NATIONAL UNIVERSITY OF

SINGAPORE

CM1502

LABORATORY REPORT

EXPERIMENT 2: Rate of An Iodine-Clock Reaction

Name: Chai Mei Xian Audrey

Matriculation number: U075391A

Laboratory Group: 3A
 Objectives

1) To determine the values of the rate constant (k) and the orders of reaction (m and
n) with respect to each of the reactants for the following reaction, using the
method of initial rates.
2 I- (aq) + S2O82- (aq) → I2 (l) + 2 SO42- (aq)
Hence, to determine the rate law as given by the following expression,
R = k [I-] n [S2O82-] m
where R is the rate of reaction.
2) To determine the activation energy Eₐ, for the following reaction from the
temperature dependence of the rate constant of the reaction.
2 MnO4- (aq) + 5C2O42- (aq) + 16 H+ → 2 Mn2+ (aq) + 10 CO2 (g) + H2O (l)

Results

Determination of Reaction Orders and Rate Constant Using Methods of Initial Rates
[S2O82-] = 0.100 M
[I-] = 0.200 M
[S2O32-] = 0.00330 M
Temperature = 30.0 oC (kept constant for all runs)

Solution Vol.S2O82- Vol. I- Vol. H2O Vol. Vol. S2O32- Time/s

/ mL / mL Starch /mL / mL
/ mL
1 10.00 10.00 0.00 1.00 5.00 19
2 10.00 8.00 2.00 1.00 5.00 26
3 10.00 6.00 4.00 1.00 5.00 39
4 10.00 5.00 5.00 1.00 5.00 48
5 10.00 3.00 7.00 1.00 5.00 86
6 10.00 10.00 0.00 1.00 5.00 21
7 8.00 10.00 2.00 1.00 5.00 27
8 6.00 10.00 4.00 1.00 5.00 38
9 5.00 10.00 5.00 1.00 5.00 45
10 3.00 10.00 7.00 1.00 5.00 82
Determination of the Temperature Effect on a Chemical Reaction.

[(COOH)2] = 0.300M
[KMnO4] = 0.100M

Temperature/oC Time/s
10.0 1144
20.0 322
30.0 86
45.0 16
60.0 4

Calculations

1) Calculation of [I-] and [S2O82-] for each reacting solution

Initial [S2O82-] = 0.100 mol/L

Initial [I-] = 0.200 mol/L
Total volume of each solution = 0.026L
η S2O82- = vol. of S2O82- used (in mL)/1000 x initial [S2O82-]
η I- = vol. of I- used (in mL)/1000 x initial [I-]
[S2O82-] after dilution = η S2O82- /total vol. of each solution
[I-] after dilution = η I- /total vol. of each solution
(where η is the number of moles.)

Vol. 0f S2O82-/
Solution Vol of I-/ mL [I-]/M [S2O82-]/M
mL
1 10.00 10.00 0.0769 0.0385
2 10.00 8.00 0.0615 0.0385
3 10.00 6.00 0.0462 0.0385
4 10.00 5.00 0.0385 0.0385
5 10.00 3.00 0.0231 0.0385
6 10.00 10.00 0.0769 0.0385
7 8.00 10.00 0.0769 0.0308
8 6.00 10.00 0.0769 0.0231
9 5.00 10.00 0.0769 0.0192
10 3.00 10.00 0.0769 0.0115
2) Calculation of the no. of moles of I2 that reacted with the S2O32- per litre per
second for each reacting solution
Vol. of S2O32- used in each reacting solution = 0.005L
[S2O32-] = 0.00330 mol/L
∴ η S2O3 = 0.005 x 0.0033
2-

