|Ethyl acetate Chemical Properties|
|mp ||−84 °C(lit.)|
|bp ||76.5-77.5 °C(lit.)|
|density ||0.902 g/mL at 25 °C(lit.)|
|vapor density ||3 (20 °C, vs air)|
|vapor pressure ||73 mm Hg ( 20 °C)|
|refractive index ||n20/D 1.3720(lit.)|
|Fp ||26 °F|
|storage temp. ||2-8°C|
|Water Solubility ||80 g/L (20 ºC)|
|Stability:||Stable. Incompatible with various plastics, strong oxidizing agents. Highly flammable. Vapour/air mixtures explosive. May be moisture sensitive.|
|CAS DataBase Reference||141-78-6(CAS DataBase Reference)|
|NIST Chemistry Reference||Ethyl acetate(141-78-6)|
|EPA Substance Registry System||Acetic acid ethyl ester(141-78-6)|
|Ethyl acetate Usage And Synthesis|
|Ethyl acetate||Ethyl acetate is a compound generated with the hydroxyl group of acetate being replaced with ethoxy. Its simplified structural formula: CH3COOCH2CH3. Pure ethyl acetate is a colorless transparent liquid with aromatic odor; melting point: -83.6 °C; boiling point: 77.06 °C; relative density (water = 1): 0.894-0.898; relative vapor density (air = 1): 3.04; it has strong ether-like odor as well as clear fruity wine flavor which is easy to spread but not lasting. It is slightly soluble in water, soluble in most kinds of organic solvents such as alcohol, ketone, ether, and chloroform. Ethyl acetate is a widely used fine chemical product with excellent solubility, quick-drying property, and wide applications and is a very important organic chemical raw material and excellent industrial solvent which is widely used in the process of producing cellulose acetate, ethyl based fiber, chlorinated rubber, vinyl resins, cellulose acetate resins, synthetic rubber, and paints. Its main functions include: being used as an industrial solvent for being applied to paints, adhesives, ethyl cellulose, leather, linoleum colorants, synthetic fibers; being used as a binder for being applied to printing inks, artificial pearl production; as extracting agent for used in the production of medicine and organic acids; as a spice raw materials being used as the main raw material for the flavors of pineapple, banana, and strawberry and whiskey, butter. We are always talking about the good taste of old wine. This is just because of that wine contains ethyl acetate which has fruit flavor. Wine contains a small amount of acetic acid, which can react with ethanol to generate ethyl acetate. Because this is a reversible reaction, so it takes a long time for the accumulation of enough ethyl acetate to lead to the aroma flavor of old wine. |
In some developed countries, it is used as a non-toxic, pollution-free solvent which is gradually replacing the benzene solvent and methyl ethyl ketone solvent which can bring great harm to humans and the environment. Currently ethyl acetate production routes can be divided into esterification, acetaldehyde condensation, ethylene adduct and ethanol dehydrogenation. The ethanol dehydrogenation method adopted in my company was a new technology developed in the late 1990s which can produce ethyl acetate through one-step dehydrogenation of ethanol while generating by-product hydrogen gas. Using this method can produce high purity ethyl acetate containing low amount of water and various kinds of heavy metals. Its quality exceeds national quality standards.
|Purification and water removal methods||Ethyl acetate generally has a content of 95% to 98% containing a small amount of water, ethanol and acetic acid. It can be further purified as following: add 100mL of acetic anhydride into 1000mL of ethyl acetate; add 10 drops of concentrated sulfuric acid, heat and reflux for 4h to remove impurities such as ethanol and water, and then further subject to distillation. Distillate is oscillated by 20 ~ 30g of anhydrous potassium carbonate and further subject to re-distillation. The product has a boiling point of 77 °C and purity being over 99%.
|Hydrolysis reaction||Ethyl acetate can be hydrolyzed into acetate and ethanol in the catalysis of acid.
|Laboratory Preparation of ethyl acetate||Add ethanol first, then further add concentrated sulfuric acid (to prevent bumping), and finally add acetic acid and then heat (to control experiments) |
The equation of acetate esterification reaction for making ethyl acetate: CH3COOH + CH3CH2OH === CH3COOC2H5 + H2O (reversible reaction, heating, concentrated sulfuric acid catalyst)
1: The esterification reaction is a reversible reaction. In order to improve the yield of the ester, the reaction must proceed by facilitating the creation of an ester direction. Generally the reaction was supplied with an excess amount of acid or alcohol. In the laboratory, the general approach is supplying excess amount of ethanol. The mass fraction of ethanol needs to be high. Using 100% ethanol to replace 95% ethanol will have a better efficacy. The amount of concentrated sulfuric acid used for catalysis is usually small with its mass reaching the 3% of ethanol being sufficient for carrying out the catalysis. However, in order to remove the water formed in the reaction, the amount of concentrated sulfuric acid should be a bit more.
2: The reaction temperature of preparation of ethyl acetate should not be too high and should be maintained at about 60 ℃ ~ 70 °C. High temperature will produce impurities such as sulfurous acid and ether. After liquid being heated to boiling, it should be changed to low heating. We can add a few slices of porcelain pieces in advance to prevent liquid bumping.
3 Airway tube should not be put into Na2CO3 solution to prevent the uneven heating which will result in Na2CO3 solution’s being sucked back into the tube of heated reactants.
3.1 Concentrated sulfuric acid can be used as both a catalyst and water-absorbing agent.
3.2: The roles of saturated Na2CO3 solution are:
(1) one role of saturated sodium carbonate solution is to condense the vapor ester and reduce the solubility of the ester (facilitates hierarchy) in the water, remove the acetic acid mixed in ethyl acetate, and dissolve the ethanol mixed in ethyl acetate.
(2) Na2CO3 can react with volatilized acetic acid to generate sodium acetate with no odor, making it easy to smell the scent of ethyl acetate.
(3) Acetate ethyl has a low solubility in the salt solution.
(4) Salt solution has a low density which can facilitate the layering.
3.3: In order to facilitate the generation of ethyl acetate, you may take the following measures:
(1) Upon preparation of ethyl acetate, the reaction temperature should not be too high (60 ℃ ~ 70 ℃). Also avoid making the liquid boil.
(2) It’s best to use glacial acetic acid and ethanol while using excess ethanol.
(3) The amount of catalytic concentrated sulfuric acid is very small, but in order to remove the water formed in the reaction, the amount of concentrated sulfuric acid should be slightly more than that of ethanol.
(4) We should use inorganic salts Na2CO3 solution for absorbing the volatilized acetic acid.
|Application||This product is an important organic chemical raw material which can be used for the manufacturing of acetamide, acetyl acetate, methyl heptyl ketene and can also widely applied to various fields of flavors, fragrances, paints, pharmaceuticals, advanced ink, collodion, nitrocellulose, leather, and dyes. It is one of the synthetic perfumes applied in edible flavor in large dosage and is used in amount in edible flavor used in different kinds of flavors such as banana, pear, peach, pineapple, and grape. It can also be used as extracting agent and dehydrating agent as well as food packaging and color printing. Its tanning products can be used in desulfurization, cigarette materials, oil drilling, metal flotation, and descaling. |
It is widely used in the production of inks, adhesives, and artificial leather. It can also be used as the extraction agent of pharmaceutical and organic acid, and also used as the ingredients of varnish and perfume.
It can be used to dissolve nitrocellulose, ink, grease, etc., it can also be used as the raw material of making paint, leather, plastics, dyes, drugs and spices.
It can be used in a small amount to be applied to magnolia, ylang, Osmanthus fragrans and cyclamen, and fruit flavor as top note for preparation of fresh fruity flavor, particularly to perfume fragrance which has mellow effect. It applies to food flavor including cherries, peaches, apricots, grapes, strawberries, raspberries, bananas, pears, pineapple, lemon, and melon. Wine flavor such as brandy, whiskey, rum, wine, liquor also use it.
GB 2760-96 ruled as the allowed food flavors. It is mainly used for incense, persimmon deastringency, making the granules or tablets of spices, and vinegar ingredients. It is also widely used in the preparation of fruity flavor such as cherries, peaches, and apricots and wine flavor such as brandy. It can also be used as the solvent of chewing gum base diluent vinyl acetate, pigment diluent as well as applied to decaffeinated coffee, tea and fruit and vegetables.
