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EXPERIMENT 1

KINETICS OF THE
PEROXYDISULFATE IODIDE REACTION
OBJECTIVES
At the end of this exercise, the students should be able to:
1. determine the order of reaction with respect to the peroxydisulfate and iodide
ions;
2. determine the rate constant of the reaction at a given temperature and ionic
strength;
3. investigate the effect of temperature on the rate of the reaction and to
calculate the activation energy of the reaction;
LIST OF CHEMICALS/MATERIALS

0.10M KI
0.10M K2S2O8
0.010M Na2S2O3

2.0% w/v starch solution


Reagent grade NaNO3

thermometer
pipette (10 mL)
parafilm
timer

LIST OF APPARATUS AND SET-UP

Erlenmeyer flask (250 mL)


Volumetric flask (250 mL)
thermostatted water bath
stirrer

DISCUSSION
In this exercise the ionic reaction

2I S2O82 I 2 2SO42

(1-1)

shall be investigated. The progress of the above reaction shall be monitored by the
following reactions:

I 2 2S2O32 2I S4O62

(1-2)

I 2 starch blue starch - iodo complex

(1-3)

since reaction (1-1) is much slower than reaction (1-2). As such, reaction (1-2)
instantaneously converts back any I 2 formed from (1-1) to I- such that no free I 2 is found
in the reaction mixture until all of the thiosulfate (S2O32-) has been consumed. Before this

CHM156L. Physical Chemistry Laboratory 2

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EXPERIMENT 1: KINETICS OF THE PEROXYDISULFATEIODIDE REACTION

point is reached, the iodide concentration [I -] remains constant and the blue starchiodo complex does not appear. When the blue complex appears, the number of moles
of peroxydisulfate (S2O82-) that have reacted is equal to half the number of moles of
S2O32- initially present.
Let us make the following definitions:
a = initial concentration of S2O82b = initial concentration of I c = initial concentration of S2O32x = number of moles (per liter) of S2O82- that have reacted at time t
At a certain time t,
[S2O82-] = a x

(1-4)

[S2O32-] = c - 2x

(1-5)

The appearance of the blue complex means that


[S2O32-] = 0

(1-6)

and equations (1-5) and (1-6) lead to

c
2

(1-7)

The general rate equation is

d [S2 O8 2- ] dx
rate = =
= k [I - ]n [S2O82- ]m
dt
dt

(1-8)

and thus,

c
c
= k [b]n a -
2t
2

(1-9)

which can be manipulated in two ways:


CASE I

c
c
log = log k' + m log a -
2t
2

(1-10)

CASE II

c
log = log k" + n log b
2t

(1-11)

CHM 156L Physical Chemistry for Engineers 2 (Laboratory)

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EXPERIMENT 1: KINETICS OF THE PEROXYDISULFATEIODIDE REACTION

where k' = k [b] = constant


n

c
k" = k a - = constant
2
PROCEDURE
General Procedure
1. Prepare 50.0 mL each of the reagent solutions in duplicate.
Reagent A a solution of KI, Na2S2O3 and inert salt
Reagent B a solution of K2S2O8 and starch
The volumes of each component of the solutions are specified in respective parts of the
procedure. As part of the pre-lab preparations, know how the volumes of each
reagent, as given in each table, were arrived at.
2. Equilibrate the reagents A and B in a thermostatted water bath at the required
temperature. Record the temperature of the bath.
3. Simultaneously with a timer, mix reagent A with reagent B. Pour the solution back
into the empty flask. Repeat until the blue complex appears.
4. Record the time it takes for the blue starch-iodo complex to appear.
Determination of the Order of Reaction and the Rate Constant
The order of the reaction with respect to [I -] and to [S2O82-] will be studied under five sets
of different initial reactant concentrations at ambient temperature.
1. Case I. The reaction order with respect to [S2O82-] is studied by keeping the [I-]
constant at 0.020 M. The initial [S2O82-] is varied as follows: 0.010, 0.015, 0.020, 0.025,
and 0.030 M.
2. Case II. The reaction order with respect to [I -] is studied by keeping the [S2O82-]
constant at 0.010 M. The initial [I -] is varied as follows: 0.010, 0.015, 0.020, 0.025, and
0.030 M.
3. The Na2S2O3 concentration is kept constant at 0.00020 M.
4. For each case, the ionic strength of the reaction mixture is maintained at 0.12 M by
adding 0.40 M NaNO3.
The following tables give the volumes of the different stock solutions needed to prepare
reagents A and B.

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EXPERIMENT 1: KINETICS OF THE PEROXYDISULFATEIODIDE REACTION

Case I. Fixed [I-], varied [S2O82-]


Table 1.1a. Composition of reagent A for determination of order with respect to S2O82-.
Solution No.
1
2
3
4
5

0.010M Na2S2O3
2.0
2.0
2.0
2.0
2.0

Volume of stock solution, mL


0.10 M KI
0.40M NaNO3
20.0
17.35
20.0
13.60
20.0
9.85
20.0
6.10
20.0
2.35

H2O
10.65
14.40
18.15
21.90
25.65

Table 1.1b. Composition of reagent B for determination of order with respect to S2O82-.
Solution No.
1
2
3
4
5

0.10 M K2S2O8
10.0
15.0
20.0
25.0
30.0

Volume of stock solution, mL


2% starch solution
2.0
2.0
2.0
2.0
2.0

H2O
38.0
33.0
28.0
23.0
18.0

Case II. Fixed [S2O82-], varied [I -]


Table 1.2a. Composition of reagent A for determination of order with respect to I-.
Solution No.
1
2
3
4
5

0.010M Na2S2O3
2.0
2.0
2.0
2.0
2.0

Volume of stock solution, mL


0.10 M KI
0.40M NaNO3
10.0
19.85
15.0
18.60
20.0
17.35
25.0
16.10
30.0
14.85

H2O
18.15
14.40
10.65
6.90
3.15

Table 1.2b. Composition of reagent B for determination of order with respect to I-.

