Chemical bonding and molecular structure

21 May 2024 11:07

Chemical Bond: It is the force of attraction between two atoms which hold them together in a
compound or molecule.
Ex: H2, CH4, SF6, etc.

Why chemical bond formation takes place?

To achieve stability

Types of Bond
1. Covalent Bond
Formed by sharing of electron.

Bond pair(b.p.): Shared pair of electron(under the influence of both nuclei)(1 b.p. has 2 electrons)
Lone pair(l.p.): unshared pair of electron(under the influence of only one nuclei)(1 l.p. has 2 electrons)

Covalency: it is defined as the number of bonds formed by and atom in a molecule.

Ex: H2, CH4, SF6, etc.
2, 4, 6

Maximum covalency of 2nd period element is 4.

2. Ionic Bond
Formed by transfer of electron.

Bond formation is favorable when:

1. Low ionization energy.

2. High electron gain enthalpy.
3. Lattice energy: It is defined as amount of energy released when gaseous cation & anions are
brought from infinity to their lattice site in the crystal lattice to form one mole of an ionic
compound.
Lattice energy is directly proportional to size and inversely proportional to distance between atom.
Ionic bond is favourable when there is high lattice energy.

Hydration energy: It is the energy released when an isolated gaseous ion gets hydrated. Unit: KJ/mol

Greater the hydration, greater the hydrated radii.

Ionic radii in

a. In gaseous phase: Li+ < Na+ < K+ < Rb+ < Cs+

Electrovalency: It is defined as the number of electron gain/lost by an atom in ionic bond formation.

Na, Cl has 1 electrovalency each for compound NaCl.

Born Haber Cycle

Used to calculate the lattice energy of an ionic solid , which is the energy required to separate the solid
into its constituent gaseous ion

3. Coordinate/Dative/Coordinate covalent Bond

In this type of bond, a donor atom donate his electron pair to some other acceptor atom, in this, The
electron pair is shared between 2 atoms.

Here, only the process of making bond is different, However after complete bonding, there is no
difference from a normal covalent bond.
A(donor): > B(acceptor)

All N-H bonds are equivalent.

Formal Charge: It is the difference between the number of valence electron in an isolated atom and the
number of electron assigned to that atom in Lewis structure.

Formal Charge: (Number of valence electron) - (number of non bonding electron) - ½ (number of
bonding electron.

4. Metallic Bond:
Free electron model/Electron sea model

The fixed positive cation in this image is known as kernels.

• According to electron sea model, metals behave as if it is an assembly of positive ions (kernels)
immersed in a sea of whole electron.
• The force that binds a metal atom to a number of electrons within its sphere of influence is
known as metallic bond.

This model can explain:

○ High electrical conductivity
○ High thermal conductivity
○ Malleability
○ Ductility
○ Bright metallic lustre.

In lewis dot structure, number of dots around the atom represent the number of valence electrons of
that atom.

Bonding Theories
1. Lewis Octet Theory
Octet theory: Every atom has a tendency to attain noble gas electronic configuration or to have 8
valence electrons.

Noble gas: General valence shell electron configuration: ns2np6(octet) (except He).

Limitation:
▪ Incomplete octet ( Hypovalent species)
Ex: BCl3, BF3, AlCl3
▪ Expanded Octet(Hypervalent species)
Ex: SF6, PCl5
▪ It gives no idea about the molecular shape of the compound:
▪ Odd electron species
Ex: NO, NO2
▪ Xe: a noble gas – but still it forms compound with flourine and oxygen.
Ex: XeF6, XeF4, XeO3, XeOF4 etc.

In general Follow below rules to choose Central atom:

• Least electronegative polyvalent element becomes central atom.

• If element belongs to same group then the atom which has higher atomic number becomes
central atom.
• If atom belongs to different groups, atom which is left most becomes central atom.
• H will bond to more electronegative atom in a molecule.

2. Valence Bond theory

Attractive forces(long range force)
N1- e1, n1-e2, n2-e1, n2-e2

Repulsive Interaction(Short range force)

N1-n2, e1-e2

Note:
Attractive force: stability: potential energy decrease
Repulsive force: destabilize: potential energy increase

• On going from top to bottom, tendency to form multiple bond decreases.

