lithium-perchlorate and propylene-carbonate

Attenuated total reflection infrared spectroscopy was used to examine the concentration dependent solvation of LiClO4 and NaClO4 electrolytes in propylene carbonate (PC). Factor analysis and curve fitting techniques were performed on the measured spectra and the results compared with ab initio computations to provide evidence for ion-solvent solution geometries. Factor analysis of the measured data allowed the identification of the spectrum of ion-associated PC that is uniquely different from the self-associated PC spectrum. The results indicate Li+ and ClO4- ions are contact ion-paired even at relatively low electrolyte concentrations whereas Na+ and ClO4- ions are not, up to approximately 2 mol dm-3.

Topics: Cations; Electrolytes; Lithium Compounds; Perchlorates; Propane; Sodium Compounds; Solutions; Solvents; Spectrophotometry, Infrared; Vibration

FTIR spectra have been recorded and analyzed for solutions of lithium perchlorate in propylene carbonate (PC), diethyl carbonate (DEC), and PC + DEC mixtures. It has been shown that the carbonyl stretch bands for PC and DEC are very sensitive to the interaction between Li+ and the solvent molecules. They split with addition of LiClO4, indicating a strong interaction of Li+ with PC and DEC through the oxygen group of PC and both oxygen and ether oxygen atoms of DEC. In conjunction with molecular orbital calculation, the optimized geometries of solvation are given. In addition, solvent separated ion pairs and contact ion pairs were observed in LiClO4/DEC solutions, and no preferential solvation of Li+ in LiClO4/PC + DEC solutions were detected.

Topics: Carbonates; Diethyl Pyrocarbonate; Lithium Compounds; Molecular Conformation; Molecular Structure; Perchlorates; Propane; Solutions; Solvents; Spectrophotometry, Infrared

The infrared (IR) spectra of propylene carbonate (PC), gamma-butyrolactone (BL) and diethyl carbonate (DEC) in the presence of LiClO4 have been investigated. It is shown that the interactions between Li+ and these solvents occur on the oxygen atoms of the carbonyl of solvent molecules. On the other hand, spectral curve fitting for band shape of perchlorate anion shows the presence of ion association in these solutions.

Topics: 4-Butyrolactone; Diethyl Pyrocarbonate; Lithium; Lithium Compounds; Organic Chemicals; Perchlorates; Propane; Solvents; Spectrophotometry, Infrared

The infrared (IR) and Raman spectra are reported for solutions of lithium perchlorate in propylene carbonate (PC), N,N-dimethylformamide (DMF) and PC + DMF mixtures. The band splittings of symmetric ring deformation for PC and O=CN deformation for DMF suggest that there is a strong interaction between lithium cations and solvent molecules. The solvent molecules have been assigned to two types, the free and complexed molecules. By a comparison of the intensity for the corresponding bands, it has been concluded that Li+ cations are preferentially solvated by DMF molecules in the LiClO4/PC-DMF solutions. This has been explained by the difference in values of donor number.

Topics: Carbonates; Dimethylformamide; Electrochemistry; Lithium Compounds; Perchlorates; Propane; Solutions; Spectroscopy, Fourier Transform Infrared; Spectrum Analysis, Raman