Chemical Bonding (Theory) Module-2-1
Chemical Bonding (Theory) Module-2-1
Chemical Bonding (Theory) Module-2-1
– –
2. Calcium Hydride (CaH2) Ca++(H–)2 H× Ca++ H ×
H
| H
×
4. Phosphene (PH3) H–P–H H ×
P ×
H
××
5. Carbon mono-oxide(CO) C O ×
× C ×
× O
× ×
7. Hydrogen Cyanide (HCN) H C N H C ×
×
N
–
+– ××
8. Potassium Isocyanide (KNC) K N C K+ × N ×
× C
–
–
9. Sodium Hydroxide (NaOH) Na+ O H Na+ × O × H
××
10. Nitrous oxide (N2O) N N O ×
× N ××
×× N ×
× O
×× ××
11. Nitric oxide (NO or N2O2) O N N O O ×
× N ×
× N ×
× O
O
O ×
12. Dinitrogen tri oxide (N2O3) O N N O ×
×× ×
O × N ×× N ×× O
O O
O O×
13. Dinitrogen tetraoxide (N2O4) O N N O ×
×× ×
O × N ×× N ×× O
O O
O O
×× ××
14. Nitrogen Penta oxide (N2O5) O N O N O O ×
× N × O × N ×× O
××
15. Nitrous acid (HNO2) H O N O H O × N ×× O
O
O
16. Nitric acid (HNO3) H O N O ××
H O × N ×× O
Compound Structure Electron dot/Cross formula
–
O
O
–
17. Nitrate Ion (NO3–) O N O
O ×
××
O
× N ×
+
H H
×
– × –
H N H Cl H × N H Cl×
18. Ammonium Chloride (NH4Cl) ×
H H
––
O O
19. Carbonate Ion (CO3– – ) –
O C O
–
O ×
××
C × O
××
20. Sulphur di-oxide (SO2) O S O O ×
× S ×
× O
O O
××
21. Sulphur Tri-oxide (SO3) O S O O ×
× S ×× O
––
O O
22. Sulphite Ion (SO3– – ) –
O S O
–
O ×
××
× O
S
××
––
O
O ××
×
– –
O S × O
23. Sulphate Ion (SO4– – ) O S O ××
O
O
––
××
××
××
S S
××
×
–
O S O
– O S × O
24. Thio-sulphate Ion (S2O3– – ) ××
O O
Compound Structure Electron dot/Cross formula
H
H
O O
×
25. Phosphoric Acid (H3PO4) H O P O H H O× P × O H
××
O O
H H
×
– O
O ×
×
– – O P × O
27. Phosphate Ion (PO4– – –) O P O ××
O O
O
O ××
O ×
Mn ×× O
28. Potassium Permagnate (KMnO4) K+ O Mn O ××
O
O
Compound Structure
+
30. Nitronium Ion (NO2+) O N O
+
32. Hydronium Ion (H3O+) H O H
Cl
33. Sulphuryl chloride (SO2Cl2)
O S O
Cl
Compound Structure
–
O
34. Potassium chlorate (KClO3) K+ O Cl O
–
O
–2
O O
O O
–3
– –
N C C N
– –
37. Ferry-cyanide Ion [Fe(CN)6]–3 N C Fe+++ C N
– –
N C C N
–4
– –
N C C N
– –
38. Fero-cyanide Ion [Fe(CN)6]–4 N C Fe++ C N
– –
N C C N
Cl Cl Cl
39. Aluminium chloride (Al2Cl6) Al Al
Cl Cl Cl
O O
O
41. Hypophosphate acid (HPO3)
H O P O
O O
O O
Compound Formula Structure
O
43. Sulphurous acid H2SO3
H O S O H
O
44. Persulphuric acid H2SO5 H O S O O H
××
46. Chlorous acid HClO2 H O Cl O
××
×× O
47. Chloric acid HClO3 H O Cl
O
O
48. Perchloric acid HClO4 H O Cl O
O
O O
O Cl O Cl O
49. Perchloric anhydride Cl2O7
O O
O
O O
51. Perchromate CrO5 Cr
O O
O
Cl Cr Cl
52. Chromyl Chloride CrO2Cl2
O
Compound Formula Structure
O Cl
54. Bleaching Powder CaOCl2 Ca
Cl
–2
C C
55. Calcium carbide CaC2 Ca or Ca+2
C C
O
56. Ozone O3
O
O
S S S
58. Ground state of sulphur S8 S
S S
S S
S
60. Sodium thiosulphate Na2S2O 3 2Na+ O
–
S
–
O
O
CHEMICAL BONDING
1. INTRODUCTION
(I) It is well known fact that except for inert gases , no other element exists as independent atoms under
ordinary condition.
(II) Most of the elements exist as molecules which are cluster of atoms. How do atoms combine to form
molecules and why do atoms form bonds ? Such doubts will be discussed in this chapter.
(III) A molecule will only be formed if it is more stable and has a lower energy, than the individual atoms.
2. CHEMICAL BOND
(I) A force that acts between two or more atoms to hold them together as a stable molecule.
(II) It is union of two or more atoms involving redistribution of e– among them.
(III) This process accompanied by decrease in energy.
(IV) Decrease in energy Strength of the bond.
(V) Therefore molecules are more stable than atoms.
Examples
based on Causes of Chemical Bond
Ex.1 When two atoms combine to form a molecule -
(A) Energy is released (B) Energy is absorbed
(C) Energy is neither released nor absorbed (D) Energy may either released or absorbed
Sol. (A) To attain stability energy is released.
H × O × H Cl × Be × Cl
Cl ×
B× Cl In BCl3
×
×
Cl
and 14 electrons respectively. Cl
Examples
based on Octet Rule
Ex.2 Which follows octet rule -
(A) FeCl 2 (B) AgCl (C) CaCl2 (D) CuCl
Sol. (C) Because in other compounds there is more than 8 e– in outermost shell of central atom.
Classification of bonds : -
CHEMICAL BONDS
(I) The chemical bond formed between two or more atoms as a result of the complete transfer of one or
more electrons from one atom to another is called Ionic or electrovalent bond.
(II) Electro +ve atom loses electron (group IA to IIIA)
(III) Electro –ve atom gains electron (group VA to VIIA)
(IV) Electrostatic force of attraction between cation and anion is called ionic bond or electrovalent bond.
