Experiment#3

Kinetic study of acid catalyzed hydrolysis of ethyl acetate.

Theory:

Chemical reaction takes place when a detectable number of molecules of one or more species
have lost their identity and assumed a new form by a change in the kind or number of atoms in the
compound and by a change in structure or configuration of these atoms.

Chemical kinetics is the part of physical chemistry that studies reaction rates. The reaction rate
or rate of reaction for a reactant or product in a particular reaction is defined as how fast a reaction
takes place. For example, the oxidation of iron under the atmosphere is a slow reaction which can take
many years, but the combustion of butane in a fire is a reaction that takes place in fractions of a second.
Consider a typical chemical reaction:

aA + bB → pP + qQ

The lowercase letters (a, b, p and q) represent stoichiometric coefficients, while the capital
letters represent the reactants (A and B) and the products (P and Q).

The rate of reaction is defined as the change in the number of molecules of reacting species per
unit volume per unit time. It is usually taken as the rate at which the reactant disappear or the rate at
which the product is formed. The rate at which the reactant ‘a’ is disappearing is proportional to its
concentration at any instance,

I.e. rate (r) α (a - x)

Rate (r) = k (a - x) where k = rate constant

The concept of rate of reaction is very important in evaluating chemical reacting systems.

The rate of reaction depends on various factors, such as

a. Availability of reactants and its surface area. The greater the surface area of a solid, the
greater the rate of reaction.

b. Concentration: increase in concentration increase the rate of reaction

c. Pressure: increase in pressure results in an increase in the rate of reaction, if the reactants
and products are gaseous

d. Catalyst: The presences of a catalyst generally increase the rate of reaction. There are
however, negative catalysts that lower the rate of reactions.

e. Temperature: increase in temperature increase rate of reaction

Rate constant, K quantifies the speed of a chemical reaction. For a chemical reaction where substance A
and B are reacting to produce C, the reaction rate has the form:

Reaction: A+BC

r = K[A]m [B]n Where K is the rate constant that depends on temperature.

 The Arrhenius equation is a simple, but remarkably accurate formula for the temperature
dependence of the rate constant, and therefore rate of a chemical reaction. Actually, the Arrhenius
equation gives: "the dependence of the rate constant (k) of chemical reactions on the temperature (T)
(in Kelvin) and activation energy (Ea) ", as shown below:

k = AeEa/RT

where: A is the pre-exponential factor or simply the prefactor

R is the molar gas constant.

The units of the pre-exponential factor are identical to those of the rate constant and will vary
depending on the order of the reaction. It can be seen, that either increasing the temperature or
decreasing the activation energy (for example through the use of catalysts) will result in an increase in
rate of reaction. The activation energy can be interpreted as the minimal energy of the molecules to
undergo reaction. This energy is needed, either, to rupture a chemical bond, e.g. in free radical gas
reactions, or to allow rearrangements when the molecules collide.

Chemicals:

Ethyl acetate, 0.5N HCl, 0.2N NaOH, Phenolphthalein indicator, Ice-cubes, distilled water

Apparatus:

Burette 50mL, Pipettes-5mL, 10mL conical flasks, Wash bottle, Reaction bottle 250mL

Procedure:

1. Exactly 100 mL of 0.5N-hydrochloric acid solution are taken in a 250 mL clean reaction bottle
2. Exactly 5 mL of the ester is added to it. Zero time is noted when half the volume of ester
solution in the pipette is transferred into the reaction bottle.
3. After thorough mixing, immediately 10mL of the solution is pipetted out into a clean conical
flask containing ice-cold water.
4. It is then titrated against 0.2 N sodium hydroxide solution from the burette using
Phenolphthalein indicator.
5. The end-point is the first appearance of a pale permanent pink colour.
6. The same volumes of the reaction mixture is withdrawn at regular intervals, say 10 minutes and
is titrated against sodium hydroxide solution.
7. The reaction is allowed to go to completion by keeping the reaction Mixture over a hot water
bath for about 90 minutes. The final reading is then noted.

Observations:

Let V0 be the volume of NaOH used at zero time and Vt be the volume of NaOH used after the time ‘t’.
Let V∞ be the reading when the reaction is completed.

