Ammonia
From Wikipedia, the free encyclopedia
| Ammonia | |||
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| Identifiers | |||
| CAS number | 7664-41-7  |
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| PubChem | 222 |
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| ChemSpider | 217 |
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| UNII | 5138Q19F1X |
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| EC number | 231-635-3 | ||
| UN number | 1005 | ||
| KEGG | D02916 |
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| MeSH | Ammonia | ||
| ChEBI | CHEBI:16134 |
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| ChEMBL | CHEMBL1160819 |
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| RTECS number | BO0875000 | ||
| Beilstein Reference | 3587154 | ||
| Gmelin Reference | 79 | ||
| 3DMet | B00004 | ||
| Jmol-3D images | Image 1 | ||
| Properties | |||
| Molecular formula | NH3 | ||
| Molar mass | 17.031 g/mol | ||
| Appearance | Colourless gas | ||
| Odor | strong pungent odor | ||
| Density | 0.86 kg/m3 (1.013 bar at boiling point) 0.769 kg/m3 (STP)[1] 0.73 kg/m3 (1.013 bar at 15 °C) 681.9 kg/m3 at −33.3 °C (liquid)[2] 817 kg/m3 at −80 °C (transparent solid)[3] |
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| Melting point | −77.73 °C (−107.91 °F; 195.42 K) | ||
| Boiling point | −33.34 °C (−28.01 °F; 239.81 K) | ||
| Solubility in water | 47% w/w (0 °C) 31% w/w (25 °C) 18% w/w (50 °C)[4] |
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| Solubility | soluble in chloroform, ether, ethanol, methanol | ||
| Vapor pressure | 8573 h Pa | ||
| Acidity (pKa) | 32.5 (−33 °C),[5] 10.5 (DMSO) | ||
| Basicity (pKb) | 4.75 | ||
| Refractive index (nD) | 1.3327 | ||
| Viscosity | 0.276 cP (-40 °C) | ||
| Structure | |||
| Point group | C3v | ||
| Molecular shape | Trigonal pyramid | ||
| Dipole moment | 1.42 D | ||
| Thermochemistry | |||
| Std molar entropy S |
193 J·mol−1·K−1[6] | ||
| Std enthalpy of formation ΔfH |
−46 kJ·mol−1[6] | ||
| Hazards | |||
| MSDS | External MSDS | ||
| GHS pictograms |     [7] |
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| GHS hazard statements | H221, H280, H314, H331, H400[7] | ||
| GHS precautionary statements | P210, P261, P273, P280, P305+351+338, P310[7] | ||
| EU Index | 007-001-00-5 (anhydrous) 007-001-01-2 (solutions) |
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| EU classification |  T  C  N |
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| R-phrases | R10, R23, R34, R50 | ||
| S-phrases | (S1/2), S9, S16, S26, S36/37/39, S45, S61 | ||
| NFPA 704 | |||
| Flash point | flammable gas (see text) | ||
| Explosive limits | 15–28% | ||
| U.S. Permissible exposure limit (PEL) |
50 ppm (25 ppm ACGIH- TLV; 35 ppm STEL) | ||
| LD50 | 0.015 mL/kg (human, oral) | ||
| Related compounds | |||
| Other cations | Phosphine Arsine Stibine |
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| Related nitrogen hydrides | Hydrazine Hydrazoic acid |
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| Related compounds | Ammonium hydroxide | ||
| Structure and properties |
n, εr, etc. | ||
| Thermodynamic data |
Phase behaviour Solid, liquid, gas |
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| Spectral data | UV, IR, NMR, MS | ||
| Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa) | |||
NH3 boils at −33.34 °C (−28.012 °F) at a pressure of one atmosphere, so the liquid must be stored under pressure or at low temperature. Household ammonia or ammonium hydroxide is a solution of NH3 in water. The concentration of such solutions is measured in units of the Baumé scale (density), with 26 degrees baumé (about 30% (by weight) ammonia at 15.5 °C or 59.9 °F) being the typical high-concentration commercial product.[10]
Natural occurrence
Ammonia is found in trace quantities in the atmosphere, being produced from the putrefaction (decay process) of nitrogenous animal and vegetable matter. Ammonia and ammonium salts are also found in small quantities in rainwater, whereas ammonium chloride (sal-ammoniac), and ammonium sulfate are found in volcanic districts; crystals of ammonium bicarbonate have been found in Patagonian guano. The kidneys secrete NH3 to neutralize excess acid.[11] Ammonium salts are found distributed through fertile soil and in seawater. Ammonia is also found throughout the Solar System on Pluto, Mars, Jupiter, Saturn, Uranus, and Neptune. Substances containing ammonia, or those that are similar to it, are called ammoniacal.Properties
Ammonia is a colourless gas with a characteristic pungent smell. It is lighter than air, its density being 0.589 times that of air. It is easily liquefied due to the strong hydrogen bonding between molecules; the liquid boils at −33.3 °C (−27.94 °F), and freezes at −77.7 °C (−107.86 °F) to white crystals.[12]Ammonia may be conveniently deodorized by reacting it with either sodium bicarbonate or acetic acid. Both of these reactions form an odorless ammonium salt.
