EP0185866A1 - Process for the preparation of silver (III) oxide - Google Patents
Process for the preparation of silver (III) oxide Download PDFInfo
- Publication number
- EP0185866A1 EP0185866A1 EP85112886A EP85112886A EP0185866A1 EP 0185866 A1 EP0185866 A1 EP 0185866A1 EP 85112886 A EP85112886 A EP 85112886A EP 85112886 A EP85112886 A EP 85112886A EP 0185866 A1 EP0185866 A1 EP 0185866A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver
- iii
- oxide
- preparation
- anodic oxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- SBGJVZHTWCTWBJ-UHFFFAOYSA-N [Ag+]=O Chemical compound [Ag+]=O SBGJVZHTWCTWBJ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims description 10
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910017744 AgPF6 Inorganic materials 0.000 abstract 1
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 150000003378 silver Chemical class 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- -1 tetrafluoroborate Chemical compound 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002547 anomalous effect Effects 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- HTQOEHYNHFXMJJ-UHFFFAOYSA-N oxosilver zinc Chemical compound [Zn].[Ag]=O HTQOEHYNHFXMJJ-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012982 x-ray structure analysis Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
Definitions
- the invention relates to a method for producing silver (III) oxide by anodic oxidation of silver salts in aqueous solutions with current densities of 40 to 200 0 A / m 2 .
- this object was achieved by that the anodic oxidation is carried out at temperatures from -15 to + 10 ° C.
- the anomalous d ic oxidation at pH values from 4.5 to 7.5 is carried out.
- the working temperature should preferably be between -12 and 0 ° C and the pH between 5.5 and 6.5.
- the process according to the invention can be carried out on silver salts with complex anions, except nitrate and sulfate. Silver salts with perchlorate, tetrafluoroborate or hexafluorophosphate are advantageously used as the anion. It has also proven to be favorable if the silver salts are present in high concentration, as close as possible to the saturation point.
- the silver (III) oxide produced in this way can be used, for example, as an oxidizing agent, as an effective component of the positive electrodes in zinc-silver oxide primary cells or as a precursor for AgO production.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Zur Herstellung von reinem Silber (III) -oxid werden Silbersalze, vorzugsweise AgClO4, AgBF4 und AgPF6, bei -15 bis +10)° C und pH-Werten zwischen 4,5 und 7,5 mit Stromdichten von 40 bis 200 A/m² elektrolytisch oxidiert.To produce pure silver (III) oxide, silver salts, preferably AgClO4, AgBF4 and AgPF6, are used at -15 to +10) ° C. and pH values between 4.5 and 7.5 with current densities of 40 to 200 A / m² electrolytically oxidized.
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Silber (III) -oxid durch anodische Oxidation von Silbersalzen in wässrigen Lösungen mit Stromdichten von 40 bis 2000 A/m 2.The invention relates to a method for producing silver (III) oxide by anodic oxidation of silver salts in aqueous solutions with current densities of 40 to 200 0 A / m 2 .
In der "Zeitschrift für anorganische und allgemeine Chemie, Band 322 (1963), Seite 286 bis 296" werden Verfahren zur Herstellung von Silber (III) -oxidphasen durch anodische Oxidation von Silbersalzen in wässriger Lösung beschrieben. Dabei wurden verdünnte AgN03-, AgF- und AgClO4-Lösungen bei pH-Werten zwischen 3 und 4 und Raumtemperatur mit Stromdichten zwischen 40 und 100 A/m2 anodisch oxidiert. Man erhielt hierbei eine kubisch flächenzentrierte Oxidphase der "idealen Zusammensetzung" Ag2O3, die aber nur in Gegenwart von Fremdionen stabil ist und in der Ag3+ und Ag+ -ionen in verschiedenen Proportionen vorliegen. Wahrscheinlich handelt es sich hierbei um Chlathrate, wie sie in "Gmelin Handbuch, System-Nr. 61, Teil B1, 1971, Seite 120-121" angeführt werden. In reiner Form wurde Silber (III) -oxid bisher nicht hergestellt.In the "Journal for inorganic and general chemistry, volume 322 (1963), pages 286 to 296" processes for the production of silver (III) oxide phases by anodic oxidation of silver salts in aqueous solution are described. Diluted AgN0 3 , AgF and AgClO 4 solutions were anodized at pH values between 3 and 4 and room temperature with current densities between 40 and 100 A / m 2 . This gave a face-centered cubic oxide phase of the "ideal composition" Ag 2 O 3 , which is stable only in the presence of foreign ions and in which Ag 3+ and Ag + ions are present in different proportions. These are probably chlathrates as listed in "Gmelin Handbook, System No. 61, Part B1, 1971, pages 120-121". So far, silver (III) oxide has not been produced in pure form.
Es war daher Aufgabe der vorliegenden Erfindung, ein Verfahren zur Herstellung von Silber (III) -oxid durch anodische Oxidation von Silbersalzen in wässrigen Lösungen mit Stromdichten von 40 bis 2000 A/m2 zu finden, mit dem sich reines Silber (III) -oxid gewinnen lässt.It was therefore an object of the present invention to find a process for the preparation of silver (III) oxide by anodic oxidation of silver salts in aqueous solutions with current densities of 40 to 2000 A / m 2 , with which pure silver (III) oxide can be found lets win.
Diese Aufgabe wurde erfindungsgemäß dadurch gelöst, daß die anodische Oxidation bei Temperaturen von -15 bis +10° C durchgeführt wird. Insbesondere erfolgt die ano- dische Oxidation bei pH-Werten zwischen 4,5 und 7,5.According to the invention, this object was achieved by that the anodic oxidation is carried out at temperatures from -15 to + 10 ° C. In particular, the anomalous d ic oxidation at pH values from 4.5 to 7.5 is carried out.
Vorzugsweise soll die Arbeitstemperatur zwischen -12 und 0° C und der pH-Wert zwischen 5,5 und 6,5 liegen. Das erfindungsgemäße Verfahren ist durchführbar bei Silbersalzen mit komplexen Anionen, außer Nitrat und Sulfat. Vorteilhafterweise verwendet man Silbersalze mit Perchlorat, Tetrafluoroborat oder Hexafluorophosphat als Anion. Als günstig hat es sich außerdem erwiesen, wenn die Silbersalze in hoher Konzentration vorliegen, möglichst in der Nähe des Sättigungspunktes.The working temperature should preferably be between -12 and 0 ° C and the pH between 5.5 and 6.5. The process according to the invention can be carried out on silver salts with complex anions, except nitrate and sulfate. Silver salts with perchlorate, tetrafluoroborate or hexafluorophosphate are advantageously used as the anion. It has also proven to be favorable if the silver salts are present in high concentration, as close as possible to the saturation point.
Bei der Elektrolyse einer wässrigen AgClO4-Lösung in einer Platinschale (als Kathode) mit einem z.B. 0,3 mm starken Platindraht als Anode erhält man bei pH=6, 0° C und einer Strondichte von 80 A/m2 metallisch glänzende, schwarze Kristalle, die sich analytisch und röntgenographisch als reines Ag2O3 identifizieren lassen. Nach der Röntgenstrukturanalyse sind die Silberatome näherungsweise quadratischplanar von Sauerstoffatomen koordiniert, wobei die Silberatome um 0,09 Ä aus der durch die vier benachbarten Sauerstoffatome definierten Ebene herausragen. Die Ag04-Baugruppen werden über gemeinsame Sauerstoffatome zu einer Raumnetzstruktur verknüpft. Der mittlere Ag-O-Abstand liegt bei 2,02 Å.The electrolysis of an aqueous AgClO 4 solution in a platinum dish (as cathode) with, for example, 0.3 mm thick platinum wire as the anode, gives a shiny black, metallic color at pH = 6.0 ° C and a stron density of 80 A / m 2 Crystals that can be identified analytically and by X-ray analysis as pure Ag 2 O 3 . According to the X-ray structure analysis, the silver atoms are coordinated approximately square-planar by oxygen atoms, the silver atoms protruding by 0.09 Å from the plane defined by the four neighboring oxygen atoms. The Ag0 4 assemblies are linked to a spatial network structure via common oxygen atoms. The average Ag-O distance is 2.02 Å.
