Lecture Notes Intermolecular Forces

Republic of the Philippines
Batangas State University

COLLEGE OF AGRICULTURE AND FORESTRY
BatStateU-Lobo Campus, Masaguitsit Lobo Batangas, 4229
(043) 980-0385 loc. 7101, lobo.campus@g.bastate-u.edu.ph, www.batstate-u.edu.ph
LECTURE NOTES
INTERMOLECULAR FORCES OF ATTRACTION
A. Polarity of Bonds and Electronegativity
Electronegativity (EN) measures the relative tendency of an atom to attract electrons to
itself when chemically combined with other atom. Take a look at the electronegativity values of
some elements on Fig.1. What have you noticed? The electronegativity increases from left to
right of a period and decreases from top to bottom of a group. Take note also that the higher
the value of EN, the element tends to attract electron towards itself.
So what is the connection of electronegativity to the polarity of bonds? We could use the
electronegativity values of the atoms involved to get the absolute electronegativity difference
(∆EN) which will help us in predicting what type of chemical bond (ionic, polar covalent or
nonpolar covalent) would exist between them. Table 1 shows the type of bond based on the
electronegativity difference of bonded atoms.
Figure 1. Pauling Electronegativity values of some elements.
Table 1. Type of bond based on electronegativity difference (∆EN) of bonded atoms

Electronegativity Difference
Type of Bond
(∆EN)
Ionic
Polar Covalent 0.5 to 1.6
Nonpolar ≤ 0.4
Covalent
For example, you are asked to predict what type of bond is present between the following pairs
of atoms by determining their electronegativity difference.
1. Ca and Cl
2. Cl and Cl
3. H and Cl
4. S and O
5. C and N
Solution:
1. ENCa = 1.0 (∆EN) = 1.0 – 3.0 = │-2.0│= 2.0 ionic bond

ENCl = 3.0
2. ENCl = 3.0 (∆EN) = 3.0 – 3.0 = 0 nonpolar covalent bond

ENCl = 3.0
3. ENH = 2.1 (∆EN) = 2.1 – 3.0 = │-0.9│= 0.9 polar covalent bond
ENCl= 3.0
4. ENS= 2.5 (∆EN) = 2.5 – 3.5 = │-1.0│= 1.0 polar covalent bond
ENO = 3.5
5. ENC= 2.5 (∆EN) = 2.5 – 3.0 = │-0.5│= 0.5 polar covalent bond
ENN = 3.0
Using the above examples, let us know more about polar and nonpolar covalent bonds. A polar
covalent bond is formed when electrons are shared unequally by two atoms in a compound.
The bonded pair of atoms form an electric dipole (represented by ). Dipole means “two
poles” which means that a molecule has one positive end and one negative end. In this type of
bond, the atom with the higher EN value becomes the partial negative pole (symbolized as ẟ-)
while the atom with the lower EN value becomes the partially positive (symbolized as ẟ+) pole.
Always bear in mind that the direction of the arrow is always pointing from a more
electropositive pole to the more electronegative pole. Take HCl for example, H has higher EN
than Cl, thus the direction of the arrow is pointing away from H and towards Cl. There is
unequal electron density as represented by a size of the circle (refer to figure 2). On the other
hand, a nonpolar covalent bond develops if both atoms equally share a pair of electrons
between them.
This occurs when the bonding atoms have approximately equal EN value or equal ability to
attract electrons to each side. Nonpolar covalent bond is an example of bond formed when two
chlorine atoms combine.
(a) (b)
Figure 2. (a) Polar bond between H and Cl and (b) nonpolar bond between two Cl atoms
B. Polarity of Molecules and Molecular Geometry

You just have learned how to predict the type of bond polarity simply by calculating the
electronegativity difference of atoms (specifically two atoms). The next question is, how about
for those molecules consisting of more than two atoms like H 2O, CCl4, NH3 and CO2? For
polyatomic molecules, both the bond polarity and molecular shape determine the overall
molecular polarity. In terms of molecular geometry, the valence shell electron pair repulsion
(VSEPR) theory would help us to determine the spatial arrangement of atoms in a polyatomic
molecule.
You can predict the shape or molecular geometry of a substance using the following steps:
Step 1: Determine the central atom of a molecule. The central atom is the least electronegative
element.
Step 2: Draw the appropriate Lewis dot structure for the molecule.
Step 3: Count the number of bonding pairs of electrons and non-bonding (or lone pairs) around
the central atom.
Step 4: Determine the electron pair orientation using the total number of electron pairs.
Step 5: Identify the shape of the molecule of based on the location of the
atoms .
Figure 3. Different Molecular Shapes

