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<p class="art-type">Research Article</p>
<p class="art-title">Thermodynamic properties Methyl- and
Ethyladamantanes </p>
<p class="art-author"><?php $authors="Amanzhan Saginayev<sup>*</sup>, M.M. Kursina and E.G. Gilazhov
"; echo (stristr($authors,$coauthor))?str_replace($coauthor,"<a href='".$extpath."authors/".$courl."' target='_blank'>".$coauthor."</a>",$authors):$authors; ?></p>
<p class="art-affl">
Atyrau Oil and Gas University, Atyrau, Kazakhstan
</p>
<p class="art-aff"><b>*Corresponding author: <?php $corresponding_author="Amanzhan Saginayev"; echo ($coauthor!="" && $coauthor==$corresponding_author)?"<a href='".$extpath."authors/".$courl."' target='_blank'>".$coauthor."</a>":$corresponding_author;?></b>, Professor, Atyrau Oil and Gas University, Atyrau, Kazakhstan, E-mail: <a href="mailto:asaginaev@mail.ru">asaginaev@mail.ru</a>
</p>
<p class="art-aff"><b>Received:</b> November 17, 2017
<b>Accepted:</b> December 7, 2017
<b>Published:</b> December 13, 2017</p>
<p class="art-aff"><b>Citation: </b> Saginayev AT, Kursina MM, Gilazhov EG. Thermodynamic properties
Methyl- and Ethyladamantanes. <i>Int J Petrochem Res.</i> 2017; 1(2) 101-104. doi: <a href="https://doi.org/10.18689/ijpr-1000118">10.18689/ijpr-1000118</a></p>
<p class="art-aff"><b>Copyright:</b> &copy; 2017 The Author(s). This work
is licensed under a Creative Commons
Attribution 4.0 International License, which
permits unrestricted use, distribution, and
reproduction in any medium, provided the
original work is properly cited.</p>
<p><a href="<?php echo $extpath;?><?php echo $jres['journal_link'];?>/ijpr-1000118.pdf" class="btn btn-danger pull-right" target="_blank">Download PDF</a></p>
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<div class="articlecontent">
<p class="art-subhead">Abstract</p>
<p class="art-para">The thermodynamic characteristics of the compounds and their total energy, transformation energies, entropies of transformations, and normal vibration frequencies
have been calculated. It is shown that the calculated free Gibbs energies for the formation
of isomerization products of per hydroaromatic hydrocarbons are in qualitative
agreement with the experimental data of isomerate products.</p>
<p class="art-para"><b>Key words:</b>  adamantane, methyladamantanes, ethyladamantanes, DFT calculation. </p>
<p class="art-subhead">Introduction</p>
<p class="art-para">In the Gulf of Mexico found tiny black diamonds- according to scientists, they were
formed from crude oil. These diamonds consist of a force of several dozen carbon atoms, which is less than one billionth of a carat. However, similar hydrocarbons of a diamondlike
structure can also find practical application. Their artificial analogues are already
used in medicines intended for the treatment of Parkinson&#700;s disease and viral infections
<a href="#1">[1</a>, <a href="#2">2]</a>. In addition, they can find application in the field of nanotechnology <a href="#3">[3]</a>. Diamond
materials are derivatives of the saturated hydrocarbon adamantane, which was found in
oil as far back as 1933. The spatial arrangement of carbon atoms in the adamantane
molecule is the same as in the crystal lattice of diamond. Numerous adamantane
molecules can join together, forming larger diamondoids.</p>
<p class="art-para">When a large number of such molecules are combined, a diamond is formed-a
characteristic regular lattice consisting of carbon atoms.</p>
<p class="art-para">A group of scientists from ChevronTexaco&#700;s research division, led by Jeremy Dhala, discovered diamondoids consisting of several (up to 11) adamantane molecules in the
oil deposits raised from the bottom of the Gulf of Mexico.</p>
