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Jimin Son

Mr. Robinson

HL Chemistry

27th September, 2017

The Determination of an Equilibrium Constant

Introduction

Chemical reactions that reach a state of equilibrium meet to conditions; the rates of the

forward and reverse reactions are equal, and the concentrations of all reactants and products

remain constant. In this state, macroscopic properties such as colour and density are also

constant. In such cases, the reaction system is said to be at a dynamic chemical equilibrium.

Furthermore, any changes in the reaction conditions, such as temperature, pressure, or

concentration of reactants or products can affect the equilibrium. The chemical reaction in

equilibrium can be written as below:

aA + bB cC + dD

The equilibrium state can be characterized by quantitatively defining its equilibrium

constant, Keq, which is the constant for a particular reaction at a particular temperature. An

equilibrium constant provides information about how far a reaction proceeds at a particular

temperature. The equilibrium constant is shown as the expression below:

[C]c [D]d
K eq = [A]a [B]b

As shown above, the equilibrium constant, K eq , is the concentration of products raised to the

power of their molar coefficients over the concentration of reactants raised to the power of their

molar coefficients.
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In this experiment, the equilibrium constant for the reaction between iron (III) ion (Fe3+)

and thiocyanate ion (SCN-) will be determined:

Fe3+ (aq) + SCN (aq) FeSCN2+ (aq)

The Fe3+ transition metal ion and the thiocyanate ligand (SCN) react, forming the FeSCN2+

complex ion. A complex ion is when the transition metal ion is attached to one or more

non-metal ligands through covalent bonding. Ligands are attached through dative covalent

bonding by donating both electrons for the bond, it therefore forms a complex ion. Hence, the

Fe3+ metal ion is the transition metal, with the thiocyanate ligand (SCN) attached.

Energy in the form of a certain frequency of visible light can be absorbed to promote an

electron from the lower set of orbitals to the higher set. The FeSCN2+ solution exhibits the color

orange because its complementary color, blue, is absorbed by the complex ion. Then, the valence

electrons in the partially-filled d sublevels transition from the ground state to the excited state.

This is possible due to the partially-filled d sublevels of the transition metal Fe3+ split into two

groups of energy levels as the electrons from the ligands interfere with it. Accordingly, the d

orbitals are now divided into a set of 3 orbitals and a set of 2 orbitals, in which the 3-orbital set is

at a lower energy level than the 2-orbital set. The energy gap between the two sets of orbitals is

small enough for the visible light to cause transitions.

In order to calculate the equilibrium constant, it is essential to determine the equilibrium

concentrations of Fe3+, SCN, and FeSCN2+. In this experiment, the concentration of FeSCN2+,

which are prepared by mixing measured volumes of Fe3+ and SCN solutions of known initial

concentrations, will be measured at equilibrium by measuring its absorbance at 470 nm (as 470

nm is the wavelength in which blue light is transmitted into the solution. The absorbance of blue
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light is measured and Beers Law is used to determine the concentration of the complex ion in

the equilibrium mixture. The ICE Table is then used to calculate the equilibrium concentrations

of the other two ions at equilibrium.

The equilibrium constant can be expressed as below:

[F eSCN 2+ ]
K eq = [F e3+ ][SCN ]

Method

Materials:

1. Vernier LabQuest

2. LabQuest App

3. Vernier Colorimeter

4. Plastic cuvette

5. 10.0 mL pipettes x2

6. Pipet pump

7. 20 X 150 mm test tubes x6

8. Test tube racks x2

9. Small beakers (50 mL - 150 mL) x8

10. 100 mL volumetric flask

11. Large beaker for cuvette waste

12. 0.200 M iron (III) nitrate, Fe(NO3)3, solution in 1.0 M HNO3

13. 0.0020 M iron (III) nitrate, Fe(NO3)3, solution in 1.0 M HNO3

14. 0.0020 M thiocyanate, SCN-

15. Distilled water

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16. Tissue to wipe each cuvette

17. Plastic pipets as needed

Procedure

Part I Prepare Standard Solutions and generate a Standard Curve

1. Obtain and wear goggles.

2. Label five 100 mL beakers 15. Obtain small volumes of 0.200 M Fe(NO3)3,

0.0020 M SCN, and distilled water. CAUTION: Fe(NO3)3 solutions in this experiment are

prepared in 1.0 M HNO3 and should be handled with care. Prepare four solutions according to

the chart below (The fifth beaker is a blank.). Use a 10.0 mL pipet and a pipet pump to transfer

each solution to a 100 mL volumetric flask. Mix each solution thoroughly. Measure and record

the temperature of one of the above solutions to use as the temperature for the equilibrium

constant, Keq.

Beaker 0.200 M Fe(NO3)3 0.0020 M SCN H2O

number (mL) (mL) (mL)

1 10.0 4.0 86.0

2 10.0 6.0 84.0

3 10.0 8.0 82.0

4 10.0 10.0 80.0

blank 10.0 0.0 90.0

Note: The fifth beaker is used as a blank for the Colorimeter calibration. It will have a slightly

yellow color due to the presence of Fe(NO3)3. By calibrating with this solution as your blank,

instead of distilled water, you will account for this slight yellow color.
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3. Prepare a blank by filling a cuvette 3/4 full of the solution in the fifth beaker. To correctly

use cuvettes, remember:

Wipe the outside of each cuvette with a lint-free tissue.

Handle cuvettes only by the top edge of the ribbed sides.

Dislodge any bubbles by gently tapping the cuvette on a hard surface.

Always position the cuvette so the light passes through the clear sides.

4. Connect the Colorimeter to LabQuest and choose New from the File menu.

5. Calibrate the Colorimeter.

a. Place the blank in the cuvette slot of the Colorimeter and close the lid.

b. Press the < or > buttons on the Colorimeter to set the wavelength to 470 nm. Press the CAL

button on the Colorimeter. When the LED stops flashing, the calibration is complete.

