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Synthesis and Purification of 1-Butyl Ethanoate in Laboratory for Organic Chemistry

Mohd Afiq Mohd Asri Chemistry 12 Period 3, International Canadian Pre-University, Taylors College, Wisma Subang Jaya, Jalan SS 15/4, 47500 Subang Jaya, Selangor Darul Ehsan. mohdafiq.mohdasri@sd.taylors.edu.my

Completed on 30 November 2010.

Abstract: Synthesis of butyl ethanoate through esterification is a common laboratory exercise in organic chemistry. The objective of the laboratory is to enlighten Chemistry 12 students about the reactions of organic compounds from functional groups ester, alcohols and carboxylic acid. Students also receive handson experience handling esterification reaction as well as purification via separation and distillation.

Introduction Esters are one of the functional groups of organic chemistry learned in the Chemistry 12 course. Esters are chemical compounds derived by reacting an oxoacid with a hydroxyl compound. Basically, esters are formed by condensing an acid with an alcohol.[1] In this process, the hydroxyl group (-OH) of the carboxylic acid is replaced by an alkoxy group (RO) of the alcohol. Esters have special properties compared to other chemical compounds; notably the fragrance it produces depending on what chemical composition it is made from. The classic synthesis is the Fischer esterification, which involves treating a carboxylic acid with an alcohol in the presence of a dehydrating agent:
RCOOH + R'OH RCOOR' + H2O

The mechanism of the Fischer esterification is as shown below. The mineral acid used as catalyst in the following example is concentration hydrochloric acid.

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The first step involves protonation (addition of H+) of the carbonyl oxygen which increases the electrophilicity of carbonyl carbon, followed by the nucleophillic attack of the alcohol, finished off with the loss of a proton. Again protonation of one of the alcohols occur and followed by loss of water. Electrons from the oxygen come down to form the double bond. The loss of a proton yields the ester.[2] In simpler words, the RC=O in the ester originates from the carboxylic acid and the OR comes from the alcohol. For this experiment, the alcohol used is butanol and the carboxylic acid used is ethanoic acid. Concentrated sulphuric acid is used as the catalyst. The chemical equation for the esterification of butanol and ethanoic acid is given as the following:
CH3COOH + CH3CH2CH2CH2OH CH3COOCH3CH2CH2CH3 + H2O

The experiment should provide students with a deeper understanding on organic chemistry; particularly on the physical and chemical properties esters, alcohols and carboxylic acids.

Background The name ester is derived from the German Essig-ther (literal: vinegar ester), an old name for ethyl acetate. [3] Fischer esterification is a type of esterification by refluxing carboxylic acid and alcohol in the presence of an acid catalyst. The reaction was first described by Emil Fischer and Arthur Speier in 1895.[4] It is the most common type esterification procedure done in school laboratories. The process of esterification is not new in our modern industry as it was dated back about 100 years ago. However, at that time, they had no modern technology to equip themselves to carry out this experiment easily. 1-butyl ethanoate, is an organic compound commonly used as a solvent in the production of lacquers and other products. It is also used as synthetic fruit flavouring in foods such as candy, ice cream, cheeses, and baked goods.

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1-butyl ethanoate, CH3COOCH3CH2CH2CH3 has the following molecular structures:

Diagram 1.0 line skeletal formula for 1-butyl ethanoate

Diagram 1.1 structural formula for 1-butyl ethanoate

Butyl ethanoate is found in many types of fruit, where along with other chemicals it imparts characteristic flavours. Apples, especially of the Red Delicious variety[5], are flavored in part by this chemical. It is a colourless flammable liquid with a sweet smell of banana.

Experimental Supplies. 1.0M butanol, C4H9OH; 1.0M ethanoic acid, CH3COOH, 1.0M concentrated sulphuric acid, H2SO4, 100.00 mL distilled water, H2O; anhydrous calcium chloride chips, CaCl2; 0.5M sodium carbonate, Na2CO3; boiling chips, Bunsen burner, retort stand, measuring cylinder, 100 mL round-bottom flask, Liebig condenser, quickfit apparatus, thermometer, beaker, reagent bottle, separatory funnel, filter funnel, filter papers, Vaseline lubricant. Hazards. Safety goggles are to be worn at all times. Do not point the tip of the separatory funnel to anyone when releasing gas pressure during purification process. Joints of the Liebig condenser may break when detached after experiment if not properly lubricated. Boiling chips is used during heating to reduce vigorousness of the reaction to ensure the glassware does not break. Handle sulphuric acid and sodium bicarbonate with care as they are corrosive. Reading of the temperature at purification must be taken immediately as the purified ester begins to form during reflux. Procedures. Step A. The Liebig condenser is to be set-up as following:

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Diagram 1.2 set-up of Liebig condenser[6]

