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| Preface | |
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| Notation | |
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| First and Second Laws | |
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| Introduction | |
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| The Molecular Nature of Energy | |
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| Intermolecular potentials for mixtures | |
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| The Molecular Nature of Entropy | |
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| Brief Summary of Several Thermodynamic Quantities | |
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| Basic Concepts | |
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| Introduction to steam tables | |
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| Interpolation | |
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| Double interpolation | |
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| Double interpolation using different tables | |
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| Double interpolation using Excel | |
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| Quality calculations | |
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| Constant volume cooling | |
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| Summary | |
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| Homework Problems | |
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| The Energy Balance | |
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| Expansion/Contraction Work | |
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| Shaft Work | |
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| Work Associated With Flow | |
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| Lost Work vs. Reversibility | |
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| Isothermal compression of an ideal gas | |
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| Path Properties and State Properties | |
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| Work as a path function | |
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| Heat Flow | |
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| The Closed-System Energy Balance | |
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| Internal energy and heat | |
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| The Open-System, Steady-State Balance | |
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| The Complete Energy Balance | |
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| Internal Energy, Enthalpy, and Heat Capacities | |
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| Enthalpy of H[subscript 2]O above its saturation pressure | |
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| Adiabatic compression of an ideal gas in a piston/cylinder | |
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| Transformation of kinetic energy into enthalpy | |
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| Kinetic and Potential Energy | |
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| On the relative magnitude of kinetic, potential, internal energy and enthalpy changes | |
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| Energy Balances for Process Equipment | |
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| The integral representing shaft work | |
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| Strategies for Solving Process Thermodynamics Problems | |
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| Closed and Steady-State Open Systems | |
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| Adiabatic, reversible expansion of an ideal gas | |
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| Continuous adiabatic, reversible compression of an ideal gas | |
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| Continuous, isothermal, reversible compression of an ideal gas | |
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| Heat loss from a turbine | |
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| Unsteady-State Open Systems (Optional) | |
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| Adiabatic expansion of an ideal gas from a leaky tank | |
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| Adiabatically filling a tank with an ideal gas | |
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| Adiabatic expansion of steam from a leaky tank | |
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| Details of Terms in the Energy Balance (Optional) | |
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| Summary | |
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| Practice Problems | |
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| Homework Problems | |
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| Entropy | |
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| The Concept of Entropy | |
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| Microscopic View of Entropy | |
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| Entropy change vs. volume change | |
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| Entropy change of mixing ideal gases | |
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| The Macroscopic Definition of Entropy | |
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| Ideal gas entropy changes in a piston/cylinder | |
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| Steam entropy changes in a piston/cylinder | |
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| Entropy generation in a temperature gradient | |
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| Entropy generation and lost work in a gas expansion | |
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| The Entropy Balance | |
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| Steady-state entropy generation | |
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| Reversible work between heat reservoirs, lost work | |
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| Entropy change of quenching | |
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| The Carnot Engine | |
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| Carnot Heat Pump | |
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| Internal Reversibility | |
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| Maximum/Minimum Work in Real Process Equipment | |
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| Entropy Balance For Process Equipment | |
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| Charts Including Entropy | |
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| Turbine Calculations | |
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| Turbine efficiency | |
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| Multistage Turbines | |
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| Pumps and Compressors | |
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| Strategies for Applying the Entropy Balance | |
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| Additional Steady-State Examples | |
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| Heat pump analysis | |
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| Entropy in a heat exchanger | |
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| Unsteady-State Open Systems (Optional) | |
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| Entropy change in a leaky tank | |
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| An ideal gas leaking through a turbine (unsteady-state) | |
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| The Entropy Balance in Brief | |
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| Summary | |
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| Practice Problems | |
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| Homework Problems | |
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| Thermodynamics of Processes | |
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| The Carnot Cycle | |
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| The Rankine Cycle | |
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| Rankine cycle | |
