The Enthalpy and Entropy

of Activation for Ethyl

Acetate Saponification
ALJANA PETEK, MAJDA KRAJNC
Faculty of Chemistry and Chemical Engineering, University of Maribor, 2000 Maribor, Slovenia
Received 25 July 2011; revised 11 October 2011, 3 November 2011; accepted 10 December 2011
DOI 10.1002/kin.20712
Published online in Wiley Online Library ([Link]).

ABSTRACT: The saponification of ethyl acetate was measured by conductimetry at different

temperatures within a batch reactor. A new mathematical model for obtaining concentration
profiles from conductivity was presented and used for reaction-kinetics’ determination. The
Arrhenius parameters (A, E a ) showed good agreement with the previously published values.
Basic transition-state theory was used for obtaining the Gibbs energy (G ‡ ), the enthalpy
(H ‡ ), and the entropy (S‡ ) of activation. The low enthalpy of activation and negative entropy
of activation were consistent with a reaction pathway when forming a transition-state complex.
The suggested mechanism involves OH− , acting as a general base for removing proton from
one of the hydroxide hydrating water, placed directly between it and the ester. The nucleophile
from the water then attacks at the electrophilic C of the ester, breaking the π bond, and creating
a tetrahedral intermediate. C 2012 Wiley Periodicals, Inc. Int J Chem Kinet 1–7, 2012

INTRODUCTION and the degradation of cocaine. Applications include

the design of transition-state analogs that inhibit acetyl-
The hydrolysis of carboxylic esters is one of the most cholinesterase and those that elicit anticocaine catalytic
thoroughly studied chemical reactions in chemistry. antibodies [2–5].
Sodium acetate, obtained as an end product during this A variety of experimental and theoretical stud-
study, is a commercially important carboxylic acid salt ies have provided insights into fundamental reaction
and is used throughout a number of industries, such mechanisms. The alkaline hydrolysis (saponification)
as petrol, cosmetics, textiles, and paint. It is used to of carboxylic esters within a solution is commonly ac-
remove insoluble calcium salts from textiles and in- cepted as taking place during a two-step mechanism,
tensify the colors of paints in the paint industry and in where the formation of a tetrahedral intermediate is
the food industry as a means of protection and preser- strongly rate determining [6] and occurs through direct
vation. It is also used as a protector in the leather in- nucleophilic collisions between hydroxide ions and es-
dustry and in the neutralization of mineral acids [1]. ter molecules (BAC 2 mechanism) [7]:
Besides extensive interests within chemistry, the mech-
anism for the base-catalyzed hydrolysis of esters fig-
ures prominently in many biological processes, such
as the metabolism of neurotransmitter acetylcholine

Correspondence to: Aljana Petek; e-mail: [Link]@

[Link].
c 2012 Wiley Periodicals, Inc.
2 PETEK AND KRAJNC

Marlier carried out heavy-atom kinetic isotope ef- at a given time t. The initial condition is x = 0 when
fect experiments for the alkaline hydrolysis of methyl t = 0, so the integration required is
formate [8] and formamide [9] in water solvent and
 x  t
challenged this commonly held view. The isotope ef- dx
   =k dt (3)
fect on the oxygen nucleophile was interpreted as a 0 cB0 − x cA0 − x 0
molecular event, where the attacking nucleophile in
aqueous alkali is water, with general base assistance At a time t after the start of the reaction, the concen-
from hydroxide. The results from a proton inventory trations can be expressed as follows:
experiment for the saponification of ethyl acetate [7]
agree with the mechanism proposed by Marlier. A  
1 cA0 cB0 − x
nuclear magnetic resonance study was performed to ln   = kt (4)
cB0 − cA0 cB0 cA0 − x
the rates of hydroxide-promoted hydrolysis regarding
formamide within an aqueous media of varying mole
fraction D2 O to shed light on whether this mechanism Therefore, a plot of the expression on the left against t
involves a nucleophilic attack of OH− on the C O or should be a straight line from which the rate constant
OH− , acting as a general base for removing protons (k) for the reaction can be obtained.
from an attacking water. Both nucleophilic and gen-
eral base mechanisms can be accommodated, but there The Arrhenius Parameters
are restraints on each mechanism, as discussed in [10].
The objective of this study was to gain additional The rate constant (k) is a function of temperature ac-
insight into the hydrolysis mechanism of ethyl acetate cording to the Arrhenius equation:
within an alkaline aqueous medium, on the basis of
the enthalpy and entropy of activation. To determine Ea
ln k = ln A − (5)
the activation energy and thermodynamics of activa- RT
tion via the transition-state theory (TST), the hydrol-
ysis rate was measured by conductimetry at different and the Arrhenius parameters A and Ea can be obtained
temperatures within a batch reactor. A new mathemat- by plotting ln k versus 1/T . The preexponential factor
ical model for obtaining concentration profiles from or the “frequency factor” (A) is given by the intercept
conductivity is also presented. of the line at 1/T = 0 and the activation energy (Ea )
is obtained from the slope of the line.

