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Physical Chemistry

by ;
Edition:
2nd
ISBN13:

9780805338423

ISBN10:
080533842X
Format:
Hardcover
Pub. Date:
1/1/2010
Publisher(s):
Prentice Hall
List Price: $162.60

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Summary

Physical Chemistry is a groundbreaking new 4-color text that explains core topics in depth with a focus on basic principles, applications, and modern research. the authors hone in on key concepts and cover them thoroughly and in detail - as opposed to the general, encyclopedic approach competing textbooks take. Excessive math formalism is avoided to keep students focused on the most important concepts and to provide greater clarity. Applications woven throughout each chapter demonstrate to students how chemical theories are used to solve real-world chemical problems in biology, environmental science, and material science. Extensive coverage of modern research and new developments in the field get students excited about this dynamic branch of science. The text has been designed in such a way that it can be used for either "Quantum first" or "Thermo first" courses. the combined text is arranged for a traditional "Thermo first" course; the split texts are organized to facilitate "Quantum first" courses. The online Chemistry Place for Physical Chemistry features interactive problems and simulations that reinforce and build upon material included in the book.

Table of Contents

Fundamental Concepts of Thermodynamics
1(12)
What Is Thermodynamics and Why Is It Useful?
1(1)
Basic Definitions Needed to Describe Thermodynamic Systems
2(2)
Thermometry
4(2)
Equations of State and the Ideal Gas Law
6(3)
A Brief Introduction to Real Gases
9(4)
Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
13(26)
The Internal Energy and the First Law of Thermodynamics
13(1)
Work
14(2)
Heat
16(3)
Heat Capacity
19(3)
State Functions and Path Functions
22(2)
Equilibrium, Change, and Reversibility
24(1)
Comparing Work for Reversible and Irreversible Processes
25(4)
Determining ΔU and Introducing Enthalpy, a New State Function
29(1)
Calculating q, w, ΔU, and ΔH for Processes Involving Ideal Gases
30(4)
The Reversible Adiabatic Expansion and Compression of an Ideal Gas
34(5)
The Importance of State Functions: Internal Energy and Enthalpy
39(24)
The Mathematical Properties of State Functions
39(5)
The Dependence of U on V and T
44(2)
Does the Internal Energy Depend More Strongly on V or T?
46(4)
The Variation of Enthalpy with Temperature at Constant Pressure
50(2)
How Are CP and CV Related?
52(1)
The Variation of Enthalpy with Pressure at Constant Temperature
53(2)
The Joule-Thompson Experiment
55(3)
Liquefying Gases Using an Isenthalpic Expansion
58(5)
Thermochemistry
63(16)
Energy Stored in Chemical Bonds Is Released or Taken Up in Chemical Reactions
63(1)
Internal Energy and Enthalpy Changes Associated with Chemical Reactions
64(4)
Hess's Law Is Based on Enthalpy Being a State Function
68(2)
The Temperature Dependence of Reaction Enthalpies
70(2)
The Experimental Determination of ΔU and ΔH for Chemical Reactions
72(3)
Differential Scanning Calorimetry
75(4)
Entropy and the Second and Third Laws of Thermodynamics
79(34)
The Universe Has a Natural Direction of Change
79(1)
Heat Engines and the Second Law of Thermodynamics
80(5)
Introducing Entropy
85(1)
Calculating Changes in Entropy
86(4)
Using Entropy to Calculate the Natural Direction of a Process in an Isolated System
90(2)
The Clausius Inequality
92(1)
The Change of Entropy in the Surroundings and ΔS total = ΔS + ΔS surroundings
93(2)
Absolute Entropies and the Third Law of Thermodynamics
95(4)
Standard States in Entropy Calculations
99(1)
Entropy Changes in Chemical Reactions
99(2)
Refrigerators, Heat Pumps, and Real Engines
101(4)
(Supplemental) Using the Fact that S Is a State Function to Determine the Dependence of S on V and T
105(1)
(Supplemental) The Dependence of S on T and P
106(2)
(Supplemental) The Thermodynamic Temperature Scale
108(5)
Chemical Equilibrium
113(36)
The Gibbs Energy and the Helmholtz Energy
113(4)
The Differential Forms of U, H, A, and G
117(2)
The Dependence of the Gibbs and Helmholtz Energies on P, V, and T
119(3)
The Gibbs Energy of a Reaction Mixture
122(1)
The Gibbs Energy of a Gas in a Mixture
123(1)
Calculating the Gibbs Energy of Mixing for Ideal Gases
124(2)
Expressing Chemical Equilibrium in an Ideal Gas Mixture in Terms of the μi
126(2)
Calculating ΔG reaction and Introducing the Equilibrium Constant for a Mixture of Ideal Gases
128(2)
Calculating the Equilibrium Partial Pressures in a Mixture of Ideal Gases
130(1)
The Variation of Kp with Temperature
131(2)
Equilibria Involving Ideal Gases and Solid or Liquid Phases
133(1)
Expressing the Equilibrium Constant in Terms of Mole Fraction or Molarity
134(1)
The Dependence of ξeq on T and P
135(1)
(Supplemental) A Case Study: The Synthesis of Ammonia
136(5)
(Supplemental) Expressing U and H and Heat Capacities Solely in Terms of Measurable Quantities
141(8)
The Properties of Real Gases
149(18)
Real Gases and Ideal Gases
149(1)
Equations of State for Real Gases and Their Range of Applicability
150(4)
The Compression Factor
154(3)
The Law of Corresponding States
157(3)
Fugacity and the Equilibrium Constant for Real Gases
160(7)
Phase Diagrams and the Relative Stability of Solids, Liquids, and Gases
167(26)
What Determines the Relative Stability of the Solid, Liquid, and Gas Phases?
