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High Temperatures-High Pressures, Vol. 46, pp. 449–458 ©2017 Old City Publishing, Inc.

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Equation of state, thermal expansivity, and


Grüneisen parameter for MgO at high
temperatures and high pressures

S. Rekha, K. Sunil* and B. S. Sharma

Department of Physics, Khandari Campus,


Dr. B. R. Ambedkar University, Agra – 282002, India

Received: February 7, 2017; Accepted: March 1, 2017.

We have used the Stacey K-primed equation of state to determine pres-


sure-volume-temperature relationships for MgO upto a temperature of
3000 K and pressure of 225 GPa. Values of bulk modulus and its pressure
derivative are also obtained for the entire range of temperatures and pres-
sures considered in the present study. We have also investigated the ther-
moelastic properties of MgO at high temperatures and high pressures
using the results based on the equation of state. The pressure dependence
of thermal expansivity and the Grüneisen parameter both are determined
using the formulations which satisfy the thermodynamic constraints at
infinite pressure.
Keywords:  Equation of state, Bulk modulus, Thermal expansivity, Grüneisen
parameter, MgO, Infinite pressure behaviour

1 Introduction

MgO is an important ceramic and geophysical mineral [1–3] with various


applications in the field of condensed matter physics and geophysics. It has
large bulk modulus, less compressibility and high melting temperature [4,5].
MgO remains stable in the rock salt (NaCl) structure starting from the room
temperature up to the melting temperature and up to a pressure of nearly
225 GPa. The melting temperature more than 3000 K for MgO is nearly three

*Corresponding author: k.sunil.ibs@gmail.com

449
450 S. Rekha et al.

times larger than its Debye temperature nearly equal to 1000 K. Also the
phase transition pressure for MgO is much higher than its bulk modulus value
(160 GPa) at atmospheric pressure. Thus we have a wide range of tempera-
tures and pressures for MgO to investigate its thermoelastic properties [6,7].
First, we determine relationships between pressure P and volume V at
selected temperatures in the range 300 K to 3000 K using the Stacey recipro-
cal K-primed equation of state [8]. Values of K and its pressure derivative
K′ = dK/dP have also been calculated for the entire range of P and T. The
results for P, K and K′ obtained from the Stacey equation are used to deter-
mine the thermal expansivity and the Grüneisen parameter with the help of
the formulations which satisfy the boundary conditions at infinite pressure.

2  Method of analysis

The Stacey reciprocal K-primed equation of state is written as follows [8]

1 1  K ∞′  P
= + 1 −  (1)
K ′ K 0′  K 0′  K

Equation (1) represents a linear relationship between 1/K′ and P/K such
that [9]

1 P
=   (2)
K ∞  K ∞

The subscripts 0 and ∞ represent values at zero-pressure and at infinite


pressure, respectively. Eq. (1) has been integrated analytically [10,11] to
find
− K 0′ / K∞

K  P
= 1 − K ∞′  (3)
K0  K

Eq. (3) has also been integrated to yield [8,10]

V K′  P  K′ P
ln = 02 ln 1 − K ∞′  +  0 −1 (4)
V0 K ∞′ 
 K   K∞  ′  K

Thus P, K, K′ and V/V0 are directly related to each other, and can be deter-
mined with the help of Eqs. (1) to (4). Stacey equation is the only formulation
which makes a direct use of the constraint, Eq. (2), an identity at infinite pres-
sure. The parameters K0 and K ′0, the bulk modulus and its pressure derivative
both at zero pressure are temperature dependent quantities [2,3]. On the

other hand, K ∞ the pressure derivative of bulk modulus at infinite pressure is
independent of temperature [10,11]. K ∞ ′
is taken equal to (3/5) K ′0 [11].
Equation of state, thermal expansivity, and Grüneisen parameter 451


Values of K ∞ must be greater than 5/3, an important thermodynamic con-
straint due to Stacey [10,11].
For determining values of thermal expansivity a at different pressures
along selected isotherms we use the formulation [12] which satisfies the ther-
modynamic constraint [10] according to which the thermal expansivity van-
ishes in the limit of infinite pressure. Values of Grüneisen parameter g as a
function of pressure are determined using the reciprocal g relationship
recently formulated by Shanker et al. [13]. This formulation yields satisfac-
tory results for the Earths lower mantle and core in good agreement with the
seismic data [10].
The formulation used for a (P) is written as follows [12]
t
α = α0 (1 − K ′P / K ) (5)

where a0 is the thermal expansivity a at zero pressure. t is a material depen-


dent constant. The validity of Eq. (5) has been demonstrated for the Earth
lower mantle [12] with t = 1.13. The equation of state parameters K ′0 and K ∞′

for the lower mantle and MgO are very similar, we have taken t = 1.13 also
for MgO. We have calculated values of a using Eq. (5) which is consistent
with the thermodynamic constraint that a tends to zero in the limit of infinite
pressure [10,11]. Eq. (2) at infinite pressure when used in Eq. (5) gives a
equal to zero.
The reciprocal gamma relationship can be written as follows [13]

