AKINPELUMI K.

F 100401013

ABSTRACT

This experiment was carried out to monitor the course of the reaction between sodium hydroxide
and ethyl acetate in a batch reactor by withdrawing samples periodically, neutralizing with
excess hydrochloric acid and back titrating with standard sodium hydroxide.

The results obtained from this experiment was then use to test the hypothesis that the reaction is
a second order, and also to evaluate the rate constant for the reaction.

The experimental data was analyzed using two different methods: the differential and integral
correlation method; with tables and graphs plotted to obtain the rate constant of the reaction.

The reaction was confirmed a second order reaction because the graphs obtained were straight
line graphs; and the rate constant obtained from both the differential and integral methods was
0.01 moldm-3s-1, and 0.00439moldm-3s-1 respectively.

As a result of the very small k1 values, the reverse reaction was neglected.
 AKINPELUMI K.F 100401013

INTRODUCTION

The aim of this experiment is to test the hypothesis that the saponification of ethyl acetate using
a batch reactor is second order, and to evaluate a rate constant for the reaction.

The term saponification is the name given to the chemical reaction that occurs when a vegetable
oil or animal fat is mixed with a strong alkali. The products of the reaction are two: soap and
glycerin. Water is also present, but it does not enter into the chemical reaction. The water is only
a vehicle for the alkali, which is otherwise a dry powder.

The name saponification literally means "soap making". The root word, "sapo", is Latin for soap.
The Italian word for soap is sapone. Soap making as an art has its origins in ancient Babylon
around 2500 - 2800 BC.

The saponification of ethyl acetate (CH3COOC2H5) with dilute sodium hydroxide (NaOH) is a
second-order reaction which can be represented by the following equation:

NaOH + CH3COOC2H5 → CH3COONa + C2H5OH

The course of the reaction between sodium hydroxide and ethyl acetate is followed in a batch
reactor by withdrawing samples periodically, neutralizing with excess hydrochloric acid and
back titrating with standard sodium hydroxide.

Assuming for the present that the reaction is reversible and second order in both directions the
specific reaction rate for the batch operation is given by:

−dCA
dt
= k1CACB – k2CCCD

−1 dN −dCA
V dt
= dt
= k1CACB – k2CCCD

Where N = moles of ethyl acetate in the reaction at time t

V = volume of reaction mixture

Kt,ks = rate constants for the forward and reverse reactions

 AKINPELUMI K.F 100401013

CA = molar concentration of ethyl acetate

CB = molar concentration of sodium hydroxide

CC = molar concentration of sodium acetate

CD = molar concentration of ethanol

For this present experiment, equal concentration of reactants are used so that C A = CB. Also,
previous equilibrium tests have shown that k is small and that as a good approximation; the
reverse reaction may be neglected, equation then becomes:

−dCA
dt
= k1CA2

Integrating between the start of the experiment CA12

CA t
dCA
−∫ = ∫ k 1 dt
CAO C A 12 0

and some time later, gives

1 1
CA
- CA 0
= k1 t

which then gives the concentration of ethyl acetate in the reactor at any time t after the start.

Second Order Reactions are characterized by the property that their rate is proportional to the
product of two reactant concentrations (or the square of one concentration). Suppose that A --->
products is second order in A, or suppose that A + B ---> products is first order in A and also first
order in B. Then the differential rate laws in these two cases are given by Differential Rate Laws:

d[A]/dt = -k [A]2 (for 2A ---> products)

or dx/dt = -k [A][B] (for A + B ---> products)

In mathematical language, these are first order differential equations because they contain the
first derivative and no higher derivatives. A chemist calls them second order rate laws because
the rate is proportional to the product of two concentrations. By elementary integration of these
differential equations Integrated Rate Laws can be obtained:

1/[A] - 1/[A]0 = k t (for 2A ---> products)

or (1/(a-b)) [ln((a-x)/(b-x))-ln(a/b)] = k t (for A + B ---> products)
 AKINPELUMI K.F 100401013

where a and b are the initial concentrations of A and B (assuming a not equal to b), and x is the
extent of reaction at time t. Note that the latter can also be written:

(a-x)/(b-x) = (a/b)exp[(a-b)kt].

