Collision frequency

Last updated June 25, 2023

Collision frequency describes the rate of collisions between two atomic or molecular species in a given volume, per unit time. In an ideal gas, assuming that the species behave like hard spheres, the collision frequency between entities of species A and species B is:^[1]

Z=N_{\text{A}}N_{\text{B}}\sigma _{\text{AB}}{\sqrt {\frac {8k_{\text{B}}T}{\pi \mu _{\text{AB}}}}},

which has units of [volume][time]⁻¹.

Here,

$N_{\text{A}}$ is the number of A molecules in the gas,
$N_{\text{B}}$ is the number of B molecules in the gas,
$\sigma _{\text{AB}}$ is the collision cross section, the "effective area" seen by two colliding molecules, simplified to $\sigma _{\text{AB}}=\pi (r_{\text{A}}+r_{\text{B}})^{2}$ , where $r_{\text{A}}$ the radius of A and $r_{\text{B}}$ the radius of B.
$k_{\text{B}}$ is the Boltzmann constant,
$T$ is the temperature,
$\mu _{\text{AB}}$ is the reduced mass of the reactants A and B, $\mu _{\text{AB}}={\frac {{m_{\text{A}}}{m_{\text{B}}}}{{m_{\text{A}}}+{m_{\text{B}}}}}$

Collision in diluted solution

In the case of equal-size particles at a concentration $n$ in a solution of viscosity $\eta$ , an expression for collision frequency $Z=V\nu$ where $V$ is the volume in question, and $\nu$ is the number of collisions per second, can be written as:^[2]

\nu ={\frac {8k_{\text{B}}T}{3\eta }}n,

Where:

$k_{B}$ is the Boltzmann constant
$T$ is the absolute temperature (unit K)
$\eta$ is the viscosity of the solution (pascal seconds)
$n$ is the concentration of particles per cm³

Here the frequency is independent of particle size, a result noted as counter-intuitive. For particles of different size, more elaborate expressions can be derived for estimating $\nu$ .^[2]

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References

↑ chem.libretexts.org: Collision Frequency
1 2 Debye, P. (1942). "Reaction Rates in Ionic Solutions". Transactions of the Electrochemical Society. 82 (1): 265. doi:10.1149/1.3071413. ISSN 0096-4743.

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[1] .libretexts.org: Collision Frequency

[:0-2] 1 2 Debye, P. (1942). "Reaction Rates in Ionic Solutions". Transactions of the Electrochemical Society. 82 (1): 265. doi:10.1149/1.3071413. ISSN 0096-4743.

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