Q.1.

Explain structure of carbonyl group. The C = O bond of carbonyl group in aldehyde and ketone is made up of one -bond and one

-bond. In the formation of carbonyl group compounds, the carbonyl carbon atom is sp2 hybridised and forms three sp2 hybrid orbitals One of the sp2 hybridised orbitals of carbon overlaps with porbital of oxygen atom forming a -bond between carbon and oxygen atom. The remaining two hybridised sp2 orbitals of carbon atom, form additional two -bonds, either by overlapping with 1s-orbital of two hydrogen atom as in formaldehyde or with 1s-orbital of one hydrogen atom and one sp3 hybrid orbitals of two alkyl groups carbon in ketones. All the three -bonds lie in the same plane and are inclined to one another at an angle 120 as shown in figure. The half-filled 2pz-orbital of carbon atom overlaps sideway with 2pz-orbital of oxygen atom to form a -bond, and the electron cloud of the -bond lies both above and below the CO -bond. Thus, the carbonyl carbon and oxygen atoms and two atoms which are directly bonded to the carbonyl carbon lie in the plane as shown in figure. This has been also confirmed by electron diffraction and spectroscopic studies.

Q.2.

Explain nature of carbonyl group. In carbonyl group the carbon-oxygen double bond is polarized due to higher electronegativity of oxygen atom relative to that carbon atom. As a result the oxygen atom tends to attract the electron cloud of the -bond towards itself. As a result the carbonyl carbon becomes an electrophile (Lewis acid) and oxygen becomes a nucleophilic (Lewis base). Thus the carbonyl group is polar in nature. Hence, such compounds have dipole moments. For example, aldehydes and ketones have 2.32.8 D dipole moments. The high polarity of the carbonyl group is explained on the basis of resonance structures shown below: C=O C=O

Q.3.

Explain physical properties of aldehydes and ketones. Aldehydes and ketones possess polar carbonyl groups and hence exhibit weak intermolecular association due to dipole-dipole interactions between the opposite ends of the C = O dipoles.

+ C=O

+ C=O

+ C=O

+ C=O

Intermolecular dipole attraction

1

So, the boiling points of aldehydes and ketones are a little higher than non-polar compounds like hydrocarbons and weakly polar compounds like ethers of comparable molecular mass. The boiling points of aldehydes and ketones are lower than those of alcohols and carboxylic acids of comparable molecular mass because in carboxylic acid and alcohol molecules there exists an intermolecular hydrogen bonding which is stronger than dipole-dipole interaction. Among the isomeric aldehydes and ketones, the ketones have slightly higher boiling points, this happens due to the presence of two electron-donating alkyl groups around the carbonyl group which makes them more polar, so the order of boiling points is carboxylic acid > alcohol > isomeric ketone > isomeric aldehyde > ether > hydrocarbon. The lower members of aldehydes and ketones up to three carbon atoms such as methanal, ethanal, propanal and propanone are soluble in water due to hydrogen bond formation between the polar carbonyl group and the water molecules.
O + C=O + H O + C=O + H + H + O=C + H + O=C

R H R R

R H R R

Hydrogen bonding of aldehyde and ketone with water molecules But the solubility of aldehydes and ketones in water decreases rapidly with the increase in length of alkyl chains. Similarly the solubility of aromatic aldehydes and ketones is much lower than their corresponding aliphatic aldehydes and ketones due to the presence of larger hydrocarbon parts (like benzene ring etc.). However all aldehydes and ketones are fairly soluble in organic solvents like benzene, ether alcohol, chloroform etc. The lower aldehydes have strong pungent odours, but as the size of the aldehyde molecules increases the odour becomes less pungent and more fragrant. However, the ketones are generally in liquid forms having pleasant smell. A number of naturally occurring aldehydes and ketones are used in the preparation and blending of perfumes and as flavouring agents.

Q.4.

Explain the mechanism of nucleophilic addition reaction.

The structure of carbonyl group is planar and it is polar, so the nucleophile is attracted to the positively charged carbon atom of carbonyl group either from above or below the plane of sp2 hybridised orbital of carbonyl group. So it results in formation of an anion (tetrahedral alkoxide) by the complete transfer of electrons of the carbon-oxygen double bond to the oxygen atom. During this process, the hybridisation of carbon atom changes from sp2 to sp3 and hence, the oxygen atom gets pushed out of the plane of the carbonyl group and form new carbon nucleophile (Nu) bond which is slow step so, it is the rate determining step and it is also reversible. In the second step the proton (which is obtained from weak acidic medium) gets attracted by oxygen of carbonyl group (tetrahedral alkoxide) and the electrically neutral product is formed. The second step is also reversible.

Q.5.

Explain the relative reactivity of aldehydes and ketones.

Aldehydes are generally more reactive than corresponding ketones in nucleophilic addition reaction, due to the following reasons.
Steric effects:

As the number and size of the alkyl group attached to the carbonyl group increase, the attachment of nucleophile on the carbonyl group carbon becomes more and more difficult, due to steric hinderance (crowding) i.e., as the crowding increases, the reactivity of carbonyl group compound decreases, so the reactivity of formaldehyde is more as there is no alkyl group, while the other aldehydes having one alkyl group the reactivity is less compared to formaldehyde while ketones having two alkyl groups, the reactivity is less than the corresponding aldehydes.
Inductive effect:

The attachment of nucleophile on the carbonyl group depends upon the magnitude of the positive charge on the carbonyl carbon. The alkyl group electron donating and hence has inductive effect (+ I effect). So more the number of alkyl groups on carbonyl carbon, the magnitude of the positive charge on carbonyl carbon decreases, which lowers the reactivity towards nucleophilic addition reaction. Therefore formaldehyde is more reactive towards nucleophilic addition reactions. Therefore formaldehyde is more reactive compared to other aldehydes and ketones which are less reactive than aldehydes. The aromatic aldehydes and ketones are less reactive than aliphatic aldehydes and ketones because the electron-donating resonance effect of benzene ring which increases the electron density on carbonyl carbon, hence it gets repelled by the nucleophiles. The aromatic aldehyde (like benzaldehyde) is more reactive than alkyl aryl ketone (like acetophenone) while diaryl ketones (like Benzophenone) are less reactive than alkyl aryl ketone.

Q.6.

Explain addition of sodium hydrogen sulphite of aldehydes and ketones.

Due to less steric hindrance most of the aldehydes and aliphatic methyl ketones, react with sodium hydrogen sulphite and form additive compounds, while the acetophenone does not react.
+ C=O Aldehyde or Ketone + + NaHSO3 Sodium hydrogen sulphite + ONa C SO3H Proton transfer OH C + SO3Na

Sodium bisulphite product (crystalline)

CH3 + C=O H Ethanal

+ + NaHSO3 Sodium hydrogen sulphite

CH3 C H

+ ONa SO3H

Proton transfer

CH3

OH C

+ SO3Na H Ethanal Sodium bisulphite

CH3 OH C

CH3 + C=O CH3 Propanone

+ + NaHSO3 Sodium hydrogen sulphite

CH3 C H

+ ONa SO3H

Proton transfer

+ SO3Na CH3 Propanone Sodium bisulphite

The person transfer equilibrium lies more towards the right side for most of the aldehydes and to the left side for most of the ketones. The bisulphite product obtained, are usually crystalline solids. If they are heated with dilute mineral acids or aqueous alkalies they decompose, due to hydrolysis and regenerate the original aldehyde or ketone.
CH3 H OH C + SO3Na

Ethanal Sodium bisulphite

CH3
CH3

Hydrolysis dil.HCl , Decomposition

CH 3CHO Ethanal

NaCl + Sodium chloride

SO 2 + Sulphur dioxide

H 2O Water

OH C + SO3Na

Propanone Sodium bisulphite

Hydrolysis dil.HCl , Decomposition

CH 3COCH 3 Propanone

Na C l + Sodium chloride

SO 2 + Sulphur dioxide

H 2O Water

Therefore, this reaction is useful for separation and purification of aldehydes and ketones from non-carbonyl compounds.

Q.7.

Explain addition of Hydrogen cyanide (HCN) of aldehydes and ketones.

