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9781891389061

Physical Chemistry for the Chemical and Biological Sciences

by
  • ISBN13:

    9781891389061

  • ISBN10:

    1891389068

  • Edition: 3rd
  • Format: Hardcover
  • Copyright: 2000-02-01
  • Publisher: Univ Science Books

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Author Biography

Raymond Chang: Williams College.

Table of Contents

Preface xv
Introduction
1(8)
Nature of Physical Chemistry
1(2)
Units
3(3)
Force
4(1)
Pressure
4(2)
Energy
6(1)
Atomic Mass, Molecular Mass, and the Chemical Mole
6(3)
The Gas Laws
9(28)
Some Basic Definitions
9(1)
An Operational Definition of Temperature
10(1)
Boyle's Law
11(1)
Charles' and Gay-Lussac's Law
11(2)
Avogadro's Law
13(1)
The Ideal Gas Equation
14(2)
Dalton's Law of Partial Pressures
16(2)
Real Gases
18(6)
The van der Waals Equation
19(3)
The Virial Equation of State
22(2)
Condensation of Gases and the Critical State
24(13)
Problems
30(7)
Kinetic Theory of Gases
37(38)
The Model
37(1)
Pressure of a Gas
38(2)
Kinetic Energy and Temperature
40(1)
The Maxwell Distribution Laws
41(6)
Molecular Collisions and the Mean Free Path
47(4)
Gas Viscosity
51(3)
Graham's Laws of Diffusion and Effusion
54(3)
Equipartition of Energy
57(18)
Derivation of Equation 3.24
64(2)
Total and Partial Differentiation
66(3)
Problems
69(6)
The First Law of Thermodynamics
75(50)
Work and Heat
75(7)
Work
75(6)
Heat
81(1)
The First Law of Thermodynamics
82(3)
Enthalpy
85(5)
A Closer Look at Heat Capacities
90(3)
Gas Expansion
93(5)
Isothermal Expansion
93(1)
Adiabatic Expansion
94(4)
Thermochemistry
98(8)
Standard Enthalpy of Formation
98(6)
Dependence of Enthalpy of Reaction on Temperature
104(2)
Bond Energies and Bond Enthalpies
106(19)
Bond Enthalpy and Bond Dissociation Enthalpy
108(5)
Exact and Inexact Differentials
113(4)
Problems
117(8)
The Second Law of Thermodynamics
125(40)
Spontaneous Process
125(2)
Entropy
127(4)
Statistical Defintion of Entropy
128(3)
Thermodynamic Definition of Entropy
131(1)
The Carnot Heat Engine
131(7)
Thermodynamic Efficiency
134(1)
The Entropy Function
135(1)
Refrigerators, Air Conditioners, and Heat Pumps
136(2)
The Second Law of Thermodynamics
138(3)
Entropy Changes
141(7)
Entropy Change due to Mixing of Ideal Gases
141(1)
Entropy Change due to Phase Transitions
142(2)
Entropy Change due to Heating
144(4)
The Third Law of Thermodynamics
148(5)
Third-Law or Absolute Entropies
148(3)
Entropy of Chemical Reactions
151(2)
Residual Entropy
153(12)
Statements of the Second Law of Thermodynamics
157(2)
Problems
159(6)
Gibbs and Helmholtz Energies and Their Applications
165(38)
Gibbs and Helmholtz Energies
165(3)
Meaning of Helmholtz and Gibbs Energies
168(4)
Helmholtz Energy
168(1)
Gibbs Energy
169(3)
Standard Molar Gibbs Energy of Formation (ΔfG°)
172(3)
Dependece of Gibbs Energy on Temperature and Pressure
175(3)
Dependence of G on Temperature
175(1)
Dependence of G on Pressure
176(2)
Gibbs Energy and Phase Equilibria
178(8)
The Clapeyron and Clausius-Clapeyron Equations
180(2)
Phase Diagrams
182(4)
The Phase Rule
186(1)
Thermodynamics of Rubber Elasticity
186(17)
Some Thermodynamic Relationships
191(3)
Derivation of the Phase Rule
194(3)
Problems
197(6)
Nonelectrolyte Solutions
203(46)
Concentration Units
203(2)
Percent by Weight
203(1)
Mole Franction (x)
204(1)
Molarity (M)
204(1)
Molality (m)
204(1)
Partial Molar Quantities
205(3)
Partial Molar Volume
205(1)
Partial Molar Gibbs Energy
206(2)
The Thermodynamics of Mixing
208(3)
Binary Mixtures of Volatile Liquids
211(6)
Real Solutions
217(4)
The Solvent Component
218(1)
The Solute Component
218(3)
Phase Equilibria of Two-Component Systems
221(7)
Distillation
221(5)
Solid-Liquid Equilibria
226(2)
Colligative Properties
228(21)
Vapor-Pressure Lowering
228(1)
Boiling-Point Elevation
229(3)
Freezing-Point Depression
232(3)
Osmotic Pressure
235(9)
Problems
244(5)
Electrolyte Solutions
249(52)
Electrical Conduction in Solution
249(10)
Some Basic Definitions
249(6)
Degree of Dissociation
255(1)
Ionic Mobility
256(2)
Applications of Conductance Measuremnts
258(1)
A Molecular View of the Solution Process
259(4)
Thermodynamics of Ions in Solution
263(3)
Enthalpy, Entropy, and Gibbs Energy of Formation of Ions in Solution
264(2)
Ionic Activity
266(5)
Debye-Huckel Theory of Electrolytes
271(6)
The Salting-In and Salting-Out Effects
274(3)
Colligative Properties of Electrolyte Solutions
277(5)
The Donnan Effect
279(3)
Biological Membranes
282(19)
Membrane Transport
284(7)
Notes on Electrostatics
291(3)
The Donnan Effect Involving Proteins Bearing Multiple Charges
294(3)
Problems
297(4)
Chemical Equilibrium
301(50)
Chemical Equilibrium in Gaseous Systems
301(8)
Ideal Gases
301(6)
Real Gases
307(2)
Reactions in Solution
309(1)
Heterogeneous Equilibria
310(2)
The Influence of Temperature, Pressure, and Catalysts on the Equilibrium Constant
312(6)
The Effect of Temperature
313(3)
The Effect of Pressure
316(1)
The Effect of a Catalyst
317(1)
Binding of Ligands and Metal Ions to Macromolecules
318(6)
One Binding Site per Macromolecule
318(1)
n Equivalent Binding Sites per Macromolecule
319(3)
Equilibrium Dialysis
322(2)
Bioenergetics
324(27)
The Standard State in Biochemistry
325(2)
ATP---The Currency of Energy
327(3)
Principles of Coupled Reactions
330(1)
Glycolysis
330(6)
Some Limitations of Thermodynamics
336(2)
The Relationship Between Fugacity and pressure
338(3)
The Relationships Between K1 and K2 and the Intrinsic Dissociation Constant K
341(4)
Problems
345(6)
Electrochemistry
351(46)
Electrochemical Cell
351(2)
Single-Electrode Potential
353(3)
Thermodynamics of Electrochemical Cells
356(7)
The Nernst Equation
360(2)
Temperature Dependence of EMF
362(1)
Types of Electrodes
363(1)
Metal Electrodes
363(1)
Gas Electrodes
363(1)
Metal-Insoluble Salt Electrodes
363(1)
The Glass Electrode
364(1)
Ion-Selective Electrodes
364(1)
Types of Electrochemical Cells
364(2)
Concentration Cells
365(1)
Fuel Cells
365(1)
Applications of EMF Measurements
366(2)
Determination of Activity Coefficients
367(1)
Determination of pH
367(1)
Potentiometric Titration of Redox Reactions
368(5)
Biological Oxidation
373(8)
The Chemiosmotic Theory of Oxidative Phosphorylation
378(3)
Membrane Potential
381(16)
The Goldman Equation
