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(2102) Lecture Notes Chemical Bonding e
(2102) Lecture Notes Chemical Bonding e
1. Types of bonding
2. octet rule & Lewis Structure
3. Limitations of octet rule & Formal charge
4. Writing resonating structures, finding average bond order.
5. VBT
6. Hybridisation Theory and VSEPR Theory
7. Hybridisation (sp, sp2, sp3)
8. Hybridisation (sp3d, sp3d2, sp3d3)
9. Bond angle prediction
10. Bond length prediction, Isomorphism in ionic compounds
11. Lewis acids. Coordinate bonding, Electron deficient bonding
12. Back Bonding
13. MOT Postulates
14. MOT (energy level diagram)
15. MOT applications
16. Multicentered species (species belongs to group 13, 14, 15)
17. Multicentered species (species belongs to group 16, 17, d-block)
18. Fajan’s rule
19. Applications of Fajan’s rule
20. Metallic bonding
21. Dipole moment
22. Intermolecular forces of attraction
23. H – bond & Effects of H –bonding
24. Complete discussion
RESONANCE page # 1
" Limitations of octet rule
" Incomplete octet
" Odd electron species
" Expanded octet/superoctet/hypervalent
" Other drawbacks
" Formal charge definition and formulae. Examples.
" Resonance in compounds
" Resonating structures (Definition)
" Rules for writing simple mononuclear structures
" Rules for writing resonating structures.
" Rules on formal charge to decide stability of resonating structures
" Resonance hybrid characteristics.
" Dependence of resonance hybrid on resonating structures and their stability
" Average bond order
" Average charge on atoms.
" Examples to explain resonance.
" H.W of 100 problems containing molecules of simple cases, hypervalent cases, odd electron
species.
Section C (Bond order in oxoanions and corresponding acids)
" Bond order in Oxoanions (exhibiting resonance),
" Bond order in oxoanions after adding H+ to it. Comparison with previous case.
Section D (VBT, Overlapping of orbitals)
" Valence bond theory
" Orbital overlap concept
" Main points of valence bond theory.
" Types of overlapping and covalent bonds
" Sigma bond
" s-s overlap
" s - p overlap
" p - p overlap
" p - d overlap
" Pi bond
" px - px or py - py
" p -d
" Comparison b/w sigma and pi bonds.
" Practice of counting sigma and pi bonds.
Section E (Hybridisation)
" Concept of hybridization (need)
" Postulates of hybridization (no - geometry considerations)
" Finding hybridization of atoms in a given compound.
" Steric number rule
" Examples of single centered molecules only.(several)
" Understanding hybridization in ground state and excited state. (examples)
Section F (VSEPR theory )
" VSEPR Theory.
" Main postulates
" Order of repulsion of electron pairs.
" Electron geometries and molecular geometries and bond angles
" SN =2, sp , linear geometry
" SN =3, sp2 , trigonal planar geometry
" SN = 4, sp3 tetrahedral geometry
" SN =5, sp3d , trigonal bipyramidal geometry
" BENT'S RULE
" SN = 6, sp3d2, octahedral geometry
" SN = 7 , sp3d3, pentagonal bipyramidal geometry
RESONANCE page # 2
Section G (Bond angle, bond length comparison)
" Drago's rule and bond angle considerations.
" Factors affecting bond angles
" Factors affecting bond lengths
" Size of atoms
" Multiplicity of bond (bond order)
" Hybridisation
" Oxidation state
" Isomorphism in ionic compounds
CHEMICAL BONDING 2.
Section A (Lewis acids and coordinate bonding + Electron deficient bonding)
" Concept of Lewis acids.
" Coordinate bond formation (Lewis bases)
" Al2Cl6, BeCl2(s), Fe2Cl6
" Electron deficient bonding (Banana bonding)
" B2H6
" BeH2(s)
" Al2(CH3)6
Section B (BACK BONDING)
" p-p bonding
" p-d bonding
" d-d bonding
" d-d bonding
Section C (MOT)
" Postulates
" LCAO for formation of molecular orbitals
" Example of formation of H2 molecule
" Bonding and Antibonding (Difference)
" Conditions for combining atomic orbitals
" Types of molecular orbitals
" molecular orbital
" molecular orbital
" Comparison b/w and orbitals (shape of electron cloud, stability)
" Shapes of molecular orbitals , location of nodal planes
" Gerade and ungerade molecular orbitals
" Energy level diagram of Molecular orbitals
" Homonuclear diatomic with total electrons 14
" Homonuclear diatomic with total electrons > 14
" Examples including charged species
Section D (MOT applications)
" HOMO
" LUMO
" Finding molecular parameters
" Bond order and its impact on bond length and bond energy.
