Molecular Geometry and Bonding Theories
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Transcript of Molecular Geometry and Bonding Theories
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MOLECULAR GEOMETRY AND BONDING THEORIES
Chapter 8
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Section 8.1 Molecular Compounds
Key Concepts:How are the melting points and boiling points of molecular compounds different from ionic compounds?
What information does a molecular formula provide?
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covalent bondmoleculediatomic moleculemolecular compoundmolecular formula
Vocabulary
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Molecules and Molecular Compounds
Key Concept: Molecular compounds tend to have relatively lower melting and boiling points than ionic compounds.
Covalent bond: when two atoms are held together by the sharing of electrons.
Water (H2O) H – O – H Carbon Dioxide (CO2) O = C = O
Molecule: a neutral group of atoms joined together by covalent bonds.
Diatomic Molecule: a molecule consisting of two atoms. Example: Oxygen molecule (O2) O = O
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Molecules and Molecular Compounds
Key Concept: Molecular compounds tend to have relatively lower melting and boiling points than ionic compounds.
Molecular compound: a compound composed of molecules, and made of different atoms (two or more nonmetals). Water (H2O) H – O – H
Carbon Dioxide (CO2) O = C = O
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Draw diagrams of ionic and covalent bonds to understand the differences:
Molecular Compound: Water• Collection of water
molecules:
Ionic Compound: Salt• Array of sodium ions
and chloride ions:
Structure: ???Chemical Formula: ???
Structure: ???Chemical Formula: ???
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Draw diagrams of ionic and covalent bonds to understand the differences:
Molecular Compound: Water• Collection of water
molecules:
Ionic Compound: Salt• Array of sodium ions
and chloride ions:
Structure: H – O – HChemical Formula: H2O
Structure: Na+ Cl-
Chemical Formula: NaCl
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Molecular Formulas Key Concept: A Molecular formula shows how many atoms
of each element a molecule contains.
Molecular formula: the chemical formula of a molecular compound.
Water Carbon dioxideAmmonia (NH3)Ethane (C2H6)
*Refer to page: 216
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PracticeWrite the electron dot structures of the following molecules:
BF3 (boron trifluoride)CH4 (methane)SF4 (sulfur tetrafluoride)CO (carbon monoxide)BeCl2 (beryllium dichloride)
*Refer to page: 216
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Sections 8.2 – 8.3 Bonding Theories
Key Concepts:
What is the VSEPR Theory?How does the VSEPR Theory predict the shape of molecules?
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molecular formula
structural formula
molecular shape
ball-and-stick model
CH4 C
H
H
HH
H
H
H
H
109.5o
C
tetrahedrontetrahedralshape ofmethane
CH
H
H
H
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Methane & Carbon Tetrachloridemolecular formula
structural formula
molecular shape
ball-and-stick model
CH4 C
H
H
HH
H
H
H
H
109.5o
C
CCl4
space-filling model
C
Cl
Cl
ClCl
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Molecular Geometry
H
H
H
H109.5o
C
Linear Trigonal planar
Tetrahedral
Trigonal pyramidalBent
109.5o
107.3o104.5o
H2O CH4 AsCl3 AsF5 BeH2 BF3 CO2
180o
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C109.5o
H
HHH
N107o HH
H
..
O104.5o H
H
..
..
CH4, methane NH3, ammonia H2O, water
..
O
O
O
lone pairelectrons
OOO
O3, ozone
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Molecular ShapesThree atoms (AB2) Four atoms (AB3)
Five atoms (AB4)
Six atoms (AB5)
Seven atoms (AB6)
• Linear (180o)• Bent
• Trigonal planar (120o)• Trigonal pyramidal• T-shaped
• Tetrahedral (109.47o)• Square planar• Seesaw
• Trigonal bipyramidal (BeABe, 120o) & (BeABa, 90o)• Square pyramidal
• Octahedral
B BA
B
B
A
B
linear trigonal planarB
A
BB
B
tetrahedral
A Be
Be
Be
Ba
BaTrigonalbipyramidalB
B
B
B
B
BA
Bailar, Moeller, Kleinberg, Guss, Castellion, Metz, Chemistry, 1984, page 313.
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Bonding and Shape of Molecules
Number of Bonds
Number of Unshared Pairs Shape Examples
2
3
4
3
2
0
0
0
1
2
Linear
Trigonal planar
Tetrahedral
Pyramidal
Bent
BeCl2
BF3
CH4, SiCl4
NH3, PCl3
H2O, H2S, SCl2
-Be-
B
C
N
:
O
:
:
CovalentStructure
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Molecular ShapesAB2
Linear
AB3
Trigonal planar AB4
Tetrahedral
AB5
Trigonal bipyramidal
AB6
Octahedral
AB3EAngular or Bent AB3E
Trigonalpyramidal
AB3E2
Angular or Bent
AB4EIrregular tetrahedral(see saw)
AB3E2
T-shapedAB2E3
Linear
AB6ESquare pyramidal
AB5E2
Square planar
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......
The VSEPR Model
O OC
Linear
The Shapes of Some Simple ABn Molecules
O OS
BentO O
S
O
Trigonalplanar
FF
F
N
Trigonalpyramidal
T-shaped Squareplanar
F FCl
F
F F
Xe
F FF
F
FP
F
FTrigonal
bipyramidalOctahedral
FF
F
S
F
F
F
SF6
SO2
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 305
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Molecular ShapesAB2
Linear
AB3
Trigonal planarAB4
Tetrahedral
AB5
Trigonal bipyramidal
AB6
Octahedral
AB2EAngular or Bent
AB3ETrigonal
pyramidal
AB2E2
Angular or Bent
AB4EIrregular tetrahedral(see saw)
AB3E2
T-shapedAB2E3
Linear
AB5ESquare pyramidal
AB4E2
Square planar
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Geometry of Covalent Molecules ABn, and ABnEm
AB2
AB2EAB2E2
AB2E3
AB3
AB3E
AB3E2
AB4
AB4E
AB4E2
AB5
AB5EAB6
222233
34
4
45
56
012301
20
1
20
10
LinearTrigonal planarTetrahedralTrigonal bipyramidalTrigonal planarTetrahedral
Triangular bipyramidalTetrahedral
Triangular bipyramidal
OctahedralTriangular bipyramidal
OctahedralOctahedral
LinearAngular, or bentAngular, or bentLinearTrigonal planarTriangular pyramidal
T-shapedTetrahedral
Irregular tetrahedral (or “see-saw”)Square planarTriangular bipyramidal
Square pyramidalOctahedral
CdBr2
SnCl2, PbI2
OH2, OF2, SCl2, TeI2
XeF2
BCl3, BF3, GaI3
NH3, NF3, PCl3, AsBr3
ClF3, BrF3
CH4, SiCl4, SnBr4, ZrI4
SF4, SeCl4, TeBr4
XeF4
PF5, PCl5(g), SbF5
ClF3, BrF3, IF5
SF6, SeF6, Te(OH)6, MoF6
TypeFormula
Shared Electron
Pairs
Unshared Electron
PairsIdeal
GeometryObserved
Molecular Shape Examples
Bailar, Moeller, Kleinberg, Guss, Castellion, Metz, Chemistry, 1984, page 317.
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Molecules with Expanded Valence ShellsAtoms that have expanded octets have AB5 (trigonal bipyramidal)
or AB6 (octahedral) electron domain geometries.
Trigonal bipyramidal structures have a plane containing three electron pairs.
• The fourth and fifth electron pairs are located above and below this plane.• In this structure two trigonal pyramids share a base.
For octahedral structures, there is a plane containing four electron pairs.• Similarly, the fifth and sixth electron pairs are located above and below this plane.• Two square pyramids share a base.
F
F
FP
F
F
FF
F
S
F
F
F
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Trigonal Bipyramid F
F
FP
F
F• The three electron pairs in the plane are called equatorial.
