# 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 . . . . . . . . . . . . . . . . . . . . . .

74 76 78 79 79 81 82 83

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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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. . . . . 228 33. .2 Mathematical Groups . . . . . . . . . . . . . .1 Direct Products . . .1 Spin Angular Momentum . General . . . . . . . . . .
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. . . . 29.1 Example: The C2v Group . . . . . . . 32. . . .1 The Two Level System .3 Symmetry of Functions . . 32. . . . . . . . . . . . . . . . . . . . . . . 32. . . . . . . . . .2 Variational method . . . . . . .2 Quantum Dynamics . . . . . . . . . . . . . . . . . . . . . . 214
VI
Symmetry and Spectroscopy
220
221 222 222 223 223 225 225
32 Symmetry and Group Theory 32. . . . . . . . . . . .2 An Example: Two Electrons . . .2 Normal Modes and Group Theory . . . . . . . . . . . . . . . . . .2. .
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201 201 202 202 203 204 205
30 Approximation Techniques 207 30. . . . .1. . . . . . . . . . . .
. . . . . . . . .1 Normal Modes . . . . . . . . . . .4 Spin Orbit Coupling . . . . . .
. . . . . . . . . . . . . .1 Symmetry Operators . . . . . . . . . . . 29. . .
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.1 The Addition of Angular Momentum: 29.
. .1 Perturbation Theory . . .
33 Molecules and Symmetry 228 33. . . . 211 31. .3. .2 Addition of Angular Momentum . . . . . . . . . . . . .29 Addition of Angular Momentum 29. . .1 Molecular Vibrations .2. .
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.2 Molecular Collisions . . . 250 38.1 Relaxing the rigid rotor . . . . . . . . . . . 35. . . . . . . . . . . . . . . . . .1. .
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. .2 Franck—Condon activity . . . . . . . . . . . . . . 245
VII
Kinetics and Gases
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38 Physical Kinetics 250 38. . . . 231 34. . . . . . .
. . . . . . . .34 Vibrational Spectroscopy and Group Theory 231 34.3 Fluorescence Spectra . . . . . . 36. . . .1 The Fourier transformation . . . . . . . . . . . .1 The Franck—Condon principle 235 236 236 237 240 240 241 241 242 243 243
. . .2 Determination of Rate Laws . . . .2 Raman Spectroscopy . . . . . .1 The Structure of the Electronic State 36. . . . . . . . . . . . . . 39. 36. . .1 Rate Laws . .
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37 Fourier Transforms 245 37. . 36 Electronic Spectroscopy of Molecules 36. . .
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. . .1 IR Spectroscopy . . .
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. . . . .3 Rotation of Polyatomic Molecules . . . . . . . .
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.2. . . . . . .2 Emission Spectra . . . . . 252 39 The Rate Laws of Chemical Kinetics 39. . . . . . . . . . . . .
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. .2 Heat Capacity of Gases Revisited . . . . . .2 α and κT for liquids and solids . .3. . . . . . 42.1 Equations of State .
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. . . V and T behavior . . . . . . . . . . .2. . . . . . . . . . .3. . . . . . .
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. . . . . . . . . . . .4 Joule expansion . . . 288
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. . . .1 Temperature corrections to the Arrhenious 40. . . . . . . .3 When P is the more convenient variable .
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43 Entropy of Gases 286 43. . . . . 42 Behavior of Gases 42. . . .2. . . . . .1.
.40 Temperature and Chemical Kinetics 40. . . . . . . . . . .1 Calculation of Entropy .
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. . .3 Expansion of Gases . .3 The Virial Series in Pressure . . . . . . . .1 The Relationship Between CP and CV . . . . . .2 The Boyle Temperature . .2. .
. .1. . . .3 Multistep Reactions . . . . . . .
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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. . . . . . . . .3. 41. .3. . 42.1. . . . . . . . . . . . . .3. . . . . . . . . . . 41. . .1 Relation to the van der Waals Equation of State 41. . . . . . . . . .
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. . . . .4 Estimation of Virial Coeﬃcients . . 41. . . . . . . 42. . .2. . . . 42. . .2 Theory of Reaction Rates . . . . . . . . . . .1 Entropy of Real Gases . .5 Joule-Thomson expansion . . . . . . . . . . . . . . . . .1 P. . . . . .
. . . . .1 Temperature Eﬀects on Rate Constants . . . . . . . . . .1 Isothermal and Adiabatic expansions . . . . . . . . . .2 Heat capacity CV for adiabatic expansions 42. . . . . . . . . . . .
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.2 Viscosity .
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.3. . .1 Diﬀusion . . . . . . . . . . . . . . 44.3. .
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. . .5 Triple Point and Phase Diagrams .
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.2 Partial Molar Volumes . . . . . 44. . . . . .2 Gas Constants from Critical Data . . . . . . . . . . 46.
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. . . . . . . . .2 Thermal Conductivity of 46 Solutions 46.3. . . 46. . . . . . . . . . . . .
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. . . . . . . . . . . . . . . . .1 Notation . . 45 Transport Properties of Fluids 45. .
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. .1 The chemical potential and T and P . . . . . .2. . Liquids . . 46. . . .1 Critical Behavior of ﬂuids . . . . . . . .2 The Law of Corresponding States . . . . . . . . . . . .
. . .1 Measures of Composition . .
. . . .2 Partial Molar Quantities . . . . . . 46. . .1 Gas Laws in the Critical Region . . . .1 Activity (a brief review) 46. . . .
. .3 Thermal conductivity . . . . 44. . . . . . . . . . . . .1. . . . 45. .3. .
. .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. . . . . . . . . . . . . . . . . . . . . . . .4 Henry’s Law . . . . 45. . . . . . . . . . .
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. . . . . . .1 Entropy Production due to Heat Flow . . . . . . . . . . .4. . .4 Thermodynamic Coupling . . . . . . . . . .1 Fundamentals . . . . .
. . . . . . . . . . . .46. . . . . . . . . . . . . . . . . . . . .5 Echo Phenonmena . . .4 Colligative Properties . . . . 47.2 Osmotic Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3. 322 322 324 325 326 328 330 331
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. . . . . . . . .1 Freezing Point Depression . . . 47. . . . . . . . . . . .3 Examples . . . . .2 Entropy Production due to Chemical Reactions . . . . . . . . . 47. . . .4. . . . . . . . .
.2 The Second Law .3. . . . . . . . . . . 318 46. 47. . 319 47 Entropy Production and Irreverisble Thermodynamics 47.

Chemistry 351: Physical Chemistry I
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Tips
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. The only way that you can be sure that you understand a concept at to be able to solve the problems associated with it. Even though there aren’t many “book” problems assigned during the year. so it might be helpful to you to see some of these problems worked out. Consequently early in the course some of the examples might seem very itimidating. Keep in mind this chapter provides some examples of how to solve problems for both physical chemistry I and physical chemistry II. you can still learn a lot be working these and looking that their solutions in the solution manual. This takes time and hard work.
Tips for solving problems
Working problem sets is the heart and sole of learning physical chemistry. 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.Solved Problems
I make-up most of the problems on the problems sets.

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

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

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

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

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

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

yes the coeﬃcient of the linear term (the term involving (R − Req ) to the ﬁrst power) is zero.
The Taylor series about Req for this function is ¯ ¯ 2 ¯ dV (x) ¯ ¯ (R − Req ) + 1 d V (x) ¯ (R − Req )2 + · · · .So. How many molecules are in the ﬁrst excited state of the ‘ring breathing’ mode (992 cm −1 )? How
9
. Solution: This problem requires the we think qualitatively about the wavefunctions and the potentials for the harmonic oscillator and the Morse oscillator. The potential for the harmonic oscillator is described by a parabola centered about the equilibrium bond length. This will always be true when you perform a Taylor series expansion about a minimum (or maximum). The force constant is given by the coeﬃcient of the quadratic term so in this case k = β 2 De . The Morse potential does not have this symmetry. (20) V (x) = V (x)|Req + dx ¯Req 2! dx2 ¯Req | {z } | {z } | {z } =0
=0 = β 2 De
Problems Dealing With Statistical Mechanics and Thermodynamics
Problem: A vial containing 10 20 benzene molecules is at 300K. 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. Problem: Without performing any calculations. 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. Therefore without performing any calculations we can at least say that hRi increases as the quantum number increases. compare hRi as a function of the vibrational quantum number for a diatomic modelled as a harmonic oscillator versus a Morse oscillator.

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 ⎦.41×10 × 100% = 0. × 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. B or C. Find the entropy per atom for this system as N → ∞. 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. ¶ ³ µ ´ 3×992 992 rb × e− 2×208 × 1020 = 8.··· . V = ⎣ 7 ⎦. V (j+1) = MV (j) . V = ⎣ 3 ⎦. Each of the atoms can be in one of three states A. So. where for this example ⎤ 1 1 0 ⎥ ⎢ M = ⎣ 1 1 1 ⎦.02×10 × 100% = 1020 0.0000402% of the benzene molecules are in the ﬁrst excited state for the C—H stretching mode. For example. 1 2 5 The V (j+1) can be found from the V (j) vector using the matrix equation. Problem: Consider a linear chain of N atoms.41 × 1017 Nv=1 = 2 sinh (21) 2 × 208 and
C—H Nv=1
We see that about 8. 0 1 1 ⎡ (24)
¶ ³ µ ´ 3063 − 3×3063 2×208 × 1020 = 4.02 × 1013 . B or C. except that an atom in state A can not be adjacent to an atom in state C.

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

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

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

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

Part I Basic Quantum Mechanics
15
15
.

The photoelectric eﬀect 2. Quantum Theory
The goal of science is uniﬁcation. experiments were being performed in which the results deﬁed explanation by means of the current understanding of physics.1. 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. Among these experiments were 1. Atomic spectral lines 4.1. Black body radiation and the ultraviolet catastrophe 16
16
.
1. Low temperature heat capacity 3. • Many phenomena described by minimal and general concepts.

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

— The system is not stable and the electron spirals into 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 atom collapses!
Bohr’s model: Niels Bohr (1885—1962)
18
.— As the electron orbits the nucleus.

~ = h/2π is Planck’s constant divided by 2π.52918 Å and is called the Bohr radius. me and e are the mass and charge of the electron respectively and 0 is the permittivity of free space. • Therefore atomic orbitals must be quantized. me e2 The total energy of the Bohr atom is related to its quantum number µ 2 ¶ e 1 2 .. N is a positive real integer called the quantum number.e. i. • If the orbital radius was continuous the gas would have a continuous spectrum.2)
19
. 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.3) Eionize = E∞ − E1 = 2a0 ∞2 1 2a0
(1.• Atoms don’t collapse =⇒ what are the consequences Experimental clues • Atomic gases have discrete spectral lines. N = 1 → N = ∞ µ ¶ 1 e2 −Z 2 e2 1 − 2 = (1.
2
The constant quantity 4π e0e~ appears often and is given the special symbol a0 ≡ m 2 4π 0 ~2 = 0.1) Zme e2 where Z is the atomic number. r=
4π 0 N 2 ~2 (1.

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 2.4.· · · 3.· · · 4. — Doing this results in the emission or absorption of a photon with energy v= ˜ 4E hc (1.7.· · · Series Name Lyman Balmer Pachen Brackett Pfund
(1.5.4)
— Since the orbitals are quantized.4.5)
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
.e — Eionize = 2a0 = 13. R is called the Rydberg constant.6.
2
— Eionize experimentally observed from spectroscopy is 13.6.· · · 5.· · · 6.3.5.7. the atom may only change its orbital radius by discrete amounts.667 cm−1 = R.606 eV = 109.8.

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

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

z)|2 to be exactly interpreted as a probability distribution.2)
space space
23
. z)|2 dxdydz < ∞ Normalization of the wavefunction In order for |ψ(x. qR That is. 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. 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.Properties of the wavefunction • Single valueness • continuous and ﬁnite • continuous and ﬁnite ﬁrst derivative R • space |ψ(x. ψ unnorm = Nψnorm . z) must be normalizable. y. y. How to normalize a wavefunction
If we have some unnormalized wavefunction. ψ(x. where N = |ψunnorm (x. y. y. (2. (2.1) 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.

So.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 . y. sZ N=
space
|ψunnorm (x. 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. Thus wherever R we see space |ψnorm |2 dxdydz we can replace it with 1. Z |ψunnorm |2 dxdydz = N 2 × 1 = N 2 . (2.
(2. z)|2 dxdydz.5)
space
Z
space
|ψnorm |2 dxdydz = 1
(2.3.4)
This gives us an expression for N. therefore this is a general procedure that will work for any wavefunction. (2. Taking the square root of both sides gives.
24
. Postulates II and II
Postulate II: Every physical observable is represented by a linear (Hermitian) operator.but
The N is just a constant so it can be pulled out of both the mod-square and the integral Z Z 2 2 |ψunnorm | dxdydz = N |ψnorm |2 dxdydz.8) 2 normalized x |ψ(x)| dx 1 −∞
2.3)
space space
because that is the very deﬁnition of a normalized wavefunction. N unnorm (2.

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

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

3. The Hamiltonian
The most important physical observable is that of the total energy E.1)
3. 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. The Setup of a Quantum Mechanical Problem
3. Deﬁne the classical Hamiltonian for the system.2. This equation is the most important equation of the course and we will use it many times throughout our discussion of quantum mechanics and statistical mechanics. (3. The eigenvalue equation for the Hamiltonian is ˆ Hψ = Eψ. 1. This equation is the (time independent) Schrödinger equation.1.

z) ψ = Eψ 2m −~2 2 ∇ ψ + (V (x.4)
• Note: Some quantum systems don’t have classical analogs so the Hamiltonian operator must be hypothesized. z) (3.7)
ˆ 3. ∂z 2
and (3.6)
ˆ V = V (ˆ. 2. Solve the Schrödinger equation. • The kinetic energy is always of the form T = ¢ 1 ¡ 2 px + p2 + p2 y z 2m (3.3)
• The potential energy is almost always a function of coordinates only V = V (x. z) H =T +V = 2m
(3.• The total energy for a classical system is Ecl = T + V.5)
where ∇2 ≡
∂2 ∂x2
+
∂2 ∂y2
+
∂2 . with their appropriate operators. Thus. −~2 2 ˆ ˆ ˆ ∇ + V (x. y. z ) = V (x. where T is the kinetic energy and V is the potential energy. x ˆ ˆ So. y.
2 2 ˆ −~ ∇2 = −~ ∇2 . z). y. z) − E) ψ = 0 (3. Hψ = Eψ. y. y. y . Use Postulate II to replace the classical variables. which is now a second order diﬀerential equation of the form ¸ ∙ 2 −~ 2 ∇ + V (x. ˆ T = 2m 2m
(3.2)
(3. px etc. x..8) ⇒ 2m
28
.

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.• Note: It is solely the form of V (x. value for the measurement. y. give an expectation. If ψ is not an eigenfunction of a particular operator. however.11)
space
ψ px ψdxdydz = −i~ ˆ
∗
Z
(3.9)
3. z) which determines whether this is easy or hard to do. or average. The Average Value Theorem
Postulate III implies that if ψ is an eigenfunction of a particular operator representing a physical observable. This is given by Z hˆ i = α ψ∗ αψdxdydz ˆ (3.3.10)
space
For example. but we cannot predict for certain which one. then all measurements of that physical property will yield the associated eigenvalue.12)
space
29
. However. then all measurements of that physical property will still yield an eigenvalue. • For one-dimensional problems −~2 d2 ψ + (V (x) − E) ψ = 0 2m dx2 (3.

We see δpx δx ≥ 1 1 |h[ˆx . The general statement of the Heisenberg uncertainty principle is 1 ¯Dh ˆ iE¯ ¯ ¯ δαδβ ≥ ¯ α.b. be simultaneously known to arbitrary precision. δpx δy = 0. This idea is the Heisenberg uncertainty principle and is of profound importance.. The commutator is ˆ where the notation α. at the very best we can only hope to simultaneously know position and momentum such that the product of the uncertainty in each is ~ . for example.3. Such variables are called complimentary. α. The Heisenberg Uncertainty Principle
In quantum mechanics certain pairs of variables can not. (n.13) 2 h i ˆ means the commutator of α and β. even in principle.) Suppose we know the position of a particle perfectly. β ¯ .4.15)
So. the y position and the x momentum to arbitrary precision. β ˆ ˆˆ ˆˆ (3. β ˆ ˆ deﬁned as h i ˆ ≡ αβ − β α. ˆ (3. ¯ 2i ¯ 2 (3. what can we say about its momentum?
30
.14) The most important example of complimentary variables is position and momentum. we can 2 know. x]i| = |hˆx x − xpx i| p ˆ p ˆ ˆˆ 2 ¯Z 2 ¯ µ ¶ ¯ 1¯ ¯ ψ ∗ ~ ∂ x − x ∂ ψdx¯ = ¯ 2¯ i ∂x ∂x ¯ ¯ ¯~¯ ~ = ¯ ¯= .

