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A Primitive Alkali: Potash
Introduction
Fire has been quite useful to us, both for the production of warmth and for the
conversion of materials from one form to another (e.g. clay to pottery). Even the
ashes left over from the fire turn out to have useful properties. Early people
discovered that wood ashes could be used for cleaning. This may seem
counterintuitive to us, since we usually associate ashes with dirt. But wood ashes
are not simply dirt. The major components of wood ashes are potassium carbonate
(potash) and sodium carbonate (soda ash). From a chemical standpoint these two
compounds are very similar. So similar that while ashes have been used for
millennia the difference between sodium and potassium carbonate was only
recognized in the 19th century. The elements in the first column of the Peridic
Table, containing sodium and potassium, are called the alkali metals.

Potash was man's first base. A base is a material which removes hydrogen ions (H+)
from aqueous solution. We also refer to such a material as an alkali. Alkali's have a
bitter taste an a slighltly soapy feel when rubbed in the fingers. The isolation of
alkali is the precursor to making true soap.

Even today potassium and sodium carbonate remain extremely important

chemicals. U.S. Production of sodium carbonate alone was 9 billion kg making it the
11th most-produced chemical in the U.S.

The Chemistry of Potash

You will recall from the metathesis project that all sodium and potassium
compounds are soluble in water. When an ionic compound dissolves in water it
dissociates into cations (positive ions) and anions (negative ions). For potash we
write:

(I) K2CO3(s) -----> 2 K+(aq) + CO32-(aq)

Before we proceed we need to discuss a little of the chemistry of water itself. Like
ionic compounds, water has the capacity to ionize, that is, to break apart into ions.
In any sample of water a tiny fraction of the water molecules will be ionized
according to the reaction:

(II) H2O(l) <-----> H+(aq) + OH-(aq)

The double arrow signifies that water is in equilibrium with hydrogen ion and
hydroxide ion. At any given time there will be lots of water, a little hydrogen ion,
and a little hydroxide ion present. In pure water at room temperature, for example,
1 water molecule out of 556 million will be ionized. Because one water splits into
one H+ and one OH-, the H+ and OH- concentrations are equal in a neutral solution.
When an ionic compound dissolves in water, it may absorb or release hyrogen or
hydroxide ions. If the net effect is that hydrogen ions outnumber hydroxide ions,
the solution is called acidic. If there are more hydroxide ions, than hydrogen ions
the solution is called basic or alkaline.

We have already seen our first acid. When wine or mead "goes sour," bacteria
oxidize ethanol to acetic acid. Acetic acid ionizes to produce hydrogen ions and
acetate ions:
CH3COOH(aq) <-----> H+(aq) + CH3COO-(aq)
The net effect is that hydrogen ions are produced and hence the solution is acidic.
An acidic solution tastes sour.

When posassium carbonate dissolves in water, it ionizes into potassium and

carbonate ions, as we have seen. Once in solution, the potassium ions simply float
around and are very unreactive. We call such an ion a spectator ion because it does
not participate in further chemical reactions. The carbonate ion, on the other hand,
acts as a base in aqueous solution, that is, it absorbs hydrogen ions wherever it
finds them. The reaction we write depends on whether the solution was acidic or
basic to begin with. In acidic solution we write:

(IIIa) CO32-(aq) + H+(aq) <-----> HCO3-(aq)

while in alkaline or neutral solution we write:

(IIIb) CO32-(aq) + H2O(l) <-----> HCO3-(aq) + OH-(aq)

The carbonate ion will react with whatever species is around. If there is lots of
hydrogen ion (acidic solution) the hydrogen ion sticks to the carbonate ion and
forms a new ion, the hydrogen carbonate ion, or bicarbonate ion. If there is not
much hydrogen ion around, carbonate in effect steals a hydrogen ion from water,
leaving a hydroxide ion behind and producing an alkaline solution. Notice that once
again we have used a double headed arrow to denote an equilibrium rather than a
reaction that goes to completion.

