Aim: Determination of the rate constant of a reaction

Requirement:
(i) Apparatus: Stoppered bottle, burette, conical flask, pipette
(ii) Chemicals: NaOH solution, HCl solution, methyl acetate, phenolphthalein

Theory:
Various chemical reactions take place at different rates. The rate of any particular reaction
depends on certain parameters, particularly on temperature and concentration. At constant
temperature, study of the influence of concentration on the rate of a reaction enables to
determine the order of the reaction.
For this purpose, the hydrolysis of methyl acetate catalyzed by hydrogen ion is to be
considered and the reaction is-

CH3COOCH3 + H2O CH3COOH + CH3OH

In the above reaction, the concentration of water is practically constant throughout the
reaction. The rate of the reaction is directly proportional to the concentration of ester (methyl
acetate), i.e. the reaction is pseudo first order reaction.
The progress of the reaction is followed by determining the change in the concentration of
methyl acetate as the function of time. This is done in an indirect way as follows. For each
mole of ester hydrolysed, one mole of acetic acid is produced. In other words, the rate of
hydrolysis of methyl acetate is equal to the rate of formation of acetic acid. Thus,
d[CH3 COOH] d[CH3 COOCH3 ]
=- = k[CH3COOCH3] ……………(1)
dt dt
where, k is the rate constant and depends on temperature, [H+], solvent used for the reaction.
k can be calculated more easily from the integrated form of equation (1). If ‘a’ is the initial
concentration of ester and x is the amount of ester decomposed at any time t,
1 𝑎 2.303 𝑎
k = 𝑡 ln𝑎−𝑥 = 𝑡 log𝑎−𝑥 …………….(2)
𝑎
Experimentally, (a-x) can be determined at various time intervals and a plot of log𝑎−𝑥 against
‘t’ would yield a straight line and the rate constant ‘k’ can be calculated from the slope.

Preparation of chemicals:
• Add 100 mL 0.5 N HCl in a 250 mL stoppered bottle
• Keep the bottle in a trough of water at 25°C or the laboratory temperature

Procedure:
• Pipette out 2 mL of methyl acetate into the given stoppered bottle and the shake the
bottle to ensure mixing and start the stop watch as soon as the ester is added
• Immediately withdraw 5 mL of reaction mixture using a pipette and transfer it into
about 20 mL of ice-cold distilled water taken in conical flask
• Add a drop of phenolphthalein to the conical flask and titrate against standard NaOH
taken in burette
• The first appearance of pale pink color is considered as the end point. Note down the
titre value (V0). This value corresponds to time t = 0. Discard the reaction mixture in
the conical flask and clean the conical flask for the next titration
 • At definite intervals like 10, 20, 30, 40, 50, 60 minutes pipette out 5 mL of the
reaction mixture, deliver it into ice-cold distilled water and titrate against standard
NaOH. Note the titre value (Vt) in each case into record book.

Measurement of Vα :
• Pipette out 2 mL of methyl acetate into the given stoppered bottle
• Keep the bottle in a water bath maintained as 80°C for 30 minutes. This enables
the entire methyl acetate to hydrolyze yielding an equivalent quantity of acetic
acid
• Cool and withdraw 5 mL of the reaction mixture into the conical flask, add
phenolphthalein indicator and titrate against the NaOH solution. Note the titre
value (Vα)

Calculation:
• (Vα – V0) corresponds to the initial concentration of the ester
• (Vα – Vt) corresponds to the concentration of the ester at any time i.e. (a-x). The
kinetic equation in terms of titre values reduces
to
2.303 V −V
k= log Vα − V0 ……….(3)
𝑡 α t
• The titre values are used instead of concentration
since they are directly proportional to each other.
V −V
• Plot of log Vα − V0 vs t gives a straight line with
α t
slope k.