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26491797 457454 Physical Chemistry Quantum Chemistry[1]

26491797 457454 Physical Chemistry Quantum Chemistry[1]

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Sections

  • Basic Quantum Mechanics
  • 1.1. The “Fall” of Classical Physics
  • 1.2. Bohr’s Atomic Theory
  • 2.2. How to normalize a wavefunction
  • 2.3. Postulates II and II
  • 3.1. The Hamiltonian
  • 3.3. The Average Value Theorem
  • 3.4. The Heisenberg Uncertainty Principle
  • 4.1. The 1D Particle in a Box Problem
  • 5.2. Spectroscopy (An Introduction)
  • Quantum Mechanics of Atoms and Molecules
  • 6. Hydrogenic Systems
  • 6.1. Hydrogenic systems
  • 6.2. Discussion of the Wavefunctions
  • 6.3. Spin of the electron
  • 6.4. Summary: the Complete Hydrogenic Wavefunction
  • 7. Multi-electron atoms
  • 7.1. Two Electron Atoms: Helium
  • 7.2. The Pauli Exclusion Principle
  • 7.3. Many Electron Atoms
  • 7.3.1. The Total Hamiltonian
  • 8. Diatomic Molecules and the Born Oppenheimer Approximation
  • 8.1. Molecular Energy
  • 8.1.1. The Hamiltonian
  • 8.1.2. The Born—Oppenheimer Approximation
  • 8.2. Molecular Vibrations
  • 8.2.1. The Morse Oscillator
  • 8.2.2. Vibrational Spectroscopy
  • 9. Molecular Orbital Theory and Symmetry
  • 9.1. Molecular Orbital Theory
  • 9.2. Symmetry
  • 10. Molecular Orbital Diagrams
  • 10.1. LCAO–Linear Combinations of Atomic Orbitals
  • 10.1.1. Classification of Molecular Orbitals
  • 10.2. The Hydrogen Molecule
  • 10.3. Molecular Orbital Diagrams
  • 10.4. The Complete Molecular Hamiltonian and Wavefunc- tion
  • 11. An Aside: Light Scattering–Why the Sky is Blue
  • 11.2. The Blue Sky
  • 11.2.1. Sunsets
  • 11.2.2. White Clouds
  • 12. Rudiments of Statistical Mechanics
  • 12.1. Statistics and Entropy
  • 12.1.1. Combinations and Permutations
  • 12.2. Fluctuations
  • 13. The Boltzmann Distribution
  • 13.1. Partition Functions
  • 13.1.1. Relation between the Q and W
  • 13.2. The Molecular Partition Function
  • 14. Statistical Thermodynamics
  • 15.1. Properties of Partial Derivatives
  • 15.1.1. Summary of Relations
  • 15.2. Definitions
  • 15.2.1. Types of Systems
  • 15.2.2. System Parameters
  • 15.3. Work and Heat
  • 15.3.1. Generalized Forces and Displacements
  • 15.3.2. PV work
  • 16. Maximum Work and Reversible changes
  • 16.2. Heat Capacity
  • 16.3. Equations of State
  • 16.3.1. Example 1: The Ideal Gas Law
  • 16.3.2. Example 2: The van der Waals Equation of State
  • 16.3.3. Other Equations of State
  • 17. The Zeroth and First Laws of Thermodynamics
  • 17.1. Temperature and the Zeroth Law of Thermodynamics
  • 17.2. The First Law of Thermodynamics
  • 17.2.1. The internal energy state function
  • 18. The Second and Third Laws of Thermodynamics
  • 18.1. Entropy and the Second Law of Thermodynamics
  • 18.1.1. Statements of the Second Law
  • 18.2. The Third Law of Thermodynamics
  • 18.2.1. The Third Law
  • 18.2.2. Debye’s Law
  • 18.3. Times Arrow
  • Basics of Thermodynamics
  • 19. Auxillary Functions and Maxwell Relations
  • 19.1. The Other Important State Functions of Thermody- namics
  • 19.2. Enthalpy
  • 19.2.1. Heuristic definition:
  • 19.3. Helmholtz Free Energy
  • 19.3.1. Heuristic definition:
  • 19.4. Gibbs Free Energy
  • 19.4.1. Heuristic definition:
  • 19.5. Heat Capacity of Gases
  • 19.5.1. The Relationship Between CP and CV
  • 19.6. The Maxwell Relations
  • 20. Chemical Potential
  • 20.1. Spontaneity of processes
  • 20.2. Chemical potential
  • 20.3. Activity and the Activity coefficient
  • 20.3.1. Reference States
  • 20.3.2. Activity and the Chemical Potential
  • 21. Equilibrium
  • 21.0.3. Equilibrium constants in terms of KC
  • 21.0.4. The Partition Coefficient
  • 22. Chemical Reactions
  • 22.1. Heats of Reactions
  • 22.1.1. Heats of Formation
  • 22.1.2. Temperature dependence of the heat of reaction
  • 22.2. Reversible reactions
  • 22.3. Temperature Dependence of Ka
  • 22.4. Extent of Reaction
  • 23. Ionics
  • 23.1. Ionic Activities
  • 23.1.1. Ionic activity coefficients
  • 23.2. Theory of Electrolytic Solutions
  • 23.3. Ion Mobility
  • 23.3.1. Ion mobility
  • 24. Thermodynamics of Solvation
  • 24.1. The Born Model
  • 24.1.1. Free Energy of Solvation for the Born Model
  • 24.1.2. Ion Transfer Between Phases
  • 24.1.3. Enthalpy and Entropy of Solvation
  • 24.2. Corrections to the Born Model
  • 25. Key Equations for Exam 4
  • Quantum Mechanics and Dynamics
  • 26. Particle in a 3D Box
  • 26.1. Particle in a Box
  • 26.2. The 3D Particle in a Box Problem
  • 27. Operators
  • 27.1. Operator Algebra
  • 27.2. Orthogonality, Completeness, and the Superposition Principle
  • 28. Angular Momentum
  • 28.1. Classical Theory of Angular Momentum
  • 28.2. Quantum theory of Angular Momentum
  • 28.3. Particle on a Ring
  • 28.4. General Theory of Angular Momentum
  • 28.5. Quantum Properties of Angular Momentum
  • 28.5.1. The rigid rotor
  • 29.1. Spin Angular Momentum
  • 29.2. Addition of Angular Momentum
  • 29.2.1. The Addition of Angular Momentum: General Theory
  • 29.2.2. An Example: Two Electrons
  • 29.2.3. Term Symbols
  • 29.2.4. Spin Orbit Coupling
  • 30.1. Perturbation Theory
  • 30.2. Variational method
  • 31. The Two Level System and Quantum Dynamics
  • 31.1. The Two Level System
  • 31.2. Quantum Dynamics
  • Symmetry and Spectroscopy
  • 32.1. Symmetry Operators
  • 32.2. Mathematical Groups
  • 32.2.1. Example: The C2v Group
  • 32.3. Symmetry of Functions
  • 32.3.1. Direct Products
  • 32.4. Symmetry Breaking and Crystal Field Splitting
  • 33.1. Molecular Vibrations
  • 33.1.1. Normal Modes
  • 33.1.2. Normal Modes and Group Theory
  • 34. Vibrational Spectroscopy and Group Theory
  • 34.1. IR Spectroscopy
  • 34.2. Raman Spectroscopy
  • 35.1. Relaxing the rigid rotor
  • 35.2. Rotational Spectroscopy
  • 35.3. Rotation of Polyatomic Molecules
  • 36. Electronic Spectroscopy of Molecules
  • 36.1. The Structure of the Electronic State
  • 36.1.1. Absorption Spectra
  • 36.1.2. Emission Spectra
  • 36.1.3. Fluorescence Spectra
  • 36.2. Franck—Condon activity
  • 36.2.1. The Franck—Condon principle
  • 37.1. The Fourier transformation
  • Kinetics and Gases
  • 38.1. kinetic theory of gases
  • 38.2. Molecular Collisions
  • 39. The Rate Laws of Chemical Kinetics
  • 39.1. Rate Laws
  • 39.2. Determination of Rate Laws
  • 39.2.1. Differential methods based on the rate law
  • 39.2.2. Integrated rate laws
  • 40. Temperature and Chemical Kinetics
  • 40.1. Temperature Effects on Rate Constants
  • 40.1.1. Temperature corrections to the Arrhenious parameters
  • 40.2. Theory of Reaction Rates
  • 40.3. Multistep Reactions
  • 40.4. Chain Reactions
  • 41. Gases and the Virial Series
  • 41.1. Equations of State
  • 41.2. The Virial Series
  • 41.2.1. Relation to the van der Waals Equation of State
  • 41.2.2. The Boyle Temperature
  • 41.2.3. The Virial Series in Pressure
  • 41.2.4. Estimation of Virial Coefficients
  • 42. Behavior of Gases
  • 42.1. P,V and T behavior
  • 42.1.1. α and κT for an ideal gas
  • 42.1.2. α and κT for liquids and solids
  • 42.2. Heat Capacity of Gases Revisited
  • 42.2.1. The Relationship Between CP and CV
  • 42.3. Expansion of Gases
  • 42.3.1. Isothermal and Adiabatic expansions
  • 42.3.2. Heat capacity CV for adiabatic expansions
  • 42.3.3. When P is the more convenient variable
  • 42.3.4. Joule expansion
  • 42.3.5. Joule-Thomson expansion
  • 43. Entropy of Gases
  • 43.1. Calculation of Entropy
  • 43.1.1. Entropy of Real Gases
  • 44. Critical Phenomena
  • 44.1. Critical Behavior of fluids
  • 44.1.1. Gas Laws in the Critical Region
  • 44.1.2. Gas Constants from Critical Data
  • 44.2. The Law of Corresponding States
  • 44.3. Phase Equilibrium
  • 44.3.1. The chemical potential and T and P
  • 44.3.2. The Clapeyron Equation
  • 44.3.3. Vapor Equilibrium and the Clausius-Clapeyron Equation
  • 44.4. Equilibria of condensed phases
  • 44.5. Triple Point and Phase Diagrams
  • 45. Transport Properties of Fluids
  • 45.2. Viscosity
  • 45.3. Thermal conductivity
  • 45.3.1. Thermal Conductivity of Gases and Liquids
  • 45.3.2. Thermal Conductivity of Solids
  • 46. Solutions
  • 46.1. Measures of Composition
  • L solution
  • 46.2. Partial Molar Quantities
  • 46.2.1. Notation
  • 46.2.2. Partial Molar Volumes
  • 46.3. Reference states for liquids
  • 46.3.1. Activity (a brief review)
  • 46.3.2. Raoult’s Law
  • 46.3.3. Ideal Solutions (RL)
  • 46.3.4. Henry’s Law

Chemistry 351 and 352 Physical Chemistry I and II

Darin J. Ulness Fall 2006 – 2007

Contents
I Basic Quantum Mechanics 15
16 16 17 17 22 22 23 24 27 27 27 29 30 31 31 34 38 40

1 Quantum Theory 1.1 The “Fall” of Classical Physics . . . . . . . . . . . . . . . . . . . . 1.2 Bohr’s Atomic Theory . . . . . . . . . . . . . . . . . . . . . . . . 1.2.1 First Attempts at the Structure of the Atom . . . . . . . . 2 The Postulates of Quantum Mechanics 2.1 Postulate I . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2 How to normalize a wavefunction . . . . . . . . . . . . . . . . . . 2.3 Postulates II and II . . . . . . . . . . . . . . . . . . . . . . . . . . 3 The 3.1 3.2 3.3 3.4 Setup of a Quantum Mechanical Problem The Hamiltonian . . . . . . . . . . . . . . . . . The Quantum Mechanical Problem . . . . . . . The Average Value Theorem . . . . . . . . . . . The Heisenberg Uncertainty Principle . . . . . .

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4 Particle in a Box 4.1 The 1D Particle in a Box Problem . . . . . . . . . . . . . . . . . . 4.2 Implications of the Particle in a Box problem . . . . . . . . . . . 5 The Harmonic Oscillator 5.1 Interesting Aspects of the Quantum Harmonic Oscillator . . . . . i

5.2 Spectroscopy (An Introduction) . . . . . . . . . . . . . . . . . . .

42

II

Quantum Mechanics of Atoms and Molecules

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6 Hydrogenic Systems 6.1 Hydrogenic systems . . . . . . . . . . . . . . . . . . 6.2 Discussion of the Wavefunctions . . . . . . . . . . . 6.3 Spin of the electron . . . . . . . . . . . . . . . . . . 6.4 Summary: the Complete Hydrogenic Wavefunction 7 Multi-electron atoms 7.1 Two Electron Atoms: Helium 7.2 The Pauli Exclusion Principle 7.3 Many Electron Atoms . . . . 7.3.1 The Total Hamiltonian

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8 Diatomic Molecules and the Born Oppenheimer Approximation 8.1 Molecular Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.1.1 The Hamiltonian . . . . . . . . . . . . . . . . . . . . . . . 8.1.2 The Born—Oppenheimer Approximation . . . . . . . . . . 8.2 Molecular Vibrations . . . . . . . . . . . . . . . . . . . . . . . . . 8.2.1 The Morse Oscillator . . . . . . . . . . . . . . . . . . . . . 8.2.2 Vibrational Spectroscopy . . . . . . . . . . . . . . . . . . . 9 Molecular Orbital Theory and Symmetry 9.1 Molecular Orbital Theory . . . . . . . . . . . . . . . . . . . . . . 9.2 Symmetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 Molecular Orbital Diagrams 10.1 LCAO–Linear Combinations of Atomic Orbitals . . . . . . . . . 10.1.1 Classification of Molecular Orbitals . . . . . . . . . . . . .

10.2 The Hydrogen Molecule . . . . . . . . . . . . . . . . . . . . . . . 10.3 Molecular Orbital Diagrams . . . . . . . . . . . . . . . . . . . . . 10.4 The Complete Molecular Hamiltonian and Wavefunction . . . . . 11 An Aside: Light Scattering–Why the Sky is Blue 11.1 The Classical Electrodynamics Treatment of Light Scattering 11.2 The Blue Sky . . . . . . . . . . . . . . . . . . . . . . . . . . 11.2.1 Sunsets . . . . . . . . . . . . . . . . . . . . . . . . . 11.2.2 White Clouds . . . . . . . . . . . . . . . . . . . . . .

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III Statistical Mechanics and The Laws of Thermodynamics 88
12 Rudiments of Statistical Mechanics 12.1 Statistics and Entropy . . . . . . . . . . . . . . . . . . . . . . . . 12.1.1 Combinations and Permutations . . . . . . . . . . . . . . . 12.2 Fluctuations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 The Boltzmann Distribution 13.1 Partition Functions . . . . . . . . . . . . . . . . . . . . . . . . . . 13.1.1 Relation between the Q and W . . . . . . . . . . . . . . . 13.2 The Molecular Partition Function . . . . . . . . . . . . . . . . . . 14 Statistical Thermodynamics 15 Work 15.1 Properties of Partial Derivatives 15.1.1 Summary of Relations . 15.2 Definitions . . . . . . . . . . . . 15.2.1 Types of Systems . . . . 15.2.2 System Parameters . . . 89 89 90 92 94 96 97 99 103 107 107 107 108 108 109

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15.3 Work and Heat . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109 15.3.1 Generalized Forces and Displacements . . . . . . . . . . . 110 15.3.2 P V work . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 16 Maximum Work and Reversible changes 16.1 Maximal Work: Reversible versus Irreversible changes . . 16.2 Heat Capacity . . . . . . . . . . . . . . . . . . . . . . . . 16.3 Equations of State . . . . . . . . . . . . . . . . . . . . . 16.3.1 Example 1: The Ideal Gas Law . . . . . . . . . . 16.3.2 Example 2: The van der Waals Equation of State 16.3.3 Other Equations of State . . . . . . . . . . . . . . 113 113 115 116 116 117 118

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17 The Zeroth and First Laws of Thermodynamics 119 17.1 Temperature and the Zeroth Law of Thermodynamics . . . . . . . 119 17.2 The First Law of Thermodynamics . . . . . . . . . . . . . . . . . 121 17.2.1 The internal energy state function . . . . . . . . . . . . . . 121 18 The Second and Third Laws of Thermodynamics 18.1 Entropy and the Second Law of Thermodynamics . 18.1.1 Statements of the Second Law . . . . . . . . 18.2 The Third Law of Thermodynamics . . . . . . . . . 18.2.1 The Third Law . . . . . . . . . . . . . . . . 18.2.2 Debye’s Law . . . . . . . . . . . . . . . . . . 18.3 Times Arrow . . . . . . . . . . . . . . . . . . . . . 124 124 127 127 128 129 130

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IV

Basics of Thermodynamics

134

19 Auxillary Functions and Maxwell Relations 135 19.1 The Other Important State Functions of Thermodynamics . . . . 135 19.2 Enthalpy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136 19.2.1 Heuristic definition: . . . . . . . . . . . . . . . . . . . . . . 137

19.3 Helmholtz Free Energy . . . . . . . . . . . . 19.3.1 Heuristic definition: . . . . . . . . . . 19.4 Gibbs Free Energy . . . . . . . . . . . . . . 19.4.1 Heuristic definition: . . . . . . . . . . 19.5 Heat Capacity of Gases . . . . . . . . . . . . 19.5.1 The Relationship Between CP and CV 19.6 The Maxwell Relations . . . . . . . . . . . . 20 Chemical Potential 20.1 Spontaneity of processes . . . . . . . . . . . 20.2 Chemical potential . . . . . . . . . . . . . . 20.3 Activity and the Activity coefficient . . . . . 20.3.1 Reference States . . . . . . . . . . . 20.3.2 Activity and the Chemical Potential

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21 Equilibrium 151 21.0.3 Equilibrium constants in terms of KC . . . . . . . . . . . . 153 21.0.4 The Partition Coefficient . . . . . . . . . . . . . . . . . . . 153 22 Chemical Reactions 22.1 Heats of Reactions . . . . . . . 22.1.1 Heats of Formation . . . 22.1.2 Temperature dependence 22.2 Reversible reactions . . . . . . . 22.3 Temperature Dependence of Ka 22.4 Extent of Reaction . . . . . . . 156 156 157 157 158 159 160

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23 Ionics 161 23.1 Ionic Activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161 23.1.1 Ionic activity coefficients . . . . . . . . . . . . . . . . . . . 162 23.2 Theory of Electrolytic Solutions . . . . . . . . . . . . . . . . . . . 163

23.3 Ion Mobility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164 23.3.1 Ion mobility . . . . . . . . . . . . . . . . . . . . . . . . . . 165 24 Thermodynamics of Solvation 24.1 The Born Model . . . . . . . . . . . . . . . 24.1.1 Free Energy of Solvation for the Born 24.1.2 Ion Transfer Between Phases . . . . . 24.1.3 Enthalpy and Entropy of Solvation . 24.2 Corrections to the Born Model . . . . . . . . 25 Key Equations for Exam 4 169 170 173 174 174 175 177

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V

Quantum Mechanics and Dynamics

180

26 Particle in a 3D Box 181 26.1 Particle in a Box . . . . . . . . . . . . . . . . . . . . . . . . . . . 181 26.2 The 3D Particle in a Box Problem . . . . . . . . . . . . . . . . . . 183 27 Operators 187 27.1 Operator Algebra . . . . . . . . . . . . . . . . . . . . . . . . . . . 187 27.2 Orthogonality, Completeness, and the Superposition Principle . . 191 28 Angular Momentum 28.1 Classical Theory of Angular Momentum . . 28.2 Quantum theory of Angular Momentum . . 28.3 Particle on a Ring . . . . . . . . . . . . . . . 28.4 General Theory of Angular Momentum . . . 28.5 Quantum Properties of Angular Momentum 28.5.1 The rigid rotor . . . . . . . . . . . . 192 192 193 194 195 199 200

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. . . Theory . . . . . . . .1 The Two Level System . . . . . . . . . . . . . . . . .2 An Example: Two Electrons . . . . . . . .2 Normal Modes and Group Theory . . . . . . . . . . . . . . . . . .1 Example: The C2v Group . . . . . . . . . . . . . . . . .4 Spin Orbit Coupling . . . . . .2. . . . . . . . . . . . . . . . . . . . . .3 Term Symbols . . . . 32. . . . . . . 228 33. . . . .2 Addition of Angular Momentum . . . . . 209 31 The Two Level System and Quantum Dynamics 211 31. . . . . . . . .3 Symmetry of Functions . . . . . . . . . 207 30. 201 201 202 202 203 204 205 30 Approximation Techniques 207 30. . . 29. . . . . . . .1. .2. . . . . . 29. . . . . . . . 32. . . . . . . . . . . .4 Symmetry Breaking and Crystal Field Splitting . . . . .1 Normal Modes . . . . . . . . . . . 229 . . . . . . . . . . . . . .2. . . . . . . . . . . . .2 Quantum Dynamics . . . . . . . . . . . . . . . . . . 32. . . . . . 214 VI Symmetry and Spectroscopy 220 221 222 222 223 223 225 225 32 Symmetry and Group Theory 32. . . . . . . . . . 32. .1 Spin Angular Momentum . . . .29 Addition of Angular Momentum 29. . . . . . . . . . . . . . . . 32. . 29. . . . . . . . . . . . . 33 Molecules and Symmetry 228 33. . . . . . . . . .2 Variational method . . . . . . . . . . . . . .1 The Addition of Angular Momentum: 29. . . . . .1 Direct Products . . . . . . . . . . . . .2. 29. . . .1 Symmetry Operators . . .2 Mathematical Groups . . General . . . . . .2. .1 Molecular Vibrations . . . . . . . . . . . . . . . 211 31. . . . . . . . . . . . . . . . 229 33. . . . . .1. . . . . . . .3. . . . . . . . . . . . . . . . . . . . . .1 Perturbation Theory . . . . .

. . . . . . . .1 The Structure of the Electronic State 36. . .2 Integrated rate laws . . . 252 39 The Rate Laws of Chemical Kinetics 39. . . . . .2 Raman Spectroscopy . . . . . . . . 36. . . . . . . . . . . . . . . . 254 254 258 259 259 . . . . . . .1 The Fourier transformation . . . . . . . . . . . . . . . . .2. . . . . . .2. . . . . . . . . . . . . 231 34. . . . . . . . . .1 Differential methods based on the rate law 39. . . . . .1 The Franck—Condon principle 235 236 236 237 240 240 241 241 242 243 243 . . . . . 233 35 Molecular Rotations 35. . . . . . . . . . . . . . . . . . . . . . . . . . 36. . . . . . . . . . . . . . . . . . . . . . . . . . .1. . . . . . . .1 IR Spectroscopy . . . . .2 Rotational Spectroscopy . . . . . . . . . . . . . 39. .2 Franck—Condon activity . . . . . . . . . . . 245 VII Kinetics and Gases 249 38 Physical Kinetics 250 38. . . . . . . . . . . . . . . . . . .1 Absorption Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1 kinetic theory of gases . . .2 Molecular Collisions . . . . . . . . . . . . . . 35.3 Rotation of Polyatomic Molecules . 37 Fourier Transforms 245 37.3 Fluorescence Spectra . . . 36 Electronic Spectroscopy of Molecules 36. . .1 Relaxing the rigid rotor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2 Emission Spectra . . . . . . . . . . . . . . . . 35. 39. .2. .1. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1. . . 36. . . . . . . . . . . .2 Determination of Rate Laws . . . 250 38. . . . . . . . . . . . . . . . 36. . . . . . .1 Rate Laws . . . . . . . . . . . . . . .34 Vibrational Spectroscopy and Group Theory 231 34. . .

42. . . . . . . . . . . . . . . . . .1 Entropy of Real Gases . . . . .1 Relation to the van der Waals Equation of State 41. . . . . . . . . 41. . . . . . . . . . .2 The Virial Series . . . . . . . . . . . . . . . 40. . . . . .2 The Boyle Temperature . . . . . .1 Equations of State . . . .4 Chain Reactions . . 40. .3. . . . . . . . . . . . . . . . . 41. . . . . . .3. . . . . . . . . . . . .1 P.2 α and κT for liquids and solids . . . . . . . 42. . . . . . .1. . . . . . . . . . . . . . . .2. . . . . . . . . . 288 . . . . . . . . . . .3. . . . . .4 Estimation of Virial Coefficients . . .3 When P is the more convenient variable . . .3 The Virial Series in Pressure . . . . . 42. 42. . . . . . . . . .2 Heat capacity CV for adiabatic expansions 42. . . . .1 Temperature Effects on Rate Constants . . . . . . . . . . . . 40. 41. . . . . . . . 42. . . .3. . . . . . . . . .1 Temperature corrections to the Arrhenious 40. .1 Isothermal and Adiabatic expansions . . . . . . .2 Theory of Reaction Rates . . . . . . . . . . . . . . . . . . . parameters . V and T behavior . . .2 Heat Capacity of Gases Revisited . . . . . . . . . . . . . . . . . . . .1 The Relationship Between CP and CV . . . . . . 286 43. 42. . . . . . . . . . . . . .4 Joule expansion . . . . . . . . . . . . . . . . . . .1 α and κT for an ideal gas . .1. . .1 Calculation of Entropy . . . . . . . . . . . . . . . . 42. .5 Joule-Thomson expansion . 42 Behavior of Gases 42. . . . . . . . . . . . . 261 261 262 262 265 267 269 269 270 271 272 272 273 274 274 275 275 276 276 279 279 280 281 282 283 41 Gases and the Virial Series 41. . . .3 Expansion of Gases . . . .2. . .40 Temperature and Chemical Kinetics 40. . . . .2. . . . . . . . . . . . .3 Multistep Reactions . . . . . . .2. .3. . . . . . . . . . . . . . .1. . . . . . . . . . . . .2. . . . . . . . . . . . . . . . . . . . . . 41. 42. . . . . .1. . . . . . . . . . . 42. . . . 43 Entropy of Gases 286 43.

. . .3. . . . . . . . . . . . . . . . . .1. . . . . . . . . . 44. . . . . . . Liquids . . . . . . . . 46. .2. . . .4 Henry’s Law . . . . . . . . . . . . . . . . . . . . . . 45. . . . 46. . . . . . .3. .1 Notation . . . . 44. . . .VIII More Thermodyanmics 292 293 293 294 295 296 296 297 298 298 299 300 301 301 303 305 306 307 308 308 308 309 310 311 311 312 314 316 44 Critical Phenomena 44. . . . . . . . . 44. . . .5 Triple Point and Phase Diagrams . . . . . .1 Thermal Conductivity of 45. . Gases and Solids . .1 Measures of Composition . . . . . . . . 45. . . . . . . . . . . . . . 44. . . . . . . . . .3. . . . . . . . . .3 Vapor Equilibrium and the Clausius-Clapeyron Equation 44.3. . . . .3 Ideal Solutions (RL) . . . .2 The Clapeyron Equation . . . . . . .2 Partial Molar Quantities . . . . . . . . . 44. . . . . . . . . . . . . . . . . . . . 46. . . . . . . . . . . . . . . . . . . . . . . . .3. . . . . . . . . . . . . . . . . . . .3. . . .2 Thermal Conductivity of 46 Solutions 46. . . . . . . . . . . . . . .1 Diffusion . . . . . . . . . . .3 Phase Equilibrium . . . . . .2 Gas Constants from Critical Data . .2 Viscosity . . .1 Gas Laws in the Critical Region . .2 Raoult’s Law . . . . . . .3 Reference states for liquids . . .2. . . . . . . . . . . .4 Equilibria of condensed phases . . .1. . . 44. . . . . . . . . .2 Partial Molar Volumes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46. . . . . . .3. . . . . . . . . . . . 45. . . . . 45 Transport Properties of Fluids 45. . . . . . . . . . . . 44. . . . . . . . 44. . . . . . .2 The Law of Corresponding States . . . . . . 46. .3. . . . . . . . . . .3. . . . . . .1 Activity (a brief review) 46. . . 46.3 Thermal conductivity . . . . . . . . . . . . . . . . . . . 46. . . . . . .1 Critical Behavior of fluids . .1 The chemical potential and T and P . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

. . .2 Osmotic Pressure . . . . . . . . . 322 322 324 325 326 328 330 331 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2 The Second Law . . 47. . .5 Echo Phenonmena . 47. . . . . . .1 Fundamentals . . . . . . . . . . 47. . . . . 319 47 Entropy Production and Irreverisble Thermodynamics 47. . . . . . . . . . . . .4 Thermodynamic Coupling . . . . . . . . 318 46. . . . .4. .4. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3 Examples . . . 47. . 47. . . .3. . . . . . 47. . . . . . . . . . . . . . . . . . . . .4 Colligative Properties . .46. . . . .3. . . . . . . . . . . . . . . . . .2 Entropy Production due to Chemical Reactions . .1 Freezing Point Depression . . . . . . . .1 Entropy Production due to Heat Flow . . . . . . . 318 46. . . . . . .

Chemistry 351: Physical Chemistry I 1 1 .

Tips for solving problems Working problem sets is the heart and sole of learning physical chemistry.Solved Problems I make-up most of the problems on the problems sets. Simply skip those examples as you scan through this chapter. so it might be helpful to you to see some of these problems worked out. Consequently early in the course some of the examples might seem very itimidating. The only way that you can be sure that you understand a concept at to be able to solve the problems associated with it. you can still learn a lot be working these and looking that their solutions in the solution manual. Tips 2 2 . Keep in mind this chapter provides some examples of how to solve problems for both physical chemistry I and physical chemistry II. This takes time and hard work. Even though there aren’t many “book” problems assigned during the year. But there are some things that you can do to help yourself with these problems.

This will make the problem sets much more efficient at helping you learn. 5. 2.. You can do the problem. • Just identify the general ideas that you think you might need. so if you solve them you will not become famous nor will you save the world. 3. If you think you can’t do the problem then maybe you need try a different way of thinking about it. • Determine wether you need to approach the problem mathematically or conceptually or both. There is a tendency to try to start solving the problem before fully understanding the question. • Do not worry about not knowing how to solve it yet. Part of the trouble is simply understanding what the problem is asking you to do. • If the question is long.1.. • Read the question carefully • Try to think about what topic(s) in lecture and in the notes the problem is dealing with. Remember nobody cares if you solve any particular problem on the problem set. Try to figure out what mathematical techniques you need to express the solution to the problem. • Do not be afraid. try to identify subsections of it. 4. For problems that require a mathematical approach. I don’t assign problems that you cannot do. 3 . Try to whip-off a few on the same day that you get the problem set. The only reason you work them is to learn. Then work on them consistently during the week. They have all been solved before. Budget your time so that you don’t have to work on an overwhelming number of problems at a time.

• Always check to see if the math makes sense when you are done. sin 2x. The second function we should remember from trig as having a period of 2π. start with a related concept that is better known by you. Problems Dealing With Quantum Mechanics Problem: What is the periodicity of the following functions • f (x) = sin2 x • f (x) = cos x • f(x) = e−2ix Solution: For the first function it is easiest to see the periodicity by writing the function as f (x) = (sin x)(sin x). 6. • Make sure that the physical idea that you are using in your argument is correct. For problems that require a conceptual approach. 4 . so the periodicity is π. . ±1.. has a period of π as does the imaginary part. n = 0. either you will be able to do this or you won’t. If you are not sure..• Do the math. We know that this function will repeat zeros when ever sin x = 0. It might take some review on your part. Does you final answer jive with what you know. . • Look for self-consistency. This occurs at x = nπ. Finally for the last function it is best to used Euler’s identity and write e−2ix = cos 2x + i sin 2x (1) The real part of this function. cos 2x. Therefore the entire function has a period of π.. ±2 .

multiply by −i~ and check to see if the eigenvalue equation holds. For the case of momentum all we need to do is take the derivative of each function. no. If ˆ this equation is true then the function is an eigenfunction with eigenvalue λ. ˆ • ψ(x) = eikx • ψ(x) = e−αx 2 • ψ(x) = cos kx Solution: We need to determine if px ψ(x) = λψ(x) where λ is a constant. px ψ(x) = −i~ ˆ dx dx 6=cos kx (4) so. this function is not an eigenfunction of the momentum operator. For the second function px ψ(x) = −i~ ˆ de−αx dψ(x) ↓ 2 = −i~ = 2i~αxe−αx = 2i~αxψ(x). px = −i~ dx . no. Problem: A quantum object is described by the wavefunction ψ(x) = e−αx . For the last function z }| { d cos kx dψ(x) = −i~ = −i~k sin kx. yes. dx dx (2) so.Problem: Which of the following functions are eigenfunction of the momentum d operator. For the first function px ψ(x) = −i~ ˆ deikx dψ(x) = −i~ = ~keikx = ~kψ(x). this function is not and eigenfunction of the momentum operator. this function is an eigenfunction of the momentum operator. dx dx 2 (3) so. What is the probability of finding the object further than α away from the origin ( x = 0)? 2 5 .

We are interested in finding the probability that the object is outside of the region −α < x < α. but we won’t. (6) e−2αx2 dx −∞ Mathematica can assist with these integrals to give the final answer of √ 3 P (|x| > α) = erfc[ 2α 2 ]. ψunnorm we know that this function must simply be some constant N multiplied by the normalized version of this function: ψ unnorm = Nψnorm We have shown generally that N is given by sZ N= |ψunnorm (x)|2 dx. (7) Solution: First of all we do not know if this wavefunction is normalized. We could normalize this wavefunction.The first integral in the numerator gives the probability that the object is at a position x < −α and the second integral in the numerator gives the probability for x > α. so we should assume that it isn’t. If you were working with a normalized wavefunction the denominator would be equal to 1 and hence not needed. The denominator accounts for the fact that the wavefunction is unnormalized. Normalize this wavefunction. space (8) (9) 6 . Solution: Following our general procedure from the notes if we have some unnormalized wavefunction. (5) |ψ(x)|2 dx −∞ Problem: A quantum object is described by the wavefunction ψ(x) = e−γx over the range 0 ≤ x < ∞. To do this using an unnormalized wavefunction we must evaluate R −α R∞ |ψ(x)|2 dx + α |ψ(x)|2 dx P (|x| > α) = −∞ R∞ . Plugging in the wavefunctions we have R −α −2αx2 R∞ 2 e dx + α e−2αx dx −∞ R∞ P (|x| > α) = . The limits of the integral in the denominator represent all space for the object.

2γ (13) So on average you will find the object at x = 1 . πa0 (15) 7 . 2γ Problem: What is the probability of finding an electron in the 1s state of hydrogen further than one Bohr radius away from the nucleus? Solution: We need to evaluate Z P (r > a0 ) = 2π 0 Z π 0 Z ∞ a0 |ψ1s |2 r2 sin θdrdθdφ. Generally and average is calculated as Z ψ∗ (x)ˆψ(x).Which for this case is N= sZ ∞ 0 |e−γx |2 dx = sZ ∞ e−2γx dx = 0 r 1 2γ (10) So finally we get the normalized wavefunction by rearanging ψunnorm = Nψnorm : p (11) ψnorm (x) = 2γe−γx . What is the average position of the object? Solution: We need to work with the normalized wavefunction that we found in √ the previous problem. ψ(x) = 2γe−γx . o (12) hˆi = o space which in this case is Z ∞p Z p −γx −γx hˆi = x 2γe x 2γe dx = 2γ 0 ∞ xe−2γx dx = 0 1 . Problem: A quantum object is described by the wavefunction ψ(x) = e−γx over the range 0 ≤ x < ∞. The normalized 1s wavefunction is 1 ψ1s = p 3 er/a0 . (14) Remember the extra r2 sin θ is needed when integrating in spherical polar coordinates.

We know that if the wavefunction is to be a product state then the Hamiltonian must be made up of a sum of independent terms. (17) + + 2m ∂x2 ∂y 2 ∂z 2 We see that indeed the Hamiltonian is a sum of term that depends only on x. To see this we write out the Laplacian to get µ ¶ −~2 ∂ 2 ∂2 ∂2 ˆ H= . a term depending only on y and a term that depends only on z. Verify that the coefficient for the linear term is zero. z) as a product state. (18) Problem: Expand the Morse potential in a Taylor’s series about Req .677. e2 (16) So.We can do this integral by hand or have Mathematica help us to give P (r > a0 ) = 5 = 0. What is the force constant associated with the Morse potential? Solution: The Morse potential is £ ¤ V (x) = De 1 − e−β(R−Req ) . Solution: This problem appears hard at first since we are not studying three dimensional systems. y. Problem: A free particle in three dimensions is described by the Hamiltonian. 2 ˆ H = −~ ∇2 . (19) 8 . Express the wavefunction (in Cartesian coordinates) as a product 2m state. z) = ψ(x)ψ(y)ψ(z). about 68% of the time the electron would be found at some distance greater then one Bohr radius from the proton. Ψ(x. y. but all it is asking is to express the wavefunction. which is a function of the three spatial dimensions. Therefore the appropriate product state is Ψ(x.

It is steeper on the “short” side of equilibrium and softer on the “long” side of equilibrium and this “softness” increases with increasing quantum number. How many molecules are in the first excited state of the ‘ring breathing’ mode (992 cm −1 )? How 9 . Hence no mater what the vibrational quantum number is there is just as much of the wavefunction on either side equilibrium thus hRi = Req for any quantum number. The Morse potential does not have this symmetry. (20) V (x) = V (x)|Req + dx ¯Req 2! dx2 ¯Req | {z } | {z } | {z } =0 =0 = β 2 De Problems Dealing With Statistical Mechanics and Thermodynamics Problem: A vial containing 10 20 benzene molecules is at 300K. The potential for the harmonic oscillator is described by a parabola centered about the equilibrium bond length. The force constant is given by the coefficient of the quadratic term so in this case k = β 2 De . yes the coefficient of the linear term (the term involving (R − Req ) to the first power) is zero. This will always be true when you perform a Taylor series expansion about a minimum (or maximum). Therefore without performing any calculations we can at least say that hRi increases as the quantum number increases. Problem: Without performing any calculations. The Taylor series about Req for this function is ¯ ¯ 2 ¯ dV (x) ¯ ¯ (R − Req ) + 1 d V (x) ¯ (R − Req )2 + · · · .So. compare hRi as a function of the vibrational quantum number for a diatomic modelled as a harmonic oscillator versus a Morse oscillator. Solution: This problem requires the we think qualitatively about the wavefunctions and the potentials for the harmonic oscillator and the Morse oscillator.

Each of the atoms can be in one of three states A.41 × 1017 Nv=1 = 2 sinh (21) 2 × 208 and C—H Nv=1 We see that about 8. Problem: Consider a linear chain of N atoms. For example. B or C. where for this example ⎤ 1 1 0 ⎥ ⎢ M = ⎣ 1 1 1 ⎦.··· . Find the entropy per atom for this system as N → ∞.41×10 × 100% = 0. V = ⎣ 7 ⎦. 1 2 5 The V (j+1) can be found from the V (j) vector using the matrix equation.02 × 1013 . B or C. except that an atom in state A can not be adjacent to an atom in state C. So. ¶ ³ µ ´ 3×992 992 rb × e− 2×208 × 1020 = 8. To solve this problem it is useful to define the set of three dimensional column vectors V (j) such that the three elements are the total number of allowed configurations of a j-atom chain having the j th atom in state A. V (j+1) = MV (j) . ⎡ ⎤ ⎡ ⎤ ⎡ ⎤ 1 2 5 ⎢ ⎥ ⎢ ⎥ ⎢ ⎥ (1) (2) (3) (23) V = ⎣ 1 ⎦. V = ⎣ 3 ⎦.0000402% of the benzene molecules are in the first excited state for the C—H stretching mode.many are in the first excited state of the symmetric C—H vibrational mode (3063 cm −1 )? Solution: This is a problem that deals with the Boltzmann distribution. 0 1 1 ⎡ (24) ¶ ³ µ ´ 3063 − 3×3063 2×208 × 1020 = 4.841% of the benzene molecules are in the 1020 13 first vibrational excited state for the ring breathing mode and 4. × e = 2 sinh 2 × 208 17 (22) (25) 10 .02×10 × 100% = 1020 0.

