Instructor: Dr Anna Toy-Palmer Name: ______________________________________

CHEMISTRY R122

EXPERIMENT 1 –
SPECTROPHOTOMETRIC DETERMINATION OF THE
EQUILIBRIUM CONSTANT FOR IRON(III) THIOCYANATE COMPLEX

INTRODUCTION

Spectrophotometry and Beer’s Law

In this experiment you will become familiar with the operation of a manual
spectrophotometer. You will use this instrument to study the interaction (absorption) of the
iron(III) thiocyanate complex solution with light. You will also use this instrument to study
the relationship between the amount of light absorbed and the concentration of the
chemical substance. Finally, from the amount of light absorbed at one selected wavelength,
you will determine the equilibrium constant for the formation of the iron(III) thiocyanate
complex.

When light is shone through a solution containing a light absorbing substance,

certain wavelengths of light are absorbed by the substance. Other wavelengths of light pass
through the substance unabsorbed. The use of the absorption of light by a chemical is an
elegant and easy method of studying that chemical. It is also an easy method of quantitative
analysis. The wavelengths absorbed often give information about the nature of the chemical
substance. In a solution containing a light absorbing substance, the amount of light
absorbed by the substance at a given wavelength is proportional to the concentration of the
substance (solute). This relationship is known as Beer’s Law.

You will first measure the amount of light transmitted or absorbed at various
wavelengths of light by a solution containing an iron(III) thiocyanate complex and then you
will plot an absorption spectrum. An absorption spectrum is a graph of the amount of light
absorbed as a function of the wavelength. A typical absorption spectrum or wavelength scan
is shown below in Figure 6.1.

Figure 6.1 – Wavelength Scan for a Light Absorbing Substance

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Instructor: Dr Anna Toy-Palmer Name: ______________________________________

The wavelength is measured in nanometers (nm). The prefix “nano” means 10 ‐9 times the base
unit. One nanometer is 1 x 10‐9 meters. The older term for nanometer is millimicron (m). A
wavelength of 500 nm = 500 m = 5000 Å. An Angstrom, Å, is strictly a unit of length: 1 Å = 1 x 10 ‐
10 m. It is used when referring to wavelengths of light typically in the ultraviolet region of the
electromagnetic spectrum.

In a wavelength scan, either the amount of light transmitted or the amount of light
absorbed can be plotted. However, since the wavelengths absorbed mean that they have
interacted with the chemical, the absorbed light is of greater interest than the transmitted light.
Transmitted light is light that has not interacted with the chemical but passes through the
substance instead.

The light transmitted can be referred to quantitatively as the transmittance or the

percent transmittance. The transmittance of the solution is defined as the ratio of the amount of
transmitted light (P) to the amount of incident light (Po).

Amount of light before entering  Solution  Amount of light transmitted

solution (incident light) = Po through solution = P

Transmittance = T = P % T = P (100)
Po Po

The absorbance (A) of a solution refers to the light that is absorbed by a light absorbing
substance at a given wavelength of light and it is a logarithmic function. The absorbance is
defined as:

Absorbance = A = ‐ log T = ‐ log P

Po

Note how similar this is to pH and the molarity of H +. You should be able to convert from
% transmittance to absorbance.

Example 1: A solution shows 60.% transmittance (T = 0.60) at a given wavelength. The

absorbance is calculated by:

A = ‐ log T = ‐ log 0.60 = 0.22

Example 2: A solution has an absorbance of 0.50. The % transmittance is: A =

‐ log T then, 0.50 = ‐ log T, and T = 10‐0.50 = 0.32

Spectrophotometers read in either % transmittance or absorbance. The

absorbance is more meaningful and more useful. One major advantage of

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Instructor: Dr Anna Toy-Palmer Name: ______________________________________

absorbance is in the determination of the concentration of the solute. A plot of

absorbance versus molarity of the solute gives a straight line. A plot of % T
versus molarity gives a curve. It is always easier to work with a straight line
than with a curve.

If absorbance (A) is proportional to concentration, then A = k c, where c is

concentration and k is a proportionality constant. The absorbance is also proportional to
the distance the light travels through the solution. The more time the light spends in the
solution, the greater the chance that it will react with the solution. The distance the light
travels through the solution would be the inside diameter of the cell containing the
solution. Therefore, the absorbance is proportional to the concentration of the solute and
to the cell thickness (inside diameter). Therefore the proportionality constant k is equal
to  times cell thickness, where is the molar absorptivity constant. So:

Absorbance A = (cell thickness)(concentration),

or A = bc,

where  is the molar absorptivity constant, b is cell thickness and c is

concentration of the solute.