• The two electron pairs above and below this plane are called axial.
• The axial electron pairs are 180o apart and 90o from to the equatorial electrons.
• The equatorial electron pairs are 120o apart.
• To minimize electron-electron repulsions, nonbonding pairs are always placed in equatorial positions, and bonding pairs in either axial or equatorial positions.
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Octahedron• The four electron pairs in the plane are 90o to each other.
• The remaining two electron pairs are 180o apart and 90o from the electrons in the plane.
• Because of the symmetry of the system, each position is equivalent.
• The equatorial electron pairs are 120o apart.
• If we have five bonding pairs and one nonbonding pair, it doesn’t matter where the nonbonding pair is placed.
The molecular geometry is square pyramidal.
• If two nonbonding pairs are present, the repulsions are minimized by pointing them toward opposite sides of the octahedron.
The molecular geometry is square planar.
FF
F
S
F
F
F
F F
Xe
F F
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Electron-Domain GeometriesNumber of Electron Domains
Arrangement ofElectron Domains
Electron-DomainGeometry
Predicted Bond Angles
2
3
4
5
6
Linear
Trigonalplanar
Tetrahedral
Trigonal-bipyramidal
Octahedral
180o
120o
109.5o
120o
90o
90o
A Be
Be
Be
Ba
Ba
B
B
B
B
B
BA
B
B
A
BB
A
BB
B
B BA
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Number of electron domains
Electron-domain geometry
Predicted bond angles
TetrahedralTrigonalplanar Tetrahedral
109.5o 120o 109.5o
C C OH H
H
H O
4 3 4
Acetic Acid, CH3COOH
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 314
Hybridization of central atom sp3 sp2 none
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Section 8.4Molecular Polarity
Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
Key Concepts
How do molecules become polarized/charged?What is a dipole-moment?What do network solids have high melting
points?
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Dipole Moment
• Direction of the polar bond in a molecule.• Arrow points toward the more
electronegative atom.
H Cl+ -
Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
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Determining Molecular Polarity
• Depends on:– dipole moments– molecular shape
Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
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Determining Molecular Polarity
• Nonpolar Molecules– Dipole moments are symmetrical and cancel
out.
BF3
F
F F
B
Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
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Determining Molecular Polarity
• Polar Molecules– Dipole moments are asymmetrical and don’t
cancel .
netdipolemoment
H2OH H
O
Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
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CHCl3
H
Cl ClCl
Determining Molecular Polarity• Therefore, polar molecules have...
– asymmetrical shape (lone pairs) or – asymmetrical atoms
netdipolemoment
Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
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Dipole Moment
Nonpolar
Polar
....
H H
O
C OO
Bond dipoles
Overall dipole moment = 0
Bond dipoles
Overall dipole moment
The overall dipole moment of a moleculeis the sum of its bond dipoles. In CO2 thebond dipoles are equal in magnitude butexactly opposite each other. The overall dipole moment is zero.
In H2O the bond dipoles are also equal inmagnitude but do not exactly oppose eachother. The molecule has a nonzero overall dipole moment.
221
dqqkF Coulomb’s lawm = Q r Dipole moment, m
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 315
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......
Polar Bonds
H Cl
Polar
A molecule has a zero dipole moment because their dipoles cancel one another.
H HO
PolarF F
B
F
Nonpolar
HH
H
N
Polar
Polar Nonpolar
F FCl
F
F F
Xe
F FCl
ClC
Cl
Nonpolar Polar
Cl
HC
Cl
H
H
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Hydrogen Bond Formation
0.74 A
- 436
0
H – H distance
Ene
rgy
(KJ/
mol
)
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 318
no interaction
increasedattraction
balanced attraction& repulsion
increasedrepulsion
Potential Energy Diagram - Attraction vs. Repulsion
(internuclear distance)
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Be
H
H
BeH2
s p
First, the formation of BeH2 using pure s and p orbitals.