1. For part (b) we need to list all states for the case of N = 3 and verify the we get the same result as calculated using the transfer matrix. Now for large N. Remembering that V (3) gives us the number of sequences that end in a given state we should organize our list in the same manner States ending in A States ending in B AAA ABA BAA BBA CBA AAB ABB BAB BBB BCB CBB CCB √ 7 states States ending in C ABC BBC BCC CBC Solution: For part (a) we simply problem (we are given V (3) ): ⎡ 1 1 ⎢ (4) V =⎣ 1 1 0 1 use the transfer matrix as directed in the ⎤ ⎤⎡ ⎤ ⎡ 12 5 0 ⎥ ⎥⎢ ⎥ ⎢ 1 ⎦ ⎣ 7 ⎦ = ⎣ 17 ⎦ . Use Boltzmann’s equation to find the entropy per atom for this chain as N goes to infinity. max N→∞ (26) 1. 3. 12 5 1 .The matrix M is the so-called transfer matrix for this system. Use M to find V (4) 2. Tr[M N ] ≈ λN . Verify W = Tr[M N ] for N = 1 and N = 2. 5 states √ 5 states √ 11 . So W = lim λN . max where λmax is the largest eigenvalue of M. It can be shown that the number of configurations W = Tr[M N ]. Verify V (3) explicitly by drawing all the allowed 3-atom configurations. 4.

one at 20000cm−1 − 992cm−1 = 19008cm−1 and one at 20000cm−1 − 3063cm−1 = 16937cm−1 . in this case. Therefore the limiting entropy per atom is ³ √ ´ S = k ln 1 + 2 . one at 20000cm−1 + 992cm−1 = 20992cm−1 and one at 20000cm−1 + 3063cm−1 = 23063cm−1 .States like AAC are not allowed because A and C are neighbors. Likewise we expect two anti-Stokes lines. BB. Assume benzene has only two active modes (992cm −1 and 3063cm −1 ) and assume the Laser light used to do the scattering is at 20000cm −1 (this is 500nm–green light). AB. Using √ Mathematica we find λmax = 1 + 2. For N = 2. ⎤⎤ ⎡⎡ ⎤⎤ ⎤⎡ ⎡⎡ 2 2 1 1 1 0 1 1 0 ⎥⎥ ⎢⎢ ⎥⎥ ⎥⎢ ⎢⎢ W = Tr[M 2 ] = Tr ⎣⎣ 1 1 1 ⎦ ⎣ 1 1 1 ⎦⎦ = Tr ⎣⎣ 2 3 2 ⎦⎦ = 7 (27) 0 1 1 0 1 1 1 2 2 This corresponds to the seven distinguishable microstates AA. is 20000cm−1 . we simply need to find the maximum eigenvalue of the Transfer matrix. Solution: Since there are two vibrational modes we expect two Stokes lines to the red of 20000cm−1 . CB and CC (Remember C and A cannot be neighbors). There is only one Rayleigh line and it is at the same frequency at the input laser beam which. For part (c) we evaluate W = Tr[M N ] for N = 1 and 2. 12 . calculate the positions of the Rayleigh. BC. W = Tr[M] = 3 This corresponds to the three distinguishable microstates A. For part (d) we use S k k k = ln W = lim ln λN = lim N ln λmax = k ln λmax . (29) N Problem: Using the classical theory of light scattering. max N→∞ N N→∞ N N N (28) So. Stokes and anti-Stokes spectral lines for benzene. BA. B. and C. For N = 1.

V ). (35) dU = ∂T V ∂V T 13 .Problem: A simple model for a crystal is a “gas” of harmonic oscillators. Determine A. Writing out the total derivative of U(T. Solution: The equation representing a Berthelot gas is P = nRT n2 a − . A = −kT ln Qcrystal = +NKT ln 2 sinh 2 (31) where we used properties of logs to pull the N out front and move the sinh term from to the numerator. S. Ã ! 1 N Qcrystal = qHO = (30) 2 sinh β~ω 2 From our formulas for statistical thermodynamics ¶ µ β~ω . V ) we get ¶ ¶ µ µ ∂U ∂U dT + dV. Solution: For this model the crystal is modelled as a collection of harmonic oscillators so we need the partition function for the harmonic oscillator. S = −kβ ∂Qcrystal + k ln Qcrystal ∂β µ ¶ β~ω β~ω Nkβ~ω coth − k ln 2 sinh = 2 2 2 U =− (32) and N~ω β~ω ∂Qcrystal = coth . and U from the partition function for this model. V − nb T V 2 (34) We are interesting in an equation of state for U(T. (33) ∂β 2 2 Problem: Express the equation of state for internal energy for a Berthelot gas.

CV .¡ ¢ ¡ ∂U ¢ Now ∂U V is just heat capacity. ¶2 µ ¶ µ ∂P ∂V . One obtains ¶ µ ¶ µ n2 a n2 a ∂P nRT nR 2n2 a + 2 2 − + T −P =T = . Cp = Cv − T ∂T P ∂V T (41) 14 . (40) P This eliminates the constant V term and so. ∂T V factor (39) Solution: Here we either remember an identity or turn to our handout of partial ¡ ¢ derivative identities to employ the cyclic rule to ∂P V : ∂T µ ∂P ∂T ¶ V ∂P =− ∂V µ ¶ µ T ∂V ∂T ¶ . but ∂V T is nothing convenient so we must ∂T proceed. We employ the “useful relation” µ ¶ ¶ µ ∂U ∂P =T −P (36) ∂V T ∂T V to eliminate U in favor of P so that we can use the equation of state for a Berthelot gas. (37) ∂T V V − nb T V V − nb T V 2 TV 2 Hence the equation of state for internal energy of a Berthelot gas is dU = CV dT + 2n2 a dV TV 2 ¡ ∂P ¢ (38) Problem: Use the identities for partial derivatives to eliminate the in ¶ µ ¶ µ ∂P ∂V Cp = Cv + T ∂T P ∂T V so that all derivatives are at constant pressure or temperature.

Part I Basic Quantum Mechanics 15 15 .

1. Atomic spectral lines 4. The “Fall” of Classical Physics A good theory: • explain known experimental results • self consistent • predictive • minimal number of postulates Around the turn of the century. • Many phenomena described by minimal and general concepts.1. Quantum Theory The goal of science is unification. experiments were being performed in which the results defied explanation by means of the current understanding of physics. The photoelectric effect 2. 1. Low temperature heat capacity 3. Among these experiments were 1. Black body radiation and the ultraviolet catastrophe 16 16 .

Bohr’s Atomic Theory 1.2. First Attempts at the Structure of the Atom The “solar system” model.2. The two slit experiment 6. • The electron orbits the nucleus with the attractive coulomb force balanced by the repulsive centrifugal force.5. Flaws of the solar system model • Newton: OK √ √ • Maxwell: problem 17 .1. The Stern-Gerlach experiment ∗ ∗ See Handouts ∗ ∗ 1.

The atom collapses! Bohr’s model: Niels Bohr (1885—1962) 18 .— As the electron orbits the nucleus. the atom acts as an oscillating dipole • — The classical theory of electromagnetism states that oscillating dipoles emit radiation and thereby lose energy. — The system is not stable and the electron spirals into the nucleus.

. r= 4π 0 N 2 ~2 (1. ~ = h/2π is Planck’s constant divided by 2π. i. EN = −Z 2a0 N 2 Tests of the Bohr atom • Ionization energy of Hydrogen atoms — The Ionization energy for Hydrogen atoms (Z = 1) is the minium energy required to completely remove an electron form it ground state. N = 1 → N = ∞ µ ¶ 1 e2 −Z 2 e2 1 − 2 = (1. • If the orbital radius was continuous the gas would have a continuous spectrum.2) 19 .e.52918 Å and is called the Bohr radius.3) Eionize = E∞ − E1 = 2a0 ∞2 1 2a0 (1. • Therefore atomic orbitals must be quantized. me e2 The total energy of the Bohr atom is related to its quantum number µ 2 ¶ e 1 2 .• Atoms don’t collapse =⇒ what are the consequences Experimental clues • Atomic gases have discrete spectral lines. 2 The constant quantity 4π e0e~ appears often and is given the special symbol a0 ≡ m 2 4π 0 ~2 = 0. me and e are the mass and charge of the electron respectively and 0 is the permittivity of free space. N is a positive real integer called the quantum number.1) Zme e2 where Z is the atomic number.

605 eV (very good agreement) • Spectroscopic lines from Hydrogen represent the difference in energy between the quantum states — Bohr theory: Difference energies µ ¶ µ ¶ 1 1 e2 1 1 Ej − Ek = − 2 =R − 2 2a0 Nj2 Nk Nj2 Nk Initial state Nk 1 2 3 4 5 • Final States Nj 2.5.· · · 6.6. R is called the Rydberg constant.5) Failure of the Bohr model • No fine structure predicted (electron-electron coupling) • No hyperfine structure predicted (electron-nucleus coupling) • No Zeeman effect predicted (response of spectrum to magnetic field) 20 .· · · 4.· · · Series Name Lyman Balmer Pachen Brackett Pfund (1.· · · 5.4.4.606 eV = 109.4) — Since the orbitals are quantized.7.667 cm−1 = R.e — Eionize = 2a0 = 13.· · · 3. — Doing this results in the emission or absorption of a photon with energy v= ˜ 4E hc (1. the atom may only change its orbital radius by discrete amounts. 2 — Eionize experimentally observed from spectroscopy is 13.8.5.3.7.6.

11.• Spin is not included in theory The Bohr quantization idea points to a wavelike behavior for the electron. The wave must satisfy periodic boundary conditions much like a vibrating ring ∗ ∗ ∗ See Fig.9 Laidler&Meiser ∗ ∗∗ The must be continuous and single valued Particles have wave-like characteristics The Bohr atom was an important step towards the formulation of quantum theory • Erwin Schrödinger (1887—1961): Wave mechanics • Werner Heisenberg (1902—1976): Matrix mechanics • Paul Dirac (1902—1984): Abstract vector space approach 21 .

we will most often deal with time independent “stationary” states ψ(x. That is. y and y +dy and z and z +dz is |ψ(x. y. z) and. in fact.1. It may. θ. ψ∗ ψ = |ψ|2 . represents a probability distribution which is directly observable. φ)|2 r2 sin θdrdθdφ in spherical coordinates). ψ. z) at the position between x and x+dx. z) Note: In general the wavefunction need not be expressed as a function of coordinate. However the mod-square of the wavefunction. y. The wavefunction ψ represents a probability amplitude and is not directly observable. The Postulates of Quantum Mechanics 2. We will normally take ψ to be a complex valued function of time and coordinates: ψ(t. be a function of momentum.2. Postulate I Postulate I: The state of a system is defined by a wavefunction. x. which contains all the information that can be known about the system. for example. 22 22 . y. z)|2 dxdydz (or |ψ(r. the probability of finding a particle which is described by ψ(x. y.

y. ψunnorm we know that this function must simply be some constant N multiplied by the normalized version of this function: ψ unnorm = Nψnorm . z)|2 dxdydz < ∞ Normalization of the wavefunction In order for |ψ(x. z)|2 to be exactly interpreted as a probability distribution. y. where N = |ψunnorm (x. (2. we take the mod-square of both sides and then integrate both sides of this equation over all space Z Z 2 |ψunnorm | dxdydz = |Nψnorm |2 dxdydz. qR That is. y. ψ unnorm = Nψnorm . z) must be normalizable. ψ(x.2) space space 23 . z)|2 dxdydz space R This assures that space |ψnorm |2 dxdydz = 1 as expected for a probability distribution From now on we will always normalize our wavefunctions.2.1) Now. (2. How to normalize a wavefunction If we have some unnormalized wavefunction.Properties of the wavefunction • Single valueness • continuous and finite • continuous and finite first derivative R • space |ψ(x. 2. y.

6) So finally we get the normalized wavefunction by reagranging ψ unnorm = Nψnorm : ψ norm = 1 ψ .4) This gives us an expression for N. Taking the square root of both sides gives. (2. Postulates II and II Postulate II: Every physical observable is represented by a linear (Hermitian) operator. sZ N= space |ψunnorm (x. y. Z |ψunnorm |2 dxdydz = N 2 × 1 = N 2 . N unnorm (2. z)|2 dxdydz. (2.8) 2 normalized x |ψ(x)| dx 1 −∞ 2. therefore this is a general procedure that will work for any wavefunction. (2. 24 . So.but The N is just a constant so it can be pulled out of both the mod-square and the integral Z Z 2 2 |ψunnorm | dxdydz = N |ψnorm |2 dxdydz. Thus wherever R we see space |ψnorm |2 dxdydz we can replace it with 1.5) space Z space |ψnorm |2 dxdydz = 1 (2.7) Notice that no where did we ever specify what ψunnorm or ψnorm actually were.3. To find the probability for the particle to be in a finite region of space we simple evaluate (here a 1D case) R x2 Z x2 |ψ(x)|2 dx if ψ(x) x1 P (x1 < x < x2 ) = R ∞ =⇒ |ψ(x)|2 dx (2.3) space space because that is the very definition of a normalized wavefunction.

There is a special operator equation called the eigenvalue equation which is ˆ Of (x) = λf (x) where λ is just a number. cylindrical. etc.9) This is just like how a function takes a number and turns it into another number. Postulate III: The measurement of a physical observable will give a result that is one of the eigenvalues of the corresponding operator. For a given operator only a special set of function satisfy this equation.An operator takes a function and turns it into another function ˆ Of (x) = g(x) (2. Nearly all operators we will need are algebraic combinations of the above.). So in quantum mechanics operators act on the wavefunction to produce a new wavefunction The two most important operators as far as we are concerned are • x=x ˆ ∂ • px = −i~ ∂x ˆ and of course the analogous operators for the other coordinates (y. z) and coordinate systems (spherical. (2. These functions are called eigenfunctions.10) 25 .

we ask ourselves what function is proportional to its own derivative? ⇒ f (x) = eλx . So the eigenfunctions are the set of functions f (x) = eλx and the eigenvalues are the numbers λ 26 .11) So. Example ˆ ˆ Let O in the eignevalue equation be the operator that takes the derivative: O = ˆ d d = dx . So solution of the eigenvalue equation gives a set of eigenfunctions and a set of eigenvalues. So we want a solution to ˆ df (x) = λf (x) df (x) = λf (x) dx (2.The number that goes with each function is called the eigenvalue.

2. The eigenvalue equation for the Hamiltonian is ˆ Hψ = Eψ. The Quantum Mechanical Problem Nearly every problem one is faced with in elementary quantum mechanics is handled by the same procedure as given in the following steps. The operator associated with the total energy is called the Hamiltonian operator ˆ (or simply the Hamiltonian) and is given the symbol H.3. This equation is the most important equation of the course and we will use it many times throughout our discussion of quantum mechanics and statistical mechanics. 27 27 . This equation is the (time independent) Schrödinger equation. 1. Define the classical Hamiltonian for the system.1. The Hamiltonian The most important physical observable is that of the total energy E. The Setup of a Quantum Mechanical Problem 3.1) 3. (3.

z). 2 2 ˆ −~ ∇2 = −~ ∇2 . y.8) ⇒ 2m 28 . • The kinetic energy is always of the form T = ¢ 1 ¡ 2 px + p2 + p2 y z 2m (3.6) ˆ V = V (ˆ. Use Postulate II to replace the classical variables. z) ψ = Eψ 2m −~2 2 ∇ ψ + (V (x. ∂z 2 and (3.7) ˆ 3. x ˆ ˆ So. Thus. which is now a second order differential equation of the form ¸ ∙ 2 −~ 2 ∇ + V (x.3) • The potential energy is almost always a function of coordinates only V = V (x. −~2 2 ˆ ˆ ˆ ∇ + V (x.4) • Note: Some quantum systems don’t have classical analogs so the Hamiltonian operator must be hypothesized.5) where ∇2 ≡ ∂2 ∂x2 + ∂2 ∂y2 + ∂2 . y. z) H =T +V = 2m (3. z) − E) ψ = 0 (3. Hψ = Eψ. y. 2.2) (3. x. y.. ˆ T = 2m 2m (3. where T is the kinetic energy and V is the potential energy. Solve the Schrödinger equation.• The total energy for a classical system is Ecl = T + V. with their appropriate operators. z) (3. z ) = V (x. y . px etc. y.

However. but we cannot predict for certain which one. y. If ψ is not an eigenfunction of a particular operator. We can.11) space ψ px ψdxdydz = −i~ ˆ ∗ Z (3.9) 3. or average. value for the measurement. z) which determines whether this is easy or hard to do. • For one-dimensional problems −~2 d2 ψ + (V (x) − E) ψ = 0 2m dx2 (3.• Note: It is solely the form of V (x. then all measurements of that physical property will yield the associated eigenvalue. then all measurements of that physical property will still yield an eigenvalue. The Average Value Theorem Postulate III implies that if ψ is an eigenfunction of a particular operator representing a physical observable.3. give an expectation. This is given by Z hˆ i = α ψ∗ αψdxdydz ˆ (3.12) space 29 . hˆi = x and hˆx i = p Z Z ψ xψdxdydz = ˆ ∗ space Z space x |ψ|2 dxdydz ψ∗ ∂ψ dxdydz ∂x (3. however.10) space For example.

13) 2 h i ˆ means the commutator of α and β. β ¯ . δpx δy = 0.b. Such variables are called complimentary.14) The most important example of complimentary variables is position and momentum.15) So. for example. The Heisenberg Uncertainty Principle In quantum mechanics certain pairs of variables can not. the y position and the x momentum to arbitrary precision. α. ˆ (3. The general statement of the Heisenberg uncertainty principle is 1 ¯Dh ˆ iE¯ ¯ ¯ δαδβ ≥ ¯ α.) Suppose we know the position of a particle perfectly. (n. be simultaneously known to arbitrary precision.3. even in principle. β ˆ ˆˆ ˆˆ (3. we can 2 know. x]i| = |hˆx x − xpx i| p ˆ p ˆ ˆˆ 2 ¯Z 2 ¯ µ ¶ ¯ 1¯ ¯ ψ ∗ ~ ∂ x − x ∂ ψdx¯ = ¯ 2¯ i ∂x ∂x ¯ ¯ ¯~¯ ~ = ¯ ¯= . ¯ 2i ¯ 2 (3. at the very best we can only hope to simultaneously know position and momentum such that the product of the uncertainty in each is ~ . The commutator is ˆ where the notation α. what can we say about its momentum? 30 .4. β ˆ ˆ defined as h i ˆ ≡ αβ − β α. This idea is the Heisenberg uncertainty principle and is of profound importance. We see δpx δx ≥ 1 1 |h[ˆx ..

V (x). we must violate one of our criteria for a good wavefunction.1) Because of the infinities at x = 0 and x = a. 4. Nevertheless it is of great pedagogical and practical value. we need to partition the x-axis into the three regions shown in the figure. It also can be used as a “zeroth order” model for certain physical systems. Particle in a Box We now will apply the general program for solving a quantum mechanical problem to our first system: the particle in a box. ⎪ ⎩ ∞ x≥a (4. The 1D Particle in a Box Problem Consider the potential. 31 31 . shown in the figure and given by ⎧ x≤0 ⎪ ∞ ⎨ V (x) = 0 0<x<a . We shall soon see that the particle in a box is a physically unrealistic system and. as a consequence.4. This system is very simple which is one reason for beginning with it.1.

3) (4. dx2 ~ The general solution of this differential equation is ψ(x) = A sin kx + B cos kx.c. 32 . Hψ 2m dx2 (4. Therefore it must satisfy the boundary conditions (b. ψ must equal zero in these regions. where k = q 2mE .): ψ(0) = 0 and ψ(a) = 0. The Schrödinger equation in region II is (V (x) = 0) 2 2 ˆ = Eψ =⇒ −~ d ψ(x) = Eψ. in region I and III. ~2 (4. the particle can never exist so. where the potential is infinite.Now.2) which can be rearranged into the form d2 ψ(x) 2mE + 2 ψ(x) = 0. The particle must be found only in region II.4) Now ψ must be continuous for all x.

now we have nπx ..8) 33 . · · · .6) The constant A is the normalization constant. nπ . So we are left with ψ(x) = A sin kx for our wavefunction. We obtain A from Z ∞ Z a nπx nπx ∗ sin dx.c.5) (4.c. 3. 2. a (4.From the ψ(0) = 0 b. As can be inferred from the following figure. we see that the constant B must be zero because cos kx|x=0 = 1. this becomes a Z π π A2 a a/ 2a = . ψ(a) = 0. ψn (x) = A sin a kn = (4. the second b. places certain restrictions on k.7) du = π dx. a The values of k are quantized. So. n = 1. 1=A sin2 nudu = A2 π 0 2 / 2 π (4. ψn (x)ψ n (x) = 1 = A2 sin a a −∞ 0 Letting u = πx . In particular.

a in a box are I II III . Implications of the Particle in a Box problem Zero Point Energy 34 .11) 4. (4.2.10) We can get the energy levels from kn = En = and kn = nπ : a h n2 π 2 ~2 ~= 2π n2 h2 = .9) Is this wavefunction OK? Thus our normalized wavefunctions for a particle ⎧ ⎪ 0 ⎪ q ⎨ 2 ψn (x) = sin nπx a ⎪ a ⎪ ⎩ 0 q 2mEn ~2 (4.Solving for A gives A= r 2 . 2ma2 8ma2 (4.

or ground state. δˆδp = 0 which violates the uncertainty principle. x ˆ Features of the Particle in a Box Energy Levels • The energy level spacing is 4E = En+1 − En = 4E = (2n + 1) (n + 1)2 h2 n2 h2 h2 − = (n2 + 2n + 1 − n2 ) / / 8ma2 8ma2 8ma2 (4. the lowest energy state. has nonzero energy. This residual energy is called the zero point energy and is a consequence of the uncertainty principle. δ p = 0.13) h2 8ma2 • This spacing increases linearly with quantum level n • This spacing decreases with increasing mass • This spacing decreases with increasing a • It is this level spacing that is what is measured experimentally The Curvature of the Wavefunction 35 .12) That is. But we also know that the particle is located within a finite region of ˆ space. x Hence.The smallest value for n is 1 which corresponds to an energy of E1 = h2 6= 0. 8ma2 (4. so δˆ 6= ∞. If the energy was zero then we would conclude that momentum was exactly zero.

Therefore it must do something between x = 0 and x = a. • We know the wavefunction is zero in regions I and III. Therefore the energy levels decrease in energy as does their difference. As another example consider the expectation value of position for a particle in the second quantum level: Z ∞ Z a 2 a 2π ∗ hxi = (4.ˆ The operator for kinetic energy is T = −~ 2 d2 . the wavefunction is less confined and so the curvature does not need to be as great to satisfy the boundary conditions. This is an important concept for the qualitative understanding of wavefunctions for any quantum system. It must have some curvature and hence some zero point energy. a wavefunction with more curvature will have a larger second derivative and hence it will posses more kinetic energy. • As a is increased. We also know that the wave function is not zero everywhere.14) ψ2 (x)xψ 2 (x)dx = x sin2 [ x]dx = a 0 a 2 −∞ 36 . 2m dx2 The important part of this is d2 . The particle in a box problem illustrates some of the many strange features of quantum mechanics. Applying this idea to the particle in a box we an anticipate both zero point energy and the behavior of the energy levels with increasing a. We have already seen such nonclassical behavior as quantized energy and zero point energy. dx2 From freshman calculus we know that the second derivative of a function describes its curvature so.

yet the probability of finding the particle at x = a is zero: ψ2 ( a ) = 0. There is 2 2 a a node at x = 2 . 37 . it can never be found at the node. So even though the particle may be found anywhere else in the box and it may get from the left side of the node to the right side.

We shall begin by reviewing the classical harmonic oscillator and than we will turn our attention to the quantum oscillator. The classical example is a ball on a spring The harmonic oscillator is arguably the single most important model in all of physics. where k is the spring constant and Req is the equilibrium position of the ball. 38 38 . Setting x = R − Req we can measure the displacement about the equilibrium position. The force exerted by the spring in the above figure is F = −k(R − Req ). The Harmonic Oscillator The harmonic oscillator model which is simply a mass undergoing simple harmonic motion.5.

5) This differential equation is not easy to solve (you can wait to solve it in graduate school). P.1) This is second order differential equation which we already know the solutions to: x = A sin ωt + B cos ωt. 2 By postulate III the Schrödinger equation becomes ⎛ ⎞ K. (5. we need to express the force of the spring in terms of potential energy V .x From Newton’s law of motion F = ma = m d 2 . 2 2 |2m dx } | {z } {z µ ¶ 1 2 kx − E ψ = 0 2 (5. We know Z 1 V = − F dx = kx2 + C. where ω = conditions.3) 2 Since energy is on an arbitrary scale we can set C = 0. Thus V = 1 kx2 .4) (5. 39 .2) and A and B are constants which are determined by the initial For quantum mechanics it is much more convenient to talk about energy rather than forces. so in going to the quantum oscillator.E. we get dt 2 d2 x k d2 x m 2 = −kx ⇒ 2 + x = 0 dt dt m (5. q k m (5.E. This can be rearrange into the form −~2 d2 ψ + 2m dx2 1 ⎜ −~2 d2 ⎟ ˆ Hψ = Eψ ⇒ ⎝ + kx2 ⎠ ψ = Eψ.

Interesting Aspects of the Quantum Harmonic Oscillator It is interesting to investigate some of the unintuitive properties of the oscillator as we have gone quantum mechanical 40 .The equation is very close to the form of a know differential equation called Hermite’s differential equation the solutions of which are called the Hermite polynominals.1.12 Laidler&Meiser ∗ ∗∗ 5. An = p √ . As it turns out.6) x. 2 where again ω = q k . y = (5. m (5.8) q k m and is called the vibrational constant. 2 ~ 2n n! π where An is the normalization constant for the nth eigenfunction and Hn (y) are the Hermite polynomials. 2 where ν 0 = 1 2π (5. the solutions (the eigenfunctions) to the Schrödinger equation for the harmonic oscillator are ¶1 µ 2 km 4 1 − y2 ψn (y) = An Hn (y)e . 11. The eigenvalues (the energy levels) are 1 En = (n + )~ω. ∗ ∗ ∗ See Fig.7) Note the energy levels are often written as 1 En = (n + )hν 0 .

Interpretation of the wavefunctions and energy levels 41 . 2. 3. the quantum system must behave like a classical system. • The wavefunctions penetrate into the region where the classical particle is forbidden to go — The wavefunction is nonzero past the classical turning point. Consider the wavefunctions. — This is a manifestation of the correspondence principle which states that for large quantum numbers. so δpδx = 0 Not allowed! — The uncertainty principle forces there to be some residual zero point energy. Consider the ground state (the lowest energy level) • There is residual energy in the ground state because 1 E0 = (0 + )~ω. then we would conclude that the momentum of the oscillator was zero. 2 • Just like for the particle in a box. δx = 0. this energy is called the zero point energy. In other words the quantum mechanics must contain classical mechanics as a limit. • It is a consequence of uncertainty principle — If the ground state energy was really zero. • The probability distribution |ψ|2 becomes more and more like what is expected for the classical oscillator when v → ∞. we would conclude the particle was located at the bottom of the potential well (at x = 0) — Thus we would have δp = 0. — On the other hand.1.

Spectroscopy (An Introduction) The primary method of measuring the energy levels of a material is through the use of electromagnetic radiation. 5. These specific values correspond to the energy level difference between the initial and final states. Experiments involving electromagnetic radiation—matter interaction are called spectroscopies.• Remember the wavefunctions are time independent and the energy levels are stationary • If a molecule is in a particular vibrational state it is NOT vibrating. 42 .2. Atoms and molecules absorb or emit light only at specific (quantized) energies.

This section should not substitute for your studying of the rest of this material. (5. Equations • The short cut for getting the normalization constant (1D.10) • The Schrödinger equation (which should be posted on your refrigerator). The equations are collected here simply for handy reference for you while working the problem sets. (5. N unnorm (5. see above for 3D).11) 43 43 . sZ N= space |ψunnorm (x)|2 dx. The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations.9) • The normalized wavefunction: ψ norm = 1 ψ . ˆ Hψ = Eψ.Key Equations for Exam 1 Listed here are some of the key equations for Exam 1.

4E = (2n + 1) h2 8ma2 (5.15) (5.18) where An is the normalization constant for the nth eigenfunction and Hn (y) are the Hermite polynomials.13) • The momentum operator px = −i~ ˆ ∂ . −~2 d2 ψ + (V (x) − E) ψ = 0. ω = 2 k m (5. r • The energy levels are 1 En = (n + )~ω. r nπx 2 ψn (x) = sin . 2ma2 8ma2 (5.12) (5.19) 44 .14) • Normalized wavefunctions for the 1D particle in a box. An = p ψn (y) = An Hn (y)e . y = √ . Z ψ∗ αψdx.16) • The energy level spacing for the 1D particle in a box. En = h n2 π 2 ~2 ~= 2π n2 h2 = . a a • The energy levels for the 1D particle in a box. 2 n n! π ~ 2 (5. ˆ hˆ i = α space (5.• The Schrödinger equation for 1D problems as a differential equation.17) • The wavefunctions for the harmonic oscillator are ¶1 µ 2 km 4 1 − y2 x. 2m dx2 • How to get the average value for some property (1D version). ∂x (5.

Part II Quantum Mechanics of Atoms and Molecules 45 45 .

The Schrödinger equation for all the other atoms on the periodic table must be solved by approximate methods.6. The obvious choice for the coordinate system is to use spherical polar coordinates 46 46 .1. Hydrogen is the only atom for which we can exactly solve the Schrödinger equation for. Hydrogenic systems Hydrogenic systems are those atomic systems which consist of a nucleus and one electron. we move onto the quantum mechanical treatment of atoms. 6. These system are centrosymmetric. So this will be the first atomic system we discuss. Hydrogenic Systems Now that we have developed the formalism of quantum theory and have discussed several important systems. That is they are completely symmetric about the nucleus. The Hydrogen atom (one proton and one electron) is the obvious example Ions such as He+ and Li2+ are also hydrogenic systems.

2) Schrödinger’s equation (in spherical polar coordinates) becomes ˆ Eψ = Hψ (6. (6.4) (6.3) ¶ µ 2 2 −Ze −~ ˆ 2 ψ ∇ + Eψ = 2me (4π 0 )ˆ r µ 2∙ ¶ µ ¶¸ −~ 1 ∂ 2 ∂ 1 ∂ 1 ∂2 1 ∂ −Ze2 Eψ = r + sin θ + ψ + 2me r2 ∂r ∂r r2 sin θ ∂θ ∂θ sin2 θ ∂φ2 (4π 0 )r The Hamiltonian is (almost) the sum of a radial part (only a function of r) and an angular part (only a function of θ and φ): 1 ˆ ˆ ˆ H = Hrad + 2 Hang . φ) It turns out that solving the Schrödinger equation. φ) = Eψang (θ. ∇ + H= 2me (4π 0 )ˆ r (6.with the origin located on the nucleus. ˆ Hang ψang (θ.8) (6.7) 47 .6) Since the Hamiltonian is the sum of two terms. ψ must be a product state. (4π 0 )r (6. θ. The classical potential energy for these hydrogenic systems is V (r) = So the Hamiltonian is −Ze2 . φ).1) −Ze2 −~2 ˆ 2 ˆ .5) −~2 ˆ Hang = 2me (6. φ) = ψrad (r)ψang (θ. ψ(r. r ˆ Hrad and ¸ ∙ Ze2 −~2 1 ∂ 2 ∂ r − = 2me r2 ∂r ∂r (4π 0 )r µ ∂ 1 ∂2 1 ∂ sin θ + sin θ ∂θ ∂θ sin2 θ ∂φ2 ¶ (6.

9) where the Ylm (θ. r ˆ Operating with Hang we get ¶ µ 2 ˆ rad + l(l + 1)~ R(r)Ylm (θ. (Mathematica knows them and you can use them just like any other built-in function like sine or cosine. φ) = ER(r)Ylm (θ.) We shall use the spherical harmonics more next semester when we develop the quantum theory of angular momentum.13) 48 . The spherical harmonics are known functions. φ) ¶ µ 1 ˆ ˆ Hrad + 2 Hang R(r)Ylm (θ. φ) = ER(r)Ylm (θ.11) l(l + 1)~2 . φ). φ) = Eψ(r.yields ψ ang (θ. θ. φ) = 2me Now let’s denote the radial part of the wavefunction as ψ rad (r) = R(r). φ) ˆ HR(r)Ylm (θ. φ) H 2me r2 (6.10) (6. 2me (6. l(l + 1)~2 ˆ ψang (θ. The full Schrödinger equation becomes ˆ Hψ(r. φ) Hang ψang (θ. θ. φ)’s are the spherical harmonic functions characterized by quantum numbers l and m. φ) = Ylm (θ. φ). ˆ It also turns out that the energy associated with Hang is found to be E = El = So. φ) = ER(r)Ylm (θ. (6.12) (6.

depends on the n and l quantum numbers as sµ ¶3 2Z (n − l − 1)! Anl = − (6. Anl . 49 .14) 2me r2 ∂r ∂r 4π 0 r r2 This differential equation is very similar to a known equation called Laguerre’s differential equation which has as solutions the Laguerre polynomials Ll (x). (6. Discussion of the Wavefunctions We are now very close to having the atomic orbitals familiar from freshman chemistry.17) Note: The energy levels are determined by n alone–l drops out.The Ylm (θ.16) na0 2n[(n + l)!]3 The energy eigenvalues. φ) = Rnl (r)Ylm (θ. the solutions to our differential equation are closely related to the Laguerre polynomials.2. i.e.15) e Ln+1 n n where the normalization constant. Also Note: the energy levels are the same as for the Bohr model. n In fact. which will be briefly discussed later) is ψ nlm (r. µ ¶l µ ¶ 2σ 2σ −σ/n 2l+1 Rnl (σ) = Anl .. θ. the total wavefunction that describes a hydrogenic system (ignoring the spin of the electron. φ) can now be cancelled to leave a one dimensional differential equation: µ ¶ Ze2 l(l + 1) −~2 1 ∂ 2 ∂ r − − R(r) = ER(r). (6. So.18) 6. φ) (6. the energy levels are given by En = − Z 2R n2 (6.

The table below lists the atomic orbitals in the “chemists” picture as linear combinations of the “physicists” picture wave functions. The wavefunctions that chemists like are pure real. ψ 2p0 . ψ 2s . The atomic orbital you are used to from freshman chemistry are the “chemists” picture of atomic orbitals In the above table ψ1s . 50 . ψ 3d0 are pure real and so these are the same in the “chemists” picture as in the “physicists” picture.We have explicitly derived the “physicists” picture of the atomic orbitals orbital n l 1s 2s 2p 3d 1 2 2 2 3 3 3 0 0 1 1 2 2 2 m 0 0 0 ±1 0 ±1 ±2 wavefunctions (σ = r/a0 ) ψ1s = ψ100 = e−σ ¡ ¢ ψ2s = ψ200 = 1 − σ e−σ/2 2 ψ2p0 = ψ210 = σe−σ/2 cos θ ψ2p±1 = ψ21±1 = σe−σ/2 sin θe±iφ ψ3d0 = ψ320 = σ2 e−σ/3 (3 cos2 θ − 1) ψ3d±1 = ψ32±1 = R32 (r) cos θ sin θe±iφ ψ3d±2 = ψ32±2 = R32 (r) sin2 θe±i2φ The wavefunctions in the “physicists” picture are complex (they have real and imaginary components). So one needs to form linear combinations of these orbitals such that these combinations are pure real.

so we can not write down an explicit function of the coordinate space variables.3.orbital n l 1s 2s 2p 1 2 2 2 2 3d 3 3 3 3 0 0 1 1 m 0 0 0 ±1 wavefunctions (σ = r/a0 ) 6. 51 . For now we must be satisfied with the following: • There are two quantum numbers associated with spin: s and ms • s is the spin quantum number and for an electron s = 1/2 (always). Spin of the electron ψ3dz2 = ψ3d0 £ ¤ 1 2 ±1 ψ3dxz = √2 ψ3d1 + ψ3d−1 £ ¤ 1 2 ±1 ψ3dyz = i√2 ψ3d1 − ψ3d−1 £ ¤ 1 2 ±2 ψ3dxy = √2 ψ3d2 + ψ3d−2 £ ¤ 1 ψ3dx2 −y2 = i√2 ψ3d2 − ψ3d−2 2 0 ψ1s = ψ1s ψ2s = ψ2s ψpz = ψ2p0 £ ¤ 1 ψ2px = √2 ψ2p1 + ψ2p−1 £ ¤ 1 1 ±1 ψ2py = i√2 ψ2p1 − ψ2p−1 As we know from freshman chemistry. Spin is actually rather peculiar so we will put off a more detailed discussion until next semester. The spin wavefunction is a function in spin space not the usual coordinate space. • ms is the spin orientation quantum number and ms = ±1/2 for electrons. electrons also posses an intrinsic quantity called spin.

It also determines the atomic sub-shells (6. 1 (the “spin-up” state) and β ≡ χ 1 .− 1 (the “spin-down” state) 2 2 2 2 6. l: determines the total angular momentum of the system. φ)χ The energy is given by Z 2R .m χs.ms and “tack it on” as another factor of the complete wavefunction. En = − The quantum numbers of the hydrogenic system • The principle quantum number.3.ms = ψn. can take on values of 1. n: determines the total energy of the systems and the atomic shells.m. When a particular spin state is needed a further notation is commonly used: α ≡ χ 1 .4.We simply denote the spin wavefunction generally as χs.2. (6. n.ms = Rnl (r)Yl. Summary: the Complete Hydrogenic Wavefunction We are now in position to fully describe all properties of hydrogenic systems (except for relativistic effects) The full wave function is Ψn.19) 52 .m (θ. Again note that for a free hydrogenic system the total energy depends only on the principle quantum number n. . . • The angular momentum quantum numbers. — The principle quantum number.20) n2 where recall.l.l.s.

l. ms : determines the projection of the spin angular momentum onto the z-axis (i. l = 1 is called p. can take on values of 0. spin-up or spin-down). We have determined all that we can about the hydrogen atom within Schrödinger’s theory of quantum mechanics. l = 3 is called f etc. This is not the full story however. s: determines the total spin angular momentum. it can not account for relativistic effects which show up in spectral data. . • The orientation quantum number. can take on values of 0.— The angular momentum quantum number. . (n − 1) — For historical reasons l = 0 is called s. We also had to add spin in an ad hoc manner to account for what we know experimentally–spin did not fall out of the theory naturally. developed a relativistic quantum theory in which the well established phenomenon of spin arose naturally. . — For electrons ms = ±1/2 We have accomplished quite a bit. His theory also made the 53 . m. ± l. ±1. . Dirac. l = 2 is called d. that is. . 1. • The spin orientation quantum number.. • The spin quantum number.e. The Schrödinger theory is a non-relativistic one. m: determine the projection of the angular momentum onto the z-axis. It also determines the orientation of the atomic sub-shells — The magnetic quantum number. — For electrons s = 1/2. in the late 1920’s. .

Both the relativistic Dirac theory and QED are beyond our reach. because there still existed experimental phenomena that was not properly described. QED is the best theory ever developed in terms of matching with experimental data. so we limit ourselves to the non-relativistic Schrödinger theory. In 1948 Richard Feynman developed the beginnings of quantum electrodynamics (QED). The Dirac theory was still not fully complete. 54 .bold prediction of the existence anti-matter that has now been verified time and again.

