i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 5 1 6 8 e1 5 1 8 0

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Construction of phase diagrams to estimate phase

transitions at high pressures: A critical point at the
solid liquid transition for benzene*

Beycan Ibrahimoglu a,d,*, Deniz Uner b, Ayfer Veziroglu c, Fuat Karakaya d,

Beycan Ibrahimoglu d
a
Industrial Engineering, Ankara Science University, Ankara, Turkey
b
Chemical Engineering Middle East Technical University ODTU, Ankara, 06800 Turkey
c
Executive VP, International Association for Hydrogen Energy
d
Anadolu Plazma Teknoloji Merkezi, Ankara, Turkey

highlights graphical abstract

The critical pressure is the highest

pressure that a solid-liquid coexists.

Beyond critical pressure, matters
may ionize and exhibit plasma
behavior.

The plasma state of the matter
should be included in the phase
diagram.

Graphic method can be used to
find critical points of a matter.

article info abstract

Article history: Phase diagrams are an integral part of the estimation of material properties in the case of
Received 29 December 2020 high temperature and pressure. The pressure-temperature (P-T) phase diagram is used to
Received in revised form determine the state of aggregation (solid, liquid, gaseous) of a substance under given
31 January 2021 conditions. This article presents a method to reveal new states in the phase diagram,
Accepted 2 February 2021 including the possibility of the plasma state. Using the empirical data of benzene, a critical
Available online 25 February 2021 pressure beyond solid-liquid equilibrium was estimated. It is highly probable that beyond
these pressures, benzene may ionize and exhibit plasma behavior. The method proposed
Keywords: in this work for benzene could also be applied to create a comprehensive phase diagram of
Phase diagram Hydrogen at certain pressure and temperature. Because the complex behavior of hydrogen,
Graphical method as well as the constant discovery of new varieties and the creation of many different
Pressure range of liquid phase phases of hydrogen makes it very difficult to construct a realistic phase diagram.
Critical pressure © 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Metastable phase
Plasma

*
NOTE: Until 1993, the articles were written as Beycan Ferzeliyev.
* Corresponding author. Industrial Engineering, Ankara Science University, Ankara, Turkey.
E-mail addresses: beycanibrahimoglu@yahoo.com, beycanibrahimoglu@gmail.com (B. Ibrahimoglu).
https://doi.org/10.1016/j.ijhydene.2021.02.010
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 5 1 6 8 e1 5 1 8 0
Introduction
The Gibbs phase rule requires the availability of two inde-
pendent state variables to estimate the state of a pure sub-
stance. Generally, the two state variables chosen to determine
the state of a substance and phase transitions are the pressure
(P) and temperature (T). At the same time, the pressure and
temperature diagram (P-T) of a pure substance marks the
phase transitions in the form of equilibrium curves, and also
fundamental transition points of that substance such as the
critical point and the triple point. In Fig. 1, the phase diagram
of a pure substance is shown, indicating three phases,
boundary curves separating these phases, and two funda-
mental points, namely the triple point and the critical point.
However, the small range and the simplicity of the phase
diagram shown in Fig. 1 prohibits the exhibition of many of
the important transition of the matter. The absolute zero is
not shown, due to the temperature ranges of interest for the
substance. The curves shown in the PT diagram are binodal,
veiling the spinodal curves indicating the metastable states of
the matter. The binodal solid vapor transition, i.e. the subli-
mation curve is not usually shown. The plasma state (the
fourth state of the matter), like the other states of matter
(solid, liquid and gas), is required to be also included in the PT
phase diagram. Because it is the aggregate state of pure mat-
ter. Studies on locating the plasma in the phase diagram have
been carried out for many years [1e3]. The hypothesis that
plasma phase transition is possible over the plasma triple
point, critical point and melting line, which was first
expressed by Norman and Starostin in 1968, has been dis-
cussed theoretically. In the 1990s, after the discovery of a tri-
ple point in the melting line experimentally, there has been
enough interest in plasma phase transitions. Finally, the
controversial critical pressure, marking the pressure bound-
ary between the solid, liquid and the plasma states is also not
indicated in the phase diagrams [4e6].
Our objective in this article is to present a graphical
method that is based on the solid geometry in order to include
these parameters in the phase diagram. Our basis will be the
experimental data of solid liquid transition of benzene
Fig. 1 e Phase diagram of a pure substance (P-Т).
15169
including the metastable state. But, it is anticipated that this
method applied for benzene could also be applied to Hydrogen
at certain pressure and temperature. The very complex
behavior of hydrogen, as well as the constant discovery of new
varieties, forms and different phases of hydrogen, which
significantly changes its phase diagram, makes it very difficult
to create a realistic phase diagram of hydrogen. Today, the
phase diagram of hydrogen is drawn experimentally and with
various models [7e9]. This work will shed light on construct-
ing the phase diagram of hydrogen by using graphical method
to cover all phases of hydrogen.
Today, studies related to Storage of Hydrogen [10e18] and
Fuel Cells [19e32] continue with acceleration. Understanding
the characteristics of hydrogen under different temperatures
and pressures is of great importance for these studies to be
more efficient. With this study, we aim to contribute to a
better understanding of hydrogen.
The rest of the paper is organized as follows. Section 2 de-
scribes materials and methods in detail. Discussion is given in
Section 3. Finally, the key findings are presented in conclusion.
Materials and methods
Graphics and solid geometry methods
Despite the highly advanced technologies in the 21st century,
the experimental validation of the absolute zero could not have
been achieved. The absolute zero was determined by Lord
Kelvin in 1840, after applying a graphical method to the gas
phase of the materials [33]. The basis of the method applied by
Lord Kelvin is shown in Fig. 2. The physical significance and
theoretical importance of the absolute temperature is not
debatable. Kelvin’s method has started from the following
postulates that are later accepted as the postulates of the ideal
gas law:
 
