Ammonium

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Ammonium
Ammonium-2D.svg
Ammonium-3D-balls.png
Ammonium-3D-vdW.png
Names
IUPAC name
Ammonium ion
Systematic IUPAC name
Azanium [1]
Other names
Aminediium
Aminium(+1)
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
MeSH D000644
PubChem CID
UNII
  • InChI=1S/H3N/h1H3/p+1
    Key: QGZKDVFQNNGYKY-UHFFFAOYSA-O
  • InChI=1/H3N/h1H3/p+1
    Key: QGZKDVFQNNGYKY-IKLDFBCSAZ
  • [NH4+]
Properties
[NH4]+
Molar mass 18.039 g·mol−1
Acidity (pKa)9.25
Conjugate base Ammonia
Structure
Tetrahedral
Related compounds
Other cations
Related compounds
Ammonium radical •NH4
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

The ammonium cation is a positively charged polyatomic ion with the chemical formula NH+4 or [NH4]+. It is formed by the protonation of ammonia (NH3). Ammonium is also a general name for positively charged (protonated) substituted amines and quaternary ammonium cations ([NR4]+), where one or more hydrogen atoms are replaced by organic or other groups (indicated by R).

Contents

Acid–base properties

Fumes from hydrochloric acid and ammonia forming a white cloud of ammonium chloride Hydrochloric acid ammonia.jpg
Fumes from hydrochloric acid and ammonia forming a white cloud of ammonium chloride

The ammonium ion is generated when ammonia, a weak base, reacts with Brønsted acids (proton donors):

H+ + NH3[NH4]+

The ammonium ion is mildly acidic, reacting with Brønsted bases to return to the uncharged ammonia molecule:

[NH4]+ + B → HB + NH3

Thus, the treatment of concentrated solutions of ammonium salts with a strong base gives ammonia. When ammonia is dissolved in water, a tiny amount of it converts to ammonium ions:

H2O + NH3 ⇌ OH + [NH4]+

The degree to which ammonia forms the ammonium ion depends on the pH of the solution. If the pH is low, the equilibrium shifts to the right: more ammonia molecules are converted into ammonium ions. If the pH is high (the concentration of hydrogen ions is low and hydroxide ions is high), the equilibrium shifts to the left: the hydroxide ion abstracts a proton from the ammonium ion, generating ammonia.

Formation of ammonium compounds can also occur in the vapor phase; for example, when ammonia vapor comes in contact with hydrogen chloride vapor, a white cloud of ammonium chloride forms, which eventually settles out as a solid in a thin white layer on surfaces.

Salts and characteristic reactions

Formation of ammonium Bildung Ammonium.svg
Formation of ammonium

Ammonium cation is found in a variety of salts such as ammonium carbonate, ammonium chloride, and ammonium nitrate. Most simple ammonium salts are very soluble in water. An exception is ammonium hexachloroplatinate, the formation of which was once used as a test for ammonium. The ammonium salts of nitrate and especially perchlorate are highly explosive, in these cases, ammonium is the reducing agent.

In an unusual process, ammonium ions form an amalgam. Such species are prepared by the addition of sodium amalgam to a solution of ammonium chloride. [2] This amalgam eventually decomposes to release ammonia and hydrogen. [3]

To find whether the ammonium ion is present in the salt, first, the salt is heated in presence of alkali hydroxide releasing a gas with a characteristic smell, which is ammonia.

[NH4]+ + OHheatNH3 + H2O

To further confirm ammonia, it passed through a glass rod dipped in an HCl solution (hydrochloric acid), creating white dense fumes of ammonium chloride.

NH3(g) + HCl(aq) → [NH4]Cl(s)

Ammonia, when passed through CuSO4 (copper(II) sulfate) solution, changes its color from blue to deep blue, forming Schweizer's reagent.

CuSO4(aq) + 4 NH3(aq) + 4 H2O → [Cu(NH3)4(H2O)2](OH)2(aq) + H2SO4(aq)

Ammonia or ammonium ion when added to Nessler's reagent gives a brown color precipitate known as the iodide of Million's base in basic medium.

