Kristin Coleman

CH 213 02
3/15/16

Purpose:

The purpose of this experiment was the saponification of an unknown ester

and identification of the resulting carboxylic acid and alcohol products. To

accomplish this, the ester was steam distilled and the products were isolated and

purified using extraction, drying agents, crstallization and rotary evaporation. The

products were then identified by characterization using gas chromatography,

nuclear magnetic resonace (NMR) spectroscopy and melting point determination.

Procedure:

A powder funnel was used to weigh 1.4 grams of solid NaOH pellets into a

100 mL round-bottomed flask. In order, 0.5 mL of water, 4.1 mL of ethylene glycol,

and 3.0 mL of the unknown ester, along with two Teflon boiling chips and a small

magnetic stir bar, were added to the flask. A lightly greased condenser was attached

to the flask supported by a ring stand and a slow, steady flow of water was started

through the condenser. The round bottomed flask was then lowered into a heating

mantle positioned on top of the magnetic stirrer and refluxed for 30 minutes.

After refluxing was complete, the reaction was cooled in an ice-water bath

and 35 mL of water was poured through the condenser. Two more boiling stones

were added and the apparatus in Appendix 3 was set up to perform a steam

distillation. A heating mantle on top of the magnetic stirrer was used to heat the

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mixture, achieving a distillation rate of 1-2 drops per second. The product was

distilled until the distillate was clear or at least 25 mL of product was collected.

The contents of the distillation pot were then cooled in an ice water bath and

transferred to a 125 Erlenmeyer flask to identify the carboxylic acid. Enough solid

NaCl was then added to the distillate in the receiving pot to decrease the solubility

of alcohol in water. The solution was decanted into a seperatory funnel and 15 mL of

methyl t-butyl ether was added to the round-bottomed flask to dissolve any residual

alcohol product in the flask. The ether was poured into the seperatory funnel and

shaken to extract the alcohol into the upper ether layer. The aqueous layer was

drained into a beaker and the ether solution was poured out of the top of the funnel

into a 50 mL Erlenmeyer flask. The water layer was returned to the seperatory

funnel and extracted again with 10 mL of methyl t-butyl ether and discarded.

The two extracts were combined and dried with anhydrous sodium sulfate.

After 10 minutes the ether solution was decanted into a dry/tared 50 mL round-

bottomed flask. The solution was rotary evaporated and the flask was reweighed. An

NMR spectroscopy was collected after it wad purified using column B in the gas

spectroscopy and performing a Jones Test.

To evaluate the carboxylic acid, HCl was added to the Erlenmeyer flask

containing the salt of the carboxylic acid to allow crystals to form. The product was

suction-filtered and the crude product was weighed and then redissolved in the

minimal amount of water. The solution was heated until it came to a boil and was

taken off the heat to allow crystals to form. The beaker was then submerged in an

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ice water bath to promote formation of crystals and then they were suction filtered,

rinsed with cold water, and transferred to a vial. The carboxylic acid was purified

and tested by using proton NMR and melting point range.

Data:

O O
NaOH
R' + R'OH
-
R O HO-CH2-CH2-OH R O Na+
Reflux

Figure 1: Saponification Reaction Performed

Table 1: Data collected from Carboxylic Acid Identification

Weight of crude product 4.32 g

amount of H2O used 17 mL

Final weight of product 1.18 g

Neutralization equivalent mass 122 g/acid/mol NaOH

Proton NMR Refer to Appendix 1

Melting point range 124-125 °c

Table 2: Data collected from identification of Alcohol

Weight of alcohol before rotary 20.71 g

evaporation

Final weight of alcohol 0.72 g

Proton NMR Refer to Appendix 2

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Figure 2: Alcohol Product, 2-methylproponal

Figure 4: Ester Product, 2-methylpropylbenzoate

Figure 3: Carboxylic Acid Product, Benzoic Acid

Calculations:

A. Carboxylic Acid Calculations

g 3.00 mL 1.46 X

g/mol 192.28 40.0 122.12

mol 0.016 0.0365 X

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Limiting Reactant: Ester

Calculate theoretical yield of carboxylic acid:

