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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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46 46 49 51 52 55 55 56 58 59 60 60 61 62 63 64 66 67 67 68 72 72 73

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
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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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137 138 138 139 139 139 140 142 142 144 146 147 148

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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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. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2 Quantum Dynamics . 228 33. . . 209 31 The Two Level System and Quantum Dynamics 211 31. . . . . . . . 211 31. . . . . . . . . . . Theory . . . . . . . . 29. . . . .1 Example: The C2v Group . . . 33 Molecules and Symmetry 228 33. . . . .1. . . . . . . . . . . . . . . . . . . . .1.4 Spin Orbit Coupling .2 Variational method . . . . . . . .1 Normal Modes . . . . . . . . . .2. . . . .2. . . 201 201 202 202 203 204 205 30 Approximation Techniques 207 30. . . . . . . . . . .1 Molecular Vibrations . . .2. 29. . . . . . . . . . . . . . . . General . . . . . . . . . . . . . . . . . . . . 32. . . . . . . . . . . . . . . .1 The Addition of Angular Momentum: 29. . . .1 Perturbation Theory . . . . . . . . . . . . . . . . . . . . . . . .2 Mathematical Groups . . . . . . . . 32. . 229 . . . . . . . . 29. . . . . . . . . . . . . . . .3 Symmetry of Functions .2 Normal Modes and Group Theory . . . . . . . . . . 29. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1 Direct Products . . . . . . . . . . . . 229 33. . . . . . . . . . . . . . .1 Symmetry Operators . . . . . . . . . . . . . . . .2 Addition of Angular Momentum . . 207 30. .4 Symmetry Breaking and Crystal Field Splitting . . . . . . . . . . . . . .2 An Example: Two Electrons . 214 VI Symmetry and Spectroscopy 220 221 222 222 223 223 225 225 32 Symmetry and Group Theory 32. . . . . . . . .3 Term Symbols . 32. . . . . .1 Spin Angular Momentum . . . . . . . . . 32. . .29 Addition of Angular Momentum 29. . . . . .3. . . . . . . . . . .2.1 The Two Level System . . . . . . . . . . . 32. . . .2.

. . . . . . . . . . . . . . . . . . . .1 Relaxing the rigid rotor . . . . . . . . . . . .2. . . . . . . . . . . . . . 39. . . . . . . . . . . . . . . . . . . . . . .1 IR Spectroscopy . . . . . . . . 254 254 258 259 259 . . .1 Absorption Spectra . . . . . . . . .1 kinetic theory of gases . .2 Raman Spectroscopy . . . . . . . . . 36. . 231 34.1.3 Fluorescence Spectra . . . . . . . . . .2. . . .2 Molecular Collisions . . . . . . . . . . . . . . . 233 35 Molecular Rotations 35. . . . . . . . . . . 36. . . . . . . . .2 Rotational Spectroscopy . . .1 Rate Laws . . . . . . . . . . . . . . 37 Fourier Transforms 245 37. . . . . . . . . . .1. . 245 VII Kinetics and Gases 249 38 Physical Kinetics 250 38. . . . . . . . . .1.34 Vibrational Spectroscopy and Group Theory 231 34. 35. . . . .1 The Structure of the Electronic State 36. . . . . . . . . .3 Rotation of Polyatomic Molecules . 250 38. . . . . . . . . . 36 Electronic Spectroscopy of Molecules 36. . . . . . . . . . . . . . . . . . . . . . . . . .1 The Franck—Condon principle 235 236 236 237 240 240 241 241 242 243 243 . . . . 39. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35. . .1 Diﬀerential methods based on the rate law 39. . . . . . . . . . . .2 Integrated rate laws . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36.2 Determination of Rate Laws . . . . . . . . . . . . . 36. . . . . . . . . . . . . . . . . .2 Emission Spectra . . . . . 252 39 The Rate Laws of Chemical Kinetics 39. . .1 The Fourier transformation . . . . . . .2. . . . . . . . . . . . . . . .2 Franck—Condon activity . . . . . . . . . . . . . . . . . . .

. .1 Temperature corrections to the Arrhenious 40. . . . . .2 α and κT for liquids and solids . . . . . . . . . . . . . . . . . . . 40. . . . . . . . . . . .3 When P is the more convenient variable . . . . . . .1. . . . . . . . . . . . . . . .1 Isothermal and Adiabatic expansions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2 The Virial Series . . . . 42. . . . . . . . . . . . 40. . . . .3. . . . . . . . . . . . 42.1 The Relationship Between CP and CV . . . . . . . .40 Temperature and Chemical Kinetics 40. . . . . . . . . 42. . . .3 Multistep Reactions . . . . . . . . . . . .2. . 288 . 42.1 P. . . . . . . . . . .1 Relation to the van der Waals Equation of State 41. .2 Heat Capacity of Gases Revisited . .3. . . . . 42. . . . . . . . .1 Calculation of Entropy . . . . . .3. . . . .2. .2. . . .1 α and κT for an ideal gas . . .1 Entropy of Real Gases . . . . . . .2 The Boyle Temperature . .3. . . . . . . . . parameters . . . . . 42. . . . . . . . . . . 43 Entropy of Gases 286 43. . 42. . . . . . . . . . . . . .4 Estimation of Virial Coeﬃcients . .1.1. . . . . . . . . . . . . . . 41. . . . . . . . . 286 43. . . 40. . . 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. 42.2 Theory of Reaction Rates . . . . . . . . . .4 Joule expansion . . . . . . . .3 The Virial Series in Pressure . . . . . .3 Expansion of Gases . .3. . . . .2. . . . . . . . . . . . . . . 42. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1 Temperature Eﬀects on Rate Constants . . 41. . . . . . . . .1. . . . . . . . .2. . . . . . . . . 42 Behavior of Gases 42.1 Equations of State . . 41. . V and T behavior . . . . . . . . . . . . . . . . . . . .5 Joule-Thomson expansion .2 Heat capacity CV for adiabatic expansions 42. . . . . . . . 41. . . . . . . . . . . . . . . . .4 Chain Reactions . . .

. . . . . . . . . . . . . . . . . . . . . . . . . .2 Raoult’s Law . . . . .3. . . . . . . . . . .1 The chemical potential and T and P . . . .3 Phase Equilibrium . . . . . . . . . .2 Viscosity .4 Henry’s Law . . .3. . . . . . . . .3. . . . . . 45. . . . .3. . . .2 The Law of Corresponding States . . 45 Transport Properties of Fluids 45. . . . . . . . . . . . . . . .1. . . . . .1 Measures of Composition . . . . . .3. . . . . . . . . . 44. . . . . . . . . . . . . . . . . . . . . . . . . . . 46. . . . 44. . . . . . . .3. . 44. . . . . . .2 The Clapeyron Equation . . . . . .1. . . . . . . . . .2. . . . . 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. . . . .3. . . . . . . . . . . . . . . . . 44. . . . . . . 44. . .2 Gas Constants from Critical Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45. . 46. .3.4 Equilibria of condensed phases .1 Notation . . 45. . . . . . . . . . . . .3 Ideal Solutions (RL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1 Gas Laws in the Critical Region .2. . . . . . . . . . . . . . . . . . . . . . . . . . . . .1 Thermal Conductivity of 45. . . . .2 Thermal Conductivity of 46 Solutions 46. . . . . . . 44. . . . . . . . . . . . . . . . . . . . 46. . . . . . . . .3 Vapor Equilibrium and the Clausius-Clapeyron Equation 44. . . . . . . . . . . . . Gases and Solids . . . .5 Triple Point and Phase Diagrams . . . .2 Partial Molar Quantities . . . . . . . . 46. . . . 44. . . . . . . . . . . . . . . . . . . . 46.1 Activity (a brief review) 46. . . . . . . . . . . . . .1 Critical Behavior of ﬂuids .1 Diﬀusion . . . . . . . . . . . . . . . . . . .2 Partial Molar Volumes . . . . . . . . . 46.3 Thermal conductivity . . . . . . 46. . . . . . . . . . . . . Liquids . . . . .3 Reference states for liquids . . . . .3. . . . . . .

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

Chemistry 351: Physical Chemistry I 1 1 .

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

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

±1.. start with a related concept that is better known by you. . This occurs at x = nπ. ±2 . • Make sure that the physical idea that you are using in your argument is correct. so the periodicity is π. • Always check to see if the math makes sense when you are done. cos 2x. Therefore the entire function has a period of π.. has a period of π as does the imaginary part. For problems that require a conceptual approach. • Look for self-consistency.. n = 0. Does you ﬁnal answer jive with what you know.• Do the math. sin 2x. . 4 . The second function we should remember from trig as having a period of 2π. If you are not sure. It might take some review on your part. 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. 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). either you will be able to do this or you won’t. We know that this function will repeat zeros when ever sin x = 0. 6.

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

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

Generally and average is calculated as Z ψ∗ (x)ˆψ(x). πa0 (15) 7 . (14) Remember the extra r2 sin θ is needed when integrating in spherical polar coordinates.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 . Problem: A quantum object is described by the wavefunction ψ(x) = e−γx over the range 0 ≤ x < ∞. ψ(x) = 2γe−γx . 2γ (13) So on average you will ﬁnd the object at x = 1 . What is the average position of the object? Solution: We need to work with the normalized wavefunction that we found in √ the previous problem. 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 . 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. The normalized 1s wavefunction is 1 ψ1s = p 3 er/a0 .

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

Solution: This problem requires the we think qualitatively about the wavefunctions and the potentials for the harmonic oscillator and the Morse oscillator. Problem: Without performing any calculations. (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. How many molecules are in the ﬁrst excited state of the ‘ring breathing’ mode (992 cm −1 )? How 9 . The Morse potential does not have this symmetry. The Taylor series about Req for this function is ¯ ¯ 2 ¯ dV (x) ¯ ¯ (R − Req ) + 1 d V (x) ¯ (R − Req )2 + · · · . Therefore without performing any calculations we can at least say that hRi increases as the quantum number increases. compare hRi as a function of the vibrational quantum number for a diatomic modelled as a harmonic oscillator versus a Morse oscillator. 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.So. yes the coeﬃcient of the linear term (the term involving (R − Req ) to the ﬁrst power) is zero. 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. This will always be true when you perform a Taylor series expansion about a minimum (or maximum). 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 .

02 × 1013 . ¶ ³ µ ´ 3×992 992 rb × e− 2×208 × 1020 = 8. B or C. × e = 2 sinh 2 × 208 17 (22) (25) 10 . Problem: Consider a linear chain of N atoms.02×10 × 100% = 1020 0.841% of the benzene molecules are in the 1020 13 ﬁrst vibrational excited state for the ring breathing mode and 4. So. ⎡ ⎤ ⎡ ⎤ ⎡ ⎤ 1 2 5 ⎢ ⎥ ⎢ ⎥ ⎢ ⎥ (1) (2) (3) (23) V = ⎣ 1 ⎦. V (j+1) = MV (j) . B or C.0000402% of the benzene molecules are in the ﬁrst excited state for the C—H stretching mode. V = ⎣ 7 ⎦.41×10 × 100% = 0. where for this example ⎤ 1 1 0 ⎥ ⎢ M = ⎣ 1 1 1 ⎦.41 × 1017 Nv=1 = 2 sinh (21) 2 × 208 and C—H Nv=1 We see that about 8. For example.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. 1 2 5 The V (j+1) can be found from the V (j) vector using the matrix equation. Each of the atoms can be in one of three states A. Find the entropy per atom for this system as N → ∞. except that an atom in state A can not be adjacent to an atom in state C.··· . 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 = ⎣ 3 ⎦.

So W = lim λN . 1. Tr[M N ] ≈ λN . 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 ⎦ . 12 5 1 . max where λmax is the largest eigenvalue of M. Now for large N. 3.The matrix M is the so-called transfer matrix for this system. Verify V (3) explicitly by drawing all the allowed 3-atom conﬁgurations. 4. 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. max N→∞ (26) 1. 5 states √ 5 states √ 11 . Use Boltzmann’s equation to ﬁnd the entropy per atom for this chain as N goes to inﬁnity. Verify W = Tr[M N ] for N = 1 and N = 2. Use M to ﬁnd V (4) 2. It can be shown that the number of conﬁgurations W = Tr[M N ].

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

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

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.¡ ¢ ¡ ∂U ¢ Now ∂U V is just heat capacity. ¶2 µ ¶ µ ∂P ∂V . but ∂V T is nothing convenient so we must ∂T proceed. ∂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 ¶ . CV . Cp = Cv − T ∂T P ∂V T (41) 14 . (40) P This eliminates the constant V term and so. One obtains ¶ µ ¶ µ n2 a n2 a ∂P nRT nR 2n2 a + 2 2 − + T −P =T = .

Part I Basic Quantum Mechanics 15 15 .

Atomic spectral lines 4. Low temperature heat capacity 3. The photoelectric eﬀect 2. Among these experiments were 1. Black body radiation and the ultraviolet catastrophe 16 16 . 1.1.1. • Many phenomena described by minimal and general concepts. Quantum Theory The goal of science is uniﬁcation. 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. experiments were being performed in which the results deﬁed explanation by means of the current understanding of physics.

1. • The electron orbits the nucleus with the attractive coulomb force balanced by the repulsive centrifugal force.2. Flaws of the solar system model • Newton: OK √ √ • Maxwell: problem 17 . First Attempts at the Structure of the Atom The “solar system” model. The two slit experiment 6.5.2. The Stern-Gerlach experiment ∗ ∗ See Handouts ∗ ∗ 1. Bohr’s Atomic Theory 1.

— 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. The atom collapses! Bohr’s model: Niels Bohr (1885—1962) 18 .

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

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 .6.7.6. 2 — Eionize experimentally observed from spectroscopy is 13.7.· · · 5. — Doing this results in the emission or absorption of a photon with energy v= ˜ 4E hc (1.4) — Since the orbitals are quantized.e — Eionize = 2a0 = 13. R is called the Rydberg constant.· · · Series Name Lyman Balmer Pachen Brackett Pfund (1.4.8.· · · 3.605 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 2.3. the atom may only change its orbital radius by discrete amounts.667 cm−1 = R.606 eV = 109.5.· · · 4.5.· · · 6.4.

The wave must satisfy periodic boundary conditions much like a vibrating ring ∗ ∗ ∗ See Fig.• Spin is not included in theory The Bohr quantization idea points to a wavelike behavior for the electron.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 . 11.

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

(2. z)|2 dxdydz < ∞ Normalization of the wavefunction In order for |ψ(x.2) space space 23 . y. 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. z) must be normalizable. (2.Properties of the wavefunction • Single valueness • continuous and ﬁnite • continuous and ﬁnite ﬁrst derivative R • space |ψ(x. 2. ψ unnorm = Nψnorm .1) Now.2. y. y. ψ(x. 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. ψunnorm we know that this function must simply be some constant N multiplied by the normalized version of this function: ψ unnorm = Nψnorm . where N = |ψunnorm (x. How to normalize a wavefunction If we have some unnormalized wavefunction. z)|2 to be exactly interpreted as a probability distribution. qR That is. y.

3) space space because that is the very deﬁnition of a normalized wavefunction. (2. Taking the square root of both sides gives. 24 .6) So ﬁnally we get the normalized wavefunction by reagranging ψ unnorm = Nψnorm : ψ norm = 1 ψ . 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. sZ N= space |ψunnorm (x. (2.8) 2 normalized x |ψ(x)| dx 1 −∞ 2. therefore this is a general procedure that will work for any wavefunction.4) This gives us an expression for N. Thus wherever R we see space |ψnorm |2 dxdydz we can replace it with 1. z)|2 dxdydz. N unnorm (2. So. Z |ψunnorm |2 dxdydz = N 2 × 1 = N 2 .5) space Z space |ψnorm |2 dxdydz = 1 (2. (2.3. y. Postulates II and II Postulate II: Every physical observable is represented by a linear (Hermitian) operator.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.7) Notice that no where did we ever specify what ψunnorm or ψnorm actually were.

Nearly all operators we will need are algebraic combinations of the above.). For a given operator only a special set of function satisfy this equation. There is a special operator equation called the eigenvalue equation which is ˆ Of (x) = λf (x) where λ is just a number. (2. These functions are called eigenfunctions.An operator takes a function and turns it into another function ˆ Of (x) = g(x) (2. 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. cylindrical. z) and coordinate systems (spherical.10) 25 . Postulate III: The measurement of a physical observable will give a result that is one of the eigenvalues of the corresponding operator.9) This is just like how a function takes a number and turns it into another number. etc.

Example ˆ ˆ Let O in the eignevalue equation be the operator that takes the derivative: O = ˆ d d = dx . So we want a solution to ˆ df (x) = λf (x) df (x) = λf (x) dx (2.11) So. we ask ourselves what function is proportional to its own derivative? ⇒ f (x) = eλx .The number that goes with each function is called the eigenvalue. So solution of the eigenvalue equation gives a set of eigenfunctions and a set of eigenvalues. So the eigenfunctions are the set of functions f (x) = eλx and the eigenvalues are the numbers λ 26 .

Deﬁne the classical Hamiltonian for the system.3. The operator associated with the total energy is called the Hamiltonian operator ˆ (or simply the Hamiltonian) and is given the symbol H. 1. This equation is the (time independent) Schrödinger equation. 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 Hamiltonian The most important physical observable is that of the total energy E. The Setup of a Quantum Mechanical Problem 3.1) 3.2. The eigenvalue equation for the Hamiltonian is ˆ Hψ = Eψ. 27 27 . 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. (3.1.

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

However. The Average Value Theorem Postulate III implies that if ψ is an eigenfunction of a particular operator representing a physical observable. but we cannot predict for certain which one. then all measurements of that physical property will yield the associated eigenvalue.12) space 29 . This is given by Z hˆ i = α ψ∗ αψdxdydz ˆ (3. hˆi = x and hˆx i = p Z Z ψ xψdxdydz = ˆ ∗ space Z space x |ψ|2 dxdydz ψ∗ ∂ψ dxdydz ∂x (3. • For one-dimensional problems −~2 d2 ψ + (V (x) − E) ψ = 0 2m dx2 (3.11) space ψ px ψdxdydz = −i~ ˆ ∗ Z (3.3. then all measurements of that physical property will still yield an eigenvalue. z) which determines whether this is easy or hard to do. give an expectation. or average. If ψ is not an eigenfunction of a particular operator. however.10) space For example.• Note: It is solely the form of V (x. We can. value for the measurement. y.9) 3.

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

⎪ ⎩ ∞ x≥a (4. We shall soon see that the particle in a box is a physically unrealistic system and. 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. Nevertheless it is of great pedagogical and practical value. 4. as a consequence. V (x). we must violate one of our criteria for a good wavefunction. we need to partition the x-axis into the three regions shown in the ﬁgure.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 .1) Because of the inﬁnities at x = 0 and x = a. It also can be used as a “zeroth order” model for certain physical systems. This system is very simple which is one reason for beginning with it.1.

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

In particular. ψ(a) = 0. a (4. · · · . this becomes a Z π π A2 a a/ 2a = . we see that the constant B must be zero because cos kx|x=0 = 1. the second b. So we are left with ψ(x) = A sin kx for our wavefunction. As can be inferred from the following ﬁgure. a The values of k are quantized. places certain restrictions on k. So..6) The constant A is the normalization constant.7) du = π dx.8) 33 .c. n = 1. 3.5) (4. 2.From the ψ(0) = 0 b. We obtain A from Z ∞ Z a nπx nπx ∗ sin dx. ψn (x) = A sin a kn = (4. ψn (x)ψ n (x) = 1 = A2 sin a a −∞ 0 Letting u = πx .c. now we have nπx . 1=A sin2 nudu = A2 π 0 2 / 2 π (4. nπ .

