You are on page 1of 4

AMERICAN JOURNAL OF SCIENTIFIC AND INDUSTRIAL RESEARCH

2015,Science Hu, http://www.scihub.org/AJSIR


ISSN: 2153-649X, doi:10.5251/ajsir.2015.6.1.1.4

Reaction rate and rate constant of the hydrolysis of ethyl acetate with
sodium hydroxide
Ikhazuangbe, Prosper Monday Ohien and Oni, Aisosa Babalola
Madonna university, Faculty of Engineering
Chemical Engineering Department, P.m.b 302
Enugu, Nigeria
ABSTRACT
Hydrolysis is a chemical decomposition involving breaking of a bond and the addition of elements
of water. In this hydrolysis of ester (ethyl acetate) with an alkali (sodium hydroxide), HCl was
used as catalyst to accelerate it. 1ml and 2ml of ethyl acetate was injected separately into the
500ml reactor vessels which contains 0.05N of NaOH and thoroughly mixed. At regular time
interval, 0, 10, 20, 30, 40, and 90 minutes, 25ml of each of the samples were withdrawn into a
250ml conical flask containing 0.05N HCl, and titrated against 0.05N NaOH solution using
phenolphthalein as indicator. From the titre values, the hydrolysis involving the 1ml ethyl acetate
was faster than that of the 2ml ethyl acetate, indicating that the higher the concentration the faster
the rate of reaction. The rate constant after evaluation from the graphs was approximately
-1 -3
0.003min cm for the 1ml and 2ml ethyl acetate, signifying that while the rate of reaction is
concentration dpendent, the rate constant is not dependent on concentration
Key words: Alkali, concentration, ester, hydrolysis and reactor
INTRODUCTION product is formed. The rate at which the reactant a
is disappearing is proportional to its concentration at
Chemical reaction takes place when a detectable
any instance,
number of molecules of one or more species have
lost their identity and assumed a new form by a I.e. rate (r) (a - x)
change in the kind or number of atoms in the
Rate (r) = k (a - x)
compound and by a change in structure or
configuration of these atoms. In this classical Where k = rate constant
approach to chemical change, it is assumed that the
total mass is neither created nor destroyed when a The concept of rate of reaction is very important in
chemical reaction occurs. evaluating chemical reacting systems. It is the core
factor in the development of performance models to
Chemical kinetics is the part of physical chemistry stimulate reactor functional parameters.
that studies reaction rates. The reaction rate for a
reactant or product in a particular reaction is Factors which determine rate of reaction
intuitively defined as how fast a reaction takes place. a. Availability of reactants and its surface area.
For example, oxidation of iron under the atmosphere The greater the surface area of a solid, the
is a slow reaction which can take years, but the greater the rate of reaction.
combustion of butane in a fire is a reaction that takes b. Concentration: increase in concentration
place in seconds. increase the rate of reaction
Rate of reaction: The rate of reaction is defined as c. Pressure: increase in pressure results in an
the change in the number of molecules of reacting increase in the rate of reaction, if the
species per unit volume per unit time. It is also reactants and products are gaseous
defined to be proportional to the concentration of d. Catalyst: The presences of a catalyst
reacting species raised to a certain power called the generally increase the rate of reaction. There
order of reaction. It is usually taken as the rate at are however, negative catalysts that lower
which the reactant disappear or the rate at which the the rate of reactions.

1
Am. J. Sci. Ind. Res., 2015, 6(1): 1-4

e. Temperature: increase in temperature measure of the rate of reaction, so the greater the
increase rate of reaction value of the rate constant, the faster the reaction.
Each reaction has a definite value of the rate
Rate constant: Rate constant, K quantifies the
constant at a particular temperature and the value of
speed of a chemical reaction. For a chemical reaction
the rate constant for the same reaction changes with
where substance A and B are reacting to produce C,
temperature and the values do not depend upon the
the reaction rate has the form:
concentration of reaction but depend upon order of
Reaction: A+B C reaction.
m n
r = K[A] [B] Hydrolysis of an ester such as acetate in
presence of a mineral acid: Hydrolysis is a
Where K is the rate constant that depends on chemical decomposition involving breaking of a bond
temperature
and the addition of elements of water. The use of an
A is the concentration of substance A in moles per acid catalyst accelerates the hydrolysis. The reaction
volume of solution assuming the reaction is taking rate is expressed in terms of chemical composition of
place throughout the volume of the solution. the reacting species.
Rate constant is the rate of reaction when the i. The hydrolysis of an ester such as ethyl acetate in
concentration of each reaction is taken as unity. That the presence of a mineral acid gives acetic acid and
is why it is also known as specific reaction rate. It is a ethyl alcohol.
CH3COOC2H5 + H2O CH3COOH + C2H5OH H+
Ethyl acetate acetic acid ethyl alcohol
Therefore, the kinetics of the reaction can be studied And verifying the constancy of the value of rate
by taking a known quantity of ethyl acetate and constant, K or in this case, (a - x) ( - Vo) and a
mixing it with a relatively large quantity of HCl. An ( Vo)
aliquot of the reaction mixture is withdrawn at
different intervals of time and titrated against a K= log
standard alkali. Obviously, as the reaction proceeds, 2
the value of alkali required to neutralize the acid (HCl
present as catalyst + CH3COOH produced by Where, Vo = initial titre value
hydrolysis of the ester) progressively increases. = final titre value at the end of the experiment and
The fact that this is a first order reaction is Vt = titre value at the various time intervals chosen
established by substituting the results in the first
order rate expression; As the hydrolysis proceeds, there will be proportional
increase in the concentration of acetic acid formed.
K= log
ii. The hydrolysis of ethyl acetate illustrates a
1 bimolecular reaction that gives sodium acetate and
ethanol as the product from which second order rate
constant can be calculated:
CH3COOC2H5 + NaOH CH3COONa + C2H5OH
Ethyl acetate sodium hydroxide sodium acetate ethanol
As the reaction proceeds, each hydroxide ion present in it direct or indirect titration with a standard
removed in the formation of ethanol removes one solution of an acid.
molecule of ethyl acetate, being the number of moles
- The fact that it is a second order reaction can be
of either OH or ethyl acetate so removed, the
established by the consistency of the values of K
concentration of the reactants decreases. If we start
determined by substituting the titration results at
with equal concentrations of the reactants, the
different time intervals in the second order rate
concentration of NaOH can be conveniently followed
equation as follows:
at different time intervals by withdrawing an aliquot
from the reaction mixture and determining the NaOH

2
Am. J. Sci. Ind. Res., 2015, 6(1): 1-4

K= . slope, the value of the rate constant, K can be


evaluated.
3
Experimental procedure: 25ml of 0.05N HCl was
Where Vo is the volume of the acid equivalent to the measured with a pipette into each of eight (6)
alkali present at the beginning of the experiment and numbered 250ml conical flasks. 400ml of 0.05N
Vt is the volume of the acid equivalent to the alkali NaOH solution was placed in the reactor (500ml
present at any selected time interval. Obviously, Vt is conical flask immersed in a thermostatic water bath
proportional to (a - x) and Vo is proportional to a in o
set at 28 C). At time zero, 1ml of ethyl acetate was
the original rate equation for the second order also measured with a syringe into the reaction vessel
reaction of TYPE I, viz: and the mixture thoroughly shaken for ten seconds.
K= . 25ml of the sample was withdrawn ( and at time 10,
20, 30, 40 and 90minutes after the reaction has gone
4 to completion) and discharged as rapidly as possible
If we start with different concentrations of the into the respective 250ml conical flask containing the
reactants, the second order rate equation TYPE II 25ml 0.05N HCl already and titrated against 0.05N of
should be used for establishing the reaction to be of NaOH solution using two drops phenolphthalein as
second order. indicator. The experiment was repeated with the
volume of ethyl acetate increased to 2ml at the same
K= . log temperature.
5 All reagents used in this experiment are of analar
If b moles of ester and a moles of NaOH are taken grade.
o
initially, then Table 2: Temperature = 28 C and volume of ethyl
acetate = 1ml
a Vo (the volume of acid equivalent to the amount
of NaOH present initially) Time Titre Vt - (Vo - Log
(min) (ml) )
(a - x) Vt (the volume of acid equivalent to the
amount of NaOH present at time, t)
(a - b) (the volume of acid equivalent to the 0 5.60 -16.70 -16.70 1.00 0.00
amount of NaOH present at the end of the reaction)
10 17.80 -4.50 -16.70 3.71 0.57
X = a (a - x) = Vo - Vt
b= a (a - b) = Vo - 20 20.90 -1.40 -16.70 11.93 1.08
Therefore,
(b - x) = a (a - b) [a (a - x)] 30 21.60 -0.70 -16.70 23.86 1.38
= a (a - b) a + (a - x)
= (a - x) (a - b) = Vt - 40 21.90 -0.40 -16.70 41.75 1.62
By substitution, equation 5 becomes
K= . log 90 22.30 0.00 -16.70 - -

