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Chemistry 210 Dr. Susan B. Piepho January 14, 2002 Chemistry 210, Physical Chemistry II Daily Schedule, Spring 2002 Readings, Exercises, and Problems are from Physical Chemistry, Sixth Edition, by Peter W. Atkins. The numbers of Exercises and Problems are italicized if no solution is provided in the Solutions Manual. Detailed solutions to all Handout Problems, and to Exercises and Problems marked with an asterisk (*) should be handed on the dates indicated. Tuesday Thursday 1/15 Read: Chapter 0, pp. 1-9 (Introduction: orientation and background – this is mainly review); Chapter 1, pp. 13-31 (perfect gas, Boyle’s law, Charles’s law, Avogadro’s principle, perfect gas equation, Dalton’s law, the kinetic theory of gases, real gases, the compression factor Z). 1/22 Hand In: Chapter 1, Problem #1.28. Read: Chapter 2, pp. 45-55 (Open and closed systems, surroundings, work, energy, heat, internal energy U, state function, First Law of Thermodynamics, adiabatic change, work of reversible and irreversible expansion). Exercises: 2.2(a), 2.6(a), 2.9(a); Problems: 2.5 (Answer: (a) w = - 0.27 kJ; (b) w = - 0.94 kJ). Derivation Worksheet (handout), Part I 1/29 Read: Chapter 2, pp. 62-65 (Relation between CV and Cp, work of adiabatic expansion, perfect gas adiabatic equations). Exercises: 2.20(a), 2.21(a), 2.24(a), 2.25(a). 1/17 Read: Chapter 1, pp. 31-39 (Virial coefficients, virial equation of state, Boyle temperature, critical constants, van der Waals equation, principle of corresponding states). Exercises: 1.3(a), 1.5(a), 1.6(b)†, 1.9(a); Problems: 1.2, 1.4, 1.7. †Answer: 2.67 x 103 kg 1/24 Read: Chapter 2, pp. 55-62 (Calorimetry, heat capacity, enthalpy H, calculation of H, variation of H with T). Exercises: 2.4(a), 2.5(a), 2.19(a); Problems: 2.4†. †Notes on Problem 2.4: Solution manual assumes this is a reversible cycle. Where? What are U and H for any cycle? Why? 1/31 Read: Chapter 2, pp. 65-74 (Thermochemistry, standard enthalpy changes, stoichiometric numbers, Hess’s law, Born-Haber cycle, enthalpy of formation, Kirchhoff’s law). Problems: 2.2, 2.11, 2.12, 2.13*, 2.14. Friday 1/18 Exercises: 1.28(a); Problems: 1.27, 1.28*. Catch-up on Chapter 1; discussion of problems. 1/25 Quiz #1: Chapters 0 and 1. 2/1 Chapter 2 Exercises: 2.10(a), 2.26(a), 2.30(a), 2.32(a), 2.36(a), 2.44(b) †, 2.45(a) (add RT to ionization energy terms and - 2 RT to electron gain term). †Answer: At 298K, Ho = -175 kJ mol-1 and Uo = -173 kJ mol-1; at 348 K, Ho = -176 kJ mol-1. 2/5 2/7 2/8 Hand In: Problems #2.13; Derivation Read: Chapter 3, pp. 84-92 (Joule Quiz #2: Chapter 2 (Reading through pg Worksheet (handout), Part I. experiment, dH expression, Joule-Thomson 65; problems through Th 1/31 Read: Further Information 1, pp. 905-906; effect, Joule-Thomson coefficient , relation assignment). Chapter 3, pp. 81-84 (State and path between CV and Cp.). functions, exact and inexact differentials, dU Exercises: 3.7(a), 3.9(a), 3.10(a); expression). Problems: 3.7, 3.21. Exercises: 3.1(a), 3.2(a), 3.4(a), 3.5(a). 2/12 2/14 2/15 Catch-up on Chapter 3 problems. Read: Chapter 4, pp. 106-110 (Calculation of entropy changes for representative Hour Test I Read: Chapter 4, pp. 97-105 (Second law of processes, Trouton’s rule, variation of This will be on Chapters 0, 1, and 2. thermodynamics, entropy: thermodynamic entropy with temperature, measurement of and molecular interpretations, Entropy as a entropy). state function, Carnot cycle, efficiency of an Exercises: 4.8(a), 4.9(a), 4.11(a), 4.14(a), engine, Clausius inequality). 4.20(a), 4.21(a), 4.21(b)*. Problems: 4.12*. Page 1 of 3 Chemistry 210 Dr. Susan B. Piepho Tuesday 2/19 Catch-up on Chapter 4 problems. 2/26 Hand In: Exercises #4.21(b); Problem #4.12. Derivation Worksheet (handout), Part II. Catch-up on Chapter 4 problems. 3/5 January 14, 2002 Thursday 2/21 Read: Chapter 4, pp. 110-113 (Third law of thermodynamics, third-law entropies, adiabatic demagnetization, efficiencies of heat engines, refrigerators, and heat pumps, work to maintain low temperatures). Exercises: 4.23(a). Problem: 4.15. 2/28 Read: Chapter 4, pp. 113-119 (Helmholtz and Gibbs free energies, dA and dG conditions for spontaneous change, A and maximum work). Exercises: 4.15(a), 4.16(a), 4.17(a). Problem: 4.11. 3/7 Friday 2/22 Quiz #3. Chapter 3. 3/1 Catch-up on Chapter 4. 3/8 Spring Break 3/12 Read: Chapter 5, pp. 125-132 (Combining the First and Second Laws, Maxwell relations, properties of the Gibbs energy G, the Gibbs-Helmholtz equation for dependence of G on T, dependence of G on p). 3/14 3/15 Exercises: 5.2(a), 5.5(a) Quiz #4. Chapter 4. Problems: 5.1, 5.2, 5.6, 5.10—part (a) only, 5.19, 5.20. 3/19 Hand In: Derivation Worksheet (handout), Part II. Read: Chapter 5, pp. 132-136 (Chemical potential of a pure substance and of a mixture, real gases and fugacity f, standard state of a real gas, fugacity coefficient ). Exercises: 5.6(a). 3/21 Catch-up on Chapter 5 problems as needed. 3/26 Read: Chapter 6, pp. 152-159 (First and second-order phase transitions, surface tension; bubbles, cavities and droplets; capillary action). Exercises: 6.1(a), 6.3(a), 6.7(a), 6.7(b), 6.8(b). Problems: 6.3, 6.8. 4/2 Catch-up on Chapter 7 problems. 3/22 Hour Test II Read: Chapter 6, pp. 141-152 (Phase diagrams, phase boundaries, triple point, phase stability, temperature and pressure dependence of phase stability for a pure substance, derivation of equations for phase boundary lines, Clapeyron and ClausiusClapeyron equations). 3/28 Read: Chapter 7, pp. 163-176 (Thermodynamics of mixtures, partial molar quantities, chemical potential = partial molar Gibbs energy, calculation of ∆G, ∆S, and ∆H for mixing of gases, ideal solutions and Raoult’s law, ideal dilute solutions and Henry’s law). Exercises: 7.9(a), 7.10(b), 7.12(a), 7.13(a), 7.18(a). 4/4 Read: Chapter 8, pp. 191-201. (Phase rule, one component systems, two component liquid-vapor systems: p vs xB and T vs xB diagrams, isopleth, tie line, lever law, distillation, azeotropes). Exercises: 8.1(a), 8.3(a), 8.5(a), 8.16(a). Page 2 of 3 This will be on Chapters 3 and 4, and on Chapter 5 as announced in class. 3/29 Read: Chapter 7, pp. 176-186 (Properties of solutions, colligative properties: vapor pressure lowering, boiling point elevation, freezing point depression, and osmotic pressure; activities and activity coefficients). Exercises: 7.6(a), 7.7(a), 7.8(a), 7.14(a), 7.16(a), 7.19(a). 4/5 Quiz #5. This will cover the parts of Chapter 5 which were not on Hour Test II, Chapter 6, and Chapter 7 through the Th 3/28 assignments. Chemistry 210 Dr. Susan B. Piepho Tuesday 4/9 Read: Chapter 8, pp. 201-208. (Liquidliquid phase diagrams, immiscible liquids, liquid-solid phase diagrams, eutectics, reacting systems, three-component systems). Exercises: 8.9(a), 8.9(b)—part (b) only, 8.11(a). Problem: 8.8*. 4/16 Hand In: Problem 8.8. Read: Chapter 9, pp. 215-227. (Reaction Gibbs energy, exergonic and endergonic reactions, thermodynamic equilibrium constant, response of equilibria to change of ptotal and to a change in T, van’t Hoff equation). 4/23 Exercises: 9.8(a), 9.15(a). January 14, 2002 Thursday 4/11 Catch-up on Chapter 8 problems. Friday 4/12 Quiz #6. Chapter 7 (parts not on Quiz #5) and Chapter 8 as announced in class. 4/18 Read: Chapter 9, pp. 227-238. (Applications to selected systems: extraction of metals from their oxides, Ellingham diagram, acids and bases, pH calculations, HendersonHasselbalch equation, buffers and indicators, thermodynamics of ATP, anaerobic and aerobic metabolism). Exercises: 9.2(a), 9.3(a), 9.4(a). 4/25 Catch-up on Chapter 9 problems. Questions in preparation for final exam. Page 3 of 3 4/19 Hour Test III This will be on the parts of Chapter 5 not on Hour Test II, Chapter 6, Chapter 7, and Chapter 8. 4/26 Reading Day