Ionic Bonding Lecture Notes

CHEMISTRY LECTURE NOTES
CHEMISTRY
Chemical Bonding
LECTURE # 1 TO 12
CHEMICAL BONDING
LECTURE # 1
Starts from lattice energy (Ionic Bond)
IONIC BOND (ELECTROVALENT BOND) :

The chemical bond formed between two or more atoms as a result of transfer of one or more electrons
between them.
FAVOURABLE CONDITION :
(i)
One of the atom must be electro +ve can easily loose es or should have few more es than a noble gas. It
should have low .E value
(ii)
Other element should be a electro ve element having high .E. value, and more negative value of electron
gain enthalpy, having few es less than noble gas.
(iii)
Energy released because of the combination of cation and anion should be high.This energy is also defined
in terms of lattice enthalpy.
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. For example, the lattice enthalpy of NaCI is 788 kJ
mol-1. This means that 788 kJ of energy is required to separate one mole of solid NaCI into one mole of Na+1
(g) and one mole of Cl(g) to an infinite distance.
This process involves both the attractive forces between Ions of opposite charges and the repulsive forces
between ions of like charge. The solid crystal being three- dimensional; it is not possible to calculate lattice
enthalpy directly from the interaction of forces of attraction and repulsion only.
Factors associated with the crystal geometry have to be included.
Na+(g) + Cl(g) NaCl(s)
H = Hlattice ve (always)
2+
Mg (g) + 2Cl (g) MgCl2 (s)
FACTORS AFFECTING L.E.

(i)
(ii)
Lattice energy (L.E.)
1
r
r = r+ + r
= interionic distance
L.E. Z+, Z
Z+ charge on cation in terms electronic charge
Z charge on anion in terms electronic charge
(a) NaCl > KCl
(size)
(b) NaCl < MgO
(size, charge)
(c) NaCl < MgCl2
(size)
In size and charge, charge will dominate
Na2O > NaF
NaCl < Na2S
(d)
Al2O3 Na2O MgO

Al2O3 > MgO > Na2O
Note : Dont discuss melting point of ionic compound here.

CALCULATION OF L.E. :
Indirect methods : Born-Haber Cycle ( Hesss law)
Hesss Law the net enthalpy change of a chemical reaction or of any process always remain same
whether the reaction takes place in 1 step or many step
RESONANCE
CHEMICAL BONDING - 1
Born Haber Cycle for NaCl (s)
Na (s)
Hf
1 Cl (g)
2
2
1( H )
BE
2
Cl(g)
Hsub
Na(g)
HI.E.
NaCl(s)
HL.E.
HEg
Na (g) + Cl (g)
Hf enthalpy of formation of any compound is defined as the enthalphy change when 1 mol of that
compound is formed form the elements in their standard states
=
Hf
Hsub
+ve/ve
Generally
Q.
H.E.
+ve
+ve
1
H
2 BE
+ve
Heg
HL.E.
+ve/-ve
Born haber cycle for Al2O3(s)
2Al (s) +
Hsub
2Al(g)
HI.E
3
O (g) Hf
2 2
3 H
B.E
2
3O(g)
Heg
Al2O3(s)
HL.E
2Al (g)
3O (g)
HI.E
Heg
2+
2Al (g)
HI.E
3+
2Al (g) + 3O (g)
Hf = 2Hsub + 2 HI.E1 + 2 HI.E 2 + 2HI.E3 +

Q.
3
HBE + 3Heg1 + 3Heg2 + HL.E.
2
Born haber for NaBr
Na (s)
Hsub
Na(g)
HI.E.
1 Br ()
2
2
1
2
Hf
NaBr(s)
Hvap
1 Br (g)
2
2
1 H
B.E.
2
Br(g)
HEg
+
Na (g) + Br (g)
Ex.
MgO found as Mg2+O2 but not as Mg +O

Mg2+ O2 L.E. is very large (-ve)
Mg+O L.E. is ve
RESONANCE
General characteristics of ionic compounds :

(a) Physical state
(c) Conductance
(e) Brittlrness
(g) Isomorphism
(b) Melting and boiling points

(d) Crystal structure
(f) Solubility
Solvation or Hydration :
Whenever any compound generally ionic or polar covalent is dissolved in an polar solvent or in water then.,
different ions of the compound will get separated and will get surrounded by polar solvent molecules. This
process is known as solvation or hydration. Energy released in this process is known as solvation energy or
hydration energy
The ionic compound will be soluble only if solvation energy (H.E.) is more than the lattice energy
Factors affecting solvtion energy or hydration energy.
S.E.
Z+ Z
1
1
1
1
r r
(nature of solvent) where is dielectric constant.

r
Greater the polarity, greater will be r

r
r
1/ r , 11/r S.E.
H2O
81
CH3OH
34
C2H5OH
27
C6H6
34
Applications of Hydration energy :

(a)
(b)
(c)
Size of the hydrated ions: Greater the hydration of the ion greater will be its hydrated radii
Li+(aq) > Na+(aq)
Mobility of the ion: more is the hydration smaller will be the mobility of the ions
Li+(aq) < Na+(aq) < K+(aq) < Rb+(aq) < Cs+(aq).
Electrical conductance : is related to mobility so follows the same order
RESONANCE
LECTURE # 2
(d)
Solubility of ionic solids :

1
Now we have
L.E. r r
and
S.E.
1 1

r r
From these 2 equations, it can be mathematically proved that if the difference between the radii of Cation &
Anion is large then, solvation energy will dominate and if radii are comparable or difference is small, then
lattice energy will dominate
Greater the difference between radii, greater will be solubility
100 10
100 20
100 30
100 40
Cs F
>
Cs Cl
>
Cs Br
>
Cs
L.E.
1
110
1
120
1
130
1
140
1
1
1
1
1
1
1
1
100 10
100 20
100 30
100 40
decreament in solvation energy > decreament in lattice energy
S.E.
Solubility Orders.
Increase difference in radii
i.
LiF
ii.
NaF
iii.
LiF
iv.
CsF
Li
vi
Be(OH)2
vii
LiOH
viii
BeSO4
solubility and viceversa

increses
LiI
increase
Na
increase
CsF
decrease
Cs
decrease
Cs
increase
Ba(OH)2
increase
CsOH
decrease
BaSO4
white ppt
ix
LiClO4
CsClO4
decrease
Explain by Fazans rule, because of covalent character

x
BeF2
xi
AgF
Be2
Ag
solubility
decrease
decrease
Q.
NaF
Na[BF4]
which is more soluble
Ans.
Na[BF4] difference will
Q.
Ans.
Which is more soluble Cs3 or [N(CH3)4]+ 3

Cs3
Ex.
Predict the product of decomposition of given polyhalides
solubility
Rb+ [Cl2] RbCl + Cl
halide with stable lattice ( having ions of comparable radii) are produced
Li
Be
F
Na
Mg
Cl
Na+ < F K+
K
Ca
Br
K+ < Cl Rb+
Rb
Sr
Cs
Br
At
KCl + Br
K+ [Br Cl]
RESONANCE
(g)
Isomerism
onic compound does not show lsomerism due to non-directional nature of ionic bond
But onic compound can show
(h)
Polymorphism If an ionic compound is having two or more than two crystalline structures then it is said
to be polymorphus
CaCO3 Calcite form
Aragonite
Zns Zinc blende
Wurtzite
(i)
somorphism If two different ionic compounds are having similar crystalline structures then, these ar
known as Isomorphism to each other.
For two compounds to be isomorphus
both should have similar formula type eg FeSO4 .7H2O cannot be isomorphus of CuSO4.5H2O
Na2CO3
NaNO3 [Not isomorphus]
MgSO4.7H2O
FeSO4.7H2O
ZnSO4 .7H2O (Isomorphus)
The cations of both compound should be of similar shape or structure ( isostructural) similarly anions of both
compound should be isostructural
Ex.
MgCO3
CO32
NaNO3
NO3
trigonal planar
trigonal planar
Can be Isomorphus
Na2CO3
CO32
SP2
Na2SO3
SO32
SP3
(Not isomorphus)
:
S
C
O
BaSO4
SO42
Sp3
KMnO4
MnO4
Sp3
Mn
S
O
NaNO3
Sp2
O
NaClO4
Sp3
Cl
N
O
RESONANCE
[X]
O
O
COVALENT CHARACTER IN IONIC COMPOUNDS (FAJANS RULE) :
There is no compound which is 100% ionic.

Covalent character in ionic compound can be explained with the help of Fajans rule.
According to Fajans rules, covalent character will be more if
Cation
Anion
(i) Small size
(i) Large size
(ii) More charge
(ii) More charge
(iii) Pseudo inert gas configuration of cation
More distortion of anion, more will be polarisation then covalent character increases.
Factors affecting the polarisation :
(i)
Small size of cation polarisation.

e.g.
(ii)
BeCl2
MgCl2
Size of cation
Polarisation
Large size of anion polarisation
CaCl2
SrCl2
BaCl2
Covalent character
e.g.
(iii)
Charge on cation or anion polarisation.

(a) Charge on cation :
NaCl
MgCl2 AlCl3
Na+
Mg+2
Al+3
Charge of cation
Polarisation
Covalent character
(b) Charge on anion :
AlF3
Al2O3 AlN
F ,
O2 , N3
Charge on anion
Polarisation
Covalent character
(iv)
Cation which has pseudo inert gas configuration, shows more polarising power in comparison of cation that
has inert gas configuration. CuCl > NaCl (Covalent character)
Cu [Ne] 3s 2p 6 d10
Na 1s 2 ,2s 2p 6
18e
8e
Pseudo inert
inert gas configurat ion
gas configurat ion
RESONANCE
LECTURE # 3
Application & Exceptions of Fajans Rules :
Applications :
(i)
Ag2S is less soluble than Ag2O in H2O because Ag2 S is more covalent due to bigger S2 ion.
(ii)
Fe(OH)3 is less soluble than Fe(OH)2 in water because Fe+3 is smaller than Fe+2 and thus charge is more.
Fe(OH)3 is more covalent than Fe(OH)2 .
(iii)
The colour of some compound can be explained on the basis of polarisation of their bigger negative ions.
For ex : AgCl is white AgBr, Ag, Ag2CO3 are yellow
The bigger anions are more polarised.
and hence their electrons get excited by partial absorption of visible light
similarly, SnCl2 is white but Sn2 is red.

PbCl2 is white but Pb2 is yellow.
(iv)
(v)
Variation of M.P. [M.P. of covalent < M.P. of ionic] :

BeCl2 , MgCl2 , CaCl2, SrCl2, BaCl2
>
>
ionic charater , r+ ion & r ion = constant
CaF2 , CaCl2 , CaBr2 , Ca2
>
>
Covalent character M.P. r ion & r+ ion = constant
MP
Thermal stability of carbonates ionic character

Li2CO3 < Na2CO3 < K2CO3 < Rb2CO3 < Cs2CO3
Li2CO3 Li2O + CO2
COVALENT BOND :
Theories explaning the nature of covalent bond are as follows
g
M
g
g
Draw Lewis dot structures
Each bond Is formed as a result of sharing of an electron pair between the atoms.
Each combining atom contributes at least one electron to the shared pair.
The combining atoms attain the outer- shell noble gas configurations as a result of the sharing of electrons.
RESONANCE
TO DECIDE THE CENTRAL ATOM

(1) In general the least electronegative atom occupies the central position in the molecule/ion. For example
in the NF3 and CO32, nitrogen and carbon are the centra atoms whereas fluorine and oxygen occupy the
terminal positions.
(2) Generally the atom which is/are less in number acts as central atom
(3) Generally central atom is the atom which can form maximum number of bonds( which is generally equal
to the number of electrons present in the valence shell of the atom).
(4) Atom of highest atomic number or largest atom atom generally acts as central atom.
Hence we can say that Flourine and Hydrogen can never act as central atoms.
After accounting for the shared pairs of electrons for single bonds, the remaining electron pairs are either
utilized for multiple bonding or remain as the lone pairs. The basic requirement being that each bonded atom
gets an octet of electrons.
Limitations of the Octet Rule :
The octet rule, though useful, is not universal. It is quite useful for understanding .the structures of most of
the organic compounds and it applies mainly to the second period elements of the periodic table. There are
three types of exceptions to the octet rule.
1. The incomplete octet of the central atom
In some compounds, the number of electrons surrounding the central atom Is less than eight. This is especially
the case with elements having less than four valence electrons. Examples are LiCl. BeH2 and BCl3.
Li. Be and B have 1,2 and 3 valence electrons only. Some other such compounds are AlCl3 and BF3.
2. Odd-electron molecules
In molecules with an odd number of electrons like nitric oxide. NO and nitrogen dioxide. NO2, the octet rule
is not satisfied for all the atoms
Cl O 2
3. The expanded octet/ super octet / hypervalent compound
Elements in and beyond the third period of the periodic table have, apart from 3s and 3p orbitals, 3d orbitals
also available for bonding. In a number of compounds of these elements there are more than eight valence
electrons around the central atom. This is termed as the expanded octet. Obviously the octet rule does not
apply in such cases.
Some of the examples of such compounds are: PF5 SF6 , H2SO4 and a number of coordination compounds.
Interestingly, sulphur also forms many compounds in which the octet rule is obeyed. In sulphur dichloride,
the S atom has an octet of electrons around it.
4. Other drawbacks of the octet theory
It is clear that octet rule is based upon the chemical Inertness of noble gases. However, some noble gases
(for example xenon and krypton) also combine with oxygen and fluorine to form a number of compounds like
XeF2 , KrF2 , XeOF2 etc.,
This theory does not account for the shape of molecules.
It does not explain the relative stability of the molecules being totally silent about the energy of a molecule.
RESONANCE
MODERN CONCEPT OF COVALENT BOND (VBT) :

