# Chemistry 351 and 352 Physical Chemistry I and II

Darin J. Ulness Fall 2006 – 2007

Contents

I Basic Quantum Mechanics 15

16 16 17 17 22 22 23 24 27 27 27 29 30 31 31 34 38 40

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

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

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

42

II

Quantum Mechanics of Atoms and Molecules

45

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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. . . . . . . . . . . . . . . . . . . .4 Spin Orbit Coupling . . . . . . . . . . . . . .
. . . . . . . .1 Example: The C2v Group . . . . . . . . .4 Symmetry Breaking and Crystal Field Splitting
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. . . . . .1 Direct Products . . .2. . . . . . . . . . . . . . . 29. . . 32. . . . . . . . . . .29 Addition of Angular Momentum 29. . .2 Mathematical Groups . . . 229 33. . . . .3 Symmetry of Functions . . . . . . 32. . . . . . . . .1 Symmetry Operators . . . . . .
. . . . . . .1 The Addition of Angular Momentum: 29. . . . . . . . . . . . . . . . . . . . . . . . . . .
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VI
Symmetry and Spectroscopy
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221 222 222 223 223 225 225
32 Symmetry and Group Theory 32. . . . . . . . 32. . Theory . . . . .1 The Two Level System . . . . . .
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. . . . . . . .1 Molecular Vibrations . . . . . . . . . .1 Spin Angular Momentum . .1 Normal Modes . . . . 29. . .
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.2. . . 211 31. . General . . 32. . .
33 Molecules and Symmetry 228 33. . . . . . . .2 Normal Modes and Group Theory . . . . . . .3 Term Symbols . . 209 31 The Two Level System and Quantum Dynamics 211 31. . . .
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30 Approximation Techniques 207 30. .
. 32. . . . . . . . . . .2. . . . . . . . . . . . . . . . . .1 Perturbation Theory . . . . .2 Addition of Angular Momentum . . . . 228 33. . . . . . . . 229
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.2. . . . . . .1 Relaxing the rigid rotor . . . . . 250 38. . . . . . . . . . . .1 The Franck—Condon principle 235 236 236 237 240 240 241 241 242 243 243
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. . 36 Electronic Spectroscopy of Molecules 36. .2 Raman Spectroscopy . . . . . . . . 39. .1 Rate Laws . . . . . . . . . . . .1. . . . . .1. . . . . . 231 34. .
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. . .2 Emission Spectra . . . . . . . .
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. . . . . . . . . .2 Integrated rate laws . .1 Diﬀerential methods based on the rate law 39.
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VII
Kinetics and Gases
249
38 Physical Kinetics 250 38. . . . 254 254 258 259 259
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. . . .2 Determination of Rate Laws . . . . . . . . . . . . . . . . 35. . . . . . 252 39 The Rate Laws of Chemical Kinetics 39. . . . . . . . . . . . .34 Vibrational Spectroscopy and Group Theory 231 34. . .
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37 Fourier Transforms 245 37. . .

1 Relation to the van der Waals Equation of State 41. .1 Calculation of Entropy . . . . . . . . . . . . 42. . . .1 Entropy of Real Gases . . . . . .
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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. . . . . . . . . . . . . .2 The Boyle Temperature . . . . . 40. . . . . 42.2. . . . . . . .
. . . . . 41. .1 α and κT for an ideal gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1 Equations of State . . . . .
. .2 Theory of Reaction Rates . . .3 Expansion of Gases . . .4 Estimation of Virial Coeﬃcients . . . .2. . . . . .2 The Virial Series . . . . . . . .
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43 Entropy of Gases 286 43. . 42. 42. . 288
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. . .1 Temperature Eﬀects on Rate Constants . . . . . . . . .40 Temperature and Chemical Kinetics 40.1 P. . . .3. . . . . . .1 Isothermal and Adiabatic expansions . . . .4 Joule expansion . . . .
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. .2 α and κT for liquids and solids . 42. . . . .4 Chain Reactions . .2 Heat capacity CV for adiabatic expansions 42. . . 41. . . . . .1. V and T behavior .2. . . . .2. . . . . . . . . . . 42. . . . . . . . . .5 Joule-Thomson expansion . . . . . . . . . . . 40. . . . . . 42. . . . . . . . . . . . . . .
. . . parameters . .2. 42. . . . . . . .
. . . 42 Behavior of Gases 42. . . . . .1. . . . . . . . .
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. . . . . . . . . . . .3 When P is the more convenient variable . . . . . . . .1. . . . . . .1. . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . .2 Heat Capacity of Gases Revisited . . 286 43. . . . .1 Temperature corrections to the Arrhenious 40. . .
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.3. .3 Multistep Reactions . .3. . . . . .3. . . . .

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.2 Partial Molar Volumes .
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.2 The Law of Corresponding States . . . 44. . . . . . . . . . . . . . . . . .2 Thermal Conductivity of 46 Solutions 46. .
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.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. . 46. .
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. . . . .1. . .3. .1 Activity (a brief review) 46.1 Notation . . . . . . . .1 Diﬀusion . . . . . . . . 46. . . . . . .4 Henry’s Law . .3. . . . . . . . . . . . . . . . . . .3 Thermal conductivity . . . . . . .3. .3 Phase Equilibrium . . . . . .2 Raoult’s Law . .
. . . . . .2 Gas Constants from Critical Data .3 Ideal Solutions (RL) . Gases and Solids . . 46. . . . . . . . . . . . . . . . . . . . . . . . . 46. . . 44. . .
. . . . . . . . . 45 Transport Properties of Fluids 45. 45. . . . . . . . . . . .
. . . .2 Viscosity . . . . . .3 Vapor Equilibrium and the Clausius-Clapeyron Equation 44.2 Partial Molar Quantities . 44. .
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. .4 Equilibria of condensed phases . . . .
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.1 Thermal Conductivity of 45. . . . . . . . . . . . . .1 Critical Behavior of ﬂuids . . . . . . .1 Measures of Composition . . . . . . . . . . . 46. . .3. . .
. .1 The chemical potential and T and P . . . .3. . . . . . . . . . .3 Reference states for liquids .

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. . . . . . . . . . . . . . . . . . . . .3. . . . . . . . . .2 Osmotic Pressure . . . . . . . . . . . .
. . . . .3. .5 Echo Phenonmena . . . . . . . . . . . . . . 318 46. . . . . .2 Entropy Production due to Chemical Reactions . . . . . .1 Fundamentals . . . . .4 Thermodynamic Coupling . . . . . 47. . . . . . . . . 47. . . . . 319 47 Entropy Production and Irreverisble Thermodynamics 47. . . . . . . . .4. . . . .4 Colligative Properties . . . . . . . 322 322 324 325 326 328 330 331
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. . . .1 Freezing Point Depression . . 47. . . . . . 47. . . . . . .3 Examples . . . . . . . .46. . . . . . . .4. . . 318 46. . . . . . . . . . . . .2 The Second Law . . 47. . .
. . . .1 Entropy Production due to Heat Flow . . . . . . .
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Chemistry 351: Physical Chemistry I
1
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you can still learn a lot be working these and looking that their solutions in the solution manual. Keep in mind this chapter provides some examples of how to solve problems for both physical chemistry I and physical chemistry II. Consequently early in the course some of the examples might seem very itimidating. Even though there aren’t many “book” problems assigned during the year. The only way that you can be sure that you understand a concept at to be able to solve the problems associated with it. Simply skip those examples as you scan through this chapter. But there are some things that you can do to help yourself with these problems. so it might be helpful to you to see some of these problems worked out. Tips
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2
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Tips for solving problems
Working problem sets is the heart and sole of learning physical chemistry. This takes time and hard work.Solved Problems
I make-up most of the problems on the problems sets.

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

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

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

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

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

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

So. 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. 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. compare hRi as a function of the vibrational quantum number for a diatomic modelled as a harmonic oscillator versus a Morse oscillator. Therefore without performing any calculations we can at least say that hRi increases as the quantum number increases. 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. (20) V (x) = V (x)|Req + dx ¯Req 2! dx2 ¯Req | {z } | {z } | {z } =0
=0 = β 2 De
Problems Dealing With Statistical Mechanics and Thermodynamics
Problem: A vial containing 10 20 benzene molecules is at 300K. The force constant is given by the coeﬃcient of the quadratic term so in this case k = β 2 De . yes the coeﬃcient of the linear term (the term involving (R − Req ) to the ﬁrst power) is zero. This will always be true when you perform a Taylor series expansion about a minimum (or maximum).
The Taylor series about Req for this function is ¯ ¯ 2 ¯ dV (x) ¯ ¯ (R − Req ) + 1 d V (x) ¯ (R − Req )2 + · · · . The potential for the harmonic oscillator is described by a parabola centered about the equilibrium bond length. 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.

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. B or C.41 × 1017 Nv=1 = 2 sinh (21) 2 × 208 and
C—H Nv=1
We see that about 8. Each of the atoms can be in one of three states A.841% of the benzene molecules are in the 1020 13 ﬁrst vibrational excited state for the ring breathing mode and 4. ⎡ ⎤ ⎡ ⎤ ⎡ ⎤ 1 2 5 ⎢ ⎥ ⎢ ⎥ ⎢ ⎥ (1) (2) (3) (23) V = ⎣ 1 ⎦. For example. V = ⎣ 7 ⎦. So. 0 1 1 ⎡ (24)
¶ ³ µ ´ 3063 − 3×3063 2×208 × 1020 = 4. ¶ ³ µ ´ 3×992 992 rb × e− 2×208 × 1020 = 8.02 × 1013 . V = ⎣ 3 ⎦. B or C. Problem: Consider a linear chain of N atoms. To solve this problem it is useful to deﬁne the set of three dimensional column vectors V (j) such that the three elements are the total number of allowed conﬁgurations of a j-atom chain having the j th atom in state A. V (j+1) = MV (j) . where for this example ⎤ 1 1 0 ⎥ ⎢ M = ⎣ 1 1 1 ⎦.0000402% of the benzene molecules are in the ﬁrst excited state for the C—H stretching mode. × e = 2 sinh 2 × 208
17
(22)
(25)
10
.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.41×10 × 100% = 0.02×10 × 100% = 1020 0. 1 2 5 The V (j+1) can be found from the V (j) vector using the matrix equation.··· .

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

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

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

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

Part I Basic Quantum Mechanics
15
15
.

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

5.
Flaws of the solar system model • Newton: OK √ √
• Maxwell: problem
17
. First Attempts at the Structure of the Atom The “solar system” model.1. The two slit experiment 6. • The electron orbits the nucleus with the attractive coulomb force balanced by the repulsive centrifugal force. The Stern-Gerlach experiment
∗ ∗ See Handouts ∗ ∗
1.2.2. 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
.

N = 1 → N = ∞ µ ¶ 1 e2 −Z 2 e2 1 − 2 = (1.1) Zme e2 where Z is the atomic number. r=
4π 0 N 2 ~2 (1. ~ = h/2π is Planck’s constant divided by 2π. me e2 The total energy of the Bohr atom is related to its quantum number µ 2 ¶ e 1 2 . • Therefore atomic orbitals must be quantized.. me and e are the mass and charge of the electron respectively and 0 is the permittivity of free space. i.• Atoms don’t collapse =⇒ what are the consequences Experimental clues • Atomic gases have discrete spectral lines. • If the orbital radius was continuous the gas would have a continuous spectrum. 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.2)
19
.3) Eionize = E∞ − E1 = 2a0 ∞2 1 2a0
(1.e.52918 Å and is called the Bohr radius. N is a positive real integer called the quantum number.
2
The constant quantity 4π e0e~ appears often and is given the special symbol a0 ≡ m 2 4π 0 ~2 = 0.

6. the atom may only change its orbital radius by discrete amounts.· · · Series Name Lyman Balmer Pachen Brackett Pfund
(1.8.7.e — Eionize = 2a0 = 13.3.· · · 5.7.
2
— Eionize experimentally observed from spectroscopy is 13.6.4.4)
— Since the orbitals are quantized.5.· · · 6. — Doing this results in the emission or absorption of a photon with energy v= ˜ 4E hc (1.4.· · · 3.667 cm−1 = R.· · · 4. R is called the Rydberg constant.5)
Failure of the Bohr model • No ﬁne structure predicted (electron-electron coupling) • No hyperﬁne structure predicted (electron-nucleus coupling) • No Zeeman eﬀect predicted (response of spectrum to magnetic ﬁeld)
20
.5.606 eV = 109.605 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.

• Spin is not included in theory The Bohr quantization idea points to a wavelike behavior for the electron. The wave must satisfy periodic boundary conditions much like a vibrating ring ∗ ∗ ∗ See Fig. 11.9 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
.

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

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

(2. 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. therefore this is a general procedure that will work for any wavefunction.8) 2 normalized x |ψ(x)| dx 1 −∞
2. (2. z)|2 dxdydz.3)
space space
because that is the very deﬁnition of a normalized wavefunction. (2.5)
space
Z
space
|ψnorm |2 dxdydz = 1
(2. Z |ψunnorm |2 dxdydz = N 2 × 1 = N 2 . sZ N=
space
|ψunnorm (x.3. y. Postulates II and II
Postulate II: Every physical observable is represented by a linear (Hermitian) operator.4)
This gives us an expression for N.
24
. Taking the square root of both sides gives.7)
Notice that no where did we ever specify what ψunnorm or ψnorm actually were.6)
So ﬁnally we get the normalized wavefunction by reagranging ψ unnorm = Nψnorm : ψ norm = 1 ψ . So. N unnorm (2.but
The N is just a constant so it can be pulled out of both the mod-square and the integral Z Z 2 2 |ψunnorm | dxdydz = N |ψnorm |2 dxdydz. Thus wherever R we see space |ψnorm |2 dxdydz we can replace it with 1.

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

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

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

Solve the Schrödinger equation. z) − E) ψ = 0 (3.• The total energy for a classical system is Ecl = T + V. z). 2.5)
where ∇2 ≡
∂2 ∂x2
+
∂2 ∂y2
+
∂2 .7)
ˆ 3.2)
(3.6)
ˆ V = V (ˆ. where T is the kinetic energy and V is the potential energy. px etc. z ) = V (x. Thus. y. Hψ = Eψ. z) ψ = Eψ 2m −~2 2 ∇ ψ + (V (x.8) ⇒ 2m
28
. with their appropriate operators. y.4)
• Note: Some quantum systems don’t have classical analogs so the Hamiltonian operator must be hypothesized.3)
• The potential energy is almost always a function of coordinates only V = V (x. • The kinetic energy is always of the form T = ¢ 1 ¡ 2 px + p2 + p2 y z 2m (3. z) H =T +V = 2m
(3. which is now a second order diﬀerential equation of the form ¸ ∙ 2 −~ 2 ∇ + V (x.
2 2 ˆ −~ ∇2 = −~ ∇2 . x. Use Postulate II to replace the classical variables. y. y .. z) (3. x ˆ ˆ So. y. −~2 2 ˆ ˆ ˆ ∇ + V (x. ˆ T = 2m 2m
(3. y. ∂z 2
and (3.

or average. value for the measurement. however.3. This is given by Z hˆ i = α ψ∗ αψdxdydz ˆ (3.9)
3. z) which determines whether this is easy or hard to do. The Average Value Theorem
Postulate III implies that if ψ is an eigenfunction of a particular operator representing a physical observable.12)
space
29
. give an expectation. then all measurements of that physical property will yield the associated eigenvalue. However. but we cannot predict for certain which one. then all measurements of that physical property will still yield an eigenvalue. We can. 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. y.11)
space
ψ px ψdxdydz = −i~ ˆ
∗
Z
(3. If ψ is not an eigenfunction of a particular operator.10)
space
For example.• Note: It is solely the form of V (x.

) Suppose we know the position of a particle perfectly. β ˆ ˆ deﬁned as h i ˆ ≡ αβ − β α. x]i| = |hˆx x − xpx i| p ˆ p ˆ ˆˆ 2 ¯Z 2 ¯ µ ¶ ¯ 1¯ ¯ ψ ∗ ~ ∂ x − x ∂ ψdx¯ = ¯ 2¯ i ∂x ∂x ¯ ¯ ¯~¯ ~ = ¯ ¯= . β ¯ . ¯ 2i ¯ 2 (3. for example. even in principle.3. δpx δy = 0. be simultaneously known to arbitrary precision. Such variables are called complimentary. what can we say about its momentum?
30
. (n. at the very best we can only hope to simultaneously know position and momentum such that the product of the uncertainty in each is ~ . the y position and the x momentum to arbitrary precision. β ˆ ˆˆ ˆˆ (3.. This idea is the Heisenberg uncertainty principle and is of profound importance.14) The most important example of complimentary variables is position and momentum. we can 2 know.b. The Heisenberg Uncertainty Principle
In quantum mechanics certain pairs of variables can not. α.15)
So. We see δpx δx ≥ 1 1 |h[ˆx . ˆ (3. The commutator is ˆ where the notation α. The general statement of the Heisenberg uncertainty principle is 1 ¯Dh ˆ iE¯ ¯ ¯ δαδβ ≥ ¯ α.4.13) 2 h i ˆ means the commutator of α and β.

It also can be used as a “zeroth order” model for certain physical systems.
31
31
. 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. 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.4. The 1D Particle in a Box Problem
Consider the potential. as a consequence. ⎪ ⎩ ∞ x≥a
(4.
4.1. V (x). Nevertheless it is of great pedagogical and practical value. We shall soon see that the particle in a box is a physically unrealistic system and. This system is very simple which is one reason for beginning with it. 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.

Therefore it must satisfy the boundary conditions (b. dx2 ~ The general solution of this diﬀerential equation is ψ(x) = A sin kx + B cos kx. the particle can never exist so. in region I and III. ψ must equal zero in these regions.Now.3)
(4.
32
.c. The Schrödinger equation in region II is (V (x) = 0)
2 2 ˆ = Eψ =⇒ −~ d ψ(x) = Eψ. where the potential is inﬁnite. ~2
(4. Hψ 2m dx2
(4.4)
Now ψ must be continuous for all x.2)
which can be rearranged into the form d2 ψ(x) 2mE + 2 ψ(x) = 0. The particle must be found only in region II.): ψ(0) = 0 and ψ(a) = 0. where k = q
2mE .

