ALCOHOLS, PHENOLS

AND ETHERS

CHAPTER – 11

ALCOHOLS, PHENOLS AND ETHERS

Alcohols → R-OH
Phenols – OH
Ethers → R-O-R
Monohydric alcohols → compounds containing Csp3-OH
bond →

Primary alcohol (R-CH2-OH), secondary alcohol (

R2CH-OH), tertiary alcohol (R3C-OH)
Depending on the number of carbon atoms which are
directly attached to the carbon that is bonded with the -
Allylic alcohols OH group, alcohols can be classified into three types.

Benzylic alcohol Primary alcohol - Primary alcohols are those alcohols where
the carbon atom of the hydroxyl group (OH) is attached to
Depending on the number of hydroxyl groups attached, only one single alkyl group. Some examples of these primary
alcohols include Methanol (propanol), ethanol, etc. The
alcohols can be classified into three types.
complexity of this alkyl chain is unrelated to the classification
• Monohydric alcohols: They contain one -OH group. of any alcohol considered as primary. The existence of only
one linkage among –OH group and an alkyl group and the
Example, CH3CH2-OH
thing that qualifies any alcohol as a primary.
• Dihydric alcohols: They contain two -OH groups.
Example, 1,2-Ethandiol. Secondary alcohol - Secondary alcohols are those where the
carbon atom of the hydroxyl group is attached to two alkyl
• Trihydric alcohols: They contain three -OH groups. groups on either side. The two alkyl groups present may be
Example 1,2,3-Propantriol. either structurally identical or even different.
Tertiary Alcohol - Tertiary alcohols are those which feature as alkyl or aryl derivatives of carbinol. Example: CH3-CH2-OH
a hydroxyl group attached to the carbon atom which is is methylcarbinol and CH3-CH2-CH2-OH is Ethylcarbinol.
connected to 3- alkyl groups. The physical properties of these
IUPAC System: In IUPAC nomenclature, we term the alcohols
alcohols mainly depend on their structure. The presence of
as Alkanols. We get the name of any alcohol by replacing the
this -OH group allows the alcohols in the formation of
last ‘e’ from the name of the corresponding alkane by the
hydrogen bonds with their neighbouring atoms. The bonds
suffix ‘–ol’. Then, we select the longest carbon chain
formed are weak, and this bond makes the boiling points of
containing the OH group as the parent chain. We, then,
alcohols higher than its alkanes.
number the longest chain in such a way that the carbon atom
carrying the OH group gets the smaller number. After this, we
show the position of the substituents by suitable numbers
allotted to their respective carbon atom.

Example
The compound CH3-OH is Methyl Alcohol but in
the IUPAC, we call it as Methanol. Here, we replace
In phenols -Or group is connected to sp2 hybridised carbon. It the last ‘e’ of the methane by ‘ol’ which indicates
can also be monohydric, dihydric etc. dihydric phenol into the presence of an alcohol group. In the naming of
ortho, meta or para derivative.
the Cyclic monohydric alcohols prefix, ‘cyclo’ is
used in writing the common or the IUPAC names
of the straight chain alcohols

2) Dihydric Alcohol
Dihydric alcohols have the general formula of (CH2)n(OH)2,
In allylic alcohols, -OH group is attached to sp3 hybridised where n= 2,3,4…. etc. Because of their sweet taste, we refer to
carbon but close to C = C bond. them as Glycols. Depending upon the relative position of the
CH2 = CH-CH2OH, Benzylic alcohol (C6H5CH2OH) two hydroxyl group, we can classify them as α, β, ϒ…..ω-
glycols, etc. Let us look at the system of their nomenclature.
Nomenclature of Alcohols
Common System: In common system, we name the α- glycols
Alcohols are of three major classes. They are:
by adding the word Glycol after the name of the alkene. In
Monohydric Alcohol contrast β, ϒ … ω – glycols get their names as the
corresponding polymethylene glycols. Example:
Dihydric Alcohol
Trihydric Alcohol

We will now discuss the nomenclature of these alcohols.

(1) Monohydric Alcohol
Monohydric alcohols have the general formula CnH2n+1OH
where n = 1, 2, etc. We can also represent them as R-OH where
R describes an alkyl group. There are three systems for the IUPAC system: In this system, we name the glycols as Diols
nomenclature of Monohydric Alcohol. and their class name is Alkanediols. We use Arabic numerals
to indicate the two hydroxyl group positions.
Common System: In this system, we name the monohydric
alcohols as Alkyl Alcohol. We get their names by adding the
name alcohol after the name of the alkyl group present in the
molecule.

Example 3) Trihydric Alcohol

The general formula of trihydric alcohols is (CH2)n(OH)3
The compound CH3-OH has one methyl group with where n = 3, 4, 5 …etc. In this system, we do not have any
an alcohol group. Hence, we call it Methyl Alcohol. general rule of nomenclature. So, there is only one IUPAC rule.
In this IUPAC system of trihydric alcohol, we call them as
Carbinol System: In this system, methyl alcohol (CH3OH) Alakanetriols. We use Arabic numerals to indicate the
gets the name Carbinol while other alcohols get their names position of the OH group.
Nomenclature of Phenols
The simplest derivative of benzene is Phenol. It is the Nomenclature of Ethers
common name as well as an accepted IUPAC name. Both in Common System: We get the common names of ethers by
the common and in the IUPAC system, we name the naming the two alkyl or aryl groups linked to the oxygen atom
substituted phenols as the derivatives of phenols.
as separate words in alphabetical order and adding the word
In the common system, we indicate the substituent position ether. In case of symmetrical ethers, we use the prefix di
present on the benzene ring with respect to –OH group by before the name of the alkyl or the aryl group.
adding the prefix such as ortho (o-) for 1:2, meta (m-) for 1,3
IUPAC system: In the IUPAC system, ethers are
and para (p-) for 1,4.
Alkoxyalkanes. The ethereal oxygen is taken with the smaller
However, in the IUPAC system, we use Arabic numerals to alkyl group and forms a part of the alkoxy group. On the other
indicate the position of the substituent w.r.t –OH group. The hand, the larger alkyl group is taken to be the part of the
carbon carrying the OH group gets the number 1. The phenols
alkane.
having a carbonyl group such as aldehyde, ketonic, carboxyl
or an ester group get their names as hydroxyl derivatives of
the parent aromatic compound.
 By hydroboration-oxidation
Q. Give IUPAC names of the following
compounds:

(ii) From carbonyl compounds

By reduction of aldehydes and ketones
Sol. (i) 4-Chloro-2,3-dimethylpentan-1-ol
(ii) 2-Ethoxypropane
(iii) 2,6-Dimethylphenol
(iv) 1-Ethoxy-2-nitrocyclohexane

Alcohol Preparation
(i) From alkenes
By acid catalysed hydration in accordance with Markownikoff
law. Aldehydes produce the primary alcohol while ketones
provide the secondary alcohol, when reduced.
By reduction of carboxylic acids and esters

Mechanism: There are three steps in the mechanism of acid

catalysed hydration of an alkene to form corresponding
alcohol.
Step 1: Carbocation formation and carbocation is formed by
attack of H3O+.
Step 2: Nucleophile H2O attacks on carbocation.
Step 3: Deprotonation to form alcohol H+ will be eliminated.
(iii) Hydrolysis of alkyl halides
R-X + KOH -> ROH + KX

If we take secondary alcohol than secondary alcohol

potassium halide and traces of alkenes is formed.
Example: If we take tertiary alkyl halide then on reacting with
KOH we get alkene as major product and potassium halide.
(iv) Preparation from Grignard reagent This method is generally carried out in breweries.
(a) The Grignard reagent reacts with formaldehyde to
form primary alcohol.

