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The Chemical Bond

Chapter 14

- Central to all aspects of Chemistry


- Reactions make them & break them
The Chemical Bond
A link between atoms?

"SOMETIMES IT SEEMS to me that a bond between


two atoms has become so real, so tangible, so friendly,
that I can almost see it. Then I awake with a little shock,
for a chemical bond is not a real thing. It does not exist.
No one has ever seen one. No one ever can. It is a
figment of our own imagination. C.A. Coulson(1910-74)

Major approaches for calculation of molecular structure:


Valence Bond Theory (VBT)
Molecular Orbital Theory (MOT)
The Chemical Bond: classification
Ionic bond:
Lewis Concept:
Octet rule

Covalent bond:

VSEPR model: Shape of Molecules


VSEPR model: Shape of Molecules
Predicts shape of molecules from
Lewis dot structure
The shape of the molecule is
determined by repulsion between
valence shell electrons (VSE).
Strength of repulsion:
lp-lp > lp-bp > bp-bp; TB > DB > SB
VSEPR model: Shape of Molecules
STRUCTURE SHAP bp+ lp=VSE
STRUCTURE SHAPE VSE
E

2 4+1=5

3
3+2=5

5
2+3=5
Solution for Molecules
Based on Born-Oppenheimer Approximation:
nuclei being much heavier than an electron, move
relatively slowly and may be treated as stationary while
the electrons move around them.

Enable to solve
Schordinger
equation for the
electron alone
at a fixed
location of Re: Equilibrium Bond Length
nuclei. De: Depth of the minimum

Potential Energy Surface


The valence bond theory
A bond is formed when an
electron in an atomic orbital on
one atom pairs its spin with that
of an electron in an atomic
orbital on an another atom.
Why this spin-pairing leads to
bonding?

For non - interactin g atoms : A B


Approx Wavefunction : A B A 2B1
Spin part of the wave function : spin
Total Wavefunction : Total spin
The valence bond theory
VB Spatial Wave function for an A-B Bond:
A BA B A 2B1

VB Electron
Density of H2

A B

- Accumulation of electron density b/w the two nuclei


- Wave function with cylindrical symmetry (-bond)
The valence bond theory of N2
Valence Electronic configuration: 2s 2 2 px1 2 p y1 2 pz1
Bonds results when Nitrogen 2p orbitals pair

Bonding in N2
Nitrogen 2pz
orbitals pair
Cylindrical
Symmetry: bond
Nitrogen 2px and
2py orbitals
No cylindrical
symmetry: bond Sigma and Pi bond formation N2
VB Theory of polyatomic molecules

2 1 1 1
e.g. H2O molecule: O atom : 2 p x 2 p y 2 p z H atom : 1s

2p orbitals of
oxygen form
bonds with H1s

Predicted bond
angle: 90o

Deficiencies of VB
Poorly estimates bond angle
Number of bond formation, e.g. C(2s2p2)
Promotion of electron: Hybridization
e.g. Methane CH4
Promotion of one electron from 2s to 2p orbital of C
atom: 2s1 2 px1 2 py1 2 pz1

(sp3 hybrid
h1 s p x p y p z
Atomic orbitals inter-mix to

orbitals)
h2 s p x p y p z
give rise four new orbitals
h3 s p x p y p z
called Hybrid orbitals
h4 s p x p y p z

Regular Tetrahedron Formation (sp3 hybrid)


VB Theory of Alkenes
Sp2 Hybridization; Trigonal Planar; Bond angle: 120o

sp2 hybrid orbitals:


h s 2 p ; h s (3 / 2) p (1 / 2) p
1 x 2,3 x y
The coefficients indicates directional properties
Squares of the coefficients indicates proportion of
atomic orbitals
VB Theory of Alkynes
Sp Hybridization; Linear; h1 s pz
Bond angle: 180o h2 s pz

Sp Hybridization: Linear
Two bonds with hybrid orbital of another C or H1s.
Two bonds perpendicular to molecular axis
Hybridization: summary

Number Shape Hybridization*


2 Linear sp
2
3 Trigonal planar sp
3
4 Tetrahedral sp
3
5 Trigonal bipyramidal sp d
3 2
6 Octahedral sp d
* Other combinations are possible.

