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{{chembox {{chembox
| Watchedfields = changed | Watchedfields = changed
| verifiedrevid = 401604451 | verifiedrevid = 438835202
| Name = Ethyl sulfate | Name = Ethyl sulfate
| ImageFile = Sulfovinic acid.svg | ImageFile = Sulfovinic acid.svg
| ImageSize = 200px | ImageSize = 200px
| ImageName = Ethyl sulfate | ImageAlt = Skeletal formula
| IUPACName = Ethyl hydrogen sulfate | ImageFile1 = Ethyl-bisulfate-3D-balls.png
| ImageAlt1 = Ball-and-stick model
| PIN = Ethyl hydrogen sulfate
| OtherNames = Ethyl sulfate; Sulfovinic acid; Ethyl bisulfate; Ethoxysulfonic acid; Ethyl sulphate | OtherNames = Ethyl sulfate; Sulfovinic acid; Ethyl bisulfate; Ethoxysulfonic acid; Ethyl sulphate
| Section1 = {{Chembox Identifiers | Section1 = {{Chembox Identifiers
Line 21: Line 23:
| CASNo_Ref = {{cascite|correct|CAS}} | CASNo_Ref = {{cascite|correct|CAS}}
| CASNo = 540-82-9 | CASNo = 540-82-9
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = P3LK0HF3B7
}} }}
| Section2 = {{Chembox Properties | Section2 = {{Chembox Properties
| C=2|H=6|O=4|S=1 | C=2|H=6|O=4|S=1
| Density = 1.46 g/cm³ | Density = 1.46 g/cm<sup>3</sup>

| MeltingPtC = -25
| BoilingPt = 209 °C (decomp.)
}} }}
}} }}


'''Ethyl sulfate''' (IUPAC name: '''ethyl hydrogen sulfate'''), also known as '''sulfovinic acid''', is an ] compound used as intermediate in the production of ] from ]. It is the ethyl ester of sulfuric acid. '''Ethyl sulfate''' (IUPAC name: '''ethyl hydrogen sulfate'''), also known as '''sulfovinic acid''', is an ] ] used as an intermediate in the production of ] from ]. It is the ethyl ] of sulfuric acid.


