EXPERIMENT 4
SPECTROPHOTOMETRIC DETERMINATION
OF THE EQUILIBRIUM CONSTANT OF A REACTION
Name: Louziel P. Gatchalian Date Performed: 03-18-22
A. Calibration
Analytical wavelength: 466 nm
Standards S1 S2 S3 S4 S5
[FeSCN2+]eq, M 2.13045E-05 3.65563E-05 0.000100848 0.000202448 0.000398843
Absorbance 0.04 0.105 0.379 0.812 1.649
Equation of the best fit line (include r2): y= 4261.8x – 0.0508 R2= 0.9998
εexpt (FeSCN2+): ε theo = 4.262 x 103 M-1cm-1
εtheo (FeSCN2+): ε theo = 4.700 x 103 M-1cm-1
Reference for the literature value: Henry S. Frank and Robert L. Oswalt, Journal of the American
Chemical Soiety 1947 69 (6), 1321-1325 DOI:
10.1021/ja01198a026
B. Determination of Keq
Unknown U1 U2 U3
Absorbance 0.256 0.352 0.437
[FeSCN2+]eq, M 7.20E-05 9.45E-05 1.15E-04
[Fe3+]initial, M 6.00E-04 8.00E-04 1.00E-03
[SCN-]initial, M 1.00E-3 1.00E-03 1.00E-03
[Fe3+]eq, M 5.28E-4 7.055E-04 8.55E-04
[SCN-]eq, M 9.28E-4 9.055E-04 8.55E-04
Keq 146.9 147.9 198.4
Average experimental Keq: 164.4
Theoretical Keq: 890
Reference for the literature value: Petrucci, R. H., Herring, F. G., Madura, J., &
Bissonette, C. (2011). Appendix D. In General Chemistry "Principles and Modern Applications" (10th ed.,
p. A27). , Pearson Canada Inc., Toronto, Ontario.
Points of Discussion. Write your responses on the space provided.
1. Explain why 0.10 M HCl should be used as solvent in all the solution preparations. Show
the relevant net ionic equations in your explanation.
• The purpose of adding HCl in a solution is done to prevent the formation of Fe(OH)3
precipitate in the solution. This is because when water dissociates, it will form a
hydroxide that will possibly combine with Fe 3+ to form a Fe(OH)3 precipitate. Adding
HCl will counter this formation by forming Iron (III) chloride and hydrogen gas.
• Fe3+ + OH- → Fe(OH)3
• Fe3+ + HCl- → FeCl2 + H2
2. Explain why absorbances are measured at λmax.
• Absorbances are measured at λmax where it reflects the largest signal possible created
by the specimen because we want to get the highest sensitivity of the given
concentration. It is also seen as the most reliable point to measure the absorbances,
making minimal deviations caused by noise in Beer’s Law.
3. Explain the importance of blank solutions in spectrophotometric analysis.
• Blank solutions are used in spectrophotometry because water and cuvette also
absorb light. By doing so, we will be able to determine the overlapping absorbance
between the blank and the sample solution. Doing this will lead us to the absorbance
of that specific solution only without the interference of absorbance of the water and
cuvette.
4. Explain why KSCN is added in large excess in preparing the standard solutions for calibration.
• KSCN is specifically added in large excess so that the reaction will be forced to favor
the forward reaction, forming the FeSCN2+ and neglecting the effect of Fe 3+. It is
chosen to be the one in excess due to its colorless property unlike Fe3+. Having more
color in the solution might affect the determination of the wavelength to be used in
calibration.
5. Explain why different blanks were used in reading the absorbances of the standards and the
unknowns.
• Different blanks are used for calibrations and determining the absorbance of
unknown because the concentration of KSCN during calibration was way higher
than the concentration of KSCN used in determining the absorbance of unknown.
Hence, it will be more reasonable to use different blanks to satisfy and come up
with an accurate measurement of absorbance.
6. Explain why lower KSCN concentrations are used in preparing the unknown solutions for the
determination of Keq.
• Lower concentrations or rather equal concentrations of Fe3+ and KSCN- were used
during the preparation of unknown solutions so that an equilibrium will start to occur.
Once established, the amount of FeSCN2+ will be measured and used in computing
the Keq.