Lecture Notes Intermolecular Forces
Lecture Notes Intermolecular Forces
Lecture Notes Intermolecular Forces
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.
1. Ca and Cl
2. Cl and Cl
3. H and Cl
4. S and O
5. C and N
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Solution:
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
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 .
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
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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:
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?
YES
Note: You must think about a molecule
in 3 - D according to VSEPR Theory The molecule
is NONPOLAR
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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.
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
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with polar substances while nonpolar substances will be soluble or miscible
with another nonpolar substance.
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.
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.
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
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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.
Ion-dipole Strongest
H-bonding
Dipole-dipole
Dipole-induced dipole
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.
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.
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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 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
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Water
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.
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.
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
Isopentane