| Ammonia | |
|---|---|
| General | |
| Systematic name | Ammonia Azane (See Text) |
| Other names | Hydrogen nitride Spirit of hartshorn Nitrosil Vaporole |
| Molecular formula | NH3 |
| Molar mass | 17.0304 g/mol |
| Appearance | Colourless gas with strong pungent odor |
| CAS number | |
| Properties | |
| Density and phase | 0.6813 g/L, gas. |
| Solubility in water | 89.9 g/100 ml at 0 °C. |
| Melting point | -77.73 °C (195.42 K) |
| Boiling point | -33.34 °C (239.81 K) |
| Acidity (pKa) | ≈34 |
| Basicity (pKb) | 4.75 |
| Structure | |
| Molecular shape | Terminus |
| Dipole moment | 1.5 D |
| Hazards | |
| MSDS | External MSDS |
| Main hazards | Toxic and corrosive. |
| NFPA 704 | |
| Flash point | 11 °C |
| R/S statement | R: , , , S: , , , , |
| RTECS number | BO0875000 |
| Supplementary data page | |
| Structure and properties | n, εr, etc. |
| Thermodynamic data | Phase behaviour Solid, liquid, gas |
| Spectral data | UV, IR, NMR, MS |
| Related compounds | |
| Other ions | Ammonium (NH4+) |
| Related compounds | Hydrazine Hydrazoic acid Hydroxylamine Chloramine |
| Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) Chemical infobox | |
An ammonia molecule has a trigonal pyramid shape, as predicted by VSEPR theory. This shape gives the molecule an overall dipole moment, and makes it polar so that ammonia readily dissolves in water. The nitrogen atom in the molecule has a lone electron pair, and ammonia acts as a base. That means that, when in aqueous solution, it can take a proton from water to produce a hydroxide anion and an ammonium cation (NH4+), which has the shape of a regular tetrahedron. The degree to which ammonia forms the ammonium ion depends on the pH of the solution—at "physiological" pH (~7), about 99% of the ammonia molecules are protonated.
The main uses of ammonia are in the production of fertilizers, explosives and polymers. It is also an ingredient in certain household glass cleaners. Ammonia is found in small quantities in the atmosphere, being produced from the putrefaction of nitrogenous animal and vegetable matter. Ammonia and ammonium salts are also found in small quantities in rainwater, while ammonium chloride (sal-ammoniac) and ammonium sulfate are found in volcanic districts; crystals of ammonium bicarbonate have been found in Patagonian guano. Ammonium salts also are found distributed through all fertile soil and in seawater. Substances containing ammonia, or that are similar to it, are called ammoniacal.
In the form of sal-ammoniac, ammonia was known to the alchemists as early as the 13th century, being mentioned by Albertus Magnus.Absolouteastronomy.com URL last accessed April 24 2006 It was also used by dyers in the Middle Ages in the form of fermented urine to alter the colour of vegetable dyes. In the 15th century, Basilius Valentinus showed that ammonia could be obtained by the action of alkalis on sal-ammoniac. At a later period, when sal-ammoniac was obtained by distilling the hoofs and horns of oxen and neutralizing the resulting carbonate with hydrochloric acid, the name "spirit of hartshorn" was applied to ammonia.
Gaseous ammonia was first isolated by Joseph Priestley in 1774 and was termed by him alkaline air; however it was acquired by the alchemist Basil Valentine. Eleven years later in 1785, Claude Louis Berthollet ascertained its composition.
The Haber process to produce ammonia from the nitrogen contained in the air was developed by Fritz Haber and Carl Bosch in 1909 and patented in 1910. It was first used on an industrial scale by the Germans during World War I,BBC.co.uk URL last accessed April 24 2006 following the allied blockade that cut off the supply of nitrates from Chile. The ammonia was used to produce explosives to sustain their war effort.
