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# Ross Angel

## I determine the atomic-scale structures of minerals, and how

they change with pressure, temperature and composition
Structure Function Geology and Geophysics

www.rossangel.com
rossjohnangel@gmail.com

## What are EoS and what are they used for?

Measurement methods (very brief)
EoS theory and formulations
PV data analysis

## Elastic versus plastic

Elastic deformation

Plastic deformation

E.g. springs
Reversible
no permanent change
Hooke law: F = -kx

Bond compression

Irreversible, permanent
change
Material flow

Bond bending

## On-line Eos class, Ross J Angel

Equation of State
Defines the elastic relationship
of volume to intensive
variables:
V = f(T,P,H,X.)
Normally V = f(P,T)
Isothermal EoS: V=f(P)
Can also be defined as = f(P)
Or as the change in elastic properties
with pressure
Hooke law: F = -kx
Linear EoS

Crust
1 GPa
Transition zone
20 GPa

## Rocks exert a pressure

Useful approximation

## 3km in the crust = 1 kbar

30km in the crust = 1 GPa

CMB
150 GPa

Centre
320 GPa

P gh

## Equations of state for minerals

An equation of state for a mineral
defines:

## the variation of density of a

mineral with P,T
(partly) the seismic velocities
Volume changes at transitions
and slopes of phase boundaries

dP
S

dT
V

Diamond inclusions
P=0

P
P

Grow at P,T

decompress

## The hole in the diamond is at

room pressure, but same V as
olivine

## Use EoS to determine pressure

at which they had same P and
V

P>0

## Equations of state chemistry and physics

The P-V behaviour implies the elastic properties

Bonding
Softening at transitions
Materials applications

## Elasticity basics: volume/bulk

Elasticity is a material property:

1.00

## relates applied stress and resulting strain

compliances describe softness
moduli describe stiffness

Stress is dP
Strain is dV/V
Compressibility
Volume compliance
Bulk modulus:

V/V0

## For volume change with pressure:

0.95

0.90

0.85

1
V P
V

0 1 2 3 4 5 6 7 8 9 10

Pressure: GPa

K V P V

## We normally describe an EoS in terms of

the room pressure parameters.
V0

Bulk modulus

K 0 V 0 P V P 0

Volume

K0 K P P 0

Etc.

K0 2 K P 2

P 0

Pressure

K0

## The diamond-anvil cell

Apply hydrostatic stress
quartz
+/-0.01 GPa

ruby
sample
+/-0.05 GPa

## On-line Eos class, Ross J Angel

Volume measurements
Almost all by diffraction: d(hkl) = /2sin hkl

## Results of diffraction experimentsPV data

1.00

V/V0

0.95

0.90

0.85
0 1 2 3 4 5 6 7 8 9 10

Pressure: GPa

Quartz, SiO2

## On-line Eos class, Ross J Angel

Albite, NaAlSi3O8

CuCO3

Choice of EoS

form for an EoS

## All EoS are based upon assumptions

The validity of the assumptions can only be judged in terms of the accuracy with
which the EoS reproduces P-V or elastic data

## An assumed inter-atomic potential

An assumed relationship between EoS parameters and P
An assumed relationship between free energy and strain
(and a choice of strain definition)

## Your choice depends on

Accuracy
Reliability in extrapolation (?)
Convenience

## Why not use a polynomial?

1.00

0.95

V/V0

V
1 aP bP 2 .. ????
V0

0.90

0.85
0 1 2 3 4 5 6 7 8 9 10

Pressure: GPa

## Derivation from inter-atomic potentials

General idea:
Inter-atomic potential gives energy as function of
distance
Includes attractive (e.g. Madelung)
12

Z1 Z 2 e 2
r12

A ij

AZ i Z j e 2
rij

Eos:
1
v12

r12n
n=6

## Derivation from inter-atomic potentials

Inter-atomic potential gives
energy as function of distance
So we have energy as function of
volume
r 3
V
E E
r
V0
0

P

E
V

## .see Anderson, O.L. (1995) Equations of State of Solids

for Geophysics and Ceramic Science. Oxford University
Press, Oxford, UK.