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

a in a box are I II III .11)
4.2.9)
Is this wavefunction OK?
Thus our normalized wavefunctions for a particle ⎧ ⎪ 0 ⎪ q ⎨ 2 ψn (x) = sin nπx a ⎪ a ⎪ ⎩ 0 q
2mEn ~2
(4.10)
We can get the energy levels from kn = En =
and kn =
nπ : a
h n2 π 2 ~2 ~= 2π n2 h2 = .
(4.Solving for A gives A=
r
2 . Implications of the Particle in a Box problem
Zero Point Energy
34
. 2ma2 8ma2
(4.

But we also know that the particle is located within a ﬁnite region of ˆ space. the lowest energy state. This residual energy is called the zero point energy and is a consequence of the uncertainty principle.12)
That is.The smallest value for n is 1 which corresponds to an energy of E1 = h2 6= 0. δˆδp = 0 which violates the uncertainty principle. 8ma2 (4.13)
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
. so δˆ 6= ∞. or ground state. x Hence. 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. δ p = 0. has nonzero energy.

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

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

The Harmonic Oscillator
The harmonic oscillator model which is simply a mass undergoing simple harmonic motion. where k is the spring constant and Req is the equilibrium position of the ball. 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. The force exerted by the spring in the above ﬁgure is F = −k(R − Req ). We shall begin by reviewing the classical harmonic oscillator and than we will turn our attention to the quantum oscillator. 38
38
.5.

(5. Thus V = 1 kx2 . q
k m
(5.4)
(5. 2 By postulate III the Schrödinger equation becomes ⎛ ⎞
K. 2 2 |2m dx } | {z } {z µ ¶ 1 2 kx − E ψ = 0 2
(5. We know Z 1 V = − F dx = kx2 + C.E.E. so in going to the quantum oscillator.5)
This diﬀerential equation is not easy to solve (you can wait to solve it in graduate school). we get dt
2
d2 x k d2 x m 2 = −kx ⇒ 2 + x = 0 dt dt m
(5.
39
.3) 2 Since energy is on an arbitrary scale we can set C = 0. where ω = conditions.1)
This is second order diﬀerential equation which we already know the solutions to: x = A sin ωt + B cos ωt.x From Newton’s law of motion F = ma = m d 2 . P.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.
This can be rearrange into the form −~2 d2 ψ + 2m dx2
1 ⎜ −~2 d2 ⎟ ˆ Hψ = Eψ ⇒ ⎝ + kx2 ⎠ ψ = Eψ. we need to express the force of the spring in terms of potential energy V .

2 where again ω = q
k . ∗ ∗ ∗ See Fig.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. y = (5. 11. 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 . An = p √ .6) x. 2 where ν 0 =
1 2π
(5. As it turns out.1.7)
Note the energy levels are often written as 1 En = (n + )hν 0 . m
(5.12 Laidler&Meiser ∗ ∗∗
5. 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
.8)
q
k m
and is called the vibrational constant. The eigenvalues (the energy levels) are 1 En = (n + )~ω.

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

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

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. sZ N=
space
|ψunnorm (x)|2 dx.9)
• The normalized wavefunction: ψ norm = 1 ψ .10)
• The Schrödinger equation (which should be posted on your refrigerator). see above for 3D).
Equations
• The short cut for getting the normalization constant (1D. 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. (5. N unnorm (5.11)
43
43
.
(5. ˆ Hψ = Eψ.

15)
(5. a a • The energy levels for the 1D particle in a box.16)
• The energy level spacing for the 1D particle in a box. r nπx 2 ψn (x) = sin . 2m dx2 • How to get the average value for some property (1D version).19)
44
. ∂x
(5. 2ma2 8ma2
(5. ω = 2
k m
(5. ˆ hˆ i = α
space
(5. y = √ .• The Schrödinger equation for 1D problems as a diﬀerential equation. An = p ψn (y) = An Hn (y)e . Z ψ∗ αψdx. En =
h n2 π 2 ~2 ~= 2π n2 h2 = .12)
(5. 4E = (2n + 1) h2 8ma2 (5. 2 n n! π ~ 2
(5.13)
• The momentum operator
px = −i~ ˆ
∂ . −~2 d2 ψ + (V (x) − E) ψ = 0.14)
• Normalized wavefunctions for the 1D particle in a box.18)
where An is the normalization constant for the nth eigenfunction and Hn (y) are the Hermite polynomials.17)
• The wavefunctions for the harmonic oscillator are ¶1 µ 2 km 4 1 − y2 x. r
• The energy levels are 1 En = (n + )~ω.

Part II Quantum Mechanics of Atoms and Molecules
45
45
.

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

ψ must be a product state.7)
47
. φ) = ψrad (r)ψang (θ. φ) It turns out that solving the Schrödinger equation. φ) = Eψang (θ.8) (6. ˆ Hang ψang (θ. ψ(r. θ.5)
−~2 ˆ Hang = 2me
(6. The classical potential energy for these hydrogenic systems is V (r) = So the Hamiltonian is −Ze2 . ∇ + H= 2me (4π 0 )ˆ r
(6.2)
Schrödinger’s equation (in spherical polar coordinates) becomes ˆ Eψ = Hψ (6.1)
−Ze2 −~2 ˆ 2 ˆ .4)
(6.3) ¶ µ 2 2 −Ze −~ ˆ 2 ψ ∇ + Eψ = 2me (4π 0 )ˆ r µ 2∙ ¶ µ ¶¸ −~ 1 ∂ 2 ∂ 1 ∂ 1 ∂2 1 ∂ −Ze2 Eψ = r + sin θ + ψ + 2me r2 ∂r ∂r r2 sin θ ∂θ ∂θ sin2 θ ∂φ2 (4π 0 )r The Hamiltonian is (almost) the sum of a radial part (only a function of r) and an angular part (only a function of θ and φ): 1 ˆ ˆ ˆ H = Hrad + 2 Hang . (6.6)
Since the Hamiltonian is the sum of two terms. (4π 0 )r (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. φ).with the origin located on the nucleus.

l(l + 1)~2 ˆ ψang (θ. φ) = ER(r)Ylm (θ. The spherical harmonics are known functions.11) l(l + 1)~2 .13)
48
. The full Schrödinger equation becomes ˆ Hψ(r. φ) = 2me Now let’s denote the radial part of the wavefunction as ψ rad (r) = R(r).12) (6. 2me (6. θ.10)
(6. φ) = ER(r)Ylm (θ. (6. φ) ˆ HR(r)Ylm (θ. θ.yields ψ ang (θ. φ) ¶ µ 1 ˆ ˆ Hrad + 2 Hang R(r)Ylm (θ. φ) = Eψ(r. φ). φ) H 2me r2 (6. φ) Hang ψang (θ. φ). φ) = Ylm (θ.) We shall use the spherical harmonics more next semester when we develop the quantum theory of angular momentum. φ) = ER(r)Ylm (θ. ˆ It also turns out that the energy associated with Hang is found to be E = El = So.9)
where the Ylm (θ. φ)’s are the spherical harmonic functions characterized by quantum numbers l and m. r ˆ Operating with Hang we get ¶ µ 2 ˆ rad + l(l + 1)~ R(r)Ylm (θ. (Mathematica knows them and you can use them just like any other built-in function like sine or cosine.

φ) = Rnl (r)Ylm (θ. n In fact.18)
6. the energy levels are given by En = − Z 2R n2 (6. (6.16) na0 2n[(n + l)!]3 The energy eigenvalues. θ.14) 2me r2 ∂r ∂r 4π 0 r r2 This diﬀerential equation is very similar to a known equation called Laguerre’s diﬀerential equation which has as solutions the Laguerre polynomials Ll (x). (6.15) e Ln+1 n n
where the normalization constant. i. Anl .17)
Note: The energy levels are determined by n alone–l drops out. So. depends on the n and l quantum numbers as sµ ¶3 2Z (n − l − 1)! Anl = − (6. Also Note: the energy levels are the same as for the Bohr model. which will be brieﬂy discussed later) is ψ nlm (r. µ ¶l µ ¶ 2σ 2σ −σ/n 2l+1 Rnl (σ) = Anl .2.The Ylm (θ.e.
49
. Discussion of the Wavefunctions
We are now very close to having the atomic orbitals familiar from freshman chemistry.. φ) (6. the solutions to our diﬀerential equation are closely related to the Laguerre polynomials. the total wavefunction that describes a hydrogenic system (ignoring the spin of the electron. φ) can now be cancelled to leave a one dimensional diﬀerential equation: µ ¶ Ze2 l(l + 1) −~2 1 ∂ 2 ∂ r − − R(r) = ER(r).

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

Spin is actually rather peculiar so we will put oﬀ a more detailed discussion until next semester.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 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. • ms is the spin orientation quantum number and ms = ±1/2 for electrons.3. so we can not write down an explicit function of the coordinate space variables. 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).
51
. The spin wavefunction is a function in spin space not the usual coordinate space. electrons also posses an intrinsic quantity called spin.

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

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

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

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

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

• Ψb and Ψc have symmetric spatial parts. So. However considering the symmetry with respect to exchange we see the following • Ψa has symmetric spatial and spin parts and is there for symmetric. 2) (7. Now let’s blindly list all possibilities for the ground state wave function of helium Ψa = ψ1s (1)α(1)ψ1s (2)α(2) Ψb = ψ1s (1)α(1)ψ1s (2)β(2) Ψc = ψ1s (1)β(1)ψ1s (2)α(2) Ψd = ψ1s (1)β(1)ψ1s (2)β(2) These appear to be four reasonable ground state wavefunctions which would imply a four-fold degeneracy. Ψ = ψ(1)ψ(2)χ(1)χ(2). • Similarly for Ψd .The total wavefunction is Ψ = ψ(1. 2)χ(1. | {z }| {z }
spatial part spin part
(7. (7. The Pauli exclusion principle implies that if the spatial part is even with respect to exchange then the spin part must be odd. It must be excluded.5)
57
.3) Since a complete solution for helium is not possible we must use approximate wavefunctions.4)
where the single particle wavefunctions are that of the hydrogenic system. we may as well simplify matters and use product state wavefunctions (products of the hydrogenic wavefunctions). but the spin part is neither symmetric or antisymmetric. one must make an antisymmetric linear combination of the spin parts. Likewise if the spatial part is odd then the spin part must be even. Since we are doing this.

. ¯ ¯ . 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. . . . Namely the wavefunction is product state that must be antisymmeterized in accordance with the Pauli exclusion principle. . .7) (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 (7.6)
7.8) . The product wavefunction for the ground state is determined by applying the aufbau principle. Many Electron Atoms
The remaining atoms on the periodic table are handled in a manner similar to helium. ¯ ¯ ¯ ¯ ¯ ψ (N)α(N) ψ (N)β(N) ψn (N )α(N) ψn (N)β(N) ¯ 1s 1s
58
. . So the ground state wave function for helium is Ψg = ψ1s (1)ψ1s (2) [α(1)β(2) − α(2)β(1)] . . . .The appropriate linear combination is α(1)β(2) − α(2)β(1). .

11) H= 2me i 4π 0 ri j>i 4π 0 rij i=1
59
.1. This agrees with the Puli exclusion principle.3. and ψ2s α (or ψ 2s β).9)
(7. As an example consider lithium: • There are three electrons so we need three hydrogenic wavefunctions: ψ1s α.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). It is also antisymmetric under exchange of columns. ψ1s β. 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. • 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
(7.10)
• The short hand notation for these states is (1s)2 (2s)1 7. 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.

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

ˆ TN is the nuclear kinetic energy operator and is given by
2 2 ~2 ˆ2 ∂ ˆ2 ∂ ˆN ˆN = − ~ ∇2 = − ~ + J .1.
61
. R T 2μ 2μR2 ∂R ∂R 2μ
(8.1)
(8.
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 . +
ZB e2 4π 0 rBi
P ˆ VNe = − i P ˆ Vee = i>j
h
ZA e2 4π 0 rAi
i
is the nuclear—electron potential energy operator. P ~2 ˆ 2 ˆ Te = i − 2me ∇ei is the kinetic energy operator for the electrons.8.1.2)
m1 m2 m1 +m2
ˆ where J is angular momentum operator for molecular rotation and μ = the reduced mass of the diatomic molecule. ˆ VNN =
ZA ZBe e2 4π 0 R
is
is the nuclear—nuclear potential energy operator.

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

(8.5)

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

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

62

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

8.2. Molecular Vibrations

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

∂2E ∂R2

´

¡ ∂E ¢

∂R Req

must be zero, so the linear term vanishes.

Req

≡ ke as the force constant.

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

63

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

ke μ . ~

(8.11)

(8.12)

1 Evib,n = hc˜ e (n + ), ω 2

ke . μ

(8.13)

where ω e ≡ ˜

1 2π

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

64

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

q

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

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

(8.16)

This is another diﬀerential equation that is diﬃcult to solve.

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

(8.18)

65

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

hc˜ e ω . 4De

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

4E hc

(in units of wavenumbers, cm−1 ).

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

66

**9. Molecular Orbital Theory and Symmetry
**

9.1. Molecular Orbital Theory

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

67

(9.1)

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

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

9.2. Symmetry

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

68

• 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. z) must equal the electron density at (−x. ˆ. −z) = aψ(x.3)
Cylindrical symmetry
69
. • Because of the symmetry the electron density at (x. (9.Inversion symmetry • The potential ﬁeld of the hydrogen molecular ion is cylindrically symmetric about the z-axis. y. −z). z) = ψ(−x. That is ı ˆψ(x. −y. −y. • The above symmetry therefore requires that the molecular orbitals be eigenfunctions of the inversion operator. ı • Moreover the eigenvalue a can be either +1 or −1. y. y. z).

.• The cylindrical symmetry implies that the potential energy can not depend on the φ. • The molecular wavefunction is described by an eigenvalue λ = 0. ±2. . — 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
. . ±1.

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

10.1. Molecular Orbital Diagrams
10. Linear combination of the 1s atomic orbital from each H atom is used for the molecular orbital of H+ : 2 (1sA ) = ke−rA /a0 (10.2)
72
72
. Useful can mean qualitatively useful or quantitatively useful. LCAO is qualitatively very useful but it lacks quantitative precision.1) and (1sB ) = ke−rB /a0 (10. Unfortunately we can’t have both. we need to ﬁnd some useful approximations for them. LCAO–Linear Combinations of Atomic Orbitals
Now that we know what symmetry the molecular orbitals must posses. 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).

But we shall also classify them according to their inversion symmetry and wether or not they are bonding or antibonding.
73
.4) (10.3)
(10. Φ+ represents a situation in which the electron density is concentrated between the nuclei and thus represents a bonding orbital. For molecular orbitals we shall also classify them according to angular momentum.1.5)
As can be seen from the above ﬁgure.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. Conversely Φ− represents a situation in which the electron density is very low between the nuclei and thus represents an antibonding orbital 10.1. Classiﬁcation of Molecular Orbitals With atoms we classiﬁed atomic orbitals according to angular momentum.

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

so one forms linear combinations of the atomic orbitals.
It is now more appropriate to speak in terms of molecular orbitals. These are σg = 1sA + 1sB and σ ∗ = 1sA − 1sB . their respective s orbitals begin to overlap. u (10.6)
75
. There are two acceptable linear combinations.7) (10.As the atom are brought closer together.

It can be shown mathematically that the energy level associated with σg is lower than σ∗ . It is also to be expected since we know H2 is a stable molecule. We will focus on the second row homonuclear diatomics and some simple heteronuclear diatomics. Molecular Orbital Diagrams
The energy levels associated with the molecular orbitals are drawn schematically is what is called a molecular orbital diagram.
10. u We can intuit this qualitatively however since the σ ∗ orbital must have a node u whereas the σ g does not.
76
. Some get very complicated.3. The molecular orbital diagram for H2 is shown below
Molecular orbital diagrams can be drawn for any molecule.

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

(Next semester will we look at the details of this for polyatomic molecules) ˆ Hmol Ψmol = Emol Ψmol (10. 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.10. Likewise we have discussed molecular orbitals which are the electronic wavefunctions.9) ´ ³ ˆ ˆ ˆ Hele + Hvib + Hrot ψele ψvib ψrot = (Eele + Evib + Erot ) ψele ψvib ψrot
78
.4. 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.

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

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

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

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

83
. 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.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.2. White Clouds We might expect that clouds should be highly colored since they consist of droplets of water which scatter light very eﬀectively.2.
11.

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

φ) = Rnl (r)Ylm (θ.6)
µ
2σ n
¶l
e
−σ/n
2l+1 Ln+1
µ
2σ n
¶
.7)
where the normalization constant. The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations. φ) • The radial part is. θ. Anl . This section should not substitute for your studying of the rest of this material.8) na0 2n[(n + l)!]3 85
85
.
(11.
Equations
• The wavefunctions for the hydrogenic system are ψnlm (r. The equations are collected here simply for handy reference for you while working the problem sets. depends on the n and l quantum numbers as sµ ¶3 2Z (n − l − 1)! Anl = − (11.Key Equations for Exam 2
Listed here are some of the key equations for Exam 2. Rnl (σ) = Anl (11.

13)
Now the zero of energy is the dissociated state (i.n = −De + hc˜ e (n + ) − hc˜ e xe (n + )2 . (11. 2 n n! π ~ 2
(11.14)
86
. R = Req . y = x.Ee (R → ∞) = 0). • The energy levels for the Morse oscillator are of the form 1 1 ω ω Evib. ω Note: this expression for the Morse potential has the zero of energy at the bottom of the well (i.e.
• The energy levels are 1 En = (n + )~ω.• The energy levels for the hydrogenic system are given by En = − Z 2R n2 (11. . 4De
(11. ω = 2 • The Morse potential is
r
k m
(11.9)
• The wavefunctions for the harmonic oscillator are ¶1 µ 2 km 4 1 − y2 ψ n (y) = An Hn (y)e .12) q μ where De is the well depth and β = 2πc˜ e 2De is the Morse parameter. (11.Ee (Req ) = 0).11)
Ee (R) = De [1 − e−β(R−Re q ) ]2 . An = p √ . • The Morse Potential can also be written as Ee (R) = De [e−2β(R−Req ) − 2e−β(R−Req ) ].10)
where An is the normalization constant for the nth eigenfunction and Hn (y) are the Hermite polynomials.e. 2 2 where ω e xe together is the anharmonicity constant. with xe = ˜
hc˜ e ω . . R → ∞.

