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SPECTROPHOTOMETRIC DETERMINATION

OF THE EQUILIBRIUM CONSTANT OF A


REACTION
V.G. ESTRADA1 AND J.E.F LU2
1
NATIONAL INSTITUTE OF PHYSICS, COLLEGE OF SCIENCE
2
DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES
DATE PERFORMED: AUGUST 26, 2015
INSTRUCTORS NAME: MARK NEIL TOLENTINO
__________________________________________________________________________________
____________________________
ABSTRACT
This experiment aims (a) to determine the analytical wavelength of the
thiocyanate-iron(III) complex ([Fe(SCN)2+]), (b) to determine the equilibrium
constant (Keq) for the formation of [Fe(SCN)2+], and (c) to calculate for the
percent difference between the average K eq and the literature value. Solutions
with varying amounts of FeCl 3, KSCN, and HCl were first prepared. Their
absorbances and the analytical wavelength were obtained using UV-Vis
spectrophotometer. Specific values were used to calculate for the concentration
of ferric ([Fe3+]eq), thiocyanate ([SCN]eq), and the Keq. The percent difference was
then calculated and it can be inferred that the experiment was not successful
because of experimental errors. The significance of this study is that through
spectrophotometry, unknown substances can be identified and observed without
actually touching them. Spectrophotometry is mainly useful for substances that
might be toxic.
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____________________________

INTRODUCTION
Spectrophotometry is a method to measure how much a chemical substance
absorbs light by measuring the intensity of light as a beam of light passes
through sample solution. The basic principle is that each compound absorbs or
transmits light over a certain range of wavelength. This measurement can also
be used to measure the amount of a known chemical substance. The
quantitative study utilizes the device called spectrophotometer. The device has
two main parts, the spectrometer that emits a specific light wavelength and the
photometer that measures the light intensity which the sample transmitted.
The main goal of experiment is to study equilibrium constant of reaction through
analysis by spectrophotometry. The experiment intends to familiarize students
with the spectrophotometer and with a new method of obtaining the equilibrium
constant of a reaction. The reaction between

iron and thiocyanite is utilized in this experiment. It has the reaction system,
Fe3+

(aq)

+ SCN-(aq) FeSCN2+(aq) + H2O(l)

In this reaction system, blood red complex [Fe(H 20)5(SCN)]2+ is formed. The
absorbance of this complex will be measured by the UV-Vis spectrophotometer
and the concentration can then be obtained through the use of the BeerLamberts Law. It relates the light absorption of the colored substance in the
system to its concentration. It has the equation,
A = bc
Where,
A= absorbance
= molar absorptivity coefficient in M-1 cm-1
b = path length
c = analyte molar concentration
With the use of the calculated concentration, the equilibrium constant can be
computed using the expression,
Keq = [FeSCN2+]/ [Fe3+] [SCN-]
The method can only be executed accurately if the solutions used are highly
diluted and the reagents have a high purity or else the data will not be in a
regressing pattern. In addition to that, the experiment must be performed with
precisely same temperature for all solutions since K eq changes with temperature.
RESULTS AND DISCUSSION
After the calibration of the spectrophotometer, the unknown solutions are tested.
Another blank solution was prepared and used for this part of the experiment to
recalibrate the base of zero of the apparatus since the amount and the
concentration of SCN- used in this part differs from that of the standard solutions
even if the same cuvette were used. In this part of experiment, more diluted
concentration of SCN- and Fe3+ is used. This is to isolate the metal complex
[FeSCN2+]. It is possible since in diluted form, SCN - and Fe3+ have negligible

absorbance. In addition, this type of spectrometry can only yield results if the
solutions to be analyzed are highly diluted and come from reagents with high
purity. Through algebraic manipulation of the the equation of the best fit curve,
Y= 2865.4x 0.0051
The equilibrium concentration of the [FeSCN2+] will be obtained. Listed in the
table below is the calculated [FeSCN2+]eq with the actual absorbance of unknown
solutions .
Table 3. Equilibrium Concentration of [FeSCN2+]
Unknow
Abs
[FeSCN2+]eq
n
Solution
1
0.341
1.17 x 10-4
2
0.471
1.62 x 10-4
3
0.570
1.97 x 10-4
Also through calculations, the initial concentration of Fe 3+ and SCN- can be
obtained. The acquired values for the unknown solutions are listed in the table
below.
Table 4. Initial Concentrations of Fe3+ and SCNSoln
[Fe3+]i
[SCN-]i
1
2
3

