Spectrophotometric Determination of the Equilibrium

Constant of a Reaction


G. RAOLA
INSTITUTE OF CHEMISTRY, COLLEGE OF SCIENCE
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES
DATE PERFORMED: JANUARY 15, 2014
INSTRUCTORS NAME: L. RAMIREZ



ABSTRACT
The experiment aims to determine the equilibrium constant for the formation of FeSCN
2+
by
applying Beer-Lamberts law through the use of spectrophotometry. Standard and unknown solutions
containing varying amounts of FeCl3, KSCN and HCl were prepared. Then, the absorptivity of solutions
with varying amounts of FeCl3, KSCN and HCl were determined using a UV-Vis spectrophotometer. The
absorbance and initial concentrations of FeCl3 and KSCN were used to determine the equilibrium
constant for the formation of FeSCN
2+
. The percent error of the experiment was 80 percent, suggesting
that the experimental values deviated greatly from the theoretical value. Therefore, the experiment is
not entirely successful in accurately determining the equilibrium constant for the formation of FeSCN
2+

by applying Beer-Lamberts law through the use of spectrophotometry.


INTRODUCTION
Spectrophotometry is regarded as an
instrumental technique, based on the
measurement of the absorption of
electromagnetic radiation in the ultraviolet
(UV, 200-380 nm), visible (VIS, 380-780 nm),
and near infrared region and near infrared
region.
1
Spectrophotometry is usually used to
determine the concentration of a substance
by using the natural ability of atoms to absorb
radiant energy of specific wavelengths.
Spectrophotometry aims to measure the
spectrum that corresponds to a samples
molecular or atomic energy levels either by
measuring a samples absorption spectrum or

emission spectrum.
2
a spectrophotometer has
three essential parts; A source that produces
radiation of different wavelengths. A
monochromator which serves for dispersion
of the radiation emitted by the source and
isolation of a beam of monochromatic
radiation of definite wavelength.
1
A detector
that measures the intensity of the transmitted
light by converting it into an electrical signal
which the computer will convert into data.
2

Through Beer-Lamberts law,
spectrophotometry is used in measuring a
samples molar concentration. Bee-Lamberts
law states that the relationship between the
path length b (in cm), concentration (in M),
absorbance of the substance, and the molar
absorptivity coefficient (in

) is
expressed as
3
:
A=bC (1)
In this experiment, the equilibrium constant
of the reaction between iron(III) and
thiocyanate ion will be determined using
spectrophotometry and Beer-Lamberts law.

Fe
3+
(aq) +SCN

(aq) FeSCN
2+
(aq) (2)

METHODOLOGY
The first part of the experiment
covers the preparations of stock, standard
and unknown solutions. In the preparation of
stock solutions, 1000 mL of 0.1 M HCl was
prepared from concentrated HCl (12.1 M).
Afterwards, an appropriate amount of KSCN
in a 50-mL beaker was weighed. Then, 20 mL
of 0.1 M HCl was added and stirred. The
solution was transferred into a 50-mL
volumetric flask and diluted to mark with 0.1
HCl. A 100 mL solution of 0.002 M KSCN was
then prepared by transferring 1.00 mL of 0.2
M KSCN in a 100 mL volumetric flask and
diluting it to mark with 0.1 M HCl afterwards.
Then an appropriate amount of FeCl3 in a 50
mL beaker was weighed. Then, 20 mL of 0.1
M HCl was added and stirred. The solution
was transferred into a 50-mL volumetric flask
and diluted to mark with 0.1 HCl. A 100 mL
solution of 0.002 M FeCl3 was then prepared
by transferring 1.00 mL of 0.2 M FeCl3 in a
100 mL volumetric flask and diluting it to
mark with 0.1 M HCl. For the preparation of
standard solutions, the solutions were
prepared in 6-inch test tubes as described in
detail in table 1.1.
Table 1.1. Components of the Standard
Solutions
Solution 0.002 M
FeCl
3,
(mL)
0.20 M
KSCN,
(mL)
0.10 M
HCl, (mL)
Blank 0 1.00 9.00
Standard
1
0.10 1.00 8.90
Standard
2
0.25 1.00 8.75
Standard
3
0.50 1.00 8.50
Standard
4
1.00 1.00 8.00
Standard
5
2.00 1.00 7.00

In the preparation of the unknown solutions,
6-inch test tubes were used to prepare the
solutions described in table 1.2.

Table 1.2. Components of Unknown
Solutions
Solution 0.002 M
FeCl
3,
(mL)
0.20 M
KSCN,
(mL)
0.10 M
HCl, (mL)
Blank 0 5.0 5.0
Standard
1
3.0 5.0 2.0
Standard
2
4.0 5.0 1.0
Standard
3
5.0 5.0 0.0

The next part of the experiment covers the
calibration of the UV-Vis Spectrophotometer.
The cuvette was rinsed three times with
distilled water followed by the blank solution.
Then the cuvette was properly placed in the
sample holder inside the spectrophotometer.
A double beam spectrophotometer was used
therefore there is no need to perform
autozero. Standard 5 was used to determine
the wavelength of maximum absorption. The
value of the wavelength obtained was used in
all subsequent readings. The wavelength was
also recorded. The cuvette containing the
blank solution was then removed and rinsed
three times with distilled water. After that,
the cuvette was rinsed with standard 1. The
rinse was discarded and the cuvette was filled
with standard 1. Then the cuvette was
properly placed in the sample holder inside
the spectrophotometer. The absorbance was
recorded afterwards. The cuvette was
removed from the spectrophotometer and the
solution was disposed in the waste beaker.
The same process was then used in standards
2 to 5. The third part of the experiment
covers the determination of equilibrium
constant for the formation of FeSCN
2+
. The
process used in Part 2 was used for all the
unknown solutions but this time the same
wavelength and a different blank solution
were used. The absorbance recorded
corresponds to the equilibrium concentration
of FeSCN
2+
.
RESULTS AND DISCUSSIONS
The balanced chemical equation for
the 1st hydrolysis of [Fe(H2O)6]
3+
is :
[Fe(H2O)6]
3+
+ H2O Fe(H2O)5(OH)]
2+

