NeuroQuantology | October 2023 | Volume 21 | Issue 7 | Page 624-647| doi: 10.48047/nq.2023.21.7.

nq23055
Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

A study assessment of the thermodynamic

properties of MgO and CaO at PREM
pressures up to the outer core’s limits of the
Earth
Abderrahim Achouri1
1
Laboratoire de Développement des Energies Renouvelables dans les Zones Arides et Sahariennes,
Département de Physique, Université d’Ouargla, 30000 Ouargla, Algeria
Salah Tlili2
Email Corresponding Author: tlilisalah2007@gmail.com
2
Univ. Ouargla, Fac. Mathematics and Material Sciences, Lab. Development of New and Renewable
Energies In Arid And Saharan Zones Laboratory (LARENZA), 30000, Ouargla, Algeria
Abdelmadjid Kaddour3
3
Unité de Recherche Appliquée en Energies Renouvelables, URAER, Centre de Développement des
Energies Renouvelables, CDER, 47133, Ghardaïa, Algeria
Benatallah Nassiba4
4
Univ. Ouargla, Fac. Mathematics and Material Sciences, Lab. Development Of New And Renewable
Energies In Arid And Saharan Zones Laboratory (LARENZA), 30000, Ouargla, Algeria
Mohammed Said Nedjimi5
5
Univ. Ouargla, Fac. Mathematics and Material Sciences, Lab. Valorisation and Promotion of Saharan
Resources Laboratory (VPRS), 30000, Ouargla, Algeria
Medjahed Driss Meddah6
6
Mechanical Engineering Department, University Center Salhi Ahmed Naama, Naama45000, Algeria
Medjadji Nassira7
7
Electrical Engineering Department, University Center Salhi Ahmed Naama, Naama45000, Algeria
Received: July 11, 2023, Revised: September 05, 2023, Accepted: October 27, 2023, Published:
November 20, 2023

