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DIY CHEMISTRY: Experiments with Manganese and some of

its compounds.
Lothar Graudins, Ph.D.
John Fleming
COPYRIGHT 2009

IMPORTANT NOTE: THIS ARTICLE IS WRITTEN SOLELY FOR INFORMATIONAL


INTEREST. IT IS INTENDED FOR THOSE INDIVIDUALS WITH AT LEAST ONE YEAR
COLLEGE CHEMISTRY EXPERIENCE. NEVERTHELESS, WE CANNOT AND DO NOT
ASSUME ANY RESPONSIBILITY WHATSOEVER FOR ANY MISUSE OR ACCIDENTS
RELATED TO THE USE OF THIS INFORMATION.

In this age of specialization, we have many experts with only a partial knowledge of a
subject. This is an outgrowth of an almost explosive development of new findings and
research. Still, it's important to have at least a general overview of our subject. In this
study of manganese, we will look at manganese ore, use an extraction process and end up
with the actual metal. Finally, we will synthesize an important manganese compound. In
the course of this process, you will find instructions for building a simple high
temperature furnace capable of reaching 1,465 degrees Centigrade. This furnace will be
useful not only in reducing Manganese (IV) Dioxide to Manganese (II) Oxide , but it
will allow you to do many useful experiments where a high temperature is needed. Part of
processing calls for obtaining the metal itself. This will be described using the
Goldschmidt or Thermite process. From the metal, you will learn how to synthesize
Potassium Permanganate using basic principles of electrochemistry. Two additional
experiments are described: an important test for unsaturated bonds and a dramatic
reaction illustrating Potassium Permanganate as a powerful oxidizing agent.

Major metals are found in the earth’s crust in complex forms called ores.
They are mined by various industrial processes and subsequently purified.
The chemistry student can often do some actual prospecting and mining as
well as reclaiming of important material. This is a challenging and
rewarding task. It is in this spirit that the procedure for processing
manganese ore is presented. You could simply buy Manganese Dioxide as
your starting point for these experiments. Manganese Dioxide is available
from commercial supply houses such as a Ceramics dealer. On the other
hand, there is some interesting “bench chemistry” not to be missed.

In the case of Manganese, there are over a dozen ores. Among the richest are
pyrolucite and braunite. I chose to start with braunite, since this is the ore I
had easy access to. You can ask about mines in your state through the State
Geological or Mining Association. Or, if you can't find this ore in a nearby
mine, you can order it from a rock (mineral) dealer found on the Internet.
Braunite is a very dense, black material with a metallic luster. It is
composed of manganese (approximately 60%) and silicates. Chemical
processing allows us to extract manganese in the form of its chloride and,
with further processing eventually obtain elemental manganese.

The following extraction process relies on a analytical procedure. Although


it may seem very elaborate and laborious, the process involves some
interesting chemistry and promotes practical “bench experience.” If you are
starting with braunite you must first obtain a coarse powder by running the
ore through a rock crusher. If you are doing the chemical extraction process
indoors, this definitely calls for a fume hood. Please read the detailed safety
instructions at this point (see Addendum). It is most advisable to do this
procedure outdoors. Incidentally, I find large coffee carafes and old tea
servers made of Pyrex glass extremely useful. They are at least 500 ml
capacity and usually come with handles. You can buy them cheaply in Thrift
Stores. Whenever temporary storage of a cold liquid is needed, use drinking
water bottles. Particularly in this process, since it is laborious to constantly
clean flasks.

Weigh out 100 grams of ore and place it in a 600 ml beaker. Cover it with
100 ml concentrated Hydrochloric Acid. Use commercial “Muriatic Acid,”
which is a cheaper and impure form of Hydrochloric Acid. Repeated
volumes of acid are added to the beaker, evaporating these additions until all
of the ore is reacted. You can heat the mixture with a hotplate to speed
evaporation but keep it below the boiling point, under 90 degrees C*. This
process generates large amounts of chlorine gas. Chlorine gas is poisonous
in larger concentrations. Use extreme caution when heating hydrochloric
acid. Use gloves and a face shield. Expect copious fumes of acrid and toxic
chlorine as well as hydrogen chloride. Do this outdoors or use a fume hood.

The process is done step-wise because manganese ores vary in their


composition. The braunite sample I processed required a total of 400 ml of
Hydrochloric acid to completely react or “digest” the braunite. When this
process is complete (or nearly so) you will notice an absence of reactivity
upon further addition of acid. Also, there will only be a minimal amount of
solid material left in the reaction vessel composed mainly of hydrated silica.

