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1 Introduction
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
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 ∞
′
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)
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].
Table 1
Values of input parameters for MgO taken from References [1–3]
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
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
Table 3
Values of bulk modulus K as a function of compression V/V0 for MgO at different temperatures
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
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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458 S. Rekha et al.