Essentials of physical chemistry:
"Particularly well-suited for students not pursuing a traditional chemistry curriculum, such as premedical and forensic science students, this book presents a stand-alone approach to teaching physical chemistry in a one-semester course, a current trend in undergraduate education. This new under...
Gespeichert in:
| 1. Verfasser: | |
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| Format: | Buch |
| Sprache: | English |
| Veröffentlicht: |
Boca Raton, Fla. [u.a.]
CRC Press
2012
|
| Schlagworte: | |
| Online-Zugang: | Inhaltsverzeichnis |
| Zusammenfassung: | "Particularly well-suited for students not pursuing a traditional chemistry curriculum, such as premedical and forensic science students, this book presents a stand-alone approach to teaching physical chemistry in a one-semester course, a current trend in undergraduate education. This new undergraduate textbook succeeds in inspiring a thorough understanding rather than merely exposing students to what they all too often perceive as a painful and confusing experience. The author includes real-world applications, worked examples, end-of-chapter problems, key solutions, thermodynamic data, and much more to assist in the teaching and learning of physical chemistry"-- |
| Beschreibung: | XXXVI, 476 S. Ill., graph. Darst. 1 CD-ROM (12 cm) |
| ISBN: | 9781439840979 |
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| adam_text | Titel: Essentials of physical chemistry
Autor: Shillady, Donald
Jahr: 2012
Contents
Preface............................................................................................................................................xiii
Author...........................................................................................................................................xvii
List of Constants............................................................................................................................xix
Periodic Table of the Elements......................................................................................................xxi
Introduction: Mathematics and Physics Review..........................................................................xxiii
Chapter 1 Ideal and Real Gas Behavior.......................................................................................1
Introduction to the First Encounter with Physical Chemistry ................................ 1
Phenomenological Derivation ofthe Ideal Gas Equation...........................................1
Charles (Jacques-Alexandre-Cesar Charles) Law......................................................4
Useful Units.................................................................................................................8
Molecular Weight from Gas Density (the Dumas Bulb Method)............................ 10
Dalton s Law of Partial Pressures.............................................................................11
Nonideal Gas Behavior.............................................................................................13
Supercritical Fluid Chromatography.........................................................................18
Fluids....................................................................................................................19
Supercritical Fluid Instrumentation......................................................................20
Supercritical Mobile Phase...................................................................................21
Sample SCF Separations......................................................................................21
Summary....................................................................................................................22
Problems....................................................................................................................23
References.................................................................................................................24
Chapter 2 Viscosity of Laminar How........................................................................................25
Introduction...............................................................................................................25
Measurement of Viscosity.........................................................................................28
Viscosity of Blood.....................................................................................................30
Staudinger s Rule for Polymer Molecular Weight....................................................31
Summary....................................................................................................................34
Problems....................................................................................................................35
References.................................................................................................................35
Chapter 3 The Kinetic Molecular Theory of Gases...................................................................37
Introduction...............................................................................................................37
Kinetic Assumptions ofthe Theory of Gases...........................................................37
Weighted Averaging: A Very important Concept....................................................39
Summary....................................................................................................................50
Problems....................................................................................................................51
References.................................................................................................................51
Chapter 4 The First Law of Thermodynamics...........................................................................53
Introduction...............................................................................................................53
Historical Development of Thermodynamics...........................................................53
Definitions.................................................................................................................54
First Law of Thermodynamics..................................................................................55
vi Contents
Isothermal Processes.................................................................................................57
Enthalpy and Heat Capacities...................................................................................59
Adiabatic Processes...................................................................................................61
Adiabatic Nozzle Expansion Spectroscopy...............................................................64
Diesel Engine Compression......................................................................................65
Calorimetry and Thermochemistry............................................................................67
Hess s Law of Heat Summation................................................................................71
Standard Heats of Formation at 298.15°K and 1 bar Pressure.................................72
Temperature Dependence of Reaction Enthalpies....................................................73
Polynomial Curve Fitting..........................................................................................74
Application to AH°nn (7 298.15°K)........................................................................75
Other Types of Thermochemistry.............................................................................78
Perspective.................................................................................................................78
Key Formulas and Equations....................................................................................78
Problems....................................................................................................................79
Testing, Grading, and Learning?...............................................................................79
References.................................................................................................................80
Chapter 5 The Second and Third Laws of Thermodynamics....................................................81
Introduction...............................................................................................................81
Carnot Cycle/Engine.................................................................................................81
CarnotCycle.........................................................................................................83
Carnot Efficiency..................................................................................................85
Efficiency of Real Heat Engines...............................................................................86
Entropy and Spontaneity...........................................................................................87
Summary ofthe Second Law of Thermodynamics..................................................88
Eight Basic Equations of Thermodynamics..............................................................88
Third Law of Thermodynamics................................................................................90
Entropy of Reactions............................................................................................92
Entropy Changes at T 298.15°K.......................................................................93
Trouton s Rule/Observation.................................................................................94
Simple Statistical Treatment of Liquids and Gases..................................................95
Summary....................................................................................................................99
Testing, Grading, and Learning?.............................................................................100
Problems..................................................................................................................101
Bibliography............................................................................................................ 102
References...............................................................................................................102
Chapter 6 Gibbs Free Energy and Equilibria..........................................................................103
Introduction.............................................................................................................103
Temperature Dependence of Equilibrium Constants..............................................106
van t Hoff Equation.................................................................................................106
Vapor Pressure of Liquids.......................................................................................108
Phase Equilibria.......................................................................................................112
How Ice Skates Work.............................................................................................113
Gibbs Phase Rule....................................................................................................113
Iodine Triple Point..................................................................................................115
(Cp-Cv) for Liquids and Solids..............................................................................117
Open Systems: Gibbs-Duhem Equation for Partial Molal Volumes.....................119
Chemical Potential for Open Systems.....................................................................123
Contents vii
Modeling Liquids.................................................................................................... 125
Summary.................................................................................................................. 128
Problems.................................................................................................................. 129
Testing, Grading, and Learning?............................................................................. 129
Bibliography............................................................................................................ 130
References...............................................................................................................130
Chapter 7 Basic Chemical Kinetics......................................................................................... 133
Introduction............................................................................................................. 133
First-Order Reactions.............................................................................................. 133
Promethium: An Introduction to Nuclear Chemistry..............................................135
Madame Curie and Radioactivity............................................................................137
Radium.................................................................................................................... 139
Second-Order Rate Processes: [A] = [B]................................................................139
Second-Order Rate Processes: [A] ^ [B]............................................................... 139
Arrhenius Activation Energy...................................................................................145
The Classic A -? B - C Consecutive First-Order Reaction.................................147
Splitting the Atom...................................................................................................150
Problems..................................................................................................................153
References............................................................................................................... 154
Chapter 8 More Kinetics and Some Mechanisms....................................................................155
Introduction.............................................................................................................155
Beyond Arrhenius to the Eyring Transition State...................................................155
Example...................................................................................................................159
Graphical-Analytical Method for A//* and AS*..................................................... 161
Summary of Graphical Method Results at 7/=25°C..............................................163
Further Consideration of SN1 Solvolysis...............................................................164
Chain Reactions and the Steady State.....................................................................165
Steady-State Example No. 1: H2 + Br2 - 2HBr...............................................165
Steady-State Example No. 2: Thermal Cracking of Acetaldehyde....................167
Steady-State Example No. 3: The Lindemann Mechanism...............................168
Enzyme Kinetics......................................................................................................169
Basic Michaelis-Menten Equation.....................................................................171
Example: A Hypothetical Enzyme..........................................................................172
Michaelis-Menten with Competitive Inhibitor..................................................174
Michaelis-Menten Summary..............................................................................176
Kinetics Conclusions...............................................................................................178
Problems..................................................................................................................178
Testing, Grading, and Learning?.............................................................................179
Bibliography............................................................................................................180
References...............................................................................................................180
Chapter 9 Basic Spectroscopy..................................................................................................181
Introduction.............................................................................................................181
Planck s Discovery.................................................................................................. 181
Radio Waves.......................................................................................................183
Balmer s Integer Formula........................................................................................184
A Very Useful Formula........................................................................................... 189
Preliminary Summary of the Bohr Atom................................................................190
viii Contents
Significance of the Bohr Quantum Number n........................................................192
Orbital Screening.....................................................................................................192
X-Ray Emission......................................................................................................193
Forensic/Analytical Use of Auger X-Rays.............................................................196
X-Ray Fluorescence................................................................................................198
X-Ray Diffraction....................................................................................................199
Electronic Absorption Spectroscopy/Spectrophotometry.......................................202
Interpreting Electronic Spectra................................................................................204
General Principles of Spectroscopy........................................................................209
Problems..................................................................................................................210
Bibliography............................................................................................................210
References...............................................................................................................211
Chapter 10 Early Experiments in Quantum Physics..................................................................213
Introduction.............................................................................................................213
Stefan-Boltzmann Law: Relating Heat and Light-Part 1.....................................213
Blackbody Radiation: Relating Heat and Light-Part II........................................214
Photoelectric Effect.................................................................................................221
