Measurement and Prediction of Molar Volumes of Bivalent Metal Sulfates and Their Mixtures in Aqueous Solution

• Published in: Journal of solution chemistry Vol. 53; no. 1; pp. 203 - 227
• Main Authors: Vielma, Tuomas, Hnedkovsky, Lubomir, Hefter, Glenn
• Format: Journal Article
• Language: English
• Published: New York Springer US 2024; Springer Nature B.V
• Subjects: Aqueous solutions; Chemistry; Chemistry and Materials Science; Condensed Matter Physics; Electrolytes; Geochemistry; Industrial Chemistry/Chemical Engineering; Inorganic Chemistry; Metal sulfates; Mixtures; Molar volume; Oceanography; Physical Chemistry; Sulfates; Temperature; Cobalt sulfate; Molar volume; Prediction; Manganese sulfate; Density; Nickel sulfate; Copper sulfate
• ISSN: 0095-9782; 1572-8927
• DOI: 10.1007/s10953-023-01252-9

Densities of aqueous solutions of MnSO
4
, CoSO
4
, NiSO
4
and CuSO
4
have been measured by vibrating tube densimetry up to near-saturation concentrations over the temperature range 293.15
≤
T
/
K
≤
343.15 at 5 K intervals and at 0.1 MPa pressure. Apparent molar volumes,
V
ϕ
, calculated from the densities revealed close similarities among all four electrolytes, with their
V
ϕ
values essentially differing by constant concentration-independent addends for each salt at each temperature. It was found that there is an almost linear relationship between
V
ϕ
(MSO
4
,aq) and the M–O bond length of the hydrated cations obtained from structural studies. This relationship can be used to predict values of
V
ϕ
(MSO
4
,aq) for other sulfate salts over wide ranges of concentration and temperature, providing that the requisite structural data are available. Measurements of selected ternary, quaternary and quinary mixtures of these electrolytes at constant total concentrations showed that their
V
ϕ
values almost always exhibit linear mixing (Young’s rule) behavior at all temperatures investigated. This finding can be exploited to predict the volumetric properties of solutions containing complex mixtures of bivalent metal sulfates.