Discussion:

1. Acidity and structure

Acetic acid is the least acidic amongst all of these

Explanation: The strength of acidity of an acid can be explained in terms of its ease with which it can
release its proton and it is directly proportional to the no of ''-I '' groups attached to it. “-I” groups are
those groups which tend to attract the sigma bond pair electron cloud towards themselves. Chloride ion
is one such group. When these groups are attached to an acid they attract the sigma bond pair electrons
towards themselves by means of inductive effect and as a result the electron density on the carbon
holding the proton is reduced as compared to the unsubstituted acid as a result it is much easier for the
carbon in that substituted acid to release its proton (Hydrogen ion) as compared to the unsubstituted
acid. The more no of -I groups attached, the more strongly this effect will take place, and the more easily
the proton will be lost and more acidic it will be.

Trichloroacetic acid> Dichloroacetic acid>Monochloroacetic acid > Acetic Acid

2. Solubility in water and in 10% NaHCO3

The solubility of
carboxylic acids in water is similar to that of alcohols, aldehydes, and ketones. Acids with fewer than
about five carbons dissolve in water; those with a higher molecular weight are insoluble owing to the
larger hydrocarbon portion, which is hydrophobic. Acetic acid among the acids has the smallest
structure (number of carbons) which is why it dissolves almost instantly in water. Oxalic acid dissolves
faster in water and NaHCO3 because it had a smaller amount of carbon atoms than lactic acid at the
same time it had more of the carbonyl and hydroxyl groups to its carbon enabling it to readily hydrogen
bond to water and NaHCO3 than lactic acid. In the case of the benzene. It did not dissolve in water
because of the presence of the aromatic benzene which is a large (contains a high number of carbon)
hydrophobic group. In the solubility in NaHCO 3 (sodium bicarbonate) all of the acids were able to
dissolve even the benzoic acid. This is because of the acid-base reaction between them. Benzoic acid is a
weak acid that will dissolve in weak base such as sodium bicarbonate.
 Second answer:

Solubility in water The carboxylic acid do not dimerize in the presence of water. Instead,
hydrogen bonds are formed between water molecules and individual acid molecules. Hence, carboxylic
acid up to four carbon atoms are fairly soluble in water. However, solubility decreases rapidly with
increase in hydrophobic part (hydrocarbon tail) of carboxylic acid molecules. This is because the longer
hydrocarbon chain of acid molecules tends to break hydrogen bonds. Thus, strong hydrogen bonds are
replaced by weaker vander waals dispersion forces in such cases.

Formic Acid Should not oxidize (should oxidize)

Ans: Formic acid is a carboxylic acid with the formula of
CH2O2 and is easily oxidized to carbon dioxide. Other
carboxylic acids are not as easy to oxidized.

Acetic Acid Should not oxidize

Propionic Should not oxidize (mali)

acid

Lactic acid Oxidize

Tartaric acid Oxidize

Citric acid Oxidize

Oxalic acid Should not oxidize

Benzoic acid Should not oxidize

 The reaction of formic acid, lactic acid, tartaric acid and citric acid to the KMnO4 is due to
oxidation reaction. Carboxylic acids are relatively resistant to oxidation but a-hydroxy acids such as lactic
acid, tartaric acid and citric acid can be oxidized to form carbon dioxide and aldehydes. While formic
acid with a hydrogen attached to the carbonyl carbon can oxidize directly to become a carbon dioxide.
Benzoic acid, propionic acid and acetic acid did not oxidize because they lack the a-hydroxy group.
Oxidation reactions generally break carbon hydrogen bonds and form carbon oxygen bonds. This is not
possible in most carboxylic acids since the carbonyl carbon does not contain any hydrogen and it already
is filled with the maximum amount of bonds to oxygen. The oxidation of a-hydroxy acids occurs with the
hydroxy group instead of the carbonyl group transforming it into a carbonyl compound breaking the
carboxylic acid to form CO2.

3. Carboxylic acid and its salts

When we put the test tube containing the salicylic acid in a cold water the salicylic acid did not dissolve.
Whereas in the hot water the salicylic acid did dissolve. Salicylic acid is soluble in water, but only small
amounts will dissolve at room temperature. Increasing the temperature increases the solubility just like
many other substances such as sugar and table salt, the hotter the water, the more will dissolve.

