Chloralkali

A Crisis in the Soap and Glass Industries

We have seen the usefulness of soda ash and potash (sodium carbonate and potassium
carbonate) both as an alkali in the production of lye for soap and as a flux in making
glass from silica and lime. By 1750, the demand for soda ash and potash exceeded the
industrial capacity for producing it from the tradional sources, i.e. the leaching of ashes.
Another development contemporaneous to this soda crisis was the increasing demand
for bleaches in the textile and paper industries. Up until that time, sour milk and potash
were used for bleaching cotton and linen. The cloth was soaked in this solution and laid
out in the sunlight for 3-6 months. This created a bottleneck in cloth production which
was time-consuming, dependent on the weather, and required large areas for laying out
the cloth. Wool was bleached by passing the fumes from burning sulfur over it. As we
have smelled, sulfur dioxide is not very pleasant to breathe, and consequently a
bleacher's job did not promote good health.
A third development at this time was the discovery that sulfuric acid could be used to
mordant indigo on wool. Indigo, one of the most popular dyes of all times, had
previously been colorfast only on cotton and linen. In 1746, John Roebuck pioneered the
lead chamber process for the manufacture of cheap sulfuric acid in several ton
quantities. The increasing availability of sulfuric acid has a bearing on our story, as we
shall see.
In 1775, the French Academy of Sciences offered a prize for a process whereby soda ash
could be produced from salt. Salt can be produced by the evaporation of seawater and it
can be mined from large underground deposits. The French Academy wanted to promote
the production of much-needed sodium carbonate from inexpensive sodium chloride.
By 1790, Nicolas Leblanc had succeeded in producing soda ash from salt by a 2-step
process. In the first step, sodium chloride is mixed with concentrated sulfuric acid at
temperatures of 800-900 C:
H2SO4(l) + 2 NaCl(s) -----> Na2SO4(s) + 2 HCl(g)
The hydrogen chloride was sent up the stack leaving solid sodium sulfate. In the second
step, the sodium sulfate is crushed, mixed with charcoal and limestone and again heated
in a furnace:
Na2SO4(s) + 2 C(s) + CaCO3(s) -----> Na2CO3(s) + CaS(s) + 2 CO2(g)
The carbon dioxide went up the stack, leaving a mixture of sodium sulfate and calcium
sulfide. Anyone who has passed the metathesis project can tell you that sodium sulfate is
soluble in water, while calcium sulfate is not. So these two can be separated by
dissolving the mixture in water, pouring off the water with its dissolved soda ash, and
then evaporating the water to produce dry soda ash.
The prize was awarded in 1783 to Nicolas Leblanc for a process which used sea salt and
sulfuric acid as the raw materials. By 1791 a plant was in operation producing 320 tons
of soda ash per year. But two years later the plant was confiscated by the French
revolutionary government, which refused to pay him the prize money he had earned ten
years earlier. In 1802 Napoleon returned the plant (but not the prize) to him but by then
Leblanc was so broke he could not afford to run it. He killed himself in 1806.
Nevertheless, the process became the mainstay of the alkali industry and by 1885 it was
being used to produce more than 400,000 tons per year.
Using only salt, sulfuric acid, charcoal, and limestone as raw materials, sodium
carbonate could be produced inexpensively. The products of this process were carbon
dioxide (up the stack), hydrogen chloride (up the stack), and calcium sulfide. The
gaseous products were no immediate concern. Granted, the acidic hydrogen chloride
(hydrochloric acid) would devastate trees and vegetation in the vicinity of the soda plant,
but progress has a price. In response to C complaints, the hydrogen chloride was
dissolved in water to produce hydrochloric acid, which was dumped into lakes and
streams. But this merely substituted water pollution for air pollution. The calcium
sulfide was another problem. Left in landfills, it slowly reacts with water producing
sulfur dioxide and hydrogen sulfide, two extremely foul and toxic gases. Aternatively, it
could be hauled off and dumped in the ocean. By 1863, the situation had become so bad
in Britain that Parliament passed the Alkali Act, forbidding such pollution.
In response, soda producers introduced several more steps to reduce this pollution. The
calcium sulfide was reacted with carbon dioxide (from the original process) and water:
CaS(s) + CO2(g) + H2O(l) -----> CaCO3(s) + H2S(g)
The hydrogen sulfide was then used as a feedstock for the lead chamber, which
produced much needed sulfuric acid. By 1874, Henry Deacon had devised a process to
reduce HCL emmissions as mandated by the Alkali Act. In this process, hydrogen
chloride is oxidized by oxygen over a copper chloride catalyst:
4 HCl(g) + O2(g) -----> H2O(g) + Cl2(g)
From this point on, the Leblanc-Deacon process became a major producer of chlorine
used as a bleach in the paper and textile industries. In time, the profits from chlorine
sales exceeded those from the sale of sodium carbonate. Thereafter, the main product of
a Leblanc plant was chlorine and sodium carbonate was sold at a loss.
By 1863 a Belgian named Ernest Solvay had developed a competitive process which
was free of many of the practical problems posed by the Leblanc process. It uses
ammonia, lime and salt as raw materials and produces sodium carbonate and calcium
chloride as products. There is a large market for sodium carbonate but not for calcium
chloride. But calcium chloride is not noxious as the waste product of the Leblanc
process were, and so the pollution problem was minimal. At first, the established alkali
producers gouged prices in order to stifle new competition. But this could only go on so
long and by 1915 sodium carbonate was being manufactured almost exclusively by the
Solvay process.
Soda ash continues to be manufactured by the Solvay process in Europe. But in the U.S.,
mining of trona ore in Wyoming increased throughout the 1960's and has all but
eliminated domestic production of Solvay soda ash. But let's remember where demand
for soda ash came from. It was needed to make lye for the soap industry. As cheap
electricity began to be available at the turn of the 20th century, the soda ash was about to
be replaced by electrolytically produced lye as the principle alkali for soap making.
Nevertheless, soda ash continues to be in demand for glass making. U.S. soda ash
production now stands at about 9 billion kg annually making it the 11th chemical in
order of domestic production volume.
And remember, the Leblanc process had created the expectation of inexpensive chlorine.
With the coming of large-scale electrical power generation in the 1890's, the chloralkali
industry was born.