15)
• The Rayleigh scattering law is I(λ) ∝ 1/λ4 ∝ ω 4 (11.16)
87
.• Bond order is deﬁned as BO = 1 (# of bonding electrons − # of antibonding electrons) 2 (11.

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

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

• 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. say.1)
The number C(N.2) (12. 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. The number of possible conﬁgurations is deﬁned as W. Combinations and Permutations Consider a random system that when measured can appear in one of two outcomes (e. This is given by the mathematical formula for combinations C(N. One valuable piece of statistical information about system is knowing how many diﬀerent ways the system appears p times in.
Boltzmann developed an equation to connect the microscopic properties of an ensemble to the macroscopic properties. p)xp . p!(N − p)! (12. The Boltzmann equation is S = k ln W Where S is entropy and k is Boltzmann’s constant.3)
90
. outcome 1 after N measurements. • Conﬁguration: The collection of all equivalent microstates.1.. 12.g.1.
(12. p) = N! . ﬂipping coins).

p)(1)p
(12. we are interested in a particular permutation. This is given by W (N.
91
. p) = N N 2 2 p!(N − p)! (12.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). So rather than a particular combination. Set x = 1 in the above.
So the probability of any one outcome of N measurements is P (N. ∗ ∗ ∗ See Examples on Handout ∗ ∗∗ For both combinations and permutations we need to evaluated factorials. p) = 1 1 N! C(N.4)
2N =
C(N.6)
where N is the total number of measurements and Ni is the number of indistinguishable results of type i. {Ni }) = N! N1 !N2 !N3 ! · · · (12.5)
For combinations we did not care what order the results of the measurements occurred. This gives (1 + 1)
N
=
N X p=0 N X p=0
C(N. Sometimes the order is important.

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

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

13.3)
A system in equilibrium always tries to maximize entropy and minimize energy and so the equilibrium conﬁguration is a compromise between these two cases.
(13.1)
Ni
(13. The total energy is given by E=
where Ni is the number of particles in energy state i. 94
94
. The total number of particles is. N1 !N2 ! · · · (13. N= X
i
X
i
Ni i . Since the system is isolated the total energy. The Boltzmann Distribution
Consider a isolated system of N molecules that has the set { i } energy levels associated with it.2)
The number of conﬁgurations for the system is then given by the number of distinct permutations of the system W = N! . and the total number of particles will be constant. of course. E.

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

Partition Functions
We have already come across both the partition functions that we will use in this class..5)
j
Since we started with a isolated system. The ﬁrst is W –the number of conﬁgurations. This is called the microcanonical partition function.
13.e. This partition function is not very useful to us so we will not discuss it further. The analysis readily generalizes to variable energy i.
96
. β and hence T are constants.The pi represents the probability of ﬁnding the a randomly chosen particle or system which has energy i . The second partition function is Q= X
j
gj e−βEj
(13. nonisolated systems by considering T as a variable. This is the Boltzmann distribution gi e−β i Pi = P −β j gj e (13.1. A given energy E will correspond to a unique temperature T.6)
and is called the canonical partition function.

But this an inconvenient connection because. Relation between the Q and W When we get to connecting quantum mechanics with thermodynamics it will prove convenient to use Boltzmann’s equation (S = k ln W ) but as was stated earlier it is not convenient to use the microcanonical partition function (W ). It is not an exact relation as we derive it.) The partition function is to statistical mechanics as the wavefunction is to quantum mechanics.1. (Note: the symbol Z is also often used for the canonical partition function. In fact we have already seen this in the S = k ln W. 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. 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). That is.1. but it is a very good approximation for large numbers of particles. for among other reasons. the partition function contains all that can be known about the ensemble. In the following we give an argument which provides a relation between the partition functions. energy levels and temperature do not explicitly appear.
97
.This was ﬁrst encountered as the denominator of the Boltzmann distribution and it is extremely important in statistical mechanics.

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

106
.Helmholtz Free Energy Free energy is the energy contained in the system which is available to do work.12) ∂β ∂β n. 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.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. We will make the distinction between the Helmholtz free energy and the more familiar Gibb’s free energy (G) later as well. 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.

15.1. The total derivative of z(x. Thermodynamics is completely independent of the microscopic structure of the system. Summary of Relations 1.1. Properties of Partial Derivatives
Of critical importance in mastering thermodynamics is to become proﬁcient with partial derivatives. Thermodynamics is a theory describing the most general properties of macroscopic systems at equilibrium and the process of transferring between equilibrium states. ∗ ∗ ∗ See Handout ∗ ∗∗ 15.1. The chain rule for partial derivatives: µ ¶ µ ¶ µ ¶ ∂u ∂z ∂z = ∂x y ∂u y ∂x y 107
107
(15. y): µ ¶ µ ¶ ∂z ∂z dz = dx + dy ∂x y ∂y x 2. Work
We now begin the study of thermodynamics.1)
(15.2)
.
15.

Microscopic systems: Systems containing a small number of particles. The cyclic rule:
¶
y
∂z =− ∂y ∂z ∂x ¶
µ
¶ µ
x
∂y ∂x
(15.2.2. Deﬁnitions
System: a collection of particles Macroscopic systems: Systems containing a large number of particles.
108
. Closed system: A system that cannot exchange matter with its environment but may exchange energy.1.4) ¶
z
5.3)
y
4.5)
u
15. The reciprocal rule:
µ µ ∂z ∂x
∂z ∂x
¶ µ
y
∂x ∂z
¶
=1 ¶
(15.3. 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. Finally
µ
∂z ∂x
¶
=
u
µ
+
y
µ
∂z ∂y
¶ µ
x
∂y ∂x
(15. Types of Systems Isolated system: A system that cannot exchange matter or energy with its environment.

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

is positive (q > 0) if heat is absorbed by the system. a.g. (15. Heat. Joules)... 15. we need a more general deﬁnition if inﬁnitesimal work.8)
Ai dai
(15. w. Any given external parameter.3. meters). Heat is negative (q < 0) if heat is released from the system.Convention Work. q.g. Newtons) and the generalized displacement need not have units of position (e. F . but the product of the two must have units of energy (e. is positive (w > 0) if work is done on the system.7)
For thermodynamics. The inﬁnitesimal amount of work done on the system is then given by dw = Ada. Generalized Forces and Displacements In physics you learned that an inﬁnitesimal change in work is given by the product of force.g.. Work is negative (w < 0) if work is done by the system. A may be considered as a ‘generalized force’ which is coupled to a particular internal parameter. which acts as ‘generalized displacement. times and inﬁnitesimal change in position.’ Note that the generalized force need not have units of force (e.1. or more generally as dw = X
i
(15.9)
110
. dx: dw = F dx.

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

Rx Recall from physics that work is the (path) integral over force: w = − x12 F dx.12)
112
.11) A |{z} x1 x1 |{z} V1 dV
Pex
If Pex is independent of V then Z Z V2 Pex dV = −Pex w=−
V1
V2
V1
dV = −Pex 4V
(15.The force exerted on a gas by a piston is equal to the external pressure times the area of the piston: F = Pex A ⇒ Pex = F/A. This can be manipulated as Z x2 Z x2 Z V2 F w=− F dx = − Adx = − Pex dV (15.

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

Namely Pgas = Pex .
114
. So. wrev = wmax . Now consider case in the ﬁgure below
The expansion is reversible.3)
w2 = −
Vi
Patm dV = −Patm (V2 − Vi )
(16. where w1 = − and Z
Vi
(16.2)
V1
Patm+2W dV = −Patm+2W (Vi − V1 ) Z
V2
(16. wrev = − Z
V2
Pgas dV
(16.5)
V1
This is the limiting case of path B in the previous ﬁgure.and wB = w1 + w2 . That is. there is always an intermediate equilibrium throughout the expansion. Thus wrev is the maximum possible work that can be done in an expansion.4)
Hence it is clear that |wB | > |wA | .

7) That is.b. Heat Capacity
Temperature and heat are diﬀerent. it is not a constant. ¡ dq ¢ ¡ dq ¢ e. divide by the number of moles to get molar heat capacity µ ¶ 1 dq CV m (T ) = n dT V 2.8)
(16. C(T ) = From this equation dq = C(t)dT. To make an intensive property 1.g.2. when the temperature of a substance having a heat capacity C(t) is changed by dT.9)
V
115
. Temperature is an intensive property and heat is an extensive property. dq amount of heat energy is transferred. divide by mass to get speciﬁc heat 1 cV = m We will discuss heat capacity more later. Temperature is not the amount of heat.. (16.16. The heat capacity also depends on the conditions during the temperature change. heat capacity is a function of T . heat is related to temperature through the heat capacity dq dT n. CV (T ) = dT V and CP (T ) = dT P are not the same Heat capacity is an extensive property. µ dq dT ¶ (16.. However.6)
(16.

ρ= nRT RT
(and molar (16.3. C(T. Equations of State
The macroscopic properties of matter are related to one another via a phenomenological equation of state.1. Example 1: The Ideal Gas Law The equation of state for volume of an ideal gas is P V = nRT . 16. (More complicated systems require more than two independent variables.16. so we will focus our development of thermodynamics on simple systems.3.10)
where R is the gas constant (8. P independent then heat capacity is a function of T and P .g. (16. (16.315 J K−1 mol−1 ) and n is the number of moles. but behave in the same way as the more simple pure system. The state of a pure. n m V
The equation of state can also be expressed in terms of density ρ = mass m/n) MP mP = .11) where Vm =
V . The ideal gas equation of state can be expressed in terms of intensive variables only P Vm = RT .. P ).) The functional dependence of any property on the two independent variables is an equation of state.12)
116
. T . e. homogeneous material (in the absence of external ﬁelds) is given by the values of any two intensive properties.

16. Example 2: The van der Waals Equation of State A more realistic equation of state was presented by van der Waals: P = nRT n2 a − 2.2. V − nb V (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
.3.

In term of intensive variables P = a RT − 2.16)
• Redlich-Kwang P = (16.15)
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. 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. Vm − b Vm (16.3.14)
16.3. Other Equations of State The van der Waals equation of state is not the only one that has been proposed.17)
118
.

Temperature scales • Celsius: A relative scale based on water (T = 0◦ C for melting ice and T = 100◦ C for boiling water) • Kelvin: An absolute temperature scale based on the ideal gas law.17. Today we will cover the zeroth and ﬁrst laws. The Zeroth and First Laws of Thermodynamics
Over the course of the next two lectures we will discuss the four core laws of thermodyanmics. Next time we will cover the second and third laws which both deal with entropy.
17.1. • Heat ﬂows from high T to Low T. The temperature at which (for ﬁxed V and n) the pressure is zero is deﬁned as T =0K • T (Kelvin) = T (Celsius) + 273.15 119
119
. which deal with temperature and total energy respectively. Temperature and the Zeroth Law of Thermodynamics
Temperature tells us the direction of thermal energy (heat) ﬂow.

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. (Vm (SATP) = 24.
120
. (Vm (STP) = 22. then the systems are in thermal equilibrium.15 K and P = 1 bar.414 L/mol) • standard ambient temperature and pressure (SATP): T = 298. 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. Thermal equilibrium: If two systems are in contact along a diathermic wall and no heat ﬂows across the wall.1)
The zeroth law implies that if an arbitrary system. The zeroth law of thermodynamics • Mathematical statement: If TA = TB and TB = TC .Standard conditions • standard temperature and pressure (STP): T = 273. Adiabatic wall: A wall the does not allow heat to ﬂow through it. C.789 L/mol)
Diathermic wall: A wall that allows heat to ﬂow through it. (17.

g. The internal energy state function For characterizing the change in energy of a system. 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.4)
121
.2.3)
4U = q + w
(17.17. V (T.1. The value of the state function depends only on that given state and on no other possible state of the 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 ﬁrst law of thermodynamics: • Mathematical statement: or in diﬀerential form dU = dq + dw (17. one is concerned with the work done on the system (w) and the heat supplied to the system (q). 17. The energy of a system is called the internal energy (U) of the system.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.

U → U(T.9)
(17. is called the internal pressure (it has no standard symbol). The total diﬀerential of U (T.in diﬀerential form this is dU = dq − Pex dV (17.8)
. 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 most convenient at this time are V and T.10)
V
122
. ¡ ∂U ¢
∂V T
(17. ¶ ¶ µ ∂U ∂U dq = CV dT = dq =⇒ = ∂T V ∂T V dT ¡ ¢ Hence the slope ∂U V is the heat capacity.6)
(17. dU = ∂T V ∂V T So. ∂T The other slope.
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
(17.5)
Although U can be expressed as a function of any two state variables. V ).7)
µ
(17.

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

and T are state functions. (18. 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. Furthermore we derived the simple relation between the Helmholtz free energy and the canonical partition function as A = −kT ln Q. A.2)
1 (dU − dA) T 124
(18. U A 1 − = (U − A).18. T T T Since U. the average energy of the system E is in fact what we call internal energy: ¯ U ≡ E.1) T ¯ Now. The Second and Third Laws of Thermodynamics
18.3)
124
. S= So we may write dS = (18. S is also a state function .1. S. Entropy and the Second Law of Thermodynamics
We learned from statistical mechanics that entropy. Hence.

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

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

3. 6. 2. So. The Third Law of Thermodynamics
Consider the ﬁrst law for a reversible change at constant volume. A useful perpetual motion machine does not exist.6)
From our earlier discussion of heat capacity dq = CV dT (CV since constant volume). Work must be done to transfer heat from a cold to a hot reservoir.1. dU = dq + dw = dq − Pex dV (18. Spontaneous processes are irreversible in character. T
(18.18. A cyclic process must transfer heat from a hot to cold reservoir if it is to convert heat into work. the second law has a number of equivalent statements 1.8)
127
.2. Statements of the Second Law Unlike the ﬁrst law. The entropy of the universe is increasing 5. 4. So CV dT =⇒ 4S = dS = T Z
T2
(18.1. The entropy of an isolated system will always increase in a spontaneous process (the principle of Clausius)
18. dU = CV dT but also dU = T dS.7)
T1
CV dT.

12)
From a macroscopic point of view S0 is arbitrary. O2 etc. To derive the mathematical statement of the third laws we starting with Z T2 CP dT (18.
128
.g. Ar.10) 4S = T T1 now let T1 → 0 4S = S2 − S0 = Z
T2
0
CP dT T
(18. CO). However.. S0 6= 0 for imperfect crystals and crystals of asymmetric molecules (e. The Third Law Verbal statement The third law of thermodynamics permits the absolute measurement of entropy.). Consider the heat capacity near T → 0.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 (18.9) 4S = T T1 18. Thus CP → 0.11)
Hence the mathematical statement of the third law is Z T2 CP S(T2 ) = dT + S0 T 0
(18. Alternative statement of the third law: Absolute zero is unattainable..g. a microscopic point of view suggests S0 = 0 for perfect crystals of atoms or of totally symmetric molecules (e. For S0 to have signiﬁcance
CP T
must be ﬁnite (not inﬁnite) as T → 0.2.1.

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

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

Equations
• The Boltzmann equation is • The Boltzmann distribution : g e−β i P i −β j gj e X
j
j
S = k ln W.16)
131
131
. The equations are collected here simply for handy reference for you while working the problem sets.Key Equations for Exam 3
Listed here are some of the key equations for Exam 3.14)
(18. This section should not substitute for your studying of the rest of this material.
(18. The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations.15)
• The canonical partition function is Q=
gj e−βEj
(18.

21)
• The ensemble average of any property is given by 1 X ¯ Oi gi e−β i .V ¡ ∂Q ¢ 1 1 = βQ ∂V n.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.V
n.17) N! • The Translational Partition Function V qtrans = 3 (18. σθr
2
(18.V ´ ∂ ln Q = −kβ ∂β n.19) 2πmkT is the thermal de Broglie wavelength.• The relation between the partition function and the molecular partition function is qN Q = mol .18) Λ where h Λ≡ √ (18. O= Q i
(18. • The Rotational Partition Function (linear molecules) is T qrot ≈ .β
132
.β = β
³
=−
+ k ln Q ¡ ∂ ln Q ¢
∂V
³
∂ ln Q ∂β
´
n. (18.22)
• The relations between the canonical partition function and the thermodynamics variables are Internal energy Entropy Helmholtz Free Energy A = −kT³ln Q ´
1 U = −Q ∂Q ∂β
S
Pressure
P
n.

23)
(18.25)
(18.27)
(18.28)
0
CP dT + S0 T
(18. dU = T dS − P dV. • The second law • The third law T dS ≥ dq. 3
(18.
133
.24)
4U = q + w. S(T2 ) = Z
T2
(18. Also.
(18.29)
• Debye’s law for entropy at very low temperatures Sm (T ∗ ) =
∗ CP m .30)
∗ where CP m is the molar heat capacity at the lowest temperature for which there is data.• P V work is • Heat capacity: • General forms of the ﬁrst law:
dw = −P dV. in diﬀerential form this is dU = dq − Pex dV. dq = C(t)dT.26)
(18.

Part IV Basics of Thermodynamics
134
134
.

19. here too is energy the key property with which to work. So far we have encountered two state functions which characterize the energy of a macroscopic system–the internal energy and. (which you are familiar with from general chemistry) serves are a common point which connects thermodynamics.19. The Other Important State Functions of Thermodynamics
As was the case in quantum mechanics.1. Consequently. 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 equilibrium constant for a thermodynamic process. and kinetics–topics we will encounter throughout the year. K.
135
135
. the concept of equilibrium plays a key role in much of what we will discuss for the remainder of the year. electrochemistry.

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.
136
.2.1)
we say that the natural (most convenient) variables for the equation of state for U are S and V . This is U = U(S. (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. The other pairs of natural variables being (S and P ). Enthalpy
We want a state function whose natural variables are S and P Let us try the deﬁnition H ≡ U + P V. it is handy to deﬁne state functions which have diﬀerent pairs of natural variables.From the ﬁrst law as stated as dU = T dS − P dV (19.

but dU = T dS − P dV. consider an reversibly expanding gas under constant pressure (dP = 0) and adiabatic (dq = 0) conditions. Since the process is adiabatic no heat energy can ﬂow in to compensate for the work done and the gas cools.3. in doing so it must lose energy. The total internal energy decreases. As Freshmen we learn this as 4H = qp . Helmholtz Free Energy
Now we want a state function whose natural variables are T and V
137
. If the process occurs at constant pressure then the enthalpy change is the heat given oﬀ or taken in.3)
Enthalpy is the total energy of the system minus the pressure volume energy.2. The enthalpy of the system on the other hand does not change–it is the internal energy adjusted by an amount of energy equal to the P V work done by the system. so (19.1. So a change in enthalpy is the change in internal energy adjusted for the P V work done.2)
/ / dH = T dS − P dV + P dV + V dP
= T dS + V dP. For example.
19. Hence Enthalpy does indeed have the desired natural variables. 19.Now formally dH = dU + d(P V ) = dU + P dV + V dP. Heuristic deﬁnition:
(19. The system does work during the expansion.

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. Hence Gibbs free energy does indeed have the desired natural variables. but from above dH = T dS + V dP.4)
/ / dA = T dS − P dV − T dS − SdT
= −P dV − SdT.4. Now formally dG = dH + d(T S) = dH − T dS − SdT.1.
(19. (19. 19. Formally dA = dU − d(T S) = dU − T dS − SdT.7) (19.Let us try the deﬁnition A ≡ U − T S. so dG = T dS + V dP − T dS − SdT / / = V dP − SdT. so (19.3. 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.
19.6)
138
.5)
Hence Helmholtz free energy does indeed have the desired natural variables. but dU = T dS − P dV.

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.
19. ¶ ¶ ¶ µ µ ∂ (U + P V ) ∂U ∂V CP = = +P (19.5.8)
The constant pressure heat capcity can then be expressed in terms of enthalpy as ¶ µ ∂H .4. Heat Capacity of Gases
19.10) (19.11) CP = ∂T P So. (19.13)
P
139
.1. 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.1.12) ∂T ∂T P ∂T P P ¡ ¢ ¡ ¢ note ∂U P is not CV we need ∂U V .5.9) (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 (19.19.

15)
∂P ∂T
¶
(19. ∂T P ∂V T ¡ ¢ ¡ ∂U ¢ Recall the expression for internal pressure ∂V T = T ∂P V − P .17) ∂T P ∂T V nRT nR nR = nR = CV + T P V PV Thus CP = CV + nR or CP m = CV m + R (19.6.14) CP = ∂V T ∂T P ∂T P V ¶ ∙µ ¶ µ ¸ ∂U ∂V = CV + +P .18)
19. 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
¶
(19.16)
V
Example: Ideal gases 1.thus ¶ µ ¶ ¶ µ ∂V ∂U ∂V + +P (19. Ideal gas (equation of state: P V = nRT ): This equation is easily made explicit in either P or V so we don’t need any of the above replacements ¶ µ ¶ µ ∂P ∂V CP = CV + T (19. The Maxwell Relations
Summary of thermodynamic relations we’ve seen so far Deﬁnitions and relations: • H = U + PV
140
.

• A = U − TS • G = H − TS • CV = ¡ ∂U ¢
∂T V
.
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. (See handout and Homework)
141
.

Hence at equilibrium (dA)T.V = dq − T dS From the second law. T dS ≥ dq for a spontaneous process.1)
(20.V ≤ 0 for a spontaneous process. Chemical Potential
20. (dA)T.2)
.V = 0. 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. Spontaneity of processes
Two factors drive spontaneous processes 1. 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. (dA)T.1.20. The tendency to minimize energy 2.

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

For constant T and P = Pex . For a reversible process dq = T dS and work is maximal. The total diﬀerential of A is also dA = dq + dw − T dS − SdT. In general dw = dw0 − Pex dV where dw0 is the non-P V work.P = dq + w0 − T dS.P = dwmax =⇒ (4G)T. As we have stated in words a number of times before. Chemical potential
What if the amount of substance can change?
144
.These expressions are quite general. The total diﬀerential of G becomes dG = dq + dw0 − Pex dV + P dV + V dP − T dS − SdT. as stated earlier. The total diﬀerential of G is also dG = dq + dw + P dV + V dP − T dS − SdT. the Gibbs free energy is the energy of the system available to do non-P V work. For reversible processes q = T dS and this becomes
0 0 (dG)T.9)
(20.7)
(20.P = wmax
(20.10)
So.
20.8)
(20. but i) only P V work and ii) closed systems. (dG)T. Hence (dA)T = dwmax =⇒ (4A)T = wmax .2.

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

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

For example. 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. Reference States Thermodynamics is founded on the concept of energy which we know to have an arbitrary scale. but it is often the case that the reference state is chosen to be some ideal state.3. Let us consider the activity of a real gas for the above reference function and reference state.18) The deﬁnition of activity implies that γ i = 1 at g(ζ ª ) (the reference state) 20. γi ≡ which we can rearrange as ai = γ i g(ζ).1. Note: the activity of gases as referenced to pressure has the special name fugacity (fugacity is a special case of activity). ai g(ζ) (20.17)
147
. (20. That is. The choice of this state is completely up to us. Because of this it is always necessary to specify a reference state to which our real state can be compared.This implicit deﬁnition is awkward so for convenience one deﬁnes the activity coeﬃcient as the argument of the above limit. we can deﬁne are zero of energy any where we want.

Activity and the Chemical Potential One cannot measure absolute chemical potentials.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.22)
148
. By convention we chose a standard state and measure relative to that state.2. i (20. i i i i i i (20. For the state of interest μi = μª + RT ln ai (20.Our reference function is very simple: g(ζ) = ζ = P . only relative potentials can be measured. This ideal state is in turn referenced to the standard state. Based on the condition that γ → 1 as we approach the reference state (P = 0 in this case) we see that the activity (or fugacity) of a real gas becomes equal to pressure for low pressures
20. μi − μª = RT ln ai . P (20.20)
Rather than referencing to the standard state one can also reference to any convenient “ideal” state. so γ= a ⇒ a = γP.3. 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 .

Thus μ = μª + RT ln f. then at a given pressure μ = μª + RT ln a.Thus. (20. (20. μi = μid − RT ln aid + RT ln ai i i (20.24)
Now we integrate from the reference state to the current state of interest Z Z RT id dP. (20. Starting from the begining dμ
id
dμid = Vm dP RT dP.26)
(20.28) (20.25) dμ = μª Pª P This gives P . μid → μª ). (Note that as P → 1. so a = f for real gasses.27)
For gases activity is usually called fugacity and given the symbol f . dμid = P
z}|{ = dGm = −Sm dT + Vm dP
=0
(20. Lets say our gas is not ideal. so μid − μª = RT ln μid = μª + RT ln P. but any pressure.29)
149
. Pª The usual standard state is the ideal gas at P ª = 1.23)
μi − μid = +RT ln ai − RT ln aid i i ai = RT ln id ai
Example: Real and ideal gases at constant temperature.

31) (20.e.33)
(20.34)
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.30)
and at elevation h
z }| { μ (0) = μ + RT ln 1 = μª μid (h) = μª + RT ln Ph
=0
(20.32)
The gas ﬁelds the gravitational force which gives it a potential energy per mole of Mgh at height h.
150
. P ª = 1 atm. We have an ideal gas so. So at sea level
id ª
(20. i. we want to reference to the ideal gas at the current pressure P. μ = μid − RT ln P + RT ln f f μ = μid + RT ln .Lets say that instead of referencing to the ideal gas at P = 1. 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. P Example: The barometric equation for an ideal gas. This is easily done by using μª = μid − RT ln P in the above equation for μ. μid = μª + RT ln P where we will take the reference state to be at sea level.

1)
151
151
. for this process. 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. The quantity aB deﬁnes the equilibrium constant. Equilibrium
First let us consider the equilibrium A B.21. if we multiply the above by n moles we have aB −4Gª = nRT ln aA as a consequence of the equilibrium condition.3) (21. Since A and B are in equilibrium their chemical potentials must be equal μA = μB Now.2) (21. aA (21. Ka .

5)
4μ = μª − μª + RT ln aB − +RT ln aA B A aB 4μ = 4μª + RT ln .4)
μª + RT ln aA + 4μ = μª + RT ln aB A B
(21. Consider a more complicated equilibrium aA + bB cC + dD. aA
If the 4G < 0 then the transition A → B proceeds spontaneously as written.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. The equilibrium condition is aμA + bμB = cμC + dμD .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
(21.9)
152
. aA
Again multiplying by n gives 4G = 4Gª + nRT ln aB . In a manner similar to the above aμª + aRT ln aA + bμª + bRT ln aB = cμª + cRT ln aC + dμª + dRT ln aD (21.7)
(21.6)
(21.

21.11)
which is related to Ka by Ka =
0 KC
. ¶
(21. 21. The Partition Coeﬃcient Up to now we have only considered miscible solutions.
(21.3.4.10)
Note: n is absent in the above since the molar values are implied by the stoichiometry. 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
.
153
.0.0. We now consider the problem of determining the equilibrium concentrations of a solute A in both phases of an immiscible mixture.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.

15)
[A]β . 4Gª ≡ Gª −Gª . [A]α
(21.14) (21. 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 .13)
where. The equilibrium constant for this process has a special α α→β β β/α name. P β/α ≡ Kpart .The equilibrium equation is Aα Aβ The equilibrium expression for this process is 4Gα→β = 0 = 4Gª − nRT ln Ka .16)
Knowledge of the partition function is important on the delivery of drugs because. it is called the partition coeﬃcient. to enter the body. the drugs must transfer between an aqueous phase and a oil phase. α aA ª
(21. for species A in the α—β mixture.
154
. α→β (21.

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

156
156
(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.22.1)
.A − bSm. 4rxn H > 0 for Endothermic reactions.C + dSm. Chemical Reactions
Up to now we have only been considering systems in the absence of chemical reactions. 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.B
22.1.D − aSm.

97 kJ H2 + 1 O2 →H2 O(liq) 4rxn H ª = −285.2)
157
.830) = 44. Example: Formation of water • H2 + 1 O2 = H2 O not 2H2 +O2 = 2H2 O 2 • 4rxn H = ponent.2.1.818 − (−285. H2 .012 kJ
22.49 kJ
The heat of formation 4f H ª is the 4rxn H at STP in forming a compound from its constituent atoms in their natural states. 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. Heats of Formation Hess’s Law of heat summation: 4rxn H is independent of chemical pathway Example: C2 H2 +H2 = C2 H4 .22.1. Temperature dependence of the heat of reaction Z T2 4rxn CP dT 4rxn H(T2 ) = 4rxn H(T1 ) +
T1
(22. P
i
ν i 4f H(i). 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. C(graphite) are examples of atoms in their natural state.1.83 kJ 2 C2 H2 +H2 = C2 H4 4rxn H ª = −174.63 kJ 2 2CO2 +2H2 O(liq)→C2 H4 + 3O2 4rxn H ª = +1410. O2 .830 kJ 2 H2 O(liq)→H2 O(gas)
4rxn H ª = −241.818 kJ 2 H2 + 1 O2 = H2 O(liq) 4f H ª = −285.

4rxn G = G(products) − G(reactants) = (remember μi = Gm. 4rxn G = i
i i 4rx n Gª
X
i
ν i μi .22. z }| { X X ν i μª + RT ν i ln ai . Ka depends on T but is independent of P.
(22.4)
(22. Reversible reactions
Recall the requirement for a spontaneous change: 4G < 0 for constant T and P.3)
(22.i for pure substance i).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. 4rxn G = 0 and Q = Ka (Thermodynamic equilibrium constant).
158
. where Q ≡
i
aν i is the activity quotient.7)
• Note that the activity of any pure solid or liquid is for all practical purposes equal to 1. i
At equilibrium. i So. As we saw before μi can be deﬁned in terms of activity μi = μª + RT ln ai .6)
4rxn G = 4rxn Gª + RT ln Q. For the reaction aA + bB = cC + dD Ka = ac ad C D aa ab A B (22.2.

15)
159
.10)
(22. we get ¶ µ 4rxn H ª ∂ ln Ka ind. a b PA PB (P ª aA )a (P ª aB )b
i
(22. Temperature Dependence of Ka
Starting with G =´H − T S or G/T = H/T − S. d ln Ka =− = ∂(1/T ) P of P d(1/T ) R or (using
d d(1/T )
(22.• For ideal gases.3.12)
=
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
(22.9)
22.13)
(22. ³ From this ∂(G/T)) = H. 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 .11)
(22. 4rxn G = 4rxn Gª + RT ln Q becomes 0 = 4rxn Gª + RT ln Ka ⇒ 4rxn Gª = −RT ln Ka . (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 .
So at equilibrium.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
(22.8)
νi
.

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

(23. To understand these processes we must know something about how ions behave in solution.
23.23. Ionics
Many chemical processes involve electrolytes and or acids and bases. 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 . Ionic Activities
Consider a salt in solution Mv+ Xv− → v+ M z+ (aq) + v− X z− (aq).4)
161
161
.1)
where v+ (v− ) is the number of cations (anions) and z+ (z− ) is the charge on the cation (anion). ln aj = RT and ln asalt = j = + or − (23.3) (23.1.2)
μsalt − μª salt . RT
(23.

alternatively. This suggests that the interesting quantity is μsalt : v μª μsalt 1/v = salt + RT ln asalt . a− = γ − m− . asalt = av+ av−
(23.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. The mean ionic activity coeﬃcient is
+ − γ ± = (γ + γ − )
(23. (23.11)
162
.
(23. Ionic activity coeﬃcients The activity coeﬃcients for ionic solutions can also be deﬁned via a+ = γ + m+ .1.5)
So.10)
v
v
1/v
. 23.9) The quantity a± is the mean ionic activity.
ln asalt = v+ ln a+ + v− ln a− or.7)
It is the case that 1 mole of salt behaves like v = v+ + v− moles of nonelectrolytes in terms of the colligative properties.1.8) v v We see that 1/v asalt = (av+ av− )1/v ≡ a± . (23. where m+ = v+ m and m− = v− m.6)
(23.

vmM1 (23. Theory of Electrolytic Solutions
Ionic strength is deﬁned as I= 1X 2 z mi . γ + and γ − cannot be measured individually.2. Recall how γ was calculated from the Gibbs-Duhem equation: Z m j ln γ ± = −j − dm0 .12)
where the subscript 1 refers to the solvent.14)
23. a− .16)
163
. It is convenient to redeﬁne the osmotic coeﬃcient as φ= −1000 g/kg ln a1 .13)
(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. Similarly freezing point depression is redeﬁned as θ = vφKf m. ln γ ± = 1 − Ba0 I
(23. m0 0 where j = 1 − φ.15)
where z is the charge of the ion and m its concentration. 2 i i
(23.The quantities a+ . So. vφ corresponds to the empirical factor i discussed earlier.

(23. (23. which is observed exP perimentally (recall I = 1 i zi2 mi ). Ion Mobility
Current. Q: I= dQ dt (23. ε is the dielectric constant for the pure solvent and L is Avogadro’s number. ρ• is the density of the pure solvent.where α= e3 (εkT )3/2 B= µ 2πρ• L 1000 ¶1/2 . I is given by the rate of change (in time) of charge. (23. Notice that the parameters α and B depend only on the solvent.20) v+ + v− 1− I This equation works well to ionic strengths of about I = 0.1
23.19) This gives the dependence of ln γ ± for dilute solutions (m → 0).21)
164
. It is seen that √ the DHLL correctly predicts the m dependence of ln γ ± .17)
8πLe2 ρ• . e is the charge on the electron. 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 .3.18) 1000εkT a0 is the radius of closest approach. 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. (23.

Ion mobility
165
. ε: w = −εQ (23.22) 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.(Electrical) work. is required to move a change through a potential (or voltage). w. • Faraday’s constant F = Le = 96485 C/mol (Avogadro’s number of electrons) 23.23)
Conductance is the inverse of the resistance (R−1 ).602177 × 10−19 C.3. Some relevant constants • charge of an electron e = 1.1.

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 = +.30)
The ions quickly reach terminal velocity. where E is the electric ﬁeld. dx
(23. −. Hence Fi = 0.29)
The moving ions experience a viscous drag f that is proportional to their velocities.27)
(23.26)
(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. (23.31) f The drag f has three basic origins. the viscous drag equals the Coulomb force. dt dt
(23. (23.. So the total force on the ions is a sum of the Coulomb force and the viscous drag Fi = zi eE − fvi (in solution).25)
Ni Ni dNi Avi 4t =⇒ = Avi V dt V Ni Avi V (in vacuum)
(23.e.
166
.24)
dQi dNi = |zi | e .28)
Fi = mai = m
dvi = zi eE. zi eE zi eE = f vi =⇒ vi = . dt
(23. i. E = Also recall Newton’s law
dε .

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

34)
Suppose a salt has a degree of dissociation α (α = 1 for strong electrolytes) to produce ν + cations and ν − anions. 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.
168
. V l (23. ui which is the ion’s velocity per ﬁeld. vi ui = . then each mole of salt gives: N+ = αν + Ln and N− = αν − Ln. where l is the separation of the l plates.32) E For the case for parallel plate capacitors E = ε .A more fundamental quantity than ion velocity is the ion mobility. (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. =1 z }| { / ν +/ |z+ | u+ A / Vεl / F / ν + |z+ | u+ u+ α n I+ = = = (23. (23. So. vi l .35)
It is of interest to determine the ratio of the current carried by the cation versus the anion.33) ui = ε Here the current carried by ion i is Ii = |zi | e Ni ui ε A .

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

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.

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

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. 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
. 4Gv→s = wdis + wtr + wch = wdis + wch (24.

1. = − 8π 0 ri
(24.5)
173
. wch = + (ze)2 8π 0 εs ri (24. 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. So. 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 .2)
where z is the oxidation state of the ion.1.4)
The above expression is 4Gv→s /ion. For n moles of ions (nL = N) 4Gv→s (24. Work done in charging the sphere: The only diﬀerence in charging the sphere is that the sign of the work will be diﬀerent and that since we are charging in a solvent we must multiply the permittivity of free space by the dielectric constant of the solvent. e is the charge of the electron.3)
24.

