H2 Chemistry 9729 Hydroxy Compounds

Anglo-Chinese Junior College

Department of Chemistry

HYDROXY COMPOUNDS
Prepared by: ACJC Chemistry Department

Section Content
A Alcohols (exemplified by ethanol)

1 Naming and Classification of Alcohols

2 Properties of Alcohols
2.1 Boiling point
2.2 Solubility
3 Preparation
3.1 Electrophilic Addition of Alkenes
3.2 Nucleophilic Substitution of Halogenoalkanes
3.3 Reduction from Carbonyl Compounds and Carboxylic Acids
4 Reactions of Alcohols
4.1 Combustion
4.2.1 Elimination to form Alkenes
4.2.2 Nucleophilic substitution to form Halogenoalkanes
4.3.1 Redox reaction with Sodium or Potassium
4.3.2 Condensation to form Esters
4.4 Oxidation to form Carbonyl Compounds and Carboxylic Acids
4.5 Oxidation with alkaline aqueous iodine (Iodoform Test)

B Phenol

5 Introduction
6 Properties of Phenol
5.1 Boiling point
5.2 Solubility
7 Chemical Reactions
7.1.1 Redox Reaction with Sodium or Potassium
7.1.2 Acid-base reaction with Bases
7.1.3 Condensation to form Esters
7.2 Electrophilic Substitution of Benzene Ring
7.3 Confirmation tests for phenol

C 8 Acidity of Hydroxy Compounds

8.1 Alcohols and Phenols as Brønsted-Lowry acids
8.2 Factors affecting acid strength
8.3 Comparing Acid Strengths of Phenol, Water and Ethanol

© 2024/JC2/Term 1/Chem Dept 1

H2 Chemistry 9729 Hydroxy Compounds

Learning Outcomes Section

Candidates should be able to:

a recall the chemistry of alcohols, exemplified by ethanol:

i. combustion 4.1
ii. nucleophilic substitution to give halogenoalkanes 4.2.2
iii. reaction with sodium 4.3.1
iv. oxidation to carbonyl compounds and carboxylic acids 4.4
v. dehydration to alkenes 4.2.1

b suggest characteristic distinguishing reactions for the different 4.4

classes of alcohols (primary, secondary and tertiary alcohols),
e.g. mild oxidation

c deduce the presence of a CH3CH(OH)– group in an alcohol from 4.5

its reaction with alkaline aqueous iodine to form tri-iodomethane

d recall the chemistry of phenol, as exemplified by the following

reactions:
i. with bases 7.1.2
ii. with sodium 7.1.1
iii. nitration of, and bromination of, the aromatic ring 7.2
e
explain the relative acidities of water, phenol and ethanol in 8.3
aqueous medium (interpret as Brønsted-Lowry acids)

Recommended readings and resources

1. Peter Cann and Peter Hughes, Cambridge International AS and A Level

Chemistry, 1st edition, Hodder Education, 2015.

2. Chan Kim Seng and Jeanne Tan, Understanding Advanced Organic and
Analytical Chemistry The Learner’s Approach, Revised Edition, WS Education,
2017.

© 2024/JC2/Term 1/Chem Dept 2

 H2 Chemistry 9729 Hydroxy Compounds

HYDROXY COMPOUNDS

Hydroxy compounds are organic compounds that contain the hydroxyl (–OH) functional
group. In general, they can be classified into two groups: Alcohols and Phenol.

Hydroxy compounds

Alcohol Phenol
OH

Aliphatic Aromatic
CH2 OH

Monohydric Polyhydric
H H H H

H C C H H C C H phenylmethanol
(benzyl alcohol)
H OH OH OH
ethanol ethane-1,2-diol

A. Alcohols

1. Naming and Classification of Alcohols

• Alcohols are named using the –ol suffix, replacing the –e of the corresponding
alkane.

• General formula: CnH2n+1OH or CnH2n+2O

• Classification of alcohols: Alcohols may be classified as a primary, secondary or

tertiary alcohols.

• It is necessary to classify alcohols because they react differently in oxidation

reactions.

Alcohol Primary (1o) Secondary (2o) Tertiary (3o)

H R R
(R = alkyl or aryl group)
H C OH H C OH R C OH
R
R R
No of alkyl / aryl groups 1 2 3

© 2024/JC2/Term 1/Chem Dept 3

 H2 Chemistry 9729 Hydroxy Compounds

Naming Aliphatic Alcohols

1) Identify the longest carbon chain bearing the most number of OH groups.
2) Each name is derived by changing the terminal ‘e’ of the corresponding alkane
name to ‘ol’
3) The location of the OH group is designated by using the lowest possible
number of the carbon atom bearing the OH group and the number is written
between the stem of the name and the 'ol'.

Examples

Molecular
CH4O C2H6O2 C3H8O C6H12O
formula
H H H
H H H
H C C C H
H
H C C C OH

H C OH
H OH H OH
Structural H H H
formula H CH3CHOHCH3
CH2OHCH2OH CH3CH2CH2OH
CH3OH

Name methanol ethane-1,2-diol propan-1-ol propan-2-ol cyclohexanol

Classification - primary (1°) primary (1°) secondary (2°) secondary (2°)

Molecular
C4H10O C8H10O C9H12O
formula
H OH H
H H H

H C C C H
H C C C OH

H H
H H
H C H H C H

Structural H H
formula
CH3CH(CH3)CH2OH CH3C(OH)(CH3)CH3

Name 2-methylpropan-1-ol 2-methylpropan-2-ol 2-phenylethan-1-ol 2-phenylpropan-2-ol

Classification primary (1°) tertiary (3°) primary (1°) tertiary (3°)

© 2024/JC2/Term 1/Chem Dept 4

 H2 Chemistry 9729 Hydroxy Compounds

Quick Check Classify the following as primary, secondary or tertiary alcohols.

