Kinetics between Ferric and Iodide Ions

*Christian Paolo Asequia, **Ercille Mae Pacamo,

***Rene Susette Ann Pontillas, **** Mariza Silagan
Department of Chemical Engineering
Xavier University-Ateneo de Cagayan
Corrales Avenue, Cagayan de Oro, Philippines
Juliet Dalagan, PhD
Department of Chemistry
Xavier University-Ateneo de Cagayan
Corrales Avenue, Cagayan de Oro, Philippines


Abstract: The experiment aims to determine the order of the
reaction rate of the reactants in the reaction: 2Fe
3+
+ 3I
-

2Fe
2+
+ I
3
-
. Also, the experiment aims to determine its over-all
reaction and its overall reaction rate. lastly, It aims to
determine the effects of adding a concentration of another
reactant to the solution. The method used was the method of
initial rates, which varies the concentration of one of the
reactants while the other is being held constant. Through this,
the time it takes to convert the product to reactant was
determined and also its respective concentration. Through this,
the rate of the reaction was determined. The logarithm of the
varied concentration of one reactant was plotted with the
logarithm of its rate. The equation of the line then was
determined and the slope, which corresponds to the order of
the reaction, was obtained. For the ferric ion, the order was
found out to be one and for the iodide, it was found out to be
2. The over-all reaction order was then found out to be three.
Furthermore, through series of calculations, the reaction rate
constant average was determined and it was found out to be
54.31. Lastly, through calculations, it was found out that the
addition of another substance reduces the rate of reaction of
the solution. Errors contributed to the experiment especially
the errors committed by the experimenters.

Keywords: Rate Constant, Rate Law, Order of Reaction,
Reaction Rate
I. INTRODUCTION

In order to write the expression of the rate of the
reaction, it is necessary to experimentally determine the
relationship between the rate and the concentration of each
reactant. More often than not, the rate of the reaction will
increase if the concentration of the reactant will be increased.
Increasing the population of the reactant also increases the
likelihood of a successful collision. According to the collision
theory, an assumption is made that for a reaction to proceed,
molecules of the reactants must collide with sufficient energy
and proper orientation.
[1]

The Rate Law states that for any general reaction
aA + bB cC + dD , the rate is proportional to [A]
m
[B]
n
, that
is:
Rate = k [A]
m
[B]
n
[Equation 1]

The expression is the general expression for the rate
law where k is the rate constant. The dependence of the rate of
the reaction on the concentration can often be expressed as a
direct proportionality in which the concentrations may appear
to be zero, first or second power. The power to which the
concentration of a substance appears in the rate law is the
order of reaction with respect to that substance. In the general
reaction, the order of the reaction is: m + n
[2]

The clock reaction approach can be used for the
kinetic study of ferric and iodide ions. This is named after the
analogy between chemical changes in such reactions and an
alarm clock. In a clock reaction, chemical change becomes
visible only after the reaction has reached a certain extent.
There are three steps in each clock reaction. The first is a slow
formation of a chemical intermediate. The second step is a fast
consumption of the intermediate by the limiting reagent and
the last step takes place after the limiting reagent has been
consumed which then causes the color change. The three steps
can be easily presented through:

A + B T ; slow
T + L X ; fast
T + I S ; fast

; Where initial reaction mixture contains variables A,
B, L and I. l is the limiting reagent and I is the indicator. S
represents chemical species that sends out the signal for color
change.




















The kinetics of the reaction transformed into a clock reaction
is easily investigated by the initial rate method. All that has to
Figure 1.Calculation of the average rate.
be measured is the time elapsed from the mixing of two
solutions to sudden color change. For the oxidation of iodide
by ferric ions, the reaction rate can be defined as:

[Equation 2]

The initial reaction rate can then be approximated by:

[Equation 3]
With [Fe
3+
] being the change in the concentration
of ferric ions in the initial period of the reaction. If t is the
time measured, then [Fe
3+
] is the decrease in ferric ion
concentration from the moment of mixing to the moment of
complete thiosulfate (limiting reagent) consumption. The
chemical reaction is then defined by:

()

()
(

()
[Equation 4]

Therefore from the stoichiometric reactions, it follows that:

- [Fe
3
+
] = [S
2
O
3
2-
] [Equation 5]

And consequently,

v
o
= k[Fe
3+
]
o
k
[I
-
]
y
o


[Equation 6]

From the latter equation, it will then follow that:

[Equation 7]

If the initial concentration of only one reactant is
varied while the initial concentrations of the others are held
constant, it is possible to determine the order of the reaction
with respect to the reaction of the reactant with varied
concentration
[3]

The reaction to be studied in the experiment is the
oxidation of I
-
by the Fe
3+
ions according to the equation:

2Fe
3+
+ 3I
-
2Fe
2+
+ I
3
-
[Equation 8]

