Bjerrum length

Comparative measure of electrostatic and thermal energy

The Bjerrum length (after Danish chemist Niels Bjerrum 1879–1958 [1]) is the separation at which the electrostatic interaction between two elementary charges is comparable in magnitude to the thermal energy scale, k B T {\displaystyle k_{\text{B}}T} , where k B {\displaystyle k_{\text{B}}} is the Boltzmann constant and T {\displaystyle T} is the absolute temperature in kelvins. This length scale arises naturally in discussions of electrostatic, electrodynamic and electrokinetic phenomena in electrolytes, polyelectrolytes and colloidal dispersions. [2]

In standard units, the Bjerrum length is given by λ B = e 2 4 π ε 0 ε r   k B T , {\displaystyle \lambda _{\text{B}}={\frac {e^{2}}{4\pi \varepsilon _{0}\varepsilon _{r}\ k_{\text{B}}T}},} where e {\displaystyle e} is the elementary charge, ε r {\displaystyle \varepsilon _{r}} is the relative dielectric constant of the medium and ε 0 {\displaystyle \varepsilon _{0}} is the vacuum permittivity. For water at room temperature ( T 293  K {\displaystyle T\approx 293{\text{ K}}} ), ε r 80 {\displaystyle \varepsilon _{r}\approx 80} , so that λ B 0.71  nm {\displaystyle \lambda _{\text{B}}\approx 0.71{\text{ nm}}} .

In Gaussian units, 4 π ε 0 = 1 {\displaystyle 4\pi \varepsilon _{0}=1} and the Bjerrum length has the simpler form

Bjerrum length in water calculated as a function of temperature.

λ B = e 2 ε r k B T . {\displaystyle \lambda _{\text{B}}={\frac {e^{2}}{\varepsilon _{r}k_{\text{B}}T}}.}

The relative permittivity εr of water decreases so strongly with temperature that the product (εr·T) decreases. Therefore, in spite of the (1/T) relation, the Bjerrum length λB increases with temperature, as shown in the graph.

See also

References

  1. ^ "Obituary: Professor Niels J. Bjerrum". Transactions of the Faraday Society. 55: X001. 1959. doi:10.1039/TF959550X001.
  2. ^ Russel, William B.; Saville, D. A.; Schowalter, William R. (1989). Colloidal Dispersions. New York: Cambridge University Press.