CHAPTER 8.

0
HYDROXY COMPOUNDS

8.1 Nomenclature
8.2 Physical Properties of Alcohols
8.3 Preparation of Alcohols
8.4 Chemical Properties of Alcohols
8.5 Phenols
 8.1 Nomenclature

LEARNING OUTCOMES:

At the end of this topic, students should be able to :

a) Draw the structure, classify and name

the hydroxy compounds (parent chain ≤ C10)
according to the IUPAC
nomenclature.
▪ Organic compounds containing hydroxyl group
(-OH) as the functional group.

▪ 2 types of hydroxy compounds :

1. Aliphatic alcohol
✓ Derivative of alkane with hydrogen atom is replaced by
the hydroxyl group (–OH group).

✓ General formula : CnH2n+1OH

2. Aromatic alcohol
✓ Derivative of benzene in which one hydrogen atoms is
replaced by a –OH group.
3
✓ -OH group attached directly to the aromatic ring.
Examples of aliphatic alcohol by using the general formula

CnH2n+1OH

CnH2n+1OH IUPAC name

C1H3OH methanol

C2H5OH ethanol
C3H7OH propanol
C4H9OH butanol
C5H11OH pentanol 4
Examples of aliphatic alcohol by using the general formula

CnH2n+1OH

CnH2n+1OH IUPAC name

C6H13OH hexanol

C7H15OH heptanol
C8H17OH octanol
C9H19OH nonanol
C10H21OH decanol 5
 Other examples of aliphatic alcohol
-OH group attached to
the side change and not
directly to the aromatic
ring.
OH CH2-OH

CH3CH2OH

ALIPHATIC ALCOHOL
(–OH group attached directly to the alkyl group)

6
 OH OH OH
CH3

Br

AROMATIC ALCOHOL
(–OH group attached directly to the aryl group)

7
 CLASSIFICATION OF ALCOHOL
▪ Alcohols are classified as according to the type of carbon
atom bonded to the hydroxyl group (-OH).
Methyl alcohol R -OH CH3OH
H
Primary (1o) alcohol
R-C-OH CH3CH2OH
-OH group attached to 1o carbon H
R
Secondary (2o) alcohol
R-C-OH CH3CHCH3
-OH group attached to 2o carbon H OH

R
Tertiary (3o) alcohol OH
R-C-OH
-OH group attached to 3o carbon CH3
R 8
 EXERCISE
Classify the types of alcohol (1o, 2o or 3o) of the
following molecules.

(a) CH3CH(OH)CH3 (b)

CH2OH
CH3
(c)

OH
H3C CH3
9
Naming the alcohol
1. The suffix ‘–e’ in the alkane parent name is replaced
by ‘–ol’
2. The location of the –OH on the longest chain is given
by the smallest possible number.

IUPAC rules for naming alcohols

1. Determine parent name.
2. Give the lowest number to the carbon bearing the
–OH group.
3. Identify substituent groups and their position.
4. Name the alcohol.
 Common Name

▪ The common name of an alcohol is obtained by

citing the name of the alkyl group to which the OH
group is attached, followed by the word “alcohol”
→ alkyl alcohol.

▪ Example :
i. ii. CH3CHCH3
CH3CH2OH
OH
ethyl alcohol isopropyl alcohol
iii. CH3 iv.
CH3 C OH OH
CH3
tert-butyl alcohol cyclohexyl alcohol
12
 Nomenclature
Structure General name @ IUPAC name
common name

methyl alcohol methanol

CH3OH
ethyl alcohol ethanol
CH3CH2OH
isopropyl alcohol 2-propanol
CH3CH(OH)CH3

OH cyclohexyl alcohol cyclohexanol

▪ If there are two or more –OH groups present, the name ends
with ‘diol’, ‘triol’ and so on.

Example :

i. ii. OH OH
OH
CH3CHCH2OH

1,2-propanediol 1-cyclohexyl-1,3-butanediol
• The –OH group is named as a hydroxy substituent

when it appears on a structure with a higher

priority functional group, or when the structure

is too difficult to name as a simple alcohol.

Example :
OH
i.
OH O ii.
CH3CHCH2C-OH
O

3-hydroxybutanoic acid 2-hydroxycyclohexanone

 Alcohol with 2 or 3 hydroxy groups

Structure IUPAC name

1,2-ethanediol
CH2(OH)CH2OH

1,2-propanediol
CH3CH(OH)CH2OH

1,3-propanediol
HOCH2CH2CH2OH

1,2,3-propanetriol
CH2(OH)CH(OH)CH2OH
 Naming Alcohols
CH2OH

H2C=CHCH2OH

IUPAC name phenylmethanol 2-propene-1-ol

common name benzyl alcohol allyl alcohol

CH3

H3C C OH HOCH2CHCH2OH

CH3 OH
IUPAC name 2-methyl-2-propanol 1,2,3-propanetriol
common name tert-butyl alcohol glycerol
▪ For phenol, C attach to the –OH group is C1.

OH OH
OH
CH3

CH2CH3 Br

3-ethylphenol 3-bromophenol 2-methylphenol

or or or
m-ethylphenol m-bromophenol o-methylphenol
Benzene derivatives with 2 –OH groups
are name as benzenediol.

OH

OH

IUPAC name 1,4-benzenediol

common name (hydroquinone)
Benzene derivatives with 2 –OH groups are name as
benzenediol.

OH
OH
OH

OH

1,3-benzenediol 1,2-benzenediol
 Exercise
1) Name the following compounds by using IUPAC
nomenclature
Br
(a) CH2CH(CH3)CH2OH (c)

OH

(b) (d)
HO CH3

CH3
OH NO2
(e) H CH(CH3)2

HO H

CH3
CHCHCH3
(f)
OH

Br
(g)

OH
ANSWER

a) 2-methyl-3-phenyl-1-propanol
b) 2-nitrocyclohexanol
c) 4-bromophenol @ p-bromophenol
d) 4,4-dimethylcyclohexanol
e) trans-3-isopropylcyclopentanol
f) 3-phenyl-2-butanol
g) 2-bromocyclopentanol
 Exercise
2) Draw the structural formulae of the following compounds

(a) 2-amino-3-bromophenol

(b) 2-chlorophenol

(c) 3-isopropylphenol

(d) 2-phenylbutanol
ANSWER

HO HO
(a) NH2 (c) Cl

Br

HO
(b) (d) CH CH CHCH OH
3 2 2

CH(CH3)2
 8.2 Physical Properties
of Alcohols

LEARNING OUTCOMES:

At the end of this topic, students should be able to:

a) Analyse the physical properties:

i. boiling point
ii. solubility in water

26
 1. Physical State
Number of Physical form
carbons

Simple alcohol • Liquid at room temperature

C < 12 • Colourless
Example : methanol and ethanol are free-
flowing volatile liquids with characteristic
of fruity odors.
C > 12 • Solids at room temperature

Phenol • Crystalline solid

27
• Corrosive and poisonous
▪ Alcohol molecules are polar due to the high
electronegativity of oxygen atom.
▪ Therefore, both C-O and O-H bond are polar.

H
δ+ δ- δ+
R C O H

▪ The polarity of alcohol molecules provides reaction

sites for many reactants and affects the physical
properties of alcohols.

▪ Polarization of O-H bond enables the alcohol

molecules to form a strong hydrogen bonds to each
28
other or with water molecules.
2. Boiling Point

▪ The boiling points of alcohols are higher than alkanes or

haloalkanes of similar relative molecular mass (Mr).

▪ Because alcohol can form intermolecular hydrogen bond

between its molecules

hydrogen bond hydrogen bond

R R
O O
H H H H
O O
R R 29
 Example :

Organic compounds Mr Boiling point

CH3CH2OH 46 78OC

CH3CH2CH3 44 - 42OC

CH3Cl 50.5 - 24OC

The boiling point of alcohol is considerably higher than those

alkane or chloroalkane of similar relative molecular mass.
Why? 30
▪ The boiling points of alcohols increases with
a) increasing of relative molecular mass, Mr
b) the number of –OH groups

Other examples:
No. Alcohol compounds Mr Boiling point

i. CH3OH 32 64

ii. CH3CH2OH 46 78

iii. CH3CH2CH2OH 60 97

iv. HOCH2CH2OH 62 197

v. HOCH2CH2CH2OH 76 215
31
▪ Alcohols with branched carbon chains have lower boiling
points than their straight chain isomers.

