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Chpt 9 - MO Theory
• Localized e- model and hybrid orbitals
• sigma () and pi () bonds
• HW: Chpt 9 - pg. 430-437, #s 11, 12, 16, 29all, 32, 37, Due Tues Nov. 17
• Chpt 6 Review Homework: #30, 36, 46, 50, 60, 74, 78
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Covalent Bonding
Recall• A bond is a combination of forces that
hold groups of atoms together and make them function as a unit.
• A bond will form if the energy of the aggregate is lower than that of the separated atoms.
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Rationale for Orbital Hybridization
What is shape and bond angles of CH4? What is the valence electron configuration of a
carbon atom? s2p2
We now want to think of the bonding orbitals for methane as being formed by an overlap of atomic orbitals.
Assume that the carbon atom has four equivalent atomic orbitals, arranged tetrahedrally.
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Hybridization
Mixing of the native atomic orbitals to form special orbitals for bonding.
sp3 Hybridization• Combination of one s and three p orbitals.
• Whenever a set of equivalent tetrahedral atomic orbitals is required by an atom, the localized electron model assumes that the atom adopts a set of sp3 orbitals; the atom becomes sp3 hybridized.
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Energy diagram for sp3
An s and 3 p orbitals become 4 equal sp3 orbitals
visualization
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C2H4 example
Draw the Lewis structure for C2H4 (ethylene)? What is the shape of an ethylene molecule?
trigonal planar around each carbon atom
What are the approximate bond angles around the carbon atoms?
120o
CH
CH
HH
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sp2 hybridization & Energy level diagram
• Combination of one s and two p orbitals.• Gives a trigonal planar arrangement of atomic
orbitals.• One p orbital is not used.
Oriented perpendicular to the plane of the sp2 orbitals can be used to form pi () bonds.
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Ethylene C2H4 hybrid bonding
Carbon atom Carbon atom
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Ethylene sigma and pi bonding
Above - sigma bonds in ethylene
Above - sigma bond & pi bond on carbon in ethylene
Left - total bonding in ethlene
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sp hybridization example
Draw the Lewis structure for CO2. What is the shape of a carbon dioxide
molecule?
linear
What are the bond angles?
180o
CO O
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sp Hybridization• Combination of one s and one p orbital.• Gives a linear arrangement of atomic
orbitals.• Two p orbitals are not used.
Needed to form the bonds.
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Sigma & Pi bonds
Sigma () bond• an Electron pair is shared in an area
centered on a line running between the atoms.
Pi () bond• Forms double and triple bonds by
sharing electron pair(s) in the space above and below the σ bond.
• Uses the unhybridized p orbitals.
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Hybrid orbitals in CO2
Yellow are 2 sp hybrid orbitals --> make bonds to O , Blue are unhybridized p orbitals that make bonds to O (double bonds)
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dsp3 hybridizationDraw the Lewis structure for PCl5.
What is the shape of a phosphorus pentachloride molecule?
trigonal bipyramidal What are the bond angles?
90o and 120o
P
Cl
Cl ClCl
Cl
•Combination of one d, one s, and three p orbitals.•Gives a trigonal bipyramidal arrangement of five equivalent hybrid orbitals.
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d2sp3 HybridizationDraw the Lewis structure for XeF4.
What is the shape of a xenon tetrafluoride molecule?
octahedral What are the bond angles?
90o and 180o
Xe
F
F F
F
•Combination of two d, one s, and three p orbitals.•Gives an octahedral arrangement of six equivalent hybrid orbitals.
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XeF4 example
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Examples
Draw the Lewis structure for HCN.
Which hybrid orbitals are used?
Draw HCN: Showing all bonds between atoms. Labeling each bond as or .
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More examples hybridization
Determine the bond angle and expected hybridization of the central atom for each of the following molecules:
NH3 SO2 KrF2
CO2 ICl5NH3 – 109.5o, sp3
SO2 – 120o, sp2
KrF2 – 90o, 120o, dsp3
CO2 – 180o, sp
ICl5 – 90o, 180o, d2sp3
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NO3-1 delocalized pi orbital