Improvements in or in connection with the Preparation of Amalgams containing Aluminium, Magnesium, or Zinc.
Year: 1897

page_text: Date of Application, 28th Jan., 1897
Complete Specification Left, 30th Sept., 1897-Accepted, 28th Jan., 1898
Improvements in or in connection with the Preparation of Amalgams
containing Aluminium, Magnesium, or Zinc.
WILHELM GUSTAV HEINRICH WOLFF, Dr. Phil., Chemist, of Berlin,
Ziethenstrasse, 23, in the Empire of Germany, do hereby declare the nature of
this invention to be as follows:-
The amalgan of aluminium is already known through the publication of
A. Cossa, as well as of Baille et Féry. This compound decomposes water, but not
alcohol. The evolution of hydrogen is not so energetic as in many other. reduc-
tions and the compound offers only a small surface. If however, in addition to
mercury, a third suitable element is introduced, as described below, the aluminium
is converted into the molecular state, forming with alcohol the alcoholates and
acquiring the qualities of sodium. The alcoholates of magnesium have not yet
been made. If aluminium is amalgamated, as is commonly done with corrosive
sublimate, washed with alcohol and heated in the latter, Hg is again precipitated
in the form of globules. The reaction takes place in an entirely different manner
in the presence of a certain amount of zinc chloride. The method is as follows:
10 parts of sheet aluminium of about 1 mm. in thickness were cut into pieces of
3-4 mm. square and put into a flask connected with a condenser, having at the
bottom a large evacuating valve covered with a fine sieve. The metal is treated
with 20 parts of water. 2 parts of corrosive sublimate and 1 part of zinc chloride
are dissolved in about 30 parts of hot water and the solution allowed to flow into
the flask. The whole is stirred slowly. Hg and Zn are precipitated on the
freshly cut surfaces of the metal; as soon as the bubbles of hydrogen become larger
and the edges of the pieces just begin to exfoliate, the hot solution is drained off,
the residue washed with a quantity of cold water and then with alcohol and 100
parts of alcohol allowed to flow to the same. All these operations have to be
carried out rapidly. If the solution is allowed to flow off too late, the reaction
soon gets beyond control, the mercury is precipitated by the overheating of the
solution, and the reaction hereby brought to a stand still. The evolution of
hydrogen becomes greater and greater, and simultaneously the complete exfoliation
of the metal takes place in the form of an extended harmonica. Thereupon the
leaves begin in turn to be subdivided into small glittering leaflets; the reaction is
accompanied by a strong developement of heat and evolution of hydrogen. There
remain aluminiumethylate, Hg. Zn as metals, and the residues off silicon, iron
etc.
Therefore I claim
(1). "Manner of preparing the alcoholates of aluminium or magnesium by
neans of zinc and mercury.
2). Manner of generation of hydrogen by means of the action of zinc chloride
and corrosive sublimate on sheet aluminium (rolled plate) in watery-alcoholic
solution "

page_text: If the reaction is interrupted, when the harmonicalike exfoliation begins and
water and alcohol are eliminated by means of indifferent solvents (benzol, etc.) the
resulting amalgam is ready for use.
Gladstone & Tribe (Journal of the Royal Society 39, 3 and 41, 5.) prepared the
aluminium alcoholates through the action of iodine on cut aluminium foil in
alcoholic solution. They explain the reaction by assuming, that aluminiumiodide
is first formed, the same decomposes alcohol, forming hydriotic acid and aluminium-
ethylate. The hydriotic acid reacts on the unattacked metal, hydrogen and
aluminium-iodide being formed etc. until the whole mass has been changed.
Although it may not appear probable, that under the circumstances, in which the
compound is formed in watery solution, as well as in the cases, in which the solid
metals are brought into contact, that aluminiumchloride can be formed, and in a
similar manner as above the iodine, generating hydrochloric acid and alcoholate,
accomplish the successive dissolution, nevertheless it has been proven by several
reactions; the aluminium contains the necessary amount of chlorine, although the
same cannot be quantitatively determined, on account of the small quantity
present. Two reactions, hence, occur side by side, the combination of Al with Hg
and Zn and the formation of aluminium chloride made possible thereby. Another
explanation of the reaction is possible. The action of the zinc can depend on the
mediatory action of chlorine; the caloric power of the dissolved Zn is greater
than that of the solid Al, and that of the dissolved Al greater than that of the
solid Mg. If Zn combined with Hg is to be regarded as dissolved, Al, Cl in a
hydroxyl solution is decomposed into the alcoholate and zinc chloride. In the pro-
gress of the reaction always more Al atoms of the large excess present in the
Hg are dissolved, Zn. is again precipitated and is dissolved in Hg etc.
