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Patented Dec. 17, 1946
2,412,890
‘ " UNITED} STATES PATENT "OFFICE
PREPARATION OF METAL AMTMCINE SALTS
Grinnell [Jones and Walter Juda, Cambridge,‘
Mass., assignors to Albi Chemical Corporation, '
New’York, N. Y., a corporation of New York
No Drawing. ‘Application June 17, 1942,
Serial No. 447,471
7 Claims.
1
The present invention relates to the prepara
tion of complex metal ammine salts.
‘By the term "ammine" it is intended to include
(Cl. 23-14)
2
A further object is to provide such a method
which will be practical and economical for use in
large scale manufacture.
-
‘ only ammonia and amines.
Yet another object is to provide a method for
Complex metal ammine salts vary widely in .3 producing solid complex metal ammine salts of
chemical structure and also in physical proper
controlled stability and controlled solubility.
ties, particularly with regard to stability and solu
bility. depending upon the nature of the metal
In general, our improved method comprises the
dry mixing and agitation of a solid metal com
(and in some cases its state of oxidation), the
pound the anion of which is‘ derived from an acid
anion, the conditions of preparation and other 10 strongerthan carbonic acid, with a solid ammine
factors. For these and other reasons, it is dif
compound which is relatively unstable and which
ficult to generalize in this ?eld and to determine
will form, with the solid metal compound, a com
in advance either the nature of the ?nal product
plex metal ammine salt. When a source of am
or the essential or optimum ingredients or pro
mine such as ammonium carbonate, ammonium
cedures to be employed. Our invention provides
carbamate, or an amine carbonate. or the like, is
a practical and ?exible procedure by the use of
used, carbon dioxide is liberated during the :mix
which a-wide variety of useful products is obtained
ing and agitation. In some cases color changes
as hereinafter disclosed.
characteristic of the metal appear. The mixture
Ma'ny complex metal ammine salts are ex
becomes wet and‘in some cases pasty, almost ?uid.
tremely soluble in water and for this reason it is ~ The solid complex metal compound may be dried
very di?icult to prepare them in the solid state,
afterthe reaction is complete, or the agitation
in view of the difficulty of precipitating them from
and drying may be accomplished simultaneously.
the solutions in which they are formed. Attempts
The product may be ground to any desired par
to prepare these soluble salts in the solidv state by
ticle size.
chilling the solutions are often ineifective and 25 In an alternate procedure, a metal salt and an
give poor yields. Attempts to recover the salt
ammine compound are mixed with a salt or salts
by evaporation of the liquid commonly result in
containing an anion which is capable of forming
loss of ammonia or of a volatile amine by vola
tilization. Other complex metal ammine salts
which are sparingly ‘soluble are not subject to
these di?lculties but involve other dif?culties in
precipitation, ?ltering, washing and drying.
an insoluble salt with one or more of the metal
salts, as claimed in our co-pending application
_
In some cases it is desirable to heat the mix
ture to start the reaction. The heat is prefer
30 Serial No. 447,470, filed June 17, 1942.
It has been proposed to form complex metal
ably moderate, of the order of ‘70-80° C., although
ammonia salts by exposing the solid metal salts to
considerable variation in this temperature is per
ammonia gas. However, with ‘this method the L3 LI missible according to the ingredients and the ?nal
formation of the complex salt is apt to be merely
product involved.
superficial and may not penetrate thoroughly into
Drying can be accelerated by the application of
the inner part of the crystals. Thus the conver
a vacuum.
sion to the complex salt may be incomplete.
As indicated above, a wide range of desirable
It has also been proposed to react basic copper d products may be obtained by our invention. The
carbonate with ammonium carbonate in the dry
solubility and stability of the ?nal product may
state to form solid copper ammonia carbonate, the
be varied inaccordance with the requirements of
reaction preferably being. carried out in the pres
the particular purpose in mind. The chemical
ence of lime to absorb the carbon dioxide which
composition is also subject to variation in the light
is liberated. It is di?icult, however, if not impos
of the same considerations.
sible to tell when this reaction. has gone to com
For a better understanding of our invention.
pletion, so that the nature of the ?nal product
the following speci?c examples of its application
and of solutions prepared therefrom are neces
may be given, it being understood that these are
sarily somewhat indeterminate. Furthermore,‘
illustrative only and are not to be construed in
this proposal results in a product of extremely un- - a limiting sense. The proportions are by weight.
stable character, which must be shipped and
Example 1.—20 parts of copper sulfate and 23
stored in sealed containers.
‘
parts of ammonium carbonate are mixed in dry
It is an object of our invention to provide an
crystalline form in a mortar and the mixture is
improved-process for the preparation of solid com
“agitated as by stirring. ‘The reaction starts almost
plex metal ammine salts. '
'
55 immediately and proceeds with the liberation of
8,418,890
3
.
carbon dioxide and of water. The water of crys
tallization is partially substituted by NR1. Since
4
tion of copper ammonia ?uoride and alsopthe
formation of sodium sulfate simultaneously with
the formation of the complex copper ammonia
the final product appears to have the composition
salt. A third possibility is that both of these
Cu(NI-11)4SO4H2O, it is likely that four molecules
of water of crystallization are directly substituted CI reactions may take place to some extent; the
?nal product may be intermediate between the
by four NH: groups while the ?fth molecule of
water of crystallization cannot be replaced.
two ?rst indicated, comprising a mixture of cop
Since the copper ammonia sulfate is a fairly
per ammonia sulfate, copper ammonia ?uoride,
stable compound, the salt can be dried by heat.
sodium sulfate and sodium ?uoride.
A short exposure to a temperature of about 105° 10
In most cases it is immaterial which of these
C. will dry the product if it is exposed to the heat
conditions prevails, since in any event the ?nal
in thin layers, without decomposing the copper
ammonia complex. A continued exposure, how
ever, will slowly decompose the complex, ammo
nia being given on and the deep blue to violet
color of the powder ‘becoming lighter.
Mixing and drying may be facilitated by car
rying out the mixing and agitation of the ingredi
ents in a closed container or ?ask to which a
product will contain ions which, when dissolved,
deposited upon a base material such as a fab
ric and the ammonia volatilized, will leave an
insoluble metal compound.
’
\
If we assume the ?nal product to be a mixture
of copper ammonia sulfate and sodium ?uoride.
the theoretical amounts of copper, ammonia and
?uorine present will be: Cu, 19%, NHa, 20.3% and
vacuum is applied, the ingredients being heated 20 F, 12%, based on the original amounts of cop
during the agitation. The evolution of carbon
per sulfate, ammonium carbonate and sodium
> ?uoride given in Example 2. If complete double
dioxide'and of water vapor during the reaction
decomposition takes place and the ?nal product
tends to reduce the vacuum but after the reac-_
tion has gone to completion, the vacuum will
consists of copper ammonia ?uoride and sodium
increase and then reach a constant value. This 25 sulfate, the relative amounts of copper, ammonia
and ?uoride in the product still would not be
gives a reliable indication of the completion of
signi?cantly changed from the percentages just
the desired reaction and the formation of the
given.
desired dry product.
For example, in one experiment it was found
If the number of ‘molecules of water of crys
that when 1 lb. of copper ammonia sulfate was 30 tallization per molecule of copper ammonia ?u
oride should be high, the above theoretical per
formed in a ?ve litre, three-neck Pyrex ?ask,
centages of copper, ammonia and ?uorine would
under a vacuum which ?nally went to about 22
millimeters of mercury, the ?ask being heated
no longer hold. This, however, seems unlikely,
since water is obviously liberated during the
in a water bath to approximately 100° 0., the
reaction was complete in less than one hour.
reaction.
The product may be ground to any desired par
Analysis of our product prepared in accordance
with Example 2 has given ?gures closely com
ticle size.
parable to the theoretical percentages just given.
