Calculation of the Dimer Equilibrium Constant of Heavy Water Saturated Vapor

TL;DR

This paper models the dimerization constant of heavy water vapor using thermodynamics and potential interactions, finding it exceeds that of normal water across temperatures, aligning with experimental data.

Contribution

It introduces a thermodynamic model incorporating interactions and potential contributions to calculate the heavy water vapor dimerization constant.

Findings

Heavy water has a higher dimerization constant than normal water at all temperatures.

The model aligns well with experimental data, confirming the influence of molecular interactions.

Differences in heat excitations and interactions explain the excess dimerization constant for heavy water.

Abstract

Water is the most common substance on Earth.The discovery of heavy water and its further study have shown that the change of hydrogen for deuterium leads to the significant differences in their properties.The triple point temperature of heavy water is higher,at the same time the critical temperature is lower.Experimental values of the second virial coefficient of the EOS for the vapor of normal and heavy water differ at all temperatures.This fact can influence the values of the dimerization constant for the heavy water vapor.The equilibrium properties of the dimerization process are described with the methods of chemical thermodynamics.The chemical potentials for monomers (m) and dimers (d)are the functions of their concentrations.The interactions of monomer-dimer and dimer-dimer types are taken into account within the solution of equation for chemical potentials.The obtained expression for the dimerization constant contains the contributions of these types.The averaged potentials are modeled by the Sutherland potential.Theoretical values of the dimerization constant for the heavy water vapor at different temperatures are compared to those for normal water.We see the exceeding of the values for the heavy water at all temperatures.This fact is in good agreement with all experimental data that is available.The excess is related to the differences in the character of the heat excitations of the dimers of normal and heavy water,their rotational constants and energy of their vibrational excitations.Significant role is also played by the monomer-dimer and dimer-dimer interactions.