Degree of dimerization, effective polarizability of molecules and heat capacity of the saturated water vapor

TL;DR

This study investigates how water vapor's effective polarizability and heat capacity are influenced by water dimers, revealing temperature-dependent dimerization effects and providing insights into molecular interactions in saturated vapor.

Contribution

It offers a detailed analysis of water dimer vibrations, their impact on dielectric properties, and the temperature dependence of dimer concentration in saturated vapor.

Findings

Dimerization becomes significant for T/Tc > 0.8.

Effective polarizability and heat capacity are mainly affected by dimer vibrations.

The model accurately reproduces experimental data, validating the dimer concentration approach.

Abstract

The work is devoted to the investigation of properties of water vapor. The main attention is focused on the physical nature of its effective polarizability and heat capacity at constant volume. We show that the specific temperature dependencies of these characteristics are mainly caused by thermal vibration excitations of water dimers. In connection with this we determine normal coordinates for the dimer vibrations. We investigate fluctuations of the dipole moments of dimers in details and consider their contributions to the dielectric permittivity of the water vapor. We also took into account the contribution of the interparticle interactions on the heat capacity. Analyzing the behavior of the effective polarizability and heat capacity we defined the temperature dependence of the dimer concentration on the coexistence vapor-liquid curve. The noticeable dimerization in the saturated water vapor takes place only for temperatures T/Tc > 0.8 (Tc is the critical temperature). It is important to note that the successful reproduction of the effective polarizability and heat capacity can serve good test for the correct description of the dimer concentration in different approaches.