Name 3-methylbutan-2-ol propane-1,2,3-triol 2,3-dimethylbutan-2-ol 2-cyclohexylethan-1-ol

Classification

2. Properties of Alcohols

2.1 Boiling point

Most simple aliphatic alcohols are liquids at room temperature. Aliphatic alcohols
with more than 12 carbons and higher aromatic alcohols are waxy solids.

Alcohols are polar due to the presence of the OH group. They allow alcohols to
form hydrogen bonding.

hydrogen bond
RECAP
To illustrate a hydrogen bond:
1. Draw lone pair of electrons on F/O/N.
2. Indicate δ+ and δ−
3. Draw dashed line and label the bond.

Question Explain the difference in boiling points for propane, methanethiol and ethanol.

Compound Mr b.p. (oC)

CH3CH2CH3 45 −42.0
CH3SH 48 5.8
CH3CH2OH 46 78.0

Answer
CH3CH2CH3, CH3SH and CH3CH2OH have simple molecular structures with weak
intermolecular forces between molecules.

CH3CH2OH molecules are attracted by the hydrogen bonds which are stronger than
permanent dipole-permanent dipole (pd – pd) interactions between CH3SH molecules
which is in turn stronger than instantaneous dipole-induced dipole (id – id) interactions
between CH3CH2CH3 molecules.

More energy is needed to overcome hydrogen bonds between CH3CH2OH molecules thus
CH3CH2OH has the highest boiling point. More energy is required to break the stronger

© 2024/JC2/Term 1/Chem Dept 5

 H2 Chemistry 9729 Hydroxy Compounds

pd – pd interactions between CH3SH molecules as compared to the id – id interactions

between CH3CH2CH3, thus CH3SH has higher boiling point than CH3CH2CH3.

Factors affecting boiling points of alcohols:

(i) Length of alkyl chain

Mr Melting Boiling
Compound
point / oC point / oC
Methanol, CH3OH 32 −98 65
Ethanol, CH3CH2OH 46 −114 78
Propan-1-ol, CH3CH2CH2OH 60 −126 97
Butan-1-ol, CH3CH2CH2CH2OH 74 −90 118
Pentan-1-ol, CH3CH2CH2CH2CH2OH 88 −78 138
Hexan-1-ol, CH3CH2CH2CH2CH2CH2OH 102 −45 157

Qn: State and explain the trend of boiling points from methanol to hexan-1-ol.

• Boiling point increases from methanol to hexan-1-ol.

• As Mr increases down the homologous series, increase in the number of
electrons gives rise to larger and more polarisable electron clouds.
• Thus stronger instantaneous dipole – induced dipole (id – id) interactions are
present between the molecules.
• More energy is needed to overcome stronger id – id interactions between the
molecules.

(ii) Branching

Alcohol pentan-1-ol 2-methylbutan-1-ol 2,2-dimethylpropanol

Structural
CH3CH2CH(CH3)CH2OH CH3C(CH3)2CH2OH
formula CH3CH2CH2CH2CH2OH

Class primary primary primary

b.p. / oC 138 129 114

• Branched-chain isomers have lower boiling point than straight chain isomers
as branched isomers have more spherical electron clouds that have smaller
surface area of contact and hence weaker id – id interactions between the
molecules.
• Less energy is needed to overcome weaker id – id interactions hence branched
alcohols have lower boiling point.

© 2024/JC2/Term 1/Chem Dept 6

H2 Chemistry 9729 Hydroxy Compounds

(iii) Number of OH groups

Compound Mr Boiling point / oC

Ethane-1,2-diol, CH2(OH)CH2OH 62 197
Propan-1-ol, CH3CH2CH2OH 60 97

• Ethane-1,2-diol has an extra OH group which leads to more extensive

hydrogen bonding than propan-1-ol. Thus more energy is needed to overcome
more extensive hydrogen bonding between molecules of ethane-1,2-diol.

2.2 Solubility

Alcohols with shorter carbon chains are soluble in water, while those with longer carbon
chains are not, even though hydrogen bonds can be formed.

• As length of non-polar carbon chain increases, the strength of instantaneous

dipole-induced dipole (id – id) interactions between alcohol molecules
increase.

• The energy released in forming id – id interactions between alcohol molecules

and water molecules is insufficient to compensate the energy needed to
overcome the stronger hydrogen bonds between water molecules and the id–
id interactions between alcohol molecules.

• Also, steric hindrance of the bulky alkyl groups reduces effective hydrogen
bonding between the alcohol functional group and water molecules.

• Hence alcohol molecules with long carbon chains cannot be solvated by water
molecules, thus they are not soluble in water.

© 2024/JC2/Term 1/Chem Dept 7

H2 Chemistry 9729 Hydroxy Compounds

3. Preparations

3.1 Electrophilic Addition of Alkenes

Type of Electrophilic Addition

reaction
Reagent and Laboratory method:
Conditions ▪ Cold concentrated H2SO4, followed by boiling with water; or
Industrial method:
▪ Steam and H3PO4 (catalyst), high temperature and high pressure
Equation

Quick Check What is the role of conc. H2SO4 in the laboratory method?

