26 Oswaal CBSE Revision Notes Chapterwise & Topicwise, CHEMISTRY, Class-XI

Effective nuclear change (Zeff) = Nuclear charge – shielding effect

Trend : Zeff increases from left to right in a period.

Zeff decreases from top to bottom in a group.

CHAPTER-4
CHEMICAL BONDING AND MOLECULAR STRUCTURE

General Introduction to Bonding: Ionic and Covalent

Topic-1 Bonds

Revision Notes

Chemical Bond: The attractive force which holds various constituent particles (atoms, ions or molecules) together
in a chemical species is known as chemical bond.
Octet Rule: The octet rule or the electronic theory of chemical bonding was developed by Kossel and Lewis.
According to this rule, atoms can combine either by transfer of valence electrons from one atom to another (gaining
or losing) or by sharing their valence electrons. The principle of attaining maximum of eight electrons in the valence
shell of atoms is called octet rule. Lewis postulated that atoms achieve the stable octet when they are linked by
chemical bonds.
Facts related to chemical bonding given by Kossel are:
l In the periodic table, the highly electronegative halogens and the highly electropositive alkali metals are
separated by the noble gases.
l The formation of a negative ion from a halogen atom and a positive ion from an alkali metal atom is associated
with the gain and loss of an electron by the respective atoms.
l The negative and positive ions thus formed attain stable noble gas electronic configuration. The noble
gases (with the exception of helium which has a duplet of electrons) have a particularly stable outer shell
configuration of eight (octet) electrons, ns2np6.
l The negative and positive ions are stabilized by electrostatic attraction.
Limitations of the Octet Rule: Some limitations of octet rule are:
l In periodic table in and beyond the third period (after silicon) this rule is not applied. These elements can
“expand their octet” and have more than eight valence electrons around the central atom, e.g. PF5 , SF6 etc.
l Molecules with an odd number of electrons such as NO and NO2 cannot satisfy the octet rule.
l In some molecules, the central atom cannot possibly have eight valence electrons. For example, LiCl, BeCl2 and
BCl3 do not obey the octet rule.
l It is based upon the chemical inertness of noble gases. However, some noble gases such as Xenon and Krypton
combine to form a number of compounds like XeF2, KrF2, XeOF2, etc.
l This theory does not account for the shape of molecules.
l It also does not explain the relative stability of the molecules.
Ionic or Electrovalent Bond: “Ionic bonding is a type of chemical bond that involves the electrostatic attraction
between oppositely charged ions together is known as ionic bond and electrovalent bond.” Thus, the electrovalence
is equal to the number of unit charge on the ion.
“Electrovalent compounds are those compounds in which constituent particles are ions or positively charged spe-
cies and they are formed by transfer of electron from a metal to a non-metal.
 Oswaal CBSE Revision Notes Chapterwise & Topicwise, CHEMISTRY, Class-XI 27

Properties of Ionic Compounds:

l Ionic compounds have high melting points and high boiling points.
l They have higher enthalpies of fusion and vaporization than molecular compounds.
l They are hard and brittle.
l These compounds conduct electricity when they are dissolved in water or in molten state.
l Ionic solids are good insulators.
l The ionic bond is non-directional. This is because each ion is surrounded by oppositely charged ions uniformly
distributed all around the ion.
Covalent Bond: A covalent bond is a chemical bond that involves the sharing of electron pairs between atoms. The
stable balance of attractive and repulsive forces between atoms when they share electrons is known as covalent
bonding.
H + H → H H Or H— H
Sharing of
electrons
The sharing of electrons can also be shown by drawing a circle around each atom. For example, H2 molecule is
shown as

Similarly, two chlorine atoms combine with each other to form a molecule of chlorine.

Chlorine atoms Chlorine molecule

Methane (CH4):

Depending upon the number of 2, 4 or 6 electrons shared between two atoms, a covalent bond is called single,
double or triple bond respectively.
If two atoms share one electron pair, bond is known as single covalent bond and is represented by one dash (–).

It two atoms share two electron pairs, bond is known as double covalent bond and is represented by two dashes
(=).

(O2 molecule)

It two atoms share three electron pairs, bond is known as triple covalent bond and is represented by three dashes
(≡).

