Preparation
Inorganic
Syntheses IV: 12 (Chapter 1B, # 3)
Silver (II) Oxide
by Robert Hammer & Jacob Kleiberg
Silver (II)
oxide has been made by the hydrolytic action of boiling water
on a substance of the approximate formula Ag7O8NO3, a material
which obtained by the electrolytic oxidation of silver (I)
nitrate solutions (Ref. 1-4). A more rapid and convenient
process for the preparation of this oxide involves the
oxidation of silver (I) nitrate by means of potassium
peroxydisulfate ("Oxone") in an alkaline medium (Ref. 5, 6).
Procedure
72 grams of
sodium hydroxide (NaOH, 1.8 mols) in pellet form is added
portionwise, with constant stirring, to 1 liter of water,
which is maintained at approximately 85°. Seventy-five (75)
grams of potassium peroxydisulfate (0.28 mols) in the form of
an aqueous slurry is added to the hot alkaline solution; this
is followed by the addition of 51 gr of silver (I) nitrate
(0.30 mol) dissolved in a minimum amount of water. The
temperature of the resulting mixture is raised to 90°, and
stirring is continued for approximately 15 minutes.
The
precipitate of black silver (II) oxide is filtered on a large
Buchner funnel, and sulfate ion is removed by washing with
water which has been made slightly alkaline with sodium
hydroxide. The product is air-dried.
Yield, 35
gr (94%).
Analysis:
Calculated for AgO: Ag, 87.08%. Found: Ag, 86.93%, 86.90% (by
gravimetric chloride method, after dissolution of the product
in 3N nitric acid).
Properties
There are
many indications that AgO is a true oxide, rather than a
peroxide, and is, therefore, properly named silver (II) oxide.
The compound does not give free hydrogen peroxide when
acidified but behaves in a manner more characteristic of a
compound in which the metal ion is present in a strongly
oxidized valence state, which may be stabilized by
coordination. In dilute acid, oxygen is immediately evolved;
in concentrated acid, intensely colored solutions are formed
(brown in nitric acid and olive green in sulfuric acid). These
latter solutions are relatively stable, though they gradually
decompose with an accompanying liberation of oxygen, and have
been show to possess paramagnetism which is quantitatively
consistent with the expected magnetic moment of the postulated
silver (II) species (Ref. 7). In the solid state, this oxide
is stable when heated to 100°, but it decomposes at higher
temperatures. The solid possesses semiconductor properties and
is diamagnetic. These phenomena have been explained by Neiding
and Kazarnovskii (Ref. 7) on the assumption that the silver is
actually trivalent in its crystal lattice with both O-Ag and
Ag-Ag bonds. The difference in the specific volumes of AgO and
Ag2O is less than would be expected if AgO were a peroxide
(Ref 7). Equilibrium of silver (II) oxide with dilute nitric
acid gives the black paramagnetic oxynitrate (Ag7O8NO3), a
substance in which part of the silver is apparently in the
tripositive state.
References
1. Mulder:
Rec. Trav. Chim. 17: 129 (1898)
2. Watson:
J. Chem. Soc. 89: 578 (1906)
3. Jirsa:
Zeit. Anorg. u. Allgem. Chem. 148: 130 (1925)
4. Noyes,
et al.: J. Amer. Chem. Soc. 59: 1326 (1937)
5.
Barbieri: Chem. Berichte 60: 2427 (1927)
6. British
Patent # 579,817; Chem. Abstr. 41: 1401h (1947)
7. Chem.
Abstr. 45: 8385h (1951)
http://81.207.88.128/science/chem/exps/Ni+persulfate/index.html
PREPARATION
OF TETRASILVER TETROXIDE
Oxidation of silver to its +3 oxidation state
Prepare a
solution of silver nitrate or silver oxide in dilute nitric
acid. Any concentration of 1 to 2 mol/l for the nitric acid is
OK.
Add some
solid sodium persulfate to the liquid. Adding a fairly
concentrated solution of sodium persulfate also works. When
this is done, then the liquid becomes brown and remains clear.
The brown color is due to silver (III) ions. The brown color
is formed quickly, although not instantaneously. It takes a
few seconds.
Silver
(III) ions are not very stable. Even in the fairly strongly
acidic liquids, the compound slowly decomposes. A black
precipitate is formed and oxygen is released very slowly. This
black precipitate is due to combined hydrolysis and reduction
of the silver (III) ions. A mixed silver (I) silver (III)
oxide is formed, which precipitates from the liquid as a black
solid.
Remarkably,
when persulfate is added to a neutral solution of silver
nitrate, then no brown color is formed. In that case the
liquid first remains colorless, but in the course of a few
minutes it slowly turns turbid and a dark brown/black
precipitate is formed. Apparently, at higher pH, the brown
silver (III) ion is not formed at all and the mixed silver (I)
silver (III) oxide is formed immediately.
Addition of sodium hydroxide, quick formation of
Ag(I)Ag(III)O2
When the
brown liquid is added to a solution of sodium hydroxide, then
the process of formation of the black silver (I) silver (III)
oxide is almost immediate. As soon as the brown liquid is
added to a solution of sodium hydroxide, a dark brown very
finely divided precipitate is formed. The solid particles
stick together quickly and larger black particles are formed.