3.2 Nucleophilic Substitution of Halogenoalkanes

RX + NaOH → ROH + NaX

Primary, secondary and tertiary halogenoalkanes undergo nucleophilic

substitution with the hydroxide ion to yield the corresponding alcohol.

Type of reaction Nucleophilic substitution

KOH (aq) or NaOH (aq). Heat under reflux
Reagent and Aqueous medium is used and not alcoholic medium. (otherwise
Conditions elimination will occur) (note: (aq) means aqueous medium)

Nucleophile :OH–

heat under reflux -

Equation CH3CH2Br + OH CH3CH2OH + Br

Tertiary halogenoalkanes are also readily undergo nucleophilic substitution with

the weaker nucleophile, water, at room temperature.

© 2024/JC2/Term 1/Chem Dept 8

H2 Chemistry 9729 Hydroxy Compounds

3.3 Reduction of Carbonyl Compounds and Carboxylic Acids

• A common reducing agent is H2(g) with nickel catalyst, at high temperature and
high pressure; or H2(g) with platinum catalyst at room temperature

• Lithium aluminium hydride and sodium borohydride are also reducing

agents.

• They reduce carboxylic acids, aldehydes and ketones to alcohols.

Lithium aluminium hydride Sodium borohydride

LiAlH4 NaBH4

• These three reducing agents may allow selective reduction of functional groups.
(refer to Quick Check)

• Carboxylic acids and aldehydes are reduced to the corresponding primary

alcohols.

LiAlH4 in dry ether OR

NaBH4 in methanol OR
H2, Pt

• Ketones are reduced to the corresponding secondary alcohols.

LiAlH4 in dry ether OR

NaBH4 in methanol OR
H2,

R1 R2

© 2024/JC2/Term 1/Chem Dept 9

 H2 Chemistry 9729 Hydroxy Compounds

Type of reaction Reduction

Reagent and For reduction of carboxylic acid:

Conditions • Lithium aluminium hydride (LiAlH4) in dry ether

For reduction of aldehydes or ketones:

• Lithium aluminium hydride (LiAlH4) in dry ether OR
• Sodium borohydride (NaBH4) in methanol OR
• H2(g) with nickel catalyst, at high temperature and high pressure; or
H2(g) with platinum catalyst at room temperature

Overall Some examples

equation
Reduction using LiAlH4 in dry ether:

Note: Add [H] to

balance the equation
when LiAlH4 or NaBH4
are the reducing
agents.

Reduction using NaBH4 in methanol:

Note: H2 is used to
balance the equation Reduction using hydrogen over nickel catalyst at high temperature and pressure:
when it is the
reducing agent. high temp

© 2024/JC2/Term 1/Chem Dept 10

 H2 Chemistry 9729 Hydroxy Compounds

Quick Check Draw the structure of the compound formed in each of the following
reactions.

H2

high pressure

methanol
H2

Think: How to obtain the product where only the alkene is reduced?

4. Reactions of Alcohols

Reactions of ROH

4.1: reactions involving

4.2: Fission of reactions involving
4.3: Fission of 4.4: Oxidation 4.5: Iodoform
tri-iodomethane
combustion oxidation
Combustion fission of the fission
O – H of the
bond reaction
reaction
C – O bond
C O bond O H bond
I2, NaOH(aq), warm
4.2.2: Nucleophilic 4.3.1: Redox
substitution of
substitution to form
OH by X
reaction with
reaction withNa or
Na oxidation of 1o ROH to aldehydes
halogenoalkanes K - K2Cr2O7, dilute H2SO4,
- dry HX and heat heat with immediate distillation
- PX3 4.3.2: Condensation
- PCl5
esterification
to form esters
oxidation of 1o ROH to RCOOH
- SOCl2 - K2Cr2O7, dilute H2SO4, heat
heat under reflux
- RCOOH,
conc. H2SO4, heat heat under reflux
- KMnO4, dilute H2SO4, heat
4.2.1: Elimination/ to
dehydration
form alkenes
elimination oxidation of 2o ROH to ketones
- excess conc. H2SO4, acylation - K2Cr2O7, dilute H2SO4, heat
heatunder reflux
heat oC
170 - KMnO4, dilute H2SO4, heat
heat under reflux
- Al2O3, heat - RCOCl,
- conc. H3PO4, heat room temperature

© 2024/JC2/Term 1/Chem Dept 11

H2 Chemistry 9729 Hydroxy Compounds

4.1 Combustion

Learning Objective
Candidates should be able to recall the chemistry of alcohols, exemplified by ethanol:
• combustion

Alcohols undergo complete combustion in excess oxygen to produce only carbon

dioxide and water.

CH3CH2OH + 3O2 → 2CO2 + 3H2O

In excess oxygen, ethanol burns with a pale blue (non-luminous) flame. With a
limited supply of oxygen, ethanol burns with a yellow (luminous) flame and some
soot is also formed.

4.2 Fission of C – O bond

4.2.1 Elimination to form Alkenes

Learning Objective
Candidates should be able to recall the chemistry of alcohols, exemplified by ethanol:
• Dehydration to alkenes

Alcohols with H and OH on adjacent carbons atoms can be eliminated to yield

alkenes.

General equation:

Type of reaction Elimination

Reagent and ▪ Excess concentrated sulfuric acid H2SO4, heat; or

Conditions ▪ Alumina Al2O3, heat; or
▪ Concentrated phosphoric acid H3PO4, heat

© 2024/JC2/Term 1/Chem Dept 12

H2 Chemistry 9729 Hydroxy Compounds

Equation Example

4.2.2 Nucleophilic Substitution to form Halogenoalkanes

Learning Objective
Candidates should be able to recall the chemistry of alcohols, exemplified by ethanol:
• Nucleophilic substitution to give halogenoalkanes

This involves the replacement of the hydroxyl (OH) group with a halide through
breaking the C-O bond.

