THEORIES OF COVALENT BOND:
VALENCE BOND THEORY :
describes and explains :
----> overlapping of atomic orbitals
---> the electronic structure of molecules
It was introduced by Pauling and Slater .then it was extended by Hitler and another scientist .
#covalent bond is formed by overlapping of atomic orbitals . Atoms should come very close for this
purpose
# only half filled orbitals with e- of opposite spin overlap
these are two half filled oribals of two diiferent atoms with opposte spin electrons , when they overlap ,
a bond is formed
#overlapping must be less than 50%.If more than 50% , then the nucleus of 2 atoms will come very close
and thus , repulsion will start between the 2 nucleus
#extent of overlapping decides strength of bond
extent of overlapping ∝ strength of bond ∝ bond energy ∝ 1/bond length
#two types of overlapping is possible :
1) Axial overlapping / Head on overlapping : sigma bond is formed
2) parallel overlapping / sidewise overlapping / lateral overlapping: pie bond is formed
#the overlapping orbitals must have same sign and orienation , only then the bond will be formed
sigma bond is the first bond between two atoms
sigma bind is the stronger one than pie bond because sigma can do more overlapping
pie bond is the second or third bond between two atoms . it can't be the first one
------------------------------------------------->TWO TYPES OF OVERLAPPING
--------------------->AXIAL / HEAD ON OVERLAPPING :: SIGMA BOND IS FORMED
sigma bond is made between s-s orbital , s- porbital and p - p orbital
These are 2 s orbitals of two diiferent atoms . they are overlapping . the bond formed between them is
sigma bond .
s-orbitals is non-directional since it has a spherical shape .so the bond formed between s and s orbital is
sigma bond even .so the bond formed between the s and p orbital is sigma .s-orbital can never form pie
bond because the overlapping of s-orbital is always axial .
------------------------------------------------------> s-s sigma bond:
let us take an example of bond between H2 molecule :
The sigma bond formed here is called 1s-1s sigma bond
-------------------------------------------------------------------> s-p sigma bond:
let us take an example of hydrogen fluoride HF
in this example, 1s-2pz sigma bond is formed .Similarly
Q which bond has more bond energy ? which has strong bond ?
so , orbital having n small , it is close to nucleus and thus , strong bond is formed .and thus , there will be
more bond energy .
another Question:
Q: which bond has more bond length ?
the orbital having n small , it is close to nucleus ,bond will be strong thus , bond length will be small and
bond energy will be more .
---------------------------------------------> p-p bond (it can either be sigma and pie )
p-orbital has 3 columns : px py pz . all of them have same energy .so you can fill electrons however you
desire .
but bond will always be formed between px-px , py-py and pz-pz . not px-py because px and py have
different orientation . px orbital is in x dimension while , py is in y dimension
p-orbital has direction , so it can form both types of bond (sigma bond or pie bond)
------------------>p-p sigma bond :
These are p-orbitals of two different atomes .
let us take an example of BF3 :
in this molecule , we have 1 boron and 3 fluorine .now , boron has to share its 3 electron , each with 1
fluorine atom .each fluorine has 1 half filled p-orbital
so ,since boron has only 1 half filled orbitals .boron atom will come in its first excited state , and will
transfer its one electrons from s orbital to p orbital . such that , boron has 3 half filled orbitals
2s-orbital of boron will form a bond with 2px orbital of fluorine . (s -orbital can from bond with any p-
orbital no matter px ,py or pz because s orbital is spherical and has no direction .)
2px-orbital of boron will form a bond with 2px orbital of fluorine .
2py-orbital of boron will form a bond with 2py orbital of fluorine .
let us take another example of O2 molecule:
--------------------------->SIDEWISE OVERLAPPING / LATERAL OVERLAPPING: pie bond is formed
pie bond is formed between p -p orbital , p - d orbital and d - d orbital
--------------->p-p pie bond :
let us take another exmaple of 02 molecule :
let us take another example of N2 molecule :
you can make sigma bond between either px and px ,or py and py ,or pz and pz . its your own choice .
but you have to make pie bond between the remaining two .
in this example , we have made sigma bond between pz and pz but its your own choice .