Example 2.—16 parts of sodium ?uoride, 45
The complex ?nal product is quite stable. Only
parts of copper sulfate and 50 parts of ammo
nium carbonate are dry mixed and agitated to 40 one-?fth of the ammonia is lost when the powder
is dried for thirty minutes at a temperature of
gether, using the above orany convenient pro
106° C. If the product is to be used in solution,
cedure, either with or without the application
the loss of ammonia during drying (if any) does
of vacuum and heating. After the reaction has
gone to completion (as indicated by the fact that
not render the product useless, since a small
carbon dioxide is no longer given o?) , the prod 45 addition of ammonia to the solution will dissolve
uct may, if desired, be dried by spreading it in
any residue.
thin layers. It may then be ground as previously
The ?nal composition which contains the the
oretical proportions within the limits given above
is soluble in water, giving a deep blue solution
accomplished, as in the case ofExample 1. For 50 characteristic of copper ammonia complex com
instance, the reaction may be carried out in a
pounds. If an excess of water is added, the solu
?ask to which a vacuum is applied during the
tion turns to a lighter blue and a’ turbidity ap
reaction, the ?ask being heated in a water bath
pears which may be due to hydrolysis. A small
or otherwise. Evolution of carbon dioxide and
addition of ammonia, however, clears the solu
indicated.
’
The mixing and drying may be simultaneously
water vapor will reduce the vacuum during the 55 tion again and causes the deep blue color to re
progress of the reaction and completion of the
appear.‘ This indicates that an excess of am
reaction will be indicated by decrease in and
monia is required to obtain stable dilute solu
stabilization of the pressure.
tions of copper ammonia compounds.
Example 2 is illustrative of a type of procedure
Example 3.-—48 parts of copper sulfate and 48
in which a ?rst or primary water-soluble metal 60 parts of ammonium carbonate are mixed in dry
salt is agitated with an ammonium compound
crystalline form in a mortar or in a closed ?ask as
and a second water-soluble salt, the anion of
in Example 1 above.‘ The mixture is stirred con
which second salt forms an insoluble salt with
stantly and when it becomes pasty or ?uid, ap
the metal of the ?rst or primary metal salt. This
proximately 6.4 parts of a wetting agent (for ex
process results in a ?nal product which is solu
ample an ester of a sulfonated bi-carboxylic acid
ble in water but which, when applied to a fabric,
such as Aerosol M. A.) are added and uniformly
for example, and the ammonia volatilized, will
distributed throughout the mixture. In the case
leave upon the fabric a deposit of a water-insolu
of solid wetting agents, uniform distribution is
ble metal compound.
facilitated by dissolving said agent in a minimum
The exact nature of the ?nal product of Exam 70 amount of hot water prior to introducing it into
ple 2 is subject to some speculation. ,
the mixture.
It is possible that the sodium ?uoride appears
The reaction proceeds to completion as in Ex
as such in the ?nal product, mixed with copper.
ample 1 and the product maythen be used if de
ammonia sulfate. or there may be a double de
sired in the formation of various compositions.
composition reaction which results in the forma 75 For example, an eifective ?re retarding compo
sitlon may be made by mixing this product with
starting materials because. in their absence, the
diammonium phosphate in the proportions of ap
completion of the reaction is indicated when car
bon dioxide is no longer liberated. Thus when ~
monia product to ten parts of diammonium
phosphate, The resulting mixture will be solu $1 ammonium carbonate is used as a source of am
monia. the metal salt will be a salt with an anion
ble in water and will have high penetrating and
different from that of the ammonium salt.
wetting qualities due to the presence of the wet
We also prefer to avoid the formation of metal
ting agent. When impregnated into combustible
ammonia
carbonates as final products. For a
materials such as wood or fabric, this composi
given
metal
the carbonate will be less stable than
tion will impart to such material desirable pre
salts containing anions derived from acids
servative and ?reproof properties.
.
stronger than carbonic, acid.
'
Example 4.—10 parts of cobaltous chloride, 20
In
place
of
ammonium
carbonate
there
may
be
parts of ammonium carbonate, and 4 parts of am
used ammonium bicarbonate. ammonium carba
monium chloride are mixed and stirred together
mate, urea, amine compounds, such as carbon
in the presence of air or other oxidizing agent.
ates, for example guanidlne carbonate, and the
The purpose of the oxidizing agent is to convert
like.