==History== ==History==
This substance was studied contemporaneously with ] by ] ] ] in 1730,<ref>{{cite journal |last1=Frobenius |first1=Joannes Sigismundus Augustus |title=An account of a ''spiritus vini æthereus'', together with several experiments tried therewith |journal=Philosophical Transactions of the Royal Society of London |date=1730 |volume=36 |issue=413 |pages=283–289 |doi=10.1098/rstl.1729.0045 |doi-access=free }}</ref> subsequently by ] ]s ] in 1797 and ] in 1815.<ref>Fourcroy, A.F. and Vauquelin, L.N. (1797) {{Webarchive|url=https://web.archive.org/web/20160319063852/https://books.google.fr/books?id=D4-jP5Fa_iMC&hl=en&pg=PA203 |date=2016-03-19 }} (On the action of sulfuric acid on alcohol and on the formation of ether), ''Annales de Chimie'', '''23''' : 203-215.</ref><ref>Gay-Lussac, L.J. (1815) (On the analysis of alcohol and sulfuric ether and on the products of fermentation), ''Annales de Chimie'', '''95''' : 311-318.</ref> ] ] ] also studied it in 1807.<ref>Théodore de Saussure (1807) {{Webarchive|url=https://web.archive.org/web/20161226222933/https://books.google.com/books?id=G-UPAAAAQAAJ&pg=PA316 |date=2016-12-26 }} ''Journal de physique, de chimie, d'histoire naturelle et des arts'', '''64''' : 316–354.</ref> In 1827, French ] and ] ] (1806-1835) along with ] noted the role of ethyl sulfate in the preparation of ] from ] and ].<ref>Dumas, J-B and Boullay, P. (1827) ''Annales de Chimie et de Physique'', '''36''' : 294-316.</ref><ref>{{cite journal |last=Wisniak |first=Jaime |year=2010 |title=Félix-Polydore Boullay |journal=Revista CENIC Ciencias Químicas |volume=41 |issue=1 |pages=59–66 |url=http://www.redalyc.org/pdf/1816/181618068009.pdf |access-date=2013-08-09 |archive-url=https://web.archive.org/web/20170816170727/http://www.redalyc.org/pdf/1816/181618068009.pdf |archive-date=2017-08-16 |url-status=live }}</ref> Further studies by the German chemist ] and the Swedish chemist ] suggested sulfuric acid was acting as a ], this eventually led to the discovery of sulfovinic acid as an intermediate in the process.<ref>E. Mitscherlich (1834) {{Webarchive|url=https://web.archive.org/web/20170113103733/https://books.google.com/books?id=wCUAAAAAMAAJ&pg=PA273 |date=2017-01-13 }} (On the formation of ether), ''Annalen der Physik und Chemie'', '''31''' (18) : 273-282.</ref><ref>J. J. Berzelius, ''Årsberättelsen om framsteg i fysik och kemi'' , (Stockholm, Sweden: Royal Swedish Academy of Sciences, 1835). After reviewing Eilhard Mitscherlich's research on the formation of ether, Berzelius coins the word ''katalys'' (catalysis) on {{Webarchive|url=https://web.archive.org/web/20170113161711/https://books.google.com/books?id=1DM1AAAAcAAJ&pg=PA245 |date=2017-01-13 }}:
This substance was studied alongside{{huh|date=November 2010}}<!-- did he study them both separately for relationships of chemistry, or study them as a mixture for their interactions, or...? --> ] for the first time by ] ] ] in 1730, subsequently by ] ]s ] and ] in 1815. ] ] ] also studied it in 1807. French ] ] discovered that a small amount of ] could convert a large amount of ] into ether and ] using a continuous process{{clarify|date=November 2010}}<!-- did he really use ], or just repeated/bolus batch -->. Further studies by German and Swedish chemists ] and ] suggested sulfuric acid was acting as a ], this eventually led discovery of sulfovinic acid as an intermediate in the process. The advent of ] by ] ] ] and ] ] ] in the 1800s confirmed ether and water were formed by the action of ] amounts of sulfuric acid on ethanol and that sulfovinic acid was formed as an intermediate in the reaction.<ref>{{cite web|title=History of Ether|work=The Composition and Structure of Ether
<blockquote>Original: ''Jag skall derföre, för att begagna en i kemien välkänd härledning, kalla den kroppars'' katalytiska kraft, ''sönderdelning genom denna kraft ''katalys, ''likasom vi med ordet analys beteckna åtskiljandet af kroppars beståndsdelar medelst den vanliga kemiska frändskapen.''</blockquote>
|url=http://classes.yale.edu/02-03/chem220a/studyaids/history/ether/ether.html |accessdate=September 7, 2005 }}</ref>
<blockquote>''Translation'': I shall, therefore, to employ a well-known derivation in chemistry, call bodies the ''catalytic force'' and the decomposition of bodies by this force ''catalysis'', just as we signify by the word ''analysis'' the separation of the constituents of bodies by the usual chemical affinities.</blockquote></ref> The advent of ] by ] ] ] and ] ] ] in the 1800s confirmed ether and water were formed by the reaction of ] amounts of sulfuric acid on ethanol and that sulfovinic acid was formed as an intermediate in the reaction.<ref>{{cite web |title=History of Ether |website=The Composition and Structure of Ether |url=http://classes.yale.edu/02-03/chem220a/studyaids/history/ether/ether.html |accessdate=September 7, 2005 |archive-url=https://web.archive.org/web/20031227101759/http://classes.yale.edu/02-03/chem220a/studyaids/history/ether/ether.html |archive-date=December 27, 2003 |url-status=live }}</ref>


==Production== ==Production==
] was produced primarily by the sulfuric acid hydration process in which ] is reacted with ] to produce ethyl sulfate followed by ],<ref>{{cite book | title = Organic Chemistry | volume = One | author = Frank C. Whitmore | publisher = Courier Corporation | date = 2012 | isbn = 9780486311159}}</ref> but this method has been mostly replaced by direct ] of ethylene.<ref>{{Cite book| doi = 10.1021/ba-1971-0103.ch008| chapter = Recent Developments in Ethylene Chemistry| title = Origin and Refining of Petroleum| volume = 103| pages = | series = Advances in Chemistry| year = 1971| last1 = Landau| first1 = Ralph| last2 = Schaffel| first2 = G. S| isbn = 978-0-8412-0120-0| chapter-url = https://archive.org/details/originrefiningof0000unse/page/150}}</ref>
⚫ Ethyl sulfate can be produced in a laboratory setting by reacting ] with ] under a gentle boil, while keeping the reaction below 140&nbsp;°C. The sulfuric acid must be added dropwise or the reaction must be actively cooled because the reaction itself is exothermic, which would cause its temperature to increase.


