the Utilization of the Products thereof.
Year: 1887

page_text: Date of Application, 25th Oct., 1887
Complete Specification Left, 25th July, 1888
Complete Specification Accepted, 2nd Nov., 1888
in the Utilization of the Products thereof.
I WILLIAM SPILKER of No. 11 Horn Strasse, Berlin Germany Chemist do hereby
declare the nature of this invention to be as follows:-
The great difficulty existing in electrolysing the haloid salts especially the
chlorides of the alkali metals was the strong polarisation produced by the halogene
especially the chlorine generated at the anode and by the impossibility firstly to gain
an alkali sufficiently free of chloride because the chlorine with its gaseous form
enters with facility into the cathode compartments containing the produced alkali
secondly to gain the chlorine without a considerable loss further in this case the
high electrical tension necessary for the decomposition makes impossible a technical
fabrication.
The method invented by me consists essentially in the following.
I obtain the suppression of the polarisation of the chlorine by the introduction of
slaked lime (or quick lime dissolved in chloride of calcium and consequently changed
into basic chloride of calcium) into the anode compartment which is separated from
the cathode compartment by a diaphragm of porous clay or similar material.
I obtain by this way by one fabrication firstly in the cathode compartment the
alkali perfectly or nearly free from chlorine, secondly in the anode compartment the
chlorates respectively by a low temperature the hypochlorites of potash or soda or
calcium mixed with chlorides of calcium. By an analagous method I obtain the
bromates and iodates.
The polarisation of the hydrogene which is produced by the decomposition of the
haloid salts of the alkali or similar metals will be suppressed by means of a continuous
current of air or steam or a mixture of both blown over the surface of the cathode so
that the solutions shall completely come in contact with the anodes and cathodes and
be decomposed. I pass a current of steam or air or a mixture of both into both
compartments in such way that an intense motion of the electrolyte is obtained. If

page_text: by the above described means I have obtained from the chlorides of the alkali metals
firstly the corresponding alkali and secondly the chlorate or hypochlorite the first can
be worked further by evaporation and introduced into commerce.
The chlorate also can be worked further by crystalisation and introduced into
commerce or as well as the hypochlorites it may be employed in an original manner
for the extraction of metals from ore for instance gold silver zine mercury &c. I omit
the further working of the solutions gained by the electrolysis and containing the
chlorates or hypochlorites of lime potash or soda besides the chlorides of calcium and
I employ them directly under this form mixed with acids especially with hydrochloric
acid for the extraction of metals from their ores whereby the chlorine respectively the
chloric acids developed in statu nascendi works as dissolving agent. Instead of using
the hypochlorites and the chlorates for the extraction of metals out of the bath I can
employ them in it for the chlorination or oxydation of a series of bodies thus for
instance I may change alcohol and.similar bodies into chloroform by conducting them
in the form of vapour during the electrolytic process through the closed and heated
anode compartments whereby chloroform is distilled. In the same manner the iodato
of lime formed in the anode compartment by the decomposition of iodides is employed
for the manufacture iodoforme. In the same manner the toluoll may be changed into
chloride of benzyl and then into anthracene or the salts of antrachinone (0.14 H 802)
from which in a well known manner the alizarine may be separated.
GEO.
CUMBERPATCH,
64, St. George's Road, Warwick Square, S.W.,
Agent for the Applicant.

