Dual-capillary dilatometer for density measurements of supercooled water

Abstract

An apparatus tailored to accurate density measurements of supercooled water, i.e. liquid water in a metastable state below the freezing point temperature, was recently developed at the Institute of Thermomechanics of the Czech Academy of Sciences. The apparatus, dual-capillary dilatometer, is described, together with the measurement procedure and the evaluation methodology. The primary result of the dual-capillary method are relative densities with respect to the density at a reference temperature and given pressure. In order to calculate absolute densities, densities at the reference temperature as a function of pressure are needed. For calculation of such pressure dependence of density, so called thermodynamic integration involving literature thermodynamic data and our experimental results is used. The dual-capillary dilatometer was successfully employed in density measurements of ordinary water, heavy water and seawater. The data in the temperature range from 238.15 to 303.15 K at pressures from atmospheric up to 200 MPa are presented and compared with respective IAPWS formulations of thermodynamic properties. The data for ordinary water are also compared with an accurate equation of state for supercooled water of Holten et al. (2014) revealing good mutual agreement. The expanded uncertainty of relative densities acquired by means of the dual-capillary method is estimated to be lower than 50 ppm.

Equation of State of Liquid Water Written by Simple Experimental Polynomials and the Liquid–Liquid Critical Point

“…As case 1, we made approximate equations using the accurate literature data for water volume ranging from −100 to 1000 MPa, 238 to 500 K, and 0.8 to 1.2 cm 3 /g. − We note that most of the volume (density) data were provided in the Data Tables of the Supporting Information of ref . As case 2, using this volume data plus the volume data for supercooled water down to 200 K obtained from experiments with emulsified supercooled water, approximate equations were created to reproduce these volume values.…”