Objectives: 1. To produce methyl benzoate by esterification. 2. To learn the reaction mechanism involved in esterification.

Introduction: Esters are produced when carboxylic acids are heated with alcohols in the presence of an acid catalyst. The catalyst is usually concentrated sulphuric acid. Dry hydrogen chloride gas is used in some cases, but these tend to involve aromatic esters. Every day fragrances, such as the smell of fresh ground coffee and food flavourings are a combination of esters. However, some esters are readily recognized by their very characteristic flavour or odour.Esters are naturally abundant and readily synthesized, but all have the same structure: RCOOR Esters are derivatives of carboxylic acids, and are mainly p repared by one of four methods, which are direct esterification of a carboxylic acid with an alcohol (Fischer esterification), alcoholysis of acid chlorides, anhydrides, or nitriles, reaction of a carboxylic acid salt with an alkyl halide or sulphate and via the trans-esterification reaction. The reaction between benzoic acid and methanol is an esterificati n process of the benzoic o acid. The acidic hydrogen of the benzoic acid attached to the hydroxide group from the methanol and floats away, whiles the methyl group attaches to the now basic oxygen one the benzoate ion. The end result of this is methyl benzoate. The esterification reaction is both slow and reversible. The equation for the reaction between an acid RCOOH and an alcohol R'OH, where R and R' can be the same or different, is:

For example, the reaction between ethanoic acid and ethanol to produce ethyl ethanoate is:

In the Fischer esterification reaction, esters can be prepared by the reversible, acid catalysed, combination of a carboxylic acid with an alcohol. Because it is reversible, the reaction must be shifted to the product side by using excess reagent, o by removing one of the products. r This reaction is also limited by any steric hindrance in the carboxylic acid or the alcohol. Esters can be prepared by the reaction of a carboxylic acid with an alcohol in the presence of a catalyst such as concentrated sulphuric acid, hydrogen chloride, p-toluenesulfonic acid, or the acid form of an ion exchange resin. This Fischer esterification reaction reaches equilibrium after a few hours of refluxing. The position of the equilibrium can be shifted by adding more of the acid or of the alcohol. The mechanism of the reaction involves initial protonation of the carboxyl group, attack by the nucleophilic hydroxyl,then a proton transfer. Next is the loss of water followed by loss of the catalyzing proton to give the ester. Because each of these steps is completely reversible, this process is also, in reverse, the mechanism for the hydrolysis of an ester. Esters can also be prepared by using a reactive carboxylic acid with an alcohol. Takinga carboxylic acid anhydride or chloride as examples, irreversible fast reactions occur; R(CO)2O + ROH RCOCl + ROH RCOOR + RCOOH RCOOR + HCl

Apparatus and materials: Round bottomed flask(250ml), condenser, separating funnel, Bunsenburner, thermometer, carbon tetrachloride, anhydrous sodium sulphate, benzoic acid, methanol, conc. sulphuric acid and anti-bumping granules.

Procedure:
12.2g of benzoic acid was placed in a 250ml round -bottomed flask and 40ml of methanol was added.

he contents were swirled whilst 5ml of conc. H 2SO4 was carefully added.

he measuring cylinder was washed with 10ml of methanol and the washings added into the flask.

he mixture was refluxed for an hour. After cooling, it was transferred into a 500ml separatory funnel filled with 150ml of water.

he reaction flask was rinsed twice with 40ml of was added to the funnel.

L 4 and this

he ester was extracted using the solvent and the aqueous layer removed. he l4 layer was washed with with 30ml of water,

he ester solution was dried using anhydrous sodium sulphate and then filtered.

he solvent was distilled off on a steam -bath and the residual ester was transferred to a smaller flask. he ester was then o distilled over a Bunsen burner. (b.p. 198 ) he water was run out of the condenser during distillation. he ester was collected in a weighed flask and the distillation temperature range was noted

he percentage theoretical yield was calculated.

lt :

Part 1 Mass of benzoi aci (g) Mass of conical flask (g) Mass of conical flask + product (g) Mass of product (g) 12.2266 73.6397 190.6621 117.0224

Part 2 Product temperature range (oC) 30-90 91-190 191-200

Conical flasks

Mass of conical flask (g)

Mass of conical flask + distillate (g)

Mass of distillate (g)