- because branched-chain alcohols have smaller surface

areas of contact.

▪ The order of the boiling points of isomeric alcohols:

32
Example:
Alcohol compounds Mr Boiling point
CH3CH2CH2CH2OH 74 118 OC

CH3CH2CHCH3
74 100 OC
OH

CH3
CH3-C-OH 74 83 OC
CH3

33
3. Solubility

▪ Water and alcohols have similar properties because of the

presence of –OH groups in the molecules.

▪ The smaller alcohols (methanol, ethanol and propanol) are

completely soluble in water because the hydrogen bonds
are formed between alcohols and water molecules.

Hydrophilic
H area
R
R O
O O R OH
H H H
Hydrophobic
34
area
▪ Example:
H Hydrogen
Bond
H3CH2C O
O

H H O CH2CH3

▪ As the number of carbon atoms (hydrophobic group) in

the alcohol molecule increases, the solubility of the
alcohol in water decreases.

▪ For alcohol with the same Mr , solubility increases with

increasing number of –OH group.
-form more hydrogen bonds with water.
35
 EXERCISE
1. Arrange the following compounds in the order of increasing
boiling point. Explain your answer.

1,2-ethanediol , n-butane , 1-propanol , 1,3-propanediol

2. Predict which of the compound is more soluble in water.

Briefly explain your answer.
(a) propane & 1-propanol
(b) 1-propanol & 1,2-propanediol
36
(c) 2-propanol & 2-pentanol
 ANSWER
1. n-butane < 1-propanol <1,2-ethanediol < 1,3-propanediol
increasing boiling point
➢ n-butane has the lowest boiling point because it has no
hydroxyl group attach to it. n-butane only form weak van der
Waals forces between molecules.
➢1-propanol has higher boiling point than n-butane because
1-propanol form intermolecular hydrogen bond which is
stronger than van der Waals forces.
➢1,2-ethanediol and 1,3-propanediol have higher boiling
point than 1-propanol because they have two hydroxyl group
which can form more number of hydrogen bonds.
➢1,3-propanediol has the highest boiling point because it has
the highest molecular weight and biggest molecular size. So,
1,3-propanediol has stronger van der Waals forces than 1,2-37
ethanediol.
 ANSWER
2. a) 1-propanol more soluble in water.
➢ It is because 1-propanol consists of hydroxyl group
which can form intermolecular hydrogen bond
with water molecules. Propane is non-polar molecule
which can not form hydrogen bond with water molecules.
So propane is insoluble in water.
b) 1,2-propanediol more soluble in water.
➢ It is because 1,2-propanediol consists more hydroxyl
group than 1-propanol.
➢ Hence, 1,2-propanediol can form more hydrogen bond
with water molecules.
c) 2-propanol more soluble in water.
➢ It is because 2-propanol has smaller molecular size
and smaller hydrophobic area compare to 2-pentanol.
38
➢ Hence, it is easier for 2-propanol to form hydrogen bond
with water molecules.
 8.3 Preparation of Alcohols

LEARNING OUTCOMES:

At the end of this topic, students should be able to:

(a) Explain the preparation of alcohol by:

i. fermentation
ii. hydration of alkenes
iii. hydrolysis of haloalkanes
iv. addition of Grignard reagent to carbonyl compounds

(b) Outline the synthesis of alcohols 39

1. Fermentation of Carbohydrates

▪ Fermentation is usually carried out by adding yeast to

a mixture of sugar and water.

▪ Important process for preparation of ethanol and other

alcohols.

▪ Example :

yeast
C6H12O6 (aq) zymase 2CH3CH2OH(aq) + 2CO2 (g)

ethanol
(~95% yield) 40
 2. Acid-catalyzed Hydration of Alkenes
▪ Alkenes was added by H2O in the presence of an
acid catalyst, H2SO4 or H3PO4.

▪ Follows Markovnikov’s rule.

