C2-Allens Made Chemistry Exercise {PART-1}

SUBJECTIVES : 9 . Given : Ag(NH3)2+  Ag+ + 2 NH3, Kc = 6.2 × 10–8 & Ksp of AgCl = 1.8 × 10–10 at 298 K. Calculate the concentration of the complex in 1.0 M aqueous ammonia. [JEE 1998] 1 0 . What will be the resultant pH when 200 mL of an aqueous solution of HCl (pH = 2.0) is mixed with 300 mL of an aqueous solution of NaOH (pH = 12.0) ? [JEE 1998] 1 1 . The solubility of Pb(OH)2 in water is 6.7 × 10–6 M. Calculate the solubility of Pb(OH)2 in a buffer solution of pH = 8. [JEE 1999] 1 2 . The average concentration of SO2 in the atmosphere over a city on a certain day is 10 ppm, when the average temperature is 298 K. Given that the solubility of SO2 in water at 298 K is 1.3653 moles litre–1 and the pKa of H2SO3 is 1.92, estimate the pH of rain on that day. [JEE 2000] 1 3 . 500 mL of 0.2 M aqueous solution of acetic acid is mixed with 500 mL of 0.2 M HCl at 25 °C. (a) Calculate the degree of dissociation of acetic acid in the resulting solution and pH of the solution. (b) If 6g of NaOH is added to the above solution, determine final pH. Assume there is no change in volume on mixing. Ka of acetic acid is 1.75 × 10–5 M. [JEE 2002] 1 4 . Will the pH of water be same at 4 °C and 25 °C ? Explain. [JEE 2003] 1 5 . 0.1 M of HA is titrated with 0.1 M NaOH, calculate the pH at end point. Given Ka(HA) = 5 × 10–6 and  << 1. [JEE 2004] 1 6 . CH3NH2 (0.1 mole, Kb = 5 × 10–4) is added to 0.08 moles of HCl and the solution is diluted to one litre, resulting hydrogen ion concentration is (A) 1.6 × 10–11 (B) 8 × 10–11 (C) 5 × 10–5 (D) 2 × 10–2 [JEE 2005] 1 7 . The species present in solution when CO2 is dissolved in water : (A) CO2, H2CO3, HCO3– , CO2– (B) H2CO3, CO32– [JEE 2006] (C) CO32– , HCO3– (D) CO2 , H2CO3 1 8 . Solubility product constants (KSP) of salts of types MX, MX2 and M3X at temperature 'T' are 4.0 ×10–8, 3.2 ×10–14 and 2.7 ×10–15 , respectively. Solubilities (mol dm–3) of the salts at temperature 'T' are in the order : (A) MX > MX2 > M3X (B) M3X > MX2 > MX [JEE 2008] (C) MX2 > M3X > MX (D) MX > M3X > MX2 22 1 9 . 2.5 mL of 5 M weak monoacidic base (Kb = 1 × 10–12 at 25°C) is titrated with 15 M HCl in water at 25°C. The concentration of H+ at equivalence point is [JEE 2008] (Kw = 1 × 10–14 at 25°C) (A) 3.7 × 10–13 M (B) 3.2 × 10–7 M (C) 3.2 × 10–2 M (D) 2.7 × 10–2 M

2 0 . The dissociation constant of a substituted benzoic acid at 25°C is 1.0 × 10–4. The pH of a 0.01 M solution of its sodium salt is [JEE 2009] 2 1 . In 1 L saturated solution of AgCl [K (AgCl) = 1.6 × 10–10], 0.1 mol of CuCl sp [Ksp(CuCl) = 1.0 × 10–6] is added. The resultant concentration of Ag+ in the solution is 1.6 × 10–x. The value of ‘x’ is. [JEE 2011] 2 2 . The Ksp of Ag2CrO4 is 1.1 × 10–12 at 298 K. The solubility (in mol/L) of Ag2 CrO4 in a 0.1 M AgNO3 solution is [JEE 2013] (A) 1.1 × 10–11 *(B) 1.1 × 10–10 (C) 1.1 × 10–12 (D) 1.1 × 10–9 2 3 . The initial rate of hydrolysis of methyl acetate (1M) by a weak acid (HA, 1M) is 1/100th of that of a strong acid (HX, 1M), at 25ºC. The Ka of HA is [JEE 2013] *(A) 1 × 10–4 (B) 1 × 10–5 (C) 1 × 10–6 (D) 1 × 10–3 JEE-[A DVANCED] : PREVIOUS YE AR QUESTIONS ANSWER KEY EXERCISE -5[B] 1 . B,C 2 . A,B,C 3. B 4. A 5. A 6. C 7. A 8. B 9 . [Ag(NH3)2+] = 0.0539 1 0 . pH = 11.3010 1 1 . s = 1.203 × 10–3 M 12. 0.4948 1 3 . (a) 0.0175 %, pH = 1, (b) 4.75 14. NO 1 5 . pH = 9 16. B 17. A 18. D 19. D 20. 8 21. 7 22. A 23. A

EXERCISE-01 CHECK YOUR GRASP SELECT THE CORRECT ALTERNATIVE (ONLY ONE CORRECT ANSWER) 1 . Type of isomerism exists between :- CH3—CH2—CH2—CN and CH3 CH CH3 CN (A) Position (B) Chain (C) Both the above (D) None of these 2 . The number of primary alcohols possible with the formula C4H10O is - (A) 2 (B) 3 (C) 4 (D) 5 3 . The total number of benzene derivatives having the molecular formula C7H7Cl is - (A) 2 (B) 3 (C) 4 (D) 5 4 . Which of the following will lead to maximum enolisation :– (A) CH3COCH3 (B) CH3COCH2CHO (C) CH3 C CH C CH3 O O Br O (D) 5. H3C CC H H H3C H3C C Exhibits :- COOH (A) Tautomerism (B) Optical isomerism (C) Geometrical isomerism (D) Geometrical and optical isomerism 6 . Tautomerism is not exhibited by :- (A) (B) (CH3)2CHNO2 (C) (D) (CH3)3CCHO 7 . Given compound exhibits x geometrical isomers and y optical isomers The value of x and y respectively are :- (A) 4 and 4 (B) 2 and 2 (C) 2 and 4 (D) 4 and 2 8 . The total number of cyclic compounds (neglecting stereoisomers) with the molecular formula C5H10 is - (A) 4 (B) 5 (C) 6 (D) 7 9 . Which of the following exhibits tautomerism ? (A) (CH3)2NH (B) (CH3)3CNO2 (C) R3CNO2 (D) RCH2NO2

1 0 . The correct structure of trans–2–hexenal is - (B) CHO (A) CHO (C) CHO (D) CHO 1 1 . The total number of benzene derivatives having the molecular formula C7H8O is - (A) 3 (B) 4 (C) 5 (D) 6 1 2 . Which of the following compounds does not exhibit tautomerism (A) CH3NO2 (B) CH3CH2NO2 (C) C6H5CH=CH–OH (D) CH3CH2OH 1 3 . The total number of benzene derivatives with the molecular formula C6H3Cl3 is - (A) 2 (B) 3 (C) 4 (D) 5 1 4 . Which of the following compounds is not chiral ? (A) DCH2CH2CH2Cl (B) CH3CHDCH2Cl (C) CH3CHClCH2D (D) CH3CH2CHDCl 1 5 . The total number of stereoisomers of 2,3–dibromobutane is - (A) 2 (B) 3 (C) 4 (D) 5 1 6 . In the structure : CH3 H OH H Br the configurations at the chiral centres are : CH3 (B) 2S, 3R (C) 2R, 3S (D) 2S, 3S (A) 2R, 3R 1 7 . Which of the following compound contains a pseudo-asymmetric carbon atom (A) CH3CHCHCH2 (B) CH3CH–CH–CHCH3 Br Br Br Br OH Br (C) CH3CHCHCHCH3 (D) CH3CHCHCHCH3 OHBr Br Br OHCl 1 8 . Consider the following structures (A), (B), (C) and (D) - CH3 C2H5 (A) Cl Br (B) Cl Br C2H5 CH3 Cl Cl (C) CH3 Br (D) C2H5 CH3 C2H5 Br Which of the following statements is not correct (A) B and C are identical (B) A and B are enantiomers (C) A and C are enantiomers (D) B and D are enantiomers

1 9 . The interchange of two groups (Br and CH3) at the chiral centre of the projection formula (A) yields the formula (B), while the interchange of another set of two groups (C2H5 and Cl) of (A) yields the projection formula (C) - CH3 Br CH3 Cl Br Cl CH3 C2H5 Br C2H5 C2H5 Cl (A) (B) (C) Which of the following statements is not correct about the structures (A), (B) and (C) - (A) B and C are identical (B) A and C are enantiomers (C) B and C are enantiomers (D) A and B are enantiomers 2 0 . How many meso stereoisomers are possible for 2, 3, 4-pentanetriol - (A) 1 (B) 2 (C) 3 (D) none of these 2 1 . The total number of stereoisomers of the compound CH3CH=CH–CH–CH=CH–CH3 is - OH (A) 2 (B) 3 (C) 4 (D) 8 2 2 . The total number of aldehydes and ketones with the molecular formula C4H8O is - (A) 2 (B) 3 (C) 4 (D) 5 2 3 . In which of the following properties do enantiomers differ from each other (A) Solubility in an achiral solvent (B) Reactivity with an achiral reagent (C) Melting point (D) Optical rotation 2 4 . (+) - Mandelic acid has a specific rotation of + 158º. What would be the observed specific rotation of a mixture of 25% (–) -mandelic acid and 75% (+) -mandelidc acid : (A) + 118.5° (B) –118.5° (C) – 79° (D) + 79° 2 5 . When C H Cl is converted into C H Cl , o-isomer will give m types of C H Cl , and p-isomer will give 64 2 63 3 63 3 q types of C H Cl . m, n, q are respectively : 63 3 (A) 1, 2, 3 (B) 2, 1, 3 (C) 1, 3, 2 (D) 2, 3, 1 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. B A C D B D B A D B C D B A B B B D C D Que. 21 22 23 24 25 Ans. C B B D B

EXERCISE–02 BRAIN TEASERS SELECT THE CORRECT ALTERNATIVES (ONE OR MORE THEN ONE CORRECT ANSWERS) 1 . Tautomerism is shown by :- OO (A) HCN (B) CH3—C—CH2—C—CH3 O (D) CCl3CHO (C) CH3—CH2—N O 2 . In which of the following cases, cis-trans nomenclature can not be used :- (A) Cl—CH=CH—Cl (B) CH3—CH=CH—CHO (C) C6H5—N=N—C6H5 (D) CH3—CH=C(Cl)C2H5 3 . Among the following, which are tautomers :- (A) CH2—C—CH3 and CH2=C—CH3 (B) CH3—CH2—CH=NH and CH3—CH=CH—NH2 OO (D) glucose and fructose (C) CH3—N O and CH3—CH=N—OH O 4 . Consider the following compounds : CH3 CH3 CH3 H———OH HO———H HO———H H———OH HO———H HO———H CH3 CH3 CH3 (I) (II) (III) Choose the correct statements : (B) I and II are diastereomers (A) I and III are enantiomers (D) I, II and III are all optically active (C) II and III are diastereomers 5 . Which will show geometrical isomerism :- (A) C6H5–CH=NOH (B) (C) C6H5–N=N–C6H5 (D) H H 6 . Which statement (s) is/are correct for :- H3C CH3 CHO CHO (B) Both are enantiomers H———OH HO———H (D) Both are in erythro form HO———H H———OH C6H5 C6H5 (I) (II) (A) Both are in threo form (C) Both are diastereomers

