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207

Carboxylic acids

a describe the formation of carboxylic acids from alcohols, aldehydes and nitriles

b describe the reactions of carboxylic acids in the formation of:

(i) salts, by the use of reactive metals, alkalis or carbonates

(ii) alkyl esters

(iii) alcohols, by use of LiAlH4

(iv) acyl chlorides

c recognise that some carboxylic acids can be further oxidised:

(i) the oxidation of methanoic acid, HCO2H, with Fehling’s and Tollens’ reagents

(ii) the oxidation of ethanedioic acid, HO2CCO2H, with warm acidified

manganate(VII)

d explain the relative acidities of carboxylic acids, phenols and alcohols

e use the concept of electronegativity to explain the acidities of chlorine-substituted

ethanoic acids

Esters

a describe the acid and base hydrolysis of esters

b state the major commercial uses of esters, e.g. solvents, perfumes, flavourings

CARBOXYLIC ACIDS

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Candidates should be 208
able to:

19.1 Carboxylic acids a) describe the formation of carboxylic acids from alcohols, aldehydes and
nitriles
b) describe the reactions of carboxylic acids in the formation of:
(i) salts, by the use of reactive metals, alkalis or carbonates
(ii) alkyl esters
(iii) alcohols, by use of LiAlH4
(iv) acyl chlorides
c) recognise that some carboxylic acids can be further oxidised:
(i) the oxidation of methanoic acid, HCO2H, with Fehling’s and
Tollens’ reagents
(ii) the oxidation of ethanedioic acid, HO2CCO2H, with warm
acidified manganate(VII)
d) explain the relative acidities of carboxylic acids, phenols and
alcohols
e) use the concept of electronegativity to explain the acidities of
chlorine-substituted ethanoic acids

19.2 Acyl chlorides a) describe the hydrolysis of acyl chlorides

b) describe the reactions of acyl chlorides with alcohols, phenols,
ammonia and primary amines
c) explain the relative ease of hydrolysis of acyl chlorides, alkyl
chlorides and aryl chlorides including the condensation (addition-
elimination) mechanism for the hydrolysis of acyl chlorides

19.3 Esters a) describe the acid and base hydrolysis of esters

b) state the major commercial uses of esters, e.g. solvents, perfumes,
flavourings

42 www.cie.org.uk/alevel Back to contents page

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CARBOXYLIC ACIDS AND ESTERS

⇐
hydgrogmb

:-t
S

•o:O
au
-

O - - -

s .
st
-
H -
-
-

o°

⇐⇐
hydgrogmbond

:-.
tt•oS
hydgrogmbond

:-.
tt
Stoos;

:O
•oS An
Stoos ;

au :O
au
-

O 0O H
0
- - -

•
-

- - - -

Hiro -0
1 -

it
s st Ts T H

o°
.

-
H -
-
- -
-

:O CARBOXYLIC
.

-
st
H -
-
- -
-

:O
ACIDS
o°
ethanol acid
When the carbonyl group bond
is directly joined to an oxygen atom, the carboxyl group is
hydrogen hydrogen
bond
formed. This occurs in carboxylic acids and esters.

An An ¥
H H H It H H It H H CHZH

ftnfyt ftnfyt
• •

Hiro -0 f- d-
/
Hiro -0
/
1 -

it 1 -

it
it .

CHZH it .

\ CHZH
alt
H
\
-

d-
alt 1 but

dimeth
H H H H H H CHZ
H H

ethanol acid ethanol acid 4- 'd

4- memylpentanoicaa memylpentanoicaa 'd 2,3
.

Hittner
¥ f-¥
H CHZH H CHZH
.

d- f- d-
aioicacidbutane -1,4 aioicacid
d-
2
butane -1,4
d-
.

*o%÷¥P÷€oy+
.

*o%÷¥P÷€oy+
H
but
-

1
1 but butanedioiuaait butanedioiuaait

dimethylbutanoicacid
dimethylbutanoicacid
H H CHZ H H CHZ

2,3 2,3
.

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CARBOXYLIC ACIDS
The reactions of the carbonyl group are drastically changed by the presence of the
electronegative oxygen atom.

These compounds have virtually none of the reactions of carbonyl compounds.

The reactivity of carboxylic acids is dominated by the tendency of the O—H bond to ionise
to give hydrogen ions, hence the incorporation of the word ‘acid’ in their name.

The extent of ionisation is small, however.

A comparison of the boiling points of aldehydes, alcohols and carboxylic

acids is shown in Figure 10.18.
Carboxylic acids have hydrogen bonding between molecules and
therefore have higher boiling points than aldehydes of similar relative
molecular mass. They also have higher boiling points than alcohols of the
BOILING
same relative molecular mass, as POINT
they have two O atoms per molecule
Boiling Points/ oC

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211

BOILING POINT
Carboxylic acids have hydrogen bonding between molecules and therefore have higher
boiling points than aldehydes of similar relative molecular mass.

⇐
Carboxylic acids have hydrogen bonding between hydgrogmbond

:-.
tt
Stoos ;

:O
•oS
au
molecules and therefore have higher boiling points
-

O - - -

0 -

than aldehydes of similar relative molecular mass.

They also have higher boiling points than alcohols

s .
st T
of the same relative molecular mass, as they have -
H -
-
- -
-

:O
o°
two O atoms per molecule and therefore have
stronger hydrogen bonding than alcohols, which
hydrogen
bond
have only one O atom per molecule.

An
H H It H

ftnfyt
•

Hiro -0 1 -

it
it .

CHZH

H H H

ethanol acid 4- memylpentanoic

SOLUBILITY

¥
Carboxylic acids with lower relative
H molecular
CHZH mass are generally soluble in water, owing to

d- f- d-
the ability to hydrogen bond to water.
*o%
H -

but
However, the solubility decreases as the length of the hydrocarbon chain (non-polar)
1

dimethylbuta
H H CHZ
increases, so octanoic acid is essentially insoluble in water.
2,3

.Q
.

0 H

.su
⇐
-

Hft
:O
. .

- - -

.tl#ItItIsE
H

Hittner
CHZ -
C
\ st / s .
.

Hst
H £ -
H -
. .
.

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HO
'¥aW
Tara
A

A- c- c- H
OH
H+/Cr20F Atlcrzoi c-
'

c- Ho OH
c-
1 11 1 11

c-
1

- A- H -> It -

heat qdistilloffme
'
heatunder |
1 1
1

H it Product # retux
μ
ethanol 'd
FROM OXIDATION OFethanol gthanoicaa
PRIMARY ALCOHOLS
.

Reagent acidified potassium dichromate, K2Cr2O7 (OR acidified potassium

manganate(VII), KMnO4)
Condition heat under reflux
Type oxidation

c- onor
t0H
Tonetti
c-c-
H+kr20F AtlcrzoiR
11

c-
'

OH
11

ttlcrzittgheatunderreinx
11

k R H H -> R

:
-7 H
-
-

-
-

HYMNOI
-

heat qdistilloffme tgheatunderrtux heat

'
I
.

1 under
A H Product retux

primary
alum
alcohol
primary aldehyde acid .

÷r
Hu
HO c-
'¥aW
Tara
A
tkrzittgheatunderreinx
11

c-
c-
,

c- c-
H+/Cr20F '
=> Atlcrzoi R 12
OH H R R
'

A- c- tgheatunderrtux Ho OH
c-
1 11 1 11

c-
-
-
1

A-
heat
1 - HYMNOI H -> It -

qdistilloffme
'
1 1
H heatunder
1 |
H it Product # retux
μ
ethanol ethanol 'd
FROM OXIDATION 0
OF ALDEHYDES gthanoicaaH H H

c-
.