Das so hergestellte Silber (III) -oxid lässt sich beispielsweise als Oxidationsmittel, als wirksamer Bestandteil der positiven Elektroden in Zink-Silberoxid-Primärzellen oder als Vorstufe für die AgO-Gewinnung verwenden.The silver (III) oxide produced in this way can be used, for example, as an oxidizing agent, as an effective component of the positive electrodes in zinc-silver oxide primary cells or as a precursor for AgO production.
Folgende Beispiele sollen das erfindungsgemäße Verfahren näher erläutern:
- 1. Eine 5-molare AgClO4-Lösung (ca. 50 Gew. %) wird bei pH=4,5 und einer Temperatur von -10° C mit einer Stromdichte von 1063 A/m2 anodisch oxidiert. Als Anode dient ein Platindraht von 0,3 mm Durchmesser und 500 mm Länge, als Kathode ein Platintiegel mit 50 mm Durchmesser. Die Oxidation erfolgt mit einer elektrischen Spannung von 10 Volt und einer Stromstärke von 50 mA.
- 2. Eine 1-molare AgBF4-Lösung wird bei pH=6 und einer Temperatur von -3° C mit einer Stromdichte von 213 A/m2 in der gleichen Vorrichtung wie Beispiel 1 anodisch oxidiert. (U = 10 Volt, I = 10 mA).
- 3. Eine 0,01-molare AgPF6-Lösung wird bei 0° C und pH=7 mit einer Stromdichte von 106 A/m2 oxidiert (U = 10 V, I = 5mA).
- 1. A 5 molar AgClO 4 solution (approx. 50% by weight) is anodized at pH = 4.5 and a temperature of -10 ° C with a current density of 1063 A / m 2 . A platinum wire with a diameter of 0.3 mm and a length of 500 mm serves as the anode, and a platinum crucible with a diameter of 50 mm serves as the cathode. The oxidation takes place with an electrical voltage of 10 volts and a current of 50 mA.
- 2. A 1-molar AgBF 4 solution is anodized at pH = 6 and a temperature of -3 ° C. with a current density of 213 A / m 2 in the same device as example 1. (U = 10 volts, I = 10 mA).
- 3. A 0.01 molar AgPF 6 solution is oxidized at 0 ° C. and pH = 7 with a current density of 106 A / m 2 (U = 10 V, I = 5mA).
In allen drei Fällen erhält man metallisch glänzende, schwarze Kristalle, die sich als reines Silber (III) -oxid identifizieren lassen.In all three cases, shiny black crystals are obtained, which can be identified as pure silver (III) oxide.
Claims (6)
dadurch gekennzeichnet,
daß die anodische Oxidation bei Temperaturen von -15 bis +10° C durchgeführt wird.1. Process for the preparation of silver (III) oxide by anodic oxidation of silver salts in aqueous solutions with current densities of 40 to 2000 A / m 2 ,
characterized,
that the anodic oxidation is carried out at temperatures from -15 to + 10 ° C.
dadurch gekennzeichnet,
daß die anodische Oxidation bei Temperaturen von -12 bis 0° C durchgeführt wird.2. A method for producing silver (III) oxide according to claim 1,
characterized,
that the anodic oxidation is carried out at temperatures from -12 to 0 ° C.
dadurch gekennzeichnet,
daß die anodische Oxidation bei pH-Werten zwischen 4,5 und 7,5 durchgeführt wird.3. A process for the preparation of silver (III) oxide according to claim 1 and 2,
characterized,
that the anodic oxidation is carried out at pH values between 4.5 and 7.5.
dadurch gekennezeichnet,
daß die anodische Oxidation bei pH-Werten zwischen 5,5 und 6,5 durchgeführt wird.4. A process for the preparation of silver (III) oxide according to claim 1 to 3,
characterized by
that the anodic oxidation is carried out at pH values between 5.5 and 6.5.