The aldehydes and ketones react with hydrogen cyanide and give product cyanohydrins. The reaction is extremely slow and so it is carried out in presence of base which acts as a catalyst. The reaction occurs very slowly with pure HCN but in presence of base (as a catalyst) the : CN is generated which is a stronger nucleophile and gets added readily to carbonyl compounds and the product cyanohydrins is obtained. For example, HCN + OH

CN + H2O

+ C=O

O + CN

C CN

H+

OH C CN Cynohydrin product

Aldehyde or Ketone

Tetrahedral intermediate product

CH3

C = O + HCN Hydrogen cyanide

[OH]

CH3 C H

OH CN

H Ethanal

Ethanal cynohydrin

CH3

C=O

+ HCN Hydrogen cyanide

[OH]

CH3 C CH3

OH CN

CH3 Propanone

Propanone cynohydrin

Cyanohydrins are important synthetic substances because they can be readily hydrolysed to give 2-hydroxy acids. CH3 C H CN Water Hydrogen chloride OH + 2H2O + HCl CH3 H OH C COOH + NH4Cl

Ethanal cynohydrin

2-Hydroxy propnoic acid Ammonium chloride (Lactic acid)

Q.8.

Explain addition of alcohol of aldehydes and ketones.

Aldehyde reacts with one equivalent of monohydric alcohol in presence of dry hydrogen chloride to yield alkoxy alcohol intermediate known as hemi acetal (hemi means half). Being unstable it immediately reacts with one more molecule of alcohol to form stable gem-di alkoxy compound known as acetal.

R C = O + R'OH H

HCl(g) H+

R C H

OR' OH

R'OH HCl(g) H2O

R C H

OR' OR' Acetal

Hemiacetal

Dry hydrogen chloride protonates the oxygen of aldehyde (carbonyl compound) hence the density of positive charge on carbonyl carbon increases i.e. the electro positivity of carbonyl carbon increases, which facilitates the nucleophilic attachment. Dry HCl gas absorbs the water molecules which is produced during acetal formation and shifts the equilibrium in the forward direction. For example,
CH3 C = O + CH3CH2OH H Ethanal Ethanol HCl(g) CH3 C H OCH2CH3 OH

Hemiacetal CH3CH2OH HCl(g) H2O CH3 C H OCH2CH3 Acetal OCH2CH3

Instead of two molecules of monohydric alcohol in presence of dry hydrochloric acid or paratoluene sulphonic acid (PTS), one molecule of dihydric alcohol such as ethane-1, 2-diol (ethylene glycol) is used, then cyclic acetal (ethylene glycol-ketal) is formed.
CH3 C=O + H Ethanal HOCH2 Ethan-1-2-diol HOCH2 Dry HCl(g) CH3 H2O H OCH2 C OCH2

Cyclic acetal

Ketones do not react with monohydric alcohols but react with dihydric alcohols in presence of dry hydrochloric acid gas or PTS and give cyclic ketals. For example,
CH3 C=O + CH3 Propanone HOCH2 Ethylene glycol HOCH2 Dry HCl(g) H2O CH3 C CH3 OCH2 Cyclic ketal (Ethylene glycol ketal) OCH2

In the formation of acetals and ketals the reactions are reversible; so they are decomposed by dilute acid and the aldehydes and ketones are regenerated. For example,
CH3 C H OCH2CH3 Acetal Water OCH2CH3 + H2 O H+ CH3 C = O + CH3CH2OH H Ethanal Ethanol

CH3 C CH3

OCH2 + H2 O OCH2 Water

H+

CH3 C=O + CH3 Propanone

HOCH2 HOCH2 Ethylene glycol

Cyclic ketal

Q.9.

Explain addition of ammonia and its derivatives. OR Explain nucleophilic addition reactions followed by elimination of water for aldehydes and ketones.
i i

i i

Aldehydes and ketones react with ammonia (N H 3 ) and its derivatives (H 2 N Z) . The reaction is catalysed by acid, hence the carbonyl groups gets protonated, so the positive charge on carbonyl carbon is increased and as a result the weak nucleophile like ammonia and its derivatives readily attach to the carbonyl group. For example,

C = O + H2NZ Aldehyde or Ketone

H+

OH C NHZ Intermediate

H+ H2O

C = NZ Product

The equilibrium favours the product formation due to rapid dehydration of the intermediate to form

C = NZ
.
i i

The N H 3 and its N-substituted derivatives and product are given in table. 6

Table Some N-Substituted Derivatives of Aldehydes and Ketones Z H Reagents Ammonia Carbonyl derivative Products name Imine

C = NH

Amine

C = NR

Substituted imine (Schiffs base) Oxime

OH

Hydroxylamine

C = NOH

NH2

Hydrazine

C = NH2

Hydrazone

Phenyl hydrazine 2, 4Dinitrophenyl hydrazine

C = NH

Phenylhydrazon e 2, 4Dinitrophenyl hydrazone

O2 N H NO2

O2N C = NH NO2

O || NH C NH 2

Semicarbazide

O || C = N NH C NH 2

Semicarbazone

Q.10. Explain reduction of aldehydes and ketones to alcohols.

Aldehydes and ketones on reduction give 1 and 2 alcohols respectively. Reduction is carried out either catalytically with H2 in presence of Ni, Pt or Pd or chemically by lithium aluminium hydride (LiAlH4) or sodium borohydride (NaBH4). LiAlH4 is a much more powerful reducing agent than NaBH4. Ni, Pt ,OR Pd/H 2 HCHO CH 3OH Methanal OR LiAlH 4 /H 2 O Methanol OR NaBH 4 /H 2 O (1 ) CH3 CH3 CH3 Ni, Pt ,OR Pd/H 2 C = O OR LiAlH /H O 4 2 CH3 OR NaBH /H O
4 2

CHOH

Propanone

Propan-2-ol (2o) (isopropyl alcohol)

Q.11. Explain reduction of aldehydes and ketones to hydrocarbons.

The carbonyl group of aldehydes or ketones is reduced to methylene (CH2) group to form hydrocarbon by using different reducing agents. 7

(a) Wolff-Kishner reduction: Aldehyde or ketone is heated with hydrazine (NH2NH2) and KOH in high boiling solvent like ethylene glycol which results into formation of hydrocarbon. For example, NH 2 NH 2 Ethylene glycol CH 3CHO CH 3CH = NNH 2 CH 3CH 3 + N 2 H 2O KOH 453 473 K Ethanal Ethanal hydrazone Ethane Nitorgen

NH 2 NH 2 , KOH CH3COCH3 CH3CH 2CH3 + H 2O + N2 4[H]Ethylene Water Nitrogen Propanone Propane glycol 453 473K (b) Clemmensen reduction: Aldehyde or ketone is reduced to hydrocarbon, on treatment with zinc amalgam and concentrated hydrochloric acid. For example, Zn Hg CH 3CHO + 4[H] CH 3CH 3 + H 2 O Hydrogen Con. HCl Ethanal Ethane Water

Zn Hg CH3COCH3 + 4[H] CH3CH 2CH3 + H 2O Con. HCl Propanone Hydrogen Propane Water (c) Reduction with HI and Red P: Aldehyde or ketone when heated with hydroiodic acid and red phosphorus is reduced to hydrocarbon. For example, Red P CH3CH3 + H 2O + 2I 2 CH3CHO + 4HI 423 K Hydrogen Ethanal Ethane Water Iodine Iodide Red P CH3COCH3 + 4HI CH3CH 2 CH3 + H 2 O + 2I 2 423 K Water Iodine Propanone Hydrogen Propane Iodide
Q.12. Explain Wolff-Kishner reduction. Aldehyde or ketone is heated with hydrazine (NH2NH2) and KOH in high boiling solvent like ethylene glycol which results into formation of hydrocarbon. For example, NH 2 NH 2 Ethylene glycol CH 3CHO CH 3CH = NNH 2 CH 3CH 3 + N 2 H 2 O KOH 453 473 K Ethanal Ethanal hydrazone Ethane Nitorgen

NH 2 NH 2 , KOH CH3COCH3 CH3CH 2CH3 + H 2O + N2 4[H]Ethylene Water Nitrogen Propanone Propane glycol 453 473K
Q.13. Explain Clemmensen reduction.
Aldehyde or ketone is reduced to hydrocarbon, on treatment with zinc amalgam and concentrated hydrochloric acid. For example, Zn Hg CH 3CHO + 4[H] CH 3CH 3 + H 2 O Con. HCl Hydrogen Ethanal Ethane Water

Zn Hg CH3COCH3 + 4[H] CH3CH 2CH3 + H 2O Con. HCl Propanone Hydrogen Propane Water
Q.14. Explain reduction with HI and Red P of aldehydes and ketones.
Aldehyde or ketone when heated with hydroiodic acid and red phosphorus is reduced to hydrocarbon. For example,
8

Red P CH3CHO + 4HI CH3CH3 + H 2O + 2I 2 423 K Hydrogen Ethanal Ethane Water Iodine Iodide
Red P CH3COCH3 + 4HI CH3CH 2 CH3 + H 2 O + 2I 2 Hydrogen 423 K Water Iodine Propanone Propane Iodide

Q.15. Explain reduction of aldehydes and ketones to pinacols.