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| Two-phase turbine output | |
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| Rankine Modifications | |
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| Rankine with reheat | |
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| Regenerative Rankine cycle | |
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| Refrigeration | |
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| Refrigeration by vapor-compression cycle | |
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| Liquefaction | |
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| Liquefaction of methane by the Linde process | |
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| Internal Combustion Engines | |
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| Air-standard Brayton cycle thermal efficiency | |
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| Thermal efficiency of the Otto engine | |
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| Thermal efficiency of a Diesel engine | |
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| Fluid Flow | |
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| Problem-Solving Strategies | |
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| Practice Problems | |
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| Homework Problems | |
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| Generalized Analysis of Fluid Properties | |
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| Classical Thermodynamics--Generalization to Any Fluid | |
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| The Fundamental Property Relation | |
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| Derivative Relations | |
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| Pressure dependence of H | |
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| Entropy change with respect to T at constant P | |
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| Entropy as a function of T and P | |
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| Entropy change for an ideal gas | |
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| Entropy change for a simple non-ideal gas | |
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| Application of the triple product relation | |
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| TCH for an ideal gas | |
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| Volumetric dependence of C[subscript V] for ideal gas | |
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| Master equation for an ideal gas | |
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| Relating C[subscript P] to C[subscript V] | |
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| Advanced Topics (Optional) | |
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| Summary | |
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| Homework Problems | |
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| Engineering Equations of State for PVT Properties | |
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| Experimental Measurements | |
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| Three-Parameter Corresponding States | |
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| Generalized Compressibility Factor Charts | |
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| Application of the generalized charts | |
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| The Virial Equation of State | |
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| Application of the virial equation | |
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| Cubic Equations of State | |
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| Solving the Equation of State for Z | |
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| Solution of the Peng-Robinson equation for molar volume | |
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| Application of the Peng-Robinson equation | |
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| Implications of Real Fluid Behavior | |
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| Derivatives of the Peng-Robinson equation | |
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| The Molecular Theory Behind Equations of State | |
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| Deriving your own equation of state | |
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| Matching the Critical Point | |
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| Critical parameters for the van der Waals equation | |
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| Summary and Concluding Remarks | |
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| Practice Problems | |
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| Homework Problems | |
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| Departure Functions | |
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| The Departure Function Pathway | |
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| Internal Energy Departure Function | |
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| Entropy Departure Function | |
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| Other Departure Functions | |
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| Summary of Density-Dependent Formulas | |
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| Enthalpy and entropy departures from the Peng-Robinson equation | |
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| Real entropy in an engine | |
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| Enthalpy departure for the Peng-Robinson equation | |
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| Gibbs departure for the Peng-Robinson equation | |
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| Pressure-Dependent Formulas | |
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| Application of pressure-dependent formulas in compression of methane | |
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| Reference States | |
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| Enthalpy and entropy from the Peng-Robinson equation | |
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| Liquefaction revisited | |
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| Adiabatically filling a tank with propane (optional) | |
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| Generalized Charts for the Enthalpy Departure | |
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| Summary | |
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| Practice Problems | |
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| Homework Problems | |
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| Phase Equilibrium in a Pure Fluid | |
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| Criteria for Equilibrium | |
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| The Clausius-Clapeyron Equation | |
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| Clausius-Clapeyron equation near or below the boiling point | |
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| Shortcut Estimation of Saturation Properties | |
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| Vapor pressure interpolation | |
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| Application of the shortcut vapor pressure equation | |
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| General application of the Clapeyron equation | |
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| Changes in Gibbs Energy With Pressure | |
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| Fugacity and Fugacity Coefficient | |
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| Fugacity Criteria for Phase Equilibria | |
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| Calculation of Fugacity (Gases) | |
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| Calculation of Fugacity (Liquids) | |
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| Calculation of Fugacity (Solids) | |
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| Saturation Conditions from an Equation of State | |
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| Vapor pressure from the Peng-Robinson equation | |