Time Volume of NaOH k = 2.303 log ( V∞ - Vo )

S.No. V∞ - Vt log (V∞ - Vt)
(min) (ml) t (V∞ - Vt )
1 0
2 10
 3 20
4 30
5 40
6 50
7 60
8 70
9 80
10 90

Concentrations of the ester at various time intervals are expressed in terms of volume of NaOH solution.

A = initial concentration of ester = (V∞ - Vo)

(a-x) = concentration of ester at any time‘t’ = (V∞ - VO) – (Vt – Vo)

= (V∞ - VO – Vt + Vo)
= (V∞ - Vt)

The specific rate constant of the reactions is given below

k = 2.303 log ( a )
t ( a-x )

k = 2.303 log ( V∞ - Vo )
t (V∞ - Vt )

k = Slope x 2.303

The rate constant values are calculated at different time intervals which should nearly be the same. A
graph is drawn between log(V∞ - Vt) and the Time ‘t’. From the slope of the plot, the rate constant is
calculated and it is compared with the experimental value.

Short questions:
1. What is chemical kinetics?

Answer: Chemical kinetics is the part of physical chemistry that studies reaction rates. The reaction rate
or rate of reaction for a reactant or product in a particular reaction is defined as how fast a reaction
takes place. For example, the oxidation of iron under the atmosphere is a slow reaction which can take
many years, but the combustion of butane in a fire is a reaction that takes place in fractions of a second

2. What are the factors affecting rate of reaction?

Answer: The rate of reaction depends on various factors, such as

a. Availability of reactants and its surface area. The greater the surface area of a solid, the
greater the rate of reaction.

b. Concentration: increase in concentration increase the rate of reaction

 c. Pressure: increase in pressure results in an increase in the rate of reaction, if the reactants
and products are gaseous

d. Catalyst: The presences of a catalyst generally increase the rate of reaction. There are
however, negative catalysts that lower the rate of reactions.

e. Temperature: increase in temperature increase rate of reaction

3. Discuss rate of reaction or rate law.

Answer: The rate of reaction or rate law is defined as the change in the number of molecules of reacting
species per unit volume per unit time. It is usually taken as the rate at which the reactant disappear or
the rate at which the product is formed. The rate at which the reactant ‘a’ is disappearing is proportional
to its concentration at any instance,
I.e. rate (r) α (a - x)

Rate (r) = k (a - x) where k = rate constant

4. Define hydrolysis and what are the Type of hydrolysis?

Answer: Hydrolysis is derived from a Greek word hydro meaning water and lysis which means to
break.
 Hydrolysis is any chemical reaction in which a molecule of water breaks one or more chemical
bonds.
 In a hydrolysis reaction, a larger molecule forms two (or more) smaller molecules and water is
consumed as a reactant

Types:
Following are the type of hydrolysis.

i. Salts: Hydrolysis occurs when salt from a weak base or acid dissolves in liquid. When this occurs,
water spontaneously ionizes into hydroxide anions and hydronium cations. This is the most
common type of hydrolysis.
ii. Acid: Water can act as an acid or a base, according to the Bronsted-Lowry acid theory. In this
case, the water molecule would give away a proton. Perhaps the oldest commercially-practiced
example of this type of hydrolysis is saponification, the formation of soap.
iii. Base: This reaction is very similar to the hydrolysis for base dissociation. Again, on a practical
note, a base that often dissociates in water is ammonia
Problem:
The kinetic study of hydrolysis of ethyl acetate is catalysed by an acid, and is followed by
titrating a fixed volume of a reaction mixture with a standard alkali solution, at different intervals
of time. The ester hydrolysis is acid catalysed. V0,Vt and V∞ are the volumes of alkali required at
t = 0, t = t and t=∞ respectively. Then, match the statements given in Column I with those in
Column II.

Column-I
a) V0 is proportional to
b) Vt is proportional to
c) (V∞ – Vt) is proportional to
d) (V∞ – V0) is proportional to
Column-ll
p) Total concentrations of acid initially present
and concentration of acid formed at time t.
q) Concentration of acid initially present as the
catalyst
r) Concentration of acid formed after the
completion of reaction
s) Concentration of ester remaining at time t.

Answer:

i. a-q
ii. b-p
iii. c-s
iv. d-r