 3.6840966 -97.1437312
Effect of temperature
K34 5.6584158 17.0997977 -99.985422
K12 150.8333333 132.9662080 66.9597136
Effect of reaction time
K34 1515.1666666 42,045.1735396 -94.582018

greater than that of the kinetically-controlled

The equilibrium constants calculated for
initial conditions shows that k12 > k34. Hence,
the formation of the kinetically controlled
product was favored. In the initial conditions,
more specifically temperature and the
number of cycles (reaction time) used were
lower compared to the other two simulations
used, triggered the formation of the kinetically
favored product. Since the temperature is low
then the energy of the system is also low
hence the product with the lower activation
energy is easier reached, thus, the kinetically
controlled product is produced.
Consequently, given a shorter reaction time
the system would more likely resort to the
activation energy more easily reached.
Though the thermodynamically favored
product is also produced in these conditions,
it would be significantly less since the
activation energy would be very difficult to
achieve given low temperature and short
reaction time making the formation of the
kinetically controlled product more favored.
The increase in temperature causes the
equilibrium constant for the formation of the
thermodynamically-controlled product to be
product (k12 < k34). Hence, the thermodynamic
product was more favored. An increase in
temperature supplies the system sufficient
energy to reach the higher activation energy.
Though it is still easier to reach the activation
energy for the formation of the kinetically-
favored product, the formation of the
thermodynamically product would be still be
more favorable since its product formed
would be more stable for having a lower gibbs
free energy.
Refer to the Gibbs energy diagram in figure
5.1. Kinetically controlled product, B, has a
lower transition state between the competing
reactions hence having lower activation
energy. Since the activation energy for the
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
kinetically favored. The thermodynamically
controlled product, on the other hand, would
have higher transition state and activation
energy thus, being a slow-occurring reaction.
But in comparison to the kinetically controlled
product, the thermodynamically favored

4
product would be more stable than the former
as it would have lower Gibbs free energy that
is, the product formed would have greatly
lower energy than the initial substrate hence
very much stable (Atkins & de Paula, 2006).
Figure 5.1. Gibbs energy diagram for kinetically
vs. thermodynamically controlled products.
Increasing the reaction time has the same
effect as that of increasing the temperature of
the system. Calculated values implies 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.
Increasing the time increases the frequency
of collisions of reactants hence the
thermodynamically favored product is formed.
Though the formation of the kinetically
favored product would still be faster the
thermodynamically-controlled product tends
to dominate due to its lower free energy
(greater ΔG), creating a stable product.
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).
Having sufficient energy ( high temperature)
and longer reaction time, the regenerated
substrate would be capable of producing the
thermodynamically controlled product and
since it is greatly stable compared to the
kinetically-favored product then the formation
of the thermodynamically product would be
more favorable hence, it would dominate in
the system.
Percentage errors of calculated
equilibrium constants were computed using
calculated equilibrium constants from
Arrhenius equation as true values.
𝑘 = 𝐴𝑒 −𝐸𝑎⁄𝑅𝑇 (5-3)
𝑘1
𝑘2
= 𝑒 (𝐸𝑎2 −𝐸𝑎1 ) ⁄𝑅𝑇 (5-4)
𝑘3
𝑘4
= 𝑒 (𝐸𝑎4 −𝐸𝑎3 ) ⁄𝑅𝑇 (5-5)
Calculated percentage errors (refer to table
5.2) show that Monte Carlo method is quite
erroneous.
The second part of the exercise involves
the experimental demonstration of the kinetic
versus thermodynamic control phenomenon
through the isomerization of HgI2. The
isomerization reaction is as follows:
Table 5.4 shows the observations on the
reaction of different concentration of HgCl2
and KI.
5
 Table 5.4. Observations on the experimental determination of the effect of concentration and
reaction time on the isomerization of HgI2.
Appearance of Mixture
Mixture
Immediately after mixing After several minutes
Concentrated
orange suspension Dark orange suspension
KI + HgCl2
Dilute
Yellowish suspension Yellow-orange suspension
KI+ HgCl2

