Orthonitrate
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| Names | |
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| IUPAC name
Orthonitrate
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| Identifiers | |
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3D model (JSmol)
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PubChem CID
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| Properties | |
| NO3− 4 | |
| Molar mass | 78.006 |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Template:Chembox Footer/trackingTemplate:Short description
Orthonitrate is a tetrahedral anion of nitrogen with the formula NO3−
4. It was first identified in 1977[1] and is currently known in only two compounds, sodium orthonitrate (Na3NO4) and potassium orthonitrate (K3NO4). The corresponding oxoacid, orthonitric acid (Page Module:Chem2/styles.css has no content.H3NO4), is hypothetical and has never been observed. Sodium and potassium orthonitrate can be prepared by fusion of the nitrate and metal oxide under high temperatures[2] and ideally high pressures (several GPa).[3]
- Page Module:Chem2/styles.css has no content.NaNO3 + Na2O → Na3NO4 (300 °C for 3 days)[4]
The resulting orthonitrates are white solids which are extremely sensitive to moisture and CO2, decomposing within minutes to hydroxides, carbonates, and nitrates upon exposure to air.[1]
- Page Module:Chem2/styles.css has no content.Na3NO4 + CO2 → NaNO3 + Na2CO3
- Page Module:Chem2/styles.css has no content.Na3NO4 + H2O → NaNO3 + 2 NaOH
The orthonitrate ion is tetrahedral with N–O bond lengths of 139 pm, which is unexpectedly short, indicating that polar interactions are shortening the bond.[4] This short bond length parallels that of hypervalent oxyanions containing third-row elements like PO3−
4 and SO2−
4, for which pπ–dπ bonding was previously proposed as the explanation for the short bond length. Since 3d orbitals of nitrogen are much too high in energy to be involved in the case of orthonitrate, the shortness of the N–O bond in orthonitrate indicates that pπ–dπ bonding is likely not the most important explanation for the bond lengths of these heavier anions either.[2]
Other nitrogen oxyanions
References
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- ^ a b Page Module:Citation/CS1/styles.css has no content.Jansen, Martin (August 1977). "Detection of an Orthonitrate by Vibrational Spectroscopy: Na3NO4". Angewandte Chemie International Edition in English. 16 (8): 534–535. doi:10.1002/anie.197705341.
- ^ a b Page Module:Citation/CS1/styles.css has no content.Jansen, Martin (1979-08-31). "Crystal Structure of Na3NO4". Angewandte Chemie International Edition in English. 18 (9): 698–699. doi:10.1002/anie.197906982.
- ^ Page Module:Citation/CS1/styles.css has no content.Quesada Cabrera, R.; Sella, A.; Bailey, E.; Leynaud, O.; McMillan, P.F. (April 2011). "High-pressure synthesis and structural behavior of sodium orthonitrate Na3NO4" (PDF). Journal of Solid State Chemistry. 184 (4): 915–920. Bibcode:2011JSSCh.184..915Q. doi:10.1016/j.jssc.2011.02.013.
- ^ a b Page Module:Citation/CS1/styles.css has no content.Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. doi:10.1016/C2009-0-30414-6. ISBN 978-0-08-037941-8.
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