Engineering Chemistry I
Unit 3 LP10
Dr A RAMESHKUMAR
Assistant Professor
Department of Chemistry
Van der Waals forces
Van der Waals forces are weak intermolecular forces that are dependent on the
distance between atoms or molecules.
Van der Waals forces driven by induced electrical interactions
Van der Waals interaction is the weakest of all intermolecular attractions between
molecules.
Van der Waals forces are the weakest chemical force and rapidly vanish when the
distance between the interacting molecules increases. The strengths of Van der Waals
forces typically range from 0.4 [Link]-1 to 4 [Link]-1 .
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Types of van der Waals forces
There are three types of van der Waals forces:
1. Dipole-dipole interactions
2. Dipole-induced interactions
3. Temporary dipole-induced dipole interaction
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Dipole - dipole interaction
These forces arise from the attraction between the positive
and negative ends of polar molecules.
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Dipole - induced dipole interaction
These forces arise between a
permanent dipole molecule
and a non-polar molecule.
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Dipole - induced dipole interaction
Examples
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Temporary dipole – induced dipole interaction
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Temporary dipole – induced dipole interaction
Spontaneous dipole-induced dipole interactions are known as dispersion or
London forces.
In non-polar molecules – the force of attraction is London dispersion force.
Molecules that have induced dipoles may also induce neighbouring
molecules to have dipole moments, so a large network of induced dipole-
induced dipole interactions may exist.
These forces are the weakest of all van derWaals forces.
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Characteristics of van der Waals forces
van derWaals forces are weak and short-range.
van der Waals forces caused by the attraction between the electron clouds
of atoms.
van derWaals forces are strongest when the atoms are close to each other.
van der Waals forces are responsible for the attraction of molecules to each
other.
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The boiling point of xenon is -108oC whereas the boiling point
of neon is -246oC. Reason out
Xenon atoms are large in size and the electrons have more space
to disperse over. This creates temporary dipoles and strong force
of attraction between the atoms.
The high boiling point of xenon is due to the stronger dispersion
forces experienced by its atoms.
The greater the number of (instantaneous) dipoles formed, the
greater the strength of the van der Waals force and hence high
boiling point.
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The structural isomers butane and isobutane have different
boiling points despite having the same chemical formulae. The
boiling point of butane is -0.5 oC and that of isobutane is -11.7
oC. Reason out
Note – frequently asked question
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The structural isomers butane and isobutane have different
boiling points despite having the same chemical formulae. The
boiling point of butane is -0.5 oC and that of isobutane is -11.7
oC. Reason out
The difference in the boiling points of these isomers is due to the
stronger van der Waals forces in the unbranched butane molecules
and the weaker van der Waals forces in the short, branched
isobutane molecules.
Note – frequently asked question
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Van der Waals force - applications
It is widely believed that Geckos exploit Van
der Waals forces hanging on to smooth
surfaces with only their toes.
The attractive forces that arise between the
spatula of the Gecko’s footpads and the
smooth surface enable the lizard effectively
climb these surfaces. Similar biological designs
observed in some spiders.
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Note – frequently asked question
Bond energy and bond dissociation energy
Bond energy (BE) is the average of all bond-dissociation energies of a
single type of bond in a given molecule when it is in gaseous state.
The bond dissociation energy of a chemical bond can be defined as the
change in enthalpy (ΔH) associated with the breakage of the chemical
bond.
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Bond energy in methane
Dissociation of C–H bonds in CH4
The bond-dissociation energies of
different bonds of the same type
can vary even within a single
molecule. Meaning all the CH
bond-dissociation energies in
methane are not equal to each
other
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Stability of a compound
The bond energy of a chemical bond is directly proportional to
the stability of that bond.
This implies that the greater the bond energy of a given chemical
bond between two atoms, the greater the stability of that
chemical bond.
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Bond Cleavage:
The splitting of chemical bonds is known as bond cleavage or
bond fission.
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Homolytic cleavage:
In homolytic cleavage, or homolysis, the two electrons in a
cleaved covalent bond are divided equally between the products.
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Note – frequently asked question
Homolytic cleavage:
The products of the homolytic cleavage are called free radicals.
The triplet excitation energy of a sigma bond is the energy
required for homolytic dissociation, but the actual excitation
energy may be higher than the bond dissociation energy due to
the repulsion between electrons in the triplet state.
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Note – frequently asked question
Heterolytic cleavage
In heterolytic cleavage, or heterolysis, the bond breaks in such a fashion
that the originally-shared pair of electrons remain with one of the
fragments. Thus, a fragment gains an electron, having both bonding
electrons, while the other fragment loses an electron.
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Note – frequently asked question
Heterolytic cleavage
The singlet excitation energy of a sigma bond is the energy required for
heterolytic dissociation, but the actual singlet excitation energy may be
lower than the bond dissociation energy of heterolysis as a result of the
Coulombic attraction between the two ion fragments.
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Note – frequently asked question
Activation energy of reactions:
Activation energy is the minimum
amount of energy which must be
provided for reactants to result in a
chemical reaction.
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Activation energy of two types of reaction:
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Effect of catalyst on activation energy:
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Note – frequently asked question
Effect of catalyst on activation energy:
• A catalyst helps to increase the rate of reaction or which supports the reaction
to carry out quickly called a positive catalyst. Such a catalyst decreases the
activation energy by accepting a smaller path, so the rate of the reaction is
increased.
• A catalyst that decreases or retards or helps in slowing down the rate of
reaction is called negative catalyst. Such a catalyst increases the activation
energy.
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Note – frequently asked question
Effect of Temperature on the rate of a chemical
reaction
For a chemical reaction to proceed at a reasonable rate, the temperature of the system
should be high enough such that there exists an appreciable number of molecules with
translational energy equal to or greater than the activation energy.
So increase in temperature increases the rate of the reaction.
Note:
Increase in temperature does not decrease activation energy of a chemical reaction but it
helps the reactant molecules to easily attain the activation energy .
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Arrhenius equation
The Arrhenius equation gives the quantitative basis of the relationship between the
activation energy and the rate at which a reaction proceeds.
From the equation, the activation energy can be found through the relation
where A is the pre-exponential factor for the reaction, R is the universal gas constant, T is the
absolute temperature (usually in kelvins), and k is the reaction rate coefficient
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