Ethyl acetate is one of the most widely used fatty acid ester and is a quick-drying solvent with excellent solubility and is an excellent industrial solvent. It can be applied to nitrocellulose, ethyl cellulose, chlorinated rubber and vinyl resins, cellulose acetate, cellulose butyl acetate and synthetic rubber; it can also be used to the liquid nitrocellulose ink for copying machine. It can also used as the solvent of adhesive and paint thinner; it can also be used as a cleaning agent in the textile industry; in the food industry, it can be used as flavor extraction agent for special modified version of alcohol; it is also used as the extractant in pharmaceutical process and organic acids. It is an important spice additive used in the perfume industry and can be used as a component of flavoring agent. Ethyl acetate is the also the raw material of manufacture of dyes, pharmaceuticals and perfume. Ethyl acetate is also a highly efficient solvent of many kinds of resins and widely used in the production of inks and leather.
It can be used as the flavoring agent of feed.
It can be used as the standard material and solvent for analytical reagents and chromatography analysis.
Extracting agent: to extract many kinds of compounds (phosphorus, tungsten, arsenic, cobalt) from aqueous solutions; organic solvents; as the standard substance for thermometer calibration upon sugar separation. Identification: bismuth, gold, iron, mercury, oxidizing agent and platinum. Determination: bismuth, boron, gold, iron, molybdenum, platinum, potassium, and thallium. Biochemical analysis: protein sequencing analysis. It can also be used for environmental protection and pesticide residues analysis. It can also be used for organic synthesis and spices production.
It can also be used as a solvent and for the synthesis of dyes and some kinds of pharmaceutical intermediates.
The above information is edited by the chemicalbook of Dai Xiongfeng.
|Content Analysis||In a pre-dried, constant-weight weighing bottle (with plug), accurately weighed sample of about 1.5g, and moved it into a corresponding flask, then add 20 mL of 0.5 mol sodium hydroxide solution 20.0ml; fit with a reflux condenser; put it in water bath for heating and reflux for about 1h. After cooling, add several drops of phenolphthalein test solution (TS-167), and further apply 0.5mol/L hydrochloric acid for titration of excess amount of sodium hydroxide. At the same time, perform a control test. Each ml of 0.5 mol/L sodium hydroxide solution corresponds to 44.06 mg of ethyl acetate (C4H8O2). |
Use non-polar column method for determination according to the protocol of GT-10-4.
|Precautions||It is one of the synthetic perfumes applied in edible flavor in large dosage and is used in amount in edible flavor used in different kinds of flavors such as banana, pear, peach, pineapple, and grape. |
1. Harm to healthy: it has irritation effect on eye, nose and throat. Inhalation of high concentrations may cause progressive anesthesia, acute pulmonary edema, liver and kidney damage. Continued large number of inhalation can cause respiratory paralysis. Coverage may produce nausea, vomiting, abdominal pain and diarrhea. It also has sensitization effect which causes bleeding gum due to neurovascular disorders; it can cause dermatitis and eczema. Chronic effects: Prolonged exposure to the product sometimes can cause corneal opacity, secondary anemia, and leukocytosis.
2. Explosion Hazard: This product is flammable, irritant, with sensitization.
3. Hazardous characteristics: it is flammable; its vapor can mix with air to form explosive mixtures which cause explosion upon fire and high heating condition. It will have violent reaction when coming across oxidants. Its vapor is heavier than air and can spread to the very distant place at relative lower place. Ignition can occur when it meets fire source.
|The maximum amount as food additives and maximal allowed residue|
|Limited use||FEMA (mg/kg). Soft drinks: 67; cold drink: 99; Candy: 170; Bakery: 170; pudding class: 200; gum: 1400; wine: 50 to 65.
|Chemical Properties||It is colorless, flammable liquid with fruit fragrance. It is miscible with various kinds of organic solvents such as ethers, alcohols, halogenated hydrocarbons, and arene. It is also slightly soluble in water.
|Production method||The direct esterification process is the major route of domestic industrial production of ethyl acetate. Take acetate and ethanol as the raw material, sulfuric acid as the catalyst for direct esterification to obtain ethyl acetate, and then by dehydration, fractionation to obtain refined products. The acetaldehyde condensation method use aluminum alkyl as catalyst, perform the condensation reaction of acetaldehyde to obtain the ethyl acetate. Most foreign industry adopts this technology. Direct esterification of ethylene and acetic acid to obtain ethyl acetate. Ethyl acetate may also be produced from the reaction between acetate and acetic anhydride or vinyl ketone and ethanol; it can also be obtained from the reactions of two molecules of acetaldehyde upon the catalysis of aluminum ethanol. In addition, the industrial production of acetate through butane oxidation can also produce ethyl acetate as byproduct. |
It is derived from the direct esterification between acetic acid and ethanol in the presence of sulfuric acid,
Production process includes: continuous and intermittent.