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

ψ must equal zero in these regions. Therefore it must satisfy the boundary conditions (b. The particle must be found only in region II.c.): ψ(0) = 0 and ψ(a) = 0. The Schrödinger equation in region II is (V (x) = 0)
2 2 ˆ = Eψ =⇒ −~ d ψ(x) = Eψ. in region I and III.
32
.Now. where the potential is inﬁnite. where k = q
2mE .4)
Now ψ must be continuous for all x. ~2
(4. dx2 ~ The general solution of this diﬀerential equation is ψ(x) = A sin kx + B cos kx.3)
(4. Hψ 2m dx2
(4.2)
which can be rearranged into the form d2 ψ(x) 2mE + 2 ψ(x) = 0. the particle can never exist so.

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

10)
We can get the energy levels from kn = En =
and kn =
nπ : a
h n2 π 2 ~2 ~= 2π n2 h2 = .9)
Is this wavefunction OK?
Thus our normalized wavefunctions for a particle ⎧ ⎪ 0 ⎪ q ⎨ 2 ψn (x) = sin nπx a ⎪ a ⎪ ⎩ 0 q
2mEn ~2
(4.2. a in a box are I II III .11)
4. Implications of the Particle in a Box problem
Zero Point Energy
34
.
(4. 2ma2 8ma2
(4.Solving for A gives A=
r
2 .

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

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

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

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

2 By postulate III the Schrödinger equation becomes ⎛ ⎞
K.x From Newton’s law of motion F = ma = m d 2 . P. we need to express the force of the spring in terms of potential energy V . where ω = conditions. q
k m
(5.E. so in going to the quantum oscillator. we get dt
2
d2 x k d2 x m 2 = −kx ⇒ 2 + x = 0 dt dt m
(5.
This can be rearrange into the form −~2 d2 ψ + 2m dx2
1 ⎜ −~2 d2 ⎟ ˆ Hψ = Eψ ⇒ ⎝ + kx2 ⎠ ψ = Eψ.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. We know Z 1 V = − F dx = kx2 + C.
39
. Thus V = 1 kx2 . (5.5)
This diﬀerential equation is not easy to solve (you can wait to solve it in graduate school).4)
(5.E. 2 2 |2m dx } | {z } {z µ ¶ 1 2 kx − E ψ = 0 2
(5.3) 2 Since energy is on an arbitrary scale we can set C = 0.1)
This is second order diﬀerential equation which we already know the solutions to: x = A sin ωt + B cos ωt.

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 . Interesting Aspects of the Quantum Harmonic Oscillator
It is interesting to investigate some of the unintuitive properties of the oscillator as we have gone quantum mechanical
40
. 2 ~ 2n n! π
where An is the normalization constant for the nth eigenfunction and Hn (y) are the Hermite polynomials.6) x. An = p √ . 11. ∗ ∗ ∗ See Fig. As it turns out. m
(5.8)
q
k m
and is called the vibrational constant.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.12 Laidler&Meiser ∗ ∗∗
5. y = (5. 2 where ν 0 =
1 2π
(5.1. 2 where again ω = q
k . The eigenvalues (the energy levels) are 1 En = (n + )~ω.7)
Note the energy levels are often written as 1 En = (n + )hν 0 .

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

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

ˆ Hψ = Eψ.
(5.Key Equations for Exam 1
Listed here are some of the key equations for Exam 1.11)
43
43
. N unnorm (5. The equations are collected here simply for handy reference for you while working the problem sets.10)
• The Schrödinger equation (which should be posted on your refrigerator). This section should not substitute for your studying of the rest of this material.
Equations
• The short cut for getting the normalization constant (1D. 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. see above for 3D). sZ N=
space
|ψunnorm (x)|2 dx.9)
• The normalized wavefunction: ψ norm = 1 ψ .

ˆ hˆ i = α
space
(5.19)
44
. 2ma2 8ma2
(5. r
• The energy levels are 1 En = (n + )~ω. 4E = (2n + 1) h2 8ma2 (5. a a • The energy levels for the 1D particle in a box. An = p ψn (y) = An Hn (y)e . ω = 2
k m
(5. 2 n n! π ~ 2
(5. y = √ .• The Schrödinger equation for 1D problems as a diﬀerential equation.12)
(5.15)
(5. r nπx 2 ψn (x) = sin .18)
where An is the normalization constant for the nth eigenfunction and Hn (y) are the Hermite polynomials. En =
h n2 π 2 ~2 ~= 2π n2 h2 = .16)
• The energy level spacing for the 1D particle in a box. ∂x
(5. −~2 d2 ψ + (V (x) − E) ψ = 0.13)
• The momentum operator
px = −i~ ˆ
∂ .17)
• The wavefunctions for the harmonic oscillator are ¶1 µ 2 km 4 1 − y2 x. Z ψ∗ αψdx.14)
• Normalized wavefunctions for the 1D particle in a box. 2m dx2 • How to get the average value for some property (1D version).

Part II Quantum Mechanics of Atoms and Molecules
45
45
.

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

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

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

the solutions to our diﬀerential equation are closely related to the Laguerre polynomials. µ ¶l µ ¶ 2σ 2σ −σ/n 2l+1 Rnl (σ) = Anl . Also Note: the energy levels are the same as for the Bohr model. depends on the n and l quantum numbers as sµ ¶3 2Z (n − l − 1)! Anl = − (6. the energy levels are given by En = − Z 2R n2 (6.15) e Ln+1 n n
where the normalization constant. which will be brieﬂy discussed later) is ψ nlm (r. 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).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. i.17)
Note: The energy levels are determined by n alone–l drops out. So. Anl .The Ylm (θ.e. the total wavefunction that describes a hydrogenic system (ignoring the spin of the electron. n In fact. θ..18)
6.2. (6.16) na0 2n[(n + l)!]3 The energy eigenvalues. φ) (6. Discussion of the Wavefunctions
We are now very close to having the atomic orbitals familiar from freshman chemistry. φ) = Rnl (r)Ylm (θ.
49
.

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

so we can not write down an explicit function of the coordinate space variables.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. electrons also posses an intrinsic quantity called spin.
51
. Spin of the electron
ψ3dz2 = ψ3d0 £ ¤ 1 2 ±1 ψ3dxz = √2 ψ3d1 + ψ3d−1 £ ¤ 1 2 ±1 ψ3dyz = i√2 ψ3d1 − ψ3d−1 £ ¤ 1 2 ±2 ψ3dxy = √2 ψ3d2 + ψ3d−2 £ ¤ 1 ψ3dx2 −y2 = i√2 ψ3d2 − ψ3d−2
2 0
ψ1s = ψ1s ψ2s = ψ2s ψpz = ψ2p0 £ ¤ 1 ψ2px = √2 ψ2p1 + ψ2p−1 £ ¤ 1 1 ±1 ψ2py = i√2 ψ2p1 − ψ2p−1
As we know from freshman chemistry. Spin is actually rather peculiar so we will put oﬀ a more detailed discussion until next semester.3. • ms is the spin orientation quantum number and ms = ±1/2 for electrons. 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). The spin wavefunction is a function in spin space not the usual coordinate space.

(6.4. Again note that for a free hydrogenic system the total energy depends only on the principle quantum number n. 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. — The principle quantum number. φ)χ The energy is given by Z 2R .ms and “tack it on” as another factor of the complete wavefunction.l. When a particular spin state is needed a further notation is commonly used: α ≡ χ 1 .s.ms = Rnl (r)Yl.We simply denote the spin wavefunction generally as χs. 1 (the “spin-up” state) and β ≡ χ 1 .3.ms = ψn. En = − The quantum numbers of the hydrogenic system • The principle quantum number. n. l: determines the total angular momentum of the system.m.m (θ. It also determines the atomic sub-shells (6.l. can take on values of 1. • The angular momentum quantum numbers. .− 1 (the “spin-down” state)
2 2 2 2
6.19)
52
. n: determines the total energy of the systems and the atomic shells. .20) n2 where recall.m χs.2.

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

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

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

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

Since we are doing this. (7. Ψ = ψ(1)ψ(2)χ(1)χ(2). However considering the symmetry with respect to exchange we see the following • Ψa has symmetric spatial and spin parts and is there for symmetric. It must be excluded. • Similarly for Ψd . 2) (7.The total wavefunction is Ψ = ψ(1.4)
where the single particle wavefunctions are that of the hydrogenic system. | {z }| {z }
spatial part spin part
(7. The Pauli exclusion principle implies that if the spatial part is even with respect to exchange then the spin part must be odd. • Ψb and Ψc have symmetric spatial parts.5)
57
. one must make an antisymmetric linear combination of the spin parts. 2)χ(1. but the spin part is neither symmetric or antisymmetric.3) Since a complete solution for helium is not possible we must use approximate wavefunctions. Likewise if the spatial part is odd then the spin part must be even. So. 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. we may as well simplify matters and use product state wavefunctions (products of the hydrogenic wavefunctions).

3. . 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=¯ (7.7) (7. Many Electron Atoms
The remaining atoms on the periodic table are handled in a manner similar to helium. . So the ground state wave function for helium is Ψg = ψ1s (1)ψ1s (2) [α(1)β(2) − α(2)β(1)] .6)
7. .The appropriate linear combination is α(1)β(2) − α(2)β(1). . . . ¯ ¯ ¯ ¯ ¯ ψ (N)α(N) ψ (N)β(N) ψn (N )α(N) ψn (N)β(N) ¯ 1s 1s
58
. . . The product wavefunction for the ground state is determined by applying the aufbau principle. ¯ ¯ . .8) . Namely the wavefunction is product state that must be antisymmeterized in accordance with the Pauli exclusion principle. . 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. . . .

9)
(7.10)
• The short hand notation for these states is (1s)2 (2s)1 7. This agrees with the Puli exclusion principle.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). • 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. 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 − + (7.11) H= 2me i 4π 0 ri j>i 4π 0 rij i=1
59
. ψ1s β. and ψ2s α (or ψ 2s β).1.3. 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. As an example consider lithium: • There are three electrons so we need three hydrogenic wavefunctions: ψ1s α. It is also antisymmetric under exchange of columns.

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

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

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

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

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

10. LCAO–Linear Combinations of Atomic Orbitals
Now that we know what symmetry the molecular orbitals must posses. Molecular Orbital Diagrams
10. we need to ﬁnd some useful approximations for them. We will discuss the approximation which models the molecular orbitals as linear combinations of atomic orbitals (LCAO). Useful can mean qualitatively useful or quantitatively useful.1.2)
72
72
. Let us again consider the hydrogen molecular ion H+ : let one H atom be labelled 2 A and the other labelled B. Unfortunately we can’t have both.1) and (1sB ) = ke−rB /a0 (10. LCAO is qualitatively very useful but it lacks quantitative precision. 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.

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

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

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

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

For example a high lying 1s orbital may combine with a low lying 2s orbital to form a σ molecular orbital. The supplement that follows this section contains some examples of heteronuclear diatomics. • Bond order is deﬁned as BO = 1 (# of bonding electrons − # of antibonding electrons) 2 (10.8)
• Examples follow in the supplement.The molecular orbital diagrams for the second row homonuclear diatomics are rather simple.
77
. This disparity is not present for homonuclear diatomics. A consequence of this energy level disparity is that molecular orbitals may be formed from nonidentical atomic orbitals. Heteronuclear diatomics are some what more complicated since there is a disparity in the energy levels of the atomic orbitals for the separated atoms. Bond order • One important property that can be predicted from the molecular orbital diagrams is bond order. ∗ ∗ ∗ See Supplement ∗ ∗∗ The supplement that follows this section contains examples for each of the second row diatomics.

(Next semester will we look at the details of this for polyatomic molecules) ˆ Hmol Ψmol = Emol Ψmol (10.9) ´ ³ ˆ ˆ ˆ Hele + Hvib + Hrot ψele ψvib ψrot = (Eele + Evib + Erot ) ψele ψvib ψrot
78
. Likewise we have discussed molecular orbitals which are the electronic wavefunctions. We can succinctly express the Schrödinger equation for a molecule as follows. 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. 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.4.

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

4)
where a trig identity was used in the last step. (11. Thus the light—matter interaction is described as μ(t) = α(t)E(t) = (α0 + α1 cos ω v t) E0 cos ωt = α0 E0 cos ωt + α1 E0 cos ω v t cos ωt ⎡ ⎤ α1 E0 ⎣ cos(ω − ω v )t + cos(ω + ω v )t ⎦ = α0 E0 cos ωt + | {z } {z } | {z } | 2
Rayleigh Stokes Raman AntiStokes Raman
(11.2)
The polarizability also depends on the positions of nuclei to some degree. The second term corresponds to Stokes Raman scattering where the scattered light is shifted to the red of the incident frequency. That is. The ﬁrst term corresponds to Rayleigh scattering where the scattered light is at the same frequency as the incident light.
According to classical electrodynamics an oscillating dipole emits an electromagnetic ﬁeld at the oscillation frequency.3)
(11.For light.
80
. In this case we see the dipole oscillates at three distinct frequencies: ω. ω − ωv and ω + ω v as part of three terms in the above expression. there is a vibrational (and rotational) contribution to the polarizability: α(t) = α0 + α1 cos ωv t (here for simplicity we assume only one vibrational mode). the electric ﬁeld part is E(t) = E0 cos ωt.

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

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

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

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

The equations are collected here simply for handy reference for you while working the problem sets. Anl . 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. Rnl (σ) = Anl (11.6)
µ
2σ n
¶l
e
−σ/n
2l+1 Ln+1
µ
2σ n
¶
. φ) • The radial part is.Key Equations for Exam 2
Listed here are some of the key equations for Exam 2. depends on the n and l quantum numbers as sµ ¶3 2Z (n − l − 1)! Anl = − (11.7)
where the normalization constant. θ.8) na0 2n[(n + l)!]3 85
85
. This section should not substitute for your studying of the rest of this material.
Equations
• The wavefunctions for the hydrogenic system are ψnlm (r. φ) = Rnl (r)Ylm (θ.
(11.

• The energy levels are 1 En = (n + )~ω. ω = 2 • The Morse potential is
r
k m
(11.13)
Now the zero of energy is the dissociated state (i. ω Note: this expression for the Morse potential has the zero of energy at the bottom of the well (i. • The Morse Potential can also be written as Ee (R) = De [e−2β(R−Req ) − 2e−β(R−Req ) ]. (11.9)
• The wavefunctions for the harmonic oscillator are ¶1 µ 2 km 4 1 − y2 ψ n (y) = An Hn (y)e . y = x.e. An = p √ .e. 4De
(11. R = Req .Ee (Req ) = 0). R → ∞.11)
Ee (R) = De [1 − e−β(R−Re q ) ]2 .Ee (R → ∞) = 0).n = −De + hc˜ e (n + ) − hc˜ e xe (n + )2 .• The energy levels for the hydrogenic system are given by En = − Z 2R n2 (11. (11. .12) q μ where De is the well depth and β = 2πc˜ e 2De is the Morse parameter. 2 2 where ω e xe together is the anharmonicity constant.14)
86
. • The energy levels for the Morse oscillator are of the form 1 1 ω ω Evib. 2 n n! π ~ 2
(11. with xe = ˜
hc˜ e ω .10)
where An is the normalization constant for the nth eigenfunction and Hn (y) are the Hermite polynomials. .

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

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

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

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

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

The ﬂuctuation about an average value for any observable property O is described by the variance which is deﬁned as ¯ σ 2 ≡ O2 − O2 . Macroscopic equilibrium is a dynamic rather than static equilibrium.7)
12. It can be shown that (12.8)
σO 1 ≈√ . but sometimes it is important. the value of a certain property ﬂuctuates about the average value. Sterlings Approximation: • In place of evaluating factorials of large number one can use Sterling’s approximation to approximate the value of the factorial.2. Consequently. but when we consider macroscopic systems (1020 or so molecules) no calculator can handle factorials of such large numbers. Fluctuations
When we list the macroscopic properties of a material such as a beaker of benzene or the air of the atmosphere. O σ O is consider the range of the observable property.This is no problem for small numbers. ¯ O N where N is the number of particles.9)
1 √ N
= 10−12
92
. we speak of the average value of the property. So for example if N = 1024 then
(12. Often this ﬂuctuation is not important. • Sterling’s approximation is ln(N!) ' N ln N − N (12.

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

13.1)
Ni
(13. N1 !N2 ! · · · (13. The total energy is given by E=
where Ni is the number of particles in energy state i. of course. and the total number of particles will be constant. Since the system is isolated the total energy. 94
94
. N= X
i
X
i
Ni i .3)
A system in equilibrium always tries to maximize entropy and minimize energy and so the equilibrium conﬁguration is a compromise between these two cases. 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! . The total number of particles is.
(13. E.

95
. We start by considering our original system–that being one with constant energy. That is all Ni = 1 or 0.4) −β j j gj e | {z }
pi
where β ≡
1 kT
and gj denotes the degeneracy of states having energy
j. These two situations are contradictory and some compromise must be obtained. The derivation using Lagrange multipliers arrives at the conﬁguration in which the gi e−β i Ni = N P . This would be the situation in which every particle was in a diﬀerent energy state.For the moment let us relax the isolation constraint. Maximizing entropy corresponds to maximizing W (via S = k ln W ). 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. Minimizing energy would be the case where all the particles are in the ground state (say 1 ). We will not discuss this method in detail and consequently we cannot derive the equilibrium conﬁguration. (13. This is done using the mathematical technique of Lagrange multipliers (page 951 of your calc book).