167(2)
The Pressure-Temperature Phas Diagram
169(7)
The Pressure-Volume and Pressure-Volume-Temperature Phase Diagrams
176(2)
Providing a Theoretical Basis for the P--T Phase Diagram
178(1)
Using the Clapcyron Equation to Calculate Vapor Pressure as a Function of T
179(2)
The Vapor Pressure of a Pure Substance Depends on the Applied Pressure
181(1)
Surface Tension
182(3)
Chemistry in Supercritical Fluids
185(1)
Liquid Crystals and LCD Displays
186(7)
Ideal and Real Solutions
193(30)
Defining the Ideal Solution
193(2)
The Chemical Potential of a Component in the Gas and Solution Phases
195(1)
Applying the Ideal Solution Model to Binary Solutions
196(4)
The Temperature-Composition Diagram and Fractional Distillation
200(2)
The Gibbs-Duhem Equation
202(2)
Colligative Properties
204(1)
The Freezing Point Depression and Boiling Point Elevation
204(3)
The Osmotic Pressure
207(1)
Real Solutions Exhibit Deviations from Raoult's Law
208(3)
The Ideal Dilute Solution
211(2)
Activities Are Defined with Respect to Standard States
213(3)
Henry's Law and the Solubility of Gases in a Solvent
216(2)
Chemical Equilibrium in Solutions
218(5)
Electrolyte Solutions
223(16)
The Enthalpy, Entropy, and Gibbs Energy of Ion Formation in Solutions
223(3)
Understanding the Thermodynamics of Ion Formation and Solvation
226(2)
Activities and Activity Coefficients for Electrolyte Solutions
228(2)
Calculating γ± Using the Debye-Huckel Theory
230(4)
Chemical Equilibrium in Electrolyte Solutions
234(5)
Electrochemical Cells, Batteries, and Fuel Cells
239(36)
The Effect of an Electrical Potential on the Chemical Potential of Charged Species
239(2)
Conventions and Standard States in Electrochemistry
241(3)
Measurement of the Reversible Cell Potential
244(1)
Chemical Reactions in Electrochemical Cells and the Nernst Equation
245(2)
Combining Standard Electrode Potentials to Determine the Cell Potential
247(2)
Obtaining Reaction Gibbs Energies and Reaction Entropies from Cell Potentials
249(1)
The Relationship between the Cell EMF and the Equilibrium Constant
249(2)
Determination of E° and Activity Coefficients Using an Electrochemical Cell
251(1)
Cell Nomenclature and Types of Electrochemical Cells
252(1)
The Electrochemical Series
253(1)
Thermodynamics of Batteries and Fuel Cells
254(1)
The Electrochemistry of Commonly Used Batteries
254(2)
Fuel Cells
256(3)
(Supplemental) Electrochemistry at the Atomic Scale
259(7)
(Supplemental) Using Electrochemistry for Nanoscale Machining
266(1)
(Supplemental) Absolute Half-Cell Potentials
267(8)
From Classical to Quantum Mechanics
275(14)
Why Study Quantum Mechanics?
275(1)
Quantum Mechanics Arose Out of the Interplay of Experiments and Theory
276(1)
Blackbody Radiation
277(2)
The Photoelectric Effect
279(2)
Particles Exhibit Wave-Like Behavior
281(1)
Diffraction by a Double Slit
281(4)
Atomic Spectra
285(4)
The Schrodinger Equation
289(22)
What Determines If a System Needs to Be Described Using Quantum Mechanics?