Electronegativity difference nature of ionic bond.
Example IA and VIIA group elements form maximum ionic compound.
Na + Cl Na+ + Cl –
2, 8, 1 2, 8, 7 2, 8 2, 8, 8
1e– (Ne configuration) (Ar configuration)
(V) More the distance between two elements in periodic table more will be ionic character of bond.
(VI) Total number of electron lose or gained is called electrovalency.
Example –
(a) Mg O
2, 8, 2 2, 6 electrovalency of Mg = 2
electrovalency of O = 2
2e–
Ca Cl
(b) 2,8,8,2 2,8,7 electrovalency of Ca = 2
electrovalency of Cl = 1
One e–
Cl
One e – 2,8,7
Ca + O CaO
(c)
Ca O
2, 8, 8, 2 2, 6 electrovalency of Ca = 2
electrovalency of O = 2
2e–
(VII) The force of attraction is equal in all direction so ionic bond is non-directional.
(VIII) Ionic compound do not have molecular formula. It has only empirical formula. eg. NaCl is empirical
formula of sodium chloride.
+ – + – + + – + – +
– + – + – – + – + –
+ – + – +
+ – + – +
– + – + –
– + – + –
Attraction Repulsion
(b) Isomorphism –
(I) Two compounds are said to be isomorphous if they have similar no. of electrons i.e.similar
configuration of their cation and anion.
(II) They have similar crystal structure.
Example –
Na+ F– Mg+2 O –2
Valency + 1, –1 + 2, –2
electronic configuration 2, 8, 2, 8 2, 8 2, 8
similarly Ca +2 2Cl –1 2K +1 S –2
2, 8, 8, 2, 8, 8 2, 8, 8
2, 8, 8
2, 8, 8 2, 8, 8
H2O–
+ – + –
H O H O
O–
+
O–
+
2 + H 2 2 + H 2
+ –
Na +
H2O– Cl +
– – H2O–
+
H 2O +
H 2O
+
+
HO–
HO–
H 2O
H 2O
2
2
–
–
+
–
Oxygen atom of H2O give its electron to Na+ H atom of H2O gain electron from Cl
(III) Thus charge on Na+ and Cl– decreases and electrostatics force of attraction also decreases which
leads to free ion.
(IV) The energy released due to interaction between solvent and solute is called solvation energy.If water
is used as solvent it is called hydration energy.
(V) For an ionic compound to be soluble in water – Hydration energy > Lattice energy
1
Lattice energy Solubility
Examples
based on Ionic Bond
1
As solubility
lattice energy
(b) in LiI covalent nature is more according to Fajan’s rule but HE > LE therefore Li is more soluble
in water.
(c) Keeping size of anion constant, the hydration energy decreases with the increase of cationic
radius. hence order of solubility of MSO4 will be –
BeSO4 > MgSO4 > CaSO4 > SrSO4 > BaSO 4 (Exception of Fajan’s rule)
(d) If size of cation and anion is very large, solubility decreases from top to bottom.
(e) Solubility decreases in a period (as ionic nature decreases and covalent nature increases)
NaCl > MgCl2 > AlCl3
(III) Polarisation of anion :
Polarisation capacity is maximum in pseudo inert gas configuration.
1
solubility
polarisation
AgF > AgCl > AgBr > AgI
– Polarisation increases.
– Covalent character increases.
– Solubility decreases.
(IV) Ionic reaction –
(a) Ionic compounds shows ionic reaction and covalent compounds shows-molecular reaction.
(b) Ionic reactions are faster than molecular reaction because of free ions.
e.g. When NaCl is added in AgNO3 solution, white ppt of AgCl is formed at once.
Na+ NO – + AgCl
Ag+NO 3– + Na+NO – 3
white ppt.
6. POLARISATION
CaF2
CaCl2 - Size of anion increases
CaBr2 - Covalent character increases
Cal2 - Ionic character decreases
(c) Charge on cation and anion : -
Polarisation charge on cation anion
(I) Charge on cation Polarisation (covalent character)
eg. NaCl MgCl2 AlCl 3 SiCl 4
Na + Mg ++ Al +++ Si ++++
Examples
based on Fajan's Rule
Ex.7 Compound with maximum ionic character is formed from -
(A) Na and Cl (B) Cs and F (C) Cs and (D) Na and F
Sol. (B) Using fajan’s rule, larger cation and smaller anion will have max. Ionic character.
Ex.8 Out of the following which one has the highest values of covalent character -
(A) ZnCl2 (B) CaCl2 (C) CdCl2 (D) CuCl
Sol. (A) Because Zn+2 has smallest size among the all.
7. COVALENT BOND
(I) A covalent bond is formed by the mutual sharing of electrons between two atoms of electro negative
elements to complete their octet. (Except H which completes its duplet).
H H H H O O O O N N N N
H2 molecule O2 molecule N2 molecule
(II) The shared pair of electrons should have opposite spins, and are localised between two atoms
concerned.
(III) Shairing of electrons may occurs in three ways –
2 1 Single bond ( )
4 2 Double bond ( )
6 3 Triple bond ( )
(I) One orbital can accomodate at the most 2 electrons with opposite spins
(II) Half filled orbital or unpaired electron orbital accepts one electron from another atom, to complete its
orbitals.
(III) Tendency to complete orbital or to pair the electron is an essential condition of covalent bond. Completion
of octet is not the essential condition of covalent bond.
(IV) Covalency : It is defined as the number of electrons contributed by an atom of the element for shairing
with other atoms to achieve noble gas configuration.
(V) If the outermost orbit has empty orbitals then covalent bonds are formed in exicted state.
Variable valency in covalent bonds :
(I) Variable valencies are shown by those elements which have empty orbitals in outermost shell.
(II) Lone pair electrons gets excited in the subshell of the same to form the maximum number of unpaired
electrons. Maximum covalency is shown in excited state.
(III) The energy required for excitation of electrons is called promotion energy.
(IV) Promotion rule – Excitation of electrons in the same orbit.
Example –
(a) Phosphorus Ground state
Covalency 3 (PCl3)
3s 3p
Phosphorus Excited state
Covalency – 5 (PCl5)
3s 3p 3d
(b) Sulphur Ground state.
