EQUILIBRIUM CONSTANT DETERMINATION OF THE

REACTION BETWEEN FERRIC AND THIOCYANATE IONS

E. D. J. G. BUNAL1
1
DEPARTMENT OF MINING, METALLURGICAL AND MATERIALS ENGINEERING, COLLEGE OF
ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES
DATE PERFORMED: SEPTEMBER 23, 2015
INSTRUCTORS NAME: SIR MARK TOLENTINO

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.

Introduction simplify calculations, it was assumed

Keq or the equilibrium constant is
generally defined as the ratio of
reactants and products at equilibrium.
For a hypothetical
occurring at 298 K,
aA + bB + gG + hH (1)
Then the corresponding equilibrium
constant Keq is presented by,
g h
Keq = ( [G] [H ]
[ A ]a [B ]b ) eq
Gilbert Lewis proposed that the
equilibrium constant be written as a
ratio of the activities between
products and reactants1. However, to
through the use of reference state that
the ions/gases involved in such a
reaction behave ideally.2 The reference
state in calculating such constant is 1
molar (M) concentration in solutions
reaction
and 1 bar partial pressure in gaseous
reactions3.
Moreover, this constant tells
whether to expect higher or lower
concentration of products at
equilibrium. Based on equation (2), it
implies that for a higher value of Keq,
(2) higher concentrations of products are
produced and the reaction proceeds in
the forward direction. On the other
hand, a lower Keq means that the
backward reaction is favored and
lower concentrations of products are
formed.

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.

Ultravioletvisible (UV-Vis) Varied amounts of 0.002 M FeCl-

spectrophotometry uses visible light in 3, 0.2 M KSCN and 0.10 M HCl were
the electromagnetic spectrum to pass mixed placed inside 6 test tubes,
through the solution in equilibrium. 4 In indicated in Table 1.1. Meanwhile, the
equation (2), it is notable that standard blank was prepared in
FeSCN2+, a blood-red coloured duplicate. These six solutions were
complex, has a high absorbance in the used in the calibration of the
visible light area.5 Due to absorbance spectrophotometer
of amount of (visible) light, its
intensity from the UV-Vis will be Table 1.1 Components of the
Standard Solutions
dropped after passing through the
cuvettes containing the solution. mL
mL mL
Solutio 0.20
The Beer-Lambert Law will then be 0.002 0.10
n M
used to determine the experimental FeCl3 M HCl
KSCN
molar absorptivity of a substance
Standar
through a calibration function. In turn, 0 1.00 9.00
d Blank
this molar absorptivity will then be
S1 0.10 1.00 8.90
used to calculate FeSCN2+ S2 0.20 1.00 8.80
concentration at equilibrium. In S3 0.50 1.00 8.50
addition, the equilibrium S4 1.00 1.00 8.00

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.

The reference cell was rinsed three

times with distilled water followed by
the standard blank solution in Table
1.1. Afterwards, it was loaded into the
single beam spectrophotometer. The
S5 solution was then loaded into the
sample cuvette and the analytical
wavelength having maximum Results and Discussions
absorbance (max) was recorded. It was A. Solution Preparation for Calibration
followed by absorbance reading of S1 and Unknowns.
to S5 at established max.
A crucial part in the solution
The standard absorbance readings preparation is the addition of 0.10 M
were plotted as a linear function of HCl. The addition of iron (III) and
[Fe(SCN)2+], with the assumption that thiocyanate ions forms complexes with
all [Fe3+] ions were converted to varying degrees of blood-red color,
Fe(SCN)2+. The calibration function