reaction takes place entirely in an alcoholic solution only half as much sublimate
is necessary, since Hg C is soluble in alcohol, if it takes place entirely in a watery
solution careful cooling is necessary. If the bright plate is rubbed with zinc-
amalgam, or if the amalgamated metal is wrapped in zinc foil, the katalytical
alloy is likewise formed. The same is the case if the earthy metals are alloyed
with the computed amount of zinc (0.1-0.4 %). All these methods are identical.
The metal is always converted into the katalytical state by the simultaneous action
of Zn and Hg, which is complete when all the metal has been used up. Magnesium
has to be cut finer. The formation is completely made in alcoholic solution and
is less energetic and takes place slower. On analysis, which can be made either
by determining Hg and Zn in the decanted solution or by direct determination,
the formula Al Hg, Zu is obtained. It is obviously the amount of the elements
precipitated on the metal, dependent on the length of the time of the action of
the Hg Zn solution on the one hand, and on the other, since a continued consumption
of Al takes place ending only after all the metal has been used up, the amount of
aluminium gradually decreasing. The relation of the zine to the mercury should
not be changed to any extent. An excess of mercury or zinc prevents the reaction.
In the latter case all the mercury is precipitated by the excess of zinc. Con-
sequently I claim
If the
(3). "Method for the preparation of zincamalgam or zinc containing aluminium
or magnesium mercury and zinc being precipitated either as metals or from their
solutions on aluminium or magnesium, or the zinc alloy being brought in con-
tact with mercury, or the mercury alloy with the zinc, in all cases approximately
corresponding to the formula Al (Mg) Hg Zn, whereby the zine in the magnesium
alloy can be replaced by aluminium."
In the alcohol or water, in which the alloy is formed organic bodies can be dis-
solved and are easily reduced. Nitro compounds are converted into amidocom-
pounds and oximes into amines. Cyclical hydrocarbon bodies containing one
nitrogen atom, as pyridines and chinolines etc. give hydrogenized dicompounds.
Therefore I claim finally
"Manner of reduction and condensation of organic bodies by means of the said
katalytical alloies.

page_text: Having now particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be performed, I declare that what I
claim is
i
1. Manner of preparing the alcoholates of aluminium or magnesium by means of
zinc and mercury..
2. Manner of generation of hydrogen. by means of the action of zinc chloride and
corrosive sublimate on sheet aluminium (rolled plate) in watery-alcoholic solution.
3. Method for the preparation of zinc amalgam or zinc, containing aluminium
or magnesium; mercury and zinc being precipitated either as metals or from their
solutions on aluminium or magnesium, or the zinc alloy being brought in contact
with mercury or the mercury alloy with the zinc, in all cases approximately corres-
ponding to the formula Al Hg Zn or Mg Hg Zn, whereby the zinc in the
magnesium alloy can be replaced by aluminium.
.
4. Manner of reduction and condensation of organic bodies by means of the said
katalytical alloyes...
This 10th dow of Folruary 1897
HEINRICH WOLFF, Dr. Phil.,
Berlin, W., 23, Ziethenstrasse, Germany.
Improvements in or in connection with the Preparation of Amalgams
containing Aluminium, Magnesium, or Zinc.
WILHELM GUSTAV HEINRICH WOLFF, of 23, Ziethenstrasse, Berlin, in the Empire
of Germany, Dr. Phil., Chemist, 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:-
--
The amalgam of aluminium is already known through the publications of
A. Cossa (Ber. d. Deutschen Chem. Ges. III 204 und 368/69) as well as of Baille
et Fery (Annales de Chim. et de Phys. 1889 serie VI tome XVII). This com-
pound decomposes water but not alcohol. The evolution of hydrogen is not so
energetic as in many other reductions and the compound offers only a small
surface. If however, in addition to mercury a third suitable element is introduced
as described below, also the alcohols are decomposed into the ethylates and hydrogen.