6. Set up the data-collection mode.

a. On the Meter screen, tap Mode. Change the mode to Events with Entry.

b. Enter the Name (Concentration) and Units (mol/L). Select OK.

c. Proceed directly to Step 7.

7. Collect absorbance-concentration data for the four standard solutions in Beakers 1-4.

a. Start data collection.

b. Empty and rinse the cuvette. Using the solution in Beaker 1, rinse the cuvette twice with ~1

mL amounts and then fill it 3/4 full. Wipe the outside with a tissue and place it in the device

(Colorimeter or Spectrometer). Close the lid on the Colorimeter.

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c. When the value displayed on the screen has stabilized, tap Keep and enter the value for the

concentration of FeSCN2+ from your Pre-Lab calculations. Select OK. The absorbance and

concentration values have now been saved for the first solution.

d. Discard the cuvette contents into the waste beaker which will ultimately be emptied into the

acid waste container. Using the solution in Beaker 2, rinse the cuvette twice with ~1 mL

amounts, and then fill it 3/4 full. Place the cuvette in the device, wait for the value displayed on

the screen to stabilize, and tap Keep. Enter the value for the concentration of FeSCN2+ in Beaker

2, then select OK.

e. Repeat the procedure for Beakers 3 and 4. Note: Wait until Step 10 to test the unknown.

8. Stop data collection. To examine the data pairs on the displayed graph, tap any data point. As

you tap each data point, the absorbance and concentration values are displayed to the right of the

graph. Record the absorbance and concentration data values in your data table.

9. Display a graph of absorbance vs. concentration with a linear regression curve.

a. Choose Graph Options from the Graph menu.

b. Select Autoscale from 0 and select OK.

c. Choose Curve Fit from the Analyze menu.

d. Select Linear as the Fit Equation. The linear-regression statistics for these two data columns

are displayed for the equation in the form

y = mx + b

e. Select OK. The graph should indicate a direct relationship between absorbance and

concentration, a relationship known as Beers law. The regression line should closely fit the four
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data points and pass through (or near) the origin of the graph. Record the linear fit equation in

your data table.

Part II Prepare and Test Equilibrium Systems

10. Using 50.0 mL volumetric flasks, prepare four mixtures according to the chart below.

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 15.00 10.00 Up to 50.0

2 15.00 15.00 Up to 50.0

3 15.00 20.00 Up to 50.0

4 15.00 25.00 Up to 50.0

11. Using the solution in the test tube, rinse a cuvette twice with ~1 mL amounts and then fill

it 3/4 full. Place the cuvette in the Colorimeter. After taking the reading, empty the cuvette into

the waste beaker.

12. Determine the concentration of the thiocyanoiron(II) solution, [FeSCN2+] using the standard

curve that you prepared in Part I of this lab.

Analysis

Data Table:

Table 1: Absorbance of Standard Solutions

Test tube number [FeSCN2+]/ M Absorbance Values at 470 nm

1 8.0 x 10-5 0.111

2 1.2 x 10-4 0.226

3 1.6 x 10-4 0.399

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4 2.0 x 10-4 0.464

*Note: The concentration of the complex, FeSCN2+, is assumed to be equal to the value of the

concentration of SCN-, because the concentration of Fe3+ is put in excess. Therefore, according to

LeChateliers Principle, the equilibrium will shift to the right (product side).

Table 2: Analysis of Solutions Used to Determine Kc

Test tube number Absorbance Values

1 0.112

2 0.166

3 0.235

Table 3: Values needed for Determination of the Equilibrium Constant

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Initial [Fe3+] M Initial [SCN] M Final [FeSCN2+] K eq

M

1 0.00060 0.00040 7.90 x 10-5 472

2 0.00060 0.00060 9.65 x 10-5 380

3 0.00060 0.00080 1.19 x 10-4 363

Calculations (based on Test tube number 1):

1. Determine the concentration of each diluted solution.

C 1V 1 = C 2V 2

(0.0020)(0.0040)
C2 = (0.100)
= 8.0 x 105

2. Determine the value of the final [FeSCN2+] M from the calibration curve.

Y = 3080(x) - 0.1312

0.112 = 3080x - 0.1312

X = 7.90 x 10-5

3. Find the value of the equilibrium constant.

In order to determine the equilibrium concentrations of the two concentrations, Fe3+ and SCN, a

reaction table known as the ICE (Initial, Change, Equilibrium) Table will be used. I indicates

initial concentrations of products and reactants, C indicates the concentration change required

for the reaction to reach equilibrium, and E indicates the concentration when the reaction

reaches the equilibrium. Before reaction, no product is present. However, as time passes, product

is formed, therefore the equilibrium concentration of the product is the change in product

concentration. The ICE table is shown below:

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Fe3+ (aq) + SCN (aq) FeSCN2+ (aq)

Initial 0.00060 0.00040 0

Change -7.90 x 10-5 -7.90 x 10-5 + 7.90 x 10-5

Equilibrium 5.21 x 10-4 3.21 x 10-4 7.90 x 10-5

4. Find the Keq value.

[F eSCN 2+ ]
K eq = [F e3+ ][SCN ]

(7.90 x 105 )
K eq = (5.21 x 104 )(3.21 x 104 )

= 472

Conclusion:

The K eq value obtained in this experiment ranged from 363 to 472. As the concentration of Fe3+

is put in excess, according to LeChateliers Principle, the equilibrium will shift to the right

(product side). This is shown in the equilibrium constant; the value of K eq is above 1, indicating

that the forward reaction is favoured as it means that there is a higher concentration of products

than that of the reactants.