CHEMICAL BONDING AND MOLECULAR STRUCTURE

Valency

• Valency is defined as combining power of an element with other atom to form chemical bond.
o It refers to electron(s) in the outer shell of an atom.
• Ionic compounds have fully filled valence shell.
o It is the complete transfer of valence electrons between atoms which generates two
oppositely charged ions.
o It is observed because metals have few electrons in its outer-most orbital. By losing
those electrons, these metals can achieve noble-gas configuration and satisfy the octet
rule.
o Similarly, nonmetals that have close to 8 electrons in its valence shell tend to readily
accept electrons to achieve its noble gas configuration.
• Covalent compounds share electrons between their atoms to attain a filled shell.
o By sharing their outer most (valence) electrons, atoms can fill up their outer electron
shell and gain stability.

Formulae
Molecular Formula

• Molecular formulas describe the exact number and type of atoms in a single molecule of a
chemical compound.
o The constituent elements are represented by their chemical symbols, and the number of
atoms of each element present in each molecule is shown as a subscript following that
element’s symbol.
o It suggests the simple chemical structures, and is not same as the full chemical structural
formula.
• Covalent compounds are usually represented by their molecular formula. For e.g., the molecular
formula of ethanol is C2H5OH.

Empirical Formula

• Empirical formulas are the simplest form of notation.

• The molecular formula for a compound is equal to, or a whole-number multiple of, its empirical
formula.
• Like molecular formulas, empirical formulas are not unique and can describe a number of
different chemical structures or isomers.
• To determine an empirical formula, the mass composition of its elements can be used to
mathematically determine their ratio.
• Ionic compounds are found in lattice structures. They can therefore be expressed in terms of
empirical formula.
 o For example, the empirical formula for calcium chloride is CaCl2. This means there are
two chloride ions per calcium ion in the lattice.

Structural Formula

• Structural formula of a compound is its complete graphical representation showing the number
of bonds between atoms.
• For e.g., the molecular formula of ethene is C2H4 and its structural formula is:

Summary

• For butane and isobutane, the empirical formula for both molecules is C2H5, and they share the
same molecular formula, C4H10. However, one structural representation for butane is
CH3CH2CH2CH3, while isobutane can be described using the structural formula (CH3)3CH.

Examples

IUPAC Name of Molecular Empirical Structural Formula

Compound Formula Formula
Sodium chloride N/A NaCl N/A
Iron(II) chloride N/A FeCl2 N/A
Acetic acid CH3COOH CH2O

Carbon disulfide CS2 CS2

Dinitrogen tetroxide N2O4 NO2

Aluminium hydroxide N/A AlO3H3

Lewis Diagrams

• Lewis postulated that atoms achieve the stable octet when they are linked by chemical bonds.
• He introduced simple notations to represent valence electrons in an atom. These notations are
known as Lewis symbols.
o For e.g., Lewis symbols for some common elements are:
 o The number of dots around the symbol represents the number of valence electrons.
o This number of valence electrons helps to calculate the common or group valence of the
elements.
o The group valence of the elements is generally either equal to the number of dots in
Lewis symbols or 8 minus the number of dots.

Lewis Structure of Ionic Compounds

• Ionic bonds are caused by electrons transferring from one atom to another. To write the Lewis
structure of ionic compounds,
o A square bracket encases the anion to show that the electrons belong to it.
o The need for the number of electrons lost being equal to the number of electrons
gained explains why ionic compounds have the ratio of cations to anions that they do.
o Take the example of Na2O and MgO:

Lewis Structure of Covalent compounds

• Lewis structures for covalent compounds show bonding in terms of shared pairs of electrons
and octet rule.
• The rules to follow when drawing Lewis structures for covalent compounds are:
o Add the valence electrons of the combining atoms to find the total number of electrons
required to write the structure.
o Distribute the total number of electrons as bonding shared pairs between the atoms in
proportion to the total bonds.
o In general, the least electronegative atom occupies the central position in the structure.
o After accounting for the shared pairs of electrons for single bonds, the remaining
electron pairs are either utilized for multiple bonding or remain as the lone pairs.
• When drawing the structures, remember the following points:
 o The elements of the second period (Li to Ne) are said to obey the octet rule even though
they never have more than eight electrons in their valence shell.
o For boron compounds, e.g., BH3, the B atom is said to be electron deficient with less
than eight electrons in the valence shell.

