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College Physics

15.7 Statistical Interpretation of Entropy and the Second Law of Thermodynamics: The Underlying Explanation

College Physics15.7 Statistical Interpretation of Entropy and the Second Law of Thermodynamics: The Underlying Explanation
  1. Preface
  2. 1 Introduction: The Nature of Science and Physics
    1. Introduction to Science and the Realm of Physics, Physical Quantities, and Units
    2. 1.1 Physics: An Introduction
    3. 1.2 Physical Quantities and Units
    4. 1.3 Accuracy, Precision, and Significant Figures
    5. 1.4 Approximation
    6. Glossary
    7. Section Summary
    8. Conceptual Questions
    9. Problems & Exercises
  3. 2 Kinematics
    1. Introduction to One-Dimensional Kinematics
    2. 2.1 Displacement
    3. 2.2 Vectors, Scalars, and Coordinate Systems
    4. 2.3 Time, Velocity, and Speed
    5. 2.4 Acceleration
    6. 2.5 Motion Equations for Constant Acceleration in One Dimension
    7. 2.6 Problem-Solving Basics for One-Dimensional Kinematics
    8. 2.7 Falling Objects
    9. 2.8 Graphical Analysis of One-Dimensional Motion
    10. Glossary
    11. Section Summary
    12. Conceptual Questions
    13. Problems & Exercises
  4. 3 Two-Dimensional Kinematics
    1. Introduction to Two-Dimensional Kinematics
    2. 3.1 Kinematics in Two Dimensions: An Introduction
    3. 3.2 Vector Addition and Subtraction: Graphical Methods
    4. 3.3 Vector Addition and Subtraction: Analytical Methods
    5. 3.4 Projectile Motion
    6. 3.5 Addition of Velocities
    7. Glossary
    8. Section Summary
    9. Conceptual Questions
    10. Problems & Exercises
  5. 4 Dynamics: Force and Newton's Laws of Motion
    1. Introduction to Dynamics: Newton’s Laws of Motion
    2. 4.1 Development of Force Concept
    3. 4.2 Newton’s First Law of Motion: Inertia
    4. 4.3 Newton’s Second Law of Motion: Concept of a System
    5. 4.4 Newton’s Third Law of Motion: Symmetry in Forces
    6. 4.5 Normal, Tension, and Other Examples of Forces
    7. 4.6 Problem-Solving Strategies
    8. 4.7 Further Applications of Newton’s Laws of Motion
    9. 4.8 Extended Topic: The Four Basic Forces—An Introduction
    10. Glossary
    11. Section Summary
    12. Conceptual Questions
    13. Problems & Exercises
  6. 5 Further Applications of Newton's Laws: Friction, Drag, and Elasticity
    1. Introduction: Further Applications of Newton’s Laws
    2. 5.1 Friction
    3. 5.2 Drag Forces
    4. 5.3 Elasticity: Stress and Strain
    5. Glossary
    6. Section Summary
    7. Conceptual Questions
    8. Problems & Exercises
  7. 6 Uniform Circular Motion and Gravitation
    1. Introduction to Uniform Circular Motion and Gravitation
    2. 6.1 Rotation Angle and Angular Velocity
    3. 6.2 Centripetal Acceleration
    4. 6.3 Centripetal Force
    5. 6.4 Fictitious Forces and Non-inertial Frames: The Coriolis Force
    6. 6.5 Newton’s Universal Law of Gravitation
    7. 6.6 Satellites and Kepler’s Laws: An Argument for Simplicity
    8. Glossary
    9. Section Summary
    10. Conceptual Questions
    11. Problems & Exercises
  8. 7 Work, Energy, and Energy Resources
    1. Introduction to Work, Energy, and Energy Resources
    2. 7.1 Work: The Scientific Definition
    3. 7.2 Kinetic Energy and the Work-Energy Theorem
    4. 7.3 Gravitational Potential Energy
    5. 7.4 Conservative Forces and Potential Energy
    6. 7.5 Nonconservative Forces
    7. 7.6 Conservation of Energy
    8. 7.7 Power
    9. 7.8 Work, Energy, and Power in Humans
    10. 7.9 World Energy Use
    11. Glossary
    12. Section Summary
    13. Conceptual Questions
    14. Problems & Exercises
  9. 8 Linear Momentum and Collisions
    1. Introduction to Linear Momentum and Collisions
    2. 8.1 Linear Momentum and Force
    3. 8.2 Impulse
    4. 8.3 Conservation of Momentum
    5. 8.4 Elastic Collisions in One Dimension
    6. 8.5 Inelastic Collisions in One Dimension
    7. 8.6 Collisions of Point Masses in Two Dimensions
    8. 8.7 Introduction to Rocket Propulsion
    9. Glossary
    10. Section Summary
    11. Conceptual Questions
    12. Problems & Exercises
  10. 9 Statics and Torque
    1. Introduction to Statics and Torque
    2. 9.1 The First Condition for Equilibrium
    3. 9.2 The Second Condition for Equilibrium
    4. 9.3 Stability
    5. 9.4 Applications of Statics, Including Problem-Solving Strategies
    6. 9.5 Simple Machines
    7. 9.6 Forces and Torques in Muscles and Joints
    8. Glossary
    9. Section Summary
    10. Conceptual Questions
