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Chemical Bonding

Chemical bond is an attractive force which keeps tow atoms or ions together in a molecule.A
molecule is formed if it is more stable and has lower energy than the individual atoms. Normally only
electrons in the outermost shell of an atom are involved in bond formation and in this process each
atom attains a stable electronic configuration of inert gas. Atoms may attain stable electronic
configuration in three different ways by losing or gaining electrons by sharing electrons. The attractive
forces which hold various constituents (atoms, ions etc) together in different chemical species are called
chemical bonds. Elements may be divided into three classes.

Electropositive elements, whose atoms give up one or more electrons easily, they have low ionization
potentials.
 Electronegative elements, which can gain electrons. They have higher value of electronegativity.
 Elements which have little tendency to loose or gain electrons.
Three different types of bond may be formed depending on electropositive or electronegative character
of atoms involved.

Electropositive element + Electronegative element = Ionic bond (electrovalent bond)

Electronegative element + Electronegative element = Covalent bond

or less electro positive + Electronegative element = Covalent bond

Electropositive + Electropositive element = Metallic bond.

The Lewis Theory

The octet rule:- The Lewis theory gave the first explanation of a covalent bond in terms of electrons
that was generally accepted. If two electrons are shared between two atoms, this constitutes a bond
and binds the atoms together. For many light atoms, a stable arrangement is attained when the atom is
surrounded by eight electrons.
This octet can be made up from some electrons which are totally owned and some electrons which are
‘shared’. Thus atoms continue to form bonds until they have made up an octet of electrons. This is
called the ‘octet rule’. The octet rule explains the observed valencies in a large number of cases. There
are exceptions to the octet rule; for example, hydrogen is stable with only two electrons. Other
exceptions are discussed later.Today, the conventional Lewis structure representation of a pair of
bonded electrons is by means of a ‘dash’ (-) usually called a ‘bond’. Lone pairs or ‘non-bonded’ electrons
are represented by ‘dots’. Some structures are represented below:

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Chemical Bonding

It is therefore useful to remember some important categories of exceptions:

 Odd-electron species like NO, NO2, O2 etc. Since it is impossible to distribute an odd number of
electrons into pairs, these species necessarily violate the octet rule.
 The Valence Bond theory handles such species rather clumsily (odd-electron bonds etc.) the
molecular orbital theory copes much better.
 Species in which the central atom `expands' its octet (so to speak) PCl5, SF6, many transition
metal compounds etc.
 Electron -deficient species like BCl3, BeCl2, AlCl3, B2H6 etc. in which the central atom has fewer
than eight electrons.

Ionic Bonding

Table of Content
 Electrovalency
 Criteria for Ionic Bond Formation
 Energy Change During the Formation of Ionic Bond
 Determination of Lattice Energy
 Characteristics of Ionic Compounds

 Electrovalency

This type of valency involves transfer of electrons from one atom to another, whereby each atom may
attain octet in their outermost shell. The resulting ions that are formed by gain or loss of electrons are
held together by electrostatic force of attraction due to opposite nature of their charges. The reaction
between potassium and chlorine to form potassium chloride is an example of this type of valency.

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Here potassium has one electron excess of it’s octet and chlorine has one deficit of octet. So potassium
donates it’s electron to chlorine forming an ionic bond.

Here the oxygen accepts two electrons from calcium atom. It may be noted that ionic bond is not a true
bond as there is no proper overlap of orbitals.
 Criteria for Ionic Bond Formation
One of the species must have electrons in excess of octet while the other should be deficit of octet.
Does this mean that all substance having surplus electron and species having deficient electron would
form ionic bond? The answer is obviously no. Now you should ask why? The reasoning is that in an ionic
bond one of the species is cation and the other is anion. To form a cation from a neutral atom energy
must be supplied to remove the electron and that energy is called ionization energy. Now it is obvious
that lower the ionization energy of the element the easier it is to remove the electron. To form the
anion, an electron adds up to a neutral atom and in this process energy is released. This process is called
electron affinity.
So for an ionic bond one of the species must have low ionization energy and the other should have high
electron affinity. Low ionization energy is mainly exhibited by the alkali and alkaline earth metals and
high electron affinity by the halogen and chalcogens. Therefore this group of elements are predominant
in the field of ionic bonding.
 Energy Change During the Formation of Ionic Bond
The formation of ionic bond can be consider to proceed in three steps
(a) Formation of gaseous cations
A(g) + I.E. → A+ (g) + e–
The energy required for this step is called ionization energy (I.E)
(b) Formation of gaseous anions
X(g) + e– → X–(g) + E.A
The energy released from this step is called electron affinity (E.A.)
(c) Packing of ions of opposite charges to form ionic solid
A+(g) + X–(g) → AX(s) + energy
The energy released in this step is called lattice energy.
Now for stable ionic bonding the total energy released should be more than the energy required.

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Chemical Bonding
From the above discussion we can develop the factors which favour formation of ionic bond and also
determine its strength. These factors have been discussed below:
(a) Ionization energy: In the formation of ionic bond a metal atom loses electron to form cation. This
process required energy equal to the ionization energy. Lesser the value of ionization energy, greater is
the tendency of the atom to form cation. For example, alkali metals form cations quite easily because of
the low values of ionization energies.
(b) Electron affinity: Electron affinity is the energy released when gaseous atom accepts electron to
form a negative ion. Thus, the value of electron affinity gives the tendency of an atom to form anion.
Now greater the value of electron affinity more is the tendency of an atom to form anion. For example,
halogens having highest electron affinities within their respective periods to form ionic compounds with
metals very easily.
(c) Lattice energy: Once the gaseous ions are formed, the ions of opposite charges come close
together and pack up three dimensionally in a definite geometric pattern to form ionic crystal.
Since the packing of ions of opposite charges takes place as a result of attractive force between them,
the process is accompanied with the release of energy referred to as lattice energy. Lattice energy may
be defined as the amount of energy released when one mole of ionic solid is formed by the close
packing of gaseous ion.
In short, the conditions for the stable ionic bonding are:
(a) I.E. of cation forming atom should be low:
(b) E.A. of anion – forming atom should be high;
(c) Lattice energy should be high.
 Determination of Lattice Energy
The direct calculation of lattice enthalpy is quite difficult because the required data is often not
available. Therefore lattice enthalpy is determined indirectly by the use of the Born – Haber cycle. The
cycle uses ionization enthalpies, electron gain enthalpies and other data for the calculation of lattice
enthalpies. The procedure is based on the Hess’s law, which states that the enthalpy of a reaction is the
same, whether it takes place in a single step or in more than one step. In order to understand it let us
consider the energy changes during the formation of sodium chloride from metallic sodium and chlorine
gas. The net energy change during the process is represented by ΔHf.

