Related Experiment Video
Updated: May 30, 2026

The Diffusion of Passive Tracers in Laminar Shear Flow
Published on: May 1, 2018
Collision limited reaction rates for arbitrarily shaped particles across the entire diffusive Knudsen number range
Ranganathan Gopalakrishnan1, Thaseem Thajudeen, Christopher J Hogan
1Department of Mechanical Engineering, University of Minnesota, Minneapolis, Minnesota 55455, USA.
Abstract:
Aerosol particle reactions with vapor molecules and molecular clusters are often collision rate limited, hence determination of particle-vapor molecule and particle-molecular cluster collision rates are of fundamental importance. These collisions typically occur in the mass transfer transition regime, wherein the collision kernel (collision rate coefficient) is dependent upon the diffusive Knudsen number, Kn(D). While this alone prohibits analytical determination of the collision kernel, aerosol particle- vapor molecule collisions are further complicated when particles are non-spherical, as is often the case for particles formed in high temperature processes (combustion). Recently, through a combination of mean first passage time simulations and dimensional analysis, it was shown that the collision kernel for spherical particles and vapor molecules could be expressed as a dimensionless number, H, which is solely a function of Kn(D). In this work, it is shown through similar mean first passage times and redefinitions of H and Kn(D) that the H(Kn(D)) relationship found for spherical particles applies for particles of arbitrary shape, including commonly encountered agglomerate particles. Specifically, it is shown that to appropriately define H and Kn(D), two geometric descriptors for a particle are necessary: its Smoluchowski radius, which defines the collision kernel in the continuum regime (Kn(D)→0) and its orientationally averaged projected area, which defines the collision kernel in the free molecular regime (Kn(D)→∞). With these two parameters, as well as the properties of the colliding vapor molecule (mass and diffusion coefficient), the particle-vapor molecule collision kernel in the continuum, transition, and free molecular regimes can be simply calculated using the H(Kn(D)) relationship.
Related Concept Videos
Reaction Mechanisms: Rate-limiting Step Approximation
Rate Laws and Equilibrium Constants for Elementary Reactions
Fast Reactions
Concentration and Rate Law
For example, in a generic reaction aA + bB ⟶ products, where a and b are stoichiometric coefficients, the rate law can be written as:
Temperature Dependence on Reaction Rate
Atoms, molecules, or ions must collide before they can react with each other. Atoms must be close together to form chemical bonds. This premise is the basis for a theory that explains many observations regarding chemical kinetics, including factors affecting reaction rates.
The collision theory is based on the postulates that (i) the reaction rate is proportional to the rate of reactant collisions, (ii) the reacting species collide in an orientation allowing contact between...
Transition State Theory

