Starting from known properties of non-specific salt effects on the surface tension at an air–water interface, we propose the first general, detailed qualitative molecular mechanism for the origins of ion-specific (Hofmeister) effects on the surface potential difference at an air–water interface; this mechanism suggests a simple model for the behaviour of water at all interfaces (including water–solute interfaces), regardless of whether the non-aqueous component is neutral or charged, polar or non-polar Specifically, water near an isolated interface is conceptually divided into three layers, each layer being 1 water-molecule thick We propose that the solute determines the behaviour of the adjacent first interfacial water layer ( I 1 ); that the bulk solution determines the behaviour of the third interfacial water layer ( I 3 ), and that both I 1 and I 3 compete for hydrogen-bonding interactions with the intervening water layer ( I 2 ), which can be thought of as a transition layer The model requires that a polar kosmotrope (polar water-structure maker) interact with I 1 more strongly than would bulk water in its place; that a chaotrope (water-structure breaker) interact with I 1 somewhat less strongly than would bulk water in its place; and that a non-polar kosmotrope (non-polar water-structure maker) interact with I 1 much less strongly than would bulk water in its place We introduce two simple new postulates to describe the behaviour of I 1 water molecules in aqueous solution The first, the ‘relative competition’ postulate, states that an I 1 water molecule, in maximizing its free energy (—δG), will favour those of its highly directional polar (hydrogen-bonding) interactions with its immediate neighbours for which the maximum pairwise enthalpy of interaction (—δ H ) is greatest; that is, it will favour the strongest interactions We describe such behaviour as ‘compliant’, since an I 1 water molecule will continually adjust its position to maximize these strong interactions Its behaviour towards its remaining immediate neighbours, with whom it interacts relatively weakly (but still favourably), we describe as ‘recalcitrant’, since it will be unable to adjust its position to maximize simultaneously these interactions The second, the ‘charge transfer’ postulate, states that the strong polar kosmotrope–water interaction has at least a small amount of covalent character, resulting in significant transfer of charge from polar kosmotropes to water–especially of negative charge from Lewis bases (both neutral and anionic); and that the water-structuring effect of polar kosmotropes is caused not only by the tight binding (partial immobilization) of the immediately adjacent ( I 1 ) water molecules, but also by an attempt to distribute among several water molecules the charge transferred from the solute When extensive, cumulative charge transfer to solvent occurs, as with macromolecular polyphosphates, the solvation layer (the layer of solvent whose behaviour is determined by the solute) can become up to 5- or 6-water-molecules thick We then use the ‘relative competition’ postulate, which lends itself to simple diagramming, in conjunction with the ‘charge transfer’ postulate to provide a new, startlingly simple and direct qualitative explanation for the heat of dilution of neutral polar solutes and the temperature dependence of relative viscosity of neutral polar solutes in aqueous solution This explanation also requires the new and intriguing general conclusion that as the temperature of aqueous solutions is lowered towards o °C, solutes tend to acquire a non-uniform distribution in the solution, becoming increasingly likely to cluster 2 water molecules away from other solutes and surfaces (the driving force for this process being the conversion of transition layer water to bulk water) The implications of these conclusions for understanding the mechanism of action of general (gaseous) anaesthetics and other important interfacial phenomena are then addressed

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S0033583500005369

The Hofmeister effect and the behaviour of water at interfaces.

Preface 1. Introduction 2. The theory of membrane potentials 3. The theory of membrane potentials in ion-selective electrodes 4. Principal properties of ion-selective electrodes 5. Experimental techniques 6. Ion-selective electrodes with solid or glassy membranes 7. Ion-selective electrodes with liquid membranes 8. Potentiometric biosensors 9. Voltammetry at the interface of two immiscible electrolyte Appendix Index.

Ion-selective electrodes

A disposable integrated miniaturized array of chemical sensors for analyzing concurrently a number of analytes in a fluid sample is described. Each sensor is a complete electrochemical cell consisting of its own individual reference and indicator electrodes and is selective with respect to a particular analyte in the sample. Where required, a sensor can be individually calibrated, such that each analysis can be read directly.

Integrated array of electrochemical sensors

It is here established that potentiometric polymeric membrane electrodes based on electrically neutral ionophores are useful analytical tools for heavy metal ion determinations in drinking water at nanomolar total concentrations. This means that they can compete with the most sophisticated techniques of instrumental analysis. With optimized ion-selective membranes based on the lead-selective ionophore 4-tert-butylcalix[4]arenetetrakis(thioacetic acid dimethylamide) as model example, a number of native and spiked drinking water samples are potentiometrically assessed for lead, and the results compared with ICPMS measurements. The goal of this work is to demonstrate that detection limits in real world samples are routinely achieved that are, with 1.5 ppb, at least 10-fold lower than the lead action limit imposed by the U.S. Environmental Protection Agency (15 ppb). In contrast to earlier reports, different conditioning and measuring protocols are followed, and membranes and inner filling solution of optimiz...

Potentiometric Polymeric Membrane Electrodes for Measurement of Environmental Samples at Trace Levels: New Requirements for Selectivities and Measuring Protocols, and Comparison with ICPMS

Richard A Durst

Papers

Ion-selective electrodes