Since the energy gets released when the bond is formed between two hydrogen atoms, the hydrogen molecule
is more stable than that of isolated hydrogen atoms. The energy so released is called as bond enthalpy,
which is corresponding to minimum in the curve depicted in Fig. 4.8. Conversely. 435.8 kJ of energy is
required to dissociate one mole of Hg molecule.
H2(g) + 435.8 kJ mol H(g) + H(g)
Fig. The potential energy curve for the formation of H2 molecule as a function of internuclear distance of the
H atoms. The minimum in the curve corresponds to the most stable state of H2 .
Orbital Overlap Concept :
In the formation of hydrogen molecule, there is a minimum energy state when two hydrogen atoms are so
near that their atomic orbltals undergo partial interpenetration. This partial merging of atomic orbitals is
called overlapping of atomic orbitals which results in the pairing of electrons. The extent of overlap decides
the strength of a covalent bond. In general, greater the overlap the stronger is the bond formed between two
atoms. Therefore, according to orbital overlap concept, the formation of a covalent bond between two atoms
results by pairing of electrons present In the valence shell having opposite spins.
Main points of valency bond theory :
(i) A covalent bond is formed by partial overlapping of two atomic orbitals
(ii) More is the extent of overlapping between the two atomic orbital, stronger will be bond.
<
<
[Principal Quantum no. same, n = 2]
()
()
()
s orbital are spherical in nature so they are least diffused hence it will provide less area for overlapping.
(iii) Orbitals which are undergoing overlapping must be such that

(a) Each orbital should have one electron with opposite spin
(for formation of covalent bond)
(b) One orbital have pair of electron and the other orbital have no electron
(for formation of co-ordinate bond)
(iv) If the overlapping is along the molecular axis then bond will be sigma () & in the perpendicular direction,
it will be pi() bond.
RESONANCE
Examples of overlapping of pure atomic orbitals.

(i) H2 (ss)
H=
H=
(ii) HCl gas molecule (s-p)
(iii) F2, Cl2, Br2, 2 (p-p)

F2
2p-2p
Cl2
3p-3p
Br2
4p-4p
2
5p-5p
Strength of Sigma and pi Bonds :

Basically the strength of a bond depends upon the extent of overlapping- In case of sigma bond, the overlaping
of orbitals takes place to a larger extent. Hence, it is stronger as compared to the pi bond where the extent
of overlapping occurs to a smaller extent. Further, it is important to note that pi bond . between two atoms is
formed in addition to a sigma bond. It is always present in the molecules containing multiple bond (double or
triple bonds)
Overlapping of Atomic Orbitals :
When two atoms come close to each other. there is overlapping of atomic orbitals. This overlap may be
positive, negative or zero depending upon the properties of overlapping of atomic orbitals. The various
arrangements of s and p orbitals resulting in positive, negative and zero overlap are depicted in Fig. 4.9.
Following overlappings are not allowed.

(A) Zero overlapping :
(a)
(i)
(ii) Also in an s-orbital, is positive throughout but in p-orbital it is positive and negative
(b)
Total overlapping will zero
this type of overlapping is not allowed.

Because it is neither along the molecular axis nor to it.
(B)
Negative overlapping :
not allowed
not allowed
not allowed
Q.
Ans.
Count the & bonds in

6&5
RESONANCE
N C C C C N
LECTURE # 4
VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR) THEORY
As already explained, Lewis concept is unable to explain the shapes of molecules. This theory provides a
simple procedure to predict the shapes of covalent molecules. Sidgwick and Powell in 1940, 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 redefined by Nyholm and Gillespie (1957).
The main postulates of VSEPR theory are as follows :
The shape of a molecule depends upon the number of valence shell electron pairs [bonded or nonbonded)
around the central atom.
Pairs of electrons in the valence shell repel one another since their electron clouds are negatively charged.
These pairs of electrons tend to occupy such positions in space that minimise repulsion and thus maximise
distance between them.
The valence shell is taken as a sphere with the electron pairs localising on the spherical surface at
maximum distance from one another.
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.
Where two or more resonance structures can represent a molecule, the VSEPR model is applicable to any
such structure.
The repulsive interaction of electron pairs decrease in the order:
Lone pair (lp) - Lone pair (Ip) > Lone pair (Ip) - Bond pair (bp) > Bond pair (bp) - Bond pair (bp)
Nyholm and Gillespie (1957) refined theVSEPR model by explaining the important difference between the
lone pairs and bonding pairs of electrons. While the lone pairs are localised on the central atom, each
bonded pair is shared between two atoms. As a result, the lone pair electrons in a molecule occupy more
space as compared to the bonding pairs of electrons. This results in greater repulsion between lone pairs of
electrons as compared to the lone pair - bond pair and bond pair - bond pair repulsions. These repulsion
effects result in deviations from idealised shapes and alterations in bond angles in molecules.
For the prediction of geometrical shapes of molecules with the help of VSEPR theory. it is convenient to
divide molecules into two categories as (i) molecules in which the central atom has no lone pair and (ii)
molecules in which the central atom has one or more lone pairs. Table shows the arrangement of electron
pairs about a central atom A (without any lone pairs) and geometries of some molecules/ions of the type AB.
Next Table shows shapes of some simple molecules and ions in which the central atom has one or more
lone pairs. Next Table explains the reasons for the distortions in the geometry of the molecule. As depicted
in first Table, in the compounds of AB2 , AB3 , AB4 , AB5 and AB6 , the arrangement of electron pairs and the
B atoms around the central atom A are : linear, trigonal planar, tetrahedral, trigonal-bipyramidal and octahedral,
respectively. Such arrangement can be seen in the molecules like BF3 (AB3) , CH4(AB4) PCl5 as depicted
below by their ball and stick models.
RESONANCE
Fig. 4.6 The shapes of molecuies in which central atom has no lone pair
Table 4.7 Shape (geometry) of Some Simple Molecules/Ions with Central Ions having One or More Lone
Pairs of Electrons (E).
RESONANCE
Table 4.8 Shapes of Molecules containing Bond Pair and Lone Pair
RESONANCE
The VSEPR Theory is able to predict geometry of a large number of molecules, especially the compounds
ofp-block elements accurately. It is also quite successful in determining the geometry quite-accuralely even
when the energy difference between possible structures is very small. The theoretical basis of the VSEPR
theory regarding the effects of electron pair repulsions on molecular shapes is not clear and continues to be
a subject of doubt and discussion.
Directional Properties of Bonds :
As we have already seen the formation of covalent bond depends on the overlapping of atomic orbitals. The
molecule of hydrogen is formed due to the overlap of 1s-orbitals of two H atoms, when they combine with
each other.
In case of polyatomic molecules like CH4 , NH3 and H2O the geometry of the molecules is also important in
addition to the bond formation. For example why is it so that CH4 molecule has tetrahedral shape and HCH
bond angles are 109.5 ? Why is the shape of NH3 molecule pyramidal ?
The valence bond theory explains the formation and directional properties of bonds in polyatomic molecules
like CH4 , NH3 and H2O, etc. in terms of overlap and hybridisation of atomic orbitals.
RESONANCE
LECTURE # 5
NEED OF NEW CONCEPT (HYBRIDISATION) :
The valance bond theory (overlapping concept) explains satisfactorily the formation of various molecules but
it fails to account the geometry and shapes of various molecules. It does not give the explanation why BeCl2
is linear , BF3 is planar, CH4 is tetrahedral , NH3 is pyramidal and water is V shaped molecule.
In order to explain these cases , the valance bond theory has been supplemented by the concept of hybridization. This is a hypothetical concept and was introduced by Pauling & Slater.
Let us first consider the CH4 (methane) molecule. The electronic configuration of carbon in its ground state is
[He]2s2 2p2 which in the excited stale becomes [He] 2s1 2px1 2px1 2px1. The energy required for this excitation
is compensated by the release of energy due to overlap between the orbitals
of carbon and the hydrogen.The four atomic orbitals of carbon, each with an unpaired electron can overlap
with the 1 s orbitals of the four H atoms which are also singly occupied. This will result in the formation of tour
C H bonds. It will , however , be observed that while the three p orbitals of carbon are at 90 to one another,
the HCH angle for these will also be 900 That Is three C H bonds will be oriented at 900 to one another. The
2s orbital of carbon and the 1s orbital of H are spherically symmetrical and they can overlap in any direction.
Therefore the direction of the fourth C H bond cannot be ascertained. This description does not fit in with the
tetrahedral HCH angles of 109.5. Clearly, it follows that simple atomic orbital overlap does not account for
the directional characterisics of bonds in CH4 . Using similar procedure and arguments, it can be seen that in
the case of NH3 and H2O molecules, the HNH and HOH angles should be 90. This is in disagreement with
the actual bond angles of 1070 and 104.5 in the NH3 and H2O molecules respectively.
Hybridisation
(i)
(ii)
(iii)
(iv)
(v)
Inter Mixing of pure atomic orbitals before bonding to produce new hybrid orbitals, specially for bonding
purpose
Postulates
It is a hypothetical concept
Only those orbitals can take part in hybridisation which have comparable ( almost equal ) energies. So,
orbitals must be having same principal quantum number or these can be a maximum different of unity (if d
orbitals are involved)
The number of hybrid orbitals generated will be equal to the number of pure atomic orbitals taking part in
hybridisation.
All three type of orbitals (having a pair of e s or having a unpaired e or completely empty can take part in
hybridisation.
empty orbitals are used in coordination compounds
The hybrid orbital generated will be represented by
nucleus
bigger lobe will

be used for bonding
(vi)
Since hybrid orbitals have been generated for the bonding purpose. So, bond formed by a hybrid orbitals are
stronger than bond formed by pure atomic orbitals
(vii)
The orientations of hybrid orbitals generated will be dependent on type of atomic orbitals and on number of
atomic orbitals taking part in hybridisation
s+p
2 new sp hybridised orbitals

(sp hybridisation)
s +2p 3 new sp2 hybridised
(sp2 hybridisation)
s + 3p
4 new sp3 hybridised
s + 3p + d sp3d
s + 3p + 2d sp3d2
s + 3p + 3d sp3 d3
d + s + 2p dsp2
RESONANCE
The orientation of hybridised orbitals will be such that there will be minimum repulsion between any two
hybridised orbitals
s + p s + px
Yaxis
SP
s + pY
x axis
180
120
s + 2p s + px + py
in x - y plane
s + py + pz in y z plane
s + px + pz in x z plane
sp3 s + px + py + pz directed along the 4 corners of tetrahedron
(viii)
hybridised orbitals will be generally used for making bond and for bond pure p-orbitals will be used
2
sp -sp bond
(unstable)
Calculation of state of Hybridisation :

Steric number rule
Steric number of any atom in a molecule = number of atoms bonded to an atom + number of lone pair left on
the atom after bonding
S.N = 2
SP.
S.N. = 3
SP2
S.N. = 4
SP3
S.N. of central atom will decide the shape or structure of the molecule
Ex.
(a) CO2
(S+Px+Pz)
:
:O
(SP2)
S.N. = 3
S.N of C=2
O:
S.N. = 3 (SP2)
SP
(S+Px)
RESONANCE
(S+Px+Py)
xy plane
py
(xy)
(xz)
:
x axis
x-z
plane
(s + px + pz)
(s + px+ py)
(s + px)
F
(b)
SF6
F S F
F
F
S.N. = 4(SP )
S.N. = 6
(SP3d2)
F
2
S.N = 3 (SP)
(c)
S.N.= 4 (SP)3
2
S.N = 3 (SP )
SO2
:O
(d)
<120
:
O
: :
S.N = 3(SP )
S.N = 3 (SP )
120
S.N = 3(SP )
N:
:C
(f)
: :
SO3
(e)
S.N = 2
.x
Or
S.N + 2 (SP)
: C N:
(SP)
Out of C & N less E.N. element i.e C will donate its .P.
CN
(g)
NH3
H H
S.N = 4 (SP )
(h)
NH4+
H
S.N = 4 (SP3)
H H
sp hybridisation :
This type of hybridisation involves the mixing of one s and one p orbital rcsull.ingin the formation of two
equivalert sp hybrid orbitals. The suitable orbiials for sp hybridisation are s and pz , if the hybrid orbitals arc to
lie along the z-axis. Each sp hybrid orbitals has 50% s-character and 50% p-character. Such a molecule in
which the central atom is sp-hybridised and linked directly to two other central atoms possesses linear
geometry. This type of hybridisation is also known as diagonal hybridisation.
The two sp hybrids point in the opposite direction along the z-axis with projecting positive lobes and very
small negative lobes, which provides more effective overlapping resulting in the formation of stronger bonds.
Example of a molecule having sp hybridisation
BeCl2 : The ground state electronic configuration of Be is 1s2 2s2. In the exited state one of the 2s-electrons
is promoted to vacant 2p orbital to account for its divalency. One 2s and one 2p-orbitals get hybridised to
form two sp hybridised orbitals. These two sp hybrid orbitals are oriented in opposite direction forming an
angle of 180. Each of the sp hybridised orbital overlaps with the 2p-orbital of chlorine axially and form two
Be-Cl sigma bonds. This is shown in Fig
RESONANCE
Fig.4.10 (A) Formation of sp hybrids from s and p orbitals ; (B) Formation of the linear BeCl2 molecule.
Examples of SP hybridisation.
C
(a)
H C N,
HC CH
O=C=O
H2C = C = CH2
(b)
SP
=C=
Q.
Will all the 4 H atom in propadiene be coplanar

