Structure of aqueous sodium sulfate solutions derived from X-ray diffraction

A rapid liquid X-ray diffractometer was used to study the time-averaged and space-averaged structure of aqueous sodium sulfate solutions at 298 and 323 K. Difference radial distribution functions of the solutions were obtained from accurate diffraction data. The interaction distances of Na+-OH2 and S-H2O in solutions were found to be 0.235 and 0.385 nm, respectively, after deconvolution of superposition peaks by Gaussian multi-peak fitting program. The characteristic distance of the NaSO4 contact ion pairs in higher concentration solutions was determined to be 0.345 nm, suggesting that the Na+ ions coordinated with SO42 ions in the mono-dentate form. Effects of concentration and temperature on the hydration structure of the solutions were discussed in the present paper. With a decrease in concentration, the contributions of the H2O to the diffraction pattern increase, the average coordination number of the Na+ ions hardly changes, while the hydration number of SO42 ions increases slightly. The formation of NaSO4 contact ion pairs becomes easier at higher temperature. The structure of hydrogen bond in dilute solutions is broken to a considerable extent with rising temperature, and the peak at 0.290 nm splits into two peaks at 0.275 and 0.305 nm, respectively. Supported by the National Natural Science Foundation of China (Grant No. 20873172) and Prior Special Fund of the Major State Basic Research Development of China (Grant No. 2008CB617612)