Chemical potential

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

$\mu ={\frac {A}{Nk_{B}T}}+{\frac {pV}{Nk_{B}T}}$

where $A$ is the Helmholtz energy function, $k_{B}$ is the Boltzmann constant, $p$ is the pressure, $T$ is the temperature and Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle V} is the volume.

Statistical mechanics

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

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \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 Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Z_N} is the partition function for a fluid of Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle N} identical particles

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Z_N= \left( \frac{2\pi m k_BT}{h^2} \right)^{3N/2} Q_N}

and Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Q_N} is the configurational integral

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Q_N = \frac{1}{N!} \int ... \int \exp (-U_N/k_B T) dr_1...dr_N}

Kirkwood charging formula

The Kirkwood charging formula is given by

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \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 Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \Phi_{12}(r)} is the intermolecular pair potential and Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle {\rm g}(r)} is the pair correlation function.

See also

• Ideal gas: Chemical potential
• Widom test-particle method
• Overlapping distribution method

References

Related reading

• G. Cook and R. H. Dickerson "Understanding the chemical potential", American Journal of Physics 63 pp. 737-742 (1995)
• T. A. Kaplan "The Chemical Potential", Journal of Statistical Physics 122 pp. 1237-1260 (2006)