An introduction to thermodynamics
Basic algorithm of thermodynamics (BAT) and its applications
Zhigang Suo
Professor of Mechanics and Materials, Harvard University
Email: [email protected]
Twitter: @zhigangsuo
Everything about ES 181 2019.
This book aims to help you master thermodynamics. I will keep updating the book. Please access the current version online. The book is written in a google doc. If you have the google doc app on your phone, pad, and computer, your copy of the book will always be synced with mine.
Also see a shorter version of this book: a review of thermodynamics
The play of thermodynamics
The cast
Thermodynamics for everyone
History
Ignore the laws
Postulates and facts
Big data
Logic, intuition, and application are distinct aspects of thermodynamics
Intuition
Application
logic
Basic algorithm of thermodynamics (BAT)
Pattern of application
Concrete examples
Reviews of books on thermodynamics and statistical physics
Ideal gas
Air
Atom and molecule
An experimental setup
What is temperature?
Ideal gas law
Boltzmann constant
Avogadro constant
Gas constants, universal and specific
Partial pressure of a species of molecules in an ideal gas mixture
Relative humidity
Moist air
Saturated vapor pressure
Relative humidity
The number of H2O molecules in a bottle of air
Dew point
Ice and water
Phase
State
Property
Temperature-energy curve
Energy of melting
Thermal capacity
Water and steam
Specific volume
An experimental setup to study water and steam
Temperature-volume plane
Process
Liquid-gas dome
Critical state
Rule of mixture
Many functions of two variables
Steam tables and steam apps
Inside the dome
Outside the dome
Pressure-volume plane
Temperature-pressure plane
Ice, water, and steam
Three-phase equilibrium
Experimental observations of three-phase equilibrium
Rule of three-phase mixture
Water expands on freezing
Temperature-volume plane
Pressure-volume-temperature surface
Pressure-volume plane
Temperature-pressure plane
Energy-volume plane
Three types of thermodynamic planes
Three phases of carbon dioxide
Isolated system
Energy, space, matter, and charge
System
A system interacts with its surroundings
Isolated system
An isolated system conserves energy, space, matter, and charge
A classification of systems
Energy
Potential energy
Definition of energy
Kinetic energy
Thermal energy (internal energy)
Electrical energy
Chemical energy
Energy belongs to many sciences
Measurement of internal energy function and energy transfer
Change in energy of several forms
Diabatic wall and adiabatic wall
Experimental determination of the internal energy of a closed system as a function of state
Experimental determination of the energy transfer from the fire to the fluid
Energy transfer depends on process
Adiabatic process
Constant-volume process
Constant-pressure process. Enthalpy
Transfer energy in various ways
Work and heat
Transfer energy by work
Transfer energy by heat
Sign convention
Misuse of the word heat
Work and heat are superfluous ideas in thermodynamics
The first law of thermodynamics
Internal energy of an ideal gas
Thermal capacity of an ideal gas
Energy transfer by work and by heat
Constant-volume process
Constant-pressure process
Isothermal process
Adiabatic process
Entropy
Sample space
Sample space of an isolated system
Definition of entropy
Entropy is a thermodynamic property
Entropy is extensive
Entropy is dimensionless
Entropy is absolute
Absolute, dimensionless entropies per molecule of H2O at various thermodynamic states
Numbers of quantum states per molecule in ice, water, and steam
Basic algorithm of thermodynamics (BAT)
Fundamental postulate of the statistics of an isolated system
Random variable
Ignorance is bliss
Dispersion of ink
Separation of phases
Subsystems
Constraint internal to an isolated system
Internal variable
Equilibrium
Reversibility
Irreversibility
Fluctuation
Kinetics
Basic algorithm of thermodynamics (BAT)
The second law of thermodynamics
Thermal system
Entropy and energy
A family of isolated systems of a single independent property
Energy-entropy plane
Common features of the function S(U)
Phrases associated with a family of isolated systems
Dissipation of energy
BAT on thermal contact
Definition of temperature
The zeroth law of thermodynamics
Degradation of energy
Features of the function T(U) common to all thermal systems
Thermal capacity
Calorimetry
Thermometry
Count the number of quantum states of an isolated system experimentally
Debye model
Theory of melting
Model melting using a thermal system
Primitive curves
A mixture of two homogeneous states
A mixture of any number of homogeneous states
Convex hull
Derived curve
Equilibrium of a single homogeneous state
Equilibrium of two homogeneous states
Equilibrium of three homogenous states does not exist in a thermal system
Temperature-entropy curve