,
the cobalt from the cobaltous to the cobaltic
In
place
of
sodium
?uoride
mentioned
in Ex
state. The reaction goes as above. The mixture
ample 2 there may be used monoammonium
‘becomes moist, carbon dioxide is liberated and
phosphate, diammonium phosphate, sodium ar
the color turns to brown, indicating the forma
proximately one part of the complex copper am
tion ‘of a cobaltic ammonia compound.
senite, sodium arsenate, or other salt the anion of
which will form, with the metal of the ?rst or
primary salt, a compound which is relatively in
soluble in water. For many purposes, water‘
soluble salts of this class are preferred.
It is to be noted that salts which are strongly
The
color of the mixture after drying is red-violet. '
The final product'contains a sparingly soluble
product, probably the chloro pentammonia co
baltichloride, [C0(NH3)5CI]C1:.
Example 5.--20 parts of copper ?uoride and 50
basic or acid are not suitable for admixture as in
parts of ammonium carbonate are mixed and agi
Example 2 with the primary metal salt and the
source of ammine prior to reaction between these
ingredients to form the complex metal ammine
tated together as in the preceding examples. ' The
reaction proceeds as above, the ?nal product be
ing, for the greater part, readily soluble in water.
' Other insoluble copper salts, for example cop
per phosphate or copper arsenite, may be used in
stead of the ?uoride in Example 5, but in these
cases the reaction proceeds with more dimculty
30
salt, because the strong alkalinity or acidity im
parted thereby would prevent the formation of
the complex salt. The ammonia or volatile amine
will be driven oif from strongly basic mixtures
and the complex formation cannot take place in
strongly acid media. The compound selected as
a third ingredient should, therefore, be one which
is substantially neutral.
As previously indicated, the proportions given
above are merely convenient examples of opera
stirred together in the presence of air or other 40 tive
proportions. The proportionsof ingredients
oxidizing agent, as‘in Example 4. Oxidation of
usable in our process are subject to wide varia
the cobalt and formation of a complex cobalt
tion. If it is desired to eifect complete conversion
guanidlne chloride proceeds and the ?nal prod
of the metal salt to the complex metal ammine
uct is violet-blue in color.
compound, su?icient ammonia or amine must ob
It will be noted that in Examples 4 and 6 the 45 viously
be supplied for this purpose.
metal is oxidized from the "ous" to the “ic" state
By our novel process we may prepare solid com
during the formation of the complexsalt. For
plex metal ammine salts which are stable at nor
maximum e?iciency it therefore becomes advisa
mal temperatures and pressures under ordinary
ble to furnish an additional supply of the anion
of this metal salt. This may be done, as in Ex 50 conditions of manufacture, handling and storage.
Such stability is possessed, for example, by the
amples 4 and 6, by supplying this anion
products obtained by the procedures given in
Examples 1, 2 and 3, above. As illustrated by
(51)
Example 3, we may produce solid complex metal
and it is advisable to heat the mixture in order
to expedite the reaction.
Example 6.—5 parts of cobaltous chloride, 10
parts of guanidine carbonate, and one to two
parts of ammonium chloride are mixed and
as a part of the source of ammonia. Or some
ammine salts which can be mixed with other in
, other source of this anion may be provided.
55 gredients to form products useful for a variety of
Both the speci?c ingredients and the relative
purposes.
amounts thereof given in the foregoing examples
are subject to wide variation.
In place of the copper sulfate mentioned. salts
of cobalt, nickel, silver, zinc, cadmium and others
For some uses less stable products may be un
' objectionable or even desirable.
Products of varying degrees of ~solubility, as
desired. may be prepared by our process. Thus
the process of Example 4 above utilizes an initial
be used.
mixture of ingredients all of which are readily
In the appended claims, we use the term "am
soluble in water to form a ?nal product which
mine complexogen metal” to designate metals
contains
a complex metal ammine salt which is
which are capable of forming ‘complex metal 65 only sparingly
soluble. In Example 5, on the
amine salts or metal ammonia salts, when mixed
other hand. the initial metal salt is relatively
in the solid state with a solid source of ammine.
insoluble in water but the ?nal product is for the
capable of forming complex ammine salts may
.
