AN IMPROVED CARBUROMETER FOR MAKING QUANTITATIVE ANALYSES OF FIRE-DAMP IN MINES, AND FOR REGULATING COMBUSTION IN INDUSTRIAL
Year: 1877

page_text: LETTERS PATENT to Jacques Coquillion, Professor of Chemistry, of 82,
Boulevard Sébastopol, Paris, in the Republic of France, for the Invention of
"AN IMPROVED CARBUROMETER FOR MAKING QUANTITATIVE ANALYSES OF
FIRE-DAMP IN MINES, AND FOR REGULATING COMBUSTION IN INDUSTRIAL
ר
Sealed the 15th September 1877, and dated the 26th March 1877.
PROVISIONAL SPECIFICATION left by the said Jacques Coquillion at the
Office of the Cominissioners of Patents on the 26th March 1877.
JACQUES COQUILLION, Professor of Chemistry, of 82, Boulevard Sébastopol, Paris,
in the Republic of France. " AN IMPROVED CARBUROMETER FOR MAKING QUANTI-
TATIVE ANALYSES OF FIRE-DAMP IN MINES, AND FOR REGULATING COMBUSTION IN
INDUSTRIAL FURNACES."
This Invention relates to the quantitative analysis of carburetted hydrogen and
other gases.
The principle on which the apparatus is based is as follows:-Hydrogen, or one
of its carburetted compounds in the form of gas or vapour, is completely burned
in presence of oxygen and a palladium wire borne to a white heat. In the case of
simple hydrogen there is formation of steam of water; in the case of carburets there
is besides a formation of carbonic acid; in either case there is diminution of volume,
and it is this diminution that is observed for the analysis either of hydrogen or its
carburetted compound. The reciprocal of this proposition is generally correct, every
oxygenated compound in a state of gas or vapour is susceptible of the decomposition
of its elements in presence of hydrogen and a palladium wire at white heat. From
these two propositions it is easy to determine a general process of analysis of gases
replacing the eudiometric process.
First, I will explain how to produce a practical apparatus for the analysis of
carburetted hydrogen in mines; next, gases evolved from industrial furnaces, and
generally, the different gases analyzed by the eudiometrical method.
It is important to be able to analyze fire-damp in mines. I will therefore describe
a simple apparatus which is in some measure the simplification of the more complete
.

page_text: apparatus for analyzing gases generally. This apparatus consists of a glass tube,
open at its two ends, and is narrowed in the middle, which is divided by a scale
into equal parts; the lower openings should remain open but the upper one should
be closed with an india-rubber stopper with three holes, in one of which a small
peg is fixed which is removed when required; in the other two brass pincers engage,
the lower ends of which hold the two ends of a palladium wire which descends into
the tube, twisting spirally. The upper part of these pincers are flush with the
middle stopper, so that the contact with the pile is effected in a closed space. This
first tube, which may be termed burner, plunges with its stopper into a glass
cylinder filled with water or glycerine, also stoppered; this cylinder is encased in
a brass or tin plate, with two openings in its upper part, so that the marks or scale
on the centre tube may be seen by a lamp.
The apparatus may be fixed by a socket on a stick which the operator bears in
hand, or may be suspended vertically by a hook. To take in gas, the external tin
plate casing being fixed vertically, the stopper is removed as well as that of the
cylinder; the central tube is raised by hand, the external air enters in this tube, as
well as the water it contains at the same time descends in the cylinder and it is
stopped as soon as the mark zero is observed level with the water; an iron wire
wound round the tube and sliding the length of the brass tube can effect this; the
little pin or wooden plug is then placed in the third hole, thus a limited volume of
air is imprisoned, say, for example, 25 centimetres. Thus the two poles of the pile
which are engaged in two pincers, held fixed by the stopper of the burner, are
brought in contact in the centre of the india-rubber in the middle of the closed
space, the thread becomes heated, the fire-damp burns, and it merely remains to let
the gas and tube cool and to remark the diminution of volume.
Another mode of operating is as follows:-Ten small empty flasks, placed in a
wooden box, may be lowered into the mine, then raised, and the gas analyzed;
both these methods can be used simultaneously, the second controlling the first.
The apparatus serving to effect this control will be designated the fire-damp
analyzer (Grisoumetre analyseur); it will also serve as eudiometer for chemists;
its precision is such that it admits of estimating a cubic millimetre of fire-damp in
a given atmosphere. It consists of a glass measuring tube, terminated above by a
capillary part T form, each horizontal branch of which bears a tap; this portion may
also be of glass or metal; the lower part graduated as in the case of the first
apparatus, is narrowed, then bent at a right angle; to this extremity a tube of
india-rubber is adapted connected to the lower tube of a flask, serving as sucker or
blower. This flask rests on the foot of a plank, bearing the whole apparatus. The
second piece is a small tube of D shape, closed by a stopper, the two holes of which
are furnished with two pincers serving to fix the spiral of palladium; laterally
this D shaped tube bears two small capillary tubes; one is connected by an india-
rubber to the first measuring tube, the other to a bell surrounded by a cylinder
filled with water, glycerine, or mercury. All these tubes are set in a groove in a
plank of open work and resting on a small foot.
