Intramolecular and intermolecular forces

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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 towels—three 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 attraction—analogous to Velcro.
We’ll 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
electronegativities—the 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 electronegativities—the 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, \text{HCl}HClH, C, l; the \text{O}-{H}O−HO, minus, H bonds in
water, \text{H}_{2}\text{O}H2OH, start subscript, 2, end subscript, O; and
hydrogen fluoride, \text{HF}HFH, F, 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
electrons—referred to as sea of electrons—and 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
property—freely moving electrons oscillate and give off photons of light—
and their ability to effectively conduct heat and electricity.

Relative strength of the intramolecular forces

Intramolecular Relative
force Basis of formation strength

Metal cations to
delocalized 1,
Metallic bond electrons strongest

Ionic bond Cations to anions 2

Partially charged
Polar covalent cation to partially
bond charged anion 3

Nonpolar Nuclei to shared

covalent bond electrons 4, weakest

Intermolecular forces of attraction

Now let’s talk about the intermolecular forces that exist between molecules.
Intermolecular forces are much weakerthan 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, \text{HCl}HClH, C, l. 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, \text{H}_{2}\text{O}H2OH, start subscript, 2, end
subscript, O, and hydrogen fluoride, \text{HF}HFH, F. Hydrogen bonding
plays an important role in biology; for example, hydrogen bonds are
responsible for holding nucleotide bases together in \text{DNA}DNAD, N,
Aand \text{RNA}RNAR, N, A.
 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 covalent—polar or nonpolar. The
more electrons a molecule has, the stronger the London dispersion forces
are. For example, bromine, \text{Br}_{2}Br2B, r, start subscript, 2, end
subscript, has more electrons than chlorine, \text{Cl}_{2}Cl2C, l, start
subscript, 2, end subscript, so bromine will have stronger London dispersion
forces than chlorine, resulting in a higher boiling point for bromine,
59 ^\text{o}ostart superscript, o, end superscriptC, compared to chlorine, –
35 ^\text{o}ostart superscript, o, end superscriptC. Also, the breaking of
London dispersion forces doesn’t require that much energy, which explains
why nonpolar covalent compounds like methane—\text{CH}_{4}CH4C, H,
start subscript, 4, end subscript—oxygen, and nitrogen—which only have
London dispersion forces of attraction between the molecules—freeze 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 Relative
force Occurs between … strength

Dipole-dipole Partially oppositely charged

attraction ions Strong

Strongest
of the
\text{H}HH atom
dipole-
Hydrogen and \text{O}OO, \text{N}NN/ dipole
bonding or \text{F}FFatom attractions

London
dispersion
attraction Temporary or induced dipoles Weakest

How forces of attraction affect properties of compounds

Polar covalent compounds—like hydrogen chloride, \text{HCl}HClH, C, l,

and hydrogen iodide, \text{HI}HIH, I—have dipole-dipole interactions
between partially charged ions and London dispersion forces between
molecules. Nonpolar covalent compounds—like methane \text{CH}_{4}CH4
C, H, start subscript, 4, end subscript and nitrogen gas, \text{N}_{2}N2N,
start subscript, 2, end subscript)—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 enthalpy of
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 Intermolecular melting
compound forces present points

Ion to ion attraction

Ionic between ions, London
compounds dispersion forces 1, highest)

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

Dipole-dipole
attraction between
Polar covalent
dipoles created by
compounds 3
partially charged ions,
 Relative
order of
boiling
and
Type of Intermolecular melting
compound forces present points

London dispersion
forces

Nonpolar
covalent London dispersion
compounds forces 4, lowest

Let’s try to identify the different kinds of intermolecular forces present in

some molecules.

1. \text{H}_{2}\text{S}H2SH, start subscript, 2, end subscript, S—London

dispersion force—by default every compound will have this force of
attraction between molecules—and dipole-dipole attraction
 Figure of H2S London dispersion force and dipole-dipole attraction

2. \text{CH}_{3}\text{OH}CH3OHC, H, start subscript, 3, end subscript,

O, H—London dispersion force, dipole-dipole attraction, and hydrogen
bonding
 Figure of CH3OH London dispersion force, dipole-dipole attraction and
hydrogen bonding

3. \text{C}_{2}\text{H}_{6}C2H6C, start subscript, 2, end subscript, H,

start subscript, 6, end subscript—London dispersion forces—it’s a nonpolar
covalent compound— and no other intermolecular attractions
Figure of C2H6 London dispersion forces

Summary of IMFAs