Before the start of World War I most ammonia was obtained by the dry distillationNobel Prize in Chemistry (1918) - Haber process. URL last accessed April 24 2006 of nitrogenous vegetable and animal waste products, including camel dung where it was distilled by the reduction of nitrous acid and nitrites with hydrogen; additionally, it was produced by the distillation of coal; and also by the decomposition of ammonium salts by alkaline hydroxidesBBC.co.uk URL last accessed April 24 2006 or by quicklime, the salt most generally used being the chloride (sal-ammoniac) thus:
Today, the typical modern ammonia-producing plant first converts natural gas (i.e. methane) or liquified petroleum gas (such gases are propane and butane) or petroleum naphtha into gaseous hydrogen. Starting with a natural gas feedstock, the processes used in producing the hydrogen are:
The steam reforming, shift conversion, carbon dioxide removal and methanation steps each operate at absolute pressures of about 25 to 35 bar, and the ammonia synthesis loop operates at absolute pressures ranging from 60 to 180 bar depending upon which proprietary design is used. There are many engineering and construction companies that offer proprietary designs for ammonia synthesis plants. Haldor Topsoe of Denmark, Lurgi AG of Germany, and Kellogg, Brown and Root of the United States are among the most experienced companies in that field.Kellogg Brown's Ammonia Process URL last accessed April 24 2006
Ammonia is also a metabolic product of amino acid deamination. In humans, it is quickly converted to urea, which is much less toxic. This urea is a major component of the dry weight of urine.
It is miscible with water. All the ammonia contained in an aqueous solution of the gas may be expelled by boiling. The aqueous solution of ammonia is basic. The maximum concentration of ammonia in water (a saturated solution) has a density of 0.880 g cm-3 and is often known as '.880 Ammonia'. Ammonia does not sustain combustion, and it does not burn readily unless mixed with oxygen, when it burns with a pale yellowish-green flame. At high temperature and in the presence of a suitable catalyst, ammonia is decomposed into its constituent elements. Chlorine catches fire when passed into ammonia, forming nitrogen and hydrochloric acid; unless the ammonia is present in excess, the highly explosive nitrogen trichloride (NCl3) is also formed.
The ammonia molecule readily undergoes nitrogen inversion at room temperature - that is, the nitrogen atom passes through the plane of symmetry of the three hydrogen atoms; a useful analogy is an umbrella turning itself inside out in a strong wind. The energy barrier to this inversion is 24.7 kJ/mol in ammonia, and the resonance frequency is 23.79 GHz, corresponding to microwave radiation of a wavelength of 1.260 cm. The absorption at this frequency was the first microwave spectrum to be observedC. E. Cleeton & N. H. Williams, 1934 - Online version; archive. URL last accessed May 8, 2006.
The salts produced by the action of ammonia on acids are known as the Ammonium compounds and all contain the ammonium ion (NH4+).
This is a Brønsted-Lowry acid-base reaction in which ammonia is acting as an acid.
Amides can be prepared by the reaction of ammonia with a number of carboxylic acid derivatives. Acyl chlorides are the most reactive, but the ammonia must be present in at least a two-fold excess to neutralise the hydrogen chloride formed. Esters and anhydrides also react with ammonia to form amides. Ammonium salts of carboxylic acids can be dehydrated to amides so long as there are no thermally sensitive groups present: temperatures of 150–200 °C are required.
The hydrogen in ammonia is capable of replacement by metals, thus magnesium burns in the gas with the formation of magnesium nitride Mg3N2, and when the gas is passed over heated sodium or potassium, sodamide, NaNH2, and potassamide, KNH2, are formed. Where necessary in substitutive nomenclature, IUPAC recommendations prefer the name azane to ammonia: hence chloramine would be named chloroazane in substitutive nomenclature, not chloroammonia.
Ammine complexes of chromium(III) were known in the late 19th century, and formed the basis of Alfred Werner's theory of coordination compounds. Werner noted that only two isomers (fac- and mer-) of the complex * could be formed, and concluded that the ligands must be arranged around the metal ion at the vertices of an octahedron. This has since been confirmed by X-ray crystallography.
An ammine ligand bound to a metal ion is markedly more acidic than a free ammonia molecule, although deprotonation in aqueous solution is still rare. One example is the Calomel reaction, where the resulting amidomercury(II) compound is highly insoluble.
