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element of physical chemistry

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  • Cover Page

  • Fundamental constants

  • Copyright Page

  • Title Page

  • About the book

    • Organizing the information

    • Mathematics support

    • Visualizing the information

    • Problem solving

  • The Book Companion Site

    • For students

    • For lecturers

    • Elements of Physical Chemistry eBook

    • Other resources

    • Solutions manual

  • Preface

  • About the authors

  • Acknowledgements

  • Brief contents

  • Detailed contents

  • Introduction

    • 0.1: The states of matter

    • 0.2: Physical state

    • 0.3: Force

    • 0.4: Energy

    • 0.5: Pressure

    • 0.6: Temperature

    • 0.7: Amount of substance

    • 0.8: Extensive and intensive properties

    • 0.9: Measures of concentration

    • 0.10: Reaction stoichiometry

      • CHECKLIST OF KEY IDEAS

      • TABLE OF KEY EQUATIONS

      • QUESTIONS AND EXERCISES

  • Chapter 1: The properties of gases

    • Equations of state

      • 1.1: The perfect gas equation of state

      • 1.2: Using the perfect gas law

        • Box 1.1: The gas laws and the weather

      • 1.3: Mixtures of gases: partial pressures

    • The kinetic model of gases

      • 1.4: The pressure of a gas according tothe kinetic model

      • 1.5: The average speed of gas molecules

      • 1.6: The Maxwell distribution of speeds

      • 1.7: Diffusion and effusion

      • 1.8: Molecular collisions

    • Real gases

      • 1.9: Molecular interactions

      • 1.10: The critical temperature

      • 1.11: The compression factor

      • 1.12: The virial equation of state

      • 1.13: The van der Waals equation of state

      • 1.14: The liquefaction of gases

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • FURTHER INFORMATION 1.1

        • QUESTIONS AND EXERCISES

  • Chapter 2: Thermodynamics: the first law

    • The conservation of energy

      • 2.1: Systems and surroundings

      • 2.2: Work and heat

      • 2.3: The measurement of work

      • 2.4: The measurement of heat

      • 2.5: Heat influx during expansion

    • Internal energy and enthalpy

      • 2.6: The internal energy

      • 2.7: The internal energy as a state function

      • 2.8: The enthalpy

      • 2.9: The temperature variation of the enthalpy

        • Box 2.1: Differential scanning calorimetry

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • QUESTIONS AND EXERCISES

  • Chapter 3: Thermodynamics: applications of the First Law

    • Physical change

      • 3.1: The enthalpy of phase transition

      • 3.2: Atomic and molecular change

    • Chemical change

      • 3.3: Enthalpies of combustion

      • 3.4: The combination of reaction enthalpies

        • Box 3.1: Fuels, food, and energyresources

      • 3.5: Standard enthalpies of formation

      • 3.6: Enthalpies of formation and molecular modelling

      • 3.7: The variation of reaction enthalpy with temperature

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • QUESTIONS AND EXERCISES

  • Chapter 4: Thermodynamics: the Second Law

    • Entropy

      • 4.1: The direction of spontaneous change

      • 4.2: Entropy and the Second Law

        • Box 4.1: Heat engines, refrigerators, and heat pumps

      • 4.3: The entropy change accompanying expansion

      • 4.4: The entropy change accompanying heating

      • 4.5: The entropy change accompanying aphase transition

      • 4.6: Entropy changes in the surroundings

      • 4.7: Absolute entropies and the Third Law of thermodynamics

      • 4.8: The statistical entropy

      • 4.9: Residual entropy

      • 4.10: The standard reaction entropy

      • 4.11: The spontaneity of chemical reactions

    • The Gibbs energy

      • 4.12: Focusing on the system

      • 4.13: Properties of the Gibbs energy

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • QUESTIONS AND EXERCISES

  • Chapter 5: Physical equilibria: pure substances

