Difference between revisions of "Hydroxylammonium chloride"

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(Created page with "{{Chembox | Name = Hydroxylammonium chloride | Reference = | IUPACName = Hydroxylammonium chloride | PIN = | SystematicName = | OtherNames = Hydroxyazanium chloride<br>Hydroxy...")
 
 
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| OtherNames = Hydroxyazanium chloride<br>Hydroxylamine chloride<br>Hydroxylamine HCl<br>Hydroxylamine hydrochloride<br>Hydroxylammoniumchloride
 
| OtherNames = Hydroxyazanium chloride<br>Hydroxylamine chloride<br>Hydroxylamine HCl<br>Hydroxylamine hydrochloride<br>Hydroxylammoniumchloride
 
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| ImageFile = Hydroxylamine_hydrochloride2.jpg
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| ImageCaption = Hydroxylamine HCl crystals
 
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| Density = 1.67 g/cm<sup>3</sup> (20 °C)
 
| Density = 1.67 g/cm<sup>3</sup> (20 °C)
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| Formula = [NH<sub>3</sub>OH]Cl<br>NH<sub>2</sub>OHHCl
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| Formula = H<sub>4</sub>NOCl<br>[NH<sub>3</sub>OH]Cl<br>NH<sub>2</sub>OH·HCl
 
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| LogP = -1.092
 
| LogP = -1.092
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| OtherFunction =  
 
| OtherFunction =  
 
| OtherFunction_label =  
 
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| OtherCompounds = [[Hydroxylammonium nitrate]]<br>[[Hydroxylammonium sulfate]]
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| OtherCompounds = [[Hydroxylammonium nitrate]]<br>[[Hydroxylammonium perchlorate]]<br>[[Hydroxylammonium sulfate]]
 
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'''Hydroxylammonium chloride''' ('''[NH<sub>3</sub>OH]Cl''') is the [[hydrochloric acid]] salt of [[hydroxylamine]].
+
'''Hydroxylammonium chloride''' or '''hydroxylamine hydrochloride''' ('''[NH<sub>3</sub>OH]Cl''') is the [[hydrochloric acid]] salt of [[hydroxylamine]].
  
 
==Properties==
 
==Properties==
 
===Chemical===
 
===Chemical===
 
Hydroxylamine hydrochloride reacts with [[ketone]]s to form oximes.
 
Hydroxylamine hydrochloride reacts with [[ketone]]s to form oximes.
 +
 +
Heating hydroxylamine hydrochloride with [[sodium nitrite]] yields [[nitrous oxide]].<ref>https://www.youtube.com/watch?v=uzSe3BDCkF8</ref>
 +
 +
: NH<sub>2</sub>OH·HCl + NaNO<sub>2</sub> → N<sub>2</sub>O + NaCl + 2 H<sub>2</sub>O
  
 
===Physical===
 
===Physical===
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==Preparation==
 
