Chemical Bonding & Molecular Structure - Key Notes

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Chemistry : Key Notes
Topics : Chemical Bonding & Molecular Structure
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1. Atoms combine with one another in a number of ways such as by transfer of electrons
(ionic bond) or by sharing of electrons (covalent bond) to form a large number of
molecules. Nature of bond formed between two atoms depends upon electropositive and
electronegative character (BEST
of bonded atoms.
ONLINE STUDY SYSTEM)
(i) For Bond formation electronegativity differences and size of atoms is considered. If
A and B are there and electronegativity of A and B are X A and XB, Then
XA – XB = 0 Pure covalent
XA – XB > 0 < 1.7 Polar covalent
XA – XB = 1.7 50% Ionic 50% Covalent
XA – XB >> 1.7 Mainly Ionic
(ii) For Ionic Bond:
(a) large cation and small anion.
(b) Ionic bonds are non directional
Note Ionic bond is non-directional in nature while covalent bonds are directional
in nature.
2. Ionic compounds have high melting and boiling points and these are soluble in polar
solvents such as water. For dissolution of ionic solid in water, hydration energy must be
higher than lattice energy. PbSO4, BaSO4, CaCO3, PbS, AgBr, AgCl, AgI, CaF2 etc are
almost insoluble in water as their hydration energy is less than lattice energy.
Higher the lattice energy greater will be the case of forming an ionic compound. The
amount of energy released when free ions combine together to form one mole of a crystal
is called lattice energy (U)
K
lattice energy =
+ −
; r + + r − is internuclear distance.
r +r
3. No bond is 100% ionic in nature. It has some percentage of covalent character.

According to Fajan’s rule, the magnitude of covalent character in the ionic bond depends
upon the extent of polarisation caused by cation. Smaller the size of cation, large is its
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its polarisability.
4. Covalent molecules have lower melting and boiling points due to relatively weaker forces
of attraction. But giant covalent molecules such as silica, diamond etc. are very hard and
have high melting and boiling points. Covalent compounds are insulators of electricity
but graphite conducts electricity even in solid state due to presence of mobile p-electrons.
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Limitation of Octet Rule
1. In many molecules octet rule is not satisfied for all atoms
For Examples, BCI3, BeF2.
2. In some molecule central atom has more than six electrons in valence shell.
For Examples, SF6, IF7, PCl5 etc.
3. Octet rule is mainly on inertness of noble gases but Xe forms the compounds.
Factors Affecting Bond Length
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1. The bond length increases with increase in the size of the atoms. For example, bond
length of H—X are in the order, HI > HBr > HCl > HF.
2. The bond length decreases with the
(BEST multiplicity
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the bond. Thus, bond length of carbon
bonds are in the order, C ≡ C < C = C < C — C.
3. As an s-orbitals is smaller in size, greater the s-character shorter is the hybrid orbital and
hence shorter is the bond length.
4. Polar bond length is usually smaller than the theoretical non-polar bond length.
Bond Energy or Bond Enthalpy Factor Affecting Bond Energy

1. Greater is the size of the atom, greater is the bond length and less is the bond dissociation
energy i.e., less is the bond strength.
2. For the bond between the two similar atoms, greater is the multiplicity of the bond
greater is the bond dissociation energy.
3. Greater the number of lone pair of electrons presented on the bonded atoms, greater is
the repulsion between the atoms and hence less is bond dissociation energy. Repulsion
is as Ip – Ip – > Ip – bp > bp – bp
Example:
4. The bond energy increases as the hybrid orbitals have greater amount of s-orbital
contribution.
Thus, bond energy decreases in the following order, sp > sp2 > sp3
5. For a poly atomic molecule containing bonds of same kind, the bond energy required
to break each bond may not be same. In such a case, the average of energy required to
break to all bonds is calculated and it is taken as average bond enthalpy.
Note Electronegativity order is sp > sp2 > sp3
Bond Angle
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Factor Affecting Bond Angle
1. Repulsion between atoms or group attached to the central atom may increase or decrease
the bond angle.
2. In hybridisation as the s-character of the s hybrid bond increases, the bond angle increases.
3. By increasing lone pair of electrons, bond angle decreases approximately by 2.5%.
4. If the electronegativity of the central atom decreases, bond angle decreases.
5. All single covalent bonds are sigma (s) bonds while multiple bonds contain one sigma
bond only, the other bonds are pi (p) bond, More is the number of bonds between
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two atoms, the shorter is the bond length. Bond length decreases with the increase in
s-character (sp3 > sp2 > sp).
number
6. Formal charge = (Total number of valence electrons in the free atom) – (Total
(BEST
1 ONLINE STUDY SYSTEM)
of lone pair electrons) + (Total number of bond pair electrons).
2
Percentage ionic character of a covalent bond (depending upon electron-egativity difference)
= 16(XA–XB) + 3.5 (XA–XB)2
where XA and XB are electronegativities of atom A and B respectively.
7. Percentage of ionic character
experimental value of dipole moment
Dipole moment = ×100
Theoretical value of dipole momeent
Dipole moment is treated as vector quantity. Non-polar diatomic molecules have a zero
dipole moment while polar diatomic molecules possess dipole moments.
8. The Molecular Orbital Theory describes bonding in terms of the combination and
arrangement of atomic orbitals to form molecular orbitals.
 The number of molecular orbitals are always equal to the number of atomic orbitals
from which they are formed.
 Bonding molecular orbitals are lower in energy than the individual atomic orbitals
while anti -bonding molecular orbitals have more energy than the individual atomic
orbitals.
9. Bond Order (B.O.) where Nb and Na are number of electrons in bonding and the
antibonding orbitals respectively.
 A positive bond order means a stable molecule while a negative or zero bond order
means an unstable molecule.
1
 Bond order ∝
Bond length
 Bond order ∝ Bond dissociation energy and stability.
 Isoelectronic species having same number of electrons have same bond order.
Bond Order is Calculated as
Valence electron sum Bond order
10 1
11 1.5
12 2
13 2.5
14 3
15 2.5
16 2
17 1.5
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18 1
Example : In O2 valance electron sum = 8 + 8 = 16, So from table bond order = 2. If CO
then 6 + 8 = 14 (BEST
B.O. =ONLINE
3 STUDY SYSTEM)
 Below’ 14’ and above ‘14’ it is symmetric.
 O2, O+2 , O2– paramagnetic O2– –, O2++ are diamagnetic
No.of Resonating bonds

For resonating structure, B.O. =
No.of Resonating structure
4
Example : CO3– – B.O =
3
No. of Resonating structures = No. of surrounding atoms
Example: CO3– – ‘3’, SO4– – ‘4’, ClO4–, ‘4’ resonating structure
Bond order of benzene = 3/2
Paramagnetic and Diamagnetic Character

For paramagnetic electrons sum should be odd except 16 and 10 electrons.
Example : O2 & B2 are paramagnetic.
For diamagnetic electron sum should be even

C2 N2 O++
2
Diamagnetic
12 14 14
O+2 O2– Paramagnetic
15 17
Hybridization
H
|
So CH 4 , H  C  H 4σ, sp3
|
H
H Hybridisation Spatial arrangement
2 sp Linear
3 sp 2
Trigonal planar
4 sp3 Tetrahedral
4 dsp2 Square planar
5 sp d or dsp
3 3
Trigonal bipyramidal
6 sp3d2 or d2sp3sp3d2 octahedral
7 pentagonal bipyramidal
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10. Hybrid orbitals follow Hund’s rule and Pauli’s principle.
In dsp3 or sp3d hybridisation the d-orbital involved are dz2. In sp3d2 or d2sp3 hybridisation
the d-orbitals involved are dz2 and dx2 – dy2 in sp3d3, dxy, dyz, dzx.
Points of Difference
Hydrogen Bonding : For hydrogen bonding, the molecule must posses a higher electronegative
atom such as F, O or N, directly linked to hydrogen atom.
 Intermolecular H-bonding (such as in NH3, HF, H2O etc.) increases the boiling point of
the compound and also its solubility in water.
 Intramolecular H-bonding (such as in o-chlorophenol, o-nitrophenol, o-hydroxy benzoic
acid etc.) decreases the boiling point of the compound and also its solubility in water.
 Order of strength of H-bonding;
H ..... F > H ..... O > H ..... N
10 Kcal, 7KCal , 5KCal
 Water contains four hydrogen bonds
The forces between molecules are intermolecular forces. These forces originate from the different
types of interactions such as dipole-dipole interactions, ion-dipole interactions, ion-induced
dipole interactions and dispersion forces.
 Metals are good conductors of electricity due to presence of mobile electrons.
 Electrical conductivity of metals decreases with increases in temperature.
 Bright lustre of metals is due to oscillating electrons.
 Malleability and ductility of metals is due to the non-directional nature of metallic bond
and mobile nature of valence electrons.
 In metals, the valence bond may be half-filled or there may be overlapping between the
valence band and conduction band. FreeContact
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electrons present metals easily move into
vacant bands.
 In semiconductors, the energy gap is very small. Electrical conductivity of semiconductors
increases as the temperature increases because some electrons move from valence band
to conduction band.

Important Hybridization Schemes in
3d-Transition Metal Complexes
Co-ordina-
tion no. of
Type of hybridization Geometry of the Examples of
the central
undergone complex complexes
metal atom
/ ion
sp Linear or diag-
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2
(4s, 4px) onal
Trigonal planar
sp (BEST ONLINE STUDY SYSTEM)
2
3 or equilateral
(4s, 4px, 4py)
triangular
dsp2 [Ni(CN)4]2–
4 Square planar
(3dx2 – y2, 4s, 4px, 4py) [PdCl4]2–
sp2d [Cu(NH3)4]2+
4 Square planar
(4s, 4px, 4py, 4dx2 – y2) [Pt(NH3)4]2+ etc.
[NiCl4]2–
sp3
4 Tetrahedral [Cu(CN)4]2–
(4s, 4px, 4py, 4pz)
Ni(CO2) etc.
Fe(CO)5
dsp3 Trigonal
5 [Cu(Cl5)]3–
(3dz2, 4s, 4px, 4py, 4pz) bipyramidal
[Ni2+ (triars) Br2]°
dsp3
Square [Co2+(triars)I2]°
5 (3dx2 – y2, 3dz2, 4s, 4px,
pyramidal [Ni(CN)6]3– etc.
4py, 4pz)
d2sp3
Inner-orbital [Ti(H2O)6]3+
6 (3dx2 – y2, 3dz2, 4s, 4px,
octahedral [Fe(CN)6]3– etc.
4py, 4pz)
sp3d2
Outer-orbital [Fe(NO)(H2O)5]2+
6 (4s, 4px, 4py, 4pz, 3dx2 –
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] etc. 6
3–
y2
, 3dz2)

Hybridisation and Structure of
Molecules Having Lone Pair
Hybridisa- Bond- Lone Bond
Shape Examples
tion ed pair pair angle
Bent
SO2
molecule
sp2 2 1 119° SnCl2
or
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PbCl2
V-shaped
NF3, PF3, SO32–

XeO3, ClO32–, P(CH3)3
sp3 3 1 107° Pyramidal N(CH3)3, AsCl3, BiCl3
SbCl3, NH3, PCl3
PH3 (Bond angle 94°)
H2O, H2S
(Bond angle 92°) SCl2,
sp3 2 2 104.5° V-shaped OF2, Cl2O, H2Se
NH2, ClOF
CH3OCH3, ClO2–
SF4, SCl4
120° Trigonal TeBr4
sp3d 3 2
90° pyramidal XeO2F2
TeCl4
ClF3, XeOF2
sp3d 3 2 90° T-shaped IF2, BrF3
ICl3, IBr3
XeF2
I3
sp3d 2 3 180° Linear
ICl2
KrF2

Hybridisation in Molecules without Lone Pair
Spatial
Hybridisa- Bond
arrange- Examples
tion angle
ment
BeH2, BeF2, BeCl2, HgCl2, C2H2, HCN
sp Linear 180° CO2, CS2, N2O, Hg2Cl2
[Ag(CN)2], MgCl2
sp2
Trigonal
planar
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120°
BF3, BCl3, C2H4, H— —H, Cl— —Cl,
COSTUDY
(BEST ONLINE 3
2–
, NO3–SYSTEM)
, SO3, H3, (CH3)3, , BH3,
AlCl3
CH4, SiH4, SnCl4, PbCl4, TlBr4, CCl4,

SiF4, [BeF4]2–, [BF4–], NH4+, [AlCl4]–,
[PH4]+, [PF4]+, [H2PO2]–, [HPO3]2–,
sp3 Tetrahedral 109°28′
[PO4]3–, POCl, SO42–, ClO4–, Ni(CO)4,
[Zn(CN)4]2–, [AsO4]3–, [SeO4]2–, [IO4]2–,
XeO4, MnO4–, CrO42–, SiCl4.
Square pla- [Cu(NH3)4]2+, [PtCl4]2–, [Ni(CN)4]2–,

dsp2 90°
nar [PdCl4]2–, [Pt(NH3)4]2–, [AuCl4]–
Trigonal 120° PCl5, PF5, AsF5, SbCl5, XeO3F2,

sp3d or dsp3
bipyramidal and 90° [Fe(CO)5]
SF6, [PF6], [BiCl6]–, [PCl6]–, [AsF6]–,

[SeF6], MoF6, [SnCl6]2–, [SbCl6]–, TeF6,
sp3d2 or d2sp3 Octahedral 90° WCl6, UF6, XeO2F4. All six coordi-
nated complexes are octahedral e.g.,
[Co(NH3)6]3+.
Pentagonal
sp3d3 72° IF7, [ZrF7]3–, [UF7]3–, [UO2F5]3–, SF7.t
bipyramidal


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BOSS

(BEST ONLINE STUDY SYSTEM)

3. No bond is 100% ionic in nature. It has some percentage of covalent character.

Factors Affecting Bond Length

Bond Energy or Bond Enthalpy Factor Affecting Bond Energy

Note Electronegativity order is sp > sp2 > sp3

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 O2, O+2 , O2– paramagnetic O2– –, O2++ are diamagnetic

No.of Resonating bonds

Paramagnetic and Diamagnetic Character

For diamagnetic electron sum should be even

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NF3, PF3, SO32–

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CH4, SiH4, SnCl4, PbCl4, TlBr4, CCl4,

Square pla- [Cu(NH3)4]2+, [PtCl4]2–, [Ni(CN)4]2–,

Trigonal 120° PCl5, PF5, AsF5, SbCl5, XeO3F2,

SF6, [PF6], [BiCl6]–, [PCl6]–, [AsF6]–,

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