384(1)
The Action Potential
384(7)
Problems
391(6)
Acids and Bases
397(48)
Definitions of Acids and Bases
397(1)
Dissociation of Acids and Bases
398(8)
The Ion Product of Water and the pH Scale
403(2)
The Relationship Between the Dissociation Constant of an Acid and Its Conjugate Base
405(1)
Salt Hydrolysis
406(1)
Acid-Base Titrations
407(5)
Acid-Base Indicators
411(1)
Diprotic and Polyprotic Acids
412(4)
Amino Acids
416(4)
Dissociation of Amino Acids
416(3)
The Isoelectric Point (pI)
419(1)
Buffer solutions
420(5)
The Effect of Ionic Strength and Temperature on Buffer Solutions
422(2)
Preparing a Buffer solution With a Specific pH
424(1)
Buffer Capacity
425(1)
Maintaining the pH of Blood
425(20)
A More Exact Treatment of Acid-Base Equilibria
431(8)
Problems
439(6)
Chemical Kinetics
445(66)
Reaction Rate
445(1)
Reaction Order
446(14)
Zero-Order Reactions
447(1)
First-Order Reactions
448(4)
Second-Order Reactions
452(6)
Determination of Reaction Order
458(2)
Molecularity of a Reaction
460(4)
Unimolecular Reactions
461(2)
Bimolecular Reactions
463(1)
Termolecular Reactions
463(1)
More Complex Reactions
464(5)
Reversible Reactions
464(2)
Consecutive Reactions
466(2)
Chain Reactions
468(1)
The Effect of Temperature on Reaction Rates
469(2)
The Arrhenius Equation
470(1)
Potential-Energy Surfaces
471(2)
Theories of Reaction Rates
473(7)
Collision Theory
473(2)
Transition-State Theory
475(1)
Thermodynamic Formulation of Transition-State Theory
476(4)
Isotope Effects in Chemical Reactions
480(3)
Reactions in solution
483(2)
Fast Reactions in Solution
485(6)
The Flow Method
487(1)
The Relaxation Method
488(3)
Oscillating Reactions
491(20)
Derivation of Equation 12.9
494(2)
Derivation of Equation 12.38
496(4)
Problems
500(11)
Enzyme Kinetics
511(50)
General Principles of Catalysis
511(3)
Enzyme Catalysis
512(2)
The Equations of Enzyme Kinetics
514(7)
Michaelis-Menten Kinetics
515(2)
Steady-State Kinetics
517(2)
The Significance of KM and Vmax
519(2)
Chymotrypsin: A Case Study
521(3)
Multisubstrate Systems
524(2)
The Sequential Mechanism
525(1)
The Nonsequential or ``Ping-Pong'' Mechanism
526(1)
Enzyme Inhibition
526(10)
Reversible Inhibition
527(8)
Irreversible Inhibition
535(1)
Allosteric Interactions
536(9)
Oxygen Binding to Myoglobin and Hemoglobin
536(2)
The Hill Equation
538(3)
The Concerted Model
541(2)
The Sequential Model
543(1)
Conformational Changes in Hemoglobin Induced by Oxygen Binding
544(1)
pH Effects on Enzyme Kinetics
545(16)
Kinetic Analysis of the Hydrolysis of p-Nitrophenyl Trimethylacetate Catalyzed by Chymotrypsin
549(2)
Derivations of Equations 13.17 and 13.19
551(2)
Derivation of Equation 13.32
553(3)
Problems
556(5)
Quantum Mechanics and Atomic Structure
561(58)
The Wave Theory of Light
561(3)
Planck's Quantum Theory
564(1)
The Photoelectric Effect
565(2)
Bohr's Theory of the Hydrogen Emission Spectrum
567(7)
de Broglie's Postulate
574(4)
The Heisenberg Uncertainty Principle
578(3)
The Schrodinger Wave Equation
581(2)
Particle in a One-Dimensional Box
583(7)
Electronic Spectra of Polyenes
588(2)
Quantum-Mechanical Tunneling
590(3)
The Schrodinger Wave Equation for the Hydrogen Atom
