Abstract
The first direct measurements over a range of temperatures from 25–350°C are reported for cation-oxygen (water) distances in aqueous solutions at equilibrium saturated vapour pressures. The silver-oxygen (first shell water) bond lengths in AgNO 3 and AgClO 4 solutions were obtained using extended X-ray absorption fine structure (EXAFS) measurements on the silver K-edge. At 25°C and 1 bar, the Ag + ion is coordinated by four inner sphere water ligands with an average silver-oxygen distance of 2.32 (±0.01) Å. With increasing temperature to 350°C, the silver-oxygen (H 2O) bond length decreases by about 0.10 (±0.01) Å and the coordination number decreases from 4 to ∼3. The Debye-Waller factors remain approximately constant with increasing temperature. Silver-nitrate ion pairing (as AgNO 0 3) was observed only at 200 and 300°C in an 0.10 AgNO 3/3.00 m HNO 3 solution for which the silver-nitrogen (nitrate) distances of 3.24 and 3.27 Å, respectively, were obtained.
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