Solvent anions in supercritical carbon dioxide : formation of complexes with polar solutes.
It is shown that high-mobility multimer (CO{sub 2}){sub n}{sup {center_dot}-} anions in supercritical (sc)-CO{sub 2} form stable complexes with water, aliphatic alcohols, alkyl halides, and alkyl nitriles. The complexation rate is 10-50% of the diffusion controlled rate or faster. The complexes are formed both with the monomer and with the dimer polar solutes. The equilibrium constants of the monomer complexation range from 10 to 350 M{sup -1}; the reaction heat is -(15-21) kJ/mol, and the reaction entropy is negative. The stability of the complex increases with the dipole moment of the polar group and decreases with the substitution at the {alpha}-carbon. None of these polar solutes directly reacts with quasifree electrons in sc-CO{sub 2}.
- Research Organization:
- Argonne National Laboratory (ANL)
- Sponsoring Organization:
- SC
- DOE Contract Number:
- AC02-06CH11357
- OSTI ID:
- 949232
- Report Number(s):
- ANL/CHM/JA-38939
- Journal Information:
- J. Phys. Chem. B, Journal Name: J. Phys. Chem. B Journal Issue: 29 ; 2001 Vol. 105; ISSN 1089-5647; ISSN JPCBFK
- Country of Publication:
- United States
- Language:
- ENGLISH
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