3.00 𝑚𝐿 0.0996𝑔 𝑒𝑠𝑡𝑒𝑟 1 𝑚𝑜𝑙 𝑒𝑠𝑡𝑒𝑟

× × = 0.017 𝑚𝑜𝑙 𝐸𝑠𝑡𝑒𝑟
1 1000𝑚𝐿 170.25 𝑔

1.46 𝑔 1 𝑚𝑜𝑙
× 40.0 𝑔 = 0.0365 𝑚𝑜𝑙 NaOH
1

Theoretical yield: TY= (mol of LR) (pdt. coeff./LR coeff.) (molar mass of pdt.)

=(0.016)(1/1)(122.12)= 1.95 g Carboxylic Acid

Calculate percent yield of carboxylic acid:

Actual Yield: 1.18 g

Percent yield = [(Actual Yield Obtained)/(Theoretical Yield)] 100 %

(1.18/1.95) 100% = 60.5 %

Calculate neutralization equivalent mass of carboxylic acid:

12.18 𝑚𝐿 1𝐿 0.1010 𝑚𝑜𝑙

× × = 0.001230 𝑚𝑜𝑙
1 1000𝑚𝐿 1𝐿

0.150 𝑔 𝑎𝑐𝑖𝑑 122 𝑔 𝑎𝑐𝑖𝑑

=
0.001230 𝑚𝑜𝑙 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻

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B. Alcohol Calculations

g 3.00 mL 1.46 X

g/mol 192.28 40.00 74.14

mol 0.016 0.0365 X

Limiting Reactant: ester

Calculate theoretical yield of alcohol:

3.00 𝑚𝐿 0.0996𝑔 𝑒𝑠𝑡𝑒𝑟 1 𝑚𝑜𝑙 𝑒𝑠𝑡𝑒𝑟

× × = 0.017 𝑚𝑜𝑙 𝐸𝑠𝑡𝑒𝑟
1 1000𝑚𝐿 170.25 𝑔

1.46 𝑔 1 𝑚𝑜𝑙
× = 0.0365 𝑚𝑜𝑙 NaOH
1 40.0 𝑔

Theoretical yield =TY= (mol of LR) (pdt. coeff./LR coeff.) (molar mass of pdt.)

(0.017)(1/1)(74.14) = 1.26 g Alcohol

Calculate percent yield of alcohol:

Actual yield: 0.72 g

Percent yield = [(Actual Yield Obtained)/(Theoretical Yield)] 100 %

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(0.72/1.26) 100% = 57.1 %

Discussion:

The reaction performed in this experiment was saponification of an unknown

ester. The saponification reaction involves refluxing the ester in the presence of a

concentrated NaOH solution in ethylene glycol solvent. Ester hydrolysis in a basic

solution is called saponification after the Latin word Sapos, meaning “soap” (666).

Saponification is an example of nucleophilic acyl substitution reaction.

This hydrolysis reaction forms the conjugate base of the acid component as

well as the alcohol component. Ester hydrolysis occurs through a typical

nucleophilic acyl substitution pathway that adds to the ester carbonyl group to give

a tetrahedral intermediate (666). NaOH was the strong base used to saponify the

ester. The saponification reaction was carried out by refluxing the solution using a

steam distillation apparatus. The steam distillation apparatus used to carry out this

reaction is pictured in appendix 3. After the distillation, the salt of the carboxylic

acid was left in the distillate pot and transferred to an Erlenmeyer flask while the

alcohol was distilled over into the receiving pot.

The separated alcohol component was extracted and purified through rotary

evaporation. The addition of NaCl pellets decreased the solubility of the alcohol in

water for the extraction process. The alcohol was extracted with methyl t-butyl

ether and the alcohol went into the ether layer, leaving a bottom aqueous layer that

was discarded. The extracts were dried with anhydrous sodium sulfate to remove

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any water residue, a common organic technique. Rotary evaporation was performed

to eliminate the ether, leaving the alcohol residue.