There are two more reactions that further complicate the picture. First, if the
solution is really acidic, the bicarbonate ion can also stick to a hydrogen ion:

(IVa) HCO3-(aq) + H+(aq) <-----> H2CO3(aq)

or
(IVb) HCO3-(aq) + H2O <-----> H2CO3(aq) + OH-(aq)

H2CO3 is called carbonic acid. Carbonic acid can can decompose into water and
carbon dioxide gas:

(V) H2CO3(aq) <-----> H2O(l) + CO2(g)

You may have noticed this phenomenon in fermenting mead. The yeast produces
carbon dioxide gas. You can detect the production of this gas because when the
bottle is sealed, it becomes pressurized. Only a thin layer of bubbles appears on top
of the mead. But if the cap is opended, the mead blossoms into a foamy brew
teaming with bubbles. Before your opened the cap, the carbon dioxide gas was
dissolved in the mead. When the cap was opened and the pressure released, carbon
dioxide came out of solution, escaping as a gas.

This sequence of equilibria is also active in carbonated beverages. When water is

pressurized under carbon dioxide gas, some of the gas dissolves. Some of the
dissolved gas combines with water to form carbonic acid. Some of the carbonic acid
splits into hydrogen ion and bicarbonate ion. Some of the bicarbonate ion further
splits into hydrogen ion and carbonate ion. All five species will be present but
depending on the acidity of the solution there will be more of one than another.

pH
It is useful to be able to quantify acidity. Scientists use the pH scale to do this. pH
(pee Aych) is defined as the negative of the common logarithm of the hydrogen ion
concentration. In mathematics, the common log is used to count the order of
magnitude of a number, i.e. to count the number of zeros. For example, in pure
water, the H+ concentration is 0.0000001 moles/L. There are seven zeros in this
number, and the pH is 7.

The flip side of this specification is the OH- concentration and the negative of the
common log of this concentration is called pOH (pee Oh Aych). Because water can
ionize into H+ and OH-, it turns out that pH + pOH = 14. In an acidic solution there
are lots of H+ ions floating around but not very many OH- ions, and the pH is low. In
a neutral solution, there are equal numbers of H+ and OH- ions and the pH is 7. And
in an alkaline solution, there are few H+ ions, lots of OH- ions, and the pH is high. Of
course, the concentration of the ions depends on the concentration of the solution.
So to make a fair comparison, we should compare solutions with the same total
concentration. Here are the pH and pOH values for several solutions with a
concentration of 1% (i.e. 1 gram of compound in 100 grams of solution):

Dominant H+ OH-
Compound pH pOH Test Paper
Species Concentration Concentration

Acetic acid CH3COOH 0.0001 4 0.0000000001 10

Carbonic H2CO3 0.00001 5 0.000000001 9

acid

Pure Water H2O 0.0000001 7 0.0000001 7

Potassium HCO3- 0.00000001 8 0.000001 6

Bicarbonate

Potassium
CO32- 0.0000000001 10 0.0001 4
Carbonate

One of the most convenient ways to measure pH is with an indicator. An indicator is

a substance which changes color when the pH changes. There are many indicators.
You may have noticed, for example, that tea turns from dark brown to tan when
lemon juice (an acid) is added. We will use test paper which changes from blue
(alkaline) to green to yellow (neutral) to orange to red (acidic).

Recrystalization as a Purification Technique

One of the most fundamental problems in chemistry is that of purifying a substance.
We have seen that most things in nature are actually mixtures, either homogeneous
or heterogeneous. But to have any control over chemical reactions, a chemist must
first be assured that his starting materials are pure. Later in the course we will look
at distillation as a technique for purifying substances that are gases or liquids under
ordinary conditions. For solids, however, we turn to recrystalization as our primary
purification technique.

We have seen that a mineral, particularly a crystalline mineral, is essentially a pure

substance, either element or compound. How are such minerals formed in nature?
One possibility is that the mineral crystals cooled from molten rock. Another is that
the crystals formed from substances dissolved in water. It is this mechanism which
we will try to exploit in this project.

In the metathesis project we discussed solubility as if it were a yes or no

proposition. In reality it is a little more complicated. You know from everyday
experience that sugar is soluble in water. If you add a single grain of sugar to 2
liters of water, the sugar will all dissolve--no solid sugar will remain. And if you add
a second grain, it too will dissolve. In fact, if you add a teaspoon of sugar, the entire
amount will dissolve. You may add a second and a third teaspoon, but anyone who
has ever added sugar to tea or coffee knows that there comes a point where the
water is saturated with sugar, that is, all the sugar that can dissolve, has dissolved.
Any sugar in excess of this amount will just settle to the bottom as a solid. The
amount of a material which will dissolve in a given amount of water is called its
solubility. Here are solubilities of some common substances:
Substance Solubility (grams/100 mL water)
Cold Hot
potassium carbonate 147 331
calcium chloride 75 159
sodium chloride 36 39
potassium chloride 34 57
sodium carbonate 22 421
calcium carbonate 0.001 0.002

Suppose, then, that I start with an ancient sea. Dissolved in the seawater are all
kinds of things dissolved out of the soils and rocks in the area which drains into the
sea. Some of these substances, like sodium chloride, have high solubility while
others, like calcium carbonate, have low solubility. Eventually, the geological
conditions change, the sea is cut off from the ocean, the drainage patterns change,
and the sea begins to dry out, perhaps over the course of hundreds of thousands of
years. The Dead Sea and the Great Salt Lake are two modern examples of such a
situation. Now, as the sea evaporates it becomes more concentrated until it becomes
saturated in the least soluble material it contains. Like the excess sugar added to
tea, this least soluble material falls to the bottom and is deposited as a layer,
perhaps calcium carbonate. As the evaporation continues, the substances present
are deposited in reverse order to their solubilibies. Finally, the most soluble
substances present are deposited as the uppermost stratum as the sea gives up the
last of its moisture. The substances deposited depend on what was present in the
original sea, and the order in which they are deposited depends on their relative
solubilities.

One more hitch in the story is that solubility depends on temperature. Notice that
while the solubility of sodium chloride is about the same in hot and cold water, the
solubility of sodium and potassium carbonate is much greater in hot water than in
cold water. We will exploit this property in separating the soluble carbonates from
the other components of wood ash.

Wood Ashes
Whatever we extract from wood ashes must be there to begin with. Wood ashes are
a complex heterogeneous mixture of all the non-flammable, non-volatile minerals
which remain after the wood and charcoal have burned away. Because of the
presence of carbon dioxide in the fire gases, many of these minerals will have been
converted to carbonates. Burned soil may also be present. So the ashes probably
contain predominately sodium and potassium carbonate, sodium and potassium
chloride, silica, and calcium carbonate.

If we add the ashes to water, the soluble potassium and sodium salts will dissolve
while the insoluble silica and calcium carbonate will settle to the bottom. We can
then drain off the water (containing the "good stuff") and throw the insoluble
material away. To separate the chlorides from the soluble carbonates, we will
exploit the greater solubility of the carbonates in hot water. We will bring the liquid
to a boil and continue boiling until enough water boils away for an insoluble
precipitate to form. This is very likely a mixture of sodium and potassium chloride.
From this point, we will continue boiling until half of the remaining water is
removed. At this point we can be reasonably certain that only the soluble
carbonates remain in solution. We will carefully pour off the hot liquid into another
container, leaving the solid material behind. As the liquid cools to room
temperature, the less soluble sodium carbonate will precipitate leaving the more
soluble potassium carbonate in solution. Finally, the remaining solution can be
drained off and boiled to dryness, producing solid potassium carbonate.

One of the observations you make should be that it takes a lot of wood to make a
little ash and a lot of ash to make a little potash. Thus, while it is not particularly
difficult to extract potash from wood, you will go through an enormous amount of
wood to produce commercial amounts (pounds and tons) of potash. This will have
implications for us later in the semester.

Other Potash Pages

Isonex is a consultant to the soda ash industry
Trona, California
Solvay is the largest producer of soda ash in the world
Solvay Minerals mines trona ore in Green River, Wyoming
USGS Soda Ash Report
Chemical Industries Newsletter report on Soda Ash
Companies that manufacture alkali
Companies that mine potash
 Arm and Hammer makes baking and washing soda

Potash Quiz
The potash quiz consist of three questions on any of the following topics discussed
in this page.

Know what species are present in a potash solution (Eqns I-V).

Know which of these species are acidic and which are alkaline.
Know the chemical names and formulas for potash and soda ash.
Know how soluble compounds are deposited geologically.
Know how recrystallization can be used to purify compounds.
Know how the pH scale is used to quantify acidity and alkalinity.
Know the difference between baking soda and washing soda.

Take a practice quiz online.

Safety and Common Sense

Just because potash and soda ash are "natural" and you are extracting them from
wood ashes, doesn't mean they are safe. Just because they are chemicals with
chemical names and formulas doesn't make them dangerous. When thinking about
chemical hazards, you should always consider the amount and concentration of the
substance in question. Potash makes up only a small percentage of wood ashes,
which are not particularly hazardous. But as the potash is extracted, concentrated,
and purified, it becomes more deserving of care.