1 2 3

43.3101 79.7914 73. 6190

133.5371 85.3900 77.0836

90.2270 5.5986 3.4646

Relati e molecular mass, r.m.m., of C6 H5C n (C6 H5C

2H

= 122.12 g/mol

= 12.2266 / 122.12 = 0.10 mol

Densit of CH3OH = 0.7918 g/cm3 Mass of CH3OH = 0.7918 x 50 = 39.59 g r.m.m. of CH3 OH = 32.04 g/mol

n (CH3 OH) = 39.59 / 32.04 = 1.236 mol Hence, t e limiting reagent in t is reaction is C6H5 CO2H n (C6 H5CO2CH3 ) = n (C6 H5CO2 H) = 0.10 mol r.m.m. of C6 H5CO2CH3 = 136.15 g/mol Theoretical yield of C6 H5CO2CH3 = 0.10 x 136.15 = 13.615g Experimental yield of C6 H5CO2CH3 = 3.4646 g Percentage yield of C6H5CO2 CH3 = (3.4646 / 13.615) x 100 % = 25.5 %

Discussion: During this experiment, the percentage yield of methyl benzoate produced was 25.5%. This yield is considered to be low, but reasonable to carried out in the laboratory. The yield could have been affected by some errors made while measuring the materials used, such as adding too much or too little benzoic acid into the mixture. It is also possible that an insufficient amount of the aqueous layer was removed during the separation process. For primary alcohols reacting with carboxylic acids, the equilibrium constant is approximately 4. According to Le Chateliers principle, we can upset the equilibrium we can increase the concentration of either the alcohol or acid. In this experiment, the more effective method would be by adding more benzoic acid since it is the limiting reagent. Another way to upset the equilibrium is to remove water. This can be done by adding molecular sieves, an artificial zeolite, to the reaction mixture, which will adsorb water. Most other drying agents, such as anhydrous sodium sulfate or calcium chloride, will not remove

water at the temperatures used to make esters. Another method to upset the equilibrium is to remove the water as an azeotrope. An azeotropes is a mixture of two or more liquids in such a ratio that its composition cannot be changed by simple distillation At reux temperatures and in the presence of an acid catalyst, both the forward and reverse esterication reactions are rapid and the system comes to equilibrium within a few minutes. In order to obtain a high yield of ester, the equilibrium must be shifted toward the products. One technique for accomplishing this is to use a large excess of one of the reagents, which would be the one that is cheaper. Another method is to remove one or more of the products as it is formed. If the alcohol or the acid contains bulky substituents, the acid-catalyzed esterication maybe very slow or may not occur at all due to steric hindrance. In such cases, conversion of the acid to its acid chloride permits a facile reaction with the alcohol. Some precaution steps have to be taken into consideration when conducting this experiment. Sulphuric acid is very corrosive, hence gloves must be worn at all times. If it comes in contact with the skin, one should ush immediately with large amounts of water. The concentrated acid should never be inhaled either. This is because the inhalation of vapors can cause severe damage to lung tissue. The methanol used is ammable, hence it should be kept away from ignited flames at all times. Protective goggles must always be worn during this experiment to protect the eyes from any splashing of chemicals.

Conclusion: The percentage yield of methyl benzoate through the esterification of methanol and benzoic acid is 25.5%.

References: 1. Esterification. (n.d.). University of Southern Maine. Retreived on 9th April 2011 from http://usm.maine.edu/~newton/Chy251_253/Lectures/Esterification/Esterification.htm l 2. Carboxylic acids. (n.d.). University of Southern Maine. Retreived on 9th April 2011 from http://usm.maine.edu/~newton/Chy251_253/Lectures/CarboxylicAcids/CarboxylicAci ds.html 3. Benzoic acid. (2011, April 8). In Wikipedia, The Free Encyclopedia. Retrieved 10th April 2011 from http://en.wikipedia.org/w/index.php?title=Benzoic_acid&oldid=423070153 4. Esterification. (n.d.). Chemguide. Retrieved on 10th April 2011 from
http://www.chemguide.co.uk/organicprops/alcohols/esterification.html

Questions:

1. How is sulphuric acid involved in the formation of methyl benzoate?

2. The ester solution is washed with alkali to remove unreacted benzoic acid. Given a
two-phase mixture of water and carbon tetrachloride, in which phase would the following concentrate be? (a) Methyl benzoate

(b) Methanol

(c) Sulphuric acid

(d) Benzoic acid

(e) Sodium benzoate

3. Given the equation below, calculate the equilibrium constant Keq for the reaction.
Keq = [C6 H5CO2CH3][H2 O] / [C6 H5CO2 H][CH3OH] =