(N2 molecule)

Lewis Symbols: G.N. Lewis an American chemist introduced simple notations to represent valence electrons in an
atom. These notations are called Lewis Symbols. For Example
Li Be B
30 Oswaal CBSE Revision Notes Chapterwise & Topicwise, CHEMISTRY, Class-XI

Properties of Covalent Compounds:

l Low melting and boiling points: Covalent compounds consist of molecules held by weak forces. These can be
easily overcome by heat.
l Non-conduction nature: Covalent compounds do not conduct electricity, i.e., electricity does not pass through
the covalent compounds. This is because the covalent compounds do not contain ions or free electrons.
l Solubility: Covalent compounds are non-polar and do not dissolve in polar solvents like water. The covalent
compounds however, dissolve in non-polar solvents like benzene, toluene, etc.
l Slow rate of reaction: The reaction of the covalent compounds are quite slow. The reaction is molecular, and
the molecular reactions are slow.
Bond Parameters: The various characteristic features shown by a bond are called the bond parameters.
l Bond length: Bond length is defined as “the equilibrium distance between the centres of the nuclei of two
bonded atoms in a molecule.” Bond lengths are measured by spectroscopic, X-ray diffraction and electron
diffraction techniques.

R = rA + rB
In case of covalent bond, the covalent radius is measured as the radius of an atom’s core which is in contact
with core of an adjacent atom in a bonded situation.

d
Covalent radius = rA + rB = [if rA = rB]
2
The van der Waals radius represents the overall size of the atom which includes its valence shell in a non-
bonded situation.

  Single covalent radius decreases from left to right along a period and increases down a group just like atomic
radii.
l Bond angle: It is defined as the angle between the orbitals containing bonding electron pairs around the
central atom in a molecule/complex ion. For example, the bond angle in some compounds can be represented
as under :

109.28°
107°

l Bond enthalpy: It is defined as the amount of energy required to break one mole of bonds of a particular
type between two atoms in a gaseous state. The unit of bond enthalpy is kJ mol–1. For example H – H bond
enthalpy in hydrogen molecule is 435.8 kJ mol–1.
H2(g) → H(g) + H(g) ; ∆aHΘ = 435.8 kJ mol–1
 Oswaal CBSE Revision Notes Chapterwise & Topicwise, CHEMISTRY, Class-XI 31
l Bond order: In the Lewis description of covalent bond, the bond order is given by the number of bonds
between the two atoms in a molecule. Bond order in H2 is one, in O2, it is two and in N2 it is three.
Isoelectronic molecules and ions have identical bond orders. For example F2 and O2– 2 have bond order
+
1 and N2, CO and NO have bond order 3.
Thus, the stabilities of molecules can be understood by the statement ”with increase in bond order, bond
enthalpy increases and bond length decreases.”
Types of Covalent Bond: Depending upon the nature of combining atoms, the covalent bonds can be of two types:
l Non-polar Covalent Bond: This type of bond is formed between the two atoms of the same element. Atoms of
the same element attract electron equally. So, in other words, the shared electron pair will lie exactly midway
between the two atoms. This type of covalent bond is described as a non-polar covalent bond.
For example: H2, O2 and Cl2, etc.
l Polar Covalent Bond: When two dissimilar atoms, having different electronegativities combined together to
form a covalent bond, the shared pair of electrons does not lie at equal distance from the nuclei of both the
bonded atom but shift towards the atom having greater electronegativity. This type of bond is called covalent
bond. For example, in case of a heteronuclear molecule like HF, the shared electron pair between the two
atoms gets displaced more towards fluorine since the electronegativity of fluorine is far greater than that of
hydrogen. The atom with higher affinity for electrons develops a slight negative charge and atom with lesser
affinity for electrons develops a slight positive charge. Eg., HCl, H2O etc.
Dipole Moment: It is defined as “the product of the magnitude of the charge and the distance of separation be-
tween the charges.”
Dipole moment (µ) = Charge (Q) × Distance of separation (r)
It is usually expressed in Debye units (D).
Dipole moment is also expressed in the units of C m (Coulomb meter):
1D = 3.33564 × 10–30 C m
The dipole of HF may be represented as :
H F
The presence of dipole moment is represented by the crossed arrow ( (.

Key Terms
Valence Electrons: The outermost shell electrons which take part in the formation of chemical bond are
called valence electrons.
Lattice Enthalpy: The lattice enthalpy of an ionic solid is defined as the energy required to completely
separate one mole of a solid ionic compound into gaseous constituent ions.
Bond Enthalpy: It is defined as the amount of energy required to break one mole of bonds of a particular
type between two atoms in a gaseous state.
Electrovalency: The valence of an ion, equal to the number of positive or negative charges acquired by an
atom through a loss or gain of electrons is known as electrovalency.
Covalency: The bond formed between two atoms by mutual sharing of electrons between them so as to
complete their octets is known as covalent bond and number of electrons involved is covalency.

Key Facts
Under normal conditions, no other element exists as an independent atom in nature, except noble gases.
Lewis postulated that atoms achieve the stable octet when they are linked by chemical bonds.
In the periodic table, the highly electronegative halogens and the highly electropositive alkali metals are
separated by the noble gases.
The formation of a negative ion from a halogen atom and a positive ion from an alkali metal atom is
associated with the gain and loss of an electron by the respective atoms.
The negative and positive ions are stabilized by electrostatic attraction.
The Lewis dot structures provide a picture of bonding in molecules and ions in terms of the shared pair
of electrons and the octet rule.
Generally the lowest energy structure is the one with the smallest formal charges on the atoms.
The formal charge is a factor based on a pure covalent view of bonding in which electron pairs are shared
equally by neighbouring atoms.

32 Oswaal CBSE Revision Notes Chapterwise & Topicwise, CHEMISTRY, Class-XI

Topic-2 Resonance and VSEPR Theory

Revision Notes

Resonance: When a molecule cannot canonically be represented by a single structure but its characteristic
properties; position of nuclei, bonding and non-bonding pairs of electrons can be described by two or more than
two canonical structures, then actual structure is said to be a resonance hybrid of these structure. Resonance is
represented by a double headed arrow. Some of the examples of resonance structure are O3 molecule, CO32–, CO2
molecule.
Conditions for Writing Resonating Structure:
l The contributing structures should have same atomic positions.
l These structures should have same number of unpaired electrons.
l These structures should have nearly same energy.
l The structures should be written such that negative charge is present on an electronegative atom and positive
charge is present on an electropositive atom.
l In these structures, the like charges should not reside on adjacent atoms.
Resonance stabilizes the molecule because the energy of the resonance hybrid is less than the energy of any single
canonical structures. Resonance also averages the bond characteristics as a whole.
Resonance Energy: It is the difference between the actual bond energy of the molecule and that of the most stable
resonating structures (having least energy). Thus,
Resonance energy = Actual bond energy
– Energy of the most stable resonating
structure
Valence Shell Electron Pair Repulsion (VSEPR) Theory: In 1940, Sidgwick and Powell proposed a simple theory
based on the repulsive interactions of the electron pairs in the valence shell of the atoms. It was further developed
and refined by Nyholm and Gillespie in 1957.
They suggested that the shapes of molecules can be determined by the number of electron pairs (bonding as well
as non-bonding) in the valence shell of the central atom.
Postulates of VSEPR Theory:
l The geometry of a molecule depends upon the total number of valence shell electron pairs (bonded or non-
bonded) around the central atom in the molecule.
l Pairs of electrons in the valence shell repel one another since their electron clouds are negatively charged.
l These pairs of electrons tend to occupy such positions in space that minimise repulsion and thus maximise
distance between them.
l The valence shell is taken as a sphere with the electron pairs localising on the spherical surface at maximum
distance from one another.
l A multiple bond is treated as if it is a single electron pair and the two or three electron pairs of a multiple bond
are treated as a single super pair.
l Where two or more resonance structures can represent a molecule, the VSEPR model is applicable to any such
structure.

Key Facts
The repulsive interaction of electron pairs decrease in the order –
lp – lp > lp – bp > bp – bp
(where, lp = lone pair, bp = bond pair)
The presence of lone pairs in addition to bond pairs will result in certain distortions in the regular geometry
of molecules.

 Oswaal CBSE Revision Notes Chapterwise & Topicwise, CHEMISTRY, Class-XI 33

Valence Bond Theory, Hybridization, Molecular

Topic-3
Orbital Theory and Hydrogen Bonding

Revision Notes
Valence bond Theory: In 1927, Heitler and London developed Valence bond theory to overcome the limitations
of VSEPR theory based on quantum mechanical principles.
According to theory, a covalent bond is formed between the two atoms by the overlap of half filled valence atomic
orbitals of each atom containing one unpaired electron.
The bond is formed when two atoms approach each other in such a way that occupied orbitals with similar
energies are able to overlap.
Greater the overlap, stronger is the bond.
Types of Overlapping and Nature of Covalent Bonds:
Depending upon the type of overlapping, the covalent bonds may be divided into two types:
(a) Sigma (s) bond and (b) Pi (p) bond
(a) Sigma (s) bond: This type of covalent bond is formed by the end to end (head on) overlapping of bonding
orbitals along the internuclear axis. The overlap is known as head on overlap or axial overlap. The sigma bond is
formed by any one of the following types of combinations of atomic orbitals :
(i) s-s overlapping: In this type, two half filled s-orbitals overlap along the internuclear axis as shown below.

(ii) s-p overlapping: This type of overlapping between the half filled s-orbital of one atom and p-orbital of the

other atom.

s-orbital p-orbital s-p overlap

(iii) p-p overlapping: This type of overlapping occurs between half filled p-orbitals of the two approaching atoms.

p-orbital p-orbital p-p-overlap

(b) Pi (p) bond: This type of covalent bond is formed by the sidewise overlapping of the half filled atomic orbitals
of bonding atoms. Such an overlap is known as sidewise or lateral overlap. The atomic orbitals overlap in such a
way that their axis remain parallel to each other and perpendicular to the internuclear axis. The orbital obtained
as a result of sidewise overlap consists of two saucer type charged clouds above and below the plane of the
participating atoms.


or

p-orbital p-orbital p-p-overlap

Strength of sigma and pi-bonds: The strength of a covalent bond depends upon the extent of overlapping of
atomic orbitals forming the bond. During the formation of a sigma bond, the overlapping of orbitals takes place
to a larger extent.
34 Oswaal CBSE Revision Notes Chapterwise & Topicwise, CHEMISTRY, Class-XI

On the other hand, during the formation of a pi-bond, the overlapping occur to a smaller extent. Therefore, a
sigma bond is strong than a pi-bond.
Hybridisation: According to Pauling, to account for the shapes of polyatomic molecules, the atomic orbitals
combine to form a new set of equivalent orbitals known as hybrid orbitals, are used in bond formation. This
process is known as hybridisation. This may be defined as—
“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.”
Characteristics of Hybridisation:
l The number of hybrid orbitals is equal to the number of the orbitals that get hybridised.
l The hybridised orbitals are always equivalent in energy and shape.
l The hybrid orbitals are more effective in forming stable bonds than the pure atomic orbitals.
l The hybrid orbitals are directed in space in some preferred directions to have stable arrangement. Therefore,
the type of hybridisation indicates the geometry of the molecule.
Conditions for Hybridisation:
l Only the orbitals present in the valence shell of the atom are hybridised.
l The orbitals undergoing hybridisation should have only a small difference in energy, i.e., should have almost
equal energy. The orbitals which differ largely in energy cannot take part in hybridisation.
l Promotion of electron is not essential condition prior to hybridisation.
l It is not essential that only half filled orbitals participate in hybridisation. In certain cases, even filled orbitals
of valence shell participate in hybridisation.
Types of Hybridisation:
l sp Hybridisation: In sp hybridisation, one s and one p orbital mix and form two equivalent sp hybrid orbitals.
The orbitals suitable for sp hybridisation are s and pz orbitals, if the hybrid orbitals are to lie along z-axis.
Each sp hybrid orbitals has 50% s-character and 50% p-character. These two sp hybrid orbitals are oriented in
opposite direction forming an angle of 180°.

Linear sp hybrids

  Formation of sp hybrid orbitals
Example: BeF2, BeCl2, etc.
l sp2 Hybridisation: The combination of one s and two p orbitals gives rise to three sp2 hybrid orbitals. These
three hybrid orbitals lie in the same plane and are directed towards the three corners of an equilateral triangle
in a plane having an angle of 120°. Each sp2 hybrid orbital has 33.3% s-character and 66.7% p-character.
 Oswaal CBSE Revision Notes Chapterwise & Topicwise, CHEMISTRY, Class-XI 35

Example : BCl3, BF3, etc.

l sp3 Hybridisation: In sp3 hybridisation, one s and three p orbitals mix and form four sp3 hybrid orbitals of
equivalent energies and shape. Each sp3 hybrid orbitals has 25% s-character and 75% p-character. The four sp3
hybrid orbitals are directed towards the four corners of the tetrahedron. The angle between sp3 hybrid orbital
is 109°5’.
x
x y
y
sp3-hybridisation 109.5°
z z

One s - orbital Three p - orbitals Four sp 3

hybrid orbitals
Formation of sp3 hybrid orbitals
Example: CH4, CCl4, etc.
l sp3d Hybridisation: This hybridisation involves the mixing of one s, three p and one d-orbitals. These five
orbitals hybridise to form five sp3d-hybrid orbitals. These hybrid orbitals point towards the corners of a
trigonal bipyramidal geometry.