as the orange product increases, the yellow

Upon mixing of the concentrated
solutions, a light orange suspension was
observed whereas a yellowish suspension
was visible on the combination of the diluted
solutions. This implies that at higher reactant
concentrations, the orange, tetragonal isomer
of HgI2 predominates, and at low
reactant concentrations, the yellow rhombic
kinetic product predominates. At higher
concentration of the reactants, there would be
a greater number of effective collisions
between the molecules that overcome the
high activation energy (Ea) of the
thermodynamically-controlled product
making it the preferred product. Reactants of
lower concentrations tend to form the
kinetically-controlled product since at low
concentrated reactants, the number of
effective collisions between molecules is less,
which only the reaction paths with low Ea can
be overcome. Furthermore, based on
Arrhenius equation, the greater the number of
effective collisions results to higher rate
constant and faster rate of reaction thereby
hastening the attainment of equilibrium. The
increase of initial concentration can speed-up
both routes to an equal extent. Nonetheless,
isomer is masked.
After several minutes of mixing with the
use of a magnetic stirrer, dark orange and
yellow-orange mixtures were observed for the
concentrated and dilute mixtures,
respectively. Increase in time favors the
formation of the thermodynamically-favored
product since increasing time will also
increase the frequency of collisions in the
system and thus product formation. The
solution appeared orange yielding the
tetragonal isomer of HgI2 at long reaction
time. The thermodynamically-controlled
product tends to dominate given that it has
lower free energy (greater ΔG), creating a
stable product. On the other hand, at shorter
reaction time, the kinetically-controlled
reaction is favored due to lower activation
energy.
IV. Conclusion
Progress curves for the reaction scheme
demonstrating kinetic versus thermodynamic
control and the effect of temperature and
reaction time were generated using the Monte
Carlo method. Equilibrium constants were
computed to compare the rate at which the
products (kinetic and thermodynamic
controlled) are formed and whichever product
predominates at specific conditions. The

6
effect of reactant concentration and reaction
time was observed experimentally by
V. References
observing the isomerization of HgI2.
The kinetic product predominates if the
ATKINS, P. and J. DE PAULA. 2006.
reaction time is shorter; while the
Physical Chemistry. 8th ed. Oxford,
thermodynamic product predominates if the
England: Oxford University Press.
reaction time is increased. The kinetic product
predominates at a lower temperature; while BALL, D.W. 2003. Physical Chemistry.
the thermodynamic product predominates at USA: Thomson Learning, Inc. Thomson
higher temperatures. Also, the kinetic product Learning.
predominates when the concentrations of LEVINE, I. N. 2002. Physical Chemistry, 6th
reactants are low; while the thermodynamic Ed. New York: McGraw-Hill.
product predominates when the
concentrations of the reactants are high.

VI. Sample Calculations

Initial Condition:
Monte Carlo keq:
[𝐵]𝑒𝑞 𝑘1
𝑘12 = =
[𝐴]𝑒𝑞 𝑘2
7714
𝑘12 = = 140.2545
55

Arrhenius keq:
𝑘1
= 𝑒 (𝐸𝑎2 −𝐸𝑎1 ) ⁄𝑅𝑇
𝑘2
𝑘1 𝑚𝑜𝑙
(800𝐾)
= 𝑒 (33525−1000) ⁄8.314 𝐽. 𝐾 = 132.966
𝑘2

Percent Error:
𝑘𝑀𝐶 − 𝑘𝐴𝑟𝑟ℎ𝑒𝑛𝑖𝑢𝑠
%error = (100)
𝑘𝐴𝑟𝑟ℎ𝑒𝑛𝑖𝑢𝑠
140.2545 − 132.966
%error = (100) = 5.481345679%
132.966