Isotopic dilution studies of the chloroform--chloroform-d system by Raman difference spectroscopy

Journal Article · Sat Nov 15 04:00:00 EST 1980 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.439974· OSTI ID:7062653

Laane, J; Kiefer, W

Raman difference spectroscopy has been used to measure small frequency shifts in the ..nu../sub 1/ and ..nu../sub 2/ bands of CHCl/sub 3/ and CDCl/sub 3/ in various mixtures of liquid chloroform and deuterochloroform. The frequency shifts relative to the pure liquids vary linearly with concentration, and at infinitive dilution are determined to be for CHCl/sub 3/: ..delta nu../sub 1/=+0.56 and ..delta nu../sub 2/=+1.92 cm/sup -1/; and for CDCl/sub 3/: ..delta nu../sub 1/=+0.33 and ..delta nu../sub 2/=+1.82 cm/sup -1/. The fact that all frequency shifts are positive indicates that an exchange effect between like molecules is responsible for the phenomenon. The ..nu../sub 4/ bands show no frequency shifts but narrow substantially in bandwidth upon isotopic dilution. The position of the composite (CHCl/sub 3/+CDCl/sub 3/) ..nu../sub 6/ band relative to the pure liquids was also measured as a function of concentration. The data confirm that the frequency difference between this band in liquid CHCl/sub 3/ and in CDCl/sub 3/ is 1.05 cm/sup -1/. The ..nu../sub 6/ frequency appear not to be significantly shifted by isotopic dilution.

• Research Organization: Physikalisches Institut, Universitaet Bayreuth, D-8580 Bayreuth, Federal Republic of Germany
• OSTI ID: 7062653
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 73:10; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
CHLORINATED ALIPHATIC HYDROCARBONS
CHLOROFORM
DEUTERIUM
FLUIDS
HALOGENATED ALIPHATIC HYDROCARBONS
HYDROGEN ISOTOPES
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
LIQUIDS
NUCLEI
ODD-ODD NUCLEI
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
RAMAN SPECTRA
SPECTRA
SPECTRAL SHIFT
STABLE ISOTOPES