Properties of Carboxylic Acids and Esters

Purpose : To study the different properties of carboxylic acids and esters.

Apparatus : test tubes, test tube rack, test tube holder, burner, watch glass, beaker, water
bath

Materials : acetic acid, butyric acid, oleic acid, stearic acid, succinic acid, benzoic acid, formic
acid, lactic acid, oxalic acid, methanol, conc. H 2SO4, potassium oxalate, 0.5%
KMnO4, ethyl acetate, methyl salicylate, amyl acetate, ethyl benzoate

Discussion:

Carboxylic acids are structurally like aldehydes (H-C=O) and ketones (C-C=O) in that
they contain the carbonyl group (C=O). The carbonyl carbon is a polar group with the carbon
having a slight excess of positive charge and the oxygen atom having a slight excess of
negative charge. The addition of a second oxygen atom increases the strength of the dipole.
Both molecules are capable of dipole-dipole interactions. One major difference between the
molecules is the hydrogen atom attached to the oxygen atom in carboxylic acids which allows
for the formation of hydrogen bonds between molecules.

However, an important structural difference is that carboxylic acids contain a hydroxyl

group (-OH) attached to the carbonyl carbon. In turn this functional group is called the carboxyl
group (HO-C=O). This combination gives the group an important characteristic; it behaves as
an acid. As a family, carboxylic acids are weak acids, which ionize only slightly in water. As
aqueous solutions typical carboxylic acids ionize to the extent of only one percent or less.

Carboxylic acids are often responsible for many flavors such as the tart taste of vinegar
which is commonly called acetic acid. The sour taste of fruits such as lemons is due to the
presence of citric acid. Unlike carboxylic acids which often have tart tastes or unpleasant
odors, many esters have pleasant flavors and fragrances.

A distinct difference between carboxylic acids and esters is in their odors. Carboxylic
acids are noted for their sour, disagreeable odors. On the other hand, esters have sweet
pleasant odors often associated with fruits; these compounds are used in the food industry as
flavoring agents. For example, while butyric acid gives rancid butter its putrid odor, the ester,
ethyl butyrate, is used as the artificial flavoring agent of pineapple and in other flavorings. The
odor and flavor of oranges is due to octyl propanoate, that of pears due to pentyl propanoate,
and raspberries from 2-methylpropyl methanoate.

Carboxylic acids are an important class of organic compounds. Other important classes
of compounds called acid derivatives are related to acids but differ from them in that the
hydroxyl portion of the carboxyl function is replaced by other groups. Among these acid
derivatives are the acyl halides, anhydrides, esters, and amides.

Acyl halide acid anhydride ester amide

http://www2.ucdsb.on.ca/tiss/stretton/chem3/Lab_13_Ester_Formation
Nomenclature of carboxylic acids

A. IUPAC Names

 Replace the -e in the alkane name with -oic acid.

CH4 methane HCOOH - methanoic acid
CH3—CH3 ethane CH3—COOH ethanoic acid

 Number substituents from the carboxyl carbon 1.

CH3 O
| ║
CH3—CH—CH2—C—OH
4 3 2 1
3 – methylbutanoic acid

Give the IUPAC name of the following acids.

a) CH3CH2CH(Br)COOH _____________________
b) CH3CH(CH3) COOH _____________________

B. Common Names

 List of common names for Unbranched or simple carboxylic acid is found in the topic
aldehydes and ketones.
 For branched or substituted carboxylic acids, locate substituents using , , γ for the
carbon atoms adjacent to the carboxyl carbon.
CH3
γ | 
(a) CH3—CH—CH2—COOH 3-methylbutanoic acid
(-methylbutryic acid)

(b) (c)

Aromatic Carboxylic Acids:

(a) (b) (c)

__________ ________________ ___________________

Dicarboxylic acids: (HOOC-COOH)

Naming of dicarboxylic acids:

 Add the suffix – dioic acid to the name of parent alkane that contains both carboxyl
groups.
 -ane becomes -anedioic acid

https://www.slideserve.com/manon/chapter-10-carboxylic-acids

Common names of dicarboxylic acids:

HOOC-COOH oxalic acid HOOC-CH2CH2CH2-COOH glutaric acid

HOOC-CH2-COOH malonic acid HOOC-CH2CH2-COOH succinic acid
HOOC-(CH2)4-COOH adipic acid HOOC-(CH2)5-COOH pimelic acid

Maleic acid fumaric acid

Phthalic acid isophthalic acid terephthalic acid

Alpha Hydroxy Acids (AHAs)

- Occur naturally in fruit, milk and sugarcane
- Are used in skin care products
Physical properties of carboxylic acids:

 are strongly polar, because of the two polar groups present, the –OH and the C=O
 boiling points are higher than alcohols, ketones, and aldehydes of similar mass
 Low molecular weight acids are soluble in water and they are more soluble than alcohols,
ethers, aldehydes, and ketones because of stronger hydrogen bonding.
 Large carboxylic acids are insoluble in water, however, conversion to a salt greatly
increases the solubility in water.

Chemical Properties:

Carboxylic acids can react with bases to form carboxylic acid salts. Many carboxylic acids
found in food products or medications are found in their soluble salt form rather than as the
acid itself.

The ability to react with sodium bicarbonate (a weak base) and produce a carboxylic acid
salt, carbon dioxide and water is a simple test for the presence of a carboxylic acid functional
group.