THE MATHEMATICAL MODEL The Activation Parameters

The rate of reaction as a function of temperature ac-
Reaction Kinetics cording to the TST is given by the Eyring equation
The reaction considered was the saponification of ethyl [11]:
acetate:
kB T −G‡ /RT
k= e (6)
CH3 COOC2 H5 + NaOH → CH3 COONa + C2 H5 OH h
(1)
This reaction is first order with respect to ethyl ac- where G‡ is the Gibbs energy of activation, kB is
etate (CH3 COOC2 H5 , reactant A) and sodium hydrox- Boltzman’s constant, h is Planck’s constant, and T is
ide (NaOH, reactant B). The rate of decomposition of the temperature. The Gibbs energy of activation may
an ester is a second-order process and is proportional be expressed as
to the product of two reactants’ concentrations:
G‡ = H ‡ − T S ‡ (7)
dcA
= −kcA cB (2) where H ‡ is the enthalpy of activation and S ‡ is
dt
the entropy of activation. Division of Eq. (6) by T
It follows from the reaction stoichiometry that when the throughout and substitution for G‡ leads to the fol-
concentration of NaOH had decreased from the initial lowing logarithmic form:
concentration of cB0 to (cB0 − x), the concentration of    
CH3 COOC2 H5 had also fallen to (cA0 − x), where x is k kB H ‡ 1 S ‡
ln = ln − + (8)
the number of moles per liter of A and B that reacted T h R T R

