Equilibrium of the Iron Thiocyanate Reaction

Many chemical reactions are found to proceed to an equilibrium at which a mixture of

both reactant and products is present. The extent to which reactants are converted to
products is expressed by the equilibrium constant, K.

This experiment will probe the equilibrium of Fe(III) ions reacting with the thiocyanate
ion, SCN . The reaction has two possible products given below, in lab this week you will
determine which of these two reactions actually occurs.

Fe3+ + SCN FeSCN2+ Rxn 1

Fe3+ + 2SCN Fe(SCN)2+ Rxn 2

The nice aspect of this equilibrium is that the reactants are colorless, but the product is a
deep red color. The concentration of the products at equilibrium will be measure by
observing the absorption of blue light.

By measuring the concentration of the product produced from five different reactant
concentrations, you will determine which equilibrium above occurs for the iron
thiocyanate reaction.

Measuring Concentration by Optical Absorption:

Along with studying a system at chemical equilibrium, this laboratory will introduce the
concept of absorption spectroscopy. The red product of the reaction is absorbing blue
light, allowing the compound to transmit red room light to your eye. There is a simple
relationship between the amount of light a sample will absorb and the concentration of
the absorbing molecule.

A lc

In this relationship A is the absorbance (read by a spectrophotometer), c is the solution

concentration (mol/L), l is the path length of the sample (cm) and is the extinction
coefficient of the molecule (in this case it has units of L / mol cm). indicates how easily
the molecule absorbs light at a specific wavelength. This relationship between solution
absorbance and analyte concentration is known as Beer s law.

The important aspect of Beer s law in this instance is that Absorbance is linearly related
to the concentration of the absorbing species. This allows the creation of a calibration
curve to be constructed between absorbance and known concentrations of the product. In
Figure 1 the iron thiocyanate ion absorbance at 460 nm is plotted as a function of
concentration. This plot allows the rapid determination of solution concentration from
solution absorbance. As you perform these absorbance measurements, consider how long
it took to make a concentration measurement using freezing point depression. (The
advantage of freezing point depression is you do not need to know the identity of the
compound.)
 ?+
[Fe(SCN)?] calibration curve at 460 nm

1.0
0.8 Abs = 4521.4[conc]
0.6
0.4
0.2
0.0
0.00E+00 5.00E-05 1.00E-04 1.50E-04 2.00E-04

[Fe(SCN)?]?+ mol/L

Figure 1. An absorbance vs. concentration plot for the product of the iron thiocyanate
equilibrium.

Experimental Procedure:

Preparing the Five Equilibrium Mixtures:

From the front of the room obtain a 5 mL pipet, a graduated pipet, a red pipet bulb
and two spectrophotometer tubes. Place the spectrophotometer tubes in your test
tube rack.

In your smallest beakers obtain from the reagent bottles 30 mL of 0.002 M

Fe(NO3)3 and 20 mL of 0.002 M KSCN.

The five solutions you will prepare will have equal amounts of iron ions and
differing quantities of thiocyanate ions. Each solution will have the same 10 ml
volume, made by adding varying amounts of H2O.

In your test tube rack add five clean test tubes. Label your test tubes 1 5 by
placing your rack on a sheet of paper and writing the number on the paper. Fill
the test tubes with the reagents indicated in Table 1. It is best to fill all tubes first
with the amounts of thiocyante using the graduated pipet. Place the pipet bulb
gently over the end of the pipet. The bulb should be on so loosely that it would
fall off if you held the pipet upside down. Do not jam the bulb onto the pipet.
Allow your partner to hold your reagent beaker. To deliver 1.0 mL of SCN ,
draw into the pipet 3 or 4 mL of solution. Remove the bulb and allow the solution
to drain back into the reagent beaker. Place your index finger over the top of the
pipet to control the flow. Slow the flow down with your finger, stopping it at the
1 mL mark (or 9 mL mark depending on the labeling of your pipet). Expect to
draw up and drain the solution several times before you get the volume correctly.
Transfer the SCN solution to the correct test tube. Repeat the addition for the
other four test tubes. (Be sure that all members of the group have the pleasure of
pipetting.)

After the SCN solutions have been added, use the 5.0 mL pipet to measure the
Fe3+ solutions. The drawing up in this 5 mL pipet is more difficult because there
is only a small volume between the 5 mL mark and the top. Have the bulb on
loosely, so that it is easily removed as the liquid nears the mark. Try hard not to
fill the red bulb with Fe(NO3)3. If the solution gets on your hands wash them
immediately. Expect to perform several extractions before the correct volume is
reached.

