Preparation of Synthetic Scents and Flavors

_________

Laboratory Report

Presented to

Ms. Leonila Adarna

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In Partial Fulfillment

of the Requirements for

CHEA 2102L

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by

Rica Mae P. Pitogo

November 2019
 I. Introduction

Ester, an organic compound in which the hydrogen in the compound’s carboxyl group is
substituted with a hydrocarbon ring, is usually derived from carboxylic acids and alcohol.
Although esters are polar compounds, the absence of direct hydrogen and oxygen bonds are
evident. This property results to esters’ incapability of engaging in intermolecular hydrogen
bonding with one another. Hence, they have considerably low boiling points than their isomeric
carboxylic acid counterparts. Further, they can also engage in hydrogen bonding with water
molecules but esters with low molar mass are somewhat soluble in water. In fact, esters having
low molecular mass are often used as fragrances because of their volatility.

Structural formula of an Ester

Source: https://www.thoughtco.com/definition-of-ester-605106

Esterification is the chemical process in making esters where it involves heating a

carboxylic acid, R-CO-OH, with an alcohol, R’-OH, while removing the water that is formed. In
order for a reaction to perform at a useful rate, a mineral acid catalyst is usually needed. In
addition, esters can also be formed by various other reactions such as reacting alcohol with acid
chloride or anhydride. The ester product is the union of the acyl group from the acid with the
alkoxide group from the alcohol.

Chemical properties of the alcohol, acids and acid catalyst used can affect esterification
reaction rate. Simple alcohols such as methanol and ethanol react quickly because they are
significantly small and contain no carbon atom side chains which can hinder the reaction.
Similar with alcohols, simple acids such as acetic acid or vinegar forms ester very easily. On the
other hand, strong acids such as hydrochloric acid are commonly used as acid catalyst.

Example of a plot of esterification with at a different temperature with constant parameters

Source: https://www.semanticscholar.org/paper/Kinetics-Study-of-Esterification-Reaction-of-Acid-Kong-
Aroua/dfd21d68e99b814c589d0a5b9416d74d45b3a984/figure/5

In this experiment, Fischer esterification is performed which involves heating of the

carboxylic acid with an alcohol in the presence of a strong acid. This reaction is reversible and
thus, to drive the reaction to completion, it should be done through continuously removing the
water formed or using large excess of alcohol.

The mechanism of Fischer esterification starts with the protonation of the carbonyl by the
acid making it activated toward nucleophilic attack. When the nucleophile attacks, proton
transfer happens and the water leaves. Lastly, deprotonation occurs. Significant ester products
of esterification include benyl acetate, linalyl acetate, geranyl acetate, and citronellyl acetate.

Illustration of the mechanism of Fischer Reaction

Source: https://en.wikipedia.org/wiki/Fischer%E2%80%93Speier_esterification

II. Methodology

One of the experiment’s objectives was to synthesize ester using a Fischer Esterification
process. This experiment was done by the following steps with a goal to produce sec-butyl
acetate:

The preparation of the desired ester started with mixing 0.65 moles sec-butyl aclohol,
0.50 moles of acetic acid, and eight grams of concentrated sulfuric acid in a 125-mL distilling
flask. Second, the apparatus needed for reflux was put up. Clay chips were then added into the
flask and the flask was attached to a reflux condenser. It was made sure that the flask was
tightly secured to the set-up using an iron camp. The mixture was then refluxed for 30 minutes.
 Set-up for the reflux
Source: google.com

The set-up used for reflux was rearranged to begin with the distillation process. The
mixture was distilled with low heat until the thermometer read 100 degrees centigrade. After
reaching the desired temperature, first ten drops of distillate was collected using a vial and
about 1 mL of distilled water was poured into it. Separation of layer was evident which indicates
the possible presence of ester. Also, a strong smell of pear was observed during the process.
The distillation was continued until all ester product was collected.

Distillation set-up by the group

Photo taken by Adrian Seth Amaba

10 mL of NaOH was added to the distillate and was shaken without the cork in the flask.
The mixture was then tested for neutrality by using litmus paper. Another 10 mL of NaOH was
added because the product still seemed acidic. After the second addition of NaOH, pH was
tested again and results came back neutral.
 Lastly, the mixture then undergone oxidation of alcohol test through decanting the ester
from the water layer. Potassium dichromate and Sulfuric acid was added to the ester and
brought it to a warm water bath.