24.3.
174
. 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 =
(24.1. Ion Transfer Between Phases We can quickly generalize the Born model to describe ion transfer between phases in a solution of two immiscible phases Consider an immiscible solution of two phases α and β having dielectric constants εα and εβ .The dielectric constant of any solvent is always greater than unity so ε1s − 1 is always negative hence 4Gv→s < 0.6)
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
(24.2. 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.7)
24. Thus ions always exist more stably in solution than in a vacuum.1.

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

1. 3. Changes in solvent structure: the local environment of the ion has a diﬀerent arrangement of solvent molecules than that of the bulk solvent. Speciﬁc interactions: any interaction energy speciﬁc to the particular ionsolvent pair: Hydrogen bonding being the prime example. 2. 4. Annihilation of defects: A small ion may be captured in a micro-cavity within the solvent releasing the energy of the micro-cavity defect.
176
. The solvophobic eﬀect: a cavity must form in the solvent to accommodate the ion. so the initial structure of the solvent must breakdown and the new structure must form.

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. 177
177
dH = T dS + V dP dA = −SdT − P dV dG = −SdT + V dP
(25.2)
.1)
(25.
Equations
• Some thermodynamic relations H = U + PV A = U − TS G = H − TS • The chemical potential equation μi = μª + RT ln ai i • The 4G equation (this should be posted on your refrigerator) 4G = 4Gª + RT ln Q.25. The equations are collected here simply for handy reference for you while working the problem sets. Key Equations for Exam 4
Listed here are some of the key equations for Exam 4. 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

ny Ez.nz . = b b r nz πz 2 sin = c c r (26.nz The total wavefunction is n2 h2 x .
(26.16)
√ ny πy nz πz 2 2 nx πx sin sin ψ=√ sin a b c abc E = Ex.20)
185
. −~2 d2 ψx −~2 1 d2 ψx = Ex =⇒ = Ex ψx 2m ψx dx2 2m dx2 −~2 d2 ψy −~2 1 d2 ψy = Ey =⇒ = Ey ψy 2m ψy dy 2 2m dy 2 −~2 d2 ψz −~2 1 d2 ψz = Ez =⇒ = Ez ψz 2m ψz dz 2 2m dz 2 which we recognize as the 1D particle in a box equations. f (x) is a constant.18) nx πx 2 sin . 8mb2 n2 h2 z = .nx = Ey. 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.17) (26.19)
and the total energy is (26. a a r ny πy 2 sin . 8ma2 n2 h2 y = . 8mc2 (26.nx + Ey. Hence we immediately have ψx = ψy ψz and Ex.So.ny + Ez.

Degeneracy The 3D particle in a box model brings up the concept of degeneracy. When n(> 1) states have the same total energy they are said to be n-fold degenerate. (nx = 1. Let the 3D box be a cube (a = b = c) then the states (nx = 2. ny = 2. ny = 1. (26. (nx = 1. ny = 1. nz = 1). nz = 1).21)
186
. nz = 2) have the same total energy and thus are degenerate.

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

e. Equality: ˆ if α = β.— 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. ˆˆ 4. Multiplication: ³ ´ ˆ (x) = α βf (x) ˆ αβf ˆ ˆ (27.3)
ˆˆ ˆ α β αf (x) = β (ˆ f (x)) . ˆ ˆ ˆ then (ˆ + β)f (x) = αf (x) + βf (x) = g(x) + h(x) α ˆ 3..5) (27. 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 (27.2)
Algebraic rules for operators 1.1) 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.g. " #" # " # 1 0 3 1 3 1 = (27.6)
188
. ˆˆ but in general αβf (x) 6= β αf (x). then αf (x) = g(x) = βf (x) ˆ ˆ ˆ 2. Addition: ˆ if αf (x) = g(x) and βf (x) = h(x).

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

then βf (x) = bf (x). Commuting operators and simultaneous sets of eigenfunctions. The only way for ˆ ˆ = bf.11)
ˆ which states that βf is an eigenfunction of α with eigenvalue a. ³ ´ ˆ α β (ˆ f ) = α βf ˆ ˆ ³ ´ ³ ´ ˆ α βf = a βf . ˆ (27. β = 0 and α and β are said to commute with one another. then α. ˆ On the other hand. ˆ ˆ (27. We shall see that eigenvalues of certain operator can be identiﬁed as experimental observables. αf (x) = g(x) ˆ ˆ becomes the eigenvalue equation αf (x) = af (x). ˆ Thus
(27. ˆ ˆ The proof goes as follows: On the one hand. then the operator equation. ˆ α ˆ ˆ β (ˆ f ) = β (af) = aβf because f is an eigenfunction of α.h i ˆ = β α. ˆ ˆ If αf (x) = af (x) and β and α commute. this to be true is if βf
190
.10)
ˆ because β and α commute.9)
(27.8)
The eigenvalue equation is of fundamental importance in quantum theory. ˆˆ ˆ ˆ If αβ ˆ ˆ ˆ The eigenvalue equation: If αf (x) = g(x) and g(x) = af(x).

j 6= k.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. Orthogonality. and the Superposition Principle
Theorem 1: The eigenfunctions of a Hermitian operator corresponding to diﬀerent eigenvalues are orthogonal: Z ψ∗ ψk = 0.2.13)
i
191
. Completeness. (27.27.

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

−l + 1 . . simplifying gives l = −l0 Thus mmax = l. mmin = −l and so m = l.46)
substituting in the relation we just found for k gives
(28.48) (28.47)
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 . φ). (28. −l. .51)
199
. ˆ L2 ψlm = l(l + 1)ψ lm ˆ Lz ψlm = mψ lm (28. Quantum Properties of Angular Momentum
The eigenfunctions of angular momentum are entirely speciﬁed by two quantum numbers l and m: ψlm . l − 2.50)
The solutions to this partial diﬀerential equation are known to be the spherical harmonic functions ψ lm = Ylm (θ.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. (28.5. . l − 1.45)
and
(28. This also implies that the number of ‘rungs’ is 2l + 1 and that l must be either an integer or a half-integer. l(l + 1) − l02 + l0 = 0. .

They are also built-in functions of Mathematica. We know that there are 2l + 1 diﬀerent m values for a particular l value. ( Z 2π Z π 1 l0 = l and m0 = m (28. φ) sin θdθdφ = 0 0 l0 6= l or m0 6= m 0 0 28. The spherical harmonics (and hence the angular momentum wavefunctions) are orthonormal. the energy levels are determined only by the value of l. meaning. The rigid rotor Rotational energy For general rotation in three dimensions the is ~2 ˆ ˆ H = L2 . Both the spherical harmonics and the Legendra polynomials are tabulated.The spherical harmonics are functions of two variables. (28. φ)Ylm (θ.
|m| |m|
(28. 2I so the Schrödinger equation is ~2 ˆ ~2 ˆ Hψ lm = Elm ψlm ⇒ L2 ψlm = Elm ψlm ⇒ l(l + 1)ψlm = Elm ψlm . φ) = APl (θ)eimφ . We say the there is a 2l + 1 degeneracy of the energy levels.56) 2I 8π2 I There is no m dependence for the energy.52)
where the Pl (θ) are the Legendra polynomials and A is normalization constant.55) (28.1. 2I 2I Thus Elm = (28. All 2l + 1 of these wavefunctions correspond to the same energy.5.53) Yl∗m0 (θ. In other words. but they are a product of a function only of θ and a function only of φ. ψlm = Ylm (θ.54)
l(l + 1)h2 l(l + 1)~2 = = El .
200
.

One peculiarity of this system is that the wavefunctions are 4π periodic (and 2π antiperiodic): ψs (θ) = −ψs (θ + 2π) (29.1. Addition of Angular Momentum
29. These systems have no classical analogs. Spin Angular Momentum
We learned above that l may take on integer or half-integer values.1) and ψ s (θ) = ψs (θ + 4π). The values of m = ms are limited to +1/2 and −1/2. One example of such a system is the spin of an electron. ∗ ∗ ∗ See in-class demonstration: the belt trick ∗ ∗∗
201
201
. (29.2)
That means that the system has to ‘rotate’ twice (in spin space not coordinate space) to get back to its original state. Systems in which l takes on half-integer values are peculiar. l = s = 1/2.29.

we use J when we speak generally. The electrons in many electron atoms couple. • we will not use this method. the total angular momentum.29. J.2. One measures. (Ms = i msi ) P • ﬁnd the total orbital angular momentum L = Mmax .max . 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 . (M = i mi ) • then J = L + S 2.2. 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.1. 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. however. The are two main coupling schemes which account for the total angular momentum of the atom.)
202
. 29. 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. 1.

j1 + j2 − 1. |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.5)
The total angular momentum is quantized is exactly the same manner as any other angular momentum.ˆ ˆ ˆ The total angular momentum is JT = J1 + J2 . 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. . Jmin = |j1 − j2 | . That is. (29. . 29. An Example: Two Electrons The table below shows the total spin angular momentum S for a two electron system (29.6)
203
. . |j1 − j2 | + 1. Thus the allowed values of J are J = j1 + j2 . .2. The maximum value of J is determined by the maximum value of M by Jmax = Mmax = m1max + m2max = j1 + j2 (29.3)
We need to determine the allowed values of the total angular momentum quantum number J.2.

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

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

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

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

(30. (0)
(30. This is given by Z (1) ˆ En = ψ(0)∗ H (1) ψ(0) dx. This process get algebraically intensive so we will only go as far as listing the ﬁrst order energy correction. . • The procedure is repeated to get higher and higher order approximations.
√ 2 This has energy levels En = ~ω(n+ 1 ) and wavefunctions An Hn ( αx)e−αx /2 .2) n n
all space
ˆ where H (1) is the ﬁrst order correction to the Hamiltonian–the perturbation. .• The ﬁrst order energy is then used to make a ﬁrst order approximation to the wavefunction.3)
• The perturbative part of the Hamiltonian is ˆ H (1) = ax4 . • The obvious solvable system is the harmonic oscillator: 1 ~2 d2 ˆ + kx2 . The nth state energy in perturbation theory:
(0) (1) En = En + En + . . 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.4)
208
. H=− 2 2m dx 2 (30. 2 q where α = km ~ (30.1)
(1)
where En is the nth state energy for the unperturbed (solvable) system and En is the ﬁrst order correction.

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

)
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.

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

° .
212
. i=1 The states ψ 1 and ψ2 are eigenfunctions of the two level Hamiltonian. we can not use our usual procedure of writing down the classical Hamiltonian and then replacing the variables with their corresponding operators.Consequently. ˆ H=
1 δ 1.2)
where δ j.°
+ 2 δ 2.
(31. 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 . j 6= k (31.° “projects out” the j th state of the wavefunction being acted on.1)
TLS
R where TLS dΩ means integration over the two level space (which is really just the P sum 2 ).

° ) (aψ 1
+ bψ2 )
2 δ 2.
We can invert above equations and solve for ψ1 and ψ2 in terms of ψL and ψR 1 1 ψ1 = √ ψL + √ ψR 2 2 and 1 1 ψ2 = √ ψL − √ ψR .° + =
1 δ 1. 2 2 (31.7)
213
. then ˆ Hψ = ( 1 δ 1.° 2 δ 2.°
(31.4)
(31.5)
states.6)
(31.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.

31.9)
ˆ En ψn (x)e− ~ En t = e− ~ En t Hψn (x) ˆ En ψn (x) = Hψ n (x)
(31. t)
i ˆ = Hψn (x)e− ~ En t i ˆ = Hψn (x)e− ~ En t i ˆ = Hψn (x)e− ~ En t i
(31.10)
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. t) ≡ ψn (x)e− ~ En t
i
(31.
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. 0)Ψn (x. This is given by ¯Z ¯2 ¯ ¯ ∗ P (x. What has been kept hidden up to now is the fact that the eigenfunctions are really multiplied by a phase factor of the form .2. t) = ¯ Ψn (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. t)dx¯ (31. Ψn (x.8)
We can verify this by obtaining the time independent Schrödinger equation from the more general time dependent ∂Ψn (x. t) ∂t i ∂ψn (x)e− ~ En t i~ ∂t i ∂e− ~ En t i~ψ n (x) ¶ ∂t µ i i i~ψ n (x) − En e− ~ En t ~ i~
i
ˆ = HΨn (x.

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

15) P (x. This leaves ¯2 ¯Z ¯ ¯ ¯ Φ∗ (x. +e +1 = = 4 2 ~ The probability of ﬁnd in the system in its original superposition states is not one for all times t. t)¯ (31.
216
.integrated because the eigenfunctions are orthogonal. 0)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 .

Equations
• The short cut for getting the normalization constant .17)
• How to get the average value for some property. z)|2 dxdydz. The equations are collected here simply for handy reference for you while working the problem sets. N unnorm (31.
(31.Key Equations for Exam 1
Listed here are some of the key equations for Exam 1. ˆ hˆ i = α
space
(31. 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. This section should not substitute for your studying of the rest of this material.18)
217
217
.16)
• The normalized wavefunction: ψnorm = 1 ψ . y. Z ψ∗ αψdxdydz.

21)
ψ∗ ψk j
=
space
1. Lz = 0. ˆ ˆ ˆ ˆ ˆ L m2 h2 ~2 m2 = . Enx .25)
• The energy levels for a particle in a ring are Em =
(31. j 6= k
(31. Lz = i~Lx . ˆ z . ˆ y .
(31.20)
(31.24) L L L and h i h i h i ˆ 2 . Lx = L2 . √ ny πy nz πz nx πx 2 2 sin sin . Ly = i~Lz . 2I 8π2 I (31. sin ψn (x) = √ a b c abc • The energy levels for the 3D particle in a box. 8ma2 8mb2 8mc (
(31.26)
• The normalized wavefunctions for a particle on a ring are 1 ψ = √ eimφ .• The Laplacian
∇ =
2
µ
∂2 ∂2 ∂2 + 2+ 2 ∂x2 ∂y ∂z
¶
. Lx = i~Ly (31.ny .27)
218
. 2π (31.19)
• Normalized wavefunctions for the 3D particle in a box.23)
• Commonly used comutators of the angular momentum operators are h i i i h h ˆ ˆ ˆ ˆ ˆ ˆ ˆ x . Ly = L2 .nz • Orthonormality: Z n2 h2 n2 h2 n2 h2 y x = + + z 2.
j=k . 0.22)
• Superpostion:
ψ=
X
i
ai ϕi
(31.

30)
(31.29) ˆ Lz ψlm = mψ lm (31. • The ﬁrst order energy correction in pertubation theory is Z (1) ˆ ψ(0)∗ H (1) ψ(0) dx.28)
• Degeneracy for general angular momentum is gJ = 2J + 1. ˆ L2 ψlm = l(l + 1)ψ lm • The energy levels for the rigid rotor are El = l(l + 1)~2 .31)
• The trial energy in variation theory is calculated by R ∗ ˆ all ψ trial Hψ trial dx space Etrial = R ∗ all ψ trial ψ trial dx
space
(31. t) ≡ ψn (x)e− ~ En t
i
(31.32)
• In general
Ψn (x.33)
• The left and right superposition states are 1 1 ψL = √ ψ1 + √ ψ2 2 2 and 1 1 ψR = √ ψ1 − √ ψ2 2 2 (31. En = n n
all space
(31.34)
(31. 2I (31.• The eigenfunctions of angular momentum are entirely speciﬁed by two quantum numbers l and m: ψ lm .35)
219
.

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.32. As far as we are concerned. we will • determine the symmetry of a particular molecule. • The types of symmetry it has will determine to which symmetry group it belongs. • The mathematical properties of all the possible groups have been worked out • These mathematical properties translate into a wide variety of variety of physical properties including — Bonding — Properties of wavefunctions — Vibrational modes — Many more applications
221
221
.

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

Example: The C2v Group ˆ ˆ ˆ The C2v group consists of the symmetry elements E.2.3. 32. The “product” of any two members of the group yield a member of the group. 4. In other words.” yields the identity element.
223
. upon “multiplication. C2 . The inverse of every member of the group is also in the group. the wavefunctions must be symmetric or antisymmetric with respect to all elements of the group. for any member of the group one can ﬁnd another member of the group which.
∗ ∗ ∗ See Handout on Naming Point Groups ∗ ∗∗ ∗ ∗ ∗ See Handout on Assigning Point Groups ∗ ∗∗ Associated with a given group is a “multiplication” table. σ v (in-plane) and σ 0v ˆ (transverse). 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
32.1. Symmetry of Functions
In the absence of degeneracy.

In this case one can collect the eigenvalues (either +1 or −1) for each of the four symmetry operators as a four component vector. ˆ — This restriction forces the eigenvalues of σv and σ 0v to be the same for ˆ the A type vectors and opposite for the B type vectors. 1. As it turns out there is four possible sets of eigenvalues–hence four diﬀerent vectors: A1 = (1. −1. 1).Connecting with the C2v group example lets consider the wavefunctions for water. −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. 1) A2 = (1. −1) B2 = (1.
224
. 1. −1. −1) B1 = (1. 1. 1. −1. consider the following. To see where these four vectors come from.

1. Altogether. the vectors represent what is call an irreducible representation of the group.) For the example of the C2v group consider B1 ⊗ B2 = (1. 1) = (1.) ⊗ (y1 . there will always be the same number of vectors as symmetry elements. 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. .4. x3 y3 . . −1. 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. . x2 y2 . . In fact.
225
. −1. −1.1.4) (32. −1) ⊗ (1. . .3. .The above considerations leave four vectors. y3 . Direct Products The direct product of a two vectors is deﬁned as (x1 . x2 . .) = (x1 y1 . y2 . −1. x3 . 1. . −1) = A2 (32.3)
32.

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

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

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

33. however. that motion is some linear combination of fundamental vibrational motions called normal modes. At low energies the normal modes are well approximated as harmonic oscillators. The number of normal modes equals the number of vibrational degrees of freedom.2. This is analogous to writing an arbitrary wavefunction as a linear combination of eigenfunctions. One example was the “left” and “right” states of the two level system. 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.1. Normal Modes Polyatomic molecules can undergo very complicated vibrational motion. Example: Water The point group symmetry of the water molecule is C2v . 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. Regardless of what type of vibrational motion is taking place.1.
229
. the symmetric stretching vibration and the asymmetric stretch. The three modes are the bending vibration.1.33.