Ammonium ion when added to chloroplatinic acid gives a yellow precipitate of ammonium hexachloroplatinate(IV).

H2[PtCl6](aq) + [NH4]+(aq) → [NH4]2[PtCl6](s) + 2 H+

Ammonium ion when added to sodium cobaltinitrite gives a yellow precipitate of ammonium cobaltinitrite.

Na3[Co(NO2)6](aq) + 3 [NH4]+(aq) → [NH4]3[Co(NO2)6](s) + 3 Na+(aq)

Ammonium ion gives a white precipitate of ammonium bitartrate when added to potassium bitartrate.

KC4H5O6(aq) + [NH4]+(aq) → [NH4]C4H5O6(s) + K+(aq)

Structure and bonding

The lone electron pair on the nitrogen atom (N) in ammonia, represented as a line above the N, forms a coordinate bond with a proton (H+). After that, all four N−H bonds are equivalent, being polar covalent bonds. The ion has a tetrahedral structure and is isoelectronic with methane and the borohydride anion. In terms of size, the ammonium cation (rionic = 175 pm)[ citation needed ] resembles the caesium cation (rionic = 183 pm).[ citation needed ]

Organic ions

The hydrogen atoms in the ammonium ion can be substituted with an alkyl group or some other organic group to form a substituted ammonium ion (IUPAC nomenclature: aminium ion). Depending on the number of organic groups, the ammonium cation is called a primary, secondary, tertiary, or quaternary. Except the quaternary ammonium cations, the organic ammonium cations are weak acids.

An example of a reaction forming an ammonium ion is that between dimethylamine, (CH3)2NH, and an acid to give the dimethylammonium cation, [(CH3)2NH2]+:

Dimethylammonium-formation-2D.png

Quaternary ammonium cations have four organic groups attached to the nitrogen atom, they lack a hydrogen atom bonded to the nitrogen atom. These cations, such as the tetra-n-butylammonium cation, are sometimes used to replace sodium or potassium ions to increase the solubility of the associated anion in organic solvents. Primary, secondary, and tertiary ammonium salts serve the same function but are less lipophilic. They are also used as phase-transfer catalysts and surfactants.

An unusual class of organic ammonium salts is derivatives of amine radical cations, [•NR3]+ such as tris(4-bromophenyl)ammoniumyl hexachloroantimonate.

Biology

Ammonium ions are a waste product of the metabolism of 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 urea 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. [4]

Ammonium is an important source of nitrogen for many plant species, especially those growing on hypoxic soils. However, it is also toxic to most crop species and is rarely applied as a sole nitrogen source. [5]

Metal

The ammonium cation has very similar properties to the heavier alkali metal cations and is often considered a close equivalent. [6] [7] [8] Ammonium is expected to behave as a metal ([NH4]+ ions in a sea of electrons) at very high pressures, such as inside giant gas planets such as Uranus and Neptune. [7] [8]

Under normal conditions, ammonium does not exist as a pure metal but does as an amalgam (alloy with mercury). [9]

See also

Related Research Articles

<span class="mw-page-title-main">Acid</span> Chemical compound giving a proton or accepting an electron pair

An acid is a molecule or ion capable of either donating a proton (i.e. hydrogen ion, H+), known as a Brønsted–Lowry acid, or forming a covalent bond with an electron pair, known as a Lewis acid.

In chemistry, amines are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia, wherein one or more hydrogen atoms have been replaced by a substituent such as an alkyl or aryl group. Important amines include amino acids, biogenic amines, trimethylamine, and aniline. Inorganic derivatives of ammonia are also called amines, such as monochloramine.

<span class="mw-page-title-main">Acid–base reaction</span> Chemical reaction between an acid and a base

In chemistry, an acid–base reaction is a chemical reaction that occurs between an acid and a base. It can be used to determine pH via titration. Several theoretical frameworks provide alternative conceptions of the reaction mechanisms and their application in solving related problems; these are called the acid–base theories, for example, Brønsted–Lowry acid–base theory.

