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Electrolyte-UNIQUAC-NRF Model Based on Ion Specific Parameters for the Correlation of Mean Activity Coefficients of Electrolyte Solutions

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Abstract

The Electrolyte-UNIQUAC-NRF excess Gibbs function was applied to estimate ion specific adjustable parameters of various salts by global optimization of the experimental activity coefficients of 54 electrolyte solutions. Twenty-three ion specific parameters were obtained for water and several cations and anions. The estimated individual ion parameters have been used to predict osmotic coefficient of electrolyte solutions. By using only the specific values for ions, the anion–cation and ion–water interaction parameters of different salts can be precisely estimated. Consequently, the interaction parameters of sparingly insoluble salts without experimental activity data can be easily calculated. For a case study, the solubility of CaSO4 was predicted in relatively good agreement with experimental values over a wide range of temperatures up to 473.18 K.

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Abbreviations

A ϕ :

Debye–Hückel constant

g :

Gibbs energy function

u :

Internal energy function

u ij :

Energy interaction parameter

I x :

Ionic strength on the mole fraction basis

m :

Molality

M W :

Molecular weight of water

R :

Universal gas constant

T :

Absolute temperature

x :

Mole fraction

X :

Effective mole fraction

Z :

Coordination number

z :

Charge number of ionic species

r i :

Volume parameter of species i

q i :

Surface parameter of species i

N p :

Number of experimental data

γ :

Activity coefficient

ν :

Stoichiometric ionization number

Γ ij :

Nonrandom factor

τ ij :

Interaction energy parameter between anion and cation

τ Kw :

Interaction energy parameter between ion and solvent

\( \theta^{\prime}_{i} \) :

Effective area fractions of i

\( \theta^{\prime}_{ij} \) :

Effective local area fractions of j around i

\( \Upphi^{\prime}_{i} \) :

Effective volume fraction

σ γ :

Standard deviation of activity coefficient

σ ϕ :

Standard deviation of osmotic coefficient

calc:

Calculated

exp:

Experimental

ex:

Excess

LR:

Long-range

SR:

Short-range

*:

Unsymmetrical convention

∞:

Infinite dilution

c:

Combinatorial

r:

Residual

A:

Anion

C:

Cation

W:

Water

±:

Mean

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Authors and Affiliations

  1. School of Chemical, Gas and Petroleum Engineering, Semnan University, Semnan, Iran

    Hengameh Ahmadi & Kiana Peyvandi

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  1. Hengameh Ahmadi
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  2. Kiana Peyvandi
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Correspondence to Kiana Peyvandi.

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Ahmadi, H., Peyvandi, K. Electrolyte-UNIQUAC-NRF Model Based on Ion Specific Parameters for the Correlation of Mean Activity Coefficients of Electrolyte Solutions. J Solution Chem 46, 1202–1219 (2017). https://doi.org/10.1007/s10953-017-0635-6

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