CHM 224: Physical Chemistry Laboratory

Experiment 5: First order kinetics Acid hydrolysis of methyl acetate (at

40C) taking different concentrations of [H+] ions.

Theory:
Rate of first order reaction is directly proportional to the first power of the concentration of the
reactant.


=

Where k is the rate constant (unit: time-1) and C A is the molar concentration of A at time t.
Integration of the rate equation with proper limits at t = 0, C A = C 0 and t = t, C A = C t and
converting the logarithmic term to base 10 :
2.303 0
= 10

Hydrolysis of an ester though appears to be bimolecular is kinetically a first order reaction with
respect to the ester, since, water (H 2 O) molecules are present in large excess.
O O
H+
CH3 C OCH3 + H2O CH3 C OH + CH3OH

The reaction is slow and efficiently catalysed by strong acids. When a known amount of ester is
hydrolysed in presence of known amount of strong acid the progress of reaction can be studied
by withdrawing measured volumes of aliquots from the reaction mixture at different intervals of
time and titrating the same with a standard alkali solution using phenolphthalein as indicator. If
V 0 , V t and V be the volumes of the standard alkali required for the same volume of the aliquots
at the beginning ( t = 0), at time t and at the end of the reaction (t = ), then,
(V - V 0 ) = C 0 (initial amount of ester)
(V t V 0 ) = amount of ester consumed = amount of weak acid formed
Amount of ester left = (V - V 0 ) - (V t V 0 ) = (V - V t ) = C t
2.303 0
= 10

0
10 =
2.303
Thus measuring V 0 , V t and V and plotting log 10 [(V - V 0 ) / (V - V t )] against t, it is possible
to determine k from the slope of the resulting straight line passing through the origin.

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k = 2.303 x slope
Note: The experimentally determined rate constant, k, is related to the concentration [H+] of the
acid (catalyst) according to : k = k solv + k 0 [H+], where, k solv is the rate constant of the
uncatalysed reaction.
Chemicals:
Methyl acetate, hydrochloric acid1 (N), phenolphthalein, sodium hydroxide
Glassware & Equipment required:
Conical flask (250 mL x 6), conical flask (250 mL, B-24), measuring cylinder (100 mL), Pipette
(25 ml, 5 ml, 2 ml), Reflux condenser, water bath, ice cold water.
Procedure:
1. Prepare 250 mL of approximately 0.1 (N) NaOH solution,
2. Fix a 250 ml (B-24) conical flask in the bath (use clamps) and set the temperature of the
bath at 40C. Take 50 mL of 1(N) HCl supplied in flask.
3. Take 50 ml (use measuring cylinder) of ice cold distilled water into a 250 ml conical
flask.
4. When temp of 1 N HCl (catalyst acid solution) reaches 400 C (Check by thermometer)
then add 5 ml of ester (use pipette) and note the time of half discharge. Mix uniformly
by shaking (use glass rod)
5. Immediately after mixing, withdraw 2 ml of an aliquot from the reaction mixture (use
pipette) into the ice-cold distilled water taken. Mix well and titrate immediately against
the 0.1 N NaOH solution using phenolphthalein as indicator. Take the titre as V 0 and time
t=0
6. Repeat step 5 at different time intervals (5, 10, 15, 20, 25, 30 minutes) of time and record
the titre (V t ) and time (t) data in a tabular form.
7. After the required titrations are over, place the residual mixture on a hot water-bath and
heat at ~60C for ~30 minutes using an air condenser. Cool to room temperature, take 2
ml aliquot into 50 ml of water and titrate against the same 0.1 N NaOH solution, using
phenolphthalein as indicator as before. This titre gives V .
8. Now half dilute the supplied HCl (Use pipettes)
9. Now with the 0.5 N HCl, repeat steps 2-7
10. Plot log 10 [V -V 0 )/(V -V t )] vs time (t) and find k 0.5N and k 1(N) from the slope
11. Also report the ratio of the two rate constants (k 1(N) /k 0.5(N) )

Note down all the observations in your lab notebook. Clean all your glassware and
hand over to the lab attendant.

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 CHM 224: Physical Chemistry Laboratory

Experiment 6: Kinetics of the iodide-hydrogen peroxide clock reaction

Theory:
In dilute acid medium (dil H 2 SO 4 ), H 2 O 2 reacts with KI according to
H 2 O 2 + 2KI+ H 2 SO 4 I2 +2H 2 O+ K 2 SO 4 (1)
Ionically, H 2 O 2 + 2I- + 2H+ I 2 + 2H 2 O (1a)
t=0 a 0
t=t (a-x) x
The overall reacting is kinetically second order, being first order in H 2 O 2 and first order to I-.
The rate of the reaction may be expressed according to:
Rate = -d[H 2 O 2 ]/dt = k[H 2 O 2 ][I-] (2)
Where, k is the second order rate constant, [ ]s represent molar concentrations of the respective
species. The unit is (mole/lit)-1. (Time)-1
The reaction actually occurs is two steps:
Slow
i) H 2 O 2 + I- H 2 O + OI- (1b)
Fast
ii) IO- + 2H+ + I- H 2 O + I2 (1c)

The first step is the rate-determining step.

