Van der Waals force

o Van der Waals force is electrostatic attraction between dipole, i.e. the attraction between the positive end of one molecule and the negative end of another molecule. o There are the types of dipoles permanent dipole, instantaneous dipole and induced dipole.

Permanent Dipole
A permanent dipole exists in all polar molecules.
Permanent Dipole
+ -

Instantaneous dipole
An instantaneous dipole is a temporary dipole that exists as a result of fluctuation in the electron cloud. The temporary dipole induces a dipole in a neighboring molecule. This results in a weak and temporary force of attraction between the two atoms.

Induced Dipole
An induced dipole is a temporary dipole that is created due to the influence of a neighbouring dipole (which may be a permanent or an instantaneous dipole)

Induced Dipole
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 Van der Waals forces consists of three types of intermolecular attractions. They include the permanent dipole -

permanent dipole interaction, permanent dipole -induced dipole interaction and instantaneous dipole induced dipole interaction .

Permanent dipole - permanent dipole interaction

Polar molecules such as HCl have permanent moments. They tends to orient one another, as a result there are attractive forces between molecules. The attraction between the + and of the permanent dipoles of neighbouring molecules is permanent dipole - permanent dipole interaction. Dipole-dipole attraction requires the presence of polar bonds and a unsymmetric molecule.
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Since there are an attractive forces between molecules, it need more energy to break the attraction.

Permanent dipole -induced dipole interaction

When a non-polar molecule approaches a polar molecule (with a permanent dipole), a dipole will be induced in the non-polar molecule. The dipole induced will be in opposite orientation to that of the polar molecule. The dipole induced dipole interactions are generally weaker than dipole dipole interactions
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Instantaneous dipole - induced dipole interaction

Take argon as an example. The electron cloud distribution is generally symmetrical around the argon nucleus. However, due to the instant mobility of the electron cloud ,its position fluctuates all the time. At any particular instant, it is likely to be concentrated on one side of the atom than the other. Thus, the atom possesses an electric dipole moment at that particular instant. It is known as the Instantaneous dipole moment.
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 The instantaneous dipole will induce a dipole moment (known as the induced dipole moment) in the neighbouring atom by attracting opposite charges. If the positive end of the dipole is pointing towards a neighbouring atom, the induced dipole will then have its negative end pointing towards the positive pole of that dipole. That makes the instantaneous dipole attract the induced dipole. It is the type of weak attraction that exists between atoms of noble gases and between non polar molecules. Instantaneous dipole-induced dipole attraction also called dispersion force or London force. They are much weaker than dipole dipole interaction,
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Determining Type of Intermolecular Force

Polar Molecules ?
YES NO

H Directly Bonded to O, N, or F ?
NO YES

Dispersion/ London Forces

Dipole/Dipole Force Hydrogen Bonding

Increasing Strength of Intermolecular Force

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Predict the trend in bp for the following species:

BaCl2, H2, CO, HF, Ne

BaCl2 > HF > CO > Ne > H2 BaCl2 : ionic bonding HF: HB + dispersion CO: dipole-dipole + dispersion Ne: dispersion H2 : dispersion

Stronger intermolecular forces, higher BP, MP

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 van der Waals forces are also known as London forces.

They are weak interactions caused by momentary changes in electron density in a molecule. They are the only attractive forces present in nonpolar compounds.
Even though CH4 has no net dipole, at any one instant its electron density may not be completely symmetrical, resulting in a temporary dipole. This can induce a temporary dipole in another molecule. The weak interaction of these temporary dipoles constitutes van der Waals forces.

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 All compounds exhibit van der Waals forces.

The surface area of a molecule determines the strength of the van der Waals interactions between molecules. The larger the surface area, the larger the attractive force between two molecules, and the stronger the intermolecular forces.

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 van der Waals forces are also affected by polarizability.

Polarizability is a measure of how the electron cloud around an atom responds to changes in its electronic environment.
Larger atoms, like iodine, which have more loosely held valence electrons, are more polarizable than smaller atoms like fluorine, which have more tightly held electrons. Thus, two F2 molecules have little attractive force between them since the electrons are tightly held and temporary dipoles are difficult to induce.