De Broglie Matter Waves........................................................................................225
Davisson-Germer Experiment................................................................................226
Summary..................................................................................................................230
Problems..................................................................................................................231
References...............................................................................................................232
Chapter 11 The Schrödinger Wave Equation............................................................................233
Introduction.............................................................................................................233
Definition of a Commutator....................................................................................242
Postulates of Quantum Mechanics..........................................................................243
Particle on a Ring....................................................................................................244
Comparison of PUB and POR Applications............................................................247
Additional Theorems in Quantum Mechanics........................................................247
Summary..................................................................................................................249
Problems..................................................................................................................250
Study, Test, and Learn?...........................................................................................251
References...............................................................................................................252
Chapter 12 The Quantized Harmonie Oscillator: Vibrational Spectroscopy.............................253
Introduction.............................................................................................................253
Harmonie Oscillator Details....................................................................................255
Harmonie Oscillator Results....................................................................................258
Reduced Mass.........................................................................................................262
Isotope Shift in the Vibrational Fundamental Frequency.......................................264
Hermite Recursion Rule..........................................................................................265
Infrared Dipole Selection Rule................................................................................265
3N-6 or 3N-5 Vibrations?.................................................................................267
Raman Spectroscopy...............................................................................................271
Summary..................................................................................................................274
Problems..................................................................................................................275
References...............................................................................................................275
Contents ix
Chapter 13 The Quantized Rigid Rotor and the Vib-Rotor.......................................................277
Introduction.............................................................................................................277
Three-Dimensional Particle-in-a-Box......................................................................277
Rigid Rotor..............................................................................................................279
Key Step!............................................................................................................281
Rigid Rotor Wave Functions..............................................................................283
Rigid Rotor Results............................................................................................285
Angular Wave Functions.........................................................................................285
Angular Momentum................................................................................................286
Rotational Spectrum of CO.....................................................................................289
Fourier Transform Spectrometry.............................................................................291
FT-IR Imaging and Microscopy..............................................................................292
Dipole Requirement................................................................................................294
Vib-Rotor Infrared Spectroscopy............................................................................295
Bond Length of H-^C1...........................................................................................302
Summary..................................................................................................................303
Problems..................................................................................................................304
References...............................................................................................................305
Chapter 14 The Schrödinger Hydrogen Atom...........................................................................307
Introduction.............................................................................................................307
Strategy to Solve the Problem.................................................................................307
Associated Laguerre Polynomials...........................................................................310
Interpretation...........................................................................................................311
Pictures of Angular Orbitals....................................................................................316
Powell Equivalent d-Orbitals..................................................................................319
Unsöld s Theorem...................................................................................................323
Aufbau Principle and the Scaled H Atom...............................................................323
Term Symbols and Spin Angular Momentum........................................................324
Hund sRule.............................................................................................................325
L, Sz) versus J, Jz) Coupling.................................................................................326
Summary..................................................................................................................328
Problems..................................................................................................................329
References...............................................................................................................329
Chapter 15 Quantum Thermodynamics.....................................................................................331
Introduction.............................................................................................................331
(Energy) Partition Function.....................................................................................333
Average Translation Energy in One Dimension.....................................................334
Average Rotational Energy of a Diatomic Molecule..............................................334
Average Vibrational Energy....................................................................................335
High-Temperature Limit for Vibrational Heat Capacity.........................................337
Heat Capacity of a Polyatomic Species: Water......................................................337
Combining Partition Functions...............................................................................339
Statistical Formulas for Other Thermodynamic Functions.....................................340
Statistical Formula for S(7).....................................................................................340
Sakur-Tetrode Formula for Absolute Entropy of a Gas.........................................341
Summary..................................................................................................................343
Problems..................................................................................................................344
References...............................................................................................................344
x Contents
Chapter 16 Approximate Methods and Linear Algebra.............................................................345
Introduction.............................................................................................................345
Simple First-Order Perturbation Theory.................................................................345
Principles of Perturbation Theory...........................................................................347
Variation Method....................................................................................................348
Molecular Orbitals and the Secular Equation.........................................................350
