ALDEHYDES, KETONES AND

CARBOXYLIC ACIDS

CHAPTER – 12

ALDEHYDES, KETONES AND CARBOXYLIC ACIDS

In aldehydes, the carbonyl group is composed of carbon and IUPAC naming of aldehydes
hydrogen, while in ketones, it is composed of two carbon • According to the IUPAC system of nomenclature -al
atoms. is attached as a suffix to parent alkane for the naming
The nature of Carbonyl groups of aldehydes.
A carbonyl group is a chemically organic functional group • For example, H2C=O is named as per the IUPAC
composed of a carbon atom double-bonded to an oxygen system as methanal, commonly known as
atom --> [C=O]. The simplest carbonyl groups are aldehydes formaldehyde.
and ketones usually attached to another carbon compound.
• The aldehyde group is always attached at the end of
These structures can be found in many aromatic compounds
contributing to smell and taste. the main carbon chain, and hence the 1st position in
the numbering is always assigned to it. It is not
Nomenclature of carbonyl compound
always necessary to include numbering in the
Important common name:
naming.
• Instead of IUPAC names, aldehydes and ketones are
also called by their common names.
• For aldehydes and ketones, the names are reflected
in Greek and Latin terms. Greek letters such as α, β
etc. are used for the location of the substituents in the
carbon chain.
• The α-carbon is directly attached to the aldehyde
group, β-carbon is attached to the carbon adjacent to
the aldehyde group and so on.
IUPAC naming of Ketones Methods for preparation of aldehydes and ketones
• Now let’s discuss the naming of ketones, according to By oxidation of alcohols: Aldehydes and ketones are usually
IUPAC guidelines, the suffix –one is assigned for the prepared by oxidation of primary and secondary alcohols,
ketones. respectively.
• The carbonyl group can be located anywhere within
the main chain and the position is decided by the
location number.
• The numbering of the chain usually starts from the
end such that the carbonyl carbon gets the lowest
number.
• But there are some ketones such as propanone and
By dehydrohalogenation of alcohols: In this way alcohol is
phenyl ethanoid which do not require any number
transferred to heavy metal catalysts (Ag or Cu). The primary
locator as there is only one possible site for ketone
and secondary alcohols provide aldehydes and ketones.
carbon.
If there are more than one functional groups in a molecule
then the functional group with the higher priority is named
first and the other ones are considered as a substituent. If
there is both a ketone and aldehyde group in a molecule then
the aldehyde group is given priority over ketone while
naming.
Examples: III By ozonolysis of alkenes

IV By hydration of Alkynes: Acetylene in water extraction

gives acetaldehyde and other alkynes in hydration gives
ketones.

Examples:

V With decarboxylation and dehydration of aromatic

acids

Aldehydes Preparation
Note I Rosenmund reduction: Rosenmund reduction is the
hydrogenation of an acyl chloride to an aldehyde, in presence
The compound in which carbonyl group is not of catalyst (Pd supported on barium sulphate). Barium
bonded directly to the benzene ring are considered sulphate partially poisons Pd metal and prevents over-
as arly substituted aliphatic aldehydes reduction. Untreated Pd catalyst is too reactive.
 Preparation of Ketones

(a) From acyl chloride

II from nitriles:
Nitriles are reduced to amine associated with stannous
chloride in the presence of hydrochloric acid, which by
hydrolysis releases the corresponding aldehyde. This
reaction is called Stephen's reduction.

(c) Friedel-Crafts acylation

III Etard reaction: Chromyl chloride (CrO2ClO2) oxidise When benzene is treated with acid chloride in the
methyl group toluene to a chromium complex, which presence of anhydrous AlCl3, a corresponding ketone is
when hydrolysis releases the corresponding formed. This reaction is known as the Friedel-craft
acylation reaction.
benzaldehyde. This reaction is called the Etard reaction.

Physical properties of Aldehydes and ketones

Lower members have unpleasant smell and up to 11
members they are liquids.
Solubility: Aldehydes are more polar in nature. As we
IV Gattermann Koch synthesis: When benzene or its
know, in ketones two alkyl groups are present. So, if
derivatives are treated with CO and HCl in the presence electron density on carbon increases, the polarity of bond
of liquid AlCl3 or CuCl, it releases benzaldehyde or decreases, due to +I effect.
convertible benzaldehyde. This reaction is called the Therefore, solubililty of aldehyde is more as they have
Gatterman-Koch reaction. more tendency to form hydrogen bonds. As number of
carbon atoms increase, the solubility decrease because of
non-polar nature.
Boiling points: Boiling point is always more for polar
compounds.
Ketones have higher boiling points than aldehyde
because of more polarity.
Their boiling point is always lower than alcohols and
carboxylic acids because they are less polar then them.
V Side chain halogenation followed by hydrolysis of In aldehydes and ketones, dipole-dipole interactions are
toluene comparitively less.
Chemical reactions of Aldehydes and Ketones
Nucleophilic addition reactions - A nucleophilic
addition reaction is a chemical addition reaction in which
a nucleophile forms a sigma bond with an electron-
deficient species. These reactions are considered very
important in organic chemistry since they enable the
conversion of carbonyl groups into a variety of functional
groups. Generally, nucleophilic addition reactions of Addition of Grignard reagent:
carbonyl compounds can be broken down into the
following three steps.
The electrophilic carbonyl carbon forms a sigma bond
with the nucleophile.
The carbon-oxygen pi bond is now broken, forming an
alkoxide intermediate (the bond pair of electrons are
transferred to the oxygen atom).
The subsequent protonation of the alkoxide yields the
alcohol derivative.

Addition of alcohols:
Alcohols are added to aldehydes and ketones in the
presence of dry hydrogen chloride to form hemiacetals.
Reactivity: Aldehyde > ketone This reaction can continue by adding another alcohol to
R-CHO > RCOR →(as the size of alkyl group increases, form an acetal.
approach of nucleophile to carbonyl carbon decreases)
Reactivity order: HCHO > CH3CHO > acetone
: Acetaldehyde > Acetone > Methyl t-butyl ketone > Di-
tert-butyl ketone

Addition of amino and its derivatives

Addition of HCN:
The nucleophilic addition reaction between hydrogen
cyanide (HCN) and carbonyl compounds (generally
aldehydes and ketones) results in the formation of
cyanohydrins. Base catalysts are often used to increase
the rate of the reaction.

Addition of sodium hydrogen sulphite:

 Above reaction is not possible with ketone.
Fehling’s test: Fehling’s solution is used to distinguish
between aldehyde and ketone functional groups.
Aldehydes oxidize to give a positive result but ketones
won’t react to the test (except for α-hydroxy ketones).
Fehling’s test is used as a general test for determining
monosaccharides and other reducing sugars

II Reduction of Aldehydes and ketones are reduced to

primary and secondary alcohol respectively sodium
borohydride (NaBH4) or lithium aluminum hydride [LiAlH4].