    • The thermodynamics of transition

      • 5.1: The condition of stability

      • 5.2: The variation of Gibbs energy with pressure

      • 5.3: The variation of Gibbs energy with temperature

    • Phase diagrams

      • 5.4: Phase boundaries

      • 5.5: The location of phase boundaries

      • 5.6: Characteristic points

        • Box 5.1: Supercritical fluids

      • 5.7: The phase rule

      • 5.8: Phase diagrams of typical materials

      • 5.9: The molecular structure of liquids

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • QUESTIONS AND EXERCISES

  • Chapter 6: The properties of mixtures

    • The thermodynamic description of mixtures

      • 6.1: Partial molar properties

      • 6.2: Spontaneous mixing

      • 6.3: Ideal solutions

      • 6.4: Ideal–dilute solutions

        • Box 6.1: Gas solubility and respiration

      • 6.5: Real solutions: activities

    • Colligative properties

      • 6.6: The modification of boiling and freezing points

      • 6.7: Osmosis

    • Phase diagrams of mixtures

      • 6.8: Mixtures of volatile liquids

      • 6.9: Liquid–liquid phase diagrams

      • 6.10: Liquid–solid phase diagrams

      • 6.11: The Nernst distribution law

        • Box 6.2: Ultrapurity and controlled impurity

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • QUESTIONS AND EXERCISES

  • Chapter 7: Chemical equilibrium: the principles

    • Thermodynamic background

      • 7.1: The reaction Gibbs energy

      • 7.2: The variation of DrG with composition

      • 7.3: Reactions at equilibrium

      • 7.4: The standard reaction Gibbs energy

      • 7.5: The equilibrium composition

      • 7.6: The equilibrium constant in terms of concentration

    • The response of equilibria to the conditions

      • 7.7: The presence of a catalyst

      • 7.8: The effect of temperature

        • Box 7.1: Coupled reactions in biochemicalprocesses

      • 7.9: The effect of compression

        • Box 7.2: Binding of oxygen to myoglobinand haemoglobin

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • QUESTIONS AND EXERCISES

  • Chapter 8: Chemical equilibrium: equilibria in solution

    • Proton transfer equilibria

      • 8.1: Brønsted–Lowry theory

      • 8.2: Protonation and deprotonation

      • 8.3: Polyprotic acids

      • 8.4: Amphiprotic systems

    • Salts in water

      • 8.5: Acid–base titrations

      • 8.6: Buffer action

        • Box 8.1 Buffer action in blood

      • 8.7: Indicators

    • Solubility equilibria

      • 8.8: The solubility constant

      • 8.9: The common-ion effect

      • 8.10: The effect of added salts on solubility

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • QUESTIONS AND EXERCISES

  • Chapter 9: Chemical equilibrium: electrochemistry

    • Ions in solution

      • 9.1: The Debye–Hückel theory

      • 9.2: The migration of ions

        • Box 9.1: Ion channels and pumps

    • Electrochemical cells

      • 9.3: Half-reactions and electrodes

        • Box 9.2: Fuel cells

      • 9.4: Reactions at electrodes

      • 9.5: Varieties of cell

      • 9.6: The cell reaction

      • 9.7: The cell potential

      • 9.8: Cells at equilibrium

      • 9.9: Standard potentials

      • 9.10: The variation of potential with pH

      • 9.11: The determination of pH

    • Applications of standard potentials

      • 9.12: The electrochemical series

      • 9.13 The determination of thermodynamic functions

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • QUESTIONS AND EXERCISES

  • Chapter 10: Chemical kinetics: the rates of reactions

    • Empirical chemical kinetics

      • 10.1: Spectrophotometry

      • 10.2: Experimental techniques

    • Reaction rates

      • 10.3: The definition of rate

      • 10.4: Rate laws and rate constants

      • 10.5: Reaction order

      • 10.6: The determination of the rate law

      • 10.7: Integrated rate laws

      • 10.8: Half-lives and time constants

    • The temperature dependence of reaction rates

      • 10.9: The Arrhenius parameters