II. EXPERIMENTAL SECTION
The experiment was divided into three parts. The first
part is the reaction order with respect to Fe
3+
. A total of ten
(10) mixtures were prepared. Five of which is with varying
concentrations of Fe
3+
and the other five is where the
Potassium iodide concentration was kept constant. Contents of
the mixture were swirled and were allowed to reach
equilibrium for 10 to 15minutes. The initial temperature of
each mixture was recorded and each mixture for each run was
rapidly added and swirled until the appearance of the blue
color. At the instant the mixtures were mixed together, the
time was recorded until the appearance of the blue color.
Temperature of the blue mixture was also recorded.
The second part of the experiment was the
determination of the reaction order with respect to I
-
. The
procedure in the first part was done again but this time, the
concentration of the ferric ion was kept constant and the
concentration of the iodine was varied. A total of three runs
were made in this part of the experiment.
The third part of the experiment was the effects of
Fe
2+
. The first run of the first part was done but the HNO
3

solution was replaced with 0.002M of Fe(NH
4
)
2
(SO
4
)
2
in
HNO
3
solution.
III. RESULTS AND DISCUSSION

The experiment aims to investigate the oxidation of
the iodide ions by the ferric ions. Several mixtures were
prepared with varying concentrations of the substances
involved for the desired reactions. Moreover, the chemical
changes necessary in this clock reaction are the reactions
mentioned earlier. The limiting reagent is the Sodium
thiosulfate and the starch is the indicator. The signaling
species in this clock reaction is the starch-pentaiodine
complex or the starch-I
5
-
complex which is blue.

Table 1. Change in Time and Initial Rate of Reactions

Table 1 shows the change in time obtained from the
experiment. Runs 1 to 5 pertains to the first part of the
experiment in which the concentration of Iodide was kept
constant. Runs 6 to 8 is for the determination of the reaction
order with respect to I
-
in which the concentration of the Ferric
Ion was held constant. Since the rates of the reaction of the
ferric and iodide ions are dependent with respect to their
respective concentrations, we can express the rate as:




Where k is the reaction rate constant and a is the reaction
order of Fe
3+
and b is the reaction order of I
-
.

To be able to determine the reaction order of the Fe
3+
ion, the
slope of the line from the graph of log rate versus the log of
[Fe
3+
] wherein the concentration of ferric ions was varied at
different runs.
Run Change
in Time
(s)
M Thiosulfate Rate Log rate
1 48.66 0.0004 4.11x10
-6
-5.38614
2 34.24 0.0004 5.84x10
-6
-5.2335
3 27.78 0.0004 7.20x10
-6
-5.1427
4 25.15 0.0004 7.95x10
-6
-5.09951
5 24.67 0.0004 8.11x10
-6
-5.09114
6 169.43 0.0004 1.18x10
-6
-5.92796
7 52.20 0.0004 3.83x10
-6
-5.41664
8 14.97 0.0004 1.34x10
-6
-4.87419
y = 0.6193x - 3.8652
R = 0.9561
-5.5
-5.4
-5.3
-5.2
-5.1
-5
-3 -2.5 -2 -1.5 -1 -0.5 0
L
o
g


[
R
a
t
e
]

Log [Fe
3+
]
Log [Rate] vs. Log [Fe
3+
]

y = 1.562x - 1.7523
R = 0.887
-7
-6
-5
-4
-3
-2
-1
0
-3 -2.5 -2 -1.5 -1 -0.5 0
L
o
g

[
R
a
t
e
}

Log [I
-
]
Log [Rate] vs. Log [I
-
]
Table 2. Log [Fe
3+
] from Initial Concentration of [Fe3+]

The average value of the initial and final concentrations of the
ferric ions was used because of the presence of sodium
thiosulfate that yields a thiosulfate complex with a reversible
reaction as can be seen from the equation:



And another redox reaction that has an order of zero and
another with a reaction order of two that is negligible and
wont change anything from the reaction that was being
investigated.



The logarithm of the initial rate was plotted against the
logarithm of the average ferric ion to be able to obtain the
equation of the line and more importantly, the slope of the line
which corresponds to the order of the reaction with respect to
the ferric ions. The equation of the line was found out to be
y=0.6193x-3.8652, and the slope is then determined which is
0.6193. Since there is no reaction order of 0.6, it was rounded
up and therefore giving a value of the order of the reaction of
approximately equal to 1. A first order of reaction has a rate
proportional to the concentration of one of the reactants,
which in this case is the ferric ion.
[4]


The second part of the experiment corresponds to
runs 6 to 8 of table 1. This was done to determine the reaction
order with respect to iodide therefore the concentration of the
ferric ion was held constant throughout the process.

Table 3. Log [I
-
] from the Initial Concentration of iodide

Table 3 shows the varied concentration of iodide with
the concentration of ferric ion was held constant. The
logarithm of the iodide ion was obtained to be plotted against
the logarithm of the initial rate and obtain the equation of the
line.