- Solid
- The crystal symmetry is cubic, Pearson symbol cP16, space group P213 No.198, lattice constant 0.5125 nm.[13]
- Liquid
- Liquid ammonia possesses strong ionising powers reflecting its high ε of 22. Liquid ammonia has a very high standard enthalpy change of vaporization (23.35 kJ/mol, cf. water 40.65 kJ/mol, methane 8.19 kJ/mol, phosphine 14.6 kJ/mol) and can therefore be used in laboratories in uninsulated vessels without additional refrigeration. See liquid ammonia as a solvent.
- Solvent properties
- Ammonia is miscible with water. In an aqueous solution, it can 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/cm3 and is often known as '.880 ammonia'. Ammonia does not burn readily or sustain combustion, except under narrow fuel-to-air mixtures of 15–25% air.
- Combustion
- When mixed with oxygen, 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. Ignition occurs when chlorine is passed into ammonia, forming nitrogen and hydrogen chloride; if chlorine is present in excess, then the highly explosive nitrogen trichloride (NCl3) is also formed.
Structure
The ammonia molecule has a trigonal pyramidal shape as predicted by the valence shell electron pair repulsion theory (VSEPR theory) with an experimentally determined bond angle of 106.7°.[14] The central nitrogen atom has five outer electrons with an additional electron from each hydrogen atom.This gives a total of eight electrons, or four electron pairs that are arranged tetrahedrally. Three of these electron pairs are used as bond pairs, which leaves one lone pair of electrons. The lone pair of electrons repel more strongly than bond pairs, therefore the bond angle is not 109.5°, as expected for a regular tetrahedral arrangement, but is measured at 106.7°.[14] The nitrogen atom in the molecule has a lone electron pair, which makes ammonia a base, a proton acceptor. This shape gives the molecule a dipole moment and makes it polar. The molecule's polarity and, especially, its ability to form hydrogen bonds, makes ammonia highly miscible with water. Ammonia is moderately basic, a 1.0 M aqueous solution has a pH of 11.6 and if a strong acid is added to such a solution until the solution is neutral (pH = 7), 99.4% of the ammonia molecules are protonated. Temperature and salinity also affect the proportion of NH4+. The latter has the shape of a regular tetrahedron and is isoelectronic with methane.
The ammonia molecule readily undergoes nitrogen inversion at room temperature; 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, 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 observed.[15]
Amphotericity
One of the most characteristic properties of ammonia is its basicity. Ammonia is considered to be a weak base. It combines with acids to form salts; thus with hydrochloric acid it forms ammonium chloride (sal-ammoniac); with nitric acid, ammonium nitrate, etc. However, perfectly dry ammonia will not combine with perfectly dry hydrogen chloride; moisture is necessary to bring about the reaction.[16] As a demonstration experiment, opened bottles of concentrated ammonia and hydrochloric acid produce clouds of ammonium chloride, which seem to appear "out of nothing" as the salt forms where the two diffusing clouds of molecules meet, somewhere between the two bottles.- NH3 + HCl → NH4Cl
Although ammonia is well known as a weak base, it can also act as an extremely weak acid. It is a protic substance and is capable of formation of amides (which contain the NH2− ion). For example, lithium dissolves in liquid ammonia to give a solution of lithium amide:
- Li + NH3 → LiNH2 + ½ H2
Self-dissociation
Like water, ammonia undergoes molecular autoionisation to form its acid and base conjugates:- 2 NH
3 (aq)NH+
4 (aq) + NH−
2 (aq)
4][NH−
2] = 10−30
Combustion
The combustion of ammonia to nitrogen and water is exothermic:- 4 NH3 + 3 O2 → 2 N2 + 6 H2O (g) (ΔH°r = −1267.20 kJ/mol)
- 4 NH3 + 5 O2 → 4 NO + 6 H2O
- 2 NO + O2 → 2 NO2
Formation of other compounds
In organic chemistry, ammonia can act as a nucleophile in substitution reactions. Amines can be formed by the reaction of ammonia with alkyl halides, although the resulting -NH2 group is also nucleophilic and secondary and tertiary amines are often formed as byproducts. An excess of ammonia helps minimise multiple substitution, and neutralises the hydrogen halide formed.Methylamine is prepared commercially by the reaction of ammonia with chloromethane, and the reaction of ammonia with 2-bromopropanoic acid has been used to prepare racemic alanine in 70% yield. Ethanolamine is prepared by a ring-opening reaction with ethylene oxide: the reaction is sometimes allowed to go further to produce diethanolamine and triethanolamine.
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 twofold 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".