    11. Problems & Exercises
  11. 10 Rotational Motion and Angular Momentum
    1. Introduction to Rotational Motion and Angular Momentum
    2. 10.1 Angular Acceleration
    3. 10.2 Kinematics of Rotational Motion
    4. 10.3 Dynamics of Rotational Motion: Rotational Inertia
    5. 10.4 Rotational Kinetic Energy: Work and Energy Revisited
    6. 10.5 Angular Momentum and Its Conservation
    7. 10.6 Collisions of Extended Bodies in Two Dimensions
    8. 10.7 Gyroscopic Effects: Vector Aspects of Angular Momentum
    9. Glossary
    10. Section Summary
    11. Conceptual Questions
    12. Problems & Exercises
  12. 11 Fluid Statics
    1. Introduction to Fluid Statics
    2. 11.1 What Is a Fluid?
    3. 11.2 Density
    4. 11.3 Pressure
    5. 11.4 Variation of Pressure with Depth in a Fluid
    6. 11.5 Pascal’s Principle
    7. 11.6 Gauge Pressure, Absolute Pressure, and Pressure Measurement
    8. 11.7 Archimedes’ Principle
    9. 11.8 Cohesion and Adhesion in Liquids: Surface Tension and Capillary Action
    10. 11.9 Pressures in the Body
    11. Glossary
    12. Section Summary
    13. Conceptual Questions
    14. Problems & Exercises
  13. 12 Fluid Dynamics and Its Biological and Medical Applications
    1. Introduction to Fluid Dynamics and Its Biological and Medical Applications
    2. 12.1 Flow Rate and Its Relation to Velocity
    3. 12.2 Bernoulli’s Equation
    4. 12.3 The Most General Applications of Bernoulli’s Equation
    5. 12.4 Viscosity and Laminar Flow; Poiseuille’s Law
    6. 12.5 The Onset of Turbulence
    7. 12.6 Motion of an Object in a Viscous Fluid
    8. 12.7 Molecular Transport Phenomena: Diffusion, Osmosis, and Related Processes
    9. Glossary
    10. Section Summary
    11. Conceptual Questions
    12. Problems & Exercises
  14. 13 Temperature, Kinetic Theory, and the Gas Laws
    1. Introduction to Temperature, Kinetic Theory, and the Gas Laws
    2. 13.1 Temperature
    3. 13.2 Thermal Expansion of Solids and Liquids
    4. 13.3 The Ideal Gas Law
    5. 13.4 Kinetic Theory: Atomic and Molecular Explanation of Pressure and Temperature
    6. 13.5 Phase Changes
    7. 13.6 Humidity, Evaporation, and Boiling
    8. Glossary
    9. Section Summary
    10. Conceptual Questions
    11. Problems & Exercises
  15. 14 Heat and Heat Transfer Methods
    1. Introduction to Heat and Heat Transfer Methods
    2. 14.1 Heat
    3. 14.2 Temperature Change and Heat Capacity
    4. 14.3 Phase Change and Latent Heat
    5. 14.4 Heat Transfer Methods
    6. 14.5 Conduction
    7. 14.6 Convection
    8. 14.7 Radiation
    9. Glossary
    10. Section Summary
    11. Conceptual Questions
    12. Problems & Exercises
  16. 15 Thermodynamics
    1. Introduction to Thermodynamics
    2. 15.1 The First Law of Thermodynamics
    3. 15.2 The First Law of Thermodynamics and Some Simple Processes
    4. 15.3 Introduction to the Second Law of Thermodynamics: Heat Engines and Their Efficiency
    5. 15.4 Carnot’s Perfect Heat Engine: The Second Law of Thermodynamics Restated
    6. 15.5 Applications of Thermodynamics: Heat Pumps and Refrigerators
    7. 15.6 Entropy and the Second Law of Thermodynamics: Disorder and the Unavailability of Energy
    8. 15.7 Statistical Interpretation of Entropy and the Second Law of Thermodynamics: The Underlying Explanation
    9. Glossary
    10. Section Summary
    11. Conceptual Questions
    12. Problems & Exercises
  17. 16 Oscillatory Motion and Waves
    1. Introduction to Oscillatory Motion and Waves
    2. 16.1 Hooke’s Law: Stress and Strain Revisited
    3. 16.2 Period and Frequency in Oscillations
    4. 16.3 Simple Harmonic Motion: A Special Periodic Motion
    5. 16.4 The Simple Pendulum
    6. 16.5 Energy and the Simple Harmonic Oscillator
    7. 16.6 Uniform Circular Motion and Simple Harmonic Motion
    8. 16.7 Damped Harmonic Motion
    9. 16.8 Forced Oscillations and Resonance
    10. 16.9 Waves
    11. 16.10 Superposition and Interference
    12. 16.11 Energy in Waves: Intensity
    13. Glossary
    14. Section Summary
    15. Conceptual Questions
    16. Problems & Exercises
  18. 17 Physics of Hearing
    1. Introduction to the Physics of Hearing
    2. 17.1 Sound
    3. 17.2 Speed of Sound, Frequency, and Wavelength
    4. 17.3 Sound Intensity and Sound Level
    5. 17.4 Doppler Effect and Sonic Booms
    6. 17.5 Sound Interference and Resonance: Standing Waves in Air Columns
    7. 17.6 Hearing
    8. 17.7 Ultrasound
    9. Glossary
    10. Section Summary
    11. Conceptual Questions
    12. Problems & Exercises