For example: Born- Haber Cycle for Soidum Chloride

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Chemical Bonding

Solved Problem on Born- Haber Cycle

Calculate the lattice enthalpy of MgBr2. Given that
Enthalpy of formation of MgBr2 = -524 kJ mol–1
Some of first & second ionization enthalpy (IE1 + IE2 ) = 148 kJ mol-1
Sublimation energy of Mg = +2187 kJ mol–1
Vaporization energy of Br2(I) = +31kJ mol–1
Dissociation energy of Br2(g) = +193kJ mol–1
Electron gain enthalpy of Br(g) = -331 kJ mol–1
Solution: ΔHof = S + I.E. + ΔHvap + D + 2 × E.A. + U
Or U = ΔHof – (S + I.E. + ΔHvap + D + 2 × E.A.)
Or U = -524 - [2187 - 148 + 31 + 193 + 2 × (-331)]
= – 524 – 1897 = –2421 kJ mol–1
 Characteristics of Ionic Compounds
The following are some of the general properties shown by these compounds
(i) Crystalline nature : These compounds are usually crystalline in nature with constituent units as
ions. Force of attraction between the ions is non-directional and extends in all directions. Each ion is
surrounded by a number of oppositely charged ions and this number is called co-ordination number.
Hence they form three dimensional solid aggregates. Since electrostatic forces of attraction act in all
directions, therefore, the ionic compounds do not posses directional characteristic and hence do not
show stereoisomerism.
(ii) Due to strong electrostatic attraction between these ions, the ionic compounds have high melting
and boiling points.
(iii) In solid state the ions are strongly attracted and hence are not free to move. Therefore, in solid
state, ionic compounds do not conduct electricity. However, in fused state or in aqueous solution, the
ions are free to move and hence conduct electricity.
(iv) Solubility : Ionic compounds are fairly soluble in polar solvents and insoluble in non-polar solvents.
This is because the polar solvents have high values of dielectric constant which defined as the capacity

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Chemical Bonding
of the solvent to weaken the force of attraction between the electrical charges immersed in that
solvent. This is why water, having high value of dielectric constant, is one of the best solvents.
The solubility in polar solvents like water can also be explained by the dipole nature of water where the
oxygen of water is the negative and hydrogen being positive, water molecules pull the ions of the ionic
compound from the crystal lattice. These ions are then surrounded by water dipoles with the oppositely
charged ends directed towards them. These solvated ions lead an independent existence and are thus
dissolved in water. The electrovalent compound dissolves in the solvent if the value of the salvation
energy is higher than the lattice energy of that compounds.
AB + Lattice energy → A+ + B–
These ions are surrounded by solvent molecules. This process is exothermic and is called salvation.
A+ + x(solv.) → [A(solv.)x]+ + energy
B– + y(solv.) → [B(solv.)y]– + energy
The value of solvation energy depend on the relative size of the ions. Smaller the ions more is the
solvation. The non-polar solvents do not solvate ions and thus do not release energy due to which they
do not dissolve ionic compounds.

(v) Ionic reactions: Ionic compound furnish ions in solutions. Chemical reactions are due to the
presence of these ions. For example
Na2SO4 → 2Na+ + SO42–
BaCl2 → Ba2+ + 2Cl–

Covalent Bonding and Valence Bond Theory

Table of Content
 Covalancy
 Valence Bond Theory (VBT)
 Sigma and Pi Bonding
 Co-ordinate Covalency
 Conditions for Formation of Covalent Bond
 Polar and Non-Polar Covalent Bonds

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 Maximum Covalency
 Dipole Moment
 Calculation of Resultant Bond Moments

 Covalancy

This type of valency involves sharing of electrons between the concerned atoms to attain the octet
configuration with the sharing pair being contributed by both species equally. The atoms are then held
by this common pair of electrons acting as a bond, known as covalent bond. If two atoms share more
than one pair then multiple bonds are formed. Some examples of covalent bonds are

 Valence Bond Theory (VBT)

A covalent bond is formed by overlapping of valence shell atomic orbitals of the two atoms having
unpaired electron. As a result of overlapping, there is maximum electron density between the bonding
atoms and large part of bonding force arises due to electrostatic force of attraction between
accumulated electron cloud and two nuclei. Greater the overlapping of atomic orbitals higher is the
strength of chemical bond. The paired electron of valence shell of an atom can take part in covalent
bonding subject to availability of vacant orbitals of slightly higher energy of the same main energy shell
and availability of energy for unpairing of paired electron and their shifting to vacant orbitals. This point
explains the trivalency of boron, tetravalency of carbon, pentavalency of phosphorous hexavalency of S
and hepta valency of Cl, Br, I.
Depending on type of overlapping atomic orbitals covalent bond can be classified into two types
1. Sigma (s)
2. Pi (p) bond
 Sigma and Pi Bonding
When two hydrogen atoms form a bond, their atomic orbitals overlap to produce a greater density of
electron cloud along the line connecting the two nuclei. In the simplified representations of the
formation of H2O and NH3 molecules, the O—H and N—H bonds are also formed in a similar manner, the
bonding electron cloud having its maximum density on the lines connecting the two nuclei. Such bonds
are called sigma bonds (σ-bond).
A covalent bond established between two atoms having the maximum density of the electron cloud
along the line connecting the centre of the bonded atoms is called a σ-bond. A σ-bond is thus said to
possess a cylindrical symmetry along the internuclear axis.

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Chemical Bonding
Let us now consider the combination of two nitrogen atoms. Of the three singly occupied p-orbitals in
each, only one p-orbital from each nitrogen (say, the px may undergo “head –on” overlap to form
a s-bond. The other two p-orbitals on each can no longer enter into a direct overlap. But each p-orbital
may undergo lateral overlap with the corresponding p-orbital on the neighbour atom. Thus we have two
additional overlaps, one by the two py orbitals, and the other by the two pz orbitals. These overlaps are
different from the type of overlap in as-bond.
For each set of p-orbitals, the overlap results in accumulation of charge cloud on two sides of the
internuclear axis. The bonding electron cloud does no more posses an axial symmetry as with
the s-bond; instead, it possess a plane of symmetry. For the overlap of the pz atomic orbital, the xy plane
provides this plane of symmetry; for the overlap of the pyatomic orbitals, the zx plane serves the
purpose. Bonds arising out of such orientation of the bonding electron cloud are designated as π-bonds.
The bond formed by lateral overlap of two atomic orbitals having maximum overlapping on both sides of
the line connecting the centres of the atoms is called a π-bond. A π-bond possess a plane of symmetry,
often referred to as the nodal plane.