The black solid slowly evolves oxygen and every few minutes it
moves to the surface, due to many small bubbles of oxygen,
which are trapped inside the precipitate. When these small
bubbles of oxygen are lost, then the solid mass sinks to the
bottom again. This 'dance' is repeated several times.
The three
pictures below show the liquid, immediately after adding it to
a slight excess amount of a solution of NaOH. The second
picture shows the same liquid a few minutes later, when the
particles of the precipitate stick to each other. The final
picture shows the precipitate near the surface, due to lots of
trapped bubbles of oxygen. All the pictures clearly show the
bubbles of oxygen.
Whether the
brown color is due to plain Ag3+ or due to some mixed valency
complex of silver (I) and silver (III) is not clear to me. It
might be that the brown color is due to a mixed valency
complex of silver (I) and silver (III). Examples of mixed
valency complexes are also given on the following pages:
copper (I) / copper (II) and titanium (III) / titanium (IV).
Reaction with silver
In acidic
media, persulfate is capable of oxidizing silver (I) ions to
silver (III) ions. These silver (III) ions are brown.
Ag+(aq) +
S2O82-(aq) ? Ag3+(aq) + 2SO42-(aq)
Silver
(III) ions are not very stable. This liquid slowly looses its
color and gives off oxygen. A black precipitate is formed of
silver (I) silver (III) oxide. The silver (III) ions slowly
oxidize the water, in which they are dissolved.
4Ag3+ +
6H2O ? 2AgIAgIIIO2 + 12H+ + O2
When the
liquid is made more basic, then the reaction proceeds much
faster, as the experiment demonstrates. The following reaction
occurs in that case.
4Ag3+ +
12OH– ? 2AgIAgIIIO2 + 6H2O + O2
The
compound AgAgO2 in turn also decomposes. It slowly looses
oxygen and is converted to simple silver (I) oxide.
2AgIAgIIIO2
? 2AgI2O + O2
General remarks
Both the
silver (III) compounds and the NiO2 compound are very strong
oxidizers. Both compounds are capable of oxidizing manganese
(IV) and manganese (II) to the +7 oxidation state as
permanganate and chromium (III) is oxidized to the +6
oxidation state as dichromate or chromate.
Silver
nitrate is a catalyst in many reactions with persulfate in
acidic media. Persulfate is a strong oxidizer, but it also is
somewhat sluggish. The reaction between silver (I) and
persulfate in acidic media, however is quite fast. Silver
(III) in turn reacts with manganese (II) or chromium (III)
quickly to form permanganate or dichromate, itself being
converted to silver (I) again. So, in the presence of a small
amount of silver nitrate, the persulfate anion can be used as
a fast and very strong oxidizer. The catalytic action of
silver is based on the fact that an other pathway for the
final redox reaction is provided, with Ag3+ as intermediate
species.
A similar
catalytic action can be observed with nickel hydroxide in
basic solutions. The reaction between nickel hydroxide and
persulfate is very fast (instantaneously, at least in terms of
human observation). Nickel (IV) oxide in turn is capable of
oxidizing e.g. manganese (IV) oxide to permanganate. This
property can be used as a sensitive method for detecting
manganese.
Another
important remark is that in both experiments, the presence of
chloride ions should be avoided. Especially with the silver
experiment, chloride ions are really disturbing. They make the
liquid cloudy, due to formation of silver (I) chloride and
they interfere, due to oxidation to chlorine.
For the
nickel experiment the presence of chloride is not of a direct
concern, but if one wants to use NiO2 for detection of
manganese by conversion to the deep purple permanganate, then
even small amounts of chloride interfere and make the
detection fail.
More info
on the interesting and remarkable subject of silver (III)
chemistry can be found in the following book: Chemistry of the
Elements, second edition, written by Greenwood and Earnshaw,
pages 1181 and 1188.
Precious Metals 16 : 141-149 ( 1992 )
Anti-Pathogenic
Silver Molecular Semiconductors"
Marvin Antelman
"Tetrasilver
tetroxide (Ag4O4 ) crystals were prepared by modifying the
procedure described by Hammer and Kleinberg in Inorganic
Syntheses (IV,12). A stock solution was prepared by dissolving
24.0 grams of potassium peroxydisulfate in distilled water and
subsequently adding to this 24.0 of sodium hydroxide and then
diluting the entire solution with said water to a final volume
of 500 ml. Into 20 ml. vials were weighed aliquots of silver
nitrate containing 1.0 g. of silver. Now 50 ml. of the
aforementioned stock solution were heated in a 100 ml. beaker,
and the contents of one of the vials was added to the solution
upon attaining a temperature of 85.degree. C. The beaker was
then maintained at 90.degree. C. for 15 minutes. The resulting
deep black oxide obtained consisting of molecular crystal
devices was washed and decanted four times with distilled
water in order to remove impurities. The purified material was
collected for further evaluation and comparison with
commercial material. The commercial material was purchased
from Johnson Matthey's Catalog Chemicals Division of the Aesar
Group of Ward Hill, Massachusetts, under product code 11607
and generically listed in its materials Safety Data Sheet as
both silver peroxide and silver suboxide, having a purity of
99.9%... "
https://www.youtube.com/watch?v=i-nI19OLyMM
Tetrasil,
tetrasilver-tetroxide, silver oxide
Tetrasilver
tetroxide - prepared at home. I prepared it from AgNO3, NaOH
and NaS2O8. I dissolved it in neutral organic solvent and
applied against my athletes feet twice and it worked-signs
disappeared.
http://81.207.88.128/science/chem/exps/Ni+persulfate/index.html
Oxidation of silver
to its +3 oxidation state.
Prepare a
solution of silver nitrate or silver oxide in dilute nitric
acid. Any concentration of 1 to 2 mol/l for the nitric acid is
OK.
Add some
solid sodium persulfate to the liquid. Adding a fairly
concentrated solution of sodium persulfate also works. When
this is done, then the liquid becomes brown and remains clear.
The brown color is due to silver (III) ions. The brown color
is formed quickly, although not instantaneously. It takes a
few seconds.
The two
pictures below show the brown liquid and a small quantity of
this liquid, diluted in some dilute nitric acid. These picture
clearly show the brown color of silver (III) ions
(*). (*) see remark below.
Silver
(III) ions are not very stable. Even in the fairly strongly
acidic liquids, the compound slowly decomposes. A black
precipitate is formed and oxygen is released very slowly. This
black precipitate is due to combined hydrolysis and reduction
of the silver (III) ions. A mixed silver (I) silver (III)
oxide is formed, which precipitates from the liquid as a black
solid.
Remarkably,
when persulfate is added to a neutral solution of silver
nitrate, then no brown color is formed. In that case the
liquid first remains colorless, but in the course of a few
minutes it slowly turns turbid and a dark brown/black
precipitate is formed. Apparently, at higher pH, the brown
silver (III) ion is not formed at all and the mixed silver (I)
silver (III) oxide is formed immediately.
Addition
of sodium hydroxide, quick formation of Ag(I)Ag(III)O2
When the
brown liquid is added to a solution of sodium hydroxide, then
the process of formation of the black silver (I) silver (III)
oxide is almost immediate. As soon as the brown liquid is
added to a solution of sodium hydroxide, a dark brown very
finely divided precipitate is formed. The solid particles
stick together quickly and larger black particles are formed.
The black solid slowly evolves oxygen and every few minutes it
moves to the surface, due to many small bubbles of oxygen,
which are trapped inside the precipitate. When these small
bubbles of oxygen are lost, then the solid mass sinks to the
bottom again. This 'dance' is repeated several times.
The three
pictures below show the liquid, immediately after adding it to
a slight excess amount of a solution of NaOH. The second
picture shows the same liquid a few minutes later, when the
particles of the precipitate stick to each other. The final
picture shows the precipitate near the surface, due to lots of
trapped bubbles of oxygen. All the pictures clearly show the
bubbles of oxygen.
Discussion
of the results
Reaction with nickel
Persulfate
oxidizes nickel hydroxide to nickel (IV) oxide in water.
Ni(OH)2 + 2OH– + S2O82- ? NiO2 + 2SO42- + 2H2O
In the wet
environment, the compound NiO2 does not exist as such, as
suggested by the simplified equation, given above. In fact a
non-stoichiometric compound, which can best be described as
NiO2.nH2O is formed, with n some indeterminate number.
On
acidification with nitric acid or sulphuric acid, the nickel
(IV) compound decomposes again:
2NiO2.nH2O(s) + 4H+(aq) ? 2Ni2+(aq) + O2(g) + 2H2O +
nH2O
When dilute
hydrochloric acid is added, then the liquid gives a strong
smell of chlorine. In that case, the chloride ion is oxidized
to chlorine. The liquid still bubbles in that case. Probably
there will be oxidation of chloride to chlorine and still the
decomposition reaction, as described above.
Reaction
with silver
In acidic
media, persulfate is capable of oxidizing silver (I) ions to
silver (III) ions. These silver (III) ions are brown.
Ag+(aq)
+ S2O82-(aq) ? Ag3+(aq) + 2SO42-(aq)
Silver
(III) ions are not very stable. This liquid slowly looses its
color and gives off oxygen. A black precipitate is formed of
silver (I) silver (III) oxide. The silver (III) ions slowly
oxidize the water, in which they are dissolved.
4Ag3+
+ 6H2O ? 2AgIAgIIIO2 + 12H+ + O2
When the
liquid is made more basic, then the reaction proceeds much
faster, as the experiment demonstrates. The following reaction
occurs in that case.
4Ag3+
+ 12OH– ? 2AgIAgIIIO2 + 6H2O + O2
The
compound AgAgO2 in turn also decomposes. It slowly looses
oxygen and is converted to simple silver (I) oxide.
2AgIAgIIIO2
? 2AgI2O + O2
(*) Remark:
Whether the brown color is due to plain Ag3+ or due to some
mixed valency complex of silver (I) and silver (III) is not
clear to me. It might be that the brown color is due to a
mixed valency complex of silver (I) and silver (III). Examples
of mixed valency complexes are also given on the following
pages: copper (I) / copper (II) and titanium (III) / titanium
(IV).
General
remarks
Both the
silver (III) compounds and the NiO2 compound are very strong
oxidizers. Both compounds are capable of oxidizing manganese
(IV) and manganese (II) to the +7 oxidation state as
permanganate and chromium (III) is oxidized to the +6
oxidation state as dichromate or chromate.
Silver
nitrate is a catalyst in many reactions with persulfate in
acidic media. Persulfate is a strong oxidizer, but it also is
somewhat sluggish. The reaction between silver (I) and
persulfate in acidic media, however is quite fast. Silver
(III) in turn reacts with manganese (II) or chromium (III)
quickly to form permanganate or dichromate, itself being
converted to silver (I) again. So, in the presence of a small
amount of silver nitrate, the persulfate anion can be used as
a fast and very strong oxidizer. The catalytic action of
silver is based on the fact that an other pathway for the
final redox reaction is provided, with Ag3+ as intermediate
species.
A similar
catalytic action can be observed with nickel hydroxide in
basic solutions. The reaction between nickel hydroxide and
persulfate is very fast (instantaneously, at least in terms of
human observation). Nickel (IV) oxide in turn is capable of
oxidizing e.g. manganese (IV) oxide to permanganate. This
property can be used as a sensitive method for detecting
manganese.
Another
important remark is that in both experiments, the presence of
chloride ions should be avoided. Especially with the silver
experiment, chloride ions are really disturbing. They make the
liquid cloudy, due to formation of silver (I) chloride and
they interfere, due to oxidation to chlorine.
For the
nickel experiment the presence of chloride is not of a direct
concern, but if one wants to use NiO2 for detection of
manganese by conversion to the deep purple permanganate, then
even small amounts of chloride interfere and make the
detection fail.
More info
on the interesting and remarkable subject of silver (III)
chemistry can be found in the following book: Chemistry of the
Elements, second edition, written by Greenwood and Earnshaw,
pages 1181 and 1188.
http://pubs.acs.org/doi/abs/10.1021/ed085p863
J. Chem. Educ., 2008, 85 (6), p 863
DOI: 10.1021/ed085p863
Silver(II)
Oxide or Silver(I,III) Oxide?
David Tudela
Abstract
The often
called silver peroxide and silver(II) oxide, AgO or Ag2O2, is
actually a mixed oxidation state silver(I,III) oxide. A
thermochemical cycle, with lattice energies calculated within
the "volume-based" thermodynamic approach, explain why the
silver(I,III) oxide is more stable than the hypothetical
silver(II) oxide. The coordination geometries of silver and
copper in their known oxides correlate with those associated
to their electron configurations in coordination compounds.
The second ionization energy is higher for Ag than for Cu,
which can be related to the small size of 3d orbitals and the
resulting high electron repulsion for the first transition
series elements.
http://pubs.acs.org/doi/abs/10.1021/ja01333a016?src=recsys
Journal of the American Chemical Society, 1933 55
(6), pp 2311–2325
The
Solubility of Silver Oxide in Water, in Alkali and in
Alkaline Salt Solutions
Johnston, Cuta, Garrett
http://pubs.acs.org/doi/abs/10.1021/j150267a005?src=recsys
The
Journal of Physical Chemistry 1926 30 (9), pp 1179–1180
Solubility of Silver Oxide
http://pubs.acs.org/doi/abs/10.1021/ed021p523?src=recsys
Journal
of Chemical Education, 1944 21 (11), p 523
The oxidation states of silver
http://pubs.acs.org/doi/abs/10.1021/ja01492a006?src=recsys
Journal of the American Chemical Society, 1960 82
(7), pp 1540–1543
The
Thermal Decomposition of Silver Oxide
Herley, Prout
http://pubs.acs.org/doi/abs/10.1021/j100078a009?src=recsys
J. Phys. Chem., 1994, 98 (27), pp 6699–6703
DOI: 10.1021/j100078a009
Electronegativity
and Bond Type. 2. Evaluation of Electronegativity Scales
Gordon
Sproul
http://en.wikipedia.org/wiki/Potassium_peroxymonosulfate
Potassium
Peroxydisulfate
Potassium
peroxymonosulfate (also known as MPS, potassium
monopersulfate, and the trade names Caroat and Oxone) is
widely used as an oxidizing agent. It is the potassium salt of
peroxymonosulfuric acid.
The
potassium salt is marketed by two companies: Evonik (formerly
Degussa) under the tradename Caroat and DuPont under the
tradename Oxone, tradenames which are now part of standard
chemistry vocabulary. It is a component of a triple salt with
the formula 2KHSO5·KHSO4·K2SO4.[1] The standard electrode
potential for this compound is +1.44 V with a half reaction
generating the hydrogen sulfate.
