GROUP 13 & 14

01. an inorganic compound (A) shows the following reactions. It is white solid
and exist as dimer. i)It gives fumes of (B) with much wet air. (ii)It
sublimes at 180 C and forms monomer if heated to 4000C. (iii)Its aqueous
0

solution turns blue litmus paper red. (iv)Addition of NH4OH and NaOH
separately to a solution of (A) gives white ppt which is however soluble in
excess of NaOH. Identify the products. [A = Al2Cl6; B = HCl;]
02. An inorganic compound (A) in its aqueous solution produced a white ppt
with NaOH, which dissolves in excess of NaOH. The aqueous solution of
(A) also produces white ppt with NH4OH which does not dissolve in excess
of NH4OH. Also its aqueous solution produced light yellow ppt with AgNO 3.
Identify (A). [AlBr3]
03. A white crystalline compound (P) swells up on heating and gives violet
colour flame on burning. Its aqueous solution gives (i)white ppt with BaCl2,
(ii)white gelatinous ppt with excess of NH4OH which dissolves in NaOH but
reappears on boiling with con NH4Cl solution. Identify (P).
[P = potash alum]
04. What is the product formed when methylenecyclohexane is reacted with
B2H6 followed by reaction with H2O2 / NaOH? [cyclohexylmethnol]
05. Complete the following reactions:
a)BCl3 + NH4Cl (1400C, C6H5Cl) 🡪 [A}; [A} + NaBH4 🡪 [B].
b)BCl3 + LiAlH4 🡪 [C] + LiCl + AlCl3
c)BCl3 + H2+ C (fibre) (18000C) 🡪 [D].
d)Na2B4O7 + NH4Cl (red hot)n🡪 [E] + B2O3 + NaCl + H2O
e)B2O3 + CaF2 + H2SO4 (heat) 🡪 [G] + [H] + [I].
f)BCl3 + (C2H5)4N+ Cl- (CHCl3) 🡪 [F].
g)Al2O3 + Co(NO3)2 (heat) 🡪 [J] + [K] + [L].
h)TiCl4 + BCl3 + H2 (heat) 🡪 [M] + [N].
A =B3N3H3Cl3 ; B = B3N3H6 C = B2H6; D = B4C; E = BN;
+ -
F = (C2H5)4N BCl4 G = BF3 H = CaSO4 I = H2O
J =2CoAl2O4 (Thenard’s blue) K = 4NO2 L = O2
M = 2TiB2 N = 20HCl;
06. Starting from boric acid how would you prepare (a)boric anhydride
(b)boron trichloride, (c)boron trifluoride, (d)boron hydrides (e)ethyl
borate, (f)meta and tetra boric acids.
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(a)2H3BO3 (red heat) 🡪 B2O3 + 3 H2O
(b)B2O3 + 3C + 3Cl2 (heated) 🡪 2BCl3 + 3CO
(c)CaF2 + H2SO4 🡪 CaSO4 + 2HF; 2H3BO3 + 3H2F2 🡪 2BF3 + 6H2O;
(d)H3BO3 (red heat) 🡪 B2O3 (magnesium heat) 🡪 Mg3B2 (with dil HCl)
 🡪mixture of boron hydrides.
(e)3EtOH + H3BO3 🡪 Et3BO3 + 3H2O.
(f)H3BO3 (1000C) 🡪 HBO2 + H2O; 4H3BO3 (1600C) 🡪 H2B4O7 + 5H2O
4HBO2 🡪 H2B4O7 + H2O;
06. Although Al is above hydrogen in the electrochemical series, the metal is
rendered passive with con nitric acid. Also the metal is stable in air and
water. Why?
07. Suggest a method to separate Fe(OH)3 and Al(OH)3. [use NH4OH / NaOH]
08. A compound (X) on reduction with LiAlH4 gives a hydride (Y) containin
21.72%
hydrogen along with other products. The compound (Y) reacts with air
explosively resulting in boron trioxide.. Identify (X) and (Y).
4BCl3 (X) + 3LiAlH4 🡪 2B2H6 (Y)+ 3AlCl3 + 3LiCl;
% of H in B2H6 = 6/27.62 x 100 = 21.725 %.
2B2H6 + 6O2 🡪 2B2O3 + 6 H2O;
Bond length of = B-H are : 1.19A0 & 1.33 A0; bond angle 970 & 121.5 0
B-B bond distance 1.78 A0 ; with 3C-2E bond.
09. A certain salt (X) gives the following tests: (i) Its aqueous solution is
alkaline to litmus. (ii) On strongly heating it swells to give a glassy material.
(iii)When con H2SO4 is added to a hot concentrated solution of (X) white
crystals of weak acid separates out. Identify (X).
(X) is an alkali metal salt. (X) is Na2B4O7 . 10H2O.
Na2B4O7 + 7 H2O 🡪 2NaOH + 4H3BO3;
Na2B4O7 . 10H2O (heat) 🡪 Na2B4O7 + 10H2O
Na2B4O7 (heat) 🡪 2NaBO2 + B2O3 (glassy mass).