σ-Bond :
When covalent bond is formed by overlapping of atomic orbitals along the same axis it is called s - bond.
Such type of bond is symmetrical about the line joining the two nuclei e.g.

(a) s-s
overlapping

(b) s-p
overlapping

(c) p-p
overlapping

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π - Bond:
This type of bond is formed by the sidewise or lateral overlapping of two half filled atomic orbitals.

|The strength of a bond depends upon the extent of overlapping of half-filled atomic orbitals. The
extent of overlapping is between two atoms is always greater when there is end to end overlapping of
orbitals than, when there is sidewise overlapping of oritals. Hence s-bond is always stronger than
p-bond.
The average distance between the nuclei of the two bonded atoms in a molecule is called bond length
and the energy required to break one mole of bonds of particular type in gaseous state is called Bond
energy or Bond strength. The same amount of energy is released in formation of one mol of particular
bond.
Limitation: VBT cannot explain the paramagnetic properties of B2,O2 etc.

 Co-ordinate Covalency
A covalent bond results from the sharing of pair of electrons between two atoms where each atom
contributes one electron to the bond. It is also possible to have an electron pair bond where both
electrons originate from one atom and none from the other. Such bonds are called coordinate
bond or dative bonds. Since in coordinate bonds two electrons are shared by two atoms, they differ
from normal covalent-bond only in the way they are formed and once formed they are identical to
normal covalent –bond.
It is represented as [——→]
Atom/ion/molecule donating electron pair is called Donor or Lewis base. Atom / ion / molecule
accepting electron pair is called Acceptor or Lewis acid, [——→] points donor to acceptor
NH4+, NH3 has three (N – H) bond & one lone pair on N – atom. In NH4+ formation this lone pair is
donated to H+ (having no electron) NH3 + H+ → NH4+

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Properties of the coordinate compounds are intermediates of ionic and covalent compounds.
 Conditions for Formation of Covalent Bond
1. The electronegativity deference between the two atoms should be less.
2. The covalent bond is formed between the two non metals.
3. Each combining atom must contribute at least one electron to the shared pair.
4. The combining atoms should attain the noble gas configuration after bond formation.
 Polar and Non-Polar Covalent Bonds
Covalent bonds can be classified into following two groups depending on the electronegativity
difference between the bonded atoms..
1. Polar covalent bond.
2. Nonpolar covalent bond.
Polar covalent bond is formed between two atoms which have large difference in electronegativity. The
electronegativity difference disturbs the distribution of shared pair of electrons between the two atoms
as the electron density would be more toward the element which is more electronegative. This will
develop partial positive charge on more electronegative element and partial positive charge on less
electronegative one. For example, bond between H and F would be polar covalent bond.

Non-polar covalent bonds are formed between two like atoms i.e. the atoms which have almost same
electronegativity. Due to almost same electronegativity, both atoms attract electron pair equally and no
charge appears on any atom, and the whole molecule becomes neutral. For example bond between two
H atoms would be non-polar.
 Maximum Covalency
Elements which have vacant d-orbital can expand their octet by transferring electrons, which arise after
unpairing, to these vacant d-orbital e.g. in sulphur.

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In excited state sulphur has six unpaired electrons and shows a valency of six e.g. in SF6. Thus an element
can show a maximum covalency equal to its group number e.g. chlorine shows maximum covalency of
seven.
 Dipole Moment
Difference in polarities of bonds is expressed on a numerical scale. The polarity of a molecule is
indicated in terms of dipole moment (μ). To measure dipole moment, a sample of the substance is
placed between two electrically charged plates. Polar molecules orient themselves in the electric field
causing the measured voltage between the plates to change.
The dipole moment is defined as the product of the distance separating charges of equal magnitude and
opposite sign, with the magnitude of the charge. The distance between the positive and negative
centres called the bond length.
Thus, = μ = electric charge × bond length = q × d
As q is in the order of 10–10 esu and d is in the order of 10–8 cm, μ is the order of10–18 esu cm. Dipole
moment is measured in ‘Debye’ unit (D)
1D = 10–18 es cm = 3.33 × 10–30 coulomb metre
Note:
1. Generally as electronegativity difference increase in diatomic molecules, polarity of bond
between the atoms increases therefore value of dipole moment increases.
2. Dipole moment is a vector quantity.

3. A symmetrical molecule is non-polar even though it contains polar bonds. For example, CO2, BF3,
CCl4 etc. because summation of all bond moments present in the molecules cancel each other.

4. Unsymmetrical non-linear polyatomic molecules have net value of dipole moment. For example,
H2O, CH3OH, NH3 etc.?
Calculation of Resultant Bond Moments

Let AB and AC are two polar bonds inclined at an angle θ their dipole moments are μ1 and μ2.

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Resultant dipole moment may be calculated using vectorial method.
μ = √μ12 + μ22 + 2μ1μ2 cos θ

when θ = 0 the resultant is maximum μR = μ1 + μ2

when, θ = 180°, the resultant is minimum μR = μ1 ∼ μ2

For example, CO2 has got dipole moment of zero. The structure of CO2 is.This is a highly symmetrical
structure with a plane of symmetry passing through the carbon. The bond dipole of C–O is directed
towards oxygen as it is the negative end. Here two equal dipoles acting in opposite direction cancel each
other and therefore the dipole moment is zero. Similarly dipole moment of CCl4 is zero while that of
CHCl3 is non zero. . Explanation is again in geometry of the molecules both CCl4 & CHCl3 have tetrahedral
structure but CCl4 is symmetrical while CHCl3 is non-symmetrical.

Due to the symmetrical structure of CCl4 the resultant of bond dipoles comes out to be zero. But in case
of CHCl3 it is not possible as the presence of hydrogen introduces some dissymmetry.

Characteristics of Bond

Table of Content

 Bond Length
 Important Features of Bond Length
 Bond Energy or Bond Strength
 Bond Angles
 Resonance
 Rules for writing Resonating Structures
Bond Length

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Chemical Bonding
The distance between the nuclei of two atoms bonded together is termed as bond length or bond
distance. It is expressed in angstrom (Å) units or picometer (pm).
[1Å = 10–8 cm; 1 pm = 10–12 m]
Bond length in ionic compound = rc+ + ra–
Similarly, in a covalent compound, bond length is obtained by adding up the covalent (atomic) radii of
two bonded atoms.
Bond length in covalent compound (AB) = rA + rB
The factors such as resonance, electronegativity, hybridization, steric effects, etc., which affect the radii
of atoms, also apply to bond lengths.