Halofrom reaction:

Reductions to hydrocarbons:

III Aldol condensation - Aldol condensation is an organic

reaction in which an enolate ion reacts with carboxyl
compound in order to form a β– hydroxy aldehyde or β–
hydroxy ketone.
➔ Hydroxide functions as a base and therefore moves the
Oxidation: Aldehyde oxidising agent RCOOH acidic a-hydrogen producing the reactive enolate ion.
Oxidising agent: HNO3/KMnO4/K2Cr2O7 This reaction can be seen as an acid-base reaction.
➔ Tollen’s reagent ➔ The aldehyde is attacked at the electrophilic carbonyl
➔ Fehling reagent carbon by the nucleophilic enolate ion. This attack is a
nucleophilic addition reaction and gives alkoxide
Test for aldehydes and ketones intermediate.
For aldehydes ➔ The alkoxide deprotonates water molecule, thereby
Tollen’s reagent – Tollens Reagent refers to the producing hydroxide and the β–hydroxy aldehyde.
chemical reagent which is used in the detection of an
aldehyde functional group, an aromatic aldehyde
functional group, or an alpha hydroxy ketone functional
group in a given test substance.
The Tollens Reagent is named after Bernhard Tollens, A
German chemist who discovered this reagent and its
uses. Tollens reagent is a solution of silver nitrate
(AgNO3) and Ammonia (NH3). This reaction is indicated by those aldehyde or ketones
containing at least one hydrogen.
Mechanism:
Step-I :
In this step, hydroxide ion from alkali removes a proton from
the α – carbon of one molecule of ethanal to give a carbanion
(i.e. enolate ion).
Step-III:
In this step, the alkoxide ion takes up a proton from water to
form β-hydroxy aldehyde (aldol).

Step-II :
In this step, there is nucleophilic addition of enolate ion to the
carbonyl carbon of second molecule of ethanal to produce an
V Cannizaro reaction - Cannizzaro reaction is an organic
alkoxide ion.
reaction of an aldehyde without active hydrogen that
undergoes a redox reaction under the action of a strong base.
Examples of aldehydes without active hydrogen include
vanillin, benzaldehyde, syringaldehyde, and formaldehyde.
They undergo intramolecular and intermolecular oxidation-
Step-III : reduction reactions under the action of a strong base (NaOH)
to form a molecule of carboxylic acid and a molecule of
In this step, the alkoxide ion takes up a proton from water to
alcohol [1-5].
form β-hydroxy aldehyde (aldol).

IV Cross Aldol Condensation - Aldol condensation between

Mechanism:
two different carbonyl compounds is called a crossed aldol
Step 1: Nucleophilic attack on the carbonyl group to give a
condensation.
dianion.

Step 2: Conversion of the dianion to a carboxylate and

another aldehyde molecule to an alkoxide ion.

Mechanism:
Step-I :
In this step, hydroxide ion from alkali removes a proton from Step 3: Protonation of the alkoxide to an alcohol and the
the α – carbon of ethanal to give a carbanion (i.e. enolate ion). carboxylate to a carboxylic acid.

Step-II:
In this step, there is nucleophilic addition of enolate ion to the
carbonyl carbon of benzaldehyde to produce an alkoxide ion.
VI Electrophilic substitution reaction – (Benzaldehyde) example of such nomenclature is the name 2-
carboxyfuran for the compound 2-Furoic acid.

Trivial Name and Formula IUPAC Name of the

Carboxylic Acid
Formic acid, H-COOH Methanoic acid
Crotonic acid, CH3CH=CH-COOH But-2-enoic acid
Carbonic acid, OH-COOH Carbonic acid
Butyric acid, CH3(CH2)2COOH Butanoic acid

Examples:

3-hydroxybutanoic acid.

2,3-dichlorobutanoic acid.

Carboxylic acids
Carboxylic acids: carboxylic acid, any class of organic Ways to prepare carboxylic acid:
compounds in which a carbon atom (C) is combined with an 1 From the oxidation of primary alcohols and
oxygen atom (O) in a double bond and a hydroxyl group aldehydes.
(―OH) in a single bond. The main chemical element of
carboxylic acid is its acidity.
Nomenclature:
• The suffix “e” in the name of the corresponding alkane is
replaced with “oic acid”.
• When the aliphatic chain contains only one carboxyl
group, the carboxylic carbon is always numbered one. 2 Aromatic carboxylic acids can be obtained by side
For example, CH3COOH is named as ethanoic acid. chain oxidation of alkyl benzenes.
• When the aliphatic chain contains more than one Aromatic carboxylic acids can be obtained after vigorous
carboxyl group, the total number of carbon atoms is oxidation of alkylbenzenes with chromic acid.
counted and the number of carboxyl groups is
represented by Greek numeral prefixes such as “di-”, “tri-
“, etc.
• A carboxylic acid is named by adding these prefixes and
suffixes to the parent alkyl chain. Arabic numerals are
used for indicating the positions of the carboxyl group.
• The name “carboxylic acid” or “carboxy” can also be
assigned for a carboxyl substituent on a carbon chain. An
3 From hydrolysis of nitriles and amides. 2. The higher acids are odourless.
Amides are prepared by the hydrolysis of nitriles and
Solubility
then converted to acids in the presence of catalysts (H+ or
1. Simple aliphatic carboxylic acids having upto four carbon
OH-1). In order to stop the reaction at the amide stage,
atoms are miscible in water due to the formation of
mild reaction conditions are used.
hydrogen bonds with water.
2. The solubility decreases with increasing number of
carbon atoms due to the increased hydrophobic
interaction of hydrocarbon part.
3. Carboxylic acids are also soluble in less polar organic
solvents like benzene, ether, alcohol, chloroform, etc.
Boiling point
1. Carboxylic acids have much higher boiling points than
hydrocarbons, alcohols, ethers, aldehydes, or ketones of
similar molecular weight.
2. This is due to more extensive association of carboxylic
4 From the reaction of the Grignard reagent with acid molecules through intermolecular hydrogen
carbon dioxide. bonding. The hydrogen bonds are not broken completely
When Grignard reagent reacts with carbon dioxide, it even in the vapour phase. In fact, most carboxylic acids
forms salts of carboxylic acids which after some times exist as dimer in the vapour phase or in the aprotic
give corresponding carboxylic acid after the solvents.
acidification with any mineral acid 3. As the molecular mass increases, boiling point of
carboxylic acid also increases.
Acidity of carboxylic acids
The acidity of a carboxylic acid is due to the resonance
stabilization of its anion.
Aliphatic carboxylic acids with four carbon atoms combine in
water due to the formation of hydrogen bonds in water.
From acyl halides and anhydrides
When acid chloride is hydrolysed with water then carboxylic
acid is produced and it is more readily hydrolysed with an
aqueous base and gives corresponding carboxylic ions which
on further acidification gives the carboxylic acid.
Because of the resonance, both the carbon oxygen bond in the
carboxylate anion have identical bond length. In the
carboxylic acid, these bond lengths are no longer identical.
The acidity of carboxylic acid depends very much on the
substituent attached to – COOH group. Since acidity is due to
the resonance stabilization of anion, substituent causing
stabilization of anion increases acidity whereas substituent
causing destabilization of anion decrease acidity. For
example, electron withdrawing group disperses the negative
BY using KMnO4/KOH charge of the anion and hence makes it more stable causing
increase in the acidity of the corresponding acid, on the other
hand, electron-releasing group increases the negative charge
on the anion and hence makes it less stable causing the
decrease in the acidity.
Few trends for the order of acidity of carboxylic acids
(a) Increase in the number of Halogen atoms on a-position
increases the acidity, eg.
Properties of carboxylic acids Cl3CCOOH > Cl2CHCOOH > ClCH2COOH > CH3COOH
Odour of carboxylic acids
(b) Increase in the distance of Halogen from COOH decreases
1. Aliphatic carboxylic acids upto nine carbon atoms have
the acidity e.g.
unpleasant odours.
 This is due to the fact that inductive effect decreases with
increasing distance.
(c) Increase in the electronegativity of halogen increases the
acidity.
FCH2COOH > BrCH2COOH > ICH2COOH