Adding Sodium hydroxide (Basic) (NaOH) to the salicylic acid(acidic) caused an acid-base reaction which
is why the salicylic acid crystals dissolved in NaOH to form sodium salicylate. When we added HCl (an
acid) to the solution. The sodium salicylate reacted to form back to Salicylic acid and also form Sodium
chloride. Which is why the crystals reformed after adding HCl. When an acid (Salicylic acid) and a base
(NaOH) are placed together, they react to neutralize the acid and base properties, producing a salt
(Sodium Salicylate). The addition of HCl which is a strong acid would attract the Na+ ions to the Cl- to
form another salt NaCl and the H+ from the HCl would bond with the salicylate to reform the salicylic
acid.

Conclusion: In conclusion, the structure of the compounds plays an important role in its solubility.•
Electronegativity plays a big role on the carboxylic acid’s acidity.• Carboxylic acids are usually resistant
to oxidization but there are some cases that they can be oxidized
Questions:

1. What is the effect of Cl on the acidity of carboxylic acids?

- Cl is electronegative which tends to pulls electrons closer to them leaving the hydrogen
more readily to leave at the same time decreasing the likeliness of the hydrogen to bond
back to the oxygen in the carbonyl making it highly acidic.
2. Explain the effect of the structure of the samples used on solubility behavior.

- Solubility in water The carboxylic acid do not dimerize in the presence of water. Instead,
hydrogen bonds are formed between water molecules and individual acid molecules. Hence,
carboxylic acid up to four carbon atoms (acetic acid, oxalic acid and lactic acid) are fairly
soluble in water. However, solubility decreases rapidly with increase in hydrophobic part
(hydrocarbon tail) of carboxylic acid molecules (for example in benzoic acid). This is because
the longer hydrocarbon chain of acid molecules tends to break hydrogen bonds. Thus,
strong hydrogen bonds are replaced by weaker vander waals dispersion forces in such cases.
The sodium, ammonium, and potassium salts of carboxylic acids, however, are generally
quite soluble in water. Thus, almost any carboxylic acid can be made to dissolve in water by
converting it to such a salt, which is easily done by adding a strong base
3. Write the equation showing the ester formation

Reactions of carboxylic acid derivatives.

Discussion:

Acid chloride and Anhydrides reaction with water

Acyl chlorides react readily with water to form carboxylic acids in a nucleophilic addition
elimination reaction. The carbon atom in the -COCl group has both an oxygen atom and a chlorine atom
attached to it. Both of these are very electronegative. They both pull electrons towards themselves,
leaving the carbon atom quite positively charged. It is that carbon atom which is attacked by one of the
lone pairs on the oxygen atom in a water molecule. The acetyl chloride molecule is also planar (flat)
around that carbon atom, and that leaves plenty of room for a nucleophile to attack either from above
or below the plane of the molecule. Acid anhydrides also follow a similar reaction with acid chlorides
except that it produces 2 carboxylic acids and the reaction is a much slower process. After adding silver
nitrate, the test tube with the acyl chloride reacted, this is because of the presence of chloride ions in
the solution with the acyl chloride. Hydrolysis of acyl chlorides results to a carboxylic acid and
Hydrochloric acid (HCl) which contains a Chlorine molecule that readily reacts with silver to form a salt
AgCl3
Esters

Acid hydrolysis of acetyl salicylic acid

The addition of HCl and water to acetyl salicylic acid results to the formation of salicylic acid and
acetic acid. This acid catalyzed hydrolysis of acetyl salicylic acid is an equilibrium reaction. The addition
of ferric chloride can serve as a test for any presence of a phenolic group. The purple color is is due to
the formation of ferric salicylate complexes.

Esterification

The addition of concentrated acetic acid and isopentyl alcohol in the presence of sulfuric acid
results to the formation of esters. The aroma of the bananas produced is due to the formation of
isoamyl acetate, an ester, formed from the esterification of isopentyl alcohol and acetic acid.

Questions:

1. Write the equations that describe the reaction mechanism for the hydrolysis of:
a. Acetyl chloride

b. Acetic anhydride
- Base hydrolysis
 2. Explain why acetyl chloride reacts faster with water than acetic anhydride does.
- The chloride ion in the acetyl chloride inductively withdraws electron density from the
already electrophilic carbon of the carbonyl group making it very reactive compared to acid
anhydride
-
- The determining factor for the reactivity is the electrophilicity of the carbonyl C; with a more
electron-withdrawing group, the electrophilicity rises (and Cl- is a relatively good leaving
group, which also speeds up the process). The acetyl group is also a relatively good leaving
group, but the carbonyl attached just isn't quite as reactive.

Conclusion: