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Issue 18, 2016
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The relative diffusive transport rate of SrI2 in water changes over the nanometer length scale as measured by coherent quasielastic neutron scattering

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Abstract

X-ray and neutron scattering have been used to provide insight into the structures of ionic solutions for over a century, but the probes have covered distances shorter than 8 Å. For the non-hydrolyzing salt SrI2 in aqueous solution, a locally ordered lattice of ions exists that scatters slow neutrons coherently down to at least 0.1 mol L−1 concentration, where the measured average distance between scatterers is over 18 Å. To investigate the motions of these scatterers, coherent quasielastic neutron scattering (CQENS) data on D2O solutions with SrI2 at 1, 0.8, 0.6, and 0.4 mol L−1 concentrations was obtained to provide an experimental measure of the diffusive transport rate for the motion between pairs of ions relative to each other. Because CQENS measures the motion of one ion relative to another, the frame of reference is centered on an ion, which is unique among all diffusion measurement methods. We call the measured quantity the pairwise diffusive transport rate Dp. In addition to this ion centered frame of reference, the diffusive transport rate can be measured as a function of the momentum transfer q, where q = (4π/λ)sin θ with a scattering angle of 2θ. Since q is related to the interion distance (d = 2π/q), for the experimental range 0.2 Å−1q ≤ 1.0 Å−1, Dp is, then, measured over interion distances from 40 Å to ≈6 Å. We find the measured diffusional transport rates increase with increasing distance between scatterers over the entire range covered and interpret this behavior to be caused by dynamic coupling among the ions. Within the model of Fickian diffusion, at the longer interionic distances Dp is greater than the Nernst–Hartley value for an infinitely dilute solution. For these nm-distance diffusional transport rates to conform with the lower, macroscopically measured diffusion coefficients, we propose that local, coordinated counter motion of at least pairs of ions is part of the transport process.

Graphical abstract: The relative diffusive transport rate of SrI2 in water changes over the nanometer length scale as measured by coherent quasielastic neutron scattering

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Publication details

The article was received on 22 Sep 2015, accepted on 08 Apr 2016 and first published on 08 Apr 2016


Article type: Paper
DOI: 10.1039/C5CP05663B
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Phys. Chem. Chem. Phys., 2016,18, 12707-12715

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    The relative diffusive transport rate of SrI2 in water changes over the nanometer length scale as measured by coherent quasielastic neutron scattering

    K. A. Rubinson and A. Faraone, Phys. Chem. Chem. Phys., 2016, 18, 12707
    DOI: 10.1039/C5CP05663B

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