Reagent
A- c-
OH
C- out
my
acidified potassiumHdichromate,
c- c-A
K2Cr2O7 (OR acidified potassium
H -

A -
H H

manganate(VII), KMnO4) OR Fehling;s reagent OR Tollen’s solution

propan -2-01 pnpanone
Condition heat under reflux
Type oxidation

or on
t0H
Tonetti
H+kr20F
c-HH Atlcrzoi
11
'

11 11

c- c-
OH

ttlcrzittgheatunderreinx
H
heat
-7 R
R -
-

- -> R -

qdistilloffme heat HYMNOI

'

tgheatunderrtux
.

I under
Product H retux

ol aldehyde
alum acid
primary
.

HO tkrzittgheatunderreinx
c-=>
c-
11
H+/Cr20F

c-
Atlcrzoi
' ,
'
12
Ho
c-
R
A- c-
11 1 11

c-
1
R
- CEDAR COLLEGE
R
-

H OH
-

-> It
HYMNOI tgheatunderrtux
-

eat qdistilloffme
' 1
heatunder
Product
1

#
H
retux
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μ
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213

FROM HYDROLYSIS OF CYANIDES

Hydrolysis of nitriles formed after the reaction of halogenoalkanes with CN— produces
carboxylic acids.
CHZCHZCN + 2h20 -7 CHZCHZCOZH t NHZ
Reagent dilute HCl or
+ NaOH
2h20
(aq)
CHZCHZCN -7 CHZCHZCOZH t NHZ
Condition heat under reflux
Type hydrolysis

""
H H H H
CHZCHZCN + 2h20 -7 CHZCHZCOZH t NHZ
C-
C-
C-
C-
""
H
CN -> A -

H
Coat
H H

C-
C-
C-
C-
t H A
CN -> A -
Coat

t H A

""
H H H H

C- +
C-
C-
C- NHK
with acids CHZCHZCN 2h20 + Ht 7 CHBCHZCOZH +
CN -> A -
Coat

t H A
CHZCHZCN to OH -7 Cttsutzcoz
NHZ NHK
-

with alkalis + +
CHZCHZCN + 2h20 + Ht 9 7 CHBCHZCOZH +

CHZCHZCN to OH
7 -7 Cttsutzcoz
NHZ
-

+
NHK
+
CHZCHZCN + 2h20 + Ht CHBCHZCOZH +

CHZCHZCN to OH -7 Cttsutzcoz
NHZ
-

+ +

ACID REACTIONS
Carboxylic acids are weak acids.
Equation CH3CO2H + H2O ⇌ CH3CO2 + H3O+

Carboxylic acids neutralised alkalis to form salts

CH3CHzBr Ntb -
CH3CO2 Na+HBN+
+
Equation CH3CO2H + + NaOH H2O

C- carbonates
Carboxylic acids neutralised
CH3CHzBr
It
I
CH3CHzNHz
-

"
H
I
H
C- C-
C
+
I
to form salts, carbon dioxide and water
-
Ntb
H - - H -
H
I

+
H

HBN
H

CH3CHzNHz
Equation CH3CHzBr
2 CH3CO2H Ntb2CO3
+ 3r Na
+ - 2CH3CO 2 Na++ +HBN
CO2 + H2O

CH3CHzNHz
H NHZ

"
H H H H

C- C- C-

"
II I I
It H H
- Na) to form salt and hydrogen gas
C H H H HH
C-with
Carboxylic acids react most metals (e.g. C- C-
- - -

I I I I

NHZ
Equation CHIt3CO2H C 3r+ H Na
-

- CH3CO2HH Na
-
+ + H½ H2 -

3r H NHZ
10

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214
C- C- at -> At
-

C- a
H H H

Condensation reactions are reactions in which two molecules join

together with the elimination of the elements of water. They are part of
a more general class of reactions called addition–elimination reactions, in
ESTERIFICATION
which molecules other than H2O are eliminated.

