Review Sheet for Physical Chemistry I 330, Lycoming College, Fall 2003, Dr. Mahler
Chapter One (all sections) States of gases; p, V, T, n and how to measure these; Ideal Gas law and laws in it (Boyle's, Charles', Dalton's, Avogadro's); Zeroth Law of Thermodynamics; Real gases - repulsive and attractive forces, compression factor; other equations of state (van der Waals, virial); critical point and constants (p, V, T); principle of corresponding states. Chapter 1: Exercises 1.4, 6, 8, 11, 13, 16, 19 (part a), 22, 25.
Chapter Twenty Four (section 1) Molecular motion in gases Kinetic Theory of Gases; Maxwell distribution and types of molecular speed; collision- diameter, -frequency, -cross section, and mean-free path. Chapter 24: Exercises 24.4, 5, 7.
Chapter Two (all sections) Definitions basic to Thermodynamics (system, surroundings, open, closed, isolated, energy, work, heat, diathermic, adiabatic, exothermic, endothermic, etc.); First Law of Thermodynamics and internal energy (U); State functions; Expansion work, types (free, (isothermal) reversible, against constant pressure); Reversible vs. irreversible processes; Calorimetry and thermochemistry; Enthalpy (heat at constant pressure), relation to U; Heat capacities; adiabatic changes; standard enthalpy changes and Hess' law, thermochemical equations; Standard enthalpies of formation; stoichiometric numbers; Group and Average Bond Enthalpies; Kirchoff's law and enthalpy temperature dependence. Chapter 2: Exercises 2.6, 7, 8, 12, 13, 16, 23, 27, 32, 37, 39, 45.
Chapter Three (all sections) State functions and exact differentials; partial derivatives and their properties; partial derivative properties for all systems and for ideal gases, and their relations (heat capacities, πT, expansion coefficient, isothermal compressibility, (isothermal) Joule-Thomson coefficient); temperature dependence of enthalpy; inversion temperature. Chapter 3: Exercises 3.9, 12a&b, 13, 18. Problems 3.12, 13, 14, 24.
Chapter Four (all sections) Second Law of Thermodynamics; spontaneous change, order-disorder, and entropy; definition and properties of entropy; applications of entropy - adiabatic processes, phase transitions (Trouton's rule), Clausius inequality, expansion of ideal gas, variation with temperature); Carnot cycle, engines, refrigerators and their efficiencies; Third Law of Thermodynamics and Nernst Heat theorem; Third law entropy and standard reaction entropies; Low temperatures; Helmholtz, A, and Gibbs, G, (Free) Energies; A and maximum work; G and maximum non-expansion work; standard Gibbs energy of formation and reaction. Chapter 4: Exercises 4.4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26.
Chapter Five (all sections) The fundamental equation (combining First and Second laws); Maxwell equations and other partial derivative relationships - VAT of UGly SHiPs; G variation with P and T; Thermodynamic equation of state; Gibbs-Helmholtz equation; chemical potential; fugacity and pressure, real and ideal gases. Chapter 5: Exercises 5.4, 5, 7, 12; Problems 5.5, 6, 7, 8.
Chapter Six (sections 1-7) One-component system phase diagrams and definitions (triple point, critical point, normal, etc.); interpreting phase diagrams (real examples); simple phase rule; equilibrium and chemical potential - phase transition boundaries; Clapeyron and Clausius-Clapeyron equations; Ehrenfest classifications. Chapter 6: Exercises 6.4, 5, 8, 11, 12, try 14; Problem 6.3.
Chapter Seven Mixtures; Partial molar quantities - volume and chemical potential; Mixing and its thermodynamics; Liquid solutions - ideal, ideal-dilute, Raoult's and Henry's Laws; Colligative properties (b.p. elevation, f.p. depression, osmotic pressure); activity -solvent and solute. Chapter 7: Exercises 7.4, 6, 7, 8, 10, 11, 12, 13, 15, 21.
Chapter Eight Multiple component phase diagrams and the Phase Rule (component, constituent, phase, variance - degree of freedom); Two component systems; Liquid-Vapor systems: pressure-composition diagrams (interpretation, tie line, isopleth, lever rule); temperature-composition diagrams (fractional distillation and theoretical plates, azeotropes, immiscible liquids); Liquid-liquid systems (miscibility, upper and lower critical temperatures); Liquid-Solid systems (eutectics, compounds, congruent and incongruent melting, immiscible solids); Ultrapurity and zone refining. Chapter 8: Exercises 8.4, 6, 9, 12, 13, 14, try 15, 16, 17, 18, 19.
Chapter Nine Spontaneous Chemical Reactions and Equilibrium; Extent of reaction and Gibbs energy minimum; Equilibrium constant, reaction Quotient (Q), relations to G; LeChatelier's Principle - response of K and systems at equilibrium to changes in composition, pressure and temperature (van't Hoff equation); Applications of Equilibria (brief acid-base chemistry). Chapter 9: Exercises 9.5, 7, 8, 10, 15, 16, 17, 18, 19.
Chapter Ten (sections 2, 3, 4, 5) Ions and Electrochemistry; Properties of Ions in solution (mean ionic activity coefficient); Debye-Hückel limiting law; Electrochemical cells & their conventions and definitions; Half cells and half reactions; Electrochemical relations (Nernst equation, standard potentials). Cell potential and Gibbs Free Energy, Equilibrium constant, solubility product; Chapter 10: Exercises 10.5, 8, 12, 15, 18, 19, 20, 21, 24, 29, 32.