  19. 18 Electric Charge and Electric Field
    1. Introduction to Electric Charge and Electric Field
    2. 18.1 Static Electricity and Charge: Conservation of Charge
    3. 18.2 Conductors and Insulators
    4. 18.3 Coulomb’s Law
    5. 18.4 Electric Field: Concept of a Field Revisited
    6. 18.5 Electric Field Lines: Multiple Charges
    7. 18.6 Electric Forces in Biology
    8. 18.7 Conductors and Electric Fields in Static Equilibrium
    9. 18.8 Applications of Electrostatics
    10. Glossary
    11. Section Summary
    12. Conceptual Questions
    13. Problems & Exercises
  20. 19 Electric Potential and Electric Field
    1. Introduction to Electric Potential and Electric Energy
    2. 19.1 Electric Potential Energy: Potential Difference
    3. 19.2 Electric Potential in a Uniform Electric Field
    4. 19.3 Electrical Potential Due to a Point Charge
    5. 19.4 Equipotential Lines
    6. 19.5 Capacitors and Dielectrics
    7. 19.6 Capacitors in Series and Parallel
    8. 19.7 Energy Stored in Capacitors
    9. Glossary
    10. Section Summary
    11. Conceptual Questions
    12. Problems & Exercises
  21. 20 Electric Current, Resistance, and Ohm's Law
    1. Introduction to Electric Current, Resistance, and Ohm's Law
    2. 20.1 Current
    3. 20.2 Ohm’s Law: Resistance and Simple Circuits
    4. 20.3 Resistance and Resistivity
    5. 20.4 Electric Power and Energy
    6. 20.5 Alternating Current versus Direct Current
    7. 20.6 Electric Hazards and the Human Body
    8. 20.7 Nerve Conduction–Electrocardiograms
    9. Glossary
    10. Section Summary
    11. Conceptual Questions
    12. Problems & Exercises
  22. 21 Circuits and DC Instruments
    1. Introduction to Circuits and DC Instruments
    2. 21.1 Resistors in Series and Parallel
    3. 21.2 Electromotive Force: Terminal Voltage
    4. 21.3 Kirchhoff’s Rules
    5. 21.4 DC Voltmeters and Ammeters
    6. 21.5 Null Measurements
    7. 21.6 DC Circuits Containing Resistors and Capacitors
    8. Glossary
    9. Section Summary
    10. Conceptual Questions
    11. Problems & Exercises
  23. 22 Magnetism
    1. Introduction to Magnetism
    2. 22.1 Magnets
    3. 22.2 Ferromagnets and Electromagnets
    4. 22.3 Magnetic Fields and Magnetic Field Lines
    5. 22.4 Magnetic Field Strength: Force on a Moving Charge in a Magnetic Field
    6. 22.5 Force on a Moving Charge in a Magnetic Field: Examples and Applications
    7. 22.6 The Hall Effect
    8. 22.7 Magnetic Force on a Current-Carrying Conductor
    9. 22.8 Torque on a Current Loop: Motors and Meters
    10. 22.9 Magnetic Fields Produced by Currents: Ampere’s Law
    11. 22.10 Magnetic Force between Two Parallel Conductors
    12. 22.11 More Applications of Magnetism
    13. Glossary
    14. Section Summary
    15. Conceptual Questions
    16. Problems & Exercises
  24. 23 Electromagnetic Induction, AC Circuits, and Electrical Technologies
    1. Introduction to Electromagnetic Induction, AC Circuits and Electrical Technologies
    2. 23.1 Induced Emf and Magnetic Flux
    3. 23.2 Faraday’s Law of Induction: Lenz’s Law
    4. 23.3 Motional Emf
    5. 23.4 Eddy Currents and Magnetic Damping
    6. 23.5 Electric Generators
    7. 23.6 Back Emf
    8. 23.7 Transformers
    9. 23.8 Electrical Safety: Systems and Devices
    10. 23.9 Inductance
    11. 23.10 RL Circuits
    12. 23.11 Reactance, Inductive and Capacitive
    13. 23.12 RLC Series AC Circuits
    14. Glossary
    15. Section Summary
    16. Conceptual Questions
    17. Problems & Exercises
  25. 24 Electromagnetic Waves
    1. Introduction to Electromagnetic Waves
    2. 24.1 Maxwell’s Equations: Electromagnetic Waves Predicted and Observed
    3. 24.2 Production of Electromagnetic Waves
    4. 24.3 The Electromagnetic Spectrum
    5. 24.4 Energy in Electromagnetic Waves
    6. Glossary
    7. Section Summary
    8. Conceptual Questions
    9. Problems & Exercises
  26. 25 Geometric Optics
    1. Introduction to Geometric Optics
    2. 25.1 The Ray Aspect of Light
    3. 25.2 The Law of Reflection
    4. 25.3 The Law of Refraction
    5. 25.4 Total Internal Reflection
    6. 25.5 Dispersion: The Rainbow and Prisms
    7. 25.6 Image Formation by Lenses
    8. 25.7 Image Formation by Mirrors
    9. Glossary
    10. Section Summary
    11. Conceptual Questions
    12. Problems & Exercises
  27. 26 Vision and Optical Instruments
    1. Introduction to Vision and Optical Instruments
    2. 26.1 Physics of the Eye
    3. 26.2 Vision Correction
    4. 26.3 Color and Color Vision
    5. 26.4 Microscopes
