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Physical Chemistry for the Chemical and Biological Sciences

Raymond Chang Williams College

Hailed by advance reviewers as "a kinder, gentler P. Chem. text," this book meets the needs of a full-year course in physical chemistry. It is an ideal choice for classes geared toward pre-medical and life sciences students.

Print Book, ISBN 978-1-891389-06-1, US $150
eBook, eISBN 978-1-891389-94-8, US $90
Copyright 2000
1018 pages, Clothbound

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Summary

Hailed by advance reviewers as “a kinder, gentler P. Chem. text,” this book meets the needs of a full-year course in physical chemistry. It is an ideal choice for classes geared toward pre-medical and life sciences students. Or, as stated in a May 2001 review in Journal of Chemical Education, “this text meets these students where they are and opens the door to physical chemistry from a perspective they can appreciate.”  Physical Chemistry for the Chemical and Biological Sciences offers a wealth of applications to chemical and biological problems, numerous chapter-ending exercises, and an accompanying solutions manual. Well known for his clear writing and careful pedagogical approach, Raymond Chang has developed yet another masterpiece in chemical education.

Key Features:

  • a student-oriented, highly readable text
  • traditional and flexible organization
  • a functional and pleasing two-color format
  • many worked examples in text
  • @1000 chapter-ending problems
  • an overview of key equations in each chapter
  • a glossary of key terms
  • answers provided to even-numbered computational problems

Translated into Italian, Japanese, Korean, Spanish & Portugese

Ancillaries

  • Art for adopting professors is available.

Resources

List of Adoptions
Preface

Table of Contents

Chapter 1 Introduction

1.1 Nature of Physical Chemistry

1.2 Units

  • Force
  • Pressure
  • Energy

1.3 Atomic Mass, Molecular Mass, and the Chemical Mole

Chapter 2 The Gas Laws

2.1 Some Basic Definitions

2.2 An Operational Definition of Temperature

2.3 Boyle’s Law

2.4 Charles’ and Gay-Lussac’s Law

2.5 Avogadro’s Law

2.6 The Ideal Gas Equation

2.7 Dalton’s Law of Partial Pressures

2.8 Real Gases

  • The van der Waals Equation
  • The Virial Equation of State

2.9 Condensation of Gases and the Critical State

Chapter 3 Kinetic Theory of Gases

3.1 The Model

3.2 Pressure of a Gas

3.3 Kinetic Energy and Temperature

3.4 The Maxwell Distribution Laws

3.5 Molecular Collisions and the Mean Free Path

3.6 Gas Viscosity

3.7 Graham’s Laws of Diffusion and Effusion

3.8 Equipartition of Energy

Appendix 3.1 Derivation of Equation (3.24)

Appendix 3.2 Total and Partial Differentiation

Chapter 4 The First Law of Thermodynamics

4.1 Work and Heat

  • Work
  • Heat

4.2 The First Law of Thermodynamics

4.3 Enthalpy

4.4 A Closer Look at Heat Capacities

4.5 Gas Expansion

  • Isothermal Expansion
  • Adiabatic Expansion

4.6 Thermochemistry

  • Standard Enthalpy of Formation
  • Dependence of Enthalpy of Reaction on Temperature

4.7 Bond Energies and Bond Enthalpies

  • Bond Enthalpy and Bond Dissociation Enthalpy

Appendix 4.1 Exact and Inexact Differentials

Chapter 5 The Second Law of Thermodynamics

5.1 Spontaneous Processes

5.2 Entropy

  • Statistical Definition of Entropy
  • Thermodynamic Definition of Entropy

5.3 The Carnot Heat Engine

  • Thermodynamic Efficiency
  • The Entropy Function
  • Refrigerators, Air Conditioners, and Heat Pumps

5.4 The Second Law of Thermodynamics

5.5 Entropy Changes

  • Entropy Change due to Mixing of Ideal Gases
  • Entropy Change due to Phase Transitions
  • Entropy Change due to Heating

