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Title: Self-diffusion measurements of methanol and 1-decanol in supercritical CO{sub 2} by {sup 13}C pulsed field gradient NMR

Conference ·
OSTI ID:563976
; ;  [1];  [2]
  1. Univ. of Utah, Salt Lake City, UT (United States). Dept. of Chemistry
  2. Los Alamos National Lab., NM (United States). Organic Analytical Chemistry Group

A small amount of a highly polar compound, such as methanol, is frequently added to supercritical fluid (SCF) carbon dioxide to enhance its ability to dissolve polar molecules in SCF separation technology. Few diffusion coefficients in SCF mixtures have been reported in the literature. The pulsed field gradient spin-echo technique (PGSE) has been used extensively to measure self-diffusion in neat monohydric alcohols under pressure. Hurle et al. and Luedemann et al. showed that the experimental diffusion coefficients of methanol may be explained by a rough hard-sphere model (RHS) with a roughness parameter, A. In this paper, diffusion measurements are reported for CO{sub 2}-methanol and CO{sub 2}-decanol mixtures in supercritical fluids. Since methanol in CO{sub 2} is primarily monomeric at low concentration, the RHS model, that is accurate for most simple, non-associated liquids, should apply. Previous nuclear spin-lattice relaxation studies in SCF CO{sub 2} suggest a large local solvent density enhancement, or solvent clustering, near a alcohol solute molecule under SCF conditions. If solvent clustering occurs in the vicinity of alcohol solute molecules, it should affect the diffusion coefficients. The authors have made the requisite measurements and found that they corroborate their previous spin-relaxation data.

Research Organization:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE, Washington, DC (United States)
DOE Contract Number:
W-7405-ENG-36
OSTI ID:
563976
Report Number(s):
LA-UR-97-1869; CONF-970629-2; ON: DE97008161; TRN: AHC29804%%1
Resource Relation:
Conference: 13. symposium on thermophysical properties, Boulder, CO (United States), 22-27 Jun 1997; Other Information: PBD: [1997]
Country of Publication:
United States
Language:
English