    6. 26.5 Telescopes
    7. 26.6 Aberrations
    8. Glossary
    9. Section Summary
    10. Conceptual Questions
    11. Problems & Exercises
  28. 27 Wave Optics
    1. Introduction to Wave Optics
    2. 27.1 The Wave Aspect of Light: Interference
    3. 27.2 Huygens's Principle: Diffraction
    4. 27.3 Young’s Double Slit Experiment
    5. 27.4 Multiple Slit Diffraction
    6. 27.5 Single Slit Diffraction
    7. 27.6 Limits of Resolution: The Rayleigh Criterion
    8. 27.7 Thin Film Interference
    9. 27.8 Polarization
    10. 27.9 *Extended Topic* Microscopy Enhanced by the Wave Characteristics of Light
    11. Glossary
    12. Section Summary
    13. Conceptual Questions
    14. Problems & Exercises
  29. 28 Special Relativity
    1. Introduction to Special Relativity
    2. 28.1 Einstein’s Postulates
    3. 28.2 Simultaneity And Time Dilation
    4. 28.3 Length Contraction
    5. 28.4 Relativistic Addition of Velocities
    6. 28.5 Relativistic Momentum
    7. 28.6 Relativistic Energy
    8. Glossary
    9. Section Summary
    10. Conceptual Questions
    11. Problems & Exercises
  30. 29 Introduction to Quantum Physics
    1. Introduction to Quantum Physics
    2. 29.1 Quantization of Energy
    3. 29.2 The Photoelectric Effect
    4. 29.3 Photon Energies and the Electromagnetic Spectrum
    5. 29.4 Photon Momentum
    6. 29.5 The Particle-Wave Duality
    7. 29.6 The Wave Nature of Matter
    8. 29.7 Probability: The Heisenberg Uncertainty Principle
    9. 29.8 The Particle-Wave Duality Reviewed
    10. Glossary
    11. Section Summary
    12. Conceptual Questions
    13. Problems & Exercises
  31. 30 Atomic Physics
    1. Introduction to Atomic Physics
    2. 30.1 Discovery of the Atom
    3. 30.2 Discovery of the Parts of the Atom: Electrons and Nuclei
    4. 30.3 Bohr’s Theory of the Hydrogen Atom
    5. 30.4 X Rays: Atomic Origins and Applications
    6. 30.5 Applications of Atomic Excitations and De-Excitations
    7. 30.6 The Wave Nature of Matter Causes Quantization
    8. 30.7 Patterns in Spectra Reveal More Quantization
    9. 30.8 Quantum Numbers and Rules
    10. 30.9 The Pauli Exclusion Principle
    11. Glossary
    12. Section Summary
    13. Conceptual Questions
    14. Problems & Exercises
  32. 31 Radioactivity and Nuclear Physics
    1. Introduction to Radioactivity and Nuclear Physics
    2. 31.1 Nuclear Radioactivity
    3. 31.2 Radiation Detection and Detectors
    4. 31.3 Substructure of the Nucleus
    5. 31.4 Nuclear Decay and Conservation Laws
    6. 31.5 Half-Life and Activity
    7. 31.6 Binding Energy
    8. 31.7 Tunneling
    9. Glossary
    10. Section Summary
    11. Conceptual Questions
    12. Problems & Exercises
  33. 32 Medical Applications of Nuclear Physics
    1. Introduction to Applications of Nuclear Physics
    2. 32.1 Medical Imaging and Diagnostics
    3. 32.2 Biological Effects of Ionizing Radiation
    4. 32.3 Therapeutic Uses of Ionizing Radiation
    5. 32.4 Food Irradiation
    6. 32.5 Fusion
    7. 32.6 Fission
    8. 32.7 Nuclear Weapons
    9. Glossary
    10. Section Summary
    11. Conceptual Questions
    12. Problems & Exercises
  34. 33 Particle Physics
    1. Introduction to Particle Physics
    2. 33.1 The Yukawa Particle and the Heisenberg Uncertainty Principle Revisited
    3. 33.2 The Four Basic Forces
    4. 33.3 Accelerators Create Matter from Energy
    5. 33.4 Particles, Patterns, and Conservation Laws
    6. 33.5 Quarks: Is That All There Is?
    7. 33.6 GUTs: The Unification of Forces
    8. Glossary
    9. Section Summary
    10. Conceptual Questions
    11. Problems & Exercises
  35. 34 Frontiers of Physics
    1. Introduction to Frontiers of Physics
    2. 34.1 Cosmology and Particle Physics
    3. 34.2 General Relativity and Quantum Gravity
    4. 34.3 Superstrings
    5. 34.4 Dark Matter and Closure
    6. 34.5 Complexity and Chaos
    7. 34.6 High-temperature Superconductors
    8. 34.7 Some Questions We Know to Ask
    9. Glossary
    10. Section Summary
    11. Conceptual Questions
    12. Problems & Exercises
  36. A | Atomic Masses
  37. B | Selected Radioactive Isotopes
  38. C | Useful Information
  39. D | Glossary of Key Symbols and Notation
  40. Index
Photograph of many coins laid down on a surface, some with heads shown up and some with tails shown up.
Figure 15.38 When you toss a coin a large number of times, heads and tails tend to come up in roughly equal numbers. Why doesn’t heads come up 100, 90, or even 80% of the time? (credit: Jon Sullivan, PDPhoto.org)