▪ General reaction :
R R
R R
H3O+
H C C R
H2O H C C R

H OH

* Refer to CHAPTER 5: Hydration of Alkenes 41

3. Hydrolysis of Haloalkanes (Substitution of Haloalkanes)

▪ Alkyl Halide react with strong bases (NaOH) to produce

alcohols and sodium halides (NaX).

▪ 1o R-X – form 1o R-OH

2o R-X – form 2o R-OH
3o R-X – form 3o R-OH

▪ General reaction :
R – X + OH- ROH + X-
R – X + NaOH(aq) ROH + NaX
42
 EXAMPLE

i. CH3CH2Cl + NaOH(aq)

ii. (CH3)2CHCl + NaOH(aq)

Cl
iii.
NaOH(aq)

CH2CH2Cl

iv. + NaOH(aq)
43
 ANSWER

i. CH3CH2Cl + NaOH(aq) CH3CH2OH

ii. (CH3)2CHCl + NaOH(aq) (CH3)2CHOH

Cl
iii.
NaOH(aq) No observable change

CH2CH2Cl CH2CH2OH

iv. +NaOH(aq) 44
4. Addition of Grignard Reagent to Carbonyl Compounds
dry ether
R-X + Mg RMgX

alkyl halides magnesium Grignard reagent

▪ Grignard reagents react with carbonyl compounds to

yield alcohol.

▪ 1o, 2o & 3o alcohols can be prepared by addition of

Grignard reagent with carbonyl compounds followed by
hydrolysis.
45
 i.
. Formation of 1o alcohols (Grignard reagent + methanal)

ii.
Formation of 2o alcohols (Grignard reagent + aldehyde)

iii. Formation of 3o alcohol (Grignard reagent + ketone)

46
 EXERCISE

1. Write the chemical equation for the following reaction:

i. tert-butyl alcohol from an alkene
ii. isopropyl alcohol from an alkyl halide
2. Draw the structure of A, B and C:

i. CH3 O
H 2O / H +
CH3C-MgCl + -C-H A

CH3

ii. H 3O +
-CH=CHCH3 + H2O B + C
47
 ANSWER

1. Write the chemical equation for the following reaction:

i. tert-butyl alcohol from an alkene

CH3
CH3 H3O+
+ H2O CH3C CH3
CH3C CH2
OH

ii. isopropyl alcohol from an alkyl halide

CH3CH(CH3)Cl + NaOH(aq) CH3CH(CH3)OH + NaCl

48
 ANSWER
2. Draw the structure of A, B and C:
i. CH3 O OH CH3
H2O / H+
CH3C-MgCl + -C-H C
H
C CH3

CH3 A
CH3

ii. H 3O + H2 H
-CH=CHCH3 + H2O C C CH3

OH
B
+
H H2
C C CH3

49
OH

C
 8.4 Chemical Properties
of Alcohols

LEARNING OUTCOMES:
At the end of this topic, students should be able to:

(a) Explain the reactions of alcohol with reference to:

i. reaction with sodium
ii. esterification
iii.dehydration
iv.substitution reactions using HX, PX3, PX5 or SOCl2

(b) Explain the oxidation reactions with KMnO4/H+,

Cr2O72-/H+, CrO3/H+ and PCC/CH2Cl2 50

50
 LEARNING OUTCOMES:

At the end of this topic, students should be able to:

(c) Explain the identification tests to distinguish classes of

alcohols using Lucas reagent, i.e. concentrated
HCl/ZnCl2
(d) Outline the synthesis of compounds related to
reactions of alcohols

(e) Explain iodoform test i.e. I2/OH- to identify methyl

carbinol CH3CH(OH).
51

51
 Reactions of Alcohols

▪ Alcohols can undergo 2 types of reactions:

1. O-H bond cleavage

➢ Alcohol act as a weak acid (donate proton).

ROH + H2O RO- + H3O+

➢ Reactions involve :
i. Reaction with Na (formation of alkoxides)
ii. Esterification
iii. Oxidation of alcohols
52
2. C-O bond cleavage

➢ Alcohols act as bases (accepts proton from an acid).

CH3CH2OH + HA CH3CH2+ A- + H2O

➢ Reactions involve :
i. dehydration of alcohols
ii. substitution using HX, PX3, PX5 and SOCl2

53
i. Reaction with Sodium (Na)

▪ Alcohols react with Na to form salts (sodium alkoxides)

and hydrogen gas.