Preparation of Phenols
(i) From haloarenes

Note (ii) From Benzene sulphonic acid

Please remember whenever Grignard reagent
reacts with formaldehyde it forms primary alcohol.
When Grignard reagent reacts with any other
alcohol it forms secondary alcohol

(v) Hydrolysis of ethers

(iii) From diazonium salts

(vi) From the primary amines - by treatment with nitrous

acid (iv) From cumene

Industrial preparation of alcohol is by two methods:

Hydration of alkene and fermentation of sugar (used in
breweries) Physical properties of alcohol
Fermentation - Breakdown of complex substance into • They are usually liquid at room temperature.
simple substance by action of enzymes released by anaerobic
• They do not emit smoke when they are burning.
bacteria.
• They are flammable and produce a blue flame.
By this method we can prepare only ethanol.
In this firstly the sugarcane juice and water are mixed and • They usually give off a pleasant aroma without glycerol
and a few alcoholic beverages.
heated to form sweet liquid called molasses.
Then in presence of yeast and enzyme invertase it breaks in • Alcohol is colourless.
to glucose and fructose and then further glucose and fructose State of existence: Lower members are colourless liquids
break into further simpler substances called ethanol and with characterize smell. Higher members with more than 12
carbon dioxide. carbons are solid.
Boiling point: They have high boiling points due to hydrogen (2) The Solubility of Phenols
bonding. The hydroxyl group determines the solubility of phenol
If we compare their boiling points with hydrocarbons they in water. The hydroxyl group in phenol is responsible
will possess higher boiling point because of existence of for the formation of intermolecular hydrogen bonding.
hydrogen bonds in them due to which they occur at Thus, hydrogen bonds form between water and phenol
associated molecules. molecules which make phenol soluble in water.
(3) The Acidity of Phenols
Phenols react with active metals such as sodium,
potassium etc. and give the corresponding phenoxide.
These reactions of phenols indicate its acidic nature. In
phenol, the sp2 hybridized carbon of the benzene ring
attached directly to the hydroxyl group acts as an
Note electron withdrawing group.
Boiling point increase with increase in carbons in Thus, it decreases the electron density of oxygen. Due
chain: As no. of carbon atoms increases Vander wall to the delocalization of negative charge in the benzene
force increases hence boiling point increases ring, phenoxide ions are more stable than alkoxide
. ions. Therefore, we can say phenols are more acidic
than alcohols.
Example
Chemical reaction of alcohol
CH3CH2CH2OH < CH3CH2CH2CH2CH2OH Alcohol is most versatile organic compound. They can behave
in different manner to give different reaction. Three type of
The Second compound will definitely have the higher boiling reaction we will study
point as it has more number of carbon atoms. 1. Alcohol behaves as nucleophiles
Boiling point decreases with branching: as surface area gets They are electron rich species
reduced therefore Vander wall force decrease and boiling R-O-H → RO- + H (Acidic character is also shown)
point also decreases. alkoxide
Example: The one degree will have higher boiling point as it 2. Alcohols behave as electrophile
has more surface area. Electron deficient
Carbocation is formed
R-OH → R+ + OH-

Acidity of alcohols and phenols

Reaction with metals: Alcohols and phenols react with
Solubility: They are soluble in water due to formation of
active metals such as sodium, potassium and aluminium to
hydrogen bonds in them .However solubility decreases with
yield corresponding alkoxides/phenoxides and hydrogen. In
increase in number of carbon atoms in chain as non-polar
addition to this, phenols react with aqueous sodium
part increases therefore solubility decreases.
hydroxide to form sodium phenoxides.
Example
CH3CH2CH2OH and CH3CH2CH2 CH2CH2OH

The second one will have lower solubility because the non-
polar part is more in it.
Physical properties of phenols
(1) The Boiling Point of Phenols
Phenols generally have higher boiling points in
comparison to other hydrocarbons with equal
molecular masses. The main reason behind this is the
presence of intermolecular hydrogen bonding between
hydroxyl groups of phenol molecules. In general, the
boiling point of phenols increases with increase in the
number of carbon atoms.
This reaction shows that alcohols and phenols can donate H+
ions so they are acidic. Note
Acidity of alcohols: The acidity of alcohol decreases in the in resonating structure of phenoxide ion –ve charge
order of primary alcohol > secondary alcohol > tertiary is present at ortho and paraposition. So –ve charge
alcohol as shown below. This decreases in acidity is because stabilising groups can increase stability of
of the more inductive effect of alkyl group (electron releasing substituted phenoxide ion. Thus is can increase the
group) in tertiary alcohol than secondary and primary acidity
alcohol that increases the electron density on oxygen thereby
decreasing the polarity of O-H bond and therefore its acidity.

Alcohols, however, are weaker acids than water as shown by

the reaction below. If the alcohols were stronger acids than
water, the reaction given below will not occur in forward
direction since water (H-O-H) will not be able to donate H to
alkoxide.

Esterification: Alcohols and phenols react with carboxylic

acids, acid chlorides and acid anhydrides to form esters.

why phenols are more acidic than alcohols?

Phenols react with aqueous sodium hydroxide to produce
phenoxide ions. This indicates that the acidity of phenols is
higher in comparison to the alcohols. The phenoxide ion is
stabilized by the delocalization of negative charge due to the
resonance in the benzene ring.
Alcohols following the elimination of H+ create an alkoxide The reaction with carboxylic acid and acid anhydride is
ion which is the conjugate base of alcohol. The negative carried out in the presence of a small amount of concentrated
charge existing on oxygen atoms in alkoxide ion increases due sulphuric acid. The reaction is reversible, and therefore,
to the +I inductive effect of the alkyl group connected to it and water is removed as soon as it is formed. The reaction with
this destabilises the conjugate base and makes alcohol less acid chloride is carried out in the presence of a base
acidic. (pyridine) so as to neutralise HCl which is formed during the
– In the case of phenols, the negative charge on the oxygen reaction. It shifts the equilibrium to the right-hand side. The
atom is delocalized around the ring by resonance, resulting in introduction of acetyl (CH3CO) group in alcohols or phenols is
phenoxide ions. The negative charge on oxygen is thereby known as acetylation. Acetylation of salicylic acid produces
delocalized to the ortho and para carbon atoms, and the aspirin.
phenoxide ion is transformed into a stable resonant
structure. This stabilises the phenoxide ion and renders
phenol more acidic than alcohol.

Cleavage of carbon-oxygen bond in alcohols:

Reaction with HX:
R-OH + HI → RI + H2O
Reaction with SOCl2/PCl3/PCl5: Dehydrogenation and rehydrogenation reactions are
reversible and the reagents and components are recyclable as
a result of which the device can be used more efficiently as a
hydrogen supply network technology compared to other
hydrogen storage materials.
Step 1: Formation of protonated alcohol

Step 2: Formation of carbocation: It is the slowest step and

hence, the rate determining step of the reaction

Dehydration: alcohols undergo dehydration to form alkenes

on treating with a protic acid e.g., concentrated H2SO4 or
H3PO4 or catalyst such as anhydrous zinc chloride or alumina

Step 3: Formation of ethane by elimination of a proton.

Secondary and tertiary alcohols are dehydrated under milder

conditions.

Oxidation of alcohols: Oxidation of alcohols involves the

formation of a carbon-oxygen double bond with cleavage of
an O-H and C-H bonds.

Relative ease of dehydration follows the order as:

Tertiary > secondary > primary
Mechanism: In this primary alcohols give aldehydes in presence of
Dehydration of alcohols follows a three-step mechanism. oxidizing agent acid

Formation of protonated alcohol Acidified K2Cr2O7, CrO3, Collins-reagent, CrO3-pyridine,PCC

Formation of carbocation (pyridinium chlorochromate), PDC (Pyridium dichromate).
Formation of alkenes CH3CH2OH K2CR2O7 [O] CH3CHO →CH3COOH

[Link] of protonated alcohol:

In this step, the alcohol is acted upon by a protic acid. Due to
the lone pairs present on the oxygen atom it acts as a Lewis
base. Protonation of alcoholic oxygen takes place which
makes it a better leaving group. It is a reversible step which
takes place very quickly.
2. Carbocation formation:
In this step, the C-O bond breaks generating a carbocation.
This step is the slowest step in the mechanism of dehydration
of an alcohol. Hence, the formation of the carbocation is
considered as the rate-determining step. Note
3. Alkene formation: If we want to stop the reaction at stage of aldehyde,
This is the last step in the dehydration of alcohol. Here the we can use mild oxidizing agent. It is to be noted that
proton generated is eliminated with the help of a base. The primary alcohols give aldehyde and secondary
carbon atom adjacent to the carbocation breaks the existing alcohols give ketones.
C-H bond to form C=C. Thus, an alkene is formed.
 Reactions of phenols
(a) Electrophilic substitution reaction: Electrophilic
aromatic substitution reactions are the reactions where
an electrophile replaces one or more hydrogen atoms
attached to the aromatic ring. Phenols are highly prone
to electrophilic substitution reactions due to rich
electron density. The hydroxyl group attached to the
aromatic ring in phenol facilitates the effective
delocalization of the charge in the aromatic ring. Thus, it
stabilizes the arenium ion through resonance. The
hydroxyl group also acts as ortho para directors.
Secondary alcohols gives ketones but under drastic Nitration: The -OH group present in phenols activates
conditions like use of potassium dichromate it gives the ring to such extent that some phenols can be
carboxylic acid with less number of carbon atom than in nitrated even with dilute nitric acid at low temperature.
alcohol.