593(7)
Atomic Orbitals
595(5)
Many-Electron Atoms and the Periodic Table
600(19)
Electron Configurations
601(4)
Variations in Periodic Properties
605(7)
Problems
612(7)
The Chemical Bond
619(50)
Lewis Structures
619(1)
Valence Bond Theory
620(3)
Hybridization of Atomic Orbitals
623(7)
Methane (CH4)
623(3)
Ethylene (C2H4)
626(1)
Acetylene (C2H2)
626(4)
Electronegativity and Dipole Moment
630(3)
Electronegativity
630(1)
Dipole Moment
630(3)
Molecular Orbital Theory
633(3)
Diatomic Molecules
636(5)
Homonuclear Diatomic Molecules of the Second-Period Elements
636(2)
Heteronuclear Diatomic Molecules of the First-and Second-Period Elements
638(3)
Resonance and Electron Delocalization
641(4)
The Peptide Bond
644(1)
Coordination Compounds
645(10)
Crystal Field Theory
647(5)
Molecular Orbital Theory
652(2)
Valence Bond Theory
654(1)
Coordination Compounds in Biological Systems
655(14)
Problems
664(5)
Intermolecular Forces
669(32)
Intermolecular Interactions
669(1)
The Ionic Bond
670(2)
Types of Intermolecular Forces
672(10)
Dipole-Dipole Interaction
672(2)
Ion-Dipole Interaction
674(1)
Ion-Induced Dipole and Dipole-Induced Dipole Interactions
675(3)
Dispersion, or London, Interactions
678(1)
Repulsive and Total Interactions
679(2)
The Role of Dispersion Forces in Sickle-Cell Anemia
681(1)
The Hydrogen Bond
682(7)
The Structure and Properties of Water
689(4)
The Structure of Ice
689(1)
The Structure of Water
689(2)
Some Physiochemical Properties of Water
691(2)
Hydrophobic Interaction
693(8)
Problems
698(3)
Spectroscopy
701(68)
Vocabulary
701(10)
Absorption and Emission
701(1)
Units
701(1)
Regions of the Spectrum
702(1)
Line Width
703(2)
Resolution
705(1)
Intensity
706(2)
Selection Rules
708(1)
Signal-to-Noise Ratio
709(1)
The Beer-Lambert Law
710(1)
Microwave Spectroscopy
711(6)
Infrared Spectroscopy
717(7)
Simultaneous Vibrational and Rotational Transitions
722(2)
Electronic Spectroscopy
724(7)
Organic Molecules
726(3)
Transition Metal Complexes
729(1)
Molecules that Undergo Charge-Transfer Interactions
729(1)
Application of the Beer-Lambert Law
729(2)
Nuclear Magnetic Resonance Spectroscopy
731(10)
The Boltzmann Distribution
734(1)
Chemical Shifts
734(3)
Spin-Spin Coupling
737(1)
NMR and Rate Processes
738(1)
NMR of Nuclei Other Than 1H
739(2)
Electron Spin Resonance Spectroscopy
741(2)
Fluorescence and Phosphorescence
743(3)
Fluorescence
743(1)
Phosphorescence
744(2)
Lasers
746(23)
Properties and Applications of Laser Light
749(4)
Fourier-Transform Spectroscopy
753(10)
Problems
763(6)
Molecular Symmetry and Optical Activity
769(14)
Symmetry of Molecules
769(3)
Proper Rotation Axis
769(1)
Plane of Symmetry
770(1)
Center of Symmetry
770(1)
Improper Rotation Axis
770(1)
Molecular Symmetry and Dipole Moment
770(1)
Molecular Symmetry and Optical Activity
771(1)
Polarized Light and Optical Rotation
772(5)
Optical Rotatory Dispersion and Circular Dichroism
777(6)
Problems
781(2)
Photochemistry and Photobiology
783(48)
Introduction
783(5)
Thermal Versus Photochemical Reactions
783(1)
Primary Versus Secondary Processes
784(1)
Quantum Yields
784(2)
Measurement of Light Intensity
786(1)
