Hydrogen Bonding

~ Chromoscience

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Five water molecules are shown near one another, but not touching. A dotted line lies between many of the hydrogen atoms on one molecule and the oxygen atom on another molecule.
Figure 1. Water molecules participate in multiple hydrogen-bonding interactions with nearby water molecules. Source: OpenStax Chemistry 2e

Hydrogen Bonding (OpenStax Chemistry 2e)

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. Figure 1 illustrates hydrogen bonding between 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 Figure 2. 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.

A line graph is shown where the y-axis is labeled “Boiling point (, degree sign, C )” and has values of “ negative 150” to “150” from bottom to top in increments of 50. The x-axis is labeled “Period” and has values of “0” to “5” in increments of 1. Three lines are shown on the graph and are labeled in the legend. The red line is labeled as “halogen family,” the blue is “oxygen family” and the green is “nitrogen family.” The first point on the red line is labeled “question mark” and is at point “2, negative 120”. The second point on the line is labeled “H C l” and is at point “3, negative 80” while the third point on the line is labeled “H B r” and is at point “4, negative 60”. The fourth point on the line is labeled “H I” and is at point “5, negative 40.” The first point on the green line is labeled “question mark” and is at point “2, negative 125.” The second point on the line is labeled “P H, subscript 3” and is at point “3, negative 80” while the third point on the line is labeled “A s H, subscript 3” and is at point “4, negative 55.” The fourth point on the line is labeled “S b H, subscript 3” and is at point “5, negative 10.” The first point on the blue line is labeled “question mark” and is at point “2, negative 80.” The second point on the line is labeled “H, subscript 2, S” and is at point “3, negative 55” while the third point on the line is labeled “H, subscript 2, S e” and is at point “4, negative 45.” The fourth point on the line is labeled “H, subscript 2, T e” and is at point “5, negative 3.”
Figure 2. 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. Source: OpenStax Chemistry 2e

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 Figure 3. The stark contrast between our naïve predictions and reality provides compelling evidence for the strength of hydrogen bonding.

A line graph is shown where the y-axis is labeled “Boiling point, ( degree sign, C )” and has values of “negative 150” to “150” from bottom to top in increments of 50. The x-axis is labeled “Period” and has values of “0” to “5” in increments of 1. Three lines are shown on the graph and are labeled in the legend. The red line is labeled as “halogen family,” the blue is “oxygen family” and the green is “nitrogen family.” The first point on the red line is labeled “H F” and is at point “2, 25.” The second point on the line is labeled “H C l” and is at point “3, negative 80” while the third point on the line is labeled “H B r” and is at point “4, negative 60.” The fourth point on the line is labeled “H I” and is at point “5, negative 40.” The first point on the green line is labeled “N H, subscript 3” and is at point “2, negative 40.” The second point on the line is labeled “P H, subscript 3” and is at point “3, negative 80” while the third point on the line is labeled “A s H, subscript 3” and is at point “4, negative 55.” The fourth point on the line is labeled “S b H, subscript 3” and is at point “5, negative 10.” The first point on the blue line is labeled “H, subscript 2, O” and is at point “2, 100.” The second point on the line is labeled “H, subscript 2, S” and is at point “3, negative 55” while the third point on the line is labeled “H, subscript 2, S e” and is at point “4, negative 45.” The fourth point on the line is labeled “H, subscript 2, T e” and is at point “5, negative 3.”
Figure 3. 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. Source: OpenStax Chemistry 2e

Source:

Flowers, P., Theopold, K., Langley, R., & Robinson, W. R. (2019, February 14). Chemistry 2e. Houston, Texas: OpenStax. Access for free at: https://openstax.org/books/chemistry-2e

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