<p class="art-para">Before, under laboratory conditions, it was not possible to combine together more
than four such molecules.</p>
<p class="art-para">It is completely incomprehensible how diamondoids can be formed from hydrocarbon
chains, of which oil consists. Perhaps, they are formed during reactions with methane, the
catalyst in which the minerals that make up the clay are. If this is so, nothing prevents them
from continuing their growth further, reaching quite sizeable dimensions. It was also
found out that diamondoids can form black agglomerations with tiny crystals of diamonds
called black technical diamonds. The latter, apparently, were formed not in the conditions
of high temperatures and pressure, like ordinary diamonds. A number of scientists believe
that they could form in space and get to Earth together with a meteorite substance.</p>
<p class="art-para">The adamantane molecule has a high degree of symmetry. Some elements of
symmetry of adamantane are preserved even when one or more substituents are
introduced in the position of the nucleus.</p>
<p class="art-para">Adamantane and its derivatives have been the object of
many studies, both experimental and theoretical.</p>
<p class="art-para">The molecular structure of adamantane was studied by
gas-phase electron diffraction <a href="4">[4]</a>, ionization electron
spectroscopy <a href="#5">[5]</a>, photoelectronic spectroscopy <a href="#6">[6]</a>, electron
spin resonance <a href="#7">[7]</a>, quantum calculations of ionization
potentials (PI) and electron affinity (SE) <a href="#8">[8]</a>.</p>
<p class="art-para">The aim of this work is to conduct experimental studies
and quantum chemical calculations by the method of
functional of the energy from the electron density the DFT
B3LYP/6-31G*, to study the structure and thermodynamic
properties of alkyladamantanes composition C<sub>11</sub>-C<sub>13</sub>.</p><br>
<p class="art-subhead">Experimental</p><br>
<p class="art-para">Methyladamantanes are of great interest both for use as
an artificial calculation field, and for determining the strain
energy within this system. Schleiere and his colleagues
calculated the strain energies for adamantane and
1,3,5,7-tetramethyladamantane (-6.9 kcal / mol and 5.0 kcal /
mol, respectively) <a href="#9">[9]</a>.</p>
<p class="art-para">The data of the exact standard enthalpy of formation of
these compounds plays a decisive role in the estimation of
calculation methods.</p>
<p class="art-para">The thermodynamic stability of some alkyladamantanes
was determined by calculation and experimental methods, and then compared with each other <a href="#10">[10]</a>.</p>
<p class="art-para">Alkyladamantanes of the composition C<sub>12</sub>H<sub>20</sub> are obtained
from perhydroacenaphthene upon passage of the latter over the
alumina catalyst in a flow type plant with a metal reactor <a href="#11">[11</a><a href="#12"></a><a href="#13"></a><a href="#14">-14]</a>. The products of this reaction include 1,3-dimethyladamantane, trans-1,4-dimethyladamantane, cis-1,4-dimethyladamantane, 1,2-dimethyladamantane, 1-ethyladamantane and
2-ethyladamantane. As is known, alkyladamantanes C<sub>13</sub>H<sub>22</sub>
are usually obtained by isomerization of perhydrofluorene <a href="11">[11</a>,<a href="#12">12</a>, <a href="#15">15]</a>. From isomerizate are allocated 1,3,5-trymethyladamantane, cis-1,3,6-trymethyladamantane, trans-1,3,6-trymethyladamantane, cis-1,3,4-trymethyladamantanes, trans-1,3,4-trymethyladamantane, 1,2,6-trymethyladamantane, 1,2,8-trymethyladamantan, 1-methyl3-ethyladamantane, cis-1-methyl-4-ethyladamantanes, trans1-methyl-4-ethyladamantanes.</p><br>
<p class="art-subhead">Calculation results and Discussion</p><br>
<p class="art-para">To minimize the errors in the calculations, 1- and
2-methyladamantanes, 2,2-dimethyladamantane, 1,3,5-