3s y

x
3px 3py

3pz
sp3d hyrbid orbitals having
trigonal bipyramidal
x geometry
3dz2

Formation of sp3d hybrid orbitals

Example : Phosphorus pentachloride, PCl5.
l sp3d2 Hybridisation: A combination of one s, three p and two d atomic orbitals (dx2–y2, dz2) leads to six sp3d2
hybrid orbitals which are directed octahedrally with bond angle of 90°.
Example: SF6

(a) Formation of SF6 molecule involving sp3d2-hybridisation (b) Octahedral geometry of SF6 molecule
l sp3d3 Hybridisation: This involves the mixing of one s, three p and three d-orbitals forming seven sp3d3-
hybrid orbitals having pentagonal bipyramidal geometry. The geometry of IF7 molecule can be explained on
the basis of sp3d3 hybridisation.
36 Oswaal CBSE Revision Notes Chapterwise & Topicwise, CHEMISTRY, Class-XI

Example: IF7

(a) Formation of IF7 molecule involving sp3d3-hybridisation (b) Pentagonal bipyramidal geometry of IF7 molecule

Molecular Orbital Theory:

Molecular orbital theory was proposed by F. Hund and R.S. Mulliken in 1932.
Salient Features of Molecular Orbital Theory:

l Just like an atom, molecule has orbitals of definite energy levels. Like electrons of atoms are present in atomic
orbitals, electrons of a molecule are present in different molecular orbitals.
l Molecular orbitals are formed by the combination of atomic orbitals of proper symmetry and comparable
energies. The atomic orbitals of these atoms merge into molecular orbitals.
l An electron in an atomic orbital is under the influence of only one nucleus. However, an electron in a
molecular orbital is under the influence of two or more nuclei depending upon the number of atoms present
in the molecule.
l The number of molecular orbitals formed is equal to the number of combining atomic orbitals. When two
atomic orbitals combine, they form two molecular orbitals. These are called bonding molecular orbital and
antibonding molecular orbital.
l The bonding molecular orbital has lower energy and hence greater stability whereas corresponding
antibonding molecular orbital has more energy and hence lesser stability.
l The molecular orbital formed by the addition of two atomic orbitals is called bonding molecular orbital.

+ + + + +
+
+
1s 1s 1s
Atomic orbital Bonding molecular orbital

Formation of bonding molecular orbital

l The molecular orbital formed by the subtraction of two atomic orbitals is called antibonding molecular orbital.

