Solutions of JEE(Main)Chemistry Paper 2013

1. Which of the following complex species is not expected to exhibit optical isomerism? (a) [Co(en)3]3+ (b) [Co(en)2Cl2]+

(c) [Co(NH3)3Cl3] (d) [Co(en)(NH3)2Cl2]+ 2. Which one of the following molecules is expected to exhibit diamagnetic behaviour? (a) C2 (b) N2 (c) O2 (d) S2 3. A solution of () -1- chloro-1-phenylethane in toluene racemises slowly in the presence of a small amount of SbCl5 due to the formation of (a) Carbanion (b) Carbene (c) Carbocation (d) Free radical 4. Given
Cr

3+ ECr

= - 0.74 V;

- 2 + = 1.51 V EMnO Mn
4

2 - 3+ = 1.33 V; ECr O Cr
2 7

ECl

Cl-

= 1.36 V;

Based on the data given above, the strongest oxidizing agent will be (a) Cl (b) Cr3+ (c) Mn2+ (d) MnO 4 5. A piston filled with 0.04 mol of an ideal gas expands reversibly from 50.0 mL to 375 mL at a constant temperature of 37.0 C. As it does so, it absorbs 208 J of heat. The values of q and w for the process will be (R = 8.314 J K1 mol1; ln 7.5 = 2.01) (a) q = + 208 J, w = 208 J (b) q = 208 J, w = 208 J (c) q = 208 J, w = +208 J (d) q = + 208 J, w = +208 J 6. The molarity of a solution obtained by mixing 750 mL of 0.5 M HCl and 250 mL of 2 M HCl will be (a) 0.875 M (b) 1.00 M (c) 1.75 M (d) 0.975 M 7. Arrange the following compounds in order of decreasing acidity:
OH ; Cl CH3
(II)

OH ;

OH ; NO2
(III)

OH

OCH3
(IV)

(I)

2 JEE(Main)Chemistry Paper 2013

(a) II > IV > I > III (b) I > II > III > IV (c) III >I > II > IV (d) IV > III > I > II 8. For gaseous state, if most probable speed is denoted by c*, average speed by c and root mean square speed by c, then for a large number of molecules the ratios of these speeds are (a) c* : c : c = 1.225 : 1.128 : 1 (b) c* : c : c = 1.128 : 1.225 : 1 (c) c* : c : c = 1 : 1.128 : 1.225 (d) c* : c : c = 1 :1.225 : 1.128 9. The rate of a reaction doubles when its temperature changes from 300 K to 310 K. The activation energy of such a reaction will be (R = 8.314 J K1 mol1 and log 2 = 0.301) (a) 53.6 kJ mol1 (b) 48.6 kJ mol1 (c) 58.5 kJ mol1 (d) 60.5 kJ mol1 10. A compound with molecular mass 180 u is acylated with CH3COCl to get a compound with molecular mass 390 u. The number of amino groups present per molecule of the former compound is (a) 2 (b) 5 (c) 4 (d) 6 11. Which of the following arrangements does not represent the correct order of the property stated against it? (a) V2+ < Cr2+ < Mn2+ < Fe2+; paramagnetic behaviour (b) Ni2+ < Co2+ < Fe2+ < Mn2+; ionic size (c) Co3+ < Fe3+ < Cr3+ < Sc3+; stability in aqueous solution (d) Sc < Ti < Cr < Mn; number of oxidation states 12. The order of stability of the following carbocations:
CH2 CH2 CH CH2 ;
(I)

CH3

CH2 CH2 ;
(II) (III)

is (a) III > II> I (b) II > III > I 13. Consider the following reaction: 14. 15. 16.

(c) I > II > III

(d) III > I > II

z 2+ + x MnO 4 + y C2 O 2 + 2 y C O2 + H 2 O 4 + z H x Mn 2 The values of x, y and z in the reaction, respectively, are (a) 5, 2 and 16 (b) 2, 5 and 8 (c) 2, 5 and 16 (d) 5, 2 and 8 Which of the following is the wrong statement? (a) ONCl and ONO are not isoelectronic (b) O3 molecule is bent (c) Ozone is violet-black in solid state (d) Ozone is diamagnetic gas A gaseous hydrocarbon gives upon combustion 0.72 g of water and 3.08 g of CO2. The empirical formula of the hydrocarbon is (a) C2H4 (b) C3H4 (c) C6H5 (d) C7H8 In which of the following pairs of molecules/ions, both the species are not likely to exist ?