trimethyladamantane were purified by standard methods (recrystallization, vacuum sublimation) before burning in the
calorimeter, and 1,3-dimethyladamantane was purified by
repeated fractional distillation under low pressure. Was used
1 cm<sup>3</sup>
 of water was placed into the calorimetric bomb of
internal volume 0.1 dm<sup>3</sup>
 with calibration and additional
equipment and then oxygen pressure up to 30 atmospheres
at 298.15 &#1050; was established. The vapor pressures of all the solid compounds were
measured in a glass Bourdon gauge that was nulled against a
mercury manometer. The vapor pressures of these compounds
were fitted by least squares to the equation
<br>log<sub>10</sub> (p/Torr) = A/T + B (1)<br>
and the enthalpy of sublimation was calculated assuming
no vapour imperfection and negligible solid volume as <a href="#16">[16]</a><br>
&#8710;H<sub>sub</sub> = - RAln10 (2)</p><br>
<p class="art-para">The vapor pressure of 1,3-dimethyladamantane is
determined by semi microebuliometric method <a href="#17">[17]</a>.</p>
<p class="art-para">The results of the calculations are presented in Table 1.</p>
<div class="art-img">
<img src="<?php echo $imgpath;?>images/IJPR-118-table1.PNG" class="img-responsive center-block"/></div>
<p class="art-para">The combustion reaction is described by the equation:<br>
C<sub>a</sub>H<sub>b</sub> + (a+b/4) O<sub>2</sub>
 = aCO<sub>2</sub> + 1/2bH<sub>2</sub>O (3)</p>
<p class="art-para">Derivatives from the standard molar combustion energy
&#8710;Eb&#730;, the standard molar enthalpy of combustion &#8710;Hb&#730; and
the molar standard enthalpy of formation of &#8710;Hf&#730; compounds
are presented in Table 2.</p>
<br>
<div class="art-img">
<img src="<?php echo $imgpath;?>images/IJPR-118-table2.PNG" class="img-responsive center-block"/></div>
<br>
<p class="art-para">Derivatives from the sublimation enthalpies of
methyladamantanes are presented in Table 3. The values of
Tm are taken from the previously studied mean temperatures. The standard enthalpy of sublimation &#8710;Hs&#730; (298.15 K) is
determined by the equation:<br>
&#8710;H<sub>s</sub>&#730; (298.15&#1050;) = &#8710;H<sub>s</sub>
&#730;(&#1058;<sub>m</sub>) +(298.15 &#1050; &#8211; &#1058;<sub>m</sub>) (&#1057;<sub>p</sub>&#730;(gas)-
&#1057;<sub>p</sub>&#730;(solid)) (4) </p>
<br>
<div class="art-img">
<img src="<?php echo $imgpath;?>images/IJPR-118-table3.PNG" class="img-responsive center-block"/></div>
<br>
<p class="art-para">Substitution of methyl groups on tertiary carbon atoms of
adamantane nuclei increases thermochemical stability.</p>
<p class="art-para">We performed quantum-chemical calculations using the
energy-functional method from the electron density of DFT
B3LYP/6-31G* perhydroacenaphthene, perhydrofluorene and
the products of their transformations <a href="#18">[18</a>,<a href="#19"> 19]</a>. Optimization of
the geometric structure of molecules and calculation of the
frequencies of normal vibrations were carried out using
atomic bases 6-31G*. Calculations were performed using the
GAUSSIAN-98 program <a href="#20">[20]</a>. DFT B3LYP is a combination of
the Charter-Fock method and the density functional theory
using the gradient-corrected Beck function with three
parameters (B3) <a href="#21">[21]</a> and the Li-Yang correlation functional
series (LYP) <a href="#22">[22]</a>. For each molecule, the geometric
arrangement of atoms was optimized using analytical
calculation methods. By calculating the frequencies of normal
vibrations using the second derivatives, it was confirmed that
the stationarity points determined in the optimization of
geometry are energy minima.</p>
<p class="art-para">Table 4 shows the calculated electronic characteristics of