==Preparation==
−
Hydroxylammonium chloride can be prepared by reducing acidified [[potassium nitrite]] (aka [[nitrous acid]]) with [[potassium bisulfite]], which yields [[hydroxylammonium sulfate]]. To obtain the chloride, [[barium chloride]] is added.<ref>https://www.prepchem.com/synthesis-of-hydroxylamine-hydrochloride/</ref>
+
Hydroxylammonium chloride can be prepared by reducing acidified [[potassium nitrite]] (aka [[nitrous acid]]) with [[potassium bisulfite]], which yields [[hydroxylammonium sulfate]]. To obtain the chloride, [[barium chloride]] is added.<ref>https://www.prepchem.com/synthesis-of-hydroxylamine-hydrochloride/</ref> An intermediate in this reaction is potassium hydroxylammonium disulfonate, which has a poor solubility in water (the sodium salt has a high solubility). Despite this it has been mentioned that often precipitation is very delayed and slow.<ref>F. Raschig, ''Ber. Dtsch. Chem. Ges.'', '''1907''', 40(''4''), 4580-4588, [https://doi.org/10.1002/cber.190704004106 doi.org/10.1002/cber.190704004106]</ref> The intermediate hydroxylammonium disulfonate (or rather the monosulfonate produced by hydrolysis in water) can be used directly to prepare oximes,<ref>W. L. Semon, V. R. Damerell, ''J. Am. Chem. Soc.'', '''1924''', 46, 5, 1290–1293, [https://doi.org/10.1021/ja01670a023 doi.org/10.1021/ja01670a023]</ref> from which hydroxylamine can be regenerated.<ref>Waldo L. Semon, ''Org. Synth.'', '''1923''', 3, 61, [https://doi.org/10.15227/orgsyn.003.0061 doi.org/10.15227/orgsyn.003.0061]</ref> It should be noted that the acetone oxime prepared in the cited procedure is quite volatile. Apart from steam distillation it can be also extracted into [[diethyl ether]], but this only works for a neutral solution and no oxime is extracted at acidic or basic pH.<ref>A. Janny, ''Ber. Dtsch. Chem. Ges.'', '''1882''', 15(''2''), 2778-2783, [https://doi.org/10.1002/cber.188201502255 doi.org/10.1002/cber.188201502255]</ref> The literature also reports a preparation of acetone oxime by the reduction of an acetone/sodium nitrite solution with zinc dust.<ref>A. Ogata, S. Hirano, ''Yakugaku Zasshi-journal of The Pharmaceutical Society of Japan'', '''1930''', 50(''6''), 555-559, [https://doi.org/10.1248/YAKUSHI1881.50.6_555 doi.org/10.1248/YAKUSHI1881.50.6_555]</ref>
  
−
Hydroxylamine hydrochloride can also be made by heating [[nitromethane]] with concentrated [[hydrochloric acid]]:
+
Hydroxylamine hydrochloride can also be made by heating [[nitromethane]] with concentrated [[hydrochloric acid]]:<ref>Axt, ''Glyoxime, Diaminofurazan and some Energetic Derivatives'', sciencemadness publication, [http://www.sciencemadness.org/member_publications/energetic_glyoxime_and_diaminofurazan_derivatives.pdf available here]</ref>
  
−
:CH<sub>3</sub>NO<sub>2</sub> + HCl → NH<sub>2</sub>OH·HCl + 2 H<sub>2</sub>O + CO
+
: CH<sub>3</sub>NO<sub>2</sub> + HCl → NH<sub>2</sub>OH·HCl + 2 H<sub>2</sub>O + CO
 +
 
 +
Higher nitroalkanes react in a similar fashion.<ref>R. B. Cundall, A. W. Locke, ''J. Chem. Soc. B'', '''1968''', 98-103, [https://doi.org/10.1039/J29680000098 doi.org/10.1039/J29680000098]</ref>
 +
 
 +
This reaction is possible to do with the nitromethane/methanol azeotrope, however the yields are considerably lower.<ref>Henry, personal experience. Yield for hydrolysis was 29%</ref>
 +
 
 +
There are reports in the literature about the electrolytic reduction of [[nitric acid]] on various cathodes including lead, tin, with and without amalgamation.<ref>J. Tafel, ''Z. Anorg. Chem.'', '''1902''', 31(1), 289-325. [https://doi.org/10.1002/zaac.19020310135 doi.org/10.1002/zaac.19020310135]</ref>
 +
 
 +
The reduction of [[ethyl nitrate]] using [[tin(II) chloride]] in [[hydrochloric acid]] also yields hydroxylammonium chloride, but separation from the tin solution is somewhat difficult, not to mention the dangers of working with highly explosive ethyl nitrate.<ref>O. F. v. Dumreicher, ''Monatshefte für Chemie'', '''1880''', 1, 724–754 [https://doi.org/10.1007/BF01517102 doi.org/10.1007/BF01517102]</ref>
  
 
==Projects==
 
==Projects==
 
*Preparation of oximes and hydroxamic acids
 
*Preparation of oximes and hydroxamic acids
 +
*Make nitrous oxide
 +
*Make glyoxime/diacetyldioxime and its red nickel complex
  
 
==Handling==
 
==Handling==
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Hydroxylammonium chloride should be kept in closed plastic bottles, in a cool and safe place.
 
