Handout on Intermolecular Forces and Intramolecular Forces

There are two kinds of forces, or attractions that operate in a molecule

intramolecular and intermolecular. Let's try to understand this difference through the following
example.

Figure of towels sewn and Velcroed representing bonds between hydrogen and chlorine atoms

We have six towelsthree are purple in color, labeled hydrogen and three are pink in color,
labeled chlorine. We are given a sewing needle and black thread to sew one hydrogen towel to
one chlorine towel. After sewing, we now have three pairs of towels: hydrogen sewed to chlorine.
The next step is to attach these three pairs of towels to each other. For this we use Velcro as
shown above.

So, the result of this exercise is that we have six towels attached to each other through thread
and Velcro. Now if I ask you to pull this assembly from both ends, what do you think will happen?
The Velcro junctions will fall apart while the sewed junctions will stay as is. The attachment
created by Velcro is much weaker than the attachment created by the thread that we used to
sew the pairs of towels together. A slight force applied to either end of the towels can easily bring
apart the Velcro junctions without tearing apart the sewed junctions.

Exactly the same situation exists in molecules. Just imagine the towels to be real atoms, such as
hydrogen and chlorine. These two atoms are bound to each other through a polar covalent bond
analogous to the thread. Each hydrogen chloride molecule in turn is bonded to the neighboring
hydrogen chloride molecule through a dipole-dipole attractionanalogous to Velcro. Well talk
about dipole-dipole interactions in detail a bit later. The polar covalent bond is much stronger in
strength than the dipole-dipole interaction. The former is termed an intramolecular
attraction while the latter is termed an intermolecular attraction.
Figure of towels sewn and Velcroed representing bonds between hydrogen and chlorine atoms,
illustrating intermolar and intramolar attractions

So now we can define the two forces:

Intramolecular forces are the forces that hold atoms together within a molecule.
Intermolecular forces are forces that exist between molecules.

Figure of intermolecular attraction between two H-Cl molecules and intramolecular attraction
within H-Cl molecule

Types of intramolecular forces of attraction

1. Ionic bond: This bond is formed by the complete transfer of valence electron(s) between
atoms. It is a type of chemical bond that generates two oppositely charged ions. In ionic
bonds, the metal loses electrons to become a positively charged cation, whereas the
nonmetal accepts those electrons to become a negatively charged anion.

Figure of ionic bond forming between Na and Cl

2. Covalent bond: This bond is formed between atoms that have similar
electronegativitiesthe affinity or desire for electrons. Because both atoms have similar
affinity for electrons and neither has a tendency to donate them, they share electrons in
order to achieve octet configuration and become more stable.

A nonpolar covalent bond is formed between same atoms or atoms with very similar
electronegativitiesthe difference in electronegativity between bonded atoms is less than 0.5.
Figure of covalent bond forming between two Cl molecules

A polar covalent bond is formed when atoms of slightly different electronegativities share
electrons. The difference in electronegativity between bonded atoms is between 0.5 and 1.9.
Hydrogen chloride, H bonds in water and hydrogen fluoride are all examples of polar covalent
bonds.

Figure of polar covalent bond forming between H and Cl

3. Metallic bonding: This type of covalent bonding specifically occurs between atoms of
metals, in which the valence electrons are free to move through the lattice. This bond is
formed via the attraction of the mobile electronsreferred to as sea of electronsand the
fixed positively charged metal ions. Metallic bonds are present in samples of pure
elemental metals, such as gold or aluminum, or alloys, like brass or bronze.

Figure of metal with positively charged atoms and mobile valence electrons

The freely moving electrons in metals are responsible for their a reflecting propertyfreely
moving electrons oscillate and give off photons of lightand their ability to effectively conduct
heat and electricity.

Relative strength of the intramolecular forces

Intramolecular Relative
force Basis of formation strength

Metallic bond Metal cations to delocalized electrons 1, strongest

Ionic bond Cations to anions 2

Partially charged cation to partially charged

Polar covalent bond anion 3

Nonpolar covalent
bond Nuclei to shared electrons 4, weakest
Intermolecular forces of attraction

Now lets talk about the intermolecular forces that exist between molecules. Intermolecular forces
are much weaker than the intramolecular forces of attraction but are important because they
determine the physical properties of molecules like their boiling point, melting point, density, and
enthalpies of fusion and vaporization.

Types of intermolecular forces that exist between molecules

1. Dipole-dipole interactions: These forces occur when the partially positively charged
part of a molecule interacts with the partially negatively charged part of the neighboring
molecule. The prerequisite for this type of attraction to exist is partially charged ions
for example, the case of polar covalent bonds such as hydrogen chloride. Dipole-dipole
interactions are the strongest intermolecular force of attraction.

Figure of H-Cl to H-Cl dipole-dipole attraction

2. Hydrogen bonding: This is a special kind of dipole-dipole interaction that occurs

specifically between a hydrogen atom bonded to either an oxygen, nitrogen, or fluorine
atom. The partially positive end of hydrogen is attracted to the partially negative end of
the oxygen, nitrogen, or fluorine of another molecule. Hydrogen bonding is a relatively
strong force of attraction between molecules, and considerable energy is required to break
hydrogen bonds. This explains the exceptionally high boiling points and melting points of
compounds like water, and hydrogen fluoride. Hydrogen bonding plays an important role
in biology; for example, hydrogen bonds are responsible for holding nucleotide bases
together in DNA and RNA.

Figure of intramolecular polar covalent bonding within H20 molecules and hydrogen bonding
between O and H atoms.
 3. London dispersion forces, under the category of van der Waal forces: These are
the weakest of the intermolecular forces and exist between all types of molecules, whether
ionic or covalentpolar or nonpolar. The more electrons a molecule has, the stronger the
London dispersion forces are. For example, bromine has more electrons than chlorine, so
bromine will have stronger London dispersion forces than chlorine, resulting in a higher
boiling point for bromine, compared to chlorine. Also, the breaking of London dispersion
forces doesnt require that much energy, which explains why nonpolar covalent
compounds like methane, oxygen, and nitrogenwhich only have London dispersion
forces of attraction between the moleculesfreeze at very low temperatures.

Figure of intramolecular nonpolar covalent bonding between Cl atoms and Long dispersion forces
between Cl-Cl molecules

Relative strength of intermolecular forces of attraction

Intermolecular force Occurs between Relative strength

Partially oppositely charged

Dipole-dipole attraction ions Strongest

As strong as dipole-dipole
Hydrogen bonding H and F, O or N attraction

London dispersion Temporary or induced

attraction dipoles Weakest

How forces of attraction affect properties of compounds

Polar covalent compoundslike hydrogen chloride, and hydrogen iodide, have dipole-dipole
interactions between partially charged ions and London dispersion forces between molecules.
Nonpolar covalent compoundslike methane and nitrogen gas,only have London dispersion
forces between molecules. The rule of thumb is that the stronger the intermolecular
forces of attraction, the more energy is required to break those forces. This translates
into ionic and polar covalent compounds having higher boiling and melting points, higher
enthalpy of fusion, and higher vaporization than covalent compounds.
Boiling and melting points of compounds depend on the type and strength of the intermolecular
forces present, as tabulated below:

Relative order of
boiling and
Type of compound Intermolecular forces present melting points

Ion to ion attraction between ions,

Ionic compounds London dispersion forces 1, highest)

Covalent compounds
containing hydrogen Hydrogen bonds, London dispersion
bonds forces 2

Dipole-dipole attraction between dipoles

Polar covalent created by partially charged ions, London
compounds dispersion forces 3

Nonpolar covalent
compounds London dispersion forces 4, lowest