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Learning goals:
• Be able to draw Lewis dot structures, assign formal charges, predict molecular
geometries (including bond angles), and calculate bond orders for molecules, including
hypervalent molecules and ions.
• Describe hypervalent molecules using no-bond resonance.
• Understand and articulate how predictions of molecular structure and bonding can be
experimentally verified.
• Use the isoelectronic principle to design new molecules and solids.
• Rationalize bond strength and chemical reactivity using bond polarity arguments.
• Interrelate bond length and bond strength.
Textbook Chapter 1
Perspective
Conceptually parallels atomic structure – begin with simplest, usually
empirical guidelines, then increase the degree of sophistication and the
quantitative nature in order to more fully account for all observations
Many of these concepts will be familiar – we will likely introduce them from
a different perspective, though, and for a more diverse range of systems.
We will also dive deeper into “reality” in these topics and systems than you
probably have previously.
Lewis structures
G.N. Lewis: The existence of many molecules can be rationalized by the
octet rule, where atoms share electrons so that they have eight valence
electrons – based on s2p6 configuration
NH3
Formal charge
NO3−
Ozone
Ozone (continued)
What is the real structure?
How would you study this experimentally?
Nitrate
Cyanate
ONF3
You perform a diffraction experiment to determine the crystal structure of
ONF3 and find the following bond lengths:
N-F: 143.1 pm
N-O: 115.8 pm
Molecular shape – same (subset of electronic shape), but ignore the lone
pairs (just the geometry defined by the actual attached atoms)
SO2
H2O
CO2
SF4
How do we
rationalize this?
Is there an
alternative option?
VSEPR lone pair / bonding pair hierarchy
Consider the various molecular geometry options for ClF3
BrF4–
(c) For (b), assign all bond orders, formal charges, and bond angles
X E(X-X) (kcal/mol)
F 38
Cl 58
Br 46
I 36
Bond strength / bond length correlation
How is this manifested in the properties of
F2 vs. the other diatomic halogens?
https://www.youtube.com/watch?v=HqhPzhJxDkk
https://www.youtube.com/watch?v=oipksRhISfM
Related phenomena
C vs. Si
N vs. P
Polarity
One consequence of the way in which atoms are arranged around a central
atom is polarity – dipoles that depend on electronegativity differences
between atoms in asymmetric structures
Trends?
Exercise
Draw Lewis structures for the following molecules and compare/contrast
CO2
N 2O
Allene (H2CCCH2)
Azide (N3–)
Which one of these is not like the others?
BF3
NF3
COF2
NO3–
CO32–
Isoelectronic principle (solids)
The isoelectronic principle also extends to solid-state materials
Al Si P S
Cd Ga Ge As Se
In Sn Sb Te