Covalency – 2 (SF2)
3s 3p 3d
Sulphur Excited state
(Ground state)
5s 5p 5d
So it shows three excited states – Maximum number unpaired electrons = 7
Variable Valencies are 1, 3, 5, 7
Unstable
Examples
based on Covalent Bond
Ex.10 A covalent bond is possible between -
(A) Similar atom (B) Dissimilar atoms
(C) Similar and dissimilar atoms (D) Similar molecules
Sol. (C) It is related to electronegativity.
Ex.12 Among LiCl, BeCl2, BCl 3 and CCl 4, the covalent bond character follows the order -
(A) LiCl < BeCl2 > BCl3 > CCl 4 (B) LiCl > BeCl2 < BCl3 < CCl 4
(C) LiCl < BeCl2 < BCl3 < CCl 4 (D) LiCl > BeCl2 > BCl3 > CCl 4
Sol (C) The covalent character increases according to charge on cation.
(I) Bond formed between two atoms by the overlapping of half filled orbitals along their axis (end to end
overlap) is called sigma bond.
(II) bond is directional.
(III) bond do not take part in resonance.
(IV) Free rotation is possible about a single bond.
(V) Maximum overlapping is possible between electron clouds and hence it is strong bond.
(VI) There can be only bond between two atoms.
Sigma bond are formed by four types of overlapping
(a) s - s overlapping (H2) - Two half filled S-orbitals overlap along the internuclear axis.
1s bond 1s 1s
1s
(Formation of H2 molecule)
(b) s - p overlapping (Formation of HF) – When half fill s-orbital of one atom overlap with half filled
p-orbital of other atom.
formation of C2H2
(d) p - p overlapping – (Coaxial) – It involves the coaxial overlapping between half filled p-orbitals of
two different atoms.
eg. Formation of Cl2, F2, Br2
p p
– + + + – –
Py Py
Pz + Pz
O2 molecule
Only py and pz of oxygen atom have unpaired e– in each orbital for bonding.
Electron configuration of oxygen is – 1s22s22px2 2py12pz1
(III) Free rotation about a bond is not possible.
(IV) bond is weaker than bond (Bond energy difference is 63.5 KJ or 15 K cal/mole)
(V) bonds are non-directional, so do not determine the shape of a molecule.
(VI) bond takes part in resonance.
(VII) bond formed by pure or unhybrid orbitals.
9. HYBRIDISATION
Consider an example of Be compound :-
If it is formed without hybridisation then -
s–p p–p
Cl Be Cl
both the Be–Cl bonds should have different parameters and p-p bond strength >s-p bond strength.
Practically bond strength and distance of both the Be-Cl bonds are same.
This problem may overcome if hybridisation of s and p-orbital occurs.
Hybridisation :
(I) It is introduced by pauling, to explain equivalent nature of covalent bonds in a molecule.
(II) Definition : Mixing of different shapes and approximate equal energy atomic orbitals, and redistribution
of energy to form new orbitals, of same shape & same energy. These new orbitals are called hybrid
orbitals. and the phenomenon is called hybridisation.
Now after considering s-p hybridisation in BeCl 2
sp – sp sp – p
Cl Be Cl
bond strength of both the bonds will be equal.
Characteristic of Hybridisation :
(III) Each hybrid orbital having two lobes, one is larger and other is smaller. Bond will be formed from large
lobe.
(IV) The number of hybrid orbitals on central atom of a molecule or ion = number of bonds
+ lone pair of electron.
(i) The 1st bond between two atoms will be sigma.
(ii) The other bond between same two atoms will be pi bond.
(iii) Maximum two pi bonds may be present on a single atom.
(iv) The electron pair of an atom which do not take part in bond formation called as lone pair of electron.
(V) One element can represent many hybridisation state depending on experimental conditions for example,
C showing sp, sp2 and sp3 hybridisation in its compounds.
(VI) Hybrid orbitals are differentiated as sp, sp 2, sp 3 etc.
(VII)The order of repulsion between Ip & bp is : Ip - Ip > Ip - bp > bp - bp
(VIII)The directional properties in hybrid orbital is more than atomic orbitals. Therefore hybrid orbitals form
stronger sigma bond. The directional property of different hybrid orbitals will be in following order.
sp < sp2 < sp 3 < sp3d < sp2d 2 < sp3d 3
Difference between hybridisation & overlapping
Overlapping Hybridisation
It occurs between orbitals of two atoms It occurs among orbitals of the same atom
1
SF 4 [ 6 + 4 ] = 5 sp3d hybridisation.
2
1
SO 24– [ 6 + 2 ] = 4 sp3 hybridisation.
2
(‘O’ is divalent so add only charge on anion)
1
NO 3– [5 + 1] = 3 sp2 hybridisation.
2
If such type of e– pairs are –
two – sp hybridisation
three – sp 2 hybridisation
four – sp 3 hybridisation
five – sp3d hybridisation
six – sp3d2 hybridisation
2s 2p
Be (excited state)
2s 2p
Be atom accepts two electrons from F in BeF2,
sp sp
sp hybridisation sp hybridisation
CO2 Molecule (O = C = O ) :
In CO2 molecule, C has two sp hybrid orbitals & two unhybridised p orbitals.
bond
bond
Molecular orbital picture of CO2
Thus, CO2 molecule is a linear in shape & having 180° bond angle.
The bond length between C–O bond is reduced due to the presence of bond.
CH CH [H CA CB H]
In CH CH molecules, each C atom contains two sp hybrid orbitals & two unhybridised p orbitals
2s 2p
C(ground state)
C(excited state)
The remaining one sp hybrid orbital of each C atom overlaps with s orbital of H, forming sigma bond
between C – H.
The two unhybridised p orbitals of each C atom (py and px) overlap laterally to form two pi() bonds.
Each C atom forms two sigma bonds but in C2H2, total sigma bonds are 3
Each C atom forms two bonds. Total bonds in C2H2 are two
Examples on sp hybridisation
CO 1 1 sp 180° Linear
B (excited state)
3.35 Å
3.35 Å
1.42 Å
SnX2 (X = F, Cl, Br, I)
5s 5p
Sn (ground state)
Sn (excited state)
Sn after hybridisation
sp2
shares 2e– with 2 atom.