10. An inorganic Lewis acid (X)shows the following reactions: (i)It fumes in
moist air. (ii)The intensity of the fumes increases when a rod dipped in aq
ammonia is brought near mouth of the test tube. (iii)An acidic solution of
(X), on addition of NH4Cl and NH4OH, gives a ppt which dissolves in NaOH
solution. (iv)an acidic solution of (X) does not give ppt with H2S. Identify (X).
[(X) = AlCl3].
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11. A white ppt (B) is formed when a mineral (A) is boiled with NaCO3 solution.
(ii) The ppt is filtered and the filtrate contains two compounds (C) and (D).
The compound (C) is removed by crystallisation and when CO2 is passed
through the mother liquor left (D), changes to (C). (iii)The compound (C)
on strong heating gives two compounds (D) and (E). (iv) (E) on heating with
cobalt oxide produces blue colourwa aubatNCE (f). Identify the ompounds.
Ca2B6O11. 5 H2O (A) + 2Na2CO3(aq)( 🡪 2CaCO3 (B) +Na2B4O7 (C) + 2NaBO2 (D)
4NaBO2(D) + CO2 🡪 Na2B4O7 (C) + Na2CO3
 Na2B4O7 (C) (heat) 🡪 2NaBO2 (D) + B2O2 (E) ; B2O3 + CoO 🡪 Co(BO2)2 (F).
12. What happens when Al4C3 and BF3 are hydrolysed?
Al4C3 + 12 H2O 🡪4Al(OH)3 + 3CH4; BF3 + 2H2O 🡪 [BF3(OH)]- H3O+
13. Why Si does not form graphite like structure?
[Pπ- pπ bonding is not prominent for silicon and other heavier
congeners of group 14.]
14. What is the energy gap between the conductance band and valance band?
[roghly 6 eV]
15. C-C bond in graphite is shorter than that of in diamond. Explain.
[sp2 & sp3 hybrisized]
16. Graphite is thermodynamically more stable than diamond. But diamond is
not readlily converted into graphite. Why?
[Eact is very high]
17. Carbon does not form divalent ions. Why?
[The lattice energy of carbon is not very high unlike the other lements]
18. Silane is more reactive than methane. Why?
[BDE Si-H = 393 kJ; C-H = 453 kL; C is more electronegative than H & Si
is more electropositive ]
19. CO2 is a gas while SiO2 , silica is a solid. Why?
[Due to a large electronegativiy difference in Si and O atoms, Si-O
bond posses considerable ionic nature and thus silica has three
dimensional infinite structure havin silicon atom tetrahedrally bonded
four oxygen atoms it is a high melting solid.]
20. PbBr4 and PbI4 do not exist. Why?
21. CO is poisonous. Why?
22. CO2 can not be used as a fire extinguisher for burning Mg. Why?
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23. In phosgene the C-O bond length is longer while the C-Cl bond is shorter
than expected. Explain.
24. When graohite is heated at 673 K, with vapours ofK, Rb or Cs bronze
colour is developed. Explain.
[The metal atoms are squeezed between the layers of graphite forming
‘Inter calation compounds’ of different composition. :C8M 🡪 C24M 🡪
C36M, etc . the colour is due to the metal atom clusters.]
25. Ge and Sn are used as reducing agent, while lead is oxidant.
[Ge & Sn have greater reduction potential]
26. CO is stable while SiO is not known. Why?
27. Explain that SnI4 is coloured white SiBr4 is colourless. [Charge transfer]
28. What is the hybridisation of C and O in C3O2?
29. Mention the examples of the nature of CO as Lewis base. [ carbonyls]
30. Explain why CN- is highly toxic.
[ CN- forms strong bonding with Fe3+ present in cyctochrome oxidase]
31. ((CH3)3COH) acts as a weaker Lewis acid than ((SiH 3)3COH). Explain.
[The vacant d-orbital in Si can accommodate a pair of electron from a
base]
32. SnO2 forms positively-charged colloid in acid medium, while it forms
negatively-charged colloid in alkaline medium. Why?
[SnO2 4H+ 🡪 Sn4+ + 2 H2O; colloid is : [SnO2]-Sn4+ +ve colloid
- 2- 2-
SnO2 + 2 OH 🡪 SnO3 + H2 [SnO2]-SnO3 -ve colloid
33. An inorganic bright red compound (A) on warming with HNO 3 changes to a
dark brown solid (B). (B) on treatment with con HCl gives out Cl 2 on
warming, leaving a yellowish white residue (C) on cooling. Identify.
Pb3O4 (A) red + 4HNO3 🡪 PbO2 (B) + 2Pb(NO3)2 + 2 H2O
PbO2 + 4HCl 🡪 PbCl2(C) + Cl2 + 2H2O
34. A colourless solution contains a metal nitrate. A little solution of NaCl is
added to it when a cloudy white ppt appears. Is it PbCl2 , or AgCl or
Hg2Cl2?
[PbCl2 –soluble in hot water’ AgCl –soluble in aq NH3; H2Cl2 –black in NH3]
35. Is Pb(II) oxide soluble in HCl, HNO3 or H2SO4?
[HNO3; the salt is soluble; PbCl2 and PbSO2 are insoluble]

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36. Predict the reaction of Pb3O4 with con HCl.
[Pb3O4 + 8HCl 🡪 3PbCl2 + Cl2 + 4H2O].; Pb3O4 🡪 3PbO + O; HCl + O 🡪]
37. A colourless poisonous gas (A) burns with a blue flame. When passed
through aq NaOH at high T and P it gives (B). (B) gives (C) on heating. (C)
gives white ppt with CaCl2 aolution. Both (C) and (D) decolourise acid
KMnO4.. [CO; HCOONa; Na2C2O4; CaC2O4]
38. Explain the action nitric acid on tin, C, Pb3O4 :
[Pb3O4 + 4HNO3 🡪 2Pb(NO3)2 PbO2 + 2H2O
39. Predict the product:
a)C3O2 + H2O 🡪 [malonic acid]
b)PdCl2 + CO + H2O 🡪 [Pd + CO2 2HCl]
c)3CS2 + 6NaOH 🡪 [Na2CO3 + 2Na2CS3 + 3H2O]
d)CS2 + 2NH3 🡪 NH4 [H2NCS2]: dithiocarbonate
e)Malonic acid (heat ; P4O10) 🡪 C3O2; a foul smelling gas.
40. An aqueous solution of a salt (A) gives white crystalline ppt (B) with NaCl
solution. The filtrate gives a black ppt with H2S. Compound (B) is dissolved
in hot water and the solution gives yellow ppt with NaI solution on cooling.
The compound (A) does not give any gas with dilute HCl, but libeatd red
 brown gas on heating strongly. Identify the compounds.
[(A) = Pb(NO3)2]
41. CS2 reacts at 300C with excess Cl2 in the presence of FeCl3 catalyst to give
(A) and (B). Compound (B) adds with two moles of ethene to give
mustered gas. (B) also reacts withCS2 at 600C in the presence of FeCl3 cat
to yield (A) and sulphur. (A) reacts with HF under anhydrous condition in
the presence of S6Cl5 cat to yield Freon. Compound (A) is hydrolysed by
super heated steam to yield a poisonous gas (C) and HCl. (C) reacts with
AgNO3 to gice a white ppt of AgCl. Gas (C) is also obtained by the aerial
Identify the compounds. [CCl4; S2Cl2; COCl2]
42. H2C2O4 (heat) 🡪 (A) + (B) + (C) [all are oxides); (A) + Cl2🡪 (D);
(D) + NH3 (heat) 🡪 (E); (B)+ NH3 (heat)🡪 (E); (C) + indicator silica gel
🡪pink; identify. [CO; CO2; H2O; COCl2; H2NCONH2]]

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43. Bluish grey highly dense metal (A) + moderately con HNO3 🡪(B)g colourless
(B) + air 🡪 (C) red brown gas;
A2+ (little affected by dil HCl / dil H2SO4) H2S / sat KCl 🡪 (D) red ppt;
(D) + H2O 🡪 (E) black ppt + (F)white ppt.
[Pb; NO; NO2; Pb2SCl2; PbS; PbCl2]
44. (A), a salt of tin + H2O (excess) 🡪 (D) basic salt;
(A) + corrosive sublimate 🡪 (B) a fuming liquid);
(A) + (NH4)2MoO4 🡪 (C) blue ppt; [SnCl2; SnCl4; HgSnCl4; Sn(OH)Cl]
45. Triethylamine is pyramidal while trisilyl amine is planar. Why?
46. Trisilyl amine is a weaker base than ammonia. Why?
47. A scarlet compound (A) is teated with con HNO3 to give a chocolate brown
ppt (B). The ppt is filtered and the filtrate is neutralised with NaOH.
Addition of KI to the resulting solution, gives a yellow ppt (C). The ppt (B)
on warming with con HNO3 in the presence of Mn(NO3)2 produces a pink-
coloured solutiondue toward the formation of (D). Identify.
[A=Pb3O4; B=PbO2; C=PbI2; D= Pb(Mn)2
48. Pyrex glass is a mixture of ------------------.
[sodium borosilicate and barium borosilicate]
49. SiH4 and O2 mixtureon bubling through water and bubbles coming in
contact with air:
A)burns with luminous flame B)vortex rings of finely divided siica are
formed C)SiH4 + 2O2 🡪 SiO2 + 2H2O; D)all of these. [Ans :D]
50. Predict the product formed: SiO2 + C (heat) 🡪 ? [Ans: SiC & CO]
51. The species present in solution when CO2 is dissolved in water are-----.
[CO2; H2CO3; HCO3-; CO32- ]
52. When PbO2 reacts with con nitric acid, the gas evolved is ----------. [O2]
53. Pb and Sn are extracted from their chief ores by ----- & ------ method.
[self reduction & carbon reduction respy ]
54. Which of the following is not hydrolysed?
A)CCl4 B)SiCl4 C)GeCl4 D)SnCl4 [CCl4]
55. Quartz is an example of --------------. [three dimensional network silicate]