Ester Synthesis

Shiane Harris

Partner: Laney Gordon

TA: John Kazan

Lab: Monday, 12:00PM Room # PSH-332

October 22, 2018

Abstract:

The learning objective of this experiment was to practice using the techniques previously learned

earlier this semester in lab. Also, it is to acquire knowledge of how to use a new technique in the

context of synthesis of a new molecule from simpler molecules, using glacial acetic acid and

hexanol. The ester synthesis encompassed refluxing the solvent in the presence of sulfuric acid,

which was required to catalyze the reaction. As a result the alcohol was condensed and the ester

product was formed. The product was isolated by extraction using sodium bicarbonate three

times. Afterwards, the product was purified by the anhydrous sodium sulfate. Using infrared

spectroscopy, this product was characterized. The percent yield of the

pure distilled ester product was 52.3%.

Introduction:

Always, performing a synthesis entails caring out multiple procedures. However, the procedures

vary upon the type of synthesis that is being performed. For a single step synthesis it comprise of

performing a reflux to perform the reaction, extraction to isolate the product, distillation to purify

the product, and infrared spectroscopy to characterize the product. The synthesis of hexyl acetate
 from glacial acetic acid requires only one chemical reaction. A ether synthesis reaction is used to

form an ether functional group from the alcohol, hexanol, see Equation 1 in figure 1.

Reaction 1:

Reaction 2:

Glacial acetic acid has an alcohol functional group, which is converted into its

conjugated base anion using a base. The reaction is performed under refluxed in sulfuric acid to

lower the activation energy and reduce the reaction time. Heating is based on boiling point of the

solvent, hexanol. At the end of the reaction the product is isolated by removing the solvent by

extraction of the product. The product is purified using sodium sulfate as a drying technique

instead of using distillation.

A chief issues is determining the chemical yield of the product. This is a measure of how

effectual the reaction is at converting the organic reactant into the anticipated product. The

chemical yield is reduced if there is unreacted reactant. Also, the chemical yield is reduced if

side products are produced due to competing reactions. Furthermore, the chemical yield is

reduced due to the reaction and method conditions preventing the product from successfully

being isolated. The chemical yield is a ratio of the number of moles of the product to the number
of moles of the starting reactant. A low chemical yield suggests one of the setbacks previously

mentioned.

The product formed in the synthesis will be characterized using infrared spectroscopy. An

infrared spectrum will be recorded for the product. This will be compared to the recorded

infrared spectrum of an authentic sample of hexanol. Vibrational peaks consistent with the alkyl

functional group and ether functional group but no alcohol functional group should be observed

in the spectrum of the product. The spectrum of the hexanol should consist of Vibrational peaks

consistent with the alcohol functional group and alkyl functional group but no ether functional

group Observations of these differences between the infrared spectra of the product sample and

the authentic hexanol will provide adequate evidence in support of assigning the product of the

reaction to hexyl acetate. chemical

Experimental:

According to the method described in the Extraction Lab Packet (Arizona State

University, 2018), roughly 1.5 mL of hexanol was added to a pre-weighed round bottom flask.

The flask was weighed after the addition and the weight of the alcohol was calculated to be 1.5 g.

Also, roughly 3.0 mL of glacial acetic acid was added to this flask and was weighed. The weight

of the glacial acetic acid was calculated to be 3.11 g. Therefore, a total of 1.5 g of hexanol and

3.11 g of glacial acetic acid was added to a round bottom flask. 2 mL of sulfuric acid is added as

a catalyst by a Pasteur pipette. The flask was fitted with an air condenser and a drying tube and

the mixture refluxed for 60 minutes. Based on the boiling point of the alcohol the heat is set to

157ºC. After the 60 minutes was up, the mixture was cooled to room temperature and then 3 mL
of 5% sodium bicarbonate solution was added to the flask with a Pasteur pipette. Then a glass

rod was taken to stir the mixture until CO2 bubbles cease to be formed. The bubbles come from

the product of sodium bicarbonate protonation which was carbonic acid reacting with water. The

mixture was transferred to a centrifuge tube and was shaken until two layers form. The aqueous

layer, which contains sulfuric acid and unreacted acetic acid, was removed into a beaker. This

extraction technique is performed two more times. The organic layer is just the ester product.

This was purified using anhydrous sodium sulfate to dry this organic product. Small quantities

were added until there was no more clumping. The purified product was weighed. Then an

infrared spectrum was obtained for the pure liquid product and authentic hexanol sample.

Results:

Based on the weight of 1.50 g, the number of moles of one of the two starting reactants hexanol

was determined to be 0.0517, using Equation 2.

