Chapter 8.

0
Hydroxy
Compound
1
Student Learning Time (SLT) Allocation
Slot Lecture Tutorial Practical Total SLT

FTF 1 3 2 6

NFTF 1 3 2 6

Total = 12

2
 Marks Contribution
UPS 2 CHEMISTRY EC025

Topic CLO % Marks Allocated

Hydrocarbons 1 5.6% 3.3/60

PSPM 2 CHEMISTRY EC025

Topic CLO % Marks Allocated

Hydrocarbons 3 6.5% 5.2

3
 Learning Outcome
8.1 Nomenclature
a) Draw the structures, classify and name the hydroxy compounds (parent chain
≤ C10 ) according to the IUPAC nomenclature

8.3 Preparation of Alcohols

a) Explain the preparation of alcohol by:
i. Fermentation
ii. Hydration of Alkenes
iii. Hydrolysis of haloalkanes
iv. Addition of Grignard reagents to carbonyl compounds
b) Outline the synthesis of alcohols
4
 Learning Outcome
8.1 Nomenclature
a) Draw the structures, classify and name the hydroxy compounds
(parent chain ≤ C10 ) according to the IUPAC nomenclature

8.2 Physical Properties of Alcohols

a) Analyse the physical properties:
i. Boiling point
ii. Solubility in water

5
 Learning Outcome

8.3 Preparation of Alcohols

a) Explain the preparation of alcohol by:
i. Fermentation
ii. Hydration of Alkenes
iii. Hydrolysis of haloalkanes
iv. Addition of Grignard reagents to carbonyl compounds
b) Outline the synthesis of alcohols

6
 Learning Outcome
8.4 Chemical Properties of Alcohols
a) Explain the reactions of alcohol with reference to:
i. Reaction with sodium
ii. Esterification
iii. Dehydration
iv. Substitution reactions using HX, PX3, PCl5 or SOCl2
b) Explain the oxidation reactions with KMnO4/H+, Cr2O72-/H+, CrO3/H+ and
PCC/CH2Cl2
c) Explain the identification tests to distinguish classes of alcohols using Lucas reagent, i.e
concentrated HCl/ZnCl2 (Experiment 5: Reactions of Hydroxy compounds)
d) Outline the synthesis of compounds related to reactions of alcohols.
e) Explain iodoform test, i.e: I2/OH- to identify methyl carbinol CH3CH2(OH)
7
 Learning Outcome

8.5 Phenol
a) Compare the acidity of phenol, alcohol and water.
b) Explain the chemical properties of phenol with reference to:
i. Reaction with sodium
ii. Reation with sodium hydroxide
iii. Identification tests using FeCl3 solution & Bromine water

8
 Introduction to Hydroxy compound
Aliphatic Alcohol Aromatic Alcohol
( –OH group attached directly on alkyl group) ( –OH group attached directly on benzene ring)

OH CH2-OH OH

CH3CH2OH

Open chain
alcohol
Closed chain
alcohol
Open chain
alcohol
Phenol

9
 Classes of Alcohol Compound
Classification of Alcohol
Alcohol can be classified into

H H CH3 CH3
H C OH H3C C OH H3C C OH H3C C OH
H
H H CH3
methyl alcohol 1° alcohol 2° alcohol 3° alcohol

10
 Learning Outcome

8.2 Physical Properties of Alcohols

a) Analyse the physical properties:
i. Boiling point
ii. Solubility in water

11
8.2 Physical Properties of Alcohol

PHYSICAL BOILING SOLUBILITY

STATES POINT IN
WATER

12
 Boiling Point of Alcohol
Comparison between alcohol compounds.
Factor: Molecular weight
Ø Molecular weight @molecular size of alcohol increases, boiling point increases due to the
increase strength of Van der Waal Forces of attraction between molecules
Ø More heat energy is required to break the strong attraction force
Ø Boiling point increases.

Example: Arrange hexanol, decanol, ethanol in ascending order of boiling point. Explain.

