Improvements in Galvanic Batteries
Year: 1890

page_text: Date of Application, 6th Dec., 1890-Accepted, 21st Mar., 1891
COMPLETE SPECIFICATION.
Improvements in Galvanic Batteries:
A communication from abroad by FRIEDRICH MARX, of 47, Alt Moabit, Berlin,
in the Empire of Germany.
I, WILLIAM PHILLIPS THOMPSON, F.C.S., M.I.M.E., of the Agency for
Foreign Patent Solicitors, 6, Lord Street, Liverpool, and 6, Bank Street,
Manchester, both in the County of Lancaster, and 323, High Holborn, in the
County of Middlesex, Civil Engineer, do hereby declare the nature of this
invention, and in what manner the same is to be performed, to be particularly
described and ascertained in and by the following statement :-
Numerous efforts have been made to render iron, the cheapest of all metals,
capable of yielding constant electric currents, which efforts have led to the
construction of the iron and carbon elements for galvanic batteries forming the
object of the present invention. They are distinguished by electrolytes being
employed, in which chlorine in loose chemical combination is found and indeed in
such a way that large quantities of chlorine are given off from the electrolytes by
means of the current passing through the cells on the closing of the circuit.
The fact, that chlorine, in a very loose combination, is found in the electrolytes
in question, can be discovered by the colour and smell in clear electrolytes, and by
the smell alone in the case of brown coloured electrolytes. The outer formation of
the cells consists of acid-resisting receptacles of stoneware, porcelain, glass, or the
like, in which suitable electrodes-consisting alternately of iron and carbon-are
placed so that the same do not come in contact.
Electrodes in the form of plates are preferably employed and, according to the
number n of iron electrodes alternately with + 1 of carbon electrodes.
Mr. Marx has found the following three kinds of iron electrodes especially
advantageous:-
1st. Ordinary iron plates,
2nd. Iron plates with bandages as hereafter described,
3rd. Boxes of indifferent porous material containing conducting electrodes of iron,
the interior of which is filled up with broken pieces of iron.
The water-white electrolyte, which is coloured greenish yellow, shortly after the
mixture, by the released chlorine, is composed of ECIO, + 6HCl in a watery
solution, in which E can be any suitable element which forms, with C1O,, a
combination soluble in water. ECI+3H,O+3FeCl is formed by the action of
the electrolytes on the electrodes which is connected with the passage of the
current. The formation of gas is caused only to a scarcely appreciable extent
by the foreign substances, such as carbon and sulphur, contained in the iron.
Although ordinary sodium chlorate, NaClO3, can be used, as the cheapest and
most soluble material, for the production of electrolytes, the same result can be
obtained by means of a substance easily obtained everywhere, namely, chlorate of
potassium.
With regard to the molecular weights, it results from the following formula
KCIO,+6HCI that to 122° 5KC10, there must be employed 4 × 219 = 876
of a 25% hydrochloric acid or 5 × 219 = 1095 of a 20% hydrochloric acid.
In practice, the chlorate combination is dissolved in a 20 to 50 fold quantity of
water, and then the above calculated quantity of hydrochloric acid is added thereto
under continuous stirring.
The liquid, at first as clear as water, has, after a very short time the colour and
slight smell of chlorine water.

