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Production and synthesis

Ethyl acetate was first synthesized by the Count de Lauraguais in 1759 by distilling a mixture of ethanol and acetic acid.²

In 2004, an estimated 1.3 million tonnes were produced worldwide.³⁴ The combined annual production in 1985 of Japan, North America, and Europe was about 400,000 tonnes. The global ethyl acetate market was valued at $3.3 billion in 2018.⁵

Ethyl acetate is synthesized in industry mainly via the classic Fischer esterification reaction of ethanol and acetic acid. This mixture converts to the ester in about 65% yield at room temperature:

CH3CO2H + CH3CH2OH → CH3CO2CH2CH3 + H2O

The reaction can be accelerated by acid catalysis and the equilibrium can be shifted to the right by removal of water.

It is also prepared in industry using the Tishchenko reaction, by combining two equivalents of acetaldehyde in the presence of an alkoxide catalyst:

2 CH3CHO → CH3CO2CH2CH3

Silicotungstic acid is used to manufacture ethyl acetate by the alkylation of acetic acid by ethylene:⁶

C2H4 + CH3CO2H → CH3CO2C2H5

Uses

Ethyl acetate is used primarily as a solvent and diluent, being favored because of its low cost, low toxicity, and agreeable odor.⁷ For example, it is commonly used to clean circuit boards and in some nail varnish removers (acetone is also used). Coffee beans and tea leaves are decaffeinated with this solvent.⁸ It is also used in paints as an activator or hardener. Ethyl acetate is present in confectionery, perfumes, and fruits. In perfumes it evaporates quickly, leaving the scent of the perfume on the skin.

Ethyl acetate is an asphyxiant for use in insect collecting and study.⁹ In a killing jar charged with ethyl acetate, the vapors will kill the collected insect quickly without destroying it. Because it is not hygroscopic, ethyl acetate also keeps the insect soft enough to allow proper mounting suitable for a collection. However, ethyl acetate is regarded as potentially doing damage to insect DNA, making specimens processed this way less than ideal for subsequent DNA sequencing.¹⁰

Laboratory uses

In the laboratory, mixtures containing ethyl acetate are commonly used in column chromatography and extractions.¹¹ Ethyl acetate is rarely selected as a reaction solvent because it is prone to hydrolysis, transesterification, and condensations.

Occurrence in wines

Ethyl acetate is the most common ester in wine, being the product of the most common volatile organic acid – acetic acid, and the ethyl alcohol generated during the fermentation. The aroma of ethyl acetate is most vivid in younger wines and contributes towards the general perception of "fruitiness" in the wine. Sensitivity varies, with most people having a perception threshold around 120 mg/L. Excessive amounts of ethyl acetate are considered a wine fault.

Reactions

Ethyl acetate is only weakly Lewis basic, like a typical carboxylic acid ester.

Ethyl acetate hydrolyses to give acetic acid and ethanol. Bases accelerate the hydrolysis, which is subject to the Fischer equilibrium mentioned above. In the laboratory, and usually for illustrative purposes only, ethyl esters are typically hydrolyzed in a two-step process starting with a stoichiometric amount of a strong base, such as sodium hydroxide. This reaction gives ethanol and sodium acetate, which is unreactive toward ethanol:

CH3CO2C2H5 + NaOH → C2H5OH + CH3CO2Na

In the Claisen condensation, anhydrous ethyl acetate and strong bases react to give ethyl acetoacetate:¹²

Properties

Physical properties

Under normal conditions, ethyl acetate exists as a colorless, low-viscosity, and flammable liquid. Its melting point is −83 °C, with a melting enthalpy of 10.48 kJ/mol. At atmospheric pressure, the compound boils at 77 °C. The vaporization enthalpy at the boiling point is 31.94 kJ/mol. The vapor pressure function follows the Antoine equation

log 10 ⁡ ( p ) = A − B T + C , {\displaystyle \log _{10}(p)=A-{\frac {B}{T+C}},}

where

p {\displaystyle p} is the vapor pressure in bars, T {\displaystyle T} is the absolute temperature in kelvins, and A = 4.22809 {\displaystyle A=4.22809} , B = 1245.702 {\displaystyle B=1245.702} , C = − 55.189 {\displaystyle C=-55.189} are constants.