Pentavalent ammonia is known as λ5-amine, or more commonly, ammonium hydride. This crystalline solid is only stable under high pressure, and decomposes back into trivalent ammonia and hydrogen gas at normal conditions. This substance was once investigated as a possible solid rocket fuel in 1966.[18]
Ammonia as a ligand
Ball-and-stick model of the tetraamminediaquacopper(II) cation, [Cu(NH3)4(H2O)2]2+
Ammonia can act as a ligand in transition metal complexes. It is a pure σ-donor, in the middle of the spectrochemical series, and shows intermediate hard-soft behaviour. For historical reasons, ammonia is named ammine in the nomenclature of coordination compounds. Some notable ammine complexes include tetraamminediaquacopper(II) ([Cu(NH3)4(H2O)2]2+), a dark blue complex formed by adding ammonia to solution of copper(II) salts. It is known as Schweizer's reagent. Diamminesilver(I) ([Ag(NH3)2]+) is the active species in Tollens' reagent. Formation of this complex can also help to distinguish between precipitates of the different silver halides: silver chloride (AgCl) is soluble in dilute (2M) ammonia solution, silver bromide (AgBr) is only soluble in concentrated ammonia solution, whereas silver iodide (AgI) is insoluble in aqueous ammonia.
Ammine complexes of chromium(III) were known in the late 19th century, and formed the basis of Alfred Werner's revolutionary theory on the structure of coordination compounds. Werner noted only two isomers (fac- and mer-) of the complex [CrCl3(NH3)3] could be formed, and concluded the ligands must be arranged around the metal ion at the vertices of an octahedron. This proposal 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.
- Hg2Cl2 + 2 NH3 → Hg + HgCl(NH2) + NH4+ + Cl−
Detection and determination
Ammonia in solution
Ammonia and ammonium salts can be readily detected, in very minute traces, by the addition of Nessler's solution, which gives a distinct yellow colouration in the presence of the least trace of ammonia or ammonium salts. The amount of ammonia in ammonium salts can be estimated quantitatively by distillation of the salts with sodium or potassium hydroxide, the ammonia evolved being absorbed in a known volume of standard sulfuric acid and the excess of acid then determined volumetrically; or the ammonia may be absorbed in hydrochloric acid and the ammonium chloride so formed precipitated as ammonium hexachloroplatinate, (NH4)2PtCl6.Gaseous Ammonia
Sulfur sticks are burnt to detect small leaks in industrial ammonia refrigeration systems. Larger quantities can be detected by warming the salts with a caustic alkali or with quicklime, when the characteristic smell of ammonia will be at once apparent. Ammonia is an irritant and irritation increases with concentration; the Permissible Exposure Limit is 25ppm, and lethal above 500ppm.[19] Higher concentrations are hardly detected by conventional detectors, the type of detector is chosen according to the sensitivity required (e.g. semiconductor, catalytic, electrochemical). Holographic sensors have been proposed for detecting concentrations up to 12.5% in volume.[20]Ammoniacal nitrogen (NH3-N)
Ammoniacal nitrogen (NH3-N) is a measure commonly used for testing the quantity of ammonium ions, derived naturally from ammonia, and returned to ammonia via organic processes, in water or waste liquids. It is a measure used mainly for quantifying values in waste treatment and water purification systems, as well as a measure of the health of natural and man made water reserves. It is measured in units of mg/L (milligram per liter).History
This high-pressure reactor was built in 1921 by BASF in Ludwigshafen and was re-erected on the premises of the University of Karlsruhe in Germany.
The Romans called the ammonium chloride deposits they collected from near the Temple of Amun (Greek Ἄμμων Ammon) in ancient Libya sal ammoniacus (salt of Amun) because of proximity to the nearby temple.[21] Salts of ammonia have been known from very early times; thus the term Hammoniacus sal appears in the writings of Pliny,[22] although it is not known whether the term is identical with the more modern sal-ammoniac (ammonium chloride).[23]
In the form of sal-ammoniac (نشادر, nushadir) ammonia was important to the Muslim alchemists as early as the 8th century, first mentioned by the Persian chemist Jābir ibn Hayyān,[24] and to the European alchemists since the 13th century, being mentioned by Albertus Magnus.[12] 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 hooves and horns of oxen and neutralizing the resulting carbonate with hydrochloric acid, the name "spirit of hartshorn" was applied to ammonia.[12][25]
Gaseous ammonia was first isolated by Joseph Priestley in 1774 and was termed by him "alkaline air".[26] Eleven years later in 1785, Claude Louis Berthollet ascertained its composition.[12]
The Haber–Bosch process to produce ammonia from the nitrogen 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 in Germany during World War I,[9] following the allied blockade that cut off the supply of nitrates from Chile. The ammonia was used to produce explosives to sustain war efforts.[27]
Prior to the availability of cheap natural gas, hydrogen as a precursor to ammonia production was produced via the electrolysis of water or using the chloralkali process.
