Chem 16 Intermolecular Forces

Non-polar vs Polar

Test yourself !
Arrange the following bonds

in increasing order of polarity :

H-H, O-H, Cl-H, S-H, F-H

Identify the type of compound :

BaCl2, O2, NH3, CsF, CH4

Interparticle Forces of Attraction

London Dispersion or induced dipole Non-polar molecules Dipole-dipole Polar molecules H-bonding H attached to F, N, O, Ionic bonding Cations and anions or electrostatic

Induced Dipole
Distortion of electron cloud Bigger molecules are more polarizable

London Forces

Dipole-Induced Dipole Interaction

Test Yourself
Which one has the highest boiling point? Explain your choice.

CH4, SiH4, GeH4

Boiling Points: Hydrides

Dipole-Dipole Interaction

Test Yourself
Which one has the highest boiling point? Explain your choice.

C3H8, CO2, CH4 CN

Test Yourself
Which one has the highest boiling point? CH4, SiH4, GeH4 Which one has the highest boiling point? OH2 , SH2 , SeH2 , TeH2

Boiling Points: Hydrides

Ionic Interaction
Between Cations and Anions Example: NaCl

http://www.cem.msu.edu/~reusch/VirtualText/intro2.htm

Hydrogen Bonding

Intermolecular Forces
Intermolecular forces are interactions that exist between molecules.

There are several types of intermolecular interactions.

Ionic compounds contain oppositely charged particles held together by extremely strong electrostatic interactions. These ionic interactions are much stronger than the intermolecular forces present between covalent molecules.

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 Covalent compounds are composed of discrete molecules. The nature of the forces between molecules depends on the functional group present. There are three different types of interactions, shown below in order of increasing strength: van der Waals forces dipole-dipole interactions hydrogen bonding
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van der Waals Forces

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.
Figure 3.1
Surface area and van der Waals forces

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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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Physical Properties Boiling 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 boiling point.

higher the

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 1-butanol. 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.
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Consider the examples below which illustrate the effect of size and polarizability on boiling points.
Figure 3.2
Effect of surface area and polarizability on boiling point

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Which has the higher boiling point and why?

O

A has only VDW, while B has both VDW and DD interactions

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H C H C 3 2

O H

H C H C 3 2

O C H 3

H3CH2C

OH

A had VDW, DDD and Hbonding, while B lacks Hbonding

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H3C (CH2)5 H3C

H3C (CH2)20 H3C

A
H3C

(CH2)20 H3C

Both A and B only have VDW interactions, but B has the higher bp b/c of a larger

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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 N H point and why?

2

A
NH2

B has stronger intermolecular forces (DD and HBZ).

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

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