SnX2 having two bonds & one LP electron therefore hybridisation is sp2 N
The bond angle is SnX2 will be less than 120° (due to presence of one LPe.) H
MolecuarpymidbtfNH3
Examples on sp 2 hybridisation
Example bond I.p.e. Hybridisation Bond angle Shape
sp3 Hybridisation :
(I) In this hybridisation one s orbital & three p orbitals of an atom of a molecule or ion, are mixed to give
four new hybrid orbitals called as sp3 hybrid orbitals.
(II) The angle between these four hybrid orbitals will be 109°28’
2s 2p
C (ground state)
C (excited state)
C atom share
(c) Two sigma bonds & two lone pair lone pair electrons :
(I) This condition is shown by following compounds and ions.
O
H2O, H2S, H2Se, H2Te, OCl2, OBr2, OF 2, OI 2 etc.
(II) In all above examples, the central atom showing sp3 hybridisation, H
angular shape and bond angle will be either less then 109°28’ or
more than 109°28’.
H
In H2O the hybridisation on O atom is sp3, but due to presence of two lone pair electrons they
repell each other and then repell their adjacent bond pair electron. These repulsion will be in
following order.
I.p. – I.p. > I.p. – b.p. > b.p. – b.p.
l.p. = lone pair electron
b.p. = bond pair electron
CH4 4 - sp 3 Tetrahedron
3
CCl4 4 - sp Tetrahedron
CBr4 4 - sp 3 Tetrahedron
PCl4+ 4 - sp 3 Tetrahedron
NH4+ 4 - sp 3 Tetrahedron
BF4– 4 - sp 3 Tetrahedron
AlF4– 4 - sp 3 Tetrahedron
BeF4–2 4 - sp 3 Tetrahedron
MgF4–2 4 - sp 3 Tetrahedron
Example bond I.p.e. Hybridisation Shape
Ni(CO)4 4 - sp 3 Tetrahedron
NF3 3 - sp 3 Pyramidal
NCl3 3 1 sp 3 Pyramidal
N(CH3)3 3 1 sp 3 Pyramidal
PF3 3 1 sp 3 Pyramidal
PCl3 3 1 sp 3 Pyramidal
AsCl3 3 1 sp 3 Pyramidal
SbCl3 3 1 sp 3 Pyramidal
BiCl3 3 1 sp 3 Pyramidal
NH3 3 1 sp 3 Pyramidal
: –CH3 3 1 sp 3 Pyramidal
H3O+ 3 1 sp 3 Pyramidal
SO32– 3 1 sp 3 Pyramidal
ClO3 3 1 sp 3 Pyramidal
XeO3 3 1 sp 3 Pyramidal
H2O 2 2 sp 3 Angular (V)
H2S 2 2 sp 3 Angular (V)
NH2– 2 2 sp 3 Angular (V)
OF2 2 2 sp 3 Angular (V)
Cl2O 2 2 sp 3 Angular (V)
SCl2 2 2 sp 3 Angular (V)
Diamond 4 - sp 3 Tetrahedron
SiO2 4 - sp 3 Tetrahedron
SiC 4 - sp 3 Tetrahedron
sp3d Hybridisation :
(I) In this hybridisation one s orbitals and one d orbital are mixed to give five new hybrid orbitals which
are equivalent in shape and energy called as sp3d hybrid orbitals.
(II) Out of these five orbitals, three hybrid orbitals are at 120° angle and two hybrid orbitals are perpendicular
to the plane of three hybrid orbitals that is trigonal planar, the shape of molecule becomes is trigonal
bipyrmaidal.
For example, PF5 showing sp3d hybridisation
3s 3p 3d
P (ground state)
3s 3p 3d
P* (excited state)
3s 3p 3d
P atom share with five e of F
3
sp hybridisation
(III) In this hybridisation dz2 orbital is hybridised with s and p orbitals.
In this way five sp3d hybrid orbitals form five sigma bond with five F atoms and give a molecule of
PF5, shape of this molecule is trigonal bipyramidal.
Axial two P–Cl bonds are longer than equatorial three P–Cl bond due to repulsion between 3 equatorial
bp of e– and 2 axial b.p. of e–
In above hybridisation there are four conditions
Cl
(a) Five sigma bonds and zero lone pair electron :
The following examples represent this conditions.
PF5, PCl5, PBr5, Pl5, AsF5, AsCl5, SbCl 5, SbF5 etc. Cl P
Cl
The shape of all above molecules is trigonal bipyramidal.
Cl
(b) Four sigma bonds and one lone pair of electron :
The following examples represent this condition.
SF4, SeF4, TeF4, PoF4, PF 4–, SbF4–, SCl4, SeCl4, TeCl 4 etc. Cl
The shape of all above examples will be irregular tetrahedron. Structure of PCl5
Examples SF4
3s 3p 3d
S ground state
F
3p 3d
F
3s
S excited state S ••
3s 3p 3d F
F
S atom share with four e– of F Structure of SF4
3
five-sp d hybrid orbitals
F
(d) Two sigma bonds & three lone pair of electrons :
Structure of CIF3
The following examples represent this condition.
ICl2–, IBr2–, ClF2–, IF2–, BrF2–, XeF2–, I3–, Br3–
The geometry of above examples will be linear
sp3d 2 Hybridisation :
(I) In this hybridisation, one s-orbitals, three p-orbitals & two d-orbitals are mixed to give six new hybrid
orbitals known as sp3d2 hybrid orbitals.
(II) The shape of molecule obtained from above six hybrid orbitals will be symmetrical octahedral.
(III) The angle between all hybrid orbitals will be 90°.
Example : SF6, AlF6–2, PF 6–, ICl5, XeF4, XeOF 4, ICl4–,
(IV) Two ‘d’ orbital participates in the hybridisation are dx2–y2 and dz2.
SF6 :
3s 3p 3d
S (ground state)
3s 3p 3d
S (excited state)
3s 3p 3d
S (after hybridisation)
3 2
sp d hybridisation
sp3d3 Hybridisation :
(I) In this hybridisation, one s-orbitals & three d-orbitals are mixed to give seven new hybrid orbitals known
as sp3d3 hybrid orbitals.
(II) In this hybridisation d-orbitals used are dxy dxz & dyz orbitals.
(III) These seven sp3d3 orbitals are configurated in pentagonal bipyramidal shape.
(IV) Five bond angles are of 72° & two bond angles of 90°.
(V) The following examples showing sp3d3 hybridisation –IF7 & XeF6.
