Equation of State of Water Under Negative Pressure

J Chem Phys. 2010 Nov 7;133(17):174507. doi: 10.1063/1.3495971.


We report on the simultaneous measurements of the speed of sound and the density in liquid water under negative pressure. Application of a focused acoustic wave to the bulk liquid is able to generate negative pressures before nucleation of the vapor phase occurs. A method for time-resolved Brillouin scattering is developed to measure the speed of sound during the passage of a 1 MHz ultrasonic wave. This is coupled with a fiber optic probe hydrophone which allows the determination of the density. Together, these methods give an ambient temperature equation of state of metastable liquid water down to the acoustic cavitation threshold. Empirical equations of state of water are based on experimental data at positive pressure; the validity of their extrapolation to negative pressures had been tested only indirectly or with very weakly metastable liquid. We provide thermodynamic data that prove the fidelity of recent equations of state down to -26 MPa. However, this raises questions regarding the nature of the cavitation threshold observed in acoustic experiments, which is far less negative than expected.