AN INTRODUCTION TO

THE CHEMISTRY
OF ALCOHOLS
Learning outcomes
You should be able to:
understand and be able to apply the
classification of alcohols
understand the oxidation of alcohols and their
products
understand the products of dehydration of
alcohols
 CLASSIFICATION OF ALCOHOLS

Aliphatic • general formula CnH2n+1OH - provided there are no rings

• the OH replaces an H in a basic hydrocarbon skeleton

Structural
differences • alcohols are classified according to the environment of the OH group
• chemical behaviour, eg oxidation, often depends on the structural type

PRIMARY 1° SECONDARY 2° TERTIARY 3°

L.O.: understand and be able to apply the classification of alcohols

 СH3CH2CH(CH3)OH
SECONDARY 2°

TERTIARY 3°

PRIMARY 1°

СH3CH2CH(OH)CH2CH3
SECONDARY 2°

SECONDARY 2°

СH3CH2C(CH3)2OH
TERTIARY 3°
 NAMING ALCOHOLS

Alcohols are named according to standard IUPAC rules

• select the longest chain of C atoms containing the O-H group;

• remove the e and add ol after the basic name

e.g. CH3 - CH(CH3) - CH2 - CH2 - CH(OH) - CH3 is called 5-methylhexan-2-ol

STRUCTURAL ISOMERISM IN ALCOHOLS

Different structures are possible due to...

A Different positions for the OH group butan-1-ol butan-2-ol

B Branching of the carbon chain 2-methylpropan-2-ol butan-2-ol

 YOUR TASK

Give the names and structures of all eight alcohols

with the formula C5H12O.
State in each case whether they are primary,
secondary or tertiary alcohols
 PHYSICAL PROPERTIES OF ALCOHOLS
BOILING POINTS OF ALCOHOLS

Alcohols have higher boiling points than similar molecular mass alkanes

Mr bp / °C
propane C3H8 44 -42 van der Waals’ forces
ethanol C2H5OH 46 +78 van der Waals’ forces + hydrogen bonding

SOLUBILITY Low molecular mass alcohols are miscible with water

Due to hydrogen bonding between the two molecules
Heavier alcohols are less miscible
 OXIDATION OF ALCOHOLS
All alcohols can be oxidised depending on the conditions

Oxidation is used to differentiate between primary, secondary and tertiary alcohols

The usual reagent is acidified potassium dichromate(VI) K2Cr2O7

Primary Easily oxidised to aldehydes and then to carboxylic acids.

Secondary Easily oxidised to ketones

Tertiary Not oxidised under normal conditions.

They do break down with very vigorous oxidation

PRIMARY 1° SECONDARY 2° TERTIARY 3°

L.O.: understand the oxidation of alcohols and their products

 OXIDATION OF PRIMARY ALCOHOLS
Primary alcohols are easily oxidised to aldehydes

e.g. CH3CH2OH(l) + [O] ——> CH3CHO(l) + H2O(l)

ethanol ethanal

it is essential to distil off the aldehyde before it gets oxidised to the acid

CH3CHO(l) + [O] ——> CH3COOH(l)

ethanal ethanoic acid
 OXIDATION OF PRIMARY ALCOHOLS
Controlling the products

e.g. CH3CH2OH(l) + [O] ——> CH3CHO(l) + H2O(l)

then CH3CHO(l) + [O] ——> CH3COOH(l)

OXIDATION TO ALDEHYDES OXIDATION TO CARBOXYLIC ACIDS

DISTILLATION REFLUX

Aldehyde has a lower boiling point so Aldehyde condenses back into the
distils off before being oxidised further mixture and gets oxidised to the acid
 OXIDATION OF SECONDARY ALCOHOLS
Secondary alcohols are easily oxidised to ketones

e.g. CH3CHOHCH3(l) + [O] ——> CH3COCH3(l) + H2O(l)

propan-2-ol propanone

The alcohol is refluxed with acidified K2Cr2O7.

However, on prolonged treatment with a powerful oxidising agent they can be further
oxidised to a mixture of acids with fewer carbon atoms than the original alcohol.

OXIDATION OF TERTIARY ALCOHOLS

Tertiary alcohols are resistant to normal oxidation
 OXIDATION OF ALCOHOLS
Why 1° and 2° alcohols are easily oxidised and 3° alcohols are not

For oxidation to take place easily you must have two hydrogen atoms on
adjacent C and O atoms.

H H
1° R C O + [O] R C O + H 2O
H H
H H
2° R C O + [O] R C O + H 2O
R R

This is possible in 1° and 2° alcohols but not in 3° alcohols.

R H
3° R C O + [O]
R
SOME PRACTICE
QUESTIONS
 CHEMICAL PROPERTIES OF ALCOHOLS

The OXYGEN ATOM HAS TWO LONE PAIRS; this makes alcohols lone pair donors

The alcohol uses one of its lone pairs to form a co-ordinate (dative) bond

NUCLEOPHILES Alcohols can use the lone pair to attack electron deficient centres
 ELIMINATION OF WATER (DEHYDRATION)

Reagent/catalyst conc. sulphuric acid (H2SO4) or conc. phosphoric acid (H3PO4)

Conditions reflux at 180°C
Product alkene
Equation e.g. C2H5OH(l) ——> CH2 = CH2(g) + H2O(l)
Mechanism

Step 1 protonation of the alcohol using a lone pair on oxygen

Step 2 loss of a water molecule to generate a carbocation
Step 3 loss of a proton (H+) to give the alkene

L.O.: understand the products of dehydration of alcohols

 ELIMINATION OF WATER (DEHYDRATION)

MECHANISM

Step 1 protonation of the alcohol using a lone pair on oxygen

Step 2 loss of a water molecule to generate a carbocation
Step 3 loss of a proton (H+) to give the alkene

Note 1 There must be an H on a carbon atom adjacent the carbon with the OH

Note 2 Alcohols with the OH in the middle of a chain

can have two ways of losing water.

In Step 3 of the mechanism, a proton can be lost

from either side of the carbocation. This gives a
mixture of alkenes from unsymmetrical alcohols...
Dehydration of butan-2-ol:
H H H H

H C C C C H loss of any of these hydrogen

+ atoms would give but-1-ene
H H H

loss of either of these hydrogen

atoms would give but-2-ene

H H H
H H H H H
C H
Butan-2-ol  but-2-ene: H C C C
+
C H H C C C

H H H H
H

H H H H H H H H
Butan-2-ol  but-1-ene H C C C C H H C C C C
+ H
H H H H H

HINT: Alcohols which have no H atoms on the C atom adjacent to the OH group cannot undergo elimination
SOME PRACTICE
QUESTIONS
Learning outcomes
You should be able to:
understand the two main routes for ethanol
production and the advantages and
disadvantages of each
understand the environmental issues of
ethanol production including those of
bioethanol fuels, and understand the concept
of carbon neutrality
be able to discuss biofuels in the context of
environmental issues
 INDUSTRIAL PREPARATION OF ALCOHOLS
FERMENTATION

Reagent(s) GLUCOSE - produced by the hydrolysis of starch

Conditions yeast
warm, but no higher than 37°C

Equation C6H12O6 ——> 2 C2H5OH + 2 CO2

 INDUSTRIAL PREPARATION OF ALCOHOLS
FERMENTATION

Reagent(s) GLUCOSE - produced by the hydrolysis of starch

Conditions yeast
warm, but no higher than 37°C

Equation C6H12O6 ——> 2 C2H5OH + 2 CO2

Advantages LOW ENERGY PROCESS

USES RENEWABLE RESOURCES - PLANT MATERIAL
SIMPLE EQUIPMENT

Disadvantages SLOW
PRODUCES IMPURE ETHANOL
BATCH PROCESS
 INDUSTRIAL PREPARATION OF ALCOHOLS
HYDRATION OF ETHENE

Reagent(s) ETHENE - from cracking of fractions from distilled crude oil

Conditions catalyst - phosphoric acid

high temperature and pressure

Equation C2H4 + H2O ——> C2H5OH

 INDUSTRIAL PREPARATION OF ALCOHOLS
HYDRATION OF ETHENE

Reagent(s) ETHENE - from cracking of fractions from distilled crude oil

Conditions catalyst - phosphoric acid

high temperature and pressure

Equation C2H4 + H2O ——> C2H5OH

Advantages FAST
PURE ETHANOL PRODUCED
CONTINUOUS PROCESS

Disadvantages HIGH ENERGY PROCESS

EXPENSIVE PLANT REQUIRED
USES NON-RENEWABLE FOSSIL FUELS TO MAKE ETHENE

Uses of ethanol ALCOHOLIC DRINKS

SOLVENT - industrial alcohol / methylated spirits
FUEL - petrol substitute in countries with limited oil reserves
SOME PRACTICE
QUESTIONS
 ETHANOL AS A FUEL
Ethanol is a useful biofuel:
- high enthalpy of combustion
- it burns with a clean flame and is increasingly used in car
- do not contain sulphur so there is less pollution
- can be obtained from renewable resources

C2H5OH(l) + 3O2(g) ———> 2CO2(g) + 3H2O(l)

Biofuels – what are they and

where do they come from?
 BIOFUELS
What are they?
Liquid fuels made from plant material and recycled elements of the food chain

Bio-ethanol https://www.youtube.com/watch?v=Qoy-adFRu44

- Ethanol can be made by fermentation.

- Fermentation is the process of using yeast to convert sugars into ethanol.
- Ethanol can be used as fuel it burns to give just carbon dioxide and water.

Biofuels are carbon-neutral.