vV
i: ¼ constant (1)
vT P
ii. There is a unique temperature where V ¼ 0 for all sub-
stances, at all pressures.
These postulates are presently translated in to the postu-
lates of the ideal gas law, as (i) the molecules in the ideal gas
state do not interact, and (ii) the volume occupied by the
molecules in the ideal gas state are negligible in comparison to
the volume between the molecules.
We will start from the point of the validity of the absolute
zero and the ideal gas theory that is accepted by the scientific
community. We will extend these postulates to the liquid
phase: If we apply the same method to the density tempera-
ture behavior of the various substances in gas phase, this time
in the opposing direction of the increasing temperature.
 
vr
i: ¼ constant (2)
vT P
ii. There is a unique temperature at which density of the fluid
is zero.
15170 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 5 1 6 8 e1 5 1 8 0

Fig. 2 e (VeT), p ¼ const diagram.

When these postulates are applied to the existing empirical

Table 1 e Decomposition and ionization temperatures.
data of monoatomic gases, the intersection points of the iso-
bars revealed an estimate of the ionization temperatures as Gas Graphical method T ¼ K References T ¼ K
shown in Fig. 3 for Xenon. Oxygen 2550 2573 [12]
The analysis of the results showed that the point collected Argon 2920 e
on the isobars (T) axis corresponds to the ionization temper- Air 2690 e
Nitrogen 3700 3573 [19]
ature of that substance in monatomic gases and the dissoci-
Fluorine 3000 e
ation temperature of polyatomic gases [34e37].
Carbon dioxide 2223 2273 [19]
Dissociation and ionization temperatures for some sub- Xenon 2500 e
stances are shown in Table 1.
Descriptive geometry uses the image-creating technique of
imaginary, parallel projectors emanating from an imaginary (V-T), P ¼ const. dependencies to gas phase of the substances.
object and intersecting an imaginary plane of projection at This situation is characteristic for all gases except hydrogen gas.
right angles. The cumulative points of intersections create the Based on experimental data [65], the (P-T), V ¼ const. dia-
desired image. There is heuristic value to studying descriptive gram of hydrogen gas is clearly different from the (P-T),
geometry. It promotes visualization and spatial analytical V ¼ const diagram of the other gases [46]. With the decreasing
abilities, as well as the intuitive ability to recognize the di- temperature, the H2 volume moves away from the law of
rection of viewing for best presenting a geometric problem for linear dependence and isobars exhibit a different parabolic
solution. These properties of space geometry have been able stance than other gases.
to determine pressure dependent boiling and freezing tem- In this case, linear extrapolation of hydrogen isobars is
peratures, critical parameters (Ttp), (Tcr) and the pressure only applicable for certain temperature ranges. For example,
corresponding to the critical temperature of the material linear extrapolation of P ¼ 50 isobars is only possible for
[38e46]. The same method can be used to estimate the abso- temperatures above 44 K and for P ¼ 60 isobars it is only
lute zero and the ionization temperature also for the pure possible for temperatures higher than 48 K.
solids. The method was applied for the phase behavior data of Isobars take a parabola form in the 16 K < T < 44 K range,
Li and demonstrated below: Figs. 4 and 5. which depends on the value of the pressure. In addition,
extrapolated isobars intersect in the range (T ¼ 33: 0 ± 0: 5 K;
Application of graphic method to hydrogen gas V ¼ 21: 0 ± 1: 0 sm3 ¼ mol) and this does not include the origin of
the (T; V) plane [44e46]. Hydrogen, being a clean and inex-
The application of the grapho-analytical method to the gas haustible energy source of the future, is also the main source of
phases of substances made it possible to determine the basic the various fuel cell. The driving forces in the 1970s for fuel cell
points that exist in substances that cannot be determined by
experimental methods. For example: It was possible to deter-
mine the absolute temperature by applying (P-T), V ¼ const. or

Fig. 4 e Lithium vapor density versus its equilibrium

Fig. 3 e Ionization temperature of Xeon gas. pressure isotherms used to estimate the absolute zero.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 5 1 6 8 e1 5 1 8 0 15171

Fig. 5 e The speed of sound through lithium as a function of temperature isobars converging to its ionization temperature of
the solid.

research and development were energy conservation, preser-

vation of fossil fuel resources, and national security. Today the
benefits of zero emission fuel cells have been proven. Hydrogen
fuel cell solutions are used today in real-world applications
ranging from industrial-scale backup power systems to mobile
power for electric trains, buses, material handling systems and
heavy-duty transport trucks. Our studies related on Fuel Cell
systems could be found in Refs. [66,67,69e78,80e86,89e92]. In
this respect, hydrogen must be examined carefully in various
pressures and temperatures.
The application of the graphic method to the gas phase of
hydrogen has been reported in previous studies that hydrogen
exhibits a different behavior than other gases. Further infor- Fig. 6 e For hydrogen (1/V ¼ P); T ¼ const relation.
mation on this subject could be obtained from Refs. [44e46]. In
our studies on pure para-hydrogen (P ¼ 0.1e10 bar), it behaves
like normal gases at the close temperature rate (0e20 K) to the The liquid phase of hydrogen
absolute zero in the bar pressure range (Fig. 6).
It shows the ionization temperature of the gas where the In all these studies, the application of the graphical method to
gases (r-T) intersect on the T axis in the direction of increasing the gas phase of hydrogen has been investigated and has clearly
the temperature of all isobars in constant pressure depen- demonstrated that the results obtained are different from other
dence [34,51,52]. However, in the same application method to gases. This brought up the application of the graphic method to
the hydrogen gas, isobars merely intersects at a point on the the liquid phase of hydrogen. Volume change at different pres-
axis of the temperature in the range of (P ¼ 1; P ¼ 2; P ¼ 4; P ¼ 6; sures and temperatures was taken in the liquid phase of
P ¼ 8 and P ¼ 10 bar). The intersectıon points of the isobars at
temperature axis corresponds to the ionization temperature
of hydrogen (Fig. 7).
At the same time, at high pressures of hydrogen
(P ¼ 100e1000), each of the isobars cuts the (T) -axis at
different points (Fig. 8). This indicates that there is a temper-
ature that corresponds to each pressure, in other words, the
ionization temperature dependent on each pressure is
different.
When both diagram results are examined, it can be
concluded that the ionization temperature of hydrogen does
not change depending on the pressure up to 10 bar pressure,
but the ionization temperature of the hydrogen varies Fig. 7 e Graph of pressure value r-T, (P ¼ const) for
depending on the pressure at high pressures. hydrogen in the range of P ¼ 1 and P ¼ 10 bar.
15172 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 5 1 6 8 e1 5 1 8 0
Fig. 8 e r-T, (P ¼ constant) graph of high pressure
hydrogen isobars.
hydrogen [43,57]. Fig. 9 shows the absolute temperature in the
liquid phase of hydrogen (VeP), T ¼ const dependence.
The intersection of isobars at an absolute temperature
(T ¼ 0 K) in the liquid phase of hydrogen reveals that the liquid
phase behaves like a hydrogen gas.
1. It is possible to say that hydrogen in the gas phase is an
ideal gas in the range of T ¼ 0e20 K, gas mixture at
T ¼ 20 Ke1820K and plasma in T ¼ 1820K.
2. Liquid Hydrogen phase behaves like normal gases.
Application of graphical method to solid-liquid transition
It is possible to adapt the graphical method to the liquid and
solid phase transitions of a substance. So far, we presented
the graphical method to the vapor-liquid equilibrium of the
pure substances. The application of the graphical method
allowed us to estimate the critical point of the substances.
This time the postulate was to see if there exist an inter-
section point for the isotherms in the r-P diagram of the liq-
uids. In other words the postulates that are under
investigation now are
 
vr
i: ¼ constant
vP T
ii. There exist a pressure where density of the fluid is zero for
all temperatures.
 
vr
By applying vP ¼ constant postulate to the liquid phase
T and a gas is indicated by the fact that the vapor needs its liquid
behavior of a substance, it was seen that there is indeed a
common pressure where isotherms are collected on the
liquid-solid equilibrium curve at high pressures. (Fig. 10).
Fig. 9 e Liquid hydrogen (VeT), P ¼ const relation.
Previous studies on various liquids indicated that this
common point where isotherms are collected on the liquid
phase at high pressures is similar to the same as the critical
point on the liquid-gas equilibrium curve [35,37]. From this
point on, we will refer to the point where the isotherms are
collected as the solid critical pressure (Psolid critical) value of
that material and the solid critical density (rsolid critical) value
corresponding to the solid critical pressure. These two pa-
rameters were estimated for various organic compounds and
are presented in Table 2. The existence of such a critical point
has been subject of a long debate. Landau [50] and Bridgeman
[51] clearly indicate that such a critical pressure does not exist.
On the other hand, recent publications [20,21] reveal the ex-
istence and the method of determination of such critical
pressures. Our experimental measurements for metastable
transitions in the liquid benzene indicate the critical pressure
[55e58].
The data presented in Fig. 10 and Table 2 revealed that the
graphical method can be used at high pressures to reveal a
second critical point on the boundary between the solid and
liquid phases. Below we will describe the details and justifi-
cation of the methodology.
Determination of the liquid-vapor phase boundary
The vapor liquid equilibrium curve: temperature range of the
liquid phase
The liquid-vapor phase boundary in the (P-T) diagram is
limited by the two fundamental points (Ttriple point) and (Tcritical
point). (Fig. 11). Depending on the pressure, the vapor-liquid
equilibrium and the transition of the material from the
liquid phase to the vapor is possible at a unique temperature,
i.e., the state on this curve has one degree of freedom. On the
other hand, the triple point is a zero degree of freedom point, a
trait also shared by the critical point. The fluid at the triple
point is converted to one of the vapor, liquid and solid phases.
(3) On the other hand, the sublimation curve, which lies below
the triple point, marks the transition between the solid and
the liquid transition (see Fig. 12).
The phase transformation at the critical point is between
vapor, liquid and gas phases. The distinction between a vapor
in equilibrium, and vapor state has one degree of freedom,
while the gas phase has two degrees of freedom and represent
the states of the matter above the critical temperature and
pressure. The pressure corresponding to the critical temper-
ature (Tcr) is the critical pressure (Pcr) and the density is critical
density (rcr) [53,54].
Fig. 10 e n-Decane pressure-density diagram. All of the
isotherms converge to the critical point.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 5 1 6 8 e1 5 1 8 0 15173

Table 2 e Solid-liquid critical pressure value of some

substances estimated by graphical method.
Matter Chemical Name Critical Pressure Density
of Matter [MPa] [kg/m3]
n-Decane C10H22 130 0.839
n-Nonan C9H20 150 0.826
n-Xylene C8H10 200 0.990
o-Xylene C8H10 205 1000
o-Toluidine C7H9N 150 1400
m-Toluidine C7H9N 140 1450
p-Toluidine C7H9N 200 1100
Benzonitrile C7H5N 185 1350
Benzene C6H6 210 1200
Fig. 12 e Metastable phase at P ¼ 500 atm.

The pressure range of the liquid phase

The general PT curve shown in Fig. 1 is now expanded to
discuss the further details of the critical and triple points in
Fig. 7. We will change the definition of the critical pressure,
broadly used for the vapor liquid transition processes in this
article. When we use the term critical pressure, it will refer to
the highest possible pressure that a solid-liquid coexistence is
possible. A close examination of Fig. 11 indicates that at points
P1, P2 and P3, co-existence of vapor liquid and solid are
compared. At P1 vapor liquid and liquid solid transition is
possible by cooling. However, at pressures greater than the
pressure corresponding to the critical temperature, only liquid
solid transition is possible by a change in temperature. Pres-
sure P1 in the diagram represents the liquid phase at values
below critical pressure, and pressures P2 and P3 represent the
liquid phase at values above critical pressure. Since the
pressure corresponding to the critical temperature, indicated
here as critical pressure (Pcr), shown in the diagram is in a
state between the P1 pressure in the liquid phase and the
pressures P2 and P3, it is not possible to determine the
pressure-dependent boundary range of the phase change and
current liquid phase. As noticed, we were careful to identify
(Pcr), as the pressure corresponding to the critical tempera-
ture, at which the difference between liquid-gas phases are
Fig. 11 e Pressure corresponding to critical temperature.
eliminated. In this case, the critical pressure Pcr, called the
critical pressure value (Pcr) of the liquid phase, is the pressure
corresponding to the critical temperature.
The result of the examination of the liquid phase (P-T) diagram
The vapor liquid transition is a single degree of freedom pro-
cess. In other words, if the pressure is fixed, the temperature
at which the transition will take place is also fixed. Hence, if
the critical temperature is known, that should eliminate the
need for a critical pressure, since this point corresponds to the
highest possible temperature where vapor and liquid coexist.
As a result, the critical pressure shown in the phase diagram is
only the pressure corresponding to the critical temperature.
The critical situation is a special case characterized by the
disappearance of the difference between liquid and gas. Un-
fortunately, the volume, density and pressure corresponding
to this condition are also called critical volume (Vcr), critical
density (rcr) and critical pressure (Pcr) [59]. As demonstrated in
Fig. 5, since the degrees of freedom is one on the vapor-liquid
transition curve, the density and pressure corresponding to a
critical situation are not needed to characterize a critical
situation.
Now we will divert our attention to the solid liquid tran-
sition. Currently, it is not possible to determine the liquid
phase limit according to the phase diagram (p-T) pressure. In
other words, there is no pressure value that determines the
critical situation in the (P-T) phase diagram. Since there is no
real critical pressure that characterizes the critical pressure of
the liquid phase, the boundary range of the liquid phase is
uncertain. The absence of such a pressure indicates that the
liquid phase will exist even at P ¼ ∞ infinity, which is not
physically possible.
Advanced technologies in recent years allowed tests that
can be carried out at very high pressures. At high pressure, the
electron shells of the atoms approach and deform, in which
case the chemical reaction ability of the substances increases.
When the pressure reaches 102e103 atm, the difference be-
tween the liquid and gas disappears. When the pressure rea-
ches 103e105 atm, the difference between the solid-liquid
phases disappears. As the pressure reaches 106 atm, a
metallic bond is formed. At a higher pressure, the irregular
conglomerate of electrons and nuclei resembling plasma ap-
pears. By increasing the pressure to 1012 atm, the relations
15174 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 5 1 6 8 e1 5 1 8 0
between the atom, the electron and the nucleus become
insignificant, and the substance acts as an electron gas at a
high density of 109 kg/m3.
Based on these general concepts, and using the graphical
method we described so far, we will check if indeed at
103e105 atm pressure a critical point for solid liquid transition
is possible [60]. For this purpose, the liquid phase must be
examined experimentally at high pressures.
The data to be used for this purpose were collected for
benzene solid-liquid transition, at high pressures. The data
and the details of the measurements were already published
[38,47,48,53,54,58,87,88].
The measurements were based on creating a metastable
benzene (C6H6) phase at elevated pressures. The ability to
create the metastable phase and the transition from the
metastable phase to the next stable phase allowed us to
postulate a solid-liquid critical pressure.
Phase transitions
From a review of various models of the thermodynamic
description of the physical properties of the medium, it is clear
that the usual classification of states in the region of high
pressures and temperatures often loses its certainty and is
conditional, and the boundaries between phases either
disappear altogether or become fuzzy and correspond, in
essence, to a continuous mutual transformation of close
states.
Melting process and the experimental determination of critical
pressure (Pc)
Although the graphic method made by us, or the various
evaluations made by physicists determine that the existence
of a basic point in the liquid-solid phase range at high pres-
sures is possible, the existence of this point should be deter-
mined experimentally. Melting is one of the most universal
and well-studied phase transformations and, being a transi-
tion from an ordered to a disordered structure, is associated
with the disappearance of long-range order in the system. An
important issue is the existence of a critical point of type II on
the melting curve, in which a first-order phase transition is
replaced by a second-order transition, since, according to
Landau’s results, the melting curve cannot end with a critical
point.
Currently available experiments on temperature mea-
surements at high pressures of 0.5e3 Mbar and volume
measurements under static conditions are in favor of the
hypothesis that there are no critical points of type II, since
jumps in volume and entropy during melting do not disap-
pear with increasing pressure. P.W Bridgman conducted ex-
periments on liquid and solid melting curve in the
temperature range of 273e473 K, and pressures up to
1.25 GPa, as well as other research groups [60], neither
confirmed the existence of a critical point on the melting
curve. In addition, studies conducted with the presence of
the metastable phase have shown that the melting and
sublimation equilibrium curves end with a critical point
[53e55,87,88]. In this study, we approached the experimental
problem through the metastable state of benzene at high
pressures.
High pressure effect on benzene pre-crystallization
metastable state
The experimental facility, details of which have already been
published [38,47,48,54,55,58]. We measured and controlled
the following parameters of the benzene meta-stable state:
pressure p, container temperature, freezing temperature,Tb
(i.e. crystallization temperature), temperature, Tc in the low
point of the meta-stable state, overcooling, DT ¼ TbeTc
relative to freezing temperature, pressure difference, DP at
the initial stage of explosive crystallization, incubation
period, t1 of liquid benzene stay in the meta-stable (over-
cooled) state, t2 e the time of an abrupt transition from the
meta-stable state to the crystalline one, t3 e the time of
isothermal freezing, the total time, t of solidification (t ¼ t1-
þ t2 þ t3). The graphical information is presented in Fig. 6.
The experiments were conducted in the pressure range of
0.1e2200 atm. Here the data are presented (Table 3) only up
to 500 atm.
Discussion
The Gibbs phase rule dictates that under the coexistence
conditions of the solid and liquid equilibrium, one state vari-
able is sufficient to specify the state of the system. In addition,
the freezing point is a function of the pressure. In other words,
as the pressure increases, the freezing point also increases.
The Clausius-Clapeyron relationship connects the tempera-
ture and pressure of the freezing through the energy needed
for the phase transitions.
The metastable state of the matter exists when the equi-
librium conditions for the temperature and pressure are
satisfied, but the transition is not initiated. In other words,
when the liquid phase persists despite the conditions for the
solidification is present. The limits of the metastable state is
determined by the thermodynamic constraints. The pressure
volume relationship of a fluid should strictly follow the
following rule
 
vP
<0 (4)
vV T
Given this, then it is only possible to cool the liquid to a
temperature where the enthalpy change by cooling is equal to
the enthalpy change of fusion:


DHfusion ¼ Cp; liquid Tequilibrium  Tminimum (5)
This relationship follows directly from the general equa-
tion of enthalpy as a thermodynamic variable which is a
function of temperature and pressure
   
vV
dH ¼ Cp dT þ V  T dP (6)
vT p
At the point of the stability limit of the metastable state, the
pressure derivative, dP term disappear, and the enthalpy
change is only a function of temperature. Hence, the minimum
temperature that can be sustained allows one to determine the
energy needed for the phase transition. Furthermore, this is
directly linked to the time it takes to reach the metastable state,
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 5 1 6 8 e1 5 1 8 0 15175

Table 3 e Experimental results of benzene (P ¼ 0.1 to P ¼ 500 atm).

P (atm) Ta (K) Tb (K) DT (K) Td ¼ Te (K) DP (atm) t1 (sec) t2 (sec) t3 (sec) t (sec)
0.1 278.5 258.5 20.0 278.5 e 160 ~6.0 260 426
100 279.0 267.0 13.0 279.0 32.0 131 ~3.0 210 343
200 280.0 270.0 10.0 280.0 27.0 112 ~2.5 180 294
300 282.8 274.6 8.2 282.8 23.0 97 ~2.0 155 254
400 284.8 277.8 7.0 284.8 20.0 85 ~2.0 135 222
500 286.7 280.7 6.0 286.7 17.5 72 ~2.0 115 189

