**Physical Chemistry 3rd Edition by Gilbert W Castellan**

## Contents of Physical Chemistry 3rd Edition Gilbert W Castellan

- Some Fundamental Chemical Concepts
- Introduction
- The kinds of matter
- The kinds of substances
- Atomic and molar masses
- Symbols Formulas
- The mole
- Chemical equations
- The International System of Units, SI
- Empirical Properties of Gases
- Boyle’s law; Charles’s law
- Molar mass of a gas Avogadro’s law; The ideal gas law
- The equation of state; Extensive and intensive properties
- Properties of the ideal gas
- Determination of molar masses of gases and volatile substances
- Mixtures; Composition variables
- Equations of state for a gas mixture; Dalton’s law
- The partial-pressure concept
- The barometric distribution law
- Real Gases
- Deviations from ideal behavior
- Modifying the ideal gas equation; The van der Waals equation
- Implications of the van der Waals equation
- The isotherms of a real gas
- Continuity of states
- The isotherms of the van der Waals equation
- The critical state
- The law of corresponding states
- Other equations of state
- The Structure of Gases
- Kinetic theory of gases; Fundamental assumptions
- Calculation of the pressure of a gas
- Dalton’s law of partial pressures
- Distributions and distribution functions
- The Maxwell distribution
- Mathematical interlude
- Evaluation of A and f
- Calculation of average values using the Maxwell distribution
- The Maxwell distribution as an energy distribution
- Average values of individual components; Equipartition of
- energy
- Equipartition of energy and quantization
- Calculation of vibrational heat capacity
- The Maxwell-Boltzmann distribution law
- Experimental verification of the Maxwell distribution law
- Some Properties of liquids and Solids
- Condensed phases
- Coefficients of thermal expansion and compressibility
- Heats of fusion; Vaporization; Sublimation
- Vapor pressure
- Other properties of liquids
- Review of structural differences between solids, liquids, and gases
- The laws of Thermodynamics: Generalities and the
- Zeroth law
- Kinds of energy and the first law of thermodynamics
- Restrictions on the conversion of energy from one form to another
- The second law of thermodynamics
- The Zeroth law of thermodynamics
- Thermometry
- Energy and the First Law of Thermodynamics;
- Thermochemistry
- Thermodynamic terms: Definitions
- Work and heat
- Expansion work
- Work of compression
- Maximum and minimum quantities of work
- Reversible and irreversible transformations
- Energy and the first law of thermodynamics
- Properties of the energy
- Mathematical interlude; Exact and inexact differentials
- Changes in energy in relation to changes in properties of the system
- Changes in state at constant volume
- Measurement of (aUlaVh; Joule’s experiment
- Changes in state at constant pressure
- The relation between Cp and Cv
- The measurement of (aHlaph; Joule-Thomson experiment
- Adiabatic changes in state
- A note about problem working
- Application of the first law of thermodynamics to chemical reactions The heat of reaction
- The formation reaction
- Conventional values of molar enthalpies
- The determination of heats of formation
- Sequences of reactions; Hess’s law
- Heats of solution and dilution
- Heats of reaction at constant volume
- Dependence of the heat of reaction on temperature
- Bond enthalpies
- Calorimetric measurements
- Introduction to the Second law of Thermodynamics
- General remarks
- The Carnot cycle
- The second law of thermodynamics
- Characteristics of a reversible cycle
- A perpetual-motion machine of the second kind
- The efficiency of heat engines
- Another impossible engine
- The thermodynamic temperature scale
- Retrospection
- Carnot cycle with an ideal gas
- The Carnot refrigerator
- The heat pump
- Definition of entropy
- General proof
- The Clausius inequality
- Properties of the Entropy and the Third law of
- Thermodynamics
- The properties of entropy
- Conditions of thermal and mechanical stability of a system
- Entropy changes in isothermal transformations
- Mathematical interlude More properties of exact differentials
- The cyclic rule
- Entropy changes in relation to changes in the state variables
- Entropy as a function of temperature and volume
- Entropy as a function of temperature and pressure
