1. Lecture 23: Lewis Dot Structures Reading: Zumdahl 13.9-13.12 Outline –Lewis Dot Structure Basics –Resonance –Formal Charge

5. Localized Bond Models Consider our energy diagram for H 2 bonding:

6. Localized Model Limitations It is important to keep in mind that the models we are discussing are just that…..models. We are operating under the assumption that when forming bonds, atoms “share” electrons using atomic orbitals. Electrons involved in bonding: “bonding pairs”. Electrons not involved in bonding: “lone pairs”.

8. Lewis Dot Structures (cont.) Developed by G. N. Lewis to serve as a way to describe bonding in polyatomic systems. Central idea: the most stable arrangement of electrons is one in which all atoms have a “noble” gas configuration. Example: NaCl versus Na + Cl - Na: [Ne]3s 1 Cl: [Ne]3s 2 3p 5 Na + : [Ne]Cl - : [Ne]3s 2 3p 6 = [Ar]

9. LDS Mechanics Atoms are represented by atomic symbols surrounded by valence electrons. Electron pairs between atoms indicate bond formation. Bonding Pair Lone Pair (6 x)

10. LDS Mechanics (cont.) Three steps for “basic” Lewis structures: 1.Sum the valence electrons for all atoms to determine total number of electrons. 2.Use pairs of electrons to form a bond between each pair of atoms (bonding pairs). 3.Arrange remaining electrons around atoms (lone pairs) to satisfy the “octet rule” (“duet” rule for hydrogen).

11. LDS Mechanics (cont.) An example: Cl 2 O 20 e - 16 e - left

12. LDS Mechanics (cont.) An example: CH 4 8 e - 0 e - left Done!

13. LDS Mechanics (cont.) An example: CO 2 16 e - 12 e - left 0 e - left Octet Violation CO double bond

14. LDS Mechanics (cont.) An example: NO + 10 e - ++ 8 e - left +

15. LDS Mechanics (cont.) NO 3 - 24 e -

16. Resonance Structures We have assumed up to this point that there is one correct Lewis structure. There are systems for which more than one Lewis structure is possible: –Different atomic linkages: Structural Isomers –Same atomic linkages, different bonding: Resonance

17. Resonance Structures (cont.) The classic example: O 3. Both structures are correct!

18. Resonance Structures (cont.) In this example, O 3 has two resonance structures: Conceptually, we think of the bonding being an average of these two structures. Electrons are delocalized between the oxygens such that on average the bond strength is equivalent to 1.5 O-O bonds.

19. Resonance Structures (cont.) NO 3 - is a classic example of resonance:

20. Structural Isomers What if different sets of atomic linkages can be used to construct correct LDSs: Both are correct, but which is “more” correct?

21. Formal Charge Formal Charge: Compare the nuclear charge (+Z) to the number of electrons (dividing bonding electron pairs by 2). Difference is known as the “formal charge”. #e- 7 6 7 7 6 7 Z + 7 6 7 7 7 6 Formal C. 0 0 0 0 +1 -1 Structure with less F. C. is more correct.

22. Formal Charge Example: CO 2 e - 6 4 6 6 4 67 4 5 Z + 6 4 6 6 6 46 6 4 FC 0 0 0 0 +2 -2-1 +2 -1 More Correct

23. Triatomic Bonding Patterns Compare CO 2 with N 3 - …both 16 e - systems: FC-1 +1 -1-2 +1 00 +1 -2 FC0 0 0-1 0 +1+1 0 -1