H spxp z spx sp xp y H
Cp C C
y
Pz
H
H
xz
xy
(f)
BeCl2(g)
: Cl
Be
: :
NO
: :
Ans.
Cl :
S.N = 2
(SP)
In solid state, BeCl2 is formed in form of polymer (BeCl2)n
Cl
Cl
Be
Be
Cl
Be
Cl
Cl
Cl
Be
Cl
Cl
Be
Cl
S.N = 4 (SP3)
Bond angle 90 95
(g)
N2
:N
N:
S.N = 2 (SP)
(h)
Azide ion N3
x.
:N
:N
.x
N:
x.
:N
N:
N:
N3 (nitride ion)
N = N = N
SP
In azide ion, both NN bond lengths are equal and it is a linear ion.
RESONANCE
Hydroazoic acid (HN3)
(i)
+
N
N
120 H
Its a bent molecule
2 N N bond length are not equal as in one bond there is extra electrostatic attraction which the bond
length.
It will be planar molecule
Q.
CH3CN is a weaker lewis base than CH3NH2
Sol.
CH3 C N :
:
H 3C
N
H
SP
SP
Nsp > N 3
sp
E.N order
more E.N., lesser will be tendency to donate the l.p.
LECTURE # 6
sp2 hybridisation :
In this hybridisation there is involvement of one s and two p-orbitals in order to form three equivalent sp2
hybridised orbitals.
For example, in BCl3 molecule , the ground state electronic configuration of central boron atom is 1s2 2s2 2p1.
In the excited state, one of the 2s electrons is promoled to vacant 2p orbital as
Fig.4.11 Formation of sp2 hybrids and the BCl3 molecule

a result boron has three unpaired electrons. These three orbltals (one 2s and two 2p) hybridise to form three
sp2 hybrid orbitals. The three hybrid orbitals so formed are oriented In a trigonal planar arrangement and
overlap with 2p orbitals of chlorine to form three B Cl bonds. Therefore, in BCl3 (Fig.4.11), the geometry is
trigonal planar with CIBCl bond angle of 120.
RESONANCE
OTHER EXAMPLES :
B
AB3
trigonal planer
120
BF3, C6H6, CO32 , B(OH)3, SO3, NO3 ,+CH3, graphite,
:
A
ALB2
(f)
Bent molcule
Allotropes of carbon :
1.
Graphite - sp2
2.
SO2, SnCl2, NOCl, O3, NO2
Diamond - sp3
3.
Fullerene - sp2 and sp3
Graphite
each C sp2
has 1 e in pure P orbital

because of this graphite is a sheet like structure (planar structure) .
the unpaired e will be used for bond formation. These bonded e will delocalised in whole of the layer
1.40 A
3.40 A
The structure of a
graphite sheet
C - C B.L in sheet = 1.40 A (benzene)
Q.
Ans.
Graphite is anisotropic with respect to electrical conductivity.

Graphite is good conductor of electricity along the layer because of delocalised electrons and poor conductor of electricity perpendicular to the layer because of large distance between the layers. On increasing
temperature conductivity increases perpendicular to the layer and decreases along the layer. Therefore it
behaves as semiconductor as well as conductor.
Q.
Ans.
Graphite is consider as diamagnetic substance.

Since e are paired due to delocalised -bond. So it is diamagnetic in nature (repelled in to the magnetic
field)
Q.
Ans.
Graphite is used as lubricants.

Attraction force between 2 layers is vanderwaal attraction force. So, layess can slide over each other. So, it
is solt lubricating substance.
Fullerenes (C60 , C48 , C30 ...........)

foot ball like spherical balls of C
Most of the C atom are bonded 3 other C atoms so, these will be sp2 hybridised.
This structure is made up of alternate pentagons and hexagons.
And Because of this all the double bond cannot be in conjugation. Hence, 2 different type of B.L. are present
in fullerenes one is C C single B.L. and the other is CC partial double bond length.
Bucky ball (C60)
RESONANCE
Structure of
buckminster fullerence
BORON TRIHALIDES
BF3
BCl 3
BBr3
sp
sp
sp
B 3
unstable
(stearic h indrance )
Discuss the structure and hybridisation inorganic benzene B3N3H6 borazine
H
N
N
H
Q.
How many dichloro borazine are possible ?
Cl
N
N
B
B
N
Cl
Inorganic benzene is chemically more reactive in comparison to benzene because N B bond is polar in
nature while in all the bonds are non-polar
HCl + C6H6 no. chemical reactions.
HCl + B3N3H6 B3N3H9 Cl3
3
H
H
Cl
sp
Cl
B
N
H
H
H
H
Cl
H
sp3 hybridisation :
This type of hybridisation can be explained by taking the example of CH4 molecule in which there is mixing
of one s-orbital and three p-orbitals of the valence shell to form four sp3 hybrid orbital of equivalent energies
and shape. There is 25% s-character and 75% p-character in each sp3 hybrid orbital. The four sp3 hybrid
orbitals so formed are directed towards the four corners of the tetrahedron. The angle between sp3 hybrid
orbital is 109.5 as shown in Fig. 4.12.
RESONANCE
The structure of NH3 and H2O molecules can also be explaned with the help of sp3 hybridisation. In NH 3 , the
valence shell (outer) electronic configuration of nitrogen in the ground state is 2s2 2px1 2py1 2pz1 having three
unpaired electrons in the sp3 hybrid orbitals and a lone pair of electrons is present in the fourth one. These
three hybrid orbitals overlap with Is orbitals of hydrogen atoms to form three N-H sigma bonds. We know that
the force of repulsion between a lone pair and a bond pair is more than the force of repulsion between two
bond pairs of electrons. The molecule thus gets distorted and the bond angle is reduced to 107 from 109.5.
The geometry of such a molecule will be pyramida as shown in Fig. 4.13.
Fig.4.13 Formation of NH3 molecule

In case of HgO molecule, the four oxygen orbitals (one 2s and three 2p) undergo sp3 hybridisation forming
four sp1 hybrid orbitals out of which two contain one electron each and the other two contain a pair of
electrons. These four sp3 hybrid orbitals acquire a tetrahedral geometry, with two corners occupied by hydrogen atoms while the other two by the lone. pairs. The bond angle in this case is reduced to 104.5 from
109.5 (Fig. 4.14) and the molecule thus acquires a V-shape or angular geometry.
Fig .4.14 Formation of H2O molecule
RESONANCE
Examples of sp3 hybridisation

AB4
tetrahedral
shape
AB3L
pyramidal
AB2L2
V shape
(bent)
ABL3
Linear
Example
CH4 (109 28)
B
<109
B 28'
..
NH3 (107)
B <109 28' B
H2O(1045)
ClO
..
Cl
.. O
..
l.p b.p. > b.p b.p.
..
A
.. B
..
..
A
109 28'
..
Compounds of berillium
1.
[BeF4] (sp3 hybridised) (already taught)
Tetraflouroberrylate (ii) ion
2.
BeCl2(s)
(BeCl2)n polymeric solid (already taught)
Cl
Cl
Cl
Be
Cl
Cl
Cl
Be
Be
Cl
S.No. = 4 sp3
Cl
Compounds of Boron, Aluminium :

[B(OH)4], [BF4], [H3 N : BF3]
3
sp
sp
AlCl3 anhydrous exist in dimer form Al2Cl6
Crystaline AlCl3 or Hydrated AlCl3 [Al(H2O)6]Cl3
Al(OH)4 , AlH4, AlCl4 are sp3
Borax Na2B4O7.10H2O
Borax anion [B4O5(OH)4]2
Compounds of Carbon :
All saturated organic compounds has C in sp3 hybridised state :
..
C H3
C
S.N = 4
3
sp
H
H
H
Diamond
Graphite is more reactive than diamond
Graphite
1500 C
Diamond
50,000 60,000 atm
Each C is bonded to 4 other C atoms.

sp3 hybridisation.
Each C C B. L. = 1.54 .
Since all the e s have taken part in bonding. so, are paired up. Hence it is diamegnetic and a bad conductor
of electricity.
The tetrahedran are linked together into a three-dimensional giant molecule. The unit cell is cubic. Strong
covalent bonds extend in all directions. Thus the melting point is abnormally high (about 3930C) and the
structure is very hard (In a rare modification of diamond.
RESONANCE
LECTURE # 7
Compounds of Silicon
Q.
CO2 is a gas but SiO2 is a high melting solid.

O=C=O
(discrete molecule)
O = Si = O
(unstable)
Si O Si
(stable)
(will form 3-D structure)
Elements forming Multiple bonds

C N O
P S Cl
SiO2 Covalently bonded 3D giant network solid like diamond.

O
Si
O
Si
O
O
O
Si
Si
O
Silicates (Si Sp3 hybridised)

Basic repeating unit of silicate [SiO4]4
O
Si
It is not O O bond
(there is no such bond)
O
O
O
Silicon atom
O O atom
CLASSIFICATION OF SILICATES :
(A)
Orthosilicates :
These contain discrete [SiO4]4 units i.e., there is no sharing of corners with one another as shown is figure.
(B)
Pyrosilicate :
In these silicates two tetrahedral units are joined by sharing oxygen at one corner thereby giving [Si2O7]6
units.
() charge will be present on the oxygen atoms which is bonded with one Si atom.
RESONANCE
(C)
Cyclic silicates :
If two oxygen atoms per tetrahedron are shared to form closed rings such that the structure with general
formula (SiO32)n or (SiO3)n2n is obtained, the silicates containing these anions are called cyclic silicates.
Si3O96 and Si6O1812 anions are the typical examples of cyclic silicates.
O
O
O
O
O
O
Si6O1812
Si3O96
(D)
Chain silicates :
Chain silicates may be further classified into simple chain & double chain compounds.
In case of simple chains two corners of each tetrahedron are shared & they form a long chain of tetrahedron.
Their general formula is also same as the cyclic silicates i.e. (SiO3)n2n
Similarly, double chain silicates can be drawn in which two simple chains are joined together by shared
oxygen. The anions of double chain silicates have general formula (Si4O11)n6n .
O
O
Compounds of P :
O
O
P4 (White phosphorus)
60
(P will be on all 4 vertexes of tetrahedron) (nothing at centre)
6PP bonds
PPP = 60
S.N. = 4 (10928)
Since B.A. is 60 so, P4 molecules is a strained molecule. Hence is chemically very reactive.
Can catch fire at normal room temperature in air.
RESONANCE
P4O6
no PP bond, 12 POP bond.

O
O
O
P4O10
OP O
O P
O
P4S3
Oxygen Family :
H2O
V-shaped molecule
H3O+ (hydronium ion)

Compounds of S :
S8 (Crown sulphur)
S32
SCl2
V-shaped
S2Cl2
open book like structure
SOCl2 (thionyl chloride) (derivative of SO2)
SO2Cl2 (sulphuryl chloride)
RESONANCE
Halogen family :
HClO4, HClO3, HClO2, HClO
Noble gases Family :
XeO4
Xenon tetraoxide
tetrahedral
XeO3
Xenon trioxide
Q.1
Ans.
pyramidal
Discuss the shape, geometry and bond angle of the following molecules.
NH3
H2O
O3
SO2
NH3 (Ammonia)
..
..
N
shape : pyramidal
H H H
Geometry : tetrahedral , bond angle = 107
:
S
B.A. < 120
118 O
O3 (Ozone)
:
O
O
:O
O:
:
O
O 117 O
Bond strength of both bond is equal diamagnetic substance. Ozonide ion (O3) from KO3 paramagnetic
substance.
unpaired e
:
O
: :
O2 Paramagnetic
(can be explained on the basis of MOT)
Q.2
Ans.
Compair the OO bond length in H2O2 and O2F2.

