Near-Infrared Studies of the Structure of Water. IV. Water in Relatively Nonpolar Solvents

The peak positions for the absorption bands of water in CCl4, CS2, CDCl3, and C2H4Cl2 have been measured. The positions agreed closely with values calculated from equations developed for water vapor, indicating the monomeric nature of water in these solutions. In addition, the shifts in frequency maxima from the vapor phase values showed a correlation with the solution dielectric constant. The experimental absorption maxima for liquid water did not agree with the calculated values nor did they fit the correlation with dielectric constant. However, the peak position assigned to water molecules with neither hydrogen involved in hydrogen bonding did agree with the dielectric constant correlation. The absorption maxima for a saturated solution of NaClO4, which was expected to have a large amount of such nonbonded species, were also in satisfactory agreement with the calculated peak positions.