1

The chemical properties of an element depend on the electronic

configuration of the outer shell. Carbon has four electrons in its outer
shell.

According to the ground state electronic configuration of carbon,

carbon is divalent. Tetravalency of carbon can be explained by
promoting one 2s - electron to a 2pz orbital. Some energy must be
supplied to the system in order to effect this promotion. This
promotion requires energy about 96 kcal/mol, but this energy is more
than regained by the concurrent formation of chemical bonds.

        
6 C 
2px 2p 2pz 1s2 2s1 2px 2py 2pz
1s2 2s2

Carbon in ground state Carbon in excited state

The four valencies of carbon atom are similar and

they are symmetrically arranged around the
carbon atom. According to Le Bel and Van’t Hoff 109o28
the four valencies of carbon do not lie in one plane. 1.09Å C

They are directed towards the corners of a regular

tetrahedron with carbon atom at the centre and the angle between any
two valencies is 109o28.
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Bonding in organic compounds

The organic compounds are carbon compounds consisting of one or

more carbon atoms. Carbon must form only covalent bonds, i.e., it
should share its valency electrons with other atoms.

According to the modern concept, a covalent bond is formed between

two atoms if there is an overlapping of an atomic orbital of one atom
with an atomic orbital of another atom. The overlapping is possible
by two ways,

(1) End to end overlapping : This type of overlapping is possible

between s  s, s  px and px  px atomic orbitals. The molecular bond

formed is termed as sigma ( ) bond.

(2) Sidewise or parallel or lateral overlapping : Such

overlapping is possible between p  p atomic orbitals. The molecular
bond formed is termed as pi ( ) bond.

 -Bond  -Bond

Formed by End to End overlap of Formed by lateral overlap of p -

AO’s. orbitals.

Has cylindrical charge symmetry Has maximum charge density in

about bond axis. the cross-sectional plane of the
orbitals.

Has free rotation No free rotation, i.e., frozen

rotation

Low energy Higher energy

Only one  bond can exist between One or two  bonds can exist
two atoms, between two atoms.
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Sigma bonds are directional. Thus  bonds are not directional.

the geometry of the molecule Geometry of the molecule not
depends on the  bonds. depends on  bond.

Area of overlapping is higher hence Area of overlapping is small hence

bond is stronger. bond is weaker.

 bond can have independent  bond always exist along with a 

existence. bond and  bond is formed after
the formation of  bond.

Hybridisation in Organic Compounds

(1) The process of mixing atomic orbitals to form a set of new

equivalent orbitals is termed as hybridisation. There are three
types of hybridisation encountered in carbon atom. These are,

(i) sp3 hybridisation (involved in saturated organic compounds

containing only single covalent bonds),

(ii) sp2 hybridisation (involved in organic compounds having carbon

linked by double bonds) and

(iii) sp hybridisation (involved in organic compounds having carbon

linked by a triple bonds).
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Type of Number Number of Bond Bon Geomet % s-

hybrid of unused d ry charact
isation orbital p-orbitals ang er
s used le

sp3 1s and Nil Four - 109. Tetrahe 25 or 1/4

3p 5 dral

sp2 1s and One Three - 120 Trigonal 33.33 or

2p One - 1/3

sp 1s and Two Two - 180 Linear 50 or 1/2

1p Two -

(2) Determination of hybridisation at different carbon atoms:

It can be done by two methods,

(i) First method : In this method hybridisation can be know by the

number of   bonds present on that particular atom.

Number of – bond/s 0 1 2

Type of hybridisation sp3 sp2 sp

O
||
Examples : (i) CH3  CH  CH C  CH3 (ii) CH2  C  CH2
       
4

2 2
sp3 sp sp sp2 sp3 sp2 sp sp2
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(iii) CH3  CH  CH  CH2  C  N

     
sp3 sp2 2
sp sp3 sp sp

(iv) HC  C  CH  CH2
   
sp sp sp2 sp2

Note :  In diamond carbon is sp3 hybridised and in graphite carbon

is sp2 hybridised.

 This method can not be used for those atoms of the molecule
which have positive charge, negative charge or odd electron.

(ii) Second method : (Electron pair method)

ep = bp + lp; where ep = electron pair present in hybrid orbitals ,

bp = bond pair present in hybrid orbitals

Number of bp = Number of atoms attached to the central atom of the

species

Central Central
First atom H atom atom
H 1
2
C=C H
Second atom H H 3
bp = 3 bp = 3
Third atom

Number of lp’s can be determined as follows,

(a) If carbon has  - bond/s or positive charge or odd electron, than

lp on carbon will be zero.
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(b) If carbon has negative charge, then lp will be equal to one.