Uses
Fertilizer
Approximately 83% (as of 2004) of ammonia is used as fertilizers either as its salts, solutions or anhydrously. When applied to soil, it helps provide increased yields of crops such as maize and wheat.[citation needed] 30% of agricultural nitrogen applied in the USA is in the form of anhydrous ammonia and worldwide 110 million tonnes are applied each year.[28]Precursor to nitrogenous compounds
Ammonia is directly or indirectly the precursor to most nitrogen-containing compounds. Virtually all synthetic nitrogen compounds are derived from ammonia. An important derivative is nitric acid. This key material is generated via the Ostwald process by oxidation of ammonia with air over a platinum catalyst at 700–850 °C (1,292–1,562 °F), ~9 atm. Nitric oxide is an intermediate in this conversion:[29]- NH3 + 2 O2 → HNO3 + H2O
Ammonia is also used to make the following compounds:
- Hydrazine, in the Olin Raschig process, the Ketazine process, and the peroxide process
- Hydrogen cyanide, in the BMA process and the Pechiney–Ugine–Kuhlmann process
- Hydroxylamine and ammonium carbonate, in the Raschig process
- Phenol, in the Raschig–Hooker process
- Urea, in the Bosch–Meiser urea process and in Wöhler synthesis
- Amino acids, using Strecker amino-acid synthesis
- Acrylonitrile, in the Sohio process
Examples of such compounds include: ammonium perchlorate, ammonium nitrate, formamide, dinitrogen tetroxide, alprazolam, ethanolamine, ethyl carbamate, hexamethylenetetramine, and ammonium bicarbonate.
Cleaner
Household ammonia is a solution of NH3 in water (i.e., ammonium hydroxide) used as a general purpose cleaner for many surfaces. Because ammonia results in a relatively streak-free shine, one of its most common uses is to clean glass, porcelain and stainless steel. It is also frequently used for cleaning ovens and soaking items to loosen baked-on grime. Household ammonia ranges in concentration by weight from 5 to 10% ammonia.Fermentation
Solutions of ammonia ranging from 16% to 25% are used in the fermentation industry as a source of nitrogen for microorganisms and to adjust pH during fermentation.Antimicrobial agent for food products
As early as in 1895, it was known that ammonia was "strongly antiseptic ... it requires 1.4 grams per litre to preserve beef tea."[30] In one study, anhydrous ammonia destroyed 99.999% of zoonotic bacteria in 3 types of animal feed, but not silage.[31][non-primary source needed] Anhydrous ammonia is currently used commercially to reduce or eliminate microbial contamination of beef.[32][33] Pink slime (or lean finely textured beef in the beef industry) is made from fatty beef trimmings (about 50–70% fat) by removing the fat using heat and centrifugation, then treating it with ammonia to kill E. coli. The process was deemed effective and safe by the US Department of Agriculture based on a study (funded by a producer of pink slime) that found that the treatment reduces E. coli to undetectable levels.[34] There have been safety concerns about the process as well as consumer complaints about the taste and smell of beef treated at optimal levels of ammonia.[35] However, the level of ammonia in any final product has not come close to toxic levels to humans.Minor and emerging uses
Refrigeration – R717
Because of ammonia's vaporization properties, it is a useful refrigerant.[9] It was commonly used prior to the popularisation of chlorofluorocarbons (Freons). Anhydrous ammonia is widely used in industrial refrigeration applications and hockey rinks because of its high energy efficiency and low cost. However, it suffers from the disadvantage of toxicity, which restricts its domestic and small-scale use. Along with its use in modern vapor-compression refrigeration it was used in a mixture along with hydrogen and water in absorption refrigerators. The Kalina cycle, which is of growing importance to geothermal power plants, depends on the wide boiling range of the ammonia-water mixture.For remediation of gaseous emissions
Ammonia is used to scrub SO2 from the burning of fossil fuels, and the resulting product is converted to ammonium sulfate for use as fertilizer. Ammonia neutralizes the nitrogen oxides (NOx) pollutants emitted by diesel engines. This technology, called SCR (selective catalytic reduction), relies on a vanadia-based catalyst.[36]Ammonia may be used to mitigate gaseous spills of phosgene.[37]
As a fuel
Ammoniacal Gas Engine Streetcar in New Orleans drawn by Alfred Waud in 1871.
Ammonia was used during World War II to power buses in Belgium, and in engine and solar energy applications prior to 1900. Liquid ammonia also fuelled the Reaction Motors XLR99 rocket engine that powered the X-15 hypersonic research aircraft. Although not as powerful as other fuels, it left no soot in the reusable rocket engine and its density approximately matches the density of the oxidizer, liquid oxygen, which simplified the aircraft's design.
Ammonia has been proposed as a practical alternative to fossil fuel for internal combustion engines.[38] The calorific value of ammonia is 22.5 MJ/kg (9690 BTU/lb), which is about half that of diesel. In a normal engine, in which the water vapour is not condensed, the calorific value of ammonia will be about 21% less than this figure.