The manipulation of the apparatus is most simple; by means of an india-rubber
the point of the apparatus is adapted to one of the small cylindro-conical tubes
which have been emptied in the mine, the lower part of this cylinder resting on a
vessel full of water, and 25 centimetres of gas are drawn up for analysis;
it is passed
to the heated palladium wire by raising and lowering the flask several times when
combustion is complete; time must be allowed for cooling the D shaped tube, or the
cooling may be hastened by damping it with a cloth dipped in water or ether, when
it may be read.
For analyzing other combustible gases one operates the same as for the proto-
carburetted hydrogen, an inert gas may be put in the burners, if, for example,
oxygen is to be analyzed, and if it is supposed that the oxygen of the air which is
there may vitiate the measuring. To measure absorbable gases it suffices generally
to replace the spiral of palladium by the absorbant, the surfaces are multiplied by
the addition of pumice-stone; for instance, to absorb carbonic acid potash is taken;

page_text: to absorb oxygen pyrogallic acid is added to the potash; to absorb carbonic oxyd
the whole is replaced by ammoniacal chloride of copper; vials ready prepared may
be used containing the suitable absorbants. Generally it is requisite to put
glycerine instead of water in the flask and bell.
In regulating industrial furnaces and analyzing the gas each moment, one of
these apparatus may be placed in proximity to the chimney of the furnace, one can
then by adopting the same principle combine the first shape with the second. In
this case the burner will be a tube in shape of a funnel, furnished at its upper part
with a bung of india-rubber with two pincers; in this instance, connected directly
with the poles of the pile, the third hole of the bung will receive the tube by which
the aspiration of the gas of the furnace is effected; this tube will be furnished with
horizontal branches with taps; following them are two vials or two analogous tubes
or burners of the second apparatus, and one of which contains potash, the other
ammoniacal chloride of copper; then come two bells containing water or glycerine.
These two bells and the burner are surrounded by movable cylinders.
When an experiment is to be made the entry tube is purged by blowing by a
branch borne by the operator, then by closing so as to exclude external air the bell
of the burner is made to descend; the gas emanating from combustion enters there,
the tap of the entry pipe is closed, and the gas is cooled; thus it is supposed 25 cubic
centimetres of gas are taken in, the palladium wire is heated, cooling is allowed,
and the difference is observed which indicates the diminution of volume resulting
from combustions which have not taken place at the furnace, and which are with
the carburots, that of carbonic oxyd, a volume of which with half a volume of
oxygen has given a volume of carbonic acid; a second draught of gas may directly
give by passing it on the re-agent (ammoniacal copper) the amount of oxygen and
carbonic oxyd, and on the potash the carbonic acid, which in the best combustions
may reach from 14 to 15%
SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said Jacques Coquillion in the Great Seal Patent Office on the 25th
*September 1877.
JACQUES COQUILLION, Professor of Chemistry, of 82, Boulevard Sébastopol, Paris,
in the Republic of France. "AN IMPROVED CARBUROMETER FOR MAKING QUANTI-
TATIVE ANALYSES OF FIRE-DAMP IN MINES, AND FOR REGULATING COMBUSTION IN
INDUSTRIAL FURNACES."
This Invention relates to the quantitative analysis of carburetted hydrogen and
other gases.
The principal on which the apparatus is based is as follows:-Hydrogen or one
of its carburetted compounds in the form of gas or vapour is completely burned in
the presence of oxygen, and a palladium wire borne to a white heat. In the case of
simple hydrogen there is a formation of steam of water; in the case of carburets
there is besides a formation of carbonic acid; in either case there is diminution of
volume, and it is this diminution that is observed for the analysis either of hydrogen
or its carburetted compound. The reciprocal of this proposition is also generally
right; every oxygenated compound in a state of gas or vapour is susceptible of the
decomposition of its elements in presence of hydrogen and a palladium wire at
white heat. From these two propositions it is easy to determine a general process
of analysis of gases replacing the eudiometric process.
First. I will explain how to produce a practical apparatus for the analysis of
proto-carburetted hydrogen in mines; next, gases evolved from industrial furnaces,
and generally, the different gases analyzed by the eudiometrical method.