If the iodide ion concentration, [I-] is kept constant, in large excess, the reaction becomes
kinetically first order in [H 2 O 2 ]. This condition is achieved by adding sodium thiosulfate
solution continuously in small amounts to the reaction mixture, when thiosulfate (S 2 O 3 2-) ions
react with the liberated I 2 and regenerate I- according to

I 2 +2S 2 O 3 2- S 4 O 6 2- + 2I- (2)

Under these conditions the rate equation (2) is transformed to

-d[H 2 O 2 ]/dt = k 1 [H 2 O 2 ] (2a)
-
Where, k 1 =k[I ] (2b)

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 k 1 is the pseudo first order rate constant of the reaction. Integrating this equation (2a) with
the boundary conditions at t=t, [H 2 O 2 ] = [a-x], where x= amount of H 2 O 2 reacted =
equivalent of I 2 liberated= equivalent of thiosulfate consumed:
2.303 a
k1 = log10 ( ) (2c)
t ax
If V 0 = titre value of thiosulfate for iodide liberated by a fixed volume (say 10 ml) of H 2 O 2
solution, this is equivalent to the initial concentration of H 2 O 2 , i.e. a.

V t =titre value of the same thiosulfate solution for the iodine liberated by the same
volume (10 ml) of H 2 O 2 present in the reaction mixture (undergoing reaction) at time
t; this is equivalent to x.

Substituting, for a and (a-x) in the rate equation (2c) one obtains the working equation
2.303 V0
k1 = log10 ( ) (2d)
t V0 Vt
V0 k
log = 1 .t (2e)
V0 Vt 2.303
V0
A plot of log against t will be straight line of slope = k 1 /2.303 and passing through
V0 Vt
the origin. k 1 may be evaluated from the slope
Chemicals:
Sulfuric acid (12N), starch solution (1%), sodium thiosulfate (0.1N), potassium iodide, hydrogen
peroxide solution (30%).
Glassware & Equipment required:
Conical flasks (250 mL x 4), conical flask (500 mL), measuring cylinders (10 mL, 100 mL),
volumetric flasks (250 mLx 2, 50 mLx 2)
Procedure:
1. Prepare the following solutions:
(i) 50 ml of 3 volume H 2 O 2 (Supplied H 2 O 2 is 30%) and 2 volume H 2 O 2.
(ii) 250 ml of KI solution, use volumetric flask (1 gm KI in 250 ml water)
(iii) 250 ml of 0.1 N sodium thiosulfate solution (6.2 g of Na 2 S 2 O 3 .5H 2 O in 250 ml
water)
2. Add 2 g of KI in 10 mL ~12 N H 2 SO 4 (supplied) in a 250 mL conical flask, shake well.
Add 10 ml of prepared 3 volume H 2 O 2 solution, cover the flask, shake and quickly keep
the reaction mixture in dark for 10 minutes. Titrate the liberated iodine with 0.1 N
thiosulfate solution using 4-5 drops of starch indicator. This titre value is V 0 .

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 3. Take 250 ml of prepared KI solution in a 500 ml conical flask, add 15 ml of ~12 N
H 2 SO 4 solution and 2 ml starch indicator. Fill the burette with prepared thiosulfate
solution.
4. Add 10 ml of the 2 Vol H 2 O 2 solution into the reaction mixture (use pipette) and start
the stop watch at the time of half discharge.
5. Shake the reaction flask to mix uniformly. A blue color will soon appear.
6. Discharge the blue color immediately by adding the (0.1N) thiosulfate solution from a
burette (2-3 ml may be required). Record the time of appearance of the blue color and
titre of the thiosulfate solution.
7. The volume of thiosulfate consumed will correspond to the time of reappearance of the
blue color.
8. These titres constitute the V t values. Continue this process till the (V t - V 0 )values are less
than 30% of V 0 .
9. Plot lo g10 [ V0 /( V0 - Vt )] against time t, and draw the best straight line passing through the
origin and the experimental points and calculate the value of the pseudo first order rate
constant from the slope.
Note down all the observations in your lab notebook. Clean all your glassware and hand
over to the lab attendant.