Mass spectrometry was used to study ion-induced water clusters [H(+)(H(2)O)(c)], where c = the cluster size, i.e.,the number of monomers per cluster. It is shown that the numbers of hydrogen bonds in populations of these clusters in water vapor vary as the square of partial pressure and inversely with temperature, with functional dependencies that are almost identical to those observed for the infrared continuum absorption and for anomalous absorption in other wavelength regions. Experimental mass spectra taken at constant temperature vs partial pressure and data obtained at constant water vapor partial pressure vs temperature are presented and discussed. These results are combined with the evidence of cloud physicists including C. T. R. Wilson to show rather conclusively that naturally occurring ionic processes in water vapor generate large populations of hydrogen-bonded neutral water clusters that are responsible for the infrared continuum absorption. These processes can be enhanced by various kinds of ionizing energy, thus increasing anomalous absorption in water vapor or in moist air. If electrical properties of the atmosphere influence the infrared continuum absorption, which is an important mechanism in determining climate at the earth's surface, it will be necessary to reexamine extensively existing models of atmospheric radiative transfer.
A Raman method was developed for determining the partial molal heats of dissolution of gaseous species vaporized from liquid mixtures, and the method was applied to concentrated aqueous HCl solutions. Raman intensities of the symmetric stretching modes from H2O and HCl at 3652 and 2886 cm-l, respectively, were measured from the vapor over concentrated HCI, 18.8-38.0 wt 7% HCl, between =20 and 110 OC. The In I versus l/Tplots ( I is the Raman intensity) yielded the average (-65 "C) heats of dissolution (negative heats of solution), which equal the partial molal heats, because the liquid concentration remains essentially constant.The (Raman) partial molal heats of dissolution for gaseous HCl are given by 16 700 -4394, in cal/mol (n2 = HCl molality). The corresponding function calculated from Thomsen's 18 OC calorimetric data (ref 2), 17 360 -432n2, differs slightly because different temperatures are involved. The (Raman) partial molal heats of dissolution of gaseous H2O also agree with the aqueous values (Thomsen's data, Gibbs-Duhem analysis) if the heat of vaporization is added. The new Raman method may be used for any solution, provided that the vapor pressures-are large enough for Raman highly reactive mixtures by virtue of Raman
New findings concerning clusters of water molecules in water vapor and in moist air are combined with observations from classical cloud physics to show that many discrepancies can be reconciled by the existence of enormous equilibrium populations ofiarge neutral water clusters in the vapor state. These water clusters are believed to be those "nuclei"responsible for the "cloudlike" condensation first described by Wilson at supersaturations of 4-5. They absorb electromagnetic radiation at infrared and longer wavelengths, and are believed to be responsible for the atmospheric infrared continuum absorption.
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