The various ways of formulating the second law of thermodynamics tell what happens rather than why it happens. Why should heat transfer occur only from hot to cold? Why should energy become ever less available to do work? Why should the universe become increasingly disorderly? The answer is that it is a matter of overwhelming probability. Disorder is simply vastly more likely than order.

When you watch an emerging rain storm begin to wet the ground, you will notice that the drops fall in a disorganized manner both in time and in space. Some fall close together, some far apart, but they never fall in straight, orderly rows. It is not impossible for rain to fall in an orderly pattern, just highly unlikely, because there are many more disorderly ways than orderly ones. To illustrate this fact, we will examine some random processes, starting with coin tosses.

Coin Tosses

What are the possible outcomes of tossing 5 coins? Each coin can land either heads or tails. On the large scale, we are concerned only with the total heads and tails and not with the order in which heads and tails appear. The following possibilities exist:

5 heads, 0 tails 4 heads, 1 tail 3 heads, 2 tails 2 heads, 3 tails 1 head, 4 tails 0 head, 5 tails 5 heads, 0 tails 4 heads, 1 tail 3 heads, 2 tails 2 heads, 3 tails 1 head, 4 tails 0 head, 5 tails alignl { stack { size 12{"5 heads, 0 tails"} {} # size 12{"4 heads, 1 tail"} {} # size 12{"3 heads, 2 tails"} {} # size 12{"2 heads, 3 tails"} {} # size 12{"1 head, 4 tails"} {} # size 12{"0 head, 5 tails"} {} } } {}
15.67

These are what we call macrostates. A macrostate is an overall property of a system. It does not specify the details of the system, such as the order in which heads and tails occur or which coins are heads or tails.

Using this nomenclature, a system of 5 coins has the 6 possible macrostates just listed. Some macrostates are more likely to occur than others. For instance, there is only one way to get 5 heads, but there are several ways to get 3 heads and 2 tails, making the latter macrostate more probable. Table 15.3 lists of all the ways in which 5 coins can be tossed, taking into account the order in which heads and tails occur. Each sequence is called a microstate—a detailed description of every element of a system.