the calculated molecules: the energy of the boundary orbitals (Ehomo, Elumo), dipole moments (&#181;), zero-point energy (ZPC) and entropy (S).</p>
<br>
<div class="art-img">
<img src="<?php echo $imgpath;?>images/IJPR-118-table4.PNG" class="img-responsive center-block"/></div>
<br>
<p class="art-para">Table 5 shows the calculated basic energy characteristics
of compounds: the values for the total energy Et, the total
energy with allowance for zero point energy Ezpc, the total
energy with correction for enthalpy EH, and the total energy
with correction for Gibbs free energy EG in atomic units of
energy. Below are the formulas for determining these
thermodynamic quantities <a href="#21">[21]</a>:<br><br>
Ezpc = Et+ ZPC, (5)<br>
EH = Et+ ZPC + Evib + Erot + Etrans, (6)<br>
EG = EH &#8211; TS, (7)<br></p>
<p class="art-para">where, Evib is the vibrational motion energy, Erot is the
energy of the rotational motion, Etrans is the translational
motion energy, S is the entropy and T is the Kelvin temperature.</p>
<br>
<div class="art-img">
<img src="<?php echo $imgpath;?>images/IJPR-118-table5.PNG" class="img-responsive center-block"/></div>
<br>
<p class="art-para">The thermodynamic characteristics obtained in our calculations
are in excellent qualitative agreement with experimental data on
the isomerization of perhydroacenaphthene <a href="#1">[1]</a>.</p>
<p class="art-para">1,3-Dimethyladamantane as the product of isomerization
has the greatest of all the other alkyladamantanes of the
C<sub>12</sub>H<sub>20</sub> composition with thermodynamic stability; it has the
lowest values of Et, Ezpc, EH, EG. The yield of
1,3-dimethyladamantane is up to 80%. The cis and trans
isomers of 1,4-dimethyladamantane have practically the same
values of all the thermodynamic characteristics that we
calculated. For these isomers, the isomerase composition is
the same (about 4%).The stability of 1,2-dimethyladamantane is lower than the stability of 1,3-adamantane and
1,4-adamantanes, which also agrees with the experiment. 1-ethyladamantane is more stable from calculations than
2-ethyladamantane. The experimental yields of these products
are consistent with our calculations.</p>
<p class="art-para">The thermodynamic characteristics obtained from our
calculations are in excellent qualitative agreement with the
experimental data on the isomerization of perhydrofluorene <a href="#1">[1]</a>. 1,3,5-Trimethyladamantane as the isomerization product has the
greatest of all the other alkyladamantanes of the C<sub>13</sub>H<sub>22</sub>
composition with thermodynamic stability; it has the lowest
values of Et, Ezpc, EH, EG. The yield of 1,3,5-trimethyladamantane
is up to 50%. The cis and trans isomers of 1,3,6-trimethyladamantane
and 1,3,4-trimethyladamantane have practically the same values
of all the thermodynamic characteristics that we calculated. For
these isomers, the isomerizate composition is approximately the
same (3 and 4%, respectively). The stability of 1-methyl-4-
ethyladamantanes is lower than the stability of 1-methyl-3-
ethyladamantane, which also agrees with the experiment. 1,2,6-
and 1,2,8-trimethyladamantanes are not stable from the
calculations. The experimental yields of these products are
consistent with our calculations.</p>
<p class="art-para">Thus, the results of the calculations presented above agree
with the previously published experimental data that the number
of different isomers of methyl- and ethyladamantane formed in
the isomerization of perhydroaromatic hydrocarbons is due to
the difference in their thermodynamic stability. It has been
established experimentally that the reaction is an equilibrium
process.</p>
<br>
<p class="art-subhead">References</p><br>
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</ol>   
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