Physical Chemistry 3rd Edition Gilbert W Castellan

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