page_text: in the Utilization of the Products thereof.
I WILLIAM SPILKER of 64 St. Georges Road Warwick Square London S.W.
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 concerns the decomposition of solutions of haloid salts by electrolysis,
especially the decomposition of solutions of chloride of potassium and chloride of
sodium.
The proceeding is characterized that by a single electrolytic operation I obtain in
the bath on one side the alkalies, caustic soda or caustic potash and on the other side
hypochlorites under chloric acid or chlorates. The principal advantage in this
proceeding consists-Firstly in the simplicity of the installation on which the
operation to suck off the gaseous formed chlorine (difficult to carry out when in large
quantities) is avoided-Secondly that the alkalies are obtained in a continuous
manner and not mixed with clorides. Thirdly in the complete utilization of the
materials and the absolute and complete gain of the products (alkalies and chlorine)
without any loss and Fourthly the proportionate low use of electric power.
In a second line it is the question to employ the hypochlorites chlorates &c. gained.
in such a manner for chlorating and oxidation purposes.
I separate the cathode from the anode by à diaphragm of porous clay or similar
material. But instead of forming the chlorine on the anode in a gaseous form which
has been necessary hitherto to obtain the alcali as well as the chlorine under the
form of hypochlorite or chlorate (by which proceeding the anode compartiment had
to be closed) I make the anode compartment open and fill it up, in addition to the
chloride to be decomposed, with a certain quantity of slaked lime, by which the
polarisation of the chlorine is abolished. Instead of lime I may employ a solution of
basic chloride of calcium 3 Ca O Ca CI 2 x 16 H 2 O which is obtained by slaking.
lime in a solution of chloride of calcium. Lastly we may employ instead of lime
other bodies which are not good conductors of electricity especially the oxide or
hydrates of Barium strontium magnesium zinc and the carbonates and bicarbonates
of them. The essential condition is in all cases that the employed materials must be
bad conductors of electricity in comparison with the chloride of potassium and the
chloride of sodium Therefore one cannot employ caustic potash or caustic soda firstly
because such solutions which are better conductors of electricity than the chlorides
of potassium and sodium, are decomposed by the current and therefor the decom-
position of the chlorides will be incomplete, and secondly because the alcali formed
on the catode will be consumed. The chlorides of the named bodies are formed (as it
will later be shewn) by the electrolytic procedure, and were they not worse conductors,
than the chloride to be decomposed, they would also be decomposed into oxide hydrate,

page_text: and chlore by the electric current, and consequently an infection of the alcali and
an obstruction of the porous diaphragm by indissolvable bodies would result.
In all these cases the chlorine formed on the surface of the anode will be tied in
statu nascendi By employing the named oxyde hydrates or basic chlorides in the
anode compartment the corresponding hypochlorites are formed or chlorates and
chlorides in a higher temperature of the solution. By employing carbonates or
bicarbonates under chloric acid by disappearing of carbonic acid is formed.
The electrolytic decomposition of the haloid salts of the alcali metals effects also,
that the anode compartment being filled up with hypochlorites underchloric acid
respectively chlorates and chlorides of calcium magnesium &c. will be diminished of
its contents of chloride of sodium and of potassium and its volume would also be
reduced whilst the catode compartment increases its volume as well as its contents
of caustic potash or caustic soda.
Thus a substitution takes place in such manner that in the anode compartment
the bad conducting bases of calcium &c. are consumed whilst in the catode
compartment the bases of potassium are produced. This fact is the principal
difference between our method and the method already known for the manufacture
of alcali containing solutions by the electrolysis, by which gaseous chlore or chlor
water is formed.
On the decomposition of the haloid salts of the alcali or similar metals at the catode,
hydrogen is formed which causes a high polarisation and consequently an augmentation
of the electric tension. This polarisation can be avoided by a continuous current of
air or steam or a mixture of both being blown over the surface of the catode, made
of coal or metal by which procedure the hydrogen sticking to the catode is constantly
carried off and therefor produces a considerable reduction of the electric tension.
If carbonic acid is employed solutions of carbonate will be formed or bicarbonates
(especially of potassium) are separated in a crystallised form.
I will now give some technical details.
I employ the inner surface of the electrolytic bath directly as catode. This
besides the simplification of the whole installation has the great advantage that
secondary electrolytic procedures are excluded. For it is a fact, that if, besides the
electrodes still other metallic bodies are in the bath a secondary decomposition of
them will take place as soon as the metal pieces are reached by the current. In our
process chlorides of metal would be formed which would corrupt the formed alcali.
On the drawing accompanying, the apparatus for blowing air or vapour over the
surface of the catode is omitted K is the bath constructed ordinarily of iron and well
isolated, D is a diaphragm of clay open at top, A is the anode, is an aflux basin,
S1 and S2 are collecting basins the dotted lines representing the electric wires.
If we wish to produce for instance caustic potash or chlorate of potash, I fill up
the bath K with a solution containing approximately two per cent. chloride of
potassium whilst D is filled with a solution concentrated in chloride of potassium, and
saturated with lime and giving therefor an alcalic reagent, S 1 is filled with lime.
If I close the current and conduct the solution from Z to D then through E2 there
will How continually to S 2 a finished lie of potash, which contains at the beginning
of the procedure a little chlore but will later be completely free from it, whilst the
siphon or sucker H holds the nivean in D on the same level and conducts the lic
containing the hypochlorite of calcium and the chloride of calcium to S 1. In $1 the
lime is slaked in. the lie forming soluble oxychloride of calcium. Then the lie is
reconducted to Z arriving again in D therefrom to S 1 and receives new quantities
of lime &c. This procedure will be continued until only a small quantity of chloride
of potassium remains in the lie only so much as is indispensable for the current. Then
Zis filled again with a fresh lie of chloride of potassium. As often as the lie passes
through D. it is able to receive fresh quantities of lime because it is more and more
saturated with chloride of calcium. If the lie is made to flow rapidly through D
no smell of chlore will be perceived. By employing a temperature over 40° C: chlorate
of calcium will be formed instead of the hypochloride of calcium which with the
chloride of potassium is changed into chlorate of potassium and chloride of calcium.