" Nature of bond and stability
" Magnetic nature
" Heteronuclear diatomic species and their molecular properties.
" Color of molecules.
Section E (Multicentered species )
" Species belonging to group 13
" Species belonging to group 14
" Species belonging to group 15
" Species belonging to group 16
" Specie belonging to group 17
" Species belonging to d - block
RESONANCE page # 3
CHEMICAL BONDING 3.
Section A (Fajan's rule)
" Fajan's rule
" Polarisation :
" Polarising power of cation and
" polarisability of anions
" Applications of Fajan's rule:
" Thermal stability
" Color of some compounds
" Basicity of oxides/hydroxides
Section B (Metallic bonding)
" Metallic bonding
" Electron sea model
" Band theory
" Explanation of metallic properties by these models
CHEMICAL BONDING 4.
Section A (Dipole moment)
" Dipole moment
" Definitions
" Formulae
" Units
" Distinguishing b/w polar and non - polar molecules
" Some orders of dipole moments
" Finding % ionic character in a given compound
" Finding fraction of electronic charge in a given compound.
Section B (Intermolecular forces of attraction and H bonding)
" VDW forces
" Ion - dipole
" Dipole - dipole
" Ion - induced dipole
" Dipole - induced dipole
" Instantaneous dipole - induced dipole
" H - bond
" Definition
" Conditions for H -bond formation
" Comparison of H - bond strength
" Some exceptional cases of H -bond
" Types of H - bonding
" Intermolecular H -bond (examples)
" Intramolecular H - bond (examples)
Section C
" Effects of H -bonding (all examples)
RESONANCE page # 4
LECTURE # 1
NOTE : All faculty members are required to read unit 4 : Chemical Bonding and
molecular stucture from NCERT text book
Start topic properly from lattice energy (Ionic Bond) and complete previous theory speedly
RESONANCE page # 5
Born Haber Cycle for NaCl (s)
1 Cl (g) Hf
Na (s) + 2 NaCl(s)
2
Hsub 1( H )
BE
2
Na(g) HL.E.
Cl(g)
HI.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
1
Hf = Hsub + H.E. + H + Heg + HL.E.
2 BE
+ve/–ve
Generally +ve +ve +ve +ve/-ve
Q. Born haber cycle for Al2O3(s)
3
2Al (s) + O (g) Hf Al2O3(s)
2 2
Hsub 3 H
B.E
2
2Al(g) 3O(g)
HI.E 1
Heg 1
+
HL.E
2Al (g) –
3O (g)
HI.E 2
2+
2Al (g) Heg 2
HI.E 3
3+ 2–
2Al (g) + 3O (g)
3
Hf = 2Hsub + 2 HI.E1 + 2 HI.E 2 + 2HI.E3 + HBE + 3Heg1 + 3Heg2 + HL.E.
2
Q. Born haber for NaBr
1 Br () Hf
Na (s) + 2 NaBr(s)
2
Hsub 1 Hvap
2
Na(g) 1 Br (g)
2
2
1 H H
B.E.
2
HI.E. Br(g)
HEg
+ -
Na (g) + Br (g)
RESONANCE page # 6
General characteristics of ionic compounds :
(a) Physical state (b) Melting and boiling points
(c) Conductance (d) Crystal structure
(e) Brittlrness (f) Solubility
(g) Isomorphism
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
1 1
S.E. Z+ Z–
r r
1
1 (nature of solvent) where is dielectric constant.
r
r
Greater the polarity, greater will be r
r 1/ r , 1–1/r S.E.
H2O CH3OH C2H5OH C6H6
r 81 34 27 34
RESONANCE page # 7
LECTURE # 2
(d) Solubility of ionic solids :
1 1 1
Now we have
L.E. r r and S.E.
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
1 1 1 1
L.E.
110 120 130 140
1 1 1 1 1 1 1 1
S.E.
100 10 100 20 100 30 100 40
decreament in solvation energy > decreament in lattice energy
Solubility Orders.
Increase difference in radii solubility and viceversa
i. LiF LiI increses
ii. NaF Na increase
iii. LiF CsF increase
iv. CsF Cs decrease
v Li Cs decrease
vi Be(OH)2 Ba(OH)2 increase
vii LiOH CsOH increase
viii BeSO4 BaSO4 decrease
white ppt
ix LiClO4 CsClO4 decrease
Explain by Fazan’s rule, because of covalent character solubility
x BeF2 Be2 decrease
xi AgF Ag decrease
Q. NaF Na[BF4]–
which is more soluble
Ans. Na[BF4]– difference will solubility
RESONANCE page # 8
(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.
O O
C N
– –
O– O
Can be Isomorphus
Na2CO3 Na2SO3 (Not isomorphus)
CO32– SO32–
SP2 SP3
O
:
S
C O
– O–
– O–
BaSO4 KMnO4
SO42– MnO4–
Sp3 Sp3
O O
S Mn
O O
– O– O–
O
O O
N Cl
O
O O– O O–
RESONANCE page # 9
COVALENT CHARACTER IN IONIC COMPOUNDS (FAJAN’S RULE) :
There is no compound which is 100% ionic.
Covalent character in ionic compound can be explained with the help of Fajan’s rule.
According to Fajan’s 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.
e.g.
– Charge of cation
– Polarisation
– Covalent character
(b) Charge on anion :
AlF3 Al2O3 AlN
F– , O–2 , N–3
– 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)
RESONANCE page # 10
LECTURE # 3
Application & Exceptions of Fajan’s 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
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 page # 11
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.
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
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.
RESONANCE page # 12
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.
(ii) More is the extent of overlapping between the two atomic orbital, stronger will be bond.
RESONANCE page # 13
Examples of overlapping of pure atomic orbitals.
(i) H2 (s–s) H= H=
F2 Cl2 Br2 2
2p-2p 3p-3p 4p-4p 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
not allowed
not allowed
not allowed
Q. Count the & bonds in N C – C C – C N
Ans. 6&5
RESONANCE page # 14
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 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.
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 page # 15
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 page # 16
Table 4.8 Shapes of Molecules containing Bond Pair and Lone Pair
RESONANCE page # 17
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.
RESONANCE page # 18
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 hybrid-
ization. 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
Inter Mixing of pure atomic orbitals before bonding to produce new hybrid orbitals, specially for bonding
purpose
Postulates
(i) It is a hypothetical concept
(ii) 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)
(iii) The number of hybrid orbitals generated will be equal to the number of pure atomic orbitals taking part in
hybridisation.
(iv) 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
(v) The hybrid orbital generated will be represented by
RESONANCE page # 19
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
180º
120º
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
sp2-sp2 bond
(unstable)
(SP2) :O C O:
S.N. = 3
S.N of C=2 S.N. = 3 (SP2)
SP
(S+Px) (S+Px+Py)
RESONANCE page # 20
xy plane
py
(xy) (xz)
:
:
x axis
x-z
plane
:
:
F
F S F
(b) SF6 S.N. = 4(SP3)
F F
S.N. = 6
(SP3d2)
F
2
B S.N = 3 (SP)
(c)
F F S.N.= 4 (SP)
3
2
S.N = 3 (SP )
:
S
(d) SO2
: :
2
:O O S.N = 3(SP )
<120º
:
:
:
O
2
S.N = 3 (SP )
:
(e) SO3 S
: 2
: :
O : O S.N = 3(SP )
120º
:C N:
S.N = 2 .x
(f) CN– S.N + 2 (SP) Or
: C N:
(SP)
Out of C & N less E.N. element i.e C will donate its .P.
