Experiment 10

PROPERTIES OF CARBOXYLIC
ACIDS AND ESTERS
I. OBJECTIVES

To study the physical and chemical properties of carboxylic acids: solubility, acidity,

aroma.
To prepare a variety of esters and note their odors.
To demonstrate saponification.

II. INTRODUCTION
Carboxylic acids are structurally like aldehydes and ketones in that they contain the
carbonyl group. However, an important difference is that carboxylic acids contain a hydroxyl
group attached to the carbonyl carbon.

The carboxylic acid group

This combination gives the group its most important characteristic; it behaves as an acid.
As a family, carboxylic acids are weak acids that ionize only slightly in water. As
aqueous solutions, typical carboxylic acids ionize to the extent of only one percent or less.

At equilibrium, most of the acid is present as un-ionized molecules. Dissociation constants,

Ka, of carboxylic acids, where R is an alkyl group, are 10 -5 or less. Water solubility depends
to a large extent on the size of the R-group. Only a few low-molecular-weight acids (up to
four carbons) are very soluble in water.
Although carboxylic acids are weak, they are capable of reacting with bases stronger
than water. Thus while benzoic acid shows limited water solubility, it reacts with sodium
hydroxide to form the soluble salt sodium benzoate. (Sodium benzoate is a preservative in
soft drinks.) Sodium carbonate, Na2CO3, and sodium bicarbonate, NaHCO3, solutions can
neutralize carboxylic acids also.

The combination of a carboxylic acid and an alcohol gives an ester; water is

eliminated. Ester formation is an equilibrium process, catalyzed by an acid catalyst.

The reaction typically gives 60% to 70% of the maximum yield. The reaction is a reversible
process. An ester reacting with water, giving the carboxylic acid and alcohol, is called
hydrolysis; it is acid catalyzed. The base-promoted decomposition of esters yields an alcohol
and a salt of the carboxylic acid; this process is called saponification. Saponification means
soap making, and the sodium salt of a fatty acid (e.g., sodium stearate) is a soap.

A distinctive difference between carboxylic acids and esters is in their characteristic

odors. Carboxylic acids are noted for their sour, disagreeable odors. On the other hand, esters
have sweet and pleasant odors often associated with fruits, and fruits smell the way they do
because they contain esters. These compounds are used in the food industry as fragrances and
flavoring agents. For example, the putrid odor of rancid butter is due to the presence of
butyric acid, while the odor of pineapple is due to the presence of the ester, ethyl butyrate.
Only those carboxylic acids of low molecular weight have odor at room temperature. Highermolecular-weight carboxylic acids form strong hydrogen bonds, are solid, and have a low
vapor pressure. Thus few molecules reach our noses. Esters, however, do not form hydrogen
bonds among themselves; they are liquid at room temperature, even when the molecular
weight is high. Thus they have high vapor pressure and many molecules can reach our noses,
providing odor.

III. EQUIPMENT & CHEMICALS

III.1. Equipment
1.
2.
3.
4.

pH paper (broad range pH 112)

Litmus paper
Pasteur pipet
Hot plate

III.2. Chemicals
1. Concentrated H2SO4
2. Glacial acetic acid
3. Benzoic acid
4. Formic acid
5. Salicylic acid
6. Benzyl alcohol
7. Ethanol (ethyl alcohol)
8. 2-Methyl-1-propanol (isobutyl alcohol)
9. 3-Methyl-1-butanol (isopentyl alcohol)
10. Methanol (methyl alcohol)
11. Methyl salicylate
12. 3 M HCl
13. 6 M HCl
14. 2 M NaOH
15. 6 M NaOH

IV. PROCEDURES
IV.1. Carboxylic Acids and Their Salts
IV.1.1. Characteristics of acetic acid
1. Place into a clean, dry test tube (100 x 13 mm) 2 mL of water and 10 drops of glacial
acetic acid. Note its odor by wafting (moving your hand quickly over the open end of
the test tube) the vapors toward your nose. Of what does it remind you?
2. Take a glass rod and dip it into the solution. Using wide-range indicator paper (pH 1
12), test the pH of the solution by touching the paper with the wet glass rod.
Determine the value of the pH by comparing the color of the paper with the chart on
the dispenser.
3. Now, add 2 mL of 2 M NaOH to the solution. Cork the test tube and sharply tap it
with your finger. Remove the cork and determine the pH of the solution as before; if
not basic, continue to add more base (dropwise) until the solution is basic. Note the
odor and compare to the odor of the solution before the addition of base.
4. By dropwise addition of 3 M HCl, carefully reacidify the solution from step no. 3
(above); test the solution as before with pH paper until the solution tests acid. Does
the original odor return?

IV.1.2. Characteristics of benzoic acid

1. Your instructor will weigh out 0.1 g of benzoic acid for sample size comparison. With
your microspatula, take some sample equivalent to the preweighed sample (an exact
quantity is not important here). Add the solid to a test tube (100 x 13 mm) along with
2 mL of water. Is there any odor? Mix the solution by sharply tapping the test tube
with your finger. How soluble is the benzoic acid?
2. Now add 1 mL of 2 M NaOH to the solution from step no. 1 (above), cork, and mix
by sharply tapping the test tube with your finger. What happens to the solid benzoic
acid? Is there any odor?
3. By dropwise addition of 3 M HCl, carefully reacidify the solution from step no. 2
(above); test as before with pH paper until acidic. As the solution becomes acidic,
what do you observe?

IV.2. Esterification
1. Into five clean, dry test tubes (100 x 13 mm), add 10 drops of liquid carboxylic acid
or 0.1 g of solid carboxylic acid and 10 drops of alcohol according to the scheme in
Table 5.1. Note the odor of each reactant.
2. Add 5 drops of concentrated sulfuric acid to each test tube and mix the contents
thoroughly by sharply tapping the test tube with your finger.
[Caution: Sulfuric acid causes severe burns. Flush any spill with lots of water. Use gloves with
thisreagent.]

3. Place the test tubes in a warm water bath at 60OC for 15 min. Remove the test tubes
from the water bath, cool, and add 2 mL of water to each. Note that there is a layer on
top of the water in each test tube. With a Pasteur pipet, take a few drops from this top
layer and place on a watch glass. Note the odor. Match the ester from each test tube
with one of the following odors: banana, peach, raspberry, nail polish remover,
wintergreen.
Table 10.1 Acids and Alcohols

Test Tube

Carbocylic

No.
1
2
3
4
5

Acid
Formic
Acetic
Acetic
Acetic
Salicylic

Alcohol
Isobutyl
Benzyl
Isopentyl
Ethyl
Methyl

IV.3. Saponification
This part of the experiment can be done while the esterification reactions are being heated.

1. Place into a test tube (150 x 18 mm) 10 drops of methyl salicylate and 5 mL of 6 M
NaOH. Heat the contents in a boiling water bath for 30 min. Record on the Report
Sheet what has happened to the ester layer (1).
2. Cool the test tube to room temperature by placing it in an ice water bath. Determine
the odor of the solution and record your observation on the Report Sheet (2).
3. Carefully add 6 M HCl to the solution, 1 mL at a time, until the solution is acidic.
After each addition, mix the contents and test the solution with litmus. When the
solution is acidic, what do you observe? What is the name of the compound formed?
Answer these questions on the Report Sheet (3).

V. POTENTIAL HAZARDS

H2SO4
- Very hazardous in case of skin contact (corrosive, irritant, permeator), of eye
contact (irritant, corrosive), of ingestion, of inhalation. Liquid or spray mist may
produce tissue damage particularly on mucous membranes of eyes, mouth and
-

respiratory tract.
Wear chemical safety goggles, protective gloves, and clothing to prevent
exposure.