Q. Arrange the following illustration in order of increasing acidity

(i) HCOOH, ClCH2COOH, CH3COOH
(ii) CH-3COOH, (CH3)2CHCOOH, (CH3)3CCOOH
(iii) ClCH2COOH, Cl2CHCOOH, Cl3CCOOH
(iv) ClCH2COOH, CH3CH2COOH, ClCH2CH2COOH, (CH3)2CHCOOH, CH3COOH
(v) CH3COOH, Cl2CHCOOH, CH3CH2COOH, Cl3CCOOH, ClCH-2COOH

Sol. (i) CH3COOH < HCOOH < ClCH2COOH

(ii) (CH3)3CCOOH < (CH3)2CHCOOH < CH3COOH
(iii) ClCH2COOH < Cl2CHCOOH < Cl3CCOOH
(iv) (CH3)2CHCOOH<CH3CH2COOH<CH3COOH<ClCH2CH2COOH<ClCH2COOH
(v) CH3CH2COOH < CH3COOH < ClCH2COOH < Cl2CHCOOH < Cl3CCOOH

Effect of substituents on the acid strength of aliphatic

Carboxylic acids react with alcohols in presence of an acid
acids
catalyst to give esters and water.
1. Substituents affect the stability of the conjugate base and
affecting the acidity of the carboxylic acids.
Mechanism of esterification
2. Electron withdrawing group increase the acidity of
carboxylic acids by stabilising the conjugate base through The esterification reaction of carboxylic acids with
delocalisation of the negative charge by inductive and/or alcohols is a kind of nucleophilic acyl substitution.
resonance effects. Protonation of the carbonyl oxygen activates the carbonyl
3. Electron donating groups decrease the acidity of group towards nucleophilic addition of the alcohol. Proton
carboxylic acids by destabilising the conjugate base by transfer in the tetrahedral intermediate converts the
inductive and/or resonance effects. hydroxyl group into
+OH2 group, which, being a better leaving group, is
The acidic strength also depends upon other factors such eliminated as neutral water molecule. The protonated
as : ester so formed finally loses a proton to give the ester.
Type of halogen attached :
F>Cl>Br
Fluroine is much more electronegative
Acidic Strength CH3COOF more stronger acid > CH3COCl
BrCH3COOH > CH3COOI
Reactions involving the cleavage of C-OH bond
Preparation of anhydrides from carboxylic acids

Carboxylic acid on heating with mineral acids such as H 2SO4

or with P2O5 forms corresponding anhydride.
Preparation of esters from carboxylic acids
Carboxylic acids react with alcohols in presence of an acid
catalyst to give esters and water.
 Reaction on hydrocarbon part:
Hell-Volhard Zelinsky Reaction (HVZ)
Hell-Volhard-Zelinsky halogenation reaction halogenates
carboxylic acids to α carbon. In its first step, a mixture of
bromine and phosphorus tribromide (catalyst) is used to
prepare 2-bromopropanoic acid, which is converted into a
racemic mixture of amino acid products by ammonolysis.

Acid chlorides can be prepared by action of SOCl2, PCl3 and

PCl5 on carboxylic acids. Hydrogen-containing carboxylic acids are incorporated into
Preparation of amines from carboxylic acids chlorine or bromine treatment where there is a small amount
Carboxylic acids can be converted to amines through schmidt of red phosphorus to provide halocarboxylic acid.
reaction. The acid-catalysed reaction of hydrogen azide with Ring subsitution reactions:
carboxylic acids gives corresponding amines with one less
carbon atom. Bromination

Reactions involving –COOH group Sulphonation

Reduction:

Nitration

Decarboxylation: Carboxylic acid loses carbon dioxide to

form hydrocarbons when its sodium salt is burned with
sodalime NaOH and CaO in a ratio of 3: 1
Solubility decreases as the number of carbon atoms
increases.
(i) The electron withdrawal group (Cl, NO2, CN, etc.)
stabilizes the carboxylate anion by dissolving the
negative charge of carboxylate anion, RCOO–, and
thereby increasing the acidic potential.
Kolbe’s electrolysis: Carboxylic acids react with alcohol or
(ii) The presence of an electron donor as an alkyl group
phenol in the presence of such mineral acids conc. H2SO4 as a
strengthens the negative charge in the RCOO– anion and
catalyst for building esters.
lowers carboxylic acid.
Uses of carboxylic acid
• Methanoic acid is used as coagulating agent in
rubber industry.
• Benzoic acid is used as antiseptic and also in
perfumery.
Ethanoic acid is used as solvent and also in cooking as
vinegar and much more
Aldehydes, ketones and carboxylic acids are some of the important reagents. The α-hydrogens in aldehydes and ketones are acidic.
classes of organic compounds containing carbonyl group. These are Therefore, aldehydes and ketones having at least one α-hydrogen,
highly polar molecules. Therefore, they boil at higher temperatures undergo Aldol condensation in the presence of a base to give α-
than the hydrocarbons and weakly polar compounds such as ethers hydroxyaldehydes (aldol) and α-hydroxyketones(ketol),
of comparable molecular masses. The lower members are more respectively. Aldehydes having no α-hydrogen undergo Cannizzaro
soluble in water because they form hydrogen bonds with water. The reaction in the presence of concentrated alkali. Aldehydes and
higher members, because of large size of hydrophobic chain of ketones are reduced to alcohols with NaBH4, LiAlH4, or by catalytic
carbon atoms, are insoluble in water but soluble in common organic hydrogenation. The carbonyl group of aldehydes and ketones can be
solvents. Aldehydes are prepared by dehydrogenation or controlled reduced to a methylene group by Clemmensen reduction or Wolff-
oxidation of primary alcohols and controlled or selective reduction Kishner reduction. Aldehydes are easily oxidised to carboxylic acids
of acyl halides. Aromatic aldehydes may also be prepared by by mild oxidising reagents such as Tollens’ reagent and Fehling’s
oxidation of (i) methylbenzene with chromyl chloride or CrO3 in the reagent. These oxidation reactions are used to distinguish aldehydes
presence of acetic anhydride, (ii) formylation of arenes with carbon from ketones. Carboxylic acids are prepared by the oxidation of
monoxide and hydrochloric acid in the presence of anhydrous primary alcohols, aldehydes and alkenes by hydrolysis of nitriles,
aluminium chloride, and (iii) cuprous chloride or by hydrolysis of and by treatment of Grignard reagents with carbon dioxide.
benzal chloride. Ketones are prepared by oxidation of secondary Aromatic carboxylic acids are also prepared by side-chain oxidation
alcohols and hydration of alkynes. Ketones are also prepared by of alkylbenzenes. Carboxylic acids are considerably more acidic than
reaction of acyl chloride with dialkylcadmium. A good method for alcohols and most of simple phenols. Carboxylic acids are reduced
the preparation of aromatic ketones is the Friedel-Crafts acylation to primary alcohols with LiAlH4, or better with diborane in ether
of aromatic hydrocarbons with acyl chlorides or anhydrides. Both solution and also undergo α-halogenation with Cl2 and Br2 in the
aldehydes and ketones can be prepared by ozonolysis of alkenes. presence of red phosphorus (Hell-Volhard Zelinsky reaction).
Aldehydes and ketones undergo nucleophilic addition reactions Methanal, ethanal, propanone, benzaldehyde, formic acid, acetic acid
onto the carbonyl group with a number of nucleophiles such as, HCN, and benzoic acid are highly useful compounds in industry.
NaHSO3, alcohols (or diols), ammonia derivatives, and Grignard
 QUESTIONS FOR PRACTICE
Q1. Compound which is used for separation of acetone and Q9. Which of the following reactions to a nucleophilic
acetophenone :- assault is the least reactive?
(a) sodium bisulphate (a) Acetaldehyde
(b) Grignard reagent (b) Di Tert-Butyl ketone
(c) sodium sulphate (c) Diisopropyl ketone
(d) ammonium chloride (d) Butanone
Q2. The polar nature of carbonyl group in aldehydes and Q10. Acetone combines with ethylene glycol in dry HCl gas
ketones is due to to generate
(a) very less electronegative difference (a) hemiacetals (b) cyclic ketals
(b) very large electronagative difference (c) cyclic acetals (d) acetals
(c) presence ot hydrogen bonding
Q11. Which of the following is not a formaldehyde
(d) presence of sp hybridised characters in carbonyl
application?
compound
(a) Preservation of biological specimens
Q3. Phenones are (b) Preparation of acetic acid
(a) aldehyde in which carbonyl group is attached with (c) Silvering of mirrors
benzene ring (d) Manufacturing of bakelite
(b) ketone in which carbonyl group is attached with
Q12. Which of the following compounds is formed when
benzene ring
benzyl alcohol is oxidised with KMnO4?
(c) phenols in which carbonyl group is attached with
(a) CO2 and H2O (b) Benzoic acid
alkyl group
(c) Benzaldehyde (d) Benzophenone
(d) phenols in which carbonyl group is attached with
group Q13. At 287K, which of the following is a gas?
(a) Propanal (b) Acetaldehyde
Q4. Which of the following is a geminal dihalide?
(c) Formaldehyde (d) Acetone
(a) Ethylene dibromide (b) propylidenechloride
(C) Isopropyl bromide (d) none of the above Q14. Which of the following substances is the least water-
soluble?
Q5. In IUPAC system
(a) Methanal (b) Pentanal
(c) Propanone (d) Ethanal
Q15. Which of these has the least unpleasant odour?
(a) Methanal (b) Butanal
is named as_________
(c) Propanal (d) Ethanal
(a) naphthalene aldehyde
(b) naphthalene carbaldehyde Q16. Ester is formed by a reaction between
(C) dibenzene aldehyde (a) An acid and an alcohol
(d) naphanal (b) An acid and a base
(c) An alkane and an alcohol
Q6. Which of the reactions below can result in ketones?
(d) A ketone and an alcohol
(a) Oxidation of primary alcohols
(b) Oxidation of secondary alcohols Q17. Vinegar is primarily composed of
(c) Dehydrogenation of tertiary alcohols (a) Tartaric acid (b) Citric acid
(d) Dehydrogenation of primary alcohols (c) Acetic acid (d) Nitric Acid
Q7. The Rosenmund reaction can produce which of the Q18. Formic acid can reduce
following carbonyl compounds? (a) Tollen's reagent
(a) Methanal (b) Benzaldehyde (b) Potassium permanganate
(c) Butanone (d) Acetone (c) Mercuric chloride
(d) All of the above
Q8. Reactions occur between aldehydes and ketones.
(a) nucleophilic addition Q19. Soap has a similar cleaning mechanism to:
(b) electrophilic substitution (a) Shaping soaps
(c) electrophilic addition (b) Liquid dishwashing detergents
(d) nucleophilic substitution (c) Toothpaste
(d) Hair conditioner
Q20. What is a characteristic of detergent? Q31. The oxidation of toluene to benzaldehyde by chromyl,
(a) Hydrophobic (b) Hydrophilic chloride is called
(c) Both (d) None (a) Etard reaction
(b) Riemer-Tiemann reaction
Q21. An aqueous NaOH solution is added to a mixture of
(c) Wurtz reaction
benzaldehyde and formaldehyde to produce (d) Cannizzaro’s reaction
(a) benzyl alcohol + sodium formate
(b) sodium benzoate + methanol Q32. The addition of HCN to carbonyl compounds is an
(c) benzyl alcohol + methanol example of
(d) sodium benzoate + sodium formate (a) nucleophilic addition (b) electrophilic addition
(c) free radical addition (d) electromeric addition
Q22. As a result of Wolff-Kishner reduction, the following
conversions can be made: Q33. Aldehydes other than formaldehyde react with
(a) Benzaldehyde into Benzyl alcohol Grignard’s reagent to give addition products which on
(b) Cyclohexanol into Cyclohexane hydrolysis give
(c) Cyclohexanone into Cyclohexanol (a) tertiary alcohols (b) secondary alcohols
(d) Benzophenone into Diphenylmethane. (c) primary alcohols (d) carboxylic acids

