Physical Chemistry for Engineering and Applied Sciences

Physical Chemistry for Engineering and Applied Sciences

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Features

  • Shows students how to use the theoretical principles and equations developed in the text via a large number of completely worked example problems
  • Provides 500 end-of-chapter problems chosen to be sufficiently interesting to encourage students to want to know the answers
  • Facilitates self-instruction by providing the answers––but not the solutions––of all exercises and problems
  • Includes a very detailed summary at the end of each chapter, and a cross-referenced index that includes examples and problems
  • Describes ionic equilibria with equations derived rigorously using mass balances, charge balances, and equilibrium constant relationships
  • Shows how simplifying assumptions lead to the more familiar simpler forms applicable in most (but not all!) cases
  • Discusses ionic reaction rates, the basis for many industrial and biological processes
  • Reviews basic integrals and logarithms for readers who need a calculus refresher in detailed and easy-to-understand appendices

Summary

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

Table of Contents

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

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