# 5.10: The implications of bond polarity

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Two important physical properties of molecules (although this applies primarily to small molecules and not macromolecules) are their melting and boiling points. Here we are are considering a pure sample that contains extremely large numbers of the molecule. Let us start at a temperature at which the sample is liquid. The molecules are moving with respect to one another, there are interactions between the molecules, but they are transient - the molecules are constantly switching neighbors. As we increase the temperature of the system, the energetics of collisions are now such that all interactions between neighboring molecules are broken, and the molecules fly away from one another. If they happen to collide with one another, they do not adhere; the bond that might form is not strong enough to resist the kinetic energy delivered by collision with other the molecules. The molecules are said to be a gaseous state and the transition from liquid to gas is the boiling point. Similarly, starting with a liquid, when we reduce the temperature, the interactions between molecules become longer lasting until such a temperature is reached that the energy transferred through collisions is no longer sufficient to disrupt the interactions between molecules163. As more and more molecules interact, neighbors become permanent - the liquid has been transformed into a solid. While liquids flow and assume the shape of their containers, because neighboring molecules are free to move with respect to one another, solids maintain their shape, and neighboring molecules stay put. The temperature at which a liquid changes to a solid is known as the melting point. These temperatures mark what are known as phase transitions: solid to liquid and liquid to gas.

At the macroscopic level, we see the rather dramatic effects of bond polarity on melting and boiling points by comparing molecules of similar size with and without polar bonds and the ability to form H-bonds. For example, neither CH4 (methane) and Ne (neon) contain polar bonds and cannot form intra-molecular H-bond-type electrostatic interactions. In contrast NH3 (ammonia), H2O (water), and FH (hydrogen fluoride) have three, two and one polar bonds, respectively, and can take part in one or more intra-molecular H-bond-type electrostatic interactions. All five compounds have the same number of electrons, ten. When we look at their melting and boiling temperatures, we see rather immediately how the presence of polar bonds influences these properties.

In particular water stands out as dramatically different from the rest of the molecules, with significantly higher (> 70ºC) melting and boiling point than its neighbors. So why is water different? Well, in addition to the presence of polar covalent bonds, we have to consider the molecule's geometry. Each water molecule can take part in four hydrogen bonding interactions with neighboring molecules - it has two partially positive Hs and two partially negative sites on its O. These sites of potential H-bond-type electrostatic interactions are arranged in a nearly tetragonal geometry. Because of this arrangement, each water molecule can interact through H-bond-type electrostatic interactions with four neighboring water molecules. To remove a molecule from its neighbors, four H-bond-type electrostatic interactions must be broken, which is relatively easy since they are each rather weak. In the liquid state, molecules jostle one another and change their H-bond-type electrostatic interaction partners constantly. Even if one is broken, however, the water molecule remains linked to multiple neighbors via H-bond-type electrostatic interactions.

This molecular hand-holding leads to water's high melting and boiling points as well as its high surface tension. We can measure the strength of surface tension in various ways. The most obvious is the weight that the surface can support. Water's surface tension has to be dealt with by those organisms that interact with a liquid-gas interface. Some, like the water strider, use it to cruise along the surface of ponds. As the water strider walks on the surface of the water, the molecules of its feet do not form H-bond-type electrostatic interactions with water molecules, they are said to be hydrophobic, although that is clearly a bad name - they are not afraid of water, rather they are simply apathetic to it. Hydrophobic molecules interact with other molecules, including water molecules, only through van der Waals interactions. Molecules that can make H-bonds with water are termed hydrophilic. As molecules increase in size they can have regions that are hydrophilic and regions that are hydrophobic (or hydroapathetic). Molecules that have distinct hydrophobic and hydrophilic regions are termed amphipathic and we will consider them in greater detail in the next chapter.