Q23. The formation of cyanohydrin from a ketone is an Q34. Which of the following will not give aldol
example of: condensation?
(a) electrophilic addition (a) Phenyl acetaldehyde (b) 2-Methylpentanal
(b) nucleophilic addition (c) Benzaldehyde (d) 1-Phenylpropanone
(c) nucleophilic substitution Q35. Benzoyl Chloride on reduction with H2/ Pd-BaSO4
(d) electrophilic substitution produces
(a) benzoic acid (b) benzyl alochol
Q24. The process of heating an inorganic compound to
(c) benzoyl sulphate (d) benzaldehyde
produce an organic compound is:
(a) ammonium cyanate (b) soda-lime Q36. What is the test to differentiate between penta-2-one
(c) sodamide (d) potassium cyanide and pentan-3-one?
(a) Iodoform test (b) Benedict’s test
Q25. Formic acid and acetic acid are distinguished by
(c) Fehling’s test (d) Aldol condensation test
(a) NaHCO3 (b) FeCl3
(c) Victor Mayer test (d) Tollen's reagent Q37. Which of the following does not undergo Cannizzarro’s
reaction?
Q26. By reacting with Grignard's reagent, other aldehydes (a) Benzaldehyde
than formaldehyde produce additional products that (b) 2-Methylpropanal
include: (c) p-Methoxybenzaldehyde
(a) tertiary alcohols (b) secondary alcohols (d) 2, 2-Dimethylpropanal
(c) primary alcohols (d) carboxylic acids
Q38. Which among the following is most reactive to give
Q27. Which of the following compounds do not react with nucleophilic addition?
NaHSO3? (a) FCH2CHO (b) ClCH2CHO
(a) HCHO (b) C6H5COCH3 (c) BrCH2CHO (d) ICH2CHO
(c) CH3COCH3 (d) CH3CHO
Q39. Which compound is obtained when acetaldehydes are
Q28. How can Penta-2-one and Pentan-3-one be treated with dilute solution of caustic soda?
differentiated? (a) Sodium acetate (b) Resinous mass
(a) Iodoform test (b) Benedict’s test (c) Aldol (d) Ethyl acetate
(c) Fehling’s test (d) Aldol condensation test
Q40. Which of the following forces explain the boiling point
Q29. Toluene is oxidized to benzaldehyde by chromyl of aldehydes and ketones?
chloride is called: (a) Hydrogen bonding
(a) Etard reaction (b) van der Waal’s forces
(b) Riemer-Tiemann reaction (c) Dipole-dipole attraction
(c) Wurtz reaction (d) None of these
(d) Cannizzaro’s reaction
Q41. Acetaldehyde reacts with
Q30. Which compound is obtained when acetaldehydes are (a) Electrophiles only
treated with a dilute solution of caustic soda? (b) Nucleophiles only
(a) Sodium acetate (b) Resinous mass (c) Free radicals only
(c) Aldol (d) Ethyl acetate (d) Both electrophiles and nucleophiles
Q42. If formaldehyde and KOH are heated, then we get (b) If both Assertion and Reason are correct but Reason
(a) methane (b) methyl alcohol is not a correct explanation of the Assertion.
(c) ethyl formate (d) acetylene (c) If the Assertion is correct but Reason is incorrect.
(d) If both the Assertion and Reason are incorrect.
Q43. Schiff’s reagent gives pink colour with
(a) acetaldehyde (b) acetone Q2. Assertion: Formaldehyde is a planar molecule.
(c) acetic acid (d) methyl acetate Reason: It contains sp2 hybridised carbon atom.
(a) If both Assertion and Reason are correct and the
Q44. The IUPAC name of CH3COCH(CH3)2 is
Reason is a correct explanation of the Assertion.
(a) 2-methyl-3-butanone
(b) If both Assertion and Reason are correct but Reason
(b) 4-methylisopropyl ketone
is not a correct explanation of the Assertion.
(c) 3-methyl-2-butanone
(c) If the Assertion is correct but Reason is incorrect.
(d) Isopropylmethyl ketone
(d) If both the Assertion and Reason are incorrect.
Q45. IUPAC name of ethyl isopropyl ketone is
Q3. Assertion: Compounds containing –CHO group are
(a) 4-methyl pent-3-one (b) 2-methyl pent-3-one
easily oxidised to corresponding carboxylic acids.
(c) 4-methyl pent-2-one (d) 2-methyl pent-2-one
Reason: Carboxylic acids can be reduced to alcohols by
Q46. The π-bond in carbonyl group is formed by treatment with LiAlH4
(a) s-s-overlapping (b) p-p-overlapping (a) If both Assertion and Reason are correct and the
(c) s-p-overlapping (d) p-d-overlapping Reason is a correct explanation of the Assertion.
(b) If both Assertion and Reason are correct but Reason
Q47. Which of the following have pleasant smell?
is not a correct explanation of the Assertion.
(a) Methanal (b) Propanal
(c) If the Assertion is correct but Reason is incorrect.
(c) Ethanal (d) Hexanal
(d) If both the Assertion and Reason are incorrect.
Q48. Which one of the following can be oxidised to the
Q4. Assertion: Acetic acid does not undergo a haloform
corresponding carbonyl compound?
reaction.
(a) 2-hydroxy-propane
Reason: Acetic acid has no alpha hydrogens.
(b) Ortho-nitrophenol
(a) If both Assertion and Reason are correct and the
(c) Phenol
Reason is a correct explanation of the Assertion.
(d) 2-methyl-2 hydroxy-propane
(b) If both Assertion and Reason are correct but
Q49. The catalyst used in Rosenmund's reduction is Reason is not a correct explanation of the
(a) HgSO4 (b) Pd/BaSO4 Assertion.
(c) anhydrous AlCl3 (d) anhydrous ZnCl2 (c) If the Assertion is correct but Reason is incorrect.
(d) If both the Assertion and Reason are incorrect.
Q50. Vinegar is a solution of acetic acid which is:
(a) 15–20% (b) 20 –25%
TRUE/FALSE
(c) 6 – 8% (d) 2 – 4%

