DATE PERFORMED: JANUARY 05, 2011

SPECTROPHOTOMETRIC DETERMINATION OF THE EQUILIBRIUM CONSTANT OF

A REACTION

M.G.V. FERNANDEZ AND J.V.D. OQUENDO

INSTITUTE OF CHEMISTRY, COLLEGE OF SCIENCE
UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES
RECEIVED JANUARY 14, 2011

ABSTRACT

The purpose of this experiment, “Spectrophotometric Determination of the

Equilibrium Constant of a Reaction”, is (a)to determine the equilibrium constant (K eq) for the
formation of thiocyanatoiron(III) complex ([Fe(SCN)]2+) base on the concept of
spectrophotometry by applying Beer – Lambert’s Law and (b) to calculate the percent
difference between the average Keq and the literature value. Solutions of varying amounts of
FeCl3, KSCN, and HCl were analyzed and their absorbances were taken using UV-Vis
spectrophotometer. The values obtained were then used to compute for the concentration
of ferric ([Fe3+]eq), the concentration of thiocyanate ([SCN-]eq), and the Keq. After the
experiment, percent errors were calculated and from the result, it can be seen that the
experimental value deviates largely from the literature value. In general, it can be
concluded that the experiment was a failure because of several errors. Due to those
limitations, it is advised to use reagents of high purity and guidance of the proper usage of
spectrophotometer in order to gain a more ideal result.