Esters are most often produced by the dehydration reaction between a carboxylic acid
and an alcohol. The reaction generally takes place in the presence of an acid catalyst and
produces an ester and water. A saponification reaction involves an ester hydrolysis in the
presence of a strong base and results in the formation of a carboxylic acid salt and an alcohol.
In general the ester is usually insoluble in water while the corresponding carboxylic acid salt
and alcohol (if small) are not.
Nomenclature:

The name of an ester contains the names of

 The alkyl group from the alcohol.
 The carbon chain from the acid with –ate ending.
 - ic of the acid is changed to –ate

O
methyl  ethanoic acid
CH3— O—C —CH3 acetic acid

Alcohol acid part

IUPAC: methylethanoate
CN: methylacetate

Give the (a) IUPAC and (b) Common names of the following esters:
1. O (a)__________________________

CH3—C—O—CH2—CH2—CH3 (b)__________________________

2. CH3(CH2)4COOCH2CH3 (a)___________________________

(b)___________________________

3. CH3(CH2)3COO(CH2)3CH3 (a)________________________

(b)________________________

NOTE: READINGS ABOVE ARE FOR YOUR REFERENCE AND INFORMATION.

Procedures:

1. Solubility/Miscibility in Water and in Sodium Bicarbonate Solution.

a. Place 10 drops of acetic and oleic acid in a separate test tube.

b. Put an equal amount of water in each tube, shake vigorously and observe.
c. Place a pinch of stearic, succinic and benzoic in a separate test tube.
d. Add 3 ml of NaHCO3 solution to each tube shake well and observe.
e. Tabulate your observations in the table shown below.

Carboxylic Acid Solubility/Miscibility in Water Solubility/Miscibility in NaHCO3

Acetic acid
Oleic acid
Stearic acid
Succinic acid
Benzoic acid
2. Action of an Oxidizing Agent on the Carboxylic Acid Group

a. Add 5 drops of acetic acid to 5 ml of 0.5% KMnO4 solution.

b. Heat the solution to boiling in a water bath and note if any reduction of the KMnO 4
occurs.
c. Repeat the test with the following acids: formic, lactic, oxalic and succinic. Observe any
change in color of KMnO4 and tabulate.

Carboxylic Acids Color before heating Color of Solution Color of precipitate

A: Acetic acid
B: Formic acid
C: Lactic acid
D: Oxalic acid
E: Succinic acid

a. What is the name of the oxidizing agent used?___________________________

b. Which of the carboxylic acids above reduced KMnO4 to Mn+2 ________________
c. Which of the carboxylic acids above reduced KMnO4 to MnO2?_______________

3. Oxidizing Property of a Dicarboxylic acid

a. Stain a piece of white cloth by rubbing it against a rusted iron nail.

b. Soak the cloth in a warm solution of oxalic acid for 10 to 15 minutes. What happens to
the stain?_______________________________________________
c. Based on your observation, what application can you suggest about oxalic acid.
__________________________________________________________.

4. Properties of Vinegar: (Vinegar contains 4-6% acetic acid)

4.1 Physical Properties

a) Note the odor, color, taste and reaction of vinegar and acetic acid to red and blue litmus
paper.
b) Record your observations in the table below.

Acids Odor Color Taste Rxn. W/ litmus

Vinegar

Acetic acid

4.2 Detection of Inorganic Substances in vinegar: Test the vinegar for the presence of
carbonates, sulfates, phosphates and halides.

I. Test for Carbonates (CO3-2)

a. Place 5 ml of vinegar in an evaporating dish and evaporate to dryness.

b. Allow cooling and adding 3 drops of conc. HCl to the residue and observe the formation
of bubbles.
c. Give the name of the residue.________________________________
d. What gas is evolved?_______________________________________
 e. Is carbonate present or absent in vinegar?______________________
f. Support your answer if letter (e)_______________________________

II. Test for Sulfates (SO4-2)

a. To 2 ml of vinegar in a test tube, add 1 ml of BaCl2 solution.

b. Note for any formation of solid particles.
c. Is sulfate present or absent in vinegar?__________________________
d. Support your answer in letter (c) of sulfates.______________________
e. What is the color, chemical name and formula of the solid substance formed in procedure
b. _________, _________, ____________

III. Test for Phosphates (PO4-3)

a. To 2 ml of vinegar in a test tube, add 2 ml of 6N HNO3 and 5 ml of ammonium

molybdate solution. Warm in a water bath and observe for any formation of solid
particles.

b. Is phosphate present or absent in vinegar?___________________________

c. Support your answer in letter (c) of sulfates.__________________________

d. What is the color, chemical name and formula of the solid substance formed in procedure
b. ____________, __________, ____________

IV. Test for Halides

a. To 2 ml of vinegar in a test tube, add 5 drops of AgNO3 solution.

b. Observe for any precipitate formed. What is the color, chemical name and chemical
formula of the precipitate?______, ________, ________
c. Is halide present in vinegar?___________________________________
d. Support your answer in procedure c.
e. From the result, what halide is present in vinegar?_________________

5. Esterification

On a watch glass, mix together a pinch of benzoic acid, 5 drops of ethanol and 5 drops of
conc. H2SO4.

Observations.________________________________________________

Equation:___________________________________________________

6. Odor

Note the odor of the following esters: ethyl acetate, methyl salicylate, amyl acetate and
ethyl benzoate. Describe the odors as pleasant, unpleasant, mild or strong odor and then
compare the odor to any familiar substance or to any fruits. Record your observations in the
table shown below.
7. Miscibility and Density

Test the miscibility of each esters in water by mixing 1 ml of the esters listed in the table
below and 1 ml of water. Shake. Take note their relative densities by writing less dense or
denser. Record your observations in the table shown below.

Results:

ESTERS ODOR MISCIBILITY IN H2O DENSITY

Ethyl acetate

Methyl salicylate

Amyl acetate

Ethyl benzoate