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Using Helmholtz Free Energy to Calculate Liquid Density

Physics Asked by sam o on January 12, 2021

My objective is to find an equation of state (EoS) for density, i.e. density as a function of pressure, temperature and concentration, for aqueous acids, bases and salts.

A StackExchange user suggested that I look into the following paper:

1. Myers JA, Sandler SI, Wood RH. An equation of state for electrolyte solutions covering wide ranges of temperature, pressure, and composition. Ind Eng Chem Res. 2002;41(13):3282–97.

The paper describes the EoS as “the total change in the Helmholtz free energy for forming the electrolyte solution on this path” in which they combine contributions from Peng-Robinson model, Born model, and MSA (Mean Spherical Approximation) model:

$$
A(T,V,bar n)-A^{IGM}(T,V,bar n)=Delta A^{PR}+Delta A^{Born}+Delta A^{MSA},
$$

where $T$ is the temperature of the system, $V$ is the system volume, $bar n$ is the vector of the number of moles of each component of the mixture, and $A^{IGM}$ is the Helmholtz free energy an ideal gas mixture.

In the paper, they included graphs of density vs. molality of aqueous $NaCl, NaBr, CaCl_2$. So it seems like this EoS is what I need, but the paper doesn’t explicitly describe how to calculate density from the EoS.

I’ve seen how taking partial derivatives of Helmholtz free energy results in equations for pressure, entropy, and $mu$, but not for density. I’m wondering if someone has already figured out how exactly one can calculate density from Helmholtz free energy.

UPDATE: Also, I don’t think the Helmholtz free energy I described above (from the paper) is the same as this.

One Answer

In the IAPWS 1995 Formulation, the Helmholz Free Energy is used in connection with the density of Water: Equation 3.2

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Answered by iha10512 on January 12, 2021

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