Individual microstates Number of microstates
5 heads, 0 tails HHHHH 1
4 heads, 1 tail HHHHT, HHHTH, HHTHH, HTHHH, THHHH 5
3 heads, 2 tails HTHTH, THTHH, HTHHT, THHTH, THHHT HTHTH, THTHH, HTHHT, THHTH, THHHT 10
2 heads, 3 tails TTTHH, TTHHT, THHTT, HHTTT, TTHTH, THTHT, HTHTT, THTTH, HTTHT, HTTTH 10
1 head, 4 tails TTTTH, TTTHT, TTHTT, THTTT, HTTTT 5
0 heads, 5 tails TTTTT 1
Total: 32
Table 15.3 5-Coin Toss

The macrostate of 3 heads and 2 tails can be achieved in 10 ways and is thus 10 times more probable than the one having 5 heads. Not surprisingly, it is equally probable to have the reverse, 2 heads and 3 tails. Similarly, it is equally probable to get 5 tails as it is to get 5 heads. Note that all of these conclusions are based on the crucial assumption that each microstate is equally probable. With coin tosses, this requires that the coins not be asymmetric in a way that favors one side over the other, as with loaded dice. With any system, the assumption that all microstates are equally probable must be valid, or the analysis will be erroneous.

The two most orderly possibilities are 5 heads or 5 tails. (They are more structured than the others.) They are also the least likely, only 2 out of 32 possibilities. The most disorderly possibilities are 3 heads and 2 tails and its reverse. (They are the least structured.) The most disorderly possibilities are also the most likely, with 20 out of 32 possibilities for the 3 heads and 2 tails and its reverse. If we start with an orderly array like 5 heads and toss the coins, it is very likely that we will get a less orderly array as a result, since 30 out of the 32 possibilities are less orderly. So even if you start with an orderly state, there is a strong tendency to go from order to disorder, from low entropy to high entropy. The reverse can happen, but it is unlikely.

Macrostate Number of microstates
Heads Tails (W)
100 0 1
99 1 1 . 0 × 10 2 1 . 0 × 10 2 size 12{1 "." 0´"10" rSup { size 8{2} } } {}
95 5 7 . 5 × 10 7 7 . 5 × 10 7 size 12{7 "." 5´"10" rSup { size 8{7} } } {}
90 10 1 . 7 × 10 13 1 . 7 × 10 13 size 12{1 "." 7´"10" rSup { size 8{"13"} } } {}
75 25 2 . 4 × 10 23 2 . 4 × 10 23 size 12{2 "." 4´"10" rSup { size 8{"23"} } } {}
60 40 1 . 4 × 10 28 1 . 4 × 10 28 size 12{1 "." 4´"10" rSup { size 8{"28"} } } {}
55 45 6 . 1 × 10 28 6 . 1 × 10 28 size 12{6 "." 1´"10" rSup { size 8{"28"} } } {}
51 49 9 . 9 × 10 28 9 . 9 × 10 28 size 12{9 "." 9´"10" rSup { size 8{"28"} } } {}
50 50 1 . 0 × 10 29 1 . 0 × 10 29 size 12{1 "." 0´"10" rSup { size 8{"29"} } } {}
49 51 9 . 9 × 10 28 9 . 9 × 10 28 size 12{9 "." 9´"10" rSup { size 8{"28"} } } {}
45 55 6 . 1 × 10 28 6 . 1 × 10 28 size 12{6 "." 1´"10" rSup { size 8{"28"} } } {}
40 60 1 . 4 × 10 28 1 . 4 × 10 28 size 12{1 "." 4´"10" rSup { size 8{"28"} } } {}
25 75 2 . 4 × 10 23 2 . 4 × 10 23 size 12{2 "." 4´"10" rSup { size 8{"23"} } } {}
10 90 1 . 7 × 10 13 1 . 7 × 10 13 size 12{1 "." 7´"10" rSup { size 8{"13"} } } {}
5 95 7 . 5 × 10 7 7 . 5 × 10 7 size 12{7 "." 5´"10" rSup { size 8{7} } } {}
1 99 1 . 0 × 10 2 1 . 0 × 10 2 size 12{1 "." 0´"10" rSup { size 8{2} } } {}
0 100 1
Total: 1.27×10301.27×1030 size 12{1 "." "27"´"10" rSup { size 8{"30"} } } {}
Table 15.4 100-Coin Toss