Important Features of Bond Length

 The bond length of the homonuclear diatomic molecules are twice the covalent radii.
 The lengths of double bonds are less than the lengths of single bonds between the same
two atoms, and triple bonds are even shorter than double bonds.Single bond > Double bond >
Triple bond (decreasing bond length)
 Bond length decreases with increase in s-character since s-orbital is smaller than a p – orbital.
 sp3 C – H = 1.112Å: sp2 C – H = 1.103Å; sp C – H =
1.08Å;
 (25% s-character as in alkanes) (33.3% s-character as in alkenes) (50% s-character as in alkynes)
 Bond length of polar bond is smaller than the theoretical non-polar bond length.

Bond Energy or Bond Strength

Bond energy or bond strength is defined as the amount of energy required to break a bond in
molecule.
Important features of bond energy:
 The magnitude of the bond energy depends on the type of bonding. Most of the covalent bonds
have energy between 50 to 100 kcal mol–1 (200-400 kJ mol–1). Strength of sigma bond is more
than that of a π-bond.
 A double bond in a diatomic molecules has a higher bond energy than a single bond and a triple
bond has a higher bond energy than a double bond between the same atoms. C ≡ C > C = C > C –
C (decreasing bond length)
 The magnitude of the bond energy depends on the size of the atoms forming the bond, i.e. bond
length. Shorter the bond length, higher is the bond energy.
 Resonance in the molecule affects the bond energy.
 The bond energy decreases with increase in number of lone pairs on the bonded atom. This is
due to electrostatic repulsion of lone pairs of electrons of the two bonded atoms.
 Homolytic and heterolytic fission involve different amounts of energies. Generally the values are
low for homolytic fission of the bond in comparison to heterolytic fission.
 Bond energy decreases down the group in case of similar molecules.
 Bond energy increase in the following order:

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s < p < sp < sp2 < sp3
C–C > N–N > O–O
(No lone pair) (One lone pair) (Two lone pair)

Bond Angles
Angle between two adjacent bonds at an atom in a molecule made up of three or more atoms is known
as the bond angle.

Bond angles mainly depend on the following three factors:

(i) Hybridization: Bond angle depends on the state of hybridization of the central atom
Hybridization Bond angle Example

sp3 109o28' CH4

sp2 120o BCl3

sp 180o BeCl2
Generally s- character increase in the hybrid bond, the bond angle increases.
(ii) Lone pair repulsion: Bond angle is affected by the presence of lone pair of electrons at the central
atom. A lone pair of electrons at the central atom always tries to repel the shared pair (bonded pair) of
electrons. Due to this, the bonds are displaced slightly inside resulting in a decrease of bond angle.
(iii) Electronegativity: If the electronegativity of the central atom decreases, bond angle decreases.

Resonance

There may be many molecules and ions for which it is not possible to draw a single Lewis structure. For
example we can write two electronic structures of O3.

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In (A) the oxygen - oxygen bond on the left is a double bond and the oxygen-oxygen bond on the right is
a single bond. In B the situation is just opposite. Experiment shows however, that the two bonds are
identical. Therefore neither structure A nor B can be correct.
One of the bonding pairs in ozone is spread over the region of all the three atom rather than associated
with particular oxygen-oxygen bond. This delocalised bonding is a type of bonding in which bonding pair
of electrons is spread over a number of atoms rather than localised between two.

Structures (A) and (B) are called resonating or canonical structures and C is the resonance hybrid. This
phenomenon is called resonance, a situation in which more than one plausible structure can be written
for a species.
Atoms gain or lose electrons to attain a more stable noble gas - like electron configuration (octet rule).
There are two ways in which atoms can share electrons to satisfy the octet rule:
Ionic Bonding - occurs when two or more ions combine to form an electrically-neutral compound
The positive cation "loses" an electron (or 2 or 3)
The negative anion "gains" the electron (or 2 or 3)
The anion steals the electrons from the cation.
Covalent Bonding - occurs when two or more atoms combine to form an electrically-neutral compound
The electrons are shared between the two atoms. Both atoms don't have charge in the beginning and
the compound remains with zero charge.
The chemical activity of an atom is determined by the number of electrons in its valence shell. With the
help of concept of chemical bonding one can define the structure of a compound and is used in many
industries for manufacturing products in which the true structure cannot be written at all.
Some other examples
(i) CO32– ion

Example
(ii) Carbon-oxygen bond lengths in carboxylate ion are equal due to resonance.

(iii) Benzene

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(iv) Vinyl Chloride

Difference in the energies of the canonical forms and resonance hybrid is called resonance stabilization
energy and provides stability to species.

Rules for writing Resonating Structures

Only electrons (not atoms) may be shifted and they may be shifted only to adjacent atoms or bond
positions.
The number of unpaired electrons should be same in all the canonical form.
The positive charge should reside as far as possible on less electronegative atom and negative charge on
more electronegative atom.
Like charge should not reside on adjacent atom
The larger the number of the resonating structures greater the stability of species. Greater number of
covalency adds to the stability of the molecule.
Example: Out of the following resonating structures for CO2 molecule, which are important for
describing the bonding in the molecule and why?

Solution: Out of the structures listed above, the structure (III) is wrong since the number of electron
pairs on oxygen atoms are not permissible. Similarly, the structures (II) has very little contribution
towards the hybrid because one of the oxygen atoms (electronegative) is show to have positive charge.
Carbon dioxide is best represented by structures (I) and (IV).

Hybridization

Table of Content
 Important Characteristics of Hybridization?
 Rule for Determination of total Number of Hybrid Orbitals

The mixing or merging of dissimilar orbitals of similar energies to form new orbitals is known
as hybridization and the new orbitals formed are known as hybrid orbitals.
Important Characteristics of Hybridization?
1. Orbitals belonging to the same atom or ion having similar energies get hybridized.