The problem must be solved by one of the following methods • Numerical solutions (we will not discuss this) 55 55 . repulsion where r12 = |r1 − r2 | is the distance between the electrons. (7. In fact. It makes a closed form solution impossible. Multi-electron atoms 7. The Hamiltonian for helium is ~2 2 ˆ H= − ∇ 2me 1 | {z } ~2 2 − ∇ 2me 2 | {z } Ze2 − 4π r | {z 0 1 } Ze2 − + 4π 0 r2 | {z } e2 4π 0 r | {z 12 } . it is so complicated that it can’t be solved exactly.7.E of electron 1 K. helium.—elec.E of electron 2 P.1) K.E of electron 1 P.E of eletcron 2 elec. Although the extension from hydrogen to helium seems simple it is actually extremely complicated. The electron—electron repulsion term is responsible for the difficulty of the problem.1. Two Electron Atoms: Helium We now consider a system consisting of two electrons and a nucleus. for example. The helium atom is an example of the “three-body-problem”–difficult to handle even in classical mechanics–one can not get a closed form solution.

only |ψ|2 is directly measurable–not ψ itself. All this implies that ⎧ ⎪ +ψ(2. photons): The total wavefunction for bosons must be symmetric under exchange of indistinguishable bosons.g. Now. The Pauli Exclusion Principle Electron are fundamentally indistinguishable. They can not truly be labelled. helium 56 . 1 and 2 must be exactly the same as when the electrons are labelled 2 and 1. All physical properties of a system where we have labelled the electrons as. 1). Note: a similar statement exists for bosons (e. ⎨ ψ(1. 2) = or ⎪ ⎩ −ψ(2.2. 1) symmetric (7.• Perturbation theory (next semester) • Variational theory (next semester) • Ignore the electron—electron repulsion (good for qualitative work only) 7. say.2) antisymmetric The Pauli exclusion principle states: The total wavefunctions for fermions (e.. electrons) must be antisymmetric under the exchange of indistinguishable fermions.. Let us consider the two electron atom.g.

• Similarly for Ψd . 2) (7. However considering the symmetry with respect to exchange we see the following • Ψa has symmetric spatial and spin parts and is there for symmetric. one must make an antisymmetric linear combination of the spin parts. So. Likewise if the spatial part is odd then the spin part must be even. • Ψb and Ψc have symmetric spatial parts. The Pauli exclusion principle implies that if the spatial part is even with respect to exchange then the spin part must be odd.3) Since a complete solution for helium is not possible we must use approximate wavefunctions. we may as well simplify matters and use product state wavefunctions (products of the hydrogenic wavefunctions). (7.4) where the single particle wavefunctions are that of the hydrogenic system. It must be excluded. Ψ = ψ(1)ψ(2)χ(1)χ(2).The total wavefunction is Ψ = ψ(1.5) 57 . 2)χ(1. but the spin part is neither symmetric or antisymmetric. Since we are doing this. | {z }| {z } spatial part spin part (7. Now let’s blindly list all possibilities for the ground state wave function of helium Ψa = ψ1s (1)α(1)ψ1s (2)α(2) Ψb = ψ1s (1)α(1)ψ1s (2)β(2) Ψc = ψ1s (1)β(1)ψ1s (2)α(2) Ψd = ψ1s (1)β(1)ψ1s (2)β(2) These appear to be four reasonable ground state wavefunctions which would imply a four-fold degeneracy.

.8) . Namely the wavefunction is product state that must be antisymmeterized in accordance with the Pauli exclusion principle.6) 7. ¯ ¯ ¯ ¯ ¯ ψ (N)α(N) ψ (N)β(N) ψn (N )α(N) ψn (N)β(N) ¯ 1s 1s 58 . . . . . . . ¯ ¯ . . . . So the ground state wave function for helium is Ψg = ψ1s (1)ψ1s (2) [α(1)β(2) − α(2)β(1)] . Many Electron Atoms The remaining atoms on the periodic table are handled in a manner similar to helium.3.7) (7. . The product wavefunction for the ground state is determined by applying the aufbau principle.The appropriate linear combination is α(1)β(2) − α(2)β(1). . . The aufbau principle states that the ground state wavefunction is built-up of hydrogenic wavefunctions To arrive at an antisymmetric wavefunction we construct the Slater determinant: ¯ ¯ ¯ ψ (1)α(1) ψ1s (1)β(1) · · · ψn (1)α(1) ψn (1)β(1) ¯ ¯ 1s ¯ ¯ ¯ ¯ ψ1s (2)α(2) ψ1s (2)β(2) · · · ψn (2)α(2) ψn (2)β(2) ¯ ¯ Ψ=¯ (7. Consequences of the Pauli exclusion principle • No two electrons can have the same five quantum numbers • Electrons occupying that same subshell must have opposite spins (7.

3.11) H= 2me i 4π 0 ri j>i 4π 0 rij i=1 59 . The Total Hamiltonian The total Hamiltonian for a many electron (ignoring spin-orbit coupling which will be discussed next semester) atom is " # N X −~2 X e2 Ze2 ˆ ∇2 − + (7.10) • The short hand notation for these states is (1s)2 (2s)1 7. ψ1s β.The reason one can be sure that this wavefunction is the antisymmeterized is that we know from linear algebra that the determinant is antisymmetric under exchange of rows (corresponds to exchanging two electrons).1.9) (7. This agrees with the Puli exclusion principle. Another property of the determinant is that if two rows are the same (corresponds to two electrons in the same state) the determinant is zero. and ψ2s α (or ψ 2s β). As an example consider lithium: • There are three electrons so we need three hydrogenic wavefunctions: ψ1s α. It is also antisymmetric under exchange of columns. • We construct the Slater determinant as ¯ ¯ ¯ ψ (1)α(1) ψ (1)β(1) ψ (1)α(1) ¯ 1s 1s 2s ¯ ¯ ¯ ¯ Ψ1 = ¯ ψ1s (2)α(2) ψ1s (2)β(2) ψ2s (2)α(2) ¯ ¯ ¯ ¯ ψ (3)α(3) ψ (3)β(3) ψ (3)α(3) ¯ 1s 1s 2s or ¯ ¯ ¯ ψ (1)α(1) ψ (1)β(1) ψ (1)β(1) ¯ 1s 2s ¯ ¯ 1s ¯ ¯ Ψ2 = ¯ ψ1s (2)α(2) ψ1s (2)β(2) ψ2s (2)β(2) ¯ ¯ ¯ ¯ ψ (3)α(3) ψ (3)β(3) ψ (3)β(3) ¯ 1s 1s 2s (7.

θ. R determines the internuclear separation and θ and φ determine the orientation. φ) which describe the position of the nuclei relative to the center of mass. This chapter will be limited to diatomic molecules. Molecular Energy A diatomic molecule with n electrons requires that 3n+6 coordinates be specified. Diatomic Molecules and the Born Oppenheimer Approximation Now that we have applied quantum mechanics to atoms.8. Three of these describe the center of mass position. 3n of these describe the position of the n electrons. This leaves three degrees of freedom (R. we are able to begin the discussion of molecules. 8. 60 60 .1.

2) m1 m2 m1 +m2 ˆ where J is angular momentum operator for molecular rotation and μ = the reduced mass of the diatomic molecule. + ZB e2 4π 0 rBi P ˆ VNe = − i P ˆ Vee = i>j h ZA e2 4π 0 rAi i is the nuclear—electron potential energy operator. P ~2 ˆ 2 ˆ Te = i − 2me ∇ei is the kinetic energy operator for the electrons.1) (8.1. 61 . e2 4π 0 rji is the electron—electron potential energy operator.8.1. ˆ VNN = ZA ZBe e2 4π 0 R is is the nuclear—nuclear potential energy operator. The Hamiltonian In the center of mass coordinates the Hamiltonian for a diatomic molecule is ˆ ˆ ˆ ˆ ˆ ˆ H = TN + Te + VN N + VNe + Vee . R T 2μ 2μR2 ∂R ∂R 2μ (8. ˆ TN is the nuclear kinetic energy operator and is given by 2 2 ~2 ˆ2 ∂ ˆ2 ∂ ˆN ˆN = − ~ ∇2 = − ~ + J .

8.1.2. The Born—Oppenheimer Approximation The Born—Oppenheimer approximation: The nuclei move much slower than the electrons. (classical picture) We put the Born—Oppenheimer approximation to work by first defining an effective Hamiltonian ˆ ˆ ˆ ˆ ˆ Hef f = Te + VN N + VNe + Vee . (8.3) The approximation comes in by treating R as a parameter rather than an operator (or variable). So one writes ˆ Hef f ψe (R, {ri }) = Ee (R)ψ e (R, {ri }). ψe is the so-called electronic wavefunction. Now the Schrödinger equation for the diatomic molecule is ³ ´ ˆ ˆ TN + Hef f ψ(R, {ri }) = Eψ(R, {ri }). (8.4)

(8.5)

Since the Hamiltonian is a sum of two terms, one can write the wavefunction ψ(R, {ri }) as a product wavefunction ψ = ψN ψe , (8.6)

where ψN is the so-called nuclear wavefunction. Substituting the product wavefunction into the Schrödinger equation gives ³ ´ ˆ ˆ (8.7) TN + Hef f ψN ψe = EψN ψe ³ ´ ˆ / / TN + Ee (R) ψ N ψe = EψN ψe ³ ´ ˆ TN + Ee (R) ψ N = EψN .

62

The last equation is exactly like a Schrödinger equation with a potential equal to Ee (R). One now models Ee (R) or determines it experimentally.

8.2. Molecular Vibrations
As stated earlier R is the internuclear separation and θ and φ determine the orientation. Consequently, R is the variable involved with vibration whereas θ and φ are involved with rotation. Considering only the R part of the Hamiltonian (under the Born—Oppenheimer approximation), we have ∙ 2 2 ¸ ~ ∂ − + Ee (R) ψvib = Evib ψvib . (8.8) 2μ ∂R2 It is convenient at this point to expand Ee (R) in a Taylor series about the equilibrium position, Req : ¶ µ ¶ µ ∂E 1 ∂2E 0 (R − Req ) + (R − Req )2 + · · · . (8.9) Ee (R) = E + 2 ∂R Req 2! ∂R Req Now E 0 is just a constant which, by choice of the zero of energy, can be set to an arbitrary value. Since we are at a minimum, One defines ³
∂2E ∂R2

´

¡ ∂E ¢

∂R Req

must be zero, so the linear term vanishes.

Req

≡ ke as the force constant.

The remaining terms in the expansion can collective be defined as O[(R−Req )3 ] ≡ Vanh , the anharmonic potential.

63

As a first approximation we can neglect the anharmonicity. With this, the Schrödinger equation becomes ∙ 2 2 ¸ ~ ∂ 1 2 − + ke (R − Req ) ψvib = Evib ψvib . (8.10) 2μ ∂R2 2 If we let x = (R − Req ) this becomes ¸ ∙ 2 2 1 ~ ∂ 2 + ke x ψvib = Evib ψvib , − 2μ ∂x2 2 which is exactly the harmonic oscillator equation. Hence √ 2 ψ vib,n = An Hn ( αx)e−αx /2 , where α ≡ And q q
ke μ . ~

(8.11)

(8.12)

1 Evib,n = hc˜ e (n + ), ω 2
ke . μ

(8.13)

where ω e ≡ ˜

1 2π

8.2.1. The Morse Oscillator Neglecting anharmonicity and using the harmonic oscillator approximation works well for low energies. However, it is a poor model for high energies. For high energies we need a more realistic potential–one that will allow of bond dissociation. The Morse potential Ee (R) = De [1 − e−β(R−Re q ) ]2 , (8.14)

64

μ where De is the well depth and β = 2πc˜ e 2De is the Morse parameter. Note: ω this expression for the Morse potential has the zero of energy at the bottom of the well (i.e. R = Req , ;Ee (Req ) = 0).

q

The Morse Potential can also be written as Ee (R) = De [e−2β(R−Req ) − 2e−β(R−Re q ) ]. (8.15)

Now the zero of energy is the dissociated state (i.e. R → ∞, ;Ee (R → ∞) = 0). We approach this quantum mechanical problem exactly like all the other. The Schrödinger equation is ¸ ∙ 2 2 ~ ∂ −β(R−Req ) 2 + De [1 − e ] ψvib = Evib ψvib − 2μ ∂R2

(8.16)

This is another differential equation that is difficult to solve.

As it turns out, this Schrödinger equation can be transformed into a one of a broad class of known differential equations called confluent hypergeometric equations– the solutions of which are the confluent hypergeometric functions, 1 F1 . Doing this yields the wavefunctions of the form ψvib,n (z) = z Apn e−z 1 F1 (−n, 1 + 2Apn , 2z), √ 2De μ −βx e , z = βh √ 2μ , A = βh p −1 − n pn = De + 2 A and energy levels of the form 1 1 Evib,n = −De + hc˜ e (n + ) − hc˜ e xe (n + )2 , ω ω 2 2 (8.17)

(8.18)

65

where ω e xe together is the anharmonicity constant, with xe = ˜ ∗ ∗ ∗ See Handout ∗ ∗∗ 8.2.2. Vibrational Spectroscopy

hc˜ e ω . 4De

Infrared (IR) and Raman spectroscopy are the two most widely used techniques to probe vibrational levels. The spectral peaks appear at v = ˜
4E hc

(in units of wavenumbers, cm−1 ).

The transition from the n = 0 to the n = 1 state is called the fundamental transition. Transitions from n = 0 to n = 2, 3, 4 · · · are called overtone transitions. Transitions from n = 1 to 2, 3, 4 · · · , n = 2 to 3, 4, 5 · · · , etc. are called hot transitions (or hot bands) Since the energy levels depend on mass, isotopes will have a different transition energy and hence appear in a different place in the spectrum. Heavier isotopes have lower transition energies.

66

9. Molecular Orbital Theory and Symmetry
9.1. Molecular Orbital Theory
One of the most important concepts in all of chemistry is the chemical bond. In freshman chemistry we learn of one model for chemical bonding–VSEPR (valence shell electron-pair repulsion) theory, where hybridized atomic orbitals determine the bonding geometry of a given molecule. We are now prepared to discuss a bonding theory that is more rigorously based in quantum mechanics. Basically we will treat the molecules in the same way as all our other quantum mechanical problems (e.g., particle in a box, harmonic oscillator, etc.) As you might expect, it is not possible to obtain the exact wavefunctions and energy levels so, we must settle for approximate solutions. As a first example, let us consider the molecular hydrogen ion H+ . 2 The Hamiltonianfor H+ is 2 ˆ ˆ ˆ ˆ ˆ H = TN + Tel + VNel + VNN 67
67

(9.1)

We use the Born-Oppenheimer approximation and treat the nuclear coordinates as a parameters rather than as variables. So we only worry about parts of the Hamiltonian that deal with the electron. The effective Hamiltonian becomes ˆ ˆ ˆ H = Tel + VNel e2 e2 −~2 2 ∇ − − . = 2me 4π 0 rA 4π 0 rB The eigenfunctions of this Hamiltonian are called molecular orbitals. The molecular orbitals are the analogues of the atomic orbitals. • Atomic orbitals: Hydrogen is the prototype and all other atomic orbitals are built from the hydrogen atomic orbitals. • Molecular orbitals: The hydrogen molecular ion is the prototype and all other molecular orbitals are built from the hydrogen molecular ion molecular orbitals. (9.2)

There is one significant difference between the above, which is the hydrogen atomic orbitals are exact whereas the hydrogen molecular ion molecular orbitals are not exact. In fact, we shall see that these molecular orbitals are constructed as linear combinations of atomic orbitals.

9.2. Symmetry
Let the atoms of the hydrogen molecular ion lie on the z-axis of the center of mass coordinate system.

68

z). y. That is ı ˆψ(x. −z) = aψ(x. • If a = +1 the molecular wavefunction is even with respect to inversion and is called gerade and labelled with a “g”: ˆψ g = ψg ı • If a = −1 the molecular wavefunction is odd with respect to inversion and is called ungerade and labelled with a “u”: ˆψ u = −ψu ı • The terms gerade and ungerade apply only to systems that posses inversion symmetry. ı • Moreover the eigenvalue a can be either +1 or −1. z) = ψ(−x. ˆ.Inversion symmetry • The potential field of the hydrogen molecular ion is cylindrically symmetric about the z-axis.3) Cylindrical symmetry 69 . −z). y. z) must equal the electron density at (−x. • Because of the symmetry the electron density at (x. −y. • The above symmetry therefore requires that the molecular orbitals be eigenfunctions of the inversion operator. y. (9. −y.

• The cylindrical symmetry implies that the potential energy can not depend on the φ. • The molecular wavefunction is described by an eigenvalue λ = 0. . . . ±1. — We use λ to label the molecular orbitals as shown in the table λ 0 label σ ±1 ±2 · · · π δ ··· Mirror plane symmetry 70 . ±2.

— If the eigenvalue is +1 (even with respect to σ h ) the molecular orbital ˆ is called a bonding orbital. 71 . but we will put that discussion off for the time being. ˆ • Thus the molecular wavefunction must be an eigenfunction of σ h with eigenˆ value ±1.• There is also a symmetry about the x-y plane called horizontal mirror plane symmetry: operator σ h . • There are also vertical mirror plane symmetries. — If the eigenvalue is −1 (odd with respect to σ h ) the molecular orbital ˆ is called an antibonding orbital.

1) and (1sB ) = ke−rB /a0 (10.1. Unfortunately we can’t have both. we need to find some useful approximations for them. Useful can mean qualitatively useful or quantitatively useful. Linear combination of the 1s atomic orbital from each H atom is used for the molecular orbital of H+ : 2 (1sA ) = ke−rA /a0 (10. LCAO–Linear Combinations of Atomic Orbitals Now that we know what symmetry the molecular orbitals must posses. We will discuss the approximation which models the molecular orbitals as linear combinations of atomic orbitals (LCAO).2) 72 72 . Molecular Orbital Diagrams 10.10. LCAO is qualitatively very useful but it lacks quantitative precision. Let us again consider the hydrogen molecular ion H+ : let one H atom be labelled 2 A and the other labelled B.

1. Classification of Molecular Orbitals With atoms we classified atomic orbitals according to angular momentum.4) (10. For molecular orbitals we shall also classify them according to angular momentum.1.We construct two molecular orbitals as Φ+ = C+ (1sA + 1sB ) and Φ− = C− (1sA − 1sB ) The normalization condition is Z Φ± Φ± dΩ = 1 (10.3) (10.5) As can be seen from the above figure. Φ+ represents a situation in which the electron density is concentrated between the nuclei and thus represents a bonding orbital. 73 . Conversely Φ− represents a situation in which the electron density is very low between the nuclei and thus represents an antibonding orbital 10. But we shall also classify them according to their inversion symmetry and wether or not they are bonding or antibonding.

The classification according to angular momentum is as follows. px ⇒ π etc. σ g is a bonding orbital and σ ∗ is an antibonding u orbital. The Hydrogen Molecule Let us now consider the hydrogen molecule. This molecules is a homonuclear diatomic with two electrons. The classification according to inversion symmetry is simply a subscript “g” or “u”. s ⇒ σ. For example. pz ⇒ σ. If the two atoms are infinitely far apart. λ 0 orbital symbol σ ±1 ±2 · · · π δ ··· Atomic orbitals with m = 0 form σ type molecular orbitals.g. e. Those with m = ±1 form π type molecular orbitals.. e. For example.2.g.. The classification according to bonding or antibonding is an asterisk is used to denote antibonding. 10. σ g or σ u etc. The ground state of the system would consist of two separate hydrogen molecules in their ground atomic states: (1s)1 74 .

There are two acceptable linear combinations.6) 75 .7) (10. u (10. It is now more appropriate to speak in terms of molecular orbitals. so one forms linear combinations of the atomic orbitals. These are σg = 1sA + 1sB and σ ∗ = 1sA − 1sB . their respective s orbitals begin to overlap.As the atom are brought closer together.

It can be shown mathematically that the energy level associated with σg is lower than σ∗ . The molecular orbital diagram for H2 is shown below Molecular orbital diagrams can be drawn for any molecule. u We can intuit this qualitatively however since the σ ∗ orbital must have a node u whereas the σ g does not. We will focus on the second row homonuclear diatomics and some simple heteronuclear diatomics. Molecular Orbital Diagrams The energy levels associated with the molecular orbitals are drawn schematically is what is called a molecular orbital diagram. 76 . It is also to be expected since we know H2 is a stable molecule. 10.3. Some get very complicated.

8) • Examples follow in the supplement. 77 .The molecular orbital diagrams for the second row homonuclear diatomics are rather simple. The supplement that follows this section contains some examples of heteronuclear diatomics. Bond order • One important property that can be predicted from the molecular orbital diagrams is bond order. Heteronuclear diatomics are some what more complicated since there is a disparity in the energy levels of the atomic orbitals for the separated atoms. This disparity is not present for homonuclear diatomics. A consequence of this energy level disparity is that molecular orbitals may be formed from nonidentical atomic orbitals. • Bond order is defined as BO = 1 (# of bonding electrons − # of antibonding electrons) 2 (10. ∗ ∗ ∗ See Supplement ∗ ∗∗ The supplement that follows this section contains examples for each of the second row diatomics. For example a high lying 1s orbital may combine with a low lying 2s orbital to form a σ molecular orbital.

The Complete Molecular Hamiltonian and Wavefunction We have discussed molecular vibrations which under the Born-Oppenheimer approximation are governed by the vibrational Hamiltonian and described by the vibrational wavefunction. Next semester we will discuss molecular rotations and just like for vibrations and electronic transitions they are governed by the rotational Hamiltonian and described by the rotational wavefunction.9) ´ ³ ˆ ˆ ˆ Hele + Hvib + Hrot ψele ψvib ψrot = (Eele + Evib + Erot ) ψele ψvib ψrot 78 .10. We can succinctly express the Schrödinger equation for a molecule as follows. Likewise we have discussed molecular orbitals which are the electronic wavefunctions.4. (Next semester will we look at the details of this for polyatomic molecules) ˆ Hmol Ψmol = Emol Ψmol (10.

An Aside: Light Scattering–Why the Sky is Blue This chapter addresses the topic of light scattering from two different perspectives. 11. we have to take several key results from that theory on faith. When the light interacts with the molecule an electric dipole is induced according to μ = αE.1) where α is the polarizability of the molecule describing the “flexibility” of its electron cloud. 79 79 .1. The Classical Electrodynamics Treatment of Light Scattering As usual we work under the electric dipole approximation and only focus on the interaction of the electric field part of light with a dipole. • Classical electrodynamics • Classical statistical mechanics Since this is not a course on electrodynamics.11. (11.

2) The polarizability also depends on the positions of nuclei to some degree.4) where a trig identity was used in the last step. Thus the light—matter interaction is described as μ(t) = α(t)E(t) = (α0 + α1 cos ω v t) E0 cos ωt = α0 E0 cos ωt + α1 E0 cos ω v t cos ωt ⎡ ⎤ α1 E0 ⎣ cos(ω − ω v )t + cos(ω + ω v )t ⎦ = α0 E0 cos ωt + | {z } {z } | {z } | 2 Rayleigh Stokes Raman AntiStokes Raman (11. In this case we see the dipole oscillates at three distinct frequencies: ω.For light.3) (11. That is. there is a vibrational (and rotational) contribution to the polarizability: α(t) = α0 + α1 cos ωv t (here for simplicity we assume only one vibrational mode). the electric field part is E(t) = E0 cos ωt. The first term corresponds to Rayleigh scattering where the scattered light is at the same frequency as the incident light. ω − ωv and ω + ω v as part of three terms in the above expression. According to classical electrodynamics an oscillating dipole emits an electromagnetic field at the oscillation frequency. The second term corresponds to Stokes Raman scattering where the scattered light is shifted to the red of the incident frequency. 80 . (11.

There is a very strong dependence on frequency (or wavelength). This quartic scattering dependence is. To explicitly derive this expression we would need a fair bit of electrodynamics and so the derivation is not shown here. 11. The important point to note is that I ∝ ω 4 or alternatively I ∝ 1/λ4 . Classical electrodynamics can describe exactly how the oscillating electric dipole emits electromagnetic radiation. The Blue Sky The spectrum of visible light from the sun incident on the outer atmosphere is essentially flat as shown below.2. the reason why the sky is blue (from the point of view of classical electrodynamics) and is called the Rayleigh scattering law. in fact.The third term corresponds to anti-Stokes Raman scattering where the scattered light is shifted to the blue of the incident frequency.5) where μ0 = α0 E0 for the case of Rayleigh scattering and μ0 = α1 E0 /2 for the case of Raman scattering. 81 . 3c3 0 (11. It can be shown that the emitted intensity is I= ω4 2 μ.

Sunsets We have focused on a blue sky.2. 82 .1.We just learned that light scatters as it traverses the atmosphere according to Rayleigh’s scattering law: I(λ) ∝ 1/λ4 . 11. The following figures illustrate why Rayleigh scattering implies that the sky is blue. but red sunsets occur for the same reason– Rayleigh scattering.

11. This more pronounced at dawn or dusk since the light must traverse more of the atmosphere at those times then at noonday at which time the sun appears yellow in color. 83 .2.2.If we look directly at the sun during a sunset (or sunrise) it appears red because most of the blue light has scattered in other directions. White Clouds We might expect that clouds should be highly colored since they consist of droplets of water which scatter light very effectively.

In some contexts. The water droplets are much larger than the wavelenght of the light–quite the opposite case as above. In this limit an entirely different analysis is made–one does not have Rayleigh scattering but instead has a process called Mie scattering.The key difference between light scattering by clouds versus by the atmosphere is the size of the scatterer. Mie scattering is referred to as Tyndall scattering 84 . particularly in liquid suspensions.

Key Equations for Exam 2 Listed here are some of the key equations for Exam 2. φ) = Rnl (r)Ylm (θ. This section should not substitute for your studying of the rest of this material. θ. (11. φ) • The radial part is. The equations are collected here simply for handy reference for you while working the problem sets.8) na0 2n[(n + l)!]3 85 85 . depends on the n and l quantum numbers as sµ ¶3 2Z (n − l − 1)! Anl = − (11.7) where the normalization constant. Rnl (σ) = Anl (11. Anl . Equations • The wavefunctions for the hydrogenic system are ψnlm (r. The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations.6) µ 2σ n ¶l e −σ/n 2l+1 Ln+1 µ 2σ n ¶ .

10) where An is the normalization constant for the nth eigenfunction and Hn (y) are the Hermite polynomials. (11. (11. • The energy levels for the Morse oscillator are of the form 1 1 ω ω Evib. 2 2 where ω e xe together is the anharmonicity constant.12) q μ where De is the well depth and β = 2πc˜ e 2De is the Morse parameter.Ee (R → ∞) = 0). .11) Ee (R) = De [1 − e−β(R−Re q ) ]2 . • The Morse Potential can also be written as Ee (R) = De [e−2β(R−Req ) − 2e−β(R−Req ) ]. • The energy levels are 1 En = (n + )~ω. with xe = ˜ hc˜ e ω . An = p √ . .n = −De + hc˜ e (n + ) − hc˜ e xe (n + )2 . R = Req .• The energy levels for the hydrogenic system are given by En = − Z 2R n2 (11. R → ∞. ω Note: this expression for the Morse potential has the zero of energy at the bottom of the well (i. 4De (11.e.13) Now the zero of energy is the dissociated state (i. ω = 2 • The Morse potential is r k m (11.Ee (Req ) = 0).14) 86 .e.9) • The wavefunctions for the harmonic oscillator are ¶1 µ 2 km 4 1 − y2 ψ n (y) = An Hn (y)e . 2 n n! π ~ 2 (11. y = x.

16) 87 .15) • The Rayleigh scattering law is I(λ) ∝ 1/λ4 ∝ ω 4 (11.• Bond order is defined as BO = 1 (# of bonding electrons − # of antibonding electrons) 2 (11.

Part III Statistical Mechanics and The Laws of Thermodynamics 88 88 .

to write down and solve the Schrödinger equation for those 100 million molecules. which allows one to handle macroscopic sized systems without losing to much of the rigor. Statistics and Entropy Probability and statistics is at the heart of statistical mechanics. 12. Rudiments of Statistical Mechanics When we study simple systems like a single molecule. We will need some definitions • Ensemble: A large collection of equivalent macroscopic systems. The systems are the same except that each one is in a different so-called microstate.12. quantum mechanics. but often Avogadro’s number of molecules. even with the fastest computers. However. most of the time in the real world we are dealing with macroscopic systems.1. say. 89 89 . It is simply impossible. at least 100 million molecules. So we need a less detailed theory called statistical mechanics. we use a very detailed theory.

12. This is given by the mathematical formula for combinations C(N. Boltzmann developed an equation to connect the microscopic properties of an ensemble to the macroscopic properties..1) The number C(N. One valuable piece of statistical information about system is knowing how many different ways the system appears p times in. • Configuration: The collection of all equivalent microstates. p) is also called the binomial coefficient because it gives the coefficient for the pth order term in the expansion (1 + x) = N N X p=0 C(N. p) = N! .• Microstate: The single particular state of one member of the ensemble given by listing the individual states of each of the microscopic systems in the macroscopic state.1.3) 90 . say.g. p)xp . outcome 1 after N measurements. flipping coins). Combinations and Permutations Consider a random system that when measured can appear in one of two outcomes (e. (12. The Boltzmann equation is S = k ln W Where S is entropy and k is Boltzmann’s constant.1. p!(N − p)! (12.2) (12. The number of possible configurations is defined as W.

{Ni }) = N! N1 !N2 !N3 ! · · · (12. Set x = 1 in the above. p) = 1 1 N! C(N. Sometimes the order is important. p)(1)p (12.6) where N is the total number of measurements and Ni is the number of indistinguishable results of type i. So the probability of any one outcome of N measurements is P (N. So rather than a particular combination. This is given by W (N.This formula will allow us to derive a normalization constant so that we can obtain the probability of obtaining p measurements of state 1.5) For combinations we did not care what order the results of the measurements occurred. 91 . ∗ ∗ ∗ See Examples on Handout ∗ ∗∗ For both combinations and permutations we need to evaluated factorials. p).4) 2N = C(N. we are interested in a particular permutation. This gives (1 + 1) N = N X p=0 N X p=0 C(N. p) = N N 2 2 p!(N − p)! (12.

Often this fluctuation is not important.This is no problem for small numbers. the value of a certain property fluctuates about the average value. ¯ O N where N is the number of particles. we speak of the average value of the property. Consequently. It can be shown that (12. but when we consider macroscopic systems (1020 or so molecules) no calculator can handle factorials of such large numbers. but sometimes it is important. Fluctuations When we list the macroscopic properties of a material such as a beaker of benzene or the air of the atmosphere. Macroscopic equilibrium is a dynamic rather than static equilibrium. • Sterling’s approximation is ln(N!) ' N ln N − N (12.2. So for example if N = 1024 then (12. The fluctuation about an average value for any observable property O is described by the variance which is defined as ¯ σ 2 ≡ O2 − O2 .7) 12.9) 1 √ N = 10−12 92 . O σ O is consider the range of the observable property.8) σO 1 ≈√ . Sterlings Approximation: • In place of evaluating factorials of large number one can use Sterling’s approximation to approximate the value of the factorial.

93 .For ensembles having large numbers of particles measured values of a property are extremely sharply peaked about the average value.

(13. and the total number of particles will be constant.2) The number of configurations for the system is then given by the number of distinct permutations of the system W = N! .13. E. 94 94 . N1 !N2 ! · · · (13. The total number of particles is. of course. N= X i X i Ni i .3) A system in equilibrium always tries to maximize entropy and minimize energy and so the equilibrium configuration is a compromise between these two cases. Since the system is isolated the total energy.1) Ni (13. The Boltzmann Distribution Consider a isolated system of N molecules that has the set { i } energy levels associated with it. The total energy is given by E= where Ni is the number of particles in energy state i.

The derivation using Lagrange multipliers arrives at the configuration in which the gi e−β i Ni = N P .For the moment let us relax the isolation constraint. Maximizing entropy corresponds to maximizing W (via S = k ln W ).4) −β j j gj e | {z } pi where β ≡ 1 kT and gj denotes the degeneracy of states having energy j. E and number of particles N To determine the equilibrium configuration we must find the maximum W subject to the constraint of constant energy and constant number of particles. This would be the situation in which every particle was in a different energy state. These two situations are contradictory and some compromise must be obtained. We will not discuss this method in detail and consequently we cannot derive the equilibrium configuration. This is done using the mathematical technique of Lagrange multipliers (page 951 of your calc book). That is all Ni = 1 or 0. 95 . We start by considering our original system–that being one with constant energy. (13. Minimizing energy would be the case where all the particles are in the ground state (say 1 ).

A given energy E will correspond to a unique temperature T.5) j Since we started with a isolated system.6) and is called the canonical partition function. This partition function is not very useful to us so we will not discuss it further. This is called the microcanonical partition function. 13. The analysis readily generalizes to variable energy i.. The second partition function is Q= X j gj e−βEj (13. β and hence T are constants.1. This is the Boltzmann distribution gi e−β i Pi = P −β j gj e (13. nonisolated systems by considering T as a variable. 96 .e. The first is W –the number of configurations. Partition Functions We have already come across both the partition functions that we will use in this class.The pi represents the probability of finding the a randomly chosen particle or system which has energy i .

the partition function contains all that can be known about the ensemble.1.This was first encountered as the denominator of the Boltzmann distribution and it is extremely important in statistical mechanics. In fact we have already seen this in the S = k ln W. That is. (Note: the symbol Z is also often used for the canonical partition function. 97 . It is not an exact relation as we derive it. We shall see in the next chapter that the partition function will provide a link between the microscopic (quantum mechanics or classical mechanics) and the macroscopic (thermodynamics). for among other reasons.1.) The partition function is to statistical mechanics as the wavefunction is to quantum mechanics. There are other partition functions that are useful in different situations but we will do nothing more than list two important ones here: i) the grand canonical partition function and ii) the isothermal—isobaric partition function 13. energy levels and temperature do not explicitly appear. But this an inconvenient connection because. Relation between the Q and W When we get to connecting quantum mechanics with thermodynamics it will prove convenient to use Boltzmann’s equation (S = k ln W ) but as was stated earlier it is not convenient to use the microcanonical partition function (W ). but it is a very good approximation for large numbers of particles. In the following we give an argument which provides a relation between the partition functions.

The microcanonical partition function describes a system at fixed energy E. In fact W is the number of available states of the ensemble at the particular energy E. This is essentially the same as the degeneracy of the ensemble gE . Conversely the canonical partition function describes a system with variable energy. However, based on our previous discussion of fluctuations, even though the energy of the ensemble is allowed to vary, the number of states with energy equal to the ¯ average energy E is overwhelmingly large. That is, almost every state available ¯ to the ensemble has energy E. We can express these ideas mathematically to come up with a relation between W and Q. The canonical partition function is Q= but to a good approximation Q ' gE e−β E . ¯
¯

X
j

gj e−β j ,

(13.7)

(13.8)

Now since the degeneracy is essentially the microcanonical partition function we have ¯ (13.9) Q ' W e−β E . So the canonical partition function is a Boltzmann weighted version of the microcanonical partition function. We will soon make use of the Boltmann’s equation in terms of the canonical

98

partition function: ln Q ' ln(W e−β E ) = ln W + ln(e−β E ) ¯ E = ln W − | {z } kT .
S/k ¯ ¯

(13.10)

so,

S = k ln Q +

¯ E T

(13.11)

13.2. The Molecular Partition Function
We ended the previous chapter by stating the total molecular energy (about the center of mass) as = ele + vib + rot . (13.12) This is a consequence of the Born Oppenheimer approximation If we include the center of mass translational motion this is = The ith total energy level is
i ele

+

vib

+

rot

+

trans

(13.13)

=

ele,n

+

vib,v

+

rot,J

+

trans,m .

(13.14)

Now if we have a collection of molecules in a macroscopic system. A given configuration (say, configuration j) of that system has total energy Ej . So the canonical partition function is Q= X
j

gj e−βEj

(13.15)

99

But, each Ej is made up of the contributions of all of the molecules: Ej =
a l

+

b m

+

c n

+ ···

(13.16)

The partition function for the molecule is written as Q = = X
j

gj e−βEj = gla e−β {z
a l

X |l

qm o l,a

where the qmol,i are the molecular partition functions.

}|m

X

l,m,n···

a gm e−β qm o l,b

X {z

b c (gla gm gn · · · )e−β( l + m + n +··· )
a m

a

b

c

(13.17)

}| n {z

X

a gn e−β n · · ·

a

qm o l,c

}

The total canonical partition function is the product of the molecular partition functions. For the case where the molecules are the same then all the qmol,i are the same: qmol,i = qmol thus qN (13.18) Q = mol . N! This allows us to focus only on a single molecule: qmol = X
i

gi e−β i = gele,n e−β
qele

X |n

n,v,J,m
ele ,n

X }| v

n s,m ) gele,n gvib,v grot,J gtrans,m e−β ( ele,n + v ib ,v + ro t,J + tra(13.19)

{z

X

gvib,v e−β
qv ib

v ib ,v

{z

}| J

X

grot,J e−β
qro t

ro t,J

{z

}|m

X

gtrans,m e−β
qtra n s

tra n s,m

{z

}

We now collect below the expression for each of these partition functions. You will get the chance to derive each of these for your home work

100

The Translational Partition Function qtrans = where V Λ3 (13.20)

h Λ≡ √ 2πmkT is the thermal de Broglie wavelength. The Rotational Partition Function (linear molecules)

(13.21)

We will discuss rotations next semester. However, the high temperature limit, which works for all gases (of linear molecules) except H2 is T (13.22) qrot ≈ σθr
h where θr ≡ 8π2 Ik (I is the moment of inertia) and σ is the so-called symmetry number in which σ = 1 for unsymmetrical molecules and σ = 2 for symmetrical molecules.
2

The Vibrational Partition Function qvib e− 2 β~ω 1 = = −β~ω 1−e 2 sinh 1 β~ω 2
1

(13.23)

Note this is for the harmonic oscillator. At temperatures well below the dissociation energy this is a very good approximation. (You will derive this as a homework problem.) The Electronic Partition Function There is usually only a very few electronic states of interest. Only at exceedingly high temperatures does any state other that the ground state(s) become important

101

so qele =

X
i

gele,i e−β

tele ,i

≈ gele,ground

(13.24)

102

14. Statistical Thermodynamics
The partition function allows one to calculate ensemble averages which correspond to macroscopically measurable properties such as internal energy, free energy, entropy etc. In this chapter we will obtain expressions for internal energy, U, pressure, P, entropy, S, and Helmholtz free energy, A. With these quantities in hand we will, in the subsequent chapters, formally develop thermodynamics with no need to refer back to the partition function. Ensemble averages The ensemble average of any property is given by 1 X ¯ O= Oi gi e−β i . Q i Internal energy One critical property of an ensemble is the average (internal) energy U. 1 X −β i ¯ . U ≡E= i gi e Q i Let us look closer at the above expression. Recall that Q= X
i

(14.1)

(14.2)

gi e−β i .

(14.3)

103
103

Now take the derivative of Q with respect to β gives à #! " ¶ µ X µ ∂e−β i ¶ ∂ X −β i ∂Q = gi e = gi ∂β n,V ∂β i ∂β n,V i n,V X = − gi i e−β i
i

(14.4)

By comparing this to the expression for U, we see µ ¶ ¶ µ 1 ∂Q ∂ ln Q U =− =− , Q ∂β n,V ∂β n,V where we used the identity
1 ∂y y ∂x

(14.5)

=

∂ ln y . ∂x

Pressure Another important property is pressure. When the ensemble is in the particular state i, d temperature and number of particles ¶ µ ∂ i pi = − ∂V n,β
i

= −pi dV . So at constant (14.6)

Thus the ensemble average pressure is given by ¶ µ 1 X ∂ i P =p=− ¯ gi e−β i . Q i ∂V n,β Multiplying by β/β we get 1 X P =− gi βQ i Using the chain rule in reverse, i.e., ∂e−β ∂V z }| ¶ µ ¶ µ ¶ µ −β i { ∂ i ∂e ∂ i = =− βe−β ∂ i ∂V ∂V
−βe−β
i

(14.7)

µ

∂ i ∂V

βe−β i .

(14.8)

n,β

i

i

(14.9)

104

10) 105 .β Entropy We have already obtained the expression for entropy.11) (14.we proceed as ! Ã µ −β i ¶ ∂e 1 1 X ∂ X −β i P = gi = gi e βQ i ∂V βQ ∂V i n. βQ ∂V n.β n.β β ∂V n. It is S = U + k ln Q T µ ¶ ∂ ln Q = −kβ + k ln Q ∂β n.β µ ¶ µ ¶ ∂Q 1 1 ∂ ln Q = = .V (14.