HSO5- + 2
H+ + 2 e- ? HSO4- + H2O
Reactions
Oxone is a
versatile oxidant. It oxidizes aldehydes to carboxylic acids;
in the presence of alcoholic solvents, the esters may be
obtained. Internal alkenes may be cleaved to two carboxylic
acids, while terminal alkenes may be epoxidized. Thioethers
give sulfones, tertiary amines give amine oxides, and
phosphines give phosphine oxides.[2]
Illustrative
of the oxidation power of this salt is the conversion of an
acridine derivative to the corresponding acridine-N-oxide.[3]
It will
also oxidize a thioether to a sulfone with 2 equivalents.[4]
With one equivalent the reaction converting sulfide to
sulfoxide is much faster than that of sulfoxide to sulfone, so
the reaction can conveniently be stopped at that stage if so
desired.
Uses
Potassium
peroxymonosulfate can be used in swimming pools to keep the
water clear, thus allowing chlorine in pools to work to
sanitize the water rather than clarify the water, resulting in
less chlorine needed to keep pools clean.[5]
References
1. "Oxone".
Spectral Database for Organic Compounds (SDBS). "National
Institute of Advanced Industrial Science and Technology
(AIST)".
2. Benjamin
R. Travis, Meenakshi Sivakumar, G. Olatunji Hollist, and Babak
Borhan (2003). "Facile Oxidation of Aldehydes to Acids and
Esters with Oxone". Organic Letters 5 (7): 1031–4.
doi:10.1021/ol0340078. PMID 12659566.
3. Thomas
W. Bell, Young-Moon Cho, Albert Firestone, Karin Healy, Jia
Liu, Richard Ludwig, and Scott D. Rothenberger (1993),
"9-n-Butyl-1,2,3,4,5,6,7,8-Octahydroacridin-4-ol", Org.
Synth.,
http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv8p0087
; Coll. Vol. 8: 87
4. James R.
McCarthy, Donald P. Matthews, and John P. Paolini (1998),
"Reaction of Sulfoxides with Diethylaminosulfur Trifluoride",
Org. Synth.,
http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv9p0446
; Coll. Vol. 9: 446
5.
"Benefits of Using a Non-Chlorine Shock Oxidizer Powered by
DuPont™ Oxone®." Dupont.com. Accessed July 2011.
DuPont
Oxone Monopersulfate Compound Applications : http://www.dupont.com/oxone/applications/index.html
Potassium
Monopersulfate – Article on precious metal extraction from
distributor Green Controll :
http://greencontroll.hu/EN_termekek_7.html
DuPont
Oxone Monopersulfate Compound Technical Information
http://www.dupont.com/oxone/techinfo/index.html
http://www.chemblink.com/products/37222-66-5.htm
Potassium
Peroxomonosulfate
Name --
Potassium peroxomonosulfate
Synonyms --
Oxone; Potassium monopersulfate; Potassium monopersulfate
triple salt
Molecular
Structure -- Potassium peroxomonosulfate, Oxone, Potassium
monopersulfate, Potassium monopersulfate triple salt, CAS # --
37222-66-5
Molecular
Formula -- H3K5O18S4
Molecular
Weight -- 614.76
CAS
Registry Number -- 37222-66-5
Water
solubility -- 250 g/L (20 ºC)
Risk Codes
-- R34;R37;R8 Details
Safety
Description -- S17;S26;S36/37/39;S45
TetraSilver TetrOxide ( TSTO )
Patents
US5336499 /
US5571520-- Molecular Crystal Device for Pharmaceuticals
[ PDF ]
A novel molecular scale
device is described which is bactericidal, fungicidal, viricidal
and algicidal. The anti-pathogenic properties of the device are
attributed to electron activity indigenous to diamagnetic
semiconducting crystals of tetrasilver tetroxide ( Ag4O4 ) which
contains two monovalent and two trivalent silver ions in each
molecular crystal. When the crystals are activated with an
oxidizing agent, they release electrons equivalent to 6.4 x
10-19 watts per molecule which in effect electrocute pathogens.
A multitude of these devices are effective at such low
concentrations as 0.3 PPM used as preservatives in a variety of
formulations ranging from cosmetics to pharmaceuticals. Indeed,
they are intended as active ingredients for pharmaceuticals
formulated to destroy such pathogens as Staphylococcus aureus,
and epidermidis, the latter of which it completely destroys in a
nutrient broth culture of about 1 million organisms at 0.6 PPM,
or Candida albercans, the vaginal yeast infection at 2.5 PPM,
and the AIDS virus at 18 PPM...
If we are to consider
one molecular device in operation, then each molecule would
release two electrons having each a charge of 4.8 x 10-10 e.s.u.
equivalent to approximately 1.6 x 10-19 coulombs. The EMF given
in my Encyclopedia of Chemical Electrode Potentials (Plenum
1982), page 88, for the oxidation of Ag(I) to Ag(II) is 1.98
volts which approximates 2.0 V. The total power output per
device can be calculated in watts by multiplying the power
output for each electron by 2. Since power is the product of the
potential times the charge, P = EI; for each electron it would
be:
2.0 x 1.6 x 10^-19 =
3.2 x 10^-19 watts ...