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| Acentric factor for the van der Waals equation | |
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| Summary | |
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| Temperature Effects on G and f (Optional) | |
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| Practice Problems | |
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| Homework Problems | |
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| Fluid Phase Equilibria in Mixtures | |
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| Introduction to Multicomponent Systems | |
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| Phase Diagrams | |
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| Concepts | |
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| Ideal Solutions | |
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| Vapor-Liquid Equilibrium (VLE) Calculations | |
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| Bubble and dew temperatures and isothermal flash of ideal solutions | |
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| Emission Modeling | |
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| Non-Ideal Systems | |
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| Advanced Topics (Optional) | |
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| Summary And Concluding Remarks | |
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| Practice Problems | |
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| Homework Problems | |
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| Phase Equilibria in Mixtures by an Equation of State | |
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| The virial equation for vapor mixtures | |
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| A Simple Model for Mixing Rules | |
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| Fugacity and Chemical Potential From An Eos | |
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| K-values from the Peng-Robinson equation | |
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| Differentiation of Mixing Rules | |
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| Fugacity coefficient from the virial equation | |
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| Fugacity coefficient for van der Waals equation | |
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| Fugacity coefficient from the Peng-Robinson equation | |
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| Vle Calculations by an Equation of State | |
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| Bubble point pressure from the Peng-Robinson equation | |
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| Isothermal flash using the Peng-Robinson equation | |
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| Phase diagram for azeotropic methanol + benzene | |
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| Phase diagram for nitrogen + methane | |
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| Ethane + heptane phase envelopes | |
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| Strategies for Applying Vle Routines | |
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| Summary and Concluding Remarks | |
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| Practice Problems | |
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| Homework Problems | |
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| Activity Models | |
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| Excess Properties | |
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| Modified Raoult's Law and Excess Gibbs Energy | |
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| Activity coefficients and the Gibbs-Duhem relation (optional) | |
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| VLE prediction using UNIFAC activity coefficients | |
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| Determination of G[superscript E] From Experimental Data | |
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| Gibbs excess energy for system 2-propanol + water | |
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| Activity coefficients by the one-parameter Margules equation | |
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| VLE predictions from the Margules one-parameter equation | |
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| The Van Der Waals' Perspective | |
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| Application of the van Laar equation | |
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| Infinite dilution activity coefficients from van Laar theory | |
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| VLE predictions using regular-solution theory | |
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| Scatchard-Hildebrand versus van Laar theory for methanol + benzene | |
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| Combinatorial contribution to the activity coefficient | |
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| Polymer mixing | |
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| Flory-Huggins and Van Der Waals' Theories (Optional) | |
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| Local Composition Theory | |
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| Local compositions in a 2-dimensional lattice | |
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| Application of Wilson's equation to VLE | |
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| Calculation of group mole fractions | |
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| Detailed calculations of activity coefficients via UNIFAC | |
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| Fitting Activity Models to Data (Optional) | |
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| Using Excel for fitting model parameters | |
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| T and P Dependence of Gibbs Energy (Optional) | |
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| The Molecular Basis of Solution Models (Optional) | |
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| Summary | |
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| Practice Problems | |
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| Homework Problems | |
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| Liquid-Liquid Phase Equilibria | |
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| The Onset of Liquid-Liquid Instability | |
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| Simple liquid-liquid-vapor equilibrium (LLVE) calculations | |
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| Stability and Excess Gibbs Energy | |
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| LLE predictions using Flory-Huggins theory: polymer mixing | |
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| LLE predictions using UNIFAC | |
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| Plotting Ternary Lle Data | |
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| Vlle With Immiscible Components | |
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| Steam distillation | |
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| Critical Points in Binary Liquid Mixtures (Optional) | |
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| Liquid-liquid critical point of the Margules one-parameter model | |
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| Liquid-liquid critical point of the Flory-Huggins model | |
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| Excel Procedure for Binary, Ternary Lle (Optional) | |
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| Summary | |
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| Practice Problems | |
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| Homework Problems | |
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| Special Topics | |
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| Phase Behavior | |
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| Solid-Liquid Equilibria | |
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| Eutectic behavior of chloronitrobenzenes | |
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| Eutectic behavior of benzene + phenol | |
