T.Y.B.Sc.

Practical Chemistry (Physical Practicals) Chemical Kinetics

To compare the relative strength of HCl and H2SO4 by studying the kinetics of hydrolysis of
an ester.
Chemicals :
Methyl acetate 0.5 N HCl, 0.5 N H2SO4, 0.1 N NaOH, phenolphthalein indicator, ice cold
water etc.
Apparatus :
Stoppered bottles, pipettes, burette, measuring cylinder, beakers, stop watch, water bath
etc.
Theory :
The hydrolysis of ester is catalyzed by H+ ions.
H+
CH3COOCH3 + H2O ⎯→ CH3COOH + CH3OH
Therefore, the rate of hydrolysis increases with increase in concentration of H+ ions. If the
hydrolysis is carried out in presence of hydrochloric acid and of sulphuric acid independently,
with their equal concentrations, the rate constants for hydrolysis, kHCl and kH2SO4, depend on
the degree of dissociation of HCl and H2SO4.
The rate of hydrolysis using either of the catalyst is proportional to the concentration of
methyl acetate (reactant) and in turn to the concentration of acetic acid (product).
Experimental measurement of the rate of reaction (kHCl and kH2SO4) can be studied by
determining the amount of acetic acid formed in the course of reaction. Amount or
concentration of acetic acid formed at different time intervals can be easily determined by
titrating the definite amount of reaction mixture with standard alkali. Hence, the relative
strength can be calculated as
kHCl
Relative strength =
kH2SO4
Thus the strength of the two acids can be compared by kinetic measurements.
Procedure :
Perform the experiment in two sets.
Set I : 5 ml methyl acetate + 100 ml 0.5 N HCl :
1. Take 100 ml 0.5 N HCl in a clean and dry stoppered bottle (bottle 1). In another
stoppered bottle take 5 ml methyl acetate (bottle 2).
2. Keep the bottles in a water bath for 10-15 minutes to attain the constant
temperature.
3. Fill the burette with 0.1 N NaOH solution upto the zero mark.
4. Take few pieces of crushed ice or around 30 ml ice cold water in a conical flask and
add to it 2-3 drops of phenolphthalein indicator.
5. Transfer the 100 ml 0.5 N HCl in bottle 1 to bottle 2 containing 5 ml methyl acetate.
Shake the mixture and start the stop watch. Note the time of mixing as zero time.

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T.Y.B.Sc. Practical Chemistry (Physical Practicals) Chemical Kinetics

6. Immediately pipette out 5 ml reaction mixture in titration flask containing ice and
phenolphthalein indicator. (Place the bottle in water bath).
7. Shake it well and titrate with 0.1 N NaOH till faint pink colour appears and persists for
30 seconds to the solution.
8. Record the titration reading as T0.
9. Shake the reaction mixture from time to time and titrate 5 ml of reaction mixture
similarly at the successive intervals of 10, 20, 30, 40 and 50 minutes. Record the
titration readings as Tt.
10. Infinity reading (T∞) : Take 25 ml of the reaction mixture in a flask. Cork it and keep
in water bath at around 50°C temperature, for 10 minutes to complete the hydrolysis.
Finally, titrate 5 ml of it against 0.1 N NaOH and record the readings as T∞.
11. Similarly carry out the experiment for set II in the same manner as the set I. The only
difference in set two is the use of H2SO4 in place of HCl.
Set II : 5 ml methyl acetate + 100 ml 0.5 N HCl :
Observations :
Set I : 5 ml methyl acetate + 100 ml 0.5 N HCl
Initial reading (T0) = ……...ml
Infinity reading (T∞) = ………ml
Initial concentration of methyl acetate a = T∞ – T0 = ……..ml

Titration
Time (t) T∞ – T t a
reading Tt – T 0 = x log a – x log k (min–1)
min = a–x a−x
(Tt) ml

10
20
30
40
50

Prepare similar observation table for set II.

Calculations :
1. Rate constant k by calculations for first order reaction :
2.303 a
k = log
t (a − x)
where, a = Initial concentration of methyl acetate

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T.Y.B.Sc. Practical Chemistry (Physical Practicals) Chemical Kinetics

(a – x) = Amount of methyl acetate remaining unreacted at time t.

Calculate the values of k for first and second set at 10, 20, 30, 40 and 50 min. intervals.
Calculate mean value of k for each set.
kHCl
∴ Relative strength =
kH2SO4
2. Rate constant (k) by graphical method :
(i) Plot the graph of log (a – x) against time for both the sets, straight line nature of
graph shows that reaction is first order.
−k
Slope =
2.303
log (a - x)
∴ −k = 2.303 × slope

time/min
Fig. 1: log (a − x) vs. t
(ii) Plot the graph of log [a/(a – x)] against time, the nature of graph is a straight line
passing through the origin.
k
Slope =
2.303
log a
∴ k = 2.303 × slope (a - x)

Find out kHCl and kH2SO4 from both the

graphs. time/min
a
Fig. 2: log vs. t
a−x
Result Table :
Sr. No. Description By calculations By graph
–1
1. Rate constant (kHCl) ……… min ……… min–1
2. Rate constant (kH2SO4) ……… min–1 ……… min–1
⎛ kHCl ⎞ ……… ………
3. Relative strength = ⎜ ⎟
⎝kH2SO4⎠
Conclusion :
For equal concentration of HCl and H2SO4, hydrochloric acid is more dissociated than
sulphuric acid.
kHCl
∴ > 1
kH2SO4

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