In the Laboratory
Colorimetric Determination of the
Iron(III)-Thiocyanate Reaction Equilibrium
Constant with Calibration and Equilibrium
Solutions Prepared in a Cuvette by Sequential
Additions of One Reagent to the Other
Frazier Nyasulu* and Rebecca Barlag
Department of Chemistry and Biochemistry, Ohio University, Athens, Ohio 45701, United States
*nyasulu@ohio.edu
Many general chemistry lab manuals (1-4) include the
colorimetric determination of the equilibrium constant for the
aqueous reaction
Fe3þ SCN - h FeðSCNÞ2þ
The Fe(SCN)2þ complex has a λmax of ∼460 nm. The equilib-
rium constant, K, is
½FeðSCNÞ2þ 
K ¼
½Fe3þ ½SCN - 
and can be determined in general chemistry labs in one of two
methods. In the first method, the most common approach, the
colorimetric determination of Fe(SCN)2þ in equilibrium solu-
tions is based on a Fe(SCN)2þ absorbance versus concentration
calibration plot (1-4). The absorbance-concentration calibra-
tion plot is constructed with [Fe3þ] . [SCN-], a condition that
allows the calculation of the Fe(SCN)2þ concentrations. In the
second method (4, 5), a calibration graph is not required because
the equilibrium constant is determined from eq 3
A AðCf þ Cs ÞK
= εbK -
Cf Cs Cf Cs
Table 1. A Comparison between Standard and the New Procedure To Determine the Equilibrium Constant of FeSCN2þ
Standard Procedure
Solutions are made using pipets or burets. The volumes are larger
than volumes needed for the measurements.
Individual calibration solutions are prepared and transferred into
the cuvette for measurement.
The volume of each of the calibration solutions is fixed.
Cuvette is loaded with new solution for each measurement.
Calibration is performed typically with 5 standards.
Much of the solution prepared to determine the equilibrium constant
is not used in the measurement. Typically four solutions are
prepared and analyzed.
_ _
r 2011 American Chemical Society and Division of Chemical Education, Inc. pubs.acs.org/jchemeduc Vol. 88 No. 3 March 2011
10.1021/ed1009927 Published on Web 01/11/2011
where A is the absorbance, Cs = [SCN-] þ [FeSCN2þ], Cf =
[Fe3þ] þ [FeSCN2þ], b is the path length, and ε is the molar
absorptivity. A plot of A/CsCf versus A(Cf þ Cs)/CfCs is linear
with a slope of -K.
ð1Þ We consider the colorimetric determination of Fe(SCN)2þ
in equilibrium solutions to be more instructive in the general
chemistry lab because it reinforces important concepts that are
discussed in the lecture. Among these are
(i) Calculation of amount of reagent and product from molarity
ð2Þ and volume added.
(ii) Consideration of reaction stoichiometry to identify and use a
limiting reagent to calculate concentration of a product.
(iii) Use of the calibration plot equation and the absorbance to
calculate the concentration of FeSCN2þ in the equilibrium
solutions.
(iv) Use (i) to (iii) to calculate amounts of Fe3þ added, SCN-
added, FeSCN2þ formed, Fe3þ unreacted, and SCN- un-
reacted and the equilibrium concentrations of Fe3þ and
SCN-.These concepts are “must learn” items in general
chemistry and the opportunity to work with these in a lab
can be very helpful. A procedural improvement to the
calibration approach is described. The differences between a
standard procedure and the procedure described herein are
ð3Þ
highlighted in Table 1.
New Procedure
Solutions are prepared using a 0.10-1.00 mL autopipettor and
solution volumes are low. All the solution prepared is used in the
measurement.
Calibration solutions are prepared by sequential additions of 0.10 mL
of a SCN- solution to 4.00 mL of an Fe3þ solution in a cuvette.
The total volume of the calibration solution is varied.
Additions are made to the cuvette already placed in the colorimeter.
Cuvette is not handled between measurements.
Calibration is performed with 10 or more standards.
To determine the equilibrium constant, sequential additions of 0.50 mL
of an SCN- solution to 4.00 mL of a Fe3þ solution are made.
Measurements with sequential addition of 0.50 mL of Fe3þ to 4.00 mL
of SCN- are also performed. Typically 10 or more equilibrium
solutions are analyzed.
_
Journal of Chemical Education 313
 In the Laboratory

Table 2. Absorbance Obtained with Sequential Additions of KSCN to Table 3. Typical Student Results for Solution Composition, Absorbance,
Fe(NO3)3 and Calculated Equilibrium Constants

Volume of KSCN/mLa [FeSCN2þ]/Mb Absorbancec Volume of Volume of

Fe(NO3)3/mLa KSCN/mLb Absorbancec Kd
0.00 0.00 0.000
0.10 2.65  10-5 0.162 4.00 0.50 0.215 106.3
0.20 5.17  10 -5
0.354 4.00 1.00 0.379 106.0
0.30 7.57  10 -5
0.521 4.00 1.50 0.472 104.9
0.40 9.86  10 -5
0.674 4.00 2.00 0.563 111.9
0.50 1.21  10 -4
0.844 4.00 2.50 0.599 111.4
0.60 1.42  10 -4
1.014 0.50 4.00 0.215 111.5

