Raman spectroscopic study of trivalent lanthanides in concentrated aqueous solutions

Abstract

Absrtact.The Raman spectra in the region of the O-H stretching vibration band are used to investigate the effect of lanthanide (III) ions on liquid water structure in concentrated aqueous solutions of CeCl 3 and GdCl 3 (C~0.5‚3 M). The differential spectra, derived from the consequent Raman spectra, have reflected the substantial discrepancy between the spectra of lanthanide (III) salt solutions and pure water as well as the spectra of standard LiCl (C~1.5‚9M) solutions. The new sharp bands (ν max ~ 3180‚3190 cm -1 ) and (ν max~3 360 cm -1 ), observed in the differential spectra, are assumed to two types of aqua-ions: Ln 3+

In situ synthesis of PuCl3 and corresponding Raman and density functional theory vibrational modes

“…57,58 Further structure from 3,300 to 3,500 cm À1 is attributed to O-H stretching due to the presence of water. 59 This is corroborated by the p-XRD data, which indicated the presence of CeCl 3 hydrate and oxide crystalline phases. The broad structure from 1,100 to 1,200 cm À1 is likely due to 2LO overtone, 60 while structure around 1,600 cm À1 can likely be attributed to graphitic carbon, which suggests the presense of some residual organic material likely introduced from the oil the Ce metal was stored in.…”

“…Additionally, minor structure around 300 and 345 cm −1 , observable in Figure 2b, may additionally be attributed to CeO 2 or Ce‐Cl vibrations of a cerium hydroxyl chloride complex and Ce‐O vibrations of the complex, respectively, which may occur due to hydroxylated and chlorinated CeO 2 material reacted with the concentrated HCl to produce mixed oxy and hydroxy chloride surface features on the oxide particles 57,58 . Further structure from 3,300 to 3,500 cm −1 is attributed to O‐H stretching due to the presence of water 59 . This is corroborated by the p‐XRD data, which indicated the presence of CeCl 3 hydrate and oxide crystalline phases.…”