Abstract:
624
Using the PBEsol function of the GGA approximation of the DFT method included in the CASTEP
program, the optimization of the geometric structure of MgO and CaO was calculated to observe the
possible phase transformation of their crystal structures in a pressure range from 0 to 140 GPa. The
evolution of the Debye temperature with pressure changes was also examined after calculating the
elastic properties. We were therefore able to study the changes in heat capacity, internal energy,
entropy, and Gibbs energy as a function of pressure and temperature. Moreover, we were able to
compare the values of these parameters for these two oxides, particularly within this field of study,
which extends from the surface of the earth's crust to the confines of its outer core. We found that
the results were in excellent agreement with previous studies. The MgO stabilizes in phase B1, while
the dioxide transforms at a pressure of 59.2 GPa from this phase to phase B2. The agreement is also
clear for the Debye temperature of both oxides, and the values of both the heat capacity with
constant volume and the entropy at 300 K for magnesium oxide. While we were not able to compare
the results of our calculation for both internal and free energy of oxides and the tow thermodynamic
parameters for calcium oxide with the results of previous studies because they are not available.
Keywords: phase transformation, Debye temperature, thermodynamic properties, MgO, CaO, PREM
model
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NeuroQuantology | October 2023 | Volume 21 | Issue 7 | Page 624-647| doi: 10.48047/nq.2023.21.7.nq23055
Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth
DOI Number: 10.48047/nq.2023.21.7.nq23055
Introduction
As one of the major earth-forming
minerals, periclase (MgO) is stable in rocksalt
(RS) structure with the pressure up to 227
GPa. This unique structural stability makes
MgO an ideal standard for calibrating pressure
in experiments at extreme conditions. [1]
It is well known that the computations of
thermodynamic functions (entropy, for
example) require knowledge of the thermal
expansivity a and compressibility K as well as
the specific heat. The pressure (or volume)
and temperature variation of a and K
contribute to the pressure (or volume) and
temperature variation of the thermodynamic
functions. [2]
It is extremely difficult to determine the
material of the Earth and the physical state
and the chemical composition of this material
at depths where is no direct observation. Rock
samples originate from depths not exceeding
Table 1: Depth, pressure, and temperature values from work [00] at the limits of the Earth's inner
layers up to the Gothenburg region
Depth
(km)
0 0
Crust
80,0
80,0
Uppermantle
670,0
670,0
Lowermantle
2891
Richet et al. 1988, calculated physical
properties from first principles for simple
compounds with promising applications for
conditions beyond the reach of current
experimental techniques. We also compare
our high pressure data with theoretical
calculations to assess their geophysical
validity.[6]
Nie et al. 2023, found that supplementation
with appropriate calcium oxide and
magnesium oxide proportions accelerates the
CO2 absorption rate and shortens the
saturation time of the MDEA solution by
9%−17%. [7]
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NeuroQuantology2023;21(7):624-647
9 km since this is the greatest depth attainable
by the present drilling techniques. Though
some rock materials find their way to the
surface by geological processes - primarily by
volcanic eruptions - from depths exceeding
those of drillings, even these samples provide
only limited information concerning at most
only some portion of the upper mantle of the
Earth. [3]
Manganese (Mn) is the 3rd most abundant
transition metal in the Earth’s crust1 and
highly sensitive to redox processes indicative
of specific aqueous environments2,3. While
Earth’s crust has an average Mn abundance of
0.019 mole/kg4, concentrated Mn exists in the
form of oxide nodules in oceanic sediments,
which are found at almost all depths and
latitude. [4]
Völgyesi et al. 1985, [5] studied the Eart’s
inner layer (see table 1).
Pressure (GPa) Temperature (K)
300
2,4539 1000
2,4546 1000
23,8334 1600
23,8342 1600
625
135,7509 4700
Randhir et al. 2019, considered the
development of a new magnesium-
manganese oxide reactive material for
thermochemical energy storage that displays
exceptional reactive stability, has a high
volumetric energy density greater than 1600
MJ.m−3, and releases heat at temperatures
greater than 1000 °C. [8]
Imashuku et al. 2020, acquired the CL spectra
of CaO and MgO containing FeO and MnO at
various contents and investigated the effects
of the dissolved FeO and MnO on the
luminescence properties of f-CaO and f-MgO
on the basis of the obtained CL spectra. [9]
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NeuroQuantology | October 2023 | Volume 21 | Issue 7 | Page 624-647| doi: 10.48047/nq.2023.21.7.nq23055
Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth
Elmi,et al. 2023, focused on Mn oxides
collected at the southern bound of the
abandoned open-pit site called Crimora Mine
(Augusta County, Virginia, USA), and they used
mineralogical and chemical features to shed
light on the origin of manganese deposits in
Crimora that occur along the western foot of
the Blue Ridge Mountains. [10]
Jia et al. 2021, convinced that this review
article will be of significant interest for
researchers working on chemical oxidation for
water decontamination processes, and they
highlighted how the literature lacks
information and data that are crucial prior to
high-scale applications. [11]
Szymoniak et al. 2022, summarized the
effectiveness of magnesium oxide (MgO)
media for soft water remineralization, as well
as its potential for divalent metal removal
(e.g., Mn, Cu, and Zn), which is of particular
interest in small or residential applications.
[12]
Miao et al. 2018, used the first principles and
quasi-harmonic Debye model in order to study
the thermodynamic properties, enthalpies,
electronic and optical properties of MgO up to
the core–mantle boundary (CMB) condition
(137 GPa and 3700 K). [13]
Bukowinski,et al. 1985, compared the
predicted B1-B2 transformation pressure for
CaO, which is 32 GPa, to the experimental
value of 61 GPa, and they found that the
corresponding pressure for MgO is 205 GPa,
which is a lower bound on the actual
transformation pressure. [14]
Zhao et al. 2007, revealed that, at 300 K, the
Debye temperatures from their obtained
elastic constants are well consistent with
other theoretical results. In addition, they
found that the Debye temperature increases
nonlinearly with increasing pressure. [15]
Riboud et al. 1963, studied the equilibria in
the systems CaO-manganese oxide and MgO-
manganese oxide in air as part of a series of
investigations dealing with the chemistry of
oxides at high temperatures. [16]
Guliyev et al. 2020, focused on the isotropic
ball using data of Preliminary Reference Earth
Model (PREM). And they demonstrated that
such a ball should be either destructed or
gone into a more stable equilibrium state with
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uneven distributed deformation under
thermobaric condition of the inner core. [17]
Tangstad,et al. 2017, described the reduction
of the MnO and the reminding slag
composition in the high-temperature zone.
[18]
Mehl et al. 1986, calculated the B1-B2 phase
transition pressures within the PIB model to
be 251 GPa (MgO), 55 GPa (CaO), 36 GPa
(SrO), and 21 GPa (BaO), in very good
agreement with available experimental data
for these compounds. [19]
Dziewonski et al. 1981, developed a standard
model for the structure of the Earth, from the
center to the surface, defining the main
parameters and principal discontinuities in
such a way that they could be adopted by the
international scientific community in any
studies that depended on the Earth’s
structure. [20]
Anderson et al. 1990, assessed the data for all
the thermodynamic functions of an important
mineral, MgO or periclase, with a temperature
range of 300 to 2000 K. [2]
After all this reminder of what was mentioned
previously, we can simply realize that the
study of the thermodynamic properties of
these two oxides and therefore the
comparison between them, in particular at the
pressures of the PREM model, is missing.
In the current work, we will support all these
studies by targeting this deficiency, starting by
presenting the calculation method adopted.
Followed by a discussion of the results of the
structural optimization of each oxide to
determine the phase transformation when
subjected to hydrostatic pressure, which
allows us to address their thermodynamic 626
properties, in addition to presenting a
comparison between these results. Finally, a
summary of the most important results
II. Methodology
Density functional theory (DFT) is one of the
most important methods used in theoretical
physics and chemistry, and thanks to it we can
determine the properties of a multiparticle
system, the total energy of the system, the
electron density of orbitals, physical and
optical parameters of matter, etc., and it is
one of the most used methods in quantum
calculations to solve the Schrödinger equation
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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

due to the possibility of applying it to various given minimum volume in an electronically

