ALCOHOLS, PHENOLS

AND ETHERS

PUNJAB BOARD
 NOTES

Alcohols, Phenols
and Ethers
Introduction Classification of Alcohols

Alcohols, phenols and ethers are classes Alcohols are classified as follows.
of organic compounds which are much
Alcohols
closer to water in structure and hence
considered as derivatives of water.

O O
Monohydric Polyhydric
Alcohols Alcohols
H H R H
Water Alcohol
Primary
Alcohols

O O Secondary
Alcohols
C₆H₅ H R R
Tertiary
Phenol Ether
Alcohols

Alcohol and phenol both have — OH in

them. Alcohol is called hydroxyl derivative
of alkane while phenol is hydroxyl
derivative of benzene. In ether both
hydrogen of water are replaced by alkyl
or aryl group.

Alcohols

“The compound in which one or more

hydrogen of alkanes are replaced by —
OH groups are called alcohols.” The
general formula of monohydric alcohol
is R — OH or CnH 2n+1 OH.

PUNJAB BOARD
 NOTES

Monohydric Alcohols
Monohydric Alcohol For Example

“The alcohol in which one hydrogen of OH

alkane is replaced by one —OH group is |
called monohydric alcohol.” e.g., CH₃ —CH —CH₃
iso-propyl alcohol

CH₃OH C₂H₅OH
Methyl Alcohol Ethyl Alcohol OH
|
CH₃ —CH —CH₂ — CH₃
CH₃ —CH₂ —CH₂ —OH sec-butyl alcohol
n-propyl alcohol

Monohydric alcohols are further classified (iii) Tertiary Alcohols

into primary, secondary and tertiary
“The alcohols in which hydroxyl group is
alcohols.
attached with tertiary carbon, are known
as tertiary alcohols.”
(i) Primary Alcohols
For Example
“The alcohols in which hydroxyl group is
atiached with primary carbon, are called OH
primary alcohols”. |
CH₃ —CH —CH₃
For Example |
CH₃
CH₃OH C₂H₅OH 2-Methyl, 2-Propanol
Methanol Ethanol (Ter-butyl alcohol)

CH₃ —CH₂ —CH₂ —OH

1-propanol

(ii) Secondary Alcohols

“The alcohols in which hvdroxvl group is

attached with secondary carbon, are
called secondary alcohols.”

PUNJAB BOARD
 NOTES

Polyhydric Alcohols
Polyhydric Alcohol

“If more than one hydroxyl group — OH

are present in a compound, it is called
polyhydric alcohol.” If number of — OH
groups are two, it its dihydric if it is three
it is called trihydric etc.

For Example
OH OH
| |
CH₂ — CH₂
1 ,2 Ethanediol
( Ethylene Glycol )

OH OH OH
| | |
CH₂ — CH — CH₂
1,2,3, Propanetriol
(Glycerine or Glycerol)

OH OH OH OH OH OH
| | | | | |
CH₂ — CH — CH — CH — CH — CH₂
(Mannitol)

PUNJAB BOARD
 NOTES

Nomenclature
of Alcohols
There are two methods for naming (1) Select longest possible chain of
alcohols. carbon atoms containing the hydroxyl
group in it.
(a) Common or Trivial Names
(2) Start numbering from that end
which is near to — OH group.
In common method of naming
word “alcohol” it's added after the
(3) The suffix used for alcohol is “ol”.
name of alkyl radical. Lowers
alcohols or simpler alcohols are
(4) The position of —OH group is
usually named by this method.
indicated by a number placed before
the name.
For Example
(5) If substituents of different nature
CH₃OH are present, they are named in
(Methyl Alcohol) alphabetical
order.

C₂H₅OH CH₃ —CH₂ —CH₂ —CH₂ —OH

(Ethyl Alcohol) 1-butanol

CH₃ —CH₂ —CH₂ —OH CH₃ OH

(n-propyl alcohol) | |
CH₃ — CH — CH₂ — CH —CH₃
4-Methyl-2-pentanol
C₆H₅ — CH₂ — OH
(Benzyl Alcohol)
(6) If more than one hydroxyl group are
present on a molecule, they are
(If one hydrogen from methyl group of indicated by an appropriate suffix diol,
toluene is removed, it is called benzyl triol, etc. For example,
radical) OH OH
| |
CH₂ — CH₂
1 ,2 Ethanediol
(Ethylene Glycol)

OH OH OH
| | |
CH₂ — CH — CH₂
1,2,3, Propanetriol
(Glycerine or Glycerol)
(b) IUPAC System
(7) The unsaturated alcohols are
Following rules are obeyed for the named in such a way that hydroxyl
nomenclature of alcohol. group rather than the point of un-
saturation gets the lower number,
e.g.,

PUNJAB BOARD
 NOTES

⁴ ³ ² ¹
CH₃ —CH = CH — CH₂OH
2 - Buten - 1 - ol

CH₂ = CH — CH₂ — OH
2 - Propen - 1 - ol

If both alkene and alcohol are present

in same group, the suffix of alkene
should be “en” rather than “ene”.

