Determining the Rate Law for a Reaction between

Iron(III) and Iodide Ion

Valentin Uzunov (author) & Francesca Frattaroli (lab partner)
PSU ID#: 964100377
CHM 228H (Lab 261), Due: 4/7/2014

ABSTRACT
The rate law of a chemical reaction is useful in determining the dependence of a reaction rate on reactant
concentrations and in identifying probable reaction mechanisms. The rate law for the reaction between
potassium iodide and iron (III) chloride was determined using the initial rate methods. A spectrometer
was used to measure change in absorption overtime for 5 solutions of different concentrations from which the
initial rates were determined. By varying the initial concentrations of only one reactant at a time the reactant orders
were calculated from the initial rates measured to be seconds with respect to I
-
ion and first order with
respect to Fe
3+
ion. The overall rate law was rate = k[I
-
]
2
[Fe
3+
] which is consistent with previous literature.

INTRODUCTION
Chemical kinetics is the study of rates of chemical reactions the change in concentration of reactants to
products with time as well as the study reaction mechanisms. In the herein experiment the rate law for
the oxidation-reduction reaction between potassium iodide and iron (III) chloride was determined:

()

()

()

() [Rxn 1]

The rate law and reactant orders can only be determined experimentally, and cannot be derived from the
stoichiometry of the balanced reaction alone. In this experiment the rate law and reactant orders were
determined using the initial rates method. The results are expected to demonstrate a dependence between
the initial rate and concentration of reactants, as well as the dependence of the reaction on the limiting
reagent.
The rate law of a chemical reaction is a mathematical equation that describes how the rate of a reaction
depends upon the concentrations of each reactant. The rate law of a reaction must be proven
experimentally by looking at either the appearance of products or disappearance of reactants with time.
The dependence of the rate of a reaction on the concentration of reactants can often be expressed as a
direct proportionality in which the concentrations may appear raised to powers of zero, one or two. The
power associated with the reactant indicates the dependence of the reaction on that reactant. The general
rate law for a bimolecular reaction has the general reaction can be expressed by the following expression:


[]

[]

[Eq 1]
Where k is the rate constant, x and y denote the orders of reactants and [A] and [B] their molar
concentrations. The rate constant of a chemical reaction is dependent entirely on the absolute temperature
at which the reaction occurs, this relationship is given by the Arrhenius equation:

[Eq 2]
Where k is the rate constant, A is the frequency factor specific to that reaction, which relates the number
of properly aligned collisions between reactants that occur per second, E
a
( ) is the activation
energy of the reaction, which it the minimum energy required in a collision for a reaction to occur. R is
the gas constant (8.314 ), and T is the absolute temperature. A substitution of Eq1 into Eq2
leads to a more detailed rate law expression:

[]

[]

[Eq 3]
This relationship shows that the rate at which a reaction proceeds is directly dependent on the absolute
temperature at which the reaction is occurring. Therefore at very high temperatures almost every collision
is successful, and the reaction rate increases.
As long elementary reverse reactions are negligibly slow, the rate law can be assumed to be proportional
to the concentration of reactants and their orders. By varying the initial concentrations of only one
reactant at a time while keeping all others participating species initial concentrations unchanged, the order
of the reagent whose concentration is being varied can be calculated using the initial the rate method.
The initial rate of a reaction was determined by measuring the absorbance of the reaction with time.
Absorbance is directly related to concentration in dilute solutions by Beer-Lamberts Law, which states
that the quantity of light absorbed by a substance dissolved in a nonabsorbent solvent (such as water) is
directly proportional to the concentration of the substance and the path length of light through the
solution. This relationship relates the change in absorption to the change in concentration of the solution
as the reaction proceeds and is thus useful measure of the rate of a reaction. In dilute solutions the initial
rate (instantaneous rate) can be fairly approximated to equal the average rate of the reaction over a short
time interval early in the reaction.