F
F
F F
I
F F
F
Structure of IF7
1. Two Linear sp
2. Three Coplaner trigonal (Triangular) sp 2
3. Four Tetrahedral sp 3
4. Five Trigonal bipyramidal sp3d
5. Six Octahedral (Square bipyramidal) sp3d 2
6. Seven Pentagonal bipyramidal sp3d 3
Examples
based on Hybridization
Ex.13 The hybridization of carbon atoms ion C – C single bond of H – C C – CH = CH2 is -
(A) sp3-sp3 (B) sp2-sp (C) sp-sp2 (D) sp3-sp
Sol. (C) As the first carbon has triple bond and second one has double bond with other two carbon atom.
Ex.14 C – C bond in C2H6 undergoes heterolytic fission, the hybridisation of carbon is/are -
(A) sp2 (B) sp3 (C) sp2, sp3 (D) sp, sp2
Sol. (C) During heterolytic fission there will be formation of CH3+ and CH3¯ which has sp2 and sp3 hybridization
respectively.
Ex.15 The enolic form of actone contain bond (a), bond (b) lone pair (c) -
(A) 9a, 1b, 2c (B) 8a, 2b, 2c (C) 10a, 1b, 1c (D) 9a, 2b, 1c
Sol. (A) This is clear from its structure as shown below.
H – H
| |
H — C — C =C — H
| |
H H
(III) By increasing one lone pair of electron, bond angle is decreased approx by 2.5°.
e.g. CH4 NH3 H2O – sp 3
109° 107° 105° hybridisation
(IV) In the different molecules if central atom have same number of lone pair of electron then bond
angle will depend on electronegativities of A & B.
In ABx type of molecules if side atoms are same EN of central atom increases the bond angle
increases
O•• S ••
••
••
>
105° 92°
H H H H
more repulsion less repulsion bp-bp
••
110° 103°
Cl Cl H H
PF3 < PCl3 < PBr3 < Pl3 (EN of side atom decrease)
OF2 < Cl2O < Br2O
SF2 < SCl2 < SBr2
Bond angle depends on size of side atom, On increasing size of atom bond angle increases.
Cl2O > H2O
•
•O •• •
•O
••
105° 110°
H H Cl Cl
Examples
based on VSEPR Theory
Ex.17 In following which central atom has different hybridisation than other –
(A) Cl2O (B) OF 2 (C) H2O (D) SO 2
Sol. 2 3
(D) Because it has sp hybridisation other three have sp hybridisation.
Ex.18 In following hydrocarbon which one has 75% p character and 25% s charater -
(A) C2H4 (B) C2H2 (C) CH4 (D) :CH2
Sol. 3
(C) CH4 because it has sp hybridisation.
Ex.22 Ether and water have same hybridization at oxygen. What angle would you
expect for them -
Sol. In H2O bond angle is less than 109º28’ due to lone pair and bond pair repulsion. But in ether, due to
strong mutual repulsion between two alkyl groups bond angle becomes greater then 109º28’
Top to bottom in a group. Vander waal’s force increases between the molecules.
(II) Covalent solid : - Those solids in which atoms are linked together by covalent bonds, forms
inifinite three dimensional giant structure.
e.g. Diamond, Graphite, AIN, SiC, SiO2 etc.
Molecular solid : - Discrete (separate) molecules are formed by covalent bonds and then the
molecules associated due to intermolecular force of attraction. (Vanderwaal force)
eg. Solid I2, dry ice (Solid CO2) etc.
(III) Conductivity : - Mostly covalent compounds are bad conductor of electricity. But few polar
covalent compounds due to self ionisation can conduct electricity.e.g. H2O, liq. NH3 etc.
H2O + H2O H3O+ + OH–
2NH3 NH4+ + NH2–
Free ions are formed which can conduct electricity.
Exceptions : - Graphite, HCl in water.
(IV) Solubility : - Non polar compound are soluble in non polar solvents. Non polar compounds forms
Vander waal bond with non polar solvent molecules.
(V) Isomerism : - Covalent bond is rigid and directional, so it shows isomerism.
eg. Organic compounds.
(VI) Reaction : - Reaction between covalent compounds are slow. Because it involves breaking of odl
bonds and formation of new bonds.
10. DIPOLE MOMENT
•• •• ••
(B) NH3 PH3 NF3
3 H H F
P H
••
N 2H
••
4 N F
••
4 4
1 H H F
=1.47D EN of P H
=0.24D
Total = 1 + 2 + 3 + 4 = 1.47D
(XI) Dipole moment of H2O is 1.85 D which is resultant of two O–H bonds.
O
H H
of H2O of H2S because electronegativity of oxygen is higher than sulphur.
(XII) Angular structure of molecule have greater dipole moment.
Application of dipole moment :
(I) To determine polarity and geometry of molecule -
If = 0 compound is non polar and symmetrical
eg. CO2, BF3, CCl4, CH4. BeF2 etc.
If 0 compound will be polar and unsymmetrical.
H2O, SO2, NH3, Cl 2O, CH3Cl, CHCl 3 etc.
Cl—C—H Cl—C—H
Cl—C—H H—C—Cl
cis-form Trans-form
Polar ( ) Non Polar ( )
(b) If two groups have opposite inductive effect than trans-isomer will have greater dipole moment \-
eg.
H Cl H Cl
C C
C C
CH3 H H CH3
1
(IV) To locate position of substituents in aromatic compounds. Bond angle
(a) If same substituents are preset in the symmetrical position of benzene ring compounds will be
zero
Cl
Cl Cl
Cl
Cl Cl
Angle 180° Angle 120° Angle 60°
p-dichloro benzene m-dichloro benzene o-dichloro benzene
Ex.24 Bond length of HCl is 1.275 Å (Charge = 4.8 × 10–10 e.s.u.) if = 1.02 D, then HCl is -
(A) 100% ionic (B) 83% covalent (C) 50% covalent (D) 40% ionic
Sol. (B) % ionic character
observed 102
.
