Critical States at Phase Transitions of Pure Substances

This book re-examines the conventional pressure-temperature phase diagrams of pure substances, taking into account a universally acknowledged, albeit often neglected, state of matter―the plasma phase. It argues that only the temperature component of the endpoint on the gas-liquid equilibrium curve is critical, not the pressure and volume, which themselves are the corresponding components of the critical temperature. The book features the compiled results of many recent experimental studies on the physical properties of benzene, hydrogen, and carbon dioxide, extracting the endpoints of the liquid-solid and solid-gas equilibria and yielding the real critical pressure and volume. These discoveries highlight the position of plasma on the phase diagram and the existence of the equilibrium ionization curve along with it. Detailed knowledge of the plasma state of matter is essential not only in many fields of physics and chemistry but in engineering and industrial applications as well. This book will easily benefit researchers, engineers, and instructors who routinely interact with phase diagrams. Foreword 7 Preface 8 Acknowledgements 11 Note 12 Contents 13 Abbreviations 17 1 Phase Diagrams 18 1.1 Introduction 18 1.2 Phase Diagram of One-Component Systems 19 1.3 Definitions 20 1.4 Solid–Liquid Equilibrium Curve 21 1.5 Liquid–Solid Phase Diagrams at High Pressures 21 References 23 2 Experimental Studies 25 2.1 Experimental Setup 25 2.2 Experimental Studies 26 2.3 Theoretical Evaluation of Experimental Results 28 2.4 Performed Measurements 29 2.5 Experimental Method 30 References 30 3 Metastable State 32 3.1 Metastable State and Its Classification 32 3.2 Experimental Determination of Metastable State and Its Existence Time 34 3.3 Experimental Studies on the Investigation of the Metastable State at High Pressures and Temperatures 36 3.4 Effect of Pressure on the Freezing of Benzene 40 3.5 Superdiscontinuous Metastable State 44 References 50 4 Material Selection 54 4.1 Benzene 54 4.2 The Effect of High Pressure and Low Temperature on Liquid–Solid Transition of Benzene 54 4.3 Evaluation of the Experimental Results 56 References 61 5 Pressure Change of the Metastable State of Benzene 63 5.1 Experimental Studies and Results 64 5.2 Interpretation of Experimental Results 66 References 71 6 Analysis of the Phase Behavior of Benzene in a Wide Range of Temperature and Pressure Variations 73 6.1 Introduction 73 6.2 Critical Point of Liquid–Solid Transition for Benzene 73 6.2.1 Introduction 73 6.2.2 Material and Method 75 6.3 Results and Discussion 75 6.3.1 ∆p–∆T Relation 76 6.3.2 Critical Pressure of Liquid–solid Transition 77 6.3.3 Temperature of Liquid–solid Transition 78 6.3.4 Proposed Benzene Liquid–Solid Equilibrium Curve 80 6.4 Conclusion 80 6.5 PVT Studies of Benzene 81 6.6 State Diagrams of Benzene 83 6.7 Conclusion 86 References 89 7 Axiogeometry 92 7.1 Geometric Studies 92 7.2 Basic Knowledge 93 7.3 Absolute Temperature 94 7.4 Determination of an Arbitrary Temperature in Celsius Corresponding to Absolute Zero 96 References 98 8 Equations of State 100 8.1 Ideal Gas Equation 100 8.2 Van Der Waals Equation 100 8.3 Thermal Decomposition Temperature 101 8.4 Temperature Measurement and Gas Thermometer 104 9 Hydrogen Gas 106 9.1 Introduction 106 9.2 Graphical Determination of the Properties of Hydrogen Gas 107 9.3 Ionization of Hydrogen Gas 112 9.4 Application of Grapho-Analytical Method to the Liquid Phase of Hydrogen 115 9.5 Formation of Hydrogen-Related Supercritical Fluid 118 9.6 Phase Diagrams 118 9.7 Density–Temperature (ρ–T) Phase Diagram at Low Pressure and Low Temperatures 119 9.8 Density–Pressure (ρ–p) Phase Diagram at Low Pressures and Temperatures 120 9.9 Density–Pressure (ρ–p) Phase Diagram at Low Pressure and High Temperatures 121 9.10 Hydrogen Density–Temperature (ρ–T) Diagram 122 9.11 Pressure–Temperature (p–T) Phase Diagrams 122 9.12 p–T Phase Diagram Arranged by Simulating Hydrogen Atom Model with Hydrogen Nucleus 123 9.13 Formation of Supercritical Fluid 123 9.14 Discussion 125 9.15 Results 126 References 127 10 Phase Diagram of Carbon Dioxide 132 10.1 Introduction 132 10.2 Method 134 10.3 Results and Discussion 134 10.4 Determination of Absolute Zero Temperature 134 10.5 Determination of Critical Pressure Related to Liquid–Solid Equilibrium Line 135 10.6 Stable Phases that Can Come to Equilibrium with Each Other 136 10.7 Supercritical Phases 137 10.8 Phase Diagram of Supercritical Fluid 138 10.9 Results 139 References 140 11 Application of the Graphical Method to the Liquid Phase 142 11.1 Critical Facts 144 11.2 Critical State 144 11.3 Determination of the Boundary Range of the Liquid Phase 145 11.4 Experimental Determination of the Critical Pressure and the Critical Density 148 11.4.1 Introduction 148 11.4.2 Experimental Technique 150 11.4.3 Experimental Results 152 11.4.4 Discussions and Results 155 11.5 Determination of Critical Pressure (pcr) by Graphical Method 155 References 160 12 Desublimation Equilibrium Curve 164 12.1 Introduction 164 12.2 Graphical Method and Experimental Studies 166 12.3 Results and Discussion 167 12.4 Conclusion 171 References 172 13 Position of Plasma at Phase Diagrams 174 13.1 Introduction 175 13.2 Experimental Studies 178 13.3 Plasma is a Clean, İnexhaustible Source of Energy 181 13.4 Geometric Thermodynamics 183 13.5 Thermodynamic Surfaces of One-Component Compounds 186 13.6 Formation of the Phase Diagrams 188 13.7 Atomic Model of Phase Diagram 188 13.8 Results 191 References 191 14 Developments in Phase Diagram and Phase Transitions 194 This book re-examines the conventional pressure-temperature phase diagrams of pure substances, taking into account a universally acknowledged, albeit often neglected, state of matter the plasma phase. It argues that only the temperature component of the endpoint on the gas-liquid equilibrium curve is critical, not the pressure and volume, which themselves are the corresponding components of the critical temperature. The book features the compiled results of many recent experimental studies on the physical properties of benzene, hydrogen, and carbon dioxide, extracting the endpoints of the liquid-solid and solid-gas equilibria and yielding the real critical pressure and volume. These discoveries highlight the position of plasma on the phase diagram and the existence of the equilibrium ionization curve along with it. Detailed knowledge of the plasma state of matter is essential not only in many fields of physics and chemistry but in engineering and industrial applications as well. This book will easily benefit researchers, engineers, and instructors who routinely interact with phase diagrams