The field of chemical kinetics is concerned with the rate or speed at which a chemical reaction
occurs. Knowledge of a chemical reaction and the integrated rate law (an expression relating
concentration with time) for the reaction allows us to accurately predict how much of a given
reactant or product exists at any time during the reaction.

The rate law can also provide useful insight into which variables control a reaction (temperature,
reactant concentration, catalysts) and how these variables can be used to maximize the amount of
product(s) formed in the reaction or minimize the time involved to obtain product(s).

The experimental kinetic data obtained during the reaction is used to help understand the
mechanism of a reaction. The reaction mechanism describes how a reaction proceeds through
single (elementary) steps on the molecular level. In its simplest explanation, rate of a reaction
means how fast the concentration of reactants diminishes or products increases.

The reaction will continue until it reaches equilibrium and in some cases until it reaches
completion. In order to measure the reaction rate, we need to be able to monitor either the
decrease in the reactant concentration or increase in product concentration.

This monitoring can be done in several ways depending on the type of reactants and products
present in the medium. When measuring reaction rates, we should be careful about changes in
temperature. All reaction rates are temperature sensitive to varying degrees. Therefore, when
measuring reaction rates, we must keep the temperature constant.

APPLICATIONS OF SAPONIFICATION
 AKINPELUMI K.F 100401013

The knowledge of saponification is relevant to many technologies and many aspects of everyday
life. Such applications include:

 Soft vs Hard Soap

 Lithium Soaps

 Fire Extinguishers

1. Soft vs Hard Soap

Depending on the nature of the alkali used in their production, soaps have distinct
properties. Sodium hydroxide (NaOH) gives ‘hard soap’ whereas when potassium
hydroxide (KOH) is used, a soft soap is formed.

2. Lithium Soap

Lithium derivatives of 12-hydroxystearate and several other carboxylic acids are

important constituents of lubricating greases. In Lithium based greases, lithium
carboxylates are thickeners. ‘Complex Soaps’ are also common, these being a
combination of metallic soaps, such as lithium and calcium soaps.

3. Fire Extinguishers

Fires involving cooking fats and oils, burn better than flammable liquids, rendering a
standard class B extinguishers ineffective. Flammable liquids have flash points under
100oF. Cooking oil is combustible liquid since it has a flash point over 100o F. Such
should be extinguished with a wet chemical extinguisher.
 AKINPELUMI K.F 100401013

FACTORS THAT AFFECT REACTION RATE

It is useful to be able to predict whether an action will affect the rate at which a
chemical reaction proceeds. There are several factors that can influence the rate of a
chemical reaction. In general, a factor that increases the number of collisions between
particles will increase the reaction rate and a factor that decreases the number of
collisions between particles will decrease the chemical reaction rate.

These factors are:

1. Temperature

2. Presence of catalysts and competitors

3. Medium

4. Concentration of reactants.
 AKINPELUMI K.F 100401013

EXPERIMENTAL PROCEDURE

500ml of standard 2ml HCl and 1000ml of standard 2g NaOH was prepared, by diluting the
stock solutions with an appropriate amount of distilled water (the molarities of both solutions
was made to be approximately 0.05M).

400ml of NaOH solution was then placed in the reaction vessel.

The burettes were filled with standard HCl and NaOH solutions.

25ml of the standard HCl was then pipetted into each of the 12 units of 250ml conical flasks.

At time t=0, 2ml of ethyl acetate was pipette into the reaction vessel and thoroughly shaken.

At specified times of 3,5,7,10,15,20,25 and 30 minutes, 25ml sample of reaction solution was
pipette out and added to the respective conical flasks containing the 25ml portions of HCl. The
time was started when half of the samples had been added.