= × 100 = × 100 = 17% ionic = 83% covalent
theoritical 1275
. x 4.8
Ex.25 The dipole moment of the ammonia molecule is 1.48D. The length of the dipole is -
(A) 3.08 × 10–11 m (B) 5 × 102 m (C) 308 m (D) None
Sol. (A) M = 1.48 × 3.33 × 10 –30 cm
= 4.93 × 10–30 cm.
q = 1.6 × 10–19C
4.93 10 30
l = = = 3.08 × 10–111 m = 0.0308 nm
q 1.6 10 19
The NH3 molecule can not have the shape of an equilateral triangle because in the case its dipole
moment would equal zero. It is actually constructed in the form of a triangular pyramid with the
nitrogen atom at its vertex and the hydrogen atoms at the corners of its base.
(I) It is a covalent bond in which the shared e– pair come from one atom is called coordinate bond.
(II) Necessary conditions for the formation of co-ordinate bond are-
(a) Octet of donor atom should be complete and should have atleast one lone pair of electron.
(b) Acceptor atom should have a defficiency of at least one pair of electron.
××
•• ×
••
••
(III) Atom which provide electron pair for shairing is called donor.
(IV) Other atom which accepts electron pair is called acceptor. That is why it is called donor-acceptor or
dative bond
H F
H N•• + B F NH3NH3
H F
BF3 is electron defficient compound.
Example:
H
H3 N + H+ H N H
H
(Lowry - Bronsted acid)
(e– acceptor)
H H
+ •• +
O+ H
H3O O H
••
••
H H
••
•• •• O
O O
••
O
••
••
O3 •• •
•O
••
O•
•• •
••
•••• ••
O
••
••
N2O N N
••
Compounds in which Ionic, covalent and co-ordinate bonds are present, are as follows-
NH4Cl, CuSO4, K4[Fe(CN)6], KNC, Na3PO 4, KNO3, etc
Examples
based on Coordinate Covalent Bond
Ex.26 The compound which contains both covalent and co-ordinate bond is -
(A) C2H5NC (B) C2H5CN (C) HCN (D) None
Sol. (A) Though all compounds have covalent bond but there is coordination bond also between N and C
in C2H5 NC
O O
H—O— S —O— S —OH
O O
H H H
| | |
H— C = C — C —CN:
|
H
O O O H H H H
H H H H F F
(ii) Hentro intermolecular :- H–bond between molecules of different compounds.
eg. alcohol, water
O — H O — H O — H O — H
R H R H
R H
Other examples–Glucose, Fructose etc, dissolve in water.
(b) Ketone, ether, alkane etc. are insoluble (no H–bond). Dimethyl ether is soluble in water while
diethyl ether is partially soluble, due to bulky ethyl groups H–bonding interupts
(c) Solubility order– CH3OCH3 < CH3OH
Primary amine > secondary amine > tertiary amine
C C
H O O — H O H
p–hydroxy benzaldehyde
It can form H–bond with water molecule so it can dissolvel
(II) Viscosity:
H – bond associates molecules together so viscosity increases
CH2 — OH
CH2 — OH
CH3OH < < CH — OH
CH3 — OH
CH2 — OH
R
|
R — NH2 > R — NH — R > R — N — R (no hydrogen with nitrogen atom)
(d) Boiling points of VA, VIA, VIIA hydrides decreases on decreasing molecular weights.
VA VIA VIIA
NH3 H2O HF b.p. HF > HI > HBr > HCl
PH3 H2S HCl H2O > TeH2 > SeH2 > H2S
AsH3 SeH2 HBr NH3 > SbH3 > AsH3 > PH3
SbH3 TeH2 HI
(e) But sudden increase in boiling point of NH3, H2O and HF is due to H–bonding
H2O > HF > NH3 PH3 < H2S < HCl
Intramolecular H–bonding gives rise to ring formation, so the force of attraction among these molecules
are vander waal force. So M.P. and B.P are low.
(IV) Molecular weight :
Molecular wt. CH3COOH is double of its molecular formula, due to dimer formation occur by H–bonding
O H — O
R—C C—R
O — H O
(V) Physical state:
H2O is liquid while H2S is gas.
Water and Ice:- Both have H–bonding even then density of ice is less than water.
Volume of ice is more because of open cage like crystal structure, from by association of water
molecules with the help of H–bond.
H2O becomes solid due to four hydrogen bond among water molecule are formed in tetrahedral manner.
H H H H
3
1
O 2 O O O
4
H H H H
(VI) Base strength
CH3NH2, (CH3)2 NH, (CH3)3 N form H–bond with water. So less hydrolysis i.e. it gives OH– ions.
–
While (CH3)4 N+ OH (ammonium compound) will give OH– ion in large amount due to no H–bonding.
H H
+ –
CH3 — N H — O CH3 — N —H + OH
H H H
+
CH3
(Ammonium compound.)
CH3 N CH3 NO H–atom bonded directly with N–atom
so no hydrogen bonding occurs.
CH3
Conjugate base
–1/2
O O –1/2
H C H
O O
+ H+
Cl H
O
Cl C C H Chloral hydrate
O
Cl H
(III) Maleic acid (cis) is stronger acid than fumaric acid (trans).
O O
H C H C
–
C OH C O +
H + H
C OH C OH
Stable conjugate base of maleic acid
H C H C
O O
H COOH
C
C
HOOC H
Fumaric acid (No-intramolecular H-bonding)
Examples
based on Hydrogen Bond
Ex.32 Which one of the following does not have intermolecular H-bonding -
(A) H2O (B) o-Nitrophenol (C) HF (D) CH3
Sol. Nitrophenol has intermolecular H bonding as shown below
Hence (2)
(a) This type of attractive forces occurs in case of non polar molecules such as H2, O2, Cl 2, CH4, CO 2
etc.
(b) The existence of weak attractive forces among the nonpolar molecule was first proposed by dutch
scientist J.D. Vander Waal
(c) Vander waal force molecular weight
Atomic weight
Boiling point
+ – +
+
Na HCl
(ii) Dipole Dipole attraction - It is again in between two polar molecules such as HF and HCl
HF HCl(g)
(iii) Ion induced dipole attraction - In this case a neutral molecule is induced by an ion as a dipole as
shown in fig
+ + +
Na+ Cl 2
Before induction after induction
(iv) Dipole - Induced dipole attraction : In this case a neutral molecule is induced as a dipole by
another dipole as shown in fig.
+ +
e.g. HCl Cl 2
(v) Induced dipole - induced dipole attraction or London dispersion force between two non polar molecules
as in Cl2, He etc.
