The Shape of Molecules and Polyatomic Ions

Based on a valid Lewis structure and the positioning of electron pairs as far apart from one another as possible.

VSEPR

Valence Shell Electron Pair Repulsion Theory

Valence e- on a central atom (both bonding and nonbonding pairs) will take up positions as far away from each other as possible (i.e., e- pairs repel each other).

Gives rise to the five fundamental electronic geometries for the arrangement of 2, 3, 4, 5 and 6 regions of electron density. Example Lewis Structure # e- pairs VSEPR central fundamental atom geometry Bond Angles

BeCl2

180o

BF3

120o

CH4

109.5o

PCl5

90o & 120o

SF6

90o

The Electronic Geometry is defined by the position of e- pairs on the central atom ( one of the five fundamental VSEPR geometries). Molecular Geometry is defined by the positions of other nuclei around the central atom and are based on (but not necessarily identical to) one of the five basic VSEPR geometries. Lone pairs on the central atom occupy space, but do not define molecular geometry. (Molecular geometries and bond angles can be experimentally verified by x-ray diffraction analysis). If there are no lone pairs on the central atom, then Electronic Geometry = Molecular Geometry.

The process of predicting geometries.

1. Draw a valid Lewis structure 2. Determine the number of regions of high electron density surrounding the central atom (multiple bonds counted as a single region of high e- density for the purpose of determining geometry) 3. Arrange e- pairs as far apart as possible to achieve one of the five fundamental VSEPR geometries. 4. Consider the affect of lone pair e- on the central atom as modifying one of these five fundamental geometries.

Examples: CO2, BH3, NO3-, CO32-, SO42-, AsF5, SeCl6

The effect of lone pairs

Repulsive forces around central atoms LP LP > LP - BP > BP BP Resulting in a contraction of bond angles.

Examples: CH4 NH3 H2O

Examples: OCN-, SO2, NO2-, ClO3-, SF4, I3-, BrF5, XeF4

In trigonal bi-pyramid and octahedral geometries, always minimize the number of 90o LP-LP interactions.

lone pairs always in equatorial positions SF4 ClF3 IF2-

In situations where several resonance structures can be drawn, any one can be used to predict geometry (remember to treat multiple bonds as effectively one bonding pair in VSEPR). SO3 COS O3

Molecular Polarity (re-visited)

Polar molecules have a net dipole moment, resulting from the unequal distribution of e- density. Depends on: Bond dipoles (electronegativity difference between atoms) Molecular geometry (Polar covalent bonds within a molecule may or may not lead to a polar molecule overall) Polar molecules have markedly different physical and chemical properties than non-polar molecules. Eg; CO2, SO2, SO3, H2CO, BrF3, BF3, CCl4, CHCl3

Molecules in which there is no single central atom. VSEPR can be used in more complex bonding schemes to describe geometries and predict bond angles.

CH3NO2

NH2OH

CH3

CH3

H : O:

Vitamin-A

CH3
: O:

H3C :O :
Caffeine

N: .. N CH3

CH3 N: H N: