1 Alcohols

The simplest alcohols form a homologous series of general formula

CnH2n+1OH provided there are no rings.

Named as substituted alkanes by removing the final -e and adding -ol

For isomers the position of the OH is given by a number propan-1-ol and

propan-2-ol

ten
*PH¥**±¥t¥*
. *±¥t¥*
'

it OH OH H

methanol ethanol
2 Alcohols
The —OH group is called the hydroxyl group. When drawing alcohols always make
sure the bond goes to the O.

*PH¥**±¥t¥*
ten
The functional *±¥t¥*
.group, however, is referred to as primary/secondary/tertiary alcohol as
'

chemical behavior of alcohols, especially withit oxidation,

OH often depends
OH H on the structure
of the alcohol.
methanol ethanol

Alcohols may be described as primary, secondary or tertiary, depending on the number

of H atoms attached to the carbon with the –OH group on it.
3 Primary Alcohols
Ethanol is a primary alcohol, as it has two hydrogens attached to the C with the
–OH attached.

A primary alcohol thus contains the –CH2OH group.

A In
,%fI
:#
a
C-
A
zaatomsatlaohed
.

Hitt
0 -
C- A

Cattachedtoott
 4 Primary Alcohols
Another way of looking at this is that the C with the –OH attached has one other C
attached to it.

One C attached = primary.

n }
H H Catomaltached

Cattachedtoott
C- I
Hμ
I

μ
H
5 Cattachedtoott
Secondary Alcohols
A In
,%fI
:# Hitt

Propan-2-ol is a secondary alcohol, as it has one H atom attached to the C

with the –OH attached. A secondary alcohol contains the –CHOH group.

¥q€t
C-
bit
E-
Zcatoms attached

c-
A
I

H -
H

ttihtirh
cattachedtout \ , ryatomaitached
 6 Tertiary Alcohols
2-methylpropan-2-ol is a tertiary alcohol, as there are no H atoms (or three C

C-
q€t
bit
E- C-C-
atoms) attached to the C with the –OH attached.

c-
H

it
I

CASH
I I
H A

"
-

t
tached
7 Properties
Alcohols are useful solvents and are key intermediates in the production of
esters, which are important solvents for the paints and plastics industries.

The polar —OH group readily forms hydrogen bonds to similar groups in other
molecules.

This accounts for the following major differences between the alcohols and the
corresponding alkanes.
8 Properties
Alcohols have higher boiling points than other organic molecules with similar
relative molecular masses. Methanol, with the lowest molar mass, is a liquid at
room temperature.

This is because of hydrogen bonding along with van der Waals’ forces between
● The boiling points of the alcohols are all much higher than the corresponding
alcohol molecules. This also explains why smaller alcohol molecules
(isoelectronic) alkanes, owing to strong intermolecular hydrogen bonding (see mix and The
to t
dissolve
Figureso well in water.
16.2).
16_
of e
CH2 CH3
δ+ Bar
H O δ– O
16
CH2 O δ– δ+H Oδ–
R 105° H As
CH3 Hδ+ CH2 CH3 the
The oxygen atom in an alcohol has two gro
Intermolecular hydrogen bonding in ethanol Figure 16.4 The oxygen atom in an alcohol
Table 16.1 and Figure 16.3 show this large difference. Ashas twolone
is usual pairs
in pairs
lone of of
homologous electrons
electrons. the
 i
9 Boiling Points s
Boiling Points/ oC
The forces between molecules
must be broken for the liquid to boil. g
b
In alcohols, hydrogen bonding is the i
strongest intermolecular force,
C
therefore, more energy is needed to
C
break the hydrogen bonds.
t
And so the boiling points of alcohols m
is higher. h
d
10 Solubility

g
dro
hy
The lower members of the series are very soluble in
water because of the hydrogen bonding.

EHL ⇐
s+
CH
For example, ethanol is soluble in water in all

°÷j÷
÷
°j÷

\gH
St

St
EL
proportions, and this is because the –OH group

jH2

/H
s+H
÷

s+
CHZ

o/Hs+
allows it to hydrogen bond to water.

