Nitrogen pentoxide

Dinitrogen pentoxide is the chemical compound with the formula , also known as nitrogen pentoxide or nitric anhydride. It is one of the binary nitrogen oxides, a family of compounds that only contain nitrogen and oxygen. It exists as colourless crystals that melt at 41 °C. Its boiling point is 47 °C, and sublimes slightly above room temperature, yielding a colorless gas.Peter Steele Connell
The Photochemistry of Dinitrogen Pentoxide
'. Ph. D. thesis, Lawrence Berkeley National Laboratory.

Dinitrogen pentoxide is an unstable and potentially dangerous oxidizer that once was used as a reagent when dissolved in chloroform for nitrations but has largely been superseded by nitronium tetrafluoroborate ().

is a rare example of a compound that adopts two structures depending on the conditions. The solid is a salt, nitronium nitrate, consisting of separate nitronium cations and nitrate anions ; but in the gas phase and under some other conditions it is a covalently-bound molecule.W. Rogie Angus, Richard W. Jones, and Glyn O. Phillips (1949): "Existence of Nitrosyl Ions (NO⁺) in Dinitrogen Tetroxide and of Nitronium Ions () in Liquid Dinitrogen Pentoxide". ''Nature'', volume 164, pages 433–434.

History

was first reported by Deville in 1840, who prepared it by treating silver nitrate () with chlorine.

Structure and physical properties

Pure solid is a salt, consisting of separated linear nitronium ions and planar trigonal nitrate anions . Both nitrogen centers have oxidation state +5. It crystallizes in the space group ''D'' (''C''6/''mmc'') with ''Z'' = 2, with the anions in the ''D''_3''h'' sites and the cations in ''D''_3''d'' sites.

The vapor pressure ''P'' (in atm) as a function of temperature ''T'' (in kelvin), in the range , is well approximated by the formula
:$\ln P = 23.2348 - \frac$
being about 48 torr at 0 °C, 424 torr at 25 °C, and 760 torr at 32 °C (9 °C below the melting point).A. H. McDaniel, J. A. Davidson, C. A. Cantrell, R. E. Shetter, and J. G. Calvert (1988): "Enthalpies of formation of dinitrogen pentoxide and the nitrate free radical". ''Journal of Physical Chemistry'', volume 92, issue 14, pages 4172–4175.

In the gas phase, or when dissolved in nonpolar solvents such as carbon tetrachloride, the compound exists as covalently-bonded molecules . In the gas phase, theoretical calculations for the minimum-energy configuration indicate that the angle in each wing is about 134° and the angle is about 112°. In that configuration, the two groups are rotated about 35° around the bonds to the central oxygen, away from the plane. The molecule thus has a propeller shape, with one axis of 180° rotational symmetry (''C''₂) S. Parthiban, B. N. Raghunandan, and R.Sumathi (1996): "Structures, energies and vibrational frequencies of dinitrogen pentoxide". ''Journal of Molecular Structure: THEOCHEM'', volume 367, pages 111–118.

When gaseous is cooled rapidly ("quenched"), one can obtain the metastable molecular form, which exothermically converts to the ionic form above −70 °C.

Gaseous absorbs ultraviolet light with dissociation into the free radicals nitrogen dioxide and nitrogen trioxide (uncharged nitrate). The absorption spectrum has a broad band with maximum at wavelength 160  nm.Bruce A. Osborne, George Marston, L. Kaminski, N. C. Jones, J. M. Gingell, Nigel Mason, Isobel C. Walker, J. Delwiche, and M.-J. Hubin-Franskin (2000): "Vacuum ultraviolet spectrum of dinitrogen pentoxide". ''Journal of Quantitative Spectroscopy and Radiative Transfer'', volume 64, issue 1, pages 67–74.

Preparation

A recommended laboratory synthesis entails dehydrating nitric acid () with phosphorus(V) oxide:
:

Another laboratory process is the reaction of lithium nitrate and bromine pentafluoride , in the ratio exceeding 3:1. The reaction first forms nitryl fluoride that reacts further with the lithium nitrate:
:
:

The compound can also be created in the gas phase by reacting nitrogen dioxide or with ozone:Francis Yao, Ivan Wilson, and Harold Johnston (1982): "Temperature-dependent ultraviolet absorption spectrum for dinitrogen pentoxide". ''Journal of Physical Chemistry'', volume 86, issue 18, pages 3611–3615.
:
However, the product catalyzes the rapid decomposition of ozone:
:

Dinitrogen pentoxide is also formed when a mixture of oxygen and nitrogen is passed through an electric
discharge.William W. Wilson and Karl O. Christe (1987): "Dinitrogen Pentoxide. New Synthesis and Laser Raman Spectrum". ''Inorganic Chemistry'', volume 26, pages 1631–1633. Another route is the reactions of Phosphoryl chloride or nitryl chloride with silver nitrate

Reactions

Dinitrogen pentoxide reacts with water (hydrolyses) to produce nitric acid . Thus, dinitrogen pentoxide is the anhydride of nitric acid:
:

Solutions of dinitrogen pentoxide in nitric acid can be seen as nitric acid with more than 100% concentration. The phase diagram of the system − shows the well-known negative azeotrope at 60% (that is, 70% ), a positive azeotrope at 85.7% (100% ), and another negative one at 87.5% ("102% ").L. Lloyd and P. A. H. Wyatt (1955): "The vapour pressures of nitric acid solutions. Part I. New azeotropes in the water–dinitrogen pentoxide system". ''Journal of the Chemical Society (Resumed)'', volume 1955, pages 2248–2252.