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Dipole-Dipole Interactions Dipoledipole interactions are the attractive forces between the permanent dipoles of two polar molecules. Consider acetone (below). The dipoles in adjacent molecules align so that the partial positive and partial negative charges are in close proximity. These attractive forces caused by permanent dipoles are much stronger than weak van der Waals forces.

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Hydrogen Bonding Hydrogen bonding typically occurs when a hydrogen atom bonded to O, N, or F, is electrostatically attracted to a lone pair of electrons on an O, N, or F atom in another molecule.

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Note: as the polarity of an organic molecule increases, so does the strength of its intermolecular forces.

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What type of intermolecular forces are exhibited by each molecule?

VDW

VDW and DD

OH

VDW
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VDW, DD and HB

Physical PropertiesBoiling Point

The boiling point of a compound is the temperature at which liquid molecules are converted into gas.
In boiling, energy is needed to overcome the attractive forces in the more ordered liquid state. The stronger the intermolecular forces, the higher the boiling point. For compounds with approximately the same molecular weight:

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Consider the example below. Note that the relative strength of the intermolecular forces increases from pentane to butanal to 1butanol. The boiling points of these compounds increase in the same order.

For two compounds with similar functional groups: The larger the surface area, the higher the boiling point. The more polarizable the atoms, the higher the boiling point.
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Consider the examples below which illustrate the effect of size and polarizability on boiling points.

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Consider the alkanes, hexane and 2,3-dimethylbutane

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 These two compounds are structural isomers and have the same number of carbon atoms.

Hexane is a straight-chain alkane and 2,3-dimethylbutane is a branched-chain alkane. Hexane has a boiling point of 69 oC and 2,3-dimethylbutane has a boiling point of 58 oC. This difference is due to the differences in surface area of the two molecules.
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 Hexane has a larger surface area, which results in stronger London forces than those occurring in 2,3dimethylbutane. Hexane molecules can also get closer together than the bulky 2,3-dimethylbutane molecules. More energy (heat) is required to overcome these stronger attractions in hexane, resulting in a higher boiling point, when compared to the boiling point of 2,3-dimethylbutane.
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 For alkanes with the same number of carbon atoms, boiling point increases from branched chain to straight-chain to cycloalkanes Branched < straight < cycloalkanes

2,2-dimethylbutane b.p.= 50 oC 2,3-dimethybutane b.p.= 58 oC Hexane b.p.= 69 oC Cyclohexane b.p.= 81 oC

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Which has the higher boiling point and why?

B
A has only VDW, while B has both VDW and DD interactions
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Which has the higher boiling point and why?

O O

H3CH2C

OH

H3CH2C

OCH3

A
O

H3CH2C

OH

A
A had VDW, DDD and H-bonding, while B lacks H-bonding
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Which has the higher boiling point and why?

H3C (CH2)5 H3C H3C H3C (CH2)20

A
H3 C (CH2)20 H3 C

B
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Both A and B only have VDW interactions, but B has the higher bp because of a larger surface area.

Melting Point
The melting point is the temperature at which a solid is converted to its liquid phase.

In melting, energy is needed to overcome the attractive forces in the more ordered crystalline solid.
The stronger the intermolecular forces, the higher the melting point. Given the same functional group, the more symmetrical the compound, the higher the melting point.

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 Because ionic compounds are held together by extremely strong interactions, they have very high melting points.
With covalent molecules, the melting point depends upon the identity of the functional group. For compounds of approximately the same molecular weight:

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 The trend in melting points of pentane, butanal, and 1-butanol parallels the trend observed in their boiling points.

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 Symmetry also plays a role in determining the melting points of compounds having the same functional group and similar molecular weights, but very different shapes.
A compact symmetrical molecule like neopentane packs well into a crystalline lattice whereas isopentane, which has a CH3 group dangling from a four-carbon chain, does not. Thus, neopentane has a much higher melting point.

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Which has the higher melting point and why?

NH2

A
NH2

B
B has stronger intermolecular forces (DD and HBZ).
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Which has the higher melting point and why?

Both only have VDW forces, so A has the higher mp because it is more symmetrical. Closer packing means higher mp.
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