°j÷
St

=H
jH2\=H\gH⇐

...
EL
\o

\o
s+H

=H/H
CHZ
However, solubility decreases as the length of the
o/Hs+

St
... bond

°s+÷
hydrogen
jH2\=H\gH⇐

jH2
hydrocarbon chain increases so that pentan-1-ol

...
Z \gH
EjH÷L
CH
...
and hexan-1-ol are only sparingly soluble in water.
CH

YH

s⇐+
Z

s ,tH ,
11 Combustion Of Alcohols
In a plentiful supply of oxygen, alcohols burn to produce carbon dioxide and
water:

C2H5OH + 3O2 ⟶ 2CO2 + 3H2O

2 C3H7OH + 9O2 ⟶ 6CO2 + 8H2O
12 Reaction With Sodium
Reagent Sodium metal, Na
Condition room temperature

CHSCHZOH + Na -7 CHZCHZO
-

Nat + kHz

WIPE . *P¥Fonat

Alcohols are organic chemistry’s equivalent of water; water reacts with sodium
to produce hydrogen and so do alcohols. The reaction is slower with alcohols.
 tit
A H H H

it
d- NW

Hk
'

13 Reaction With Sodium - -

it -

Hk
'
it
atH

tit
A H H

itd- )

at
NW

Hk
'

CHZCHZCHCOH - -
it -

Hk
'
it
at

at
CHZCHZCHCOH)

it it
t H

it .
'±E .
'
-
,

it
TH TH t

it
H
it
'±E
-

'
it .
.
-
,

TH TH
CCHDZCHCHGH)CHCoH)CHz
it -
14 Alcohols To Alkenes
When an alcohol is heated with excess concentrated sulphuric acid at around
200 oC an alkene is formed. (Refer to the notes on Alkenes).
Dehydration of the alcohol can also be carried out by passing the alcohol
vapour overeither
alumina at 350 C.
Esters can be hydrolysed by heating
an acid or a base.
o under reflux with
ceramic wool
soaked in ethanol
Refluxing with an acid simply reverses the preparation
Reagent ofConc
the ester H 2SO
from 4
an alcohol and a carboxylic acid. The acid
pumice

catalyses the reaction. The reaction is reversible and forms ethene gas collected
Condition an200 oC
equilibrium mixture. In acid hydrolysis, there are always over water
both reactants and products present after the reaction. The
Alternativelyequation
Alumina at 350
for the acid oCof ethyl ethanoate is:
hydrolysis
heat
Type Elimination
O H+(aq) O
H3C C + H2O H3C C + CH3CH2OH
O CH2CH3 O H

However, when an ester is refluxed with an alkali (a

soluble base), such as aqueous sodium hydroxide, it is
fully hydrolysed. Unlike acid hydrolysis, this is not a Figure 16.7 The dehydration of ethanol to give ethene.
 A A H H

ctt
d-
'

15it Alcohols to Alkenes

# .
.

Ak ath
' '

A A H H

ctt
d-
'
CHZCHZCHCOH

¥s#at
it .
.
#

Ak ath
' '

)CH:
CHZCHZCHCOH

¥s#at
)CH:
+ A
Magana heat

)CHCoH)CH:
+,
.it#3E.i.i-H
THH
TH
-

+ A
Magana heat

)CHCoH)CH:
+,
.it#3E.i.i-H
THH ( HDZCHCHGH
C

TH
-
16 Alcohols To Halogenoalkanes
Reagent PCl5, (PCl3 or SOCl2)
Condition room temperature (heat for PCl3 and SOCl2)
Type nucleophilic substitution

I
It It It It

C- C- at -> At
-

C- a
H H H

The reaction releases white fumes of HCl with PCl5

Note: this is another test for the “OH” group in alcohols and carboxylic acids
17 Alcohols To Halogenoalkanes
Reagent conc. HBr or conc. HI
Condition heat under reflux

I
It It It It
Type nucleophilic substitution
Alternatively Red C- C- at
Phosphorous At C- a
and Br2 or Red Phosphorous and I2 can
->
-

H H H
also be used.
Conc H2SO4 and NaBr can also be used to produce conc HBr.