Consider the examples below:
Example 1: Predict the molecular geometry of BCl3
Step 1: ENB = 2.0 ENCl= 3.0 therefore, B will be the central atom and three Cl atoms are
attached to it. By looking at the chemical formula, you will also have an idea that boron will be
the central atom and three atoms of choline are attached to it.
Step 2:
Step 3: The central atom has three electron pairs: 3 bonded pairs and no lone pair
Step 4: The electron pair orientation for three electrons is trigonal planar.
Step 5: The molecular shape of BCl3 is trigonal planar.
Example 2: Predict the molecular geometry of CO2
Step 1: ENC= 2.5 ENO= 3.0 therefore, C will be the central atom and two O atoms will be the
attached to it. (Use may also use the chemical formula to predict which atom will be the
central atom
Step 2:
Step 3: For the purpose of determining the position of the bonding pairs, let us count the
double bonds as one bonding pair. Therefore, CO2 has two bonding pairs of electron.
Step 4: The electron pair orientation for two electron pairs is linear.
Step 5: The molecular shape of CO2 is linear.
Example 3: Predict the molecular geometry of CHCl3.
Step 1: ENC = 2.5, ENH= 2.1 and ENCl= 3.0. Because carbon is less electronegative than
chlorine and hydrogen is normally terminal atom, C must be the central atom.
Step 2:
Step 3: There are four bonding electron pairs.

Step 4: The electron pair orientation for four electron pairs is tetrahedral.
Step 5: The molecular shape of CHCl3 is linear.
Now that you have learned how to determine the molecular geometry, let us now go on to our
discussion of polarity of molecules based on molecular shapes. You may study the diagram
below and we will use it as our guide.
Is the shape
NO symmetrical
YES
in 3D?
The molecule Are all atoms

is POLAR
NO bonded to the
central atoms
the same ?
YES
Note: You must think about a molecule
in 3 - D according to VSEPR Theory The molecule
is NONPOLAR
Figure 4. Flowchart to determine if a molecule is polar or nonpolar
Going back to our previous examples, let us try to determine the polarity of molecules of BCl 3,
CO2 and CHCl3.
For both BCl3 and CO2, the atoms are symmetrically arranged (trigonal planar and linear) and
the attached atoms to the central atom are also the same. You must also take note that in a
symmetrical molecule, the sum of the bond dipole is equal to zero (because they cancel out)
and leads to the formation of nonpolar molecule. Therefore, both BCl 3 and CO2 are nonpolar.
On the other hand, CHCl3, although it has a symmetrical arrangement (tetrahedral), the atoms
attached to the central atom are not all the same (3 chlorine atoms and 1 hydrogen atom). This
causes CHCl3 to become a polar molecule.
Now, let us see if you fully understood our discussion. I want you to try answering the
exercises below.
Identify which molecule is polar and which is nonpolar given the Lewis structure and
molecular shapes of the following molecules.
Molecule Lewis Structure Molecular Geometry Molecular
(based on VSEPR) Shape
1. NH3 Trigonal
pyramidal
2. H2O
Bent or
angular
3. CCl4
Tetrahedral
4. Linear
If you were able to answer that NH 3 and H2O are polar molecules because the bond dipole
cannot be cancelled because of the presence of lone pairs on the central atom and CCl 4 and
HBr are nonpolar molecules, you are correct. Job well done! You may now proceed to the rest of
this module.
Properties of Molecules based on its Polarity
A. Polarity, Solubility, and Miscibility
One of the practical applications of polarity of molecule in real-life scenario is
manifested on the solubility and miscibility of substances to form solution.
Solubility is defined as the ability of a solid substance to be dissolved in a

given amount of solvent while miscibility is the ability of the two liquids to
combine or mix in all proportions, creating a homogenous mixture.
The general rule to remember about the solubility and miscibility of molecular
compounds can be summarized in a phrase, “like dissolves like” or “like mixes
with like”. This means that polar substances will only be dissolved or mixed
with polar substances while nonpolar substances will be soluble or miscible
with another nonpolar substance.
B. Bond Strength and Physical Properties of Covalent Compounds
From the previous module, you learned the intramolecular forces of