The catalyst is essential, as the normal oxidation (or combustion) of ammonia gives dinitrogen and water: the production of nitric oxide is an example of kinetic control. As the gas mixture cools to 200–250 °C, the nitric oxide is in turn oxidized by the excess of oxygen present in the mixture, to give nitrogen dioxide. This is reacted with water to give nitric acid for use in the production of fertilizers and explosives.
In addition to serving as a fertilizer ingredient, ammonia can also be used directly as a fertilizer by forming a solution with irrigation water, without additional chemical processing. This later use allows the continuous growing of nitrogen dependent crops such as maize (corn) without crop rotation but this type of use leads to poor soil health.
Ammonia has thermodynamic properties that make it very well suited as a refrigerant, since it liquefies readily under pressure, and was used in virtually all refrigeration units prior to the advent of haloalkanes such as Freon. However, ammonia is a toxic irritant and its corrosiveness to any copper alloys increases the risk that an undesirable leak may develop and cause a noxious hazard. Its use in small refrigeration units has been largely replaced by haloalkanes, which are not toxic irritants and are practically not flammable. Ammonia continues to be used as a refrigerant in large industrial processes such as bulk icemaking and industrial food processing. Ammonia is also useful as a component in absorption-type refrigerators, which do not use compression and expansion cycles but can exploit heat differences. Since the implication of haloalkane being major contributors to ozone depletion, ammonia is again seeing increasing use as a refrigerant.
It is also sometimes added to drinking water along with chlorine to form chloramine, a disinfectant. Unlike chlorine on its own, chloramine does not combine with organic (carbon containing) materials to form carcinogenic halomethanes such as chloroform.
During the 1960s, Tobacco companies such as Brown & Williamson and Philip Morris began using ammonia in cigarettes. The addition of ammonia serves to enhance the delivery of nicotine into the blood stream. As a result the reinforcement effect of the nicotine was enhanced, increasing its addictive ability without actually increasing the portion of nicotine. Alix M. Freedman, "'Impact Booster': Tobacco Firm Shows How Ammonia Spurs Delivery of Nicotine", The Wall Street Journal, Dec. 28, 1995.
Ammonia also plays a role in both normal and abnormal animal physiology. Ammonia is created through normal amino acid metabolism and is toxic in high concentrations. The liver converts ammonia to urea through a series of reactions known as the urea cycle. Liver dysfunction, such as that seen in cirrhosis, may lead to elevated amounts of ammonia in the blood (hyperammonemia). Likewise, defects in the enzymes responsible for the urea cycle, such as ornithine transcarbamylase, lead to hyperammonemia. Hyperammonemia contributes to the confusion and coma of hepatic encephalopathy as well as the neurologic disease common in people with urea cycle defects and organic acidurias.Zschocke, Johannes, and Georg Hoffman. Vademecum Metabolism. Friedrichsdorf, Germany: Milupa GmbH, 2004.
Ammonia is important for normal animal acid/base balance. After formation of ammonium from glutamine, α-ketoglutarate may be degraded to produce two molecules of bicarbonate which are then available as buffers for dietary acids. Ammonium is excreted in the urine resulting in net acid loss. Ammonia may itself diffuse across the renal tubules, combine with a hydrogen ion, and thus allow for further acid excretion.Rose, Burton, and Helmut Rennke. Renal Pathophysiology. Baltimore, Maryland: Williams & Wilkins, 1994.
| Solubility (g per 100 g) | |
|---|---|
| Ammonium acetate | 253.2 |
| Ammonium nitrate | 389.6 |
| Lithium nitrate | 243.7 |
| Sodium nitrate | 97.6 |
| Potassium nitrate | 10.4 |
| Sodium fluoride | 0.35 |
| Sodium chloride | 3.0 |
| Sodium bromide | 138.0 |
| Sodium iodide | 161.9 |
| Sodium thiocyanate | 205.5 |
Liquid ammonia is an ionizing solvent, although less so than water, and dissolves a range of ionic compounds including many nitrates, nitrites, cyanides and thiocyanates. Most ammonium salts are soluble, and these salts act as acids in liquid ammonia solutions. The solubility of halide salts increases from fluoride to iodide. A saturated solution of ammonium nitrate contains 0.83 mol solute per mole of ammonia, and has a vapour pressure of less than 1 bar even at 25 °C.
These solutions are very useful as strong reducing agents. At higher concentrations, the solutions are metallic in appearance and in electrical conductivity. At low temperatures, the two types of solution can coexist as immiscible phases.
The range of thermodynamic stability of liquid ammonia solutions is very narrow, as the potential for oxidation to dinitrogen, E° (N2 + 6NH4+ + 6e− 8NH3), is only +0.04 V. In practice, both oxidation to dinitrogen and reduction to dihydrogen are slow. This is particularly true of reducing solutions: the solutions of the alkali metals mentioned above are stable for several days, slowly decomposing to the metal amide and dihydrogen. Most studies involving liquid ammonia solutions are done in reducing conditions: although oxidation of liquid ammonia is usually slow, there is still a risk of explosion, particularly if transition metal ions are present as possible catalysts.
The following isotopic species of ammonia have been detected:
The detection of triply-deuterated ammonia was considered a surprise as deuterium is relatively scarce. It is thought that the low-temperature conditions allow this molecule to survive and accumulate.T. J. Millar, "Deuterium Fractionation in Interstellar Clouds", Space Science Reviews, Vol. 106, Issue 1, pp 73-86. The ammonia molecule has also been detected in the atmospheres of the gas giant planets, including Jupiter, along with other gases like methane, hydrogen, and helium. The interior of Saturn may include frozen crystals of ammonia.Edited by Kirk Munsell. Image page credit Lunar and Planetary Institute. NASA. "NASA's Solar Exploration: Multimedia: Gallery: Gas Giant Interiors". URL accessed April 26, 2006.| Concentration by weight | Molarity | Classification | R-Phrases |
|---|---|---|---|
| 5–10% | 2.87–5.62 mol/L | Irritant (Xi) | |
| 10–25% | 5.62–13.29 mol/L | Corrosive (C) | |
| >25% | >13.29 mol/L | Corrosive (C) Dangerous for the environment (N) | , |
The ammonia vapour from concentrated ammonia solutions is severely irritating to the eyes and the respiratory tract, and these solutions should only be handled in a fume hood. Saturated ("0.880") solutions can develop a significant pressure inside a closed bottle in warm weather, and the bottle should be opened with care: this is not usually a problem for 25% ("0.900") solutions.
Ammonia solutions should not be mixed with halogens, as toxic and/or explosive products are formed. Prolonged contact of ammonia solutions with silver, mercury or iodide salts can also lead to explosive products: such mixtures are often formed in qualitative chemical analysis, and should be acidified and diluted before disposal once the test is completed.
Anhydrous ammonia is classified as toxic (T) and dangerous for the environment (N). The gas is flammable (autoignition temperature: 651 °C) and can form explosive mixtures with air (16–25%). The permissible exposure limit (PEL) in the United States is 50 ppm (35 mg/m3), while the IDLH concentration is estimated at 300 ppm. Repeated exposure to ammonia lowers the sensitivity to the smell of the gas: normally the odour is detectable at concentrations of less than 0.5 ppm, but desensitized individuals may not detect it even at concentrations of 100 ppm. Anhydrous ammonia corrodes copper- and zinc-containing alloys, and so brass fittings should not be used for handling the gas. Liquid ammonia can also attack rubber and certain plastics.
Ammonia reacts violently with the halogens, and causes the explosive polymerization of ethylene oxide. It also forms explosive compounds with compounds of gold, silver, mercury, germanium or tellurium, and with stibine. Violent reactions have also been reported with acetaldehyde, hypochlorite solutions, potassium ferricyanide and peroxides.
Hydrogen compounds | Bases | Nitrogen metabolism | Household chemicals | Refrigerants
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