▪ This reaction shows the acidic properties of alcohol.

▪ General reaction :
ROH(l ) + Na(s) RO-Na+ + ½ H2(g)
(sodium alkoxide)
▪ Example :

CH3CH2OH(l ) + Na(s) CH3CH2O-Na+ + ½ H2(g)

54
ii. Esterification Reaction

▪ Acid-catalyzed condensation of an alcohol and carboxylic

acid yields an ester and water known as Fischer
Esterification.

▪ General reaction :
O O
H+
R-O-H + H-O-C-R' R-O-C-R' + H2O
(alcohol) (carboxylic acid) (ester)
Example :
H+
CH3COOH + CH3OH CH3COOCH3 + H2O
ethanoic acid methanol methyl ethanoate 55
iii. Dehydration of Alcohol
▪ Dehydrations requires an acidic catalyst to protonate the –
OH group of alcohol - convert it to a good leaving group.

▪ Loss of water, followed by loss of a proton, gives the alkene.

- used Saytzeff Rule to predict major alkene product.
General equation:

conc. H2SO4
C C C C + H2O
H OH

Example:
conc. H2SO4
CH3CH2CH2OH CH3CH=CH2 + H2O 56
iv. Substitution Reaction

(i) Reaction with Hydrogen Halides (HX)

▪ When alcohol react with a hydrogen halide, a

substitution takes place producing alkyl halide and
water.
R-OH + HX R-X + H2O
▪ The increasing order of reactivity of hydrogen halides
toward R-OH :
HCl < HBr < HI

▪ The increasing order of reactivity of alcohols : 57

methyl < 1o < 2o < 3o
(ii) Reaction with Phosphorus Trihalides
(PX3)
▪ General reaction :
where : X = Br or Cl
R-OH + PX3 RX + H3PO3

▪ Example :

CH3
CH3
CH3-C-CH2OH + PBr3 H3C C CH2Br

CH3
CH3
58
+ H3PO3
(iii) Reaction with Phosphorus Pentahalides (PX5)
▪ General reaction :
R-OH + PX5 RX + POX3 + HX

▪ Example :

C
HO
2 H P
Cl5 C
HC
2 l + POCl3 + HCl

(iv) Reaction with Thionyl Chloride (SOCl2)

pyridine
• General reaction : RO H + SO C l RC l+ SO
2 2 + HC l(g)
Example : (white fume)

CH2OH CH2Cl
pyridine 59
+ SOCl2 + SO2 + HCl (g)
thionyl chloride (white fume)
 EXERCISE

Identify the reagents (a) to (c) in the following scheme:

OH Br
(a)

CH2OH CHO
(b) (c)

60

60
ANSWER

OH Br
a) PBr3

cyclohexanol bromocyclohexane

Note: HBr also can be used

61

61
ANSWER
Br Mg, dry ether Mg–Br

b)
Grignard reagent
bromocyclohexane
O
(i) H–C–H
methanal
(ii) H2O/H+

CH2OH

cyclohexylmethanol
62

62
 ANSWER

c) CH2OH CHO
PCC/CH2Cl2

cyclohexylmethanol cyclohexanecarbaldehyde

63

63
 Oxidation Reaction of Alcohol

▪ Oxidation of an alcohol yields a carbonyl compounds

(aldehyde, ketone or carboxylic acid).
▪ The decreasing order of reactivity of alcohols on oxidation
reaction:

Tertiary alcohol only can be

oxidised under forcing
condition
Examples of oxidizing agents:

No. Oxidizing agent Molecular Formula

Pyridinium
i. chlorochromate PCC / CH2Cl2
in dichloromethane

Potassium i. KMnO4 / OH- , heat

ii.
permanganate ii. H+

H2CrO4 or CrO3/H+
iii. Chromic acid @ Na2Cr2O7 / H2SO4
65
@ K2Cr2O7 / H2SO4
▪ Oxidation of 1o and 2o alcohols forms a carbonyl
group by the removal of two hydrogen atom.
- one from the carbinol carbon and one from
the hydroxyl group.