106 . The Helmholtz free energy has the most direct relation to the partition function as can be seen from µ ¶ ¶ µ ∂ ln Q ∂ ln Q A ≡ U − TS = − + kT β − kT ln Q (14. That is.V n. it is the energy of the system minus the energy that is “tied-up” in the random (unusable) thermal motion of the particle in the system: A ≡ U − T S Free energy is probably the key concept in thermodynamics and so we will discuss it in much greater detail later.Helmholtz Free Energy Free energy is the energy contained in the system which is available to do work.V = −kT ln Q Any thermodynamic property can now be obtained from the above functions as we shall see in the following chapters.12) ∂β ∂β n. We will make the distinction between the Helmholtz free energy and the more familiar Gibb’s free energy (G) later as well.

15.15. ∗ ∗ ∗ See Handout ∗ ∗∗ 15. Work We now begin the study of thermodynamics.1) (15. Thermodynamics is a theory describing the most general properties of macroscopic systems at equilibrium and the process of transferring between equilibrium states.2) .1.1. y): µ ¶ µ ¶ ∂z ∂z dz = dx + dy ∂x y ∂y x 2. The total derivative of z(x. Summary of Relations 1. Thermodynamics is completely independent of the microscopic structure of the system. The chain rule for partial derivatives: µ ¶ µ ¶ µ ¶ ∂u ∂z ∂z = ∂x y ∂u y ∂x y 107 107 (15.1. Properties of Partial Derivatives Of critical importance in mastering thermodynamics is to become proficient with partial derivatives.

Definitions System: a collection of particles Macroscopic systems: Systems containing a large number of particles.2. 15.3) y 4. The cyclic rule: ¶ y ∂z =− ∂y ∂z ∂x ¶ µ ¶ µ x ∂y ∂x (15.4) ¶ z 5.2. The reciprocal rule: µ µ ∂z ∂x ∂z ∂x ¶ µ y ∂x ∂z ¶ =1 ¶ (15. Closed system: A system that cannot exchange matter with its environment but may exchange energy. Microscopic systems: Systems containing a small number of particles. Environment: Everything not included in the system (or set of systems) Note that the distinction between the system and the environment is arbitrary and is chosen as a matter of convenience.1.5) u 15.3. 108 . Finally µ ∂z ∂x ¶ = u µ + y µ ∂z ∂y ¶ µ x ∂y ∂x (15. Types of Systems Isolated system: A system that cannot exchange matter or energy with its environment.

3. density. 109 . • For example. 15. heat capacity. Extensive property For example mass volume (15. Intensive parameters (or properties): properties that are independent of the amount of matter. volume. heat capacity mass 15. = density. volume moles = molar volume.Open system: A system that may exchange matter and energy with its environment. Extensive properties can be “converted” to intensive properties through ratios: Extensive property → Intensive property.2. mass. • Heat is exchanged if only internal parameters are changed during the process. System Parameters Extensive parameters (or properties): properties that depend on the amount of matter. • For example. Adiabatic system: A closed system that also can not exchange heat energy with its environment. Work and Heat A system may exchange energy with its environment or another system in the form of work or heat.2.6) = specific heat. • Work is exchanged if external parameters are changed during the process. pressure. temperature.

we need a more general definition if infinitesimal work.g. dx: dw = F dx. times and infinitesimal change in position. Newtons) and the generalized displacement need not have units of position (e. The infinitesimal amount of work done on the system is then given by dw = Ada.7) For thermodynamics. a.9) 110 . meters). Joules). which acts as ‘generalized displacement. Heat. w.8) Ai dai (15..Convention Work. (15. 15.g. F . is positive (w > 0) if work is done on the system.1... A may be considered as a ‘generalized force’ which is coupled to a particular internal parameter. Heat is negative (q < 0) if heat is released from the system. q. Work is negative (w < 0) if work is done by the system. but the product of the two must have units of energy (e.g.’ Note that the generalized force need not have units of force (e. Any given external parameter. or more generally as dw = X i (15. is positive (q > 0) if heat is absorbed by the system.3. Generalized Forces and Displacements In physics you learned that an infinitesimal change in work is given by the product of force.

E Magnetic Field. dn Height. The following table gives some examples of generalized forces and displacements Generalized Force. dQ Magnetization. a Contribution to dw Pressure.2. dV Strain. −P Stress.if more than one set of parameters change. dM Moles. γ Voltage. dh −P dV σdε γdA EdQ HdM μdn mgdh 15.10) Expanding Gases Consider the work done by a gas expanding in piston from volume V1 to V2 against some constant external pressure P = Pex (see figure) 111 . P V work In principle all work is interchangeable so that without loss of generality we will develop the formal aspects of thermodynamics assuming all work is due to changes in volume under a given pressure. dε Surface area. dA Charge. When we get to applications of thermodynamics we will then be concerned with the various forms of work like those shown in the table above. mg Volume. H Chemical Potential. That is dw = −P dV. this is called P V work. μ Gravity.3. σ Surface tension. A Generalized Displacement. (15.

This can be manipulated as Z x2 Z x2 Z V2 F w=− F dx = − Adx = − Pex dV (15.12) 112 .11) A |{z} x1 x1 |{z} V1 dV Pex If Pex is independent of V then Z Z V2 Pex dV = −Pex w=− V1 V2 V1 dV = −Pex 4V (15.The force exerted on a gas by a piston is equal to the external pressure times the area of the piston: F = Pex A ⇒ Pex = F/A. Rx Recall from physics that work is the (path) integral over force: w = − x12 F dx.

Maximal Work: Reversible versus Irreversible changes The value of w depends on Pex during the entire expansion. 16.1) 113 113 .1. Maximum Work and Reversible changes Now that we have learned about PV work we will consider the situation where the system does the maximum amount of work possible.16. In the figure wA = − Z V2 V1 Patm dV = −Patm (V2 − V1 ) (16.

there is always an intermediate equilibrium throughout the expansion.3) w2 = − Vi Patm dV = −Patm (V2 − Vi ) (16. 114 .2) V1 Patm+2W dV = −Patm+2W (Vi − V1 ) Z V2 (16.and wB = w1 + w2 . Thus wrev is the maximum possible work that can be done in an expansion. Namely Pgas = Pex .5) V1 This is the limiting case of path B in the previous figure. That is. wrev = wmax .4) Hence it is clear that |wB | > |wA | . So. wrev = − Z V2 Pgas dV (16. where w1 = − and Z Vi (16. Now consider case in the figure below The expansion is reversible.

µ dq dT ¶ (16.. To make an intensive property 1. Heat Capacity Temperature and heat are different.7) That is. Temperature is an intensive property and heat is an extensive property. C(T ) = From this equation dq = C(t)dT.16. The heat capacity also depends on the conditions during the temperature change. it is not a constant.9) V 115 . ¡ dq ¢ ¡ dq ¢ e. heat is related to temperature through the heat capacity dq dT n..b.8) (16. divide by the number of moles to get molar heat capacity µ ¶ 1 dq CV m (T ) = n dT V 2.6) (16.2.g. However. dq amount of heat energy is transferred. CV (T ) = dT V and CP (T ) = dT P are not the same Heat capacity is an extensive property. heat capacity is a function of T . when the temperature of a substance having a heat capacity C(t) is changed by dT. divide by mass to get specific heat 1 cV = m We will discuss heat capacity more later. Temperature is not the amount of heat. (16.

so we will focus our development of thermodynamics on simple systems. (16. ρ= nRT RT (and molar (16.16. 16. P independent then heat capacity is a function of T and P .3. C(T.) The functional dependence of any property on the two independent variables is an equation of state.11) where Vm = V .315 J K−1 mol−1 ) and n is the number of moles. e.g. Example 1: The Ideal Gas Law The equation of state for volume of an ideal gas is P V = nRT . (More complicated systems require more than two independent variables. T .1. The ideal gas equation of state can be expressed in terms of intensive variables only P Vm = RT . but behave in the same way as the more simple pure system. The state of a pure. Equations of State The macroscopic properties of matter are related to one another via a phenomenological equation of state.12) 116 .10) where R is the gas constant (8. homogeneous material (in the absence of external fields) is given by the values of any two intensive properties.. n m V The equation of state can also be expressed in terms of density ρ = mass m/n) MP mP = . P ). (16.3.

3.13) The parameter a attempts to account for the attractive forces among the particles The parameter b attempts to account for the repulsive forces among the particles b originates from hard sphere collisions (see figure): 117 . V − nb V (16.2.16. Example 2: The van der Waals Equation of State A more realistic equation of state was presented by van der Waals: P = nRT n2 a − 2.

Vm − b Vm (16.17) 118 .3. Some other equations of state are • Berthelot • Dieterici n2 a a nRT RT − − = 2 2 V − nb T V Vm − b T Vm an a P = (16. Other Equations of State The van der Waals equation of state is not the only one that has been proposed.15) RT e− RT Vm nRT e− RT V = P = V − nb Vm − b nRT n2 a a RT −√ −√ = V − nb Vm − b T V (V − nb) T Vm (Vm − b) (16.14) 16.In term of intensive variables P = a RT − 2.16) • Redlich-Kwang P = (16.3.

Today we will cover the zeroth and first laws. Temperature scales • Celsius: A relative scale based on water (T = 0◦ C for melting ice and T = 100◦ C for boiling water) • Kelvin: An absolute temperature scale based on the ideal gas law. 17. Temperature and the Zeroth Law of Thermodynamics Temperature tells us the direction of thermal energy (heat) flow. Next time we will cover the second and third laws which both deal with entropy.17. • Heat flows from high T to Low T. which deal with temperature and total energy respectively.1.15 119 119 . The temperature at which (for fixed V and n) the pressure is zero is defined as T =0K • T (Kelvin) = T (Celsius) + 273. The Zeroth and First Laws of Thermodynamics Over the course of the next two lectures we will discuss the four core laws of thermodyanmics.

then the systems are in thermal equilibrium. (Vm (STP) = 22. C. then TA = TC This the mathematical statement of transitivity • Verbal statement: If system A is in thermal equilibrium with system B and system B is in thermal equilibrium system C then system A is also in thermal equilibrium with system C. is chosen as a thermometer then it will read the same temperature when it is in thermal contact along a diathermic wall with system A as when it is in thermal contact along a diathermic wall with system B.15 K and P = 1 bar. Thermal equilibrium: If two systems are in contact along a diathermic wall and no heat flows across the wall.789 L/mol) Diathermic wall: A wall that allows heat to flow through it. 120 .1) The zeroth law implies that if an arbitrary system.Standard conditions • standard temperature and pressure (STP): T = 273. The zeroth law of thermodynamics • Mathematical statement: If TA = TB and TB = TC . Adiabatic wall: A wall the does not allow heat to flow through it. (17.15 K and P = 1 atm. (Vm (SATP) = 24.414 L/mol) • standard ambient temperature and pressure (SATP): T = 298.

The value of the state function depends only on that given state and on no other possible state of the system.17.. V (T.2. The First Law of Thermodynamics Definitions: • State: the state of a system is defined by specifying a minimum number in intensive variables • State Function: A function of the chosen independent variables that describes a property of the state (e.1.3) 4U = q + w (17.2. The first law of thermodynamics: • Mathematical statement: or in differential form dU = dq + dw (17. The internal energy state function For characterizing the change in energy of a system.4) 121 . P )). The energy of a system is called the internal energy (U) of the system. 17.2) • Verbal statement: The change in internal energy of a system is equal to the amount of work done on the system plus the amount of heat provided to the system. one is concerned with the work done on the system (w) and the heat supplied to the system (q).g. So for a system where all the work is P V work the first law becomes Z V2 4U = q − Pex dV V1 (17.

∂T The other slope.8) .5) Although U can be expressed as a function of any two state variables.6) (17.10) V 122 . is called the internal pressure (it has no standard symbol). V ) is µ ¶ ¶ µ ∂U ∂U dU = dT + dV ∂T V ∂V T Consider adding heat at a constant volume then ¶ ¶ µ µ ∂U ∂U dT + dV = dq − Pex dV.7) µ (17. ¡ ∂U ¢ ∂V T (17. A useful relation (derivation to come) is ¶ ¶ µ µ ∂U ∂P =T −P ∂V T ∂T V Example: A van der Waals gas n2 a nRT − 2 ⇒ P = V − nb V µ ∂P ∂T ¶ = nR V − nb (17. The total differential of U (T.in differential form this is dU = dq − Pex dV (17. U → U(T. V ).9) (17. dU = ∂T V ∂V T So. the most convenient at this time are V and T. ¶ ¶ µ ∂U ∂U dq = CV dT = dq =⇒ = ∂T V ∂T V dT ¡ ¢ Hence the slope ∂U V is the heat capacity.

A useful approximation is 4U = CV 4T which is valid for i) heat capacity nearly constant over 4T and with no phase transitions. ii) ideal gas or at constant volume.12) (17. and P. Hence ∂T ∂T ¶ ∙ µ ¸ ∂P − P dV dU = CV dT + T ∂T V (17.so the useful relation becomes ¶ µ nRT nRT n2 a nR ∂U −P = − + 2 = T ∂V T V − nb V − nb V − nb V 2 na = + 2 V (17. V. 123 . Start with the total differential of U ¶ ¶ µ µ ∂U ∂U dT + dV dU = ∂T V ∂V T ¡ ∂U ¢ ¡ ¢ ¡ ¢ but ∂U V = CV and ∂V T = T ∂P V − P (useful relation).13) is the equation of state for U.11) The equation of state for U : Express U in terms of T.

1) T ¯ Now. (18. Hence. the average energy of the system E is in fact what we call internal energy: ¯ U ≡ E. S. U A 1 − = (U − A). A. The Second and Third Laws of Thermodynamics 18.18. Furthermore we derived the simple relation between the Helmholtz free energy and the canonical partition function as A = −kT ln Q.1. T T T Since U.3) 124 .2) 1 (dU − dA) T 124 (18. S= So we may write dS = (18. S is also a state function . is a measure of the disorder of the system and is expressed via Boltzmann’s equation S = k ln W (where W is the micocanonical partition function) We expressed Boltzmann’s law in terms of the more convenient canonical partition function as ¯ E S = + k ln Q. Entropy and the Second Law of Thermodynamics We learned from statistical mechanics that entropy. and T are state functions.

for an isothermal process. For now let us limit the discussion to reversible processes. Then dS = 1 1 (dU − dwrev ) = (dqrev + dw rev − dw rev ) / / T T dqrev .4) Note: An alternative approach to thermodynamics which makes no reference to molecules or statistical mechanics is to simply begin by defining entropy as dS ≡ dqrev T The principle of Clausius • “The entropy of an isolated system will always increase in a spontaneous process” • Mathematical statement: (dS)U. Recall the definition of Helmholtz free energy–the energy of the system available to do work. (Reversible process) = T (18. We learned previously that the maximum amount of work one can extract from the system is the work done during a reversible process.V ≥ 0 For a general process: dU = dq − Pex dV For a reversible process Pex = P and dq = T dS so dU = T dS − P dV 125 . Hence dA = dwrev .

5) 126 . dq − Pex dV = T dS − P dV ⇒ T dS = dq − Pex dV + P dV T dS = dq + (P − Pex ) dV • Case i) Pex > P then (spontaneous) dV is negative so (P −Pex )dV is positive. • Case iii) P = Pex then (spontaneous) dV is zero so (P − Pex )dV is zero. (see figure) T dS is heat and −P dV is work only for reversible processes. • Case ii) P > Pex then (spontaneous) dV is positive so (P −Pex )dV is positive. S. P. Thus for any spontaneous process T dS ≥ dq. For some dU. T dS is not heat and −P dV is not work. and V are state functions. This is a mathematical statement of the second law of thermodynamics (18.Since U. dU = T dS − P dV holds for any process. but in general. T.

Spontaneous processes are irreversible in character.1.7) T1 CV dT.18. Work must be done to transfer heat from a cold to a hot reservoir.2.1. A useful perpetual motion machine does not exist.8) 127 . The entropy of an isolated system will always increase in a spontaneous process (the principle of Clausius) 18. 4. the second law has a number of equivalent statements 1. dU = dq + dw = dq − Pex dV (18. 3. T (18. 2. So CV dT =⇒ 4S = dS = T Z T2 (18. Statements of the Second Law Unlike the first law. 6. The entropy of the universe is increasing 5. dU = CV dT but also dU = T dS. The Third Law of Thermodynamics Consider the first law for a reversible change at constant volume. A cyclic process must transfer heat from a hot to cold reservoir if it is to convert heat into work. So.6) From our earlier discussion of heat capacity dq = CV dT (CV since constant volume).

CO). O2 etc. Ar.A very similar derivation can be done for a reversible change at constant pressure (we can not do it quite yet) to yield Z T2 CP dT (18.. However. 128 .g.g.1.). Consider the heat capacity near T → 0.11) Hence the mathematical statement of the third law is Z T2 CP S(T2 ) = dT + S0 T 0 (18.9) 4S = T T1 18. For S0 to have significance CP T must be finite (not infinite) as T → 0.12) From a macroscopic point of view S0 is arbitrary. S0 6= 0 for imperfect crystals and crystals of asymmetric molecules (e.. Alternative statement of the third law: Absolute zero is unattainable. Thus CP → 0. a microscopic point of view suggests S0 = 0 for perfect crystals of atoms or of totally symmetric molecules (e.10) 4S = T T1 now let T1 → 0 4S = S2 − S0 = Z T2 0 CP dT T (18. The Third Law Verbal statement The third law of thermodynamics permits the absolute measurement of entropy.2. To derive the mathematical statement of the third laws we starting with Z T2 CP dT (18.

(Debye) Postulate: CP m = aT 3 . So. ∗ ∗ CP m .But CP = dq dT → 0 implies dT dq → ∞.2. So one needs a theoretical extrapolation down to T = 0. In other words. an infinitesimal amount of heat causes an infinite change in temperature. Debye’s Law Heat capacity data only goes down so far. a = CP m /T ∗3 . the ever present random fluctuations in energy provide the infinitesimal amount of heat and so you can never reach absolute zero corresponding to an average energy of zero.2. That is at low temperatures heat capacity goes as the cube of the temperature. 18. T ∗ are the lowest temperature data points. 129 . In view of what we have learned about fluctuations.

13) 0 Entropy and the second law give a direction to time. the behavior of the macrosystem definitely changes if you replace t with −t. For example. We know which picture was taken first.The molar entropy is Sm (T ) = = ∗ Z 18. Thus the simple fact that you have an enormous number of particles induces a perceived asymmetry in time. Times Arrow ∗ CP C =aT 3 CP m dT P m = T T ∗3 0 ¯T ∗ ∗ ∗ CP m T 3 ¯ ¯ = CP m . The interesting thing is that each molecule in a macroscopic system obeys time invariant dynamics. if we see a picture of your PChem book in mint condition and we see a picture of your PChem book all battered and beaten.3. T ∗3 3 ¯ 3 0 T∗ Z T∗ T 2 dT (18. 130 . Both Newton’s laws and Quantum dynamics (next semester) are the same if you replace t with −t. Yet.

The equations are collected here simply for handy reference for you while working the problem sets.15) • The canonical partition function is Q= gj e−βEj (18. The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations. This section should not substitute for your studying of the rest of this material. Equations • The Boltzmann equation is • The Boltzmann distribution : g e−β i P i −β j gj e X j j S = k ln W.16) 131 131 .14) (18.Key Equations for Exam 3 Listed here are some of the key equations for Exam 3. (18.

19) 2πmkT is the thermal de Broglie wavelength. 2 sinh 1 β~ω 2 (18.21) • The ensemble average of any property is given by 1 X ¯ Oi gi e−β i .β = β ³ =− + k ln Q ¡ ∂ ln Q ¢ ∂V ³ ∂ ln Q ∂β ´ n.V ¡ ∂Q ¢ 1 1 = βQ ∂V n.18) Λ where h Λ≡ √ (18. O= Q i (18. σθr 2 (18.22) • The relations between the canonical partition function and the thermodynamics variables are Internal energy Entropy Helmholtz Free Energy A = −kT³ln Q ´ 1 U = −Q ∂Q ∂β S Pressure P n. (18.20) h where θr ≡ 8π2 Ik (I is the moment of inertia) and σ is the so-called symmetry number in which σ = 1 for unsymmetrical molecules and σ = 2 for symmetrical molecules • The Vibrational Partition Function is qvib = 1 .• The relation between the partition function and the molecular partition function is qN Q = mol .V ´ ∂ ln Q = −kβ ∂β n.17) N! • The Translational Partition Function V qtrans = 3 (18.V n. • The Rotational Partition Function (linear molecules) is T qrot ≈ .β 132 .

(18. dU = T dS − P dV. in differential form this is dU = dq − Pex dV.23) (18. 3 (18.29) • Debye’s law for entropy at very low temperatures Sm (T ∗ ) = ∗ CP m .27) (18. Also.25) (18.24) 4U = q + w. dq = C(t)dT.28) 0 CP dT + S0 T (18.26) (18.• P V work is • Heat capacity: • General forms of the first law: dw = −P dV.30) ∗ where CP m is the molar heat capacity at the lowest temperature for which there is data. • The second law • The third law T dS ≥ dq. S(T2 ) = Z T2 (18. 133 .

Part IV Basics of Thermodynamics 134 134 .

19. the concept of equilibrium plays a key role in much of what we will discuss for the remainder of the year. The Other Important State Functions of Thermodynamics As was the case in quantum mechanics. So far we have encountered two state functions which characterize the energy of a macroscopic system–the internal energy and. Auxillary Functions and Maxwell Relations We have stated that thermodynamics as we are studying it deals with states in equilibrium or transitions between equilibrium states. electrochemistry. Consequently. here too is energy the key property with which to work. 135 135 . K. briefly the Helmholtz free energy. and kinetics–topics we will encounter throughout the year. (which you are familiar with from general chemistry) serves are a common point which connects thermodynamics. The equilibrium constant for a thermodynamic process. 19.1.

it is handy to define state functions which have different pairs of natural variables. (T and V ) and (T and P ) The table below lists these state functions State function Internal Energy Enthalpy Helmholtz free energy Gibbs free energy Symbol Natural variables U H A G S S T T and V and P and V and P Definition H ≡ U + PV A ≡ U − TS G ≡ H − TS Units energy energy energy energy We consider each of these functions in turn 19. V ) Unfortunately S can not be directly measured and most often P is a more convenient variable than V Because of this fact. 136 . This is U = U(S. so that no mater what situation arises we have convenient equations of state to work with.From the first law as stated as dU = T dS − P dV (19. The other pairs of natural variables being (S and P ).2. Enthalpy We want a state function whose natural variables are S and P Let us try the definition H ≡ U + P V.1) we say that the natural (most convenient) variables for the equation of state for U are S and V .

19.3.2.Now formally dH = dU + d(P V ) = dU + P dV + V dP.3) Enthalpy is the total energy of the system minus the pressure volume energy. Since the process is adiabatic no heat energy can flow in to compensate for the work done and the gas cools. 19. Helmholtz Free Energy Now we want a state function whose natural variables are T and V 137 . consider an reversibly expanding gas under constant pressure (dP = 0) and adiabatic (dq = 0) conditions. The total internal energy decreases. in doing so it must lose energy. Hence Enthalpy does indeed have the desired natural variables. So a change in enthalpy is the change in internal energy adjusted for the P V work done.1. The enthalpy of the system on the other hand does not change–it is the internal energy adjusted by an amount of energy equal to the P V work done by the system. so (19. As Freshmen we learn this as 4H = qp .2) / / dH = T dS − P dV + P dV + V dP = T dS + V dP. but dU = T dS − P dV. For example. The system does work during the expansion. Heuristic definition: (19. If the process occurs at constant pressure then the enthalpy change is the heat given off or taken in.

7) (19. but dU = T dS − P dV. but from above dH = T dS + V dP. Hence Gibbs free energy does indeed have the desired natural variables. Now formally dG = dH + d(T S) = dH − T dS − SdT.4) / / dA = T dS − P dV − T dS − SdT = −P dV − SdT.Let us try the definition A ≡ U − T S. Heuristic definition: As we have said before Helmholtz free energy is the energy of the system which is available to do work–It is the internal energy minus that energy which is “used up” by the random thermal motion of the molecules. 19. Formally dA = dU − d(T S) = dU − T dS − SdT. Gibbs Free Energy Finally we want a state function whose natural variables are T and P Let us try the definition G ≡ H − T S.4. so dG = T dS + V dP − T dS − SdT / / = V dP − SdT. (19.1.5) Hence Helmholtz free energy does indeed have the desired natural variables. 19. so (19.3.6) 138 . (19.

1.4.19.12) ∂T ∂T P ∂T P P ¡ ¢ ¡ ¢ note ∂U P is not CV we need ∂U V .5. 19. ¶ ¶ ¶ µ µ ∂ (U + P V ) ∂U ∂V CP = = +P (19.11) CP = ∂T P So. Heuristic definition: Gibbs free energy is the energy of the system which is available to do non P V work–It is the internal minus both that energy which is “used up” by the random thermal motion of the molecules and used up in doing the P V work. Heat Capacity of Gases 19.10) (19.13) P 139 .8) The constant pressure heat capcity can then be expressed in terms of enthalpy as ¶ µ ∂H . Use an identity of partial derivatives ∂T ∂T µ µ ∂U ∂T ¶ = P µ ∂U ∂T ¶ + V µ ∂U ∂V ¶ µ T ∂V ∂T ¶ (19.1.9) (19. (19. The Relationship Between CP and CV To find how CP and CV are related we begin with dH = T dS + V dP at constant pressure and reversible conditions dH = T dS dH = dq but dq = CP dT (19.5.

14) CP = ∂V T ∂T P ∂T P V ¶ ∙µ ¶ µ ¸ ∂U ∂V = CV + +P .15) ∂P ∂T ¶ (19.thus ¶ µ ¶ ¶ µ ∂V ∂U ∂V + +P (19.18) 19. ∂T P ∂V T ¡ ¢ ¡ ∂U ¢ Recall the expression for internal pressure ∂V T = T ∂P V − P .16) V Example: Ideal gases 1.6. Then ∂T µ ∂U ∂T µ CP = CV + Finally CP = CV + T µ ∂V ∂T ¶ ∙ µ ¶ ¸ ∂P T −P +P / / ∂T V P µ ∂V ∂T ¶ µ P ¶ (19.17) ∂T P ∂T V nRT nR nR = nR = CV + T P V PV Thus CP = CV + nR or CP m = CV m + R (19. Ideal gas (equation of state: P V = nRT ): This equation is easily made explicit in either P or V so we don’t need any of the above replacements ¶ µ ¶ µ ∂P ∂V CP = CV + T (19. The Maxwell Relations Summary of thermodynamic relations we’ve seen so far Definitions and relations: • H = U + PV 140 .

(See handout and Homework) 141 . CP = ¡ ∂H ¢ ∂T P basic equations dU = T dS − P dV dH = T dS + V dP dA = −P dV − SdT dG = V dP − SdT Maxwell relations ¡ ∂T ¢ ¡ ¢ = − ∂P V ∂V S ¡ ∂T ¢ ¡ ∂S ¢ = ∂V P ∂P S ∂S ¡ ∂S ¢ ¡ ¢ = + ∂P V ∂V T ¡ ∂S ¢ ¡ ∂T ¢ = − ∂V P ∂P T ∂T working equations £ ¡ ¢ ¤ dU = CV dT + T ∂P V − P dV ∂T £ ¡ ¢ ¤ dH = CP dT − T ∂V P − V dP ∂T ¡ ¢ dS = CV dT + ∂P V dV T ¡ ∂T ¢ dS = CP dT − ∂V P dP T ∂T We will get plenty of practice with derivations based on these equations and on the properties of partial derivatives.• A = U − TS • G = H − TS • CV = ¡ ∂U ¢ ∂T V .

V = 0. Chemical Potential 20.1.20.1) (20. Hence at equilibrium (dA)T. The tendency to maximize entropy Let us begin with Helmholtz free energy The total differential of A is (A = U − T S) dA = dU − T dS − SdT = dq − Pex dV − T dS − SdT For constant T and V. For chemistry it is most often more convenient to use Gibbs free energy The total differential of G is dG = dH − T dS − SdT = dq − Pex dV + P dV + V dP − T dS − SdT 142 142 (20.2) . The tendency to minimize energy 2. T dS ≥ dq for a spontaneous process.V = dq − T dS From the second law.V ≤ 0 for a spontaneous process. Spontaneity of processes Two factors drive spontaneous processes 1. (dA)T. (dA)T.

Hence at equilibrium (dG)T.P ≤ 0 for a spontaneous process.4) Expressing dU and dH generally as dU = T dS − P dV and dH = T dS + V dP (remember that in general T dS cannot be identified with dq and P dV cannot be identified with −w). So free energy provides a measure of the thermodynamic driving force towards equilibrium.P = dq − T dS Again from the second law. dA = dU − T dS − SdT and dG = dH − T dS − SdT.5) (20. Note free energy provides no information about how fast a process proceeds to equilibrium. (20. (dG)T. (dG)T.6) (20. T dS ≥ dq for a spontaneous process. Plugging these into the total differentials of free energy gives dA = −SdT − P dV and dG = −SdT + V dP (20.P = 0. The free energy functions are the workhorses of applied thermodynamics so we want to get a feel for them.For constant T and P = Pex .3) 143 . Returning to the total differentials of free energy.

P = dq + w0 − T dS.10) So. For a reversible process dq = T dS and work is maximal. The total differential of A is also dA = dq + dw − T dS − SdT. The total differential of G is also dG = dq + dw + P dV + V dP − T dS − SdT.P = wmax (20. Chemical potential What if the amount of substance can change? 144 . The total differential of G becomes dG = dq + dw0 − Pex dV + P dV + V dP − T dS − SdT. In general dw = dw0 − Pex dV where dw0 is the non-P V work. but i) only P V work and ii) closed systems. the Gibbs free energy is the energy of the system available to do non-P V work.P = dwmax =⇒ (4G)T.2. (dG)T. As we have stated in words a number of times before. Hence (dA)T = dwmax =⇒ (4A)T = wmax . 20. as stated earlier.7) (20. For constant T and P = Pex . For reversible processes q = T dS and this becomes 0 0 (dG)T.8) (20.These expressions are quite general.9) (20.

(20.13) = −SdT − P dV + P dV + V dP + μdn / / / / = −SdT + V dP + μdn. n) = dT + dV + dn (20. V. • This is a measure of the change in Helmholtz free energy of a system (at constant T and V ) with the change in the amount of material.Extensive properties depend on the amount of “stuff” For example A(T. • It defines the chemical potential μ ≡ So we can also write dA = −SdT − P dV + μdn What about the relation of the chemical potential to Gibbs’ free energy? G = H − T S = U − T S + P V = A + P V so. this is a measure of the potential to change the amount of material.14) P.T . | {z } =A ¡ ∂A ¢ ∂n V.T 145 . but from dG = µ ∂G ∂T ¶ dT + µ ∂G ∂P ¶ dP + µ ∂G ∂n ¶ dn (20. n) and the total differential becomes µ ¶ ¶ µ µ ¶ ∂A ∂A ∂A dA(T.11) ∂T V.n ∂V T.T . • Physically.n ∂n V. V.n T. V ) now becomes A(T.T Let’s focus on the slope ¡ ∂A ¢ ∂n V.n P.12) dG = dA + P dV + V dP (20.

The mathematical definition of activity ai of some species i is implicitly stated as ζ→ζ lim ª ai =1 g(ζ) (20.16) where g(ζ) is any reference function (e. and ζ ª is the value of ζ at the reference state.we see that μ= µ ∂G ∂n ¶ .. pressure. (Gm = μ) 20. The Gibbs free energy per mole (Gm ) for a pure substance is equal to the chemical potential. (20. To account for this one must introduce the concept of activity and the activity coefficient. Activity is hard to define in words and indeed it has an awkward mathematical definition as we will soon see. mole fraction. μ is also a measure of the change in Gibbs free energy of a system (at constant T and P ) with the change in the amount of material and it still has the same physical meaning. The activity coefficient has a more convenient definition which is that it is the measure of how a particular real system deviates from some reference system which is usually taken to be ideal. there exist complicated interactions which cause deviations from ideal behavior. concentration etc.15) P. a solute is dissolved in a solvent. Activity and the Activity coefficient When.g.).T So. for example. 146 .3.

Because of this it is always necessary to specify a reference state to which our real state can be compared.18) The definition of activity implies that γ i = 1 at g(ζ ª ) (the reference state) 20. ai g(ζ) (20. we can define are zero of energy any where we want. if we are talking about a gas we will mostly likely choose the ideal gas law in terms of pressure (P = nRT /V ) as our reference function and the reference state being when P = 0 since we know all gases behave ideally in the limit of zero pressure. γi ≡ which we can rearrange as ai = γ i g(ζ).1. but it is often the case that the reference state is chosen to be some ideal state.17) 147 . For example. Let us consider the activity of a real gas for the above reference function and reference state.3. The choice of this state is completely up to us. Note: the activity of gases as referenced to pressure has the special name fugacity (fugacity is a special case of activity).This implicit definition is awkward so for convenience one defines the activity coefficient as the argument of the above limit. (20. Reference States Thermodynamics is founded on the concept of energy which we know to have an arbitrary scale. That is.

21) i and for the ideal state μid = μª + RT ln aid ⇒ μª = μid − RT ln aid .2. i (20. Activity and the Chemical Potential One cannot measure absolute chemical potentials.20) Rather than referencing to the standard state one can also reference to any convenient “ideal” state.22) 148 . The deviation of the chemical potential at the state of interest versus at the reference state is determined by the activity at the current state (the activity at the reference state is unity by definition). μi − μª = RT ln ai .Our reference function is very simple: g(ζ) = ζ = P . For the state of interest μi = μª + RT ln ai (20.19) Thus the activity of our real gas is given by the activity coefficient times the pressure of an ideal gas under the same conditions. P (20. i i i i i i (20.3. so γ= a ⇒ a = γP. By convention we chose a standard state and measure relative to that state. Based on the condition that γ → 1 as we approach the reference state (P = 0 in this case) we see that the activity (or fugacity) of a real gas becomes equal to pressure for low pressures 20. only relative potentials can be measured. This ideal state is in turn referenced to the standard state.

μid → μª ).23) μi − μid = +RT ln ai − RT ln aid i i ai = RT ln id ai Example: Real and ideal gases at constant temperature. Lets say our gas is not ideal. (20. Starting from the begining dμ id dμid = Vm dP RT dP. Thus μ = μª + RT ln f. (20.Thus.28) (20.26) (20.25) dμ = μª Pª P This gives P .29) 149 . (20. (Note that as P → 1. so a = f for real gasses. so μid − μª = RT ln μid = μª + RT ln P.27) For gases activity is usually called fugacity and given the symbol f . Pª The usual standard state is the ideal gas at P ª = 1. μi = μid − RT ln aid + RT ln ai i i (20. but any pressure.24) Now we integrate from the reference state to the current state of interest Z Z RT id dP. then at a given pressure μ = μª + RT ln a. dμid = P z}|{ = dGm = −Sm dT + Vm dP =0 (20.

e. We have an ideal gas so. we want to reference to the ideal gas at the current pressure P. So at sea level id ª (20. μid = μª + RT ln P where we will take the reference state to be at sea level. i. μ = μid − RT ln P + RT ln f f μ = μid + RT ln .33) (20.Lets say that instead of referencing to the ideal gas at P = 1.32) The gas fields the gravitational force which gives it a potential energy per mole of Mgh at height h.31) (20. We add this energy per mole term to the chemical potential (which is free energy per mole) thus at equilibrium μid (0) = μid (h) + Mgh Referencing to the reference state we get ª ª μ/ = μ/ + RT ln Ph + Mgh (20. 150 .34) RT ln Ph = −Mgh Ph = e −M gh RT The last line is the barometric equation and it shows that pressure is exponentially decreasing function of altitude. This is easily done by using μª = μid − RT ln P in the above equation for μ. P Example: The barometric equation for an ideal gas.30) and at elevation h z }| { μ (0) = μ + RT ln 1 = μª μid (h) = μª + RT ln Ph =0 (20. P ª = 1 atm.

Since A and B are in equilibrium their chemical potentials must be equal μA = μB Now. Ka . for this process. The quantity aB defines the equilibrium constant.2) (21. Equilibrium First let us consider the equilibrium A ­ B. μA = μª + RT ln aA A and μB = μª + RT ln aB B So the equilibrium condition becomes μª + RT ln aA = μª + RT ln aB A B −4μª = μª − μª = RT ln aB − RT ln aA A B aB −4μª = RT ln aA Since chemical potential is free energy per mole.3) (21.21.1) 151 151 . aA (21. if we multiply the above by n moles we have aB −4Gª = nRT ln aA as a consequence of the equilibrium condition.

In a manner similar to the above aμª + aRT ln aA + bμª + bRT ln aB = cμª + cRT ln aC + dμª + dRT ln aD (21.7) (21. aA If the 4G < 0 then the transition A → B proceeds spontaneously as written. aA Again multiplying by n gives 4G = 4Gª + nRT ln aB .6) (21.4) μª + RT ln aA + 4μ = μª + RT ln aB A B (21. Consider a more complicated equilibrium aA + bB ­ cC + dD.5) 4μ = μª − μª + RT ln aB − +RT ln aA B A aB 4μ = 4μª + RT ln .9) 152 .Say the system A → B is not in equilibrium then we can not write μA = μB but we can write 4μ Proceeding as above we get z }| { μA + μB − μA = μB (21. The equilibrium condition is aμA + bμB = cμC + dμD .8) A B C D Rearranging gives z }| { ac ad aμª + bμª − cμª − dμª = RT ln C D A B C D aa ab A B ≡−4rx n Gª (21.

4. Equilibrium constants in terms of KC Equilibrium constant in terms of a condensed phase concentration: 0 KC = [C]c [D]d [A]a [B]b µ γc γd C D γa γb A B .the equilibrium constant is ac ad Ka = C D =⇒ 4Gª = −RT ln Ka aa ab A B (21.0. (21. 153 .3.0.11) which is related to Ka by Ka = 0 KC . 21. 21.12) If the reactants are solutes then as the solution is diluted all the activity coefficients 0 go to unity and KC → Ka .10) Note: n is absent in the above since the molar values are implied by the stoichiometry. ¶ (21. The Partition Coefficient Up to now we have only considered miscible solutions. We now consider the problem of determining the equilibrium concentrations of a solute A in both phases of an immiscible mixture.

The equilibrium constant for this process has a special α α→β β β/α name. 4Gª ≡ Gª −Gª . P β/α ≡ Kpart . We can solve for the partition coefficient to yield P For low concentrations P β/α ' β/α 4G α→β aβ = A = e− nRT .15) [A]β . 154 .16) Knowledge of the partition function is important on the delivery of drugs because. to enter the body.14) (21. α aA ª (21. [A]α (21. the drugs must transfer between an aqueous phase and a oil phase.The equilibrium equation is Aα ­ Aβ The equilibrium expression for this process is 4Gα→β = 0 = 4Gª − nRT ln Ka . it is called the partition coefficient.13) where. α→β (21. for species A in the α—β mixture.

can the drug handle the acidic environment of the stomach? 155 .For most drugs 0 < Ppart < 4 o/w (21. For example.17) Partition coefficient o/w Delivery mechanism low Ppart (likes water) injection o/w medium Ppart oral o/w high Ppart (likes oil) skin patch/ointment Factors other than the partition coefficient influence the drug delivery choice.

1) . 4rxn H > 0 for Endothermic reactions.22.1. 156 156 (22.A − bSm.C + dSm. After chemical reactions take place the system is in a final “product” thermodynamic state that is in general different from the initial “reactant” state.D − aSm. For any extensive property • 4rxn (Property) = property of products − property of reactants • Example — Reaction: aA+bB= cC+dD — 4rxn S = cSm. Heats of Reactions Exothermic reaction: heat is given off to the surroundings Endothermic reaction: heat is given taken in from the surroundings At constant pressure (Pex = P q = 4rxn U − w = 4rxn U − P 4rxn V = 4rxn H 4rxn H < 0 for Exothermic reactions. Chemical Reactions Up to now we have only been considering systems in the absence of chemical reactions.B 22.