This function is valid within the temperature range of 289 to 349 K (16–76 °C).

The enthalpy of vaporization in kJ/mol is calculated according to the empirical equation by Majer and Svoboda¹³

Δ H vap = A exp ⁡ ( − β T r ) ( 1 − T r ) β , {\displaystyle \Delta H_{\text{vap}}=A\exp(-\beta \,T_{\text{r}})\,(1-T_{\text{r}})^{\beta },}

where

T r = T / T c {\displaystyle T_{\text{r}}=T/T_{\text{c}}} is the reduced temperature, and T c {\displaystyle T_{\text{c}}} = 523.2 K is the critical temperature. A {\displaystyle A} = 54.26 kJ/mol and β {\displaystyle \beta } = 0.2982 are constants.

The following table summarizes the most important thermodynamic properties of ethyl acetate under various conditions.

Compilation of key thermodynamic properties

Property	Type	Value	Remarks	References
Standard enthalpy of formation	Δ f H liquid 0 {\displaystyle \Delta _{f}H_{\text{liquid}}^{0}} Δ f H gas 0 {\displaystyle \Delta _{f}H_{\text{gas}}^{0}}	−480.57 kJ/mol −445.43 kJ/mol	as liquid as gas	14
Standard entropy	S liquid 0 {\displaystyle S_{\text{liquid}}^{0}} S gas 0 {\displaystyle S_{\text{gas}}^{0}}	259.4 J/(mol·K) 362.75 J/(mol·K)	as liquid as gas	1516
Combustion enthalpy	Δ c H liquid 0 {\displaystyle \Delta _{c}H_{\text{liquid}}^{0}}	−2235.4 kJ/mol		17
Heat capacity (25 °C)	c p {\displaystyle c_{p}}	168.94 J/(mol·K) 1.92 J/(g·K) 113.64 J/(mol·K) 1.29 J/(g·K)	as liquid as gas	1819
Critical temperature	T c {\displaystyle T_{\text{c}}}	523.2 K		20
Critical pressure	p c {\displaystyle p_{\text{c}}}	38.82 bar		21
Critical density	ρ c {\displaystyle \rho _{\text{c}}}	3.497 mol/L		22
Acentric factor	ω c {\displaystyle \omega _{c}}	0.36641		23

Safety

The LD50 for rats is 5620 mg/kg,²⁴ indicating low acute toxicity. Given that the chemical is naturally present in many organisms, there is little risk of toxicity.

Overexposure to ethyl acetate may cause irritation of the eyes, nose, and throat. Severe overexposure may cause weakness, drowsiness, and unconsciousness.²⁵ Humans exposed to a concentration of 400 ppm in 1.4 mg/L ethyl acetate for a short time were affected by nose and throat irritation.²⁶ Ethyl acetate is an irritant of the conjunctiva and mucous membrane of the respiratory tract. Animal experiments have shown that, at very high concentrations, the ester has central nervous system depressant and lethal effects; at concentrations of 20,000 to 43,000 ppm (2.0–4.3%), there may be pulmonary edema with hemorrhages, symptoms of central nervous system depression, secondary anemia and liver damage. In humans, concentrations of 400 ppm cause irritation of the nose and pharynx; cases have also been known of irritation of the conjunctiva with temporary opacity of the cornea. In rare cases exposure may cause sensitization of the mucous membrane and eruptions of the skin. The irritant effect of ethyl acetate is weaker than that of propyl acetate or butyl acetate.²⁷