H +
:
3
N S.N = 4 (SP ) N S.N = 4 (SP3)
(g) NH3 (h) NH4+
H
H H H
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 page # 21
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, H–C C–H
SP
(b) =C= O=C=O H2C = C = CH2
: :
(f) BeCl2(g) : Cl Be Cl :
:
S.N = 2
(SP)
In solid state, BeCl2 is formed in form of polymer (BeCl2)n
Cl Cl Cl Cl Cl
Be Be Be Be Be
Cl Cl Cl Cl
S.N = 4 (SP3)
.x
:N N N:
:
x.
:N N N:
N = N = N
SP
In azide ion, both N–N bond lengths are equal and it is a linear ion.
RESONANCE page # 22
(i) Hydroazoic acid (HN3)
+
:
N N N
120º 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
H
:
Sol. CH3 C N : H 3C N
H
3
SP SP
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
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 page # 23
OTHER EXAMPLES :
B
AB3 A 120º trigonal planer BF3, C6H6, CO32– , B(OH)3, SO3, NO3– ,+CH3, graphite,
B B
:
A
ALB2 Bent molcule SO2, SnCl2, NOCl, O3, NO2–
B B
3.40 Aº
The structure of a
graphite sheet
C - C B.L in sheet = 1.40 Aº (benzene)
Q. Graphite is anisotropic with respect to electrical conductivity.
Ans. Graphite is good conductor of electricity along the layer because of delocalised electrons and poor conduc-
tor 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. Graphite is consider as diamagnetic substance.
Ans. Since e– are paired due to delocalised -bond. So it is diamagnetic in nature (repelled in to the magnetic
field)
Q. Graphite is used as lubricants.
Ans. 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 C–C partial double bond length.
RESONANCE page # 24
BORON TRIHALIDES
H
N N H
H
B B B B
N N N N
H H
B B
B 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.
3
Cl sp
H
H B H
H N N H
Cl B B H
H N
Cl
H 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 page # 25
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.
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 hydro-
gen 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.
RESONANCE page # 26
Examples of sp3 hybridisation
AB4 AB3L AB2L2 ABL3
shape tetrahedral pyramidal V shape Linear
(bent)
B
109º 28' Ä ..
A
..
A B ºB ..
<109
A
..
B B B 28' B <109º 28' B .. – B
B
..
Example CH4 (109º 28’) NH3 (107º) H2O(104º5º) ClO–
..
l.p – b.p. > b.p – b.p. Cl
–
..
.. – O
Compounds of berillium
1. [BeF4]– (sp3 hybridised) (already taught)
Tetraflouroberrylate (ii) ion
2. BeCl2(s)
(BeCl2)n polymeric solid (already taught)
Cl Cl Cl Cl
Be Be Be
S.No. = 4 sp3
Cl Cl Cl Cl
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
H H sp
H
Diamond
Graphite is more reactive than diamond
1500 º C
Graphite Diamond
50,000 60,000 atm
Each C is bonded to 4 other C atoms.
sp3 hybridisation.
Each C – C B. L. = 1.54 Å.
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 3930ºC) and the
structure is very hard (In a rare modification of diamond.
RESONANCE page # 27
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 (will form 3-D structure)
(stable)
Elements forming Multiple bonds
C N O
P S Cl
SiO2 Covalently bonded 3D giant network solid like diamond.
Si
O O O
O
Si Si O
O Si O
O O
O O
O
Si
O O
– –
O
–
O
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 page # 28
(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 O O
O– O–
O–
O O O O
O– O– O– O–
–
–
O O O –
O O O O
–
O–
–
O
Si3O96– Si6O1812–
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
O– O–
O O
O O O O
O O
O– O– O–
O O O
O– O– O–
O O O O O O
O– O––
O– O–
P P
60º (P will be on all 4 vertexes of tetrahedron) (nothing at centre)
RESONANCE page # 29
P4O6
O
P
O O
O
O P OP O
P4O10
O P O
O
P4S3
Oxygen Family :
Compounds of S :
S8 (Crown sulphur)
S32–
SCl2
V-shaped
S2Cl2
RESONANCE page # 30
Halogen family :
HClO4, HClO3, HClO2, HClO
XeO4
Xenon tetraoxide tetrahedral
XeO3
Q.1 Discuss the shape, geometry and bond angle of the following molecules.
NH3 H2O O3 SO2
Ans. NH3 (Ammonia)
..
..
