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Lime and Lye: Two Strong Alkalis
Introduction
Lime is a very important chemical which is of central importance to many industries
including several that we will discuss in these pages. We will use it initially to
produce lye for making soap. Later we will use it to make glass. Lime is also widely
used in agriculture, water treatment, paper manufacture, and in mixing cement and
concrete. Unlike many other chemicals whose manufacturing technology has changed
over time, lime is manufactured today by essentially the same process as was used in
antiquity. Calcium appears in the second column of the periodic table, the alkaline
earths, along with magnesium and barium.

U.S. Production of lime was 15 billion kg in 1989 making it the 6th most-produced
chemical in the U.S.

One problem with lime, however, is that it is not very soluble in water. When lime
and soda ash combine in a classic metathesis reaction, they produce lye, or sodium
hydroxide. Lye combines the solubility of soda ash with the strong alkalinity of lime.
We will need this combination of strength and solubility when we make soap.

U.S. Production of lye was 10 billion kg in 1989 making it the 9th most-produced
chemical in the U.S.

The Chemistry of Lime

We have learned about two classes of minerals: the silicates and the aluminosilicates.
The carbonates form another commercially important class of minerals. Aragonite
and calcite are two minerals formed from calcium carbonate (CaCO3), while dolomite
is a mineral containing calcium magnesium carbonate (CaMg(CO3)2). Rocks formed
from calcite and dolomite minerals are called limestones. They are formed either from
the accretion of carbonaceous animal remains (seashells, coral, microfossils) or from
the precipitation of dissolved calcium carbonate from mineral waters. Calcium
carbonate is white in color, though impurities may lend color to rocks and minerals.
The carbonates are chalky in consistency. In fact, chalk is one variety of limestone,
though modern classrooms use "chalk" made of gypsum (calcium sulfate).

Lime (calcium oxide) is produced by heating limestone or seashells (calcium

carbonate). The chemistry of calcium carbonate is similar to that of sodium carbonate
and potassium carbonate except that calcium carbonate is not soluble in water.
Consequently, calcium carbonate does not produce an alkaline solution in water as
sodium and potassium carbonate do. When calcium carbonate is heated, carbon
dioxide is driven off leaving calcium oxide behind.

(I) CaCO3(s) -----> CaO(s) + CO2(g)

In order to effect this conversion, the limestone must be heated to temperatures in

excess of 1000°C (1800°F), approximately the same temperature as required to vitrify
clay to pottery. In ancient times this was done by simply heating crushed limestone in
a bonfire in a process called simply "burning lime." Today, huge drums are used to
hold the crushed limestone, which is heated by coal, oil, or natural gas, but the
chemical process is essentially the same. Another name for "heating the bejeesus" out
of something is calcination. Another name for calcium oxide is quicklime.

When lime is added to water in a process called "slaking," calcium oxide is converted
to calcium hydroxide, or "slaked lime."

(II) CaO(s) + H2O(l) <-----> Ca(OH)2(s)

While limestone is insoluble in water, slaked lime is marginally soluble in water.

(III) Ca(OH)2(s) <-----> Ca2+(aq) + 2 OH-(aq)

Such a solution is more alkaline than an equivalent solution of potash or soda ash.
Thus lime is often used when large quantities of a strong but inexpensive base are
required. Agriculture, water treatment, and paper manufacture are industries which
use lime for this reason.

Lime has two advantages over potash. First, it is a stronger base than either sodium or
potassium carbonate. Second, unlike potash, it can be produced in large quantities.
Remember: a lot of wood produces a little ash and a lot of ash produces a little potash.
But limestone is a very common stone. We can quarry it and produce lime on a grand
scale.
The main disadvantage of lime is its limited solubility. Whereas sodium carbonate has
a solubility of 22 g/100 mL and potassium carbonate has a solubility of 147 g/100 mL
(!), the solubility of calcium hydroxide is only 0.19 g/100 mL. Even worse, most
calcium compounds are even less soluble, e.g. calcium carbonate has a solubility of
only 0.001 g/100 mL. So many anions present in the solution may form insoluble
precipitates in limewater. In particular, soap contains anions which, in the presence of
calcium, form the insoluble precipitate commonly known as "soap scum."

If lime is left exposed to the atmosphere, it will, over time revert back to calcium
carbonate by absorbing carbon dioxide from the air:

(IV) Ca(OH)2(s) + CO2(g) <-----> CaCO3(s) + H2O(l)

In other words, the soluble material, slaked lime, if left exposed to the air converts to
the insoluble material, limestone. What we have here is the first cement! Modern
cements are more sophisticated and "cure" more quickly than slaked lime, but lime
continues to be a major compenent of modern cements. When quicklime is painted on
wood, it forms a rock-hard white coating called whitewash.

The Chemistry of Lye

Lye can be made very easily from lime and soda ash using a classic metathesis
reaction:

(V) Ca(OH)2(aq) + Na2CO3(aq) -----> 2 NaOH(aq) + CaCO3(s)

Two solutions are mixed together and a solid precipitate forms. The "good stuff," lye,
remains in solution. If potash replaces soda ash, the result is potassium hydroxide.

While lime is more alkaline than soda ash, when reacted together they produce a
stronger alkali than either of the two separately. Synonyms for lye are caustic soda,
and sodium hydroxide. It remains one of the most important alkalis in modern
chemical industry though it is no longer manufactured from lime and soda ash. In
addition to its many uses in chemical manufacture, it is the most common ingredient
in drain openers and can be bought in the grocery store in the drain opener section. It
combines the strength of lime with the solubility of potash. Because of this
combination, it is ideal for making soap. However, because it requires both lime and
potash for its manufacture, it remained a rather expensive alkali well into this century.

pH
The pH scale is discussed under potash . We have seen the pH and pOH values for
several solutions with a concentration of 1% (i.e. 1 gram of compound in 100 grams
of solution). But the solubility of calcium hydroxide is only 0.19 g/100 mL. That is,
no matter how much calcium hydroxide we add to 100 mL of water, only 0.19 g will
actually dissolve. Even so, a saturated solution of calcium hydroxide has a pH of 12.