At, ro = bond length, fattr = frepulsion

At, r>ro, fattr>frepulsion
At, r<ro, fattr<frepulsion

Assumption
• Atoms retain their individuality.
• Bond is formed when valence orbitals of two atoms overlap(inner orbitals would be
undisturbed)
• Overlapping can be of two types:
○ 2 half filled orbitals (covalent bond)
○ One fully filled orbital + 1 vacant orbital ( coordinate covalent bond)
• Two completely filled orbitals will never overlap

Orbital overlap concept

Zero overlap( out of phase due to different orientation direction of approach).

Positive overlap: involves overlap of the lobes of same sign.

Result in bond formation
Leads to attractive interaction.

Negative overlap: involves overlap of the lobes of opposite sign.

Leads to repulsive interaction.

Zero overlap: No interaction.

Types of Overlapping
a. Head on overlapping(end to end overlapping)
Result in sigma bond(σ)
Internuclear axis: Axis along which head on overlapping occurs.

By default z-axis is taken as internuclear axis.

If, Z-axis (I.N.A): Pz-Pz overlap: σ bond
And, Px-Px overlap: π bond
Py-Py overlap: π bond
 b. Sideways Overlapping(or lateral overlapping)
• Side to side overlap
• Result in pi-bond (π ) formation.
• Π-bons formation is followed by σ-bond formation.

Strength of sigma bond is greater than that of pi bond because strength of bond is directly
proportional to effective overlapping and indirectly proportional to bond length.

Comparing Bond strength

• C-C < C=C< C≡C

• , σS-S < σS-P < σP-P ( Reasons: directional nature of p orbital, s-orbital is symmetrical.
Electron density is equally distributed in all the direction).

• As n increases, effective overlapping decreases.

• S-orbital cannot form π bond.

Concept of Hybridisation
It is the process of intermixing of the orbitals of slightly different energies so as to redistribute their
energies, resulting in the formation of new set of orbitals of equivalent energies and shape.

Lets took an example of methane, to make bond, it need to get in excited state,
According to this, we should observe 2 bond lengths in CH4 but, all bond length are same

To explain this, we introduce a hypothetical concept of hybridisation in which all 4 bond length are
equal.

In CH4, One 2s + Three 2p gives 4 new sp3 hybrid orbitals

It has tetrahedral shape

Important points:
• It is an intermixing of orbitals to form identical orbitals (in terms of shape and energy)
known as hybrid orbitals.
• It is a theoretical concept.
• Number of hybrid orbitals = number of atomic orbitals participating in hybridisation.
• Ony those orbitals can form hybrid orbitals which don’t have more energy difference between
them.
• Hybrid orbitals will always form sigma bond(due to s character in it).
• Hybrid orbitals are more directional than unhybridized orbitals. They are more effective in bond
formation as compared to pure AO.s
• The energy and shape of Hybrid orbitals depend upon the % character in them.
• %s character in hybrid orbital is directly proportional to thickness of lobe.
• Hybrid orbitals: They tend to rearrange themselves in such a way that there will be minimum
repulsion among them, and that is why they have fixed geometry and fixed bond angles.
• Promotion of electron is not essential condition prior to hybridization.
• It is not necessary that only half filled orbitals participate in hybridization.

Types Of Hrbridisation

Prediction of State of Hybridisation

Number of A.O.S = Number of H.O.S = Steric number = Number of sigma bond + number of Lone
pair
 Steric number = ½ (V(number of valence electron) + M(Monovalent atom/group) - C(cationic
charge) + A(Anionic charge).

Ex:
• XeF6 = 7 = sp3d3
• SO3 = 3 = sp2
• XeF4 = 6 = sp3d2
• XeF2 = 5 = sp3d
• CH3+ = 3 = sp2
• CH3- = 4 = sp3
• SOF4 = 5 = sp3d
• XeOF4 = 6 = sp3d2
• XeO3 = 4 = sp3
• SO2 = 3 = sp2
• I3- = 5 = sp3d
• ClF3 = 5 = sp3d

Valence shell electron pair repulsion(VSPER) theory

According to this theory, shape of compound depends upon number and types of electron pair around
central atom.

Bond Pair: pair of electrons present under influence of 2 atoms.

Lone Pair: pair of electrons localised on one atom.

l.p-l.p>l.p-b.p>b.p-b.p (sequence of repulsion)

Triple bond> double bond> Single Bond

○ According to Lewis, electron pair acceptor are acid, and electron pair donor is base.

Bond Parameters:
1. Bond angle:
Defined as angle between the orbitals containing bonding electron pair around central atom in a
molecule/ion.
For ex: in NH3- : bond angle is approximately 107 degree.

Bond angle comparison:

CH4 > NH3 >H2O (Reason: angle is smaller due to the introduction of lone pair)

NH3 >PH3 > AsH3 > SbH3 > BiH3 (Reason: If electronegativity of central atom decreases, bond angle
also decreases.

OF2 < OH2 < OCl2 (Reason: If electronegativity of surrounding atom decreases, Bond angle increases.

If surrounding atoms are bulky, then steric repulsion increases and hence bond angle also increases.
Ex: H2O < H3COH < H3COH3C

Bond angle is directly proportional to percentage s-character

2. Bond length:
It is defined as equilibrium distance between the nuclei of two bonded atoms in a molecule.

General trend
Bond length is directly proportional to size of atom
Bond length comparison: single>double>triple

Bond order = number of bonds.

3. Bond enthalpy:
Amount of energy required to break one mole of bonds of a particular type between two atoms in
gaseous state. Unit: KJ/mol , bond breaking is endothermic process.

Bond enthalpy comparison: triple>double>single

BENT'S RULE STATEMENT:

• More electronegative substituent prefers hybrid orbitals having less s character ( small bond
angle ) and vice versa.
• Hybrid orbitals of central atom connected to more electronegative surround atom has less s-
character.
• Hybrid orbitals of central atom containing multiple bond/lone pair has more s-character;
Ex: IN CCl2H2 , H will have more s-character as compared to Cl.

Applications of Bent's Rule:

In TBP: eqv; s + px + py and in ax: Pz + dz2
More electronegative element in TBP will be placed at axial position

In TBP geometry, axial bond lengths are longer than the equatorial bond length. (always applicable
when all surrounding atoms are same).

Drago's Rule
If element has Principal quantum number greater than or equal to 3 and it has minimum 1 l.p. ,
electronegativity of surrounding atom should be less than or equal to 2.1 and last s-orbital does not
participate in hybridization, then it is Drago's compound.

Theta is nearly equal to 90 degree.

Compare basic strength of Group 15 element.

NH3 > PH3 > AsH3 > SbH3 > BiH3 (Reason: In NH3 . L.p. Is present in sp3 hybrid orbital whereas, in
other members l.p. is present in almost 100 s-orbital, greater the s-character, difficult it is to donate the
electron pair and hence, less basic strength)

Hybridization in solid state:

Polarity in Covalent Compound

In a covalent bond due to electronegativity difference, the electron cloud shared between the 2 nuclei
shift to nuclei which has more electronegativity

Partial ionic character can be estimated by electronegativity difference, or dipole moment of

compound.

1. Electronegativity difference & %ionic character

2. Dipole moment of compound & %ionic character.

• It is a vector quantity.
• If dipole moment is zero, than it is non-polar molecule.
• If dipole moment is non-zero, than it is polar molecule.
• There is no compulsion that if there are polar bonds, the molecule will always be polar.

For a regular geometry molecule, if surrounding all atoms have asme electronegativity, then dipole
moment is zero.
Ionic character of a bond in a molecule
% ionic character = observed dipole moment * 100 / theoretical dipole moment.

Dipole moment = q.d

Q=e= 4.8 * 10-10 esu

Covalent character in Ionic compound

• There is distortion/deformation or polarization of anion(anion doesn't remain spherical but gets
distorted)
• Due to this polarization, electron density is concentrated between 2 nuclei resulting in covalent
character.
• No compound is 100% ionic.
• Polarization: Polarization of an ionic compound is a result of distortion of anion by a cation

Fajan's Rule:
Covalent character is directly proportional to extent of polarization

For cations: Polarizing power

For anions: Polarize ability

Polarizing power is directly proportional to charge of cation and inversely proportional to size of
cation.
Polarize ability is directly proportional to both charge and size of anion.

Cation with 18 electron in outermost shell that is pseudo noble gas configuration will have more
polarizing power than that of a cation with 8 electron in outermost shell ( noble gas configuration).

Application:

• Melting point is inversely proportional to covalent character

• Solubility in H2O is inversely proportional to covalent character.

Molecular orbital Theory (MOT)

By VBT theory, oxygen gas is diamagnetic species but by experiment results oxygen gas is a
paramagnetic in nature

• To tell para or di molecule.

• Color of molecule.

[Link] = Atomic orbital

[Link] = Molecular orbital
B.M.O = Bonding MO
A.B.M.O = Antibonding MO

Postulate
1. Atoms combine to form molecules.
2. In molecules, [Link] combine to form [Link] ( Total [Link] = Total [Link])
3. [Link] are formed from [Link] by LCAO ( Linear combination of atomic orbitals) method.

Two atomic orbital make two molecular orbital which in turn make one A.B.M.O AND ONE B.M.O

• Atomic orbitals, Hybrid orbitals are monocentric while molecular orbitals are polycentric.
• B.M.O: formed by addition of lobes of Atomic orbitals or symmetrical mixing of electron waves.
• A.B.M.O: Formed by subtraction of lobes of A.O or unsymmetrical mixing of electron waves.
• M.O follow the electronic configuration.

Condition for M.O formation

• Comparable energies between combining orbitals.
• Combining orbitals must have proper symmetry.

Molecular Orbital Nodal Plane: nodal plane passers from both the nuclei or none the nuclei.

BMO: electron density is maximize and thus, stabilize the molecule.

ABMO: electron density is minimize thus, destabilize the molecule.

Energy level diagram

Reason for change in orbital is sp mixing (energy gap is small and symmetry match)

Bond order = ½ (Nb[number of electron in BMO] - Na[Number of electron in ABMO])

• Bond order = 0 , Molecule doesn't exist.

• Greater the bond order, greater the stability.
• Removal of electron from BMO, bond order decreases and vice versa.
• B.O is directly proportional to B.S, B.E and inversely proportional to B.L.
• If Nb > Na , then molecule is stable.
• If Nb = Na , then molecule is unstable.

Ex: Bond length comparison: H2- > H2+ > H2 (Reason: In H2- , last electron enters in ABMO so more
repulsion)

Concept of Homo & Lumo:

Homo: Highest occupied MO

Lumo: Lowest unoccupied MO.

Ex: In H2, Homo is sigma 1s, and lumo is sigma star 1s.
Find the above parameters for NO and CN-.

Concept of gerade(g) & ungerade(u) (applied only to homonuclear

molecules)

If orbital has a center of symmetry I.e. if along passing through the center and at equal distance from
it, orbital signs are same, then designation is gerade. If opposite sign, then it's designation is
ungerade.

I. Sigma BMO : gerade

II. Sigma ABMO : ungerade
III. Pi BMO : ungerade
IV. Pi ABMO : gerade

Resonance
When a compound has same molecular formula but different structures differ with respect to
electrons only.
These structures are known as resonating structures or canonical structures. None of these
structures can explain all the properties of that compound. This phenomenon is known as
Resonance.
 Bond order in a compound showing resonating structure = total number of bonds/total number
of resonating structures.

Ex: in CO3-2 = 4/3

Resonance Hybrid
It is the hypothetical mixture of all contributing or resonating structure.

More the number of resonating structure, more the stable compound.

Conditions for writing a resonating structure.

I. Maximum valency of an atom should not be violated.

II. Sum of number of pi-bond and lone pair of electrons in every structure must be same.

In general neutral structure are more stable than charge structure.

Structure with more number of bonds>structure3 with less number of bonds (stability)

Hydrogen Bonding
• Special type of Keesom interaction.
• Exists between the molecules containing hydrogen atom linked to (F, N or O).

Types of Hydrogen Bonding

I. Intermolecular H-bonding: It is a type of H-Bonding between 2 similar or dissimilar molecule.

Ex: H2O, HF, etc.

2. Intramolecular H-bonding: It is a type of H-bonding within the molecule.

Ex: Salicyladehyde

Applications of hydrogen bonding

1. State: H-bonding may affect the state of system.
Ex: HF & H2O are liquid at room temperature whereas HCl & H2S are gas at room temperature.

Reason: Intermolecular H-bonding in HF & H2O.

2. Solubility: Those covalent molecules are soluble in H2O which have tendency to form internuclear
H-bonding with H2O molecules.

• Alcohols, NH3 , 1 degree amine, secondary amine etc are soluble.

Reason: Can form H-bond with H2O.

Alkyl halides and 3 degree amine are almost insoluble(Cannot form H-bonding with H2O)
3. Boiling point: directly proportional to intermolecular H-bonding.

NH3 > PH3 (Boiling point)

Para-nitrophenol > ortho-nitrophenol (boiling point)
Para-nitrophenol < ortho-nitrophenol (volatility: tendency to become gas faster)

4. Density of ice is less than density of water because in Ice, hydrogen bonding gives rise to cage
like structure which increases its volume. H-O-H molecule is linked tetrahedrally to four other H-
 O-H molecule.

5. HF > H2O > NH3

1. Boiling point: HF < H2O (Reason: Number of bonds are greater in water molecule).