2ma2 8ma2 (4.9) Is this wavefunction OK? Thus our normalized wavefunctions for a particle ⎧ ⎪ 0 ⎪ q ⎨ 2 ψn (x) = sin nπx a ⎪ a ⎪ ⎩ 0 q 2mEn ~2 (4.2.Solving for A gives A= r 2 . (4.11) 4. Implications of the Particle in a Box problem Zero Point Energy 34 .10) We can get the energy levels from kn = En = and kn = nπ : a h n2 π 2 ~2 ~= 2π n2 h2 = . a in a box are I II III .

This residual energy is called the zero point energy and is a consequence of the uncertainty principle. so δˆ 6= ∞. has nonzero energy. δˆδp = 0 which violates the uncertainty principle. or ground state. 8ma2 (4.12) That is. the lowest energy state.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 . 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. If the energy was zero then we would conclude that momentum was exactly zero. But we also know that the particle is located within a ﬁnite region of ˆ space. δ p = 0.The smallest value for n is 1 which corresponds to an energy of E1 = h2 6= 0. x Hence.

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

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. 37 . There is 2 2 a a node at x = 2 .yet the probability of ﬁnding the particle at x = a is zero: ψ2 ( a ) = 0. it can never be found at the node.

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

where ω = conditions.5) This diﬀerential equation is not easy to solve (you can wait to solve it in graduate school).4) (5. P.x From Newton’s law of motion F = ma = m d 2 .E. Thus V = 1 kx2 . q k m (5. we need to express the force of the spring in terms of potential energy V . 39 . We know Z 1 V = − F dx = kx2 + C. This can be rearrange into the form −~2 d2 ψ + 2m dx2 1 ⎜ −~2 d2 ⎟ ˆ Hψ = Eψ ⇒ ⎝ + kx2 ⎠ ψ = Eψ.E. we get dt 2 d2 x k d2 x m 2 = −kx ⇒ 2 + x = 0 dt dt m (5. so in going to the quantum oscillator. 2 By postulate III the Schrödinger equation becomes ⎛ ⎞ K.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. 2 2 |2m dx } | {z } {z µ ¶ 1 2 kx − E ψ = 0 2 (5. (5.1) This is second order diﬀerential equation which we already know the solutions to: x = A sin ωt + B cos ωt.3) 2 Since energy is on an arbitrary scale we can set C = 0.

1.12 Laidler&Meiser ∗ ∗∗ 5.7) Note the energy levels are often written as 1 En = (n + )hν 0 . 11. An = p √ . ∗ ∗ ∗ See Fig. y = (5.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. 2 ~ 2n n! π where An is the normalization constant for the nth eigenfunction and Hn (y) are the Hermite polynomials. As it turns out. 2 where again ω = q k . 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 . 2 where ν 0 = 1 2π (5. The eigenvalues (the energy levels) are 1 En = (n + )~ω.6) x. 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 . m (5.8) q k m and is called the vibrational constant.

— On the other hand. • It is a consequence of uncertainty principle — If the ground state energy was really zero. then we would conclude that the momentum of the oscillator was zero. so δpδx = 0 Not allowed! — The uncertainty principle forces there to be some residual zero point energy. 2.1. δx = 0. this energy is called the zero point energy. Consider the ground state (the lowest energy level) • There is residual energy in the ground state because 1 E0 = (0 + )~ω. the quantum system must behave like a classical system. Consider the wavefunctions. we would conclude the particle was located at the bottom of the potential well (at x = 0) — Thus we would have δp = 0. 2 • Just like for the particle in a box. 3. • The wavefunctions penetrate into the region where the classical particle is forbidden to go — The wavefunction is nonzero past the classical turning point. Interpretation of the wavefunctions and energy levels 41 . In other words the quantum mechanics must contain classical mechanics as a limit. • The probability distribution |ψ|2 becomes more and more like what is expected for the classical oscillator when v → ∞. — This is a manifestation of the correspondence principle which states that for large quantum numbers.

5. Spectroscopy (An Introduction) The primary method of measuring the energy levels of a material is through the use of electromagnetic radiation. Atoms and molecules absorb or emit light only at speciﬁc (quantized) energies. Experiments involving electromagnetic radiation—matter interaction are called spectroscopies.2. 42 . These speciﬁc values correspond to the energy level diﬀerence between the initial and ﬁnal states.• 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.

Equations • The short cut for getting the normalization constant (1D. N unnorm (5.11) 43 43 . (5.10) • The Schrödinger equation (which should be posted on your refrigerator). ˆ Hψ = Eψ. (5. see above for 3D).9) • The normalized wavefunction: ψ norm = 1 ψ . 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. The equations are collected here simply for handy reference for you while working the problem sets. 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. sZ N= space |ψunnorm (x)|2 dx.

∂x (5. ω = 2 k m (5.14) • Normalized wavefunctions for the 1D particle in a box.17) • The wavefunctions for the harmonic oscillator are ¶1 µ 2 km 4 1 − y2 x. 2 n n! π ~ 2 (5. y = √ .16) • The energy level spacing for the 1D particle in a box. Z ψ∗ αψdx.15) (5. 4E = (2n + 1) h2 8ma2 (5.19) 44 .12) (5. −~2 d2 ψ + (V (x) − E) ψ = 0. a a • The energy levels for the 1D particle in a box. ˆ hˆ i = α space (5. An = p ψn (y) = An Hn (y)e .13) • The momentum operator px = −i~ ˆ ∂ .18) where An is the normalization constant for the nth eigenfunction and Hn (y) are the Hermite polynomials. r nπx 2 ψn (x) = sin . En = h n2 π 2 ~2 ~= 2π n2 h2 = . 2ma2 8ma2 (5. 2m dx2 • How to get the average value for some property (1D version).• The Schrödinger equation for 1D problems as a diﬀerential equation. r • The energy levels are 1 En = (n + )~ω.

Part II Quantum Mechanics of Atoms and Molecules 45 45 .

Hydrogenic systems Hydrogenic systems are those atomic systems which consist of a nucleus and one electron. Hydrogen is the only atom for which we can exactly solve the Schrödinger equation for.6. The obvious choice for the coordinate system is to use spherical polar coordinates 46 46 . The Hydrogen atom (one proton and one electron) is the obvious example Ions such as He+ and Li2+ are also hydrogenic systems. 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.1. The Schrödinger equation for all the other atoms on the periodic table must be solved by approximate methods. That is they are completely symmetric about the nucleus. we move onto the quantum mechanical treatment of atoms. 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 .with the origin located on the nucleus. (4π 0 )r (6. ˆ Hang ψang (θ. φ) It turns out that solving the Schrödinger equation. φ).7) 47 . ψ(r. The classical potential energy for these hydrogenic systems is V (r) = So the Hamiltonian is −Ze2 . θ. φ) = ψrad (r)ψang (θ. ψ must be a product state.8) (6.2) Schrödinger’s equation (in spherical polar coordinates) becomes ˆ Eψ = Hψ (6.5) −~2 ˆ Hang = 2me (6.1) −Ze2 −~2 ˆ 2 ˆ . ∇ + H= 2me (4π 0 )ˆ r (6.4) (6.6) Since the Hamiltonian is the sum of two terms. φ) = Eψang (θ. (6. 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.

11) l(l + 1)~2 . φ) = ER(r)Ylm (θ. θ. The full Schrödinger equation becomes ˆ Hψ(r. φ) = ER(r)Ylm (θ. φ). φ) = Eψ(r.yields ψ ang (θ. φ). φ) ˆ HR(r)Ylm (θ. φ) = 2me Now let’s denote the radial part of the wavefunction as ψ rad (r) = R(r). ˆ It also turns out that the energy associated with Hang is found to be E = El = So. φ) ¶ µ 1 ˆ ˆ Hrad + 2 Hang R(r)Ylm (θ. (Mathematica knows them and you can use them just like any other built-in function like sine or cosine. 2me (6. φ)’s are the spherical harmonic functions characterized by quantum numbers l and m. (6. φ) = Ylm (θ.) We shall use the spherical harmonics more next semester when we develop the quantum theory of angular momentum. φ) Hang ψang (θ.12) (6. θ. The spherical harmonics are known functions. l(l + 1)~2 ˆ ψang (θ. r ˆ Operating with Hang we get ¶ µ 2 ˆ rad + l(l + 1)~ R(r)Ylm (θ. φ) = ER(r)Ylm (θ.13) 48 .10) (6.9) where the Ylm (θ. φ) H 2me r2 (6.

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

ψ 3d0 are pure real and so these are the same in the “chemists” picture as in the “physicists” picture. The wavefunctions that chemists like are pure real. The table below lists the atomic orbitals in the “chemists” picture as linear combinations of the “physicists” picture wave functions.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). ψ 2p0 . The atomic orbital you are used to from freshman chemistry are the “chemists” picture of atomic orbitals In the above table ψ1s . ψ 2s . So one needs to form linear combinations of these orbitals such that these combinations are pure real. 50 .

The spin wavefunction is a function in spin space not the usual coordinate space. 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. electrons also posses an intrinsic quantity called spin.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. Spin is actually rather peculiar so we will put oﬀ a more detailed discussion until next semester. so we can not write down an explicit function of the coordinate space variables. 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).3. • ms is the spin orientation quantum number and ms = ±1/2 for electrons.

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

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

In 1948 Richard Feynman developed the beginnings of quantum electrodynamics (QED). The Dirac theory was still not fully complete.bold prediction of the existence anti-matter that has now been veriﬁed time and again. so we limit ourselves to the non-relativistic Schrödinger theory. 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. 54 .

for example. It makes a closed form solution impossible. repulsion where r12 = |r1 − r2 | is the distance between the electrons.7. it is so complicated that it can’t be solved exactly.1) K. The electron—electron repulsion term is responsible for the diﬃculty of the problem. In fact.E of electron 1 P.1. helium. Two Electron Atoms: Helium We now consider a system consisting of two electrons and a nucleus. Although the extension from hydrogen to helium seems simple it is actually extremely complicated. The problem must be solved by one of the following methods • Numerical solutions (we will not discuss this) 55 55 .E of eletcron 2 elec. 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. (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 } .E of electron 2 P.—elec. Multi-electron atoms 7.E of electron 1 K.

⎨ ψ(1. 2) = or ⎪ ⎩ −ψ(2. All physical properties of a system where we have labelled the electrons as.g. helium 56 . The Pauli Exclusion Principle Electron are fundamentally indistinguishable.. say..g. Note: a similar statement exists for bosons (e. They can not truly be labelled. Now. 1). photons): The total wavefunction for bosons must be symmetric under exchange of indistinguishable bosons. Let us consider the two electron atom. 1 and 2 must be exactly the same as when the electrons are labelled 2 and 1.2.2) antisymmetric The Pauli exclusion principle states: The total wavefunctions for fermions (e.• Perturbation theory (next semester) • Variational theory (next semester) • Ignore the electron—electron repulsion (good for qualitative work only) 7. All this implies that ⎧ ⎪ +ψ(2. electrons) must be antisymmetric under the exchange of indistinguishable fermions. only |ψ|2 is directly measurable–not ψ itself. 1) symmetric (7.

one must make an antisymmetric linear combination of the spin parts. • Similarly for Ψd . • Ψb and Ψc have symmetric spatial parts. So. | {z }| {z } spatial part spin part (7.3) Since a complete solution for helium is not possible we must use approximate wavefunctions. but the spin part is neither symmetric or antisymmetric.4) where the single particle wavefunctions are that of the hydrogenic system.The total wavefunction is Ψ = ψ(1. The Pauli exclusion principle implies that if the spatial part is even with respect to exchange then the spin part must be odd. 2)χ(1. 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. Since we are doing this. we may as well simplify matters and use product state wavefunctions (products of the hydrogenic wavefunctions). Ψ = ψ(1)ψ(2)χ(1)χ(2). 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. Likewise if the spatial part is odd then the spin part must be even.5) 57 . It must be excluded. (7.

¯ ¯ . . Namely the wavefunction is product state that must be antisymmeterized in accordance with the Pauli exclusion principle. . . 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. .3. 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. 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.6) 7. . .7) (7. . . ¯ ¯ ¯ ¯ ¯ ψ (N)α(N) ψ (N)β(N) ψn (N )α(N) ψn (N)β(N) ¯ 1s 1s 58 . .The appropriate linear combination is α(1)β(2) − α(2)β(1). . The product wavefunction for the ground state is determined by applying the aufbau principle.8) .

9) (7. As an example consider lithium: • There are three electrons so we need three hydrogenic wavefunctions: ψ1s α. 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. This agrees with the Puli exclusion principle.11) H= 2me i 4π 0 ri j>i 4π 0 rij i=1 59 . • 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. ψ1s β. It is also antisymmetric under exchange of columns.1.3. 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.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). and ψ2s α (or ψ 2s β).

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

1. e2 4π 0 rji is the electron—electron 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 .1) (8. P ~2 ˆ 2 ˆ Te = i − 2me ∇ei is the kinetic energy operator for the electrons. + 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.1.8. ˆ TN is the nuclear kinetic energy operator and is given by 2 2 ~2 ˆ2 ∂ ˆ2 ∂ ˆN ˆN = − ~ ∇2 = − ~ + J . ˆ VNN = ZA ZBe e2 4π 0 R is is the nuclear—nuclear potential energy operator.2) m1 m2 m1 +m2 ˆ where J is angular momentum operator for molecular rotation and μ = the reduced mass of the diatomic molecule. 61 . R T 2μ 2μR2 ∂R ∂R 2μ (8.

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 .

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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

• 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. y. y. y.Inversion symmetry • The potential ﬁeld of the hydrogen molecular ion is cylindrically symmetric about the z-axis. z). z) = ψ(−x. • Because of the symmetry the electron density at (x. z) must equal the electron density at (−x. −z). ˆ. (9.3) Cylindrical symmetry 69 . −y. −y. ı • Moreover the eigenvalue a can be either +1 or −1. −z) = aψ(x. • The above symmetry therefore requires that the molecular orbitals be eigenfunctions of the inversion operator. That is ı ˆψ(x.

. . . • The molecular wavefunction is described by an eigenvalue λ = 0.• The cylindrical symmetry implies that the potential energy can not depend on the φ. — 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. ±1.

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

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 need to ﬁnd some useful approximations for them.2) 72 72 . LCAO is qualitatively very useful but it lacks quantitative precision. Molecular Orbital Diagrams 10. Unfortunately we can’t have both.1) and (1sB ) = ke−rB /a0 (10. Let us again consider the hydrogen molecular ion H+ : let one H atom be labelled 2 A and the other labelled B. We will discuss the approximation which models the molecular orbitals as linear combinations of atomic orbitals (LCAO).10.1.

4) (10. Conversely Φ− represents a situation in which the electron density is very low between the nuclei and thus represents an antibonding orbital 10. Classiﬁcation of Molecular Orbitals With atoms we classiﬁed atomic orbitals 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. But we shall also classify them according to their inversion symmetry and wether or not they are bonding or antibonding.1.3) (10.5) As can be seen from the above ﬁgure. For molecular orbitals we shall also classify them according to angular momentum. 73 . Φ+ represents a situation in which the electron density is concentrated between the nuclei and thus represents a bonding orbital.

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

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

Some get very complicated. 10.3. It is also to be expected since we know H2 is a stable 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. 76 .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. Molecular Orbital Diagrams The energy levels associated with the molecular orbitals are drawn schematically is what is called a molecular orbital diagram.

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

(Next semester will we look at the details of this for polyatomic molecules) ˆ Hmol Ψmol = Emol Ψmol (10.9) ´ ³ ˆ ˆ ˆ Hele + Hvib + Hrot ψele ψvib ψrot = (Eele + Evib + Erot ) ψele ψvib ψrot 78 . We can succinctly express the Schrödinger equation for a molecule as follows. 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.4.10. Likewise we have discussed molecular orbitals which are the electronic wavefunctions.

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. An Aside: Light Scattering–Why the Sky is Blue This chapter addresses the topic of light scattering from two diﬀerent perspectives. • Classical electrodynamics • Classical statistical mechanics Since this is not a course on electrodynamics. 11. we have to take several key results from that theory on faith.1. (11.1) where α is the polarizability of the molecule describing the “ﬂexibility” of its electron cloud. 79 79 . When the light interacts with the molecule an electric dipole is induced according to μ = αE.11.

The second term corresponds to Stokes Raman scattering where the scattered light is shifted to the red of the incident frequency. 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 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.2) The polarizability also depends on the positions of nuclei to some degree. 80 .4) where a trig identity was used in the last step.For light. (11. 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. That is. In this case we see the dipole oscillates at three distinct frequencies: ω. According to classical electrodynamics an oscillating dipole emits an electromagnetic ﬁeld at the oscillation frequency.3) (11. the electric ﬁeld part is E(t) = E0 cos ωt.

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

but red sunsets occur for the same reason– Rayleigh scattering. The following ﬁgures illustrate why Rayleigh scattering implies that the sky is blue.2. 11.1.We just learned that light scatters as it traverses the atmosphere according to Rayleigh’s scattering law: I(λ) ∝ 1/λ4 . Sunsets We have focused on a blue sky. 82 .

White Clouds We might expect that clouds should be highly colored since they consist of droplets of water which scatter light very eﬀectively.2.2. 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 .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. 11.

particularly in liquid suspensions. In this limit an entirely diﬀerent analysis is made–one does not have Rayleigh scattering but instead has a process called Mie scattering. In some contexts. The water droplets are much larger than the wavelenght of the light–quite the opposite case as above.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 .

(11. This section should not substitute for your studying of the rest of this material. θ. Equations • The wavefunctions for the hydrogenic system are ψnlm (r.8) na0 2n[(n + l)!]3 85 85 .7) where the normalization constant. φ) • The radial part is.Key Equations for Exam 2 Listed here are some of the key equations for Exam 2.6) µ 2σ n ¶l e −σ/n 2l+1 Ln+1 µ 2σ n ¶ . 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. φ) = Rnl (r)Ylm (θ. The equations are collected here simply for handy reference for you while working the problem sets. Rnl (σ) = Anl (11. Anl . depends on the n and l quantum numbers as sµ ¶3 2Z (n − l − 1)! Anl = − (11.

2 2 where ω e xe together is the anharmonicity constant. y = x. • The energy levels are 1 En = (n + )~ω.13) Now the zero of energy is the dissociated state (i.n = −De + hc˜ e (n + ) − hc˜ e xe (n + )2 .10) where An is the normalization constant for the nth eigenfunction and Hn (y) are the Hermite polynomials.14) 86 . (11.Ee (Req ) = 0).12) q μ where De is the well depth and β = 2πc˜ e 2De is the Morse parameter. • The energy levels for the Morse oscillator are of the form 1 1 ω ω Evib. . 2 n n! π ~ 2 (11.Ee (R → ∞) = 0).e. An = p √ . (11. • The Morse Potential can also be written as Ee (R) = De [e−2β(R−Req ) − 2e−β(R−Req ) ].• The energy levels for the hydrogenic system are given by En = − Z 2R n2 (11. . ω Note: this expression for the Morse potential has the zero of energy at the bottom of the well (i.e.9) • The wavefunctions for the harmonic oscillator are ¶1 µ 2 km 4 1 − y2 ψ n (y) = An Hn (y)e . ω = 2 • The Morse potential is r k m (11.11) Ee (R) = De [1 − e−β(R−Re q ) ]2 . R = Req . 4De (11. R → ∞. with xe = ˜ hc˜ e ω .

