CARBOXYLIC ACIDS

INTRODUCTION

Aliphatic monocarboxylic acids form a homologous series corresponding to the general

molecular formula, CnH2nO2. Carboxylic acids are organic compounds that contain the
carboxyl group that is made of carbonyl group and hydroxyl group.

The number of the carboxyl group present in acid classifies acids as: Monocarboxylic acids
which are monobasic with one carboxyl while dicarboxylic acid are dibasic.

The simplest dicarboxylic acid are:

COOH
COOH COOH

COOH
COOH Butane-1,4-dioic acid
Ethanedioic acid COOH (Succinic acid)
Propane-1,3-dioic acid (Malonic acid)

NOMENCLATURE

The IUPAC names are afforded by taking the name of the appropriate alkane and replacing
the ending –“e” with the suffix “oic acid”. Positions of the substitution are denoted in the
usual way by numbering the longest unbranched chain containing the carboxyl group.

Sturcture Name
HCOOH methanoic acid

CH3CH2COOH Propanoic acid

CH3(CH2)2COOH Butanoic acid

(CH3)2CHCOOH 2-methylpropanoic acid

CH3(CH2)14COOH Hexadecanoic acid

C6H5CH2COOH 2-phenylethanoic acid
HOOCCOOH ethanedioic acid
HOOCCH2COOH Propane-1,3-dioic acid

PHYSICAL PROPERTIES OF CARBOXYLIC ACIDS

All simple aliphatic acids as far as C10 are liquids at room temperature while aromatic acids
are crystalline solids. Ethanoic acid has a sharp, pungent odor.

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Boiling points of the acids increase with increase molecular mass. The boiling points are
higher than expected because of the ability of the molecule to associate through hydrogen
bonding which requires extra energy to break.

The first four aliphatic acids are completely miscible with water due to the ability of the
functional group to form hydrogen bonds with water molecules.

Because of their greater hydrocarbon hence covalent character, the higher homologues
become progressively less soluble in water.

Benzoic acid is only slightly soluble in cold water but dissolves readily in hot.

N.B. The molecular mass determination of carboxylic acids using Colligative properties such
as freezing point in non-polar solvents gives the results that are twice than expected due
dimerization of the molecule through hydrogen bonding in such solvents.

Acidic nature of carboxylic acids

Carboxylic acids are weak acids which partially dissociate in aqueous solutions. However,
they are stronger acids than alcohols and phenols.

The acidic strength of carboxylic acids depends on degree of ionization and the acid
dissociation constant denoted Ka defined as

Ka = for a weak monobasic HX acid.

The nature of the groups close to the carboxyl group has a great effect on the acid strength
therefore a phenomenon known as inductive effect. Electron withdrawing groups e.g.,
halogens make carboxylic acid stronger thus oxygen-hydrogen bond becomes weaken hence
release of hydrogen ions in aqueous solution. i.e.

Acid CH3COOH CH2ClCOOH CHCl2COOH CCl3COOH

Ka 1.7x 10-5 1.3x10-3 5.0x10-2 2.3x10-1

1.29 0.65
PKa 4.76 2.86

Electron releasing groups e.g., alkyl groups make carboxylic acid weaker thus oxygen-
hydrogen bond strengthen hence less amount of hydrogen ions in aqueous solution

SYNTHETIC PREPARATIONS

1) Oxidation of Primary Alcohol or Aldehydes

Primary Alcohols or Aldehydes are oxidized by acidified potassium dichromate

solution or acidified chromium (VI) oxide to carboxylic acid.

2
 CrO3 /H+ CrO3 /H+
RCHO RCOOH
RCH2OH
heat heat
Aldehyde Carboxylic acid
1oAlcohol

Orange solution turns green due to reduction of chromium (VI) ions to chromium (III)
ions.

2) Grignard synthesis

Mg CO2 H2O
RMgBr RCOOMgBr RCOOH + MgBrCl
RBr dil.HCl
dry ether dry ether
o o o
R may be 1 ,2 ,3 or Aromatic
Example

Mg CO2 H2O
CH3CH2Br CH3CH2MgBr CH3CH2COOMgBr CH3CH2COOH
dry ether dry ether dil.H+

In Preparation of Benzoic acid, solid carbon dioxide or dry ice is used.

3) From Methyl Benzene

MnO4- /H+
CH3 COOH
heat

4) From Cyanide compounds.

KCN/EtOH H2O/H+
RX RCN RCOOH
heat Reflux

HBr KCN/EtOH
CH3CH CH2 CH3CH2CH2Br CH3CH2CH2CN
peroxide heat
H2O /H+ reflux

CH3CH2CH2COOH

The reaction is unsuitable for preparation of aromatic carboxylic acid.

5) Cannizzaro reaction

Aromatic Aldehydes and aliphatic ones containing no α-hydrogen atom undergo self-
oxidation and reduction.

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 NaOH (aq) HCOONa + CH3OH
HCHO
dil.H+

HCOOH

6) Alkali Hydrolysis of Esters

The hydrolysis of Esters generates the corresponding alcohol and Acid.

