Experiment 6: Determination of an Equilibrium

Constant
PURPOSE
To study the properties of a system at chemical equilibrium, and determine the value of the
equilibrium constant.
Equipment Needed
spectrophotometer, burets
Chemicals Needed
-3

-1

-3

2.00 X 10 M Fe(NO3)3 in 1 M HNO3, 2.00 X 10 M Fe(NO3)3 in 1 M HNO3, 2.00 x 10

KSCN

Discussion
In many chemical reactions, as reactants combine to form products, the competing reverse
reaction can also occur; that is, the products can react to reform the original reactants. The
forward reaction will occur at an initial quick rate, but will slow with time, while the reverse
reaction will speed up with time as more and more product is formed. Eventually, the two
reactions will be occurring in opposite directions at the same rate. When this happens, there will
be no further change in the amounts of reactant and product present, and the system is said to
have reached equilibrium.
The mathematical relationship between the concentrations of the reactants and products is given
by the law of mass action. In general, for a reaction
aA + bB
cC + dD
the equilibrium constant is given by

K=

[C] [D]
[A] [B]

In this experiment you will use spectrophotometric measurements to determine the equilibrium
2+

constant for the formation of FeSCN . In dilute solution, iron(III) nitrate, Fe(NO3)3(aq) and
potassium thiocyanate, KSCN(aq), are completely dissociated. When these two solutions are
mixed, the following equilibrium is established:
3+
2+
Fe (aq) + SCN (aq)
FeSCN (aq)
+

(eq. 1)
-

3+

Of the five ions in solution, K (aq), NO3 (aq), and SCN (aq) are colorless, Fe (aq) is nearly
2+(aq)
2+
colorless, and FeSCN
is deep red. Changes in the concentration of FeSCN are indicated
by changes in the intensity of the color of the solution.

33

Experiment 6

Determination of an Equilibrium Constant

2+

The equilibrium expression for the reaction is

K=

[ FeSCN

3+

(eq. 2)

[Fe ][SCN ]

where brackets indicate molar concentrations. To calculate K for this reaction, it is necessary to
3+

2+

determine the molar concentration of Fe , SCN , and FeSCN

equilibrium.

present in the reaction mix at

Spectrophotometric Determinations
Atoms, molecules and ions absorb electromagnetic radiation. Electromagnetic radiation in the
visible part of the spectrum (wavelengths of 400-750 nm) has energy sufficient to move loosely
2+

bound electrons to slightly higher unoccupied orbitals. In Fe(SCN) , the presence of the SCN
ion causes the d orbitals on the Fe atom to split in energy just enough to cause electronic
transitions between d orbitals to result in absorption or emission of visible light at wavelengths
2+

centered around 447 nm. The FeSCN ion will be the only absorbing species present in the
equilibrium mixture if the starting Fe(NO3)3 solution is acidified to minimize the yellow-brown
3+

color of Fe .
Absorbance of light is measured by a spectrophotometer. Light from a source passes through
either a prism or diffraction grating so that a beam of a single wavelength (monochromatic light)
passes through the sample and into a detector.

Source

Prism or
Grating

Slit

Detector
Sample

Figure 1: schematic of a spectrophotometer

The relationship between absorption and concentration of the absorbing species is given by
Beer's law. Absorption of monochromatic light is directly proportional to the distance that the
light travels through an absorbing medium and the molar concentration of the absorbing species.
A=abc

A = absorption
a = absorptivity coefficient
b = path length that light travels through solution
c = molar concentration of the absorbing species.

34

(eq. 3)

Experiment 6

Determination of an Equilibrium Constant

The absorptivity coefficient a is a proportionality constant, and its value depends both on the
nature of the absorbing species and on the wavelength of light chosen for the measurement. At a
given wavelength, using a sample cell of constant pathlength, absorption is directly proportional
to concentration. Thus, a measurement of A can be used to determine concentration.
2+

You will prepare an FeSCN

solution of known concentration by reacting a given quantity of

3+

3+

SCN with a very large excess of Fe . The excess of Fe

2+

insures that essentially all of the SCN

-

is converted to FeSCN (equilibrium concentration of SCN is nearly zero), and the very high
3+

2+

[Fe ]/[SCN ] ratio essentially prevents the formation of higher complexes such as Fe(SCN)
which would otherwise interfere with your measurements.
2+

When the absorbance A of a solution of known [FeSCN ] is determined in a cell of known path
length, it can be used to determine the absorbtivity coefficient in eq. 3. Once a is known, the
2+

FeSCN concentration of an unknown solution can be determined from its absorbance

measurement.
EXPERIMENTAL PROCEDURE
A. Preparation of Solutions
Work in pairs or threes as assigned by your instructor. Record all volumes of reagents used on
the data sheet.
Turn on the Spectronic 20 and allow it to warm up for at least 5 minutes before taking any
measurements.
-3

