>\Karihant NCERT SOLUTIONS CHEMISTRY CLASS 12" With Selected NCERT Exemplar ProblemsNCERT SOLUTIONS CHEMISTRY CLASS 12" by Geeta Rastogi : >< arihant ARIHANT PRAKASHAN, MEERUTPreface Feeling the immense importance and value of NCERT books, we are presenting this book, having the NCERT Exercises Solutions. For the overall benefit of the students we have made this book unique in such a way that it presents not only solutions but also detailed explanations. Through these detailed and through explanations, students can learn the concepts which will enhance their thinking and learning abilities. We have introduced some Additional Features with the solutions which are given below: Thinking Process (3) Before giving solutions to questions we have discussed the points that tell how to approach to solve aproblem. Here we have tried to cover all those loopholes which may lead to confusion. All formulae and hints are discussed in full detail. Note We have provided notes also to solutions in which special points are mentioned which are of great value for the students. This book also covers Solutions to selected problems of NCERT Exemplar Problems. With the hope that this book will be of great help to the students, we wish great success to our readers. Geeta RastogiCoe NXagers 1. 12. 13. 14. 15. 16. Contents . The Solid State . Solutions . Electrochemistry . Chemical Kinetics . Surface Chemistry . Process of Isolation of Elements . The p-block Elements . The d- and f-block Elements . Coordination Compounds . Haloalkanes & Haloarenes Alcohols,Phenols & Ethers Aldehydes, Ketons & Carboxylic Acids Amines Biomolecules Polymers Chemistry in Everyday Life 1-26 27-68 69-96 97-128 129-146 147-161 162-192 193-221 222-261 262-301 302-343 344-985 386-417 418-437 438-450 451-462Course Structure Class XII (Theory) Paper One Time : 3 Hrs Max Marks: 70 Class Xil : Weightage Unit Solid State 4 Uniti | Solutions 5 Uniti | Electrochemistry 5 UnitlV | Chemical Kinetics 5 UnitY | Surface Chemistry 4 UnitVI General Principles and Processes ofisolation of Elements 3 Unitvil | p-Block Elements 8 Uniti | d-and?-Block Elements 5 Unitix” | Coordination Compounds 3 UnitX | Haloalkanes and Haloarenes 4 Unitx’ | Alcohols, Phenols andEthers 4 UnitxiT _ | Aldehydes, Ketones and Carboxylic Acids 6 UnitxI | Organic Compounds containing Nitrogen 4 UnitxiV | Biomolecules a UnitxV | Polymers 3 UnitxvI__| Chemistry in Everyday Life 3 Total 70 Unit! Solid State Classification of solids based on different binding forces:. molecular, ionic, covalent and metallic solids, amorphous and crystalline solids (elementary idea). Unit cell in two dimensional and three dimensional lattices, calculation of density of unit cell, packing in solids, packing efficiency, voids, number of atoms perunitcellinacubic unit cell, point defects, electrical and magnetic properties. Band theory of metals, conductors, semiconductors and insulators and n & p typesemiconductors. Unit Il Solutions Types of solutions, expression of concentration of solutions of solids in liquids, solubility of gases in liquids, solid solutions, colligative properties - relative lowering of vapour pressure, Raoult's law, elevation of boiling point, depression of freezing point, osmotic pressure, determination of molecular masses using colligative properties, abnormal molecular mass, van't Hoff factor.Unit III Electrochemistry Redox reactions, conductance in electrolytic solutions, specific and molar conductivity, variations of conductivity with concentration, Kohlrausch's Law, electrolysis and law of electrolysis (elementary idea), dry cell -electrolytic cells and Galvanic ells, lead accumulator, EMF of acell, standard electrode potential, Nernst equation and its application to chemical cells, Relation between Gibbs energy change and emfofacell, fuel cells, corrosion. Unit IV Chemical Kinetics Rate ofa reaction (Average and instantaneous), factors affecting rate of reaction: concentration, temperature, catalyst; order and molecularity of a reaction, rate law and specific rate constant, integrated rate equations and half life (only for zero and first order reactions), concept of collision theory (elementary idea, no mathematical treatment). Activation energy, Arrhenious equation. Unit V Surface Chemistry ‘Adsorption - physisorption and chemisorption, factors affecting adsorption of gases on solids, catalysis; homogenous and’ heterogenous activity and selectivity; enzyme catalysis colloidal state distinction between true solutions, colloids and suspension; lyophilic , lyophobic multimolecular and macromolecular colloids; properties of colloids; Tyndall effect, Brownian movement, electrophoresis, coagulation, emulsion types of emulsions. Unit VI General Principles and Processes of Isolation of Elements Principles and methods of extraction - concentration, oxidation, reduction - electrolytic method and refining; occurrence and principles of extraction of aluminium, copper, zincand iron. Unit VII_p-Block Elements Group -15 Elements: General introduction, electronic configuration, occurrence, oxidation states, trends in physical and chemical properties; nitrogen preparation properties & uses ; compounds of nitrogen, preparation and properties of ammonia and nitric acid, oxides of nitrogen (Structure only) ; Phosphorus - allotropic forms, compounds of phosphorus: preparation and properties of phosphine, halides PC, Pcl, and oxoacids (elementary idea only). Group 16 Elements: General introduction, electronic configuration, oxidation states, occurrence, trends in physical and chemical properties,dioxygen: Preparation, Properties and uses, classification of oxides, Ozone, Sulphur - allotropic forms; compounds of sulphur: Preparation properties and uses of sulphur-dioxide, sulphuric acid: industrial process of manufacture, properties and uses; Oxoacids of sulphur (Structures only). Group 17 Elements: General introduction, electronic configuration, oxidation states, occurrence, trends in physical and chemical properties; compounds of halogens, Preparation, properties and uses of chlorine and hydrochloric acid, interhalogen compounds, oxoacids of halogens (structures only).Group 18 Elements: General introduction, electronic configuration, occurrence, trends in physical and chemical properties, uses. Unit VIII d and f Block Elements General introduction, electronic configuration, occurrence and characteristics of transition metals, general trends in properties of the first row transition metals - metallic character, ionization enthalpy, oxidation states, ionic radii, colour, catalytic property, magnetic properties, interstitial compounds, alloy formation, preparation and properties of K,Cr,0, and KMn04, Lanthanoids - Electronic configuration, oxidation states, chemical reactivity and lanthanoid contraction andits consequences. Actinoids - Electronic configuration, oxidation states and comparison with lanthanoids. Unit IX. Coordination Compounds Coordination compounds Introduction, ligands, coordination number, colour, ‘magnetic properties and shapes, IUPAC nomenclature of mononuclear coordination compounds. Bonding, Werner's theory, VBT, and CFT; structure and stereoisomerism, importance of coordination compounds (in qualitative inclusion, extraction of metals and biological system). UnitX Haloalkanes and Haloarenes. Haloalkanes: Nomenclature, nature of C -X bond, physical and chemical properties, mechanism of substitution reactions, optical rotation. Haloarenes: Nature of C -X bond, substitution reactions (Directive influence of halogen in monosubstituted compounds only). Uses and environmental effects of - dichloromethane, trichloromethane, tetrachloromethane, iodoform, freons, DDT. Unit XI Alcohols, Phenols and Ethers Alcohols: Nomenclature, methods of preparation, physical and chemical ~ properties( of primary alcohols only), identification of primary, secondary and tertiary alcohols, mechanism of dehydration, uses with special reference to methanol and ethanol. Phenols: Nomenclature, methods of preparation, physical and chemical properties, acidic nature of phenol, electrophillic substitution reactions, uses of phenols. Ethers: Nomenclature, methods of preparation, physical and chemical Properties, uses, UnitXII Aldehydes, Ketones and Carboxylic Acids Aldehydes and Ketones: Nomenclature, nature of carbonyl group, methods of Preparation, physical and chemical properties, mechanism of nucleophilic addition, reactivity of alpha hydrogen in aldehydes: uses. : Carboxylic Acids: Nomenclature, acidic nature, methods of preparation, physical and chemical properties; uses.Unit XIII Organic compounds containing Nitrogen Amines: Nomenclature, classification, structure, methods of preparation, physicaland chemical properties, uses, identification of primary, secondary and tertiaryamines. Cyanidesand Isocyanides-will be mentioned atrelevant places intext. Diazonium salts: Preparation, chemical reactions and importance in synthetic organicchemistry. UnitXIV Biomolecules Carbohydrates - Classification (aldoses and ketoses), monosaccahrides (glucose and fructose), D-L configuration oligosaccharides (sucrose, lactose, maltose), polysaccharides (starch, cellulose, glycogen); Importance of carbohydrates. Proteins -Elementary idea of a - amino acids, peptide bond, polypeptides, proteins, structure of proteins - primary, secondary, tertiary structure and quaternary structures (qualitative idea only), denaturation of proteins; enzymes. Hormones-Elementaryidea excludingstructure. Vitamins-Classification and functions. Nucleic Acids: DNA and RNA. Unit XV Polymers Classification - natural and synthetic, methods of polymerization (addition and condensation), copolymerization, some important polymers: natural and synthetic like polythene, nylon polyesters, bakelite, rubber. Biodegradable and non-biodegradable polymers. Unit XVI Chemistry in Everyday life Chemicals in medicines - analgesics, tranquilizers antiseptics, disinfectants, antimicrobials, antifertility drugs, antibiotics, antacids, antihistamines. Chemicals in food - preservations, artificial sweetening agents, elementary idea ofantioxidants. Cleansing agents- soaps and detergents, cleansingaction. Practicals Evaluation Scheme for Examination Marks Evaluation Scheme secsiee asa Volumetric Analysis. 10 Salt Analysis ae Content Based Experiment lo ea Cass record project workand viva erate Total [0% 8. 9 10. 11. 12. 13. 14, Chapter 1 0 Haloalkanes and Haloarenes Important Results Alkyl or aryl halides are classified as mono, di or polyhalogen compounds. They are polar in nature. . Haloalkanes are prepared by electrophilic addition of halogen acids with alkenes. . Haloalkanes are also prepared by the reaction of alcohols with halogen acids, phosphorus halides and thionyl chloride. . Aryl halides or haloarenes are ‘prepared by electrophilic substitution of arenes. Fluorides and iodides are best prepared by halogen exchange method. Haloalkanes participate in Sy-reactions due to polar C—X bond. Reactivity order of haloalkanés in S,.2 reactions : Primary > Secondary > Tertiary Reactivity order of haloalkanes in Sy1 reactions : Primary < Secondary < Tertiary Optical isomerism in these compounds is found due to the presence of chiral carbon atom. Sy2 mechanism leads to inversion of configuration in haloalkanes whereas Sy1 mechanism leads to racemization. Haloarenes. are less reactive towards nucleophilic substitution reactions as compared to haloalkanes. Melting point of p-dichlorobenzene is higher than that of o- and m-isomers. Reason is its symmetry. Halogenation of benzene proceeds by electrophilic substitution mechanism. Polyhalogen compounds have various industrial applications. Chloroform is not used as anaesthetic due to its toxic nature (formation of phosgene gas).Haloalkanes and Haloarenes 263 15. Pyrene fire extinguishers are not used in presence of water due to the formation of phosgene gas by CCl. 16. DDT is not preferred now-a-days due to its non-biodegradable nature. 17. Freons are used as refrigerants but damage the ozone layer. Ozone layer is a protective cover for ultraviolet radiations of sun. 18. In haloalkanes, carbon atom of C—X bond is sp® hybridized while in haloarenes, it is sp? hybridized. Intext Questions Question 1. Write the structures of the following compounds. (i) 2-chloro-3-methylpentane (ii) L-chloro-4-ethyl cyclohexane Giii) 4-tert- butyl-3-iodoheptane (iv) 1,4-dibromobut-2-ene (v) 1-bromo-4-sec-butyl-2-methylbenzene To write the structure of the compounds first draw the continuous C-chain according to the name of parent hydrocarbon, Then place the substituents at the positions as mention in the name. (i) C-chain of &-atoms; —Cl at C-2 and —CH, at C-3. (ii) Cyclic arrangement of 6 C-atoms; —Cl at C-1 and —C.H, at C-4, (iii) C-chain of 7 atoms; ter-butyl [—C(CH,),] at C-4 and —I at C-3, (iv) C-chain of 4 atoms; —Br at C-1 and C-4; Double bond between C-2 and C-3. (Benzene ring with.6 C-atoms and 3 double bonds at alternate positions; —Br at C-1; —CH, at C-2 and sec. butyl —CH—CH,—CH, |at'C-4 position. Hy 1 ea aes Solution. (i) CH;—CH—CH— CH,—CH, cl CH, 2-chloro-3-methylpentane cl 1 6 2 (ii) 5 3 4 CoHs 1-chloro-4-ethyleyclohexane264 NCERT Class XII Chemistry Solutions 1 ac a aL Boe ip © ik (ii) cece at CH,—CH,—CHy I HC I —CHy CH, 4-tert.butyl-3-iodoheptane 3 1 2 fi (iv) Br—CH, —CH=CH—CH,—Br 1,4-dibromobut-2-ene Br 1 ™ 6 cls 4 HjC—CH—CH,—CHy 