78.37 °C 157 °C 230 °C

ethanol< hexanol < decanol
The bigger the molecular size/molecular mass, the stronger the van der Waals forces between molecules. More heat
energy is required to break the strong attraction force. Hence, Decanol has highest boiling point 13
 Boiling Point of Alcohol
Comparison between alcohol & hydrocarbon compound.
Factor: Type of Intermolecular forces of attraction

Ø Boiling Point of alcohol, R-OH is higher than the corresponding hydrocarbons (alkane, alkene,
haloalkane) due to the ability of alcohol to form hydrogen bonds attraction force with the other
alcohol molecule.
Ø Hydrocarbons/ Haloalkanes can only form weak Van Der Waals Forces of attraction (Dipole2 interaction
/ London force)

14
 Boiling Point of Alcohol
Example: Arrange butanol, butane and ethene in ascending order of boiling point. Explain.

Ethene < Butane < Butanol

-103.7 °C -1 °C 117.7 °C

Ø Butanol is a polar molecule while butane and ethene is a non-polar molecule

Ø Butanol can form strong hydrogen bond attraction force while butane and ethene form weak
London force. 15
Ø So, butanol require more heat energy to break the strong attraction force between butanol
molecule.
Ø The boiling point of butanol is higher than butane and ethene.
Ø Butane has higher boiling point than ethene due to molecular size of butane is bigger than ethene
molecule.
Ø More heat energy required to break the attraction force between butane molecule.
 Boiling Point of Alcohol
Comparison between alcohol with different number of OH group.
Factor: Strength of Hydrogen Bond attraction force.

Ø As Number of –OH group increases , Boiling Point increases due to the increase in
the number of hydrogen bond attraction force that exist between the alcohol

16
 Boiling Point of Alcohol
Example: Arrange propane, 1,2-ethanediol, 1-propanol in ascending order of boiling point. Explain.
-42 °C 97 °C 197 °C
propane < 1-propanol < 1,2-ethanediol
Increasing boiling point

Ø propane is a non-polar molecule where it has weak van der Waals forces between molecules
Ø 1-propanol and 1,2- ethanediol can form hydrogen bonds between molecules
17
Ø hydrogen bonds attraction force are stronger than van der Waals forces of attraction
Ø Since 1,2-ethane diol has two hydroxyl groups, can form stronger hydrogen bonds than 1-propanol

17
 Solubility of Alcohol in water
In general, alcohol is soluble in polar solvent of water because alcohol (polar molecule)
can form Hydrogen bond attraction force with water molecule (polar molecule)

Hydrogen bond between Alcohol

Hydrogen bond between & water molecule
Alcohol & water molecule 𝛅+ 𝛅−
𝛅+ H bonds attraction force formed when:
• H atom bonded with F,O,N atom
𝛅− 𝛅+ • Alcohol has H atom bonded with O atom
𝜹− 𝜹+
R O-H
Hydrogen bond between Alcohol & water molecule

18
 Solubility of Alcohol in water
The solubility level of alcohol in water is dependent on the number of C atoms in alcohol
molecule

𝛅+ 𝛅− 𝛅+
R O -H
Hydrophobic part Hydrophilic part
non-polar O-H group is polar.
Weak interaction with Form strong H-bonds with water
water molecules. molecules.
(insoluble in water) (Soluble in water)

19
Solubility of Alcohol in water
Alcohol with different number of C atoms

Smaller alcohols (≤ 5C) are soluble in water. Bigger alcohols ( >5C) are insoluble in water.

Ø It is because, the hydrophobic part is Ø It is because, the hydrophobic part

low(alkyl portion is low number) in which (alkyl portion is in large number) will
it makes the alcohol to be soluble in polar cause alcohol to be gradually insoluble in water.
solvent of water.
Ø The small Hydrophobic part in alcohol
makes the alcohol to be soluble in water
20
Solubility of Alcohol in water
Alcohol with different number of C atoms

Example: Arrange ethanol hexanol, decanol in ascending order of solubility in water. Explain.

