Inorganic Chemistry II

Chemical Bonding and

Geometry
 A Chemical Bond is defined as the strong force of attraction which can
hold two species (ions, atoms or molecules) together.

Causes of Bonding:

Overall decrease in energy

Every system in the universe has a tendency to stay in the lowest
energy firm. Whenever a bond is formed, energy is released so that the
system has lesser energy. So a bond formation is a natural tendency.

Attainment of stable configuration

- Noble gases electron configuration
- ns2,ns2np6
-Octet Rule: atoms are most stable when they have 8 electrons in
their outermost shell (only period 2 elements).

What about elements in period 1, 3, 4, etc.?

 Types of Bonds

Covalent bonding

sharing of electrons between atoms, e.g. F2

Ionic bonding

transfer and gain of electrons causing charged ions that attract, e.g.
CsF.

Metallic bonding

Metals share electrons amongst all atoms, e.g. Cs

Define/Compare covalent radius and Van der Waals
radius!
 Figure 1. A Ketelaar triangle: Average electronegativity vs
electronegativity difference

Question: Use the Ketelaar triangle and the electronegativity values to predict the
type of bonding in CaO, AlCl3 and P2O5.
 The Born-Haber Cycle

an enthalpy cycle used to calculate the standard enthalpy change of

formation of ionic compounds. (after Max Born and Fritz Haber)

Application of Hesss law to ionic compounds.

Hesss law states that the value of the standard enthalpy change of a
reaction is independent of the route taken.

e.g. The formation of sodium chloride from its elements is

shown below:

Na(s) + 1/2Cl2(g) NaCl(s)

this equation represent the direct route, where the

reactants and product are in their standard state.

The indirect route consists of five separate steps:

1. Sublimation enthalpy, HS
2. Dissociation enthalpy, HD

3. Ionization enthalpy, HI

4. Electron-gain enthalpy, HEG

5. Lattice enthalpy, HL

Using Hesss law, the sum of the standard enthalpy changes for this
indirect route equals -411kJ mol-1 = Hf NaCl.

Hf = HS + HD + HI + HEG + HL

Any of the above enthalpies can be calculated e.g. HL, if all the others
are known.

A cycle can also be drawn showing both the direct and indirect routes
leading to the formation of solid NaCl. (illustration!).
 Lewis Theory and Structures

Lewis structures (Lewis-dot diagrams), are diagrams that show the

bonding between atoms of a molecule, and the lone pairs of electrons that
may exist in the molecule.

The Lewis structure was named after Gilbert N. Lewis, who introduced it in
1916. It can be drawn for any covalently-bonded molecule, as well as
coordination compounds.

Lewis-dot diagrams are similar to electron dot diagrams in that the valence
electrons ( lone pairs) are represented as dots, but they also contain lines to
represent shared electron pairs in a chemical bond (single, double, etc.).

Lewis structures show each atom in the structure of the molecule using its
chemical symbol. Lines are drawn between atoms that are bonded to one
another (rarely, pairs of dots are used instead of lines). Excess electrons
that form lone pairs are represented as pairs of dots, and are placed next to
the atoms.
 Choosing a central atom:
The central atom is usually the least electronegative atom, except hydrogen.
For example, in thionyl chloride (SOCl2), the sulfur atom is the central
atom.

Counting electrons:
The total number of electrons represented in a Lewis structure is equal to
the sum of the numbers of valence electrons on each individual atom. Non-
valence electrons are not represented in Lewis structures.

Examples:
H2, HCl, BeCl2, BF3, BF4-, CH4, NH3, H2O, PF3, PCl5 and SF6.
 When the Lewis structure of an ion is written, the entire structure is placed in
square brackets, and the charge is written as a superscript on the upper
right, outside the brackets.

Formal Charge:
The formal charge is the charge an atom would have if electron pairs were
shared equally. The total of the formal charges on an ion should be equal to
the charge on the ion, and the total of the formal charges on a neutral
molecule should be equal to zero.

f = V L 1/2B where:

f is the Formal charge.

V represents the number of valence electrons in a free atom of the element.
L represents the number of unshared (lone pair) electrons on the atom.
B represents the total number of bonding electrons the atom has with
another.
 Examples of Formal Charge calculations:
HOCl, CN- and NO+.

Resonance
For some molecules and ions, it is difficult to determine which lone pairs
should be moved to form double or triple bonds. This is sometimes the case
when multiple atoms of the same type surround the central atom, and is
especially common for polyatomic ions.
When this situation occurs, the Lewis structure is said to be a resonance
structure, and the molecule exists as a resonance hybrid. Each of the
different possibilities is superimposed on the others, and the molecule is
considered to have a Lewis structure equivalent to an average of these
states.

When comparing resonance structures for the same molecule, usually those
with the fewest formal charges contribute more to the overall resonance
hybrid. When formal charges are necessary, resonance structures that
have negative charges on the more electronegative elements and positive
charges on the less electronegative elements are favored.
 Example:
NO2-

Other examples:
NO3- and SO42-.

References
1. Zumdahl, S. (2005) Chemical Principles Houghton-Mifflin (ISBN 0-618-37206-7)
2. Miessler, G. L., Tar, D. A., (2003) "Inorganic Chemistry" 2nd ed. Pearson Prentice-
Hall (ISBN 0-130-35471-6)
3. Lewis, G. N. The Atom and the Molecule. J. Am. Chem. Soc. 1916, 38, 762-785.
4. Miessler, G. L., Tar, D. A., (2003), p53 - Explanation of formal charge usage.
 Hybridization

Hybridization is the concept (theory) of mixing atomic orbitals to form new

hybrid orbitals suitable for the qualitative description of atomic bonding
properties.

Hybridised orbitals are very useful in the explanation of the shape of

molecular orbitals for molecules. It is an integral part of valence bond theory.

Examples: sp hybridization BeCl2 (Linear shape)

sp2 hybridization BF3 (Trigonal planar shape)
sp3 hybridization CH4 (Tetrahedral shape)
sp3d hybridization PF5 (Trigonal bipyramidal)
sp3d2 hybridization SF6 (Octahedral)

The shape/geometry of a molecule is obtained by joining the bonding atoms

with straight lines.
 Valence shell electron pair repulsion (VSEPR) theory:

a model in chemistry, which is used for predicting the shapes of individual

molecules.

VSEPR theory is based on the idea that the geometry of a molecule or

polyatomic ion is determined primarily by repulsion among the pairs of
electrons associated with a central atom. The pairs of electrons may be
bonding or nonbonding (lone pairs). Only valence electrons of the central
atom influence the molecular shape in a meaningful way.

Three types of repulsion take place between the electrons of a molecule:

The lone pair-lone pair repulsion > The lone pair-bonding pair
repulsion > The bonding pair-bonding pair repulsion.
 VSEPR Basic assumptions

Pairs of electrons in the valence shell of a central atom repel each other.

These pairs of electrons tend to occupy positions in space that minimize

repulsions and maximize the distance of separation between them.

The valence shell is taken as a sphere with electron pairs localizing on the
spherical surface at maximum distance from one another.

A multiple bond is treated as if it is a single electron pair and the two or three
electron pairs of a multiple bond are treated as a single super pair.

Where two or more resonance structures can depict a molecule the VSEPR
model is applicable to any such structure.

A molecule must avoid these repulsions to remain stable. When repulsion

cannot be avoided, the weaker repulsion (i.e. the one that causes the
smallest deviation from the ideal shape) is preferred.

Examples: BeCl2, BF3, CH4, NH3, H2O and SF4 (slide no.13)