      • 10.10: Collision theory

      • 10.11: Transition-state theory

        • Box 10.1 Femtochemistry

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • QUESTIONS AND EXERCISES

  • Chapter 11: Chemical kinetics: accounting forthe rate laws

    • Reaction schemes

      • 11.1: The approach to equilibrium

      • 11.2: Relaxation methods

        • Box 11.1: Kinetics of protein folding

      • 11.3: Consecutive reactions

    • Reaction mechanisms

      • 11.4: Elementary reactions

      • 11.5: The formulation of rate laws

      • 11.6: The steady-state approximation

      • 11.7: The rate-determining step

      • 11.8: Kinetic control

      • 11.9: Unimolecular reactions

    • Reactions in solution

      • 11.10: Activation control and diffusion control

      • 11.11: Diffusion

    • Catalysis

      • 11.12: Homogeneous catalysis

      • 11.13: Enzymes

    • Chain reactions

      • 11.14: The structure of chain reactions

      • 11.15: The rate laws of chain reactions

        • Box 11.2 Explosions

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • FURTHER INFORMATION 11.1 FICK’SLAWS OF DIFFUSION

        • QUESTIONS AND EXERCISES

  • Chapter 12: Quantum theory

    • Three crucial experiments

      • 12.1: Atomic and molecular spectra

      • 12.2: The photoelectric effect

      • 12.3: Electron diffraction

    • The dynamics of microscopic systems

      • 12.4: The Schrödinger equation

      • 12.5: The Born interpretation

      • 12.6: The uncertainty principle

    • Applications of quantum mechanics

      • 12.7: Translational motion

        • (a): Motion in one dimension

        • (b): Tunnelling

        • (c): Motion in two dimensions

      • 12.8: Rotational motion

        • (a): Rotation in two dimensions

        • (b): Rotation in three dimensions

      • 12.9: Vibrational motion

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • QUESTIONS AND EXERCISES

  • Chapter 13: Quantum chemistry: atomic structure

    • Hydrogenic atoms

      • 13.1: The spectra of hydrogenic atoms

      • 13.2: The permitted energies of hydrogenicatoms

      • 13.3: Quantum numbers

      • 13.4: The wavefunctions: s orbitals

      • 13.5: The wavefunctions: p and d orbitals

      • 13.6: Electron spin

      • 13.7: Spectral transitions and selection rules

    • The structures of many-electron atoms

      • 13.8: The orbital approximation

      • 13.9: The Pauli principle

      • 13.10: Penetration and shielding

      • 13.11: The building-up principle

      • 13.12: The occupation of d orbitals

      • 13.13: The configurations of cations and anions

      • 13.14: Self-consistent field orbitals

    • Periodic trends in atomic properties

      • 13.15: Atomic radius

      • 13.16: Ionization energy and electron affinity

    • The spectra of complex atoms

      • 13.17: Term symbols

        • Box 13.1 Spectroscopy of stars

      • 13.18: Spin–orbit coupling

    • 13.19: Selection rules

      • CHECKLIST OF KEY IDEAS

      • TABLE OF KEY EQUATIONS

      • FURTHER INFORMATION 13.1:THE PAULI PRINCIPLE

      • QUESTIONS AND EXERCISES

  • Chapter 14: Quantum chemistry: the chemical bond

    • Introductory concepts

      • 14.1: The classification of bonds

      • 14.2: Potential-energy curves

    • Valence bond theory

      • 14.3: Diatomic molecules

      • 14.4: Polyatomic molecules

      • 14.5: Promotion and hybridization

      • 14.6: Resonance

    • Molecular orbitals

      • 14.7: Linear combinations of atomic orbitals

      • 14.8: Bonding and antibonding orbitals

      • 14.9: The structures of diatomic molecules

      • 14.10: Hydrogen and helium molecules

      • 14.11: Period 2 diatomic molecules

      • 14.12: Symmetry and overlap

      • 14.13: The electronic structures of homonuclear diatomic molecules

      • 14.14: Heteronuclear diatomic molecules

      • 14.15: The structures of polyatomic molecules

      • 14.16: The Hückel method

    • Computational chemistry

      • 14.17: Techniques

