Experiment 1

Spectrophotometric Determination of the Stability Constant of a

Complex Ion

Student Name:
Student Number:
Partner Name:
Practical Section Number: 0128
Date the Experiment was Performed: 16/01/2015
Date the Report was Submitted: 23/01/2015
Submitted to: Clarissa Sooklal

Introduction
Stable complex ions can be formed from the reaction between transition metal cations
and ligands. The stability of these ions can be expressed by the equilibrium constant for the
formation of the complex and these constants are referred to as stability constants. Knowledge of
the value of stability constants has many applications such as guiding the synthesis of new
inorganic materials, complexometric titration, and colorimetric analysis. In this experiment, an
aqueous solution of ferric ions is made to react with the thiocyanate ion to form a complex ion as
follows:
[Fe(H2O)6]+3(aq) + SCN-(aq) [Fe(H2O)5(SCN)]+2(aq) + H2O (1)
The purpose of this experiment is to determine the value of the stability constant for the
formation of the complex ion, Fe(SCN)+2 which can be expressed as:
K = [Fe(SCN)+2]/[Fe+3][SCN-] (2)
In Part A of this work, five different solutions were prepared using constant amounts of
excess SCN- and varying amounts of Fe+3, acting as the limiting reagent, thus ensuring the
reaction goes to completion. The absorbance of each solution was measured using the Spectronic
200 calibrated to 447 nm, then plotted versus the molar concentration of Fe(SCN) +2, which was
determined from the initial concentration of the limiting reactant,

in order to establish a

calibration curve. In Part B, five different mixtures with the same amount of Fe +3 but different
amounts of SCN- were prepared. In these mixtures an equilibrium between products and
reactants was established and the absorbance of each solution was measured. Using the
calibration curve as well as dilution calculations, the equilibrium concentrations, and thus the
stability

constant,

were

determined.

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spectrophotometric determination of stability constants.

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Experimental Method
The determination of the stability constant for the Fe(SCN)+2 complex via
spectrophotometry was performed according to the procedures given in pages 21-26 of the lab
manual. The calculations to determine the stability constant are presented in Appendix I. The
original data sheet from the experiment is presented in Appendix II.

Results
In Part A of the experiment, 4.0 mL 0.2000 M NaSCN and varying volumes of 0.0005 M
Fe(NO3)3 were added to solutions 0-5, with 0 as the blank solution. The absorbance of each
solution was measured using the Spectronic 200 calibrated to 447 nm and the results are shown
in Table 1. below.
Solution Number
0
1
2
3
4
5

Absorbance
0
0.072
0.297
0.513
0.680
0.874

Table 1. Absorbance of solutions 0-5

Using this data and the calculated concentration of Fe(SCN)+2 for each solution, a calibration
curve of absorbance vs. concentration of Fe(SCN)+2 was created which can be seen in Figure 1.
below.

1
0.9
f(x) = 6424.88x - 0.02
R = 1

0.8

Absorbance

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0

Concentration (mol/L)

Figure 1. Calibration curve of absorbance vs. concentration of Fe(SCN)+2 for solutions 0-5

In Part B, 5.0 mL of 0.002 M Fe(NO 3)3 and varying amounts of 0.002 M NaSCN were
added to solutions 6-10. The absorbance of each solution was measured and the results are
shown in Table 2. below.
Solution Number
6
7
8
9
10

Absorbance
0.224
0.480
0.472
0.614
0.758

Table 2. Absorbance of solutions 6-10

Using the calibration curve and the absorbance data, the stability constant for Fe(SCN) +2 in
solutions 6-10 was determined to be 246.5788, 263.5339, 159.3441, 158.3861 and 157.3476,
respectfully, for an average value of 1.97 x 102.

Discussion
The Fe(SCN)+2 complex is a stable ion which means that in the formation reaction of
Fe(SCN)+2 the equilibrium lies far to the right. Thus, the larger the stability constant, the more
stable the complex. In this work, the stability constant was determined to be a large number of
1.97 x 102, which is in correspondence with theory. The spectrophotometer used in this
experiment was the Spectronic 200 which is accurate to 2 nm and 0.01 A at 0.3 A.

