CHEMISTRY (CHEMICAL BONDING AND MOLECULAR STRUCTURE)

ANSWER KEY

1. (a) 2. (a) 3. (c) 4. (a)

5. (a) 6. (b) 7. (a) 8. (c)
9. (c) 10. (d) 11. (b) 12. (b)
13. (d) 14. (d) 15. (a) 16. (d)
17. (a) 18. (a) 19. (c) 20. (a)
21. (d) 22. (b) 23. (b) 24. (a)
25. (a) 26. (a), (b), (c), (d) 27. (a), (c), (d) 28. (2211)
29. (634) 30. (3.00) 31. (28) 32. (6.00)
33. (7.00) 34. (4.00) 35. (b) 36. (b)
37. (a) 38. (c) 39. (b)

SOLUTIONS

SINGLE CHOICE QUESTIONS

Solution 1: (a) STATEMENT-1 is true, STATEMENT-2 is true and STATEMENT-2 is correct

explanation for STATEMENT-1.
Solution 2: (a) One water molecule is coordinated to lone pair of electrons on SnCl2 and the
other is hydrogen bonded to coordinated water molecule.

Solution 3: (c) N – N bond in N2O4 and N–N bond in N2H4

145 pm

Solution 4: (a) two C – H bonds are in the same plane of axial S – F bonds

Solution 5: (a) (BeH2)n

Solution 6: (b) two in molecular plane and one in a plane perpendicular to molecular plane
which contains C–C  -bond.

Solution 7: (a) Aqueous hydrolysis of CCl4 is not possible due to absence of vacant orbital on
carbon, while hydrolysis of MgCl2, AlC13, SiCl4 and PCl5 is possible. Extent of hydrolysis is
proportional to the amount of positive formation charge present on the atomic site prone to attack
of H2O molecules.

CCl4 < MgCl2 < AlCl3 < SiCl4 < PCl5

Solution 8: (c) σ-bonding molecular orbital is gerade due to having center of symmetry.

Solution 9: (c)
IO2 F2− : Hyb.sp 3d ,   spx p y pz d z 2 

ClF4− : Hyb.sp 3d 2   spx p y pz d x2 − y 2 d z 2 

 
IF7 : Hyb.sp 3d 3 .  spx p y pz d x2 − y 2 d xy d z 2 
 
d xy : orbital has two nodal planes xz and yz

Solution 10: (d)

Due to steric repulsion among Cl-atoms observed ∠CI C Cl is found to be greater than expected

Bond angle between both C–Cl bonds is greater than 60o due to steric repulsion between both
Cl-atoms, hence  D (observed) <  D (Theoretical)

Observed bond angle between both C–NO2 bonds is found to be greater than 60o due to steric
repulsion, between NO2 groups, hence  D (observed) <  D (Theoretical)

observed bond angle between C–O and C–Cl bond is found to be less than 60o due to
intramolecular H-bonding present in it, hence,  D (observed) <  D (Theoretical)

Solution 11: (b)

According to Bent's Rule more electronegative substituents attached to hybrid orbital that
contains more p-character. Hence, more p-character, longer will be bond length.
Solution 12: (b)

It can be explained on the basis of Bent's rule. In N2F4, N–N bond has more s-character hence
bond length decreases.
While in N2H4, N–N bond has less s-character (i.e., more p-character), hence bigger bond length.

Solution 13: (d) N2

LUMO

HOMO
Solution 14: (d)
In CdI2, Pink colour is due to polarization of I– by Cd2+ has pseudo noble gas configuration. In
CdCl2, extent of polarization of Cl– by Cd2+ is relatively less, hence specific colour cannot be
predicted.

Solution 15: (a) (I) Thermal stability: BeSO4 < MgSO4 < CaSO4 < SrSO4 < BaSO4
(IV) Melting point: NaCl > KCI > RbCl > CsCl > LiCl

Solution 16: (d) (I) CaCO3 > SrCO3 > BaCO3

(II) Li2CO3 < Na2CO3 < K2CO3
(III) K2CO3 < Rb2CO3 < Cs2CO3

Solution 17: (a) (II) NaH (III) Li2CO3

Solution 18: (a) ClF3O2

Solution 19: (c)

IE1 of N2 is larger than that of O2 because, as per MOT, HOMO of N2 is a BMO i.e.,  2 p x while
2

that of O2 is an ABMO i.e.,

 • 2 p1x =  • 2 p1y It is easier to remove an electron from an ABMO
.
than to remove and electron from a BMO. Again, as per MOT an electron is always removed
from the ABMO while it is added to the LUMO. However, if the HOMO is partly filled, then the
added electron goes to HOMO instead of LUMO. Both in the case of O2 and N2, the added
electron goes to ABMO and hence the addition lowers the bond order of O2 from 2 to 1.5 and of
N2 from 3 to 2.5. In both the cases, addition of an electron lowers the stability of the respective
species. But in case O2, the addition of an electron leads to lowering of the spin while in case of
N2 the addition raises the spin. Hence, addition of an electron to N2 is more energy consuming
than that needed for O2. So, EA of O2 is higher than N2. EA is conventionally measured in terms
of energy released.