7 . Which of the following compounds are chiral and resolvable :- (A) C6H5N(CH3) (C2H5)  (B) [C6H5 N (CH3) (C2H5) (C3H7)] Cl– COOH (C) CH3–CH2–CH(CH3) N (CH3) (C2H5) (D) COOH 8 . Observe the following structures and pick up the correct option (s) mentioned below :- CH3 CH3 H Cl H Cl H HH H CH2Cl Cl (A) (B) (A) The two are position isomers (B) None of the two shows optical isomerism (C) Only A shows optical isomerism (D) The two are not related to each other regarding isomerism CH3 CH3 H———Cl H———Cl Cl———H H———Cl 9. CH2CH3 CH2CH3 (II) (I) (A) I and II are enantiomers (B) I is 2S, 3S; while II is 2S, 3R (C) I is 2R, 3R; While II is 2R, 3S (D) I and II are diastereomers 1 0 . Which of the following statements are true regarding following structures :- COOCH3 COOH COOH H———OH H———OH H———OH H———OH H———OH HO———H COOH COOCH3 COOCH3 (a) (b) (c) (A) A and B are diastereomers (B) A and C are diastereomers (C) B and C are diastereomers (D) A and B are enantiomers 1 1 . The R and S enantiomers of an optically active compound differ in :- (A) their reactivity with chiral reagents (B) their melting points (C) their optical rotation of plane polarized light (D) their solubility in achiral reagents

1 2 . Which of the following statements (s) is (are) incorrect :- XY (A) X is cis- and Y is trans (B) X is Z and Y is E (C) X is trans and Y is cis (D) X and Y are diastereomers 1 3 . Which of the following compounds will show geometrical isomerism :- (A) 2-butene (B) propene (C) 1-phenylpropene (D) 2-methyl-2-butene 1 4 . Tautomerism is exhibited by :- (A) –CH=CH–OH (B) O= =O (C) O (D) O O O 1 5 . Which of the following notations are correct : Br F Br C=C Cl (B) I (A) I C=C Cl (Z) I (E) (C) H3C C=C CH3 (D) H3C C=C CH2CH2CH3 H H H (E) CH3 (Z) 1 6 . For which of the following pairs of compounds are the correct notation given :- Ph Ph Ph N=N and N=N (A) Ph Anti-azobenzene Syn-azobenzene H3C H3C OH C=N C=N and H (B) H OH Syn-acetaldoxime Anti-acetaldoxime HH CO2H H C=C H and C=C CO2H (C) NH2 NH2 Trans-o-aminocinnamic acid Cis-o-aminocinnamic acid H3C C=C CH2CH2CH3 ClCH2 C=C CH3 (D) H BrH2C CH3 CH3 and Z-isomer E-isomer

1 7 . Which of the following statements are correct :- CH3 (A) CH3CH2CH2CH2OH and CH3CHCH2OH represent chain isomerism (B) CH3CH2CH2CH=CH2 and CH3CH2CH = CHCH3 are examples of position isomerism (C) C2H5OCH3 and CH3CH2CH2OH represent functional-group isomerism (D) CH3CH2NH2 and CH3NHCH3 are examples of metamerism 1 8 . Which of the following are optically active :- (A) H2C=C=CH2 (B) C=C=C FF Cl H H (D) —CO2H (C) H2N NH2 FF 1 9 . An enantiomerically pure acid is treated with racemic mixture of an alcohol having one chiral carbon. The ester formed will be : (A) optically active mixture (B) pure enantiomer (C) meso compound (D) racemic mixture 2 0 . Tartaric acid molecule contains two asymmetric carbon atoms. The number of optical isomers of tartaric acid is :- (A) 2 (B) 3 (C) 4 (D) 5 BRAIN TEASERS ANSWER KEY EXERCISE -2 Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 An s . A,B,C B,C,D B,C A,B,C A,B,C,D A,B B,C A,C B,D B,C,D A,C A,B A,C A,C,D A,C Que. 16 17 18 19 20 An s . B,C,D A,B,C,D B,C A B

EXERCISE–03 MISCELLANEOUS TYPE QUESTIONS TRUE OR FALSE : 1 . Stereo-isomers which are not mirror image of each other are known as diastereoisomers. 2 . In every case, a pair of enantiomers have a mirror-image relationship. 3 . If a compound has an enantiomer it must be chiral. 4 . If a compound has a diastereomer it must be chiral 5 . Any molecule containing a stereocentre must be chiral. 6 . Any chiral compound with a single asymmetric carbon must have a positive optical rotation if the compound has the R configuration. FILL IN THE BLANKS : 1 . The possible number of dichloro derivatives of propane are ...................... . 2 . Ethyl benzene is ................... isomer to xylenes. 3 . The compound CHCl = CHCl can show .................... isomerism. 4 . d- and - lactic acid are known as ................ . 5 . Maleic and fumaric acids are a pair of ............... . MATCH THE COLUMN N—OH (p) Column-II (stereoisomers) 2 1 . Match the column I with column II. Column-I (reaction) (A) CH3—CH CH—CH (B) (q) 4 (C) CH3—CH CH—CH CH—CH CH—CH3 ( r ) 6 (D) CH3—CH CH—CH CH—CH CH—Ph ( s ) 8 2 . Match the following compounds of column I with column II. Column-I (Molecule) Column-II (Property) HH ( p ) Chiral compound ( q ) Presence of stereocenter (A) C C C Cl Cl H CH3 (B) CH3 H Cl Br F ( r ) Optically active compound (C) I CH3 OH (D) C N ( s ) Compound containing plane Et • • of symmetry

3 . Match the column I with column II. Column-II (stereoisomers) Column-I (reaction) Homologs ( A ) & Cl (p) Functional isomers Cl OCH2–CH3 OCH3 CH3 (B) & (q) OCH3 OH CH3 ( C ) & (r) Metamer (D) CH3–CH2– –CH2–CH3 & (s) Chain isomers CH3– –CH2–CH2–CH3 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 : Staggered and eclipsed ethane can not be separated. Because Statement-II : Energy barrier between staggered and eclipsed form of ethane is 12.6 kJ/mole. 2 . Statement-I : All double bond containing compounds show geometrical isomerism. Because Statement-II : Alkenes have restricted rotation about the double bond. 3 . Statement-I : Meso-tartaric acid is optically active. Because Statement-II : Optically active molecule is a molecule that cannot be superimposed on its mirror image. 4 . Statement-I : Cyclohexanone exhibits keto-enol tautomerism. Because Statement-II : In cyclohexanone, one form contains the keto group (C=O) while other contains enolic group (–C=C–OH). 5 . Statement-I : Staggered form is less stable than the eclipsed form. Because Statement-II : The conformation in which the bond pairs of two central atoms are very far from one another is called staggered from.

6 . Statement-I : Trans-isomers are more stable than cis-isomer. Because Statement-II : The cis-isomer is the one in which two similar groups are on the same side of double bond. 7 . Statement-I : Propadiene is optically inactive. Because Statement-II : Propadiene has a plane of symmetry. COMPREHENSION BASED QUESTIONS : Comprehension # 1 Geometrical isomerism is a kind of stereoisomerism which is present in the compounds containing a double bond (C=C, C=N, N=N) and arise due to the restricted or frozen rotation about the double bond. The atoms or groups attached to the doubly bonded carbons must be different. In aldoximes, the isomer is named as syn if hydrogen and hydroxyl groups are on the same side of C=N bond and if these are on opposite sides, the isomer is named as anti. In ketoximes, the prefixes syn and anti indicate which group of ketoxime is syn or anti to hydroxyl group. 1 . Which of the following does not show geometrical isomerism ? (A) 1,2-Dichloropent-1-ene (B) 1,3-Dichloropent-2-ene (C) 1,1-Dichloropent-1-ene (D) 1,4-Dichloropent-2-ene 2 . On treating with NH2OH, which can form two products ? (A) Acetaldehyde (B) Acetone (C) Formaldehyde (D) Benzophenone 3 . Number of stereoisomers of the compound 2-chloro-4-methylhex-2-ene is/are (A) 1 (B) 2 (C) 4 (D) 16 4 . The correct structure of trans-2-hexenal is - CHO (A) CHO (B) (C) CHO CHO (D) 5 . The geometrical isomerism is shown by : CH2 CH2 CHCl CHCl (A) (B) (C) (D) Comprehension # 2 The optical isomers rotate the plane of plane-polarised light. A sp3-hybridised carbon atom attached to four different atoms or groups is called an asymmetrical centre or chiral centre. Chiral molecules do not possess any of the elements of symmetry. A chiral molecule cannot be superimposed on its mirror image. These stereoisomers are called enantiomers. Molecules having a plane of symmetry or centre of symmetry are superimposable on their mirror images and are achiral. The stereoisomers that are not mirror images of each other are called diastereomers. A mesoisomer has a plane of symmetry and is optically inactive due to internal compensation.

1 . Which of the following has a meso isomer also ? (A) 2-Chlorobutane (B) 2-3, Dichlorobutane (C) 2, 3-Dichloropentane (D) 2-Hydroxypentanoic acid 2 . Which of the following compounds is not chiral ? (A) DCH2CH2CH2Cl (B) CH3CH2CHDCl (C) CH3CHDCH2Cl (D) CH3CHClCH2D 3 . The total number of acylic isomers including the stereoisomers (geometrical and optical) possible with the molecular formula C4H7Cl is : (A) 12 (B) 11 (C) 10 (D) 9 4 . Which among the following compounds will be dissymmetric but not asymmetric : COOH OH (A) H—C—OH (B) CH3—C—COOH H—C—OH C2H5 CH3 COOH CH3 CH3 (C) H—C—Br (D) C=C=C H—C—Br COOH HH 5 . Two isomeric alkenes A and B have molecular formula C5H9Cl. On adding H2, A gives optically inactive compound while B gives chiral compound. The two isomers are : (A) A is 3-Chlorpoent-1-ene and B is 1-chloropent-2-ene (B) A is 2-Chloro-3-methylbut-2-ene while B is 1-Chloro-3-methylbut-1-ene (C) A is 3-Chloropent-2-ene and B is 2-Chloropent-2-ene (D) A is 4-Chloropent-2-ene and B is 4-Chloropent-1-ene Comprehension # 3 Different spatial arrangements of the atoms that result from rotation about a single bond are conformers. n-Butane has four conformers eclipsed, fully eclipsed, gauche and anti. The stability order of these conformers are as follows : Anti > gauche > Partial eclipsed > Fully eclipsed Although anti is more stable than gauche but in some cases gauche is more stable than anti. 1 . Which one of the following is most stable conformer : Cl Cl Cl Cl Cl CH3 H Cl H Cl H3C H (D) H (B) (C) H H3CCH3 (A) H H CH3 H CH3 H CH3 CH3 Cl

2 . Which one of the following is the most stable conformer ? CH3 CH3 CH3 H OH HO H H CH3 H OH CH3 (C) (D) (A) H OH (B) H OH H OH H CH3 OH CH3 OH CH3 3 . Number of possible conformers of n-butane is : (A) 2 (B) 4 (C) 6 (D) infinite MISCELLANEOUS TYPE QUESTION ANSWER KEY EXERCISE -3  True / False 1. T 2. T 3. T 4. F 5. T 6. F  Fill in the Blanks 1. four 2. chain 3. geometrical 4. enantiomer 5. geometrical  Match the Column 1. (A) q ; B p ; (C)  r ; (D) s 2. (A) p, q, r ; (B) q, s ; (C)  p, q, r ; (D) q, s 3. (A) p ; (B) r ; (C)  q ; (D) r, s  Assertion - Reason Questions 1. A 2. D 3. D 4. B 5. D 6. B 7. A  Comprehension Based Questions Comprehension #1 : 1. (C) 2. (A) 3. (C) 4. (B) 5. (D) Comprehension #2 : 1. (B) 2. (A) 3. (C) 4. (D) 5. (C) Comprehension #3 : 1. (A) 2. (C) 3. (D)