Rinse the graduated pipet with water and add the necessary amounts of water to
each test tube. This should take the volume of each test tube to 10 mL. You will
need a little beaker of DI water from which you will draw the water into the pipet.

mL of 0.002M SCN mL of 0.002M Fe3+ mL H2O

Tube 1 1.0 5.0 4.0
Tube 2 2.0 5.0 3.0
Tube 3 3.0 5.0 2.0
Tube 4 4.0 5.0 1.0
Tube 5 5.0 5.0 0.0

Obtain from the front of the room a piece of parafilm so that the test tubes can
be shaken. Cover the top of each test tube with the parafilm and press down
with your thumb. Invert the tube several times to completely mix the solution.
Start with the most dilute SCN solution so that as the next solution is mixed
the parafilm does not accidentally contaminate a less dilute solution.

Any reagent remaining in your beakers should be placed in the waste-beaker

in the hood.

Calculate the initial concentrations of Fe3+ and SCN in each test tube 1 - 5.
This is just a dilution calculation.
Measurement of the Product Concentration:

Take your solutions to the spectrophotometer (Spec 20) to measure the

absorbance of the FeSCN ion-complex.

Since you have the absorbance vs. concentration curve at a wavelength of 460
nm, dial your spectrometer to that wavelength. Examine the spec 20
schematic in Figure 2 to see the location of the control knobs.

Sample Compartment Wavelength Control

0 % Transmission 100 % Transmission

Control: Adjust to 0% T Control: Adjust to 100% T
when no sample present. when blank present.
On/Off Switch

Figure 2. Schematic of a Spec 20

Turn on the Spectronic 20 or spectrometer by turning the zero control knob (left
front) clockwise, close the sample compartment door, and allow the instrument to
warm up at least 10 minutes.

After the instrument has warmed up, adjust the wavelength control to 460 nm and
adjust the zero control knob until the meter reads 0% T.

Pour a small amount of the blank solution or DI water into the spectrometer
tube. Rotate the spectrometer tube so the solution coats the wall of the
spectrometer tube. Discard DI water down the sink. Refill the spectrometer tube
to ¾ full with DI water.

Wipe the outside of the spectrometer tube with a Chemwipe or paper-towel.

Insert the cuvette into the Spectronic 20. Line up the white hash mark on the
spectrometer tube with the raised mark on the sample compartment. Close the
sample compartment door.

Slowly rotate the light control knob (right front) clockwise until the meter reads
100% T. Be careful not to change the zero control knob during this process. The
Spectronic 20 is now internally calibrated (meaning the instrument is properly
adjusted for operation).

After the spectrometer has been calibrated, measure the percent transmittance
(%T) for each FeSCN solution.

Fill the second spectrometer tube with solution #1 (the most dilute). Place the
solution in the spectrometer and record the absorbance.

After the %T is recorded the solution can be returned to the test tube and the
second most concentrated solution can be measured. Continue in this way until
all solution percent transmittances have been measured.

Convert all recorded %T to absorbance (A) using the following equations:

A = - log T

%T
T=
100%

Determine the concentration of the FeSCN ion-complex in each reaction tube by

converting all calculated absorbance to concentration using the linear equation in
the Figure 1 calibration curve.

All of the test tube solutions can be placed in the waste beaker. The Spec 20
tubes should be rinsed thoroughly with DI water and returned to the front of the
room.

To prepare for next week s lab on Acid-Base Titration, prepare approximately

500 mL of 0.1 M NaOH solution from a stock NaOH solution of 6 M. This
requires you to do a dilution calculation. The 500 mL 0.1M NaOH solution can
be stored in a corked flask until next week s lab.
 Determining the Equilibrium Constant for the Two Proposed Reactions:

In this experiment data collection is rather quick and data analysis is rather lengthy. As
you did in the pre-lab assignment, determine K for each proposed reaction using all five
initial concentrations. Recall that you have measured the [FeSCN]eq concentration and
you will have to use the reaction stoichiometry to calculate [Fe3+]eq and [SCN ]eq from
the initial concentrations of [Fe3+]0 and [SCN ]0. It is probably a good idea to write the
ICE tables for each reaction and create a data table that contains the components needed
to calculate K (ex. [Fe3+]eq, [SCN ]eq and [Fe(SCN)??+]eq) for each test tube.

From the reproducibility of the equilibrium constant, which equilibrium reaction

Fe3+ + SCN FeSCN2+ Rxn 1

Fe3+ + 2SCN Fe(SCN)2+ Rxn 2

occurs in the reaction of Fe3+ with SCN ?

Report the equilibrium constant, K, as an average of the five experimental measurements.

The uncertainty in your measurement can be given as the standard deviation in your
measurement. If you are unfamiliar with standard deviation calculations, ask the TA to
show you how this can quickly be calculated in Excel.

In your abstract briefly describe the system studied and the experimental method used to
determine K. Also report the equilibrium constant and its uncertainty.

Turn in your lab sheets before you leave lab.

Place your 0.1 M NaOH solution at the front of the room. It will be stored until next
week.