The Ostwald process is a chemical process used for making nitric acid (HNO 3 ). The Ostwald process is a mainstay of the modern chemical industry , and it provides the main raw material for the most common type of fertilizer production. Historically and practically, the Ostwald process is closely associated with the Haber process , which provides the requisite raw material, ammonia (NH 3 ). This method is preferred over other methods of nitric acid production, in that it is less expensive and more efficient.
76-505: Ammonia is converted to nitric acid in 2 stages. The Ostwald process begins with burning ammonia . Ammonia burns in oxygen at temperature about 900 °C (1,650 °F) and pressure up to 8 standard atmospheres (810 kPa) in the presence of a catalyst such as platinum gauze, alloyed with 10% rhodium to increase its strength and nitric oxide yield, platinum metal on fused silica wool, copper or nickel to form nitric oxide (nitrogen(II) oxide) and water (as steam). This reaction
152-513: A base , a proton acceptor. 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 ammonium [NH 4 ] . The latter has the shape of a regular tetrahedron and is isoelectronic with methane . The ammonia molecule readily undergoes nitrogen inversion at room temperature;
228-460: A cyanobiont (cyanobacteria such as Nostoc ) which fix nitrogen for them: Some symbiotic relationships involving agriculturally-important plants are: A method for nitrogen fixation was first described by Henry Cavendish in 1784 using electric arcs reacting nitrogen and oxygen in air. This method was implemented in the Birkeland–Eyde process of 1903. The fixation of nitrogen by lightning
304-399: A nitrogenase enzyme. The overall reaction for BNF is: N 2 + 16ATP + 16H 2 O + 8e + 8H → 2NH 3 +H 2 + 16ADP + 16P i The process is coupled to the hydrolysis of 16 equivalents of ATP and is accompanied by the co-formation of one equivalent of H 2 . The conversion of N 2 into ammonia occurs at a metal cluster called FeMoco , an abbreviation for
380-484: A vapour pressure of less than 1 bar even at 25 °C (77 °F). However, few oxyanion salts with other cations dissolve. Liquid ammonia will dissolve all of the alkali metals and other electropositive metals such as Ca , Sr , Ba , Eu and Yb (also Mg using an electrolytic process ). At low concentrations (<0.06 mol/L), deep blue solutions are formed: these contain metal cations and solvated electrons , free electrons that are surrounded by
456-444: A cage of ammonia molecules. These solutions are 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 ° ( N 2 + 6 [NH 4 ] + 6 e ⇌ 8 NH 3 ),
532-415: A cloud of ammonium chloride , which seems to appear 'out of nothing' as the salt aerosol forms where the two diffusing clouds of reagents meet between the two bottles. The salts produced by the action of ammonia on acids are known as the ammonium salts and all contain the ammonium ion ( [NH 4 ] ). Although ammonia is well known as a weak base, it can also act as an extremely weak acid. It
608-550: A colourless liquid , which boils at −33.1 °C (−27.58 °F), and freezes to colourless crystals at −77.7 °C (−107.86 °F). Little data is available at very high temperatures and pressures, but the liquid-vapor critical point occurs at 405 K and 11.35 MPa. The crystal symmetry is cubic, Pearson symbol cP16, space group P2 1 3 No.198, lattice constant 0.5125 nm . Liquid ammonia possesses strong ionising powers reflecting its high ε of 22 at −35 °C (−31 °F). Liquid ammonia has
684-543: A critical threshold. The specialized heterocyst cell is necessary for the performance of nitrogenase as a result of its sensitivity to ambient oxygen. Nitrogenase consist of two proteins, a catalytic iron-dependent protein, commonly referred to as MoFe protein and a reducing iron-only protein (Fe protein). There are three different iron dependent proteins, molybdenum -dependent, vanadium -dependent, and iron -only, with all three nitrogenase protein variations containing an iron protein component. Molybdenum-dependent nitrogenase
760-406: A far lower temperature than would be possible with water alone. Substances containing ammonia, or those that are similar to it, are called ammoniacal . Ammonia is a colourless gas with a characteristically 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. Gaseous ammonia turns to
836-407: A fuel for thermal power production. The flammable range of ammonia in dry air is 15.15–27.35% and in 100% relative humidity air is 15.95–26.55%. For studying the kinetics of ammonia combustion, knowledge of a detailed reliable reaction mechanism is required, but this has been challenging to obtain. Ammonia is a direct or indirect precursor to most manufactured nitrogen-containing compounds . It
