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Lecture 24: Beyond the Octet. Reading: Zumdahl 13.9-13.12 Outline Sub-octet systems Valence-shell expansion Radicals: odd-electron systems. Beyond the Octet Rule. There are numerous exceptions to the octet rule. . We’ll deal with three types of exceptions here:

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Lecture 24: Beyond the Octet


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    1. Lecture 24: Beyond the Octet • Reading: Zumdahl 13.9-13.12 • Outline • Sub-octet systems • Valence-shell expansion • Radicals: odd-electron systems

    2. Beyond the Octet Rule There are numerous exceptions to the octet rule. We’ll deal with three types of exceptions here: 1. Sub-octet systems (less than 8 electrons) 2. Valence shell expansion (more than 8 electrons) 3. Radicals ( an odd number of electrons)

    3. Sub-Valent Systems • Some atoms (for example, Be, B, and Al) undergo bonding, but will form stable molecules that do not fulfill the octet rule. • Experiments demonstrate that the B-F bond strength is consistent with single bonds only.

    4. The octet rule is satisfied by the reacting partner providing an electron pair. A bond in which both electrons come from one of the atoms is called a coordinate covalent bond. • Sub-valent molecules will react with other molecules such that the octet rule is satisfied.

    5. Valence Shell Expansion For third-row elements (Period 3) and beyond, the available nearby d-orbitals allows for the participation of these orbitals in bonding. When this occurs, more than 8 electrons can surround a third-row element. • Example: ClF3 (a 28 e- system) F obey octet rule Cl has 10e-

    6. Typical atoms that demonstrate valence-shell expansion are P, S, and larger halogens (Cl, Br, and I). • Example: PCl5 (40 electrons)

    7. Lewis-dot structure for valence shell expansion: Assign all electrons to bonds and electrons so as to give each atom an octet. For halogen complexes (like PCl5), expand the octet of period-3 elements using single bonds until halogens are bonded. Finally, assign any remaining electrons to the period-3 element. 22 e- • Example: I3-

    8. A famous example: XeO3 26 e- Bonding in molecules containing nobel-gas atoms involves valence shell expansion +3 +2 -1 -1 -1 -1 -1 0 0 +1 0 0 0 -1 0 0

    9. Radicals: Odd-Electron Systems • Finally, one can encounter odd electron systems where full electron pairs will not exist. • Example: Chlorine Dioxide. 19 e- Unpaired electron

    10. Radicals: Odd-Electron Systems Strategy: Generally, attempt to put the odd electron on the central atom. However, the LDS rules were not intended to be applied to odd-electron systems. • Example: NO2. 17 e- N is sub-octet; therefore, predict that NO2 is highly reactive.

    11. Lewis Dot Rules Summary Remember the following: *(C, N, O, and F) almost always obey the octet rule. *(B, Be, and Al) are often sub-octet *Second row (Period 2) elements never exceed the octet rule *Third Row (Period 3) elements and beyond can use valence shell expansion to exceed the octet rule. • In the end, you have to practice…..a lot!