CHEM360 Lab Manual 2009/12 Experiment 10

Experiment 10 Date: 10th June 2018

Student Name: Helen Holy Espedido Student ID: 3330816

Title
Fischer Esterification: An ester from a carboxylic acid and an alcohol.

Purpose/Objective of Lab
This experiment focuses on the synthesis of an ester using a carboxylic acid and an alcohol. The

basic purpose of this experiment is to provide a practical example of the synthesis of an ester, using

the Fischer esterification method.

The product will be purified by distillation and assessed by refractive index. Furthermore, this lab

will help in providing practice in obtaining and interpreting infrared spectra and 1H-NMR.

Introduction:
Esters are naturally abundant and readily synthesized, but all have the same following structure,

Figure 10.2 Structure of Ester

This experiment centers around the synthesis of an ester utilizing a carboxylic acid and an

alcohol. In this reaction, the oxygen on the alcohol serves as the nucleophile. In terms of

nucleophilic strength, this nucleophile is neither a very powerful nucleophile, nor is it a frail

nucleophile, yet rather lies somewhere in the middle of the two extremes. The carbonyl carbon of

the carboxylic acid serves as the electrophile in this Fischer esterification reaction. This

electrophile is a poor electrophile. These two reactants taken together are not sufficiently strong
CHEM360 Lab Manual 2009/12 Experiment 10

to effectively form the ester, as the activation energy is too high, so a few changes in the reaction

must occur to effectively produce the product. Warmth or light are potential changes that aid in

providing a few reactions with enough energy to progress; however, those won't do the trick with

regards to this experiment. Rather, the emphasis is on making one of the reactants stronger.

On the off chance that the alcohol is converted into an oxide, this would make a very strong

nucleophile, actually sufficiently strong to push the Fischer esterification reaction further.

However, the oxide Is additionally a very strong base and will react with the carboxylic acid in

an acid base fashion, rather than the Fischer esterification reaction. The carboxylic acid will be

deprotonated, rather than esterified. Conversion of the carboxylic acid generates a carboxylate,

which is a worse electrophile than the carboxylic acid.

The carboxylic acid can be converted into an acyl halide to effectively form a stronger

electrophile. However, this alteration isn't practical, as these are costly and have restricted

timeframes of realistic usability. Acyl halides can be produced by means of a reaction, however

once more, this isn't practical for this experiment.

To properly carry out the reaction, the reaction is run under acidic conditions. This protonates the

carbonyl oxygen, improving the atom an electrophile. From here, the alcohol is a sufficiently

strong nucleophile to attack the electrophilic carbon, forming a tetrahedral intermediate. A

proton is then lost, at that point picked up on the hydroxyl group of the carboxylic acid. This is

then released as water. At long last, the extra proton appended to the carbonyl group oxygen is

released, resulting in the formation of an ester.

CHEM360 Lab Manual 2009/12 Experiment 10

Equations:

Figure 10.2 Fischer esterification reaction for ester formation from a carboxylic acid.
The acid catalysed mechanism for a Fischer esterification is shown below in Figure 10.3.

Equilibrium is reached at every step in the reaction’s multi-step mechanism. The reaction is driven

to the right, towards the desired end product (i.e., Le Châtelier’s Principle). In this experiment, a

large excess of one of the reactants is used. The acids used in this experiment have a strong

dehydrating capability and help ‘soak up’ the reaction water, also assisting in pulling the reaction to

the right.
CHEM360 Lab Manual 2009/12 Experiment 10

Figure 10.3 Reaction mechanism for the Fischer esterification (under acidic conditions)

Procedure:
Reference to Lab Manual:
Carmichael, Robert. Browne, Lois. Jaleel, Nyron. Shaw, Lawton. Law, David. Last, Arthur.
2017. CHEM 360 Lab Manual, Athabasca University, Canada, 58-60.

Table 10.1 Table of Reagents for Experiment 10 Fisher Esterification.

 CHEM360 Lab Manual 2009/12 Experiment 10

Reagent Formula Mwt. d Mp* Bp* Haz. Properties

(g/mol) (g/ml) (C) (C)

Acetic acid, glacial (conc.) 17.4 M

Isoamyl alcohol (CH3)2CH(CH2) 88.15 130 Irritant

2OH
(3-methyl -1-butanol)

Sulfuric acid, conc. 18 M H2SO4 1.840

Distilled water H2O 18.02 1.000 0 100 none

Diethyl ether

5% sodium carbonate (aq) Na2CO3 (aq)

Sat. sodium chloride (aq) (brine) NaCl (aq)

Calcium chloride (anhydr) CaCl2

acetone, wash

Isoamyl acetate CH3CO2C5H11 130.19 142

Flow Chart:
CHEM360 Lab Manual 2009/12 Experiment 10
CHEM360 Lab Manual 2009/12 Experiment 10

Results & Calculations:

CHEM360 Lab Manual 2009/12 Experiment 10
CHEM360 Lab Manual 2009/12 Experiment 10
CHEM360 Lab Manual 2009/12 Experiment 10

Discussion:
There are three main factors involving the Fischer esterification process, beginning with

the proton source used. The proton source is generally a very strong acid in order to push the

weak base to the product of a protonated carboxylic acid. Sulfuric acid and chloric acid have

been identified as common acids in this procedure. An equilibrium issue also rises from the

Fischer esterification reaction. The overall reaction is an equilibrium reaction. The K eq for this

reaction tends to be approximately 4. The amount of carboxylic acid and alcohol used are kept
CHEM360 Lab Manual 2009/12 Experiment 10

equal to limit the amount of waste generated by the product. Originally, the expected yield for

this reaction is 67%, which is 33% less than normally expected for reactions

Post Lab Question:

Answers to be submitted with report.

1. If the cost of both the alcohol and carboxylic acid were prohibitive,

how would you

maximize the yield of your Fischer esterification product while

keeping costs down?

1) If the cost of both the alcohol and carboxylic acid were prohibitive, one would use a acid as

the catalyst for the Fischer esterification process. The acid would increase the electrophilicity of

the electrophile in the reaction and alcohol would than attack this highly electrophilic species to

yield maximum product from this reaction.

2. Why did you wash your product with water (3X), before washing

it with the solution

of sodium hydrogen carbonate? What was the purpose of washing

with sodium

hydrogen carbonate?

Washing with water ensures all of the acid used as the catalyst is washed off from the reaction

system. Acid-base reaction is exothermic in nature, which generates a lot of heat and may cleave

the ester product (reversal of esterification) formed in the reaction. Thus, water wash is essential

prior to addition of any base (NaHCO3 in this case) in the reaction mixture. Once this is done,
CHEM360 Lab Manual 2009/12 Experiment 10

NaHCO3 (aq) is added to remove any remaining acid present in the reaction. NaOH is a strong

base and would end up hydrolysing the ester product back to the carboxylate. Hence NaOH

cannot be used for washing the reaction mixture.

3. Explain the function of the acid catalyst in a Fisher esterification

reaction.

3) The acid protonates the C=O oxygen and generates a more electrophilic carbon center. This is

then attacked by the nucleophile alcohol oxygen to form ester product as shown below.

4. What would the reactants be to produce isoamyl valerate via

Fischer esterification

reaction?
CHEM360 Lab Manual 2009/12 Experiment 10

Conclusion:

This lab focused on synthesizing an ester product from an unknown carboxylic acid and an

unknown alcohol via Fischer esterification. This reaction was conducted using the alcohol as

solvent to drive the reaction to the products and to drive the expected yield of the reaction closer

to 100%. Once the reaction was complete, the final product was purified by distillation and

assessed by refractive index.