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

IR Spectroscopy
IR absorption is exactly the same as regular electronic absorption except the frequency of the electromagnetic radiation is much less. This is in the Infrared region of the electromagnetic spectrum. As for electronic absorption one typically employs the electric dipole approximation.1. Vibrational Spectroscopy and Group Theory
We now investigate how group theory and. The electric dipole approximation • Molecule is viewed as a collection of charges • Multipole expansion monopole + dipole + quadrapole+ · · · 231
231
(34.1)
. in particular. The typical “energies” for IR absorption are from 400 to 4000 cm−1 .34. the character tables can be used to determine IR and Raman spectra and selection rules for polyatomic molecules
34.

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

So we can see immediately that the IR active modes of any molecule having this point group will be A1 .Among these functions are x. B1 . 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). From before we know the modes of water have A1. y. and z. 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. 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.
233
. and B2 . This lose of energy shows up in the scattered light as a new down shifted frequency from that of the original input light frequency. Unlike IR absorption which is based on the electric dipole. The light loses energy to the material in an amount equal to the vibrational energy of the molecules is the sample.2. and B1 symmetry and hence are all IR active and appear in the IR spectrum
34.

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

4)
(35.35. The R was involved in vibrations. under the Born-Oppenheimer approximation. ~2 ˆ2 (35.3)
This is the so-called rigid rotor energy. (35. 2I Now.2) J . R is a parameter. 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 . θ. Then Erot = J(J + 1)hBe with a degeneracy of gJ = 2J + 1 235
235
h 8π 2 I
(35. φ).6)
.1) R 2μ 2μR2 ∂R ∂R 2μ We will now be concerned only with the angular part. = 2μR2 8π 2 I (35. It is common to deﬁne Be ≡ as the rotational constant. For constant R the rotational energy is given by − Erot = J(J + 1)~2 J(J + 1)h2 .5)
(35. Molecular Rotations
Recall that the three degrees of freedom that described the position of the nuclei about the center of mass were (R. We now turn our attention to the angular components to describe rotations.

2. a rotational transition can accompany a vibrational transition.8)
(35. Rotational Spectroscopy
A rotational transition can occur in the same vibrational level n.1.35. This is called a pure rotational transition. Vibrational state dependence: • The R value is dependent on the particular vibrational level. n.9)
is the centrifugal stretching constant. In either case the selection rule for the transition is 4J = ±1. 2.7) 2 where αe is an empirical rotational—vibrational interaction constant. • This is corrected for by the term −J 2 (J + 1)2 Dc . Centrifugal stretching: • Rotation tends to stretch the diatomic distance R. ¶ µ 1 Bn ≡ Be − n + αe . There are two corrections we will now make 1. (35. Alternatively.
236
. • One deﬁnes a rotational interaction constant that depends on the vibrational level. Relaxing the rigid rotor
Of course the rigid rotor is not a perfectly correct model for a diatomic molecule. where Dc ≡
3 4Be ω2 ˜e
(35.
35.

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

carbon dioxide) • Izz = 0. (35. where B= 2.g.There are four classes of polyatomic molecules regarding rotations 1. Ixx = Iyy ˆ ˆ2 ˆ2 • J 2 = Jx + Jy • The Hamiltonian is • The rotational energy is Erot = hBJ(J + 1).12)
~2 ˆ2 ˆ J H= 2Ixx
(35. where A= (35.16) 8π 2 Izz h (35.g.. benzene) • Ixx = Iyy h 8π2 Ixx (35.15)
h .14)
• The rotational energy is Erot = hBJ(J + 1) + h(A − B)K 2 .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. Linear (e.. Symmetric tops (e.17) B= 2 8π Ixx and K is the quantum number describing the projection of the angular momentum onto the z-axis
238
.11)
(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
.g.20)
4.18)
(35. methane) • Ixx = Iyy = Izz
ˆ ˆ2 ˆ2 ˆ2 • J 2 = Jx + Jy + Jz • The Hamiltonian is • The rotational energy is Erot = hBJ(J + 1). where B= h 8π2 Ixx (35.19) ~2 ˆ2 ˆ J H= 2Ixx (35.

240
240
. Molecular spectra. 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. was parameterized by the internuclear distance. We found that in doing so the electronic energy level. on the other hand. Electronic Spectroscopy of Molecules
The electronic spectra of molecules are quite diﬀerent than that of atoms. Atomic spectra consist of single sharp lines due to transitions between energy levels. have numerous lines (bands) due to the fact that electronic transitions are accompanied by vibrational and rotational transitions. Ee . R. Ee as a function of R describe the eﬀective potential for the nuclei.36.1.
36. It had a qualitative shape similar to the Morse potential.

2. ∗ ∗ ∗ See Spectroscopy Supplement p1 ∗ ∗∗ 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. 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. Note: The potential minima are not at the same value of R for each of the electronic states.
241
.1.
36. Absorption Spectra In absorption spectroscopy.1.1.In the ﬁgure below the ground and ﬁrst excited electronic levels (as a function of R) are shown.

Fluorescence Spectra All during the process of absorption.3.1. the process of is taking place. • This requires a lower energy (or “more red”) photon. This is known as the Stokes shift.∗ ∗ ∗ See Spectroscopy Supplement p2 ∗ ∗∗ 36. • The system then very rapidly (on the order of tens to hundreds of femtoseconds) relaxes to the ground vibrational state of the excited electronic state. 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. Hence the Stokes shift.
242
. ∗ ∗ ∗ See Spectroscopy Supplement p3 ∗ ∗∗ As seen in the supplement the ﬂuorescence spectrum is shifted to lower energies (red shifted) from the absorption spectrum.

i → Ψf = ψel. ˆ el.i ψvib.f vib.
36.f ¯ (36. Mathematically this means that the strength of a transition from Ψi = ψel. The Franck—Condon principle When the Born—Oppenheimer approximation is applied to spectroscopic transitions.1)
all space
el space
vib space
243
.2.36. This is down by evaulating the Franck—Condon integral. but we will ingore this). The Franck—Condon principle states that the nuclei do not move during an electronic transition. one obtains the Franck—Condon principle.f ψvib.i ¯ . 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. Assuming the electronic transition is allowed one must calculate the probability of the vibrational transistion as well.f is given by ¯Z ¯ ¯ ¯ ¯ ¯2 ¯Z ¯ ¯ ¯ ¯ Ψ∗ μel Ψi ¯ = ¯ ˆ f ¯ ¯ Z ¯2 ¯ ¯ ψ∗ ψ∗ μel ψel.i ψvib.1.2. 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.

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

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

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

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

(37.i ¯ vib.f ¯ Z
∞
(37.7)
−∞
• The inverse Fourier transformation is Z ∞ h i 1 −1 ˜ ˜ = f(ω)e−iωt dω. f (ω) = f (t) = 2π −∞
(37.5)
vib space
(37.8)
248
.6)
• The Fourier transformation is
˜ = [f (t)] = f (ω) =
f (t)eiωt dt.• The degeneracy of the rigid rotor is gJ = 2J + 1 • Franck—Condon Factor: ¯Z ¯ ¯ ¯ ¯ ¯2 ¯ ¯ ψ∗ ψvib.

Part VII Kinetics and Gases
249
249
.

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

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

n RT |{z}
=L
A simple model for molecular collisions:
252
. For an ideal gas (V = P ). It can be shown from ﬁrst principles that µ ¶3 2 −mv 2 m F (v) = 4π e 2kb T v 2 (38.2.5) 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. So F (v) represents a distribution of speeds.380658 × 10−23 is Boltzmann’s constant.We shall consider stationary isotropic distributions F (v).4) 2πkb T where kb = 1. n = = RT .
38. 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. This is the Maxwell’s distribution (of speeds).

Since the molecules are moving relative to one another we must ﬁnd the average relative velocity. ¯ πM frequency
(38.• Particles are hard spheres of radius σ. P = 1 bar): v = 380.7)
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. v12 = h|v1 − v2 |i ¯ It can be shown that r v12 = ¯
√ √ collision 16RT = 2¯ =⇒ v = 2n∗ πσ 2 v .25 × 109 s−1 . s
collision = 5.6) • The collision frequency = n∗ πσ 2 v For the above model we need to ﬁnd the average collision frequency. frequency λ = 72.8)
Example: Ar at SATP (T = 298 K. • A Particle moving at v sweeps out a cylinder of radius σ and length v4t =⇒ V = πσ2 v4t.5 nm
253
.48 ¯ m .

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

(39. rate laws are empirical. v = f (conc. rate laws are of the form v = k[A1 ]xA 1 [A2 ]xA 2 · · · [An ]xA n . This deﬁnition is useful but must be used with caution since for complicated reactions all the v’s may not be equal.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
. An example of this is ½ bB → cC + dD aA + (39. −b. B.4) 0 B0 → c0 C0 + d0 D0 b A rate law is the mathematical statement of how the reaction velocity depends on concentration. but certainly not all.We deﬁne the reaction velocity as v= 1 d[I] vi dt (39. Many. c or d and I = A. In general an overall reaction is made up of so called elementary reactions Reactant Reactant = → Product overall rxn (39.6)
The reaction is said to be of order xAi in species Ai and it is of overall order P i xA i .5) For the most part. C.3)
where vi = −a.) (39. or D.

One possible set of elementary steps could be elementary rxn A + A → A0 A00 + 2B→ C + D A0 → A00 molecularity Bimolecular Unimolecular Trimolecular .10)
256
. Now.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. Connection to thermodynamics Consider the overall or elementary reaction aA + bB cC + dD
kr kf
(39. 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.Let 2A + 2B = C + D be the overall reaction.9)
where kf is the rate constant for the reaction to proceed in the forward direction and kr is the rate constant for the reaction to proceed in the reverse direction. 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.

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

• 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.
258
. • 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.2. The rates of chemical reactions vary enormously from sub-seconds to years. To obtain the rate from the concentration we must take its time derivative dc(t) . Determination of Rate Laws
Concentrations c(t) are measured not rates. Consequently no one experimental technique can be used.• 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. • For slow reactions (hrs/days) almost any technique for measuring the concentration can be used.

• 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. say. if the concentration drops very sharply 2. Method of isolation • for v = k[A]x [B]y rate laws • start with initial concentrations a and b equal to the stoichometry. 1. if there is an induction period 2.
259
. Integrated rate laws The above diﬀerential methods look directly at the rate law which is a diﬀerential equation.1. Method of initial velocities • for v = k[A]x [B]y rate laws. The main problem with such a method is that randomness in the concentration measurements gets ampliﬁed when taking the derivative. • problems 1. A so v ≈ kax [B]y 39. this gives the overall order of x + y • ﬂood with. The diﬀerential equation is not solved. 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.39.2.2.2.

We now solve the diﬀerential equations to yield what are called the integrated rate law.b. 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.. vi is a negative number).
− (n − 1)vi kt
260
. For example n = 3/2 is a three-halves order rate law. b) The order need not be an integer.

This is the Arrhenious equation Recall the equilibrium constant can also be obtained from kinetics
0 Kc =
kf ' Ka . Temperature and Chemical Kinetics
40. 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 = . take the log of this: ¸ kf = ln kf − ln kr .3)
(A is the constant of integration).4)
Now.1. ln Ka = ln kr ∙ 261
261
(40.5)
. d(1/T ) R where Ea is the Arrhenious activation energy.40. Integration of the above yields ln k = ln A −
Ea Ea =⇒ k = Ae− RT RT
(40.2)
(40.1) (40. kr
(40.

6)
(40. Theoretical approaches to reaction rates predict rate constants of the form k = aT j e−E /RT .8)
(40.1.7)
(40.10)
40.1. Forcing this to coincide with the Arrhenious implies Ea = E 0 + jRT and A = aT j ej
0
(40. Temperature corrections to the Arrhenious parameters The Arrhenious parameters A and Ea are constants.2. Theory of Reaction Rates
Simple collision theory (SCT) • Bimolecular reactions (A. 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.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 40.9)
We can verify this by starting with the Arrhenious equation and substituting the above expressions.B) • Reaction rate determined by molecular collisions
262
.

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
(40.12)
• The rate constant for a bimolecular reaction is v k= [A][B] so SCT predicts k=
pzA B e− L
Em in RT
(40.14)
263
.
• The maximum reaction velocity is vmax = reaction velocity will be less because
zA B L
. 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.

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

Parallel reactions:
265
. Reactions may occur in series or in parallel or both.3.• Deﬁnition: transmission factor.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.19)
• Thermodynamics tells us that
‡ 4G‡ = −RT ln Ka
(40. Multistep Reactions
Up to now. there is many steps from initial reactants to ﬁnal products. f — accounts for the fraction of activated complex that becomes product. • The reaction rate constant for reactants going to products for ACT is
‡ k = f Ka =
kb T ‡ K h a
(40.21)
where 4G‡ = 4H ‡ − T 4S ‡ . • The ACT reaction rate constant now becomes k= This is Eyring’s equation kb T − 4H ‡ 4S‡ e RT e R .22)
40. In general. in what is called a reaction network. — From statistical mechanics. the reactions we have studied have been single step reactions. h
(40.

24) • The concentrations of A. B and C are determined by the system of diﬀerential equations: − d[A] = k1 [A] dt d[B] = k1 [A] − k2 [B] dt d[C] = k2 [B]. They are of the form k1 k2 A→B→C (40.• Parallel reactions are of the form.
1 A + B1 → C
k
(40.23)
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. when solved yields [A] = [A0 ]e−k1 t ¢ k1 [A0 ] ¡ −k1 t [B] = − ek2 t e k2 − k1
¶ µ k2 e−k1 t − k1 ek2 t [C] = [A0 ] − [A] − [B] = [A0 ] 1 − k2 − k1
• See in class animation
266
. for example.

267
. The simplest chain reactions have three distinct steps (discussed below) Chain reactions are extremely important in polymer chemistry Steps of a chain reaction 1. Initiation: Typically a molecule M reacts to form some highly reactive radical M → R·.40.4. Chain Reactions
Chain reactions are reactions which have at least one step that is repeated indefinitely.

Propagation: The radical formed in the initiation step reacts with some so molecule M0 to form another molecule M00 and another radical R0 ·. This step repeats an indeﬁnite number of times.2. 3. 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
. R·+M0 → M00 + R0 ·.

41.1. Gases and the Virial Series
Unlike liquids and solids. (41.3)
a RT − 2. • The ideal gas equation of state P V = nRT. The equation of state can also be expressed in term of density ρ = ρ= mP . This simpliﬁes the theoretical treatment of gases.2)
• The van der Waals gas equation of state P = or
n2 a nRT − 2 V − nb V
(41.41. nRT
m V
(41. We will now look in detail at the gases.4) Vm − b Vm where the parameter a accounts for the attractive forces among the particles and parameter b accounts for the repulsive forces among the particles P = 269
269
. a particular particle has much less signiﬁcant interactions with the other particles.1)
(41. Equations of State
Recall from last semester several of the equations of states for gases.

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

hence
1 Vm
µ
b Vm
¶2
+ ··· . etc.13) (41. 1−x Therefore b a +1+ + z=− RT Vm Vm the ﬁrst term is proportional to in the series expansion.11)
= z so z= 1 a − .
(41.12)
The ﬁrst term is of the form
1 1−x
1 = 1 + x + x2 + · · · . C(t) = b2 .1. b RT Vm 1 − Vm which has the power series expansion (41.14)
1 Vm
and so it can be combined with the
term
µ ¶2 ³ a ´ 1 b z =1+ b− + + ··· .15)
This series can now be compared term by term to the virial series to give expression for the virial coeﬃcients: ³ a ´ .2. RT Vm Vm
(41. D(T ) = b3 .41. 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. (41.16) 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.

Tb . 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 ) + ··· . The Boyle Temperature The temperature at which B(T ) = 0 is called the Boyle temperature.3. The gas behaves more like an ideal The lowest order correction are now V1 m gas at Tb then for other temperatures. 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 + · · · .2. 41.18)
The relation of this expansion to the one in V1 can be obtained.41.17) = 1 + C(T ) Vm Vm ³ ´2 .2.2. (41. (41. (41.19) RT
272
. One ﬁnds (see m homework) B(T ) B 0 (T ) = .

for now treat them as empirical parameters): µ ¶ 9RTc 6Tc2 B(T ) = 1− 2 .2. (41. T3 B(T ) = B0 − where A0 .20)
D(T ) − 3B(T )C(T ) − 2B(T )3 (RT )3
(41. a. b.25) 128Pc T (41. RT T A0 a B0 c − B0 b − 3 . Estimation of Virial Coeﬃcients The virial coeﬃcients can be estimated using empirical equations and tabulated parameters.22) (41.4.23) (41. C(T ) = RT T B0 bc D(T ) = . B0 .C 0 (T ) = and D0 (T ) =
C(T ) − B(T )2 (RT )2
(41. c are tabulated constants • Estimates based on critical values (we will discuss critical values shortly.
• Estimates based on Beattie-Bridgeman constants: c A0 − 3.24)
273
.21)
41.

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

5)
This approximation is quite good even over a rather large pressure range (P −P0 = 100 atm or so). P Ã ¡ ¢! µ ¶ µ ¶ nRT −1 ∂V −1 ∂ nRT −1 P − 2 κT = (42.
275
. α and κT for liquids and solids
Ã ¡ ¢! ∂ nRT 1 1 P = /R = n/ ∂T VP T |{z} P
=n R / /T
(42.b. it is. of course.
V (P ) ≈ V0 [1 − κT (P − P0 )] . Starting with the ideal gas law: V = nRT . the compressibility and expansion of liquids (and solids) are very small.2) = = V ∂P T V ∂P V P
T
=
and
n/T 1 /R/ 1 1 nRT = = (P V ) P P /R/ P n/T | {z }
=nRT
1 α= V
µ
∂V ∂T
¶
P
1 = V
42.42. α and κT for an ideal gas As an exercise we shall calculate α and κT using the ideal gas equation of state (n.1.1. So one can expand the volume in a Taylor series about a known pressure.
(42.1.4)
so.3)
In general. absurd to treat a liquid as an ideal gas)..2. At constant T ¶ ¶2 µ ∂V ∂V (P − P0 ) + (P − P0 )2 + · · · V (P ) = V0 + ∂P ∂P T | {z T } µ
−V0 κT
(42. P0 .

