Carboxyllic acid notes

a) Production of Carboxylic Acids

 Carboxylic acids are compounds with a -COOH functional group
 They can be prepared by a series of different reactions

1. Oxidation of primary alcohols & aldehydes

 Carboxylic acids can be formed from the oxidation of primary

alcohols and aldehydes by either acidified K2Cr2O7 or acidified
KMnO4 and reflux
 The oxidising agents themselves get reduced causing the solutions to change
colour
o In K2Cr2O7 the orange dichromate ions (Cr2O72-) are reduced to green
Cr3+ ions
o In KMnO4 the purple manganate ions (MnO4-) are reduced to colourless
Mn2+ ions

Oxidation of primary alcohols and aldehydes

Oxidation of primary alcohols (1) and aldehydes (2) gives carboxylic acids
2. Hydrolysis of nitriles
 Carboxylic acids can also be prepared from the hydrolysis of nitriles using
either dilute acid or dilute alkali followed by acidification
o Hydrolysis by dilute acid results in the formation of a carboxylic acid and
ammonium salt
 o Hydrolysis by dilute alkali results in the formation of a sodium carboxylate
salt and ammonia; Acidification is required to change the carboxylate ion
into a carboxylic acid
 The -CN group at the end of the hydrocarbon chain is converted to a -COOH
group

Hydrolysis of nitriles

Hydrolysis of nitriles by either dilute acid (1) or dilute alkali and acidification (2)
will form a carboxylic acid

Hydrolysis of esters
 Esters are formed from the condensation reaction between an alcohol and a
carboxylic acid
 Hydrolysis of esters by dilute acid or dilute alkali and heat followed by
acidification will reform the alcohol and the carboxylic acid
o Hydrolysis by dilute acid is a reversible reaction where an equilibrium is
established
o Hydrolysis by dilute alkali is an irreversible reaction as all the ester is
broken down to form a sodium carboxylate salt and an alcohol;
acidification is required to change the carboxylate ion into a carboxylic
acid
 3. Hydrolysis of esters

Hydrolysis of esters by either dilute acid (1) or dilute alkali and heat followed
acidification (2) will form a carboxylic acid
 b) Reactions of Carboxylic Acids
 Carboxylic acids are weak acids as they do not completely dissociate in water
 This means that the position of the equilibrium lies to the left and that the
concentration of H+ is much smaller than the concentration of the carboxylic acid
 The solution has a pH value of less than 7

Example dissociation of a carboxylic acid

Carboxylic acids are weak acids that do not fully dissociate in water, the position
of the equilibrium lies to the left
 Carboxylic acids are reactive compounds which can undergo many types of
reactions including:
o Redox reactions with reactive metals
o Neutralization reactions with alkali
o Acid-base reactions with carbonates
o Esterification with alcohols
o Reduction by LiAlH4
Different reactions of carboxylic acids

Ca
rboxylic acids undergo these reactions
 Test of functional group
Functional Group Test Production
Hydrogenation of alkenes using H2, Pt/Ni catalyst and
heat
Alkane No specific chemical test
Cracking of crude oil using heat and Al2O3 catalyst
Elimination of halogenoalkanes by heating it with
ethanolic NaOH
Alkene Decolourises bromine water
Dehydration of alcohols using hot Al2O3 catalyst

Cracking of crude oil using heat and Al2O3 catalyst

Free-radical substitution of alkanes using UV and a
halogen
Halogenoalkane Form silver halide precipitate with dilute
Electrophilic addition of hydrogen halides to alkenes
nitric acid, silver nitrate and dilute ammonia
(primary, secondary solution (AgCI = white, AgBr = cream and
Nucleophilic substitution of an alcohol, e.g. by reaction
and tertiary) AgI = yellow)
with HX (g) or with KCl and concentrated H2SO4 or
concentrated H3PO4 or with PCl3 and heat or with PCl5 or
with SOCl2
Electrophilic addition of alkenes using hot steam,
concentrated phosphoric(VI) acid as a catalyst
React with carboxylic acid and sulfuric acid
to make esters which have fruity smells Oxidation of alkenes using cold, dilute KMnO4 to form
a diol
Primary alcohols get oxidised to aldehydes
Alcohol (give positive test with Fehling's and Nucleophilic substitution of halogenoalkanes using heat
Tollens' solution and carboxylic acids and NaOH (aq)
(primary, secondary
and tertiary) Secondary alcohols are oxidised to ketones Reduction of aldehydes and ketones using NaBH4 and
(positive test with 2,4-DNPH but not LiAlH4 (aldehydes are reduced to primary alcohols and
Fehling's and Tollens' solution) ketones are reduced to secondary alcohols)

Tertiary alcohols cannot be oxidised Reduction of carboxylic acid using LiAlH4

Hydrolysis of esters using dilute acid or dilute alkali

Silver mirror in Tollens' reagent
Primary alcohols can be oxidised to aldehydes using
Aldehyde Red precipitate in Fehling's solution acidified K2Cr2O7 or KMnO4, with distillation to prevent
further oxidation to carboxylic acids
Orange precipitate with 2,4-DNPH
 Oxidation of secondary alcohols in acidified K2Cr2O7 or
Ketone Orange precipitate with 2,4-DNPH
KMnO4 and under distillation
Oxidation of aldehydes and alcohols using acidified
K2Cr2O7 or KMnO4 under reflux

React with carbonates to form CO2 gas Hydrolysis of nitriles with dilute acid or dilute alkali
Carboxylic Acid
which will turn limewater cloudy followed by acidification