Glacial acetic acid

- Causes severe irritation and burns. May Be harmful if swallowed. Avoid breathing
vapor or dust. Use with adequate ventilation. Avoid contact with eyes, skin, and
-

exposure.
Benzoic acid
- Hazardous in case of skin contact (irritant), of eye contact (irritant), of ingestion,
-

clothes. Wash thoroughly after handling. Keep container closed.

Wear chemical safety goggles, protective gloves, and clothing to prevent

of inhalation. Slightly hazardous in case of skin contact (permeator).

Wear chemical safety goggles, protective gloves, and clothing to prevent

exposure.
Formic acid
- Very hazardous in case of skin contact (irritant), of eye contact (irritant,
corrosive), of ingestion, . Hazardous in case of skin contact (corrosive,
-

permeator).
Wear chemical safety goggles, protective gloves, and clothing to prevent
exposure.
Salicylic acid

Hazardous in case of skin contact (irritant), of eye contact (irritant), of ingestion,

of inhalation (lung irritant). Slightly hazardous in case of skin contact (permeator).

Severe over-exposure can result in death.

Wear chemical safety goggles, protective gloves, and clothing to prevent

exposure.
Benzyl alcohol
- Hazardous in case of skin contact (irritant), of eye contact (irritant), of inhalation.
-

Slightly hazardous in case of skin contact (permeator), of ingestion.

Wear chemical safety goggles, protective gloves, and clothing to prevent

exposure.
Ethanol
- Flammable liquid and vapor. Cause severe eye irritation and moderate skin
irritation.
Wear protective clothing and masker to prevent exposure.
Methanol (methyl alcohol)
- Toxic by ingestion and inhalation. Can be toxic by skin absorption.Affects central
-

nervous system, especially optic nerve.Causes dizziness, nausea, muscle

weakness, narcosis, respiratory failure.Prolonged or repeated skin contact may
cause irritation.
- Wear safety glasses, protective clothing and masker to prevent exposure
HCl
- Corrosive to skin, eyes, nose mucous membranes, respiratory & gastrointestinal
tract.

Inhalation:respiratory

tract

irritation/infection.

Severe

&

fatal

gastrointestinal burns w/necrosis. Severe burns to eyes & blindness. Changes in

pulmonary function, chronic bronchitis,dermatitis, tooth erosion, & conjunctivitis.
- Wear splash chemical goggles , protective gloves, and clothing to prevent exposure.

NaOH
- Mucous membrane irritant. Skin: severe irritation, sensitization, dermatitis & burns.
Eyes: irritation,conjunctivitis& burns. Ingestion: damage to mucous membranes or
tissues.

- Wear protective gloves, and clothing to prevent exposure.

VI. QUESTIONS AND PROBLEMS
VI.1. Pre-Lab Questions
1. Write the structures of the following carboxylic acids:
a)
acetic acid
b)
formic acid

c)
salicylic acid
2. Write the products from the reaction of benzoic acid and sodium hydroxide.
3. Octylformate has the flavor of oranges. Name the alcohol and the carboxylic acid
needed to synthesize this ester.
4. What is a soap?

VI.2. Post-Lab Questions

1. How do carboxylic acids and esters differ in their characteristic odors?
2. Write equations for each of the five esterification reactions.
3. Benzoic acid and diphenyl ketone are both insoluble in water. Suggest a method for
separating a mixture of these compounds.

VII. REPORT FORMAT

Name ______________

Date

______________

Partner ______________

Lab. Assistant ______________

REPORT SHEET

Carboxylic acids and their salts

Characteristics of Acetic Acid
Property

Water Solution

NaOH Solution

HCl
Solution

Odor
Solubility
pH
Characteristics of Benzoic Acid
Property

Water Solution

NaOH Solution

HCl
Solution

Odor
Solubility
pH
Esterification
Test Tube

Acid

Odor

Alcohol

Odor

Ester

Odor

1
2
3
4
5
6

Name ______________

Date

______________

Partner ______________

Lab. Assistant ______________

REPORT SHEET

Saponification
1. What has happened to the ester layer?
2. What has happened to the odor of the ester?
3. What forms on reacidification of the solution? Name the compound.
4. Write the chemical equation for the saponification of methyl salicylate