3
which is useful in spectrophotometry,
as these complexes have a high
absorbance in the visible light region
of the electromagnetic spectrum.
The primary complexation
involved in this experiment is shown in
(7).
Fe3+(aq) + SCN-(aq) + 5H2O(l) [Fe(SCN)
(H2O)5]2+ (7)
Equation (7) could be
simplified, owing to the fact that water
ligands do not change the net charge of the
6
species. Hence, equation (3) would be the
result.
Fe3+(aq) + SCN-(aq) FeSCN2+(aq) (3)
A common problem that would
likely to be encountered in this
complexation is that the SCN- ions
could further react with Fe 3+ to form
another set of thiocyano-complexes,
i.e, Fe(SCN)2+ , Fe(SCN)2+ , Fe(SCN)3, or
Fe(SCN)4.
Furthermore, Fe3+ ions poses
another complication due to its ability
to react with water forming solid iron
(III) hydroxide {equation (5) or (6)},
which could interference with the
absorbance reading of the solutions.
3+
Fe (aq) + 3 H2O(l) Fe(OH)3(s) + 3 H
[Fe(H2O)6]3+ [Fe(H2O)5(OH)]2+ + H+
HCl would then work by
suppressing the formation of iron (III)
hydroxide by pushing the equilibrium
far from the left. Neither hydrogen nor
nitrate ions are components of
equation (3); therefore, the
equilibrium position is not affected.
Another point to be emphasized
is the KSCN concentration. Given the
net equation (3), it was assumed
earlier in methodology for
further computational advantage that [Fe3+]
should be approximately equal to
[FeSCN2+].
For that condition to happen,
Fe3+ should the limiting reactant. Using
equation (3) and Le Chateliers
Principle, SCN- should be in great
excess, as displayed on Table 2.1. As a
result, the reaction would move
forward, which would use up all the
available Fe3+ amount. From
stoichiometry, it implies that the
amount (in moles) of Fe3+ consumed
would be equal to the amount (in
moles) of FeSCN2+ produced.
On the other hand, during the
preparation of the unknowns, in order
for the controlled formation of
monothiocyanatoiron (III) ion complex
(FeSCN2+) and not the other higher
order ligands to be formed is ensured,
the concentration of KSCN must be
low.
B. Calibration
+
(aq)
Table 2.1 shows the calculated
(5)
amounts of each component in the
standard solution, together with its
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

4.0 x 10- A = bc (7)

S2 5 4.0 x 10-5 0.070
where A is the Absorbance
-
1.0 x 10 reading (in absorbance units);
S3 4 1.0 x 10-4 0.147
corresponds to molar absorptivity
(L/mol-cm) and c which is equivalent
2.0 x 10-
S4 4 2.0 x 10-4 0.310 to the concentration of absorbing
species (M).
4.0 x 10-
S5 4 4.0 x 10-4 0.752
Beer-Lamberts Law could also
be expressed in the general equation
of the line y= mx +b.In this particular
The purpose of a blank solution best-fit line, y is the absorbance, the
is to be used as a basis of absorbance slope {m} is equivalent to the molar
of the standards and the unknowns. absorptivity (L/ mol-cm), x is the
The blank reading would be performed concentration of absorbing species (M)
as to obtain an absorbance reading of and b points to the experimental error.
the SCN- and the cuvettes/cell. This
reading shall be subtracted from the Figure 1.1 Absorbance
reading at different equilibrium
absorbance reading of the sample
concentrations of FeSCN2+
solutions. The final result would be the
absorbance reading due to the
absorbing component of the solution -
[Fe(SCN)]2+(eq).

The analytical wavelength,

(max) must be used to measure the
absorbance because at this
wavelength, the absorbance is the
most sensitive to the change of
concentration of the analyte.

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

The average value of Keq,

obtained is 780.49. Compared to the
literature value of 8909 at about 18-
25C, this value incurred a percent
deviation of 12.30%. This relatively
small error might be due to the
experimental procedures and the
varying temperature.

Conclusions and
Recommendations

The experiment successfully

determined the equilibrium
2+
constant of FeSCN , with a percent
deviation of about 12.30%.
Meanwhile, the experimental molar
absorptivity is also valid even due
to high deviation of data ( 47.07%)
since the linearity of the graph is
0.99, which is close to 1.

However, this experiment could

still be further improved by a more
careful measurement (e.g pipetting
of volume required, measuring of
weight) and instrumentation (UV-
Vis handling procedure; avoidance
of stray light among others) and
analysis/handling of data to further
minimize the errors.

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}

[2] Petrucci, R.H.; Herring, F.G.;

Madura, J.D.;Bissonnette, C.
[7] Chemical Equilibrium
General Chemistry: Principles and
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Pearson Prentice Hall: Canada, try/arias/Lab4Equilibriasp11.pdf
2011; pp 656-661 {Date accessed: September 27,
2015}
[3] Lecture 19: Chemical
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Beer's Law
http://ocw.mit.edu/courses/chemist
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{Date accessed: September 26,
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[4] SPECTROPHOTOMETRY
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[10] Petrucci, R.H.; Herring, F.G.;
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Pearson Prentice Hall: Canada,
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Complex-Ion formation constants
[6] Determination of Kc for a
Complex Ion Formation

https://www.smc.edu/AcademicProg
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Chemistry_12_Experiments/Determ