Hybridization of N atomic orbitals always results


in the formation of N hybrid orbitals
Resonance
Superposition of wave functions with different electron
distributions in the same nuclear framework
For purely covalent HCl:
H Cl H C l H 2 Cl 1
Ionic form H Cl : H Cl Cl1Cl 2

Superposition of ionic & covalent HCl:


HCl H Cl H
Cl

In General, covalent ionic

2 denotes proportion of Ionic Contribution: smaller


implies lesser ionic (or greater covalent) character of
Resonance
Resonance
Covalent: Kekule
Superposition of wave
functions of two Kekule
Structures with identical
energies. (covalent)
Double bond character
around the ring
Energy of the molecule is Ionic-covalent
lowered (Resonance
Stabilization) +
Ionic Covalent Resonance -

Energy is still lowered


Molecular Orbital Theory
-Electrons spread through out the entire molecule
-Every electron contributes to the strength of every bond
-The one electron wave function is called molecular
orbital
The of the molecule is written as the Linear
Combinations of Atomic Orbitals (LCAO)

c A A cB B

CA2 and CB2 are proportion of AO corresponding to MO


MO Theory of Diatomics
For Homonuclear diatomics, CA2 = CB2
A B ( Bonding)
A B ( Antibonding )
Bonding

Antibonding
MO Theory of diatomics
Antibonding Orbital
Bonding Orbital
Higher energy than the
Constructive interference
bonding orbital
Electron accumulated in
Nodal plane, destructive
the internuclear region
interference on this plane
Electron relocate outside the
bonding region
Bond Formation
Lower energy in bonding orbital ()
Higher energy antibonding orbital (*)
For, H2+ ,
bond length: 130pm (106)
For H2
bond dissociation energy :171 kJ mol-1 (250)
Orbital Symmetry
Inversion Symmetry Same Sign, Gerade Symmetry)
Behavior of when it
is inverted through
center of inversion.
identical sign of
around center of
molecule (Gerade Opposite Sign, Ungerade Symmetry)
Symmetry)
Opposite sign of ,
(Ungerade)
Symmetry
Symmetry and Overlap
e.g. S and p overlap

End-on overlap Side overlap


non-zero overlap No net overlap
axially symmetric orbital No bonding
Overlap Integral
The extent of overlap b/w two orbitals A and B
is given by the
overlap Integral:

The overlap Integral b/w two


H1s orbitals separated by R:
Contribution of different AO to MO
Contribution of p orbitals Contribution of d orbitals
Building up molecules
Construct MO by LCAO of all suitable valence
atomic orbitals.

N atomic orbitals results in N molecular orbitals

Accommodate the valence electrons supplied by


the atoms so as to achieve the lowest overall
energy subject to Pauli exclusion principle

If more than one molecular orbital of the


same energy is available, add the electrons to
each individual orbital before doubly
occupying any one orbital (Hunds rule)
Structure of homonuclear diatomics
Two atomic orbitals (AOs) forms two molecular
orbitals (MOs): 1 (bonding) and 1* (anti-bonding).

AO MOs AO

The energy gain while occupying the 1* is more than


the energy lowering in occupying the 1. Thus, Helium
atoms do not form a bond.
Structure of homonuclear diatomics
AOs on A or B of 2s and 2 p :
c1 A2 s c2 B 2 s c3 A2 pz c4 B 2 pz (LCAO)

Electronic Configuration of N2
No. of Valence Electrons: 10
Ground-State
1g2 1u*21u42g2
Bond Order
b= ()(n-n*) (For N2 , b=3)
n=number of electrons in
bonding orbitals
n*=number of electrons in
antibinding orbitals
Variation of orbital energies

2g < 1u
Heteronuclear diatomics
The bonding electron pair is shared unequally by two
atoms resulting Polar Bond. e.g: CO and HCl
LCAO gives
c A A cB B
with c A2 cB2
Polarity depends on
electronegativity ( )

For A B :
Relative Contribution of
c c (bonding),
2
A
2
B Atoms in a Polar Bond
c A2 cB2 (antibonding )
Heteronuclear diatomics
Pauling Electronegativity Scale:
A B 0.102 (E / kJ mol )
1 1/ 2

Mulliken Electronegativity Scale: 0.5 ( I Eea ) / eV

Atom having higher


electronegitivity have
usually higher
ionization energy
Heteronuclear diatomics: CO