The Remarkable
Chemistry of Potassium Superoxide
research conducted by Andrew Allen
research director: Dr. Mike Anderson (primary) and Dr. Bruce Mattson
Potassium superoxide is a
yellow paramagnetic solid that is air and moisture sensitive. Its
formula is KO2 and because potassium is
+1, the superoxide has a charge of -1. Potassium superoxide has a
number of remarkable physical and chemical properties that we present
at this web page.
Part 1. Physical properties of
potassium superoxide.
Potassium superoxide is a yellow
solid. If we were to leave the solid out in the air, it would
soon decompose to a white solid due to either carbon dioxide or water
vapor in the air.
Potassium superoxide is
paramagnetic. The simple explanation is that with a formula of O2-2,
there are simply an odd number of electrons in the anion (6 e- + 6 e-
+ 1 e-
= 13 e- ),
hence it is paramagnetic. From a molecular orbital
explanation, the peroxide ion has a molecular orbital configuration of
(sigma)s2 (sigma*)s2
(sigma)p4
(pi)43
(pi*)3. The unpaired electron in the pi*
orbital accounts for the paramagnetic behavior or potassium
superoxide. This also accounts for the yellow color of the
substance. In order to demonstrate the paramagnetism of postasium
superoxide, we suspended a test tube of the substance from a thread as
shown below. When we bring a neodymium magnet up close to the
material, there is a noticeable attraction towards the magnet.
The small picture that below these two is a composite picture of the
tube with and without the magent present.

.
Composite picture of the KO2-filled
test tube with (foreground) and without (background) the neodymium
magent present.
Part 2. Chemical properties of potassium superoxide.
For the reactions that we are about to describe, we used the following
apparatus. We constructed a glass tube from a disposible glass
pipet. The tube was plugged on one end with some glass wool and
then filled with about 0.6 g KO2 followed
by another glass wool plug. The photo shows how two short lengths of
latex tubing are inserted inside
the pipet. The glass tubes are connected to syringes as shown in
a number of the following photos.

Experiment Series 1. Conversion of carbon dioxide to oxygen:
2 CO2(g) + 4 KO2(s)
--> 3 O2(g) + 2 K2CO3(s)
The above reaction was conducted in the following sequence of
pictures. The syringe pictured on the left contains CO2,
the KO2 tube is in the middle and the
receiver syringe is on the right. Note the yellow color of KO2
changing to white K2CO3
as the CO2 is passed through the
solid. In terms of moles, we used approximately 2 mmol of CO2
and 8 mmol KO2. Thus we expect that
CO2 is the limiting reagent. The receiver
syringe is expected to contain O2.
.
.
The gas produced and collected in the right syringe, expected to
contain O2 is tested, along with CO2
with universal indicator. This is a picture of the universal
indicator solution that is used for the tests.

The solution above was divided
evenly into two beakers as pictured below. On the left we have the receiver syringe
from the above reaction, expected to contain O2.
On the right we have another
syringe filled with CO2.

The product syringe does not
change the pH of the solution, while the same amount of CO2
lowers the pH appreciably.

Next, the product gas is tested using the traditional glowing splint
test for O2, as shown in the next
sequence of three pictures.

Buring splint blown out and...

... plunged into the receiver syringe, proving the presence of O2.

The limewater test. Both CO2 and
product gas (O2) are bubbled through test
tubes containing Ca(OH)2(sat'd), commonly
called limewater. The solution turns cloudy if CO2
is present as the gas reacts with Ca(OH)2(sat'd)
to form CaCO3(s). The test is
positive for the CO2 in the reactant
syringe as shown in the left test tube, but negative for the gas in the
product syringe, shown at right.

In this final test, the two gases (unreacted CO2
and product gas O2) are mixed with 6 M
NaOH(aq), Oxygen does not react, however CO2
does, forming Na2CO3(aq)
+ H2O(l). The result is that all of
the CO2(g) "disappears" as it becomes
part of the solution phase. In this photo, the syringe on the
left contained 60 mL CO2(g) + 10 mL 6 M
NaOH. Note that all of the CO2(g)
has reacted and is gone. The receiver syringe on the right contains 60 mL O2(g)
produced from the reaction + 10 mL 6 M NaOH. No reaction occurs.

In this next sequence of three pictures, NO(g), the colorless gas in
the left syringe, is being passed through the KO2(s)
forming red-brown nitrogen dioxide, NO2(g).
The reaction is highly exothermic.



In this final sequence of five
pictures, SO2(g), the colorless gas in
the left syringe, is being passed through the KO2(s)
forming, we presume, sulfur trioxide, SO3(g).
The reaction is highly
exothermic. More work is
planned here.


In this closeup, the reaction area is shown as the dark area to the
left. The areas moves rightward as the reaction proceeds.
Red "mini-flames" are noted in the KO2
tube! (We have not successfully captured them on film yet,
however.)


