1st Edition

Physical Chemistry for Engineering and Applied Sciences

By Frank R. Foulkes Copyright 2013
    704 Pages 159 B/W Illustrations
    by CRC Press

    Physical Chemistry for Engineering and Applied Sciences is the product of over 30 years of teaching first-year Physical Chemistry as part of the Faculty of Applied Science and Engineering at the University of Toronto. Designed to be as rigorous as compatible with a first-year student’s ability to understand, the text presents detailed step-by-step derivations of the equations that permit the student to follow the underlying logic and, of equal importance, to appreciate any simplifying assumptions made or mathematical tricks employed.

    In addition to the 600 exercises and end-of-chapter problems, the text is rich in worked non-trivial examples, many of which are designed to be inspiring and thought-provoking. Step-by-step derivation of all equations enables the student to smoothly follow the derivation by sight, and can be understood relatively easily by students with moderate skills and backgrounds in mathematics.

    Clear and accessible, Physical Chemistry for Engineering and Applied Sciences includes:

    • The answers to all of the 112 worked examples, 99 exercises following many of the worked examples, and 496 end-of-chapter problems
    • Topics not normally seen in introductory physical chemistry textbooks (ionic reaction rates, activities and activity coefficients) or not regularly explained in much detail (electrochemistry, chemical kinetics), with an eye on industrial applications
    • Special appendices that provide detailed explanations of basic integration and natural logarithms for students lacking a background in integral calculus
    • An in-depth chapter on electrochemistry, in which activities and activity coefficients are used extensively, as required for accurate calculations

    THINGS YOU SHOULD KNOW BUT PROBABLY FORGOT
    Basic Definitions
    SI Units
    Dalton’s Atomic Theory
    Stoichiometry
    Equivalent Weight
    Amount of Substance: the Mole
    Avogadro’s Hypothesis
    Conservation of Mass
    Conservation of Charge
    Atomic Mass Scales
    STATES OF MATTER AND THE PROPERTIES OF GASES
    The Three States of Matter
    Pressure
    Archimedes’ Principle
    Temperature
    THE IDEAL GAS
    The Ideal Gas Equation of State
    Molar Volumes
    Combined Gas Equation
    Dalton’s Law of Partial Pressures
    Mole Fractions
    Partial Volumes
    THE KINETIC THEORY OF GASES
    Postulates
    Simplified Derivation of the Ideal Gas Law
    The Meaning of Pressure
    The Meaning of Temperature
    Diffusion and Effusion
    The Speeds of Gas Molecules
    Effect of Pressure on Speed
    Distribution of Molecular Speeds
    The Maxwell-Boltzmann Distribution as an Energy Distribution
    Fraction of Molecules Having E > E'
    Concluding Remarks
    REAL GASES
    Real Gases
    Isotherms for Real Gases
    Equations of State for Real Gases
    The Virial Equation
    The Van der Waals Equation
    Liquefaction of Gases
    THERMODYNAMICS (I)
    Thermodynamics
    Definitions Used In Thermodynamics
    Work
    PV-Work
    Maximum Work Obtainable from the Isothermal Expansion of an Ideal Gas
    Reversible Processes
    THERMODYNAMICS (II)
    Internal Energy (U) and the First Law of Thermodynamics
    State Functions
    Work and Heat Are Not State Functions
    Q and W Have Algebraic Signs
    Another Look At PV-Work
    Chemical Reaction in a Constant Volume System
    The Heat Capacity of a Single Phase System
    ΔU for the Isothermal Expansion of an Ideal Gas
    The Internal Energy of a Monatomic Ideal Gas
    THERMODYNAMICS (III)
    Enthalpy (H)
    Constant Pressure Processes
    Thermochemistry
    ΔH for Fusion (Melting) and Freezing
    ΔH for Vaporization and Condensation
    ΔH for Sublimation
    Ionization Enthalpies
    Electron Affinities
    Bond Enthalpies
    THERMODYNAMICS (IV)
    The Standard State for Chemical Reactions
    Hess’s Law of Constant Heat Summation
    Standard Enthalpies of Formation
    Variation of ΔH with Temperature at Constant Pressure
    THERMODYNAMICS (V)
    Spontaneous Processes
    Entropy (S)
    ΔS for the Isothermal Expansion of an Ideal Gas
    ΔS for a Constant Pressure Heating or Cooling Process
    ΔS for a Constant Volume Heating or Cooling Process
    ΔS for a Reversible Phase Change
    Whenever a Real Process Takes Place ΔSuniv Increases
    Trouton’s Rule
    THERMODYNAMICS (VI)
    Absolute Entropies and the Third Law of Thermodynamics
    Dealing With Phase Transitions
    Entropy Changes for Chemical Reactions
    THERMODYNAMICS (VII)
    Gibbs Free Energy (G)
    Gibbs Free Energy Changes, "Other" Work, and Spontaneity
    Evaluation of ΔGT,P
    ΔG° for a Chemical Reaction
    Thermodynamic Stability
    CHEMICAL EQUILIBRIUM (I)
    Equilibrium Constants
    The Reaction Quotient (Q) and Relative Activities (ai)
    Formulation of Equilibrium Constants
    Molar Free Energies
    ΔGR for Chemical Reactions
    CHEMICAL EQUILIBRIUM (II)
    Calculations Using Thermodynamic Equilibrium Constants
    Effect of Catalyst on K
    Effect of Temperature on K
    Effect of Pressure on K
    PHASE EQUILIBRIUM (I)
    Phase Change and Gibbs Free Energy
    Phase Diagram for a Single Pure Substance
    The Phase Rule
    PHASE EQUILIBRIUM (II)
    Phase Diagram for CO2
    Phase Diagram for Water
    The Clapeyron Equation
    Phase Diagram for Carbon
    Phase Diagram for Helium
    The Clausius-Clapeyron Equation
    MIXTURES
    Expressions for Concentration
    Partial Molar Volumes
    The Chemical Potential (μ)
    The Chemical Potential of a Component in an Ideal Gas Mixture
    More About Activities
    Ideal Liquid Solutions of Volatile Solutes: Raoult’s Law
    Ideal Liquid Solutions of Non-Volatile Solutes
    Ideal Liquid Solutions of Two Volatile Liquids
    Real (Non-Ideal) Solutions
    Chemical Potential and Solvent Activity
    Ideal Dilute Solutions of Volatile Solutes: Henry’s Law
    The Solubility of Gases
    Distillation
    The Lever Rule
    Liquid-Liquid Phase Diagrams
    Liquid-Solid Phase Diagrams
    Compound Formation
    COLLIGATIVE PROPERTIES
    Colligative Properties
    Vapor Pressure Depression
    Boiling Point Elevation and Freezing Point Depression
    Osmotic Pressure
    IONIC EQUILIBRIUM
    Ionic Equilibrium
    Activities of Dissolved Species in Solution
    Activities and Activity Coefficients of Electrolytes in Solution
    Acids and Bases: The Brønsted–Lowry Concept
    The Self-Dissociation of Water
    Neutral Solutions
    ACID AND BASE DISSOCIATION
    Acid Dissociation Constants, Ka
    Dissociation of a Weak Acid
    Polyprotic Acid Calculation: Charge and Mass Balances
    Simplified Approach
    BASES AND THEIR SALTS
    Weak Bases: B or BOH
    The Salt of a Weak Acid: Hydrolysis
    The Rigorous Method
    The Salt of a Weak Base
    Acid-Base Titrations
    BUFFER SOLUTIONS
    Buffer Solutions
    Buffer of a Weak Acid and its Salt: HA + NaA
    Rigorous Derivation: HA/NaA Buffer
    Buffer of a Weak Base and Its Salt: BOH + BCl
    Rigorous Expression for BOH/BCl Buffer
    Acid-Base Indicators: HIn
    SOLUBILITY EQUILIBRIA
    Solubility Equilibria
    Relationship Between KSP and Solubility for Different Salt Types
    Activity Effects and Solubility
    The Common Ion Effect
    Salting In
    Selective Precipitation
    OXIDATION–REDUCTION REACTIONS
    Oxidation–Reduction (Redox) Reactions
    Rules for Assignment of Oxidation Numbers
    Steps for Balancing Redox Reactions
    ELECTROCHEMISTRY
    Half-Reactions, Electrodes, and Electrochemical Cells
    Electrical Work
    Types of Cells
    Liquid Junctions and Salt Bridges
    Equilibrium Voltages
    The Nernst Equation
    Single Electrode Potentials
    Calculation of Equilibrium Cell Voltages from Half-Cell Potentials
    Equilibrium Constants from Cell Voltages
    Thermodynamic Functions from Cell Voltages
    Concentration Cells
    CHEMICAL REACTION KINETICS
    Rates of Reactions: Chemical Kinetics
    Concentration Profiles
    Expression of Reaction Rates
    Differential Rate Laws
    First Order Reactions
    Half-Lives
    Second Order Reactions
    Zeroth Order Reactions
    Experimental Determination of k, m, and n
    Reaction Mechanisms
    The Rate-Determining Step
    Reaction Rates and Equilibrium
    Reaction Intermediates
    Effect of Temperature
    Rates of Ionic Reactions
    APPENDICES
    Properties of the Elements
    Thermodynamic Data for Selected Gases and Vapors
    Thermodynamic Data for Selected Liquids
    Thermodynamic Data for Selected Solids
    Thermodynamic Data for Selected Aqueous Ions
    Analytical Solution of a Cubic Equation
    The Newton-Raphson Method
    Understanding Basic Integration
    Understanding Logarithms, Exponentials, and the Integral of 1/x
    Standard Reduction Potentials
    Answers to Exercises
    Answers to Problems

    Biography

    Frank R. Foulkes