Electronegativity of an atom is directly proportional to its bond multiplicity. Because the higher
the bond multiplicity smaller is the size and hence more is the electronegativity. Therefore, EN
C  Csp  Csp
2 3
of Carbon atom in different hybrid state is sp

Both in N2 and CO, the bond order is 3. Still then the bond energy of the two species differs
because radii of C  N   O Rather, the correct order of these radii is C  N   O (Radii
along period always decreases). Therefore, CO is slightly less stable than N2.
BLCO = 113pm and BLN2 = 110pm

Solution 20: (a)

Solution 21: (d) A – p, q, r, s; B – p, q, r, s; C – q, r; D – q, r

Solution 22: (b)

→ 2 p − 3d back bond

→ Can exhibit intermolecular H-bonding as II-atom is bonded to O-atom
→ Proton donor acid; basicity = 4

→ back bond is absent

→ can form intermolecular H-bond as H-atom is directly bonded to O-atom
→ Proton donor acid, basicity = 2
→ Hypervalent, Number of e–s at Se = 12

→ 2 p − 2 p back bond is present

→ Hypovalent, as number of e–s at B-atom = 6
→ Does not furnish H+
→ 2 p − 2 p back bond is present
→ Can form intermolecular H-bonding as H-atom is directly bonded to N-atom Hypovalent
number of e–s at B-atom = 6
→ Does not furnish H+

Solution 23: (b)

• Central atom is sp3 hybridized

• M–O–M oxo linkage is absent
• Non-planar

H6B2O72– or (OH)3B.O.B(OH)3

Two tetrahedral units are joined by sharing one corner. Thus,

• Central atom is sp3 hybridized
• M–O–M oxo linkage is present
• Non-planar

• Central atom is sp3 hybridized

• M–O–M oxo linkage is absent
• Non-planar

• Central atom is sp3 hybridized

• M–O–M oxo linkage is present
• Non-planar
Solution 24: (a)
B2 H 6 + 2 NaH → 2 Na  BH 4 
• no change in hybridization of underlined atom
• breaking of 3c – 2e– bond

H3 BO3 + water → B ( OH )4
−

• sp2 → sp3 (change in hybridization of underlined atom)

BeH 2 → ( BeH 2 )( s )
• In solid state the compound exists in polymeric form having 3c – 2e– bonds.

BF3 + NaF → NaBF4

• sp2 → sp3 (change in hybridization of underlined atom)

Solution 25: (a)

Compound Steric Lone Pairs Bond Pairs Shape

Number
ClF2– 5 3 2 linear
ClF2+ 4 2 2 bent shaped
IO2F2– 5 1 4 See – saw
F2SeO 4 1 3 pyramidal shaped
IOF4– 6 1 5 Square pyramidal (sp3d2)
XeOF2 5 2 3 T-shaped (sp3d)
BrF5 6 1 5 Square pyramidal (sp3d2)
XeOF4 6 1 5 Square pyramidal (sp3d2)

MULTIPLE CHOICE QUESTIONS

Solution 26: (a), (b), (c), (d)

All given orders are correct.

Solution 27: (a), (c), (d)

(a) Al ( OH )3 + NaOH → Na  Al ( OH )4 
( sp2 ) ( sp3 )
(b)
(c) SiF4 + 2 HF → H 2 SiF6
sp3d sp3d 2

(d) 2 PCl5 ⎯⎯⎯⎯→

solidification
PCl4 + PCl6
( sp d )
3
( sp3 ) ( sp3d 2 )

NUMRIC ANSWER TYPE

Solution 28:

According to the question, the structure of S2 will be analogous to O2, i.e.,

P: Number of unpaired electrons = 2

8−4
Q: The bond order of S2 = =2
2
R: The number of  bond(s) in S2 = 1
 8−6
S: The bond order of S22– = =1
2

Solution 29: (634) Structures are:

Thus,
The number of P–S bonds in P4S3 = x = 6
The number of P– P bonds in P4S3 = y = 3
The number of  –bonds in P4O10 = z = 4

Solution 30: (3.00)

Solution 31: 28.00

Total a = 4, b = 2, c = 2, d = 2.
Therefore, a2+b2+2cd = 28

Solution 32: 6.00

⟶ Unsymmetrical cleavage of B2H6: with small sized strong Lewis base like: NH3, MNH2,
Me2NH
⟶ Symmetrical cleavage of B2H6: with large sized strong Lewis base or weaker Lewis base like:
PH3, PF3, H, CO, T.H.F. Me3N, Pyridine.

Solution 33: 7.00

B(OMe)3 and HCHO cannot form H-bond.

