Scientific American Supplement, No. 401, September 8, 1883

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Manganese is one of the heavy metals of which iron may he taken as the
representative. It is of a grayish white color, presents a metallic
brilliancy, and is capable of a high degree of polish, is so hard as to
scratch glass and steel, is non-magnetic, and is only fused at a white
heat. As it oxidizes rapidly on exposure to the atmosphere, it should be
preserved under naphtha.

It occurs in small quantity in association with iron in meteoric stones;
with this exception it is not found native. The metal may be obtained by
the reduction of its sesquioxide by carbon at an extreme heat.

Manganese forms no less than six different oxides--viz., protoxide,
sesquioxide the red oxide, the binoxide or peroxide, manganic acid, and
permanganic acid. The protoxide occurs as olive-green powder, and is
obtained by igniting carbonate of manganese in a current of hydrogen.
Its salts are colorless, or of a pale rose color, and have a strong
tendency to form double salts with the salts of ammonia. The carbonate
forms the mineral known as manganese spar. The sulphate is obtained by
heating the peroxide with sulphuric acid till there is faint ignition,
dissolving the residue in water and crystallizing. It is employed
largely in calico printing. The silicate occurs in various minerals.

The sesquioxide is found crystallized in an anhydrous form in braunite,
and hydrated in manganite. It is obtained artificially as a black powder
by exposing the peroxide to a prolonged heat. When ignited it loses
oxygen, and is converted into red oxide. Its salts are isomorphous with
those of alumina and sesquioxide of iron. It imparts a violet color to
glass, and gives the amethyst its characteristic tint. Its sulphate is a
powerful oxidizing agent.

The red oxide corresponds to the black oxide of iron. It occurs native
in hausmannite, and may be obtained artificially by igniting the
sesquioxide or peroxide in the open air. It is a compound of the two
preceding oxides.

The binoxide, or peroxide, is the black manganese of commerce, and the
pyrolusite of mineralogists, and is by far the most abundant of the
manganese ores. It occurs in a hydrated form in varvicite and wad. Its
commercial value depends upon the proportion of chlorine which a given
weight of it will liberate when it is heated with hydrochloric acid, the
quantity of chlorine being proportional to the excess of oxygen which
this oxide contains over that contained in the same weight of protoxide.
When mixed with chloride of sodium and sulphuric acid it causes an
evolution of chlorine, the other resulting products being sulphate of
soda and sulphate of protoxide of manganese. When mixed with acids, it
is a valuable oxidizing agent. It is much used for the preparation of
oxygen, either by simply heating it, when it yields 12 per cent. of
gas, or by heating it with sulphuric acid, when it yields 18 per
cent. Besides its many uses in the laboratory, it is employed in the
manufacture of glass, porcelain, and kindred wares.

Manganic acid is not known in a free state. Manganate of potash is
formed by fusing together hydrated potash and binoxide of manganese. The
black mass which results from this operation is soluble in water,
to which it communicates a green color, due to the presence of the
manganate. From this water the salt is obtained _in vacuo_ in beautiful
green crystals. On allowing the solution to stand exposed to the air, it
rapidly becomes blue, violet, purple, and finally red, by the gradual
conversion of the manganate into the permanganate of potash; and on
account of these changes of color the black mass has received the name
of mineral chameleon.

Permanganic acid is only known in solution or in a state of combination.
Its solution is of a splendid red color, but appears of a dark violet
tint when seen by transmitted light. It is obtained by treating a
solution of permanganate of baryta with sulphuric acid, when sulphate of
baryta falls, and the permanganic acid remains dissolved in the water.
Permanganate of potash, which crystallizes in reddish purple prisms, is
the most important of its salts. It is largely employed in analytical
chemistry, and is the basis of Condy's Disinfectant Fluid.

Manganese is a constituent of many mineral waters, and is found in small
quantities in the ash of most vegetables and animal substances. It is
always associated with iron.

Various preparations of manganese have been employed in medicine. The
sulphate of the protoxide in doses of one or two drachms produces
purgative effects, and is supposed to increase the excretion of bile;
and in small doses, both this salt and the carbonate have been given
with the intention of improving the condition of the blood in cases of
anaemia. Manganic acid and permanganate of potash are of great use when
applied in lotions (as in Condy's Fluid diluted) to foul and fetid
ulcers. In connection with the medicinal applications of manganese it
may be mentioned that manganic acid is the agent employed in Dr. Angus
Smith's celebrated test for the impurity of the air.