Colt
WhenIt Itan alcohol is heated
Conca HI
with a carboxylicH acid It in the presenceConc of a.HB
Describe
small the
amount of IItof esters
formation It

Arndt
I I
And Brz
1
1 I
reap reap
C- I sulfuric acid an alcohol is heated with a carboxylic acid in the C-
concentrated
the
-
OR
= as a catalyst, an At ester is formed.
OR
Understand
- how to name Ht estersBr -

Whenjoin presence of a
-

ndensation reactions are reactions inhehtanderretwk

1 1
which two molecules Understand how polyesters
hehtanderrettux
1
1 1 1

H H small A
amount It of concentrated sulfuric acid as a catalyst, an H H ester is formed.
ther with the elimination
Reagent of the elements
carboxylicof water. acid They
andare conc. part of
sulfuric acid, H2SO may4 be formed in condensation
For example:

I
ore general classCondition
of reactions called addition–elimination
60°C It
/It heat reactions, in It It polymerisation reactions
ch molecules other than H2O are eliminated. C- C- at At C- a
Describe
H2SO4 the formation of
->
-

Type of reaction esterification / condensation / nucleophilic conc.

substitution
H alcohol + carboxylic H H acid amides from ester + water
amines and
heat

.tt#et+i+o
CHZCOZH + CHSCHZOH T CHZCECHZCH
carboxylic
t
acids
HZO
en an alcohol is heated with a carboxylic acid in the presence of a Understand
conc. H2SO4 how to name
}

ll amount of concentrated sulfuric acid as a catalyst, an ethanol ester is formed. + ethanoic acid amides ethyl ethanoate + water
its
heat

rotted
Colt
example:
'T Understand how polyamides
H It .HB It

OR,F¥
It It It
* 'PHE*
Conca HI Conc

Arndt
I
reap
1 't = reap And Brz I 1 I I

C- C- in condensation
OR
the I =
-

At - may be formed
Ht Br -
-

conc. H2SO4 hehtanderretwk

1 1
hehtanderrettux H
1
1 1 1

cohol + carboxylic acidethanoicaa 'd ester + water

H H
ethanol
A It polymerisationH H reactions
heat ethydetnanoate
Describe the economic
conc. H2SO4
11 importance of condensation
thanol + ethanoic acid ethyl ethanoate + water reactions

.tt#et+i+o
heat CHZCOZH + CHSCHZOH T CHZCECHZCH } t HZO

Hal
( Codtk
+
cone . HzS04

rotted its,F¥ 'T

ZCHSCHZOH
* 'PHE* 't =
0
0 The alcohol and the carboxylic acid have been joined together and
ethandiocacid
c- OH
H

toe # ethydetnanoate
ethanol cone .HzS04
HO -
c-
ethanoicaa 'd
+ H - water has been
- H eliminated (one H atom from the alcohol and –OH from
I

It H
I
the carboxylic acid molecule).
ethanol

ESTERIFICATION
t

Hal
( Codtk
+
cone . HzS04

ZCHSCHZOH
ZH
The alcohol and The alcohol and 0the carboxylic acid have been joined together and water has been

n
0
H ethandiocacid
the carboxylic 0 acid have been H joined together and
c- A

toe #
.HzS04
c-
cone

#from the carboxylic out

OH cone HzS04 H
eliminated HO 11
(one H atom from the alcohol c-
and –OH +
Examiner’s
H
tip
acid molecule). 1 -

er has been eliminated (one H atom

c- OH from H the alcohol and H –OH from
1 -
-
1 .

-0
I I
+
-
-
-

carboxylic acid molecule).

It
ethanol
The product formed when H

t H H
any alcohol and any carboxylic
ethanoicaa 'd ethane -1,2 did
acid come together can be
-

ZH
n
H
0 A H
worked out simply by putting
c- OH
out #
1 11HzS04 1 1 cone

c-
.

-0
-
H +
the alcohol and carboxylic acid
H -
-

t H
together, so that the two O–H H

ethanoicaa 'd -1,2 did ethane -

groups are next to each other,

How
±
removing H from the OH of

HO
A
the alcohol and OH from the
A- c- c- it
OH A- c-
Hilo
1

c-
-7 H -7 OH
carboxylic acid and joining the
-

c-How
HO ±gthanoica
+
A H O of the
H alcohol to the C=O
ethanol
A- c- c-
OH A- c- ethanol
Hilo of the carboxylic acid.
1

it -7 H -7 OH -

12
+ H H

gthanoica
ethanol ethanol

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 .tt#et+i+o
hehtanderretwk
rotted its,F¥ 'T
Colt
hehtanderrettux

.tt#et+i+o
1 1 1
1 1 1

H
* 'PHE*
H CHZCOZH + CHSCHZOH
Online Classes : Megalecture@gmail.com
't A= T It CHZCECHZCH } HZO t H H

215 H

ethanoicaa
* 'PHE*
'd

rotted
ethanol
't = its,F¥ethydetnanoate
'T
H

.tt#et+i+o
CHZCOZH
'd + CHSCHZOH
ethanol T CHZCECHZCH t HZO
ethanoicaa ethydetnanoate }

t its

Hal
( ESTERIFICATION Codtk+
cone . HzS04

'PHE*
* rotted = ,F¥ 'T 't

ZCHSCHZOH t.HzS04

Hal
( Codtk 0 0 +
cone . HzS04
H

ethandiocacid c- OH
toe #
'd ethanol cone
ethanoicaa ethydetnanoate

ZCHSCHZOH
+ H H
HO c-
-
-
-

0 0 I I

ethandiocacid
c- OH
toe #
It H cone .HzS04
+ H H
HO c-
ethanol
-
-
-

I I

Hal
It H
( Codtk
+
ethanol
cone . HzS04

c-ZCHSCHZOH
ZH
c- n toe
H 0 H A

c-c-
out
0

##
011
ethandiocacid
1 1 1 cone HzS04

ZH
.

n
-0
OH + H H A H cone .HzS04
0
-

H
-

OH H
-

HO + H

out
c-
-

#
-

HzS04
-

1 11 1 1 cone

c-
I
.

-0
I
t OH + H H H -
H
It H
-
-

ethanoicaa 'd ethane -1,2 did

Hethanol
-

t H

ethanoicaa 'd ethane -1,2 -

did

ZH
n
H 0 H A

c- OH
out #
1 11 1 1 cone HzS04
13
c-
.

-0
- + H -
-
H

HOHow
±
tA H H

HOHow
±
A- c- c- it
'd did

Hilo
A
ethanoicaa ethane -1,2
OH
-

c-
1

c-
OH
c- c- it
-7 H -7
Hilo
A-
OH
c-
-
1

c-
A- -7 A- H -7 -
OH
+ H H
+ H

gthanoica
H
ethanol ethanol

gthanoica
ethanol ethanol

How
HO ±
A

c- c-
OH it HYDROLYSIS
A- c- OF Hilo OH
ESTERS 1

c-
A- -7 H -7 -

+ H H
The most common type of reaction that esters undergo is nucleophilic substitution,

gthanoica
ethanol ethanol
illustrated by their hydrolysis.

The hydrolysis of an ester is a slow process, taking several hours of heating under reflux
with dilute aqueous acids. Acid catalysed hydrolysis does not go completion.

Ester hydrolysis can also be carried out in alkaline solution. The reaction is quicker than in
acid solution: OH— is a stronger nucleophile than water. Additionally, it does not reach
equilibrium, but goes to completion.

This is because the carboxylic acid produced reacts with an excess of the alkali to form the
carboxylate salt.

14

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- R
COZH :
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216 g- i -
OH

HYDROLYSIS OF ESTERS

CH3CHzCO[
With HCI CHZCHZCOZCHZ + HZO -> CHZCHZCCKH + CHZOH

With NAOH CH3CHzC0zCHz + HZO -> + CHZOH

I I
H tl 0 H 0 H tl

Ct
dil HCI
I 11 I I

Ct
I 11

;D
1

C- C -0 H -
It -0 C

isttz
"¥o¥+*a* o*rEo "d¥
t'
- -
-
-

heat
-

I I I

H H H H H

to
CHZCHZOCOCHZCOZCHZCHZ

i.
15

HYDROLYSIS OF ESTERS
-
Hydrolyse the following esters using dil HCl. an
" "
0 0

AO
0
"
H -
C A -
c

\0 -

CHZCHZCHG
\
0 -

CHCCHDZ

thorn
0

A -
c
"
0 "
0
tan
\
0 CHCCHDZ
ZCHZCHG
-

16

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0
"
H -
C A -
c

\0Classes : Megalecture@gmail.com
Online -
\
0
CHZCHZCHG 217
-

CHCCHDZ

CH3CHzCO[
With HCI CHZCHZCOZCHZ + HZO -> CHZCHZCCKH + CHZOH

With NAOH CH3CHzC0zCHz

HYDROLYSIS OF ESTERS + HZO -> + CHZOH

I I
H tl 0 H 0 H tl

Ct
dil HCI
I 11 I I

Ct
1 I 11

C- C -0 H -
It -0 C - -
-
-

heat
-

I I I

H H H H H

CHZCHZOCOCHZCOZCHZCHZ

;D

isttz
"¥o¥+*a* o*rEo "d¥
t'
17
to

i.

HYDROLYSIS OF ESTERS
Hydrolyse the following esters using NaOH (aq).

- an
" "
0 0

thorn
0

"
0
tan
18

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HYDROLYSIS OF ESTERS
Hydrolyse the following esters using dil HCl.

an
218

-
"
0

thorn
0

19

ESTERS
Esters often have a sweet, fruity smell and are used as artificial flavours and odours. Esters
are good organic solvents.

Fats and oils are esters of propane-1,2,3-triol (glycerol) and long-chain carboxylic acids (fatty
acids).

Despite containing two oxygen atoms, they do not form strong hydrogen bonds with water
molecules. Neither do they form hydrogen bonds with other ester molecules (because they
do not contain δ+ hydrogen atoms).

Their major intermolecular bonding is van der Waals. Their boiling points are therefore a
few degrees higher than those of the alkanes of similar molecular mass lower than those of
corresponding carboxylic acids.

20

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219

REDUCTION OF THE –CO 2 H GROUP

Carboxylic acids can be reduced to alcohols by reacting with lithium
tetrahydridoaluminate(III) (lithium aluminium hydride), LiAlH4, in dry ether.

¢
OH
O
4 LIAIHY
R C - H
R
- - -

\
dry other
0 -

µ
H

The reaction requires the powerful reducing agent LiAlH4: neither NaBH4 nor H2 + Ni are
strong enough to reduce carboxylic acids.

CHZCOZH + 4ft ] → CAZCHZOH +

HZO
21

REDUCTION OF CARBOXYLIC ACIDS

¢
OH
Carboxylic acids can be reducedO to their corresponding primary alcohol by using the
4 LIAIHY
R C - LiAlH4, in H
reducing agent lithium tetrahydridoaluminate, R dry ether at room temperature. Dry
- - -

\
dry other
ether is used because LiAlH4 reacts
0 violently
µ with water.
-

In the simplified reduction equation, the symbol [H] can be used to represent the hydrogen
atoms from the reducing agent (remember that in organic chemistry, reduction can be
thought of as the addition of hydrogen atoms). So for ethanoic acid being reduced to
ethanol, we can show the reaction as:

CHZCOZH + 4ft ] → CAZCHZOH +

HZO

22

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