This relationship is known as Beer's Law.

The Spectrophotometer

A schematic diagram of a spectrophotometer is shown below in Figure 6.2:

Figure 6.2 – Schematic Diagram of a Spectrophotometer

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Instructor: Dr Anna Toy-Palmer Name: ______________________________________

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Instructor: Dr Anna Toy-Palmer Name: ______________________________________

"White" light is emitted by the lamp “A”. White light is light that emits all visible
wavelengths. The light passes through the slit at “B” and strikes a prism (or diffraction
grating) at “C”. The prism or diffraction grating spreads the light into a continuous spectrum
at “D”. For a prism, the short wavelengths (violet) are bent the most and the long
wavelengths (red) are bent the least.

The slit “E” allows only a narrow band of wavelengths to pass. When the prism is
rotated, the spectrum will move up or down on “D”, changing the average wavelengths
passing through the slit at “E”. The prism is on a calibrated wheel so that the average
wavelength passing through the slit “E” can be read. The light passing through the slit then
passes through the cell “F”, which contains the solvent or the solution. It then passes on to
the photocell “P”. The photocell converts light energy to an electrical signal that shows on
the meter as either % transmittance or absorbance.

In general, the light source must deliver sufficient energy in the region of the
electromagnetic spectrum in use. Tungsten lamps (auto headlights) are usually used for the
visible region while hydrogen discharge lamps are used in the ultraviolet (UV) region of the
spectrum. The intensity of the light coming from the lamp varies with the wavelength. The
output (sensitivity) of the phototube also varies with wavelength. Also, the light absorbed
by the cell and by water will vary with wavelength. To account for these variations, the
instrument is adjusted at each wavelength so that the light passing through the cell
containing only water (or other solvent) reads zero absorbance (or 100 % transmittance).
The solution is then substituted, and the amount of light absorbed (absorbance) is due only
to the solute.

Equilibrium

Equilibrium is the condition where the rate of a reaction forward is equal to the rate
of the reaction in reverse. It can be characterized by quantitatively defining its equilibrium
constant, Keq, at a specific temperature.

In this experiment, the value of Keq for the reaction between Fe3+ and SCN‾ ions
(shown below) will be determined.

Fe3+ (aq) + SCN‾ (aq) FeSCN2+ (aq)

The equilibrium expression is:

Keq = [FeSCN2+]
[Fe3+][SCN‾ ]

When Fe3+ and SCN‾ are mixed, a reaction occurs to produce FeSCN 2+, an ion that in
an aqueous solution will produce a reddish color. However, the reactants will not react
completely. Thus the reaction mixture will contain some of each of these three ions (Fe 3+,
SCN‾, FeSCN2+). Since Fe3+ and SCN‾ are essentially colorless in solution, the red color
observed when conducting the reaction is produced by the FeSCN2+ ions.

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Instructor: Dr Anna Toy-Palmer Name: ______________________________________

To find the value of Keq at a given temperature, it is necessary to determine the molar
concentration of each of the three ionic species in solution at equilibrium. You will
determine the concentrations by using a spectrometer to measure the amount of light of a
specific wavelength that passes through a sample of the equilibrium mixtures. The amount
of light absorbed by a colored solution is proportional to its concentration, as discussed
above regarding Beer’s law. The specific wavelength used will be determined by the
absorbance spectrum of the solution. Ideally, the wavelength chosen will occur where the
solution has the maximum absorbance. (For the iron(III) thiocyanate complex, the
wavelength will be in the range of 450 - 470 nm).

To evaluate this equilibrium system, two separate tests will be required.

Part I: A series of standard solutions of FeSCN 2+ will be formed from solutions of varying
concentrations of SCN‾ combined with solutions of containing constant concentrations of
H+ and Fe3+. The excess H+ ensures that the Fe3+ ion does not engage in any side reactions
(for example, formation of Fe(OH) 2+) which could interfere with the measurements. In the
presence of excess Fe3+ ions, the SCN‾ ions will be the limiting reagent, thus all of the SCN‾
will form FeSCN2+ ions. Complex formation occurs slowly, taking at least one minute to
develop color. Take the absorbance readings between two and five minutes after preparing
the equilibrium mixture. Waiting past five minutes will lead to larger errors in the
readings, because the mixture is light sensitive and the iron(III) thiocyanate ions will
slowly decompose.