Tertiary alcohols give alkene because they do not have H

atom so oxidation is not possible and they show elimination Q. Why ortho-nitrophenol is more volatile
reaction. than para-nitrophenol?
Sol. O-Nitrophenol forms intramolecular H
bond whereas molecules of P-Nitrophenol
get associated through intermolecular H
bond. During boiling, the strong
intermolecular H bonding increases the
boiling point but intramolecular H
bonding cannot do so. Therefore, O-
Nitrophenol is more steam volatile than P-
Dehydrogenation - removal of Hydrogen. Nitrophenol.

Sulphonation: Phenol's can be sulphonated readily at O-

(ortho) and P(para) positions by the action of concentrated
sulphuric acid.

Note
C2H5OH is used for drinking purpose are beverage (b) Kolbe reaction: When phenol is treated with sodium
but hydroxide, phenoxide ion is generated. The phenoxide
CH3 OH is not good to consume. When in C2H5OH, ion generated is more reactive than phenol towards
CH3OH is added it becomes denatured alcohol if it is electrophilic aromatic substitution reaction. Hence, it
consumed by anyone it causes death. It hits the undergoes electrophilic substitution reaction with
nervous system and can cause blindness. carbon dioxide, which is a weak electrophile. Ortho-
 hydroxybenzoic acid (salicylic acid) is formed as the
(b) Williamsons synthesis: It is used for the preparation of
primary product. This reaction is popularly known as
simple as well as mixed ethers. Alkyl halide is heated
Kolbe’s reaction.
with alcoholic sodium or potassium alkoxide to form
corresponding ethers.
Thus, methyl iodide, on heating with alcoholic sodium
methoxide forms dimethyl ether.

(c) Reimer-Tiemann reaction: The Reimer Tiemann

reaction is an organic chemical reaction where phenol is
converted into an ortho hydroxy benzaldehyde using
chloroform, a base, and acid workup. This reaction can
also be described as the chemical reaction used for the Mechanism:
ortho-formylation of phenols. Step 1: Alcohol reacts with sodium metal to form the
conjugate base sodium alkoxide and realeases hydrogen gas.

Reaction of Phenol with zinc dust: Step 2: Sodium alkoxide is added to primary alkyl halide to
form the desired ether along with sodium halide.

Oxidation of phenol:

(c) In aryl ethers, sodium phenoxide reacts with RX

Preparation of Ethers
(a) Alcohol dehydration:

Physical properties of ethers

Existence: Lower members are gases and higher members
Mechanism: The formation of ether is a nucleophilic may be liquids or solid due to increase in the Vander wall
bimolecular reaction (SN2) involving the attack of alcohol force.
molecule on a protonated alcohol, as indicated below: Dipole moment: Ethers have higher dipole moments
because of electro negativity difference and structure is bent.
They have larger bond angles than alcohol. Alcohol have one
hydrogen and ether there are two bulky groups so, repulsion
between bulky groups are more therefore Bond angle will
increase.
More the bulky group’s, lower is the value of dipole moments.
CH3 - O - CH3 (1.3 D) C2H5OC2H5 (1.18 D)
Boiling point: Ethers have low boiling point because of less When HI is in excess and the reaction is carried out at high
polarity. temperature, ethanol reacts with another molecule of HI and
CH3 CH2 O CH2 CH3 CH3 CH2CH2CH2 OH is converted to ethyl iodide.
Step 3:
Boiling point – 307.6k boiling point – 390k (more
polarity)
Solubility: lower members are more soluble.
Example – C2 H5 OH CH3OCH3 ] same solubility
But as number of Carbon atoms increase, solubility decrease
because non polar part increase.
However, when one of the alkyl group is a tertiary group, the
Chemical properties halide formed is a tertiary halide as shown below. It is
(a) Cleavage of CO bond in ethers: The order of reactivity of because in step 2 of the reaction, the departure of leaving
halogen acids towards this reaction is: group (HO–CH3) creates a more stable carbocation
HI > HBr > HCl > Hl [(CH3)3C+], and the reaction follows SN1 mechanism.
The HI bond is broken easily but HF bond can’t be broken
.The reaction involved is
Ether cleavage with strong acid
R-o-R’ HI R-OH + I-R’
First step is protonation.
Second step is cleavage of a C-O bond (b) Electrophilic Substitution: The alkoxy group (-OR) is
Can proceed through SN1 or SN2 depending on substrate ortho, para directing and activates the aromatic ring towards
If ‘excess’ HI is present, the alcohol product will be electrophilic substitution in the same way as in phenol. The
coverted to an alkyl iodide. ortho, and para directing nature can be seen from it's
resonance structure as shown below.

Halogenation (addition of halogen):

Mechanism:
The reaction of an ether with concentrated HI starts with
protonation of ether molecule. Friedel-Crafts reaction (addition of alkyl and acyl group):

Step 2:
Iodide is a good nucleophile. It attacks the least substituted
carbon of the oxonium ion formed in step 1 and displaces an
alcohol molecule by SN2 mechanism. Thus, in the cleavage of
mixed ethers with two different alkyl groups, the alcohol and
alkyl iodide formed, depend on the nature of alkyl groups.
When primary or secondary alkyl groups are present, it is the
lower alkyl group that forms alkyl iodide (SN2 reaction).
iii) Nitration: Uses of ethers
• Ethers are used as a refrigerant.
• They are used as industrial solvent for fat and oils.
• When mixed with alcohol they make alcohol denatured.
• They are used in Perfumery like:
• In aniseeds – Anethol is present which is a phenyl ether.
• In clove oil – Eugenol is present.
• In vanilla extract vanillin is present.
• In mint – Thymol is present.
Alcohols and phenols are classified Alcohols and phenols are acidic in nature. Electron
(i) On the basis of the number of hydroxyl groups withdrawing groups in phenols increase its acidic strength
(ii) According to the hybridization of the carbon atom, and electron releasing groups decrease it. Alcohols undergo
sp3 or sp2 to which the -OH group is attached. nucleophilic substitution with hydrogen halides to yield
Ethers are classified on the basis of groups attached alkyl halides. Dehydration of alcohols gives alkenes. On
to the oxygen atom. oxidation, primary alcohols yield aldehydes with mild
oxidising agents and carboxylic acids with strong oxidising
Alcohols may be prepared
agents while secondary alcohols yield ketons. Tertiary
(1) By hybridization of alkenes
alcohols are resistant to oxidation.
(i) In presence of an acid
(ii) By hydroboration-oxidation reaction The presence of -OH group in phenols activates the aromatic
ring towards electrophilic substitution and directs the
(2) From carbonyl compounds by
incoming group to ortho and para positions due to
(i) Catalytic reduction
resonance effect. Reimer-Tiemann reaction of phenol yields
(ii) The action of Grignard reagents.
salicylaldehyde. In presence of sodium hydroxide, phenol
Phenols may be prepared by generates phenoxide ion which is even more reactive than
(1) Substitution of phenol. Thus, in alkaline medium, phenol undergoes Kolbe’s
(i) Halogen atom in haloarenes reaction.
(ii) Sulphonic acid group in aryl sulphonic acids, by -OH
Ether may be prepared by
group
(i) Dehydration of alcohols
(2) By hydrolysis of diazonium salt (ii) Williamson synthesis
(3) Industrially from cumene The boiling points of ethers resemble those of alkanes while
their solubility is comparable to those of alcohols having
Alcohols have higher boiling point than other classes of
same molecular mass. The C-O bond in ethers can be cleaved
compounds, namely hydrocarbons, ethers and haloakanes of
by hydrogen halides. In electrophilic substitution, the alkoxy
comparable molecular massses. The ability of alcohols,
group activates the aromatic ring and directs the incoming
phenols and ethers to form intermolecular hydrogen bonding
group at ortho and para positions.
with water makes them soluble in it.
 QUESTIONS FOR PRACTICE
1. The heating of phenyl methyl ether with HI produces (c) NaBH4 (d) all of these
(a) Iodobenzene (b) Phenol
11 Which of the following reagents can be used to oxidise
(c) Benzene (d) Ethyl chloride
primary alcohols to aldehydes?
2. Among the following sets of reactants which one (a) CrO3 in anhydrous medium.
produces anisole? (b) KMnO4 in acidic medium.
(a) CH3CHO; RMgX (c) Pyridinium chlorochromate.
(b) C6H5OH; NaOH, CH3I (d) Heat in the presence of Cu at 573K.
(c) C6H5OH, neutral FeCl3
12 One mole of ethyl acetate on tatment with an excess of
(d) C6H5 —CH3; CH3COCl; AlCl3
LiAlH4 in dry ether and subsequent acidification
3. Monochlorination of toluene in sunlight followed by produces
hydrolysis with aq. NaOH yields. (a) 1 mole acetic acid + 1 mole ethyl alcohol
(a) o-Cresol (b) m-Cresol (b) 1 mole ethyl alcohol + 1 mole methyl alcohol
(c) 2, 4-Dihydroxytoluene (d) Benzyl alcohol (c) 2 moles of ethyl alcohol
(d) 1 mole of 2-butanol
4. CH3CH2OH can be converted into CH3CHO by ____ .
(a) Catalytic hydrogenation 13 Which of the following alcohols will give the most
(b) Treatment with LiAlH4 stable carbocation during dehydration?
(c) Treatment with pyridinium chlorochromate (a) 2-methyl-1-propanol (b) 2-methyl-2-propanol
(d) Treatment with KMnO4 (c) 1-Butanol (d) 2-Butanol
5. The correct order of boiling point of primary (1°), 14 A compound X with the molecular formula C3H8O can
secondary (2°) and tertiary (3°) alcohols is be oxidised to another compound Y whose molecular
(a) 1° > 2° > 3° (b) 3° > 2° > 1° formulae is C3H6O2. The compound X may be
(c) 2° > 1° > 3° (d) 2° > 3° > 1° (a) CH3CH2OCH3 (b) CH3CH2CHO
(c) CH3CH2CH2OH (d) CH3CHOHCH3
6. Which compound is predominantly formed when
phenol is allowed to react with bromine in aqueous 15 Order of esterification of alcohols are
medium? (a) 3° > 1° > 2° (b) 2°> 3° > 1°
(a) Picric acid (b) O-Bromophenol (c) 1 ° > 2° > 3° (d) None of these
(c) 2, 4, 6-Tribromophenol (d) p-Bromophenol
16 What happens when tertiary butyl alcohol is passed
7. Phenols are more acidic than alcohols because over heated copper at 300°C?
(a) Phenoxide ion is stabilised by resonance (a) Secondary butyl alcohol is formed
(b) Phenols are more soluble in polar solvents (b) 2-methylpropene is formed
(c) Phenoxide ion does not exhibit resonance (c) 1-butene is formed
(d) Alcohols do not lose H atoms at all (d) Butanol is formed
8. Which of the following reagents cannot be used to 17 What would be the reactant and reagent used to obtain
distinguish between phenol and benzyl alcohol? 2, 4-dimenthyl pentan-3-ol?
(a) FeCl3 (b) Litmus soln (a) Propanal and propyl magnesium bromide
(c) Br2/CCl4 (d) All of these (b) 3-methylbutanal and 2-methyl magnesium iodide
(c) 2-dimethylpropanone and methyl magnesium
9. 1-propanol and 2-propanol can be best distinguished
odide
by
(d) 2-methylpropanal and isopropyl magnesium iodide
(a) Oxidation with KMnO4 followed by reaction with
Fehling solution. 18 The decreasing order of boiling point of the following
(b) Oxidation with acidic dichromate followed by alcohols is
reaction with Fehling solution. (a) 3-methylbuan-2-ol> 2-methylbutan-2-ol > pentan-
(c) Oxidation by heating with copper followed by 1-ol
reaction with Fehling solution. (b) Pentan-1-ol>3-methylbutan-2-ol> 2-methylbutan-
(d) Oxidation with concentrated H2SO4 followed by 2-ol
reaction with Fehling solution. (c) 2-methylbutan-2-ol>3-methylbutan-2-ol> pentan-
1-ol
10 Which of the following are used to convert RCHO into
(d) 2-methylbutan-2-ol > pental-1-ol> 3-methylbutan-
RCH2OH?
2-ol
(a) H2/Pd (b) LiAlH4
19 Acid catalysed dehydration of t-butanol is faster than (b) Williamson’s synthesis and Hydrobration-
that of n-butanol because oxidation
(a) tertiary carbocation is more stable than primary (c) Kolbe’s reaction and Williamson’s synthesis
carbocation (d) Kolbe’s reaction and Reimer-Tiemann reaction
(b) primary carbocation is more stable than tertiary
27 Which of the following is phenol?
carbocation
(a) Cresol (b) Catechol
(c) t-butanol has a higher boiling point
(c)Benzenol (d) All of these
(d) rearrangement takes place during dehydration of
t- butanol 28 Benzoquinone is prepared by reaction of phenol with
(a) Na2Cr2O7, H2SO4 (b) KMnO4, H2SO4
20 An alcohol X when treated with hot cone. H2SO4 gave
(c) Na2CrO4, HCl (d) K2MnO4, H2SO4
an alkene Y with formula C4H8. This alkene on
ozonolysis gives single product with molecular 29 The major product obtained on interaction of phenol
formula C2H4O. The alcohol is with sodium hydroxide and carbon dioxide is
(a) butan-1-ol, (a) benzoic acid (b) salicyaldehyde
(b) butan-2-ol (c) salicylic acid (d) phthalic acid
(c) 2-methylpropan-1-ol
30 The most suitable reagent for the conversion of
(d) 2,2-dimethylbutynal-1-oI
RCH2OH → RCHO is
21 Vapours of an alcohol X when passed over hot reduced (a) K2Cr2O7 (b) CrO3
copper, produce an alkene, the alcohol is (c) KMnO4 (d) PCC
(a) primary alcohol
31 In the reduction
(b) secondary alcohol
R — CHO + H2 → RCH2OH the catalyst used is :
(c) tertiary alcohol
(a) Ni (b) Pd
(d) dihydric alcohol
(c) Pt (d) All of these
22 Picric acid is a yellow coloured compound. Its chemical
32 The compound which reacts fastest with Lucas reagent
name is
at room temperature is
(a) m-nitrobenzoic acid
(a) Butan-1-ol
(b) 2, 4, 6-trinitrophenol
(b) Butan-2-ol
(c) 2, 4, 6-tribromophenol
(c) 2-Methyl propan-1-ol
(d) p-nitrophenol
(d) 2-Methylpropan-2-ol
23 Ortho-nitrophenol is less soluble in water than, p- and
33 Ethyl alcohol can be prepared from Grignard reagent
m- nitrophenols because
by the reaction of :
(a) o-nitrophenol shows intramolecular H-bonding
(a) R2CO (b) HCHO
(b) o-nitrophenol shows intermolecular H-bonding
(c) RCN (d) RCOCl
(c) melting point of o-nitrophenol is lower than those
of m- and p-isomers 34 Isopropyl alcohol is obtained by reacting which of the
(d) o-nitrophenol is more volatile in steam than those following alkenes with concentrated H2SO4 followed by
of m- and p-isomers boiling with H2O?
(a) Ethylene (b) Propylene
24 The best reagent to convert pent-3-en-2-ol into pent-3-
(c) 2-Methylpropene (d) Isoprene
en- 2-one is
(a) acidic permanganate 35 Ethyl alcohol is industrially prepared from ethylene by
(b) acidic dichromate (a) Permanganate oxidation
(c) chromic anhydride in glacial acetic acid (b) Catalytic reduction
(d) pyridiriium chlorochromate (c) Absorbing in H2SO4 followed by hydrolysis
(d) All the three
25 Tertiary butyl alcohol gives tertiary butyl chlorideon
treatment with 36 Sodium salt of benzene sulphonic acid on fusion with
(a) Conc HCl/anhydrous ZnCl2 caustic soda gives
(b) KCN (a) Benzene (b) Phenol
(c) NaOCl (c) Thiophenol (d) Benzoic acid
(d) Cl2
37 Which of the following reacts with NaOH to give an
26 Conversion of phenol to salicyclic acid and to alcohol?
salicyaldehyde are known as (respectively) (a) Propene (b) Butene
(a) Reimer-Tiemann reaction and Kolbe’s reaction (c) Ethanal (d) Methanal
38 Which of the following compounds is oxidised to 48.
prepare methyl ethyl ketone?
(a) 2-Propanol (b) l-Butanol
(c) 2-Butanol (d) t-Butyl alcohol
(a) C6H5OC2H5 (b) C2H5OC2H5
39 HBr reacts fastest with (c) C6H5OC6H5 (d) C6H5I
(a) 2-Mehtylpropan-1-ol (b) 2-Methylpropan-2-ol
49 Which of the following alcohols reacts most readily
(c) propan-2-ol (d) propan-1-ol
with Lucas reagent?
40 n-Propyl alcohol and isopropyl alcohol can be (a) CH3CH2CH2OH
chemically distinguished by which reagent?
(a) PCl5
(b) Reduction
(c) Oxidation with potassium dichromate
(d) Ozonolysis
41 Lucas reagent is
(a) Conc. HCl and anhydrous ZnCl2
(b) Conc. HNO3 and hydrous ZnCl2
(c) Conc. HCl and hydrous ZnCl2
(d) Conc. HNO3 and anhydrous ZnCl2
42 Chloro-Ethane reacts with Which of the Following to 50 Identify the final product of the reaction sequence.
Give Diethyl Ether?
(a) NaOH (b) H2SO4
(c) C2H5ONa (d) Na2S2O3
43 Catalytic Dehydrogenation of Primary Alcohol gives (a) Benzophenone
a___ (b) Acetophenone
(a) Ketone (b) Aldehyde (c) Diphenyl
(c) Alcohol (d) Ester (d) Methyl salicylate
44 Dehydration of Alcohol is an Example of___
(a) addition reaction (b) elimination reaction ASSERTION AND REASONING
(c) substitution reaction (d) redox reaction
Q1. Assertion: Lucas reagent is a mixture of anhydrous
45 In the following compounds: ZnCl2 and concentrate HCl.
Reason: Primary alcohol produce ppt. with Lucas
reagents.
(a) If both Assertion and Reason are correct and the
The order of acidity is Reason is a correct explanation of the Assertion.
(a) III > IV > I > II (b) I > IV > III > II (b) If both Assertion and Reason are correct but Reason
(c) II > I > III > IV (d) IV > III > I > II is not a correct explanation of the Assertion.
(c) If the Assertion is correct but Reason is incorrect.
46 The I.U.P.A.C. name of the ether CH2 = CH-CH2O CH3 is
(d) If both the Assertion and Reason are incorrect.
(a) Allyl methyl ether (b) l-Methoxy-2-propene
(c) 3-Methoxy-l-propene (d) Vinyl dimethyl ether Q2. Assertion: Conc. HCl and anhydrous ZnCl2 in 1:1
mixture is called Lucas reagent.
47.
Reason: Generally 30 alcohols give immediate white
turbidity with HCl/ZnCl2. Conc. HCl and anhydrous
ZnCl2 in 1:1 mixture is called Lucas reagent.
(a) If both Assertion and Reason are correct and the
Reason is a correct explanation of the Assertion.
(b) If both Assertion and Reason are correct but Reason
is not a correct explanation of the Assertion.
(c) If the Assertion is correct but Reason is incorrect.
(d) If both the Assertion and Reason are incorrect.
Q3. Assertion: In Lucas test, 3º alcohols react immediately.
 Reaso : An equimolar mixture of anhyd. ZnCl2 and (b) If both Assertion and Reason are correct but Reason
conc. HCl is called Lucas reagent. is not a correct explanation of the Assertion.
(a) If both Assertion and Reason are correct and the (c) If the Assertion is correct but Reason is incorrect.
Reason is a correct explanation of the Assertion. (d) If both the Assertion and Reason are incorrect.
(b) If both Assertion and Reason are correct but
Reason is not a correct explanation of the TRUE/FALSE
Assertion.
(c) If the Assertion is correct but Reason is incorrect. Q1. Ether is soluble in water.
(d) If both the Assertion and Reason are incorrect. (a) True (b) False
Q4. Assertion: Reimer-Tiemann reaction of phenol with Q2. Ethers are insoluble in cone. H2SO4 while alkanes are
CCl4 in NaOH at 340 K gives salicyclic acid as the major soluble.
product. (a) True (b) False
Reason: The reaction occurs through intermediate
formation of dichlorocarbene. Q3. Diethyl ether and 1-butanol have the same solubility in
(a) If both Assertion and Reason are correct and the water.
Reason is a correct explanation of the Assertion. (a) True (b) False

HOMEWORK
Q1. Glucose and fructose are converted to ethanol in the
Q9. Which of the following phenols is not dihydric?
presence of ________
(a) Quinol (b) p-Cresol
(a) reductase (b) invertase
(c) Catechol (d) Resorcinol
(c) zymase (d) oxidase
Q10. What is the correct IUPAC name of the following
Q2. Which of the following compounds is not used in the
phenol?
denaturation of alcohol?
(a) Ethyl alcohol (b) Copper sulphate
(c) Methyl alcohol (d) Pyridine
Q3. What is the common name of Butan-2-ol?
(a) tert-Butyl alcohol (b) n-Butyl alcohol
(c) sec-Butyl alcohol (d) Isobutyl alcohol
Q4. How many carbon atoms are present in the parent
(a) 1,2,4-Triphenol (b) Benzene-1,2,4-triol
chain of tert-Butyl alcohol?
(c) 1,2,4-Benzenetriol (d) Benzene-1,2,4-triphenol
(a) 2 (b) 3
(c) 4 (d) 5 Q11. What is the correct common name of 2-Bromophenol?
(a) 2-Hydroxybromobenzene
Q5. What is the IUPAC name of Isopropyl alcohol?
(b) 2-Bromophenol
(a) 2-Methylpropan-2-ol (b) Propan-1-ol
(c) m-Bromophenol
(c) Propan-2-ol (d) 2-Methylpropan-1-ol
(d) o-Bromophenol
Q6. Which of the following is not a polyhydric alcohol?
Q12. Which of the following is given highest preference
(a) Benzene-1,2-diol (b) Cyclohexanol
while naming when present in the same structure?
(c) Ethylene glycol (d) Propylene glycol
(a) Halogen group (b) Hydroxyl group
Q7. Identify the correct IUPAC name for the given (c) Nitro group (d) Triple bond
compound.
Q13. Which of the following compounds is ethoxyethane?
(a) C2H5OC3H7 (b) CH3OCH3
(c) CH3OC2H5 (d) C2H5OC2H5
(a) Butane-1,4-diol (b) Butane-diol Q14. What is the IUPAC name of CH3-O-CH2-CH2-OCH3?
(c) Butylene glycol (d) Butane-1,3-diol (a) 1,4-Dimethoxypropane (b) 1,2-Dimethoxyethane
Q8. Which of the following is an incorrect name for the (c) 1,3-Dimethoxybutane (d) 2,3-Dimethoxyethane
compound with aromatic ring having hydroxyl groups Q15. What is the IUPAC name of CH3(CH2)6-OC6H5?
at para positions? (a) Phenyl heptyl ether (b) Heptyl phenyl ether
(a) Quinol (b) Hydroquinone (c) 1-Phenoxyheptane (d) 1-Hepoxybenzene
(c) Benzene-1,4-diol (d) Resorcinol
Q16. How many lone pairs of electrons does O atom have in (a) Deprotonation (b) Protonation
methanol? (c) Electrophilic attack (d) Nucleophilic attack
(a) 4 (b) 0
Q26. Which compound reacts with propene to form
(c) 1 (d) 2
tripropyl borane?
Q17. Which of the following is not a correct reason for the C- (a) Sodium borohydride (b) Borane
O bond length in phenol to be less than that in (c) Diborane (d) Boric acid
methanol?
(a) Repulsion between the electron lone pairs of Q27. Which of the following is not required for the
oxygen conversion of trialkyl borane to an alcohol?
(b) Partial double bond character of C-O bond (a) Diborane
(c) Conjugation of lone pair of electrons with the (b) Water
aromatic ring (c) Sodium hydroxide
(d) sp2 hybridised sate of carbon of C-O bond (d) Hydrogen peroxide

Q18. If the dipole moment of methanol is 1. 71D, Q28. What happens when an aldehyde is treated with
predict the dipole moment of phenol. lithium aluminium hydride?
(a) 1.96D (b) 1.54D (a) No reaction
(c) 1.71D (d) 1.89D (b) Primary alcohol is formed
(c) Secondary alcohol is formed
Q19. If the C-O bond length in methanol is 142pm, what will (d) Tertiary alcohol is formed
be the C-O bond length in the given compound?
Q29. Which carbonyl compound yields secondary alcohols
when treated with LiAlH4?
(a) Ester (b) Aldehyde
(c) Ketone (d) Carboxylic acid
(a) 202 pm (b) 96pm
(c) 121pm (d) 141pm Q30. Which of the following aldehydes can produce 1o
alcohols when treated with Grignard reagent?
Q20. How are alcohols prepared from haloalkanes? (a) Butanal (b) Methanal
(a) By treating with Mg metal (c) Ethanal (d) Propanal
(b) By treating with concentrated H2SO4
(c) By heating with aqueous NaOH ASSERTION AND REASONING
(d) By treating with a strong reducing agent
Q21. Which of the following process do not yield alcohols? Q1. Assertion: Phenol is more reactive than benzene
(a) Free radical halogenation of alkanes towards electrophilic substitution reaction.
(b) Acid catalysed hydration of alkenes Reason: In the case of phenol, the intermediate
(c) Hydroboration-oxidation of alkenes carbocation is more resonance stabilized.
(d) Reduction of aldehydes (a) If both Assertion and Reason are correct and the
Reason is a correct explanation of the Assertion.
Q22. Identify the catalyst in the hydration of alkenes to
(b) If both Assertion and Reason are correct but Reason
produce alcohols.
is not a correct explanation of the Assertion.
(a) Ni (b) HCl
(c) FeCl3 (d) Pt (c) If the Assertion is correct but Reason is incorrect.
(d) If both the Assertion and Reason are incorrect.
Q23. Propene when reacted with water in the presence of
H2SO4 gives Q2. Assertion: Like bromination of benzene, bromination
(a) 2-Methylpropan-2-ol (b) Propan-1-ol of phenol is also carried out in the presence of Lewis
(c) Propan-2-ol (d) 2-Methylpropan-1-ol acid.
Reason: Lewis acid polarises the bromine molecule.
Q24. Identify the nucleophile that attacks the carbocation in Like bromination of benzene, bromination of phenol is
the second step of acid catalysed hydration of alkenes? also carried out in the presence of Lewis acid.
(a) H3O+ (b) OH– (a) If both Assertion and Reason are correct and the
(c) H2O (d) H+ Reason is a correct explanation of the Assertion.
Q25. Name the following step from the mechanism of acid (b) If both Assertion and Reason are correct but Reason
catalysed hydration of ethene. is not a correct explanation of the Assertion.
(c) If the Assertion is correct but Reason is incorrect.
(d) If both the Assertion and Reason are incorrect.
(e) Assertion is wrong reason is correct.
Q3. Assertion: Ethers behave as bases in the presence of Reason: m- and p- Nitrophenols exist as associated
mineral acids. molecules.
Reason: Due to the presence of lone pairs of electrons (a) If both Assertion and Reason are correct and the
on oxygen. Reason is a correct explanation of the Assertion.
(a) If both Assertion and Reason are correct and the (b) If both Assertion and Reason are correct but Reason
Reason is a correct explanation of the Assertion. is not a correct explanation of the Assertion.
(b) If both Assertion and Reason are correct but Reason (c) If the Assertion is correct but Reason is incorrect.
is not a correct explanation of the Assertion. (d) If both the Assertion and Reason are incorrect.
(c) If the Assertion is correct but Reason is incorrect. (e) Assertion is wrong reason is correct.
(d) If both the Assertion and Reason are incorrect.
(e) Assertion is wrong reason is correct. TRUE/FALSE
Q4. Assertion: Ethanol is a weaker acid than phenol.
Reason: Sodium ethoxide may be prepared by the Q1. All alcohols are equally miscible with water.
reaction of ethanol with aqueous NaOH. (a) True (b) False
(a) If both Assertion and Reason are correct and the Q2. Phenols are stronger acids than alcohols.
Reason is a correct explanation of the Assertion. (a) True (b) False
(b) If both Assertion and Reason are correct but Reason
is not a correct explanation of the Assertion. Q3. An electron withdrawing group present at o− and p−
(c) If the Assertion is correct but Reason is incorrect. positions increases the acidic strength of a phenol.
(d) If both the Assertion and Reason are incorrect. (a) True (b) False
(e) Assertion is wrong reason is correct. Q4. Chlorophenols are stronger acids than phenol.
Q5. Assertion: o-Nitrophenol is less soluble in water than (a) True (b) False
the m- and p-isomers.
 SOLUTIONS
S1. (b) The heating of phenyl-methyl ether with HI releasing group decreases the acidity of phenol by
produces phenol. destabilising phenoxide ion
S8. (a) Ferric chloride can be used to distinguish
between phenol and benzyl alcohol. This is
because, phenols react with neutral ferric
chloride solution to give blue, violet or green
colouration whereas alcohols do not react.
S9. (a) When 1-propanol is heated with copper, it is
oxidized to aldehyde which on passing through
Fehling's solution gives red ppt. whereas 2-
propanol on heating with copper, get oxidized to
S2. (b) The above reaction is the preparation of Anisole ketone which doesn't react with Fehling's
phenol+NaOH+CH3I gives anisole. C6H5OH, NaOH, solution.
CH3I is the correct answer. S10. (d) Aldehydes and ketones are reduced to the
corresponding alcohols by addition of hydrogen
in the presence of catalysts (catalytic
hydrogenation). It is also prepared by treating
aldehydes and ketones with sodium borohydride
(NaBH4) or lithium aluminium hydride (LiAlH4).

S3. (d) Monochlorination of toluene in sunlight gives

benzyl chloride. On hydrolysis with aq. NaOH,
benzyl chloride shows nucleophilic substitution
reaction to give benzyl alcohol.
The reaction of RMgX with any aldehyde other
than methanal gives secondary alcohols not the
primary alcohols.

