Synthesis of Butyl Propionate via Fischer Esterification

Sinead Camacho

500744127

TA: Mackenzie Brauer

CHY 142-132
Introduction

Many esters contribute widely to the food industry in artificial flavoring and to the

production of certain odors, since esters possess the characteristic of pleasant smell and taste1.

The flavor and smell of the ester butyl propionate is floral and fragrance like. There are various

uses for butyl propionate however, it is mainly used for painting, appliance coatings or for

automobile repaintings1.

Esters, an organic compound, are produced from the synthesis Fischer Esterification

reaction of a carboxylic acid with an alcohol. This reaction can also be characterized as a kind of

nucleophilic substitution reaction since the alcohol acts as the nucleophile which in turn removes

the hydroxyl group from the carboxylic acid to create an ester functional group1. The ester butyl

propionate will form using propionic acid as the carboxylic acid, and butanol as the alcohol. The

balanced chemical equation for the reaction is:

C4H9OH(aq) + C2H5CO2H(aq) <====> C2H5CO2C4H9(aq) + H2O(l)

Fischer esterification is a reaction that is also acid-catalyzed and reversible. The products

and reactants are in equilibrium. Sulfuric acid is used as a catalyst for this experiment, and

during the experiment, the acid will act as a proton donor to stipulate the reaction with necessary

protons3.

Equilibrium simply means that the reaction can revert and move toward the reactant side.

To prevent this from occurring, an excess of one of the reactants will be necessary so that the

reaction can favor the product side according to Le Chatelier’s principle. This excess reactant,

propionic acid, will cause the reaction to generate more product so that it can alleviate the

tension that is applied on the reactant side3.

 The ratio between the alcohol and carboxylic acid is critical because it determines the

amount of maximum possible yield. For this experiment, the molar ratio between the alcohol and

carboxylic acid is 1:4 as it produces a maximum possible yield of 93%4. When a large amount of

the product is generated, both the ester and water will be present. However, only the ester is the

desirable product, thus, the anhydrous magnesium sulfate dehydrating agent will be necessary in

order to remove the water.

A reflux is performed for one hour on the combined mixture of propionic acid, butanol

and sulfuric acid. The purpose of performing a reflux is to" cook" the reaction, essentially

heating the reaction of the reagents at a constant temperature without letting any of the solvent

escape to evaporation5. Heating under reflux is used in this reaction over any other method

because in order for the reaction to occur, the mixture must be heated, however, the added heat

causes evaporation5. To prevent the solvent from evaporating, a reflux condenser is used to cool

the vapor that has evaporated and sends it back down to the liquid, ultimately resulting in no loss

of the solvent. This is the advantage of performing the lab using a reflux; there is little to no loss

of the heated solvent5.

An extraction is also performed in this lab to separate the components of the mixture that

do not make up the ester6. Not all liquids are miscible which means that some liquids will have

different densities resulting in two layers to form even after they are mixed6. In this lab, the ester

has a lower density than water which means it is insoluble and will be the top layer of the two
 phases. By using a separatory funnel and the process of extraction to separate the aqueous

solution from the organic solution, the ester is obtained6.

To purify the obtained substances, a distillation is performed7. A distillation allows the

separation of liquids from other impure liquids by producing vapor at different boiling points of

the compounds7. When the solution has reached the expected boiling point range of the ester,

evaporation of the pure ester will distill out. This process is completed to purify the solutions.

To test the purity of the obtained ester two tests, the refractive index and infrared

spectroscopy can be performed7. However, in this experiment, only the infrared spectroscopy is

done. Infrared spectroscopy is the analysis of the wavelength of energy (infrared light)

interacting with molecules in the substance7. The functional groups of the literature IR of the

ester is compared to the functional groups produced from the experimental ester for purity.

