Experiment # 10

“Chemical Equilibrium:
Determination of an
Equilibrium Constant”

Aya Sabry Safan

CHEM 117-501

1 December 2010

Lab partner: Varun Chauhan

Lab instructor: Layne Sarvela

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Abstract

The purpose of this experiment was to evaluate the equilibrium constant for the reaction between
iron(III) ions and thiocyanate ions, forming thiocyanoiron(III). As well, the experiment aimed to
observe the effect of LeChatlier’s principle in determining the equilibrium concentrations of each
species. This is done through preparing four solutions with different concentrations of the three
ions. The equilibrium concentrations of the three ions will be experimentally determined. These
values were substituted into the equilibrium constant expression. In order to determine
[FeSCN2+]eq, the absorbance of the four solutions was measured using the colorimeter, then
comparing the values as the slandered solution has a known concentration of FeSCN2+. As result,
experimental equilibrium constant of the reaction was 134. This result is significant in industries.
If the equilibrium constant is known, the chemical reactions can be maintained by the
manufacturers in order to optimize the products productions, putting in consideration the time
and the profit.
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Results

Before the experiment was preformed, several assumptions were made. First, calibrate the
colorimeter. The cuvettes should be handled only from the top edge of the ribbed sides. The
chemicals should be handled carefully. As well, the solutions should be free from bubbles.
When putting the cuvettes in the colorimeter, the clear sides should be facing toward the white
reference mark at the right of the cuvette slot on the colorimeter. Blue light (470 nm) will be
used as it will be absorbed quickly by the red orange solution. The chemicals should be handled
carefully. As well, all the solutions should be swirled thoroughly.

The concentration of present in the solution at equilibrium should be determined first, in order to
determine the Keq of the following reaction:

𝐹𝑒 3+ (𝑎𝑞) + 𝑆𝐶𝑁 − (𝑎𝑞) ⇌ 𝐹𝑒𝑆𝐶𝑁 2+

Consequently, the first step was to determine the initial concentration of the reactants and the
absorbance.

In table 1, the initial concentrations of Fe3+ and SCN − for the different concentrated solutions are
shown.

Table 1: The initial concentrations of 𝐅𝐞𝟑+ and 𝐒𝐂𝐍−

Sample number [𝐅𝐞𝟑+ ]𝐢 (𝐌) [𝐒𝐂𝐍− ]𝐢 (𝐌)
1 0.001 4.0 × 10−4
2 0.001 6.0 × 10−4
3 0.001 8.0 × 10−4
4 0.001 1.0 × 10−3

In the table above, the initial concentrations were calculated based on the dilution that resulted
from adding KSCN solution and water to 0.002M Fe(NO3)3 in the case of [Fe3+]i and in the case
of [SCN-]i was adding water and Fe(NO3)3. The concentration of [Fe3+ ]i constant among the four
solutions as its volume was constant through the experiment. On the other hand, the
concentration of [SCN-]i increases as its volume increases. In solution five, the concentration of
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both reactants is the same as the solution was not diluted (it was used in comparing the effect of
the dilution in the other solutions).

In table 2, the concentrations of FeSCN 2− at equilibrium for the different concentrated solutions
are shown.

Table 2: The concentrations of 𝐅𝐞𝐒𝐂𝐍𝟐− at equilibrium

Sample number [𝐅𝐞𝐒𝐂𝐍𝟐+ ]𝐞𝐪 (𝐌)
1 5.0 × 10−5
2 6.0 × 10−5
3 8.0 × 10−5
4 1.0 × 10−4

In the above, the values of [FeSCN2+ ]eq are presented. It resulted from comparing the
absorbance for the equilibrium and standard sample respectively, multiplying it with
2.0 × 10−4 𝑀, standards concentration of FeSCN2+ , which was constant through the experiment.
The value of [FeSCN2+ ]eq was helpful in determining the concentrations of the reactants at
equilibrium.

In table 3, the concentrations of Fe3+ and SCN− at equilibrium for the different concentrated
solutions are shown.