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When all of the ore has reacted, allow the mixture to cool to room
temperature. If you wish to see crystals of manganese chloride, allow the
mixture to stand for several days. Large, beautiful crystals will appear. (See
Figure 1) below:

While naturally pink to rose in color, these will usually be stained yellow
due to the presence of iron. Notice the distinct shape of these crystals. Into
which category of crystal structure do they belong? It may also have
occurred to you by now that you have transformed a very solid rock into
soluble crystals.

At his stage, redissolve the crystals with additions of hot water. Save the
solution and add it to the beaker. OR, if you have not allowed for crystal-

Figure 1. CRYSTALS OF MANGANESE CHLORIDE STAINED WITH IRON.

lization, add 400 ml water to the above cooled mixture. The insoluble
silicates will now appear. This grainy material looks much like common
sand (which most of it is!) Filter the solution. The manganese is present in
your filtrate as Manganese Chloride. Discard the silicates.

In order for the next step to work you must also have iron present in your
solution. This is most often the case, as manganese ore contains iron ore as
well. In my sample the intense yellow color was sufficient evidence.
Nevertheless, if you have some Ammonium Thiocyanate (a common reagent
for testing the presence of iron), make up a 10% solution and add a few
drops to your filtrate. A deep red color appears in the presence of iron. ( See
Figure 2).

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FIGURE 2. THIOCYANATE TEST FOR IRON

The next step is to oxidize the Manganese Chloride to the oxide by using
chlorine. Obtain some Calcium Hypochloride from a swimming pool supply
store. This product is sold as a chlorinating agent under various brand
names. Read the ingredient list and avoid the organic chlorides. Calcium
Hypochloride (as a commercial product) is relatively stable and contains up
to 50 % available chlorine. One important caution: Never add a granulated
oxidizer directly to an acid. The reaction is violent and can easily cause
injury. Remember also that chlorine gas is very poisonous in higher
concentrations.

Use a fume hood, face shield and gloves for this next procedure. Make a
slurry of Calcium Hypochloride by adding 20 grams of the powder to 50 ml
cold water. Use a 100 ml flask with a stopper. Shake well and slowly add this
mixture (Calcium Hypochloride is only slightly soluble in water) to your
cold acid mixture. You will notice bubbling and foaming as well as a black
precipitate of Manganese Dioxide.
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Slowly bring your mixture to a boil. You are converting Manganese Chloride
to Manganese Dioxide. (Don’t forget to use the fume hood!) You will see the
mixture turn increasingly black as the Manganese Dioxide is formed. Boil
for 20 minutes, cool and filter.** Extended boiling time results in larger
crystals which is helpful during filtration. This is also a step-wise process.
For my sample, I used about 500 grams of Calcium Hypochloride until the
conversion was complete. Filtration is done with standard laboratory filter
paper (such as Whatman #2), although ordinary coffee filters will work. The
product is rinsed off the filter using a wash bottle filled with distilled water.
You will obtain a clear yellow liquid. Test this filtrate for additional
Manganese Chloride . Use a test tube with about 10 ml filtrate, add a few
drops of the slurry. If you obtain more precipitate, repeat the above process.
Finally the filtrate will become clear and no further Manganese Dioxide can
be recovered. Dry the product and weigh it. What was your percent yield?
My sample yielded about 30 %. What is likely to be your largest
contaminant?

Regardless of how you obtained your Manganese (IV) Dioxide, the next step
is to convert it to Manganese (II) Oxide. This is done in a high temperature
furnace that you can easily build. Manganese Oxide is most appropriate to a
thermite reaction that produces raw manganese metal.

The furnace uses a light-weight, easily shaped thermal brick with high
insulating properties. In fact, the secret of obtaining very high temperatures
(this furnace is capable of boiling ordinary salt, B.P. 1,413 C.) is adequate
insulation. You use an ordinary propane torch for the heat source. (See
Figure 3) The principle of adequate insulation is important to remember for
any high temperature work you might consider.
FIGURE 3. A SIMPLE TORCH FURNACE CABABLE OF REACHING 1400 DEGREES CENTIGRADE

This type of brick is often available from larger hobby ceramic stores. You
also can order the bricks from Thermal Ceramics posted on the Internet.
Order Insulating Firebrick K-23. Although the recommended operating limit
is 1260 degrees C, the bricks will not melt below 1510 C. I built a simple
wooden frame to contain the bricks. Using a pocket knife, cut a cavity about
1/4 inch larger than the crucible. Cut a hole on one side of the crucible.
Bring in the torch nozzle at a 45 degree angle. The idea is to allow the hot
gasses to swirl around the crucible. (See Figure 3, above.)

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Fill a crucible with the Manganese (IV) Dioxide you have produced. Heat at
800 C., a dull-red color, for 30 minutes in the above furnace. Your product
will change color from black to a reddish tone. Repeat until you have
converted about 100 grams to Manganese (II) Oxide. Mix this oxide with 25
grams aluminum powder. The balanced reaction or stoichiometric ratio calls
for 212.7 grams MnO mixed with. 54 grams powdered aluminum. Below is
the balanced equation:

3MnO + 2Al > 3 Mn + Al 2 O 3

As you can calculate from the atomic or molecular weights involved, 266.7
grams of the mixture theoretically yields 164.7 grams of manganese metal.
Of course, life (and chemistry) are never that simple. Remember that you are
starting with an impure product. In addition, there is significant loss due to
vaporization at this high temperature as well as side-reactions whereby the
Manganese (II) Oxide reverts back to the initial form. Finally, the “slag” or
aluminum oxide entraps the metal. Nevertheless, you may be successful at
the last step.
If not, use pure Manganese (IV) Oxide as a starting point in the conversion
procedure. Follow up with small increments of reactants going into the
thermite mixture.

The resulting mixture is known as Thermite aka the Goldschmitt process. In


general, a thermite mixture results in a molten metal of an oxide that has
been reduced by a highly reactive metal powder, usually aluminum or
magnesium. Historically, iron oxide and aluminum powder was used to
weld railroad track by actually allowing molten iron to fuse the ends.
Thermite reactions produce extreme heat and light, molten metal splashings
and hot sparks. If not carefully conducted, it is a dangerous reaction! To
begin with, never exceed the recommended amount of reactants for a
specific application. In this case, start with 125 grams of reactants. Also,
important in this particular case, use only Manganese (II) Oxide. The
dioxide produces “flash powder,” a violent reaction similar to igniting black
powder. Never grind the combined ingredients. Always wear protective
clothing and eye gear when using thermite or its ingredients.

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To obtain a globule of manganese metal, prepare the reaction vessel. Use a
small ceramic pot (flower pot) and place a crucible in the center of the pot
after you have nearly filled it with sand. Surround the pot with sand. Also
buy a ceramic dish for the pot. Drill a half-inch hole through the middle of
the dish, to be used as a cover. (See Illustration 1 below).

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Be sure you do this outdoors only, in an area that contains no flammable
material. Place the thermite powder in the crucible. Cover with the lid.
Ignition is done with a piece of magnesium ribbon or a “sparkler.” A welding
torch can be used if neither of the above is available. However, be extra
careful with a welding torch to avoid overheating the mixture. Remember
you are dealing with molten metal. This reaction typically sprays molten
droplets, so allow for a large perimeter. Once the reaction is completed,
wait at least 20 minutes. Using insulated gloves, empty the contents of the
crucible and carefully sift through the material. You will find small metallic
globules of manganese, usually trapped in a matrix of aluminum oxide. This
condition can be improved upon by first heating the reaction vessel and
adding reactants step-wise. But, in fact, for now, you only need a small
nodule.

The next portion of these experiments calls for synthesizing some Potassium
Permanganate from a metal globule. Potassium Permanganate is a powerful
oxidizer commonly used as a disinfectant and in water treatment. It is also
used in analytical chemistry when a powerful oxidizer is needed. The usual
synthesis calls for fusing manganese dioxide with potassium hydroxide in
the presence of an oxidizer such as potassium nitrate or chlorate. However, it
is very instructive to use a method employing electrochemistry. At this point
you might review basic electrochemistry.

In this experiment we prepare the permanganate by anode oxidation of


manganese metal. Using a 600ml beaker, prepare about 300 ml of a saturated
solution of Potassium Carbonate. This is done by stirring small amounts of
Potassium Carbonate into 300ml of cold water (room temperature) until no
more will dissolve. Let the beaker stand for 10 minutes until the solution is
clear. The anode (positive terminal) and the cathode are simple iron wires.
Connect the cathode to a power supply, which can be a set of DC batteries
adding up to 6 Volts. I used a Regulated power supply with a DC voltage of
3.5 V and .15 amps. The anode is also an iron wire, with one end wrapped
around the nodule. Immediately after introducing current, you will see a
plume of violet permanganate drifting off the anode. Run the experiment for
about ½ hour to get a reasonably concentrated solution of potassium
permanganate. See Figure 4 below.