Decanol< Hexanol < Ethanol

Ø Decanol has larger number of C atom which means it has larger hydrophobic part of alkyl group
in structure compared to Hexanol and Ethanol.
Ø Larger hydrophobic part in structure will decrease the solubility level of decanol in water
compared to the other compound.
Ø Therefore, Decanol has the lowest solubility level compared to hexanol and ethanol
Ø Ethanol is very soluble in water due to smaller hydrophobic part in structure.
21
 Solubility of Alcohol in water
Comparison between alcohols with different number of OH group.
Factor: Strength of Hydrogen bond attraction force.
Ø For alcohol R-OH with the same number of carbon atoms, when number of –OH groups increases,
the solubility increases due to increase in number of Hydrogen Bond that can form with water
molecules.
Arrange the following compound according to increasing order of solubility in water solvent:

1-propanol < 1,2-ethanediol < 1,2,3-butanetriol

22
 Learning Outcome

8.3 Preparation of Alcohols

a) Explain the preparation of alcohol by:
i. Fermentation
ii. Hydration of Alkenes
iii. Hydrolysis of haloalkanes
iv. Addition of Grignard reagents to carbonyl compounds
b) Outline the synthesis of alcohols

24
 Preparation of Alcohol compound
Fermentation
of Sugar

Hydration of * (Recall : 5.2 Reactions of alkene)

Alkenes

Hydrolysis of * (Recall : 7.2 Reactions of Haloalkanes)

Haloalkanes

Addition of Grignard reagents

* (Recall : 7.2 Reactions of Grignard reagent)
to Carbonyl Compounds 25
 Preparation of Alcohol compound
1. Fermentation of Sugar

zymase
C6H12O6 2C2H5OH + 2CO2
glucose ethanol

Ø This method applies only to ethanol and NOT any other alcohol this way.
Ø The reaction is catalyzed by the enzymes in yeast.
Ø The enzymes are denatured at temperature above 45℃. Therefore, fermentation
must be carried out at temperature 25℃ to 45℃.
26
 Preparation of Alcohol compound
2. Hydration of Alkenes
Ø Reactants : alkenes + water

Ø Catalyst : H2SO4 or H3PO4

Ø Rule : Markovnikov’s rule
H OH
Ø General reaction : H3O+
C C + H2 O C C

alkene alcohol

27
 Preparation of Alcohol compound
2. Hydration of Alkenes
Example :
H3O+ H OH
H C C H + H2 O
H C C H
H H
H H
ethene ethanol

H3O+ OH H
H3 C C CH CH3 + H2O
H3 C C CH CH3
H3 C
H3 C
2-methylbut-2-ene 2-methylbutan-2-ol
28
 Preparation of Alcohol compound
3. Hydrolysis of Haloalkanes
Reactants : haloalkane + NaOH (aq)
General reaction :

X H OH
C C + NaOH(aq) C C + NaX
reflux

haloalkane alcohol

29
 Preparation of Alcohol compound
3. Hydrolysis of Haloalkanes

Example :
H H
Na OH (a q)
H C Br H C OH + NaBr
reflux
H H

CH3 CH3
NaOH (aq)
H3C CH Cl reflux H3C CH OH + NaCl

30
 Preparation of Alcohol compound
4. Addition of Grignard reagents H
1° 𝑎𝑙𝑐𝑜ℎ𝑜𝑙
to Carbonyl Compounds C H H
methanal

i O CH3CH2C H + Mg(OH)Br
ii.H3O+
OH
H Ethanal @
aldehyde other H
CH3CH2MgBr i CH3C O than methanal
CH3CH2 C CH3 + Mg(OH)Br
ii.H3O+
Grignard reagents OH
2° 𝑎𝑙𝑐𝑜ℎ𝑜𝑙