• Bond order is deﬁned as BO = 1 (# of bonding electrons − # of antibonding electrons) 2 (11.15) • The Rayleigh scattering law is I(λ) ∝ 1/λ4 ∝ ω 4 (11.16) 87 .

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

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

12. The number of possible conﬁgurations is deﬁned as W. • Conﬁguration: The collection of all equivalent microstates.g. p!(N − p)! (12. p) = N! . outcome 1 after N measurements. The Boltzmann equation is S = k ln W Where S is entropy and k is Boltzmann’s constant. Boltzmann developed an equation to connect the microscopic properties of an ensemble to the macroscopic properties.1) The number C(N.1.3) 90 . (12..2) (12.• 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. 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. ﬂipping coins). p)xp . One valuable piece of statistical information about system is knowing how many diﬀerent ways the system appears p times in. This is given by the mathematical formula for combinations C(N. say. Combinations and Permutations Consider a random system that when measured can appear in one of two outcomes (e.

5) For combinations we did not care what order the results of the measurements occurred. 91 . p) = N N 2 2 p!(N − p)! (12. So rather than a particular combination. Sometimes the order is important.4) 2N = C(N. p). This is given by W (N. This gives (1 + 1) N = N X p=0 N X p=0 C(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. p) = 1 1 N! C(N. So the probability of any one outcome of N measurements is P (N.6) where N is the total number of measurements and Ni is the number of indistinguishable results of type i. Set x = 1 in the above. {Ni }) = N! N1 !N2 !N3 ! · · · (12. p)(1)p (12. we are interested in a particular permutation. ∗ ∗ ∗ See Examples on Handout ∗ ∗∗ For both combinations and permutations we need to evaluated factorials.

Macroscopic equilibrium is a dynamic rather than static equilibrium. It can be shown that (12. So for example if N = 1024 then (12. Sterlings Approximation: • In place of evaluating factorials of large number one can use Sterling’s approximation to approximate the value of the factorial.This is no problem for small numbers. but when we consider macroscopic systems (1020 or so molecules) no calculator can handle factorials of such large numbers. Consequently. • Sterling’s approximation is ln(N!) ' N ln N − N (12.2. ¯ O N where N is the number of particles. The ﬂuctuation about an average value for any observable property O is described by the variance which is deﬁned as ¯ σ 2 ≡ O2 − O2 . O σ O is consider the range of the observable property. but sometimes it is important.9) 1 √ N = 10−12 92 . we speak of the average value of the property. Often this ﬂuctuation is not important.7) 12. Fluctuations When we list the macroscopic properties of a material such as a beaker of benzene or the air of the atmosphere. the value of a certain property ﬂuctuates about the average value.8) σO 1 ≈√ .

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

E. 94 94 .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. The Boltzmann Distribution Consider a isolated system of N molecules that has the set { i } energy levels associated with it. and the total number of particles will be constant. The total energy is given by E= where Ni is the number of particles in energy state i. N= X i X i Ni i . of course. Since the system is isolated the total energy. (13. The total number of particles is. N1 !N2 ! · · · (13.2) The number of conﬁgurations for the system is then given by the number of distinct permutations of the system W = N! .13.1) Ni (13.

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

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

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. 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 ).) The partition function is to statistical mechanics as the wavefunction is to quantum mechanics. In the following we give an argument which provides a relation between the partition functions. but it is a very good approximation for large numbers of particles. In fact we have already seen this in the S = k ln W. That is. 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).1. for among other reasons. the partition function contains all that can be known about the ensemble. But this an inconvenient connection because. 97 .This was ﬁrst encountered as the denominator of the Boltzmann distribution and it is extremely important in statistical mechanics.1. It is not an exact relation as we derive it. (Note: the symbol Z is also often used for the canonical partition function.

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 Ã #! " ¶ 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

β Entropy We have already obtained the expression for entropy.11) (14.β µ ¶ µ ¶ ∂Q 1 1 ∂ ln Q = = . It is S = U + k ln Q T µ ¶ ∂ ln Q = −kβ + k ln Q ∂β n.β n.β β ∂V n.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.10) 105 .V (14.

We will make the distinction between the Helmholtz free energy and the more familiar Gibb’s free energy (G) later as well. 106 .V n. 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. 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. That is.V = −kT ln Q Any thermodynamic property can now be obtained from the above functions as we shall see in the following chapters.Helmholtz Free Energy Free energy is the energy contained in the system which is available to do work.12) ∂β ∂β n.

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

15.5) u 15.2.3) y 4. Closed system: A system that cannot exchange matter with its environment but may exchange energy.3. The cyclic rule: ¶ y ∂z =− ∂y ∂z ∂x ¶ µ ¶ µ x ∂y ∂x (15. The reciprocal rule: µ µ ∂z ∂x ∂z ∂x ¶ µ y ∂x ∂z ¶ =1 ¶ (15. Finally µ ∂z ∂x ¶ = u µ + y µ ∂z ∂y ¶ µ x ∂y ∂x (15. 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. Types of Systems Isolated system: A system that cannot exchange matter or energy with its environment.2. Microscopic systems: Systems containing a small number of particles. Deﬁnitions System: a collection of particles Macroscopic systems: Systems containing a large number of particles.4) ¶ z 5. 108 .1.

mass.2. Work and Heat A system may exchange energy with its environment or another system in the form of work or heat. density. volume moles = molar volume.6) = speciﬁc heat. • Work is exchanged if external parameters are changed during the process. temperature. = density. pressure. Extensive properties can be “converted” to intensive properties through ratios: Extensive property → Intensive property. heat capacity. • For example. 15. Intensive parameters (or properties): properties that are independent of the amount of matter.2. volume. System Parameters Extensive parameters (or properties): properties that depend on the amount of matter.Open system: A system that may exchange matter and energy with its environment. Adiabatic system: A closed system that also can not exchange heat energy with its environment. • Heat is exchanged if only internal parameters are changed during the process. • For example. Extensive property For example mass volume (15.3. heat capacity mass 15. 109 .

g. or more generally as dw = X i (15. Joules). Generalized Forces and Displacements In physics you learned that an inﬁnitesimal change in work is given by the product of force. but the product of the two must have units of energy (e.3. Work is negative (w < 0) if work is done by the system. a. times and inﬁnitesimal change in position. which acts as ‘generalized displacement.Convention Work. F . w.’ Note that the generalized force need not have units of force (e.. 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. Heat. 15. meters). A may be considered as a ‘generalized force’ which is coupled to a particular internal parameter.g.1. Heat is negative (q < 0) if heat is released from the system.g.7) For thermodynamics.. q. dx: dw = F dx. (15.8) Ai dai (15.. is positive (q > 0) if heat is absorbed by the system. is positive (w > 0) if work is done on the system. we need a more general deﬁnition if inﬁnitesimal work.9) 110 . Any given external parameter.

dM Moles.3.if more than one set of parameters change. dn Height. dQ Magnetization. dV Strain. this is called P V work. σ Surface tension. dε Surface area. mg Volume. a Contribution to dw Pressure. A Generalized Displacement. dA Charge.2. H Chemical Potential. E Magnetic Field. (15. γ Voltage. 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. dh −P dV σdε γdA EdQ HdM μdn mgdh 15. The following table gives some examples of generalized forces and displacements Generalized Force. That is dw = −P dV. −P Stress.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. μ Gravity.

Rx Recall from physics that work is the (path) integral over force: w = − x12 F dx.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. This can be manipulated as Z x2 Z x2 Z V2 F w=− F dx = − Adx = − Pex dV (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.12) 112 .

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. Maximal Work: Reversible versus Irreversible changes The value of w depends on Pex during the entire expansion. 16.16.1) 113 113 . In the ﬁgure wA = − Z V2 V1 Patm dV = −Patm (V2 − V1 ) (16.1.

Thus wrev is the maximum possible work that can be done in an expansion.and wB = w1 + w2 . wrev = − Z V2 Pgas dV (16.4) Hence it is clear that |wB | > |wA | . Now consider case in the ﬁgure below The expansion is reversible. where w1 = − and Z Vi (16. 114 . That is.3) w2 = − Vi Patm dV = −Patm (V2 − Vi ) (16. Namely Pgas = Pex . there is always an intermediate equilibrium throughout the expansion.2) V1 Patm+2W dV = −Patm+2W (Vi − V1 ) Z V2 (16. wrev = wmax .5) V1 This is the limiting case of path B in the previous ﬁgure. So.

16. C(T ) = From this equation dq = C(t)dT.b. dq amount of heat energy is transferred..9) V 115 . Temperature is not the amount of heat.8) (16.. divide by the number of moles to get molar heat capacity µ ¶ 1 dq CV m (T ) = n dT V 2. heat capacity is a function of T . heat is related to temperature through the heat capacity dq dT n. ¡ dq ¢ ¡ dq ¢ e. Temperature is an intensive property and heat is an extensive property. divide by mass to get speciﬁc heat 1 cV = m We will discuss heat capacity more later. Heat Capacity Temperature and heat are diﬀerent.2. To make an intensive property 1. (16.6) (16. it is not a constant.g. µ dq dT ¶ (16. CV (T ) = dT V and CP (T ) = dT P are not the same Heat capacity is an extensive property. The heat capacity also depends on the conditions during the temperature change. when the temperature of a substance having a heat capacity C(t) is changed by dT.7) That is. However.

16. The state of a pure. (More complicated systems require more than two independent variables. homogeneous material (in the absence of external ﬁelds) is given by the values of any two intensive properties. Example 1: The Ideal Gas Law The equation of state for volume of an ideal gas is P V = nRT . but behave in the same way as the more simple pure system.3.3. e.11) where Vm = V .1.12) 116 . P ).g. so we will focus our development of thermodynamics on simple systems. P independent then heat capacity is a function of T and P . (16. ρ= nRT RT (and molar (16. The ideal gas equation of state can be expressed in terms of intensive variables only P Vm = RT . n m V The equation of state can also be expressed in terms of density ρ = mass m/n) MP mP = .10) where R is the gas constant (8. C(T. 16.. (16.315 J K−1 mol−1 ) and n is the number of moles. Equations of State The macroscopic properties of matter are related to one another via a phenomenological equation of state.) The functional dependence of any property on the two independent variables is an equation of state. T .

2. V − nb V (16.3.16.13) 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 . 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.

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.In term of intensive variables P = a RT − 2.15) 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. Vm − b Vm (16.14) 16.3. Other Equations of State The van der Waals equation of state is not the only one that has been proposed.3.16) • Redlich-Kwang P = (16.17) 118 .

Today we will cover the zeroth and ﬁrst laws.17. Next time we will cover the second and third laws which both deal with entropy. which deal with temperature and total energy respectively. The temperature at which (for ﬁxed V and n) the pressure is zero is deﬁned as T =0K • T (Kelvin) = T (Celsius) + 273. 17. The Zeroth and First Laws of Thermodynamics Over the course of the next two lectures we will discuss the four core laws of thermodyanmics. 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. Temperature and the Zeroth Law of Thermodynamics Temperature tells us the direction of thermal energy (heat) ﬂow.15 119 119 . • Heat ﬂows from high T to Low T.1.

Standard conditions • standard temperature and pressure (STP): T = 273. (17. 120 .414 L/mol) • standard ambient temperature and pressure (SATP): T = 298. (Vm (STP) = 22. 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. The zeroth law of thermodynamics • Mathematical statement: If TA = TB and TB = TC . (Vm (SATP) = 24. Adiabatic wall: A wall the does not allow heat to ﬂow through it. 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 atm.789 L/mol) Diathermic wall: A wall that allows heat to ﬂow through it. C.1) The zeroth law implies that if an arbitrary system.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. then the systems are in thermal equilibrium.

The internal energy state function For characterizing the change in energy of a system. P )). So for a system where all the work is P V work the ﬁrst law becomes Z V2 4U = q − Pex dV V1 (17. The value of the state function depends only on that given state and on no other possible state of the system. The energy of a system is called the internal energy (U) of the system. one is concerned with the work done on the system (w) and the heat supplied to the system (q).g. The ﬁrst law of thermodynamics: • Mathematical statement: or in diﬀerential form dU = dq + dw (17.2..2.2) • 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.4) 121 . 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.1.17. 17. V (T.3) 4U = q + w (17.

∂T The other slope.8) . 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 (17.9) (17.7) µ (17.5) Although U can be expressed as a function of any two state variables. U → U(T. is called the internal pressure (it has no standard symbol). dU = ∂T V ∂V T So. ¶ ¶ µ ∂U ∂U dq = CV dT = dq =⇒ = ∂T V ∂T V dT ¡ ¢ Hence the slope ∂U V is the heat capacity. the most convenient at this time are V and T. V ).6) (17.in diﬀerential form this is dU = dq − Pex dV (17.10) V 122 . 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. The total diﬀerential of U (T. ¡ ∂U ¢ ∂V T (17.

123 .13) is the equation of state for U. ii) ideal gas or at constant volume. Hence ∂T ∂T ¶ ∙ µ ¸ ∂P − P dV dU = CV dT + T ∂T V (17.12) (17.11) The equation of state for U : Express U in terms of T. and P. A useful approximation is 4U = CV 4T which is valid for i) heat capacity nearly constant over 4T and with no phase transitions. V. 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).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.

1. 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. S= So we may write dS = (18. S. A.18. S is also a state function . The Second and Third Laws of Thermodynamics 18. U A 1 − = (U − A). Hence.2) 1 (dU − dA) T 124 (18.1) T ¯ Now. Entropy and the Second Law of Thermodynamics We learned from statistical mechanics that entropy. the average energy of the system E is in fact what we call internal energy: ¯ U ≡ E.3) 124 . and T are state functions. (18. Furthermore we derived the simple relation between the Helmholtz free energy and the canonical partition function as A = −kT ln Q. T T T Since U.

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.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 .for an isothermal process. Hence dA = dwrev . For now let us limit the discussion to reversible processes. Then dS = 1 1 (dU − dwrev ) = (dqrev + dw rev − dw rev ) / / T T dqrev . We learned previously that the maximum amount of work one can extract from the system is the work done during a reversible process. (Reversible process) = T (18. Recall the deﬁnition of Helmholtz free energy–the energy of the system available to do work.

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

3. 4. Work must be done to transfer heat from a cold to a hot reservoir. A cyclic process must transfer heat from a hot to cold reservoir if it is to convert heat into work.2.1. 2.6) From our earlier discussion of heat capacity dq = CV dT (CV since constant volume). So.18. Spontaneous processes are irreversible in character. dU = dq + dw = dq − Pex dV (18.7) T1 CV dT. Statements of the Second Law Unlike the ﬁrst law. T (18. the second law has a number of equivalent statements 1.1. 6. The entropy of the universe is increasing 5. The Third Law of Thermodynamics Consider the ﬁrst law for a reversible change at constant volume. The entropy of an isolated system will always increase in a spontaneous process (the principle of Clausius) 18. So CV dT =⇒ 4S = dS = T Z T2 (18. A useful perpetual motion machine does not exist.8) 127 . dU = CV dT but also dU = T dS.

Alternative statement of the third law: Absolute zero is unattainable.11) Hence the mathematical statement of the third law is Z T2 CP S(T2 ) = dT + S0 T 0 (18. For S0 to have signiﬁcance CP T must be ﬁnite (not inﬁnite) as T → 0. CO).10) 4S = T T1 now let T1 → 0 4S = S2 − S0 = Z T2 0 CP dT T (18..g. a microscopic point of view suggests S0 = 0 for perfect crystals of atoms or of totally symmetric molecules (e. The Third Law Verbal statement The third law of thermodynamics permits the absolute measurement of entropy.g. To derive the mathematical statement of the third laws we starting with Z T2 CP dT (18. O2 etc.2. Consider the heat capacity near T → 0. S0 6= 0 for imperfect crystals and crystals of asymmetric molecules (e.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 (18.1.12) From a macroscopic point of view S0 is arbitrary.9) 4S = T T1 18. 128 . Ar. Thus CP → 0..). However.

2. In other words.2. 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. ∗ ∗ CP m . In view of what we have learned about ﬂuctuations. 18. a = CP m /T ∗3 . Debye’s Law Heat capacity data only goes down so far. 129 . (Debye) Postulate: CP m = aT 3 . So one needs a theoretical extrapolation down to T = 0.But CP = dq dT → 0 implies dT dq → ∞. T ∗ are the lowest temperature data points. That is at low temperatures heat capacity goes as the cube of the temperature. an inﬁnitesimal amount of heat causes an inﬁnite change in temperature. So.

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

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.14) (18. The equations are collected here simply for handy reference for you while working the problem sets.16) 131 131 .15) • The canonical partition function is Q= gj e−βEj (18.Key Equations for Exam 3 Listed here are some of the key equations for Exam 3. (18. 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.

σθr 2 (18.18) Λ where h Λ≡ √ (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 . 2 sinh 1 β~ω 2 (18.19) 2πmkT is the thermal de Broglie wavelength.• 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.β = β ³ =− + k ln Q ¡ ∂ ln Q ¢ ∂V ³ ∂ ln Q ∂β ´ n. • The Rotational Partition Function (linear molecules) is T qrot ≈ . (18.21) • The ensemble average of any property is given by 1 X ¯ Oi gi e−β i .V n.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.V ¡ ∂Q ¢ 1 1 = βQ ∂V n. O= Q i (18.β 132 .

• The second law • The third law T dS ≥ dq.29) • Debye’s law for entropy at very low temperatures Sm (T ∗ ) = ∗ CP m . 3 (18. dq = C(t)dT.25) (18.• P V work is • Heat capacity: • General forms of the ﬁrst law: dw = −P dV. S(T2 ) = Z T2 (18. Also.24) 4U = q + w.23) (18.26) (18.28) 0 CP dT + S0 T (18. in diﬀerential form this is dU = dq − Pex dV. 133 . (18.30) ∗ where CP m is the molar heat capacity at the lowest temperature for which there is data.27) (18. dU = T dS − P dV.

Part IV Basics of Thermodynamics 134 134 .

electrochemistry. 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. brieﬂy the Helmholtz free energy. the concept of equilibrium plays a key role in much of what we will discuss for the remainder of the year.1. 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. Consequently. K. The equilibrium constant for a thermodynamic process. So far we have encountered two state functions which characterize the energy of a macroscopic system–the internal energy and. 19. here too is energy the key property with which to work. 135 135 .19. The Other Important State Functions of Thermodynamics As was the case in quantum mechanics.

136 . Enthalpy We want a state function whose natural variables are S and P Let us try the deﬁnition H ≡ U + P V. The other pairs of natural variables being (S and P ). This is U = U(S.From the ﬁrst law as stated as dU = T dS − P dV (19. V ) Unfortunately S can not be directly measured and most often P is a more convenient variable than V Because of this fact. so that no mater what situation arises we have convenient equations of state to work with. (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 19.1) we say that the natural (most convenient) variables for the equation of state for U are S and V . it is handy to deﬁne state functions which have diﬀerent pairs of natural variables.2.

