polarity by adding the individual bond dipoles, one can determine the overall dipole moment for the...
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Polarity
By adding the individual bond dipoles, one can determine the overall dipole moment for the molecule.
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Polarity
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Polarity
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Electron Domains
• We can refer to the electron pairs as electron domains.
• In a double or triple bond, all electrons shared between those two atoms are on the same side of the central atom; therefore, they count as one electron domain.
• The central atom in this molecule, A, has four electron domains.
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Valence-Shell Electron-Pair Repulsion Theory (VSEPR)
“The best arrangement of a given number of electron domains is the one that minimizes the repulsions among them.”
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Molecular Geometries
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Molecular Geometries
Within each electron domain, then, there might be more than one molecular geometry.
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Linear Electron Domain
• In the linear domain, there is only one molecular geometry: linear.
• NOTE: If there are only two atoms in the molecule, the molecule will be linear no matter what the electron domain is.
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Trigonal Planar Electron Domain
• There are two molecular geometries:– Trigonal planar, if all the electron domains are
bonding,– Bent, if one of the domains is a nonbonding pair.
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Tetrahedral Electron Domain
• There are three molecular geometries:– Tetrahedral, if all are bonding pairs,– Trigonal pyramidal, if one is a nonbonding pair,– Bent, if there are two nonbonding pairs.
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Trigonal Bipyramidal Electron Domain
• There are four distinct molecular geometries in this domain:– Trigonal bipyramidal– Seesaw– T-shaped– Linear
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Trigonal Bipyramidal Electron Domain
Lower-energy conformations result from having nonbonding electron pairs in equatorial, rather than axial, positions in this geometry.
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Octahedral Electron Domain
• All positions are equivalent in the octahedral domain.
• There are three molecular geometries:– Octahedral– Square pyramidal– Square planar
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Nonbonding Pairs and Bond Angle• Nonbonding pairs are physically
larger than bonding pairs.• Therefore, their repulsions are
greater; this tends to decrease bond angles in a molecule.
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Multiple Bonds and Bond Angles
• Double and triple bonds place greater electron density on one side of the central atom than do single bonds.
• Therefore, they also affect bond angles.
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Larger Molecules
In larger molecules, it makes more sense to talk about the geometry about a particular atom rather than the geometry of the molecule as a whole.
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Overlap and Bonding
• We think of covalent bonds forming through the sharing of electrons by adjacent atoms.
• In such an approach this can only occur when orbitals on the two atoms overlap.
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Overlap and Bonding
• Increased overlap brings the electrons and nuclei closer together while simultaneously decreasing electron– electron repulsion.
• However, if atoms get too close, the internuclear repulsion greatly raises the energy.
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Hybrid Orbitals• These two degenerate orbitals would align
themselves 180 from each other.• This is consistent with the observed geometry of
beryllium compounds: linear.
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Hybrid Orbitals
With carbon, we get four degenerate sp3 orbitals.
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Electron-Domain Geometries
Table 9.1 contains the electron-domain geometries for two through six electron domains around a central atom.
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Bonds
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Multiple Bonds
• In a molecule like formaldehyde (shown at left), an sp2 orbital on carbon overlaps in fashion with the corresponding orbital on the oxygen.
• The unhybridized p orbitals overlap in fashion.
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Multiple Bonds
In triple bonds, as in acetylene, two sp orbitals form a bond between the carbons, and two pairs of p orbitals overlap in fashion to form the two bonds.
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Delocalized Electrons: Resonance
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Delocalized Electrons: Resonance
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ResonanceThe organic molecule benzene has six bonds and a p orbital on each carbon atom.
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Resonance• In reality the electrons in benzene are not
localized, but delocalized.• The even distribution of the electrons in benzene
makes the molecule unusually stable.
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Molecular-Orbital (MO) Theory
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MO Theory
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MO Theory
• For atoms with both s and p orbitals, there are two types of interactions:– The s and the p orbitals
that face each other overlap in fashion.
– The other two sets of p orbitals overlap in fashion.
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MO Theory
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MO Theory
• The smaller p-block elements in the second period have a sizable interaction between the s and p orbitals.
• This flips the order of the and molecular orbitals in these elements.
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Second-Row MO Diagrams