EFFECT OF THE ACIDITY AND

BASICITY OF ORGANIC COMPOUNDS

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Brønsted-Lowry Acids and Bases
• A Brønsted-Lowry acid is a proton (H+) donor.
• A Brønsted-Lowry base is a proton (H+) acceptor.

Examples of acids and bases:

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 Lewis Acids and Bases
• A Lewis acid is a substance that can accept a pair of electrons.
Examples: H+ , AlCl3, ZnCl2

• A Lewis base is a substance that can donate a pair of electrons.

Examples: OH- , NH3

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 NOTE:

Some molecules contain both hydrogen atoms and lone pairs

and thus, can act either as acids or bases, depending on the
particular reaction. An example is the addictive pain reliever
morphine.

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Question

i. Which of the following molecules is a Bronsted-

Lowry acid?
HBr NH3 CCl4
Bromsted-Lowry acid must contain a proton.

ii. Which of the following is not a Bronsted-Lowry

base?

H3C CH3 O

Bromsted-Lowry bases must have a lone pair or pi bond to

donate.
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Reactions of Brønsted-Lowry Acids and Bases
• 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.

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• 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.
Examples:

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• The Lewis concept of acid-base reaction involves the
transfer of electrons.
• Many organic reactions can be considered to be
reactions of Lewis acids or bases.

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Label the acid, base, conjugate acid and conjugate base in
the following reaction.

O O
+ O CH3 +
HO CH3
H3C CH3 H3C CH2

Use curved arrows to show the movement of electron pairs.

O O
+ O CH3 +
HO CH3
H3C CH2 H3C CH2

H
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Draw the products of the following reaction ( use curved arrows
to show movement of electron pairs)

H3C NH2 + HCl

H3C NH2 + H Cl
H3C NH3 + Cl

H H + H

+ H + H H
H H H

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Basicity of Amines
• Amines are organic bases because they contain a
nitrogen atom, which has a lone pair or unshared
valence electrons. e .g methyl amine (CH3NH2)

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Carboxylic Acids
• These are organic acids. An example is ethanoic acic (CH 3COOH).
• They contain the –COOH functional group.

• In aqueous solution, the acid ionizes with H 2O acting as a base:

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Acidity and Basicity Constant and their uses
• 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.

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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.

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• Hence, a strong acid will have a large Ka value but
a low pKa value.
• A weak acid will have a small Ka value and a high
pKa value.

Therefore as Ka gets larger (stronger acid), pKa gets

smaller. The smaller the value for pKa , the stronger the
acid.

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Factors Affecting Acid Strength
• Factors affecting the acidity are:

Structure of the compound

Electronegative of the atom bonded to hydrogen
Hybridization
Inductive effect
Resonance stability

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Structure of the compound
• Anything that stabilizes a conjugate base A¯ makes the starting acid H—A more acidic (I).

• If HA is more stable than A- then, HA is a weak acid (II).

(I)
• If A- is more stable than HA, then HA is a weak acid (III).

(II)

(III)

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Electronegative of the atom bonded to hydrogen
• This is reflected in the fact that:
The pKa of methanol, CH3O-H = 16,
while the pKa of methane, CH3-H = 43

• This is due to the presence of oxygen (which is more

electronegative than carbon) in methanol.

• Hence, methanol is more acidic than methane because

of the electronegativity of the oxygen atom that is
attached directly to hydrogen.
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Hybridization
• Increasing s-character of the hybrid orbital of the carbon
increases the electronegativity of the carbon.
• Thus leading to increasing polarity and acid strength of the C -
H bond.

The strongest acid of the series yields the anion that is the weakest
base

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Inductive effect
• Ethanoic acid (CH3COOH), pKa = 4.75
Chloroethanoic acid (ClCH2COOH), pKa = 2.81.
Hence, acidity of ClCH2COOH > CH3COOH
• The difference in the pKa value of the two compounds arises
from the inductive effect of the chlorine atom on the molecule.

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Resonance stability
• The more the resonance stability of the conjugate
base of a compound, the more acidic the compound.
E.g., phenol is more acidic than alcohol due to the
resonance stability of the phenoxide ion compared
to the alkoxide ion.

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Basicity Constants and Uses
• A In water, a weak base (NH3) dissociates thus:

Where pKb = - log Kb

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Factors Affecting Base Strenght
The factors affecting the strength of a base
are:
 Structure of the compound
 Hybridization of the compound
 Resonanace

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Structure of the compound
• Amines are basic compounds due to the lone
pair of electrons on nitrogen.
• In aqueous solution, an amine is a weak base
and accepts a proton from water in a reversible
acid-base reaction.

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• If the free amine is stabilized relative to the cation, the
amine is less basic because the acidic proton is not
welcomed by the nitrogen lone pair.

• If the cation is stabilized relative to the free amine, the

amine is a stronger base because the H+ is most welcome
to pick up the lone pair of nitrogen.

• An electron-releasing group, such as alkyl groups, on the

nitrogen increases basicity by increasing the availability of
electrons on the nitrogen

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Hybridization of the compound
• An sp2 orbital contains more s-character than an sp3
orbital; therefore an sp2 nitrogen (being more
electronegative) holds its six electrons more tightly
than the sp3 nitrogen.
• A molecule with an sp2 nitrogen is less basic because
its unshared electrons are more tightly held and the
free nitrogen compound is stabilized rather than the
cation.
• Thus, the lone pair electrons are not available for
sharing with a proton. This is exemplified by the pKa
values of piperidine and pyridine.

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Question

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Resonance
• Resonance stabilization (or lack of it) also affects the base
strength of an amine.
• For example, in an amide
The acyl group due to its electron withdrawing effect
(mesomeric effect), makes the e- pair on the N less available.

• Resonance stabilization, therefore, makes the amide weaker

bases and this explains why amides are at best very weakly
basic in aqueous solutions.

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Questions

1. Calculate the pka’s and which is the stronger

acid? OH CH
3

ka= 10-10 10-41

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2. Which is the strongest base?
H20 (pka= 15.7) NH3 (pka= 38)
CH4 (pka= 58)

3. Draw the products and determine the direction of the

equilibrium.

CH4 + OH

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4. Which of these bases is strong enough to
deprotonate CH3COOH (pka= 4.8) ?

H Cl
pka= 25 35 -7
Both acetylene and hydrogen will work (must
have higher pka)

5. Not using pka, which is the stronger acid?

H2S HBr

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7. Which is the stronger acid? F2CHCH2COOH OR
Cl2CH2COOH

8. Which is the stronger acid and why?

H
H H

B/c the C-H bond involves sp2

hybridized orbital instead of sp3

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9. Which is not a Lewis base?
NH3

Lewis base must have an electron pair to donate.

10. Which is not a Lewis acid?

Br
CH
OH
B
Br Br

None, all are Lewis acids b/c they either contain an

unfilled valence shell or an acidic proton.

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