Ammonia cannot be easily or efficiently used in existing Otto cycle engines because of its very low octane rating, although with only minor modifications to carburettors/injectors and a drastic reduction in compression ratio, which would require new pistons, a gasoline engine could be made to work exclusively with ammonia, at a low fraction of its power output before conversion and much higher fuel consumption.[citation needed]
An automobile fuel tank could store Ammonia as a liquid as long as the tank was pressurized appropriately, depending on the temperature. Ammonia's thermodynamic properties are such that at -30 C, the tank pressure would only have to be 27.5 psi, about the same as a car tire. At +30 C, about 125 degrees Fahrenheit, the pressure in the tank would need to be 170 psi to keep the ammonia liquid. If tank pressure was released, the liquid ammonia would turn gaseous and raise the pressure again to that level. Common pneumatic tool air compressors operate at this pressure, so fuel tank pressure is not a barrier to adoption of automobile fuel usage.
However, there are other barriers to widespread automobile usage. In terms of raw ammonia supplies, plants would have to be built to increase production levels, requiring significant capital and energy sources. Although it is the second most produced chemical, the scale of ammonia production is a small fraction of world petroleum usage. It could be manufactured from renewable energy sources, as well as coal or nuclear power. The 60 MW Rjukan dam in Telemark, Norway produced ammonia via electrolysis of water for many years from 1913 producing fertilizer for much of Europe. If produced from coal, the CO2 could be sequestered, but Carbon capture and storage from coal power plants is not yet beyond prototype stages.
In 1981, a Canadian company converted a 1981 Chevrolet Impala to operate using ammonia as fuel.[39][40]
In 2007, a University of Michigan pickup powered by ammonia drove from Detroit to San Francisco as part of a demonstration, requiring only one fill-up in Wyoming.[41]
Ammonia engines or ammonia motors, using ammonia as a working fluid, have been proposed and occasionally used.[42] The principle is similar to that used in a fireless locomotive, but with ammonia as the working fluid, instead of steam or compressed air. Ammonia engines were used experimentally in the 19th century by Goldsworthy Gurney in the UK and in streetcars in New Orleans.
As a stimulant
Anti-meth sign on tank of anhydrous ammonia, Otley, Iowa.
Anhydrous ammonia is a common farm fertilizer that is also a critical
ingredient in making methamphetamine. In 2005, Iowa state used grant
money to give out thousands of locks to prevent criminals from getting
into the tanks.[43]
Ammonia, as the vapor released by smelling salts, has found significant use as a respiratory stimulant. Ammonia is commonly used in the illegal manufacture of methamphetamine through a Birch reduction.[44] The Birch method of making methamphetamine is dangerous because the alkali metal and liquid ammonia are both extremely reactive, and the temperature of liquid ammonia makes it susceptible to explosive boiling when reactants are added.[citation needed]
Textile
Liquid ammonia is used for treatment of cotton materials, giving properties like mercerisation, using alkalis. In particular, it is used for prewashing of wool.[45]Lifting gas
At standard temperature and pressure, ammonia is less dense than atmosphere, and has approximately 60% of the lifting power of hydrogen or helium. Ammonia has sometimes been used to fill weather balloons as a lifting gas. Because of its relatively high boiling point (compared to helium and hydrogen), ammonia could potentially be refrigerated and liquefied aboard an airship to reduce lift and add ballast (and returned to a gas to add lift and reduce ballast).Woodworking
Ammonia has been used to darken quartersawn white oak in Arts & Crafts and Mission-style furniture. Ammonia fumes react with the natural tannins in the wood and cause it to change colours.[46]Safety precautions
The world's longest ammonia pipeline, running from the TogliattiAzot plant in Russia to Odessa in Ukraine.
The U. S. Occupational Safety and Health Administration (OSHA) has set a 15-minute exposure limit for gaseous ammonia of 35 ppm by volume in the environmental air and an 8-hour exposure limit of 25 ppm by volume.[47] NIOSH recently reduced the IDLH from 500 to 300 based on recent more conservative interpretations of original research in 1943. IDLH (Immediately Dangerous to Life and Health) is the level to which a healthy worker can be exposed for 30 minutes without suffering irreversible health effects. Other organizations have varying exposure levels. U.S. Navy Standards [U.S. Bureau of Ships 1962] maximum allowable concentrations (MACs):continuous exposure (60 days): 25 ppm / 1 hour: 400 ppm[48] Ammonia vapour has a sharp, irritating, pungent odour that acts as a warning of potentially dangerous exposure. The average odour threshold is 5 ppm, well below any danger or damage. Exposure to very high concentrations of gaseous ammonia can result in lung damage and death.[47] Although ammonia is regulated in the United States as a non-flammable gas, it still meets the definition of a material that is toxic by inhalation and requires a hazardous safety permit when transported in quantities greater than 13,248 L (3,500 gallons).[49]
Toxicity
The toxicity of ammonia solutions does not usually cause problems for humans and other mammals, as a specific mechanism exists to prevent its build-up in the bloodstream. Ammonia is converted to carbamoyl phosphate by the enzyme carbamoyl phosphate synthetase, and then enters the urea cycle to be either incorporated into amino acids or excreted in the urine[citation needed]. However, fish and amphibians lack this mechanism, as they can usually eliminate ammonia from their bodies by direct excretion. Ammonia even at dilute concentrations is highly toxic to aquatic animals, and for this reason it is classified as dangerous for the environment.Storage information
Similar to propane, anhydrous ammonia boils below room temperature when at atmospheric pressure. A storage vessel capable of 250 psi (1.7 MPa) is suitable to contain the liquid.[50] Ammonium compounds should never be allowed to come in contact with bases (unless in an intended and contained reaction), as dangerous quantities of ammonia gas could be released.Household use
Solutions of ammonia (5–10% by weight) are used as household cleaners, particularly for glass. These solutions are irritating to the eyes and mucous membranes (respiratory and digestive tracts), and to a lesser extent the skin. Caution should be used that the chemical is never mixed into any liquid containing bleach, as a poisonous gas may result. Mixing with chlorine-containing products or strong oxidants, such as household bleach, can lead to hazardous compounds such as chloramines.[51]Laboratory use of ammonia solutions
Hydrochloric acid sample releasing HCl fumes, which are reacting with
ammonia fumes to produce a white smoke of ammonium chloride.
