(Final) Spectrophotometric Determination of The Equilibrium Constant of A Reaction
(Final) Spectrophotometric Determination of The Equilibrium Constant of A Reaction
(Final) Spectrophotometric Determination of The Equilibrium Constant of A Reaction
ABSTRACT
Equilibrium reactions happen when the rates of the backward and forward
reactions are equal. The purpose of this experiment is to find out the experimental
equilibrium constant (Keq) in the reaction between potassium thiocyanate and ferric
chloride. Using the theory of electromagnetism, the UV-Vis spectrophotometer
determined the absorbance of the standards and the unknowns. Then, with the aid
of stoichiometry and Beer-Lamberts law, the experimental equilibrium constant is
determined to be 1878.9 L/ mol-cm which has a 47.07% deviation from the
literature value. From this value and other computations, the average experimental
Keq of the formation of the Fe(SCN) 2+ was found to be 780.49, which falls at about
12% of the literature value. This error might have been occurred due to
instrumental limitations as well as flaws of the solution preparation.
1
This experiment determines the concentrations of Fe3+ and SCN- will be
experimental value of Keq for the calculated through stoichiometry and
following net equilibrium reaction: known initial concentrations. From
these values and using equation (4),
Fe3+(aq) + SCN-(aq) FeSCN2+(aq) (3) the experimental Keq of equation (3)
will then be computed, which
Using equation (2), the equilibrium
corresponds to the primary objective
constant expression is given by:
of this experiment.
FeSCN
Methodology
2+
A. Solution Preparation
Fe The following stock solutions were
prepared using concentrated HCl (12.1
3+ M) and solid KSCN and FeCl3:
Keq = SCN eq (4)
500 mL 0.10 M HCl
50 mL 0.20 M KSCN
50 mL 0.002 M KSCN
50 mL 0.002 FeCl3
B. Preparation of stock solutions for
calibration.
2
S5 2.00 1.00 7.00 (equation of the line) was then
generated along with the r2. From that
equation, the experimental molar
C. Preparation of Solutions with
absorptivity () of Fe(SCN)2+ was then
Unknown concentration of Fe(SCN)2+
determined and compared to the
Shown in table 1.2 are solutions literature value.
prepared with different concentrations
F. Keq determination
of 0.002 M FeCl3, 0.2 M KSCN and 0.10
M HCl, which were mixed in 6 test This part was done similarly to the
tubes. The unknown blank was Spectrophotometer Calibration, except
prepared in duplicate. that the Unknown blank was loaded
into the reference cell. The
Table 1.2 Components of the
absorbance reading of solutions U1 to
Unknown Solutions
U3, were then determined at max.
mL
mL mL From the calibration curve acquired
0.002
Solution 0.002 0.1 M in the previous part and using Beer-
M
FeCl3 HCl Lamberts law, the equilibrium
KSCN
concentration of Fe(SCN)2+ was
Unknown
0 5.00 5.00 calculated.
Blank
S1 3.00 5.00 2.00 Meanwhile, using stoichiometry
S2 4.00 5.00 1.00
together with the known initial
S3 5.00 5.00 0
reactant concentrations, [Fe3+]eq and
[SCN-]eq at equilibrium were computed.
D. Spectrophotometer Calibration All these data gathered would be
and Calibration Plot Constuction substituted to (4) to obtain Keq.
3
which is useful in spectrophotometry, HCl would then work by
as these complexes have a high suppressing the formation of iron (III)
absorbance in the visible light region hydroxide by pushing the equilibrium
of the electromagnetic spectrum. far from the left. Neither hydrogen nor
nitrate ions are components of
The primary complexation equation (3); therefore, the
involved in this experiment is shown in equilibrium position is not affected.
(7).
Another point to be emphasized
Fe3+(aq) + SCN-(aq) + 5H2O(l) [Fe(SCN) is the KSCN concentration. Given the
(H2O)5]2+ (7) net equation (3), it was assumed
earlier in methodology for
Equation (7) could be further computational advantage that [Fe3+]
simplified, owing to the fact that water should be approximately equal to
ligands do not change the net charge of the [FeSCN2+].
6
species. Hence, equation (3) would be the For that condition to happen,
result. Fe3+ should the limiting reactant. Using
equation (3) and Le Chateliers
Fe3+(aq) + SCN-(aq) FeSCN2+(aq) (3) Principle, SCN- should be in great
excess, as displayed on Table 2.1. As a
A common problem that would
result, the reaction would move
likely to be encountered in this
forward, which would use up all the
complexation is that the SCN- ions
available Fe3+ amount. From
could further react with Fe 3+ to form
stoichiometry, it implies that the
another set of thiocyano-complexes,
amount (in moles) of Fe3+ consumed
i.e, Fe(SCN)2+ , Fe(SCN)2+ , Fe(SCN)3, or
would be equal to the amount (in
Fe(SCN)4.
moles) of FeSCN2+ produced.
Furthermore, Fe3+ ions poses
On the other hand, during the
another complication due to its ability
preparation of the unknowns, in order
to react with water forming solid iron
for the controlled formation of
(III) hydroxide {equation (5) or (6)},
monothiocyanatoiron (III) ion complex
which could interference with the
(FeSCN2+) and not the other higher
absorbance reading of the solutions.
order ligands to be formed is ensured,
the concentration of KSCN must be
low.
B. Calibration
3+ +
Fe (aq) + 3 H2O(l) Fe(OH)3(s) + 3 H (aq)
Table 2.1 shows the calculated
(5)
amounts of each component in the
standard solution, together with its
[Fe(H2O)6]3+ [Fe(H2O)5(OH)]2+ + H+
absorbance. Meanwhile the
(6)
4
concentration of KSCN is constant at C. Calibration Curve
0.02 M.
Figure 1 shows the graph of the
Table 2.1 Initial Amount of concentration of FeSCN2+ plotted
Components in Standard Solution linearly against the absorbance
Absorbanc reading resulting from the calibration,
Solutio [FeCl3], [FeSCN2
+ e (Abs. which resulted to having an analytical
n M ], M
Units)
wavelength of 0.751 absorbance units.
Standar The best-fit line was plotted in
0.00 0.00 correspondence to Beer-Lambert Law
dBlank
(which is also a linear equation) given
2.0 x 10- by (7),
S1 5 2.0 x 10-5 0.035
5
0.8 monochromatic and at high
concentrations or temperature, the
0.7 f(x) = 1878.86x - 0.02 Beers Law would be invalid.) 8
0.6 R = 0.99
D. Keq Determination of the
0.5
Unknown Solutions
0.4
Absorbance
Table 3.1 summarizes the
0.3
resulting data from the given
0.2 variables. Solutions are fully shown in
0.1 detail in Appendix A. The
2+
0 concentrations of FeSCN at
0 0 0 0 0 0 0 0 0 0 equilibrium were computed using
Beer-Lamberts Law (7), using the
[FeSCN2+] at Equilibrium
molar absorptivity obtained from the
linear regression of data and the
individual absorbance reading of the
The slope of the best-fit line was unknowns. Meanwhile, using the
the resulting experimental dilution of concentration M1V1 = M2V2,
wavelength, 1878.9 L/ mol-cm. The the initial concentrations of SCN- and
experimental value of molar Fe3+ ions were determined. Finally, by
absorptivity on the other hand is 3550 setting up an ICE table, it could be
M-1cm-1.7 This produced a percent shown that the calculations of the
deviation of about 47.07%. concentrations of SCN- and Fe3+ ions at
equilibrium could be simplified to (8)
This amount of error might have
and (9).
resulted from the limitations of Beer-
Lamberts Law. (This law is only [Fe3+]eq = [Fe3+]initial [FeSCN2+]eq (8)
applicable to cases where (a) incident
light source is monochromatic; (b) no [SCN-]eq = [SCN-]initial [FeSCN2+]eq (9)
side reactions of the solution causing
reading interference; (c) dilute
solutions are used. Also, a particular
deviation is not due to the failures of
this law but rather the failure of the
Table 3.1 Raw Data Obtained
UV-Vis instrument to comply with the
from Unknown Solutions for Keq
conditions wherein this law is applied. determination
It might be due to the entry of stray
light. It is also important to consider Solution U1 U2 U3
that Beers Law is derived under the Absorbance 0.318 0.417 0.506
principle that every photon of [FeSCN2+]eq, 1.692E- 2.219E- 2.693E-
light striking the detector must have M 4 4 4
3+
an equal chance of absorption. [Fe ]initial, M 0.0006 0.0008 0.0001
Otherwise, deviations would occur. For [SCN-]initial, M 0.001 0.001 0.001
another reason, light is not perfectly [Fe3+]eq, M 4.308E- 3.781E- 3.307E-
6
4 4 4 [SCN-]eq, M 8.308E- 7.781E- 7.307E-
4 4 4
Keq 472.75 754.25 1114.4
6
Conclusions and
Recommendations
References
7
[1] G.N Lewis and M. Randall, ination%20of%20Kc%20Procedure
Thermodynamics, McGraw Hill, %20and%20Report.pdf {Date
New York, 1923 accessed: September 26, 2015}
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