Redox Reactions
We have seen that we can use redox reactions to produce electricity. It turns out that we
can also use electricity to drive redox reactions. In particular, we can use electricity to
accomplish reactions which normally don't want to go. We take as an example the
production of lye and chlorine from sea salt.

Chloralkali
Traditionally, lye had been manufactured from soda ash and lime. But in the 1890's
cheap electricity became available in large quantities for the first time. If electric current
is passed through a saltwater solution, hydrogen bubbles off one electrode and chlorine
bubbles off the other. Over time, the sodium chloride is converted to sodium hydroxide,
which, after all, is an even more powerful alkali than sodium carbonate. The chlorine gas
produced found a market in the paper industry as a bleach wood pulp that would not
otherwise be usable. If you had to rely on battery power, the process would not be
economical since it takes considerable energy to produce the metals used in the battery.
But at the dawn of the 20th century, cheap electrical power was becoming available,
particularly in areas where hydroelectric power was available. Consequently, alkali
plants were established in Norway and in the Niagara Falls area. Domestic production of
chlorine and lye stand at about 10 billion kg each, making them 8th and 9th in U.S.
production volume.
The chloralkali process is a redox reaction:
2 NaCl(aq) + 2 H2O(l) -----> 2 NaOH(aq) + H2(g) + Cl2(g)
Normally this reaction doesn't go. Saltwater does not spontaneously decompose into
hydrogen (explosive) and chlorine (poisonous). Lucky for us! But let us look at the half
reactions:
2 NaCl(aq) + 2 H2O(l) -----> 2 NaOH(aq) + Cl2(g) + 2 H+ + 2 e-
2 H+ + 2 e- -----> H2(g)
Just as in the galvanic cell, we can separate the oxidation and the reduction in separate
compartments. In a reaction which wants to go, we can charge the electrons a price for
the priviledge of passing through the wire which connects the anode to the cathode. We
collect this price in the form of work which the electrons perform as they pass through
an electromagnet or motor.
But if the reaction doesn't want to go, we can force the electrons through the wire in the
direction opposite to that which they would normally go. In essence, we perform work
on the electrons by sending them through the wire backwards and thus drive the reaction
in the opposite direction from the one it would normally take.

Two New Hotdogs

We can even do stoichiometry with these electrons by realizing that we measure out a
mole of electrons by their charge rather than their mass. For example, let's figure out
how long it would take to produce a kilogram of lye by passing a 100 Amps of current
through a saltwater solution:
hour = (1000 g NaOH/100 amp)(1 mole NaOH/40 g NaOH)(2 mole e/2 mole NaOH)
(96500 coulomb/mole e)(1 amp second/coulomb)(1 hour/3600 second)
=6.7 hours
How much energy are we talking about? Well, we are passing 100 amps at 3 volts for
6.7 hours so the total energy consumed is
kW-hr = (100 amps)(3 volts)(6.7 hours)(1 Watt/volt amp)(1 kW/1000 W)
=2.0 kW-hr
In Virginia electricity costs about 6 cents per kW-hr, so to produce 1 kg of lye we are
talking about 12 cents worth of electricity.
We are also producing gases. It turns out that a mole of any gas occupies about 24 L at
room temperature. So in producing our 1 kg of lye, we will also produce:
L Cl2 = (1000 g NaOH)(1 mole NaOH/40 g NaOH)(1 mole Cl2/2 mole NaOH)(24 L
Cl2/mole Cl2)
=300 L Cl2
This sounds like a lot of chlorine, but it is less than 1 cubic meter (1000 L). How many
liters of hydrogen will be produced along with the production of 1 kg of lye?
We can do any stoichiometry problems involving elecricity if we just remember two new
hotdogs:
(96500 coulomb/mole e)
and
(1 amp second/coulomb)
We will also find useful an old hotdog we haven't used too much:
(24 L / mol of gas)

Sodium
Let's first consider why lye is produced in the electrolysis of brine instead of sodium.
Sodium is a very reactive metal, so reactive that it reacts violently with water to produce
hydrogen gas:
2 Na(s) + 2 H2O -----> 2 NaOH(aq) + H2(g)
That is, sodium is a more powerful reducing agent than water. Sodium metal reacts with
water releasing enough heat to melt the sodium and set fire to the hydrogen. When we
electrolyse brine, any sodium produced reacts immediately with water and so the
products are chlorine, hydrogen, and lye rather than chlorine and sodium.
If we want to produce sodium, we have to do away with the water. But we have to have
an electrolyte in order to conduct the electricity. now we used aqueous solutions in the
first place because electrolytes ionize in water:
NaCl(s) -----> Na+(aq) + Cl-(aq)
and these ions are what carries the electric current through the solution.
What we really need is a non-aqueous, ionized electrolyte. We can produce this simply
by melting the salt. If electric current passes through molten sodium chloride, metallic
sodium will be produced at the cathode and chlorine gas will bubble off of the anode:
2 NaCl(l) -----> 2 Na(l) + Cl2(g)
Can you balance this redox reaction to determine how much current is needed to
produce a given amount of sodium in a given time? The melting point of sodium
chloride is fairly modest: 801°C Sodium is produced commercially by the electrolysis of
molten sodium chloride.