The hazards of ammonia solutions depend on the concentration: "dilute" ammonia solutions are usually 5–10% by weight (<5 .62="" are="" at="" concentrated="" mol="" nbsp="" prepared="" solutions="" usually="">25% by weight. A 25% (by weight) solution has a density of 0.907 g/cm3, and a solution that has a lower density will be more concentrated. The European Union classification of ammonia solutions is given in the table.
| Concentration by weight (w/w) |
Molarity | Concentration mass/volume (w/v) |
Classification | R-Phrases |
|---|---|---|---|---|
| 5–10% | 2.87–5.62 mol/L | 48.9–95.7 g/L | Irritant (Xi) | R36/37/38 |
| 10–25% | 5.62–13.29 mol/L | 95.7–226.3 g/L | Corrosive (C) | R34 |
| >25% | >13.29 mol/L | >226.3 g/L | Corrosive (C) Dangerous for the environment (N) |
R34, R50 |
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 inorganic analysis, and should be lightly acidified but not concentrated (<6 before="" completed.="" disposal="" is="" once="" p="" test="" the="" v="" w="">
Laboratory use of anhydrous ammonia (gas or liquid)
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 50 ppm, but desensitised 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. Nitrogen triiodide, a primary high explosive, is formed when ammonia comes in contact with iodine. Ammonia causes the explosive polymerisation of ethylene oxide. It also forms explosive fulminating 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.
Synthesis and production
Production trend of ammonia between 1947 and 2007
Because of its many uses, ammonia is one of the most highly produced inorganic chemicals. Dozens of chemical plants worldwide produce ammonia. Consuming more than 1% of all man-made power, ammonia production is a significant component of the world energy budget.[9] Market research reports total ammonia production in 2012 is 198 million tonnes and is predicted to increase by about 35 million tonnes by 2019.[8] China produced 28.4% of the worldwide production (increasingly from coal as part of urea synthesis)[52] followed by India with 8.6%, Russia with 8.4%, and the United States with 8.2%.[53] About 80% or more of the ammonia produced is used for fertilizing agricultural crops.[53]
Before the start of World War I, most ammonia was obtained by the dry distillation[54] of nitrogenous vegetable and animal waste products, including camel dung, where it was distilled by the reduction of nitrous acid and nitrites with hydrogen; in addition, it was produced by the distillation of coal, and also by the decomposition of ammonium salts by alkaline hydroxides[55] such as quicklime, the salt most generally used being the chloride (sal-ammoniac) thus:
- 2 NH4Cl + 2 CaO → CaCl2 + Ca(OH)2 + 2 NH3
Modern ammonia-producing plants depend on industrial hydrogen production to react with atmospheric nitrogen using a magnetite catalyst or over a promoted Fe catalyst under high pressure (100 standard atmospheres (10,000 kPa)) and temperature (450 °C) to form anhydrous liquid ammonia. This step is known as the ammonia synthesis loop (also referred to as the Haber–Bosch process):[57]
- 3 H2 + N2 → 2 NH3
As a sustainable alternative to the relatively inefficient electrolysis, hydrogen can be generated from organic wastes (such as biomass or food-industry waste), using catalytic reforming. This releases hydrogen from carbonaceous substances at only 10-20% of energy used by electrolysis and may lead to hydrogen being produced from municipal wastes at below zero cost (allowing for the tipping fees and efficient catalytic reforming, such as cold-plasma). Catalytic (thermal) reforming is possible in small, distributed (even mobile) plants, to take advantage of low-value, stranded biomass/biowaste or natural gas deposits. Conversion of such wastes into ammonia solves the problem of hydrogen storage, as hydrogen can be released economically from ammonia on-demand, without the need for high-pressure or cryogenic storage.
