Lecture 2: Further reading

Intermolecular Forces

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 Intramolecular Bonding
vs Intermolecular Forces
• Intramolecular bonding: between atoms of the same molecule
(ionic or covalent bonding)
• Intermolecular forces: Attractive forces between molecules

• Strength: Intramolecular bonds > intermolecular forces

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 Intermolecular Forces (IF) vs phases Weak IF

• IF: → how molecules are

“connected” together
• Thermal energy: internal kinetic
energy (including vibrational,
rotational, translational) → how
“free” the molecules are

Free to move
IF Thermal
energy

• IF vs thermal energy → State of

matter (s, l, g)
IF Thermal
energy
gas weak high
liquid Locked in the crystal

solid strong low Strong IF

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Types of covalent IF

• Hydrogen Bonding

• Dipole-Dipole Forces

• Dispersion Forces (London Forces or Van der Waals Forces)

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Dipole-Dipole Forces
- Dipole: when a molecule is polar, it has a dipole

- Permanent dipole: when the polarity is permanent (always)

acetone
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Dipole-Dipole Example

• Which of the following have dipole forces:

• CI4

• CH3Cl

• CO2

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 Dipole-Dipole Forces vs Boiling Point
• Polar molecules have higher boiling point and melting
points than nonpolar molecules (similar MW)

• Which one has a higher boiling point?

• CO and N2?

• C3H8 and CH3OCH3?

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 Dipole-Dipole Forces vs Boiling Point
• Polar molecules have higher boiling point and melting
points than nonpolar molecules (similar MW)

• Which one has a higher boiling point?

• CO and N2? (-191.5 °C and -195.8 °C)

• C3H8 and CH3OCH3? (-42 °C and -24 °C)

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 Hydrogen Bonding
• Dipole-dipole force between H and a high
electronegativity atom (N, O, F) → H – bond

• Hydrogen bonds are between molecules and are

not a type of chemical bond which is between
atoms

• Strongest among IF → compounds with H-bonds

have higher melting and boiling points

• 1: Which has a higher boiling point HF or HCl?

• 2: Compare boiling points of NH3 and HF.

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Dispersion Forces
(London Forces or Van der Waals Forces)
• All molecules have dispersion forces:
• Result of fluctuations in the electron distribution
• Electrons are not always symmetrically arranged
• Charge separation causes an instantaneous dipole

• Bigger MW → bigger dispersion forces → higher boiling point

Molecule CH4 SiH4 GeH4 SnH4
Boiling point -164.0 °C -111.8 °C -88.5 °C -52.0 °C
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Boiling Points Affected by IF’s
• In general (when MW are relatively similar),
Energy of H-bond > dipole-dipole > dispersion
So compound with H bond will have the highest boiling point
• As molar mass increases (significantly), boiling point increases
(dispersion forces dominate)

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Covalent Intermolecular Forces

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Notes

• HCl is considered to not have H-bond

• Although Cl and N both have similar EN, Cl has a bigger
radius, making the partial negative charge in N to be more
dense compared to Cl; therefore the H-bond exists only
with H-F, H-O or H-N; not H-Cl
• HF has lower boiling point than H2O
• Some explanation
http://www.chemguide.co.uk/atoms/bonding/hbond.html

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Practice

Which gas would behave more ideally at the same

conditions of P and T?

CO or N2

Why?

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Practice

• Compare the boiling point

• N2, CO, H2O
• C2H5OH, CH3OCH3
• Do dispersion forces exist between molecules have H-bond?

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