Building research at the National Bureau of Standards 1968-1974

Gallagher, Neil Ignatius

doi:10.6028/nbs.bss.75

Cited by 1 publication

(2 citation statements)

References 15 publications

(17 reference statements)

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“…The limiting conductance of NaCl that would be given by the Stokes friction (stick, eq 3) using the bare-ion radii for Na + and Cl -(0.9 and 1.8 Å, respectively, taken from ref 8) is shown in Figure 1 along with the bulk solvent shear viscosity. 27 It is interesting to note at the outset that the increase in conductivity with decreasing solvent density obtained via this expression is somewhat superlinear. Hence, even the observation of a linear rate of increase with decreasing density would, in itself, signify increasing effective ion sizes.…”

Section: Limiting Ionic Conductancementioning

confidence: 95%

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Structural and Dynamical Origins of Ionic Mobilities in Supercritical Water

2001

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We report the results of simulations of the ionic mobility of Na+ and Cl- in supercritical water at 673 K, including solvent densities below those previously considered in simulation or experimental data. By considering these results along with earlier published analyses, we find that the spatially inhomogeneous solvation structure around the ions and solvent dynamics are strongly coupled in determining transport rates. The appearance of a plateau in the infinite-dilution conductivity over a wide range of intermediate solvent densities is a result of a subtle balance of excess (dielectric) friction and a nonlinear variation in the viscous friction. The result is strongly influenced by the inhomogeneous solvent density around the ions, but cannot be rationalized on the basis of only structural criteria. A reduced effective ionic radius is introduced that is inversely proportional to the Walden product and can be trivially evaluated from experimental conductivity results. It is shown that when represented in this way, conductivity data smoothly and continuously vary with solvent density over the entire density range and are much more readily interpreted. In particular, this effective ionic size exhibits a maximum at a density of ca. 0.2 g/cm3, providing a natural division between high- and low-density solvents. At higher densities, the structure of the first hydration shell of the ions is only weakly dependent on solvent density, while at lower densities, entropic forces increasingly lead to the loss of this primary solvation shell. These results are consistent with the view that, with decreasing solvent density down to this natural division, an increasing imbalance between ion−water and water−water interactions produces an increasingly rigid ionic solvation shell and thus an increasing friction on the ion.

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Section: Limiting Ionic Conductancementioning

confidence: 95%

“…In the solvent density range of 0.2-0.7 g/cm 3 , the viscosity of water at 673 K varies by ca. 300% and in a highly nonlinear manner, 27 as shown in Figure 1. This strongly suggests that the structural view provides an incomplete picture.…”

Section: Introductionmentioning

confidence: 93%