<span class="mw-page-title-main">Hydroxide</span> Chemical compound

Hydroxide is a diatomic anion with chemical formula OH. It consists of an oxygen and hydrogen atom held together by a single covalent bond, and carries a negative electric charge. It is an important but usually minor constituent of water. It functions as a base, a ligand, a nucleophile, and a catalyst. The hydroxide ion forms salts, some of which dissociate in aqueous solution, liberating solvated hydroxide ions. Sodium hydroxide is a multi-million-ton per annum commodity chemical. The corresponding electrically neutral compound HO is the hydroxyl radical. The corresponding covalently bound group –OH of atoms is the hydroxy group. Both the hydroxide ion and hydroxy group are nucleophiles and can act as catalysts in organic chemistry.

In chemistry, a salt is a chemical compound consisting of an ionic assembly of positively charged cations and negatively charged anions, which results in a compound with no net electric charge. A common example is table salt, with positively charged sodium ions and negatively charged chloride ions.

<span class="mw-page-title-main">Base (chemistry)</span> Type of chemical substance

In chemistry, there are three definitions in common use of the word "base": Arrhenius bases, Brønsted bases, and Lewis bases. All definitions agree that bases are substances that react with acids, as originally proposed by G.-F. Rouelle in the mid-18th century.

<span class="mw-page-title-main">Hydride</span> Molecule with a hydrogen bound to a more electropositive element or group

In chemistry, a hydride is formally the anion of hydrogen (H), a hydrogen atom with two electrons. The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride of nitrogen, etc. For inorganic chemists, hydrides refer to compounds and ions in which hydrogen is covalently attached to a less electronegative element. In such cases, the H centre has nucleophilic character, which contrasts with the protic character of acids. The hydride anion is very rarely observed.

In chemistry, an amphoteric compound is a molecule or ion that can react both as an acid and as a base. What exactly this can mean depends on which definitions of acids and bases are being used.

<span class="mw-page-title-main">Hydroxylamine</span> Inorganic compound

Hydroxylamine is an inorganic compound with the formula NH2OH. The material is a white crystalline, hygroscopic compound. Hydroxylamine is almost always provided and used as an aqueous solution. It is consumed almost exclusively to produce Nylon-6. The oxidation of NH3 to hydroxylamine is a step in biological nitrification.

A weak base is a base that, upon dissolution in water, does not dissociate completely, so that the resulting aqueous solution contains only a small proportion of hydroxide ions and the concerned basic radical, and a large proportion of undissociated molecules of the base.

The Brønsted–Lowry theory (also called proton theory of acids and bases) is an acid–base reaction theory which was first developed by Johannes Nicolaus Brønsted and Thomas Martin Lowry independently in 1923. The basic concept of this theory is that when an acid and a base react with each other, the acid forms its conjugate base, and the base forms its conjugate acid by exchange of a proton (the hydrogen cation, or H+). This theory generalises the Arrhenius theory.

Acid salts are a class of salts that produce an acidic solution after being dissolved in a solvent. Its formation as a substance has a greater electrical conductivity than that of the pure solvent. An acidic solution formed by acid salt is made during partial neutralization of diprotic or polyprotic acids. A half-neutralization occurs due to the remaining of replaceable hydrogen atoms from the partial dissociation of weak acids that have not been reacted with hydroxide ions to create water molecules.

The chemical element nitrogen is one of the most abundant elements in the universe and can form many compounds. It can take several oxidation states; but the most common oxidation states are -3 and +3. Nitrogen can form nitride and nitrate ions. It also forms a part of nitric acid and nitrate salts. Nitrogen compounds also have an important role in organic chemistry, as nitrogen is part of proteins, amino acids and adenosine triphosphate.

In chemistry, an onium ion is a cation formally obtained by the protonation of mononuclear parent hydride of a pnictogen, chalcogen, or halogen. The oldest-known onium ion, and the namesake for the class, is ammonium, NH+4, the protonated derivative of ammonia, NH3.