Now formally dH = dU + d(P V ) = dU + P dV + V dP. in doing so it must lose energy.2. 19. Heuristic deﬁnition: (19. so (19.3. For example.2) / / dH = T dS − P dV + P dV + V dP = T dS + V dP. As Freshmen we learn this as 4H = qp . Since the process is adiabatic no heat energy can ﬂow in to compensate for the work done and the gas cools. 19. If the process occurs at constant pressure then the enthalpy change is the heat given oﬀ or taken in. So a change in enthalpy is the change in internal energy adjusted for the P V work done. Hence Enthalpy does indeed have the desired natural variables.1.3) Enthalpy is the total energy of the system minus the pressure volume energy. consider an reversibly expanding gas under constant pressure (dP = 0) and adiabatic (dq = 0) conditions. The total internal energy decreases. Helmholtz Free Energy Now we want a state function whose natural variables are T and V 137 . 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. The system does work during the expansion. but dU = T dS − P dV.

so (19.3. 19.Let us try the deﬁnition A ≡ U − T S. (19.4. Hence Gibbs free energy does indeed have the desired natural variables.7) (19. Formally dA = dU − d(T S) = dU − T dS − SdT.1. (19.6) 138 . so dG = T dS + V dP − T dS − SdT / / = V dP − SdT. Now formally dG = dH + d(T S) = dH − T dS − SdT. but dU = T dS − P dV.5) Hence Helmholtz free energy does indeed have the desired natural variables. but from above dH = T dS + V dP. 19. 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. 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) / / dA = T dS − P dV − T dS − SdT = −P dV − SdT.

19.10) (19. ¶ ¶ ¶ µ µ ∂ (U + P V ) ∂U ∂V CP = = +P (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 (19.8) The constant pressure heat capcity can then be expressed in terms of enthalpy as ¶ µ ∂H .11) CP = ∂T P So. 19. Heat Capacity of Gases 19. (19. 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.1. Use an identity of partial derivatives ∂T ∂T µ µ ∂U ∂T ¶ = P µ ∂U ∂T ¶ + V µ ∂U ∂V ¶ µ T ∂V ∂T ¶ (19.5.13) P 139 .12) ∂T ∂T P ∂T P P ¡ ¢ ¡ ¢ note ∂U P is not CV we need ∂U V .4.9) (19.1.5.

∂T P ∂V T ¡ ¢ ¡ ∂U ¢ Recall the expression for internal pressure ∂V T = T ∂P V − P .14) CP = ∂V T ∂T P ∂T P V ¶ ∙µ ¶ µ ¸ ∂U ∂V = CV + +P . 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 (19.6.thus ¶ µ ¶ ¶ µ ∂V ∂U ∂V + +P (19.15) ∂P ∂T ¶ (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 (19.16) V Example: Ideal gases 1. 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. The Maxwell Relations Summary of thermodynamic relations we’ve seen so far Deﬁnitions and relations: • H = U + PV 140 .18) 19.

(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 .

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.V ≤ 0 for a spontaneous process. 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.2) . Chemical Potential 20.V = dq − T dS From the second law. Spontaneity of processes Two factors drive spontaneous processes 1. T dS ≥ dq for a spontaneous process. (dA)T.20. Hence at equilibrium (dA)T.1) (20.V = 0.1. (dA)T. The tendency to minimize energy 2.

For constant T and P = Pex . T dS ≥ dq for a spontaneous process. dA = dU − T dS − SdT and dG = dH − T dS − SdT. The free energy functions are the workhorses of applied thermodynamics so we want to get a feel for them.P = dq − T dS Again from the second law. Hence at equilibrium (dG)T. (dG)T.P ≤ 0 for a spontaneous process. Note free energy provides no information about how fast a process proceeds to equilibrium. Returning to the total diﬀerentials of free energy.5) (20.4) 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). (dG)T. Plugging these into the total diﬀerentials of free energy gives dA = −SdT − P dV and dG = −SdT + V dP (20.6) (20. (20.3) 143 . So free energy provides a measure of the thermodynamic driving force towards equilibrium.P = 0.

The total diﬀerential of G is also dG = dq + dw + P dV + V dP − T dS − SdT. In general dw = dw0 − Pex dV where dw0 is the non-P V work. Chemical potential What if the amount of substance can change? 144 . (dG)T. For reversible processes q = T dS and this becomes 0 0 (dG)T.P = wmax (20. but i) only P V work and ii) closed systems.2.7) (20.10) So.8) (20. For constant T and P = Pex .9) (20.P = dq + w0 − T dS. For a reversible process dq = T dS and work is maximal. The total diﬀerential of A is also dA = dq + dw − T dS − SdT. as stated earlier. As we have stated in words a number of times before. The total diﬀerential of G becomes dG = dq + dw0 − Pex dV + P dV + V dP − T dS − SdT.P = dwmax =⇒ (4G)T. 20. Hence (dA)T = dwmax =⇒ (4A)T = wmax . the Gibbs free energy is the energy of the system available to do non-P V work.These expressions are quite general.

Extensive properties depend on the amount of “stuﬀ” For example A(T. • 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.n T.12) dG = dA + P dV + V dP (20. • 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.14) P.n ∂V T. V.13) = −SdT − P dV + P dV + V dP + μdn / / / / = −SdT + V dP + μdn.T 145 . | {z } =A ¡ ∂A ¢ ∂n V.n ∂n V.T Let’s focus on the slope ¡ ∂A ¢ ∂n V. n) and the total diﬀerential becomes µ ¶ ¶ µ µ ¶ ∂A ∂A ∂A dA(T. (20.n P. n) = dT + dV + dn (20. this is a measure of the potential to change the amount of material.11) ∂T V. V. • Physically. but from dG = µ ∂G ∂T ¶ dT + µ ∂G ∂P ¶ dP + µ ∂G ∂n ¶ dn (20.T .T . V ) now becomes A(T.

(Gm = μ) 20. To account for this one must introduce the concept of activity and the activity coeﬃcient.we see that μ= µ ∂G ∂n ¶ .g. The Gibbs free energy per mole (Gm ) for a pure substance is equal to the chemical potential. pressure. 146 .15) P.3. 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.T So. mole fraction. Activity is hard to deﬁne in words and indeed it has an awkward mathematical deﬁnition as we will soon see.16) where g(ζ) is any reference function (e. 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. there exist complicated interactions which cause deviations from ideal behavior. Activity and the Activity coeﬃcient When. concentration etc. The mathematical deﬁnition of activity ai of some species i is implicitly stated as ζ→ζ lim ª ai =1 g(ζ) (20.). for example. (20. a solute is dissolved in a solvent.. and ζ ª is the value of ζ at the reference state.

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

For the state of interest μi = μª + RT ln ai (20.Our reference function is very simple: g(ζ) = ζ = P . i (20.3.20) Rather than referencing to the standard state one can also reference to any convenient “ideal” state. μi − μª = RT ln ai . By convention we chose a standard state and measure relative to that state.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. Activity and the Chemical Potential One cannot measure absolute chemical potentials. 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).21) i and for the ideal state μid = μª + RT ln aid ⇒ μª = μid − RT ln aid . so γ= a ⇒ a = γP.2. This ideal state is in turn referenced to the standard state.22) 148 . 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. i i i i i i (20. only relative potentials can be measured. P (20.

then at a given pressure μ = μª + RT ln a. Starting from the begining dμ id dμid = Vm dP RT dP. Thus μ = μª + RT ln f. μid → μª ). so a = f for real gasses.25) dμ = μª Pª P This gives P . μi = μid − RT ln aid + RT ln ai i i (20.29) 149 . dμid = P z}|{ = dGm = −Sm dT + Vm dP =0 (20. Lets say our gas is not ideal.23) μi − μid = +RT ln ai − RT ln aid i i ai = RT ln id ai Example: Real and ideal gases at constant temperature.24) Now we integrate from the reference state to the current state of interest Z Z RT id dP.27) For gases activity is usually called fugacity and given the symbol f . but any pressure. Pª The usual standard state is the ideal gas at P ª = 1. so μid − μª = RT ln μid = μª + RT ln P. (20. (20.26) (20. (20.Thus.28) (20. (Note that as P → 1.

This is easily done by using μª = μid − RT ln P in the above equation for μ.Lets say that instead of referencing to the ideal gas at P = 1. i. P ª = 1 atm. we want to reference to the ideal gas at the current pressure P. We have an ideal gas so. So at sea level id ª (20.33) (20. 150 . 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 (20.30) and at elevation h z }| { μ (0) = μ + RT ln 1 = μª μid (h) = μª + RT ln Ph =0 (20. μ = μid − RT ln P + RT ln f f μ = μid + RT ln .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.e.32) The gas ﬁelds the gravitational force which gives it a potential energy per mole of Mgh at height h. P Example: The barometric equation for an ideal gas. μid = μª + RT ln P where we will take the reference state to be at sea level.31) (20.

for this process. aA (21. The quantity aB deﬁnes the equilibrium constant. 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.21. Ka . Equilibrium First let us consider the equilibrium A B.3) (21.1) 151 151 . Since A and B are in equilibrium their chemical potentials must be equal μA = μB Now. if we multiply the above by n moles we have aB −4Gª = nRT ln aA as a consequence of the equilibrium condition.2) (21.

9) 152 . 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 .6) (21.7) (21. The equilibrium condition is aμA + bμB = cμC + dμD . aA If the 4G < 0 then the transition A → B proceeds spontaneously as written.4) μª + RT ln aA + 4μ = μª + RT ln aB A B (21.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. In a manner similar to the above aμª + aRT ln aA + bμª + bRT ln aB = cμª + cRT ln aC + dμª + dRT ln aD (21.8) 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. aA Again multiplying by n gives 4G = 4Gª + nRT ln aB .

¶ (21.3. 153 .11) which is related to Ka by Ka = 0 KC . 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 Partition Coeﬃcient Up to now we have only considered miscible solutions.10) Note: n is absent in the above since the molar values are implied by the stoichiometry. 21.0.12) If the reactants are solutes then as the solution is diluted all the activity coeﬃcients 0 go to unity and KC → Ka .the equilibrium constant is ac ad Ka = C D =⇒ 4Gª = −RT ln Ka aa ab A B (21. We now consider the problem of determining the equilibrium concentrations of a solute A in both phases of an immiscible mixture. (21. 21.0.4.

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

can the drug handle the acidic environment of the stomach? 155 .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. For example.For most drugs 0 < Ppart < 4 o/w (21.

A − bSm.1) . 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.D − aSm.1.B 22. 156 156 (22. Chemical Reactions Up to now we have only been considering systems in the absence of chemical reactions.C + dSm.22. After chemical reactions take place the system is in a ﬁnal “product” thermodynamic state that is in general diﬀerent from the initial “reactant” state. 4rxn H > 0 for Endothermic reactions.

818 − (−285.63 kJ 2 2CO2 +2H2 O(liq)→C2 H4 + 3O2 4rxn H ª = +1410.012 kJ 22.818 kJ 2 H2 + 1 O2 = H2 O(liq) 4f H ª = −285. O2 .2) 157 .830) = 44.1.1. Heats of Formation Hess’s Law of heat summation: 4rxn H is independent of chemical pathway Example: C2 H2 +H2 = C2 H4 .97 kJ H2 + 1 O2 →H2 O(liq) 4rxn H ª = −285.49 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.830 kJ 2 H2 O(liq)→H2 O(gas) 4rxn H ª = −241. H2 . 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. C(graphite) are examples of atoms in their natural state.2.1. This direct reaction is not easy but it can be done in steps C2 H2 + 5 O2 → 2CO2 +H2 O(liq) 4rxn H ª = −1299.22.83 kJ 2 C2 H2 +H2 = C2 H4 4rxn H ª = −174. Example: Formation of water • H2 + 1 O2 = H2 O not 2H2 +O2 = 2H2 O 2 • 4rxn H = ponent. P i ν i 4f H(i). Temperature dependence of the heat of reaction Z T2 4rxn CP dT 4rxn H(T2 ) = 4rxn H(T1 ) + T1 (22.

Ka depends on T but is independent of P.i for pure substance i). i At equilibrium. 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 (22.2. 4rxn G = i i i 4rx n Gª X i ν i μi . where Q ≡ i aν i is the activity quotient. 4rxn G = G(products) − G(reactants) = (remember μi = Gm. As we saw before μi can be deﬁned in terms of activity μi = μª + RT ln ai .7) • Note that the activity of any pure solid or liquid is for all practical purposes equal to 1. 158 . z }| { X X ν i μª + RT ν i ln ai .4) (22.6) 4rxn G = 4rxn Gª + RT ln Q. (22. i So. Reversible reactions Recall the requirement for a spontaneous change: 4G < 0 for constant T and P.3) (22.22. For the reaction aA + bB = cC + dD Ka = ac ad C D aa ab A B (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. d ln Ka =− = ∂(1/T ) P of P d(1/T ) R or (using d d(1/T ) (22.8) νi .• For ideal gases. 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 .10) (22.9) 22.11) (22. Temperature Dependence of Ka Starting with G =´H − T S or G/T = H/T − S.3.15) 159 . a b PA PB (P ª aA )a (P ª aB )b i (22.13) (22. (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 . 4rxn G = 4rxn Gª + RT ln Q becomes 0 = 4rxn Gª + RT ln Ka ⇒ 4rxn Gª = −RT ln Ka .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. we get ¶ µ 4rxn H ª ∂ ln Ka ind. So at equilibrium. ³ From this ∂(G/T)) = H.

KX = KP P −4υg V • From nj = Pj RT (ideal gas approximation). • From Pj = Xj P .4.22. Extent of Reaction There are other equilibrium “constants” that are used in the literature. P is known when V is known and constant when concentration known (RT )−4υg ¡ RT ¢−4υg 160 . Kn = KP • From concentration Cj = Equilibrium “constants” “constants” expression Ka KP KX Kn KC nj V = Pj . 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.

2) μsalt − μª salt . Ionic Activities Consider a salt in solution Mv+ Xv− → v+ M z+ (aq) + v− X z− (aq). Ionics Many chemical processes involve electrolytes and or acids and bases. 23.1) where v+ (v− ) is the number of cations (anions) and z+ (z− ) is the charge on the cation (anion).4) 161 161 .3) (23.23. 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 . ln aj = RT and ln asalt = j = + or − (23. To understand these processes we must know something about how ions behave in solution. RT (23.1. (23.

23. alternatively. where m+ = v+ m and m− = v− m.1. (23. (23.10) v v 1/v . Ionic activity coeﬃcients The activity coeﬃcients for ionic solutions can also be deﬁned via a+ = γ + m+ . The mean ionic activity coeﬃcient is + − γ ± = (γ + γ − ) (23.11) 162 .5) So.8) v v We see that 1/v asalt = (av+ av− )1/v ≡ a± .1.6) (23. (23. a− = γ − m− . ln asalt = v+ ln a+ + v− ln a− or. This suggests that the interesting quantity is μsalt : v μª μsalt 1/v = salt + RT ln asalt .7) It is the case that 1 mole of salt behaves like v = v+ + v− moles of nonelectrolytes in terms of the colligative properties.9) The quantity a± is the mean ionic activity.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. asalt = av+ av− (23.

13) (23.14) 23.15) where z is the charge of the ion and m its concentration.16) 163 . Recall how γ was calculated from the Gibbs-Duhem equation: Z m j ln γ ± = −j − dm0 .2. m0 0 where j = 1 − φ. So. It is convenient to redeﬁne the osmotic coeﬃcient as φ= −1000 g/kg ln a1 . ln γ ± = 1 − Ba0 I (23. a− . γ + and γ − cannot be measured individually. Similarly freezing point depression is redeﬁned as θ = vφKf m. vmM1 (23. Theory of Electrolytic Solutions Ionic strength is deﬁned as I= 1X 2 z mi .The quantities a+ .12) where the subscript 1 refers to the solvent. 2 i i (23. Results from Debye—Hückel theory: point charge in a continuum The Debye—Hückel equation: √ −α |z+ z− | I √ . (23. One can use the colligative properties to measure the ionic activity coeﬃcients. vφ corresponds to the empirical factor i discussed earlier.

ρ• is the density of the pure solvent. (23. e is the charge on the electron.20) v+ + v− 1− I This equation works well to ionic strengths of about I = 0. (23. (23. Q: I= dQ dt (23. It is seen that √ the DHLL correctly predicts the m dependence of ln γ ± . 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.17) 8πLe2 ρ• . which is observed exP perimentally (recall I = 1 i zi2 mi ). I is given by the rate of change (in time) of charge.18) 1000εkT a0 is the radius of closest approach.3. Ion Mobility Current.1 23.where α= e3 (εkT )3/2 B= µ 2πρ• L 1000 ¶1/2 .19) This gives the dependence of ln γ ± for dilute solutions (m → 0). (23. ε is the dielectric constant for the pure solvent and L is Avogadro’s number.21) 164 . Notice that the parameters α and B depend only on the solvent. 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 .

ε: w = −εQ (23.23) Conductance is the inverse of the resistance (R−1 ). • Faraday’s constant F = Le = 96485 C/mol (Avogadro’s number of electrons) 23. is required to move a change through a potential (or voltage).1.3. Some relevant constants • charge of an electron e = 1. w.(Electrical) work. Ion mobility 165 .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.

e.29) The moving ions experience a viscous drag f that is proportional to their velocities. (23. 166 . (23..28) Fi = mai = m dvi = zi eE. dx (23.25) Ni Ni dNi Avi 4t =⇒ = Avi V dt V Ni Avi V (in vacuum) (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. i.24) dQi dNi = |zi | e . where E is the electric ﬁeld. E = Also recall Newton’s law dε .30) The ions quickly reach terminal velocity. zi eE zi eE = f vi =⇒ vi = . the viscous drag equals the Coulomb force. Hence Fi = 0.26) (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 = +. dt (23. −.27) (23. dt dt (23.31) f The drag f has three basic origins. So the total force on the ions is a sum of the Coulomb force and the viscous drag Fi = zi eE − fvi (in solution).

167 . 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. Electrophoretic eﬀect. a “dressed” ion. • oppositely charged ions “pull” at each other 3.1.

32) E For the case for parallel plate capacitors E = ε . (23.36) 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. 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.A more fundamental quantity than ion velocity is the ion mobility. So.35) It is of interest to determine the ratio of the current carried by the cation versus the anion. vi ui = .33) ui = ε Here the current carried by ion i is Ii = |zi | e Ni ui ε A . ui which is the ion’s velocity per ﬁeld. 168 . V l (23.34) Suppose a salt has a degree of dissociation α (α = 1 for strong electrolytes) to produce ν + cations and ν − anions. then each mole of salt gives: N+ = αν + Ln and N− = αν − Ln. where l is the separation of the l plates. (23. vi l . =1 z }| { / ν +/ |z+ | u+ A / Vεl / F / ν + |z+ | u+ u+ α n I+ = = = (23.

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

1. 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.

(This is an approximation). • Assume the uncharged sphere can pass from the (neutral) vacuum to the neutral solvent without doing any work.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. wch . done in discharging the sphere. 171 . wdis . done in charging the sphere which is now in the solvent. • Determine the work. • Determine the work. wtr = 0.

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. 172 .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.So.

For n moles of ions (nL = N) 4Gv→s (24.1. So. = − 8π 0 ri (24.2) where z is the oxidation state of the ion.3) 24. ri is the radius of the sphere (ion) and 0 is the permittivity of free space.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 . 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 (24.5) 173 .4) The above expression is 4Gv→s /ion. e is the charge of the electron. 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. wch = + (ze)2 8π 0 εs ri (24.1.