6.0x10-4
8.0x10-4
1.0x10-3

1.0x10-3
1.0x10-3
1.0x10-3

After obtaining the equilibrium concentrations and the initial concentrations of


the reactants, the equilibrium concentrations of Fe 3+ and SCN- were calculated
using the ICE Table as shown below.
Table 5. ICE Table of Concentrations
[Fe3+ [SCN- [FeS
]
]
CN2+]
3+
Initial
[Fe
[SCN ]
0
]i
i
Change
-X
-X
X
Equilibriu
[Fe3+ [SCN-]
X
m
]i-X
i-X
Calculated values for the equilibrium concentration of the reactants and products
are shown in the table below.
Table 6. Equilibrium Concentrations
Solution [Fe3+]eq
[SCN-]eq [FeSCN2+
]eq
1
4.83
x 8.83
x 1.17 x 10-4
-4
4
10
10
2
6.38
x 8.38
x 1.62 x 10-4
-4
4
10
10
3
8.03
x 8.03
x 1.97 x 10-4
-4
4
10
10

After gathering all the information regarding the equilibrium concentrations of


the unknown, the equilibrium constant can now be obtained with the use of the
expression,
Keq = [FeSCN2+]eq / [Fe3+]eq [SCN-]eq
With all the pertinent information gathered, are then calculated. The equilibrium
constants obtained are shown in the table below.
Table 7. Equilibrium Constant
Unknown Solution
Equilibrium
Constants
1
274.3
2
303.0
3
305.5
Ave:
294.3
When compared to the theoretical value of K eq which is 890. The percent error is
about 66.9% which basically means that the experimentation has wide margin of
errors. The possible errors that affected the experimental values are listed in the
table below.
Table 8. Sources of Errors
Sources of
Errors
Inconsistent
Room
Temperature
Not properly
rinsed
cuvette
Inaccurate
amount
of
sample
Not enough
dilution
Impurity of
the reagents

Determinat
e/
Indetermin
ate
Indeterminat
e

Systematic/
Random/Gr
oss
Random

Determinate

Systematic

Determinate

Systematic

Determinate

Systematic

Determinate

Systematic

CONCLUSION AND RECOMMENDATION


The experiment made use of the Beer-Lamberts law to obtain the calibration
curve. The best-fit line was determined through regression analysis and the
equation is y = 1464.65x + 0.306. The linearity coefficient is r 2 = 0.179. This is
not an acceptable value because it deviates from the ideal value.
The calculated average value of Keq is 518.95 and a 41.69% difference to the
literature value was also computed. This goes to show that the experiment was
not successful. The large percent difference is due to experimental errors. Some
of the sources may include the improper handling of the cuvette, inaccuracy of
the amount of solutions used, over-dilution or not enough dilution, and impurity
of substances. In order to have better results, it is recommended to use solutions
that are more diluted and to use substances with higher purity.
REFERENCES
[1] Petrucci, R. H., Herring, F., Madura, J., Bissonnette, C. General Chemistry 10th
ed. Pearson Education, Canada. 2011.
[2] Silberberg, M. S. Principles of General Chemistry 3rd ed. The McGraw-Hill
Companies, Inc., New York. 2013.
[3] McGraw-Hill Online Learning Center. The Importance of Spectrophotometry.
http://highered.mheducation.com/sites/0073031216/student_view0/exercise7/spe
ctrophotometry_importance.html (accessed June 27, 2015)