Carbamic acid, which might also be called aminoformic acid or aminocarboxylic acid, is the chemical compound with the formula H2NCOOH. It can be obtained by the reaction of ammonia NH3 and carbon dioxide CO2 at very low temperatures, which also yields ammonium carbamate [NH4]+[NH2CO2]. The compound is stable only up to about 250 K (−23 °C); at higher temperatures it decomposes into those two gases. The solid apparently consists of dimers, with the two molecules connected by hydrogen bonds between the two carboxyl groups –COOH.

An organic base is an organic compound which acts as a base. Organic bases are usually, but not always, proton acceptors. They usually contain nitrogen atoms, which can easily be protonated. For example, amines or nitrogen-containing heterocyclic compounds have a lone pair of electrons on the nitrogen atom and can thus act as proton acceptors. Examples include:

<span class="mw-page-title-main">Ammonium cyanide</span> Chemical compound

Ammonium cyanide is an unstable inorganic compound with the formula NH4CN.

In chemistry, a fatty amine is loosely defined as any amine possessing a mostly linear hydrocarbon chain of eight or more carbon atoms. They are typically prepared from the more abundant fatty acids, with vegetable or seed-oils being the ultimate starting material. As such they are often mixtures of chain lengths, ranging up to about C22. They can be classified as oleochemicals. Commercially important members include coco amine, oleylamine, tallow amine, and soya amine. These compounds and their derivatives are used as fabric softeners, froth flotation agents, corrosion inhibitors, lubricants and friction modifiers. They are also the basis for a variety of cosmetic formulations.

Nickel compounds are chemical compounds containing the element nickel which is a member of the group 10 of the periodic table. Most compounds in the group have an oxidation state of +2. Nickel is classified as a transition metal with nickel(II) having much chemical behaviour in common with iron(II) and cobalt(II). Many salts of nickel(II) are isomorphous with salts of magnesium due to the ionic radii of the cations being almost the same. Nickel forms many coordination complexes. Nickel tetracarbonyl was the first pure metal carbonyl produced, and is unusual in its volatility. Metalloproteins containing nickel are found in biological systems.

<span class="mw-page-title-main">Ammonium iodate</span> Chemical compound

Ammonium iodate is an inorganic salt which is sparingly soluble in cold, and moderately soluble in hot water, like all iodate salts, it is a strong oxidizer.

References

  1. International Union of Pure and Applied Chemistry (2005). Nomenclature of Inorganic Chemistry (IUPAC Recommendations 2005). Cambridge (UK): RSCIUPAC. ISBN   0-85404-438-8. pp. 71,105,314. Electronic version.
  2. "Pseudo-binary compounds". Archived from the original on 2020-07-27. Retrieved 2007-10-12.
  3. "Ammonium Salts". VIAS Encyclopedia.
  4. Campbell, Neil A.; Jane B. Reece (2002). "44" . Biology (6th ed.). San Francisco: Pearson Education, Inc. pp.  937–938. ISBN   978-0-8053-6624-2.
  5. Britto, DT; Kronzucker, HJ (2002). "NH4+ toxicity in higher plants: a critical review" (PDF). Journal of Plant Physiology. 159 (6): 567–584. doi:10.1078/0176-1617-0774.
  6. Holleman, Arnold Frederik; Wiberg, Egon (2001), Wiberg, Nils (ed.), Inorganic Chemistry, translated by Eagleson, Mary; Brewer, William, San Diego/Berlin: Academic Press/De Gruyter, ISBN   0-12-352651-5
  7. 1 2 Stevenson, D. J. (November 20, 1975). "Does metallic ammonium exist?". Nature . 258 (5532): 222–223. Bibcode:1975Natur.258..222S. doi:10.1038/258222a0. S2CID   4199721.
  8. 1 2 Bernal, M. J. M.; Massey, H. S. W. (February 3, 1954). "Metallic Ammonium". Monthly Notices of the Royal Astronomical Society . 114 (2): 172–179. Bibcode:1954MNRAS.114..172B. doi: 10.1093/mnras/114.2.172 .
  9. Reedy, J.H. (October 1, 1929). "Lecture demonstration of ammonium amalgam". Journal of Chemical Education. 6 (10): 1767. Bibcode:1929JChEd...6.1767R. doi:10.1021/ed006p1767.