EXERCISE–04 [A] CONCEPTUAL SUBJECTIVE EXERCISE SUBJECTIVE QUESTIONS : 1 . How many isomers are there corresponding to the formula C H O ? 4 10 2 . If the bonds in dichloro benzene, C6H4Cl2, were localized between specific carbon atoms, how may isomers of this compound would exist ? How many isomers actually exists. 3 . Which of the following compounds can exist as geometric isomers ? CH Cl , CH Cl—CH Cl, CHBr = CHCl, CH Cl—CH Br. 22 2 2 22 4 . How will you distinguish between Maleic acid and Fumaric acid ? 5 . Why does cyclopentene not exhibit geometric isomerism though it has a double bond. 6 . Why does 2-butene exhibit cis-trans isomerism but 2-yne does not ? 7 . Which of the following pairs show tautomerism. (a) and + (b) O HO and OCH3 OMe NN H3C—C—NMe2 H3C—C—NMe2 H 8 . Write structural isomer of C H . What is relation between them ? 6 14 9 . Arrange the following in the order of their enolic content : O OO O O O O IV I II III 1 0 . Which of the following does/do not exhibits tautomerism. O OO (i) CH3—C—CH3, (ii) CH3—C—CH2—C—OC2H5 O (iv) —OH (iii) CH2=CH—C—H

CONCEPTUAL SUBJECTIVE EXERCISE ANSWER KEY EXERCISE -4(A) 1 . There are 7—1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, diethyl ether, methyl propyl ether, and methylisopropyl ether. 2 . If the bonds were localized, there would be 4 isomers ; actually there are only 3 of the following, the first two are identical, because the bods are not localized. Cl Cl Cl Cl Cl Cl Cl Cl 3 . Only CHBr = CHCl can exist as geometric isomers : Br Cl Br H HC C and C C H H Cl In CH2Cl— CH2Cl and CH2Cl—CH2Br, the carbon atoms are connected by a single bond about which the groups can rotate relatively freely. Thus any conformation of the halogen atoms may be converted into any other simply by rotation about the single bond. In CH2Cl2, the configuration of the molecule is tetrahedral and all interchanges of atoms yield exactly equivalent configurations. 4 . Maleic acid forms an anhydride where as fumaric acid does not. O CO2H H C H CO2H CH H O CO2H H no anhydride. CH CO2H H  C   O H HH 5 . This is cis form. Two H atoms on the same side. To get trans, ring must be twisted. Double bond becomes severely twisted-destabilized. Effective overlap of P orbitals is missing, so does not exist. 6 . The Pz orbitals forming -bonds and the empty Pz orbital of the carbon with +ve charge are parallel. So the electrons may be delocalized. The +ve charge is effectively spread out over two carbons; delocalized. H -orbital C empty orbital H C C+ H H  CH2=CH— C H2  C H2 —CH= CH In n-propyl cation, + I effect of R increases the stability. In allyl + M effect increases the stability. But + M effect in allyl cation is more effective. So allyl > propyl. A group with + M effect stabilizes cation; destabilizes anion. 7 . Lone pair - p conjugation between fluorine and carbon will be more effective than between chlorine and carbon. 9. III > IV > I > II

EXERCISE–04 [B] BRAIN STORMING SUBJECTIVE EXERCISE SUBJECTIVE QUESTIONS : 1 . What is relation between (a), (b), (c) ? O O– HN NH OH ++ (a) HN NH NN ON O (b) (c) –O + O– H N HO N OH H 2 . Which side is favoured at equilibrium, provide quantitative explanation : O O H2O  OO + HO– O O pKa  16 OO pKa =13 3 . (+) 2-butanol has specific rotation of + 13.9° when measured in pure form. A sample of 2-butanol was found to have an optical rotation of –3°. What is the stereomeric composition of this mixture ? 4 . N-methylethenamine as such does not show any stereoisomerism but one of its resonance form exhibit stereoisomerism. Explain. 5 . Assign Cahn-ingold prelog priorites to the following sets of substituents : (i) —H, —Br, —CH2CH3, —CH2CH2OH (ii) —COOH, —COOCH3, —CH2OH, —OH (iii) —CN, —CH NH , —CH NHCH , —NH (iv) —Br, —CH Br, —Cl, —CH Cl 22 23 2 22 6 . Identify whether the stereogenic centre is present or not : (i) 2-Cyclo penten-1-ol (ii) 3-cyclo penten-1-ol (iii) 2-bromopentane (iii) 3-bromopentane 7 . Discuss the optical activity of tertiary amines of the type R1R2R3N : 8 . Draw the enantiomer of the following structure : CH3 HC Cl C2H5 9 . 2,4-Hexadiene has three geometrical isomers. Draw their structures. 1 0 . Assign R and S configuration to the chiral carbons in the following : CH3 CH3 H———OH HO———H (ii) (i) H———OH H———OH CH3 CH3

BRAIN STORMING SUBJECTIVE EXERCISE ANSWER KEY EXERCISE -4(B) 1. a & b are tautomers and a & c are resonating structures. 3. Let x is the % of (+) 2-butanol. 13.9 x – 13.9 (100 – x) = – 300. x = 39.2, % of d form = 39.2, % of  form = 60.8. : : CH2 =CH — NH—CH3 4.  CH2 —CH = NH—CH3 (this shows Geometrical isomerism) 5. (a) —Br > —CH2CH2OH > —CH2CH3 >— H, (b) —OH > —COOCH3 >—COOH >—CH2OH (c) —NH2 >—CN >—CH2NHCH3 >—CH2NH2 (d) —Br >—Cl >—CH2Br >—CH2Cl 4=3 3=4 6. (i) Hydroxyl bearing carbon is stereogenic centre., (ii) 5=2 2=5 It has no stereogenic centre. H OH H OH Br (iii) CH3—C—CH2—CH2—CH3 bromine bearing carbon is stereogenic centre. H Br (vi) CH3—CH2—CH—CH2—CH3 It has no stereogenic centre. •• 7 . Ter tiar y amines have pyramideal geometry with sp3-hybridization at nitrogen. N It should be a chiral molecule (assuming lone pair to be a substituent). Thus, R1 R3 tertiary amines exist as racemic mixture but they cannot be resolved. R2 This is due to the reason that the energy difference between the isomer is very small (25 kJ mol–1). Hence, rapid nitrogen or amine inversion takes palce. R1 sp2 sp2-hybridized sp2 R1 R1 R2 N ••N N R2 • • •• R3 R2 R3 R3 Planar transition state Enantiomers Tertiary amine N-oxide has four group hence nitrogen inversion is not possible, thus tertiary amine -N-oxide can be resolved. CH3 8 . Cl C H C2H5 10. (i) 2R, 3R (ii) 2S, 3R

EXERCISE–05(A) PREVIOUS YEARS QUESTIONS 1 . Recemic mixture is formed by mixing two- [AIEEE-2002] (1) isomeric compounds (2) chiral compounds (3) meso compounds (4) enantiomers with chiral carbon 2 . Geometrical isomerism is not shown by- [AIEEE-2002] (1) 1,1–dichloro–1–pentene (2) 1,2–dichloro–1–pentene (3) 1,3–dichloro–2–pentene (4) 1,4–dichloro–2–pentene 3 . Following types of compounds I and II [AIEEE-2002] (I) CH CH=CHCH (2) position isomerism 33 (4) stereo isomerism (II) CH3 CH OH, are studied [AIEEE-2003] CH2CH3 in terms of isomerism in- (1) chain isomerism (3) conformers 4 . Among the following four structures I to IV C2H5 CH C3H7 C2H5 C CH C2H5 H C2H5 CH C2H5 CH3 O CH3 + CH3 (I) (II) (IV) HC H (III) It is true that- (1) All four are chiral compounds (2) only I and II are chiral compounds (3) only III is a chiral compound (4) only II and IV are chiral compounds 5 . Which of the following will have a meso-isomer also- [AIEEE-2004] (1) 2–chlorobutane (2) 2,3–dichlorobutane (3) 2,3–dichloropentene (4) 2–hydroxy propanoic acid 6 . Amongst the following compounds, the optically active alkane having lowest molecular mass is (1) CH3 CH2 C CH [AIEEE-2004] CH3 (2) CH3 CH2 CH CH3 H (3) CH3 C (4) CH3 C2H5 CH2 CH2 CH3

7 . Which of following compounds is not chiral [AIEEE-2005] (1) 1–chloropentane (2) 2–chloropentane (3) 1–chloro–2–methyl pentane (4) 3–chloro–2–methyl pentane 8 . Of the five isomeric hexanes, the isomer which can give two monochlorinated compounds is- (1) 2-methyl pentane [AIEEE-2005] (2) 2,2–dimethyl butane (3) 2,3–dimethyl butane (4) n-hexane 9 . Which types of isomerism is shown by 2,3–dichloro butane- [AIEEE-2005] (1) structural (2) geometric (3) optical (4) diastereo 1 0 . Increasing order of stability among the three main conformations (i.e. Eclipse, Anti, Gauche) of 2-fluoroethanol is [AIEEE-2006] (1) Gauche, Eclipse, Anti (2) Eclipse, Anti, Gauche (3) Anti, Gauche, Eclipse (4) Eclipse, Gauche, Anti 1 1 . Which one of the following conformations of cyclohexane is chiral ? [AIEEE - 2007] (1) Twist boat (2) Rigid (3) Chair (4) Boat 1 2 . Which of the following molecules is expected to rotated the plane of plane-polarised light ? (1) HO CHO (2) [AIEEE - 2007] H SH CH2OH COOH H2N NH2 (4) H2N H H (3) H Ph Ph H HO2C CO2H [AIEEE - 2008] 1 3 . The absolute configuration of is (4) S, R [AIEEE - 2008] HO H H OH (1) S, S (2) R, R (3) R, S 1 4 .   D    glu cos e and   D    glu cos e are (1) conformers (2) epimers (3) anomers (4) enantiomers

1 5 . The alkene that exhibits geometrical isomerism is :- [AIEEE - 2009] (1) 2–butene (2) 2–methyl–2–butene (3) Propene (4) 2–methyl propene 1 6 . The number of stereoisomers possible for a compound of the molecular formula CH3–CH = CH–CH(OH)–Me is :- [AIEEE - 2009] (4) 2 (1) 4 (2) 6 (3) 3 1 7 . Out of the following, the alkene that exhibits optical isomerism is :- [AIEEE-2010] (1) 2-methyl-2-pentene (2) 3-methyl-2-pentene (3) 4-methyl-1-pentene (4) 3-methyl-1-pentene 1 8 . Identify the compound that exhibits tautomerism :- [AIEEE-2011] (1) 2-Pentanone (2) Phenol (3) 2-Butene (4) Lactic acid 1 9 . How many chiral compounds are possible on monochlorination of 2–methyl butane ? [AIEEE-2012] (1) 6 (2) 8 (3) 2 (4) 4 2 0 . Which branched chain isomer of the hydrocarbon with molecular mass 72 u gives only one isomer of mono substituted alkyl halide ? [AIEEE-2012] (1) Neohexane (2) Tertiary butyl chloride (3) Neopentane (4) Isohexane 2 1 . How many cyclic structures are possible for C4H6 :- [AIEEE-2012(Online)] (4) 6 (1) 3 (2) 5 (3) 4 2 2 . Maleic acid and fumaric acids are :- [AIEEE-2012(Online)] (1) Tautomers (2) Chain isomers (3) Geometrical isomers (4) Functional isomers PREVIOUS YEAR QUESTIONS ANSWER KEY EXERCISE-5(A) Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Ans 4 1 4 2 2 3 1 3 3211231 Que. 16 17 18 19 20 21 22 Ans 1 4 1 4 3 3 3

