Birch-murnaghan Equation Of State

In continuum mechanics, an equation of state suitable for modeling solids is naturally rather different from the ideal gas law. A solid has a certain equilibrium volume V_0, and the energy increases quadratically as volume is increased or decreased a small amount from that value. The simplest plausible dependence of energy on volume would be a harmonic solid, with
E = E_0 + \frac{1}{2} B_0 \frac{(V-V_0)^2}{V_0}. The next simplest reasonable model would be with a constant bulk modulus
B = - V \left( \frac{\partial P}{\partial V} \right)_T. (2)
E = E_0 + B_0 \left( V_0 - V + V \ln(V/V_0) \right). A more sophisticated equation of state was derived by F. D. Murnaghan. To begin with, we consider the pressure
P = - \left( \frac{\partial E}{\partial V} \right)_S (1)
and the bulk modulus
B = - V \left( \frac{\partial P}{\partial V} \right)_T. (2) Experimentally, the bulk modulus pressure derivative
B' = \left( \frac{\partial B}{\partial P} \right)_T (3) is found to change little with pressure. If we take B' = B'_0 to be a constant, then
B = B_0 + B'_0 P (4) where B_0 is the value of B when P = 0. We may equate this with (2) and rearrange as
\frac{d V}{V} = -\frac{d P}{B_0 + B'_0 P}. (5) Integrating this results in
P(V) = \frac{B_0}{B'_0} \left(\left(\frac{V_0}{V}\right)^{B'_0}
     - 1\right)	(6) 
or equivalently
V(P) = V_0 \left(1+B'_0
     \frac{P}{B_0}\right)^{-1/B'_0}.		(7) 
Substituting (6) into E = E_0 - \int P dV then results in the Birch--Murnaghan equation of state for energy.
E(V) = E_0
  + \frac{ B_0 V }{ B_0' } \left( \frac{ (V_0/V)^{B_0'} }{ B_0' - 1 } + 1 \right)  - \frac{ B_0 V_0 }{ B_0' - 1 }. 	(8) 
Many substances have a fairly constant B'_0 of about 3.5.

References

  • F. D. Murnaghan, Proceedings of the National Academy of Sciences, vol. 30, p. 244, 1944.

 

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