Chemistry 102 Summary July 2nd

- So far in our discussion of molecules we have focused on the

arrangement of valence electrons.
- Today we are going to concentrate on the atomic orbitals that hold
these valence electrons and more specifically what happens to
these atomic orbitals when bonds form.

Example: H2

Question: Why does bonding represent a lower energy state?

Answer:

Example: F2 1s22s22p5

pz pz ! bond
- Electron density is on the internuclear axis (designated as z).
- End-end or head to head overlap of orbitals, ex. pz+pz or 1s +1s as in
H2.
- Sigma (σ) bonds can be rotated since orbitals still overlap when
atoms rotate.

Example: O2 1s22s22p4

- We have two bonds to account for.

- Obvious choice of orbitals is the two 2p atomic orbitals with
unpaired electrons.
- Assume the z axis is the internuclear axis, then the 2pz orbitals
overlap to form the sigma bond.
- The second bond is formed from side to side overlap of the 2px
orbitals.
 z-axis

px px ! bond
- Electron density in a π (pi) bond is above and below the
internuclear axis.
- Pi bonds are formed through side to side overlap of parallel p
atomic orbitals (px + px or py + py).
- Pi bonds cannot be rotated without breaking the bond.
- All multiple bonds contain at least one pi bond.
- A single bond consists of one sigma bond.
- A double bond consists of one sigma bond and one pi bond (px+px
or py+py).
- A triple bond consists of one sigma bond and two pi bonds (px+px
and py+py).

Example: N2

Bonding in more complicated molecules:

Example: CH4

-Simple overlap of atomic orbitals can’t explain the 109.5 degree bond
angles of CH4.
- if s,p and d orbitals overlapped to form all bonds then all bond angles
would be ninety and 180 degrees and this is not the case!

Hybrid Orbitals – used to explain the geometry seen in polyatomic

molecules. This is a human construct which mixes atomic orbitals to form
hybrid orbitals.

- For the central carbon atom in CH4 we combine the carbon 2 s

orbital and three carbon 2 p orbitals to result in four sp3 hybrid
orbitals.
 - These sp3 hybrid orbitals are at bond angles of 109.5 degrees and
overlap with the hydrogen 1s orbitals to form four equivalent C-H
bonds in CH4..
- Figures 9.3 and 9.6.
- After overlap the electrons in the bonds are on average localized
between the two nuclei.

Examples:
(i) NH3
(ii) H2O
(iii) C2H4

Question: What do all these molecules have in common?

Answer:

Example: C2H4

Question: What is the geometry around each carbon?

Answer:

- Molecules which exhibit trigonal planar geometry exhibit sp2

hybridization.
- In sp2 hybridization, the 2s orbital is combined with two of the three
2 p atomic orbitals to form 3 equivalent sp2 hybrid oribitals, one p
orbital is left unhybridized.

Example: C2H2

Question: What is the geometry around each carbon?

Answer:

- In linear geometry we mix one s orbital with one p orbital to form

two sp hybrid orbitals and leave two p orbitals unhybridized.

Examples:
(i) CO2
(ii) O2
(iii) N2
Requisite Skills

- Know how to predict hybridization around central atoms.

- Know difference between sigma and pi bonds.
- Be able to count the number of sigma and pi bonds.
- Be able to predict which orbitals overlap to form sigma and pi
bonds.

Example: Fill in the following table and also list the sigma and pi bonds
and the orbitals that overlap to form them.

O H

H C1 C2 C3 N

Atom Geometry Bond Angles Hybrid

Orbitals
C1
C2
C3
N
O

Example: Is allene (C3H4) a planar molecule?

Example: PCl5
Question: What is the geometry about phosphorous?
Answer:

- In trigonal bipyramidal geometry dsp3 hybrids are employed – they

are formed through mixing one s orbital + one d orbital + three p
orbitals to give five dsp3 hybrid orbtials.

Example: SF6
Question: What is the geometry about sulfur?
Answer:

- In octahedral geometry d2sp3 hybrid orbitals are employed – they

are formed through mixing one s orbital + two d orbitals + three p
orbitals to give six d2sp3 hybrid oribtials.

Delocalization

Example: NO2-

- Experiment tells us that NO bonds are equal in length and strength.

- We explain equal bond lengths in molecules that exhibit resonance
by saying the pi electrons are delocalized over the entire surface of
the molecule/ion.
- One unhybridized p orbital from nitrogen and one from each of the
two oxygen atoms all overlap together to give a pi bond
delocalized above and below the entire plane of the NO2- ion.
- There is an extra stability associated with the greater number of
resonance structures that can be drawn for a molecule because
electron-electron repulsions are minimized.

Example: Benzene (C6H6)