The reaction with hydrogen chloride also gives nitric acid and nitryl chloride :Robert A. Wilkins Jr. and I. C. Hisatsune (1976): "The Reaction of Dinitrogen Pentoxide with Hydrogen Chloride". ''Industrial & Engineering Chemistry Fundamentals'', volume 15, issue 4, pages 246–248.
:

Dinitrogen pentoxide eventually decomposes at room temperature into and . Decomposition is negligible if the solid is kept at 0 °C, in suitably inert containers.

Dinitrogen pentoxide reacts with ammonia to give several products, including nitrous oxide , ammonium nitrate , nitramide and ammonium dinitramide , depending on reaction conditions.C. Frenck and W. Weisweiler (2002): "Modeling the Reactions Between Ammonia and Dinitrogen Pentoxide to Synthesize Ammonium Dinitramide (ADN)". ''Chemical Engineering & Technology'', volume 25, issue 2, pages 123–128.

Decomposition of dinitrogen pentoxide at high temperatures

Dinitrogen pentoxide between high temperatures of , is decomposed in two successive stoichiometric steps:
:
:
In the shock wave, has decomposed stoichiometrically into nitrogen dioxide and oxygen. At temperatures of 600 K and higher, nitrogen dioxide is unstable with respect to nitrogen oxide and oxygen. The thermal decomposition of 0.1 mM nitrogen dioxide at 1000 K is known to require about two seconds.Schott, G., & Davidson, N. (1958). Shock Waves in Chemical Kinetics: The Decomposition of N₂O₅ at High Temperatures. Journal of the American Chemical Society, 80(8), 1841–1853.

Decomposition of dinitrogen pentoxide in carbon tetrachloride at 30 °C

Apart from the decomposition of at high temperatures, it can also be decomposed in carbon tetrachloride at .J.,Jaime, R. (2008)
Determinación de orden de reacción haciendo uso de integrales definidas
Universidad Nacional Autónoma de Nicaragua, Managua.
Both and are soluble in and remain in solution while oxygen is insoluble and escapes. The volume of the oxygen formed in the reaction can be measured in a gas burette. After this step we can proceed with the decomposition, measuring the quantity of that is produced over time because the only form to obtain is with the decomposition.
The equation below refers to the decomposition of in :

:

And this reaction follows the first order rate law that says:

:-\frac = k mathrm/math>

Decomposition of nitrogen pentoxide in the presence of nitric oxide

can also be decomposed in the presence of nitric oxide :

:

The rate of the initial reaction between dinitrogen pentoxide and nitric oxide of the elementary unimolecular decomposition.

Applications

Nitration of organic compounds

Dinitrogen pentoxide, for example as a solution in chloroform, has been used as a reagent to introduce the functionality in organic compounds. This nitration reaction is represented as follows:

:

where Ar represents an arene moiety. The reactivity of the can be further enhanced with strong acids that generate the "super-electrophile" .

In this use, has been largely replaced by nitronium tetrafluoroborate . This salt retains the high reactivity of , but it is thermally stable, decomposing at about 180 °C (into and ).

Dinitrogen pentoxide is relevant to the preparation of explosives.

Atmospheric occurrence

In the atmosphere, dinitrogen pentoxide is an important reservoir of the species that are responsible for ozone depletion: its formation provides a null cycle with which and are temporarily held in an unreactive state. Mixing ratios of several parts per billion by volume have been observed in polluted regions of the nighttime troposphere. Dinitrogen pentoxide has also been observed in the stratosphere at similar levels, the reservoir formation having been postulated in considering the puzzling observations of a sudden drop in stratospheric levels above 50 °N, the so-called ' Noxon cliff'.

Variations in reactivity in aerosols can result in significant losses in tropospheric ozone, hydroxyl radicals, and concentrations. Two important reactions of in atmospheric aerosols are hydrolysis to form nitric acid and reaction with halide ions, particularly , to form molecules which may serve as precursors to reactive chlorine atoms in the atmosphere.

Hazards

is a strong oxidizer that forms explosive mixtures with organic compounds and ammonium salts. The decomposition of dinitrogen pentoxide produces the highly toxic nitrogen dioxide gas.

References

{{DEFAULTSORT:Dinitrogen Pentoxide
Nitrogen oxides
Acid anhydrides
Acidic oxides
Nitrates
Nitronium compounds