Part II: A new series of solutions that differ in the concentrations of SCN‾ ions but have
constant concentrations of H+ and Fe3+ ions will be prepared. You will record the
absorbances of each solution at the appropriate wavelengths and use the results to
accurately determine the equilibrium concentrations of each species. You will then be able
to calculate the Keq of the reaction.

Prelab:

In addition to the assigned prelab work as described in the syllabus, please complete the
table below based on Experimental Procedure Part 1: Preparation of Standard
Solutions.
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Instructor: Dr Anna Toy-Palmer Name: ______________________________________

Calculate the concentration of the iron(III) thiocyanate ion, [FeSCN 2+], for each beaker.
Assume all SCN‾ ions react (SCN‾ is the limiting reactant). Note for Part 1, mols SCN‾ =
Mols FeSCN2+.

Beaker Number [FeSCN2+]

Experimental Procedure

1. Preparation of Standard Solutions

• Label four 100.-mL beakers 1-4.

• Pipette volumes of 0.200 M Fe(NO3)3, 0.0020 M SCN‾ and deionized water

based on the table below. Mix thoroughly.

• Measure the temperature of one of the solutions.

• Be certain to measure the absorbance of these four mixtures within 2-5

minutes of preparing them because the solutions are light sensitive.

Beaker Number Volume of 0.200 Volume of Deionized H2O

M Fe(NO3)3 in 0.0020 M SCN‾ in mL
mL in mL

1 5.0 4.0 41.0

2 5.0 3.0 42.0

3 5.0 2.0 43.0

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4 5.0 1.0 44.0

 Prepare a blank by filling a cuvette ¾ full with 0.200 M Fe(NO 3)3 solution.

To correctly use cuvettes, remember:

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

ii. Handle cuvettes only by the top edge of the ribbed sides.
iii. Dislodge any bubbles by gently tapping the cuvette on a hard surface.
iv. Always position the cuvette so the light passes through the clear sides.

The Spectrometer

1. Connect the spectrometer to the LabQuest via a USB cable.

2. Calibrate the spectrometer.
a. Click on red box that says “USB: Abs”.
b. Select “Spectrophotometer mode” then “Absorbance”.
c. Click on red box that says “USB: Abs”, select calibrate then “OK” for the dark
sample
d. After the lamp is warm (~90 s), place the cuvette with the blank in
spectrophotometer. [NOTE: When prompted for the blank cuvette, use the
prepared blank that contains the 0.200 M Fe(NO 3)3 solution.]
e. Use a Kimwipe to clean the clear sides of the cuvette. Handle cuvette by holding
them at the top and on the translucent sides. [NOTE: The clear sides should face
the arrow and lamp symbols on the top of the spectrophotometer.]
f. Click on “Finish Calibration”.
g. Click on “OK”.

3. Determine the optimum wavelength for the equilibrium mixture

a. On the LabQuest, click on “Mode”
b. Select Full spectrum (take default)
i. Sample time90 ms
ii. smoothing 1
iii. samples to average 6
iv. Wavelength range: 380 – 950 nm
c. Place a cuvette that is filled ¾ full with the equilibrium mixture from beaker 1.
d. Wipe the outside of the cuvette with a tissue and place the cuvette in the
spectrometer.

4. Click the lower red triangle (collect). The absorbance vs. wavelength spectrum will be
displayed.
a. Note the wavelength which has the highest peak – this is max. (The wavelength
typically occurs between 400 – 480 nm)
b. Save your graph on the LabQuest
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Instructor: Dr Anna Toy-Palmer Name: ______________________________________

c. Using the stylus, move the cross hair to the highest peak and record the
wavelength (nm)
d. Go to File_Save_As then type eq_full_spectrum with your initials. Click
on the “Save.” This will save your data on the LabQuest.

5. Setting up the Mode to collect Data

a. Locate the Data Collection Details box and tap it to modify the settings.
b. In “Mode” options select “Events with Entry”
c. Change the Name to “Concentration” and Units to “M”, leave the other
options unchecked.
d. Press OK.

6. Collecting the absorbance-concentration data for the four standard equilibrium mixtures.
a. Leave the cuvette, containing the Beaker 1 mixture (see Step 3 above), in
the device.
b. Click the lower red triangle (collect).
c. After the absorbance reading stabilizes, click the button “Keep” and type
the concentration of FeSCN2+ (in molarity) in the edit box.
d. Click “OK”
e. Replace the cuvette containing the Beaker 1 mixture with the cuvette
containing the Beaker 2 mixture.
f. After the reading stabilizes, click “Keep” and type in the concentration of
FeSCN2+ in the edit box. Click “OK”.
g. Repeat steps e and f for the solutions in Beakers 3 and 4.
h. Click the square button (Stop) after you have finished collecting the data
from the four beakers of reaction mixtures.
i. Save your data on the LabQuest: Go to File_Save_As then type
abs_conc_eq with your initials. Click on the “Save.” This will
save your data on the LabQuest.

Part II. Test Equilibrium Systems

1. Preparing the equilibrium solutions

a. Label three large clean test tubes A-C.
b. Prepare the solutions according to the table below.

Test Tube 0.0020 M Fe(NO3)3 0.0020 M SCN‾ (mL) DI Water

(mL) (mL)
A 3.00 3.00 4.00
B 3.00 4.00 3.00
C 3.00 5.00 2.00

2. Collect absorbances of the three equilibrium solutions. Again be sure to record the
absorbances within 2-5 minutes of preparing them.
a. Fill a clean cuvette about ¾ full of solution A.
b. Wipe the outside with a tissue and place in the spectrometer.
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Instructor: Dr Anna Toy-Palmer Name: ______________________________________

c. Record the absorbance of the sample.

d. Repeat steps a-c for solutions B and C.

Data Tables:

Part 1.

Temperature: ______________________________ oC

Wavelength: ______________________________nm with maximum absorbance (based on

absorbance spectrum of solution from Beaker 1)

Beaker [FeSCN2+] Absorbance

1
2
3
4

Make a graph Absorbance vs [FeSCN2+] using Excel and create a best-fit line (linear
regression).

 Record the linear regression equation and R2.

Linear regression R2
equation

Part 2: Equilibrium concentrations

Test Tube Absorbance [FeSCN2+] at

equilibrium
A
B
C

A common method that is used to organize and calculate the concentrations of the species in
an equilibrium system is known as an ICE table or ICE chart. “ICE” stands for Initial
concentration, Change in concentration, and the Equilibrium concentration. The initial
concentrations of the Fe3+ and SCN‾ ions can be calculated from the mixing charge in part II.
The equilibrium concentrations were determined when completing the table in Part 2, see
above.
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Instructor: Dr Anna Toy-Palmer Name: ______________________________________

ICE Tables

Test Tube A

Fe3+ SCN‾ FeSCN2+

Initial
Change
Equilibrium

Test Tube B

Fe3+ SCN‾ FeSCN2+

Initial
Change
Equilibrium

Test Tube C

Fe3+ SCN‾ FeSCN2+

Initial
Change
Equilibrium

Data Analysis: Calculating Keq for each reaction

Use your data from Part 2 to complete the table below for equilibrium concentrations for each
of the mixtures A-C. Then show the Keq expression and your calculations used to determine
the Keq for each reaction (A-C). Finally, give the average Keq.

Test Tube A Test Tube B Test Tube C

[FeSCN2+]eq
[Fe3+]eq
[SCN‾]eq

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Instructor: Dr Anna Toy-Palmer Name: ______________________________________

Keq

Average Keq: _____________________________________

Application of Principles
1. Why must absorbance readings of the reaction mixture be taken before 5 minutes? Why
must it occur after one minute?

2. How would the value of Keq be affected if there is no H + in solution so there is significant
Fe(OH)2+ formed?

3. Write the equilibrium constant expression for the reaction shown below

2 N2O5 (g) 4 NO2 (g) + O2 (g)

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Instructor: Dr Anna Toy-Palmer Name: ______________________________________

4. Initially, a system contains 1.00 mol of NOCl in a 2.00 L container. At equilibrium, the system
contains 0.056 mol of Cl2 in a 2.00 L container. Create an ICE table and determine
the equilibrium concentrations and the value of K eq.

2 NOCl (g) ⇌ 2 NO(g) + Cl2 (g)

5. An equilibrium mixture contains 1.50 mol of nitrogen, 4.45 mol of hydrogen and 7.05 mol
of ammonia in a 5.00-L reaction vessel. Calculate the Kc for the reaction shown below:

N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)

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Instructor: Dr Anna Toy-Palmer Name: ______________________________________

References:

Chem R122 Lab Packet. Crockett, Luanne. Fall 2022 edition. Experiment 6.

Advanced Chemistry with Vernier, 4th edition. Randall, Jack. 2020. Pgs. 10-1 to 10-7

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