Colt
It It Conca HI H It Conc .HB It It

Arndt
I I I
And Brz
1
1 I
reap reap
C- C-
OR OR
the
-

I = At -

- Ht
-

Br
1 1 hehtanderretwk 1
1
hehtanderrettux 1 1

H H A It H H
18 Alcohol To Esters

Colt
WhenIt It an alcohol is heatedHI with a carboxylic
Conca H It acid in the presence.HB of a small Conc It It

Arndt
I I
amount of concentrated sulfuric acid as a catalyst, an ester is formed.
I
And Brz
1
1 I
reap reap
C- I C-
OR OR
the
-

= At -

- Ht
-

B
1 hehtanderretwk hehtanderrettux 1

carboxylic acid andA conc. sulfuric acid, H2SO4

1
1 1 1

Reagent
H H It H H

Condition 60°C / heat

Type esterification / condensation / nucleophilic
substitution

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

* 'PHE* rotted 't = its,F¥ 'T

H

'd ethanol
ethanoicaa ethydetnanoate
 the carboxylic acid molecule).
19 Alcohol To Esters
The alcohol and the carboxylic acid have been joined together and water has
l and the carboxylic acid have been joined together and
been eliminated (one H atom from the alcohol and –OH from the carboxylic
Examiner’s tip
n eliminated (one H atom from the alcohol and –OH from
acid molecule).
acid molecule). The product formed when
any alcohol and any carboxylic
acid come together can be
worked out simply by putting
the alcohol and carboxylic acid
together, so that the two O–H
groups are next to each other,
removing H from the OH of
the alcohol and OH from the
carboxylic acid and joining the
O of the alcohol to the C=O
of the carboxylic acid.
 .tt#et+i+o t its,F¥ 'T

Hal
Codtk
( HzS04

rotted
cone
+
.

Hal
AlcoholCodtk
20'PHE*
cone HzS04
* ( to Esters + 't = .

ZCHSCHZOH
ZCHSCHZOH
H
0 0
ethandiocacid
c- OH
toe
0 'd ethanol
ethydetnanoate
#
ethanoicaa
0 .HzS04
HO ethandiocacid
cone

c- OH
toe #
H
c- + H cone .HzS04
-
-
-

+ H I H
HO c- I
-
-
-

It H
I I
It
ethanol H

ethanol

Hal
( Codtk
+
cone . HzS04

ZH
ZCHSCHZOH
n
H 0 H A

ZH
n
c- OH
out #
0 H11 00 H1 A HzS04
ethandiocacid
cone

c- c-
c-OHOH
1 1 .

-0 toe
out ##
1 11 + H - 1 1
-
H cone cone HzS04
.HzS04
c-
- .

-0
HO - -
c- + + HH - -
- H -
H
t H I H I

t 'd It H HH
ethanoicaa ethane -1,2 did -

ethanoicaa 'd ethanol

ethane -1,2 -
did
 ¥q€t
C-
bit
E- C-C-
c-
A
0 H

*Pjf
I

21 Oxidation
.tt#E*HttitceH*PHEat
it
heat heat I

CASH
H I I
H -

Primary and secondary alcohols may be oxidised using an oxidising agent,

A H

"
-

ttihtirh
ethanol ethanol ethanoicacid
such as:
cattachedtout \ , ryatomaitached
t

acidified potassium dichromate(VI) (K2Cr2O7/H+)

acidified potassiumt[O]
CHZCHZOH manganate(VII)
CHZCHO (KMnO4/H+).
+Hz0

PrimaryCHZCHO
alcohols are
t[] oxidised
CHzCOzH first of all to an aldehyde (partial oxidation), and
then the aldehyde is oxidised further to a carboxylic acid (complete oxidation).
crzoihtt crzoiilitt
primary > aldehyde > carboxylic
alcohol heat heat acid