It is also easier to store ammonia on board vehicles than to store hydrogen, as ammonia is less flammable than gasoline or LPG.
Liquid ammonia as a solvent
Liquid ammonia is the best-known and most widely studied nonaqueous ionising solvent. Its most conspicuous property is its ability to dissolve alkali metals to form highly coloured, electrically conductive solutions containing solvated electrons. Apart from these remarkable solutions, much of the chemistry in liquid ammonia can be classified by analogy with related reactions in aqueous solutions. Comparison of the physical properties of NH3 with those of water shows NH3 has the lower melting point, boiling point, density, viscosity, dielectric constant and electrical conductivity; this is due at least in part to the weaker hydrogen bonding in NH3 and because such bonding cannot form cross-linked networks, since each NH3 molecule has only one lone-pair of electrons compared with two for each H2O molecule. The ionic self-dissociation constant of liquid NH3 at −50 °C is about 10−33 mol2·l−2.Solubility of salts
| Solubility (g of salt per 100 g liquid NH3) | |
|---|---|
| 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 | 157.0 |
| Sodium bromide | 138.0 |
| Sodium iodide | 161.9 |
| Sodium thiocyanate | 205.5 |
Liquid ammonia is an ionising 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 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 (77 °F).
Solutions of metals
Liquid ammonia will dissolve the alkali metals and other electropositive metals such as magnesium, calcium, strontium, barium, europium and ytterbium. At low concentrations (<0 .06="" a="" and="" are="" blue="" cations="" contain="" deep="" formed:="" href="http://en.wikipedia.org/wiki/Solvated_electron" l="" metal="" mol="" nbsp="" solutions="" these="" title="Solvated electron">solvated electrons, free electrons that are surrounded by a cage of ammonia molecules.
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.
Redox properties of liquid ammonia
| E° (V, ammonia) | E° (V, water) | |
|---|---|---|
| Li+ + e− ⇌ Li | −2.24 | −3.04 |
| K+ + e− ⇌ K | −1.98 | −2.93 |
| Na+ + e− ⇌ Na | −1.85 | −2.71 |
| Zn2+ + 2e− ⇌ Zn | −0.53 | −0.76 |
| NH4+ + e− ⇌ ½ H2 + NH3 | 0.00 | — |
| Cu2+ + 2e− ⇌ Cu | +0.43 | +0.34 |
| Ag+ + e− ⇌ Ag | +0.83 | +0.80 |
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.
Ammonia's role in biological systems and human disease
Main symptoms of hyperammonemia (ammonia reaching toxic concentrations).[58]
Ammonia is an important source of nitrogen for living systems. Although atmospheric nitrogen abounds (more than 75%), few living creatures are capable of using this atmospheric nitrogen in its diatomic form, N2 gas. Therefore, nitrogen fixation is required for the synthesis of amino acids, which are the building blocks of protein. Some plants rely on ammonia and other nitrogenous wastes incorporated into the soil by decaying matter. Others, such as nitrogen-fixing legumes, benefit from symbiotic relationships with rhizobia that create ammonia from atmospheric nitrogen.[59]
Biosynthesis
In certain organisms, ammonia is produced from atmospheric nitrogen by enzymes called nitrogenases. The overall process is called nitrogen fixation. Although it is unlikely that biomimetic methods that are competitive with the Haber process will be developed, intense effort has been directed toward understanding the mechanism of biological nitrogen fixation. The scientific interest in this problem is motivated by the unusual structure of the active site of the enzyme, which consists of an Fe7MoS9 ensemble.Ammonia is also a metabolic product of amino acid deamination catalyzed by enzymes such as glutamate dehydrogenase 1. Ammonia excretion is common in aquatic animals. In humans, it is quickly converted to urea, which is much less toxic, particularly less basic. This urea is a major component of the dry weight of urine. Most reptiles, birds, insects, and snails excrete uric acid solely as nitrogenous waste.
In physiology
Ammonia also plays a role in both normal and abnormal animal physiology. It is biosynthesised through normal amino acid metabolism and is toxic in high concentrations.[60] 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.[61]
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.[62]
Excretion
Ammonium ions are a toxic waste product of the metabolism in animals. In fish and aquatic invertebrates, it is excreted directly into the water. In mammals, sharks, and amphibians, it is converted in the urea cycle to urea, because it is less toxic and can be stored more efficiently. In birds, reptiles, and terrestrial snails, metabolic ammonium is converted into uric acid, which is solid, and can therefore be excreted with minimal water loss.[63]
Reference ranges for blood tests, comparing blood content of ammonia (shown in yellow near middle) with other constituents
In astronomy
Ammonia occurs in the atmospheres of the outer gas planets such as Jupiter (0.026% ammonia) and Saturn (0.012% ammonia).
Ammonia has 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.[64] It is naturally found on Deimos and Phobos – the two moons of Mars.
