Anhydrous nitric acid
3D model (JSmol)
CompTox Dashboard (EPA)
|Molar mass||108.01 g/mol|
|Density||1.642 g/cm3 (18 °C)|
|Melting point||41 °C (106 °F; 314 K) |
|Boiling point||47 °C (117 °F; 320 K) sublimes|
|reacts to give HNO3|
|Solubility||soluble in chloroform |
negligible in CCl4
|−35.6·10−6 cm3/mol (aq)|
|planar, C2v (approx. D2h)|
N–O–N ≈ 180°
|178.2 J K−1 mol−1 (s)|
355.6 J K−1 mol−1 (g)
Std enthalpy of
|−43.1 kJ/mol (s)|
+11.3 kJ/mol (g)
Gibbs free energy (ΔfG˚)
|Main hazards||strong oxidizer, forms strong acid in contact with water|
|NFPA 704 (fire diamond)|
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
|what is ?)(|
Dinitrogen pentoxide is the chemical compound with the formula N2O5, 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.
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dangerous oxidizer that once was used as a reagent when dissolved in chloroform for nitrations but has largely been superseded by NO2BF4 (nitronium tetrafluoroborate).
N2O5 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 [NO2]+ and nitrate anions [NO3]−; but in the gas phase and under some other conditions it is a covalently bound molecule.
Structure and physical properties
Pure solid N2O5 is a salt, consisting of separated linear nitronium ions NO2+ and planar trigonal nitrate anions NO3−. Both nitrogen centers have oxidation state +5. It crystallizes in the space group D46h (C6/mmc) with Z = 2, with the NO−
3 anions in the D3h sites and the NO+
2 cations in D3d sites.
being about 48 torr at 0 °C, 424 torr at 25 °C, and 760 torr at 32 °C (9 degrees below the melting point).
In the gas phase, or when dissolved in a nonpolar solvents such as CCl4, the compound exists as covalently bound molecules O2N–O–NO2. In the gas phase, theoretical calculations for the minimum-energy configuration indicate that the O–N–O angle in each NO
2 wing is about 134° and the N–O–N angle is about 112°. In that configuration, the two NO
2 groups are rotated about 35° around the bonds to the central oxygen, away from the N–O–N plane. The molecule thus has a propeller shape, with one axis of 180° rotational symmetry (C2) 
5 absorbs ultraviolet light with dissociation into the radicals nitrogen dioxide NO
2 and nitrogen trioxide NO
3 (uncharged nitrate). The absorption spectrum has a broad band with maximum at wavelength 160 nm.
- P4O10 + 12 HNO3 → 4 H3PO4 + 6 N2O5
Another laboratory process is the reaction of lithium nitrate LiNO
3 and bromine pentafluoride BrF
5, in the ratio exceeding 3:1. The reaction first forms nitryl fluoride FNO
2 that reacts further with the lithium nitrate:
5 + 3LiNO
3 → 3LiF + BrONO
2 + O
2 + 2FNO
2 + LiNO
3 → LiF + N
2 + O
3 → N
5 + O
3 + N
5 → 3O
2 + N
- N2O5 + H2O → 2 HNO
Solutions of dinitrogen pentoxide in nitric acid can be seen as nitric acid with more than 100% concentration. The phase diagram of the system H
5 shows the well-known negative azeotrope at 60% N
5 (that is, 70% HNO
3), a positive azeotrope at 85.7% N
5 (100% HNO
3), and another negative one at 87.5% N
5 ("102% HNO
5 + HCl → HNO
3 + NO
Dinitrogen pentoxide reacts with ammonia NH
3 to give several products, including nitrous oxide N
2O, ammonium nitrate NH
3, nitramide NH
2 and ammonium dinitramide NH
2, depending on reaction conditions.
Decomposition of dinitrogen pentoxide at high temperatures
Dinitrogen pentoxide between high temperatures of 600 and 1100°K, is decomposed in two successive stoichiometric steps:
5 → NO
2 + NO
3 → NO
2 + ½ O
In the shock wave, N
5 has decomposed stoichiometrically into nitrogen dioxide NO
2 and oxygen O
2. At temperatures of 600°K and higher, nitrogen dioxide NO
2 is unstable with respect to nitrogen oxide NO and oxygen. The thermal decomposition of 10-4 mole/L nitrogen dioxide NO
2 at 1000°K is known to require about two seconds.
Decomposition of dinitrogen pentoxide in CCl4 at 30ºC. 
Apart from the decomposition of N2O5 at high temperatures, it can also be decomposed in carbon tetrachloride at 30 °C (86 °F). Both N2O5 and NO2 are soluble in CCl4 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 O2 that is produced over time because the only form to obtain O2 is with the N2O5 decomposition. The equation below refers to the decomposition of N2O5 in CCl4:
And this reaction follows the first order rate law that says:
-d[A]/dt = k [A]
Decomposition of Nitrogen Pentoxide in the presence of Nitric Oxide
Also you can descompone dinitrogen pentoxide (N
5) in the presence of nitric oxide (NO). You can see the reaction in the equation below:
5 + NO → 3NO
Nitration of organic compounds
- N2O5 + Ar–H → HNO3 + Ar–NO2
In this use, N
5 has been largely replaced by nitronium tetrafluoroborate [NO
4]−. This salt retains the high reactivity of NO2+, but it is thermally stable, decomposing at about 180 °C (into NO2F and BF3).
In the atmosphere, dinitrogen pentoxide is an important reservoir of the NOx species that are responsible for ozone depletion: its formation provides a null cycle with which NO and NO2 are temporarily held in an unreactive state. Mixing ratios of several ppbv have been observed in polluted regions of the night-time 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 NO2 levels above 50 °N, the so-called 'Noxon cliff'.
Variations in N2O5 reactivity in aerosols can result in significant losses in tropospheric ozone, hydroxyl radicals, and NOx concentrations. Two important reactions of N2O5 in atmospheric aerosols are: 1) Hydrolysis to form nitric acid and 2) Reaction with halide ions, particularly Cl−, to form ClNO2 molecules which may serve as precursors to reactive chlorine atoms in the atmosphere.
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