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Concise Physical Chemistry

  • ID: 1580356
  • Book
  • 404 Pages
  • John Wiley and Sons Ltd
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An introduction to the fundamentals of physical chemistry for the working scientist

Physical chemistry is the key to understanding how the universe of atomic and molecular interactions impacts on such observable macroscopic phenomena as changes in temperature, pressure, heat, and volume, as well as solid, liquid, or gas phase systems. Fundamental to an understanding of materials science, the principles of physical chemistry are also essential to the work of the scientist in organic chemistry, mathematical biology, or population modeling.

Concise Physical Chemistry offers readers a clear introduction to the conceptual development of physical chemistry, in a well–paced discussion, of twenty–one chapters. It traces the modest beginnings of physical chemistry in gas laws and thermodynamics through its role in solution chemistry and such contemporary fields as electrochemical cells, computational kinetics, and photochemistry. Emphasizing theory over math, detailed coverage includes:

  • Ideal gas laws, real gases, the thermodynamics of simple systems, thermochemistry, entropy and the second law, Gibbs free energy, equilibrium, statistical approaches to thermodynamics, the phase rule, liquids and solids, solution chemistry, conductivity, and electrochemical cells

  • Atomic theory, wave mechanics of simple systems, molecular orbital theory, experimental determination of molecular structure, photochemistry, and the theory of chemical kinetics

A cogent introduction to the theory and basic concepts central to understanding physical chemistry, the book is a complete, one–volume resource for professionals and students alike. Offering computational physical chemical methods as well as worked examples and problems, and illustrating critical points throughout the text, Concise Physical Chemistry is an unmatched resource for mastering the subject in one′s spare time or in one semester.

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Chapter 1 Ideal Gas Laws.

1.1 Empirical Gas Laws.

1.2 The Mole.

1.3 Equations of State.

1.4 Dalton′s Law.

1.5 The Mole Fraction.

1.6 Extensive and Intensive Variables.

1.7 Graham′s Law of Effusion.

1.8 The Maxwell–Boltzmann Distribution.

1.9 A Digression on "Space".

1.10 The Sum–Over–States or Partition Function.

Chapter 2 Real Gases: Empirical Equations.

2.1 The van der Waals Equation.

2.2 The Virial Equation: A Parametric Curve Fit.

2.3 The Compressibility Factor.

2.4 The Critical Temperature.

2.5 Reduced Variables.

2.6 The Law of Corresponding States, Another View.

2.7 Compressibility Factors Calculated From the van der Waals Constants.

2.8 Boyle′s Law Plot for an Ideal Gas (lower curve) and for Nitrogen (upper curve).

2.9 Determining the Molecular Weight of a Nonideal Gas.

Chapter 3 The Thermodynamics of Simple Systems.

3.1 Conservation Laws and Exact Differentials.

3.2 Thermodynamic Cycles.

3.3 Line Integrals in General.

3.3 Pythagorean Approximation to the Short Arc of a Curve.

3.4 Thermodynamic States and Systems.

3.5 State Functions.

3.6 Reversible Processes and Path Independence.

3.7 Heat Capacity.

3.8 Energy and Enthalpy.

3.9 The Joule and Joule–Thomson Experiments.

3.10 The Heat Capacity of an Ideal Gas.

3.11 Adiabatic Work.

Chapter 4 Thermochemistry.

4.1 Calorimetry.

4.2 Energies and Enthalpies of Formation.

4.3 Standard States.

4.4 Molecular Enthalpies of Formation.

4.5 Enthalpies of Reaction.

4.6 Group Additivity.

4.7 from Classical Mechanics.

4.8 The Schroedinger Equation.

4.9 Variation of with T.

4.10 Differential Scanning Calorimetry.

Chapter 5 Entropy and the Second Law.

5.1 Entropy.

5.2 Entropy Changes.

5.3 Spontaneous Processes.

5.4 The Third Law.

Chapter 6 The Gibbs Free Energy.

6.1 Combining Enthalpy and Entropy.

6.2 Free Energies of Formation.

6.3 Some Fundamental Thermodynamic Identities.

6.4 The Free Energy of Reaction.

6.5 Pressure Dependence of the Chemical Potential.

6.6 The Temperature dependence of the Free Energy.

Chapter 7 Equilibrium.

7.1 The Equilibrium Constant.

7.2 General Formulation.

7.3 The Extent of Reaction.

7.4 Fugacity and Activity.

7.5 Variation of the Equilibrium Constant with Temperature.

7.6 Computational Thermochemistry.

7.7 Chemical Potential: Nonideal Systems .

7.8 Free Energy and Equilibria in Biochemical Systems.

Chapter 8 A Statistical Approach to Thermodynamics.

8.1 Equilibrium.

8.2 Degeneracy and Equilibrium.

8.3 Gibbs Free Energy and the Partition Function.

8.4 Entropy and Probability.

8.5 The Thermodynamic Functions .

8.6 The Partition Function of a Simple System.

8.7 The Partition Function for Different modes of Motion.

8.8 The Equilibrium Constant: A Statistical Approach.

8.9 Computational Statistical Thermodynamics.

Chapter 9 The Phase Rule.

9.1 Components, Phases, and Degrees of Freedom.

9.2 Coexistance Curves.

9.3 The Clausius–Clapeyron Equation.

9.4 Partial Molar Volume.

9.5 The Gibbs Phase Rule.

9.6 Two Component Phase Diagrams.

9.7 Compound Phase Diagrams.

9.8 Ternary Phase Diagrams.

Chapter 10 Chemical Kinetics.

