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The aim of this experiment is to measure the rate constant of the reaction between
ethyl acetate and sodium hydroxide under batch condition.


Chemical processes may be categorized into three main groups that are batch,
continuous or semibatch process; and as either steady-state or transient operation. In batch
process, the inputs are fed to a vessel before starting the process and the outputs are removed
when the process has completed. As for continuous process, the input and output flow
constantly throughout the process. On the other hand, semibatch process is any process that is
neither batch nor continuous process. A process is said to be in steady-state when the process
variable do not change with time. On the contrary, transient or unsteady-state operation is
when any of the process variable change with time (Richard M. Felder,).

This experiment aims to calculate the rate constant for the saponification reaction
between ethyl acetate and sodium hydroxide under batch condition. It is believed, the rate
constant can be determined using two methods which are the integrated rate law method and
the half-life method.

Saponification is the hydrolysis of a carboxylic acid ester under basic condition

producing carboxylic acid salt and an alcohol. This process is crucial in the manufacture of
soap. Soaps are used heavily in both domestic and industrial sectors for hygiene, detergents,
household cleanser, paints and insecticides.

This experiment is conducted to calculate the rate constant from the saponification
process of the reaction between ethyl acetate (ester) and sodium hydroxide (lye) under batch
condition. By definition, saponification is a process where triglycerides react with sodium or
potassium hydroxide (lye) to produce glycerol and a fatty acid salt, called 'soap'. Specifically
in this experiment; ethyl acetate acts as the triglyceride, reacts with sodium hydroxide to
produce sodium acetate (soap) and ethanol (byproduct). The mechanism of saponification can
be showed from Figure 1.


Ethyl Acetate Sodium Hydroxide Sodium Acetate Ethanol

Figure 1: Mechanism of saponification

Theoretically in a saponification process, the hydroxide anion moves to the carbonyl

group of the ester and form a tetrahedral intermediate. Next, the intermediate leaves the ester
as alkoxide anion. A carboxylic acid is forms and then is deprotonated by the alkoxide anion.
Saponification of an ester applied the acyl substitution mechanism. In these reactions, attack
of the nucleophile forms a reactive intermediate. The tetrahedral intermediate collapses. The
carbon-oxygen double bond re-forms, and the original acyl X group is expelled. This is how
carboxylic acid derivatives are changed from one type to another.
Basically, this experiment involved about a few of methods and theory which were
first, the titration. Titration is defined as a volumetric technique in which a solution of one
reactant (titrant) added to a solution of second reactant (analyte) until equivalence point is
reached. In this experiment, sodium hydroxide as titrant had been reacted with the sample
from the saponification process of ethyl acetate and sodium hydroxide which later was added
with hydrochloric acid.

During the saponification process, sodium hydroxide reacted with ethyl acetate and is
continuously consumed. When acid is added to the sample from the product of
saponification, the sample become an acidic solution. This is because the excess hydrochloric
acid will first react with unconsumed sodium hydroxide in the sample to neutralize the
solution and thereby halted any further reaction of ethyl acetate. Phenolphthalein is added to
the solution as an indicator. By using the method of titration to neutralize the acidic solution,
the volume and concentration of sodium hydroxide needed for the neutralization process can
be known. It can be said that the volume of sodium hydroxide needed to change the
colourless colour of solution to pink indicates the amount of ethyl acetate concentration. To
relate sodium hydroxide and ester in the original sample, the following formula can be used.

Original quantity of 0.1 M acid = 0.1*25 / 1000 mol

Acid neutralized by the sample = 0.1(25-y)/1000 mol = moles of NaOH present in

sample withdrawn from reactor.