It is important to be able to analyze fire-damp in mines; I will therefore describe
a simple apparatus which is, in some measure, the simplification of the more

page_text: complete apparatus for analyzing gases generally. This apparatus consists of a glass
tube A, Fig. 1, open at its two ends, and is narrowed in the middle, which is divided
by a scale into equal parts. The lower openings should remain open, but the upper
one should be closed with an india-rubber stopper with three holes, in one of which
a small peg is fixed which is removed when required; in the other two brass pincers
engage, the lower onds of which hold the two ends of a palladium wire, which
descends into the tube, twisting spirally. The upper part of these pincers are flush
with the middle of the stoppor, so that the contact with the pile is effected in a
closed space. This first tube, which may be termed the burner, plunges with its
stopper into a glass cylinder filled with water or glycerine, see B, Fig. 2, also
stoppored; this cylinder is encased in a brass or tin plate, with two openings in
its upper part, so that the marks or scale on the central tube may be seen by a
lamp.
The apparatus may be fixed by a socket on a stick which the operator bears in
hand, or may be suspended vertically by a hook. To take in gas, the external tin 1
plate casing being fixed vertically, the stopper is removed, as well as that of the
cylinder, the central tube is raised by hand; the external air enters in this tube
as well as the water it contains at the same time descends in the cylinder, and it is
stopped as soon as the mark zero is observed level with the water; an iron wire
wound round the tube and sliding the length of the brass tube can effect this; the 2
little pin or wooden plug is then placed in the 3rd hole; thus a limited volume of
air is imprisoned, say for example, 25 cubic centimètres; these, the two poles of the
pile, which are engaged in two pincers held fixed by the stopper of the burner, are
brought in contact in the centre of the india-rubber; in the middle of the closed
space the thread becomes heated, the fire-damp burns, and it merely remains to let
the gas and tube cool, and to remark the diminution of volume.
To effect the cooling the tube can be immersed in the water in the cylinder and
wait a minute or two; it can be read by leading the inner and outer levels on the
same horizontal line. The diminution of the gascous volume will'give the quantity
of fire-damp of the ambient medium or surrounding fire-damp.
3
The division of the tube may be arbitrary, but there is an advantage in getting
the quantity of fire-damp in centimètres; thus, supposing zero marked where the
tube is 25 centimètres, and 10 where the narrow part commences, which is the
point where the tube is 20 centimètres, then the interval, which is 5 cubic centi-
inètres, is divided into 10 equal parts, each representing 1/2 cubic centimètre, and 3
corresponds to 1 per cent. of fire-damp. In effect a volume of pure carburetted
hydrogen requiring 2 volumes of oxygen to burn 2 volumes of steam of water is
formed, which disappear in a rose and volume of carbonic acid, which remains or
may be absorbed for 1 volume of fire-damp burned; there is, therefore, a disappear.
ance of 2 volumes, but if one volume comprises two divisions a single division will
correspond to the centisiinal composition.
The operation can be more accurately performed by the use of glycerine instead
of water, which may absorb a little carbonic acid arising from the combustion, but
this absorption is always very feeble if one operates rapidly. As to the pile which
should heat the palladium wire two Bunsen appliances may be used, but it is more
simple to have recourse to Plante's piles or 'piles Planté,' which can remain charged
several weeks, and admit of making several experiments.
The mine manager, if he thinks fit, can operate in another way. He can empty.
ten small flasks of 60 cubic centimètres placed in a wooden box, raise these flasks, and
analyze the gas in its turp; it is as well to observe that both methods can be used
simultaneously, the second controlling the first. The apparatus serving to effect this
control will be designated the fire-damp analyzer. It will also serve as eudiometer
for chemists, its precision is such that it admits of estimating a cubic millimètre of
fire-damp in a given atmosphere. It consists of a glass measuring tube, see Fig. 3,
terminated above by capillary part of T form, each horizontal branch of which 5
bears a tap; this portion may also be of glass or metal, the lower part graduated, and
as in the case of the first apparatus is narrowed, then bent at a right angle to this

page_text: extremity a tube of india-rubber is adapted, connected to the lower tube of a flask
serving as sucker or blower. This flask rests on the foot of a plank bearing the
whole apparatus. Each of the divisions marking the centimes is divided in its turn
into 10 equal parts, which admits of obtaining To00 of a cubic centimètre, nearly
the quantity of proto-carburetted hydrogen. The second piece is a small tube B of
D shaped, bent and closed by a stopper or bung, the two holes of which are
furnished with two pincers serving to fix the spiral of palladium laterally; this
D shaped tube bears two small capillary tubes; one is connected by an india-rubber
to the first measuring tube, the other to a bell surrounded by a cylinder filled with
water, glycerine, or mercury. All these tubes are set in a groove in a plank of wood
pierced with open work and resting on a small foot.
it
The manipulation of the apparatus is' most simple; by means of an india-rubber
the point of the apparatus is adapted to one of the small cylindro-conical tubes,
which have been emptied in the mine, the lower part of this cylinder resting on a
vessel full of water, and 25 cubic centimètres of gas are drawn up for analysis;
is passed to the heated palladium wire by raising and lowering the flask several
times when combustion is complete time must be allowed for cooling the D shaped
tube, or the cooling may be hastened by damping it with a cloth dipped in water
or ether, when it may be read.
