Acids and Bases in Organic Chemistry: 1. An Arrhenius Acid Is A Source of H

Acids and Bases in Organic Chemistry
As you work with chemical reactions in organic chemistry, you

will find that you can classify nearly all them as acid-base
reactions. The key to understanding organic chemical reactions
is knowledge of acids and bases. When considering a reaction,
you need to ask three questions: Where's the acid? Where's the
base? How can the acid react with the base?
Three major definitions of acids and bases have influenced the
thinking of chemists.
1. An Arrhenius acid is a source of H⊕ ion.

An Arrhenius base is a source of -OH ion.
2. A Brønsted-Lowry acid is a proton(H⊕) donor.

A Brønsted-Lowry base is a proton(H⊕) acceptor.
3. A Lewis acid is an electron-pair acceptor.
A Lewis base is an electron-pair donor.
A BrØnsted-Lowry acid base reaction results in the transfer of

a proton from an acid to a base.
In an acid-base reaction, one bond is broken, and another one
is formed. The electron pair of the base B: forms a new bond to
the proton of the acid.The acid H—A loses a proton, leaving the
electron pair in the H—A bond on A.
Compiled by Prof. RM Gengan- April 2021

The movement of electrons in reactions can be illustrated using
curved arrow notation. Because two electron pairs are involved
in this reaction, two curved arrows are needed.
• Loss of a proton from an acid forms its conjugate base.
• Gain of a proton by a base forms its conjugate acid.
• A double reaction arrow is used between starting materials and
products to indicate that the reaction can proceed in the forward
and reverse directions. These are equilibrium arrows.
Acid Strength and pKa

Acid strength is the tendency of an acid to donate a proton. The
more readily a compound donates a proton, the stronger an acid
it is. Acidity is measured by an equilibrium constant. When a
BrØnsted-Lowry acid H—A is dissolved in water, an acid base
reaction occurs, and an equilibrium constant can be written for
the reaction.
Because the concentration of the solvent H2O is essentially

constant, the equation can be rearranged and a new equilibrium
constant, called the acidity constant, Ka, can be defined.

It is generally more convenient when describing acid strength
to use “pKa” values than Ka values.
Factors that Determine Acid Strength

Anything that stabilizes a conjugate base A:¯ makes the
starting acid H—A more acidic.
Four factors affect the acidity of H—A. These are:
1. Element effects
2. Inductive effects
3. Resonance effects
4. Hybridization effects
No matter which factor is discussed, the same procedure is
always followed. To compare the acidity of any two acids:
Always draw the conjugate bases.
Determine which conjugate base is more stable.
The more stable the conjugate base, the more acidic the acid.
1. Element Effect
Across a row of the periodic table, the acidity of H—A increases
as the electronegativity of A increases.
Positive or negative charge is stabilized when it is spread over

a larger volume

Down a column of the periodic table, the acidity of H—A increases
as the size of A increases.
2. Inductive Effects
An inductive effect is the pull of electron density through σ
bonds caused by electronegativity differences in atoms.
In the example below, when we compare the acidities of ethanol
and 2,2,2-trifluoroethanol, we note that the latter is more
acidic than the former.
The reason for the increased acidity of 2,2,2- trifluoroethanol

is that the three electronegative fluorine atoms stabilize the
negatively charged conjugate base.

When electron density is pulled away from the negative charge
through σ bonds by very electronegative atoms, it is referred
to as an electron withdrawing inductive effect.
• More electronegative atoms stabilize regions of high electron
density by an electron withdrawing inductive effect.
• The more electronegative the atom and the closer it is to the
site of the negative charge, the greater the effect.
• The acidity of H—A increases with the presence of electron
withdrawing groups in A.
3. Resonance Effects
Resonance is a third factor that influences acidity. In the
example below, when we compare the acidities of ethanol and
acetic acid, we note that the latter is more acidic
than the former.
When the conjugate bases of the two species are compared, it is

evident that the conjugate base of acetic acid enjoys resonance
stabilization, whereas that of ethanol does not.
Resonance delocalization makes CH3COO¯ more stable than

CH3CH2O¯, so CH3COOH is a stronger acid than CH3CH2OH.
The acidity of H—A increases when the conjugate base A:¯ is

resonance stabilized.

4. Hybridization Effects
The final factor affecting the acidity of H—A is the
hybridization of A.
Let us consider the relative acidities of three different
compounds containing C—H bonds.
The higher the percent of s-character of the hybrid orbital, the

closer the lone pair is held to the nucleus, and the more stable
the conjugate base.
Summary of Factors that Determine Acid Strength

Commonly Used Acids in Organic Chemistry
In addition to the familiar acids HCl, H2SO4 and HNO3, a number
of other acids are often used on organic reactions. Two examples
are acetic acid and p-toluenesulfonic acid (TsOH).
Commonly Used Bases in Organic Chemistry

Common strong bases used in organic reactions are more varied
in structure.
It should be noted that:

• Strong bases have weak conjugate acids with high pKa values,
usually > 12.
• Strong bases have a net negative charge, but not all negatively
charged species are strong bases. For example, none of the
halides F¯, Cl¯, Br¯, or I¯, is a strong base.
• Carbanions, negatively charged carbon atoms, are especially
strong bases. A common example is butyllithium. Two other weaker
organic bases are triethylamine and pyridine.

