CHEM 203

Introductory Chemical Techniques

Lab Report
Exp. 3: Determination of an Equilibrium Constant

Student Name Carl-Etienne Chaaya Section # 7-A

Student ID # 201900730 Date 13/10/2020

I. Purpose:

1- Reviewing the concept and principles of chemical equilibrium.

2- Learning the principles of chemical analysis by spectrophotometric means.
3- Determination of lambda max of FeSCN2+
4- Determining the equilibrium constant spectrophotometrically from the reaction between ion III and
thiocyomate iron (SCN-) at a given temperature.

II. Reaction(s) involved:

Fe3+ + SCN- <--> Fe(SCN)2+
Fe3+ + SCN- --> Fe(SCN)2+

III. Results and Calculations:

Determination of λmax of FeSCN 2+

Table 1: Absorption Spectrum of an FeSCN2+ Solution

 (nm) A %T
350 0.298 50.4
375 0.311 48.9
400 0.548 28.3
425 0.925 11.9
450 1.177 6.65
475 1.151 7.06
500 0.919 12.1
525 0.606 24.8
550 0.358 43.8
575 0.175 66.8
600 0.080 83.2

 max = 450 nm
Determination of b of FeSCN 2+

Concentration of Fe(NO3)3= 0.200 M

Concentration of KSCN = 2.00  10−3 M

Table 2: Absorbance measurements of FeSCN 2+ standard solutions

Mixture Volume of Volume of Volume % Absorbance [FeSCN2+]

Fe(NO3)3 KSCN of H2O Transmittance
0 5.00 0.00 15.00 100.0 0 0.00 M
1 5.00 0.50 14.50 61.2 0.213 5.00 * 10-5 M
2 5.00 1.00 14.00 43.3 0.364 1.00 * 10-4 M
3 5.00 1.50 13.50 31.6 0.501 1.05 * 10-4 M
4 5.00 2.00 13.00 14.7 0.832 2.00 * 10-4 M
5 5.00 3.00 12.00 6.65 1.177 3.00 * 10-4 M

Slope of Calibration Curve: b (M−1) = 3.86 * 103

Show one sample calculation for one mixture only.

Mixture 5:
[FeSCN2+] = ([KSCN] * VKSCN) / 20.00 = (0.00200 * 3.00)/20.00 = 3.00 * 10-4 M
SCN is limiting:
nSCN = [SCN-] * VSCN-
nFeSCN2+ = nSCN-
[FeSCN2+] = nFeSCN2+/VFeSCN2+ = (0.00200 * 3.00)/20.00 = 3.00 * 10-4 M

Determination of Keq of FeSCN 2+

Concentration of Fe(NO3)3= 2.00  10−3 M

Concentration of KSCN = 2.00  10−3 M

Table 3: Composition of different mixtures and their absorbance measurements at λmax

Mixture Volume of Volume of Volume % Absorbance [FeSCN2+]

Fe(NO3)3 KSCN of H2O Transmittance
6 5.00 0.00 5.00 100.0 0 0.00 M
7 5.00 1.00 4.00 75.8 0.120 3.08 * 10-5 M
8 5.00 2.00 3.00 61.8 0.209 5.36 * 10-5 M
9 5.00 3.00 2.00 48.8 0.312 8.00 * 10-5 M
10 5.00 4.00 1.00 40.7 0.390 1.00 * 10-4 M
11 5.00 5.00 0.00 33.9 0.469 1.20 * 10-4 M
Table 4: Equilibrium concentrations and equilibrium constant

Mixt
n0 Fe3+ n0 SCN− [FeSCN2+] n FeSCN2+ n Fe3+ n SCN− [Fe3+] [SCN−] Kc
ure
6 1.00 * 10-5 0.00 0.00 0.00 1.00 * 10-5 0.00 1.00 * 10-3 0.00 0.00

7 1.00 * 10-5 2.00 * 10-6 3.08 * 10-5 3.08 * 10-7 9.70 * 10-6 1.70 * 10-6 9.70 * 10-4 1.70 * 10-4 187

8 1.00 * 10-5 4.00 * 10-6 5.36 * 10-5 5.36 * 10-7 9.46 * 10-6 3.46 * 10-6 9.46 * 10-4 3.46 * 10-4 164

9 1.00 * 10-5 6.00 * 10-6 8.00 * 10-5 8.00 * 10-7 9.20 * 10-6 5.20 * 10-6 9.20 * 10-4 5.20 * 10-4 167

10 1.00 * 10-5 8.00 * 10-6 1.00 * 10-4 1.00 * 10-6 9.00 * 10-6 7.00 * 10-6 9.00 * 10-4 7.00 * 10-4 159

11 1.00 * 10-5 1.00 * 10-5 1.20 * 10-4 1.20 * 10-6 8.80 * 10-6 8.80 * 10-6 8.80 * 10-4 8.80 * 10-4 155

Show one sample calculation for each calculated quantity (for one mixture only).