= 1.65 x 10-5 mol

Based on the reaction between I2 and S2O32-,
I2 + 2 S2O32- → 2 I- + S4O62-
η I2 reacted = 0.5 x η S2O32-
= 0.5 x 1.65 x 10-5
= 8.25 x 10-6 mol
Total vol. of each reacting solution = 0.026L
η I2 that reacted with S2O32- per litre per second for each reacting solution
= (η I2 reacted/ Total vol. of each reacting solution)/ Time taken for solution to turn blue
= (8.25 x 10-6 mol/ 0.026L) / Time taken for solution to turn blue
= (3.17 x 10-4) / Time taken for solution to turn blue

Rate of Iodide-Persulfate Reaction

2I- + S2O82-  I2 + 2SO42-
I2 + 2S2O32-  2I- + S4O62-
∴ Rate of iodide-persulfate reaction = rate of I2 produced
= η I2 that reacted with S2O32- per litre per second
(since all the iodine produced per litre per second reacted with S2O32- before excess
iodine produced turned solution blue.)
= (3.17 x 10-4) / Time taken for solution to turn blue
 η I2 that reacted with S2O32- Rate of iodide-
Vol.S2O82- Vol. I- /
Solution Time/s per litre per second /mol persulfate reaction
/ mL mL
/mol L-1s-1
1 10.00 10.00 19 1.67 x 10-5 1.67 x 10-5
2 10.00 8.00 26 1.22 x 10-5 1.22 x 10-5
3 10.00 6.00 39 8.13 x 10-6 8.13 x 10-6
4 10.00 5.00 48 6.60 x 10-6 6.60 x 10-6
5 10.00 3.00 86 3.69 x 10-6 3.69 x 10-6
6 10.00 10.00 21 1.51 x 10-5 1.51 x 10-5
7 8.00 10.00 27 1.17 x 10-5 1.17 x 10-5
8 6.00 10.00 38 8.34 x 10-6 8.34 x 10-6
9 5.00 10.00 45 7.04 x 10-6 7.04 x 10-6
10 3.00 10.00 82 3.87 x 10-6 3.87 x 10-6

3) Calculation of the values for the logs of [I-], [S2O82-] and the rate R

R
Solution [S2O82-]/M [I-]/M log([S2O82-]/M) log([I-]/M) log(R/Ms-1)
/mol L-1s-1
1 0.0385 0.0769 1.67 x 10-5 -1.42 -1.11 -4.77
-5
2 0.0385 0.0615 1.22 x 10 -1.42 -1.21 -4.91
3 0.0385 0.0462 8.13 x 10-6 -1.42 -1.34 -5.09
-6
4 0.0385 0.0385 6.60 x 10 -1.42 -1.42 -5.18
-6
5 0.0385 0.0231 3.69 x 10 -1.42 -1.64 -5.43
-5
6 0.0385 0.0769 1.51 x 10 -1.42 -1.11 -4.82
-5
7 0.0308 0.0769 1.17 x 10 -1.51 -1.11 -4.93
-6
8 0.0231 0.0769 8.34 x 10 -1.64 -1.11 -5.08
-6
9 0.0192 0.0769 7.04 x 10 -1.72 -1.11 -5.15
-6
10 0.0115 0.0769 3.87 x 10 -1.94 -1.11 -5.41

4) Graph of log(R/Ms-1) against log([I-]/M)

Figure 1

Solution log([I-]/M) log(R/Ms-1)

1 -1.11 -4.77
2 -1.21 -4.91
3 -1.34 -5.09
4 -1.42 -5.18
5 -1.64 -5.43
Slope of best-fit line = 1.243

5) Graph of log(R/Ms-1) against log([S2O82-]/M)

Solution log([S2O82-]/M) log(R/Ms-1)

6 -1.42 -4.82
7 -1.51 -4.93
Slope of best-fit line = 1.122
8 -1.64 -5.08
9 -1.72 -5.15 Figure 2
10 -1.94 -5.41
6) Experimental determination of the values, m and n in the rate equation and the
calculation of the rate constant, k, for each solution
The rate law governing the reaction
2 I- (aq) + S2O82- (aq) → I2 (l) + 2 SO42- (aq)
is given by R = k [I-] n [S2O82-] m

Since [S2O82-] is held constant in solutions 1 to 5,

R = k1 [I-] n , where k1 = k [S2O82-]m
Hence, log R = log k1 + n log [I-]
and a plot of log R against log [I-] in Figure 1 gives a straight line of slope n.

From Figure 1,
Slope of best-fit line = 1.243
∴ n = 1 (to the nearest integer)

Likewise, since [I-] is held constant in solutions 6 to 10,

R = k2 [S2O82-]m , where k2 = k [I-] n
Hence, log R = log k2 + m log [S2O82-]
And a plot of log R against log [S2O82-] in Figure 2 gives a straight line of slope m.

From Figure 2,
Slope of best-fit line = 1.122
∴ m = 1 (to the nearest integer)

Calculation of k values for each solution

Since m = 1 and n = 1, k = R / ([S2O82-] [I-] )

Solution [S2O82-]/M [I-]/M R /mol L-1s-1 k /M-1s-1

1 0.0385 0.0769 1.67 x 10-5 5.64 x 10-3
2 0.0385 0.0615 1.22 x 10-5 5.15 x 10-3
3 0.0385 0.0462 8.13 x 10-6 4.57 x 10-3
4 0.0385 0.0385 6.60 x 10-6 4.45 x 10-3
5 0.0385 0.0231 3.69 x 10-6 4.15 x 10-3
6 0.0385 0.0769 1.51 x 10-5 5.10 x 10-3
7 0.0308 0.0769 1.17 x 10-5 4.94 x 10-3
8 0.0231 0.0769 8.34 x 10-6 4.69 x 10-3
9 0.0192 0.0769 7.04 x 10-6 4.77 x 10-3
10 0.0115 0.0769 3.87 x 10-6 4.38 x 10-3

7) Calculation of the mean of k and the mean deviation

kmean = (∑ Values of k) / 10
= 4.784 x 10-3 M-1s-1
= 4.78 x 10-3 M-1s-1 ( 3 sig.f)
Deviation = k- kmean
Deviation
Solution k /M-1s-1 kmean / M-1s-1 (= k- kmean) / M-1s-1
1 5.64 x 10-3 8.56 x 10-4
2 5.15 x 10-3 3.66 x 10-4
3 4.57 x 10-3 -2.14 x 10-4
4 4.45 x 10-3 -3.34 x 10-4
5 4.15 x 10-3 -6.34 x 10-4
4.784 x 10-3
6 5.10 x 10-3 3.16 x 10-4
7 4.94 x 10-3 1.56 x 10-4
8 4.69 x 10-3 -0.94 x 10-4
9 4.77 x 10-3 -0.14 x 10-4
10 4.38 x 10-3 -4.04 x 10-4

∴ Mean deviation in k = (∑ Values of deviation) / 10

=0

8) Graph of loge t against 1/T for the temperature-dependence experiment

Temperature
Temperature,T / K Time,t /s (1/T) / K -1 ln(t/s)
/ oC
10.0 283.15 1144 3.53 x 10-3 7.04
20.0 293.15 322 3.41 x 10-3 5.77
30.0 303.15 86 3.30 x 10 -3
4.45
45.0 318.15 16 3.14 x 10-3 2.77
60.0 333.15 4 3.00 x 10-3 1.39

Figure 3

Combining the equations derived from Arrhenius equation, we get

loge t = Ea / RT + D
Hence, the plot of loge t against 1/T in Figure 3 will give a straight line with slope Ea/R.
From Figure 3, slope of best-fit line = 10735
∴ Ea/R = 10735
Ea = 10735 x 8.314 J mol-1 K-1
= 89.3 kJ mol-1

Discussion

1) Method of Initial Rates

When we use the method of initial reaction rates to determine the rate law of a
 chemical reaction, we measure the initial rate of reaction at short instantaneous
intervals before any significant changes in the concentrations of reactants occur. For
us to determine the order of reaction with respect to each participating reactants, the
initial concentration of that reactant is varied and the subsequent change in the rate of
reaction observed.
Such a method is useful as it saves time since complete reaction is not necessary in
observing the initial rates. It is also a relatively efficient way of determining the rate
law of a chemical reaction, especially for the study of slow reactions.
However, its disadvantages include:
1. Requiring the need to perform multiple experiments with only the concentration
of a single reactant varied, just to determine the order of reaction with respect to a
that reactant.
2. Only working for slow reactions as, if the reaction proceeds too fast, the
uncertainty as well as percentage error in measurements would be significantly
high.

2) Keeping the temperature for each reacting solution constant

Arrhenius proposed that for every reaction, the colliding molecules must exceed a
minimum energy threshold called the activation energy, Ea, in order to react. At a
given temperature, molecules possess a range of kinetic energies as shown by the
Maxwell-Boltzmann distribution curve. Effective collisions would only occur
between reacting molecules with energies greater than the activation energy required
of the reaction.

As the temperature is increased, the distribution curve shifts right (as shown in the
figure below) resulting in a higher fraction of molecules having energies greater than
Ea. Therefore, there is an increase in the number of effective collisions, leading to an
increase in the rate of reaction.
 In the first part of our experiment, where we seek to determine the order of reaction
with respect to the reactants, varying concentrations of reactants should be the only
factor affecting the rate of reaction. By keeping the temperature constant for all the
runs, it was ensured that the rate constant remained the same and any changes in the
rate of reaction were solely due to changes in the initial concentrations of the
reactants and hence, the order of reaction with respect to each reactant can be
determined accurately.

3) Keeping the total volume of the mixture constant

For our experiment, varying amounts of de-ionized water were added to each
reacting solution so as to keep the total volume constant. Thus, the concentration of
each reactant is proportional to the volume of reactant used. And so, by maintaining
the volumes of all other reactants as constant, it is easy for us to vary the initial
concentrations of the reactant simply by changing the volume of that reactant used.
Essentially, the total volume was kept constant by adding de-ionized water to
maintain the ionic strength of the reacting solution.

The ionic strength, on a concentration basis, of a solution is a function of the

concentration of all ions present in a solution.
Ic = ½ Σ cBzB2

(where cB is the molar concentration of ion B (mol dm-3), zB is the charge number of
that ion, and the sum is taken over all ions in the solution.)
 In the study of solution reaction kinetics, it is more desirable to change the
concentration of an active species without changing the ionic strength of the solution
as the latter affects the rate constant by the kinetic ionic-strength effect. Since the
charges of the reacting iodide and persulfate ions have the same sign, the activated
complex would be much more charged than its reactants. Hence, increasing the ionic
strength of the solution would increase the stability of the activated complex causing
a decrease in the Ea and thus, increasing the rate constant.

Our aim at the beginning of the experiment was to determine the rate law of the
reaction, with all factors except one, being kept constant all the time. By maintaining
the ionic strength of the solution, it ensured that the rate constant was kept
unchanged and that any changes in the rate of reaction were solely due to changes in
concentrations of the iodide and persulfate ion.

4) Pseudo-1st order / Isolation method

From the rate equation of the earlier experiment,
R = k [I-] [S2O82-]
we gather that 2 reactant molecules are involved in the rate determining step. By
keeping the concentration of any one reactant constant (i.e. [S2O82-]) as the reaction
progresses, the reaction can then be said to be pseudo-1st order with respect to the
other reactant (i.e. [I-]) with new rate constant kobs = k [S2O82-] and now the rate of
reaction only depends on changes in that reactant’s concentration (i.e. [I-]).
The [S2O82-] should be set to be much higher than [I-] to ensure that changes in the
concentration of S2O82- would not be significant throughout the course of the
reaction.

