10.3: Acidity and Basicity of Alcohols and Phenols

Like water, alcohols are weak acids and bases. This is attributed to the polarization of the O–H bond making the hydrogen partially positive. Moreover, the electron pairs on the oxygen atom of alcohol make it both basic and nucleophilic. Protonation of an alcohol converts hydroxide, a poor leaving group, into water—a good one. The two acid–base equilibria corresponding to ethanol are depicted below.

Figure 1. Loss of proton

Figure 2. Gain of proton

Methanol (pK_a = 15.5) is the only alcohol that is slightly stronger than water (pK_a = 15.7). Ethanol (pK_a = 15.9), tert-butanol (pK_a = 18.0), and others are weaker acids. However, all alcohols are stronger acids than terminal alkynes, and they are much stronger than hydrogen, ammonia, and alkanes.

Figure 3. Relative acidity

Since alcohols are weaker acids than water, their conjugate base alkoxide ions are stronger bases than the hydroxide ion. Alcohol can be converted into metal alkoxide using strong bases such as sodium/potassium hydride or sodium/potassium metal, which react violently but controllably with alcohol. When the alkyl substitution is bulky, the alkoxide ion is not solvated enough due to the steric effect, leading to less stabilization. Additionally, destabilization is favored by inductive effects. Consequently, the equilibrium lies predominantly towards alcohol.

Alcohols can also act as a base and accept protons from strong acids. Notably, conjugate bases of compounds with higher pK_a than an alcohol will deprotonate that alcohol.

Figure 4. Relative basicity

Phenols are more acidic than alcohols. The conjugate base of a phenol is a phenoxide or phenolate ion. Resonance stabilization of the phenoxide ion coupled with the polar effect of the benzene ring enhances the acidity of phenols by eight orders of magnitude (100,000,000 times) over cyclohexanol. Therefore, phenol does not need to be deprotonated with a base as strong as sodium hydride. Instead, it can be deprotonated by hydroxide, unlike an alcohol.

Although phenol is a million-fold higher in acidity than ethanol, it is a hundred thousand-fold less acidic than acetic acid. Their relative acid–base properties can be used to separate each other from a mixture. When an ether solution of a mixture of alcohol and phenol is extracted with dilute sodium hydroxide, phenol gets completely partitioned into the aqueous phase as its sodium salt, while alcohol stays in the ether layer. On the other hand, dilute sodium bicarbonate is used to extract phenol and carboxylic acid from an ether solution of their mixture. Carboxylic acid gets quantitatively converted into its sodium salt and gets extracted from water while phenol remains in the ether phase.

Figure 5. Acid–base equilibria of phenol

A phenoxide ion can be stabilized by delocalization of the oxygen's negative charge on the benzene ring. This is reinforced by electron-withdrawing functional groups like nitro, halide, etc. A substantial change in acidity is noted in phenols with an electron-withdrawing substituent, like a nitro group. An ortho- or para-nitro group stabilizes the phenoxide ion by delocalizing the negative charge on its own oxygen atoms. On the other hand, a meta-nitro group, being not directly conjugated to the phenoxide oxygen, stabilizes the phenolate ion to a lesser extent. Therefore, m-nitrophenol (pK_a = 8.4) is more acidic than phenol but less acidic than o- or p-nitrophenol (pK_a = 7.2). This also explains the extremely high acidity of 2,4-⁠dinitrophenol (pK_a = 4.0) and 2,4,6-trinitrophenol (pK_a = 0.4).

Table 1. The acidity constants (pK_a) of acids (blue) and their conjugate bases.

Compound	Acid	Conjugate base	pKa
Hydrogen chloride			−6.30
Nitrophenol			7.07
Phenol			9.89
m-Cresol			10.1
2,2,2-Trifluoroethanol			12.0
Water			15.7
Ethanol			15.9
Cyclohexanol			16.0

While the neutral forms of alcohols and phenols are amphoteric in nature, their corresponding anions form weak bases.

The oxygen atom of an alcohol polarizes both its adjacent bonds. While the polarization of the O–H bond makes alcohol a weak acid, the lone pairs on oxygen make it both basic and nucleophilic. 

The conjugate base of an aliphatic alcohol is an alkoxide ion, and that of a phenol is a phenoxide or phenolate ion. A negative charge is more stable on an oxygen atom than on nitrogen or carbon but most stable on a halogen atom. 

Recall that conjugate base stability is a measure of acidity. Therefore, alcohols are more acidic than terminal alkynes, amines, and alkanes but less acidic than hydrogen halides.      

Typical alcohols like methanol or ethanol are almost as acidic and basic as water. However, phenols are more acidic than alcohols but less acidic than carboxylic acids. Unlike alkoxide ions, the negative charge on the oxygen atom of phenoxide is stabilized by resonance and polarization via its aromatic ring.

Therefore, phenols can be deprotonated by a relatively weak base like hydroxide. However, alcohols can only be deprotonated by stronger bases like sodium metal or potassium metal or sodium hydride with hydrogen evolution.

The acidity of an alcohol is further influenced by the inductive effect and the positions of its substituents, as seen here with fluoride. Trifluoro- and trichloroethanol are stronger acids than ethanol, since their conjugate bases are stabilized by the electron-withdrawing effect of the adjacent halogen atoms.

In phenols, while electron-withdrawing nitro and chloro substituents enhance the acidity, methoxy and alkyl substituents only change it marginally. Naphthols are slightly more acidic than unsubstituted phenol.

The relative gas-phase acidity of alcohols increases from methyl to tertiary because of the polarization effect of α-alkyl substituents.

This trend is reversed in the solution phase due to the solvation effect, which makes a branched tert-butanol molecule less acidic than unhindered ethanol.

Phenol acidity – More acidic than alcohols due to resonance stabilization (eg: phenoxide) Phenoxide ion – Conjugate base of phenol stabilized by resonance (eg: C₆H₅O⁻) Effect of substituents – Nitro groups increase acidity depending on position (eg: para-nitro) Phenol vs ethanol – Phenol is 100,000,000× more acidic than cyclohexanol (eg: pKa 9.89) Phenol extraction – Can be separated from alcohols with dilute NaOH (eg: partitioning

Define Alcohol Acidity and Basicity – Recognize alcohols as weak acids and bases due to their O–H bond polarity (e.g., ethanol) Compare pKa Values – Differentiate acidity among alcohols, phenols, and carboxylic acids (e.g., phenol vs. acetic acid) Identify Resonance Effects – Explain how resonance stabilizes phenoxide ions (e.g., nitrophenol) Explain Mechanism or Process – Describe protonation, deprotonation, and alkoxide formation mechanisms Apply in Context – Use base extraction to separate alcohols from phenols in mixtures (e.g., NaOH vs. NaHCO₃)

What makes phenol more acidic than alcohols like ethanol or cyclohexanol? How do nitro substituents affect the acidity of phenol molecules? What is the difference between phenol and alcohol in acid-base extraction methods?

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