Perhaps the Most Important Lesson in the

Whole Course
Popular culture is fond of blanket statements, particularly about chemistry. Sodium is
bad for you. Lead is bad for you. Chlorine is bad for you. What most people in the world
today don't understand is the enormous difference between the properties of elements
and their compounds. The chemistry of sodium and chlorine couldn't be a better case in
point.
 •Sodium is a low-melting metal which reacts violently, and even explosively with
water.
•Chlorine is an acutely toxic gas used on the battlefields of World War I.
•Sodium chloride is a common household product which can be eaten by the
spoonful without immediate health risk. Chronic exposure, however, weakens the
kidneys. Sodium chloride is neutral in pH.
•Sodium bicarbonate is a mild alkali that can be eaten by the spoonful. In fact, it is
a major ingredient in many antacid tablets.
•Sodium carbonate is a moderate alkali. Eating it by the spoonful would not be
lethal but it would be uncomfortable.
•Sodium hydroxide is a strong alkali that can eat flesh off of bones. A spoonful
would probably be lethal.
•Sodium cyanide does not eat flesh. You could wash your hands in it without
effect. If you eat it, it's a different story. A spoonful is certainly lethal.
As you can see, the properties of "sodium" depend very much on the form in which it is
found. The same is true of chlorine, lead, mercury, and every other chemical element.
No chemical or compound is bad. It depends on what compound, where it is used,
and how much of it there is. The dose makes the poison.

Aluminum
You may not have thought of it, but aluminum is a powerful reducing agent just like
sodium. Recall that reducing agents are easily oxidized, i.e. they burn. Powdered
aluminum is such a flammable substance that it is among the best fuels for use in
fireworks. Now the history of metals can be seen largely as the perfection of furnaces to
produce higher temperatures. Bronze can be smelted at a relatively modest temperature
of 1000°C. Iron must be smelted above about 1600°C. And aluminum ore must be
heated to 2500°C to be smelted from its ore using carbon as a reducing agent. In 1855,
the cost of aluminum was $100,000/lb and it was considered a precious metal. By 1895,
the price had dropped to $0.50/lb. What happened?
In 1886, an Oberlin student named Charles Martin Hall attended a lecture in which the
aluminum "problem" was discussed. The details of electrolysis had been worked out by
Faraday in the 1840's. Cheap electrical power was about to become available as Edison
and Westinghouse battled it out. If electric current could be passed through molten
bauxite (alumina, Al2O3), aluminum should be produced at the cathode. The problem is,
the melting point of alumina is 2050°C. What he needed was to lower the melting point
of alumina. We have seen this problem before when we talked about glass and glazes:
what Hall needed was a flux for alumina. Just as soda ash and colemanite are good
fluxes for silica, he needed a good, cheap flux for alumina. He found it in a mineral
called cryolite, Na3AlF6. Cryolite lowers the melting point of alumina to about 950°C.
At this modest temperature, the production of aluminum by electrolysis becomes
economically feasable and consequently, aluminum has become a major structural
material in the 20th century.

Other Alkali Pages

•USGS Soda Ash Report
•Solvay manufactures soda ash, caustic soda, and chlorine
•Olin operates the Niagara Falls chloralkali plant opened in 1897
•Companies that manufacture alkali
•Companies that mine potash

The Chloralkali and Aluminum Quiz

This quiz will consist of three questions on the following material:
•Know the balanced equations for the production of soda ash from salt, sulfuric
acid, charcoal, and limestone.
•Know the balanced equation for the production of lye, chlorine, and hydrogen by
the electrolysis of brine.
•Know the balanced equation for the production of sodium from salt.
•Know how to relate time and current to the grams or liters (gas) produced by
electrolysis.
•Know the story of how and why soda ash came to be produced by the Leblanc
process and the Solvay process.
•Know the story of how and why lye and chlorine came to be produced by the
chloralkali process.
•Know the story of how and why aluminum came to be produced by the
electrolysis of molten bauxite and cryolite.
•Know perhaps the most important lesson in the whole course.
•Take a practice quiz online.
Instructions
We talked about the production of lye from
soda ash and lime but none of your projects
so far required you to produce lye by this
method. We will produce lye directly by the
electrolysis of saltwater. You will need a 2
liter bottle, two smaller bottles, and
two ordinary flashlight batteries. I will
provide epoxy glue. Click on the picture to
get a slideshow of the instructions.

Criteria for Success

When you bring your chloralkali generator for evaluation, you must be able to tell me
which of the gases is hydrogen and which is chlorine. You can tell this by paying
attention to which terminal of the battery (+ or -) produced which gas. Your hydrogen
must be flammable, your chlorine must smell like chlorine, and your lye must turn test
paper blue.