page_text: Although these batteries, by the use of iron, already yield a very cheap current,
it can yet be obtained more cheaply still by constructing a similar battery with a
brown electrolyte which utilises the residual products, after the same have been
chemically improved for the further production of the electric current.
The electrolyte, altered by the action on the iron electrodes, which now represents
principally a solution of proto-chloride of iron, can, in spite of its containing foreign
salts, be employed as a residual product for the production of cheap chemical
products, for instance, of a perchloride of iron sufficiently pure for electrical and
other technical purposes.
For the transformation of the protochloride of iron into perchloride, either gaseous
chlorine is introduced, or, after the addition of hydrochloric acid, the material is
oxidised with nitric acid by means of heat, or the process is completed by the
action of the electric current in the electro-chemical way. The brown electrolyte,
which, immediately on its preparation, has a slight smell of released chlorine, has,
in a chemically pure condition, the following composition :-
Fe,Cl + xHCI in watery solution.
For the sake of cheapness, however, crude perchloride of iron and crude
hydrochloric acid can be used, as the impurities contained in these products do not
act injuriously on the development of the electric current.
Among the batteries with one liquid, there are already several perchloride of
iron, iron and carbon batteries, but none of them have succeeded in avoiding the
polarisation which soon sets in, through the separation of iron oxide. Before the
iron oxide becomes separated, it is dissolved in the yet undecomposed iron
perchloride; the liquid becomes darker through the formation of peroxychloride;
on further decomposition, however, a portion of the iron, dislodged from the
dissolved electrode metals, which (iron) was before combined with chlorine, is
precipitated as iron oxide, whilst another part remains in solution as protochloride.
In order to prevent the formation of iron peroxychloride, as well as the separation
of iron oxide, it suffices to add to 1 kilo. of 29 to 30 per cent. iron perchloride liquid,
135 grammes of hydrochloric acid of 25% HCl.
The decomposed electrolyte has a clearly green colour without sediment. An
addition of 100 grammes of the same acid already suffices to prevent the deposit of
iron oxide; the electrolyte, however, to which this is added, is not pure green but
is dirty and even brown green, owing to the oxyperchloride contained in the
solution. These experiments succeed very clearly if the described quantity of
acid or the whole amount of the electrolyte be diluted with 500 to 1000 grammes
of water.
With an addition of hydrochloric acid, to the amount of 135 grammes to
the 1 kilo. of 29 to 30% iron perchloride liquid, this acid acts decidedly as a
depolariser.
That a greater addition of acid is requisite for depolarisation is contradicted by
the appearance of the entirely decomposed electrolyte. The entire amount of
available chlorine is hereby furnished by the perchloride of iron.
It is shown, from further experiments with mixtures of iron perchloride and
hydrochloric acid, that, by the addition of greater quantities than were requisite
for depolarisation, a much more active electrolyte was obtained, although it is
known that hydrochloric acid is not a suitable electrolyte for iron-carbon-batteries.
To 1 kilo. of 29 to 30% iron perchloride, there can be added with advantage as
much as 650 grammes of hydrochloric acid, but no more with advantage. A. further
excess of hydrochloric acid, although unnecessary, is not injurious.
It appears that, in such a mixture of both substances, the action is reversed, and,
when the whole amount of the chlorine contained in the hydrochloric acid comes
into action, then the iron perchloride forms the depolariser.
Here, however, the middle course appears to be the correct one, in so much that
both processes, by mutual depolarisation, in the following practical serviceable
mixture, induce the complete release of the chlorine.

page_text: 1 kilogramme iron perchloride liquid (29 to 30% Fе,C₁₂)
kilogramme hydrochloric acid (25% HCI)
kilogramme water.
Instead of the 25 percental acid, a correspondingly larger quantity of weaker acid
can be used.
With this liquid in the iron and carbon battery, constant currents for a period of
25 hours are yielded by protecting the iron electrodes, by means of porous bodies,
from too speedy contact with the whole contents of the cells.
In the ordinary way
of using, with unprotected electrodes, this clectrolyte yields at least for 5 hours a
constant current of 0.6 to 0.8 volt tension per cell.
The exhausted product of the electrolytes is an acid solution of iron proto-
chloride. This decomposed electrolyte can be chemically regenerated by the
introduction of chlorine and the addition of acid and constitutes then a store of
chemical energy, which, on its employment as an electrolyte, can be recovered as
electrical energy.
But the electrolytes can also be obtained, fully regenerated, in an electro-chemical
way, by simply conducting an electric current through the cells when all the iron
previously dissolved is again deposited at the negative electrode, and chemical iron
perchloride and a watery solution of hydrochloric acid are again formed, whereby
the iron electrode is also regenerated.
This iron and carbon battery differs (by the employment of the above described
composition) essentially from other iron perchloride, iron and carbon batteries,
which are not regenerative, as well as from accumulators, as these latter must be first
charged if it be desired to obtain a current therefrom.
A protective covering to hinder the, to some extent, undesired access of the
electrolyte to the iron electrodes, is made in the following manner :-
The electrode is first wrapped in one layer of damped silk paper, round that
comes a layer of damped thick English blotting paper, round that again a covering
of shirting, dowlas, linen or similar material, which has been freed from its finish,
and over all the coverings a cord of the material of the last layer is wrapped round
both as a further covering, and also to hold them firm, and is fastened at the upper
end of the electrode.
If the metal electrodes of the battery are provided with this protective bandage
this regenerative primary battery has all the properties of a good accumulator cell,
which retains the charge for months.
It should be noted, with reference to the composition of the electrolyte, that
other quantities than those herein enumerated can be proportionately employed,
without thereby altering anything in the essential part of this invention, such
alterations would however be made at the expense of the result, as the further
the figures of the proportion differ from those given above, the smaller will be the
useful effect.
It is advantageous, as a measure of precaution, wherever it is possible, to conduct,
to the outside air, the traces of carburetted hydrogen and sulphuretted hydrogen
resulting from the use of impure iron.
The battery of this invention shows a very great superiority over all hitherto
existing primary and secondary batteries, inasmuch as, in the production of the iron
perchloride employed as the electrolyte, valuable bye products, such as metals,
alkalies, lyes, etcetera, can be recovered, which enable the expenses of the battery to
be so much diminished that the current produced by this battery can compete with
that produced by machines.
Having now particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be performed, as communicated to me
by my foreign correspondent, I declare that what I claim is :-
1. A regenerative iron and carbon battery distinguished by an electrolyte