1-bromo-4-sec. butyl, 2-methylbenzene Note After drawing the structures, count the valencies of every element and complete them by using H-atoms (if incomplete). Question 2. Why is sulphuric acid not used during the reaction of alcohols with KIP 23% Sulphuric acid is a good oxidizing agent. Solution. When KI reacts with H,SO,, it produces HI. In order to produce alkyl iodides (R—I), this HI should react with alcohols (R—OH). But the reaction does not take place in this manner as H,SO, oxidises HI to I, which in turn does not react with alcohol. KI+H,so, #2, KHso, + HI HSO, ——> H,0 +SO, +[0] 2HI + [0] ——> H,0 +1, Note Instead of H,SO4; HPO, can be used to produce alkyl iodides. Question 3. Write the structures of different dihalogen derivatives of propane. : a a 3 1 2.3 Solution. Br—CH,—CH,—CH,—Br Br—CH,—CH—CH 1,3-dibromopropane | ii} Br 1,2-dibromopropane imHaloalkanes and Haloarenes 265 ic 3 2 A 1 ats CH;—CH,— seated eee as CH; Br Br 1,1-dibromopropane 2,2-dibromopropane funy uv] Question 4. Among the isomeric alkanes of molecular formula CsH;2, identify the one that on photochemical chlorination yields (i a single monochloride (ii) three isomeric monochlorides iii) four isomeric monochlorides. () The molecular formula CzHi, can be represented by three structural isomers. These are CH, HC—C—CH, CH,—CH,—CH,—CH,—CH, | Pentane CH, ui 2,2-,dimethylpropane (neo-pentane) w cHy— Cc cH, Hy 2methyibutan Costa (ii) Number of monochlorides depends upon the types of hydrogen atoms present in the molecule. So, find the different types of hydrogen atoms and give answer on this basis. Solution. () A single monochloride [IV] can be produced only when all the hydrogen atoms are equivalent. This isomer must be symmetrical. Its structure is given by [I]. CH, CHy | H,C—C—CH,+ Cl, + HC —C—CH,Cl+ Hel | CH, enn 1 a 1-chloro-2, 2-dimethylpropane (i) Isomer [Il] has three groups of equivalent hydrogen atoms. Therefore, three isomeric monochlorides [V, VI and VII] are Produced,266 NCERT Class Xll Chemistry Solutions (a) (b) © (b) fa) CH,— CH,— CH,— CH,— CH, + Cl; —“> Penne 5 4 2 2 1 CH,— CH,— CH,— CH,— CH,— Cl 1-chloropentane [Vv] Eases a aca 4+CH,— CH,— CH,— CH— CH, cl 2-chloropentane (vu) en gona 1 +CH,— CH,— Ce CH,— CH; a 3-chloropentane [vil] (iii) Isomer [II] has four groups of equivalent hydrogen atoms. Therefore, it can produce four isomeric monochlorides [VIII, IX, X and XI}. (a) (b) co] @ CH, — CH— CH,— CH, +Cl, —> © CH, 2-methylbutane (aq) a 1 a3 cH, ¢—CH—CH, —CH, +cH,—t— CH,— CH, CH, CH; t-chloro-2-methylbutane __2-chloro-2-methylbutane (vil) (xy 4 a a + CHy— a eos cH, cl 2-chloro-3-methylbutane [xX] a aad + CH,—CH— CH,—CH,— Cl CH, 1-chloro-3-methylbutane (xq)Haloalkanes and Haloarenes 267 Question 5. Draw the structures of major monohalo products in each of the following reactions : OH aC sea, — ‘CH,CH; : B's _ Bry heat or Gi) UV light O2N CH,OH +He) Hest Hi CH, oy +HI — (v) CH,CH,Br + Nal — “7 He bp O + Be Wi” (i) SOCI, converts aliphatic —OH group into —C| (ii) In the presence of light allylic substitution takes place ie.,H of allylic position is replaced by Br-. (iii) HCI at high temperature replaces aliphatic —OH group by —Cl. (iv) In case of asymmetric unsaturated compounds, addition of HI takes place according to Markownikoff's rule. (It isa halide exchange reaction. (vi) Same as (ii) on Pyridin vi Solution. (i) + soch ——“*, Thiony! Cyclohexanol chloride Chlorocyclohexane +G0}+ HCl Note The reaction takes place in the presence of pyridine. The method is known as Darzen’s method. 7 CH,CH, | , en Bry Hat CHCH, (ay + Br Gyiight +HBr OnN’ ON 4-nitroethy] 1-bromo-1-(4-nitrophenyl) ethane benzene268 NCERT Class XII Chemistry Solutions Note Bromination does not take place in benzene ring. 4_CH,OH 4_-CH,CI Heat (ii) IS +Ho) Ay 1 , +H,0 HO! HO % % 4-hydroxymethy! 4-chloromethyl phenol phenol Note Phenolic —OH group is not replaced by —Cl group. CH CHy A Markownikoit's rule oo Cen anes, CTS 1-methy! 1-iodo-1-methy! cyclohexene cylohexane Note According to Markownikoff's rule, iodine will add to the carbon atom having less number of hydrogen atoms. (v) CH,CH,Br +Nal —> CH,CH,I +NaBr Bromoethane Todoethane Note Iodide ion is a strong nucleophile so it displaces bromide ion. Br 3 Heat or . Cyclohexene ‘3-bromocyclohexene Note Under above specified conditions, allylic halogenation takes place. Addition reaction can take place only if reaction is at room temperature. Question 6. Arrange each set of compounds in order of increasing boiling points : (i) Bromomethane, bromoform, chloromethane, dibromomethane (ii) 1-chloropropane, iso-propyl chloride, I-chlorobutane 9% (Boiling point increases with increase in molecular mass. It also depends on the size and number of halogen atoms, Gi) Along with the above criteria, branching of the carbonchain is also considered. More branching decreases the boiling point. Solution. (i) CH,Cl (chloromethane) < CH,Br (bromomethane) < CH,Br (dibromomethane) < CHBr, (bromoform) (i) (CH;),CHCI (iso-propylchloride or —2-chloropropane) < CICH,CH,CH, (J-chloropropane) =< _— CICH,CH,CH,CHs (1-chlorobutane).Haloalkanes and Haloarenes 269 Question 7, Which alkyl halide from the following pairs would you expect to react more rapidly by an §y2 mechanism? Explain your answer. () CHyCH,CH,CH,Br or CH;CH, GHCH, Br CH; i) maid CH, or ,c—b— Br : cu, (ii) CHy GHCH,CH,Br or CH,CH, CHCH,Br CH, CH, If the leaving group is same in two isomers then the reactivity towards ‘S\2 reaction decreases with increase in steric hindrance. Solution. (i) CHyCH,CH,CH,Br Reason Being a primary halide, it is more reactive than the other isomer which is a secondary halide. (i) CH,CH,CHCH, | Br Reason Being a secondary halide, it is more reactive than the tertiary halide. 