Otirzoitlllt Craqtlttt
11 11

-> ->
hμ
-

A c

c-
heat heat / -
| o -
A
H 0
 crzoihtt crzoiilitt
22 crzoihtt
primary > crzoiilitt
Oxidation Of Primary Alcohols aldehyde > carboxylic
primary >
alcohol
aldehyde
heat > carboxylic
heat acid
alcohol heat heat acid

Primary alcohols are oxidised to aldehydes, which, in turn, are even more easily
oxidised to carboxylic acids. For example:
0

*Pjf
0

*Pjf .tt#E*HttitceH*PHEat
.tt#E*HttitceH*PHEat heat
heat
heat
heat

ethanol ethanol ethanoicacid

ethanol ethanol ethanoicacid

CHZCHZOH t[O] CHZCHO +Hz0

CHZCHZOH t[O] CHZCHO +Hz0

CHZCHO
t[]
CHZCHO
t[] CHzCOzH CHzCOzH
23 Oxidation of Primary Alcohols

Otirzoitlllt Craqtlttt
11 11

Otirzoitlllt
-> ->
hμ
-

A c

c-
heat heat / -
| 11
Craqtlttt 11 o -
A
-> ->
hμ
A c
H
-

c-
heat heat / -
| o -
A
H

*tEtI±I
.int#.tEtIte**e*ittEtIttEo
*tEtI±I
.

.int#.tEtIte**e*ittEtIttEo
heat heat .
heat heat
zmemylpropom -1-01 zmemylpbpanal Zmethylpbpanoicacid
zmemylpropom -1-01 zmemylpbpanal Zmethylpbpanoicacid
24 Oxidation of Primary Alcohols
As soon as any aldehyde is formed it can be oxidised further by the oxidising
agent, to the carboxylic acid, and so special techniques are needed to stop the
oxidation at the aldehyde stage.

One such method makes use of the lower volatility of the alcohol (due to
hydrogen bonding) compared with the aldehyde. The reaction mixture is warmed
to a temperature that is above the boiling point of the aldehyde, but below that of
the alcohol.

The aldehyde is allowed to distill out as soon as it is formed, thus avoiding any
further contact with the oxidising agent.
25 Oxidation Of Primary Alcohols
(b) Apparatus set up for distillation,
producing the aldehyde.

(a) Apparatus set up

for reflux, producing
the carboxylic acid.
26 Oxidation Of Primary Alcohols
If the reaction mixture is heated under reflux, carboxylic acid is obtained as the
main product and the aldehyde is not usually isolated.

However, it is possible to set up the experiment so that the aldehyde is distilled

off as soon as it is formed and before it can be oxidised further.

or
t0H
Tonetti
H+kr20F
c- H Atlcrzoi
'

11 11

c-
k -

-7 R -
H -
1
heat qdistilloffme
'
heat under
.

A Product retux

primary
alcohol aldehyde acid .
 HO
'¥aW
Tara
c- c-
OH H
H+/Cr20F Atlcrzoi c- OH
'

c- Ho
c-
1 11 1 11

c- Alcohols
1

A- - A- H -> It -

heat qdistilloffme
'

27 Oxidation Of Primary
H
1 1

it Product
1

#
heatunder
retux
|
μ
ethanol ethanol 'd
gthanoicaa
Using an excess of oxidising agent and heating the reaction under reflux to
.

prevent any escape of the aldehyde before distillation, allows the alcohol to be
oxidised all the way to the carboxylic acid.

This oxidation reaction can be used to distinguish between primary, secondary

and tertiary alcohols.

c- H
on
11

c-
OH

ttlcrzittgheatunderreinx
R -

-> R -

I HYMNOI tgheatunderrtux
H

alum
primary
 on
28 Oxidation Of Secondary Alcohols
c- H
11

c-
OH

ttlcrzittgheatunderreinx
R -

-> R -

Secondary alcohols
I HYMNOI
are also tgheatunderrtux
oxidised by heating with acidified potassium
H
dichromate(VI) (or acidi ed potassium manganate(VII)).
alum
primary

They are oxidised to ketones, which cannot be oxidised any further.