49 kJ The heat of formation 4f H ª is the 4rxn H at STP in forming a compound from its constituent atoms in their natural states.2) 157 . O2 .1.1.63 kJ 2 2CO2 +2H2 O(liq)→C2 H4 + 3O2 4rxn H ª = +1410. H2 .1.97 kJ H2 + 1 O2 →H2 O(liq) 4rxn H ª = −285. C(graphite) are examples of atoms in their natural state.818 − (−285.830) = 44. Heats of Formation Hess’s Law of heat summation: 4rxn H is independent of chemical pathway Example: C2 H2 +H2 = C2 H4 .012 kJ 22. Example: Formation of water • H2 + 1 O2 = H2 O not 2H2 +O2 = 2H2 O 2 • 4rxn H = ponent.818 kJ 2 H2 + 1 O2 = H2 O(liq) 4f H ª = −285.830 kJ 2 H2 O(liq)→H2 O(gas) 4rxn H ª = −241. P i ν i 4f H(i). where ν i is the stoichiometric factor of the ith com- Example: H2 O(liq)→H2 O(gas) at SATP H2 + 1 O2 = H2 O(gas) 4f H ª = −241. Temperature dependence of the heat of reaction Z T2 4rxn CP dT 4rxn H(T2 ) = 4rxn H(T1 ) + T1 (22.22. This direct reaction is not easy but it can be done in steps C2 H2 + 5 O2 → 2CO2 +H2 O(liq) 4rxn H ª = −1299.83 kJ 2 C2 H2 +H2 = C2 H4 4rxn H ª = −174.2.

4rxn G = i i i 4rx n Gª X i ν i μi . z }| { X X ν i μª + RT ν i ln ai . 158 . i So. As we saw before μi can be defined in terms of activity μi = μª + RT ln ai .22.i for pure substance i). 4rxn G = G(products) − G(reactants) = (remember μi = Gm.6) 4rxn G = 4rxn Gª + RT ln Q.3) (22.7) • Note that the activity of any pure solid or liquid is for all practical purposes equal to 1. Ka depends on T but is independent of P.2.4) (22. where Q ≡ i aν i is the activity quotient. 4rxn G = 0 and Q = Ka (Thermodynamic equilibrium constant).5) Using the property of logarithms: a ln x + b ln y = ln(xa y b ) the above expression becomes 4rxn G = 4rxn Gª + RT ln Q Y i aν i i (22. For the reaction aA + bB = cC + dD Ka = ac ad C D aa ab A B (22. (22. Reversible reactions Recall the requirement for a spontaneous change: 4G < 0 for constant T and P. i At equilibrium.

3. we get ¶ µ 4rxn H ª ∂ ln Ka ind. ³ From this ∂(G/T)) = H.12) = dT d d(1/T ) dT d = −T 2 dT ) 4rxn H ª d ln Ka = dT RT 2 Integration gives 1 ln Ka (T2 ) = ln Ka (T1 ) + R Z T2 ª 4rxn Hm T2 (22. ∂(1/T P Applying this to 4rxn H ª 4rxn Gª = − 4rxn S T T gives ¶ µ ∂(4rxn Gª /T ) = 4rxn H ª ∂(1/T ) P ª Using 4rxn G = −RT ln Ka .13) (22.9) 22.14) T1 For a reasonably small range T2 − T1 this is well approximated by µ ¶ ª 4rxn Hm 1 1 − ln Ka (T2 ) = ln Ka (T1 ) − R T2 T1 (22. ai = useful relation KP = Pi Pª = Xi P Pª (P ª = 1 bar) This leads to the sometimes or more generally KP = Ka (P ª ) c d ¡ ¢c+d−a−b PC PD (P ª aC )c (P ª aD )d = = Ka P ª . a b PA PB (P ª aA )a (P ª aB )b i (22. (22.15) 159 .8) νi .• For ideal gases.10) (22. Temperature Dependence of Ka Starting with G =´H − T S or G/T = H/T − S. So at equilibrium.11) (22. 4rxn G = 4rxn Gª + RT ln Q becomes 0 = 4rxn Gª + RT ln Ka ⇒ 4rxn Gª = −RT ln Ka . d ln Ka =− = ∂(1/T ) P of P d(1/T ) R or (using d d(1/T ) (22.

4. Kn = KP • From concentration Cj = Equilibrium “constants” “constants” expression Ka KP KX Kn KC nj V = Pj . KX = KP P −4υg V • From nj = Pj RT (ideal gas approximation).22. P is known when V is known and constant when concentration known (RT )−4υg ¡ RT ¢−4υg 160 . • From Pj = Xj P . RT KC = KP (RT )−4υg ¡ RT ¢−4υg V relation to Ka – µ Ka −4υ g Kγ P ª ¶ situation used when an exact answer is needed gas reactions activity(products) activity(reactants) partial pressure(products) partial pressure(reactants) mole fraction(products) mole fraction(reactants) moles(products) moles(reactants) concentration(products) concentration(reactants) µ µ Ka −4υ g Kγ P ª Ka −4υ g Kγ P ª Ka −4υ g Kγ P ª ¶ ¶ P V −4υ g when eq. Extent of Reaction There are other equilibrium “constants” that are used in the literature.

Ionics Many chemical processes involve electrolytes and or acids and bases.23.3) (23. The chemical potential for the salt may be written in terms of the chemical potential for each of the ions: μsalt = v+ μ+ + v− μ− To determine the activity we start with μj − μª j . To understand these processes we must know something about how ions behave in solution.2) μsalt − μª salt . ln aj = RT and ln asalt = j = + or − (23.4) 161 161 . RT (23. Ionic Activities Consider a salt in solution Mv+ Xv− → v+ M z+ (aq) + v− X z− (aq).1) where v+ (v− ) is the number of cations (anions) and z+ (z− ) is the charge on the cation (anion). (23. 23.1.

8) v v We see that 1/v asalt = (av+ av− )1/v ≡ a± . (23.11) 162 . ln asalt = v+ ln a+ + v− ln a− or.6) (23. (23. alternatively.1. Ionic activity coefficients The activity coefficients for ionic solutions can also be defined via a+ = γ + m+ .Substituting the expression for μsalt into this gives ln asalt v+ μ+ − v− μ− + v+ μª − v− μª + − = RT v+ μ+ − v+ μª v− μ− − v− μª + − + = RT RT | {z } | {z } v+ ln a+ v− ln a− (23.9) The quantity a± is the mean ionic activity. The mean ionic activity coefficient is + − γ ± = (γ + γ − ) (23. This suggests that the interesting quantity is μsalt : v μª μsalt 1/v = salt + RT ln asalt . where m+ = v+ m and m− = v− m.5) So. asalt = av+ av− (23. 23.10) v v 1/v . a− = γ − m− . (23.1.7) It is the case that 1 mole of salt behaves like v = v+ + v− moles of nonelectrolytes in terms of the colligative properties.

vmM1 (23. So. vφ corresponds to the empirical factor i discussed earlier. One can use the colligative properties to measure the ionic activity coefficients. Recall how γ was calculated from the Gibbs-Duhem equation: Z m j ln γ ± = −j − dm0 . γ + and γ − cannot be measured individually. ln γ ± = 1 − Ba0 I (23. It is convenient to redefine the osmotic coefficient as φ= −1000 g/kg ln a1 .13) (23. a− .16) 163 .14) 23. Similarly freezing point depression is redefined as θ = vφKf m.The quantities a+ . Theory of Electrolytic Solutions Ionic strength is defined as I= 1X 2 z mi . m0 0 where j = 1 − φ.2. Results from Debye—Hückel theory: point charge in a continuum The Debye—Hückel equation: √ −α |z+ z− | I √ .12) where the subscript 1 refers to the solvent. (23. 2 i i (23.15) where z is the charge of the ion and m its concentration.

(23.18) 1000εkT a0 is the radius of closest approach.17) 8πLe2 ρ• . (23. I is given by the rate of change (in time) of charge. ρ• is the density of the pure solvent. Notice that the parameters α and B depend only on the solvent.3. ε is the dielectric constant for the pure solvent and L is Avogadro’s number. Q: I= dQ dt (23.where α= e3 (εkT )3/2 B= µ 2πρ• L 1000 ¶1/2 . e is the charge on the electron. One important approximation to this equation is to neglect the B term to get the Debye—Hukel limiting Law (DHLL): √ ln γ ± = −α |z+ z− | I.1 23.21) 164 .20) v+ + v− 1− I This equation works well to ionic strengths of about I = 0. 2 A useful empirical approximation is to set Ba0 = 1 and to add an empirical correction to get the : √ µ 2 ¶ 2 v+ + v− −α |z+ z− | I √ ln γ ± = + 2βm . It is seen that √ the DHLL correctly predicts the m dependence of ln γ ± . (23. Ion Mobility Current.19) This gives the dependence of ln γ ± for dilute solutions (m → 0). which is observed exP perimentally (recall I = 1 i zi2 mi ). (23.

Ion mobility 165 . w. ε: w = −εQ (23.602177 × 10−19 C.22) Power is given by the product of the voltage and the current: p = −εI Resistance is given by the ratio of the voltage to current: R= ε I (23. Some relevant constants • charge of an electron e = 1.(Electrical) work.1. is required to move a change through a potential (or voltage). • Faraday’s constant F = Le = 96485 C/mol (Avogadro’s number of electrons) 23.3.23) Conductance is the inverse of the resistance (R−1 ).

the viscous drag equals the Coulomb force.24) dQi dNi = |zi | e . E = Also recall Newton’s law dε . i. So the total force on the ions is a sum of the Coulomb force and the viscous drag Fi = zi eE − fvi (in solution).31) f The drag f has three basic origins. dx (23.The total current passing through an ionic solution is determined by the sum of the current carried by the cations and by the anions I = I+ + I− Now Ii = where i = +. −.28) Fi = mai = m dvi = zi eE. dt (23. 166 .30) The ions quickly reach terminal velocity.e. (23.25) Ni Ni dNi Avi 4t =⇒ = Avi V dt V Ni Avi V (in vacuum) (23. Hence Fi = 0. zi eE zi eE = f vi =⇒ vi = .29) The moving ions experience a viscous drag f that is proportional to their velocities.26) (23.27) (23. (23.. where E is the electric field. dt dt (23. For uniform ion velocity (vi ) the number of ions arriving at the electrode during any given time interval 4t is 4Ni = so Ii = |zi | e Recall Coulomb’s law Fi = zi eE.

167 . Electrophoretic effect. Relaxation effects • solvation shell must re-adjust as ion moves. Stoke’s Law type force • “spherical” ion moving through a continuous medium • this contribution is independent of the other ions 2. a “dressed” ion.1. • oppositely charged ions “pull” at each other 3.

then each mole of salt gives: N+ = αν + Ln and N− = αν − Ln. =1 z }| { / ν +/ |z+ | u+ A / Vεl / F / ν + |z+ | u+ u+ α n I+ = = = (23. (23. vi l .35) It is of interest to determine the ratio of the current carried by the cation versus the anion.32) E For the case for parallel plate capacitors E = ε . vi ui = . where l is the separation of the l plates. V l (23. So.33) ui = ε Here the current carried by ion i is Ii = |zi | e Ni ui ε A . The current then becomes Ii = |zi | e αν i Ln ui ε F=Le ε A = αν i n |zi | ui AF V l Vl (23.34) Suppose a salt has a degree of dissociation α (α = 1 for strong electrolytes) to produce ν + cations and ν − anions. (23.A more fundamental quantity than ion velocity is the ion mobility. 168 .36) I− / ν −/ |z− | u− A / Vεl α n / F / ν − |z− | u− u− Thus the ratio of the currents is determined by simply the ratio of the mobilities. ui which is the ion’s velocity per field.

Thermodynamics of Solvation An extremely important application of thermodynamics is to that of ion solvation. Solvation describes how a solute dissolves in a solvent. − Gion in vac .24. Since Gibbs free energy corresponds to non-P V work. Of course this is an approximation and numerous statistical mechanical models for solvents which incorporate a more realistic structure can be used. 4Gv→s can be determined by calculating the reversible work done in transferring an ion into the bulk of the solvent. The way to investigate the ion—solvent interaction upon solvation from a thermodynamics point of view is to consider the change in the properties of the ion in a vacuum versus the ion in solution. As a basic treatment of solvation we shall consider the solvent as a non-structural continuum and the ion as a charged particle. We will focus on ions in solution. but we will stick with this simple thermodynamic model. 169 169 . Primarily we will determine 4Gv→s ≡ Gion in solv.

The Born Model The Born model is a simple solvation model in which the ions are taken to be charged spheres and the solvent is take to be a continuum with dielectric constant εs 170 .24.1.

• Determine the work. 171 . • Assume the uncharged sphere can pass from the (neutral) vacuum to the neutral solvent without doing any work. • Determine the work. done in charging the sphere which is now in the solvent. (This is an approximation). done in discharging the sphere.4Gv→s for the Born model is obtained by considering the following contribution to the work of ion transfer from the vacuum state to the solvated state (see figure) • Begin with the state in which the charged sphere (the ion) is in a vacuum. wtr = 0. wch . wdis .

1) Work done in discharging the sphere: The act of discharging a sphere involves bringing out to infinity from the surface infinitesimal amounts of charge. 4Gv→s = wdis + wtr + wch = wdis + wch (24. The work done is discharging is some what complicated since as one removes the charge the work done in removing more charge changes according to the amount of charge currently on the sphere.So. 172 .

4) The above expression is 4Gv→s /ion. Free Energy of Solvation for the Born Model Combining the above two expression for work gives 4Gv→s = − (ze)2 (ze)2 + 8π 0 ri 8π 0 εs ri µ ¶ (ze)2 1 = −1 8π 0 ri εs N (ze)2 = 8π 0 ri µ ¶ 1 −1 εs (24. Work done in charging the sphere: The only difference in charging the sphere is that the sign of the work will be different and that since we are charging in a solvent we must multiply the permittivity of free space by the dielectric constant of the solvent.3) 24.1.5) 173 . ri is the radius of the sphere (ion) and 0 is the permittivity of free space.2) where z is the oxidation state of the ion. e is the charge of the electron.This is expressed mathematically as Z 0Z ∞ σ wdis = drdσ 2 ze ri 4π 0 r Z 0 σ dσ = ze 4π 0 ri (ze)2 .1. = − 8π 0 ri (24. For n moles of ions (nL = N) 4Gv→s (24. wch = + (ze)2 8π 0 εs ri (24. So.

1. Ion Transfer Between Phases We can quickly generalize the Born model to describe ion transfer between phases in a solution of two immiscible phases Consider an immiscible solution of two phases α and β having dielectric constants εα and εβ .The dielectric constant of any solvent is always greater than unity so ε1s − 1 is always negative hence 4Gv→s < 0.2.7) 24.6) The Partition Coefficient We can now write the partition coefficient for the Born model as α/β Pi =e −4Gª β→α nRT =e − 8πr L(ze)2 i 0 RT 1 − ε1 εα β (24. 174 . Enthalpy and Entropy of Solvation We may employ the standard thermodynamic relations which we have derived earlier to obtain the entropy and enthalpy for the Born model.3. 24. Since Gibbs free energy is a state function we can write the change in free energy for transfer of an ion form the β phase to the α phase as z }| { 4Gβ→v + 4Gv→α µ µ ¶ ¶ N (ze)2 1 N (ze)2 1 = − −1 + −1 8π 0 ri εβ 8π 0 ri εα µ ¶ 1 N (ze)2 1 − = 8π 0 ri εα εβ =−4Gv →β 4Gβ→α = (24. Thus ions always exist more stably in solution than in a vacuum.1.

εs (24. the Born model does not make quantitatively correct predictions in many cases. Corrections to the Born Model The Born model is very valuable because of its simplicity–qualitative statements about solvation and ion transfer between phases can be made.9) The only variable in the above equation that has a temperature dependence is the dielectric constant of the solvent so. µ ¶ 1 N (ze)2 ∂εs N (ze)2 ∂ .From µ ∂G ∂T ¶ P = −S ⇒ µ ∂4Gv→s ∂T ¶ P = −4Sv→s .10) = 4Sv→s = − 8π 0 ri ∂T εs 8π 0 ri ε2 ∂T s Enthalpy is obtained via the relation: 4Hv→s = 4Gv→s + T 4Sv→s µ ¶ N (ze)2 1 N (ze)2 T ∂εs = −1 + 8π 0 ri εs 8π 0 ri ε2 ∂T s ¶ µ 2 N (ze) 1 T ∂εs −1 = + 2 8π 0 ri εs εs ∂T (24.11) 24.2. (24.8) we find entropy to be 4Sv→s ∂ =− ∂T " N (ze)2 8π 0 ri µ ¶# 1 −1 . (24. Unfortunately however. We simply list here several phenomena that more sophisticated theories of solvation must consider 175 .

Changes in solvent structure: the local environment of the ion has a different arrangement of solvent molecules than that of the bulk solvent. so the initial structure of the solvent must breakdown and the new structure must form. Annihilation of defects: A small ion may be captured in a micro-cavity within the solvent releasing the energy of the micro-cavity defect. The solvophobic effect: a cavity must form in the solvent to accommodate the ion. 2.1. 4. Specific interactions: any interaction energy specific to the particular ionsolvent pair: Hydrogen bonding being the prime example. 3. 176 .

Key Equations for Exam 4 Listed here are some of the key equations for Exam 4.2) .25.1) (25. 177 177 dH = T dS + V dP dA = −SdT − P dV dG = −SdT + V dP (25. Equations • Some thermodynamic relations H = U + PV A = U − TS G = H − TS • The chemical potential equation μi = μª + RT ln ai i • The 4G equation (this should be posted on your refrigerator) 4G = 4Gª + RT ln Q. The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations. The equations are collected here simply for handy reference for you while working the problem sets. This section should not substitute for your studying of the rest of this material.

At equilibrium 4G = 0 and 4Gª = −RT ln Ka • For an ideal gas CP m = Cvm + R (25.3)

(25.4)

• The Debye—Hukel limiting Law (DHLL):

√ ln γ ± = −α |z+ z− | I.

(25.5)

• The ratio of the current carried by the cation versus the anion in terms of ion mobility is I+ u+ = (25.6) I− u− • The chemical potential equation μi = μª + RT ln ai i • The 4G equation (this should be posted on your refrigerator) 4G = 4Gª + RT ln Q. At equilibrium 4G = 0 and 4Gª = −RT ln Ka • 4G for the Born model: 4Gv→s N (ze)2 = 8π 0 rs µ ¶ 1 −1 εs (25.9) (25.8) (25.7)

(25.10)

• 4G for transfer of an ion form the β phase to the α phase, µ ¶ N (ze)2 1 1 − 4Gβ→α = 8π 0 ri εα εβ

(25.11)

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Chemistry 352: Physical Chemistry II

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Part V Quantum Mechanics and Dynamics

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26. Particle in a 3D Box
We now return to quantum mechanics and investigate some of the important models that we omitted from the first semester. In particular we will look at the particle in a box in more than one dimension. We will also solve models which deal with rotations.

26.1. Particle in a Box
Recall that the important ideas from the 1D particle in a box problem were The potential, V (x), is given by ⎧ ⎪ ⎨ ⎪ ⎩ ∞ ∞ x≤0 0<x<a . x≥a

V (x) =

0

(26.1)

Because of the infinities at x = 0 and x = a, we need to partition the x-axis into the three regions shown in the figure.

181
181

Now, in region I and III, where the potential is infinite, the particle can never exist so, ψ must equal zero in these regions. The particle must be found only in region II. The Schrödinger equation in region II is (V (x) = 0) −~2 d2 ψ(x) ˆ Hψ = Eψ =⇒ = Eψ, 2m dx2 The general solution of this differential equation is ψ(x) = A sin kx + B cos kx, where k = q
2mE . ~2

(26.2)

(26.3)

Now ψ must be continuous for all x. Therefore it must satisfy the boundary conditions (b.c.): ψ(0) = 0 and ψ(a) = 0. From the ψ(0) = 0 b.c. we see that the constant B must be zero because cos kx|x=0 = 1. So we are left with ψ(x) = A sin kx for our wavefunction.

182

The second b.c., ψ(a) = 0, places certain restrictions on k. In particular,

nπ , n = 1, 2, 3, · · · . a The values of k are quantized. So, now we have kn = ψn (x) = A sin nπx . a

(26.4)

(26.5)

The constant A is the normalization constant. Solving for A gives A= r

2 . a

(26.6)

Thus our normalized wavefunctions for a particle in a box are (in region II) r nπx 2 sin . (26.7) ψ n (x) = a a We found the energy levels to be En =
h n2 π 2 ~2 ~= 2π n2 h2 = . 2ma2 8ma2

(26.8)

26.2. The 3D Particle in a Box Problem
We now consider the three dimensional version of the problem. The potential is now V (x, y, z) = ( 0, 0 < x < a, 0 < y < b, 0 < z < c . ∞, else (26.9)

183

Now the Schrödinger equation is −~2 2 ˆ ∇ ψ = Eψ Hψ = Eψ ⇒ 2m µ ¶ −~2 ∂ 2 ψ ∂ 2 ψ ∂ 2 ψ + 2 + 2 = Eψ. ⇒ 2m ∂x2 ∂y ∂z

(26.10)

It is generally true that when the Hamiltonian is a sum of independent terms, we can write the wavefunction as a product of wavefunctions ψ(x, y, z) = ψx (x)ψ y (y)ψ z (z). (26.11)

This lets us perform a mathematical trick which is sometimes useful in solving partial differential equations. Subbing the product wavefunction into the Schrödinger equation we get µ ¶ −~2 ∂ 2 ψx ψy ψz ∂ 2 ψx ψy ψz ∂ 2 ψx ψy ψz = Eψ x ψy ψz + + (26.12) 2m ∂x2 ∂y 2 ∂z 2 µ ¶ −~2 ψy ψz ∂ 2 ψx ψx ψz ∂ 2 ψy ψx ψy ∂ 2 ψz = Eψ x ψy ψz . + + 2m ∂x2 ∂y 2 ∂z 2

We now divide both sides by ψx ψy ψz to get µ ¶ 1 ∂ 2ψy 1 ∂ 2ψz −~2 1 ∂ 2 ψx = E. + + 2m ψx ∂x2 ψy ∂y 2 ψz ∂z 2 This equation is now of the form f (x) + g(y) + h(z) = C, where C is a constant. If we take the derivative with respect to x we get d→ f (x) + g(y) + h(z) = C, dx → dC df (x) dg(y) dh(z) + + = , dx dx dx dx df (x) = 0, dx

(26.13)

(26.14)

(26.15)

184

ny Ez.nz The total wavefunction is n2 h2 x .18) nx πx 2 sin . 8mc2 (26.nz . a a r ny πy 2 sin .ny + Ez. Similarly for g(y) and h(z) Applying this to our Schrödinger equation means that we have converted our partial differential equation into three independent ordinary differential equations. = b b r nz πz 2 sin = c c r (26. 8mb2 n2 h2 z = .20) 185 . −~2 d2 ψx −~2 1 d2 ψx = Ex =⇒ = Ex ψx 2m ψx dx2 2m dx2 −~2 d2 ψy −~2 1 d2 ψy = Ey =⇒ = Ey ψy 2m ψy dy 2 2m dy 2 −~2 d2 ψz −~2 1 d2 ψz = Ez =⇒ = Ez ψz 2m ψz dz 2 2m dz 2 which we recognize as the 1D particle in a box equations.16) √ ny πy nz πz 2 2 nx πx sin sin ψ=√ sin a b c abc E = Ex. (26. f (x) is a constant.nx = Ey.17) (26.So. 8ma2 n2 h2 y = . Hence we immediately have ψx = ψy ψz and Ex.nx + Ey.19) and the total energy is (26.

When n(> 1) states have the same total energy they are said to be n-fold degenerate. nz = 1).Degeneracy The 3D particle in a box model brings up the concept of degeneracy. nz = 1). Let the 3D box be a cube (a = b = c) then the states (nx = 2. ny = 2.21) 186 . (26. ny = 1. (nx = 1. (nx = 1. ny = 1. nz = 2) have the same total energy and thus are degenerate.

• Algebra: An algebra is a specific collection of rules applied to a set of objects and a particular operation — Rules ∗ Transitivity ∗ Associativity ∗ Existence of an identity ∗ Existence of an inverse — e.. Multiplication on the set of real numbers 187 187 . ˆ • Operator: An operator. Operator Algebra We now take a mathematical excursion and discuss the algebra of operators. transforms a function.1. etc. say f. Definitions • Function: A function. Addition on the set of real numbers. say O.g. say f . say y. Operators 27. is related to an independent variable.. describes how a dependent variable.27. say g: Of(x) = g(x). into another ˆ function. y = sin x. say x: y = f(x) — e. y = x2 .g.

5) (27. " #" # " # 1 0 3 1 3 1 = (27. then αf (x) = g(x) = βf (x) ˆ ˆ ˆ 2.3) ˆˆ ˆ α β αf (x) = β (ˆ f (x)) . ˆˆ 4..— Note: Commutivity is not a requirement of an algebra ∗ example 1: multiplication on the set of real number is commutive: ab = ba ∗ example 2: multiplication on the set of n × n matrices is not commutive: ab 6= ba in general. ˆ ˆ ˆ then (ˆ + β)f (x) = αf (x) + βf (x) = g(x) + h(x) α ˆ 3. e. Inverse: ˆ if αf (x) = g(x) and βg(x) = f (x) ˆ ˆ ˆ then β = α−1 and is said to be α inverse ˆ (27. Addition: ˆ if αf (x) = g(x) and βf (x) = h(x).4) (27.g.2) Algebraic rules for operators 1. ˆˆ but in general αβf (x) 6= β αf (x). Equality: ˆ if α = β.1) 2 1 1 1 7 3 but " 3 1 1 1 #" 1 0 2 1 # " 5 1 3 1 # " 3 1 7 3 # = 6= (27.6) 188 . Multiplication: ³ ´ ˆ (x) = α βf (x) ˆ αβf ˆ ˆ (27.

[◦. ◦]: h i ˆ ≡ αβ − β α. This leads to the construction of the ˆˆ ˆˆ commutator. and ˆ ˆ ˆ — α(λf (x)) = λˆ f (x). y. z) ¡d dx ¢ f (x) = d2 f (x) dx2 Commutators: We have seen that in general αβ 6= β α. ˆ α Hermitian operators: • A special class of linear operators • All observables in quantum mechanics are associated with Hermitian operators • The eigenvalues of Hermitian operators are real Some important operators 1. z) = ∂ ex + ∂ ey + ∂ ez f(x. • x: xf(x) = xf(x) ˆ ˆ ³ ´ ¢ ¡ ˆ ˆ ˆ ˆ ˆ d • d2 : d2 f (x) = d df (x) = d dx f (x) = d f (x) dx d dx ˆ ˆ • d: df (x) = • ˆ: ˆf (x. z) ˆ • ∇: ∂x ∂y ∂z ´ ³ 2 2 2 ∂ ∂2 ∂2 ˆ ˆ • ∇ : ∇ f (x. β ˆ ˆˆ ˆˆ (27. y. α.7) 189 . y.Linear operators: • A special and important class of operators • They obey all of the above properties in addition to — α (f (x) + g(x)) = αf (x) + αg(x). y. z) = ∂x2 + ∂y2 + ∂z2 f (x. −y. −z) ı ı ´ ³ ˆ ∇f(x. z) = f (−x. y. where λ is a complex number.

10) ˆ because β and α commute. ˆ Thus (27. then βf (x) = bf (x). β = 0 and α and β are said to commute with one another. ˆ ˆ The proof goes as follows: On the one hand. The only way for ˆ ˆ = bf. then α.9) (27. We shall see that eigenvalues of certain operator can be identified as experimental observables. ˆ ˆ If αf (x) = af (x) and β and α commute. this to be true is if βf 190 . ˆ (27. ³ ´ ˆ α β (ˆ f ) = α βf ˆ ˆ ³ ´ ³ ´ ˆ α βf = a βf . then the operator equation.8) The eigenvalue equation is of fundamental importance in quantum theory. ˆ α ˆ ˆ β (ˆ f ) = β (af) = aβf because f is an eigenfunction of α.11) ˆ which states that βf is an eigenfunction of α with eigenvalue a.h i ˆ = β α. ˆˆ ˆ ˆ If αβ ˆ ˆ ˆ The eigenvalue equation: If αf (x) = g(x) and g(x) = af(x). αf (x) = g(x) ˆ ˆ becomes the eigenvalue equation αf (x) = af (x). ˆ On the other hand. ˆ ˆ (27. Commuting operators and simultaneous sets of eigenfunctions.

27.2. j 6= k.13) i 191 . (27. Completeness.12) j space Theorem 2: The eigenfunctions of a Hermitian operator form a complete set Corollary (the superposition principle): Any arbitrary function ψ in the space of eigenfunctions {ϕi } can be written as a superposition of these eigenfunctions: X ψ= ai ϕi (27. and the Superposition Principle Theorem 1: The eigenfunctions of a Hermitian operator corresponding to different eigenvalues are orthogonal: Z ψ∗ ψk = 0. Orthogonality.

28. Angular Momentum
We will encounter several different types of angular momenta, but fortunately they are all described by a single theory Before starting with the quantum mechanical treatment of angular momentum, we first review the classical treatment.

28.1. Classical Theory of Angular Momentum
The classical angular momentum, L, is given by L=x×p (28.1)

Hence,

The vector cross-product can be computed by finding the following determinant: ¯ ¯ ¯ ex ey ez ¯ Ly Lx Lz ¯ z }| { ¯ z }| { z }| { ¯ ¯ (28.2) L = ¯ x y z ¯ = (ypz − zpy )ex + (zpx − xpz )ey + (xpy − ypx )ez ¯ ¯ ¯ px py pz ¯ Lx = (ypz − zpy ) , Ly = (zpx − xpz ) , Lz = (xpy − ypx ) . (28.3) (28.4) (28.5)

Another quantity that we will find useful is L2 = L · L = L2 + L2 + L2 x y z 192
192

(28.6)

28.2. Quantum theory of Angular Momentum
So, in accordance with postulate II, we replace the classical variables with their operators. That is, µ ¶ ˆ x = (ˆpz − z py ) = ~ y ∂ − z ∂ , (28.7) L yˆ ˆˆ i ∂z ∂y µ ¶ ∂ ∂ ~ ˆ z −x , (28.8) zˆ ˆˆ Ly = (ˆpx − xpz ) = i ∂x ∂z µ ¶ ∂ ∂ ~ ˆ x −y . (28.9) xˆ ˆˆ Lz = (ˆpy − y px ) = i ∂y ∂x Recall the basic commutators. ∙ ¸ ∂ , u = 1, ∂u ∙ ¸ ∂ , v = 0, ∂u (28.10)

where u, v = x, y, or z and u 6= v. From these basic commutators one can derive h i i h ˆ ˆ ˆ ˆ ˆ x , Ly = i~Lz , ˆ y , Lz = i~Lx , L L

and

i h ˆ ˆ ˆ z , Lx = i~Ly L

(28.11)

i h i h i h ˆ ˆ ˆ ˆ ˆ ˆ 2 , Lx = L2 , Ly = L2 , Lz = 0 L

(28.12)

It is often convenient to express the angular momentum operators in spherical polar coordinates as follows. ¶ µ ∂ ∂ ˆ Lx = i~ sin φ + cot θ cos φ , (28.13) ∂θ ∂φ ¶ µ ˆ y = −i~ cos φ ∂ − cot θ sin φ ∂ , (28.14) L ∂θ ∂φ

193

∂ ˆ Lz = −i~ ∂φ µ 2 ¶ 1 ∂2 ∂ ∂ 2 2 ˆ + cot θ + L = −~ ∂θ sin2 θ ∂φ2 ∂θ2

(28.15) (28.16)

28.3. Particle on a Ring
Consider a particle of mass μ confined to move on a ring of radius R. The moment of inertia is I = μR2 The Hamiltonian is given by ˆ −~2 d2 L2 ˆ H= z = 2I 2I dφ2 (note that we use d rather than ∂ since the problem is one-dimensional). The Schrödinger equation becomes −~2 d2 ψ = Eψ 2I dφ2 (28.18) (28.17)

Notice that this Schrödinger equation is exactly the same form as the particle in a box. The only difference is the boundary conditions. The boundary condition for the particle in a box were ψ was zero outside the box. Now the boundary condition is that ψ(φ) = ψ(φ + 2π). The wavefunction must by 2π periodic. The allowable wavefunctions are

⎧ ⎪ A cos mφ ⎨ ψm (φ) = A sin mφ , ⎪ ⎩ Aeimφ

(28.19)

194

m = 0, ±1, ±2, ±3, . . . These wavefunctions are really the “same.” It will be most convenient to use ψm (φ) = Aeimφ as our wave functions. Plugging ψm (φ) = Aeimφ into the Schrödinger equation gives −~2 d2 Aeimφ = Em Aeimφ 2I dφ2 ~2 m2 imφ Ae = Em Aeimφ 2I Therefore the energy levels (the eigenvalues) for a particle in a ring are m2 h2 ~2 m2 = . 2I 8π2 I Next we need to find the normalization constant, A. Z 2π ψ∗ ψdφ 1 = Z0 2π 1 = A2 e−imφ eimφ dφ 0 Z 2π 2 1 = A dφ = 2πA2 , Em =
0

(28.20)

(28.21)

(28.22)

thus

1 . 2π Hence the normalized wavefunctions for a particle on a ring are 1 ψ = √ eimφ . 2π A=

r

(28.23)

(28.24)

28.4. General Theory of Angular Momentum
To discuss angular momentum in a more general way it is convenient to define two so-called ‘ladder’ operators ˆ ˆ ˆ L+ ≡ Lx + iLy (28.25)

195

and ˆ ˆ We collect here the commutators of L+ and L− : h i ˆ ˆ ˆ ˆ ˆ ˆ ˆ ˆ Lz , L+ = L+ ⇒ L+ Lz = Lz L+ − L+ i h ˆ ˆ ˆ ˆ ˆ ˆ ˆ ˆ Lz , L− = −L− ⇒ L− Lz = Lz L− + L− ˆ ˆ ˆ L− ≡ Lx − iLy (28.26)

(28.27) (28.28)

ˆ ˆ Now, since Lz and L2 commute there must exist a set of simultaneous eigenfunctions {ψi } ˆ (28.29) Lz ψi = mψ i and ˆ L2 ψi = k2 ψi (28.30) Physically, k~ represents the length of the angular momentum vector and m~ represents the projection onto the z-axis. (Note: for simplicity in writing we are ‘hiding’ the ~ in the wavefunctions.) On these physical grounds we conclude |m| ≤ k, i.e., k sets an upper and lower limit on m. Let’s define the maximum value of m to be a new quantum number l ≡ mmax . (Thus l ≤ k). And let’s define the minium value of m to be a new quantum number l0 ≡ mmin . (Thus −l0 ≤ k) Now, at least one of the eigenfunctions in the set {ψ i } yields the eigenvalue mmax ˆ (or l) when operated on by Lz . Let’s call that eigenfunction ψl ; ˆ Lz ψl = lψ l . ˆ Now we can operate on both sides of this equation with L− : ˆ ˆ ˆ L− Lz ψl = L− lψ l (28.32) (28.31)

196

ˆ ˆ ˆ ˆ ˆ Using the commutator relation L− Lz = Lz L− + L− we get ´ ³ ˆ ˆ ˆ ˆ Lz L− + L− ψl = lL− ψl ˆ ˆ ˆ ˆ Lz L− ψl + L− ψl = lL− ψl

(28.33)

Bringing the second term on the left hand side over to the right hand side gives ˆ ˆ ˆ ˆ Lz L− ψl = lL− ψl − L− ψl ˆ ˆ ˆ Lz L− ψl = (l − 1)L− ψl | {z } | {z }
ψ l−1 ψ l−1

(28.34)

ˆ ˆ We see that L− ψl ≡ ψl−1 is in fact an eigenfunction of Lz (with associated eigenvalue (l − 1)) and is thus a member of {ψi } . The eigenfunction ψl−1 has an associated eigenvalue that is one unit less then the maximum value. ˆ− The above procedure can be repeated n times so that Ln ψl = ψl−n provided n does not exceed l − l0 . The eigenfunction ψ l−n has an associated eigenvalue that is n units less then the maximum value, i.e., ˆ Lz ψl−n = (l − n)ψ l−n . (28.35) The largest value of n is l − l0 . For that case, ˆ Lz ψl0 = (l − l + l0 )ψl0 = l0 ψl0 . (28.36)

ˆ Similar behavior is seen for the operator L+ , except in the opposite direction–the ˆ eigenvalue is increased by one unit for each action of L+ . For example ˆ ˆ ˆ L+ Lz ψl0 = L+ l0 ψl0 ´ ³ ˆ ˆ ˆ ˆ Lz L+ − L+ ψl0 = l0 L+ ψl0 (28.37)

ˆ ˆ ˆ Lz L+ ψl0 = (l0 + 1)L+ ψl0 .

197

ˆ ˆ The raising and lowering nature of L+ and L− is why they are called ladder operators. ˆ ˆ We can not act with L+ and L− indefinitely since we are limited by l–we reach the ends of the ladder. This requires that ˆ L− ψl0 = 0 (we can’t go lower than the lowest step) and ˆ L+ ψl = 0 (we can’t go higher than the highest step). ˆ ˆ ˆ ˆ Often times the ladder operators appear in tandem either as L− L+ or L+ L− so it is useful list some identities for these products ˆ ˆ ˆ ˆz ˆ L− L+ = L2 − L2 − Lz and ˆ ˆ ˆ ˆz ˆ L+ L− = L2 − L2 + Lz (28.41) (28.40) (28.39) (28.38)

We can use these identities to derive a relation between the quantum numbers k and l. We begin with ³ ´ ˆ ˆ − L+ ψl = L− L+ ψl = 0, ˆ ˆ L

(28.42)

Therefore

but from the first of the above identities ´ ³ ˆz ˆ ˆ ˆ ˆ L− L+ ψl = L2 − L2 − Lz ψl = (k2 − l2 − l)ψ l k2 − l2 − l = 0 ⇒ k = p l(l + 1).

(28.43)

(28.44)

198

Quantum Properties of Angular Momentum The eigenfunctions of angular momentum are entirely specified by two quantum numbers l and m: ψlm . −l + 1 . This also implies that the number of ‘rungs’ is 2l + 1 and that l must be either an integer or a half-integer. l − 2. l − 1. φ). . −l.50) The solutions to this partial differential equation are known to be the spherical harmonic functions ψ lm = Ylm (θ. .47) 28. . l(l + 1) − l02 + l0 = 0. ˆ L2 ψlm = l(l + 1)ψ lm ˆ Lz ψlm = mψ lm (28.46) substituting in the relation we just found for k gives (28. (28. (28.49) If we write out the first of these explicitly in spherical polar coordinates as a partial differential equation we obtain 1 ∂ 2 ψlm ∂ 2 ψlm ∂ψlm + + cot θ + l(l + 1)ψ lm = 0 ∂θ sin2 θ ∂φ2 ∂θ2 (28.45) and (28.48) (28.5. .51) 199 . simplifying gives l = −l0 Thus mmax = l. mmin = −l and so m = l.We we can also consider ³ ´ ˆ ˆ ˆ ˆ L+ L− ψl0 = L+ L− ψl0 = 0 ´ ³ ˆ ˆ ˆz ˆ ˆ L+ L− ψl0 = L2 − L2 + Lz ψl0 = (k 2 − l02 + l0 )ψl0 .

φ) sin θdθdφ = 0 0 l0 6= l or m0 6= m 0 0 28. All 2l + 1 of these wavefunctions correspond to the same energy. We say the there is a 2l + 1 degeneracy of the energy levels.The spherical harmonics are functions of two variables. The rigid rotor Rotational energy For general rotation in three dimensions the is ~2 ˆ ˆ H = L2 . In other words. φ)Ylm (θ. |m| |m| (28. The spherical harmonics (and hence the angular momentum wavefunctions) are orthonormal.54) l(l + 1)h2 l(l + 1)~2 = = El .1.53) Yl∗m0 (θ. 2I so the Schrödinger equation is ~2 ˆ ~2 ˆ Hψ lm = Elm ψlm ⇒ L2 ψlm = Elm ψlm ⇒ l(l + 1)ψlm = Elm ψlm . Both the spherical harmonics and the Legendra polynomials are tabulated. φ) = APl (θ)eimφ . They are also built-in functions of Mathematica. but they are a product of a function only of θ and a function only of φ. ψlm = Ylm (θ. (28. 200 . We know that there are 2l + 1 different m values for a particular l value.52) where the Pl (θ) are the Legendra polynomials and A is normalization constant. ( Z 2π Z π 1 l0 = l and m0 = m (28.55) (28. 2I 2I Thus Elm = (28.5. the energy levels are determined only by the value of l. meaning.56) 2I 8π2 I There is no m dependence for the energy.