1. Oxidation of primary (1o) alcohols

▪ 1o alcohols can be oxidized to aldehydes or

carboxylic acids depend on the oxidizing agent
which is used.

66
▪ General reaction :

H O

K2Cr2O7 / H+
R C OH R C OH

carboxylic acid
H

1o alcohol

CH2Cl2

1o alcohol aldehyde
67
▪ Primary alcohols can be oxidized to aldehydes by using PCC

(less powerful oxidizing agent)

▪ General reaction :
O
PCC CH2Cl2
RCH2OH R C H
1o alcohol aldehyde

Example:
P C C / C H 2C l2
C H 3C H 2O H C H 3C HO
ethanol ethanal
68
▪ Strong oxidizing agent is required to oxidizes 1o alcohol to
carboxylic acid.

▪ General reaction :
[O]
R – CH2-OH RCOOH
1o alcohol carboxylic acid

- where [O] = (Cr2O72-/H+) or (KMnO4 /H+)

69
Observation :

Strong Oxidizing
Observation
Agent
Chromic acid
• orange colour of chromic acid changes to
(CrO3/H+) or
green colour
Dichromic acid
• CrO3 or Cr2O72- change to Cr3+
(Cr2O72-/H+)

Hot acidified potassium • Purple colour of KMnO4 changes to

i permanganate colourless @ Purple colour of KMnO4
(KMnO4/H+) decolourised 70
 Example:

i.
K2Cr2O7/H+
CH3CH2OH CH3COOH
ethanol ethanoic acid

ii.
C H 2O H COO H
K M nO 4 / H +

cyclohexyl cyclohexanecarboxylic
methanol acid
71
2. Oxidation of Secondary (2o) Alcohols

▪ Secondary alcohols are oxidized to ketones.

▪ General reaction :

where [O] = (Cr2O72-/H+) or (KMnO4 /H+)

R O
[O]
R-CHOH R-C-R
2o alcohol ketone

▪ Example :

CH3 CH3
KMnO4/H+
CH3CH-OH CH3C=O + H2O
2-propanol propanone 72
3. Oxidation of Tertiary (3o) Alcohols

▪ Tertiary alcohol is not easily oxidize because there

is no hydrogen atom available on the carbinol
carbon.

▪ General reaction : where [O] = (Cr2O72-/H+) or (KMnO4 /H+)

R
[O]
R-C-OH no reaction
R (except under forcing conditions)

▪ Example :
CH3
Na2Cr2O7/H+
CH3-C-OH no reaction
H2SO
∆ 4
73

CH3
 Identification test to distinguish
classes of alcohols
Lucas Test

▪ Method used to distinguish 1o, 2o and 3o alcohols by

observing the rates of reaction between alcohols and
Lucas reagent to form alkyl chlorides.

▪ Lucas reagent is a mixture of concentrated HCl and

ZnCl2.

▪ General equation :

conc. HCl / ZnCl2

ROH RC l + H 2O 74
 Identification test to distinguish
classes of alcohols

• The formation of the alkyl chloride is indicated when the

reaction mixture become cloudy (or 2 layers formed).

▪ The time required for cloudiness to appear is a

measure of the alcohol reactivity .

75
 Lucas Test : (to distinguish 1o, 2o and 3o alcohol)
Alcohol Observation

➢does not formed cloudy solution even after

1o alcohol heating for 10 minutes

➢ cloudy solution appears within 5-10

2o alcohol
minutes after heating
➢ 2 layers formed
3o alcohol ➢ cloudy solution appears immediately at
room temperature
➢ 2 layers formed
(please take note: cloudy solution formed after shaking, 2 layers will form after you let the test tube
stand still for a while after shaking)

The decreasing order of reactivity of alcohols toward Lucas Test:

76
3o alcohol > 2o alcohol > 1o alcohol
 EXAMPLE:

CH2 OH
i.
conc. HCl / ZnCl2
no observable reaction

Observation: The solution does not turn cloudy

OH Cl
ii. + H2 O
conc.HCl / ZnCl2

Observation: The solution turn cloudy within 5 to 10 minutes after heating

CH3 CH3
OH conc. HCl / ZnCl2 Cl
iii. + H2 O
77
Observation: The solution turn cloudy immediately
 Iodoform Test To Identify
Methyl Carbinol Group
▪ Is an example of a haloform reaction.
▪ Methyl carbinol cleavage to give carboxylic acids and haloform
▪ If Cl2 and Br2 in aqueous NaOH is used, chloroform and
bromoform are form.