The formation of BeH2 using hybridized orbitals.
atomic orbitals atomic orbitals
Be
s p
Be H
H
s p
atomic orbitals
hybrid orbitals
No overlap = no bond!
sp p
Be HH
All hybridized bonds have equal strength and have orbitals with identical energies.
BeH2Be
Be = 1s22s2
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Hybrid OrbitalsGround-state Be atom
1s 2s 2p
1s 2s 2p
Be atom with one electron “promoted”
s
px py pz
sp
hybrid orbitals
Ene
rgy
hybridize
s orbital p orbital
two sp hybrid orbitals sp hybrid orbitals shown together(large lobes only)
1s sp 2pBe atom of BeH2 orbital diagram
H HBen = 1
n = 2
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Hybrid Orbitals
2s 2p
Ground-state B atom
s
px py pzEne
rgy
sp2 2pB atom of BH3 orbital diagram
hybridize
s orbital
2s 2p
B atom with one electron “promoted”
sp2
hybrid orbitals
p orbitals sp2 hybrid orbitals shown together(large lobes only)three sps hybrid orbitals
H
H
HB
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s
px py pz
Carbon 1s22s22p2
Carbon could only make two bondsif no hybridization occurs. However,carbon can make four equivalent bonds.
sp3
hybrid orbitals
Ene
rgy
sp3
C atom of CH4 orbital diagram
B
ABB
B
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 321
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Hybridization Involving d Orbitals
3s 3p 3d 3s 3p 3d
promote
five sp3d orbitals 3dF
F
FP
F
F
A Be
Be
Be
Ba
Ba
Trigonal bipyramidal
hybridize
degenerateorbitals
(all EQUAL)
unhybridized P atomP = [Ne]3s23p3
vacant d orbitals
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Multiple Bonds
2s 2p 2s 2p sp2 2p
promote hybridize
C CH
H H
H
C2H4, ethene
one s bond and one p bond
H
H
CC
H
H s
ss
s
s
H
H
CC
H
H
Two lobes ofone p bond
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 325-326
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Multiple Bonds
2s 2p 2s 2p sp2 2p
promote hybridize
C CH
H H
HC2H4, ethene
one s bond and one p bond
H
H
CC
H
H s
ss
s
s
H
H
CC
H
H
Two lobes ofone p bond
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 325-326
C C
H
H
sp2
sp2
sp2
H
Hsp2
sp2
sp2
p p
p p
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p bond
Internuclear axis
p p
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Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 326
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s bonds
H
CHC
H
C
H
C
H C
H
C
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 329
C6H6 = benzene
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2p atomic orbitals
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 329
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s bonds and p bonds
H
C
HCH
C
H
C
H C
H
C
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 329
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s bondsH
CH
C
HC
H
C
H
C
H
C
HC
H
C
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 329
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s bondsH
C
H
C
HC
H
C
H
C
H
C
HC
H
C
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 329
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N NO
O
O
O
dinitrogen tetraoxide
N2O4
NO
ON
O
O
hn 2 NO2nitrogen dioxide
(free radical)
colorless red-brown
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1s 1s
s1s
s*1s
1s 1s
s1s
s*1s
H2 molecule
He2 molecule
H atom H atom
He atom He atom
Ene
rgy
Ene
rgy
Energy-level diagram for (a) the H2 molecule and (b) the hypothetical He2 molecule
(a)
(b)
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 332
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Bond Order
Bond order = ½ (# or bonding electrons - # of antibonding electrons)
• A bond order of 1 represents a single bond,
• A bond order of 2 represents a double bond,
• A bond order of 3 represents a triple bond.
• A bond order of 0 means no bond exists.
Because MO theory also treats molecules with an odd number of electrons, Bond orders of 1/2 , 3/2 , or 5/2 are possible.
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1s2 1s2
s1s
s*1s
2s1 2s1
s2s
s*2s
Energy-level diagram for the Li2 molecule
Li = 1s22s1
Li Li
Li2
Ene
rgy
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 334
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2s 2s
s2s
s*2s
2p 2p
s2p
s*2p
p2p
p*2p
Energy-level diagram for molecular orbitals of second-row homonuclear diatomic molecules.
