TABLE OF CONTENT

TABLE OF CONTENT ........................................................................................................................ 1

1.0 ABSTRACT ..................................................................................................................................... 2
2.0 THEORY ......................................................................................................................................... 3
3.0 EXPERIMENTAL PART .............................................................................................................. 5
3.1 APPARATUS ............................................................................................................................... 5
3.2 CHEMICALS AND REAGENTS ................................................................................................ 5
3.3 EXPERIMENT PROCEDURES .................................................................................................. 5
4.0 EXPERIMENTAL RESULTS ....................................................................................................... 7
4.2 ORDER DETERMINATION OF THE REACTION FROM THE GRAPH ............................. 10
4.3 DETERMINATION OF THE AVERAGE RATE CONSTANT, K .......................................... 11
4.4 THE ABSOLUTE MEAN DEVIATION AND STANDARD DEVIATION FOR THE RATE
CONSTANT ..................................................................................................................................... 13
4.5 RATE LAW AND PROPOSED REACTION MECHANISM .................................................. 14
5.0 DISCUSSION ................................................................................................................................ 14
5.1 SOURCES OF ERROR .............................................................................................................. 14
5.2 MODIFICATIONS TO MINIMIZE THE ERRORS .................................................................. 15
6.0 CONCLUSION ............................................................................................................................. 15
7.0 REFERENCE. ............................................................................................................................... 16

1
1.0 ABSTRACT
The aim of the experiment was to study the kinetic rate law of the reaction. The reaction
concerned involved Iodide ions {I-} and Persulphate ions {S2O82-} where the rate constant
and the order of reaction with respect to both Iodide and Persulphate ions were determined at
room temperature. The method used was initial rates method whereby the experiment was
divided into two parts A and B. In part A, the concentration of Iodide ions {I-} was kept
constant while varying the concentration of Persulphate ion {S2O82-}. In part B, the
concentration of Persulphate ions {S2O82-} was kept constant while varying the concentration
of Iodide ions {I-}. Finally the order of reaction with respect to {I-} was found to be one (1)
and that with respect to {S2O82-} was found to be one (1) and hence overall order of reaction
was two (2). The average rate constant, K was 7.9539 X 10-4 mol-1 dm3 s-1. Therefore, the rate
law was R = K [I-] [S2O82-], where K is rate constant.

2
2.0 THEORY

According to the rate law which state that “the rate of reaction is direct proportional to the
product of concentration of reactants each raised to their respective order of reaction

Consider the reaction equation: aA + bB → cC

Where a, b and c are stoichiometric coefficients while A and B are reactants and C is the
product, then the rate law will be, Rate = K [A]m[B]n

Where K is the rate constant, [A] and [B] are concentrations of reactants A and B
respectively and ‘m’ and ‘n’ are the orders of reaction with respect to A and B respectively.
The overall order of reaction will be m+n

The measure of how quickly the reactants are consumed of products are formed can give the
rate at which the reaction proceed

Rate = -1/a d[A]/dt = -1/b d[B]/dt = 1/c d[C]/dt

The reaction rates evaluated initially at t=0, give the initial rates of reaction whereby this
initial rate method can be used in determination of rate law. In this method the time to
consume a very small fraction (approximately 1%) of one of the reactants, for example A is
measured and recorded with is corresponding initial concentration [A]0. The initial rate of
reaction is given by the slope of the line joining [A]0 and [A]t from the graph of [A] vs. time

Fig 1: a graph of [A] vs. time

Rate = -1/a {([A]t - [A] 0 )/∆t}

3
When varying initial concentration of A, [A]0 while keeping constant that of B, [B]0 , different
values of initial rates can be obtained thereafter the order of reaction with respect to A may
be determined as follows:

Initial rate, R = K [A0]m[B0]n , since [B]0 is constant, then

R = K’ [A0]m

By applying natural logarithm both sides, we have

ln R = m ln[A]0 + ln K’

From the above relation, a graph of ln R vs. ln[A]0 gives a straight line with positive slope
corresponding to order of reaction with respect to reactant A, (m) and it’s Intercept as ln K’

With [B]0 varying and [A]0 kept constant the parallel set of experiments can be done which
will help to evaluate the order of reaction with respect to reactant B, (n), and K” = {K [A0] m}

As long as ‘m’ and ‘n’ are known then together with the values of K’ and K” reaction rate
constant, K can be evaluated