1.) 10 parts of sheet aluminium of about 1 mm. in thickness were cut into pieces
of 3-4 mm. square and put into a flask connected with a condenser having at the
bottom a large evacuating valve covered with a fine sieve. The metal is treated
with 20 parts of water. 2 parts of corrosive sublimate and 1 part of zincchloride
are dissolved in about 30 parts of hot water and the solution allowed to flow into
the flask. The whole is stirred slowly. Hg and Zn are precipitated' on the freshly
cut surfaces of the metal; as soon as the bubbles of hydrogen become larger and
the and the edges of the pieces just begin to exfoliate the hot solution is let off,
the residue washed with a quantity of cold water and then with alcoliol, and 100
parts of alcohol allowed to flow to the same. All these operations have to be
carried out rapidly. If the solution is allowed to flow off too late the reaction soon
gets beyond control, the mercury is precipitated by the overheating of the solution,
and the reaction hereby, brought to a stand-still. The evolution of hydrogen
becomes greater and greater and simultaneously the complete exfoliation of the
metal takes place in the form of an extended accordion. Thereupon the leaves
begin in turn to be subdivided into small glittering leaflets, the reaction is accom-
panied by a strong developement of heat and evolution of hydrogen. There remain

page_text: aluminium-ethylate and Hg, Zn as metals and the residues of, silicon, iron etc.
If the reaction is interrupted, when the accordion-like exfoliation begins and water
and alcohol are eliminated by means of indifferent liquids, like benzol, petrol etc.,
the resulting amalgam is ready for use.
2. 10 parts of sheet magnesium of about 1 mm. in thickness were cut into pieces
of 1-2 mm. square and put into a flask as described. 1 part of corrosive sublimate
and 1 part of zinc chloride or of aluminium chloride (Al, Cl) are dissolved in
30 parts of hot alcohol and the solution allowed to flow to the same. If mercury
and zinc are precipitated and a quantity of magnesium ethylate is dissolved in the
alcohol, the solution is let off, just before the alcohol begins to congeal by the
surplus of ethylate. The remainder is washed with alcohol and 100 parts of
alcohol put to the same. The reaction softly commences and its duration is
dependent of the fineness of the metal. There remain magnesium-ethylate, Hg
and Zn.
3. 10 parts of aluminium are molten and alloyed with about 2 per cent. of zinc and
then rolled into plates of about 1 mm. in thickness and cut in the manner as already
said, 1 part of corrosive sublimate is dissolved in about 30 parts of hot water and
the triple alloy formed in the manner as described under No. 1.
10 parts of magnesium are molten and alloyed with 2 per cent. of zinc or
1 per cent. of aluminium, then rolled into plates and cut into pieces of 1-2 mm.
square 1 part of corrosive sublimate is dissolved in about 30 parts of hot alcohol
and the triple alloy formed in the manner as said under No. 2.
On analysis, which can be made or by determining Hg and Zn in the decanted
solution or by direct determination, the formulæ Mg2 Hg Zn and Al Hg Zn
are obtained.
125
Gladstone and Tribe prepared the aluminiumethylates through the action of
iodine on cut aluminium foil in alcoholic solution. They explain the reaction by
assuming, that aluminiumiodide is first formed, the same decomposes alcohol form-
ing hydriodic acid and aluminiumethylate. The hydriodic acid reacts on the
unattacked metal, hydrogen and aluminiumiodide being formed, etc. Although it
may not appear probable, that aluminiumchloride can be formed, when Al Hg Zn
is formed in watery solution, as well as in the cases in which the solid metals are
brought into contact, nevertheless it has been proven by several reactions. The
aluminium contains the necessary amount of chlorine although the same cannot be
determined quantitatively on account of the small quantity present, and in a
similar manner as above the iodine, generating hydrochloric acid and ethylate the
successive dissolution is accomplished. Two reactions, hence, occur side by side, the
combination of Al or Mg with Hg and Zn and the formation of aluminiumchloride
made possible thereby.
Having now particularly described and ascertained the nature of my said inven- 4
tion and in what manner the same is to be performed, I declare that what I
claim is:
The process of combining the triple alloies of aluminium zinc and mercury or
of magnesium zinc and mercury or of magnesium aluminium and mercury in
all cases approximately corresponding to the formulæ Al Zn Hg, Mg125 Zn Hg,
Mg125 Al Hg, consisting in precipitating mercury and zinc on cut aluminium or
magnesium, or in precipitating mercury alone on the zinc alloy Al111 (Mg 125) Zn,
whereby the zine in the magnesium alloy can be replaced by aluminium.
Dated this 17th day of January 1898.
WILHELM GUSTAV HEINRICH WOLFF,
23, Ziethenstrasse, Berlin, W., Germany.