ASSERTION AND REASONING Q1. Highly branched carboxylic acids are more acidic than
unbranched acids.
(a) True (b) False
Q1. Assertion: The boiling points of aldehydes and
ketones are higher than hydrocarbons and ethers of Q2. Aldol condensation is given by all aldehydes and
comparable molecular masses. ketones.
Reason: There is a weak molecular association in (a) True (b) False
aldehydes and ketones arising out of the dipole-dipole
Q3. Aldehydes and ketones form functional pairs.
interactions.
(a) True (b) False
(a) If both Assertion and Reason are correct and the
Reason is a correct explanation of the Assertion.

HOMEWORK
Q1. Which of the following is used to shift the esterification
Q2. Which is the most preferred reagent in the product of
reaction of carboxylic acids towards the right?
acetyl chloride from acetic acid?
(a) Removal of ester by distillation
(a) SOCl2 (b) Cl2
(b) Using excess of carboxylic acid
(c) PCl3 (d) PCl5
(c) Using excess of acid catalyst
(d) Removal of water by distillation
Q3. Benzoic acid reacts with phosphorus pentachloride to
Q14. Which of the following is not a reason for carboxylic
give
acids having higher boiling point than alcohols of
(a) chlorobenzoic acid comparable molecular masses?
(b) chlorobenzene (a) Presence of more alkyl groups in carboxylic acids
(c) benzyl chloride (b) Presence of electron withdrawing carbonyl group
(d) benzoyl chloride (c) Higher polarity of OH bond than in alcohols
Q4. Benzoic acid reacts with ______ to give ammonium (d) Formation of two hydrogen bonds to form cyclic
dimers
benzoate salt, which on further dehydration gives
benzamide. Q15. What is the correct order of boiling points of the
(a) N2 (b) NH3 following?
(c) NH4OH (d) HNO3 (a) CH3COOH > HCOOH > C2H5COOH
(b) HCOOH > CH3COOH > C2H5COOH
Q5. The conversion of phthalamide to phthalimide is (c) C2H5COOH > CH3COOH > HCOOH
brought about by the loss of ______ molecule. (d) HCOOH > C2H5COOH > CH3COOH
(a) two NH3 (b) one H2O
(c) two H2O (d) one NH3 Q16. If the boiling point of propanol is 370 K, predict the
boiling point of acetic acid.
Q6. Soda lime consists of NaOH and CaO respectively, in (a) 390 K (b) 322 K
the ratio of _______ (c) 329 K (d) 370 K
(a) 3:1 (b) 1:2
Q17. Which of the following methods cannot produce
(c) 2:1 (d) 1:3
aldehydes?
Q7. Sodium acetate on heating with NaOH and CaO (3:1 (a) Oxidation of primary alcohols
mixture) gives _______ (b) Dehydrogenation of secondary alcohols
(a) ethanal (b) methane (c) Ozonolysis of alkenes
(c) ethane (d) methanol (d) Hydration of ethyne with acid
Q18. Which of the following reactions can produce ketones?
Q8. What is formed when benzoic acid undergoes
(a) Oxidation of secondary alcohols
nitration in the presence of conc. HNO3 and conc.
(b) Oxidation of primary alcohols
H2SO4?
(c) Dehydrogenation of primary alcohols
(a) 3,5-Dinitrobenzoic acid (b) o-Nitrobenzoic acid
(d) Dehydrogenation of tertiary alcohols
(c) m-Nitrobenzoic acid (d) p-Nitrobenzoic acid
Q19. Conversion of propyne to acetone requires three
Q9. Benzoic acid reacts with ______ to give m- important reagents. Identify which of the following is
Bromobenzoic acid. not one of the three?
(a) PBr3/heat (b) Br2/light (a) HgSO4 (b) Water
(c) Br2-FeBr3 (d) NaBr (c) Zinc dust (d) H2SO4
Q10. Which of the following aliphatic carboxylic acids is a Q20. Which of the following carbonyl compounds can be
solid at room temperature? prepared from Rosenmund reaction?
(a) Decanoic acid (b) Heptanoic acid (a) Benzaldehyde (b) Methanal
(c) Octanoic acid (d) Nonanoic acid (c) Acetone (d) Butanone

