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1|Page, , Chemistry Notes for class 12 Chapter 12, Aldehydes, Ketones and Carboxylic Acids, In aldehydes, the carbonyl group ( )C=O) is bonded to carbon and hydrogen, while in the, ketones, it is bonded to two carbon atoms, Nature of Carbonyl Group, The carbon and oxygen of the carbonyl group are Sp2 hybridised and the carbonyl double bond, contains one o-bond and one π-bond., , The electronegativity of oxygen is much higher than that of the carbon, so there electron cloud, is shifted towards the oxygen. Therefore, C-O bond is polar in nature., Nomenclature, (i) Nomenclature of aldehydes In IUPAC system, the suffix “e” of alkane is replaced by the, suffIX “al”. e.g.,, , (ii) Nomenclature of ketones In IUPAC system, the suffix “e” of alkane is replaced by “one”., e.g.,, , Preparation of Aldehydes and Ketones, (i) By oxidation of alcohols Aldehydes and ketones are generally prepared by oxidation of, primary and secondary alcohols, respectively.
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2|Page, , (ii) By dehydrogenation of alcohols In this method, alcohol vapours are passed over heavy, metal catalysts (Ag or Cu). Primary and secondary alcohols give aldehydes and ketones., , (iii) By ozonolysis of alkenes, , (iv) By hydration of alkynes Acetylene on hydration gives acetaldehyde and other alkynes on, hydration give ketones.
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5|Page, , Preparation of Ketones
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6|Page, , Physical Properties of Aldehydes and Ketones, 1. Methanal (HCHO) is a gas at room temperature. and its 40% aqueous solution is known as, formalin. It is a reducing agent in silvering of mirrors and decolourising vat dyes., 2. Ethanal (CH3CHO) is a volatile liquid. Other aldehydes and ketones are liquid or solid at, room temperature., 3. The boiling point of aldehydes and ketones are higher than hydrocarbons and ethers of, comparable molecular mass due to high magnitude of dipole-dipole interactions., 4. Aldehydes and ketones have lower boiling point than those of alcohols of similar molecular
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7|Page, , masses due to absence of intermolecular hydrogen bonding., 5. The lower members of aldehydes and ketones are miscible with water due to the formation, of hydrogen bond with water. However, the solubility decreases with increase in length of alkyl, chain., 6. Acetophenone is a hypnotic (sleep producing drug) so used as a medicine under the name, hypnone., Chemical Reactions of Aldehydes and Ketones
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8|Page, , (ii) Addition of ammonia and its derivatives Reaction with ammonia
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9|Page, , Some N-substituted Derivatives of Aldehydes and Ketones
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11 | P a g e, , During oxidation of unsymmetrical ketones the point of cleavage is such that keto group stays, preferentially with the smaller alkyl group popoff‟s rule)., , [Fehling solution is a mixture of Fehling solution A and Fehling solution B in 1: 1 ratio., Fehling solution A is aqueous copper sulphate and Fehling solution B is alkaline sodium, potassium tartrate which is also called, Rochelle salt.], (c) Benedict solution With it, aldehydes (except benzaldehyde) also give red ppt. of CU2O., (d) Schiff’s reagent It is an aqueous solution of magenta or pink coloured rosaniline, hydrochloride which has been decolourised by passing SO2, Aldehydes give pink colour with, this reagent but ketones do not., Haloform reaction Aldehydes and ketones having at east one methyl group [3-α hydrogen], linked to the carbonyl carbon atom (methyl ketones) are oxidised by sodium hypohalite to, sodium salts of corresponding carboxylic acids having one carbon atom less than that of, carbonyl compound. The methyl group is converted to haloform.
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12 | P a g e, , Iodoform reaction with sodium hypoiodite is also used for the detection of CH 3 – group or, CH3CH(OH)- group by producing yellow solid CHI3., (v) Aldol condensation, , Its further condensation gives phorone,, This reaction is exhibited by those aldehydes and ketones which have at least one a-hydrogen.