INTRODUCTION and the photometer, which measures light

Spectrophotometry is a branch of
spectrometry that deals with the
quantitative study of electromagnetic
spectra. It determines the concentration of
the unknown by using the ability of atoms
to absorb radiant energy of specific
wavelengths. In general,
spectrophotometry is the study of the
intensity of light, particularly the visible,
near-ultraviolet, and near-infrared, that is
emitted, transmitted, or absorbed.
Spectrophotometry deals with the
amount of light absorbed by the sample to
determine the concentration of the
unknown sample. In order to do so, it
needs a device called spectrophotometer.
A spectrophotometer has two main
instruments, the spectrometer, which
produces the light of a specific color,
intensity. A cuvette, a small container for
colored solutions, is properly placed in the
device so that the amount of light that
passed through the tube is measured. The
absorbance is then acquired by the
photometer by measuring the amount of
light of the sample solution passing
through a tube. The photometer then
delivers a voltage signal to a
galvanometer, which displays the
absorbance value. With the known
absorbance, the concentration can be
calculated using the Beer-Lambert’s law,
which shows the direct proportional
relationship between the concentrations of
colored substance in different solutions to
the amount of light it absorbs. The
relationship is shown in the equation:
A = εbc
Where
A = absorbance
ε = molar absorptivity
coefficient
b = path length in cm
c = analyte molar concentration
This equation, however, is not
applicable to all kinds of set-
up. It is only limited to
solutions which are highly
diluted since solutions which
are concentrated will not follow
a perfectly-straight line path.
Aside from that, high purity of
the reagents must be ensured
for the accuracy of the result.
Also, the experiment must be
done simultaneously in a
condition where temperature is
constant since a change in
temperature will change the
value of Keq considerably.
In the experiment, varying
amounts of FeCl3 were reacted
with KSCN with the addition of
HCl to form the complex
[Fe(SCN)]2+. Standard solutions
(solutions with known
concentration) were prepared
in order to know the standard
curve of the solution. Also,
solutions with unknown
concentration were prepared
for the determination of Keq.
The standard solutions were
placed in the
spectrophotometer to
determine their absorbance
value. The readings were
measured and tabulated.
[Fe(SCN)]2+(eq) Line Fit Plot
ABSORBANC
1
0.5 ABSORBANCE
E
0
Predicted
0 0.0001 0.0002 0.0003
[Fe(SCN)]2+(eq)
ABSORBANCE
Figure I. Concentration of [Fe(SCN)]2+ VS.
Absorbance Scattered Diagram
Plot.
The concentration of the
[Fe(SCN)]2+ and their corresponding
absorbance were plotted in a scattered
diagram plot as shown in Figure 1. Blue
dots represent their actual absorbance
while pink dots represent their predicted
absorbance. As observed, blue dots tend
to follow a standard curve and not a
perfectly-straight line due to some
inaccuracy throughout the experiment
which is inevitable. In an ideal situation, it
should follow a perfectly-straight line.
Same procedure in determining the
absorbance was done in the unknown
solutions. The [Fe(SCN)]2+eq is obtained by
applying Beer-Lambert’s law. After all the
absorbance readings had been obtained,
the [Fe3+]eq and [SCN-]eq can be calculated
using the following equations:
[Fe3+]eq = [Fe3+]init - [Fe(SCN)]2+eq
[SCN-]eq = [SCN-]init - [Fe(SCN)]2+eq
The following equations were
derived from the chemical equation of the
reaction. Since products and reactants are
in a 1:1 mole ratio, and any product
formed decreases the amount of the
reactant remaining. This is further and
straightforwardly explained using a simple
ICE table as below:
Table I. ICE Table of Concentrations
Fe3+ SCN- [Fe(SCN)
Initial [Fe3+]init [SCN-]init 0
Change -x -x x
Equilibri [Fe3+]init - [SCN-]init - x
Where x is equal to [Fe(SCN)]2+eq.
K eq is determined using the equation:
K eq = [Fe(SCN)]2+
[Fe3+][SCN-]
From the obtained values of K eq,
average K eq was determined
and compared with the
 literature value to know the solutions by means of UV-Vis
percent difference or error. spectrophotometer.
Percent error is calculated Concentration of [Fe3+] and
using the equation: [SCN-](not included in the
table) were taken from number
% Error = Abs [(Theoretical Value – Actual of moles of the corresponding
Value) / Theoretical Value] x reactant multiplied to the
100 volume of the corresponding
reactant divided by the total
The purpose of this experiment is volume of the solution.
to determine the Keq for the formation of Concentration of [Fe(SCN)]2+
[Fe(SCN)]2+ based on the concept of was taken from the value of
spectrophotometry applying Beer – the concentration of the
Lambert’s Law and to calculate the limiting reactant ([SCN-]) in the
percent difference between the average reaction. Using stoichiometry,
Keq and the literature value. it is determined that the
concentration of [Fe(SCN)]2+ is
RESULTS AND DISCUSSION equivalent to the concentration
of the limiting reactant since
The experiment was comprised of the reaction that occurred was
four procedures: the solution in 1:1 mole ratio.
preparation, the preparation of
the standard solutions, the Using linear regression, the
preparation of unknown following values were
solutions, and the obtained:
determination of the
absorbance of the solutions. In Equation of the Best Fit Line: y =
all of these procedures, the 3362.5x – 0.109
system that is under R2 Value: 0.979
observation is the reaction
between Fe3+ and SCN- to In the computation, the R2
produce metal-ligand complex value acquired is an acceptable value
[Fe(SCN)]2+. showing that the result obtained in
the experiment deviated minimally on
Table II. Calibration Curve the theoretical result base on
Solution Absorbanc [Fe(SCN)]2+eq
linearity. Also, the equation of the
e (
best fit line is taken to be used later
M
in the determination of the
)
concentration of the [Fe(SCN)]2+ in the
Standard 1 0.002 4.0x10-5 unknown solutions. The equation of the
Standard 2 0.156 8.0x10-5 best fit line is equivalent to the Beer-
Standard 3 0.337 1.2x10-4 Lambert’s Law such that y represents
Standard 4 0.447 1.6x10-4 absorbance, slope (m) represents εb (In
Standard 5 0.529 2.0x10-4 the case of this experiment, the m
value is equal to ε since b is
Molar Concentration of FeCl3: 0.20M equivalent to 1cm), and x represents