289(5)
Classical Waves and the Nondispersive Wave Equation
294(3)
Waves Are Conveniently Represented as Complex Functions
297(2)
Quantum Mechanical Waves and the Schrodinger Equation
299(1)
Solving the Schrodinger Equation: Operators, Observables, Eigenfunctions, and Eigenvalues
300(2)
The Eigenfunctions of a Quantum Mechanical Operator Are Orthogonal
302(3)
The Eigenfunctions of a Quantum Mechanical Operator Form a Complete Set
305(1)
Summing Up the New Concepts
306(5)
The Quantum Mechanical Postulates
311(8)
The Physical Meaning Associated with the Wave Function
311(1)
Every Observable Has a Corresponding Operator
312(1)
The Result of an Individual Measurement
313(1)
The Expectation Value
314(3)
The Evolution in Time of a Quantum Mechanical System
317(2)
Using Quantum Mechanics on Simple Systems
319(18)
The Free Particle
319(1)
The Particle in a One-Dimensional Box
320(5)
Two- and Three-Dimensional Boxes
325(2)
Using the Postulates to Understand the Particle in the Box and Vice Versa
327(10)
The Particle in the Box and the Real World
337(18)
The Particle in the Finite Depth Box
337(1)
Differences in Overlap between Core and Valence Electrons
338(1)
Pi Electrons in Conjugated Molecules Can Be Treated as Moving Freely in a Box
339(1)
Why Does Sodium Conduct Electricity and Why Is Diamond an Insulator?
340(1)
Tunneling through a Barrier
341(1)
The Scanning Tunneling Microscope
342(4)
Tunneling in Chemical Reactions
346(1)
(Supplemental) Quantum Wells and Quantum Dots
347(8)
Commuting and Noncommuting Operators and the Surprising Consequences of Entanglement
355(22)
Commutation Relations
355(2)
The Stern-Gerlach Experiment
357(3)
The Heisenberg Uncertainty Principle
360(4)
(Supplemental) The Heisenberg Uncertainty Principle Expressed in Terms of Standard Deviations
364(2)
(Supplemental) A Thought Experiment Using a Particle in a Three-Dimensional Box
366(2)
(Supplemental) Entangled States, Teleportation, and Quantum Computers
368(9)
A Quantum Mechanical Model for the Vibration and Rotation of Molecules
377(26)
Solving the Schrodinger Equation for the Quantum Mechanical Harmonic Oscillator
377(5)
Solving the Schrodinger Equation for Rotation in Two Dimensions
382(3)
Solving the Schrodinger Equation for Rotation in Three Dimensions
385(3)
The Quantization of Angular Momentum
388(2)
The Spherical Harmonic Functions
390(2)
(Optional Review) The Classical Harmonic Oscillator
392(4)
(Optional Review) Angular Motion and the Classical Rigid Rotor
396(2)
(Supplemental) Spatial Quantization
398(5)
The Vibrational and Rotational Spectroscopy of Diatomic Molecules
403(32)
An Introduction to Spectroscopy
403(3)
Absorption, Spontaneous Emission, and Stimulated Emission
406(1)
An Introduction to Vibrational Spectroscopy
407(3)
The Origin of Selection Rules
410(2)
Infrared Absorption Spectroscopy
412(4)
Rotational Spectroscopy
416(5)
(Supplemental) Fourier Transform Infrared Spectroscopy
421(3)
(Supplemental) Raman Spectroscopy
424(2)
(Supplemental) How Does the Transition Rate between States Depend on Frequency?