43 24 (ii) CHACHCHLCHBr CH, Reason Here both are primary halides. The presence of methyl group closer to halide group increases the steric hindrance and 432d decreases the rate inCHCHANCH CH, Question 8. In the following pairs of halogen compounds, which compound undergoes faster Syl reaction?270 ion depends upon th Reactivity of a halogen derivative towards Sy! reaction deps pon the stability vo the carbocation formed. So, compare the stability of carbocation formed. Solution. The order of relative stabilities of carbocations is as follows : Tertiary > Secondary > Primary. () C1 It is a tertiary halide. So, the carbocation formed is comparatively more stable making the compound more reactive. i a SHUG It is a secondary halide. So, its carbocation is more stable than that of the primary halide, Question 9. Identify A, B,C, D, E, R and R’ in the following : ther @ Cae Devether, 4 120, 5 D,0 Gi) R—Br+ Mg DSH, ¢ B20, CH,GHCH, D CH; CH; Mj (ii) CH; cu, ~Nestet p_y Mp 4H, p CH; CH; (@) Haloalkanes react with Mg in dry ether to form Grignard reagents Oe (RMgX), which reacts with water to form hydrocarbons. (b) Haloalkanes react with Na in dry ether to give hydrocarbons containing double number of C-atoms. Solution. w Dry ether C= + Mg ‘MgBr Bromocyclohexane Cyclohexyl magnesium bromide [A] (Grignard reagent)] 1,0 fae © era Cyclohexane [B]Haloalkanes and Haloarenes 271 Dry eth (i) CH;—CH—Br +Mg “YS cy, oH MgBr CH; CH; Iso-propyl bromide Iso-propyl magnesium bromide [C] (Grignard reagent) D. ©, cH,—cH—D + Mg(OD)Br CH, 2-deutero propane oe a Na/ether (ii) CH; —C—C—cH, 8 oy, cx mt Ware CH, CH; feet CH, 2,2,3,3-tetramethyl ‘butane CH, CH, CH, CH; | CH, —¢—H + Mg(OH)X M *S, cH,—c—mgx 2, CH, CH, Grignard reagent 2-methylpropane 1D} El Exercises Question 1. Name the following halides according to IUPAC system and classify them as alkyl, allyl, benzyl (primary, secondary, tertiary), vinyl or aryl halides : () (CH3),CHCH(CNCH; (ii) CHyCH,CH(CH;)CH(C,H,)CI (ii) CH;CH,C(CH;),CH1 (iv) (CH3);CCH,CH(Br)C,H, (v) CH;CH(CH;)CH(Br)CH; (vi) CH;C(C,H,),CH,Br (vii) CH;C(CI)(C;Hs)CH,CH C(Cl)CH,CH(CH;), -CHC(Br)(CH3)2 (x) p- CIC H,CH,CH(CH;),272 NCERT Class XII Chemistry Solutions (xi) m- CICH,C,H,CH,C(CHs)3 (xii) 0-Br—C,H ,CH(CH,) CH,CH, () To write the IUPAC name draw the structures and find the longest C-chain, find the position of the substituents and name them. (ii) To classify the compounds find the group with which halogen atom is attached. If attached with R- it is called alkyl halide, if attached with CHj=CH—CH, group, it is called allyl halide, if attached with CiHCH,group, it is called benzyl halide, if attached to CH,==CH group, it is called vinyl halide and if attached directly to benzene nucleus, it is called aryl halide. Solution. aah, afewiad 4 “ Gr CH— CH, CH, Cl 2.chloro-3-methylbutane [Secondary alkyl halide] bat ee eb acter eee 1 (i) CH,—CH, —CH— CH— CH,— CH, CH, Cl S.chloro-4-methylhexane [Secondary alky! halide] CH CH, aereromera cr Feta cai tes (iii) CH»—CH, fae (iv) CH CH CH, CH, B 1-fodo-2,2-dimethyIbutane a 7 [Primary alkyl halide] 1-bromo-3,3-dimethyl-1-phenylbutane [Secondary benzyl halide] CH, -CH, aceon eta ee a4 (wv) Ci GH CH (vi) CH,—C—CH,—Br | CH, Br ra CHCH. 2-bromo-3-methylbutane ‘-bromo-2-¢thy ) yyl-2-methylbutane {Secondary alkyl halide} [Primary alkyl halide} ae CH,—CHg _ a2. ot al) uytlgt htgt 5 (vit) ee ts (viii) CHy — CH= C— CH, —CH—CHs a cl CH, ‘Schloro-3-methylpentane -chloro-5-methylhex-2-ene [Tertiary alkyl halide} {Vinyl halide}Haloalkanes and Haloarenes CH, iat eme tse lati (ix) CHy— cH ce —CH, Br 4-bromo-4-methylpent-2-ene [Allyl halide} CHy 1 ala CHy—C—CHy 3 2 CH 1 ‘CHCl (xi) 1-chloromethyl-3-(2, 2-dimethylpropyl) benzene [Benzyl halide] Questi (@® CH,CH(CNCH(Br)CH, (ii) CHF,CBrCIF (ii) CICH,C=CCH,Br (iv) (CCls)sCCl 273 CHy—GB—CHy CH; 1-chloro-4-(2-methylpropyl) benzene [Aryl halide] cea HyC—CH—CH,—CH, 2 1-Br (xii) 1-bromo-2-(1-methylpropyl) benzene [Aryl halide] m 2. Give the IUPAC names of the following compounds : (v) CHC (p-CIGH,), CH(B)CHs (vi) (CH;);CCH =C- CIC HyE-p To write IUPAC name draw the structures. Find the longest C-chain, Give the numbers and name them. Solution. ot a Al ae al ees eae is ) CHy—CH_ HCH, (i) F cl Br F 2-bromo-3-chlorobutane 1-bromo-1-chloro-1,2,2- trifluoroethane 4 sae (iii) CL—CH, -C=C—CH,—Br 1-bromo-4-chlorobut-2-yne274 NCERT Class XI! Chemistry Solutions a cl a a-c-a ly la (iv) cl—c——c— cl ) Br [, sel cals aoq—¢—a HgC—C—CH—CH, | ca 4,1, 1, 2, 3, 3, -heptachloro- 2\(trichloromethy!) propane al 2-bromo-3, 3-bis (4-chloropheny!) butane CH; a o 4al 20k (vi) mec aey Mt CH 1-chloro-1-(4-iodophenyl)- 3, 3-dimethylbut -1-ene Question 3. Write the structures of the following organic halogen compounds : (i) 2-chloro-3-methylpentane _ (ii). p-bromochlorobenzene (iii) 1-chloro-4-ethyleyclohexane (iv) 2-(2-chlorophenyl)-I-iodooctane (v) 2-bromobutane (vi) 4-tert-butyl-3-iodoheptane (vii) 1-bromo-4-sec-butyl-2-methylbenzene (viii) 1,4-dibromobut-2-ene oS To write the structure of organic compound draw the carbon chain (2 according to the parent hydrocarbon. Then, place the substituent groups at their mentioned positions, . ji a Solution. (i) CH,— a CH—CH,— CH, cl cH, 2-chloro-3-methylpentane Br a a A oe i) (ai) 4 : sly Ja sl Js 4a 4 = CoHs p-bromochlorobenzene 1-chloro-4-ethylcylohexaneHaloalkanes and Haloarenes 275 cantly Steed Sage ate (iv) I-CH,—CH—CH,—CH,—CH,—CH,—CHy—CH 1 2c 2-(2-chlorophenyl)-1-iodooctane Peas 4 3) CHy—CH—CH,—CH, Br 2-bromobutane 1 fete gr al oF (vi) ee ere ances 1 C(CH,); 4-tert-butyl-3-iodoheptane Br CH (vii) HyC—CH—CH,—CH, 1-bromo-4-sec-butyl-2-methyl benzene | Br Br 1,4-dibromobut-2-ene 1 mea ete (viii) CH,—CH=C. HoGh Question 4. Which one of the following has the highest dipole moment? @ CHCl, (ii) CHCl; (ii) CCl, Draw the structures and observe the symmetry of each molecule to find 4 their dipole moment as it is zero for symmetrical molecule. Solution, uv \, of \, of XN @)n=162D = (ii) p= 1.03D (iii) p= 00D276 NCERT Class XII Chemistry Solutions (i) CCl, (tetrachloromethane) is a symmetrical molecule so, it has zero dipole moment. (ii) In CHC, (trichloromethane/chloroform), the resultant of two C—Cl dipole moments is opposed by the resultant of C—H and C—C1 bond, Since, the latter resultant dipole moment is smaller than the former, CHCl, has a dipole moment = 1.03 D. (ii) In CH,Cl, (dichloromethane), the resultant of two C—Cl dipole moments is reinforced by the resultant of two C—H bonds. Thus, CH,Cl, has a dipole moment = 1.62 D. Therefore, CH,Cl, has the highest dipole moment amongst the above three molecules. Note CCl, is also called carbon tetrachloride; CH,Cl, is methylene chloride. Question 5. A hydrocarbon CsHjg does not react with chlorine in dark but gives a single monochloro compound CsH,Cl in bright sunlight. Identify the hydrocarbon. Enlist the possibilities of structures for molecular formula CsHyo. Which isomer reacts in dark, which in sunlight. Then give the reactions. Solution. () Molecular formula C ;H,o can be either alkene or cycloalkane. (ii) Since, the hydrocarbon does not react with chlorine in dark, it is not an alkene. So, it is a cycloalkane, i.e., cyclopentane. (ii) Since, it forms only single monochloro derivative in bright sunlight, all the H-atoms should be identical. So, it is cyclopentane. Dark - CHssCNa + NH] Bry (ii) CH; — CH; ————___> CH, — CH, — Br + HB: (9) Cprane 2 w/520- 6701) Bromcathane’ JNO, (iii) CH,CH=CH, —*_, cH— CH, — cH, —Br A2N%, v Propene Pear 1-bromopropane 1H — CH, —CH—NO2 1-nitropropane CH,C1 CH,OH (iv) _ChyfBoll KOH (ag) —acr Toluene Benzyl chloride Benzyl alcoholHaloalkanes and Haloarenes 281 Bi (v) CH, — CH=CH, #2 cH,— cH— , KOH(alc) Propene Br { 1, 