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pi

Fig. The shapes of molecuies in which central atom has no lone pair
Hybridization
(Steric No)
e
EXAMPLES OF DIFFERENT HYBRIDISATION
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
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
Q. Will all the 4 H atom in propadiene be coplanar

H spxp z spx sp xp y H
Cp C C
Ans. NO y Pz
H xz xy H
+
C

(c) (ion radical  CH2
S.N =2(sp)
.
(d) C .CH2 ( triplet carbene)
:
C : CH2
:
S.N. = 3 C
2
(sp ) (sin glet Carbene )
Total spin multiplicity of any molecule = 2S + 1
S = |summation of all the spins|
 1 1
Triplet  S =    = 1
2 2
Total spin multiplicity = 3 (triplet)
Singlet S = zero
Total spin multiplicity = 1 (singlet)
Q. Which is more stable
triplet carbene or singlet carbene?
Ans. triplet carbene
Cl :
: :
: Cl Be
S.N= 4(SP3)
:
(f) BeCl2(g) 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 (SP )
3
Bond angle  90º – 95º
(g) N2
:N N:
S.N = 2 (SP)
(h) Azide ion N3 –
N3– (nitride ion)
x.
:N N N:
:
.x
:N N N:
:
x.
:N N N:
  
SP  N = N = N SP
 SP
In azide ion, both N–N bond lengths are equal and it is a linear ion.
(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 :
:
H3C N
 H
3
SP SP
Nsp > N 3 E.N order

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

EXAMPLES OF sp2 HYBRIDISATION
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°.
OTHER EXAMPLES :
B
A 120º
AB3 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
(f) Allotropes of carbon :

1. Graphite - sp2
2. 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 Aº
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.
Bucky ball (C60) Structure of

buckminster fullerence
BORON TRIHALIDES
BF3 BCl 3 BBr3 B 3
   
sp 2
sp 2
sp 2 unstable
(stearic h indrance )
Discuss the structure and hybridisation inorganic benzene B3N3H6 borazine
H
N N
H H
B B B B

N N N N
H H
B B
H
Q. How many dichloro borazine are possible ?
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.
HCl + B3N3H6  B3N3H9 Cl3
Cl sp3
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.
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

I n c a s e o f H g O m o l e c u l e , t h hybridisation forming
e f o u r o x y g e n o r b i t a l s ( o n e 2 s a n d t h r e e 2 p ) u n d e r g o s p
3
four sp hybrid orbitals out of which two contain one electron each and the other two contain a pair of
1
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.
Fig .4.14 Formation of H2O molecule
Examples of sp3 hybridisation

AB4 AB3L AB2L2 ABL3
shape tetrahedral pyramidal V shape Linear
(bent)
B
109º 28' Ä ..
A A
..
B <109
ºB ..
B B B 28' B <109º 28' B A
.. – 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
Compounds of Boron :
[B(OH)4]–, [BF4]–, [H3 N :  BF3]
sp sp
3 3
Compounds of Carbon :
 All saturated organic compounds has C in sp3 hybridised state :
..
– C S.N = 4
C H3  sp
3
H H
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.
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
Silicates (Si  Sp3 hybridised)

Basic repeating unit of silicate [SiO4]4–
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
Cyclic Silicates
Chain Silicates
Sheet Silicates
3 – D network
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–
Cyclic silicates : (SiO32–)n or (SiO3)n2n–
Pyrosilicate : [Si2O7]6–
Compounds of P : P4 (White phosphorus)
P P
60º (P will be on all 4 vertexes of tetrahedron) (nothing at centre)
6–P–P bonds P–P–P = 60º S.N. = 4 (109º28’)

Since B.A. is 60º so, P4 molecules is a strained molecule. Hence is chemically very reactive.
Can catch fire at normal room temperature in air.
P4O6
no P–P bond, 12 POP bond.
O
P
O O
O
O P OP O
P4O10
O P O
O
Oxygen Family :
H2O V-shaped molecule
H3O+ (hydronium ion)
Compounds of S :
S8 (Crown sulphur)
SCl2
V-shaped
S2Cl2
open book like structure
SOCl2 (thionyl chloride) (derivative of SO2)
SO2Cl2 (sulphuryl chloride)
Halogen family :
HClO4, HClO3, HClO2, HClO
Noble gases Family :

XeO4
Xenon tetraoxide tetrahedral
XeO3
Xenon trioxide pyramidal
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)
Q.2 Compair the O–O bond length in H2O2 and O2F2.
Ans. H2O2 (hydrogen peroxide)
open book like structure
O – O BL is more than the expected.
O2F2 open book like structure
O – O B.L. is smaller than H2O2 because of smaller electron density on O atom in comparison
to H2O2.
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, N2H4, 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 unexpected N–N length in hydrazine.
.. ..
–
N
Ans. V–shaped like H2O molecule
H H
N2H4 (Hydrazine) (NH2NH2)

H H
.. ..
N N
H H
N – N B.L. is larger than expected because of .p. – .p. repulsions.
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
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
Ex. PF5 SF4 ClF3 XeF2