H2O2 (hydrogen peroxide)

O O BL is more than the expected.
O2F2
OO B.L. is smaller then H2O2 because of smaller electron density on O atom in comparison to H2O2.
RESONANCE
NOTE: If bond length in any molecule is found to be more than the expected then the main reason will be lone pair
lone pair( and lone pair lone pair repulsion is considered when both the bonded atoms are of
second period and both are having lone pairs on them) repulsion or decrement of electron density of
the bond may be because of sharing or donation
For example: H2O2, F2, NH2OH, NF3,
The carbon carbon bond length increases in many -bonded complexe which we will study in coordination
compounds. such as zeisses salt.
Q.3
Discuss the shape of NH2 (Amide ion) an
Ans.
.. ..
N
Vshaped like H2O molecule
H
H
NH2OH (Hydroxylamine)
..
N
H H
..
O
.. H
N O B.L. is larger than the expected (.p. .p. repulsion)

Order of base strength
NH3 > NH2 NH2 > NH2OH
STRUCTURE OF OXY ACIDS OF P, S, Cl, N

OXY-ACIDS OF PHOSPHORUS (P, atom is sp3 hybridised)
S. NO.
NAME
1.
H3PO2
Hypophosphorus acid (monobasic)
2.
H3PO3
Phosphorus acid (Dibasic)
3.
H4P2O6
Hypophosphoric acid (tetrabasic)
4.
H4P2O7
Pyrophospho ric acid ( tetrabasic )
STRUCTURE
or
Dipolyphos phoric acid
5.
H3PO4
Phosphoric acid (tribasic)
6.
H4P2O5
Pyrophosphorus acid
7.
HPO3
Metaphosphoric acid
RESONANCE
8.
9.
Cyclic-metaphosphoric
(HPO3)n
(n = 2)
Dimeta posphoric acid
n=3
Trimeta phosphoric acid
OXY-ACIDS OF SULPHUR
(S atom in sp3 hybridised)
A. Sulphurous acid series.
1.
2.
3.
H2SO3
Sulphurous acid
H2S2O4
Dithionous acid
H2S2O5
O
||
HOS
.. O H
O O
|| ||
H O S
. . S
. . O H
Pyrosulphurous acid
O O
|| ||
H O S S
. . O H
||
O
Sulphuric acid
O
||
H O S O H
||
O
Thiosulphuric acid
O
||
H O S O H
||
S
B. Sulphuric acid series.
1.
2.
H2SO4
H2S2O3
Oleum
O
O
||
||
HOS OSOH
||
||
O
O
3.
H2S2O7
C.
Thionic acid series (General formula H2Sn+2O6, n = 0 to 12 are practicaly known)

O
O
||
||
H O S (S )n S O H
||
||
O
O
H2S2O6 (n = 0)
RESONANCE
Dithionic acid
D.
Peroxy acids of S
1.
2.
H2SO5
H2S2O8
Peroxymonosulphuric acid (caros acid)
O
||
HO O S O H
||
O
Peroxydisulphuric acid (Marshalls acid)
O
O
||
||
HO S O O S O H
||
||
O
O
OXY-ACIDS OF Cl
(Cl atom is sp3 hybridised)
1.
HClO
Hypochlorous acid
2.
HClO2
Chlorous acid
3.
HClO3
Chloric acid
4.
HClO4
Perchloric acid
OXY-ACIDS OF NITROGEN
(N atom sp2 hybridised)
1.
HNO3
Nitric acid (Colourless)
2.
HNO2
Nitrous acid (Pale blue)
3.
H2N2O2
Hyponitrous acid
4.
HNO 4
or
HNO 2 (O 2 )
Pernitric acid
or
Peroxy nitric acid
5.
HNO(O2)
Peroxy nitrous acid
.. ..
RESONANCE
HO
. . N O
LECTURE # 8
Example of sp3d hybridisation :
(s + px + py + pz + dz2)
sp3d
Steric number = 5
molecular gemetry TBP
Bond angle
120 & 90
E axial
A
E
E
axial
E = equitorial position
(i) In this type of geometry, . p. or .ps will always occupy E positions.

(ii) the more negative atom occupies axial positions
(iii) since in this geometry, axial bonds are found to be slightly longer and weaker as composed to equitorial
bonds. Therefore db will always occupy equitorial positions
All the examples of this category can be classified into following 4 types.
Type
AB5
AB4L
AB3L2
AB2L3
Shape
TBP
see-saw
T-shape
Linear
Ex.
PF5 :
PF5
SF4
ClF3
XeF2
PCl5
XeO2F2
XeF3+
3
PBr5
Cl2
P5
PF5 is a gaseous molecule in which all the P-F BL are found to be equal which is due to continuous
exchange between the axial and equitorial F atoms at very highrate (1200 times per sec.)
Cl Cl
90
0
12 P
PCl5 :
Cl
net = 0
Cl
Cl
Two types of P-Cl BL

axial bonds are longer & weaker
PCl5 (g)
PCl3 (g) + Cl2(g)
PCl5 (s) consist of PCl4+ and PCl6
sp3
sp3d2
+
PBr5(s) consist of PBr4 and Br
P5(s) is expected to be P4+ and
Cl F
PF2Cl3
P
Cl
net = 0
Cl
F
P
PCl2F3
Cl
Cl
=0
F
AB4L
RESONANCE
SF4
Seasaw
F
F
F
Xe
XeO2 F2
Seasaw
O
F
AB3L2
F
Cl
ClF3
T-shaped
F
F
> 180
Due to .p. b.p. repulsions therefore FClF is not linear
+
[XeF3]+
Xe
F
F
It appear that all interhalogens of AB3 type where A is central halogen (not F) will have sp3d hybridisation on
A.
But it is found that Cl3 exists as a dimer 2Cl6 (bright yellow solid with the following structure.
Cl
Cl
Cl
Cl
Cl
Cl
On the basis of above structure must be in sp3d2 hybridisation state.
F
Xe
AB2 L3 XeF2
+
3+
S. No. = 4
sp3
bent
Cl
Cl2
Cl
RESONANCE
Q.
Select the correct structure of ClF3 amongs the following with proper reasoning.
Cl
(A)
(B)
F
Cl
(C*)
Example of sp3d2 hybridisation

S.N. = 6 geometry Octahedral
B.A. = 90
Types
AB6
Shape
Octhedral
Ex.
SF6
PF6
[SiF6]2
[AlF6]3
[XeO6]4
Perxenate ion
AB5L
sq. pyramidal
ICl4
XeOF4
BrF5
AB4L2
Sq. planar
XeF4
__
PF6
[SiF6]2-
S
SF6
[AlF6]3-
Si
F
2-
[XeO6]4
XeO3 + NaOH Na+[HXeO4]
Sodium Xenate
H2XeO4
S.N. = 5
Xenic Acid
Xe
sp3d
O
H
H4XeO6
Perxenic Acid
(No peroxide group)
Structure of [XeO6]4
4-
O
O
Xe
Xe
OR
O
O
O
RESONANCE
O
O
AB5L : BrF5
F
Br
..
Presence of 1 l.p. doesnot create any problem. It can be placed any where because all the 6 comes of the
octahedron are equivalents.
But in case of XeOF4 d.p. and .p. are kept at 180.
F
Xe
..
AB4L2 : Cl4
..
Cl
Cl
Cl4
=0
Cl
2.
..
Cl
l.p. of are found to be at trans position so as to have min. repulsion.

..
F
Xe
XeF4
=0
F
..
Examples of sp3d3 hybridisation

Type
Example
Shape
AB7
F7
Pentagonal bipyramidal
AB6L
XeF6
Distorted octahedral
F
F
90
F
72
Xe
F
F
But XeF6(s) is found to exist in tetrameric form when [XeF5]+ units are linked by F
RESONANCE
hyb of Xe in [XeF5]+ is found to be sp3d2

+
[XeF5]
Electrostatic Attraction
F
+
[XeF5]
[XeF5]
F
+
[XeF5]
BOND LENGTH (IT HAVE FOLLOWING SEQUENCE)

(i)
Size of atom (see along the group) bond length

HF < HCl < HBr < HI
F F < Cl Cl < Br Br <
CH4 < SiH4 < GeH4 < SnH4
(ii)
Multiplicity of bond (nearly same period element)

single bond > double bond > triple bond
CC > C=C > CC
FF > O=O > NN
(iii)
Electronegativity difference (See along the period)

HC > HN > HO > HF
HOW TO COMPARE BOND ANGLES

Ans.
Bond angle depends on the following factor

I.
Hybridisaition
II.
No. of lone pair
III.
Size or electronegativity of central atom
IV.
Size or electronegativity of terminal atom
1.
Hybridisaition :
sp > sp2 > sp3
180 120
10928
2.
No. of lone pair : If hybridisaition of the central atom is same but no. of lone pair is diffrent then
more in the lone pair len in the bond angle.
e.g.
CH4
NH3
H2O
hybridisaition
sp3
sp3
sp3
lone pair
.P. = 0
.P. = 1
.P. = 2
B.A.
10928
107
104
3.
Size or electronegativity of central atom : When hybridisation same no. of lone pair is same but
central atom is different then see the electronegativity of central atom. More is the electronegativity
more is the bond angle.
e.g.
NH3
PH3
AsH3
SbH3
hybridisaition
sp3
no
no
no
lone pair
.P. = 1
.P. = 1
.P. = 1
.P. = 1
B.A.
107
93
92
91
3
Note : But if we apply steric no. rule than all have sp hybridisation.
RESONANCE
Drago rule :
Element of 3rd period (p-Block) and lower than 3rd period does not allowed hybridisation in
molecule when they form compound with less electronegative elements such as hydrogen
eg :
PH3, SiH4, AsH3 , H2S not have hybridisation
4.
Size or electronegativity of terminal atom :

Hybridisation same, lone pair same, central atom same but terminal atom is different then greater is the size
of the terminal atom greater will be the bond angle. Only in case of flourine the electronegativity factor is
considered, due to greater electronegativity of the flourine atom the bond angle for it comes out to be
smallest( due to smaller bond bond pair repulsions)
e.g.
PF3
PCl3
PBr3
PI3
hybridisaition
sp3
sp3
sp3
sp3
lone pair
.P. = 1
.P. = 1
.P. = 1
.P. = 1
B.A.
98
100
101
102
Reasion : As the E.N. of x , b.p.b.p. repulsion will less but l.p. compression will work as usual
Q.4
Compair bond angle of OF2 and Cl2O.
Ans.
OF2
Cl2O
because of large size of Cl atom
Q.5
Discuss the bond angle in carbonyl halides COF2 , COCl2 , COBr2 , CO2
Ans.
Carbonyl Hallide
B.A. COF2 < COCl2 < COBr2 < CO2
Explanation
(A) double bonds require more room than single bonds. Hence C = O group compresses the molecule and
bond angle max. in COF2. Later on halogen atom becomes bigger and less (ve) also so
inter atomic repulsion between the halogens causes in B.L.
As X (halogen) becomes less and less (ve) b.p.-b.p. repulsion also becomes imp and therefore
Q.6
Ans.
Discuss the bond angle in Thionyl halide.

Thionyl hallides
E.N. of halogen
b.p. b.p. repulsion
l.p. on the S atom and more space required S = O grp will compress the molecule
SOF2 b.p b.p. repulsion min
SO Br2 b.p. b.p repulsion max.
RESONANCE
Q.7
Ans.
Discuss the basic strength and bond angle hydride of nitrogen family.
NH3
PH3
AsH3 SbH3
B.A.
107
92-93
92
91
l.p. availability on the centre atom
Lewis base strength
(Due to fact that l.p. on N in NH3 is in sp3 hybrid orbital which is more diffused and directional on the other
hand concept of hybridisation is not applicable in the rest of the molecules.
The l.p is present in a S orbital which is contracted and non-directional.
This observation that the members of nitrogen family( other than N) and members of Oxygen family( other
than O) do not use hybridised orbitals to make bond with hydrogen atom( or any atom with
electronegativity less than 2.1) is called Dragos rule.
Q.8
Comment on the bond angle of the following species.
Ans.
NO2
NO2
NO 2
[O = N = O]+
B.A.
Q.9
ONO
NO 2 < NO2 < NO 2

115
132 180
Compare bond angles in NOCl and NO3.

NOCl
NO 3
<
LECTURE # 9
Some special bonding situations:
(a) Electron deficient bonding:
There are many compounds in which some electron deficient bonds are present apart from normal covalent
bonds or coordinate bonds which are 2c-2e bonds( two centre two electron bonds). These electron deficient
bonds have less number of electrons than the expected such as three centre-two electron bonds(3c-2e)
present in diborane B2H6, Al2(CH3)6, BeH2(s), bridging metal carbonyls.
B2H6 (diborane) It is having (3centre 2electron) bond
(banana bond)
(electron deficient bond)
A
B
Single bond
(2c 2e) bond
3C 2e bond
H x
2
Ht
H
B
Hb
3C 2e bond
2 = 3c 2e
bond
4 = 2c 2e
bond
B.L.
y>x
B.L. of 3c 2e bond > B.L. of 2c 2e bond

2 > 1
B.A.
RESONANCE
Ht terminal H atom
Hb bridging H atom
B. A < Ht BHt > HbBHb
If all the 4 Ht are considered in one plane then, the 2 3c 2e bonds will not be in that plane. These will be in
a perpendicular plane.
If substitution (like chlorination) then Ht will be substituted only. Hb cannot be substituted with out breaking
the molecule.
(BeH2)n Polymeric solid.
Al2(CH3)6
Ga2(CH3)6
H H H
H3C
CH3
C
Al
Al
H3C
CH3
C
H
But Al2Cl6 hame covalent bond only no electron deficient bonding.