Ketones on reduction with magnesium amalgam and water form pinacols. For example, CH 3CH 3 CH3 CH3 | | Mg Mg O=C C=O + + 2[H] CH3 C C CH 3 H2O CH3 Hydrogen CH3 | |

Propanone

Propanone

OH OH 2,3-Dimethyl-butane-2,3-diol (Pinacol)

Q.16. Why are aldehydes easily oxidized, but ketones not?

Aldehydes are easily oxidized to carboxylic acids containing the same number of carbon atoms, because of the presence of hydrogen atom on carbonyl group which is converted to OH group, without involving the cleavage of any other bond. So they easily get oxidized by both strong and weak oxidized agent. While ketones can be oxidized by powerful oxidizing agent only, because during oxidation carbon-carbon bond cleavage results into mixture of carboxylic acids, each containing less number of carbon atoms than the original ketone.

Q.17. Explain the tests to distinguish aldehydes from ketones. Following tests distinguish aldehydes from ketones. (i) Tollens test: Aldehyde and freshly prepared ammoniacal silver nitrate solution (Tollens reagent) when gently warmed, the aldehyde is oxidized to carboxylate ion, Tollens reagent is reduced to metallic silver which gets deposited on the inner wall of test-tube giving shining surface like mirror. Hence this test is also known as silver mirror test. Aromatic and aliphatic aldehydes are both oxidized by Tollens reagent. In laboratory the aldehydes can be detected by Tollens test.
RCHO + 2[Ag (NH3 ) 2 ]+ + 3OH RCOO + 2Ag + 4NH3 + 2H 2 O Aldehyde Tollen's reagent Hydroxide ion Carboxylate ion Silver mirror Ammonia Water

(ii) Fehlings test: Fehling solution A (CuSO4 solution) and Fehling solution B (alkaline solution of sodium potassium tartarate-Rochelle salt) are mixed in equal proportion and the mixture is heated with aldehyde, gives red precipitate of cuprous oxide. This test is known as Fehlings test. This test is only for aliphatic aldehydes because the aromatic aldehydes are not reduced by the Fehling solution. In laboratory the aldehydes can be detected by Fehlings test. RCHO + 2Cu 2+ + 5OH RCOO + Cu2 O + 3H 2 O Aldehyde Cupric ion Hydroxide ion Carboxylate ion Red ppts Water (iii) Benedicts test: This test is similar to Fehlings test but instead of tartarate ions the citrate ions were used. The reaction is same and this test is also not given by aromatic aldehydes.
9

Q.18. Explain Tollens test. Aldehyde and freshly prepared ammoniacal silver nitrate solution (Tollens reagent) when gently warmed, the aldehyde is oxidized to carboxylate ion, Tollens reagent is reduced to metallic silver which gets deposited on the inner wall of test-tube giving shining surface like mirror. Hence this test is also known as silver mirror test. Aromatic and aliphatic aldehydes are both oxidized by Tollens reagent. In laboratory the aldehydes can be detected by Tollens test.
RCHO + 2[Ag (NH3 ) 2 ]+ + 3OH RCOO + 2Ag + 4NH 3 + 2H 2 O Aldehyde Tollen's reagent Hydroxide ion Carboxylate ion Silver mirror Ammonia Water

Q.19. Explain Fehlings test. Fehling solution A (CuSO4 solution) and Fehling solution B (alkaline solution of sodium potassium tartarate-Rochelle salt) are mixed in equal proportion and the mixture is heated with aldehyde, gives red precipitate of cuprous oxide. This test is known as Fehlings test. This test is only for aliphatic aldehydes because the aromatic aldehydes are not reduced by the Fehling solution. In laboratory the aldehydes can be detected by Fehlings test.
RCHO + 2Cu 2+ + 5OH RCOO + Cu2 O + 3H 2 O Aldehyde Cupric ion Hydroxide ion Carboxylate ion Red ppts Water

Q.20. Explain oxidation of ketones by strong oxidizing agents.

The ketones are oxidized by strong oxidizing agents like con. HNO3, KMnO4/H2SO4, K2Cr2O7/H2SO4 etc. and give minute of carboxylic acids. Symmetrical ketones give mixture of two carboxylic acids. For example, K 2Cr2O7 CH3COCH3 + 3[O] CH3COOH + HCOOH + H 2SO4 Methanoic Oxygen Propanone Ethanoic acid acid [O], CH3COOH + CO2 + H 2 O Ethanoic acid Carbon Water dioxide Unsymmetrical ketone gives mixture of four carboxylic acids. For example,
b
CH3 CO

a
CH2CH2CH3 Conc. HNO3

'a' clevage Main product

CH 3COOH + CH 3CH 2 COOH Ethanoic acid Propanoic acid

Pantan-2-one

'b' clevage Coproduct

HCOOH + CH 3CH 2 CH 2 COOH Methanoic acid Butanoic acid

In case of unsymmetrical ketones, the keto group stays preferentially with the smaller alkyl group and is the main product and this is known as Popoffs rule.

Q.21. Explain oxidation of ketones with sodium hypohalide. OR Explain Iodoform test.
Aldehydes or ketones containing CH3CO group, when treated with an excess of halogen in presence of alkali give haloform. For example, O O || || NaOX R C CH 3 R C ONa + CHX 3 (X = Cl , Br , I) Sodium Ketone Carboxylate Haloform

During halo formation reaction, if carbon-carbon double bond is present in the molecules, the double bond is not oxidized; hence, double bond remains unaffected. For example,

10

CH 3 | CH3CH = C C CH3 || O 3-Methylpent-3-en-2-one

CH 3 | NaOCl CH3 CH = C C ONa || O Sodium-2-Methylbut-2-enoate + CH 3Cl Chloroform

Q.22. Explain oxidation of ketones. (i) By strong oxidizing agents: The ketones are oxidized by strong oxidizing agents like con. HNO3, KMnO4/H2SO4, K2Cr2O7/H2SO4 etc. and give minute of carboxylic acids. Symmetrical ketones give mixture of two carboxylic acids. For example, K 2Cr2O7 CH3COCH3 + 3[O] CH3COOH + HCOOH + H 2SO4 Methanoic Oxygen Propanone Ethanoic acid acid [O], CH3COOH + CO2 + H 2 O Ethanoic acid Carbon Water dioxide Unsymmetrical ketone gives mixture of four carboxylic acids. For example,
b CH3 CO a CH2CH2CH3 Conc. HNO3 'b' clevage Coproduct HCOOH + CH3CH 2 CH 2 COOH Methanoic acid Butanoic acid 'a' clevage Main product CH3COOH + CH3CH 2 COOH Ethanoic acid Propanoic acid

Pantan-2-one

In case of unsymmetrical ketones, the keto group stays preferentially with the smaller alkyl group and is the main product and this is known as Popoffs rule. (ii) Oxidation with sodium hypohalide (NaOX or X2 + NaOH) (Iodoform test): Aldehydes or ketones containing CH3CO group, when treated with an excess of halogen in presence of alkali give haloform. For example, O O || || NaOX R C CH 3 R C ONa + CHX3 (X = Cl , Br , I) Sodium Ketone Haloform Carboxylate During halo formation reaction, if carbon-carbon double bond is present in the molecules, the double bond is not oxidized; hence, double bond remains unaffected. For example, CH 3 | CH3CH = C C CH3 || O 3-Methylpent-3-en-2-one CH 3 | NaOCl CH3 CH = C C ONa || O Sodium-2-Methylbut-2-enoate + CH 3Cl Chloroform

11

Q.23. Explain reduction due to -hydrogen of aldehydes and ketones.