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2. Number of hybrid orbitals is equal to the no. of orbitals taking part in hybridization.
3. The hybrid orbitals are always equivalent in energy and shape.
4. The hybrid orbitals form more stable bond than the pure atom orbital.
5. The reason hybridization takes place is to produce equivalent orbitals which give maximum
symmetry.
6. It is not known whether actually hybridization takes place or not. It is a concept which explains
the known behaviour of molecules.
7. The hybrid orbitals are directed in space in same preferred direction to have some stable
arrangement and giving suitable geometry to the molecule.
Depending upon the different combination of s and p orbitals, these types of hybridization are
known.
sp3 hybridization: In this case, one s and three p orbitals hybridise to form four sp3 hybrid orbitals.
These four sp3 hybrid orbitals are oriented in a tetrahedral arrangement.

sp2 hybridization: In this case one s and two p orbitals mix together to form three sp2 hybrid orbitals
and are oriented in a trigonal planar geometry.

The remaining p orbital if required form side ways overlapping with the other unhybridized p orbital of
other C atom and leads to formation of p2C = CH2 bond as in H

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sp hybridization: In this case, one s and one p orbital mix together to form two sp hybrid orbitals and
are oriented in a linear shape.

The remaining two unhybridised p orbitals overlap with another unhybridised p orbital leading to the
formation of triple bond as in HC CH.
Shape Hybridisation

Linear sp

Trigonal planar sp2

Tetrahedral sp3

Trigonal bipyramidal sp3d

Octahedral sp3d2

Pentagonal bipyramidal sp3d3

Rule for Determination of total Number of Hybrid Orbitals

Detect the central atom along with the peripheral atoms.
Count the valence electrons of the central atom and the peripheral atoms.
Divide the above value by 8. Then the quotient gives the number of s bonds and the remainder gives
the non-bonded electrons. So number of lone pair = non bonded electrons/2 .
The number of s bonds and the lone pair gives the total number of hybrid orbitals.
An Example Will Make This Method Clear:- SF4 Central atom S, Peripheral atom F
∴ total number of valence electrons = 6 + (4 × 7) = 34
Now 34/8 = 4 2/8
∴ Number of hybrid orbitals = 4σ bonds + 1 lone pair)
So, five hybrid orbitals are necessary and hybridization mode is sp3d and it is trigonal bipyramidal (TBP).
Note:Whenever there are lone pairs in TBP geometry they should be placed in equatorial position so
that repulsion is minimum.

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Compound and its Hybridization Molecular geometry

1. NCl3 Total valence electrons = 26

Requirement = 3σ bonds + 1 lone pair
Hybridization = sp3
Shape = pyramidal

2. BBr3 Total valence electron = 24

Requirement = 3σ bonds
Hybridization = sp2
Shape = planar trigonal

3. SiCl4 Total valence electrons = 32

Requirement = 4σ bonds
Hybridization = sp3
Shape = Tetrahedral
4. CI4 Total valence electron = 32
Requirements = 4σ bonds
Hybridization = sp3
Shape = Tetrahedral

5. SF6 Total valence electrons = 48

Requirement = 6σ bonds
Hybridization = sp3d2
Shape = octahedral/square bipyramidal
6. BeF2 Total valence electrons : 16 F – Be – F
Requirement : 2σ bonds
Hybridization : sp
Shape : Linear
7. ClF3 Total valence electrons : 28
Requirement: 3σ bonds + 2 lone pairs
Hybridization : sp3d
Shape : T – shaped

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8. PF5 Total valence electrons : 40

Requirement : 5σ bonds
Hybridization : sp3d
Shape : Trigonal bipyramidal (TBP)
9. XeF4 Total valence electrons : 36
Requirement:4σ bonds+ 2 lone pairs
Hybridisation : sp3d
Shape : Square planar

Here three arrangements are possible out of which A and B are

same. A and B can be inter converted by simple rotation of
molecule. The basic difference of (B) and (C) is that in (B) the lone
pair is present in the anti position which minimizes the repulsion
which is not possible in structure (C) where the lone pairs are
adjacent. So in a octahedral structure the lone pairs must be
placed at the anti positions to minimize repulsion. So both
structure (A) and (B) are correct.
10. XeF2 Total valence electrons : 22
Requirements : 2σ bonds + 3 lone pairs
Hybridisation: sp3d
Shape : Linear
11. Total valence electrons : 32
Requirement : 4σbonds
Hybridisation: sp3
Shape: tetrahedral

Here all the structures drawn are resonating structures with

O– resonating with double bonded oxygen.
12. NO2– Total valence electron: 18
Requirement : 2σ bonds + 1 lone pair
Hybridisation: sp2
Shape: angular

13. CO32– Total valence electrons: 24 But C has 4 valence electrons of these 3 form s bonds \ the rest
Requirement = 3σ bonds will form a p bond.
Hybrdisation = sp2
Shape: planar trigonal

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In the structure one bond is a double bond and the other 2 are
single. The position of the double bonds keeps changing in the
figure. Since peripheral atoms are isovalent, so contribution of the
resonanting structures are equal. Thus it is seen that none of the
bonds are actually single or double. The actual state is

14. CO2 Total valence electrons:16

Requirement: 2σ bonds O=C=O
Hybridisation: sp
Shape: linear
15. Total valence electrons = 32
Requirement= 4σ bonds
Hybridisation: sp3
Shape: Tetrahedral
16. Total valence electron = 26
Requirement = 3σ bond + 1 lone pair
Hybridization: sp3
Shape: pyramidal
17. XeO2F2 Total valence electrons : 34
Requirement: 4σ bonds +1 lone pairs
Hybridization : sp3d
Shape: Distorted TBP (sea-saw geometry)

18. XeO3 Total valence electrons : 26

Requirement: 3σ bonds + 1 lone pair
Hybridization: sp3
Shape: Pyramidal

19. XeOF4 Total valence electrons : 42

Requirement: 5σ bonds + 1 lone pair
Hybridization: sp3d2
Shape: square pyramidal.