For analyzing other combustible gases one operates the same as for the proto-
carburettod hydrogen; an inert gas may be put in the burner, if, for example, oxygen
is to be analyzed, and if it is supposed that the oxygen of the air which is there may
vitiate the measuring.
It is observed that for gases other than the proto-carburet and the bicarburet, the
graduation adopted no longer gives the composition in centines; it will be easily
obtained. To measure absorbable gases it suffices generally to replace the spiral of
palladium by the absorbant; the surfaces are multiplied by the addition of a pumice-
stone; for instance, to absorb carbonic acid potash is taken; to absorb oxygen
pyrogallic acid is added to the potash; to absorb carbonic oxyd the whole is replaced
by ammoniacal chloride of copper. Vials ready prepared may be used containing
the suitable absorbants. Generally it is requisite to put glycerine instead of water in
the flask and bell.
In regulating industrial furnaces and analyzing the gas cach moment one of these
apparatus may be placed in proximity to the chimney of the furnace, one can then
by adopting the same principle combine the first shape, Fig. 1, with the second, Fig. 2.
In this case the burner will be a tube in shape of a funnel furnished at its upper
part with a bung of india-rubber, with 2 pincers in this instance connected directly
with the poles of the pile the 3rd pole of the bung will receive the tube, by which
the aspiration of the gas of the furnace is effected this tube will be furnished with
horizontal branches with taps following them are two vials or two analogous
tubes or burners of the second apparatus, and one of which contains potash, the
other ammoniacal chloride of copper, then come two bells containing water or
glycerine; these 2 bells and the burner are surrounded by movable cylinders.
When an experiment is to be made the entry tube is purged by blowing by a
branch borne by the operator; then by closing so as to exclude external air the bell
of the burner is made to descend; the gas emanating from combustion entors there,
the tap of the entry pipe is closed, and the gas is cooled; thus it is supposed 25 cubic
centimetres of gas are taken in, the palladium wire is heated, cooling is allowed,
and the difference is observed which indicates the diminution of volume resulting
from combustions which have not taken place at the furnace, and which are with
the carburets, that of carbonic oxyd, a volume of which with 1/, a volume of oxygen
has given a volume of carbonic acid, a second draught of gas may directly give
by passing it on the test or re-agent, the amount of oxygen and carbonic oxyd,
and on the potash the carbonic acid, which in the best combustions may reach 14
to 15%.
The passage of the gas of the burner in the bells is easily understood if the bell
of the burner is raised, and that of the right bell lowered in opening the corre

page_text: sponding tap, it will be seen that the gas will pass on the re-agent, and will con-
sequently be absorbed. Here it is indispensable to put glycerine, if not in the
3 tubes at least in the burner, where the absorption of the carbonic acid would be too
great on account of the coolings which require a certain time. One may limit
oneself to analyzing separately, either the carbonic acid alone or the carbonic oxyd
and oxygen, the burner simply plays the part of measurer, thus the progress of com-
bustion at each moment may be proved in any furnace. The graduation will be by
cubic centimètres, and it is simple if 25 cubic centimètres are operated upon, to bring
to 100 parts. If each cubic centimetre is divided into 10 equal parts, and the gases
sought will be obtained at nearly 1 cubic millimètre.
The three cylinders should be surrounded by metallic tubes for protection these
tubes would be cast or open cut to allow of the divisions being seen, they may slide
in the grooves in drawing the cylinders along. The whole system would be
supported by a plate which could be suspended at a convenient point on the
passage of the tube where the gas is taken in. The apparatus thus applied, specially
for analyzing gas engendered by combustion. would be designated the combustio-
meter.
Having thus described my Invention and the best means of carrying it out, I do
not restrict myself to the precise details of the present description, but I claim as
my Invention,-
1. The use of a palladium wire for analyzing carburets in mines, and the regulating
combustion in furnaces.
2. The special description of apparatus for the particular purpose of analyzing
carburets.
3. All the other applications of which they are susceptible by the dispositions
described previously, and especially their use as eudiometers, capable in all cases of
replacing the chemists' eudiometer.
In witness whereof, I, the said Jacques Coquillion, have horeunto set my hand
and seal, this Twenty-fourth day of September, in the year of our Lord
One thousand eight hundred and seventy-seven.
NAAT