6
K= [ ] o
Table 1: Temperature = 28 C and volume of ethyl
Log = + log acetate = 2ml
Time Titre Vt - (Vo - Log
7 (min) (ml) )
Since this equation is of the form: y = mx + c, this
represents an equation for a straight line.
0 9.70 -15.20 -15.20 1.00 0.00
Therefore, a plot of log vs. t gives a straight
10 22.80 -2.10 -15.20 7.24 0.86
line with a slope equal to . From the value of the
20 24.00 -0.90 -15.20 16.89 1.23

3
Am. J. Sci. Ind. Res., 2015, 6(1): 1-4

30 24.40 -0.50 -15.20 30.40 1.48 gives a slope which is equal to , from which K is
40 24.70 -0.20 -15.20 76.00 1.88 evaluated:
-1
90 24.90 0.00 -15.20 - - Slope = 0.034min =

Therefore,
( ) 0.034 =
Log
( )
1.8
K=
1.6
K = 0.0031
1.4
-1 -3
1.2 K 0.003min cm
1 Also, for the 2ml ethyl acetate:
0.8 From equation 7, Log = + log . Using
0.6
table 1, a plot of Log against time in figure 1,
0.4
gives a slope which is equal to , from which K is
0.2
evaluated:
0
-1
0 10 20 30 40 50 Slope = 0.027min =
Tiime (min) Therefore,
o
Fig.2: graph for 1ml of ethyl acetate at 28 C 0.027 =

K=
( 2)
Log = 0.0028
( 1.8
)
-1 -3
1.6 K 0.003min cm
1.4 Conclusion: In conclusion, it can be seen from this
experiment that rate of reaction is concentration
1.2
dependent while rate constant is not. Also, that the
1 rate constant for the hydrolysis of ethyl acetate with
o
0.8 sodium hydroxide using HCl as a catalyst at 28 C is
-1 -3
approximately 0.003min cm .
0.6
0.4 REFERENCE
0.2 E.U. Akusoba and G.O. Ewelukwa, (2006); Calculations in
chemistry for senior secondary schools, Africana first
0 publishers limited, Owerri, Nigeria. Pg 123 124
0 10 20 30
Time (min) 40 50
H.S. Fogler (2008); Elements of chemical reaction
o engineering, Fourth edition, Pearson Education
Fig.1: graph for 2ml of ethyl acetate at 28 C international, Massachusetts, USA. Pg. 4-7
For the 1ml ethyl acetate: Octave Levenspiel, (2008); chemical reaction engineering,
rd
3 edition, Choudhary Press, Delhi, India. Pg 27 -28
From equation 7, Log = + log , using
S.S. Dara (2009); A textbook of engineering chemistry, S.
table 2, a plot of Log against time in figure 2, Chand and company Limited, Ram Nagar, New Delhi.
pg.845 862