What Is Carbon Neutral and Biofuels?

https://www.youtube.com/watch?v=I7VaTFscyFE
DESCRIBE WHAT YOU CAN SEE IN THE CARTOON
DEBATE CORNER
ADVANTAGES AND DISADVANTAGES OF BIOFUELS
 BIOFUELS

Advantages • renewable - derived from sugar beet, rape seed

• dramatically reduces emissions
• carbon neutral
• biodegradable
• non-toxic
• fuel & exhaust emissions are less unpleasant
• can be used directly in unmodified diesel engine
• high flashpoint - safer to store & transport
• simple to make
• used neat or blended in any ratio with petroleum diesel
 BIOFUELS

Advantages • renewable - derived from sugar beet, rape seed

• dramatically reduces emissions
• carbon neutral
• biodegradable
• non-toxic
• fuel & exhaust emissions are less unpleasant
• can be used directly in unmodified diesel engine
• high flashpoint - safer to store & transport
• simple to make
• used neat or blended in any ratio with petroleum diesel

Disadvantages • poor availability - very few outlets & manufacturers

• more expensive to produce
• poorly made biodiesel can cause engine problems
 BIOFUELS

Advantages • renewable - derived from sugar beet, rape seed

• dramatically reduces emissions
• carbon neutral
• biodegradable
• non-toxic
• fuel & exhaust emissions are less unpleasant
• can be used directly in unmodified diesel engine
• high flashpoint - safer to store & transport
• simple to make
• used neat or blended in any ratio with petroleum diesel

Disadvantages • poor availability - very few outlets & manufacturers

• more expensive to produce
• poorly made biodiesel can cause engine problems

Future
problems • there isn’t enough food waste to produce large amounts
• crops grown for biodiesel use land for food crops
• a suitable climate is needed to grow most crops
• some countries have limited water resources
 GREEN PEN
(a) C4H10O + 6O2  4CO2 + 5H2O (1) 1

(a) (i) 3-methylpentan-3-ol (1)

(ii) carbonium ion/carbocation (1)

CH 3 H CH 3 CH 2
C C (1) C CH 2
(iii) CH 3 CH 2 CH 3 CH 3 CH 2
(1)

C (1)

(b) lone pair (1)

(c) (i) orange (1)
tertiary alcohol (1)
not oxidised (1)
 (ii) two from:
CH 3

CH 3 CH CH2 CH CH 3

OH

CH3

CH 3 CH 2 CH CH CH 3

OH

CH3

CH 3 C CH CH 3

CH3 OH (2x1)
(a) A = tertiary alcohol/ 3° (1)
B = secondary alcohol/ 2° (1) 2
(b) (2)-methylpropan-2-ol (1) 1

(c) (i) (selects isomer C and) gives suitable structure for butanal (1)
or
(selects isomer D and) gives suitable structure for
2-methylpropanal (1) 1
(ii) (sodium / potassium) dichromate / manganate VII (1)
acidic conditions / H+ (this mark dependent on first mark) (1)
not HCl with KMnO4
distill(ation) not reflux (1) 3
(d) (i) removal of water (1) 1
(ii) alkene / ether (not a named example) (1) 1
(iii) concentrated sulphuric acid / concentrated or solid phosphoric acid
(strong) heat / high temperature / 150 – 200 °C / reflux
or
suitable catalyst eg aluminium oxide / broken porcelain (1)
strong heat / high temperature / 300+ °C (1)
mark for conditions dependent on mark for reagents 2
(iv) (selects isomer C and) gives suitable structure for but-1-ene
(accept but-2-ene structure if primary to secondary carbocation
rearrangement mentioned)
or
(selects isomer A or D and) gives suitable structure for
2-methylpropene (1)
also accept structures for ethers 1
(v) selects isomer B (1)
suitable structure for but-1-ene (mark independently of isomer
chosen) (1)
suitable structure for but-2-ene (either cis or trans not both) (1)
dehydration ‘involves the removal of OH and H to make water,
and H can be
either from C1 or from C3 so two isomers formed (1) 4
(a) (i) C6H12O6  2C2H5OH + 2CO2 1
(Or CH3CH2OH)
(Ignore state symbols in the equation)
(ii) Fermentation 1

(b) (i) C2H5OH + 3O2  2CO2 + 3H2O 1

(Or C2H6O or CH3CH2OH)
(ii) CO or carbon monoxide or C or carbon ONLY 1
(iii) 2CO + 2NO  2CO2 + N2
OR 2NO  N2 + O2
OR 2NO + C  N2 + CO2
OR C8H18 + 25NO  8CO2 12½N2 + 9H2O 1
(In equation 2, allow additional O2 on both sides of the
equation)
(c) Elimination 1
(Penalise additional words such as “electrophilic”)
18. (a) M1 fermentation 1
M2 dehydration or elimination 1

(b) (i) yeast OR zymase OR an enzyme 1

(ii) concentrated sulphuric or phosphoric acid 1
(penalise aqueous or dilute as a contradiction)

(c) (i) primary or 1° 1

(ii) sugar or glucose or ethanol is renewable 1
OR ethanol does not contain sulphur-containing impurities
OR ethanol produces less pollution or is less smoky or less CO/C
(the objective is a positive statement about ethanol)
(penalise the idea that ethanol is an infinite source or vague
statements that ethanol has less impurities) (penalise the idea
that ethanol produces no pollution)

(d) C2H6  C2H4 + H2 1

(e) Addition 1
(ignore self or chain as a preface to “addition “)
(penalise additional)