physical chemistry - What's the relationship between Van der Waals forces and hydrophobic interactions?

A question on a past exam for a course I'm studying for asks:

What's the relation between Van der Waals forces and hydrophobic interactions?

From what I understand, Van der Waals forces are just a name to summarize a bunch of little weak forces that only come into play when molecules are placed close to one other, based off this previous answer to my question.

I understand that hydrophobic interactions arise because non-polar components of a molecule are unable to form bonds with hydrogen in water, but disrupt the hydrogen, forcing them to make a cage-like structure (although I'm not clear on why), based off this entry in the Chemistry wiki.

Is the relation between these two forces that Van der Waals forces can be encouraged by hydrophic forces? Is there some other relation I'm missing here? Does it have something to do with the interactions denaturing at high temperatures?

Answer

Van der Waals forces are the attractions/repulsions - the forces - between molecules or atoms, other than attractions like ionic attractions, and covalent attractions. These forces are:

1. Keesom Effect - This is an effect caused by two polar atoms interacting with each other. Two permanent dipoles are involved, meaning the molecules/atoms involved are polar. This may be attractive or repulsive, depending on the dipoles involved.


2. Deybe force - This is an effect caused between a molecule with is polar, and one that is not. Because the one that is polar affects the electrons on the second (non-polar) molecule, it creates an attractive force between the two molecules.


3. London dispersal effect - This is a force that acts between two non-polar molecules/atoms. Because the electrons around each molecule/atom repel each other, it creates a redistribution of charge, inducing an instantaneous dipole moment. This is the force that acts in liquid noble gases, to make them liquid, or between methane molecules in liquid form.

Hydrophobic forces are caused because molecules like ethane and other hydrocarbons - petrol etc. and oils like sunflower oil etc. are non-polar, and therefore don't "like" being dissolved in a polar solvent like water. In water, there are hydrogen bonds between the individual molecules, which is why water is a liquid - the van der Waals forces are far too small in water to bind the water as a liquid at room temperature. If we introduce non-polar substances into the water - polar solvent - it upsets these hydrogen bonds, and creates an increase in enthalpy because of this. Therefore the lowest energy state is for the hydrophobic hydrocarbons to separate themselves from the water.

The relationship between van der waals forces and hydrophobic interactions is that the van der waals act to bind the hydrophobe - non-polar substance - together, to separate from the polar solvent/water, and these contribute to the energy needed to separate the two substances. The seperation causes a decrease in the entropy of the system. To counter this decrease in entropy, there must be some decrease in enthalpy. Because the hydrophobe disrupts the hydrogen bonding in water, when they separate, the hydrogen bonding then causes an decrease in enthalpy, because of the favorable interactions. This is also where the van der Waals forces come in. They are favourable interactions, so cause a decrease in enthalpy, and this helps the separation of the hydrophobe and the water into two separate phases, because it makes the separation more energetically favourable. They are not necessary, but make separation more favourable, because the enthalpy change is greater for the separation process. This makes it more favourable.