      • 14.18: Graphical output

      • 14.19: Applications

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • QUESTIONS AND EXERCISES

  • Chapter 15: Molecular interactions

    • van der Waals interactions

      • 15.1: Interactions between partial charges

      • 15.2: Electric dipole moments

      • 15.3: Interactions between dipoles

      • 15.4: Induced dipole moments

      • 15.5: Dispersion interactions

    • The total interaction

      • 15.6: Hydrogen bonding

        • Box 15.1 Molecular recognition

      • 15.7: The hydrophobic effect

      • 15.8: Modelling the total interaction

      • 15.9: Molecules in motion

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • QUESTIONS AND EXERCISES

  • Chapter 16: Materials: macromolecules and aggregates

    • Synthetic and biological macromolecules

      • 16.1: Determination of size and shape

      • 16.2: Models of structure: random coils

      • 16.3: Models of structure: polypeptides and polynucleotides

      • 16.4: Mechanical properties of polymers

        • Box 16.1 The prediction of protein structure

    • Mesophases and disperse systems

      • 16.5: Liquid crystals

        • Box 16.2 Biological membranes

      • 16.6: Classification of disperse systems

      • 16.7: Surface, structure, and stability

      • 16.8: The electric double layer

      • 16.9: Liquid surfaces and surfactants

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • QUESTIONS AND EXERCISES

  • Chapter 17: Metallic, ionic, and covalent solids

    • Bonding in solids

      • 17.1: The band theory of solids

      • 17.2: The occupation of bands

      • 17.3: The optical properties of junctions

      • 17.4: Superconductivity

      • 17.5: The ionic model of bonding

      • 17.6: Lattice enthalpy

      • 17.7: The origin of lattice enthalpy

      • 17.8: Covalent networks

      • 17.9: Magnetic properties of solids

        • Box 17.1 Nanowires

    • Crystal structure

      • 17.10: Unit cells

      • 17.11: The identification of crystal planes

      • 17.12: The determination of structure

      • 17.13: Bragg’s law

      • 17.14: Experimental techniques

      • 17.15: Metal crystals

      • 17.16: Ionic crystals

      • 17.17: Molecular crystals

        • Box 17.2 X-ray crystallography of biological macromolecules

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • QUESTIONS AND EXERCISES

  • Chapter 18: Solid surfaces

    • The growth and structure of surfaces

      • 18.1: Surface growth

      • 18.2: Surface composition and structure

    • The extent of adsorption

      • 18.3: Physisorption and chemisorption

      • 18.4: Adsorption isotherms

      • 18.5: The rates of surface processes

    • Catalytic activity at surfaces

      • 18.6: Mechanisms of heterogeneous catalysis

      • 18.7: Examples of heterogeneous catalysis

    • Processes at electrodes

      • 18.8: The electrode–solution interface

        • Box 18.1 Fuel cells

      • 18.9: The rate of electron transfer

      • 18.10: Voltammetry

      • 18.11: Electrolysis

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • QUESTIONS AND EXERCISES

  • Chapter 19: Spectroscopy: molecular rotations and vibrations

    • Rotational spectroscopy

      • 19.1: The rotational energy levels of molecules

      • 19.2: The populations of rotational states

      • 19.3: Rotational transitions: microwavespectroscopy

      • 19.4: Linewidths

      • 19.5: Rotational Raman spectra

    • Vibrational spectroscopy

      • 19.6: The vibrations of molecules

      • 19.7: Vibrational transitions

      • 19.8: Anharmonicity

      • 19.9: The technique

      • 19.10: Vibrational Raman spectra of diatomic molecules

      • 19.11: The vibrations of polyatomic molecules

        • Box 19.1 Climate change

      • 19.12: Vibration–rotation spectra

      • 19.13: Vibrational Raman spectra of polyatomic molecules

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • FURTHER INFORMATION 19.1 THE ROTATIONAL ENERGY LEVELS OF MOLECULES

