Why Does the Ocean Take Up so Much Heat? The Molecular Basis for Heat
Capacity.
Abstract
The ocean covers 70% of the surface of the planet, yet absorbs a
remarkable 93% of the additional heat trapped by anthropogenic
greenhouse gases due to its large size, the omnipresent stirring by
wind, and the “high heat capacity” of water; yet the molecular basis
for the high specific heat of water (CP) is not well known. It has long
been established that specific heats are closely tied to molecular
weight. Ironically, water has no fixed molecular weight: it exists as a
bi-molecular fluid consisting of the singlet H2O form and an ensemble of
hydrogen bonded forms in a temperature dependent equilibrium. We show
that the mean molecular weight of water over the range 0-40°C is 82-79.
The warming of water induces the breaking of hydrogen bonds (8.364
kJ/mol), increasing the population of the singlet H2O form at the
expense of the hydrogen bonded forms. Although warming of sea water by
10°C yields only a 2% increase in free H2O, this accounts for some 36%
of the energy consumed. Consequently, the high heat capacity of water,
and water in sea water, is attributable (64%) to the large molecular
weight of the hydrogen bonded forms, dominantly as the tetrahedral
pentamer (H2O)5, and also (36%) to the energy required to break
hydrogen bonds. The CP for pure water decreases with increased
temperature due to the decrease in the ensemble molecular weight with
warming, while the CP for sea water increases with increasing
temperature due the work required to increase the translational energy
of the large hydrated cations, which are dominantly Na(H2O)6 with a
molecular weight of 131. Thus, it is the multiple forms of water and
their hydrogen bonding that accounts for the high specific heat of both
pure water and sea water.