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#1732854738541912-452: A laboratorial setting, gaseous ammonia can be detected by using concentrated hydrochloric acid or gaseous hydrogen chloride. A dense white fume (which is ammonium chloride vapor) arises from the reaction between ammonia and HCl(g). Ammoniacal nitrogen (NH 3 –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
988-447: A low nitrogen content, has been shown to host a diazotrophic community. The bacteria enrich the wood substrate with nitrogen through fixation, thus enabling deadwood decomposition by fungi. Nitrogenases are rapidly degraded by oxygen. For this reason, many bacteria cease production of the enzyme in the presence of oxygen. Many nitrogen-fixing organisms exist only in anaerobic conditions, respiring to draw down oxygen levels, or binding
1064-424: A new era of soil science ." In 1901, Beijerinck showed that Azotobacter chroococcum was able to fix atmospheric nitrogen. This was the first species of the azotobacter genus, so-named by him. It is also the first known diazotroph , species that use diatomic nitrogen as a step in the complete nitrogen cycle . Biological nitrogen fixation (BNF) occurs when atmospheric nitrogen is converted to ammonia by
1140-432: A pale yellowish-green flame. 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 ( NCl 3 ) is also formed. The combustion of ammonia to form nitrogen and water is exothermic : The standard enthalpy change of combustion , Δ H ° c , expressed per mole of ammonia and with condensation of
1216-444: A precursor to fertilisers . Around 70% of ammonia produced industrially is used to make fertilisers in various forms and composition, such as urea and diammonium phosphate . Ammonia in pure form is also applied directly into the soil. Ammonia, either directly or indirectly, is also a building block for the synthesis of many chemicals. Ammonia occurs in nature and has been detected in the interstellar medium. In many countries, it
1292-580: A pressure of one atmosphere , but the liquid can often be handled in the laboratory without external cooling. Household ammonia or ammonium hydroxide is a solution of ammonia in water. Pliny , in Book XXXI of his Natural History , refers to a salt named hammoniacum , so called because of the proximity of its source to the Temple of Jupiter Amun ( Greek Ἄμμων Ammon ) in the Roman province of Cyrenaica . However,
1368-451: A second metal (usually molybdenum , but sometimes vanadium ). Some nitrogen-fixing bacteria have symbiotic relationships with plants , especially legumes , mosses and aquatic ferns such as Azolla . Looser non-symbiotic relationships between diazotrophs and plants are often referred to as associative, as seen in nitrogen fixation on rice roots. Nitrogen fixation occurs between some termites and fungi . It occurs naturally in
1444-559: 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 repels more strongly than bond pairs; therefore, the bond angle is not 109.5°, as expected for a regular tetrahedral arrangement, but 106.8°. 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. The lone pair makes ammonia
1520-438: 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 and was used in the first maser . One of the most characteristic properties of ammonia
1596-465: A very high standard enthalpy change of vapourization (23.5 kJ/mol ; for comparison, water 's is 40.65 kJ/mol, methane 8.19 kJ/mol and phosphine 14.6 kJ/mol) and can be transported in pressurized or refrigerated vessels; however, at standard temperature and pressure liquid anhydrous ammonia will vaporize. Ammonia readily dissolves in water. In an aqueous solution, it can be expelled by boiling. The aqueous solution of ammonia
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#17328547385411672-497: Is basic , and may be described as aqueous ammonia or ammonium hydroxide . The maximum concentration of ammonia in water (a saturated solution ) has a specific gravity of 0.880 and is often known as '.880 ammonia'. Liquid ammonia is a 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
1748-443: Is a chemical process by which molecular dinitrogen ( N 2 ) is converted into ammonia ( NH 3 ). It occurs both biologically and abiologically in chemical industries . Biological nitrogen fixation or diazotrophy is catalyzed by enzymes called nitrogenases . These enzyme complexes are encoded by the Nif genes (or Nif homologs ) and contain iron , often with