## On-line Eos class, Ross J Angel

Vinet EoS
Derived from general interatomic potential
1

V 3
fV
V0
1 f
P 3K 0 2 V
f
V

exp 3 K 11 fV
2

## Simple, 3 parameter equation of state, but has an implied

2
value of K:
1 K K 19
K

K 0 2 2 36

Excellent for simple solids
Accurate to high compression

Not intended for complex materials with significant degrees of
internal structural freedom.
No extension to refinable K

EoS of quartz

K V P V

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## Equations of state: Murnaghan

Actually derived from concept of finite strain

## But also can be derived by assuming K is linear with P

V

Bulk Modulus

K K 0 K P

P
K 0 K P
V
P
V
V
P
0 K 0 K P Vo V
1

K P K

V V0 1
K 0

K V
P 0 0 1
K V

K0

Can be inverted, easily integrated
great for thermo databases

Pressure

K is constant, K = 0
Does not fit P-V data for V/V0 < 0.9
crust only

## Finite strain EoS

Assumes strain energy is a polynomial in strain f

af 2 bf 3 cf 4 .....
Pressure is then:

E
V

d
d df

dV
df dV
df
P
2af 3bf 2 4cf 3 ....
dV
P

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## Infinitesimal and Finite strain

Conventional elasticity theory works with infinitesimal
strains:

l l0
l0

V V0 V
1
V0
V0

## Under compression the

volume changes are not
smallfinite strain
V 0.142
f L 0.049

fL

1 V

2 V0

2/3

## Finite strain definitions

Infinitesimal strains defined with respect to the initial state
are called Lagrangian:
V

V V0 V
1
V0
V0

initial state:
fL

1 V

2 V0

2/3

## Eulerian strains are defined with respect to the final state:

Note sign convention
fE

## On-line Eos class, Ross J Angel

1 V0

2 V

2/3

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Birch-Murnaghan EoS
Finite strain EoS

af 2 bf 3 cf 4
d
d df

P
dV
df dV
df
P
2af 3bf 2 4cf 3
dV

V 2 3
0 1
V

fE
2

## Do derivatives up to K, substitute back and.

5
35
3
3
P 3K 0 f E 1 2 f E 2 1 K 0 4 f E K 0 K 0 K 0 4 K 0 3 f E2
9
2
2
5
35
9
K K 0 1 2 f E 2 1 3K 0 5 f E K 0 K 0 K 0 K 0 4 f E2
9
2

## Birch-Murnaghan EoS full expression

5
35
3
3
P 3K 0 f E 1 2 f E 2 1 K 0 4 f E K 0 K 0 K 0 4 K 0 3 f E2
9
2
2
5
35
9
K K 0 1 2 f E 2 1 3K 0 5 f E K 0 K 0 K 0 K 0 4 f E2
9
2

V 2 3
0 1
V

fE
2

Fits P-V data for V/V0 to 0.8
Provides correct K0
Good for crust and mantle

Cannot be inverted
VdP integrals must be numerical
Problem for thermo databases

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## Birch-Murnaghan EoS truncations

5
35
3
3
P 3K 0 f E 1 2 f E 2 1 K 0 4 f E K 0 K 0 K 0 4 K 0 3 f E2
9
2
2

5
35
9
K K 0 1 2 f E 2 1 3K 0 5 f E K 0 K 0 K 0 K 0 4 f E2
9
2

Truncation:
2nd order (in energy)
Coefficient of fE must be zero
V0 and K0 are material parameters
K0 = 4

P 3K 0 1 2 f

5/ 2

K K 0 1 2 f (1 7 f )
4 49 f 3 K 0 49 f 3
K
1 7 f
1 7 f
5/ 2

## Birch-Murnaghan EoS truncations

5
35
3
3
P 3K 0 f E 1 2 f E 2 1 K 0 4 f E K 0 K 0 K 0 4 K 0 3 f E2
9
2
2

5
35
9
K K 0 1 2 f E 2 1 3K 0 5 f E K 0 K 0 K 0 K 0 4 f E2
9
2

Truncation:
3rd order (in energy)
Coefficient of f2E must be zero
V0 K0 K0 are material parameters

