mos_s09 - Outline for second exam period Molecular orbitals...

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Outline for second exam period Molecular orbitals in diatomics, triatomics and higher Bonding in metals – crystal lattices and unit cells Bonding in ionic solids Electrostatic model of ionic bond Lattice energy Thermochemical (Born-Haber) cycles Intermolecular forces (weak bonding interactions) Solubilities of ionic compounds Second Exam – Wednesday, February 25
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The Lewis structure for molecular oxygen Lewis structures of the superoxide and peroxide ions suggest that each has a single bond Experiment indicates that superoxide has a bond order of 1.5 OO 2- 1- Predicts an oxygen-oxygen double bond and no unpaired electrons. Experiment indicates that the oxygen-oxygen bond order is 2, but that there are two unpaired electrons. Molecular oxygen can be reduced by one electron, to superoxide ion, and by two electrons to peroxide ion. The former has one unpaired electron.
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Molecular orbitals from two H 1s orbitals E H(1) H(2) N 1 + N 2 N 1 - N 2 F 1s ( F 1 ) F *( F 2 ) Electron densities for MO’s (from Coulson, 2 nd ed., p. 84) Contour maps for MO’s (from Coulson) N 1 + N 2 N 1 - N 2 H 2 + σ 1 0.5 1.05 256 H 2 σ 2 10 . 7 4 432 B.O. D/ D E, kJ/mol
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MO’s for homonuclear 2nd period diatomics N 1 + N 2 N 1 - N 2 N 1 - N 2 N 1 + N 2 s s p p E E N 1 + N 2 N 1 - N 2 s s p p N 1 - N 2 N 1 + N 2
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s & p orbital energies vs Z -60 -50 -40 -30 -20 -10 0 L i B e BCNOF E/eV s p
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Molecular orbitals from p orbitals N 1 - N 2 N 1 + N 2 N 1 + N 2 N 1 - N 2
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s s p p σ s σ s * σ p σ p * π π * σ sp s s p p σ sp * σ ps σ ps * π π * B 2 KK 4 σ 2 σ * 2 π 2 11 . 5 9 2 9 1 C 2 KK 4 σ 2 σ * 2 π 4 21 . 2 4 5 9 9 N 2 KK 4 σ 2 σ * 2 π 4 σ 2 31 . 1 0 9 4 2 O 2 KK 4 σ 2 σ * 2 σ 2 π 4 π * 2 . 2 1 4 9 4 F 2 KK 4 σ 2
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mos_s09 - Outline for second exam period Molecular orbitals...

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