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 337
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Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 338
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s2s
s*2s
s2p
p2pEnergy of molecular orbitals
O2, F2, Ne2 B2, C2, N2
Increasing 2s – 2p interaction
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 338
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s2s
s*2s
p2p
s2p
p*2p
s*2p
Large 2s – 2p interaction Small 2s – 2p interaction
s2s
s*2s
s2p
p2p
p*2p
s*2p
C2 N2B2 F2 Ne2O2
Bond order
Bond enthalpy (kJ/mol)
Bond length (angstrom)
Magnetic behavior
1 2 3 2 1 0
290 620 941 495 155 -----
1.59 1.31 1.10 1.21 1.43 -----
Paramagnetic Diamagnetic Diamagnetic Paramagnetic Diamagnetic _____
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 339
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Magnetic Properties of a Sample
PARAMAGNETISM – molecules with one or more unpaired electrons are attracted into a magnetic field. (appears to weigh MORE in a magnetic field)
DIAMAGNETISM – substances with no unpaired electrons are weakly repelled from
a magnetic field. (appears to weigh LESS in a magnetic field)
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Experiment for determining the magnetic properties of a sample
The sample is first weighed in the absence of a magnetic field.
When a field is applied, a diamagneticsample tends to move out of the fieldand appears to have a lower mass.
A paramagnetic sample is drawninto the field and thus appears to gain mass.
Paramagnetism is a much stronger effect than is diamagnetism.
sample N SN SN S
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 339
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Experiment for determining the magnetic properties of a sample
N S N S
The sample is first weighed in the absence of a magnetic field.
When a field is applied, a diamagneticsample tends to move out of the fieldand appears to have a lower mass.
A paramagnetic sample is drawninto the field and thus appears to gain mass.
Paramagnetism is a much stronger effect than is diamagnetism.
sample
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 339
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Lone Pair Single bond Double bond Triple bond
Electron Domains
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Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
Review: Molecular Geometry
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VSEPR TheoryValence Shell Electron Pair Repulsion Theory
Electron pairs orient themselves in order to minimize repulsive forces.
Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
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VSEPR TheoryTypes of e- Pairs
– Bonding pairs - form bonds– Lone pairs - nonbonding electrons
Lone pairs repel more strongly than
bonding pairs!!!Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
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VSEPR TheoryLone pairs reduce the bond angle between
atoms.
Bond AngleCourtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
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Determining Molecular Shape1. Draw the Lewis Diagram.2. Tally up e- pairs on central atom.
- double/triple bonds = ONE pair
3. Shape is determined by the # of bonding pairs and lone pairs.
Know the 7 common shapes & their bond angles!
Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
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Common Molecular Shapes
2 total2 bond0 lone
LINEAR180°BeH2
Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
B BA
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Common Molecular Shapes
3 total3 bond0 lone
TRIGONAL PLANAR120°
BF3
Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
B
B
A
B
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Common Molecular Shapes
4 total4 bond0 lone
TETRAHEDRAL109.5°
CH4
Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
B
A
BB
B
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Common Molecular Shapes
4 total3 bond1 lone
TRIGONAL PYRAMIDAL107°
NH3
Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
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Common Molecular Shapes
4 total2 bond2 lone
BENT104.5°
H2OCourtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
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Common Molecular Shapes
5 total5 bond0 lone
TRIGONAL BIPYRAMIDAL120°/90°
PCl5Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
A Be
Be
Be
Ba
Ba
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Common Molecular Shapes
6 total6 bond0 lone
OCTAHEDRAL90°
SF6
Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
B
B
B
B
B
BA
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Examples
PF3
4 total3 bond1 lone
TRIGONAL PYRAMIDAL
107°
F P FF
Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem
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ExamplesCO2
O C O2 total2 bond0 lone LINEAR
180°
Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem