C2-Allens Made Chemistry Exercise {PART-1}

1 5 . Find the major product in the reaction the following : (i) HNO2 (ii) P–Ts–OH  H HO HO NH2 OAc O H (iv) HClO4 (iii) Me THF H 1 6 . Decreasing order of E.S.R. O O OH NH O H–N O NH NH O N NH (A) (B) (C) 1 7 . Complete the following equations : O  (A) H+ NaOH H3O O O O  + NaOH H3O CHO (B) 2-equivalent 1-equivalent (C) NaOH CHO 1 8 . Suggest the mechanism of the following reaction : OH CH3 C H (i) CH3–CH2–CH–CH3 H2SO4 C H CH3 trans CH3 NaOH CH2 (ii) CH3–C–Br alc. CH3 –C CH3 CH3 H OAC  CH3 C C CH3 (iii) CH3–CH–CH–CH3 H cis H

Br H (iv) –CH –CH2 NaOH –CH= CH2 alc. Br H (v) –CH–CH2–CH3 NaOH Ph H alc. C= C H CH3 19. Y CH3OH H2C—CHCH3 CH3OH X ; Here X and Y respectively are. CH3ONa H O 20. COOC2H5 C2H5ONa Z ; the product Z is. 21. COOC2H5 OH H3C CH3 14 CH2=CHCH2Cl 200°C P; Here P is. O H 2 2 . [X] ; most likely the compound [X] is. RR 23. H O O O ; the above intermediatory involves. OH 2 4 . Suggest the product of the reactions : H  /H NH CHCl3 NC NaOH (A) CH3–CH= CH2 (B) OO CH3 (B) O–H (C) CH3–C–O–C–CH3 + (D) + H–CCl3 NaOH C AlCl3 O  F (E) –C–H NaOH D N2Cl (F) (G) OH H P O2N —— C –CH3 NaOH OH (H)  Cl N OH

BRAIN STORMING SUBJECTIVE EXERCISE ANSWER KEY EXERCISE -4(B) 1 . (a) O2NCH2CH•• < CH2••< CH3CH••< C6H5CH••< (C6H5)2 C•• (b) + + << + + O O + OOO O+ OO OO (c) CH2—C—NH2 < CH2—C—CH2—OCH3< CH2—C—CH3 < CH2—C—H 2 . (i) 2 < 1 < 3 (ii) 3 < 1 < 2 3 . Conjugate base of benzene sulphonic acid has greater resonance stabilization than benzoate ion, hence benzene sulphonic acid is stronger acid than benzoic acid. PhSO – has three equivalent resonance structure, so more 3 stable.but PhCOO– has only two equivalent resonance structure, so less stable. 4 . B is stronger base than A. Here basic strength is controlled by –R effect of —NO . In B, due to steric inhibition 2 to resonance of —NO by two bulky tertiary butyl group, it is not decreasing basic strenght by —R effect, 2 hence B is stronger base than Al. 5. (a) Due to resonance in vinyl chloride, C—Cl bond acquire some double bond character while in chloroethane, C—Cl bond is pure, single sigma covalent bond. (b) Due to resonance in methyl vinyl ether, bond order of C—C is slightly reduced from two while in ethene C—C bond order is exactly 2. (c) Larger size of sulphur compared to oxygen gives greater acidity to CH SH. 3 (d) Lone-pair of electron in vinyl amine is involved partly in resonance delocalization and less avaiable for donation to a lewis acid, hence a weaker Lewis base. 6 . Lone pair of the basic nitorgen is fully available with ::N Basic nitrogen, i.e. not involved in delocalization while lone pair N Non-basic of non-basic nitrogen is part of aromatic delocalization. H Benzimidazole 7. (i) CH3NH2, (ii) H2N—C—NH2 (iii) PhNH2 NH 8. (i) Hc > Ha > Hb (ii) Ha : Conjugate base is aromatic 9. Acidic strength  stability of anion formed after removal of H+  number of e– withdrawing groups. 10. III > II > I 1 B.D.E.  stability of intermediate formed 1 9 . X : HOCH2 – CHCH3 and Y : CH2– CHCH3 OCH3 OCH3 OH

OH O H3C CH3 20. 21. COOC2H5 14CH2CH=CH2 OH 23. H O O 22.  R R

EXERCISE–05(A) PREVIOUS YEARS QUESTIONS 1 . In the following benzyl/allyl system R–CH=CH or R [AIEEE 2002] 2 (R is alkyl group) decreasing order of inductive effect is- (1) (CH3)3C– > (CH3)2CH– > CH3CH2– (2) CH –CH – > (CH ) CH– > (CH ) C– 32 32 33 (3) (CH ) CH– > CH CH – > (CH ) CH– 32 32 33 (4) None of these 2 . In the anion HCOO– the two carbon-oxygen bonds are found to be of equal length. What is the reason for it- [AIEEE 2003] (1) Electronic orbits of carbon atoms are hybridised (2) The C=O bond is weaker than the C–O bond (3) The anion HCOO– has two resonating structure (4) The anion is obtained by removal of a proton form the acid molecule 3 . The correct order of increasing basic nature for the bases NH , CH NH and (CH ) NH is-[AIEEE 2003] 3 32 32 (1) CH NH < NH < (CH ) NH 32 3 32 (2) (CH3)2NH < NH3 < CH3NH2 (3) NH < CH NH < (CH ) NH 3 32 32 (4) CH NH < (CH ) NH < NH 32 32 4 . Consider the acidity of the carboxylic acids- [AIEEE 2004] (i) PhCOOH (ii) o–NO C H COOH 26 4 (iii) p-NO2C6H4COOH (iv) m-NO2C6H4COOH which of the following order is correct for acidic strength- (1) i > ii > iii > iv (2) ii > iv > iii > i (3) ii > iv > i > iii (4) ii > iii > iv > i 5 . Which of the following is the strongest base- [AIEEE 2004] (1) NH2 (2) NHCH3 (3) NH2 (4) CH2NH2 CH3 [AIEEE 2004] O O [AIEEE 2004] [AIEEE-2005] 6 . Rate of the reaction R–C + Nu R–C + Z is fastest when Z is Z Nu (1) OCOCH (2) NH 3 2 (3) OC H (4) Cl 25 7 . Which one of the following does not have sp2 hybridised carbon (1) Acetamide (2) Acetic acid (3) Acetonitrile (4) Acetone 8 . Due to the presence of an unpaired electron, free radicals are (1) Chemically inactive (2) Chemically reactive (3) Cations (4) Anions

9 . The decreasing order of nucleophilicity among the nucleophiles [AIEEE-2005] (a) CH3–C–O— (b) CH O– (c) CN– (d) H C O O 3 3 S O–is O (1) (d) , (c), (b), (a) (2) (a), (b), (c), (d) (3) (c), (b), (a), (d) (4) (b), (c), (a), (d) 1 0 . Ter tiary alkyl halides are practically inert to substitution by SN2 mechanism because of [ A I E E E - 2 0 0 5 ] (1) unstability (2) insolubility (3) steric hinderance (4) inductive effect 1 1 . Among the following acids which has the lowest pk value- [AIEEE-2005] a [AIEEE-2005] (1) CH CH COOH (2) (CH ) CHCOOH 32 32 (3) HCOOH (4) CH COOH 3 1 2 . Amongest the following the most basic compound is- (1) p-nitro aniline (2) Acetanilide (3) Aniline (4) Benzylamine 1 3 . The increasing order of the rate of HCN addition to compounds A–D is [AIEEE-2006] (A) HCHO (B) CH3COCH3 (C) PhCOCH3 (D) PhCOPh (1) D < B < C < A (2) D < C < B < A (3) C < D < B < A (4) A < B < C < D 1 4 . The increasing order of stability of the following free radicals is [AIEEE-2006]   (1) (C6 H5 )3 C  (C6 H5 )2 C H  (CH3 )3 C  (CH3 )2 C H   (2) (C6 H5 )2 C H  (C6 H5 )3 C  (CH3 )3 C  (CH3 )2 C H   (3) (CH3 )2 C H  (CH3 )3 C  (C6 H5 )3 C  (C6 H5 )2 C H    (4) (CH 3 )2 C H  (CH3 )3 C  (C6 H5 )2 C H  (C6 H5 )3 C 1 5 . CH3Br + Nu–  CH3 – Nu + Br– The decreasing order of the rate of the above reaction with nucleophiles (Nu–) A to D is [AIEEE- 2006] [Nu– = (A) PhO–, (B) AcO–, (C) HO–, (D) CH3O–] (1) D > C > B > A (2) A > B > C > D (3) B > D > C > A (4) D > C > A > B 1 6 . The correct order of increasing acid strength of the compounds is [AIEEE-2006] (a) CH3CO2H (b) MeOCH2CO2H (c) CF3CO2H Me CO2 H (d) Me (1) d < a < c < b (2) d < a < b < c (3) a < d < c < b (4) b < d < a < c

OH O— Na+ 1 7 . + CHCl3 + NaOH   CHO The electrophile involved in the above reaction is [AIEEE-2006] (1) dichlorocarbene ( :CCl2)  (2) trichloromethyl anion (C Cl3 )  (3) formyl cation (C HO)  (4) dichloromethyl cation (C HCl2 ) 1 8 . Which one of the following is the strongest base in aqueous solution ? [AIEEE-2007] (1) Trimethylamine (2) Aniline (3) Dimethylamine (4) Methylamine 1 9 . The electrophile, E attacks the benzene ring to generate the intermediate  –complex. Of the following, which  –complex is of lowest energy? [AIEEE-2008] NO2 NO2 NO2 (1) + (2) + H (3) + H (4) + H E E E HE 2 0 . Arrange the carbanions, (CH3)3 C , CCl3 , (CH3)2 CH , C6H5 CH2 , in order of their decreasing stability :- (1) CCl3  C6H 5 CH2  (CH3 )2 CH  (CH3 )3 C [AIEEE-2009] (2) (CH3 )3 C  (CH3 )2 CH  C6H5 CH2  CCl3 (3) C 6H 5 CH 2  CCl3   C H 3  C  (CH3 )2 CH 3 (4) CH3 2 CH  CCl3  C6H5 CH2  CH3 3 C 2 1 . The correct order of increasing basicity of the given conjugate base (R=CH3) is :- [AIEEE-2010] (1) RCOO < HC  C < NH2 < R (2) RCOO < HC  C < R < NH2 (3) R < HC  C < RCOO < NH2 (4) RCOO < NH2 < HC  C < R [AIEEE-2011] 2 2 . The strongest acid amongst the following compounds is ? (1) CH3CH2CH(Cl)CO2H (2) ClCH2CH2CH2COOH (3) CH3COOH (4) HCOOH

2 3 . Ortho-Nitrophenol is less soluble in water than p– and m– Nitrophenols because :- [AIEEE-2012] (1) Melting point of o–Nitrophenol is lower than those of m– and p– isomers (2) o–Nitrophenol is more volatile in steam than those of m– and p– isomers (3) o–Nitrophenol shows Intramolecular H–bonding (4) o–Nitrophenol shows Intermolecular H–bonding 2 4 . Which of the following compounds are antiaromatic :- [AIEEE-2012(Online)] (I) .. (II) (III) O.. (IV) (V) (VI) – + (2) (II) and (V) (4) (V) and (VI) (1) (III) and (VI) (3) (I) and (V) [AIEEE-2012(Online)] 2 5 . In the following compounds : (I) (II) O (IV) N N (III) N H N H H the order of basicity is as follows : (1) IV > III > II > I (2) II > III > I > IV (3) I > III > II > IV (4) III > I > II > IV 2 6 . Dipole moment is shown by :- [AIEEE-2012(Online)] (1) trans-2, 3-dichloro- 2-butene (2) 1, 2-dichlorobenzene (3) 1, 4-dichlorobenzene (4) trans-1, 2-dinitroethene 2 7 . Among the following chloro-compound having the lowest dipole moment is :- [AIEEE-2012(Online)] (1) CH2Cl2 (2) CH3Cl Cl Cl Cl H (3) C=C (4) C=C H3C H H3C Cl 2 8 . In the below mentioned compounds the decreasing order of reactivity towards electrophilic substitution is : [AIEEE-2012(Online)] OCH3 CH3 (iii) CF3 (i) (ii) (iv) (1) (iii) > (i) > (iv) > (ii) (2) (iv) > (i) > (ii) > (iii) (3) (ii) > (iii) > (i) > (iv) (4) (i) > (ii) > (iii) > (iv) 2 9 . Among the following the molecule with the lowest dipole moment is :- [AIEEE-2012(Online)] [AIEEE-2012(Online)] (1) CHCl3 (2) CH2Cl2 (3) CCl4 (4) CH3Cl 3 0 . The most basic compound among the following is :- (1) Acetanilide (2) Benzylamine (3) p-Nitro aniline (4) Aniline

3 1 . Among the following the order of reactivity toward nucleophilic addition is :-[ A I E E E - 2 0 1 2 ( O n l i n e ) ] (1) HCHO > CH3CHO > CH3COCH3 (2) CH3CHO > HCHO > CH3COCH3 (3) CH3CHO > CH3COCH3 > HCHO (4) CH3COCH3 > CH3CHO > HCHO 3 2 . The order of stability of the following carbocations: ++ + is :- [JEE(MAIN)-2013] CH2=CH–CH2 ; CH3–CH2–CH2 ; CH2 III (4) III > I > II I II [JEE(MAIN)-2013] (1) III > II > I (2) II > III > I (3) I > II > III 3 3 . Arrange the following compounds in order of decreasing acidity : OH OH OH OH ; ;; OCH3 (IV) Cl CH3 NO2 (I) (II) (III) (1) II > IV > I > III (2) I > II > III > IV (3) III > I > II > IV (4) IV > III > I > II PREVIOUS YEAR QUESTIONS ANSWER KEY EXERCISE-05(A) Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Ans 1 3 3 4 4 4 3 2 4 3 34244 Que. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 Ans 2 1 3 2 1 1 1 3 4 3 21432 Que. 31 32 33 Ans 1 4 3

EXERCISE–05(B) PREVIOUS YEARS QUESTIONS 1 . Which one of the following has the smallest heat of hydrogenation per mole ? [IIT-93] [IIT-93] (A) 1–Butene (B) trans–2–Butene (C) cis–2–Butene (D) 1, 3–Butadiene 2 . What is the decreasing order of strength of bases OH, NH2, HCC, CH3–CH2 (A) CH3–CH2> NH2> HCC > OH (B) HCC > CH3–CH2 > NH2> OH (C) OH > NH2 > HCC > CH3–CH2 (D) NH2 > HCC > OH > CH3–CH2 3 . In the following compounds [IIT-96] OH OH OH OH NO2 CH3 NO2 I II III IV The order of acidity is - (B) I > IV > III > II (A) III > IV > I > II (D) IV > III > I > II (C) II > I > III > IV 4 . The formation of cyanohydrin from a ketone is an examples of - [IIT-98] [IIT-99] (A) Electrophilic addition (B) Nucleophilic addition (C) Nucleophilic substitution (D) Electrophilic substitution 5 . The most unlikely representation of resonance structure of p-nitrophenoxide ion is -     O–N=O O–N–O O=N=O O–N=O (A) (B) (C) (D) O O O O 6 . An aromatic molecule will not [IIT-99] [IIT-2000] (A) have 4n  electrons (B) have (4n + 2) electrons (C) be planar (D) be cyclic 7 . Amongst the following, the most basic compound is - (A) C6H5NH2 (B) p–NO2–C6H4NH2 (C) m–NO2–C6H4NH2 (D) C6H5CH2NH2

8 . Which of the following alkenes will react fastest with H2 under catalytic hydrogenation conditions [IIT-2001] R R R HR RR R H R (A) (B) (C) (D) H R HR HR 9 . The correct order of basicities of the following compounds is : [IIT-2001] NH CH3CH2NH2 (CH3)2NH O CH3–C , , CH3CNH2 NH2, 2 3 4 1 (A) 2 > 1 > 3 > 4 (B) 1 > 3 > 2 > 4 (C) 3 > 1 > 2 > 4 (D) 1 > 2 > 3 > 4 [IIT-2005] 1 0 . Which of the following is least stable :   (B) CH3–O=CH–CH=HC–CH2 (A) CH3–O=CH–CH–HC=CH2   (C) CH3–O–CH–CH–HC=CH2 (D) CH3–O–CH=CH–HC–CH2 1 1 . Among the following, the least stable resonance structure is - [IIT-2007]  O O (B)  N (A) N O O (C)  O (D)  O N N O O 1 2 . The major product of the following reaction is : [IIT-2008] Me Br F  PhS Na dimethylformamide NO2 Me SPh Me SPh Me Br Me SPh (A) F (B) F (C) SPh (D) SPh NO2 NO2 NO2 NO2

1 3 . The correct stability order for the following species is : [IIT-2008]     O (II) O (IV) (I) (III) (A) II > IV > I > III (B) I > II > III > IV (C) II > I > IV > III (D) I > III > II > IV 1 4 . Statement-I : p-Hydroxybenzoic acid has a lower boiling point that o-hydroxybenzoic acid. Because Statement-II : o-Hydroxybenzoic acid has intramolecular hydrogen bonding. [IIT 2003] (A) Statement-I is True, Statement-II is True ; Statement-II is a correct explanation for Statement-I (B) Statement-I is True, Statement-II is True ; Statement-II is NOT a correct explanation for Statement-I (C) Statement-I is True, Statement-II is False. (D) Statement-I is False, Statement-II is True. 1 5 . Statement-I : Bromobenzene upon reaction with Br2/Fe gives 1, 4-dibromobenzene as the major product. Because Statement-II : In bromobenzene, the inductive effect of the bromo group is more dominant than the mesomeric effect in directing the incoming electrophile. [IIT 2008] (A) Statement-I is True, Statement-II is True ; Statement-II is a correct explanation for Statement-I (B) Statement-I is True, Statement-II is True ; Statement-II is NOT a correct explanation for Statement-I (C) Statement-I is True, Statement-II is False. (D) Statement-I is False, Statement-II is True. 1 6 . Out of anhydrous AlCl3 and hydrous AlCl3 which is more suluble in diethyl ether ? Explain with reason. [IIT 2003] 1 7 . Match Ka values with suitable acid : [IIT 2003] Ka Acid (A) 3.3 × 105 (p) —COOH (B) 4.2 × 10–5 (q) Me— —COOH (C) 6.3 × 10–5 (r) Cl— —COOH (D) 6.4 × 10–5 (s) MeO— —COOH (E) 30.6 × 10–5 (t) O2N— —COOH

1 8 . Give resonating structures of following compound. [IIT 2003] [IIT 2004] OH 1 9 . Which of the following is more acidic and why ?   NH3 NH3 F (I) (II) 2 0 . The compound that does NOT liberate CO2, on treatment with aqueous sodium bicarbonate solution, is - [JEE ADVANCED 2013] (A) Benzoic acid (B) Benzenesulphonic acid (C) Salicylic acid (D) Carbolic acid (phenol) 2 1 . The hyperconjugative stbilities of tert-butyl cation and 2-butene, respectively, are due to (A) p (empty) and * electron delocalisations [JEE ADVANCED 2013] (B) * and  electron delocalisations (C) p (filled) and  electron delocalisations (D) p (filled)* and * electron delocalisations 2 2 . The total number of lone-pairs of electrons in melamine is [JEE ADVANCED 2013] PREVIOUS YEARS QUESTIONS ANSWER KEY EXERCISE -5(B) 1. (D) 2. (A) 3. (D) 4.(B) 5. (C) 6. (A) 7.(D) 8. (A) 13. (D) 14. (D) 15. (C) 9. (B) 10. (D) 11. (A) 12. (A) 16. Anhydrous AlCl is more soluble. 3 17. A-(s) ; B-(q) ; C-(p) ; D-(r) ; E-(t) ; 19. II is more acidic. 20. (D) 21. (A) 22. (6)



EXERCISE-01 CHECK YOUR GRASP SELECT THE CORRECT ALTERNATIVE (ONLY ONE CORRECT ANSWER) 1 . Alkaline earth metals (group 2 or IIA elements) differ from group 12 (or IIB) elements in the electronic configuration of their : (A) Antipenultimate shell (B) Innermost shell (C) Outermost shell (D) Penultimate shell 2 . The first ionization enthalpy of magnesium is lower than the first ionization enthalpy of : (A) Lithium (B) Sodium (C) Calcium (D) Beryllium 3 . Chemical A is used for water softening to remove temporary hardness. A reacts with Na2CO3 to generate caustic soda. When CO2 is bubbled through A, it turns cloudly. What is the chemical formula of A : (A) CaCO3 (B) CaO (C) Ca(OH)2 (D) Ca(HCO3)2 4 . The substance not likely to contain CaCO3 is : (A) Calcined gypsum (B) Sea shells (C) Dolomite (D) A marble statue 5 . A metal M readily forms water soluble sulphate MSO4, water insoluble hydroxide M(OH)2 and oxide MO which becomes inert on heating. The hydroxide is soluble in NaOH. The M is : (A) Be (B) Mg (C) Ca (D) Sr 6 . A chloride dissolves appreciably in cold water. When placed on a Pt wire in Bunsen flame, no distinctive colour is noted. Which cation could be present? (A) Be2+ (B) Ba2+ (C) Pb2+ (D) Ca2+ 7 . The hydroxide which is best soluble in water is : (A) Ba(OH)2 (B) Mg(OH)2 (C) Sr(OH)2 (D) Ca(OH)2 8 . What is X in the following reaction? MgCl2 + 2 H2O  X + 2 HCl + H2O (A) MgO (B) Mg (C) Mg(OH)2 (D) Mg(OH) Cl 9 . (Yellow ppt) T K2CrO4  X dil. HCl Y (Yellow ppt) + Z (pungent smelling gas) If X gives green flame test. Then, X is : (A) MgSO4 (B) BaS2O3 (C) CuSO4 (D) PbS2O3 1 0 . The correct statement is/are : (A) BeCl2 is a covalent compound (B) BeCl2 is an electron deficient molecule (C) BeCl2 can form dimer (D) The hybrid state of Be in BeCl2 is sp2 1 1 . The reaction of an element A with water produces combustible gas B and an aqueous solution of C. When another substance D reacts with this solution C also produces the same gas B. D also produces the same gas even on reaction with dilute H2SO4 at room temperature. Element A imparts golden yellow colour to Bunsen flame. Then A, B, C and D may be identified as : (A) Na, H2 NaOH and Zn (B) K, H2, KOH and Zn (C) K, H2, NaOH and Zn (D) Ca, H2, CaCOH2 and Zn 1 2 . An alkaline earth metal (M) gives a salt with chlorine, which is insoluble in water at room temperature but soluble in boiling water. It also forms an insoluble sulphate whose mixture with a sulphide of a transition metal is called 'lithopone'a white pigment. Metal M is : (A) Ca (B) Mg (C) Ba (D) Sr 1 3 . In electrolysis of NaCl when Pt electrode is taken then H2 is liberated at cathode while with Hg cathode it forms sodium amalgam: (A) Hg is more inert than Pt (B) More voltage is required to reduce H+ at Hg than at Pt (C) Na is dissolved in Hg while it does not dissolve in Pt (D) Conc. of H+ ions is larger when Pt electrode is taken

