Journal of Chemical Thermodynamics, Vol.37, No.7, 671-683, 2005
Deuterium isotope differences in 2-propanone, (CH3)(2)CO/(CD3)(2)CO: a high-pressure sound-speed, density, and heat capacities study
A new high-pressure, non-intrusive ultrasonic microcell [J. Chem. Thermodyn. 36 (2004) 211-222] was used to carry out sound-speed measurements in deuteriated 2-propanone (acetone-d(6)) in broad ranges of temperature (288 < T/K < 338) and pressure (0.1 < p/MPa < 160). To the best of our knowledge, there are no data regarding speed of sound of acetone-d(6). (p, p, 7) data for acetone-d6 were also determined but in a narrower T,p range (298 to 333 K; 0.1 to 60 MPa). In this interval, several thermodynamic properties were thus determined, such as: isentropic (kappa(S)) and isothermal (kappa(T)) compressibility, isobaric thermal expansivity (alpha(p)), isobaric (c(p)) and isochoric (c(v)) specific heat capacity, and the thermal pressure coefficient (gamma(v)). Comparisons with our data for acetone-h(6) enabled us to establish the magnitude and sign of deuterium isotope effects for identical properties. These effects are a consequence of distinct vibrational mode frequencies in an isotope-invariant force constants' field. Molar heat capacities and their isotope effects were theoretically determined by employing an Einstein-like model for the vibrational frequencies of acetone-h6 and acetone-d(6). (c) 2004 Elsevier Ltd. All rights reserved.