Seung Chung

Chem 114
05/23/12
Kinetics in Solution
Abstract: The physical property of conductivity in solutions was used in order to examine the
kinetics of saponification reactions.Comparisons of R
2
values of the respective fitted curves
represented by the first order reaction equations, and the second order reaction equations suggest
that the saponification reaction behaves much more like a second order reaction. Furthermore, the
physical properties of the saponification reaction were obtained by using the transition state
theory to calculate the enthalpy, entropy, and the activation energy. The reaction at standard
conditions had the following properties: an enthalpy value of 155 kJ/mol, entropy value of 525
J/mol, and activation energy of 185 kJ/ mol. Lastly, different ester reagents were used in the
same saponification reaction in order to examine the inductivity effects of larger esters. Results
show that indeed larger esters react much slower than the smaller counterparts according to the
rate constants obtained: 0.13180.0005s
-1
*mol
-1
for methyl acetate, 0.0109350.00009 s
-1
*mol
-1
for ethyl acetate, and

0.06830.0004 for propyl acetate.
Introduction
The saponification reaction involves hydrolysis of acetate esters according to the following
formula:
AcO-R + Na
+
+ OH
-
AcO
-
+ Na
+
+ R-OH
Eqn. 1)
The physical values such as the change in enthalpy, the change of entropy, and the activation
energy of the reaction can all be determined by examining the kinetics of the saponification
reaction. Furthermore, the kinetics of this reaction can be examined by monitoring the conductivity
of the ions because there is a large difference in conductivity values between the AcO
-
ion and the
OH
-
ion of Eqn. 1, in which conductivity values are larger for OH
-
ions than it is for AcO
-
ions.
Thus, as more OH
-
molecules react to form an alcohol and AcO
-
ions, the conductivity values of
the solution steadily decreases.
However, since solutions are examined, the conductivity values that were measured were
obtained using Eqn 2.

Na Na A A OH OH
C C C + +
Eqn. 2)
Since Na
+
ions are not part of the reaction, the conductivity contribution of the amount of Na
+
ions
is constant, and the measured conductivity values are solely dependent on the OH
-
concentration
and the AcO
-
ion concentration.
To determine the rate constant of the saponification reaction:

,
_

0
1 b C
A
or

,
_

0
1 a C
A
Eqn. 3)
a= the concentration of the ester; b= the concentration of hydroxide ions, and both (a) and (b) can
represent the limiting reagent for the reaction mixture; C
A
= the amount of product formed
assuming that the reaction follows Eqn. 1. Using Eqn. 3, and the equations of second order
reactions or first order equations, a direct relationship between the conductivity values and time
can be made to determine the rate constant of the reaction. Finally using this relationship, other
physical values can be obtained such as enthalpy, entropy, and the activation energy of the system.
Experimental Results
Using a conductivity meter that was connected to a computer running a Lab View software,
the conductivity values of solutions were obtained. A stock solution of 0.06 M NaOH was
prepared by mixing 2.4450.001 g of NaOH pellets and 1 L of deionized water. Furthermore,
another stock solution of 0.04 M NaOH was prepared by mixing _____g of NaOH pellets and 1 L
of deionized water. Then 100 mL of the stock solution was put into a 150 mL beaker, and a
magnetic stir bar was placed inside the beaker, and the solution was stirred on top of a hot plate.
Afterwards, the Lab View software was started and the probe was placed inside the 150 mL
beaker. The conductivity values of the solution was recorded to be
0
. Once a stable
0
value was
obtained with the correct parameters, 99.5% pure ethyl acetate was added to the solution. The
amounts of ethyl acetate added, and which stock solution was used to measure a specific rate
constant were all consistent with the concentrations of the solutions prepared accordingly to the
following table:
0.06M NaOH,0.06MAcO-R 0.04 M NaOH, 0.06 M AcO-
R
0.06M NaOH, 0.04 M
AcO-R
k
1st Order
(3.120.02)*10
-3
[s
-1
] (0.3010.002)*10
-2
[s
-1
] (1.500.02)*10
-3

[s
-1
]
k
2nd Order
0.1480.001 [s
-1
*mol
-1
] (9.6000.008)*10
-2

[s
-1
*mol
-1
]
(1.09350.0009)*10
-1
[s
-1
*mol
-1
]
Table 1. The Rate Constant Values of the Saponification Reaction at Differing Concentrations.
Furthermore, the reactions of all solutions prepared were allowed to reach