page_text: The chemical procedure during the electrolysis is as follows
1. On the beginning of the electrolysis
compartment loses the chloride of potassium.
The same apparatus may serve in the employment of the solutions of bicarbonates
especially magnesium.
Then S 1 is filled with the carbonate of magnesium which is reduced by the carbonic
acid under pressure into soluble bicarbonates.
At last I may employ the same apparatus for the application of a milk of lime
magnesia &c. in the anode compartment D.
Then I produce by means of a steam blower or other apparatus a vivacious motion
in the compartiment D to prevent a deposition of the lime, &c. This procedure may
be employed where carnallit exists which may be employed directly instead of chloride
of potassium, to fill the compartment D with magnesia or magnesit. I employ also
the carnallit so that by means of lime or basic chloride of calcium we precipitate the
magnesia and we use the remaining lie containing chloride of potassium and chloride
of calcium for the apparatus. In all cases I may put the lie remaining from the
crystallization of the chlorate of potash and containing a little chloride of potassium or
chlorate of kalium again into the apparatus after having saturated it with chloride of
potassium. It may be employed until the lie is too full of chloride of calcium or
magnesium.
In the same manner caustic soda and solutions of chloride of lime or chloride of
sodium are made. The same procedure is employed for the decomposition of other
laloid salts from other metals.
Instead of one bath K which is supplied from Z I can place more baths K' K &c.
oue behind the other in the form of a staircase joining the anode and catode compart-
ments by suckers or syphons. The solution of the catode then is flowing from K to
K and therefrom to and so on until it reaches S 2. The solution of the anode
compartment is going from Z to D, and from D to D1 D2 and so on until it reaches $ 1.
I also arrange it in such manner that metal suckers from bath to bath may be
employed.
The solutions containing underchloric acid or hypochlorites gained in the above
described manner may also be employed immediately for bleaching purposes while at
the same time the lies containing alkalis may be utilized.
The solutions may also be used for the extraction of metals especially gold and
silver from their ores.

