Intermolecular Forces Section 4.3

Introduction There are ionic, giant covalent, and simple molecular covalent bonds between atoms If there are no attractive forces between molecules, then all substances would be gases There must be some force that attracts molecules to other molecules that does not create a real bond These are known collectively as intermolecular forces

Types of Intermolecular Forces In order of increasing strength: van der Waals' forces (AKA London forces or dispersion forces) Dipole-dipole forces Hydrogen bonding

van der Waals' Forces Exist between all species Is the only intermolecular force between non-polar species Result of temporary (instantaneous) dipoles when one side of the molecule becomes partially negative because of the random motion of electrons

Van der Waals Continued This results in a weak dipole moment that then attracts other molecules Strength of this force increases with molar mass as more electrons are available for temporary dipoles

Effect of van der Waals' Forces on Boiling Point Higher boiling point means more energy is needed to break the intermolecular forces As the molar mass increases, the boiling point increases As the surface area increases, the boiling point increases (again, more electrons available) More elongated the molecule, the stronger the van der Waals' forces, so the higher the boiling point

Continued Sometimes the van der Waals' force can be quite strong as in the case of some polymers that have high mass and are very long molecules

Dipole-dipole forces Dipole moment: a measure of the polarity of a molecule Arrows are used to represent the polarity of the bond (heading toward the partially negative part) The permanent dipoles formed cause electrostatic attraction between molecules that have the permanent dipoles Stronger than van der Waals' forces in molecules of similar size

Effect of Dipole-dipole Forces on Boiling Point Compared to molecules of similar mass with only van der Waals' forces, much higher boiling point Polar molecules have van der Waals' forces and dipole-dipole forces Stronger intermolecular force: higher boiling point

Hydrogen Bonding Not a “true” bond Occurs when hydrogen is bonded to highly electronegative, small atoms, like N, O, or F Creates a very high dipole moment as the more electronegative atom attracts the electrons, leaving the hydrogen very partially positive Can be thought of as part way between a dipole- dipole force and a dative covalent bond

Continued For maximum strength, the 2 atoms and the hydrogen should be in a straight line When X and Y are N, O, or F: X δ- : hydrogen bond H δ+ - Y δ- Usually much stronger than other intermolecular forces

Effect of H-bonding on Boiling Point Consider HF and HCl: HF has van der Waals' forces, dipole-dipole forces, and H-bonding HCl has van der Waals' forces and dipole- dipole forces Boiling point of HF is higher than HCl More energy is needed to break the intermolecular forces

Consider H 2 O and H 2 S H-bonding present in H 2 O, but not in H 2 S Boiling point of water is higher than H 2 S H-bonding allows water to form tetrahedral shapes when it is a liquid H-bonding allows water to form hexagons when it freezes, so ice is less dense than liquid water H-bonding in water also forms temporary hexagon arrays on the surface of water, giving it a high surface tension

Consider NH 3 and PH 3 NH 3 can hydrogen bond with itself and with the water when the ammonia is aqueous PH 3 can only hydrogen bond with water, not with itself Ammonia has the higher boiling point

More to Consider Considering CH 3 OCH 3 and CH 3 CH 2 OH CH 3 OCH 3 has the hydrogens bonded to the carbons, not the oxygen, so no hydrogen bonding occurs CH 3 CH 2 OH has the hydrogen bonded to the oxygen, so H-bonding occurs CH 3 CH 2 OH has a higher boiling point than CH 3 OCH 3

Another Consideration CH 3 CH 2 CH 3, CH 3 CHO, and CH 3 CH 2 OH All have about the same mass CH 3 CH 2 CH 3 cannot hydrogen bond with itself or with water CH 3 CHO cannot hydrogen bond with itself, but can with water CH 3 CH 2 OH can hydrogen bond with itself and water b. p. trend: CH 3 CH 2 CH 3 < CH 3 CHO < CH 3 CH 2 OH

Biological Importance The weak bond between the nitrogenous bases in nucleic acids is a H-bond Occurs between thymine and adenine as well as between cytosine and guanine Easily broken by enzymes