+H3O
+
(3)
Due to the dilution of FeSCN
2+
, a light orange
solution was obtained from the 1
st
hydrolysis
of [Fe(H2O)6]
3+
. This implies that color
intensity is directly proportional to the
concentration and absorptivity of the
solution. A wavelength of 462 nm was used
for the entire experiment. A blank solution
containing KSCN and HCl was used so that
FeCl3 will serve as the independent variable
for the experiment.
In the formation of FeSCN
2+
, the reaction is
assumed to be complete. Therefore, the initial
concentration of the limiting reactant, Fe
3+
is
equal to the equilibrium concentration of
FeSCN
2+
. After the calibration of the UV-Vis
spectrophotometer, the table 2.1 shows the
absorbance for each standard.
Table 2.1. Standards and their absorbance
Solution [Fe
3+
]i
(in M)
[SCN
-
]i
(in M)
[FeSCN]
2+
eq
(in M)
Abs
Standard
1
2x10
-
5
0.02 2x10
-5
0.083
Standard
2
5 x10
-
5

0.02 5 x10
-5
0.182
Standard
3
1 x10
-
4

0.02 1 x10
-4
0.377
Standard
4
2 x10
-
4

0.02 2 x10
-4
0.749
Standard
5
4 x10
-
4

0.02 4 x10
-4
1.548

The absorbance vs [FeSCN]
2+
eq graph is
shown in figure 1.1.
Figure 1.1. Calibration Curve








According to graph, the value of R
2
is 0.9996.
This means that the R
2
value is acceptable
and that the results obtained in the
experiment deviated minimally from the
y = 3868.3x - 0.0079
R = 0.9996
0
0.5
1
1.5
2
0 0.0001 0.0002 0.0003 0.0004 0.0005
A
b
s

[FeSCN]
2+

Abs vs [FeSCN]
2+

theoretical results. Using the equation of the
best fit line, the concentration of FeSCN
2+
eq for
unknown solutions can be calculated. The
slope of the graph is equal to the absorptivity
constant and the path length b is equal to
1cm, therefore [FeSCN]
2+
eq is calculated using
equation 4:

(4)
Where x=[FeSCN]
2+
eq
The table 2.2 shows the values of the initial
and equilibrium concentrations of Fe
3+
, SCN
-
,
FeSCN
2+
.
Table 2.2. Unknowns and their absorbance
Solution [Fe
3+
]i
(in M)
[SCN
-
]i
(in M)
[FeSCN]
2+
eq
(in M)
Abs
Unknown
1
6x10
-4
1 x10
-3
8.66x10
-5
0.327
Unknown
2
8 x10
-4
1 x10
-3
1.13x10
-4
0.43
Unknown
3
1 x10
-3
1 x10
-3
1.33 x10
-4
0.507

Subtracting [FeSCN]
2+
eq to the initial
concentrations of Fe
3+
and SCN
-
, the
following equilibrium concentrations were
obtained and shown in table 2.3.
Table 2.3. Equilibrium concentrations
Solution [Fe
3+
]eq [SCN
-
]eq
Unknown 1 5.13x10
-4
9.13x10
-4
Unknown 2 6.87x10
-4
8.87x10
-4
Unknown 3 8.67x10
-4
8.67x10
-4

]
[

][

]
(5)

Using equation 5, the equilibrium constants
for the three unknowns were calculated.
Table 2.4 shows the results.
Table 2.4 Equilibrium constants
Solution Kc
Unknown 1 184.6

Unknown 2 185.9

Unknown 3 176.3

Table 2.5. Results
Theoretical
Value
890
Average Kc 182.3
%error 80%

As shown in the tables 2.4 and 2.5, the
average Kc for the unknown solutions is
182.3. The acquired percent error is 80%,
suggesting that a considerable degree of error
occurred.

CONCLUSION AND RECOMMENDATION
In the experiment, the equilibrium
constant was determined using the UV-Vis
spectrophotometer and through the
application of Beer-Lamberts law. The
calculated R
2
value of the calibration curve is
.9996 yet the theoretical value of Kc , 890 is
far from the average calculated value of Kc,
182.3. Due to the considerably large value of
the %error of the experiment, we can
conclude that the experiment is not entirely
successful in accurately demonstrating the
application of Beer-Lamberts law in the
determination of the equilibrium constant for
the formation of FeSCN
2+
.
Using spectrophotometry in
determining the equilibrium constant for the
formation of FeSCN
2+
may be advantageous
because the concentration is not disturbed in
the process of determination but some
external factors like temperature, external
sources of light and human error may greatly
affect the value of the experimental
equilibrium constant. Advanced methods for
measuring the volumes in the preparation of
solutions are highly recommended in order to
minimize the errors committed.
REFERENCES
[1] Marczenko, Z., Balcerzak, M. Separation,
Preconcentration and Spectrophotometry in
Inorganic Analysis, Elsevier, Amsterdam.
2000
[2] Silberberg, M. Chemistry: The Molecular
Nature of Matter and Change, 5
th
Ed. McGraw-
Hill, New York, 2010
[3] Petrucci, R., Herring, G., Madura J.,
Bissonenette, C. General Chemistry, Principles
and Modern Application, 10
th
Ed. Prentice
Hall, New Jersey. 2010