+ + + – + –
–

1s 1s
1s
Atomic orbital Node
Antibonding molecular orbital

Formation of antibonding molecular orbital

It is clear from the figure that the electron density in between the two nuclei is practically zero and is
concentrated in regions away from each nucleus. In this case, the electron probability densities of two atomic
orbitals get cancelled in the centre (by subtraction) so that there is no probability of finding the electron in the
region of overlap, i.e. between the nuclei. This situation does not favour the bond formation. Such an orbital
is called antibonding molecular orbital. It is designated as s*1s (called sigma star 1s). The asterisk ‘*‘ is used
to represent antibonding molecular orbital.
 Oswaal CBSE Revision Notes Chapterwise & Topicwise, CHEMISTRY, Class-XI 37
Conditions for the Combination of Atomic Orbitals:
l The combining atomic orbitals must have same or nearly the same energies.
l The extent of overlapping between the atomic orbitals of two atoms should be maximum.
l The combining atomic orbitals must have the same symmetry about the molecular axis.
Types of Molecular Orbitals:
l Bonding molecular orbitals: A molecular orbital that is obtained by the addition overlap (i.e, when the lobes
of atomic orbital overlap with the same sign) of two atomic orbitals is known as bonding molecular orbital.
The energy of bonding molecular orbital is less than that of the constituent overlapping atomic orbitals. The
difference in energy between the combining atomic orbitals and the bonding molecular orbital formed, is
called the stabilisation energy, because, it stabilizes the molecule.
l Non-bonding molecular orbitals: Orbital which are completely inside the closed shell of atom, do not play
any part in the formation of molecule. They remain unaffected and are termed non-bonding molecular
orbitals. When atomic orbitals do not interact with each other, formation of non-bonding molecular orbitals
takes place. The reasons for no interaction may be one of the following:
(i) One orbital is far away from other orbital, so overlapping is not possible.
(ii) Symmetries of atomic orbitals are not same.
(iii) Energies of atomic orbitals are not same.
l Antibonding molecular orbitals: A molecular orbital that is obtained by the subtraction overlap (i.e., when
the lobes of atomic orbitals overlap with the opposite sign) of two atomic orbitals is known as antibonding
molecular orbital. The energy of antibonding molecular orbital is higher than that of the constituent
overlapping atomic orbitals. The difference in energy between the antibonding molecular orbital and the
combining atomic orbital is known as destabilisation energy, because it destabilizes the molecule.
For molecules O2 onwards, the increasing order of energies for molecular orbitals in which they are filled is
as follows :
σ1s < σ*1s < σ2s < σ*2s < σ2pz < (p2pz = p2py) < (p*2pz = p*2py) < σ*2pz
However, for homonuclear diatomic molecules of second row elements such as, Li2, Be2, B2, C2, N2, the s2pz MO
is higher in energy than p2px and p2py MOs.
The increasing order of energies order for MOs for their molecules is
σ1s < σ*1s < σ2s < σ*2s < (p2px = p2py) < σ2pz < (p*2px = p*2py) < σ*2pz
The filling of molecular orbitals take place by following the rules of Aufbau principle, Pauli’s exclusion principle
and Hund’s rule in the similar way as for atomic orbitals.
Presence of unpaired electron shows that molecule is paramagnetic, however, paired electrons show that it is
diamagnetic.
Hydrogen Bonding: When hydrogen atom is bonded to atoms of highly electronegative elements such as
fluorine, oxygen or nitrogen, the hydrogen atom forms a weak bond with the electronegative atom of the other
molecule. This weak bond is called hydrogen bond. For example, in hydrogen fluoride, HF, hydrogen atom forms
a weak bond with fluorine atom of the high bonding molecule while remaining bonded to its fluorine atom. This
may be shown as :
........Hd+ — Fd– .......... Hd+ — Fd– ........ Hd+— Fd–
The hydrogen bond is represented by dotted line ( _ _ _ _ _ ) while the covalent bond is represented by solid line
(––).
Types of Hydrogen Bond:Hydrogen bonds can be classified into two types:
(a) Intermolecular hydrogen bond

(b) Intramolecular hydrogen bond

(a) Intermolecular hydrogen bond: Intermolecular hydrogen bond is formed between different molecules of the

same or different substances.
For example,
(i) hydrogen bond between the molecules of hydrogen fluoride.
(ii) hydrogen bond in alcohol or water molecules.
(b) Intramolecular hydrogen bond: Intramolecular hydrogen bond is formed when the hydrogen atom is

between the two highly electronegative atom (F, O or N) present within the same molecule.
For example,
38 Oswaal CBSE Revision Notes Chapterwise & Topicwise, CHEMISTRY, Class-XI

Applications of Intermolecular H-bonding:

l Melting point and boiling point of water: Water has the lowest molecular weight among the hydrides of
group 16 elements yet it has the highest melting and boiling points. It is due to intermolecular H–bonding in
H2O.
l Ice has less density than water: In crystal structure of ice, every water molecule is associated with four other
water molecules by H-bonding in a cage like tetrahedral structure. On melting, H-bonds in the ice are broken
and space between water molecules decreases and density of water increases up to 4°C. Above 4°C, more
H-bond are broken. The water molecules get apart from each other and the density again decreases. Thus,
water has maximum density at 4°C.
Applications of Intramolecular H-Bonding:
l Volatile character of nitrophenols: ortho-nitrophenol is more volatile (b.p. 214°C) as compared to meta (b.p.
290°C) and para (b.p. 279°C). It is due to chelation.
O 
H
O –
N
—
—

O
l In meta and para isomer, chelation is not possible due to the formation of desired size of ring.

Key Term
Bond Order: It is defined as one half the difference between the number of electrons present in the
1
bonding and the anti bonding orbitals. [Bond order = (Nb – Na)]
2

Key Facts
When orbitals of two atoms come close to form bond, their overlap may be positive, negative or zero
depending upon the sign (phase) and direction of orientation of amplitude of orbital wave function
in space.
The number of hybrid orbitals is equal to the number of the atomic orbitals that get hybridised.
The sigma (s) molecular orbitals are symmetrical around the bond axis whereas pi (p) molecular
orbitals are not symmetrical.
Density of H2O is maximum at 4° C due to strongest intermolecular hydrogen bonding.
A positive bond order (i.e., Nb > Na) means a stable molecule while a negative (i.e., Nb<Na) or zero
(i.e., Nb = Na) bond order means an unstable molecule.
where, Nb = No. of electrons in bonding molecular orbital.
Na = No of electrons in anti-bonding molecular orbital.