Htkrzoi Htkrzoi
' '

secondary - ketone -
alcohol heat heat

c-
tkrzittgheatunderreinx
11

c-
,

=> 12
'
R R R

Ot
-
-

"
1
HYMNOI tgheatunderrtux
ftp.eptttt#IinPHEPFt
'
H
 CHZCHCOH )CHzt[o] CHZCOCHZTHZO
CHZCHCOH )CHzt[o] CHZCOCHZTHZO
29 Oxidation Of Secondary Alcohols

Ot
"

ftp.eptttt#IinPHEPFt
'

Ot
"

ftp.eptttt#IinPHEPFt
'
OH 0

' Htkrzont 11
OH -2-01 0
propanone
c- pnpan
+ - c- c- C
'I heat
Htkrzont 11
c-+ - c- c- C
pnpanH-2-01
I heat propanone
H
CHZCHCOH )CHzt[o] CHZCOCHZTHZO

11
CHZCHCOH
H OH )CHzt[o] CHZCOCHZTHZO
H 0

11
I I I c- it I
Httcrzof I
c- it
I I

11
c-
H OH
c- c- c-
H 0
c- c-
11
A-
I
e
I
-

CHZH I
OH- A-
I
e 0
-

CHZH I
I Httcrzof
heat I1

c- A CHZH
c- c- c-
1 1
' Htkrzont 1 11 1

A-
H
e -

H
it
H c- -+ A-
- H
e
c-
-

CHZH
c-
H
C
H
it
1 1 heat
I heat 1 1 1

H A H H OH H H 0 H H
' Htkrzont 11
Zmethylbutan
c-
-2-01+
-
3-c-methyl butanone
c- C
I heat
-2-01 3- butanone
30 Oxidation Of Tertiary Alcohols
Tertiary alcohols do not oxidise.

c-
c-
H OH H

u ?
Htkrzont
CHZH
1 1 1

H -

H noreaction

Zmethylpwpan -2-01
 ::
31 Oxidation Examples
c-
H H H
cites
I I H+/KzCrz0y

'T d- c- H -
* -

heatunarrlmx
c-
,
H cites
H bit H 'oH
I I H+/KzCrz0y

'T d- c- H -
* -

, heatunarrlmx
bit 'oH

c-
t H H
CH3 H+/KzCrzOy
, 1

+1¥ - d- c- H -

c-
t
CH3
1 H
by H
fμ H+/KzCrzOy
, 1

+1¥ - d- c- H -

1
by fμ
32 Oxidation Examples

'T
*
heattgdishlloffpndnct
t

it
-
CHZ

,
OH
d- c-
H
,

bit
H
,

'oH
c-
:
H

"
Atl KMNOY
-
heatunarrlmx

c-
IItE¥#E¥I
H H H
cites
I I H+/KzCrz0y

'T d- c- H -
* -

heatunarrlmx

#
,
bit 'oH
33 Alcohols From Carbonyls (Reduction)
Reagent sodium borohydride, NaBH4(aq) or lithium
aluminiumhydride, LiAlH4, in ether.
Condition heat
Type Reduction
Alternate hydrogen gas over a nickel or platinum catalyst and heat
Aldehydes give primary alcohols, while ketones give secondary alcohols.

!
' '
RCHO +2ft ] => RCHZOH RCOR +2ft ] -7 RCHCOHK

0 0
"
Red
" 1

H OH '
OH '
Rt -

-> -
H R -

C -
R -> Re R-

H
34 Primary Alcohols From Aldehydes

Utzut
Ctbutz
utzatz
ctbutz
-
0 0

Utzut
"