426(9)
The Hydrogen Atom
435(18)
Formulating the Schrodinger Equation
435(1)
Solving the Schrodinger Equation for the Hydrogen Atom
436(1)
Eigenvalues and Eigenfunctions for the Total Energy
437(6)
The Hydrogen Atom Orbitals
443(2)
The Radial Probability Distribution Function
445(4)
The Validity of the Shell Model of an Atom
449(4)
Many-Electron Atoms
453(34)
Helium: The Smallest Many-Electron Atom
453(2)
Introducing Electron Spin
455(1)
Wave Functions Must Reflect the Indistinguishability of Electrons
456(4)
Using the Variational Method to Solve the Schrodinger Equation
460(1)
The Hartree-Fock Self-Consistent Field Method
461(5)
Understanding Trends in the Periodic Table from Hartree-Fock Calculations
466(3)
Good Quantum Numbers, Terms, Levels, and States
469(2)
The Energy of a Configuration Depends on Both Orbital and Spin Angular Momentum
471(7)
Spin-Orbit Coupling Breaks Up a Term into Levels
478(1)
(Supplemental) Configurations with Paired and Unpaired Electron Spins Differ in Energy
479(8)
Examples of Spectroscopy Involving Atoms
487(18)
The Essentials of Atomic Spectroscopy
487(3)
Analytical Techniques Based on Atomic Spectroscopy
490(3)
The Doppler Effect
493(1)
The Helium-Neon Laser
494(4)
Laser Isotope Separation
498(1)
Auger Electron and X-Ray Photoelectron Spectroscopies
498(4)
Selective Chemistry of Excited States: O(3P) and O(1D)
502(3)
Chemical Bonding in H2+ and H2
505
Quantum Mechanics and the Chemical Bond
505(1)
The Simplest One-Electron Molecule: H2+
505(1)
The Molecular Wave Function for Ground-State H2+
506(2)
The Energy Corresponding to the Molecular Wave Functions ψg and ψu
508(4)
A Closer Look at the Molecular Wave Functions ψg and ψu
512(2)
The H2 Molecule: Molecular Orbital and Valence Bond Models
514(3)
Comparing the Valence Bond and Molecular Orbital Models of the Chemical Bond
517
Chemical Bonding in Diatomic Molecules
247(298)
Solving the Schrodinger Equation for Many-Electron Molecules
521(1)
Expressing Molecular Orbitals as a Linear Combination of Atomic Orbitals
522(4)
The Molecular Orbital Energy Diagram
526(2)
Molecular Orbitals for Homonuclear Diatomic Molecules
528(4)
The Electronic Structure of Many-Electron Molecules
532(3)
Bond Order, Bond Energy, and Bond Length
535(2)
Heteronuclear Diatomic Molecules
537(1)
(Supplemental) The Molecular Electrostatic Potential
538(7)
Molecular Structure and Energy Levels for Polyatomic Molecules
545(30)
Lewis Structures and the VSEPR Model
545(3)
Describing Localized Bonds Using Hybridization for Methane, Ethene, and Ethyne
548(3)
Constructing Hybrid Orbitals for Nonequivalent Ligands
551(5)
Using Hybridization to Describe Chemical Bonding
556(1)
Predicting Molecular Structure Using Molecular Orbital Theory
557(4)
How Different Are Localized and Delocalized Bonding Models?
561(2)
Qualitative Molecular Orbital Theory for Conjugated and Aromatic Molecules: The Huckel Model
563(7)
From Molecules to Solids
570(1)
Making Semiconductors Conductive at Room Temperature
571(4)
Electronic Spectroscopy
575(22)
The Energy of Electronic Transitions
575(1)
Molecular Term Symbols
576(2)
Transitions Between Electronic States of Diatomic Molecules
578(2)
The Vibrational Fine Structure of Electronic Transitions in Diatomic Molecules
580(2)
UV-Visible Light Absorption in Polyatomic Molecules
582(3)
Transitions among the Ground and Excited States
585(1)
Singlet-Singlet Transitions: Absorption and Fluorescence
585(2)
Intersystem Crossing and Phosphorescence
587(1)
Fluorescence Spectroscopy and Analytical Chemistry
588(2)
Ultraviolet Photoelectron Spectroscopy
590(3)
(Supplemental) Assigning + and - to Σ Terms of Diatomic Molecules
593(4)
Computational Chemistry
597(60)
Warren Hehre
The Promise of Computational Chemistry
597(1)
Potential Energy Surfaces
598(4)
Hartree-Fock Molecular Orbital Theory: A Direct Descendant of the Schrodinger Equation
602(2)
Properties of Limiting Hartree-Fock Models
604(5)
Theoretical Models and Theoretical Model Chemistry
609(1)
Moving Beyond Hartree-Fock Theory
610(6)
Gaussian Basis Sets
616(2)
Selection of a Theoretical Model
618(15)
Graphical Models
633(9)
Conclusion
642(15)
Molecular Symmetry
657(30)
Symmetry Elements, Symmetry Operations, and Point Groups
657(2)
Assigning Molecules to Point Groups
659(2)
The H2O Molecule and the C2v Point Group
661(5)
Representations of Symmetry Operators, Bases for Representations, and the Character Table
666(3)
The Dimension of a Representation
669(4)
Using the C2v Representations to Construct Molecular Orbitals for H2O
673(2)
The Symmetries of the Normal Modes of Vibration of Molecules
675(5)
Selection Rules and Infrared versus Raman Activity
680(1)
(Supplemental) Using the Projection Operator Method to Generate MOs That Are Bases for Irreducible Representations
681(6)
Nuclear Magnetic Resonance Spectroscopy
687(34)
Intrinsic Nuclear Angular Momentum and Magnetic Moment
687(1)
The Energy of Nuclei of Nonzero Nuclear Spin in a Magnetic Field
688(3)
The Chemical Shift for an Isolated Atom
691(1)
The Chemical Shift for an Atom Embedded in a Molecule
692(1)
Electronegativity of Neighboring Groups and Chemical Shifts
693(1)
Magnetic Fields of Neighboring Groups and Chemical Shifts
694(1)
Multiplet Splitting of NMR Peaks Arises through Spin-Spin Coupling
695(5)
Multiplet Splitting When More Than Two Spins Interact
700(3)
Peak Widths in NMR Spectroscopy
703(1)
Solid-State NMR
704(1)
NMR Imaging
705(1)
(Supplemental) The NMR Experiment in the Laboratory and Rotating Frames
706(2)
(Supplemental) Fourier Transform NMR Spectroscopy
708(4)
(Supplemental) Two-Dimensional NMR
712(9)
Probability
721(24)
Why Probability?
