ACADEMIA Letters

Determination of the Real Critical Pressure and Critical

Density of Substances
Beycan IBRAHIMOGLU, Ankara Science University, Ankara - Turkey
Fuat KARAKAYA, Anadolu Plasma Technology Center, Ankara - Turkey
Beycan Jr. IBRAHIMOGLU, Anadolu Plasma Technology Center, Ankara - Turkey

Notes
i. All experimental data used in this article is taken from the main author’s doc-
toral dissertation.
ii. In all publications before 1993, the main author’s name was Beycan Farzaliyev.

Abstract
The critical density (ρc) and critical pressure (Pc) in the pressure (P-T) phase diagram of pure
substance, represent only the pressure and density values corresponding to the critical tem-
perature (Tc). Therefore, the critical pressure and critical density used in the equations do
not correspond to the actual critical values of pressure and density. In this study, axiomatic
geometry system was applied to experimental data of benzonitrile and for some other hydro-
carbons and the results obtained were determined as the true critical pressure and density on
the solid-liquid equilibrium curve at high pressure and temperature.

Keywords: Phase diagram, benzonitrile, graphical method, critical point, solid-liquid equi-
librium

Academia Letters, August 2021 ©2021 by the authors — Open Access — Distributed under CC BY 4.0

Corresponding Author: Fuat KARAKAYA, karakaya.f@gmail.com

Citation: Ibrahimoglu, B., Karakaya, F., Ibrahimoglu, B.J. (2021). Determination of the Real Critical Pressure
and Critical Density of Substances. Academia Letters, Article 2704. https://doi.org/10.20935/AL2704.

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1. Introduction
The phase diagram of the pure substance (Fig. 1) is visually plotted on the P-T phase diagram
based on pressure and temperature dependent experimental results. In the phase diagram, all
three phases are present and the triple point where these phases are in equilibrium. In addition,
a point on a liquid-gas equilibrium curve, commonly known as a critical point is also available
on the phase diagram [1].

Fig. 1 Critical parameters shown on P-T phase diagram.

In the classical P-T phase diagram used today, only shows the three phase and boundary
curves that separate these phases from each other, the triple point where the three phases are
at one point and the critical parameters where the liquid gas equilibrium curve ends (Tcr, Pcr,
ρcr).
Examining the diagram in Fig. 2 which determines the pressure and temperature depen-
dent boundary range of the liquid phase, it seems that the critical pressure (Pcr) and critical
density (ρcr) in the classical phase diagram (Fig. 1) do not characterize the real critical pres-
sure and density values.
When the diagram in Figure 2, which determines the pressure and temperature dependent
boundary range of the liquid phase, is examined, it is seen that the critical pressure (Pcr) and
critical density (ρcr) in the classical phase diagram (Figure 1) do not characterize the actual

Academia Letters, August 2021 ©2021 by the authors — Open Access — Distributed under CC BY 4.0

Corresponding Author: Fuat KARAKAYA, karakaya.f@gmail.com

Citation: Ibrahimoglu, B., Karakaya, F., Ibrahimoglu, B.J. (2021). Determination of the Real Critical Pressure
and Critical Density of Substances. Academia Letters, Article 2704. https://doi.org/10.20935/AL2704.

2
pressure and density, values.

Fig. 2 The P-T phase diagram determining the boundary range of the liquid phase.

Based on the high pressure and temperature experiments of the benzene metastable phase,
we have reported that there is a critical point on the melting equilibrium curve [10,17-25].
In this study, the existence of a critical point at high pressures on the liquid-solid equi-
librium curve based on the laws of geometric thermodynamics will be discussed. For this
purpose, it is important to examine the state of the boundary range of the liquid phase de-
pending on temperature and pressure in the diagram given in Fig. 2. In the diagram, it is clear
that the temperature-dependent boundary interval of the liquid phase exists between the triple
point Ttp and the critical point Tcr. With the same approach, when the pressure range of the
liquid phase is examined in the diagram, it is obvious that the triple point, PTP and Pcr points
do not determine limit range of the liquid phase. Because the P1 point in the diagram is the
liquid phase below the critical Pcr pressure, the P2 and P3 points are in the liquid phase above
the critical pressure Pcr. In this case, the presence of liquid phase above and below the Pcr
point (Fig. 2) indicates that the Pcr critical point does not characterize the critical pressure.
This is the case also for the critical density ρcr.