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Number of electron pairs (ep) tells us the type of hybridisation as

follows,

ep 2 3 4 5 6

Type of sp sp2 sp3 sp3 d sp3 d2

hybridisation

Example :
 
(i) CH2  CH (ii) CH2  CH
 
bp  2 bp  2
lp  0 lp  1
ep  2, sp ep  3, sp2
 
(iii) CH2  C  CH3 (iv) CH  C
| 
bp1
CH3 lp  1
bp  3 ep  2, sp
lp  0
ep  3, sp2

(v) CH3  CH CH3

bp3
lp  1
ep  4, sp3
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(3) Applications of hybridisation

(i) Size of the hybrid orbitals : Since s - orbitals are closer to

nucleus than p - orbitals, it is reasonable to expect that greater the s

character of an orbital the smaller it is. Thus the decreasing order of

the size of the three hybrid orbitals is opposite to that of the
decreasing order of s orbital character in the three hybrid orbitals.

sp3  sp2  sp

(ii) Electronegativity of different orbitals

(a) Electronegativity of s-orbital is maximum.

(b) Electronegativity of hybrid orbital  % s-character in hybrid

orbitals

Orbital sp sp2 sp3

% s -character 50 33.33 25
 

s-character in decreasing order and electronegativity in decreasing order

Thus sp-hybrid carbon is always electronegative in character and sp3 -

hybrid carbon is electropositive in character. sp2 -hybrid carbon can
behave as electropositive (in carbocation) as well as electronegative
(in carbanion) in character.
 
CH3  CH2 CH2  CH
sp

Electropositive carbon Electronegative carbon

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having positive charge

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(c) Electronegativity of different hybrid and unhybrid orbitals in

decreasing order is as follows

s  sp  sp2  sp3  p
 

% s-character in decreasing order and electronegativity in decreasing order.

(iii) Bond length variation in hydrocarbons

1 1
% s orbital character  
C  C bond length C  H bond length

Bond type (C – Bond length Bond type (C – Bond length

H) C)

sp3  s (alkanes) 1.112Å sp3  sp3 1.54 Å

(alkanes)

sp2  s (alkenes) 1.103Å sp2  sp2 1.34Å

(alkenes)

sp  s (alkynes) 1.08Å sp  sp (alkynes) 1.20Å

Note :  C–C bond length in benzene lies between single and double
bond due to resonance. (1.40Å).
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(iv) Bond strength in hydrocarbons : The shorter the bond, the

greater the compression between atomic nuclei and hence greater the
strength of that bond is. Thus the bond formed by sp hybridised
carbon is strongest (i.e., it has maximum bond energy) while that
formed by sp 3 hybridised carbon is the weakest (i.e., it has minimum
bond energy). This is evident by the bond energies of the various types
of C  H and C  C bonds.

Bond type (C – Bond energy Bond type (C – Bond energy

H) (kcal/mole) C) (kcal/mole)

sp3  s (in 104 sp3  sp3 (in 80 – 90

alkanes) alkanes)

sp2  s (in 106 sp2  sp2 (in 122 – 164

alkenes) alkenes)

sp  s (in 121 sp  sp (in 123 – 199

alkynes) alkynes)

(v) Acidity of hydrocarbons

(a) Hydrogen present on electronegative carbon is acidic in

character.

(b) Acidity of hydrogen is directly proportional to the

electronegativity of atom on which hydrogen is present.
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Thus
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H O  H
3 NH CH CH


Electronegativity of atom in decreasing order
Acidity of compounds in deceasing order

(c) Acidity of hydrocarbon  % s-character

CH  CH CH2  CH2 CH3  CH3

% s-character 50 33.33 25

pKa 25 44 50

s- character in decreasing order and acidity in decreasing order

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Note :  Acidity  Ka and Acidity  (pKa   log Ka)
pKa

 Order of acidic nature of alkynes is, HC  CH  HC  C  CH3

 The relative acidic character follows the order;

H2O  ROH  HC  CH  NH3  CH2  CH2  CH3  CH3

Obviously, the basic character of their conjugate bases follows the

reverse order, i.e.,

CH 3 CH 2  CH 2  CH   NH 2  HC  C   RO   HO 
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