Table 1: Properties for Reagents and Products2

MP BP Solubility
Weight Physical Density
Compound Formula Structure (°C) (°C) (in water,
(g/mol) Characteristics (g/mL)
at 20oC)

Butyl
130.18 C7H14O2 -89°C 146.8°C Colourless liquid Solubility is poor 0.875
Propionate

Propionic Soluble in water, as well as

74.08 C2H5CO2H -20.5°C 141.15°C Colourless liquid 0.993
Acid alcohol, and ether

Colourless liquid
Soluble in water; and as
Butan-1-ol 74.12 C4H9OH -88.6°C 117.73°C with a strong 0.810
well as ethanol and ether
alcoholic odour

Colourless, volatile
Only slightly in water;
Diethyl Ether 74.12 C4H10O -116.2°C 34.5°C liquid with a putrid, 0.714
soluble in ethanol
sweetish odour

Sodium White hygroscopic, Somewhat soluble in

84.01 NaHCO3 >300°C 851°C 1.50
Bicarbonate odourless powder water; insoluble in ethanol

Colourless, oily
Sulfuric Acid 98.07 H2SO4 10°C 337°C Soluble in water 1.83
liquid

Sodium White crystalline Soluble in water, slightly

58.44 NaCl 800.7°C 1465°C 2.17
Chloride solid soluble in ethanol
Procedure

Part A –Reaction

The reflux apparatus was set up. Using two graduated cylinders and a dropper to obtain

more accurate measurements, 7.3 mL of butanol and 14.4 mL of propionic acid were obtained.

These were combined into a 250 mL round-bottom flask. 2.5 mL of sulfuric acid was added to

the flask and the contents were mixed together. Two to four boiling chips were added to the

mixture to prevent bumping as the solution was heated. A reflux was performed for one hour and

the mixture was heated at a constant temperature to produce the product of the reaction.

Part B –Separation

The reaction contents from the round-bottom flask were transferred to a separatory funnel

using a funnel. 15 mL of diethyl ether was used to wash the reaction flask to ensure all the

mixture was collected. 25 mL of distilled water was added for the first extraction to be done. The

contents were vented under the fume hood and the bottom aqueous layer was removed into a

beaker and discarded. Another extraction using 25 mL sodium bicarbonate was performed. This

extraction was done three times with the sodium bicarbonate in order for the aqueous layer to test

basic using litmus paper. Lastly, an extraction was performed with 25 mL of sodium chloride.

The organic layer was extracted into an Erlenmeyer flask and a small amount of magnesium

sulfate drying agent was added to absorb any traces of water. The flask was swirled, covered

tightly with Parafilm and stored until the next lab period.

Part C –Purification

Simple distillation apparatus was set up. The product was transferred to the distillation

flask using filter paper and a funnel and two to four boiling chips were added. The solution was

heated firstly to the boiling point of diethyl ether in order for all the ether to evaporate out. This
was collected in a small beaker. Once signs showing the distillation had stopped, the remaining

solution was heated to the boiling point of the alcohol followed by the boiling point of the acid

and then finally, the boiling point of the ester. The ester product was collected into a pre-weighed

beaker and was weighed to determine the amount of ester obtained. Infrared spectroscopy was

done to determine the purity of the ester. A few drops of the sample were placed onto the center

of the Agilent Cary 630 spectrophotometer using a Pasteur pipette and the spectrum of the

sample was created through the software. The results were obtained and then transferred to a

USB.

Results and Calculations

Percentage Yield:
Theoretical yield of ester: 10 g
𝐴𝑐𝑡𝑢𝑎𝑙 𝑌𝑖𝑒𝑙𝑑
Weight of beaker used to collect pure ester: 35.3 g %𝑌𝑖𝑒𝑙𝑑 = × 100%
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙

Weight of beaker + pure ester: 36.1 g 0.8 𝑔

%𝑌𝑖𝑒𝑙𝑑 = × 100%
10.0 𝑔
Weight of pure ester: 36.1 g - 35.3 g = 0.8 g
%𝑌𝑖𝑒𝑙𝑑 = 8%

Table 2: Data collected for Reagents and Products

Experimental
Volume/ Literature
Compound Boiling Point
Mass Boiling Point2
Range
Diethyl
15 mL 34.5°C 28-34°C
Ether

Butanol 7.3 mL 117.73°C 100-109°C

Propionic
14.4 mL 141.15°C N/A
Acid

Butyl
0.8 g 146.8°C N/A
Propionate
Figure 1: Literature Infrared Spectrum of Functional Groups of Butyl Propionate8

Figure 2: Experimental Infrared Spectrum of Functional Groups of Butyl Propionate

Table 3: Functional Groups Present in the Infrared Peaks of the Experimental IR Spectrum
Literature Position Sample Position
Functional Group
(wavenumber cm-1)9 (wavenumber cm-1)
Alkane: CH3 2840-3000 2959.548
Alkane: C-H 2840-3000 2874.669
Aldehyde: C=O 1720-1740 1736.068
Ester: C-O 1163-1210 1182.665

Discussion

When making esters through the Fischer Esterification reaction, a carboxylic acid and an

alcohol are the main reactants involved. In this lab, the acid was the excess reagent and the

alcohol was the limiting reagent. This was determined based on the prices of the reagents.