International Journal of Chemical Kinetics DOI 10.1002/kin

 ENTHALPY AND ENTROPY OF ACTIVATION FOR ETHYL ACETATE SAPONIFICATION 3

In terms of TST, the activation energy is equal to Ea = M

H ‡ + RT for the reaction in solution. E
T

Conductivity and Concentration

Relationship R

The conductivity (κ) was measured to monitor the

changing concentrations of reactants during the saponi- J C
fication reaction. Sodium hydroxide and sodium ac-
etate (CH3 COONa) would contribute to the conductiv-
4.54 mS/cm
ity of the solution since both are strong electrolytes. /
Let κ0 be the conductivity at the start of reaction:
Figure 1 Experiment apparatus: J, thermostat; E, electrode;
κ0 = (aλNa+ + aλOH− ) + (bλNa+ + bλOH− ) (9) T, thermometer; M, mixer; R, batch reactor; C, conductome-
ter.
where a = cA0 and a + b = cB0 , and λi is the mo-
and in a batch-mode operation. The experimental mea-
lar conductivity of the ions. As the reaction proceeds,
surements of conductivity were obtained in a 2-L glass
sodium acetate starts forming after the consumption of
reactor, which was immersed in a thermostat filled with
x sodium hydroxide. Thus, we can write the conduc-
water (Fig. 1).
tivity at any time t:
A volume of 0.6 L of the reactant NaOH solution
was poured into a clean and closed batch reactor and
κt = (aλNa+ + aλOH− ) − xλOH− + xλCH3 COO−
heated/cooled to the desired temperature, but 0.6 L
+ (bλNa+ + bλOH− ) (10) of reactant EtAc was heated/cooled in the thermostat
separately within a closed volumetric flask. When both
At the end of the reaction, the conductivity of the so- reactant solutions reached the experimental tempera-
lution is ture, the reactor was equipped with a mixer, which
continuously mixed the reaction mixture. Then EtAc
κ∞ = (aλNa+ + aλCH3 COO− ) + (bλNa+ + bλOH− ) solution was added into the reactor at t = 0, and the
(11) reactor was closed by its cover. There was no temper-
Subtracting Eq. (10) from Eq. (9) leads to ature change as a result of the mixing of the solution
(addition of EtAc). After that, the conductivity κt was
κ0 − κt = xλOH− − xλCH3 COO− (12) measured continuously at different times, i.e., at the be-
ginning this was at shorter time differences (0.5 min),
and subtracting Eq. (11) from Eq. (10) to and when the reaction slowed down this was at wider
time differences (1, 2, 5 min, . . .). κ∞ was determined
κt − κ∞ = (a − x)(λOH− − λCH3 COO− ) (13) when κ became [Link] addition, 50 mL of the reac-
tant NaOH solution was diluted with the same volume
The above equations allow us for the determination of of distilled water and placed in the thermostat. When
x, in the following way: the experimental temperature was reached, the κ0 was
measured.
κ0 − κt Experiments were carried out in duplicate at seven
x=a (14) different temperatures: 19.1, 21, 23, 24, 25, 27.1,
κt − κ∞
and 32◦ C and were used to validate the mathemati-
cal model, as presented in the Mathematical Model
DEVELOPMENT OF THE EXPERIMENT section. Table I indicates the initial concentrations of
the reactants at each experiment, the conductivity at
The kinetic analysis of chemical reactions frequently t = 0, and the conductivity at t = ∞.
takes place within a homogeneous liquid phase under
RESULTS AND DISCUSSION
isothermal conditions, as in the case of the saponifi-
cation reaction, because it is possible to easily con-
Reaction Kinetics
trol the reactor’s temperature [12]. The experiments
for obtaining a kinetic expression for the saponifica- At each temperature, the values of κ0 , κ∞ , and the se-
tion reaction were carried out at different temperatures ries of κt were determined. These data and Eq. (14)

International Journal of Chemical Kinetics DOI 10.1002/kin

4 PETEK AND KRAJNC

Table I Operational Conditions and Experimental Measurements

Experiment No. T (K) cA0 (M) cB0 (M) κ0 (mS cm−1 ) κ∞ (mS cm−1 )
1 292.25 0.030 0.040 8.070 3.942
2 292.25 0.030 0.040 8.070 3.962
3 294.15 0.028 0.039 8.197 4.195
4 294.15 0.030 0.040 8.180 4.093
5 296.15 0.030 0.040 8.670 4.100
6 296.15 0.030 0.040 8.880 4.438
7 297.15 0.031 0.040 8.860 4.230
8 297.15 0.031 0.040 8.887 4.281
9 298.15 0.026 0.037 8.320 4.372
10 298.15 0.026 0.037 8.262 4.285
11 300.25 0.030 0.040 9.293 5.062
12 300.25 0.030 0.040 9.289 4.668
13 305.15 0.030 0.040 9.920 5.188
14 305.15 0.030 0.040 10.069 5.284

