Esterification of an Acid

Synthesis of Banana Oil

Lab 20

Organic Chemistry 211

Fall 2017

Abstract:
As a derivate from carboxylic acids, esters are synthesized from either organic or inorganic acids
through a process called esterification. In this reaction, a carboxylic acid (RCOOH) and an
alcohol (R’OH) mix in the presence of a strong acid catalyst to form a neutral, water-insoluble
ester (RCOO’R) that gives off a pleasant smell.  The following reaction represents the formation
of 3-methylbutyl ethanoate from ethanoic acid, 3-methylbutanol, and an acid catalyst. The
purpose of the experiment performed was to synthesize isopentyl acetate, or more commonly
known as banana oil, from isopentyl alcohol and acetic acid. Both liquids were combined and
remained clear until the addition of concentrated sulfuric acid. The addition of an acid caused a
reaction to occur that resulted in a polymer, which gave the mixture color. The liquid turned dark
brown when the polymer formed. The polymer was removed via distillation.

Introduction:
The Fischer Esterification reaction is driven by shifts in equilibrium. In part, the yield of the
desired ester can never be 100%.  Although the alcohol, 3-methyl-1-butanol was added in excess
to drive the forward reaction, methodologies limit the extent to produce an ester.
Esterification is the process of cleaving hydrogen from the carboxylic acid and a hydrogen along
with an oxygen from the alcohol to form water as a byproduct.  During the reflux of this ester, all
of the substances in the original solution remained in the 100mL round bottom flask; this
included the water byproduct.  As more water was formed, the amount of products began to
surpass the amount of reactants and the reaction started to run in the reverse direction.  Had the
water been dispensed into another container, the reaction would have continuously run toward to
the products.  Conversely, methodological approaches can contribute to an increased yield
resulting from the presence of impurities as well.  The addition of sodium bicarbonate was not
precise; therefore, the amount added may not represent the final amount
In order to yield the highest amount of ester, the solution requires to be refluxed until the
maximum rate of equilibrium is achieved. This process require a reflux condenser apparatus and
a source of heat such as a heating mantle. Although Le Chatlier’s principle states that this
reaction is reversible, using one of the reagents in excess helps to drive the forward reaction to
favor the production of the desired ester. However, if this reaction yields a product it would
contain both an ester (as residual alcohol) and an acid solution. This whole reaction was first
done and called the Fischer esterification. The general reaction scheme can be seen above. In the
experiment, isopentyl alcohol and acetic acid react in the presence of sulfuric acid to form
isopentyl acetate. This reaction mechanism can be seen below

To extract the ester, sodium bicarbonate must be added to the solution to remove the remaining
acid from the catalyst and water entice a reaction of the hydroxyl from the alcohol with the
hydrogen bonding of the water.  The inorganic water layer should easily separate from the ester
as the ester is organic in comparison and will not mix. In the reaction above, Acetic acid takes a
proton from concentrated sulfuric acid. Then it reacts with isopropentyl alcohol. Delocalization
of electrons and protons in later steps leads to elimination of water molecule to form final
product. The final ester product (dry precipitant) can then be placed into an infrared spectrometer
to display bands of photon energy indicative of functional groups within the ester.  The
spectrometer can generate a numeric value to represent the probability that the substance scanned
is an ester.

Materials
Alcohol (benzyl alcohol, isobutyl alcohol, isopentyl alcohol, octanol or 1propanol), carboxylic
acid (acetic acid or proponoic acid), concentrated sulfuric acid, 5% sodium bicarbonate,
anhydrous sodium sulfate, ether, methylene chloride, 25 mL round-bottom flask, water-cooled
condenser, boiling stones, centrifuge tube with cap, transfer pipettes, test tube, small beaker,
spatula.

Methods:
For the esterification reaction we used 23 mL of 3-methyl-1-butanol, 18 mL of ethanoic acid, 2
mL of sulfuric acid, and a stir rod were combined into a 100 mL round bottom flask. We set the
flask over a heating plate and inserted into a condenser apparatus. The flask was heated until
condensed fluids dripped from the top of the apparatus.

After 55 minutes of heating, the flask was removed from the heating mantle and allowed to cool
in a beaker containing room temperature water. Once cooled, the solution was decanted into a
separatory funnel along with 25 mL of cold D.I. water.  An additional 5 mL of cold D.I. water
rinsed the flask to collect any leftover substances left behind. 
The ester/ water solution was inverted and mixed thoroughly; the top was removed so that the
organic and inorganic layers could separate.

 The aqueous inorganic bottom layer was extracted into a collection flask. Sodium bicarbonate
was added to the remaining organic layer in increments of 5 mL. Following each addition of
sodium bicarbonate, the separator funnel was inverted and the stopcock was opened to release
built up pressure, sub sequentially, each newly formed bottom layer was extracted into a
collection flask and tested with litmus paper until a basic pH indicate all sulfuric and ethanoic
acid were removed.
An additional 10 mL of cold tap water was added to the solution, the bottom layer was extracted
and pH level testing steps were repeated.
The remaining organic layer was drained into a 125 mL Erlenmeyer flask containing 1.5 g of
anhydrous calcium chloride. The flask was corked and let sit for 10 minutes while the calcium
chloride absorbed the water. The solution was transferred into a pre-weighed 50 mL round
bottom flask and massed to determine the actual yield of the product.