EXERCISE–05(B) PREVIOUS YEARS QUESTIONS MCQ's WITH ONE CORRECT ANSWER [IIT-90] 1 . The enolic form of acetone contains : (B) 8 bonds, 2 bonds and 2 lone pairs (D) 9 bonds, 2 bond and 1 lone pair (A) 9 bonds, 1 bond and 2 lone pairs (C) 10 bonds, 1 bonds and 1 lone pair 2 . An organic molecule necessarity shows optical activitiy if it : [IIT-93] (A) Contains asymmetric carbon atoms (B) is non polar (C) is non superimposable on its mirror image (D) is superimposable on its mirror image 3 . The compound which is not isomeric with diethyl ether is : [IIT-93] (A) butan–1–ol (B) butanone (C) 2–methyl propan–2–ol (D) n–propyl methyl ether 4 . Ordinary light can be converted into plane polarized light with the help of a : [IIT-93] (A) Nickel prism (B) Nicol prism (C) Diffraction grating (D) Quartz cell 5 . The structure shows : [IIT-95] H3C C=C H H H3C C COOH CH3 (B) Optical isomerism (A) Geometrical isomerism (C) Geometrical & optical isomerism (D) tautomerism 6 . How many optically active stereoisomers are possible for butane –2,3–diol : [IIT-97] (A) 1 (B) 2 (C) 3 (D) 4 7 . Isomers which can be interconverted through rotation around of single bond are - [IIT-97] (A) Conformers (B) Diastereomers (C) Enantiomers (D) Positional isomers 8 . The number of possible enantiomeric pairs that can be produced during monochlorination of 2–methyl butane is : [IIT-97] (A) 2 (B) 3 (C) 4 (D) 1 9 . Tautomerism is not exhibited by : [IIT-98] O (D) O (A) CH=CH–OH(B) O O (C) O [IIT-98] O (D) Viscometer 1 0 . Rotation of polarised light can be measured by : (A) Monometer (B) Galvanometer (C) Polarimeter 1 1 . The optically active tartaric acid is named as D–(+) tartaric acid because it has a positive : [IIT-99] (A) optical rotation and is derived from D–glucose (B) pH in an organic solvent (C) optical rotation and is derived from D–(+)– glyceraldehyde (D) optical rotation only when substituted by deuterium

1 2 . The enol form of acetone, after treatment with D2O gives [IIT-99] OD O (A) CH3–C=CH2 (B) CD3–C–CD3 OH OH (C) CH2–C=CH2D (D) CD2=C–CD3 1 3 . Which of the following compound will exhibits geometrical isomerism : [IIT-2000] (A) 1–phenyl–2–butene (B) 3–phenyl–1–butene (C) 2–phenyl–1–butene (D) 1, 1–diphenyl–1–propene 1 4 . The number of isomers for the compound with molecular formula C2BrCIFI is : [IIT-2000] (A) 3 (B) 4 (C) 5 (D) 6 1 5 . Which of the following exhibits stereoisomerism– [IIT-2000] (A) 2–Methylbutene–1 (B) 3–Methylbutyne–1 (C) 3–Methylbutanoic acid (D) 2–Methylbutanoic acid 1 6 . Hydrogen of the following compound in the presence of poisoned palladium catalyst gives : [IIT-2002] Me H Me H Me H (A) optically active compound (B) an optically inactive compound (C) a racemic mixture (D) a diastereomeric mixture 1 7 . Which of the following has the lowest dipole moment : [IIT-2002] CH3 C=C CH3 (C) CH3CH2CCH (D) CH2=CH–CCH H (B) CH3–CC–CH3 (A) H 1 8 . If C2 in below compound is rotated by 120º angle in anticlockwise direction along C2–C3, which of the following form will be produced : [IIT-2004] 1 CH3 HH 2 3 (A) Partial eclipsed HH (C) Perfectly staggered (D) Gauche conformation CH3 4 (B) Per fectly eclipsed CH3 1 9 . CH3–CH–CH2–CH3 Cl2/hv N  no. of isomers Fractionaldistillation  F , (N) and (F) are : [IIT-2006] (A) 6, 4 (B) 4, 4 (C) 6, 6 (D) 3, 3

2 0 . The number of structural isomers of C6H14 is : [IIT-2007] (A) 3 (B) 4 (C) 5 (D) 6 2 1 . The number of stereoisomers obtained by bromination of trans–2–butene is : [IIT-2007] (A) 1 (B) 2 (C) 3 (D) 4 2 2 . Statement-I : Molecules that are not superimposable on their mirror images are chiral Because Statement-II : All chiral molecules have chiral centres. [IIT-2007] (A) Statement-1 is True, Statement-2 is True ; Statement-2 is a correct explanation for Statement-1 (B) Statement-1 is True, Statement-2 is True ; Statement-2 is NOT a correct explanation for Statement-1 (C) Statement-1 is True, Statement-2 is False. (D) Statement-1 is False, Statement-2 is True. 2 3 . The correct statement(s) concerning the structures E, F and G is (are) [IIT-2008] H3C O H3C OH H3C CH3 H3C CH3 H3C CH3 H3C (E ) (F) OH (G ) (A) E, F and G are resonance structures [IIT-2008] (B) E, F and E, G are tautomers (C) F and G are geometrical isomers (D) F and G are diastereomers 2 4 . The correct statement(s) about the compound given below is (are) :- Cl H CH3 H3C H Cl (A) The compound is optically active (B) The compound possesses centre of symmetry (C) The compound possesses plane of symmetry (D) The compound possesses axis of symmetry 2 5 . The correct statement(s) about the compound H3C(HO)HC – CH = CH – CH(OH)CH3 (X) is (are) : (A) The total number of stereoisomers possible for X is 6 [IIT-2009] (B) The total number of diastereomers possible for X is 3 (C) If the stereochemistry about the double bond in X is trans, the number of enantiomers possible for X is 4 (D) If the stereochemistry about the double bond in X is cis, the number of enantiomers possible for X is 2 2 6 . The bond energy (in kcal mol–1) of a C–C single bond is approximately : [IIT-2010] (A) 1 (B) 10 (C) 100 (D) 1000

2 7 . In the Newman projection for 2,2–dimethylbutane [IIT-2010] X H3C CH3 HH Y X and Y can respectively be – (A) H and H (B) H and C H (C) C H and H (D) CH and CH 25 25 33 2 8 . Amongst the given option, the compound(s) in which all the atoms are in one plane in all the possible conformations (if any), is (are) - [IIT-2011] HH H (A) C – C CH2 (B) H – C  C – C (C) H C = C = O (D) H C = C = CH H2C 2 22 CH2 2 9 . Which of the given statement(s) about N,O,P and Q with respect to M is (are) correct ? [IIT-2012] HO H HO H Cl CH3 CH3 H OH OH HO H H H HO Cl CH3 HO H Cl H Q Cl OH HO H HO CH3 Cl CH3 Cl MN O P (A) M and N are non-mirror image stereoisomers (B) M and O are identical (C) M and P are enantiomers (D) M and Q are identical P & Q are isomers of dicarboxylic acid C4H4O4. Both decolorize Br2/H2O, On heating P forms the cyclic anhydride. Upon treatment with dilute alkaline KMnO4, P as well as Q could produce one or more than one from S, T and U. [JEE ADVANCED-2013] COOH COOH COOH H OH H OH HO H H OH HO H H OH COOH COOH COOH (S) (T) (U) 3 0 . Compounds formed from P and Q are respectively (A) Optically active S and optically active pair (T, U) (B) Optically inactive S and optically inactive pair (T, U) (C) Optically active pair (T, U) and optically active S (D) Optically inactive pair (T, U) and optically inactive S PREVIOUS YEARS QUESTIONS ANSWER KEY EXERCISE -5(B) 1. (A) 2. (C) 3. (B) 4.(B) 5. (B) 6. (B) 7.(A) 8. (A) 16. (B) 9. (B) 10. (C) 11. (C) 12. (A) 13.(A) 14. (D) 15.(D) 23. (B, C, D) 30. (B) 17. (B) 18. (D) 19. (B) 20. (C) 21. (A) 22. (C) 24. (A, D) 25. (A, D) 26. (C) 27. (B, D) 28. (B, C) 29. (A, B, C)



EXERCISE-01 CHECK YOUR GRASP SELECT THE CORRECT ALTERNATIVE (ONLY ONE CORRECT ANSWER) 1 . The most abundant element found in the earth's crust is:- (A) Tin (B) Hydrogen (C) Silicon (D) Oxygen 2 . Which of the following element is found in its native state:- (A) Sodium (B) Gold (C) Silver (D) Both (B) and (C) 3 . Which of the following contain both calcium and magnesium:- (A) Magnesite (B) Calamine (C) Carnalite (D) Dolomite 4 . Which of the following is not an ore of Iron:- (A) Haematite (B) Limonite (C) Cassiterite (D) Magnetite 5 . Litharge is a mineral of:- (A) Magnesium (B) Lithium (C) Lead (D) Zinc 6 . Which one is mineral of manganese:- (A) Magnesite (B) Malachite (C) Magnetite (D) Pyrolusite 7 . Calamine is:- (A) BaCO3 (B) ZnCO3 (C) ZnS (D) ZnO 8 . Black Jack is:- (A) Silicate ore (B) Oxide ore (C) Carbonate ore (D) Sulphide ore 9 . Pyrolusite is:- (A) MnO (B) Mn3O2 (C) SnO2 (D) MnO2 1 0 . The impurities present in the ore is called:- (A) Slag (B) Flux (C) Alloy (D) Gangue 1 1 . Leaching method is used to concentrate the ores of:- (A) Gold (B) Silver (C) Aluminium (D) All of these 1 2 . Which of the following can be obtained by hydrometallurgy :- (A) Copper (B) Gold (C) Silver (D) All of these 1 3 . Which is wrongly mached:- (A) Gun metal- Cu+Zn+Sn (B) Duralumin - Cu+Al+Mn (C) German silver Cu+Zn+Ni (D) Electron Pb+Sn 1 4 . The process of converting hydrated Alumina into anhydrous Alumina is called:- (A) Roasting (B) Calcination (C) Smelting (D) Dressing 1 5 . The metallurgical process in which a metal is obtained in a fused state is called:- (A) Smelting (B) Roasting (C) Calcination (D) Froth floatation 1 6 . Blister copper is:- (A) Pure copper (B) Ore of copper (C) Alloy of copper (D) Copper having 2% impurity 1 7 . Among the following pairs of oxides, In which pair both are reduced by carbon :- (A) SnO2 , MnO2 (B) Fe2O3, PbO (C) ZnO, K2O (D) CaO, Cr2O3