        • QUESTIONS AND EXERCISES

  • Chapter 20: Spectroscopy: electronic transitions and photochemistry

    • Ultraviolet and visible spectra

      • 20.1: Practical considerations

      • 20.2: Absorption intensities

      • 20.3: The Franck–Condon principle

      • 20.4: Specific types of transitions

        • Box 20.1 Vision

    • Radiative and nonradiative decay

      • 20.5: Fluorescence

      • 20.6: Phosphorescence

      • 20.7: Lasers

      • 20.8: Applications of lasers in chemistry

    • Photoelectron spectroscopy

    • Photochemistry

      • 20.9: Quantum yield

        • Box 20.2 Photosynthesis

      • 20.10: Mechanisms of photochemical reactions

      • 20.11: The kinetics of decay of excited states

      • 20.12: Fluorescence quenching

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • FURTHER INFORMATION 20.1 THE BEER–LAMBERT LAW

        • FURTHER INFORMATION 20.2 THE EINSTEIN TRANSITION PROBABILITIES

        • QUESTIONS AND EXERCISES

  • Chapter 21: Spectroscopy: magnetic resonance

    • Principles of magnetic resonance

      • 21.1: Electrons and nuclei in magnetic fields

      • 21.2: The technique

    • The information in NMR spectra

      • 21.3: The chemical shift

        • Box 21.1 Magnetic resonance imaging

      • 21.4: The fine structure

      • 21.5: Spin relaxation

      • 21.6: Proton decoupling

      • 21.7: Conformational conversion and chemical exchange

      • 21.8: The nuclear Overhauser effect

      • 21.9: Two-dimensional NMR

      • 21.10: Solid-state NMR

    • The information in EPR spectra

      • 21.11: The g-value

      • 21.12: Hyperfine structure

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • QUESTIONS AND EXERCISES

  • Chapter 22: Statistical thermodynamics

    • The partition function

      • 22.1: The Boltzmann distribution

      • 22.2: The interpretation of the partition function

      • 22.3: Examples of partition functions

      • 22.4: The molecular partition function

    • Thermodynamic properties

      • 22.5: The internal energy and the heat capacity

      • 22.6: The entropy and the Gibbs energy

      • 22.7: The statistical basis of chemical equilibrium

      • 22.8: The calculation of the equilibrium constant

        • CHECKLIST OF KEY IDEAS

        • TABLE OF KEY EQUATIONS

        • FURTHER INFORMATION 22.1 THE CALCULATION OF PARTITION FUNCTIONS

        • FURTHER INFORMATION 22.2 THE EQUILIBRIUM CONSTANT FROM THE PARTITION FUNCTION

        • QUESTIONS AND EXERCISES

  • Appendix 1: Quantities and units

  • Appendix 2: Mathematical techniques

    • Basic procedures

      • A2.1 Algebraic equations and graphs

      • A2.3 Vectors

    • Calculus

      • A2.4 Differentiation

      • A2.6 Integration

      • A2.6 Differential equations

  • Appendix 3: Concepts of physics

    • Classical mechanics

      • A3.1 Energy

      • A3.2 Force

    • Electrostatics

      • A3.3 The Coulomb interaction

      • A3.4 The Coulomb potential

      • A3.5 Current, resistance, and Ohm’s law

    • Electromagnetic radiation

      • A3.6 The electromagnetic field

      • A3.7 Features of electromagnetic radiation

  • Appendix 4: Review of chemical principles

    • A4.1 Oxidation numbers

    • A4.2 The Lewis theory of covalent bonding

    • A4.3 The VSEPR model

  • Data section

  • Index

Nội dung