Academia Letters, August 2021 ©2021 by the authors — Open Access — Distributed under CC BY 4.0

Corresponding Author: Fuat KARAKAYA, karakaya.f@gmail.com

Citation: Ibrahimoglu, B., Karakaya, F., Ibrahimoglu, B.J. (2021). Determination of the Real Critical Pressure
and Critical Density of Substances. Academia Letters, Article 2704. https://doi.org/10.20935/AL2704.

3
2. Determination of true critical pressure and density in P-T phase
diagram
Based on the general laws of thermodynamics, certain physical laws are established using
geometrical methods, different from ordinary analytical methods. Therefore, it is very impor-
tant from a thermodynamic point of view to use the axiomatic method, which is a method for
constructing a mathematical theory in which, when applying geometrical thermodynamics to
some parameters, axiomatic principles are accepted (axioms) and the rest are purely logical.
By applying the axiomatic method to thermodynamic parameters, it was possible to determine
the equilibrium curves and critical points of all phases.
In the 1840s, Kelvin applied graphical methods to P-T, V = const and V-T, P = const dia-
grams of the gas phase of substances, and the absolute temperature of substances in the solid
phase was determined as T (K) = t (C) + 273.15 ° ฀ with great accuracy. Even today, despite
the development of high technology, this base point has not been reached experimentally (Fig.
3).

Fig. 3 Determination of absolute temperature in P-T, V =constant diagram

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:

Academia Letters, August 2021 ©2021 by the authors — Open Access — Distributed under CC BY 4.0

Corresponding Author: Fuat KARAKAYA, karakaya.f@gmail.com

Citation: Ibrahimoglu, B., Karakaya, F., Ibrahimoglu, B.J. (2021). Determination of the Real Critical Pressure
and Critical Density of Substances. Academia Letters, Article 2704. https://doi.org/10.20935/AL2704.

4
 Using the same method, we were able to determine the temperature of ionization and
decomposition [11-12] of the substance, using the ρ-P, T = const dependence on the gas phase
of the substances (Fig. 4).

Fig. 4 Determination of ionization temperature in the ρ-P, T = const diagram.

Studies revealed that the ρ-P, T = const dependence shows the ionization point in monatomic
gases and the decomposition temperature in polyatomic gases.

3. Application of geometric method to liquid phase of substances

The geometric method was applied to the experimental results of Benzonitrile (C6H5 (CN)
given in Table 1 and the presence of a base point [12-15] on the melting equilibrium curve at
high pressures was determined (Figure 5).

Academia Letters, August 2021 ©2021 by the authors — Open Access — Distributed under CC BY 4.0

Corresponding Author: Fuat KARAKAYA, karakaya.f@gmail.com

Citation: Ibrahimoglu, B., Karakaya, F., Ibrahimoglu, B.J. (2021). Determination of the Real Critical Pressure
and Critical Density of Substances. Academia Letters, Article 2704. https://doi.org/10.20935/AL2704.

5
Table 1 Experimental density data of benzonitrile at high pressures and temperatures (ρ,
kg/m3)

The experimental results of benzonitrile at high pressure and temperature are shown in
Fig. 5 in (ρ –P), T = const. diagram.

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Corresponding Author: Fuat KARAKAYA, karakaya.f@gmail.com

Citation: Ibrahimoglu, B., Karakaya, F., Ibrahimoglu, B.J. (2021). Determination of the Real Critical Pressure
and Critical Density of Substances. Academia Letters, Article 2704. https://doi.org/10.20935/AL2704.

6
Fig. 5 Point where the isotherms of benzonitrile, at P-ρ, T = const dependency, intersect on
the P axis (P = 270 MPa and density ρ = 1100kg / m3)

When the graphical method was applied in the P-ρ, T=const diagram, it was observed that
at high pressure, the isotherms are collected at a point for liquid phase of hydrocarbons. For
example, P-ρ, T = const dependencies were applied to the liquid phase of benzonitrile at high
pressure and temperature. It was observed that in the liquid phase of benzonitrile, isotherms
are collected at an unknown point (Fig. 5) and this point is considered as the real critical
pressure:

In Fig. 6 the critical pressure and density values of benzonitrile are shown in P-T Phase
diagram.

Academia Letters, August 2021 ©2021 by the authors — Open Access — Distributed under CC BY 4.0

Corresponding Author: Fuat KARAKAYA, karakaya.f@gmail.com

Citation: Ibrahimoglu, B., Karakaya, F., Ibrahimoglu, B.J. (2021). Determination of the Real Critical Pressure
and Critical Density of Substances. Academia Letters, Article 2704. https://doi.org/10.20935/AL2704.