Action Spectrum
787(1)
Earth's Atmosphere
788(5)
Composition of the Atmosphere
788(1)
Regions of the Atmosphere
789(3)
Residence Time
792(1)
The Greenhouse Effect
793(3)
Photochemical Smog
796(4)
Formation of Nitrogen Oxides
796(1)
Formation of O3
797(1)
Formation of Hydroxyl Radical
798(1)
Formation of Other Secondary Pollutants
798(1)
Harmful Effects and Prevention of Photochemical Smog
799(1)
The Essential Role of Ozone in the Stratosphere
800(5)
Formation of the Ozone Layer
800(1)
Destruction of Ozone
801(2)
Polar Ozone Holes
803(1)
Ways to Curb Ozone Depletion
804(1)
Photosynthesis
805(8)
The Chloroplast
806(1)
Chlorophyll and Other Pigment Molecules
807(1)
The Reaction Center
808(1)
Photosystems I and II
809(3)
Dark Reactions
812(1)
Vision
813(4)
Structure of Rhodopsin
814(1)
Mechanism of Vision
815(1)
Rotation About the C=C Bond
816(1)
Biological Effects of Radiation
817(14)
Sunlight and Skin Cancer
817(2)
Photomedicin
819(1)
Light-Activated Drugs
820(5)
Problems
825(6)
The Solid State
831(32)
Classification of Crystal Systems
831(3)
The Bragg Equation
834(2)
Structural Determination by X-ray Diffraction
836(9)
The Powder Method
838(1)
Determination of the Crystal Structure of NaCl
839(2)
The Structure Factor
841(3)
Neutron Diffraction
844(1)
Types of Crystals
845(18)
Metallic Crystals
845(6)
Ionic Crystals
851(5)
Covalent Crystals
856(1)
Molecular Crystals
857(1)
Derivation of Equation 20.3
858(3)
Problems
861(2)
The Liquid State
863(32)
Structure of Liquids
863(2)
Viscosity
865(5)
Surface Tension
870(6)
The Capillary-Rise Method
871(3)
Surface Tension in the Lungs
874(2)
Diffusion
876(7)
Fick's Laws of Diffusion
876(7)
Liquid Crystals
883(12)
Thermotropic Liqud Crystals
884(4)
Lyotropic Liquid Crystals
888(1)
Derivation of Equation 21.13
889(2)
Problems
891(4)
Macromolecules
895(46)
Methods for Determining Size, Shape, and Molar Mass of Macromolecules
895(14)
Molar Mass of Macromolecules
895(1)
Sedimentation in the Ultracentrifuge
896(8)
Viscosity
904(1)
Electrophoresis
905(4)
Structure of Synthetic Polymers
909(4)
Configuration and Conformation
910(1)
The Random-Walk Model
910(3)
Structure of Proteins and DNA
913(10)
Proteins
913(7)
DNA
920(3)
Protein Stability
923(18)
Hydrophobic Interaction
923(1)
Denaturation
924(4)
Protein Folding
928(6)
DNA Fingerprinting
934(4)
Problems
938(3)
Statistical Thermodynamics
941(36)
Macrostates and Microstates
941(3)
The Boltzmann Distribution Law
944(4)
The partition Function
948(3)
Molecular Partition Function
951(5)
Translational Partition Function
951(2)
Rotational Partition Function
953(1)
Vibrational Partition Function
954(2)
Electronic Partition Function
956(1)
Thermodynamic Quantities from Partition Functions
956(6)
Internal Energy and Heat Capacity
956(2)
Entropy
958(4)
Chemical Equilibrium
962(6)
Transition-State Theory
968(9)
Justification of Q = qN / N! for Indistinguishable Molecules
973(2)
Problems
975(2)
Appendix A Review of Mathematics and Physics 977(9)
Appendix B Thermodynamic Data 986(5)
Glossary 991(14)
Answers to Even-Numbered Computational Problems 1005(4)
Index 1009

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