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. 174 . Thus ions always exist more stably in solution than in a vacuum.1.2. 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 .7) 24.1.3. 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 = (24.6) 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. 24.The dielectric constant of any solvent is always greater than unity so ε1s − 1 is always negative hence 4Gv→s < 0.

µ ¶ 1 N (ze)2 ∂εs N (ze)2 ∂ .2. (24.8) we ﬁnd entropy to be 4Sv→s ∂ =− ∂T " N (ze)2 8π 0 ri µ ¶# 1 −1 .11) 24.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 (24.9) The only variable in the above equation that has a temperature dependence is the dielectric constant of the solvent so. Unfortunately however. the Born model does not make quantitatively correct predictions in many cases. (24. We simply list here several phenomena that more sophisticated theories of solvation must consider 175 . 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. εs (24.

3. 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.1. so the initial structure of the solvent must breakdown and the new structure must form. 176 . Speciﬁc interactions: any interaction energy speciﬁc to the particular ionsolvent pair: Hydrogen bonding being the prime example. 2. 4. Changes in solvent structure: the local environment of the ion has a diﬀerent arrangement of solvent molecules than that of the bulk solvent.

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 are collected here simply for handy reference for you while working the problem sets.2) . Key Equations for Exam 4 Listed here are some of the key equations for Exam 4.1) (25. 177 177 dH = T dS + V dP dA = −SdT − P dV dG = −SdT + V dP (25.25. 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.

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)

178

Chemistry 352: Physical Chemistry II

179

179

Part V Quantum Mechanics and Dynamics

180

180

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

f (x) is a constant. −~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.So.16) √ ny πy nz πz 2 2 nx πx sin sin ψ=√ sin a b c abc E = Ex.nz .18) nx πx 2 sin .ny Ez. (26. 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. 8mb2 n2 h2 z = .nx = Ey.17) (26. a a r ny πy 2 sin . 8mc2 (26.19) and the total energy is (26. = b b r nz πz 2 sin = c c r (26. 8ma2 n2 h2 y = . Hence we immediately have ψx = ψy ψz and Ex.nx + Ey.20) 185 .nz The total wavefunction is n2 h2 x .ny + Ez.

(nx = 1. (nx = 1. nz = 2) have the same total energy and thus are degenerate. nz = 1).Degeneracy The 3D particle in a box model brings up the concept of degeneracy. Let the 3D box be a cube (a = b = c) then the states (nx = 2. (26.21) 186 . ny = 2. nz = 1). ny = 1. When n(> 1) states have the same total energy they are said to be n-fold degenerate. ny = 1.

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

6) 188 . then αf (x) = g(x) = βf (x) ˆ ˆ ˆ 2.1) 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.. " #" # " # 1 0 3 1 3 1 = (27. Multiplication: ³ ´ ˆ (x) = α βf (x) ˆ αβf ˆ ˆ (27. ˆˆ 4. Equality: ˆ if α = β.2) Algebraic rules for operators 1.— 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.4) (27. ˆ ˆ ˆ then (ˆ + β)f (x) = αf (x) + βf (x) = g(x) + h(x) α ˆ 3. Addition: ˆ if αf (x) = g(x) and βf (x) = h(x).g. e.3) ˆˆ ˆ α β αf (x) = β (ˆ f (x)) . ˆˆ but in general αβf (x) 6= β αf (x). 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 (27.5) (27.

z) ¡d dx ¢ f (x) = d2 f (x) dx2 Commutators: We have seen that in general αβ 6= β α. This leads to the construction of the ˆˆ ˆˆ commutator. z) ˆ • ∇: ∂x ∂y ∂z ´ ³ 2 2 2 ∂ ∂2 ∂2 ˆ ˆ • ∇ : ∇ f (x.7) 189 . y. y. β ˆ ˆˆ ˆˆ (27. α. −y. z) = ∂x2 + ∂y2 + ∂z2 f (x. 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. 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. y. y. −z) ı ı ´ ³ ˆ ∇f(x. 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). z) = f (−x. where λ is a complex number. and ˆ ˆ ˆ — α(λf (x)) = λˆ f (x). ◦]: h i ˆ ≡ αβ − β α. [◦.

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

2. (27.13) i 191 .27. j 6= k. Orthogonality. and the Superposition Principle Theorem 1: The eigenfunctions of a Hermitian operator corresponding to diﬀerent eigenvalues are orthogonal: Z ψ∗ ψk = 0. 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.

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

ˆ L2 ψlm = l(l + 1)ψ lm ˆ Lz ψlm = mψ lm (28.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 . Quantum Properties of Angular Momentum The eigenfunctions of angular momentum are entirely speciﬁed by two quantum numbers l and m: ψlm . l − 1. (28. . . This also implies that the number of ‘rungs’ is 2l + 1 and that l must be either an integer or a half-integer.46) substituting in the relation we just found for k gives (28. . simplifying gives l = −l0 Thus mmax = l. .50) The solutions to this partial diﬀerential equation are known to be the spherical harmonic functions ψ lm = Ylm (θ. l(l + 1) − l02 + l0 = 0. mmin = −l and so m = l.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 (28.5.48) (28.51) 199 . l − 2. −l + 1 . φ). −l.47) 28. (28.45) and (28.

The spherical harmonics are functions of two variables. We know that there are 2l + 1 diﬀerent m values for a particular l value.55) (28. Both the spherical harmonics and the Legendra polynomials are tabulated. The spherical harmonics (and hence the angular momentum wavefunctions) are orthonormal. They are also built-in functions of Mathematica. φ) sin θdθdφ = 0 0 l0 6= l or m0 6= m 0 0 28. The rigid rotor Rotational energy For general rotation in three dimensions the is ~2 ˆ ˆ H = L2 .56) 2I 8π2 I There is no m dependence for the energy.53) Yl∗m0 (θ. All 2l + 1 of these wavefunctions correspond to the same energy.54) l(l + 1)h2 l(l + 1)~2 = = El . φ)Ylm (θ. ( Z 2π Z π 1 l0 = l and m0 = m (28. meaning.5. In other words.52) where the Pl (θ) are the Legendra polynomials and A is normalization constant. 2I 2I Thus Elm = (28.1. 200 . but they are a product of a function only of θ and a function only of φ. |m| |m| (28. φ) = APl (θ)eimφ . (28. ψlm = Ylm (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 . the energy levels are determined only by the value of l. We say the there is a 2l + 1 degeneracy of the energy levels.

Addition of Angular Momentum 29.1. (29. Spin Angular Momentum We learned above that l may take on integer or half-integer values. Systems in which l takes on half-integer values are peculiar. ∗ ∗ ∗ See in-class demonstration: the belt trick ∗ ∗∗ 201 201 . The values of m = ms are limited to +1/2 and −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. l = s = 1/2. 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. These systems have no classical analogs.29.

The are two main coupling schemes which account for the total angular momentum of the atom. the total angular momentum. (M = i mi ) • then J = L + S 2. • we will not use this method.1. 29.2. The electrons in many electron atoms couple. 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.) 202 .29. however. J. 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.2. 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.max . we use J when we speak generally. 1. (Ms = i msi ) P • ﬁnd the total orbital angular momentum L = Mmax . 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 . One measures.

(29. |j1 − j2 | . Jmin = |j1 − j2 | . . That is. . 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.ˆ ˆ ˆ The total angular momentum is JT = J1 + J2 . |j1 − j2 | + 1.3) We need to determine the allowed values of the total angular momentum quantum number J. The maximum value of J is determined by the maximum value of M by Jmax = Mmax = m1max + m2max = j1 + j2 (29. Thus the allowed values of J are J = j1 + j2 .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. .2. 29. . j1 + j2 − 1. An Example: Two Electrons The table below shows the total spin angular momentum S for a two electron system (29.2.5) The total angular momentum is quantized is exactly the same manner as any other angular momentum.6) 203 .

So. Term symbols are simply shorthand notion used to identify states. In the above example the degeneracy is gS = 3 for the S = 1 states and gS = 1 for the S = 0 states. of the states is given by 2S + 1. 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). 29.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. L 0 symbol S 1 P 2 D 3 F 4 5 . The orbital degeneracy is given by gL = 2L + 1. gS . those being 1 S and 3 S during our discussion of helium. Term Symbols We have already seen several term symbols. For historical reasons L values are associated with a letter like the l values of a hydrogenic system are. G H 204 .3.2. Term symbols are useful for predict and understanding spectroscopic data. it is worthwhile to brieﬂy discuss them.

1. 2. Highest J value (inverted) “hole” 29. notated by 1 S 2. All closed shells have zero spin and orbital angular momentums: L = 0. Lowest J value (regular) “electron”.The term symbol for a particular states is constructed from the following general template gS LJ .2. Rules: 1.7) 205 . These dipoles interact with a certain spin—orbit interaction energy ESO . H 2 (29. If several terms have the same multiplicity then ground state will be that of the largest L. 3. • E.4. An electron and a “hole” lead to equivalent term symbols. Many electron atoms have term symbols associated with their states. Spin Orbit Coupling A charge possessing angular momentum has a magnetic dipole associated with it. p1 and p5 have the same term symbol.. The spin—orbit Hamiltonian is [ ˆ HSO = hcAL · S ´ ³ ˆ ˆ ˆ ˆ SO = hcA J 2 − L2 − S 2 . S = 0. An electron has orbital and spin magnetic dipoles.g. 3. The ground state will have maximum multiplicity. These states are all singlet S states. Hund’s Rule for the ground state only.

where A is the spin—orbit coupling constant. From the Hamiltonian the spin—orbit interaction energy is ESO = hcA [J(J + 1) − L(L + 1) − S(S + 1)] 2 (29.8) 206 .

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

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

7) 209 . the ground state energy correction is then calculation from Z ∞ (1) (0)∗ ˆ (0) ψ0 H (1) ψ0 dx (30.• For example. The trial energy is calculated by Etrial = R R all space ˆ ψ∗ Hψtrial dx trial ψ∗ ψtrial dx trial (30. The basis for this is the variation theorem which states Etrial ≥ E.6) all space The trial energy is now a function of the adjustable parameter. p. Variational method The basic idea behind the variational method is to use a trial wavefunction with an adjustable parameter. The value of the parameter which minimizes the energy. that we use to minimize the trial energy by setting dEtrial =0 dp (30. 5 4α 2 so the ﬁrst order ground state energy for a quartic oscillator is √ ~ω 3 πaA2 0 + E0 ' . gives a trial wavefunction which is closest to the real wavefunction.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 = .2. We will not prove this theorem here. Etrial . 5 2 2 4α 30.

) 210 .and solving for p. (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.

ﬁring an electron down a particle accelerator. The two level system is inherently quantum mechanical in nature. 31. The Two Level System and Quantum Dynamics Our entire discussion of quantum mechanics thus far had dealt only with time independent quantum mechanics.31.1. Unlike the harmonic oscillator it has no classical analogue. The Two Level System If the harmonic oscillator is the most important model in all a physics. The spin system discussed above is an example of a two level system. We shall ﬁnally get to quantum dynamics in this chapter. but ﬁrst we will discuss the very important model of the two level system. For example. Obviously there are cases where quantum objects move with time. The time variable never appears in any expression. 211 211 . the two level system is a close second.

2) where δ j.° “projects out” the j th state of the wavefunction being acted on. 212 . we can not use our usual procedure of writing down the classical Hamiltonian and then replacing the variables with their corresponding operators. ˆ H= 1 δ 1. 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 .° .Consequently. i=1 The states ψ 1 and ψ2 are eigenfunctions of the two level Hamiltonian. (31. j 6= k (31.1) TLS R where TLS dΩ means integration over the two level space (which is really just the P sum 2 ).° + 2 δ 2.

2 2 (31.° ) (aψ 1 + bψ2 ) 2 δ 2.For example let some arbitrary wavefunction ψ = aψ 1 + bψ2 .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. 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 .5) states.7) 213 .° 2 δ 2.° + = 1 δ 1.° (31. then ˆ Hψ = ( 1 δ 1.6) (31.4) (31.

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.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)¯ = 1.2.10) 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.9) ˆ En ψn (x)e− ~ En t = e− ~ En t Hψn (x) ˆ En ψn (x) = Hψ n (x) (31. Ψn (x. 214 . 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) = ¯ Ψn (x.31.8) We can verify this by obtaining the time independent Schrödinger equation from the more general time dependent ∂Ψn (x. t)dx¯ (31. 0)Ψn (x. This is given by ¯Z ¯2 ¯ ¯ ∗ P (x. t) i ˆ = Hψn (x)e− ~ En t i ˆ = Hψn (x)e− ~ En t i ˆ = Hψn (x)e− ~ En t i (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 . t) ≡ ψn (x)e− ~ En t i (31.

Thus the eigenstates are stationary states. t) = √ Ψ1 (x. The “left” and “right” wavefunctions that we saw in the discussion of the two level system are examples of superposition states. t) + √ Ψ2 (x. = ¯ (31.14) 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) = √ ψ1 (x)e− ~ E1 t + √ ψ2 (x)e− ~ E2 t 2 2 (31. it may be in a superposition of any number of eigenstates. t)¯ P (x. Similar to before we calculate ¯2 ¯Z ¯ ¯ ¯ Φ∗ (x. The phase factor does become important for superposition states.so no matter what time t we check we will always ﬁnd the system in the same eigenstate. 0)Φ(x. In general the state of the system need not be in one particular eigenstate. t) 2 2 exposing the phase factors we get i i 1 1 Φ(x. As an example consider the state 1 1 Φ(x.12) (31. 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 Ã ! ¯2 i i ¯ ¯1 ψ ∗ (x)ψ 1 (x)e− ~ E1 t + ψ∗ (x)ψ 2 (x)e− ~ E2 t ¯ ¯ 1 1 dx¯ .13) Let’s now track the probability of ﬁnding the particle in the same superposition state.

+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. This leaves ¯2 ¯Z ¯ ¯ ¯ Φ∗ (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 . t)¯ (31.15) P (x.integrated because the eigenfunctions are orthogonal. 216 .

17) • How to get the average value for some property. (31. sZ N= space |ψunnorm (x. z)|2 dxdydz. N unnorm (31.16) • The normalized wavefunction: ψnorm = 1 ψ . Z ψ∗ αψdxdydz. 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.18) 217 217 . Equations • The short cut for getting the normalization constant .Key Equations for Exam 1 Listed here are some of the key equations for Exam 1. The equations are collected here simply for handy reference for you while working the problem sets. y. ˆ hˆ i = α space (31. This section should not substitute for your studying of the rest of this material.

sin ψn (x) = √ a b c abc • The energy levels for the 3D particle in a box. 2I 8π2 I (31. j 6= k (31.24) L L L and h i h i h i ˆ 2 .21) ψ∗ ψk j = space 1.• The Laplacian ∇ = 2 µ ∂2 ∂2 ∂2 + 2+ 2 ∂x2 ∂y ∂z ¶ .26) • The normalized wavefunctions for a particle on a ring are 1 ψ = √ eimφ . 8ma2 8mb2 8mc ( (31.25) • The energy levels for a particle in a ring are Em = (31.23) • Commonly used comutators of the angular momentum operators are h i i i h h ˆ ˆ ˆ ˆ ˆ ˆ ˆ x .22) • Superpostion: ψ= X i ai ϕi (31.20) (31. Ly = L2 .19) • Normalized wavefunctions for the 3D particle in a box. ˆ y . Enx .ny . (31. 2π (31. Lz = i~Lx . ˆ ˆ ˆ ˆ ˆ L m2 h2 ~2 m2 = . Ly = i~Lz . Lx = i~Ly (31. ˆ z . j=k . Lx = L2 .27) 218 .nz • Orthonormality: Z n2 h2 n2 h2 n2 h2 y x = + + z 2. 0. √ ny πy nz πz nx πx 2 2 sin sin . Lz = 0.

32) • In general Ψn (x.29) ˆ Lz ψlm = mψ lm (31.30) (31.34) (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. t) ≡ ψn (x)e− ~ En t i (31. 2I (31. En = n n all space (31. • The ﬁrst order energy correction in pertubation theory is Z (1) ˆ ψ(0)∗ H (1) ψ(0) dx.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 (31.28) • Degeneracy for general angular momentum is gJ = 2J + 1.• The eigenfunctions of angular momentum are entirely speciﬁed by two quantum numbers l and m: ψ lm .35) 219 . ˆ L2 ψlm = l(l + 1)ψ lm • The energy levels for the rigid rotor are El = l(l + 1)~2 .

Part VI Symmetry and Spectroscopy 220 220 .

Inherent to group theory is symmetry. 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. • 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 . • The types of symmetry it has will determine to which symmetry group it belongs.32. we will • determine the symmetry of a particular molecule.

It is a set of objects and a single operation. Symmetry Operators Any operator that leaves |ψ|2 invariant are symmetry operators for that particular system: ˆ O |ψ|2 = |ψ|2 . which has the following properties. These operators deal with symmetry about the center of mass. For molecules we will be dealing with point group symmetry operators.1. (32.2) 32. That is. the eigenvalues for the particular symmetry operator are 1 or −1. We have seen two such operators in ˆ and σ h . This type of operator arrises in the treatment of extended crystal structures. ∗ ∗ ∗ See Handout on Symmetry Elements ∗ ∗∗ (32.32. 1. 2. 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.2. The group is associative (but not necessarily communative) with respect to the operation. Mathematical Groups In mathematics the term “group” has special meaning.1) This implies ˆ Oψ = ±ψ. An identity element exits and is a member of the group 222 .

Symmetry of Functions In the absence of degeneracy. C2 . The inverse of every member of the group is also in the group.” yields the identity element. ∗ ∗ ∗ See Handout on Naming Point Groups ∗ ∗∗ ∗ ∗ ∗ See Handout on Assigning Point Groups ∗ ∗∗ Associated with a given group is a “multiplication” table. for any member of the group one can ﬁnd another member of the group which. Example: The C2v Group ˆ ˆ ˆ The C2v group consists of the symmetry elements E.2. In other words. upon “multiplication. 32. The “product” of any two members of the group yield a member of the group. σ v (in-plane) and σ 0v ˆ (transverse).3. Water is an example of a molecule described by this point group.3. 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. the wavefunctions must be symmetric or antisymmetric with respect to all elements of the group. 223 . 4.1.

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. 224 . 1. consider the following.Connecting with the C2v group example lets consider the wavefunctions for water. To see where these four vectors come from. −1. −1. 1. −1) B1 = (1. 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. 1) A2 = (1. 1. −1) B2 = (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.

y2 . −1. . x3 . x2 . y3 .4) (32. . . 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.The above considerations leave four vectors. . −1) ⊗ (1. . −1) = A2 (32. the vectors represent what is call an irreducible representation of the group. 225 . Direct Products The direct product of a two vectors is deﬁned as (x1 . there will always be the same number of vectors as symmetry elements. In fact. −1. .) = (x1 y1 . x2 y2 .1.3. 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. 1) = (1.) ⊗ (y1 . . 1.4. −1. 1. x3 y3 . . .) For the example of the C2v group consider B1 ⊗ B2 = (1.3) 32. Altogether. −1.