As previously indicated, theanions combined
greater part readily soluble in water. '
with the metals in these salts will be anions de
will thus be seen that by our invention there
rived from acids stronger than carbonic acid. In 70 is It
provided a novel and improved process for the
determining the relative strengths of acids, the
preparation of solid complex metal ammine salts.
dissociation constant is to be taken into consid
which‘ process is practical and economical for
eration, in accordance with well established
large scale manufacture and results in a greatly
principles.
,
_
-
It is desirable to avoid metal carbonates as
improved yield of desirable products having a
wide range of commercial applications.
l
2,412,890
7
.We claim:
1. A method for the preparation of a solid com
. plex metal ammine salt, which comprises the steps
_
l
monia salt, and continuing said agitation until
said salt is substantially converted to a complex
of mixing and agitating together a solid salt of an
ammine complexogen metal, said salt having an
anion derived from an acid stronger than car
metal
5. Aammonia
method for
salt.
the preparation of a solid com
plex copper ammonia salt, said method compris
ing mixing and agitating together a solid copper
bonic acid, and a solid ammine salt which is un
' stable and which will form, with the solid metal
salt which has an anion derived from an acid
stronger than carbonic acid, and ammonium car
bonate, until the mixture becomes moist and car
compound, a complex metal ammine salt, con
tinuing said mixing and agitation until the mix--. 10 bon dioxide is evolved, then continuing said agi
tation until the evolution of carbon dioxide'and
ture becomes moist and the metal salt is substan
water vapor substantially ceases, and drying the
tially converted into a complex metal ammine
resulting complex salt.
salt, and drying the complex salt.
6. In a method for the preparation of solid
2. A method for the preparation of a solid com
plex metal ammonia salt, which comprises the 15 complex metal ammonia salts. the steps'which
comprise mixing, agitating and heating together,
steps of mixing and agitating together a solid salt
in the solid state and under a vacuum, a'metal
of an ammine complexogen metal, said salt hav-_
salt selected from the group consisting of those
ing an anion derived from an acid stronger than
carbonic acid, and ammonium carbonate, con
salts of copper, cobalt and silver having an anion
salt is substantially converted into a complex
and a solid ammonium compound which is un
tinuing said mixing and agitation until the metal 20 derived from an acid stronger than carbonic acid,
stable and which will form, with the solid metal
compound, a complex metal ammonia salt, and
continuing said agitation until the metal salt is
plex metal guanidine salt, which comprises the
steps of mixing and agitating together a solid 25 substantially converted into a complex metal am
monia salt.
salt of an ammine complexogen metal, said salt
7. A method for the preparation of a solid
having an anion derived from an acid stronger
complex metal ammonia compound, which com
than carbonic acid, and guanidine carbonate, and
’ metal ammonia ‘salt, and drying the complex salt.
3. A method for the preparation of a solid com
continuing said mixing and agitation until the
prises the steps of mixing and agitating together
30 a solid salt of an ammine complexogen metaLsald
salt having an anion derived from an acid
stronger than carbonic acid, and a solid ammoni
4. In a method for the preparation of a solid
um compound which is unstable and which will
complex metal ammonia salt, the steps which
form, with the metal compound, a complex metal '
comprise mixing and agitating together a solid
metal salt is substantially convertedinto a com
plex metal guanidine salt.
salt of a metal selected from the group consisting
of copper, cobalt, and silver, said salt having an
anion derived from an acid stronger than car
bonic acid, and a solid ammonium compound
which is relatively unstable and which will form,
with the said metal salt. a complex metal am 40
ammonia salt, agitating the mixture until it be
comes pasty or ?uid, and continuing the agitation
until said metal salt is substantially converted
into a solid complex metal ammonia compound.
’
GRINNELL JONES.
WALTER JUDA.
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