Hydrolysis of ester with dilute acid or dilute alkali

followed by acidification
Condensation reaction of alcohols and carboxylic acids
Ester Have sweet, fruity smells
with hot, concentrated H2SO4 as catalyst
Turns damp red litmus paper blue
Nucleophilic substitution of halogenoalkanes when
Amine
heated under pressure with NH3 (ethanol)
Turns universal indicator blue / purple
Nucleophilic substitution of halogenoalkanes when
Nitrile No official test
heated under pressure with KCN (ethanol) and heat

Elucidating Organic Molecules

 You are expected to be able to identify organic functional groups, their
properties, how to test for their presence and how they are made

Functional groups
 The table below summarises the tests to identify the presence of certain
functional groups and the reactions to make them

Functional groups, their reactions & identifying tests

table
-

Types of reactions
 You should also be aware of the different type of reactions that functional groups
can undergo
 Type of
Definition Reagents Products
reaction
Hydrogenation The addition of alkenes with hydrogen H2, Pt / Ni catalyst Alkanes
The process in which large, less useful hydrocarbon
Al2O3 catalyst and
Cracking molecules are broken down into smaller, more useful Alkanes and alkenes
heat
molecules in an oil refinery
The reaction in which halogen atoms substitute for
hydrogen atoms in alkanes, The mechanism involves
Free-radical Halogen and UV
steps in which reactive free radicals are produced Halogenoalkane
substitution light
(initiation), regenerated (propagation) and consumed
(termination)
The mechanism of the reaction in which an Electrophile (eg. Br2,
Electrophilic Halogenoalkane, alcohol
electrophile attacks the C=C bond and addition across HBr, H2O and
Addition or alkane
the double bond occurs H2SO4)
The mechanism of the reaction in which a nucleophile
Nucleophilic Nucleophile (e.g. Halogenoalkane, alcohol,
attacks the carbon atom in a carbonyl group and
Addition HCN) nitrile or amine
addition across the C=O bond occurs
The replacement of an atom by another atom or group Electrophile (eg. Br2,
Electrophilic
of atoms after initial attack by an electron—deficient NaOH, KCN,
Substitution
species NH3 and HBr
The mechanism of the organic reaction in which a
nucleophile attacks a carbon atom carrying a potential
Nucleophilic Nucleophile (eg.
positive charge. This results in the replacement of an
Substitution HCN)
atom carrying a partial negative charge by the
nucleophile
Oxidising agent such
The loss of electrons or gain of oxygen of an atom, ion Alcohol, aldehyde, ketone
Oxidation as acidified
or molecule or carboxylic acid
K2Cr2O7 or KMnO4
Alkene, aldehyde, primary
The gain of electrons or loss of oxygen of an atom, ion Reducing agent such
Reduction and secondary alcohol,
or molecules as NaBH4 or LiAlH4
carboxylic acid
The breakdown of a compound by water or by dilute Water or dilute acid or
Hydrolysis
acids or alkali alkali
A reaction in which two organic molecules join Two molecules that
Small molecule and a
Condensation together and in the process eliminate a small molecule can react with each
larger molecule
such as water or hydrogen chloride other
Reactions of functional groups table
 Oxidising & reducing agents
 Certain functional groups only react with specific oxidising and reducing agents
which you should be aware of

Oxidising Agent
Oxidises Oxidation Product Colour Change
Aldehydes then carboxylic
Primary alcohols Orange to green
acids
Secondary
Ketones Orange to green
Acidified potassium dichromate (K2Cr2O7 / H2SO4) alcohols
Tertiary alcohols X
Aldehydes Carboxylic acids Orange to green
Ketones X
Aldehydes then carboxylic Purple to
Primary alcohols
acids colourless
Secondary Purple to
Ketones
alcohols colourless
Acidified potassium permanganate (KMnO4 / Tertiary alcohols X
H2SO4) Purple to
Aldehydes Carboxylic acids
colourless
Ketones X
Purple to
Alkenes Diol
colourless
Oxidising & reducing agents table
Reducing Agent
Reduces Reduction Product
Carboxylic acids X
Aldehyde Primary alcohol
Sodium borohydride (NaBH4)
Ketone Secondary alcohol
Alkene X
Carboxylic acids Aldehyde then primary alcohol
Aldehyde Primary alcohol
Lithium aluminium hydride (LiAlH4)
Ketone Secondary alcohol
Alkene X
Hydrogen and Pt / Ni Catalyst (H2, Pt / Ni catalyst) Carboxylic acids X
Aldehyde Primary alcohol*
Ketone Secondary alcohol*
 Alkene Alkane
*Catalytic hydrogenation can reduce aldehydes and ketones to alcohols. However, this
reaction often requires different (sometimes harsher) conditions than the hydrogenation
of an alkene.

Tests
 The test also requires you to distinguish between the different tests that identify
functional groups in a compound

Tests identifying functional groups in a compound

table
Functional Group Tested Colour Change
Clear blue solution turns opaque red/orange as a precipitate is
Fehling's Solution Aldehydes
formed
Tollens' Reagent Aldehydes Silver mirror

Bromine water Alkenes Bromine water changes from orange to colourless

2,4—
Carbonyl compounds
dinitrophenylhydrazine Orange precipitate
(aldehydes and ketones)
(2,4—DNPH)
Methyl ketone (CH3CO—)
Iodoform Yellow precipitate of triiodomethane
group
Silver nitrate and
Halogens AgCl = white AgBr = cream & Agl = yellow
ammonia
Worked Example
Identify which tests give positive results with the following compounds and which
oxidising and reducing agents the compounds react with.
Answers: