J, Phys. Chem. Solids Vol. 54. NO. 5. pp. 629-633, 1993 OOZZ-3697/93 56.00 + 0.

00
Printed in Great Britain. ,TJ 1993 Fcrgamon Press Ltd

THERMAL EXPANSIVITY OF PERICLASE AT HIGH

TEMPERATURE AND HIGH PRESSURE

XIANG XIA and JING-KAI XIAO

Institute of Geochemistry, Academia Sinica, Guiyang 550002, China

(Received 3 January 1992; accepted in revisedform 21 September 1992)

At&act--The enthafpy at high pressure and the effect of pressure on the heat capacity of periciase arc
calculated. The calculational results of enthalpy and heat capacity show that at small compression the
enthalpy and heat capacity are linear with pressure. The heat capacity can also be estimated using the
Debye model. An equation is presented to formulate the heat capacity at high pressure. Using the linear
relation for pcriclase at small compression, the formulas for thermal expansivity of periclase at high
temperature and high pressure are presented according to the themodynamic identities. Computed thermal
expansivity of pcriclase for temperatures of 3OCk1800K, and pressure to 50 GPa is given.

Keywords: Thermal expansivity, enthalpy, heat capacity, periclase.

1. ~NTRODU~ON different authors. Since the thermal expansivity is

Computations of thermodynamic functions of min-
erals require accurate knowledge of the thermal ex-
pansivity, bulk modulus and heat capacity over the
temperature and pressure range of interest. In ad-
dition a suitable equation of state is needed for the
enthalpy and internal energy functions. The product
CIKT of the thermal expansivity and bulk modulus is
an important thermodynamic variable and the ther-
modynamic functions for minerals can be presented
in terms of it [l, 21. It is very important for compu-
tations of the~odynamic functions to acquire accu-
rate data for the a K7 variation with temperature,
pressure and volume. Recently progress has been
made in specifying the variation of the isothermal
bulk modulus at high temperature for several min-
erals. Using a new resonance measurement technique
RPR, the elastic constants can be measured with high
accuracy at high temperature (as high as 1825 K). But
the accuracy of thermal expansivity is low and the
experimental values from different authors do not
very difficult to measure at high temperature and
pressure, it is necessary to present an empirical
formula based on the thermodynamic relation to
calculate the thermal expansivity. With the recent
experimental data, we calculate the enthalpy at high
pressure from the thermodynamic relation and the
effect of pressure on the heat capacity. We discuss the
effect of pressure on heat capacity and give an
equation to calculate the heat capacity at high press-
ure. We also apply the &bye model to the calcu-
lation of the effect of pressure on the heat capacity.
According to thermodynamic identities, we present
the formulas for calculating the thermal expansivity
at high temperature and high pressure. With these
relations we can extrapolate the thermal expansivity
with high accuracy to high temperature and high
pressure.
2 THE ENTHALPY AT HIGH PRESSURE AND
THE EFFRCI’ OF PRESSURE ON THE

agree well. The differences in thermal expansivity of HEAT CAPACITY

forsterite are as much as 20% at 1400 K between the The knowledge of enthalpy at high pressure is
recent experimental results [2]. This uncertainty in important in understanding the effect of pressure on
thermal expansivity can lead to certain uncertainties the heat capacity. We start with the thermodynamic
of the thermodynamic functions at high temperature. relation
Thus, the most serious error in the calculation of
thermodynamic functions arises from the uncertainty
of thermal expansivity at high temperature.
In the literature, the thermal expansivity of min-
erals is usually expressed as a function of temperature Integrating along an isotherm, we have
and is expanded in the form of a polynomial of the
temperature. The form of the polynomial varies H(T, P) - HfT, 0) = [VdP--T~I’xdP. (2)
greatly and it is very difficult to compare results from

629
630 XIANGXIA and JING-KMXuo

Table 1, Calculation of enthalpy at hi& pressure For perkhue

VW., ”
0.98 0.95 0.90 0.85
l-c AH” AH/Pb AH AH]P AH AH/P AH AH/P
300 934.2 273.59 2492.1 269.25 5569.4 261.39 9373.8 252.77
400 915.6 273.19 2442.9 268.92 5461.7 261.17 9196.1 252.66
500 897.5 272.93 2395.2 268.73 5357.0 261.09 9023.2 252.67
600 879.4 272.68 2347.5 268.55 5252.5 261.02 8850.6 252.70
700 861.4 272.43 2299.9 268.36 5148.1 260.95 8677.8 252.72
800 843.4 272.18 2252.5 268.20 5044.1 260.89 8505.9 252.77
900 825.4 271.94 2205.2 268.03 4940.1 260.84 8333.9 252.82
1000 807.4 271.65 2157.5 267.82 4835.5 260.75 8160.8 252.84
1100 789.4 271.38 2110.1 267.62 4731.3 260.68 7988.5 252.88
1200 771.4 271.08 2062.5 267.41 4626.9 260.59 7815.6 252.90
1300 753.5 270.80 2015.2 267.21 4522.7 260.51 7643.0 252.94
1400 735.3 270.43 1967.3 266.93 4417.5 260.37 7458.6 252.91
1500 717.3 270.08 1919.7 266.67 4312.8 260.25 7295.1 252.92
1600 699.3 269.70 1871.9 266.37 4207.7 260.10 7120.8 252.90
1700 681.3 269.33 1824.4 266.09 4102.8 259.96 6946.8 252.89
1800 662.9 268.82 1775.9 265.68 3996.3 259.70 6770.0 252.77
AH”: in Jg-‘.
AH/Pb: in lo-) cm3 g-l.
T? in K.
Data used in calculation come from Ref. 2.