- The temperature dependence of the entropy
- Entropy changes in the ideal gas
- The third law of thermodynamics
- Entropy changes in chemical reactions
- Entropy and probability
- General form for omega
- The energy distribution
- Entropy of mixing and exceptions to the third law of thermodynamics
- Spontaneity and Equilibrium
- The general conditions for equilibrium and for spontaneity
- Conditions for equilibrium and spontaneity under constraints
- Recollection
- Driving forces for natural changes
- The fundamental equations of thermodynamics
- The thermodynamic equation of state
- The properties of A
- The properties of G
- The Gibbs energy of real gases
- Temperature dependence of the Gibbs energy
- Systems of Variable Composition; Chemical Equilibrium
- The fundamental equation
- The Gibbs energy of a mixture
- The chemical potential of a pure ideal gas
- Chemical potential of an ideal gas in a mixture of ideal gases
- Gibbs energy and entropy of mixing
- Chemical equilibrium in a mixture
- The general behavior of Gas a function of
- Chemical equilibrium in a mixture of ideal gases
- Chemical equilibrium in a mixture of real gases
- The equilibrium constants, Kx and Kc
- Standard Gibbs energies of formation
- The temperature dependence of the equilibrium constant
- Equilibria between ideal gases and pure condensed phases
- The LeChatelier principle
- Equilibrium constants from cal fimetric measurements The
- third law in its historical context
- Chemical reactions and the entropy of the universe
- Coupled reactions
- Dependence of the other thermodynamic functions on composition
- Partial molar quantities and additivity rules
- The Gibbs-Duhem equation
- Partial molar quantities in mixtures of ideal gases
- Differential heat of solution
- Phase Equilibrium in Simple Systems; The Phase Rule
- The equilibrium condition
- Stability of the phases of a pure substance
- Pressure dependence of f L versus T curves
- The Clapeyron equation
- The phase diagram
- The integration of the Clapeyron equation
- Effect of pressure on the vapor pressure
- The phase rule
- The problem of components
- I The Ideal Solution and Colligative Properties
- Kinds of solutions
- Definition of the ideal solution
- Analytical form of the chemical potential in ideal liquid
- solutions
- Chemical potential of the solute in a binary ideal solution;
- Application of the Gibbs-Duhem equation
- Colligative properties
- The freezing-point depression
- Solubility
- Elevation of the boiling point
- Osmotic pressure
- More Than One Volatile Component; The Ideal Dilute
- Solution
- General characteristics of the ideal solution
- The chemical potential in ideal solutions
- Binary solutions
- The lever rule
- Changes in state as the pressure is reduced isothermally
- Temperature-composition diagrams
- Changes in state with increase in temperature
- Fractional distillation
- Azeotropes
- The ideal dilute solution
- The chemical potentials in the ideal dilute solution
- Henry’s law and the solubility of gases
- Distribution of a solute between two solvents
- Chemical equilibrium in the ideal solution
- Equilibria between Condensed Phases
- Liquid-liquid equilibria
- Distillation of partially miscible and immiscible liquids
- Solid-liquid equilibria; The simple eutectic diagram
- Freezing-point diagram with compound formation
- Compounds having incongruent melting points
- Miscibility in the solid state
- Freezing-point elevation
- Partial miscibility in the solid state
- Gas-solid equilibria; Vapor pressure of salt hydrates
- Systems of three components
- Solubility of salts; Common-ion effect
- Double-salt formation
- The method of “wet residues”
- Equilibria in Nonideal Systems
- The concept of activity
- The rational system of activities
- Colligative properties
- The practical system
- Activities and reaction equilibrium
- Activities in electrolytic solutions
- The Debye-Huckel theory of the structure of dilute ionic solutions
- Equilibria in ionic solutions
- Equilibria in Electrochemical Cells
- Introduction
- Definitions
- The chemical potential of charged species
- Cell diagrams
- The Daniell cell
- Gibbs energy and the cell potential
- The N ernst equation
- The hydrogen electrode
- Electrode potentials
- Temperature dependence of the cell potential
- Kinds of electrodes