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

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

• 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. 33. To do so we begin with the 3N nuclear degrees of freedom. 228 228 . Molecules and Symmetry From our chapter on diatomic molecules last semester we have learned a great deal which caries over directly to polyatomic molecules. One must now consider two diﬀerent types of polyatomic molecules: Linear and Nonlinear. With polyatomic molecules one needs to specify the coordinates of N nuclei rather than just two nuclei.33. So. in this chapter we simply investigate some of the speciﬁc details regarding polyatomic molecules. Molecular Vibrations As for diatomic molecules. That leaves us with 3N − 3 coordinates to specify.1. it is convenient to work with center of mass coordinates. As for the diatomic case 3 degrees of freedom determine the center of mass motion.

1. The number of normal modes equals the number of vibrational degrees of freedom. Normal Modes Polyatomic molecules can undergo very complicated vibrational motion. Regardless of what type of vibrational motion is taking place. 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. At low energies the normal modes are well approximated as harmonic oscillators. the symmetric stretching vibration and the asymmetric stretch. 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. The three modes are the bending vibration. that motion is some linear combination of fundamental vibrational motions called normal modes. Example: Water The point group symmetry of the water molecule is C2v . One example was the “left” and “right” states of the two level system.33. This is analogous to writing an arbitrary wavefunction as a linear combination of eigenfunctions. 33. however.1.2. 229 .

Consequently the bending mode is associated with A1 The same is true for the symmetric stretching mode. ˆ 230 . For the bending mode. It too is associated with A1 . the vibration is complete unchanged by any of the symmetry elements. ˆ The asymmetric stretch.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. however. is associated with B1 since C2 and σ0v transform ˆ the mode into its opposite and σ v leaves it unchanged.

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

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. or z for the particular group.2) 1 1 1 1 z. The electric dipole is μ = μx ex + μy ey + μz ez where μx = qx. In order for absorption of the electromagnetic radiation to take place. Example: Water Recall that the point group symmetry of the water molecule is C2v .• Light—matter interaction is dominated by the light—dipole coupling so the other interactions are ignored. μy = qy. z 2 1 1 −1 −1 xy 1 −1 1 −1 x. 232 . y 2 . y. The character table is C2v A1 A2 B1 B2 ˆ E ˆ C2 σv ˆ σ 0v ˆ Functions (34. We now need a column of the character table which we have ignored up to this point. xz 1 −1 −1 1 y. it must be able to couple to a changing (oscillating) electric dipole. x2 . μz = qz. yz The last column describes the symmetry of several important functions for the point group.

and B2 . 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). 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. and z. From before we know the modes of water have A1. 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. The light loses energy to the material in an amount equal to the vibrational energy of the molecules is the sample. Unlike IR absorption which is based on the electric dipole.2. 233 . B1 . This lose of energy shows up in the scattered light as a new down shifted frequency from that of the original input light frequency.

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

6) .5) (35. φ). 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 . = 2μR2 8π 2 I (35.3) This is the so-called rigid rotor energy. The R was involved in vibrations. We now turn our attention to the angular components to describe rotations. Molecular Rotations Recall that the three degrees of freedom that described the position of the nuclei about the center of mass were (R. Then Erot = J(J + 1)hBe with a degeneracy of gJ = 2J + 1 235 235 h 8π 2 I (35.1) R 2μ 2μR2 ∂R ∂R 2μ We will now be concerned only with the angular part. (35. For constant R the rotational energy is given by − Erot = J(J + 1)~2 J(J + 1)h2 .2) J . ~2 ˆ2 (35.4) (35. θ. under the Born-Oppenheimer approximation. R is a parameter. 2I Now. It is common to deﬁne Be ≡ as the rotational constant.35.

a rotational transition can accompany a vibrational transition. 236 . n. (35. Rotational Spectroscopy A rotational transition can occur in the same vibrational level n. Vibrational state dependence: • The R value is dependent on the particular vibrational level. This is called a pure rotational transition. In either case the selection rule for the transition is 4J = ±1.1.2. Relaxing the rigid rotor Of course the rigid rotor is not a perfectly correct model for a diatomic molecule. 2. • One deﬁnes a rotational interaction constant that depends on the vibrational level. • This is corrected for by the term −J 2 (J + 1)2 Dc .8) (35. Centrifugal stretching: • Rotation tends to stretch the diatomic distance R.7) 2 where αe is an empirical rotational—vibrational interaction constant. There are two corrections we will now make 1. 35. where Dc ≡ 3 4Be ω2 ˜e (35.35. ¶ µ 1 Bn ≡ Be − n + αe .9) is the centrifugal stretching constant. Alternatively.

The principle axes coordinate system is the one in which the z-axis is taken to be along the principle symmetry axis. kT. But one system is special–the principle axes coordinate system. 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. The total moment of inertia. This means that at room temperature the many excited rotational states are populated.10) 237 . 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.3. ∗ ∗ ∗ See Handout ∗ ∗∗ The selection rules and the thermalized states combine to yield a multi-peaked ro-vibrational spectrum. Thermal energy. ∗ ∗ ∗ See Handout ∗ ∗∗ 35. 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.

15) h . benzene) • Ixx = Iyy h 8π2 Ixx (35.g. Symmetric tops (e. (35.11) (35.There are four classes of polyatomic molecules regarding rotations 1.13) 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. where A= (35. Linear (e.g.14) • The rotational energy is Erot = hBJ(J + 1) + h(A − B)K 2 .12) ~2 ˆ2 ˆ J H= 2Ixx (35. carbon dioxide) • Izz = 0.. Ixx = Iyy ˆ ˆ2 ˆ2 • J 2 = Jx + Jy • The Hamiltonian is • The rotational energy is Erot = hBJ(J + 1).17) B= 2 8π Ixx and K is the quantum number describing the projection of the angular momentum onto the z-axis 238 . where B= 2.

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

Atomic spectra consist of single sharp lines due to transitions between energy levels. 36. Ee . 240 240 . R. Ee as a function of R describe the eﬀective potential for the nuclei. Electronic Spectroscopy of Molecules The electronic spectra of molecules are quite diﬀerent than that of atoms. on the other hand. was parameterized by the internuclear distance.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.1. We found that in doing so the electronic energy level. Molecular spectra. It had a qualitative shape similar to the Morse potential. have numerous lines (bands) due to the fact that electronic transitions are accompanied by vibrational and rotational transitions.

1.1.2. 36. 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. Emission Spectra In emission spectroscopy.In the ﬁgure below the ground and ﬁrst excited electronic levels (as a function of R) are shown. Note: The potential minima are not at the same value of R for each of the electronic states. Absorption Spectra In absorption spectroscopy. 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. 241 . ∗ ∗ ∗ See Spectroscopy Supplement p1 ∗ ∗∗ 36.1.

242 . • 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.∗ ∗ ∗ See Spectroscopy Supplement p2 ∗ ∗∗ 36. This is known as the Stokes shift. Hence the Stokes shift. • This requires a lower energy (or “more red”) photon. ∗ ∗ ∗ See Spectroscopy Supplement p3 ∗ ∗∗ As seen in the supplement the ﬂuorescence spectrum is shifted to lower energies (red shifted) from the absorption spectrum. 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. • 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 process of is taking place. Fluorescence Spectra All during the process of absorption.1.3.

2. ˆ el.i → Ψf = ψel.f vib.f ψvib. 36. The Franck—Condon principle states that the nuclei do not move during an electronic transition. but we will ingore this).36. Mathematically this means that the strength of a transition from Ψi = ψel.i ¯ . 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.1. Assuming the electronic transition is allowed one must calculate the probability of the vibrational transistion as well.i ψvib.2.f is given by ¯Z ¯ ¯ ¯ ¯ ¯2 ¯Z ¯ ¯ ¯ ¯ Ψ∗ μel Ψi ¯ = ¯ ˆ f ¯ ¯ Z ¯2 ¯ ¯ ψ∗ ψ∗ μel ψel. 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. This is down by evaulating the Franck—Condon integral.1) all space el space vib space 243 .i ψvib. one obtains the Franck—Condon principle.f ¯ (36.

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

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. The Fourier transformation The Fourier transformation. if the signal decays rapidly it will have a broad spectrum and. if the signal decays slowly it will have a narrow spectrum. of a function f (t) will. conversely.1) −∞ 245 245 . One should be familiar with qualitative aspects of this time—frequency relation. =. (37. f (ω).37.1. 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. and is given by Z ∞ ˜(ω) = = [f (t)] = f f(t)eiωt dt. Fourier Transforms As a spectroscopist it is imperative to have a deep understanding of the relationship between time and frequency. Furthermore. in this work. 37. The mathematics which governs these qualitative statements is Fourier transform theory which we now review. by denoted ˜ by a tilde.

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

The equations are collected here simply for handy reference for you while working the problem sets. Equations • Vibrational degrees of freedom — linear: 3N − 5 — not linear: 3N − 6 • The so-called rigid rotor energy is Erot = J(J + 1)hBe .4) . where Be ≡ is the rotational constant.Key Equations for Exam 2 Listed here are some of the key equations for Exam 2.3) h 8π 2 I (37. 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. 247 247 (37.

6) • The Fourier transformation is ˜ = [f (t)] = f (ω) = f (t)eiωt dt.8) 248 .i ¯ vib. (37.• The degeneracy of the rigid rotor is gJ = 2J + 1 • Franck—Condon Factor: ¯Z ¯ ¯ ¯ ¯ ¯2 ¯ ¯ ψ∗ ψvib. f (ω) = f (t) = 2π −∞ (37.f ¯ Z ∞ (37.7) −∞ • The inverse Fourier transformation is Z ∞ h i 1 −1 ˜ ˜ = f(ω)e−iωt dω.5) vib space (37.

Part VII Kinetics and Gases 249 249 .

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

φ. θ.1) Vv Vv It is more convenient to switch to spherical polar coordinates in velocity space (v. t)dvx dvy dvz (38. t)dv = N F (vx . (38. t).b. θ. t) = F (v. (38.3) 251 . φ). vy . then for many cases the velocity distribution will be isotropic–independent of θ and φ. t) = F (v. F (v. NVv . θ. Vv . F (v. φ. v is simply a magnitude (not a vector)–it is the speed. φ). n.2) Furthermore. vz .The number of particles. stationary distributions–those independent of time–are often encountered. φ. θ. The probability distribution function then becomes F (v. having velocities in a macroscopic volume.. in velocity space is Z Z Z Z NVv = N F (v. θ. t) If we choose the origin of our coordinate system to be at the center of mass of the gas.

n RT |{z} =L A simple model for molecular collisions: 252 . 38.We shall consider stationary isotropic distributions F (v). 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. So F (v) represents a distribution of speeds.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. It can be shown from ﬁrst principles that µ ¶3 2 −mv 2 m F (v) = 4π e 2kb T v 2 (38.380658 × 10−23 is Boltzmann’s constant. n = = RT .2. This is the Maxwell’s distribution (of speeds). For an ideal gas (V = P ).4) 2πkb T where kb = 1.

5 nm 253 .6) • The collision frequency = n∗ πσ 2 v For the above model we need to ﬁnd the average collision frequency. v12 = h|v1 − v2 |i ¯ It can be shown that r v12 = ¯ √ √ collision 16RT = 2¯ =⇒ v = 2n∗ πσ 2 v .48 ¯ m . • A Particle moving at v sweeps out a cylinder of radius σ and length v4t =⇒ V = πσ2 v4t.• Particles are hard spheres of radius σ.25 × 109 s−1 . frequency λ = 72.8) Example: Ar at SATP (T = 298 K. Since the molecules are moving relative to one another we must ﬁnd the average relative velocity.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. ∗ ∗ ∗ See Handout ∗ ∗∗ • The number of collisions equals the number of particles with their centers in V : number of collisions = n∗ πσ 2 v4t (38. s collision = 5. ¯ πM frequency (38. P = 1 bar): v = 380.

That is. 254 254 . The Rate Laws of Chemical Kinetics Thermodynamics described chemical systems in equilibrium. equal b. in general. For the study of chemical reactions it is important understand systems that can be very far from equilibrium. address the question. however. answer the question: How fast will the reaction occur? 39.39.1. Will the reaction occur? We need kinetics. Rate Laws Consider a general four component reaction aA + bB = cC + dD (39. We must account for the stoichiometry.2) − dt dt dt dt BUT this is ambiguous because a moles of A reacts with b moles of B and a does not. For this we turn to the ﬁeld of chemical kinetics.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. d[B] d[C] d[D] d[A] or − or or (39. from thermodynamics. We can.

We deﬁne the reaction velocity as v= 1 d[I] vi dt (39. or D. This deﬁnition is useful but must be used with caution since for complicated reactions all the v’s may not be equal. An example of this is ½ bB → cC + dD aA + (39.) (39. v = f (conc. In general an overall reaction is made up of so called elementary reactions Reactant Reactant = → Product overall rxn (39. c or d and I = A.3) where vi = −a. Many. rate laws are of the form v = k[A1 ]xA 1 [A2 ]xA 2 · · · [An ]xA n . rate laws are empirical. B.5) For the most part. 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 . −b.6) The reaction is said to be of order xAi in species Ai and it is of overall order P i xA i . C. (39.4) 0 B0 → c0 C0 + d0 D0 b A rate law is the mathematical statement of how the reaction velocity depends on concentration.

Let 2A + 2B = C + D be the overall reaction. 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. at equilibrium vf = vb which implies kf [A]a [B]b = kr [C]c [D]d (39. rate laws for overall reactions can not be determined by stoichiometry. (39.10) 256 . Now.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.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] .

(39. v= k[H2 ][Br2 ]1/2 1+ k0 [HBr] [Br2 ] (39. H2 + Br2 = 2HBr. Objectives of chemical kinetics 257 . the reaction is not elementary. H2 + I2 = 2HI. Next consider the reaction between molecular hydrogen and molecular bromine. The above two example are seemingly very similar but they have very diﬀerent observed rate laws.13) . The velocity of a reaction is lost in this ratio and hence we still can not determine the speed of a reaction from thermodynamics. Examples of rate laws Consider the (overall) reaction between molecular hydrogen and molecular iodine.12) The observed rate laws are vf = kf [H2 ][I2 ] and vr = kr [HI]2 . Moral: Kinetics is very much an empirical science.” (39. this does not obey any common form. In fact. Moral: Kinetics is very much an empirical science. The observed rate law for this reaction is very complicated.11) So. we have succeeded in connecting thermodynamics to kinetics BUT we have done so through the ratio of rate constants.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. This suggests that the reaction is elementary.

• 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. 258 . To obtain the rate from the concentration we must take its time derivative dc(t) . • 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. • 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. Determination of Rate Laws Concentrations c(t) are measured not rates.

2.2. A so v ≈ kax [B]y 39. The diﬀerential equation is not solved. this gives the overall order of x + y • ﬂood with. 259 . 1. if the concentration drops very sharply 2. Method of initial velocities • for v = k[A]x [B]y rate laws. • problems 1. Method of isolation • for v = k[A]x [B]y rate laws • start with initial concentrations a and b equal to the stoichometry. The main problem with such a method is that randomness in the concentration measurements gets ampliﬁed when taking the derivative.39. 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. say. if there is an induction period 2.2. • 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.1. Integrated rate laws The above diﬀerential methods look directly at the rate law which is a diﬀerential equation.

For example n = 3/2 is a three-halves order rate law. vi is a negative number).We now solve the diﬀerential equations to yield what are called the integrated rate law. − (n − 1)vi kt 260 .b. 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..

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 = . d(1/T ) R where Ea is the Arrhenious activation energy. kr (40. This is the Arrhenious equation Recall the equilibrium constant can also be obtained from kinetics 0 Kc = kf ' Ka .4) Now.3) (A is the constant of integration). take the log of this: ¸ kf = ln kf − ln kr .2) (40. ln Ka = ln kr ∙ 261 261 (40.5) . Integration of the above yields ln k = ln A − Ea Ea =⇒ k = Ae− RT RT (40. Temperature and Chemical Kinetics 40.1) (40.1.40.

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 √ (40.6) (40. Theory of Reaction Rates Simple collision theory (SCT) • Bimolecular reactions (A.7) (40. Theoretical approaches to reaction rates predict rate constants of the form k = aT j e−E /RT . Forcing this to coincide with the Arrhenious implies Ea = E 0 + jRT and A = aT j ej 0 (40.1.8) (40.2.1.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.B) • Reaction rate determined by molecular collisions 262 . Temperature corrections to the Arrhenious parameters The Arrhenious parameters A and Ea are constants.9) We can verify this by starting with the Arrhenious equation and substituting the above expressions.10) 40.

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. • The maximum reaction velocity is vmax = reaction velocity will be less because zA B L .14) 263 .13) [A][B] = pπσ AB L s 8RT − Em in e RT πLμ (40.11) is the reduced mass and σAB is the collision diameter.— Collision frequency for A–B collisions s 8RT zAB = πσ AB L2 [A][B] πLμ where μ ≡ mA mB mA +mB (40.

18) 264 .17) • The active complex is a state in the thermodynamic sense. A + B → (AB)‡ → products.g. (40. [A][B] (40.16) Activated complex theory (ACT) • An intermediate active complex is formed during the reaction. ACT is not limited to bimolecular reactions.• Comparison to the (temperature corrected) Arrhenious equation suggests s 8RT 1 e2 (40.. • For the above example. thus we can apply thermodynamics to it. the equilibrium constant is deﬁned as ‡ Ka = a‡ low [‡] ' aA aB conc. e.15) A = pπσ AB L πLμ and 1 Ea = Emin + RT 2 (40.

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

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].• Parallel reactions are of the form. They are of the form k1 k2 A→B→C (40.24) • The concentrations of A. 1 A + B1 → C k (40. for example. 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 .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. dt which.

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. 267 . Chain Reactions Chain reactions are reactions which have at least one step that is repeated indefinitely.40. Initiation: Typically a molecule M reacts to form some highly reactive radical M → R·.

3. R·+M0 → M00 + R0 ·. 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 . This step repeats an indeﬁnite number of times.2.

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

etc.6) • Redlich-Kwang P = (41. C(T ) represents triplet interactions. n • For a real gas z must approach unity upon dilution ( V → 0).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. (41. • z can be expended in a power series called the virial series.9) B(T ). C(T ). RT • z is unity for an ideal gas because for such a gas P V = nRT.7) 41.2. + ··· .8) ³n´ 1 z = 1 + B(T ) Vm ¶ 1 + C(T ) Vm 1 + D(T ) Vm (41. Conceptually B(T ) represents pair-wise interaction of the particles. 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. 270 . are called the virial coeﬃcients. etc. 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 +··· .

D(T ) = b3 . RT Vm Vm (41. (41.1. etc.2.13) (41.41. hence 1 Vm µ b Vm ¶2 + ··· .11) = z so z= 1 a − .12) The ﬁrst term is of the form 1 1−x 1 = 1 + x + x2 + · · · . 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−x Therefore b a +1+ + z=− RT Vm Vm the ﬁrst term is proportional to in the series expansion. b RT Vm 1 − Vm which has the power series expansion (41.16) B(T ) = b − RT 271 .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 (41.14) 1 Vm and so it can be combined with the term µ ¶2 ³ a ´ 1 b z =1+ b− + + ··· . C(t) = b2 .15) This series can now be compared term by term to the virial series to give expression for the virial coeﬃcients: ³ a ´ .