C C
OH X

(i) With hydrogen halide (HX)

Alcohols are converted to halogenoalkanes when reacted with hydrogen

halide. These reactions are most suitable for tertiary alcohols.

General equation: R−OH + HX → R─X + H2O

a) To produce RCl:
Add dry HCl gas or concentrated HCl to the alcohol in the presence of
anhydrous ZnCl2 to form the chloroalkanes.

Type of reaction Nucleophilic substitution

Reagent and 1) dry HCl(g) OR

Conditions
2) concentrated HCl, anhydrous ZnCl2

Overall
equation R OH + HX R X + H2O

Example: CH3CH2OH + HCl → CH3CH2Cl + H2O

© 2024/JC2/Term 1/Chem Dept 13

H2 Chemistry 9729 Hydroxy Compounds

b) To produce RCl or RBr:

Alcohol is refluxed with NaX and concentrated H2SO4. Concentrated H2SO4
and the sodium salt of the halide (NaX, where X = Br or Cl) form hydrogen
halide (HX) in-situ. HX reacts immediately with the alcohol to form the
halogenoalkane.

Type of reaction Nucleophilic substitution

Reagent and NaX with concentrated H2SO4 (for X = Cl and Br), heat under
Conditions reflux
Remarks Formation of HCl in-situ: Formation of HBr in-situ:
NaCl + H2SO4 NaBr + H2SO4
→ HCl + NaHSO4 → HBr + NaHSO4

Equation CH3CH2OH + HCl CH3CH2OH + HBr

→ CH3CH2Cl + H2O → CH3CH2Br + H2O

c) To produce RI:
Alcohol is refluxed with NaI and concentrated H3PO4. The HI gas that is
produced in–situ reacts with the alcohol to form iodoalkane. H3PO4 is used
instead of H2SO4 because HI is readily oxidised by concentrated H2SO4 to
I2.

Type of reaction Nucleophilic substitution

Reagent and NaI and concentrated H3PO4, heat under reflux

Conditions
Remarks Formation of HI in-situ: NaI + H3PO4 → NaH2PO4 + HI

Equation CH3CH2OH + HI → CH3CH2I + H2O

Primary and secondary alcohols are more resistant towards reaction with
acids, making them less likely to undergo reaction with hydrogen halides.

In order to form primary and secondary halogenoalkanes from alcohols, other reagents
such as phosphorus halides or thionyl chlorides should be used. (see section below)

(ii) With phosphorus halide: PCl5(s) or PX3

• Alcohols react with either PCl3 or PCl5 to form of chloroalkanes. They

react more readily with PCl5.

• Alcohols are heated with phosphorus and the respective halogen to

produce PBr3 or PI3 in-situ. PX3 react with alcohols to form
bromoalkanes or iodoalkanes.

© 2024/JC2/Term 1/Chem Dept 14

 H2 Chemistry 9729 Hydroxy Compounds

SOCl2 and PCl5 are the

Type of reaction Nucleophilic substitution most common reagents
to synthesise R-Cl.
Reagent and 1) PCl5 at room temperature
Conditions 2) PX3 (X = Cl, Br or I) and heat under reflux

Observation For PCl5: Evolution of white fumes of HCl which turns damp
blue litmus paper red indicates the presence of the alcoholic OH
group.

Overall
equation R OH + PCl 5
rt
R Cl + POCl 3 + HCl
Example CH3CH2OH + PCl5 → CH3CH2Cl + POCl3 + HCl

3R OH + PX3
heat
3R X + H3PO 3 PBr3 and PI3 are
the most common
where X is Cl or Br or I reagents to
synthesise R-Br and
Example 3CH3CH2OH + PBr3 → 3CH3CH2Br + H3PO3
R-I respectively.

A liquid mixture of the halogenoalkanes and phosphorus product is formed

in the above reactions. Fractional distillation is required to obtain the pure
halogenoalkane.

(iii) With thionyl chloride (SOCl2)

• Advantage of using SOCl2: All by-

products are gaseous and can be
removed easily from the solution, making
it easy to isolate the pure
halogenoalkanes.

Type of reaction Nucleophilic substitution

Reagent and SOCl2
Conditions

Observation Evolution of white fumes of HCl which turns damp blue litmus
paper red indicates the presence of the alcoholic OH group.
See the observable
changes for this Overall ROH + SOCl2 → RCl + SO2 + HCl
chemical reaction
by scanning the QR
equation
code. Example CH3CH2OH + SOCl2 → CH3CH2Cl + SO2 + HCl
.

© 2024/JC2/Term 1/Chem Dept 15

H2 Chemistry 9729 Hydroxy Compounds

4.3 Fission of O – H bond

4.3.1 Redox reaction with sodium or potassium

Learning Objective
Candidates should be able to recall the chemistry of alcohols, exemplified by ethanol:
• Reaction with sodium

Alcohols react with sodium or potassium to form alkoxide ion (e.g. ethoxide) and
hydrogen gas. It involves the breaking of the O−H bond:

_ +
C O H + M C O M + 1/2 H2

Type of reaction: Redox

Example: 2CH3CH2OH + 2Na → 2 CH3CH2O¯ Na+ + H2

sodium ethoxide

4.3.2 Condensation to form ester

With carboxylic acid (esterification)

Alcohols react with carboxylic acids to form esters.

