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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 V0, 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 = B0 + B'0P(4)

where B0 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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