EXPERIMENT 1: PERSULPHATE-IODIDE CLOCK

REACTION BY INITIAL RATES METHOD

NAME: TIRELO ROWLAND GAJEKGOMO
ID NO: 201602327
PARTNERS: EBULENG EBULENG 201603753
BOTLHE MOJUTA 201600351
TEBATSO JANKIE 201603874
DATE: 03/08/2018
GROUP: MONDAY 7-10 AM
AIMS OF THE EXPERIMENT
The aims of this experiment are to determine the rate equation, activation and Arrhenius pre-
exponential factor, and to gain an insight into the nature of the activated complex, for the
reaction of the iodide with persulphate ions.
INTRODUCTION
A clock reaction is any chemical reaction where no visible change occurs for a period of time,
until a sudden change happens unexpectedly. This experiment makes use of the iodine clock
reaction, where a mixture of two colourless solutions remains colourless for a short time and
suddenly turns dark blue.
In this experiment, reaction that proceeds at an easily measured rate at room temperature will be
studied:
S2O82- + 2I- →2SO42- + I2 slow (1)
2S2O32- + I2 → S4O62- + 21- fast (2)
I2 + (C6H10O5)n.H2O → blue complex (3)
The iodide (I-) and persulfate ions (S2O82-) react to produce iodine (I2) and sulfate (SO42-) in
reaction (1). This iodine is immediately consumed by the thiosulfate ions (S2O32-) in a pathway
described by reaction (2). As soon as all of the S2O32- ions are consumed, the excess iodine
produced in (1) is free to react with starch, turning the solution blue (3). The amount of
thiosulfate ions added tells us how much iodine had been produced in the time taken for the
reaction to turn blue.
The amount of I2 formed before the color change can be calculated from the known amount of
S2O32- added using the molar ratio in Equation 2. To find the rate of Equation 1, the change in
the concentration of I2 is monitored over time. Below, ∆[I2] is the change in the concentration of
I2 , and ∆t represents the change in time:
∆[I₂]
𝑅𝑎𝑡𝑒 =
∆t
As soon as all of the S2O32- ions have reacted, the I₂ still being formed (Equation 1) starts to
accumulate and reacts with starch. Starch serves as an indicator to help us “see” the I₂, since the
interaction between starch and I₂ forms a blue starch-iodine complex (equation 3). Thus, "∆t" is
simply the time elapsed between mixing the reagents and the appearance of the blue color.
Because the S2O32- ion concentration in the reaction mixture is known, ∆[I₂] can be calculated
using the stoichiometry of the “clock” reaction. Since the same amount of S2O32- is added to
each run, ∆[I₂] is also the same for each run. However, the amount of time for the appearance of
the blue color varies with initial reactant concentrations or with temperature so ∆t is not constant.
At constant temperature and ionic strength, the rate equation for the reaction may be written;
Rate = k[S2O82-]m[I-]n.
The initial rates method could be used to determine the values of m and n or using the graphical
approach. A plot of ln(1/∆t) against ln[S2O82-] at constant [I-] will yield a straight line slope m
and a plot of ln(1/∆t) against ln[I-] at constant [S2O82-] will yield a straight line slope.
When the temperatures are varied the rate coefficients also vary, and this is illustrated by
Arrhenius equation;
k = Ae-(Ea/RT)
Taking the logarithms to both sides of the equation gives;
lnk = lnA – (Ea/RT)
thus a plot of lnk against 1/T will yield a straight line slope equal to (Ea/RT) there both A and Ea
can be obtained from the graph.
PROCEDURE
The experiment was divided into three parts: Part A; the rate equation: Part B; effect of
temperature: Part B; effect of ionic strength.
Part A
The experiment was started by preparing a standard solution of potassium iodide (0.1 M) in
water as ammonium persulphate (0.1 M), ammonium sulphate (0.1 M) and sodium thiosulphate
(0.01 M) were readily availed in the lab. 10 ml of S2O82- was placed into a beaker and added five
drops of starch. The KI solution(10 ml) was placed in a conical flask and 5 ml of S2O32- solution
and mixed with the S2O82- and starch mixture the recorded the time taken for the blue colour to
appear. Six more runs were done recording time of varying volumes of components of the
mixture as shown in the table below.
Table 1.1.: Compositions of the solutions (ml)
Run S2O82- (solution a) (NH4)2SO4 (solution b) S2O32- solution c) I- (solution d)
1 10 0 5 10
2 10 2 5 8
3 10 4 5 6
4 10 6 5 4
5 8 2 5 10
6 6 4 5 10
7 4 6 5 10