⚫ Ethyl sulfate can be produced in a laboratory setting by reacting ] with ] under a gentle boil, while keeping the reaction below 140&nbsp;°C. The sulfuric acid must be added dropwise or the reaction must be actively cooled because the reaction itself is highly exothermic.
:CH<sub>3</sub>CH<sub>2</sub>OH + H<sub>2</sub>SO<sub>4</sub> → CH<sub>3</sub>-CH<sub>2</sub>-O-SO<sub>3</sub>H + H<sub>2</sub>O


:<chem>CH3CH2OH + H2SO4 -> CH3-CH2-O-SO3H + H2O</chem>
⚫ If the temperature exceeds 140&nbsp;°C, the ethyl sulfate product tends to react with the unreacted ethanol starting material, producing ]. If the temperature exceeds 170&nbsp;°C in a considerable excess of sulfuric acid, the ethyl sulfate breaks down into ] and sulfuric acid.<ref>{{cite book|title=Practical Organic Chemistry (preparation 5)|author=Julius B. Cohen|publisher=Macmillan|year=1930}}</ref><ref name=Mann1960>{{cite book|title=Practical Organic Chemistry (Preparations, The Interaction of Ethanol and Sulfuric acid)|author=Frederick George Mann and Bernard Charles Saunders|publisher=Longman Inc.|year=1960}}</ref>


⚫ If the temperature exceeds 140&nbsp;°C, the ethyl sulfate product tends to react with residual ethanol starting material, producing ]. If the temperature exceeds 170&nbsp;°C in a considerable excess of sulfuric acid, the ethyl sulfate breaks down into ] and sulfuric acid.<ref>{{cite book|title=Practical Organic Chemistry (preparation 5)|author=Julius B. Cohen|publisher=Macmillan|year=1930}}</ref><ref name=Mann1960>{{cite book|title=Practical Organic Chemistry (Preparations, The Interaction of Ethanol and Sulfuric acid)|author=Frederick George Mann and Bernard Charles Saunders|publisher=Longman Inc.|year=1960}}</ref>
==Reaction==
⚫ The mechanism of the formation of ethyl sulfate, diethyl ether, and ethylene is based on the reaction between ethanol and sulfuric acid, which involves ] of the ethanolic oxygen to form the{{vague|date=November 2010}}<!-- EtO+H2 involved in SN2-like with H2SO4, vs Et+ SN1-like? --> oxonium ion.<ref name=Mann1960/>


==Salts== ==Reactions==
⚫ The mechanism of the formation of ethyl sulfate, ], and ] is based on the reaction between ethanol and ], which involves ] of the ethanolic oxygen to form the{{vague|date=November 2010}}<!-- EtO+H2 involved in SN2-like with H2SO4, vs Et+ SN1-like? --> oxonium ion.<ref name=Mann1960/>
⚫ Ethyl sulfate can exist in salt forms, such as sodium ethyl sulfate, potassium ethyl sulfate, and calcium ethyl sulfate. The salt can be formed by adding the according carbonate, or bicarbonate salt, as an example ethyl sulfate and ] forms potassium ethyl sulfate and ].<ref name=Mann1960/>


Ethyl sulfate accumulates in hair after chronic alcohol consumption and its detection can be used as a ] for alcohol consumption.<ref>{{Cite journal | doi = 10.1002/dta.2410 | pmid = 29923331 | title = Assessment of ethyl sulphate in hair as a marker for alcohol consumption using liquid chromatography-tandem mass spectrometry | journal = Drug Testing and Analysis | volume = 10 | issue = 10 | pages = 1566–1572 | year = 2018 | last1 = Cappelle | first1 = Delphine | last2 = Lai | first2 = Foon Yin | last3 = Covaci | first3 = Adrian | last4 = Vermassen | first4 = Annemie | last5 = Crunelle | first5 = Cleo L. | last6 = Neels | first6 = Hugo | last7 = Van Nuijs | first7 = Alexander L.N. | s2cid = 49314901 }}</ref>
:CH<sub>3</sub>-CH<sub>2</sub>-O-SO<sub>3</sub>H + K<sub>2</sub>CO<sub>3</sub> → CH<sub>3</sub>-CH<sub>2</sub>-O-SO<sub>2</sub>K + KHCO<sub>3</sub>

==Salts==
⚫ Ethyl sulfate can exist in salt forms, such as sodium ethyl sulfate, potassium ethyl sulfate, and calcium ethyl sulfate. The salt can be formed by adding the according carbonate, or bicarbonate salt. As an example, ethyl sulfate and ] forms potassium ethyl sulfate and ].<ref name=Mann1960/>
:<chem>CH3-CH2-O-SO3H + K2CO3 -> CH3-CH2-O-SO3K + KHCO3</chem>


==See also== ==See also==
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==References== ==References==
{{reflist}} {{Reflist}}


{{DEFAULTSORT:Ethyl Sulfate}} {{DEFAULTSORT:Ethyl Sulfate}}

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