CHEE 323

Design Exercise 1
Date: Jan 25th, 2017

Members:
Yusuf Ahmed 10130098
Kashir Khan 10108540
Theory and Assumptions
This report highlights process of determining the rate of reaction for the acid-
catalyzed fatty acid esterification. Steps 2-5 form intermediate products which are
then consumed to form other products. A reaction coordinate, shown below, was
constructed initially in order to understand the energy level required for each step.

Figure 1 Reaction Coordinate diagram

As can be seen, there are two steps that had significant energy barriers to
overcome relative to the others: step 2 and step 5, labelled as slow. The other
reactions are much quicker and have relatively smaller energy barriers to overcome
because they are either a protonation or deprotonation. Steps 2 and 5 also require
large energy barriers because of the double-bond and carbon-oxygen bond being
broken. As such, steps 2 and 5 were determined to be the rate determining
steps. They were assumed to be equal to each other. This assumption was
necessary when isolating for the tetrahedral intermediate later on. As can also be
seen on the diagram, the reactant (FA) is at a higher energy level than Ester. This is
because the reaction was assumed to be exergonic. An exergonic reaction
has a G of less than zero, meaning it runs voluntarily. This will require the reactant
to be at a higher energy level than the product. As mentioned previously, the
protonation steps occur very quickly. Due to the speed at which they occur, all
protonation steps were assumed to be in equilibrium.
Knowing that steps 1, 3, 4, and 6 were at equilibrium, equations were formed for the
equilibrium constant (K) based on the reactants and products. These equations were
used to calculate the concentration of the intermediates which are required to
calculate the rate of reaction. In order to calculate the concentration of the
intermediate in the second and the fifth reaction, the rate of reactions of these two
equations were assumed to be equal to each other as they are both the slowest
reactions.

The final rate for this reaction can only be written in terms of the observable
species: FA, H+, H20, Ester and MeOH. No intermediates can be included in the final
rate, as they dissociate very quickly and cannot be observed.

Equilibrium constant equations

+
FAH

+
H

+
Step 1: FAH

+
H
[ FA ]

K 1=

+
H

+
THIMeO H

+
THIMeO H
Step 3:
+
H

[ THI ]

[ THI ]
K 3 =
 +
THIH 2 O

+
H

+
Step 4: THIH 2 O

+
H
[ THI ]

K 4 =

+
H

+
EsterH

+
EsterH
Step 6:
+
H

[ Ester ]

[ Ester ]
K 6 =

Rate Law equations for the slow reactions

The quilibrium constant equations are used to substitute the intermediates in the
rate law equations to express the rates in terms of
+
FAH

r 2=r rds=k 2

Plug in for [FA-H+] and [THI-MeOH+]

+
H


 +
THIH 2 O

+
EsterH [ H 2 O]
r 5=r rds =k 5

Plug in for [THI-H2O+] and [Ester-H+]

+
H

+
H

[H 2 O]
k 5 [ Ester ]
k 5 K 4 [ THI ]

In order to express the overall rate equation, the concentration of [THI] is needed
which is an intermediate. To obtain [THI] in terms of the reactants and the
observable species, r2 was set equal to r5. As they are both rate determining steps so
they are assumed to be equal.

r 2=r 5

+ +
H H
=

)[ ]
K3 k 5 [ Ester ] [ H 2 O ]
[ THI ] = ( 1
+
k 5 K 4 k 2
k 2 K 1 [ FA ][ MeOH ] +
K6

This [THI] concentration was plugged in to r 2 to obtain the overall rate equation.
After substitution and simplification the resulting equation is shown below.
+
H

+
H

k 2
r ester =k 2 K 1

The overall reaction equation can be written as.

[ FA ][ MeOH ] [ Ester ] [ H 2 O]