Mixture 7:
n0 Fe3+ = [Fe3+]A * VFe3+ = 0.00200 * 5.00 * 10-3 = 1.00 * 10-5 mol
n0 SCN- = [SCN-]B * VSCN- = 2.00 * 10-3 * 1.00 * 10-3 = 2.00 * 10-6 mol
nFeSCN2+ = [FeSCN2+] * VFeSCN2+ = 3.08 * 10-5 * 10.00 * 10-3 = 3.08 * 10-7 mol
nFe3+ = n0 Fe3+ - nFeSCN2+ = 1.00 * 10-5 - 3.08 * 10-5 = 9.70 * 10-6 mol
nSCN- = n0 SCN- - nFeSCN2+ = 2.00 * 10-6 - 3.08 * 10-5 = 1.70 * 10-6 mol
[Fe3+] = nFe3+/Vsol = 9.70 * 10-6 / 10.00 * 10-3 = 9.70 * 10-4 M
[SCN-] = nSCN-/Vsol = 1.70 * 10-6 / 10.00 * 10-3 = 1.70 * 10-4 M

Kc = [FeSCN2+]/[Fe3+][SCN-] = 3.08 * 10-5 / (9.70 * 10-4 * 1.70 * 10-4) = 187

[FeSCN2+] = 3.08 * 10-5 M

A = ε * b * c c = A/(ε * b) = A/slope
IV. Questions

1. The iron nitrate solutions used in this experiment have been prepared in acidic media. Write an
expression for the equilibrium constant of the following chemical reaction and conclude the reason for
using the nitric acid along with the iron nitrate.

Fe3+ (aq) + H2O ⇌ Fe(OH)2+ (aq) + H+ (aq)

Kc = [Fe(OH)2+][H+]/[Fe3+]
Adding nitric acid is necessary to avoid the formation of brown color species such as Fe(OH) 2+, which
interferes with the analysis of FeSCN2+.

2. While doing the second part of this experiment, a student was given a solution of iron thiocyanate
(FeSCN2+) of an unknown concentration. The student took a sample of this solution, put it in a cuvette
of an optical path length equal to 0.10 cm, and measured the absorbance of this solution at λmax. The
student measured an absorbance of 0.105. What is the concentration of this unknown solutions?

For ε * b = 3.86 * 103:

c = A / ε * b = 0.105 / (3.86 * 103) = 2.72 * 10-5 M

3. Consider the chemical reaction studied in this experiment:

Fe3+ (aq) + SCN− (aq) ⇌ FeSCN 2+ (aq) Kc = 115

During a certain experiment, 5.00 mL of a 1.00  10−3 M Fe3+ were mixed with 5.00 mL of a 2.00  10−3 M
SCN- solution and 5.00 mL of a 1.00  10−3 M FeSCN2+. Predict in which direction does the reaction
proceeds and calculate the concentrations of Fe3+, SCN-, and FeSCN2+ at equilibrium.

Fe3+ SCN- FeSCN2+

t0 3.33 * 10-4 M 6.67 * 10-4 M 3.33 * 10-4 M
Equilibrium 3.33 * 10-4 - x 6.67 * 10-4 - x 3.33 * 10-4 + x

Initial Concentrations Calculations:

[Fe3+] = C1V1/V2 = 1.00 * 10-3 * 5.00 / 15.00 = 3.33 * 10-4 M
[SCN-] = C1V1/V2 = 2.00 * 10-3 * 5.00 / 15.00 = 6.67 * 10-4 M
[FeSCN2+] = C1V1/V2 = 1.00 * 10-3 * 5.00 / 15.00 = 3.33 * 10-4 M

Equilibrium Calculations, with the reaction going to the right as prediction:

Kc = [FeSCN2+]/( [SCN-][Fe3+] ) = (3.33 * 10-4 + x) /((3.33 * 10-4 – x) * (6.67 * 10-4 – x))

Solving for x:
x = -2.68 * 10-4
x is negative, so our prediction was wrong, and the reaction is going to the left:

[Fe3+]equilibrium = 6.01 * 10 -4 M
[SCN-]equilibrium = 9.35 * 10-4 M
[FeSCN2+]equilibrium = 6.50 * 10-5 M