New equation of state for fluid water based on hard-sphere perturbation theory and dimerization equilibria

Conference · Wed Aug 01 00:00:00 EDT 1979

OSTI ID:5794543

Whiting, W B; Prausnitz, J M

The perturbation theory of Barker, Henderson, Alder, and others has been extended to gaseous and liquid water first by inclusion of Prigogine's parameter c to account for external degrees of freedom due to rotation and vibration and second by including chemical and hydrogen bonding. Water molecules are assumed to form dimers in chemical equilibrium with monomers in both liquid and vapor phases. Using our equation of state, which contains only two parameters characterizing the water molecule and a temperature-dependent dimerization constant, we fit the saturation pressure of water to within 0.1% (from the triple point to just below the critical point) and the saturated liquid and vapor volumes to within 1.8 and 3.2%, respectively. Superheated-steam and compressed-water volumes and enthalpies (to 800{sup 0}C, 1000 bars) agree with experiment to within 1.2 and 5.4%, respectively. Consideration is also given to the effect of multiple associations (trimers, tetramers, etc.). Our equation may be useful for engineering applications where the above-quoted accuracy is adequate and where a relatively simple analytic equation of state is desirable for computational efficiency.

• Research Organization: California Univ., Berkeley (USA). Lawrence Berkeley Lab.
• DOE Contract Number: W-7405-ENG-48
• OSTI ID: 5794543
• Report Number(s): LBL-9571; CONF-790925-1
• Resource Relation: Conference: 9. international conference on the properties of steam, Munich, F.R. Germany, 10 Sep 1979
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
15 GEOTHERMAL ENERGY
WATER
EQUATIONS OF STATE
DIMERIZATION
ENTHALPY
PERTURBATION THEORY
VAPOR PRESSURE
VOLUME
CHEMICAL REACTIONS
EQUATIONS
HYDROGEN COMPOUNDS
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
POLYMERIZATION
THERMODYNAMIC PROPERTIES
Geothermal Legacy
400201* - Chemical & Physicochemical Properties
152001 - Geothermal Data & Theory- Properties of Aqueous Solutions