Estimation of local density augmentation and hydrogen bonding between pyridazine and water under sub- and supercritical conditions Using UV-Vis spectroscopy

The local density around pyridazine was evaluated by examining the UV-vis spectral shift of pyridazine in a high-pressure liquid state and supercritical water from 25 to 450°C and from 20 to 45 MPa. Augmentation of the local density was observed from 380 to 420°C, and showed the maximum at a lower density than the critical density of water. The degree of hydrogen bonding was estimated in consideration of the local density augmentation. The estimated degree of hydrogen bonding under subcritical conditions without any difference between the local density and the bulk density corresponded to the previously reported results with a UV-vis absorbance spectral shift of quinoline and an NMR proton chemical shift. However, the degree of hydrogen bonding near the critical point of water was larger than that in the case that the local density augmentation was not taken into account. At 380°C and 0.2 g cm^-3 of the bulk density there are 30% as many hydrogen bonds as those under the ambient condition, and it was around 1.5-times that without considering local-density augmentation. 2006