Intermolecular potential parameters and combining rules determined from viscosity data
The Law of Corresponding States has been demonstrated for a number of pure substances and binary mixtures, and provides evidence that the transport properties viscosity and diffusion can be determined from a molecular shape function, often taken to be a Lennard-Jones 12-6 potential, that requires two scaling parameters: a well depth {var_epsilon}{sub ij} and a collision diameter {sigma}{sub ij}, both of which depend on the interacting species i and j. We obtain estimates for {var_epsilon}{sub ij} and {sigma}{sub ij} of interacting species by finding the values that provide the best fit to viscosity data for binary mixtures, and compare these to calculated parameters using several 'combining rules' that have been suggested for determining parameter values for binary collisions from parameter values that describe collisions of like molecules. Different combining rules give different values for {sigma}{sub ij} and {var_epsilon}{sub ij} and for some mixtures the differences between these values and the best-fit parameter values are rather large. There is a curve in ({var_epsilon}{sub ij}, {sigma}{sub ij}) space such that parameter values on the curve generate a calculated viscosity in good agreement with measurements for a pure gas or a binary mixture. The various combining rules produce couples of parameters {var_epsilon}{sub ij}, {sigma}{sub ij} that lie close to the curve and therefore generate predicted mixture viscosities in satisfactory agreement with experiment. Although the combining rules were found to underpredict the viscosity in most of the cases, Kong's rule was found to work better than the others, but none of the combining rules consistently yields parameter values near the best-fit values, suggesting that improved rules could be developed.
- Research Organization:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Organization:
- Environmental Energy Technologies Division
- DOE Contract Number:
- DE-AC02-05CH11231
- OSTI ID:
- 984743
- Report Number(s):
- LBNL-3592E; IJCKBO; TRN: US201016%%1448
- Journal Information:
- International Journal of Chemical Kinetics, Journal Name: International Journal of Chemical Kinetics; ISSN 0538-8066
- Country of Publication:
- United States
- Language:
- English
Similar Records
Critical point and phase behavior of the pure fluid and a Lennard-Jones mixture
Infrared absorption spectra of gaseous HD. IV. Analysis of the collision-induced fundamental band of the pure gas