Please use this identifier to cite or link to this item: https://hdl.handle.net/2440/128773
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Type: Journal article
Title: A study of the relationship between water and anions of the Hofmeister series using pressure perturbation calorimetry
Author: Bye, J.
Falconer, R.
Citation: Physical Chemistry Chemical Physics, 2015; 17(21):14130-14137
Publisher: Royal Society of Chemistry
Issue Date: 2015
ISSN: 1463-9076
1463-9084
Statement of
Responsibility: 
Jordan W. Bye and Robert J. Falconer
Abstract: Pressure perturbation calorimetry (PPC) was used to study the relationship between water and sodium salts with a range of different anions. At temperatures around 25 °C the heat on pressurisation (ΔQ) from 1 to 5 bar was negative for all solutions relative to pure water. The raw data showed that as the temperature rose, the gradient was positive relative to pure water and the transition temperature where ΔQ was zero was related to anion surface charge density and was more pronounced for the low-charge density anions. A three component model was developed comprising bulk water, the hydration layer and the solute to calculate the molar expansivity of the hydration layer around the ions in solution. The calculated molar expansivities of water in the hydration layer around the ions were consistently less than pure water. ΔQ at different disodium hydrogen phosphate concentrations showed that the change in molar enthalpy relative to pure water was not linear even as it approached infinite dilution suggesting that while hydration layers can be allocated to the water around ions this does not rule out interactions between water and ions extending beyond the immediate hydration layer.
Keywords: Anions
Sodium
Water
Salts
Solutions
Calorimetry
Pressure
Thermodynamics
Models, Molecular
Rights: This journal is©the Owner Societies 2015. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
DOI: 10.1039/c5cp00571j
Appears in Collections:Aurora harvest 8
Chemistry and Physics publications

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