1824-811: Is a protic substance and is capable of formation of amides (which contain the NH − 2 ion). For example, lithium dissolves in liquid ammonia to give a blue solution ( solvated electron ) of lithium amide : Like water, liquid ammonia undergoes molecular autoionisation to form its acid and base conjugates : Ammonia often functions as a weak base , so it has some buffering ability. Shifts in pH will cause more or fewer ammonium cations ( NH + 4 ) and amide anions ( NH − 2 ) to be present in solution . At standard pressure and temperature, Ammonia does not burn readily or sustain combustion , except under narrow fuel-to-air mixtures of 15–28% ammonia by volume in air. When mixed with oxygen , it burns with
1900-402: 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 litre ). The ancient Greek historian Herodotus mentioned that there were outcrops of salt in an area of Libya that was inhabited by a people called the 'Ammonians' (now
1976-408: Is a required precursor to fertilizers , explosives , and other products. The Haber process requires high pressures (around 200 atm) and high temperatures (at least 400 °C), which are routine conditions for industrial catalysis. This process uses natural gas as a hydrogen source and air as a nitrogen source. The ammonia product has resulted in an intensification of nitrogen fertilizer globally and
2052-532: Is a very similar natural occurring process. The possibility that atmospheric nitrogen reacts with certain chemicals was first observed by Desfosses in 1828. He observed that mixtures of alkali metal oxides and carbon react with nitrogen at high temperatures. With the use of barium carbonate as starting material, the first commercial process became available in the 1860s, developed by Margueritte and Sourdeval. The resulting barium cyanide reacts with steam, yielding ammonia. In 1898 Frank and Caro developed what
2128-568: Is about 10 . Liquid ammonia is an ionising solvent, although less so than water, and dissolves a range of ionic compounds, including many nitrates , nitrites , cyanides , thiocyanates , metal cyclopentadienyl complexes and metal bis(trimethylsilyl)amides . 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 ( Divers' solution , named after Edward Divers ) contains 0.83 mol solute per mole of ammonia and has
2204-437: Is an irritant and irritation increases with concentration; the permissible exposure limit is 25 ppm , and lethal above 500 ppm by volume. 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. In
2280-466: Is carried out in an absorption apparatus, a plate column containing water. This gas is then readily absorbed by the water, yielding the desired product (nitric acid in a dilute form), while reducing a portion of it back to nitric oxide: The NO is recycled, and the acid is concentrated to the required strength by distillation . This is only one of over 40 absorption reactions of nitrous oxides recorded, with other common reactions including: And, if
2356-583: Is classified as an extremely hazardous substance . Ammonia is produced biologically in a process called nitrogen fixation , but even more is generated industrially by the Haber process . The process helped revolutionize agriculture by providing cheap fertilizers. The global industrial production of ammonia in 2021 was 235 million tonnes. Industrial ammonia is transported by road in tankers , by rail in tank wagons , by sea in gas carriers , or in cylinders . Ammonia boils at −33.34 °C (−28.012 °F) at
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2432-562: Is credited with supporting the expansion of the human population from around 2 billion in the early 20th century to roughly 8 billion people now. Much research has been conducted on the discovery of catalysts for nitrogen fixation, often with the goal of lowering energy requirements. However, such research has thus far failed to approach the efficiency and ease of the Haber process. Many compounds react with atmospheric nitrogen to give dinitrogen complexes . The first dinitrogen complex to be reported
2508-442: Is dependent on many factors, including the legume and air and soil conditions. For example, nitrogen fixation by red clover can range from 50 to 200 lb/acre (56 to 224 kg/ha). The ability to fix nitrogen in nodules is present in actinorhizal plants such as alder and bayberry , with the help of Frankia bacteria. They are found in 25 genera in the orders Cucurbitales , Fagales and Rosales , which together with
2584-403: Is formed. Pentavalent ammonia is known as λ -amine, nitrogen pentahydride decomposes spontaneously into trivalent ammonia (λ -amine) and hydrogen gas at normal conditions. This substance was once investigated as a possible solid rocket fuel in 1966. Ammonia is also used to make the following compounds: Ammonia is a ligand forming metal ammine complexes . For historical reasons, ammonia