N
shape : pyramidal
H H H
Geometry : tetrahedral , bond angle = 107°
:
S
B.A. < 120º
O
118º O
O3 (Ozone)
:
O
O O
:
:
:O O O:
:
O
O 117º O
Bond strength of both bond is equal diamagnetic substance. Ozonide ion (O3–) from KO3 paramagnetic
substance.
–
unpaired e
:
O
:
: :
O : O :
:
O2 Paramagnetic
(can be explained on the basis of MOT)
O–O B.L. is smaller then H2O2 because of smaller electron density on O atom in comparison to H2O2.
RESONANCE page # 31
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 zeisse’s salt.
Q.3 Discuss the shape of NH2– (Amide ion) an
.. ..
–
N
Ans. V–shaped 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
RESONANCE page # 32
8. Cyclic-metaphosphoric
(HPO3)n
OXY-ACIDS OF SULPHUR
(S atom in sp3 hybridised)
O O
|| ||
2. H2S2O4 Dithionous acid H O S
. . S
. . O H
O O
|| ||
3. H2S2O5 Pyrosulphurous acid H O S S
. . O H
||
O
B. Sulphuric acid series.
O
||
1. H2SO4 Sulphuric acid H O S O H
||
O
O
||
2. H2S2O3 Thiosulphuric acid H O S O H
||
S
O O
|| ||
HOS OSOH
3. H2S2O7 Oleum || ||
O O
RESONANCE page # 33
Peroxy acids of S
O
||
1. H2SO5 Peroxymonosulphuric acid (caro’s acid) HO O S O H
||
O
O O
|| ||
2. H2S2O8 Peroxydisulphuric acid (Marshall’s acid) HO S O O S O H
|| ||
O O
OXY-ACIDS OF ‘Cl’
(Cl atom is sp3 hybridised)
OXY-ACIDS OF NITROGEN
(N atom sp2 hybridised)
.. ..
2. HNO2 Nitrous acid (Pale blue) HO
. . N O
RESONANCE page # 34
LECTURE # 8
Example of sp3d hybridisation :
sp3d (s + px + py + pz + dz2)
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
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
P
PF2Cl3 net = 0
Cl Cl
F
F F
P
PCl2F3 =0
Cl Cl
F
AB4L
RESONANCE page # 35
•• F
S
SF4 Seasaw
F F
F
•• F
Xe
XeO2 F2 Seasaw
O O
F
AB3L2
•• F
Cl
ClF3 T-shaped
••
F
F
> 180°
Due to .p. – b.p. repulsions therefore FClF is not linear
+
•• F
[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
AB2 L3 XeF2 Xe
••
••
F
–
••
3–
••
••
+
•• ••
3+ S. No. = 4 sp3
bent
–
• • Cl
Cl2–
••
••
Cl
RESONANCE page # 36
Q. Select the correct structure of ClF3 amongs the following with proper reasoning.
F •• F F
__
PF6¯ F 2-
F F
F F F F F F [AlF6]3-
S P [SiF6]2- Si
SF6
F F F F F F
F F F
[XeO6]4–
H
•• O
Xe
sp3d O O
O
H
4-
O O
O O ¯O O¯
Xe Xe
OR
O O ¯O O¯
O O
RESONANCE page # 37
AB5L : BrF5
F
F F
Br
F F
..
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.
O
F F
Xe
F F
..
AB4L2 : Cl4¯
_
..
Cl Cl
Cl4¯ µ=0
Cl .. Cl
F F
F 90° F
F
72°
F F Xe
F F
F F
F F
But XeF6(s) is found to exist in tetrameric form when [XeF5]+ units are linked by F¯
RESONANCE page # 38
hyb of Xe in [XeF5]+ is found to be sp3d2
[XeF5]
+ Electrostatic Attraction
F¯ F¯
+ +
[XeF5] [XeF5]
F¯ F¯
+
[XeF5]
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. 109°28’ 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 page # 39
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
Ans. OF2
Cl2O
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 Discuss the bond angle in Thionyl halide.
Ans. 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 page # 40
Q.7 Discuss the basic strength and bond angle hydride of nitrogen family.