(multivariate) systems [21]. The CASTEP
program is based on this theory [22], which
uses several approximations, including;
Local density approximation (LDA) is a local
approximation of the inhomogeneous
electronic system as a homogeneous position,
based on dividing the total volume by the
homogeneous gas, formed in the case of an
interaction, and it is precise in a particular
case where the electrons exist in a region of
space with a regular external potential to
maintain the stability of the system, that is,
they are connected to an electronically regular
gas. [23]

In this case, the density function is related to the exchange and bond energy of a gas particle with
uniform electron density, where the bond exchange energy is given by the following equation:

The total energy is divided into two parts, where Correlation energy, Exchange energy

The generalized gradient approximation (GGA) was introduced [24] to improve the accuracy obtained
in LDA, where the exchange and binding energy are written as a function of the electron density ρ(r)
and the gradient |ρ (ρ)∇ | is not considered a regular property of electron gas.
.
627

This approximation has developed and strengthened due to its multiple possibilities of use. In 2008,
the PBEsol approximation used here and explained in detail in [25] appeared.
In addition, to determine the modification of certain parameters with changes in pressure, there are
multiple methods, including those that allow compensating or bringing any function in a certain
domain closer to another function. Among these functions are polynomials, which are widely used.
The pattern often defined as generation or polarization [26] can be used here, where it can be
written:

It is necessary to determine the coefficients ai
of the polynomials of degree n. One of the
following numerical methods can be adopted:
Lagrange method, finite difference method,
Newton method, partitioned difference
method, diving method, Stirlich method,
Bessel method, and inverse polarization
method in the case of regular points and
irregular
Finally, integrals are calculated by various
numerical methods that depend on the
repetition of certain operations. Romberg is
the least reproducible and most accurate
method, as described in [27].
III. Results and interpretation:
III-1 Transformation phase:
After calculating the enthalpy of the B1 and B2
phase structures for MgO and CaO in the field
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of this study, i.e., between 0 and 140 GPa, we
obtain:
Figure (2) presents the change in enthalpy of
formation for phases B1 and B2 of calcium
magnesium oxide with a change in pressure,
from which the following can be observed:
There is a clear increase in the values of this
quantity with increasing pressure, and this
increase is almost linear. At the limits of the
study field and for the first phase, the values
of this quantity are limited between -2129.81
and -2116.67 eV, and for the second oxide,
they are between -1446.09 and -1428.15 eV.
As for the second phase, it is limited between
-2128.37 and -2115.73 eV and between -
1445.17 and -1429.16 eV for the two oxides,
respectively. From these values, it appears
that the values of this quantity for calcium
oxide are greater than those of the first oxide,
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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

and in addition, it increases faster for the
same oxide compared to the ever-increasing
speed of the first oxide.
In addition, its development for stage B2 is
much faster than its development for the
other stage. The difference in its values
between these two phases decreases until the
pressure reaches 59 GPa, where it is almost
non-existent, and from the pressure of 60
GPa, this difference begins to increase, taking
a negative sign (see Table 1). This means that
there is a phase transformation occurring
between these two pressures, and with
careful calculation, the resulting longitudinal
transformation pressure in our study is at a
pressure of 59.2 GPa. Based on the
relationship between pressure and earth
depth, it can be said that the phase
transformation of this oxide takes place at a
depth of 1435 km from the earth's crust, i.e.,
in the lower mantle of the earth, at a distance
of 1456 km from the earth's surface.
Gutenberg region, which represents the
dividing limit between this part of the mantle
and the outer core.
For magnesium oxide, the enthalpy values of
the formation of phase B2 are higher than
At absolute zero, at which the calculation is carried out in our case, the change in free energy ∆G of
crystal formation is equal to the enthalpy H or the enthalpy of formation, where :
those of phase B1, with its development being
slightly slower, resulting in a decreasing
difference but with small quantities. All this
proves the stability of the salt structure of this
oxide over the entire area of our study, that is
to say, the instability of the other phase. This
result confirms the stability of MgO in its first
phase over the entire study area, which
means that this oxide, up to the limits of the
earth's outer core, remains stable in this
structure.
For magnesium oxide, this result is consistent
with the theoretical work of Bukowinski, M. S.
T [14] from 1985, who found the phase
transition to be around 205 GPa. This also
agrees with the result of the experimental
work of Vassiliou and Ahrens [30] 1981, who
experimentally determined that the phase
transition occurs at a pressure of about 200
GPa.
As for calcium oxide, this result is very close to
the degree of agreement with what was found
experimentally in the work of P. Richet et al
[6], since it is 0.8 GPa lower than this. which
was determined in this study.
628

where T is the temperature and S is the entropy of formation.

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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

Figure (1): Enthalpy changes of formation of the B1 and B2 phases of the MgO structure with
changing pressure

Figure (2): Enthalpy changes of formation of the B1 and B2 phases of the CaO structure with
changing pressure

III-1 Debye temperature:
The CASTEP program used calculates the
Debye temperature, and we know how to
calculate it as described in [1], for example.
The values presented in Figure (3) evolve with
the changes in pressure for each of the two
oxides at the pressures used in the calculation
by the program, at the pressures of the PREM
model, and finally at those representing the
polynomial approximating their change.
From this figure, it is clear that there is an
increase in the values of this coefficient for
both oxides, but this increase occurs at
different speeds. The fastest increase appears
for its values related to the B2 phase of
calcium oxide, while the slowest also appears
in the other phase of this oxide. This is
confirmed by calculating the increase field or
value range of this parameter using the values
recorded in Table 1. These values are: 415.40,
91.75, and 271.42 K for magnesium oxide in its
stable phase, calcium oxide in phase B2, and
finally in its second phase.
Through the same figure and the values in the
same table, we can see that the Debye
629
temperature of calcium oxide is always lower
than that of magnesium oxide, and even more
so in the first phase of calcium oxide, its
values are lower than those of its second
phase. All this causes the difference between
the oxide values for the stability of the B1
phase of calcium oxide to increase, in contrast
to the difference for the stability of the B2
phase. This difference at pressures of 0, 50,
60, and 140 GPa is estimated at 240.60,
390.65, 348.86, and 222.86 K, respectively.

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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

Figure 3: Debye temperature changes of MgO and CaO with a change in pressure
At zero pressure, the Debye temperature
value of magnesium oxide, according to the
theoretical work of Oganov and Dorogokupets
[25], is 3.97 K higher than our value, which is
30 K lower than the experimental work of S.V.
Sinogeikin and J.D. Basse [28]. Comparing the
value of this degree resulting from the
computational work of A. Jemmy Cinthia et al.
[29] on calcium oxide, it is 25.57 K higher than
the value of our results, while the value of the
experimental work by E. Gmelin and Z.
Naturforsch [7] is lower by 0.60.43 K. These
results show that the values for magnesium
oxide are more consistent, although
agreement is present even for calcium oxide.
After determining the appropriate
630
polynomials for the change in Debye
temperature with the change in pressure, we
found that they have degrees and are: The
sixth relates to magnesium oxide, and the
fourth relates to the two phases of
magnesium oxide and calcium. This result is
sufficient to determine the values of this
parameter for all pressure values, especially
those that represent significant depths in the
subsoil, such as the border areas between its
most important sections, as shown in Table 2.

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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

Table 2: Values of polynomial coefficients suitable for changes in the Debye temperature of MgO

Degree of
Polynomial coefficients
polynomial
a6 a5 a4 a3 a2 a1 a0
Elastic -7.75E- -10.83E- 13.95E- -11.57E-
MgO 6 4.55E-08 8.23 905.93
Debye 11 06 04 02
temperature -8.44E- 16.13E- -13.81E-
CaO/B1 4 5.77 665.41
(K) 06 04 02
and CaO with changes in pressure.

This result also allows us to determine the
values of the thermal properties with great
precision and also helps us to simplify the rest
of the study.
III-3 Thermodynamic Properties:
III-3-1 Internal energy:
In fact, the internal energy of a crystal is the
sum of the energies of translation, rotation,
and vibration. The latter (the vibration energy
of the 𝐸 atoms) is very important in the
calculation of the specific heat of solids,
because it constitutes the fundamental part of
the energies possessed by the system Debye
assumed in his theory of the specific heat of
solids that the atoms of solids oscillate
collectively; that is, he considered the
movement of the lattice as a whole instead of
considering each atom as oscillating 631
independently. From each other, as Einstein
supposed in his theory. It is calculated from
the following relationship [17]:

N is the number of molecules, kB is the Baltzmann constant, and T is the temperature.

And

ħ is Planck's constant, and ωD is the vibration frequency.

From Figures 4 to 7 and Table 3, it can be seen
that the internal energy of calcium oxide is
limited to the spheres, the longest of which is
60.683 GPa for pressure, which is estimated at
103.71 kjoule/mole, and the narrowest is for a
pressure of 23.8334 GPa, which is estimated
at 29.64 kjoule/mole. As for magnesium oxide,
it is confined to spheres, the longest of which
is estimated at 103.46 kjoule/mole and the
narrowest of which is estimated at 29.30
kjoule/mole, which are for the same pressures
as previously. But the real limitation of the
values of this energy for calcium oxide is in the
longest ranges, estimated at 99.14
kjoule/mole, while the narrowest ranges are
estimated at 28.61 kjoule/mole. As for the
second oxide, it is estimated at 101.05 and
27.41 kjoule/mole, respectively. These two
intervals appear in the same region for the
two oxides, respectively, in the field of
appearance of the second phase of calcium
oxide and in the upper terrestrial mantle. The
values of this energy change inversely with
changes in pressure, because for lower
pressure values, its values are higher in the
same layer.
For all pressures and for the two oxides, the
values of this energy increase linearly with the
increase in temperature, with very close
inclinations, since the difference in
inclinations does not exceed 50 joule/mole.
Therefore, we find that the values of the
difference between their values are very close
in the earth's crust, as it appears identical in
figure (4), and it is the smallest difference for
the two oxides, which are estimated
respectively at 116.37, 120.62 joule/mole at
300 K and at 215.07, 296.62 joule/mole at
1000 K. This difference is also very close and
almost applicable for calcium oxide in its first
phase of the Earth's lower mantle (see Figure
(6)), since this difference is estimated,

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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

respectively, at 201.90 and 209.59 joules per
mole, from temperatures of 1600 and 2488 K.
This difference takes approximately the same
values starting from the Earth's upper mantle
(see Figure (5)) to the limits of the phase
transition of the other oxide in the Earth's
lower mantle (see Figure (6)). This is
consecutive, with values estimated at 1889.54
and 2024.29 joule/mole for 1000 and 1600 K,
respectively. It also takes estimated values of
1783.42 and 1888.83 joule/mole for 1600 and
2488 K, respectively. The highest values of the
difference appear at the end of the Earth's
lower mantle, where at 2620 K the value is of
the same order as the two oxides, and it is
4395.41, 2286.40 joule/mole, while 'at 4700 K
its values are still in the same order as the two
oxides, and it is 4572.85, 2409.43 joule/mole
(see Figure (7)).
The values of this energy at the boundaries
separating the layers are almost equal, since
the difference between the boundaries of the
Mohosevich region is estimated at 0.06
joule/mole for calcium oxide and 0.08
joule/mole for calcium oxide. magnesium
oxide, while it is estimated at 0.02 and 0.06
joule/mole for the oxides and in the same
sequence between the limits of the region
separating the two layers of the mantle.
Unfortunately, no previous studies have
indicated this energy so that a comparison can
be made with it.

632

Figure (4): Changes in internal energy with changes in temperature and pressure at the boundaries
of the Earth’s crust

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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

Figure (5): Internal energy changes with temperature and upper mantle boundary pressure

633

Figure (6): Internal energy changes with temperature and lower mantle boundary pressure up to
the phase transition pressure for CaO

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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

634

Figure (7): Internal energy changes with temperature and lower mantle boundary pressure starting
from the phase transition pressure of CaO
III-3-2 Heat capacity at constant pressure:
The heat capacity of a solid body at constant volume, Cv, is defined as the change in the thermal
energy of the solid body resulting from a change in the temperature of the steel by one degree [18].
Or

According to Debye's law, the mathematical formula for heat capacity can be written as follows:

By substituting into this equation the speed of sound resulting from the

relation And by introducing the notion of Debye temperature, we obtain:

R is the gas constant.

From table (3) and figures (8 to 11), it is noted
that the constant pressure heat capacity of
calcium oxide and magnesium oxide is limited
to narrower ranges, of which the pressure is
60.683 GPa, estimated 0.14 and 0.27
joule/mole.K, respectively. And the longest of
them is for the pressure of 2.4539 GPa, which
is estimated 10.07 and 16.25 joule/mole.K,
respectively. But the real limit of the values of
this calcium oxide capacity lies in the ranges of
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which the longest is estimated 9.71
joule/mole.K, while the narrowest is
estimated 0.09 kjoule/mole.K. As for the
second oxide, they are respectively estimated
at 15.71 joule/mole.K and 0.24 joule/mole.K.
These two zones appear in the same zone for
the two oxides, namely, respectively, in the
earth's crust and in the zone where the
second phase of calcium oxide appears. The
values of this capacity change inversely with
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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

changes in pressure, because for lower same layer.

pressure values, their values are higher in the

635
Figure 8: Changes in heat capacity with constant volume with changes in temperature and pressure
at the boundaries of the Earth’s crust

Figure (9): Changes in heat capacity with constant volume with changes in temperature and
pressure at the boundaries of the upper Earth’s mantle

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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

636
Figure (10): Changes in heat capacity with constant volume with changes in temperature and lower
mantle boundary pressure up to the phase transformation pressure of CaO

Figure (11): Heat capacity changes with constant volume with changes in temperature and lower
mantle boundary pressure starting from the phase transformation pressure of CaO.
The values of this capacity increase non- they always decrease with increasing
linearly with increasing temperature, for all temperature. It appears identical in figure (8)
pressures and for both oxides, since this at higher degrees, i.e., at 1000 K, which is the
increase occurs as usual in the earth's crust smallest difference for the two oxides and is
but slows down in the rest of the layers. It is estimated at 0.03 and 0.05 joule/mole.K,
also noted that the differences between their respectively. While at 300 K, they are also
values are very close in the earth's crust, and respectively 0.12 and 0.23 joule/mole.K,

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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

because it is clear that they are higher. As for oxide exceeds its value at the temperature of
figure (10), it is clear that this difference is 1000 K from the Earth's upper mantle (Figure
constant and also very close and almost 9) by 0.05 joule/mole.K, while it decreases by
applicable for calcium oxide in its first phase in the same amount at the temperature of 1600
the Earth's lower mantle, since its value is K and in the same region.
estimated at 0.01 joule/mole.K at The values of this capacitance at the
temperatures of 1600 and 2488 K. In the same boundaries separating the layers are equal,
region (Figure 10) and starting from the upper the difference is therefore zero. The value
terrestrial mantle (Figure 9) and for resulting from our study at room temperature
magnesium oxide, this difference takes almost is approximately 3 joule per mole, which is
the same value and is estimated at 0.17 at a higher than that resulting either from the
temperature of 1600 K, while at 1000 and mathematical work of B.B. Karki et al. [31] or
2488 K it is estimated at 0.08 and 0.37 from experimental work [32]. It remains
joule/mole.K, respectively. At 2620 and 4700 impossible to compare the values of our
K, the difference is estimated, respectively, for calculations for the second oxide with the
magnesium oxide at 0.10 and 0.03 values of the results of other studies due to 637
joule/mole.K and for calcium oxide at 0.15 and their lack of availability.
0.05 joule/mole.K. This difference for calcium
III-3-3 Entropy:
Entropy is the amount of randomness in matter and is calculated based on the second law of
thermodynamics with the following relationship:

It is still clear from figure (12) and table (3)
that the change in entropy with a change in
temperature for both oxides is consistent with
what has been stated about the change in
heat capacity with a change in temperature,
because the values of this entropy also
increase in a non-linear manner and only in
the earth's crust. The values of this entropy
are limited to intervals with widths of 25.08
and 34.64 joule/mole.K for a 0 GPa,
respectively, for calcium oxide and magnesium
oxide. As for 2.4539 GPa, the width of these
intervals in the same sequence as for the two
oxides is estimated to be 8.23 and 13.75
joule/mole.K. But the width of the real
intervals is 25.69 and 34.64 joules/mole.K,
respectively, theses intervals are considered
the longest of all. We also notice that the
values of the difference between their values
are very close in the earth's crust and that
they always decrease with increasing
temperature. It also appears identical at
higher temperatures, i.e., at 1000 K, which is
the smallest difference between the two
oxides and is estimated at 0.06 and 0.17
joule/mole.K, respectively. While at 300 K,
they are also respectively 0.66 and 0.73
joule/mole.K, because it is clear that they are
higher.

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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

638
Figure (12): Entropy changes with changes in temperature and pressure at the boundaries of the
Earth’s crust

Figure 13: Entropy changes with changes in temperature and pressure at the Earth’s upper mantle
boundaries

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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

639

Figure (14): Entropy changes with change in temperature and lower mantle boundary pressure up
to the phase transformation pressure of CaO