1 8 . Calomel is the name of :- (A) HgCl2 (B) Hg2Cl2 (C) HgCl2 + Hg (D) Hg2Cl2 + Hg 1 9 . \"Hydro metallurgy\" method is used for the extraction of the following metals :- (A) Zn & Ag (B) Ag & Cu (C) Zn & Hg (D) Hg & Cu 2 0 . Heating of pyrites to remove sulphur is called as:- (A) Roasting (B) Calcination (C) Smelting (D) Froth-floatation 2 1 . In which of the following reaction \"Philosopher's wool\" is formed:- (A) Zn + S  ZnS (B) Zn + Cl2  ZnCl2 (C) FeS + O2  FeO + SO2 (D) Zn + H2O (steam)  ZnO + H2 2 2 . Which one of the following metals can not be extracted by using Al as a reducing agent :- (A) Na from Na2O (B) Cr from Cr2O3 (C) Mn from MnO2 (D) Fe from Fe2O3 2 3 . The correct set of carbonate ores is : - (a) Magnesite (b) Siderite (c) Zincite (d) Argentite (A) a, b (B) a, d (C) c, d (D) b, c 2 4 . Calcination is the process of heating the ore :- (A) in inert gas (B) in the presence of air (C) in the absence air (D) in the presence of CaO and MgO 2 5 . Matte :- (A) Cu2S + FeS (B) Cu2O + FeS (C) Cu2O + Cu2S (D) FeS + SiO2 2 6 . Which of the following statement is correct for roasting :- (A) Convert sulphide to oxide (B) Convert sulphide to sulphate (C) Remove arsenic and sulphur impurities (D) All 2 7 . Among the following statements, the incorrect one is (A) Cassiterite ore of tin contains the impurities of Wolframite which are separated by electromagnetic separator. (B) Tin metal is obtained by the carbon reduction of black tin. (C) In the extraction of lead from galena, the roasting and self-reduction are carried out in the same furnance at different temperature. (D) None of these 2 8 . Fe can displace which of the following ions from their aqueous solutions ? (a) Na+ (b) Zn2+ (c) Cu2+ (d) Ag+ (A) a & b (B) b & c (C) c & d (D) b, c, d 2 9 . There are following extraction process of silver but not : (A) as a side product in electrolytic refining of copper (B) Parke's process in which Zn is used to extract silver by solvent extraction from molten lead (C) by reaction of silver sulphide with KCN and then reaction of soluble complex with Zn (D) by heating Na[Ag(CN2)] 3 0 . Which of the following is not an ore : (A) malacite (B) calamine (C) stellite (D) cerussite

3 1 . In the Pidgeon process, Mg is produced by : (A) electrolysis of fused MgCl2 (B) reducing calcined dolomite with ferrosilicon at high temperature under pressure (C) both are correct (D) none is correct 3 2 . \"Fool's gold\" is (A) iron pyrites (B) horn silver (C) copper pyrites (D) bronze 3 3 . Which one of the following reactions is an example for calcination process :- (A) 2Ag + 2HCl + (O)  2AgCl + H2O (B) 2 Zn + O2  2ZnO2 (C) 2ZnS + 3O2  2ZnO + 2SO2 (D) MgCO3  MgO + CO2 3 4 . Identify the process to which the following reaction belongs : Al2O3.2H2O + Na2CO3  2NaAlO2 + 2H2O + CO2 2NaAlO2 + 2H2O + CO2  5060C  Al2O3.2H2O + Na2CO3 (A) Hall's process (B) Baeyer's process (C) Serpeck's process (D) None of these LayerX 3 5 . (Ag + Pb) alloy Melt andaddzinc  (Ag + Pb + Zn) melt Cool  LayerY Select correct statement based on above scheme : (A) Layer X contains zinc and silver (B) Layer Y contains lead and silver but amount of silver in this layer is smaller than in the layer X (C) X and Y are immiscible layers (D) All are correct statements 3 6 . Formation of metallic copper from the sulphide ore in the normal thermo-metallurgical process essentially involves which one of the following reaction : 3 CuO + C  Cu + CO (A) CuS + 2 O2  CuO + SO2; 2CuO + CuS  3Cu + SO2 CuSO4 + CuS  2Cu + 2SO2 3 CuO + CO  Cu + CO2 (B) CuS + 2 O2  CuO + SO2; (C) CuS + 2O2  CuSO4; 3 (D) CuS + 2 O2  CuP + SO2; 3 7 . Bessemerisation is carried out for (i) Fe (ii) Cu (iii) Al (iv) silver (A) i, ii (B) ii, iii (C) iii, iv (D) i, iii

3 8 . Consider the following statement : Roasting is carried out to : (i) convert sulphide to oxide and sulphate (ii) remove water of hydration (iii) melt the ore (iv) remove arsenic and sulphur impurities Of these statements : (A) (i), (ii) and (iii) are correct (B) (i) and (iv) are correct (C) (i), (ii) and (iv) are correct (D) (ii), (iii) and (iv) are correct 3 9 . For extraction of sodium from NaCl, the electrolytic mixture NaCl + Na3AlF6 + CaCl2 is used. During extraction process, only sodium is deposited on cathode but K and Ca do not because (A) Na is more reactive than K and Ca (B) Na is less reactive than K and Ca (C) NaCl is less stable than Na3AlF6 and CaCl2 (D) the discharge potential of Na+ is less than that of K+ and Ca2+ ions. 4 0 . Among the following statements, the incorrect one is : (A) Calamine and siderite are carbonates (B) Argentite and cuprite are oxides (C) Zinc blende and pyrites are sulphides (D) Malachite and azurite are ores of copper 4 1 . Pb and Sn are extracted from their chief ore by : (A) Carbon reduction and self reduction respectively. (B) Self reduction and carbon reduction respectively. (C) Electrolysis and self reduction respectively. (D) Self reduction and electrolysis respectively. CHECK YOUR GRASP ANSWER KEY E X E R C IS E -1 Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Ans. D D D C CDBDDDDD DB A Que. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 Ans. D B B B A D AACA DD CDC Que. 31 32 33 34 35 36 37 38 39 40 41 Ans. B A D A DB ACDB B

EXERCISE–02 BRAIN TEASERS SELECT THE CORRECT ALTERNATIVES (ONE OR MORE THEN ONE CORRECT ANSWERS) 1 . During the extraction of Ag and Au using a KCN solution, cyanide ions react with metal ions as (A) a reducing agent (B) a complexing agent (C) an oxidizing agent (D) a lewis base 2 . Which of the following is dolomite:- (A) CaCO3. MgCO3 (B) Cu2S Fe2S3 (C) CdS (D) ZnS 3 . Which of the following ores is a double salt composition :- (A) Carnallite (B) Alum (C) Dolomite (D) Cerrusite 4 . The following metal- ore combination is correct :- (A) Pb-Galena (B) Fe-siderite (C) Al-Bauxite (D) Mn-Magnesite 5 . NaCN used in the froth floatation method for the purification of ore is:- (A) ZnS which contain PbS (B) Cu2S which contain Fe2S3 (C) PbS which contain ZnS (D) PbS which contain SiO2 6 . Which of the following metal can not be extracted by smelting process:- (A) Lead (B) Zinc (C) Iron (D) Aluminium 7 . The reduction of Cr2O3, by heating it with aluminium is known as:- (A) Smelting (B) Roasting (C) Calcination (D) Aluminothermic process 8 . Which metal is leached from its ore by the use of KCN :- (A) Copper (B) Zinc (C) Gold (D) Iron 9 . Name the flux to remove the impurity of SiO2 :- (A) P4O10 (B) CaO (C) N2O5 (D) Al2O3 1 0 . Mercury containers are made of:- (A) Fe (B) Pb (C) Sn (D) Zn 1 1 . Autoreduction process is used in the extraction of:- (A) Cu & Pb (B) Zn & Hg (C) Cu & Al (D) Fe & Pb 1 2 . When Alumina is electrolysed in presence of cryolite, the gas liberated at graphite anode is:- (A) F2 (B) O2 (C) CF4 (D) Cl2 1 3 . In the extraction of copper, metal is formed in the Bessemer converter due to reaction:- (A) Cu2S + 2Cu2O  6Cu + SO2 (B) Cu2S  2Cu + S (C) Fe + Cu2O  2Cu + FeO (D) 2Cu2O  4Cu + O2 1 4 . x, y and z in the following processes are respectively:- (i) P2O5 + .......x.....  Ca3(PO4)2 (ii) 2Cu2O + Cu2S  ......y..... + SO2  (iii) Fe2O3 + 3CO  .......z ..... + 3CO2  (A) 3Ca, CuSO4, Fe (B) 3Ca(OH)2, 6Cu, FeO (C) 3CaO, 6Cu, 2Fe (D) 3CaO2 , CuS, FeO 1 5 . Which of the following process involves smelting (A) 2 PbS + 3O2  2PbO + 2SO2  (B) Al2O3. 2H2O  Al2O3 + 2H2O (C) Fe2O3 + CO  2Fe + 2CO2 (D) Cr2O3 + 2Al  Al2O3 + 2Cr + Heat

1 6 . Out of the following, which ores are calcinated during extraction :- (a) Copper pyrites (b) Malachite (c) Bauxite Correct answer is :- (A) a, b, c (B) b, c (C) Only a (D) All 1 7 . Which of the following match are incorrect :- (A) Goldschmidt aluminothermite process - Cr2O3 (B) Mac Arther cyanide process - Fe (C) Mond process - Ni (D) Van Arkel process – Au 1 8 . Malachite on calcination gives  'A' + CO2 + H2O. Compound 'A' on reduction with carbon gives  CO + 'B' . Here 'A' and 'B' are :- (A) Fe2O3, Fe (B) CuO, Cu (C) CuCO3, CuO (D) MgO, Mg 1 9 . Which of the following ores are calcinated during extraction :- (A) Argentite (B) Calamine (C) Azurite (D) Copper pyrites 2 0 . Which method of purification is represented by the following equations Ti + 2I2 523K  TiI4 1700 K  Ti + 2I2 (A) Cupellation (B) Poling (C) Van Arkel (D) Zone refining 2 1 . Which are correctly is matched :- (A) Poling – refining of copper (B) Cupellation – refining of silver (C) Smelting – An oxidation process (D) Roasting – An oxidation process 2 2 . Which of the following reaction is a part of Serpeck's process :- (A) Al2O3 + 2NaOH  2NaAlO2 + H2O (B) Fe2O3 + 2Al  2Fe + Al2O3 (C) AlN + 3H2O  Al(OH)3 + NH3 (D) Al2O3. 2H2O + 2Na2CO3  2NaAlO2+CO2 + 2H2O 2 3 . The following equation represents a method of purification of nickel by :- Ni + 4CO 320K  Ni(CO)4 420K  Ni + 4CO impure pure (A) Cupellation (B) Mond's process (C) Van Arkel method (D) Zone refining 2 4 . Which substance is used as basic refractory material in furnace :- (A) Al2O3 (B) SiO2 (C) CaO (D) Fe2O3 2 5 . Carbon cannot be used in the reduction of Al2O3 because :- (A) it is an expensive (B) the enthalpy of formation of CO2 is more than that of Al2O3 (C) pure carbon is not easily available (D) the enthalpy of formation of Al2O3 is too high 2 6 . Which of the following reaction is not involved in themite process :- (A) 3Mn3O4 + 8Al  9Mn + 4Al2O3 (B) Cr2O3 + 2AI  Al2O3 + 2Cr (C) 2Fe + Al2O3  2Al + Fe2O3 (D) B2O3 + 2Al  2B + Al2O3 2 7 . Which of the following reduction processes are correct :- (A) Fe2O3 + C  Re duction  Fe (B) ZnO + C  Re duction  Zn (C) SnO2 + C  Re duction  Sn (D) PbO + C  Re duction  Pb