2H+ (a) H 2+ H2 , He 2+ H2 , He 2 2 , He 2 (b) 2 , He 2 (d) 2 (c) 17. Which of the following exists as covalent crystals in the solid state? (a) Iodine (b) Silicon (c) Sulphur (d) Phosphorus 18. Synthesis of each molecule of glucose in photosynthesis involves: (a) 18 molecules of ATP (b) 10 molecules of ATP (c) 8 molecules of ATP (d) 6 molecules of ATP 19. The coagulating powers of electrolytes having ions Na+,Al3+ and Ba2+ for arsentic sulphide sol increases in the order: (a) Al3+ < Ba2+ < Na+ (b) Na+ < Ba2+ < Al3+ 2+ + 3+ (c) Ba < Na < Al (d) Al3+ < Na+ < Ba2+

JEE(Main)Chemistry Paper 2013 3

20. Which of the following represents the correct order of increasing first ionization enthalpy for Ca, Ba, S, Se and Ar ? (a) Ca < S < Ba < Se < Ar (b) S < Se < Ca < Ba < Ar (c) Ba < Ca < Se < S < Ar (d) Ca < Ba < S < Se < Ar 21. Energy of an electron is given by E = (2.178 1018 J) (Z2/n2). Wavelength of light required to excite an electron in an hydrogen atom from level n = 1 to n = 2 will be : (h =6.62 1034 J s and c = 3.0 108 m s1) (a) 1.214 107 m (b) 2.816 107 m (c) 6.500 107 m (d) 8.500 107 m 22. Compound (A) C8H9Br, gives a white precipitate when warmed with alcoholic AgNO3. Oxidation of (A) gives an acid (B), C8H6O4. (B) easily forms anhydride on heating. Indentify the compound (A).
(a) CH3 CH2Br (c) (d) CH3 CH2Br CH3 CH2Br (b) C2H5 Br

23. Four successive members of the first row transition elements are listed below with atomic numbers. Which one of them is expected to have the highest E 3+ 2 + value ?
M M

(a) Cr (Z = 24) (b) Mn (Z = 25) (c) Fe (Z = 26) (d) Co (Z = 27) 24. How many liters of water must be added to 1 L of an aqueous solution of HCl with a pH of 1 to create an aqueous solution with pH of 2 ? (a) 0.1 L (b) 0.9 L (c) 2.0 L (d) 9.0 L 25. The first ionization potential of Na is 5.1 eV. The value of electron gain enthalpy of Na+ will be (a) 2.55 eV (b) 5.1 eV (c) 10.2 eV (d) +2.55 eV 26. An organic compound A upon reacting with NH3 gives B. On heating B gives C. The compound C in presence of KOH reacts with Br2 to give CH3CH2NH2. The compound A is (a) CH3COOH (b) CH3CH2CH2COOH (c) CH3 CH COOH | CH3
Li2 < Li+ (a) 2 < Li 2 (c) Li 2 < Li 2 < Li + 2

(d) CH3CH2 COOH

27. Stability of the species Li2, Li2 and Li+ 2 increases in the order of: + (b) Li 2 < Li 2 < Li 2 + (d) Li 2 < Li 2 < Li 2

28. An unknown alcohol is treated with the Lucas reagent to determine whether the alcohol is primary, secondary or tertiary. Which alcohol reacts fastest and by what mechanism? (a) secondary alcohol by SN1 (b) tertiary alcohol by SN1 (c) secondary alcohol by SN2 (d) tertiary alcohol by SN2 29. The gas leaked from a storage tank of the Union Carbide plant in Bhopal gas tragedy was: (a) Methyl isocyanate (b) Methylamine (c) Ammonia (d) Phosgene 30. Experimentally it was found that a metal oxide has formula M0.98O. Metal M is present as M2+ and M3+ in its oxide. Fraction of the metal which exists as M3+ would be (a) 7.01% (b) 4.08% (c) 6.05% (d) 5.08%

4 JEE(Main)Chemistry Paper 2013

ANSWERS
1. (c) 7. (c) 13. (c) 19. (b) 25. (b) 2. (a), (b) 8. (c) 14. None 20. (c) 26. (d) 3. (c) 9. (a) 15. (d) 21. (a) 27. (b) 4. (d) 10. (b) 16. (c) 22. (d) 28. (b) 5. (a) 11. (a) 17. (b) 23. (d) 29. (a) 6. (a) 12. (d) 18. (a) 24. (d) 30. (b)