Q11. Which among the following has the most unpleasant Q21. Which of the following is required in Stephen
odour? reaction?
(a) Palmitic acid (b) Caproic acid (a) TiCl4 (b) LiCl
(c) Lauric acid (d) Myristic acid (c) NiCl2 (d) SnCl2
Q22. Which of the following compounds helps in reducing
Q12. Benzoic acid is almost insoluble in which of the
esters to aldehydes?
following solvents?
(a) TBAF (b) BINAL-H
(a) Alcohol (b) Cold water
(c) DIBAL-H (d) DIPT
(c) Benzene (d) Ether
Q23. Acetyl chloride reacts with _______ to give butan-2-one.
Q13. As a result of intermolecular hydrogen bonding, (a) diethyl cadmium
carboxylic acids exists as (b) cadmium chloride
(a) dimers (b) acetals (c) methyl magnesium chloride
(c) aldols (d) hemiacetals (d) dimethyl cadmium
 Q2. Assertion: Acetaldehyde on treatment with alkaline
Q24. What is formed after the hydrolysis of the product of
gives aldol.
the reaction between benzonitrile and methyl
Reason: Acetaldehyde molecules contain a hydrogen
magnesium bromide in dry ether?
atom.
(a) Benzaldehyde (b) Phenyl acetaldehyde
(a) If both Assertion and Reason are correct and the
(c) Acetophenone (d) 1-Phenylpropanone
Reason is a correct explanation of the Assertion.
Q25. Friedel-Crafts benzoylation of benzene gives ________ (b) If both Assertion and Reason are correct but Reason
(a) no reaction (b) acetophenone is not a correct explanation of the Assertion.
(c) propiophenone (d) benzophenone (c) If the Assertion is correct but Reason is incorrect.
(d) If both the Assertion and Reason are incorrect.
Q26. Which of the following reactions does not give
benzaldehyde? Q3. Assertion: Acetylene on treatment with alkaline
(a) Friedel-Craft acylation reaction KMnO4 produce acetaldehyde.
(b) Rosenmund reaction Reason: Alkaline KMnO4 is a reducing agent.
(c) Etard reaction (a) If both Assertion and Reason are correct and the
(d) Gatterman-Koch reaction Reason is a correct explanation of the Assertion.
(b) If both Assertion and Reason are correct but Reason
Q27. Which of the following exists as a gas at 287K?
is not a correct explanation of the Assertion.
(a) Acetone (b) Formaldehyde
(c) If the Assertion is correct but Reason is incorrect.
(c) Acetaldehyde (d) Propanal
(d) If both the Assertion and Reason are incorrect.
Q28. If the boiling points of methoxyethane and propanol
Q4. Assertion: Acetophenone and benzophenone can be
are 281 K and 370 K respectively, predict the boiling
distinguished by the iodoform test.
point of propanal.
Reason: Acetophenone and benzophenone both are
(a) 370 K (b) 273 K
carbonyl compounds.
(c) 281 K (d) 322 K
(a) If both Assertion and Reason are correct and the
Q29. Which of the following is the least soluble in water? Reason is a correct explanation of the Assertion.
(a) Pentanal (b) Methanal (b) If both Assertion and Reason are correct but Reason
(c) Ethanal (d) Propanone is not a correct explanation of the Assertion.
(c) If the Assertion is correct but Reason is incorrect.
Q30. Two compounds A and B were being tested for their
(d) If both the Assertion and Reason are incorrect.
boiling points. It was observed that A started boiling
after B, when both were subjected to same conditions.
TRUE/FALSE
If the compound B is acetone, which of the following
can be compound A?
(a) Propanol (b) n-Butane Q1. Unsymmetrical ketones can be prepared by distilling a
(c) Methoxyethane (d) Propanal mixture of calcium salts of two different carboxylic
acids.
(a) True (b) False
ASSERTION AND REASONING Q2. In Rosenmund's reduction, BaSO4 and S act as
promoters and increase the catalytic activity of Pd
Q1. Assertion: Lower aldehyde and ketones are soluble in which acts as catalyst.
water but the solubility decreases as molecular mass (a) True (b) False
increases.
Q3. Ketones can be obtained by the reductive ozonolysis of
Reason: Aldehydes and ketones can be distinguished
alkenes possessing no branching at the carbon atoms
by Tollen’s reagent.
involved in double bond formation.
(a) If both Assertion and Reason are correct and the
(a) True (b) False
Reason is a correct explanation of the Assertion.
(b) If both Assertion and Reason are correct but Reason Q4. Aldehydes and ketones possess higher boiling points
is not a correct explanation of the Assertion. as compared to those of corresponding alkanes due to
(c) If the Assertion is correct but Reason is incorrect. intermolecular hydrogen bonding.
(d) If both the Assertion and Reason are incorrect. (a) True (b) False
 SOLUTIONS
S1. (a) Sodium bisulphite is used for separation of acetone items. In the silvering of mirrors, it also works as a
and acetophenone. Acetophenone (an aromatic reducing agent.
ketone) does not react with sodium bisulphite
S12. (b) When benzyl alcohol is oxidised with KMnO4,
whereas acetone (an aliphatic ketone) reacts with
benzoic acid is the result.
sodium bisulphite to form a solid adduct which can
be filtered. Then, it can be decomposed by acid or S13. (c) At room temperature, methane is a foul-smelling
base to regenerate acetone. gas. Ethanal is a volatile liquid that boils at 294
degrees Fahrenheit. At room temperature, other
S2. (b)
aldehydes and ketones exist as liquids or solids.
S3. (b)
S14. (b) As polar carbonyl group may establish hydrogen
S4. (b) Geminal refers to the relationship between two bonds with water molecules, the lower aldehydes
atoms or functional groups that are attached to the and ketones are miscible in water in all quantities.
same atom. Propylidene chloride is the common However, as the length of the alkyl chain grows
name of IUPAC compound 1,1−dichloropropane. longer, the solubility drops dramatically.
Aldehydes and ketones with more than four
S5. (b)
carbon atoms are nearly water- insoluble.
S6. (b) Ketones are formed when secondary alcohols are
S15. (b) The odour gets less strong and more fragrant as
oxidised and dehydrogenated. Aldehydes are
the size of the aldehyde molecule grows. Methanal
produced by the same processes with primary
has the strongest odour of all the aldehydes.
alcohols.
S16. (a) Esters are formed when the reaction of an acid and
S7. (b) The Rosenmund reaction, which involves
alcohol takes place.
replacing chloride with hydrogen, is only utilised
The reaction is known as the esterification reaction.
to make aldehydes. Methanal cannot be produced
The reaction is
from this process because the acyl chloride that
CH3COOH + CH3CH2COOH → CH3COOCH2CH3
corresponds to it, formyl chloride, is unstable at
The reaction takes place in the presence of Sulphuric acid
ambient temperature. Benzoyl chloride produces
(H2SO4).
benzaldehyde.
S17. (c) Vinegar contains acetic acid, also known as
S8. (a) The polar CO group in aldehydes and ketones
ethanol.
consists of double bond. The nucleophile attacks
Acetic acid is a colourless liquid with a sour and pungent
the sp2 hybridised carbon, shattering the double
smell
bond and converting it to sp3, resulting in the
In its chemical formula, it has carbon atoms so it is considered
formation of a tetrahedral alkoxide intermediate.
to be an organic compound.
This goes through another quick step to create an
additional product. S18. (d) Due to its carboxyl group and aldehyde, formic
acid is unique.
S9. (b) When comparing these substances, the steric
Due to the carbonyl group, this acid reacts with aldehydes in
effects are taken into account. The tert-butyl
a way that does.
groups on either side of the carbonyl atom of the
Aldehydes and acidified KMNO4 are also reduced by this
ketone are highly bulky. This reduces reactivity by
compound.
increasing the hindrance to the approaching
In combination with Tollen's reagent, potassium
nucleophile.
permanganate, and mercuric chloride, formic acid
S10. (b) Dihydric alcohols, such as ethylene glycol, react gives a silver mirror.
immediately with aldehydes and ketones to
S19. (b) Soaps are molecules in which two ends have
generate cyclic acetals and cyclic ketals,
different properties.
respectively. Ethylene glycol ketals are another
• Water interacts with the head, while hydrocarbons
name for cyclic ketals.
interact with the tail.
S11. (b) Because formaldehyde has only one carbon atom, • Water interacts with the ionic end of soap while oil
it cannot be employed as a starting material for the interacts with the carbon end.
production of acetic acid. It is, nevertheless, • Consequently, soap molecules are arranged in
utilised to make bakelite, glues, and polymeric micelles with one end facing the droplet of oil and
the other facing the outside.
 • This forms an emulsion in water.
S30. (c)
• The soap micelles thus help in pulling out the dirt
in water and we can wash our clothes and utensils S31. (a) oxidation of toluene to benzaldehyde by the use of
clean. chromyl chloride is called Etard's reaction.
S20. (c) Detergents have characteristics similar to that of S32. (a) The reaction of HCN with carbonyl compounds is
soap. an example of the nucleophilic addition reaction.
The head of an ant is hydrophilic, since it interacts
S33. (b) aldehydes other than formaldehyde react with
with water, while the tail is hydrophobic because Grignard's reagent to give additional products
it interacts with hydrocarbons.
which on hydrolysis give secondary alcohols.
During soaping, the ionic end interacts with the
water, while the carbon ends interact with the oil. S34. (c) Benzaldehyde will not give aldol condensation due
Soap molecules thus form micelles, structures to absence of α-H atom.
where the oil droplet is on one end and the outside S35. (d) Benzoyl chloride on reduction with hydrogen in
is on the other.
the presence of Pd and `BaSO4 gives
Water emulsifies the soap molecules. acetophenone/ benzaldehyde.
As a result, soap micelles help to remove dirt from
water, so that we can wash our clothes and S36. (a) Iodoform test is performed to differentiate
utensils. between pentan-2-one and pentan-3-one.
S21. (a) When a mixture of formaldehyde and another S37. (b) The alpha carbon i.e., the carbon atom adjacent to
aldehyde without an α-hydrogen atom is treated the carbonyl group is connected to three methyl
with concentrated alkali, it oxidizes formaldehyde groups and no hydrogen atom is bonded to it. Thus,
to carboxylic acid and reduces another aldehyde to the compound has no alpha hydrogen and can
alcohol. undergo a Cannizzaro reaction. Hence, the
compound which cannot undergo a Cannizzaro
S22. (d) Under Wolff Kishner reduction, an aldehyde or reaction is 2-methylpropanal.
ketone is converted into the corresponding alkane.
S38. (a) FCH2CHO is most reactive towards nucleophilic
S23. (b) Since the initial attack is by CN− (nucleophile), it is
addition since presence of most electrophilic
an example of nucleophilic addition reaction addition since presence of most electronegative F
S24. (a) Upon decomposition, ammonium cyanate withdraws electrons from carbon of carbonyl
transforms into an organic compound called urea group making it more polar.
through the reaction of ammonia and cyanic acid. S39. (c) Aldehyde and ketones which have at least one α-
S25. (d) Formic acid has an aldehyde group. It reduces hydrogen atom are known to react with dilute
Tollen's reagent to a silver mirror-like other aqueous caustic soda. As a result, they produce α-
aldehydes. Tollen's test is not given by Carboxylic hydroxy aldehydes. These compounds are known
acids. as aldols and reaction is known as aldol reaction.
S26. (b) Upon reaction with Grignard's reagent followed by S40. (c) The boiling point of molecules depends on the
hydrolysis, formaldehyde forms primary alcohol, intermolecular force of attraction, stronger the
while all other aldehydes from secondary alcohols. force, higher is the boiling point. Boiling points of
aldehydes and ketone depend on intermolecular
S27. (b) Compared with aliphatic ketones, aromatic
dipole-dipole attraction. This is because of
ketones are less reactive than aldehydes. The electronegative oxygen attached to the carbon
reaction between acetophenone and NaHSO3 is
atom.
therefore not initiated.
S41. (b) The carbonyl group is highly reactive polar group.
S28. (a) Pentan-2-one is a methyl ketone useful for It is polarised due to the higher electronegativity
Iodoform testing.
of oxygen in comparison to carbon. As a result, the
Benedict's test will result in both positive results.
electrons present between carbon and oxygen are
Both tests will be negative for Fehling. more attracted towards oxygen atom. The actual
Both can give Aldol.
structure may be represented as consequently, the
S29. (a) Oxidation of toluene with chromyl chloride in the carbonyl carbon is positively charged while the
Etard reaction gives benzaldehyde. In this oxygen is negatively charged. The positively
reaction, the chromyl chloride first forms a brown charged carbon is easily attacked by a nucleophilic
complex, which is separated and then decomposed reagent (Nu-).
with H2O to give benzaldehyde.
S42. (b) When α-hydrogen is absent in carbonyl group, (containing water) solution of 5%-8% of acetic
those compound gives cannizaro reaction. This acid. Other names are Ethanoic acid or Methane
reaction show disproportionation. The oxidation carboxylic acid.
product is salt of carboxylic acid and reduced
product is alcohol. HCHO + HCHO → CH3OH + ASSERTION AND REASONING
HCOO−K+
S43. (a) Schiff's reagent is used to detect the presence of S1. (a)
aldehydic and ketonic group. It consists of fuchsin S2. (a)
dye decolourised by sulphurous acid. Immediate
red/pink colour appearance detects the presence S3. (b) If R-CHO + H2O → R-COOH + 2H+ + 2e-
of aliphatic aldehyde. Aliphatic ketone and For example: Tollen’s reagent:
aromatic aldehydes takes time and slowly pink RCHO + 2Ag(NH3)2 + 3OH- → RCOO- + 2Ag + 4NH3
colour blooms. + 2H2O
That means –CHO group easily oxidised to
S44. (a) The IUPAC name of CH3COCH(CH3)2 (c) 3-methyl- corresponding COOH.
2-butanone. Whereas, RCOOH LiAlH4 H3O+ RCH2OH
S45. (b) The IUPAC name of ethyl isopropyl ketone is 2- That means carboxylic acids can be reduced to
methyl-3-pentanone. alcohols by treatment with LiAlH4. But it doesn’t
justified the reason of Assertion.
S46. (b) π bonds are formed by the sidewise or lateral
overlapping of p orbitals. Where, as σ bonds are S4. (c) Haloform test identifies the presence of a CH3
formed by axial overlapping of molecular orbitals. CO group in aldehydes and ketones.
CH3COR + 3I2 + 4OH− → CHI3 + RCOO− + 3I− + 3H2O
S47. (d) Hexanal, also called hexanaldehyde or Acetic acid does not undergo haloform reaction
caproaldehyde is an alkyl aldehyde used in the because in presence of OH− ions it acts as an acid
flavor industry to produce fruity flavors. Its scent and does not forms CHX3 haloform. Therefore
resembles freshly cut grass, like cis-3-hexenal. It is assertion is correct.
potentially useful as a natural extract that prevents Acetic acid has three α hydrogens, thus the reason
fruit spoilage. is incorrect.
S48. (a) 2-hydroxy propane or secondary alcohol is
oxidised into propanone (corresponding because TRUE/FALSE
in 2-hydroxy propane, secondary alcoholic group
is present and it is oxidised into ketone). S1. (b) false- highly branched acids are less acidic

S49. (b) The reaction, a hydrogenolysis, is catalysed by S2. (b) Aldol condensation is given by all aldehydes and
palladium on barium sulfate, which is sometimes ketones.
called the Rosenmund catalyst. Barium sulfate has S3. (a) Aldehydes have a general formula RCHO while
a low surface area which reduces the activity of the ketones have the general formula RCOR.
palladium, preventing over-reduction. They can have the same molecular formula of
S50. (c) An aqueous of acetic acid is called vinegar which different arrangement and combination of atoms.
contains 5-8% acetic acid. Vinegar is a solution of Thus, they form a functional pair.
5-8% acetic acid in water, that's why it is aqueous

HOMEWORK
S1. (d) Since the esterification of carboxylic acids is a S3. (d) The hydroxyl group (OH) of benzoic acid id easily
reversible reaction, it can be shifted towards the replaced by chlorine atom on treatment with PCl5.
right by using excess of alcohol or by the removal This results in the formation of C6H5COCl, or
the water formed by distillation. benzoyl chloride.
S2. (a) Thionyl chloride reacts with acetic acid to form S4. (b) Benzoic acid reacts with ammonia in a reversible
acetyl chloride along with two gaseous compounds reaction to form ammonium benzoate by addition
(SO2 and HCl) that escape the reaction mixture, reaction. This salt then loses water on heating to
making the purification of the product easier. form benzamide.
S5. (d) Phthalic acid on reaction with NH3 forms S15. (c) The boiling points increase with the increase in
ammonium phthalate, which on heating loses two molecular mass, because as the size of alkyl group
H2O molecules, one from each COONH4 group, to increases, the magnitude of van der Waal forces
form phthalamide. This on further strong heating increases, thus making the bonds difficult to break.
loses one NH3 molecule to form phthalimide,
S16. (a) Acetic acid and propanol both have same
which is an imide derivative of phthalic anhydride.
molecular mass. Acetic acid should have a higher
S6. (a) Soda lime is the 3:1 mixture of sodium hydroxide boiling point than propanol because of its stronger
and calcium oxide, and is used in the hydrogen bonds and the fact that it forms cyclic
decarboxylation reaction (loss of carbon dioxide) dimers.
of carboxylic acids.
S17. (b) The dehydrogenation of secondary alcohols give
S7. (b) Sodium acetate undergoes decarboxylation (loss ketones. Aldehydes are obtained by the
of CO2) when heated with soda lime. This is dehydrogenation of primary alcohols.
proceeded by the loss of COONa from the sodium
S18. (a) Oxidation and dehydrogenation of secondary
salt and NaO from sodium hydroxide. They
alcohols results in ketones. The same reactions
combine to form CH4 and Na2CO3. The
with primary alcohols give aldehydes.
hydrocarbon formed has one less carbon atom
than the parent acid. S19. (c) Addition of water to propyne in the presence of
H2SO4 and HgSO4 gives acetone. Zinc dust is an
S8. (c) Benzoic acid undergoes ring substitution in which
important reagent in the ozonolysis of alkenes.
the COOH group acts as a deactivating group and is
meta-directing in nature. S20. (a) Rosenmund reaction is exclusively used for the
preparation of aldehydes by the substitution of
S9. (c) Benzoic acid undergoes electrophilic substitution
chloride by hydrogen. Given this, methanal cannot
with bromine at the meta position in the presence
be formed from this reaction because its
of FeBr3 to form 3-bromobenzoic acid and
corresponding acyl chloride, i.e., formyl chloride, is
hydrogen bromide as side product.
unstable at room temperature. Benzaldehyde is
S10. (a) The members butanoic acid to nonanoic acid are formed from benzoyl chloride.
colourless oily liquids at room temperature. The
S21. (d) Nitriles are converted to respective imines with
compounds with ten or more carbon atoms exists
SnCl2 in the presence of HCl, which on hydrolysis
as waxy solids at room temperature.
gives corresponding aldehyde.
S11. (b) The first three members of carboxylic acids have
S22. (c) DIBAL-H or diisobutylaluminium hydride is a
pungent smell. The next six members have a faint
reducing agent which are used to reduce nitriles to
unpleasant odour. The higher members (lauric
imines or esters to aldehydes. These are important
acid, myristic acid, palmitic acid) are practically
in the preparation of aldehydes.
odourless due to their low volatility.
S23. (a) For butan-2-one to form from acetyl chloride, the
S12. (b) The large hydrophobic benzene ring of benzoic
Cl group needs to be replaced by an ethyl group.
acid prevents the carboxyl group from taking part
This ethyl group is obtained from diethyl cadmium
in hydrogen bonding. However, benzoic acid is
which is produced from the reaction between ethyl
soluble in non-polar solvents like benzene, ether,
magnesium bromide and cadmium chloride.
alcohol, chloroform, etc.
S24. (c) When a nitrile is treated with a Grignard reagent in
S13. (a) The intermolecular hydrogen bonds between
the presence of dry ether, an addition product is
carboxylic acids are not broken even in vapour
formed which on hydrolysis gives a ketone.
phase. In fact, most carboxylic acids exist as dimer
in vapour phase or in aprotic solvents. S25. (d) When benzene is treated with benzoyl chloride in
the presence of anhydrous aluminium chloride, it
S14. (a) The OH bond in carboxylic acids is more strongly
forms benzophenone which is an aromatic ketone.
polarised due to the presence of adjacent electron
withdrawing CO group. This results in stronger S26. (a) Friedel-Crafts acylation of benzene produces an
hydrogen bonds. Also, the presence of alkyl groups aromatic ketone and not benzaldehyde. Benzene
should increase the polarity of OH bond as they are on Gatterman-Koch reaction gives benzaldehyde,
electron releasing in nature. Furthermore, so does toluene on Etard reaction. Rosenmund
carboxylic acids form two hydrogen bonds reaction also gives benzaldehyde but from benzoyl
between molecules compared to the only one chloride.
between alcohols.
S27. (b) Methanal exists as foul-smelling gas at room S4. (b) Acetophenone and benzophenone can be
temperature. Ethanal is a volatile liquid which distinguish by iodoform test. Both are carbonyl
boils at 294K. Other aldehydes and ketones exist as compounds.
either liquids or solids at room temperature.
TRUE/FALSE
S28. (d) The boiling point of aldehydes are higher than
those of non-polar hydrocarbons of comparable
S1. (a) When a mixture of calcium salts of two different
molecular masses. However, their boiling points
carboxylic acids is dry distilled, it results in the
are lower than comparable alcohols, due to the
formation of unsymmetrical ketones.
absence of intermolecular hydrogen bonding.
S29. (a) The lower aldehydes and ketones are miscible in
water in all proportions due to the ability of the
polar carbonyl group to form hydrogen bonds with
water molecules. However, the solubility rapidly
decreases as the length of the alkyl chain increases.
Precisely, aldehydes and ketones with more than 4
carbon atoms are practically insoluble in water. S2. (b) In Rosenmund's reduction, the palladium catalyst
is poisoned by barium sulphate and sulphur to
S30. (a) It can be inferred that B has a higher boiling point check the further reduction of aldehyde to
than A. Since hydrocarbons, ethers and aldehydes corresponding alcohol.
have lower boiling points than ketones of similar
molecular masses, none of them can be compound
A. Also, alcohols have a higher boiling point than
similar ketones hence, the compound A is
propanol. It decreases the catalytic activity of palladium.

ASSERTION AND REASONING S3. (b) The formation of ketones from the reductive
ozonolysis reaction of alkenes requires alkenes
S1. (b) Lower aldelnydes and ketones are soluble in water have branching at the carbon atoms involved in
due to polar effect of >C=O which makes liydrogen double bond formation.
bonds with water molecules.
As the size of the aldehydes and ketones increases the
hydrophobic part i.e., alkyl chain increases which
weakens the H-bond formations with H2O
molecules and decreases the solubility.
S2. (a) Carbonyl compounds having α-hydrogen
condenses to produce aldol in presence of alkali.
S4. (b) Aldehydes and ketones have a polar carbonyl
group.
The polarity of the carbonyl group results in the
intermolecular association between the molecules
S3. (d) Acetylene, on treatment with alkaline KMnO4 is in aldehydes and ketones due to dipole-dipole
oxidised to produce oxalic acid. interactions.
Therefore, the boiling points of aldehydes and
ketones are higher than those of alkanes and
ethers.