The reagents need to be heated under reflux with a few drops of concentrated
sulfuric acid (catalyst). The reaction is slow and reversible.

General equation:
O H conc H2SO4 O H
+
R C OH H O C R ' R C O C R ' + H2O

H heat under reflux H

NOTE: C – O bond of carboxylic acid and O – H bond of alcohol cleaves

Type of reaction Condensation

Reagent and Carboxylic acid and a small amount of concentrated H2SO4

Conditions Heat the mixture under reflux

© 2024/JC2/Term 1/Chem Dept 16

H2 Chemistry 9729 Hydroxy Compounds

Overall Example:
equation

(ii) With acyl halide (acylation)

O

Acylation is the introduction of the acyl group ( R C ) into a molecule.

Alcohols react with acyl halides to form esters.

The reactions are faster, irreversible and give much higher yield compared to
the previous reaction.

Type of reaction Condensation

Reagent and Acyl halide at room temperature

Conditions
Overall Example:
equation

Observation White fumes of HCl which turns damp blue litmus red

© 2024/JC2/Term 1/Chem Dept 17

H2 Chemistry 9729 Hydroxy Compounds

4.4 Oxidation to give Carbonyl Compounds and Carboxylic Acids

Learning Objective
Candidates should be able to
• Recall the chemistry of alcohols, exemplified by ethanol:
o Oxidation to carbonyl compounds and carboxylic acids
• Suggest characteristic distinguishing reactions for the different classes of alcohols
(primary, secondary and tertiary alcohols), e.g. mild oxidation
•
• (i) Primary alcohol

Primary alcohols are easily oxidised to aldehydes, and further oxidised

to carboxylic acids.

K2Cr2O7, H2SO4 (aq) Heat under reflux with

Heat under K2Cr2O7, H2SO4(aq),
distillation OR KMnO4, H2SO4(aq)

Heat under reflux with K2Cr2O7, H2SO4(aq), OR KMnO4, H2SO4(aq)

a) Primary alcohols are oxidised to the corresponding aldehydes by heating

under distillation with K2Cr2O7(aq) and dilute H2SO4.

KMnO4(aq) should not be used as it is a stronger oxidising agent and will

oxidise the primary alcohol directly to carboxylic acid.

Type of reaction Oxidation

Reagent and K2Cr2O7(aq), dilute H2SO4(aq) and heat under distillation

Conditions
Observations The solution turns from orange (Cr2O72−) to green (Cr3+).

Overall
equation

The ethanal formed is distilled out of the reaction mixture to prevent

further oxidation.

Without distillation, ethanal will be further oxidised to ethanoic acid.

© 2024/JC2/Term 1/Chem Dept 18

 H2 Chemistry 9729 Hydroxy Compounds

b) Primary alcohols are oxidised to the correspond carboxylic acids by

heating under reflux with either K2Cr2O7(aq) or KMnO4(aq) and dilute
H2SO4.

Type of reaction Oxidation

Reagent and K2Cr2O7 (aq), dilute H2SO4 (aq) and heat under reflux
Conditions or
Watch videos of the KMnO4 (aq), dilute H2SO4 (aq) and heat under reflux
oxidation of ethanol
using Observations For K2Cr2O7 (aq), the solution turns from orange (Cr2O72−) to
1) acidified K2Cr2O7 green (Cr3+).

For KMnO4, the solution turns from purple (MnO4-) to pale pink
(Mn2+) OR the purple solution (MnO4-) is decolourised.

Overall
2) acidified KMnO4 equation

Example:

(ii) Secondary alcohol

.
Heat under reflux with
K2Cr2O7, H2SO4(aq),
OR KMnO4, H2SO4(aq)

Secondary alcohols are oxidised to the corresponding ketones by

heating under reflux with either K2Cr2O7 (aq) or KMnO4 (aq) and dilute
H2SO4.

Ketones are generally resistant to further oxidation.

Type of reaction Oxidation

Reagent and K2Cr2O7 (aq), dilute H2SO4 (aq) and heat under reflux
Conditions or
KMnO4 (aq), dilute H2SO4 (aq) and heat under reflux

Observations (same as primary alcohol)

© 2024/JC2/Term 1/Chem Dept 19

H2 Chemistry 9729 Hydroxy Compounds

Overall Example:
equation

(iii) Tertiary alcohol

Tertiary alcohols are resistant to oxidation. This is because 3o alcohols do

not have any hydrogen atom to be removed from the carbon atom to which
the OH group is attached. Hence, they will not be oxidised.

Quick Check
Draw the structure of the compound formed, if any, in each of the following reactions.

1)
CH3 H KMnO 4, dilute H 2SO 4
H3C C C CH3 No Reaction
OH CH3 heat under reflux

2)
KMnO4(aq)
OH dilute H2SO4 COOH
+ 2[O]
+ H2O
heat under reflux

© 2024/JC2/Term 1/Chem Dept 20

H2 Chemistry 9729 Hydroxy Compounds

Clarification
What are the differences between the two processes, distillation and reflux?

Similarity
Both processes require the use of a condenser with cool water running in from the
bottom to condense hot vapours.

Differences
1) Setup – In the distillation setup, the condenser is joined as a side arm so that the
condensed liquid will flow into a second container. This allows it to be separated from
its original mixture. For reflux, the condenser is set up vertically so that the condensed
liquid returns to the original mixture, ie. the reaction mixture.

2) Purpose – distillation is used for separating two liquids that have different boiling
points, while reflux is used to condense the solvent of a reaction mixture back into the
original flask. In simplistic terms, distillation enables separation, while reflux prevents
separation.
Here is a video
that compares
Distillation Reflux
the experimental
setups for reflux
and distillation.
Temp controlled just over 21oC,
but well below 70oC Any alcohol that
boils will condense
and drips back into
the reaction flask
until it is eventually
oxidised.

For greater
elaboration, view
the next video.

Mixture of excess
ethanol (b.p. 78oC)
+ K2Cr2O7 + dilute
H2SO4

Aldehyde

Used for the conversion of
• primary alcohol to aldehyde
.
Used for the conversion of
• primary alcohol to carboxylic acid
or
• secondary alcohol to ketone

© 2024/JC2/Term 1/Chem Dept 21

H2 Chemistry 9729 Hydroxy Compounds

4.5 Oxidation with alkaline aqueous iodine (Iodoform Test)

Learning Objective Candidates should be able to deduce the presence of a CH3CH(OH)–

group in an alcohol from its reaction with alkaline aqueous iodine to form tri-iodomethane.

The formation of the triiodomethane (or iodoform) is a positive test for alcohols with
the following structure:
OH

CH3 C R

H where R = H or C

General equation:

As Na+ is a spectator ion, it may not be written in the equation.

Type of reaction Oxidation

(Overall)
Reagent and I2 (aq), NaOH (aq), heat
Conditions
Observations Yellow crystals of triiodomethane (CHI3) with a characteristic
‘antiseptic smell’.

Overall Example
equation

A positive test is also obtained for carbonyl compounds (ie. aldehyde and ketone)
with the following structure:

O Note: The reaction with carbonyl

compounds will be taught in-depth
in the next topic.
CH3 C R where R = H or C
R

Equation: CH3CHO + 3I2 + 4OH– → CHI3 + 3I– + 3H2O + HCOO–

Quick Check Which of the following alcohols give a positive triiodomethane test?
(i) methanol (ii) ethanol (iii) propan-2-ol (iv) butan-1-ol (v) butan-2-ol

© 2024/JC2/Term 1/Chem Dept 22

 H2 Chemistry 9729 Hydroxy Compounds

The first surgical antiseptic

Extra reading - Application of organic chemistry

During the Victorian era in England, hospitals were filthy.

Doctors wore blood-stained operating coats and used dirty
surgical instruments. Bed linens were rarely washed and
doctors sacrificed the cleanliness of their hands for the speed
of their work. Many patients who survived their surgeries
(sans anesthesia!) would subsequently die from gangrene
that developed on their surgical wounds.

Joseph Lister, a practicing surgeon, had read Louis Pasteur’s

theory of invisible ‘germs’ that are carried in the air. Lister
theorized that germs in the air caused infection of wounds, so
killing the germs could prevent death from infections.

Lister used a known deodorizing agent, carbolic acid, as an

antiseptic to kill germs on surgical instruments, doctors’
hands, wounds and bandages. His theory and actions were
ridiculed by his colleagues, but eventually proved to reduce
the rate of deaths due to hospital infections. By 1875, Lister’s
method of ‘carbolic treatment’ was widely followed by the
medical communities in many European countries.

Carbolic acid, now known as phenol, is no longer used

directly on wounds due to its corrosive nature.
Derivatives of phenol are used instead; a commonly
used phenol derivative is chloroxylenol, the active
ingredient in Dettol.

When diluted, Dettol may be used to clean cuts and

wounds, as well as to disinfect environmental surfaces
like household floors and kitchen work surfaces. As
several of its ingredients are insoluble in water, it
produces a milky emulsion of oil droplets when diluted in
water, exhibiting the ouzo effect. This effect, which is
also known as spontaneous emulsification, is due to an
oil-in-water emulsion whose fine droplets scatter the
light, giving rise to the milky-white colour.
Chloroxylenol
(IUPAC: 4-chloro-3,5-dimethylphenol)
References:
1. Joseph Lister: father of modern surgery, Dennis Pitt, MD MEd and Jean-Michel Aubin, MD
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3468637/
2. Image credit: http://www.dailymail.co.uk/news/article-1130463/Revealed-The-18th-century-guide-amputations-
operations-medical-tips.html

© 2024/JC2/Term 1/Chem Dept 23

H2 Chemistry 9729 Hydroxy Compounds

B. Phenol

5. Introduction

Phenols are compounds containing a hydroxyl (OH) group directly attached to an

aromatic ring.

Phenol is a colourless, hygroscopic, crystalline solid (m.p. 42 oC).

They are corrosive and powerful antiseptics.

Example: 4-chloro-3,5-dimethylphenol in Dettol.

Some members of the phenol family include:

OH OH OH
Br Br COOH

Br
phenol 2,4,6-tribromophenol 2-hydroxybenzoic acid

6. Properties of Phenol

6.1 Boiling point

Large amount of energy is needed to overcome the strong hydrogen bonding

between their phenol molecules. Hence, phenols are colourless crystalline solids
as they have high boiling point of 181 oC. However, phenols often appear pale pink
in colour due to impurities.

6.2 Solubility

Phenol is moderately soluble in water because it is able to form hydrogen bonds

with the water molecules. Most other bigger molecules containing the phenolic
functional group are generally insoluble in water (due to large hydrophobic
character of benzene ring).

© 2024/JC2/Term 1/Chem Dept 24

H2 Chemistry 9729 Hydroxy Compounds

7. Chemical Reactions

7.2: Electrophilic 7.1: Reactions of

substitution on hydroxyl group
benzene ring O–H bond fission

7.1 Reactions of the hydroxyl group

7.1.1 Redox Reaction with Sodium or Potassium

Learning Objective Candidates should be able to recall the chemistry of phenol with sodium

Phenol reacts with sodium to form salt and hydrogen gas, thus effervescence is
observed.

Type of reaction Redox

Reagent and Conditions Na(s) added to pure phenol

Observations Effervescence is observed. The gas extinguishes a

lighted splint with a ‘pop’ sound.

Overall
equation

7.1.2 Acid-base Reaction with Bases e.g. NaOH

Learning Objective Candidates should be able to recall the chemistry of phenol with bases

Phenol reacts with bases to form salt and water.

Type of reaction Acid-base

Reagent and Conditions NaOH(aq) or KOH(aq) added to phenol (aq)

© 2024/JC2/Term 1/Chem Dept 25

H2 Chemistry 9729 Hydroxy Compounds

Observations The cloudy mixture of aqueous phenol forms a

colourless solution.

Overall
equation

partially soluble in water soluble in water

(cloudy mixture) (colourless aq solution)

Adding dilute acid to sodium phenoxide is sufficient to convert it back to phenol.

7.1.3 Condensation to form Ester

Unlike alcohols, phenols do not react with carboxylic acids to form esters. This is
because phenols are weaker nucleophiles than alcohols.

To form phenyl esters from phenols,

1) Phenol is first converted to phenoxide ion by adding an alkali. The phenoxide
ion is a stronger nucleophile than phenol.

2) Acyl chloride (RCOCl) is used instead of carboxylic acid.

Type of reaction Condensation

Reagent and 1. NaOH (aq): To convert phenol to phenoxide ion.

Conditions 2. Acid chlorides, RCOCl

© 2024/JC2/Term 1/Chem Dept 26

H2 Chemistry 9729 Hydroxy Compounds

Overall Example:
equation

Observation White fumes of HCl turns damp blue litmus red.

7.2 Electrophilic Substitution of Benzene Ring

• In phenols, the hydroxyl group is strongly ring-activating, thus electrophilic

substitution takes place readily on the aromatic ring.

• The OH group is electron-donating by resonance effect:

o The p orbital of the O atom can interact with the p orbitals of the benzene ring.

o This allows the lone pair of electrons on the O atom to delocalise into the
ring, thus increases the electron density in the benzene ring.

OH

• The hydroxyl group is 2,4-directing, so electrophilic substitution takes place at

positions 2 and/or 4 with respect to the hydroxyl OH group.

7.2.1 Reaction with nitric acid

Learning Objective
Candidates should be able to recall the chemistry of phenol, as exemplified by the
following reactions:
(i) Mono-substitution
• Nitration of, and bromination of, the aromatic ring

The strong ring-activating effect of the OH group allows phenols to undergo

nitration and bromination more readily than benzene and alkylbenzenes.

This is exemplified by the nitration of phenol in the absence of sulfuric acid catalyst
or heat.

Reaction with dilute nitric acid forms a mixture of mono-substituted products.

© 2024/JC2/Term 1/Chem Dept 27

H2 Chemistry 9729 Hydroxy Compounds

Type of reaction Electrophilic substitution

Reagent and Conditions dilute HNO3 (aq) at room temperature
Overall equation Example:

(ii) Multiple-substitution

Reaction with concentrated nitric acid forms a tri-substituted product,

2,4,6-trinitrophenol.

Type of reaction Electrophilic substitution

Reagent and Conditions concentrated HNO3 at room temperature
Overall
equation

© 2024/JC2/Term 1/Chem Dept 28

 H2 Chemistry 9729 Hydroxy Compounds

7.2.2 Reaction with halogens

Learning Objective
Candidates should be able to recall the chemistry of phenol, as exemplified by the
following reactions:
• Nitration of, and bromination of, the aromatic ring

The ring activating effect of the OH group allows phenol to undergo halogenation
more readily than benzene.

In comparison with benzene, phenols undergo halogenation without any Lewis

acid catalyst.

(i) Mono-substitution

When bromine dissolved in CCl4 is used, a mixture of monosubstituted product is

obtained.

Watch the Type of reaction Electrophilic substitution

changes when Reagent and Conditions Br2 (CCl4) at room temperature
bromine water
is mixed with Observations Orange bromine is decolourised. White fumes of HBr are
phenol. given off that turn damp blue litmus red.
Overall
equation

2-bromophenol

4-bromophenol

(ii) Multiple-substitution

When bromine dissolved in aqueous medium is used, a mixture of trisubstituted

product is obtained.

Type of reaction Electrophilic substitution

Reagent and Br2(aq) at room temperature
Conditions

© 2024/JC2/Term 1/Chem Dept 29

H2 Chemistry 9729 Hydroxy Compounds

Observations Orange bromine is decolourised and a white precipitate of

2,4,6-tribromophenol is formed.
White fumes of HBr are given off that turn damp blue litmus red.
Overall
equation

7.3 Confirmation tests for Phenol

7.3.1 Neutral solution of FeCl3 (aq)

Violet colouration is obtained with the above reagent indicates the presence of
phenol. This can be used as a confirmatory test for the presence of phenol.

Reagent and Conditions neutral FeCl3 (aq)

Observations Violet complex formed

7.3.2 PCl5 or SOCl2

Unlike alcohols, phenols do not react with PCl5 or SOCl2 to produce white fumes
of HCl. This can be used as a distinguishing test between alcohol and phenol.

