Raman spectral studies of solutions of alkali metal perchlorates in dimethyl sulfoxide and water

1985 ◽  
Vol 63 (7) ◽  
pp. 1351-1356 ◽  
Author(s):  
M. I. S. Sastry ◽  
Surjit Singh
Keyword(s):  
Alkali Metal ◽  
Aqueous Solutions ◽  
Dimethyl Sulfoxide ◽  
Raman Spectra ◽  
Ion Pairs ◽  
Spectral Studies ◽  
Increase With Increase ◽  
Raman Spectral ◽  
Depolarization Ratios

Raman spectra of solutions of alkali metal perchlorates in dimethyl sulfoxide (DMSO) in the Cl—O, C—S, and S=O stretching regions, as well as of perchlorates in aqueous solutions in the Cl—O stretching region are reported. The results are discussed in terms of half-bandwidths, relative intensities, and depolarization ratios. For H2O the half-bandwidth of the Cl—O stretching band at ~935 cm−1 is almost double the value in DMSO solutions. Solutions of perchlorates in DMSO show two symmetric bands in the Cl—O stretching region, whereas in aqueous solutions only one band is observed. The half-bandwidths in perchlorate solutions in DMSO for the C—S stretching band increase with increase in concentration of perchlorate compared to that of liquid DMSO. The band contours in the S=O stretching region in DMSO solutions also show significant changes. These observations are explained on the basis of formation of ion pairs of metal perchlorates in solutions of DMSO and ion hydrates in the case of aqueous solutions.

Vibrational Spectral Studies of Hexaquozinc Nitrate and Hexaquozinc Nitrate-d2

1971 ◽  
Vol 49 (9) ◽  
pp. 1510-1514 ◽  
Author(s):  
M. H. Brooker ◽  
D. E. Irish
Keyword(s):  
Aqueous Solutions ◽  
Raman Spectra ◽  
Deuterium Oxide ◽  
Ionic Association ◽  
Spectral Studies ◽  
Site Symmetry ◽  
Infrared And Raman Spectra ◽  
Concentrated Aqueous Solutions ◽  
Site Group ◽  
A Site

Infrared and Raman spectra are reported for the hexaquozinc nitrate crystal. Replacement of water by deuterium oxide causes a remarkable intensity reversal of components in the ν3 nitrate region and provides Raman spectra free from interference in the 2ν2 and ν4 regions. The nitrate spectrum is interpreted in terms of a site group approximation. The spectra are compared with those of concentrated aqueous solutions and partially dehydrated crystals to point up changes which result from a lowered site symmetry and those which result from ionic association.

scholarly journals Raman Spectral Studies of Aqueous Acidic Pyrazine Solutions

1995 ◽  
Vol 50 (2-3) ◽  
pp. 274-282 ◽  
Author(s):  
Alexandre G. Brolo ◽  
Donald E. Irish
Keyword(s):  
Raman Spectra ◽  
Species Distribution ◽  
Spectral Studies ◽  
Acidic Media ◽  
Distribution Diagram ◽  
Protonated Forms ◽  
Species Distribution Diagram ◽  
Diprotonated Form ◽  
High Concentrations ◽  
Raman Spectral

Abstract Raman spectra of aqueous pyrazine have been investigated in acidic media: HCl from pH = 4 up to 11 M; HCLO4 from 0.1 M to 12 M; H2SO4 form 0.1 M to 18 M. From observation of the shifts of the bands from neutral solutions, it has been possible to identify bands uniquely characteristic of unprotonated pyrazine and its two protonated forms. The diprotonated form was only observed for high concentrations of HCLO4 and H2SO4. From bandfitting of the spectral contours it has been possible to construct the species distribution diagram and estimate the pK values. Raman bands of the three species have been identified and assigned. The results are used to explain an unassigned band at 1235 cm-1, reported by several authors, in SERS from pyrazine on silver and gold electrodes.

Raman Spectral Studies of Cadmium–Nitrite Interactions in Aqueous Solutions and Crystals

1975 ◽  
Vol 53 (10) ◽  
pp. 1414-1423 ◽  
Author(s):  
Donald E. Irish ◽  
Roderick V. Thorpe
Keyword(s):  
Aqueous Solutions ◽  
High Frequency ◽  
Deformation Mode ◽  
Formation Constants ◽  
Ratio Method ◽  
Spectral Studies ◽  
Nitrite Concentration ◽  
Nitrite Ion ◽  
Mole Ratio Method ◽  
Raman Spectral

Raman spectra of aqueous solutions containing Cd2+ and NO2− clearly reveal the presence of solvated nitrite ion and of complexes. A band at 861 cm−1 is characteristic of the latter. The free nitrite concentration was measured from the intensity of the 817 cm−1 line and the average ligand number was evaluated for solutions with composition prescribed by the mole-ratio method. Four cumulative formation constants were deduced: β1 = 61.6; β2 = 993; β3 = 2390; β4 = 1899. Evidence that nitrite chelates Cd2+ through the two oxygen atoms is presented. The diagnostic spectral evidence consists of a high intensity, high frequency deformation mode and low intensity N—O stretching Raman bands with frequencies almost identical to those of the solvated nitrite ion. Data are also presented for solid Cd(NO2)2 and Kx−2Cd(NO2)x(x = 3,4,5).

Vibrational Spectral Studies of Solutions at Elevated Temperatures and Pressures. III. A Furnace Assembly for Raman Spectral Studies to 300°C and 15 MPa

1982 ◽  
Vol 36 (2) ◽  
pp. 137-140 ◽  
Author(s):  
D. E. Irish ◽  
T. Jarv ◽  
C. I. Ratcliffe
Keyword(s):  
High Temperature ◽  
Aqueous Solutions ◽  
Elevated Temperatures ◽  
Chemical Processes ◽  
Spectral Studies ◽  
Raman Spectral

The design of a furnace assembly for maintaining aqueous solutions at temperatures up to 300°C and controlled pressures of up to 15 MPa is described. The apparatus is being used to monitor the chemical processes taking place in high-temperature aqueous solutions. Spectra of the Zn(NO3)2/H2O system and the HCl/H2O system are presented as examples.

Raman spectral studies of solutions at elevated temperatures and pressures.13. Sodium formate – water

1993 ◽  
Vol 71 (10) ◽  
pp. 1728-1733 ◽  
Author(s):  
Richard J. Bartholomew ◽  
Donald E. Irish
Keyword(s):  
Raman Spectra ◽  
Elevated Temperatures ◽  
Sodium Formate ◽  
Fermi Resonance ◽  
Spectral Studies ◽  
Coupling Constant ◽  
Ambient Conditions ◽  
Modes Of Vibration ◽  
Resonance Doublet ◽  
Raman Spectral

Raman spectra of the formate anion in water (H2O and D2O) have been measured for four concentrations under ambient conditions and for two concentrations at temperatures ranging from 49 to 239 °C and a pressure of 10 MPa. Five of the six fundamental modes of vibration are polarized. This result is inconsistent with C2ν symmetry. The Fermi resonance doublet clearly results from the interaction of 2ν5 and ν1. The latter mode decreases in frequency as the temperature rises, thus increasing the coupling and hence the intensity of the 2ν5 component. The coupling constant, W, and the positions of the unperturbed bands [Formula: see text] and [Formula: see text] have been calculated. No evidence to support a bifurcated structure for the solvated anion was found.

Sign in / Sign up

Export Citation Format

Share Document