1 1  1 1 P
= + K ∞′  −  (6)
γ γ0  γ ∞ γ 0  K

where g0 and g∞ are respectively the values of g at zero pressure and in the
limit of infinite pressure. It should be mentioned that Eq. (6) satisfies the
boundary conditions at zero pressure (γ → γ 0 ), and γ → γ ∞ in the limit of
infinite pressure. Expressions for higher order Grüneisen parameters [13]
obtained from Eq. (6) have been found to be identical with those determined
from the basic principles of calculus [14–16].

3 Results and Discussions

For investigating the pressure-volume relationships at high temperatures, the


thermal pressure is of central importance [1,17,18]. We can determine ther-
mal pressure by knowing the values of thermal expansivity and bulk modulus
at high temperatures [2,3,9]. An alternative method for determining pressure-
volume relationships at higher temperatures has been developed [2,3,20]
using phenomenological equations of state with temperature dependent val-
ues of input parameters K0 and K ′0. For MgO, we use the Stacey K-primed
equation and the input parameters [1–3] given in Table 1.
452 S. Rekha et al.

Table 1
Values of input parameters for MgO taken from References [1–3]

300 K 500 K 1000 K 1500 K 2000 K 2500 K 3000 K


K0 (GPa) 162 156 141 126 109 94 79
K ′
0 4.15 4.21 4.36 4.53 4.74 4.95 5.16
a0 (10-5 K-1) 3.17 3.79 4.44 4.93 5.48 6.13 6.89

K∞  = 2.49, g0 = 1.54, g∞ = 1.08.

It should be mentioned that values of P/K in Eqs. (1), (3) and (4) range from

0 to 1/K ∞ . At P = 0, we have P/K = 0, and at infinite pressure, P/K becomes

1/K ∞ (Eq 2). Stacey [11] found that K ∞ ′
is nearly equal to (3/5) K ′0. When we
′ ′ ′
take K 0 = 4.15 for MgO [2,3] we get K ∞ = 2.49. Value of K ∞ is independent
of temperature [11], i.e. it remains same at different temperatures. Following
the procedure suggested by Stacey and Davis [10] we select values of P/K

ranging from 0 to 1/K ∞ equal to 0.4 for MgO. Values of P/K when substituted
in Eqs. (3) and (4) give K and V/V0, where V0 is the volume at P = 0. By
multiplying values of K and P/K we get the corresponding values of P. Finally,
we have determined values of K′ using P/K in Eq. (1). The results for P, K and
K′ are given in Tables 2–4. These are found to present good agreement with
the experimental data [21–25].
Now we use Eq. (5) to evaluate a(T,P) taking P, K and K′ from Tables 2–4
and a0(T) given in Table 1. The results are given in Table 5. Values of a(P) along
2000 K isotherm in Figure 1, and a(T) along selected isobars in Figure 2 are
compared with the available experimental data [21,26–29]. Calculated values of
thermal expansivity a present close agreement with the experimental data.
We have determined values of g as a function of pressure for MgO at 300 K
with the help of Eq. (6) taking data on P and K from Tables 2 and 3, and the

input parameters g0, g∞ and K ∞ from Table 1. The volume derivatives of g,
represented by q and λ are determined using the following expressions [13].
q  1 1  P
= K ∞′  − 1 − K ′  (7)
γ  γ ∞ γ 0  K

where q = (d ln γ / d ln V )T . The next derivative

λ = (d ln q / d ln V )T

 KK ′′  P
=   + K ′ + q (8)
1 − K ′P / K  K


where g∞ is related to K ∞ as follows [10]
K ∞′ 1
γ∞ = − (9)
2 6
Equation of state, thermal expansivity, and Grüneisen parameter 453

Table 2
Pressure–volume relationships for MgO at different temperatures

V/V0 Pressure, P(GPa)


300 K 500 K 1000 K 1500 K 2000 K 2500 K 3000 K
1.00 0 0 0 0 0 0 0
0.979 3.52 3.40 3.08 2.76 2.40 2.08 1.75
0.957 7.72 7.44 6.76 6.08 5.32 4.64 3.93
0.934 12.7 12.3 11.2 10.1 8.88 7.80 6.60
0.909 18.7 18.2 16.6 15.1 13.3 11.7 10.0
0.883 26.1 25.3 23.3 21.2 18.8 16.6 14.3
0.854 35.2 34.0 31.4 28.8 25.6 22.8 19.8
0.824 46.3 45.0 41.8 38.5 34.4 30.8 26.8
0.792 60.5 58.8 54.8 50.7 45.9 41.3 36.2
0.757 78.5 76.6 71.8 67.0 60.8 55.1 48.6
0.720 102 100 94.2 88.2 81.0 74.0 65.1
0.701 117 114 108 102 93.7 85.9 76.9
0.681 134 131 124 117 109 100 90.0
0.660 154 151 144 136 126 117 106
0.638 177 174 167 158 148 138 125
0.615 205 202 194 185 174 163 149
0.592 239 236 227 218 206 194 178

Table 3
Values of bulk modulus K as a function of compression V/V0 for MgO at different temperatures

V/V0 Bulk modulus, K(GPa)


300 K 500 K 1000 K 1500 K 2000 K 2500 K 3000 K
1.00 162 156 141 126 109 94 79
0.979 176 170 154 138 120 104 87.8
0.957 193 186 169 152 133 116 98.2
0.934 212 205 187 169 148 130 110
0.909 234 227 208 189 166 146 125
0.883 261 253 233 212 188 166 143
0.854 293 284 262 240 214 190 165
0.824 331 322 299 275 246 220 192
0.792 378 368 343 317 287 258 226
0.757 436 426 399 372 338 306 270
0.720 511 500 471 441 405 370 329
0.701 556 545 515 484 446 409 366
0.681 608 597 566 534 494 455 409
0.660 668 656 625 592 550 510 460
0.638 739 727 694 660 617 574 521
0.615 822 810 776 741 697 652 595
0.592 921 909 875 839 793 747 685
454 S. Rekha et al.

Table 4
Values of K′, the pressure derivative of bulk modulus as a function of compression V/V0 for MgO
at different temperatures

V/V0 K′ = dK/dP
300 K 500 K 1000 K 1500 K 2000 K 2500 K 3000 K
1.00 4.15 4.21 4.36 4.53 4.74 4.95 5.16
0.979 4.02 4.07 4.20 4.35 4.54 4.72 4.90
0.957 3.89 3.94 4.06 4.19 4.35 4.51 4.66
0.934 3.77 3.82 3.92 4.03 4.18 4.31 4.45
0.909 3.66 3.70 3.79 3.89 4.02 4.13 4.25
0.883 3.56 3.59 3.67 3.76 3.87 3.97 4.07
0.854 3.46 3.49 3.56 3.63 3.73 3.82 3.91
0.824 3.36 3.39 3.45 3.52 3.60 3.68 3.76
0.792 3.27 3.30 3.35 3.41 3.48 3.55 3.61
0.757 3.19 3.22 3.26 3.31 3.37 3.43 3.48
0.720 3.11 3.13 3.17 3.22 3.27 3.32 3.36
0.701 3.07 3.09 3.13 3.17 3.22 3.26 3.31
0.681 3.03 3.06 3.09 3.13 3.17 3.21 3.25
0.660 3.00 3.02 3.05 3.08 3.12 3.16 3.20
0.638 2.96 2.98 3.01 3.04 3.08 3.11 3.14
0.615 2.93 2.94 2.97 3.00 3.03 3.06 3.09
0.592 2.89 2.91 2.93 2.96 2.99 3.02 3.05

Table 5
Values of thermal expansivity a as a function of compression for MgO at different temperatures

P a × 105 K
V/V0
(GPa) 300 K 500 K 1000K 1500K 2000K 2500K 3000K
1.00 0 3.17 3.79 4.44 4.93 5.48 6.13 6.89
0.979 3.52 2.88 3.44 4.02 4.45 4.92 5.48 6.49
0.957 7.72 2.62 3.12 3.63 4.01 4.42 4.90 6.04
0.934 12.7 2.37 2.82 3.28 3.61 3.95 4.37 4.85
0.909 18.7 2.14 2.55 2.96 3.24 3.53 3.89 4.31
0.883 26.1 1.93 2.29 2.65 2.89 3.15 3.46 3.82
0.854 35.2 1.73 2.06 2.37 2.58 2.81 3.07 3.37
0.824 46.3 1.55 1.83 2.11 2.29 2.48 2.70 2.97
0.792 60.5 1.37 1.63 1.87 2.02 2.19 2.37 2.60
0.757 78.5 1.21 1.43 1.64 1.77 1.91 2.07 2.26
0.720 102 1.06 1.25 1.43 1.53 1.65 1.79 2.00
0.701 117 0.980 1.17 1.33 1.42 1.53 1.66 1.80
0.681 134 0.913 1.08 1.24 1.33 1.41 1.54 1.67
0.660 154 0.839 0.990 1.13 1.23 1.33 1.43 1.52
0.638 177 0.786 0.924 1.04 1.13 1.20 1.29 1.42
0.615 205 0.720 0.852 0.958 1.03 1.11 1.19 1.28
0.592 239 0.662 0.772 0.885 0.941 1.01 1.08 1.17
Equation of state, thermal expansivity, and Grüneisen parameter 455