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

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

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

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

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.
106
. We will make the distinction between the Helmholtz free energy and the more familiar Gibb’s free energy (G) later as well.12) ∂β ∂β n. it is the energy of the system minus the energy that is “tied-up” in the random (unusable) thermal motion of the particle in the system: A ≡ U − T S Free energy is probably the key concept in thermodynamics and so we will discuss it in much greater detail later.Helmholtz Free Energy Free energy is the energy contained in the system which is available to do work.V 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.

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

Closed system: A system that cannot exchange matter with its environment but may exchange energy. Types of Systems Isolated system: A system that cannot exchange matter or energy with its environment.4) ¶
z
5.1.3. Microscopic systems: Systems containing a small number of particles. Finally
µ
∂z ∂x
¶
=
u
µ
+
y
µ
∂z ∂y
¶ µ
x
∂y ∂x
(15.3)
y
4. 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. The cyclic rule:
¶
y
∂z =− ∂y ∂z ∂x ¶
µ
¶ µ
x
∂y ∂x
(15. Deﬁnitions
System: a collection of particles Macroscopic systems: Systems containing a large number of particles.2.5)
u
15. 15.
108
. The reciprocal rule:
µ µ ∂z ∂x
∂z ∂x
¶ µ
y
∂x ∂z
¶
=1 ¶
(15.2.

temperature.
volume moles
= molar volume. • Heat is exchanged if only internal parameters are changed during the process.2. Extensive properties can be “converted” to intensive properties through ratios: Extensive property → Intensive property.
109
.
= density. pressure. heat capacity. Work and Heat
A system may exchange energy with its environment or another system in the form of work or heat. Extensive property For example
mass volume
(15. 15. volume.Open system: A system that may exchange matter and energy with its environment. • Work is exchanged if external parameters are changed during the process.2. density. Adiabatic system: A closed system that also can not exchange heat energy with its environment. • For example.
heat capacity mass
15. System Parameters
Extensive parameters (or properties): properties that depend on the amount of matter.6) = speciﬁc heat. • For example. Intensive parameters (or properties): properties that are independent of the amount of matter.3. mass.

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

dM Moles. σ Surface tension. dA Charge.if more than one set of parameters change. dε Surface area. dV Strain. 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. dQ Magnetization. A Generalized Displacement.3. μ Gravity. E Magnetic Field. That is dw = −P dV. H Chemical Potential. −P Stress. 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. a Contribution to dw Pressure. The following table gives some examples of generalized forces and displacements Generalized Force. dh −P dV σdε γdA EdQ HdM μdn mgdh
15. this is called P V work. mg Volume. dn Height.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
. γ Voltage. (15.2.

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

16. 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.1.16.
In the ﬁgure wA = −
Z
V2
V1
Patm dV = −Patm (V2 − V1 )
(16.1)
113
113
. Maximal Work: Reversible versus Irreversible changes
The value of w depends on Pex during the entire expansion.

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

7) That is.8)
(16.b. divide by mass to get speciﬁc heat 1 cV = m We will discuss heat capacity more later. Heat Capacity
Temperature and heat are diﬀerent.. it is not a constant.g. ¡ dq ¢ ¡ dq ¢ e. Temperature is not the amount of heat.6)
(16. heat is related to temperature through the heat capacity dq dT n. µ dq dT ¶ (16. dq amount of heat energy is transferred. To make an intensive property 1. The heat capacity also depends on the conditions during the temperature change. C(T ) = From this equation dq = C(t)dT. CV (T ) = dT V and CP (T ) = dT P are not the same Heat capacity is an extensive property.16. when the temperature of a substance having a heat capacity C(t) is changed by dT.2. heat capacity is a function of T . divide by the number of moles to get molar heat capacity µ ¶ 1 dq CV m (T ) = n dT V 2.9)
V
115
. (16. However.. Temperature is an intensive property and heat is an extensive property.

Equations of State
The macroscopic properties of matter are related to one another via a phenomenological equation of state. (16. T . n m V
The equation of state can also be expressed in terms of density ρ = mass m/n) MP mP = .. but behave in the same way as the more simple pure system. homogeneous material (in the absence of external ﬁelds) is given by the values of any two intensive properties. ρ= nRT RT
(and molar (16.g.11) where Vm =
V .315 J K−1 mol−1 ) and n is the number of moles. (More complicated systems require more than two independent variables. 16. C(T. (16.16.) The functional dependence of any property on the two independent variables is an equation of state. P independent then heat capacity is a function of T and P .1.3.10)
where R is the gas constant (8.12)
116
. e. The state of a pure. so we will focus our development of thermodynamics on simple systems. Example 1: The Ideal Gas Law The equation of state for volume of an ideal gas is P V = nRT .3. The ideal gas equation of state can be expressed in terms of intensive variables only P Vm = RT . P ).

13)
The parameter a attempts to account for the attractive forces among the particles The parameter b attempts to account for the repulsive forces among the particles b originates from hard sphere collisions (see ﬁgure):
117
. Example 2: The van der Waals Equation of State A more realistic equation of state was presented by van der Waals: P = nRT n2 a − 2.16.3.2. V − nb V (16.

17)
118
.16)
• Redlich-Kwang P = (16.3.14)
16.In term of intensive variables P = a RT − 2. Other Equations of State The van der Waals equation of state is not the only one that has been proposed.15)
RT e− RT Vm nRT e− RT V = P = V − nb Vm − b nRT n2 a a RT −√ −√ = V − nb Vm − b T V (V − nb) T Vm (Vm − b)
(16. Vm − b Vm (16.3. Some other equations of state are • Berthelot • Dieterici n2 a a nRT RT − − = 2 2 V − nb T V Vm − b T Vm
an a
P =
(16.

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

15 K and P = 1 bar.15 K and P = 1 atm. (17.1)
The zeroth law implies that if an arbitrary system. Adiabatic wall: A wall the does not allow heat to ﬂow through it. C. (Vm (SATP) = 24. The zeroth law of thermodynamics • Mathematical statement: If TA = TB and TB = TC .789 L/mol)
Diathermic wall: A wall that allows heat to ﬂow through it.414 L/mol) • standard ambient temperature and pressure (SATP): T = 298. (Vm (STP) = 22. 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.
120
. Thermal equilibrium: If two systems are in contact along a diathermic wall and no heat ﬂows across the wall.Standard conditions • standard temperature and pressure (STP): T = 273. then the systems are in thermal equilibrium. then TA = TC This the mathematical statement of transitivity • Verbal statement: If system A is in thermal equilibrium with system B and system B is in thermal equilibrium system C then system A is also in thermal equilibrium with system C.

The internal energy state function For characterizing the change in energy of a system. The value of the state function depends only on that given state and on no other possible state of the system. V (T.2..3)
4U = q + w
(17. P )). one is concerned with the work done on the system (w) and the heat supplied to the system (q).g. The First Law of Thermodynamics
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
. The energy of a system is called the internal energy (U) of the system.2.1.2)
• 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. The ﬁrst law of thermodynamics: • Mathematical statement: or in diﬀerential form dU = dq + dw (17.
So for a system where all the work is P V work the ﬁrst law becomes Z V2 4U = q − Pex dV
V1
(17.17. 17.

The total diﬀerential of U (T. V ). the most convenient at this time are V and T.
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. ∂T The other slope. ¡ ∂U ¢
∂V T
(17.8)
.6)
(17. is called the internal pressure (it has no standard symbol). ¶ ¶ µ ∂U ∂U dq = CV dT = dq =⇒ = ∂T V ∂T V dT ¡ ¢ Hence the slope ∂U V is the heat capacity.5)
Although U can be expressed as a function of any two state variables. 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.9)
(17.7)
µ
(17. U → U(T. dU = ∂T V ∂V T So.in diﬀerential form this is dU = dq − Pex dV (17.10)
V
122
.

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. A useful approximation is 4U = CV 4T which is valid for i) heat capacity nearly constant over 4T and with no phase transitions. Hence ∂T ∂T ¶ ∙ µ ¸ ∂P − P dV dU = CV dT + T ∂T V
(17. and P.11)
The equation of state for U : Express U in terms of T. 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). ii) ideal gas or at constant volume.
123
.12)
(17.13)
is the equation of state for U. V.

S. S is also a state function .1) T ¯ Now. A. and T are state functions. T T T Since U. is a measure of the disorder of the system and is expressed via Boltzmann’s equation S = k ln W (where W is the micocanonical partition function) We expressed Boltzmann’s law in terms of the more convenient canonical partition function as ¯ E S = + k ln Q. S= So we may write dS = (18. The Second and Third Laws of Thermodynamics
18.2)
1 (dU − dA) T 124
(18.18. Furthermore we derived the simple relation between the Helmholtz free energy and the canonical partition function as A = −kT ln Q. U A 1 − = (U − A). the average energy of the system E is in fact what we call internal energy: ¯ U ≡ E.3)
124
. (18.1. Hence. Entropy and the Second Law of Thermodynamics
We learned from statistical mechanics that entropy.

We learned previously that the maximum amount of work one can extract from the system is the work done during a reversible process. 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. For now let us limit the discussion to reversible processes. Hence dA = dwrev . (Reversible process) = T (18.for an isothermal process.V ≥ 0 For a general process: dU = dq − Pex dV For a reversible process Pex = P and dq = T dS so dU = T dS − P dV
125
.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.

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

Work must be done to transfer heat from a cold to a hot reservoir. So CV dT =⇒ 4S = dS = T Z
T2
(18. 2.2. So.6)
From our earlier discussion of heat capacity dq = CV dT (CV since constant volume). dU = dq + dw = dq − Pex dV (18. The entropy of the universe is increasing 5. the second law has a number of equivalent statements 1. 3. The entropy of an isolated system will always increase in a spontaneous process (the principle of Clausius)
18. T
(18. The Third Law of Thermodynamics
Consider the ﬁrst law for a reversible change at constant volume. 4.1. dU = CV dT but also dU = T dS.1.7)
T1
CV dT. A useful perpetual motion machine does not exist. 6. Spontaneous processes are irreversible in character.18. Statements of the Second Law Unlike the ﬁrst law.8)
127
. A cyclic process must transfer heat from a hot to cold reservoir if it is to convert heat into work.

1.2. The Third Law Verbal statement The third law of thermodynamics permits the absolute measurement of entropy. To derive the mathematical statement of the third laws we starting with Z T2 CP dT (18.12)
From a macroscopic point of view S0 is arbitrary. a microscopic point of view suggests S0 = 0 for perfect crystals of atoms or of totally symmetric molecules (e.). Thus CP → 0. Consider the heat capacity near T → 0. However. O2 etc.g. Alternative statement of the third law: Absolute zero is unattainable. Ar. S0 6= 0 for imperfect crystals and crystals of asymmetric molecules (e.
128
. CO).9) 4S = T T1 18.10) 4S = T T1 now let T1 → 0 4S = S2 − S0 = Z
T2
0
CP dT T
(18...g. For S0 to have signiﬁcance
CP T
must be ﬁnite (not inﬁnite) as 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 (18.11)
Hence the mathematical statement of the third law is Z T2 CP S(T2 ) = dT + S0 T 0
(18.

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

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

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.Key Equations for Exam 3
Listed here are some of the key equations for Exam 3. The equations are collected here simply for handy reference for you while working the problem sets.16)
131
131
. 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.15)
• The canonical partition function is Q=
gj e−βEj
(18.14)
(18.
(18.

V ´ ∂ ln Q = −kβ ∂β n.17) N! • The Translational Partition Function V qtrans = 3 (18.18) Λ where h Λ≡ √ (18.β = β
³
=−
+ k ln Q ¡ ∂ ln Q ¢
∂V
³
∂ ln Q ∂β
´
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 .V ¡ ∂Q ¢ 1 1 = βQ ∂V n. O= Q i
(18.β
132
. (18.21)
• The ensemble average of any property is given by 1 X ¯ Oi gi e−β i .19) 2πmkT is the thermal de Broglie wavelength.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. σθr
2
(18.• The relation between the partition function and the molecular partition function is qN Q = mol . • The Rotational Partition Function (linear molecules) is T qrot ≈ . 2 sinh 1 β~ω 2 (18.V
n.

Also.30)
∗ where CP m is the molar heat capacity at the lowest temperature for which there is data.25)
(18. dU = T dS − P dV.
(18.29)
• Debye’s law for entropy at very low temperatures Sm (T ∗ ) =
∗ CP m .28)
0
CP dT + S0 T
(18.26)
(18. S(T2 ) = Z
T2
(18.• P V work is • Heat capacity: • General forms of the ﬁrst law:
dw = −P dV. 3
(18. dq = C(t)dT.
133
. in diﬀerential form this is dU = dq − Pex dV.27)
(18. • The second law • The third law T dS ≥ dq.24)
4U = q + w.23)
(18.

Part IV Basics of Thermodynamics
134
134
.

brieﬂy the Helmholtz free energy.1. and kinetics–topics we will encounter throughout the year. electrochemistry. 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.
135
135
. here too is energy the key property with which to work. 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.
19. The Other Important State Functions of Thermodynamics
As was the case in quantum mechanics.19. K. Consequently. The equilibrium constant for a thermodynamic process. the concept of equilibrium plays a key role in much of what we will discuss for the remainder of the year.

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

consider an reversibly expanding gas under constant pressure (dP = 0) and adiabatic (dq = 0) conditions. but dU = T dS − P dV. 19. in doing so it must lose energy. The system does work during the expansion. If the process occurs at constant pressure then the enthalpy change is the heat given oﬀ or taken in.2)
/ / dH = T dS − P dV + P dV + V dP
= T dS + V dP. For example.
19.3. Hence Enthalpy does indeed have the desired natural variables. Since the process is adiabatic no heat energy can ﬂow in to compensate for the work done and the gas cools.1. The total internal energy decreases.Now formally dH = dU + d(P V ) = dU + P dV + V dP. As Freshmen we learn this as 4H = qp . so (19.3)
Enthalpy is the total energy of the system minus the pressure volume energy. 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. Heuristic deﬁnition:
(19.2. Helmholtz Free Energy
Now we want a state function whose natural variables are T and V
137
. So a change in enthalpy is the change in internal energy adjusted for the P V work done.

4.
(19.3.
19.1.4)
/ / dA = T dS − P dV − T dS − SdT
= −P dV − SdT. so dG = T dS + V dP − T dS − SdT / / = V dP − SdT.7) (19.Let us try the deﬁnition A ≡ U − T S. (19. but dU = T dS − P dV. 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. Formally dA = dU − d(T S) = dU − T dS − SdT.5)
Hence Helmholtz free energy does indeed have the desired natural variables. but from above dH = T dS + V dP. Hence Gibbs free energy does indeed have the desired natural variables. 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. Now formally dG = dH + d(T S) = dH − T dS − SdT.6)
138
. 19. so (19.

11) CP = ∂T P So. 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 (19.1.8)
The constant pressure heat capcity can then be expressed in terms of enthalpy as ¶ µ ∂H .5.9) (19.10) (19.1. ¶ ¶ ¶ µ µ ∂ (U + P V ) ∂U ∂V CP = = +P (19. Heuristic deﬁnition: Gibbs free energy is the energy of the system which is available to do non P V work–It is the internal minus both that energy which is “used up” by the random thermal motion of the molecules and used up in doing the P V work.4. (19.12) ∂T ∂T P ∂T P P ¡ ¢ ¡ ¢ note ∂U P is not CV we need ∂U V . Heat Capacity of Gases
19. 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.
19.5.13)
P
139
.

14) CP = ∂V T ∂T P ∂T P V ¶ ∙µ ¶ µ ¸ ∂U ∂V = CV + +P .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 (19.18)
19.17) ∂T P ∂T V nRT nR nR = nR = CV + T P V PV Thus CP = CV + nR or CP m = CV m + R (19.15)
∂P ∂T
¶
(19. The Maxwell Relations
Summary of thermodynamic relations we’ve seen so far Deﬁnitions and relations: • H = U + PV
140
.16)
V
Example: Ideal gases 1. ∂T P ∂V T ¡ ¢ ¡ ∂U ¢ Recall the expression for internal pressure ∂V T = T ∂P V − P .6. Then ∂T µ ∂U ∂T µ CP = CV + Finally CP = CV + T µ ∂V ∂T ¶ ∙ µ ¶ ¸ ∂P T −P +P / / ∂T V P µ ∂V ∂T ¶ µ
P
¶
(19.

• 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
.

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. Hence at equilibrium (dA)T.V = 0. Spontaneity of processes
Two factors drive spontaneous processes 1.2)
. T dS ≥ dq for a spontaneous process. The tendency to maximize entropy
Let us begin with Helmholtz free energy The total diﬀerential of A is (A = U − T S) dA = dU − T dS − SdT = dq − Pex dV − T dS − SdT For constant T and V.1)
(20.V ≤ 0 for a spontaneous process. Chemical Potential
20.1. The tendency to minimize energy 2.20. (dA)T. (dA)T.V = dq − T dS From the second law.

P = dq − T dS Again from the second law. Hence at equilibrium (dG)T. Note free energy provides no information about how fast a process proceeds to equilibrium.5) (20. The free energy functions are the workhorses of applied thermodynamics so we want to get a feel for them. dA = dU − T dS − SdT and dG = dH − T dS − SdT. (dG)T.P ≤ 0 for a spontaneous process. Plugging these into the total diﬀerentials of free energy gives dA = −SdT − P dV and dG = −SdT + V dP (20. (dG)T.P = 0. T dS ≥ dq for a spontaneous process.6) (20.4) Expressing dU and dH generally as dU = T dS − P dV and dH = T dS + V dP (remember that in general T dS cannot be identiﬁed with dq and P dV cannot be identiﬁed with −w). (20. So free energy provides a measure of the thermodynamic driving force towards equilibrium.3)
143
. Returning to the total diﬀerentials of free energy.For constant T and P = Pex .