721(1)
Basic Probability Theory
722(8)
Stirling's Approximation
730(1)
Probability Distribution Functions
731(3)
Probability Distributions Involving Discrete and Continuous Variables
734(2)
Characterizing Distribution Functions
736(9)
The Boltzmann Distribution
745(22)
Microstates and Configurations
745(6)
Derivation of the Boltzmann Distribution
751(5)
Dominance of the Boltzmann Distribution
756(2)
Physical Meaning of the Boltzmann Distribution Law
758(2)
The Definition of β
760(7)
Ensemble and Molecular Partition Functions
767(32)
The Canonical Ensemble
767(2)
Relating Q to q for an Ideal Gas
769(2)
Molecular Energy Levels
771(1)
Translational Partition Function
772(2)
Rotational Partition Function: Diatomics
774(8)
Rotational Partition Function: Polyatomics
782(2)
Vibrational Partition Function
784(6)
The Equipartition Theorem
790(1)
Electronic Partition Function
791(4)
Review
795(4)
Statistical Thermodynamics
799(32)
Energy
799(4)
Energy and Molecular Energetic Degrees of Freedom
803(5)
Heat Capacity
808(4)
Entropy
812(5)
Residual Entropy
817(1)
Other Thermodynamic Functions
818(4)
Chemical Equilibrium
822(9)
Kinetic Theory of Gases
831(22)
Kinetic Theory of Gas Motion and Pressure
831(3)
Velocity Distribution in One Dimension
834(4)
The Maxwell Distribution of Molecular Speeds
838(2)
Comparative Values for Speed Distribution: νave, νmp, and νrms
840(2)
Gas Effusion
842(3)
Molecular Collisions
845(3)
The Mean Free Path
848(5)
Transport Phenomena
853(34)
What Is Transport?
853(2)
Mass Transport: Diffusion
855(3)
The Time Evolution of a Concentration Gradient
858(2)
(Supplemental) Statistical View of Diffusion
860(2)
Thermal Conduction
862(4)
Viscosity of Gases
866(3)
Measuring Viscosity
869(2)
Diffusion in Liquids and Viscosity of Liquids
871(2)
(Supplemental) Sedimentation and Centrifugation
873(3)
Ionic Conduction
876(11)
Elementary Chemical Kinetics
887(44)
Introduction to Kinetics
887(1)
Reaction Rates
888(2)
Rate Laws
890(6)
Reaction Mechanisms
896(1)
Integrated Rate Law Expressions
897(5)
(Supplemental) Numerical Approaches
902(1)
Sequential First-Order Reactions
903(5)
Parallel Reactions
908(2)
Temperature Dependence of Rate Constants
910(2)
Reversible Reactions and Equilibrium
912(4)
(Supplemental) Perturbation-Relaxation Methods
916(2)
(Supplemental) The Autoionization of Water: A T-Jump Example
918(1)
Potential Energy Surfaces
919(2)
Activated Complex Theory
921(10)
Complex Reaction Mechanisms
931(40)
Reaction Mechanisms and Rate Laws
931(2)
The Preequilibrium Approximation
933(2)
The Lindemann Mechanisms
935(2)
Catalysis
937(12)
Radical-Chain Reactions
949(3)
Radical-Chain Polymerization
952(1)
Explosions
953(2)
Photochemistry
955(16)
Appendix A Math Supplement 971(22)
Appendix B Data Tables 993(22)
Appendix C Point Group Character Tables 1015(8)
Appendix D Answers to Selected End-of-Chapter Problems 1023(16)
Index 1039


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