The method is not commonly used since esters are obtained from carboxylic acid.

NaOH (aq)
RCOOR' RCOONa + R'OH

dil.H+

RCOOH

REACTIONS OF CARBOXYLIC ACIDS

The reactions of carboxylic acids involve the hydroxyl group which either undergoes the loss
of proton or replaced by another atom or group.

Some of the reactions include:

1) With Bases

They react to form salts and water

RCOOH + NaOH RCOONa + H2O

2) With electropositive metals.

They react to form salts and hydrogen

2 RCOOH + Mg (RCOO)2Mg + H2

3) With sodium carbonate or Sodium hydrogen carbonate

They react to liberate carbon dioxide gas. They are stronger acids than carbonic acid.

2RCOOH + Na2CO3 2RCOONa + CO2 + H2O

RCOOH + NaHCO3 RCOONa + CO2 + H2O

4) With Primary Alcohols

Carboxylic acids react with primary alcohols in presence of concentrated sulphuric

acid as catalyst to form esters.

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 H+
RCOOH + R'OH RCOOR' + H2O
heat

(See Alcohols for mechanism of the reaction)

5) With Phosphorous halides

They react to acid chlorides.

PCl5
RCOOH RCOCl + POCl3 + HCl
PCl3
RCOOH RCOCl + H3PO3

6) With Thionyl chloride

They react also to form acid chlorides. This is the convenient method for preparation
of acid chlorides since the other two products are gaseous.

SOCl2
RCOOH RCOCl + SO2 + HCl
(white fumes)

7) With Iron (III) chloride solution

They react forming a reddish-brown precipitate or solution. Lower molecular mass

acids form a solution.

3RCOO- + Fe3+ (RCOO)3Fe

3C6H5COO-(aq) + Fe3+ (aq) (C6H5COO)3Fe (s)

8) Reduction reaction

Carboxylic acids are reduced to primary alcohols using lithium aluminum hydride.

LiAlH4
RCOOH RCH2OH
dry ether

9) Reaction of the Alkyl group

When chlorine gas is bubbled through hot carboxylic acid in presence of ultraviolet
light, one or all the hydrogen atoms adjacent are substituted.

Cl2 Cl2 Cl2

CH3COOH ClCH2COOH Cl2CHCOOH Cl3CCOOH
U.V.light U.V.light U.V.light

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10) Decarboxylation reaction.

This reaction decreases the carbon length of the sodium salt of carboxylic acid to form
an alkane.

sodalime
RCOONa RH + Na2CO3
heat (Alkane)

11) Amide formation.

SOCl2 NH3 LiAlH4 RCH2NH2

RCOCl RCONH2 dry ether
RCOOH
(Amide)

Br2 / Conc.NaOH (aq) heat

RNH2

Sample reaction scheme is shown below

SOCl2 CH3NH2 CH3CONHCH3
CH3COOH CH3COCl

NH3 Br2 / LiAlH4 dry ether

conc. NaOH (aq) heat
heat
H+ /H2O

CH3CONH2
CH3NHCH3 CH3CH2NHCH3
Br2 /
heat
conc. NaOH (aq)

CH3Br
CH3NH2

12) With Ammoniacal Silver nitrate solution

Methanoic acid is the only carboxylic acid that reacts with ammoniacal silver nitrate
solution on warming due to presence of Aldehydes group to form silver mirror
alongside a clean test tube.

HCOOH + 2Ag+ CO2 + 2H+ +Ag

13) Dehydration reaction

Methanoic acid and Ethanedioic acid are the only carboxylic acid that can be
dehydrated using concentrated sulphuric acid.

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 conc. H2SO4
HCOOH CO + H2O
conc.H2SO4
(COOH)2 CO + CO2 + H2O

Question

1. How would one carry out the following conversions in the laboratory? Indicate the
necessary conditions of the reaction.

(a) CH3CHO to CH3COOCH3

(b) CH2 CH2 to CH3CH2COOH

(c) CH3COOH to CH3CH2NHCH3

(d) C6H5CH3 to C6H5COOCH3

2. Three isomeric acids A, B and C have molecular formula C8H6O4 and all contain a
benzene ring. In each case, one mole of the acid will react with 2moles of sodium
hydroxide. Suggest structures for the acids. When the three acids are separately
heated, A and B melt without decomposing, but C loses a molecule of water at about
250oC to form D,C8H4O3.Suggest structures of C and D

3. Explain the following observations:

a) When dilute hydrochloric acid is added to aqueous solution of soap, a white

insoluble substance is formed.

b) Butane, Propan-1-ol, Propanal and Ethanoic acid have approximately the same
molecular mass yet their boiling points are 273, 370 and 391K respectively.

c) Methanoic acid reacts with ammoniacal silver nitrate solution while Ethanoic
acid does not.

d) Ethanedioic acid decolorizes potassium manganate (VII) solution on warming

while Ethanoic acid does not.