- Equilibrium constants from standard half-cell potentials
- Significance of the half-cell potential
- The measurement of cell potentials
- Reversibility
- The determination of a half-cell
- The determination of activities and activity coefficients from cell potentials
- Concentration cells
- Technical electrochemical processes
- Electrochemical cells as power sources
- Two practical power sources
- Surface Phenomena
- Surface energy and surface tension
- Magnitude of surface tension
- Measurement of surface tension
- Thermodynamic formulation
- Capillary rise and capillary depression
- Properties of very small particles
- Bubbles; Sessile drops
- Liquid-liquid and solid-liquid interfaces
- Surface tension and adsorption
- Surface films
- Adsorption on solids
- Physical and chemisorption
- The Brunauer, Emmet, and Teller (BET) isotherm
- Electrical phenomena at interfaces; The double layer
- Electrokinetic effects
- Colloids
- Colloidal electrolytes; Soaps and detergents
- Emulsions and foams
- The Structure of Matter
- Introduction
- Nineteenth century
- The earthquake
- Discovery of the electron
- Positive rays and isotopes
- Radioactivity
- Alpha-ray scattering
- Radiation and matter
- The photoelectric effect
- Bohr’s model of the atom
- Particles and Louis de Broglie
- The classical wave equation
- The Schrodinger equation
- The Interpretation of I/J
- Retrospection
- Introduction to Quantum Mechanical Principles
- Introduction
- Postulates of the quantum mechanics
- Mathematical interlude: Operator algebra
- The Schrodinger equation
- The eigenvalue spectrum
- Expansion theorem
- Concluding remarks on the general equations
- The Quantum Mechanics of Some Simple Systems
- Introduction
- The free particle
- Particle in a “box”
- The uncertainty principle
- The harmonic oscillator
- Multidimensional problems
- The two-body problem
- The rigid rotor
- The Hydrogen Atom
- The central-field problem
- The hydrogen atom
- Significance of the quantum numbers in the hydrogen atom
- Probability distribution of the electron cloud in the hydrogen atom
- Electron spin and the magnetic properties of atoms
- The structure of complex atoms
- Some general trends in the periodic system
- The Covalent Bond
- General remarks
- The electron pair
- The hydrogen molecule; Valence bond method
- The covalent bond
- Overlap and directional character of the covalent bond
- Molecular geometry
- Structures with multiple bonds
- Structures involving two double bonds or a triple bond
- Bond order and bond length
- The covalent bond in elements of the second and higher periods
- Molecular energy levels
- Wave functions and symmetry
- Mathematical interlude
- The water molecule (group CZv): Example
- Representations of a group
- Reducible representations; The orthogonality theorem
- Atomic Spectroscopy
- Spectral regions
- Basic spectroscopic experiments
- Origins of spectra
- Light absorption; Beer’s law
- Theory of atomic spectra
- Quantum numbers in multielectron atoms
- Atomic spectroscopy; Term symbols
- Atoms with closed shells
- Obtaining term symbols from the electron configuration
- Examples of atomic spectra
- The magnetic properties of atoms
- X-ray spectroscopy
- X-ray fluorescence spectroscopy
- X-ray microanalysis with the electron probe
- X-ray photoelectron spectroscopy
- Ultraviolet photoelectron spectroscopy
- Molecular Spectroscopy
- Nuclear motions; Rotation and vibration
- Rotations
- The rotational spectrum
- Vibrations
- The vibration-rotation spectrum
- Rotational and vibration-rotation spectra of polyatomic molecules
- Applications of infrared spectroscopy
- Raman effect
- Electronic spectra
- Electronic spectra of polyatomic molecules
- Quantum mechanical description of time-dependent systems
- Variation in the state of a system with time
- Selection rules for the harmonic oscillator
- Selection rules and symmetry
- Selection rules for the hydrogen atom
- Selection rules for polyatomic molecules
- Intermolecular Forces
- Introduction
- Polarization in a dielectric
- Molar polarization
- Intermolecular forces
- Interaction energy and the van der Waals “a”
- Laws of interaction
- Comparison of the contributions to the interaction energy
- The hydrogen bond
- Structure of Solids
- The structural distinction between solids and liquids
- An empirical classification of solid types
- Geometrical requirements in the close-packed structures
- Geometric requirements in covalent crystals
- The symmetry of crystals
- The crystal classes
- Symmetry in the atomic pattern
- The designation of crystal planes and faces
- The x-ray examination of crystals
- Debye-Scherrer (powder) method
- Intensities and structure determination
- X-ray diffraction in liquids
- Electronic Structure and Macroscopic Properties
- Preliminary remarks
- Cohesive energy in ionic crystals
- The electronic structure of solids
- Conductors and insulators
- Ionic crystals
- Semiconductors
- Cohesive energy in metals
- Structure and Thermodynamic Properties
- The energy of a system
- Definition of the entropy
- The thermodynamic functions in terms of the partition function
- The molecular partition function
- The chemical potential
- Application to translational degrees of freedom
- Partition function of the harmonic oscillator
- The monatomic solid
- The rotational partition function
- The electronic partition function
- Ortho- and para-hydrogen
- General expressions for the partition function
- The equilibrium constant in terms of the partition functions
- Transport Properties
- Introductory remarks
- Transport properties
- The general equation for transport
- Thermal conductivity in a gas
- Collisions in a gas; The mean free path
- Final expression for the thermal conductivity
- Viscosity
- Molecular diameters
- Diffusion
- Summary of transport properties in a gas
- The nonsteady state
- The Poiseuille Formula
- The viscosimeter
- Electrical Conduction
- Electrical transport
- Conduction in metals
- The Hall effect
- The electrical current in ionic solutions
- The measurement of conductivity in electrolytic solutions
- The migration of ions
- The determination of A oc
- Transference numbers
- Molar ion conductivities
- Applications of conductance measurements
- Stokes’s law
- Conductivities of the hydrogen and hydroxyl ions
- Temperature dependence of the ion conductivities
- The Onsager equation
- Conductance at high fields and high frequencies
- Conductance in nonaqueous solvents
- Diffusion and charge transport
- Chemical Kinetics
- I Empirical Laws and Mechanism
- Introduction
- Rate measurements
- Rate laws
- First-order reactions
- Second-order reactions
- Higher-order reactions
- Determining the order of a reaction
- The dependence of rate of reaction on temperature
- Mechanism
- Opposing reactions; The hydrogen-iodine reaction
- Consecutive reactions
- Unimolecular decompositions; Lindemann mechanism
- Complex reactions The hydrogen-bromine reaction
- Free-radical mechanisms
- The temperature dependence of the rate constant for a
- complex reaction
- Branching chains; Explosions
- Nuclear fission; The nuclear reactor and the “atomic” bomb
- Reactions in solution
- Relaxation methods
- Catalysis
- Enzyme catalysis
- Acid-base catalysis
- Chemical Kinetics
- Theoretical Aspects
- Introduction
- The activation energy
- The collision theory of reaction rates
- Termolecular reactions
- Unimolecular reactions
- Irreversible thermodynamics
- The theory of absolute reaction rates
- Comparison of the collision theory with the absolute reaction rate theory
- Gibbs energy and entropy of activation
- Reactions in solution
- Ionic reactions; Salt effects
- Chemical Kinetics
- Heterogeneous Reactions, Electrolysis, Photochemistry
- Heterogeneous reactions
- Steps in the mechanism of surface reactions
- Simple decompositions on surfaces
- Bimolecular reactions on surfaces
- The role of the surface in catalysis
- Electrolysis and polarization
- Polarization at an electrode
- Measurement of overvoltage
- The current-potential relation
- General consequences of the current-potential relation
- Corrosion
- Photochemistry
- The Stark-Einstein law of photochemical equivalence
- Photophysical processes; Fluorescence and phosphorescence
- Flash photolysis
- Absorption and emission spectra of organic molecules
- Absorption with dissociation
- Examples of photochemical reactions
- Photosensitized reactions
- Photosynthesis
- The photo stationary state
- Chemiluminescence
- Polymers
- Introduction
- Types of macromolecules
- Polymer solutions
- The thermodynamics of polymer solutions
- Molar masses and molar mass distributions
- Methods of measuring molar masses