Addition of Angular Momentum 29. l = s = 1/2.1) and ψ s (θ) = ψs (θ + 4π).2) That means that the system has to ‘rotate’ twice (in spin space not coordinate space) to get back to its original state. (29. Systems in which l takes on half-integer values are peculiar. One peculiarity of this system is that the wavefunctions are 4π periodic (and 2π antiperiodic): ψs (θ) = −ψs (θ + 2π) (29. One example of such a system is the spin of an electron. ∗ ∗ ∗ See in-class demonstration: the belt trick ∗ ∗∗ 201 201 .1.29. The values of m = ms are limited to +1/2 and −1/2. These systems have no classical analogs. Spin Angular Momentum We learned above that l may take on integer or half-integer values.

we use J when we speak generally. LS coupling (also called Russell-Saunders coupling) • works well for low atomic weight atoms (first couple of rows of the periodic table) P • find the total spin angular momentum S = Ms.29. One measures. The are two main coupling schemes which account for the total angular momentum of the atom. The electrons in many electron atoms couple.max . (M = i mi ) • then J = L + S 2. 1.2. the total angular momentum. J. (Ms = i msi ) P • find the total orbital angular momentum L = Mmax .) 202 . Addition of Angular Momentum In atoms the are a number of sources of angular momentum: The l’s and s’s of each of the electrons.2. The Addition of Angular Momentum: General Theory Consider two sources of angular momentum for a system represented by the opˆ ˆ ˆ ˆ ˆ ˆ ˆ erators J1 and J2 (J1 and J2 could be L or S angular momentum. however.1. jj coupling • applies to higher atomic weight atoms • find subtotal angular momentum for each electron ji = li + si P • then find total angular momentum by J = i ji . • we will not use this method. 29.

6) 203 .2. . 29.2. An Example: Two Electrons The table below shows the total spin angular momentum S for a two electron system (29. That is. |j1 − j2 | . . . .ˆ ˆ ˆ The total angular momentum is JT = J1 + J2 . (29.4) This corresponds to a situation in which component angular momentums add in the most favorable manner The minimum value of J is determined by the case when the components add in the least favorable manner. Thus the allowed values of J are J = j1 + j2 . The maximum value of J is determined by the maximum value of M by Jmax = Mmax = m1max + m2max = j1 + j2 (29. |j1 − j2 | + 1. Jmin = |j1 − j2 | .3) We need to determine the allowed values of the total angular momentum quantum number J. j1 + j2 − 1. ˆ ˆ ˆ The total z-component of the angular momentum is JzT = Jz1 + Jz2 The last statement implies that the orientation quantum number of the total system is simple the sum of that for the components M = m1 + m2 (29.5) The total angular momentum is quantized is exactly the same manner as any other angular momentum.

Term symbols are useful for predict and understanding spectroscopic data. those being 1 S and 3 S during our discussion of helium. Term Symbols We have already seen several term symbols.3.spin state α(1)α(2) β(1)β(2) α(1)β(2) + β(1)α(2) α(1)β(2) − β(1)α(2) ms1 1 2 ms1 1 2 MS 1 −1 0 0 S 1 1 1 0 −1 2 0 0 −1 2 0 0 Counting states: The spin degeneracy. it is worthwhile to briefly discuss them. In general the term symbol is simply notates the total orbital angular momentum and spin degeneracies of a particular set of states (or a state in the case of a singlet state). The orbital degeneracy is given by gL = 2L + 1. gS . G H 204 . Term symbols are simply shorthand notion used to identify states. So. of the states is given by 2S + 1. For historical reasons L values are associated with a letter like the l values of a hydrogenic system are. L 0 symbol S 1 P 2 D 3 F 4 5 .2. In the above example the degeneracy is gS = 3 for the S = 1 states and gS = 1 for the S = 0 states. 29.

The term symbol for a particular states is constructed from the following general template gS LJ . Hund’s Rule for the ground state only. These dipoles interact with a certain spin—orbit interaction energy ESO . S = 0. 1. Highest J value (inverted) “hole” 29. If several terms have the same multiplicity then ground state will be that of the largest L. Many electron atoms have term symbols associated with their states.4. • E.. All closed shells have zero spin and orbital angular momentums: L = 0. The spin—orbit Hamiltonian is [ ˆ HSO = hcAL · S ´ ³ ˆ ˆ ˆ ˆ SO = hcA J 2 − L2 − S 2 . H 2 (29.g. These states are all singlet S states. An electron has orbital and spin magnetic dipoles. p1 and p5 have the same term symbol.7) 205 . Spin Orbit Coupling A charge possessing angular momentum has a magnetic dipole associated with it. notated by 1 S 2. An electron and a “hole” lead to equivalent term symbols. 2. 3. The ground state will have maximum multiplicity. 3.2. Lowest J value (regular) “electron”. Rules: 1.

From the Hamiltonian the spin—orbit interaction energy is ESO = hcA [J(J + 1) − L(L + 1) − S(S + 1)] 2 (29.where A is the spin—orbit coupling constant.8) 206 .

30. Perturbation Theory The basic procedure of perturbation theory • Find a solvable system that is similar to the system at hand. Approximation Techniques As we learned last semester. 207 207 . Consequently we must be satisfied with using approximation methods. • Treat the difference between the two systems as a perturbation to the solvable system • Use the solvable system’s wavefunctions as a zeroth order approximation to the wavefunctions for the unsolvable system. Last semester. we always took the simplest approximation to give the qualitative properties of the unsolvable system. there are very few models for which we can obtain an exact solution.1. Now we will consider two important quantitative approximation methods: (i) perturbation theory and (ii) variational theory 30. • These wavefunctions are used to find a first order correction to the energy.

3) • The perturbative part of the Hamiltonian is ˆ H (1) = ax4 . • The procedure is repeated to get higher and higher order approximations. Example: the quartic oscillator • Consider the quartic oscillator described by the potential V (x) = 1 kx2 +ax4 2 where a is very small and can be treated as a perturbation. The nth state energy in perturbation theory: (0) (1) En = En + En + .• The first order energy is then used to make a first order approximation to the wavefunction.1) (1) where En is the nth state energy for the unperturbed (solvable) system and En is the first order correction. . This process get algebraically intensive so we will only go as far as listing the first order energy correction.2) n n all space ˆ where H (1) is the first order correction to the Hamiltonian–the perturbation. • The obvious solvable system is the harmonic oscillator: 1 ~2 d2 ˆ + kx2 . (30. √ 2 This has energy levels En = ~ω(n+ 1 ) and wavefunctions An Hn ( αx)e−αx /2 . 2 q where α = km ~ (30. .4) 208 . (0) (30. H=− 2 2m dx 2 (30. This is given by Z (1) ˆ En = ψ(0)∗ H (1) ψ(0) dx. .

We will not prove this theorem here. The value of the parameter which minimizes the energy.2. Etrial . gives a trial wavefunction which is closest to the real wavefunction. Variational method The basic idea behind the variational method is to use a trial wavefunction with an adjustable parameter. the ground state energy correction is then calculation from Z ∞ (1) (0)∗ ˆ (0) ψ0 H (1) ψ0 dx (30.7) 209 . The basis for this is the variation theorem which states Etrial ≥ E.5) E0 = −∞ Z ∞ 2 2 A0 e−αx /2 ax4 A0 e−αx /2 dx = −∞ Z ∞ 2 2 x4 e−αx dx = aA0 √ −∞ 3 πaA2 0 = . The trial energy is calculated by Etrial = R R all space ˆ ψ∗ Hψtrial dx trial ψ∗ ψtrial dx trial (30. 5 2 2 4α 30. 5 4α 2 so the first order ground state energy for a quartic oscillator is √ ~ω 3 πaA2 0 + E0 ' .• For example. p. that we use to minimize the trial energy by setting dEtrial =0 dp (30.6) all space The trial energy is now a function of the adjustable parameter.

and solving for p.) 210 . (Strictly speaking we should check that we have a minimum and not a maximum or inflection point. but with reasonably good trial functions one is pretty safe in having a minimum.

1. Unlike the harmonic oscillator it has no classical analogue. The two level system is inherently quantum mechanical in nature. 31. We shall finally get to quantum dynamics in this chapter. The time variable never appears in any expression. The spin system discussed above is an example of a two level system.31. The Two Level System and Quantum Dynamics Our entire discussion of quantum mechanics thus far had dealt only with time independent quantum mechanics. the two level system is a close second. but first we will discuss the very important model of the two level system. For example. The Two Level System If the harmonic oscillator is the most important model in all a physics. Obviously there are cases where quantum objects move with time. firing an electron down a particle accelerator. 211 211 .

212 . ˆ H= 1 δ 1.° + 2 δ 2.° “projects out” the j th state of the wavefunction being acted on.2) where δ j. we can not use our usual procedure of writing down the classical Hamiltonian and then replacing the variables with their corresponding operators. (31.Consequently. The two level system consists of two states ψ1 and ψ2 separated by energy 4 = 2 − 1 as shown below The states ψ1 and ψ2 are orthonormal: Z ψ∗ ψk dΩ = j ( 1 0 j=k .1) TLS R where TLS dΩ means integration over the two level space (which is really just the P sum 2 ).° . i=1 The states ψ 1 and ψ2 are eigenfunctions of the two level Hamiltonian. j 6= k (31.

2 2 (31. then ˆ Hψ = ( 1 δ 1.° (31.5) states.° 2 δ 2. We can invert above equations and solve for ψ1 and ψ2 in terms of ψL and ψR 1 1 ψ1 = √ ψL + √ ψR 2 2 and 1 1 ψ2 = √ ψL − √ ψR .° ) (aψ 1 + bψ2 ) 2 δ 2.4) (31.For example let some arbitrary wavefunction ψ = aψ 1 + bψ2 .° + = 1 δ 1.7) 213 .3) (aψ1 + bψ2 ) + (aψ1 + bψ2 ) = a 1 ψ1 + b 2ψ2 Another orthonormal set of wavefunctions are the so-called ‘left’ 1 1 ψL = √ ψ1 + √ ψ2 2 2 and ‘right’ 1 1 ψR = √ ψ1 − √ ψ2 2 2 (31.6) (31.

t) = ¯ Ψn (x. Ψn (x. This is given by ¯Z ¯2 ¯ ¯ ∗ P (x. t) ∂t i ∂ψn (x)e− ~ En t i~ ∂t i ∂e− ~ En t i~ψ n (x) ¶ ∂t µ i i i~ψ n (x) − En e− ~ En t ~ i~ i ˆ = HΨn (x. t)dx¯ (31. What has been kept hidden up to now is the fact that the eigenfunctions are really multiplied by a phase factor of the form . 214 .8) We can verify this by obtaining the time independent Schrödinger equation from the more general time dependent ∂Ψn (x.31. Quantum Dynamics So far we have been concerned with the eigenfunctions and eigenvalues (energy levels) of the various quantum systems that we have discussed. t) i ˆ = Hψn (x)e− ~ En t i ˆ = Hψn (x)e− ~ En t i ˆ = Hψn (x)e− ~ En t i (31.2.10) Does this mean the eigenstates are not stationary states? To determine this we need to calculate the probability of finding the particle in the same eigenstate at some future time. 0)Ψn (x.9) ˆ En ψn (x)e− ~ En t = e− ~ En t Hψn (x) ˆ En ψn (x) = Hψ n (x) (31. t) ≡ ψn (x)e− ~ En t i (31.11) ¯ ¯ ¯2 ¯Z ¯ ¯ i ∗ − ~ En t dx¯ = ¯ ψ n (x)ψ n (x)e ¯ ¯ ¯ ¯2 Z ¯ −iE t ¯ ∗ ¯e ~ n ψn (x)ψ n (x)dx¯ = ¯ ¯ ¯ i ¯2 ¯ ¯ = ¯e− ~ En t (1)¯ = 1.

it may be in a superposition of any number of eigenstates.12) (31. The phase factor does become important for superposition states. As an example consider the state 1 1 Φ(x.14) i i ∗ ∗ − ~ E1 t − ~ E2 t ¯ ¯2 +ψ2 (x)ψ 1 (x)e + ψ2 (x)ψ 2 (x)e The “cross-terms” (those of the form ψ∗ (x)ψ 2 (x) and ψ ∗ (x)ψ 1 (x)) are zero when 1 2 215 . t)¯ P (x.13) Let’s now track the probability of finding the particle in the same superposition state. In general the state of the system need not be in one particular eigenstate. 0)Φ(x. Thus the eigenstates are stationary states. t) 2 2 exposing the phase factors we get i i 1 1 Φ(x. t) = √ ψ1 (x)e− ~ E1 t + √ ψ2 (x)e− ~ E2 t 2 2 (31.so no matter what time t we check we will always find the system in the same eigenstate. The “left” and “right” wavefunctions that we saw in the discussion of the two level system are examples of superposition states. Similar to before we calculate ¯2 ¯Z ¯ ¯ ¯ Φ∗ (x. = ¯ (31. t) + √ Ψ2 (x. t) = √ Ψ1 (x. t) = ¯ ¯ ¯Z µ ¶¯2 ¶µ ¯ ¯ i i 1 ∗ 1 ∗ 1 1 − ~ E1 t − ~ E2 t ¯ ¯ √ ψ1 (x) + √ ψ2 (x) √ ψ1 (x)e = ¯ + √ ψ2 (x)e ¯ 2 2 2 2 ¯ Z à ! ¯2 i i ¯ ¯1 ψ ∗ (x)ψ 1 (x)e− ~ E1 t + ψ∗ (x)ψ 2 (x)e− ~ E2 t ¯ ¯ 1 1 dx¯ .

This leaves ¯2 ¯Z ¯ ¯ ¯ Φ∗ (x. t)¯ (31. +e +1 = = 4 2 ~ The probability of find in the system in its original superposition states is not one for all times t. 0)Φ(x.15) P (x. t) = ¯ ¯ ¯ Z ³ ´ ¯2 ¯ ¯1 i i ∗ ∗ − ~ E1 t − ~ E2 t dx¯ ψ 1 (x)ψ 1 (x)e + ψ2 (x)ψ 2 (x)e = ¯ ¯ ¯2 ¯ µ ¶¯2 Z Z ¯1 − i E t ¯ i ∗ ∗ − ~ E2 t 1 ¯ e ~ ψ1 (x)ψ 1 (x)dx + e ψ2 (x)ψ 2 (x)dx ¯ = ¯ ¯ 2 ¯ ³ ´¯2 ´³ i ´ ³ i ¯1 − i E t ¯ i i i ¯ e ~ 1 + e− ~ E2 t ¯ = 1 e+ ~ E1 t + e+ ~ E2 t e− ~ E1 t + e− ~ E2 t = ¯ ¯ 2 4 ¶ ³ ´ 1µ i i (E1 − E2 ) 1 + ~ (E1 −E2 )t − ~ (E1 −E2 )t 1+e 1 + cos t . 216 .integrated because the eigenfunctions are orthogonal.

16) • The normalized wavefunction: ψnorm = 1 ψ . sZ N= space |ψunnorm (x. z)|2 dxdydz. N unnorm (31. This section should not substitute for your studying of the rest of this material.Key Equations for Exam 1 Listed here are some of the key equations for Exam 1. ˆ hˆ i = α space (31. y. The equations are collected here simply for handy reference for you while working the problem sets. Equations • The short cut for getting the normalization constant . The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations. Z ψ∗ αψdxdydz. (31.18) 217 217 .17) • How to get the average value for some property.

8ma2 8mb2 8mc ( (31.nz • Orthonormality: Z n2 h2 n2 h2 n2 h2 y x = + + z 2. (31. j 6= k (31. Lx = L2 .ny . sin ψn (x) = √ a b c abc • The energy levels for the 3D particle in a box.22) • Superpostion: ψ= X i ai ϕi (31.27) 218 .19) • Normalized wavefunctions for the 3D particle in a box.24) L L L and h i h i h i ˆ 2 . ˆ ˆ ˆ ˆ ˆ L m2 h2 ~2 m2 = . 2π (31. ˆ z .• The Laplacian ∇ = 2 µ ∂2 ∂2 ∂2 + 2+ 2 ∂x2 ∂y ∂z ¶ .20) (31. 2I 8π2 I (31.25) • The energy levels for a particle in a ring are Em = (31. Enx .23) • Commonly used comutators of the angular momentum operators are h i i i h h ˆ ˆ ˆ ˆ ˆ ˆ ˆ x . Ly = L2 . ˆ y . Lx = i~Ly (31. j=k . Lz = i~Lx . Lz = 0.26) • The normalized wavefunctions for a particle on a ring are 1 ψ = √ eimφ . √ ny πy nz πz nx πx 2 2 sin sin .21) ψ∗ ψk j = space 1. 0. Ly = i~Lz .

31) • The trial energy in variation theory is calculated by R ∗ ˆ all ψ trial Hψ trial dx space Etrial = R ∗ all ψ trial ψ trial dx space (31. t) ≡ ψn (x)e− ~ En t i (31.33) • The left and right superposition states are 1 1 ψL = √ ψ1 + √ ψ2 2 2 and 1 1 ψR = √ ψ1 − √ ψ2 2 2 (31. • The first order energy correction in pertubation theory is Z (1) ˆ ψ(0)∗ H (1) ψ(0) dx. 2I (31.32) • In general Ψn (x. En = n n all space (31. ˆ L2 ψlm = l(l + 1)ψ lm • The energy levels for the rigid rotor are El = l(l + 1)~2 .35) 219 .• The eigenfunctions of angular momentum are entirely specified by two quantum numbers l and m: ψ lm .34) (31.29) ˆ Lz ψlm = mψ lm (31.30) (31.28) • Degeneracy for general angular momentum is gJ = 2J + 1.

Part VI Symmetry and Spectroscopy 220 220 .

Symmetry and Group Theory We now take a short break from physical chemistry to discuss ideas from the mathematical field of group theory. As far as we are concerned. we will • determine the symmetry of a particular molecule. Inherent to group theory is symmetry. • The types of symmetry it has will determine to which symmetry group it belongs. • The mathematical properties of all the possible groups have been worked out • These mathematical properties translate into a wide variety of variety of physical properties including — Bonding — Properties of wavefunctions — Vibrational modes — Many more applications 221 221 .32.

ı ˆ An example of symmetry operator that is not a point group symmetry operator would be an operator that performed some sort of translation in space. An identity element exits and is a member of the group 222 . Mathematical Groups In mathematics the term “group” has special meaning. ∗ ∗ ∗ See Handout on Symmetry Elements ∗ ∗∗ (32.1) This implies ˆ Oψ = ±ψ. This type of operator arrises in the treatment of extended crystal structures. These operators deal with symmetry about the center of mass.2) 32. The group is associative (but not necessarily communative) with respect to the operation. Symmetry Operators Any operator that leaves |ψ|2 invariant are symmetry operators for that particular system: ˆ O |ψ|2 = |ψ|2 .32. the eigenvalues for the particular symmetry operator are 1 or −1. which has the following properties.1. That is. (32. We have seen two such operators in ˆ and σ h . It is a set of objects and a single operation. For molecules we will be dealing with point group symmetry operators.2. 2. 1.

The inverse of every member of the group is also in the group.3. C2 . 223 .2. 4. Water is an example of a molecule described by this point group. The “product” of any two members of the group yield a member of the group. 32. for any member of the group one can find another member of the group which. Symmetry of Functions In the absence of degeneracy.” yields the identity element. The multiplication table for the C2v group is C2v ˆ E ˆ C2 σv ˆ σ 0v ˆ ˆ E ˆ E ˆ C2 σv ˆ σ 0v ˆ ˆ C2 ˆ C2 ˆ E σ 0v ˆ σv ˆ σv ˆ σv ˆ σ 0v ˆ ˆ E ˆ C2 σ 0v ˆ σ 0v ˆ σv ˆ ˆ C2 ˆ E 32. In other words. Example: The C2v Group ˆ ˆ ˆ The C2v group consists of the symmetry elements E. σ v (in-plane) and σ 0v ˆ (transverse). ∗ ∗ ∗ See Handout on Naming Point Groups ∗ ∗∗ ∗ ∗ ∗ See Handout on Assigning Point Groups ∗ ∗∗ Associated with a given group is a “multiplication” table. the wavefunctions must be symmetric or antisymmetric with respect to all elements of the group.1. upon “multiplication.3.

ˆ • The first value has to be +1 since the only eigenvalue of E is 1 ˆ • The eigenvalue of C2 can be +1 or −1 — When it is +1 the vectors are labelled A — When it is −1 the vectors are labelled B • The eigenvalue of σ v can be either +1 or −1 ˆ — When it is +1 the vectors are labelled with a subscript 1 — When it is −1 the vectors are labelled with a subscript 2 • The eigenvalue of σ 0v can be either +1 or −1 ˆ • Finally there is a restriction do to the fact that the eigenvalues must obey the group multiplication table. consider the following. To see where these four vectors come from. −1) B1 = (1. −1) B2 = (1. In this case one can collect the eigenvalues (either +1 or −1) for each of the four symmetry operators as a four component vector. 1. As it turns out there is four possible sets of eigenvalues–hence four different vectors: A1 = (1. 224 . −1.Connecting with the C2v group example lets consider the wavefunctions for water. −1. 1) A2 = (1. 1). 1. 1. −1. ˆ — This restriction forces the eigenvalues of σv and σ 0v to be the same for ˆ the A type vectors and opposite for the B type vectors. −1. 1.

−1.1. the vectors represent what is call an irreducible representation of the group. These vectors make up the : C2v A1 A2 B1 B2 ˆ E ˆ C2 σv ˆ σ 0v ˆ 1 1 1 1 1 1 −1 −1 1 −1 1 −1 1 −1 −1 1 ∗ ∗ ∗ See Handout on Character Tables ∗ ∗∗ 32.3) 32.4) (32. 1) = (1. x3 y3 . x2 . Altogether. 1. x3 . Symmetry Breaking and Crystal Field Splitting We shall investigate how degeneracies of energy levels are broken as one reduces the overall symmetry of the system. . y3 . −1) ⊗ (1. . −1) = A2 (32. . . there will always be the same number of vectors as symmetry elements. −1. −1. x2 y2 . In fact. .) = (x1 y1 . y2 . 1.The above considerations leave four vectors.4.) ⊗ (y1 . 225 . . . −1. . . Direct Products The direct product of a two vectors is defined as (x1 .) For the example of the C2v group consider B1 ⊗ B2 = (1.3.

y and z as we see from the character table for the spherical group. When moving to octahedral symmetry we now must look at the character table for such a case–the O group (remember we are considering only proper rotations). The vectors are the labeled according to the angular momentum quantum numbers S. It remains totally symmetric so it is now represented by the vector A1 . Thus the symmetry group is the spherical group (see character table handout. The P vector is triply degenerate and has the symmetry of x. For example placed at the center of a cube which has other atoms at the centers of each face of the cube. 5 for D and so on as is familiar to us already. F. consider only proper rotations (Cn ). In the octahedral crystal the degeneracy remains in tact and these states are represented by the T1 group. In this case there is complete rotational symmetry. 3 for P. The S vector has the symmetry of a sphere (x2 + y 2 + z 2 ) and hence is totally symmetric.) This is the group associated with the particle on a sphere model and the angular part of the hydrogen atom. of course.In doing this we will. D. It is also nondegenerate so it will be. 226 . etc. nondegenerate in the octahedral case. Now consider the free atom being placed in a crystal lattice of octahedral symmetry. Mirror symmetry will not be considered (although in real applications one must consider all symmetry). The degeneracies of these vectors are 1 for S. P. for simplicity. First consider a free atom.

The octahedral group is still highly symmetric. 227 .The D vector has a degeneracy of five and the symmetry of 2z 2 − x2 − y 2 . xy. This is not readily apparent from the character tables so one needs to inspect a little harder to see it (see homework). Now the A1 vector of the O group becomes the A1 vector of the D4 group. three becoming T1 and three becoming T2 . The F states have a degeneracy of 7 and the symmetry of z 3 . The T2 states from the O group become a B2 and a E type state. The triply degenerate T1 vector splits into a A2 state and a doubly degenerate E state. Lets say that two atoms on opposite sides of the cube are moved slightly inward. x(x2 − 3y 2 ) and y(3x2 − y 2 ). x2 − y 2 . yz. xyz. yz 2 . In an octahedral environment the states split with one becoming A2 . z(x2 − y 2 ). This breaks the octahedral symmetry and the system now assumes D4 symmetry. The remaining four atoms remain in place. Looking at the table for the O group we see the degeneracy splits: two states become E type and the remaining three become T2 type. xz. xz 2 . The E states from the O group become a A1 type state and a B1 type state. The T1 states from the O group become a A2 type state and a E type state.

As for the diatomic case 3 degrees of freedom determine the center of mass motion. 33. One must now consider two different types of polyatomic molecules: Linear and Nonlinear.1.33. That leaves us with 3N − 3 coordinates to specify. Molecular Vibrations As for diatomic molecules. With polyatomic molecules one needs to specify the coordinates of N nuclei rather than just two nuclei. 228 228 . So. • For linear molecules there are 2 rotational degrees of freedom • For nonlinear molecules there are 3 rotational degrees of freedom This now leaves one with 3N − 5 vibrational degrees of freedom for linear polyatomic molecules and 3N − 6 vibrational degrees of freedom for nonlinear molecules. Molecules and Symmetry From our chapter on diatomic molecules last semester we have learned a great deal which caries over directly to polyatomic molecules. it is convenient to work with center of mass coordinates. in this chapter we simply investigate some of the specific details regarding polyatomic molecules. To do so we begin with the 3N nuclear degrees of freedom.

Normal Modes Polyatomic molecules can undergo very complicated vibrational motion. At low energies the normal modes are well approximated as harmonic oscillators. This is analogous to writing an arbitrary wavefunction as a linear combination of eigenfunctions. Normal Modes and Group Theory The symmetry of the normal modes are associated with entries in the character table of the point group of any particular polyatomic molecule.1. Regardless of what type of vibrational motion is taking place.1. One example was the “left” and “right” states of the two level system.2. 229 . The three modes are the bending vibration. however. The character table is C2v A1 A2 B1 B2 ˆ E ˆ C2 σv ˆ σ 0v ˆ 1 1 1 1 1 1 −1 −1 1 −1 1 −1 1 −1 −1 1 Water has three nuclei and it is nonlinear so it has 3(3) − 6 = 3 normal modes.33. that motion is some linear combination of fundamental vibrational motions called normal modes.1. The number of normal modes equals the number of vibrational degrees of freedom. Example: Water The point group symmetry of the water molecule is C2v . the symmetric stretching vibration and the asymmetric stretch. 33.

ˆ 230 . For the bending mode. Consequently the bending mode is associated with A1 The same is true for the symmetric stretching mode. however.The normal modes are associated with a particular vector (row) of the character table by considering the action of the each of the symmetry elements on the normal mode. the vibration is complete unchanged by any of the symmetry elements. It too is associated with A1 . is associated with B1 since C2 and σ0v transform ˆ the mode into its opposite and σ v leaves it unchanged. ˆ The asymmetric stretch.

1. This is in the Infrared region of the electromagnetic spectrum.1) . As for electronic absorption one typically employs the electric dipole approximation. in particular. The electric dipole approximation • Molecule is viewed as a collection of charges • Multipole expansion monopole + dipole + quadrapole+ · · · 231 231 (34. Vibrational Spectroscopy and Group Theory We now investigate how group theory and.34. The typical “energies” for IR absorption are from 400 to 4000 cm−1 . IR Spectroscopy IR absorption is exactly the same as regular electronic absorption except the frequency of the electromagnetic radiation is much less. the character tables can be used to determine IR and Raman spectra and selection rules for polyatomic molecules 34.

Example: Water Recall that the point group symmetry of the water molecule is C2v . y. The electric dipole is μ = μx ex + μy ey + μz ez where μx = qx. z 2 1 1 −1 −1 xy 1 −1 1 −1 x. We now need a column of the character table which we have ignored up to this point. or z for the particular group. The upshot of all this is as far as group theory is concerned is the following selection rule: • The vibrational coordinates for an IR active transition must have the same symmetry as either x. The character table is C2v A1 A2 B1 B2 ˆ E ˆ C2 σv ˆ σ 0v ˆ Functions (34.2) 1 1 1 1 z. xz 1 −1 −1 1 y. yz The last column describes the symmetry of several important functions for the point group. y 2 . In order for absorption of the electromagnetic radiation to take place. 232 .• Light—matter interaction is dominated by the light—dipole coupling so the other interactions are ignored. it must be able to couple to a changing (oscillating) electric dipole. x2 . μy = qy. μz = qz.

y. Raman scattering is based on the polarizability of the molecule Roughly speaking the polarizability of a molecule determines how the electron density is distorted through interaction with an electromagnetic field. Raman Spectroscopy Raman spectroscopy is somewhat different than IR spectroscopy in that vibrational frequencies are measured by way of inelastic scattering of high frequency (usually visible) light. This lose of energy shows up in the scattered light as a new down shifted frequency from that of the original input light frequency. Unlike IR absorption which is based on the electric dipole. The light loses energy to the material in an amount equal to the vibrational energy of the molecules is the sample. 233 . So we can see immediately that the IR active modes of any molecule having this point group will be A1 . and B1 symmetry and hence are all IR active and appear in the IR spectrum 34.Among these functions are x. B1 .2. The A2 mode is IR forbidden and any vibrations having this symmetry will not appear in the IR spectrum (or it may appear as a very weak line). and B2 . and z. From before we know the modes of water have A1.

One can now inspect the character table to determine which modes will be Raman active. ↔ 234 . y 2 . (or any combinations thereof). We will not get into tensors in this course except to say the polarizability tensor elements are proportional to the quadratic functions. z 2 . yz. all modes are Raman active Rule of Mutual exclusion • Vibrational mode can be both IR and Raman active or inactive • If. xy.The molecular quantity of interest is the polarizability tensor. the molecule has inversion symmetry (contains ˆ as a symmetry ı element) then no modes will be both IR and Raman active. x2 . For the example of water. xz. α. however.

For constant R the rotational energy is given by − Erot = J(J + 1)~2 J(J + 1)h2 . θ.2) J . It is common to define Be ≡ as the rotational constant. under the Born-Oppenheimer approximation. (35. ~2 ˆ2 (35. Then Erot = J(J + 1)hBe with a degeneracy of gJ = 2J + 1 235 235 h 8π 2 I (35. φ).3) This is the so-called rigid rotor energy. = 2μR2 8π 2 I (35. 2I Now.6) . R is a parameter.4) (35. Molecular Rotations Recall that the three degrees of freedom that described the position of the nuclei about the center of mass were (R.1) R 2μ 2μR2 ∂R ∂R 2μ We will now be concerned only with the angular part. The R was involved in vibrations. Recall also the Kinetic energy operator for the nuclei in the center of mass coordinates 2 2 ~2 ˆ2 ∂ ˆ2 ∂ ˆN = − ~ ∇2 = − ~ ˆN T + J .5) (35. We now turn our attention to the angular components to describe rotations.35.

35. a rotational transition can accompany a vibrational transition. Rotational Spectroscopy A rotational transition can occur in the same vibrational level n. n.8) (35. There are two corrections we will now make 1. ¶ µ 1 Bn ≡ Be − n + αe . 236 .1. Alternatively. where Dc ≡ 3 4Be ω2 ˜e (35. • One defines a rotational interaction constant that depends on the vibrational level.7) 2 where αe is an empirical rotational—vibrational interaction constant. Relaxing the rigid rotor Of course the rigid rotor is not a perfectly correct model for a diatomic molecule. 2.2. Centrifugal stretching: • Rotation tends to stretch the diatomic distance R. (35. This is called a pure rotational transition. 35. In either case the selection rule for the transition is 4J = ±1.9) is the centrifugal stretching constant. • This is corrected for by the term −J 2 (J + 1)2 Dc . Vibrational state dependence: • The R value is dependent on the particular vibrational level.

I = Ixx + Iyy + Izz The Hamiltonian in the principle axes system is # " ˆ2 ˆ2 ˆ2 Jy ~2 Jx Jz ˆ + + H= 2 Ixx Iyy Izz (35. Rotation of Polyatomic Molecules There are a few additional details regarding rotations for polyatomic molecules as compared to diatomics Of course one could set-up an arbitrary center of mass coordinate system.10) 237 . kT. But one system is special–the principle axes coordinate system.3. Thermal energy. The total moment of inertia. This means that at room temperature the many excited rotational states are populated. ∗ ∗ ∗ See Handout ∗ ∗∗ 35. The principle axes coordinate system is the one in which the z-axis is taken to be along the principle symmetry axis. at room temperature is about 200 cm−1 .It turns out that typical rotational energy gaps are on the order of a few wavenumbers or less. ∗ ∗ ∗ See Handout ∗ ∗∗ The selection rules and the thermalized states combine to yield a multi-peaked ro-vibrational spectrum.

There are four classes of polyatomic molecules regarding rotations 1. Ixx = Iyy ˆ ˆ2 ˆ2 • J 2 = Jx + Jy • The Hamiltonian is • The rotational energy is Erot = hBJ(J + 1). carbon dioxide) • Izz = 0. Linear (e. where B= 2.11) (35. (35. Symmetric tops (e.g. benzene) • Ixx = Iyy h 8π2 Ixx (35..17) B= 2 8π Ixx and K is the quantum number describing the projection of the angular momentum onto the z-axis 238 .14) • The rotational energy is Erot = hBJ(J + 1) + h(A − B)K 2 . where A= (35.12) ~2 ˆ2 ˆ J H= 2Ixx (35.13) ˆ ˆ2 ˆ2 ˆ2 • J 2 = Jx + Jy + Jz • The Hamiltonian is # " ˆ2 ˆ2 ˆ2 ~2 Jx + Jy Jz ˆ + H= 2 Ixx Izz (35.16) 8π 2 Izz h (35..g.15) h .

methane) • Ixx = Iyy = Izz ˆ ˆ2 ˆ2 ˆ2 • J 2 = Jx + Jy + Jz • The Hamiltonian is • The rotational energy is Erot = hBJ(J + 1).3.g.20) 4.18) (35.19) ~2 ˆ2 ˆ J H= 2Ixx (35.. Spherical tops (e. where B= h 8π2 Ixx (35. Asymmetric tops • Ixx 6= Iyy 6= Izz • These are more complicated and we will not discuss them in detail 239 .

36. Molecular spectra. Atomic spectra consist of single sharp lines due to transitions between energy levels. Electronic Spectroscopy of Molecules The electronic spectra of molecules are quite different than that of atoms. It had a qualitative shape similar to the Morse potential. 240 240 . have numerous lines (bands) due to the fact that electronic transitions are accompanied by vibrational and rotational transitions. We found that in doing so the electronic energy level.36. The Structure of the Electronic State Last semester we saw that under the Born—Oppenheimer approximation we were able to write the molecular wavefunction as a product of an electronic part and a nuclear part. Ee . on the other hand. Ee as a function of R describe the effective potential for the nuclei. R. was parameterized by the internuclear distance.1.

2. ∗ ∗ ∗ See Spectroscopy Supplement p1 ∗ ∗∗ 36. Absorption Spectra In absorption spectroscopy.In the figure below the ground and first excited electronic levels (as a function of R) are shown. light demotes an electron from the ground vibrational state of the excited electronic state to any one of a number of excited vibrational levels in the ground electronic state.1.1. 36. Note: The potential minima are not at the same value of R for each of the electronic states. 241 . light promotes an electron from the ground electronic state (and usually from the ground vibrational state too) to the excited electronic state and any of the excited vibrational states of the excited electronic state. Emission Spectra In emission spectroscopy.1.

• This requires a lower energy (or “more red”) photon.∗ ∗ ∗ See Spectroscopy Supplement p2 ∗ ∗∗ 36. • The system then very rapidly (on the order of tens to hundreds of femtoseconds) relaxes to the ground vibrational state of the excited electronic state.3. the process of is taking place. Hence the Stokes shift. 242 . Fluorescence Spectra All during the process of absorption. • This process is called • The molecule than emits a photon to drop back down into an excited vibrational state of the ground electronic state. The main stream explanation for the stokes shift is as follows • Light promotes the system from the ground vibrational and ground electronic state to excited vibrational levels in the excited electronic state.1. ∗ ∗ ∗ See Spectroscopy Supplement p3 ∗ ∗∗ As seen in the supplement the fluorescence spectrum is shifted to lower energies (red shifted) from the absorption spectrum. This is known as the Stokes shift.

The Franck—Condon principle states that the nuclei do not move during an electronic transition.f is given by ¯Z ¯ ¯ ¯ ¯ ¯2 ¯Z ¯ ¯ ¯ ¯ Ψ∗ μel Ψi ¯ = ¯ ˆ f ¯ ¯ Z ¯2 ¯ ¯ ψ∗ ψ∗ μel ψel.i ¯ . ˆ el. This is down by evaulating the Franck—Condon integral. Franck—Condon activity We have seen than an electronic tranistion involves not only a change in the electronic state but also in the vibrational state in general (and in the rotaitonal state as well. 36.f vib.i ψvib.i ψvib. one obtains the Franck—Condon principle. but we will ingore this).36. The Franck—Condon principle When the Born—Oppenheimer approximation is applied to spectroscopic transitions. Physically this means that for a particular transition to be Franck—Condon active there must be good overlap of the vibrational wavefunctions involved in the transition.2.1.f ψvib. Assuming the electronic transition is allowed one must calculate the probability of the vibrational transistion as well.i → Ψf = ψel. Mathematically this means that the strength of a transition from Ψi = ψel.1) all space el space vib space 243 .2.f ¯ (36.

f μel ψel.f ψvib.where μel is the electronic transition dipole. (36. We can separate the integrals as ˆ ¯2 ¯Z ¯2 ¯Z ¯¯ ¯ ¯ ¯¯ ¯ ¯ ∗ ∗ ψel.i ¯ ¯ ˆ ψvib.i ¯ .2) ¯ ¯ ¯ vib ¯ ¯ el space space | {z }| {z } if 6=0. allowed Franck—Condon 244 .

conversely. One should be familiar with qualitative aspects of this time—frequency relation.1.1) −∞ 245 245 . (37. if the signal decays rapidly it will have a broad spectrum and. of a function f (t) will. 37. in this work. Spectroscopic data is obtained either in the time domain or in the frequency domain and one should readily be able to look at data in one domain and know what is happening in the other domain. Fourier Transforms As a spectroscopist it is imperative to have a deep understanding of the relationship between time and frequency. =. Furthermore.37. and is given by Z ∞ ˜(ω) = = [f (t)] = f f(t)eiωt dt. The Fourier transformation The Fourier transformation. by denoted ˜ by a tilde. if the signal decays slowly it will have a narrow spectrum. The mathematics which governs these qualitative statements is Fourier transform theory which we now review. f (ω). such as if a signal oscillates in time it will have a peak in it frequency spectrum at the frequency with which it is oscillating.

which is given by Z ∞ h i 1 −1 ˜ ˜ = (37.e. so one must take care to know exactly which convention is being used. f (ω) = f (t) = 2π −∞ The above two relations form the convention used throughout this work. i. For simplicity the symbol = will be used to represent the Fourier transformation ˜ operation. i...e. Other authors use different conventions. = f(ω) = f(t). Whereas the symbol =−1 will represent the inverse h i −1 ˜ Fourier transformation. = [f (t)] = f (ω). 246 .The Fourier transformation is unique and it has a unique inverse.2) f(ω)e−iωt dω. =−1 .

Equations • Vibrational degrees of freedom — linear: 3N − 5 — not linear: 3N − 6 • The so-called rigid rotor energy is Erot = J(J + 1)hBe . This section should not substitute for your studying of the rest of this material.Key Equations for Exam 2 Listed here are some of the key equations for Exam 2.4) . The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations. 247 247 (37.3) h 8π 2 I (37. where Be ≡ is the rotational constant. The equations are collected here simply for handy reference for you while working the problem sets.

• The degeneracy of the rigid rotor is gJ = 2J + 1 • Franck—Condon Factor: ¯Z ¯ ¯ ¯ ¯ ¯2 ¯ ¯ ψ∗ ψvib.i ¯ vib.f ¯ Z ∞ (37.6) • The Fourier transformation is ˜ = [f (t)] = f (ω) = f (t)eiωt dt.8) 248 . (37. f (ω) = f (t) = 2π −∞ (37.5) vib space (37.7) −∞ • The inverse Fourier transformation is Z ∞ h i 1 −1 ˜ ˜ = f(ω)e−iωt dω.

Part VII Kinetics and Gases 249 249 .

vzi ). 250 250 . t) which is in general a function of time. ¡ ¢ Its velocity is vi = dxi = dxi . vz . 38.1. vyi . m is the molecular (or atomic) mass • Each particle of mass m has velocity v.38. t. dzi . vy . 2 2 • A sample of N molecules is characterized by its number density n∗ = • From the ideal gas law P V = nRT = N PL = RT = n∗ V N RT L N . z) in coordinate (position) space. dyi . The velocities of the particles are characterized by a probability distribution function for velocities F (vx . kinetic theory of gases A microscopic view of gases Consider a gas of point mass (m). y. Physical Kinetics We now turn our attention to the molecular level and in particular to molecular motion. V (L is Avogadro’s number): Consider the ith particle at position xi = (x. hence a momentum of p = mv and a kinetic energy of KE = 1 mv · v = 1 mv 2 . This can represented in velocity space by dt dt dt dt the vector vi = (vxi .

φ. φ). φ. t) = F (v. in velocity space is Z Z Z Z NVv = N F (v.. φ). θ.b. θ. (38. θ. t)dvx dvy dvz (38. (38. v is simply a magnitude (not a vector)–it is the speed. θ.2) Furthermore.3) 251 . then for many cases the velocity distribution will be isotropic–independent of θ and φ. t) If we choose the origin of our coordinate system to be at the center of mass of the gas. Vv . NVv . vz . θ. vy . t) = F (v. n.1) Vv Vv It is more convenient to switch to spherical polar coordinates in velocity space (v. stationary distributions–those independent of time–are often encountered. F (v. t). t)dv = N F (vx . having velocities in a macroscopic volume. F (v. The probability distribution function then becomes F (v.The number of particles. φ.

n = = RT .5) 2πkT 0 0 s r µ ¶ 8kT L Lk=R 8RT = = πm L Lm=M πM It will be convenient to define number density as n∗ ≡ N where N is the number V N P nRT LP ∗ of particles.We shall consider stationary isotropic distributions F (v). This is the Maxwell’s distribution (of speeds). It can be shown from first principles that µ ¶3 2 −mv 2 m F (v) = 4π e 2kb T v 2 (38. For an ideal gas (V = P ). Molecular Collisions The average speed of a particle can calculated from Maxwell’s distribution: Z ∞ Z ∞ m 3 − mv2 ) 2 e 2kT dv hvi = v = ¯ vF (v)dv = v 3 4π( (38. n RT |{z} =L A simple model for molecular collisions: 252 .4) 2πkb T where kb = 1.380658 × 10−23 is Boltzmann’s constant. 38. So F (v) represents a distribution of speeds.2.

• Particles are hard spheres of radius σ. Since the molecules are moving relative to one another we must find the average relative velocity.48 ¯ m .7) From the above expression one defines the mean free path λ to be v ¯ / λ= √ 2n∗ πσ 2/ v ¯ LP n∗ = RT = RT √ 2P Lπσ 2 (38. • A Particle moving at v sweeps out a cylinder of radius σ and length v4t =⇒ V = πσ2 v4t. ¯ πM frequency (38.5 nm 253 . ∗ ∗ ∗ See Handout ∗ ∗∗ • The number of collisions equals the number of particles with their centers in V : number of collisions = n∗ πσ 2 v4t (38. P = 1 bar): v = 380.6) • The collision frequency = n∗ πσ 2 v For the above model we need to find the average collision frequency. frequency λ = 72. s collision = 5.25 × 109 s−1 .8) Example: Ar at SATP (T = 298 K. v12 = h|v1 − v2 |i ¯ It can be shown that r v12 = ¯ √ √ collision 16RT = 2¯ =⇒ v = 2n∗ πσ 2 v .

The Rate Laws of Chemical Kinetics Thermodynamics described chemical systems in equilibrium. equal b.2) − dt dt dt dt BUT this is ambiguous because a moles of A reacts with b moles of B and a does not. Rate Laws Consider a general four component reaction aA + bB = cC + dD (39.39. in general. We can. d[B] d[C] d[D] d[A] or − or or (39. For this we turn to the field of chemical kinetics. address the question.1. For the study of chemical reactions it is important understand systems that can be very far from equilibrium. however. Will the reaction occur? We need kinetics. from thermodynamics. answer the question: How fast will the reaction occur? 39. We must account for the stoichiometry. 254 254 .1) The time dependence of this reaction can be observed by following the disappearance of either of the reactants or appearance of either of the products. That is.

rate laws are empirical. B. C. −b. This definition is useful but must be used with caution since for complicated reactions all the v’s may not be equal. Many.) (39. or D. v = f (conc. An example of this is ½ bB → cC + dD aA + (39.We define the reaction velocity as v= 1 d[I] vi dt (39. rate laws are of the form v = k[A1 ]xA 1 [A2 ]xA 2 · · · [An ]xA n . c or d and I = A. but certainly not all.7) Intermediates → Product Note that we shall use an equal sign when talking about the overall reaction and arrows when talking about the elementary reactions Example 255 .6) The reaction is said to be of order xAi in species Ai and it is of overall order P i xA i . (39. In general an overall reaction is made up of so called elementary reactions Reactant Reactant = → Product overall rxn (39.5) For the most part.3) where vi = −a.4) 0 B0 → c0 C0 + d0 D0 b A rate law is the mathematical statement of how the reaction velocity depends on concentration.

8) The rate laws for elementary reactions can be determined from the stoichiometry molecularity elementary rxn rate law Unimolecular A → Product v = k[A] Bimolecular A + A → Product v = k[A]2 Bimolecular A + B → Product v = k[A][B] . at equilibrium vf = vb which implies kf [A]a [B]b = kr [C]c [D]d (39.Let 2A + 2B = C + D be the overall reaction.9) where kf is the rate constant for the reaction to proceed in the forward direction and kr is the rate constant for the reaction to proceed in the reverse direction. Trimolecular A + A + A → Product v = k[A]3 Trimolecular A + A + B → Product v = k[A]2 [B] Trimolecular A + B + C → Product v = k[A][B][C] Conversely. One possible set of elementary steps could be elementary rxn A + A → A0 A00 + 2B→ C + D A0 → A00 molecularity Bimolecular Unimolecular Trimolecular . Connection to thermodynamics Consider the overall or elementary reaction aA + bB ­ cC + dD kr kf (39.10) 256 . (39. Now. rate laws for overall reactions can not be determined by stoichiometry.

This suggests that the reaction is elementary. The observed rate law for this reaction is very complicated. Examples of rate laws Consider the (overall) reaction between molecular hydrogen and molecular iodine. The velocity of a reaction is lost in this ratio and hence we still can not determine the speed of a reaction from thermodynamics. The above two example are seemingly very similar but they have very different observed rate laws. the reaction is not elementary.” (39.11) So. (39. Moral: Kinetics is very much an empirical science. H2 + Br2 = 2HBr. Objectives of chemical kinetics 257 . Next consider the reaction between molecular hydrogen and molecular bromine. In fact. this does not obey any common form.bringing kr to the LHS and [A][B] to the RHS we get [C]c [D]d kf 0 = = Kc a [B]b kr [A] 0 where Kc is the thermodynamic equilibrium “constant. H2 + I2 = 2HI. Moral: Kinetics is very much an empirical science. we have succeeded in connecting thermodynamics to kinetics BUT we have done so through the ratio of rate constants. v= k[H2 ][Br2 ]1/2 1+ k0 [HBr] [Br2 ] (39.12) The observed rate laws are vf = kf [H2 ][I2 ] and vr = kr [HI]2 .13) .

258 . To obtain the rate from the concentration we must take its time derivative dc(t) . • For slow reactions (hrs/days) almost any technique for measuring the concentration can be used. The rates of chemical reactions vary enormously from sub-seconds to years.2.• To establish empirical rate laws • To determine mechanisms of overall reactions • To empirically study elementary reactions • To establish theoretical links to statistical mechanics and quantum mechanics — This involve nonequilibrium thermodynamics–more difficult • To study chemical reaction dynamics — the dynamics of molecular collisions that result in reactions 39. Determination of Rate Laws Concentrations c(t) are measured not rates. • For medium reactions (min) either a continuous monitoring technique or a stopping technique can be used — A stopping technique used rapid cooling or destruction of the catalysts to stop a reaction at a given point. • Very fast (sec/subsec) reactions cause problems because the reaction goes faster than one can mix the reactants. That is we must measure c(t) as a dt function of time and find the rate of change of this concentration curve. Consequently no one experimental technique can be used.

Method of isolation • for v = k[A]x [B]y rate laws • start with initial concentrations a and b equal to the stoichometry. Integrated rate laws The above differential methods look directly at the rate law which is a differential equation. A so v ≈ kax [B]y 39. say. 259 . if the concentration drops very sharply 2. Method of initial velocities • for v = k[A]x [B]y rate laws. Differential methods based on the rate law Methods based directly on the rate law rely on the determination of the time derivative of the concentration.1. • initially v0 = kax by where a and b are the initial concentrations of A and B respectively • taking the log of both sides gives lnv0 = ln[kax by ] = ln k + x ln a + y ln b • a and b can be varied independently so both x and y can be determined.39.2. if there is an induction period 2. • problems 1. The main problem with such a method is that randomness in the concentration measurements gets amplified when taking the derivative. 1. this gives the overall order of x + y • flood with.2.2. The differential equation is not solved.

b) The order need not be an integer. type rate lawa) integrated rate lawa) 1st order 2nd order nth orderb) 1 vi 1 vi 1 vi 1 vi d[I] dt d[I] dt d[I] dt d[I] dt = k[I] = k[I]2 = k[I]n [I] = [I0 ]evi kt 1 = [I10 ] − vi kt [I] 1 [I]n−1 = 1 [I0 ]n−1 k[I] enyzme = km +[I] km ln [I0 ] + ([I0 ] − [I]) = −vi kt [I] a) [I] is the concentration of one of the reactants in an elementary reaction and vi is the stoichiometric factor for [I] (n. The differential equations (rate law) and their solutions (integrated rate law) are simply listed here for a few rate laws. For example n = 3/2 is a three-halves order rate law. vi is a negative number)..b.We now solve the differential equations to yield what are called the integrated rate law. − (n − 1)vi kt 260 .

ln Ka = ln kr ∙ 261 261 (40. Temperature and Chemical Kinetics 40. d(1/T ) R where Ea is the Arrhenious activation energy. Temperature Effects on Rate Constants An empirical rate constant was proposed by Arrhenious: Ea d ln k = or dT RT 2 Ea d ln k = . Integration of the above yields ln k = ln A − Ea Ea =⇒ k = Ae− RT RT (40.4) Now.1) (40. take the log of this: ¸ kf = ln kf − ln kr .1.2) (40. This is the Arrhenious equation Recall the equilibrium constant can also be obtained from kinetics 0 Kc = kf ' Ka .40.5) .3) (A is the constant of integration). kr (40.

Theoretical approaches to reaction rates predict rate constants of the form k = aT j e−E /RT .10) 40.7) (40. Theory of Reaction Rates Simple collision theory (SCT) • Bimolecular reactions (A. Forcing this to coincide with the Arrhenious implies Ea = E 0 + jRT and A = aT j ej 0 (40.Substituting the Arrhenious equation for the rate constants gives ¸ ∙ i h Ea Ear f − RT − ln Ar e− RT ln Ka = ln Af e ∙ ¸ Ear − Eaf Af = ln + Ar RT 40.2. Temperature corrections to the Arrhenious parameters The Arrhenious parameters A and Ea are constants.6) (40.B) • Reaction rate determined by molecular collisions 262 .1.8) (40.9) We can verify this by starting with the Arrhenious equation and substituting the above expressions. k = Ae− RT = aT j ej e− Ea E 0 +jRT RT = aT j ej e/ e RT = aT j e RT / −j −E 0 −E 0 √ (40.1.

13) [A][B] = pπσ AB L s 8RT − Em in e RT πLμ (40.14) 263 .11) is the reduced mass and σAB is the collision diameter. • The maximum reaction velocity is vmax = reaction velocity will be less because zA B L .12) • The rate constant for a bimolecular reaction is v k= [A][B] so SCT predicts k= pzA B e− L Em in RT (40. but intuitively the actual — the ability to react depends on orientation =⇒ a steric factor p — a minimum amount of collisional energy is required=⇒ e−Em in /RT • The actual reaction velocity is pzAB e− v= L Em in RT (40.— Collision frequency for A–B collisions s 8RT zAB = πσ AB L2 [A][B] πLμ where μ ≡ mA mB mA +mB (40.

ACT is not limited to bimolecular reactions. e. A + B → (AB)‡ → products.. • For the above example.g.16) Activated complex theory (ACT) • An intermediate active complex is formed during the reaction.17) • The active complex is a state in the thermodynamic sense. thus we can apply thermodynamics to it.• Comparison to the (temperature corrected) Arrhenious equation suggests s 8RT 1 e2 (40.15) A = pπσ AB L πLμ and 1 Ea = Emin + RT 2 (40. (40. [A][B] (40. the equilibrium constant is defined as ‡ Ka = a‡ low [‡] ' aA aB conc.18) 264 .

the reactions we have studied have been single step reactions. — From statistical mechanics.3. it can be shown that f = kb T /h where kb is Boltzmann’s constant and h is Planck’s constant. h (40.20) which can be written as ‡ Ka = e− 4G‡ RT = e− 4H ‡ RT e 4S ‡ R (40. Parallel reactions: 265 . In general.19) • Thermodynamics tells us that ‡ 4G‡ = −RT ln Ka (40. Reactions may occur in series or in parallel or both.21) where 4G‡ = 4H ‡ − T 4S ‡ . there is many steps from initial reactants to final products. in what is called a reaction network.• Definition: transmission factor. • The reaction rate constant for reactants going to products for ACT is ‡ k = f Ka = kb T ‡ K h a (40.22) 40. Multistep Reactions Up to now. • The ACT reaction rate constant now becomes k= This is Eyring’s equation kb T − 4H ‡ 4S‡ e RT e R . f — accounts for the fraction of activated complex that becomes product.

• Parallel reactions are of the form.24) • The concentrations of A. dt which.23) A + B2 → D • The rate constant for the disappearance of [A] is simply the sum of the two rate constants: k = k1 + k2 k2 Series reactions: • Series reactions necessarily include and intermediate product. 1 A + B1 → C k (40. when solved yields [A] = [A0 ]e−k1 t ¢ k1 [A0 ] ¡ −k1 t [B] = − ek2 t e k2 − k1 ¶ µ k2 e−k1 t − k1 ek2 t [C] = [A0 ] − [A] − [B] = [A0 ] 1 − k2 − k1 • See in class animation 266 . for example. B and C are determined by the system of differential equations: − d[A] = k1 [A] dt d[B] = k1 [A] − k2 [B] dt d[C] = k2 [B]. They are of the form k1 k2 A→B→C (40.

Initiation: Typically a molecule M reacts to form some highly reactive radical M → R·.40. 267 . The simplest chain reactions have three distinct steps (discussed below) Chain reactions are extremely important in polymer chemistry Steps of a chain reaction 1.4. Chain Reactions Chain reactions are reactions which have at least one step that is repeated indefinitely.

This step repeats an indefinite number of times. Propagation: The radical formed in the initiation step reacts with some so molecule M0 to form another molecule M00 and another radical R0 ·. Termination: The radicals interact with each other or with the walls of the container to forma stable molecule R0 ·+R0 · → M000 or R0 ·+wall → removed 268 .2. 3. R·+M0 → M00 + R0 ·.

2) • The van der Waals gas equation of state P = or n2 a nRT − 2 V − nb V (41. This simplifies the theoretical treatment of gases. The equation of state can also be expressed in term of density ρ = ρ= mP . • The ideal gas equation of state P V = nRT. Gases and the Virial Series Unlike liquids and solids. We will now look in detail at the gases.4) Vm − b Vm where the parameter a accounts for the attractive forces among the particles and parameter b accounts for the repulsive forces among the particles P = 269 269 . (41. Equations of State Recall from last semester several of the equations of states for gases. 41. nRT m V (41.3) a RT − 2.1) (41. a particular particle has much less significant interactions with the other particles.41.1.

270 . (41. RT • z is unity for an ideal gas because for such a gas P V = nRT.7) 41. Conceptually B(T ) represents pair-wise interaction of the particles.6) • Redlich-Kwang P = (41. etc. • z can be expended in a power series called the virial series.2. + ··· .9) B(T ). n • For a real gas z must approach unity upon dilution ( V → 0). etc. C(T ).8) ³n´ 1 z = 1 + B(T ) Vm ¶ 1 + C(T ) Vm 1 + D(T ) Vm (41. The Virial Series Definition: Compressibility Factor: z = PV nRT = P Vm .• Berthelot • Dieterici P = nRT n2 a a RT − − = 2 2 V − nb T V Vm − b T Vm an a (41.5) RT e− RT Vm nRT e− RT V = P = V − nb Vm − b nRT n2 a a RT −√ −√ = V − nb Vm − b T V (V − nb) T Vm (Vm − b) (41. C(T ) represents triplet interactions. are called the virial coefficients. The virial series in powers of z = 1 + B(T ) or µ V n V is + C(T ) µ ³ n ´2 V ¶2 + D(T ) µ ³ n ´3 V ¶3 +··· .

hence 1 Vm µ b Vm ¶2 + ··· .10) to get V / a /T Vm R / P Vm = − m / 2 RT R / Vm − b RT Vm /T a Vm − = Vm − b RT Vm 1 a = − b RT Vm 1 − Vm but P Vm RT (41. etc.15) This series can now be compared term by term to the virial series to give expression for the virial coefficients: ³ a ´ . RT Vm Vm (41.11) = z so z= 1 a − . b RT Vm 1 − Vm which has the power series expansion (41.16) B(T ) = b − RT 271 . (41.12) The first term is of the form 1 1−x 1 = 1 + x + x2 + · · · .13) (41. D(T ) = b3 .14) 1 Vm and so it can be combined with the term µ ¶2 ³ a ´ 1 b z =1+ b− + + ··· . 1−x Therefore b a +1+ + z=− RT Vm Vm the first term is proportional to in the series expansion.41. C(t) = b2 . Relation to the van der Waals Equation of State Recall the van der Waals equation P = multiply both sides by Vm RT a RT − 2 Vm − b Vm (41. (41.1.2.

(41.3.17) = 1 + C(T ) Vm Vm ³ ´2 . The Boyle Temperature The temperature at which B(T ) = 0 is called the Boyle temperature. The gas behaves more like an ideal The lowest order correction are now V1 m gas at Tb then for other temperatures.2. 41.18) The relation of this expansion to the one in V1 can be obtained. The virial series at Tb becomes µ ¶2 µ ¶ µ ¶3 1 1 1 z(T = Tb ) = 1 + 0 + C(T ) + D(T ) + ··· Vm Vm Vm µ ¶3 µ ¶2 1 1 + D(T ) + ··· . One finds (see m homework) B(T ) B 0 (T ) = . (41.41.2.19) RT 272 .2. (41. The Virial Series in Pressure One can also expand the compressibility factor in pressure z = 1 + B 0 (T )P + C 0 (T )P 2 + D0 (T )P 3 + · · · . Tb .

a.25) 128Pc T (41.2.23) (41. Estimation of Virial Coefficients The virial coefficients can be estimated using empirical equations and tabulated parameters. T3 B(T ) = B0 − where A0 . RT T A0 a B0 c − B0 b − 3 .C 0 (T ) = and D0 (T ) = C(T ) − B(T )2 (RT )2 (41. b.21) 41. C(T ) = RT T B0 bc D(T ) = .22) (41. for now treat them as empirical parameters): µ ¶ 9RTc 6Tc2 B(T ) = 1− 2 . • Estimates based on Beattie-Bridgeman constants: c A0 − 3. B0 .4.20) D(T ) − 3B(T )C(T ) − 2B(T )3 (RT )3 (41. c are tabulated constants • Estimates based on critical values (we will discuss critical values shortly.24) 273 . (41.

κT is the isothermal compressibility • At a given temperature. the compressibility factor.42.1. V and T behavior of dense fluids (e. • Positive κT means the volume of the fluid decreases with increasing pressure. κT describes the change in volume with pressure. • Positive α means the volume of the fluid increases with increasing temperature. 274 274 . V V ∂T P V ∂P T | {z } | {z } α −κT α is the coefficient of thermal expansion.g. α describes the change in volume with temperature. P ) = ∂T P ∂P T We can change this from a extensive property equation to an intensive property equation by dividing by V : µ ¶ µ ¶ 1 ∂V 1 ∂V dV = dT + dP.. liquids). • κT is different from z. Taking volume as a function of P and T. V and T behavior We shall briefly consider the P. P. Behavior of Gases 42.1) dV (T. we consider the total derivative ¶ ¶ µ µ ∂V ∂V dT + dP. (42. • At a given pressure.

α and κT for liquids and solids à ¡ ¢! ∂ nRT 1 1 P = /R = n/ ∂T VP T |{z} P =n R / /T (42. of course. α and κT for an ideal gas As an exercise we shall calculate α and κT using the ideal gas equation of state (n. the compressibility and expansion of liquids (and solids) are very small..2) = = V ∂P T V ∂P V P T = and n/T 1 /R/ 1 1 nRT = = (P V ) P P /R/ P n/T | {z } =nRT 1 α= V µ ∂V ∂T ¶ P 1 = V 42.1. Starting with the ideal gas law: V = nRT . P0 . So one can expand the volume in a Taylor series about a known pressure. (42.1. At constant T ¶ ¶2 µ ∂V ∂V (P − P0 ) + (P − P0 )2 + · · · V (P ) = V0 + ∂P ∂P T | {z T } µ −V0 κT (42.b.3) In general. V (P ) ≈ V0 [1 − κT (P − P0 )] .1.2. 275 .4) so. P à ¡ ¢! µ ¶ µ ¶ nRT −1 ∂V −1 ∂ nRT −1 P − 2 κT = (42.42.5) This approximation is quite good even over a rather large pressure range (P −P0 = 100 atm or so). absurd to treat a liquid as an ideal gas). it is.

2.H = U + PV CP = ∂T P so µ (42.11) P 276 . The Relationship Between CP and CV To find how CP and CV are related we begin with ¶ µ ∂H .10) CP = ∂T ∂T P ∂T P P ¡ ¢ ¡ ¢ note ∂U P is not CV we need ∂U V .6) so.2. we can apply the cyclic rule for partial derivatives to determine the ratio κα : T ¡ ∂V ¢ ¶ µ α ∂P ∂T P cyclic = ¡ ∂V ¢ = (42. 42.8) κT − ∂P T rule ∂T V 42. Heat Capacity of Gases Revisited This section is a review from the first semester with an additional example beyond the ideal gas.Likewise at constant P ¶ ¶2 µ ∂V ∂V (T − T0 ) + (T − T0 )2 + · · · V (T ) = V0 + ∂T P ∂T T | {z } µ V0 α (42. (42.1.7) As one final point.9) ¶ ¶ ¶ µ µ ∂ (U + P V ) ∂U ∂V = +P (42. V (T ) ≈ V0 [1 + α(T − T0 )] . Use an identity of partial derivatives ∂T ∂T µ ∂U ∂T ¶ = P µ ∂U ∂T ¶ + V µ ∂U ∂V ¶ µ T ∂V ∂T ¶ (42.

Explicit in P : Replace µ 2.thus ¶ µ ¶ ¶ µ ∂V ∂U ∂V + +P (42. Explicit in V : Replace µ ∂P ∂T ¶ ∂V ∂T ¶ with − ¡ ∂T ¢V ∂P ∂V P ¡ ∂P ¢ (42. Then ∂T µ ∂U ∂T µ CP = CV + Finally CP = CV + T µ ∂V ∂T ¶ ∙ µ ¶ ¸ ∂P T −P +P / / ∂T V P µ ∂V ∂T ¶ µ P ¶ (42.18) 277 .13) ∂P ∂T ¶ (42.17) T V ∂T with − ¡ ∂V ¢P ∂P T ¡ ∂V ¢ (42. ∂T P ∂V T ¡ ¢ ¡ ∂U ¢ Recall the expression for internal pressure ∂V T = T ∂P V − P .14) V For solids and liquids: µ so ∂V ∂T ¶ = V α. µ ∂P ∂T ¶ = α κT (42.15) P V α2 T V (42.16) κT For gases we need the equation of state which often is conveniently explicit in P or V but not both CP = CV + 1.12) CP = ∂V T ∂T P ∂T P V ¶ ∙µ ¶ µ ¸ ∂U ∂V = CV + +P .

P2 (42. This is explicit P in V so use case 2 above ¶ µ ¶ ¶ ¡ ∂V ¢ µ µ ∂P ∂V ∂V ∂T ¡ ∂V ¢P CP = CV + T = CV − T (42. nRT − P2 / RT n (42.19) CP = CV + T ∂T P ∂T V nRT nR nR = = nR = CV + T P V PV Thus CP = CV + nR or CP m = CV m + R 2.23) or (42. = ∂T P P ∂T − ¡ ∂V ¢P = − ∂P T µ ∂V ∂P ¶ T =− nRT .24) 278 .21) so ¡ ∂V ¢ nR P + nB 0 / P (R + P B 0 ) n = .Examples 1.22) Thus CP ! ¶Ã nR P (R + P B 0 ) + nB 0 = CV + / T P RT / ¶2 µ P B0 = CV + nR 1 + R µ CP m ¶2 µ P B0 = CV m + R 1 + R (42. One term viral equation (equation of state: V = nRT + nB).20) ∂T P ∂T V ∂T P ∂P T The partial derivatives are ¶ µ ∂V nR + nB 0 . Ideal gas (equation of state: P V = nRT ): This equation is easily made explicit in either P or V so we don’t need any of the above replacements ¶ µ ¶ µ ∂P ∂V (42.

3. U (T.27) Also recall that −wrev is the maximum possible work that can be done in an expansion. So. Recall that if the expansion is reversible.26) V1 this becomes Z V2 −wrev = V1 µ ¶ V2 nRT dV = nRT ln V V1 (42. Isothermal and Adiabatic expansions We shall consider two limits for the expansion of gases 1. 42. there is always an intermediate equilibrium throughout the expansion. −wrev = For an ideal gas (P = nRT ) V Z V2 Pgas dV (42.1. Isothermal expansion T is constant 2.25) V1 As we learned last semester the value of w depends on Pex during the expansion.3. So for isothermal expansion 4U = 0 = q + w =⇒ q = −w. V ) = U(T ) (independent of V ). 279 . Namely Pgas = Pex .42. Expansion of Gases Expanding gases do work: −w = Z V2 Pex dV (42. Adiabatic expansion q = 0. −wrev = −wmax . Isothermal expansion • For the case of a ideal gas.

Recall ¶ µ ∂U CV = =⇒ dU = CV dT ∂T V So from above CV dT −nRdV −nRT dV =⇒ = V T V Going from (T1 .30) T1 CV dT = T Z V2 V1 −nR dV. Heat capacity CV for adiabatic expansions Considering an ideal gas going adiabatically from (T1 .29) (42.31) If CV (T ) is reasonably constant over the internal T1 to T2 then this is approximately µ ¶ µ ¶ V2 T2 ¯ = −nR ln (42.33) 280 . V2 ).2. • For an ideal gas dU = −P dV = −nRT dV V (42. dU = dw = −Pex dV = −P dV (reversible).32) CV ln T1 V1 ¯ where CV = 1 (CV (T1 ) + CV (T2 )) .28) 42. V2 ): CV dT = Z T2 (42. Or. V1 ) to (T2 . in terms of molar heat capacity 2 T2 ¯ CV m ln T1 µ ¶ V2 = −R ln V1 µ ¶ (42.Adiabatic expansion • Since q = 0.3. V (42. V1 ) to (T2 .

in general. P (42.3. CP = µ ∂H ∂T ¶ (42. P1 ) to (T2 . Or.3.37) If CP (T ) is reasonably constant over the internal T1 to T2 then this is approximately µ ¶ µ ¶ P2 T2 ¯ = nR ln (42. dH = dU + P dV + V dP (because both P and V can.40) 281 . When P is the more convenient variable What if P is the more convenient variable? Then use H instead of U Let us still consider an adiabatic expansion H = U + P V.34) =⇒ dH = Cp dT = V dP (42.39) From the above two cases µ ¶ µ ¶ µ ¶ R −R P2 V2 T2 = ¯ ln = ¯ ln ln T1 P1 V1 CP m CV m (42. Now.36) CP dT = T P2 P1 nR dP. in terms of molar heat capacity 2 T2 ¯ CP m ln T1 µ ¶ P2 = R ln P1 µ ¶ (42. change) / / dH = dq + dw + P dV + V dP dH = V dP. P2 ): Z T2 T1 nRT dP P Z (42.38) CP ln T1 P1 ¯ where CP = 1 (CP (T1 ) + CP (T2 )) .42.35) P For an ideal gas this becomes Cp dT = Going from (T1 .

So P2 ln P1 µ ¶ µ µ ¶ hence P2 ln P1 V2 = −γ ln V1 P2 P1 ¶ = µ V1 V2 Thus µ µ ¶ ¯ V2 CP m = − ¯ ln V1 CV | {zm } ≡γ (42.43) 42. Joule expansion Consider a gas expanding adiabatically against a vacuum (Pex = 0). 282 .4. (42.41) ¶ V1 = γ ln V2 µ ¶ V1 = ln V2 µ ¶γ (42. In this case q = 0 (adiabatic) and w = 0 (since −dw = Pex dV ).42) but Pi Viγ are arbitrary so this implies P V γ = constant (** NOTE: The axes should be reversed **) ¶γ ⇒ P2 V2γ = P1 V1γ .3.

Joule-Thomson expansion Consider the adiabatic expansion as illustrated by the figure below ¡ ∂U ¢ 283 . Thus in as much as the ¡ ∂T ¢ gas can be considered ideal ∂V U = 0. For real gases this is not strictly equal to zero.3. We want to find Identity: ¡ ∂T ¢ ∂V (42.45) U For an ideal gas ∂V T = 0 (since U(T. 42.44) U . That is.This implies 4U = q + w = 0. Internal energy is constant.5. for Joule type expansion the temperature of the gas does not change. V ) = U(T )). ¶ µ ¶ ¶ µ µ ∂U ∂U ∂T 1 =− = ∂U V ∂V T CV ∂V T | {z } 1/CV µ ∂T ∂V ¶ (42.

(the Joule-Thomson coefficient).50) H 284 .49) H ≡ μ.47) (42.46) (42. The work done on the right is wR = −P2 4V = −P2 (V2 − 0) = −P2 V2 . ¶ µ ¶ ¶ µ µ ∂H ∂T 1 ∂H =− = =μ ∂H P ∂P T CP ∂P T | {z } 1/CP ∂T ∂P ¶ (42. 4U = U2 − U1 = wL + wR = P1 V1 − P2 V2 Thus U2 + P2 V2 = U1 + P1 V1 ⇒ H2 = H1 For Joule-Thomson expansion the enthalpy is constant. Now. We want to find Identity: µ ¡ ∂T ¢ ∂V (42.48) (42.The work done on the left is wL = −P1 4V = −P1 (0 − V1 ) = P1 V1 .

Recall the useful identity µ Thus ∂H ∂P ¶ =V −T µ ∂V ∂T ¶ (42. so μ is positive–the gas cools upon expansion • High T : B 0 is nearly zero and B is positive. so μ is negative–the gas warms upon expansion • The Joule-Thomson inversion temperature is the temperature where μ = 0. (42. μ = CP m Limts: • Low T : B 0 is positive and B is negative.52) Example: The one term virial equation: (equation of state P V = nRT + nB) µ ¶ nRT 1 −nRT 0 − nB + + nT B μ = CP P P −B + T B 0 .53) 285 .51) T P ¡ ¢ −V + T ∂V P ∂T μ= CP (42.

2) dS = T T T1 dq=C dT Isothermal expansion of an ideal gas (P V = nRT ): • Recall that for isothermal expansion of an ideal gas dU = 0 = T dS − P dV dV ⇒ dS = P T . dS = T T T1 (43.1.1) At constant P : (use H = U + P V instead of U) P — dH = dU +P dV +V dP = dq−P dV +P dV +V dP . Calculation of Entropy Entropy must be calculated along reversible paths.43. Entropy of Gases 43. 286 286 . So Z T2 CV CV dT =⇒ 4S = dT. So dH = dq =⇒ dq=T dS dH = CP dT. (43. but also dU = T dS. So Z T2 CP CP dT =⇒ 4S = dT. • At constant V : — dU = dq + dw dq=CV dT =⇒ dU = CV dT. Entropy change for changes in temperature. but also dH = T dS. This is not a problem though since entropy is a state function.

V2 P2 dS = nR ln = nR ln P2 = −nR ln .4) If two variables change in going from the initial to final states break the path into two paths in which only one variable changes at a time.5) 287 .• Using the equation of state nRdV =⇒ 4S = dS = V Z V2 V1 V2 nR dV = nR ln . V1 P1 /R / n / T P1 /R / n / T (43.3) • Using the equation of state to express V1 and V2 in terms of P1 and P2 . VA 4SB = nB R ln VB + VA VB (43.6) VA + VB . V V1 (43. Entropy of Mixing of an ideal gas • Since the gas is ideal. there are simply two separate equations: 4SA = nA R ln and 4Smix = 4SA + 4SB (43.

13) 288 . V = Hence ¶ T ∂V =− ∂T µ ¶ P =− nR − nB 0 P (43.12) ideal Defining S2 . so ideal ideal S2 − S1 = −nR ln (43.10) Thus ideal ideal S2 − S1 = S2 − S1 − nB 0 (P2 − P1 ) (43.7) 43. P So ¡ ∂S ¢ µ ∂S ∂P ∂P T = − ¡ ∂V ¢ ∂T P and single term viral equation. P2 → P θ as S θ . ⎛ ⎞ 1/XA 1/XB ⎜ nA + nB nB + nA ⎟ ⎜ ⎟ + nB ln 4Smix = R ⎜nA ln ⎟ = −R (nA ln XA + nB ln XB ) nA nB ⎠ ⎝ | {z } | {z } (43.8) µ ¶ → nR P2 → 0 − nB dP =⇒ S2 − S1 = −nR ln dS = − − nB 0 (P2 − P1 ) P P1 P2 P1 (43.9) For an ideal gas B 0 = 0.1. this becomes S2 − / 1 S ideal ideal = S2 − / 1 S ideal − nB 0 (P2 − P1 ) (43. S(P θ ) = S θ − nB 0 P θ (43.1.11) Letting P1 → 0 and P2 → P θ (Standard pressure 1 bar). So.• Recall Avogadro’s principle: n ∝ V for an ideal gas. So. Entropy of Real Gases Consider the question: How does S → S ideal as P → 0 ? Use Maxwell relation nRT + nB.

14) (43.15) 289 .The entropy at any P and T can be obtained expresses as S(T. P ) = S θ (T ) − nR ln P − nB 0 P Pθ (43. P ) − nB 0 P Thus S(T. P ) = S ideal (T.

This section should not substitute for your studying of the rest of this material. −mv2 (43. Equations • The Maxwell’s distribution of speeds is F (v) = 4π µ m 2πkb T ¶3 2 e 2kb T v2 .Key Equations for Exam 3 Listed here are some of the key equations for Exam 3.18) 290 290 .16) • The average speed of a particle is hvi = • The mean free path is r 8RT πM (43. The equations are collected here simply for handy reference for you while working the problem sets.17) RT λ= √ 2P Lπσ 2 (43. The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations.

27) 291 .22) • The van der Waals gas equation of state: P = • Compressibility Factor: a RT − 2. nRT RT (43.25) • The virial series is µ ¶ µ ¶2 µ ¶3 1 1 1 z = 1 + B(T ) + C(T ) + D(T ) + ··· .26) (43.21) • Important thermodynamic relation: 4G = 4H − T 4S • Eyring’s equation is k= kb T − 4H ‡ 4S‡ kb T − 4G‡ e RT = e RT e R h h (43.20) kr • The Arrhenious equation k = Ae− RT Ea (43.24) z= (43.19) • The relation between the rate constant and the thermodynamic equilibrium constant is kf Kc = (43. Vm − b Vm P Vm PV = .23) (43.• The reaction velocity is v= 1 d[I] vi dt (43. Vm Vm Vm • Relation between heat capacities for an ideal gas: CP m = CV m + R (43.

Part VIII More Thermodyanmics 292 292 .

It is characterized by a critical temperature. Critical Phenomena 44. 293 293 .44. and a critical density ρc . Law of rectilinear diameters: The average density [ρave = 1 (ρliq + ρvap )] is 2 linear in temperature.1. Tc . Critical Behavior of fluids The point on the top of the coexistence curve is called the critical point.

294 .44.1. Simple gas laws do not work well near critical points.1. Gas Laws in the Critical Region The vapor pressure of a substance is taken from the gas laws as the pressures where A1 = A2 in the above figure.

2) 3 dVm ¯c (Vmc − b)2 Vmc and solving these three equations for Pc . The other equations of state give similar results van der Waals Berthelot Dieterici Redlich-Kwong zc 3/8 = 0.5) (44. Tc . z. Pc = 27b2 ¯ d2 P ¯ ¯ = 2RTc − 6a = 0 2¯ 4 dVm c (Vmc − b)3 Vmc (44.4) (44. So. setting 2 m the first and second derivatives at the critical point equal to zero we get ¯ dP ¯ ¯ = −RTc + 2a = 0 (44.2. dVP = 0) at the critical point.375 for all gases.375 3/8 = 0.3) (44. RTc 8 (44.1.27 0. That is (for the van der Waals Equation) zc = 0. 8a .1) dP d There is an inflection point ( dVm = 0.7) Notice that both a and b whose values depend on the particular gas have dropped out.375 2/e2 ' 0. Vmc − b Vmc 2 (44. Tc and Vmc gives Vmc = 3b.375. at the critical point zc = Pc Vmc 3 = = 0. Vmc ) Pc = a RTc − 2 . Gas Constants from Critical Data Consider the van der Waals equation at the critical point (Pc .44. Tc = 27bR a .33 295 .6) These values can be used to find the compressibility factor.