External links

• https://pubchem.ncbi.nlm.nih.gov/compound/ethyl_acetate#section=Toxicity
• NIOSH Pocket Guide to Chemical Hazards
• International Chemical Safety Cards
• Material safety data (MSDS) for ethyl acetate
• National Pollutant Inventory – Ethyl acetate fact sheet
• Ethyl Acetate: Molecule of the Month
• Purpose of Using Concentrated Sulfuric Acid in Esterification for Catalysis
• Basic facts and contact SEKAB [1] SEKAB ethyl acetate
• A Techno Commercial Profile of Ethyl Acetate in India
• Calculation of vapor pressure, liquid density, dynamic liquid viscosity, surface tension of ethyl acetate

References

1. Riemenschneider, Wilhelm; Bolt, Hermann M. "Esters, Organic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a09_565.pub2. ISBN 978-3-527-30673-2. 978-3-527-30673-2 ↩

2. Parker, Joseph (1832). "The Edinburgh Encyclopaedia". The Edinburgh Encyclopaedia. 5. https://books.google.com/books?id=8-JEAQAAMAAJ ↩

3. Riemenschneider, Wilhelm; Bolt, Hermann M. "Esters, Organic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a09_565.pub2. ISBN 978-3-527-30673-2. 978-3-527-30673-2 ↩

4. Dutia, Pankaj (August 10, 2004). "Ethyl Acetate: A Techno-Commercial Profile" (PDF). Chemical Weekly: 184. Retrieved 2009-03-21. http://www.chemicalweekly.com/Profiles/Ethyl_Acetate.pdf#page=6 ↩

5. ""Global Ethyl Acetate Market to be valued at $3.3 billion in 2018" reports Visiongain". Visiongain. 2019-09-05. Retrieved 2019-09-05. https://www.visiongain.com/global-ethyl-acetate-market-to-be-valued-at-3-3-billion-in-2018-reports-visiongain/ ↩

6. Misono, Makoto (2009). "Recent progress in the practical applications of heteropolyacid and perovskite catalysts: Catalytic technology for the sustainable society". Catalysis Today. 144 (3–4): 285–291. doi:10.1016/j.cattod.2008.10.054. /wiki/Doi_(identifier) ↩

7. Riemenschneider, Wilhelm; Bolt, Hermann M. "Esters, Organic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a09_565.pub2. ISBN 978-3-527-30673-2. 978-3-527-30673-2 ↩

8. ico.org Archived 2007-04-29 at the Wayback Machine http://www.ico.org/decaffeination.asp ↩

9. Littledyke, M.; Cherrett, J. M. (June 1976). "Direct ingestion of plant sap from cut leaves by the leaf-cutting ants Atta cephalotes (L.) and acromyrmex octospinosus (reich) (Formicidae, Attini)". Bulletin of Entomological Research. 66 (2): 205–217. doi:10.1017/S0007485300006647. ISSN 1475-2670. https://www.cambridge.org/core/journals/bulletin-of-entomological-research/article/abs/direct-ingestion-of-plant-sap-from-cut-leaves-by-the-leafcutting-ants-atta-cephalotes-l-and-acromyrmex-octospinosus-reich-formicidae-attini/AF32CE2FBBD06C93D5FC3DE8287B1777 ↩

10. Cilia, G.; Flaminio, S.; Quaranta, M. (2022). "A novel and non-invasive method for DNA extraction from dry bee specimens". Scientific Reports. 12 (1): 11679. Bibcode:2022NatSR..1211679C. doi:10.1038/s41598-022-15595-8. PMC 9270346. PMID 35804181. https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9270346 ↩

11. Tan, Wei Wen; Wu, Bin; Wei, Ye; Yoshikai, Naohiko (2018). "Copper and Secondary Amine-Catalyzed Pyridine Synthesis from O-Acetyl Oximes and α,β-Unsaturated Aldehydes". Organic Syntheses. 95: 1–14. doi:10.15227/orgsyn.095.0001. http://www.orgsyn.org/demo.aspx?prep=v95p0001 ↩

12. Inglis, J. K. H.; Roberts, K. C. (1926). "Ethyl Acetoacetate". Org. Synth. 6: 36. doi:10.15227/orgsyn.006.0036. /wiki/Doi_(identifier) ↩

13. V. Majer, V. Svoboda: Enthalpies of Vaporization of Organic Compounds: A Critical Review and Data Compilation. Blackwell Scientific Publications, Oxford 1985, ISBN 0-632-01529-2. ↩

14. K. B. Wiberg, L. S. Crocker, K. M. Morgan: Thermochemical studies of carbonyl compounds. 5. Enthalpies of reduction of carbonyl groups. In: J. Am. Chem. Soc. 113, 1991, pp. 3447–3450. doi:10.1021/ja00009a033. /wiki/J._Am._Chem._Soc. ↩

15. G. S. Parks, H. M. Huffman, M. Barmore: Thermal data on organic compounds. XI. The heat capacities, entropies and free energies of ten compounds containing oxygen or nitrogen. In: J. Am. Chem. Soc. 55, 1933, S. 2733–2740, doi:10.1021/ja01334a016. //doi.org/10.1021/ja01334a016 ↩

16. D. R. Stull, Jr.: The Chemical Thermodynamics of Organic Compounds. Wiley, New York, 1969. ↩

17. M. E. Butwill, J. D. Rockenfeller: Heats of combustion and formation of ethyl acetate and isopropyl acetate. In: Thermochim. Acta. 1, 1970, pp. 289–295. doi:10.1016/0040-6031(70)80033-8. /wiki/Thermochim._Acta ↩

18. Pintos, M.; Bravo, R.; Baluja, M. C.; Paz Andrade, M. I.; Roux-Desgranges, G.; Grolier, J.-P. E. (1988). "Thermodynamics of alkanoate + alkane binary mixtures. Concentration dependence of excess heat capacities and volumes". Can. J. Chem. 66 (5): 1179–1186. doi:10.1139/v88-193. /wiki/Doi_(identifier) ↩

19. D. R. Stull, Jr.: The Chemical Thermodynamics of Organic Compounds. Wiley, New York, 1969. ↩

20. V. Majer, V. Svoboda: Enthalpies of Vaporization of Organic Compounds: A Critical Review and Data Compilation. Blackwell Scientific Publications, Oxford 1985, ISBN 0-632-01529-2. ↩

21. D. Ambrose, J. H. Ellender, H. A. Gundry, D. A. Lee, R. Townsend: Thermodynamic properties of organic oxygen compounds. LI. The vapour pressures of some esters and fatty acids. In: J. Chem. Thermodyn. 13, 1981, S. 795–802. doi:10.1016/0021-9614(81)90069-0. /wiki/J._Chem._Thermodyn. ↩

22. S. Young, G. L. Thomas: The vapour pressures, molecular volumes, and critical constants of ten of the lower esters. In: J. Chem. Soc. 63, 1893, S. 1191. /wiki/J._Chem._Soc. ↩

23. J. Schmidt: Auslegung von Sicherheitsventilen für Mehrzweckanlagen nach ISO 4126-10 (in German). In: Chem. Ing. Techn. 83, 2011, pp. 796–812. doi:10.1002/cite.201000202. /w/index.php?title=Chem._Ing._Techn.&action=edit&redlink=1 ↩

24. Hazard Ethyl Acetate MSDS "Ethyl Acetate MSDS Number: E2850". http://hazard.com/msds/mf/baker/baker/files/e2850.htm ↩

25. Mackison, F. W.; Stricoff, R. S.; Partridge, L. J. Jr., eds. (January 1981). NIOSH/OSHA – Occupational Health Guidelines for Chemical Hazards. DHHS (NIOSH) Publication No. 81–123. Washington, DC: U.S. Government Printing Office. ↩

26. Clayton, G.D.; Clayton, F.E., eds. (1993–1994). Patty's Industrial Hygiene and Toxicology. Volumes 2A, 2B, 2C, 2D, 2E, 2F: Toxicology (4th ed.). New York, NY: John Wiley & Sons. p. 2981. ↩

27. Encyclopedia of Occupational Health and Safety, Geneva, Switzerland: International Labour Office, 1983, p. 782 ↩