2 8 . Consider the following steps : Cu2S roast in air  A Heatingwithout air  B Which is not the correct statement : (A) it is self-reduction (B) A is only Cu2O & B is a mixture of Cu & SO3 (C) A is a mixture of Cu2O and Cu2S and B is a mixture of Cu & SO2 (D) all are incorrect statements 2 9 . Main source of lead is PbS. It is converted to Pb by :- (i) PbS air  PbO + SO2 C  Pb + CO2   (ii) PbS air  PbO + PbS   Pb + SO2  Self reduction process is : (A) i (B) ii (C) Both (D) None 3 0 . Ag2S + NaCN  A A + Zn  B B is a metal. Hence A and B :- (A) Na2 [Zn(CN)4], Zn (B) Na[Ag(CN)2], Ag (C) Na[Ag(CN)4], Ag (D) Na3[Ag(CN)4], Ag 3 1 . Ca3(PO4)2 is :- (A) Thomas slag (B) Used in cement manufacturing (C) Used in manufacturing of phosphorus fertilizer (D) Used as a refactory material 3 2 . Bauxite is purified by :- (A) Hall's process (B) Baeyer's process (C) Serpeck's process (D) L.D. process 3 3 . The processes which do use catalysts are :- (A) Contact process (B) Thermite process (C) Ostwald's process (D) Haber's process 3 4 . Metallurgy involves steps :- (A) concentration of ore (B) Oxidation of ore (C) purification (D) Reduction of ore 3 5 . Which of the following metals are extracted by electrolytic reduction ? (A) Cu (B) Al (C) Mg (D) Ag 3 6 . Which of the following ores is/are oxide ore(s) ? (A) Cassiterite (B) Bauxite (C) Cryolite (D) Haematite 3 7 . Which of the following are correctly matched ? (A) Schweitzer's reagent  An ammoniacal solution of cupric sulphate (B) Bordeaus mixture  CuSO4 and Ca(OH)2 (C) Semiconductor  Ge (D) Horn silver  AgNO3 3 8 . In which of the following pair(s), the minerals are converted in to metals by self-reduction process? (A) Cu2S, PbS (B) PbS, HgS (C) PbS, ZnS (D) Ag2S, Cu2S (C) Leaching (D) Calcination 3 9 . Cassiterite ore (SnO2) is purified by :- (A) Magnetic separator (B) Roasting

4 0 . The reaction(s) which does (do) not occur in the reduction zone in the extraction of iron from haematite ore is (are) :- (A) Fe2O3 + CO  2FeO + CO2 (B) FeO + CO  Fe + CO2 (C) Fe2O3 + 3C  2Fe + 3CO (D) CaO + SiO2  CaSiO3 4 1 . Which of the following statement(s) is (are) true ? (A) In process of the precipitation of silver sodium dicyano argentate (l), the zinc acts as reducing agent as well as complexing agent. (B) In process of the roasting, the copper pyrites is converted into a mixture of Cu2S & FeS which, in turn, are partially oxidised (C) Limonite, haematite and magnesite are ores of iron. (D) Tin and lead both are extracted from their ores by self-reduction. 4 2 . The role of fluorspar (CaF2) which is added in the electrolytic reduction of alumina dissolved in fused cryolite is (are) :- (A) to acts as a catalyst (B) to make the fused mixture very conducting (C) to lower the temperature of the melt (D) to decrease the rate of oxidation of carbon at the anode 4 3 . Which of the followgin are correctly mathched ? (A) Turquoise  (CuAl6PO4)4 (OH)8 . 4H2O (B) Peacock ore  Cu4FeS2 (C) Malachite  CuCO3 . Cu(OH)2 (D) Chalcopyrites  CuFeS2 4 4 . Which of the following statements are correct in connection with the extraction of silver ? (A) Silver is obtained as a by-product in the extraction of copper, lead and zinc. (B) Silver is obtained from the anode slime formed in the electrolytic refining of copper and zinc (C) Zinc is used to extract silver by solvent extraction from molten lead in Parke's process. (D) Pttinsons process is used for desilverization of lead 4 5 . Which of the following does not disproportionate ? (A) Cu+ (B) Au3+ (C) Cu2+ (D) Au+ B R AIN TE AS E R S ANSWER KEY E X E R C IS E -2 Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 A n s . B,D A A ,B,C A ,B,C C D D C B A A B A C C Que. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 A n s . B B,D B B,C C A ,B,D C B C D C A,B,C,D B B B Que. 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 A n s . A ,B,C A ,B,C A ,C ,D A ,C ,D B,C A ,B,D A ,B,C A ,B A C ,D A ,B B,C A ,C ,D A,B,C,D B,C

EXERCISE–03 MISCELLANEOUS TYPE QUESTIONS TRUE / FALSE 1 . Metals can be recovered from their ores by chemical methods. 2 . Sulphide ore of copper can be concentrated by froth floatation process. 3 . Silver is purified by distillation process. 4 . Highly pure metal can be obtained by zone refining. 5 . Zinc is precipitated from a solution of zinc sulphate by addition of iron. 6 . The slag obtained during the extraction of copper pyrites is composed mainly of FeSiO . 3 7 . In calcination, ore is heated strongly in the absence of air. FILL IN THE BLANKS 1 . The most abundant metal in the earth's crust is ................... 2 . Cassiterite is an ore of ................... . 3 . In the metallurgical process for the electro-refining of the metal, the anode is made of ................... metal. 4 . In a thermite process, ................... is used as a reducing agent. 5 . The mineral carnallite contains magnesium and ................... metal. 6 . The actual reducing agent of haematite in blast furnace is ................... 7 . In the basic Bessemer's process of the manufacture of steel, the linning of the converter is made of .................... The slag formed consists of ................... 8 . The transition metal present in the alloy gun metal is ................... 9 . The slag formed during the metallurgy of copper pyrites is ................... 1 0 . Iron is ................... copper in the electrochemical series and hence displaces ................... from a solution of copper sulphate. MATCH THE COLUMN 1. Column-I (Ore) Column-II (Created formula & properties) (A) Iron pyrites (p) FeS (B) Fool's gold 2 (C) Galena (D) Haematite (q) Sulphide ore (r) Fe O 23 (s) Concentrated by froth 2. Column-I (Metal) Column-II (A) Magnesite (p) Ore of magnesium (B) Siderite (q) Ore of aluminium (C) Corundum (r) Oxide ore (D) Bauxite (s) Carbonate ore 3. Column-I (Ore) Column-II (A) Iron (p) Carbon reduction method (B) Lead (q) Self reduction (C) Copper (r) Thermite process (D) Chromium (s) Hydrometallurgical process

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 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 : All the ores are mineral Statement-II : Most of the ores contains metals in combined state 2 . Statement-I : In the extraction of Ag the complex Na[Ag(CN)2] is reacted with Zn Statement-II : Zn is transition metal according to electronic theory 3 . Statement-I : Thermite mixture Fe O +Al (powder) is used in the welding. 23 Statement-II : Al is a good reductant 4 . Statement-I : CuFeS is concentrated by froath floatation method 2 Statement-II : CuFeS is main ore of copper 2 5 . Statement-I : In the smelting of copper ore coke is added in the blast furnace. Statement-II : Coke reduces, CuO into Cu. 6 . Statement-I : Extraction of iron metal from iron oxide ore is carried out by heating with coke. S t a t e m e n t - I I : The reaction Fe2O3(s) Fe(s) + 3/2O2(g) is a spontaneous process at standarde condition. 7 . S tatem ent- I : Wolframite impurities are separated from cassiterite by electromagnetic separation. S t a t e m e n t - I I : Cassiterite being magnetic is attached by the magnet and forms a separate heap. 8 . S t a t e m e n t - I : Lead, tin and bismuth are purified by liquation method. S t a t e m e n t - I I : Lead, tin and bismuth have low m.p. as compared to impurities. COMPREHENSION BASED QUESTIONS Comprehension # 1 Dow's process of extraction of Mg involves extraction of Mg from sea water. Sea water is concentrated in sun light and is then treated with skaked lime. Magnesium hydroxide is heated in a stream of HCl to give MgCl 2 which is electrolysed to dischatge Mg. The mixture is in the ratio 35% MgCl + 50% NaCl + 15% CaCl . 22 NaCl and CaCl are added to lower the fusion temperature and to increase the conductance. 2 Mg2+ + Ca(OH)2  Mg(OH)2 + Ca2+ Mg(OH) + 2HCl  MgCl + 2H O (liquid) 2 2 2 Electrolysis of fused MgCl A n ode  2Cl–  Cl + 2 e° 2 2 –1 Cathode Mg2+ + 2 e°  Mg –1 Mg electrolysed is protected from atmospheric oxidation by a blanket of inert gases.

1 . Mg2+ + Ca(OH)2  Mg(OH)2  + Ca2+ This reaction indicates : (A) Mg(OH)2 is weaker base than Ca(OH)2 (B) Soubility products of Mg(OH)2 is less than that of Ca(OH)2 (C) Polarising power of Mg2+ is more than that of Ca2+ ion (D) Both (B) and (C). 2 . In the hydrated chloride of Mg the value of of x is (A) 6 (B) 4 (C) 8 (D) 10 3 . Molten mixture contains Mg2+, Na+ and Ca2+ but at cathode only Mg is discharged because : (A) Standard reduction potential of Mg is least among the three (B) Standard oxidation potential of Mg is least among the three (C) Discharge potential of Mg is highest (D) None of these 4 . Molten mixture of NaCl of CaCl2 is added to the heated MgCl2.xH2O with dry HCl gas because : (A) MgCl2.xH2O + dry HCl 9731023 K Partially dehydrated MgCl2 and molten (NaCl + CaCl2) makes it fully dehydrated (B) CaCl2 is dehydrating agent (C) (CaCl2 + NaCl) lowers the m.pt. of MgCl2 (D) None of the above Comprehension # 2 Extraction of Aluminium can be understand by : Bauxite Conc. of Oreby Pure Alumina Re duction of alumina Al im pure Electrolysis  Al-Pure Al2O 3 .2H 2O Chemical method Al2O3 by electrolysis u sin g suspended graphite roads anode and C lining inside the Fecontainer electrolytic reduction of Al O 23 Electrolyte : (Al O + Cryolite) 23 Cathode : Graphite inside the Fe container Anode : Graphite rods 1 . The purpose of adding cryolite is : (A) to increase the electrical conductivity of pure aluminium (B) to lower the melting point of Al2O3 (C) to remove the impurities as slag (D) to increase the Al% in the yield