5.6 The Third Law of Thermodynamics

  • Third-Law or Absolute Entropies
  • Entropy of Chemical Reactions

5.7 Residual Entropy

Appendix 5.1 Statements of the Second Law of Thermodynamics

Chapter 6 Gibbs and Helmholtz Energies and Their Applications

6.1 Gibbs and Helmholtz Energies

6.2 Meaning of Helmholtz and Gibbs Energies

  • Helmholtz Energy
  • Gibbs Energy

6.3 Standard Molar Gibbs Energy of Formation (ÆfG°)

6.4 Dependence of Gibbs Energy on Temperature and Pressure

  • Dependence of G on Temperature
  • Dependence of G on Pressure

6.5 Gibbs Energy and Phase Equilibria

  • The Clapeyron and Clausius-Clapeyron Equations
  • Phase Diagrams
  • The Phase Rule

6.6 Thermodynamics of Rubber Elasticity

Appendix 6.1 Some Thermodynamic Relationships

Appendix 6.2 Derivation of the Phase Rule

Chapter 7 Nonelectrolyte Solutions

7.1 Concentration Units

  • Percent by Weight
  • Mole fraction (x)
  • Molarity (M)
  • Molality (m)

7.2 Partial Molar Quantities

  • Partial Molar Volume
  • Partial Molar Gibbs Energy

7.3 The Thermodynamics of Mixing

7.4 Binary Mixtures of Volatile Liquids

7.5 Real Solutions

  • The Solvent Component
  • The Solute Component

7.6 Phase Equilibria of Two-Component Systems

  • Distillation
  • Solid-Liquid Equilibria

7.7 Colligative Properties

  • Vapor-Pressure Lowering
  • Boiling-Point Elevation
  • Freezing-Point Depression
  • Osmotic Pressure

Chapter 8 Electrolyte Solutions

8.1 Electrical Conduction in Solution

  • Some Basic Definitions
  • Degree of Dissociation
  • Ionic Mobility
  • Applications of Conductance Measurements

8.2 A Molecular View of the Solution Process

8.3 Thermodynamics of Ions in Solution

  • Enthalpy, Entropy, and Gibbs Energy of Formation of Ions in Solution

8.4 Ionic Activity

8.5 Debye-Huckel Theory of Electrolytes

  • The Salting-In and Salting-Out Effects

8.6 Colligative Properties of Electrolyte Solutions

  • The Donnan Effect

8.7 Biological Membranes

  • Membrane Transport

Appendix 8.1 Notes on Electrostatics

Appendix 8.2 The Donnan Effect Involving Proteins Bearing Multiple Charges

Chapter 9 Chemical Equilibrium

9.1 Chemical Equilibrium in Gaseous Systems

  • Ideal Gases
  • Real Gases

9.2 Reactions in Solution

9.3 Heterogeneous Equilibria

9.4 The Influence of Temperature, Pressure, and Catalysts on the Equilibrium Constant

  • The Effect of Temperature
  • The Effect of Pressure
  • The Effect of a Catalyst

9.5 Binding of Ligands and Metal Ions to Macromolecules

  • One Binding Site per Macromolecule
  • n Equivalent Binding Sites per Macromolecule
  • Equilibrium Dialysis

9.6 Bioenergetics

  • The Standard State in Biochemistry
  • ATP – The Currency of Energy
  • Principles of Coupled Reactions
  • Glycolysis
  • Some Limitations of Thermodynamics

Appendix 9.1 The Relationship Between Fugacity and Pressure

Appendix 9.2 The Relationships Between K1 and K2 and the Intrinsic Dissociation Constant K

Chapter 10 Electrochemistry

10.1 Electrochemical Cells

10.2 Single-Electrode Potential

10.3 Thermodynamics of Electrochemical Cells

  • The Nernst Equation
  • Temperature Dependence of EMF

10.4 Types of Electrodes

  • Metal Electrodes
  • Gas Electrodes
  • Metal-Insoluble Salt Electrodes
  • Gas Electrodes
  • The Glass Electrode
  • Ion-Selective Electrodes