Ans. NH3 PH3 AsH3 SbH3
B.A. 107º 92º-93º 92º 91º
[O = N = O]+
<
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 y H H
2 B 1 B
Ht Hb H
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
–
B.A. 2 > 1
RESONANCE page # 41
Ht terminal H atom
Hb bridging H atom
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 C CH3
Al Al
H3C C CH3
H H
H
But Al2Cl6 hame covalent bond only no electron deficient bonding.
Cl Cl Cl
Al Al
Cl Cl Cl
BORON TRIHALIDES
Q. Observed bond length in BF3 molecule in found to less than the expected.
Ans. B There will be p - p back bonding between 2p of B atom & 2p of F atom. Bond length of B
:F F
:
- F will decreases
RESONANCE page # 42
Q. Compare B-F bond length in BF3 and [BF4]–.
Ans. BF3 + KF K + [BF4]–
F
B SP3 hybridised [No back bonding]
F F F
Q. Explain all boron trihalides are lewis acids also explain their order.
Ans. Boron trihalides are electron deficient molecules therefore act as a Lewis acids
Cl
But in BCl3 B P -P back bonding 2p of B & 3p of Cl less effective
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
N S.N = 3 |
CH3 CH CH3
3
SiH3 SiH3
:
N (CH3)3 pyramidal
Planar
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.
Q. Silyl isocyanate (SiH3NCO) is linear but methyl isocyanate (CH3NCO) is bent explain !
H H
:
:
:
Sol. H Si N C O H C N C O
H H
vacant No vacant
d-orbitals orbitals
RESONANCE page # 43
(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
OH2 O
O H
H
OH
2
H
H2 O
O
H
O
H H
(hydration) many such layer will
form.
LECTURE # 10
Hydrolysis via co-ordinate bond formation.
Hydrolysis of BCl3( due to presence of vacant orbitals on boron)
H
H Cl O
vacant pure Cl H
p- orbital O H B
B
Cl Cl
Cl Cl
OH OH Cl OH
H2O
B + HCl B + HCl
OH Cl
RESONANCE page # 44
Hydrolysis of boron trihalides :
Cl Cl
B undergo hydrolysis by coordinate
B (OH)3 (Boric acid) + 3HCl
bond formation
Cl
H O
:
N
H NH3 + HOCl
Cl Cl Cl
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.
RESONANCE page # 45
3rd period
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
H3PO4
(Phosphoric acid)
DIPOLE MOMENT
P 2 Q 2 2PQ cos
RESONANCE page # 46
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
µExperiment al ( Observed)
% Ionic character = 100 = 100
µTheoretica l (100% Ionic compound)
CH3
Cl
RESONANCE page # 47
(v) N
H N
3
F
3
Q. CH3–F CD3–F
APPLICATION OF D.M.
for calculation of theoritical it is assumed that 1e– is completely transferred from one atom to another.
1 1
= 4.8 × 10–10 e.s.u. A B
x = given to us as B.L. (cm)
Q. For H–Cl gas molecule exp = 1.03D
Bond distance = 1.275 Å
Calculate the % ionic character.
Sol. theo = 4.8 ×10–10 × 1.275 × 10–8
= 6.12 × 10–18
1.03 10 18
% ionic char. = 100 = 17%
6.12 10 18
RESONANCE page # 48
Q. If OH bond distance in water = 0.572 Å
Then calculate what fraction of electronic charge is present on the O atom.
x = 0.572
10–8 x 1.51 = × x
1.51 10 18
=
0.527 10 8
Fraction of electronic charge =
4.8 10 10
Q. Net of SO2 = 1.61 D. B.L. S–O = 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 S–O–bond.
x 100
25 = 10
4.8 10 0.145 10 7 cm
x = 1.74 D
1.61 = x 2 x 2 2 x 2 cos
cos = – 0.572
125 º
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 mo-
lecular orbital are formed.
(v) The bonding molecular orbital has lower energy and hence greater stability than the corresponding antibonding
molecular orbital.
RESONANCE page # 49
(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 Hund’s 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.)
Antibonding orbital
higher enrgy than
that of atomic orbitals
Molecular
orbitals Atomic
Atomic
Increasing energy
orbital orbital
*A – B
A B
=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 be-
tween 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 page # 50
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.
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 page # 51
Molecular Antibonding sigma
orbitals molecular orbital
Atomic Atomic –
+ + +
orbital orbital
1s 1s
Energy
*1s *1s
1s 1s Bonding sigma
molecular orbital
+ +
1s + +
1s 1s 1s
(a)
Atomic Atomic – + – + – – + – +
orbital orbital
2pz 2pz
Energy
*2pz *1s
Bonding sigma
molecular orbital
2pz 2Pz
– + + + – – + –
*2px
2pz 2pz *2px
Bonding sigma
2px 2Px molecular orbital
+ + +
–
– – –
2px
2px 2px 2px
(c)
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.
** 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.
(i) The molecule is stable if Nb is greater than Na, and
(ii) 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 MO’s.
RESONANCE page # 52
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.) = ½ (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.
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 )
RESONANCE page # 53
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
B.O. of N2 = (10 – 4) = 3. one sigma and two bonds.
2
6. 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
1
B.O. of N2¯ = (10 – 5) = 2.5
2
7. 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.
*2p *2p
*2p *2p
2p
2p
Energy
2p 2p
*2s *2s
2s 2s
–1
Bond energy/kJmol
Bond length/pm
900 150
159 945 143
131 121
600 110 100
620
498
300 50
290
290
Bond order 1 2 3 2 1 0
configuration
RESONANCE page # 54
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
Bond order = 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 paramag-
netic, 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.
10 10
B.O. = =0
2
Species BE (kJ/mol) B.L. (pm)
H2 432 74
H2+ 255 106
He2+ 230 108
22px
1s2 , 1s2 , 2s2 , ( 2py 2 , 2pz 2 ) ,
HOMO
B.O. = 3
1 and 2 bond
RESONANCE page # 55
The MO configuration of CO has given above cannot be considered to be 100% correct because if CO is
94
converted into CO+ then, its B.O. = = 2.5. B.L. must
2
B.L.CO = 1.128 Å
B.L.CO+ = 1.115 Å
10 4
(D) B.O. = =3
2
1 and 2 bond
RESONANCE page # 56
LINEAR COMBINATION OF 2p-ORBITALS
(a) Along the Molecular Axis ()
nodal plane
n
Addition Sub
– + + + – – – – + – +
2px 2px
2px
gerade
2px
ungerade
+ + +
Addition ungerade
+
– –
– 2py
2py 2py
Subn gerade
–
2py
Conclusion :
s s
p all gerade. *p ungerade
p *p
MOT FOR HF
HF
H * F
p
2py 2pz 2px 2py 2pz
(NBD)
MO
NBD 2s
NBD 1s
2–0
B.O. = =1
2
Atomic orbitals is always monocentric But molecular orbitals is always polycentric.
RESONANCE page # 57
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.
(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
+
A H ----- :B
(-ve) (-ve)
H-bond
(v) H-bonds are found to be much stronger with F-atoms but in case of other atoms the relative strength of H-
bond 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)
(C) N H - - - - - - :N (D) N H - - - - - - :O
A H- - - - - :B
(vi) x y (generally distance x < y)
But in case of very strong H-bonding
x = y,
Ex. K+[HF2]–
RESONANCE page # 58
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
R
1.74Å 1.01Å
H O- - -H O
| |
H H
F F
H 120° H H H
to
F 140° F
O H O
H3C C C H
O H O
HCO3– in KHCO3 In dimeric form but HCO3– in NaHCO3 is in linear polymeric form.
O H O
O=C C=O
O¯ H O
H
|
O
O
H B H
O |
H3BO3(s) O
|
H B H H
O O
(B) Intramolecular :
O
O O
N
(i) O-nitrophenol
O
H
Cl O
Cl C C H
Cl O
RESONANCE page # 59
(iii) Maleic Acid :
O
||
H C COOH H C C O
|| || H + H+
H C COOH H C C O K2 << K1
||
O
(iv) Anion of Caro’s Acid :
O
|| O O
O
H O O S O H S H
|| st O O
O 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 H–bond
B.L.OH x = 122 pm ; B.L. N–H y = 100 pm
RESONANCE page # 60
Questions based upon H-bonding
R O HO
| | Association is very small
R H
solubility of ether is much less.
