Partial molal expansibilities from the temperature of maximum density of aqueous solutions

Kuppers, James R.

doi:10.1021/j100603a020

Cited by 7 publications

(6 citation statements)

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“…Also, by extrapolating measured values of AO/x to infinite dilution, one may obtain a value of the partial molal expansibility of the solute at 3.98 "C, a potentially meaningful indicator of solution structural properties (5). The apparent molal expansibility of solutes in aqueous solution was used earlier as an index of the structural interaction of solutes with water (6).…”

Section: J A~~e Smentioning

confidence: 99%

Comment: A problem in extracting structure information from the temperature of maximum density for aqueous solutions

Kuppers¹

1977

Can. J. Chem.

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(ii.l1?7ent of'C!~erilicti:v. The Ut~il.el.sitj, oj'fiortiz Corolinci i i r Chiirlotte, Cl~trriurre, NC28223 Received September 26. 1976 JAMES R. KUPPERS. Can. J. Chem. 55, 798 (1977).The shift in the temperature of maximum ddnsity for aqueous solutions customarily has been dissected into an ideal and a str~lctnral contribution. This analysis demonstrates that the dissection leads to the formulation of an ideal state which is attained by a fortuitous superposition of temperature dependent properties of pure components and, hence, cannot serve as a reliable reference state for comparing the influence of different solutes upon solution structure. J A~~E SR. KUPPERS. Can. J. Cheni. 55,798 (1977). Le deplacement dans la temperature de densite maximuni de solutions aqueuses est gCn6rale-ment disstqui en termes de contributions idkale et strucrurale. Cette analyse dimonire que cette dissection conduit i la formulation d'un &tat ideal qui peut &tre obtenu par une superposition fortuite de proprittes des coniposants purs qui dependent de la tempirature et qu'ainsi il ne peut pas servir comrne etat de reference adiquat pour comparer l'influence de differents solutes sur la structure de la solution.[Traduit par Ie journal] The shift in the temperature of maximum analogous to identifying conditions under density, TMD, of a water solution relative to which the compressibility factor of an imperfect that of pure water is given by the relation of gas is unity. Wada and U~neda (1)To further clarify this issue let us examine in where x is the mole fraction of solute, u is the thermal coefficient of expansion of pure solute (assumed to be constant over the temperature range considered), f3 1s the coefficient in the parabolic relation to temperature of the molar volume of water In the vicinity of 3.98 "C, V,' is the molar volume of pure solute at 0 "C, V," 1s the molar volume of water at 3.98 "C. and detail the necessary consequences of assuming that AB,, = 0 signifies that the solute has no influence upon the structure of water near its TMD, and then determine whether or not these consequences are consistent with our special concepts of 'ideality' of mixing. Suppose that AQ,, = 0 for a particular solute over a small finite range of concentration. This implies that 8AVMlaT must be zero at any concentration within this range. Now recall that -AV" is the excess volume of mixing.[4]It has been assumed (1-4) that A0 could be decomposed into an 'ideal' term and a 'struc-where V,, V,, and V are the molar volumes of tural' term such that A0 = A@, + A@,,, where pure solute, pure solvent, and solution, all at88, = -xu.V;/(l -x)2f3Vls some specified temperature. Furthermore and The 'ideal' state inferred by this deco~nposition If we now apply eq. 5 at the TMD, then aV/aT = is one in which AV" is not necessarily zero but 0, and it 1s immediately revealed that aAVM/t3T one in which it remains constant over some at the TMD is uniquely determined by aV,jaT finite temperature range. In order that a solution and a V,/aT, which are prop...

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Section: J A~~e Smentioning

confidence: 99%

Comment: A problem in extracting structure information from the temperature of maximum density for aqueous solutions

Kuppers¹

1977

Can. J. Chem.

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“…The shift in the temperature of maximum density (TMD) of water that occurs on dissolution of a solute is now recognized as a useful tool for the investigation of solute induced changes in the structure of liquid water (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13). However, a number of recent papers (6,(10)(11)(12) suggest that some confusion exists as to the appropriate interpretation of the data.…”

Section: Introductionmentioning

confidence: 99%

“…However, a number of recent papers (6,(10)(11)(12) suggest that some confusion exists as to the appropriate interpretation of the data. In particular, a few authors (6,11,12) have used the overall experimentally observed shift in the T M D (AOobs), or parameters derived therefrom (e.g. partial molal expansibility), as a measure of change in the structure of water caused by solid solutes.…”

Section: Introductionmentioning

confidence: 99%

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The interrelationship between partial molal expansibility and the solute induced shift in the temperature of maximum density of water

Macdonald¹,

Hyne²

1976

Can. J. Chem.

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. Can. J. Chem. 54, 3073 (1976).The effect of solutes on the temperature of maximum density (TMD) of water is analysed with emphasis upon the applicability of thermodynamic dissection of the observed change in the TMD (ABobs) into ideal (&Bid) and structural (AO,,) components. The use of TMD as a probe for examining the effect of dissolved solutes on the structural properties of water is critically compared with methods based upon apparent and partial molal expansibilities.

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“…where m is the molality and where the second derivative is to be evaluated at 3.98°and infinite dilution. Subsequently it has been shown4 that eq 1 can be cast into a form which provides a direct link between experiment and a value for the partial molal expansibility of solute at 3.98°and infinite dilution a V2*/aT = -2/3Vi*[A0/*]l (3) or the thermal coefficient of partial volume expansion of solute a* = -2/8Vi"'/P'2*[A»/x]l (4) where [ / ]^i s the limiting value of / at infinite dilution and V2* is the partial molal volume of solute at 3.98°a nd infinite dilution, The reliability of such solute expansibility data will be limited by the precision of extrapolation from experimental measurements. / is quite insensitive to solute concentration for a large number of electrolytes4 at high dilution.…”

Section: Introductionmentioning

confidence: 99%

Partial volume expansibility of simple organic solutes from the temperature of maximum density of aqueous solutions

Kuppers¹

1975

J. Phys. Chem.

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Partial molal expansibilities from the temperature of maximum density of aqueous solutions

Cited by 7 publications

References 2 publications

Comment: A problem in extracting structure information from the temperature of maximum density for aqueous solutions

Comment: A problem in extracting structure information from the temperature of maximum density for aqueous solutions

The interrelationship between partial molal expansibility and the solute induced shift in the temperature of maximum density of water

Partial volume expansibility of simple organic solutes from the temperature of maximum density of aqueous solutions

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