It was then titrated with standard NaOH solution using phenolphthalein as an indicator.
 AKINPELUMI K.F 100401013

INSTRUMENTATION AND EQUIPMENT

Thermostatic bath,

Timer,

Burettes,

Pipettes

Conical flask

Measuring cylinder

Ethyl acetate

Standard solutions of hydrochloric acid and sodium hydroxide,

Phenolphthalein indicator.
 AKINPELUMI K.F 100401013

RESULTS

The solutions containing the 2ml ethyl acetate solution in 400ml of NaOH was pipetted out into
beakers containing 25ml of HCl solution at stated time intervals and the resulting solutions were
back-titrated against HCl.

The experimental result is shown in the table below:

Time (mins) Initial Burette reading Final burette Vol. of base (NaOH)
(cm3) reading used
(cm3) (cm3)
3 0.20 11.00 10.80
5 32.50 17.70 14.80
7 0.00 17.70 17.70
10 0.70 21.20 19.50
12 1.70 21.30 19.60
15 0.30 25.90 25.60
20 1.90 31.30 29.40
25 0.00 32.00 32.00
30 2.20 35.40 33.40

From the preparation of the acid,

 AKINPELUMI K.F 100401013

1000ml of standard 4ml HCl was prepared.

Volume of HCl = 4ml

Density of HCl = 1.189g/mol

Mass of HCl = 1.189g/mol * 4ml = 4.756g

Molecular mass of HCl = 36.5g

1mol 1
Molar concentration of HCl = 4.756g * * = 0.1303mol/dm3
36.5 g 1 dm 3

The Balanced equation of reaction is:

HCl + NaOH → NaCl + H2O

nNaOH = nHCl = 1

The Stoichiometry of the above reaction shows that nNaOH = nHCl

Initial concentration of NaOH = C2 = 0.05mol/dm3

Initial concentration of HCl = C1 = 0.1303mol/dm3

Concentration of NaOH at varying time intervals = CB ?

Vol of NaOH needed for titration at varying time intervals = V2 (titre value)

Vol of HCl used = V1 = 25ml

The CB at the various time intervals would be calculated thus:

CB = C A

C 1V 1−C 2 V 2
CB = C A =
V1

Where: CB = Concentration of NaOH at varying time intervals

C1 = Initial concentration of HCl = 0.1303mol/dm3

 AKINPELUMI K.F 100401013

C2 = Initial concentration of NaOH = 0.05mol/dm3

V1 = Vol of HCl used = 25ml

V2 = Vol of NaOH needed for titration at varying time intervals (titre value)

At time, t = 3min:

V2 = 10.8ml

( 0.1303× 25 )−(0.05 ×10.8)

CB = C A = = 0.1087mol/dm3
25

At time, t = 5min:

V2 = 14.8ml

( 0.1303× 25 )−(0.05 ×14.8)

CB = C A = = 0.1087mol/dm3
25

At time, t = 7min:

V2 = 17.70ml

( 0.1303× 25 )−(0.05 ×17.70)

CB = C A = = 0.0949mol/dm3
25

At time, t = 10min:

V2 = 19.50ml

( 0.1303× 25 )−(0.05 ×19.50)

CB = C A = = 0.0913mol/dm3
25
 AKINPELUMI K.F 100401013

At time, t = 12min:

V2 = 19.60ml

( 0.1303× 25 )−(0.05 ×19.60)

CB = C A = = 0.0911mol/dm3
25

At time, t = 15min:

V2 = 25.60ml

( 0.1303× 25 )−(0.05 ×25.60)

CB = C A = = 0.0791mol/dm3
25

At time, t = 20min:

V2 = 29.40ml

( 0.1303× 25 )−(0.05 ×29.40)

CB = C A = = 0.0715mol/dm3
25

At time, t = 25min:

V2 = 32.00ml

( 0.1303× 25 )−(0.05 ×32.00)

CB = C A = = 0.0663mol/dm3
25

At time, t = 30min:

V2 = 33.40ml

( 0.1303× 25 )−(0.05 ×33.40)