2-dibromopropane CH,— C=CH Proypne socl, Hg,F. (vi) CH,CHOH “2, cy,cu,c1 —2?2, cH CHF Ethanol (Pyridine) Chloroethane -Hg2Cl2 Fluoroethane (Ethyl fluoride) Pr KCNialc) ‘CH3MgBr (vil) CHyBr SONG), yy coy SES Bromomethane KBr, 3 (ether) —Mg(OH)Br, CH,;—C =NMgBr| —Gi,07%" |-NHs | CH, H, —C=O | cH, Propanone (viii) CH,— CH,— CH=CH, #85 cH,—CH,— CH—CH, But-1-ene | Br 2-bromobutane _ KOH oy, CHeCH_cH, But-2ene - Dry ether (3). Css CH ee SAAN ie ential — CH, — CH, — CH, — CH,— CH, — CH, — CH, n-octane +2NaCl _BrolFeBrs _2Nalethor (ary), & “Fittig reaction)” Benzene Bromobenzene aia Biphenyl282 NCERT Class XII Chemistry Solutions Question 12. Explain why (i) the dipole moment of chlorobenzene is lower than that of cyclohexyl chloride? )) alkyl halides, though polar, are immiscible with water? (ii) Grignard reagents should be prepared under anhydrous conditions? (i) Find the hybridization of C-atoms in chlorobenzene and cyclohexyi chloride and electronegativity to find the bond polarity and thus, dipole moment. (ii) Strong intermolecular H-bonding among water molecules. (ili) Consider reactive nature of Grignard reagents with water. Solution. w a sp? hybridized carbon q sp? hybridized carbon Chlorobenzene Cyclohexyl chloride Due to sp” hybridization of C-atom in chlorobenzene, C-atom is more electronegative (greater s-character) whereas in cyclohexyl chloride, C-atom is sp* hybridized, i.e., less electronegative (lesser s-character). So. polarity of C—Cl bond in chlorobenzene is less than the C—Cl bond in cyclohexyl chloride. Therefore, the dipole moment of chlorobenzene is lower than that of cyclohexyl chloride. (ii) Water molecules have enough strong H-bonding (intermolecular) which is difficult to be broken by alkyl halides, though they are also polar in nature. Therefore, alkyl halides do not dissolve in water and form separate layers. (ii) Grignard reagents (R—Mg—x) are readily decomposed by water to produce alkanes. That is why they should be prepared under anhydrous conditions. Instead, ether is used as a solvent during the preparation of Grignard reagent. R—Mg—X +H,O——> RI eo Alkane 7 SOH Question 13. Give the uses of freon 12, DDT, carbon tetrachloride and iodoform, Solution. Uses of freon 12 [CCLF,] () Itis used as a refrigerant. ii) It is used as propellants in aerosols and foams. It is also used for air conditioning purposes.Haloalkanes and Haloarenes 283 Uses of DDT [p p’-dichlorodiphenyltrichloroethane] a ca O - C’ i cl H DDT (i It is an effective insecticide against the mosquito that spreads malaria and lice that carry typhus. (ii) It is also used in many countries as insecticide for sugarcane and fodder crops, [Due to its non-biodegradable nature, its use has been banned in various countries including U.S.A.] Use of carbon tetrachloride [CCl,] ( It is used in the manufacture of refrigerants. (i) Itis used in the manufacture of propellants of aerosol cans. (iii) Itis also used as feedstock in synthesis of chlorofluoro carbons and other chemicals, (iv) It is used as a fire-extinguisher under the name pyrene due to its non-inflammable nature. (v) It is used as a cleansing agent in home and industries. (vi) It is also used as an important solvent. Uses of lodoform [Triodomethane CHI] (i) Itis used as an antiseptic, particularly for dressing wounds. Note Use of freons is not environment friendly, as it damages the ozone layer in the atmosphere. Due to unpleasant odour of iodoform, its use as an antiseptic is replaced by other iodine containing compounds. Question 14. Write the structure for the major organi of the folléwing reactions. () GHyCH,CH,Cl + Nal -Asetoos, Gi) (CHy)CBr + KOH Ethanol, (ii) CH;CH(BrCH,CH; + NaOH —Wster_, (iv) CH,CH,Br + KCN —Aasthanol, (v) CsHsONa + C,HsC1—> product in each284 NCERT Class ‘XII Chemistry Solutions (vi) CH,CH,CH,OH + SOCI,——> (vii) CH;CH,CH=CH,+ HBr P=“, (viii) CH;CH =C(CH,), + HBr —> (i) Replacement of —Clby —L (ji) Dehydrohalogenation @-elimination). (iii) Replacement of —Br by — OH. (iv) Replacement of —Br by —CN (v) Elimination of NaCl, formation of ether. (Williamson's synthesis) (vi) Replacement of —OH by —CI; formation of alkyl halide. (vii) Addition of HBr across the double bond (peroxide effect) (vill) Addition of HBr according to Markownikoff's rule. Solution. fe t A () HyC— CH, — CH, — C1 + Nat “PS, ‘-chloropropane kent CH,— CH,—CH,—I + NaCl 1-iodopropane CHy i (i) HyC —C—Br+ kon aml, CH,—C | +KBr+H,0 fal CH; CH; oe 2-methylpropene iii) HyC— CH— CH, — CH, + NaOH —Water ye ual a Me Tayarolysis” ir 2-bromobutane CH,— CH—CH, — CH, + NaBr+H,0 OH 2-butanol or butane -2-ol (iv) CH,— CH,—Br + KCN —AethANOL Cys CH, CaN + KBr Bromoethane : Ethyl cyanide Williamson's aereeH 1 synthesis” Cois— O— CH, + NaCl (v) CgHjONa + C,H,CI Sodium Chloroethane Phenyl ethyl ether phenoxide (vi) CH;— CH,— CH,— OH + SOCI, Pytidine, Propan-1-ol CH,— CH,— CH,— Cl +SO, +HCl 1-chloropropaneHaloalkanes:and Haloarenes 285 (vii) CHy— CH,— CH=CH, + HBr—eoxide But-lene CH,— CH,— CH,— CH,Br 1-bromobutane cH, (vii) CHy—CH=C—CH, + Hr —Markounikott_, CH, | CH,— CH, — C—CH; Br 2-bromo-2-methyl butane Question 15. Write the mechanism of the following reaction. nBuBr+ KCN £°8—#29, nBuCN () Write the resonating structures of KCN. (ii) Due to the presence of polar solvent, find the possibility, which product will be formed preferentially? Solution. Resonating forms of KCN are the following. =X Kis a Cyanide ion is an ambident nucleophile. It can attack through C-atom or through N-atom. Thus, two possible products are cyanides and isocyanides respectively. Here in the presence of the polar solvent, KCN readily ionises to furnish ions. As C—C bond is more stable than C_N bond, so cyanide is predominantly formed. let + be Ce KCN +CH,— CH,— CH,— CH,‘ Br—_, ‘n-butyl bromide CH;— CH,— CH,— CH,C=N + Br n-butyl cyanide Question 16. Arrange the compounds of each set in order of reactivity towards Sy2 displacement : (i) 2-bromo-2-methylbutane, 1-bromopentane, 2-bromopentane (i) L-bromo-3-methylbutane, 2-bromo-2-methylbutane, 2-bromo-3-methylbutane (iii) 1-bromobutane, 1-bromo-2, 2-dimethylpropane, 1-bromo-2-methylbutane, 1-bromo-3-methylbutane.286 NCERT Class XI|_ Chemistry Solutions 4 §,2 reactions involve the formation of transition state. Higher the steric 29% Mndrance, lesser the stability of transition state and so lesser the reactivity towards Sy2. Solution. The order of decreasing reactivity of compounds is given as (i) CH,CH,CH,CH,CH, Br > CH, CHCH,CH,CH 1-bromopentane(19) | Br 2-bromopentane(2) Br > CH,CCH,CH, CH, 2-bromo-2-methyl -butane (39) (i) CH, FeCH CHE > CH, 1-bromo-3-methylbutane ay Br cH. ee ee —CH, > CH, — C—CH,— CH, Bis Cs CH, 2-bromo-3-methyl ? = butane(29 2-bromo. er (iii), CHjCH,CH,CH,Br > CH; CHCH,CH,Br 1-bromobutane | a cH, 1-bromo-3-methyl butane(19, CH, | > CH,;CH, | a CH,Br >CH, —C—CH,Br | . CH CH, \-bromo-2-methyl 4. promo-2,2 dimethyl butane(19, propane(19 Question 17. Out of CgHsCHCIC,Hy and CgHsCH,Cl which is more easily hydrolysed by aqueous KOH? En S\t reactions, stability of carbocations is responsible for the reactivity: The reaction is more likely to take place by Sy! reaction,Haloalkanes and Haloarenes 287 Solution. CgH;—CH— C,H, nization, cay, CH C,H, +Cl | Carbocation stabilized cl by delocalisation 1-chloro-1, 1-diphenyl over CgH, rings methane(29 (More stable) CgH,CH,C] —Lonization CHH;CH, = +Cl Benzyl chloride Carbocation (9, stabilized by delocalisation over one CeH, ring (Less Stable) In Sy! reaction, reactivity depends upon the stability of carbocations. CeHs— CH— CH, carbocation is more stable as compared to CiHsCHz. Therefore, CgH; CHCIC, Hs gets hydrolysed more easily . than CgH,CHCL Question 18. p-dichlorobenzene has higher melting point and lower solubility than those of o-and m-isomers. Discuss. ‘Symmetry of the molecule is related to its crystal lattice structure and 7® hence, to its melting point and solubility. A highly symmetrical structure has a higher melting point e Solution. a cl a cl a o-dichlorobenzene —_m-dichlorobenzene p-dichlorobenzene Out of the above three isomers of dichlorobenzene , the p-isomer is more symmetrical than other two isomers. So, it has more closely packed arrangement of molecules in its crystal lattice. So, p-dichlorobenzene has a higher melting point and lower solubility as compared to ortho and meta isomers. Question 19. How the following conversions can be carried out? (i) Propene to propan-l-ol i) Ethanol to but-1-yne ii) L-bromopropane to 2-bromopropane (iv) Toluene to benzyl alcohol (v) Benzene to 4-bromonitrobenzene (vi) Benzyl alcohol to 2-phenyl ethanoic acid (vii) Ethanol to propane nitrile (viii) Aniline to chlorobenzene288 NCERT Class XII Chemistry Solutions (ix) 2-chlorobutane to 3, 4-dimethylhexane (x) 2-methyl-1-propene to 2-chloro-2-methylpropane (xi) Ethyl chloride to propanoic acid (xii) But-L-ene to n-butyliodide (xiii) 2-chloropropane to 1-propanol (xiv) Iso-propyl alcohol to iodoform (xv) Chlorobenzene to p-nitrophenol (xvi) 2-bromopropane to 1-bromopropane (xvii) Chloroethane to butane (xviii) Benzene to diphenyl (xix) tert-butyl bromide to iso-butyl bromide (xx) Aniline to phenyl isocyanide (i) Addition of HBr (peroxide effect); Replacement of —Br by —OH (ii) —OH is substituted by —Cl; then substitution by alkynyl group to form higher alkyne. (iii) Dehydrohalogenation by alc. KOH @-elimination), Addition of HBr (Markownikoff rule) (iv), Chlorination of —CH, group; Replacement of —Cl by —OH. (Vv) Bromination of benzene; Nitration of bromobenzene at p-position. (vi) Replacement of —OH by —Cl; then —Cl by —CN and at last by —COOH group. (vii) Replacement of —OH by +1 and then +1 by —CN. (vill) Diazotization; Formation of chlorobenzene. (i) Preparation of alkane with double number of C-atoms (Wurtz reaction) () Addition of HCI across the double bond (Markownikoff rule) (xi) Substitution of —Cl by CN; Acidic hydrolysis. (xii) Addition of HBr (peroxide effect or Anti-Markownikoff's rule); Substitution of —Br by —1. (xiii) Dehydrohalogenation (B-elimination); Addition of HBr (peroxide effect); Substituting —Br by —OH by aqueous KOH, (xiv) Oxidation of alcohol to ketone, lodoform reaction. (xv) Nitration replacement of —Cl by —OH; (xvi) Dehydrohalogenation (B-elimination); Addition of HBr (peroxide effect) (xvii) Wurtz reaction-Formation of hydrocarbon with double number of carbon atoms. (xix) Dehydrohalogenation; Addition of HBr (peroxide effect). (0) Carbylamine reaction Solution. HBr @ CH,—CH=CH, =>" Propene CHj—CH,—CH,—Br-XOH(a9), cp}, CH, —CH, OH 1-bromopropane Propan-1-olHaloalkanes and Haloarenes 289 SO,Cl. ld (ii) CHJCH,OH=——, cH,CH,c1 —SH=EN@ , CHCH,C=CH Ethanol Pyridine Chioroethane _ ~NaCl But-I-yne (iii) CH —CH, —CH, —Br KOH(@le) , op; CH=CH, ‘1-bromopropane Propene EBs CH;—FH—CHh Br q 2-bromopropane CHy CHACL CH,OH Cl,/ (Boil) tv) 2/ (Bo O KOH (aq) O Toluene ~» Benzyl chloride Benzyl alcohol Br Br “O Bro/FeBrs OQ HNOs/H2SOx O Toluene Bromobenzene 27) NO 4-bromonitro benzene CH,OH CHACL CH,CN PCl. 2 Oo ; O O Benzyl alcohol Benzyl Benzyl chloride cyanide CH,COOH 2H,0/H* = 2-phenyl acetic acid RedP/1, (vii) CH, —CH, OH ———*» CH, —CH, —I Ethanol Todoethane —KEN_, cH,—CH,—CN Propane nitrile290 NCERT Class XI. Chemistry Solutions NH, N,Cl a _ Diazotisation CuCVHC1 (wit) ‘NaNO2/HCI > Aniline Benzene Chlorobenzene diazonium chloride athe (ix) 2CH,—CH,— oa —leiyana}Dv etter, ‘Wurtz CH; reaction 2-chlorobutane CH,—CH, —CH— ccs CH,—CH, + 2NaCl cH, CH; 3, 4-dimethylhexane a HCL I (x) CH, —C=CH, —> CHy—G—CHy | CH, CH, 2-methyl propene 2-chloro-2-methy] propane (xi) CH, —CH,—c1-KCN_, cH, —cH,—C=N Ethyl chloride Ethy! nitrile (chloroethane) (cyanopropane) 2H,0/H* —— cH,—CH,—COOH Propanoic acid HBr ii) CH,CH,CH=CH ———"_> CH,CH,CH,CH,Br ae 0-0-8 oan beats but-l-ene —Nal_, CH.CH,CH,CHI ‘Acetone’ ~n:butyl iodide (xiii) CH, —CH—CH, KOHlaleliheat, oy, CH=CH, Propene a 2-chloropropane HBr, Peroxide KOH(aq), A CH,CH,CH,Br ——“2", cH.CH,CH,OH Anti-Markwonikoff 4. Nucleophilic * ‘+bromopropane Nucleophiic ~ -propanolHaloalkanes and Haloarenes 291 ° K,Cr,0,/H,SO. ll (xiv) CH, —CH— CH, a CH,;—C—CH, Propanone HH Iso-propyl alcohol NaOl, Cri, + CHj;COONa Todoform Sodium ethanoate ca a oH (xv) HNOs NaOH HaSOx 433K NO, NO p-nitrophenol (xvi) CH, —CH—CH, 20H, cH, CH=CH, | Propene Br 2-bromopropane HBr —_HEI_, cH,—CH,—CH, —Br __ 2-0-0“ -bromopropane T+ 2 Na + Cl|_CH,—CH, Dry eth Dares, CHy—CH,—CH,—CH Sea Butane +2NaCl (xviii) For answer, consult answer of Q. 11 (part x) ie CHy (xix) CH, —C—CH, KOH, cH,—C = CH, | Iso-butylene Br (or 2-methyl Tert. butyl bromide ‘1-propene) (or 2-bromo-2- methylpropane) Iso-butyl bromide (or 1-bromo-2-methyl Propane)292 NCERT Class XI|_ Chemistry Solutions NH N==C (x) + CHCl, +3KOH “a> + 3KCl +3H,0 Aniline Question 20. The treatment of alkyl chlorides with aqueous KOH leads to the formation of alcohols but in the presence of aleoholic KOH, alkenes are major products. Explain. {2G Ditference les in the made and extent of dissociation of KOH in the presence of different solvents, OH" is a good nucleophile while CH,0" is a strong base, Solution, In the presence of water, KOH dissociates completely intoOH ions. These are strong nucleophiles and produce alcohols from alkyl halides. Hydration of OH ions also takes place. So they are not able to abstract H* from p+C-atom. So alkenes are not formed. In alcoholic medium, solution also contains C;H,O, ethoxide ions in addition toOH ions. Being a stronger base, they abstract H* ion from B-C-atom giving rise to alkene. (Dehydrohalogenation). Question 21. Primary alkyl halide C;H9Br (4) reacted with alcoholic KOH to give compound (B). Compound (B) is reacted with HBr to give (C) which is.an isomer of (A). When (A) is reacted with sodium metal, it gives compound (D), CyH,g which is different from the compound formed when n-butyl bromide is reacted with sodium. Give the structural formula of(A) and write the equations for all the reactions. () Write the possible isomers of C,H,Br. (ii) Write the equation for the reaction of mbuty! bromide with sodium. (iii) Write the equation for all possible reactions and identify the compounds (A), (8), (C) and (D). Solution. Two possible isomers of C,H,Br are : CH;—CH, —CH,—CH,—Br CH, — CH,—Br iW) ay CHy () ay According to the question, compound (A) on reaction with sodium does not give the same product produced by n-butyl bromide. So (A) cannot be {i}. 