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Monochloramine, NH2Cl

Gattermann came to the conclusion that the chlorination of ammonia occurs in three stages:

  1. NH3 + Cl2 = NH2Cl (monochloramine) + HCl,
  2. NH2Cl + Cl2 = NHCl2 (dichloramine) + HCl,
  3. NHCl2 + Cl2 = NCl3 (trichloramine) + HCl;

but it was not found possible to isolate either mono- or di-chloramine by this method. Raschig,5 however, prepared monochloramine by mixing dilute equimolecular solutions of ammonia and sodium hypochlorite, and distilling the mixture at low temperatures in a vacuum:

NH3 + NaOCl = NH2Cl + NaOH.

An unstable yellow liquid is obtained which can be solidified into colourless unstable crystals with melting-point -66° C.

Monochloramine is also produced by the hydrolysis of potassium cliloramino-sulphonate with dilute mineral acids:

NHCl.SO3K + H2O = NH2Cl + KHSO4.

Monochloramine is decomposed by alkalies with the formation of ammonia and nitrogen:

(i) 3NH2Cl + 3KOH = NH3 + N2 + 3KCl + 3H2O,

(ii) 3NH2Cl + 2NH3 = N2 + 3NH4Cl;

but at the same time some of the ammonia reacts with the chloramine to produce a small amount of hydrazine hydrochloride:

(iii) NH2Cl + NH3 = N2H4.HCl.

Monochloramine reacts with potassium iodide to form nitrogen iodide.

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