The reaction from the experiment done involved persulphate ions and iodide ions in aqueous
solution S2O82-(aq) + 2I-(aq) → 2SO42-(aq) + I2(s)

The initial rate of reaction was determined experimentally by measuring the time taken for a
given fraction of persulphate to react. This was found by introducing an appropriate amount
of thiosulphate with iodine indicator into the system so that the below reaction took place

2S2O32-(aq) + I2(s) → S4O62-(aq) + 2I-(aq)

When all thiosulphate ions were consumed by this reaction, the liberated iodine was detected
by iodine indicator (starch) which was turning blue.

4
3.0 EXPERIMENTAL PART
3.1 APPARATUS
 Two conical flasks, A and B
 25ml pipette
 10ml pipette
 50ml flat bottomed flask
 White tile
 Stop watch

3.2 CHEMICALS AND REAGENTS

 Distilled water
 0.01M sodium thiosulphate solution
 0.1M EDTA solution
 Iodine indicator (starch)
 0.2M potassium persulphate solution
 0.2M potassium iodide solution

3.3 EXPERIMENT PROCEDURES

Part A: Determination of order and rate constant at constant iodide concentration

1. 50ml of potassium persulphate was put in a flat bottomed flask

2. 25ml of potassium persulphate from flat bottomed flask was pipetted into a conical
flask A
3. To a conical flask B, 25ml of potassium iodide solution was pipetted followed by
10ml of thiosulphate
4. Three (3) drops of iodine indicator (starch) and one (1) drop of EDTA were added to a
conical flask B. EDTA solution prevented catalysis by metal impurities. Starch was
there to detect the presence of iodine which were turning blue.
5. The mixture from flask B was then added into flask A. At the instant of adding, stop
watch was started to record the time when first colour change of the mixture observed
which was blue. Thereafter the conical flasks were cleaned by distilled water ready
for next experiment.

5
 6. From the remained 25ml persulphate in flat bottomed flask, 20ml of Potassium nitrate
was added which then topped up by 5ml of distilled water. This was the dilution
process which resulted to half the concentration of persulphate, 0.1M. Potassium
nitrate did not participate in the chemical reaction, it was added in order to keep the
overall ionic strength of each solution constant.
7. From diluted persulphate in flat bottomed flask, the procedures 1, 2, 3, 4 and 5 were
repeated to get another time for reaction completion.
8. The same procedures of dilution, mixing the solutions for them to react and time
recording were done for other two concentrations, 0.05M and 0.025M of persulpate.
9. The experimental results for this part is attached

Part B: Determination of order and rate constant at constant persulphate concentration

1. 25ml of potassium persulphate was pipetted into conical flask A

2. 50ml of potassium iodide was put in a flat bottomed flask which then 25ml of it from
flat bottomed flask was pipetted into a conical flask B followed by 10ml of
thiosulphate.
3. Three (3) drops of iodine indicator (starch) and one (1) drop of EDTA were added to a
conical flask B.
4. The mixture from flask A was then added into flask B. At the instant of adding, stop
watch was started to record the time when first colour change of the mixture observed
which was blue. Thereafter the conical flasks were cleaned by distilled water ready
for next experiment
5. From the remained 25ml potassium iodide in flat bottomed flask, 20ml of Potassium
nitrate was added which then topped up by 5ml of distilled water. This was the
dilution process which resulted to half the concentration of iodide solution, 0.1M.
6. From diluted iodide solution in flat bottomed flask, the procedures 1, 2, 3 and 4 were
repeated to get another time for reaction completion.
7. The same procedures of dilution, mixing the solutions for them to react and time
recording were done for other two concentrations, 0.05M and 0.025M of iodide
solution.
8. The experimental results for this part is also attached

6
4.0 EXPERIMENTAL RESULTS
To determine the reduced concentration of both iodide ions and persulphate ions.

The aim of experiment reveal determination of the order of reaction and the rate constant of
the following reactions:

2I-(aq) + S2O82- (aq) ⟶ I2(aq) + 2SO42-(aq) ……………(i)

I2(aq) + 2S2O32-(aq) ⟶ 2I-(aq) + S4O62-(aq)…..………….(ii)

Having the initial number of moles of S2O32- initially present in the flask and the volume of
the mixture amount to 60cm3 then we can find the reduced concentration of persulphate and
iodide ions as show below.

 First, number of moles of S2O32- given in 10 cm3

Morality of S2O32- = 0.01mol dm-3
Number of moles = 0.01mol dm-3 x 10 x 10-3 dm-3
= 1 x 10-4 mol of S2O32-
 From the reaction (ii), the mole ration between S2O32- and I- is 1:1 hence the number
of moles of iodide ions formed also were = 1 x 10-4 mol of I-

 To determine the number of moles of S2O82- ,consider the reaction (i)

The mole ratio between S2O8 2- and I- was 1:2 hence
Number of moles of S2O8 2- reacted = 1∕2 x 1 x 10-4 mol
= 0.5 x 10-4 mol of S2O8 2- used.
 The concentration of persulphate ions.
Since the ions were present in 60ml mixture, hence its concentration is given by:
Morality of S2O82- = (no. of moles)/ (volume of the mixture)
= (0.5 *10-4 mol of S2O8 2-)/ (60*10-3 dm-3)
= 8.333 x 10-4 mol dm-3 of S2O8 2-
Therefore the reduced concentration of the persulphate ions is 8.333 x 10-4 mol dm-3
 To determine the reduced concentration of iodide ions, consider the reaction (i)
The mole ration between S2O8 2- and I- is 1:2 hence
1 mol of S2O82- ⟶ 2 moles of I-
8.333 x 10-4 mol dm-3 of S2O82- ⟶ ?

Therefore the reduced concentration of iodide ions were 1.667 x 10-3 mol dm-3 of I-

7
4.1 DETERMINATION OF THE INITIAL RATE OF REACTION FOR EACH
EXPERIMENT

 Experiment part A:
From the equation
Rate (t=0) = [-1/a] x {([A]t - [A]
o) / △t }
Where “a” is a stoichiometry constant from a balanced chemical reaction.

In experiment part A, [S2O82-] was varied while [I-] was kept constant.

Initial rate = K [S2O82-]m [I-]n where K[I-]n is another constant k’

= K’ [S2O82-]m

Hence, initial rate{t=0) = (-1/a ) x {([ S2O82- ]t – [S2O82- ]o) / △t }

Where a = 1 from a balanced chemical reaction.

The reduced concentration of persulphate solution is 8.333 x 10-4 moldm-3

[S2O82-]o = [S2O82-]t + 8.333x10-4 moldm-3

[S2O82-]t - [S2O82-]o = -8.333x10-4 moldm-3

The initial rates were as follows:

i. RI = -1/1 x (-8.333 x 10-4) / △t1 =

-1
/1 x (-8.333 x 10-4) / 36.3 s
= 2.2956 x 10-5 moldm-3s-1
ii. R2 = -1/1 x (-8.333 x 10-4) / △t2 =
-1
/1 x (-8.333 x 10-4) / 89.4 s
= 9.3210 x 10-6 moldm-3s-1
iii. R3 = -1/1 x (-8.333 x 10-4) / △t3 =
-1
/1 x (-8.333 x 10-4) / 226.6 s
= 3.6774 x 10-6 moldm-3s-1
iv. R4 = 1/1 x (-8.333 x 10-4) / △t4 =
-1
/1 x (-8.333 x 10-4) / 504.4 s
= 1.6521 x 10-6 moldm-3s-1

8
Table of results for part A:

Exp no. [I-] moldm-3 [S2O82-]moldm-3 Initial rate(R) ln [S2O82-] ln R

moldm-3s-1

1 0.20 0.200 2.2956 x 10-5 -1.609 -10.68

2 0.20 0.100 9.3210 x 10-6 -2.303 -11.58

3 0.20 0.050 3.6774 x 10-6 -2.996 -12.51

4 0.20 0.025 1.6521 x 10-6 -3.689 -13.31

 Experimental part B:
From the equation
Rate (t=0) = [-1/b]x {( [A]t - [A]
o) / △t }
Where “b” is a stoichiometry constant from a balanced chemical reaction.

In experiment part A, [I-] was varied while [S2O82-] was kept constant.

Initial rate = K [S2O82-]m [I-]n where K[S2O82-]m gave another constant k’’

= K’’ [I-]n

Hence, initial rate {t=0) = (-1/b ) x {([I-]t –[I-]o) / △t }

Where b = 2 from a balanced chemical reaction.

The reduced concentration of iodide solution is 1.667 x 10-3 moldm-3

[I-] o = [I-] t + 1.667 x 10-3 moldm-3

[I-] t - [I-]o = -1.667 x 10-3 moldm-3

The initial rates were as follows:

i. RI = -1/2 x (-1.667 x 10-3) / △t1 =

-1
/2 x (-1.667 x 10-3) / 33.9s
= 2.4581 x 10-5 moldm-3s-1
ii. R2 = -1/2 x (-1.667 x 10-3) / △t2 =
-1
/2 x (-1.667 x 10-3) / 67.4 s
= 1.2364 x 10-5 moldm-3s-1

9
 iii. R3= -1/2 x (-1.667 x 10-3) / △t3 =
-1
/2 x (-1.667 x 10-3) / 161.9 s
= 5.1470 x 10-6 moldm-3s-1
iv. R4 = 1/2 x (-1.667 x 10-3) / △t4 =
-1
/2 x (-1.667 x 10-3) / 298.3 s
= 2.7935x 10-6 moldm-3s-1

Table of results for part B:

Exp no. [S2O82-] [I-] Initial rate(R) ln [S2O82-] ln R

moldm-3
moldm-3 moldm-3s-1

1 0.20 0.200 2.4581 x 10-5 -1.609 -10.61

2 0.20 0.100 1.2364 x 10-5 -2.303 -11.30

3 0.20 0.050 5.1470 x 10-6 -2.996 -12.18

4 0.20 0.025 2.7935x 10-6 -3.689 -12.79

4.2 ORDER DETERMINATION OF THE REACTION FROM THE GRAPH

 Part A.

From the drawn graph of In [R] against In [S2O82-]. The slope of the graph gave the order of
reaction with respect to persulphate ions as the iodide ions were kept constant. The y- intercepy
of the graph gave the rate constant of the reaction. On calculation:

Slope = (△ In [R]) / (Δ ln[S2O82-])

= [(-10.4)-(-9.36)] / [ (-1.4)-(-0.5)]

= 1.16

Therefore the order of reaction with respect to persulphate ions (S2O82-) is approximately to
one (1)

10
  Part B

From the drawn graph of In [R] against In [I-]. The slope of the graph gave the order of reaction
with respect to iodide ions as the persulphate ions were kept constant. The y- intercept of the
graph gave the rate constant of the reaction. On calculation:

Slope = (△ In [R]) / (Δ ln [I-])

= ((-11.05) – (-8.99)) / ((-2) - (-1))

= 1.06

Therefore the order of reaction with respect to iodide ions (I-) is approximately to one (1)

4.3 DETERMINATION OF THE AVERAGE RATE CONSTANT, K

So long as the orders of reaction with respect to both persulphate and iodide ions, the initial
rate and the concentrations of reactants are all known, the rate constant of reaction can be found
from equation given below:

Initial rate (Ro) = K [S2O82-]m [I-]n

Where Ro = initial rate

K = rate constant

[S2O82-] = concentration of persulphate

[I-] = concentration of iodide

m = order of reaction with respect to persulphate =1.16

n = order of reaction with respect to iodide = 1.06

Hence K = {Ro}/ {[S2O82-] m [I-]n }

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For part A:

Exp no. [I-] moldm-3 [S2O82-] moldm-3 Initial rates Rate constant

moldm-3s-1

1 0.200 0.200 2.2956 x10-5 8.1773 x10-4

2 0.200 0.100 9.3210 x10-6 7.4194 x10-4

3 0.200 0.050 3.6774 x10-6 6.5410 x10-4

4 0.200 0.025 1.6521 x10-6 6.5665 x10-4

For Part B:

Exp no. [I-] moldm-3 [S2O82-] moldm- Initial rates Rate constant
3
mol-1dm3s-1
moldm-3s-1

1 0.200 0.200 2.4581 x10-5 8.7561 x10-4

2 0.100 0.200 1.2364 x10-5 9.1825 x10-4

3 0.050 0.200 5.1470 x10-6 7.9699 x10-4

4 0.025 0.200 2.7935 x10-6 9.0185 x10-4

The average rate constant for the reaction is calculated as:

= {K1 + K2 +K3 +K4 +K5 +K6 +K7 +K8} / 8

= {(8.1773 + 7.4194 + 6.5410 + 6.5665 +8.7561 + 9.1825 + 7.9699 + 9.0185) X10-4} / 8

= 7.9539 X 10-4 mol-1 dm3 s-1

Therefore, the average rate constant for the given reaction is 7.9539 X 10-4 mol-1 dm3 s-1

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4.4 THE ABSOLUTE MEAN DEVIATION AND STANDARD DEVIATION FOR THE
RATE CONSTANT
Consider the table below

K (mol-1 dm3 s-1) ∣K- Kmean∣ (mol-1 dm3 s-1) (K-Kmean)2 (mol-2dm6s-2)

8.1773 x10-4 0.2243 x10-4 5.0310 x10-10

7.4194 x10-4 0.5336 x10-4 2.8473 x10-9

6.5410 x10-4 1.4120 x10-4 1.9937 x10-8

6.5665 x10-4 1.3865 x10-4 1.9224 x10-8

8.7561 x10-4 0.8031 x10-4 6.4497 x10-9

9.1825 x10-4 1.2295 x10-4 1.5117 x10-8

7.9699 x10-4 0.0169 x10-4 2.8561 x10-12

9.0185 x10-4 1.0655 x10-4 1.1353 x10-8

TOTAL 6.6714 x 10-4 7.5434 x10-8

Mean deviation = ∑ ∣K – Kmean∣ / n

= 6.6714 x 10-4 / 8

= 8.33925 x 10-5 mol-1 dm3 s-1

Standard deviation = √ {∑ (K – Kmean)2 / (n-1)}

= √ {(7.5434 x 10-8) / (8-1)}

= 1.0381 x 10-4 mol-1 dm3 s-1

Therefore, the mean deviation is 8.33925 x 10-5 mol-1 dm3 s-1 and

standard deviation is 1.0381 x 10-4 mol-1 dm3 s-1

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4.5 RATE LAW AND PROPOSED REACTION MECHANISM
The kinetic rate law states that “The rate of reaction is directly proportional to the product of
concentrations of reactants each raised to its respective order of reaction”

Reaction mechanism:

S2O82- + I- ⟶ IS2O83-………… (i)

IS2O83- ⟶ I+ + 2SO42-………... (ii)

I+ + I- ⟶ I2 …………………… (iii)

The overall reaction: S2O82- + 2I- ⟶ 2SO42- + I2

Hence the rate law: Rate = 7.9539 X 10-4 [S2O82-] 1.16 [I-] 1.06

5.0 DISCUSSION
The experiment aimed at investigating the kinetic rate law where the rate constant and orders
of reaction were determined. The reaction involved persuphate ions and iodide ions as per
ionic equation

S2O82-(aq) + 2I-(aq) → 2SO42-(aq) + I2(s).

The presence of iodine in reaction mixture was detected by iodine indicator (starch) in which
their reaction led to formation of blue coloured solution

The results obtained from the experiment may not be accurate due to presence of sources of
errors, as briefly explained below together with some modifications to minimize them

5.1 SOURCES OF ERROR

 Error due to contamination of the apparatus and chemicals like using the same
pipette and conical flasks in two different experiment
 Incorrect timing while starting and stopping the stop watch hence wrong time
recording

14
  Incorrect measures of the amounts of reactants may lead to different
concentration from that required, as one of the factors affecting reaction rate is
concentration hence may result wrong answers

5.2 MODIFICATIONS TO MINIMIZE THE ERRORS

 The apparatus should be washed after each experiment to avoid errors due to
contamination
 Careful time recording
 Accuracy in measuring amounts of reactants
 Careful observing the first colour change

6.0 CONCLUSION
From the experiment, it has been shown that the rate of reaction is directly proportional to the
product of concentrations of reactants each raised to its respective order of reaction. The
order of reaction with respect to both persulphate and iodide ions were found to be one (1)
and the average rate constant for the reaction was 7.9539 X 10-4 mol-1 dm3 s-1

15
7.0 REFERENCE.
 Burns, B (1966), “The kinetic of the reaction between peroxydisulphate and iodise
ions in dimethyl sulfoxide” Oregon state university

 Forester, T,R (2002), “practical 1.12-kinetic rate laws guiding hand out”

 Espenson, J,H. (2002). “Chemical kinetics and reaction mechanism” 2nd edition.,
McGraw Hill

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