Modified by Jason Marmon and George Lisensky from J. J. Garcia-Jareño,
D. Benito, J. Navarro-Laboulais, and F. Vicente, "Electrochemical Behavior of
Electrodeposited Prussian Blue Films on ITO Electrodes," J. Chem. Educ.,
75, 881-884 (1998).
In this experiment K3[Fe(III)(CN)6]
is electrochemically reduced at a glass electrode to produce K4[Fe(II)(CN)6].
The K4[Fe(II)(CN)6] at the electrode reacts with Fe(III)Cl3
in solution to give insoluble Prussian Blue, Fe(III)4[Fe(II)(CN)6]3,
on the electrode. The approximately 100 nm thick layer exhibits visible electrochromism,
i.e., the coating on the glass changes color with applied voltage. (Prussian
Blue has been made by chemists for 300 hundred years. For more information on
its history, see http://webexhibits.org/pigments/indiv/overview/prussblue.html.)
Add 5 mL 0.05 M HCl, then 10 mL 0.05 M K3[Fe(CN)6],
and then 10 mL 0.05 M FeCl3.6H2O to a
50 mL beaker. The mixed solution should be prepared just before use.
Identify the conducting side of a tin oxide-coated piece of glass
by using a multimeter to measure resistance. The conducting side will
have a resistance of 20-30 ohms.
Face the conducting side of the glass towards a platinum wire coil
or graphite electrode. Connect the negative lead of a voltage source to
the glass and the positive lead to a platinum wire coil or graphite electrode.
Dip the electrodes (but not the aligator clips) into the solution prepared
above and quickly adjust the voltage to produce 40µA/cm2
for 60 seconds. See electrical circuit
diagram on another page.
Rinse the electrode with pure water. The approximately 50 nm coating
(see calculation) after 60 seconds of deposition can be seen by eye on
the conducting surface.
(The sixth term in the equation above comes from the cubic
unit cell dimensions. Inorg. Chem., 16(11),
2704-2710, (1977)).
Longer electrolysis times give thicker coatings. In this movie, after
passing 80 µA current for 30 seconds (40µA/cm2
times an electrode area of 2 cm2) the electrode is rinsed to
show the color change. The rinsing steps are repeated after every 30 seconds
to show the changing color but would not be needed otherwise unless you
are recording visible absorbance (690 nm) as a function of layer thickness.
The total electrolysis time for this relative thick coating is 300 seconds.
Place the rinsed electrodes in 25 mL 1.0 M KCl, keeping the clip above
the solution.
Changing the applied voltage (next step) will change the color of the thin film.
Remove the battery from the circuit and alternately connect
the electrodes as follows:
Glass electrode connected to battery (–) and platinum or graphite
electrode connected to battery (+); negative voltage applied.
Glass electrode directly connected to platinum or graphite electrode;
zero volts applied.
Films are reported to be more stable if you repeat steps 1 and 2 several
times before going on.
Glass electrode connected to battery (+) and platinum or graphite electrode
connected to battery (–); positive voltage applied.
Glass electrode directly connected to platinum or graphite electrode;
zero volts applied.
Repeat.
Record the cylic voltammogram of the coated glass at 20 mV/sec from
+550 mV to -250 mV to +1200 mV to +550 mV versus a Ag/AgCl reference electrode.
When the voltage matches a redox reaction the current increases.
What color is the reduction product? What is the redox potential for
the reaction?
Fe(III)4[Fe(II)(CN)6]3 + 4 K+
+ 4 e- = K4Fe(II)4[Fe(II)(CN)6]3
What color is the oxidation product? What is the redox potential for the
reaction?
Fe(III)4[Fe(II)(CN)6]3 + 3 Cl-
= Fe(III)4[Fe(III)(CN)6]3Cl3
+ 3 e-
What is the source of the K+ and Cl- ions in the
redox reactions?
Materials
0.05 M HCl (Each preparation needs 5 mL. Dilute 5 mL conc HCl to 250
mL with water.)
0.05 M K3[Fe(CN)6] (Each preparation needs 10 mL.
Dissolve 1.65 g in 100 mL water.)
0.05 M FeCl3.6H2O (Each preparation needs
10 mL. Dissolve 1.35 g in 100 mL water with a drop of HCl.)
1.0 M KCl (Each preparation needs 25 mL. Dissolve 18.6 g in 250 mL water
with two drops of HCl to lower the pH.)
Equipment
50 mL beaker
Conductive Glass (1" x 1" x 2.3mm TEC 15 glass) Hartford Glass Co,
735 E Water Street, Hartford City, IN 47348 Phone: 765-348-1282. Glass can be reused
by removing prussian blue coatings with concentrated ammonia (solubility
increases with pH).
Ohmeter
Pt wire or graphite electrode
1.5 Volt battery, holder, and 50 K ohm variable resistor for controlling
deposition current. See electrical
diagram.
Electrochemical apparatus for obtaining cyclic voltammograms