page_text: containing chlorine in loose chemical combination, which can be made either of
hydrochloric acid (HCI) and a chlorate of any suitable element, or of hydrochloric
acid (HCl) and iron perchloride in a watery solution.
2. In the battery described in Claim 1, a protective bandage for the iron
electrode consisting of a covering of damped silk paper, with a covering of thick
blotting paper over that, and, surrounding both of these coverings, a cover of
shirting, dowlas, linen or other similar material from which the finishing has been
removed.
Deted this 5th day of Dacomber 1800
WM. P. THOMPSON & Co.,
Agents for the Applicant.

page_text: Date of Application, 6th Dec., 1890-Accepted, 16th May, 1891
COMPLETE SPECIFICATION.
'
Improvements in the Electro-chemical Formation of Chlorine and
Chlorine Compounds.
A communication from abroad by FRIEDRICH MARX, of 47, Alt Moabit, Berlin, in
the Empire of Germany, Chemist.
I, WILLIAM PHILLIPS THOMPSON F.C.S., M.I.M.E., of the Agency for Foreign
Patent Solicitors, 6, Lord Street, Liverpool & 6, Bank Street, Manchester, both in
the County of Lancaster & 323 High Holborn in the County of Middlesex, Civil
Engineer, do hereby declare the nature of this invention and in what manner
the same is to be performed, to be particularly described and ascertained in
and by the following statement :-
This invention relates to the electro-chemical formation of chlorine and chlorine
compounds and especially has for its object the process of producing proto-chloride
of iron and perchloride of iron in the cheapest way conceivable. By the invention
are obtained as direct bye-products, metals, alkalies, and lyes, and as indirect bye-
products, caustic lime, chloride of lime and salts.
This process is founded on the application of electrolytic chlorine, and its great
advantage consists as follows:-
Chlorine is obtained by the electrolysis of metallic chlorides. The electrolytic
decomposition of the metallic chlorides can be of two kinds :-
1. Electrolytic decomposition of watery solutions of the metallic chlorides. The
main product of this is chlorine.
The bye-products are the hydrated oxides of the metals and alkalies. More
rarely the hydrated oxides of alkaline earths and other earths, and from the
remaining metallic chlorides, the metals as such.
2. Electrolytic decomposition of melted metallic chlorides or mixtures thereof or
double combinations of the same.
The main product is chlorine.
The bye-products are metals or metallic alloys.
The electrodes employed for the decomposition consist of—
(a) The positive-carbon.
(b) The negative-carbon or metal.
Negative carbon electrodes should be used, for instance in the decomposition of
alkaline chloride combinations in watery solution and negative metallic electrodes
in the decomposition of melted metallic chlorides, and, when possible, of the metal
which is obtained as a bye-product of the decomposition.
The apparatus, serving to produce the above-named chlorine combinations,
consists of decomposing cells, under which a heating apparatus is placed. The
vessel holding the decomposing cells can be made, either of metal or of porcelain,
glass or the like.
A tight-closing cover with a pipe for conveying the chlorine away is placed on
each decomposing cell, after that the same has been supplied with the material to
be electrolysed and the electrodes have been inserted, this cover only allows the
electric connecting wires to pass through.
The material to be preferred for the cover is glass, stoneware, porcelain or
enamelled iron.
On the accompanying drawing, the apparatus, suitable for the hereindescribed
process of this invention, is shown.
In the trough A, the electrolyte B is placed, and in it are plunged the positive