US5223149 --
Trivalent Silver Water Treatment Compositions
[ PDF ]
Said trivalent silver
complexes were subsequently evaluated as to their efficacy in
killing gram positive and gram negative bacteria in algae in
accordance with the EPA protocols for swimming pools, which
require 100% kills of bacteria within ten minutes. The compounds
far exceeded the bacteria requirements at concentrations of one
PPM or less of silver. They were evaluated with and without
persulfate salts at 10 PPM and were effective without
persulfates as bactericides.
US5211855 -- Method
of Treating Water Employing Tetrasilver Tetroxide Crystals
[ PDF ]
A novel molecular scale
device is described which is bactericidal, fungicidal and
algicidal. The antipathogenic properties of the device are
attributed to electron activity indigenous to diamagnetic
semiconducting crystals of tetrasilver tetroxide (Ag4O4) which
contains two monovalent and two trivalent silver ions in each
molecular crystal. When the crystals are activated with an
oxidizing agent, they release electrons equivalent to 6.4 x
10-19 watts per molecule which in effect electrocute pathogens.
A multitude of these devices are effective at such low
concentrations as 0.3 PPM where they can kill 100% of 100 K/cc
Streptococcus faecalis, and E. coli colonies in three minutes
meeting the ten-minute EPA criteria of 100% kills within ten
minutes for swimming pool and hot-tub applications. The devices
can be used in utilitarian bodies of water, such as municipal
and industrial water reservoirs...
Acute Oral Toxicity --
LD.sub.50 Greater than 5,000 mg/Kg
Acute Dermal Toxicity
-- LD.sub.50 Greater than 2,000 mg/Kg
Primary Eye Irritation
-- Mildly irritating
Primary Skin Irritation
-- No irritation
Skin Sensitization --
Non-Sensitizing
US5676977 -- Method
of Curing AIDS with Tetrasilver Tetroxide Molecular Crystal
Devices
[ PDF ]
The diamagnetic
semiconducting molecular crystal tetrasilver tetroxide ( Ag4O4 )
is utilized for destroying the AIDS virus, destroying AIDS
synergistic pathogens and immunity suppressing moieties (ISM) in
humans. A single intravenous injection of the devices is all
that is required for efficacy at levels of about 40 PPM of human
blood. The device molecular crystal contains two mono and two
trivalent silver ions capable of "firing" electrons capable of
electrocuting the AIDS virus, pathogens and ISM. When
administered into the bloodstream, the device electrons will be
triggered by pathogens, a proliferating virus and ISM, and when
fired will simultaneously trigger a redox chelation mechanism
resulting in divalent silver moieties which chelate and bind
active sites of the entities destroying them. The devices are
completely non-toxic. However, they put stress on the liver
causing hepatomegaly, but there is no loss of liver function.
US6258385 --
Tetrasilver Tetroxide Treatment for Skin Conditions
[ PDF ]
The invention relates
to the use of electron active molecular crystals comprising
tetrasilver tetroxide (Ag.sub.4 O.sub.4) for the treatment and
cure of dermatological skin conditions (diseases) ranging from
dermatitis, acne and psoiasis to herpes and skin ulcers.
US5073382 --
Divalent Silver Alkaline Bactericide Compositions
[ PDF ]
Solid alkaline
bactericidal compositions are disclosed suitable for compounding
alkaline end products such as food and dairy cleaners and
surgical scrubbing soaps, formed by the neutralization of acid
stabilized inorganic divalent silver complexes and capable of
effecting 100% kills upon cultures of anaerobic bacteria
colonies of 100K/cc. within 5 minutes.
US5098582 --Divalent
Silver Oxide Bactericides
[ PDF ]
Divalent silver oxide
provides a source for divalent bactericidal silver ions in the
presence of persulfate. This oxide is especially effective when
applied to water used in industrial cooling towers, hot tubs and
swimming pools and conforms to stringent EPA requirements of
100% kills of 100K/cc Streptococcus faecalis within 10 minutes.
The oxide also can be used in water with exceptionally high salt
content without halide curdy precipitate formation and will not
stain the skin of users who may inadvertently be exposed to it.
US5089275 --
Stabilized Divalent Silver Bactericides
[ PDF ]
Solid bactericidal
compositions are disclosed based on divalent silver (Ag(II)) as
the active sanitized agent. The compositions are prepared by
reacting acid liquid Ag(II) complexes with anhydrous calcium
sulfate so as to form a solid matrix in which the bactericide is
entrapped in the resulting hydrated calcium sulfate. Optimum
compositions are described consisting of Ag(II) phosphate
dissolved in phosphoric acid where the ratio of solid (by
weight) to liquid (by volume) is 5:2. The resulting solid
bactericides can be used in water cooling installations. They
are capable of causing 100% kills within 10 minutes of E. Coli
conforms in conformity with EPA protocols, allowing them to
quality as swimming pool and hot tub sanitizers. Since the
compositions are based on calcium sulfate, they are also
suitable as mineralizers, thus providing a dual function.