This result becomes dramatic for larger systems. Consider what happens if you have 100 coins instead of just 5. The most orderly arrangements (most structured) are 100 heads or 100 tails. The least orderly (least structured) is that of 50 heads and 50 tails. There is only 1 way (1 microstate) to get the most orderly arrangement of 100 heads. There are 100 ways (100 microstates) to get the next most orderly arrangement of 99 heads and 1 tail (also 100 to get its reverse). And there are 1.0×10291.0×1029 size 12{1 "." 0 times "10" rSup { size 8{"29"} } } {} ways to get 50 heads and 50 tails, the least orderly arrangement. Table 15.4 is an abbreviated list of the various macrostates and the number of microstates for each macrostate. The total number of microstates—the total number of different ways 100 coins can be tossed—is an impressively large 1.27×10301.27×1030 size 12{1 "." "27" times "10" rSup { size 8{"30"} } } {}. Now, if we start with an orderly macrostate like 100 heads and toss the coins, there is a virtual certainty that we will get a less orderly macrostate. If we keep tossing the coins, it is possible, but exceedingly unlikely, that we will ever get back to the most orderly macrostate. If you tossed the coins once each second, you could expect to get either 100 heads or 100 tails once in 2×10222×1022 size 12{2 times "10" rSup { size 8{"22"} } } {} years! This period is 1 trillion (10121012 size 12{"10" rSup { size 8{"12"} } } {}) times longer than the age of the universe, and so the chances are essentially zero. In contrast, there is an 8% chance of getting 50 heads, a 73% chance of getting from 45 to 55 heads, and a 96% chance of getting from 40 to 60 heads. Disorder is highly likely.

Disorder in a Gas

The fantastic growth in the odds favoring disorder that we see in going from 5 to 100 coins continues as the number of entities in the system increases. Let us now imagine applying this approach to perhaps a small sample of gas. Because counting microstates and macrostates involves statistics, this is called statistical analysis. The macrostates of a gas correspond to its macroscopic properties, such as volume, temperature, and pressure; and its microstates correspond to the detailed description of the positions and velocities of its atoms. Even a small amount of gas has a huge number of atoms: 1.0 cm31.0 cm3 size 12{1 "." 0" cm" rSup { size 8{3} } } {} of an ideal gas at 1.0 atm and 0º C0º C size 12{0°C} {} has 2.7×10192.7×1019 size 12{2 "." 7 times "10" rSup { size 8{"19"} } } {} atoms. So each macrostate has an immense number of microstates. In plain language, this means that there are an immense number of ways in which the atoms in a gas can be arranged, while still having the same pressure, temperature, and so on.

The most likely conditions (or macrostates) for a gas are those we see all the time—a random distribution of atoms in space with a Maxwell-Boltzmann distribution of speeds in random directions, as predicted by kinetic theory. This is the most disorderly and least structured condition we can imagine. In contrast, one type of very orderly and structured macrostate has all of the atoms in one corner of a container with identical velocities. There are very few ways to accomplish this (very few microstates corresponding to it), and so it is exceedingly unlikely ever to occur. (See Figure 15.39(b).) Indeed, it is so unlikely that we have a law saying that it is impossible, which has never been observed to be violated—the second law of thermodynamics.

Two states of a container of gas are shown. In state a, the gas molecules, depicted as small green spheres, are randomly distributed in the container, with random velocities (an arrow is attached to each sphere, and the arrows vary in length and direction). This state is labeled likely. In state b, the molecules are clustered in the lower left-hand corner of the container and the arrows are much shorter. This state is labeled highly unlikely.
Figure 15.39 (a) The ordinary state of gas in a container is a disorderly, random distribution of atoms or molecules with a Maxwell-Boltzmann distribution of speeds. It is so unlikely that these atoms or molecules would ever end up in one corner of the container that it might as well be impossible. (b) With energy transfer, the gas can be forced into one corner and its entropy greatly reduced. But left alone, it will spontaneously increase its entropy and return to the normal conditions, because they are immensely more likely.

The disordered condition is one of high entropy, and the ordered one has low entropy. With a transfer of energy from another system, we could force all of the atoms into one corner and have a local decrease in entropy, but at the cost of an overall increase in entropy of the universe. If the atoms start out in one corner, they will quickly disperse and become uniformly distributed and will never return to the orderly original state (Figure 15.39(b)). Entropy will increase. With such a large sample of atoms, it is possible—but unimaginably unlikely—for entropy to decrease. Disorder is vastly more likely than order.

The arguments that disorder and high entropy are the most probable states are quite convincing. The great Austrian physicist Ludwig Boltzmann (1844–1906)—who, along with Maxwell, made so many contributions to kinetic theory—proved that the entropy of a system in a given state (a macrostate) can be written as

S=k lnW,S=k lnW, size 12{S=k" ln"W} {}
15.68

where k=1.38×1023J/Kk=1.38×1023J/K size 12{k=1 "." "38" times "10" rSup { size 8{ - "23"} } "J/K"} {} is Boltzmann’s constant, and lnWlnW size 12{"ln" W} {} is the natural logarithm of the number of microstates WW size 12{ W} {} corresponding to the given macrostate. WW size 12{ W} {} is proportional to the probability that the macrostate will occur. Thus entropy is directly related to the probability of a state—the more likely the state, the greater its entropy. Boltzmann proved that this expression for SS size 12{ S} {} is equivalent to the definition ΔS=Q/TΔS=Q/T size 12{ ΔS=Q/T} {}, which we have used extensively.