CB = C A = = 0.0635mol/dm3
25

These values can be tabulated thus:

 AKINPELUMI K.F 100401013

Time CA (CA)2 dCA/dt

(min) (mol/dm3) (mol /dm6) *103
2
(mol/dm3.s) * 103
0 0.1303 16.978 ------
3 0.1087 11.816 -7.20
5 0.1007 10.140 -5.92
7 0.0949 9.006 -5.06
10 0.0913 8.336 -3.90
12 0.0911 8.299 -3.27
15 0.0791 6.257 -3.41
20 0.0715 5.112 -2.94
25 0.0663 4.396 -2.56
30 0.0635 4.032 -2.23

 From the differential expression:

−dCA
dt
= k1CA2

The graph of dCA /dt against CA2 is plotted in figure 1

The slope of the graph = -k1

Slope = (-1.5 – (-5.7)) *10-3 / (2.75 – 9.75) *10-3 = 4.2 / -0.6 = -0.60moldm-3min-1

But slope = - k1

Therefore, k1 = 0.60moldm-3min-1 = 0.01 moldm-3s-1

 Using the integral correlation method:

1 1
CA
- CA 0
= k1 t
 AKINPELUMI K.F 100401013

Time (min)
CA 1 1
CA
- CA 0
(mol/dm3)
(dm3/mol)
0 0.1303 0
3 0.1087 1.525
5 0.1007 2.256
7 0.0949 2.863
10 0.0913 3.278
12 0.0911 3.302
15 0.0791 4.968
20 0.0715 6.311
25 0.0663 7.408
30 0.0635 8.073

1 1
CA
- CA 0
= k1 t

1 1
The graph of
CA
- CA 0
against time (min) is plotted in figure 1

The slope of this graph is k1

From the graph, slope = (7.7 – 2.3) / (26.5 – 6) = 5.4 / 20.5 = 0.2634moldm-3min-1

Since k1 = slope;

k1 = 0.2634moldm-3min-1 = 0.00439moldm-3s-1
 AKINPELUMI K.F 100401013

DISCUSSION

The kinetic or experimental data obtained was analyzed using the differential and integral
correlation methods.

dCA
The differential correlation method involves determining at the various time intervals
dt
2
and plotting its values against CA . The gradient of the graph gave the rate constant K1 for the
reaction.

The result gotten from this method of analysis emphasized the hypothesis that the reaction is
second order. This is so because the graph obtained was a straight line graph which denotes a
second order reaction. The rate constant gotten from the differential correlation method was 0.01
moldm-3s-1.

The second method of analysis used is the integral correlation method. This method was carried
1 1
out by plotting the graph of
CA
- CA 0
against t. The straight line graph obtained
 AKINPELUMI K.F 100401013

confirmed that the reaction is a second order reaction; and a rate constant of 0.00439moldm-3s-1
was obtained.

The difference between the rate constant obtained by the two methods is due chiefly to
experimental errors that occurred while carrying out the experiment.

As a result of the fact that the k1 i.e rate constant value is small, the reverse reaction may be
neglected.

Also, it was noticed that the concentration of the base reduced with an increase in time. This
implies that the base kept on reacting in the batch reactor until it was stopped by the HCl in the
conical flasks after specified time intervals.

CONCLUSION

It can be concluded that the reaction is a second order since the two method of analysis gave a
straight line graph.

The rate constant from the differential correlation method is 0.01 moldm-3s-1, while that obtained
from the integral correlation method was 0.00439moldm-3s-1.

The assumption made that the reverse reaction be neglected holds since the rate constant values
gotten from both integral and differential correlation methods are very small.

The concentration of the base reduced with an increase in time. This implies that the base kept on
reacting in the batch reactor until it was stopped by the HCl in the conical flasks after specified
time intervals.
 AKINPELUMI K.F 100401013

PRECAUTIONS

I ensured that the laboratory apparatus used was thoroughly cleaned before and after the
experiment.

I was careful while handling the reactant or reagents used.

AKINPELUMI K.F 100401013