(1) Gap process. Add acetic acid, ethanol and a small amount of sulfuric acid to the kettle and heat and reflux for 5-6h. Then ethyl acetate was distilled off, and washed with 5% sodium chloride water; further use the mixture solution of sodium hydroxide and sodium chloride for neutralizing to PH = 8. Further apply calcium oxide solution to wash it and add anhydrous potassium carbonate to dry it. Finally distill it, and collect the 76-77 °C fractions to obtain the final products.
(2) Continuous process. Add 1: 1.15 (mass ratio) of ethanol and acetic acid continuously into the esterification column reactor and perform the esterification reaction at 105-110 °C in the catalysis of sulfuric acid. The resulting ethyl acetate and water is distilled out in the tower top in the form of azeotrope; after condensation and stratification, the upper portion of the ester is refluxed with the remaining portion entering into crude tank; the lower layer of water is discarded after the recycling of ethyl acetate. The crude ester went through the distillation tower for removing a small amount of water and then entered into the refining tower again to obtain the final product at the top of the tower. This process is better than gap method.
2 Acetaldehyde methods
Acetaldehyde is converted into ethyl acetate in the catalysis of aluminum ethanol.
Add Acetaldehyde, aluminum ethanol continuously to two reactors in tandem; the reaction was carried out at 0-20 °C with the outlet conversion rate being higher than 99.5% in the second reactor. Then further perform distillation to obtain the ethyl acetate with a yield of 95% -96%. This process is more economical.
|Chemical Properties||Colorless liquid|
|Usage||Suitable for HPLC, spectrophotometry, environmental testing|
|Usage||Meets urethane grade requirements (H2O ≤ 0.05%)|
|Usage||Ethyl Acetate is generally used as a solvent in organic reactions.|
|Acute oral toxicity||rat LD50: 5620 mg/kg; Oral - Mouse LD50: 4100 mg / kg
|Irritation data||eye-people 400 PPM
|Hazardous characteristics of explosive||explosive when mixed with air
|Flammability and hazard characteristics||it is flammable in case of fire, high temperature, and oxidant with burning causing irritated smoke
|Storage characteristics||Treasury: ventilation, low-temperature and dry; store it separately from oxidants
|Extinguishing agent||dry powder, dry sand, carbon dioxide, foam, and 1211 fire extinguishing agent
|Professional standards||TWA 1400 mg / m³; STEL 2000 mg / m³
|General Description||A clear colorless liquid with a fruity odor. Flash point 24°F. Less dense than water. Vapors heavier than air.|
|Air & Water Reactions||Highly flammable. Slightly soluble in water. Ethyl acetate is slowly hydrolyzed by moisture.|
|Reactivity Profile||Ethyl acetate is also sensitive to heat. On prolonged storage, materials containing similar functional groups have formed explosive peroxides. Ethyl acetate may ignite or explode with lithium aluminum hydride. Ethyl acetate may also ignite with potassium tert-butoxide. Ethyl acetate is incompatible with nitrates, strong alkalis and strong acids. Ethyl acetate will attack some forms of plastics, rubber and coatings. Ethyl acetate is incompatible with oxidizers such as hydrogen peroxide, nitric acid, perchloric acid and chromium trioxide. Violent reactions occur with chlorosulfonic acid. . SOCl2 reacts with esters, such as Ethyl acetate, forming toxic SO2 gas and water soluble/toxic acyl chlorides, catalyzed by Fe or Zn (Spagnuolo, C.J. et al. 1992. Chemical and Engineering News 70(22):2.).|
|Health Hazard||Headache, irritation of respiratory passages and eyes, dizziness and nausea, weakness, loss of consciousness.|
|Fire Hazard||HIGHLY FLAMMABLE: Will be easily ignited by heat, sparks or flames. Vapors may form explosive mixtures with air. Vapors may travel to source of ignition and flash back. Most vapors are heavier than air. They will spread along ground and collect in low or confined areas (sewers, basements, tanks). Vapor explosion hazard indoors, outdoors or in sewers. Runoff to sewer may create fire or explosion hazard. Containers may explode when heated. Many liquids are lighter than water.|
|Ethyl acetate Preparation Products And Raw materials|