IMPROVE- MENTS IN THE MANUFACTURE OF CYANIDES OF BARIUM AND STRONTIUM
Year: 1860

page_text: LETTERS PATENT to William Clark, of 53, Chaucery Lane, in the County
of Middlesex, Engineer & Patent Agent, for the Invention of "IMPROVE-
MENTS IN THE MANUFACTURE OF CYANIDES OF BARIUM AND STRONTIUM."-A.
communication from abroad by Louis Joseph Frederic Margueritte,
Chemist, and Alfred Lalouël de Sourdeval, both of Paris, in the Empire
of France.
Sealed the 1st November 1860, and dated the 11th May 1860.
PROVISIONAL SPECIFICATION left by the said William Clark at the
Office of the Commissioners of Patents, with his Petition, on the
11th May 1860.
I, WILLIAM CLARK, of 53, Chancery Lane, in the County of Middlesex,
Engineer & Patent Agent, do hereby declare the nature of the said Invontion
for "IMPROVEMENTS IN THE MANUFACTURE OF CYANIDES OF BARIUM & STRONTIUM,"
being a communication from abroad by Messrs. Louis Joseph Frederic
Margueritte, Chemist, & Alfred Lalouël de Sourdeval, both of Paris, in the
Empire of France, to be as follows:-
If carbonate of baryta be intimately mixed with charcoal, subdivided by
means of sawdust, and heated in a crucible, a porous mass is obtained after a
lengthened calcination, which, when cooled and washed in water, will furnish
au abundance of crystallized hydrate of baryta. On carefully examining this
solution, it will be found to contain cyanide of barium as well as caustic baryta.

page_text: The formation of this substance appears at first to be inexplicable, as it it readily
understood and proved that the matters employed do not contain azote in any
form; we have, however, found that cyanideof barium is formed from theazote of
the atmosphere, as,under the conditions in which the operation is effected, with
an imperfectly closed crucible, a circulation of air is established, the action of
which is the more considerable as the mixture is more porous and the calcina
tion of longer duration. Although the formation of cyanide of barium under
the above conditions has never been observed, nor in the calcination of baryta
with azoted matters, its production is not the less certain. Taking this as
admitted, we pass a current of azote through a tube heated to redness,on to a
mixture of carbonate of baryta and charcoal, subdivided by means of sawdust;
the current of gas being maintained during the reduction of the baryta and the
cooling of the mass.
The matter when treated with water will be found to furnish large quantities
of cyanide of barium. This easy and simple chemical action appears to be of
great commercial value, we have therefore spared no effort to render it practical
and economical.
The following are the various methods of operation which we have found to
produce the best results:-1st, carbonate of baryta being taken, we mix with
it from 10 to 30 per cent. of pitch, coal tar, or resin, and a certain quantity of
sawdust or charcoal or coke to subdivide the mass and render it porous, we
then calcine this mixture and slowly pass into it a current of atmospheric air
or of azote at a high temperature; the azote combines with the minutely sub-
divided carbon deposited by the pitch, formscyanogen, and ultimately cyanide
of barium. 2ndly, on a mixture of carbonate of baryta and sawdust or charcoal,
we pass a mixture of illuminating gas and azoteat a red heat, the carbonate of
baryta will be reduced to baryta under the influence of the carbonated hydrogen,
the carbon of which unites with the azote and forms cyanogen,and ultimately
cyanide of barium. 3rdly, on a mixture of carbonate of baryta and animal
matters subdivided with charcoal or sawdust, we pass a current of atmospheric
air or of azote at a red heat; in this manner the quantity of cyanide of barium
produced will be considerably augmented.
The principaladvantages which the preparation of cyanide of bariumpresent
over those of cyanides of potassium or sodium by means of the azote of the
air, are,
1st, the relatively low temperaturent which the production of the cyanide
is effected.
2ndly, the infusibility of the baryta which remains porous and penetrableby

