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  • HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired
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HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired in the orbital By definition: z is the direction along the internuclear axis

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Page 1: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

HF H: 1s1 F: 1s22s22p5

Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds

Note: electron spin is paired in the orbital

By definition: z is the direction along the internuclear axis

Page 2: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

N2 N: 1s22s22p3

The two pz orbitals from each N can overlap to form a orbital.

The px and py orbitals are perpendicular to the internuclear axis

Page 3: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

bond - overlap of two pz orbitals

bond - overlap of two px orbitals and/or two py orbitals

Page 4: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

In a bond, electron density has a nodal plane that contains the bond axis

Page 5: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

According to the VB theory

A single bond is a -bond

A double bond is -bond plus a -bond

A triple bond is a -bond and two -bonds.

VB theory: assumes bonds form

when unpaired electrons in valence shell atomic orbitals pair

the atomic orbitals overlap end to end to form -bonds or side by side to form -bonds.

Page 6: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

Hybridization of Orbitals

C: Is2 2s2 2p2

VB theory, as described so far, would predict that C can form just two bonds

Page 7: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

In CH4, C forms four bonds.

C needs four unpaired electrons so that each can pair with a H atom - need to revise valence-bond theory

“Promote” a 2s electron to a 2p orbital - this requires energy.

But now C has four unpaired electron and since bonding releases energy the cost of promoting is overcome by the lowering of energy on bond formation

Page 8: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

CH4

Promoting a 2s electron to 2p allows C to have four unpaired electrons.

All bonds on CH4 are equivalent

“Mix” the 2s and the three 2p orbitals to form four hybrid orbitals all of the same energy and spatial distribution - hybridization.

One s + three p = four sp3 orbitals

C

H

HH

H

Page 9: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired
Page 10: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

Hybrid orbitals are constructed on an atom to reproduce the electron arrangement of the experimentally determined shape of the molecule.

In CH4: each sp3 orbital has one unpaired electron

Each overlaps with a 1s orbital of H to form -bond

The four resulting -bonds point towards the corners of a tetrahedron.

All four -bonds are identical

http://www.whfreeman.com/chemicalprinciples/

http://www.whfreeman.com/chemicalprinciples/con_index.htm
Page 11: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

Ethane: C2H6

Each C has four sp3 hybrid orbitals, pointing towards the corner of a tetrahedron, each with one electron

Three of these four overlap with three H atoms forming -bonds (C sp3, H 1s).

The C-C bond is formed by an overlap of the remaining sp3 orbital on each C forming a -bond (C sp3, C sp3).

Page 12: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

NH3

H: Is1 N: Is2 2s2 2p3

Hybridize the 2s and 2p orbitals in N to form four sp3 hybrid orbitals.

One of the sp3 has two paired electrons - the lone pair on N

The three other sp3 orbitals form s-orbitals with each of the three H 1s orbitals

NH

H

H

Page 13: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

H2O

H: Is1 O: Is2 2s2 2p4

Hybridize the 2s and 2p orbitals in O to form four sp3 hybrid orbitals.

O 2p

2s

O sp3

Two of the sp3 have two paired electrons - the two lone pairs

The two other sp3 orbitals overlap with H 1s orbitals

OH H

Page 14: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

An s orbital and two p orbitals can hybridize to form three sp2 hybrid orbitals which point to the corners of an equilateral triangle - trigonal planar geometry

Example: BF3

Page 15: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

An s and a p orbital can hybridize into two sp orbitals that point in opposite directions - linear geometry

Page 16: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

PCl5 P: [Ne] 3s2 3p3 Cl: [Ne] 3s2 3p5

P Cl 3p 3p

3s 3s

Promote a 3s electron to the 3d orbital

P _ _ _ _

sp3d empty 3d

Valence shell expansion - expansion to include d orbitals along with s and p orbitals

Page 17: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

One 2, three p, and one d orbital form five sp3d hybrid orbitals, each pointing towards a corner of a trigonal bipyramid

Page 18: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

One 2, three p, and two d orbital form six sp3d2 hybrid orbitals, each pointing towards a corner of a octahedron

Page 19: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

SF6 S: [Ne] 3s2 3p4 F: [He] 2s2 2p5

S

3p

3s

Include two 3d orbital and hybridize one s, three p and two d

S _ _ _ sp3d2 empty 3d

Page 20: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired
Page 21: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

Multiple Bonds

Ethylene: CH2CH2

Experimental data: all six atoms lie in the same plane and the H-C-H and C-C-H bond angles are 120o.

Trigonal planar geometry indicates that each C is sp2 hybridized

For each C: two of the sp2 orbitals bond with two H 1s orbitals to form -bonds, The third Csp2 bond on each bond with each other to form a C-C -bond

Page 22: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

The “pure” 2p orbitals on each C overlap to form a -bond between the two C atoms

The electron density of this -orbital lies above and below the axis of the C-C -bond

http://www.whfreeman.com/chemicalprinciples/

http://www.whfreeman.com/chemicalprinciples/con_index.htm
Page 23: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

Acetylene: C2H2

Linear molecule; each C is sp hybridized, leaving two pure p orbitals on each C

http://www.whfreeman.com/chemicalprinciples/

http://www.whfreeman.com/chemicalprinciples/con_index.htm
Page 24: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

Multiple bonds are formed when an atom forms a -bond by using an sp or sp2 hybrid orbital and one or more -bonds by using un-hybridized p orbitals

Page 25: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

Formic acid: HCOOH

Page 26: HF H: 1s 1 F: 1s 2 2s 2 2p 5 Overlap between the valence orbital of H (1s) and valence orbital of F (2p) to form a bonds Note: electron spin is paired

Electron Configuration Na: 1s 2 2s 2 2p 6 3s 1 Na: [Ne] 3s 1

1s orbital 2s orbital 2p orbitals 3s3s orbital Nucleus Electron energy levels have sublevels of different shapes

5B: 1s 2s 2p 2 1

Electron Configuration and Periodic Trends Na: 1s 2 2s 2 2p 6 3s 1 Na: [Ne] 3s 1

Il carbonio (Z=6) 2 possibilità: configurazione elettronica del C nello stato fondamentale di tripletto di spin 1s 2s 2p + 2p o 2p - [He] (2s) 2 (2p) 2

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