The liquid and supercritical fluid states of matter. (2020)

• Record Type: Book
• Further Information: Note: John E. Proctor.
• Authors: Proctor, John Edward
• Contents: Contents Preface...................................................................................................xi Useful Equations and Definitions.......................................................xv Definitions.......................................................................................... xxi 1 Some Remarks on the Gas State 1.1 Equation of State (EOS) of Real Gases................................................................ 1 1.1.1 The Van der Waals Equation................................................................. 1 1.1.2 The Virial Equation.................................................................................2 1.2 Order in the Gas State............................................................................................3 1.3 Heat Capacity of Gases......................................................................................... 4 1.3.1 How Well Does This Model Work?...................................................... 4 1.4 Vibrational Raman Spectroscopy of Gases........................................................6 1.5 Viscosity of Gases...................................................................................................8 1.6 Why Are Liquids so Difficult?............................................................................ 10 1.6.1 Molecular Dynamics (MD)................................................................. 10 1.6.2 The Fundamental EOS (Section 3.3)....................................................11 1.6.3 Treat the Fluid as Gas-Like.................................................................. 12 1.6.4 Treat the Fluid as Solid-Like................................................................ 12 References.......................................................................................................................... 13 2 The Vapour Pressure Curve and the Liquid State Close to the Vapour Pressure Curve 2.1 Classical Versus Quantum Liquids.................................................................... 15 2.2 The Transition Across the Vapour Pressure Curve......................................... 17 2.3 The Clausius-Clapeyron Equation.....................................................................19 2.3.1 Validity of the Clausius-Clapeyron Equation.................................. 20 2.4 The Critical Point................................................................................................. 20 2.4.1 Critical Constants and the Van Der Waals Equation of State....................................................................................25 2.5 Summary............................................................................................................... 29 References......................................................................................................................... 30 3 Equations of State for Fluids 3.1 Cubic EOS Based on the Van der Waals Equation..........................................32 3.1.1 Volume Translation of Cubic EOS..................................................... 34 3.2 The Carnahan-Starling EOS...............................................................................35 3.3 The Fundamental EOS........................................................................................ 36 3.3.1 Ideal Gas Component of the Helmholtz Function.......................... 36 3.3.2 Residual Component of the Helmholtz Function............................39 3.3.3 Fitting the Helmholtz Function to the Experimental Data................................................................................39 3.4 Conclusions...........................................................................................................41 3.4.1 For What Fluids Is a Fundamental EOS Available?.........................41 3.4.2 How Can We Test the Validity of an EOS?........................................41 3.4.3 What Is the Best Way to Implement Your Chosen EOS? ............................................................................................................... 44 References......................................................................................................................... 46 4 The Liquid State Close to the Melting Curve (I): Static Properties 4.1 Density and Bulk Modulus of Fluids Close to the Melting Curve............... 47 4.1.1 Density of Fluid Ar Close to the Melting Curve.............................. 48 4.1.2 Density and Bulk Modulus of Fluid N2 Close to the Melting Curve................................................................................ 49 4.2 Elastic Neutron and X-ray Diffraction from Liquids Close to the Melting Curve....................................................................................................... 51 4.2.1 Distinctions Between X-ray and Neutron Diffraction Experiments......................................................................53 4.2.2 Fourier Transform of Fluid Diffraction Data to Obtain g (r ) ....................................................................................55 4.2.3 Fourier Transform of Modified Fluid Diffraction Data to Obtain g (r ) ..................................................................................................58 4.2.4 Comparison of Diffraction Data to Simulated Fluid Structures in Reciprocal Space............................................................61 4.2.5 Relation Between g (r ), the Partition Function, Internal Energy, and Pressure.............................................................................63 4.2.6 Relation Between g (r ) and Entropy....................................................65 4.2.7 Relation Between g (r ) and Co-ordination Number (CN)............. 66 4.3 Short-Range Order and Phase Transitions in Fluids Close to the Melting Curve...................................................................................................... 67 4.3.1 Co-ordination Number....................................................................... 67 4.3.2 Liquid-Liquid Phase Transitions........................................................ 67 4.4 Equations to Fit the Melting Curve on the P, T Phase Diagram................... 69 4.5 What Happens to the Melting Curve in the High P, T Limit?........................72 4.6 Summary................................................................................................................74 References..........................................................................................................................77 5 The Liquid State Close to the Melting Curve (II): Dynamic Properties 5.1 Phonon Theory of Liquids...................................................................................79 5.1.1 Frenkel and Maxwell Models..............................................................79 5.1.2 Prediction of Liquid Heat Capacity....................................................82 5.2 Raman Spectroscopy of Liquids and Supercritical Fluids Close to the Melting Curve................................................................................ 88 5.2.1 Grüneisen Model for Vibrational Raman Peak Position ........................................................................................................................90 5.2.2 Hard Sphere Fluid Theory of Vibrational Raman Peak Positions.......................................................................... 91 5.2.3 Peak Position of Rotational Raman Spectra.....................................93 5.2.4 Peak Intensity and Linewidth of Fluid Raman Spectra..................93 5.2.5 Prediction of Fluid Raman Spectra Using MD............................... 94 5.3 Brillouin Spectroscopy of
• Edition: 1st
• Publisher Details: Boca Raton : CRC Press
• Publication Date: 2020
• Extent: 1 online resource, illustrations (black and white)
• Subjects: 530.42; Supercritical fluids
• Languages: English
• ISBNs: 9780429957918; 9780429957925; 9780429957901; 9780429491443
• Related ISBNs: 9781138589735
• Notes: Note: Includes bibliographical references and index.; Note: Description based on CIP data; resource not viewed.
• Access Rights: Legal Deposit; Only available on premises controlled by the deposit library and to one user at any one time; The Legal Deposit Libraries (Non-Print Works) Regulations (UK).
• Access Usage: Restricted: Printing from this resource is governed by The Legal Deposit Libraries (Non-Print Works) Regulations (UK) and UK copyright law currently in force.