2CHy—CH,—CH,—CH,—Br + 2Na Ether, n-butylbromide CH;—CH,—CH,—CH, —CH,—CH,—CH,—CH A-octane (not formed in the reaction) CoHHaloalkanes and Haloarenes 293 Now [II] must be the correct isomer. CHy—EH—cH,— Br KOH (alc) CH, Iso-butylbromide (1-bromo-2-methylpropane (4) H,—C =CH, + KBr + H,0 | CH, 2-methylpropene (B) ¥ ee ‘CH,—C—CH, | CH, 2-bromo-2 methylpropane © 2CH,—CH—CH,—Br + 2Na—Divether_, | ‘Wurtz reaction CH, (4) CHs— CH—CH;—CHy—CH—CHy | CH, cH, 2,5-dimethythexane (CoHye) (D) Question 22. What happens when (i) m butyl chloride is treated with alcoholic KOH. Gi) bromobenzene is treated with Mgin the presence of dry ether. (iii)-chlorobenzene is subjected to hydrolysis. (iv) ethyl chloride is treated with aqueous KOH. (v) methyl bromide is treated with sodium in the presence of dry ether. (vi) methyl chloride is treated with KCNP oS ( Dehydrohalogenation (B elimination) as alc. KOH is a dehydrohalogenating reagent. i) Formation of Grignard reagent. (ii) No reaction, due to double bond character in C—C! bond. (iv) (S2)—Clis replaced by —OH. (W) Wurtz reaction (vi) (Sy2) —Clis replaced by — CN.294 NCERT Class XIl_ Chemistry Solutions Solution. (i) But-1-ene is formed as a result of dehydrohalogenation. CH,—CH,— CH,— CH,—Cl + KOH —> n-butylchloride ale. CH,— CH,— CH =CH, + KC1+H,0 But-1-ene (i) Phenyl magnesium bromide is formed. Br MgBr Dry ether + Mg ———> Bromo- Phenyl magnesium benzene bromide (Grignard reagent) (iii) Chlorobenzene does not react or hydrolysed by NaOH. (iv) Ethanol is formed. CH,—CH,—Cl+ KOH —> Ethyl chloride (aq) CH,—CH;— OH + KC1+H,0 Ethanol (v) Ethane is formed as a result of Wurtz reaction. CH,—!Br + 2Na + Bri—cH, —Dvether_, Methy bromide CH;—CH; + 2NaBr Ethane (vi) Cyano methane is formed, CH,—Cl +KCN—+CH,;—C=N+ KCI Chloromethane Acetonitrile (Methyl chloride) Selected NCERT Exemplar Problems Short Answer Type Question 1. Aryl chlorides and bromides can be easily prepared by electrophilic substitution of arenes with chloride and bromide respectively in the presence of Lewis acid catalysts. But why does preparation of aryl iodides requires presence of an oxidising agent? Solution. Reactions of arenes with iodine are reversible in nature 5° aryl iodides are prepared in the presence of an oxidising agent such aS HNO,, HIO, etc., in order to oxidise the HI formed during iodination.Haloalkanes and Haloarenes 295 Question 2. Out of o and p- dichlorobenzene which one has the higher melting point and why? Solution. See Q. 18 of exercises. Question 3. Haloarenes are less reactive than haloalkanes and haloalkenes. Explain. Solution. Haloarenes are less reactive than haloalkanes and haloalkenes due to the following reasons : (i) Resonance effect In haloarenes, the electron pairs on halogen atom are in conjugation with x-electrons of the ring. It consists of the following resonating forms : Cl: C—C1 bond acquires a partial double bond character due to resonance. So this bond cleavage is difficult. (i) Hybridization of carbon atom in C—X bond Carbon atom being sp’ hybridized has greater s-character and more electronegativity in haloarenes. While in halloalkanes C-atom is sp’ hybridised and less electronegative. So C—X bond in haloarenes is shorter and stronger than it is in halo alkanes. (ii) Instability of phenyl cation In haloarenes, the phenyl cation is not stabilised by resonance. Question 4, Classify the following compounds as primary, secondary and tertiary halides. : @ L-bromobut-2-ene (ii) 4-bromo pent-2-ene i (ii) 2-bromo-2-methyl propane Solution. agra 2 () CHy—CH —CH—CH,Br i 1-bromobut-2-ene (primary 1) Ripe f s .al 9 23 (i) CH, —CH—CH=CH—CH, 4-bromo pent-2-ene (Secondary 29 Br sala (iii) CH,;—C—CH, | i CH, 2-bromo-2-methylpropane (Tertiary 39296 NCERT Class’XIl Chemistry Solutions Question 5. Write the structures and names of the compounds formed when compound ‘A’ with molecular formula C,H, is treated with Cl, in the presence of FeCls. Solution. CHg CHg i FeCly cs Toluene or o-chlorotoluene methyl benzene [Al p- chlorotoluene (C7He] Question 6. Identify the products A and B formed in the following reaction. CH;—CH,—CH=CH—CH, + HCI—> 4+ B Solution. CH;—CH,—CH=CH—CH, + HCl —> Pent-2-ene a area ale a CH,—CH,—CH, —CH— CH 2-chloropentane [A] + a $) wiidviewal Bete CH;—CH,—CH— CH,—CH; 3-chloropentane (B] Question 7. Which of the following compounds will have the highest melting point and why? Hy CHy CH cl cl cL. Cl Cl * 9G ; CH CHy CH f) tm) (i) Solution. I!) structure being more symmetrical, will have the highest meltiing point [For more details, consult answer of Question 2]Haloalkanes and Haloarenes 297 Question 8. Write down the structure and IUPAC name of neo-pentyl bromide. CH, 21 3 1 Solution, HyC —C—CH,—Br CH, or (CH)sC-CH,Br; 1-bromo-2,2-dimethylpropane Question 9. A hydrocarbon of molecular mass 72 g mol” gives a single monochloro derivative and two dichloroderivatives on photochlorination. Give the structure of the hydrocarbon. Solution. Hydrocarbon C,H,, has molecular mass 72 g mol", It has three isomers : (CH, —CH,—CH, —CH,—CH, n-pentane i) Cl, /UV light Sees CH,—CH,—CH, —CH,— CHCl 1-chloro pentane + CH) —CH,—CH, —CHCI— CH, 2-chloropentane [1] Forms 3 mono chloro derivatives, so it is not possible. CH; | CH,—CH,—CH—CH, —Sh/WV light 2-methylbutane [II] CH, sl cH,— cna ‘cH—¢H, + 2-chloro-3-methyl butane CH; t CH, ald lea cit, — tH, cH én, +¢H,— en, —CH, 1-chloro-3-methyl butane 1 2-chloro-2- methyl butane cH, -methylbutane {M] isomer is also not possible because it forms four-imono chloro derivatives.298 NCERT Class XI Chemistry Solutions CH; nie 1 al 3 ight Buea neta, Stam, Hee da CHg CH, - di 1-chloro-2,2-dimethylpropane faa — {monochicro derivative) So [III] structure is correct. Its two dichloro derivatives are CH, CHCl, la 2 H,C—C—CH,Cl HyC—C—CH, 4 4 CH,CL CHy 1,3-dichloro-2,2-dimethylpropane ‘tichloro-2,2gimethylpropane fay Question 10. Allyl chloride is hydrolysed more readily than m propyl chloride, why? Solution. Allyl chloride readily ionises to give allyl carbocation which is resonance stabilised. -a- CH, =CH—CH,—Cl == (cH, cH GH, Allyl chloride ° «> CH, —CH=CH)] The other compound n-propyl chloride {(n -C3H,Cl) is very little ionised since the n- propyl carbocation is not resonance stabilised. Therefore, ionisation leading to Sy1 reaction is quicker in allyl chloride than in n-propyl chloride. So allyl chloride is hydrolysed more readily than n-propyl chloride, Question 11. Why is it necessary to avoid even traces of moisture during the use of a Grignard reagent? 