Exceptions to the octet rule

• The elements in the third period and beyond are said to be hypervalent. They have expanded
octets of more than eight valence electrons. For e.g., PCl5 and XeO3.
• When calculating the total number of electrons required to draw the structure, the central atom
is hypervalent if:
o the number of bonds calculated is lower than the minimum number of bonds required
to link the atoms to one another.

Examples

The Lewis representation of some molecules are shown below:

1. H2O.

o Two H atoms provide one electron each and the O atom provides six electrons. The total
number of valence electrons is eight.
o Each H atom needs one more electron and the O atom needs two more electrons to
have filled shells, i.e., a total of four electrons are needed.
o Therefore, 2 bonds are formed using four electrons.
o The remaining four electrons exist as lone pairs.

2. HCl

o Total number of valence electrons = 1 x 1 (H) + 1 x 7 (Cl) = 8 electrons

o The number of electrons needed to have filled shell = 1 x 1 (H) + 1 x 1 (Cl) = 2 electrons
o The number of bonds formed = 2/2 = 1

3. NH3

o Total number of valence electrons = 3 x 1 (H) + 1 x 5 (N) = 8 electrons

o The number of electrons needed to have filled shell = 3 x 1 (H) + 1 x 3 (N) = 6 electrons
o The number of bonds formed = 6/2 = 3
4. N2

o Total number of valence electrons = 2 x 5 (N) = 10 electrons

o The number of electrons needed to have filled shell = 2 x 3 (N) = 6 electrons
o The number of bonds formed = 6/2 = 3

5. BF3

o Total number of valence electrons = 1 x 3 (B) + 3 x 7 (F) = 24 electrons

o The number of electrons needed to have filled shell = 1 x 5 (B) + 3 x 1 (F) = 8 electrons
o The number of bonds formed = 8/2 = 4, but since there are three F atoms, only three
B—F bonds are formed. B remains electron deficient (as discussed above).

6. CH4

o Total number of valence electrons = 1 x 4 (C) + 1 x 4 (H) = 8 electrons

o The number of electrons needed to have filled shell = 1 x 4 (C) + 1 x 4 (H) = 8 electrons
o The number of bonds formed = 8/2 = 3

7. CO2
o Total number of valence electrons = 1 x 4 (C) + 1 x 6 (O) = 10 electrons
o The number of electrons needed to have filled shell = 1 x 4 (C) + 2 x 2 (O) = 8 electrons
o The number of bonds formed = 8/2 = 4
Molecular shapes

• Lewis concept is unable to explain the shape of molecules.

• The valence shell electron pair repulsion theory (VSEPR) provides a simple procedure to predict
the shapes of covalent molecules.

The main postulates of the VSEPR theory

• The shape of a molecule depends upon the number of valence shell electron pairs (bonded or
nonbonded) around the central atom.
• Pairs of electrons in the valence shell repel one another since their electron clouds are
negatively charged.
• These pairs of electrons tend to occupy such position in space that minimize repulsion and and
thus maximize distance between them.
• The valence shell is taken as a sphere with the 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.
• When two or more resonance structures can represent a molecule, the VSEPR model is
applicable to any such structure.
• Within the structure, the repulsive interaction of electron pairs decrease in the order:
Lone pair (LP) – Lone pair (LP) > Lone pair (LP) – Bond pair (BP) > Bond pair (BP) – Bond pair (BP)
• The electron group geometry of a covalent molecule is determined by all the electron groups in
the molecule while the molecular geometry is determined purely by the bonding groups.

In the table below, BG = bonding group (group of single/double/triple bond), LP = lone pairs, and steric
number = BG + LP.