The hydrogen atoms present on the carbon atom next to the carbonyl group of aldehydes and ketones are called -hydrogen atoms, and the acidity of -hydrogen atom is due to electron withdrawing, inductive effect of the carbonyl group and also due to resonance stabilization of the conjugate base (enolate ion).
O HO + HCC C O C O + H2 O

C = C

Carbanion

Enolate ion

Due to acidity of -hydrogen of aldehydes and ketones, they undergo a number of reactions such as aldol condensation, cross aldol condensation etc.

(i) Aldol condensation:

In this reaction, two same molecules of an aldehyde or ketone, having atleast one -hydrogen atom undergo a reaction in presence of dilute alkali (dil. NaOH, Na2CO3, Ba(OH)2 etc.) to form -hydroxy aldehyde (Aldol) or -hydroxy ketone (Ketol) respectively. This reaction is known as aldol condensation reaction. The name aldol is derived from the name of two functional group aldehyde and alcohol present in the product. Same way ketol is derived from two functional group of ketone and alcohol present in the product. The aldol and ketol readily lose water molecule to give - unsaturated carbonyl compounds which are aldol condensation product and the reaction is called aldol condensation. For example,
2CH 3CHO Ethanal dil. NaOH CH 3CHCH 2 CHO CH 3CH=CHCHO + H 2O | But-2-enal Water OH (aldol condensation product) 3-Hydroxy butanal

CH3 | dil.Ba(OH) 2CH3COCH3 Propanone 2

CH3 |

CH3 C CH 2COCH3 CH3 C = CHCOCH3 + H 2 O | 4-Methylpent-3-en-2-one Water OH 4-Hydroxy-4-Methy pentan-2-one

Formaldehyde, benzaldehyde and benzophenone do not undergo aldol condensation since they do not have an -hydrogen atom.

(ii) Cross-aldol condensation: An aldol condensation between two different aldehydes or two different ketones or between one aldehyde and one ketone is called cross aldol condensation and gives mixture of four products which are difficult to separate. So cross aldol condensations are of little synthetic value.
However, if one carbonyl compound does not possess -hydrogen atom then cross aldol condensations are of great synthetic utility. e.g.,

12

CH3 | 1. dil. NaOH CH 3CHO + CH 3CH 2 CHO CH3CH = CHCHO + CH3CH 2 CH = C CHO 2. Ethanal Propanal But-2-enal 2-Methylpent-2-enal self aldol condensation product CH 3 | + CH 3CH = C CHO + CH 3CH 2 CH = CHCHO + 2-Methylbut-2-enal Pent-2-enal cross aldol condensation product H2O Water

CHO + Benzaldehyde

COCH3 Acetophenone

1. dil. NaOH 2. , H2O

CH=CHCO 1,3diphenyl prop-2-en-1-one (major product)

CH=CHCHO

CHO + Benzaldehyde

CH3CHO Ethanal

1. dil. NaOH 2. , H2O

3Phenyl prop-2-enal (cinnamaldehyde) (major product)

(iii) Cannizzaro reaction:

Aldehydes which do not have an -hydrogen atom, when treated with concentrated alkali solution, undergo disproportionation, i.e., self-oxidation and reduction occurs. One molecule of aldehyde is reduced to the corresponding alcohol, at the cost of the other molecule of aldehyde which is oxidized to the corresponding carboxylic acid salts. This reaction is called Cannizzaro reaction. For example,
50% NaOH 2HCHO CH 3OH + HCOONa Methanal or con.KOH Methanol Sodium formate + H 2O (or HCOOK)

CHO Benzaldehyde

50% NaOH +H2O

CH2OH + Phenyl metahnol (Benzyl alcohol)

COONa Sodium benzoate

Q.24. Explain Aldol condensation.

In this reaction, two same molecules of an aldehyde or ketone, having at least one -hydrogen atom undergo a reaction in presence of dilute alkali (dil. NaOH, Na2CO3, Ba(OH)2 etc.) to form -hydroxy aldehyde (Aldol) or -hydroxy ketone (Ketol) respectively. This reaction is known as aldol condensation reaction. The name aldol is derived from the name of two functional group aldehyde and alcohol present in the product. Same way ketol is derived from two functional group of ketone and alcohol present in the product. The aldol and ketol readily lose water molecule to give - unsaturated carbonyl compounds which are aldol condensation product and the reaction is called aldol condensation. For example,

13

2CH 3CHO Ethanal

dil. NaOH

CH 3CHCH 2 CHO | OH 3-Hydroxy butanal

CH 3CH=CHCHO

H 2O Water

But-2-enal (aldol condensation product)

CH3 | dil.Ba(OH) 2CH3COCH3 Propanone 2

CH3 |

CH3 C CH 2COCH3 CH3 C = CHCOCH3 + H 2 O | 4-Methylpent-3-en-2-one Water OH 4-Hydroxy-4-Methy pentan-2-one

Formaldehyde, benzaldehyde and benzophenone do not undergo aldol condensation since they do not have an -hydrogen atom.

Q.25. Explain cross-aldol condensation.

An aldol condensation between two different aldehydes or two different ketones or between one aldehyde and one ketone is called cross aldol condensation and gives mixture of four products which are difficult to separate. So cross aldol condensations are of little synthetic value. However, if one carbonyl compound does not possess -hydrogen atom then cross aldol condensations are of great synthetic utility. e.g., CH 3 | 1. dil. NaOH CH 3CHO + CH 3CH 2 CHO CH 3CH = CHCHO + CH 3CH 2 CH = C CHO 2. Ethanal Propanal But-2-enal 2-Methylpent-2-enal self aldol condensation product CH 3 | + CH 3CH = C CHO + CH 3CH 2 CH = CHCHO + 2-Methylbut-2-enal Pent-2-enal cross aldol condensation product
CHO + Benzaldehyde COCH3 Acetophenone 1. dil. NaOH 2. , H2O

H2 O Water

CH=CHCO 1,3diphenyl prop-2-en-1-one (major product)

CHO + Benzaldehyde

CH3CHO Ethanal

1. dil. NaOH 2. , H2O

CH=CHCHO
3Phenyl prop-2-enal (cinnamaldehyde)

(major product)

Q.26. Explain cannizzaro reaction.

Aldehydes which do not have an -hydrogen atom, when treated with concentrated alkali solution, undergo disproportionation, i.e., self-oxidation and reduction occur. 14

One molecule of aldehyde is reduced to the corresponding alcohol, at the cost of the other molecule of aldehyde which is oxidized to the corresponding carboxylic acid salts. This reaction is called Cannizzaro reaction. For example,
50% NaOH 2HCHO CH 3OH + HCOONa Methanal or con.KOH Methanol Sodium formate + H 2O (or HCOOK)

CHO Benzaldehyde

50% NaOH +H2O

CH2OH + Phenyl metahnol (Benzyl alcohol)

COONa Sodium benzoate

Q.27. Explain nitration of aromatic aldehydes and ketones. OR Explain electrophilic substitution reactions of aromatic aldehydes and ketones.
Aromatic aldehydes and ketones undergo the electrophilic substitution reactions of the benzene nucleus. Since the aldehyde and ketone functional groups are electron withdrawing groups and so act as deactivating group and hence act as meta-directing group. So substitution occurs at meta-position. For example,
CHO
Con. Con. HNO3 H 2SO 4 low temperature 273 283K CHO + H2 O NO2 3-Nitrobenzaldehyde (m-Nitrobenzaldehyde) Water

Benzaldehyde

COCH3 Con. Con. HNO3 H 2SO 4 low temperature 273 283K Acetophenone

COCH3 + H2 O NO2 1-(3-Nitrophenyl)ethan-1-one Water (m-Nitroacetophenone)

Substitution reactions like halogenation, sulphonation also occur at m-position.

Q.28. Write down the uses of aldehydes and ketones.

In chemical industry, aldehydes and ketones are used as solvents, starting materials and reagents, for the synthesis of other products. Formaldehyde is used in manufacturing of Bakelite, resins and other polymers. A 40% solution of formaldehyde in water is called formalin which is used for the preservation of dead bodies of animals of biological or anatomical specimens. It is also used as a disinfectant and germicide. Formaldehyde is used in leather industry. Acetaldehyde is used for giving the shining like silver to mirror. 15

Benzaldehyde is used as a flavouring agent in perfume industry and is also used in manufacturing of dye like malachite green. Acetone is used in manufacturing liquid nail polish and also as nail polish remover. Acetone and methylethyl ketone are common industrial solvents. Some aldehydes and ketones for example butyraldehyde, vanillin, acetophenone, camphor etc. are well-known for their odours and flavours.

Q.29. Explain structure of carboxylic group.

In carboxylic acid compounds the carbon atom of carboxyl group is attached to one oxygen atom by single bond and another by double bond, but electron and neutron diffraction studies have proved that COOH has planar structure having angle of about 120, so the two oxygen atoms are sp2 hybridised. The electrons of double bond are delocalized between carbon and oxygen bond as shown in figure.

O R C O H

Here, and bond between carbon and oxygen, carbon and both oxygen atoms are sp2 hybridised RCO and OCO angle 120.

Q.30. Explain the method to prepare carboxylic acid from primary alcohols and aldehydes.
The primary alcohols are readily oxidized to the corresponding carboxylic acids with common oxidizing agents such as KMnO4 in neutral, acidic or alkaline medium or by K2Cr2O7 or CrO3 (chromium trioxide) in acidic medium. Oxidation with KMnO4 or CrO3 in acidic medium often gives some amount of esters. Therefore the oxidation with KMnO4 is preferred. Under these conditions the potassium salts of the carboxylic acid is first obtained, which on treatment with dil. H2SO4 gives carboxylic acids. For example,

3CH3CH 2 OH + 4KMnO 4 Potassium Ethanol Permanganate

3CH 3COOK + KOH + 4MnO 2 + 4H 2 O Potassium Maganese Water Potassium Hydroxide Dioxide ethanoate

2CH3COOK + H 2SO 4 2CH 3COOH + K 2SO4 Sulphuric acid Potassium ethanoate Ethanoic acid Potassium Sulphate CrO3 / H 2SO4 CH3 (CH 2 )6 OH CH3 (CH 2 )5COOH Heptanol Heptanoic acid Aldehydes are easily oxidized to corresponding carboxylic acids with KMnO4 in neutral, acidic or alkaline medium or by K2Cr2O7 or CrO3 in acidic medium and also even with mild oxidizing agent such as Tollens reagent. Manganese
16

Q.31. Explain the method to prepare carboxylic acid from alkyl benzene and alkenes. Aromatic carboxylic acids are prepared by the vigorous oxidation of alkylbenzene with acidic or alkaline KMnO4 or acidified K2Cr2O7 (chromic acid) or dil. HNO3. During these oxidation the entire side chain is oxidized to carboxylic acid group irrespective of the length of the side chain. 1 and 2 alkyl groups are oxidized in this manner but the 3 alkyl group is not oxidized and remains unaffected. For example,
CH3 + 3[O] (i) KMnO4 / KOH, (ii) dil. H2SO4 Benzoic acid COOH + 6[O] (i) KMnO4 / KOH, (ii) dil. H2SO4 Benzoic acid + CO2 + 2H2O COOH + H2 O

Toluene CH2CH3

Oxygen

Water

Ethyl benzene

Oxygen

Carbon dioxide

Water

CH3 CH CH3 + 9[O] (i) KMnO4 / KOH, (ii) dil. H2SO4 Benzoic acid COOH + 2CO2 + 3H2O

Isopropyl benzene
CH3 H3 C C

Oxygen

Carbon dioxide

Water

CH3 (i) KMnO4 / KOH, (ii) dil. H2SO4 No reaction

Tertbutyl benzene If there are no two or more than two alkyl groups is benzene ring, each group is oxidized to COOH group. For example,
CH3 + CH3 1,2-Dimethylbenzene (o-Xylene) Oxygen 6[O] (i) KMnO4 / KOH, (ii) dil. H2SO4 COOH

2H2O

COOH Benzene-1,2dicarboxylic acid

Water

17

CH3

CH3 + 6[O]

(i) KMnO4 / KOH, (ii) dil. H2SO4

COOH Benzene-1,4dicarboxylic acid

COOH + 2H2O

1,4-Dimethylbenzene (p-Xylene)

Oxygen

Water

Substituted alkenes are also oxidized to carboxylic acid by acidic K2Cr2O7 or alkaline KMnO4. For example,

(i) KMnO4 /KOH, CH3 CH = CH CH3 2CH3COOH (ii) dil. H 2SO4 But 2 ene Ethanoic acid Q.32. Explain the method to prepare carboxylic acid from nitrides and amides. Nitriles are hydrolysed to amide and then to carboxylic acid on boiling with mineral acids or alkalies as catalyst. For example, [H + ] or [OH ] [H + ] or [OH ] CH 3CN CH 3CONH 2 CH 3COOH + NH 3 H 2O Ethane nitrile Ethanamide Ethanoic acid Ammonia
CONH2
[H + ] or [OH ] H2O

COOH

+ NH3 Benzoic acid Ammonia

Benzamide

Q.33. Explain the method to prepare carboxylic acid from Grignard reaction. The theory of collision for chemical reaction was developed by Max Trauz and William Lewis in 1916-18. This principle deals with the energetic and mechanistic matter of reaction. It is based on the kinetic energy of gases. Carboxylic acids can be prepared by bubbling CO2 gas into the ethereal solution of a suitable Grignard reagent or by adding the solution of Grignard reagent to crushed dry ice (solid CO2) suspended in ether. First the addition product is obtained, which on decomposition with mineral acid gives carboxylic acid. For example,
O || H + /OH dry ether RMgX + O = C = O R C OMgX RCOOH + Mg (OH)X or H3O+ Carboxylic Grignard acid reagent Addition product
O || H O+ dry ether 3 CH 3CH 2 MgI + O = C = O CH 3CH 2 C OMgI Ethyl megnesium Carbon dioxide iodide Addition product CH 3CH 2COOH + Propanoic acid

Mg (OH)I Hydroxy magnesium iodide

18

MgBr dry ether + O = C = O

O C

OMgBr
H 3O +

Benzamide

Carbon dioxide

Addition product
COOH

+ Mg(OH)Br
Benzoic acid

Hydroxy magnesium bromide

In both the methods-nitriles and Grignard reagent are useful for converting the alkyl halide to the carboxylic acid, having carbon atom or atoms more than that present in alkyl halide.

Q.34. Explain the method to prepare carboxylic acid from acid chloride and anhydride.
Acid chloride when hydrolysed by water gives carboxylic acid, and more readily hydrolysed with aqueous alkali to give carboxylate ions, which on acidification gives corresponding carboxylic acids. For example,

R COCl Acid chloride

H 2O RCOOH + HCl Hydrolysis Carboxylic acid Hydrogen Chloride

OH /H 2 O H 3O + RCOO RCOOH + H 2 O Hydrolysis Carboxylate ion Carboxylic acid Water HCl

H2O CH3COOH + HCl Hydrolysis Ethanoic acid Hydrogen Chloride

CH 3COCl Ethanoyl chloride (Acetyl chloride)

OH /H 2 O H 3O + CH 3COO CH 3COOH + H 2 O Hydrolysis Ethanoate ion Ethanoic acid Water HCl

Anhydrides on hydrolysis with water give carboxylic acids. For example,

H 2O / (CH 3CO) 2 O 2CH 3COOH Ethanoic anhydride Hydrolysis Ethanoic acid (Acetic anhydride)

H 2O / (C6 H5 CO)2 O 2C6 H5COOH Hydrolysis Benzoic anhydride Benzoic acid

19

C6H5CO

H 2O / O CH 3COOH + C6 H 5 COOH Hydrolysis Ethanoic acid Benzoic acid CH3CO

Benzoic ethanoic anhydride

Q.35. Explain the method to prepare carboxylic acid from ester. Hydrolysis of esters in presence of mineral acids give carboxylic acids directly while hydrolysis in presence of alkali gives carboxylates, which on acidification give corresponding carboxylic acid.
For example,
CH 3COOCH 2 CH 3 Ethylethanoate H 3O + CH 3COOH + CH 3CH 2 OH Ethanoic acid Ethanol

