Solution of DPP # 8

TARGET : JEE (ADVANCED) 2015

CHEMISTRY
1. (A) There is irregular trend in the first ionisation enthalpy of the 3d metals.
Se Ti V Cr Mn F Co Ni Cu Zn
In kJ/mol : 631 656 650 653 717 762 758 736 745 906

1 1
3. AgNO 3  Ag  NO 2  O2 ; Cu(NO3)2  CuO + 2NO2 + O
2 2 2

1 3
Pb NO 3 2  PbO  2NO 2  O2 ; 2AlNO 3 2  Al 2 O 3  6NO 2  O2
2 2

4. 2MnO4– + 3Mn2+ + 2H2O  5MnO2 + 4H+

5. V2O5 + NaOH 2Na3VO4 + 3H2O

6._ Pb2+ + S2–  PbS  (black)

PbS + HNO3  Pb(NO3)2 + H2S 

SO42– + Pb(NO3)2  PbSO4  (white precipitate)

7._ Pb2+ and Ag+

8. Ni2+ + S2–  NiS  (black)

NiS + HNO3 + 3HCl  Ni2+ + S  + NOCl  + 2Cl– + 2H2O

CH3 – C  N – OH NH4OH
Ni2+ + 2 |   [Ni(dmg)2]  (red) + 2H+

CH3 – C  N – OH

9. Carbon monoxide is better reducing agent than carbon below 983 K.

10. (a)  van – Arkel method for Zr – Hg

Based on volatile nature of halides of methods.

Leaching
12. (A) Al2O3(s) + 3H2O (  ) + 2NaOH (aq)  2Na[Al(OH)4] (aq)

2Na[Al(OH)4] (aq) + CO2(g)  Al2O3 . xH2O(s) + 2NaHCO3 (aq)

1470 K
Al2O3 . xH2O(s)   Al2O3 (s) + xH2O (g)
Calcinatio n

Electrolytic reduction of molten pure Al2O3 mixed with Na3AlF6 or CaF2

Method is known as Hall-Heroult process
Cathode : Al3+ (melt) + 3e–  Al(l)
Anode : C(s) + O2– (melt)  CO(g) + 2e–
C(s) + 2O2– (melt)  CO2 (g) + 4e–
 (B) Leaching :
Ag2S + 4NaCN 2Na[Ag(CN)2] + Na2S

Na2S + 2O2  Na2SO4

Displacement by zinc in aqueous solution :
2Na[Ag(CN)2] + Zn  Na2[Zn(CN)4] + 2Ag 
(C) Roasting :

2PbS + 3O2  2PbO + 2SO2
Self reduction :
2PbO + PbS  3Pb + SO2
(D) Calcination :
 ( calcination )
MgCl2. 6H2O      MgCl2 + 6H2O
Dry HCl( g)

It is not made anhydrous by simple heating because it gets hydrolysed


MgCl2. 6H2O  MgO + 5H2O + 2HCl
Electrolytic reduction :
Electrolytic reduction of molten anhydrous carnallite.
MgCl2 Mg2+ + 2Cl–
At cathode : Mg2+ + 2e–  Mg(99% pure) ;
At anode : 2Cl–  Cl2 + 2e–

13. HgCl2 due to covalent characters, sufficient chloride ions are not obtained.

16.* (D) Oxidation state of iron in Mohr’s salt, FeSO4.(NH4)2SO4.6H2O is +2

17.* (A) 2Cu2+ + 5I–  Cu2I2 (white) + I3– ; Pb2+ + 2I–  PbI2  (yellow)

(B) Cu2+ + 4NH3  [Cu(NH3)4]2+ (deep blue solution)

Pb2+ + 2NH3 + 2H2O  Pb(OH)2  (white) + 2NH4+ (Pb2+ does not form soluble complex)

(C) Cu2+ + 2OH–  Cu(OH)2  (blue) ; Pb2+ + 2OH–  Pb(OH)2  (white)

Pb(OH)2  + 2OH–  [Pb(OH)4] soluble complex.

(D) Pb2+ + 2Cl–  PbCl2  (white) ; Cu2+ + 2Cl–  CuCl2 (green solution).

18.* Na3[AlF6]  3NaF + AlF3

NaF and AlF3 both are ionic compounds and so ionise to give ions. This increases the electrical conductivity
and lowers the melting point of Al2O3 .

At cathode : Al3+ (melt) + 3e–  Al.

At anode : C(s) + O2– (melt) — CO (g) + 2e– ; C(s) + 2O2– (melt) — CO2 (g) + 4e–.

19.* ZnCO3 

 ZnO + CO2. ZnO is yellow when hot.
(white)
1
Co(NO3)2.6H2O 
 CoO (black) + 2NO2 + O  + 6H2O
2 2
2FeSO4.6H2O 
 Fe2O3 (brown) + SO2 + SO3 + 6H2O
3MnSO4 
 Mn3O4 + 2SO2 + SO3
(faint pink) (black)
20.*– Cyanide process used for Au and Ag comlexes formed in this, are : Na[Au(CN)2], Na[Ag(CN)2], Na2[Zn(CN)4].

