61.CHEMICAL BONDING (8)- Covalent Bonding(7)- Hybridization(2).


CONCEPT
OF HYBRIDIZATION

As we studied in the last post, Linus Pauling introduced an imaginary concept of ‘hybridization of atomic orbitals’  to explain the valency and geometry of certain molecules.

Hybridization essentially means mixing. This term is often used in biology , where animal and plant hybrids are created by cross breeding two different species , to get a hybrid fruit/vegetable/plant/ animal of better quality.

Similarly , in this theory, atomic orbitals are mixed to form new orbitals. This process of mixing of atomic orbitals of slightly different energies in an atom to form new set of orbitals of equivalent energies with maximum symmetry, is called hybridization.
611

How do Orbitals hybridise?

Hybridization involves the following steps –

STEP # 1 – FORMATION OF EXCITED STATE.

In the atom – that undergoes hybridization – electron/s from the lower energy valence orbitals/sub shells  get promoted to higher energy vacant valence sub shells i.e they get excited  to a higher energy state.
Energy is released when  extra bonds are formed i.e formation of extra bonds is an energetically favored process.The electrons in the lower energy valence sub shell ,  get excited by absorbing energy.This excitation is favored on account of the fact that more bonds can be formed , thus lowering the energy of the system. The energy absorbed to excite the ground state electrons to higher energy level, is compensated by the energy that is released during bond formation. Note that theoretically these steps happen one after other.However , in reality it is a combined process.

e.g.- In carbon atom, there are only 2 unpaired valence electrons in 2p sub shell.

C (6) 1s2 2s2 2p2612

During hybridization, one electron from the 2s sub shell gets promoted to 2p level as seen in the following figure –

613.jpg

Now carbon atom has four unpaired electrons , which can form four bonds.These four valence electrons have different energies. In reality , however, all the four bonds have similar energies. This can be explained by the next step in hybridization process.

STEP # 2 – MIXING AND RECASTING OF ATOMIC ORBITALS.

In this step , the atomic orbitals of the atom mix to form new equivalent number of hybrid orbitals of equal energy. This mixing of orbitals to form new orbitals is called hybridization.The orbitals having higher energy are slightly demoted in energy and the orbitals with lower energy are sligthly promoted to higher energy , thus making all the orbitals of equal energy.
(
NOTEHere ‘orbitals’ means only the ‘valence orbitals’ , which actually take part in bond formation)

614.jpg

As seen in the above figure , the 2s and 2p orbitals DO NOT have same energy .So, Linus Pauling suggested that , the 2p orbitals be slightly demoted in energy and 2s orbitals be promoted in energy and all orbitals be mixed to form four hybrid orbitals of same energy. These new orbitals are however different from 2s and 2p orbitals. The four new hybrid orbitals are four sp3 orbitals . These new hybrid orbitals form 4 equivalent bonds with other species as seen in practice. 

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In the above example , we have considered a carbon atom, which has one 2s and three 2p orbitals.Thus, we get four new sp3 orbitals.

Similarly , sp2 and sp orbitals are also formed in molecules having one s ,two p  and one s, one p orbitals respectively.

1033

No. of hybrid orbitals

# of unhybridized orbitals involved

Type of hybridisation

4

   one s + three p

sp3

3

one s + two p

sp2

2

one s + one p

sp

e.g. –1.jpg

However, there is an exception to this rule.

0If an atom –
I) has one or more lone pairs and
II)is attached to an sp2atom, then that atom is also sp2 hybridized.

e.g. –

1.jpg


STEP #3 – RE-ORIENTATION

The new hybrid orbitals have different shape than the parent orbitals. These new orbitals orient themselves in space in order to minimize repulsion between each other as seen in VSEPR model. So, the s-orbital is spherical in shape and p- orbitals are dumbbell shaped. However, the sporbitals are neither spherical nor dumbbell shaped, they have a  shape intermediate between the two (tetrahedral).
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Important Features of the hybridization theory –

  1. Hybridization takes place only between atomic orbitals of nearly same energy. Thus, 2s and 2p orbitals can hybridise, but 2s and 4p cannot.
  2. For a given atom ,# of hybrid orbitals = (# of bonded atoms) + (# of lone pairs)  EXCEPTION – single bonded terminal atoms.
    e.g.- Formyl chloride , CHClO.
    617.jpg
    As seen in the above figure, the carbon atom is sphybridized. How did we know that? Use the formula given above –
     # of hybrid orbitals = (# of bonded atoms) + (# of lone pairs)
    Carbon atom is bonded to three atoms namely H,Cl and O  and it has no lone pair of electrons.
    ∴ # of hybrid orbitals = 3 + 0 = 3.
    Thus, carbon atom is sphybridized.H and Cl are single bonded atoms so they are not hybridized. The 1s and 3p valence orbitals of H and Cl respectively, directly participate in bond formation with carbon’s sporbitals.
    Oxygen atom is bonded to carbon atom and has two lone pair of electrons. so again using the above formula,
    # of hybrid orbitals = (# of bonded atoms) + (# of lone pairs)  
    # of hybrid orbitals for O atom = 1+ 2 = 3.
    Thus, oxygen atom is sphybridized too. So, one C-O σ bond is sp2 – sp2 hybridized. The other double bond is a π bond .The π bonds, formed by p-p overlap are not formed by hybridization.
  3. It is not necessary that all the atomic orbitals in an atom take part in hybridization.Hybrid orbitals only form sigma bonds.Orbitals involved in π bond formation (double/triple bonds) do not take part in hybridization. Also , single bonded terminal atoms are not involved in hybridization.
  4. Hybridization takes place only in orbitals, electrons are not involved in it.
  5. Each hybridized orbital is more concentrated on one side of the nucleus, so that greater overlapping can take place and thus a stronger bond is formed.Thus, the hybrid orbitals form stronger bonds.

We can conclude that –

Type of hybridization Hybrid Orbitals # unhybridized p orbitals

sp3

Four sp3  orbitals

none

sp2

Three sp2  orbitals

One p orbital

sp

Two sp orbitals

Two p orbitals


What exactly happens while mixing of atomic orbitals?

Consider a simple example of sp hybridization. One s orbital and one p orbital overlap to form a sp hybrid orbital. We know from our ‘quantum mechanics’ posts (post no 32 and 33) , that an orbital is a region ,where probability of finding the electron( which behaves as a wave) is the most. So, an orbital is a mathematical function , which describes the behaviour of electron in it.

When two atomic orbitals overlap , there is constructive as well as destructive interference between the electrons (behaving as waves)  in those two orbitals. In sp hybridization, the larger lobe of the hybrid orbital shows the region of constructive interference and the smaller lobe (the tail region) shows the area of destructive interference.

Constructive interference → Probability of finding the electron is highest.
Destructive interference → Probability of finding the electron is lowest.

I
6191.jpg

Bond angle.

The angle formed between the centra and terminal atoms in a molecule is caed a sthe bond angle or inter orbital angle.It is represented as θ ,
6196.jpg

In our next post , we shall study molecules formed by hybridization process. Till then ,

Be a perpetual student of life and keep learning…

Good Day !

References and Further reading –

1.https://www.emedicalprep.com/study-material/chemistry/chemical-bonding/hybridization/

2.https://www.youtube.com/watch?v=SbabED1wRMo

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