Chemical potential
What if the amount of substance can change?
144
.10)
So. as stated earlier.7)
(20. In general dw = dw0 − Pex dV where dw0 is the non-P V work. The total diﬀerential of G is also dG = dq + dw + P dV + V dP − T dS − SdT.P = wmax
(20. The total diﬀerential of G becomes dG = dq + dw0 − Pex dV + P dV + V dP − T dS − SdT.2.8)
(20.P = dq + w0 − T dS. For reversible processes q = T dS and this becomes
0 0 (dG)T. the Gibbs free energy is the energy of the system available to do non-P V work. Hence (dA)T = dwmax =⇒ (4A)T = wmax . As we have stated in words a number of times before. The total diﬀerential of A is also dA = dq + dw − T dS − SdT.
20.P = dwmax =⇒ (4G)T. (dG)T. For constant T and P = Pex . For a reversible process dq = T dS and work is maximal. but i) only P V work and ii) closed systems.9)
(20.These expressions are quite general.

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

146
.16)
where g(ζ) is any reference function (e.
(20. 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. concentration etc. a solute is dissolved in a solvent. for example. pressure..we see that μ=
µ
∂G ∂n
¶
. 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. mole fraction. The Gibbs free energy per mole (Gm ) for a pure substance is equal to the chemical potential. Activity is hard to deﬁne in words and indeed it has an awkward mathematical deﬁnition as we will soon see. (Gm = μ)
20. and ζ ª is the value of ζ at the reference state.T
So.).g. The mathematical deﬁnition of activity ai of some species i is implicitly stated as
ζ→ζ
lim ª
ai =1 g(ζ)
(20. there exist complicated interactions which cause deviations from ideal behavior.3.15)
P. Activity and the Activity coeﬃcient
When. To account for this one must introduce the concept of activity and the activity coeﬃcient.

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

μi − μª = RT ln ai . P (20.3. i (20. only relative potentials can be measured.20)
Rather than referencing to the standard state one can also reference to any convenient “ideal” state. This ideal state is in turn referenced to the standard state.2.22)
148
. Activity and the Chemical Potential One cannot measure absolute chemical potentials. The deviation of the chemical potential at the state of interest versus at the reference state is determined by the activity at the current state (the activity at the reference state is unity by deﬁnition). For the state of interest μi = μª + RT ln ai (20. By convention we chose a standard state and measure relative to that state. so γ= a ⇒ a = γP.21) i and for the ideal state μid = μª + RT ln aid ⇒ μª = μid − RT ln aid . i i i i i i (20.Our reference function is very simple: g(ζ) = ζ = P . 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
20.19)
Thus the activity of our real gas is given by the activity coeﬃcient times the pressure of an ideal gas under the same conditions.

(20.26)
(20. (20. Pª The usual standard state is the ideal gas at P ª = 1. μid → μª ). (20.23)
μi − μid = +RT ln ai − RT ln aid i i ai = RT ln id ai
Example: Real and ideal gases at constant temperature. Thus μ = μª + RT ln f. so a = f for real gasses.25) dμ = μª Pª P This gives P . dμid = P
z}|{ = dGm = −Sm dT + Vm dP
=0
(20.27)
For gases activity is usually called fugacity and given the symbol f . 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. Starting from the begining dμ
id
dμid = Vm dP RT dP.Thus.28) (20.29)
149
. (Note that as P → 1. so μid − μª = RT ln μid = μª + RT ln P. Lets say our gas is not ideal. then at a given pressure μ = μª + RT ln a. but any pressure.

30)
and at elevation h
z }| { μ (0) = μ + RT ln 1 = μª μid (h) = μª + RT ln Ph
=0
(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.33)
(20.
150
. 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.e. μid = μª + RT ln P where we will take the reference state to be at sea level. i. So at sea level
id ª
(20. This is easily done by using μª = μid − RT ln P in the above equation for μ. we want to reference to the ideal gas at the current pressure P.31) (20. P ª = 1 atm. We have an ideal gas so.32)
The gas ﬁelds the gravitational force which gives it a potential energy per mole of Mgh at height h. 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.

1)
151
151
. Ka . The quantity aB deﬁnes the equilibrium constant.21.2) (21. aA (21. Since A and B are in equilibrium their chemical potentials must be equal μA = μB Now. for this process. if we multiply the above by n moles we have aB −4Gª = nRT ln aA as a consequence of the equilibrium condition. Equilibrium
First let us consider the equilibrium A B.3) (21. 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 equilibrium condition is aμA + bμB = cμC + dμD .7)
(21. Consider a more complicated equilibrium aA + bB cC + dD.6)
(21. In a manner similar to the above aμª + aRT ln aA + bμª + bRT ln aB = cμª + cRT ln aC + dμª + dRT ln aD (21.5)
4μ = μª − μª + RT ln aB − +RT ln aA B A aB 4μ = 4μª + RT ln .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. aA
Again multiplying by n gives 4G = 4Gª + nRT ln aB . aA
If the 4G < 0 then the transition A → B proceeds spontaneously as written.4)
μª + RT ln aA + 4μ = μª + RT ln aB A B
(21.8) 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
(21.9)
152
.

0. 21. We now consider the problem of determining the equilibrium concentrations of a solute A in both phases of an immiscible mixture.
(21. Equilibrium constants in terms of KC Equilibrium constant in terms of a condensed phase concentration:
0 KC =
[C]c [D]d [A]a [B]b µ γc γd C D γa γb A B
. The Partition Coeﬃcient Up to now we have only considered miscible solutions.3.11)
which is related to Ka by Ka =
0 KC
. ¶
(21.4.10)
Note: n is absent in the above since the molar values are implied by the stoichiometry.0.12)
If the reactants are solutes then as the solution is diluted all the activity coeﬃcients 0 go to unity and KC → Ka .
21.
153
.the equilibrium constant is ac ad Ka = C D =⇒ 4Gª = −RT ln Ka aa ab A B (21.

for species A in the α—β mixture. the drugs must transfer between an aqueous phase and a oil phase. P β/α ≡ Kpart . α aA ª
(21. it is called the partition coeﬃcient. 4Gª ≡ Gª −Gª .The equilibrium equation is Aα Aβ The equilibrium expression for this process is 4Gα→β = 0 = 4Gª − nRT ln Ka .13)
where. to enter the body.
154
. α→β (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 . The equilibrium constant for this process has a special α α→β β β/α name.15)
[A]β .14) (21. [A]α
(21.16)
Knowledge of the partition function is important on the delivery of drugs because.

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

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

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 = −285.1.1.012 kJ
22.1. Heats of Formation Hess’s Law of heat summation: 4rxn H is independent of chemical pathway Example: C2 H2 +H2 = C2 H4 .63 kJ 2 2CO2 +2H2 O(liq)→C2 H4 + 3O2 4rxn H ª = +1410. This direct reaction is not easy but it can be done in steps C2 H2 + 5 O2 → 2CO2 +H2 O(liq) 4rxn H ª = −1299.97 kJ H2 + 1 O2 →H2 O(liq) 4rxn H ª = −285.49 kJ
The heat of formation 4f H ª is the 4rxn H at STP in forming a compound from its constituent atoms in their natural states. H2 .83 kJ 2 C2 H2 +H2 = C2 H4 4rxn H ª = −174.818 − (−285.2. Example: Formation of water • H2 + 1 O2 = H2 O not 2H2 +O2 = 2H2 O 2 • 4rxn H = ponent. O2 .22.2)
157
. 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 = −241.830) = 44. P
i
ν i 4f H(i). Temperature dependence of the heat of reaction Z T2 4rxn CP dT 4rxn H(T2 ) = 4rxn H(T1 ) +
T1
(22. C(graphite) are examples of atoms in their natural state.

Reversible reactions
Recall the requirement for a spontaneous change: 4G < 0 for constant T and P.22. i So. where Q ≡
i
aν i is the activity quotient. 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.3)
(22.i for pure substance i). 4rxn G = 0 and Q = Ka (Thermodynamic equilibrium constant). For the reaction aA + bB = cC + dD Ka = ac ad C D aa ab A B (22.
(22. 4rxn G = i
i i 4rx n Gª
X
i
ν i μi .
158
.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. i
At equilibrium.4)
(22. 4rxn G = G(products) − G(reactants) = (remember μi = Gm. Ka depends on T but is independent of P. z }| { X X ν i μª + RT ν i ln ai .7)
• Note that the activity of any pure solid or liquid is for all practical purposes equal to 1.2.

15)
159
. 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 . Temperature Dependence of Ka
Starting with G =´H − T S or G/T = H/T − S. ∂(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 .11)
(22.10)
(22.
So at equilibrium.9)
22. ³ From this ∂(G/T)) = H. a b PA PB (P ª aA )a (P ª aB )b
i
(22. we get ¶ µ 4rxn H ª ∂ ln Ka ind. 4rxn G = 4rxn Gª + RT ln Q becomes 0 = 4rxn Gª + RT ln Ka ⇒ 4rxn Gª = −RT ln Ka .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
.• For ideal gases.3. (22.12)
=
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. d ln Ka =− = ∂(1/T ) P of P d(1/T ) R or (using
d d(1/T )
(22.13)
(22.

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

23. Ionic Activities
Consider a salt in solution Mv+ Xv− → v+ M z+ (aq) + v− X z− (aq). ln aj = RT and ln asalt = j = + or − (23. RT
(23.4)
161
161
.1)
where v+ (v− ) is the number of cations (anions) and z+ (z− ) is the charge on the cation (anion). (23.3) (23.23.2)
μsalt − μª salt . The chemical potential for the salt may be written in terms of the chemical potential for each of the ions: μsalt = v+ μ+ + v− μ− To determine the activity we start with μj − μª j . To understand these processes we must know something about how ions behave in solution.1. Ionics
Many chemical processes involve electrolytes and or acids and bases.

1.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−
(23.7)
It is the case that 1 mole of salt behaves like v = v+ + v− moles of nonelectrolytes in terms of the colligative properties. a− = γ − m− . alternatively.8) v v We see that 1/v asalt = (av+ av− )1/v ≡ a± .1. This suggests that the interesting quantity is μsalt : v μª μsalt 1/v = salt + RT ln asalt .9) The quantity a± is the mean ionic activity. The mean ionic activity coeﬃcient is
+ − γ ± = (γ + γ − )
(23. 23. Ionic activity coeﬃcients The activity coeﬃcients for ionic solutions can also be deﬁned via a+ = γ + m+ .
(23.6)
(23. where m+ = v+ m and m− = v− m.
ln asalt = v+ ln a+ + v− ln a− or. (23. (23.5)
So.11)
162
. asalt = av+ av−
(23.10)
v
v
1/v
.

15)
where z is the charge of the ion and m its concentration. m0 0 where j = 1 − φ. vφ corresponds to the empirical factor i discussed earlier. vmM1 (23. (23. a− . Results from Debye—Hückel theory: point charge in a continuum The Debye—Hückel equation: √ −α |z+ z− | I √ .16)
163
.The quantities a+ . Recall how γ was calculated from the Gibbs-Duhem equation: Z m j ln γ ± = −j − dm0 .14)
23. So. ln γ ± = 1 − Ba0 I
(23.2. 2 i i
(23. It is convenient to redeﬁne the osmotic coeﬃcient as φ= −1000 g/kg ln a1 .12)
where the subscript 1 refers to the solvent.13)
(23. γ + and γ − cannot be measured individually. Similarly freezing point depression is redeﬁned as θ = vφKf m. Theory of Electrolytic Solutions
Ionic strength is deﬁned as I= 1X 2 z mi . One can use the colligative properties to measure the ionic activity coeﬃcients.

which is observed exP perimentally (recall I = 1 i zi2 mi ). 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 .19) This gives the dependence of ln γ ± for dilute solutions (m → 0).3. Q: I= dQ dt (23.21)
164
.18) 1000εkT a0 is the radius of closest approach. Notice that the parameters α and B depend only on the solvent.17)
8πLe2 ρ• . (23.where α= e3 (εkT )3/2 B= µ 2πρ• L 1000 ¶1/2 . Ion Mobility
Current. 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. ρ• is the density of the pure solvent. I is given by the rate of change (in time) of charge. ε is the dielectric constant for the pure solvent and L is Avogadro’s number. (23. e is the charge on the electron. (23. (23. It is seen that √ the DHLL correctly predicts the m dependence of ln γ ± .1
23.20) v+ + v− 1− I This equation works well to ionic strengths of about I = 0.

3.602177 × 10−19 C.(Electrical) work. • Faraday’s constant F = Le = 96485 C/mol (Avogadro’s number of electrons) 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. Some relevant constants • charge of an electron e = 1.1. w. Ion mobility
165
. ε: w = −εQ (23.23)
Conductance is the inverse of the resistance (R−1 ). is required to move a change through a potential (or voltage).

zi eE zi eE = f vi =⇒ vi = . 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.e. where E is the electric ﬁeld. (23.31) f The drag f has three basic origins.30)
The ions quickly reach terminal velocity. So the total force on the ions is a sum of the Coulomb force and the viscous drag Fi = zi eE − fvi (in solution). −. dx
(23.25)
Ni Ni dNi Avi 4t =⇒ = Avi V dt V Ni Avi V (in vacuum)
(23.24)
dQi dNi = |zi | e . Hence Fi = 0.
166
. the viscous drag equals the Coulomb force. dt
(23.The total current passing through an ionic solution is determined by the sum of the current carried by the cations and by the anions I = I+ + I− Now Ii = where i = +. i. E = Also recall Newton’s law
dε .26)
(23.27)
(23. dt dt
(23. (23.29)
The moving ions experience a viscous drag f that is proportional to their velocities..28)
Fi = mai = m
dvi = zi eE.

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

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

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

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
.1.24.

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

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. 4Gv→s = wdis + wtr + wch = wdis + wch (24.
172
.1)
Work done in discharging the sphere: The act of discharging a sphere involves bringing out to inﬁnity from the surface inﬁnitesimal amounts of charge.So.

For n moles of ions (nL = N) 4Gv→s (24. e is the charge of the electron.2)
where z is the oxidation state of the ion. Free Energy of Solvation for the Born Model Combining the above two expression for work gives 4Gv→s = − (ze)2 (ze)2 + 8π 0 ri 8π 0 εs ri µ ¶ (ze)2 1 = −1 8π 0 ri εs N (ze)2 = 8π 0 ri µ ¶ 1 −1 εs (24.1.3)
24. = − 8π 0 ri
(24. ri is the radius of the sphere (ion) and 0 is the permittivity of free space. So.4)
The above expression is 4Gv→s /ion.1. 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.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 .5)
173
. wch = + (ze)2 8π 0 εs ri (24.

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.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. 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 .2.1.
24.
174
. Thus ions always exist more stably in solution than in a vacuum.7)
24.1.The dielectric constant of any solvent is always greater than unity so ε1s − 1 is always negative hence 4Gv→s < 0. 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 =
(24.3.

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.8)
we ﬁnd entropy to be 4Sv→s ∂ =− ∂T " N (ze)2 8π 0 ri µ ¶# 1 −1 .2. We simply list here several phenomena that more sophisticated theories of solvation must consider
175
. the Born model does not make quantitatively correct predictions in many cases.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. (24. εs (24.11)
24.From
µ
∂G ∂T
¶
P
= −S ⇒
µ
∂4Gv→s ∂T
¶
P
= −4Sv→s . Unfortunately however.
(24.9)
The only variable in the above equation that has a temperature dependence is the dielectric constant of the solvent so. µ ¶ 1 N (ze)2 ∂εs N (ze)2 ∂ .

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

Key Equations for Exam 4
Listed here are some of the key equations for Exam 4.1)
(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.2)
. 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.25. This section should not substitute for your studying of the rest of this material. 177
177
dH = T dS + V dP dA = −SdT − P dV dG = −SdT + V dP
(25.

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

16)
√ ny πy nz πz 2 2 nx πx sin sin ψ=√ sin a b c abc E = Ex. −~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.20)
185
. 8ma2 n2 h2 y = .17) (26.ny + Ez. 8mc2 (26.nz The total wavefunction is n2 h2 x . 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.ny Ez.18) nx πx 2 sin . = b b r nz πz 2 sin = c c r (26.nx = Ey.nx + Ey. f (x) is a constant.
(26. a a r ny πy 2 sin . Hence we immediately have ψx = ψy ψz and Ex. 8mb2 n2 h2 z = .So.19)
and the total energy is (26.nz .