4 . 8 ee Solution. Grignard reagent is a polar molecule R—Mg X. So, Grignard reagents are highly reactive and react with water (a good source of proton) to give hydrocarbons, RMgX + H,O—> RH + Mg(OH)X So, traces of moisture must be avoided during the use of a Grignard reagent. Question 12. Write a test to detect the presence of double bond in # molecule, Solution, Presence of double bond can be detected by bromine water test. Addition of bromine in CCl, to an alkene results in discharge of reddish brown colour of bromine.Haloalkanes.and Haloarenes 299 H, H » cK + BR —SCl , pr—cH,—CH,—Br H_ (Brown) Vie-dibromide (colourless) Question 13. How will you obtain monobromobenzene from aniline? Solution. + =NCl Br Diazotisation Cu/HBr Ose “NaNO,/HCI O O Benzene Monobromo- diazonium benzene chloride Question 14. Predict the major product formed when HCI is added to iso-butylene. Explain the mechanism involved. CH, CH, 1 2 3 Solution. CH, —C=CH, —H"., cH, —¢—cH, Iso-butylene Markownt: ‘off rule a 2-chloro-2-methylproy le (Major produey re Mechanism. Hydrogen chloride: provides an electrophile, H*,which attacks the double bond to form 2 carbocations (a) less stable; (b) more stable. sided HyC—C=CH, + H—Cl Ht CHy CHy a 2 = H,C—CH—CH, + Cr HyC—C—CH, + CI (a) Less stable (b) More stable (primary carbocation) (secondary carbocation) (i) Carbocation (b) predominates because it is formed at a faster rate. (ii) Carbocation (b) reacts with CI” ion to form the major product 2-chloro-2- methylpropane.300 NCERT Class XII ‘Chemistry Solutions CH, CHy ake HyC —C—CH,;—+ H,C aie CH cl 2-chloro-2-methy! propane (Major product) Question 15. How can you obtain iodoethane from ethanol when no other iodine containing reagent except Nal is available in the laboratory? Solution. By heating ethanol with Nal in 95% phosphoric acid, we can obtain iodoethane. C,H,OH+ Nat —SS%HsPO4_, cH, + NaOH. . Long Answer Type Question 16. (i) Why are aryl halides less reactive towards nucleophilic substitution reactions than alkyl halides? (ii) How can we enhance the reactivity of aryl halides? Solution. (i) For answer consult exemplar problems, short answer type Q.3, (ii) Presence of electron withdrawing groups such as —NO,, —CN etc., at 0 and p- positions in the ring makes the bond cleavage easy. Greater the number of such groups, more is the reactivity of haloarene. For example, Introducing —NO, group at o- and p-positions enhances the activity of chlorobenzene. It can be understood by observing the decrease in temperature required with increase in the number —NO, group. a OH () NaOH, 623 K, 300 atm Gi) HY Chlorobenzene Phenol {NAOH 443 K 9) 4-nitrochlorobenzene 4a stiriHaloalkanes and Haloarenes 301 a OH NOz (i) NaOH, 368 K INOz —__r—_ Gi) H* > NO, NO, 2, 4-dinitrochloro 2, 4-dinitrophenol benzene ca OH N- ‘NO; OLN: On 2 warm 02 NO; HO NO2 NO, 2, 4, 6-trinitro- 2, 4, 6-trinitrophenol chlorobenzene (Picric acid)Chapter 1 1 Alcohols, Phenols and 1. 2. Pre PrpxeP 10. 11. 12. 13. 14. 15. 16. 17. Ethers Important Results Alcohols are prepared by hydration of alkenes in the presence of acid or by hydroboration-oxidation reaction. Aldehydes form alcohols (primary and secondary) with Grignard reagent whereas ketones give tertiary alcohols. Methanol is manufactured from water gas. Ethanol is manufactured by fermentation of carbohydrates. Phenols may be prepared from haloarenes, aryl sulphonic acids by substitution reactions and also from diazonium salts. Phenols are manufactured from cumene. Alcohols and phenols are acidic in nature. Phenolic —OH group is ortho an para directing in nature. Salicylic acid is prepared commercially from phenol by Kolbe's reaction. Reimer-Tiemann reaction is used to introduce —CHO group at o-position in phenol (formation of salicylaldehyde). Electron withdrawing groups in phenol increase its acidic strength and electron releasing groups decrease it. Solubility of alcohols in water decreases with increase in size of alkyl group. Dehydration of alcohols produces alkenes. 1°, 2° and 3° alcohols are distinguished by Victor Meyer and Lucas tests. Ethers can be prepared by dehydration of alcohols and Williamson synthesis. Cleavage of C—O bond in ethers takes place by hydroge? halides. In electrophilic substitution, the alkoxy group activates the aromatic ring and directs the incoming group to ortho and par positions.Alcohols, Phenols and Ethers 303 Intext Questions Question 1. Classify the following as primary, secondary and tertiary alcohols. fe @ CH; —¢—CH,OH (i) H,C=CH—CH,0H CH, OH | CH—CH, (ii) CH; —CH,—CH,— OH (iv) CH; | CH;—CH—CH, .CH=CH—C—OH ) Cr oH wi) Cr buy If —CH,OH group is present, alcohol is 1° (primary), if >CHOH group is present is 2° (secondary) and if >COH group is present, alcohol is 3°. So Classify on this basis. Solution. (i) Primary alcohol (i) Primary alcohol (ii) Primary alcohol (iv) Secondary alcohol (v) Secondary alcohol (vi) Tertiary alcohol Question 2. Identify allylic aleohols in the above examples. Following groups are included in allylic alcohols. i oH CH,=CH—CH,—OHCH,=CH—C—OH CH=CH toy Primary (1°) | i allyl alcohol = —c— Secondary (2°) Tertiary (3°) allyl alcohol allyl alcohol Solution. (ii) H,C—=CH—CH,OH en .CH==CH—C—OH Cr buy304 NCERT Class XII Chemistry Solutions Question 3. Name the following compounds according to the IUPAC system. CH,OH () CH;—CH,—CH —CH— CH—CH, | | CH,Cl CH, CH,OH | i) H}3C—CH— CH,—CH —CH— CH, SH; OH OH (ii) Br (i) HaC=CH —CH— CH,—CH,—CH, OH o) Shoe CH,0H CH,Br Prefix according to the C-chain; for alcohol add suffix —ol; for double bond —ene; tell the position of substituents, double bond and functional group (s).Then, given the name in the following manner. Name of substituent with position (in alphabetical order) + parent C:chain name + primary suffix (antiene etc.) + secondary suffix with position (for main functional group). Solution. 1 CH,OH 5 4 a (i) CH,—CH, a CH a CH, cH CH, ‘CH,OH 6 5 4 3 *h (i) CHC CHy CH, OH 2,5 dimethylhexan-1,3-di-ol