DOI: 10.1139/v83-084. The partial molar volumes of aqueous metal cations: their prediction and relation to volumes of activation for water exchange

The partial molar volumes of aqueous metal cations: their prediction and relation to volumes of activation for water exchange

10.1139/v83-084

Crossref journal-article

Canadian Science Publishing

Canadian Journal of Chemistry (155)

Abstract

Partial molar volumes [Formula: see text] of the Fe2+, Ni2+, Fe3+, Cr3+, Rh3+, and M(NH3)5OH3+ (M = Cr, Co, Rh, Ir) aqueous ions have been obtained by extrapolation from density measurements at 298.15 K on the perchlorate salt solutions containing added HClO4 where necessary to suppress hydrolysis or oxidation. The values for these high-spin aqua-ions and others in the literature can be represented satisfactorily for ionic charges z = 1 through 4 by[Formula: see text]where [Formula: see text] is the absolute partial molar volume in cm3 mol−1 of Mz+(aq) relative to [Formula: see text] for H+(aq), and r is the Shannon radius in pm of Mz+ with coordination number nc. Volumes of activation ΔVex* for water exchange correlate inversely with [Formula: see text] within the series M2+(aq) and M(NH3)5OH23+(aq) at least, allowing predictions of ΔVex* to be made from [Formula: see text] or the above equation. The physical origin of these correlations is considered.

Bibliography

Swaddle, T. W., & Mak, M. K. S. (1983). The partial molar volumes of aqueous metal cations: their prediction and relation to volumes of activation for water exchange. Canadian Journal of Chemistry, 61(3), 473â480.

Authors 2

Thomas W. Swaddle (first)
Mark K. S. Mak (additional)

References 3 Referenced 65

{'key': 'p_1/p_1_1', 'unstructured': ''}
{'key': 'p_2/p_2_1', 'unstructured': ''}
" - 14.2 5

Dates

Type	When
Created	19 years, 3 months ago (May 8, 2006, 7:06 p.m.)
Deposited	1 month, 3 weeks ago (July 2, 2025, 1:06 p.m.)
Indexed	1 month, 3 weeks ago (July 3, 2025, 12:13 a.m.)
Issued	42 years, 5 months ago (March 1, 1983)
Published	42 years, 5 months ago (March 1, 1983)
Published Print	42 years, 5 months ago (March 1, 1983)

Funders 0

None

BibTeX

@article{Swaddle_1983, title={The partial molar volumes of aqueous metal cations: their prediction and relation to volumes of activation for water exchange}, volume={61}, ISSN={1480-3291}, url={http://dx.doi.org/10.1139/v83-084}, DOI={10.1139/v83-084}, number={3}, journal={Canadian Journal of Chemistry}, publisher={Canadian Science Publishing}, author={Swaddle, Thomas W. and Mak, Mark K. S.}, year={1983}, month=mar, pages={473–480} }

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  "abstract": "<jats:p> Partial molar volumes [Formula: see text] of the Fe<jats:sup>2+</jats:sup>, Ni<jats:sup>2+</jats:sup>, Fe<jats:sup>3+</jats:sup>, Cr<jats:sup>3+</jats:sup>, Rh<jats:sup>3+</jats:sup>, and M(NH<jats:sub>3</jats:sub>)<jats:sub>5</jats:sub>OH<jats:sup>3+</jats:sup> (M\u2002=\u2002Cr, Co, Rh, Ir) aqueous ions have been obtained by extrapolation from density measurements at 298.15\u2002K on the perchlorate salt solutions containing added HClO<jats:sub>4</jats:sub> where necessary to suppress hydrolysis or oxidation. The values for these high-spin aqua-ions and others in the literature can be represented satisfactorily for ionic charges z\u2002=\u20021 through 4 by[Formula: see text]where [Formula: see text] is the absolute partial molar volume in cm<jats:sup>3</jats:sup> mol<jats:sup>\u22121</jats:sup> of M<jats:sup>z+</jats:sup>(aq) relative to [Formula: see text] for H<jats:sup>+</jats:sup>(aq), and r is the Shannon radius in pm of M<jats:sup>z+</jats:sup> with coordination number n<jats:sub>c</jats:sub>. Volumes of activation \u0394V<jats:sub>ex</jats:sub>* for water exchange correlate inversely with [Formula: see text] within the series M<jats:sup>2+</jats:sup>(aq) and M(NH<jats:sub>3</jats:sub>)<jats:sub>5</jats:sub>OH<jats:sub>2</jats:sub><jats:sup>3+</jats:sup>(aq) at least, allowing predictions of \u0394V<jats:sub>ex</jats:sub>* to be made from [Formula: see text] or the above equation. The physical origin of these correlations is considered. </jats:p>",
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