US6436420 -- High
performance silver (I,III) oxide antimicrobial textile
articles
[ PDF ]
Fibrous textile
articles possessing enhanced antimicrobial properties are
prepared by the deposition or interstitial precipitation of
tetrasilver tetroxide (Ag4O4) crystals within the interstices of
fibers, yarns and/or fabrics forming such articles.
US6485755 -- Methods
of using electron active compounds for managing cancer
Also published
as: WO200149303 / WO200149302 / WO200149301
[ PDF ]
The present invention
provides methods for preventing, treating, and/or managing one
or more cancerous conditions in a patient, such as a human. A
multivalent metal oxide, such as Ag(I,III), Cu(I,III),
Pr(III,IV), and Bi(III,V) oxides or a pharmaceutically
acceptable derivative thereof, may be administered to the
patient in an amount and for a period of time which is
therapeutically effective to prevent, treat, and/or manage such
condition(s). These cancerous conditions include systemic and
external cancers, and may also include conditions and symptoms
associated with cancer. The present invention also provides a
pharmaceutical composition suitable for treating such cancerous
conditions. The compositions of the invention may be adapted for
at least one of subcutaneous injection, intramuscular injection,
intravenous injection, infusion, transdermal, or topical
application.
US2006105057 /
US2004022868 -- Compositions using tetrasilver tetroxide and
methods for management of skin conditions using same
[ PDF ]
Pharmaceutical
compositions including tetrasilver tetroxide, such as in
crystalline form, and methods of using such compositions for the
prevention, treatment, and management various of dermatological
skin conditions and diseases. In one embodiment, these
compositions are substantially free of added persulfates. These
dermatological conditions and diseases that may be prevented,
treated, or managed with the compositions of the invention vary
and include, but are not limited to, eczema, psoriasis,
dermatitis, disease-induced skin ulcers, undefined tropical
diseases, shingles, rashes, bedsores, cold sores, blisters,
boils, herpes simplex, acne, pimples, skin chafing, skin
cracking, itchiness, skin peeling, and warts.
US20080233161 --
DEPOSITION PRODUCTS, COMPOSITE MATERIALS AND PROCESSES FOR THE
PRODUCTION THEREOF
A composite material
comprising a substrate and a deposition product and the use of a
deposition product for providing an antimicrobial effect. The
substrate of the composite material is a medical device.
Further, in each of the composite material and the use, the
deposition product consists essentially of at least one oxidized
silver species and wherein the deposition product is comprised
of a compound having the formula Ag.sub.7O.sub.8X, where X is an
anion.
US5017295 --
Divalent Silver Bactericide for Water Treatment
[ PDF
]
A method or
methods of controlling the growth of bacteria in the water of
swimming pools and/or industrial water supplies by adding to the
water a specified concentration of a stable divalent silver
compound. The invention has the advantage over chlorination in
that it is odorless and non-volatile. It furthermore is superior
to monovalent silver compounds as these compounds do not
decompose in the presence of light and resist precipitation by
halides and form divalent soluble complexes which in the
monovalent state are invariably insoluble solids.
US6669966 --
Compositions for facilitating skin growth and methods and
articles using same
[ PDF ]
Skin-growth-enhancing
compounds and compositions including a therapeutically effective
amount of at least one electron active compound, or a
pharmaceutically acceptable derivative thereof, that has at
least two polyvalent cations, at least one of which has a first
valence state and at least one of which has a second, different
valence state. Preferred compounds include Bi(III,V) oxide,
Co(II,III) oxide, Cu(I,III) oxide, Fe(II,III) oxide, Mn(II,III)
oxide, and Pr(III,IV) oxide, and Ag(I,III) oxide, or a
combination thereof. These compounds may be in a crystalline
state having metallic cations of two different valences, or
electronic states, in the inorganic crystal. Also included are
articles containing such compositions, such as wound dressings,
and methods for facilitating or enhancing skin growth using
these compounds, compositions, and articles, such as for the
treatment or management of burns or skin grafts.
US6645531 --
Multivalent electron active compositions and methods of making
and using same
[ PDF
]
The present
invention is directed to pharmaceutical compositions that
include a therapeutically effective amount of at least one
electron active compound, or a pharmaceutically acceptable
derivative thereof, that has at least two polyvalent cations, at
least one of which has a first valence state and at least one of
which has a second, different valence state. Preferred compounds
include Bi(III,V) oxide, Co(II,III) oxide, Cu(I,III) oxide,
Fe(II,III) oxide, Mn(II,III) oxide, and Pr(III,IV) oxide, and
optionally Ag(I,III) oxide. These compounds may be in a
crystalline state having metallic cations of two different
valences, or electronic states, in the inorganic crystal. In
addition, the invention relates to methods for prevention,
management, or treatment of a condition using these compounds or
pharmaceutical compositions including the same.
