Chemical potential

From SklogWiki

Jump to: navigation, search

Contents

[edit] Classical thermodynamics

Definition:

\mu=\left. \frac{\partial G}{\partial N}\right\vert_{T,p} = \left. \frac{\partial A}{\partial N}\right\vert_{T,V}

where G is the Gibbs energy function, leading to

\mu=\frac{A}{Nk_B T} + \frac{pV}{Nk_BT}

where A is the Helmholtz energy function, kB is the Boltzmann constant, p is the pressure, T is the temperature and V is the volume.

[edit] Statistical mechanics

The chemical potential is the derivative of the Helmholtz energy function with respect to the number of particles

\mu= \left. \frac{\partial A}{\partial N}\right\vert_{T,V}=\frac{\partial (-k_B T \ln Z_N)}{\partial N} = -\frac{3}{2} k_BT \ln \left(\frac{2\pi m k_BT}{h^2}\right) + \frac{\partial \ln Q_N}{\partial N}

where ZN is the partition function for a fluid of N identical particles

Z_N= \left( \frac{2\pi m k_BT}{h^2} \right)^{3N/2} Q_N

and QN is the configurational integral

Q_N = \frac{1}{N!} \int ... \int \exp (-U_N/k_B T) dr_1...dr_N

[edit] Kirkwood charging formula

See Ref. 2

\beta \mu_{\rm ex} = \rho \int_0^1 d\lambda \int \frac{\partial \beta \Phi_{12} (r,\lambda)}{\partial \lambda} {\rm g}(r,\lambda) dr

where Φ12(r) is the intermolecular pair potential and g(r) is the pair correlation function.

[edit] See also

[edit] References

  1. T. A. Kaplan "The Chemical Potential", Journal of Statistical Physics 122 pp. 1237-1260 (2006)
  2. John G. Kirkwood "Statistical Mechanics of Fluid Mixtures", Journal of Chemical Physics 3 pp. 300-313 (1935)
  3. G. Cook and R. H. Dickerson "Understanding the chemical potential", American Journal of Physics 63 pp. 737-742 (1995)
Personal tools