attraction, the attractive force that binds atoms together. In this module, you
will learn another type of attractive force, the intermolecular forces of
attraction (IMFA) which exists between molecules.
In this lesson, we will not discuss IMFA in so much detail because it will be
tackled next module. We will just focus on the following salient features of
IMFA and its effect on the physical properties of covalent compounds:
1. There are several types of IMFA and below they are arranged from
STRONGEST to WEAKEST.
Ion-dipole → H-bonding→ dipole-dipole→dipole-induced dipole→
London forces of attraction
2. The strength of IMFA greatly affects the physical properties of
substances such as boiling point, melting point, vapor pressure,
surface tension, etc.
How well did you perform in this exercise? Continue reading for you to find out
the correct answers for this activity.
From the above discussion you learned that there are several types of IMFA
and their relative strength as compared to other types. Strong intermolecular
forces tend to yield solids and liquids while weak intermolecular forces favor
formation of gases.
Table 1 shows the comparison of the various types of IMFA while table 2 shows
the physical properties of polar and nonpolar molecules as affected by the type
of IMFA present.
Table 1. Summary of Types of Intermolecular Forces of Attraction (IMFA)

Type of IMFA Interacting Substances Examples
Ion-dipole Ion (cation or anion) and a NaCl dissolved in H2O;
polar molecule Ca2+ and PCl3
Hydrogen bonding Polar molecules H2O, NH3, CH3OH
containing H chemically
bonded to a small and
highly electronegative
nonmetal atom such as N,
O, and F
Dipole –dipole Polar molecules CH3F and H2S; HCl;
Dipole-induced dipole Polar and nonpolar HI and CH4
molecules
London forces All substances and solely O2, N2, He gas, Br2
for nonpolar molecules
and noble gases
Table 2. General Properties of polar and nonpolar molecules
Polar molecules Nonpolar molecules

• IMFA type: H-bonding • IMFA type: London
and dipole-dipole dispersion
• exist as solids or liquids • exist as gases at room
at room temperature temperature
• High boiling point • Low boiling point
• High melting point • Low melting point
• High surface tension • Low surface tension
• Low vapor pressure • High vapor pressure
• Low volatility • High volatility
• Soluble in water • Insoluble in water
Let us define the physical properties of substances:
A. Boiling point: temperature at which the vapor pressure and atmospheric

pressure of a liquid substance are equal.
B. Melting point: temperature at which solid becomes liquid. At this point,

the solid and liquid phases exist in equilibrium.
C. Surface tension: energy needed to increase the surface area by a unit

amount;
D. Viscosity: the resistance of the liquid to flow
E. Vapor pressure: pressure exerted by a substance in its gaseous state.
F. Volatility: measures the rate at which a substance vaporizes (changes