III. Presentation and Discussions of Results and Conclusions

Table I. Reactant Information

REACTANT VOLUME USED DENSITY MOLES
Sec-butyl alcohol 59.63 mL 0.808 g/mL 0.65
Acetic acid 28.60 mL 1.05 g/mL 0.50

Table I lists the basic information of the reactants used in preparing the ester. Basing on
the table, sec-butyl acetate is will be formed using Fischer Esterification. Further, the limiting
reactant of this synthesis will be the acetic acid and the theoretical yield is 0.50 mol/65.81 mL of
sec-butyl acetate.

When the experiment was carried out, these are the following information collected:

Table II. Properties of Sec-butyl Acetate

PROPERTY
Chemical Formula C6H12O2
Molar Mass 116.160 g/mol
Appearance Clear liquid
Odor Fruity
Density 0.87 g/cm3 , liquid
Melting Point -99 degrees Centigrade
Boiling Point 112 degrees Centigrade
Solubility in Water 0.80 g / 100 mL
Vapor Pressure 10 mmHg

Table II shows the basic properties of sec-butyl acetate. Sec-butyl acetate is a

compound bearing a chemical formula of C6H12O2. It is a clear flammable liquid with sweet scent
in which it is commonly used as a solvent in lacquers and enamels. Further, this is also used in
the production of acyclic polymers, vinyl resins, and nitrocellulose.

The expected yield of the synthesis is 65.81 mL of sec-butyl acetate. However, about 70
mL of the product was obtained. This then produced 106. 37 % percent yield. This indicates that
the measured product contains impurities that cause the mass to be greater than it actually
would be if the product was pure. A yield with over 100% can also happen when other reactions
are occurring that also formed the product or an incomplete removal of water.
Table III. pH Testing of Ester Product
AMOUNT OF SODIUM HYDROXIDE RESULTS
10 mL blue litmus paper turned red
red litmus paper remained red
20 mL blue litmus paper remained blue
red litmus paper remained red

Table III shows the pH testing of the ester product obtained. In the first addition of 10 mL
of NaOH results to a change of blue litmus paper to red. This indicates that the product is still
acidic. The acidity is due to the presence of the acid catalyst, H2SO4, and the unreacted acetic
acid used in the preparation of ester. Given the result, a second addition of 10 mL was needed
to continue to neutralize the product. This then resulted to a neutral product. In this experiment,
neutralization of acid catalyst and acetic acid is needed to isolate the ester product.

The Jones test which is used in testing for the presence of primary and secondary
alcohol was used in the last part of the experiment. The test came back positive which only
indicates the presence of alcohol and that the preparation and synthesis of the product was
inefficient. Since esterification is a slow and reversible reaction, hydrolysis of ester to carboxylic
acid and alcohol is possible. The reason why the reaction cannot go into completion is that the
reaction is in equilibrium. Thus, it can never shift completely towards the products. Further, the
quick addition of sulfuric acid disallows the reaction to fully mix and the protonation of the acetic
acid occurring at low frequency is also a possible source of error. These instances lead to the
production of more reactants than the product. Hence, the positive test for the presence of
alcohol.

There are also other sources of error such as faulty thermometer that may cause
temperature reading accuracy resulting to either excessive heat or lack of heat and/or
decomposition. Also, faulty Bunsen burner which does not allow the regulation of heat output
can cause hydrolysis, decomposition, and etc. Improper insulation, loss of product during
transfer, contamination, and incomplete removal of water from organic product also contributes
to an error.

In conclusion, the preparation of an ester requires an alcohol, carboxylic acid and an

acid catalyst. In order to obtain desirable amount and purity of the product, one must be keen
and careful in performing the experiment as to avoid errors. Lastly, possible sources of error
indicated beforehand must be known first in order to avoid the generation of error.
 IV. Bibliography

Acetic acid", Ullman's encyclopedia of industrial chemistry (2003, 6th ed., Vol. 1, pp. 170–171).

Weinheim, Germany: Wiley-VCH.

Howard, H. H. (1993). sec-Butyl acetate. In Handbook of environmental fate and exposure data for

organic chemists (Vol. 5, pp. 60–65). Chelsea, MI: Lewis.

PhD, S. C. B. S. (H. (2009, November 17). Families of compounds that occur in essential oils.

Retrieved October 24, 2019, from

https://www.sciencedirect.com/science/article/pii/B9780443104039000030.

Science, C. (2019, July 4). Theoretical Yield and Percent Yield. Retrieved from

https://www.ck12.org/chemistry/theoretical-yield-and-percent-yield/lesson/Theoretical-Yield-and-

Percent-Yield-CHEM/.