Reason
• p Orbitals containing the lone pair of electrons on the O atom can interact with the p
orbitals of the benzene ring and delocalises into the ring.
• The C–O bond in phenol has partial double bond character which makes it stronger
and more difficult to break.

Overlapping
of p orbitals
OH

Quick Check Suggest a simple chemical test to distinguish between the following
isomers.

© 2024/JC2/Term 1/Chem Dept 30

H2 Chemistry 9729 Hydroxy Compounds

Phenylmethanol 2-methylphenol

Chemical test:

Observations:

C. Acidic property of alcohol and phenols

8.1 Alcohols and phenols as Brønsted-Lowry acids

• Alcohols and phenols behave as Brønsted-Lowry acids by donating protons.

ROH + H2O RO− + H3O+

alcohol alkoxide ion
(acid) (conjugate base)

phenol phenoxide ion

(acid) (conjugate base)

The strength of an acid depends on

the stability of the conjugate base.

The more stable the conjugate base, the stronger the acid.

© 2024/JC2/Term 1/Chem Dept 31

 H2 Chemistry 9729 Hydroxy Compounds

8.2 Factors affecting strength of acids

Electron Donating Groups (EDG) Electron Withdrawing Groups

decrease the strength of an acid (EWG)
increase the strength of an acid
where the EDG can be
• alkyl (e.g. –CH3, –CH2CH3) where the EWG can be
• –NO2, –F, –Cl, –Br, –COR, –CHO, –CN,
• –OH –NH2 (if directly attached to the –COOH
benzene ring) • –OH –NH2 (if directly attached to the sp3
hybridised carbon)

alkoxide ion carboxylate ion alkoxide ion carboxylate ion

phenoxide ion phenoxide ion

Explanation Explanation
• The EDG intensifies the negative charge • The EWG disperses the negative charge
on the conjugate base on the conjugate base
• Making the conjugate base less stable • Making the conjugate base more stable
• Thus decreases acidity of the organic acid • Thus increases acidity of the organic
acid
Example 1 Example 2

Stability of conjugate bases: Stability of conjugate bases:

© 2024/JC2/Term 1/Chem Dept 32

 H2 Chemistry 9729 Hydroxy Compounds

From left to right, the increasing number of electron- From left to right, the increasing number of
donating alkyl groups intensify the negative electron-withdrawing chlorine atoms disperse
charge on the conjugate bases to a greater extent. the negative charge on the conjugate bases to a
greater extent.
This makes the conjugate bases less stable, thus This makes the conjugate bases more stable,
the corresponding acids decrease in acid strength. thus the corresponding acids increase in acid
strength.

Example 3 Comparing the acidity of 1o, 2o and 3o alcohols

Relative stability of conjugate bases: CH3CH2O– > (CH3)2CHO– > (CH3)3CO–

Relative acidity: CH3CH2OH > (CH3)2CHOH > (CH3)3COH

1o alcohol 2o alcohol 3o alcohol

From the primary to tertiary alkoxide ions, the increasing number of electron-donating alkyl groups
intensifies the negative charge on the conjugate base.

This makes the conjugate bases less stable, thus the alcohols decrease in acid strength from primary
to tertiary alcohol.

In general, relative acid strength:

primary alcohol > secondary alcohol > tertiary alcohol

8.3 Comparing Acid Strengths of Phenol, Water and Ethanol

Learning Objective
Candidates should be able to explain the relative acidities of water, phenol and ethanol
in aqueous medium (interpret as Brønsted-Lowry acids).

Phenol Water Ethanol

pKa 10 14 16
Ka (mol dm–3) 1 × 10–10 1 × 10–14 1 × 10–16
Relative acidity Phenol > Water > Ethanol

© 2024/JC2/Term 1/Chem Dept 33

H2 Chemistry 9729 Hydroxy Compounds

Phenol

phenol (acid) phenoxide ion (conjugate base)

Phenol is a stronger acid than water and ethanol because its conjugate base, the
phenoxide ion, is more stable.

In the phenoxide ion,

i. the p-orbital of oxygen overlaps with the -cloud of
the benzene ring
ii. which enables the delocalisation of the negative
charge on oxygen into the benzene ring.
iii. The phenoxide ion is stabilized to a greater extent
than the hydroxide ion and ethoxide ion.

Water
2H2O OH– + H3O+

Water is a stronger acid than ethanol. The hydroxide ion OH– is more stable than the
ethoxide ion.

Ethanol

CH3CH2OH + H2O CH3CH2O− + H3O+

ethoxide ion

Ethanol is a weaker acid than water and phenol.

In the ethoxide ion,

i. the electron-donating ethyl group intensifies the negative charge on the
oxygen atom of the conjugate base (ethoxide ion),
ii. thus destablising the ethoxide ion relative to ethanol.

© 2024/JC2/Term 1/Chem Dept 34

H2 Chemistry 9729 Hydroxy Compounds

However, phenol is a weaker acid than carbonic acid (H2CO3) and carboxylic
acids and does not displace carbon dioxide from carbonates.

Reaction with
Na (s) NaOH (aq) Na2CO3 (aq)

Alcohol increasing √ - -
Water acidity √ - -
Phenol √ √ -
Carboxylic acid √ √ √

Quick Check Arrange the following phenols in order of increasing acidity.

OH OH OH
OH
NO2 NO2

NO2 NH2 NO2

phenol 4-nitrophenol 4-aminophenol 2,4,6-trinitrophenol

© 2024/JC2/Term 1/Chem Dept 35