Data:
The collection of this data was possible by inserting the formulas of the compounds used and the
measured values obtained during lab for calculation at www.onlinechemdatabase.edu. Images
thanks to google.
Table1. Fischer Esterification values
Results:
When 18.00 mL of ethanoic acid, 23.00 mL of 3-methyl-1-butanol, and 2 mL of sulfuric acid
were combined, they produced a solid yellowish colored solution.  The solution was boiled in a
100 mL round bottom flask placed into a heating mantle and reflux condenser apparatus for 55
minutes.   As the reaction progressed, the solution produced a banana-like fragrance.  Following
the reflux, the flask was removed from the apparatus and the solution was decanted into a
separator funnel along with approximately 30 mL of cold deionized water.  The ester portion of
the solution formed a foamy organic layer on the top while the water and alcohol constituted the
aqueous inorganic layer underneath because the density of the ester was less than the density of
water.  The ester solution was flushed with sodium bicarbonate and water to extract all alcohol
and sulfuric acid in the mixture; the pure ester was drained into a beaker with 1.5 g of anhydrous
calcium chloride to absorb the water.  The ester was poured into a 50 mL round bottom flask and
weighed to determine the mass of the ester.  The final product was 7.42 g.  The expected yield of
the ester was 9.45 g; therefore, the percent yield of this reaction was 78.5%.
Upon completing this experiment, the actual yield of the ester was massed at 7.42 g whereas the
theoretically mass of the ester was approx. 9.45 g. and a percent yield of the ester at
approx.78.5%.  The decrease in yield resulted from the use of the acid catalyst, sulfuric acid. 
Although sulfuric acid is necessary to start the reaction, the acid catalyst is capable of driving the
reaction in both the forward and reverse reactions; with a reverse reaction still occurring, the
yield could never be 100%.  This reverse reaction also occurred because of one of the products,
water. 
We were not able to place the final product into the infrared spectrometer for the energy
comparison However, since the compound had identified them as an ester.  There are 3 unique
spikes in the graph that indicate the presence of an ester we can hypothesize the energy levels to
reflect a sp3 hybridized C-H bond and the C=O bond expected to form from the ester.  Finally,
we could predict the presence of a C-O bond from where the alcohol joined with the acetic acid
to form the ester. Based on a comparison with other IR spectra databases found on google, the
spectrometer determined that 935 times out of 1000, the product was the ester 3-methylbutyl
ethanoate. to an increased yield resulting from the presence of impurities as well.  The addition
of sodium bicarbonate was not precise; therefore, the amount added may not represent the
amount necessary to absorb all of the acid present.  Without the proper mass of sodium
bicarbonate added to the final solution, residual acid could have been left behind.  The impurities
in the final product contribute to the increased yield of the ester.
Pictures:

Answers to Conclusion Questions

3. In this experiment, after the reaction mixture was refluxed for 30 min it contained n-
butyl acetate, n-butyl alcohol, acetic acid, water, and sulfuric acid as major components.
Your final product should have been pure n-butyl acetate. What becomes of the other
components of the reaction mixture? (In each case indicate the principal way or ways the
component was removed.) a). n-butyl alcohol, b) acetic acid, c) sulfuric acid, d). water.
The alcohol was removed from the final solution by adding water.  Alcohol is an inorganic
substance that contains hydrogen bonding.  Since alcohol dissolve in water over the organic ester
solution (likes dissolve likes) the hydroxyl end of the alcohol interacts with the hydrogen
bonding of water resulting in the separation of organic and inorganic substances.  The ethanoic
acid and the sulfuric acid were separated from the ester by adding sodium bicarbonate. The
reaction of the carbonate ions with the free H+ ions from the acid produces a carbonic acid
which dissociates into carbon dioxide and water.  The sodium then, reacts with the acetate and
sulfate ions to produce a salt that will dissolve in water over the organic ester solution.
4. Aside from improvements in laboratory technique, how might the percent yield of n-
butyl acetate have been increased? (Hint: Consider the factors that control the
equilibrium composition.) Whose principle is involved?
Sulfuric acid acts as the catalyst for the reaction; it allows the reaction to reach equilibrium.
If the reaction were to continue past 55 minutes, no more products would have been produced
because the esterification reaction is equilibrium based.  The time frame of 50 to 60 minutes is
when the reaction reaches the maximum equilibrium; any further reactivity could drive a reverse
reaction to decrease the yield of the product. Le Chatlier’s principle states that this reaction is
reversible, using one of the reagents in excess helps to drive the forward reaction to favor the
production of the desired ester.
5. Using structural formulas write an equation for the synthesis of ethyl benzoate by the
Fischer method.