CH3 CH3
ketone
i CH3C O CH3CH2C CH3 + Mg(OH)Br

ii.H3O+ OH 31
3° 𝑎𝑙𝑐𝑜ℎ𝑜𝑙
 Learning Outcome
8.4 Chemical Properties of Alcohols
a) Explain the reactions of alcohol with reference to:
i. Reaction with sodium
ii. Esterification
iii. Dehydration
iv. Substitution reactions using HX, PX3, PCl5 or SOCl2
b) Explain the oxidation reactions with KMnO4/H+, Cr2O72-/H+, CrO3/H+ and
PCC/CH2Cl2
c) Explain the identification tests to distinguish classes of alcohols using Lucas reagent, i.e
concentrated HCl/ZnCl2 (Experiment 5: Reactions of Hydroxy compounds)
d) Outline the synthesis of compounds related to reactions of alcohols.
e) Explain iodoform test, i.e: I2/OH- to identify methyl carbinol CH3CH2(OH)
33
 Chemical Properties of Alcohol
Chemical Reactions of Aliphatic Alcohol Chemical Test of Aliphatic Alcohol

1. Reaction with metal, Na 1. Lucas Test :

To differentiate the classes of alcohol
2. Esterification
2. Iodoform Test :
3. Dehydration of Alcohol To test the presence of methyl carbinol
group in alcohol.
4. Substitution reaction with HX, PX3, 34

PCl5, or SOCl2 in pyridine

5. Oxidation reaction with KMnO4/H+

or K2Cr2O7/H+ or PCC/CH2Cl2
34
 Chemical Properties of Alcohol
Reaction of Alcohols

Alcohol acts
as a weak acid Involves O—H bond Involves C—OH bond Alcohol acts as
(proton bases (proton
donor).
cleavage in alcohol cleavage in alcohol acceptor).

R-OH + HA → R-A + H2O

R-O-H + H2O → R-O- + H3O+

Reaction Substitution with

Oxidation
with Na HX, PX3 , PCl5 @ SOCl2

Esterification
Dehydration 35
 Chemical Properties of Alcohol
1. Reaction with Na

RO - H + Na RO- Na+ + ½ H2
General equation : 25°C
Alcohol Alkoxide salt

H - +

Example : H3 C C O H + Na + ½ H2
25°C
H
ethanol Sodium ethoxide
36
 Chemical Properties of Alcohol
2. Esterification
Alcohol reacts with carboxylic acid under reflux & is catalysed by mineral acids
(H2SO4 or HCl) to produce ester.
H+
General equation : ROH + RCOOH RCOOR + H2O
reflux
Alcohol Ester

O O
H+
Example : CH3-OH + CH3C-OH CH3C-OCH3 + H-O-H
reflux
Methanol Methyl methanoate

37
 Chemical Properties of Alcohol
3. Dehydration of Alcohol
Ø Dehydration of alcohol means alcohol removes/eliminates water H2O to form an alkene
Ø 'De' = remove/eliminate
Ø Alcohol removes H and OH atoms from adjacent (next to) Carbon atom
Ø This dehydration process occur with the presence of concentrated acid solution and heat.
Ø General equation of dehydration process of alcohol

Con. H2SO4
General equation : C C C C + H2O
heat
H OH Alkene

H H H H
Con. H2SO4
Example : H3C C C H H3C C C H + H2O
heat
Propanol H OH Propene 38
 Chemical Properties of Alcohol
4. Substitution Reaction
Ø Alcohol undergo nucleophilic substitution reactions with these reagent to form
Haloalkane compound:
a) Hydrogen halide, HX
b) Phosphorus trihalides ,PX3 (X= Br, Cl) or phosphorus pentachloride ,PCl5
c) Thionyl chloride, SOCl2 in pyridine

39
 Substitution reaction of Alcohol
a) Reaction with Hydrogen Halide, HX

General equation : R-OH + H-X → R-X + H2O

CH3 CH3
Example : H 3C C OH + HCl H 3C C Cl + H2 O

CH3 CH3
Haloalkane
40
 Substitution reaction of Alcohol
b) Reaction with PX3
X= Br or Cl atom