transition was estimated and plotted against the experi-

Table 4 e The thermodynamic symmetry status of the mental data as shown in Fig. 15.
system in the P-T diagram.
The results obtained by graphical and experimental
L-S-G (Ttр) L-P-G (Tcr) SeP-L (Pcr) methods at high pressure for benzene on the melting curve at
P ¼ 0.1 atm. P ¼ 4.92 atm. P ¼ 2200 atm, high pressures are quite close.
T ¼ 278.5 K T ¼ 561.5 K T ¼ 347 K The critical pressure of benzene by graphical method
P ¼ 2100 atm.
if the system is designed to provide a constant rate of heat
The critical pressure of benzene by experimental method
transfer. Under pressure, benzene molecules C6H6 can be force
P ¼ 2200 atm.
incorporated into the ordered crystal lattice and the degree of
The Gibbs phase law determines the phase equilibrium
overcooling, the incubation period of a new phase nucleation
conditions in a given system. Gibbs also shows that there can
and the time of freezing therewith decrease. As to the critical
be no more than three phase equilibrium states in a homo-
point M in which the meta-stable parameters disappear, it is
geneous system. Although the benzene phase diagram
characterized by some critical values of temperature ~356 K
(Fig. 15) shows that four phases (solid, liquid, gas and plasma)
and pressure ~2200 atm under which a difference between
coexist, only three phases will always be in equilibrium (see
liquid and crystalline states disappears. At this state the
Table 4).
enthalpy of melting should also disappear, which is also esti-
mated by the diminishing temperature difference as the pres-
Analysis of the phase behavior of benzene
sure increased, as indicated in Table 3.
Fig. 9 illustrates the temperature-time diagram of the
The thermobaric parameters of benzene were calculated and
metastable phase at different pressures. Temperature and
compared with experimental results at pressures above
pressure values characterizing the metastable phase
200 MPa given in Refs. [54e56]. The peculiarity of this experi-
decreased with increasing pressure. When the pressure rea-
mental study is that the transition of the liquid into the solid
ches 2200 atm, the temperature Dt, pressure Dp and life (m)
was recorded after the pressure was established and the
values are reset. Resetting the temperature Dt, Dp pressure
temperature was lowered, in contrast to the standard exper-
and life (m) values in the metastable phase means that the
imental procedure for the phase transformations of solid
metastable phase is disappeared (terminated). This indicates
benzene into liquid, in which, on the contrary, the pressure
that the system is in single phase.
decreases at a constant temperature. This allowed the study
Using the information presented in Table 3, and Fig. 12, it
of [54e56] to study the metastable state of supercooled ben-
was possible to construct a graph similar to Fig. 10 in order to
zene and to detect the existence of a metastability endpoint at
determine a limiting value for a pressure beyond which a solid
a pressure of 220 MPa and a temperature of 356 K, as well as
liquid coexistence no longer exists. The value of this pressure
the liquid-solid properties of benzene in its vicinity.
is denoted as critical pressure of the liquid [48,55e58,61]. This
pressure determines the pressure-dependent range of the
liquid phase (see Fig. 13).
Based on the test results the critical pressure is Pcr-
¼ 2200 atm and the corresponding temperature is Tkr ¼ 356 K
for benzene (Fig. 14).
The most promising way to build state diagrams is the
optimal combination of both theoretical and experimental
methods, followed by computer calculations. In this article, to
compare the values of thermobaric parameters obtained
experimentally, the Tait equation of state is used

