Confocal Raman study on ZnSO4 droplets in the efflorescence process
2009
Confocal Raman technique was used to investigate the structure changes of the ZnSO4 droplets deposited on Teflon substrate in the efflorescence process at the molecular level.Upon decreasing the relative humidity(RH),the symmetric stretching band(ν1-SO2-4)of ZnSO4 droplet blue shifted from 981 cm-1 gradually to 987,998 and 1 008 cm-1,respectively,indicating that the free SO2-4 ion associates with Zn2+ ion as the solution concentration increases and forms various contact ion pairs(CIPs),i.e.,monodentate,bidentate and complicated multidentate chain-structured or web-structured CIPs.Accordingly,two obvious transition points were also observed in the hygroscopic curve of ZnSO4 droplet,implying the structure transformations in the droplet.In order to obtain the information about the contents and evolutions of various components in the droplets,curve fitting technique was used to extract the components at positions of 981,987,998 and 1 008 cm-1 in the spectral range of 945-1 065 cm-1 representing the free SO2-4 ion,monodentate,bidentate and complicated CIPs,respectively.The results indicated that the main component in droplets was free hydrated SO2-4 ion at high RHs.With decreasing the RH,monodentate and bidentate CIPs were formed by Zn2+ and SO2-4 and achieved their highest contents at RHs of 66% to 34%,respectively.Further decreasing the RH,the monodentate and bidentate CIPs gradually changed into multidentate chain-structured CIPs or complicated CIPs webs,which became the main components in supersaturated ZnSO4 droplets as the RH decreased below 34%.
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