page_text: If the solutions coming from D out of the bath are brought into contact with ores
saturated with acids (hydrochloric acid) the chlore retained by the electrolysis will be
free again and acting in statu nascendi energetically dissolving upon the metals. As
soon as the lie after having received gold &c. has lost its contents of working chlore,
it may be freed from the gold or other precious metals by employing metals or
sulphuretted hydrogen in a well known manner.
The solution after being filtered may be saturated again with lime and again sent
through the electrolytic anode compartment D. A part of the solution of chloride of
calcium may be employed for the manufacture of muriatic or hydrochloric acid from
sulphuric acid.
At last I may employ the above described procedure to execute within the bath
directly procedures of chlorination and oxydation. Such a chlorination gives of course
other products than those produced by the chlore itself. On joining for instance to
the anode compartment D 1 which is filled with the chloride to be decomposed and with
basic bodies or carbonates, still a body of alcohol, the chloroform will be produced
which in an airtight closed anode compartment and at an appropriate temperature will
be distilled off.
The best manner is to induce the alcohol under the form of vapour. One obtains
then in the anode compartiment chloride of calcium carbonic acid and chloroform.
One may execute this chlorination also in the closed collecting basin § 1 by adding
continually or from time to time some alcohol.
With great advantage I may produce in the described apparatus the alizarine by the
anthracene. For this purpose the anthracene is dissolved in sulphuric acid, neutralized
with carbonic lime and this solution is added to the lie going through D and com-
posed as above described. If now the whole electrolytic bath is brought to a high
temperature we obtain in D a solution of anthrachinone bisulphonate of lime. This
solution mixed with soda or potash gives anthrachinono sodium or potassium
bisulphonotes.
The latter solution after being clarified is evaporated and then dissolved with the
alcali formed in K.
From the alizarine kali gained in such a way the alizarine may be produced in a
well known way.
Having now particularly described and ascertained the nature of my said invention
and in what manner the same is to be performed I declare that what I claim is..
On the electrolysis of watery solutions of the chlorides bromides and iodides
1. The application of oxyd hydrates carbonates or bicarbonates of the calcium,
magnesium baryum strontium and zinc (which are not good conductors of electricity)
in the anode compartment seperated from the catode by a diaphragm for the
depolarisation of the chlorine bromide and iodine and the fabrication of solutions of
hypochlorites under chloric acid chlorates bromates and iodates.
2. The substitute for the named oxid hydrates by basic solutions, of haloid salts
especially by the oxychloride of calcium for the same purposes as at 1.
3. The simultaneous production of caustic soda or potash on the one part and of
hypochlorites underchloric acids and chlorates on the other part in the same electrolytic
bath in such manner that the catode compartment is filled with a solution of chloride
of sodium or chloride of potassium and the anode compartment beside a solution of
chloride of sodium or potassium contains still a suspension of the above-named oxyd
hydrates carbonates, bicarbonates or basic solutions of haloid salts.
4. The depolarisation of the hydrogen by means of a continuous current of air
steam or vapour or of another gaseous body blown over the surface of the catode.
5. The injection of gaseous formed bodies into the anode compartments filled with
the named oxyd hydrates or carbonates, or the application of a mechanical apparatus
for the purpose of removing or agitating the liquid.
6. The application of the hypochlorites gained by the procedure described under
1, 2, 3, 4 and 5 or the solutions containing underchloric acids for bleaching purposes.
7. The application of the hypochlorites or the solutions containing underchloric

page_text: acids or chlorates gained by the procedures described under 1 2 3 4 and 5, for the
extraction of metals from their ores out of the electrolytic bath.
8. The application of the solutions containing underchloric acid hypochlorites and
chlorates gained by the procedure described under 1 2 3 4 and 5 for the chlorination
or the oxydation of organic bodies within and out of the electrolytic bath especially
for the fabrication of chloroform and alizarine by introducing alcohol or anthrazenotes
in the anode compartments filled with the bodies named under 1 and 2.
9. The execution of the procedure described under 1 2 3 4 5 and 8 in such manner
that the solution of haloid salts to be decomposed containing besides the basic haloid
salts or bicarbonates or oxyd-hydrates or carbonates named under 1 and 2 is passing
continually through the anode compartments and conducted into vessels, in which the
oxyd-hydrates carbonates bicarbonates, and basic haloid salts partially consumed are
taken up again and conducted again through the anode compartment whilst at the
same time the solution of alkali formed on the decomposition of the haloid salts of the
alkali metals is flowing continually out of the catode compartment without being
restored by fresh solution.
10. The arrangement that for the procedure described under 1 2 3 4 5 8 and 9 the
inside of the electrolytic bath may be employed directly as catode.
11. The arrangement of the electrolytic bath, placed in the form of a stair case
joined together by the electric wires in such manner that the application of metal
suckers is practicable as they are not consumed by the current substantially as shewn
in the drawings the electric wires being shewn in dotted lines.
UITIS
wood tray of ey
1000
GEO. CUMBERPATCH,
6, Annette Road, Loraine Road, Holloway, N.,
Agent for the Applicant.