LabQuest10

The Determination of an Equilibrium Constant

Chemical reactions occur to reach a state of equilibrium. The equilibrium state can be characterized by
quantitatively defining its equilibrium constant, Keq. In this experiment, you will determine the value of Keq
for the reaction between iron (III) ions and thiocyanate ions, SCN –.
Fe3+ (aq) + SCN– (aq) → FeSCN2+ (aq)
To find the value of Keq, which depends only upon temperature, it is necessary to determine the molar
concentration of each of the three species in solution at equilibrium. You will use a SpectroVis Plus to help
you measure the concentrations (see Figure 1). The amount of light absorbed by a colored solution is
proportional to its concentration. The red FeSCN2+ solution absorbs blue light, and it will be analyzed at 470
nm (blue light).
In order to successfully evaluate this equilibrium system, it is necessary to conduct three separate tests. First,
you will prepare a series of standard solutions of FeSCN 2+ from solutions of varying concentrations of SCN–
and constant concentrations of H+ and Fe3+ that are in stoichiometric excess. The excess of H+ ions will
ensure that Fe3+ engages in no side reactions (to form FeOH2+, for example). The excess of Fe3+ ions will
make the SCN– ions the limiting reagent, thus all of the SCN– used will form FeSCN2+ ions. The FeSCN2+
complex forms slowly, taking at least one minute for the color to develop. It is best to take absorbance
readings after a specific amount of time has elapsed, between two and four minutes after preparing the
equilibrium mixture. Do not wait much longer than four minutes to take readings, however, because the
mixture is light sensitive and the FeSCN2+ ions will slowly decompose.
In Part II of the experiment, you will analyze a solution of unknown [SCN –] by using the same procedure
that you followed in Part I. In this manner, you will determine the molar concentration of the SCN – solution.
Third, you will prepare a new series of solutions that have varied concentrations of the Fe 3+ ions and the
SCN– ions, with a constant concentration of H+ ions. You will use the results of this test to accurately
evaluate the equilibrium concentrations of each species.
OBJECTIVES
In this experiment, you will
 Prepare and test standard solutions of FeSCN 2+ in equilibrium.
 Test solutions of SCN– of unknown molar concentration.
 Determine the molar concentrations of the ions present in an equilibrium system.
 Determine the value of the equilibrium constant, Keq, for the reaction.
MATERIALS
LabQuest & LabQuest App 0.200 M iron (III) nitrate, Fe(NO3)3, solution in 1.0 M HNO3
Vernier SpectroVis Plus 0.0020 M iron (III) nitrate, Fe(NO3)3, solution in 1.0 M HNO3
plastic cuvette potassium thiocyanate, KSCN solution of unknown concentration
pipet pump or bulb 0.0020 M thiocyanate, SCN–
six 20 × 150 mm test tubes (large) test tube rack
50 mL volumetric flask distilled water
100 mL beakers tissue
Pipets (Beral, volumetric, serological) Temperature Probe

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PRE-LAB EXERCISE
1. For the solutions that you will prepare in Step 2 of Part I below, calculate the [FeSCN 2+]. Presume that all of
the SCN– ions react. In Part I of the experiment, mol of SCN– = mol of FeSCN2+. Thus, the calculation of
[FeSCN2+] is: mol FeSCN2+ ÷ L of total solution. Record these values in the table below. You only need to
show one example of your calculations.
Beaker number [FeSCN2+]
1 0.00 M
2
3
4
5
2. Write the equilibrium constant expression for the reaction given in the introduction.
PROCEDURE
Part I Prepare and Test Standard Solutions
1. Obtain and wear goggles.
2. Connect the SpectroVis Plus to LabQuest and choose New from the File menu. If you have an older sensor
that does not auto-ID, manually set up the sensor.
3. Calibrate the SpectroVis Plus.
a. Prepare a blank by filling an empty cuvette 3/4 full with distilled water.
b. Place the blank in the cuvette slot of the SpectroVis.
c. Choose Calibrate from the Sensors menu. The following message is displayed: “Waiting 60 seconds
for lamp to warm up.” After 60 seconds, the message will change to “Warmup complete.”
d. Select Finish Calibration. When the message “Calibration completed” appears, select Ok.
4. Select the correct wavelength:
a. Tap on the red box and select “change wavelength.”
b. Enter the wavelength (470 nm) and select Ok.
5. On the Meter screen, tap Mode. Change the data-collection mode to Events with Entry. Enter the Name
(Concentration) and Units (mol/L). Select OK.
6. You are now ready to collect absorbance data for the standard solutions. Note: Take readings within 10
minutes of preparing the mixtures. You must wait for all groups to reach this step before proceeding!
a. The standards will be made by your instructor. As each standard is completed it will be passed from
group to group to collect data.
b. Use a temperature probe to measure the temperature of the first solution to use as the temperature for
the equilibrium constant, Keq. Record the temperature in your data section.
Standard
0.200 M Fe(NO3)3 (mL) 0.0020 M SCN– (mL) H2O (mL)
Number
1 5.0 0.0 45.0
2 5.0 2.0 43.0
3 5.0 3.0 42.0
4 5.0 4.0 41.0
5 5.0 5.0 40.0