Figure 1
Calculated thermal expansivity (a × 105 K) as a function of pressure for MgO compared with
the experimental data at 2000 K. The symbol ¨ rerpresents vibrational spectroscopic data [26],
Φ shock-wave data [21], and x the ab-initio values [29].

Figure 2
Calculated thermal expansivity curves for MgO. a × 105 K versus temperatures are plotted along
selected isobars. The symbols O, ¨ and x represent the data from Wang and Reeber [28], Cynn
et al. [27] and Karki [29], respectively.

In view of Eq. (2), Eq. (7) reveals that q∞, value of q in the limit of infinite
pressure, tends to zero. Eq. (8) at infinite pressure gives
1  KK ′′ 
λ∞ = K ∞′ +   (10)
K ∞′ 1 − K ′P / K ∞
456 S. Rekha et al.

Eq. (10) represents an identity for the third order Grüneisen parameter derived
by Shanker et al. [15]. Eq. (10) also reveals that λ∞ is positive and finite [16].
Eqs. (7) and (8) thus satisfy the constraints for q and λ at infinite pressure
found by Stacey and Davis [10].
Values of KK″ are determined from the Stacey equation (1) using the fol-
lowing expression [10]

K ′2
KK ′′ = − (K ′ − K∞′ ) (11)
K 0′

Values of g, q and λ for MgO obtained from Eqs. (6)–(8) are reported in
Table 6. The results are found to present agreement with the empirical values
of g, q and λ for MgO determined by Kushwah and Sharma [6].

Table 6
Values of the Grüneisen parameter g and its volume derivatives q and λ as a function of pressure
for MgO at 300 K

V/V0 P (GPa) g q l

1.00 0 1.54 1.06 5.21

0.979 3.52 1.51 0.96 4.85

0.957 7.72 1.48 0.86 4.51

0.934 12.7 1.45 0.77 4.20

0.909 18.7 1.42 0.69 3.93

0.883 26.1 1.39 0.62 3.67

0.854 35.2 1.37 0.55 3.43

0.824 46.3 1.33 0.49 3.22

0.792 60.5 1.32 0.43 3.03

0.757 78.5 1.29 0.38 2.84

0.720 102 1.27 0.33 2.68

0.701 117 1.26 0.31 2.59

0.681 134 1.25 0.29 2.52

0.660 154 1.24 0.26 2.44

0.638 177 1.23 0.25 2.39

0.615 205 1.22 0.23 2.31

0.592 239 1.21 0.21 2.26


Equation of state, thermal expansivity, and Grüneisen parameter 457

4 Conclusions

We have used the Stacey reciprocal K-primed equation of state which satis-
fies important boundary conditions at infinite pressure. These conditions

reveal that K ∞  > 5/3, γ ∞ > 2 / 3, q ∞ → 0 and λ∞ is positive finite. It is found
from the P-V-T results obtained for MgO that for producing the same amount
of compression (V/V0), the magnitude of required pressure becomes smaller
and smaller as the temperature is increased from 300 K towards higher tem-
peratures upto 3000 K. Values of bulk modulus K increase with the increase
in pressure, and decrease with the increase in temperature. Since the bulk
modulus is inverse of compressibility, it becomes harder to compress the
solid at higher pressures because of the increasing bulk modulus. On the
other hand, at higher temperatures the solid becomes softer and can be com-
pressed to the same extent by a less amount of pressure. Values of K′, rate of
change of bulk modulus with pressure, decrease continuously with the

increase in pressure. K′ attains a positive finite value equal to K ∞ at very high
pressures in the limit of extreme compression.
One of the most important thermodynamic constraints due to Stacey [11]
is the fact that thermal expansivity of a material vanishes in the limit of infi-
nite pressure. Eq. (5) for a satisfies this constraint in view of Eq. (2). Values
of a calculated from Eq. (5) for MgO at finite pressures present good agree-
ment with the experimental data. Values of the Grüneisen parameter g, and its
volume derivatives. q and λ determined from Eqs. (6)–(8) satisfy the thermo-
dynamic constraints due to Stacey and Davis [10]. The present study has thus
demonstrated the usefulness of the Stacey equation of state for determining
thermoelastic properties of MgO under high pressures and high temperatures.

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