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 ) + ··· .41. (41.3. Tb . 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 + · · · . (41. The gas behaves more like an ideal The lowest order correction are now V1 m gas at Tb then for other temperatures.2. One ﬁnds (see m homework) B(T ) B 0 (T ) = .18) The relation of this expansion to the one in V1 can be obtained.17) = 1 + C(T ) Vm Vm ³ ´2 .19) RT 272 . The Boyle Temperature The temperature at which B(T ) = 0 is called the Boyle temperature.2.2. (41. 41.

a. B0 . • Estimates based on Beattie-Bridgeman constants: c A0 − 3.2.23) (41. b. RT T A0 a B0 c − B0 b − 3 .24) 273 . for now treat them as empirical parameters): µ ¶ 9RTc 6Tc2 B(T ) = 1− 2 .4.21) 41. T3 B(T ) = B0 − where A0 .22) (41.20) D(T ) − 3B(T )C(T ) − 2B(T )3 (RT )3 (41. C(T ) = RT T B0 bc D(T ) = . (41. Estimation of Virial Coeﬃcients The virial coeﬃcients can be estimated using empirical equations and tabulated parameters. c are tabulated constants • Estimates based on critical values (we will discuss critical values shortly.C 0 (T ) = and D0 (T ) = C(T ) − B(T )2 (RT )2 (41.25) 128Pc T (41.

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

absurd to treat a liquid as an ideal gas). of course. P Ã ¡ ¢! µ ¶ µ ¶ nRT −1 ∂V −1 ∂ nRT −1 P − 2 κT = (42. it is. So one can expand the volume in a Taylor series about a known pressure. α and κT for liquids and solids Ã ¡ ¢! ∂ nRT 1 1 P = /R = n/ ∂T VP T |{z} P =n R / /T (42.5) This approximation is quite good even over a rather large pressure range (P −P0 = 100 atm or so).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. 275 . Starting with the ideal gas law: V = nRT . the compressibility and expansion of liquids (and solids) are very small.1.42.1.2.. (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 (42.3) In general.b. α and κT for an ideal gas As an exercise we shall calculate α and κT using the ideal gas equation of state (n. V (P ) ≈ V0 [1 − κT (P − P0 )] . P0 .4) so.

Heat Capacity of Gases Revisited This section is a review from the ﬁrst semester with an additional example beyond the ideal gas.10) CP = ∂T ∂T P ∂T P P ¡ ¢ ¡ ¢ note ∂U P is not CV we need ∂U V . The Relationship Between CP and CV To ﬁnd how CP and CV are related we begin with ¶ µ ∂H . V (T ) ≈ V0 [1 + α(T − T0 )] .8) κT − ∂P T rule ∂T V 42. we can apply the cyclic rule for partial derivatives to determine the ratio κα : T ¡ ∂V ¢ ¶ µ α ∂P ∂T P cyclic = ¡ ∂V ¢ = (42.7) As one ﬁnal point.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. Use an identity of partial derivatives ∂T ∂T µ ∂U ∂T ¶ = P µ ∂U ∂T ¶ + V µ ∂U ∂V ¶ µ T ∂V ∂T ¶ (42.6) so.9) ¶ ¶ ¶ µ µ ∂ (U + P V ) ∂U ∂V = +P (42. 42.H = U + PV CP = ∂T P so µ (42.2.1.11) P 276 .2.

16) κT For gases we need the equation of state which often is conveniently explicit in P or V but not both CP = CV + 1.14) V For solids and liquids: µ so ∂V ∂T ¶ = V α.12) CP = ∂V T ∂T P ∂T P V ¶ ∙µ ¶ µ ¸ ∂U ∂V = CV + +P .15) P V α2 T V (42. Explicit in P : Replace µ 2. µ ∂P ∂T ¶ = α κT (42. Explicit in V : Replace µ ∂P ∂T ¶ ∂V ∂T ¶ with − ¡ ∂T ¢V ∂P ∂V P ¡ ∂P ¢ (42.18) 277 .thus ¶ µ ¶ ¶ µ ∂V ∂U ∂V + +P (42.17) T V ∂T with − ¡ ∂V ¢P ∂P T ¡ ∂V ¢ (42.13) ∂P ∂T ¶ (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. ∂T P ∂V T ¡ ¢ ¡ ∂U ¢ Recall the expression for internal pressure ∂V T = T ∂P V − P .

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. P2 (42.24) 278 .21) so ¡ ∂V ¢ nR P + nB 0 / P (R + P B 0 ) n = . 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. nRT − P2 / RT n (42. One term viral equation (equation of state: V = nRT + nB). = ∂T P P ∂T − ¡ ∂V ¢P = − ∂P T µ ∂V ∂P ¶ T =− nRT . 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 (42.20) ∂T P ∂T V ∂T P ∂P T The partial derivatives are ¶ µ ∂V nR + nB 0 .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.

3.25) V1 As we learned last semester the value of w depends on Pex during the expansion. Isothermal expansion T is constant 2. −wrev = For an ideal gas (P = nRT ) V Z V2 Pgas dV (42. 42. So. V ) = U(T ) (independent of V ). Isothermal expansion • For the case of a ideal gas. U (T. Adiabatic expansion q = 0. 279 . Recall that if the expansion is reversible.42. −wrev = −wmax . Namely Pgas = Pex .27) Also recall that −wrev is the maximum possible work that can be done in an expansion. Expansion of Gases Expanding gases do work: −w = Z V2 Pex dV (42.1. So for isothermal expansion 4U = 0 = q + w =⇒ q = −w. Isothermal and Adiabatic expansions We shall consider two limits for the expansion of gases 1.26) V1 this becomes Z V2 −wrev = V1 µ ¶ V2 nRT dV = nRT ln V V1 (42.3. there is always an intermediate equilibrium throughout the expansion.

V2 ): CV dT = Z T2 (42. Heat capacity CV for adiabatic expansions Considering an ideal gas going adiabatically from (T1 .2. V (42.28) 42. in terms of molar heat capacity 2 T2 ¯ CV m ln T1 µ ¶ V2 = −R ln V1 µ ¶ (42.30) T1 CV dT = T Z V2 V1 −nR dV.29) (42. V2 ). Recall ¶ µ ∂U CV = =⇒ dU = CV dT ∂T V So from above CV dT −nRdV −nRT dV =⇒ = V T V Going from (T1 . V1 ) to (T2 .Adiabatic expansion • Since q = 0. dU = dw = −Pex dV = −P dV (reversible).33) 280 . • For an ideal gas dU = −P dV = −nRT dV V (42.3.31) If CV (T ) is reasonably constant over the internal T1 to T2 then this is approximately µ ¶ µ ¶ V2 T2 ¯ = −nR ln (42.32) CV ln T1 V1 ¯ where CV = 1 (CV (T1 ) + CV (T2 )) . Or. V1 ) to (T2 .

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.40) 281 . P2 ): Z T2 T1 nRT dP P Z (42. P (42. dH = dU + P dV + V dP (because both P and V can.42.35) P For an ideal gas this becomes Cp dT = Going from (T1 . CP = µ ∂H ∂T ¶ (42.3. P1 ) to (T2 . Or.3. 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. in general. change) / / dH = dq + dw + P dV + V dP dH = V dP.34) =⇒ dH = Cp dT = V dP (42.37) If CP (T ) is reasonably constant over the internal T1 to T2 then this is approximately µ ¶ µ ¶ P2 T2 ¯ = nR ln (42.36) 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 ¶ (42.38) CP ln T1 P1 ¯ where CP = 1 (CP (T1 ) + CP (T2 )) .

42) but Pi Viγ are arbitrary so this implies P V γ = constant (** NOTE: The axes should be reversed **) ¶γ ⇒ P2 V2γ = P1 V1γ . 282 . In this case q = 0 (adiabatic) and w = 0 (since −dw = Pex dV ).3.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. Joule expansion Consider a gas expanding adiabatically against a vacuum (Pex = 0). (42.4.43) 42.41) ¶ V1 = γ ln V2 µ ¶ V1 = ln V2 µ ¶γ (42.

V ) = U(T )). We want to ﬁnd Identity: ¡ ∂T ¢ ∂V (42.45) U For an ideal gas ∂V T = 0 (since U(T.44) U . For real gases this is not strictly equal to zero. Joule-Thomson expansion Consider the adiabatic expansion as illustrated by the ﬁgure below ¡ ∂U ¢ 283 .3. ¶ µ ¶ ¶ µ µ ∂U ∂U ∂T 1 =− = ∂U V ∂V T CV ∂V T | {z } 1/CV µ ∂T ∂V ¶ (42. 42.This implies 4U = q + w = 0. Internal energy is constant. for Joule type expansion the temperature of the gas does not change.5. That is. Thus in as much as the ¡ ∂T ¢ gas can be considered ideal ∂V U = 0.

We want to ﬁnd Identity: µ ¡ ∂T ¢ ∂V (42.50) H 284 . (the Joule-Thomson coeﬃcient). ¶ µ ¶ ¶ µ µ ∂H ∂T 1 ∂H =− = =μ ∂H P ∂P T CP ∂P T | {z } 1/CP ∂T ∂P ¶ (42.47) (42. The work done on the right is wR = −P2 4V = −P2 (V2 − 0) = −P2 V2 .49) H ≡ μ. 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.The work done on the left is wL = −P1 4V = −P1 (0 − V1 ) = P1 V1 . Now.48) (42.46) (42.

(42.53) 285 .Recall the useful identity µ Thus ∂H ∂P ¶ =V −T µ ∂V ∂T ¶ (42.51) T P ¡ ¢ −V + T ∂V P ∂T μ= CP (42.52) 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 . so μ is negative–the gas warms upon expansion • The Joule-Thomson inversion temperature is the temperature where μ = 0. μ = CP m Limts: • Low T : B 0 is positive and B is negative. so μ is positive–the gas cools upon expansion • High T : B 0 is nearly zero and B is positive.

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 . 286 286 . but also dH = T dS. • At constant V : — dU = dq + dw dq=CV dT =⇒ dU = CV dT. (43. So dH = dq =⇒ dq=T dS dH = CP dT. So Z T2 CV CV dT =⇒ 4S = dT. dS = T T T1 (43. but also dU = T dS. Entropy of Gases 43.1. This is not a problem though since entropy is a state function.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 . Entropy change for changes in temperature.43. So Z T2 CP CP dT =⇒ 4S = dT. Calculation of Entropy Entropy must be calculated along reversible paths.

Entropy of Mixing of an ideal gas • Since the gas is ideal. V2 P2 dS = nR ln = nR ln P2 = −nR ln . V1 P1 /R / n / T P1 /R / n / T (43. VA 4SB = nB R ln VB + VA VB (43.• Using the equation of state nRdV =⇒ 4S = dS = V Z V2 V1 V2 nR dV = nR ln . V V1 (43.6) VA + VB . there are simply two separate equations: 4SA = nA R ln and 4Smix = 4SA + 4SB (43.4) 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.3) • Using the equation of state to express V1 and V2 in terms of P1 and P2 .5) 287 .

12) ideal Deﬁning S2 . V = Hence ¶ T ∂V =− ∂T µ ¶ P =− nR − nB 0 P (43. Entropy of Real Gases Consider the question: How does S → S ideal as P → 0 ? Use Maxwell relation nRT + nB. this becomes S2 − / 1 S ideal ideal = S2 − / 1 S ideal − nB 0 (P2 − P1 ) (43. P2 → P θ as S θ . So.• Recall Avogadro’s principle: n ∝ V for an ideal gas.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. So.1.13) 288 .1.8) µ ¶ → nR P2 → 0 − nB dP =⇒ S2 − S1 = −nR ln dS = − − nB 0 (P2 − P1 ) P P1 P2 P1 (43. so ideal ideal S2 − S1 = −nR ln (43. S(P θ ) = S θ − nB 0 P θ (43. ⎛ ⎞ 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 } (43.9) For an ideal gas B 0 = 0.11) Letting P1 → 0 and P2 → P θ (Standard pressure 1 bar).

The entropy at any P and T can be obtained expresses as S(T.15) 289 . P ) − nB 0 P Thus S(T. P ) = S ideal (T.14) (43. P ) = S θ (T ) − nR ln P − nB 0 P Pθ (43.

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. 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.17) RT λ= √ 2P Lπσ 2 (43.Key Equations for Exam 3 Listed here are some of the key equations for Exam 3. −mv2 (43.18) 290 290 .16) • The average speed of a particle is hvi = • The mean free path is r 8RT πM (43. Equations • The Maxwell’s distribution of speeds is F (v) = 4π µ m 2πkb T ¶3 2 e 2kb T v2 .

25) • The virial series is µ ¶ µ ¶2 µ ¶3 1 1 1 z = 1 + B(T ) + C(T ) + D(T ) + ··· .23) (43. Vm Vm Vm • Relation between heat capacities for an ideal gas: CP m = CV m + R (43.22) • The van der Waals gas equation of state: P = • Compressibility Factor: a RT − 2. nRT RT (43.24) z= (43. Vm − b Vm P Vm PV = .20) kr • The Arrhenious equation k = Ae− RT Ea (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 (43.26) (43.27) 291 .19) • The relation between the rate constant and the thermodynamic equilibrium constant is kf Kc = (43.• The reaction velocity is v= 1 d[I] vi dt (43.

Part VIII More Thermodyanmics 292 292 .

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

294 . 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.44.1. Simple gas laws do not work well near critical points.1.

Pc = 27b2 ¯ d2 P ¯ ¯ = 2RTc − 6a = 0 2¯ 4 dVm c (Vmc − b)3 Vmc (44.6) These values can be used to ﬁnd the compressibility factor.375. z.27 0.375 2/e2 ' 0. RTc 8 (44. Vmc − b Vmc 2 (44.7) Notice that both a and b whose values depend on the particular gas have dropped out. That is (for the van der Waals Equation) zc = 0. Vmc ) Pc = a RTc − 2 .5) (44. Tc . Gas Constants from Critical Data Consider the van der Waals equation at the critical point (Pc .2.33 295 .4) (44. 8a . The other equations of state give similar results van der Waals Berthelot Dieterici Redlich-Kwong zc 3/8 = 0.375 for all gases. Tc and Vmc gives Vmc = 3b. dVP = 0) at the critical point.3) (44. Tc = 27bR a . So.375 3/8 = 0. setting 2 m the ﬁrst and second derivatives at the critical point equal to zero we get ¯ dP ¯ ¯ = −RTc + 2a = 0 (44.1.1) dP d There is an inﬂection point ( dVm = 0.44.2) 3 dVm ¯c (Vmc − b)2 Vmc and solving these three equations for Pc . at the critical point zc = Pc Vmc 3 = = 0.

The Law of Corresponding States We have found that zc is predicted by the equations of state to be independent of the particular gas. Phase Equilibrium Consider a homogeneous substance consisting of two phases α and β at a constant T and V. and Vr = V /Vc . Suppose some amount of material. This implies μβ = μα is the condition for equilibrium. 296 .44. Then zr = Pr Vrr . β denote liquid (or solid) and vapor phases. ∗ ∗ See Fig. dn. the pressure of the system when μβ = μα is the called the vapor pressure of the material at temperature T. Pr = P/Pc . 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. then for a given T .3.18 Laidler&Meiser ∗ ∗ 44. 1.2. RT zr is a “universal” function–it is nearly the same for all gasses. When α. goes from α → β • (dAα )T = −P dVα − μα dn • (dAβ )T = −P dVβ + μβ dn = 0 since V is constant • (dA)T. One can deﬁne unitless “reduced” variables Tr = T /Tc .

11) P Similarly.12) T Now the total diﬀerential of μ is m z z m µ }|¶ { µ }| ¶ { ∂μ ∂μ dT + dP dμ(T.8) (44. So again μβ = μα is the condition for equilibrium.n P. µ ∂μ ∂P ¶ (44. ∂G S=− ∂T So.T µ ¶ ∂ ∂G ∂μ ∂ ∂G =− =− =− . 44. P ) = −Sm dT + Vm dP −S V (44. dG = −SdT + V dP + μdn Now.1.10) But S = nSm (T. = Vm . (44.13) 297 .3. The chemical potential and T and P How does μ vary with T and P ? Generally for homogeneous substances.P = μβ − μα dn. µ ∂S ∂n ¶ µ ¶ (44.¡ ¢ For phase changes at constant T and P then (dG)T. (44.9) P. ∂n ∂T ∂T ∂n ∂T P µ ∂μ ∂T ¶ = −Sm . P ) so. P ) = ∂T P ∂P T dμ(T.

14) = This is the Clapeyron Equation 4φ Hm T 4φ Vm (44. 4v V = RT P (44.19) Collecting the T ’s on one side of the equation and the P ’s on the other we get (44.liq ' Vm.21) d(ln P ) = − 298 .20) = d(ln P ) and dT T2 = −d(1/T ) so this becomes 4v Hm d(1/T ) R (44.15) (44.2.3. Vapor Equilibrium and the Clausius-Clapeyron Equation The above Clapeyron equation applies to any phase transition.16) 44.17) 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 (44.3.44.vap − Vm.vap Assuming the vapor phase obeys the ideal gas equation of state. consider the liquidvapor phase transition.3. The Clapeyron Equation At equilibrium μβ = μα so. −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 (44.18) (44. Now 4v V = Vm.

Rearranging again leads to 4v Hm d(ln P ) =− d(1/T ) R This is the Clausius-Clapeyron equation.24) α β 299 .22) 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.4. (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. Equilibria of condensed phases Examples • Solid—liquid — ice—water. “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.

44.Thus for any given T only one P allows for equilibrium.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. 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 (44.27) 300 .26) 4f Hm 4f Hm Tf → T ª where Tf is the freezing temperature at standard pressure (1 bar). At temperatures above the critical point there is no distinction between vapor and liquid. Triple Point and Phase Diagrams Deﬁnitions • Phase Diagram: A graph of P vs. Recall the Clapeyron equation 4f Hm Hmβ − Hmα dP = = dT T 4f Vm T (Vmβ − Vmα ) (44.5.

J. So if there exists a concentration gradient there will be a net ﬂux. Viscosity: The ﬂux of momentum down a velocity gradient 3.1. of material from high concentration to low concentration so as to establish an equilibrium.45. We now consider three transport properties of ﬂuids: 1. Flux: movement of something through a unit area.1) 301 301 . J= 1 dn A dt (45. Diﬀusion At equilibrium concentration on a bulk solution will be uniform. Diﬀusion: The ﬂux of material down a concentration gradient 2. Transport Properties of Fluids Transport properties of matter deal with the ﬂow (or ﬂux) of some property along a gradient of some other property. Thermal Conductivity: The ﬂux of energy down a temperature gradient ∗ ∗ See Transport Phenomena handout ∗ ∗ 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 .2) (45.3) (45.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).5) 302 . ∂t ∂x (45. ∂t ∂x ∂x If D is truly constant we get Fick’s second law of diﬀusion: ∂ 2C ∂C =D 2.4) (45.

t) = √ e− 4Dt 2 πDt (45. η. t) = C0 2 π 0 ¶¸ ∙ µ x 1 C0 1 − erf √ = 2 4Dt ¶ µ 1 x = C0 erfc √ 2 4Dt " (45.2.e.6) 2. The solution for two special boundary conditions are of interest and will simply be presented here without derivation 1.. Step function solution # Z √x 4Dt 1 1 2 −√ e−y dy C(x. Point source solution x2 C0 C(x. 303 . The tendency of a liquid to ﬂow at the same velocity throughout. 45. i. Numerous methods of solution exist for this equation but they are beyond the scope of the course.The solution of this partial diﬀerential equation depends on the boundary conditions. Viscosity Viscosity.7) where erf and erfc are tabulated functions respectively called the error function and complementary error function. is the resistance to diﬀerential ﬂuid ﬂow.