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 The Determination of an Equilibrium Constant

7. Start data collection.

a. Empty the water from the cuvette. Using the solution for one of the standards, rinse the cuvette twice with ~0.5
mL amounts and then fill it 3/4 full. Wipe the outside with a tissue and place it in the SpectroVis Plus. When
the absorbance readings stabilize, tap Keep and enter the concentration of FeSCN 2+ (from your Pre-Lab
exercise) for the first trial. Select OK to continue.
b. When all groups at your bench have finished with the solution, pass it clockwise to the next bench.
c. Discard the cuvette contents as directed. Rinse and fill the cuvette with the next standard solution. Wipe the
outside with a tissue and place it in the SpectroVis Plus. Follow the procedure in Part b of this step to measure
the absorbance and enter the concentration of this solution.
d. Repeat this process to find the absorbance of the remaining standard solutions.
e. When all standard data has been collected, stop data collection to view a graph of absorbance vs. concentration.
To examine the data pairs on the displayed graph, select any data point. As you tap each point, the absorbance
and concentration values of each data point are displayed to the right of the graph.
7. Record the absorbance values, for each of the five solutions, in your data table.
8. Display a graph of absorbance vs. concentration with a linear regression curve.
a. Choose Curve Fit from the Analyze menu.
b. Select Linear as the Fit Equation. The linear-regression statistics are displayed to the right of the graph for the
equation in the form y  mx  b where x is time, y is absorbance, m is the slope, and b is the y-intercept.
c. Record the best-fit line equation in your data table and select OK.
Part II Test an Unknown Solution of SCN–
9. Obtain about 10 mL of the unknown SCN– solution. Use a pipet to measure out 5.0 mL of the unknown into a
clean and dry 100 mL beaker. Add precisely 5.0 mL of 0.200 M Fe(NO 3)3 and 40.0 mL of distilled water to the
beaker. Stir the mixture thoroughly.
10. Using the solution in the test tube, rinse a cuvette twice with ~1 mL amounts and then fill it 3/4 full. Wipe the
outside with a tissue and place it in the SpectroVis Plus.
11. Determine the absorbance of the unknown.
a. Tap Meter. Monitor the absorbance readings on the screen.
b. When the readings stabilize, record the absorbance value for your unknown in your data table.
c. Remove and clean the cuvette.
Part III Prepare and Test Equilibrium Systems
12. Prepare five test tubes of solutions according to the chart below. Follow the necessary steps from Part I to test the
absorbance values of each mixture. Record the results in your data table. Note: You are using 0.0020 M Fe(NO3)3
in this test.
Test tube 0.0020 M Fe(NO3)3 0.0020 M SCN– H2O
number (mL) (mL) (mL)
1 3.00 0.00 7.00
2 3.00 2.00 5.00
3 3.00 3.00 4.00
4 3.00 4.00 3.00
5 3.00 5.00 2.00

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13. To get good data for the calculation of Keq, you must determine the net absorbance of the solutions in Test Tubes
2–5. To do this, subtract the absorbance reading for Test Tube 1 from the absorbance readings of Test Tubes 2–5,
and record these values as net absorbance in your data table.
DATA TABLE
Parts I and II

Beaker number Absorbance

1
2
3
4
5
Unknown, Part II

Best-fit line equation for the Part I standard solutions:

Part III

Test tube number Absorbance Net absorbance

1
2
3
4
5

DATA ANALYSIS
1. (Part II) Use the best-fit line and the absorbance reading for your unknown solution to determine [SCN –].
2. (Part II) Compare your experimental [SCN–], of your unknown, with the actual [SCN–]. Suggest reasons for the
disparity.
3. (Part III) Use the net absorbance values, along with the best fit line equation of the standard solutions in Part I to
determine the [FeSCN2+] at equilibrium for each of the mixtures that you prepared in Part III. Complete the table
below and give an example of your calculations.
Test tube # 2 3 4 5
[FeSCN2+]

Questions 4-5 will be answered after notes from Section 15.5 are complete.
4. (Part III) Calculate the equilibrium concentrations for Fe3+ and SCN– for the mixtures in Test tubes 2-5 in Part III.
Complete the table below and give an example of your calculations.

Test tube # 2 3 4 5
[Fe3+]
[SCN–]

5. Calculate the value of Keq for the reaction.

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