FUJIKAWA, AKI MYRIANE J.

CHEM 31L

EXERCISE 14: REACTIONS OF CARBOXYLIC ACIDS

I. OBJECTIVES
1. To study some of the physical and chemical properties of carboxylic acids; and
2. To understand how esters are formed.

II. RESULTS

Table 14.1 Acidity of Carboxylic Compounds.

Acetic Acid Monochloroacetic Acid Trichloroacetic Acid
pH 3.0 1.2 1.0

Table 14.2 Solubility of Carboxylic Acids in Water and NaHCO3.

Water 10% NaHCO3
Acetic Acid 1 mL (one layer) 0.5 mL (purple solution)
Benzoic Acid >2 mL 2 mL (slowly dissolved)
Oxalic Acid >2 mL 1 mL (dissolved;
effervescence observed)
Lactic Acid 1 mL (one layer) 0.5 mL (effervescence
observed)

Table 14.3 Effect of Oxidizing Agents in Carboxylic Acids.

Alkaline KMnO4 Tollens Reagent
Formic Acid Clear solution with red brick precipitate Silver mirror formed
Acetic Acid Red violet solution with red brick White precipitate
precipitate
Propionic Acid Red wine solution with red brick No silver mirror formed
precipitate
Lactic Acid Yellowish solution with red brick Blackish clear solution
precipitate
Tartaric Acid Yellowish solution with red brick Pale yellow precipitate
precipitate
Citric Acid Yellowish solution with red brick Pale yellow solution
precipitate
Oxalic Acid Black green solution with red brick White precipitate
precipitate
Benzoic Acid Blackish solution with red brick precipitate No silver mirror formed
Water (control) No change in color No silver mirror formed

ESTERIFICATION
Table 14.4 Qualitative Description of Ester
CH3COOH + H2SO4 Sweet, aromatic scent; immiscible in water
CARBOXYLIC ACID AND ITS SALTS
Table 14.5 Qualitative Observation of Reactions of Carboxylic Acid Salts
Observation
Cold water Salicylic acid did not dissolve
Hot water Salicylic acid did not dissolve
Room temperature Crystals were formed
3M NaOH Crystals dissolved
3M HCl Crystals were reformed

III. DISCUSSION
The R group attached to the carboxyl group may increase or decrease the acidity of a
carboxylic acid. Like the carbonyl oxygen of the carboxyl group itself, an R group
that is strongly electron attracting polarizes the O-H bond. The proton is released
more easily, and the acid is stronger. Chlorine is electronegative. If the hydrogen on
the carbon in acetic acid are replaced by one, two, or three chlorine atoms, the
resulting acids are successively stronger. Trichloroacetic acid is more acidic because
of the presence of three chlorine atoms which tend to pull the electrons closer leaving
the Hydrogen more prone to leave.

Carboxylic acids containing up to four carbons are soluble in water. Beyond four
carbons solubility decreases rapidly. This situation is similar to that of alcohols. When
the carboxylic acid has a small hydrocarbon tail the ability of the carboxyl group to
hydrogen bond with water causes the acid to be soluble.

Carboxylic acids are relatively resistant to oxidation. However, some acids, like
alpha-hydroxy acids may be oxidized, such as acetic acid and lactic acid.

Mild oxidizing agents like Tollens reagent are easily reduced by aldehydes to silver
mirror, such as formic acid.

Two evidences of esterification reactions: (1) the change in solubility: the product
ester is not water soluble, hence two layers were formed and (2) a distinct change in
odor: esters are usually sharp and pleasant-smelling.

IV. CONCLUSION
In summary, the structure of compounds plays a vital role in its solubility. For the
acidity of carboxylic acids, electronegativity serves to be vital as well. Moreover,
carboxylic acids are usually resistant to oxidation but there are some compounds that
can undergo oxidation, such as alpha-hydroxy acids.
V. POST-LABORATORY QUESTIONS
1. What is the effect of Cl on the acidity of carboxylic acids?
The Chlorine atom is electronegative which tends to pull electrons closer to it,
leaving the Hydrogen more readily to leave hence making it highly acidic.

2. Explain the effect of the structure of the samples used on solubility behavior.
Carboxylic acids containing up to four carbons are soluble in water. Beyond four
carbons solubility decreases rapidly. This situation is similar to that of alcohols.
When the carboxylic acid has a small hydrocarbon tail the ability of the
carboxyl group to hydrogen bond with water causes the acid to be soluble. As the
hydrophobic hydrocarbon tail grows in size, however, the acids become less
soluble. As is the case with alcohols, the boiling points of carboxylic acids
increase with molecular weight. As the boiling point increases the volatility
decreases.

3. Write the equation showing the ester formation