Acid-Base Strength of Organic Compounds

Background

The relative acidity of organic molecules plays a large role in their reactivity and physical properties. Knowledge of pK as
is critical for predicting acid-base reactions and understanding extractions in organic chemistry lab.

In aqueous solution, an acid reacts with water to form hydronium ion (H3O+) and its conjugate base, known as acid
hydrolysis. A base reacts with water to form hydroxide (OH-) and its conjugate acid, known as base hydrolysis.

Acid Hydrolysis:

Base Hydrolysis

A strong acids have conjugate bases (A-) that stabilize a negative charges – the more stable the conjugate base, the
more the equilibrium gets pushed to the right. The pH scale is based on hydronium concentration, and the more
hydronium, the more acidic the solution and the lower the pH. If the conjugate base has resonance, it helps to stabilize
the negative charge thus resulting in a stronger acid. For instance, carboxylic acids are more acidic than alcohols because
their conjugate bases are resonance stabilized.

O O O
+ H2O H3O+ +
OH O O

OH + H2O H3O+ + O

In aqueous solution, bases produce hydroxide, which lowers the hydronium concentration and raises the pH. All bases
have lone pairs. If a lone pair is conjugated or involved in resonance it decreases the basicity because protonation
interrupts those stabilizations. For instance, pyridine’s lone pair is perpendicular to the aromatic ring. When pyridine
acts as a base and picks up a proton, it does not lose its aromaticity. Pyrrole’s lone pair is part of an aromatic system and
the aromaticity is lost during protonation. Therefore, pyridine is more basic than pyrrole.

N + H2O OH - + N H still aromatic

pyridine

H
N H + H2O OH - + N lost aromaticity
H
pyrrole
Procedure

50% ethanol solutions of benzenesulfonic acid, benzoic acid, benzyl alcohol, benzylamine, p-cresol, and p-toluidine will
be prepared ahead of time. Obtain a well plate and transfer 5 drops of each solution into the separate wells and 1 drop
of universal indicator solution into each well. Assume that the benzyl alcohol solution is neutral (neutral 50% ethanol
solutions will not have a pH of 7). Decide which compounds are acidic and which are basic. Arrange the compounds
from most acidic to least acidic and compare the acidity/basicity order to your original prediction. Explain why the
compounds are ordered as they are and try to account for any differences with your original ordering.

OH
O OH OH NH 2
O S O OH NH2

CH 3 CH3
benzenesulfonic benzoic benzyl benzylamine p-cresol p-toluidine
acid acid alcohol