Potash and soda ash are relatively strong alkali's. The are moderately caustic, which
means they will damage skin. Consequently, you should not rub them all over your
body or get them in your eyes and you should not eat them. Nevertheless, they don't
warrant paranoia. If you get some on your skin, wash it off. You should wear glasses
to protect your eyes, but if some gets in, you should splash cold water into your
eyes. You should not eat it. It's not good for you. But a little taste will do you no
harm. If you are foolhardy enough to eat several teaspoons of it, call the local
poison control center (VA 1-800-451-1428).

Information on chemical hazards is summarized in a Material Safety Data Sheet for

each compound. These sheets often tell you more than you want to know, but they
are worth looking at.

Potassium Carbonate
Sodium Carbonate

Instructions
Our goal is to extract as much of the soluble carbonates from wood ashes as
possible while leaving behind the insoluble components. You will need a couple of
handsful of wood ashes, some water, our old friend, the 2 L soft drink bottle, and a
pottery bowl, non-aluminum saucepan, or glass beaker. The first container (2 L
bottle) need only hold water. We use the soft drink bottle for convenience. The
second container needs to be fire and water proof. If we were going for historical
accuracy, we would use pottery. But any pan or beaker that can be used on a stove
will work. Do not use an aluminum pot. Aluminum reacts with strong bases and
your project will be ruined.

Place your wood ashes into the 2 L bottle until it is about 1/3 full of ashes. Fill the
rest of the bottle with hot water, place the cap on the bottle and shake it up. The
soluble carbonates (as well as any other soluble materials) will dissolve while the
insoluble silicates, carbonates, aluminosilicates, and any other insoluble materials
will settle to the bottom. Any charcoal present will float to the top. Place the bottle
where it will not be disturbed and let it sit overnight.

The next day you should find that the sediment has settled to the bottom, the
charcoal is floating on the top, and the water in between is clean and clear. Remove
the cap and give the bottle a gentle squeeze to force the charcoal up and out of the
bottle. Then carefully pour about 1 L of the clear water into a pan or beaker. Stop
pouring before any of the stirred-up sediment reaches the mouth of the bottle. What
you should have now is a pan with about 1 L of what looks like clear water. If you
taste it and it tastes a little bitter or soapy, you are on the right track.

Place the pan onto the stove or hotplate and place a spoon or glass rod into it to
prevent superheating (which can lead to splattering). Bring the water to a boil and
continue boiling until all the water has evaporated. A little bit of scale or fine grey
powder will remain in the pan. Let it cool and then scrape it into a container. This is
your product. It contains all of the soluble materials which were present in the the
ashes to begin with. This could include sodium and potassium chlorides, sulfates,
hydroxides, and carbonates. Of these, only the hydroxides and carbonates are basic.
I will test your product with pH test paper to determine whether it is alkaline.

If you were interested in further purifying your product, you could recrystalize it
again. This time you would start with your crude product (instead of ashes), dissolve
it in water, boil it until it was almost dry, and filter it while hot to remove any
materials less soluble than the carbonates. You would then allow it to cool and the
carbonates would precipitate out leaving anything more soluble still in solution. By
repeated application of this procedure, you could even separate sodium carbonate
from potassium carbonate. But for our purposes, you crude potash should be
alkaline enough. To test it for yourself, just taste it. It should taste bitter, like soap.

Criteria for Success

You will have already passed the potash quiz when you bring your potash for
evaluation. Your potash must be grey or white, with no obvious contamination. A
wet pH test paper should turn blue when touched to your potash. Of course, if you
fail, you can try again (once per day) until you pass.

Sodium carbonate is sold as washing soda. Other synonyms are soda ash and soda.
You can buy washing soda in some grocery stores, on the laundry detergent aisle,
next to the borax. It is used to remove calcium from hard water by forming an
insoluble precipitate of calcium carbonate.
 Sodium bicarbonate, a much milder alkali than sodium
carbonate, is sold as baking soda. It is also called sodium
hydrogen carbonate. It is used in baking, as the name
suggests, and is a common ingredient in antacid tablets. You
can buy baking soda in the grocery store on the baking goods
aisle. In the presence of acids, it gives off carbon dioxide,
which makes bread and cake nice and fluffy. Baking powder
contains baking soda along with an acid.

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