r0
r¼  ; (7)
1  A$ln BþP
BþP
ат М

where r0 is the density at atmospheric pressure Patm and

temperature T, r is the density at some pressure P and tem- Fig. 13 e Temperature-time diagram of the phase under
perature T. Using the Tait equation of state, the liquid vapor pressure P ¼ 0.1; 500; 1000; 1500; 2200.
15176 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 5 1 6 8 e1 5 1 8 0
Fig. 14 e The critical pressure of the liquid phase of
benzene is Pcr ¼ 2200 atm and temperature T ¼ 356 K.
Fig. 15 e A fragment of a PT benzene phase diagram with
an endpoint of metastability.
A more detailed experimental study of the behavior of
benzene in a wide range of temperature and pressure changes
shows that the transition time from the metastable to crys-
talline state and the isothermal freezing time decreases with
increasing external pressure and disappears at a pressure of
222 MPa and a temperature of 356 K, which can be called the
endpoint of metastability. In this case, the liquid-crystal
transformations at the final point of metastability are
similar to the gas-liquid phase transitions at the critical point.
State diagrams of benzene
As a rule, experimental data of various methods are used to
construct state diagrams, such as X-ray diffraction, calori-
metric, thermal, dilatometric, optical, and electron micro-
scopy, NMR, etc. based graphical method. The graphical
method [40,43,47,55] reports the presence of a critical point on
the melting curve at high pressures to the liquid phase.
The experimental fact established in Ref. [33] that the
critical temperature and the melting temperature increases
with increasing external pressure in accordance with the
Clausius e Clapeyron law indicates a certain solid-state
transformation of the first order. Such phase transitions in
which the first derivatives of the thermodynamic potential
suffer a discontinuity correspond to first-order trans-
formations. Sometimes they are also called discontinuous
phase transitions, in contrast to continuous phase transitions
(or phase transitions of the second kind), in which the first
derivatives are continuous, and the second derivatives change
abruptly.
The question of how far one can advance into the region of
metastable states raises. The answer to this question is given
by the theory of phase stability with respect to continuously
changing thermodynamic parameters, formulated by Gibbs.
The critical point of the phase transition is a singular point in
the mathematical sense for the thermodynamic potentials of
a substance, in particular, at this point not only isothermal
compressibility, but also the second derivative of pressure
with respect to volume is equal to zero. The latter means that
the critical point is the inflection point of the critical isotherm.
However, like any theory of transformations, the Clausius-
Clapeyron theory is only some approximation that interprets
the phase processes that occur in reality. Experimental
detection of the endpoint of benzene metastability indicated
in a small interval of variation of the thermodynamic pa-
rameters is an example of a fast but still continuous phase
transition (or, according to P. Ehrenfest’s classification, a
phase transition of the second kind), where the first de-
rivatives of the thermodynamic potential are continuous, and
the second derivatives change abruptly, then in this case the
second derivatives of thermodynamic potentials are the so-
called thermodynamic coefficients. A differential equation
for a line of a second-order phase transition, which relates
jumps in thermodynamic coefficients to the corresponding
temperature derivative of pressure, can be obtained by
differentiating the relations determining the equality of the
first derivatives of the chemical potential of two phases,
which reflect the fact that entropy and volume do not change
during a continuous phase transition. As a result, we can get
the Ehrenfest equations. In contrast to the Clapeyron-Clausius
phase equilibrium curve, the Ehrenfest equation determines
the phase transition line, on which the “critical point” ob-
tained in the work must apparently lie. However, during such
phase transformations there are no metastable states and a
new phase appears immediately in the entire volume of the
substance and, accordingly, there is no interface between
phases and surface energy. In this case, the task of obtaining
theoretical values of the phase transition parameters using
the Ehrenfest equation of phase transformations corre-
sponding to those obtained experimentally in Ref. [33].
The phase diagram is a graphic indicator of various phases
and the main points of a substance under experimental con-
ditions of temperature and pressure. The construction of all
atomic structures of a substance occurs according to the
scheme: highly organized plasma / material body (solid) /
liquid / gases and carries the physicochemical properties of
the substance. Physical properties include: appearance,
texture, color, smell, melting point, boiling point, critical
temperature, density, solubility, polarity, and many others.
Based on the fact that the atomic structure is a harmonious
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 5 1 6 8 e1 5 1 8 0
system, all calculations in atomic structures are performed
only using fractals of the golden ratio [64]. In this regard, we
built a state diagram of benzene based on the atom model.
The proposed state diagram will be the first one which
includes plasma state (Fig. 16). Inclusion of the plasma state in
the phase diagram will lead to better understanding as well as
finer applications of the technology [68,79,93]. Plasma could be
defined as the fourth state of the matter, constitutes 98% of
the universe. As such it has many known applications in the
industry and also in medicine. The ionization of the matter
can be induced by electromagnetic actions, by high tempera-
tures and pressures and also by the action of catalysts [62,63].
Assuming experimental detection of the benzene meta-
stability endpoint of the change in the thermodynamic pa-
rameters indicated in the work on a small interval is an
example of a fast but still continuous phase transition (or,
according to P. Ehrenfest’s classification, a phase transition of
the second kind), in which the first derivatives of the ther-
modynamic potential are continuous, and the second de-
rivatives change abruptly, then in this case the second
derivatives of thermodynamic potentials are the so-called
thermodynamic coefficients. Among them, the most impor-
tant are the coefficient of thermal expansion, the coefficient of
isothermal compression, the coefficient of adiabatic
compression, isobaric and isochoric heat capacities. A differ-
ential equation for a line of a second-order phase transition,
which relates jumps in thermodynamic coefficients to the
corresponding pressure derivative with respect to tempera-
ture, can be obtained by differentiating the relations deter-
mining the equality of the first derivatives of the chemical
potential of two phases, which reflect the fact that entropy
and volume do not change during continuous phase transi-
tion. As a result, we can obtain the Ehrenfest equations. In
contrast to the Clapeyron-Clausius phase equilibrium curve,
the Ehrenfest equation determines the phase transition line,
on which the “critical point” obtained in the work should
apparently lie. However, during such phase transformations
Fig. 16 e The qualitative representation of the benzene
phase diagram.
15177
there are no metastable states, and a new phase appears
immediately in the entire volume of the substance and,
accordingly, there is no interphase interface and surface
energy.
Conclusion
The Gibbs phase rule dictates that only one state variable is
needed to specify the state of the system. As such, being the
final point of the coexistence curve, critical temperature
should be sufficient to specify the critical point. At the critical
point, the enthalpy of phase change disappears, as well as the
existence of any metastable states. Using this aspect of the
coexistence behavior, a new critical point was determined for
solid liquid transition of Benzene at 2200 atm. At this pressure,
the metastable state disappeared. This point exhibit a second
order, Ehrenfest phase transition, where there are no meta-
stable states, and a new phase appears immediately in the
entire volume of the substance and, accordingly, there is no
interphase interface and surface energy.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
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