Hydroxylammonium chloride should be kept in closed plastic bottles, in a cool and safe place.
  
−
Hydroxylamine hydrochloride is stable up to 60 °C, above this temperature there will be significant degradation.<ref>Cisneros, Lizbeth O.; Rogers, William J.; Mannan, M. Sam; Thermochimica Acta; vol. 414; nb. 2; (2004); p. 177 - 183</ref>
+
Hydroxylamine hydrochloride is stable up to 60 °C, above this temperature there will be significant degradation.<ref>L. O. Cisneros, W. J. Rogers, M. S. Mannan, ''Thermochimica Acta'', '''2004''', 414(''2''), 177-183, [https://doi.org/10.1016/j.tca.2003.09.023 doi.org/10.1016/j.tca.2003.09.023]</ref>
  
 
===Disposal===
 
===Disposal===
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Reduction of hydroxylamine with Zn/HCl yields [[ammonia]].  
 
Reduction of hydroxylamine with Zn/HCl yields [[ammonia]].  
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 +
==Gallery==
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<gallery widths="200" position="center" columns="4" orientation="none">
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Hydroxylamine_hydrochloride1.jpg|Very large crystals of slightly discolored hydroxylamine hydrochloride
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Hydroxylamine_hydrochloride_micro.jpg|Microscopic view of the crystals, horizontal view window is about 3 mm
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</gallery>
  
 
==References==
 
==References==

Latest revision as of 09:47, 25 June 2023

Hydroxylammonium chloride
Hydroxylamine hydrochloride2.jpg
Hydroxylamine HCl crystals
Names
IUPAC name
Hydroxylammonium chloride
Other names
Hydroxyazanium chloride
Hydroxylamine chloride
Hydroxylamine HCl
Hydroxylamine hydrochloride
Hydroxylammoniumchloride
Properties
H4NOCl
[NH3OH]Cl
NH2OH·HCl
Molar mass 69.49 g/mol
Appearance White solid
Odor Odorless
Density 1.67 g/cm3 (20 °C)
Melting point 154–156 °C (309–313 °F; 427–429 K) (decomposition)
94 g/100 ml (25 °C)
Solubility Insoluble in hydrocarbons
Solubility in ethanol 4.43 g/100 ml (20 °C)[1]
Solubility in methanol 16.1 g/100 ml (20 °C)[2]
Hazards
Safety data sheet Sigma-Aldrich
Lethal dose or concentration (LD, LC):
642 mg/kg (rat, oral)
Related compounds
Related compounds
 Hydroxylammonium nitrate
Hydroxylammonium perchlorate
Hydroxylammonium sulfate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Hydroxylammonium chloride or hydroxylamine hydrochloride ([NH3OH]Cl) is the hydrochloric acid salt of hydroxylamine.

Properties

Chemical

Hydroxylamine hydrochloride reacts with ketones to form oximes.

Heating hydroxylamine hydrochloride with sodium nitrite yields nitrous oxide.[3]

NH2OH·HCl + NaNO2 → N2O + NaCl + 2 H2O

Physical

Hydroxylammonium chloride is a white solid, very soluble in water.

Availability

Hydroxylammonium chloride is sold by lab suppliers.

Preparation

Hydroxylammonium chloride can be prepared by reducing acidified potassium nitrite (aka nitrous acid) with potassium bisulfite, which yields hydroxylammonium sulfate. To obtain the chloride, barium chloride is added.[4] An intermediate in this reaction is potassium hydroxylammonium disulfonate, which has a poor solubility in water (the sodium salt has a high solubility). Despite this it has been mentioned that often precipitation is very delayed and slow.[5] The intermediate hydroxylammonium disulfonate (or rather the monosulfonate produced by hydrolysis in water) can be used directly to prepare oximes,[6] from which hydroxylamine can be regenerated.[7] It should be noted that the acetone oxime prepared in the cited procedure is quite volatile. Apart from steam distillation it can be also extracted into diethyl ether, but this only works for a neutral solution and no oxime is extracted at acidic or basic pH.[8] The literature also reports a preparation of acetone oxime by the reduction of an acetone/sodium nitrite solution with zinc dust.[9]

Hydroxylamine hydrochloride can also be made by heating nitromethane with concentrated hydrochloric acid:[10]

CH3NO2 + HCl → NH2OH·HCl + 2 H2O + CO

Higher nitroalkanes react in a similar fashion.[11]

This reaction is possible to do with the nitromethane/methanol azeotrope, however the yields are considerably lower.[12]

There are reports in the literature about the electrolytic reduction of nitric acid on various cathodes including lead, tin, with and without amalgamation.[13]

The reduction of ethyl nitrate using tin(II) chloride in hydrochloric acid also yields hydroxylammonium chloride, but separation from the tin solution is somewhat difficult, not to mention the dangers of working with highly explosive ethyl nitrate.[14]

Projects

  • Preparation of oximes and hydroxamic acids
  • Make nitrous oxide
  • Make glyoxime/diacetyldioxime and its red nickel complex

Handling

Safety

Hydroxylammonium chloride is an irritant to the respiratory tract, skin, eyes, and other mucous membranes. It is harmful if swallowed and may be absorbed through the skin. Hydroxylamine and its compounds are considered possible mutagen.

Storage

Hydroxylammonium chloride should be kept in closed plastic bottles, in a cool and safe place.

Hydroxylamine hydrochloride is stable up to 60 °C, above this temperature there will be significant degradation.[15]

Disposal

Hydroxylamine hydrochloride can be neutralized by using a ketone and then gently heating the resulting oxime, which reforms the ketone and releases nitrogen gas and water. It can also be neutralized by diluting it with water and carefully adding ferric salts or other compounds known to accelerate its decomposition.

Reduction of hydroxylamine with Zn/HCl yields ammonia.

Gallery

  • Very large crystals of slightly discolored hydroxylamine hydrochloride

  • Microscopic view of the crystals, horizontal view window is about 3 mm

References

  1. ↑ Lobry de Bruyn, C. A.; Rec. Trav. chim.; vol. 10; (1891); p. 102
  2. ↑ Lobry de Bruyn, C. A.; Rec. Trav. chim.; vol. 10; (1891); p. 102
  3. ↑ https://www.youtube.com/watch?v=uzSe3BDCkF8
  4. ↑ https://www.prepchem.com/synthesis-of-hydroxylamine-hydrochloride/
  5. ↑ F. Raschig, Ber. Dtsch. Chem. Ges., 1907, 40(4), 4580-4588, doi.org/10.1002/cber.190704004106
  6. ↑ W. L. Semon, V. R. Damerell, J. Am. Chem. Soc., 1924, 46, 5, 1290–1293, doi.org/10.1021/ja01670a023
  7. ↑ Waldo L. Semon, Org. Synth., 1923, 3, 61, doi.org/10.15227/orgsyn.003.0061
  8. ↑ A. Janny, Ber. Dtsch. Chem. Ges., 1882, 15(2), 2778-2783, doi.org/10.1002/cber.188201502255
  9. ↑ A. Ogata, S. Hirano, Yakugaku Zasshi-journal of The Pharmaceutical Society of Japan, 1930, 50(6), 555-559, doi.org/10.1248/YAKUSHI1881.50.6_555
  10. ↑ Axt, Glyoxime, Diaminofurazan and some Energetic Derivatives, sciencemadness publication, available here
  11. ↑ R. B. Cundall, A. W. Locke, J. Chem. Soc. B, 1968, 98-103, doi.org/10.1039/J29680000098
  12. ↑ Henry, personal experience. Yield for hydrolysis was 29%
  13. ↑ J. Tafel, Z. Anorg. Chem., 1902, 31(1), 289-325. doi.org/10.1002/zaac.19020310135
  14. ↑ O. F. v. Dumreicher, Monatshefte für Chemie, 1880, 1, 724–754 doi.org/10.1007/BF01517102
  15. ↑ L. O. Cisneros, W. J. Rogers, M. S. Mannan, Thermochimica Acta, 2004, 414(2), 177-183, doi.org/10.1016/j.tca.2003.09.023

Relevant Sciencemadness threads

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