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Max Appl
Copyright 0 WILEY-VCH Verlag GmbH, I999
231
atom by metals. Finally, there are the nitrides, such as lithium or magnesium nitride,
Li,N or Mg,N,.
. - The nitrides of reactive metals, such as lithium, magnesium, calcium,
aluminum, and titanium, are formed directly from the elements at elevated tempera-
ture. In many cases, it is better to obtain nitrides through the action of ammonia on
the metals or metal compounds at higher temperature. A nitride also may result from
thermal decomposition of an amide.
Sulfur, phosphorus, and halogens also can take the place of the hydrogen atoms in
ammonia. At relatively low temperatures, halogens react with ammonia to form
nitrogen -halogen compounds and ammonium halides. At higher temperatures the pro-
ducts are nitrogen and hydrogen halides. With sodium hypochlorite, ammonia forms
hydrazine hydrate (Raschig synthesis) with chloramine, H,NCI, as an intermediate.
Reactions in liquid ammonia [1414] sometimes proceed differently from those in
water because of the solubility difference of many salts between water and ammonia.
For example, the reaction
H2 0
2 AgNO, -t BaC12 2 AgCl + Ba(NO,), (97)
NH3
2 32
or obtainable only with difficulty. Examples are the sodium selenides, Na,Se through
.t
Na,Se,, tellurides up to Na,Te,, antimonides, arsenides, polystannides, and polyplunl-
bides. Introducing oxygen into the solution of alkali metals forms peroxides, Na,O,,
z
E
- - as well as dioxides, KO,, RbO,, and CsO,. White explosive salts of the hypothe-
K,O,, 2
tical acetylenediols, such as KO-C = C-OK, result with carbon monoxide [ 14161: with
0
vI
12.2. U s e s of Ammonia
In 1997 about 85 % of ammonia production was consumed for fertilizers. Ammonia
is either converted into solid fertilizers (urea; ammonium nitrate, phosphate, sulfate) or
directly applied to arable soil.
The industrial use of ammonia is around 15%. Actually every nitrogen atom in
industrially produced chemical compounds comes directly or indirectly from ammonia.
An important use of the ammonia nitrogen, partly after conversion to nitric acid, is the
production of plastics and fibers, such as polyamides, urea -formaldehyde -phenol
resins, melamine-based resins, polyurethanes, and polyacrylonitrile.
Some examples of industrially important uses are the following reactions: With alkyl
halides or alcohols amines or imines can be manufactured. For example, methanol
forms mono- through trimethylamine; dichloromethane yields ethylene imine in the
presence of calcium oxide. Amines can also be produced by reacting ainnionia with
alkyl halides in multistage processes [14251.
233
.! Acid Amides can be produced by acylating ammonia with esters, acid anhydrides, or
the acids themselves (above 100 "C); an important product is formamide from methyl
E formate. Alternatively acid amides can be synthesized by reacting acid halides with
50 ammonia. Catalytic hydrogenation converts the acid amides to primary amines. Am-
uI monia and aldehydes or ketones are the basis for different stable products. With
! formaldehyde hexamethylenetetramine (urotropine) is obtained; with acetaldehyde,
3
'0 ammono acetaldehyde; with benzaldehyde, hydrobenzamide; with ethylene and pro-
C
(d pylene oxides, aqueous ammonia reacts to form ethanol- or propanolamine.
ul
The catalytic gas-phase oxidation of olefins in the presence of ammonia on vana-
.-
$ dium- or molybdenum-containing catalysts, so-called ammonoxidation, results in eco-
(d
2 nomic yields of the commercially important acid nitriles, for example, acrylonitrile from
- propylene 114261. Ammonoxidation of o-xylene yields phthalodinitrile in a single
.-3 reaction step.
234