Steric Number Electron Group Molecular Example Structure

Geometry Geometry
2 Linear Linear BeH2
(2BG + 0 LP)

3 Trigonal Planar Trigonal Planar SO3

(3 BG + 0 LP) (120°) (120°)

3 Trigonal Planar Bent SO2

(2 BG + 1 LP) (120°)
 4 Tetrahedral Tetrahedral PO43-
(4 BG + 0 LP) (109.5°)

4 Tetrahedral Trigonal pyramidal NF3

(3 BG + 1 LP) (107°)

4 Tetrahedral Bent (104.5°) H2O

(2 BG + 2 LP)

5 Trigonal Trigonal PCl5

(5 BG + 0 LP) Bipyramidal Bipyramidal

5 Trigonal See-saw XeO2F2

(4 BG + 1 LP) Bipyramidal

5 Trigonal T-shape ClF3

(3 BG + 2 LP) Bipyramidal

5 Trigonal Linear I3-

(2 BG + 3 LP) Bipyramidal
 6 Octahedral Octahedral SF6
(6 BG + 0 LP)

6 Octahedral Square Pyramidal IF5

(5 BG + 1 LP)

6 Octahedral Square Planar KrF4

(4 BG + 2 LP)

CHEMICAL STRUCTURES OF ATOMS AND ELEMENTS

Ionic Networks

• In ionic and molecular solids, there are no chemical bonds between the molecules, atoms, or
ions.
• The solid consists of discrete chemical species held together by intermolecular forces that
are electrostatic or Coulombic in nature.
• This behavior is most obvious for an ionic solid such as NaCl.
o In the reaction of Na (sodium) and Cl (chlorine), each Cl atom takes one electron from a
Na atom.
o Therefore each Na becomes a Na+ cation and each Cl atom becomes a Cl- anion.
o Due to their opposite charges, they attract each other to form an ionic lattice.
o These ions are arranged in solid NaCl in a regular three-dimensional arrangement (or
lattice):
 • The properties of such ionic network structures depend on the size and charge of the ions, and
the strength of the attractive forces between them.
• They have high melting and boiling points, are hard, but brittle.
• Ionic solids are poor conductors of electricity in solid form, but can turn into good conductors in
the liquid state.
o This is because the ions are freed from the crystal lattice and are available to move with
ease.

Covalent Networks

• Covalent solids are formed by networks or chains of atoms or molecules held together by
covalent bonds.
• A perfect single crystal of a covalent solid is therefore a single giant molecule.
• For e.g., the structure of diamond (a) and graphite (b) are shown below.

• Covalent network structures generally have high melting and boiling points, are hard, and
nonconducting.
• Since covalent bonds are directional in nature, they break when tried to deform.
• They do not melt nor dissolve in water.

Exceptions to these physical properties

• Graphite is a good conductor of electricity.

Metallic Structure

• The structure of metallic crystals is often described as a uniform distribution of atomic nuclei
within a “sea” of delocalized electrons.
• The atoms within such a metallic solid are held together by a unique force known as metallic
bonding that gives rise to many useful and varied bulk properties.
o Metallic bonding is multidirectional in nature.
• All exhibit high thermal and electrical conductivity, metallic luster, and malleability.
• Many are very hard and quite strong, but not as strong as covalent or ionic networks.
• Because of their malleability and ductility, they do not shatter and, therefore, make useful
construction materials.
• Metallic structures contain free electrons that can conduct electricity in the solid and molten
states.
• For e.g., copper exists as a metallic solid.

Covalent Molecular

• Covalent molecular solids consist of atoms or molecules held to each other by dipole–dipole
interactions, London dispersion forces, or hydrogen bonds, or any combination of these.
• For e.g., the arrangement of the molecules in solid benzene is as follows:
 • The bonds in molecular solids are weaker than chemical or ionic bonds. This makes them soft.
• Covalent molecular solids have low melting and boiling points, and are nonconducting.
• Depending on the structure of the molecule, it may be malleable or brittle.
o For example, rubber is malleable while plastic brush is brittle.

The table below summarizes the four kinds of solid structures:

Type of Solid Type of Properties Examples

Interaction
Ionic network Electrostatic/ionic Hard, brittle, high melting and NaCl, MgO, KCl
boiling points, good
conductors of electricity in
liquid state
Covalent network Covalent bonding Hard, high melting and boiling Diamond, graphite, SiO2
points, brittle, strong,
nonconductor of electricity
(except graphite)
Metallic Metallic bonding Quite hard, malleable, ductile, Copper, Iron, Zinc
lustrous, conducting
Covalent molecular Hydrogen Soft, low melting and boiling H2O, CO2
bonding, dipole- points, can be brittle or
dipole, London flexible, nonconducting
dispersion