Questions :
we will do this question by drawing lewis dot structure .
DIFFERNCE BETWEEN SIGMA AND PIE BOND
--------------> p - d pie bond and d-d pie bond:
# p - p pie bond is stronger than p-d pie bond and d-d pie bond .
here , sulpher has a valency of 2 but has made 4 bonds . so , sulpher will go in excited state .
so , the answer is :
in this
question , sulpher is showing 2 valency but it is making 6 bonds . so , sulpher will go in ecited state .
so , the answer is :
here , phosphorus has 3 valency but it is making 5 bonds . so , phosphorus will go in excited state .
so , the answer is :
here , sulpher has 2 valency but it is making 6 bonds .so , sulpher will go in excited state .
so , th answer is :
CONCEPT OF
HYBRIDIZATION :gives us
geometry of molecule
this is a question of valence born theory :
here , carbon has two valency but it is making 4 bonds , so , it will go in excited state .
valence
born theory says that bond formed between such as s-s will be differnt and bond formed between s-p
orbitals will be different , in this case .
simply , all bonds (s-s , s-p , p-p) will be different from each other but will be same with each other e.g
s-s bond will be diifernt from p-p bond but all p-p bonds will be same .
but here hybridization jumps into the story , all 4 bonds of CH4 are equivalent in all respects
(bond length is same and bond energy is also same .)
now they will have same bond length and bond energy .
all these hybrid sp3 orbitals repel each other and take such orientation in which repulsion is least .so ,
the geometry of methane is tetrahedral
# hybridization is responsible for compund's geometry
POINTS OF HYBRIDIZATION :
# the hybrid orbitals orientate in such a way that repulion between them is minium . this provide more
stability . due to this reasons , hybrid orbitals give geometry of compound .
geometry of sp orbital is always linear and have an angle of 180.
let us take an example :
here , Be has no valency but it is making two bonds . so , Be will go in excited state .
geometry of sp2 hybrid orbital is always triangular planar and the angle between them is 120 .
let us take an exmaple :
the geometry of sp3 orbital is always tetrahedral and the bond angle is 109.5
an exmaple of sp3 hybird orbital is CH4 .
the geometry of sp3d hybrid orbital is alaways trigonal bypyramidal e.g PCL5
the geometry of sp3d2 is always octahedral .e.g SF6
the geometry of sp3d3 is always pentagonal .
Q:how to find hybridization ?
Structural method :
BY FORMULA : SUPER TRICK OF FINDING HYBRIDIZATION
carbon show three hybridization
sp : if 2 pie bonds
sp2 : if 1 pie bond
sp3 : if 0 pie bond
VSEPR THEORY :
valence shell electron pair repulsion theory ---> gives the
exact shape of molecule
first , we will find out hybridiization of some molecules .
hybridization gives the geometry of a molecule .
VASPER theory gives the shape of a molecule .
geometry ----> arrangment of bond pair and lone pair (includes lone pair)
shape----------> arrangment of atoms around central atom (lone pair exclurded)
the bond angle between these 3 molecules should have been 109.5° or 109° 28' (109 degrees and 28
minutes) according to hybridization theory
but in fact , the bond angle between NH3 is 107 and H20 is 105 .this is because in CH4 , all the all
electron pair are bond pair . but in NH3 , there are 3 bond pairs and 1 lone pair and in H20 , there are
two bond pairs and two lone pairs .
# the compund having only bond pairs and no lone pair , then geometry is same
# lone pair -lone pair repulsion is greatest .
# lone pair -bond pair repulsion is less
# bond pair - bond pair repulsion is least .
POINTS OF VSPER THEORY :
now, it can be that surrounding atoms are same e.g PCl5 .here , we can put chlorine any where
but it can also be that surrounding atoms are different e.g in PF2Cl2 and XeO3F2 , we can not put
oxygen and fluorine atoms wherever we want .
in this case , the more electronegative atom occupy equitorial position .and the less electronegative
atom occupy axial position .
in PF3Cl2 ,
# this is important for finding angles . between atoms .
MOLECULAR ORBITAL THEORY :
Valence Bond THeory simply states that atmic orbitals of atoms overlap and form a bond
