Nitronium ion

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Nitronium ion
Skeletal formula of nitronium with some dimensions added Nitronium-2D-dimensions.png
Skeletal formula of nitronium with some dimensions added
Spacefill model of nitronium Nitronium-3D-vdW.png
Spacefill model of nitronium
Nitronium-3D-balls.png
Names
IUPAC name
Nitronium ion
Systematic IUPAC name
Dioxidonitrogen(1+) [1]
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
PubChem CID
  • InChI=1S/NO2/c2-1-3/q+1
    Key: OMBRFUXPXNIUCZ-UHFFFAOYSA-N
  • O=[N+]=O
Properties
[NO2]+
Molar mass 46.005 g·mol−1
Thermochemistry
Std molar
entropy
(S298)
233.86 J K−1 mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

The nitronium ion, [ N O 2]+, is a cation. It is an onium ion because its nitrogen atom has +1 charge, similar to ammonium ion [NH4]+. It is created by the removal of an electron from the paramagnetic nitrogen dioxide molecule NO2, or the protonation of nitric acid HNO3 (with removal of H2O). [2]

Contents

It is stable enough to exist in normal conditions, but it is generally reactive and used extensively as an electrophile in the nitration of other substances. The ion is generated in situ for this purpose by mixing concentrated sulfuric acid and concentrated nitric acid according to the equilibrium:

H2SO4 + HNO3 → HSO4 + [NO2]+ + H2O

Structure

The nitronium ion is isoelectronic with carbon dioxide and nitrous oxide, and has the same linear structure and bond angle of 180°. For this reason it has a similar vibrational spectrum to carbon dioxide. Historically, the nitronium ion was detected by Raman spectroscopy, because its symmetric stretch is Raman-active but infrared-inactive. The Raman-active symmetrical stretch was first used to identify the ion in nitrating mixtures. [3]

Salts

A few stable nitronium salts with anions of weak nucleophilicity can be isolated. These include nitronium perchlorate [NO2]+[ClO4], nitronium tetrafluoroborate [NO2]+[BF4], nitronium hexafluorophosphate [NO2]+[PF6], nitronium hexafluoroarsenate [NO2]+[AsF6], and nitronium hexafluoroantimonate [NO2]+[SbF6]. These are all very hygroscopic compounds. [4]

The solid form of dinitrogen pentoxide, N2O5, actually consists of nitronium and nitrate ions, so it is an ionic compound, nitronium nitrate [NO2]+[NO3], not a molecular solid. However, dinitrogen pentoxide in liquid or gaseous state is molecular and does not contain nitronium ions. [2] [5]

The compounds nitryl fluoride, NO2F, and nitryl chloride, NO2Cl, are not nitronium salts but molecular compounds, as shown by their low boiling points (−72 °C and −6 °C respectively) and short nitrogen–halogen bond lengths (N–F 135 pm, N–Cl 184 pm). [6]

Addition of one electron forms the neutral nitryl radical, NO2; in fact, this is fairly stable and known as the compound nitrogen dioxide.

The related negatively charged species is NO2, the nitrite ion.

See also

Related Research Articles

<span class="mw-page-title-main">Nitrogen</span> Chemical element, symbol N and atomic number 7

Nitrogen is a chemical element; it has symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at seventh in total abundance in the Milky Way and the Solar System. At standard temperature and pressure, two atoms of the element bond to form N2, a colorless and odorless diatomic gas. N2 forms about 78% of Earth's atmosphere, making it the most abundant uncombined element in air. Because of the volatility of nitrogen compounds, nitrogen is relatively rare in the solid parts of the Earth.

<span class="mw-page-title-main">Nitric acid</span> Highly corrosive mineral acid

Nitric acid is the inorganic compound with the formula HNO3. It is a highly corrosive mineral acid. The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition into oxides of nitrogen. Most commercially available nitric acid has a concentration of 68% in water. When the solution contains more than 86% HNO3, it is referred to as fuming nitric acid. Depending on the amount of nitrogen dioxide present, fuming nitric acid is further characterized as red fuming nitric acid at concentrations above 86%, or white fuming nitric acid at concentrations above 95%.

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

Dinitrogen tetroxide, commonly referred to as nitrogen tetroxide (NTO), and occasionally (usually among ex-USSR/Russia rocket engineers) as amyl, is the chemical compound N2O4. It is a useful reagent in chemical synthesis. It forms an equilibrium mixture with nitrogen dioxide. Its molar mass is 92.011 g/mol.

<span class="mw-page-title-main">Lead(II) nitrate</span> Chemical compound

Lead(II) nitrate is an inorganic compound with the chemical formula Pb(NO3)2. It commonly occurs as a colourless crystal or white powder and, unlike most other lead(II) salts, is soluble in water.