page_text: electrodes P and the negative electrodes N. A tight-fitting cover C is placed on
this trough, through which the conducting wires p and n pass.
The conducting pipe F leads from the cover to the first of a number of
absorption vessels H, arranged one behind the other.
The chlorine-conveying pipe F is brought down nearly to the bottom of the first
absorption vessel H. Near the top of this vessel, a bent-down connecting pipe K
leads in a similar manner nearly to the bottom of the second receptacle, and so forth.
The chlorine evolved by the passing of the electric current through the
decomposing cells, is thus conducted into the absorption vessels. The best
material for these absorption vessels is stone-ware. It is self-evident, however,
that other material, suitable for this special purpose, such as glass carboys or the
like, can be employed. It is advantageous to give the absorption vessels convenient
wide openings for the insertion and removal of the materials, which openings are
provided with a tight fitting stopper.
Suppose iron filings and water be placed in the absorption vessels and chlorine
be conducted therein until, not only the iron is dissolved and is transformed into
protochloride of iron, but also the iron protochloride formed is converted into iron
perchloride. In place of iron and water, the electrolyte decomposed in iron and
carbon batteries can be used; the main constituent of which is also a solution of
iron protochloride. The decomposing cells are filled with a solution of chloride of
sodium, for instance, and preferably carbon electrodes are inserted therein, which
are connected alternately with the positive and negative poles of a current producer,
and the cells are then closed with the cover. After having carefully ascertained
that the conducting pipe debouches under the level of the liquid in the absorption
vessels, the current is passed through the decomposing cells, and the result is the
formation of chlorine gas.
If large decomposing cells be employed, it is advantageous to warm the same
during the process of decomposition in order to prevent large quantities of chlorine
remaining behind in solution in the liquid of the decomposing cells.
Both direct and indirect means of firing for warming the decomposition cells can
be employed. In the drawing, the decomposing cells are placed in a sand-bath D,
which is heated by means of a stove E.
In place of chloride of sodium, the application of Stassfurt waste salts, as well
as sea salt, when that can be cheaply had, is specially advantageous.
If it be desired to obtain the chlorine from melted metallic chlorides, the use of
the double chloride of sodium and aluminium is especially to be recommended. The
finished iron perchloride is reduced to the requisite dilution of 29 to 30% Fе,Cl,
the superfluous chlorine contained in the same need not be driven off, because, when
employed for electrical purposes, it is not harmful, but, on the contrary, desirable.
As described, the chlorine is partly obtained by the electrolytic decomposition of
alkaline metallic chlorides, whereby alkali hydrates remain, which are further
worked up into alkaline carbonates in the following way :-
Furnaces are built in which lime is burnt, the carbonic acid resulting therefrom
is confined in gasometers, washed and purified, and utilised for transforming the
alkali hydrate, resulting from the electrolytic preparation of chlorine, and which is
collected from several decompositions into alkali carbonate. The burnt lime
obtained can, if required, be converted into hydrate of lime, and, by saturation
with electrolytic chlorine, can be then transformed into chloride of lime.
Having now particularly described and ascertained the nature of the said
invention, and in what manner the same is to be performed, as communicated to me
by my foreign correspondent, I declare that what I claim is :-
1. The hereindescribed process for the manufacture of iron protochloride, iron
perchloride, and chloride of lime, in which chlorine gas, produced by means of
electrolytes, formed of metallic chloride compounds, or of a mixture of the same,

page_text: is employed for the dissolving of iron and transforming the iron protochloride into
iron perchloride and for the saturation of hydrate of lime.
2. In the process described in Claim 1, the obtaining of metals, lyes and
alkalies as bye-products, substantially as described.
Dated this 5th day of December 1890.
WM. P. THOMPSON & Co.,
Agents for the Applicant.