Solutions
1. All the isomers of [Co(NH3)3 Cl3] have plane of symmetry. Hence, this complex species is expected not to exhibit optical isomers. Therefore, choice (c) is correct. 2. The electronic configurations of the given molecules are as follows. C2(s 2s)2 (s *2s)2 (p2px)2 (p2py)2 N2(s 2s)2 (s *2s)2 (p2px)2 (p2py)2 (s 2pz)2 O2(s 2s)2 (s *2s)2 (p2px)2 (p2py)2 (s 2pz)2 (p*2px)1 (p*2py)1 S2(s 3s)2 (s *3s)2 (p3px)2 (p3py)2 (s 3pz)2 (p*3px)1 (p*3py)1 The molecules C2 and N2 do not possess unpaired electrons. Hence, these are expected to exhibit diamagnetic behaviour. Therefore, the choices (a) and (b) are correct. 3. The reaction proceeds as follows. H H H + SbCl5 + SbCl6 + C Cl C CH3 Ph C Cl - SbCl6 Ph CH - SbCl5 Ph 3 CH 3 There is formation of intermediate carbocation. Hence, choice (c) is correct. 4. The more positive the reduction potential of a species, the larger its reduction tendency. Thus, it acts as a strongest oxidising agent. In the present choices, Mn O 4 acts as a strongest oxidising agent. Therefore choice (d) is correct. 5. For an isothermal expansion of an ideal gas, DU = 0. From the first law of thermodynamics, q = w. Since heat is absorbed, q = 208 J and w = 208 J. Thus, choice (a) is correct. 6. Amount of HCl in the resultant solution is n = M1V1+ M2V2 = (0.5 M) (750 103 L) + (2 M) (250 103 L) = 875 103 mol Total volume of the resultant solution is V = V1 + V2 = (750 + 250) 103 L = 1 L Molarity of the resultant solution is M = n 875 10-3 mol = 0.875 mol L1 = 0.875 M = V 1L

Therefore, choice (a) is correct. 7. Electron-releasing group decreases the acidity while electron-attracting group increases the acidity. Thus, the molecule III will have maximum acidity and the molecule IV will have minimum acidity. Thus, the choice (c) is correct. 8. We have c* : c : c :: 2 RT 8RT 3RT : : :: M pM M 2 : 8 / p : 3 :: 1 : 4 / p : 3 / 2 :: 1 : 1.128 : 1.225

Thus, choice (c) is correct.

JEE(Main)Chemistry Paper 2013 5

9. We have k = A eEa/RT ln k = ln A Ea/RT Ea 1 1 Ea T2 - T1 RT T - = Ea = 1 2 T2 T1 R T1 T2 R T1 T2 Substituting the given values, we get ln (k2/k1) = k2 2.303 log k 1

(8.314 J K -1mol -1 ) (300 K )(310 K ) 1 1 Ea = (2.303 log 2) = 53.599 J mol = 53.6 kJ mol (310 K - 300 K ) Thus, choice (a) is correct. 10. Let the compound be R(NH2) x. Its acetylation will give R(NHCOCH3) x. Their molecular masses will be m1(R(NH2)x) = mR +(14 u)x m2 (R(CHCOCH3)x) = mR + (56 u)x Increase in molecular mass = (56 u 14 u)x = (42 u)x Given increase in the molecular mass = 210 u 210 u Hence, x = =5 42 u Thus, choice (b) is correct. 11. In the choice (a), the electronic configurations of given ions are as follows. 23V2+; 3d3; 24Cr2+; 3d4 : 25Mn2+; 3d5 : 26Fe2+; 3d6 The number of unpaired electrons in these ions will be V2+; 3Cr2+: 4 Mn2+: 5Fe2+ : 4 Hence, the paramagnetic behaviour of Fe2+ will be less than that of Mn2+. Thus the choice (a) is in correct. 12. Based on the number of resonating structures, the order of stability will be III > I > II
CH2 CH2 CH2 CH2 CH2

CH 2 = CH - C H 2 C H 2 - CH = CH 2 CH3 - CH 2 - C H 2
Hence, the choice (d) is correct. 13. The balanced chemical equation may be obtained as follows.
2+ + MnO + 4 H 2 O] 2 4 + 8H + 5e Mn C 2 O2 4 2CO 2 + 2e ] 5

14. 15.