+
+
Cl2 Cl 2
Note: The relative strength of various bonds is as follows
Ionic bond > Covalent bond > Metallic bond > H-bond > Vander waal bond
POINTS TO REMEMBER
(a) Bond energy of a diatomic molecule is enthalpy change to dissociate one mole of the diatomic
gaseous molecule to form the respective gaseous atoms.
(b) Strong metallic bonding is favoured by smaller size of kernel.
(c) Band theory is related with metallic nature
(d) The resonance structure do not have independent existence.
(e) The hydration of ionic compounds involves evolution of heat, weakening of attractive forces and
dissociation into ions
(f) The maximum covalency is equal to the actual number of s-and p-electrons in the outermost shell
(g) Many ionic crystals dissolve in water because water decreases the interionic attraction in the crystal
lattice due to solvation.
(h) Hydrogen bond stabilizes the secondary structure of proteins.
(i) Isoelectronic molecular species have similar molecular orbitals and similar structure according to iso
electric principle
(j) The amount of energy required to break one mole of the bond and separate the bonded atoms in the
gaseous state is known as bond dissociation energy
(k) The average angle between the bonded orbitals is known as bond angle .
(l) Bond length may be defined as the average distance between the centres of nuclei of two bond atoms.
(m) Polymorphism (Allotropy) is a term used when one and the same substance can crystallise in more
than one forms.
(n) In SO2 there is p - p bonding as well as p - d bonding due to overlap of filled p orbitals of oxygen
with the vacant 3d orbitals of sulphur.
(o) H2SO 3 exists in two forms which are always in equilibrium with one another
The unsymmetrical form containing S – H bond explains the reducing character of H2SO 3.
(p) The anion of H2SO 3 i.e. SO 32– has a pyramidal structure with S atom in sp3 hybridization and all the
S – O bonds are of equal bond length (134 pm)
(q) In the gas phase, SO3 is a planar triangular molecule with sulphur atom in sp2 hybridization state
In order to account for the equivalency of all the S – O bonds and short S – O distance of 143 pm,
SO3 may be considered as a resonanchybrid involving p-p S – O bonding along with additional p-
p bonding.
(r) In the solid phase, SO3 polymerizes to puckered rings or the more stable layer structure as shown.
O O O O
S S S S
O O
O O O
O O
O O O
S
O O O O O O
Bonding MOis the result fo the linear ABMO is result of linear combination of AO
combination of AO when their wave when their wave function are substracted
function are added b = A + B b = A + B
It does not have node. It always have a node between two nuclei of
bonded atom.
Charge density increase between two Charge density decrease in between two nuclei,
nuclei resulting attraction between two leads to repulsion between two atoms.
atoms
Energy of BMO is less, hense stable Energy of ABMO is high, hence unstable
Notation of molecular orbitals:
As atomic orbitals are known by letters s, p, d and f depending on their shapes. Similarly for molecular
orbital.
On the basis of Aufbau’s rule - increasing order of energies of various molecular orbitals is-
1s < 1s < 2s < 2s < 2pz < 2px 2py < 2px 2py < 2pz
Energy level diagram for homonuclear diatomic molecules like, O 2, F2, Ne2
For O2 molecule-
'2pz
1
Bond order =2 (8 – 4) = 2
’ ’
2px 2py Bond order O2 = 1/2 [8 – 4] = 2
2p 2p O2+ = 1/2 [8 – 4] = 2.5
Having two unpaired
'2px '2py O–2 = 1/2 [8 – 5] = 1.5
electrons so paramagnetic
O2–
2 = 1/2 [8 – 5] = 1.5
2pz O+2
2 = 3
Increasing energy
Stability order –
+2 +
'2s O2 >O2 > O2> O2– > O22–
Bond length –
2– –
O2 >O2 > O2> O+2 > O+2
2
2s 2s
2s
'1s
1s 1s
s
’ ’
2px 2py
2p 2p
'2pz
2s 2s
2s
'1s
1s 1s
s
1
(ii) Bond length :- (distance between two nuclei) Bond length
Bond order
If Nb Na Molecule exists
Nb Na
Molecule do not exists
Nb Na
(iii) Stability of molecules - stability Bond order of molecule
(iv) Dissociation energy - Bond disssociation energy Bond order
(v) Magnetic property -
(a) When electron in MO are paired – diamagnetic
(b) When electron in MO are unpaired – paramagnetic
Bonding in molecules :-
(I) Hydrogen molecule-
Having two H atoms with one electron each (1s’)
2s
1s' 1s'
(Atomic orbital) H2 (Atomic orbital)
1s
Molecular orbital
Diamagnetic
Bond order = ½ [2 – 2] = 0 (zero)
1s
Bond order zero indicates no linkage
1s 1s
between He atoms. Hence He2 molecule does not exist
Stability (He2) Highly unstable molecule He2 1s
Examples
based on M.O.T.
Ex.34 The bond order of N2¯ anion is -
(A) 1 (B) 2 (C) 2.5 (D) 3
Sol. (C) Out of 15 e¯ in N2¯, 10 are in bonding MO’s and 5e¯ are in the anti bonding MO’s Hence bond order
1
= (10 - 5) = 2.5
2
Ex.36 Which of the molecules B2 and C2 has a higher energy of dissociation into atoms? compare the
magnetic properties of these molecules.
Sol. We draw energy level diagrams showing the formation of B2 and C2 molecules
AO’s MO’s AO’s
B B2 B
AO’s MO’s AO’s
C C2 C
(I) Bond Lengthe (Bond distance) (II) Bond Angle (III) Bond Energy
(I) Bond Lenght :- The average distance between the nucleus of two atoms is known as bond lenght,
normally it is represented in Å. eg. A B
C N C N C N
1.47 Å 1.28 Å 1.15 Å
eg. 2.Bond length of C—O in CO2 is 1.15 Å Resonance occurs in CO2 a follows-
O C O O– — C O+ O+ C — O–
Bond length = 1.15 Å (Between double & triple bond)
1
(d) Hybridisation : - Bond length s character
sp3 2
sp 1.51 Å
sp3 sp 1.47 Å
2 2
sp sp 1.46 Å
2
sp sp 1.42 Å
sp sp 1.37 Å
(II) Bond Angle :- The angle between any two adjacent bond is known as bond angle. It is represented
in degree (°), min (‘) and second (‘’)
Factors affecting the bond angle-
(a) Number of bond : Bond angle Number of bonds (Bond order)
109° 120° 180°
C C C C C C
(b) Hybridisation :-
Case 1
When hybridisation is same, bonded atoms are same, central atom and lone pair are different.
