Ammonia: Principles and Industrial Practice

Max Appl
Copyright 0 WILEY-VCH Verlag GmbH, I999

12. Chemical Reactions and Uses of

Ammonia
12. I . Reactions of Ammonia
By addition of a proton ammonia forms the ammonium ion which is similar to the
alkali metal ions with respect to its alkaline and salt-forming properties.
The free radical NH, has been isolated only in the form of its amalgam (DAw, 1811)
which precipitates the more noble metals, such as copper, cadmium, and zinc, from
their solutions. Solutions of ammonium in liquid ammonia are blue and usually exhibit
properties similar to liquid ammonia solutions of sodium and potassium.
Aqueous solutions of ammonia react as weak bases because hydroxyl ions result
from the addition of a proton or H,O+ from the water to the ammonia molecule.
However, the equilibrium is very strongly shifted to the side of free ammonia, as may
be seen from the equilibrium constant at 18 "C:

A 1 N solution of ammonium hydroxide has a pH of 11.77 at 18 "C.

Ammonium salts result from reaction with acids in aqueous solution or in the gas
phase.
Ammonia is oxidized by oxygen or air, depending on the reaction conditions, to NO,
NO,, or N,O or to nitrogen and water. On alkaline surfaces, such as quicklime or soda
lime, ammonia - air mixtures are oxidized readily at 350 "C to nitrite and further to
nitrate. The reaction rate can be increased by adding traces of nickel and cobalt oxides
to the catalyst surfaces 114131. Gaseous ammonia reacts very violently or even explo-
sively with nitrogen oxides to form nitrogen, water, ammonium nitrate or nitrite. The
reaction with N,O requires ignition. The controlled catalytic oxidation of ammonia to
produce nitric acid or pure NO for hydroxylamine production is described in
[14191- [14211.
At higher temperatures, especially in the presence of surface-active materials, am-
monia forms hydrogen qunide with carbon monoxide, methane, or charcoal. The
catalytic oxidation of methane in the presence of ammonia is employed for the
industrial production of hydrogen cyanide. With CO,, SO,, and P,O,, NH, forms
amides of carbonic acid (e.g., Urea [14221), sulfuric acid 114231, and phosphoric acid
[ 14241.
Metals may replace one or all of the hydrogen atoms of ammonia. Sodium amide
(NaNH,), for example, is obtained with evolution of hydrogen by passing ammonia
vapor over metallic sodium. Sodium amide reacts with N,O to form the highly
explosive sodium azide. An ammonium azide, NH,N,, may be prepared also. The
imide, for example, lithium imide, Li,NH, results from replacing a further hydrogen

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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

leads in water to precipitation of silver chloride, and in ammonia, to precipitation of

barium chloride. In liquid ammonia, ammonium salts have an “acid” character. For
example, alkali and alkaline-earth metals, cerium, lanthanum, manganese, cobalt,
nickel, and iron and its alloys are soluble in solutions of ammonium bromide, iodide,
cyanide, and thiocyanide, with formation of the corresponding metal amine salt and
evolution of hydrogen:
2 NH: + Mg + Mg’+ + 2 NH, + H, (98)
Correspondingly, metal amides in liquid ammonia have a “basic” character. The
reaction of ammonium salt with metal amide in liquid ammonia is analogous to the
neutralization of acid and base in water. The heats of neutralization in ammonia are
even larger than in water. The process of hydrolysis corresponds to ammonolysis in
ammonia. This results in ammonobasic compounds, for example, in the infusible
precipitate HgNH,Cl from HgCI,.
Liquid ammonia is a good solvent for white phosphorus. Rhombic sulfur is dissolved
by liquid ammonia at -11.5 “C. Once dissolved, at lower temperature a blue solution
results in which partial ammonolysis of sulfur to sulfur nitride and ammonium sulfides
or polysulfides takes place.
Liquid ammonia’s ability to dissolve alkali and alkaline-earth metals has been well
known for a long time. In concentrated solutions, the metals largely remain in the
metallic state. The magnetic properties and the electrical conductivity, which is com-
parable to that of mercury, confirm this. In the more dilute blue solutions, the metals
are completely dissociated to positive metal ions and solvated electrons [14151. The
ammoniacal solutions allow preparation of many compounds otherwise unobtainable

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

acetylene, NaC-CH; and with phosphine, KPH,. Reactions of ammoniacal metal

3
solutions with halogen-containing organic compounds can be used for the synthesis
of higher hydrocarbons, amines, and free radicals. For example, reacting triphenyl-
chloromethane with dissolved sodium produces the triphenylmethyl radical Ph C..
Generally liquid ammonia is a good solvent for many salts, such as nitrates, nitrites,
iodides, cyanides, thiocyanides, and acetates. Ammonium salts are especially soluble.
The hydroxides, fluorides, and salts with di- and trivalent anions, such as oxides and
sulfides, in general are insoluble. Apart from alkali metals, some other metals and
nonmetals are also soluble. A compilation of the solubilities of organic compounds in
liquid ammonia shows notable solubility of saccharoses [ 14171.
Because of its dipole moment, the ammonia molecule interacts with these ions to
form solvates in a manner analogous to the water molecule in aqueous solutions.
Solutions in liquid ammonia show significant electrical conductance. Pure ammonia.
like water, itself has a conductivity that, although limited, is based on dissociation
according to:

2NH, + NH; NH; (99)

Liquid ammonia in combination with water as antisolvent and methylamine as
prosolvnet is also an excellent extraction medium for all types of petroleum fractions
[1418].
A survey of organic reactions in liquid ammonia appears in [1494].

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.

"2 Another application is the manufacture of explosives, hydrazine, amines, amides,

nitriles and other organic nitrogen compounds, which serve as intermediates for dyes
and pharmaceuticals.
Major inorganic products are nitric acid, sodium nitrate, sodium qanide, ammonium
chloride, and am~noniumbicarbonate. Urea production consumed about 40 % of the
ammonia produced in 1995.
In the environmental sector ammonia is used in various processes for removing SO,
from flue gases of fossil-fuel power plants. The resulting ammonium sulfate is sold as
fertilizer. In the selective cataIytic reduction process (SCR) the NO, in flue gases is reduced
in a catalytic reaction of the nitrogen oxides with a stoichiometric amount of ammonia
[14271- [1430]. Also noncatalytic reduction is applied with ammonia or urea solutions.
Ammonia is also applied as a solvent in certain processes. Another application is the
nitriding ofsteel. An old an still flourishing business is the use of ammonia as re3igerant,
based on its low boiling point and its high heat of evaporation. For some time heavy
competition came from chlorofluorocarbons (CFCs), but with increasing environmental
concern regarding the application of CFCs ammonia's position is strenghening again.
Ammonia is applied in a large number of industrial and commercial refrigeration units
and air-conditioning installations [14311- [1434]. In addition to the high specific
refrigeration effect, the ammonia has the following advantages: it is noncorrosive; it
tolerates moisture, dirt, and oil contaminants; it is cheap and there are many suppliers.
A drawback is its toxicity.
The production of smaller volumes of hydrogednitrogen mixtures used as protective
gases for chemical products 114351 and for metal-working processes [14361 by decom-
position ~ ammoniu over iron- or nickel-based catalysts at 800- 900 "C may be an
economic alternative where production or purchase of pure hydrogen is too expensive
[ 14371, [1443]. Energy-related applications of ammonia are proposed in [1429].

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