Logo image
Back
An investigation of Zdanovskii's rule for predicting the water activity of multicomponent aqueous strong electrolyte solutions
Journal article   Peer reviewed

An investigation of Zdanovskii's rule for predicting the water activity of multicomponent aqueous strong electrolyte solutions

D. Rowland and P.M. May
Journal of Chemical & Engineering Data, Vol.57(9), pp.2589-2602
2012
DOI: https://doi.org/10.1021/je3006612
url
Link to Published Version *Subscription may be requiredView

Abstract

The effectiveness of Zdanovskii's rule as a fundamental method of predicting water activities in mixed aqueous strong electrolyte solutions has been investigated. Unfortunately, when literature data available for more than 100 ternary systems (i.e., two electrolytes plus water) were examined, sufficient measurements were rarely available to test Zdanovskii's rule conclusively. This is because few mixed systems have been studied by more than one (independent) investigator and, in these few cases, the differences between reported water activities are generally much larger than typical estimates of experimental uncertainty. Most of the electrolyte systems considered in this work are found statistically to conform with Zdanovskii's rule but often only within a worryingly large tolerance in residuals. However, when data are taken from a single source, deviations from Zdanovskii's rule, significant in comparison to the stated experimental precision, can often be attributed equally well to small, unrecognized, systematic errors. This dilemma can only be resolved by more experimental measurements of sufficient accuracy to achieve better agreement between independent observers. Our findings imply that (a) confidence in deviations from Zdanovskii's rule typically depends on a subjective judgment of data quality and (b) Zdanovskii's rule, albeit often difficult to validate, provides an impressively general method for estimating water activities in mixed aqueous strong electrolyte solutions, with a certainty that, objectively, is as good as or better than current experimental capability.

Details

Metrics

108 Record Views
18 Times Cited - Web of Science

InCites Highlights

These are selected metrics from InCites Benchmarking & Analytics tool, related to this output

Citation topics
2 Chemistry
2.89 Ionic, Molecular & Complex Liquids
2.89.462 Excess Molar Volumes
Web Of Science research areas
Chemistry, Multidisciplinary
Engineering, Chemical
Thermodynamics
ESI research areas
Chemistry
Logo image