H
X2 / OH-
CH 3 C R CHX 3 + R C O-
OH O
H
I2 / OH-
CH 3 C R CHI 3 (S) + R C O-
Triiodomethane
OH (iodoform) O 78

Yellow precipitate
 i.
H
I2 / OH-
CH 3 C H CHI 3 (S) + H C O-
Triiodomethane
OH (iodoform) O
Yellow precipitate
ii. H
I2 / NaOH
CH 3 C CH3 CHI 3 (S) + CH3 C O- Na+
Triiodomethane
OH (iodoform) O
Yellow precipitate
iii.
H H -
I2 / OH
CH 3 C C H No observable reaction
H OH
79
 EXERCISE
Differentiate 2-pentanol and 3-pentanol by using a suitable chemical test.

ANSWER:
Iodoform Test
Reagent: I2/OH-
I2 / OH-
CH3CH(OH)CH2CH2CH3 CHI3 + CH3CH2CH2COO-
2-pentanol
Observation: Formation of yellow precipitate.
I2 / OH-
CH3CH2CH(OH)CH2CH3 no observable reaction
3-pentanol
Observation: No formation of yellow precipitate.
 8.5 Phenol

LEARNING OUTCOMES:

At the end of this topic, students should be able to:

a) Compare the acidity of phenol, alcohol and water.
b) Explain the chemical properties of phenol with reference to:
i. reaction with sodium
ii. reaction with sodium hydroxide
iii. identification tests using
- FeCl3 solution
81
- bromine water
A. Physical Properties of Phenols

• Physical state
- Liquid or low-melting solids at room temperature.

• Boiling point and solubility

- High boiling points because of intermolecular
hydrogen bonding.

- Partially miscible in water because of hydrogen

bonding with water molecule.

82
1. ACIDIC PROPERTIES OF PHENOL

▪ Phenol is classified as a weak acid because it can act as

a proton donor .

▪ Phenol dissociates to form phenoxide and hydroxonium

(oxonium or hydronium) ion which is resonance
stabilized.

▪ The acidity of phenol is due to the delocalisation of the

negative charge of the phenoxide ion .

▪ The phenoxide ion is less likely to accept a proton to form

phenol. As a result, phenol acts as an acid.
83

83
 Phenoxide Ion Stability

δ- δ+
O H O -

+ H2O + H3O+

Phenoxide ion

O - O O O O δ-

- - δ- δ-

- δ-
84
Diagram 1
84
Phenol (aromatic alcohol) is the most acidic alcohol if
compared to the aliphatic alcohol because the phenoxide
ion @conjugate base is stable which the negative
charge on oxygen can be delocalised onto the
benzene ring as shown in the diagram 1. Equilibrium
tends to shift to the right and more H3O+ is formed.
Therefore, phenol is more acidic.
(alternative ans: Phenoxide ion can be stabilized by
delocalisation of electrons into benzene ring)
Table below shows that phenol is more acidic
compared to ethanol because phenol can reacts
with NaOH in aqueous form

Na NaOH Na2CO3@
NaHCO3

Ethanol √ X X

Phenol √ √ X 86
2. Acidity of Phenols, Alcohol and Water

▪ Phenol is a stronger acid compared to alcohols.

pKa Ka

Ethanol
16 1x10-16
Water
14 1x10-14
Phenol
10 1x10-10

Ethanol < Water < Phenol

87
increasing acidity
Ethanol
CH3CH2OH + H2O CH3CH2O- + H3O+
Ethanol is less acidic than water because of the presence of electron
donating group (EDG), -CH2CH3 (alkyl). The EDG will increase the
density of negative charge on the oxygen atom making the CH3CH2O- @
conjugate base less stable and the equilibrium direction shifts to the left forming
less H3O+. As a result, acidity decreases.