Part B
A solution containing 10 ml of S2O82- solution and a few drops of starch was prepared. Another
solution prepared was containing 10 ml of S2O32- solution and 10 ml of KI solution then the two
mixtures were placed in a thermostat water bath for 15 minutes and recorded the temperature if
the bath. The solutions were then mixed and recorded the time taken for the blue colour to
appear. This procedure was repeated at 5 different temperatures from room temperature to 50 °C.
Part C
In the first run, a solution containing 10 ml of S2O82- solution and a few drops of starch was
prepared. Then a solution containing 5 ml of S2O32- solution, 10 ml of KI solution and 10 ml of
(NH4)2SO4 was prepared. The two mixtures were mixed and recorded the time taken for the blue
colour to appear. This procedure was repeated but water was used instead of (NH4)2SO4.
ABSTRACT
The persulphate iodide reaction was used to determine the relation of concentration, temperature
and ionic strength with the rate of reaction of a solution. Seven different runs were used in this
experiment with each run involving a mixture of potassium iodide, ammonium persulphate,
ammonium sulphate, sodium thiosulphate and starch and time until the mixture turned blue. The
use of initial rates method was used to determine the rate law of the reaction between [I-] and
[S2O82-] and the resulting rate order is a first order with respect to both iodide and persulphate.
The rate law is rate = k[S2O82-][I-]. The use of Arrhenius equation was made to solve for the
Arrhenius constant and activation energy for reactions with varying temperatures. The calculated
values for Arrhenius constant and activation energy are 7.69× 108 M-1s-1 and 57.0 kJ/mol
respectively.
RESULTS
Moles of KI= 0.998 M
Table 1.2: Effect of Concentration on Reaction Rate
Run ∆t(s) 1/∆t(s-1) Ln(1/∆t) [S2O82-](molL- Ln[S2O82-] [I-](molL- Ln[I-] Rate(Ms-1)
1) 1)

1 417.28 0.00240 -6.03 0.040 -3.22 0.040 -3.22 0.00000240

2 434.01 0.00230 -6.07 0.040 -3.22 0.032 -3.44 0.00000230
3 464.32 0.00215 -6.14 0.040 -3.22 0.024 -3.73 0.00000211
4 574.18 0.00174 -6.35 0.040 -3.22 0.016 -4.14 0.00000174
5 367.56 0.00272 -5.91 0.032 -3.44 0.040 -3.22 0.00000272
6 381.13 0.00232 -5.94 0.024 -3.73 0.040 -3.22 0.00000262
7 410.50 0.00244 -6.02 0.016 -4.14 0.040 -3.22 0.00000245
 ln(1/∆t) against ln(I-) at constant [S2O82-]

0
-6.4 -6.35 -6.3 -6.25 -6.2 -6.15 -6.1 -6.05 -6

-0.5

-1

-1.5

-2
ln[I-]

-2.5

-3

y = 2.7175x + 13.073
R² = 0.9478
-3.5

-4

-4.5
ln(1/∆t)
Table 1.3: Effect of Temperature on the Reaction Rate and Rate Constant
Temperat Temperatur [S2O82- [I-](M) Time(s) Rate(Ms-1) (k) 1/T(K-1) ln k
ur(ºC) e(K) ](M)

20.4 293.55 0.0333 0.0333 1181.52 0.0000564 0.0509 0.00341 -2.98

29.4 302.55 0.0333 0.0333 504.22 0.000132 0.119 0.00331 -2.13

44.7 317.85 0.0333 0.0333 158.51 0.000421 0.380 0.00315 -0.968

33.1 306.25 0.0333 0.0333 389.90 0.000171 0.154 0.00326 -1.87

43.7 316.85 0.0333 0.0333 250.39 0.000266 0.240 0.00316 -1.43

Rate= - d[S2O82-] / dt

= - (0.0333 – 0.1)M / (1181.52- 0)s

= 0.0000565Ms-1

Calculating the rate for the rate coeficient(k) for temperature 293.25k
Rate = k[S2O82-]m[I-]n
0.000111 = k (0.0333)1(0.0333)1
0.000111 = k (0.0333) x (0.0333)
k = 0.000111
0.001109
= 0.100

Calculations of activation energy (Ea) and pre-exponencial factor A

From the graph:

Slope = -Ea / R
-Ea = -6855.9 K ×8.314 J K-1 mol-1
Ea = 56999.96 J/mol

Intercept = 20.461 = In A
A = e20.461 = 7.69× 108 dm3/mol/s
 A plot of ln k versus 1/T
0
0.00310 0.00315 0.00320 0.00325 0.00330 0.00335 0.00340 0.00345

-0.5

-1

-1.5
ln k

-2

-2.5

y = -6855.9x + 20.461
R² = 0.9593
-3

-3.5
1/T(K-1)
Table 1.4: Effect of ionic strength on the rate of reaction
Run Time(seconds)
1 514.08
2 654.87

PART C
[SO42-] = 0.03 [S2O82-] = 0.03
[S2O32-] = 0.001 [I-] = 0.03
Run 1 Run 2
I= 0.5∑ci zi2
I=0.5 ∑ (0.03x3+.001)(7) I=0.5 ∑ (0.03x2+0.001)(5)
= 0.5x 0.637 = 0.5x0.305
= 0.319 = 0.152

Run 1 has more ionic strength than run 2 and looking at their times of blue black colour appearance,
run 2 takes more time to colour change because of a weaker ionic strength.

ANALYSIS OF DATA

DISCUSSION

CONCLUSION
The concepts of chemical kinetics were well shown by the different portions in the experiment.
The reaction rate increased with increasing concentration, temperature and ionic strength. All the
objectives were successfully achieved using the data gathered from the three parts of the
experiment. The initial rate method was used in determining the rate law of the equation which
is: Rate = k[S2O82-]m[I-]n .The orders of the reaction were first order for both the iodide and
persulphate ions. With the use of Arrhenius equation the activation energy and Arrhenius
constant were determined to be 57.0 kJ/mol and 7.69× 108 M-1s-1 respectively.