Lesson 14

ACIDIC AND BASIC CHARACTER

OF
ORGANIC COMPOUNDS

Acidity Measurements
The acidity constant, Ka, measures the extent to which a Brnsted acid
transfers a proton to water
[A] [H3O+]
Ka = and pKa = log Ka
[HA]
Relative acidities are more conveniently presented on a logarithmic scale,
pKa,

pKa Values for Typical OH Compounds

ACIDITY OF ALCOHOLS, PHENOL AND CARBOXYLIC ACIDS

Brnsted-Lowry definition of acid
An acid is a proton donor
Note: a proton is a hydrogen ion (H+)
An acid in solution sets up this equilibrium:

hydroxonium ion

STRENGTHS OF WEAK ACIDS

The strengths of weak acids are measured on the pKa scale. The smaller the
number on this scale, the stronger the acid is.

Ethanoic
acid

4.76

Phenol

10.00

ethanol

Increasing
Acidity

about 16

Ethanol is so weak with a pKa of about 16 that it hardly counts as

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acidic at all!

 Resonance stabilization accounts for why carboxylic acids are more acidic
than other compounds with OH bondsnamely alcohols and phenols.

To understand the relative acidity of ethanol, phenol and acetic acid, we

must compare the stability of their conjugate bases and use the following
rule:
- Anything that stabilizes a conjugate base A: makes the starting acid HA more
acidic.

ACIDITY OF ETHANOIC ACID

The ethanoic acid molecule has a hydroxyl group attached to the carbonyl group. The
negative charge on the ethanoate ion is delocalized with the C=O double bond. Carboxylic
acids are therefore more acidic than phenol.

The dotted line represents the delocalisation. The negative charge is written
centrally on that end of the molecule to show that it isn't localised on one of
the oxygen atoms.
The more you can spread charge around, the more stable an ion becomes. In
this case, if you delocalise the negative charge over several atoms, it is going
to be much less attractive to hydrogen ions - and so you are less likely to reform the ethanoic acid.
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ACIDITY OF ETHANOL
Ethoxide, the conjugate base of ethanol, bears a negative charge on the O
atom, but there are no additional factors to further stabilize the anion.
Because ethoxide is less stable than acetate, ethanol is a weaker acid than
acetic acid.

ACIDITY OF PHENOL
Phenoxide, the conjugate base of phenol, is more stable than ethoxide, but less stable
than acetate because acetate has two electronegative O atoms upon which to delocalize
the negative charge, whereas phenoxide has only one.

Phenoxide ion
Phenols (pKa ~10) are much more acidic than alcohols (pKa ~ 16) due to resonance
stabilization of the phenoxide ion
Phenols react with NaOH solutions (but alcohols do not), forming salts that are soluble in
dilute aqueous solution

Inductive Effect :
Inductive effect is defined as permanent displacement
of shared electron pair in a carbon chain towards more
electronegative atom or group.

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Types of Inductive effect :

1.Negative Inductive Effect :
(I effect, Electron withdrawing effect)
when an electronegative atom or group(more electronegative than
hydrogen) is attached to the terminal of the carbon chain in a
compound, the electrons are displaced in the direction of the attached
atom or group.
-NO2 > -CN > -COOH > F > Cl > Br > I > OH > C6H5> H

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2. Positive Inductive effect :

(+I effect, Electron releasing effect)
When an electropositive atom or group (more electropositive
than hydrogen) is attached to the terminal of the carbon chain
in a compound, the electrons are displaced away from the
attached atom or group.
(CH3)3C- > (CH3)2CH- > -C2H5 > - CH3.

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Inductive effect is useful in explaining the strength of some organic acids and bases.
a) Effect of substituent on the acid strength of aliphatic acids.
HCOOH > CH3COOH > (CH3)2CHCOOH
Reason : Acidic strength decreases as +I effect of the alkyl group increases.
b) O2NCH2COOH > FCH2COOH >CICH2COOH >BrCH2COOH> ICH2COOH > CH3COOH
Reason : Acidic strength decreases as -I effect of the group or halogen decreases.

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INDUCTIVE EFFECTS
Electronegative atoms can draw negative charge toward themselves,
which can lead to considerable stabilization of conjugate bases.
Electron-withdrawing groups make an alcohol a stronger acid by
stabilizing the conjugate base (alkoxide)

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THE INDUCTIVE EFFECT IN ALIPHATIC CARBOXYLIC ACIDS

Acidity increases
- Due to stabilizing effect of EWGs on the conjugate base (the carboxylate ion)

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Basic character of aliphatic amines, amides and aromatic amines

pKb
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amides

Phenylamine(aniline)
(an aromatic amine)

C6H5NH2

9.4

ammonia

NH3

4.8

methylamine

CH3NH2

3.4

ethylamine

CH3CH2NH2

3.2

Aliphatic
amines

Kb = base dissociation constant

pKb =-log10Kb

Basicity
increases

Basicity of Aliphatic amines

For aliphatic amines, base strength increases with the size and number of alkyl
groups attached to the nitrogen atom.
Alkyl groups donate electron density toward the nitrogen atom, increasing the
ability of the N atom to donate its lone pair of electrons.
(an example of a positive inductive effect)

R = alkyl group

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BASICITY OF AROMATIC AMINES

Aromatic amines(e.g. phenylamine, pKb 9.4 ) are much weaker bases than
ammonia. The reason for the difference is that the nitrogens lone pair is
delocalized with the delocalized electrons in the benzene ring and so is
substantially more difficult to protonate.

Lone
pair

delocalised
electrons

Can only be protonated by strong acids

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BASICITY OF AMIDES

Amides are extremely weak acids and also very weak bases much weaker
bases than amines.
Amides are regarded as being essentially neutral in water, eg. Ethanamide
(CH3CONH2) has a pH of 7.

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Amides are NOT basic because the nitrogen lone pair is no longer
available for protonation. Instead it is delocalized with the carbonyl group.

Recall: a base is an electron pair donor

lone pair

Note: protonation refers to the addition of H+

delocalised
lone pair

Amino acids contain 2 functional groups

They all have a similar structure - the identity of R1 and R2 vary

ZWITTERIONS
a zwitterion is a dipolar ion
it has a plus and a minus charge in its structure
a proton from the COOH group moves to NH2
amino acids exist as zwitterions at a certain pH
the pH value is called the isoelectric point
produces increased inter-molecular forces
melting and boiling points are higher
A zwitterion is a compound with no
overall electrical charge, but which
contains separate parts which are
positively and negatively charged.

Acid/base properties of Amino acids

amino acids possess acidic and basic properties due to their
functional groups
they will form salts when treated with acids or alkalis.

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PROTEINS

Neutral amino acids

If the R group does not contain any acidic groups, the amino acid is neutral overall

Acidic amino acids

If the R group has more acidic groups then the amino acid is acidic.

Basic amino acids

If the R group has more basic groups then the amino acid
is basic.