Acidic And Basic Character

of Organic Compounds
Chemistry @ MBCC
Science Year 2

3.1 Explain the difference in

acidity of alcohols, phenols
and carboxylic acids

Acidity
Acidity may be defined by:
the tendency of compound to yield hydrogen in
H2O (Arrhenius acid)
The ability to donate H+ (Bronsted-Lowry acid)
the ability to accept an electron pair to form a
covalent bond (Lewis acid)

Acid Strength
The strengths of weak
acids are measured
on the pKa scale
The smaller the pKa,
the stronger the acid
is
pKa = -log10Ka
The larger the Ka, the
stronger the acid
In terms of acidity:
Ethanoic acid >
phenol > ethanol

Acidity of Alcohols
Alcohols are extremely weak acids

Acidity of Alcohols
See page 316 of Maraj and Samai.
1. Can you explain the trend in the table below?
2. What is an alpha () carbon?

Acidity of Alcohols
As the number of alkyl groups attached to the -C increases:
Electron density of the -C increases.
-

Alkyl groups are donating electron density and pushes

electron density onto the -C (positive inductive effect)

Oxygen in the alkoxide ion becomes more negatively

charged and wants to hold on to the hydrogen more
(polarity of O-H bond decreases)
The alkoxide anion is less stable and the alcohol is less
ready to lose a proton
In terms of acidity of alcohols:
10 alcohol > 20 alcohol > 30 alcohol

Acidity of Phenols

Acidity of phenols is dependent on the stability of the

phenoxide ion
In the phenoxide ion, the lone pairs on oxygen becomes
delocalised and overlaps with the pi ring system of the
benzene ring
The electron on the oxygen of the phenoxide ion is therefore
less available to accept a proton and go back to the phenol
The pH of a typical dilute solution of phenol in water is likely
to be around 5 - 6 (depending on its concentration)

Acidity of Phenols
Any substituents on the benzene ring which stabilizes the
phenoxide ion makes the compound more acidic
Can you explain the trend in acidity as shown below:

Hint:
Are the groups on the benzene ring Electron Donating Groups
(EDGs) or Electron Withdrawing Groups (EWGs)?

Acidity of Phenols

Answer:
EDGs such as alkyl groups and alkoxide groups makes the
benzene ring more electron rich and reduces the extent of
delocalization of the oxygen lone pair into the aromatic ring. The
electron density on oxygen remains and is available to accept a
proton less acidic
EWGs such as COOH, NO2 and Cl make the benzene ring more
electron poor. The lone pair of the oxygen is therefore delocalized
to a large extent into the pi ring system and is less available
more acidic

Acidity of Carboxylic Acids

Carboxylic acids partially ionise in solution and the strength
depends on equilibrium constant

Acidity depends on the stability of the carboxylate ion. The more

stable the ion, the less readily it will recombine with H+ ions to
reform the carboxylic acid

Acidity of Carboxylic Acids

The carboxylate ion is resonance-stabilized unlike the

alkoxide ion in phenols
The negative charge is spread (delocalized) over both
the oxygen atoms and will be unavailable to accept a
proton
Carboxylate ion is protonated less easily than
phenoxide ion and alkoxide ion, therefore, carboxylic
acid is more acidic than phenols and alcohols

Phenols vs. Carboxylic Acids

In carboxylate ion, the negative
charge is equally distributed over
two electronegative atoms (oxygen
atoms) while in phenoxide ion, it is
present only on one oxygen
Carboxylate ion is more stabilized
than phenoxide ion. Hence,
carboxylic acids ionize to the greater
extent than phenols furnishing higher
concentration of H+ ions
Therefore carboxylic acids behave as
stronger acids than phenols

Acidity of Carboxylic Acids

Electronegative atoms for eg. Cl
on the carbon chain pulls electron
density to itself and away from
the carboxylate group
This leads to a loss of electron
density from the oxygen atom,
which decreases the ability of the
COO- ion to accept a proton

pKa

Carboxylic acid
CH3COOH

4.76

CH2ClCOOH

2.86

CHCl2COOH

1.29

CCl3COOH

0.65

The greater the amount of

electronegative atoms and the
closer in proximity to the COOgroup, the stronger the acid

Carboxylic acid

pKa

CH2FCOOH

2.66

CH2ClCOOH

2.86

The more electronegative the

atom, the stronger the acid

CH2BrCOOH

2.90

CH2ICOOH

3.17

Acidity of Carboxylic Acids

pKa

Carboxylic acid
CH3CH2CH2COOH

4.82

CH3CH2CHClCOOH

2.84

CH3CHClCH2COOH

4.06

CH2ClCH2CH2COOH

4.52

The chlorine is effective at withdrawing charge when it is

next-door to the -COO- group, and much less so as it gets
even one carbon further away
The greater the amount of electronegative atoms and the
closer in proximity to the carboxylate group, the stronger
the acid

Acidity of Carboxylic Acids

Can you explain the trend in acidity of the following acids?
pKa

Carboxylic Acid
HCOOH
CH3COOH

3.75

CH3CH2COOH

4.87

CH3CH2CH2COOH

4.82

4.76

The less the charge is delocalized, the less stable the ion, and the
weaker the acid
Alkyl groups have a tendency to "push" electrons away from
themselves. That means that there will be a small amount of extra
negative charge built up on the -COO - group
Any build-up of charge will make the ion less stable, and more
attractive to hydrogen ions
The more alkyl groups present, the weaker the acid

3.2 Explain differences in

basic character of aliphatic
amines, amides and
aromatic amines

Basicity
Basicity may be defined by:
The ability of a substance to accept a
proton
The ability to donate an electron pair
-

Basicity is measured in the degree of

availability of lone pair for conjugation with
acids

RNH2 + H2O RNH3 +

OH-

Basicity
The lower the pKb the more basic the compound
Can you account for the trend below?