from liquid to gas)
In the simplest sense, boiling point, melting point, viscosity and surface
tension increase as the strength of intermolecular forces increases. On the
other hand, vapor pressure and volatility decrease with increasing strength of
IMFA. London dispersion forces increase as the molecular mass of a substance
increases.
TYPES OF INTERMOLECULAR FORCES
Atoms are held together in molecules by strong intramolecular forces, like covalent and ionic
bonds. On the other hand, other forms of attractive forces are present to keep these
molecules together giving rise to the different states of matter, which, then exhibit their own
bulk properties such as boiling, melting, and freezing points, and viscosity among others.
There are three general types of intermolecular forces (IMF), namely, van der Waals forces,
ion-dipole interaction, and H-bonding.
Van der Waals forces, after the Dutch chemist Johannes van der Waals (1837-1923) consist
of dipole-dipole interaction, dipole-induced dipole interaction, and dispersion forces. Dipole-
dipole attraction is present among polar molecules. Through constant movement, the
charges of the molecules align in such a way that the positive (+) end of one molecule is
attracted to the negative (-) end of the other molecule. This happens due to the shift of
electron density towards the more electronegative element in the molecule resulting to (+)
and (-) ends. The measure of this electron shift is known as dipole moment, represented by
crossed arrow, .
Dipole-induced dipole interaction, just like the dipole-dipole forces, depends on the
presence of polar molecules. The other molecule needs not be a polar one. The partial
charges present in the dipole cause the polarization or distortion of the electron distribution
in the other molecule. This gives rise to regions of partial (+) and (-) poles. The other
molecule then becomes an induced dipole. The induced dipole will be attracted to the
original polar molecules, resulting to dipole-induced dipole attraction.
Dispersion forces (London dispersion forces), were named after the German physicist Fritz
London (1900-1954). The electron cloud of a neutral substance can be normally distributed
around the nucleus. At any given time, the electron distribution may be uneven and results
to an instantaneous dipole. This temporary dipole will then influence the neighboring atoms
through attractive and repulsive forces. Eventually, the substances will become
instantaneous dipoles, too. Attraction between opposite charges will happen among the
species present. These are true for ion-induced dipole and induced dipole-induced dipole
interactions.
Ion-dipole interaction results from the attraction either between a cation (+) or an anion (-)
with permanent polar molecules. The ions will be attracted to the opposite charges present
in the dipole resulting to this type of attraction.
H-bonding is a special type of dipole-dipole interaction between the Hatoms in a polar bond.
It requires that the H-atoms in the molecules be bonded with more electronegative atoms
such as O, N, or F to form H-bonds with other molecules.
All interacting substances exhibit the presence of London dispersion forces in addition to
other forces of attraction among them.
INTERMOLECULAR FORCES (IMF) PRESENT AMONG SPECIES
Polar substances exhibit dipole-dipole interaction due to the presence of (+) and (-) ends of
the molecules. In the exercise above, sulfur dioxide (SO 2) has polar ends that will participate
in the dipole-dipole forces of attraction.
With the presence of an ion (cation or anion), the charged ends of polar molecules will
be attracted to the dipole. This is true in the case of Na + and formaldehyde. The positive
sodium ion will be attracted to the partially-negative oxygen in formaldehyde, resulting to an
ion-dipole interaction.
For the third example, CO2 is a nonpolar substance. It is a linear molecule and the
electron shift at the right of C is balanced by the electron shift to the left. Thus there is no
net shift in electron density and no net charged is produced. For nonpolar molecules, only
dispersion forces are present.
In both NH3 and H2O, the hydrogen atoms are bonded to more electronegative atoms,
nitrogen and oxygen, respectively. This permits them to form H-bonds with other molecules
with the same condition. Thus, H-bond is present between NH 3 and H2O.
Ion-induced dipole forces of attraction are present among Fe 2+ ions together with
oxygen molecules. The charge in iron will distort the electron distribution in O 2 resulting to
temporary poles in oxygen. The Fe 2+ and partiallynegative end of O 2 will then be attracted to
form the above-mentioned force of attraction.
Effects of Intermolecular Forces on the Properties of Substances

This section gives brief and thorough explanation on how intermolecular
forces affect the bulk properties of matter, namely surface tension, viscosity,
boiling, melting, and freezing points, and solubility.
Activity 1:
The properties of substances as viewed on the macroscopic level can be
explained by the types of intermolecular forces present between and among
substances. These bulk properties can be predicted through an analysis of
the interplay of intermolecular forces in each substance.
The chart below tells us of the relative strengths of intermolecular forces.

This can be used as reference when the IMF is being related to the properties
of substances.
Relative Strengths of Intermolecular Forces
Ion-dipole Strongest
H-bonding
Dipole-dipole
Dipole-induced dipole
London dispersion forces

Weakest
Properties of substances affected by intermolecular forces
 Surface Tension
This is the amount of energy required to stretch the surface area of liquids
(e.g., 1 cm2). Liquids with high intermolecular forces tend to have high
surface tensions. When water is dropped on a waxy surface, it tends to form
a round bead to minimize the surface area that it occupies.
An example of surface tension is capillary action. It is the ability of liquid

molecules to move against gravity. The forces bringing about capillary action
are cohesion (intermolecular attraction between like molecules) and adhesion
(an attraction between unlike molecules.
Water molecules exhibit cohesion while the attraction between water and the
sides of the glass tube is adhesion. If adhesion is stronger than cohesion, the
liquid is pulled upward.
If cohesion is greater than adhesion, there is a depression or lowering,
resulting to a lower height of the liquid in the capillary tube.
The stronger the intermolecular forces possessed by molecules, the higher is