This implies μβ = μα is the condition for equilibrium. dn. 296 . 1. One can define unitless “reduced” variables Tr = T /Tc . RT zr is a “universal” function–it is nearly the same for all gasses. β denote liquid (or solid) and vapor phases. This is actually not too far from the truth experimentally.V = −P For a spontaneous process A deceases (dA < 0) z }| { (dVα + dVβ ) ¡ ¢ + μβ − μα dn At equilibrium dA = 0.2. Then zr = Pr Vrr . Pr = P/Pc . Phase Equilibrium Consider a homogeneous substance consisting of two phases α and β at a constant T and V. goes from α → β • (dAα )T = −P dVα − μα dn • (dAβ )T = −P dVβ + μβ dn = 0 since V is constant • (dA)T. then for a given T . Suppose some amount of material. The Law of Corresponding States We have found that zc is predicted by the equations of state to be independent of the particular gas.3.18 Laidler&Meiser ∗ ∗ 44. and Vr = V /Vc . When α.44. ∗ ∗ See Fig. the pressure of the system when μβ = μα is the called the vapor pressure of the material at temperature T.

n P. dG = −SdT + V dP + μdn Now.13) 297 .1. So again μβ = μα is the condition for equilibrium.T µ ¶ ∂ ∂G ∂μ ∂ ∂G =− =− =− . = Vm .P = μβ − μα dn. (44.3. 44. (44.11) P Similarly.10) But S = nSm (T.12) T Now the total differential of μ is m z z m µ }|¶ { µ }| ¶ { ∂μ ∂μ dT + dP dμ(T. µ ∂S ∂n ¶ µ ¶ (44. P ) = −Sm dT + Vm dP −S V (44. ∂n ∂T ∂T ∂n ∂T P µ ∂μ ∂T ¶ = −Sm . P ) = ∂T P ∂P T dμ(T. P ) so.8) (44. The chemical potential and T and P How does μ vary with T and P ? Generally for homogeneous substances.¡ ¢ For phase changes at constant T and P then (dG)T. ∂G S=− ∂T So. µ ∂μ ∂P ¶ (44.9) P.

vap − Vm.3.liq ' Vm.19) Collecting the T ’s on one side of the equation and the P ’s on the other we get (44.2. The Clapeyron Equation At equilibrium μβ = μα so.18) (44. 4v V = RT P (44. Now 4v V = Vm. consider the liquidvapor phase transition.21) d(ln P ) = − 298 .20) = d(ln P ) and dT T2 = −d(1/T ) so this becomes 4v Hm d(1/T ) R (44.14) = This is the Clapeyron Equation 4φ Hm T 4φ Vm (44. Vapor Equilibrium and the Clausius-Clapeyron Equation The above Clapeyron equation applies to any phase transition.15) (44.vap Assuming the vapor phase obeys the ideal gas equation of state.17) Substituting this into the Clapeyron equation gives 4v Hm 4v Hm P dP = = RT dT RT 2 T P 4v Hm dT dP = P R T2 Now we identify dP P (44.44.16) 44.3.3. −Smα dT + Vmα dP = −Smβ dT + Vmβ dP Now Smα − Smβ −4φ Sm dP = = dT Vmα − Vmβ −4φ Vm 4φ Hm dP = dT T 4φ Vm 4S= 4H T (44.

most other common liquids • Solid—solid — rhombic sulfur—monoclinic sulfur — grey tin—white tin — graphite—diamond For example a diamond at STP is metastable with respect to graphite. (44. “A diamond is not forever!” At equilibrium μα = μβ this implies (for incompressible liquids and solids) μª + Vmα (P − P ª ) = μª + Vmβ (P − P ª ) α β (44.24) α β 299 .4. Equilibria of condensed phases Examples • Solid—liquid — ice—water.Rearranging again leads to 4v Hm d(ln P ) =− d(1/T ) R This is the Clausius-Clapeyron equation.22) 44.23) This can be rearranged so that terms independent of pressure (the standard chemical potentials) are one side and the terms that depend of pressure are on the other side μª − μª = (Vmβ − Vmα ) (P − P ª ) (44.

5. Recall the Clapeyron equation 4f Hm Hmβ − Hmα dP = = dT T 4f Vm T (Vmβ − Vmα ) (44. At temperatures above the critical point there is no distinction between vapor and liquid. 44.26) 4f Hm 4f Hm Tf → T ª where Tf is the freezing temperature at standard pressure (1 bar).Thus for any given T only one P allows for equilibrium. T for a system which shows the lines of equal chemical potential • Critical Point: The terminal point of the liquid-vapor line. • Triple Point: The point where all three phases coexist in equilibrium: μsolid = μliq = μvap (44.25) We make the good approximation that 4f Hm is independent of T and solve the Clapeyron equation Z → 4f Vm dP Tf 4f Vm (P − P ª ) dT = ⇒ ln ª = (44. Triple Point and Phase Diagrams Definitions • Phase Diagram: A graph of P vs.27) 300 .

J. Viscosity: The flux of momentum down a velocity gradient 3. Diffusion At equilibrium concentration on a bulk solution will be uniform. Flux: movement of something through a unit area. So if there exists a concentration gradient there will be a net flux.45. We now consider three transport properties of fluids: 1. Diffusion: The flux of material down a concentration gradient 2.1. of material from high concentration to low concentration so as to establish an equilibrium. Thermal Conductivity: The flux of energy down a temperature gradient ∗ ∗ See Transport Phenomena handout ∗ ∗ 45. J= 1 dn A dt (45. Transport Properties of Fluids Transport properties of matter deal with the flow (or flux) of some property along a gradient of some other property.1) 301 301 .

∂t ∂x (45. ∂t ∂x ∂x If D is truly constant we get Fick’s second law of diffusion: ∂ 2C ∂C =D 2.5) 302 .3) (45.2) (45. The change in concentration in a lamina between x and dx with time is given by the flux in minus the flux out of the lamina: J(x) − J(x + dx) ∂J ∂C = =− ∂t dx ∂x Using Fick’s first law for J ∂ ∂C ∂C = D .The flux of material through a plane depends on the concentration difference J = −D dC 1 dn dC =⇒ = −D dx A dt dx where D is the diffusion constant dC 1 dn = −D A dt dx This is Fick’s first law of diffusion (in one dimension).4) (45.

i. The solution for two special boundary conditions are of interest and will simply be presented here without derivation 1. t) = √ e− 4Dt 2 πDt (45. Viscosity Viscosity.2. The tendency of a liquid to flow at the same velocity throughout. η.7) where erf and erfc are tabulated functions respectively called the error function and complementary error function.6) 2. t) = C0 2 π 0 ¶¸ ∙ µ x 1 C0 1 − erf √ = 2 4Dt ¶ µ 1 x = C0 erfc √ 2 4Dt " (45. 45.The solution of this partial differential equation depends on the boundary conditions.. Numerous methods of solution exist for this equation but they are beyond the scope of the course. is the resistance to differential fluid flow. Step function solution # Z √x 4Dt 1 1 2 −√ e−y dy C(x. Point source solution x2 C0 C(x. 303 .e.

dv The frictional (viscous) force is F = ηA dx . Pf is the outlet pressure and P0 is the pressure at which the volume is read. lenght·time 1 poise Poiseuille’s Formula • Applies to Laminar (nonturbulent) flow • For a liquid flowing trough a tube (radius r.. i. (The units of η are g = cm·s .9) Stoke’s law: spheres falling through fluids 304 .) mass . length l). ¶ (45. the volume of flow 4V in time 4t is πr4 4P 4V =− (45.8) 4t 8ηl where 4P is the driving pressure.e. • For a gas 4V πr2 = 4t 16ηl µ 2 Pi2 − Pf P0 where Pi is the inlet pressure. the difference in pressure on either side of the tube.

305 . Stewart and E.12) 45.B. N. Bird. Thermal conductivity (This section closely follows parts of chapter 8 in Transport Phenomena by R.• The frictional force (exerted upwards) is proportional to velocity: Ff = −fv. Stokes showed f = 6πηr • Gravitational force (exerted downwards): Fg = gravitational acceleration (9.11) • Related to diffusion constant: = kT 6πηr (45. The plates are held at constant but different temperatures T1 and T2 (T1 > T2 ) for a sufficiently long time that a steady state exists.3.8 m/s2 ). κ. Consider a slab of solid material of area A between two large parallel plates a distance D apart. 4πr3 (ρ − ρ0 )g. of a material is a measure of the tendency of energy in the form of heat to flow through the material.10) (45. W.E. Lightfoot Wiley New York 1960) The thermal conductivity. 3 where g is the • Terminal velocity is reached when Ff + Fg = 0 giving −f vterm + vterm = using f = 6πηr vterm 4π r/ (ρ − ρ0 )g / 3 2r2 (ρ − ρ0 )g ¡ ¢ = = 9η 3 6π ηr / / D= kT f f =6πηr 4πr3 (ρ − ρ0 )g = 0 3 4πr3 (ρ − ρ0 )g 3f (45.

a linear steady state temperature distribution across the material is established.13) A dt D If we take the limit where D becomes infinitesimally small (D → dx) we obtain a differential form of this equation: 1 dq dT = Qf = −κ .Under such conditions.1. (45. from hot to cold. And a constant rate of heat flow dq is needed to maintain dt the temperature difference 4T = (T1 − T2 ) 4T 1 dq = −κ . 306 . (45.14) A dt dx where Qf is the heat flux. 45. This is called Fourier’s law of heat conduction (one-dimensional version). Thermal Conductivity of Gases and Liquids ∗ ∗ See Reduced thermal conductivity handout ∗ ∗ From this handout we see that typically the thermal conductivity of gases at low densities increases with increasing temperature. Thermal conductivities are positive quantities so Fourier’s law says that heat flow down a temperature gradient.3. whereas the thermal conductivity of most liquids decrease with increasing temperature.e.. i.

Dry porous materials are poor heat conductors Rule of Thumb: Thermal conductivity and electrical conductivity go hand in hand.2.45. The Wiedemann. Frantz and Lorenz equation breaks down at low temperature because metals become superconductive. There is no analog to superconductivity for thermal conductivity. κel T where L is the Lorenz number (typically 22 to 29 × 10−9 V2 /K2 ). (45. Frantz and Lorenz equation relates the thermal conductivity to electrical conductivity. κel for pure metals: κ = L = const. The Lorenz number is taken as constant because it is only a very weak function of temperature with a change of 10 to 20% per 1000 degrees being typical.15) 307 . the thermal conductivity of solids have to be determined experimentally because many factors contributing to the thermal conductivity are difficult to predict. Thermal Conductivity of Solids For the most part. In general metals are better heat conductors than nonmetals and crystals are better heat conductors than amorphous materials. The Wiedemann.3.

volume. Solutions Solutions are mixtures of two or more pure substances.2. For example. one also needs to keep track of the amount of individual species in solution 46.1.1) (46. in general change upon mixing X 4mix = properties of soln − properties of pure. n1 +n2 • mole fraction X2 = • molality m = • Molarity c2 = X1 = 1 − X2 1000X2 .2) . say. 4mix V = Vsoln − Vsolute − Vsolvent Consider a thermodynamic quantity. M1 X1 where M1 is the molecular weight of species 1 n2 L solution 46. Partial Molar Quantities Thermodynamic properties. in addition to the parameters needed to characterize a pure substance. 308 308 (46.46. So. Measures of Composition There are several measures of composition of solutions • mole ratio r = n1 n2 n2 .

dG = ∂T P. the partial molar volume.In general.n1 . n2 ). n1 and n2 : V (T.n1 . P.n1 (46. it is a function of T. Notation The study of solutions brings with it here for future reference.P. So.nj Similarly ¶ ¶ ¶ ¶ µ µ µ µ ∂G ∂G ∂G ∂G dT + dP + dn1 + dn2 .P. ∂ni T.2.n2 ∂n1 T. P. Material Pure liquid i Vi• • Pure liquid i per mole Vmi Whole solution V Solution/(total moles) Vm ¯ Partial molar of i in solution Vi Apparent molar (of solute) φ V Reference state Viª a large number of symbols which we collect Hi• • Hmi H Hm ¯ Hi φ H Hiª Si• • Smi S Sm ¯ Si Siª G• i • μi G Gm μi μª i 309 .P.n1 . 46.P.n2 ∂n2 T.P. ∂T P. rather than simply the molar free energy as it was earlier. n1 .1.4) ³ ´ ∂G ≡ μi .3) ³ ´ ∂V ¯ ≡ Vi .n2 ∂n1 T. ∂ni T.n2 ∂P T.nj So now for the more general case of mixtures the chemical potential of a species of the partial molar free energy for that species.P.n1 (46. the total derivative is ¶ ¶ µ ¶ ¶ µ µ µ ∂V ∂V ∂V ∂V dV = dT + dP + dn1 + dn2 .n1 .n2 ∂n2 T.n2 ∂P T.

310 . 4mix V > 0. 4mix V < 0. Vi depends on concentration. the total volume of the solution is equal to the sum of the partial molar volumes each weighted by their respective number of moles. however.46. so change each amount of substance proportional to the amount substance present. one unit of baseballs are mixed with one unit of books.2. 1. For example. Partial Molar Volumes Consider the partial molar volume For constant T and P ¯ ¯ dV = V1 dn1 + V2 dn2 (46. negative or zero.8) 4mix V can be positive.2.6) That is.5) ¯ Now. More specifically 4mix V • • = V − (Vm1 n1 + Vm2 n2 ) ¡ ¢ • • ¯ ¯ = V1 n1 + V2 n2 − (Vm1 n1 + Vm2 n2 ) ¡ ¡ ¢ ¢ • • ¯ ¯ = V1 − Vm1 n1 + V2 − Vm2 n2 ¢ ¡ dλ ¯ ¯ ¯ ¯ dV = V1 n1 + V2 n2 dλ =⇒ V = V1 n1 + V2 n2 (46. The total volume. (46.7) (46. one unit of baseballs are mixed with one unit of basketballs. dn1 = n1 dλ. So. dn2 = n2 dλ. 2. is not necessarily the mole weighted sum of the volumes of each component in its pure (unmixed) state.

1.3. all neighboring molecules are different than the given molecule 2. all neighboring molecules are same as the given molecule 2.3. the ideal state for Raoult’s law 2.46. Activity (a brief review) Henry’s law limit Recall that activity gives a measure of the deviation of the real state from some reference state 311 . Reference states for liquids For liquids there are two more convenient ideal states 1. the ideal state for Henry’s law Raoult’s law limit 46. infinite dilution limit 1. neat (pure) solvent limit 1.

).2.g.12) i ai g(ζ) (46. and ζ ª is the value of ζ at the reference state.10) 46. pressure. Raoult’s Law In discussing both Raoult’s law and Henry’s law. Connecting with the chemical potential we saw last semester that the deviation of the chemical potential at the state of interest versus at the reference state is determined by the activity at the current state (the activity at the reference state is unity by definition). This implicit definition is awkward so for convenience one defines the activity coefficient as the argument of the above limit.9) ζ→ζ ª g(ζ) where g(ζ) is any reference function (e. (46. γi ≡ which we can rearrange as ai = γ i g(ζ).Also recall that the mathematical definition of activity ai of some species i is implicitly stated as ai lim =1 (46. concentration etc.11) The definition of activity implies that γ i = 1 at g(ζ ª ) (the reference state) That is γ i → 1 as the real system approaches the reference state.3. we are describing the behavior of a liquid solution by measuring the vapor (partial) pressures of the components 312 . mole fraction. μi − μª = RT ln ai . (46..

13) = (μ1 − μ• ) n1 + (μ2 − μ• ) n2 .16) (46.17) (46. μ1 − μ• = RT ln 1 where Pi is the vapor pressure of the ith component above the solution. Recall that 4mix G = G(soln) − G(pure components) Hence. 1 2 ai low P Pi ' RT ln • .15) (46.18) Now. Take differential change along a line of constant concentration.For simplicity we consider here only a two component solution. 313 . • ai Pi (46.14) (46. 4mix G = μ1 n1 + μ2 n2 − μ• n1 − μ• n2 1 2 (46. dG = μ1 dn1 + μ2 dn2 . so dG = (μ1 n1 + μ2 n2 ) dλ then G = μ1 n1 + μ2 n2 .

22) • • P1 / P2 / 4mix G = RT (n1 ln X1 + n2 ln X2 ) Again. From ¶ ¶ µ ∂G ∂ (G/T ) S=− and H = − .26) 314 .23) (46. Ideal Solutions (RL) Raoult’s Law: Pi = Xi Pi• (46. The change in free energy upon mixing for solutions ideally obeying Raoult’s law is à ! • • X1 P/ X2 P/ id(RL) 1 2 4mix G = RT n1 ln + n2 ln (46.3. ∂T P ∂ (1/T ) P the entropy of mixing for an ideal Raoult solution is µ 4mix S = −R (n1 ln X1 + n2 ln X2 ) and the enthalpy of mixing is 4mix H = 0 id(RL) id(RL) id(RL) (46.19) (46. this is for an ideal solution in the Raoult’s Law sense.24) (46.25) (46.20) 46.3.21) That is. the vapor partial pressure of a component of a mixture is equal to the mole fraction of the component times the vapor pressure that the component would have if it were pure.Thus or at low P ¶ µ P1 P2 4mix G = RT n1 ln • + n2 ln • P1 P2 ¶ µ a1 a2 4mix G = RT n1 ln • + n2 ln • a1 a2 (46.

The physical interpretation of deviation from Raoult’s law is • positive deviation: the molecules prefer to be around themselves rather than other types of molecules. 315 . The reference function is g(ζ) = ζ = Xi . It does not require any kind of interaction among the constituent particle making up the solution. ai =1 Xi →1 Xi lim implies ai and γ i (RL) (RL) (RL) (46. and the reference state is Xi = 1 So.27) = γi (RL) Xi . (46. • negative deviation: the molecules prefer to be around other types of molecules than themselves. there are specific interactions between particles. real solutions generally deviate from Raoult’s law. • no deviation: the molecules have no preference. Since. in reality. The Reference State (RL) Let us apply the definition of activity for the Raoult’s law reference state.28) → 1 as Xi → 1 Deviations from Raoult’s Law Raoult’s law is a purely statistical law.(since G/T is independent of 1/T ).

Henry’s Law Henry’s Law: Pi = kXi Xi . kXi = lim µ Pi Xi ¶ (46. Positive deviation from Raoult’s lawNegative deviation from Raoult’s law 46.29) Xi →0 Henry’s law applies to the solute not to the solvent and becomes more correct for real solution as the concentration of solute goes to zero (Xi → 0). For example.It is very important to note that this deviation from Raoult’s law is a property of the solution and NOT any given component.3.e.. mixing with one substance may lead to a positive deviation but mixing with another substance may lead to a negative deviation.30) (46. i. at infinite dilution. where kXi is the Henry’s law constant. 316 .4. for a given component.

The Reference State (HL) Referring to the definition of activity again we see that the reference function is g(ζ) = ζ = Xi . But. (HL) ai lim =1 (46. in summary • Raoult’s law: γ 1 → 1 as X1 → 1 • Henry’s law: γ 2 → 1 as X2 → 0 (HL) (HL) (HL) = γ (HL) mi mi (46. Raoult’s law applies to the dominant species. So. molality or molarity is used then ai and ai respectively. X1 → 1.34) 317 .33) = γ Mi Mi (HL) (46. they apply to opposite species in the solution.31) Xi →0 Xi implies (HL) (HL) = γ i Xi . whereas Henry’s law applies to the subdominant species X2 → 0. Comparison of Raoult’s Law and Henry’s Law Both Raoult’s law and Henry’s law become better approximations for real solutions as the solution becomes pure. (46.32) ai → 1 as Xi → 0 and γ i If instead of mole fraction. and the reference state is now Xi = 0 So.

Colligative Properties Colligative properties: Properties of dilute solutions that are independent of the chemical nature of the solute Examples • Freezing point depression • Boiling point elevation • Vapor pressure lowering • Osmotic pressure We will consider the examples of freezing point depression and osmotic pressure 46.4. Freezing Point Depression At Tf (freezing point). | {z } μs 1 318 .4. μ1 (solid) = μ1 (soln).1.46.

The freezing point depression is Θ=− 46. μ1 (soln) = μ• + RT ln a1 : 1 μs = μ• + RT ln a1 1 1 Rearranging this and taking the derivative with respect to T yields ¶ µ −1 ∂μs ∂μ• 1 ∂ ln a1 ∂ → 1 1 s • (μ − μ1 ) =⇒ = − ln a1 = ∂T → RT 1 ∂T RT 2 ∂T ∂T Now.4. Z Tf −4f H 4f H ln a1 ' dT = Θ.2. Osmotic Pressure RTf•2 ln a1 4f H We consider the osmotic pressure at a constant temperature. T. (so.Using the Raoult’s law reference state (since we are interested in the behavior of the dominant species).36) = H and integrating we get µ ¶ Z → −1 4f H s • d ln a1 = (H1 − H1 ) dT = dT 2 RT RT 2 → Z Tf 4f H dT ln a1 = • RT 2 Tf (46. (46.37) • For small changes in the freezing point we may approximate T by Tf in the integrand. 319 .35) (46. using ∂μ ∂T (46. dG = V dP ).38) •2 •2 • RTf Tf RTf • where Θ ≡ Tf − Tf . So.

39) ¯ where V1 is the partial molar volume of the solvent in solution (difficult to measure) and Π is the hydrostatic (osmotic) pressure.42) ' n2 n1 for dilute solutions.43) 320 .41) For dilute solutions X2 is small so ln(1 − X2 ) may be expanded as ln(1 − X2 ) = −X2 + but X2 = n2 n1 +n2 2 X3 X2 − 2 − · · · ' −X2 . ' m1 =⇒ n2 ' n1 RT RT V• (46.40) (46. 1 1 (46. From the above equation ¯ V1 Π RT • ¯ Now we make the approximations V1 = Vm1 .In the above figure μ1 (left) = μ1 (right). hence ¯ μ• = μ• + RT ln a1 + V1 Π. Thus 1 z }| { • • V Π n1 Vm1 Π n2 . a1 = X1 = 1 − X2 : ln a1 = ln(1 − X2 ) = • Vm1 Π RT (46. 2 3 (46.

44) Note the similarity of this equation with the ideal gas equation: P = cRT. V1• |{z} 'c (46.or. 321 . n2 RT = cRT. Thus the solute in a very dilute solution behaves as if it were an ideal gas. Π= where c is the concentration of the solute.

we will state their respective definitions here in a manner best suited for this chapter. However. 322 322 . The main concept of this approach is the idea of entropy production and. Fundamentals We know the difference between reversible and irreversible processes from before. We now we consider thermodynamics of nonequilibrium states and investigate how (and how fast) these state move towards equilibrium. ultimately.1. Entropy Production and Irreverisble Thermodynamics We have seen that thermodynamics tells us if a process will occur and kinetics tells us how fast a process will occur. 47. These two areas of physical chemistry appear to be rather disjoint.47. This allows us to make a stronger connection between thermodynamics and kinetics. entropy production per unit time–how fast we are producing entropy.

1 ∂ 2 u ∂ 2 u t→−t 1 ∂ 2 u ∂2u 1 ∂2u ∂2u = 2 =⇒ = 2 =⇒ = 2. the one dimensional wave equation. • e.Reversible process: dynamical equations are invariant under time inversion (t → −t).2) (47. the one dimensional heat equation. 323 . • di S is the change in entropy due to internal changes of the system The quantity di S is called the entropy production. (47.g. Definitions • de S is the change in entropy due to interactions with the exterior environment. ∂ 2 T t→−t 1 ∂T ∂ 2T ∂2T 1 ∂T 1 ∂T = = = =⇒ =⇒ − .g. κ ∂t ∂x2 κ ∂(−t) ∂x2 κ ∂t ∂x2 is not invariant under time reversal. which can be split into two components dS = de S + di S. c ∂t2 ∂x c ∂(−t)2 ∂x c ∂t2 ∂x is invariant under time reversal Irreversible process: dynamical equations are not invariant under time inversion (t → −t).1) We will be concerned with the change in entropy.. • e. dS..

324 . 47. the second law underlies all the concepts of this chapter. compensated by a sufficient production in another part is prohibited — i.2.. We need a “local” formulation of the second law: • Absorption of entropy in one part of the system. holds. General criteria for irreversibility: • di S = 0 (reversible change) • di S > 0 (irreversible change) For isolated systems have di S = dS and the principle of Clausius.Splitting up dS into these two parts permits an easy discussion of both open and isolated systems–the difference between the two appearing only in de S. in every macroscopic region of the system the entropy production due to irreversible processes is positive. The Second Law As you might expect. di S = dS ≥ 0.e. This is simply another in our long list of alternative statements of the second law.

3) The local formulation statement implies di S I ≥ 0 and di S II ≥ 0 (47. Examples The idea of entropy production can be applied to any of the processes we have talked about.3. phase changes. 325 .4) ¡ ¢ and the possibility of. chemical reactions. we write the principle of Clausius as dS = dS I + dS II ≥ 0. mixing. (47. di S I < 0 and di S II > 0 such that di S I + S II > 0 is excluded. for example. As example we now consider the last two of these: heat flow and chemical reactions. heat flow.I II Considering the above figure of an isolated system. etc. 47.

326 . so. using Qf = κA4T q =− 4t D in differential form this is dT dq = −κA . (47.7) dt dx Example: Find the entropy production in a system consisting of two identical connected blocks of metal (I and II).1. Entropy Production due to Heat Flow Recall from the lecture on transport phenomena that the heat flux Qf is given by Qf = −κ 4T D q 4t (47.6) We are now interested in exposing the time dependence. one of which is held at temperature T1 and ¯ ¯ the other at T2 (take T1 > T > T2 ) where T is the temperature at the interface.3.5) we get (47.47.

9) (47. T1 T2 T1 T2 d S dS dS = (47. We have still not made a connection to kinetics. Furthermore the heat going out of I through the connecting wall is equal to the heat coming into II through the connecting wall: di qI = −di qII . To do so we must consider the entropy production per unit time di S .Considering the whole system dqI dqII + T1 T2 e i z }| { z }| { de qI de qII di qI di qII = + + + .10) 327 . dt (47.8) The quantity de qj is the amount of heat supplied by the environment to hold block j at its fixed temperature. Using this we see that the entropy production is µ ¶ 1 1 . − di S = di qI T1 T2 which we see is positive because di qI < 0 when T1 > T2 .

(47.14) a result we might have guessed. T1 − T = − T − T2 ⇒ T = 2 D / D / (47.13) dt dt ¯ Using the above expression for heat flow gives us T since. − ¢ ¢ κ/ κ/ /A ¡ / A ¡¯ ¯ ¯ T1 + T2 . where ni is the number of moles vi of the ith component and vi the stoichiometric factor of the ith component.V = 2.11) ¶ −Aκ4T di qI = . Entropy Production due to Chemical Reactions Definitions: 1. Chemical affinity: a ≡ − (4rxn G)T.12) ¯ To determine T we use the fact that the heat flow out of I is equal to the heat flow into II: di qI −di qII = . 47. −Aκ4T di S = dt D µ 1 1 − T1 T2 (47. 328 . dt D So. Extent of reaction: ξ is defined by dξ = dni .2.P = − P − i vi μi P i vi μi and a ≡ − (4rxn A)T.3.For this example di qI di S = dt dt From chapter 24 we know µ 1 1 − T1 T2 ¶ (47.

V dq − = (dU)T.g. This is because a = − (4rxn A)T.17) z }| { z }| { (dA)T..19) The entropy production per unit time for a chemical reaction is a function of both the chemical affinity and of the reaction rate a dξ a di S = = v≥0 dt T dt T (47.18) d S dS (47.15) (47.16) but (dA)T. for the reaction N2 + 3H2 → 2NH3 dξ = and a = 2μNH3 − μN2 − 3μH2 The connection to kinetics: reaction rate v = The connection to thermodynamics: (dA)T.V is positive as is v.V so µ ¶ 1 dni = −adξ μi dni = vi μi vi | i {z }| {z } X −a dξ −adξ (47.V = X i dξ dt dnH2 dnNH3 dnN2 = = (−1) (−3) (2) (47.V − T dS ⇒ dS = T T dq e i z}|{ z}|{ dq adξ + dS = T T (47. 329 .• e.20) We see that for a spontaneous process the entropy production per unit time is positive.

diffusion is the flux of matter down a concentration gradient. (47. The socalled Soret effect is flux of matter down a temperature gradient.Simultaneous Reactions For N simultaneous chemical reactions. That is.4. Conversely. the so-called Dufour effect is heat flux down a concentration gradient 330 . the entropy production per unit time generalizes to N 1X di S = aj vj ≥ 0. Thermodynamic Coupling Processes may be what is called thermodynamically coupled such that a process that normally is not thermodynamically favored can be coupled to another process that is thermodynamically favored so as to allow for the unfavorable process to proceed spontaneously. 47. We just saw an example of such a situation with the discussion of simultaneous reactions.21) dt T j=1 The second law requires that the total entropy production for simultaneous reactions is positive. It says nothing about the entropy production of the individual component reactions other then the sum of all the component entropy productions must be positive. a2 v2 > 0 such that a1 v1 + a2 v2 > 0. Thermodynamic coupling need not be confined to coupling between the same types of processes. For example in a system of two coupled reactions we could have a1 v1 < 0.

Echo Phenonmena Consider an ensemble that is perturbed away from thermal equilibrium by some means such as by applying a field.The following table lists a number of thermodynamically coupled phenomena Flux Gradient q Thermoconductivity Mechanocaloric effect m Thermomechanical effect Hydrodynamic flow material Soret effect Reverse osmosis Q (charge) Seebeck effect Potential of flow Nernst Potential Electoconductivity T P C ε Dufour effect Peltier effect Osmosis Electrophoresis Diffusion Migration 47. 331 . The ensemble evolves in two ways • Reversibly — A second perturbation can “undo” or reverse the evolution. • Irreversibly — The evolution towards equilibrium cannot be undone–it is irreversible Example: The spin echo in pulsed NMR • A radio frequency pulse prepares an ensemble of nuclear spins such that they are all spinning coherently.5. If the perturbation is released the system will begin to evolve in time as it heads back towards the thermalized equilibrium state.

• This cannot be undone with the second radio pulse. • Each nucleus is in a slightly different environment so each spin frequency is slightly different. 332 . • The different environment (spin frequencies) cause the ensemble spinning nuclei to dephase • Dephasing causes a decrease in the observed signal because now not all nuclei are cooperating.• A strong signal is seen because all the spinning nuclei cooperate. • Now a radio pulse with the opposite phase is applied to make the nuclei spin in the opposite direction • This undoes or reverses the dephasing process and the signal regains strength • The full signal is not recovered however since all the while random thermalization is taking place to irreversibly destroy the coherence among the nuclei.

23) (47. The equations are collected here simply for handy reference for you while working the problem sets. dT T 4φ Vm • The Clausius-Clapeyron equation is 4φ Hm d(ln P ) =− d(1/T ) R • Fick’s first law of diffusion is dC 1 dn = −D A dt dx (47.Key Equations for Exam 4 Listed here are some of the key equations for Exam 4.22) 333 333 .24) (47. Equations • The Clapeyron Equation is 4φ Hm dP = . This section should not substitute for your studying of the rest of this material. The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations.

33) = γi (HL) Xi .34) 334 .28) μ = μª + RT ln a (47.32) where kXi is the Henry’s law constant. ∂t ∂x (47.25) • Relation between the viscosity and the diffusion constant: D= kT f f =6πηr = kT . (47.26) • Fourier’s law of heat conduction is dT 1 dq = Qf = −κ .27) • Mixing 4mix = properties of soln − • Chemical potential • Raoult’s Law: • Raoult’s law reference ai • Henry’s Law: (RL) properties of pure. kXi = lim • Henry’s law reference ai (HL) Xi →0 Pi Xi . γi (HL) → 1 as Xi → 0. A dt dx X (47. µ ¶ (47. (47.• Fick’s second law of diffusion: ∂ 2C ∂C =D 2.31) Pi = kXi Xi . (47. γi (RL) → 1 as Xi → 1 (47.29) Pi = Xi Pi• (47. 6πηr (47.30) = γi (RL) Xi .

178 partition coefficient 174 Born—Oppenheimer approximation 62.Index absorption spectroscopy 241 activity 146. 270 binominal coefficient 90 blue sky 81 Bohr model 18 335 335 Bohr radius 19 Boltzmann distribution 10. 99. 96. 312 adiabatic expansion 280 and heat capacity 280 adiabatic wall 120 angular momentum addition of 202 classical 192 eigenfunctions for 199. 97. 131 bond order 77 bonding orbital 71 Born model 170 corrections to 175 enthalpy of solvation 174 entropy of solvation 174 free energy of solvation 173. 291 temperature corrected 262 atomic orbitals 49 chemists picture 50 physicists picture 50 aufbau principle 58 average value theorem 29 Berthelot gas 13. 240 and the Franck—Condon principle 243 bosons 56 Boyle temperature 272 chain rule for partial derivatives 107 character table for the C2v group 225 chemical affinity 328 chemical potential 144 for a salt 161 relation to activity 148 relation to Gibbs free energy 145 relation to Helmhotz free energy 145 . 235. 219 spin 201 angular momentum quantum number 52 antibonding orbital 71 Arrhenious activation energy 261 Arrhenious equation 261. 131 Boltzmann’s equation 90. 124. 311 mathematical definition of 146 activity coefficient 146. 219 jj coupling 202 LS coupling 202 quantum numbers 199.

333 Clausius-Clapeyron equation 299. 323 due to chemical reactions 328 due to heat flow 326 equation of state 116 for a Berthelot gas 118 for a Dieterici gas 118 for a Redlich—Kwang gas 118 for a van der Waals gas 117 for an ideal gas 116 for gases 269 equilibrium constant 135 336 . 178 Debye—Huckel theory 163 Debye—Huckel—Guggenheim equation 164 Debye’s law 129. 132 enthalpy 136 entropy 105 change for changes in temperature 286 change for isothermal expansion 286 change for mixing 287 of real gases 288 entropy production 322. 333 coefficient of thermal expansion 274 coexistence curve 293 colligative properties 318 commutator 30. 189 completeness 191 complimentary variables 30 compressibility factor at the critical point 295 compressibilty factor 270.Clapeyron equation 298. 133 degeneracy 186 of the ensemble 98 diathermic wall 120 diatomic molecules electron-electron potential energy operator for 61 electronic kinetric energy operator for 61 electronic wavefunction for 62 Hamiltonian for 61 nuclear kinetic energy operator for 61 nuclear-electron potential energy operator for 61 nuclear-nuclear potential energy operator for 61 Schrodinger equation for 62 Dieterici gas 270 diffusion 301 diffusion constant 302 eigenfunction 5 eigenvalue 5 eigenvalue equation 190 electric dipole approximation 79. 231 electrolytes strong 161 electrophoretic effect 167 elementary reactions 255 and stoichiometry 256 molecularity 256 emission spectroscopy 241 enemble 89 ensemble average 103. 300. 108 cylindrical symmetry 69 Debye—Huckel limiting law 164. 291 configuration 90 confluent hypergeometric functions 65 correspondence principle 41 critical point 300 cyclic rule 14.

333 Fick’s second law 302. 334 Hermite polynominals 40 hot bands 66 Hund’s rule 205 hydrogen atom ioniztion energy of 19 hydrogen molecule 74 hydrogenic systems 46 energy levels for 49. 316. 86 Hamiltonian 47 normalization constant 49. 86 potential energy 39 Schrodinger equation for 39 heat 109 sign convention 110 heat capacity 115. 121 intramolecular vibrational relaxation (IVR) 242 337 . 44. 334 Franck—Condon integral 243 Franck—Condon principle 243 free energy Gibbs 138 Helmholtz 137 fugacity 147 fundamental transistions 66 general equlibrium 151 generalized displacement 110 generalized force 110 gerade 69 Gibb’s free energy 106 Gibbs-Duhem equation 163 good theory 16 group mathematical definition of 222 multiplication table 223 group theory 221 Hamiltonian operator 27 Hamitonian classical 27 harmonic oscillator 38 energy levels for 40. 85 potential energy for 47 Schrodinger equation for 47 wavefunction (no spin) 49 wavefunction (with spin) 52 ideal solution Raoult’s law 314 immiscible solutions 153 infrared spectroscopy 66 internal energy 103. 133 Heisenberg uncertainty principle 30 and the harmonic oscillator 41 helium 55 electron-electron repulsion term 55 Hamiltonian 55 Helmholtz free energy 106 Henry’s law 311.equlibrium constant 153 Euler’s identity 4 expansion of gases 111 reversible 114 extent of reaction 328 Eyring’s equation 265. 334 first law of thermodynamics 121. 133 flipping coins 90 fluctuation 92 fluorescence 242 stokes shift 242 Fourier’s law of heat conduction 306. 291 fermions 56 Fick’s first law 302. 334 Henry’s law constant 316.

86 Schrodinger equation for 65 wavefunction for 65 Morse potential 64. 290 mean ionic activity 162 mean ionic activity coefficient 162 method of initial velocities 259 method of isolation 259 microstate 90 Mie scattering 84 mirror plane symmetry 70 molar heat capacity 115 molecular collisions simple model for 252 molecular hydrogen ion 67 Hamiltonian for 67 molecular orbital diagram 76 molecular orbitals 68 molecular rotations 235 asymmetric tops 239 centrifugal stretching 236 linear tops 238 polyatomic molecules 237 spherical tops 239 symmetric tops 238 vibrational state dependence of 236 molecular vibrations 228 molecule Scrodinger equation for 78 momentum operator 5 Morse oscillator 64 energy levels for 65. 86. 290 mean free path 253.inversion symmetry 69 operator 69 ion mobility 166 and current 168 ion transfer 174 IR spectroscopy 231 and the character table 232 isothermal compressibility 274 isothermal expansion 279 Joule expansion 282 Joule-Thomson expansion 283 kinetic theory of gases 250 Lagrange multipliers 95 Laguerre polynominals 49 laminar flow 304 law of corresponding states 296 law of rectilinear diameters 293 Legendra polynomials 200 linear combinations of atomic orbitals (LCAO) 72 Lorenz number 307 many electron atom Hamlitonian for 59 maximal work 113 Maxwell relations 140 Maxwell’s distribution of speeds 252. 240 force constant associated with 9 Taylor series expansion of 8 normal modes 229 operator Hermitian 189 ladder 195 linear 189 symmetry 222 operator algebra 187 orientation quantum number 53 orthogonality 191 overtone transitions 66 parameters extensive 109 intensive 109 338 .

312. 276 relaxation effects 167 rigid rotor 200 degeneracy of 235. 218 Hamitonian for 194 wavefunctions for 195. 218 particle on a ring 194 boundary conditions 194 energy levels for 195. 233 and the character table 234 Raoult’s law 311. 218 partition coefficient 154 and drug delivery 155 for the Born model 174 partition function canonical 96. 291 reciprocal rule 108 red sunsets 82 Redlich-Kwang gas 270 reference states 147 relationship between CP and CV 139. 132 vibrational 101. 334 deviations from 315 reference state 315 rate law 255 rate laws 254 determination of 258 integrated 259 Rayleigh scattering 80 Rayleigh scattering law 81. 314. 218 features of the energy levels 35 normalization constant for 33 potenial energy 31 Schrodinger equation for 32 three dimensional 183 three dimensional energy levels 185 three dimensional wavefunction 185 wavefunction for 183 wavefunctions for 34. 219 339 . 181 energy levels 183 energy levels for 34. 132 translational 101.particle in a box 31. 131 electronic 101 grand canonical 97 isothermal—isobaric 97 microcanonical 96 molecular 100 rotational 101. 247 rotational energy levels 200. 44. 87 reaction velocity 255. 82. 133 Raman scattering 80 Raman spectroscopy 66. 324 principle quantum number 52 probability amplitude 22 probability distribution 22 PV work 111. 44. 132 Pauli exclusion principle 56 consquences of 58 perturbation theory 207 example of the quartic oscillator 208 phase diagram 300 Poiseuille’s formula 304 polarizability 79 postulate I (of quantum mechanics) 22 postulate II (of quantum mechanics) 24 postulate III (of quantum mechanics) 25 pressure 104 principle of Clausius 125. 248 energy 235.

219 Hamiltonian for 212 Tyndall scattering 84 ungerade 69 van der Waals equation 340 .degeneracy of 200 rotational Hamiltonian 200 rule of mutual exclusion 234 Rydberg constant 20 SATP 120 Schrodinger equation time dependent 214 time independent 27 second law “local” formulation 324 second law of thermodynamics 126. 53 spin-orbit coupling 205 Hamiltonian 205 interaction energy 205 spontaneous process 142 state function 121 table of important ones 136 Sterlings approximation 92 Stoke’s law 167. 304 STP 120 superposition 191 systems types of 108 temperature 115 term symbols 204 thermal conductivity 301 of gases 306 of liquids 306 thermal equilibrium 120 third law of thermodynamics 128. 53 wavefunction 51 spin orientation quantum number 51. 133 statements of 127 simple collision theory 262 Slater determinant 58 for lithium 59 solar system model 17 solvation 169 solvophobic effect 176 specific heat 115 spherical harmonic functions 48. 200 spin 201 quantum number 51. 133 tips for solving problems 2 total derivative 107 transfer matrix 11 triple point 300 two level system 211 ‘left’ and ‘right’ states 213.

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