(8) When hydroxyl group is not a

preferred functional group as in
hydroxyl acids, aldehydes and ketones,
the substituent name hydroxyl is used
as a prefix to indicate the position of
OH group, e.g;

HO — CH — COOH
—

HO— CH — COOH
2,3 Dihydroxy butandioic acid
(Tartaric Acid)

OH
—

³ ² ¹
CH₃ — CH — COOH HO
2 - Hydroxy Propanoic acid
(Lactic Acid)

PUNJAB BOARD
 NOTES

The Name of Some Alcohols in the Two Systems

Formula Common Name IUPAC Name

CH₃OH Methyl Alcohol Methanol

CH₃CH₂OH Ethyl Alcohol Ethanol

CH₃CH₂CH₂OH n-propyl Alcohol 1-Propanol

CH₃
|
CH —OH iso-propyl alcohol 2-Propanol
|
CH₃

CH₃ —CH₂ —CH₂ —CH₂ —OH n-butyl alcohol 1-Butanol

CH₃—CH —CH₂—OH
| iso-butyl alcohol 2-Methyl,1-Propanol
CH₃

CH₃—CH₂ —CH—OH
|
sec-butyl alcohol 2-Butanol
CH₃

CH₃
|
CH₃ — C — CH tert-butyl alcohol 2-Methyl,2-Propanol
|
CH₃

CH₃
|
2,2-dimethyl,1-
CH₃ — C—CH₂—OH neo-pentyl alcohol
propanol
|
CH₃

PUNJAB BOARD

Industrial preparation
of Alcohols
(1)Methanol or Methyl Alcohol or
Wood Spirit (Wood Naphtha)
Methyl alcohol was obtained by the
destructive distillation of wood logs
and also called “wood spirit”. Now a
days, methanol is prepared from
carbon monoxide and hydrogen or
water gas.
CO reacts with H⁺ at high
temperature (450°C), 200
atmospheric pressure and in the
presence of ZnO, + Cr₂0 catalyst
following reaction take place.
First of all, a mixture of carbon monoxide
and hydrogen (water gas) is purified,
compressed under a pressure of 200
atmospheres and taken into ' a reaction
chamber by means of coiled pipe. Here
the catalyst is heated upto 450-500°C.
Gases react to form methanol vapours.
These vapours are passed through a
condenser to get methanol. Unreacted
gases are re-cycled through compressor
nto reaction chamber.
PUNJAB BOARD
NOTES
Properties of Methyl Alcohol
It's specific gravity is 0.793 g/cm³.
It boils at 64.5°C.
It is solvent for oils and fats.
It is poisonous.
It causes blindness and even death.
It is used for denaturing of alcohol.
(2) Ethanol or Ethyl Alcohol or Grain
alcohol
Ethanol is prepared on industrial scale
by the process of fermentation.
“Fermentation is a chemical, change in
which larger molecules are broken
down to smaller molecules in the
presence of enzymes (living catalyst)
present in the bacteria or yeast.
Optimum Conditions
The optimum conditions of
temperature is 25—35°C, which is a
optimum temperature for the growth
of enzymes. Moreover, proper aeration,
dilution of solution and the absence of
any preservative are essential
conditions for fermentation.
In Pakistan, ethanol is prepared by the
fermentation of molasses, starch grains
or fruit juices.
From Molasses
The residue obtained after the
crystallization of sugar from
concentrated sugar cane juice is called
molasses. It undergoes fermentation in
the presence of enzymes present in
yeast to give ethanol.
Invertase
C₁₂O₂₂H₁₁ + H₂O C₆H₁₂O₆ + C₆H₁₂O₆
Yeast
Sucrose Glucose Fructose
Zymase
C₆H₁₂O₆ 2C₂H₅OH + 2CO₂
Yeast
 NOTES

Industrial preparation
of Alcohols
From Starch

Starch is a natural polymer of

glucose. It is mostly present in
grains of wheat or barley or
potatoes.

Rectified Spirit

Alcohol obtained by fermentation i1s only

upto 12% and never exceeds 14% because
beyond this limit, enzymes become
inactive. This alcohol is distilled again and
again to obtain 95% alcohol which is called
rectified spirit.

Absolute Alcohol

“Ethyl alcohol which is 100% pure is

called absolute alcohol.” Absolute
alcohol is obtained by re-distillation of
rectified spirit in the presence of quick-
lime. CaO, which absorb moisture.

Denaturing of Alcohol

Sometimes, ethanol is denatured by

the addition of 10% methanol to avoid
its use for drinking purposes. Such
alcohol is called “methylated spirit".
Methanol is toxic to humans, causing
blindness in low dose (15 cm) and death
in larger amount (100 — 250 cm).

A Small quantity of pyridine or acetone

may also be added for denaturing of
alcohol.

PUNJAB BOARD
 NOTES

Physical Properties
1. Lower alcohols are generally
colourless liquids with characteristic
sweet smell and burning taste.

2. They are readily soluble in water

but solubility decreases in higher
alcohols. The solubility of alcohols is
due to hydrogen bonding which is
prominent in lower alcohols but
diminish in higher alcohol.

3.Melting and boiling points of

alcohols are higher than
corresponding alkanes. Methyl
alcohol and ethyl alcohol are liquids
while methane and ethane are
gases. This is also due to hydrogen
bonding which is present in
alcohols but absent in alkanes

PUNJAB BOARD
 NOTES

Reactions of Alcohol
Alcohols are reactive in two ways.