2 . Coke powder is spreaded over the molten electrolyte due to : (A) prevent the heat radiation from the surface (B) prevent the corrosion of graphite anode (C) prevent oxidation of molten aluminium by air (D) both (A) & (B) 3 . The function of fluorspar (CaF2) is : (A) to decrease the melting point of electrolyte (B) to increase electrolytic conductivity power (C) to remove the impurities as slag (D) all of the above 4 . The molten electrolytes contains Na+, Al3+, Ca2+ but only Al gets deposited at cathode because : (A) Standard reduction potential of Al is more than those of Na & Ca (B) Standard oxidation potential of Al is more than those of Na & Ca (C) Discharge potential of Al3+ is higher than Na+ & Ca2+ (D) Graphite reacts only with Al3+ and not with Na+ & Ca2+ 5 . What is wrong if anode is made of nickel instead of graphite? (A) Ni is costly (B) Anode will be affected by produced Cl2 (C) Graphite remain unaffected by produced Cl2 (D) Ni may be affected by high temp. MISCELLANEOUS TYPE QUESTION ANSWER KEY EXERCISE -3  True / False 1. T 2. T 3. F 4. T 5. F 6. T 7. T  Fill in the Blanks 1. Al 2.Tin 3.Impure 4.Al 5.K 6. CO 7.MgO,CaO, silicate, phosphate 8. Cu 9.FeSiO 10.Above, Cu 3  Match the Column 1. (A)  p,q,s; (B) p,q,s ; (C)  q,s ; (D) r 2. (A) p,s ; (B) s ; (C)  q,r ; (D) q,r 3. (A) p ; (B) p,q ; (C)  q,s ; (D) r  Assertion - Reason Questions 1. B 2. C 3. B 4. B 5. C 6. C 7. C 8. A  Comprehension Based Questions Comprehension #1 : 1. D 2. A 3. B 4. C Comprehension #2 : 1.B 2. D 3. B 4. A 5. B

EXERCISE–04 [A] CONCEPTUAL SUBJECTIVE EXERCISE 1 . Which of the metals Na, Ag and Fe are extracted by, (i) Complex formation (ii) Reduction with carbon and (iii) Electrolysis of fused salt ? 2 . How the following impurities can be removed? (a) An impurity of lead in silver. (b) An impurity of cuprous oxide in copper. (c) Impurities of Fe, Cu etc. in aluminium. 3 . Tin stone is amphoteric. Explain. 4 . Predict the mode of occurance of the following three type of metal. (i) Highly reactive (Na) (ii) Moderatyl reactive (Fe) (iii) Noble Metal (Au) 5 . Which is better reducing agent at 7100C, Coke or CO. 6 . Name the process from which chlorine is obtained as by product. What will happen if an aqueous solution of NaCl is subjected to electrolysis. 7 . What is Lintz-Dusenverfahren (L–D) process? 8 . Identify (A) to (F) in the following : FeSO 4   (A )  (B) (C ) Solid gas (B ) O2 (C ) (E ) H2O(D ) brown ppt (D )  (A ) (A ) HCl deep yellow solution (E) (E ) K4 [Fe(CN )6]  blue ppt. (F ) CONCEPTUAL SUBJECTIVE EXERCISE ANSWER KEY EXERCISE -4(A) 1 . Na – (iii), Ag–(i), Fe–(ii) 2 . (a) Cupellation, (b) Poling, (c) Electrolytic (Hoop's process) 3. SnO + 2H SO  Sn(SO ) + HO (SnO react with both acid and base) 2 24 42 2 2 SnO2 + NaOH  Na2SnO3 4 . (i) Na  Combined form (ii) Fe  Combined form (iii) Au  Native/Noble form 5 . C O (Ellingham diagram) 6 . Down cell process NaOH, H , Cl 22 7 . It is pyrometallurgical process in the manufacturing of steel to oxidise impurities. 8 . (A) : Fe O (B) : SO (C) : SO (D) : Fe(OH) (E) : FeCl (F) : KFeIII[FeII(CN) ], Prussian blue. 23 2 3 33 6

EXERCISE–04 [B] BRAIN STORMING SUBJECTIVE EXERCISE 1 . Write example of two metals which are manufactured by the electrolysis of their fused salts. 2 . Write example of two metals which are used for the reduction in metallurgical process. 3 . Which of the following metals can be obtained by the electrolytic reduction of aqueous solution of their salts – Al, Na, Cu and Ag ? 4 . Zinc and not copper is used for the recovery of Ag from the complex [Ag(CN) ]–. 2 5 . Partial roasting of sulphide ore is done in the metallurgy of copper. 6 . 6 . Why is chalcocite roasted and not calcined during recovery of copper? 7 . Egg shell is made up of a chemical. In which of the two ores this chemical is present. 8 . 8 . You are provided with sample of some impure metal. Such as zinc, copper and germanium which method would you recommended for the purification of each of these metal. 9 . Name the metal which are associated with the following term in their extraction from their ores. (i) Bessmer's convertor (ii) Blast furnace (iii) Alumino thermic process (iv) Magnetic separation 1 0 . Carbon monoxide is more effective reducing agent than carbon below 983 K but above this temperature the reverse is true. How would you explain this? 1 1 . Write balanced equations for the extraction of aluminium from bauxite by electrolysis. 1 2 . The following are two reaction schemes involving Mg. Scheme-I : Mg air  colourless solid A HCl colourless soltuion B Na2CO3 white ppt C   D colourless gas E Ca(OH)2  white ppt F Scheme-II : Mg dil. H2SO4  colourless solution G NaOH white ppt H HNO3  colourless solution evaporate  I   J gas + O + D 2

CONCEPTUAL SUBJECTIVE EXERCISE ANSWER KEY EXERCISE -4(B) 1 . Na, Al 2 . Al, Mg, Na 3 . Cu, Ag, 4 . Zn is powerful, Reducing agent than Cu 5 . Self/auto reduction 6 . Chalcosite is a sulphide ore so on roasting it converted into oxide. 7 . Lime stone : CaCO Dolomite : CaCO .MgCO 3 33 8 . Zn  Fractional distillation Cu  Poling & electro refining Ge  Zone refining/fractional crystallisation 9 . (i) Cu (ii) Fe (iii) Al (iv) Tin stone and Chromite ore 1 0 . The three reactions are as : C + O  CO .....(i) C (iii) O (s) 2 2  G° 2CO+O2  CO2 (i) C(S) + O2 CO2 2C + O  2CO .....(ii) 2C +O2 (s) 2 (S) 2CO 2CO + O  2CO .....(iii) T 983 K (ii) 22 Below 983 K reaction 2CO + O  2CO is more favoured due to more negative G value thus CO is better 2 2 reducing agent than carbon. Above 983 K, reaction 2C + O  2CO has more negative G than oxidation of CO to CO , so carbon will (s) 2 2 be better reducing agent. 1 1 . The following reactions take place. 4AlF  4Al3+ + 12F– 3 12F–  12F + 12e At cathode : 2Al O + 12F  4AlF + 3O 23 3 2 4C + 3O  2CO + 2CO 22 At Anode : 4Al3+ + 12e–  4Al 1 1 2 . A : MgO; B : MgCl ; C : MgCO ; D : MgO; E : CO ; F : CaCO ; G : MgSO ; 23 23 4 H : Mg(OH) ; I : Mg(NO ) ; J : NO 2 32 2

EXERCISE–05 [A] PREVIOUS YEARS QUESTIONS 1 . Aluminium is extracted by the electrolysis of :- (1) Bauxite [AlEEE-2002] (2) Alumina (3) Alumina mixed with molten cryolite (4) Molten cryolite 2 . Pyrolusite is a/an :- [AlEEE-2002] (1) Oxide ore (2) Sulphide ore (3) Carbide ore (4) Not an ore 3 . Which one of the following ores is best concentrated by froth-flotation method : [AIEEE-2004] (1) Galena (2) Cassiterite (3) Magnetite (4) Malachite 4 . Which of the following factors is of no significance for roasting sulphide ores to the oxides and not subjecting the sulphide ores to carbon reduction directly ? [AlEEE-2008] (1) Metal sulphides are thermodynamically more stable than CS 2 (2) CO is thermodynamically more stable than CS 22 (3) Metal sulphides are less stable than the corresponding oxides (4) CO2 is more volatile than CS2 5 . In context with the industrial preparation of hydrogen from water gas (CO + H ), which of the following is the 2 correct statement? [AlEEE-2008] (1) CO and H are fractionally separated using differences in their densities 2 (2) CO is removed by absorption in aqueous Cu Cl solution 22 (3) H is removed through occlusion with Pd 2 (4) CO is oxidised to CO with steam in the presence of a catalyst followed by absorption of CO in alkali 22 6 . Which method of purification is represented by the following equation : [AlEEE-2012] Ti(s) + 2I2(g) 523K TiI4(g) 1700K Ti(s) + 2I2(g) (1) Van Arkel (2) Zone refining (3) Cupellation (4) Poling PREVIOUS YEARS QUESTIONS ANSWER KEY EXERCISE -5 [A] Que. 1 2345 6 Ans 3 1134 1

EXERCISE–05 [B] PREVIOUS YEARS QUESTIONS 1 . When the ore haematite is burnt in air with coke around 2000°C alongwith lime, the process not only produces steel but also produces a silicate slag, that is useful in making building materials such as cement. Discuss the same and show through balanced chemical equation : [1998 ; 4M] 2 . In the commercial electrochemical process for aluminium extraction, the electrolyte used as:[IIT-1999] (A) Al(OH)3 in NaOH solution (B) An aqueous solution of Al2(SO4)3 (C) A molten mixture of Al2O3 and Na3AlF6 (D) A molten mixture of AlO(OH) and Al(OH)3 3 . Write the chemical reactions involved in the extraction of metallic silver from argentite. [IIT-2000] 4 . Write down reactions involved in the extraction of Pb. What is the oxidation number of lead in litharge? [IIT-2000] 5 . The chemical process in the production of steel from haematite ore involve : [IIT-2000] (A) Reduction (B) Oxidation (C) Reduction followed by oxidation (D) Oxidation followed by reduction 6. Electrolyte reduction of alumina to aluminium by Hall-Heroult process is carried out : [IIT-2000] (A) In the presence of NaCl (B) In the presence of fluorite (C) In the presence of cryolite which forms a melt with lower melting temperature (D) In the presence of cryolite which forms a melt with higher melting temperature 7 . The chemical composition of slag formed during smelting process in the extraction of Cu is :[IIT-2001] (A) Cu2O + FeS (B) FeSiO3 (C) CuFeS2 (D) Cu2S + FeO [IIT-2002] 8 . Which of the process is used in the extractive metallurgy of Mg : (A) Fused salt electrolysis (B) Self reduction (C) Aqueous solution electrolysis (D) Thermite reduction 9 . Roasted gold ore + CN– + H2O O2  [X] + OH– [IIT-2003] [X] + Zn  [Y] + Au. [X] and [Y] are : (A) X = [Au(CN)2]– ; Y = [Zn(CN)4]2– (B) X = [Au(CN)4]3– ; Y = [Zn(CN)4]2– (C) X = [Au(CN)2]– ; Y = [Zn(CN)6]4– (D) X = [Au(CN)4]3– ; Y = [Zn(CN)6]2– 1 0 . The methods chiefly used for the extraction of lead and tin from their ores are respectively :[IIT-2004] (A) self reduction and carbon reduction (B) self reduction and electrolytic reduction (C) carbon reduction and self reduction (D) cyanide process and carbon reduction 1 1 . Which ore contains both iron and copper? [IIT-2004] (A) Cuprite (B) Chalcocite (C) Chalcopyrite (D) Malachite 1 2 . A1 and A2 are two ores of metal M. A1 on calcination gives black precipitate, CO2 and water.[IIT-2004] A1 Calcination Black solid + CO2 + H2O dKil.IHCl I2 + ppt. A2 Roasting M etal  gas K2Cr2O7  Green Colour H 2 SO 4 Identify A1 and A2.

13. Match the column : Column I Column II [IIT-2006] (A) Self reduction (p) Lead (B) Carbon reduction (q) Silver (C) Complex formation and displacement by metal (r) Copper (D) Decomposition of iodide (s) Boron 1 4 . Extraction of zinc from zinc blende is achieved by : [IIT-2007] (A) electrolytic reduction (B) roasting followed by reduction with carbon (C) roasting followed by reduction with another metal (D) roasting followed by self-reduction 15. Match the column : Column I Column II [IIT-2008] (A) PbS  PbO (p) Roasting (B) CaCO3  CaO (q) Calcination (C) ZnS  Zn (r) Carbon reduction (D) Cu2S  Cu (s) Self reduction 1 6 . Native silver metal forms a water soluble complex with a dilute aqueous solution of NaCN in the presence of (A) nitrogen (B) oxygen [IIT-2008] (C) carbon dioxide (D) argon Paragraph for questions 17 to 19 Copper is the most nobel of the first row transition metals and occurs in small deposits in several countries. Ores of copper include chalcanthite (CuSO4 . 5H2O), atacamite (Cu2Cl(OH)3), cuprite (Cu2O), copper glance (Cu2S) and malachite (Cu2(OH)2CO3). However, 80% of the world copper production comes from the ore chalcopyrite (CuFeS2). The extraction of copper from chalcopyrite involves partial roasting, removal of iron and self-reduction. 1 7 . Partial roasting of chalcopyrite produces :- [IIT-2010] (A) Cu2S and FeO (B) Cu2O and FeO (C) CuS and Fe2O3 (D) Cu2O and Fe2O3 1 8 . Iron is removed from chalcopyrite as :- (A) FeO (B) FeS (C) Fe2O3 (D) FeSiO3 1 9 . In self-reduction, the reducing species is :- (A) S (B) O2– (C) S2– (D) SO2 [IIT-2011] 2 0 . Extraction of metal from the ore cassiterite involves (A) carbon reduction of an oxide ore (B) self-reduction of a sulphide ore (C) removal of copper impurity (D) removal of iron impurity 2 1 . Oxidation states of the metal in the minerals haematite and magnetite, respectively, are [IIT-2011] (A) II, III in haematite and III in magnetite (B) II, III in haematite and II in magnetite (C) II in haematite and II, III in magnetite (D) III in haematite and II, III in magnetite 2 2 . In the cyanide extraction process of silver from argentite ore, the oxidizing and reducing agents used are : (A) O2 and CO respectively. (B) O2 and Zn dust respectively. [IIT-2012] (C) HNO3 and Zn dust respectively. (D) HNO3 and CO respectively.

2 3 . Sulfide ores are common for the metals - [IIT-2013] [IIT-2013] (A) Ag, Cu and Pb (B) Ag, Cu and Sn (C) Ag, Mg and Pb (D) Al, Cu and Pb 2 4 . The carbon-based reduction method is NOT used for the extraction of (A) tin from SnO2 (B) Iron from Fe2O3 (C) aluminium from Al2O3 (D) magnesium from MgCO3.CaCO3 PREVIOUS YEARS QUESTIONS ANSWER KEY EXERCISE -5 [B] 1 . Heamatite (Fe2O3) on burning with coke and lime at 2000 K in blast furnace results in the following. (i) Upper zone (400°C to 700°C) Fe2O3 + 3CO  2Fe + 3CO2 3Fe2O3 + CO  2Fe3O4 + CO2 Fe3O4 + CO  3FeO + CO2 FeO + CO  Fe + CO2 ———————————————— This reaction occurs in following steps: (ii) Middle zone (800°C to 1000°C) C + CO2  2CO FeO + CO  Fe(s) + CO2 (iii) Upper lower zone Impure iron metals (1200°C to 1500°C) CaO + SiO2  CaSiO3 (slag) (iv) Lower zone Phosphates and silicates are reduced. (1500°C to 1600°C) P and S pass into molten iron C + O2  CO2 2. (C) 3. Ag2S + 4 NaCN 2Na[Ag(CN)2] + Na2S Argentite (0.7% solution) sodium argentocyanide 2Na[Ag(CN)2] + Zn  Na2[Zn(CN)4] + 2Ag This Na2S is oxidised into Na2SO4 to avoid reversibility of reaction. 4Na2S + 5O2 + 2H2O  2Na2SO4 + 4NaOH + 2S 4 . 2PbS + 3O2 2PbO + 2SO2 Roasting PbS + 2O2 PbSO4 The roasted mineral is smelted into lead. 2PbO + PbS 3Pb + 3SO2 PbSO4 + PbS 2Pb + 2SO2 Smelting This lead is purified by any suitable method. In litharge (PbO) oxidation state of lead is +2. 5.D 6. C 7. B 8. A 9. A 10. A 11. C 12. A1 : Malachite A2 : Copper glance 13. (A) p,r ; (B) p ; (C)  q ; (D) s 14. B 15. (A) p ; (B) q ; (C)  p,r ; (D) p,s 16. B 17. A 18. D 23. (A) 19. C 20. (A, C, D) 21. D 22. B 24. (C, D)



EXERCISE-01 CHECK YOUR GRASP SELECT THE CORRECT ALTERNATIVE (ONLY ONE CORRECT ANSWER) 1 . The final product obtained when boric acid is heated to red heat is – (A) Metaboric acid (B) Tetraboric acid (C) Boron oxide (D) Pyroboric acid 2 . Which of the following can be detected by the borax-bead test ? (A) Ni2+ (B) Co2+ (C) Pb+2 (D) Both (A) & (B) 3 . Boric acid polymerizes due to – (A) The presence of hydrogen bonds (B) Its acidic nature (C) Its geometry (D) Its monobasic nautre 4 . Aluminium is obtained by– (A) Reduction of Al O with coke 23 (B) Electrolysis of Al O dissolved in Na AlF 23 36 (C) Reduction of Al O with chromium 23 (D) Heating cryolite and alumina 5 . In thermite welding, aluminium acts as – (A) A solder (B) A flux (C) An oxidising agent (D) A reducing agent 6 . From B H , all the following can be prepared except – 26 (A) B O (B) H BO (C) B (CH ) (D) NaBH 23 33 2 36 4 7 . The product formed in the reaction, BCl + H O  Product is – 32 (A) H BO + HCl (B) B O + HOCl (C) B H + HCl (D) No reaction 33 23 26 8 . The hydrides of boron are called (A) Boron hydrogen compounds (B) Hydrogen borides (C) Boranes (D) Hydroboric acids 9 . Which one of the following mixed sulphates is not an alum ? (A) K SO .Al (SO ) .24H O (B) K SO .Cr (SO ) .24H O 2 42 43 2 242 43 2 (C) Na SO .Fe(SO ) .24H O (D) CuSO .Al (SO ) .24H O 24 43 2 42 43 2 1 0 . Higher percentage of carbon is found in – (A) Anthracite (B) Lignite (C) Bituminous (D) Peat 1 1 . Silicones have the general formula – (A) SiO44– (B) Si2O76– (C) (R2SiO)n (D) (SiO3)n2– 1 2 . In which of the following there exists a p – d bonding – (A) Diamond (B) Graphite (C) Dimethylamine (D) Trisilylamines 1 3 . Glass or silica soluble in – (A) HClO (B) HF (C) Aqua-regia (D) H SO 4 24

1 4 . Producer gas is a mixture of – (A) CO and N (B) CO and H (C) CO and H (D) CO and N 2 22 2 22 1 5 . Which variety of glass is used for manufacture of optical glasses ? (D) Quartz (D) Red (A) Sodium glass (B) Flint glass (C) Ground glass 1 6 . The colour imparted by Co(II) compounds to glass is – (A) Green (B) Deep–Blue (C) Yellow 1 7 . The species present in solution when CO is dissolved in water are – 2 (A) CO ,H CO , HCO –,CO 2– (B) H CO ,CO 2– 22 3 33 23 3 (C) CO 2– ,HCO – (D) CO ,H CO 33 22 3 1 8 . P O is used extensively as a – 25 (A) Dehydrating agent (B) Catalytic agent (C) Reducing agent (D) Preservative 1 9 . The number of molecules of water needed to convert one molecules of P2O5 into orthophosphoric acid is – (A) 2 (B) 3 (C) 4 (D) 5 2 0 . In warfare smoke screens are prepared from – (A) PH (B) CaC (C) P O (D) COCl 3 2 25 2 2 1 . In Haber's process for the manufacture of ammonia, the catalyst used is – (A) Finely divided nickel (B) Finely divided molybdenum (C) Finely divided iron (D) Finely divided platinum 2 2 . Which one of the following nitrogen oxides is the anhydride of nitrous acid ? (A) N O (B) N O (C) N O (D) NO 2 23 24 2 3 . Which acts both an oxidising as well as reducing agent – (A) HNO (B) HNO (C) H SO (D) HCl 3 2 24 (D) NaNO 2 4 . NO is released by heating – 3 2 (A) Pb(NO ) (B) KNO (C) NaNO 32 3 2 2 5 . A deep brown gas is formed by mixing two colourless gases which are – (A) NO and O (B) N O and NO (C) NO and O (D) NH and HCl 22 2 2 3 2 6 . A metal X on heating in nitrogen gas gives Y. Y on treatment with H O gives a colourless gas which when 2 passed through CuSO solution gives a blue colour. Y is – 4 (A) Mg(NO3)2 (B) Mg3N2 (C) NH3 (D) MgO 2 7 . Oil of vitriol is – (A) H SO (B) H SO (C) H S O (D) H S O 24 23 22 9 22 8 2 8 . The compound which gives off oxygen on moderate heating is – (A) Cupric oxide (B) Mercuric oxide (C) Zinc oxide (D) Aluminium oxide

2 9 . When conc. H SO comes in contact with sugar, it becomes black due to – 24 (A) Hydrolysis (B) Hydration (C) Decolourisation (D) Dehydration 3 0 . Which one of the following reacts with conc. H SO ? 24 (A) Au (B) Ag (C) Pt (D) All 3 1 . HCOOH reacts with conc.H SO to produce – 24 (A) CO (B) CO (C) NO (D) NO 2 2 3 2 . Chlorine is manufactured by – (A) Brikland and Eyde's process (B) Deacon's process (C) Bosch process (D) Solvey's process 3 3 . When chlorine water is kept in sunlight oxygen is evolved therefore – (A) Affinity of hydrogen for oxygen is less (B) Affinity of hydrogen for oxygen is more (C) Affinity of hydrogen for chlorine is more (D) Hydrogen is a reducing agent 3 4 . The following acids have been arranged in the order of decreasing acid strength. Identify the correct order- ClOH(I) BrOH(II) IOH(III) (A) I > II > III (B) II > I > III (C) III > II > I (D) I > III > II 3 5 . Sea weed are important source of – (A) Iron (B) Chlorine (C) Iodine (D) Bromine 3 6 . Euchlorine is a mixture of – (A) Cl and SO (B) Cl and ClO (C) Cl and CO (D) None of these 22 22 2 3 7 . Which of the following represents the correct order of increasing pK values of the given acids – a (A) HClO < HNO < H CO < B(OH) (B) HNO < HClO < B(OH) < H CO 4 3 23 3 34 3 23 (C) B(OH) < H CO < HClO < HNO (D) HClO < HNO < B(OH) < H CO 3 23 43 43 3 23 3 8 . The word Argon means – (A) Noble (B) Now (C) Strange (D) Lazy 3 9 . lodine and hypo react to produce – (A) Na2S (B) Na2SO3 (C) Na2SO4 (D) Na2 S4 O6 CHECK YOUR GRASP ANSWER KEY EXER CISE-1 Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Ans. C D A B D C A C D A C D B A B Que. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 Ans. B A A B A C B B A C B A B D B Que. 31 32 33 34 35 36 37 38 39 Ans. A B C A C B A D D