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

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

Multiplication: ³ ´ ˆ (x) = α βf (x) ˆ αβf ˆ ˆ (27.5) (27.1) 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. Addition: ˆ if αf (x) = g(x) and βf (x) = h(x). Equality: ˆ if α = β. ˆˆ but in general αβf (x) 6= β αf (x). e.g.4) (27. ˆˆ 4.. then αf (x) = g(x) = βf (x) ˆ ˆ ˆ 2.3)
ˆˆ ˆ α β αf (x) = β (ˆ f (x)) . Inverse: ˆ if αf (x) = g(x) and βg(x) = f (x) ˆ ˆ ˆ then β = α−1 and is said to be α inverse ˆ (27.6)
188
. " #" # " # 1 0 3 1 3 1 = (27.2)
Algebraic rules for operators 1. ˆ ˆ ˆ then (ˆ + β)f (x) = αf (x) + βf (x) = g(x) + h(x) α ˆ 3.— 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.

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

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

(27. j 6= k.27.13)
i
191
. Orthogonality. and the Superposition Principle
Theorem 1: The eigenfunctions of a Hermitian operator corresponding to diﬀerent eigenvalues are orthogonal: Z ψ∗ ψk = 0.12) 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. Completeness.2.

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

50)
The solutions to this partial diﬀerential equation are known to be the spherical harmonic functions ψ lm = Ylm (θ. −l. φ).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 . Quantum Properties of Angular Momentum
The eigenfunctions of angular momentum are entirely speciﬁed by two quantum numbers l and m: ψlm .46)
substituting in the relation we just found for k gives
(28. . (28.45)
and
(28. . l − 2. ˆ L2 ψlm = l(l + 1)ψ lm ˆ Lz ψlm = mψ lm (28. mmin = −l and so m = l. This also implies that the number of ‘rungs’ is 2l + 1 and that l must be either an integer or a half-integer.47)
28. l − 1. .48) (28. simplifying gives l = −l0 Thus mmax = l. l(l + 1) − l02 + l0 = 0.51)
199
.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 . .

meaning. The spherical harmonics (and hence the angular momentum wavefunctions) are orthonormal.55) (28.56) 2I 8π2 I There is no m dependence for the energy.54)
l(l + 1)h2 l(l + 1)~2 = = El . In other words. 2I 2I Thus Elm = (28.The spherical harmonics are functions of two variables. The rigid rotor Rotational energy For general rotation in three dimensions the is ~2 ˆ ˆ H = L2 . 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)Ylm (θ. (28. We know that there are 2l + 1 diﬀerent m values for a particular l value.52)
where the Pl (θ) are the Legendra polynomials and A is normalization constant. ψlm = Ylm (θ. φ) sin θdθdφ = 0 0 l0 6= l or m0 6= m 0 0 28. φ) = APl (θ)eimφ .53) Yl∗m0 (θ. but they are a product of a function only of θ and a function only of φ. All 2l + 1 of these wavefunctions correspond to the same energy. ( Z 2π Z π 1 l0 = l and m0 = m (28.1. Both the spherical harmonics and the Legendra polynomials are tabulated. We say the there is a 2l + 1 degeneracy of the energy levels. the energy levels are determined only by the value of l.
|m| |m|
(28.5.
200
. They are also built-in functions of Mathematica.

(29. One example of such a system is the spin of an electron.29. ∗ ∗ ∗ See in-class demonstration: the belt trick ∗ ∗∗
201
201
. Spin Angular Momentum
We learned above that l may take on integer or half-integer values. Addition of Angular Momentum
29.2)
That means that the system has to ‘rotate’ twice (in spin space not coordinate space) to get back to its original state. One peculiarity of this system is that the wavefunctions are 4π periodic (and 2π antiperiodic): ψs (θ) = −ψs (θ + 2π) (29. The values of m = ms are limited to +1/2 and −1/2.1. l = s = 1/2. These systems have no classical analogs. Systems in which l takes on half-integer values are peculiar.1) and ψ s (θ) = ψs (θ + 4π).

(M = i mi ) • then J = L + S 2.1.max .29. 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. 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. 29. J.)
202
. 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. One measures.2. 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 . the total angular momentum. • we will not use this method. 1. The are two main coupling schemes which account for the total angular momentum of the atom. we use J when we speak generally. (Ms = i msi ) P • ﬁnd the total orbital angular momentum L = Mmax . however.2. The electrons in many electron atoms couple.

The maximum value of J is determined by the maximum value of M by Jmax = Mmax = m1max + m2max = j1 + j2 (29.2. That is. Thus the allowed values of J are J = j1 + j2 . |j1 − j2 | .5)
The total angular momentum is quantized is exactly the same manner as any other angular momentum. 29. . An Example: Two Electrons The table below shows the total spin angular momentum S for a two electron system (29. .2. j1 + j2 − 1.6)
203
. Jmin = |j1 − j2 | . |j1 − j2 | + 1. . (29. .3)
We need to determine the allowed values of the total angular momentum quantum number J. 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 (29.4)
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.ˆ ˆ ˆ The total angular momentum is JT = J1 + J2 .

29. The orbital degeneracy is given by gL = 2L + 1. So. G H
204
. gS . of the states is given by 2S + 1.2. L 0 symbol S 1 P 2 D 3 F 4 5 . In the above example the degeneracy is gS = 3 for the S = 1 states and gS = 1 for the S = 0 states.3. it is worthwhile to brieﬂy discuss them. Term Symbols We have already seen several term symbols. Term symbols are useful for predict and understanding spectroscopic data. 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). those being 1 S and 3 S during our discussion of helium.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. Term symbols are simply shorthand notion used to identify states. For historical reasons L values are associated with a letter like the l values of a hydrogenic system are.

Hund’s Rule for the ground state only. All closed shells have zero spin and orbital angular momentums: L = 0. These states are all singlet S states. • E. If several terms have the same multiplicity then ground state will be that of the largest L. An electron and a “hole” lead to equivalent term symbols. These dipoles interact with a certain spin—orbit interaction energy ESO . Lowest J value (regular) “electron”. notated by 1 S 2. S = 0. 3. Rules: 1. Spin Orbit Coupling A charge possessing angular momentum has a magnetic dipole associated with it. 1. Many electron atoms have term symbols associated with their states.4.7)
205
. 3. An electron has orbital and spin magnetic dipoles..g.2. H 2 (29.The term symbol for a particular states is constructed from the following general template gS LJ . The ground state will have maximum multiplicity. 2. Highest J value (inverted) “hole” 29. p1 and p5 have the same term symbol. The spin—orbit Hamiltonian is [ ˆ HSO = hcAL · S ´ ³ ˆ ˆ ˆ ˆ SO = hcA J 2 − L2 − S 2 .

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

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

This is given by Z (1) ˆ En = ψ(0)∗ H (1) ψ(0) dx. • The obvious solvable system is the harmonic oscillator: 1 ~2 d2 ˆ + kx2 .
√ 2 This has energy levels En = ~ω(n+ 1 ) and wavefunctions An Hn ( αx)e−αx /2 . 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
.1)
(1)
where En is the nth state energy for the unperturbed (solvable) system and En is the ﬁrst order correction. The nth state energy in perturbation theory:
(0) (1) En = En + En + .2) n n
all space
ˆ where H (1) is the ﬁrst order correction to the Hamiltonian–the perturbation. (0)
(30. (30.3)
• The perturbative part of the Hamiltonian is ˆ H (1) = ax4 .• The ﬁrst order energy is then used to make a ﬁrst order approximation to the wavefunction. . This process get algebraically intensive so we will only go as far as listing the ﬁrst order energy correction. . 2 q where α = km ~ (30. H=− 2 2m dx 2 (30. • The procedure is repeated to get higher and higher order approximations.

Etrial . 5 4α 2 so the ﬁrst order ground state energy for a quartic oscillator is √ ~ω 3 πaA2 0 + E0 ' . 5 2 2 4α
30.7)
209
. gives a trial wavefunction which is closest to the real wavefunction.• For example. The value of the parameter which minimizes the energy. We will not prove this theorem here. p. The trial energy is calculated by Etrial = R R
all space
ˆ ψ∗ Hψtrial dx trial ψ∗ ψtrial dx trial (30. The basis for this is the variation theorem which states Etrial ≥ E.2.5) 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 = . Variational method
The basic idea behind the variational method is to use a trial wavefunction with an adjustable parameter. the ground state energy correction is then calculation from Z ∞ (1) (0)∗ ˆ (0) ψ0 H (1) ψ0 dx (30.6)
all space
The trial energy is now a function of the adjustable parameter. that we use to minimize the trial energy by setting dEtrial =0 dp (30.

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

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

° “projects out” the j th state of the wavefunction being acted on. j 6= k (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 .Consequently.°
+ 2 δ 2. we can not use our usual procedure of writing down the classical Hamiltonian and then replacing the variables with their corresponding operators.
212
.
(31.2)
where δ j.1)
TLS
R where TLS dΩ means integration over the two level space (which is really just the P sum 2 ). ˆ H=
1 δ 1. i=1 The states ψ 1 and ψ2 are eigenfunctions of the two level Hamiltonian.

5)
states.° + =
1 δ 1.For example let some arbitrary wavefunction ψ = aψ 1 + bψ2 .7)
213
.3)
(aψ1 + bψ2 ) +
(aψ1 + bψ2 )
= a 1 ψ1 + b 2ψ2 Another orthonormal set of wavefunctions are the so-called ‘left’ 1 1 ψL = √ ψ1 + √ ψ2 2 2 and ‘right’ 1 1 ψR = √ ψ1 − √ ψ2 2 2 (31. 2 2 (31.° 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 .4)
(31.°
(31.6)
(31. then ˆ Hψ = ( 1 δ 1.° ) (aψ 1
+ bψ2 )
2 δ 2.

31.9)
ˆ En ψn (x)e− ~ En t = e− ~ En t Hψn (x) ˆ En ψn (x) = Hψ n (x)
(31. t)dx¯ (31. t) = ¯ Ψn (x.2.
214
.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. 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. This is given by ¯Z ¯2 ¯ ¯ ∗ P (x. 0)Ψn (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 .8)
We can verify this by obtaining the time independent Schrödinger equation from the more general time dependent ∂Ψn (x. t)
i ˆ = Hψn (x)e− ~ En t i ˆ = Hψn (x)e− ~ En t i ˆ = Hψn (x)e− ~ En t i
(31. Quantum Dynamics
So far we have been concerned with the eigenfunctions and eigenvalues (energy levels) of the various quantum systems that we have discussed. t) ≡ ψn (x)e− ~ En t
i
(31.11) ¯ ¯ ¯2 ¯Z ¯ ¯ i ∗ − ~ En t dx¯ = ¯ ψ n (x)ψ n (x)e ¯ ¯ ¯ ¯2 Z ¯ −iE t ¯ ∗ ¯e ~ n ψn (x)ψ n (x)dx¯ = ¯ ¯ ¯ i ¯2 ¯ ¯ = ¯e− ~ En t (1)¯ = 1.

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

This leaves ¯2 ¯Z ¯ ¯ ¯ Φ∗ (x. 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 .
216
. +e +1 = = 4 2 ~ The probability of ﬁnd in the system in its original superposition states is not one for all times t.integrated because the eigenfunctions are orthogonal. t)¯ (31.15) P (x.

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

√ ny πy nz πz nx πx 2 2 sin sin .
(31. ˆ ˆ ˆ ˆ ˆ L m2 h2 ~2 m2 = . Lx = L2 . Lz = i~Lx . j 6= k
(31.21)
ψ∗ ψk j
=
space
1. ˆ y . ˆ z .24) L L L and h i h i h i ˆ 2 .23)
• Commonly used comutators of the angular momentum operators are h i i i h h ˆ ˆ ˆ ˆ ˆ ˆ ˆ x . 2I 8π2 I (31.27)
218
. sin ψn (x) = √ a b c abc • The energy levels for the 3D particle in a box.19)
• Normalized wavefunctions for the 3D particle in a box.nz • Orthonormality: Z n2 h2 n2 h2 n2 h2 y x = + + z 2.26)
• The normalized wavefunctions for a particle on a ring are 1 ψ = √ eimφ . Enx . Ly = i~Lz . 0. Lz = 0.25)
• The energy levels for a particle in a ring are Em =
(31.20)
(31. Lx = i~Ly (31. Ly = L2 . 2π (31.• The Laplacian
∇ =
2
µ
∂2 ∂2 ∂2 + 2+ 2 ∂x2 ∂y ∂z
¶
.ny .22)
• Superpostion:
ψ=
X
i
ai ϕi
(31.
j=k . 8ma2 8mb2 8mc (
(31.

• The eigenfunctions of angular momentum are entirely speciﬁed by two quantum numbers l and m: ψ lm .28)
• Degeneracy for general angular momentum is gJ = 2J + 1.29) ˆ Lz ψlm = mψ lm (31.31)
• 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. ˆ L2 ψlm = l(l + 1)ψ lm • The energy levels for the rigid rotor are El = l(l + 1)~2 .33)
• The left and right superposition states are 1 1 ψL = √ ψ1 + √ ψ2 2 2 and 1 1 ψR = √ ψ1 − √ ψ2 2 2 (31.32)
• In general
Ψn (x. • The ﬁrst order energy correction in pertubation theory is Z (1) ˆ ψ(0)∗ H (1) ψ(0) dx. En = n n
all space
(31.34)
(31. t) ≡ ψn (x)e− ~ En t
i
(31. 2I (31.30)
(31.35)
219
.

Part VI Symmetry and Spectroscopy
220
220
.

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

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

Water is an example of a molecule described by this point group. C2 .
223
. Example: The C2v Group ˆ ˆ ˆ The C2v group consists of the symmetry elements E.3. for any member of the group one can ﬁnd another member of the group which.” yields the identity element. In other words.
∗ ∗ ∗ 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). The “product” of any two members of the group yield a member of the group.2. 4. upon “multiplication. Symmetry of Functions
In the absence of degeneracy. 32.1. The inverse of every member of the group is also in the group.3. The multiplication table for the C2v group is C2v ˆ E ˆ C2 σv ˆ σ 0v ˆ ˆ E ˆ E ˆ C2 σv ˆ σ 0v ˆ ˆ C2 ˆ C2 ˆ E σ 0v ˆ σv ˆ σv ˆ σv ˆ σ 0v ˆ ˆ E ˆ C2 σ 0v ˆ σ 0v ˆ σv ˆ ˆ C2 ˆ E
32. the wavefunctions must be symmetric or antisymmetric with respect to all elements of the group.

1. −1) B1 = (1.Connecting with the C2v group example lets consider the wavefunctions for water. −1. consider the following. As it turns out there is four possible sets of eigenvalues–hence four diﬀerent vectors: A1 = (1. −1) B2 = (1. −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. 1. 1). To see where these four vectors come from. 1) A2 = (1. In this case one can collect the eigenvalues (either +1 or −1) for each of the four symmetry operators as a four component vector. 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.
224
. −1. −1. 1.

1. −1) ⊗ (1. 1) = (1. . . 1. x2 y2 . .4) (32. x3 . −1.) For the example of the C2v group consider B1 ⊗ B2 = (1. .The above considerations leave four vectors. x3 y3 . Altogether.4.3)
32.3. . x2 . y2 . the vectors represent what is call an irreducible representation of the group. −1.) = (x1 y1 . These vectors make up the : C2v A1 A2 B1 B2 ˆ E ˆ C2 σv ˆ σ 0v ˆ
1 1 1 1 1 1 −1 −1 1 −1 1 −1 1 −1 −1 1
∗ ∗ ∗ See Handout on Character Tables ∗ ∗∗ 32. 1.) ⊗ (y1 . . . y3 . In fact.
225
. −1) = A2 (32. there will always be the same number of vectors as symmetry elements. . Direct Products The direct product of a two vectors is deﬁned as (x1 . . 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. −1. −1.

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

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

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

One example was the “left” and “right” states of the two level system. The number of normal modes equals the number of vibrational degrees of freedom. The three modes are the bending vibration.
229
. Regardless of what type of vibrational motion is taking place.
33. that motion is some linear combination of fundamental vibrational motions called normal modes.1. Example: Water The point group symmetry of the water molecule is C2v .1. 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. This is analogous to writing an arbitrary wavefunction as a linear combination of eigenfunctions. however. Normal Modes Polyatomic molecules can undergo very complicated vibrational motion.1.2. The character table is C2v A1 A2 B1 B2 ˆ E ˆ C2 σv ˆ σ 0v ˆ
1 1 1 1 1 1 −1 −1 1 −1 1 −1 1 −1 −1 1
Water has three nuclei and it is nonlinear so it has 3(3) − 6 = 3 normal modes. At low energies the normal modes are well approximated as harmonic oscillators.33. the symmetric stretching vibration and the asymmetric stretch.

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

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

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

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

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

The R was involved in vibrations. For constant R the rotational energy is given by − Erot = J(J + 1)~2 J(J + 1)h2 .3)
This is the so-called rigid rotor energy. 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 . ~2 ˆ2 (35.4)
(35.35. 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. 2I Now. under the Born-Oppenheimer approximation. Then Erot = J(J + 1)hBe with a degeneracy of gJ = 2J + 1 235
235
h 8π 2 I
(35. It is common to deﬁne Be ≡ as the rotational constant. = 2μR2 8π 2 I (35.5)
(35.1) R 2μ 2μR2 ∂R ∂R 2μ We will now be concerned only with the angular part.2) J .6)
. (35. θ. φ).

35. • One deﬁnes a rotational interaction constant that depends on the vibrational level. ¶ µ 1 Bn ≡ Be − n + αe . Alternatively. n. where Dc ≡
3 4Be ω2 ˜e
(35.2.9)
is the centrifugal stretching constant. There are two corrections we will now make 1. Relaxing the rigid rotor
Of course the rigid rotor is not a perfectly correct model for a diatomic molecule. This is called a pure rotational transition.7) 2 where αe is an empirical rotational—vibrational interaction constant.1. a rotational transition can accompany a vibrational transition.8)
(35. In either case the selection rule for the transition is 4J = ±1. Vibrational state dependence: • The R value is dependent on the particular vibrational level.
35. (35. • This is corrected for by the term −J 2 (J + 1)2 Dc . Rotational Spectroscopy
A rotational transition can occur in the same vibrational level n. Centrifugal stretching: • Rotation tends to stretch the diatomic distance R.
236
. 2.

It turns out that typical rotational energy gaps are on the order of a few wavenumbers or less.3. The total moment of inertia. 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. But one system is special–the principle axes coordinate system. I = Ixx + Iyy + Izz The Hamiltonian in the principle axes system is # " ˆ2 ˆ2 ˆ2 Jy ~2 Jx Jz ˆ + + H= 2 Ixx Iyy Izz
(35. at room temperature is about 200 cm−1 . This means that at room temperature the many excited rotational states are populated. Thermal energy. kT. 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.10)
237
. ∗ ∗ ∗ See Handout ∗ ∗∗
35.

Linear (e.. Ixx = Iyy ˆ ˆ2 ˆ2 • J 2 = Jx + Jy • The Hamiltonian is • The rotational energy is Erot = hBJ(J + 1).There are four classes of polyatomic molecules regarding rotations 1.g. where B= 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
(35.12)
~2 ˆ2 ˆ J H= 2Ixx
(35.14)
• The rotational energy is Erot = hBJ(J + 1) + h(A − B)K 2 . where A= (35.16) 8π 2 Izz h (35.. carbon dioxide) • Izz = 0.11)
(35. benzene) • Ixx = Iyy h 8π2 Ixx (35.15)
h .17) B= 2 8π Ixx and K is the quantum number describing the projection of the angular momentum onto the z-axis
238
.g. Symmetric tops (e. (35.

Spherical tops (e.20)
4.18)
(35.3. where B= h 8π2 Ixx (35.g. Asymmetric tops • Ixx 6= Iyy 6= Izz • These are more complicated and we will not discuss them in detail
239
.. methane) • Ixx = Iyy = Izz
ˆ ˆ2 ˆ2 ˆ2 • J 2 = Jx + Jy + Jz • The Hamiltonian is • The rotational energy is Erot = hBJ(J + 1).19) ~2 ˆ2 ˆ J H= 2Ixx (35.

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

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

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

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

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

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

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

Key Equations for Exam 2
Listed here are some of the key equations for Exam 2.3)
h 8π 2 I
(37.4)
. This section should not substitute for your studying of the rest of this material.
Equations
• Vibrational degrees of freedom — linear: 3N − 5 — not linear: 3N − 6 • The so-called rigid rotor energy is Erot = J(J + 1)hBe . The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations. The equations are collected here simply for handy reference for you while working the problem sets. 247
247
(37. where Be ≡ is the rotational constant.

5)
vib space
(37.f ¯ Z
∞
(37.• The degeneracy of the rigid rotor is gJ = 2J + 1 • Franck—Condon Factor: ¯Z ¯ ¯ ¯ ¯ ¯2 ¯ ¯ ψ∗ ψvib.7)
−∞
• The inverse Fourier transformation is Z ∞ h i 1 −1 ˜ ˜ = f(ω)e−iωt dω.i ¯ vib. f (ω) = f (t) = 2π −∞
(37.
(37.6)
• The Fourier transformation is
˜ = [f (t)] = f (ω) =
f (t)eiωt dt.8)
248
.

Part VII Kinetics and Gases
249
249
.

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

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

380658 × 10−23 is Boltzmann’s constant. Molecular Collisions
The average speed of a particle can calculated from Maxwell’s distribution: Z ∞ Z ∞ m 3 − mv2 ) 2 e 2kT dv hvi = v = ¯ vF (v)dv = v 3 4π( (38. n RT |{z}
=L
A simple model for molecular collisions:
252
.
38. n = = RT .5) 2πkT 0 0 s r µ ¶ 8kT L Lk=R 8RT = = πm L Lm=M πM It will be convenient to deﬁne number density as n∗ ≡ N where N is the number V N P nRT LP ∗ of particles. For an ideal gas (V = P ).2.We shall consider stationary isotropic distributions F (v). This is the Maxwell’s distribution (of speeds). So F (v) represents a distribution of speeds. It can be shown from ﬁrst principles that µ ¶3 2 −mv 2 m F (v) = 4π e 2kb T v 2 (38.4) 2πkb T where kb = 1.

Since the molecules are moving relative to one another we must ﬁnd the average relative velocity.5 nm
253
. v12 = h|v1 − v2 |i ¯ It can be shown that r v12 = ¯
√ √ collision 16RT = 2¯ =⇒ v = 2n∗ πσ 2 v . s
collision = 5. P = 1 bar): v = 380. ∗ ∗ ∗ See Handout ∗ ∗∗ • The number of collisions equals the number of particles with their centers in V : number of collisions = n∗ πσ 2 v4t (38.• Particles are hard spheres of radius σ.25 × 109 s−1 .6) • The collision frequency = n∗ πσ 2 v For the above model we need to ﬁnd the average collision frequency. ¯ πM frequency
(38.8)
Example: Ar at SATP (T = 298 K.48 ¯ m .7)
From the above expression one deﬁnes the mean free path λ to be v ¯ / λ= √ 2n∗ πσ 2/ v ¯
LP n∗ = RT
=
RT √ 2P Lπσ 2
(38. frequency λ = 72. • A Particle moving at v sweeps out a cylinder of radius σ and length v4t =⇒ V = πσ2 v4t.

Will the reaction occur? We need kinetics. however.
254
254
. We can. from thermodynamics. in general. That is. Rate Laws
Consider a general four component reaction aA + bB = cC + dD (39. answer the question: How fast will the reaction occur?
39.1)
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.1. d[B] d[C] d[D] d[A] or − or or (39. equal b. We must account for the stoichiometry.2) − dt dt dt dt BUT this is ambiguous because a moles of A reacts with b moles of B and a does not. The Rate Laws of Chemical Kinetics
Thermodynamics described chemical systems in equilibrium.39. address the question. For this we turn to the ﬁeld of chemical kinetics. For the study of chemical reactions it is important understand systems that can be very far from equilibrium.

B.) (39. v = f (conc. −b. but certainly not all. (39. or D.We deﬁne the reaction velocity as v= 1 d[I] vi dt (39.3)
where vi = −a.5) For the most part. c or d and I = A. rate laws are empirical. In general an overall reaction is made up of so called elementary reactions Reactant Reactant = → Product overall rxn (39.4) 0 B0 → c0 C0 + d0 D0 b A rate law is the mathematical statement of how the reaction velocity depends on concentration. rate laws are of the form v = k[A1 ]xA 1 [A2 ]xA 2 · · · [An ]xA n . An example of this is ½ bB → cC + dD aA + (39. This deﬁnition is useful but must be used with caution since for complicated reactions all the v’s may not be equal. C.6)
The reaction is said to be of order xAi in species Ai and it is of overall order P i xA i .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
. Many.

10)
256
. (39.9)
where kf is the rate constant for the reaction to proceed in the forward direction and kr is the rate constant for the reaction to proceed in the reverse direction. Trimolecular A + A + A → Product v = k[A]3 Trimolecular A + A + B → Product v = k[A]2 [B] Trimolecular A + B + C → Product v = k[A][B][C] Conversely. One possible set of elementary steps could be elementary rxn A + A → A0 A00 + 2B→ C + D A0 → A00 molecularity Bimolecular Unimolecular Trimolecular .Let 2A + 2B = C + D be the overall reaction.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] . Now. 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. Connection to thermodynamics Consider the overall or elementary reaction aA + bB cC + dD
kr kf
(39.

The velocity of a reaction is lost in this ratio and hence we still can not determine the speed of a reaction from thermodynamics.
this does not obey any common form. The above two example are seemingly very similar but they have very diﬀerent observed rate laws. H2 + Br2 = 2HBr. (39. Objectives of chemical kinetics
257
. The observed rate law for this reaction is very complicated.12)
The observed rate laws are vf = kf [H2 ][I2 ] and vr = kr [HI]2 . In fact. H2 + I2 = 2HI. Next consider the reaction between molecular hydrogen and molecular bromine.11)
So. Moral: Kinetics is very much an empirical science. the reaction is not elementary. we have succeeded in connecting thermodynamics to kinetics BUT we have done so through the ratio of rate constants.”
(39.13)
. Moral: Kinetics is very much an empirical science. This suggests that the reaction is elementary. Examples of rate laws Consider the (overall) reaction between molecular hydrogen and molecular iodine. v= k[H2 ][Br2 ]1/2 1+
k0 [HBr] [Br2 ]
(39.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.

Determination of Rate Laws
Concentrations c(t) are measured not rates.• 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. To obtain the rate from the concentration we must take its time derivative dc(t) . That is we must measure c(t) as a dt function of time and ﬁnd the rate of change of this concentration curve. • Very fast (sec/subsec) reactions cause problems because the reaction goes faster than one can mix the reactants.
258
. • 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. Consequently no one experimental technique can be used.2. • For slow reactions (hrs/days) almost any technique for measuring the concentration can be used. The rates of chemical reactions vary enormously from sub-seconds to years.

Diﬀerential methods based on the rate law Methods based directly on the rate law rely on the determination of the time derivative of the concentration.1.2.
259
.2. this gives the overall order of x + y • ﬂood with. Method of initial velocities • for v = k[A]x [B]y rate laws. if there is an induction period 2. if the concentration drops very sharply 2. • problems 1. A so v ≈ kax [B]y 39.2. • initially v0 = kax by where a and b are the initial concentrations of A and B respectively • taking the log of both sides gives lnv0 = ln[kax by ] = ln k + x ln a + y ln b • a and b can be varied independently so both x and y can be determined. The main problem with such a method is that randomness in the concentration measurements gets ampliﬁed when taking the derivative. 1. The diﬀerential equation is not solved.39. Method of isolation • for v = k[A]x [B]y rate laws • start with initial concentrations a and b equal to the stoichometry. Integrated rate laws The above diﬀerential methods look directly at the rate law which is a diﬀerential equation. say.

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

40. kr
(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 .5)
. This is the Arrhenious equation Recall the equilibrium constant can also be obtained from kinetics
0 Kc =
kf ' Ka .1. ln Ka = ln kr ∙ 261
261
(40.1) (40.3)
(A is the constant of integration).4)
Now. d(1/T ) R where Ea is the Arrhenious activation energy.2)
(40. Integration of the above yields ln k = ln A −
Ea Ea =⇒ k = Ae− RT RT
(40. Temperature and Chemical Kinetics
40.

7)
(40.B) • Reaction rate determined by molecular collisions
262
.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. Theoretical approaches to reaction rates predict rate constants of the form k = aT j e−E /RT . k = Ae− RT = aT j ej e−
Ea E 0 +jRT RT
= aT j ej e/ e RT = aT j e RT / −j
−E 0
−E 0
√
(40.1. Forcing this to coincide with the Arrhenious implies Ea = E 0 + jRT and A = aT j ej
0
(40.10)
40.2.9)
We can verify this by starting with the Arrhenious equation and substituting the above expressions.1.8)
(40. Temperature corrections to the Arrhenious parameters The Arrhenious parameters A and Ea are constants.6)
(40. Theory of Reaction Rates
Simple collision theory (SCT) • Bimolecular reactions (A.

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
(40.13)
[A][B]
= pπσ AB L
s
8RT − Em in e RT πLμ
(40.
• 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
(40.14)
263
.

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

— From statistical mechanics. Parallel reactions:
265
. • The reaction rate constant for reactants going to products for ACT is
‡ k = f Ka =
kb T ‡ K h a
(40. there is many steps from initial reactants to ﬁnal products. In general.20)
which can be written as
‡ Ka = e−
4G‡ RT
= e−
4H ‡ RT
e
4S ‡ R
(40. in what is called a reaction network. the reactions we have studied have been single step reactions. h
(40.19)
• Thermodynamics tells us that
‡ 4G‡ = −RT ln Ka
(40.• Deﬁnition: transmission factor.3. Reactions may occur in series or in parallel or both.22)
40.21)
where 4G‡ = 4H ‡ − T 4S ‡ . Multistep Reactions
Up to now. • The ACT reaction rate constant now becomes k= This is Eyring’s equation kb T − 4H ‡ 4S‡ e RT e R . it can be shown that f = kb T /h where kb is Boltzmann’s constant and h is Planck’s constant. f — accounts for the fraction of activated complex that becomes product.

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

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

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

Equations of State
Recall from last semester several of the equations of states for gases.3)
a RT − 2.1. (41. nRT
m V
(41. This simpliﬁes the theoretical treatment of gases. The equation of state can also be expressed in term of density ρ = ρ= mP . Gases and the Virial Series
Unlike liquids and solids.4) Vm − b Vm where the parameter a accounts for the attractive forces among the particles and parameter b accounts for the repulsive forces among the particles P = 269
269
.41. We will now look in detail at the gases. • The ideal gas equation of state P V = nRT.1)
(41.2)
• The van der Waals gas equation of state P = or
n2 a nRT − 2 V − nb V
(41. a particular particle has much less signiﬁcant interactions with the other particles.
41.

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

41.
(41.13) (41. hence
1 Vm
µ
b Vm
¶2
+ ··· .10)
to get
V / a /T Vm R / P Vm = − m / 2 RT R / Vm − b RT Vm /T a Vm − = Vm − b RT Vm 1 a = − b RT Vm 1 − Vm but
P Vm RT
(41. b RT Vm 1 − Vm which has the power series expansion (41. C(t) = b2 .1.14)
1 Vm
and so it can be combined with the
term
µ ¶2 ³ a ´ 1 b z =1+ b− + + ··· . D(T ) = b3 .15)
This series can now be compared term by term to the virial series to give expression for the virial coeﬃcients: ³ a ´ . (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
(41.16) B(T ) = b − RT
271
. etc.2. RT Vm Vm
(41.12)
The ﬁrst term is of the form
1 1−x
1 = 1 + x + x2 + · · · .11)
= z so z= 1 a − . 1−x Therefore b a +1+ + z=− RT Vm Vm the ﬁrst term is proportional to in the series expansion.

18)
The relation of this expansion to the one in V1 can be obtained. 41.41. (41. (41. One ﬁnds (see m homework) B(T ) B 0 (T ) = .3. 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 + · · · . The gas behaves more like an ideal The lowest order correction are now V1 m gas at Tb then for other temperatures. (41. Tb .2. 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 ) + ··· .2.2.17) = 1 + C(T ) Vm Vm ³ ´2 .19) RT
272
. The Boyle Temperature The temperature at which B(T ) = 0 is called the Boyle temperature.

23) (41.21)
41. B0 . T3 B(T ) = B0 − where A0 .2. b.24)
273
.C 0 (T ) = and D0 (T ) =
C(T ) − B(T )2 (RT )2
(41.4.25) 128Pc T (41.22) (41. a. C(T ) = RT T B0 bc D(T ) = . for now treat them as empirical parameters): µ ¶ 9RTc 6Tc2 B(T ) = 1− 2 . Estimation of Virial Coeﬃcients The virial coeﬃcients can be estimated using empirical equations and tabulated parameters. (41.
• Estimates based on Beattie-Bridgeman constants: c A0 − 3.20)
D(T ) − 3B(T )C(T ) − 2B(T )3 (RT )3
(41. c are tabulated constants • Estimates based on critical values (we will discuss critical values shortly. RT T A0 a B0 c − B0 b − 3 .

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

b. absurd to treat a liquid as an ideal gas).4)
so.1. P Ã ¡ ¢! µ ¶ µ ¶ nRT −1 ∂V −1 ∂ nRT −1 P − 2 κT = (42.
V (P ) ≈ V0 [1 − κT (P − P0 )] .1.2. P0 . α and κT for liquids and solids
Ã ¡ ¢! ∂ nRT 1 1 P = /R = n/ ∂T VP T |{z} P
=n R / /T
(42.42. Starting with the ideal gas law: V = nRT .3)
In general.5)
This approximation is quite good even over a rather large pressure range (P −P0 = 100 atm or so)..
(42.2) = = 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. At constant T ¶ ¶2 µ ∂V ∂V (P − P0 ) + (P − P0 )2 + · · · V (P ) = V0 + ∂P ∂P T | {z T } µ
−V0 κT
(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. the compressibility and expansion of liquids (and solids) are very small. it is.1. So one can expand the volume in a Taylor series about a known pressure. of course.
275
.

we can apply the cyclic rule for partial derivatives to determine the ratio κα : T ¡ ∂V ¢ ¶ µ α ∂P ∂T P cyclic = ¡ ∂V ¢ = (42.2.8) κT − ∂P T rule ∂T V
42.9)
¶ ¶ ¶ µ µ ∂ (U + P V ) ∂U ∂V = +P (42.2. Use an identity of partial derivatives ∂T ∂T µ ∂U ∂T ¶ =
P
µ
∂U ∂T
¶
+
V
µ
∂U ∂V
¶ µ
T
∂V ∂T
¶
(42.1.11)
P
276
.
(42.6)
so.10) CP = ∂T ∂T P ∂T P P ¡ ¢ ¡ ¢ note ∂U P is not CV we need ∂U V .H = U + PV CP = ∂T P so µ
(42.
V (T ) ≈ V0 [1 + α(T − T0 )] . The Relationship Between CP and CV To ﬁnd how CP and CV are related we begin with ¶ µ ∂H . Heat Capacity of Gases Revisited
This section is a review from the ﬁrst semester with an additional example beyond the ideal gas.7)
As one ﬁnal point.Likewise at constant P ¶ ¶2 µ ∂V ∂V (T − T0 ) + (T − T0 )2 + · · · V (T ) = V0 + ∂T P ∂T T | {z } µ
V0 α
(42. 42.

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. Explicit in P : Replace µ 2.12) CP = ∂V T ∂T P ∂T P V ¶ ∙µ ¶ µ ¸ ∂U ∂V = CV + +P .14)
V
For solids and liquids: µ so ∂V ∂T ¶ = V α. Explicit in V : Replace µ ∂P ∂T ¶ ∂V ∂T ¶ with − ¡ ∂T ¢V ∂P
∂V
P
¡ ∂P ¢
(42.17)
T
V
∂T with − ¡ ∂V ¢P ∂P T
¡ ∂V ¢
(42.13)
∂P ∂T
¶
(42.thus ¶ µ ¶ ¶ µ ∂V ∂U ∂V + +P (42. Then ∂T µ ∂U ∂T µ CP = CV + Finally CP = CV + T µ ∂V ∂T ¶ ∙ µ ¶ ¸ ∂P T −P +P / / ∂T V P µ ∂V ∂T ¶ µ
P
¶
(42. ∂T P ∂V T ¡ ¢ ¡ ∂U ¢ Recall the expression for internal pressure ∂V T = T ∂P V − P .18)
277
.15)
P
V
α2 T V (42. µ ∂P ∂T ¶ = α κT (42.

Examples 1. One term viral equation (equation of state: V = nRT + nB). = ∂T P P
∂T − ¡ ∂V ¢P = − ∂P T
µ
∂V ∂P
¶
T
=−
nRT . This is explicit P in V so use case 2 above ¶ µ ¶ ¶ ¡ ∂V ¢ µ µ ∂P ∂V ∂V ∂T ¡ ∂V ¢P CP = CV + T = CV − T (42.22)
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
(42.21)
so
¡ ∂V ¢
nR P
+ nB 0 / P (R + P B 0 ) n = . nRT − P2 / RT n
(42. P2
(42.24)
278
.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. 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 (42.23)
or
(42.20) ∂T P ∂T V ∂T P ∂P T The partial derivatives are ¶ µ ∂V nR + nB 0 .

Isothermal expansion • For the case of a ideal gas.3. Recall that if the expansion is reversible. Expansion of Gases
Expanding gases do work: −w = Z
V2
Pex dV
(42. U (T. −wrev = For an ideal gas (P =
nRT ) V
Z
V2
Pgas dV
(42. Isothermal expansion T is constant 2. Isothermal and Adiabatic expansions We shall consider two limits for the expansion of gases 1. Adiabatic expansion q = 0.25)
V1
As we learned last semester the value of w depends on Pex during the expansion. 42. V ) = U(T ) (independent of V ). So for isothermal expansion 4U = 0 = q + w =⇒ q = −w.26)
V1
this becomes Z
V2
−wrev =
V1
µ ¶ V2 nRT dV = nRT ln V V1
(42. there is always an intermediate equilibrium throughout the expansion. So. Namely Pgas = Pex .3. −wrev = −wmax .27)
Also recall that −wrev is the maximum possible work that can be done in an expansion.
279
.1.42.

dU = dw = −Pex dV = −P dV (reversible). • For an ideal gas dU = −P dV = −nRT dV V (42. V1 ) to (T2 .3. V2 ).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. Recall ¶ µ ∂U CV = =⇒ dU = CV dT ∂T V So from above CV dT −nRdV −nRT dV =⇒ = V T V Going from (T1 .28)
42.30)
T1
CV dT = T
Z
V2
V1
−nR dV.33)
280
. in terms of molar heat capacity
2
T2 ¯ CV m ln T1
µ
¶
V2 = −R ln V1
µ
¶
(42. Heat capacity CV for adiabatic expansions Considering an ideal gas going adiabatically from (T1 .32) CV ln T1 V1 ¯ where CV = 1 (CV (T1 ) + CV (T2 )) . V
(42. V2 ): CV dT = Z
T2
(42. Or. V1 ) to (T2 .29)
(42.Adiabatic expansion • Since q = 0.

36)
CP dT = T
P2
P1
nR dP. dH = dU + P dV + V dP (because both P and V can.34)
=⇒ dH = Cp dT = V dP
(42. in terms of molar heat capacity
2
T2 ¯ CP m ln T1
µ
¶
P2 = R ln P1
µ
¶
(42. 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.3.40)
281
.35)
P
For an ideal gas this becomes
Cp dT = Going from (T1 . Now.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.3.39)
From the above two cases µ ¶ µ ¶ µ ¶ R −R P2 V2 T2 = ¯ ln = ¯ ln ln T1 P1 V1 CP m CV m
(42.42. in general. CP = µ ∂H ∂T ¶
(42. P1 ) to (T2 . P
(42. P2 ): Z T2
T1
nRT dP P Z
(42. Or.38) CP ln T1 P1 ¯ where CP = 1 (CP (T1 ) + CP (T2 )) .

43)
42.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
(42.3. In this case q = 0 (adiabatic) and w = 0 (since −dw = Pex dV ).
282
.
(42. Joule expansion Consider a gas expanding adiabatically against a vacuum (Pex = 0).4.42)
but Pi Viγ are arbitrary so this implies P V γ = constant (** NOTE: The axes should be reversed **)
¶γ
⇒ P2 V2γ = P1 V1γ .41)
¶
V1 = γ ln V2
µ
¶
V1 = ln V2
µ
¶γ
(42.

Thus in as much as the ¡ ∂T ¢ gas can be considered ideal ∂V U = 0. for Joule type expansion the temperature of the gas does not change.3. Internal energy is constant. Joule-Thomson expansion Consider the adiabatic expansion as illustrated by the ﬁgure below
¡ ∂U ¢
283
. That is.5. For real gases this is not strictly equal to zero. ¶ µ ¶ ¶ µ µ ∂U ∂U ∂T 1 =− = ∂U V ∂V T CV ∂V T | {z }
1/CV
µ
∂T ∂V
¶
(42. V ) = U(T )).44)
U
. We want to ﬁnd Identity: ¡ ∂T ¢
∂V
(42. 42.This implies 4U = q + w = 0.45)
U
For an ideal gas ∂V T = 0 (since U(T.

Now.49)
H
≡ μ. 4U = U2 − U1 = wL + wR = P1 V1 − P2 V2 Thus U2 + P2 V2 = U1 + P1 V1 ⇒ H2 = H1 For Joule-Thomson expansion the enthalpy is constant.48)
(42.46)
(42. We want to ﬁnd Identity: µ ¡ ∂T ¢
∂V
(42. The work done on the right is wR = −P2 4V = −P2 (V2 − 0) = −P2 V2 .50)
H
284
.47)
(42. (the Joule-Thomson coeﬃcient). ¶ µ ¶ ¶ µ µ ∂H ∂T 1 ∂H =− = =μ ∂H P ∂P T CP ∂P T | {z }
1/CP
∂T ∂P
¶
(42.The work done on the left is wL = −P1 4V = −P1 (0 − V1 ) = P1 V1 .

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

286
286
. Entropy of Gases
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 . This is not a problem though since entropy is a state function. (43. So Z T2 CP CP dT =⇒ 4S = dT. So Z T2 CV CV dT =⇒ 4S = dT. Calculation of Entropy
Entropy must be calculated along reversible paths. Entropy change for changes in temperature. dS = T T T1
(43. but also dH = T dS.1.43. but also dU = T dS. • At constant V : — dU = dq + dw
dq=CV dT
=⇒
dU = CV 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 . So dH = dq =⇒ dq=T dS dH = CP dT.

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

• Recall Avogadro’s principle: n ∝ V for an ideal gas. Entropy of Real Gases Consider the question: How does S → S ideal as P → 0 ? Use Maxwell relation nRT + nB. P2 → P θ as S θ . So. so
ideal ideal S2 − S1 = −nR ln
(43.13)
288
.10)
Thus
ideal ideal S2 − S1 = S2 − S1 − nB 0 (P2 − P1 )
(43.8)
µ ¶ → nR P2 → 0 − nB dP =⇒ S2 − S1 = −nR ln dS = − − nB 0 (P2 − P1 ) P P1 P2 P1
(43.12)
ideal Deﬁning S2 . ⎛ ⎞
1/XA 1/XB
⎜ nA + nB nB + nA ⎟ ⎜ ⎟ + nB ln 4Smix = R ⎜nA ln ⎟ = −R (nA ln XA + nB ln XB ) nA nB ⎠ ⎝ | {z } | {z } (43.9)
For an ideal gas B 0 = 0.1. this becomes S2 − / 1 S
ideal ideal = S2 − / 1 S ideal
− nB 0 (P2 − P1 )
(43. V =
Hence
¶
T
∂V =− ∂T
µ
¶
P
=−
nR − nB 0 P
(43.11)
Letting P1 → 0 and P2 → P θ (Standard pressure 1 bar).
S(P θ ) = S θ − nB 0 P θ
(43. So. P So ¡ ∂S ¢ µ ∂S ∂P
∂P T
= −
¡ ∂V ¢
∂T
P
and single term viral equation.7)
43.1.

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

Key Equations for Exam 3
Listed here are some of the key equations for Exam 3.18)
290
290
.17)
RT λ= √ 2P Lπσ 2
(43.
−mv2
(43. 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.16)
• The average speed of a particle is hvi = • The mean free path is
r
8RT πM
(43.
Equations
• The Maxwell’s distribution of speeds is F (v) = 4π µ m 2πkb T
¶3 2
e 2kb T v2 . The equations are collected here simply for handy reference for you while working the problem sets.

24)
z=
(43.20) kr • The Arrhenious equation k = Ae− RT
Ea
(43.22)
• The van der Waals gas equation of state: P = • Compressibility Factor: a RT − 2.21)
• 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. Vm Vm Vm • Relation between heat capacities for an ideal gas: CP m = CV m + R
(43.23) (43.19)
• The relation between the rate constant and the thermodynamic equilibrium constant is kf Kc = (43.27)
291
.• The reaction velocity is v=
1 d[I] vi dt
(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 ) + ··· .26)
(43. Vm − b Vm P Vm PV = .

Part VIII More Thermodyanmics
292
292
.

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

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.
294
.1.44.1.

dVP = 0) at the critical point.44. Tc = 27bR a .2) 3 dVm ¯c (Vmc − b)2 Vmc
and
solving these three equations for Pc .6)
These values can be used to ﬁnd the compressibility factor. Vmc − b Vmc
2
(44. setting 2 m the ﬁrst and second derivatives at the critical point equal to zero we get ¯ dP ¯ ¯ = −RTc + 2a = 0 (44. at the critical point zc = Pc Vmc 3 = = 0.375 2/e2 ' 0.375 3/8 = 0. 8a .375.33
295
.7)
Notice that both a and b whose values depend on the particular gas have dropped out. Tc . z.4) (44.27 0.3)
(44.2.1)
dP d There is an inﬂection point ( dVm = 0.1. Gas Constants from Critical Data Consider the van der Waals equation at the critical point (Pc .375 for all gases. Vmc ) Pc = a RTc − 2 . So. 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 = 0.5) (44. Tc and Vmc gives Vmc = 3b. The other equations of state give similar results van der Waals Berthelot Dieterici Redlich-Kwong zc 3/8 = 0. RTc 8 (44.

∗ ∗ See Fig. Then zr = Pr Vrr . Suppose some amount of material. This implies μβ = μα is the condition for equilibrium.V = −P
For a spontaneous process A deceases (dA < 0)
z }| { (dVα + dVβ )
¡ ¢ + μβ − μα dn
At equilibrium dA = 0. then for a given T .18 Laidler&Meiser ∗ ∗
44. Pr = P/Pc . When α.3. dn. RT zr is a “universal” function–it is nearly the same for all gasses. goes from α → β • (dAα )T = −P dVα − μα dn • (dAβ )T = −P dVβ + μβ dn
= 0 since V is constant
• (dA)T.44.2. and Vr = V /Vc . Phase Equilibrium
Consider a homogeneous substance consisting of two phases α and β at a constant T and V. 1. One can deﬁne unitless “reduced” variables Tr = T /Tc . The Law of Corresponding States
We have found that zc is predicted by the equations of state to be independent of the particular gas. β denote liquid (or solid) and vapor phases. This is actually not too far from the truth experimentally. the pressure of the system when μβ = μα is the called the vapor pressure of the material at temperature T.
296
.

44. µ ∂S ∂n ¶ µ ¶ (44.9)
P.3. = Vm .
µ
∂μ ∂P
¶
(44. ∂n ∂T ∂T ∂n ∂T P µ ∂μ ∂T ¶ = −Sm .8)
(44.10)
But S = nSm (T. P ) so.11)
P
Similarly. ∂G S=− ∂T So. The chemical potential and T and P How does μ vary with T and P ? Generally for homogeneous substances.
(44.12)
T
Now the total diﬀerential of μ is
m z z m µ }|¶ { µ }| ¶ { ∂μ ∂μ dT + dP dμ(T.P = μβ − μα dn. dG = −SdT + V dP + μdn Now.13)
297
. So again μβ = μα is the condition for equilibrium.n
P. P ) = ∂T P ∂P T dμ(T.T
µ ¶ ∂ ∂G ∂μ ∂ ∂G =− =− =− .¡ ¢ For phase changes at constant T and P then (dG)T.1. P ) = −Sm dT + Vm dP
−S
V
(44.
(44.

15)
(44.14)
=
This is the Clapeyron Equation
4φ Hm T 4φ Vm
(44.44. Now 4v V = Vm.liq ' Vm. The Clapeyron Equation At equilibrium μβ = μα so.21)
d(ln P ) = −
298
.20)
= d(ln P ) and
dT T2
= −d(1/T ) so this becomes 4v Hm d(1/T ) R (44.16)
44.vap Assuming the vapor phase obeys the ideal gas equation of state.19)
Collecting the T ’s on one side of the equation and the P ’s on the other we get (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
(44.3.17)
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. 4v V = RT P (44.2.18) (44.vap − Vm.3. consider the liquidvapor phase transition.3. Vapor Equilibrium and the Clausius-Clapeyron Equation The above Clapeyron equation applies to any phase transition.

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 ) (44.24) α β
299
. 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.22)
44.Rearranging again leads to 4v Hm d(ln P ) =− d(1/T ) R This is the Clausius-Clapeyron equation. Equilibria of condensed phases
Examples • Solid—liquid — ice—water. (44.4. “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.

T for a system which shows the lines of equal chemical potential • Critical Point: The terminal point of the liquid-vapor line.26) 4f Hm 4f Hm Tf → T
ª where Tf is the freezing temperature at standard pressure (1 bar). • 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. Recall the Clapeyron equation 4f Hm Hmβ − Hmα dP = = dT T 4f Vm T (Vmβ − Vmα ) (44.25)
We make the good approximation that 4f Hm is independent of T and solve the Clapeyron equation Z → 4f Vm dP Tf 4f Vm (P − P ª ) dT = ⇒ ln ª = (44.5.
44. At temperatures above the critical point there is no distinction between vapor and liquid.27)
300
.Thus for any given T only one P allows for equilibrium.

Diﬀusion
At equilibrium concentration on a bulk solution will be uniform.1)
301
301
. Viscosity: The ﬂux of momentum down a velocity gradient 3. Diﬀusion: The ﬂux of material down a concentration gradient 2. So if there exists a concentration gradient there will be a net ﬂux. Transport Properties of Fluids
Transport properties of matter deal with the ﬂow (or ﬂux) of some property along a gradient of some other property. of material from high concentration to low concentration so as to establish an equilibrium.1. Thermal Conductivity: The ﬂux of energy down a temperature gradient
∗ ∗ See Transport Phenomena handout ∗ ∗
45.45. We now consider three transport properties of ﬂuids: 1. J= 1 dn A dt (45. J. Flux: movement of something through a unit area.

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.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). ∂t ∂x (45.5)
302
. ∂t ∂x ∂x If D is truly constant we get Fick’s second law of diﬀusion: ∂ 2C ∂C =D 2.2)
(45.3) (45.

e.
303
. t) = C0 2 π 0 ¶¸ ∙ µ x 1 C0 1 − erf √ = 2 4Dt ¶ µ 1 x = C0 erfc √ 2 4Dt " (45.2. The tendency of a liquid to ﬂow at the same velocity throughout.
45.. t) = √ e− 4Dt 2 πDt
(45. Point source solution
x2 C0 C(x. η. Viscosity
Viscosity. 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. i.6)
2.7)
where erf and erfc are tabulated functions respectively called the error function and complementary error function. is the resistance to diﬀerential ﬂuid ﬂow.The solution of this partial diﬀerential equation depends on the boundary conditions. The solution for two special boundary conditions are of interest and will simply be presented here without derivation 1.

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

E. Bird.11)
• Related to diﬀusion constant:
=
kT 6πηr
(45. of a material is a measure of the tendency of energy in the form of heat to ﬂow through the material.10)
(45. Stewart and E.
4πr3 (ρ − ρ0 )g. N. 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. The plates are held at constant but diﬀerent temperatures T1 and T2 (T1 > T2 ) for a suﬃciently long time that a steady state exists. W. Consider a slab of solid material of area A between two large parallel plates a distance D apart. Thermal conductivity
(This section closely follows parts of chapter 8 in Transport Phenomena by R.3.
305
.8 m/s2 ). Stokes showed f = 6πηr • Gravitational force (exerted downwards): Fg = gravitational acceleration (9.12)
45.• The frictional force (exerted upwards) is proportional to velocity: Ff = −fv.B. κ. Lightfoot Wiley New York 1960) The thermal conductivity.

whereas the thermal conductivity of most liquids decrease with increasing temperature.14) A dt dx where Qf is the heat ﬂux.
306
.1. from hot to cold. 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.e. a linear steady state temperature distribution across the material is established. (45. 45.Under such conditions. Thermal conductivities are positive quantities so Fourier’s law says that heat ﬂow down a temperature gradient. i. This is called Fourier’s law of heat conduction (one-dimensional version). And a constant rate of heat ﬂow dq is needed to maintain dt the temperature diﬀerence 4T = (T1 − T2 ) 4T 1 dq = −κ ..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 . (45.3.

15)
307
. (45. Dry porous materials are poor heat conductors Rule of Thumb: Thermal conductivity and electrical conductivity go hand in hand.45. There is no analog to superconductivity for thermal conductivity. The Wiedemann. κel T where L is the Lorenz number (typically 22 to 29 × 10−9 V2 /K2 ). 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.3. In general metals are better heat conductors than nonmetals and crystals are better heat conductors than amorphous materials. Frantz and Lorenz equation relates the thermal conductivity to electrical conductivity. The Wiedemann. Frantz and Lorenz equation breaks down at low temperature because metals become superconductive. the thermal conductivity of solids have to be determined experimentally because many factors contributing to the thermal conductivity are diﬃcult to predict. Thermal Conductivity of Solids For the most part.2. κel for pure metals: κ = L = const.

2. in general change upon mixing X 4mix = properties of soln − properties of pure. 308
308
(46. one also needs to keep track of the amount of individual species in solution
46. 4mix V = Vsoln − Vsolute − Vsolvent Consider a thermodynamic quantity. n1 +n2
• mole fraction X2 = • molality m = • Molarity c2 =
X1 = 1 − X2
1000X2 . Measures of Composition
There are several measures of composition of solutions • mole ratio r =
n1 n2 n2 . Partial Molar Quantities
Thermodynamic properties. volume. say.1)
(46. For example.1. in addition to the parameters needed to characterize a pure substance. M1 X1
where M1 is the molecular weight of species 1
n2 L solution
46.2)
.46. So. Solutions
Solutions are mixtures of two or more pure substances.

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

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. 2. dn2 = n2 dλ. the total volume of the solution is equal to the sum of the partial molar volumes each weighted by their respective number of moles. negative or zero.
310
. For example.8)
4mix V can be positive. The total volume. (46. one unit of baseballs are mixed with one unit of basketballs.7)
(46. So. one unit of baseballs are mixed with one unit of books. however.5) ¯ Now. dn1 = n1 dλ. 4mix V < 0.6)
That is.46. is not necessarily the mole weighted sum of the volumes of each component in its pure (unmixed) state. Partial Molar Volumes Consider the partial molar volume For constant T and P ¯ ¯ dV = V1 dn1 + V2 dn2 (46.2.2. Vi depends on concentration. 4mix V > 0.
1. so change each amount of substance proportional to the amount substance present.

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

Raoult’s Law In discussing both Raoult’s law and Henry’s law.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. we are describing the behavior of a liquid solution by measuring the vapor (partial) pressures of the components
312
. 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). mole fraction.12) i ai g(ζ) (46. concentration etc.). pressure.. This implicit deﬁnition is awkward so for convenience one deﬁnes the activity coeﬃcient as the argument of the above limit. (46. γi ≡ which we can rearrange as ai = γ i g(ζ).g.10)
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. and ζ ª is the value of ζ at the reference state.2. (46. μi − μª = RT ln ai .3.

4mix G = μ1 n1 + μ2 n2 − μ• n1 − μ• n2 1 2 (46.For simplicity we consider here only a two component solution.18)
Now. so dG = (μ1 n1 + μ2 n2 ) dλ then G = μ1 n1 + μ2 n2 . 1 2 ai low P Pi ' RT ln • .17) (46.15) (46.
313
. dG = μ1 dn1 + μ2 dn2 . Take diﬀerential change along a line of constant concentration.13)
= (μ1 − μ• ) n1 + (μ2 − μ• ) n2 . μ1 − μ• = RT ln 1
where Pi is the vapor pressure of the ith component above the solution.16) (46.14) (46. Recall that 4mix G = G(soln) − G(pure components) Hence. • ai Pi (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
(46.21)
That is.22) • • P1 / P2 / 4mix G = RT (n1 ln X1 + n2 ln X2 ) Again. this is for an ideal solution in the Raoult’s Law sense.3. From ¶ ¶ µ ∂G ∂ (G/T ) S=− and H = − .24)
(46.25)
(46.26)
314
.3.20)
46.19)
(46. 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.23)
(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. 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.

there are speciﬁc interactions between particles. The reference function is g(ζ) = ζ = Xi . • negative deviation: the molecules prefer to be around other types of molecules than themselves. 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. • no deviation: the molecules have no preference. ai =1 Xi →1 Xi lim implies ai and γ i
(RL) (RL) (RL)
(46.28)
→ 1 as Xi → 1
Deviations from Raoult’s Law Raoult’s law is a purely statistical law.
315
. in reality. The Reference State (RL) Let us apply the deﬁnition of activity for the Raoult’s law reference state.(since G/T is independent of 1/T ).
(46. and the reference state is Xi = 1 So. It does not require any kind of interaction among the constituent particle making up the solution. Since.27)
= γi
(RL)
Xi .

e.30) (46. mixing with one substance may lead to a positive deviation but mixing with another substance may lead to a negative deviation. kXi = lim µ Pi Xi ¶ (46.3.4. where kXi is the Henry’s law constant.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). i.It is very important to note that this deviation from Raoult’s law is a property of the solution and NOT any given component.. For example. at inﬁnite dilution.
316
.
Positive deviation from Raoult’s lawNegative deviation from Raoult’s law 46. Henry’s Law Henry’s Law: Pi = kXi Xi . for a given component.

34)
317
. whereas Henry’s law applies to the subdominant species X2 → 0. (HL) ai lim =1 (46.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
(46.33)
= γ Mi Mi
(HL)
(46. X1 → 1. Raoult’s law applies to the dominant species. But. So. molality or molarity is used then ai and ai respectively.31) Xi →0 Xi implies (HL) (HL) = γ i Xi . (46. they apply to opposite species in the solution.32) ai → 1 as Xi → 0 and γ i If instead of mole fraction. 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. and the reference state is now Xi = 0 So.

μ1 (solid) = μ1 (soln). Freezing Point Depression At Tf (freezing point). | {z }
μs 1
318
.1.4. 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 46.4.46.

35)
(46.Using the Raoult’s law reference state (since we are interested in the behavior of the dominant species). The freezing point depression is
Θ=− 46.2. (so. Osmotic Pressure
RTf•2 ln a1 4f H
We consider the osmotic pressure at a constant temperature.4. (46. using
∂μ ∂T
(46. T.
319
.38) •2 •2 • RTf Tf RTf • where Θ ≡ Tf − Tf . So.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. dG = V dP ). 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.37)
• For small changes in the freezing point we may approximate T by Tf in the integrand. Z Tf −4f H 4f H ln a1 ' dT = Θ.

Thus
1 z }| { • • V Π n1 Vm1 Π n2 .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 .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. 2 3
(46. hence ¯ μ• = μ• + RT ln a1 + V1 Π. a1 = X1 = 1 − X2 : ln a1 = ln(1 − X2 ) =
• Vm1 Π RT
(46.43)
320
. 1 1 (46.42)
'
n2 n1
for dilute solutions.39)
¯ where V1 is the partial molar volume of the solvent in solution (diﬃcult to measure) and Π is the hydrostatic (osmotic) pressure.40)
(46.

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

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

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

This is simply another in our long list of alternative statements of the second law.
324
.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. di S = dS ≥ 0.2. the second law underlies all the concepts of this chapter. holds. in every macroscopic region of the system the entropy production due to irreversible processes is positive. 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..e. compensated by a suﬃcient production in another part is prohibited — i.
47. The Second Law
As you might expect.

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

6)
We are now interested in exposing the time dependence. so.5) we get (47. using Qf = κA4T q =− 4t D in diﬀerential form this is
dT dq = −κA .47. one of which is held at temperature T1 and ¯ ¯ the other at T2 (take T1 > T > T2 ) where T is the temperature at the interface.
326
.7) dt dx Example: Find the entropy production in a system consisting of two identical connected blocks of metal (I and II). (47.1.3. 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.

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

14)
a result we might have guessed. Extent of reaction: ξ is deﬁned by dξ = dni .P = − P − i vi μi P
i
vi μi and a ≡ − (4rxn A)T.11) ¶
−Aκ4T di qI = .3. dt D So.V =
2.13) dt dt ¯ Using the above expression for heat ﬂow gives us T since. Chemical aﬃnity: a ≡ − (4rxn G)T.12)
¯ To determine T we use the fact that the heat ﬂow out of I is equal to the heat ﬂow into II: di qI −di qII = .2. where ni is the number of moles vi of the ith component and vi the stoichiometric factor of the ith component. T1 − T = − T − T2 ⇒ T = 2 D / D / (47. −Aκ4T di S = dt D µ 1 1 − T1 T2
(47.For this example di qI di S = dt dt From chapter 24 we know
µ
1 1 − T1 T2
¶ (47. − ¢ ¢ κ/ κ/ /A ¡ / A ¡¯ ¯ ¯ T1 + T2 .
47.
328
. Entropy Production due to Chemical Reactions Deﬁnitions: 1. (47.

V is positive as is v. This is because a = − (4rxn A)T.15)
(47.18)
d S
dS
(47.17)
z }| { z }| { (dA)T.20)
We see that for a spontaneous process the entropy production per unit time is positive. 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.V dq − = (dU)T.V − T dS ⇒ dS = T T
dq
e i z}|{ z}|{ dq adξ + dS = T T
(47..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 so
µ ¶ 1 dni = −adξ μi dni = vi μi vi | i {z }| {z } X
−a dξ −adξ
(47.
329
.16)
but (dA)T.V = X
i dξ dt
dnH2 dnNH3 dnN2 = = (−1) (−3) (2)
(47.• e.

the so-called Dufour eﬀect is heat ﬂux down a concentration gradient
330
. the entropy production per unit time generalizes to N 1X di S = aj vj ≥ 0.Simultaneous Reactions For N simultaneous chemical reactions.4. Thermodynamic coupling need not be conﬁned to coupling between the same types of processes.
47. Conversely. a2 v2 > 0 such that a1 v1 + a2 v2 > 0. The socalled Soret eﬀect is ﬂux of matter down a temperature gradient. diﬀusion is the ﬂux of matter down a concentration gradient. Thermodynamic Coupling
Processes may be what is called thermodynamically coupled such that a process that normally is not thermodynamically favored can be coupled to another process that is thermodynamically favored so as to allow for the unfavorable process to proceed spontaneously. (47.
For example in a system of two coupled reactions we could have a1 v1 < 0. 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. That is. We just saw an example of such a situation with the discussion of simultaneous reactions.21) dt T j=1
The second law requires that the total entropy production for simultaneous reactions is positive.

If the perturbation is released the system will begin to evolve in time as it heads back towards the thermalized equilibrium state. • Irreversibly — The evolution towards equilibrium cannot be undone–it is irreversible Example: The spin echo in pulsed NMR • A radio frequency pulse prepares an ensemble of nuclear spins such that they are all spinning coherently. Echo Phenonmena
Consider an ensemble that is perturbed away from thermal equilibrium by some means such as by applying a ﬁeld.
331
.5.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. The ensemble evolves in two ways • Reversibly — A second perturbation can “undo” or reverse the evolution.

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

22)
333
333
.Key Equations for Exam 4
Listed here are some of the key equations for Exam 4.23) (47. This section should not substitute for your studying of the rest of this material.24) (47. dT T 4φ Vm • The Clausius-Clapeyron equation is 4φ Hm d(ln P ) =− d(1/T ) R • Fick’s ﬁrst law of diﬀusion is dC 1 dn = −D A dt dx (47. 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.
Equations
• The Clapeyron Equation is 4φ Hm dP = .

31)
Pi = kXi Xi .34)
334
.
γi
(RL)
→ 1 as Xi → 1
(47.30)
= γi
(RL)
Xi .
(47.32)
where kXi is the Henry’s law constant.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 .
(47. A dt dx X
(47. kXi = lim • Henry’s law reference ai
(HL) Xi →0
Pi Xi
.
(47. ∂t ∂x
(47.
γi
(HL)
→ 1 as Xi → 0.33)
= γi
(HL)
Xi . 6πηr
(47.• Fick’s second law of diﬀusion:
∂ 2C ∂C =D 2.26)
• Fourier’s law of heat conduction is
dT 1 dq = Qf = −κ . µ ¶
(47.27)
• Mixing 4mix = properties of soln − • Chemical potential • Raoult’s Law: • Raoult’s law reference ai • Henry’s Law:
(RL)
properties of pure.

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

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

334 Henry’s law constant 316. 86 Hamiltonian 47 normalization constant 49. 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.equlibrium constant 153 Euler’s identity 4 expansion of gases 111 reversible 114 extent of reaction 328 Eyring’s equation 265. 334 ﬁrst law of thermodynamics 121. 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. 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. 86 potential energy 39 Schrodinger equation for 39 heat 109 sign convention 110 heat capacity 115. 333 Fick’s second law 302. 291 fermions 56 Fick’s ﬁrst law 302. 133 Heisenberg uncertainty principle 30 and the harmonic oscillator 41 helium 55 electron-electron repulsion term 55 Hamiltonian 55 Helmholtz free energy 106 Henry’s law 311. 316. 121 intramolecular vibrational relaxation (IVR) 242
337
. 44. 133 ﬂipping coins 90 ﬂuctuation 92 ﬂuorescence 242 stokes shift 242 Fourier’s law of heat conduction 306.

290 mean ionic activity 162 mean ionic activity coeﬃcient 162 method of initial velocities 259 method of isolation 259 microstate 90 Mie scattering 84 mirror plane symmetry 70 molar heat capacity 115 molecular collisions simple model for 252
molecular hydrogen ion 67 Hamiltonian for 67 molecular orbital diagram 76 molecular orbitals 68 molecular rotations 235 asymmetric tops 239 centrifugal stretching 236 linear tops 238 polyatomic molecules 237 spherical tops 239 symmetric tops 238 vibrational state dependence of 236 molecular vibrations 228 molecule Scrodinger equation for 78 momentum operator 5 Morse oscillator 64 energy levels for 65. 86. 240 force constant associated with 9 Taylor series expansion of 8 normal modes 229 operator Hermitian 189 ladder 195 linear 189 symmetry 222 operator algebra 187 orientation quantum number 53 orthogonality 191 overtone transitions 66 parameters extensive 109 intensive 109
338
. 86 Schrodinger equation for 65 wavefunction for 65 Morse potential 64.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. 290 mean free path 253.

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. 132 vibrational 101. 233 and the character table 234 Raoult’s law 311. 82. 219
339
. 291 reciprocal rule 108 red sunsets 82 Redlich-Kwang gas 270 reference states 147 relationship between CP and CV 139. 314. 312. 248 energy 235. 276 relaxation eﬀects 167 rigid rotor 200 degeneracy of 235. 181 energy levels 183 energy levels for 34. 131 electronic 101 grand canonical 97 isothermal—isobaric 97 microcanonical 96 molecular 100 rotational 101. 132 translational 101. 218 partition coeﬃcient 154 and drug delivery 155 for the Born model 174 partition function canonical 96. 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. 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. 218 particle on a ring 194 boundary conditions 194 energy levels for 195. 44. 133 Raman scattering 80 Raman spectroscopy 66. 247 rotational energy levels 200.particle in a box 31. 87 reaction velocity 255. 324 principle quantum number 52 probability amplitude 22 probability distribution 22 PV work 111. 218 Hamitonian for 194 wavefunctions for 195. 44.

219 Hamiltonian for 212 Tyndall scattering 84 ungerade 69 van der Waals equation
340
. 133 tips for solving problems 2 total derivative 107 transfer matrix 11 triple point 300 two level system 211 ‘left’ and ‘right’ states 213. 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. 53 wavefunction 51 spin orientation quantum number 51.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 statements of 127 simple collision theory 262 Slater determinant 58 for lithium 59 solar system model 17 solvation 169 solvophobic eﬀect 176 speciﬁc heat 115 spherical harmonic functions 48. 200 spin 201 quantum number 51.