<span class="mw-page-title-main">Nitrogen dioxide</span> Chemical compound with formula NO₂

Nitrogen dioxide is a chemical compound with the formula NO2. One of several nitrogen oxides, nitrogen dioxide is a reddish-brown gas. It is a paramagnetic, bent molecule with C2v point group symmetry. Industrially, NO2 is an intermediate in the synthesis of nitric acid, millions of tons of which are produced each year, primarily for the production of fertilizers.

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

Nitrous acid is a weak and monoprotic acid known only in solution, in the gas phase, and in the form of nitrite salts. It was discovered by Carl Wilhelm Scheele, who called it "phlogisticated acid of niter". Nitrous acid is used to make diazonium salts from amines. The resulting diazonium salts are reagents in azo coupling reactions to give azo dyes.

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

Dinitrogen pentoxide is the chemical compound with the formula N2O5. It is one of the binary nitrogen oxides, a family of compounds that only contain nitrogen and oxygen. It exists as colourless crystals that sublime slightly above room temperature, yielding a colorless gas.

In atmospheric chemistry, NOx is shorthand for nitric oxide and nitrogen dioxide, the nitrogen oxides that are most relevant for air pollution. These gases contribute to the formation of smog and acid rain, as well as affecting tropospheric ozone.

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.

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

Nitrogen trioxide or nitrate radical is an oxide of nitrogen with formula NO
3
, consisting of three oxygen atoms covalently bound to a nitrogen atom. This highly unstable blue compound has not been isolated in pure form, but can be generated and observed as a short-lived component of gas, liquid, or solid systems.

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

Dinitrogen trioxide is the inorganic compound with the formula N2O3. It is a nitrogen oxide. It forms upon mixing equal parts of nitric oxide and nitrogen dioxide and cooling the mixture below −21 °C (−6 °F):

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

Tetranitratoaluminate is an anion of aluminium and nitrate groups with formula [Al(NO3)4] that can form salts called tetranitratoaluminates. It is unusual in being a nitrate complex of a light element.

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

Zirconium nitrate is a volatile anhydrous transition metal nitrate salt of zirconium with formula Zr(NO3)4. It has alternate names of zirconium tetranitrate, or zirconium(IV) nitrate.

Barbara J. Finlayson-Pitts is a Canadian-American atmospheric chemist. She is a professor in the chemistry department at the University of California, Irvine and is the Director of AirUCI Institute. Finlayson-Pitts and James N. Pitts, Jr. are the authors of Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications (1999). She has been a member of the National Academy of Sciences since 2006 and is the laureate for the 2017 Garvan–Olin Medal. In 2016 she co-chaired the National Academy of Science report "The Future of Atmospheric Chemistry Research"

Indium(III) nitrate is a nitrate salt of indium which forms various hydrates. Only the pentahydrate has been crystallographically verified. Other hydrates are also reported in literature, such as the trihydrate.

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

Nitratoauric acid, hydrogen tetranitratoaurate, or simply called gold(III) nitrate is a crystalline gold compound that forms the trihydrate, HAu(NO3)4·3H2O or more correctly H5O2Au(NO3)4·H2O. This compound is an intermediate in the process of extracting gold. In older literature it is also known as aurinitric acid.

<span class="mw-page-title-main">Tin(IV) nitrate</span> Chemical compound

Tin(IV) nitrate is a salt of tin with nitric acid. It is a volatile white solid, subliming at 40 °C under a vacuum. Unlike other nitrates, it reacts with water to produce nitrogen dioxide.

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

Nitryl chloride is a volatile inorganic compound with formula ClNO2. At standard conditions it is a gas.

<span class="mw-page-title-main">Transition metal nitrate complex</span> Compound of nitrate ligands

A transition metal nitrate complex is a coordination compound containing one or more nitrate ligands. Such complexes are common starting reagents for the preparation of other compounds.

References

  1. "dioxidonitrogen(1+) (CHEBI:29424)". Chemical Entities of Biological Interest (ChEBI). UK: European Bioinformatics Institute.
  2. 1 2 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.
  3. Ingold, C. K.; Millen, D. J.; Poole, H. G. (1946). "Spectroscopic Identification of the Nitronium Ion". Nature. 158 (4014): 480–481. Bibcode:1946Natur.158..480I. doi:10.1038/158480c0. S2CID   4106964.
  4. Kenneth Schofield (1980). Aromatic nitration. CUP Archive. p. 88. ISBN   0-521-23362-3.
  5. Cantrell, C. A.; Davidson, J. A.; McDaniel, A. H.; Shetter, R. E.; Calvert, J. G. (1988). "The equilibrium constant for N2O5⇄NO2+NO3: Absolute determination by direct measurement from 243 to 397 K". The Journal of Chemical Physics. 88 (8): 4997–5006. doi:10.1063/1.454679.
  6. F. A. Cotton and G.Wilkinson, Advanced Inorganic Chemistry, 5th edition (1988), Wiley, p.333