S11. (b) KMnO4 in acidic medium cannot be used to

S4. (c) Pyridinium chlorochromate (PCC), a complex of oxidize primary alcohols to aldehydes. The
chromium trioxide with pyridine and HCl gives oxidation will not stop at aldehyde stage. It will
good yield of aldehydes and prevents further further continue to carboxylic acid. To stop
oxidation to carboxylic acids. oxidation at aldehyde stage, we need mild
oxidising agent such as PCC or PDC is used.
S12. (c) Ethyl Acetate on treatment with LiAlH4 undergo
reductions gives 2 moles of ethyl alcohol.
S5. (a) The presence of −OH groups in a compound leads
to Hydrogen-bonding which greatly increases its
boiling. Generally, the more 'exposed' the −OH
S13. (b) The tertiary carbocation formed during
group, the better it can participate in
dehydration of 2-methyl-2-propanol is most
intermolecular H-bonding and thus, the boiling
stable.
point will elevate. By that logic, primary alcohols
will have the highest boiling point while tertiary
alcohols will have the lowest boiling point.
1°>2°>3°
S6. (c)
S7. (a) Phenol is more acidic than alcohols due to
stabilisation of phenoxide ion through resonance.
Presence of electron withdrawing group
increases the acidity of phenol by , stabilising
phenoxide ion while presence of electron
S14. (c) By molecular formula, it can be concluded that, it
is an alcohol and terminal alcohols can undergo
oxidation.

S15. (c) The relative order of esterification of alcohols is S20. (b)

10>20>30. Thus as the steric hinderance (or
bulkiness) increases from primary to secondary S21. (c) Given: X(ROH)+Cu(hot)→alkene primary alcohol
to tertiary alcohol, the order of esterification passed over Cu at 3000C is dehydrogenated to
decreases. aldehydes and hydrogen gas liberates secondary
alcohols are dehydrogenated to ketones with
S16. (b) Tertiary alcohol when passed over Cu at 3000 C is liberation of hydrogen gas tertiary alcohol is
dehydrated to alkene. dehydrated to alkene. This method can therefore
be used to distinguish between primary,
secondary and tertiary alcohol. Thus X should be
a tertiary alcohol
S22. (b) Picric acid is a yellow coloured compound. Its
chemical name is 2,4,6 -trinitrophenol.
S17. (d)

S23. (a) Due to intramolecular H-bonding, −OH group is

not available to form a hydrogen bond with water.
Hence o-nitrophenol is sparingly soluble in water
while m- and p-nitrophenol are soluble due to
intermolecular H-bonding with water.
S18. (b) The boiling point of alcohol is determined by the
ease and extent of H-bonding among the alcohol
molecules.
Therefore the order of boiling point is primary
alcohol > secondary alcohol > tertiary alcohol as:
Pentan-1-ol > 3-methylbutan-2-ol > 2-
methylbutan-2-ol.
S19. (a) Alcohol + H2SO4 → Alkene S24. (c) Only suitable reagent is chromic anhydride in
The dehydration reaction is an elimination glacial acetic acid. Other will also effect (C=C)
reaction that goes via carbocation formation. bond.
Since tertiary carbocations are most stable due to
+ Inductive effect of alkyl groups, then is the
secondary and least stable is primary.
Therefore the reactivity of alcohol is governed by
the stability of carbocation that follows the order
as
Tertiary > secondary > primary
Hence, acid catalysed dehydration of t-butanol is
faster than that of n-butanol because tertiary S25. (a)
carbocation formed by t-butanol is more stable
than primary carbocation formed by n-butanol.
S26. (d) Phenol on reaction with carbon dioxide in the S32. (d) Tertiary alcohol reacts fastest with Lucas reagent
presence of a base like NaOH gives Salicylic acid. at room temperature.
It is Kolbe's Reaction 2-methyl propan-2-ol is a tertiary alcohol, thus
Phenol on reaction with chloroform in the presence of reacts immediately with Lucas reagent.
a base like NaOH gives Salicylaldehyde. It is
S33. (b) Ethyl alcohol can be prepared by reaction of
Reimer-Tiemann reaction.
Grignard reagent with formaldehyde.
CH3-MgBr + H-CO-H → CH3CH2-OMgBr →
CH3CH2OH

S34. (b)

S27. (d) Compounds containing —OH group directly

S35. (c)
attached to benzene ring are called phenolic
compounds. S36. (b)

S37. (d)

S28. (a) Phenol to benzoquinone is an oxidation reaction S38. (c)

where a strong oxidising agent dichromate in S39. (b) Reactivity of alcohol with HBr is 30 > 20 > 10
acidified medium is used.
S40. (c)

S29. (c)

S41. (a) Lucas' reagent is a solution of anhydrous Zinc

Chloride in concentrated HCl.
S30. (d) RCH2OH→RCHO
This solution is used to classify alcohols of low
It’s an oxidation reaction.
molecular weight. The reaction is a substitution in
Pyridinium chlorochromate is amild oxidising
which the chloride replaces a hydroxyl group.
agent that oxidises primary alcohol to aldehydes
The best results for this test are observed in
and secondary alcohols to ketones. It does not
tertiary alcohols, as they form the respective alkyl
effect any other functional group and therefore
halides fastest due to higher stability of the
have high selectivity for oxidation of alcohols.
intermediate tertiary carbocation.
Whereas acidic permanganate, acidic dichromate,
chromic anhydride in glacial acetic acid are The Lucas test in alcohols is a test to differentiate
strong oxidising agents and can do further between Primary, secondary, and Tertiary
oxidation to carboxylic acid. Alcohols . It is based on the difference in reactivity
The most suitable reagent for RCH2OH→RCHO is of the three classes of alcohols with hydrogen
pyridinium chlorochromate (PCC) halides via an SN1 reaction.
S31. (d) Since, the Lucas reagent is Anhydrous ZnCl2 and
Conc. HCl.
S42. (c) Chloroethane reacts with X to give diethyl ether. because 2° cation is less stable as compared
The compound X is NaOEt (sodium ethanolate). It to 3° cation.
is an example of Williamson ether synthesis in (5) With 1° alcohols,it does not give [Link]
which alkyl halide reacts with sodium alkoxide to is because at room temperature Lucas
form an ether. reagent doesn't react with 1° alcohols.
S4. (c) Nucleophilic attack of phenolate ion through the
ortho-carbon atom occurs on CCl4 to form an
intermediate which on hydrolysis gives salicylic
acid.
TRUE/FALSE
S43. (b) (b)Primary alcohols get dehydrogenated with
reduced copper at 573K, to give corresponding
S1. (a) Lower ethers such as dimethyl ether or diethyl
aldehydes.
ethers are fairly soluble in water due to the
presence of hydrogen bonding with water. But
higher ethers do not form H-bonds with water so
they are not soluble to much extent.
S44. (b) Dehydration of alcohol is an example β- H-bonding between ethers and H2O →
elimination. It involves the loss of two
atoms/groups from adjacent carbon atoms.

S2. (b) The C-O bonds in ethers are polar whereas

S45. (d)
alkanes are non-polar molecules. Due to the polar
S46. (a) CH2=CH−CH2− is called ally 1 radical. Therefore, nature of ethers, they are very soluble in
its-name is allyl methyl ether. concentrated acids like H2SO4. Their solubility in
S47. (a) conc. H2SO4 is due to the formation of oxonium
ions.
S48. (b)
S49. (c)
S50. (b)
S3. (a) The miscibility of ethers with water resembles
ASSERTION AND REASONING those of alcohols of the some molecular mass.
Both diethyl ether and 1-butanol are miscible to
S1. (c) Lucas reagent is a mixture of anhydrous ZnCl2 and almost the same extent i.e. 7.5 and 9 g/ 100 mL
conc. HCl is used for the distinction of water. This is due to the fact that just like alcohols,
monohydric alcohol. Tertiary alcohols on oxygen of ether can also form hydrogen bonds
addition produce a precipitate immediately while with water molecule as shown:
secondary alcohols produce ppt. after 5 minutes.
Primary alcohols do not produce any precipitate.
Therefore, assertion is true but reason is false.
S2. (b)
S3. (b) Both assertion and reason are true but reason is
not the correct explaination of assertion.
(1) Lucas test is carried out to distinguish
between 1° , 2° and 3° alcohols.
(2) Lucas reagent is a solution of anhydrous
ZnCl2 and concentrate HCl.
(3) With 3° alcohols it gives turbidity
[Link] is because 3° cation is very
stable and the reaction takes place quickly.
(4) With 2° alcohols it does not give turbidity
immediately, it takes 2-5 [Link] is
 HOMEWORK
S1. (c) Glucose and fructose undergo fermentation in the S12. (b) Functional groups are given the highest preference
presence of an enzyme called zymase, which is while naming compounds according to the IUPAC
found in yeast. system.

