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Spectrophotometric Determination of the Equilibrium Constant of a

Reaction


F. G. T. Bartolome
Department of Chemical Engineering
University of the Philippines, Diliman, Quezon City, Philippines
Submitted April 5, 2012



ABSTRACT

This study aimed to determine the equilibrium constant of the reaction Fe
3+
(aq)
+ SCN
-
(aq)
=
FeSCN
2+
(aq)
using a spectrophotometer. The experiment was divided into the calibration using standard
solutions and the determination of concentrations using unknown solutions. A single beam UV-Vis
spectrophotometer was used to determine the absorbance of the standard and unknown solutions. Using
the three concentrations, the experimental equilibrium constant value K
eq
was calculated to be 551 that
has a 96.79% error compared to the 280 literature value.



INTRODUCTION

Spectrophotometry deals with the
relationship of the solutions concentration and
the amount of light it absorbs or transmits.
A spectrophotometer is the device used
to measure the amount of light a particular
solution absorbs.
The Beer-Lamberts Law, A=bc, where
A is the absorbance of a certain solution, is the
molar absorptivity coefficient, b is the path
length and c is the molar concentration of the
solution to be experimented upon, shows the
relationship between the concentration of a
colored solution and its absorbance (A).
In the reaction Fe
3+
(aq)
+ SCN
-
(aq)
=
FeSCN
2+
(aq)
, the equilibrium constant is:

The purpose of this experiment is to
determine the equilibrium constant of the system
give

while at the same time teach the students to
be familiar with the spectrophotometer, how the
Beer-Lamberts Law is applied, and how the
value of the equilibrium constant relates to the
direction of the reaction.


METHODOLOGY

First, solutions of 500mL 0.10 M HCl,
(in 0.10 M HCl) 50mL 0.20 M KSCN, 50mL
0.20 M FeCL
3
, 100mL 0.002 M KSCN and
50mL 0.002 M FeCl
3
were prepared. With these,
the standard solutions for the calibration and the
unknown solutions were prepared using the
following values shown in Tables 1 and 2.

Table 1. Data used in the preparation of the standard
solutions
Test
Tube
0.20M
KSCN, ml
0.002M
FeCl3, ml
0.10M
HCl, ml
Blank 1.00 0.00 9.00
1 1.00 0.10 8.90
2 1.00 0.25 8.75
3 1.00 0.50 8.50
4 1.00 1.00 8.00
5 1.00 2.00 7.00

Table 2. Data used in the preparation of the unknown
solutions
Test
Tube
0.20M
KSCN, ml
0.002M
FeCl3, ml
0.10M
HCl, ml
Blank 5.00 0.00 5.00
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1 5.00 3.00 2.00
2 5.00 4.00 1.00
3 5.00 5.00 0.00

In the calibration process, the cuvette
was first rinsed with distilled water three times
and at least twice with the solution to be
observed after. It was dried by hugging a piece
of tissue on its surface - holding it only on its
frosted sides to have minimal error as possible.
The blank solution was the first placed in the
spectrophotometer and auto zero was performed.
The standard solutions 1 to 5 were then placed in
the device for their absorbance to be recorded.
This also applies to the determination of the
absorbance of the unknown solutions but the
auto zero was performed using the blank
unknown solution.

The data obtained in the absorbance of
the standard solutions in the calibration process
was plotted against their respective
concentration of FeSCN
2+
. The regression line
of the plotted points was used to calculate for the
equilibrium concentration of FeSCN
2+
of the
unknown solutions. The value of [FeSCN
2+
] was
subtracted to [Fe
3+
]
in
and [SCN
-
]
in
to obtain their
respective equilibrium concentration. These
were then used to calculate for the equilibrium
constant of the system.


RESULTS AND DISCUSSIONS

In the solution preparation, 0.10 HCl
was used as a solvent because unlike water, HCl
fully dissociates Fe
3+
ions therefore producing a
colorless solution instead of an orange one with
particles that are not dissolved.

The first hydrolysis of Fe
3+
(represented
by Eq.1) is an orange solution. It reduces the
concentration of the reactant side and the
absorbance of the system therefore causing the
equilibrium state to shift towards the reactants
(favoring the backward reaction).

Eq.1 Fe
3+
(aq)
+ H2O
(l)
= Fe(OH)
2+
(aq)
+ H
+
(aq)


In this experiment, the analytical
wavelength is directly proportional to the
concentration of the solution therefore the darker
the solution, the higher is its concentration and
analytical wavelength. The solution with the
darkest color was used to determine the
analytical wavelength of FeSCN
2+
which is
466nm.

The blank solution contains no
concentration of the ion to be tested. It was used
in the auto zero process of the calibration as the
basis for obtaining the absorbance of the other
standard solutions. In this part of the experiment,
KSCN was added in large excess to ensure that
Fe
3+
is the limiting reactant so that we can
assume that [FeSCN
2+
] is equal to [Fe
3+
]. The
plot of the obtained absorbance of the standard
solutions against their corresponding [FeSCN
2+
]
is shown on Figure 1.

Figure 1. The plot of the Absorbance vs [FeSCN2+]
eq




The regression line of the graph is y =
1265x - 0.0164. Relating this equation to the
Beer-Lamberts Law, the new equation is A =
1265c - 0.0164 where A is the absorbance and c
is the concentration of the ion or complex to be
analyzed. Using the values obtained from the
regression line, the actual molar absorptivity
coefficient of the solutions was then computed.
It is found that the actual molar absorptivity
coefficient value is less than the theoretical
value.

In the determination of unknown
FeSCN
2+
concentration, a different blank
solution was used for the auto zero as a basis for
the unknown solutions to ensure that only the
absorbance of Fe
3+
will be measured. In this
part, 0.002M KSCN was used instead of 0.20M
y = 1265x - 0.0164
R = 0.997
0
0.1
0.2
0.3
0.4
0.5
0.6
0 0.0002 0.0004 0.0006
A
b
s
o
r
b
a
n
c
e

[FeSCN2+]
Absorbance VS [FeSCN2+]
Absorbance
Linear
(Absorbance)
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so that the concentration of SCN
-
is close to the
concentration of Fe
3+
and FeSCN
2+
.

CONCLUSIONS




REFERENCES

[1] Petrucci, e. a. (2011). Equilibrium
Calculations: Some Illustrative Examples. In e.a.
Petrucci, General Chemistry (pp. 647-649).

[2] Silberberg, M. (2010). The Equilibrium State
and the Equilibrium Constant. In M. Silberberg,
Principles of General Chemistry (pp. 553-555).

[3] Spectrophotometric Determination of the
Equilibrium Constant of a Reaction. (2011). In
Institute of Chemistry UP Diliman General
Chemistry Laboratory II (pp. 29-33).

[4] Scheneider R. F. (2012). Beers Law.
Retrieved from Stonybrook University:
http://www.ic.sunysb.edu/Class/che133/lectures/
beerslaw.html

[5] Blaunch, D. N. (2009). Spectrophotometry.
Retrieved from Spectrophotometry.html version
2.01,http://www.chm.davidson.edu/vce/spectrop
hotometry/Spectrophotometry.html