Potensi Bahaya
H2SO4
- Sangat berbahaya dalam kasus kontak kulit (korosif, mengiritasi, permeator), kontak mata
(iritan, korosif), menelan, inhalasi. Cair atau kabut semprotan dapat menghasilkan kerusakan
jaringan terutama pada selaput lendir mata, mulut dan saluran pernapasan.
- Kacamata keselamatan Wear kimia, sarung tangan pelindung, dan pakaian untuk mencegah
pajanan.
asam asetat glasial
- Menyebabkan iritasi parah dan luka bakar. Mungkin berbahaya jika tertelan. Hindari
menghirup uap atau debu. Gunakan dengan ventilasi yang memadai. Hindari kontak dengan
mata, kulit, dan pakaian. Cuci sampai bersih setelah menangani. Simpan wadah tertutup.
- Kacamata keselamatan Wear kimia, sarung tangan pelindung, dan pakaian untuk mencegah
pajanan.
Asam benzoat
- Berbahaya dalam kasus kontak kulit (iritan), kontak mata (iritan), menelan, inhalasi. Sedikit
berbahaya dalam kasus kontak kulit (permeator).
- Kacamata keselamatan Wear kimia, sarung tangan pelindung, dan pakaian untuk mencegah
pajanan.
Asam format
- Sangat berbahaya dalam kasus kontak kulit (iritan), kontak mata (iritan, korosif), menelan,.
Berbahaya dalam kasus kontak kulit (korosif, permeator).
- Kacamata keselamatan Wear kimia, sarung tangan pelindung, dan pakaian untuk mencegah
pajanan.
Asam salisilat
- Berbahaya dalam kasus kontak kulit (iritan), kontak mata (iritan), menelan, inhalasi (paruparu iritan). Sedikit berbahaya dalam kasus kontak kulit (permeator). Parah over-exposure
dapat mengakibatkan kematian.
- Kacamata keselamatan Wear kimia, sarung tangan pelindung, dan pakaian untuk mencegah
pajanan.
Benzil alkohol
- Berbahaya dalam kasus kontak kulit (iritan), kontak mata (iritan), inhalasi. Sedikit
berbahaya dalam kasus kontak kulit (permeator), menelan.

- Kacamata keselamatan Wear kimia, sarung tangan pelindung, dan pakaian untuk mencegah
pajanan.
Etanol
- Cairan dan uap yang mudah terbakar. Menyebabkan iritasi mata dan iritasi kulit moderat.
- Kenakan pakaian pelindung dan masker untuk mencegah pajanan.
Metanol (metil alkohol)
- Toxic oleh konsumsi dan inhalasi. Dapat menjadi racun oleh absorption.Affects kulit sistem
saraf pusat, terutama optik nerve.Causes pusing, mual, kelemahan otot, narkosis,
failure.Prolonged pernapasan atau kontak kulit berulang dapat menyebabkan iritasi.
- Gelas Wear keselamatan, pakaian pelindung dan masker untuk mencegah pajanan
HCl
- Korosif terhadap kulit, mata, selaput lendir hidung, pernapasan & saluran pencernaan.
Inhalasi: iritasi saluran pernapasan / infeksi. Parah & mematikan gastrointestinal membakar
w / nekrosis. Luka bakar yang parah mata & kebutaan. Perubahan fungsi paru, bronkitis
kronis, dermatitis, erosi gigi, & konjungtivitis.
- Kacamata Wear percikan kimia, sarung tangan pelindung, dan pakaian untuk mencegah
pajanan.
NaOH
- Lendir membran iritasi. Kulit: parah iritasi, sensitisasi, dermatitis & luka bakar. Mata:
iritasi, konjungtivitis & luka bakar. Tertelan: kerusakan membran mukosa atau jaringan.
- Pakailah sarung tangan pelindung, dan pakaian untuk mencegah pajanan.