WO9745133 -- USE
OF TETRASILVER TETROXIDE MOLECULAR CRYSTALS IN THE PREPARATION
OF A MEDICAMENT FOR TREATMENT OF AIDS
The diamagnetic
semiconducting molecular crystal tetrasilver tetroxide (Ag4O4)
is utilized for destroying the AIDS virus, destroying AIDS
synergistic pathogens and immunity suppressing moieties (ISM) in
humans. A single intravenous injection of the devices is all
that is required for efficacy at levels of about 40 PPM of human
blood. The device molecular crystal contains two mono and two
trivalent silver ions capable of "firing" electrons capable of
electrocuting the AIDS virus, pathogens and ISM. When
administered into the bloodstream, the device electrons will be
triggered by pathogens, a proliferating virus and ISM, and when
fired will simultaneously trigger a redox chelation mechanism
resulting in divalent silver moieties which chelate and bind
active sites of the entities destroying them. The devices are
completely non-toxic.; However, they put stress on the liver
causing hepatomegaly, but there is no loss of liver function.
WO0149115 -- High
Performance Silver ( I, III ) Oxide& Cobalt ( II,III )
Antimicrobial Textile Articles
[ PDF
]
Fibrous textile
articles possessing enhanced antimicrobial properties are
prepared by the deposition or interstitial precipitation of
tetrasilver tetroxide (Ag4O4) or cobalt (II, III) oxide (Co3O4)
crystals within the interstices of fibers, yarns, or f abrics
forming such articles, as well as methods of preparing the same.
WO03043537 --
Improvement in Curing AIDS with Tetrasilver Tetroxide
Molecular Crystal Devices
[ PDF
]
A cure for treatment of
AIDS which specifically represents an improvement over the
instant inventor's U.S. Patent 5,676,977 entitled Method of
curing aids with tetrasilver tetroxide molecular crystal
devices. The improvement embodies curing non-terminal AIDS
patients with 15 PPM of the tetroxide, as well as curing
terminal patients by the administration of slow injections at 40
PPM so as to reduce side effects such as benign hepatomegaly.
Only a single injection is required to achieve a cure.
WO01077030 --
OZONATED SOLUTIONS OF TETRASILVER TETROXIDE
[ PDF
]
The invention provides
an ozonated form of the compound tetrasilver tetroxide, a water
disinfection method employing the ozonated tetrasilver tetroxide
and compositions comprising the ozonated tetrasilver tetroxide.
Examples of compositions of the invention include beverages,
sterilants and disinfectants. In addition, the invention
provides a method for increasing a half-life of ozone in water,
where the method includes providing tetrasilver tetroxide in the
water along with the ozone.
WO03003809 --
Methods of using electron active compounds for managing
conditions afflicting mammals
[ PDF
]
The present invention
relates to a method of preventing, treating, or managing a
condition of an animal, such as a mammal. The animal is
administered with a therapeutically effective amount of at least
one electron active compound, or a pharmaceutically acceptable
derivative thereof, that has at least two polyvalent cations, at
least one of which has a first valence state and at least one of
which has a second different valence state, to prevent, treat,
or manage the condition, or a symptom thereof. A multivalent
metal oxide, such as Ag(I,III), Cu(I,III), Pr(III,IV), and
Bi(III, V) oxides or a pharmaceutically acceptable derivative
thereof, may be administered to the animal in an amount and for
a period of time which is therapeutically effective to prevent,
treat, and/or manage such a condition(s) afflicting the animal.
WO0149303 --
MULTIVALENT ELECTRON ACTIVE COMPOSITIONS AND METHODS OF MAKING
AND USING SAME
The present invention
is directed to pharmaceutical compositions that include a
therapeutically effective amount of at least one electron active
compound, or a pharmaceutically acceptable derivative thereof,
that has at least two polyvalent cations, at least one of which
has a first valence state and at least one of which has a
second, different valence state. Preferred compounds include
Bi(III,V) oxide, Co(II,III) oxide, Cu(I,III) oxide, Fe(II,III)
oxide, Mn(II,III) oxide, and Pr(III,IV) oxide, and optionally
Ag(I,III) oxide. These compounds may be in a crystalline state
having metallic cations of two different valences, or electronic
states, in the inorganic crystal. In addition, the invention
relates to methods for prevention, management, or treatment of a
condition using these compounds or pharmaceutical compositions
including the same.
CN101336640 --
Tetrasilver tetroxide bactericide, preparation method and use
thereof
[ PDF
Translation ]
The present invention
discloses a tetrasilver tetroxide fungicide, a preparing method
and an application thereof. The tetrasilver tetroxide fungicide
comprises the following components by weight part: weak alkaline
solution 800-1200 parts, tetrasilver tetroxide 0.1-0.5 parts,
and polyvinyl alcohol 8-20 parts. The preparing method of the
tetrasilver tetroxide fungicide comprises the following steps:
using the weak alkaline solution with pH value of 7.0-7.5 as
dissolvent, fetching 800-1200 parts of weak alkaline solution,
and adding 0.1-0.5 parts of tetrasilver tetroxide, sufficiently
diluting and uniformly mixing 8-20 parts of polyvinyl alcohol
with the obtained solution in which the polyvinyl alcohol is
used as carrier, and then the tetrasilver tetroxide fungicide is
prepared. The invention also discloses the application of the
tetrasilver tetroxide fungicide as a disinfection additive. The
preparing method of the tetrasilver tetroxide fungicide
according to the invention is simple and is suitable for
large-scale production.