Thermal system of a nonconvex characteristic function s(u)
Metastability
Thermal environment
Temperature as an independent variable
Thermostat
Thermal reservoir
A thermal system in a thermal environment
Partial equilibrium
Massieu function
Helmholtz function
Melting analyzed using the Helmholtz function
Closed system
A family of isolated systems of two independent variables
Energy-volume plane
Energy-volume-entropy space
Constant-volume process
Adiabatic process
Experimental determination of the function S(U,V) of a closed system
BAT on two closed systems in contact
Features of the function S(U,V) common to all closed systems
Thermal capacity
Theory of ideal gas
Ideal gas law derived
Energy of an ideal gas
Enthalpy of an ideal gas
Entropy of an ideal gas
Summary of equations of ideal gas
Entropic elasticity
Theory of osmosis
Theory of pure substance
Primitive surfaces
Rule of mixture
Derived surface
Equilibrium of a single homogeneous state
Equilibrium of two homogeneous states
Equilibrium of three homogeneous states
Equilibrium of four homogeneous states is impossible for a pure substance
Critical state
Metastability
Energy-volume plane
Temperature and pressure
Alternative independent properties
Entropy S(U,V)
Energy U(S,V)
Enthalpy H(S,P)
A closed system and a weight together constitute a thermal system
Enthalpy of a closed system
H(S,P) is a characteristic function of a closed system
Thermal capacity of a closed system in a constant-pressure process
Helmholtz function F(T,V)
Helmholtz function F(T,V) is a characteristic function of a closed system
Maxwell relation
Increment of the function U(T,V)
Increment of the function S(T,V)
A closed system in a thermal environment
Massieu function
Gibbs function G(T,P)
Gibbs function G(T,P) is a characteristic function of a closed system
Other mathematical relations
A closed system in a thermomechanical environment
Planck function
Free entropy vs free energy
Equilibrium of two homogeneous states by equating the Gibbs function
Clapeyron equation
Breed thermodynamic relations like rabbits
Van der Waals model of liquid-gas phase transition
Equation of state, P(T,V)
Critical state
Helmholtz function
Entropy
Energy
Competition between entropy and energy
Maxwell rule
From ideal gas to real fluid, multicomponent materials, and materials genome
Fossil-fueled civilization
Steam engine
Generator
From sunlight to electricity—an indirect route
From sunlight to electricity—a direct route
Energy flow chart
Rejected energy
Carnot cycle
Carnot question
Carnot engine
BAT on an engine
Reversible work
Energy efficiency
Carnot efficiency
Entropy efficiency
Entropy generation
Entropic price
Exergy
Carnot refrigerator
Produce mechanical energy using a thermal system and environment
Produce mechanical energy using a closed system and environment
Steady flow devices
Motion of a fluid
Control volume
Energy transfer at inlet and exit
Adiabatic turbine
Diabatic turbine
Compressor
Condenser
Nozzle
Throttle
Heat exchanger
Slides: engine and refrigerator
Ideal gas mixture
Thermodynamic states of an ideal gas mixture
Volume of an ideal gas mixture
Sliding semipermeable boxes
Energy of an ideal gas mixture
Enthalpy of an ideal gas mixture
Entropy of an ideal gas mixture
Entropy of mixing
Psychrometrics
Psychrometric state
Psychrometric chart
Psychrometric property
Psychrometric process
Open system
A family of isolated systems of many independent variables
Definition of chemical potentials
Temperature vs. chemical potential
BAT on two open systems in contact
Experimental determination of the chemical potential of a species of molecules in an open system
No litter
Gibbs function
Binary system
Unfinished business of collecting big data
Homogeneous function
Chemical potentials of molecules in simple systems
Pure substance
Incompressible pure substance
Pure ideal gas
Ideal gas mixture
Electronic nose
Relative humidity
The ascent of sap
The cost of an invasion
Transpiration pulls liquid water up
The tensile stress in xylem at the top of a tree
BAT on a tree
Mechanical, thermal, and chemical environment
Thermochemical environment
An open system in mechanical, thermal, and chemical environment
Partial equilibrium
Work
Chemical reaction
Stoichiometry
Absolute entropy
Conservation of energy
Change of enthalpy in several processes
BAT on a reaction
Enthalpy-entropy conflict
Fuel cell
Lithium ion batteries
Theoretical air
Dew point
Energy transfer by heat
Adiabatic flame temperature
Chemical equilibrium
Degree of reaction
Condition of chemical equilibrium
Ideal gas reaction
Simultaneous reactions
Linear algebra of chemical reaction
Dimensionless chemical potential
Flexibility in defining chemical potentials
Dimensionless chemical potential
Pure substance
Ideal gas
Summary of this play of thermodynamics
Our accomplishments
Isol