S2. (a) Ethyl alcohol is drinkable and is made unfit to S13. (d) Ethoxyethane is an ether which is a derivative of
drink to avoid misuse in industries. This is done by ethane with one hydrogen atom replaced by
adding some methanol, copper sulphate (to give it ethoxy group (OC2H5).
colour) and pyridine (to make it foul smelling).
S14. (b) The base hydrocarbon is ethane, in which one
This is known as denaturation of alcohol.
hydrogen of each carbon atom is replaced by a
S3. (c) Butan-2-ol has a parent chain of 4 carbon atoms methoxy group, making it a dimethoxy ether.
and the OH group at the second carbon. Such
S15. (c) Since heptane is a larger group than benzene, it is
configurations have the prefix sec- in the common
chosen as the parent hydrocarbon and the
name.
compound is named as an aryloxy derivative of
S4. (b) The IUPAC name of tert-Butyl alcohol is 2- heptane.
methylpropan-2-ol, which has two substituent
groups at the C-2 position, namely one methyl and S16. (d) The oxygen atom in methanol is sp3 hybridised.
one hydroxyl group. One of the sp3 orbitals overlaps with 1s orbital of
hydrogen (of OH group) and one sp3 orbital
S5. (c) Isopropyl alcohol has a parent chain of three overlaps with sp3 orbital of C atom. The remaining
carbon atoms with the hydroxyl group at the two sp3 orbitals contain one lone pair of electrons
second carbon, hence propan-2-ol. each.
S6. (b) Polyhydric alcohols have two or more hydroxyl
S17. (a) The two lone pairs of electrons of oxygen are
groups in their structure and are named as either
present in OH groups of both phenol and methanol
glycols in the common system or as diols and triols
and has an effect on the C-O-H bond angle and not
in the IUPAC system.
the C-O bond length.
S7. (d) This is a dihydric alcohol with OH groups at the
S18. (b) Phenol has a smaller dipole moment than
first and third carbon positions. Butylene glycol is
methanol because the C-O bond in phenols is polar
also the correct name but in the common system.
due to the electron withdrawing effect of the
S8. (d) Resorcinol is the common name for the dihydric aromatic ring.
phenolic compound with the OH groups at meta
S19. (d) The shown compound in methoxymethane which
positions or 1, 3 positions.
is an ether. The C-O bond length in ethers is almost
S9. (b) m-Cresol is a monohydric phenol with a methyl the same as that in alcohols.
group at meta position with respect to OH. Its
S20. (c) Haloalkanes when heated with aqueous NaOH or
IUPAC name is 3-Methylphenol.
KOH give respective alcohols. This is a nucleophilic
S10. (b) Polyhydric phenols are named as hydroxy substitution reaction where the halide group is
derivatives of benzene in the IUPAC system. The replaced by the OH nucleophile.
positions 1,2,4 comply with the lowest set of
locants rule. S21. (a) Alkanes on free radical halogenation produce a
mixture of haloalkanes and not alcohols. Alcohols
S11. (d) Phenol is used as the common as well as the IUPAC can be prepared from alkenes by acid catalysed
name and haloarenes with hydroxy groups are hydration and hydroboration-oxidation or from
named as halo derivatives of phenols. reduction of aldehydes.
S22. (b) Alkenes react with water in the presence of a
mineral acid as a catalyst to form alcohols. The H+
ion from the acid helps to form a carbocation for
nucleophilic attack.

S23. (c) Since propene is an unsymmetrical alkene, the S2. (e)

given hydration reaction takes place in accordance
to Markovnikov’s rule, to form propan-2-ol. The
double bond is broken and the OH group attaches
at the second carbon.
S24. (c) Nucleophiles are electron rich species that attack
the part of the structure that is electron deficient.
In this step, the H2O nucleophile attacks the
carbocation forming a protonated alcohol.
S25. (a) In this step, the electron pair of water attack the
protonated alcohol, resulting in the loss of H+ from
oxygen (deprotonation) to form an alcohol.
Lewis acid is not recognised as –OH group polarises
S26. (c) Diborane (B2H6) reacts with alkenes to give trialkyl the Br2 molecule. Hence, assertion is wrong
boranes as a product of successive addition. statement.
Firstly, CH3CH2CH2(BH2) is formed which reacts Bromine molecule in the presence of Lewis acid,
with propene to give (CH3CH2CH2)2BH, which Br2 gets polarised to form ar+.
further reacts with propene to finally give
Br-Br + FeBr3 → Br+ + FeBr4-
(CH3CH2CH2)B, which is tripropyl borane.
Hence reason is correct.
S27. (a) Trialkyl boranes are oxidised by hydrogen
peroxide in the presence of aqueous NaOH to form S3. (a) Because of the presence of lone pairs of electrons,
alcohols. Diborane is not required for this the ether can act as a base in presence of mineral
conversion but is essential in the production of acid.
trialkyl boranes.
S28. (b) LiAlH4 acts as a reducing agent which reduces an
aldehyde by adding hydrogen atoms to it result in
the formation of a primary alcohol.
S29. (c) Ketones react with reducing agents LiAlH4 or
NaBH4 to get reduced to alcohol where the OH
group is formed at the C of the C-O group. This
results in the C being bonded to two alkyl groups S4. (b) EtOH is weaker acid than phenol because it is
apart from the OH and H atom. tough to remove H+ ion from EtOH whereas phenol
readily gives H+ to form phenoxide ion (highly
S30. (b) Methanal on treatment with Grignard reagent
stable due to resonance).
forms an adduct which has only one alkyl group
attached to the C atom along with two hydrogens → However, Sodium ethoxide may be prepared by the
and one O-Mg-X (X=halogen) group. This on reaction of EtOH with NaOH but the reason is not
hydrolysis will form a primary alcohol where the the correct explanation for Assertion
OH group will replace the O-Mg-X group. S5. (b) Intramolecular H-bonding is present in –
nitrophenol. It does not form hydrogen bonds with
ASSERTION AND REASONING
water, thus is less soluble in water.
S1. (a) Phenol is more reactive than benzene towards
electrophilic substitution reaction. The donation of
the oxygen's lone pair into the ring system
increases the electron density around the ring.
That makes the ring much more reactive than it is
in benzene. The intermediate carbocation is more
resonance stabilized.
 m-nitrophenol and p-nitrophenol forms PhOH ⇄PhO−+H+, where PhO− is known as
intermolecular hydrogen bonds with water. phenoxide ion,
Hence, assertion is a correct statement. Also, m- Phenol gives phenoxide anion as a product. Due to
nitrophenol and p-nitrophenol exist as associated resonance stabilization of phenoxide ion the
molecules due to formation of H-bonds with water. acidity of phenol is stronger than alcohol.
Thus reason is also correct, but is not a correct S3. (a) An electron withdrawing group present at ortho
explanation for assertion. and para positions increase the acidic strength of a
phenol because of delocalization of negative
TRUE/FALSE charge will be more effecting the phenoxide ion.
The negative charge in dispersed and thus leads to
S1. (b) Miscibility decreases with increase in molecular higher acidic strength of phenol.
mass and increases with branching of chains. S4. (a) Chlorophenol are stronger acids than phenol. As
Because the relative proportion of the we know chlorine is an electron withdrawing
hydrocarbon part in alcohols increases with group and consist -I effect (minus inductive effect)
increasing molecular weight which outweighs the and +R effect (plus resonance effect). Thus due to
effect of hydrogen bond formation with water and electron withdrawing nature chlorophenols can
decreases solubility. easily remove its protons than phenol. Hence,
S2. (a) Phenols are stronger acids than alcohols is due to higher will be the acidity of chlorophenols than
delocalization of negative charge stabilises the phenol.
phenoxide ions due to resonance in benzene ring.