EXPERIMENTAL
The experimental procedure involves deciding on an experimental matrix of solutions of FeCl
3
(0.02 M),
KI (0.02 M) at different molar concentrations. The total volume of each solution was 9 mL. Upon mixing
the reactants, a solution sample was transferred into a cuvette and placed in a spectrometer for analysis
within 15 sec. The absorbance of the solution (using 430nm wavelength) was measured by a the
spectrometer and plotted by computer software over the course of the reaction. The initial rate of the
reaction is then determined from the slope of the first time interval, and used in subsequent analytical
analysis. Same procedure is repeated for all trials.
DATA
Table 1 - Initial concentrations and rates measured for each trial
Trial
Volume KI
(mL)
Volume
FeCl
3
(mL)
Volume
H
2
O (mL)
[KI] (M)
[FeCl
3
]
(M)
Initial Rate
( M/s )
1 6 3 0 0.0133 0.00667 0.0113
2 3 6 0 0.00667 0.0133 0.00606
3 3 3 3 0.00667 0.00667 0.00419
4 3 1.5 4.5 0.00667 0.00333 0.00261
5 1.5 3 4.5 0.00333 0.00667 0.00162
RESULTS & DISCUSSION
Table 2- Initial rates, concentrations and orders of reactants.
Trial [I
-
] (M) [Fe
3+
] (M)
Initial Rate
( Abs / s )
1 0.0133 0.00667 0.0113
2 0.00667 0.0133 0.00606
3 0.00667 0.00667 0.00419
4 0.00667 0.00333 0.00261
5 0.00333 0.00667 0.00162
Order 2 1

Table 2 shows the measured initial rates between I
-
and Fe
3+
ions at different initial concentrations for
Rxn 1. The results of the experiment show that rate of the reaction has a higher dependence on I
-
ion
concentrations than Fe
3+
. When the concentration of I
-
is doubled as between trials 3 and 1, the initial rate
is 2.7 times greater, compared to when the initial concentration of Fe
3+
was doubled as show between
trials 3 and 2, rate only increased on by a factor of 1.4. It was calculated that rate dependence of Rxn 1 is
second order with respect to I
-
and first order with respect to Fe
3+
. These findings are consistent with the
literature [1].

Figure 1 - Shows the change in absorbance with time for solutions of different initial Fe
3+
and I
-
concentration solutions. Trial 1
had equal initial concentrations of I
-
and Fe
3+
, in Trial 2 I
-
had twice the initial concentration of Fe
3+
(no dilution), Trial 3 the
concentration of I
-
was half of Fe
3+
(highly diluted), Trial 4 had twice as much Fe
3+
compared to I
-
(no dilution), and Trial 5 had
twice as much I
-
compared to Fe
3+
(high dilution).
The dependence of the reaction can be visually observed by examining figure 1. As the concentration of I
-

decreases between consecutive trials (or is held constant, while Fe
3+
concentration increases). The graph
shows how as the concentration of I is decreased the initial rate of the reaction also decreases, marked by
the lower initial absorbance, and reduced slopes between first intervals of each trial. These results are
consistent with the calculated reactant orders, and with expected rates of reactions measured.
On the basis above the rate law for the reaction between potassium iodide and iron (III) chloride can be
expressed as:
[

] [Eq 4]
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0 10 20 30 40 50 60 70 80 90 100
A
b
s
o
r
b
a
n
c
e


Time (s)
Trial 1
Trial 2
Trial 3
Trial 4
Trial 5
A potential source of error in the experiment could be due to experimental procedure. It was assumed that
by using dilute solutions, the reaction rate very early in the reaction is very slow. This allowed time to
mix reagents outside the spectrometer, before inserting. However this delay between when the reaction
starts and the measurement of the absorption begins could explain why the measured increase in reaction
rates were not quite consistent with the measured orders. It would be expected being able to measure the
absorbance as the reactants are mixed would yield more precise results, and reduce potential for error in
measurement.
The rate constant could not be calculated because initial rates were not determined in terms of
concentration over time.

CITATIONS
1 - Petar B. A. Vrkljan, Jurica Bauer, and Vladislav Tomisic (2008). Kinetics and Mechanism of Iodide
Oxidation by Iron(III): A Clock Reaction Approach, Journal of Chemical Education. 85 (8), 1123

CALCULATIONS