According to the data from the laboratory manual, the acid exhibited a lower price of $47.60

compared to the alcohol which was $74.20 therefore, more of the cheaper reagent and less of the

more expensive reagent were used, and this allowed the lab to be more cost efficient.

During the distillation of butyl propionate, diethyl ether was produced through the

condenser at a boiling point range of 28-34°C. The boiling point range of butyl propionate is

146.8°C (Table 1) therefore, the ether had a range that was lower and more broad and proved

that it was very impure and did not contain contents of the ester. Following the ether came the

butanol and this was produced at a boiling point range of 100-109°C. Attempts to get the

temperature to rise to the boiling point of the propionic acid were to no avail and in turn, led to

no formation of the butyl propionate product through the condenser. The heating mantle was

dropped and this allowed all the condensation to form back to liquid in the flask. After the

distillation was completed, the product that was left in the flask was weighed in a pre-weighed

beaker and the mass was determined. From the initial 10g of butyl propionate that was supposed
to be created, only 0.8 g was produced. This led to a percent yield of 8%, which was much too

low of a yield, harboring a percent error of 92%.

Infrared spectroscopy was performed to further determine the purity of the ester

produced. When comparing the experimental butyl propionate IR to the literature IR, the overall

shape of the spectrum is almost exact except for a few extra peaks in between and on the right

side. However, these extra peaks weren’t taken into much consideration when analyzing, and

may have been due to some impurity from the collected ester. The peaks that were evidently

similar were the functional groups that make up the ester. These functional groups are displayed

on Figure 2 and are provided in Table 3. They provide evidence for the purity of the collected

sample. The literature position ranges for the CH3 and C-H alkane functional groups is 2840-

3000 cm-1. The experimental position for these groups were 2959.548 cm-1 and 2874.669 cm-1

respectively, which clearly shows that they are within the acceptable range. A C=O aldehyde

functional group is also observed at sample position 1736.068 cm-1. This functional group also is

within its acceptable literature range of 1720-1740 cm-1. Lastly, the main functional group of

butyl propionate, an ester, can be observed. The literature position for the C-O ester functional

group is 1163-1210 cm-1 and the sample position was shown at 1182.665 cm-1. The presence of

an OH functional group is what really makes the final product stand out. The absence of an OH

peak in the spectrum indicates that the product went through completion to an ester. All in all,

from the data provided, it shows that the functional group positions are within their acceptable

ranges and when looking at both IR spectrums, the similarities of the functional groups that make

up butyl propionate indicate that the collected sample from the experiment is pure.

Sources of error are sometimes inevitable during laboratory experiments. The low percent

yield could have been due to loss of product during extraction of the aqueous layers and/or that
the reaction may have not gotten enough time to reflux in order to complete the reaction, which

led to less product being collected and more starting material separating out during extraction.

The low yield could have also been due to the evaporation of the product while left stored for a

week, and due to errors in equipment such as a loose joint between the condenser and the flask,

which may have caused the product to escape as vapor. Some product could have also been lost

during transfers between glassware. The actual boiling point of butyl propionate is 146.8°C. The

experimental boiling point temperature was not determined as the temperature was not rising

above 109°C. Impurities such as diethyl ether, alcohol, acid or water left in the solution could

have altered the boiling point and prevented the temperature from rising. These impurities can

also be the cause of the extra peaks in the experimental IR spectrum. This experiment can be

improved by adding more amounts of one of the reactants, in this case the acid, so that the

reaction can go to the right and drive more product. Newer equipment can also be used to

facilitate better results and more time to for the reaction to go to completion should be given.

Conclusion

The purpose of this lab was to synthesize 10g of the ester butyl propionate from a

carboxylic acid and an alcohol. Propionic acid and butanol were identified as the best reagents to

use, making the acid the excess reagent and the alcohol the limiting reagent. Looking over the

data collected, it is evident that a pure sample of butyl propionate was produced since the peaks

from the spectrums and the presence of major functional groups indicate pure results. Although

the percent yield was only 8%, it is fair to say that the lab was completed with limited success

based on the amount of ester produced, but successful in producing a pure sample of butyl

propionate.
References

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