10.5 Types of Electrochemical Cells

  • Concentration Cells
  • Fuel Cells

10.6 Applications of EMF Measurements

  • Determination of Activity Coefficients
  • Determination of pH

10.7 Potentiometric Titration of Redox Reactions

10.8 Biological Oxidation

  • The Chemiosmotic Theory of Oxidative Phosphorylation

10.9 Membrane Potential

  • The Goldman Equation
  • The Action Potential

Chapter 11 Acids and Bases

11.1 Definitions of Acids and Bases

11.2 Dissociation of Acids and Bases

  • The Ion Product of Water and the pH scale
  • The Relationship Between the Dissociation Constant of An Acid and Its Conjugate Base

11.3 Salt Hydrolysis

11.4 Acid-Base Titrations

  • Acid-Base Indicators

11.5 Diprotic and Polyprotic Acids

11.6 Amino Acids

  • Dissociation of Amino Acids
  • Isoelectric Point

11.7 Buffer Solutions

  • Effect of Ionic Strength and Temperature on Buffer Solutions
  • Preparing a Buffer Solution With a Specific pH
  • Buffer Capacity

11.8 Maintaining the pH of Blood

Appendix 11.1 A More Exact Treatment of Acid-Base Equilibria

Chapter 12 Chemical Kinetics

12.1 Reaction Rate

12.2 Reaction Order

  • Zero-Order Reactions
  • First-Order Reactions
  • Second-Order Reactions
  • Determination of Reaction Order

12.3 Molecularity of a Reaction

  • Unimolecular Reactions
  • Bimolecular Reactions
  • Termolecular Reactions

12.4 More Complex Reactions

  • Reversible Reactions
  • Consecutive Reactions
  • Chain Reactions

12.5 Effect of Temperature on Reaction Rates

  • The Arrhenius Equation

12.6 Potential-Energy Surfaces

12.7 Theories of Reaction Rates

  • Collision Theory
  • Transition-State Theory
  • Thermodynamic Formulation of the Transition-State Theory

12.8 Isotope Effects in Chemical Reactions

12.9 Reactions in Solution

12.10 Fast Reactions in Solution

  • The Flow Method
  • The Relaxation Method

12.10 Oscillating Reactions

Appendix 12.1 Derivation of Equation (12.9)

Appendix 12.2 Derivation of Equation (12.38)

Chapter 13 Enzyme Kinetics

13.1 General Principles of Catalysis

  • Enzyme Catalysis

13.2 The Equations of Enzyme Kinetics

  • Michaelis-Menten Kinetics
  • Steady-State Kinetics
  • The Significance of KM and Vmax

13.3 Chymotrypsin: A Case Study

13.4 Multisubstrate Systems

  • The Sequential Mechanism
  • The Nonsequential or “Ping-Pong” Mechanism

13.5 Enzyme Inhibition

  • Reversible Inhibition
  • Irreversible Inhibitions

13.6 Allosteric Interactions

  • Oxygen Binding to Myoglobin and Hemoglobin
  • The Hill Equation
  • The Concerted Model
  • The Sequential Model
  • Conformational Changes in Hemoglobin Induced by Oxygen Binding

13.7 pH Effects on Enzyme Kinetics

Appendix 13.1 Kinetic Analysis of the Hydrolysis of p-Nitrophenyl Trimethylacetate Catalyzed by Chymotrypsin

Appendix 13.2 Derivations of Equations (13.17) and (13.19)

Appendix 13.3 Derivation of Equation (13.32)

Chapter 14 Quantum Mechanics

14.1 The Wave Theory of Light

14.2 Planck’s Quantum Theory

14.3 The Photoelectric Effect

14.4 Bohr’s Theory of Hydrogen Emission Spectra

14.5 de Broglie’s Postulate

14.6 The Heisenberg Uncertainty Principle

14.7 The Schrodinger Wave Equation

14.8 Particle in a One Dimensional Box

  • Electronic Spectra of Polyenes

14.9 Quantum-Mechanical Tunneling

14.10 The Schrodinger Wave Equation for the Hydrogen Atom

  • Atomic Orbitals

14.11 Many-Electron Atoms and the Periodic Table

  • Electron Configurations
  • Variations in Periodic Properties

Chapter 15 The Chemical Bond

15.1 Lewis Structures

15.2 Valence Bond Theory

15.3 Hybridization of Atomic Orbitals

  • Methane (CH4)
  • Ethylene (C2H4)
  • Acetylene (C2H2)

