ALLOTROPY AND INTERMOLECULAR FORCES

Allotropy
Allotropy is the property of some chemical elements to exist in two or more different forms, or
allotropes, when found in nature.
 Allotropes may display very different chemical and physical properties. For example, graphite
and diamond are both allotropes of carbon that occur in the solid state.
 The different forms arise from the different ways atoms may be bonded together.
 Examples of allotropes include:

Classification Element Allotrope Examples (other forms may exist)

Carbon Diamond, Graphite, Fullerenes
Non-metal Oxygen Oxygen gas, Ozone
Phosphorus Red, Yellow, White phosphorus
Iron Alpha, Gamma, Delta iron
Metal Tin White tin, Gray tin
Cobalt Alpha cobalt, Beta cobalt
Silicon Amorphous silicon, Crystalline silicon
Metalloid Arsenic Gray, Yellow, Black arsenic
Germanium Alpha germanium, Beta germanium

Allotropes of Carbon

 Carbon exhibits at least ten 10 allotropic forms.

 The most common carbon allotropes are: diamond, graphite and buckminsterfullerene.
 Other allotropes include:
o Amorphous carbon found in soot
o Carbon nanotubes and nanobuds
o Carbide-derived carbon
o Lonsdaleite (hexagonal diamond)
o Glassy carbon

Diamond
  Diamond has a crystalline lattice structure.
 In diamond, each carbon atom is linked to four other carbon atoms in a tetrahedral fashion.
 The structure extends in space and produces a rigid three-dimensional network of carbon
atoms.
 Directional covalent bonds are present throughout the lattice.
o It is very difficult to break extended covalent bonding.
o Therefore, diamond is the hardest naturally occurring substance on earth.
o Due to this property, diamond is used in stone cutting and polishing, and in tips of many
fine drilling tools.
 Some other physical properties of diamonds include:
o It is a nonconductor of electricity as there are no free electrons in the network.
o It has very high melting and boiling points because of the high amount of energy needed
to break the strong covalent bonds.
o It is lustrous, colourless, and transparent. Therefore, diamonds are extensively used in
jewellery.

Graphite

 Graphite is composed of layers of carbon atoms that are arranged in 6-membered, hexagonal
rings, similar to a honeycomb.
  These rings are attached to one another on their edges. 
 Each carbon atoms in these ring arrays is attached to three other carbon atoms in a trigonal
planar geometry.
o The fourth electron in each C atom is free to move between the layers.
o This makes graphite a relatively good conductor of electricity.
 These “ring arrays” are arranged in large sheets of carbon atoms, and individual sheets are
known as graphene layers.
 Graphene layers are stacked one on top of another parallel to each other.
o The carbon atoms in the first layer are located in precise alignment with the carbon
atoms of the third layer indexed.
o Correspondingly, the carbon atoms of the second graphene layer are in alignment with
the atoms of the forth layer.
o This configuration is known as an “ABABAB” structure. 
 Some physical properties of graphite include:
o Graphite is a soft crystalline solid.
o It is slippery because the graphene layers slide on top of each other.
o Graphite has a very high melting point and boiling point as high energy is needed to
break the covalent bonds.
 Graphite is used as:
o Pencil leads
o Lubricants
o Electrodes in some batteries

Buckminsterfullerene

 Fullerene, also called buckminsterfullerene, is any of a series of hollow carbon molecules that

form either a closed cage (“buckyballs”) or a cylinder (carbon “nanotubes”).
 Buckyballs are defined as compounds composed solely of an even number of carbon atoms,
which form a cage-like system.
o They contain twelve five-membered rings and the rest six-membered rings.
o The most common example is C60 fullerene.
 Some physical properties of buckminsterfullerenes include:
 o Buckminsterfullerene is slippery and has a low melting and boiling point because of the
weak intermolecular forces between its molecules that need little energy to overcome.
o It is a very poor conductor of electricity but can be turned into a semiconductor under
suitable conditions.
o It is black in colour but turns deep red when dissolved in octane (petrol).
 Uses of buckminsterfullerene:
o Store hydrogen as a fuel tank
o Reduce the growth of bacteria in pipes
o Have potential antiviral activity

Extension: Nanotubes

 Carbon nanotubes, also called buckytube, are nanoscale hollow tubes composed of carbon
atoms. 
 They can be described as a long tube formed by wrapping a single graphene sheet into a cylinder
with diameter of about 1 nanometer.
 They have high thermal and electrical conductivity and are one of the strongest materials on
earth.
 They are used as additives to various structural materials for electronics, optics, plastics, and
other materials of nanotechnology fields.

The key points of the carbon allotropes are tabulated below:

Carbon allotrope Type of structure Physical properties

Diamond Covalent network Very hard, very high melting and boiling points,
nonconductor of electricity
Graphite Layers of covalent network Soft and slippery, high melting and boiling points,
moderate electrical conductivity
Buckminsterfullerene Covalent molecular Soft and slippery, low melting and boiling points,
low electrical conductivity

Polarity of Bonds
The polarity of a bond between two atoms—1 and 2—can be of the following kinds:

Atom 1 (Element) Atom 2 (Element) Type of bond

Non-metal Same non-metal Non-polar covalent
Non-metal Different non-metal Polar covalent
Non-metal Metal (Polar) Ionic
Metal Metal (Non-polar) Metallic

Exceptions to the table:

 C-H bonds are non-polar as C and H have similar electronegativities.