2660-502: Is found throughout the Solar System on Mars , Jupiter , Saturn , Uranus , Neptune , and Pluto , among other places: on smaller, icy bodies such as Pluto, ammonia can act as a geologically important antifreeze, as a mixture of water and ammonia can have a melting point as low as −100 °C (−148 °F; 173 K) if the ammonia concentration is high enough and thus allow such bodies to retain internal oceans and active geology at
2736-423: Is frequently replaced due to decomposition as a result of the extreme conditions which it operates under, leading to a form of degradation called cauliflowering . The exact mechanism of this process is unknown, the main theories being physical degradation by hydrogen atoms penetrating the platinum-rhodium lattice, or by metal atom transport from the centre of the metal to the surface. The nitric oxide (NO) formed in
2812-582: 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 and nitrogen dioxide are intermediate in this conversion: Nitric acid is used for the production of fertilisers , explosives , and many organonitrogen compounds. The hydrogen in ammonia is susceptible to replacement by a myriad substituents. Ammonia gas reacts with metallic sodium to give sodamide , NaNH 2 . With chlorine, monochloramine
2888-408: Is genetically regulated, and the activity of the protein complex is dependent on ambient oxygen concentrations, and intra- and extracellular concentrations of ammonia and oxidized nitrogen species (nitrate and nitrite). Additionally, the combined concentrations of both ammonium and nitrate are thought to inhibit N Fix , specifically when intracellular concentrations of 2- oxoglutarate (2-OG) exceed
2964-519: Is its basicity . Ammonia is considered to be a weak base. It combines with acids to form ammonium salts ; thus, with hydrochloric acid it forms ammonium chloride (sal ammoniac); with nitric acid , ammonium nitrate , etc. Perfectly dry ammonia gas will not combine with perfectly dry hydrogen chloride gas; moisture is necessary to bring about the reaction. As a demonstration experiment under air with ambient moisture, opened bottles of concentrated ammonia and hydrochloric acid solutions produce
3040-514: Is known as the Frank–Caro process to fix nitrogen in the form of calcium cyanamide . The process was eclipsed by the Haber process , which was discovered in 1909. The dominant industrial method for producing ammonia is the Haber process also known as the Haber-Bosch process. Fertilizer production is now the largest source of human-produced fixed nitrogen in the terrestrial ecosystem . Ammonia
3116-440: Is named ammine in the nomenclature of coordination compounds . One notable ammine complex is cisplatin ( Pt(NH 3 ) 2 Cl 2 , a widely used anticancer drug. Ammine complexes of chromium (III) 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 [CrCl 3 (NH 3 ) 3 ] could be formed, and concluded
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3192-791: Is no conclusive agreement on which form of nitrogenase arose first. Diazotrophs are widespread within domain Bacteria including cyanobacteria (e.g. the highly significant Trichodesmium and Cyanothece ), green sulfur bacteria , purple sulfur bacteria , Azotobacteraceae , rhizobia and Frankia . Several obligately anaerobic bacteria fix nitrogen including many (but not all) Clostridium spp. Some archaea such as Methanosarcina acetivorans also fix nitrogen, and several other methanogenic taxa , are significant contributors to nitrogen fixation in oxygen-deficient soils. Cyanobacteria , commonly known as blue-green algae, inhabit nearly all illuminated environments on Earth and play key roles in
3268-553: Is not known whether the term is equivalent to the more modern sal ammoniac (ammonium chloride). The fermentation of urine by bacteria produces a solution of ammonia ; hence fermented urine was used in Classical Antiquity to wash cloth and clothing, to remove hair from hides in preparation for tanning, to serve as a mordant in dying cloth, and to remove rust from iron. It was also used by ancient dentists to wash teeth. Nitrogen fixation Nitrogen fixation
3344-404: 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
3420-405: Is strongly exothermic , making it a useful heat source once initiated: A number of side reactions compete with the formation of nitric oxide. Some reactions convert the ammonia to N 2 , such as: This is a secondary reaction that is minimised by reducing the time the gas mixtures are in contact with the catalyst. Another side reaction produces nitrous oxide : The platinum and rhodium catalyst