CH3COOCH 2 CH 3 Ethylethanoate

NaOH

CH 3COONa + CH 3CH 2 OH Sodium ethanoate Ethanol

H3 O+ CH3COOH + Ethanoic acid Na+(aq) + Sodium ion H2 O Water

COOCH2CH3 NaOH

COONa

+ Sodium banzoate

CH3CH2OH Ethanol

Ethaylbenzoate

H3O+ COOH

+ Benzoic acid

Na+(aq) + Sodium ion

H2O Water

Q.36. Discuss the physical properties of carboxylic acids. The first three aliphatic acids (C1 to C3) are colourless liquids with pungent smell. The next three (C4 to C6) are colourless oily liquids with upleasant smell and remaining three (C7 to C9) are
20

colourless liquids with unpleasant smell at room temperature, while carboxylic acids with ten or more carbon atoms are colourless, waxy solids with no distinct smell due to low volatility. Aromatic carboxylic acids are solid with no distinct smell. C1 to C4 aliphatic carboxylic acid are fairly soluble in water, while C5 and C6 are slightly soluble and remaining are insoluble in water. The aromatic acids are almost insoluble in cold water, but soluble in hot water. The solubility of lower members of aliphatic carboxylic acids in due to hydrogen bond formation. The hydrogen bonding of carboxylic acid is stronger than that of alcohol, so the melting points and bonding points of carboxylic acid are more than those of alcohols of comparable molecular mass. In liquid state, the carboxylic acid molecules are associated with other carboxylic acid by formation of strong hydrogen bonding. The hydrogen bonding is so strong that they are not broken even in vapour phase. In vapour phase or in aprotic solvents most of the carboxylic acids exist as cyclic dimmers.

O O C

H O H O

O C O

C O H O

Association of carboxylic acidmolecules in liquid state

O R C O H O H O C R

Dimer form in aprotic solvent or vapour phase O O R C O H O H H H H

Hydrogen bonding in aqueous solution

Carboxylic acids in aqueous solution form intermolecular hydrogen bond with water molecules, so the carboxylic acids with lower molecular masses are soluble in water.

Q.37. Explain acidic nature of carboxylic acid.

Alcohols, phenols and carboxylic acid contain an OH group, but the carboxylic acids are much stronger acid than alcohols and phenols. Comparison of acidic character of alcohols, phenols and carboxylic acids are based on the stability of resonance structure of their negative ions.

21

R OH + OH Alcohol
OH

RO + H 3O + Not stabilized

+ Phenol

H2O

H3O+

(I)

(II)

(III)

As shown in reaction (a) carboxylate anions are stabilized by their resonance structure, so tendency to release proton is more, while the alkoxide ions as shown in reaction (b) are not stabilised by resonance, hence, alcohols have less tendency to release a proton, so the alcohols are much weaker acids than carboxylic acids, though both contain an OH group. In case of phenoxide ion as shown in reaction (c) having resonating structure I to III, but the structures carry a negative charge on the less electronegative carbon atom. Therefore their contribution towards the resonance stabilization of phenoxide ion is very small, while in carboxylate ion the negative charge on the more electronegative oxygen atom, so carboxylic acids are stronger acids than alcohols and phenols. But are weaker acids than the mineral acids (HCl, HNO3, H2SO4) and sulphonic acids. In aqueous solutions, the carboxylic acid ionizes and exist in dynamic equilibrium between carboxylate ion and hydronium ion. RCOOH + H2O RCCO + H3O+ [RCOO ][H 3O + ] [RCOOH][H 2 O]

So the equilibrium constant can be expressed as K eq =

Since water is taken in large excess hence [H2O] remains constant, so the equation can be written as

K eq [H 2 O]=

[RCOO ][H3O+ ] =K a [RCOOH]

The equilibrium constant Ka is called the dissociation constant of the acid, and it varies with the temperature for a given acid. From equation it is clear that at constant temperature, Ka is directly proportional to the [H3O+]. Therefore the value Ka is a measure of the acid strength of an acid, so higher the value of Ka, greater is the tendency of the acid to ionize and hence stronger is the acid. For convenience, the strength of an acid is generally indicated by its pKa value, rather than its Ka value pKa = log Ka

22

So, if carboxylic acid having smaller numerical value of pKa, then it is very strong i.e., better is a proton donor. Stronger acids have pKa values < 1, the acids with pKa values between 1 and 5 are considered to be moderately strong acids, weak acids have pKa values between 5 and 15 and extremely weak acids have pKa values > 15. The acid strength of carboxylic acid depends on the effect of various substituents. For example,

(i) Effect of electron donating groups (EDG): The alkyl group has electron donating inductive effect (+I effect), hence it will increase the electron density in the OH bond, so release of H+ ions will be more difficult, hence, the formic acid is stronger acid than acetic acid. Further the +I effect of the alkyl groups increases in the order CH3 < CH3CH2 < (CH3)2CH < (CH3)3C Hence the relative strength of carboxylic acid will be as CH3COOH > CH3CH2COOH > (CH3)2CHCOOH > (CH3)3CCOOH (ii) Effect of electron withdrawing group (EWG): Electron withdrawing group having I effect, and it decreases in the order F > Cl > Br > I > Ph. So the strength of the carboxylic acids will be as. FCH2COOH > ClCH2COOH > BrCH2COOH > ICH2COOH > C6H5CH2COOH Further, greater the number of electron withdrawing groups (substituents), stronger will be the acid (strength). Cl3 C COOH > Cl2 CH COOH > Cl CH2 COOH The inductive effect decreases rapidly with distance, so acidic strength order is

Cl |

Cl |

Cl |

CH3CH 2CHCOOH > CH3CHCH 2COOH > CH 2 CH 2 CH 2 COOH

(iii) The phenyl or vinyl group directly attached to carboxyl group have weaker electron donating effect than alkyl group. So unsubstituted aromatic carboxylic acids are stronger acids than unsubstituted aliphatic carboxylic acids, but formic acids does not contain any alkyl group, therefore it is stronger acid than unsubstituted aromatic acid, so the order of acidic strength is Formic acid > Benzoic acid > Acetic acid. For substituted aromatic carboxylic acid the presence of electron withdrawing group on the phenyl or aromatic carboxylic acid increases their acidic strength, while electron donating group, and decreases their acidic strength. For example,

NO 2

COOH

>

COOH Benzoic acid

>

CH3

COOH

4-Nitrobenzoic acid

4-Methylbenzoic acid
23

Electron withdrawing or electron donating group effect is more pronounced at 1, 2 position (ortho position) than 1, 4 position (para position) than 1, 3 position (meta position). For example the acid strength is

COOH NO2

COOH

COOH

COOH

>
NO2 4-Nitrobenzoic acid

>
NO2 3-Nitrobenzoic acid

>
Benzoic acid

2-Nitrobenzoic acid

Q.38. Explain the reaction involving cleavage of O-H bond.

The reaction showing the acidic character of the carboxylic acids i.e. cleavage of OH bond are given below:

(i) Reaction with metal:

Carboxylic acids like alcohols react with electropositive metals such as Na, K, Ca, Mg, Zn etc. to form their respective salts and liberate H2 gas. For example,

CH3COOH + Na CH3COONa + Acetic acid Sodium Sodium acetate

1 H2 2 Hydrogen

2CH 3COOH + Zn (CH 3COO) 2 Zn + H2 Zinc Hydrogen Acetic acid Zinc acetate

(ii) Reaction with alkalies:

Similar to phenols the carboxylic acids neutralize alkalies and form salts. For example,

CH 3COOH + NaOH CH 3COONa + H 2 O Sodium Acetic acid Hydroxide Sodium acetate Water
CH 3COOH + NH 4 OH CH 3COONH 4 + H 2 O Ammonium Acetic acid Ammonium acetate Water Hydroxide

(iii) Reaction with carbonates and hydrogen carbonates:

However unlike phenols the carboxylic acids react with weaker bases such as carbonates and hydrogen carbonates to evolve CO2 gas. For example,

2CH 3COOH + Na2 CO3 2CH 3COONa + CO 2 + H 2 O Acetic acid Sodium Sodium acetate Carbon Water dioxide Carbonet CH3COOH + NaHCO3 CH3COONa + CO 2 + H 2 O Sodium Acetic acid Sodium acetate Carbon Water dioxide bicarbonet
This reaction is used to detect the presence of COOH group in organic compounds. As most of the phenols do not produce CO2 gas with NaHCO3. Hence this reaction is also useful to distinguish phenols from carboxylic acids.

Q.39. Explain reaction of carboxylic acid with metal.

Carboxylic acids like alcohols react with electropositive metals such as Na, K, Ca, Mg, Zn etc. to form their respective salts and liberate H2 gas. For example, 24

CH3COOH + Na CH3COONa + Sodium Acetic acid Sodium acetate

1 H2 2 Hydrogen

2CH 3COOH + Zn (CH 3COO) 2 Zn + H2 Zinc Hydrogen Acetic acid Zinc acetate

Q.40. Explain reaction of carboxylic acid with alkalies.

Similar to phenols the carboxylic acids neutralize alkalies and form salts. For example,

CH 3COOH + NaOH CH 3COONa + H 2 O Sodium Acetic acid Hydroxide Sodium acetate Water
CH 3COOH + NH 4 OH CH 3COONH 4 + H 2 O Ammonium Acetic acid Ammonium acetate Water Hydroxide

Q.41. Explain reaction of carboxylic acid with carbonates and hydrogen carbonates.
However unlike phenols the carboxylic acids react with weaker bases such as carbonates and hydrogen carbonates to evolve CO2 gas. For example, 2CH 3COOH + Na2 CO3 2CH 3COONa + CO 2 + H 2 O Acetic acid Sodium Sodium acetate Carbon Water dioxide Carbonet CH3COOH + NaHCO3 CH3COONa + CO 2 + H 2 O Sodium Acetic acid Sodium acetate Carbon Water dioxide bicarbonet This reaction is used to detect the presence of COOH group in organic compounds. As most of the phenols do not produce CO2 gas with NaHCO3. Hence this reaction is also useful to distinguish phenols from carboxylic acids.

Q.42. Explain reaction involving cleavage of C-OH bond.

The hydroxyl group of a carboxylic acid like the hydroxyl group in alcohols, can be replaced (substituted) by group like Cl, OR, NH2 and OCOR to form acid chloride, esters, amides, and anhydrides, respectively. These derivatives are known as functional group derivatives of carboxylic acids. (i) Formation of acid chlorides: Carboxylic acid reacts with SOCl2 (thionyl chloride) or PCl5 or PCl3 to form acid chloride. For example, CH 3COOH + SOCl2 CH 3COCl + SO 2(g) + HCl(g) Ethanoyl chloride Sulphur Hydrogen Acetic acid Thionyl chloride (Acetyl chloride) dioxide chloride 3CH 3COOH + PCl3 3CH 3COCl + H 3 PO3 Phosphorous Ethanoyl chloride Phosphorous Acetic acid trichloride acid (Acetyl chloride)

CH3COOH + PCl5 CH 3COCl + POCl3 + HCl Ethanoyl chloride Phosphorous Hydrogen Acetic acid Phosphorous pentachloride (Acetyl chloride) oxychloride chloride For the production of acid chloride, the reaction with SOCl2 is preferred, because in this reaction the other two products SO2 and HCl both are in gaseous state, so it is very easy to remove them from acid chloride, hence purification of acid chloride becomes very easy. (ii) Formation of esters: When carboxylic acids are heated with alcohols or phenols in presence of con. H2SO4 or HCl, esters are formed. The reactions are known as esterifications (Fischer-Speier esterification). This reaction is reversible and hence the rate of reaction can be increased by taking excess amount of carboxylic acid or alcohol or by removing water from the reaction mixture.
25

CH3COOH + CH3CH 2 OH Acetic acid Ethanol

con.H 2SO4

CH 3COOCH 2CH3 + H 2 O Ethyl ethanoate Water (Ethyl acetate)

con.H 2SO4 C6 H5COOH + CH3OH C6 H5COOCH3 + H 2 O Benzoic acid Methanol Methyl benzoate Water (iii) Formation of anhydrides: Two molecules of carboxylic acids combine in presence of strong dehydrating agent such as P2O5 or mineral acid, such as con. H2SO4, on heating gives acid anhydrides. For example, P2 O5 2CH 3COOH (CH 3CO) 2 O + H 2 O Ethanoic anhydride Water Acetic acid (Acetic anhydride) By treating acid chlorides with sodium salts of carboxylic acids, the acid anhydrides are obtained. CH 3COCl + CH 3COONa (CH 3CO)2 O + NaC l Ethanoyl chloride Sodium acetate Ethanoic anhydride Sodium (Acetyl chloride) (Acetic anhydride) chloride (iv) Formation of Amides: Carboxylic acids react with NH3 to give ammonium salts, which on further heating at high temperature, lose a molecule of water to form amide, For example,
COOH COONH4
+

CONH2

NH3 Ammonia Ammonium banzoate

COONH4

H2 O

Benzoic acid

Benzamide

Water
CONH2 CONH2

COOH COOH + 2NH3

COONH4 2H2O Ammonium phthlate

Phthalic acid

Ammonia

Phthalamide

CO NH3 Ammonia + CO Phthalimide NH

Strong heating

CH3COOH + NH3 CH3COONH 4 CH3CONH 2 + H 2O Higher temperature Water Acetic acid Ammonia Ammonium acetate Acetamide

Q.43. Explain formation of acid chlorides from carboxylic acid.

Carboxylic acid reacts with SOCl2 (thionyl chloride) or PCl5 or PCl3 to form acid chloride. For example, 26

CH 3COOH + SOCl2 CH 3COCl + SO 2(g) + HCl(g) Ethanoyl chloride Sulphur Hydrogen Acetic acid Thionyl chloride (Acetyl chloride) dioxide chloride 3CH 3COOH + PCl3 3CH 3COCl + H 3 PO3 Phosphorous Ethanoyl chloride Phosphorous Acetic acid trichloride acid (Acetyl chloride)

CH3COOH + PCl5 CH 3COCl + POCl3 + HCl Phosphorous Ethanoyl chloride Phosphorous Hydrogen Acetic acid pentachloride (Acetyl chloride) oxychloride chloride
For the production of acid chloride, the reaction with SOCl2 is preferred, because in this reaction the other two products SO2 and HCl both are in gaseous state, so it is very easy to remove them from acid chloride, hence purification of acid chloride becomes very easy.

Q.44. Explain formation of esters from carboxylic acid.

When carboxylic acids are heated with alcohols or phenols in presence of conc. H2SO4 or HCl, esters are formed. The reactions are known as esterification (Fischer-Speier esterification). This reaction is reversible and hence the rate of reaction can be increased by taking excess amount of carboxylic acid or alcohol or by removing water from the reaction mixture.

CH3COOH + CH3CH 2 OH Acetic acid Ethanol

con.H 2SO4

CH 3COOCH 2CH3 + H 2 O Ethyl ethanoate Water (Ethyl acetate)

C6 H5COOH + CH3OH Benzoic acid Methanol

con.H 2SO4

C6 H5COOCH3 + H 2 O Methyl benzoate Water

Q.45. Explain formation of anhydride from carboxylic acid.

Two molecules of carboxylic acids combine in presence of strong dehydrating agent such as P2O5 or mineral acid, such as con. H2SO4, on heating gives acid anhydrides. For example, P2 O5 2CH 3COOH (CH 3CO)2 O + H 2 O Ethanoic anhydride Acetic acid (Acetic anhydride) By treating acid chlorides with sodium salts of carboxylic acids, the acid anhydrides are obtained. CH 3COCl + CH 3COONa (CH 3CO) 2 O + NaC l Ethanoyl chloride Sodium acetate Ethanoic anhydride (Acetyl chloride) (Acetic anhydride)

Q.46. Explain formation of amides from carboxylic acid.