7
 Fig. 6 P-T Phase diagram of benzonitrile showing real critical pressure.

Space geometry was applied for liquid phases of some organic and inorganic materi-
als: (Oxygen (O2), Nitrogen (N2), Argon (Ar), Ammonia (NH3), Sodium (Na), Potassium
(K), Benzene (C6H6), Toluene (C7H8), orto-, meta-, para- Toluidine (C7H9N), Benzonitrile
(C6H5(CN) and the real critical pressure and density values determined on the melting curve
are given in Table 2.

Academia Letters, August 2021 ©2021 by the authors — Open Access — Distributed under CC BY 4.0

Corresponding Author: Fuat KARAKAYA, karakaya.f@gmail.com

Citation: Ibrahimoglu, B., Karakaya, F., Ibrahimoglu, B.J. (2021). Determination of the Real Critical Pressure
and Critical Density of Substances. Academia Letters, Article 2704. https://doi.org/10.20935/AL2704.

8
 Table 2 Critical pressure and critical density values of some hydrocarbons.

4. Experimental Results
In this study, the space geometry system was applied to the density of some organic and in-
organic substances in liquid phases at high pressure and temperature and the actual critical
pressure and density values of the substances were determined.
By applying the (ρ –P), T=const dependence to the benzonitrile (C6H5 (CN)) experimen-
tal results, the critical pressure and critical density of benzonitrile on the melting equilibrium

Academia Letters, August 2021 ©2021 by the authors — Open Access — Distributed under CC BY 4.0

Corresponding Author: Fuat KARAKAYA, karakaya.f@gmail.com

Citation: Ibrahimoglu, B., Karakaya, F., Ibrahimoglu, B.J. (2021). Determination of the Real Critical Pressure
and Critical Density of Substances. Academia Letters, Article 2704. https://doi.org/10.20935/AL2704.

9
curve were determined.
Based on the results of the benzene metastable phase experiments at high pressure and
temperature, it has been reported that there is a critical point on the melting equilibrium
curve[10,17,22].

5. Discussions and Results

The point where the benzene metastable phase ends at high pressure and temperature, there
is a critical point on the melting equilibrium curve [2-5]. In order to show that this point
existing on the melting equilibrium curve of benzene also exists in other organic and inorganic
substances, a graphic method has been applied to the gas and liquid phases of the substances
and the results are given in Table 2.
The graphic method is the most suitable method for determining the thermodynamic pa-
rameters of substances.
The application of the graphical method to the gas phase of the substances with (V-T),
P=const the dependence determined the absolute temperature, the application of (1 / V-T) P =
const diagram determined the ionization and decomposition temperatures. By applying the (1
/ V-T) P = const diagram to the liquid phase of the substances, the critical pressure and critical
density were determined. The existence of critical pressure and critical density determined
in the liquid phase of the substances is based on the purely logical statement of the previous
ones.

For Example:
Fowler formulated the zeroth law of thermodynamics as “If two bodies are in
equilibrium with the third body then they are in equilibrium with each other”.
If A = B and R = C systems are in thermal equilibrium then A = C is in equilib-
rium. This equality isa purely logical expression of axiomatic accepted principles

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Corresponding Author: Fuat KARAKAYA, karakaya.f@gmail.com

Citation: Ibrahimoglu, B., Karakaya, F., Ibrahimoglu, B.J. (2021). Determination of the Real Critical Pressure
and Critical Density of Substances. Academia Letters, Article 2704. https://doi.org/10.20935/AL2704.

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Corresponding Author: Fuat KARAKAYA, karakaya.f@gmail.com

Citation: Ibrahimoglu, B., Karakaya, F., Ibrahimoglu, B.J. (2021). Determination of the Real Critical Pressure
and Critical Density of Substances. Academia Letters, Article 2704. https://doi.org/10.20935/AL2704.

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Corresponding Author: Fuat KARAKAYA, karakaya.f@gmail.com

Citation: Ibrahimoglu, B., Karakaya, F., Ibrahimoglu, B.J. (2021). Determination of the Real Critical Pressure
and Critical Density of Substances. Academia Letters, Article 2704. https://doi.org/10.20935/AL2704.

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Corresponding Author: Fuat KARAKAYA, karakaya.f@gmail.com

Citation: Ibrahimoglu, B., Karakaya, F., Ibrahimoglu, B.J. (2021). Determination of the Real Critical Pressure
and Critical Density of Substances. Academia Letters, Article 2704. https://doi.org/10.20935/AL2704.

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