Label five clean, dry 13 x 100-mm test tubes 1 through 5. Obtain about 40 mL of 2.00 X 10 M
iron(III) nitrate (Fe(NO3)3) solution in 1 M HNO3 in a clean, dry 150-mL or larger beaker. Using
a buret, measure 5.0 mL portions of the Fe(NO3)3 solution into each test tube. Next obtain 30
-3

mL of 2.00 x 10 M potassium thiocyanate (KSCN) solution in another clean, dry 150-mL or

larger beaker. Using a second buret, measure 1.0, 2.0, 3.0, 4.0, and 5.0 mL portions of the KSCN
solution into the tubes labeled 1 through 5, respectively. Empty and thoroughly clean the buret
containing Fe(NO3)3 solution, and then fill the buret with deionized water. Add 4.0 mL of
distilled water to tube 1; 3.0 mL to tube 2; 2.0 mL to tube 3; and 1.0 mL to tube 4. No water is
added to tube 5. Mix each solution thoroughly with a glass stirring rod. Be sure to rinse and dry
the stirring rod after mixing each solution.
2+

Prepare a solution of FeSCN of known concentration by combining 10.0 mL of 0.200 M

Fe(NO3)3 in 1 M HNO3 (this is not the same solution you used to prepare the five samples
above) measured with your 10-mL graduated cylinder, 2.00 mL of 0.0020 M KSCN measured by
buret, and 8.00 mL of distilled water measured by buret. Mix the solution thoroughly with a
3+

clean stirring rod. In this solution, the concentration of Fe

35

is much greater than that of SCN .

Experiment 6

Determination of an Equilibrium Constant

2+

Consequently, formation of FeSCN

is driven to the right, essentially to completion. You can

-

2+

assume without serious error that all the SCN is converted to FeSCN .
B. Spectrophotometric Measurements
2+

The concentration of FeSCN in test tubes 1 through 5 will be determined by measuring the
absorbance of each solution and comparing it with that measured for the solution of known
concentration. The absorbances will be measured at a wavelength of 447 nm using a Bausch and
Lomb Spectronic 20 spectrophotometer.
Add about 5 mL of deionized H2O to a clean cuvet. This is the blank. [NOTE: The cuvets are
special (and expensive) tubes. Be careful with them and do not scratch their surface.] Deionized
water is used as a reference in this experiment because it is the solvent and it does not absorb any
light at 447 nm.
Set the spectrophotometer wavelength to 447 nm. With the cell compartment empty, set the
needle to 0% T (infinite A) with the dark current control (using the left-hand knob). You should
not have to change this setting during the experiment.
Insert the blank cuvet into the cell compartment, align the mark on the front of the tube with the
mark on the compartment, close the lid, and set the 100% T value (zero A) with the right-hand
knob.
Rinse the other cuvette with two small portions of the solution of known concentration, discard
the rinsings, and fill the cuvette three-quarters full of the solution. Insert the cuvette containing
2+

the known FeSCN solution and read the meter to the nearest 0.1 division on the absorbance
scale. Record the absorbance readings on the data sheet.
Rinse and repeat the absorbance measurements on solutions from test tubes 1 through 5, and
record your absorbance readings on the data sheet.
C. Calculations
2+

To calculate the concentration of FeSCN

in the known solution, assume all the SCN is

2+

converted to FeSCN . Use n = MV to determine the number of moles of KSCN added to the
known, then divide by the total volume of the known solution to determine the concentration of
2+

FeSCN

in the known solution. Using Beers law (eq. 3), the cell path length (10 mm) and the
2+

concentration of the known, determine the absorbtivity coefficient a for FeSCN .

Next, use Beers Law, the measured absorbances of the five unknowns, and the known cell path
2+

length (10 mm) to calculate [FeSCN ] in each unknown.

36

Experiment 6

Determination of an Equilibrium Constant

3+

The initial concentrations of Fe and SCN in each test tube are calculated by considering the
dilution of the original volumes of Fe(NO3)3 and KSCN to the new sample volume. The
3+

equilibrium concentrations of Fe and SCN are equal to the initial values minus the
2+

concentration of FeSCN

in each sample.

The experimental equilibrium constant for each sample is calculated by eq. 2.

37

Experiment 6

Determination of an Equilibrium Constant

38

Lab Report
Experiment 6
Determination of an Equilibrium Constant

Name
Date
Lab Partner

A. Preparation of Solutions
volume (mL)
test
tube

-3

2.00 x 10 M
Fe(NO3)3

volume (mL)

volume (mL)

Total Volume

-3

2.00 x 10 M
KSCN

H2O

1
2
3
4
5
known

B. Spectrophotometric Measurements
test tube

known

absorbance

39

Lab Report
Experiment 6
Determination of an Equilibrium Constant

Name

C. Calculations
2+

1. Concentration of FeSCN in known solution

2. Absorbtivity coefficient a =
test
tube

absorbance

2+

[FeSCN ]

Aknown
bxC
initial
3+

[Fe ]

3+

[Fe ]eq

initial
-

[SCN ]

[SCN ]eq

1
2
3
4
5
average K

40

equilibrium
constant K