Cl
Cl
Al
Cl
Al
Cl
Cl
Cl
(b) Back Bonding:

Back bonding generally takes place when out of two bonded atoms one of the atom has vacant orbitals(
generally this atom is from second or third period) and the other bonded atom is having some non-bonded
electron pair( generally this atom is from the second period)
Back bonding increases the bond strength and decreases the bond length
* The extent of back bonding the much larger if the orbitals involved in the back bonding are of same size, for
example Back bonding in boron trihalides
BORON TRIHALIDES
BF3
BCl 3
BBr3
sp
sp
sp
B 3
unstable
(stearic h indrance )
Q.
Observed bond length in BF3 molecule in found to less than the expected.
Ans.
:F
There will be p - p back bonding between 2p of B atom & 2p of F atom. Bond length of B
- F will decreases
RESONANCE
Q.
Compare B-F bond length in BF3 and [BF4].
Ans.
BF3 + KF K + [BF4]
F
[No back bonding]
SP3 hybridised
B
F F F
BF Bond length (order) [BF4] > BF3

Q.
Ans.
Explain all boron trihalides are lewis acids also explain their order.
Boron trihalides are electron deficient molecules therefore act as a Lewis acids
Cl
But in BCl3
P -P back bonding 2p of B & 3p of Cl less effective
B
Cl
Cl
tendency to accept L.P in BCl3 > BF3. Lewis acid strength BF3 < BCl3 < BBr3.
* The extent of back bonding decreases if the atom having vacant orbitals is also having some non-bonded
electron pairs on it. So among the atoms of third period the extent of back bonding follows the order
Si > P > S > Cl
for example,
Q.
Trisilylamine is a planar molecular and does not act as a lewis base while trimethyl is a pyramidal and act as
lewis base
SiH3
N
|
CH3 CH CH3
3
S.N = 3
SiH3
SiH3
Planar
N (CH3)3 pyramidal
delocalised .P.
S.N. = 3 sp2
Localised .P.
sp3
S.No. = 4
But in a similar compound N(PH2)3 the shape is found to be pyramidal, so N atom must be sp3 hybridised
due to much less extent of back bonding into the vacant orbitals of P.
Silyl isocyanate (SiH3NCO) is linear but methyl isocyanate (CH3NCO) is bent explain !
Sol.
H
H
H
vacant
d-orbitals
.P. of N can be delocalised
(Back bonding)
S.N of N = 2 (sp)
p d back bonding.
RESONANCE
H
H
C N
H
No vacant
orbitals
Si
Q.
S.N = 3 (sp2)
(c) Hydrolysis
Hydrolysis means reaction with water molecules ultimately leading to breaking of O-H bond into H+ and OH
ions. While the term Hydration means the surrouding of and polar molecule or ions by polar molecules of
water.
Hydrolysis complex formation with water molecule or reaction with water molecule.
Hydration cluster formation by water molecule around the ion or molecule of solute.
Ionic compounds will under go hydrolysis st then hydration
Covalent compound mainly hydrolysis will takes place and negligible hydration.
Hydrolysis in covalent compounds takes place generally by two mechanisms
(a) By H-bond formation: As of Nitrogen Trihalides
(b) By Coordinate bond formation : Generally in halides of atoms having vacant d-orbitals or of halides of
atoms having vacant orbitals.
2nd period
LiCl
BCl3
Li+
C Cl4
NCl3
2s 2p sp3 hybridisation
H
OH2
Primary layer (hydrolysis)
Li
H2O
H2 O
OH
2
H
H
Be2+
H
(hydration) many such layer will
form.
2s 2p = sp3 hybridisation
LECTURE # 10
Hydrolysis via co-ordinate bond formation.
Hydrolysis of BCl3( due to presence of vacant orbitals on boron)
H
vacant pure Cl
p- orbital
B
Cl
Cl
OH
OH
B
+ HCl
OH
RESONANCE
Cl
H
O H
Cl
H2O
Cl
Cl
OH
B
+ HCl
Cl
Hydrolysis of boron trihalides :
Cl
Cl
undergo hydrolysis by coordinate
bond formation
Cl
Q.
B (OH)3 (Boric acid) + 3HCl
BF3 does not undergo complete hydrolysis

OR
Hydrolysis of BF3 is only partial ? Explain.
BF3 + 3H2O B(OH)3 + 3HF
But the produced HF will react with the reactant BF3 to form BF4 ion
BF3 + HF H+ [BF4]
Hydrogen tetrafluoroborate (III) (stable species)
BCl3 + H2O B (OH)3 + 3HCl
BCl3 + HCl H [BCl4]
unstable
BCl4 ion is unstable because of steric hindered
Ex. of sp2 hybridisation
CCl4 no vacant orbitals

So, will not under go hydrolysis.
NCl3 no vacant orbitals.

Hydrolysis of NCl3 takes place by H bond formation
H
O
H
Cl Cl Cl
NH3 + HOCl
By similar mechanism there will be hydrolysis of NBr3 and NI3 but NF3 does not undergo hydrolysis mainly
because it is a nonpolar molecule and also the hydrolysis produft FOH is an unstable compound.
NF3 is almost a non-polar molecular : It has = 0.23 D much less than NH3 .
In NF3 molecule, the resultant of bond moments is going to oppose the l.p. moment.
NF3 reacts with water very slowly or it undergoes hydrolysis very slowly.
Because (a) NF3 is almost non-polar
(b) If NF3 is hydrolysised HOF is formed which is unstable.
NF3 + 3H2O NH3 + HOF
unstable
So above equation is mainly backword shifted.
RESONANCE
3rd period
sp d
MgCl2
<
NaCl
S,P,d
<
SiCl4
AlCl3
PCl5 SCl4
(not found)
Ionic
+
2+
3+
([Na(H2O)6] Cl )[Mg(H2O)6 ] [Al(H2O)6 ]

SiCl4 vacant 3d orbitals
Si(OH)4 + 4HCl
unstable
H2 SiO3 + H2O
silicic acid
(cannot be isolated,formed only in aq. phase)
H2CO3 & H2SiO3 both are unstable are found only in aq. solution phase.
H2CO3 H2O + CO2
H2SiO3 H2O + SiO2
PCl3 ( p cannot form H bond)
Hydrolysis will takes place by coordinate bond formation
P (OH)3 + HCl.
H3PO3 (Phosphorus acid)

PCl5 P(OH)5 + HCl
H3PO4
(Phosphoric acid)
DIPOLE MOMENT
Let B is more ve than A.

Dipole moment of the bond = x
unit for DM = esu cm
1D = 1010 esu 108 = 1018 esu cm
1D = 3.33 1030 coloumb metre.
Resultant DM
P 2 Q 2 2PQ cos
RESONANCE
SOME IMPORTANT POINTS ABOUT DIPOLE MOMENT :
A polyatomic molecule having polar covalent bonds but zero dipole moment indicates the symmetrical
structure of the molecule. e.g. B - F bonds are polar in BF3 but BF3 has = 0 due to its symmetrical
geometry.
If molecule have = 0.
then it should be linear or having symmetrical geometry.
e.g. linear CO2, CS2, BeCl2 (g).
symmetrical geometry BF3 , CH4 , PCl5 , SF6 , IF7 , XeF4
If molecule has 0 then it should be angular or having unsymmetrical geometry.

e.g. angular SnCl2 , PbCl2 , SO2 ,
Unsymmetrical geometry NH3, H2O, NF3, SF4, H2S,
% Ionic character =
Experiment al
Theoretica l
( Observed)
100
100 =
(100% Ionic compound)
Following compounds have zero dipole moment BF3 ,CO2 , SO3 , CF4 , PF5 (g) , SF6 , XeF2 , CS2 , CCl4 , PCl5 (g) , XeF4
(i)
Some orders of D.M.

HF > HCl > HBr > HI
1.92 D 1.08
0.78
0.38
& HF (aq) weak acid
(ii)
CH3Cl > CH2Cl2 > CHCl3 > CCl4

1.8D
1.6D
1.0
0.0 D
(iii)
Usually net D.M. of cis isomer is more than trans.

but there can be exceptions also
CH3 CH=CHCl
(iv)
For substituted benzene usually the order is

o>m>p
CH3
exceptional case
p > (m/o)
Cl
RESONANCE
(v)
H N
F
N
3
3
HCN
2.95D
Q.
H2O
1.84D
H2S
0.92D
CH3F
CD3F
DM = 1.847 D
D is more (+ve) than H
D.M. = 1.858D
SO2
1.63D
O3
0.52
CO
0.10D
APPLICATION OF D.M.
Q.
Given that the net D.M. of H2O = 1.85 D and

B.A. = 104.5C (cos 104.5 = 0.25)
ignoring the effect of l.p. calculate OH bone D.M.
(1.85)2 = x2 + x2 + 2x2 (0.25)
3.1025 = 2x2 1.5 x2 = 1.5 x2
x2 =
Q.
3.1025
; x2 = 2.69 ;
1 .5
x=
2.69 = 1.51
You are given a triatomic molecule AB2 B more ve than A. For which of the following B.A. net = max.
(A) 0
(B) 30
(C) 45C
(D) 90C
cos max. = 30
# 0 : (diatomic molecule)
(ii) Calculation of % ionic character in covalent polar bond
observed
100
% ionic character = u
calculated theoritica lly
for calculation of theoritical it is assumed that 1e is completely transferred from one atom to another.
1
= 4.8 1010 e.s.u. A B

x = given to us as B.L. (cm)
Q.
Sol.
For HCl gas molecule exp = 1.03D

Bond distance = 1.275
Calculate the % ionic character.
theo = 4.8 1010 1.275 108
= 6.12 1018
% ionic char. =
RESONANCE
1.03 10 18
6.12 10 18
100 = 17%
Q.
If OH bond distance in water = 0.572

Then calculate what fraction of electronic charge is present on the O atom.
x = 0.572
108 x 1.51 = x
=
1.51 10 18
0.527 10 8
Fraction of electronic charge =

Q.
4.8 10 10
Net of SO2 = 1.61 D. B.L. SO = 0.145 nm and each bond has approx. 25% ionic character. Ignoring the
effect of I.P. on S atom. Calculate the B.A. for SObond.
25 =
x 100
4.8 10
10
0.145 10 7 cm
x = 1.74 D
1.61 =
x 2 x 2 2 x 2 cos
cos = 0.572
125
The % of ionic character in a covalent bond can also be calculated by Haney & smith eq.
% ionic character = 16 + 3.52
= absolute diff. of E.N. of bonded atoms on pauling scale
for 50% ionic character = 2.1
But in many cases even at a diff. of 1.7
50% ionic character is observed.
LECTURE # 11
Introduction to MOT :
A molecule is formed from the combination of two or more than two atoms of the same or different
elememnts and has characteristic properties of its own. A molecule is formed because it has a lower
energy( and hence is stable) as compared to the constituent atoms existing separately. It is convenient to
think that the atoms in a molecule are linked by chemical bonds. A chemical bond may be defined as
the force that holds the atoms together within a molecule.
Two thoeries of chemical bonding, namely valence bond theory and molecular orbital theory have been
proposed to describe covalent bond formation and the electronic structure of molecules. Both these theories
are quantum mechanical theories of chemical bonding.
MOLECULAR ORBITAL THEORY :
The molecular orbital theory was developed by F. Hund and R.S. Mulliken in 1932. The salient features are:
(i)
Just as elctrons of any atom are present in various atomic orbitals, electrons of the molecule are present in
various molecular orbitals. We know the names of atomic orbitals like s, p, d and f orbitals but the molecular
orbitals will be having different names as well as different electronic distributions.
(ii)
Molecular orbitals are formed by the combination of atomic orbitals of comparable energies and proper
symmetry.
(iii)
While an electron in an atomic orbital is influenced by one nucleus, in a molecular orbital it is influenced by
two or more nuclie depending upon the number of the atoms in the molecule. Thus an atomic orbital is
monocentric while a molecular orbital is polycentric.
(iv)
The number of molecular orbitals formed is equal to the number of combining atomic orbitals. When two
atomic orbitals combine, two molecular orbitals called bonding molecular orbital and anti-bonding molecular orbital are formed.
(v)
The bonding molecular orbital has lower energy and hence greater stability than the corresponding antibonding
molecular orbital.
RESONANCE
(vi)
Just as the electron probability distribution around a nuclues in an atom is given by an atomic orbital , the
electron probablity distribution around a group of nuclei in a molecule is given by molecular orbital.
(vii)
The molecular orbitals like the atomic orbitals are filled in accordance with the Aufbau principle obeying
the Pauli Exclusion principle and the Hunds Rule of Maximum Multiplicity. But the filling order of
these molecular orbitals is always experimentally decided, there is no rule like (n + l) rule in case of
atomic orbitals.
( In Valence Bond Theory we modify the pure orbitals of a single atom first - in hybridisation and
then use these modified or hybridised orbitals to form the bonds while in Molecular orbital Theory
orbitals of different atom are used to form new kind of orbitals called molecular orbitals.)
Formation of Molecular Orbitals: Linear Combination of Atomic Orbitals(LCAO)
In principle, Schrodinger equation can be written for any molecule. However, since it can not be solved
exactly for any system containing more than one electron, molecular orbitals which are one electron wave
functions for the molecules are difficult to obtain directly from the solution of the Schrodinger equation. This
difficulty is overcome by resorting to an approximation methid called the Linear Combination of Atomic
Orbitals(LCAO) method to form molecular orbitals.
Let us consider the application of the LCAO method to the homonuclear diatomic hydrogen molecule. The
two hydrogen atoms in the H2 molecule, fot the sake of converience may be labeled as A and B. Each
hydrogen atom in ground state has one electron in the 1s orbital. These atomic orbitals may be represented
by the wave functions A and B. Mathermatically the formation of molecular orbitals is described by the
linear combination (addition or subtraction of the wave functions of the individual atomic orbitals) of A and B
as shown below.
MO = A B
Therefore, two molecular orbitals and * are formed
= A + B
* = A B
The molecular orbital formed by the addition of atomic orbitals is called the bonding molecular orbital
and the molecular orbital * formed by the subtraction of atomic orbitals is called antibonding molecular
orbital (Fig.)
Atomic
orbital
Molecular
orbitals
Atomic
orbital
*A B
Increasing energy
Antibonding orbital
higher enrgy than
that of atomic orbitals
=A + B
Bonding orbital
lower energy than
that of atomic orbital
Fig. Formation of bodnding () and antibonding (*) molecular
orbitals by the linear combination of atomic orbitals A and B
centered on two atoms A and B respectively.
Qualitatively, the formation of molecular orbitals can be understood in terms of the constrcutive or destructive
interference of the electron waves of the combining atoms. In the formation of bonding melecular orbital, the
two electron waves of he bonding atoms reinforce each other (constructive interference) while in th formation
of antibonding molecular orbital, these electron waves cancel each other (destructive interference). The
result is that in a bonding molecular orbital most of the electron density is located between the nuclei of the
bonded atoms and hence the repulsion between the nuclei is very low while in an antibonding molecular
orbital, most of the electron denstity is located away from the space between the nuclei, as a matter of fact
there is a nodal plane (i.e., plane in which the electron density is zero) between the nuclei. Electrons placed
in a bonding molecular orbital tend to hod the nuclei together and stabilize a molecule. A bonding molecular
orbital is, therfore, always of lower energy than either of the atomic orbitals that have combined to form it. In
contrast, electrons placed in the antibonding molecular orbital destabilize the molecule. The attraction between the electrons and the nuclei is less than the mutual repulsion of electrons in this orbital and this
produces a net increase in enrgy. Consequently, the electrons placed in this molecular orbital tend to destabilise
the molecule and that is why this orbital is said to be antibonding.
RESONANCE
It needs to be pointed out that the energy of the antibonding orbital is raised above the energy of the atomic
orbitals that have combined by an amount more than that by which the energy of the bonding orbital has been
lowered. The total energy for two molecular orbitals however remains the same as that of the two orginal
atomic orbitals.
CONDITIONS FOR THE COMBINATION OF ATOMIC ORBITALS :
The linear combination of atomic orbitals to from molecular orbitals takes place only if the following conditions are satisfied :
1.
The combining atomic orbitals must have the same or neraly the same energy. This means that 1s
orbital can combine with another 1s orbital but not with 2s orbital because the energy of 2s orbital is appreciably higher than that of 1s orbital. It, therefore, means that only a limited number of combinations of atomic
orbitals are possible.
2.
The combining atomic orbitals must have the same symmetry about the molecular axis. By convention z-axis is taken as the molecular axis. It is important to note that atomic orbitals having same or nearly
the same energy will not combine if they do not have the same symmetry. For example, 2pz orbital of one
atom can combine with 2pz orbital of the other atom but not with the 2px or 2py orbitals because of their
different symmetries.
3.
The combining atomic orbitals must overlap to the maximum extent. Greater the extent of overlap,
the greater will be the electron-density between the nuclei of a molecular orbital.
TYPES OF MOLEUCLAR ORBITALS :
Molcular orbitals of diatomic moelcules are designated as (sigma), (delta), etc.
In this nomenclature, the sigma () moleuclar orbitals are symmetrical around the bond-axis while pi
() molecular orbitals are not symmetrical. For example, the linear combination of 1s orbitals centered
on two nuclei produces two molecular orbitals which are symmetrical around the bond-axis. Such molecular
orbitals are of the type and are designated as 1s and *1s [Fig.(a)]. If internuclear axis is taken to be in
the direction, it can be seen that a linear comination of 2pz - orbitals of two atoms also produces two sigma
molecular orbitals designated as 2pz and * 2pz. [Fig. (b)] Molecular orbitals obtained from 2px and 2py
orbitlas are not symmetrical around the bond axis because of the presence of positive lobes plane. Such
molecular orbitals, are labelled as and * [Fig. (c)]. A bonding MO has large electron density above and
below the inter nuclear axis. The * antibonding MO has a node between the nuclei.
-type of molecular orbitals are obtained by in involment of d-orbitals into bonding which is not required for us
to study.
ENERGY LEVEL DIAGRAM FOR MOLECULAR ORBITALS :
We have seen that 1s atomic orbitlas on two atoms from two molecular orbitals designated as 1s and *
1s. In the same manner, the 2s and 2p atomic orbitals (eight atomic orbitals on two atoms) give rise to the
following eight molecular orbitals :
Antibonding
MOs *2s
*2pz *2px *2py
Bonding
MOs 2s
2pz
2px
2py
The energy levels of these molecular orbitals have been dtermined expermientally from spectrospic data for
homonuclear diatomic molecules of second row elements of the periodic table. The increasing order of
energies of various molecular orbitals for O2 and F2 is given below 1s < *1s < 2s < *2s < 2Pz <
(2px =2py) < *2px = *2pz < *2pz
However, this sequence of energy levels of moleuclar orbitals is not correct for the remaining molecules Li2,
Be2, B2, C2, N2. For instance, it has been observed experimentally that for molecules such as B2, C2, N2 etc.
the increasing order of energies of various molecular orbitals is
1s < * 1s < 2s < *2s < (2Px = 2py) < 2pz < (*2Px = *2py) < *2pz
The important characteristic feature of this order is that the energy of 2pz moleuclar orbital is higher
than that of 2px and 2py molecular orbitals.
Do tell the students to make up the above energy level diagram second order is for species having number of
electrons N < 14 and for species derived from the species having number of e < 14. While the Ist order is
valid for species having number of e > 15.
RESONANCE
Molecular
orbitals
Antibonding sigma
molecular orbital
Energy
Atomic
orbital
Atomic
orbital
+
1s
+
1s
+
*1s
*1s
1s
Bonding sigma
molecular orbital
1s
+
1s
1s
+
+
1s
1s
(a)
Molecular
orbitals
Atomic
orbital
2pz
2Pz
2pz
2pz
+ +
*1s
Bonding sigma
molecular orbital
*2pz
Energy
Atomic
orbital
Antibonding sigma
molecular orbital
+ +
2pz
2pz
2pz
2pz
(b)
Antibonding sigma
molecular orbital
Molecular
orbitals
Energy
Atomic
orbital
Atomic
orbital
*2px
2pz
2pz
2px
(c)
*2px
Bonding sigma
molecular orbital
2Px
2px
2px
2px
2px
Fig. Constours and energies of bonding and antibonding molecular orbitals formed through
combinations of (a) 1s atomic orbitals; (b) 2pz atomic orbitals and (c) 2px atomic orbitals.
**
(i)
(ii)
Write dawn electronic configurations of H2, He2, Li2, Be2, B2, C2, N2, O2, F2, Na2, H2+, H2, He2+, He2,
N2+, N2, O2+, O2, O22, CO, NO, CN, CN, NO+, CO+
Do tell the students to write down all these electronic configurations Ist either in the class or from
their homes.
ELECTRONIC CONFIGURATION AND MOLECULAR BEHAVIOUR
The distribution of electrons among varous molecular orbitals is called the electronic configuration of the
moelcule. From the electronic configuraiton of the molecule, it is possible to get important information about
the molecule as discussed below.
The molecule is stable if Nb is greater than Na, and
The molecule is unstable if Nb is less than Na In (i) more bonding orbitals are occupied and so the bonding
influence is stroger and a stable molecule results. In (ii) the antibonding influence is strogner and therfore the
moleucle is unstable.
Na number of e in bonding molecular orbitals and Nb number of e in antibonding MOs.
RESONANCE
BOND ORDER
Bond order (b.o.) is defined as one half the difference between the number of electrons present in
the bonding and the antibonding orbitals i.e.,
Bond order (b.o.) = (Nb Na)
The rules discussed above regarding the stability of the moleuclar can be restated in terms of bond order as
follows : 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 moelcule.
NATURE OF THE BOND
Integral bond order values of 1, 2 or 3 correspond to single, double or tripll bonds respectively as studied in
the classical concept.
BOND-LENGTH
The bond order between two atoms in a molecule may be taken as an approximate measure of the bond
length. The bond length decreases as bond order increases.
MAGNETIC NATURE
If all the molecular orbitals in a molecule are doubly occupied, the substance is diamagnetic (repelled by
magnetic field). However if one or more molecular orbitals are singly occupied it is paramagnetic (attracted
by magnetic field), e.g., O2 moleucle.
BONDING IN SOME HOWONUCLEAR DIATOMIC MOLECULES
In this section we shall discuss bonding in some homonuclear diatomic molecules.
1.
Hydrogen molecule (H2) : It is formed by the combination of two hydrogen atoms. Each hydrogen atoms
has one electron in 1s orbital. Therefore, in all there are two electrons in hydrogen molecule which are
present in 1s molecular orbital. So electronic configuration of hydrogen molecule is
H2 : (1s)2
The bond order of H2 molecule can be calculated as given below :
Nb Na 2 0
1
2
2
This means that the two hydrogen atoms are bonded together by a single covalent bond. The bond dissociation energy of hydrogen molecule has been found to be 438 kJ mol1 and bond length equal to 74 pm. Since
no unpaired electron is present in hydrogen molecule, therefore, it is diamagnetic.
Bond order =
2.
Helium molecule (He2) : The electronic configuration of helium atoms is 1s2. Each helium atom contains 2
electrons, therefore, in He2 molecule there would be 4 elctrons. These electrons will be accommodated in
1s and *1s molecular orbitals leading to electronic configuration :
He2 : (1s)2 (*1s)2
Bond order of He2 is (2 2) = 0
He2 molecule is therefore unstable and does not exist. Similarly, it can be shown that Be2 moelcule (1s)2
(*1s)2 (2s)2 (*2s)2 does not exist.
3.
Lithium molecule (Li2) : The electronic configuration of lithium is 1s2, 2s1 . There are six electrons is Li2.
The electrons in Li2. The electronic confiugraiton of Li2 molecule, therefore, is
Li2 : (1s)2 (*1s)2 (2s)2
The above configuration is also written as KK(2s)2 where KK represents the closed K shell structure (1s)2
(*1s)2.
From the electronic configuration of Li2 molecule it is clear that there are four electrons present in bonding
molecular orbitals and two electrons present in antibonding moleuclar orbitals. Its bond order, therefore, is
(4 2) = 1. It means that Li2 molecule is stable and since it has no unpaired electrons it should be
diamagnetic. Indeed diamagnetic Li2 molecules are known to exist in the vapour phase.
4.
Carbond molecule (C2) : The electronic configuration of carbons is 1s2 2s2 2p2. There are twelve electrons
in C2. The electronic configuraiton of C2 molecule, therefore, is
C2 : (1s)2 (*1s)2 (2s)2 (*s)2 (2p2x = 2p2y ) or KK (2s)2 (*2s)2 (2p2x = 2p2y )
The bond order of C2 is (8 4) = 2 = 2 and C2 should be diamagnetic. Diamagnetic C2 molecules have
indeed been detected in vapour phase. It is important to note that double bond in C2 consists of both pi bonds
because of the presence of four electrons in two pi molecular orbitals. In most of the other molecules a
double bond is made up of a sigma bond and a pi bond.
RESONANCE
5.
Nitrogen molecule (N2) :

Electronic configuration : (1s)2 (*1s)2 (2s)2 (*2s)2 (2p2x = 2p2y ) 2pz)2
or
KK (2s)2 (*2s)2 (2p2x = 2p2y ) 2pz)2
1
(10 4) = 3. one sigma and two bonds.
2
N2 : Though 15e but derived from N2, hence EC will be occording to N2
Electronic configuration : (1s)2 (*1s)2 (2s)2 (*2s)2 (2p2x = 2p2y ) 2pz)2 , *2px)1
or
KK (2s)2 (*2s)2 (2p2x = 2p2y ) 2pz)2 , *2px)1
B.O. of N2 =
6.
1
(10 5) = 2.5
2
N2+ : B.O. = 2.5, out of N2+ and N2, N2 is less stable though both have equal bond order but N2 has greater
number of antibonding electrons.
B.O. of N2 =
With 2s-2p mixing
Without 2s-2p mixing
C2
N2
O2
F2
Ne2
B2
2s
2s
*2s
*2s
2p
2p
2p
Energy
*2p
*2p
2p
*2p
*2p
900
150
159
945
143
131
600
121
110
620
100
498
300
50
290
290
Bond order
Magnetic
properties
Paramagnetic
2
Valence
electron
configuration
Bond length/pm
Bond energy/kJmol
7.
(2s) (*2s)
(2p)2
Diamagnetic
2
(2s) (*2s)
(2p)4
Diamagnetic
Paramagnetic
(2s) (*2s)
(2p)4 (2p)2
(2s) (*2s)
(2p)2 (2p)4
2
(*2s)
Diamagnetic
2
(2s) (*2s)
(2p)2 (2p)4
4
(*2s)
(2s) (*2s)
(2p)2 ( 2p)4
4
2
(*2s) (*2s)
Fig. MO occupancy and molecular properties for B2 through Ne2.
RESONANCE
8.
Oxygen molecule (O2) :

The electronic configuration of oxygen atoms is 1s2 2s2 2p4 . Each oxygen atom has 8 electrons, hence, in
O2 moleucle there are 16 electrons. The electronic configuration of O2 molecule, therefore, is
O2 : (1s)2 (*1s)2 (2s)2 (*2pz)2 (2p2x = 2p2y ) (*2px1 = *2p1y)
or
2
2
2
O2 : KK (22s) (2* 2s) (21p z )

1
( 2p x 2p y ),( * 2p x * 2p y )
From the electronic configuration of O2 moleucle it is clear that ten electrons are present in bonding moleclar
orbitals and six electrons are present in antibonding molcular orbitals. Its bond order, therefore, is
1
Nb Na 1 [10 6] 2
2
2
So in oxgyen molecule, atoms are held by a double bond. Moreover, it may be noted that it contains two
unpaired electrons in *2px and *2py molecular orbitals, therefore, O2 molecule should be paramagnetic, a prediction that corresponds to experimental observation. In this way, the theory successfully
explains the paramagnetic nature of oxygen.
Similarly, the electronic configurations of other homonuclear diatomic molecules of the second row of the
periodic table can be written. In Fig. are given the molecular orbital occupancy and molecular properties for
B2 through Ne2. The sequence of MOs and their electron population are shown. The bond energy bond length,
bond order, magnetic properties and valence electron configuraiton appear below the orbital diagrams.
Bond order =
9.
O2+ : B.O. = 2.5 paramagnetic.
10.
O2 : B.O. = 1.5 paramagnetic.
11.
O22 : B.O. = 1 diamagnetic.
HOMO : Highest Occupied Molecular Orbital.

