Structure of the electrical double layer at aqueous gold and silver interfaces for saline solutions

We report the structure of the electrical double layer, determined from molecular dynamics simulations, for a range of saline solutions (NaCl, KCl, MgCl2 and CaCl2) at both 0.16 and 0.60molkg(-1) on different facets of the gold and silver aqueous interfaces. We consider the Au/Ag(111), native Au/Ag(100) and reconstructed Au(100)(5×1) facets. For a given combination of metallic surface and facet, some variations in density profile are apparent across the different cations in solution, with the corresponding chloride counterion profiles remaining broadly invariant. All density profiles at the higher concentration are predicted to be very similar to their low-concentration counterparts. We find that each electrolyte responds differently to the different metallic surface and facets, particularly those of the divalent metal ions. Our findings reveal marked differences in density profiles between facets for a given metallic interface for both Mg(2+) and Ca(2+), with Na(+) and K(+) showing much less distinction. Mg(2+) was the only ion for which we find evidence of materials-dependent differences in interfacial solution structuring between the Ag and Au.

Effect of multiple cations in the feed solution on the performance of forward osmosis

In this study, different combinations of feed stream such as 0.2, 0.3 and 0.4 M of CaCl2 were, respectively, added with 1.0, 0.9 and 0.8 M of NaCl while maintaining the draw solution concentration at either 2.0 M of NaCl or CaCl2 in order to compare likely changes to the flux generated when the feed stream contained NaCl only. The results obtained showed that more constituents in feed stream generated lesser flux. Increase in CaCl2 concentration in feed stream resulted in more severe dilutive internal concentration polarisation (DICP) and hence, reduction in the performance ratio. The temperature and distribution of aggregated particle size also played a significant role in the overall performance of forward osmosis process. Further analysis showed that there is a relationship between the normalised driving force and flux behaviour which is governed by the effect of DICP. Additionally, the reflection coefficient was not unity as less than 2% traces of salt was found to permeate alongside with water towards the draw solution side. © 2014 © 2014 Balaban Desalination Publications. All rights reserved.

Characterisation of ion transport in sulfonate based ionomer systems containing lithium and quaternary ammonium cations

Two sulfonated ionomers based on poly(triethylmethyl ammonium 2-acrylamido-2-methyl-1-propane sulfonic acid) (PAMPS) and containing mixtures of Li⁺ and quaternary ammonium cations are characterised. The first system contains Li⁺ and the methyltriethyl ammonium cation (N1222) in a 1:9 molar ratio, and the ⁷Li NMR line widths showed that the Li⁺ ions are mobile in this system below the glass transition temperature (105°C) and are therefore decoupled from the polymer segmental motion. The conductivity in this system was measured as 10^-5 Scm^-1 at 130°C. A second PAMPS system containing Li⁺ and the dimethylbutylmethoxyethyl ammonium cation (N114(2O1)) in a 2:8 molar ratio showed much lower conductivities despite a significantly lower Tg (60°C), possibly due to associations between the Li⁺ and the ether group on the ammonium cation, or between the latter cations and the sulfonate groups.

Competition between cluster fragmentation, C–C bond coupling and C–X bond activation in silver hexynyl cluster cations, [(C4H9CCAg)nAg]+. Size does matter!

Silver hexynyl cluster cations, [(C4H9CCAg)nAg]+, exhibit a rich unimolecular chemistry that is dependant on the cluster size, n (1–5), cluster fragmentation (for all n > 1); C–C bond coupling (n = 3 & 4); C–H bond activation with comcomitant silver hydride formation (n = 1 & 4); C–C bond activation (n = 1 & 4).