C2H5OC2H5 8 gm/100gm H2O
CH3CH2CH2CH2OH
Hydrocarbon chain solubility
Infinite solubility
CH3OH
C2H5OH
CH3CH2CH2OH
CH3 CH CH3
|
OH
CH2=CH–CH2OH
H O H O D O D O
| | | |
(vi)
H H D D
RESONANCE page # 61
(vii) Ice floats on water
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 4ºC
slightly
H2O(s)
warm
ice T < 4ºC
d >0ºC
In this temperature region some of the ice melts and hence some H2O molecule go into the cages of
remaining ice structure.
V d becoming max at 4ºC but beyond this temp thermal effects become dominating V d
(ix) Water can extinguish the burning alcohol but not the burning petrol or a Hydrocarbon (in general).
H2O(l) + R–OH(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
(x) Which is a stronger base why?
(a) Trimethyl ammonium hydroxide
RESONANCE page # 62
C2H2 is highly soluble in acetone due to H bonding
– + – +
e.g. ,
Cl
Cl
Cl
Cl
RESONANCE page # 63
Strength of vander waal force molecular mass.
van der Waal’s force Boiling point.
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 (n–1) 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 page # 64
LECTURE # 13
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 – peroxide
O2 – superoxide
2–
S – sulphide
Se–2 – selenide
Te–2 – telluride
Nitrogen family
N3– – nitride
N3 – azide
3–
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) Ca3P2 (2) Ba(CN)2 (3) Na2S
(4) ClF3 (5) SF4
Write down the formula of
(1) Sulphur hexafluoride (2) Lithium nitride (3) stroncium chloride
(4) dioxygen di fluoride (5) barium azide
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
1. 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)
2. 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 page # 65
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 in four. O.No.
Then highest – per – ic
next lower – ic
next lower – us
lowest – hypo – us.
Chlorine
+7 HClO4 perchloric acid
+5 HClO3 chloric acid
+3 HClO2 chlorus acid
+1 HClO 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
2HClO4 Cl2O7 not oxiacid it is an oxide
H O
2
2H2SO3
H 2 O
H S O pyro sulphurous acid
2 2 5
Nitrogen
No pyro acid (as an oxide will be obtained)
phosphorous
2H3PO4 H P O pyro phospheric acid
H 2 O 4 2 7
2H3PO3
H 2 O
H P O pyro phosphoros acid
4 2 5
meta acid: If one water molecule is derived from one acid molecule then meta acid is obtained.
One acid molecule meta acid
H O 2
Naming of oxoanions
– ic acid – ate ; – us acid – ite
Chlorine
HClO4 ClO4– perchlorate ; HClO3 ClO3– chlorate
HClO2 ClO2– chlorite ; HClO ClO– hypochlorite
RESONANCE page # 66
sulphur
H2SO4 SO42– sulphate
HSO4– bisulphate (hydrogen sulphate)
H2SO3 SO32– – sulphite
HSO3– – bisulphite (hydrogen sulphite)
H2S2O7 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 SiO44– – silicate
H6Si2O7 Si2O76– – pyro silicate
H2SiO3 SiO32– meta silicate
Carbon
H2CO3 CO32– – Carbonate
HCO3– – bicabonate { hydrogen carbonate)
Boron
H3BO3 BO33– borate
H4B2O5 B2O54– pyroborate
HBO2 BO2– meta borate
Q. Write the formula of
(1) barium perchlorate (2) sodium hypochlorite (3) calcium phosphate
(4) magnesium pyro 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
7
higher oxidation state of manganese MnO 4
So called permanganate HMnO4– permanganic acid
Polysulphides
S2x ( x = 2, 3, 4, 5..........)
structures S22 –S – S– disulphide
S
S23 –
trisulphide
S S
–
S
– S
S24 S –
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 page # 67
O S
|| ||
S S
|| ||
O
–
–
O O– O O O
–
OH2 O
O H
H
OH
2
H
H2 O
O
H
O
H H
(hydration) many such layer will
form.
Be2+ 2sº 2pº = sp3 hybridisation
RESONANCE page # 68
CHEMISTRY LECTURE NOTES
(2012-13)
CHEMISTRY
CHEMICAL BONDING
LECTURE # 1 TO 12