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15 | P a g e
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16 | P a g e, , Carboxylic Acids, , Classification, Depending upon the number of -COOH groups, they are classified as, (i) monocarboxylic acids; containing one -COOH group, (ii) dicarboxylic acids: containing two -COOH groups., Sources of carboxylic acids
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18 | P a g e, , (iii) From acid derivatives All acid derivatives like amides (RCONH2), acid halides (RCOCl),, esters (RCOOR‟), acid anhydrides (RCO-O-COR) on hydrolysis give carboxylic acids. All acid, derivatives break from RCO+., , (iv) From nitriles and amides Nitriles are hydrolysed to amides and then to acids in the, presence of H+or OH- as catalyst. Mild reaction conditions are used to stop the reaction at the, amide stage., , (v) From Grignard reagents Grignard reagents react with carbon dioxide (dry ice) to form, salts of carboxylic acids which in turn give corresponding carboxylic acids after acidification, with mineral acid
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19 | P a g e, , Physical Properties of Carboxylic Acids, 1. Aliphatic carboxylic acids up to nine carbon atoms are colourless liquids at room, temperature with unpleasant odours. The higher acids are wax like solids., 2. The lower carboxylic acids are freely miscible with water due to the presence of, intermolecular hydrogen bonding with H2O molecules. However, the solubility in water, decreases gradually due to increase in the size of alkyl group., 3. Monocarboxylic acids have higher boiling points as compared to the alcohols of comparable, molecular masses due to the presence of stronger intermolecular hydrogen bonding as shown, below., , 4. Melting points of aliphatic monocarboxylic acids shows alternation or oscillation effect, i.e.,, the m.p. of an acid with even number of carbon atoms is higher than the next lower and next, higher homologue containing odd number of carbon atoms. This is because, in case of acids, with even number of carbon atoms, the terminal -CH3 and -COOH groups lie on the opposite, sides of the zig-zag chain. As a result, they get closely packed in the crystal lattice., 5. Glacial acetic acid is completely pure acetic acid and represents the solid state of acetic acid., Below 16.6°C temperature pure acetic acid is converted into ice like solid hence it is called, glacial acetic acid., Chemical Properties of Carboxylic Acids
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20 | P a g e, , Carboxylic acids do not give reactions of carbonyl groups as it enters into resonance with lone, pair of O of -OH group., (i) Acidity, , Above reactions are used to detect the presence of carboxyl group Ul an organic compound. ,, Carboxylic acids dissociate in water to give resonance stabilised carboxylate anions and, hydronium ion., , The strength of the acid is expressed in terms of the dissociation constant (Ka), also called, acidity constant. A stronger acid has higher Ka but lesser pKavalue (pKa == -log Ka)., The electron releasing substituents (+1 effect) decrease the acidic strength of the carboxylic, acids by destabilising the carboxylate ion., , The electron withdrawing substituents (-1 effect) such as halogen atoms (X), nitro (NO2) group, increase the acidic strength by decreasing the magnitude of the negative charge on the, carboxylate anion and thus stabilising it. The release of H+ ion becomes easy., Acidic strength order
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21 | P a g e, , This is because -1 effect decreases in the order : F > C1 > Br > I., , This is because – I effect decreases with distance., Per acetic acid (CH3COOO-H) is a weaker acid than acetic acid as acetate ion is stabilised by, resonance., Acidic strength of aromatic acids The parent member of the family benzoic acid which is a, weaker acid (Ka = 6.3 x 10-5) than acid (Ka = 17.7 x 10-5) but stronger than acetic acid., Some order of acidity are, , (b) Similarly, Ka values of methyl substituted (toluic acids) at 298 K are as follows:
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22 | P a g e, , From the Ka values, it is evident that with the exception of o-isomer, both p and m-toluic acids, are weaker acids than benzoic acid whereas the three isomeric nitro benzoic acids are stronger, acids than benzoic acid., (ii) Reactions involving cleavage of C-O-H bond, (a) Formation of anhydride, , Mechanism
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23 | P a g e, , (iii) Chemical reactions involving – COOH group
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24 | P a g e, , (iv) Substitution reactions in the hydrocarbon part α -hydrogen atoms in carboxylic acids, are acidic in nature and can be easily replaced by halogen atoms in HVZ reaction, , The reaction is known as Hell-Volhard-Zelinsky reaction., (v) Arndt-Eistert reaction It is method of converting lower carboxylic acids to their higher, homologues, , (vi) Reducing property Among carboxylic acids, formic acid is the only acid that acts as, reducing agent. It reduces, acidified KMnO4 to MnSO4, HgCl2 to Hg, Tollen‟s reagent to silver, mirror and Fehling‟s solution to red ppt. and itself gets oxidised to CO 2 and H2O., HCOOH + HgCl2→ Hg + 2HCI + CO2, (vii) Electrophilic substitution reactions of aromatic acids -COOH group shows -R effect,, therefore, acts as a deactivating and meta-directing group. Carboxylic acids do not undergo, Friedel-Craft‟s reaction because the carboxylic group IS deactivating and the catalyst, AlCl3 (anhy.) gets bonded to the carboxyl group.
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25 | P a g e, , Uses, 1. Formic acid is used in leather tanning, textile dyeing and finishing., 2. Acetic acid is used in the manufacture of rayon and in plastics, in in rubber and silk, industries, in cooking and in vinegar (a 8-10% solution of acetic acid)., 3. Benzoic acid and its salts are used as urinary antiseptics., 4. Formic acid can act as a reducing agent., Derivatives of Carboxylic acids, These are obtained when -OH group of carboxylic acids is replaced by Cl, NH2, OR‟ and, OCOR and are called respectively acid chloride, acid amide, ester and acid anhydride.
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26 | P a g e, , Properties of Acid Derivatives, 1. Chemical reactions of acid halides, , 2. Chemical reactions of acid amides, , 3. Chemical reactions of ester, , 4. Chemical reactions of anhydrides