2+ 2+ + 8H 2 O + 10 CO2 2MnO 4 + 5C 2 O 4 + 16 H 2 Mn Thus x = 2, y = 5 and z = 16 Hence, the choice (c) is correct. The number of electrons in ONCl and ONO are : ONCl 8 + 7 + 17 = 32 ONO 8 + 7 + 8 + 1 = 24 Thus, these two species are not isoelectronic. Ozone is bent molecule, violet-black in colour in solid phase and diamagnetic in nature. Thus, all the four choices are correct and none of them is incorrect. Mass of H in the obtained water is

2 2M H mH 2O = 0.72 g = 0.08 g 18 M H2O

6 JEE(Main)Chemistry Paper 2013

Amount of H in the molecule is nH = mH 0.08 g = 0.08 mol = M H 1 g mol-1

Mass of C in the obtained CO2 is 12 MC mCO2 = 3.08 g = 0.84 g 44 M CO2 Amount of C in the molecule is m 0.84 g nC = C = = 0.07 mol M C 12 g mol-1 The ratio of C and H in the molecule is nC : nH :: 0.07 mol : 0.08 mol :: 0.07 : 0.08 :: 7 : 8 Hence, the empirical formula of the compound is C7H8. Therefore, the choice (d) is correct.

+ 16. The species H 2 2 (which is 2H) and He2 (an inert gas) do not exist. Thus, the choice (c) is correct.

17. Iodine, sulphur and phosphorus exist as I2, S6 and P4, respectively. Silicon does exist as covalent crystal in the solid state. Thus the choice (b) is correct. 18. Eighteen molecules of ATP are involved in the synthesis of one molecule of glucose. Therefore, the choice (a) is correct. 19. The larger the charge, larger is the coagulating power. Thus the order is Na+ < Ba2+ < Al3+. Hence the choice (b) is correct. 20. The electronic configurations of the given elements are 2 2 2 4 2 4 2 6 20Ca(4s ), 56Ba(6s ), 16S(3s 3p ), 32Se(4s 4p ) and 18Ar(3r 3p ) The increasing order of first ionization enthalphy will be Ba < Ca < Se < S < Ar Thus, the choice (c) is correct. 1 1 21. DE = E2 E1= (2.178 1018 J) = 1.6335 1018J 4 1

( )

l =

hc (6.62 10 -34 J ) (3 108 m s-1 ) = 1.214 107m = (1.6335 10 -18 J ) DE

Therefore, the choice (a) is correct. 22. Aliphatic Br gives precipitate with AgNO3.The Oxidation of CH2Br gives COOH and alsoCH3 gives COOH. The two COOH group must be in ortho positions to give anhydride. Hence,
O D CH COOH CO 3 Thus, the choice (d) is correct. 23. The ion Co3+ has the maximum oxidising ability also has least slability in aqueous solution amongst the ions Cr3+, CH2Br
[O]

COOH

CO

3+ 2 + Mn3+, Fe3+ and Co3+. Hence, ECo Co 24. will have the maximum value. Therefore, the choice (d) is correct. pH = 1 (H+) = 101 M pH = 2 (H+) = 102 M To change the solution having 101M H+ ions to 102M H+, the solution will have to be diluted 10 times. Thus 9L of water will have to be added to 1 L of the original solution. Therefore, the choice (d) is correct.

JEE(Main)Chemistry Paper 2013 7

25. Electron gain enthalpy will be negative of ionization potential, Thus its value will be 5.1 eV Therefore, the choice (b) is correct. 26. We have
CH3CH2NH2
Br2/KOH

CH3CH2CONH2
(c) NH3

CH3CH2COOH
(A)

CH3CH2COONH4
(B)

Therefore, the choice (d) is correct. Li 2 (s 2s )2

Bond order =1
+( Li 2 s 2s )1 -( Li 2 s 2s )2 (s * 2s )

27. The electronic configurations of Li 2 , Li + 2 and Li 2 and their bond orders are

Bond order =1/2

Bond order =1/2

+ The species Li 2 will have larger electronic repulsion as compared to Li 2 and thus will be less stable. + Thus, the stability order is Li 2 < Li 2 < Li 2 .

Therefore, the choice (b) is correct. 28. Tertiary alcohol reacts fastest with lucas reagent. Because of bulkiness at the site of reaction the alcohol reacts with Lucas reagent via SN1 mechanism. Therefore, the choice (b) is correct. 29. The gas leaked from a storage tank of the Union Carbide was methylisocyanate. Therefore, the choice (a) is correct. 30. Let x out 0.98 of the metal M be present as M3+ and the rest (i.e. 0.98 x) be present as M2+. The balancing of positive and negative charges gives. x (+3) + (0.98 x) (+2) = 2 This gives x = 0.04. The percent of M3+ present will be (0.04/0.98) 100 = 4.08% Therefore, the choice (b) is correct.