(1) Reactions in which C — O (1) Reaction in which C — O

Bond Breaks Bond is Broken

(2) Reaction in which O — H

Bond Breaks

(2) Reactions in which O —H

bond is broken

Which bond will break, depends upon

the nature of the attacking reagent. If a Mg
nucleophile attacks, it attacks the C — O
bond which breaks. On the other hand, if
an electrophile attacks on alcohol, it is
the O — H bond which breaks.

The order of reactivity of alcohols

when C — O bond breaks.

Tertiary Alcohol = Secondary Alcohol =

Primary Alcohol

The order of reactivity of alcohols

when O — H bond breaks.

CH₃OH > Primary Alcohol > Secondary

Alcohol > Tertiary Alcohol

PUNJAB BOARD
 NOTES

Reactions of Alcohol
(3) Oxidation of Alcohols
3. Oxidation of Tertiary Alcohol
Alcohol are oxidised in the presence
CH₃ CH₃
of concentrated H₂SO₄ and

__

__
K₂Cr₂O₇
potassium dichromate to aldehyde CH₃ — C — OOH H₂SO₄
CH₂ = C — CH₃ +H₂O

__
and then to carboxylic acid. CH₃

CH₃
Primary alcohol > Aldehyde >> O O

_
__

=
K₂Cr₂O₇

=
Carboxylic Acid CH₂ = C + 3 [O] H — C —OH + CH₃ — C —CH₃
H₂SO₄

__
_
CH₃

1. Oxidation of Primary Alcohol: (3) Dehydration

Alcohols reacts with concentrated

H₂SO₄ and different products are
formed. Formation of products,
depend upon the temperature and
the amount of H₂SO₄ taken.

1. At 180°C and greater amount of

H₂SO₄, alkene is formed.

3C₂H₅ — OH + PCl₃ C₂H₅Cl CH₃

+ H₃PO₃
— CH₂ — OH + HO
180C
CH₂ = CH₂ + H₂O
2. Oxidation of Secondary Alcohol
H₂SO₄

2. At 140°C and greater amount of

alcohol, ether is formed.

140C
3CH₃ — CH₂ — OH + HO — CH₂ — CH₃ H₂SO₄
CH₃ — CH₂
— O — CH₂ — CH₃ + H₂

(3) Reactions with Phosphorus

Halides, PX₃ and PX₅

3C₂H₅ — OH + PCl₃ C₂H₅Cl + H₃PO₃

C₂H₅OH + PCl₅ C₂H₅Cl + POCl₃ +HCl

PUNJAB BOARD
 NOTES

Distinction between
primary, secondary
and tertiary alcohols
Distinction between methanol and
Lucas Test
ethanol by Iodoform test
Primary, secondary and tertiary Ethanol reacts with iodine in the
alcohols are identified and presence of NaOH to form yellow
distinguished by reacting them with crystalline solid iodoform, CHI₃
con. HCI in anhydrous ZnCl₂. An oily Methanol does not give iodoform test.
layer of alkyl halides separates out in
Iodoform
these reactions. yellow ppt
C₂H₅OH + 4I₂ +6NaOH CH₂OH CHI₃
Tertiary alcohols form an oily + HCOONa + 5NaI +5H₂O
layer immediately.
Secondary alcohols form an oily
layer in 5 — 10 minutes.
Primary alcohols form an oil layer
only on heating only.

Secondary Alcohol

R R
ZNCl 2
__

__

R___ CH___ OH + HCl

_

R___CH ___ Cl + H₂O

_

5-10mins
_

_
__

__

R R

Tertiary Alcohol

R R
ZnCl₂
__

__

R___ C___ OH + HCl R___ C ___ Cl + H₂O

_

Immediately
_

_
__

__

R R

PUNJAB BOARD
 NOTES

Uses of Alcohols
Methanol is used as a solvent for
fats, oils, paints, varnishes.
It is also used as antifreeze in the
radiators of automobiles and for
denaturing of alcohol.
Ethanol is also used as a solvent
for paints, oils, drugs, dyes,
perfumes, gums and
varnishes, as a drink and as a fuel
in some countries.
It is used in pharmaceutical
preparation and as a
preservative for biological
specimen.
As preservative for biological
specimens.

PUNJAB BOARD
 NOTES

Phenols
The aromatic compounds which
contain one or more — OH groups
attached directly to benzene ring
are called phenols. e.g. carbolic acid
or phenol, CH₅ — OH is the simplest
example of phenols.

Carbolic acid or phenol was

discovered by Runge in 1834 from
coal tar.

PUNJAB BOARD

17
 NOTES

Preparation of
Phenols
(1) From Chlorobenzene (2) Fusion of Sodium
(Dow’s Process) Benzenesulphonate with NaOH

this process, chlorobenzene is

Phenol is obtained by fusing the
heated at 360°C with dilute solution
mixture of sodium benzene sulphonate
(10%) of NaOH at 200° atmospheric
and solid sodium hydroxide at 250°C.
pressure.

Sodium phenoxide is converted to The resulting sodium phenoxide is

phenol by treating it with treated with an acid stronger than
hydrochloric acid. phenol to regenerate the free
product.

PUNJAB BOARD

18
 NOTES

Physical properties of
Phenols
Phenol is colourless, crystalline
solid and is deliquescent. The
dellquescence is the process in
which a substance absorbs
moisture and changes into a
hiquid form.
Its melting point is 41°C and
boiling point is 182°C.
It is sparingly soluble in water
forming pink solution at room
temperature but completely.
soluble at 65.9°C which is the
consulate temperature, for
water-phenol system.
It is poisonous and used as
disinfectant in hospitals and
washrooms.

Reactions of Phenol

Phenol shows two types of

reactions.
(1) Reactions due to — OH group. 0
(2) Reactions due to benzene ring.

Following structure helps to

understand the behaviour of
phenol.

Phenols are less reactive to

nucleophile so nucleophilic attack is
less

favoured i e. OH is not easy to

replace while electrophilic attack on
the ring is easy.

3C;Hs —OH + PCl;arrow 3C,HsCl +

HsPOs

C>HsOH + PCls arrow C-HsCl+ POCI;

+ HCI

PUNJAB BOARD
 NOTES

Reactions of Phenol
Phenol shows two types of
reactions.
(1) Reactions due to — OH group. 0
(2) Reactions due to benzene ring.

Following structure helps to

understand the behavior of phenol.

Phenols are less reactive to

nucleophile so nucleophilic attack is
less favored i e. OH is not easy to
replace while electrophilic attack on
the ring is easy.

PUNJAB BOARD

20
 NOTES

Acidity Phenols
1. Phenol is less acidic than
carboxylic acids and more acidic
than alcohols. It is partially
soluble in water but highly
soluble in a alkali like NaOH.
2. Phenol does not reacts with
NaHCO₃ and no CO₂ evolved
while carboxylic acids evolve CO₂
due to greater reactivity.
3. When phenol is dissolved in
water it, dissociate slightly. The
dissociation constant of phenol Relative acidic strength of alcohol,
is 1.3 x 10⁻¹⁰ and pH of solution is phenol, water and carboxylic acid is
between 5 to 6. It dissociates as. as follows:
Carboxylic acid > Phenol > Water >
Alcohol

(a) Reaction of Phenol Due to

OH Group
(1) Salt Formation
Phenol reacts with alkalis to form
salt (sodium phenoxide and water)
Acidity of phenol is due to the
resonance stability in phenoxide ion.
Strength of an acid, depends upon
the stability of conjugate base or
anion of an acid. Greater will be the
stability of anion or conjugate base,
stronger will be the acid. In (2) Ester Formation
phenoxide ion, the negative charge Phenol reacts with acetyl chloride in
on oxygen atom can become the presence of a base to form an
mvolved with the m-electron cloud ester.
on the benzene ring. The negative
charge is thus delocalized on the
ring and the phenoxide ion
becomes relatively stable. This type
of delocalization is not possible with
alcohol
(3) Reaction with Zinc

Phenol is reduced to benzene when

reacts with Zinc dust.

PUNJAB BOARD
 NOTES

(b) Reaction Due to Benzene (4) Hydrogenation

Ring When hydrogen is passed through
phenol at 150°C in the presence of
(1) Nitration Ni catalyst it gives cyclohexanol.
Phenol reacts with dil, and conc.
HNO₃ at different temperature as
follows.

(5) Reaction with Formaldehyde

Phenol react with formaldehyde
(methanal) in the presence of acid
or alkah to give hydroxy benzyl
alcohol which on further reaction
with other phenol molecules yield a
polymer called bakelite.

(2) Sulphonation
Phenol reacts with conc. H2SO4 at
room temperature giving ortho and
para benzens sulphonic acids.

(3) Halogenation
Aqueous solution of phenol reacts
with bromine water to give white
ppt. of 2, 4, 6 tribromophenol.

PUNJAB BOARD

22
 NOTES

Bakelite

PUNJAB BOARD
 NOTES

Uses of Phenols
Phenol is used for the
preparation of bakelite (plastic
resin)
Phenol is used to prepare picric
acid. Picric acid and its salts are
used as explosives.
Phenol is used as antiseptic
(dettol), herbicide and wood and
ink preservatives.As antiseptic, it
is used in soaps, lotions and
ointments.
Phenol is used as starting
material for many
pharmaceuticals like salicylic
acid, aspirin, phenacetin, salol
etc.
It is used to prepare
cyclohexanol which is a good
organic solvent.

PUNJAB BOARD
 NOTES

Ethers
The organic compounds in which
different alkyl or aryl groups are
atiached on both side of oxygen
atom are called ethers. these are
classified into two types.

(1) Simple or Symmetrical

Ethers

The ethers in which two similar alkyl

or aryl are present on both side of
oxygen atom e.g.,CH₃ — OCH₃
dimethyl ether, (C₂H₅)₂O diethyl
ethyl, (C₆H₅)₂O diphenyl ether.

(2) Mixed or Unsymmetrical

Ethers

The ethers in which two different

groups (alkyl or aryl) are attached
with oxygen atom are called mixed
ethers. e.g., methyl ethyl ether
CH₃OC₂H₅.

PUNJAB BOARD
 NOTES

Nomenclature
Ethers are named either by IUPAC
system or by common names. In
IUPAC system the large alkyl groups
is taken as parent molecule and
given the last name (suffix) while
the smaller alkyl group along with
oxygen is used as prefix and given
the name alkoxy (e.g methoxy,
ethoxy, propoxy etc).

IUPAC names are not common as

they are difficult. Usually ethers are
known by their general names, as
given below:

Formula Common Names IUPAC

CH₃OCH₃ Dimethyl ether Methoxy methane

CH₃OC₂H₅ Ethyl-methyl ether Methoxy ethane

C₂H₅OC₂H₅ Diethyl ether Ethoxy ethane

C₂H₅O CH₂— CH₂— CH₃ Ethyl n-propylether Ethoxy propane

CH₃OC₆H₅ Methyl phenyl ether Methoxy benzene

C₆H₅OC₆H₅ Dipheyl ether Phenoxy benzene

PUNJAB BOARD
 NOTES

Preparation of Ether
Ethers are prepared from alcohols
either directly or indirectly. Usually
(3) Action of H₂SO₄ on Ethanol
they are obtained by the following
methods:

(1) Williamson’s Synthesis

H₂SO₄
2CH₃ — CH₂OH CH₃ — CH₂ — O — CH₂ — CH₃ + H₂O
100C

Alcohols are reacted with metallic

sodium to form alkoxides. This
alkoxide is a strong nucleophile and
readily reacts with alkyl halide to
produce an ether.

2C₂H₅OH + 2Na C₂H₅ONa + H₂

C₂H₅ONa + C₂H₅Br C₂H₅OC₂H₅ + NaBr

(2) From Silver Oxide and Alkyl

Halides

When alkyl halides are heated with

silver oxide, ethers are formed.

2C₃Br + Ag₂O CH₃OCH₃ +2AgBr

2CH₃ — CH₂ — Br + Ag₂O CH₃ — CH₂ — O — CH₂ —CH₃ +2AgBr

PUNJAB BOARD
 NOTES

Physical properties
Usually ethers are volatile liquids,
highly inflammable with low
boiling points.
They are slightly soluble in water
but fairly soluble in organic
solvent.
Ether molecules do not show
hydrogen bonding with one
another but they show week
hydrogen bonding with water
molecules due to which they are
slightly soluble in water.

PUNJAB BOARD
 NOTES

Chemical properties
Ethers are less reactive than (ii) Ethers also react with hot
alcohols because no hydrogen atom phosphorous pentachloride to give
is attached with oxygen atom alkyl chloride.
directly. Ethers do not react with
alkalies, NH₃, sodium metal dilute
C₂H₅ — O — C₂H₅+ PCl₅
acids, oxidising agents or reducing
agents. However ethers react with
halogen acid HI. Ethers do not react
with HF, HCl
2C₂H₅Cl + POCl₃
(i) Reaction of Ether with HBr

C₂H₅ — O — C₂H₅+ HBr C₂H₅OH — O — C₂H₅ + Br

—
H

Oxonium Ion

(ii) Reaction of Ether with HI

C₂H₅OC₂H₅+ HI C₂H₅OH +O + C₂H₅I + I

—

H
Oxonium Ion

C₂H₅ — O — C₂H₅+ I C₂H₅OH + C₂H₅I

—

H
C₂H₅OH
H + HI C₂H₅OH + H₂O

Note: In case of mixed either,

smaller radical is attached to the
halide and bigger radical is attached
to the alcohol.

PUNJAB BOARD
 NOTES

Uses of Ethers
As anesthetic
As refrigerant
Solvent for extraction of organic
compounds.
For dissolving oils, fats, resins.
For the manufacture of
smokeless gunpowder.

PUNJAB BOARD
 NOTES

Exercise
Fill in the blanks True or False

(i) Primary, secondary and tertiary alcohols (i) Methylated spirit contains 95%
can be identified by Lucas test. methyl alcohol and 5% ethyl alcohol.
False
(ii) Oxidation of Secondary alcohols give
ketones. (i) Ethyl alcohol 1s a very good anti-
freezing agent.
(iii) Alcohols on heating with H₂SO₄ give False
alkenes at high temperature.
(iii) Methanol 1s also called wood spirit.
(iv) Alcohols have high boiling points than True
ethers due to stronger hydrogen
bonding. (iv) Only 14% ethyl alcohol can be
prepared by fermentation.
(v) Williamson’s synthesis is used to True
prepare ether.
(v) Ethers do not show hydrogen
(vi) Methanol is also called wood spirit. bonding.
True
(vii) Carbolic acid is the other name of
phenol. (vi) Alcohols are more acidic than
phenols.
(viii) Primary, secondary and tertiary False
alcohols can be prepared by reacting
Grignard reagent with carbonyl (vii) Phenol is more soluble in water
compound. than lower alcohols.
False
(ix) Alcohols and carboxylic acids react to
produce esters. (viii) Alcohols are more basic than
ethers.
(x) Glycol is used as anti-freezing agent in False
automobile radiator.
(ix) Ethers have higher boiling points
(xi) The process of conversion of starch than alcohols and phenols.
into alcohol with the help of False
microorganisms is called fermentation.
(x) Methanol and ethanol can be
(xii) Ketones on reduction give secondary distinguished by iodoform test.
alcohols. True

PUNJAB BOARD
 NOTES

Multiple Choice Questions

(i) Which compound shows hydrogen ((vii) Which compound is called a
bonding: universal solvent:
(a) C₂H₆ (a) H₂O
(b) C₂H₅CI (b) CH₃OH
(c) CH₃ — O — CH₃ (c) C₂H₅OOH
(d) C₂H₅OH (d) CH₃—O—CH₃