Molar Concentration of KSCN: 0.002M the concentration of the analyte. The
y-intercept in the equation of the line
The table above contains the data is very minimal and also negligible
from the conducted but it is taken into consideration in
experiment wherein the five the succeeding computations.
standard solutions were under
observation. The absorbance Table III. Absorbance of Unknown
values were taken from the Solutions
readings of the standard
Solutio Absorba [Fe3+]init [SCN-]ini
 reactants in equilibrium necessary for the
Unknow 0.081 1.0x10-3 2.0x10-4 computation of K eq which is also shown in
the table. The average K eq is compared
Unknow 0.206 1.0x10-3 4.0x10-4 with the literature value of the complex
wherein a value of 66.26% is acquired
Unknow 0.286 9.09x10- 2.0x10-4 suggesting that a gross error had
occurred. Some possible causes of this
Unknow 0.373 8.33x10- 1.0x10-3 error might be the sudden change in
temperature as it is brought in a different
Unknow 0.456 7.69x10- 1.23x10- room since this will cause a significant
change in the Keq, the wrong handling and
cleaning of the cuvette will leave tissue
Molar Concentration of FeCl3: 0.002M marks which will cause fake readings, and
Molar Concentration of KSCN: 0.002M the placement of too less or too much of
the solution will cause the
The table above contains the spectrophotometer to fluctuate since light
absorbance, as well as the beam will not pass on the solution alone.
concentration of the five Other minimal causes of error might be in
unknown solutions. Same as the preparation of the stock solutions and
shown in Table 1, absorbance the purity of the reagents used.
values were obtained using
UV-Vis spectrophotometer and CONCLUSION AND
using the same process of RECOMMENDATIONS
calculation, concentration of
the two reactants were In this experiment, determination
determined. of the equilibrium constant was
done using UV-Vis
Table IVa. Equilibrium Constant spectrophotometer and
Determination, K eq through the application of
Solution [Fe3+]eq (M) [SCN-]eq Beer-Lambert’s Law.
( Application of linear regression
M provided the equation of the
) best fit line, y = 3362.5x –
Unknown 1 9.44x10-4 1.44x10-4 0.109, and the R2 value, 0.979.
Although the linearity (R2)
Unknown 2 9.06x10-4 3.06x10-4
attained is close to 1, it does
Unknown 3 7.92x10-4 6.10x10-4
not guarantee that the
Unknown 4 6.90x10-4 8.57x10-4
resulting data would be close
Unknown 5 6.01x10-4 1.06x10-3
to the theoretical data. The
experimental value of Keq,
Table IVb. Equilibrium Constant taken from the average of
Determination, K eq different Keq of the formation of
[Fe(SCN)]2+eq (M) K eq [Fe(SCN)]2+ with varying
5.65 x10-5 415.64 amounts, was found to be
9.37 x10-5 337.98 300.268. This yielded a large
1.17 x10-4 242.18 percent difference of 66.26%
1.43 x10-4 241.83 from the literature value of
1.68 x10-4 263.71 890. Hence, it is concluded
that the experiment was not a
Average K eq: 300.268 success.
Literature Value: 890
% Difference: 66.26% Spectrophotometrical
determination of Keq have the
The table above contains the advantage of obtaining the
concentration of the product and the concentration of a substance
 without disturbing the set-up
but it have limitations such as,
it is only applicable to solutions
with considerably
distinguishable color. Also, the
Beer-Lambert’s Law has its
own disadvantages. It is only
restricted with samples of high
purity and highly diluted. Thus,
the experimenters recommend
that more vital procedures
should be done in the lab to
further understand the concept
behind determining Keq.
Other methods of determining Keq
of high significance and
efficiency were potentiometry
and specific metal ion
electrodes. Potentiometry
accounts for 80% of literature
values. If the same method is
used in the laboratory, it might
be possible to get closer values
to the literature values. On the
other hand, a specific metal
ion electrode is used for stable
metal ion complex that goes
into completion at a relatively
low pH.
Other recommendation that might
be helpful for future studies is
the use of other methods that
scopes a wide range of
solutions. In an experiment
conducted by C. L. Cobb and G.
A., they provided a University of the Philippines-
modification of determining
the equilibrium constant of the
formation of [Fe(SCN)]2+.
Instead of using the usual
diluted solutions, they
make use of concentrated
solutions. This adjustment
allows a more realistic view
of the concept because in
real life applications,
solutions with high
concentration are
processed in the laboratory
for mass production.
ANSWERS TO QUESTIONS
1. Discuss the significance of the HCl in
the solution preparation.
2. Explain why is there a need to do a
blank reading. Why not use
distilled water as the blank
which has zero absorbance?
3. Account for the difference between the
literature value and the
experimentally determined
value of the equilibrium
constant.
APPLICATIONS
REFERENCES
[1] Dodd, R.E. Chemical Spectroscopy.
Elsevier Publishing Company.
1925.
[2] Petrucci, R.H., et al. General
Chemistry, 9th Ed. 2007.
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[4] Bettelhelm, F.A., et al. Laboratory
Experiments For General,
Organic, and Biochemistry, 7th
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[5] Martell, A.E., Hancock, R.D. Metal
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[6] Institute of Chemistry. General
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Diliman. 2010.
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75, Number 1. 1 January 1998,
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[8] General Chemistry Online.
http://antoine.frostburg.edu/chem/senese/
101/glossary/s.shtml
[9] Principles of Spectrophotometry.
http://www.ruf.rice.edu/~biosla
bs/methods/protein/spectropho
tometer.html
[10] Determination of an Equilibrium
Constant.
http://www.ar.cc.mn.us/chemis
 try/Chem1062/Labs/Equilibriu
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[11] Extended Definition of
Spectrophotometry.
http://www.websters-online-
dictionary.org/definitions/spect
rophotometry?cx=partner-pub-
0939450753529744%3Av0qd0
1-tdlq&cof=FORID
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8&q=spectrophotometry&sa=
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[12] Atomic Absorption
Spectrophotometry.
http://www.biology-
online.org/dictionary/Atomic_a
bsorption_spectrophotometry

APPENDIX

A. WORKING EQUATIONS

B. SAMPLE CALCULATIONS