1 4 . The correct sequence of increasing covalent character is represented by – (A) BeCl2 < NaCl < LiCl (B) NaCl < LiCl < BeCl2 (C) BeCl2 < LiCl < NaCl (D) LiCl < NaCl < BeCl2 1 5 . The paramagnetic species is : (A) KO2 (B) SiO2 (C) TiO2 (D) BaO2 1 6 . The pair of amphoteric hydroxides is :- (A) Al(OH) , LiOH (B) Be(OH) , Mg(OH) 3 22 (C) B(OH) , Be(OH) (D) Be(OH) , Zn(OH) 32 22 1 7 . Maximum thermal stability is shown by (A) MgCO (B) CaCO (C) SrCO (D) BaCO 3 3 3 3 1 8 . Stable oxide is obtained by heating the carbonate of the element (A) Li (B) K (C) Na (D) Rb 1 9 . The stable superoxide is formed by the element (A) Li (B) Na (C) K (D) Ca 2 0 . The metallic lustre exhibited by sodium is explained by (A) diffusion of sodium ions (B) oscillation of loose electrons (C) excitation of free protons (D) existence of body centred cubic lattice 2 1 . A solution of sodium sulphate in water is electrolysed using inert electrodes. The products at the cathode and anode are respectively (A) H2 , O2 (B) O2 , H2 (C) O2 Na (D) O2, SO2 2 2 . The hydration energy of Mg2+ is greater than that of (A) Al3+ (B) Na+ (C) Be2+ (D) Mg3+ 2 3 . Calcium is obtained by the (A) electrolysis of molten calcium chloride (B) electrolysis of a solution of CaCl in water 2 (C) reduction of CaCl with carbon 2 (D) roasting of limestone 2 4 . The material used in photoelectric cells contains – (A) Cs (B) Si (C) Sn (D) Ti 2 5 . Four alkali metals A, B, C and D are having respectively standard reduction potentials as –3.05, –1.66, –0.40 and 0.80 V. Which one will be the most reducing agent ? (A) A (B) B (C) C (D) D 2 6 . Which of the following imparts violet colouration to the Bunsen burner non-luminous flame (A) NaCl (B) BaCl (C) CaCl (D) KCl 2 2 2 7 . Which one of the following is most basic ? (A) Al O (B) MgO (C) SiO (D) P O 23 2 25 2 8 . Molten sodium is used in nuclear reactors to (A) absorb neutrons in order to control the chain reaction (B) slow down the fast neutrons (C) absorb the heat generated by nuclear fission (D) extract radio-isotopes produced in the reactor

2 9 . Bone ash contains (A) CaO (B) CaSO 4 (C) Ca (PO ) 3 42 (D) Ca(H PO ) 2 42 3 0 . Which of the following does not illustrate the anomalous properties of Li ? (A) The m.p. and b.p. of Li are comparatively high (B) Li is much softer than the other I group metals (C) Li forms a nitride Li N unlike group I metals 3 (D) The ion of Li and its compounds are more heavily hydrated than those of the rest of the group 3 1 . Of the following the commonly used as a laboratory desicator is (A) Na CO 23 (B) CaCl 2 (C) NaCl (D) None of the above 3 2 . The increasing order of solubility is (A) CaCO .KHCO , NaHCO 33 3 (B) NaHCO , KHCO , CaCO 3 33 (C) KHCO3, NaHCO3, CaCO3 (D) CaCO , NaHCO , KHCO 3 33 3 3 . Which one of the following compounds gives methane on treatment with water ? (A) Al4C3 (B) CaC2 (C) VC (D) SiC 3 4 . Sodium loses its lustre on exposure to air due to formation of – (A) Na O, NaOH and Na CO 2 23 (B) Na O and NaOH 2 (C) Na O and Na CO 2 23 (D) NaOH and Na CO 23 3 5 . Which of the following hydride is covalent and polymeric :- (A) CaH 2 (B) BeH 2 (C) NaH (D) BaH 2 CHECK YOUR GRASP ANSWER KEY EXERCISE -1 Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Ans. D D C A A A A A B A,B,C A C D B A Que. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 Ans. D D A C B A BAAADB C CB 34 35 Que. 31 32 33 Ans. B D A A B

EXERCISE–02 BRAIN TEASERS SELECT THE CORRECT ALTERNATIVES (ONE OR MORE THEN ONE CORRECT NSWERS) 1 . Which of the following is incorrect? (A) Mg burns in air releasing dazzling light rich in UV rays. (B) CaCl2 · 6 H2O when mixed with ice gives freezing mixture. (C) Mg cannot form complexes (D) Be can form complexes due to its very small size. 2 . On dissolving moderate amount of sodium metal in liquid NH at low temperature, which one of the following 3 does not occur (A) Blue coloured solution is obtained. (B) Na+ ions are formed in the solution. (C) Liquid NH becomes good conductor of electricity. 3 (D) Liquid ammonia remains diamagnetic. 3 . The minimum equivalent conductance in fused state is shown by – (A) MgCl (B) BeCl (C) CaCl (D) SrCl 2 2 2 2 4 . The metal which cannot be produced on reduction of its oxide by aluminium is (A) K (B) Mn (C) Cr (D) Fe 5 . Magnesium on reaction with very dilute HNO gives 3 (A) NO (B) N O (C) H (D) NO 2 2 2 6 . The alkali metal that reacts with nitrogen directly to form nitride is (A) Li (B) Na (C) K (D) Rb 7 . Which of the following statement is/are false for alkali metals ? (A) Lithium is the strongest reducing agent (B) Na is amphoteric in nautre (C) Li+ is exceptionally small (D) All alkali metals give blue solution in liquid ammonia 8 . Amongst LiCl, RbCl, BeCl and MgCl , the compounds with the greatest and least ionic character respectively 22 are :- (A) LiCl, RbCl (B) RbCl, BeCl2 (C) RbCl, MgCl2 (D) MgCl2, BeCl2 (C) thiocarbonate (D) thiocyanate 9 . K CS can be called potassium 23 (A) sulphocyanide (B) thiocarbide 1 0 . Anhydrous MgCl2 can be prepared by heating MgCl2.6H2O (A) in a current of dry HCl gas (B) with carbon (C) until it fuses (D) with lime 1 1 . Oxygen ions structure in its peroxide, superoxide, ozonide : (A) O —, O 2, O —2 (B) O —2, O -—, O — (C) O —2, O—2, O — (D) O —, O —3, O —2 2 23 2 23 23 22 3

1 2 . In presence of iron, alkali metal react with liquid ammonia and form (A) Metal mixture + H2 (B) Iron metal mixture + H2 (C) Metal mixture (D) Metal amide + H2 1 3 . The ionic conductance of following cation in a given concentration are in the order (A) Li+ < Na+ < K+ < Rb+ (B) Li+ > Na+ > K+ > Rb+ (C) Li+ < Na+ > K+ > Rb+ (D) Li+ = Na+ < K+ < Rb+ 1 4 . Which of the following does not give an oxide on heating – (A) MgCO (B) Li CO (C) ZnCO (D) K CO 3 23 3 23 1 5 . On heating sodium metal in the current of dry ammonia leads to the formation of which gas– (A) NaNH (B) NaN (C) NH (D) H 2 3 3 2 1 6 . On allowing ammonia solution of s-block metals to stand for a long time, blue colour becomes fade. The reason is:- (A) Formation of NH3 gas (B) Formation of metal amide (C) Cluster formation of metal ions (D) Formation of metal nitrate 1 7 . When Na and Li placed in dry air we get :- (A) NaOH, Na O, Li O (B) Na CO , Na O , Li O 22 23 22 2 (C) Na O, Li N, NH 3 (D) Na O, Li O, Li N 23 223 1 8 . The hydride ion H– is stronger base than its hydroxide ion OH–. Which of the following reaction will occur if sodium hydride is dissolved in water:- (A) – + H2O  H3O+ – + H2O  OH– + H2 H(aq) (B) H(aq) – – (C) H + H2O  H2 + O2 (D) H + H2O  No reaction 1 9 . Which can not be used to generate H :– 2 (A) Al + NaOH (B) Zn + NaOH (C) Mg + NaOH (D) LiH + H O 2 2 0 . Only those elements of s-block can produce superoxides which have :- (A) High ionisation energy (B) High electronegativity (C) High charge density (D) Low ionisation potential 2 1 . Alum is the name used for all double salts having the composition M I SO .M III(SO ) .24H O. Where MIII 2 42 43 2 stands for Al+3, Cr+3, Fe+3, while MI stands for:- (A) Li+, Cu+, Ag+ (B) Li+, NH +, Na+ (C) Na+, K+, Rb+ (D) Ca+2, Mg+2, Sr+2 4 2 2 . Identify the correct statement - (A) Gypsum contains a lower percentage of Ca than plaster of paris (B) Gypsum is obtained by heating plaster of paris (C) Plaster of paris can be obtained by hydration of gypsum (D) Plaster of paris is obtained by partial oxidation of gypsum 23. In the reaction M + O  MO (super oxide) the metal is 2 2 (A) Li (B) Na (C) K (D) Ba

2 4 . Na+ and Ag+ differ in (A) Na CO is thermally stable while Ag CO decomposes into Ag, CO and O 23 23 22 (B) Ag+ forms complexes, Na+ does not (C) NaCl is water soluble, AgCl is insoluble (D) NaBr-yellow and AgBr pale yellow 2 5 . The stability order of oxide, peroxide and superoxide of alkali metal is (A) Normal oxide > super oxide > per oxide (B) Normal oxide > per oxide > super oxide (C) super oxide > per oxide > normal oxide (D) per oxide > normal oxide > super oxide 2 6 . Match list I with list II and choose the correct answer from the codes given below List I List II (A) NaNO (a) Baking soda 3 (b) Chile salt peter (c) Microcosmic salt (B) Na(NH )HPO (d) Washing soda 44 (C) NaHCO 3 (D) Na CO .10H O 23 2 Codes is : A BC D (A) a bc d (B) b ca d (C) c ab d (D) d ab c 2 7 . Which of the following statement is not correct (A) LiOH is amphoteric in nature (B) LiCl is soluble in pyridine (C) Li N is stable while Na N doesn't exist even at room temperature 33 (D) BeO is amphoteric in nature 2 8 . Which of the following statement is correct for s–block elements :- (A) Be has smallest atomic size in II A group (B) Li is most metallic (C) Mg impart red colour to the flame (D) Cs is most reducing in water 2 9 . Which of the following are ionic carbides? (A) CaC2 (B) Al4C3 (C) SiC (D) Be2C 3 0 . Which of the following groups of elements have chemical properties that are most similar : (A) Na, K, Ca (B) Mg, Sr, Ba (C) Be, Al, Ca (D) Be, Ra, Cs

3 1 . Which of the following statements are false? (A) BeCl2 is a linear molecule in the vapour state but it is polymeric in the solid state (B) Calcium hydride is called hydrolith (C) Carbides of both Be and Ca react with water to form acetylene (D) Oxides of both Be and Ca are amphoteric. 3 2 . The incorrect statement(s) is/are : (A) Mg cannot form complexes (B) Be can form complexes due to a very small atomic size (C) The first ionisation potential of Be is higher than that of Mg. (D) Mg forms an alkaline hydroxide while Be forms amphoteric oxides. 3 3 . Na2SO4 is water soluble but BaSO4 is insoluble because : (A) The hydration energy of Na2SO4 is higher than that of its lattice energy (B) The hydration energy of Na2SO4 is less than that of its lattice energy (C) The hydration energy of BaSO4 is less than that of its lattice energy (D) The hydration energy of BaSO4 is higher than that of its lattice energy 3 4 . BeCl2 + LiAlH4  X + LiCl + AlCl3 (A) X is lithium hydride (B) X is BeH2 (C) X is BeCl2 · 2H2O (D) X is LiH 3 5 . X CaCl2  CaCl2 + Y  ; the effective ingredient of X is : (A) OCl– (B) Cl– (C) OCl+ (D) OCl2– 3 6 . Which of the following substance(s) is/are used in laboratory for drying purposes? (A) Anhydrous P2O5 (B) Graphite (C) Anhydrous CaCl2 (D) Na3PO4 3 7 . If X and Y are the second ionisation potentials of alkali and alkaline earth metals of same period, then : (A) X > Y (B) X < Y (C) X = Y (D) X << Y 3 8 . X N2 ,  Y H2O Z (colourless gas) CuSO4 T (blue colour) : Then, substances Y and T are – (A) Y = Mg3N2 and T = CuSO4 · 5H2O (B) Y = Mg3N2 and T = CuSO4 · 4NH3 (C) Y = Mg(NO3)2 and T = CuO (D) Y = MgO and T = CuSO4 · 4NH3 3 9 . When K2O is added to water, the solution becomes basic in nature because it contains a significant concentration of : (A) K+ (B) O2– (C) OH– (D) O 2  2

40. (White ppt) D Na2CO3  A (inKa2cCetricOa4cid  B (Yellow ppt) dil. H2SO4 C(White ppt) If A is the metallic salt, then the white ppt. of D must be of (A) Magnesium oxide (B) Red lead (C) Barium carbonate (D) Calcium carbonate 4 1 . Which of the following compounds are paramagnetic in nature? (A) KO2 (B) K2O2 (C) Na2O2 (D) RbO2 4 2 . NaOH(Solid) + CO 200ºC X; product X is : (A) NaHCO3 (B) NaHCO2 (C) HCOONa (D) H2CO3 4 3 . EDTA is used in the estimation of : (A) Mg2+ ions (B) Ca2+ ions (D) Mg2+ ions but not Ca2+ ions (C) Both Ca2+ and Mg2+ ions 44. Na + Al2O3 hightemperature  X CwOa2teirn Y; compouind Y is : (A) NaAlO2 (B) NaHCO3 (C) Na2CO3 (D) Na2O2 4 5 . The compound(s) which have –O–O– bond(s) is/are : (A) BaO2 (B) Na2O2 (C) CrO5 (D) Fe2O3 4 6 . KO2 finds use in oxygen cylinders used for space and submarines. The fact(s) related to such use of KO2 is/are : (A) it produces O2 (B) It produces O3 (C) It absorbs CO2 (D) It absorbs both CO and CO2 4 7 . CsBr3 contains : (A) Cs–Br covalent bonds (B) Cs3+ and Br– ions (C) Cs+ and Br3– ions (D) Cs3+ and Br33– ions 4 8 . Fire extinguishers contain : (A) conc. H2SO4 solution (B) H2SO4 and NaHCO3 solutions (C) NaHCO3 solution (D) CaCO3 solution BRAIN TEASERS ANSWER KEY EXERCISE -2 Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Ans. C D B A C A BBCABD A DD 19 20 21 22 23 24 25 26 27 28 29 30 Que. 16 17 18 Ans. B D B C D C A C D B B A A A,B,D B,C 34 35 36 37 38 39 40 41 42 43 44 45 Que. 31 32 33 Ans. C,D, A A,C, B A A,C A B B C A,D C C C A,B,C Que. 46 47 48 Ans. A,C C B

EXERCISE–03 MISCELLANEOUS TYPE QUESTIONS TRUE / FALSE 1 . Magnesium is an essential constituent of chlorophyll, the green colouring matter of plants. 2 . Setting of cement is an endothermic process. 3 . Calcium bicarbonate is known in solid state. 4 . BeH is an ionic hydride. 2 5 . BeCO is thermally stable compounds. 3 6 . In the electrolysis of fused calcium hydride, hydrogen is liberated at cathode. 7 . MgCl .6H O on heating forms MgCl . 22 2 8 . Sodium when heated in excess of oxygen gives sodium oxide. 9 . In group IA of alkali metals, the ionisation potential decreases down the group. Therefore, lithium is a poorer reducing agent in gaseous medium. 1 0 . The softness of group IA metals increases down the group with increasing atomic number. FILL IN THE BLANKS 1 . Anhydrous magnesium chloride is obtained by heating the hydrated salt with................... 2 . Ca(OH) is..................... basic than Mg(OH) . 22 3 . CaH is comercially known as..................... 2 4 . Magnesium burn is air forming ..................... and ..................... 5 . Ba react with cold water ..................... Mg reacts with..................... while Be has..................... with boiling water. 6 . A standard solution of sodium hydroxide cannot be prepared by direct weighing because..................... 7 . Potassium bicarbonate cannot be prepared by solvay process because..................... 8 . Solution of alkali metals in liquid ammonia conducts electricity due to..................... MATCH THE COLUMN 1. Column-I Column-II (A) Hydrolith (p) Contain Ca (B) Nitrolium (q) Used as a fertilizer (C) Dolomite (r) Used to prepare H (D) Pearl's ash 2 (s) Contain potassium 2. Column-I Column-II (A) Solvay process (p) NaCl (q) Na O (B) Evolve CO  on heating 2 22 (C) aq. soln. is neutral towards litmus (r) NaHCO 3 (D) Oxone (s) Na CO 23

3. Column-I Column-II (A) Metal sulphate  metal oxide + SO + O (p) Ba 2 2 Sr (B) Metal cation + K CrO  yellow ppt (q) Na 24 Mg (C) Metal + NH (liquid) blue solution (r) 3 (s) (D) MCl + conc. H SO  white ppt. 2 24 ASSERTION & REASON QUESTIONS These questions contains, Statement I (assertion) and Statement II (reason). (A) Statement-I is true, Statement-II is true ; Statement-II is correct explanation for Statement-I. (B) Statement-I is true, Statement-II is true ; Statement-II is not a correct explanation for statement-I (C) Statement-I is true, Statement-II is false (D) Statement-I is false, Statement-II is true 1 . S t a t e m e n t - I : Li SO do not form double salt like alum. 24 Because S t a t e me n t - I I : Atomic size of Li is too small. 2 . S t a t e m e n t - I : NaCl when exposed in air it becomes wet. Because S t a t e me n t - I I : NaCl contains hygroscopic impurities like CaCl2, MgCl2 etc. 3 . Statem ent-I : Lithium is the weakest reducing agent among alkali metals. Because S t a t e me n t - I I : In alkali metals I.P. decreases down the group. 4 . S t a t e m e n t - I : BaCO is more soluble in HNO than in plain water. 33 Because Statement-II : Carbonate is a weak base and reacts with the H+ from the strong acid causing the barium salt to dissociate. 5 . S t a t e m e n t - I : BeCl fumes in moist air. 2 Because S t a t e me n t - I I : BeCl reacts with moisture of form HCl gas. 2 COMPREHENSION BASED QUESTIONS Comprehension # 1 A   B (oxide) + CO 2 B + HO  C 2 C + CO2  A (milky) C + NH Cl  D (gas) 4 D + H O + CO  E 22 E + NaCl  F F   Na CO + CO + HO 23 2 2 1 . A is : (A) Ca(HCO ) (B) CaCO 32 3 (C) CaO (D) Na CO 23

2 . B and C are : (A) CaO, Ca(OH) (B) Ca(OH) , CaCO 2 23 (C) CaCO , Ca(OH) (D) Ca(OH) , CaO 32 2 3 . D, E and F are : (A) NH , NH Cl, NH HCO 34 43 (B) NH , NH HCO , NaHCO 343 3 (C) NH HCO , Na CO , NaHCO 4 3 23 3 (D) None Comprehension # 2 Following given passage the five observation regarding alkali metals are mentioned. (i) On exposure to air, sodium hydroxide becomes liquid and after some time it changes to white powder. (ii) In water LiF is least soluble fluorides among fluorides of alkali metal, but its solublity increases as HF is added in aqueous solution. (iii) LiH more stable than NaH when heated separately (iv) When excess of Na S O solution is added to the FeCl solution an intense violet colouration is produced, 22 3 3 but violet colour disappeared shortly (v) Between Na+ and Ag+, Ag+ is stronger Lewis acid. 1 . The explanation of observation (v) is : (A) Because Na+ has inert gas configuration which has greater polarisation power (B) Because Ag+ has inert gas configuration which has greater polarisation power (C) Because Ag+ has pseudo inert gas configuration which has lesser polarisation power (D) Because Ag+ has pseudo inert gas configuration which has greater polarisation power 2 . The explanation for the observation (iv) is : (A) Initialy with FeCl3, Na2S2O3 produce an intense violet colour substance Fe2(S2O)3. But Fe2(S2O3)3 changes to Fe2+ & S4O62– on standing (B) Initially with FeCl3, is reduced to FeCl2 by Na2S2O3. FeCl2 so produced undergo unstable complex formation Fe(S2O3)34– which is violet in colour. (C) Initially with FeCl3, Na2S2O3 produce colloidal Fe which is violet in colour. After sometime, the colloidal suspension changes to the ppt of Fe. (D) There is no reaction 3 . As per observation (iii) LiH is more stable than NaH, because : (A) Due to small size of Li+, the lattice energy of LiH is greater (B) Due to greater size of H–, the lattice energy of LiH is greater (C) LiH is more covalent than NaH (D) Due to greater size of Na+, the lattice energy of NaH is greater. 4 . As per observation (ii) the solubility of LiF increases in the presence of HF, because : (A) The HF further ionises to H+ & F– (B) In the presence of HF, there will be a comon ion effect (C) In the presence HF, F– is converted to HF2 (D) All of the above

5 . The reaction for observation (i) can be explained as – (A) NaOH (S) H2O NaOH(aq) p; H2O N (B) NaOH (S) H2O NaOH(aq) H2O Na2O (S) (C) NaOH (S) H2O NaOH(aq) O2 / air Na2O (S) (D) NaOH (S) H2O NaOH(aq) CO2  Na2CO (S) Comprehension # 3 Na H2O a CO2 B SO2 C Na2S/I2 D Ag+/salt E (complex)   1 . The compound B and C are : (A) Na CO , Na SO 23 24 (B) NaHCO , Na SO 3 24 (C) Na CO , Na SO 23 23 (D) None of these 2 . The compound D is : (A) Na2SO4 (B) Na2S4O6 (C) Na2S2O5 (D) Na2S2O3 3 . Oxidation number of each 'S' atom in compound D : (A) + 2, + 2 (B) + 4, 0 (C) + 6, – 2 (D) + 5, – 1 Comprehension # 4 Alkali metals readily react with oxyacids forming corresponding salts like M CO , MHCO , MNO , M SO 23 3 3 24 etc. with evolution of hydrogen. They also dissolve in liquid NH but without the evolution of hydrogen. The 3 colour of its dilute solution is blue but when it is heated and concentrated then its colour becomes bronze. 1 . Among the nitrate of alkali metals which one can be decomposed to its oxide? (A) NaNO3 (B) KNO3 (C) LiNO3 (D) All of these 2 . Among the carbonates of alkali metals which one has highest stability? (A) Cs2CO3 (B) Rb2CO3 (C) K2CO3 (D) Na2CO3 3 . Which of the following statement about the sulphate of alkali metal is correct? (A) Except Li2SO4 all sulphate of other alkali metals are soluble in water (B) All sulphates of alkali metals except lithium sulphate forms alum. (C) The sulphates of alkali metals cannot be hydrolysed. (D) All of these

4 . Which of the following statement about solution of alkali metals in liquid ammonia is correct? (A) The solution have strong oxidizing properties. (B) Both the dilute solution as well as concentrated solution are paramagnetic in nature (C) Charge transfer is the responsible for the colour of the solution (D) None of these 5 . Which metal bicarbonates does not exist in solid state? (i) LiHCO3 (ii) Ca(HCO3)2 (iii) Zn (HCO3)2 (iv) NaHCO3 (v) AgHCO3 (A) (ii), (iii), (v) (B) (i), (ii), (iii) (C) (i), (ii), (v) (D) (ii), (iii), (iv) MISCELLANEOUS TYPE QUESTION ANSWER KEY EXERCISE -3  True / False 1. T 2. F 3. F 4. F 5. F 6. F 7. F 8. F 9. T 10. T  Fill in the Blanks 1. Dry HCl 2. More 3. Hydrolyth 4. Mgo, Mg N 5. Vigrowly, slowly, no action 32 6. Absorb moisture & CO from atmosphere 7. Ammonated e– 2  Match the Column 1. (A) p,r ; (B) p,q ; (C)  p ; (D) s 2. (A) r,s ; (B) r,s ; (C)  p ; (D) q 3. (A) p,q,s ; (B) p,q; (C)  p,q,r,s ; (D) p,q  Assertion - Reason Questions 1. A 2. A 3. D 4. C 5. A  Comprehension Based Questions Comprehension #1 : 1. (B) 2. (A) 3. (B) Comprehension #2 : 1. (D) 2. (A) 3. (A) 4. (C) 5. (D) Comprehension #3 : 1. (C) 2. (D) 3. (C) Comprehension #4 : 1. (C) 2. (A) 3. (D) 4. (D) 5. (A)

EXERCISE–04 [A] CONCEPTUAL SUBJECTIVE EXERCISE 1 . Explain the following : (i) The reaction between marble and dilute H SO is not used to prepare carbon dioxide. 24 (ii) Lime water becomes turbid on passing CO though it, but becomes clear when more CO is passed. 22 (iii) Alkaline earth metals have higher melting points than alkali metals. (iv) Beryllium does not exhibit a covalency beyond 4. 2 . PbO is soluble in NaOH and also in HCl. What does it reflect about the nature of PbO ? 22 3 . What happens when : (i) Hot and concentrated caustic soda solution reacts with iodine. (ii) White phosphorus is heated with caustic soda. (iii) Excess of caustic soda reacts with zinc sulphate solution. (iv) Excess of NaOH is added to AlCl solution. 3 4 . Write balanced equation for reaction between (i) Na2O2 and water (ii) KO2 and water (iii) Na2O2 and CO2 5 . Element A bruns in nitrogen to give an ionic compound B. Compound B reacts with water to give C and D. A solution of C becomes milky on bubbling carbon dioxide . Identify A, B, C and D. 6 . In water LiF is least soluble fluoride among fluorides of alkali metals, but its solubility increases as HF is added in aqueous solution, why? 7 . What happens when CuSO (aq.) is treated with excess of Na S O solution? 4 22 3 8 . Arrange the following in order of increasing .............. (i) Thermal stability BeSO4, MgSO4, CaSO4 (ii) Polarising power Be2+, Mg2+, Ca2+ (iii) Solubility in H2O Be(OH)2, Mg(OH)2, Ca(OH)2 (iv) Covalent nature BeCl2, MgCl2, CaCl2 (v) Hydrolysis nature BeCl2 MgCl2, CaCl2 (vi) Lattice energy CaF2, MgF2, BaF2 (vii) Hydration energy Be2+, Mg2+, Ba2+ (viii) Solubility in water MgF2, BaF2, BeF2 (ix) Basic nature Be, Mg, Ca, Sr 9 . Hydrogen reacts with a metal (A) to give an ionic hydride (B). The metal (A) gives brick red colour with bunsen flame. The hydride formed is commonly known by its trade name. The compound (B) on treating with water gives back H2 and (C). Identify (A), (B) and (C).

CONCEPTUAL SUBJECTIVE EXERCISE ANSWER KEY EXERCISE -4(A) 1 . (i) Insoluble CaSO is formed which deposists on the surface of marble and prevents further action of dilute 4 H SO , so the evolution of CO ceases after sometime. 24 2 (ii) Insoluble CaCO is first precipitated which dissolves in excess of CO due to the form of Ca(HCO ) . 3 2 32 Ca(OH) + CO  CaCO + H O; 2 2 3 2 (Insoluble) CaCO + HO + CO  Ca(HCO ) 3 2 2 32 (Soluble) (iii) Metallic bonding is much stronger in alkaline earth metals as two electrons are present in valence shell. (iv) The outermost energy shell in beryllium is the second. It cannot accommodate more than 8 electrons and hence a covalency limit 4 cannot be exceeded. 2 . PbO are amphoteric nature 2 PbO + 4HCl  PbCl + 2H O 2 4 2 PbO + 2NaOH  Na PbO + H O 2 23 2 3 . (i) 3I + 6NaOH  5NaI + NaIO + 3H O (ii) P + 3NaOH + 3H O  PH +3NaH PO 2 3 2 4 2 3 22 (iii) ZnSO + 2NaOH   Zn(OH) +Na SO 4 (iv) AlCl + 3NaOH  Al(OH) +3NaCl 4 22 3 3 ppt ppt Zn(OH) +2NaOH  Na [ Zn(OH ) 4 Al(OH) + NaOH  Na[Al(OH) ] 2 2 3 4 or NaAlO 2 4 . (i) Na O + 2H O  2NaOH + HO 22 2 22 (ii) KO + HO  KOH + HO + O 2 2 22 2 (iii) 2Na O + 2CO  2Na CO + O 22 2 23 2 5 . A = Ca, B = Ca N C = Ca(OH) D = NH 32 2 3 6 . In presence of HF, F– is converted into bifluoride ion HF2–, allowing further dissolution of solid LiF. 7. CuSO + Na S O   Cu S O 3 + Na SO 4 22 3 24 2 2CuS O + Na S O    C u S O + Na S O 23 22 3 24 6 23 Cupric thiosulphate 3Cu2S2O3 + 2Na2S2O3  Na4[Cu6(S2O3)5] Sodium cuprothiosulphate. 8 . (i) BeSO < MgSO < CaSO (ii) Ca2+ < Mg2+ < Be2+ 4 44 (iii) Be (OH) < Mg(OH) < Ca(OH) (iv) CaCl < MgCl < BeCl 22 2 22 (v) CaCl < MgCl < BeCl 2 22 (vi) BaF < CaF < MgF 2 (vii) Ba2+ < Mg2+ < Be2+ 22 (ix) Be < Mg < Ca < Sr (viii) BaF < MgF < BeF 9 . (i) Ca gives brick red colour to flame 2 22 (ii) Ca + H  CaH (hydrolith, trade name) 2 2 (A) (B) (iii) CaH + 2H O  Ca(OH)2 + 2H 2 2 2 (B) (C)

EXERCISE–04 [B] BRAIN STORMING SUBJECTIVE EXERCISE 1 . When a gas (A) is passed through dry KOH at low temperature, a deep red coloured compound (B) and a gas (C) are obtained. The gas (A) on reaction with but-2-ene followed by treatment with Zn/H2O yields acetaldehyde. Identify (A), (B) and (C) 2 . A compound (X) imports a golden yellow flame and shows the following reactions: (i) Zinc powder when boiled with a concentrated aqueous solution of (X) dissolves and hydrogen is evolved. (ii) When an aqueous solution of (X) is added to an aqueous solution of stannous chloride, a white precipitate is obtained first which dissolves in excess of solution of (X). Identify (X) and write equations at step (i) and (ii). 3 . A white solid is either Na2O or Na2O2. A piece of red litmus paper turns white when it is dipped into a freshly made aqueous solution of the white solid. (i) Identify the substance and explain with balanced equation (ii) Explain what would happen to the red litmus if the white solid were the other compound 4 . (A) is binary compound of a univalent metal. 1.422 g of (A) reacts completely with 0.321 g of sulphur in an evacuated and sealed tube to give 1.743 g of a white crystalline solid (B) that formed a hydrated double salt (C) with Al2(SO4). Identify (A),(B) and (C). 5 . Element (M) is a shiny and highly reactive metal (melting point 63ºC) and element (X) is a highly reactive non-metal (melting point – 7.2ºC). They react to form a compound with the empirical formula MX, a colourless, brittle solid that melts at 734ºC. When dissolved in water or when in the molten state, the substance conduct electricity. When chlorine gas is bubbled through an aqueous solution containing (MX), a reddish-brown liquid appears and and Cl– are formed. From these observations, identify M and X. 6 . Name an element which is invariable bivalent and whose oxide is soluble in excess of NaOH and its dipositive ion has a noble gas core. 7 . Out of the elements marked A, B, C, D, E, F, G and H: (a) Which form superoxide? (b) Which form thermally stable carbonate? (c) Which forms strongest base? (d) Which show diagonal relationship? (e) Which forms amphoteric oxide? AB CD EF GH

CONCEPTUAL SUBJECTIVE EXERCISE ANSWER KEY EXERCISE -4(B) 1 . The gas (A) on treatment with but-2-ene followed by treatment with Zn/H O yields acetaldehyde and thus (A) is 2 ozone (i) O + CH — CH=CH–CH  C H — CH—O—CH—CH3 3 3 3 3 OO Mono ozonide 2CH3CHO H2O Zn Acetaldehyde (ii) 5O3 + 2KOH 2KO3 + H2O(g) + 5O2 (A) Potassium ozonide (C) Deep red (B) 2 . (i) Zn + 2NaOH  Na2ZnO2 + H2 (X) (ii) (X) is also justified by step 2 reactions: 2NaOH + SnCl2  Sn(OH)2 + 2NaCl (X) White ppt. Sn(OH)2 + 2NaOH  Na2SnO2 + 2H2O (Excess) Soluble (X) 3 . (i) Na O + 2H O  2NaOH + HO + [O] 22 2 2 [O] + Litmus  White (bleaching) Red (ii) The other compound Na O will give NaOH on dissolution in water. The red litmus will turn to blue. 2 4. 2KO + S  K SO Al2(aSqO. 4)3K2SO4 · Al (SO ) · 24H O 2 24 2 43 2 (A) (B) (C) 5 . The given facts suggest M to be potassium (K) and (X) to be bromine (Br ). 2 2K + Br  2KBr 2 (Ionic solid with m. pt. 734°C) 6. Be 7 . (a) E and G (b) C, E and G (c) G (d) A and D (e) B

EXERCISE–05 (A) PREVIOUS YEARS QUESTIONS 1. A metal M readily forms its sulphate MSO4 which is water soluble. It forms oxide MO which becomes inert on heating. It forms insoluble hydroxide which is soluble in NaOH. The metal M is:- [AIEEE-2002] (1) Mg (2) Ba (3) Ca (4) Be 2. KO2 is used in space and submarines because it [AIEEE-2002] (1) Absorbs CO2 and increase O2 concentration (2) Absorbs moisture (3) Absorbs CO2 (4) Produces ozone 3. In curing cement plasters, water is sprinkled from time to time. This helps in :- [AIEEE-2003] (1) Hydrating sand and gravel mixed with cement (2) Converting sand into silicate (3) Developing interlocking needle like crystals of hydrated silicates (4) Keeping it cool 4. The solubilities of carbonates decreases down the magnesium group due to decrease in- [AIEEE-2003] (1) Inter-ionic attraction (2) Entropy of solution formation (3) Lattice energy of solids (4) Hydration energy of cations 5. The substance not likely to contain CaCO3 is :- [AIEEE-2003] (1) Sea shells (2) Dolomite (3) A marble statue (4) Calcined gypsum 6. One mole of magnesium nitride on reaction with excess of water gives :- [AIEEE-2004] (1) Two mole of HNO3 (2) Two mole of NH3 (3) 1 mole of NH3 (4) 1 mole of HNO3 7. The ionic mobility of alkali metal ioins in aqueous solution is maximum for :- [AIEEE-2006] (1) Rb+ (2) Li+ (3) Na+ (4) K+ 8. Which of the following on thermal-decomposition yields a basic as well as an acidic oxide ? [AIEEE -20 12 ] (1) NH4NO3 (2) NaNO3 (3) KClO3 (4) CaCO3 9. Fire extinguishers contain H2SO4 and which one of the following :- [AIEEE-2012 (Online)] (1) CaCO3 (2) NaHCO3 and Na2CO3 (3) Na2CO3 (4) NaHCO3 10. Which one of the following will react most vigorously with water ? [AIEEE-2012 (Online)] (1) Li (2) K (3) Rb (4) Na 11. A metal M on heating in nitrogen gas gives Y. Y on treatment with H2O gives a colourless gas which when passed through CuSO4 solution gives a blue colour, Y is :- [AIEEE-2012 (Online)] (1) NH3 (2) MgO (3) Mg3N2 (4) Mg(NO3)2 PREVIOUS YEAR QUESTIONS s-BLOCK EXERCISE-05(A) 9 10 11 Q. 1 2 3 4 5 6 7 8 333 A. 4 1 3 4 4 2 1 4

EXERCISE–05 (B) PREVIOUS YEARS QUESTIONS 1 . Which process is used in the extractive metallurgy of Mg : (A) Fused salt electrolysis (B) Self reduction (C) Aquaous solution electrolysis (D) Thermite reduction 2 . A sodium salt on treatment with MgCl2 gives white precipitate only on heating. The anion of sodium salt is : (A) H CO – (B) C O 2 – (C) N O – (D) SO 2 – 3 3 3 4 3 . The following compounds have been arranged in order of their increasing thermal stabilities. Identify the correct order: (IIT 96) (I) K2CO3 (II) MgCO3 (III) CaCO3 (IV) BeCO3 (A) I < II < III < IV (B) IV < II < III < I (C) IV < II < I < III (D) II < IV < III < I 4 . Property of the alkaline earth metals that increases with their atomic number is – (IIT 97) (A) Ionisation energy (B) Solubility of their hydroxides (C) Solubility of their sulphates (D) Electronegativity 5 . The characteristics of solid sodium chloride are (REE 96) (1) Brittle (2) Ionic (3) Covalent (4) Non-conductor (A) 1 & 2 (B) 3 & 4 (C) 1, 2, & 4 (D) 1, 3, & 4 6 . Which of the following are not amphoteric – (REE 97) (1) Be(OH) (2) Sr(OH) (3) Ca(OH) (4) Al(OH) 2 2 2 3 (A) 1 & 3 (B) 2 & 3 (C) 1 & 4 (D) 2 & 4 7 . Highly dilute solution of sodium in liquid ammonia : (i) Shows blue colour (ii) Exhibits electrical conducitive (iii) Produces sodium amide (iv) Produces hydrogen gas (A) (i), (ii), (iii) (B) (i), (ii) (C) (iii), (iv) (D) Only (ii) 8 . Which of the following hydrides is not ionic (A) CaH2 (B) BaH2 (C) SrH2 (D) BeH2 9 . The compound(s) formed upon combustion of sodium metal in excess air is (are) [JEE 2009] (A) Na2O2 (B) Na2O (C) NaO2 (D) NaOH ASSERTION & REASON QUESTIONS (A) Statement–I is true, statement–II is true ; statement–II is a correct explanation for statement–I (B) Statement–I is true, statement–II is true ; statement–II is NOT a correct explanation for statement–I (C) Statement–I is true, statement–II is false (D) Statement–I is false, statement–II is true 1 . Statement–I : Alkali metals dissolve inz liquid ammonia to give blue solutions. (IIT 2007) Because : Statement–II : Alkali metals in liquid ammonia give solvated species of the type [M(NH )n]+ (M = alkali metals) 3

SUBJECTIVE QUESTIONS 1 . Identify the following: Na CO SO2 A Na2CO3 B Elemental S C I2 D 23 Also mention the oxidation state of S in all the compounds. 2 . Beryllium chloride shows acidic nature in water or why BeCl is easily hydrolysed? 2 3 . The crystalline salts of alkaline earth metals contain more water of crystallisation than the corresponding alkali metal salts, why? 4 . Arrange the following sulphates of alkaline earth metals in order of their decreasing thermal stability. BeSO4, MgSO4, CaSO4, SrSO4. 5 . Why the solubility of calcium acetate decreases while that of lead nitrate increases with increase in temperature. 6 . Why magnesium is not precipitated from a solution of its salt by NH OH In the presence of NH Cl. 44 PREVIOUS YEARS QUESTIONS ANSWER KEY EXERCISE -05(B)  1. (A) 2. (A) 3. (B) 4. B 5. C 6. B 7. B 8. D 9. A, B  Assertion - Reason Questions 1. B  Subjective Questions 1 . A = NaHSO , Oxidation state of S = + 4 3 B = Na SO , Oxidation state of S = + 4 23 C = Na S O , Oxidation state of S = + 6 & – 2 22 3 D = Na S O , Oxidation state of S = + 5 & 0 24 6 2. BeCl is a salt of weak base Be(OH) and strong acid HCl and thus undergoes hydrolysis to result in an 22 acidic solution in water. BeCl + 4H O Hydration [Be(H O) ]2+ + 2Cl– 22 24 3. Alkaline earth metals have smaller size and more nuclear charge. 4. SrSO > CaSO > MgSO > BeSO 44 44 5. (CH COO) Ca shows exothermic dissolution whereas Pb(NO ) show endothermic dissolution. 32 32 6. The dissociation of NH4OH (a weak electrolyte) is suppressed in presence of NH4Cl due to common ion effect. Thus, [OH–] in solution becomes low. The ionic product of concentrations of Mg2+ and OH– ions does not exceed the solubility product of Mg(OH) and thus Mg(OH) is not precipitated. 22

EXERCISE-01 CHECK YOUR GRASP SELECT THE CORRECT ALTERNATIVE (ONLY ONE CORRECT ANSWER) 1 . The smallest alkane which can show optical isomerism possesses - (A) 5 carbons (B) 6 carbons (C) 7 carbons (D) 8 carbons 2 . The appropriate reagent for the transformation O CH3 is- HO HO (A) Zn(Hg)/HCl (B) NH2NH2,OH– (C) H2/Ni (D) NaBH4 3 . The relative reactivity of 1ºH, 2ºH and 3ºH in bromination reaction has been found to be 1 : 82 : 1600 respectively. In the reaction - CH3 CH3 CH3 hv CH3–C–CH3+CH3–CH–CH2–Br CH3–CH–CH3 (excess) + Br2 Br (A) (B) the percentage yields of the products (A) and (B) are expected to be - (A) 99.4%, 0.6% (B) 50%, 50% (C) 0.6%, 99.4% (D) 80%,20% 4 . The least reactive alkane towards free-radical substitution reactions is- (A) CH4 (B) (CH3)3CH (C) CH3CH3 (D) CH3CH2CH3 5 . For the reaction CH2OH H2SO4 the major product is : (A) CH2 (B) CH3 (C) (D) 6 . Propene is allowed to react with B2D6 and the product is treated with acetic acid. The final product obtained is - (A) 1–deuteriopropane (B) 2–deuteriopropane (C) 1–deuteriopropene (D) 2–deuteriopropene 7 . 1–Methylcyclohexene is allowed to react with B2H6. The product is then treated with H2O2 and NaOH. The reaction is - 1.B2H6 (B) 2–methylcyclohexanol 2.H2O2/OH– (D) cyclohexanol CH3 The product formed is (A) 1–methylcyclohexanol (C) methylcyclohexane

8 . Propene on reaction with ICl produces mainly - (A) 1–chloro–2–iodopropene (B) 2–chloro–1–iodopropane (C) (±)–2–chloro–1–iodopropane (D) (±)–1–chloro–2–iodopropane 9 . Consider the reaction CH3 + OH– Heat CH3CH2CH2–N–CH2CH3 CH3 Which of the following is formed in major amount (A) CH2=CH2 (B) CH3CH=CH2 (C) Both (A) and (B) in equal amount (D) None, as no reaction takes place 1 0 . In the addition of HBr to propene in the absence of a peroxide, the first step involves the addition of - (A) H+ (B) Br– (C) H (D) Br 1 1 . In the reaction CH3CH2CH=CH21.Hg2(.ONAaBc )D24,H2O the product obtained is - (A) CH3CH2CHOHCH2D (B) CH3CH2CHDCH2OH (C) CH3CH2CD(OH)CH3 (D) CH3CH2CD2CH2OH 1 2 . The major product obtained in the reaction of 1,3-Butadiene with HCl (1 mole) at a higher temperature (100ºC or above) is (A) 3,4–dichloro–1–butene (B) 3–chloro–1–butene (C) 1–chloro–2–butene (D) 2–chloro–2–butene 1 3 . An optically active hydrocarbon (X) on catalytic hydrogenation gives an optically inactive compound (Y), C6H14. The hydrocarbon (X) is- (A) 3–methyl–1–pentene (B) 3–methyl–2–pentene (C) 2–ethyl–1–butene (D) 3–methylcyclopentene 1 4 . The addition of HCl to 1–phenylpropene gives- (A) C6H5CHClCH2CH3 (B) C6H5CH2CHClCH3 (C) C6H5CH2CH2CH2Cl (D) C6H5CH(CH3)CH2Cl 1 5 . The reduction of 4–octyne with H2 in the presence of Pd/CaCO3 – quinoline gives- (A) trans–4–octene (B) cis–4–octene (C) a mixture of cis–and trans–4–octene (D) a completely reduced product C8H18 1 6 . The ease of formation of free radicals follows the order -   (A) 3º  2º  1º  C H3 (B) C H3  1º  2º  3º   (C) 1º  2º  3º  C H3 (D) 2º  1º  3º  C H3 1 7 . Which of the following has the lowest heat of hydrogenation per mole - (A) cis–2–Butene (B) trans–2–Butene (C) 1–Butene (D) 1,3–Butadiene 1 8 . The intermediate formed during the addition of HCl to propene in the presence of peroxide is-     (A) CH 3 C HCH2Cl (B) CH 3CH 2 C H2 (C) CH 3 C HCH3 (D) CH 3CH2 C H2

1 9 . The order of stability of the alkenes R2C=CR2, R2C=CHR, R2C=CH2, RCH=CHR, and RCH=CH2 I II III IV V is - (A) I > II > III > IV > V (B) I = II > III > IV > V (C) II > I > IV > III > V (D) V > IV > III > I > II 2 0 . Which of the following will not react with an ammonical silver nitrate solution : (A) CH3CCH (B) (CH3)2CH–CH (C) CH3CCCH3 (D) HCCH CHECK YOUR GRASP ANSWER KEY EXERCISE -1 Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 Ans. C B A A C B B B A A A C A A B A D C A C

EXERCISE–02 BRAIN TEASERS SELECT THE CORRECT ALTERNATIVES (ONE OR MORE THEN ONE CORRECT ANSWERS) 1 . Which of the following reactions will result in the formation of a chiral centre in the product - (A) CH3CH=CHCH3+HBr  (B) CH3CH=CH2+HOBr  (C) CH3CH2CH=CH2+HBr H2O2  (D) CH3CH2CH=CH2+HBr  2 . Propene on reaction with N–bromosuccinimide in CCl4 produces - (A) 1, 2–dibromopropane (B) 3–bromopropene (C) 1–bromopropene (D) 2–bromopropene 3 . cis–2–Butene on reaction with Br2 in CCl4 produces mainly - (A) 1–bromo–2–butene (B) 2,3–dibromobutane (C) meso–2,3–dibromobutane (D) (±) 2,3–dibromobutane 4 . The bond dissociation energies of the following CH3–H CH3CH2–H CH2=CH–CH2–H C6H5–H I II III IV vary in the order : (A) I > II > III > IV (B) IV > III > II > I (C) IV > I > II > III (D) II > I > IV > III 5 . Which of the following decolourises alkaline KMnO4 solution (A) C3H8 (B) C2H4 (C) CH4 (D) CCl4 6 . Compounds capable of reacting with ammonical AgNO3 solution are (A) CH3 CH C CH (B) HC CH (C) 1- Butyne (D) all the above CH3 7 . A hydrocarbon which decolourises KMnO4 but does not give any precipitate with ammoniated AgNO3 (A) Benzene (B) Acetylene (C) Butyne (D) 2–Butene 8 . Compound 'A' on chlorination gives compound 'B', compound 'B' reacts with alc. KOH gives gas 'C', which decolourise Baeyer reagent. ozonolysis of compound 'C' gives only HCHO compound. 'A' is : (A) C2H6 (B) C2H4 (C) C4H10 (D) C2H5Cl 9 . Which reagent converts propene to 1–propanol (A) H2O, H2SO4 (B) B2H6, H2O2, OH– (C) Hg(OAc)2,NaBH4/H2O (D) Aq. KOH 1 0 . Which one of the following alkenes will react faster with H under catalytic hydrogenation conditions : 2 [R = Alkyl Substituent] R R R R R R R H R H H H (A) (B) (C) (D) R H R R

1 1 . Arrange the following in order of increase/decrease in boiling point. CH3CH2CH2CH2CH3 (CH3)2CHCH2CH3 (CH3)4C I II III (A) I > II > III (B) II > I > III (C) III > I > II (D) III < II < I (D)CH3COCH2CH3 1 2 . What are the products obtained upon the ozonolysis of 2-pentene ? (A) CH3CH2CHO (B) CH3CHO (C) CH3COCH3 1 3 . Which of the following can be used for the preparation of propane ? (A) CH3CH=CH2 1.B2H6 (B) CH3CH2CH2Cl 1.Mg /ether 2 .C H 3 C O O H 2.H2O (C) CH3CH2CH2I Re d P /HI/ 150C  (D) CH3CH2CH2COONa NaOH/ CaO  1 4 . Which of the following are correct :  (A) 1.O 3  OHC–CH2CH2CH2–C HO H 2. Zn,H2O (B) H H O C6H5C–OOH H H H CH2Cl2 O (C) KMnO4 H H H cold dilute solution H OH OH (D) OO H OKHM–n,hOe4at –O—CCH2CH2CH2C—O– H 1 5 . 2-Bromo-3-phenylpropane can be synthesised by (A) C6H5CH2CH(OH)CH3+PBr3  (B) C6H5CH=CHCH3+HBr+ benzoyl peroxide  (C) C6H5CH2CH2CH3+Br2+ light  (D) none of these 1 6 . The nitration of propane with concentrated HNO3 gives : (A) CH3CH2CH2NO2 (B) CH3CHCH3 (C) CH3CH2NO2 (D) CH3NO2 NO2 (D) Ethane 1 7 . Which of the follwing will react with sodium metal : (A) Ethyne (B) 1-Butyne (C) 2-Butyne

1 8 . —CH=CH2 A —CH2CH2OH B —CHCH3 OH C —CH2CH3 OH A, B and C are : (A) simple hydration (B) hydroboronation, mercuration-demercuration, hydration (C) hydration, hydroboronation, mercuration-demercuration (D) mercuration-demercuration, hydration, hydroboronation O O 19. C9H14 ozonolysis (A) Hence A is : (A) (B) (C) (D) (D) X -II, Y- II 20. Y X OH HO OH HO (C) X -I, Y- I Select X and Y out of : I: M n O  /OH– II : HCO3H 4 (A) X -I, Y- II (B) X -II, Y- I BRAIN TEASERS ANSWER KEY EXERCISE -2 10 11 12 13 14 15 Que. 1 2 3 4 5 6789 B A , D A , B A ,BC,D A ,BC,D A ,B A n s . A , B,D B D C B DDAB Que. 16 17 18 19 20 A n s . A ,BC,D A , B B B A

EXERCISE–03 MISCELLANEOUS TYPE QUESTIONS TRUE OR FALSE : 1 . Although acetylene acidic in nature it does not react with NaOH/KOH. 2 . Although C—H bond in acetylene has greatest bond energy of all C—H bond, yet it is most acidic. : : 3 . CH2=CH is less basic than HC C 4 . —C  C— has two  bond yet it is less reactive than —C=C— towards electrophilic addition reaction. 5 . Partial reduction of alkynes is either syn or anti. FILL IN THE BLANKS : 1 . Out of cis-2 butene and trans-2-butene, ...................... has the lower melting point. 2 . A four-carbon alkyne having weakly acidic character is ...................... 3 . Alkanes undergo ................... reactions whereas alkynes give .............. reaction. 4 . ..................... is a versatile method for locating the position of the double bond in an alkene. 5 . The valence atomic orbital on carbon in silver acetylide is ................... hybridized. MATCH THE COLUMN (p) Column-II 1 . Match the column I with column II. (q) Electrophilic substitution reaction (r) Free radical substitution Column-I (s) Electrophilic addition reaction ( A ) Wurtz reaction Nucleophilic substitution ( B ) Hydration of alkenes ( C ) Nitration of alkane Column-II ( D ) Reaction of alkene with NBS HBr 2 . Match the column I with column II. HBr + peroxide Column-I NBS Br2, low temp., dark CH3—CH=CH2 (A) (p) CH3—CH2—CH2Br (q) Column-II (r) Kolbe reaction (B) (s) CH3—CHBr—CH3 Alc. KOH Addition product of ethylene (C) Sodalime CH3—CHBr—CH2Br Alkene (D) BrCH2—CH=CH2 3 . Match the column I with column II. (p) Column-I (q) ( A ) Dehydrohalogenation (r) of alkyl halides (s) (t) ( B ) Electrolysis of sodium salt ( C ) Ozonolysis ( D ) Dichloro ethylene ( E) Decarboxylation

ASSERTION & REASON QUESTION : These questions contains, Statement-I (assertion) and Statement-II (reason). (A) Statement-I is True, Statement-II is True ; Statement-II is a correct explanation for Statement-I (B) Statement-I is True, Statement-II is True ; Statement-II is NOT a correct explanation for Statement-I (C) Statement-I is True, Statement-II is False. (D) Statement-I is False, Statement-II is True. 1 . Statement-I : Of two isomeric alkenes shown, II is more stable than I. II I Because Statement-II : The alkene (II) has sp2-hybridized carbons. 2 . Statement-I : Addition of HBr to 1-butene gives two optical isomers. Because Statement-II : The product contains one asymmetric carbon. 3 . Statement-I : 1-Butene on reaction with HBr in the presence of a peroxide produces 1-bromobutane. Because Statement-II : It involves the formation of a primary radical. 4 . Statement-I : Addition of Br2- water containing dissolved NaCl to ethylene gives a mixture of 1, 2- dibromoethane, 1-bromo-2-chloroethane and 2-bromoethanol. Because Statement-II : Addition occurs through a carbocation intermediate. 5 . Statement-I : Addition of bromine to trans-2-butene yields meso-2,3-dibromobutane. Because Statement-II : Bromine addition to an alkene is an electrophilic addition. 6 . Statement-I : Alkynes are more reactive than alkenes towards electrophilic reagents like H+. Because Statement-II : The alkyl carbocation formed from alkene is more stable than the vinyl carbocation formed from alkyne. 7 . Statement-I : Neopentane forms only one monochlorinated product. Because Statement-II : Neopentane has four identical methyl group attached to a quaternary carbon. 8 . Statement-I : Buta-1,3-diene is less stable than Penta-1, 4-diene. Because Statement-II : Buta-1,3-diene has greater number of resonating structures and delocalised electron cloud, 9 . Statement-I : Iodination of alkanes is carried out in the presence of iodic acid. Because Statement-II : Iodic acid removes I2 gas from the reaction mixture. 1 0 . Statement-I : Propene is more reactive than ethene with HCl. Because Statement-II : Propene is more stable than ethene.

COMPREHENSION BASED QUESTIONS : Comprehension # 1 X(C4H9Br) alc.KOH  Y Br2 Z (Dibromide) NaNH2 W (gas) ASgNolOn 3  white ppt. X, Y and Z are 1. X Y Z (A) CH3—CH2CH2CH2Br CH3—CH=CH—CH3 CH3—CH—CH2—CH2 Br Br (B) CH3—CH2CH2CH2Br CH3—CH2—CH=CH2 CH3—CH2—CH—CH2 Br Br (C) CH3—CH2—CH2—CH3 CH3—CH=CH—CH3 CH3—CH—CH—CH3 Br Br (D) CH3—CH2—CH—CH3 CH3—CH=CH—CH3 CH3—CH2—CH—CH2 Br Br Br 2 . Reductive ozonolysis of Y yields : (B) CH3CH2CHO & HCHO (A) 2 moles of CH3CHO (C) CH3—C—CH3 & HCHO (D) CH3CH2COOH & HCOOH O 3 . Which of the following statement (s) is/are correct : (A) Compound W has 2 DU (B) Y & W are functional isomers (C) W can be converted into Y with Lindlar catalyst (D) W can be converted into Y with Ni/Pt Comprehension # 2 : Borane is an electron deficient compound. It has only six valence electrons, so the boron atom lacks an octet. Acquiring an octet is the driving force for the unusual bonding structure found in boron compounds. As an electron deficient compound, BH3 is a strong electrophile, capable of adding to a double bond. This hydroboration of double bond is though to occur in one step, with the boron atom adding to the less highly substituted end of the double bond. In transition state, the boron atom withdraws electrons from the pi bond and the carbon at the other end of the double bond acquires a partial positive charge. This positive charge is more stable on the more highly substituted carbon atom. The second step is the oxidation of boron atom, removing it from carbon and replacing it with a hydroxyl group by using H2O2/ OH . The simultaneous addition of boron and hydrogen to the double bond leads to a syn addition. Oxidation of the trialkyl borane replaces boron with a hydroxyl group in the same stereochemical position. Thus, hydroboration of alkene is an example of stereospecific reaction, in which different stereoisomers of starting compounds react to give different stereoisomers of the product.

1 . What will be the product of following reaction (i) BH3/THF product : (ii) H2O2/OH :: :H CH3 (A) OHH3C (B) H H3C (C) H H (D) H H3C HH HO H HO CH3 H OH 2 . Find the product of following reaction CH3 (D) CH3 OH (i) BH3/THF X (ii) H2O2/OH CH3 HO CH3 CH3 (A) OH (B) (C) H OH 3. D (i) BH3/THF Y. (ii) H2O2/OH D Y is : (A) Meso OH (B) Racemic OH (C) both D (D) None of these D DH DH CH3 4. CH3—C—CH=CH2 (i) BH3/THF Z. (ii) H2O2/OH : CH3 : Z is : (B) Optically active 2°-alcohol (D) Optically inactive 3°-alcohol (A) Optically active 1°-alcohol (C) Optically inactive 1°-alcohol D 5. (i) BH3/THF Product. The product is D (ii) H2O2/OH (A) Threo cyclic alcohol (B) Erythreo cyclic alcohol (C) Optically active alcohol (D) Both (B) and (C)

Comprehension # 3 Hydrocarbon (A) C6H10 on treatment with H2/Ni, H2/Lindlar's catalyst or Na/liq. NH3 forms three different reduction products (B), (C), (D) respectively. (A) does not form any salt with ammonical AgNO3 solution, but (E) forms salt on heating with NaNH2 in an inert solvent. Compound (E) reacts with CH3I to give (F). Compound (D) on oxidative ozonolysis gives n-butanoic acid along with other product. 1 . (D) and (C) are (A) Isomeric alkane (B) Isomeric alkene (C) Not isomers (D) (C) is an alkene and (D) is salt 2 . If (E) is reacted with acetaldehyde followed by acidification, product is (A) acid (B) ketone (C) ether (D) alcohol 3 . (F) on ozonolysis will produce - (A) acetic aicd (B) formic acid (C) propanoic acid (D) formaldehyde MISCELLANEOUS TYPE QUESTION ANSWER KEY EXERCISE -3  True / False 2. T 3. F 4. T 5. T 1. T 3. Free radical substitution, electrophilic substitution  Fill in the Blanks 1. Cis-2-butene 2. 1-Butyne 4. Ozonolysis 5. sp  Match the Column 1. (A) s ; B r ; (C)  p ; (D) q 2. (A) q ; (B) p ; (C)  s ; (D) r 3. (A) q ; (B) p ; (C)  t ; (D) r ; (E) s  Assertion - Reason Questions 1. C 2. A 3. C 4. A 5. B 6. D 7. A 8. D 9. C 10. B  Comprehension Based Questions Comprehension #1 : 1. (B) 2. (B) 3. (A, C) 4. (C) 5. (D) Comprehension #2 : 1. (B) 2. (D) 3. (B) Comprehension #3 : 1. (B) 2. (D) 3. (A)

EXERCISE–04 [A] CONCEPTUAL SUBJECTIVE EXERCISE CC 1 . (Y) Na,NH3  H2  (X). Lindlar's catalyst What are X and Y in above reaction. 2 . Find out reagents involved in following conversions : CH3—CH2—CC—H O (a) CH3—CH2—C—CH3 O (b) CH3—CH2—CH2—C—H Cl (c) CH3—CH2—C—CH3 Cl (d) CH3—CH2—CC—CH3 (e) CH3—CH2—CC—D 3 . Select one from the following pair of isomer that has higher heat of combustion, justifying your choice. (a) and (b) and (I) (II) (I) (II) and (d) and (c) (I) (II) (I) (II) 4 . The reaction of the diene shown below with dry HCl can lead to four products. Provide structural formula of all the products. OneHCml ole 5 . Write major product in the following reactions : (a) F C—CH = CH + HI  32 (b) C H —CH=CHCH +HBr P e ro xide  65 3 (c) CH3CH=C—CH3 CHBr3 Peroxide CH3 (d) C H —CH=CH +B H H2O2  65 2 26 NaOH (e) CH —CH=CH—CH=CH HCl  32 50C

6 . Propose mechanism : Br Br + + HBr  + Br 7 . A hydrocarbon (A) was found to have vapour density 36. It forms only single mono chlorosubstitution product. Suggest (A). 8 . An olefin was treated with ozone and the resulting product on reductive hydrolysis gave 2-pentanone and acetaldehyde. What is the structure of olefin ? Write reactions. 9 . Why n-Pentane has higher boilign point than neopentane ? 1 0 . Write a plausible mechanism for the following transformation. conc. + HO 2 H2SO4 OH CONCEPTUAL SUBJECTIVE EXERCISE ANSWER KEY EXERCISE -4(A) 1 . (X) : (Y) : Cis trans : 2 . (a) H2O/Hg2+/H+ , (b) (Sia)2 BH/H2O2, OH, (c) 2HCl, (d) Na, CH3 – I, (e) Na, D–O–D 3 . (a) II ; (b) I ; (c) II ; (d) I 4. +H+ + + II I Cl– I Cl Cl + II Cl– + Cl Cl

+ 6 . + H+ Br– + Br H–shift Br + + Br– Br– Br Br– H–shift Br + 7 . Mol.wt of alkane = Vapour density × 2 = 36 × 2 = 72 Alkane is CnH2n+2  12n + 2n + 2 = 72 n=5  Alkane is C5H12 Thus alkane C5H12 showing only one mono substitution product is CH3 CH3 CH3—C—CH3 Cl2 CH3—C—CH2Cl CH3 CH3 (A) (2,2-dimethylpropane) 8. (i) Olefin O3 ozonide 2H CH3—CH2—CH2—C=O+CH3CHO (ethanal) CH3 (pentan-2-one) (ii) Thus olefin has 7 carbon atoms with two units round double bond as CH3CH2CH2 CH3 C=O C=O and H H3C (iii) The olefin is therefore CH3—CH2—CH2—C=CH—CH3 CH3 (iv) The reaction is CH3—CH2—CH2—C=CH—CH3 (i) O3 CH3—CH2—CH2—C=O+CH3CHO (ii) 2H CH3 (ethanal) (3-methylhex-2-ene) CH3 (pentan-2-one) 9 . n-Pentane has higher b.p. (36.2°C) than neopentane (9.5°C). It is due to vander waals forces. n-Pentane has a rod-like shape, while neopentane is sphere-like. Rods can touch along their entire length, while the spheres touch only at a point. The more the contanct between molecules, the greater the vander waals forces and hence higher the b.p.

EXERCISE–04 [B] BRAIN STORMING SUBJECTIVE EXERCISE CH2OH CH2 CH2 1. conc. H2SO4  ++ major Give mechanism of this reaction. 2 . Identify the products in the following, giving their configurations. (if any) (a) COOH (b) COOH HOOC OsO4  HOOC CH3CO3H  H2O2 H2O COOH CH3CO3H  COOH OsO4  (c) H2O (d) H2 O2 COOH COOH 3 . Write one reagent in each case to make distinction between (a) 1-butyne and 2-butyne ............ (b) 1-butene and 1-butyne ............ (c) ethene and ethane ............ 4 . 2-Butyne undergoes following reactions in steps as indicated. Identify A to H. CH3C CCH3 H2 A D2/Pt B Ni2B (P-2) Na/EtOH C D2/Pt Br2 F D H2 E Ni2B (P-2) Br2 G H2 H Ni 5 . Identify A, B, C with proper explanation. n—BuCCMe Li, NH3(I) A C H2 B Lindlar's catalyst 6 . A hydrocarbon A(C10H12) has no chiral carbon. A gives a white precipitate with ammonical solution of silver nitrate. A on traeatment with H2/Pt gives B(C10H20). A on ozonolysis gives C(C8H12O4) as one product which on heating with soda lime gives D(C6H12). D on monochlorination with Cl2/hv gives C6H11Cl as sole isomer. Identify A to D. 7 . Identify A to D in the following scheme. CH3Br Mg /ether  A D2O B Cl2 ,hv  C Na /ether  D one mol

CH3 CH3 .............. CHCH2CH2CH 8 . C 4 H 9 Cl Na /ether  CH3 CH3 Write structure of C H Cl. 49 9 . Specify the reagents in which addition to alkene is syn or anti (i) Br water (ii) H /pd 2 2 (iii) MnO4–/OH– (iv) HCO3H (v) MCPBA — (vi) OsO4 in ether, followed by OH/ H2O 1 0 . C5H10 represents three isomeric alkenes A1, A2 and A3. Each on hydrogenation gives 2-methylbutane. A1 and A2 on oxymercuration-demercuration give the same 3º alcohol. A2 and A3 on hydroboration oxidation give different 1º alcohol. Assign structures to A1, A2 and A3 and explain the reactions. BRAIN STORMING SUBJECTIVE EXERCISE ANSWER KEY EXERCISE -4(B) CH2OH + CH2OH2 1 . Step (I) : H  (H2 SO4 ) Step (II) : Step (III) : (a) (b) Step (IV) : + CH2 (b)  –H2O (c) + CH2 CH2 H H minor + CH2 + (ringalekxylpsahnifstion ) Step (V) : + H H major