LUMO : Lowest Unoccupied Molecular Orbital
O22
No. of unpaired e s
0
B.O.
1.0
B.L.
O2
1
1.5
O2
2
2.0
O2+
1
2.5
O22+
0
3.0
B.L.
Ne2
1s2 , *1s2 , * 2s2 , 2s2 , * 2s2 , 2 2 s2 ( 22py , 22pz )

( *2py , *2pz ) * 2px 2 (HOMO)
10 10
=0
2
Species
H2
H2+
He2+
B.O. =
BE (kJ/mol)
432
255
230
B.L. (pm)
74
106
108
MOT FOR HETERONUCLEAR DIATOMIC MOLECULES :

CO is donor in metal complexes by
This is isoelectronic with N2 molecule
This is isoelectronic with N2 molecule

Its configuration must be simular to N2.
1s2 , 1s2 , 2s2 , ( 2py 2 , 2pz 2 ) ,
22px
HOMO
B.O. = 3
1 and 2 bond
RESONANCE
The MO configuration of CO has given above cannot be considered to be 100% correct because if CO is
converted into CO+ then, its B.O. =
94
= 2.5.
2
B.L. must
B.L.CO = 1.128
B.L.CO+ = 1.115
NO O2+
(Acc. of spectroscopy)
Total no. of e = 15
1s2 , *1s2 , 2s2 , * 2s2 , 2px 2 , ( 2py 2 , 2pz 2 ) ,
( * 2py ' , * 2pz ) * 2px

HOMO
LUMO
10 5
= 2.5
2
1 1.5 bond
Odd e B.O. =
NO+............................. ( 2py 2 , 2 z 2 )( * 2py , 2pz )
(D)
10 4
=3
2
1 and 2 bond
B.O. =
NO+ > NO
3
2.5
O 2+ > O 2
2.5
2
more stable
Formation of NO+ and O2+ is endothermic (difficult)

Diagrams for M.O.
1s + 1s
Add
Electron
Density
or + +
+
1s
1s
Due to presence of electrong density between two nuclei, repulasion between two nucleis rather attraction
takes place.
bonding M.O. type
Nodal plane
Add
+
1s
1s
AMO = a - b
*1s
more repulsion (ungerade)

GERADE OR UNGERADE ORBITALS
If we move equal dist in the opp. direction from the centre of a MO and sign of the wave functions remains the
same, the MO will be known as gerade otherwise it will be ungerade.
is gerade and *1s is ungerade.
H2 1s2 (g) *1s0 (u)
RESONANCE
LINEAR COMBINATION OF 2p-ORBITALS

(a)
Along the Molecular Axis ()
nodal plane
+ + +
2px
Addition
Subn
2px
2px
gerade
(b)
2px
ungerade
Of 2py And 2py orbitals
+
+
Addition
2py 2py
ungerade
2py
Subn
gerade
2py
Conclusion :
s
p
p
s
*p
*p
all gerade.
MOT
FOR
ungerade
HF
HF
p
2py
2pz
(NBD)
2px
2py
2pz
MO
NBD
2s
NBD
1s
20
=1
2
Atomic orbitals is always monocentric But molecular orbitals is always polycentric.
B.O. =
RESONANCE
LECTURE # 12
INTERMOLECULAR BONDS :
HYDROGEN BOND :
Nitrogen, oxygen and fluorine are the higly tronegative elements. When they are died to a hydrogen atom to
form covalent bond , the electrons of the covalent bond are ted towards the more electronegative atom. This
partially positively charged hydrogen atom forms a bond with the other electronegative atom. This bond is i
as hydrogen bond and is weaker than avalent bond. For example, in HF molcule, the hydrogen bond exists
between hydrogen atom of one molecule and fluorine atom of another molecule as depicted below :
H+ F H+ F H+ F
Here , hydrogen bond acts as a bridge between toms which holds one atom by covalent bond and the other
by hydrogen bond. Hydrogen bond is represented by a dotted line ( ) while a solid line represents the
covalent bond. Thus, hydrogen bond can be defined as the attractive force which binds hydrogen atom of one
molecule with the electronegative atom (F, O or N) of another molecule.
(I) Cause of Formation of Hydrogen Bond
When hydrogen is bonded to strongly electronegative element 'X'. the electron pair shared between the two
atoms moves far away from hydrogen atom. As a result the hydrogen atom becomes highly electropositive
with respect to the other atom 'X'. Since there is displacement of electrons towards X, the hydrogen acquires
fractional positive charge (+) while X' attain fractional negative charge (). This results in the formation of a
polar molecule having electrostatic force of attraction which can be representes as :
H+ X H+ X H+ F
The magnitude of H bonding depends on the physical state of the compound. It is maximum in the solid
state and minimum in the gaseous state. Thus, the hydrogen bonds have strong Influence on the structure
and properties of the compounds.
(ii)
Infact energy of H-bond is usually low but there are examples in which H-bond energy is found to be nearly
220 kJ/mol (comparable to covalent bond) Therefore H-bond can be classified into 3 categories.
(a) Weak BE < 25 kJ/mol.
(b) Medium 25 35
(c) Strong > 35 kJ/mol ex : K+HF2 or [HF2] ion energy = 220 kJ/mol.
(iii)
Discovered by Huggius, Latimer and Rodbush.
(iv)
Infact H-bond is due to electrostatics attraction between the pole of H and .p. of e s on another ve atom
(v)
Ex.
+
A
H ----- :B
(-ve)
(-ve)
H-bond
H-bonds are found to be much stronger with F-atoms but in case of other atoms the relative strength of Hbond will depend upon + charge of H( possiblity when atom A is more -ve) and availability of l.p. on B-atom.
(B must be relatively less ve)
Max H-bond strength

(A)
+
O
H - - - - - - :N
(B)
H - - - - - - :O
(C)
H - - - - - - :N
(D)
H - - - - - - :O
Order of H-bond strength A > B > C > D

(vi)
Ex.
Ans. (A)
H- - - - - :B
(generally distance x < y)
x
y
But in case of very strong H-bonding
x = y,
K+[HF2]
RESONANCE
TYPES OF H-BONDING.
(A)
Intermolecular
Ex. : H2O, HF, R OH, CH3COOH / HCOOH, NH3(R), R NH2,
R
NH, HCN, H BO (s) etc.
3
3
1.74 1.01
O- - -H
|
H
O
|
H
F
120
to
140
H
F
H3C
C
O
HCO3 in KHCO3 In dimeric form but HCO3 in NaHCO3 is in linear polymeric form.
O
C=O
O=C
O
O
H
|
O
H
O
|
B
H3BO3(s)
H
O
(B)
B
|
O
Intramolecular :
O
O
(i)
O
N
O-nitrophenol
(ii)
Chloral-hydrate CCl3CH(OH)2
CCl3CHO (Chloral)
Cl
O
C
Cl
Cl
H
2 OH groups are stabilised on the same C-atom.
RESONANCE
(iii)
Maleic Acid :
H
H
(iv)
C
||
C
COOH
COOH
C
||
C
O
||
C
O
+ H+
H
C
||
O
K2 << K1
Anion of Caros Acid :
O
||
S
||
O
S
st
It goes out I
HSO5
K2 << K1
(v)
Enolic form of Acetoacetic ester (AAE)
(vi)
An interesting hydrate of Hydronium ion with the formula H3O+(H2O)20 in which H2O molecules are hydrogen
bonded. Some lower species like H5 O 2 have also been observed where the 2 water molecules are linked
three H bonds.
Similarly H3 O 2 ions are also observed which is actually hydrate OH ion.
It is found urea and phosphoric Acid form H bond with each other
NH2CONH2 + H3PO4
2 types of Hbond
B.L.OH x = 122 pm ;
RESONANCE
B.L. NH y = 100 pm
Questions based upon H-bonding

(i)
(ii)
H2O is liquid but H2S is gas

HF is liquid but HCl is gas.
Due to intermolecular H bonding molecules undergo association (molecular assoication) due to which that
substance become liquid or solid at room temperature.
its B.pt
(iii)
C2H5OH is soluble in water but ether is much less soluble

H O H O
|
|
H
R
Association is large
R O HO
|
|
R
H
Association is very small
solubility of ether is much less.

C2H5OC2H5 8 gm/100gm H2O
CH3CH2CH2CH2OH
Hydrocarbon chain solubility
(iv)
Hydrolysis of NCl3
Some imp solubility

data In 100 gm of H2O
n-Butyl alcohol
sec-butyl alcohol
iso-butyl alcohol
C6H5CH2OH
= 8 gm
= 12.7 gm
= 10 gm
= 4 gm
Infinite solubility
CH3OH
C2H5OH
CH3CH2CH2OH
CH3 CH CH3
|
OH
CH2=CHCH2OH
(v)
HF(aq.) is a weak acid

HF < HCl < HBr < HI
H O H O
(vi)
D O D O
EH / H 0
2
ED / D 0.01V
2
D is more +ve than H

It is capable of forming slightly more H bond than H thats why D2O molecule are more associated and its
B.pt is more than the B.pt of H2O liq.
RESONANCE
(vii)
Ice floats on water
No. of water molecule attached to 1 H2O molecule = 4

No. of H bonds in a molecule = 2
One H2O is tetrahedrally bonded with 4H2O molecules.
Intermolecular specing of ice
D2O(s)
density of D2O(s) > density of H2O(l)
it sinks in H2O(l) but floats on D2O(l)
Due to open structure, ice is capable of forming Clatherates. (cage like compounds)
Xe will be captured by ice.

Xe(g) because of its bigger atomic size is trapped in the cages formed by H2O molecules in the structures of
ice. He cannot be trapped due to smaller size. Such compounds are called clatherates compounds.
(No chemical bonding)
(viii)
Density of water max at 4C

slightly
H2O(s)
warm
ice
d
T < 4C
>0C
In this temperature region some of the ice melts and hence some H2O molecule go into the cages of
remaining ice structure.
(ix)
(x)
V d becoming max at 4C but beyond this temp thermal effects become dominating V d
Water can extinguish the burning alcohol but not the burning petrol or a Hydrocarbon (in general).
H2O(l) + ROH(l) solution
(miscible)
H2O(l) + Petrol or hydrocarbon (l) Not miscible
(No H bonding)
density of open chain HC < dH2O lighter than water. continue burning even in presence of H2O
Which is a stronger base why?
(a)
Trimethyl ammonium hydroxide
(b)
Tetramethyl ammonium hydroxide NCH3 4 OH
b is more basic
(CH3)3N: - - - - H O
Due to nitramolecular H bonding, release of OH ion become difficult it is a weaker base.
(xi)
C2H2 is most soluble in

(A) H2O
(B) C2H5OH
RESONANCE
(C*) CH3COCH3
(D) none or equally
C2H2 is highly soluble in acetone due to H bonding
None of the above 2 has H-bonding individually.

But C2H2 is not soluble in water because water molecules already so much associated through H-bond that
it is almost impossible for C2H2 molecules to break that association.
it is not soluble in H2O (l)
(xii)
B.pt of o-nitrophenol is less than m-nitrophenol or p-nitrophenol and this compound is much less soluble in
water than the remaining 2.
Due to intromalecular H-bonding in O
Due to intermolecular H-bonding in m-p-
INTERMOLECULAR FORCES (VAN DER WAALS FORCES) :

Intermolecular attractions hold two or more molecules together. These are weakest chemical forces and can
be of following types.
(a) Ion-dipole attraction :
(b) Dipole-dipole attraction :
(c) Ion-induced dipole attraction :
(d) Dipole-induced dipole attraction :
(e) Induced dipole-Induced dipole : (Dispersion force or London forces)
strength of van der Waals forces a > b > c > d > e
Note : According to NCERT ion-dipole attraction is not considered as a van der Waals forces
(a) Ion-dipole attraction :
Exists between an ion and a polar molecule. Its strength depends on (i) size of ion (ii) charge on the ion (iii)
dipole moment of the polar molecule.
Na
O
H
This force is responsible for hydration.
(b) Dipole-dipole attraction :

Electrostatic attractions between the oppositively charged ends of permanent dipoles. Exists between polar
molecules and due to this force gas can be liquified.
H
Cl
H
Cl
(c) Ion-induced dipole attraction :
Exists between ion and non-polar molecules
Na +
Cl
Cl
(d) Dipole-induced dipole attraction :

Exists between polar and non-polar molecules.
+
Cl
Cl
Cl
(e) Instantaneous dipole- Instantaneous induced dipole attraction :

Exists among the non-polar molecules like H2 , O2 , Cl2 etc. in solid or liquid states
e.g. ,
Cl
Cl
RESONANCE
Cl
Cl
Strength of vander waal force molecular mass.
Q.1
Give the order of boiling point of following

Cl2 , HCl
Ans.
Cl2 Cl2
<
dispersion force
Q.2
Arrange the inert gases, according to their increasing order of boiling points
Ans.
He < Ne < Ar < Kr < Xe Boiling point

Because strength of van der Waals force increases down the group with increase in molecular mass.
van der Waals force Boiling point.
HCl HCl
dipole-dipole attraction
(B.P.)
METALLIC BOND :
Nature electrical attraction between delocalised electrons (i.e. mobile electrons) and the positive part of the
atom (i.e. kernel). Strength of metallic bond depends upon following factors :
(i)
No of metallic bonds per atom :

Larger the number of metallic bonds (number of valence electrons) per atom, stronger is the metallic bonding.
Alkali metals-only one valence electron and therefore, one metallic bond per atom and thus gives weakest
metallic bonding. Hence their melting points are low.
Alkaline earth metals-two valence electrons and form two metallic bonds per atom and, therefore, gives a
comparatively bit stronger metallicbonding.
Transition metals may use inner -d-electrons along with the outers electrons for bonding as (n1) d and ns
have nearly same energy. So in them number of metallic bonds per atoms is quite large (more than two
always). Hence their melting points are higher.
(ii)
Type of hybrid orbitals participating in metallic bonding.

More directional and diffused hybrid orbitals form more stronger metallic bonds. ds hybrid orbitals (in transition
metals) are more directional and diffused than sp hybrid orbitals (in alkali & alkaline earth metals)
Therefore, much stronger metallic bonding takes place in transition metals.
(iii)
Radius of metallic atom :

Smaller the radius of atom, shorter is the bond length, hence greater is the bond strength.
RESONANCE
REVISION
LECTURE # 1
Naming of Inorganic compounds
Name of inorganic compounds mainly consist of two parts

st part - name of cationic part or name of less electronegative atom or part
Name of cationic part is generally now modified and generally this name ends in - ium
Ex.
NaCl sodium chloride

(NH4)2SO4 ammonium sulphate
2nd part - name of anionic part generally follow name of cationic part. The name of anionic part is modified
and depending of nature of anion if generally ends with
ide
ate
ite
Elemental or non oxoanion
Name of these anions ends with ide
Ex.
Halogen family
F flouride
Cl Chloride
Br Bromide
iodide
Oxygen family
O2
oxide
O 22
O2
peroxide
Se2
Te2
Nitrogen family
N3
N3
superoxide
sulphide
selenide
telluride
nitride
azide
P
phosphide
Carbon family
C4
carbide
Combined elemental anions
OH
hydroxide
SH
bisulphide
CN
cyanide
NC
isocyanide
If both element are non-metallic then more electronegative element is anionic part
As2O3 arsenic (III) oxide
OF2 oxygen di flouride
(1)
(4)
Ca3P2
ClF3
Write down the formula of

(1)
Sulphur hexafluoride
(4)
dioxygen di fluoride
1.
2.
(2)
(5)
Ba(CN)2
SF4
(3)
Na2S
(2)
(5)
Lithium nitride
barium azide
(3)
stroncium chloride
Naming of oxoanions
The anions of oxyacids of different element are called oxoanions. The names of oxoanions are derived
from the names of their parent oxyacids.
If name of acid ends with ic then name of anion will end with ate
If name of acid ends with us then name of anion will end with ite
Name of oxyacid should end with ic or us is decided by oxidation no of element in the oxyacid.
The following naming procedure is applied for naming oxyacids
If an element forms only one oxyacid then name of that generally ends with ic
H3BO3 boric acid (only oxyacid of boron + 3 )
H2CO3 carbonic acid ( + 4 = O.No.)
H4SiO4 Silica acid ( + 4 = O.No)
If any element forms oxyacids in two oxidation. States. Then acid of higher O.No. ends with ic & acid
with lower O.No. ends with us like sulphur
H2SO4
Sulphuric
(+6 O.No.)
H2SO3
sulphurus
(+4 O.N0.)
RESONANCE
3.
If any element forms oxyacids in 3 O.No. Then for highest ic

middle one us
Nitrogen
+ 5 HNO3
nitric acid
+3 HNO2
nitric acid
+1 H2N2O2
hypo nitrius acid
Phosphorous
+ 5 H3PO4
phosphoric acid
+ 3 H3PO3
phosphorus acid
+ 1 H2PO2
hypo phosphorus acid
4.
If element forms oxyacid

Then
highest per
next lower
next lower
lowest hypo
Chlorine
+7
HClO4
+5
HClO3
+3
HClO2
+1
HClO
in four. O.No.
ic
ic
us
us.
perchloric acid
chloric acid
chlorus acid
hypo chlorus acid
per ic
ic only one oxyacid } two oxyacids ] three oxyacids } four oxiacids
us
hypo us
There can also be some derived oxyacids such as
pyro acids
meta acids
pyro name is attached with acid if it is derived by removing one water molecule from two acid molecules.
H2 O
Two acid molecules
pyro acid
Cl2O7 not oxiacid it is an oxide
2HClO4
H O
2
so there will not be any pyro or metra acid of oxiacids of chlorine.

Sulphur
H S O pyro sulphuric acid (Oleum)
2H2SO4
H 2 O
2 2 7
2H2SO3
H
S O pyro sulphurous acid
H 2 O
2 2 5
Nitrogen
No pyro acid (as an oxide will be obtained)
phosphorous
H P O pyro phospheric acid
2H3PO4
H 2 O
4 2 7
2H3PO3
H
P O pyro phosphoros acid
H 2 O
4 2 5
Carbon family pyro not found
H6SiO7
Silicon 2H4SiO4
pyro silicic acid
H 2 O
Boron 2H3BO3
H
B
O
pyroboric
acid
4 2
5
H O
2
meta acid: If one water molecule is derived from one acid molecule then meta acid is obtained.
meta acid
One acid molecule
H O
2
Chlorine no meta acid

Sulphur no meta acid
Nitrogen no meta acid
HPO3
phosporus
H3PO4
H 2 O
H2SiO3
Silicon
H4SiO4
H O
meta boric acid
Carbon
Boron
meta boric acid
no meta acid
HBO2
H3BO3
H O
meta phosphoric acid
Naming of oxoanions
ic acid ate
;
us acid ite
Chlorine
HClO4 ClO4 perchlorate
HClO2 ClO2 chlorite
;
;
RESONANCE
HClO3
HClO
ClO3 chlorate
ClO hypochlorite
sulphur
H2SO4
H2SO3
H2S2O7
SO42 sulphate
HSO4 bisulphate (hydrogen sulphate)
SO32 sulphite
HSO3 bisulphite (hydrogen sulphite)
S2O72 pyrosulphate
Nitrogen
HNO3 NO3 nitrate
HNO2 NO2 nitrite
H2N2O2 N2O22 hyponitrite
phosphorous
H3PO4 N2O23 phosphate
H3PO3 PO43 phosphite
H3PO3 PO23 hypo phosphite
H4P2O7 P2O74 pyrophosphate
HPO3 PO3 meta phosprous
Silicon
H4SiO4
H6Si2O7
H2SiO3
Q.
:
SiO44 silicate
Si2O76 pyro silicate
SiO32 meta silicate
Carbon
H2CO3 CO32 Carbonate
HCO3 bicabonate { hydrogen carbonate)
Boron
H3BO3 BO33 borate
H4B2O5 B2O54 pyroborate
HBO2 BO2 meta borate
Write the formula of
(1) barium perchlorate
(2) sodium hypochlorite
(4) magnesium pyro phosphate
(3) calcium phosphate

(5) Copper () metaborate
Q.
Write the name of

(1) Co(BO2)2
(2) Sc2Si2O7
(3) Na2S2O7
(4) Ba(NO3)2
(5) Na2SiO3
There are some more anions which are very common like
+ 6 CrO42 Chromate ( name is derived from SO42 sulphate as all features are same)
+ 6 FeO42 ferrate
+ 6 MoO42 molybolate
+ 6 WO42 tungstate
+ 6 MnO42 manganate
corresponding acids can be
H2CrO4 chromic acid
H2MnO4 manganic acid
higher oxidation state of manganese MnO 4

So called permanganate HMnO4 permanganic acid
Polysulphides
S2x ( x = 2, 3, 4, 5..........)
S22 S S disulphide
structures
S
S23
trisulphide
S24
tetra sulphide
S
Sodium disulphide NO2S2

Sulphate & thiosulphate (hypo)
when ever oxygen of normal compound is replaced with sulphur then thio word is used before name of normal
compound
alcohol OH
Thioalcohol SH
ether O
Thioether S
sulphate SO42
thriosulphate (S2O32)
RESONANCE
O
||
S
||
O
S
||
S
||
O
O
O
There oxygens can not be replaced
cyanate ion & Thiocyanate ion

cyanic acid (HOCN)
N C O
cyanate ion
NCO
N C S
Thio cyanate ion
Resonating structure
Resonating structure
NCS
Chromate & dichromate

dichronate ion is stable in acidie medium while chromate is stable in basic medium
Cr2O72 + 2OH (not a redox char)
H2O + 2CrO42
Cations higher oxidation state of Cations ends with ic & leaver by us

Fe3+ ferric
Cu2+ cupric
2+
Fe ferrous
Cu2 2+ cuprous
Hg2+ mercuric
Hg22+ mercurous
xenon
perxenic acid H4xeO6
XeO64 perxenate ion
O
||
Xe
||
O
Xenic acid
H2XeO4 Xenic acid
XeO42 Xenate ion
(c) Hydrolysis :
Hydrolysis means reaction with water molecules ultimately leading to breaking of O-H bond into H+ and OH ions.
While the term Hydration means the surrouding of and polar molecule or ions by polar molecules of water.
Hydrolysis complex formation with water molecule or reaction with water molecule.
Hydration cluster formation by water molecule around the ion or molecule of solute.
Ionic compounds will under go hydrolysis st then hydration
Covalent compound mainly hydrolysis will takes place and negligible hydration.
Hydrolysis in covalent compounds takes place generally by two mechanisms
(a) By H-bond formation: As of Nitrogen Trihalides
(b) By Coordinate bond formation : Generally in halides of atoms having vacant d-orbitals or of halides of
atoms having vacant orbitals.
2nd period
LiCl
C Cl4
NCl3
2s 2p sp3 hybridisation
H
Li+
BCl3
OH2
Primary layer (hydrolysis)
Li
H2O
H2 O
OH
2
Be2+
H
(hydration) many such layer will
form.
2s 2p = sp3 hybridisation
RESONANCE

Ionic Bonding Lecture Notes

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Ionic Bonding Lecture Notes

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CHEMISTRY LECTURE NOTES

IONIC BOND (ELECTROVALENT BOND) :

Mg (g) + 2Cl (g) MgCl2 (s)

FACTORS AFFECTING L.E.

Lattice energy (L.E.)

Al2O3 Na2O MgO

Note : Dont discuss melting point of ionic compound here.

Born Haber Cycle for NaCl (s)

Born haber cycle for Al2O3(s)

2Al (g) + 3O (g)

Hf = 2Hsub + 2 HI.E1 + 2 HI.E 2 + 2HI.E3 +

Born haber for NaBr

MgO found as Mg2+O2 but not as Mg +O

General characteristics of ionic compounds :

(b) Melting and boiling points

(nature of solvent) where is dielectric constant.

Greater the polarity, greater will be r

Applications of Hydration energy :

Solubility of ionic solids :

solubility and viceversa

Explain by Fazans rule, because of covalent character

Na[BF4] difference will

Which is more soluble Cs3 or [N(CH3)4]+ 3

Predict the product of decomposition of given polyhalides

Rb+ [Cl2] RbCl + Cl

COVALENT CHARACTER IN IONIC COMPOUNDS (FAJANS RULE) :

There is no compound which is 100% ionic.

Small size of cation polarisation.

Charge on cation or anion polarisation.

Fe(OH)3 is more covalent than Fe(OH)2 .

similarly, SnCl2 is white but Sn2 is red.

Variation of M.P. [M.P. of covalent < M.P. of ionic] :

ionic charater , r+ ion & r ion = constant

CaF2 , CaCl2 , CaBr2 , Ca2

Thermal stability of carbonates ionic character

Li2CO3 Li2O + CO2

TO DECIDE THE CENTRAL ATOM

MODERN CONCEPT OF COVALENT BOND (VBT) :

[Principal Quantum no. same, n = 2]

(iii) Orbitals which are undergoing overlapping must be such that

Examples of overlapping of pure atomic orbitals.

(ii) HCl gas molecule (s-p)

(iii) F2, Cl2, Br2, 2 (p-p)

Strength of Sigma and pi Bonds :

Following overlappings are not allowed.

Total overlapping will zero

this type of overlapping is not allowed.

Count the & bonds in

bigger lobe will

2 new sp hybridised orbitals

4 new sp3 hybridised

Calculation of state of Hybridisation :

Will all the 4 H atom in propadiene be coplanar

Hydroazoic acid (HN3)

CH3CN is a weaker lewis base than CH3NH2

more E.N., lesser will be tendency to donate the l.p.

Fig.4.11 Formation of sp2 hybrids and the BCl3 molecule

BF3, C6H6, CO32 , B(OH)3, SO3, NO3 ,+CH3, graphite,

SO2, SnCl2, NOCl, O3, NO2

Fullerene - sp2 and sp3

has 1 e in pure P orbital

Graphite is anisotropic with respect to electrical conductivity.