were used to first calculate x, i.e., moles per liter of is formed it immediately results in the formation of
ethyl acetate and sodium hydroxide that reacted at dif- products.
ferent t, and then Eq. (4) was used for determining the
left side of the expression (dependent variable Y ), as
necessary for a graphical evaluation of the rate constant
k. From the slopes of these plots (Figs. 2a–2d present The Arrhenius Parameters
a few samples), the second-order rate constants were
The Arrhenius parameters could be determined using
derived and are summarized in Table II. Correlation co-
the results for the k values [Eq. (5)]. From the linear-
efficients of the linear regressions were usually higher
least-squared fitting of the data in Fig. 3, the values
than 0.99. Repeating an experiment at the same tem-
of Ea and A were calculated to be 48.7 kJ mol−1 and
perature gives the error of the determination of the rate
2.0 × 109 L mol−1 min−1 , respectively. The ideal gas
constant at a single temperature, as shown in Table II.
constant value was R = 8.314 J mol−1 K−1 . Now, the
The reproducibility of the method is good; a margin
Arrhenius equation can be expressed as
of error is between 0.3% and 3.8%. All data for the
reaction are consistent with the BAC 2 mechanism in  
which the formation of the tetrahedral intermediate mol s 48.7 kJ mol−1
ln kOH− 3 = 10.42 −
is rate limiting. If the first step in the mechanism is m RT
rate determining, then the rate of the overall reaction
is equal to the rate of the first step because a subse- The results show good agreement with those
quent step is so fast that once the first intermediate found by other investigators, as can be seen in

Table II Kinetics for Ethyl Acetate Saponification as a Function of Temperature

Experiment No. θ (◦ C) T (K) T −1 (K−1 ) k (L mol−1 min−1 ) ln k ln (k/T )
1 19.1 292.25 3.422 × 10−3 3.88 ± 0.08 1.36 −4.32
2 21.0 294.15 3.399 × 10−3 4.65 ± 0.03 1.54 −4.15
3 23.0 296.15 3.377 × 10−3 5.2 ± 0.2 1.65 −4.04
4 24.0 297.15 3.365 × 10−3 5.77 ± 0.09 1.75 −3.94
5 25.0 298.15 3.354 × 10−3 6.0 ± 0.1 1.79 −3.90
6 27.1 300.25 3.331 × 10−3 6.92 ± 0.02 1.93 −3.77
7 32.0 305.15 3.277 × 10−3 9.2 ± 0.2 2.22 −3.50

International Journal of Chemical Kinetics DOI 10.1002/kin

 ENTHALPY AND ENTROPY OF ACTIVATION FOR ETHYL ACETATE SAPONIFICATION 5

Figure 2 Determination of the reaction-rate constant at θ = 19.1, 23, 25, and 32◦ C.

2.4
–3.5
2.2

–3.7
ln(k / (L mol −1 min −1))

2
ln (k / T )

1.8 –3.9

1.6
–4.1 y = −5571.2x + 14.778
y = −5853.5x + 21.42
1.4 R 2 = 0.9954 R 2 = 0.9934
–4.3
1.2

1 –4.5
0.00325 0.0033 0.00335 0.0034 0.00345 0.00325 0.0033 0.00335 0.0034 0.00345
T −1 / K−1 T −1 / K−1

Figure 3 Arrhenius plot for ethyl acetate saponification Figure 4 Eyring plot for ethyl acetate saponification using
using the data presented in Table II. the data presented in Table II.

the following equation, where the different literature The Activation Parameters
data for rate constants were summarized by Richter
The kinetic data presented in Table II were used for
et al. [13]:
determining the activation parameters. As can be seen
  in Eq. (8), the enthalpy and entropy of activation may
mol s 48.0 kJ mol−1
ln kOH− 3 = 10.26 − be readily determined by plotting ln(k/T ) as a function
m RT of 1/T (Fig. 4). The points are experimental, and the