Figure (15): Entropy changes with temperature and lower mantle boundary pressure starting from
the phase transformation pressure of CaO
As for the Earth's upper mantle, figure (13) and 1.50 joules/mole.K, always with the same
and the values in table (3) show that the arrangement of the two oxides. The values of
widths of the intervals in which the this entropy also continue to increase with
capacitance values of each oxide are confined temperature, with the exception of the values
are respectively 0.25 and 1.86 joule/mole.K. of calcium oxide at a pressure of 23.8334 GPa,
At 1000 K, they are 0.66 and 2.70 which stabilize at high temperatures. As for
joule/mole.K, respectively, at 1600 K. But the the values for the same oxide and for the
width of the real intervals is estimated at 0.33 pressure of 2.4546 GPa, they increase until the
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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth
temperature of 1440 K approximately reaches
the highest entropy value, then it starts to
decrease after this temperature. Therefore,
the difference decreases for magnesium
oxide, where its quantities at 1000 K are 1.21
joule/mole.K, while at 1600 K they are 0.36
joule/mole.K. As for calcium oxide, the
difference is estimated at 1000 K, or 0.33
joule/mole.K, so this difference decreases
until the temperature of 1440 K, at which
point the entropy value is equal between the
two pressures of 2.4546 and 23.8334 GPa.
This difference increases up to 1600 K, or 0.08
joule per mole.
In the lower earth mantle in its first part,
where calcium oxide is in its first phase, it
appears from figure 14 and the values in table
3 that the width of the intervals within which
the values of capacity for this confined oxide
are 0.75 joule/mole.K at 1600 K, 0.71
joule/mole.K, or 2488 K. But the width of the
real intervals is estimated at 0.70
joule/mole.K, with constantly decreasing
entropy values and an increasing difference.
This very small difference at the beginning is
estimated at 0.01 joule/mole.K, while at the
end it is estimated at 0.05 joule/mole.K. As for
magnesium oxide, the width of the entropy
change field here is 0.48 joule/mole.K at 1600
K and 0.97 joule/mole.K at 2488 K, but the
true width of the field of this change is
estimated at approximately 0.55 joule/mole.K.
The values of this parameter always increase
as they change with increasing temperature,
and they are related to the pressure value of
55.8991 GPa, while that of the pressure value
of 23.8342 GPa increases until the
temperature is estimated to be approximately
1600 K. This temperature represents a
temperature that corresponds to the entropy
of the two pressure values, from which its
values begin to decrease. This here reduces
the difference in values before this degree,
where its value is initially estimated at 0.46
joule/mole.K. And increasing to reach a value
III-3-4 Free energy:
Or the Gibbs function, which is written in the following form [35]:
eISSN1303-5150
of 0.04 joule/mole.K at the highest
temperature.
In the second part of the Earth's lower mantle,
that is, in the second phase of calcium oxide,
as shown in Figure (15) and the values in Table
(3), the ranges of change values of entropy for
this oxide and the second oxide is
respectively; 2.03 and 1.19 joule/mole.K at
2620 K are 1.44 and 0.78 joule/mole.K at 4700
K. As for displaying the intervals of actual
change in entropy values for each d they are
also 0.92 and 0.82 joules/mole.K, respectively.
The values of this factor decrease with
increasing temperature and the second oxide
reaches a pressure value of 60.683 GPa, with
an increasing difference for the first oxide,
where the difference values at lower
temperatures are 0.52 joule/mole.K , while at
higher temperatures it is 1.12 joule/mole.K. As
for magnesium oxide, the values of this
coefficient increase for the pressure of 60.683
GPa up to the temperature of 3000 K, and
from there the entropy values begin to
decrease like the rest. But there is a lower
temperature at which the entropy values of
the two pressures coincide. This temperature
640
is estimated at 2760 K. The difference
decreases before this temperature and
increases afterward, because its value at the
lowest temperatures is 0.04 joule/mole.K,
while its value at higher temperatures is 0.38
joule/mole.K.
The entropy values at the boundaries
separating the classes are equal, so the
difference is zero. By comparing the results of
our calculations for magnesium oxide with the
value resulting from the computer study [33]
or [34], we noted that the difference,
estimated 0.01 joule/mole.K, is very small,
which proves that the compatibility is very
large. However, it is not possible to compare
the values of our calculations for the second
oxide with the values of the results of other
studies, due to their lack of availability.
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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

where is the total energy as a function of the initial cell volume, is equivalent to the
hydrostatic pressure constant, is the Debye temperature and is the vibration term, which
can be written as l using the Debye phonon density of states model :

Where represents the number of atoms in the initial cell, represents the Debye integral.

From Figures (16–19) and the values recorded
in Table (3), it can be seen that the change in
free energy with change in temperature at all
pressures, and for both oxides, corresponds to
the change in internal energy, but with non-
linear decreasing values and an always
increasing difference. Where the highest value
for the width of the change intervals for both
oxides appears at the beginning pressure of
the Earth's lower mantle in the first section,
where calcium oxide is stable in its first phase,
their values for this oxide and the other oxide,
respectively, are: 299.10 and 271.16
kjoule/mole. The lowest of them appears at
the pressure of the end of the Earth's upper
mantle, where their values are 62.44 and
52.21 kjoule/mole. As for the display of the
real areas of change, the highest ones appear
in the same place as before, at values 236.78
and 237.98 kjoule/mole, while the place
where their lowest values appear varies, as
they appear at the beginning of the Earth’s
upper mantle and take values 40.50 and 35.37
kjoule/mole.
641

Figure (16): Free energy changes with changes in temperature and pressure at the boundaries of
the Earth’s crust.