Solution 34: 4.00

G-1 A (Li), B(Na), C(I), D(Rb), E(Cs)
G-2 F(Be), G(Mg), H(Ca), I(Sr), J(Ba)
G-13 K(B), L(Al), M(Ga), N(ln), O(Tl)
G-15 P(N), Q(P), R(As), S(Sb), T(Bi)
G-17 U(F), V(Cl), W(Br), X(I), Y(At)
(i) Tl+ > Ca2+; Polarising power (T)
(ii) Bi3+ > Sb3+ > As3+; Stability of cation (T)
(iii) F–(aq) > Cl–(aq) > Br–(aq) > I–(aq); Size (T)
(iv) BaCl2 > SrCl2 < MgCl2 < AlCl3; Covalent Nature (T)
(v) MgCO3 > CaCO3 > SrCO3 > BaCO3; Thermal stability (F)
(vi) LiCl > NaCl > KCl > RbCl > CsCl; Thermal stability (T)
(vii) K3N > Na3N > Li3N; Lattice energy (F)
(viii) BF3 < BCl3 < BBr3 < BI3; Melting point (T)
⇒ |p – q|2 |6 – 2|2 = 16

COMPREHENSION # 1

Solution 35: (b) Both are blue coloured compound because colour arises due to transfer of
electron between FeII and FeIII cation.

COMPREHENSION # 2

Solution 36: (b)

In AsH3, P4 and H2Se → No Hybridisation [Acc. To Drago’s rule]
GeH4 → sp3 -hybridisation [% s = 25%] maximum.

Solution 37: (a)

PH 4 → sp 3 10928'
OF2 → sp 3  B. A.  10928'
SF2 → sp 3  B. A.  10928'
SbH 3 → No hybridization,  B. A.  90
Order of B.A.: PH4  OF2  SF2  SbH3  H2Te

COMPREHENSION # 3

Solution 38: (c) sp4

4
% p-character = 100 = 80%
5

COMPREHENSION # 4

Solution 39: (b) 6, 6

All the B-H-Al bonds are 3c-2e- bonds.

All the B-H bonds are 2c-2e- bonds.

SUBJECTIVE ANSWER TYPE

Solution 40:
(i) I = 1.9 D, II = 1.1 D, III = 1.9 D
(ii) 2.9 D

(i) I) CH3CCl3
II) CHCl3:

III) CH3Cl:

(ii) Acetone:
Solution 41:

Solution 42: As the difference in the size of p and d orbitals decreases the extent of p − d 
overlapping increases and thus tendency of polymerization decreases.

Solution 43: (a) Disulphate: 4 p − d  bonds

(b) triphosphate: 3 p − d  bonds

(c) trimetaphosphate: 3 p − d  bonds

(d) trimer of SO3: 6 p − d  bonds

(e) P4O10: 4 p − d  bonds

(f) P4O6: 0 p − d  bonds

Solution 44: Solid PCl5 exists as [PCl4]+ (sp3) and [PCl6]– (sp3d2); N2O5 as NO2+(sp) and NO3–
(sp2); XeF6 as XeF5+ (sp3d2) and F– (as bridging ion).
Solution 45: In O2 and N2 energy gap between HOMO and LUMO is large so electronic
excitation is not possible with visible light. But for halogens, the electronic excitation can be
done with visible light because energy difference between HOMO and LUMO is small.

Solution 46:
(i) Na[B3O3(OH)4]

(ii) Na2[B4O5(OH)4].8H2O

(iii) Na6P6O18:

(iv) S3O62-:

(v) S3O9:
(vi) (CN)2:

Solution 47: False Statements - 1, 5, 6, 7, 15, 19, 20, 28

Corrected Statements:

(1) PbI2 is yellow due to high polarization of I-

(5) The order of Xe–F bond length in various fluorides of Xenon is

XeF2(1.977) > XeF4(1.94) > XeF6 (1.94 & 1.850, two bond types).

(6) In case of PH5 molecules, hydrogen cannot unpair and excite an electron from 3s atomic
orbital of phosphorous to 3p atomic orbital. This is because hydrogen has much lower
electronegativity than chlorine. Hence, sp3d hybridization is not possible with PH5 molecule.
This molecule is unstable and does not exist.

(7) CH3Cl has larger dipole moment than CH3F because dipole moment is based on the product
of distance and charge, and not just charge alone. Fluorine is more electronegative than chlorine,
but the carbon-fluorine bond is also much shorter than the carbon-chlorine bond: 139 pm vs 178
pm.

(15)

Individual oxidation number of two Sulphur atoms in thiosulphate (S2O32–) ion are +5 and -1,
however the average oxidation number of Sulphur is +2.
(19) HOMO is  * 2 pz .

(20) Bond order of O2– is less then O2+.

B.O. for O2– = 1/2 × [10 – 7]

B.O. for O2– = 1.5
B.O. for O2+ = 1/2 × [10 – 5]
B.O. for O2+ = 2.5

(28) Delta bonds (δ bonds) are covalent chemical bonds, where four lobes of one involved atomic
orbital overlap four lobes of the other involved atomic orbital. This overlap leads to the
formation of a bonding molecular orbital with two nodal planes which contain the internuclear
axis and go through both atoms.