%0 Journal Article %1 Redlich1964 %A Redlich, Otto %A Meyer, Diane M. %D 1964 %J Chemical Reviews %K density 1964 electrolyte %N 3 %P 221-227 %R 10.1021/cr60229a001 %T The Molal Volumes of Electrolytes %U http://dx.doi.org/10.1021/cr60229a001 %V 64 %X Molal volumes of solutes furnish some interesting informationregarding molecular state and structure.The molal volumes of electrolytes, moreover, round offour understanding of the theory of electrolytes.Special attention may be paid to this topic since itdemonstrates in a very clear manner the importanceof the critical judgment of observations.The molal volumes of nonelectrolytes in solutionsvary little, and nearly linearly, with the concentration(53). Those of electrolytes vary appreciably. Masson(41) found that they can be represented over ratherwide ranges by linear functions of the square root of theconcentration. Redlich and Rosenfeld (51, 52) deriveda linear square root relation from the theory ofDebye and Huckel in 1931. Their relation predictsthe slope for each valence type as a function of the temperature,the compressibility, the dielectric constant Dof the solvent, and its pressure dependence dD/dP.The theory predicts only a limiting law, to be approachedat low concentrations, but the common limitingslope does not depend on the nature of the electrolyte(except its valence type). According to Redlichand Rosenfeld, the individual differences in theslopes found by Masson are due to deviations from thelimiting law at higher concentrations; consequently,Masson’s equations with empirical slopes are unfit forextrapolation to zero concentration.Though this quite simple situation has been clearlydescribed more than 30 years ago, widespread misunderstandinghas existed until now. On one hand, awrong value of the limiting slope was derived from inaccuratedeterminations of dD/dP; on the other hand,the existence of a common limiting slope was often denied on the basis of density determinations of insufficientaccuracy, or just disregarded.Nothing can be easier than the measurement of a densitywith error limits of or but considerableproblems arise when the limits should be reduced to 10-6or 10-7. Yet such accuracy is required for the experimentalproof or disproof of the theoretical limiting law.In view of the thermodynamic connection, a failureof the limiting law for the molal volume implies afailure of the theory of Debye and Huckel. This inevitableconclusion has frequently been ignored.The whole development was reviewed (54) in 1940.In the following, the attention will be concentratedmainly on later literature.

@article{Redlich1964, abstract = {Molal volumes of solutes furnish some interesting informationregarding molecular state and structure.The molal volumes of electrolytes, moreover, round offour understanding of the theory of electrolytes.Special attention may be paid to this topic since itdemonstrates in a very clear manner the importanceof the critical judgment of observations.The molal volumes of nonelectrolytes in solutionsvary little, and nearly linearly, with the concentration(53). Those of electrolytes vary appreciably. Masson(41) found that they can be represented over ratherwide ranges by linear functions of the square root of theconcentration. Redlich and Rosenfeld (51, 52) deriveda linear square root relation from the theory ofDebye and Huckel in 1931. Their relation predictsthe slope for each valence type as a function of the temperature,the compressibility, the dielectric constant Dof the solvent, and its pressure dependence dD/dP.The theory predicts only a limiting law, to be approachedat low concentrations, but the common limitingslope does not depend on the nature of the electrolyte(except its valence type). According to Redlichand Rosenfeld, the individual differences in theslopes found by Masson are due to deviations from thelimiting law at higher concentrations; consequently,Masson’s equations with empirical slopes are unfit forextrapolation to zero concentration.Though this quite simple situation has been clearlydescribed more than 30 years ago, widespread misunderstandinghas existed until now. On one hand, awrong value of the limiting slope was derived from inaccuratedeterminations of dD/dP; on the other hand,the existence of a common limiting slope was often denied on the basis of density determinations of insufficientaccuracy, or just disregarded.Nothing can be easier than the measurement of a densitywith error limits of or but considerableproblems arise when the limits should be reduced to 10-6or 10-7. Yet such accuracy is required for the experimentalproof or disproof of the theoretical limiting law.In view of the thermodynamic connection, a failureof the limiting law for the molal volume implies afailure of the theory of Debye and Huckel. This inevitableconclusion has frequently been ignored.The whole development was reviewed (54) in 1940.In the following, the attention will be concentratedmainly on later literature.}, added-at = {2011-01-19T18:07:19.000+0100}, author = {Redlich, Otto and Meyer, Diane M.}, biburl = {https://www.bibsonomy.org/bibtex/2085f393dca486e9de792886a73ad37a3/thorade}, description = {The Molal Volumes of Electrolytes - Chemical Reviews (ACS Publications)}, doi = {10.1021/cr60229a001}, eprint = {http://pubs.acs.org/doi/pdf/10.1021/cr60229a001}, interhash = {cc58ce3185edd44e122c77d2f10ae901}, intrahash = {085f393dca486e9de792886a73ad37a3}, journal = {Chemical Reviews}, keywords = {density 1964 electrolyte}, number = 3, pages = {221-227}, timestamp = {2011-01-19T18:07:19.000+0100}, title = {The Molal Volumes of Electrolytes}, url = {http://dx.doi.org/10.1021/cr60229a001}, volume = 64, year = 1964 }