It is the glass maker's soap of glass manufacture, and is used to
correct the green color of glass, which is owing to the presence of
protoxide of iron. This it converts into the comparatively colorless
peroxide.

It is also used in the Bessemer and similar processes, to decompose the
oxide of iron. Spiegeleisen, an iron which contains a natural alloy of
from 10 to 12 per cent. of manganese, is used for this purpose when
conveniently attainable.--_Glassware Reporter_.

* * * * *

OZOKERITE, OR EARTH-WAX.

By WILLIAM L. LAY.

ON THE DEPOSITS OF EARTH WAX (OZOKERITE) IN EUROPE AND AMERICA.

[Footnote: Abstract from a paper read before the New York Academy of
Sciences.]

There exists a large mining and manufacturing industry in Austria, that
of ozokerite, or earth-wax, which has nothing like it in any other part
of the known world, an industry that supplies Europe with a part of its
beeswax, without the aid of the bees. It may not be generally known that
the mining of petroleum was a profitable industry in Austria long before
it was in this country. In 1852, a druggist near Tarnow distilled the
oil and had an exhibit of it in the first World's Fair in London.
In America, the first borings were made in 1859. Indeed, the use of
petroleum as an illuminator was common at a very early age in the
world's history. In Persia at Baku, in India on the Irawada, also in the
Crimea, and on the river Kuban in Russia, petroleum has been used
in lamps for thousands of years. At Baku the fire worshipers have a
never-ceasing flame, which has burned from time immemorial. The mines of
ozokerite are located in Austrian Poland, now known as Galicia. Near the
city of Drohabich, on the railway line running from Cracow to Lemberg,
is a town of six thousand inhabitants, called Borislau, which is
entirely supported by the ozokerite industry. It lies at the foot of
the Carpathian Mountains. About the year 1862, a shaft was sunk for
petroleum at that place. After descending about one hundred and eighty
feet, the miners found all the cracks in the clay or rock filled with
a brown substance, resembling beeswax. At first, the layers were not
thicker than writing paper; but they grew thicker gradually below, until
at a depth of three hundred feet they attained a thickness of three or
four inches. Upon examination, it was found that a yellow wax could be
made of a portion of this substance, and at once a substitute for wax
was manufactured.

The discovery caused an excitement like the oil fever of 1865 in
America. A large number of leases were made. When I saw the wells of
Pennsylvania, in 1879, there were more than two thousand. The owner
of the land received one-fourth of the product, and the miners
three-fourths. In the petroleum region, the leases at first were whole
farms, then they were reduced to 20, then 10, then 5, and at last to 1
acre, which is a square of 209 feet.

But in the ozokerite region of Poland, where everything is done on a
small scale, when compared with like enterprises in this country, the
leases were on tracts thirty-two feet square. These were so small that
the surface was not large enough to contain the earth that had to be
raised to sink the shaft; consequently the earth had to be transported
to a distance, and, when I saw it, there was a mound sixty or seventy
feet high. Its weight had become so great that it caused a sinking
of the earth, and endangered the shafts to such an extent that the
government ordered its removal to a distance and its deposit on ground
that was not undermined. The shafts are four feet square, and the sides
are supported by timbers six inches through, which leaves a shaft three
feet square. The miner digs the well or shaft just as we dig our water
wells, and the dirt and rock are hoisted up in a bucket by a rope and
windlass. But one man can work in the shaft at a time. For many years
no water was found; but, as there is a deposit of petroleum under the
ozokerite, at a depth of six hundred feet from the surface, the miners
were troubled with gas. This is got rid of by blowing a current of fresh
air from a rotary fan through a pipe extending down the shaft as fast as
the curbing of timber is put in place. The ozokerite is embedded in a
very stiff blue clay for a depth of several hundred feet; below, it is
interlaid with rock. [Specimens of crude and manufactured ozokerite were
on exhibition, through the kindness of Dr. J. S. Newberry.]