A more straightforward calculation leads to the Rearranging eqn (41, we have

results given by Anderson and Zou [2],
H(T, I’) - H(T, 0) = AP + BPT. (9
H(T, P) - H(T, 0) = TV&&~ (x - 1)
For temperature To, we have
+w(x lnx -_x + 111
H(T,, P) - H(T,, 0) = AP + BPT,. (6)

Substracting eqn (6) from eqn (5) and arranging, we

have
+ 3@- 2)
- 1 (3)
4 1 H(T, I’) - H(T,,P) = H(T, 0)

where H(T, P) is the enthaipy at T, P, & is the -H(T~,O)+BP(T-TV). (7)

isothermal bulk modulus, V, is the volume at zero
pressure. 1y’ is the pressure derivative of Kr and
e = $(3k’ - 5), x = V/V,,, w = (dK,/dT),.
The temperature dependence of K’ is very small
[2,6,8], and as an approximation we take K’ = 4.2.
With eqn (3) we calculate the enthalpy at different
compression ratios and the results are shown in
Table 1. We find that at small compression the
enthalpy is linear with pressure. The enthalpy divided
by pressure is nearly constant at pressures less than
3OGPa (Fig. 1). We note also that the enthalpy
divided by the pressure varies with tincture at
smail compression and in the range of 500-1200 K,
the increment of enthalpy divided by the pressure can
be approximated by a constant (Fig. 2). Therefore, we
present an empirical relation,

AH/P = A + BT, (4) pm4

Fig. 1. Plot of AH v.s pressure for periclase calculated from
where A and B can be calculated easily, and eqn (3) at 300 K. The straight line is shown for comparison.
B = -3.18 x 10-6cm3g-’ K-l. The compression ratio is shown on the top.
 The heat capacity Cv can be expressed as a function
of the calorimetric Debye temperature and expressed
in powers of x = 8/T,
Cv=3R[l -&~2+&~4+..-]. (12)
According to the the~~~amic relation, the iso-
baric heat capacity can be determined in the form,

c, = Cv * &/k-T, (13)
where 4 is the adiabatic bulk modulus and Rr is the
@I isothermat bulk modulus. The heat capacity at high
.P
pressure is computed from eqns (f 2) and ( i I) and KS
;-I’ l and Rr at high pressure are taken from the Mur-
naghan formalism.
3-4- l The results of the calculation are shown in Fig. 3.
le l e
We note that only at very small compression can the
**a* heat capacity be approximated by a linear relation.
i-3 e**ee
-2- We note again that in the range of 500-1200 K, the
I t I increment of heat capacity divided by the pressure is
400 a00 12w la0
nearly a constant (Fig. 4). For periclase the elastic
Ikbye temperature is 94S-gIf K [5], eqn (9) is the
best fit to the experimentd data.

4. THE THERMAL EXF’ANSWITY AS A FUNCTION

OF TEMPERATURE
Noting the relation between heat capacity and eu-
The knowledge of the dependence of thermal ex-
thalpy, we have
pansivity on the temperature can be acquired from
the ~e~~~arnic identity,

and therefore we obtain the important relation,

C,=Co,+BP fe)

where C.“pis the heat capacity at zero pressure. Uut

calculation shows that, at small compression, the
isobaric heat capacity is linear with pressure and this
is important for the simple relation to calculate the
thermal expansivity.

3. THE HEAT CAPACITY AND DERYE

TEMPERATURE

Since very little thermodynamic data at high press-

ure are available, we apply the calorimetric Debye
temperature to the cakulation of the heat capacity at
high pressure and compare the results with those
computed from the enthaipy at high pressure, With
the Gruneisen parameter,

-- a 1n8 w
‘= dlnv Fig. 3. plot ofheat capacity C,, vs pressure for pwiclase to
60 GPa. The heat ~tipacitiesat differenttemperaturesare
where 8 is the Debye temperature we have indiited on the plot. The calorimetric Debyetemperature
c&dated from cqn (IZ), and the Debyetemperatureat high
pressure&k&a&d from eqn (11) and the heat capacityat
high pressurecalculatedfrom eqn (13).
632 XIANGXIA and JINCWAIXJAO

Table 2. The thermal expansivity of pericbtse at high tem- Table 3. The thermal expansivity of periclase at high press-
perature ure (10e6/K). The data are calculated from eqn (25). The
parameters used come from Ref. 2
P
(IG (g a-‘) (lO!& (lO$)
0 0.98 0.95 0.90 0.85 0.80
300 3.585 31.2 31.2
400 3.573 35.7 34.1 300 31.2 27.9 23.3 16.7 11.2 6.7
500 3.559 38.4 37.4 400 35.7 32.4 27.8 21.2 15.6 11.2
600 3.545 40.2 39.8 500 38.4 34.9 30.0 23.0 17.3 12.5
700 3.531 41.4 41.3 600 40.2 36.6 31.6 24.3 18.3 13.4
800 3.516 42.6 42.8 700 41.4 37.6 32.5 25.0 18.8 13.7
900 3.501 43.8 44.1 42.6 38.6 33.1 25. I 18.5 13.0
1000 3.488 44.7 45.2 z 43.8 39.1 34.1 25.8 19.1 13.6
1100 3.470 45.6 46.2 1000 44.7 40.5 34.8 26.5 19.6 14.0
1200 3.454 46.5 47.0 1100 45.6 41.2 35.2 26.5 19.2 13.3
1300 3.438 47.1 47.8 1200 46.5 42.0 35.8 26.9 19.5 13.5
1400 3.422 48.0 48.5 1300 47.1 42.8 36.1 26.9 19.2 13.0
1500 3.405 48.9 49.0 1400 48.0 43.2 36.5 27.0 18.9 12.4
1600 3.388 49.8 49.6 1500 48.9 441 31.4 27.7 19.8 13.2
1700 3.371 50.4 50.1 1600 49.8 45.0 38.4 28.7 20.8 14.3
1800 3.354 51.3 50.5 1700 50.4 45.5 38.9 29.3 21.3 14.8
1800 51.3 46.5 40.0 30.5 22.7 16.3
(a) Ref. 2.
(b) Calculated from eqn (18).

tal data in the range of elastic Debye temperatures

From the definition of isobaric thermal expansivity,
to calculate the constant B, and we obtain
eqn (14) becomes
B = -3.5442 x 10-6cm3g-’ K-l. Table 3 lists the
results of the calculation.
We must point out that it is difficult to calculate
with high accuracy the constant B from the enthalpy
at high pressure because of the uncertainty of the
Equation (15) can he rearranged as
experimental data and the small variation of enthalpy
with temperature. It is comparatively easy to
(16) measure the thermal expansivity in the range of
elastic Debye temperature and it is better to
obtain the constant B from these data. We have
Integrating eqn (16) and taking a, V0 when V = V,,,
already pointed out that at small compression the
a = a,, as a boundary condition, we find
heat capacity is linear with pressure. In fact we want
only to calculate the thermal expansivity at zero
aV-QV,= - dT. (17) pressure, and the subscript P in eqn (14) refers to the
zero pressure condition hence the derivative of the
heat capacity is the derivative at zero pressure. We
Substituting eqn (9) in eqn (17), we have
need only to use the data at very low pressure to
estimate the derivative. Therefore the linear approxi-
aV-a,V,= -BlnT/T,. (18)
mation we made is the best fit to the experimental
data.
We have already pointed out that in the range of
elastic Debye temperature, eqn (9) is the best fit to the
experimental data. Therefore, we use the experimen- 5. THE THERMAL EXPANSIVITY AS A
FUNCTION OF PRESSURE

According to the thermodynamic identity

Fig. 4. Plot of A&/P vs temperature for periclase at a (20)

compression V/V,, = 0.98.
 Thermal expansivity of per&se 633

Table 4. Comparison of 8,. (a) Ref. 9 from

1
0
- l/aK,(X#T),; (b) Ref. 3 from (a In u/d In v),; (c) this
work, calculated from (a In a/aIn V), ‘\
300K 12OOK 17OOK Reference ‘\ 3mc
1.

7
MgO 6.2 5.1 4.7
6.5 5.5 5.5 :
6.4 5.3 5.3 C
e -1.0
\
.

Integrating eqn (20) and considering q as a boundary \

I I
l -
condition, we have -0.1 -0.2

p
s0
Qn WN(J
1 aK dP
a-%= (21) Fig. 5. Plot of In 01vs In V for periclase. The data calculated
07?aTp .
from eqn (25). The temperature is indicated on the plot.

Using a Murnaghan equation of state, we have

K=&+K’P,
where K’ is the pressure derivative of KT and con-
sidered as a constant K’ = 4.2. Differentiating eqn
(22) at pressure P, we have
V/V, =0.85 and varies with temperature. Many
(22) papers have tabulated 6, = (a In a/a In V)r for many
minerals and 6r ranges from 6.5 to 4.5 for periclase
[I. We list the results of 6, at different temperatures
in Table 5. The results agree with the data calculated
from 6, = - l/aK,(dK,/dT)p [3,4].

Acknowledgement-The author would like to thank

(qp=(zgp +$K,P],=
aT
5
(ar ); (23) Professor J. Xiao for his support.

Because & is the isothermal bulk modulus at zero REFERENCES

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(Z),=(gp_:
Inserting eqn (24) into eqn (21), we have
Table 4 lists the results of the calculation. The plot
of In a vs In V is shown in Fig. 5. We find that
d In a/d In V is a constant to compression
(24)
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