Two-dimensional kinetics of binary nucleation in sulfuric acid--water mixtures
- Environmental Chemistry Division, Brookhaven National Laboratory, Upton New York 11973 (United States)
Homogeneous nucleation theory for binary mixtures is developed as a two-component extension of the classical multistate kinetics rate theory. A matrix formulation, based on the stochastic model of Shugard and Reiss [J. Chem. Phys. [bold 65], 2827 (1976)], provides the framework for solving the strongly coupled two-dimensional flux network associated with tracking the evaporation and growth kinetics of each component for several thousand binary clusters, of varying composition, throughout the region of critical size. This approach avoids the assumption of a single nucleation path, e.g., through the saddle point of the binary free-energy surface, and considers, instead, all possible paths whose current density contributes to the nucleation rate. Calculations are presented for the steady-state nucleation rate and, by a new method based on the negative eigenvalue theorem, for the distribution of relaxation times in sulfuric acid--water mixtures. At water relative humidities typical of the atmosphere, quantitative agreement with the predictions of a closed-form rate expression due to Shugard [ital et] [ital al]. is found. At high supersaturations, typical of diffusion cloud chamber operation, the nucleation current is found to bypass the saddle point, due to kinetic forcing, resulting in a higher-than-expected nucleation rate.
- DOE Contract Number:
- AC02-76CH00016
- OSTI ID:
- 6658005
- Journal Information:
- Journal of Chemical Physics; (United States), Vol. 102:5; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
BINARY MIXTURES
NUCLEATION
SULFURIC ACID
WATER
EIGENVALUES
FREE ENERGY
HUMIDITY
KINETIC EQUATIONS
MATRICES
RELAXATION
SADDLE-POINT METHOD
STOCHASTIC PROCESSES
TWO-DIMENSIONAL CALCULATIONS
CALCULATION METHODS
DISPERSIONS
ENERGY
EQUATIONS
HYDROGEN COMPOUNDS
INORGANIC ACIDS
MIXTURES
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
THERMODYNAMIC PROPERTIES
400201* - Chemical & Physicochemical Properties
661300 - Other Aspects of Physical Science- (1992-)