0.10 M K2S2O8
10.0

Volume of stock solution, mL


2% starch solution
2.0

H2O
38.0

5. a. Follow the general procedure.


b. Mix solution 1 of reagent A with solution 1 of reagent B.
c. Mix the rest of the solutions in the same manner.

CHM 156L Physical Chemistry for Engineers 2 (Laboratory)

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EXPERIMENT 1: KINETICS OF THE PEROXYDISULFATEIODIDE REACTION

Effect of Temperature on Reaction Rate


The effect of temperature on reaction rate is studied under five values of temperature
from 15o to 35oC at constant concentration.
1. Prepare ten flasks (five each group) of reagent A which will give final concentrations
of 0.02 M KI, 2.0 x 10-4 M Na2S2O3 and 0.12 M total ionic strength.
Table 1.3a. Composition of reagent A for the effect of temperature.
Volumes of stock solution, mL
0.010M Na2S2O3
0.10 M KI
0.40 M NaNO3
2.0
20.0
17.35

H2O
10.65

2. Prepare ten flasks of reagent B which will give a final concentration of 0.010 M K 2S2O8
with starch.
Table 1.3b. Composition of reagent B for the effect of temperature.
Volumes of stock solution, mL
0.10 M K2S2O8
2% starch solution
10.0
2.0

H2O
38.0

3. Adjust the temperature of the water bath to 35oC.


a. Equilibrate two flasks each of reagents A and B in the water bath for 15
minutes.
b. Simultaneously with a timer mix reagent A with reagent B keeping the flasks
immersed in the water bath. Pour back the solution into the empty flask
repeatedly until the blue complex appears.
c. Record the time it takes for the blue complex to appear.
4. Repeat step 3 for temperatures 30, 25, 20 and 15oC.
ANALYSIS OF DATA
1. Calculate the initial rate for each set of data.
experimental concentrations used

initial rate = -

Assume that over the entire range of

d [S 2 O8 2- ] [S 2O3 2- ]o
c
=
=
dt
2t
2t

where t is the time it takes for the blue complex to appear.

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EXPERIMENT 1: KINETICS OF THE PEROXYDISULFATEIODIDE REACTION

2. Use the data obtained in Case I and Case II and equations (1-10) and (1-11) to calculate m
and n, the order of reaction with respect to S2O82- and I-, respectively. Round off the
computed values of m and n to the nearest whole number.
3. Solve for k, the rate constant of the reaction, from k and k (of equations (1-10) and (1-11))
and using the values of m and n, obtained in 2. Log k and log k are the intercepts of
equations (1-10) and 1-11), respectively.
4. Using equation 1-9, solve for the rate constant k at each temperature and using the
literature values of m and n.
5. Plot ln k against 1/T and calculate the Ea and A using the Arrhenius equation.

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EXPERIMENT 1: KINETICS OF THE PEROXYDISULFATEIODIDE REACTION

CHM 156L
Section:
Professor:
Group No:
Members :

_____________________
Date Performed:
_____________________
_____________________
Date Submitted:
_____________________
_____________________
____________________________
____________________________
____________________________
____________________________
____________________________
____________________________
REPORT SHEET
EXPERIMENT 1
KINETICS OF THE PEROXYDISULFATE-IODIDE REACTION

Table 1.1. Time required for the appearance of the blue complex for the determination
of order with respect to S2O82-.

1
Time

Solution number
3

I
II

Table 1.2. Derived data from Case I: Fixed [I-], varied [S2O82-].

log ( )
2

log ( )
2

Solution number
3

Slope = m
y-intercept = log k
r2
k from k
Table 1.3. Time required for the appearance of the blue complex for the determination
of order with respect to I-.

1
Time

Solution number
3

I
II

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EXPERIMENT 1: KINETICS OF THE PEROXYDISULFATEIODIDE REACTION

Table 1.4. Derived data from Case II: Fixed [S2O82-], varied [I-].

Solution number
3

log()

log ( )
2
Slope = n
y-intercept = log k
r2
k from k
Table 1.5. Time required for the appearance of the blue complex at different
temperatures.

15
Time

20

Temperature, oC
25

30

35

30

35

I
II

Table 1.6. Derived data for the effect of temperature.

15

20

Temperature, oC
25

ln k
1/T
y-intercept = ln A
Slope = - Ea/R
r2
A
Ea
Theoretical value: n = _____; m = ______
Signature: ______________
Date completed: ______________

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EXPERIMENT 1: KINETICS OF THE PEROXYDISULFATEIODIDE REACTION

POST LAB QUESTIONS


1. What are the possible sources of errors in the experiment? Discuss the effect of
these errors on the results of the experiment.
2. What is the effect of increasing temperature on the rate, rate constant and
activation energy? Explain the answer using the collision theory of reaction rates.
3. What is a catalyst and how does it work?
4. CuSO4 catalyzes the reaction of iodide with peroxydisulfate. Propose a possible
mechanism for such catalysis considering the electrophilic character of Cu2+.

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