That part of the earth's surface has more miners' shafts to the acre
than any other part of the globe. As wages are very low in Poland,
averaging not more than forty cents a day for men and ten cents for
children, a very small quantity of ozokerite pays for the working. If
thirty or forty pounds a day is obtained, it remunerates the two men
and one or two children required to work each lease. When the bucket,
containing the earth, rock, and wax, is dumped in the little shed
covering the shaft, it is picked over by the children, who detach the
wax from the clay or rock with knives. The miners use galvanized wire
ropes and wooden buckets. When preparing to descend, they invariably
cross themselves and utter a short prayer. The business is not free from
danger, carelessness on the part of the boy supplying the fresh air, or
the caving in of the unsupported roof, causing a large number of deaths.
One of the government inspectors of the mines informed me that in one
week there had been eight deaths from accidents.

The ozokerite is taken to a crude furnace, and put into a common cast
iron kettle, and melted. This allows the dirt to sink to the bottom, and
the ozokerite, freed from all other solids, is skimmed off with a ladle,
poured into conical moulds, and allowed to cool, in which form it is
sold to the refiners, for about six cents per pound. The quantity
produced is uncertain, as the miners take care to understate it, for
the reason that the government lays a tax upon all incomes, and the
landowner demands his one-fourth of the quantity mined. The best
authority is Leo Strippelman, who states the quantity produced in
fifteen years at from 375,000,000 to 400,000,000 pounds, worth
twenty-four millions of dollars. As the owners of the land get
one-fourth of the sum, they received six millions. This is at the rate
of four hundred thousand a year, a rather valuable crop from some two
hundred acres of land.

The miners do not support the earth by timber or pillars, as they
should; the result is that the whole plot of about two hundred acres is
gradually sinking, and this will eventually ruin the industry in that
part of the deposit. In another part of the same field, a French company
has purchased forty acres, and it is mining the whole tract and hoisting
through one shaft by steam power. In that shaft they have sunk to a
depth of six hundred feet, and are troubled with water and petroleum.
These they pump out very much the same way as in coal and other mines,
worked in a scientific manner. The thickest layer of ozokerite found is
about eighteen inches, and this layer or pocket was a great curiosity.
When first removed at the bottom of the shaft, it was found to be so
soft that it was shoveled out like putty. During the night it oozed
into the space that had been emptied the day before; this continued for
weeks, or until the pressure of the gas had become too weak to force it
out.

I have been occupied in the petroleum region of Pennsylvania since 1860,
have seen all the wonderful development of the oil wells, and was very
much interested in contrasting the Austrian ozokerite and petroleum
industry with the American. It is a good illustration of the difference
between the lower class of Poles and Jews and the Yankee. Borislau,
after twenty years' work, was unimproved, dirty, squalid, and brutal. It
contained one school house, but no church nor printing office. None of
its streets were paved, and, in the main road through the town, the mud
came up to the hubs of the wagon wheels for over a mile of its length.
In places, plank had to be set up on edge to keep the mud out of the
houses, which were lower than the road. It contained numerous shops,
where potato whisky was sold to men, women, and children. It depends on
a dirty, muddy creek for its supply of water. Its houses were generally
one-story, built of logs and mud.

On the other hand, Oil City, a town of the same age and size, contained
eight school houses (one a high school building), twelve churches, and
two printing offices. It has paved streets, which, in 1863, were as deep
with mud as those in Borislau in 1879. It has no whisky shops where
women and children can drink. Many of its houses are of brick, two,
three, four, and five stories high. Its water works cost one hundred and
fifty thousand dollars. All this has been done since 1860, when it did
not contain forty houses.

I saw in the market place of Borislau women standing ankle deep in the
mud, selling vegetables. One woman really had to build a platform of
straw, on which to place a bushel of potatoes; if the straw foundation
had not been there, the potatoes would have sunk out of sight. Borislau
is three miles from Drohobich, a city of thirty thousand inhabitants;
between the two places, in wet weather, the road was impassable. For a
third of the way, it was in the bed of the creek; and I had to wait a
day for the water to fall so as to navigate it in a wagon. On inquiring
why they did not improve the road, I found the same difficulty as the
Arkansas settler encountered with his leaky roof; when it rained he
could not repair it, and when it was dry it did not need repair: so with
the road to Borislau.

Ozokerite (from the Greek words, "Ozein," to smell, and "Keros," wax) is
found in Turkistan, east of the Caspian Sea; in the Caucasian Mountains,
in Russia; in the Carpathian Mountains, in Austria; in the Apennines,
in Italy; in Texas, California, and in the Wahsatch Mountains, in the
United States. Commercially, it is not worked anywhere but in Austria;
although, I believe, we have in Utah a larger deposit than in any other
place. I made two journeys to examine the deposits in the Wahsatch
Mountains. For a distance of forty miles, it crops out in many places,
and on the Minnie Maud, a stream emptying into the Colorado, I found
a stratum of sand rock, from ten to twelve feet thick, filled with
ozokerite.