Polarity of a bond and Dipole Moment

 A dipole usually refers to the separation of charges within a molecule between two covalently
bonded atoms or atoms that share an ionic bond.
 A dipole is quantified by its dipole moment (μ).
 The dipole of a polar bond is shown by an arrow arrow which points towards the more
electronegative element. For example, in H 2O:

Polarity of covalent molecules

Polar covalent bonds are usually formed between two nonmetal atoms having different
electronegativities. In that case, the bond possesses a net dipole moment.
 The polarity of a covalent molecule depends on:
o The polarity of the individual bonds
o The molecular geometry of the molecule
 Steps to figure out if a molecule is polar or non-polar:
o Draw the molecule with its acceptable geometry.
o Draw the dipoles for the individual bonds.
o As dipole moment is directional, summing up the individual dipoles will give the dipole
moment of the molecule.
o If the dipole moment is zero (either by non-polar bonds, or by cancellation of opposite
dipoles), the molecule is non-polar.
o If the dipole moment is non-zero, the molecule is polar.

Examples:

Determine whether the following molecules are polar:

1. HCl

HCl is polar as there is electronegativity difference between H and Cl.

2. NH3
 NH3 is a polar molecule. The dipole moments of the three N-H bonds are directed towards N. As
H atoms are at the base of a trigonal pyramid, the net dipole moment moves upward.

3. CH4

CH4 is non-polar as none of the C-H bonds have polarity.

4. CO2

CO2 is non-polar. Although the two C=O bonds have polarity, they are directed such that the
individual dipole moments cancel each other.

5. SF6

SF6 is non-polar. The individual S-F bonds have dipole moment, but they are arranged around S
in an octahedral structure. The individual dipoles cancel each other to give a non-polar
molecule.

Intermolecular bonds/forces
Dipole-Dipole Interactions
  Dipole-Dipole interactions are a type of electrostatic attraction.
 They result when two dipolar molecules interact with each other through space.
 When this occurs, the partially negative portion of one of the polar molecules is attracted to the
partially positive portion of the second polar molecule.
 The dipoles are arranged such that the molecules attract each other in space.

 They are much weaker than ionic or covalent bonds and have a significant effect only when the
molecules involved are close together.
 The larger the dipole moment, the stronger the attraction between the molecules.
o Dipole moment is larger for molecules having significant difference in
electronegativities.

Hydrogen bonding

 A hydrogen bond is a special type of dipole-dipole attraction that occurs when a hydrogen atom
bonded to a strongly electronegative atom exists in the vicinity of another electronegative atom
with a lone pair of electrons.
 The H atom is attached directly to a highly electronegative atom such as F, O, or N, causing it to
acquire a highly positive charge.
 This is because:
o The high electronegativity difference results in a stronger dipole.
o H being a small atom, allows dipoles to come as close to each other as possible.
 H-bonding is stronger than typical dipole-dipole interactions, but still weaker than covalent or
ionic bonds.

Dispersion Forces
  Non-polar molecules show some attraction, indicating that there are some types of
intermolecular interactions that cannot be attributed to simple electrostatic attractions.
 These interactions are generally called dispersion forces.
 These are temporary attractive forces that results when the electrons in two adjacent atoms
occupy positions that make the atoms form temporary dipoles.
o This temporary dipole then interacts with a neighbouring atom or molecule to induce a
similar dipole.
 Dispersion forces are the weakest among all intermolecular forces.
o However, these forces can accumulate to be quite significant in long-chain polymers.
 This type of interaction exists between noble gases and non-polar molecules like CH 4.
 Dispersion forces are directly proportional to size of atoms.
o The larger the molecules, the more are the number of electrons present in them.
o With greater number of electrons, the chances of forming temporary dipoles are more.

Melting and boiling covalent molecules

 There are two kinds of attractive forces: intermolecular and intramolecular.
o Intermolecular forces exists between molecules, such as H-bonding, dipole-dipole
interactions, etc.
o Intramolecular forces exist between atoms of a molecule, such as ionic bonding,
covalent bonding, etc.
 Melting and boiling covalent compounds breaks the intermolecular forces between the
compounds.
 The melting and boiling points are high if the forces are strong.
o Stronger the forces, greater the energy required to break them.

These differences between intermolecular and intramolecular forces are tabulated below:

Intermolecular Forces Intramolecular Forces

Attractive forces between atoms in a molecule or Attractive forces between molecules in space
compound
High in strength and requires high energy to break Weak in strength and can be broken with little
energy
Examples: Ionic bonds, covalent bonds, metallic Examples: H-bonding, dipole-dipole interactions,
bonds dispersion forces