Figure 3. Log rate vs Log [I
-
]

The plot of the logarithm of the rate of reaction was
plotted against the logarithm of the average concentration of
Iodide. The equation of the line was determined and found out
to be y = 1.562x-1.7523. Though this, the slope of the line can
directly be determined which then gives the value of 1.562.
This slope of the line corresponds to the order of the reaction
with respect to iodide. But since there is no order of reaction
which is 1.562, the value was rounded up and therefore will
give a value of the order of reaction approximately equal to 2,
which indicates a second order of reaction with respect to the
concentration of iodide. A second order of reactions implies
that the initial rate of the reaction quadruples.
[5]

By determining the reaction order of the two
reactants, the overall order of the reaction can be determined
by summing up the two values of the orders which then will
lead to an overall reaction order of three which implies that the
rate of reaction increases eightfold. Moreover, by obtaining
the orders of reaction, the rate constant denoted with k will be
determined through the rate equation:

Rate = k[Fe
3+
][I
-
]
2
Run [Fe
3+
]i [Fe
3+
]f [Fe
3+
]ave
log
[Fe
3+
]av
[I
-
]ave log rate
1 0.004 0.0036 0.0038
-2.42022

0.004 -5.3861
2 0.006 0.0056 0.0058 -2.23657 0.004 -5.2335
3 0.008 0.0076 0.0078 -2.10791 0.004 -5.1427
4 0.010 0.0096 0.0098 -2.00877 0.004 -5.0991
5 0.012 0.0116 0.0118 -1.92812 0.004 -5.0914
Run [Fe3+] [I-]ave log [I-]ave log rate
6 0.004 0.002 -2.69897 -5.92796
7 0.004 0.006 -2.22184 -5.41664
8 0.004 0.008 -2.09691 -4.87419
Figure1. Log [Rate] vs Log [Fe
3+
]

Table 4. Average Rate Constant

Table 4 shows the calculation of the average rate
constant for the chemical reaction. Through the use of the
identified rate law with the orders of the respective reactants
known, the rate constant was found out to be 54.31.
The last part of the experiment is to identify the
effect of Fe
2+
on the rate of reaction of the ferric and iodide
ions. The change in time that was recorded in the experiment
was 76.77 seconds. The same concept as the run 1 of the first
part was followed for the calculation of the rate,

M/s

Comparing the rate that was obtained in the first run
of the first part, the rate was reduced by approximately 63%
which indicates that with the addition of Fe
2+
to the solution
reduces the rate of the reaction of Iodide and Ferric ions.

IV. ERROR ANALYSIS
The errors in the experiment may have surfaced and
caused a deviation from the true values. The change of time
may have caused an error since it varies from one person to
another. Another error that may have surfaced in the
experiment is the end point interpretation since it was done
by different persons and again may vary from one person to
another. Lastly, in the preparation of the solutions, there
might be excess or lack of the amount of substance in the
mixture that may have caused the change in concentration.
Moreover, impurities in the equipment used also may play a
big factor in the execution of the experiment since this may
cause a change in the concentration of the solutions and the
experiment depends greatly on the concentration of the
solution.
V. CONCLUSION

The order of the reactants was obtained in the
experiment. For the ferric ion, it was found out to be one or
the first order. On the other hand the order of reaction with
respect to iodide is 2 which is in second order. The over-all
order of the reaction was also determined through summing up
the orders of reaction of the reactants and it lead to a third
order of the reaction. Moreover, the reaction rate constant was
also obtained and it gave a reaction rate constant of 54.31.

REFERENCES
[1]
HTTP://WWW.CHM.DAVIDSON.EDU/VCE/KINETICS/METHODOFI
NITIALRATES.HTML (DATE ACCESSED: FEBRUARY 22,2014)

[2] http://www.chem4kids.com/files/react_rates.html (date
accessed: 02/22/2014)

[3] http://www.kbcc.cuny.edu/academicdepartments/ (date
accessed 02/22/2014)

[4]
http://chemwiki.ucdavis.edu/Physical_Chemistry/Kinetics/Rat
e_Laws/The_Rate_Law (data accessed: 03/01/2014)

[5]
http://www.chemguide.co.uk/physical/basicrates/experimental
.html (date accesed: 03/01/2014)

APPENDICES
I. CALCULATIONS
(a) Determination of the Concentration of Sodium Thiosulfate


(b) Determination of Initial Rate
[Rate] = 4.11x10
-6
M/s
(c) Calculation of Iodide Concentration


Rate M [Fe
3+]
M [I
-
] k Kave

4.11x10-6 0.0038 0.004 67.60
54.31
5.84x10
-6
0.0058 0.004 62.94
7.20x10
-6
0.0078 0.004 57.69
7.95x10
-6
0.0098 0.004 50.72
8.11x10
-6
0.0118 0.004 42.94
1.18x10
-6
0.004 0.002 73.78
3.83x10
-6
0.004 0.006 26.61
1.34x10
-6
0.004 0.008 52.19

(d) Calculation of Ferric Ion Concentration



(e) Calculation of Ferric ions final Concentration

(f) Calculation of Average Ferric Ion Concentration
(g) Calculation of the rate Constant, k:
k = 67.60