Summary
In this experiment, the stability constant for Fe(SCN) +2 was determined via
spectrophotometry. In Part A, a constant amount of SCN - and varying amounts of Fe+3 were
added to solutions 0-5, with the reaction going to completion and Fe +3 acting as the limiting
reactant. The absorbance of each solution was measured using the Spectronic 200 calibrated to
447 nm. Using this data, a calibration curve of absorbance vs. concentration of Fe(SCN) +2 was
created. In Part B, varying amounts of SCN- and a constant amount of Fe+3 was added to
solutions 6-10 such that the reaction would reach an equilibrium instead of going to completion.
Consequently, the absorbance of solutions 6-10 were measured. Using this data and the
calibration curve, the equilibrium concentrations of Fe+3, SCN-, and Fe(SCN)+2 were calculated.
The stability constant was determined to be 1.97 x 102.

Appendices
Please find attached Appendix I and Appendix II. Appendix I shows the calculations for
the stability constant, K. Appendix II contains the original data sheet from the lab.

References
1.
2.

Judith, P. CHM 120 Course Manual; University of Toronto; Mississauga; 2015; p 21-26
Zumdahl, S. and Decoste, D. Chemical Principles, 7th Edition ; Brooks/Cole; Belmont, CA;

3.

2013, p. 256.
The Perfect Teaching Instrument.
http://www.thermoscientific.com/content/dam/tfs/ATG/CAD/CAD%20Documents/Catalogs
%20&%20Brochures/Molecular%20Spectroscopy/UV%20Visible
%20Spectrophotometers/Spectrophotometer
%20Systems/BR51930_E_0913M_SPECT200Ed_L.pdf (accessed January 22, 2015),
Thermo Scientific.

Appendix I - Calculations
Part A
In Part A of this experiment, the composition of solutions 1-5 included varying amounts
of 0.1 M HNO3 and 0.0005 M Fe(NO3)3 as well as a constant 4 mL of excess 0.2 M NaSCN. In
these solutions, Fe+3 was the limiting reactant and so the concentration of Fe(SCN) +2 formed in
the reaction is equal to the initial concentration of Fe +3 put into the solution. To find the initial
concentration of Fe+3 in each solution, dilution calculations must be performed. This can be done
by multiplying the volume and concentration of Fe(NO 3)3 added and then dividing by the total
volume of the solution.
Solution 1-5: [Fe+3]initial = (initial concentration)(volume Fe(NO3)3 added)/total volume
Solution 1: [Fe+3]initial = (0.0005 M)(0.4 mL)/10 mL = 2.0 x 10-5 M
Solution 2: [Fe+3]initial = (0.0005 M)(1.0 mL)/10 mL = 5.0 x 10-5 M
Solution 3: [Fe+3]initial = (0.0005 M)(1.6 mL)/10 mL = 8.0 x 10-5 M
Solution 4: [Fe+3]initial = (0.0005 M)(2.2 mL)/10 mL = 1.1 x 10-4 M
Solution 5: [Fe+3]initial = (0.0005 M)(2.8 mL)/10 mL = 1.4 x 10-4 M
The absorbance of each solution was then measured (as indicated in the data sheet found
in Appendix II) using a spectrophotometer, and a calibration curve for Fe(SCN) +2 was created
(found in Results section).
Part B
In Part B of this experiment, the composition of solutions 6-10 included varying amounts
of 0.1 M HNO3 and 0.002 M NaSCN as well as a constant volume of 5.00 mL 0.002 M Fe(NO 3)3.
Since the reaction does not go to completion, the equilibrium concentrations of Fe +3, SCN-, and
Fe(SCN)+2 must be calculated. The equilibrium concentration of Fe(SCN)+2 can be read off the
calibration curve from the measured absorbance for each solution (as indicated in the data sheet
found in Appendix II) using the linear line of best fit. The equilibrium concentrations of Fe +3 and
SCN- can be determined by subtracting the equilibrium concentration of the complex (since the
ions and the complex react in a one-to-one ratio) from the initial concentrations (determined by a
dilution calculation as in Part A).
Solution 6-10: [Fe+3]initial = (initial concentration)(volume Fe(NO3)3 added)/total volume
Solution 6-10: [Fe+3]initial = (0.002 M)(5.0 mL)/10 mL = 0.001 M
mol Fe+3 = (0.002 M)(0.005 L) = 1 x 10-5 mol