Ctbut
utzatz
"

ctbutz
-
0 H OH
-

- -
H
" IOH pnpomtol
pnpanal
H bntana
- H
H
-
-

pnpanal I pnpomtol bnt

H

H 0 H H 0
Ctt
11
c-
OH c-
c-0 d-
1 1 11

c-H
1

H -> H H
H
- -
H H -

I
Ctt
11
I

c-
OH
I 1
c
c- d-
1 1

c-
1
H H It H
H -> H H
- -
H -

Iethanol ethanol
I I
popanon
1

H H It H

ethanol ethanol
popa
zutzt
H
!
ed H

OHH
-
35 Secondary Alcohols From Ketones

H
R

-
-

c-
H
1

popanone
0
"
C R
0 H
-

c-
11
'

c-
H
1

I
A
->

A
OH
1

Re H R

H
-
'
-

d- ctI
I

H
1

propan -2-01
1

H
-
H

Ctbutzt
utzatzt
ctbutzt
-
0
" 1

CHZ OH
-> CHZ
-

l bntananonl 1
baton -2-01
H
36 Alcohols From Alkenes
Alkenes react with acid catalyst and steam at temperatures of around 350oC
and pressures over 100 atm to form alcohols.

Reagent Steam and dil phosphoric acid (H3PO4)

Condition 350 oC and 100 atm
Type Electrophilic addition
CHECK + Ha CHZCHZOH
ethene ethanol

ice + to
1¥ -
OH
37 Alcohols From Halogenoalkanes
Hydrolysis of halogenoalkanes via NaOH (aq) produces alcohols.

Reagent Aqueous sodium (or potassium) hydroxide.

Condition heat under reflux in aqueous solution
Type nucleophilic substitution

Ator Htbr
Br H OH H
I

c-
I

c-
I

A-
c- d-
-> It -

1 1
heat 1
/

A H H H
38 Alcohols From Halogenoalkanes

CH3CHzBr + NNOH - CH3CHzOH

NABR
+

CH3CHzBr + OH - CH3CHzOH+ Bt
-

"
H H H H

C-
1 1
C- C-
1 1

It - C -
H 7 It - H

3r H OH
39 Tests For The Presence of 'OH’ Group
1. With phosphorous pentachloride, PCl5, gives white fumes (of HCl)

CH3CH2OH + PCl5 ⟶ CH3CH2Cl + POCl3 + HCl

2. With sodium, gives out bubbles of gas that gives a pop sound with
a lighted splinter (hydrogen).

CH3CH2OH + Na ⟶ CH3CH2ONa + ½ H2
40 Tests to Differentiate Between Alcohols
Warm the alcohol with acidified sodium dichromate. If the orange color of
dichromate turns green, distill off the product and then warm it with Fehling’s
solution.
Tertiary alcohol: The orange color remains unaffected.
Secondary alcohol: The orange color turns green but Fehling’s solution is
unaffected.
Primary alcohol: The orange color turns green and with Fehling’s gives a brick-
red precipitate.
Note: Tollen’s reagent can also be used instead of Fehling’s solution. The result
would be a silver mirror or silver ppt.
 Htv EY
Hz CHZ CHZ

41 Iodoform Reaction
H '
a
Alcohols that contain the group CH3CH(OH)-, that is, those that have a methyl group
and a hydrogen atom on the same carbon atom that bears the OH group, can be
oxidised by alkaline aqueous iodine to the corresponding carbonyl compound
CH3C(O)-, which is further oxidised a salt of a carboxylic acid (with one less carbon)
and a pale yellow ppt of tri-iodomethane.
μ
CHZCHZ -

g- CHZ §tHz CHzCHz-§tIs

IZTOHTAQ )
#
CHZCHZ -
CHzCHz
§-5 OH
'

-
+ CHI
,

The overall reaction is:

42 Iodoform Reaction
Except for ethanol, all the alcohols that undergo this reaction are secondary
alcohols, with the OH group on the second carbon atom of the chain, that is,
they are alkan-2-ols.
43 Iodoform Reaction
The exception, ethanol, is the only primary alcohol to give the pale yellow
precipitate of tri-iodomethane (iodoform) with alkaline aqueous iodine:
 CHZCHCOH ) CHAO
- -

44 Skill Check
Which of these alcohols will undergo the iodoform reaction?

Hutti t ,
OH
It