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Quantification of hydroxide in aqueous solutions by Raman spectroscopy

Conference ·
OSTI ID:634000
Quantification of hydroxide in aqueous solutions by Raman spectroscopy is complicated by the fact that the O-H stretching band of hydroxide is overlapped by the broad, symmetric O-H stretching band of water. This overlap is further complicated by the fact that the shape of the O-H stretching band of water is strongly influenced by the concentration of hydroxide. The O-H stretching band of water is believed to consist of five components that result from differing configurations of intramolecular hydrogen bonding. The Raman spectral region from 300 to 4,450 cm{sup {minus}1} was investigated for NaOH solutions ranging in concentration from 0.2 to 50 weight percent. At approximately 5 weight percent NaOH, a distinct shoulder appears on the high energy side of the O-H stretching band of water. As the NaOH concentration increases, this shoulder becomes a sharp distinct band at 3,600 cm{sup {minus}1} which is still not resolved from the O-H stretching band of water. As the O-H stretching band of hydroxide increases, the O-H stretching band of water broadens and its contour becomes smoother. By curve fitting five Gaussian functions to the O-H stretching band of water, the asymmetric band due to hydroxide was extracted from the composite band of the NaOH solution. The curve fitting routine resulted in a linear relationship for the area of the hydroxide band in the concentration range from 5 to 50 weight percent NaOH. The uncertainty in the curve fitting at concentrations below 5 weight percent was too large to establish a reliable calibration curve. Below 5 weight percent NaOH, direct spectral subtraction of the water band from the NaOH solution band resulted in a linear relationship in the range of 5 down to 0.2 weight percent NaOH. The peak shape obtained for the hydroxide band by the two different techniques was very similar. A comparison of the results obtained from peak fitting and spectral subtraction is presented.
Research Organization:
Bettis Atomic Power Lab., West Mifflin, PA (United States)
Sponsoring Organization:
USDOE, Washington, DC (United States); USDOE Assistant Secretary for Nuclear Energy, Washington, DC (United States)
DOE Contract Number:
AC11-93PN38195
OSTI ID:
634000
Report Number(s):
WAPD-T--3169; CONF-980310--; ON: DE98002720
Country of Publication:
United States
Language:
English