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ATOMI. ATOMIC HYBRIDAZATION. Hybridisation may be defined as the phenomenon of intermixing of the orbitals of slightly different energies so as to redistribute their energies and to give new set of orbitals of equivalent energy and shape. The new orbitals formed as a result

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Hybridisation may be defined as the phenomenon of intermixing of the orbitals of

slightly different energies so as to redistribute their energies and to give new set

of orbitals of equivalent energy and shape. The new orbitals formed as a result

of hybridization are called hybrid or hybridized orbitals. Thus, to form four

equivalent bonds, one 2s and three 2p-orbitals of carbon hybridize and form four

new orbitals.such orbitals are called sp3hybrid orbitals

  • The important characteristics of hybridisation are listed below:
  • The number of hybridized orbitals formed is equal to the number of orbitals that
  • get hybridized.
  • (ii) The hybridized orbitals are always equivalent in energy and shape.
  • (iii) The hybrid orbitals are more effective in forming stable bonds than the pure atomic
  • orbitals.
  • (iv) The hybrid orbitals are directed in space in some preferred directions to have stable
  • arrangements.Therefore, the type of hybridization gives the geometry of the molecule.
  • Depending upon the different combinations of s- and three p-orbitals, three types of
  • hybridizations are known.

Hybridization and concept of sigma and pi bond

HybridizationThe structures of different molecules can be explained on the basis

of hybridization. For e.g., in case of carbon, the ground state electronic

To explain the tetravalency of carbon, it was proposed that one of the electrons

from 2s filled orbital is promoted to the 2p empty orbital (2pz), which is in a higher

energy state. Thus, four half-filled orbitals form in the valence shell this accounts

for the bonding capacity of four carbon atoms.

This state is known as excited state and the configuration of carbon in the excited

state is:

The above configuration reveals that all the four bonds formed by carbon will not be

identical. For e.g., in the formation of CH4 molecule, one C-H bond will be formed

by the overlapping of 2s-orbital of C and 1s-orbital of H whereas the other three

C-H bonds will be formed by the overlapping of 2p-orbitals of C and 1s-orbital of H.

Therefore, all the bonds will not be equivalent.

But actually, in most of the carbon compounds, such as methane (CH4),

carbon tetrachloride (CCl4) etc., all the four bonds of carbon atom are equivalent.

The equivalent character of the bonds can be explained with the help of hybridisation.


sp hybridization

This involves the mixing of one s- and one p-orbital forming two sp-hybrid


The two sp-hybrid orbitals are oriented in a linear arrangement and bond angle

is 180°. For e.g., BeF2 involves sp-hybridization and is, therefore,


sp2 hybridization

In this case, one s- and two p-orbitals hybridize to form three sp2 hybrid orbitals.

These three sp2 hybrid orbitals are oriented in a trigonal planar arrangement.

For e.g., in BH3 boron atom undergoes sp2hybridization and therefore,

BH3 has trigonal planar geometry and HBH bond angle is 120o.3-hybridization"

sp3 hybridization

In this case, one s- and three p-orbitals hybridize to form four sp3 hybrid orbitals.

These four sp3-hybrid orbitals are oriented in a tetrahedral arrangement.

The common example of molecule involving sp3-hybridisation is methane (CH4).

Therefore, CH4 has tetrahedral geometry and HCH bond angle is 109.5o


Valence Shell Electron Pair RepulsionVSEPR

Valence shell electron pair repulsion, VSEPR, is a super-simple technique for

predicting the geometry of atomic centres in small molecules and molecular ions:

Crucially, atomic centres with VSEPR determined geometry can be joined together

into molecular entities like cyclohexane and glucose:

The VSEPR Technique

Six or so steps are required to generate the VSEPR geometry of an atomic centre

such as:

Carbon in methane, CH4Nitrogen in ammonia, NH3Xenon in xenon tetrafluoride, XeF4Iodine in the iodide difluoride ion, [IF2]–

First, determine the number of electrons in the outer (valence) shell about the

central atom (C, N, Xe, I, etc.)


Third, construct a valid Lewis structure of the molecule in question showing

all of the bonds and all of the lone pairs (nonbonded pairs) of electrons.

If the structure is a molecular ion, add one valence electron for each negative

charge and remove one valence electron for each positive charge.


Not all Lewis structures have eight electrons about the central atom A

(as emphasized by very simple Lewis octet theory). For example,

Sulfuric acid, H2SO4, has two monovalent OH functions and two doubly bonded

oxygens that behave as single ligands:


Fourth, determine the "total coordination number" of the central atom, where:

total coordination number =                  number of electron pairs =                                    number of electrons in outer shell divided by 2

Methane, CH4, ammonia, NH3, the ammonium ion, [NH4]+ and the nitranion

(amide ion), [NH2]–, [above] all have eight electrons in the valence shell of the

central atom and all have a total coordination number of 4.

Fifth, the overall geometry of the atomic centre is determined by the mutual

repulsion between the electron pairs of the total coordination number.

The effect can be replicated by holding 2, 3, 4, 5 or 6 balloons together:


2 Balloons give a linear geometry3 Balloons give a trigonal planar geometry4 Balloons give a tetrahedral geometry5 Balloons give a trigonal bipyramidal geometry6 Balloons give an octahedral geometry

Sixth, there two adjustments are required by the VSEPR method to find the geometry

of an atomic centre:

Lone pairs of electrons (nonbonded pairs) are taken into account in determining the

total coordination number and VSEPR geometry, but they are NOT used when

defining the geometry of an atomic centre, only the atoms are used:

Lone-pairs of electrons (blue) behave as if they are slightly bigger than bonded

electron pairs (green) and act to distort the geometry about the atomic centre so

that bond angles are slightly smaller than expected:

Methane, CH4, has a perfect tetrahedral bond angle of 109° 28' (109.47°),

while the H-N-H bond angle of ammonia, H3N:, is slightly less at 107°


The oxygen of water has two bonded electron pairs (green) and two nonbonded

"lone" electron pairs (blue) giving a total VSEPR coordination number of 4.

But the geometry is defined by the relationship between the H-O-H atoms and

water is said to be "bent" or "angular" shape of 104.5°.


Some Words About The Nature of VSEPR "Theory"

Valence shell electron pair repulsion – extraordinary though this may

sound – is not based on any deep theory. It is simply a 'neat trick' that works

extraordinarily well.

VSEPR 'theory' only says that ligands arrange themselves about an atomic

centres so as to maximise spherical symmetry.

The 'theory' does not in any way explain why non-bonding lone pairs of

electrons behave as they do.

It is often said that the VSEPR structure of water shows "two lone pairs of

electrons sticking out like a pair of rabbit's ears"