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Copyright©2000 by Houghton Mifflin Company. All rights reserved. 1 Covalent Bonding: Orbitals Chapter 09

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Covalent Bonding: OrbitalsChapter 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 bondingFrom 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

formation of four  sp

3

 orbitals.

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Hybridize at n=2 sp3 sp3 sp3 sp3

s  px  py  pz

s px  py  pz

Hybridization

sp3 sp3  sp3  sp3

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

Ground state of C 1s2 2s2 sp2

Promote electron at n=2 2s1

2p3

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Hybridization

The mixing of atomic orbitals to formspecial orbitals for bonding.

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

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Valence Bond Theory and NH3 

N  – 1s22s22p3 

3 H  – 1s1 

If use the

three 2p orbitals

predict 900 

 Actual H-N-H bond angle is 107.30 

How do you explain this?

2s 2px  2py  2pz

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10 

2s 2px 2py 2pzOriginal

Mix 1s and 3pAnd generate four

Equivalent sp3

Hybridized orbitals

sp3 sp3 sp3 sp3

3 bonding orbitals

Which can accommodate

The 1s1 electron from

hydrogen

1 sp3

lone

 pair

Consider the n=2 for N

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11 

The nitrogen atom in ammonia is  sp3 

hybridized.

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12 

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13 

An orbital energy-level diagram for  sp2 

hybridization. Note that one  p  orbital

remains unchanged.

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14 

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15 

When an  s and two  p orbitals are mixed to form a set

of three  sp2 orbitals, one  p orbital remains unchanged

and is perpendicular to the plane of the hybrid orbitals.

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16 

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17 

Figure 9.13: (a) The orbitals used to form

the bonds in ethylene. (b) The Lewis

structure for ethylene.

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18 

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19 Sigma bond (s) –

 electron density between the 2 atomsPi bond (p)  – electron density above and below plane of nuclei

of the bonding atoms

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20 

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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21 

A sigma (s

) bond centers along theinternuclear axis.

A pi (p) bond occupies the space above and

 below the internuclear axis.

CC

H H

HH

s

p

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22 

(a)The orbitals used

to form the bondsin ethylene.

(b) The Lewis

structure forethylene.

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23 

The orbital energy-level diagram for the

formation of  sp hybrid orbitals on carbon.

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24 

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25 

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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26 

The orbitals of an  sp hybridized

carbon atom.

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27 

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28 

The orbital arrangement for an  sp2hybridized

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

( ) A h b idi d i (b) h b d i h

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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 bond1 sigma bond

Double bond 1 sigma bond and 1 pi bond

Triple bond 1 sigma bond and 2 pi bonds

How many s and p bonds are in the acetic acid

(vinegar) molecule CH3COOH?

C

H

H

CH

 O 

O Hs bonds = 6 + 1 = 7

p bonds = 1

10.5

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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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s p p p d d d d d

Hybridize 1s and 3p and 1d

Result in 5 dsp3 orbitals

dsp3  dsp3  dsp3  dsp3  dsp3

1 2 3 4 5

A f d 3 h b id bi l h h

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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.)

(a) The PCl5 molecule (b) The orbitals used to form the bonds in

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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.

f 6 bi l ?

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s p p p d d d d d

Hybridize 1s and 3p and 2d

Result in 6 d2sp3 orbitals

d2sp3  ds2 p3  d2sp3  d2sp3  d2sp3 d2sp3

How to form 6 orbitals?

1 2 3 4 5 6