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20. PF2Br3 Total valence electrons : 40
Requirements : 5σ bonds
Hybridisation: sp3d
Shape : trigonal bipyramidal

Valence Shell Electron Pair Repulsion (VSPER)

Theory

Regular Geometry of Molecules

Geometry of the molecules in which the central atom has no lone pairs are regular and can be predicted
simply.
Bond ange of any molecule with regular geometry = 360o /Number of bond pairs
Number of Arrangement of
Molecular geometry Examples
electron pairs electrons

B–A–B BeCl2,
2
Linear HgCl2

3
BF3, AlCl3

θ = 120° θ = 120°

4 CH4, NH4+,
SiF4

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5
PCl5, PF5

6 SF6

Irregular Geometry of Molecules and VSPER Theory

Geometry of the molecules having lone pair of electrons can not be predicted simpley using above
mentioned method. The geometric arrangement of atoms in molecules and ions may be predicted by
means of the valence-shell electron-pair repulsion (VSEPR) theory. This type includes molecules which
may or may not obey the octet rule but have only single bonds.
Postulates of VSEPR theory:
 The shape of the molecule is determined by repulsions between all of the electron pairs present
in the valence shell.
 A lone pair of electrons takes up more space around the central atom than a bond-pair, since
the lone pair is attracted to one nucleus whilst the bond pair is shared by two nuclei. It follows
that repulsion between two lone pairs is greater than repulsion between a lone pair and a bond
pair, which in turn is greater than the repulsion between two bond pairs. Thus the presence of
lone pairs on the central atom causes slight distortion of the bond angles from the ideal shape. If
the angle between a lone pair, the central atom and a bond pair is increased, it follows that the
actual bond angle between the atoms must be decreased.The descending order of repulsion is
 (lp – lp) > (lp – bp) > (bp – bp)
 where lp-Lone pair; bp-bond pair
 The magnitude of repulsions between bonding pairs of electrons depends on the
electronegativity difference between the central atom and the other atoms.
 Double bonds cause more repulsion than single bonds and triple bonds cause more repulsion
than double bonds.

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 A brief summary of molecular shapes resulting from different configurations of electrons pairs is
presented below:
 With very few exceptions, the predictions based on the VSEPR theory have been shown to be
correct.
Refer to the following video for geometry of the different molecules

Molecule No. of Bonding No. of Arrangement of Shape

Examples
Type pairs lone pair electrons pairs (Geometry)

AB2E 2 1 Bent SO2, O3

Trigonal
AB3E 3 1 NH3
pyramidal

AB2E2 2 2 Bent H2O

See saw SF4

AB4E 4 1

AB3E2 3 2 T – shaped CIF3

Square pyramidal BrF5

AB5E 5 1

XeF4
AB4E2 4 2 Square planar

To find the shape of a molecule follow the steps given below:

 Identify the central atom and count the number of valence electrons.
 Add to this, number of other atoms.

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 If it is an ion, add negative charges and subtract positive charges. Call it total N
 Divide N by 2 and compare the result with chart I and obtain the shape.

Total N/2 Shape of molecule or ion Example

2 Linear HgCl2/BeCl2

3 Triangular planar BF3

3 Angular SnCl2, NO2

4 Tetrahedral CH4, BF4-

4 Trigonal Pyramidal NH3, PCl3

4 Angular H2O

5 Trigonal bipyramidal PCl5, PF5

5 Irregular tetrahedral SF4, IF4+

5 T-shaped CIF3, BrF3

5 Linear XeF2, I3-

6 Octahedral SF6, PF6-

6 Square Pyramidal IF5

6 Square planar XeF4, ICI4

Molecular Orbital Theory

Table of Content

 Introduction to Molecular Orbital Theory

 Bond Order
 Application of MOT to Homonuclear Diatomic Molecules
 M.O. of Some Diatomic Heteronuclei Molecules
o Inert Pair Effect

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Introduction to Molecular Orbital Theory
One of the most important theories developed is the wave-particle, duality of particles. Electrons can be
considered as particles and waves also. Based on this, it can be concluded that electrons behaving as
waves can interact with each other and the process is called interference.
As in waves, two types of interferences are possible: (1) constructive and (2) Destructive.
In molecules the atomic orbitals of all the atoms are assumed to interfere with each other in the form of
waves and depending on the nature of interferences, two molecular orbitals result. The one which
results from constructive interference is called bonding molecular orbital and the one which results from
destructive interference is called anti-bonding molecular orbital. Obviously anti-bonding MO is of higher
energy than Bonding MO.
In Molecular Orbital Theory (MOT) the atoms in a molecule are supposed to loose their individual
control over the electrons. The nuclei of the bonded atoms are considered to be present at equilibrium
inter-nuclear positions. The orbitals where the probability of finding the electrons is maximum are
multicentred orbitals called molecular orbitals extending over two or more nuclei.
In MOT the atomic orbitals loose their identity and the total number of electrons present are placed in
Mo’s according to increasing energy sequence (Auf Bau Principle) with due reference to Pauli’s Exclusion
Principle and Hund’s Rule of Maximum Multiplicity.
As mentioned above, when a pair of atomic orbitals combine they give rise to a pair of molecular
orbitals, the bonding and the anti-bonding. The number of molecular orbitals produced must always be
equal to the number of atomic orbitals involved. Electron density is increased for the bonding MO’s in
the inter-nuclear region but decreased for the anti-bonding MO’s, Shielding of the nuclei by increased
electron density in bonding MO’s reduces inter nuclei repulsion and thus stabilizes the molecule
whereas lower electron density even as compared to the individual atom in anti-bonding MO’s increases
the repulsion and destabilizes the system.
In simple homonuclear diatomic molecules the order of MO's based on increasing energy is :

For molecules including O2 and above, the order is

This order is true except B2, C2 & N2. If the molecule contains unpaired electrons in MO’s it will be
paramagnetic but if all the electrons are paired up then the molecule will be diamagnetic.

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Bond Order
Bond order is a number which indicates the no. of bonds a molecule possesses and the stability of the
molecule in comparison to another. An integral value implies that so many bonds exist in the molecule.
Anything fractional indicates that the bond is intermediate.
Bond-order = 1/2 (no. of bonding electrons - No. of antibonding electrons).

Application of MOT to Homonuclear Diatomic Molecules

H2+ molecule ion. Total no. of electrons = 1
 Arrangement : s 1s1
 An unpaired electron always indicates that the molecule is paramagnetic.
H2 molecule, Total no. of electrons = 2
 Arrangement : s 1s2
 Paired electrons , so diamagnetic.
 BO = 1/2 (2-0) = 1
 Therefore No. of bonds = 1
+
He2 molecule ion, Total no. of electrons = 3,
 Arrangement : s1s2, s* 1s1
 Unpaired electron, so paramagnetic
 BO = 1/2 (2-1) = 1/2
 Bond existing by virtue of a single electron.
He2 molecule. Total No. of electrons = 4,
 Arrangement : s1s2, s* 1s2
 Diamagnetic BO = 0
 Molecule does not exist.
Example: Which diatomic molecule of second period besides O2 should be paramagnetic?
Solution:

As, paramagnetism arises due to unpaired electron. Therefore B2is paramagnetic molecule.