10.1 First Order Kinetic Rate Laws.

10.2 Second Order Reactions.

10.3 Other Reaction Orders.

10.4 Experimental Determination of the Rate Equation.

10.5 Reaction Mechanisms.

10.6 The Influence of Temperature on Rate.

10.7 Collision Theory.

10.8 Computational Kinetics.

Chapter 11 Liquids and Solids.

11.1 Surface Tension.

11.2 Heat Capacity of Liquids and Solids.

11.3 Viscosity of Liquids.

11.4 Crystals.

11.5 Bravais Lattices.

11.6 Computational Geometries.

11.7 Lattice Energies (Enthalpies).

Chapter 12 Solution Chemistry.

12.1 The Ideal Solution.

12.2 Raoult s Law.

12.3 A Digression on Concentration Units Real Solutions..

12.4 Real Solutions.

12.5 Henry s Law.

12.6 Vapor Pressure.

12.7 Boiling Point Elevation.

12.8 Osmotic Presure.

12.9 Colligative Properties.

Chapter 13 Conductivity.

13.1 Electrical Potential.

13.2 Resistivity, Conductivity and Conductance.

13.3 Molar Conductivity.

13.4 Partial Ionization: Weak Electrolytes.

13.5 Ion Mobilities.

13.6 Faraday s Laws.

13.7 Mobility and Conductance.

13.8 The Hittorf Cell.

13.9 Ion Activities.

Chapter 14 Electrochemical Cells.

14.1 The Daniell Cell.

14.2 Half Cells.

14.3 Half Cell Potentials.

14.4 Cell Diagrams.

14.5 Electrical Work.

14.6 The Nernst Equation.

14.7 Concentration Cells.

14.8 Finding .

14.9 Solubility and Stability Products.

14.10 Mean Ionic Activity Coefficients.

14.11 The Calomel Electrode.

14.12 The Glass electrode.

Chapter 15 Early Atomic Theory: A Summary.

15.1 The Hydrogen Spectrum.

15.2 Early Quantum Theory.

15.3 Molecular Quantum Chemistry.

15.4 The Hartree Independent Electron Method.

Chapter 16 Wave Mechanics of Simple Systems.

16.1 Wave Motion.

16.2 Wave Equations.

16.3 The Schroedinger Equation.

16.4 Quantum Mechanical Systems.

16.5 The Particle in a One Dimensional Box.

16.6 The Particle in a Cubic Box.

16.7 The Hydrogen Atom.

16.8 Breaking Degeneracy.

16.9 Orthogonality and Overlap.

16.10 Many Electron Atomic Systems.

Chapter 17 The Variational Method: Atoms.

17.1 More on The Variational Method.

17.2 The Secular Determinant.

17.3 A Variational Treatment for the Hydrogen Atom: The Energy Spectrum .

17.4 Helium.

17.5 Spin.

17.6 Bosons and Fermions.

17.7 Slater Determinants.

17.8 The Aufbau Principle.

17.9 The SCF Energies of First Row Atoms and Ions.

17.10 Slater–Type Orbitals STO.

17.11 Spin–Orbit Coupling.

Chapter 18 Experimental Determination of Molecular Structure.

18.1 The Harmonic Oscillator.

18.2 The Hooke s Law Potential Well.

18.3 Diatomic Molecules.

18.4 The Quantum Rigid Rotor.

18.5 Microwave Spectroscopy: Bond strength and Bond Length.

18.6 Electronic Spectra.

18.7 Dipole Moments.

18.8 Nuclear Magnetic Resonance (NMR).

18.9 Electron Spin Resonance.

Chapter 19 Part A Classical Molecular Modeling.

19.1 Enthalpy: Additive Methods.

19.2 Bond Enthalpies.

19.3 Structure.

19.4 Geometry and Enthalpy: Molecular Mechanics .

19.5 Molecular Modeling.

19.6 The gui.

19.7 Finding Thermodynamic Properties.

19.8 The Outside World.

19.9 Transition States.

Chapter 20. Quantum Molecular Modeling.

20.1 The Molecular Variational Method.

20.2 The Hydrogen Molecule Ion.

20.3 Higher Molecular Orbital Calculations .

20.4 Semiempirical Methods.

20.5 Ab Initio Methods.

20.6 The Gaussian Basis Set.

20.7 Stored Parameters.

20.8 Molecular Orbitals.

20.9 Methane.

20.10 Split Valence Basis Sets.

20.11 Polarized Basis Functions.

20.12 Heteroatoms: Oxygen.

20.13 Finding of Methanol.

20.14 Further Basis Set Improvements.

20.15 Post Hartree–Fock Calculations.

20.16 Perturbation.

20.17 Combined or Scripted Methods.

20.18 Density Functional Theory (DFT).

Chapter 21 Photochemistry and the Theory of Chemical Kinetics.

21.1 Einstein s Law.

21.2 Quantum Yields.

21.3 Bond Dissociation Energies (BDE).

21.4 Isodesmic Reactions.

21.5 The Eyring Theory of Reaction Rates.

21.6 The Potential Energy Surface.

21.7 Steady State Pseudo Equilibrium.

21.8 Entropies of Activation.

21.9 The Structure of the Activated Complex.

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Donald W. Rogers
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