, and its value was

recorded at the end of the lab period, since it is a required aspect when evaluating rate constants of
reactions as shown in equation 3.
If the rate of the reaction is assumed to be a first order reaction, the rate of the reaction is
only proportional to the concentration of ethyl acetate added since the reaction is only started when
ethyl acetate is added to the reaction mixture.
) (
A
A
C a k
dt
dC
Eqn. 4)
k= rate constant of the reaction. Integrating Eqn. 4 yields a much more convenient result that can
be used to obtain the rate constant:
( )
A
C a kt ln Eqn. 5)
However, in a second order reaction, the rate of the reaction depends on both concentrations of
OH
-
ions and ethyl acetate according to the following formula:
( ) ( )
A A
A
C a C b k
dt
dC
Eqn. 6)

t b a k
C b a
C a b
A
A
) (
(
) (
ln
1
]
1

Eqn. 7)
Thus, the rate constants of the all the three different solutions represented by the first row of table
1, were calculated by using the respective formulas for first order reactions and second order
reactions.
Second Order Fit of Experimental Data y = 0.1093x + 0.0083
R
2
= 0.9998
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 2 4 6 8 10 12
F(time)
F
(
c
o
n
d
u
c
t
i
v
i
t
y
)

Figure 1. The Fit of Experimental Values of Conductivity vs. Time, Representing a Second Order
Equation.
First Order Fit Of Experimentally Obtained Data
y = 0.0015x + 2.9967
R
2
= 0.946
0
0.5
1
1.5
2
2.5
3
3.5
4
0 100 200 300 400 500 600
f(Time)
f
(
C
o
n
d
u
c
t
i
v
i
t
y
)
Figure 2. The Trend Line That Doesnt Fit Quite as Well as the Second Order Reaction Trend
Line.
0.06M NaOH,0.06MAcO-R 0.06M NaOH, 0.04 M AcO-
R
0.04 M NaOH, 0.06 M
AcO-R
R
2
1st Order
0.9780 0.9859 0.9460
R
2
2ndOrder
0.9940 0.9997 0.9998
Table 2. R
2
Values of the Fitted Curve of Equations 4, and 7 for First Order Reactions and Second
Order Reactions Respectively.
In order to determine the activation energy of the system, rate constants at two different
temperatures must be experimentally obtained. Thus two rate constants at temperatures ~4 C and
~ 45 C were obtained. First the cold experiment: a solution of 100 mL of NaOH 0.06M in a 150
mL beaker was put in an ice bath in order to obtain a stable teperature of 1-4 C. Once the
temperature was stable, 0.25 equivalents of ethyl acetate (148 L) was added to the solution to
examine the kinetics of the cold temperature saponification reaction.
Determining the Rate Constant
y = 0.0059x + 0.9953
R
2
= 0.987
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 10 20 30 40 50 60
LN((b(a-C)/(a(b-C))
k
(
a
-
b
)
t
Figure 3. Rate Constant Obtained for a Cold Solution at Temperature ~2774 K.
Then the hot Scan: a solution of 100 mL of NaOH 0.06M in a 150 mL beaker was put on a
hot plate until the temperature was stable from 40-45 C. Once a stable temperature was obtained,
0.06 equivalents of ethyl acetate ( 36 L ) was added, and the measurement of the conductivity was
obtained.
Determining k2 at Temperature~ 318 K
y = 0.0161x + 0.9615
R
2
= 0.8237
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
0 5 10 15 20 25
LN((b(a-C))/(a(b-C)))
k
(
a
-
b
)
t
Figure 4. Determining the Rate Constant of the Saponification Reaction at Higher Temperatures
Then using data obtained from Figure 3, and Figure 4, the rate constant values can be used
to determine the activation energy of the system. The equation that allows the determination of the
activation energy of the system is a modified form of the Arrhenius equation, and its equation is
as follows:

,
_

,
_

2 1 1
2
1 1
ln
T T R
E
k
k
a
Eqn. 8)

( ) ( )

,
_

,
_

t
t

K K mol K J
E
a
4 318
1
4 277
1
* / 3145 . 8 03 . 0 88 . 5
05 . 0 1 . 16
ln
mol kJ E
a
/ 5 18t
By definition of enthalpy, the following equation is obtained :
RT E H
a

mol kJ K
mol K
J
kJ H / 5 15 ) 4 298 (
*
3145 . 8 ) 5 18 ( t t t
Using the Transition State Theory, the entropy of the saponification reaction can also be obtained
according to the following equation:

,
_

,
_

kT
H
k
S
h
kT
CONSTANT RATE exp exp
Eqn. 9)
where k= to Boltzmanns constant Eqn. Thus plugging in experimental values gives:
( )
( )