No systematic effort has been made to ascertain the quantity of
ozokerite in Utah. I saw a drift of some fourteen feet at one place, and
a shaft twenty-three feet deep at another. In this shaft, the vein was
about ten inches wide; and it could be traced along the slope of the
hill, for several hundred feet. The largest vein of pure ozokerite is
seen on Soldiers' Fork of Spanish Canon, which enters Salt Lake Valley
near the town of Provo. This vein is very much like the ozokerite of
Austria, and contains between thirty and forty per cent. of white
ceresin (which resembles bleached beeswax), about thirty per cent. of
yellow ceresin (which resembles yellow wax), and twenty per cent. of
black petroleum; the residue is dirt. Dr. J. S. Newberry, of Columbia
College, and Prof. S. B. Newberry, of Cornell University, made
examinations of the ozokerite found in Utah; those who are interested
in the subject will find the papers published in the _Engineering and
Mining Journal_ for the year 1879.

A deposit of white ozokerite occurs on the top of the Apennine
Mountains, in Italy, of which a specimen is here exhibited. An
interesting story is told of its discovery. A church at Modena was
robbed; among other articles taken was a quantity of wax candles. A
short time afterward, a woman brought to a druggist a quantity of wax
and offered it for sale. The druggist bought it and afterward suspected
it consisted of the stolen candles melted down. Soon after ward she
brought another lot. He had her arrested. When questioned by the
magistrate, she said she found the wax in the clay on her farm, about
twenty miles from the city. This story confirmed him in the belief that
she had stolen the candles, or was the receiver of the stolen goods; for
such a thing as a deposit of wax in the soil was unheard of. She was
therefore remanded to jail. On three several days, she was brought
before the court, and, when questioned, told the same story. She was a
member of the church, and requested the priest to be sent for. He came,
and, after an interview between them, he said it was easy to disprove
her story, if it was a lie, by sending her home, in company with an
officer, to investigate. The court sent the priest, who was the only one
who believed her. On coming to her house, she took her pick and shovel,
and going to the place at the top of the hill, she dug out of the clay
a quantity of while ozokerite, proved her case, and was at once set at
liberty. She performed the same service for me, and I saw her dig the
specimen and heard her tell the story as I have told it to you. The hill
was composed of loose clay and stones. It appeared as if it had been
forced up by gas or some power from below the surface. The quantity that
could be gathered, by one person, laboring constantly for a week, was
only twenty-five or thirty pounds. An attempt had been made to sink a
shaft; but, at a depth of fourteen feet, the pressure of the clay was
sufficient to break the boards that held up the sides. The earth caved
in, and the shaft was abandoned.

It is not necessary here to describe the various processes of
manufacture; it will be sufficient to enumerate some of the forms of
ozokerite, and the uses to which it is put. At Borislau, there are
several refineries, where candles, tapers, and lubricating oils are
made. In Vienna, there are five factories; in one of these, they make
white wax, wax candles, matches, yellow beeswax, black heel-ball,
colored tapers, and crayon pencils. In Europe, large quantities of the
yellow wax are used to wax the floors of the houses, many of the finer
ones being waxed every day. It is a curious fact that the Catholic
Church does not allow the use of paraffine, sperm, or stearine candles;
at the same time nearly all the candles used in the churches in Europe
are made from ozokerite, which is a natural paraffine, made from
petroleum in nature's laboratory. In the United States, the only
uses made of ozokerite, so far as I know, are chewing gum and the
adulteration of beeswax. In this the Yankee gives another illustration
of the ruling passion strong in money making, which gives us wooden
nutmegs, wooden hams, shoddy cloth, glucose candy, chiccory coffee,
oleomargarine butter, mineral sperm oil made from petroleum, and beeswax
made without bees.

After this paper was written, the following translation from a pamphlet,
published by the First Hungarian Galician Railway Company, in 1879, came
to my notice. The writer's name is not published:

"Mineral wax, in the condition in which it is taken from the shafts,
is not well adapted for exportation, since it occurs with much earthy
matter; and, at any rate, an expensive packing in sacks would be
necessary. It is therefore first freed from all foreign substances by
melting, and cooled in conical cakes of about 25 kilos. weight, and
these cakes are exported. There are now, in Borislau, 25 melting works,
which, in 1877, with 1 steam and 60 fire kettles, produced 95,000 metric
centners (9,500,000 lb.).