1
3 K 4 K 35
9
K 0

## 4th order (in energy)

Coefficient of f2E non-zero
V0 K0 K0 K0 are material parameters

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K V P V

## Birch-Murnaghan EoS for quartz

K K P

V 2 3
0 1
V

fE
2

K 2 K P2

5
3
3
35
P 3K 0 f E 1 2 f E 2 1 K 4 f E K 0 K K 4 K 3 f E2
2
9
2

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Derived from

## An assumed relationship between free energy and strain

and a choice of strain definition

## Natural Strain (Poirier)

1 V
f N ln
3 V0
3
V 3

2
P 3K 0 0 f N 1 K 2 f N 1 K 0 K K 2 K 2 f N2
2
V 2

## Choice of EoS: Precision and Accuracy

The bulk modulus and its derivatives are
thermodynamic variables of precise definition:
K V P V K K P

K K P 2 K P

## An EoS says how these change with P

But there is no absolute thermodynamic basis for
specifying a correct form for an EoS

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## Equations of state choice of form

Assume how parameters vary with pressure

Murnaghan

## Assume how energy varies with strain

Birch-Murnaghan
Vinet
Natural strain

Assume a truncation
The validity of the assumptions can only be judged in terms
of the accuracy with which the EoS reproduces P-V or
elastic data

## Equations of State Further reading

Angel RJ (2000) Equations of state.

In RM Hazen and RT Downs (eds.), High-temperature and highpressure crystal chemistry, MSA. pp. 35-60, Reviews in Mineralogy and
Geochemistry, vol. 41
Available from www.minsocam.org
Short version in EoSFit manual at www.rossangel.com

## Anderson OL (1995) Equations of State of Solids for

Geophysics and Ceramic Science. Oxford University Press,
Oxford
Technical papers:

## Murnaghan (1937) Am. J. Maths 59:235

Birch (1947) Phys. Rev. 71:809
Stacy (1981) Geophys. Surveys 4:189
Jeanloz (1988) Phys Rev B38:805

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## The validity of an EoS can only be judged in terms of the accuracy

with which it reproduces P-V or elastic data
V0 : 3

K0 : GPa

K'

K" : GPa-1

2w

Pobs Pcalc

BM2

112.97(2)

41.5(3)

[4.0]

[-.094]

128

0.32

BM3

112.981(2)

37.12(9)

5.99(5)

[-.265]

0.95

0.025

BM4

112.981(2)

36.89(22)

6.26(24)

-.41(12)

0.93

0.026

NS2

112.95(5)

46.5(6)

[2.0]

[-.022]

580

0.65

max

1.00

NS3

112.982(2)

36.39(11)

6.91(7)

[-.825]

1.15

0.026

NS4

112.981(2)

36.90(24)

6.25(29)

-.39(11)

0.93

0.026

Vinet

112.981(2)

37.02(9)

6.10(4)

[-.319]

0.90

0.025

Murn.

112.981(2)

37.63(10)

5.43(4)

[0]

1.57

0.033

V/V0

0.95

0.90

0.85
0

9 10

Pressure: GPa

## Step 1: start the analysis

Not precise: large (V), (P)

P-V plots

Data consistency/scatter
Esd evaluation

no help with K, K

## Precise: small (V), (P)

Nestola et al., (2008) Canadian
Mineralogist 46:1433-1454.

## On-line Eos class, Ross J Angel

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Birch-Murnaghan EoS
5
3
3
35
P 3K 0 f E 1 2 f E 2 1 K 4 f E K 0 K K 4 K 3 f E2
2
2
9

Truncation:
2nd order (in energy)
Coefficient of fE must be zero
V0 and K0 refined
K = 4

## 3rd order (in energy)

Coefficient of f2E must be zero
V0 K0 K refined

1
3 K 4 K 35
9
K 0

## 4th order (in energy)

Coefficient of f2E non-zero
V0 K0 K K refined

## Step 2: f-F plots

Rearrange BM4 Eos:
3K
3K
35
F K0 0 K0 4 f 0 K0 K K 4 K 3 f 2...
E
E 2
9 E
2

FE

P
3f 1 2 f E

5
2

V 2 3
0 1

V
fE
2

EoS

K 4
K0

## On-line Eos class, Ross J Angel

K 4

K 4
Eulerian strain: f

19

## Using f-F plots

BM4 Eos:
3K
3K
35
F K0 0 K0 4 f 0 K0 K K 4 K 3 f 2...
E
E 2
9 E
2

FE

P
3f 1 2 f E

5
2

V 2 3
0 1

V
fE
2

## Curved line: 4th order EoS

K 4

K
K 0
P

K 4

KK
44
Eulerian strain: f

V 2 3
0 1
V

fE
2

FE

P
3f 1 2 f E

5
2

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## Step 3: Fit Equations of State

Birch-Murnaghan EoS
V 2 3
0 1
V

fE
2
5
35
3
3
P 3K 0 f E 1 2 f E 2 1 K 4 f E K 0 K K 4 K 3 f E2
9
2
2

## Fit by least squares

Use esd(P) and esd(V) to weight the data

## Refine increasing derivatives (K, K) until:

no improvement in fit,
or results meaningless

Lets do it!

Using EoSFit
DOS executable from www.rossangel.com

No graphics
Plot data in Excel, Origin etc

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## Quality of fit: did we get it right??

There is no substitute for
visual examination and
critical thinking!

## Is the fit correct?

Does the model represent
the data?
Does V0 from the fit
match the observed
value?
.misfit vs esd(P)

## Quality of fit: fF plot

There is no substitute for visual examination and critical
thinking!

## Is the fit correct?

Does the model represent the data?

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## Overall quality of fit

Unweighted R value

Rw

## Smaller is perhaps better

Goodness of fit

obs

calc

obs

Weighted R-value

y y
y

Weighted-chi-squared
Allows for degrees of freedom
S
Smaller really is better
=1 when model agrees with data within
the uncertainties of the data

w2

w y y
wy
obs

2
obs

w y

calc

ycalc 2

n p

obs

Goodness of fit

S=1

## model agrees with data within the

uncertainties of the data
Line passes through 2/3 of 1 error bars
Line passes through 95% of 2 error
bars

w yobs ycalc 2 2
n p

S>1

w2

## Line misses 2/3 of 1 error bars

Esds too small, or.
Look at pattern of residuals

S<1

## Line passes >2/3 of 1 error bars

Esds too big, or.
Model over-fitted

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2w

V0 : 3

K0 : GPa

K'

K" : GPa-1

BM2

683.02(18)

56.1(3)

[4.0]

[-.069]

21.2

-.14

BM3

682.76(14)

58.0(6)

3.41(15)

[-.063]

10.6

-.073

BM4

682.92

54.4(4)

6.4(3)

-1.16(13)

0.75

-.017

## Conclude: BM4 fits data best. Is this correct?

Are the parameters physically reasonable?

## Is the result reasonable?

There is no substitute for critical thinking!

Are the parameters K, K what you expect for the type of structure?
Do they agree with independent measurements?
Do they form systematic trends with composition or other parameters?

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## Anorthoclase: bulk modulus variation

K is not constant!

## A warning about f-F plots

3K
3K
35
F K0 0 K0 4 f 0 K0 K K 4 K 3 f 2...
E
E 2
9 E
2

FE

P
3f 12f E

5
2

V 2 3
0 1
V

fE
2

## V0 is not known exactly, only experimentally with esd!

An incorrect V0 curves the f-F data
And the fitted EoS will not pass through the data points!

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## Analysing PV data - summary

Use f-F plots to examine the data

## They indicate order of EoS

And whether the behaviour is normal

## Use proper weighting

Refine the correct parameters
Critically examine the results

quartz

EoS: Summary

## The bulk modulus and its derivatives are

thermodynamic variables of precise
definition:
K V P V

K K P 2 K P

K K P

## But there is no absolute thermodynamic

basis for specifying a correct form for an
EoS
All EoS are based upon assumptions

www.rossangel.com
rossjohnangel@gmail.com

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