Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B21/00—Nitrogen; Compounds thereof
  • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
  • C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms

Definitions

• a nitrosodisulfonate of Formula I above can be produced in almost quantitative yields from a hydroxylamine disulfonate 'of the formula wherein X and m are as above by subjecting an aqueous medium containing the hydroxylamine disulfonate of Formula 11 above to electrolysis.
• This process provides the nitrosodisulfonate of the Formula I above in high yields without any danger of contamination from metal oxides.
• another advantage of this process is that the hydroxylamine disulfonate of Formula II above, which is prepared from sulfur dioxide and an alkali metal nitrite or alkaline earth metal nitrite, .need not be isolated from its reaction medium, but can be directly converted by electrolysis to the nitrosodisulfonate of Formula I above.
• a process is provided for directly converting the reaction product of sulfur dioxide with an alkali metal nitrite or alkaline earth metal nitrite into the nitrosodisulfonate of Formula I above without the necessity of isolating any intermediates. Therefore, the process of this invention provides a simple and economical method for producing the nitrosodisulfonate of Formula I above.
• X can be any conventional alkali metal or alkaline earth metal.
• conventional alkali metals which X can designate are included sodium, potassium, lithium, rubidium, etc.
• alkaline earth metals which are designated by X are included magnesium, calcium, etc.
• reaction of this invention is carried out by electrolytically treating an aqueous reaction medium containing the hydroxylamine disulfonate of Formula 11 above. This reaction can take place by any conventional electrolytic process.
• an aqueous solution containing the hydroxylamine derivative of Formula II above is placed in an electrolytic cell, e. g., an electrolysis tank which may or may not be provided with a cell divider or membrane, and which is provided with an anode and a cathode.
• the cathode and the anode can be made of any material commonly employed for making cathodes and anodes in the electro-chemical art, e.g., carbon, monel, stianless steel, platinum, palladium, nickel, nickel-alloy, etc.
• the electrolytic cell can be provided with a stirrer or mechanical agitator, or the reaction medium can be circulated by means of pumps.
• the electrolysis can be carried out by applying voltages of from 0.5 to 50 volts to the liquid aqueous reaction medium. Generally, it is preferred to carry out the reaction utilizing from 5 to 25 volts.
• the electric current passed through the solution can be of a current density of up to 50 amperes per square decimeter and can be as low as 0.01 ampere per square decimeter. Generally, it is preferred to utilize a current density of from 0.02 to 5 amperes per square decimeter.
• a conventional electrolyte can be added to the aqueous medium.
• conventional electrolytes which can, if desired, be added to the liquid aqueous reaction medium prior to electrolysis are included, sodium hydroxide, acetic acid, sodium acetate, sodium carbonate, sodium bicarbonate, sodium phosphates, sodium chloride, etc.
• the pH of the reaction medium is maintained at 4 or above. Optimally this reaction is carried out at a pH of from 4 to 13.
• the aforementioned electrolytes can be utilized to obtain the desired pH.
• the aqueous solution which is subjected to electrolysis generally contains the hydroxylamine derivative of Formula II above in a concentration of at least 0.1 mole per 1,000 ml., preferably from 0.1 mole to 2 moles per 1,000 ml. of solution.
• the electrolysis reaction can be carried out at any temperature of from -l5 C. to 50 C. Generally it is preferred to carry out this reaction at a temperature of -l0 C. to +10 C.
• the electrolysis reaction can be carried out for a period of at least /2 hour or longer. Generally, it is preferred to carry out the electrolysis for a period of from 1 to 10 hours. If desired, electrolysis can be carried out for periods longer than 10 hours. However, since the use of electrolysis time of greater than 10 hours produces no additional beneficial results, these prolonged reaction times are seldom employed.
• the hydroxylamine of Formula II above can be prepared by reacting an alkali metal or alkaline earth metal nitrite with sulfur dioxide in an aqueous medium.
• the sulfur dioxide can be bubbled in as a gas into the aqueous reaction medium.
• the reaction medium can contain any source capable of liberating sulfur dioxide such as a mixture of an organic acid such as acetic acid and an alkali metal or alkaline earth metal bisulfite or sulfite.
• the nitrite salt and sulfur dioxide or sulfur dioxide liberating source are reacted together at a temperature of from -15 C. to 50 C. to produce the hydroxylamine disulfonate of Formula II above, with -l0 C.
• This reaction is carried out by reacting 1 mole of the nitrite salt with 2 moles of the sulfur dioxide which can be either bubbled or liberated from the sulfur dioxide liberating source in water. Furthermore, this reaction is carried out at a pH of at least 2, preferably, from 2 to 4. This pH is obtained by the addition of acetic acid or other lower alkanoic acids to the reaction medium when these acids are utilized as a component of the sulfur dioxide liberating material. However, this pH can be obtained by the addition of weakly basic inorganic salts such as sodium phosphates, sodium carbonates, sodium bicarbonates, etc.
• This aqueous reaction medium containing the hydroxylamine disulfonate can be directly subjected to electrolysis to form the nitrosodisulfonate of Formula I above without isolating the hydroxylamine disulfonate of Formula II above.
• the hydroxylamine of Formula II can be prepared by reacting ammonium nitrite with sulfur dioxide in the aforementioned manner.
• ammonium bisulfite or sulfite can be utilized in place of alkali metal or alkaline earth metal sulfite or bisulfite in forming sulfur dioxide.
• the aqueous reaction medium which is produced by electrolysis contains the compound of Formula I in solution.
• This reaction medium can be utilized as an oxidizing medium.
• the compound of Formula I can be recovered in solid form by conventional crystalliza tion techniques such as by treating the aqueous reaction medium with a saturated solution of an alkali metal salt.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=25285299

Family Applications (1)

Country Status (8)

• 1969
  • 1969-07-14 US US841614A patent/US3591471A/en not_active Expired - Lifetime
• 1970
  • 1970-05-28 NL NL7007718A patent/NL7007718A/xx unknown
  • 1970-06-25 SE SE08847/70A patent/SE359521B/xx unknown
  • 1970-06-26 DK DK332970A patent/DK132790C/da active
  • 1970-06-29 DE DE19702032084 patent/DE2032084A1/de active Pending
  • 1970-06-30 GB GB31504/70A patent/GB1293068A/en not_active Expired
  • 1970-07-10 FR FR7025764A patent/FR2055034A5/fr not_active Expired
  • 1970-07-10 BE BE753275D patent/BE753275A/xx unknown

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