3496-590: Is the most commonly present nitrogenase. The different types of nitrogenase can be determined by the specific iron protein component. Nitrogenase is highly conserved. Gene expression through DNA sequencing can distinguish which protein complex is present in the microorganism and potentially being expressed. Most frequently, the nif H gene is used to identify the presence of molybdenum-dependent nitrogenase, followed by closely related nitrogenase reductases (component II) vnf H and anf H representing vanadium-dependent and iron-only nitrogenase, respectively. In studying
3572-543: Is the precursor to nitric acid, which is the source for most N-substituted aromatic compounds. Amines can be formed by the reaction of ammonia with alkyl halides or, more commonly, with alcohols : Its ring-opening reaction with ethylene oxide give ethanolamine , diethanolamine , and triethanolamine . Amides can be prepared by the reaction of ammonia with carboxylic acid and their derivatives. For example, ammonia reacts with formic acid (HCOOH) to yield formamide ( HCONH 2 ) when heated. Acyl chlorides are
3648-438: Is usually slow, there is still a risk of explosion, particularly if transition metal ions are present as possible catalysts. 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°. The central nitrogen atom has five outer electrons with an additional electron from each hydrogen atom. This gives
3724-461: Is very difficult in the absence of a catalyst (such as platinum gauze or warm chromium(III) oxide ), due to the relatively low heat of combustion , a lower laminar burning velocity, high auto-ignition temperature , high heat of vapourization , and a narrow flammability range . However, recent studies have shown that efficient and stable combustion of ammonia can be achieved using swirl combustors, thereby rekindling research interest in ammonia as
3800-480: The Fabales form a nitrogen-fixing clade of eurosids . The ability to fix nitrogen is not universally present in these families. For example, of 122 Rosaceae genera, only four fix nitrogen. Fabales were the first lineage to branch off this nitrogen-fixing clade; thus, the ability to fix nitrogen may be plesiomorphic and subsequently lost in most descendants of the original nitrogen-fixing plant; however, it may be that
3876-473: The Siwa oasis in northwestern Egypt, where salt lakes still exist). The Greek geographer Strabo also mentioned the salt from this region. However, the ancient authors Dioscorides , Apicius , Arrian , Synesius , and Aëtius of Amida described this salt as forming clear crystals that could be used for cooking and that were essentially rock salt . Hammoniacus sal appears in the writings of Pliny , although it
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#17328547385413952-443: The addition of Nessler's solution , which gives a distinct yellow colouration in the presence of the slightest trace of ammonia or ammonium salts. The amount of ammonia in ammonium salts can be estimated quantitatively by distillation of the salts with sodium (NaOH) or potassium hydroxide (KOH), the ammonia evolved being absorbed in a known volume of standard sulfuric acid and the excess of acid then determined volumetrically ; or
4028-414: The air by means of NO x production by lightning . Nitrogen fixation is essential to life on Earth because fixed inorganic nitrogen compounds are required for the biosynthesis of all nitrogen-containing organic compounds such as amino acids , polypeptides and proteins , nucleoside triphosphates and nucleic acids . As part of the nitrogen cycle , it is essential for soil fertility and
4104-443: The ammonia may be absorbed in hydrochloric acid and the ammonium chloride so formed precipitated as ammonium hexachloroplatinate , [NH 4 ] 2 [PtCl 6 ] . 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
4180-690: The amount of nitrogen fixed in the ocean is at least as much as that on land. The colonial marine cyanobacterium Trichodesmium is thought to fix nitrogen on such a scale that it accounts for almost half of the nitrogen fixation in marine systems globally. Marine surface lichens and non-photosynthetic bacteria belonging in Proteobacteria and Planctomycetes fixate significant atmospheric nitrogen. Species of nitrogen fixing cyanobacteria in fresh waters include: Aphanizomenon and Dolichospermum (previously Anabaena). Such species have specialized cells called heterocytes , in which nitrogen fixation occurs via