the surface tension of the substance.
 Viscosity
This is a measure of a liquid’s resistance to flow. The greater the viscosity of

a liquid, the more slowly it flows. The viscosity of substances decreases with
high temperatures; thus, syrup flows faster when hot.
The strength of intermolecular forces affects the ease with which substances
flow. Liquids that have high intermolecular forces are highly viscous. Also,
the presence of strong H-bonds in some liquids makes these substances
highly viscous. The LEDS of glycerol below shows three (3) OH - groups that
can participate in H-bonding whereas water has only one OH - group to form
Hbonding. Glycerol is more viscous than water.
Glycerol
Water
 Boiling Point and Melting Point
Boiling point depends on the equilibrium vapor pressure exerted by the liquid
or solid above the liquid or the solid. This means that the rate of vaporization is
equal to the rate of condensation of the substance in a closed container. Vapor
pressure also varies with temperature. The graph below shows the effect of
temperature on the vapor pressure of water.
Source: https://www.chem.purdue.edu/gchelp/liquids/vpress.html
At 100OC, the vapor pressure is equal to the atmospheric pressure of 1.00 atm.
Boiling occurs at this point, where the vapor pressure of water is equal to the
pressure of the atmosphere.
There are substances that boil at a lower temperature and some at a higher
temperature. These temperatures depend on the vapor pressure exerted by the
liquids or solids. Vapor pressure, on the other hand, depends on the
intermolecular forces present in the substances. When the intermolecular
forces are strong, the vapor pressure is low.
As a consequence, boiling will occur at a higher temperature because more

energy is needed to break the intermolecular bonds for the substance to
change into vapor. Water, for example, exhibits strong H-bonds such that
vaporization needs more energy to change the liquid to vapor.
London dispersion forces predominate in methane, CH 4. These are the weakest
forces of attraction among molecules. It needs a little energy to break the
bonds such that methane changes to vapor easily. As a consequence, more
vapor are released in which vapor pressure will eventually equal to
atmospheric pressure. Boiling then will occur. This explains why water has a
higher boiling point than methane.
This condition is also true for melting point. The ease with which bond breaks
affects the melting points of substances. The greater intermolecular forces
there are among molecules, the higher is their melting point.
The strength of dispersion forces also depends on the size of the molecules of
the substance or the number of electrons in the molecules of the substance.
The ease with which the electron distribution is distorted explains the amount
of dispersion forces that a substance exhibits. The distortion of the electron
distribution is known as polarizability.
The greater the polarizability of the electron distribution the greater are the
dispersion forces. When the dispersion forces are high, the boiling and melting
points are also high.
Br2 and F2 are both diatomic gases. They are also both nonpolar, but Br 2 is a
bigger molecule than F2. The polarizability of Br 2 is greater than F2 so it has
greater dispersion forces. This explains why Br 2 has a higher boiling point than
F2. Greater amount of energy is needed to overcome the big dispersion forces in
Br2 than in F2.
 Solubility
Solubility is the ability of a substance (solid, liquid, or gas) to dissolve in a
given substance (solid, liquid, or gas). The amount of any substance dissolved
in a solvent (the substance that dissolves another substance) depends on the
types of interaction among molecules, pressure, and temperature.
The rule “like dissolves like” applies to solubility. This means that the kind of
substances being dissolved should exhibit the same properties or should be
compatible for them to form solutions. The polarity of molecules is an
important factor for substances to dissolve in certain molecules. Highly polar
molecules will dissolve substances that have dipoles. The negatively-charged
particles will be attracted to the positively-charged particles of the involved
substances. This attraction will subsist in the solutions.
Water is often considered as a universal solvent because of its ability to

dissolve almost numerous substances. Remember that water is incapable of
dissolving all solutes (especially non polar substances), but water has the
ability to form H-bonds with polar substances, and polar substances abound in
nature.
Nonpolar substances, on the other hand will also dissolve nonpolar

substances. Intermolecular forces, such as dispersion forces, will prevail to
maintain the dissolution of substances.
To predict the behaviour of substances, several considerations should be