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FIGURE 4. ELECTROLYSIS OF MANGANESE METAL IN A SOLUTION OF POTASSIUM
CARBONATE.

Using the above solution of potassium permanganate, you can now test for
organic unsaturated bonds. Compounds containing unsaturated bonds will
discolor the purple solution producing a brown, peach colored precipitate of
manganese dioxide. You will learn more about unsaturated bonds in your
study of organic chemistry. Unsaturation refers to a compound where double
carbon-to-carbon chemical bonds are readily available for uptake of new
constituents. Common vegetable oils are composed of fatty acid esters that
contain unsaturated carbon bonds. When these bonds are altered, the
permanganate is reduced and becomes colorless. Fill a test tube half-way
with the solution you have just prepared. Now add about 2ml of a vegetable
oil, such as Canola Harvest brand. Stopper tube and shake well. A color
change to neutral or faint brown can be observed. If you perform this test
with a more concentrated permanganate solution, you will find a very fine
precipitate of manganese dioxide at the bottom of your container. You've
come full circle.
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Finally, the powerful oxidizing action of potassium permanganate can be
shown in a dramatic reaction. For this experiment you will need about 20
grams of pure potassium permanganate. Place this amount in a small
crucible. DO THIS EXPERIMENT OUTDOORS ONLY, AWAY FROM
ALL FLAMMABLE MATERIALS. Quickly add about 5ml of glycerine to
the crucible and stand back. A violent reaction ensues, with smoke and fire,
as the glycerin is oxidized.

* You can use an ordinary thermometer. However, a better method is to use a


thermocouple within a thin glass tube or sleeve. Use a little silicone oil for
better heat transfer. This device is not only more accurate, but, more
importantly for this experiment, easy to read.

**If you do much filtration, you will want to invest in a suction filter and
vacuum pump. For this work, due to Hydrochloric Acid fumes, you need a
pump consisting of non-metal parts. Or, alternately, you can use a simple
aspirator driven by water or compressed air. Compressed air devices are
available from Auto Supply houses at low cost. These devices achieve a
respectable vacuum and make short work of filtration. (See Figure 4) below:

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FIGURE 4. RIGHT ANGLE VALVE FOR GARDEN HOSE JOINED TO LAB WATER ASPIRATOR.

Advanced Topics and Experiments:

1. Ammonium Thiocyanate forms a deeply red and soluble complex in


the presence of iron. Use a separatory funnel and extract it with ethyl
ether. Crystallize the remaining Manganese Chloride.

2. Use a analytical chemistry flow chart to separate iron from


manganese. You will probably need a pH controlled solution.

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Addendum: A word about safety

1. For all procedures, closely follow instructions. If you are not


clear about a particular step, do the research to find out.

2. Always stick to recommended amounts of reagents. Usually


very small amounts are all that’s necessary to complete an
experiment.

3. Use protective gear such as gloves, safety glasses or a face


shield.

4. Many experiments call for a fume hood or outdoor


environment. Don’t compromise this safety rule.

5. Never taste a chemical or solution. Most are highly toxic.


If you spill a chemical or come in contact with a corrosive
agent, immediately wash with plenty of cold water. Read the
MSDS sheets on all chemicals you plan to use.

6. Learn about and practice safe disposal of all reagents.

While most chemicals are not inherently dangerous, careless


use can result in risky situations and harmful consequences. As
in all aspects of your life, you must assume complete
responsibility for what you do. In that respect, we, the authors,
are not responsible for any accident, injury or mishap resulting
from the information given in this article. There is no
mandate or recommendation that you do any of the
procedures. That part is entirely up to you. The above
experiments may be hazardous for the novice. We recommend
at least one year of college chemistry experience.
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If you are under 18 and/or have no experience with chemical
experimentation, you should choose less hazardous tasks and
always ask for supervision. Most practices of applied
chemistry, experimental rocketry, for example, have excellent
to near-perfect safety records. This comes from intelligent and
methodical work.

If you enjoy high risk behavior, chemistry is not for you. Try
skateboarding, motorcycle racing or even the celebrated
Running of the Bulls in Spain.

GRAUDINS AND FLEMING


COPYRIGHT 2009

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