11)
P
276
.1. Use an identity of partial derivatives ∂T ∂T µ ∂U ∂T ¶ =
P
µ
∂U ∂T
¶
+
V
µ
∂U ∂V
¶ µ
T
∂V ∂T
¶
(42.
(42.8) κT − ∂P T rule ∂T V
42. The Relationship Between CP and CV To ﬁnd how CP and CV are related we begin with ¶ µ ∂H . 42.10) CP = ∂T ∂T P ∂T P P ¡ ¢ ¡ ¢ note ∂U P is not CV we need ∂U V . we can apply the cyclic rule for partial derivatives to determine the ratio κα : T ¡ ∂V ¢ ¶ µ α ∂P ∂T P cyclic = ¡ ∂V ¢ = (42.9)
¶ ¶ ¶ µ µ ∂ (U + P V ) ∂U ∂V = +P (42.2.2.
V (T ) ≈ V0 [1 + α(T − T0 )] . Heat Capacity of Gases Revisited
This section is a review from the ﬁrst semester with an additional example beyond the ideal gas.6)
so.7)
As one ﬁnal point.H = U + PV CP = ∂T P so µ
(42.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.

14)
V
For solids and liquids: µ so ∂V ∂T ¶ = V α.17)
T
V
∂T with − ¡ ∂V ¢P ∂P T
¡ ∂V ¢
(42. ∂T P ∂V T ¡ ¢ ¡ ∂U ¢ Recall the expression for internal pressure ∂V T = T ∂P V − P .13)
∂P ∂T
¶
(42. Explicit in P : Replace µ 2.18)
277
. 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.thus ¶ µ ¶ ¶ µ ∂V ∂U ∂V + +P (42. µ ∂P ∂T ¶ = α κT (42. Explicit in V : Replace µ ∂P ∂T ¶ ∂V ∂T ¶ with − ¡ ∂T ¢V ∂P
∂V
P
¡ ∂P ¢
(42.16) κT For gases we need the equation of state which often is conveniently explicit in P or V but not both CP = CV + 1.12) CP = ∂V T ∂T P ∂T P V ¶ ∙µ ¶ µ ¸ ∂U ∂V = CV + +P .15)
P
V
α2 T V (42.

This is explicit P in V so use case 2 above ¶ µ ¶ ¶ ¡ ∂V ¢ µ µ ∂P ∂V ∂V ∂T ¡ ∂V ¢P CP = CV + T = CV − T (42.23)
or
(42.21)
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 (42.20) ∂T P ∂T V ∂T P ∂P T The partial derivatives are ¶ µ ∂V nR + nB 0 . One term viral equation (equation of state: V = nRT + nB).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. nRT − P2 / RT n
(42. P2
(42. = ∂T P P
∂T − ¡ ∂V ¢P = − ∂P T
µ
∂V ∂P
¶
T
=−
nRT .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 2.24)
278
.Examples 1.

27)
Also recall that −wrev is the maximum possible work that can be done in an expansion. Namely Pgas = Pex . there is always an intermediate equilibrium throughout the expansion. Isothermal and Adiabatic expansions We shall consider two limits for the expansion of gases 1.
279
. −wrev = −wmax . Recall that if the expansion is reversible.3. −wrev = For an ideal gas (P =
nRT ) V
Z
V2
Pgas dV
(42. Expansion of Gases
Expanding gases do work: −w = Z
V2
Pex dV
(42. Adiabatic expansion q = 0. So.3. 42. U (T. So for isothermal expansion 4U = 0 = q + w =⇒ q = −w.1.26)
V1
this becomes Z
V2
−wrev =
V1
µ ¶ V2 nRT dV = nRT ln V V1
(42. Isothermal expansion T is constant 2.42. V ) = U(T ) (independent of V ).25)
V1
As we learned last semester the value of w depends on Pex during the expansion.
Isothermal expansion • For the case of a ideal gas.

Or. Heat capacity CV for adiabatic expansions Considering an ideal gas going adiabatically from (T1 . in terms of molar heat capacity
2
T2 ¯ CV m ln T1
µ
¶
V2 = −R ln V1
µ
¶
(42.32) CV ln T1 V1 ¯ where CV = 1 (CV (T1 ) + CV (T2 )) .33)
280
.Adiabatic expansion • Since q = 0. • For an ideal gas dU = −P dV = −nRT dV V (42.3. V2 ). V2 ): CV dT = Z
T2
(42.31)
If CV (T ) is reasonably constant over the internal T1 to T2 then this is approximately µ ¶ µ ¶ V2 T2 ¯ = −nR ln (42.2. V1 ) to (T2 . dU = dw = −Pex dV = −P dV (reversible). Recall ¶ µ ∂U CV = =⇒ dU = CV dT ∂T V So from above CV dT −nRdV −nRT dV =⇒ = V T V Going from (T1 . V
(42.28)
42.29)
(42. V1 ) to (T2 .30)
T1
CV dT = T
Z
V2
V1
−nR dV.

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. P2 ): Z T2
T1
nRT dP P Z
(42.38) CP ln T1 P1 ¯ where CP = 1 (CP (T1 ) + CP (T2 )) .40)
281
.42.3. Or.36)
CP dT = T
P2
P1
nR dP. CP = µ ∂H ∂T ¶
(42.35)
P
For an ideal gas this becomes
Cp dT = Going from (T1 . P1 ) 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
(42.37)
If CP (T ) is reasonably constant over the internal T1 to T2 then this is approximately µ ¶ µ ¶ P2 T2 ¯ = nR ln (42. change)
/ / dH = dq + dw + P dV + V dP
dH = V dP. Now.34)
=⇒ dH = Cp dT = V dP
(42.3. dH = dU + P dV + V dP (because both P and V can. in general. in terms of molar heat capacity
2
T2 ¯ CP m ln T1
µ
¶
P2 = R ln P1
µ
¶
(42. P
(42.

43)
42.42)
but Pi Viγ are arbitrary so this implies P V γ = constant (** NOTE: The axes should be reversed **)
¶γ
⇒ P2 V2γ = P1 V1γ . Joule expansion Consider a gas expanding adiabatically against a vacuum (Pex = 0).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.
(42.3.4. In this case q = 0 (adiabatic) and w = 0 (since −dw = Pex dV ).41)
¶
V1 = γ ln V2
µ
¶
V1 = ln V2
µ
¶γ
(42.
282
.

For real gases this is not strictly equal to zero.3.45)
U
For an ideal gas ∂V T = 0 (since U(T. Internal energy is constant. for Joule type expansion the temperature of the gas does not change. V ) = U(T )).This implies 4U = q + w = 0.44)
U
. That is.5. Joule-Thomson expansion Consider the adiabatic expansion as illustrated by the ﬁgure below
¡ ∂U ¢
283
. Thus in as much as the ¡ ∂T ¢ gas can be considered ideal ∂V U = 0. ¶ µ ¶ ¶ µ µ ∂U ∂U ∂T 1 =− = ∂U V ∂V T CV ∂V T | {z }
1/CV
µ
∂T ∂V
¶
(42. We want to ﬁnd Identity: ¡ ∂T ¢
∂V
(42. 42.

4U = U2 − U1 = wL + wR = P1 V1 − P2 V2 Thus U2 + P2 V2 = U1 + P1 V1 ⇒ H2 = H1 For Joule-Thomson expansion the enthalpy is constant. We want to ﬁnd Identity: µ ¡ ∂T ¢
∂V
(42.48)
(42.50)
H
284
.49)
H
≡ μ. ¶ µ ¶ ¶ µ µ ∂H ∂T 1 ∂H =− = =μ ∂H P ∂P T CP ∂P T | {z }
1/CP
∂T ∂P
¶
(42. The work done on the right is wR = −P2 4V = −P2 (V2 − 0) = −P2 V2 .The work done on the left is wL = −P1 4V = −P1 (0 − V1 ) = P1 V1 . (the Joule-Thomson coeﬃcient).46)
(42. Now.47)
(42.

(42. so μ is negative–the gas warms upon expansion • The Joule-Thomson inversion temperature is the temperature where μ = 0.52)
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 . 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.53)
285
.51)
T
P
¡ ¢ −V + T ∂V P ∂T μ= CP
(42.Recall the useful identity µ Thus ∂H ∂P ¶ =V −T µ ∂V ∂T ¶ (42.

This is not a problem though since entropy is a state function. (43.2) 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 . So dH = dq =⇒ dq=T dS dH = CP dT.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. Entropy of Gases
43. but also dH = T dS. but also dU = T dS. So Z T2 CV CV dT =⇒ 4S = dT. 286
286
.1. Calculation of Entropy
Entropy must be calculated along reversible paths. • At constant V : — dU = dq + dw
dq=CV dT
=⇒
dU = CV dT. dS = T T T1
(43. So Z T2 CP CP dT =⇒ 4S = dT.43.

VA 4SB = nB R ln VB + VA VB (43. V1 P1 /R / n / T
P1
/R / n / T
(43.3)
• Using the equation of state to express V1 and V2 in terms of P1 and P2 .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. V V1
(43. Entropy of Mixing of an ideal gas
• Since the gas is ideal.5)
287
.6) VA + VB . V2 P2 dS = nR ln = nR ln P2 = −nR ln .• Using the equation of state nRdV =⇒ 4S = dS = V
Z
V2
V1
V2 nR dV = nR ln . there are simply two separate equations: 4SA = nA R ln and 4Smix = 4SA + 4SB (43.

So.1. P So ¡ ∂S ¢ µ ∂S ∂P
∂P T
= −
¡ ∂V ¢
∂T
P
and single term viral equation.• Recall Avogadro’s principle: n ∝ V for an ideal gas. So. ⎛ ⎞
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. 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.9)
For an ideal gas B 0 = 0. so
ideal ideal S2 − S1 = −nR ln
(43.12)
ideal Deﬁning S2 . P2 → P θ as S θ .7)
43.11)
Letting P1 → 0 and P2 → P θ (Standard pressure 1 bar). this becomes S2 − / 1 S
ideal ideal = S2 − / 1 S ideal
− nB 0 (P2 − P1 )
(43.
S(P θ ) = S θ − nB 0 P θ
(43.1.8)
µ ¶ → nR P2 → 0 − nB dP =⇒ S2 − S1 = −nR ln dS = − − nB 0 (P2 − P1 ) P P1 P2 P1
(43.10)
Thus
ideal ideal S2 − S1 = S2 − S1 − nB 0 (P2 − P1 )
(43.13)
288
.

15)
289
. P ) = S θ (T ) − nR ln P − nB 0 P Pθ (43.14)
(43. P ) − nB 0 P Thus S(T. P ) = S ideal (T.The entropy at any P and T can be obtained expresses as S(T.

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.16)
• The average speed of a particle is hvi = • The mean free path is
r
8RT πM
(43.
−mv2
(43.Key Equations for Exam 3
Listed here are some of the key equations for Exam 3.17)
RT λ= √ 2P Lπσ 2
(43.18)
290
290
. 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.
Equations
• The Maxwell’s distribution of speeds is F (v) = 4π µ m 2πkb T
¶3 2
e 2kb T v2 .

Vm − b Vm P Vm PV = .26)
(43.21)
• Important thermodynamic relation: 4G = 4H − T 4S • Eyring’s equation is k= kb T − 4H ‡ 4S‡ kb T − 4G‡ e RT = e RT e R h h (43.• The reaction velocity is v=
1 d[I] vi dt
(43.23) (43. Vm Vm Vm • Relation between heat capacities for an ideal gas: CP m = CV m + R
(43. nRT RT (43.25)
• The virial series is µ ¶ µ ¶2 µ ¶3 1 1 1 z = 1 + B(T ) + C(T ) + D(T ) + ··· .19)
• The relation between the rate constant and the thermodynamic equilibrium constant is kf Kc = (43.22)
• The van der Waals gas equation of state: P = • Compressibility Factor: a RT − 2.24)
z=
(43.27)
291
.20) kr • The Arrhenious equation k = Ae− RT
Ea
(43.

Part VIII More Thermodyanmics
292
292
.

44. 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. It is characterized by a critical temperature. Critical Behavior of ﬂuids
The point on the top of the coexistence curve is called the critical point.
293
293
.

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

3)
(44.27 0.5) (44. So.375 3/8 = 0.33
295
.2) 3 dVm ¯c (Vmc − b)2 Vmc
and
solving these three equations for Pc .375.6)
These values can be used to ﬁnd the compressibility factor. 8a . Tc = 27bR a .375 2/e2 ' 0. Pc = 27b2
¯ d2 P ¯ ¯ = 2RTc − 6a = 0 2¯ 4 dVm c (Vmc − b)3 Vmc
(44. That is (for the van der Waals Equation) zc = 0.1)
dP d There is an inﬂection point ( dVm = 0. RTc 8 (44.1. Vmc − b Vmc
2
(44.44.2. Tc . at the critical point zc = Pc Vmc 3 = = 0. Gas Constants from Critical Data Consider the van der Waals equation at the critical point (Pc . Vmc ) Pc = a RTc − 2 .375 for all gases. dVP = 0) at the critical point.7)
Notice that both a and b whose values depend on the particular gas have dropped out. z.4) (44. Tc and Vmc gives Vmc = 3b. setting 2 m the ﬁrst and second derivatives at the critical point equal to zero we get ¯ dP ¯ ¯ = −RTc + 2a = 0 (44. The other equations of state give similar results van der Waals Berthelot Dieterici Redlich-Kwong zc 3/8 = 0.

When α. This implies μβ = μα is the condition for equilibrium.44. dn. then for a given T . The Law of Corresponding States
We have found that zc is predicted by the equations of state to be independent of the particular gas.V = −P
For a spontaneous process A deceases (dA < 0)
z }| { (dVα + dVβ )
¡ ¢ + μβ − μα dn
At equilibrium dA = 0.3.2. One can deﬁne unitless “reduced” variables Tr = T /Tc .18 Laidler&Meiser ∗ ∗
44. Phase Equilibrium
Consider a homogeneous substance consisting of two phases α and β at a constant T and V. Suppose some amount of material. RT zr is a “universal” function–it is nearly the same for all gasses.
296
. Then zr = Pr Vrr . and Vr = V /Vc . ∗ ∗ See Fig. β denote liquid (or solid) and vapor phases. the pressure of the system when μβ = μα is the called the vapor pressure of the material at temperature T. This is actually not too far from the truth experimentally. 1. Pr = P/Pc . goes from α → β • (dAα )T = −P dVα − μα dn • (dAβ )T = −P dVβ + μβ dn
= 0 since V is constant
• (dA)T.

10)
But S = nSm (T.12)
T
Now the total diﬀerential of μ is
m z z m µ }|¶ { µ }| ¶ { ∂μ ∂μ dT + dP dμ(T.13)
297
. P ) so.3. ∂G S=− ∂T So. ∂n ∂T ∂T ∂n ∂T P µ ∂μ ∂T ¶ = −Sm .¡ ¢ For phase changes at constant T and P then (dG)T. P ) = ∂T P ∂P T dμ(T. 44.T
µ ¶ ∂ ∂G ∂μ ∂ ∂G =− =− =− . dG = −SdT + V dP + μdn Now. = Vm .n
P.
(44. So again μβ = μα is the condition for equilibrium.
(44.9)
P.P = μβ − μα dn. The chemical potential and T and P How does μ vary with T and P ? Generally for homogeneous substances. P ) = −Sm dT + Vm dP
−S
V
(44.11)
P
Similarly.1. µ ∂S ∂n ¶ µ ¶ (44.
µ
∂μ ∂P
¶
(44.8)
(44.

Vapor Equilibrium and the Clausius-Clapeyron Equation The above Clapeyron equation applies to any phase transition. 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. The Clapeyron Equation At equilibrium μβ = μα so. Now 4v V = Vm.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
(44.3.16)
44.2.3.21)
d(ln P ) = −
298
.3.vap Assuming the vapor phase obeys the ideal gas equation of state.44.20)
= d(ln P ) and
dT T2
= −d(1/T ) so this becomes 4v Hm d(1/T ) R (44.14)
=
This is the Clapeyron Equation
4φ Hm T 4φ Vm
(44.liq ' Vm.vap − Vm. consider the liquidvapor phase transition.15)
(44.18) (44. −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.

(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.Rearranging again leads to 4v Hm d(ln P ) =− d(1/T ) R This is the Clausius-Clapeyron equation.24) α β
299
.4.23)
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. “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. Equilibria of condensed phases
Examples • Solid—liquid — ice—water.22)
44.

26) 4f Hm 4f Hm Tf → T
ª where Tf is the freezing temperature at standard pressure (1 bar).27)
300
. • Triple Point: The point where all three phases coexist in equilibrium: μsolid = μliq = μvap (44. Triple Point and Phase Diagrams
Deﬁnitions • Phase Diagram: A graph of P vs.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.Thus for any given T only one P allows for equilibrium. T for a system which shows the lines of equal chemical potential • Critical Point: The terminal point of the liquid-vapor line. Recall the Clapeyron equation 4f Hm Hmβ − Hmα dP = = dT T 4f Vm T (Vmβ − Vmα ) (44.5.
44. At temperatures above the critical point there is no distinction between vapor and liquid.

of material from high concentration to low concentration so as to establish an equilibrium.1)
301
301
. Diﬀusion: The ﬂux of material down a concentration gradient 2. Flux: movement of something through a unit area. Thermal Conductivity: The ﬂux of energy down a temperature gradient
∗ ∗ See Transport Phenomena handout ∗ ∗
45. J= 1 dn A dt (45. Viscosity: The ﬂux of momentum down a velocity gradient 3.1.45. So if there exists a concentration gradient there will be a net ﬂux. We now consider three transport properties of ﬂuids: 1. J. Diﬀusion
At equilibrium concentration on a bulk solution will be uniform. Transport Properties of Fluids
Transport properties of matter deal with the ﬂow (or ﬂux) of some property along a gradient of some other property.

3) (45.5)
302
. ∂t ∂x ∂x If D is truly constant we get Fick’s second law of diﬀusion: ∂ 2C ∂C =D 2.2)
(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). 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 .4) (45. ∂t ∂x (45.