General equation : 3R-OH + PX3 ® 3R-X + H3PO3

Haloalkane

Example : CH3CH2OH + PCl3 ® CH3CH2Cl + H3PO3

Haloalkane

CH3CH2OH + PBr3 ® CH3CH2Br + H3PO3

Haloalkane
41
 Substitution reaction of Alcohol
b) Reaction with PCl5

General equation : R-OH + PCl5 ® R-Cl + POCl3 + HCl

Haloalkane

Example : CH3CH2OH + PCl5 ® CH3CH2Cl + POCl3 + HCl

Haloalkane

42
 Substitution reaction of Alcohol
c) Reaction with thionyl chloride, SOCl2 in pyridine

Pyridine
General equation : R-OH + SOCl2 ® R-Cl + SO2 + HCl
Haloalkane

Pyridine
Example : CH3CH2OH + SOCl2 ® CH3CH2Cl + SO2 + HCl
Haloalkane

43
 Oxidation reaction of Alcohol
5. Oxidation reaction with KMnO4/H+ or K2Cr2O7/H+ or PCC/CH2Cl2
Ø Oxidation of alcohol yields a carbonyl compounds (aldehyde, ketone) or carboxylic
acid, COOH
Ø The process involve the removal of hydrogen atom (one from the carbinol carbon and
one from the hydroxyl group). H

Ø The order of reactivity towards oxidation reaction: R-C OH

R R H
methyl carbinol group
R—C—OH < R—C—OH < R—C—OH
R H H
Increase reactivity
3° alcohol 2° alcohol 1° alcohol towards oxidation
reaction 44
 Oxidation reaction of Alcohol
5. Oxidation reaction with KMnO4/H+ or K2Cr2O7/H+ or PCC/CH2Cl2
Common oxidizing agents are :
Type of Oxidising Oxidizing Agent Molecular Observation
agent Formula
-
Pyridinium chlorochromate
Mild oxidising agent PCC in CH2Cl2 We do not conduct experiment/test
in dichloromethane using this.
§ Purple colour of KMnO4
Hot Acidified Potassium decolorised
KMnO4 / H+ , heat
permanganate § Brown precipitate formed (MnO2)
Strong oxidising
agent H2CrO4 or
CrO3/H+ Orange colour of chromic acid change
Hot acidified Chromic acid to green.
@ Na2Cr2O7 / H+
@ K2Cr2O7 /H+
45
Oxidation of 1° alcohol
Ø 1o alcohols can be oxidized to aldehydes or carboxylic acid by using suitable oxidizing agent
Mild oxidation reaction:

Ø Oxidation of 1o alcohol using H H

mild oxidizing agent of PCC in PCC in CH2Cl2
R—C—OH —
CH2Cl2 will produce an R—C—O
aldehyde H
1o alcohol Aldehyde

Strong oxidation reaction:

Ø Carboxylic acid can be obtained
with a strong oxidizing agent such H OH
as hot acidified:
KMnO4 / H+
1. KMnO4/H+ R — C — OH R — C—
—O
2. H2CrO4 ∆
H
3. CrO3/H+ Carboxylic acid
1o alcohol
4. Na2Cr2O7 / H+ or K2Cr2O7 /H+ 46
Oxidation of 2° alcohol
Ø Oxidation of 2o alcohols using any type of oxidizing agent (mild/strong) will yield a
ketone.

R KMnO4 / H+
∆ R
R—C—OH —O
R— C—
PCC in CH2Cl2
H
2o alcohol Ketone

47
Oxidation of 3° alcohol
Ø 3o alcohol cannot be oxidized
Ø This is due to the absence of hydrogen atom at the carbinol carbon.
Ø General reaction :

KMnO4 / H+
R ∆
NO REACTION
R—C—OH C atom with OH group is already bonded to 3
other C atoms.
\ There is no H atom that is bonded to
R PCC in CH2Cl2
carbinol carbon atom! So, unable to form the
C–O bond
3o alcohol

48
 Summary of OH
KMnO4 / H+
Oxidation of Alcohol Strong [O]
—
CH3—C—O Carboxylic acid
∆
CH3CH2OH H
1° alcohol PCC in CH2Cl2 —
Mild [O] CH3—C—O Aldehyde