!"#$%& () *"+,&+-& ($) 7.9: $

Moles of reactant = 3 = 7:;.7< $/0(1 = 0.0147 mol
0(1",21+* !"#$%& ( )
456

Based on the weight of 3.11 g, the number of moles of the other starting reactant glacial acetic

acid was determined to be 0.0517, using Equation 3.

!"#$%& () *"+,&+-& ($) >.77 $

Moles of reactant = 3 = ?:.7 $/0(1 = 0.0517 mol
0(1",21+* !"#$%& ( )
456

Based on the weight of 4.1 g, the number of moles of the product was determined to be 0.0284,

using equation 4.

!"#$%& () *"+,&+-& ($) 9 $

Moles of product = 3 = 7@@.;7 $/0(1 = 0.0347 mol
0(1",21+* !"#$%& ( )
456

Using these values, the chemical yield of 64% was obtained for the purified product, Equation 4.

A(1" () B*(C2,& :.:;E@ 0(1

yield = x 100% = :.:7@< 0(1F:.:97< 0(1
x 100 = 52.3%
A(1"D () *"+,&+-&
The product was characterized using infrared spectroscopy, see Figure 1. The characteristic peak

vibration frequencies for those vibrations that can be assigned to a specific functional group are

summarized in Table 1.

Figure 1. ATR infrared spectrum of the pure hexyl acetate sample obtained as the product of the

synthesis reaction

Table 1. Frequencies and assignments for peaks in the infrared spectrum of the pure hexyl

acetate synthesis product.

 Product

sample Functional
Specific Bond
frequency (cm- Group
Vibration
1)

2860 alkyl C(sp3)-H

C(sp3)-H
2957 alkyl

2931 alkyl C(sp3)-H

1739 ester C(sp3)-H

Only peaks with vibration frequencies larger than 1500 cm-1 and that are assigned to specific

functional groups are summarized here.

The product smells like plum.

Discussion:

In this experiment, hexyl acetate was synthesized from hexanol, Equation 1, using glacial acetic

acid in the presence of sulfuric acid which is the catalyst. This reaction has an activation energy

that must be overcome. Therefore, it was performed under reflux for 60 minutes to ensure a

complete reaction. During this reaction the C-O bond in the acetic acid is broken and the O-H

bond in the hexanol is broken. However, a new C-O bond in that broken acetic acid molecule is

made to produce an ester and a new O-H bond in the broken hexanol molecule hexanol is made

to produce water. Due to Le Chatelier’s principle this reaction is irreversible. The boiling point
of the hexanol is 157°C, which was thus the temperature of the reaction. Once the reflux was

complete, the acid acetic acid is EXTRACTED INTO THE aqueous layer by reacting it with the

base sodium bicarbonate that neutralizes the strong acids and also converts them into anionic

form for extraction. Since carbon dioxide gas escapes during this deprotonation, this acid base

reaction is irreversible. Anhydrous sodium sulfate was used to dry away any impurities.

Evidence that hexyl acetate was formed as the product of the reaction was obtained from the

infrared spectrum, Figure 1 and Table 2. The string O-H vibration peak of the starting material is

absent in the product, and the ether functional group is present.

The chemical yield of 42.8% for the pure recrystallized product was considered reasonable.

Losses would have occurred during the reaction due to incomplete product formation, and in the

extraction and anhydrous sodium sulfate drying.

This lab experiment demonstrated many customary techniques that are frequently

encountered when performing ester synthesis, specifically, refluxing a mixture to provide a

stable thermal energy and extraction of in-organic by-products using aqueous layer extraction.

lab experiment also demonstrated techniques learned previously to characterize organic

chemicals in content, specifically, infrared spectroscopy. This lab experiment perfectly

illustrated the impact of thermal energy has on chemical reactions.

Conclusion:
The purpose of this lab experiment was to synthesize hexyl acetate from hexanol. This was

accomplished in 64% yield after purification by anhydrous sodium sulfate and the product was

characterized using infrared spectroscopy. The lab demonstrated the techniques of reflux for

chemical reaction and extraction for isolation and purification, and also infrared spectroscopy for

characterization. The synthesis was found to be successful based on characterization of the

product. Infrared spectroscopy was the only characterization method used.

References Cited:

Arizona State University (2018). Extraction Package. Retrieved from

https://myasucourses.asu.edu/bbcswebdav/pid-19240638-dt-content-rid-

137052823_1/courses/2018Fall-T-CHM235-83632-74516-74515/ExtractionPackage2018g.pdf

Sigma-Aldrich (2018). Sigma-Aldrich Online Catalogue. Retrieved from

http://www.sigmaaldrich.com/unitedstates.html