Covalent Bonding: Orbitals

Chapter 09

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The four bonds around C are of equal length and Energy

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Can you explain this based on your knowledge of electron energy levels?

6C

1s2 2s2 2p2

Bonding from s is Different from bonding From p. In addition the Angles should be within 900!
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How to generate four equal orbitals?

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Hint: A key to wave mechanics is superposition Which is creating new waves from interference of old ones

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An energy-level diagram showing the 3 formation of four sp orbitals.

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Hybridization
Ground state of C 1s2 2s2 sp2 s px py pz

Promote electron at n=2

2s12p3

px

py

pz

Hybridize at n=2

sp3 sp3 sp3 sp3 sp3 sp3 sp3 sp3

Four sp3 orbitals of equal length, energy and in tetrahedral shape

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Hybridization
The mixing of atomic orbitals to form special orbitals for bonding.

The atoms are responding as needed to give the minimum energy for the molecule.

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Valence Bond Theory and NH3 N 1s22s22p3 3 H 1s1

2s 2px 2py 2pz If use the three 2p orbitals predict 900

Actual H-N-H bond angle is 107.30

How do you explain this?
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Consider the n=2 for N

Original
2s

2px 2py 2pz

Mix 1s and 3p And generate four

sp3 sp3 sp3

sp3

Equivalent sp3
Hybridized orbitals
1 sp3 lone pair

3 bonding orbitals Which can accommodate The 1s1 electron from hydrogen
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The nitrogen atom in ammonia is sp hybridized.

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An orbital energy-level diagram for sp hybridization. Note that one p orbital remains unchanged.

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When an s and two p orbitals are mixed to form a set 2 of three sp orbitals, one p orbital remains unchanged and is perpendicular to the plane of the hybrid orbitals.

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Figure 9.13: (a) The orbitals used to form the bonds in ethylene. (b) The Lewis structure for ethylene.

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Pi bond (p) electron density above and below plane of nuclei Copyright2000 bybetween Houghton 19 Sigma bond (s) electron density the 2 atoms Mifflin Company. All rights reserved. of the bonding atoms

The s bonds in ethylene. Note that for each bond the shared electron pair occupies the region directly between the atoms.

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A sigma (s) bond centers along the internuclear axis.

A pi (p) bond occupies the space above and below the internuclear axis.

H H

H H
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C sC
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(a)The orbitals used to form the bonds in ethylene.

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(b) The Lewis structure for ethylene.

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The orbital energy-level diagram for the formation of sp hybrid orbitals on carbon.

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When one s orbital and one p orbital are hybridized, a set of two sp orbitals oriented at 180 degrees results.

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The orbitals of an sp hybridized carbon atom.

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The orbital arrangement for an sp hybridized oxygen atom to form CO2.

8O

1s22s22p4

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The hybrid orbitals in the CO2 molecule.

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(a) The orbitals used to form the bonds in carbon dioxide. Note that the carbon-oxygen double bonds each consist of one s bond and one p bond. (b) The Lewis structure for carbon dioxide.

2sp orbitals from C to form two double bonds

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(a) An sp hybridized nitrogen atom. (b) The s bond in the N2 molecule. (c) The two p bonds in N2 are formed when electron pairs are shared between two sets of parallel p orbitals. (d) The total bonding picture for N2.

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Sigma (s) and Pi Bonds (p)

Single bond Double bond Triple bond 1 sigma bond

1 sigma bond and 1 pi bond

1 sigma bond and 2 pi bonds

How many s and p bonds are in the acetic acid (vinegar) molecule CH3COOH? O s bonds = 6 + 1 = 7 p bonds = 1
32

H H C H

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10.5

How to generate more than 4 bonds?

Remember the PCl5, SF6, etc The s and 3p can generate 4 orbitals

Include d orbitals to generate more!

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Hybridize 1s and 3p and 1d

Result in 5 dsp3 orbitals 1 2 3 4 5

dsp3 dsp3

dsp3 dsp3

dsp3
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A set of dsp3 hybrid orbitals on a phosphorus atom. Note that the set of five dsp3 orbitals has a trigonal bipyramidal arrangement. (Each dsp3 orbital also has a small lobe that is not shown in this diagram.)

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(a) The PCl5 molecule. (b) The orbitals used to form the bonds in PCl5. The phosphorus uses a set of five dsp3 orbitals to share electron pairs with sp3 orbitals on the five chlorine atoms. The other sp3 orbitals on each chlorine atom hold lone pairs.

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How to form 6 orbitals?

Hybridize 1s and 3p and 2d Result in 6 d2sp3 orbitals 2 3 4 5

d2sp3 ds2p3

d2sp3

d2sp3 d2sp3 d2sp3

37

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