Gas chromatography was a technique used to make sure that the alcohol

product being analyzed was pure. A sample of the alcohol was injected into the GC

and when the alcohol peak started to plot on the machine, the gas coming out of

Column B on the machine was collected. This small collection of liquid is pure

alcohol. This guaranteed a clean reading of the NMR.

A Jones Test was performed on the alcohol to help narrow down its true

structure. A Jones test is also known as a Chromic Acid oxidation test (notes). This

test can rule out a tertiary alcohol if the test is positive. It is a powerful oxidizing

agent and any easily oxidized compound such as primary and secondary alcohols

will be oxidized in the solution. When the Jones test was performed on the unknown

alcohol, it resulted in a positive test, meaning the alcohol was either primary or

secondary. This data, combined with a proton NMR, can help confirm the structure

of the unknown alcohol.

Assignment of the proton NMR allowed the scientist to determine the

structure of the unknown alcohol (and carboxylic acid). It is one of the most useful

tools for determining a molecule’s structure. Proton NMR determines the relative

amount of different atoms in a compound. It does this by measuring the different

number of hydrogens, arranging them into peaks (in-class notes). In appendix 2, the

proton NMR of alcohol is shown. The hydrogens are arranged into a ratio that helps

to determine where each set of hydrogens fits into the overall structure. There was a

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prominent peak at 1PPM that integrated to 6 hydrogens. This was determined to

symbolize two methyl groups. There was another smaller peak at 1.2 PPM that

integrated to 1 hydrogen and was determined to be a hydroxyl group. The last

prominent peak was located at 3.4 PPM and integrated to 2 hydrogens, making it a

‘CH2’ group.

The Jones test as well as the proton NMR allowed the students to determine

the structure of the alcohol formed during this reaction. The alcohol created in this

reaction was 2-methylpropanol. The Jones test had confirmed that the alcohol was

primary or secondary and the peaks of the NMR correspond to the peaks created by

this specific alcohol.

The carboxylic acid was isolated by extraction and purified by

recrystallization. The carboxylic acid that was isolated in the Erlenmeyer flask was

actually the conjugate base (salt) of the carboxylic acid. To turn the salt into the true

acid, the concentrated HCl solution was added. This is a common organic technique

called protonation. A concentrated HCl solution was used to limit the amount

needed for a precipitate to form. Once the precipitate was formed it was suction

filtered, which created the crude product. The water was added and the product was

recrystallized to get as pure of a product as possible. The minimum amount of water

was used to expedite the reheating process.

One technique used to determine the structure of the carboxylic acid was

melting point range (MPR). The melting point range of the product can help narrow

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down the possibilities of the carboxylic acid and confirm the results of the NMR. The

melting point found for the unknown carboxylic acid was 124-125 °c.

The proton NMR of the carboxylic acid was also done to determine the

structure of the carboxylic acid. Refer to appendix 1 for the proton NMR of the

carboxylic acid. There is a large couplet at 8 PPM that integrates to 5 hydrogens and

it was determined to be the hydrogens that are part of the benzene ring. The singlet

right past 12 PPM integrates to 1 hydrogen and was determined to be the hydrogen

in the hydroxyl group.

The melting point range as well as the proton NMR of the carboxylic acid

helped aid to determine the structure of unknown carboxylic acid. The carboxylic

acid created in the reaction was benzoic acid. The melting point of benzoic acid is

122°c. This confirms the MPR I got for the acid, which was 124-125 °c. The peaks of

the NMR also confirm the identity of the acid because they correspond to the peaks

of benzoic acid.

The ester saponified in this reaction was 3-methylpropylbenzoate. Since both

of the parts of the ester have been identified, they can be put back together to form

the structure of the unknown ester that was saponified. The hydrolysis split the two

compounds and since both compounds were identified, the ester can also be

accurately identified. A proton NMR or IR spectroscopy could prove the structure of

the ester identified.

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Bibliography:

McMurry, John. Organic Chemistry Hybrid: 8th edition. 2012. Brooks/Cole Cengage

Learning. Print.

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