taken.
First, the polarity of substances should be determined together with the

predominant intermolecular forces present in the substances. For example,
consider NaCl (sodium chloride) and CH 4 (methane). NaCl is a dipole while
methane is nonpolar. Dipole-dipole interaction is predominant in NaCl while
dispersion forces are present among methane molecules.
Since dipole-dipole forces are stronger than dispersion forces, NaCl will have
higher boiling and melting points. It is also highly soluble in water due to ion
dipole interaction that will prevail. Methane is not soluble in water because
there are no poles that will participate in the dissolution process with water.
Between CCl4 (carbon tetrachloride) and CHCl3 (trichloromethane),

trichloromethane has a higher boiling and melting points than carbon
tetrachloride. It is also slightly soluble in water. Trichloromethane is a polar
molecule while carbon tetrachloride is a nonpolar molecule. The dipole-
dipole interaction in CHCl 3 is stronger than the dispersion forces in CCl 4.
Again the boiling and melting points are higher in CHCl 3 than in CCl4.
Hence, since CHCl3 is polar, then it is soluble in water.
Ammonia (NH3) and methyl fluoride (CH3F) are both polar but the ability of
NH3 to form H-bonds qualifies it for higher boiling and melting points than
CH3F. At the same time, H-bonding also enables NH3 to be more soluble in
water than CH3F.
Phosphorus pentachloride (PCL5) and phosphorus pentabromide (PBr 5) have
the same molecular shape and polarity. What matters here is the size of the
molecule when comparing the properties of these substances. Bromine
contains more electrons than chlorine. This makes PBr 5 bigger and heavier.
In this case, dispersion forces are greater in PBr 5 so it has higher boiling and
melting points than PCL5. Since these two substances are both nonpolar,
then they are not soluble in water.
Pentane (C5H12) and isopentane (C5H12) both contain the same number of C
and H atoms in the formula. However, their molecular structures are
different. Below are the LEDS of the two substances.
Pentane has an extended structure while isopentane has a compact

structure. Extended structures provide more opportunities for interactions
than compact structures. Extended molecules have stronger intermolecular
forces than the compact structures. As such the boiling point of pentane is
higher than that of isopentane. It is also true for their melting points. Both
molecules are nonpolar so they are not soluble in water.
Pentane
Isopentane

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Republic of the Philippines

Batangas State University

Figure 1. Pauling Electronegativity values of some elements.

Table 1. Type of bond based on electronegativity difference (∆EN) of bonded atoms

1. ENCa = 1.0 (∆EN) = 1.0 – 3.0 = │-2.0│= 2.0 ionic bond

2. ENCl = 3.0 (∆EN) = 3.0 – 3.0 = 0 nonpolar covalent bond

B. Polarity of Molecules and Molecular Geometry

Figure 3. Different Molecular Shapes

Example 1: Predict the molecular geometry of BCl3

Step 3: There are four bonding electron pairs.

The molecule Are all atoms

Solubility is defined as the ability of a solid substance to be dissolved in a

B. Bond Strength and Physical Properties of Covalent Compounds

From the previous module, you learned the intramolecular forces of

Table 1. Summary of Types of Intermolecular Forces of Attraction (IMFA)

Polar molecules Nonpolar molecules

A. Boiling point: temperature at which the vapor pressure and atmospheric

B. Melting point: temperature at which solid becomes liquid. At this point,

C. Surface tension: energy needed to increase the surface area by a unit

D. Viscosity: the resistance of the liquid to flow

E. Vapor pressure: pressure exerted by a substance in its gaseous state.

F. Volatility: measures the rate at which a substance vaporizes (changes

INTERMOLECULAR FORCES (IMF) PRESENT AMONG SPECIES

Effects of Intermolecular Forces on the Properties of Substances

The chart below tells us of the relative strengths of intermolecular forces.

London dispersion forces

Properties of substances affected by intermolecular forces

An example of surface tension is capillary action. It is the ability of liquid

The stronger the intermolecular forces possessed by molecules, the higher is

This is a measure of a liquid’s resistance to flow. The greater the viscosity of

 Boiling Point and Melting Point

As a consequence, boiling will occur at a higher temperature because more

Water is often considered as a universal solvent because of its ability to

Nonpolar substances, on the other hand will also dissolve nonpolar

To predict the behaviour of substances, several considerations should be

First, the polarity of substances should be determined together with the

Between CCl4 (carbon tetrachloride) and CHCl3 (trichloromethane),

Pentane has an extended structure while isopentane has a compact

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