Interstellar space
Ammonia was first detected in interstellar space in 1968, based on microwave emissions from the direction of the galactic core.[65] This was the first polyatomic molecule to be so detected. The sensitivity of the molecule to a broad range of excitations and the ease with which it can be observed in a number of regions has made ammonia one of the most important molecules for studies of molecular clouds.[66] The relative intensity of the ammonia lines can be used to measure the temperature of the emitting medium.The following isotopic species of ammonia have been detected:
- NH3, 15NH3, NH2D, NHD2, and ND3
Since its interstellar discovery, NH3 has proved to be an invaluable spectroscopic tool in the study of the interstellar medium. With a large number of transitions sensitive to a wide range of excitation conditions, NH3 has been widely astronomically detected – its detection has been reported in hundreds of journal articles. Listed below is a sample of journal articles that highlights the range of detectors that have been used to identify ammonia.
The study of interstellar ammonia has been important to a number of areas of research in the last few decades. Some of these are delineated below and primarily involve using ammonia as an interstellar thermometer.
Interstellar formation mechanisms
Ball-and-stick model of the diamminesilver(I) cation, [Ag(NH3)2]+
The interstellar abundance for ammonia has been measured for a variety of environments. The [NH3]/[H2] ratio has been estimated to range from 10−7 in small dark clouds[68] up to 10−5 in the dense core of the Orion Molecular Cloud Complex.[69] Although a total of 18 total production routes have been proposed,[70] the principal formation mechanism for interstellar NH3 is the reaction:
- NH4+ + e− → NH3 + H·
All other proposed formation reactions have rate constants of between 2 and 13 orders of magnitude smaller, making their contribution to the abundance of ammonia relatively insignificant.[73] As an example of the minor contribution other formation reactions play, the reaction:
- H2 + NH2 → NH3 + H
Some of the other possible formation reactions are:
- H− + NH4+ → NH3 + H2
- PNH3+ + e− → P + NH3
Interstellar destruction mechanisms
There are 113 total proposed reactions leading to the destruction of NH3. Of these, 39 were tabulated in extensive tables of the chemistry among C, N, and O compounds.[74] A review of interstellar ammonia cites the following reactions as the principal dissociation mechanisms:[66]- (1) NH3 + H3+ → NH4+ + H2
- (2) NH3 + HCO+ → NH4+ + CO
This is due to the relatively high abundance of H3+.
Single antenna detections
Radio observations of NH3 from the Effelsberg 100-m Radio Telescope reveal that the ammonia line is separated into two components – a background ridge and an unresolved core. The background corresponds well with the locations previously detected CO.[78] The 25 m Chilbolton telescope in England detected radio signatures of ammonia in H II regions, HNH2O masers, H-H objects, and other objects associated with star formation. A comparison of emission line widths indicates that turbulent or systematic velocities do not increase in the central cores of molecular clouds.[79]Microwave radiation from ammonia was observed in several galactic objects including W3(OH), Orion A, W43, W51, and five sources in the galactic centre. The high detection rate indicates that this is a common molecule in the interstellar medium and that high-density regions are common in the galaxy.[80]
Interferometric studies
VLA observations of NH3 in seven regions with high-velocity gaseous outflows revealed condensations of less than 0.1 pc in L1551, S140, and Cepheus A. Three individual condensations were detected in Cepheus A, one of them with a highly elongated shape. They may play an important role in creating the bipolar outflow in the region.[81]Extragalactic ammonia was imaged using the VLA in IC 342. The hot gas has temperatures above 70 K, which was inferred from ammonia line ratios and appears to be closely associated with the innermost portions of the nuclear bar seen in CO.[82] NH3 was also monitored by VLA toward a sample of four galactic ultracompact HII regions: G9.62+0.19, G10.47+0.03, G29.96−0.02, and G31.41+0.31. Based upon temperature and density diagnostics, it is concluded that in general such clumps are likely to be the sites of massive star formation in an early evolutionary phase prior to the development of an ultracompact HII region.[83]
Infrared detections
Absorption at 2.97 micrometres due to solid ammonia was recorded from interstellar grains in the Becklin-Neugebauer Object and probably in NGC 2264-IR as well. This detection helped explain the physical shape of previously poorly understood and related ice absorption lines.[84]A spectrum of the disk of Jupiter was obtained from the Kuiper Airborne Observatory, covering the 100 to 300 cm−1 spectral range. Analysis of the spectrum provides information on global mean properties of ammonia gas and an ammonia ice haze.[85]
A total of 149 dark cloud positions were surveyed for evidence of 'dense cores' by using the (J,K) = (1,1) rotating inversion line of NH3. In general, the cores are not spherically shaped, with aspect ratios ranging from 1.1 to 4.4. It is also found that cores with stars have broader lines than cores without stars.[86]
Ammonia has been detected in the Draco Nebula and in one or possibly two molecular clouds, which are associated with the high-latitude galactic infrared cirrus. The finding is significant because they may represent the birthplaces for the Population I metallicity B-type stars in the galactic halo that could have been borne in the galactic disk.[87]