Basicity
pKb

Base
NH3

4.74

CH3NH2

3.36

CH3CH2NH2

3.27

CH3CH2CH2NH2

3.16

Amines are basic because the lone pair on nitrogen is

available to form a dative bond with an H + ion in solution
All aliphatic primary amines are stronger bases than
ammonia
In terms of basicity:
30 amines > 20 amines > 20 amines

Basicity of Amines
As the number of alkyl groups attached increases, the
basicity of the amine increases as well
- EDGs push electron density onto the nitrogen atom
- The N is more electron rich and the lone pair is more
available for forming a dative bond with H+
(CH3)3N: >

(CH3)2NH > CH3NH2

Basicity: Aromatic Amines

Aromatic amines are weaker bases
than aliphatic amines
Phenylamine is a weaker base
than methylamine
In phenylamine the p orbitals of
nitrogen (which contain the lone
pair) can overlap with the ring
system and become delocalized in
the ring system (conjugative
effect)
Delocalization means the lone pair
is unavailable to accept a proton
weaker base than methylamine

pKb

Base
NH3

4.74

Methylamine

3.36

Phenylamine

9.38

H2N

Basicity: Amides
The lone pair on the N atom is
almost parallel to the p orbitals
on C and O and overlaps with
them as they form the pi bond

http://www.chemguide.co.uk/organicprops/amides/other.html

Basicity: Amides
the lone pair on N is unavailable to accept a proton
because they are used up in the delocalized electron
cloud
Amides show little or no tendency to accept a
proton and hence are very weak bases, almost
neutral
Amides are not soluble in dilute HCl as simple
amines because of lesser availability of lone pair of
electron of the N of amides compared with simple
amines
http://www.chemguide.co.uk/organicprops/amides/other.html

3.3 Explain the acid-base

properties of amino acids

Amino Acids
compounds containing an
amino group, -NH2, and a
carboxylic acid group, -COOH
biologically important amino
acids have the amino group
attached to the carbon atom
next door to the -COOH group.
They are known as 2-amino
acids. They are also known
(slightly confusingly) as alphaamino acids.
the two simplest of these amino
acids are 2-aminoethanoic acid
and 2-aminopropanoic acid
http://www.chemguide.co.uk/organicprops/aminoacids/background.html

Amino Acids: Properties

Amino acids are crystalline solids
with surprisingly high melting
points (200 - 300C)
It is difficult to pin the melting
points down exactly because the
amino acids tend to decompose
before they melt
Amino acids have both a basic
amine group and an acidic
carboxylic acid group
There is an internal transfer of a
hydrogen ion from the -COOH
group to the -NH2 group to give a
dipolar ion called a zwitterion

Amino Acids: Zwitterions

Zwitterion has no overall electrical charge
Soluble in water (polar) but insoluble in non-polar organic
solvents such as hydrocarbons
Amino acids exist in even in the solid state
Q. What accounts for the high melting points of amino acids?
Answer.
Instead of the weaker hydrogen bonds and other intermolecular
forces that you might have expected, you actually have much
stronger ionic attractions between one ion and its neighbours.
These ionic attractions take more energy to break and so the
amino acids have high melting points for the size of the molecules

Zwitterions: Buffer Capacity

Zwitterions are amphoteric and can behave
as a buffer in biological systems
If

some acid (H+) is added to an aqueous

solution of amino acids the COO- group of
the zwitterion will be protonated
If some base (OH-) is added to aqueous
solution of amino acids the NH3+ group is
deprotenated
In each case the zwitterion helps to
maintain the pH

Amino Acids:Optical Activity

Apart from glycine the carbon at the centre of the
structure has four different groups attached ( In
glycine, the "R" group is another hydrogen atom)

Because of these four different groups attached to

the same carbon atom, amino acids (apart from
glycine) are chiral

Questions?
So how much did you learn?

Which is more acidic? Why?

O
Cl

CH 2

OH

Cl

Cl

CH

OH

More acidic

Negative electron inductive effect of the Cl atom

pulls electron away from thethe delocalization of the
lone pair from O. This will enhance the removal of H
from the carboxyl group.

Which is more acidic? Why?

Cl
H2CH 3C CH

Cl

O
C

OH

H3 C

HC CH 2

O
C

OH

More acidic

Electron attracting inductive effect of Cl is

stronger at the position, thus inductive effect
decreases with distance.

Why are alcohols weaker acids than phenols?

Alcohols are weaker acids than

phenol because the OH bond in
phenol is greatly weakened as a
result of electron delocalization
towards the ring. In alcohol the
weakening of the OH bond is only
due to the electron attracting
inductive effect of O.

Question.
Solubility of organic compounds in dilute sodium
bicarbonate (NaHCO3) can reflect strength in acidity
of these systems. Suggest why does phenol and
aliphatic alcohols not react with NaHCO3, but 2,4,6
trinitrophenol reacts.
Answer:
Phenols and aliphatic alcohols which are regarded as
weak acids do not dissolve in NaHCO3, but 2, 4, 6trinitrophenol is an exception, because the 3 NO2
increases the acidity of phenol.