0.70 1.62  10 -4
1.158
0.80 1.81  10 -4
1.296
0.90 1.99  10 -4
1.428
1.00 2.17  10 -4
1.555
a
The concentration of the KSCN aqueous solution was 0.00108 M. The
concentration of the Fe(NO3)3 aqueous solution was 0.200 M Fe(NO3)3 in 1.0
M HNO3 and the volume was 4.00 mL. c Absorbance was measured at 468 nm.
Experiment
Materials and Equipment
Datalogger, colorimeter, cuvette (∼7.5 mL), small stir bar,
0.10-1.00 mL variable autopipettor, 0.200 M Fe(NO3)3 in
1.0 M HNO3, 0.0020 M Fe(NO3)3 in 1.0 M HNO3, 0.0010 M
KSCN in 1.0 M HNO3, 0.0020 M KSCN in 1.0 M HNO3. All
solutions are freshly prepared by the instructor.
Calibration Plot
The colorimeter is calibrated (0% T and 100% T) with
distilled water. A small stir bar is placed in a dry cuvette and
4.00 mL of 0.200 M Fe(NO3)3 is added. A 0.10 mL aliquot of
0.0010 M KSCN is added, the solution is stirred, and the
absorbance recorded. Additional 0.100 mL aliquots are added
until a total of 1.00 mL of 0.0010 M KSCN has been added.
Equilibrium Constant
The equilibrium constant is determined with sequential
additions of 0.50 mL of 0.0020 M KSCN to 4.00 mL of
0.0020 M Fe(NO3)3 in a cuvette. The procedure is repeated
with sequential additions of 0.50 mL of 0.0020 M Fe(NO3)3 to
4.00 mL of 0.0020 M KSCN.
Hazards
FeCl3 is an oxidizer, is harmful if swallowed or inhaled, and
causes irritation to skin, eyes, and respiratory tract. HNO3 is corrosive
and causes burns to all body tissue. KSCN is harmful if swallowed or
inhaled, and causes irritation to skin, eyes, and respiratory tract.
Results and Discussion
The colorimeter measures the absorbance at four fixed wave-
lengths: 468, 565, 610, and 660 nm. On the basis of these, λmax is 468
nm. Typical student calibration data obtained by adding 0.10 mL
increments of 0.00108 M KSCN(aq) to 4.00 mL of 0.200 M
Fe(NO3)3(aq) in 1.0 M HNO3 are shown in Table 2. The plot of
absorbance versus concentration of FeSCN2þ gives a slope of (7.26 (
0.05)  103 L/mol, a y intercept of -0.02 ( 0.07, and R2 = 0.9994.
1.00 4.00 0.389 109.1
1.50 4.00 0.494 110.5
2.00 4.00 0.557 110.6
2.50 4.00 0.593 110.1
a
b The concentration of the Fe(NO3)3 aqueous solution was 0.00200 M
Fe(NO3)3 in 1.0 M HNO3. b The concentration of the KSCN aqueous solution
was 0.00200 M. c Absorbance was measured at 468 nm. d The average
value for K is 109.2 ( 2.6.
The equilibrium constants calculated for the various mix-
tures are shown in Table 3. Students perform calculations in
an Excel spreadsheet; a template is provided in the supporting
information. The average value reported by students is 113 ( 3
(N = 120) at ∼20 °C. The literature values for the equilibrium
constant are in the range 138-146 (6, 7). Our values are lower
because activity coefficients are ignored and the less rigorous
calibration approach is adopted.
Conclusion
A well-known and highly practiced lab to determine an
equilibrium constant is improved. The improvement is based on
the ability of the autopipettor to deliver small and precise volumes of
solutions directly into a cuvette. In today's world of calculators and
computers, it is not essential to keep the volumes of the calibration
solutions and the equilibrium solutions fixed because these are easy
to calculate. For those instructors who prefer the graphical approach
based on eq 3, the same procedure described here can be used.
Literature Cited
1. Stanton, S.; Zhu, L.; Atwood, C. H. Experiments in General
Chemistry Featuring MeasureNet; Thompson Brooks/Cole: Belmont,
CA, 2006; p 311.
2. Beran, J. A. Laboratory Manual for Principles of General Chemistry,
7th ed.; John Wiley: New York, 2004; p 293.
3. Postma, J. M.; Roberts, J. L.; Hollenberg, J. L. Chemistry in the
Laboratory, 5th ed.; Freeman: New York, 2004; p 24-1.
4. Bramwell, F. B.; Dillard, C. R.; Wieder, G. M. Basic Laboratory Principles
in General Chemistry with Quantitative Techniques; Kendal/Hunt:
Dubuque, IA, 1990; p 233.
5. Ramette, R. W. J. Chem. Educ. 1963, 40, 71–72.
6. Lawrence, G. S. Trans. Faraday Soc. 1956, 52, 236.
7. Cobb, C. L.; Love, G. A. J. Chem. Educ. 1998, 75, 90.
Supporting Information Available
Notes for the instructor; handouts for the students; Excel spread-
sheet for the calculations. This material is available via the Internet at
http://pubs.acs.org.

_ _ _
314 Journal of Chemical Education Vol. 88 No. 3 March 2011 pubs.acs.org/jchemeduc r 2011 American Chemical Society and Division of Chemical Education, Inc.