Equations of state

R. Wentzcovitch U. of Minnesota VLab tutorial

-EoSs relate P, V, and T in materials -EoSs of minerals are necessary to build Earth models -In this lecture: isothermal EoSs only (EoS parameters are T dependent). (They are used in calculations of thermal properties thermo.f program)
Poiriers Introduction to the Physics of the Earth Interior, Cambridge Press

The definition of the bulk modulus offers an EoS

dP dP K = V = dV d ln V

dV dP = V K Vo 0 P V = V0 exp K0

(with K=cte=K0)

-This is only a naive example of how to generate an EoS. -K is not cte. It varies with P, except for really ifinitesimal volume changes.

Murnaghan EoS
It can be similarly derive assuming

K = K0 + K P
' 0

K 0 ' is cte

dP K0 + K P = V dV
' 0
P dV dP V K0 ' P 1+ V0 V = 0 K0 + K0 ' P V0 = K0 V
K0 ' K 0 V0 P= 1 K0 ' V

K0 '

Strains
Eulerian strain (f>0 for compression) 2 l0 = l (1 + f ) 1 V0 3 f = 1 1 2 V l0 = l (1 + 2 f ) 2 Lagrangian strain (<0 for compression)

l = l0 (1 + ) l = l0 (1 + 2 )
l

1 2

2 1 V 3 = 1 2 V0

Hencky strain (logarithmic strain)

dl l d = H = d H = ln l l0 l0
For hydrostatic compression

1 V H = ln 3 V0

 One more relation to be used: V 1 = 1 3 f For f 0 3 V0 (1 + 2 f ) 2

dV = 3V0 Therefore df
Bulk modulus
K 0 = lim V dP VP dV = lim = 3 f V V0 V V0 dV dV 1 dF V with 9 K V lim = 0 0 1 1 dF P 0 dF f df K 0 = lim P = P 0 3 f 3V df dV 0

Now we will expand the free energy in terms of (eulerian) strains and derive relationships P(V), K(V), K(V) F=af2+bf3+cf+

Birch Murnaghan EoS (2nd order)

2nd order expansion of the free energy F=af2
2 1 V0 3 with f = 1 2 V Recall that 1 F 9 K 0V0 = lim P 0 f f T

9 Therefore a = K 0V0 2 F F f with P= = V T f V

5 F 1 = (1 + 2 f ) 2 3V0 V

P = 3K 0 f (1 + 2 f )

7 3K 0 3 = 2 0

7 5 3 3 K0 dP dP = = K= 7 5 0 d 0 2 0 d 0

K = K 0 (1 + 7 f )(1 + 2 f )

3 w/ = (1 + 2 f ) 2 0

K K f 12 + 49 f K0 ' = = = P f P 3 + 21 f

Therefore for f0 K 0 ' = 4

LM assemblage
2 nd PBM R= PM ( K ' = 4)

Murnaghan EoS overestimates P for noninfinitesimal strain

Birch-Murnaghan 3rd order

F = af 2 + bf 3
F Take into account: P = V
T

F f = f V

with

5 f 1 = (1 + 2 f ) 2 3V0 V

with 9 K 0V0 = lim P 0 Then one gets:

1 F f f T
5 2

P = 3K 0 f (1 + 2 f )

3bf 1 + 2 a

At P=0 (f=0), K=K0 K=K0

7 3K 0 3 P= 2 0

2 eq.s for 2 unknowns, a and b

5 3

2 3 1 + 1 0 0

3 ( K 0 ' 4 ) 4

If K0=4 we recover the 2nd order BM

 One needs measurements in a larger pressure range to fit a 3rd order EoS There are trade offs between K0 and K0 If the pressure range is small K0 is usually constrained to 4.

Vinet EoS
This EoS is based on a different expansion of F F = F0 (1 + a) exp(a) l is a scaling length (r r0 ) a= l 4 3 Defining V = r and changing variables (rV) in F 3
P= F F = 0 2 a exp( a ) 4 lr V F0 2r0 K0 = K0 ' = 1 + 4 l 2 r0 3l
2 / 3 1 V 13 V 3 3 1 exp ( K 0 ' 1) 1 V0 V0 2

Replace a, l, K0, and K0 from relations above and get

V P = 3K 0 V0

Logarithmic EoS
Expand F in powers of Hencky strains, H, like the Birch-Murnaghan To 2nd order in H one gets P = K0 ln 0 0 And to 3rd order one gets
ln P = K0 0 0
K 0 ' 2 1 + ln 2 0

Comparison between parameters offered by various EoSs

Summary
The same data set produces different parameters V0, K0, K0, etc (trade offs) when fit to different EoSs. Be careful when comparing parameters obtained from different EoSs. Preferable to compare raw data of curves instead of parameters. High order finite strain EoSs require data in larger pressure ranges. The Vinet EoS is a fine and decent EoS for any pressure range.