Chapter 19: Carboxylic Acids

Carboxylic Acids
Nomenclature:
Functional group suffix = -oic acid (review)
If the acid is substituted onto a ring the suffix -carboxylic acid is used.

IUPAC
methanoic acid ethanoic acid propanedioic acid butanedioic acid
name:
Trivial
formic acid acetic acid malonic acid succinic acid
name:

The anion dervived by deprotonation of a carboxylic acids is the carboxylate.

Physical Properties:

The polar nature of both the O-H and C=O bonds (due to the electonegativity difference of
the atoms) results in the formation of strong hydrogen bonds with other carboxylic acid
molecules or other H-bonding systems (e.g. water). The implications are:
higher melting and boiling points compared to analogous alcohols
high solubility in aqueous media
hydrogen bonded dimers in gas phase and dimers or aggregates in pure liquid

Structure:

The CO2H unit is planar and consistant with sp2 hydridisation and a resonance interaction of
the lone pairs of the hydroxyl oxygen with the π system of the carbonyl.

Acidity:

Carboxylic acids are the most acidic simple organic compounds (pKa ~ 5).
But they are only weak acids compared to acids like HCl or H2SO4. (Remember the lower the
pKa, the stronger the acid)
Resonance stabilisation of the carboxylate ion allows the negative charge to be delocalised
between the two electronegative oxygen atoms (compare with alcohols, pKa ~ 16).
Adjacent electron withdrawing substituents increase the acidity by further stabilising the
carboxylate.

Carboxylic Acid Structure pKa

Ethanoic acid CH3CO2H 4.7

Propanoic acid CH3CH2CO2H 4.9

 Fluoroethanoic acid CH2FCO2H 2.6

Chloroethanoic acid CH2ClCO2H 2.9

Dichloroethanoic acid CHCl2CO2H 1.3

Trichloroethanoic acid CCl3CO2H 0.9

Nitroethanoic acid O2NCH2CO2H 1.7

Reactivity:

The image shows the electrostatic potential for acetic acid

(ethanoic acid).
The more red an area is, the higher the electron density and
the more blue an area is, the lower the electron density.

There is low electron density (blue) on H atom of the -

CO2H group alcohol, i.e. H+ character.
The H atom of the RCO2H is acidic (pKa ~ 5).
The most important reactions of carboxylic acids converts
them into carboxylic acid derivatives such as acyl halides,
esters and amides via nucleophilic acyl substitution
reactions.

The image shows the electrostatic potential for the acetate ion
(ethanoate ion)
The more red an area is, the higher the electron density and
the more blue an area is, the lower the electron density.

There is high electron density (red) on both O atoms of

the -CO2- group alcohol, i.e. resonance and basic or
nucleophilic behaviour

© Dr. Ian Hunt, Department of Chemistry, University of Calgary