KMnO4 / H+
Strong [O]
∆ O
CH3CH(OH)CH3 CH3—C—CH3 Ketone
2° alcohol PCC in CH2Cl2
Mild [O]
Note: Oxidation of
KMnO4 / H+ alcohol requires at
Strong [O] No Reaction least 1 H atom
∆ bonded to Carbinol
C atom
(CH3)3C-OH
3° alcohol PCC in CH2Cl2 No Reaction 49
Mild [O]
 Chemical Properties of Alcohol
Chemical Tests for Alcohol

Lucas Test Iodoform Test

To distinguish
different classes of alcohol
(1o, 2o and 3o ) To identify presence of methyl
carbinol group (CH3-CH-OH)

50
 Chemical Test of Alcohol
Lucas Test
Ø is used to differentiate 1o, 2o and 3o alcohols by observing the rate of reaction between
alcohols and Lucas reagent to form alkyl chlorides (haloalkane).
Ø Lucas reagent is a mixture of concentrated HCl and anhydrous ZnCl2.
Ø General reaction :

ZnCl2
R–OH + conc. HCl R–Cl + H2O
1o, 2o or 3o alcohols Haloalkane

51
 Chemical Test of Alcohol
Lucas Test
Ø The reaction mixture becomes cloudy due to the
formation of alkyl chloride (haloalkane).
Ø 2 layers are formed because the alkyl chloride formed is
insoluble in water.
Ø The time taken for cloudiness of solution to appear is a
measure of the alcohol reactivity.
Ø The reactivity of alcohols towards Lucas Test :
H R R

R—C—OH < R—C—OH < R—C—OH

H H R

10 alcohol 20 alcohol 30 alcohol 52

 Chemical Test of Alcohol
Lucas Test
Class of
Alcohols
Observation Equation of reaction
Primary No cloudy solution formed even
(1°) after 10 minutes upon heating

Secondary Cloudy solution appears within

(2°) 10 minutes upon heating

Tertiary Cloudy solution appears

(3°) immediately
53
 Chemical Test of Alcohol
Lucas Test Chemical equation
Conc. HCl / ZnCl2
i. CH2OH No observable reaction
1° alcohol

OH Cl
Conc. HCl / ZnCl2
+ H2 O
ii.
2° alcohol Solution turned cloudy within 10 minute

CH3 CH3
OH Cl
Conc. HCl / ZnCl2
iii. + H2 O

3° alcohol Solution turned cloudy immediately 54

 Chemical Test of Alcohol
Iodoform Test
Ø A test to identify the presence of the methyl carbinol group in alcohol compound.
H
Ø Reagent : excess I2 in NaOH(aq)
CH3C OH
Ø Observation : Formation of yellow precipitate.
Ø Methyl alcohol group cleavage to form carboxylate ion and haloform. R
methyl carbinol group
General reaction :
OH O
Excess I2 , NaOH
R–C–CH3 R–C–O- + CHI3 ¯
Carboxylate ion Triiodomethane
H (iodoform)
Yellow precipitate

55
Note: Iodoform Test represents oxidation reaction on carbinol carbon atom.
 Chemical Test of Alcohol H

Iodoform Test CH3C OH

methyl carbinol group

OH O
Excess I2, NaOH + CHI3 ¯
CH3CHCH3 CH3—C—O- Iodoform
Ethanoate ion (triiodomethane)

OH O
Excess I2 , NaOH + CHI3 ¯
CH3CH2CHCH3 CH3CH2C—O-
propanoate ion Iodoform
(triiodomethane)

Excess I2 , NaOH
CH2OH No observable change
(because there’s no methyl carbinol group present in compound) 56
 Learning Outcome

8.5 Phenol
a) Compare the acidity of phenol, alcohol and water.
b) Explain the chemical properties of phenol with reference to:
i. Reaction with sodium
ii. Reation with sodium hydroxide
iii. Identification tests using FeCl3 solution & Bromine water

58
 Introduction of Phenol
OH
Phenol

Phenol is a compound where there is one OH group directly

bonded to the Benzene ring

Physical Properties of Phenol

Ø Phenol is a colourless, crystalline solid,
Ø has boiling point of 182°C.