dadurch gekennzeichnet,
daß als Silbersalze AgClO4, AgBF4 und AgPF6 eingesetzt werden.5. A process for the preparation of silver (III) oxide according to claim 1 to 4,
characterized,
that AgClO 4 , AgBF 4 and AgPF 6 are used as silver salts.
dadurch gekennzeichnet,
daß die Konzentrationen der Silbersalze nahe dem Sättigungspunkt liegen.6. A process for the preparation of silver (III) oxide according to claim 1 to 5,
characterized,
that the concentrations of the silver salts are close to the saturation point.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3442719A DE3442719C1 (en) | 1984-11-23 | 1984-11-23 | Process for the production of silver (III) oxide |
| DE3442719 | 1984-11-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0185866A1 true EP0185866A1 (en) | 1986-07-02 |
| EP0185866B1 EP0185866B1 (en) | 1988-06-01 |
Family
ID=6250960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85112886A Expired EP0185866B1 (en) | 1984-11-23 | 1985-10-11 | Process for the preparation of silver (iii) oxide |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US4695353A (en) |
| EP (1) | EP0185866B1 (en) |
| JP (1) | JPS61127881A (en) |
| DE (2) | DE3442719C1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5336499A (en) * | 1992-01-10 | 1994-08-09 | Antelman Technologies, Ltd. | Molecular crystal device for pharmaceuticals |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1687056A (en) * | 1922-11-24 | 1928-10-09 | Carl Rudolf | Process of electrolytically separating the alloys of silver with other precious or base metals |
| US3003935A (en) * | 1958-09-08 | 1961-10-10 | Yardney International Corp | Argentous oxide, powder and method for making same |
| US3048469A (en) * | 1958-12-22 | 1962-08-07 | Yardney International Corp | Method of manufacturing soluble silver salts |
| US4067788A (en) * | 1976-09-20 | 1978-01-10 | Electromedia, Inc. | Electrochemical production of finely divided metal oxides, metal hydroxides and metals |
| US4298506A (en) * | 1978-11-03 | 1981-11-03 | Duracell International Inc. | Method of treating silver oxide powder and the product formed therefrom |
-
1984
- 1984-11-23 DE DE3442719A patent/DE3442719C1/en not_active Expired
-
1985
- 1985-10-11 DE DE8585112886T patent/DE3563073D1/en not_active Expired
- 1985-10-11 EP EP85112886A patent/EP0185866B1/en not_active Expired
- 1985-11-13 US US06/797,527 patent/US4695353A/en not_active Expired - Fee Related
- 1985-11-20 JP JP60258832A patent/JPS61127881A/en active Pending
-
1987
- 1987-04-14 US US07/037,970 patent/US4717562A/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| ANGEWANDTE CHEMIE, Band 24, Nr. 2, Februar 1985, Seiten 118-119, VCH Velagsgesellschaft mbH, Weinheim, DE; B. STANDKE et al.: "Ag2O3, a novel binary silver oxide" * |
| CHEMICAL ABSTRACTS, Band 73, Nr. 14, 5. Oktober 1970, Seite 441, Nr. 72539n, Columbus, Ohio, US; R.G. BARRADAS et al.: "Conditions for the electrochemical formation of Ag2O3 in silver in aqueous potassium hydroxide solutions", & CAN. J. CHEM. 1970, 48(15), 2453-4 * |
| ZEITSCHRIFT FÜR ANORGANISCHE UND ALLGEMEINE CHEMIE, Band 332,1963, Seiten 286-296, J.A. Barth Verlag, Leipzig, DD; I. NARAY-SZABO et al.: "Die Darstellung und die Eigenschaften der Silber(III)-oxidphase" * |
Also Published As
| Publication number | Publication date |
|---|---|
| US4717562A (en) | 1988-01-05 |
| JPS61127881A (en) | 1986-06-16 |
| DE3442719C1 (en) | 1985-12-12 |
| EP0185866B1 (en) | 1988-06-01 |
| DE3563073D1 (en) | 1988-07-07 |
| US4695353A (en) | 1987-09-22 |
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