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On the Relative Roles of Free Volume and Activation Energy in the Viscosity of Liquids
Abstract
The rate-theory approach of Eyring and the free-volume theory of Cohen and Turnbull for liquid viscosities have been reconsidered. The rate theory has been reformulated using the Cohen and Turnbull expression for the probability of finding a vacant site and yields an equation of the form η=A0exp[Ev*/RT+γV0/Vf].This result has been applied to many liquids ranging from fused silica to liquid argon and including polyatomic van der Waals as well as hydrogen-bonded liquids. Consistent fits to both temperature and pressure dependence of viscosity were obtained. A significant conclusion is that the free volume of liquids is considerably higher than that suggested by the WLF and Cohen and Turnbull equations.
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Cites
Williams, M. L., Landel, R. F., & Ferry, J. D. (1955) · Journal of the American Chemical Society · doi:10.1021/ja01619a008 · Cited by 8,083
Studies in Newtonian Flow. II. The Dependence of the Viscosity of Liquids on Free-Space
Doolittle, A. K. (1951) · Journal of Applied Physics · doi:10.1063/1.1699894 · Cited by 1,831
Cited by
Characteristics and Significance of the Amorphous State in Pharmaceutical Systems
Hancock, B. C., & Zografi, G. (1997) · Journal of Pharmaceutical Sciences · doi:10.1021/js9601896 · Cited by 1,922
Enthalpy relaxation and recovery in amorphous materials
Hodge, I. M. (1994) · Journal of Non-Crystalline Solids · doi:10.1016/0022-3093(94)90321-2 · Cited by 1,206
A ring to rule them all: the effect of cyclopropane fatty acids on the fluidity of lipid bilayers
Poger, D., & Mark, A. E. (2015) · The Journal of Physical Chemistry B · doi:10.1021/acs.jpcb.5b00958 · Cited by 162
Harmandaris, V. A., Doxastakis, M., Mavrantzas, V. G., & Theodorou, D. N. (2002) · The Journal of Chemical Physics · doi:10.1063/1.1416872 · Cited by 98
Metadata
- Authors
- Macedo, P. B., & Litovitz, T. A.
- Venue
- The Journal of Chemical Physics
- Publisher
- AIP Publishing
- Published
- 1965-01-01
- Volume
- 42
- Issue
- 1
- Pages
- 245-256
- ISSN
- 0021-9606 (ISSN-L)
- 1089-7690
- OpenAlex
- W2069364236
- Cited by
- 550
- References
- 2
- FWCI
- 18.00
- Type
- journal article
- Language
- en
- Open access
- closed
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- Macedo, P. B., & Litovitz, T. A. (1965). On the Relative Roles of Free Volume and Activation Energy in the Viscosity of Liquids. The Journal of Chemical Physics. https://doi.org/10.1063/1.1695683
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Contains information from the Semantic Scholar Academic Graph Datasets, made available under the ODC Attribution License (ODC-BY 1.0).
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