59
 Comparison of Boiling Point of Phenol with other
aliphatic alcohols and hydrocarbons
𝛅+ 𝛅− 𝛅+ 𝛅− 𝛅+ 𝛅− 𝛅+
OH OH OH OH
Hydrogen bond

Ø Phenol & aliphatic alcohols have the same Intermolecular forces of attraction which
is Hydrogen bond.
Ø But, since the polarity difference of OH bond in phenol is higher than in aliphatic
alcohols, then more heat energy is needed to break the
Ø Strong intermolecular force of Hydrogen bond between the OH group of phenol than
aliphatic alcohols
Ø Therefore, phenol has higher boiling point than aliphatic alcohols 60
 Comparison of Boiling Point of Phenol with other aliphatic
alcohols and hydrocarbons
Phenol > Alcohols > Hydrocarbons (alkane & alkene)

Intermolecular Hydrogen bond (HB) Van Der Waals forces of attraction

Forces (IMF) But HB between Phenol is Ø London Force
of Attraction much stronger
than between aliphatic alcohols
Strength of
IMF of Hydrogen bond > Van Der Waals Forces of attraction
attraction
Stronger IMF of attraction will require more heat energy to break
the strong attraction force. Therefor, the higher the Boiling Point 61
 Acidity of Phenol
Acidity Definition: Acidity is the ability of a compound to release a proton.

HA + H2O A- + H3 O +
Acid Base Conjugate Conjugate
base acid

Ø Acidity is determined by the stability of the conjugate base of an acid.

Ø Anything that stabilizes the conjugate base makes the acid more acidic.
Ø The higher the stability of the conjugate base the higher the acidity.

62
 Acidity of Phenol
Phenol dissociates in water to form phenoxide ion & hydronium ion.

Ø The acidity of phenol is due to the delocalisation of the negative charge of the phenoxide
ion inside the benzene ring in which causes the phenoxide ion to be stabilized by the
resonance effect. 63
 Comparison of acidity between phenol, alcohol & water
Alcohols, water and phenol are classified as weak acid.
Ø act as proton donor in aqueous solution.
Ø Alcohol, water and phenol have different acidity
Ø (different Ka values : Higher Ka value, higher the Acidity)
Ø The acidity of phenol and alcohols is influenced by :
Compounds pKa Ka
i. Inductive Effect
Ethanol 16 1x10-16
ii. Resonance Effect Water 14 1x10-14
Phenol 10 1x10-10
Ethanol < H2O < Phenol Acidity
increases 64
 Comparison of acidity between phenol, alcohol & water
Order of Acidity : Ethanol < H2O < Phenol
This equations shows the dissociation of compound in water

- + H3O+
OH + H O O
2

Phenol Phenoxide ion

CH3CH2OH + H2O CH3CH2O- + H3O+

Ethanol Ethoxide ion

H2O + H2O OH- + H3O+

Water Hydroxide ion 65
 Comparison of acidity between phenol, alcohol & water
Explanation : Ethanol < Water < Phenol
CH3CH2OH H2O
acidity increase
Ø Ethanol is less acidic compared to water.
Ø The presence of alkyl group as electron donating group (EDG) : ethoxide ion increases the density of
electron on the oxygen atom. Increase in electron density of ethoxide ion will decrease the stability of
ion.This phenomenon is call Inductive effect.
CH CH O - +
CH3CH2OH + H 2 O 3 2 + H 3 O
Ethoxide ion

H2O + H2 O OH- + H3O+

Hydroxide ion

Ø This makes the ethoxide ion less stable compared to hydroxide ion. 66
 Inductive Effect on Alkoxide Ion
CH3CH2 > O- The arrow shows the Inductive Effect of
Electron Donating Group (EDG) of Alkyl
Towards the O atoms

Ø CH3CH2 group in ethoxide ion is the alkyl group that has the Electron Donating Effect
(EDG) through the single bond with O atom.