Table 3: The concentrations of 𝐅𝐞𝟑+ and 𝐒𝐂𝐍− at equilibrium

Sample number [𝐅𝐞𝟑+ ]𝐞𝐪 (𝐌) [𝐒𝐂𝐍 − ]𝐞𝐪 (𝐌)
1 9.0 × 10−4 3.0 × 10−4
2 9.0 × 10−4 5.0 × 10−4
3 9.0 × 10−4 7.0 × 10−4
4 9.0 × 10−4 9.0 × 10−4

In the above table, the concentrations of the reactants at equilibrium are shown. Based on the
stoichiometry of the reaction, one mole of FeSCN 2− is produced from one moles of Fe3+ and
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one mole of SCN− . Thus, the change in concentration was the same as [FeSCN 2+ ]eq . From these
results, the above values were out.

Since the initial concentration of FeSCN 2− was zero M, the system tent to shift to the product
side to reach equilibrium. By keeping the concentration of Fe3+ and varying [SCN − ], the
concentration of FeSCN 2− changed. When it decreases the product decreases, and vice versa.
Referring to Le Chatelier’s principle and based on the obtained results, the system tends to undo
any changes in concentrations to maintain the equilibrium state.

In table 4, the values of equilibrium constant for the four solutions, as well as, their average are
shown.

Table 4: The values of equilibrium constant and their average

Sample number 𝑲𝒆𝒒
1 150.4
2 133.3
3 126.9
4 123.5
Average 134

In the table above, it is shown clearly that the value of Keq is almost constant. However, it was a
bigger value for the first solutions compared to the other ones. This might be a human error
which might be considered because of not swirling the solution well. The values were constant
because changing in concentration at a given temperature does not affect the equilibrium
constant. Equilibrium constant is the relation between the reactant and products involved in an
equilibrium system. The average value for Keq is considered the equilibrium constant of the
reaction, which is 133.5.
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Calculations

Initial concentration:

[𝑋]𝑚𝐿
[𝑋]𝑖 = × 0.002𝑀
𝑇𝑜𝑙𝑡𝑎𝑙 𝑚𝐿
[𝐹𝑒(𝑁𝑂3 )3 ]𝑚𝐿
[𝐹𝑒 3+ ]𝑖 = × 0.002𝑀
𝑇𝑜𝑙𝑡𝑎𝑙 𝑚𝐿
5𝑚𝐿
[𝐹𝑒 3+ ]𝑖 = ∗ 0.002𝑀
10 𝑚𝐿
[𝐹𝑒 3+ ]𝑖 = 0.001𝑀

Concentration at equilibrium:

𝐴𝑒𝑞
[𝐹𝑒𝑆𝐶𝑁 2+ ]𝑒𝑞 = × [𝐹𝑒𝑆𝐶𝑁 2+ ]𝑠𝑡𝑑
𝐴𝑠𝑡𝑑
0.166
[𝐹𝑒𝑆𝐶𝑁 2+ ]𝑒𝑞 = × 0.0002𝑀
0.732
[𝐹𝑒𝑆𝐶𝑁 2+ ]𝑒𝑞 = 4.5 × 10−5 𝑀

Calculating the concentration at equilibrium: “ICE table: (Initial, Change, Equilibrium)”

[𝐅𝐞𝟑+ ](𝐌) [𝐒𝐂𝐍− ](𝐌) [𝐅𝐞𝐒𝐂𝐍𝟐− ](𝐌)

I 0.001 0.0006 0
C -6.0 × 10−5 -6.0 × 10−5 +6.0 × 10−5
E 9.0 × 10−4 5.0 × 10−4 6.0 × 10−5
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Equilibrium constant value:

[𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠]
𝑘𝑒𝑞 =
[𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠]

[FeSCN 2− ]
𝑘𝑒𝑞 =
[Fe3+ ][SCN − ]

[6.0 × 10−5 ]𝑀
𝑘𝑒𝑞 =
[9.0 × 10−4 ]M[5.0 × 10−4 ]M
𝑘𝑒𝑞 = 133.3

Average equilibrium constant:

𝑘𝑒𝑞1 + 𝑘𝑒𝑞2 + 𝑘𝑒𝑞3 + 𝑘𝑒𝑞4

𝑘𝐴𝑣.𝑒𝑞 =
4
150.4 + 133.3 + 126.9 + 123.5
𝑘𝐴𝑣.𝑒𝑞 =
4
534.1
𝑘𝐴𝑣.𝑒𝑞 =
4

𝑘𝑒𝑞 ≈ 134