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| Wax precipitation | |
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| Residue Curves | |
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| Homework Problems | |
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| Reacting Systems | |
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| Reacting Systems | |
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| Reaction Coordinate | |
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| Stoichiometry and the reaction coordinate | |
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| Equilibrium Constraint | |
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| Calculation of standard state Gibbs energy of reaction | |
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| Reaction Equilibria for Ideal Solutions | |
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| Computing the reaction coordinate | |
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| Butadiene revisited | |
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| Temperature Effects | |
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| Equilibrium constant as a function of temperature | |
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| Shortcut Estimation of Temperature Effects | |
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| Application of the shortcut van't Hoff equation | |
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| Energy Balances for Reactions | |
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| Adiabatic reaction in an ammonia reactor | |
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| General Observations About Pressure Effects | |
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| Multireaction Equilibria | |
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| Simultaneous reactions that can be solved by hand | |
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| Solving multireaction equilibrium equations by EXCEL | |
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| Direct minimization of the Gibbs energy with EXCEL | |
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| Pressure effects for Gibbs energy minimization | |
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| Simultaneous Reaction and Phase Equilibrium | |
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| The solvent methanol process | |
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| NO[subscript 2] absorption | |
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| Electrolyte Thermodynamics | |
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| Chlorine + water electrolyte solutions | |
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| Solid Components in Reactions | |
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| Thermal decomposition of methane | |
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| Summary and Concluding Remarks | |
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| Practice Problems | |
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| Homework Problems | |
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| Molecular Association and Solvation | |
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| Association and Solvation | |
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| Equilibrium Criteria | |
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| Balance Equations | |
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| Ideal Chemical Theory | |
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| Compressibility factors in associating/solvating systems | |
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| Dimerization of carboxylic acids | |
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| Activity coefficients in a solvated system | |
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| Chemical-Physical Theory | |
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| Pure Species With Linear Association | |
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| A Van Der Waals H-Bonding Model | |
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| Molecules of H[subscript 2]O in a 100-ml beaker | |
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| The Esd Equation for Associating Fluids | |
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| Extension to Complex Mixtures | |
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| Statistical Associating Fluid Theory (SAFT) | |
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| Summary Analysis of Association Models | |
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| Homework Problems | |
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| Glossary | |
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| Summary of Computer Programs | |
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| HP48 Calculator Programs | |
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| TI-85 Programs | |
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| PC Programs for Pure Component Properties | |
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| PC Programs for Mixture Phase Equilibria | |
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| Reaction Equilibria | |
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| How to Load Programs | |
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| Downloading HP Programs | |
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| Using Fortran Programs | |
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| Notes on Excel Spreadsheets | |
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| Notes on HP Calculator | |
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| Disclaimer | |
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| Mathematics | |
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| Important Relations | |
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| Solutions to Cubic Equations | |
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| The Dirac Delta Function | |
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| The Hard Sphere Equation of State | |
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| The Square-Well Equation of State | |
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| Strategy for Solving Vle Problems | |
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| Eos Methods | |
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| Activity Coefficient (Gamma-Phi) Method | |
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| Models for Process Simulators | |
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| Overview | |
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| Equations of State | |
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| Solutions Models | |
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| Hybrid Models | |
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| Recommended Decision Tree | |
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| Thermal Properties of Mixtures | |
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| Contamination from a reactor leak | |
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| Literature Cited | |
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| Pure Component Properties | |
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| Ideal Gas Heat Capacities | |
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| Liquid Heat Capacities | |
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| Solid Heat Capacities | |
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| Antoine Constants | |
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| Latent Heats | |
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| Enthalpies and Gibbs Energies of Formation | |
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| Properties of Water | |
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| Pressure-Enthalpy Diagram for Methane | |
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| Pressure-Enthalpy Diagram for Propane | |
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| Thermodynamic Properties of Hfc-134a | |
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| Index | |