23. Due to common ion effect the concentrations of OH– ions is just sufficient to precipitate the cations of 
group as their hydroxides. (As they have low Ksp values).


30. NH4NO2  N2 + 2H2O
NO2– gives brown vapours of NO2 with dil H2SO4

31. 2MnO4– (Y) + 3Mn2+ (Z) + 2H2O  5MnO2 + 4H+

This reaction is Vohhard method for estimation of manganese carried out in presence of ZnSO4 or suspended
ZnO which catalyses the oxidation.

6 7 4
32. 3 MnO24 + H+  2 MnO 4 + MnO 2 + 2H2O

33. 2Mn2+ + 5S2O82– + 8H2O 2MnO4– + 10SO42– + 16H+

Mn(VII) – [Ar]18 3dº. No unpaired electron so 'spin only' magnetic moment of compound is .

34. Ti3+ – 3d1 (purple) ; V4+ 3d1 (blue) ; Cr3+ — 3d3 (Green), Pb2+ – (colourless) ; Fe2+ – 3d6 (green) ; Zn2+ – 3d10
(colourless) ; Ni2+ – 3d8 (green) ; Sc3+ – 3d0 (colourless) ; Hg2+ (colourless).

VI
35. All except BaCl2 36._ X  CrO2Cl2 ''sp3''


H O2 H
37. K2Cr2O7 2   CrO5  Cr3+ + O 
2
H O 2

KCrO2 (green)
So the answer is 3.

2 3 2 1 2 3 3
38. , O , Fe3O4 ( O + Fe2O3), [ (H O) (NO)]2+, Na2[ (CN)5(NO)], [ (CN)6],
Fe S 2 Fe2 3 Fe Fe 2 5 Fe Fe Fe
2 2 2 2
K2 [ (CN)6], (C5H5)2, WO4
Fe Fe Fe Fe

39. 2I– + Pb2+ PbI2  (yellow) + 2K+

2NH3 + 2H2O + Pb2+  Pb(OH)2  (white) + 2NH4+
2Pb2+ + 2CO32– + H2O  Pb(OH)2  (white) + PbCO3  (white) + CO2
Pb2+ + CrO42– PbCrO4  (yellow)
Pb2+ + 2Cl–  PbCl2  (white)
Pb2+ + SO32–  PbSO3  (white)
Pb2+ + S2–  PbS  (black)
Pb2+ + KNO3  No precipitate is formed.
Pb(ClO4)2 is water soluble.


40. Al2O3 + 2NaOH + 2H2O  2NaAlO2 + 3H2O ; Ag2S + 2CN–  [Ag(CN)2]– + S2–

Au + 2CN– + 2H2O + O2  [Au(CN)2]– + 4OH– ; CuFeS2  No leaching

PbS  No leaching ; MgCl2  No leaching ; FeCO3  No leaching

2Cu2O (s) + 4H2SO4 (aq) + O2 (g)  4CuSO4 (aq) + 4H2O () ; HgS  No leaching
41. At 500 – 800 K (lower temperature range in the blast furnace)

3 Fe2O3 + CO  2 Fe3O4 + CO2

Fe3O4 + CO  3Fe + 4 CO2

Fe2O3 + CO  2FeO + CO2

At 900 – 1500 K (higher temperature range in the blast furnace):

C + CO2  2 CO ; FeO + CO  Fe + CO2

42. (A) FeSO4  Fe2O3 + SO2 + SO3

(B) NH4NO3  N2O + 2H2O

(C) Ba(N3)2  N2 + Ba

(D) MgCl2 . 6H2O  MgO + 2HCl + 5H2O

43. (A) S2O32– + H+  S + SO2


(B) 2Cu2+ + 4I–   Cu2I2  + I2

(C) 2 CrO24– + 2H+   Cr2 O72– + H2O

(D) 2 Mg(NH4)VO4  Mg2V2O7 + 2NH3 + H2O

44. (A) Pb2+ + CrO42–  PbCrO4  (yellow) ; Pb2+ + 2I–  PbI2 (yellow)

(B) Zn2+ + 2OH–  Zn(OH)2  (White) ; Zn(OH)2  + 2OH–  [Zn(OH)4]2– soluble

Zn2+ + 2NH3 + 2H2O  Zn(OH)2  (White) + 2NH4+

(C) Ni2+ + 2OH–  Ni(OH)2  (Green) ; Ni2++2NH3+2H2O  Ni(OH)2  (Green) + 2NH4+

Ni2+ + 2CN–  Ni(CN)2  (Green)

(D) Cu2+ + 2OH–  Cu(OH)2  (blue)

Cu2+ + 2NH3 + 2H2O  Cu(OH)2  (blue) + 2NH4+