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

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

4πr3 (ρ − ρ0 )g.11)
• Related to diﬀusion constant:
=
kT 6πηr
(45. Lightfoot Wiley New York 1960) The thermal conductivity.3. Bird. κ.• The frictional force (exerted upwards) is proportional to velocity: Ff = −fv. 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. Thermal conductivity
(This section closely follows parts of chapter 8 in Transport Phenomena by R. The plates are held at constant but diﬀerent temperatures T1 and T2 (T1 > T2 ) for a suﬃciently long time that a steady state exists. Consider a slab of solid material of area A between two large parallel plates a distance D apart.B.12)
45. Stokes showed f = 6πηr • Gravitational force (exerted downwards): Fg = gravitational acceleration (9. of a material is a measure of the tendency of energy in the form of heat to ﬂow through the material. N.10)
(45. Stewart and E. W.
305
.8 m/s2 ).E.

3. whereas the thermal conductivity of most liquids decrease with increasing temperature.e. 45. (45.1.Under such conditions.. (45. from hot to cold. And a constant rate of heat ﬂow dq is needed to maintain dt the temperature diﬀerence 4T = (T1 − T2 ) 4T 1 dq = −κ . 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.
306
. This is called Fourier’s law of heat conduction (one-dimensional version).14) A dt dx where Qf is the heat ﬂux.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 . a linear steady state temperature distribution across the material is established. Thermal conductivities are positive quantities so Fourier’s law says that heat ﬂow down a temperature gradient. i.

There is no analog to superconductivity for thermal conductivity.15)
307
.3. 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. (45. Frantz and Lorenz equation relates the thermal conductivity to electrical conductivity. the thermal conductivity of solids have to be determined experimentally because many factors contributing to the thermal conductivity are diﬃcult to predict. κel T where L is the Lorenz number (typically 22 to 29 × 10−9 V2 /K2 ).2. κel for pure metals: κ = L = const. The Lorenz number is taken as constant because it is only a very weak function of temperature with a change of 10 to 20% per 1000 degrees being typical. Thermal Conductivity of Solids For the most part. Frantz and Lorenz equation breaks down at low temperature because metals become superconductive. The Wiedemann. The Wiedemann.45.

say. 308
308
(46. Partial Molar Quantities
Thermodynamic properties. in addition to the parameters needed to characterize a pure substance. So. 4mix V = Vsoln − Vsolute − Vsolvent Consider a thermodynamic quantity. n1 +n2
• mole fraction X2 = • molality m = • Molarity c2 =
X1 = 1 − X2
1000X2 .2)
. in general change upon mixing X 4mix = properties of soln − properties of pure. Solutions
Solutions are mixtures of two or more pure substances.46. M1 X1
where M1 is the molecular weight of species 1
n2 L solution
46. Measures of Composition
There are several measures of composition of solutions • mole ratio r =
n1 n2 n2 .1.2. volume. one also needs to keep track of the amount of individual species in solution
46.1)
(46. For example.

In general.1. n1 and n2 : V (T.n1 .n1 .n1 (46.P.4) ³ ´ ∂G ≡ μi .n2 ∂n1 T. So.P. n2 ). Notation The study of solutions brings with it here for future reference. ∂ni
T. ∂T P. the total derivative is ¶ ¶ µ ¶ ¶ µ µ µ ∂V ∂V ∂V ∂V dV = dT + dP + dn1 + dn2 . Material Pure liquid i Vi• • Pure liquid i per mole Vmi Whole solution V Solution/(total moles) Vm ¯ Partial molar of i in solution Vi Apparent molar (of solute) φ V Reference state Viª a large number of symbols which we collect
Hi• • Hmi H Hm ¯ Hi φ H Hiª
Si• • Smi S Sm ¯ Si Siª
G• i • μi G Gm μi μª i
309
.P.n2 ∂P T.3) ³ ´ ∂V ¯ ≡ Vi .n2 ∂n2 T.n1 .n2 ∂P T.n2 ∂n2 T.2. it is a function of T.n1 . P.n2 ∂n1 T. 46.nj
Similarly ¶ ¶ ¶ ¶ µ µ µ µ ∂G ∂G ∂G ∂G dT + dP + dn1 + dn2 .P. P.n1 (46. rather than simply the molar free energy as it was earlier. ∂ni
T.P.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. n1 . the partial molar volume.P. dG = ∂T P.

negative or zero. dn1 = n1 dλ.46. Partial Molar Volumes Consider the partial molar volume For constant T and P ¯ ¯ dV = V1 dn1 + V2 dn2 (46. one unit of baseballs are mixed with one unit of basketballs.7)
(46.
310
. dn2 = n2 dλ.6)
That is. So. however.2. 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. so change each amount of substance proportional to the amount substance present. For example.
1. The total volume. 2.2. Vi depends on concentration. the total volume of the solution is equal to the sum of the partial molar volumes each weighted by their respective number of moles. one unit of baseballs are mixed with one unit of books. 4mix V < 0. 4mix V > 0. (46.5) ¯ Now.8)
4mix V can be positive. is not necessarily the mole weighted sum of the volumes of each component in its pure (unmixed) state.

inﬁnite dilution limit 1. all neighboring molecules are same as the given molecule 2. neat (pure) solvent limit 1. 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
.3.1. Reference states for liquids
For liquids there are two more convenient ideal states 1.3.46. the ideal state for Raoult’s law 2. the ideal state for Henry’s law
Raoult’s law limit 46. all neighboring molecules are diﬀerent than the given molecule 2.

(46.3. (46.9) ζ→ζ ª g(ζ) where g(ζ) is any reference function (e..Also recall that the mathematical deﬁnition of activity ai of some species i is implicitly stated as ai lim =1 (46. we are describing the behavior of a liquid solution by measuring the vapor (partial) pressures of the components
312
.12) i ai g(ζ) (46. and ζ ª is the value of ζ at the reference state. This implicit deﬁnition is awkward so for convenience one deﬁnes the activity coeﬃcient as the argument of the above limit.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.2. 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). γi ≡ which we can rearrange as ai = γ i g(ζ). concentration etc.). μi − μª = RT ln ai .10)
46.g. pressure. Raoult’s Law In discussing both Raoult’s law and Henry’s law. mole fraction.

Recall that 4mix G = G(soln) − G(pure components) Hence. so dG = (μ1 n1 + μ2 n2 ) dλ then G = μ1 n1 + μ2 n2 .15) (46. 4mix G = μ1 n1 + μ2 n2 − μ• n1 − μ• n2 1 2 (46.17) (46.14) (46. • ai Pi (46. μ1 − μ• = RT ln 1
where Pi is the vapor pressure of the ith component above the solution.18)
Now.13)
= (μ1 − μ• ) n1 + (μ2 − μ• ) n2 . dG = μ1 dn1 + μ2 dn2 .16) (46. Take diﬀerential change along a line of constant concentration.
313
. 1 2 ai low P Pi ' RT ln • .For simplicity we consider here only a two component solution.

3.21)
That is.24)
(46. ∂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)
(46.20)
46.23)
(46.25)
(46. this is for an ideal solution in the Raoult’s Law sense.22) • • P1 / P2 / 4mix G = RT (n1 ln X1 + n2 ln X2 ) Again.3.19)
(46.Thus
or at low P
¶ µ P1 P2 4mix G = RT n1 ln • + n2 ln • P1 P2
¶ µ a1 a2 4mix G = RT n1 ln • + n2 ln • a1 a2
(46. The 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. Ideal Solutions (RL) Raoult’s Law: Pi = Xi Pi• (46. From ¶ ¶ µ ∂G ∂ (G/T ) S=− and H = − . 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.26)
314
.

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

29)
Xi →0
Henry’s law applies to the solute not to the solvent and becomes more correct for real solution as the concentration of solute goes to zero (Xi → 0). mixing with one substance may lead to a positive deviation but mixing with another substance may lead to a negative deviation.3.4. where kXi is the Henry’s law constant. at inﬁnite dilution. i. For example.
316
.
Positive deviation from Raoult’s lawNegative deviation from Raoult’s law 46. for a given component. Henry’s Law Henry’s Law: Pi = kXi Xi . 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..e.30) (46.

33)
= γ Mi Mi
(HL)
(46. Raoult’s law applies to the dominant species.The Reference State (HL) Referring to the deﬁnition of activity again we see that the reference function is g(ζ) = ζ = Xi . 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
(46.34)
317
. (46. and the reference state is now Xi = 0 So. So. (HL) ai lim =1 (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. X1 → 1.32) ai → 1 as Xi → 0 and γ i If instead of mole fraction. they apply to opposite species in the solution. whereas Henry’s law applies to the subdominant species X2 → 0.31) Xi →0 Xi implies (HL) (HL) = γ i Xi . molality or molarity is used then ai and ai respectively. But.

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. | {z }
μs 1
318
.46. Freezing Point Depression At Tf (freezing point).4. μ1 (solid) = μ1 (soln).

(so.37)
• For small changes in the freezing point we may approximate T by Tf in the integrand.Using the Raoult’s law reference state (since we are interested in the behavior of the dominant species). The freezing point depression is
Θ=− 46.
319
.35)
(46. So. 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. using
∂μ ∂T
(46. 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. T. (46. Z Tf −4f H 4f H ln a1 ' dT = Θ. Osmotic Pressure
RTf•2 ln a1 4f H
We consider the osmotic pressure at a constant temperature.38) •2 •2 • RTf Tf RTf • where Θ ≡ Tf − Tf .2.4.

a1 = X1 = 1 − X2 : ln a1 = ln(1 − X2 ) =
• Vm1 Π RT
(46.42)
'
n2 n1
for dilute solutions.In the above ﬁgure μ1 (left) = μ1 (right). From the above equation
¯ V1 Π RT • ¯ Now we make the approximations V1 = Vm1 . ' m1 =⇒ n2 ' n1 RT RT
V•
(46. hence ¯ μ• = μ• + RT ln a1 + V1 Π.40)
(46.39)
¯ where V1 is the partial molar volume of the solvent in solution (diﬃcult to measure) and Π is the hydrostatic (osmotic) pressure. 1 1 (46.41)
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 . 2 3
(46. Thus
1 z }| { • • V Π n1 Vm1 Π n2 .43)
320
.

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

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

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

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

4)
¡ ¢ and the possibility of. As example we now consider the last two of these: heat ﬂow and chemical reactions.3. heat ﬂow. Examples
The idea of entropy production can be applied to any of the processes we have talked about. di S I < 0 and di S II > 0 such that di S I + S II > 0 is excluded. (47.3) The local formulation statement implies di S I ≥ 0 and di S II ≥ 0 (47. phase changes.
47. chemical reactions.I II
Considering the above ﬁgure of an isolated system.
325
. for example. we write the principle of Clausius as dS = dS I + dS II ≥ 0. mixing. etc.

1.
326
. 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.7) dt dx Example: Find the entropy production in a system consisting of two identical connected blocks of metal (I and II).3. (47. so.5) we get (47.6)
We are now interested in exposing the time dependence. 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. using Qf = κA4T q =− 4t D in diﬀerential form this is
dT dq = −κA .47.

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

47. where ni is the number of moles vi of the ith component and vi the stoichiometric factor of the ith component. Extent of reaction: ξ is deﬁned by dξ = dni . (47.13) dt dt ¯ Using the above expression for heat ﬂow gives us T since. Entropy Production due to Chemical Reactions Deﬁnitions: 1. Chemical aﬃnity: a ≡ − (4rxn G)T. dt D So.11) ¶
−Aκ4T di qI = . − ¢ ¢ κ/ κ/ /A ¡ / A ¡¯ ¯ ¯ T1 + T2 .For this example di qI di S = dt dt From chapter 24 we know
µ
1 1 − T1 T2
¶ (47. T1 − T = − T − T2 ⇒ T = 2 D / D / (47.3.12)
¯ 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 = . −Aκ4T di S = dt D µ 1 1 − T1 T2
(47.14)
a result we might have guessed.P = − P − i vi μi P
i
vi μi and a ≡ − (4rxn A)T.V =
2.
328
.2.

17)
z }| { z }| { (dA)T. for the reaction N2 + 3H2 → 2NH3 dξ = and a = 2μNH3 − μN2 − 3μH2 The connection to kinetics: reaction rate v = The connection to thermodynamics: (dA)T.g.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 is positive as is v.15)
(47.V − T dS ⇒ dS = T T
dq
e i z}|{ z}|{ dq adξ + dS = T T
(47.V = X
i dξ dt
dnH2 dnNH3 dnN2 = = (−1) (−3) (2)
(47. This is because a = − (4rxn A)T..18)
d S
dS
(47.V dq − = (dU)T.V so
µ ¶ 1 dni = −adξ μi dni = vi μi vi | i {z }| {z } X
−a dξ −adξ
(47.20)
We see that for a spontaneous process the entropy production per unit time is positive.16)
but (dA)T.
329
.• e.

47. 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. We just saw an example of such a situation with the discussion of simultaneous reactions. the so-called Dufour eﬀect is heat ﬂux down a concentration gradient
330
. diﬀusion is the ﬂux of matter down a concentration gradient.
For example in a system of two coupled reactions we could have a1 v1 < 0. Conversely. Thermodynamic coupling need not be conﬁned to coupling between the same types of processes. the entropy production per unit time generalizes to N 1X di S = aj vj ≥ 0. a2 v2 > 0 such that a1 v1 + a2 v2 > 0. (47.4. 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.Simultaneous Reactions For N simultaneous chemical reactions. That is. The socalled Soret eﬀect is ﬂux of matter down a temperature gradient.21) dt T j=1
The second law requires that the total entropy production for simultaneous reactions is positive.

• 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.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
47.5.
331
. If the perturbation is released the system will begin to evolve in time as it heads back towards the thermalized equilibrium state. 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.

• 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. • This cannot be undone with the second radio pulse. • Each nucleus is in a slightly diﬀerent environment so each spin frequency is slightly diﬀerent.• A strong signal is seen because all the spinning nuclei cooperate.
332
. • The diﬀerent environment (spin frequencies) cause the ensemble spinning nuclei to dephase • Dephasing causes a decrease in the observed signal because now not all nuclei are cooperating.

The equations are collected here simply for handy reference for you while working the problem sets. dT T 4φ Vm • The Clausius-Clapeyron equation is 4φ Hm d(ln P ) =− d(1/T ) R • Fick’s ﬁrst law of diﬀusion is dC 1 dn = −D A dt dx (47.Key Equations for Exam 4
Listed here are some of the key equations for Exam 4.23) (47.
Equations
• The Clapeyron Equation is 4φ Hm dP = .22)
333
333
.24) (47. 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.

µ ¶
(47.
(47. A dt dx X
(47.31)
Pi = kXi Xi .
(47.• Fick’s second law of diﬀusion:
∂ 2C ∂C =D 2.28)
μ = μª + RT ln a
(47.29)
Pi = Xi Pi•
(47.25)
• Relation between the viscosity and the diﬀusion constant: D= kT f
f =6πηr
=
kT .27)
• Mixing 4mix = properties of soln − • Chemical potential • Raoult’s Law: • Raoult’s law reference ai • Henry’s Law:
(RL)
properties of pure.32)
where kXi is the Henry’s law constant.
(47. ∂t ∂x
(47.26)
• Fourier’s law of heat conduction is
dT 1 dq = Qf = −κ . 6πηr
(47.33)
= γi
(HL)
Xi .30)
= γi
(RL)
Xi .
γi
(HL)
→ 1 as Xi → 0.34)
334
. kXi = lim • Henry’s law reference ai
(HL) Xi →0
Pi Xi
.
γi
(RL)
→ 1 as Xi → 1
(47.

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

108 cylindrical symmetry 69 Debye—Huckel limiting law 164. 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. 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. 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.Clapeyron equation 298. 178 Debye—Huckel theory 163 Debye—Huckel—Guggenheim equation 164 Debye’s law 129. 333 coeﬃcient of thermal expansion 274 coexistence curve 293 colligative properties 318 commutator 30. 132 enthalpy 136 entropy 105 change for changes in temperature 286 change for isothermal expansion 286 change for mixing 287 of real gases 288 entropy production 322. 333 Clausius-Clapeyron equation 299.

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. 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. 316. 133 ﬂipping coins 90 ﬂuctuation 92 ﬂuorescence 242 stokes shift 242 Fourier’s law of heat conduction 306. 334 Henry’s law constant 316.equlibrium constant 153 Euler’s identity 4 expansion of gases 111 reversible 114 extent of reaction 328 Eyring’s equation 265. 86 potential energy 39 Schrodinger equation for 39 heat 109 sign convention 110 heat capacity 115. 86 Hamiltonian 47 normalization constant 49. 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. 291 fermions 56 Fick’s ﬁrst law 302. 334 ﬁrst law of thermodynamics 121. 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. 333 Fick’s second law 302. 44. 121 intramolecular vibrational relaxation (IVR) 242
337
.

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

218 Hamitonian for 194 wavefunctions for 195. 276 relaxation eﬀects 167 rigid rotor 200 degeneracy of 235. 312. 87 reaction velocity 255. 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.particle in a box 31. 181 energy levels 183 energy levels for 34. 247 rotational energy levels 200. 219
339
. 291 reciprocal rule 108 red sunsets 82 Redlich-Kwang gas 270 reference states 147 relationship between CP and CV 139. 132 translational 101. 44. 131 electronic 101 grand canonical 97 isothermal—isobaric 97 microcanonical 96 molecular 100 rotational 101. 218 particle on a ring 194 boundary conditions 194 energy levels for 195. 314. 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. 324 principle quantum number 52 probability amplitude 22 probability distribution 22 PV work 111. 82. 133 Raman scattering 80 Raman spectroscopy 66. 218 partition coeﬃcient 154 and drug delivery 155 for the Born model 174 partition function canonical 96. 132 vibrational 101. 233 and the character table 234 Raoult’s law 311. 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. 44. 248 energy 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. 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. 133 tips for solving problems 2 total derivative 107 transfer matrix 11 triple point 300 two level system 211 ‘left’ and ‘right’ states 213. 53 wavefunction 51 spin orientation quantum number 51. 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. 200 spin 201 quantum number 51. 219 Hamiltonian for 212 Tyndall scattering 84 ungerade 69 van der Waals equation
340
. 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.