Thus the second law of thermodynamics is explained on a very basic level: entropy either remains the same or increases in every process. This phenomenon is due to the extraordinarily small probability of a decrease, based on the extraordinarily larger number of microstates in systems with greater entropy. Entropy can decrease, but for any macroscopic system, this outcome is so unlikely that it will never be observed.

Example 15.9 Entropy Increases in a Coin Toss

Suppose you toss 100 coins starting with 60 heads and 40 tails, and you get the most likely result, 50 heads and 50 tails. What is the change in entropy?

Strategy

Noting that the number of microstates is labeled WW size 12{W} {} in Table 15.4 for the 100-coin toss, we can use ΔS=SfSi=k lnWf-klnWiΔS=SfSi=k lnWf-klnWi size 12{DS=S rSub { size 8{f} } -S rSub { size 8{i} } =k" ln"W rSub { size 8{f} } +- k"ln"W rSub { size 8{i} } } {} to calculate the change in entropy.

Solution

The change in entropy is

ΔS=SfSi=k lnWfklnWi,ΔS=SfSi=k lnWfklnWi, size 12{DS=S rSub { size 8{f} } -S rSub { size 8{i} } =k" ln"W rSub { size 8{f} } +- k"ln"W rSub { size 8{i} } } {}
15.69

where the subscript i stands for the initial 60 heads and 40 tails state, and the subscript f for the final 50 heads and 50 tails state. Substituting the values for WW size 12{W} {} from Table 15.4 gives

ΔS = ( 1 . 38 × 10 23 J/K ) [ ln ( 1 . 0 × 10 29 ) ln ( 1 . 4 × 10 28 ) ] = 2.7 × 10 23 J/K ΔS = ( 1 . 38 × 10 23 J/K ) [ ln ( 1 . 0 × 10 29 ) ln ( 1 . 4 × 10 28 ) ] = 2.7 × 10 23 J/K alignl { stack { size 12{DS= \( 1 "." "38"´"10" rSup { size 8{-"23"} } " J/K" \) \[ "ln" \( 1 "." 0´"10" rSup { size 8{"29"} } \) +- "ln " \( 1 "." 4´"10" rSup { size 8{"28"} } \) \] } {} # " =2" "." 7´"10" rSup { size 8{ +- "23"} } " J/K" {} } } {}
15.70

Discussion

This increase in entropy means we have moved to a less orderly situation. It is not impossible for further tosses to produce the initial state of 60 heads and 40 tails, but it is less likely. There is about a 1 in 90 chance for that decrease in entropy (2.7×1023 J/K2.7×1023 J/K size 12{ +- 2 "." 7´"10" rSup { size 8{ +- "23"} } " J/K"} {}) to occur. If we calculate the decrease in entropy to move to the most orderly state, we get ΔS=92×1023 J/KΔS=92×1023 J/K size 12{DS= +- "92"´"10" rSup { size 8{ +- "23"} } " J/K"} {}. There is about a 1 in 10301 in 1030 size 12{1" in ""10" rSup { size 8{"30"} } } {} chance of this change occurring. So while very small decreases in entropy are unlikely, slightly greater decreases are impossibly unlikely. These probabilities imply, again, that for a macroscopic system, a decrease in entropy is impossible. For example, for heat transfer to occur spontaneously from 1.00 kg of CC size 12{0ºC} {} ice to its CC size 12{0°C} {} environment, there would be a decrease in entropy of 1.22×103 J/K1.22×103 J/K size 12{1 "." "22" times "10" rSup { size 8{3} } " J/K"} {}. Given that a ΔS of 1021 J/KΔS of 1021 J/K size 12{DS" of 10" rSup { size 8{ +- "21"} } " J/K"} {} corresponds to about a 1 in 10301 in 1030 chance, a decrease of this size (103 J/K103 J/K size 12{"10" rSup { size 8{3} } " J/K"} {}) is an utter impossibility. Even for a milligram of melted ice to spontaneously refreeze is impossible.

Problem-Solving Strategies for Entropy

  1. Examine the situation to determine if entropy is involved.
  2. Identify the system of interest and draw a labeled diagram of the system showing energy flow.
  3. Identify exactly what needs to be determined in the problem (identify the unknowns). A written list is useful.
  4. Make a list of what is given or can be inferred from the problem as stated (identify the knowns). You must carefully identify the heat transfer, if any, and the temperature at which the process takes place. It is also important to identify the initial and final states.
  5. Solve the appropriate equation for the quantity to be determined (the unknown). Note that the change in entropy can be determined between any states by calculating it for a reversible process.
  6. Substitute the known value along with their units into the appropriate equation, and obtain numerical solutions complete with units.
  7. To see if it is reasonable: Does it make sense? For example, total entropy should increase for any real process or be constant for a reversible process. Disordered states should be more probable and have greater entropy than ordered states.
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