,
_

t
t

,
_

+
t
t

K K J
mol J
K J
S
K
J
mol s
) 4 298 ( * 10 * 38 . 1
/ 10 * ) 5 15 (
exp
* 10 * 38 . 1
exp
) 4 298 (
10 * 38 . 1
0009 . 0 0935 . 1
1 23
3
1 23 2
23
1 1
mol J S / ) 5 52 ( t
Additional experiments were done in which propyl acetate and methyl acetate were used to
react with the OH
-
ions. 3251% L of 99% pure methyl acetate was transferred into a beaker
containing 100 mL of the 0.06 NaOH stock solution and the measurements of conductivity were
made. Lastly, 4751% L of 98% pure propyl acetate was added into a beaker containing 100 mL
of the 0.06 NaOH stock solution, and the conductivity was measured. Using the same procedure to
obtain rate constants in table 1, the rate constant values are: methyl acetate rate constant =
0.13180.0005 s
-1
*mol
-1
; ethyl acetate rate constant =(0.109350.0009)*10
-1
s
-1
*mol
-1
; propyl
acetate rate constant= 0.06830.0004.
Superposition Graph of the Three Different Reagents Used
0
2
4
6
8
10
12
14
16
0 200 400 600 800 1000 1200 1400
Time (seconds)
C
o
n
d
u
c
t
i
v
i
t
y

1
/
(
o
h
m
*
c
m
)
Methyl Acetate
Ethyl Acetate
Propyl Acetate
Figure 5. The Trend of Increasing Carbons of the Ester Reagent Used for Saponification.
Discussion
The R
2
value obtained when fitting the data into a graph that represents a first order
reaction is poorer than the data that is fitted to represent a second order reaction. This results
suggests that the reaction is second order. Moreover, Figure 1 is obviously a better fit than is figure
2 because figure 1s trend line doesnt reach the end points of the datathere is a kind of curve at
the ends; however, figure 2s fitted line is a straight line throughout the whole range of the
experimental data. Moreover, according to table 1, the rate constants are larger for the second order
reaction fitted parameters than the first order reaction fitted parameters. These large differences in
values suggest that one is the preferred model, which is the second order reaction model.
Furthermore, according to Mata-Segreda (2002), a saponification reaction obeys the Tetrahedral
Bimolecular Mechanism. A reaction that is bimolecular is by definition a second order reaction
since the rate of the reaction depends on the concentration of two species.
Furthermore, the physical properties of the saponification reaction were obtained by using
the transition state theory to calculate the enthalpy, entropy, and the activation energy of the
system. The reaction at standard conditions had the following properties: an enthalpy value of
155 kJ/mol, entropy value of 525 J/mol, and an activation energy of 185 kJ/ mol. The positive
entropy value signifies that the system is becoming more disorderly. The positive enthalpy value
signifies that the reaction is an endothermic reaction in which heat is absorbed by the system. The
magnetic stir bar was set to vigorously stir the solution which was used make the system obtain the
energy required to step upbove the threshold activation energy for the reaction to start.
Polar, steric, and resonance effects of the R-group of Eqn 1 all have an effect on the free
energy of activation of the saponification reaction (Pavelich et. al. 1957). The longer the chain, the
larger the inductivity effect, and thus the free energy of activation becomes larger. Experimental
results support this trend when examining the rate constants of each reagent used 0.13180.0005s
-
1
*mol
-1
for methyl acetate, 0.0109350.00009 s
-1
*mol
-1
for ethyl acetate, and

0.06830.0004 for
propyl acetate. A larger rate constant signifies that the reaction will reach equilibrium faster, or that
the formation of products will be much faster. Thus, methyl acetate, because it has less of an
inductive effect, will create products faster than ethyl acetate or propyl acetate. Lastly, when
observing figure 5, it is obvious that propyl acetate takes the longest amount of time to react with
OH
-
. The curve that represents the propyl acetate reagent is drastically shifted to the right in terms
of the methyl acetate curve, and the ethyl acetate curve is shifted only a bit to the right.
Results show consistent values that make sense. There could be systematic errors in the
system that requires additional experiments to pinpoint; however, the experiment was sufficient in
that various physical values were obtained from just measuring conductivity values over time. That
in of itself is quite a feat. Thus, errors were propagated, and analyzed, and all the reported values
were shown with their respective errors.
Conclusion
Thus, physical properties were examined and rate constants were examined. Although
experimentally derived rate constants, and physical values greatly deviate from the literature values
of other articles, the experiments of those articles didnt have the same instrument, nor the same
conditions as the experiment that was conducted. Thus, values are expected to be different, and
values of the experiment are considered satisfactory because they give values that make sense, and
they are consistent with the expected trends that the data was supposed to take.
References
1. Atkins, P.; De Paula, J. Physical Chemistry, 7
th
Ed. Freeman N.Y.
2. Mata-Segreda, J.F. 2002. Hydroxide as General Base in the Saponification of Ethyl
Acetate. J. Am. Chem. Soc., 124, No. 10.
3. Pavelich, W.A.; Taft Jr., R.W. 1957. The Evaluation of Inductive and Steric Effects on
Reactivity. The Methoxide Ioncatalyzed Rates of Methanolysis of I-Menthyl Esters in
Methanol1 J. Am. Chem. Soc. Vol. 79, 4935-4940.