NaOH concentration in 25 cm3 sample from reactor = ester concentration (c)

According to the Le Chatelier's principle; when a system that is at equilibrium but

then subjected to changes such as in concentration, temperature, volume, or pressure, the
system will alter itself to counteract (partially) the effect of the applied change and a new
equilibrium will be established. In other words, whenever a system in equilibrium is
disturbed the system will adjust itself in such a way that the effect of the change will be
nullified. In this case, this principle is applied during the neutralization of acidic solution of
sample with the base, sodium hydroxide.
Rate of reaction can be defined in many ways. Firstly, it can be explained as the
change in the number of molecules of reacting species per unit volume per unit time. Besides,
rate of reaction also defined to be proportional to the concentration of the reacting species
raised to a power called as the order of the reaction. It can also be understand as the rate of
disappearance of the reactant and the rate of formation of the product. For a chemical reaction
where substance A and B reacts to produce C, the reaction rate has the form:


r = k [A]m[B]n

r = rate
k = rate constant
A = concentration of substance A
B = concentration of substance B
m and n = order of the reaction

Rate constant (k) quantifies the speed of a chemical reaction and can be
acknowledged as rate of reaction when the concentration of each reaction is taken as unity. It
can be said that the greater the value of the rate constant, the faster the reaction. Each reaction
has the same value of the rate constant at a particular temperature. The value of the rate
constant for the same reaction changes with temperature as rate constant depends on
temperature. Besides, the rate constant value does not depend on the concentration of reaction
but depend on the order of reaction. There are two ways of calculating rate constant which
are the integrated rate law method and using the half life method. Also, different order of
reaction has different styles of calculating the rate constant.

The order of reaction is the exponent to which the concentration of the reactant is
raised, and it shows to what extent the concentration of a species affects the rate of a reaction,
as well as which species has the greatest effect on the rate of the reaction. Orders of reaction
for each reactant are often positive integers, but they may also be zero, fractional, or negative.
As an example, if a reaction rate depends on a single reactant and the value of the exponent is
one, then the reaction is said to be first order. A reaction is said to be second order when the
overall order is two. The rate of a second-order reaction may be proportional to one
concentration squared or to the product of two concentrations. For zero-order reactions,
the reaction rate is independent of the concentration of a reactant, so that any changes in the
concentration has no effect on the speed of the reaction.
Integrated rate law method for each order of reactions is different and can be show
from the following equations. Firstly, for zeroth order reactions:

Rate = k [A]

Differential rate law; =0

Integrated rate law; [A] = [A]0 kt

The graph for zeroth order of reaction should shows a negative gradient.

Next, for first order reaction:

Rate = k [A]

Differential rate law; = k[A]

Integrated rate law; ln [] = -kt

The plot for first order reaction will produce a straight line.

Lastly for second order of reaction, the ways of expressing the rate law is depending
on the reactants. As example for the reaction between reactant A and reactant B:

Rate = k [A][B]

[] []
Differential rate law; = = k[A][B]

1 1
Integrated rate law; [] - [] = kt

A plot of 1/[A]t vs time will produce a straight line.

Theoretically, this experiment portrayed the second order of reaction. As the

saponification process takes place, each hydroxide ion that is removed in the formation of
ethanol removes one molecule of ethyl acetate and thus, the concentration of the reactants
decreases. If the process starts with an equal concentrations of the reactants, the concentration
of NaOH can be conveniently followed at different time intervals by withdrawing a sample
from the reaction mixture and determining the NaOH present in using the method of titration
with a standard solution of an acid. The fact that it is a second order reaction can be
established by the consistency of the values of K determined by substituting the titration
results at different time intervals in the second order rate equation.
Half-life of a reaction, t1/2 is important to predict the concentration of reactants over
time. It can be defined as the amount of time needed to reduce the concentration of a
particular reactant to one-half of its original concentration. Different type of reactions have
different half-life calculation. The t1/2 formula for a zero order reaction suggests the half-life
depends on the amount of initial concentration and rate constant. While for first order of
reaction, the half-life depends only on the rate constant (k). Thus, it can be said that for first
order or reaction, the half-life is independent of its initial concentration. Next for second
order of reaction, the half-life depends on the initial concentration and the rate constant. The
formula to calculate half-life for different order of reactions are as the following:

Zero order reaction, 1/2 = 2

ln 2
First order reaction, 1/2 =

Second order reaction, 1/2 = []

Focusing on the second order of reaction, by rearranging the formula of half-life; it is

found that the time taken to halve the concentration of ester is inversely proportional to the
initial concentration. So by plotting a graph of ester concentration versus time, it is possible
to find the t1/2 and the rate constant value. Figure 2 shows the summarized formula for
integrated rate law, half-life and how the graph of different order of reaction should be and
also few other information.
Figure 2: Summarized information for different orders of reaction