4256-409: The basic genetic and physiological requirements were present in an incipient state in the most recent common ancestors of all these plants, but only evolved to full function in some of them. In addition, Trema ( Parasponia ), a tropical genus in the family Cannabaceae , is unusually able to interact with rhizobia and form nitrogen-fixing nodules. Some other plants live in association with
4332-556: The carbon and nitrogen cycle of the biosphere . In general, cyanobacteria can use various inorganic and organic sources of combined nitrogen, such as nitrate , nitrite , ammonium , urea , or some amino acids . Several cyanobacteria strains are also capable of diazotrophic growth, an ability that may have been present in their last common ancestor in the Archean eon. Nitrogen fixation not only naturally occurs in soils but also aquatic systems, including both freshwater and marine. Indeed,
4408-490: The chemistry in liquid ammonia can be classified by analogy with related reactions in aqueous solutions . Comparison of the physical properties of NH 3 with those of water shows NH 3 has the lower melting point, boiling point, density, viscosity , dielectric constant and electrical conductivity . These differences are attributed at least in part to the weaker hydrogen bonding in NH 3 . The ionic self- dissociation constant of liquid NH 3 at −50 °C
4484-626: The description Pliny gives of the salt does not conform to the properties of ammonium chloride . According to Herbert Hoover 's commentary in his English translation of Georgius Agricola 's De re metallica , it is likely to have been common sea salt. In any case, that salt ultimately gave ammonia and ammonium compounds their name. Traces of ammonia/ammonium are found in rainwater. Ammonium chloride ( sal ammoniac ), and ammonium sulfate are found in volcanic districts. Crystals of ammonium bicarbonate have been found in Patagonia guano . Ammonia
4560-498: The ecology and evolution of nitrogen-fixing bacteria , the nifH gene is the biomarker most widely used. nif H has two similar genes anf H and vnfH that also encode for the nitrogenase reductase component of the nitrogenase complex. Nitrogenase is thought to have evolved sometime between 1.5-2.2 billion years ago (Ga), although some isotopic support showing nitrogenase evolution as early as around 3.2 Ga. Nitrogenase appears to have evolved from maturase -like proteins, although
4636-410: The function of the preceding protein is currently unknown. Nitrogenase has three different forms ( Nif, Anf, and Vnf ) that correspond with the metal found in the active site of the protein (Molybdenum, Iron, and Vanadium respectively). Marine metal abundances over Earth’s geologic timeline are thought to have driven the relative abundance of which form of nitrogenase was most common. Currently, there
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#17328547385414712-406: The growth of terrestrial and semiaquatic vegetations , upon which all consumers of those ecosystems rely for biomass . Nitrogen fixation is thus crucial to the food security of human societies in sustaining agricultural yields (especially staple crops ), livestock feeds ( forage or fodder ) and fishery (both wild and farmed ) harvests . It is also indirectly relevant to
4788-544: The iron- molybdenum cofactor. The mechanism proceeds via a series of protonation and reduction steps wherein the FeMoco active site hydrogenates the N 2 substrate. In free-living diazotrophs , nitrogenase-generated ammonia is assimilated into glutamate through the glutamine synthetase /glutamate synthase pathway. The microbial nif genes required for nitrogen fixation are widely distributed in diverse environments. For example, decomposing wood, which generally has
4864-409: The last step is carried out in air: The overall reaction is the sum of the first equation, 3 times the second equation, and 2 times the last equation; all divided by 2: Alternatively, if the last step is carried out in the air, the overall reaction is the sum of equation 1, 2 times equation 2, and equation 4; all divided by 2. Without considering the state of the water, Wilhelm Ostwald developed
4940-511: The ligands must be arranged around the metal ion at the vertices of an octahedron . Ammonia forms 1:1 adducts with a variety of Lewis acids such as I 2 , phenol , and Al(CH 3 ) 3 . Ammonia is a hard base (HSAB theory) and its E & C parameters are E B = 2.31 and C B = 2.04. Its relative donor strength toward a series of acids, versus other Lewis bases, can be illustrated by C-B plots . Ammonia and ammonium salts can be readily detected, in very minute traces, by
5016-492: The manufacture of all nitrogenous industrial products , which include fertilizers , pharmaceuticals , textiles , dyes and explosives . Biological nitrogen fixation was discovered by Jean-Baptiste Boussingault in 1838. Later, in 1880, the process by which it happens was discovered by German agronomist Hermann Hellriegel and Hermann Wilfarth [ de ] and was fully described by Dutch microbiologist Martinus Beijerinck . "The protracted investigations of
5092-474: 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 by heating to 150–200 °C as long as no thermally sensitive groups are present. Other organonitrogen compounds include alprazolam , ethanolamine , ethyl carbamate and hexamethylenetetramine . Nitric acid
5168-473: The nitrogenase enzyme. One type of organelle can turn nitrogen gas into a biologically available form. This nitroplast was discovered in algae . Plants that contribute to nitrogen fixation include those of the legume family — Fabaceae — with taxa such as kudzu , clover , soybean , alfalfa , lupin , peanut and rooibos . They contain symbiotic rhizobia bacteria within nodules in their root systems , producing nitrogen compounds that help
5244-409: The oxygen with a protein such as leghemoglobin . Atmospheric nitrogen is inaccessible to most organisms, because its triple covalent bond is very strong. Most take up fixed nitrogen from various sources. For every 100 atoms of carbon, roughly 2 to 20 atoms of nitrogen are assimilated. The atomic ratio of carbon (C) : nitrogen (N) : phosphorus (P) observed on average in planktonic biomass
5320-475: The plant to grow and compete with other plants. When the plant dies, the fixed nitrogen is released, making it available to other plants; this helps to fertilize the soil . The great majority of legumes have this association, but a few genera (e.g., Styphnolobium ) do not. In many traditional farming practices, fields are rotated through various types of crops, which usually include one consisting mainly or entirely of clover . Fixation efficiency in soil
5396-402: The prior catalysed reaction is then cooled down from around 900˚C to roughly 250˚C to be further oxidised to nitrogen dioxide (NO 2 ) by the reaction: 2NO + O 2 → 2NO 2 (Δ H = -114.2 kJ/mol) The reaction: 2NO 2 → N 2 O 4 (Δ H = -57.2 kJ/mol) also occurs once the nitrogen dioxide has formed. Stage two encompasses the absorption of nitrous oxides in water and
5472-455: The process, and he patented it in 1902. Ammonia Ammonia is an inorganic chemical compound of nitrogen and hydrogen with the formula N H 3 . A stable binary hydride and the simplest pnictogen hydride , ammonia is a colourless gas with a distinctive pungent smell. Biologically, it is a common nitrogenous waste , and it contributes significantly to the nutritional needs of terrestrial organisms by serving as
5548-462: The relation of plants to the acquisition of nitrogen begun by de Saussure , Ville , Lawes , Gilbert and others, and culminated in the discovery of symbiotic fixation by Hellriegel and Wilfarth in 1887." "Experiments by Bossingault in 1855 and Pugh, Gilbert & Lawes in 1887 had shown that nitrogen did not enter the plant directly. The discovery of the role of nitrogen fixing bacteria by Herman Hellriegel and Herman Wilfarth in 1886-1888 would open
5624-488: The water formed, is −382.81 kJ/mol. Dinitrogen is the thermodynamic product of combustion : all nitrogen oxides are unstable with respect to N 2 and O 2 , which is the principle behind the catalytic converter . Nitrogen oxides can be formed as kinetic products in the presence of appropriate catalysts , a reaction of great industrial importance in the production of nitric acid : A subsequent reaction leads to NO 2 : The combustion of ammonia in air
5700-767: Was Ru(NH 3 ) 5 ( N 2 ) . Some soluble complexes do catalyze nitrogen fixation. Nitrogen can be fixed by lightning converting nitrogen gas ( N 2 ) and oxygen gas ( O 2 ) in the atmosphere into NO x ( nitrogen oxides ). The N 2 molecule is highly stable and nonreactive due to the triple bond between the nitrogen atoms. Lightning produces enough energy and heat to break this bond allowing nitrogen atoms to react with oxygen, forming NO x . These compounds cannot be used by plants, but as this molecule cools, it reacts with oxygen to form NO 2 , which in turn reacts with water to produce HNO 2 ( nitrous acid ) or HNO 3 ( nitric acid ). When these acids seep into
5776-422: Was originally described by Alfred Redfield, who determined the stoichiometric relationship between C:N:P atoms, The Redfield Ratio, to be 106:16:1. The protein complex nitrogenase is responsible for catalyzing the reduction of nitrogen gas (N 2 ) to ammonia (NH 3 ). In cyanobacteria , this enzyme system is housed in a specialized cell called the heterocyst . The production of the nitrogenase complex
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