PCl5 XeO2F2 XeF3+ 3–
PBr5 Cl2–
P5
PF5 : 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
0° 90°
12 P
PCl5 : net = 0
Cl 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–
+
P5(s) is expected to be P4+ and –

Cl F
P
PF2Cl3 net = 0
Cl Cl
F
F F
P
PCl2F3 =0
Cl Cl
F
AB4L
•• 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
Xe
[XeF3]+
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
••
••
F
–
•• 

3–
••
••

+
•• ••

 3+ S. No. = 4 sp3 
bent

–
• • Cl

Cl2–
••
••
Cl
Q. Select the correct structure of ClF3 amongs the following with proper reasoning.
F •• F F
(A) Cl (B) Cl (C*)

F F • F
•• •
••
Example of sp3d2 hybridisation

S.N. = 6 geometry Þ Octahedral
B.A. = 90°
Types AB6 AB5L AB4L2
Shape Octhedral sq. pyramidal Sq. planar
Ex. SF6 ICl4¯
PF6¯ XeOF4 XeF4
[SiF6]2– BrF5
[AlF6]3–
[XeO6]4–
Perxenate ion
__
PF6¯ F 2-
F F
F F F F F F [AlF6]
3-
[SiF6]
2-
S P Si
SF6
F F F F F F
F F F
[XeO6]4–
XeO3 + NaOH  Na+[HXeO4]¯
Sodium Xenate
H2XeO4 Xenic Acid
S.N. = 5
H
•• O
Xe
sp3d O O
O
H
H4XeO6 Perxenic Acid
(No peroxide group)
Structure of [XeO6]4–
4-
O O
O O ¯O O¯
Xe Xe
OR
O O ¯O O¯
O O
“Y2 Careers LLP” [41] website : www.y2c.co.in

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.
B u t i n c a s e o f X e O F d.b. and .p. are kept at 180°.

O
F F
Xe
F F
..
AB4L2 : Cl4¯
_
..
Cl Cl

Cl4¯ µ=0
Cl .. Cl
2. l.p. of are found to be at trans position so as to have min. repulsion.

..
F F
Xe
XeF4 µ=0
F F
..
Examples of sp3d3 hybridisation
Type AB7 AB6L
Example F7 XeF6
Shape Pentagonal bipyramidal Distorted octahedral
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¯
 hyb of Xe in [XeF5]+ is found to be sp3d2

[XeF ]+ Electrostatic Attraction
5
F¯ F¯
[XeF5]+ [XeF5]+
F¯ F¯
[XeF5] +
“Y2 Careers LLP” [42] website : www.y2c.co.in

Isomorphism in ionic compounds :
Isomerism 
onic compound does not show lsomerism due to non-directional nature of ionic bond
But onic compound can show
i 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
ii 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

(a) 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)
(b) The cations of both compound should be of similar shape or structure ( isostructural) similarly anions of both
compound should be isostructural
Ex.  MgCO3 NaNO3

CO32– NO3–
trigonal planar trigonal planar
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
NaNO3 NaClO4 [X]

Sp2 Sp3
O O
N Cl
O
O O– O–
O
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Q. Will all the 4 H atom in propadiene be coplanar

Bond angle  90º – 95º

Nsp > N 3 E.N order

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

Fig.4.11 Formation of sp2 hybrids and the BCl3 molecule

(f) Allotropes of carbon :

Graphite each C  sp2

Q. Graphite is anisotropic with respect to electrical conductivity.

Q. Graphite is consider as diamagnetic substance.

Q. Graphite is used as lubricants.

Fullerenes (C60 , C48 , C30 ...........)

Bucky ball (C60) Structure of

Fig.4.13 Formation of NH3 molecule

Examples of sp3 hybridisation

Si –– O –– Si (will form 3-D structure)

 Elements forming Multiple bonds

SiO2  Covalently bonded 3D giant network solid like diamond.

Silicates (Si  Sp3 hybridised)

Compounds of P : P4 (White phosphorus)

6–P–P bonds P–P–P = 60º S.N. = 4 (109º28’)

no P–P bond, 12 POP bond.

H2O V-shaped molecule

H3O+ (hydronium ion)

open book like structure

SOCl2 (thionyl chloride) (derivative of SO2)

SO2Cl2 (sulphuryl chloride)

Noble gases Family :

Xenon trioxide pyramidal

open book like structure

O – O BL is more than the expected.

O2F2 open book like structure

N2H4 (Hydrazine) (NH2NH2)

N – N B.L. is larger than expected because of .p. – .p. repulsions.

Order of base strength

Ex. PF5 SF4 ClF3 XeF2

P5(s) is expected to be P4+ and –

(A) Cl (B) Cl (C*)

Example of sp3d2 hybridisation

“Y2 Careers LLP” [41] website : www.y2c.co.in

B u t i n c a s e o f X e O F d.b. and .p. are kept at 180°.

2. l.p. of are found to be at trans position so as to have min. repulsion.

 hyb of Xe in [XeF5]+ is found to be sp3d2

“Y2 Careers LLP” [42] website : www.y2c.co.in

 For two compounds to be isomorphus

Na2CO3 NaNO3 [Not isomorphus]

Ex.  MgCO3 NaNO3

NaNO3 NaClO4 [X]

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