Supplementary Lecture Notes* for Chapter 1

Exceptions (or Limitations) to the Octet Rule Lewis structures are drawn based on the assumptions that all the atoms in a molecule have the noble gas electron configuration in their valence shell (that is, each of them has 8 valence electrons). But unfortunately, this assumptions (often dubbed as the Octet Rule) couldnt always be met. There are certain exceptions to this rule. Or in other words, when drawing Lewis structures, not all atoms can be straightaway assumed to have 8 valence electrons. There are four types of limitations of the Octet Rule: 1) Compounds or ions containing an odd number of total valence electrons. Examples are NO, with 11 valence shell electrons, and NO2, with 17 valence shell electrons. 2) Electron deficient structures, where the central atom does not have 8 electrons around it. Often involved beryllium (Be) and most covalent compound of Group 3A in the periodic table, especially boron (B). Example 1: Draw suitable Lewis structure for beryllium chloride, BeCl2 Solutions:

Example 2: Write the Lewis formula for boron trichloride, BCl3, a covalent compound.

Solutions:

3) Expanded octet, where the central atom of a Lewis structure has more than 8 electrons. Mostly observed in elements of period 3, due to the involvement of d-orbitals in bonding. By contrast, elements of period 2 of the periodic table can never exceed 8 electrons in their valence shells, because each atom has only 1 s and 3 p orbitals in that shell, with no d-orbitals to be filled. Sulfur (S) and Phosphorus (P) are most likely to follow this expansion, although sometimes they do follow the Octet Rule. (You must always use formal charge to check whether your Lewis structure is correct or not!) Example 3: Write the Lewis structure for sulfur tetrafluoride, SF4. Solutions:

Example 4: Write the Lewis structure for ICl4-

Solutions:

Do this yourself!: Draw the Lewis structures for PF5, XeF2, AlCl3 and I3-. Notes:

Lewis formulas are not normally written for compounds containing d- and f-transition metals. The d- and f-transition metals utilize d or f orbitals (or both) in bonding as well as s and p orbitals. Thus, they can accommodate more than eight valence electrons. Since Be, a compound in 2A Group of periodic table is most likely to violate the Octet Rule, one might expect a similar situation for compounds of the other 2A metals, Mg, Ca, Sr, Ba, and Ra. These elements, however, have lower ionization energies and larger radii than Be, so they usually form ions by losing two electrons.

Polarity in covalent bond As you all should know by now, covalent bonds maybe either polar or nonpolar. Nonpolar covalent bond: - Electron pair is shared equally between the two atoms that build the bond. the shared electrons are equally attracted to both atoms nuclei and therefore True for all homonuclear diatomic molecules.
spend equal amounts of time near each nucleus (both atoms have the same electronegativity).

Polar covalent bond:

Electron pairs are shared unequally between the two atoms that build the bond.
The unequal sharing is due to different electronegativities of both atoms, causing one atom to hug or attract electrons more than the other atom, hence causing some degree of polarity in the bond.

Obviously involves heteronuclear electronegativities. Example: hydrogen fluoride, HF:

atoms

with

different

The separation of charge in a polar covalent bond creates an electric dipole.

The word dipole means two poles. Here it refers to the positive and negative poles that result from the separation of charge within a molecule.

Dipole Moment

 Bond polarities in polar covalent compound is best to be quantified using a numeric scale. Besides using electronegativity differences (EN, which is by the way, arguably not the most accurate method of determining the bond polarities), a more precise way in determining the magnitude of polarity in a polar covalent bond is by using dipole moment. Dipole moment, , is expressed as:

=qxd
where, q = the quantity of charge separated d = distance of separation a.k.a the internuclear distance a.k.a the bond length q is measured in unit coulomb (C, recall that the charge on 1 electron is 1.6022 x 10-19 C) while d is measure in meter (m). As a result, unit for dipole moment, is Cm. However, as an honour to Peter Debye who did the pioneering work on polar molecules, dipole moment is often measured in the unit debye:
1 debye = 1 D = 3.33564 x 10-30 Cm

Another way of estimating dipole moment is by using the percent ionic characteristic. Dear students, to avoid excessive spoonfeeding by your lecturer, you are advise to
learn and find out about this percent ionic characteristic and its connection with dipole moment by yourself.

Sample question: The dipole moment of LiH is 1.964 10-29 Cm, and the
LiH distance is 159.6 pm. What is the approximate percent ionic character in LiH? Answer: 76.8%