Kinetic Study of The Reaction

Kinetic Study of The Reaction

Between Ferric and Iodine Ions
Between Ferric and Iodine Ions

Chemicals Apparatus
Ferric nitrate, Fe(NO3)3
Nitric acid, HNO3 Beaker (100 and 250 mL)
Potassium iodide, KI Water bath
Sodium thiosulfate, Na2S2O3 Pipette
Starch Graduated cylinder

OBJECTIVE

In this experiment to the students will study the kinetics of an oxidation-reduction reaction
between ferric (Fe3+) and iodide (I-) ions and determine the order of the reaction with
respect to both ions.

THEORY
Chemical kinetics is study of reaction rates and reaction mechanisms. The Reaction
Rate for a given chemical reaction is the measure of the change in concentration of the
reactants or the change in concentration of the products per unit time. Reaction rates can
occur over very different time scales.

Four factors affect the rate at which any particular reaction occurs:
1- Physical state of the reaction
2- Reactant concentrations
3- Reaction temperature
4- Presence of a catalyst

For a given chemical reaction,

aA + bB → cC + dD

the reaction rate depends only on the concentrations of the reactants under certain
experimental conditions (temperature, presence of catalysts, etc.). The rate law describes
how the reaction rate depends on the concentrations of the reactants.

1 d[A] 1 d[B] 1 d[C] 1 d[D]

𝑟𝑎𝑡𝑒 = − =− = = = k [A]m [B]n
a dt b dt 𝑐 dt d dt

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The constant k is the specific rate constant for the reaction at a given temperature. The
exponents m and n are called reaction orders determined from experiment with respect to A
and B, respectively. The overall reaction order is the sum of m and n.

The reaction of today’s the experiment is

2Fe3+ + 3I − → 2Fe2+ + I3−

The rate expression, then becomes,

1 d[Fe3+ ] 1 d[I− ] 1 d[Fe2+ ] d[I3− ]

rate = − =− = = = k[Fe3+ ]a [I− ]b
2 dt 3 dt 2 dt dt

Parts A and B of this experiment are related to the determination of rate order of reaction
between Fe3+ and I- ions. The following slow reaction takes place when Fe3+ and I- are
mixed, by which Fe3+ is reduced to Fe2+ and triiodide ion, I3- forms.

2Fe3+ + 3I − → 2Fe2+ + I3− (slow)

The initial rate is determined by measuring the time in seconds required for the Fe3+
reduction to Fe2+. The amount of Fe3+ reduced is equal to the consumed thiosulfate, S2O32-
amount, 4x10-5 mole. This is because, as soon as each I3- formed in the slow reaction is
being consumed by S2O32- through the following fast reaction;

I3- + 2S2O32- → 3I- + S4O62- (fast)

The consumption of 2S2O32- is determined by addition of starch which is used as an

indicator. As soon as all of the S2O32- is consumed, any additional I3- is formed by the
reaction between ferric and iodide ions will react with the starch to form a characteristic
blue color.

I3 − + Starch → Blue colored mixture

excess

Note that when the blue color first appears, the decrease in the concentration of Fe3+ ions
from its initial value is just equal to the concentration of S2O32- in the mixture. Thus,
2−
1 d[Fe3+ ] 1 [S2 O3 ]i
the initial rate = − = 𝐸𝑞. 1
2 dt 2 ∆t

where [S2O32-]i is the initial concentration of S2O32- and t is the time in seconds between
mixing and the appearance of the blue color.

In order to obtain reasonable reaction times, it is necessary to use initial rate intervals
which allow the Fe3+ concentration to decrease slightly (about 4 to 10 percent) from its
initial value. Therefore, it is suggested that the average Fe3+ concentration during this time
interval be used which should correspond to 5% concentration change, equals to the half of
the S2O32- amount.

[Fe3+ ]f = [Fe3+]ini – [S2O32-]

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The average Fe3+ concentration is determined by

[Fe3+ ]ini + [Fe3+ ]f [S2 O3 2− ]

[Fe3+ ]ave = 3+
= [Fe ]ini −
2 2

PROCEDURE

CAUTION

1. Temperature changes affect the rate constant. Be careful on performing all

the experiments at the same temperature; make sure to use water bath to keep
temperature constant.

2. During the reactions, HNO3 is used to prevent hydrolysis of the Fe+3 in water
environment

3. Use 50 mL burettes to dispense H2O, Fe(NO3)3, and HNO3 solutions;

10 mL pipettes to dispense the KI and Na2S2O3 solutions, and
10 mL graduated cylinder to dispense the starch solution.

Reaction Order With Respect to Fe3+ and I-

The following sets of solutions in 250 mL and 100 mL beakers will be prepared and mixed
during the experiment.

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Table 9.1 Volume of the reagents that should be added to prepare 250 mL and 100
mL solutions for each set
Volume (mL) added Volume (mL) added to 100 mL
Set to 250 mL beaker beaker
Number 0.04M 0.15M 0.04M 0.004M
H2O Starch H2O
Fe3+ HNO3 KI S2O32-
1 10 10 30 10 10 5 25
2 15 10 25 10 10 5 25
3 20 10 20 10 10 5 25
4 25 10 15 10 10 5 25
5 30 10 10 10 10 5 25
6 10 10 30 5 10 5 30
7 10 10 30 15 10 5 20
8 10 10 30 20 10 5 15

Note for sets 1 to 5, Fe3+ concentration is varied while I- concentration is kept constant;
whereas for sets 6 to 8, Fe3+ concentration is kept constant while I- concentration is
varied.

A. Reaction Order with Respect to Fe3+

1. Prepare the first set of solutions in 250 mL beaker and 100 mL beaker using the
information given in the Table 9.1. Mark the beakers with set “# 1”.

2. Swirl the solutions in each beaker for a short time to mix well and place the beakers in a
constant temperature water bath for 10 minutes.

Similarly, prepare the second set and mark the set with “set #2”. Place these beakers
also into the same water bath.

3. By this time the first set should have reached to the bath temperature (if unsure measure
the temperature of the solutions). Then, while starting the timer, add (quickly) the
contents of the 100 mL beaker to the 250 mL beaker. You may remove the solutions
from the water bath during addition. Swirl the solutions until they are mixed well, then
replace the 250 mL beaker to the water bath.

4. Stop the timer at the first appearance of the blue color.

Record the time, Δt (s) in Table 1 in your report sheet.

Clean and make sure there is no remaining water in the beakers, prepare the next set, and
place the beakers in the water bath.

5. Then repeat the same procedure for sets 3-5.

Dispose your chemicals into aqueous waste container!

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B. Reaction Order with Respect to I-

1. Perform exactly the same procedures as in Part A for sets 6, 7 and 8.

In this case the concentration of ferric ion is kept constant while the concentration of
iodide ion is varied.

The amounts of chemicals to be used is given in Table 9.1.

2. Record the times, Δt (s) for each set in Table 1 in your report sheet.

Dispose your chemicals into aqueous waste container!

CALCULATIONS

1. Follow the given steps below and record your results in Table 2 in your report sheet.

a) Calculate the initial [S2O32-]i.

b) Calculate the initial reaction rate by using Equation 1.

c) Take logarithm of the calculated initial rates.

d) Calculate the initial Fe3+ concentration.

e) Calculate the average Fe3+ concentration by using the equation given below:

[Fe3+ ]f 4 × 10−5 mole S2 O3 2−

[Fe3+ ]av = ([Fe3+ ]i − )− = [Fe3+ ]i − 2 × 10−4
2 0,1 L solution x 2

f) Take logarithm of average Fe3+ concentrations of each of the prepared solutions.

g) Calculate the initial I- concentration. This will be equal to average I-

concentration.

h) Take logarithm of the average I- concentrations.

2. a) Plot log rate vs. log[Fe3+]av for experiments 1 to 5.

b) Find the slope of the line, this will be equal to a, reaction order with respect to
ferric ion.

3. a) Plot log rate vs. log[I-]av for experiments 1, 6, 7, 8.

b) Find the slope of the line, this will be equal to b, reaction order with respect to
iodide ion.

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