15.4 Electronegativity and Dipole Moments

  • Electronegativity
  • Dipole Moment

15.5 Molecular Orbital Theory

15.6 Diatomic Molecules

  • Homonuclear Diatomic Molecules of the Second-Period Elements
  • Heteronuclear Diatomic Molecules of the First and Second-Period Elements

15.7 Resonance and Electron Delocalization

  • The Peptide Bond

15.8 Coordination Compounds

  • Crystal Field Theory
  • Molecular Orbital Theory
  • Valence Bond Theory

15.9 Coordination Compounds in Biological Systems

Chapter 16 Intermolecular Forces

16.1 Intermolecular Interactions

16.2 The Ionic Bond

16.3 Types of Intermolecular Forces

  • Dipole-Dipole Interaction
  • Ion-Dipole Interaction
  • Ion-Induced Dipole and Dipole-Induced Dipole Interactions
  • Dispersion or London Interactions
  • Repulsive and Total Interactions
  • The Role of Dispersion Forces in Sickle-Cell Anemia

16.4 The Hydrogen Bond

16.5 Structure and Properties of Water

  • Structure of Ice
  • Structure of Water
  • Some Physiochemical Properties of Water

16.4 The Hydrophobic Interaction

Chapter 17 Spectroscopy

17.1 Vocabulary

  • Absorption and Emission
  • Units
  • Regions of the Spectrum
  • Line Width
  • Resolution
  • Intensity
  • Selection Rules
  • Signal-to-Noise Ratio
  • The Beer-Lambert Law

17.2 Microwave Spectroscopy

17.3 Infrared Spectroscopy

  • Simultaneous Vibrational and Rotational Transitions

17.4 Electronic Spectroscopy

  • Organic Molecules
  • Transition Metal Complexes
  • Molecules that Undergo Charge-Transfer Interactions
  • Application of the Beer-Lambert Law

17.5 Nuclear Magnetic Resonance Spectroscopy

  • The Boltzmann Distribution
  • Chemical Shifts
  • Spin-Spin Coupling
  • NMR and Rate Processes
  • NMR of Nuclei Other Than 1H

17.6 Electron Spin Resonance Spectroscopy

17.7 Fluorescence and Phosphorescence

  • Fluorescence
  • Phosphorescence

17.8 Lasers

  • Properties and Applications of Laser Light

Appendix 17.1 Fourier-Transform Spectroscopy

Chapter 18 Molecular Symmetry and Optical Activity

18.1 Symmetry of Molecules

  • Proper Rotation Axis
  • Plane of Symmetry
  • Center of Symmetry
  • Improper Rotation Axis
  • Molecular Symmetry and Dipole Moment
  • Molecular Symmetry and Optical Activity

18.2 Polarized Light and Optical Rotation

18.3 Optical Rotatory Dispersion and Circular Dichroism

Chapter 19 Photochemistry and Photobiology

19.1 Introduction

  • Thermal versus Photochemical Reactions
  • Primary versus Secondary Processes
  • Quantum Yields
  • Measurement of Light Intensity
  • Action Spectrum

19.2 Earth’s Atmosphere

  • Composition of the Atmosphere
  • Regions of the Atmosphere
  • Residence Time

19.3 The Greenhouse Effect

19.4 Photochemical Smog

  • Formation of Nitrogen Oxides
  • Formation of O• Formation of Hydroxyl Radical
  • Formation of Other Secondary Pollutants
  • Harmful Effects and Prevention of Photochemical Smog

19.5 The Essential Role of Ozone in the Stratosphere

  • Formation of the Ozone Layer
  • Destruction of Ozone
  • Polar Ozone Holes
  • Ways to Curb Ozone Depletion

19.6 Photosynthesis

  • The Chloroplast
  • Chlorophyll and Other Pigment Molecules
  • The Reaction Center
  • Photosystems I and II
  • Dark Reactions