"The melted earth wax is sent from Borislau to almost all European
countries, to be further refined. Outside of Austro-Hungary, we may
specially mention Germany, England, Italy, France, Belgium, and Russia
as large purchasers of this article of commerce.

"PRODUCTS AND THEIR APPLICATIONS.

"The products of mineral wax, are:

"(a.) _Ceresine_, also called ozocerotine or refined ozokerite, a
product which possesses a striking resemblance to ordinarily refined
beeswax. It replaces this in almost all its uses, and, by its cheapness,
is employed for many purposes for which beeswax is too dear. It is much
used for wax candles, for waxing floors, and for dressing linen and
colored papers. Wax crayons must be mentioned among these products. The
house of Offenheim & Ziffer, in Elbeteinitz, makes them of many colors.
These crayons are especially adapted to marking wood, stone, and iron;
also, for marking linen and paper, as well as for writing and drawing.
The writings and drawings made with these crayons can be effaced neither
by water, by acids, nor by rubbing.

"Concerning the technical process for the production of ceresine, it
should be said that, when the industry was new (the production of
ceresine has been known only about eight years, since 1874), it was
controlled by patents, which are kept secret. This much is known, that
the color and odor are removed by fuming sulphuric acid.

"From mineral wax of good quality about 70 per cent. of white ceresine
is obtained. The yellow ceresine is tinted by the addition of coloring
matter (annatto).

"(b.) _Paraffine_, a firm, white, translucent substance, without odor.
It is used, chiefly, in the manufacture of candles, and also as a
protection against the action of acids, and to make casks and other
wooden vessels water-tight, for coating corks, etc., for air-tight
wrappings, and, finally, for the preparation of tracing paper. There
are several methods of obtaining paraffine from ozokerite (see the
Encyclopedic Handbook of Chemistry, by Benno Karl and F. Strohmann, vol.
iv., Brunswick, 1877).

"The details of the technical process consists, in every case, in the
distillation of the crude material, pressure of the distillate by
hydraulic presses, melting, and treating by sulphuric acid.

"In the manufacture of paraffine from ozokerite, there are produced from
2 to 8 per cent. of benzine, from 15 to 20 per cent. of naphtha, 36
to 50 per cent. of paraffine, 15 to 20 per cent. of heavy oil for
lubricating, and 10 to 20 per cent. of coke, as a residue.

"(c.) _Mineral oils_, which are obtained at the same time with
paraffine, and are the same as those produced from crude petroleum,
described above. The process consists, as in the natural rock oils,
besides the distillation, in the treatment of the incidental products
with acids and alkalies.

"Of the products of ozokerite, manufactured in Galicia, the greater part
goes to Russia, Roumania, Turkey, Italy, and Upper Hungary. The common
paraffine candles made in Galicia--which are of various sizes, from
28 to 160 per kilo--are used by the Jews in all Galicia, Bukowuina,
Roumania, Upper Hungary, and Southern Russia, and form an important
article of commerce. Ceresine is exported to all the ports of the world.
Of late a considerable quantity is said to have been sent to the East
Indies, where it is used in the printing of cotton."

The President, Dr. J. S. Newberry, stated that ozokerite was undoubtedly
a product of petroleum. Little was known by the public concerning its
use and value. He exhibited specimens of natural brown ozokerite, of
yellow ozokerite, sold as beeswax, and of a white purified form, which
had been treated by sulphuric acid. Specimens from Utah had already been
shown before the Academy. There was no mystery as to its genesis in
either region, as it had been shown to be the result of inspissation of
a thick and viscid variety of petroleum. The term "petroleum" includes a
great variety of substances, from a limpid liquid, too light to burn,
to one that is thick and tarry. These differ widely also in chemical
composition: some yielding much asphalt by distillation, resembling a
solution of asphalt in turpentine; some containing so much paraffine
that a considerable quantity can be strained out in cold weather. The
asphalt in its natural form is a solid rock, to which the term "gum
beds" has been applied in Canada. These differences in constitution have
originated in the differences in the bituminous shales from which the
petroleum, ozokerite, etc., have been derived. In Canada, as excavations
are sunk through the asphalt, this becomes softer and softer, and
finally passes into petroleum. This is also the case in Utah.

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