M.O. of Some Diatomic Heteronuclei Molecules

The molecular orbitals of heteronuclei diatomic molecules should differ from those of homonuclei
species because of unequal contribution from the participating atomic orbitals. Let’s take the example
of CO.
The M.O. energy level diagram for CO should be similar to that of the isoelectronic molecule N2. But C &
O differ much in electronegativity and so will their corresponding atomic orbitals. But the actual MO for
this species is very much complicated since it involves a hybridisation approach between the orbital of
oxygen and carbon.

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HCl Molecule: Combination between the hydrogen 1s A.O’s. and the chlorine 1s, 2s, 2p & 3s orbitals can
be ruled out because their energies are too low. The combination of H 1s1 and 3p1x gives both bonding
and anti-bonding orbitals, and the 2 electrons occupy the bonding M.O. leaving the anti-bonding MO
empty.
NO Molecule: The M.O. of NO is also quite complicated due to energy difference of the atomic orbitals
of N and O.
As the M.O.’s of the heteronuclei species are quite complicated, so we should concentrate in knowing
the bond order and the magnetic behaviour.

Molecules/Ions Total No. of Electrons Magnetic Behaviour

CO 14 Diamagnetic

NO 15 Paramagnetic

NO+ 14 Diamagnetic

NO– 16 Diamagnetic

CN 13 Paramagnetic

CN– 14 Diamagnetic

Inert Pair Effect

Heavier p-block and d-block elements show two oxidation states. One is equal to group number and
second is group number minus two. For example Pb(5s25p2) shows two OS, +II and +IV. Here +II is more
stable than +IV which arises after loss of all four valence electrons. Reason given for more stability of +II
O.S. that 5s2 electrons are reluctant to participate in chemical bonding because bond energy released
after the bond formation is less than that required to unpair these electrons (lead forms a weak covalent
bond because of greater bond length).
Example: Why does PbI4 not exist?
Solution: Pb(+IV) is less table than Pb(+II) due to inert pair effect and therefore Pb(+IV) is reduced to
Pb(+II) by I– which changes to I2(I– is a good reducing agent)

Covalent Character in Ionic Compounds

Fajan's Rule
Although atomic bond in a compound like M+X- is considered to be 100% ionic, actually it also has some
covalent character. An explanation for the partial covalent character of an ionic bond has been given by
Fajan. According to Fajan, if two oppositely charged ions are brought together, the nature of the bond
between them depends upon the effect of one ion on the other.
When two oppositely charged ions (say A+ and B- ) approach each other the positive ion attracts
electrons on the outermost shell of the anion and repels its positively charged nucleus. This results in

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the distortion,deformation or polarization of the anion. If the polarization is quite small, an ionic bond is
formed, while if the degree of polarization is large, a covalent bond results.
Thus the power of an ion (cation) to distort the other ion is known as its polarization power and the
tendency of the ion(anion) to get polarized by the other ion is known as its polarisability. Greater the
polarization power or polarisability of an ion, greater will be its tendency to form a covalent bond.
The polarising power, or polarisability and hence formation of covalent bond is favoured by the
following factors:
 Small Positive Ion (Cation): Due to greater concentration of positive charge on a small area, the
smaller cation has high polarising power. This explains why LiCl is more covalent than KCl.
 Large Negative Ion (Anion): The larger the anion, the greater is its polarisability, i.e.
susceptibility to get polarised. It is due to the fact that the outer electrons of a large anion are
loosely held and hence can be more easily pulled out by the cation. This explains why iodides,
among halides, are most covalent in nature.
 Large Charge on Either of the Two Ions: As the charge on the ion increases, the electrostatic
attraction of the cation for the outer electrons of the anion also increases, with the result its
ability for forming the covalent bond increases. Thus covalency increases in the order : Na+ Cl-,
Mg2+ (Cl2)2-, Al3+ (Cl3)3 -
 Electronic Configuration of the Cation : For the two ions of the same size and charge, one with
a pseudo noble gas configuration (i.e., 18 electrons in outer-most shell) than a cation with noble
gas configuration (i.e. 8 electrons in outermost shell) will be more polarising. Thus copper (I)
chloride is more covalent than sodium chloride although Cu+ ion (0.96A°) and Na+ ion (0.95A°)
have same size and charge.
The orbital overlapping involved in covalency reduces, the charge on each ion and so weakens the
electrovalent forces throughout the solid, as is evident from the melting point of lithium halides.
LiF = 870°C LiCl = 613°C
LiBr = 547°C LiI = 446°C
From the above discussion, we find that greater the possibility of polarisation, lower is the melting
point and heat of sublimation and greater is the solubility in non-polar solvents.
Example: The melting point of KCl is higher than that of AgCl though the crystal radii of Ag+ and K+ ions
are almost the same.
Solution : Now whenever any comparison is asked about the melting point of the compounds which
are fully ionic from the electron transfer concept it means that the compound having lower melting
point has got lesser amount of ionic character than the other one. To analyse such a question first find
out the difference between the 2 given compounds. Here in both the compounds the anion is the same.
So the deciding factor would be the cation. Now if the anion is different, then the answer should be
from the variation of the anion. Now in the above example, the difference of the cation is their
electronic configuration. K+ = [Ar]; Ag+ = [Kr] 4d10. This is now a comparison between a noble gas core
and pseudo noble gas core, the analysis of which we have already done. So try to finish off this answer.

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Percentage of Ionic Character
Every ionic compound having some percentage of covalent character according to Fajan’s rule. The
percentage of ionic character in a compound having some covalent character can be calculated by the
following equation.
The percent ionic character = Observed dipole moment/Calculated dipole moment assuming 100%
ionic bond × 100
Example: Dipole moment of KCl is 3.336 × 10–29 coulomb metre which indicates that it is highly polar
molecule. The interatomic distance between k+ and Cl– is 2.6 ×10–10 m. Calculate the dipole moment of
KCl molecule if there were opposite charges of one fundamental unit located at each nucleus. Calculate
the percentage ionic character of KCl.
Solution: Dipole moment μ = e × d coulomb metre
For KCl d = 2.6 × 10–10 m
For complete separation of unit charge
e = 1.602 × 10–19 C
Hence μ = 1.602 × 10–19 × 2.6 × 10–10 = 4.1652 × 10–29 Cm
μKCl = 3.336 × 10–29 Cm
∴ % ionic character of KCl = 3.336×10–29/4.165×10–29 = 80.09%
Example. Calculate the % of ionic character of a bond having length = 0.83 Å and 1.82 D as it’s observed
dipole moment.
Solution: Tocalculate μ considering 100% ionic bond
= 4.8 × 10–10 × 0.83 × 10–8esu cm
= 4.8 × 0.83 × 10–18 esu cm = 3.984 D
∴ % ionic character = 1.82/3.984 × 100 = 45.68
The example given above is of a very familiar compound called HF. The % ionic character is nearly
43.25%, so the % covalent character is (100 – 43.25) = 56.75%. But from the octet rule HF should have
been a purely covalent compound but actually it has some amount of ionic character in it, which is due
to the electronegativity difference of H and F. Similarly knowing the bond length and observed dipole
moment of HCl, the % ionic character can be known. It was found that HCl has 17% ionic character. Thus
it can be clearly seen that although we call HCl and HF as covalent compounds but it has got appreciable
amount of ionic character. So from now onwards we should call a compound having more of ionic less of
covalent and vice versa rather than fully ionic or covalent.

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Metallic and Hydrogen Bonding

Table of Content
 Metallic Bonding
o Hydrogen Bonding
o Conditions for Hydrogen Bonding
o Types of Hydrogen Bonding
o Importance of Hydrogen Bonding in Biological Systems
o Effect of Hydrogen Bonding

Metallic Bonding
Metals are characterised by bright, lustre, high electrical and thermal conductivity, malleability, ductility
and high tensile strength. A metallic crystal consists of very large number of atoms arranged in a regular
pattern. Different model have been proposed to explain the nature of metallic bonding two most
important modules are as follows

The electron sea Model In this model a metal is assumed to consist of a lattice of positive ion (or
kernels) immersed in a sea of mobile valence electrons, which move freely within the boundaries of a
crystal. A positive kernel consists of the nucleus of the atom together with its core on a kernel is,
therefore, equal in magnitude to the total valence electronic charge per atom. The free electrons shield
the positively charged ion cores from mutual electrostatic repulsive forces which they would otherwise
exert upon one another. In a way these free electrons act as ‘glue’ to hold the ion cores together.
The forces that hold the atoms together in a metal as a result of the attraction between positive ions
and surrounding freely mobile electrons are known as metallic bonds.
Through the electron sea predated quantum mechanics it still satisfactorily explains certain properties of
the metals. The electrical and thermal conductivity of metals for example, can be explained by the
presence of mobile electrons in metals. On applying an electron field, these mobile electrons conduct
electricity throughout the metals from one end to other. Similarly, if one part of metal is heated, the
mobile electrons in the part of the metals acquire a large amount of kinetic energy. Being free and

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mobile, these electrons move rapidly throughout the metal and conduct heat to the other part of the
metal.
On the whole this model is not satisfactory.
Hydrogen Bonding
An atom of hydrogen linked covalently to a strongly electronegative atom can establish an extra
weak attachment to another electronegative atom in the same or different molecules. This attachment
is called a hydrogen bond. To distinguish from a normal covalent bond, a hydrogen bond is represented
by a broken line eg X – H…Y where X & Y are two electronegative atoms. The strength of hydrogen bond
is quite low about 2-10 kcal mol–1 or 8.4–42 kJ mol–1 as compared to a covalent bond strength 50–100
kcal mol–1 or 209 –419 kJ mol–1
Conditions for Hydrogen Bonding
Hydrogen should be linked to a highly electronegative element.
The size of the electronegative element must be small.
These two criteria are fulfilled by F, O, and N in the periodic table. Greater the electronegativity and
smaller the size, the stronger is the hydrogen bond which is evident from the relative order of energies
of hydrogen bonds.
Types of Hydrogen Bonding
Intermolecular hydrogen bonding:This type of bonding takes place between two molecules of the same
or different types. For example,
H H H
| | |
O—H—O—H—O—H—
Intermolecular hydrogen bonding leads to molecular association in liquids like water etc. Thus in water
only a few percent of the water molecules appear not to be hydrogen bonded even at 90°C. Breaking of
those hydrogen bonds throughout the entire liquid requires appreciable heat energy. This is indicated in
the relatively higher boiling points of hydrogen bonded liquids. Crystalline hydrogen fluoride consists of
the polymer (HF)n. This has a zig-zag chain structure involving
H-bond.

Intramolecular hydrogen bonding: This type of bonding occurs between atoms of the same molecule
present on different sites. Intramolecular hydrogen bonding gives rise to a closed ring structure for
which the term chelation is sometimes used. Examples are
o-nitrophenol, salicylaldehyde.

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Chemical Bonding

Importance of Hydrogen Bonding in Biological Systems

Hydrogen bonding plays a vital role in physiological systems. Proteins contain chains of amino acids. The
amino acid units are arranged in a spiral form somewhat like a stretched coil spring (forming a helix).
The N-H group of each amino acid unit and the fourth C=O group following it along the chain, establishes
the N–H---O hydrogen bonds. These bonds are partly responsible for the stability of the spiral structure.
Double helix structure of DNA also consists of two strands forming a double helix and are joined to each
other through hydrogen bond.
Effect of Hydrogen Bonding
Hydrogen bonding has got a very pronounced effects on certain properties of the molecules. They have
got effects on
 State of the substance
 Solubility of the substance
 Boiling point
 Acidity of different isomers
These can be evident from the following examples.
Example. H2O is a liquid at ordinary temperature while H2S is a gas although both O and S belong to the
same group of the periodic table.
Solution: H2O is capable of forming intermolecular hydrogen bonds. This is possible due to high
electronegativity and small size of oxygen. Due to intermolecular H-bonding, molecular association takes
place. As a result the effective molecular weight increases and hence the boiling point increases. So H2O
is a liquid. But in H2S no hydrogen bonding is possible due to large size and less electronegativity of S. So
it’s boiling point is equal to that of an isolated H2S molecule and therefore it is a gas.
Example.Ethyl alcohol (C2H5OH) has got a higher boiling point than dimethyl ether (CH3-O-CH3) although
the molecular weight of both are same.
Solution: Though ethyl alcohol and dimethyl ether have the same molecular weight but in ethyl alcohol
the hydrogen of the O-H groups forms intermolecular hydrogen bonding with the OH group in another
molecule. But in case of ether the hydrogen is linked to C is not so electronegative to encourage the
hydrogen to from hydrogen bonding.
—H—O—H—O—H—O—
| | |
C2H5 C2H5 C2H5
Due to intermolecular H-bonding, ethyl alcohol remains in the associated form and therefore boils at a
higher temperature compared to dimethyl ether.

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