page_text: 3rdly, the durability and resistance of the apparatus which are neither
vitrified nor destroyed.
4thly, the great inferiority of the price of baryta, as compared with potash,
and further, the capability of obtaining cyanide of potassium by a double
decomposition of sulphate of potash with cyanide of barium.
In conclusion, carbonates of potash and soda have hitherto been solely
employed for producing cyanides by contact with the air; but what we consider
as new and never before attempted, is obtaining cyanides from baryta by means
of the azote of the air; this Invention therefore consists in the preparation of
cyanides of barium and strontium by the means herein-before described.
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said William Clark in the Great Seal Patent Office on the
5th November 1860.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, WILLIAM
CLARK, of 53, Chancery Lane, in the County of Middlesex, Engineer and
Patent Agent, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by ler Letters
Patent, bearing date the Eleventh day of May, in the year of our Lord
One thousand eight hundred and sixty, in the twenty-third year of Her
reign, did, for Herself, Her heirs and successors, give and grant unto me, the
said William Clark, Her special licence that I, the said William Clark,
my executors, administrators, and assigns, or such others as I, the said
William Clark, my executors, administrators, and assigns, should at any
time agree with, and no others, from time to time and at all times there-
after during the term therein expressed, should and lawfully might make,
use, exercise, and vend, within the United Kingdom of Great Britain and
Ireland, the Channel Islands, and Isle of Man, an Invention for "IMPROVE.
MENTS IN THE MANUFACTURE OF CYANIDES OF BARIUM AND STRONTIUM," a com-
munication from abroad by Louis Joseph Frédéric Margueritte& Alfred Lalouël
de Sourdeval, both of Paris, in the Empire of France, upon the condition
(amongst others) that I, the said William Clark, my executors or adminis-
trators, by an instrument in writing under my, or their, or one of their hands
and seals, should particularly describe and ascertain the nature of the said
Invention, and in what manner the same was to be performed, and cause
the same to be filed in the Great Seal Patent Office within six calendar
months next and immediately after the date of the said Letters Pateut.

page_text: NOW KNOW YE, that I, the said William Clark, do hereby declare the
nature of the said Invention, and in what manner the same is to be per-
formed, to be particularly described and ascertained in and by the following
statement (that is to say) :-
If carbonate of baryta be intimately mixed with charcoal, subdivided by
means of sawdust, and heated in a crucible, a porous mass is obtained after a
lengthened calcination, which, when cooled and washed in water, will furnish
an abundance of crystallized hydrate of baryta. On carefully examining this
solution, it will be found to contain cyanide of barium aswell as caustic baryta.
The formation of this substance appears at first to be inexplicable, as it is
readily understood and proved that the matters employed lo not contain azote
in any form; I have, however, found that the cyanide of barium is formed
from the azote of the atmosphere as under the conditions in which the operation
is effected with an imperfectly closed crucible, a circulation of air is established,
the action of which is the more considerable as the mixture is more porous,
and the calcination of longer duration. Although the formation of cyanide of
barium under the above conditions has never been observed, nor in the calcina-
tion of baryia with zoted matters, its production is not the less certain.
Taking this as admitted, I pass a current of azote through a tube heated to
redness on to a mixture of carbonate of baryta and charcoal, subdivided by
means of sawdust, the current of gas being maintained during the reduction of
the baryta and the cooling of the mass. The matter when treated with water
will be found to furnish large quantities of cyanide of barium. This easy and
simple chemical action appears to be of great commercial value, I have there-
fore spared no effort to render it practicable and economical.
The following are the various methods of operation, which I have found to
produce the best results:-First, carbonate of baryta being taken, I mix with
it from ten to thirty per cent.of pitch, coal tar, or resin,and a certain quantity
of sawdust, or charcoal, or coke, to subdivide the mass and render it porons; I
then calcine this mixture and slowly pass on to it a current of atmospheric air
or of azote at a high temperature; the azote combines with the minutely sub-
divided carbon deposited by the pitch, and forms cyanogen and ultimately
cyanide of barium. Secondly, on a mixture of carbonate of baryta and sawdust
or charcoal, I pass a mixture of illuminating gas and azote at a red leat,
the carbonate of baryta will be reduced to baryta under the influence of
the carbonated hydrogen, the carbon of which unites with the azote and
forms cyanogen, and ultimately cyanide of barium. Thirdly, on a mixture
of carbonate of baryta and animal matters subdivided with charcoal or
sawdust, I pass a current of atmospheric air or of azote at a red heat, in

page_text: this manner the quantity of the cyanideof bariumproduced willbe considerably
augmented.
The principal advantages which the preparation of cyanide of barium present
over those of cyanides of potassium or sodium by means of the azote of the
air, are,
First, the relatively low temperature at which the production of the cyanide
is effected.
Secondly, the infusibility of the baryta which remains porous and penetrable
by the azote, from which a more perfect action results.
Thirdly, the durability and resistance of the apparatus which are neither
vitrified nor destroyed.
Fourthly, the great inferiority of the price of baryta as compared with
potash,and further, the capabilityof obtaining cyanide of potassium bya double
decomposition of sulphate of potash with cyanide of barium.
In conclusion, I mayobserve that carbonates of potash and soda have hitherto
been solely employed for producing cyanides bycontact with the air, butwhat
I consider as new and never before attempted, and therefore claim as the
Invention to be protected by the herein-before in part recited Letters Patent,
is, obtaining cyanides from baryta by means of the azote of the air, and
the preparation of cyanides of barium and strontium by the means and as
herein-before described.
In witness whereof, I, the said William Clark, have hereunto set my
hand and seal, this Fifth day of November, in the year of our Lord
One thousand eight hundred and sixty.
5
Witness,
W. G. E. SWINNOCK,
53, Chancery Lane.
WILLIAM CLARK. (L.S.)