International Journal of Chemical Kinetics DOI 10.1002/kin

6 PETEK AND KRAJNC

line was obtained by linear regression. Extrapolation

of the line to zero on the abscissa provides ln(kB / h) +
S ‡ /R as the ordinate intercepts; the slope provides
−H ‡ /R. For the saponification of ethyl acetate, the
entropy of activation was determined to be S ‡ =
−74.7 J mol−1 K−1 and enthalpy of activation H ‡ =
46.3 kJ mol−1 . The Boltzmann’s constant value was kB
= 1.381 × 10−23 J K−1 and the Planck constant h =
6.626 × 10−34 J s. The free- energy barrier on moving Figure 5 Suggested mechanism for the nucleophilic attack
from the reactants state to the activated state is given of a hydroxyl ion on the carbonyl carbon of the ester.
by Eq. (7) and is calculated as G‡ = 68.6 kJ mol−1
at 25◦ C.
We found negative activation entropy and positive tional states. This agrees with the view of the transition
activation enthalpy. The lower activation enthalpy and state in that two reactants (a hydroxide and ethyl ac-
high free energy of activation support the formation etate) must come together to make one bigger molecule
of the transition-state complex. It is interesting to note and can no longer move independently of each other.
that the negative activation entropy agrees with the One possible way of forming the tetrahedral interme-
accepted addition–elimination mechanism [14]. diate is presented in Fig. 5 (the solvating waters are
omitted for simplicity).
Although hydroxide is a better nucleophile than wa-
ter, it is hydrated with three waters in aqueous so-
Reaction through an Activated Complex
lution and may not be sterically free to attack the
and a Suggested Mechanism
carbonyl carbon of the ester. The ethyl acetate ester
for the OH− Attack
undergoes alkaline hydrolysis with relatively low en-
We represent a reaction between ethyl acetate and thalpy of activation (46.3 kJ mol−1 ), too low a value
sodium hydroxide as proceeding through the forma- to account for desolvation of OH− , which would be
tion of an activated complex (tetrahedral intermediate). required to form an available pair of electrons on hy-
The second-order rate equation is applicable only when droxide for direct nucleophilic attack. But when the
the concentration of the tetrahedral intermediate is very hydroxide ion is placed in such a way that one water
small and when the reverse reaction rate is negligible in molecule is directly spaced between it and the ester,
comparison with the forward reaction rate. K ‡ denotes the water can act as the actual nucleophile. The water
the equilibrium constant, which tells us the ratio of ac- molecule is probably one of those hydrating a hydrox-
tivated complex species to reactants. We can express it ide ion and is now in the field, where the van der Waals
in terms of Gibbs energy of activation through the defi- force operates over δ + excess charge on the carbonyl
nition and found it to be equal to 9.57 × 10−13 at 25◦ C. carbon of the ester and δ − excess charge on the oxygen
The mechanism has been confirmed by the obtained atom of the water. This makes the proton in a water to
K ‡ because the concentration of the tetrahedral inter- be labile and capable of being donated. The hydroxide
mediate is indeed very small. The activated complex ion then acts more as a general base and removes this
falls apart by unimolecular decay into products, with labile proton by shifting it along a hydrogen bond to
a rate constant k ‡ = (k · c0 /K ‡ ) = 6.3 × 1012 min−1 . generate water. After that the “new formed hydroxide
The characteristic lifetime of the activated complex is nucleophile” attacks the electrophilic C of the ester,
thus 10 ps. breaking the π bond and creating the tetrahedral in-
TST proposes equilibrium between reactants and termediate. These events occur in a concerted process
the transition state, so each of the activation parame- (single step).
ters may be viewed as a difference between the ther-
modynamic function of the transition state and the sum
of the thermodynamic functions of the reactants. The CONCLUSION
energy needed to raise the reactants to the transition-
state energy level is called the enthalpy of activation A new mathematical model has been developed for ob-
and is determined to be 46.3 kJ mol−1 . The negative taining a concentration profile from conductivity data
S ‡ (−74.7 J mol−1 K−1 ) indicates a transition state on the basis of the ethyl acetate saponification reaction,
that has a more ordered structure than the reactants in which was carried out within a batch reactor. The model
the ground state, which means that energy must be par- is rather simple and interesting for understanding reac-
titioned into fewer vibrational, rotational, and transi- tion behavior and provides a useful way of following