19.7 Vision

  • Structure of Rhodopsin
  • Mechanism of Vision
  • Rotation About the C=C Bond

19.8 Biological Effects of Radiation

  • Sunlight and Skin Cancer
  • Light-Activated Drugs

Chapter 20 The Solid State

20.1 Classification of Crystal Systems

20.2 The Bragg Equation

20.3 Structural Determination by X-ray Diffraction

  • The Powder Method
  • Determination of the Crystal Structure of NaCl
  • The Structure Factor
  • Neutron Diffraction

20.4 Types of Crystals

  • Metallic Crystals
  • Ionic Crystals
  • Covalent Crystals
  • Molecular Crystals

Appendix 20.1 Derivation of Equation (20.3)

Chapter 21 The Liquid State

21.1 Structure of Liquids

21.2 Viscosity

21.3 Surface Tension

  • The Capillary-Rise Method
  • Surface Tension in the Lungs

21.4 Diffusion

  • Fick’s Laws of Diffusion

21.5 Liquid Crystals

  • Thermotropic Liquid Crystals
  • Lyotropic Liquid Crystals

Appendix 21.1 Derivation of Equation (21.13)

Chapter 22 Macromolecules

22.1 Methods for Determining the Size, Shape, and Molar Mass of Macromolecules

  • Molar Mass of Macromolecules
  • Sedimentation in the Ultracentrifuge
  • Viscosity
  • Electrophoresis

22.2 Structure of Synthetic Polymers

  • Configuration and Conformation
  • The Random-Walk Model

22.3 Structure of Proteins and DNA

  • Proteins
  • DNA

22.4 Protein Stability

  • The Hydrophobic Interaction
  • Denaturation
  • Protein Folding

Appendix 22.1 DNA Fingerprinting

Chapter 23 Statistical Thermodynamics

23.1 Macrostates and Microstates

23.2 The Boltzmann Distribution Law

23.3 The Partition Function

23.4 Molecular Partition Function

  • Translational Partition Function
  • Rotational Partition Function
  • Vibrational Partition Function
  • Electronic Partition Function

23.5 Thermodynamic Quantities from Partition Functions

  • Internal Energy and Heat Capacity
  • Entropy

23.6 Chemical Equilibrium

23.7 Transition-State Theory

Appendix 23.1 Justification of Q = qN/N! for Indistinguishable Particles

Appendices

A. Review of Mathematics and Physics

B. Thermodynamic Data

Glossary

Answers to Even-Numbered Numerical Problems

Index

Reviews

“I have found Ray Chang’s P Chem book to be the ideal textbook for students from the life sciences. Whereas so many other textbooks seem to be written for the instructor, this text works well with students who have traditionally struggled with this course.”
-George Bodner, Purdue University

“I adopted the P Chem text by Raymond Chang here at McGill two years ago, for a course populated with ~180 biochemistry and biology students, many of them ‘pre-med.’ I had formerly used a well-known text by a different author, but I (and the students) found it a little short on good explanations, and there were many errors in the end-of-chapter problems and answers. I am very pleased with how the Chang text approaches thermodynamics, especially applications, such as in the chapter on macromolecules. Similarly, I very much appreciate the biological emphasis in this text, and especially the relevance of the problems. Overall, I consider this to be an excellent text.”
-Christopher J. Barrett, McGill University

“This book offers an alternative approach to physical chemistry that is particularly well suited for those who want to pursue a course of study more focused on the biological sciences.”
-Journal of Chemical Education

“A distinct and excellent publication worth recommending to biological chemists…I have learnt something new about biology, [the book] is very refreshing in its aims and clarity.”
-The Times Higher

Raymond Chang

Raymond Chang Williams College

Raymond Chang was born in Hong Kong and grew up in Shanghai and Hong Kong, China. He received his B.Sc. degree in chemistry from London University, England and his Ph.D. in physical chemistry from Yale University. After doing postdoctoral research at Washington University and teaching for a year at Hunter College of the City University of New York, he joined the chemistry department at Williams College. Chang has served on the American Chemical Society Examination Committee and the Graduate Record Examination (GRE) Committee. He has also served as editor of The Chemical Educator and has authored books on general chemistry and spectroscopy.

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