Compou Dominan H+ Concentrati p OH- Concentrat pO

Test Paper
nd t Species on H ion H
Acetic CH3COO
0.0001 4 0.0000000001 10
acid H
Carbonic
H2CO3 0.00001 5 0.000000001 9
acid
Pure
H2O 0.0000001 7 0.0000001 7
Water
Potassium
Bicarbona HCO3- 0.00000001 8 0.000001 6
te
Potassium
CO32- 0.0000000001 10 0.0001 4
Carbonate
Calcium
0.00000000000
Hydroxid OH- 12 0.01 2
1
e
Potassium
0.00000000000
Hydroxid OH- 13 0.1 1
01
e

Other Lime Pages

 Calcite
 Aragonite
 Companies that produce lime
 Restoration of a lime kiln in Kansas
 Vulcan Ironworks builds lime kilns
 Riverside Cement's Oro Grande lime kiln
 Lime Kiln Theater in Lexington, VA

Lime and Lye Quiz

The lime and lye quiz consist of three questions on any of the following topics
discussed in this page.

 Know how lime is made from limestone (Eqns I-IV).

 Know how lye is made from lime and soda ash (Eqn V).
 Know which compounds of calcium are soluble in water (see metathesis).
 Know the relative advantages and disadvantages of lime compared to potash.
 Know the relative advantages and disadvantages of lye compared to lime and
potash.
 Know the chemical names and formulas for lime and lye.
 Know where calcium carbonate is found in nature.
 Know how the pH scale is used to quantify acidity and alkalinity.
 Know the meaning of the terms calcination and slaking.

 Take a practice quiz online.

Safety and Common Sense

Calcium carbonate is about as harmless as harmless gets. Of course, it is possible to
hurt yourself, but it seems rather farfetched outside an industrial setting. You
shouldn't breath the dust, or eat it by the spoonful, but it is a common ingredient in
foods and the principle ingredient in antacids that promote themselves as supplying
calcium.

Lime is another matter. More caustic than potash or soda, quicklime (calcium oxide)
gets hot when water is added, and even slaked lime (calcium hydroxide) is caustic
enough to warrant respect. You shouldn't eat it or get it in your eyes. First aid for eyes
is to wash with cold water. If you eat a lot you can call a poison control center(VA 1-
800-451-1428). But don't go overboard. Slaked lime is added to many foods to
counteract excess acidity. It is used in pickling, for example.

Lye is the most caustic of the alkalis we will use. You should definitely keep it off
skin, out of eyes, and out of mouth. Skin should be washed if you get a little careless.
If you get it in your eyes, you should wash them immediately with cold water and call
a hospital. A taste will leave a very unpleasant taste in your mouth. If you are
foolhardy enough to eat it by the spoonful, you should call a poison control center and
head immediately for the emergency room. I hope you make it.

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.
  Calcium Carbonate
 Calcium Oxide
 Calcium Hydroxide
 Sodium Hydroxide

Instructions
Our goal is the conversion of insoluble limestone to soluble lime. To accomplish this,
we need to heat the bejeesus out of crushed limestone. It might be possible to get a
campfire hot enough to accomplish the conversion. But to secure the efficient
conversion to lime, it is better to use a kiln. This can be as simple as a chimney loaded
with wood and limestone. We will use our pottery kiln (either woodfired or electric)
to reach these high temperatures.

Limestone continues to be quarried to this day and can be bought in 50 pound sacks at
any agricultural or gardening supply. You will need a handfull of limestone and a pot
to put it in. You can use the pot you made in the pottery project or you can build a
new pot just for this purpose. Place your pot of limestone in the kiln and fire it as you
would any other pot. The kiln should be set to cone 06 (980°C, 1800°F). Higher
temperatures would accomplish the conversion more quickly and completely, but
would require a higher temperature clay than the one we are using.

If you are firing with wood, it is essential that you do not put the fire out with water.
Water would wash away your lime (which is soluble in water) and ruin all your hard
work.

When the kiln is cool, take your calcined limestone, which may contain a mixture of
lime and limestone, and place it in a 2 L soda bottle. Fill the bottle with water. If the
solution gets hot, you know you are on the right track, since lime heats up as it slakes.
Let the unreacted limestone settle to the bottom. The "good stuff," the lime, should be
in solution. Let it settle and clear and then pour it into a second bottle, leaving the
sediment behind.

If you wanted dry lime, you could boil the water away, as you did when you made
potash. But for this project, slaked lime solution is good enough. You will know your
solution is good if it tastes bitter.

Criteria for Success

You should already have passed the lime and lye quiz when you bring me your lime
solution for evaluation. It should turn test paper blue. When I add a solution of
washing soda, your solution should get cloudy. Of course, you know why. If your
solution does not turn test paper blue, or does not turn cloudy when washing soda is
added, or you don't know why it should turn cloudy, you fail. Of course, you can try
again.

The word lime means different things to

different industries. In agriculture, it may
refer to limestone or to slaked lime. You
have to take care to understand what you
are getting. This bag is actually slaked
 lime.

Slaked lime is also used in making pickles.

Sodium hydroxide is sold as lye in the drain opener department of many gorcery and
hardware stores. Most solid drain openers contain lye plus other ingredients. Red
Devil lye claims to be 100% lye (but of course, we know that nothing is 100% pure).
Still, it doesn't intentionally contain anything but sodium hydroxide. Another
synonyms for lye is caustic soda.

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