Ø The EDG donates electron density on O atom in ethoxide ion where this causes the O
atom in ethoxide ion to be less stable than Hydroxide ion, OH-

Ø Hence, ethoxide ion becomes less acidic than hydroxide ion.

67
 Resonance Structure on phenoxide Ion
Ø Phenol is more acidic than aliphatic alcohol of ethanol because the phenoxide ion formed is stabilized
by the delocalization of negative charge of O atom into the benzene ring (Resonance Effect )

Resonance structure of phenoxide ion

Ø Ethanol is less acidic than phenol because the negative charge on O atom of ethoxide ion cannot be
delocalized over alkyl group. 68
Stability of Phenoxide ion through Resonance Effect
Ø The acidity of Phenoxide ion increases due to the ability of negative charge of Oxygen
atom to be delocalized into the Benzene ring. This will cause in increasing stability of
phenoxide ion through resonance effect.

resonance structure of phenoxide ion 69

Comparison of acidity between phenol, alcohol & water

Factor: Resonance effect

Order of Acidity : Ethanol < H2O < Phenol

Factor: Inductive Effect

70
 Chemical Properties of Phenol
Chemical Reactions of Phenol Confirmatory Test of Phenol

1. Reaction with metal, Na Ø The purpose of this confirmatory test is to

detect/identify if OH group is bonded
2. Reaction with Sodium Hydroxide, NaOH(aq) directly to a Benzene ring.
Ø Confirmatory Test can be conducted by
using:
1. Bromine Water
71
2. FeCl3 Solution

71
 Chemical Reaction of Phenol
1. Reaction with Sodium metal, Na
Ø Addition of Na to a solution of phenol in ether at room temperature, produces
phenoxide salt and H2 gas.

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 Chemical Reaction of Phenol
2. Reaction with Sodium hydroxide, NaOH
Ø Phenol is slightly soluble in water but dissolve in aqueous solution of NaOH at room
temperature to produce sodium phenoxide and water.

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 Confirmatory Test of Phenol
Using Bromine Water Using FeCl3 solution
Ø Reagent : Br2 in H2O Ø Reagent : FeCl3 solution
Ø Condition :At room temperature Ø Condition : At room temperature
Ø Observation: Ø Observation : Formation of purple complex
Reddish brown colour of Bromine
decolourised and white precipitate
formed.
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Phenol
2,4,6-tribromophenol
(white precipitate)
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 Involves
HCl
cleavage
R-Cl

Substitution reaction:
Produce Haloalkane
on R-OH PCl3 /PBr3
bond R-Cl/R-Br
PCl5
Na REACTIONS OF AROMATIC ALCOHOL REACTIONS OF ALIPHATIC ALCOHOL
R-Cl
SOCl2 in pyridine R-Cl
Aromatic Alcohol Aliphatic Alcohol
Lucas Conc. HCl, ZnCl2 R-Cl
NaOH Test
R-OH Conc. H2SO4 C C Dehydration
∆ of alcohol
Br2, H2O
Test of Phenol

Na
Confirmatory

Involves R-O-Na+
C C H2O, H3O+ (5.2) Hydration cleavage Sodium alkoxide
PREPARATIONS OF ALIPHATIC ALCOHOL

FeCl3 alkene of Alkenes on O-H Conc. CH3COOH, Conc.H+ CH3COOR

bond reflux
X Ester
NaOH(aq) (7.2) Hydrolysis
C C of Haloalkanes PCC in CH2Cl2 CHO Aldehyde
reflux
/CCOC /Ketone
Haloalkane Oxidation
i. Aldehyde/ketone
(7.2) Addition of KMnO4, H+ COOH Carboxylic Acid/
of alcohol
CH3CH2MgBr Grignard reagent ∆ /CCOC Ketone
Grignard reagent ii.H3O+ to carbonyl
compounds 11 K2Cr2O7 /H+ COOH Carboxylic Acid/
∆ /CCOC Ketone
zymase Iodoform
Glucose C6H12O6 Fermentation of glucose Test 12 Excess I2 , OH ! COO- + CHI3↓