1
Then bond angle
No. of lone pair
•• ••
Example :- CH4 N H3 H 2O
••
Hybridisation sp 3 sp 3 sp 3
Bond angle 109 > 107 > 105
No 1.p. one 1.p. two 1.p.
Case-II
When hybridisation is same, bonded atoms are same lone pair is same but central atom is different.
Then bond angle electrongativity of central atom
•• •• ••
Example:- NH3 P H3 As H3
Bond angle 107° 93° 91°
– Eletronegativity decreasing
– Bond angle will decrease
Case-III
When hybridisation is same, lone pair are same, Central atom is same, bonded atoms are different.
sp 3 OF2 103 – 105° Electronegativity
sp 3 Cl2O 109 – 111° of bonded atom is
sp 3 Br2O 116 – 118° decreasing
1
Here bond angle size of side atom
electrongativity of bonded atom
(III) Bond Energy (BE) :- Bond energy may be difined as-
(a) Bond formation energy:- Energy released when any bond is formed is known as bond formation
energy or bond energy.
(b) Bond dissociation energy :- Energy required to dissociate any bond is known as bond dissociation
energy.
Calculation of released energy is more diffcult than the dissociation energy therefore dissociation
energy of bond is calculated and is assumed as bond energy or bond formation energy.
Case-I In diatomic molecule :
Bond energy = bond dissociation energy
eg :- N2 > O 2 > H2 > F 2
Case-II For polyatomic molecule :-
Bond energy Bond dissociation energy (D)
H
|
eg;- H C H Bond energy = per CH bond is 99.5 K. Cal/mole
|
H
Theoritical values of bond dissociation energy (D) of individual CH bonds CH4 are given below-
D (CH3H) = 102 K Cal/mole
D (CH2H) = 105 K Cal/mole
D (CHH) = 108 K Cal/mole
D (CH) = 83 K Cal/mole
398
Hence bond energy E per CH bond in methane = 99.5 K Cal/mole.
4
×× ×× ×× ×× ×× ××
×
C C > N N > O O > ×F ×F×××
×× ×× ××
Size of F and O atoms small so their bond energy should be high (small atomic radius) but it is actually
less due to lone pair of electrons present on F and O atoms, which repells each other in FF and
OO type of bonds.
15. RESONANCE
(I) The concept of resonance was introduced by heisen berg (1920) , and later developed by pauling and
ingold, to explain the properties of certain molecules,
(II) It has been found that the observed properties of certain compounds cannot be satisfactorily explained
by writing a single lewis structure. The molecule is then supposed to have many structures, each of
which can explain most of the properties of the molecule but none can explain all the properties of the
molecules. The actual structure is in between of all these contributing structures and is called resonane
hybrid and the different individual structures are called resonating structures or canonical forms. This
phenomeni is called resonance.
(III) Let us discuss resonance in ozone, according to its resonance structure it should have one single bond
(OO = 1.48Å) but experiments show that both the bonds are same which can be proved by its
resonance hybrid as shown below.
O O O
O O O O O O
Resonance hybrid
To calculate bond order in the polyatomic molecule or ion use following formula :
O¯
O P O¯ 5
PO Bond order 1.25
4
O¯
O
O P O¯ 7
ClO Bond order 1.75
4
O¯
(a) The constituent particles of metallic solids are metal atoms which are held together by metallic
bond.
(b) In order to explain the nature of metallic bond Lorentz proposed a simple theory known as electron
gas model or electron sea model.
(c) A metal atom is supposed to consist of two parts, valence electrons and the remaining part (the
nucleus and the inner shells) called kernel.
(d) The kernels of metal atoms occupy the lattice sites while the space between the kernel is occupied
by valence electrons.
(e) Due to small ionisation energy the valence electrons of metal atoms are not held by the nucleus
firmly. Therefore, the electrons leave the field of influence of one kernel and come under the
influence of another kernel. Thus the electrons are not localised but are mobile.
(f) The simultaneous attraction between the kernels and the mobile electrons which hold the kernel
together is known as metallic bond.
11.1 Properties of metals and their explanation by electron sea model :
1. Metallic lusture :
(a) It is due to presence of delocalised mobile electrons
(b) These loosely bond electrons vibrate due to energy photon of incident light and radiates energy
immediately
2. Electrical conductivity :
(a) It is due to mobile electrons.
(b) These electrons flow equaly in all direction.
(c) While applying a potential difference across a metal, there will be a directed flow of electrons
towards the positive electrode.
(d) The directed flow of electrons carries the electric current from one point to another and therefore,
the metals are known to be good conductors.
3. Thermal conductivity :
(a) It can also be explained on the basis of electron gas model.
(b) While heating a metal kinetic energy of electron increases and propagates through collisons.
••
(C) (D)
• • Cl
Q.19 Enol form of acetone contains the following: Cl Cl
(A) 9–bond, I -bond and two lone pair of
5s 5p
electrons
Sol.(D) Sn[Z = 50], [Kr]
(B) 8–bond, 2 -bond and two lone pair of
electrons
(C) 10–bond, I -bond and one lone pair of sp2 – hybridisation :
electrons
(D) 9–bond, 2 -bond and one lone pair of Q.23 In which case hydrogen bond will not be
electrons observed
Sol.(A) Enol form of acetone is
(A) H3O2 (B) H2O
CH2=C–CH3 [9 and 1 bond and 2p]
| (C) H5O2 (D) H3O +
••
OH
••
Sol.(D) H 3O 2 species H bonding in H2O
Q.20 The decreasing order of solubility of silver
halide is
H H
(A) Agl > AgBr > AgCl > AgF
(A) O H O H (B) O H O H
(B) AgF > AgCl > AgBr > Agl
H
(C) AgCl > AgF > AgBr > Agl
(D) AgBr > AgF > Agl > AgCl
H5 O2 (H-bonding) H3O +(no H-bonding)
Sol.(B) Agl has maximum covalent character [ I¯
is a large anion], while AgF has minimum + +
H H H
covalent character, Therefore, it has more (C) O H O (D) O H
H H H
solubility