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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

642

Figure (17): Free energy changes with changes in temperature and pressure at the Earth’s upper
mantle boundaries

Figure (18): Free energy changes with temperature and lower mantle boundary pressure up to the
phase transition pressure for CaO

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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

Figure (19): Free energy changes with changes in temperature and lower mantle boundary
pressure, starting with the phase transition pressure of CaO.
643

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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

Table 3: Values of the parameters studied at the pressures of the basic discontinuities in the
Earth’s interior up to the Gothenburg region for both MgO and CaO

Heat
Pressur Elastic Debye Internalenerg Entropy
Temperature capacities Free energy
e Oxides temperature y (Joule/mole.
(K) (Joule/mole. (Joule/mole)
(GPa) (K) (Joule/mole) K)
K)
300 6017,72 39,56 37,34 -3735,65
CaO 665,51
1000 52025,25 49,30 62,42 -74527,54
0
300 4219,66 32,97 26,79 -2158,46
MgO 905,93
1000 48254,07 48,74 60,68 -59040,43
300 5901,35 39,21 36,68 -3617,37
CaO 678,86
1000 51810,18 49,28 62,37 -73497,08
2,4539
300 4099,04 32,43 26,06 -2069,77
MgO 925,45
1000 47957,45 48,68 60,70 -58014,60
1000 51810,12 49,28 62,37 -73496,80
CaO 678,86
1600 81510,52 49,65 62,62 -138644,00
2,4546
1000 47957,37 48,68 60,70 -68823,14
MgO 925,46
1600 77414,10 49,38 62,55 -131267,00
1000 50775,96 49,14 62,04 -58014,32
CaO 743,61
1600 80419,35 49,59 62,70 -113992,09
23,8334
1000 46067,83 48,31 59,49 -51981,10
MgO 1052,14
1600 75371,81 49,20 62,19 -104189,24
1600 80419,33 49,59 62,70 -131266,87
CaO 743,61
2488 124565,35 49,80 61,95 -240730,70
23,8342
1600 75371,75 49,20 62,19 -129975,36
MgO 1052,14
2488 119282,89 49,62 62,67 -238729,39
1600 80217,43 49,58 62,71 -104188,98
CaO 755,67
2488 124355,76 49,79 62,00 -198367,57
55,8991
1600 73588,33 49,03 61,74 -96601,84
MgO 1164,95
2488 117394,06 49,54 62,71 -186313,23
2620 129619,56 49,77 62,14 -243850,39
CaO 831,07
4700 233329,11 49,91 60,10 -542950,65
60,683
2620 123719,90 49,57 62,71 -199622,21
MgO 1177,85
4700 227179,19 49,84 61,52 -462593,70 644
2620 125224,15 49,63 62,66 -209468,79
CaO 1088,27
135,750 4700 228756,26 49,86 61,22 -480626,98
9 2620 121433,50 49,47 62,67 -186063,09
MgO 1315,60
4700 224769,76 49,81 61,89 -437598,45
The difference values between their values is also very close and almost applicable for
are very close in the Earth’s crust, as it calcium oxide in its first phase of the Earth’s
appears identical in Figure (16), and it is the lower mantle (see Figure 18), as this
smallest difference for the two oxides, which difference is estimated at 27.078 and 42.363
are estimated respectively at 118.28 and kjoule/mole, respectively, at temperatures of
88.69 joule/mole at 300 K and at 1030.46 and 1600 and 2488 K. This difference takes
1025.83 joule/mole at 1000 K. This difference approximately the same values starting from
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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

the Earth’s upper mantle (see Figure 17) until The Debye temperature values for both oxides
the limits of the phase transformation of the were determined at the pressures of the
other oxide from the Earth’s lower mantle PREM model representing the earth’s matter
(see Figure 18). This is in a row, with values after choosing polynomials to vary this
estimated at 16.842 and 27.078 kjoule/mol for parameter with pressure by calculating the
1000 and 1600 K, respectively. It also takes constants of these functions.
values estimated at 33.373 and 52.416 This determination enabled us to calculate the
kjoule/mol for 1600 and 2488 K, respectively. change in internal energy, free energy,
The highest values of the difference appear at entropy, and heat capacity with a change in
the end of the Earth's lower mantle, where at temperature at the boundary pressures of the
2620 K the value is in the same order as the layers within the boundaries of the study.
two oxides and is 34.382, 13.559 kjoule/mole, At 300 K the agreement is very good between
while at 4700 K the value is always in the same the results of our study and previous studies
order as the two oxides and is 62.324, 24.995 on magnesium oxide, especially the value of
kjoule/mole (see figure 19). entropy, while the agreement in the value of
The values of this energy at the boundaries heat capacity and volume constant is not that
separating the layers are almost equal, only strong.
for calcium oxide on the border of the In the future, it is possible to suggest a
Mohosevich region, which is estimated at 0.27 number of research directions that always fall
joule/mole. On the same border, for within this scope, which are:
magnesium oxide, this difference is estimated Investing in the results of this study to
at 10.809 kjoule/mole, while on the border of calculate other parameters, such as heat
the region separating the two layers of the capacity at constant pressure, thermal
mantle, the difference for the same oxide is expansion, thermal conductivity, etc.
estimated at 25,786 kjoule/mole, and for The same study steps can be repeated on
calcium oxide, it is estimated at 17,275 many other subjects.
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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

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Abderrahim Achouri et al/ A study assessment of the thermodynamic properties of MgO and CaO at PREM pressures up to the outer core’s
limits of the Earth

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