Water
H2O + H2O H3O+ + OH-
Water is less acidic than phenol but more acidic than ethanol because water
has no electron donating group (EDG) attached to the hydroxide ion and
has no resonance structures like phenoxide ion.
 Phenol

OH -
O

+ H 2O + H3 O +

phenoxide ion

Phenol is the most acidic if compared to the water and ethanol

because the phenoxide ion @ conjugate base is stable which
the negative charge on oxygen can be delocalised onto the
benzene ring. Equilibrium tends to shift to the right and more
H3O+ is formed. Therefore, phenol is the most acidic.
B. Chemical Properties of Phenols

1. Reactions at functional group -OH

i) Reaction with sodium
When Na is added to a solution of phenol in ethoxyethane
(ether, C2H5OC2H5) at room temperature, H2 gas is
librated.
OH O-Na+

ether
+ Na + ½ H2(g)

ether
CH3CH2OH + Na CH3CH2O-Na+ + ½ H2(g)
90
ii) Reaction with sodium hydroxide
Phenol is slightly soluble in water but dissolve in
aqueous NaOH at room temperature to form
sodium phenoxide and water.

OH O-Na+

+ NaOH + H2O

CH3CH2OH + NaOH no observable change

91
iii) Identification Test of Phenols
Aqueous iron (III) chloride and aqueous bromine are
used to test for phenols.

1. Using aqueous FeCl3

OH OH

+ FeCl3 (aq)
( yellow ) FeCl3
( purple complex )

2. Using aqueous Bromine

OH
OH
Br2 / H2O Br Br
+ 3HBr
92
Br
( white precipitate )
3. Using HNO3
OH OH
O 2N NO2

conc. HNO3

NO2

(yellow oil)

93
 EXERCISE

1. Suggest a chemical test to differentiate the

following pairs of compounds. State the reagents,
observations and write chemical equations involved.

(a) methanol from ethanol

(b) 2-methyl-1-propanol from 2-methyl-2-propanol
(c) cyclohexanol from cyclohexane
(d) phenol from benzyl alcohol

94

94
ANSWER
(a) methanol from ethanol
Iodoform test
Equation:

I2 / OH-
CH3OH No observable change
Observation: No formation of yellow precipitate

Equation:
I2 / OH-
CH3CH2OH CHI3 (s) + HCOO-

Observation: Yellow precipitate was formed

95
 (b) 2-methyl-1-propanol from 2-methyl-2-propanol
Test with Lucas reagent
Equation:
conc. HCl / ZnCl2
CH3CH(CH3)CH2OH No observable change

Observation: No cloudiness appears

Equation:

conc. HCl / ZnCl2

CH3C(OH)(CH3)2 CH3C(Cl)(CH3)2 +H2O

Observation: Cloudiness appears immediately

96
 (c) cyclohexanol from cyclohexane
Test with Lucas reagent
Equation:

OH Cl

conc. HCl / ZnCl2

+ H2O

Observation: Cloudy solution appears within 5 to 10 minutes

Equation:

conc. HCl / ZnCl2

No observable change

Observation: No formation of cloudy solution 97

 (d) phenol from benzyl alcohol
Test with aqueous iron (III) chloride, FeCl3
Equation:
OH OH

+ FeCl3 (aq)
( yellow )
FeCl3
( purple complex )

Observation: Yellow colour of FeCl3 change to purple complex

Equation:
C H 2O H

No observable change
+ FeCl3 (aq)
( yellow )
98
Observation: Yellow colour of FeCl3 remains unchanged
Alternative: can use bromine water @ HNO3
 EXERCISE

2. Compound A (C4H10O) undergoes oxidation to form

compound B (C4H8O). Oxidation of B gives compound C
(C4H8O2). Reaction of A with hot concentrated sulphuric
acid yields compound D (C4H8). Hydration of D gives
compound E (C4H10O) which cannot be oxidised. A and E
are isomeric. Suggest the structure of A, B, C, D and E.

99

99
ANSWER

2. A = CH3CH(CH3)CH2OH
B = CH3CH(CH3)CHO
C = CH3CH(CH3)COOH
D = CH3C(CH3)=CH2
E = CH3C(OH)(CH3)2

100