Physical Chemistry for the Chemical and Biological Sciences

by Chang, Raymond

• ISBN13: 9781891389061
• ISBN10: 1891389068
• Edition: 3rd
• Format: Hardcover
• Copyright: 2000-02-01
• Publisher: Univ Science Books

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