Solution 6-10: [Fe+3]eq = [Fe+3]initial - [Fe(SCN)+2]eq

The line of best fit of the calibration curve yields the following equation:
y = 6424.9x - 0.0223
The absorbance of solution 6 was measured to be 0.224 (y-value) and so the x-value is the
concentration of Fe(SCN)+2 at equilibrium.
(0.224 + 0.0223)/6424.9 = x = Fe(SCN)+2 = 3.8335 x 10-5 M
The same calculations were done for solutions 7-10 using their respectful absorbance data.
Solution 6: [Fe+3]eq = (0.001 M) - (3.8335 x 10-5 M) = 9.61665 x 10-4 M
Solution 7: [Fe+3]eq = (0.001 M) - (7.818 x 10-5 M) = 9.2182 x 10-4 M
Solution 8: [Fe+3]eq = (0.001 M) - (7.6935 x 10-5 M) = 9.23065 x 10-4 M
Solution 9: [Fe+3]eq = (0.001 M) - (9.99037 x 10-5 M) = 9.00963 x 10-4 M
Solution 10: [Fe+3]eq = (0.001 M) - (1.21449 x 10-4 M) = 8.78551 x 10-4 M
The same calculations must be done in order to find the concentration of SCN- at equilibrium:
Solution 6-10: [SCN-]initial = (initial concentration)(volume NaSCN added)/total volume
Solution 6-10: [SCN-]eq = [SCN-]initial - [Fe(SCN)+2]eq
Solution 6: [SCN-]initial = (0.002 M)(1.0 mL)/10 mL = 2.0 x 10-4 M
mol SCN- = (0.002)(0.001 L) = 2 x 10-6 mol
[SCN-]eq = (2.0 x 10-4 M) - (3.8335 x 10-5 M) = 1.61665 x 10-4 M
Solution 7: [SCN-]initial = (0.002 M)(2.0 mL)/10 mL = 4.0 x 10-4 M
mol SCN- = (0.002)(0.002 L) = 4 x 10-6 mol
[SCN-]eq = (4.0 x 10-4 M) - (7.818 x 10-5 M) = 3.2182 x 10-4 M
Solution 8: [SCN-]initial = (0.002 M)(3.0 mL)/10 mL = 6.0 x 10-4 M
mol SCN- = (0.002)(0.003 L) = 6 x 10-6 mol
[SCN-]eq = (6.0 x 10-4 M) - (7.6935 x 10-5 M) = 5.23065 x 10-4 M
Solution 9: [SCN-]initial = (0.002 M)(4.0 mL)/10 mL = 8.0 x 10-4 M
mol SCN- = (0.002)(0.004 L) = 8 x 10-6 mol
[SCN-]eq = (8.0 x 10-4 M) - (9.99037 x 10-5 M) = 7.00096 x 10-4 M
Solution 10: [SCN-]initial = (0.002 M)(5.0 mL)/10 mL = 1.0 x 10-3 M

mol SCN- = (0.002)(0.005 L) = 1 x 10-5 mol

[SCN-]eq = (1.0 x 10-3 M) - (1.21449 x 10-4 M) = 8.78551 x 10-4 M
Using the equilibrium concentrations of the ions calculated above and the equilibrium
concentration of the complex read off the calibration curve, the stability constant can be
determined using the following equation:
K = [Fe(SCN)+2]/[Fe+3][SCN-] (A1)
6. K = (3.8335 x 10-5 M) / (9.61665 x 10-4 M)(1.61665 x 10-4 M) = 246.5788
7. K = (7.818 x 10-5 M) / (9.2182 x 10-4 M)(3.2182 x 10-4 M) = 263.5339
8. K = (7.6935 x 10-5 M) / (9.23065 x 10-4 M)(5.23065 x 10-4 M) = 159.3441
9. K = (9.99037 x 10-5 M) / (9.00963 x 10-4 M)(7.00096 x 10-4 M) = 158.3861
10. K = (1.21449 x 10-4 M) / (8.78551 x 10-4 M)(8.78551 x 10-4 M) = 157.3476
Thus, the average of the stability constants is:
Kavg = (246.5788 + 263.5339 + 159.3441 + 158.3861 + 157.3476) / 5
= 197.0381
The average Kstability for Fe(SCN)+2 in this experiment was therefore determined to be 1.97 x 102.

Appendix II - Data Sheets

Please see the next pages for data sheets.