20 mL butanol and 20 mL of ethanoic acid are measured using measuring cylinders. The measured solutions are then added into a round bottomed flask containing 3 pieces of boiling chips. 1 mL concentrated sulphuric acid is added into the mixture. The solution is heated and refluxed for 30 minutes. The heat source is then removed and solution is allowed to cool. Impure 1-butyl ethanoate produced is then filtered and transferred into a reagent bottle. Step B. Impure 1-butyl ethanoate is added into a separatory funnel. 40 mL of distilled water is added to the ester. The separatory funnel is stopped and the mixture is shaken. Tilt the funnel so that the tip is pointed upwards. Turn the stopcock to release gas pressure accumulating in the funnel. The stopcock is then closed and the funnel is set upright. As two separate layers are formed in the separatory funnel, the lower layer is removed. 40 mL of sodium carbonate is added into the remaining mixture. The mixture is shaken and gas pressure is released. Two separate layers are formed in the separatory funnel and the lower layer is again removed. 40 mL of water is added into the remaining mixture. The mixture is shaken and gas pressure is released. Two separate layers are formed in the separatory funnel. The lower layer is removed and the remaining mixture is extracted into a beaker. Step C. The extract is poured into a beaker and anhydrous calcium chloride chips are added into the flask. The beaker is swirled and the extract is filtered into a round bottom flask. The extract is then refluxed using a Liebig condenser and pure 1-butyl ethanoate is retrieved. The temperature at the time when the pure ester starts to form is recorded. The colour and odour of the extract is observed.

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Results The product yielded from the experiment was 1-butyl ethanoate. The temperature when the pure ester flows out of the condenser is 124C. The first reaction produces a purplish coloured liquid while the extract is colourless after the purification process. Butyl ethanoate has a pungent odour similar to thinner.

Discussions H2SO4 acts as a catalyst to the reaction. The acid provides the H+ ions required for the protonation mechanism as explained in introduction. Esterification reaction is a reversible process that obeys the Le Chateliers principle. As the reaction is reversible, the yield of 1-butyl ethanoate cannot achieve 100%, especially under standard temperature and pressure. At equilibrium, the product yielded is an impure ester containing mixture of 1-butyl ethanoate with unreacted butanol and ethanoic acid. The yield of ester may be increased by having one of the reactants in excess amount, as the equilibrium is favoured towards the product side. The impurities in the mixture need to be removed in order to obtain pure 1-butyl ethanoate, hence the purification process is required. In the purification process, the mixture was washed thrice using different chemical compounds. During the separation step of the purification process, an understanding of the difference in densities of butyl ethanoate, sodium ethanoate and water is essential. Butyl ethanoate has the density of 0.88 g/cm3 [1], water has density of 1.00 g/cm3 and sodium ethanoate has density of 1.53 g/cm3 [7]. The differences in densities are vital in forming the separated layers of the mixture during the separation. The purpose of the first wash using distilled water is to dissolve the excess butanol. Butanol is soluble in water. Butanol-water solution is denser than butyl ethanoate and forms the lower layer. The dissolved butanol is then removed from the separatory funnel. The purpose of washing the ester mixture with sodium carbonate, Na2CO3 is to make it react with ethanoic acid to form sodium ethanoate, CH3COONa; water, H2O and carbon dioxide gas, CO2:
Na2CO3 + 2CH3COOH 2CH3COONa + H2O + CO2

The second wash using distilled water is to separate the layers of sodium ethanoate and the 1butyl ethanoate. The difference in densities causes the water to act as the middle layer that separates the denser sodium ethanoate and the lesser dense 1-butyl ethanoate. This allows the sodium ethanoate to be removed. Anhydrous calcium chloride is added to the extract to remove the remaining water residue from the extract. The beaker is swirled to ensure the dehydration is even and thorough. Also, during the separation process, the stopcock had to be opened a few times at regular intervals to release gas pressure. The pressure is caused by the production of carbon dioxide gas, CO2 which is a by-product of the reaction of the mixture in the separatory funnel. If the separatory funnel is not opened at regular interval, glassware will break due to accumulated pressure.

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The boiling point of 1-butyl ethanoate is 126C[5]. At the boiling point, the ester begins to vaporise into gas. The vapour is condensed by the Liebig condenser, reverting the vapour back into liquid pure 1-butyl ethanoate and flows out of the condenser. The difference between the actual boiling point and the value obtained from the experiment is due to the presence of impurities in the extract which lowers the boiling point of the solution. The difference is also due to the fact that human error could have occurred when the temperature was taken.

Conclusion 1-butyl ethanoate can be synthesized in a laboratory by esterification reaction of butanol and ethanoic acid using concentrated sulphuric acid as a catalyst. The reaction must be done using a condenser. The experiment does not yield 100% 1-butyl ethanoate hence the product has to be purified to obtain pure ester. This method of ester synthesis is suitable for the purpose of educating Chemistry 12 students regarding organic reactions as it can be carried out easily in a school laboratory and is economical.

References 1. Ester. Wikipedia, the free encyclopedia. Wikimedia Foundation, 19 Nov. 2010. Web. 28 Nov. 2010. 2. Clark, Jim. The Mechanism for Esterification Reaction. ChemGuide.co.uk, 2004. Web. 29 Nov. 2010. 3. Ester. WorldLingo, n.d. Web. 29 Nov. 2010. 4. Fischer-Speier esterification. Wikipedia, the free encyclopedia. Wikimedia Foundation, 21 Oct. 2010. Web. 26 Nov. 2010. 5. Butyl ethanoate. Wikipedia, the free encyclopedia. Wikimedia Foundation, 22 Nov. 2010. Web. 26 Nov. 2010. 6. Figure 11-1.jpg. Blenders and Beakers. 16 May 2009. Web. 29 Nov. 2010. 7. Sodium ethanoate. Wikipedia, the free encyclopedia. Wikimedia Foundation, 23 Nov. 2010. Web. 30 Nov. 2010.