ethyl nitrate
{{distinguish|nitroethane|ethyl nitrite}}
{{chembox
| Verifiedfields = changed
| Watchedfields = changed
| verifiedrevid = 428846955
| ImageFile = Ethyl Nitrate Structural Formulae V.1.svg
| ImageSize = 160
| ImageAlt = Skeletal formula of ethyl nitrate
| ImageFile1 = Ethyl nitrate 3D ball.png
| ImageSize1 = 160
| ImageAlt1 = Ball-and-stick model of the ethyl nitrate molecule
| PIN = Ethyl nitrate
| OtherNames = Nitric acid ethyl ester
| IUPACName = 1-Nitrosooxyethane
| Section1 = {{Chembox Identifiers
| CASNo_Ref = {{cascite|correct|??}}
| CASNo = 625-58-1
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 11756
| EC_number = 210-903-3
| PubChem = 12259
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = E1ZT886LR5
| UNNumber = 1993
| InChI = 1/C2H5NO3/c1-2-6-3(4)5/h2H2,1H3
| InChIKey = IDNUEBSJWINEMI-UHFFFAOYAM
| StdInChI_Ref = {{stdinchicite|changed|chemspider}}
| StdInChI = 1S/C2H5NO3/c1-2-6-3(4)5/h2H2,1H3
| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}}
| StdInChIKey = IDNUEBSJWINEMI-UHFFFAOYSA-N
| SMILES = CCO[N+](=O)[O-]
}}
| Section2 = {{Chembox Properties
| C = 2 | H = 5 | N = 1 | O = 3
| Appearance = colorless liquid
| Odor = sweet
| Density = 1.10g/cm3
| MeltingPtC = −102
| BoilingPtC = 87.5
| Solubility = soluble
}}
| Section3 = {{Chembox Hazards
| MainHazards =
| NFPA-H = 2
| NFPA-F = 3
| NFPA-R = 4
| NFPA-S =
| FlashPtF = -34
| AutoignitionPtC =
| ExploLimits = 4.1–50%
| GHS_ref=[https://pubchem.ncbi.nlm.nih.gov/compound/12259#section=Safety-and-Hazards]
| GHSPictograms = {{GHS01}}
| GHSSignalWord = Danger
| HPhrases = {{H-phrases|200}}
| PPhrases = {{P-phrases|201|202|281|372|373|380|401|501}}
}}
| Section8 = {{Chembox Related
| OtherFunction_label = Alkyl nitrates
| OtherFunction = Methyl nitrate
Ethylene glycol dinitrate
Isopropyl nitrate
}}
}}
Ethyl nitrate is the ethyl ester of nitric acid and has the chemical formula {{chem2|C2H5NO3|auto=1}}. It is a colourless, volatile, explosive, and extremely flammable liquid. It is used in organic synthesis with use as a nitrating agent and as an intermediate in the preparation of some drugs, dyes, and perfumes.{{Cite book|title=Aromatic nitration|author=Schofield, Kenneth|date=1980|publisher=Cambridge University Press|isbn=9780521233620|location=Cambridge|oclc=6357479|page=94}} Like nitroglycerin, it's a vasodilator.
Ethyl nitrate is found in the atmosphere, where it can react with other gases to form smog. The pollutant was originally thought to have been formed mainly by the combustion of fossil fuels. However recent analysis of ocean water samples reveal that in places where cool water rises from the deep, the water is saturated with alkyl nitrates, likely formed by natural processes.{{cite news
| title =Ocean yields gases that had seemed humanmade
| author =S. Perkins
| publisher = Science News (only available to subscribers)
| date = August 12, 2002
| url = https://www.sciencenews.org/article/natures-own-ocean-yields-gases-had-seemed-humanmade
}}
History and synthesis
Reaction of ethanol with nitric acid was investigated since the Middle Ages, but the fact that it produces mostly ethyl nitrite was not discovered until the 19th century. Eugène Millon was the first to synthesize ethyl nitrate in 1843 by adding urea to the mixture in order to remove any nitrous acid.{{Cite book |last1=Roscoe |first1=Henry Enfield |url=https://books.google.com/books?id=eq-WSFGQX5wC&pg=PA359 |title=A Treatise on Chemistry: The chemistry of the hydrocarbons and their derivatives, or, Organic chemistry |last2=Schorlemmer |first2=Carl |date=1881 |publisher=Macmillan |language=en}}{{Cite book |url=https://books.google.com/books?id=J6hJAQAAMAAJ&pg=PA233 |title=Annales de chimie et de physique |date=1843 |publisher=Masson. |language=fr}}
Ethyl nitrate can be prepared by nitroxylating ethanol with fuming nitric acid or a mixture of concentrated sulfuric and nitric acids. Besides decomposing nitrous acid, the aforementioned necessary addition of urea prevents explosion.{{Cite book |last=William M. Cumming |first=I. Vance Hopper |url=http://archive.org/details/Cumming1937 |title=Systematic Organic Chemistry 3ed |date=1937}} Further purifying by distillation carries a risk of explosion.{{Cite book |last=Cohen |first=Julius B. (Julius Berend) |url=https://archive.org/details/theoreticalorgan00coherich |title=Theoretical organic chemistry |date=1920 |publisher=London, Macmillan |others=University of California Libraries |page=[https://archive.org/details/theoreticalorgan00coherich/page/189 189]}}
Ethyl nitrate has also been prepared by bubbling gaseous nitryl fluoride through ethanol at −10 °C.{{cite journal
| title =Nitryl fluoride as a nitrating agent
| author =G. Hetherington and R. L. Robinson
| date = 1954
| journal = J. Chem. Soc.
| doi = 10.1039/JR9540003512
| pages = 3512
}} The reaction was subsequently studied in detail.{{cite journal
| author =B. S. Fedorov and L. T. Eremenko
| title = Nitration of alcohols by nitryl fluoride
| date = 1997
| volume = 46
| issue = 5
| journal = Russian Chemical Bulletin
| doi = 10.1007/BF02496138
| pages = 1022–1023
}}
Explosives, 6th Edition, R. Meyer, J. Kohler, A. Homburg; page 125
A nucleophilic substitution reaction of ethyl halides and silver nitrate can also yield ethyl nitrate. Again, purification poses explosion risks.
Chemical reactions
Ethyl nitrate can be reduced with stannous chloride to form hydroxylammonium chloride, though product separation is somewhat difficult.{{Cite journal |last=Dumreicher |first=Oscar Freih v. |date=December 1880 |title=Untersuchungen über die Einwirkung von Zinnchlorür auf die Stickstoffsauerstoffverbindungen |url=http://link.springer.com/10.1007/BF01517102 |journal=Monatshefte für Chemie |language=de |volume=1 |issue=1 |pages=724–754 |doi=10.1007/BF01517102 |issn=0026-9247}}
Explosive properties
Ethyl nitrate is a sensitive explosive that is prone to detonating upon impact or high temperatures, though is less so than methyl nitrate. It has a detonation velocity of 6,010 m/s,{{Cite journal |last=Kozak |first=G. D. |date=September 1998 |title=Measurement and calculation of the ideal detonation velocity for liquid nitrocompounds |url=http://link.springer.com/10.1007/BF02672682 |journal=Combustion, Explosion, and Shock Waves |language=en |volume=34 |issue=5 |pages=581–586 |doi=10.1007/BF02672682 |bibcode=1998CESW...34..581K |issn=0010-5082|url-access=subscription }} and is therefore a high explosive.