• 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.) mass . Pf is the outlet pressure and P0 is the pressure at which the volume is read.e.. ¶ (45.8) 4t 8ηl where 4P is the driving pressure. length l). i.dv The frictional (viscous) force is F = ηA dx . (The units of η are g = cm·s . lenght·time 1 poise Poiseuille’s Formula • Applies to Laminar (nonturbulent) ﬂow • For a liquid ﬂowing trough a tube (radius r. the volume of ﬂow 4V in time 4t is πr4 4P 4V =− (45.9) Stoke’s law: spheres falling through ﬂuids 304 .

8 m/s2 ). κ.11) • Related to diﬀusion constant: = kT 6πηr (45. 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. 305 . Thermal conductivity (This section closely follows parts of chapter 8 in Transport Phenomena by R. Consider a slab of solid material of area A between two large parallel plates a distance D apart.10) (45. Lightfoot Wiley New York 1960) The thermal conductivity. Stewart and E.12) 45. W. N.B. of a material is a measure of the tendency of energy in the form of heat to ﬂow through the material. 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.E. Stokes showed f = 6πηr • Gravitational force (exerted downwards): Fg = gravitational acceleration (9.• The frictional force (exerted upwards) is proportional to velocity: Ff = −fv. Bird. 4πr3 (ρ − ρ0 )g.

whereas the thermal conductivity of most liquids decrease with increasing temperature..3. And a constant rate of heat ﬂow dq is needed to maintain dt the temperature diﬀerence 4T = (T1 − T2 ) 4T 1 dq = −κ .e.Under such conditions. (45. (45. a linear steady state temperature distribution across the material is established. 306 . i. This is called Fourier’s law of heat conduction (one-dimensional version). 45.13) 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 .14) A dt dx where Qf is the heat ﬂux.1. 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. from hot to cold. Thermal conductivities are positive quantities so Fourier’s law says that heat ﬂow down a temperature gradient.

There is no analog to superconductivity for thermal conductivity.45.3. Thermal Conductivity of Solids For the most part. The Wiedemann. (45.2. The Wiedemann. Frantz and Lorenz equation relates the thermal conductivity to electrical conductivity. κel for pure metals: κ = L = const. Frantz and Lorenz equation breaks down at low temperature because metals become superconductive. the thermal conductivity of solids have to be determined experimentally because many factors contributing to the thermal conductivity are diﬃcult to predict. 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. κel T where L is the Lorenz number (typically 22 to 29 × 10−9 V2 /K2 ). Dry porous materials are poor heat conductors Rule of Thumb: Thermal conductivity and electrical conductivity go hand in hand. In general metals are better heat conductors than nonmetals and crystals are better heat conductors than amorphous materials.15) 307 .

2. For example. Measures of Composition There are several measures of composition of solutions • mole ratio r = n1 n2 n2 . Solutions Solutions are mixtures of two or more pure substances. n1 +n2 • mole fraction X2 = • molality m = • Molarity c2 = X1 = 1 − X2 1000X2 . So. M1 X1 where M1 is the molecular weight of species 1 n2 L solution 46. volume.1) (46. Partial Molar Quantities Thermodynamic properties. in general change upon mixing X 4mix = properties of soln − properties of pure. say.46. in addition to the parameters needed to characterize a pure substance.2) . 4mix V = Vsoln − Vsolute − Vsolvent Consider a thermodynamic quantity. 308 308 (46.1. one also needs to keep track of the amount of individual species in solution 46.

So. n1 and n2 : V (T.n1 .3) ³ ´ ∂V ¯ ≡ Vi .n2 ∂n1 T.nj Similarly ¶ ¶ ¶ ¶ µ µ µ µ ∂G ∂G ∂G ∂G dT + dP + dn1 + dn2 .P.P. P. n2 ). Notation The study of solutions brings with it here for future reference.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. ∂T P.n2 ∂P T. it is a function of T.n1 (46.n1 . 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 .n1 (46.In general. ∂ni T. 46.P.n1 . n1 . the total derivative is ¶ ¶ µ ¶ ¶ µ µ µ ∂V ∂V ∂V ∂V dV = dT + dP + dn1 + dn2 .2.P.n2 ∂n2 T. ∂ni T. rather than simply the molar free energy as it was earlier.n1 .P.n2 ∂n2 T.n2 ∂P T.1. the partial molar volume. P.4) ³ ´ ∂G ≡ μi .P.n2 ∂n1 T. dG = ∂T P.

however.8) 4mix V can be positive.6) That is. 4mix V > 0. is not necessarily the mole weighted sum of the volumes of each component in its pure (unmixed) state. so change each amount of substance proportional to the amount substance present. one unit of baseballs are mixed with one unit of basketballs. negative or zero. 4mix V < 0. The total volume.2.7) (46.2.5) ¯ Now. one unit of baseballs are mixed with one unit of books. 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. dn2 = n2 dλ. Vi depends on concentration.46. dn1 = n1 dλ. 310 . For example. the total volume of the solution is equal to the sum of the partial molar volumes each weighted by their respective number of moles. 2. 1. Partial Molar Volumes Consider the partial molar volume For constant T and P ¯ ¯ dV = V1 dn1 + V2 dn2 (46. So. (46.

46. the ideal state for Henry’s law Raoult’s law limit 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 . all neighboring molecules are diﬀerent than the given molecule 2.1. all neighboring molecules are same as the given molecule 2. Reference states for liquids For liquids there are two more convenient ideal states 1. the ideal state for Raoult’s law 2.3.3. neat (pure) solvent limit 1. inﬁnite dilution limit 1.

(46.12) i ai g(ζ) (46. This implicit deﬁnition is awkward so for convenience one deﬁnes the activity coeﬃcient as the argument of the above limit. mole fraction. 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).). and ζ ª is the value of ζ at the reference state. pressure. μi − μª = RT ln ai .2. (46.10) 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. Raoult’s Law In discussing both Raoult’s law and Henry’s law.3.11) 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. concentration etc.9) ζ→ζ ª g(ζ) where g(ζ) is any reference function (e. we are describing the behavior of a liquid solution by measuring the vapor (partial) pressures of the components 312 .g..

16) (46. μ1 − μ• = RT ln 1 where Pi is the vapor pressure of the ith component above the solution. 1 2 ai low P Pi ' RT ln • . Take diﬀerential change along a line of constant concentration.13) = (μ1 − μ• ) n1 + (μ2 − μ• ) n2 . 4mix G = μ1 n1 + μ2 n2 − μ• n1 − μ• n2 1 2 (46. so dG = (μ1 n1 + μ2 n2 ) dλ then G = μ1 n1 + μ2 n2 .15) (46.14) (46.For simplicity we consider here only a two component solution.17) (46.18) Now. Recall that 4mix G = G(soln) − G(pure components) Hence. dG = μ1 dn1 + μ2 dn2 . • ai Pi (46. 313 .

3. The change in free energy upon mixing for solutions ideally obeying Raoult’s law is Ã ! • • X1 P/ X2 P/ id(RL) 1 2 4mix G = RT n1 ln + n2 ln (46.26) 314 . ∂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) (46.25) (46. Ideal Solutions (RL) Raoult’s Law: Pi = Xi Pi• (46.21) That is. this is for an ideal solution in the Raoult’s Law sense.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 (46.22) • • P1 / P2 / 4mix G = RT (n1 ln X1 + n2 ln X2 ) Again. 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. From ¶ ¶ µ ∂G ∂ (G/T ) S=− and H = − .23) (46.24) (46.19) (46.20) 46.3.

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 ). real solutions generally deviate from Raoult’s law. there are speciﬁc interactions between particles. Since. (46.27) = γi (RL) Xi . It does not require any kind of interaction among the constituent particle making up the solution. The Reference State (RL) Let us apply the deﬁnition of activity for the Raoult’s law reference state. and the reference state is Xi = 1 So. 315 . 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. The reference function is g(ζ) = ζ = Xi . • negative deviation: the molecules prefer to be around other types of molecules than themselves. in reality. ai =1 Xi →1 Xi lim implies ai and γ i (RL) (RL) (RL) (46. • no deviation: the molecules have no preference.

30) (46.e.3.29) 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). kXi = lim µ Pi Xi ¶ (46.It is very important to note that this deviation from Raoult’s law is a property of the solution and NOT any given component. For example. i. Henry’s Law Henry’s Law: Pi = kXi Xi . at inﬁnite dilution.. where kXi is the Henry’s law constant. for a given component. mixing with one substance may lead to a positive deviation but mixing with another substance may lead to a negative deviation. 316 .4. Positive deviation from Raoult’s lawNegative deviation from Raoult’s law 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 (46.33) = γ Mi Mi (HL) (46. 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.The Reference State (HL) Referring to the deﬁnition of activity again we see that the reference function is g(ζ) = ζ = Xi . So.34) 317 . X1 → 1. whereas Henry’s law applies to the subdominant species X2 → 0.32) ai → 1 as Xi → 0 and γ i If instead of mole fraction. and the reference state is now Xi = 0 So. they apply to opposite species in the solution.31) Xi →0 Xi implies (HL) (HL) = γ i Xi . (46. Raoult’s law applies to the dominant species. molality or molarity is used then ai and ai respectively. But. (HL) ai lim =1 (46.

46. 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 46.4.1.4. μ1 (solid) = μ1 (soln). | {z } μs 1 318 . Freezing Point Depression At Tf (freezing point).

So. Osmotic Pressure RTf•2 ln a1 4f H We consider the osmotic pressure at a constant temperature. (46. using ∂μ ∂T (46. 319 . The freezing point depression is Θ=− 46. (so.38) •2 •2 • RTf Tf RTf • where Θ ≡ Tf − Tf .Using the Raoult’s law reference state (since we are interested in the behavior of the dominant species).4.2. 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. dG = V dP ).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. Z Tf −4f H 4f H ln a1 ' dT = Θ.35) (46. T.37) • For small changes in the freezing point we may approximate T by Tf in the integrand.

From the above equation ¯ V1 Π RT • ¯ Now we make the approximations V1 = Vm1 . 2 3 (46. 1 1 (46.39) ¯ 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.40) (46.In the above ﬁgure μ1 (left) = μ1 (right).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• (46.43) 320 . Thus 1 z }| { • • V Π n1 Vm1 Π n2 . hence ¯ μ• = μ• + RT ln a1 + V1 Π. a1 = X1 = 1 − X2 : ln a1 = ln(1 − X2 ) = • Vm1 Π RT (46.

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

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

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

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. 324 . 47. di S = dS ≥ 0. the second law underlies all the concepts of this chapter. holds. The Second Law As you might expect. 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. This is simply another in our long list of alternative statements of the second law.e. in every macroscopic region of the system the entropy production due to irreversible processes is positive. We need a “local” formulation of the second law: • Absorption of entropy in one part of the system. compensated by a suﬃcient production in another part is prohibited — i.2..

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

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 (47.7) dt dx Example: Find the entropy production in a system consisting of two identical connected blocks of metal (I and II).47. 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.5) we get (47.3.1. using Qf = κA4T q =− 4t D in diﬀerential form this is dT dq = −κA . (47. 326 .6) We are now interested in exposing the time dependence. so.

We have still not made a connection to kinetics. To do so we must consider the entropy production per unit time di S . Using this we see that the entropy production is µ ¶ 1 1 .8) The quantity de qj is the amount of heat supplied by the environment to hold block j at its ﬁxed temperature.Considering the whole system dqI dqII + T1 T2 e i z }| { z }| { de qI de qII di qI di qII = + + + . − di S = di qI T1 T2 which we see is positive because di qI < 0 when T1 > T2 .9) (47.10) 327 . T1 T2 T1 T2 d S dS dS = (47. dt (47. 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 .

P = − P − i vi μi P i vi μi and a ≡ − (4rxn A)T. (47. − ¢ ¢ κ/ κ/ /A ¡ / A ¡¯ ¯ ¯ T1 + T2 .13) dt dt ¯ Using the above expression for heat ﬂow gives us T since. T1 − T = − T − T2 ⇒ T = 2 D / D / (47. dt D So. Extent of reaction: ξ is deﬁned by dξ = dni . 328 .14) a result we might have guessed.V = 2. Chemical aﬃnity: a ≡ − (4rxn G)T. where ni is the number of moles vi of the ith component and vi the stoichiometric factor of the ith component. −Aκ4T di S = dt D µ 1 1 − T1 T2 (47.12) ¯ 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 = .2. Entropy Production due to Chemical Reactions Deﬁnitions: 1. 47.11) ¶ −Aκ4T di qI = .3.For this example di qI di S = dt dt From chapter 24 we know µ 1 1 − T1 T2 ¶ (47.

329 .V = X i dξ dt dnH2 dnNH3 dnN2 = = (−1) (−3) (2) (47. This is because a = − (4rxn A)T.V so µ ¶ 1 dni = −adξ μi dni = vi μi vi | i {z }| {z } X −a dξ −adξ (47.16) but (dA)T.20) We see that for a spontaneous process the entropy production per unit time is positive.15) (47.V − T dS ⇒ dS = T T dq e i z}|{ z}|{ dq adξ + dS = T T (47.. 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.g.17) z }| { z }| { (dA)T.• e.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.V dq − = (dU)T.18) d S dS (47.V is positive as is v.

(47. diﬀusion is the ﬂux of matter down a concentration gradient. That is. the so-called Dufour eﬀect is heat ﬂux down a concentration gradient 330 .4. a2 v2 > 0 such that a1 v1 + a2 v2 > 0.Simultaneous Reactions For N simultaneous chemical reactions. Conversely. 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. 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. For example in a system of two coupled reactions we could have a1 v1 < 0.21) dt T j=1 The second law requires that the total entropy production for simultaneous reactions is positive. 47. The socalled Soret eﬀect is ﬂux of matter down a temperature gradient. the entropy production per unit time generalizes to N 1X di S = aj vj ≥ 0. We just saw an example of such a situation with the discussion of simultaneous reactions. Thermodynamic coupling need not be conﬁned to coupling between the same types of processes.

The ensemble evolves in two ways • Reversibly — A second perturbation can “undo” or reverse the evolution. 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. If the perturbation is released the system will begin to evolve in time as it heads back towards the thermalized equilibrium state. • 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. 331 .

• This cannot be undone with the second radio pulse. 332 . • Each nucleus is in a slightly diﬀerent environment so each spin frequency is slightly diﬀerent. • 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.• A strong signal is seen because all the spinning nuclei cooperate. • 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.

23) (47.22) 333 333 .Key Equations for Exam 4 Listed here are some of the key equations for Exam 4.24) (47. 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. This section should not substitute for your studying of the rest of this material. Equations • The Clapeyron Equation is 4φ Hm dP = . The equations are collected here simply for handy reference for you while working the problem sets. 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.

• Fick’s second law of diﬀusion: ∂ 2C ∂C =D 2.28) μ = μª + RT ln a (47.32) where kXi is the Henry’s law constant.30) = γi (RL) Xi . 6πηr (47. γi (RL) → 1 as Xi → 1 (47.31) Pi = kXi Xi .33) = γi (HL) Xi . (47. kXi = lim • Henry’s law reference ai (HL) Xi →0 Pi Xi . µ ¶ (47. (47.25) • Relation between the viscosity and the diﬀusion constant: D= kT f f =6πηr = kT .29) Pi = Xi Pi• (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. A dt dx X (47. ∂t ∂x (47. γi (HL) → 1 as Xi → 0. (47.34) 334 .

235. 97. 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 . 270 binominal coeﬃcient 90 blue sky 81 Bohr model 18 335 335 Bohr radius 19 Boltzmann distribution 10.Index absorption spectroscopy 241 activity 146. 178 partition coeﬃcient 174 Born—Oppenheimer approximation 62. 311 mathematical deﬁnition of 146 activity coeﬃcient 146. 96. 124. 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. 99. 219 spin 201 angular momentum quantum number 52 antibonding orbital 71 Arrhenious activation energy 261 Arrhenious equation 261. 291 temperature corrected 262 atomic orbitals 49 chemists picture 50 physicists picture 50 aufbau principle 58 average value theorem 29 Berthelot gas 13. 219 jj coupling 202 LS coupling 202 quantum numbers 199. 131 Boltzmann’s equation 90. 312 adiabatic expansion 280 and heat capacity 280 adiabatic wall 120 angular momentum addition of 202 classical 192 eigenfunctions for 199.

178 Debye—Huckel theory 163 Debye—Huckel—Guggenheim equation 164 Debye’s law 129. 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 . 300. 333 coeﬃcient of thermal expansion 274 coexistence curve 293 colligative properties 318 commutator 30. 231 electrolytes strong 161 electrophoretic eﬀect 167 elementary reactions 255 and stoichiometry 256 molecularity 256 emission spectroscopy 241 enemble 89 ensemble average 103. 189 completeness 191 complimentary variables 30 compressibility factor at the critical point 295 compressibilty factor 270. 291 conﬁguration 90 conﬂuent hypergeometric functions 65 correspondence principle 41 critical point 300 cyclic rule 14.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. 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. 108 cylindrical symmetry 69 Debye—Huckel limiting law 164. 333 Clausius-Clapeyron equation 299.

334 Henry’s law constant 316. 133 ﬂipping coins 90 ﬂuctuation 92 ﬂuorescence 242 stokes shift 242 Fourier’s law of heat conduction 306. 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. 121 intramolecular vibrational relaxation (IVR) 242 337 . 291 fermions 56 Fick’s ﬁrst law 302. 334 ﬁrst law of thermodynamics 121. 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. 316. 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. 86 potential energy 39 Schrodinger equation for 39 heat 109 sign convention 110 heat capacity 115.equlibrium constant 153 Euler’s identity 4 expansion of gases 111 reversible 114 extent of reaction 328 Eyring’s equation 265. 86 Hamiltonian 47 normalization constant 49. 44.

290 mean free path 253. 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 . 86 Schrodinger equation for 65 wavefunction for 65 Morse potential 64. 86. 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.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.

324 principle quantum number 52 probability amplitude 22 probability distribution 22 PV work 111. 291 reciprocal rule 108 red sunsets 82 Redlich-Kwang gas 270 reference states 147 relationship between CP and CV 139. 44. 132 vibrational 101. 312. 218 Hamitonian for 194 wavefunctions for 195. 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. 44. 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. 132 translational 101. 219 339 . 82. 218 partition coeﬃcient 154 and drug delivery 155 for the Born model 174 partition function canonical 96. 131 electronic 101 grand canonical 97 isothermal—isobaric 97 microcanonical 96 molecular 100 rotational 101. 233 and the character table 234 Raoult’s law 311. 181 energy levels 183 energy levels for 34.particle in a box 31. 87 reaction velocity 255. 247 rotational energy levels 200. 218 particle on a ring 194 boundary conditions 194 energy levels for 195. 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. 133 Raman scattering 80 Raman spectroscopy 66. 276 relaxation eﬀects 167 rigid rotor 200 degeneracy of 235.

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. 200 spin 201 quantum number 51. 219 Hamiltonian for 212 Tyndall scattering 84 ungerade 69 van der Waals equation 340 . 133 tips for solving problems 2 total derivative 107 transfer matrix 11 triple point 300 two level system 211 ‘left’ and ‘right’ states 213. 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. 53 wavefunction 51 spin orientation quantum number 51.

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