US630612A - Process of producing chromic acid by electrolysis. - Google Patents
Process of producing chromic acid by electrolysis. Download PDFInfo
- Publication number
- US630612A US630612A US68900998A US1898689009A US630612A US 630612 A US630612 A US 630612A US 68900998 A US68900998 A US 68900998A US 1898689009 A US1898689009 A US 1898689009A US 630612 A US630612 A US 630612A
- Authority
- US
- United States
- Prior art keywords
- acid
- solution
- cathode
- anode
- chromium
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title description 15
- 230000008569 process Effects 0.000 title description 14
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 title description 12
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 title description 10
- 238000005868 electrolysis reaction Methods 0.000 title description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 229940032330 sulfuric acid Drugs 0.000 description 18
- 239000002253 acid Substances 0.000 description 10
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- JZULKTSSLJNBQJ-UHFFFAOYSA-N chromium;sulfuric acid Chemical compound [Cr].OS(O)(=O)=O JZULKTSSLJNBQJ-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/02—Oxides or hydrates thereof
- C01G37/033—Chromium trioxide; Chromic acid
Definitions
- MAX LE BLANQ OF FRANKFORT-ON-TIIE-MAIN, AND HERMANN REISENEG- GER, OF HOCHST-ON-THE-MAIN, GERMANY, ASSIGNORS TO THE FARE- W'ERKE, VORMALS MEISTER, LUOIUS & BRUNING, OF H6CHST-ON-THE- MAIN, GERMANY.
- the chromium oxid is dissolved in an excess of caustic-soda lye, and this solution is poured into the anode-compartment of a vessel provided with a diaphragm, while as cathode a fluidfor instance, caustic-soda lye-is employed.
- caustic-soda lye-is employed At the anode sodium chromate is formed by the current, while causticsoda lye is produced at the cathode.
- the so dium chromate thus formed can be changed into bichromatebyfurtherelectrolysis.
- Electrochem'istry (,hapt. IV, 1896, London, Macmillan & 00., Ltd.) ⁇ Ve have originally at the cathode as ions H, 1180,, S6,; at the anode, in a strong acid solution, also II, 1180,, S0 and Cr, negative ions of chromium sulfuric acid of the type Cr (S0 and CrO Apart from the slight action of the diffusion the positive ions move on the passing of the current to the cathode and the negative ions to the anode. Consequently S?) and HO pass from the cathode through the diaphragm to the anode and from the latter H and Or to the cathode.
- the re sult is that some chromium oxidthe quantity of Or not being great-4s formed at the cathode, and besides an increase of sulfuric acid has taken place at the anode and a decrease at the cathode. That this latter concentration change is of importance is shown by an experiment which we have made on another occasion, the result of which, however, may also be applied in this case.
- the solution oxidized at the anode can at once be employed in manufacture,and the chromic acid therein being thus retransformed into chromium oxid can then be moved to the cathode,while the solution atfirst in the cathode-compartment is now transferred to the anode-compartment.
- the cathode solution is at the beginning of the second operation richer in sulfuric acid than the anode solution, yet on the, passing of the current the excess of sulfuric acid is transferred to the anode.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
UNITED STATES PATENT CFFICE.
MAX LE BLANQ, OF FRANKFORT-ON-TIIE-MAIN, AND HERMANN REISENEG- GER, OF HOCHST-ON-THE-MAIN, GERMANY, ASSIGNORS TO THE FARE- W'ERKE, VORMALS MEISTER, LUOIUS & BRUNING, OF H6CHST-ON-THE- MAIN, GERMANY.
PROCESS OF PRODUCING CHROMIC ACID BY ELECTROLYSIS.
SPECIFICATION formingpart of Letters Patent No. 630,612, dated August 8, 1899.
Application filed August 19, 1898- Serial No. 689,009. (No specimens.)
To all whmn it may concern:
Be it known that we, MAX LE BLANO, pro fessor of chemistry, residing at Frankfort-onthe-Main, and HERMANN REISENEGGER, doctor of philosophy, residing at Hochst-on-the Main, Germany, citizens of the Empire of Germany, have invented certain new and useful Improvements in the Production of Ghromic Acid by Electrolytic Oxidation of Solutions of Ohromium-Oxid Salts, of which the following is a specification.