5) Precautions taken
Determination of Reaction Orders and Rate Constant
i) The conical flasks used to hold the reacting solution were shaken as dry as possible
between runs so as to ensure that the concentrations of the reactants are kept as
accurate as possible since it has a direct effect on the rate of reaction.
ii) For each run, the contents were swirled for approximately the same length of time and
then left to stand. This is to ensure that all reacting solutions were mixed
 homogeneously and avoid significant changes between the rate of reactions caused by
difference in swirling.
iii) Before the addition of the variable reactant for the reaction to occur, the temperature of
the solution was taken and necessary alterations made to ensure that for all the runs,
the reaction was occurring at a constant temperature. Any discrepancies in temperature
would affect the rate constant.
iv) When timing, the stopwatch was only started when the last drop of reactant in the test
tube was added to the reactant in the conical flask. This minimizes lapses in timings.
v) The conical flasks of the solutions were placed on a white piece of paper in every run
so that any colour changes would be distinct and observed instantaneously.

Determination of the Temperature Effect on a Chemical Reaction

i) The temperature of the water bath was constantly checked to ensure that it is kept
almost constant. For the runs carried out between 0oC to 20oC, any change in the
temperature of the water bath was promptly reversed by adding ice or water.
ii) During the course of the reaction, the reacting mixtures were fully immersed in the
water bath to ensure that all parts of the mixture are at constant temperature throughout
the experiment. Any slight changes in temperature would result in significant changes
in the reaction rates and thus, affect the accuracy of results.
iii) To accurately determine when the reacting mixture turns colourless, a flask of
colourless reactant was placed next to the reacting mixture for simple comparison.
iv) More than one set of timings were taken for each run so as to reduce the effect of
human error.

Conclusion
Determination of Reaction Orders and Rate Constant
Experimental results have shown that the order of reaction with respect to I- and S2O82-
for the reaction, 2 I- (aq) + S2O82- (aq) → I2 (l) + 2 SO42- (aq) are both 1 respectively.
Thus, it is an overall second order reaction. Using these values, the average rate constant
of the reaction, kmean, was calculated to be 4.78 x 10-3 M-1s-1. Since the mean deviation of
the value k is 0, we conclude that the method of initial reaction rates is a relatively
accurate approach to determine the reaction orders, rate constants and hence, the rate law
for the reaction between iodide and persulfate ions.

Determination of the Temperature Effect on a Chemical Reaction

From our experimental results, the activation energy, Ea of the reaction between KMnO4
and oxalic acid was found to be 89.3 kJ mol-1. We can infer that temperature is inversely
proportional to the time needed for the reaction to be completed. Hence, we conclude that
temperature is linearly related to the rate of reaction and this agrees with the relation
offered by the Arrhenius equation.

References

P.W. Atkins & J.de. Paula, 2006. Atkins’ Physical Chemistry 8th Ed. Published by
Oxford, Portland.

M.S. Silberberg, 2003. Chemistry the Molecular Nature of Matter and Change 3rd
Edition. Published by McGraw Hill.
Chemical Kinetics: Method of Initial Rates
Retrieved 18th February 2008 from the World Wide Web:
http://www.chm.davidson.edu/ChemistryApplets/kinetics/MethodOfInitialRates.html

Chemical Kinetics: Isolation Method

Retrieved 18th February 2008 from the World Wide Web:
http://www.chm.davidson.edu/ChemistryApplets/kinetics/IsolationMethod.html

Wikipedia – Ionic Strength

Retrieved 18th February 2008 from the World Wide Web:
http://en.wikipedia.org/wiki/Ionic_strength

Kinetic electrolyte effect

Retrieved 18th February 2008 from the World Wide Web:
http://www.iupac.org/goldbook/K03401.pdf

Kinetics of the Persulfate-iodide Clock Reaction

Retrieved 18th February 2008 from the World Wide Web:
http://ptcl.chem.ox.ac.uk/~hmc/tlab/experiments/502.pdf.