Hydrogen Bonding

Nitrosyl fluoride (ONF, molecular mass 49 amu) is a gas at room temperature. Water (H2O, molecular mass 18 amu) is a liquid, even though it has a lower molecular mass. We clearly cannot attribute this difference between the two compounds to dispersion forces. Both molecules have about the same shape and ONF is the heavier and larger molecule. It is, therefore, expected to experience more significant dispersion forces. Additionally, we cannot attribute this difference in boiling points to differences in the dipole moments of the molecules. Both molecules are polar and exhibit comparable dipole moments. The large difference between the boiling points is due to a particularly strong dipole-dipole attraction that may occur when a molecule contains a hydrogen atom bonded to a fluorine, oxygen, or nitrogen atom (the three most electronegative elements). The very large difference in electronegativity between the H atom (2.1) and the atom to which it is bonded (4.0 for an F atom, 3.5 for an O atom, or 3.0 for a N atom), combined with the very small size of a H atom and the relatively small sizes of F, O, or N atoms, leads to highly concentrated partial charges with these atoms. Molecules with F-H, O-H, or N-H moieties are very strongly attracted to similar moieties in nearby molecules, a particularly strong type of dipole-dipole attraction called hydrogen bonding. Examples of hydrogen bonds include HF⋯HF, H2O⋯HOH, and H3N⋯HNH2, in which the hydrogen bonds are denoted by dots. The figure below illustrates hydrogen bonding between water molecules.

Water molecules participate in multiple hydrogen-bonding interactions with nearby water molecules.

Despite use of the word “bond,” keep in mind that hydrogen bonds are intermolecular attractive forces, not intramolecular attractive forces (covalent bonds). Hydrogen bonds are much weaker than covalent bonds, only about 5 to 10% as strong, but are generally much stronger than other dipole-dipole attractions and dispersion forces.

Hydrogen bonds have a pronounced effect on the properties of condensed phases (liquids and solids). For example, consider the trends in boiling points for the binary hydrides of group 15 (NH3, PH3, AsH3, and SbH3), group 16 hydrides (H2O, H2S, H2Se, and H2Te), and group 17 hydrides (HF, HCl, HBr, and HI). The boiling points of the heaviest three hydrides for each group are plotted in the graph below. As we progress down any of these groups, the polarities of the molecules decrease slightly, whereas the sizes of the molecules increase substantially. The effect of increasingly stronger dispersion forces dominates that of increasingly weaker dipole-dipole attractions, and the boiling points are observed to increase steadily.

For the group 15, 16, and 17 hydrides, the boiling points for each class of compounds increase with increasing molecular mass for elements in periods 3, 4, and 5.

If we use this trend to predict the boiling points for the lightest hydride for each group, we would expect NH3 to boil at about −120 °C, H2O to boil at about −80 °C, and HF to boil at about −110 °C. However, when we measure the boiling points for these compounds, we find that they are dramatically higher than the trends would predict, as shown in the plot below. The stark contrast between our naïve predictions and reality provides compelling evidence for the strength of hydrogen bonding.

In comparison to periods 3−5, the binary hydrides of period 2 elements in groups 17, 16 and 15 (F, O and N, respectively) exhibit anomalously high boiling points due to hydrogen bonding.

Effect of Hydrogen Bonding on Boiling Points

Consider the compounds dimethylether (CH3OCH3), ethanol (CH3CH2OH), and propane (CH3CH2CH3). Their boiling points, not necessarily in order, are −42.1 °C, −24.8 °C, and 78.4 °C. Match each compound with its boiling point. Explain your reasoning.

The VSEPR-predicted shapes of CH3OCH3, CH3CH2OH, and CH3CH2CH3 are similar, as are their molar masses (46 g/mol, 46 g/mol, and 44 g/mol, respectively), so they will exhibit similar dispersion forces. Since CH3CH2CH3 is nonpolar, it may exhibit only dispersion forces. Because CH3OCH3 is polar, it will also experience dipole-dipole attractions. Finally, CH3CH2OH has an −OH group, and so it will experience the uniquely strong dipole-dipole attraction known as hydrogen bonding. So the ordering in terms of strength of IMFs, and thus boiling points, is CH3CH2CH3 < CH3OCH3 < CH3CH2OH. The boiling point of propane is −42.1 °C, the boiling point of dimethylether is −24.8 °C, and the boiling point of ethanol is 78.5 °C.

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Hydrogen Bonding and DNA

Deoxyribonucleic acid (DNA) is found in every living organism and contains the genetic information that determines the organism’s characteristics, provides the blueprint for making the proteins necessary for life, and serves as a template to pass this information on to the organism’s offspring. A DNA molecule consists of two (anti-)parallel chains of repeating nucleotides, which form its well-known double helical structure, as shown in the figure below.

Two separate DNA molecules form a double-stranded helix in which the molecules are held together via hydrogen bonding. (credit: modification of work by Jerome Walker, Dennis Myts)

Each nucleotide contains a (deoxyribose) sugar bound to a phosphate group on one side, and one of four nitrogenous bases on the other. Two of the bases, cytosine (C) and thymine (T), are single-ringed structures known as pyrimidines. The other two, adenine (A) and guanine (G), are double-ringed structures called purines. These bases form complementary base pairs consisting of one purine and one pyrimidine, with adenine pairing with thymine, and cytosine with guanine. Each base pair is held together by hydrogen bonding. A and T share two hydrogen bonds, C and G share three, and both pairings have a similar shape and structure.

The geometries of the base molecules result in maximum hydrogen bonding between adenine and thymine (AT) and between guanine and cytosine (GC), so-called “complementary base pairs.”

The cumulative effect of millions of hydrogen bonds effectively holds the two strands of DNA together. Importantly, the two strands of DNA can relatively easily “unzip” down the middle since hydrogen bonds are relatively weak compared to the covalent bonds that hold the atoms of the individual DNA molecules together. This allows both strands to function as a template for replication.