Carboxylic acids react with NH3 to give ammonium salts, which on further heating at high temperature, lose a molecule of water to form amide, For example,
COOH COONH4
+

CONH2

NH3 Ammonia Ammonium banzoate

H2 O

Benzoic acid

Benzamide

Water

27

COOH COOH + 2NH3

COONH4 COONH4 2H2O Ammonium phthlate

CONH2 CONH2

Phthalic acid

Ammonia

Phthalamide

CO NH3 Ammonia + CO Phthalimide NH

Strong heating

CH3COOH + NH3 CH3COONH 4 CH3CONH 2 + H 2O Higher temperature Water Acetic acid Ammonia Ammonium acetate Acetamide

Q.47. Explain reaction involving COOH group as a whole. (i) Reduction: The reduction of carboxylic acids with Lithium Aluminium hydride (LiAlH4) or better with diborane (B2H6) gives primary alcohol. Using this reaction the CO group can be reduced to CH2 group. For example, (i) LiAlH 4 or B2 H 6 CH 3COOH CH 3CH 2 OH H 2O Ethanoic acid Ethanol (10 alcohol) Diborane does not easily reduce functional groups like esters, nitro, halo etc., and sodium borohydride does not reduce the carboxyl group. Carboxylic acids on reduction with hydroiodic acid and phosphorus at 473 K give alkanes. In this reaction the COOH group is reduced to CH3 group. Red P CH3COOH + 6HI CH3 CH3 + 2H 2O + 3I 2 Hydrogen 473 K Water Iodine Ethanoic acid Ethane iodide (ii) Decarboxylation: Carboxylic acid and their salts lose carbon dioxide to form hydrocarbon and reaction is known as decarboxylation reaction. The sodium salts of carboxylic acid are heated with sodalime (NaOH and CaO mixture in the proportion ratio of 3:1) give alkane e.g., CaO / CH3COONa + NaOH CH 4 + Na2CO3 Sodium Methane Sodium Sodium acetate hydroxide carbonet If two carboxylic groups are attached to the same carbon atom called gem-dicarboxylic acid undergo decarboxylation simply on heating at 415-435 K temperature. For example,

COOH CH2 COOH Propanedioic acid

415435

CH3COOH Ethanoic acid

CO2 Carbon dioxide

28

On electrolysis of aqueous solution of sodium or potassium salts of fatty acids at anode due to oxidation, CO2 is liberated and alkane having double carbon is obtained. At cathode H2 gas liberated and this process is called Kolbes electrolytic reduction or electrolytic decarboxylation.

Q.48. Explain reduction of carboxylic cid.

The reduction of carboxylic acids with Lithium Aluminium hydride (LiAlH4) or better with diborane (B2H6) gives primary alcohol. Using this reaction the CO group can be reduced to CH2 group. For example, (i) LiAlH 4 or B2 H 6 CH 3COOH CH 3CH 2 OH H 2O Ethanoic acid Ethanol (10 alcohol) Diborane does not easily reduce functional groups like esters, nitro, halo etc., and sodium borohydride does not reduce the carboxyl group. Carboxylic acids on reduction with hydroiodic acid and phosphorus at 473 K give alkanes. In this reaction the COOH group is reduced to CH3 group. Red P Q.49. CH3COOH + 6HI CH3 CH3 + 2H 2O + 3I 2 Hydrogen 473 K Water Iodine Ethanoic acid Ethane iodide

Q.50. Explain decarboxylation of carboxylic acid.

Carboxylic acid and their salts lose carbon dioxide to form hydrocarbon and reaction is known as decarboxylation reaction. The sodium salts of carboxylic acid are heated with sodalime (NaOH and CaO mixture in the proportion ratio of 3:1) give alkane e.g., CaO / CH3COONa + NaOH CH 4 + Na2CO3 Sodium Methane Sodium Sodium acetate hydroxide carbonet If two carboxylic groups are attached to the same carbon atom called gem-dicarboxylic acid undergo decarboxylation simply on heating at 415-435 K temperature. For example,

COOH CH2 COOH Propanedioic acid

415435

CH3COOH Ethanoic acid

CO2 Carbon dioxide

On electrolysis of aqueous solution of sodium or potassium salts of fatty acids at anode due to oxidation, CO2 is liberated and alkane having double carbon is obtained. At cathode H2 gas liberated and this process is called Kolbes electrolytic reduction or electrolytic decarboxylation.

Q.51. Explain substitution reaction in the hydrocarbon part of carboxylic acid. (i) Halogenation: Carboxylic acid having an -hydrogen atoms are halogenated at the -position on treatment with dichlorine or dibromine in the presence of small amount of red phosphorus to give halocarboxylic acid. This reaction is known as Hell-Volhard Zelinsky reaction. For example, Cl | (i) Cl 2 /Red P CH 3CH 2 COOH CH 3CHCOOH + HCl (ii) H 2 O Hydrogen -ChloroPropanoic acid chloride propanoic acid If more than one mole of Cl2 or Br2 are used then the 2nd and 3rd -hydrogen atoms are successively substituted. For example,

29

Cl2 / Re d P Cl2 Re d P CH 3COOH ClCH 2 COOH H 2 O, HCl H 2 O, HCl Ethanoic acid Chloro ethanoic acid Cl2 Re d P HCl + Cl2 CHCOOH Cl3CCOOH H 2O Hydrogen Dichloro ethanoic acid Trichloro chloride ethanoic acid (ii) Ring substitution: Aromatic carboxylic acid undergo the electrophilic substitution reactions like halogenations, nitration and sulphonation. Since the COOH group acts as a deactivating and hence m-directing group, so the reactions take place only under vigorous conditions. The COOH group deactivates the benzene ring and catalyst aluminium chloride (Lewis acid) gets bonded to the carbonyl group. So they do not undergo-Crafts reactions.

COOH Bromination Br2/FeBr3, Br 3-Bromobenzoic acid COOH Nitration, Conc. HNO3/ Conc. H2SO4 Benzoic acid NO2 3-Nitrobenzoic acid COOH Conc. H2SO4, Sulphonation SO3H 3-Sulphobenzoic acid
Q.52. Explain halogenations of carboxylic acid.
Carboxylic acid having an -hydrogen atoms are halogenated at the -position on treatment with dichlorine or dibromine in the presence of small amount of red phosphorus to give halocarboxylic acid. This reaction is known as Hell-Volhard Zelinsky reaction. For example, Cl | (i) Cl 2 /Red P CH 3CH 2 COOH CH 3CHCOOH + (ii) H 2 O -ChloroPropanoic acid propanoic acid HCl Hydrogen chloride

HBr Hydrogen bromide

COOH + H2O

Water

H2O

Water

If more than one mole of Cl2 or Br2 are used then the 2nd and 3rd -hydrogen atoms are successively substituted. For example,

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Cl2 / Re d P Cl2 Re d P CH 3COOH ClCH 2 COOH H 2 O, HCl H 2 O, HCl Ethanoic acid Chloro ethanoic acid Cl2 Re d P HCl + Cl2 CHCOOH Cl3CCOOH H 2O Hydrogen Dichloro ethanoic acid Trichloro chloride ethanoic acid

Q.53. Explain ring substitution of aromatic carboxylic acid.

Aromatic carboxylic acid undergo the electrophilic substitution reactions like halogenations, nitration and sulphonation. Since the COOH group acts as a deactivating and hence m-directing group, so the reactions take place only under vigorous conditions. The COOH group deactivates the benzene ring and catalyst aluminium chloride (Lewis acid) gets bonded to the carbonyl group. So they do not undergo-Crafts reactions.

COOH Bromination Br2/FeBr3, Br 3-Bromobenzoic acid COOH Nitration, Conc. HNO3/ Conc. H2SO4 Benzoic acid NO2 3-Nitrobenzoic acid COOH Conc. H2SO4, Sulphonation SO3H 3-Sulphobenzoic acid
Q.54. Explain the uses of carboxylic acid.
Methanoic acid is used in leather industry, rubber industry, in medicine, in dyeing and electroplating industry. Ethanoic acid is used as coagulant for latex, manufacturing of plastic, rayon and silk. It is also used as a solventin laboratory ans as vinegar in the manufacturing of pickles in food industry. Hexanedioic acid is used in manufacturing of nylon 6, 6. Benzoic acid is used in medicine as urinary antiseptic and for making aniline blue in dye industry, and sodium benzoate as food preservatives higher fatty are used for manufacturing of soaps and detergents. Benzene-1, 2-dicorboxylic acid is used in the manufacturing of resins and benzene-1, 4dicarboxylic acid is used in manufacturing of polyesters.

HBr Hydrogen bromide

COOH + H2O

Water

H2O

Water

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