International Journal of Chemical Kinetics DOI 10.1002/kin

 ENTHALPY AND ENTROPY OF ACTIVATION FOR ETHYL ACETATE SAPONIFICATION 7

the concentration change in the reactants during the Y Dependent variable—the left-side expression
reaction. of Eq. (4), L mol−1
Experiments were carried out at seven different tem- G‡ Gibbs energy of activation, J mol−1
peratures. The kinetic results (A, Ea ) obtained show H ‡ Enthalpy of activation, J mol−1
good agreement with previously published values. The S ‡ Entropy of activation, J mol−1 K−1
mechanism of ethyl ester saponification consists of δ Excess charge
the formation of a tetrahedral intermediate, which is κt Conductivity at t, mS cm−1
the rate-determining step, followed by the decompo- κ0 Conductivity at t = 0, mS cm−1
sition of the tetrahedral intermediate into products κ∞ Conductivity at t = ∞, mS cm−1
(CH3 COO− + C2 H5 OH). The value of the activation λi Molar ionic conductivity, S m2 mol−1
enthalpy is too small for the formation of a tetra- θ Temperature, ◦ C
hedral intermediate through direct nucleophilic col-
lisions between hydroxide ions and ester molecules.
The suggested mechanism involves the addition of BIBLIOGRAPHY
a hydroxide ion into the ester carbonyl group via
water molecule, with general base assistance from 1. Bursali, N.; Ertunc, S.; Akay, B. Chem Eng Process
hydroxide. 2006, 45, 980.
2. Zhan, C. G.; Landry, D. W.; Ornstein, R. L. J Phys Chem
2000, 104, 7672.
NOMENCLATURE 3. Williams, A. In Enzyme Mechanisms; Page, M. I.;
Williams, A., Eds.; Burlington: London, 1987; p. 123.
A Preexponential factor, L mol−1 min−1 4. Dugas, H. Bioorganic Chemistry, A Chemical Approach
a Mathematical variable, mol L−1 to Enzyme Action, 3rd ed.; Springer: New York, 1996;
b Mathematical variable, mol L−1 Ch. 7.
5. Landry, D. W.; Zhao, K.; Yang, G. X. Q.; Glickman, M.;
cA Concentration of reactant A, mol L−1
Georgiadis, T. M. Science 1993, 259, 1899.
cA0 Initial concentration of EtAc 6. Kirby, A. J. In Comprehensive Chemical Kinetics; Bam-
at t = 0, mol L−1 ford, C. H., Tipper, C. F. H., Eds.; Elsevier: Amsterdam,
cB Concentration of reactant B, mol L−1 1972; Vol. 10.
cB0 Initial concentration of NaOH 7. Mata-Segreda, J. F. J Am Chem Soc 2002, 124, 2259.
at t = 0, mol L−1 8. Marlier, J. F. J Am Chem Soc 1993, 115, 5953.
c0 Standard concentration, mol L−1 9. Marlier, J. F.; Dopke, N. C.; Johnstone, K. R.; Wirdzig,
Ea Activation energy, J mol−1 T. J. J Am Chem Soc 1999, 121, 4356.
h Planck’s constant, J s 10. Ślebocka-Tilk, H.; Neverov, A. A.; Brown, R. S. J Am
K‡ Equilibrium constant Chem Soc 2003, 125, 1851.
k Second-order rate constant, L mol−1 min−1 11. Kuhn, H.; Försterling, H.-D.; Waldeck, D. H. Princi-
ples of Physical Chemistry; Wiley: Hoboken, NJ, 2009;
kB Boltzmann’s constant, J K−1
Ch. 25.
k‡ Rate constant, min−1 12. Grau, M. D.; Nougués, J. M.; Puigjaner, L. Chem Eng J
R Ideal gas constant, J mol−1 K−1 2002, 88, 225.
T Temperature, K 13. Richter, O.; Menges, M.; Kraushaar-Czarnetzki, B.
t Time, min Chem Eng Sci 2009, 64, 2384.
x Moles per liter of A and B that has reacted 14. El Guesmi, N.; Boubaker, T. Int J Chem Kinet 2011, 43,
at time t, mol L−1 255.

International Journal of Chemical Kinetics DOI 10.1002/kin