Chemical Bonds of Ethylene...................................................................................352
Elementary Linear Algebra.....................................................................................356
Unitary Similarity Diagonalization of a Square Hermitian Matrix.........................359
Jacobi Algorithm for Diagonalization Using a Computer......................................361
Order Matters!.........................................................................................................361
Summary..................................................................................................................362
Problems..................................................................................................................363
Testing, Grading, and Learning?.............................................................................363
Study, Test, and Learn?...........................................................................................365
References...............................................................................................................366
Chapter 17 Electronic Structure of Molecules...........................................................................367
Introduction.............................................................................................................367
Hartree-Fock-Roothan LCAO Calculations...........................................................367
Chemical Effects in Orbital Screening....................................................................368
Many-Electron Wave Functions..............................................................................370
Determinantal Wave Functions for Many-Electron Systems.............................370
Atomic Units...........................................................................................................371
Roothaan s LCAO Hartree-Fock Equation.............................................................372
Electron Exchange Energy.................................................................................373
The Hartree-Fock-Roothaan Equations for 2n Electrons..................................374
Practical Implementation and Examples.................................................................375
SCF Iteration......................................................................................................377
Gaussian Basis Sets............................................................................................377
Dipole Moment of BH............................................................................................392
Excited States of BH...............................................................................................392
Mesoionic Bond Orders..........................................................................................393
Summary..................................................................................................................399
Problems..................................................................................................................399
References...............................................................................................................401
Chapter 18 Point Group Theory and Electrospray Mass Spectrometry....................................403
Introduction.............................................................................................................403
Basic Point Group Theory.......................................................................................403
Calculation of Molecular Vibrations.......................................................................410
Future Development of Electrospray Mass Spectrometry?.....................................412
Making Elephants Fly .........................................................................................414
Summary..................................................................................................................419
Problems..................................................................................................................419
References...............................................................................................................420
Chapter 19 Essentials of Nuclear Magnetic Resonance............................................................423
Introduction.............................................................................................................423
Early NMR Spectrometers......................................................................................423
Contents xi
NMR Spin Hamiltonian..........................................................................................424
Forensic Application of 1D-NMR..........................................................................427
Nuclear Magnetic Resonance: Pulse Analysis........................................................430
Rotating Coordinate System....................................................................................432
Detection of Magnetic Fields..................................................................................433
Bloch Equations......................................................................................................434
Complex Fourier Transform....................................................................................438
2D-NMRCOSY......................................................................................................438
Coherent Spectroscopy............................................................................................439
Product Operator COSY Analysis Using Dr. Brown s Automated Software........440
Anatomy of a 2D Experiment.................................................................................443
Summary..................................................................................................................447
Problems..................................................................................................................447
References...............................................................................................................447
Appendix A: Relation between Legendre and Associated Legendre Polynomials..................449
Appendix B: The Hartree-Fock-Roothaan SCF Equation.......................................................451
Appendix C: Gaussian Lobe Basis Integrals............................................................................457
Appendix D: Spin-Orbit Coupling in the H Atom...................................................................459
Index.............................................................................................................................................465
UseofPCLOBE..........................................................................................................................475
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| spelling | Shillady, Donald 1937- Verfasser (DE-588)135857252 aut Essentials of physical chemistry Don Shillady Boca Raton, Fla. [u.a.] CRC Press 2012 XXXVI, 476 S. Ill., graph. Darst. 1 CD-ROM (12 cm) txt rdacontent n rdamedia nc rdacarrier "Particularly well-suited for students not pursuing a traditional chemistry curriculum, such as premedical and forensic science students, this book presents a stand-alone approach to teaching physical chemistry in a one-semester course, a current trend in undergraduate education. This new undergraduate textbook succeeds in inspiring a thorough understanding rather than merely exposing students to what they all too often perceive as a painful and confusing experience. The author includes real-world applications, worked examples, end-of-chapter problems, key solutions, thermodynamic data, and much more to assist in the teaching and learning of physical chemistry"-- Chemistry, Physical and theoretical / Textbooks SCIENCE / Chemistry / Physical & Theoretical bisacsh Chemie Lehrbuch (DE-588)4123623-3 gnd rswk-swf Physikalische Chemie (DE-588)4045959-7 gnd rswk-swf Physikalische Chemie (DE-588)4045959-7 s Lehrbuch (DE-588)4123623-3 s DE-604 HBZ Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=022491524&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Shillady, Donald 1937- Essentials of physical chemistry Chemistry, Physical and theoretical / Textbooks SCIENCE / Chemistry / Physical & Theoretical bisacsh Chemie Lehrbuch (DE-588)4123623-3 gnd Physikalische Chemie (DE-588)4045959-7 gnd |
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| title | Essentials of physical chemistry |
| title_auth | Essentials of physical chemistry |
| title_exact_search | Essentials of physical chemistry |
| title_full | Essentials of physical chemistry Don Shillady |
| title_fullStr | Essentials of physical chemistry Don Shillady |
| title_full_unstemmed | Essentials of physical chemistry Don Shillady |
| title_short | Essentials of physical chemistry |
| title_sort | essentials of physical chemistry |
| topic | Chemistry, Physical and theoretical / Textbooks SCIENCE / Chemistry / Physical & Theoretical bisacsh Chemie Lehrbuch (DE-588)4123623-3 gnd Physikalische Chemie (DE-588)4045959-7 gnd |
| topic_facet | Chemistry, Physical and theoretical / Textbooks SCIENCE / Chemistry / Physical & Theoretical Chemie Lehrbuch Physikalische Chemie |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=022491524&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
| work_keys_str_mv | AT shilladydonald essentialsofphysicalchemistry |