(ii) Which compound shows maximum (viii) Methyl alcohol is not used:
hydrogen bonding with water: (a) As a solvent
(a) CH₃OH (b) As an anti-freezing agent
(b) C₂H₅OH (c) As a substitute for petrol
(c) CH₃ — O — CH₃ (d) For denaturing of ethyl alcohol
(d) C₆H₅OH
(ix) Rectified spirit contains alcohol
(iii) Which compound is more soluble in about:
water: (a) 80%
(a) C₂H₅OH (b) 83%
(b) C₆H₅OH (c) 90%
(c) CH₃COCH₃ (d) 95%
(d) n-Hexanol
(x) According to Lewis concept ethers
(iv). Which compound will have the behave as:
maximum repulsion with H,O: (a) Acid
(a) C₆H₆ (b) Base
(b) C₂H₅OH (c) Acid as well as a base
(c) CH₃CH₂CH₂OOH (d) None of these
(d) CH₃ — O — CH₃

(v) Ethanol can be converted into

ethanoic acid by:
(a) Hydrogenation
(b) Hydration
(c) Oxidation
(d) Fermentation

(vi) Which enzyme is not involved in

fermentation:
(a) Diastase
(b) Zymase
(c) Urease
(d) Invertase

PUNJAB BOARD

Short Questions
Question : 01
What are alcohols? How are they
classified? How will you
distinguish between primary,
secondary and tertiary alcohols?
Answer
The organic compounds having
formula ROH are called alcohols.
They are of three types:
(1) Primary alcohols
(2) Secondary alcohols
(3) Tertiary alcohols
They can be distinguished by the
Lucas test. (See Answer of Q.8)
Question : 02
How is methyl alcohol obtained on
large scale? How it may be
distinguished from ethyl alcohol?
Answer
First part is detailed question
Consult text book for answer:
Ethanol gives iodoform test with
1odine in the presence of NaOH.
Formation of yellow crystals indicate
the presence of ethanol or ethyl
alcohol.
C₂H₅OH + 4I₂ + 6NaOH
CH₃I + HCOONa + 5NaI + 5H₂O
While methyl alcohol does not give
this reaction.
CH₃OH + I₂ + NaOH No yellow ppt
PUNJAB BOARD
NOTES
Question : 03
What is fermentation? Which
compound may be obtained on
industrial scale by fermentation?
Answer
Fermentation :
It is a biochemical process which
occurs in the presence of certain
enzymes secreted by
microorganisms such as yeast.
More detail see in the text book.
Ethanol (C₂H₅OH) is obtained by
fermentation at industrial scale.
Question : 04
Explain the following terms:
(i) Absolute alcohol
(ii) Methylated spirit
(iii) Rectified spirit
(iv) Denaturing of alcohols
Answer
(i) Absolute alcohol
100% ethyl alcohol is called absolute
alcohol. It is obtained by redistilation
of rectified spirit with CaO which
absorbs moisture.
(ii) Methylated spirit
Ethyl alcohol containing small
amount of methyl alcohol is called
methylated spirit.
(iii) Rectified spirit
Alohol obtained by fermentation 1s
12 — 14%. It 1s distilled again and
again to obtain 95% alcohol which is
called rectified spirit.
(iv) Denaturing of alcohols
The addition of methanol
(poisonous) into ethanol to render it
unfit for the drinking purpose is
called denaturing of alcohol.
 NOTES

Question : 06
Question : 05
How will you distinguish between:
How does ethylalcohol react with
(i) An alcohol and a phenol
the following reagents?
(ii) An alcohol and an ether
Answer (iii) Methanol and ethanol
(iv) A tertiary alcohol and a
(i) Conc. H₂SO₄ primary alcohol
(v) 1-propanol and 2-propanol
Con H₂SO₄
CH₃CH₂ — OH CH₂=CH₂ + H₂O
140 ‫﮿‬C
Answer
(1) Phenol gives white ppt. with
bromine water.
(ii) Na
OH
1
CH₃⁻CH₂ ⁻OH + Na CH₃CH₂ONa + — H₂
2
+ 3Br₂(aq)

(iii) PCl₃

CH₃ — CH₂ — OH + PCl₃ CHCH₂ — Cl +

POCl₃ + HCl OH

(iv) CH₃COOH Br Br

+ 3HBr

CH₃ — CH₂OH + CH₃COO

Br
White ppt
Con H₂SO₄
140 ‫﮿‬C

While alcohols do not react with

bromine water.

CH₃ — C — OC₂H + H₂O

(iv) SOCl₂ Pyridine

CH₃ — CH₂OH + SOCl₂ CH₃ — CH₂ — Cl

SO₂ + HCl

PUNJAB BOARD

(2) Alcohols give oily layer of alkyl
halides while reacting with conc.
HCI in anhydrous ZnCl₂
ZnCl₂
R — CH₂OH + HCl
Heat
While ethers do not give this
reactions
(3) Ethanol gives iodoform with
iodine in the presence of NaOH.
Formation of yellow crystals indicate
the presence of ethanol.
C₂H₅OH + 4I₂ + 6NaOH
CHI₃ + HCOONa + 5NaI + 5H₂O
While methanol does not give
yellow ppt. of CH₃I
(4) Tertiary alcohol form an oily layer
immediately when react with conc.
HCI in anhydrous ZnCl₂
R R
ZnCl₂
R — C — OH + HCl
Immediately
R R
While primary alcohol form an oily
layer only on heating,.
ZnCl₂
R — CH₂ — OH + HCl
Cl Heat
+ H₂O
(5) 1-propanol is primary alcohol and
2-propanol is secondary alcohol. We
can distinguish them by Lucas test
as following:
CH₃ — CH₂ — CH₂ — OH + HCl
ZnCl₂
Heat
CH₃ — CH₂ — CH₂ — Cl + H₂O
PUNJAB BOARD
NOTES
CH₃
ZnCl₂
CH₃ — CH — CH₃ + HCl H — C — Cl
5-10 min
OH CH₃
R — CH₂Cl 2- propanol + H₂O
+ H₂O
Q.7 Give reasons for the followings
(i) Ethyl alcohol is a liquid which
methyl chloride is a gas.
Ethyl alcohol has strong hydrogen
bonding between its molecule whereas
methyl chloride does not have, rather its
molecules experience weaker dipole-
dipole forces. That 1s why ethyl alcohol 1s
liquid while methyl chloride is gas.
(ii) Ethanol has higher boiling point
than diethyl ether.
Ethanol has higher boiling point than
diethyl ether because strong hydrogen
bonding is present in ethanol. Whereas
diethyl ether has dipole-dipole forces
which are weaker than hydrogen
bonding due to this ethanol has higher
boiling point than diethyl ether.
(iii) Absolute alcohol cannot be
prepared by fermentation process.
Alcohol obtained by fermentation i1s
only upto 12% and never exceeds 14%
because beyond this limit enzymes
R — C — Cl + H₂O become inactive and the process is
ceased, that 1s why absolute (100%)
alcohol cannot prepared from
fermentation process.
(iv) Ethanol gives different products
with conc. H₂SO₄ under different
conditions.
High concentration of ethanol when
R — CH₂ — treated with conc. H2SO₄ at 140°C
produce diethyl ether.
Conc. H₂SO₄
2C₂H₅OH H₅C₂ — O — C₂H₅ + H₂O
140°
Whereas at lower concentration of ethanol
when treated with conc. H>SQ4 at 180°C
then it produce ethene.
Conc. H₂SO₄
C₂H₅OH H₅C₂ — O — C₂H₅ + H₂O
180°
 NOTES

(v) Water has higher boiling point O

than ethanol ||
Pd/Pt
(d) 2H — C — H + H₂ CH₃OH
In case of water, there is strong
Ni
three dimensional hydrogen OH
bonding due to two hydrogen |
bonds per molecule. (iii) C₂H₅OH CH₃—C—CH₃
Whereas, in case of ethanol, there is
weak hydrogen bonding due to only OH
one hydrogen bond per molecule. K₂Cr₂O₇ H₂SO₄ |
Hence, boiling point of water 1s (a) C₂H₅OH+[O] CH₃—C—H + H₂O
higher than ethanol. Ether

Q.8 How will you convert:

(i) Methanol into ethanol O
(ii) Ethanol into methanol || Ether
(iii) Ethanol into isopropyl alcohol (b) CH₃—C—H+CH₃—MgBr
(iv) Formaldehyde into ethyl
alcohol H₃O
+

(v) Acetone into ethyl alcohol CH₃CH — OMgBr CH₃CH₂CH — OH

Answer . + MgBrOH

(i) CH₃ — OH C₂H₅OH O

||
(iv) H—C—H C₂H₅OH
ZnCl₂
(a) CH₃ — OH + HCl CH₃Cl + H₂O
O
||
(a) H—C—H+CH₃—MgBr CH₃CH₂ — OMgBr
(b) 2CH₃ — Cl + 2Na Ether CH₃CH₃

H₃O
. hv
+ 2NaCl

+
(c) CH₃ — CH₃ + Cl₂ CH₃ — CH₂ — Cl CH₃CH₂OH + MgBrOH
+ HCl
(d) CH₃ — CH₂ — Cl + KOH O
(aq) ||
(v) CH₃ — C — OCH₃ C₂H₅OH

CH₃ — CH₂ — OH+ KCL O O O

|| K₂Cr₂O₇ || ||
Ethanol
(a) CH₃—C—CH₃+3[O] CH₃—C—OH+H—C—OH
H₂SO₄
(ii) C₂H₅OH CH₃OH
O
H₂SO₄ || LiAlH₄
(a) C₂H₅OH CH₂ = CH₂+ H₂O
180° (b) CH₃—C—OH+4[H] C₂H₅OH+H₂O
O

CH₂ CH₂
(b) CH₂ = CH₂ + O₃

O O

CH₂ CH₂
(c) + Zn 2H — C — H + ZnO
O O

PUNJAB BOARD
 NOTES

Question : 09 (iv) Ether Formation:

Explain the following terms using ethyl
alcohol as an example.
When excess amount of ethyl alcohol
reacts with less amount of conc. H₂SO₄
at 140°C ether is formed.
CH₃CH₂OH + CH₃—CH₂—OH

Conc. H₂SO₄
Answer

180 °C
(i) Oxidation:
Ethyl alcohol on oxidation changes to CH₃—CH₂—O—CH₂—CH₃ + H₂O
acetaldehyde and on further oxidation
changes to acetic acid. Mixture of
K₂Cr₂O₇ and conc. H₂SO₄ 1s good
oxidizing agent.
K₂Cr₂O₇
CH₃—CH₂—OH + [O] CH₃CHO + H₂O
H₂SO₄

CH₃CHO + [O] CH₃COOH

(ii) Dehydration:
Ethyl alcohol when reacted with conc. H-
SO4 at 180°C, dehydration takes place.
Removal of water from a substance in
called dehydration.

Conc. H₂SO₄
CH₃—CH₂—OH CH₂—CH₂ + H₂O
180 °C

(iii) Esterification: The process i which

alcohol and carboxylic acid reacts
together to form ester.

O
|
CH₃ — CH₂ — OH + CH₃ —| C —
OH
H+

O
||
CH₃ — C — OC₂H₅+ H₂O

PUNJAB BOARD
 NOTES

Question : 10
Compare the reactions of phenol with
that of ehtanol. Discuss the difference
if any.

Answer

Ethanol
Properties Phenol C₆H₅OH
C₂H₅OH

Solubility in H₂O Partially miscible Soluble in all proportions

Acidity Weakly acidic Neutral

Physical state Solid at room temp Liquid state

Hydrogenation in the Cyclohexanol is

No reaction
presence of Ni formed

Bromination Ring is brominated No reaction

Reduction with hot Zn

Benzene is formed No reaction
dust

Action of dilute nitric acid Ring is nitrated No reaction

Purple color is
Action of ferric chloride No purple color
obtained

Formation of esters takes

Action of organic acids No reaction
place

Formation of alkyl halides

Action of HX No reaction
takes place

Ethylene or ether is formed

Action of conc. H₂SO₄ Ring is sulphonated
according to the conditions

Iodoform reaction No ppt. Yellow ppt. of CHI₃

PUNJAB BOARD
 NOTES

Question : 11 Question : 12

Arrange the following compounds in Write down two methods for

order to their increasing acid strength preparing phenol. What is the action of
and give reason. H₂O, C₂H₅OH, C₆H₅OH, following on phenol.
C₆H₅COOH.

Answer Answer

Increasing acid strength 1s the following

See articles “Preparation of Phenols™
order.
and “reaction of phenols™.

C₂H₅OH > H₂O > C₆H₅OH > C₆H₅COOH

Acid strength depend upon the Question : 13

dissociation of compound and stability
of the anion conjugate base. Give the uses of phenols. How bakelite
is prepared from it.
Carboxylate ions RCOO are more stable
-
than phenolate 1on due to resonance
stability. Answer

O
See article “Uses of Phenol™.
O O
R—C R—C
- -
O O
Phenolate Carboxylate
Ion Ion

Alcohol are less acidic than phenol

because in phenoxide ion, charge of
oxygen is delocalized while charge of
-
oxygen in RO is localized.

-
Anion of water OH is least stable and most
reactive.

Dissociation of compounds is as follows.

_
H₂O H++_ OH
+
ROH RO + H_
+
C₆H₅OH C₆H₅O + H_
+
C₆H₅COOH C₆H₅COO + H

PUNJAB BOARD
 NOTES

Question : 14 Question : 15

(a) Write I.U.P.A.C. names of the (a) Name the following compounds:
following compounds:
(i) (CH₃)₂CH-OH, CH₃ — CH₂ — CH₂ — O — CH₃
(ii) (CH₃)₂CHCH₂OH C₆H₅ — O — C₆H₅
(iii) (CH₃)₃COH (CH₃)₂CH—O—CH(CH₃)₂
(iv) C₂H₅—CH -OH CH₃ — O — C₆H₅
| CH₃ — CH₂ — CH₃ — O — CH₂ — CH₃
CH₃
(b) Write down structural formulas of
(b) Write structure formulas for the the following compounds:
following compounds: Methoxy ethane, Ethoxy benzene,
Glycol, Glycerol, Carbolic acid, Sodium ethoxide, Sodium phenoxide,
Acetophenone, Picric acid Propoxy propane

Answer
(a) Write I.U.P.A.C. names of the following Answer
compounds:

(i) (CH₃)₂CH-OH 2-Propanol (a):

(i) CH₃ — CH₂ — CH₂ — O — CH₃
(ii) (CH₃)₂CHCH₂OH 2-Methyl-1-propanol Methoxy propane

(iii) (CH₃)₃COH 2-Methyl-2-propanol (ii) C₆H₅ — O — C₆H₅

Phenoxy benzene
(iv) C₂H₅—CH -OH 2-Butanol
| (iii) (CH₃)₂CH—O—CH(CH₃)₂
CH₃ Isopropoxy iso-propane

(b) Write structure formulas for the (iv) CH₃ — O — C₆H₅

following compounds: Methoxy benzene

(i) Glycol CH₂—CH₂ (v) CH₃ — CH₂ — CH₃ — O — CH₂ — CH₃

| | Ethoxy propane
OH OH

(ii) Glycerol CH₂—CH—CH₂ (b):

| | | (i) Methoxy ethane CH₃—O—C₂H₅
OH OH OH
(iii) Carbolic acid (ii) Ethoxy benzene C₂H₅—O—C₆H₅
OH _
+
(iii) Sodium ethoxide CH₃—CH₂—ONa
_
+
(iv) Sodium phenoxide ONa

(iv) Acetophenone
O=C—CH₃

(v) Propoxy propane

CH₃—CH₂—CH₂—O—CH₂—CH₂— CH₃
(v) Picric acid
OH
NO₂ NO₂

PUNJAB BOARD
NO₂