Organic Acids and Bases
Organic acids and organic bases are acids and bases that contain
a carbon skeleton. Within these categories are a number of
classes of neutral proton acids and bases (that is, uncharged
acids and bases.)
Three main types of neutral organic Brønsted-Lowry acids are
carboxylic acids, phenols, and alcohols. Each of these three
functional groups has an —OH group. Each is acidic because of
the electronegativity difference between the oxygen and the
hydrogen involved in the O—H bond. The differences in acid
strength of the three functional groups are due to the
differences in stability of the conjugate base. The most acidic
of the three groups are the carboxylic acids. Carboxylic acids
are characterized by the presence of the carboxyl group.
The reason for the relative strength of the carboxylic acids is

the conjugate base is resonance-stabilized, which makes it a
weak base.
In the carboxylate ion the negative charge spreads over the two
oxygen atoms as a resonance hybrid. This reduces the energy of
the anion and makes the carboxylic acid more acidic.
The second main type of neutral organic acids are the phenols.
Phenols are much less acidic than carboxylic acids. An —OH group
attached to an aromatic ring is characteristic of phenols.
Phenol has a pKa of 10.0 in aqueous media, indicating that in
water only a very small portion of it ionizes.
Phenols are moderately strong organic acids because their

conjugate bases are resonance-stabilized. The aromatic ring is
involved in resonance, which stabilizes the negative charge.

However, this stabilization is less significant than it is for
carboxylic acids for two reasons: the resonance stabilization
of the phenolate ion disrupts the aromaticity of the aromatic
ring, and the resonance stabilization places a negative charge
on the carbon atoms, which, when compared to oxygen, are not
very electronegative.
The third type of neutral organic acids are alcohols. An —OH
group attached to an alkyl group characterizes an alcohol:
Alcohols are much less acidic than phenols. In fact, most
alcohols have an acid strength slightly lower than that of water.
The most common of the organic bases are the amines. Amines are
derivatives of ammonia (NH3) and most are weak bases in aqueous
media.
The pKa of methyl ammonium ion is 10.6 meaning that the methyl
ammonium ion is a relatively weak acid. Thus, methylamine is a
moderately strong base.
Amines are stronger bases than other neutral organic bases
because the nonbonding pair of electrons on the nitrogen is more
available than nonbonding pairs of electrons on other neutral
organic bases. The atoms that are found in these other neutral
organic bases are oxygen, sulfur, or the halogens. Nitrogen
holds its electrons less tightly than these other atoms, so its
compounds are the stronger bases.

Tutorial
1. Identify the strongest acid. Give a reason.
2. Identify the strongest acid. Give a reason.
3. Consider the following pairs of Brønsted-Lowry acids. Which

member of each pair is the stronger acid? Why?
4.
5. Predict the products of the following acid-base reactions.

Indicate the side favored by the equilibrium.
6. Predict whether CH3CH2OH is more acidic or less acidic than

CF3CH2OH. Explain
-------------------------------------------------------------

Bronsted Acidity of Aldehydes and Ketones
The hydrogens of -dicarbonylcompounds are especially acidic
Ionization of a proton from the #-carbon of an aldehyde or a

ketone via attack by a Bronsted base results in formation of an
anion called an enolate.
Compare to the ionization of an proton further removed from the

C=O bond:
Aldehydes and ketones undergo a reaction called the aldol

addition to form -hydroxy aldehydes and ketones:

Under more severe basic conditions, or under acidic conditions,
the reaction proceeds further.
• Dehydration to form an -unsaturated carbonyl compound is
called the aldol condensation:
The base-catalyzed aldol reaction proceeds via an enolate

intermediate:
Aldol condensation occurs under basic conditions.

• Dehydration is more difficult in base because OH- is a poor
leaving group.
• More concentrated base or heat helps to drive the reaction.

TUT. What are the products of?
1.
2.
Claisen Schmidt Reaction

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Acids and Bases in Organic Chemistry

As you work with chemical reactions in organic chemistry, you

1. An Arrhenius acid is a source of H⊕ ion.

2. A Brønsted-Lowry acid is a proton(H⊕) donor.

A BrØnsted-Lowry acid base reaction results in the transfer of

Compiled by Prof. RM Gengan- April 2021

Acid Strength and pKa

Because the concentration of the solvent H2O is essentially

Compiled by Prof. RM Gengan- April 2021

Factors that Determine Acid Strength

Positive or negative charge is stabilized when it is spread over

Compiled by Prof. RM Gengan- April 2021

The reason for the increased acidity of 2,2,2- trifluoroethanol

Compiled by Prof. RM Gengan- April 2021

When the conjugate bases of the two species are compared, it is

Resonance delocalization makes CH3COO¯ more stable than

The acidity of H—A increases when the conjugate base A:¯ is

Compiled by Prof. RM Gengan- April 2021

The higher the percent of s-character of the hybrid orbital, the

Summary of Factors that Determine Acid Strength

Compiled by Prof. RM Gengan- April 2021

Commonly Used Bases in Organic Chemistry

It should be noted that:

Compiled by Prof. RM Gengan- April 2021

The reason for the relative strength of the carboxylic acids is

Phenols are moderately strong organic acids because their

Compiled by Prof. RM Gengan- April 2021

Compiled by Prof. RM Gengan- April 2021

2. Identify the strongest acid. Give a reason.

3. Consider the following pairs of Brønsted-Lowry acids. Which

5. Predict the products of the following acid-base reactions.

6. Predict whether CH3CH2OH is more acidic or less acidic than

Compiled by Prof. RM Gengan- April 2021

The hydrogens of -dicarbonylcompounds are especially acidic

Ionization of a proton from the #-carbon of an aldehyde or a

Compare to the ionization of an proton further removed from the

Aldehydes and ketones undergo a reaction called the aldol

Compiled by Prof. RM Gengan- April 2021

The base-catalyzed aldol reaction proceeds via an enolate

Aldol condensation occurs under basic conditions.

Compiled by Prof. RM Gengan- April 2021

Claisen Schmidt Reaction

Compiled by Prof. RM Gengan- April 2021

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