CHM 2045 Molecular Geometry & Chemical Bonding Chapter 10
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Transcript of CHM 2045 Molecular Geometry & Chemical Bonding Chapter 10
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• CHM 2045• Molecular Geometry & Chemical Bonding Chapter 10
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Using Lewis Theory to PredictMolecular Shapes
• Lewis theory says that these regions of electron groups should repel each other
• This idea can then be extended to predict the shapes of molecules– the position of atoms surrounding a central atom will be
determined by where the bonding electron groups are– the positions of the electron groups will be determined by
trying to minimize repulsions between them
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VSEPR Theory• Electron groups around the central atom will be
most stable when they are as far apart as possible – we call this valence shell electron pair repulsion theory
• The resulting geometric arrangement will allow us to predict the shapes and bond angles in the molecule
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Electron Group Geometry• There are five basic arrangements of electron
groups around a central atom
• Each of these five basic arrangements results in five different basic electron geometries
• For molecules that exhibit resonance, it doesn’t matter which resonance form you use – the electron geometry will be the same
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Linear Electron Geometry• When there are two electron groups around the
central atom, they will occupy positions on opposite sides of the central atom
• This results in the electron groups taking a linear geometry
• The bond angle is 180°
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Trigonal Planar Electron Geometry• When there are three electron groups around the
central atom, they will occupy positions in the shape of a triangle around the central atom
• This results in the electron groups taking a trigonal planar geometry
• The bond angle is 120°
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Tetrahedral Electron Geometry• When there are four electron groups around the
central atom, they will occupy positions in the shape of a tetrahedron around the central atom
• This results in the electron groups taking a tetrahedral geometry
• The bond angle is 109.5°
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Tetrahedral Geometry
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Trigonal Bipyramidal Electron Geometry
• When there are five electron groups around the central atom, they will occupy positions in the shape of two tetrahedra that are base-to-base with the central atom in the center of the shared bases.
• This results in the electron groups taking a trigonal bipyramidal geometry
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Trigonal Bipyramidal Geometry
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Octahedral Electron Geometry• When there are six electron groups around the
central atom, they will occupy positions in the shape of two square-base pyramids that are base-to-base with the central atom in the center of the shared bases
• This results in the electron groups taking an octahedral geometry
• All positions are equivalent• The bond angle is 90°
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Octahedral Geometry
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Octahedral Geometry
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Molecular Geometry• The actual geometry of the molecule may be
different from the electron geometry• When the electron groups are attached to
atoms of different size,• when the bonding to one atom is different than
the bonding to another, • When there are lone pairs since they occupy
space on the central atom, but are not “seen” as points on the molecular geometry
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The Effect of Lone Pairs• Lone pair groups “occupy more space” on the
central atom
• Relative sizes of repulsive force interactions isLone Pair – Lone Pair > Lone Pair – Bonding Pair > Bonding Pair – Bonding Pair
• This affects the bond angles, making the bonding pair – bonding pair angles smaller than expected
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Bond Angle Distortion from Lone Pairs
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Bond Angle Distortion from Lone Pairs
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Molecular Geometry
Example 1Which molecule or ion has a trigonal planar molecular geometry?a)PCl3
b)AsF3
c) HCNd)HCCHe)CO3
2–
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Molecular GeometryExample 2Which molecule or ion has a trigonal pyramidal molecular geometry?a)CO3
2–
b)SO3
c) BF3
d)C2H4
e)SO32–
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Molecular Geometry
Example 3What is the bond angle in a linear molecule or ion?a)90°b)109°c) 120°d)180°
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Molecular Geometry
Example 4The approximate H—C—C bond angle in ethane, C2H6, isa)60°.b)90°.c) 109°.d)120°.e)180°.
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Molecular Geometry
Example 5What is the H—O—H bond angle in water?a)180°b)120°c) 90°d)109°e)slightly less than 109°
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Dipole moment ,the measure of charge separation
• A molecule has a dipole moment when there is charge separation
• The strength of the dipole moment depends on the difference in the electronegativity of the atoms in the molecule
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Dipole moment ,the measure of charge separation
• Dipole moment can be shown with an arrow with a cross on one end:
• An arrow indicates the direction in which the electrons concentrate.
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Molecule Polarity
The O─C bond is polar. The bonding electrons are pulled equally toward both O ends of the molecule. The net result is a nonpolar molecule.
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Molecule Polarity
The H─O bond is polar. Both sets of bonding electrons are pulled toward the O end of the molecule. The net result is a polar molecule.