[...]... International Union of Pure and Applied Chemistry and was a member of IUPAC’s Physical and Biophysical Chemistry Division Julio de Paula is Professor of Chemistry and Dean of the College of Arts & Sciences at Lewis & Clark College A native of Brazil, Professor de Paula received a B.A degree in chemistry from Rutgers, The State University of New Jersey, and a Ph.D in biophysical chemistry from Yale... concentration 0.10 Reaction stoichiometry CHECKLIST OF KEY IDEAS TABLE OF KEY EQUATIONS QUESTIONS AND EXERCISES Chemistry is the science of matter and the changes it can undergo The branch of the subject called physical chemistry is concerned with the physical principles that underlie chemistry Physical chemistry seeks to account for the properties of matter in terms of fundamental concepts such as atoms, electrons,... framework for all other branches of chemistry for inorganic chemistry, organic chemistry, biochemistry, geochemistry, and chemical engineering It also provides the basis of modern methods of analysis, the determination of structure, and the elucidation of the manner in which chemical reactions occur To do all this, it draws on two of the great foundations of modern physical science, thermodynamics... INTRODUCTION One of the roles of physical chemistry is to establish the link between the properties of bulk matter and the behaviour of the particles—atoms, ions, or molecules of which it is composed A physical chemist formulates a model, a simplified description, of each physical state and then shows how the state’s properties can be understood in terms of this model The existence of different states of matter... numerical value of the molar mass of an element or compound, respectively More precisely (but equivalently), the RAM of an element or the RMM of a compound is its average atomic or molecular mass relative to the mass of an atom of carbon-12 set equal to 12 The atomic weight (or RAM) of a natural sample of carbon is 12.01 and the molecular weight (or RMM) of water is 18.02 The molar mass of an element is... The molar mass of H2O is 18.02 g mol−1, so the mass of water produced is (2 × 1.38 mol) × (18.02 g mol−1) = 49.7 g Checklist of key ideas You should now be familiar with the following concepts 1 Physical chemistry is the branch of chemistry that establishes and develops the principles of chemistry in terms of the underlying concepts of physics and the language of mathematics 2 The states of matter are... 100 cm3 of solution: 2.11 g Molar mass of B: 234.01 g mol−1 Density of solution in water: 1.01 g cm−3 Density of solution in benzene: 0.881 g cm−3 0.30 Calculate the mole fractions of the molecules of a mixture that contains 56 g of benzene and 120 g of methylbenzene (toluene) 0.31 A simple model of dry air at sea level is that it consists of 75.53 per cent (by mass) of nitrogen, 23.14 per cent of oxygen,... University of Keele Anthony Meijer, University of Sheffield Marcelo de Miranda, University of Leeds Damien Murphy, University of Cardiff Gavin Reid, University of Leeds Stephen Roser, University of Bath Karl Ryder, University of Leicester Sven Schroeder, University of Manchester David Steytler, University of East Anglia Michael Stockenhuber, University of Newcastle, New South Wales Svein Stolen, University of. .. measurement of the mass of its atoms and then multiplication of the mass of one atom by Avogadro’s constant (the number of atoms per mole) Care has to be taken to allow for the isotopic composition of an element, so we must use a suitably weighted mean of the masses of the isotopes present The values obtained in this way are printed on the periodic table inside the back cover The molar mass of a compound of. .. follows: 1 mol of specified particles is equal to the number of atoms in exactly 12 g of carbon-12 (12C) This number is determined experimentally by dividing 12 g by the mass of one atom of carbon-12 Because the mass of one carbon-12 atom is measured by using a mass spectrometer as 1.992 65 × 10−23 g, the number of atoms in exactly 12 g of carbon-12 is Number of atoms = total mass of sample mass of one atom

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