| Abstrakt: |
We report on laboratory and field Raman spectroscopy experiments on the structure of water in sea water and describe this as a function of temperature and pressure. The Raman spectrum of water/seawater is dominated by the water stretching mode band with a frequency shift in the range 2,800–3,800 cm−1. Here the hydrogen bonded (HB) clusters of several water molecules and nonhydrogen bonded (nHB, singlet H2O) forms are revealed with an isoskedastic point, similar to the isosbestic point for pH sensitive dyes. This band can be deconvolved into five Gaussian peaks, each with a specific spectroscopic assignment. We find that within the temperature range of 0–40 °C the vastly greater mass and volume of ocean water (78–85%) is in the HB forms, dominantly as (H2O)5. Without hydrogen bonding there would be no ocean, and nowhere in the bulk ocean does the simple H2O molecule exceed 20% of the total. The fraction of water molecules in the solvation shell around ions in seawater represents a third type of water, bound to an ion but not hydrogen bonded. Approximately 6% of the water molecules present at 35 salinity are in this form, and their concentration is not affected by temperature or pressure. The HB forms are a continuum of species in rapid exchange. The fraction of nHB is driven solely by temperature. We find no evidence that increased pressure changes the population of the free singlet nHB molecule; pressure drives the dominantly (H2O)5 population toward a lower volume, nested, molecular state. Plain Language Summary: For over 50 years ocean scientists have represented the important physical properties of sea water as a collection of bulk fluid coefficients that simply provided a statistical fit to the observed compressibility, sound speed, etc.—but with no underlying molecular basis. Sea water is 96.5% water, and for over 50 years chemists describing the molecular physics of pure water have evolved an understanding that water is composed of a temperature‐driven balance between the hydrogen bonded and nonhydrogen bonded forms, but this knowledge has not been applied to the oceans—the largest body of water on Earth. Here we link these two fields by using laser Raman spectroscopy. We show that by far the greater volume of the ocean—some 78–85% is composed of the hydrogen bonded form (H2O)5. Without this water would not be liquid and we would literally have no ocean at all. With this knowledge we are better able to understand the processes occurring under climate‐driven ocean warming. Key Points: Seawater is comprised dominantly (75–85%) of the hydrogen bonded pentamer (H2O)5The simple H2O molecule exists in temperature‐controlled equilibrium with the dominant (H2O)5 speciesPressure forces the (H2O)5 species into a lower‐volume nested state [ABSTRACT FROM AUTHOR] |
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