CHEMICAL ENGINEERING THERMODYNAMICS Andrew S. Rosen SYMBOL DICTIONARY | 1 TABLE OF CONTENTS Symbol Dictionary ........................................................................................................................ 3 1. Measured Thermodynamic Properties and Other Basic Concepts .................................. 5 1.1 Preliminary Concepts – The Language of Thermodynamics ........................................................ 5 1.2 Measured Thermodynamic Properties .......................................................................................... 5 1.2.1 Volume .................................................................................................................................................... 5 1.2.2 Temperature ............................................................................................................................................. 5 1.2.3 Pressure .................................................................................................................................................... 6 1.3 Equilibrium ................................................................................................................................... 7 1.3.1 Fundamental Definitions .......................................................................................................................... 7 1.3.2 Independent and Dependent Thermodynamic Properties ........................................................................ 7 1.3.3 Phases ...................................................................................................................................................... 8 2 The First Law of Thermodynamics ..................................................................................... 8 2.1 Definition of the First Law............................................................................................................ 8 2.2 Fundamental Definitions ............................................................................................................... 9 2.3 Work ............................................................................................................................................. 9 2.4 Hypothetical Paths ........................................................................................................................ 9 2.5 Reversible and Irreversible Processes ......................................................................................... 10 2.6 Closed Systems ........................................................................................................................... 10 2.6.1 Integral Balance ..................................................................................................................................... 10 2.6.2 Differential Balance ............................................................................................................................... 11 2.7 Isolated Systems .......................................................................................................................... 11 2.8 Open Systems .............................................................................................................................. 11 2.9 Open-System Energy Balance on Process Equipment ................................................................ 12 2.9.1 Introduction............................................................................................................................................ 12 2.9.2 Nozzles and Diffusers ............................................................................................................................ 13 2.9.3 Turbines and Pumps............................................................................................................................... 13 2.9.4 Heat Exchangers .................................................................................................................................... 13 2.9.5 Throttling Devices ................................................................................................................................. 13 2.10 Thermodynamic Data for 푈 and 퐻 ............................................................................................. 13 2.10.1 Heat Capacity .................................................................................................................................... 13 2.10.2 Latent Heat ........................................................................................................................................ 14 2.10.3 Enthalpy of Reaction ......................................................................................................................... 14 2.11 Calculating First-Law Quantities in Closed Systems .................................................................. 15 2.11.1 Starting Point ..................................................................................................................................... 15 2.11.2 Reversible, Isobaric Process .............................................................................................................. 16 2.11.3 Reversible, Isochoric Process ............................................................................................................ 16 2.11.4 Reversible, Isothermal Process .......................................................................................................... 16 2.11.5 Reversible, Adiabatic Process ........................................................................................................... 16 2.11.6 Irreversible, Adiabatic Expansion into a Vacuum ............................................................................. 17 2.12 Thermodynamic Cycles and the Carnot Cycle............................................................................ 17 3 Entropy and the Second Law of Thermodynamics .......................................................... 18 3.1 Definition of Entropy and the Second Law................................................................................. 18 3.2 The Second Law of Thermodynamics for Closed Systems ........................................................ 19 3.2.1 Reversible, Adiabatic Processes ............................................................................................................ 19 3.2.2 Reversible, Isothermal Processes ........................................................................................................... 19 3.2.3 Reversible, Isobaric Processes ............................................................................................................... 19 3.2.4 Reversible, Isochoric Processes ............................................................................................................. 19 3.2.5 Reversible Phase Change at Constant 푇 and 푃 ...................................................................................... 19 3.2.6 Irreversible Processes for Ideal Gases ................................................................................................... 20 3.2.7 Entropy Change of Mixing .................................................................................................................... 20 3.3 The Second Law of Thermodynamics for Open Systems ........................................................... 20 SYMBOL DICTIONARY | 2 3.4 The Mechanical Energy Balance ................................................................................................ 21 3.5 Vapor-Compression Power and Refrigeration Cycles ................................................................ 21 3.5.1 Rankine Cycle ........................................................................................................................................ 21 3.5.2 The Vapor-Compression Refrigeration Cycle ....................................................................................... 21 3.6 Molecular View of Entropy ........................................................................................................ 22 4 Equations of State and Intermolecular Forces ................................................................. 22 4.1 Review of the Ideal Gas Law ...................................................................................................... 22 4.2 Equations of State ....................................................................................................................... 22 4.2.1 Choosing an Equation of State ............................................................................................................... 22 4.2.2 Compressibility Equation ...................................................................................................................... 23 4.2.3 Van der Waals Equation ........................................................................................................................ 23 5 The Thermodynamic Web .................................................................................................. 23 5.1 Mathematical Relations............................................................................................................... 23 5.2 Derived Thermodynamic Quantities ........................................................................................... 24 5.3 Fundamental Property Relations ................................................................................................. 24 5.4 Maxwell Relations .....................................................................................................................