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Predicting Polarity of Molecules1. Draw the Lewis structure and determine the
molecular geometry2. Determine whether the bonds in the
molecule are polara) if there are no polar bonds, the molecule
is nonpolar3. Determine whether the polar bonds add
together to give a net dipole moment
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Decide whether the following molecules Are polar
polarnonpolar
1. polar bonds, N-O2. asymmetrical shape 1. polar bonds, all S-O
2. symmetrical shape
TrigonalBent Trigonal
Planar2.5
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Polar or NonpolarExample 6Which of the following molecule is polar?
a)CF4
b)SO2
c) CS2
d)C2H4
e)C6H6
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Polar or NonpolarExample 7Which of the following compounds is nonpolar?
a)XeF2
b)HClc) SO2
d)H2Se)N2O
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Dipole MomentExample 8Which of the following molecules has a dipole moment?a)NF3
b)CCl4
c) SiCl4
d)SF6
e)BF3
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Dipole MomentExample 9For which molecule or ion does the nitrogen atom have the positive end of the dipole moment?a)NH4
+
b)Ca3N2
c) HCNd)AlNe)NO
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Valence Bond Theory
• Linus Pauling and others applied the principles of quantum mechanics to molecules
• They reasoned that bonds between atoms would occur when the orbitals on those atoms interacted to make a bond
• The kind of interaction depends on whether the orbitals align along the axis between the nuclei, or outside the axis
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Valence Bond Theory
• Linus Pauling and others applied the principles of quantum mechanics to molecules
• They reasoned that bonds between atoms would occur when the orbitals on those atoms interacted to make a bond
• The kind of interaction depends on whether the orbitals align along the axis between the nuclei, or outside the axis
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Valence Bond Theory – Hybridization• One of the issues that arises is that the number
of partially filled or empty atomic orbitals did not predict the number of bonds or orientation of bonds – C = 2s22px
12py12pz
0 would predict two or three bonds that are 90° apart, rather than four bonds that are 109.5° apart
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Hybridization• To adjust for these inconsistencies, it was
postulated that the valence atomic orbitals could hybridize/mix before bonding took place
– one hybridization of C is to mix all the 2s and 2p orbitals to get four orbitals that point at the corners of a tetrahedron
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Unhybridized C Orbitals Predict the Wrong Bonding & Geometry
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Hybridization• Some atoms hybridize their orbitals to maximize
bonding• Hybridizing is mixing different types of orbitals
in the valence shell to make a new set of degenerate orbitals– sp, sp2, sp3, sp3d, sp3d2
• Same type of atom can have different types of hybridization– C = sp, sp2, sp3
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Hybrid Orbitals
• The number of atomic orbitals combined = the number of hybrid orbitals formed
• The number and type of standard atomic orbitals combined determines the shape of the hybrid orbitals
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Orbital Diagram of the sp3 Hybridization of C
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Methane Formation with sp3 C
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sp3 Hybridized AtomsOrbital Diagrams
Unhybridized atom
2s 2p
sp3 hybridized atom
2sp3
C
2s 2p
2sp3
N
• Place electrons into hybrid and unhybridized valence orbitals
as if all the orbitals have equal energy• Lone pairs generally occupy hybrid orbitals
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Bonding with Valence Bond Theory
• According to valence bond theory, bonding takes place between atoms when their atomic or hybrid orbitals “overlap”
• To interact, the orbitals must either be aligned along the axis between the atoms, or
• The orbitals must be parallel to each other and perpendicular to the interatomic axis
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Types of Bonds• A sigma (s) bond results when the interacting atomic
orbitals point along the axis connecting the two bonding nuclei
• A pi (p) bond results when the bonding atomic orbitals are parallel to each other and perpendicular to the axis connecting the two bonding nuclei
• The interaction between parallel orbitals is not as strong as between orbitals that point at each other; therefore s bonds are stronger than p bonds
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Orbital Diagrams of Bonding
• “Overlap” between a hybrid orbital on one atom with a hybrid or nonhybridized orbital on another atom results in a s bond
• “Overlap” between unhybridized p orbitals on bonded atoms results in a p bond
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sp2 Hybridized AtomsOrbital Diagrams
Unhybridized atom
2s 2p
sp2 hybridized atom
2sp2
2p
C3 s1 p
2s 2p
2sp2
2p
N2 s1 p
48Tro: Chemistry: A Molecular Approach, 2/e
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sp2 hybridization in Ethylene
• Two sp2-hybridized orbitals overlap to form a s bond
• p orbitals overlap side-to-side to formation a pi (p) bond
• sp2–sp2 s bond and 2p–2p p bond result in sharing four electrons and formation of C-C double bond
• Electrons in the p bond occupy regions on either side of a line between nuclei
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sp2 hybridization in Ethylene, C 2H4
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sp hybridization in Acetylene, C2H2
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Hybridization & Molecular Geometry
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Hybridization
Example 11The hybridization of the central atom in a molecule is described as sp2. The arrangement in space of the hybrid orbitals about that atom isa) linear.b) trigonal planar.c) tetrahedral.d) trigonal bipyramidal.
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Hybridization
Example 12Which of the following statements is incorrect
regarding the water molecule?a)The molecule is polar.b)The hybridization of oxygen is sp3.c) There are two lone pairs and two bonding
pairs on the central atom.d)The molecular geometry is bent.e)The hybridization of hydrogen is sp.
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Hybridization
Example13What is the hybridization of Se in SeF6?
a)spb)sp2
c) sp3
d)dsp3
e)d2sp3