The process employed on a large scale for regenerating chromic acid from solutions containing chromium-oxid salts is complicated and scarcely rational. As is known, the solutions containing for the most part chromium sulfate are mixed with lime, and the paste thus obtained, which consists of chromium oxid, an excess of quicklime, besides large quantities of calcium sulfate, is heated to blood-red with access of air. Ohromate of lime is thus formed, which in an aqueous solution of sodium sulfate changes into soluble sodium chromate and calcium sulfate. On removing the latter the solution of sodium chromate may be converted into chromic acid by addition of sulfuric acid and employed for oxidation. Not only is the quantity of chro mic acid obtained by this process small com-' pared with the quantity of chromium oxid employed, but also considerable quantities of sulfuric acid are lost and many other inconveniences attend the process, for the sodium chromate can only have a sufficient oxidizing action in an acid solution, in this case a sulfuric-acid solution, and the whole of the acid added forms by this process of regeneration a worthless prod uct-namely, refuse calcium sulfate.
It has been proposed to regenerate the chromic acid from the solutions containing chromium-oxid salts by means of the electric current. (Zet'tschr. f. Angew. Chem, 1893, p. 360; Hilfsbuch f. d. Elecirotechm'lc 'v. Grawinkel at Strecker, 4: Aufi, p. 506, 1895; British Patent 5,542 of 1886.) According to the first process the chromium oxid is dissolved in an excess of caustic-soda lye, and this solution is poured into the anode-compartment of a vessel provided with a diaphragm, while as cathode a fluidfor instance, caustic-soda lye-is employed. At the anode sodium chromate is formed by the current, while causticsoda lye is produced at the cathode. The so dium chromate thus formed can be changed into bichromatebyfurtherelectrolysis. Apart from the great consumption of energy, according to the description, (at least five volts at a current density of somewhat more than two hundred amperes to the square meter,) this method of oxidation is impractical, as sodium chromate is employed for oxidation in a sulfuric-acid solution, and the loss of sulfuric acid is in this process accompanied bya further loss of the expensive caustic-soda lye. In the second process the chromic solutions which originate from exhausted galvanic elements are the main source of supply. These solutions are placed in the anode-compartment of a cell provided with a diaphragm, while in the cathode-compartment is put an acid solualum with zinc oxid dissolved therein. If the electric current be conducted through it, then chromic acid or chromates are formed at the anode and metallic zinc separates at the cathode. It is at once evident that to carry out the process in this form on a large scale would in most cases be unsatisfactory, as the requisite quantities of zinc sulfate would. be wanting. But could this process not be carried out with advantage in employing a pure sulfuric-acid solution instead of the cathode solution, while having at the anode chromium sulfate in an aqueous solution of sulfuric acid to be regenerated? Suppose electrolysis taking place, then hydrogen 'tion of zinc sulfate ora solution of ammonia is developed at the cathode, while chromic tion changes take place. (Vz'de Le Blane, The
Elements of Electrochem'istry, (,hapt. IV, 1896, London, Macmillan & 00., Ltd.) \Ve have originally at the cathode as ions H, 1180,, S6,; at the anode, in a strong acid solution, also II, 1180,, S0 and Cr, negative ions of chromium sulfuric acid of the type Cr (S0 and CrO Apart from the slight action of the diffusion the positive ions move on the passing of the current to the cathode and the negative ions to the anode. Consequently S?) and HO pass from the cathode through the diaphragm to the anode and from the latter H and Or to the cathode. The re sult is that some chromium oxidthe quantity of Or not being great-4s formed at the cathode, and besides an increase of sulfuric acid has taken place at the anode and a decrease at the cathode. That this latter concentration change is of importance is shown by an experiment which we have made on another occasion, the result of which, however, may also be applied in this case. We had the same solution at the anode and cathode, containing in one-hundred grams thirty.- five grams ll SO and 7.5 grams 01- 0 After having oxidized one per cent. of the chromium oxid the quantity of sulfuric acid at the anode had increased about fifteen per cent., if eompared to the original quantity.
The above explanation shows that to carry out this process would cause great drawbacks. It would, for instance, be necessary to separate often the excess of sulfuric acid from the anode solution by means of lime, as the conductivity of the solution is only good within certain concentration changes of the sulfuric acid. By this separation (apart from the actual labor) besides the sulfuric acid also some chromium solution is lost, and the lime is liable to cause troublesome impurities. Moreover, the sulfuric acid becomes too diluted at the cathode and will have to be replaced by fresh concentrated acid, or else the electric current would encounter too much resistance. The dilute acid, with the chromium oxid migrated over, will have to beconsidered as lost.
All the drawbacks mentioned are avoided by a new rational process of great economical importance, as has been shown by experiments on a large scale. There is used the solution of a chromium salt in the corresponding acid-for instance, chromium sulfate dissolved in sulfuric acid-and preferably a so lution of the highest possible electric conductivity, about one hundred grams C13 0 and three hundred and fifty grams I-I SO can be made up with water to one liter. This solution is placed in the anode and cathode compartments of a vessel coated with lead, provided with adiaphragm, and having lead plates as electrodes. By the action of the current chromic acid is formed at the anode, while hydrogen is evolved at the cathode. As already said above, a migration of sulfuric acid also takes place, the concentration increasing at the anode and decreasing at the cathode. The solution oxidized at the anode can at once be employed in manufacture,and the chromic acid therein being thus retransformed into chromium oxid can then be moved to the cathode,while the solution atfirst in the cathode-compartment is now transferred to the anode-compartment. The cathode solution is at the beginning of the second operation richer in sulfuric acid than the anode solution, yet on the, passing of the current the excess of sulfuric acid is transferred to the anode. By this arrangement of circulation, moving alternately the solution from the cathode to the anode, it results that an accumulation of sulfuric acid nowhere takes place and that, in fact, the same solution can be employed indefinitely in its unchanged composition and without any loss in substance as an excellent carrier of oxygen. At a current density of more than three hundred amperes per square meter the tension amounts to hardly 3.5 volts at about 50 centigrade.
Having thus described our invention, we claim as new and desire to secure by Letters Patent The herein-described process of producing chromic acid, which consists in first electrolyzing a solution of a chromium-oxid salt in an aqueous solution of the corresponding acid, as for instance solution of chromium sulfate in aqueous sulfuric acid, then employing the mixture of chromic and other acid resulting from the electrolysis for reactions by which it is reconverted into the solution of the oxid salt in an acid, charging this at the cathode when the fluid formerly at the cathode has been transferred to the anode for formation again of chromic acid, and so oncontinuously, substantially as set forth.
In testimony that we claim the foregoing as our invention we have signed our names in presence of two subscribing witnesses.
MAX LE BLANO. I-IERMANN REISENEGGE Pt.
\Vitnesses:
BERNHARD LEYDECKER, ALFRED BRISBOIS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68900998A US630612A (en) | 1898-08-19 | 1898-08-19 | Process of producing chromic acid by electrolysis. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68900998A US630612A (en) | 1898-08-19 | 1898-08-19 | Process of producing chromic acid by electrolysis. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US630612A true US630612A (en) | 1899-08-08 |
Family
ID=2699207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US68900998A Expired - Lifetime US630612A (en) | 1898-08-19 | 1898-08-19 | Process of producing chromic acid by electrolysis. |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US630612A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2600171A (en) * | 1942-10-24 | 1952-06-10 | Sagen Gunnar | Regeneration of chromic acid baths utilized in electrodeposition of chromium |
| US3423300A (en) * | 1967-10-25 | 1969-01-21 | Great Lakes Carbon Corp | Electrolytic regeneration of reduced chromium compounds |
| US20220127740A1 (en) * | 2019-05-02 | 2022-04-28 | Universitaet Ulm | Electrolyte for chromium deposition from cr(iii)-compounds |
-
1898
- 1898-08-19 US US68900998A patent/US630612A/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2600171A (en) * | 1942-10-24 | 1952-06-10 | Sagen Gunnar | Regeneration of chromic acid baths utilized in electrodeposition of chromium |
| US3423300A (en) * | 1967-10-25 | 1969-01-21 | Great Lakes Carbon Corp | Electrolytic regeneration of reduced chromium compounds |
| US20220127740A1 (en) * | 2019-05-02 | 2022-04-28 | Universitaet Ulm | Electrolyte for chromium deposition from cr(iii)-compounds |
| US11932958B2 (en) * | 2019-05-02 | 2024-03-19 | Universitaet Ulm | Electrolyte for chromium deposition from Cr(III)-compounds |
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