CHEMISTRY DEPARTMENT, PORTLAND STATE UNIVERSITY CHEMISTRY 440/540, PHYSICAL CHEMISTRY. FALL, 2014 Venue: CR 250 Instructor: R. H. Simoyi (SB2 372) Syllabus: The chapters and page numbers referred to in this syllabus are from Physical Chemistry, Thermodynamics, Structure and Change; by Atkins and de Paula, W. H. Freeman and Company. ISBN 13: 978-1- 4292-9019-7 (2014, Tenth Edition) Lecture No. Date Topic Pages 0 bef. 9/29 Fundamentals; Matter,, Nuclear model, bulk matter, This is just revision to get us all on the same page. You should be familiar with all the topics dealt with on pages 1 8 001-008 0 bef. 9/29 Energy, Newton s laws, work and energy, Boltzmann distribution; equipartition 009 017 0 bef. 9/29 Waves, electromagnetic field 019-022 1 Mon, 9/29 Properties of gases, ideal gas, state variables equations of state 030-035 Mixture of gases 030-036 2 Wed, 10/1 Kinetic theory of gases (introduction), Molecular speeds, Maxwell-Boltzmann 037 044 Collisions, Collision frequency, mean free path 037-044 3 Fri, 10/3 Real gases, deviations from ideal behavior. Compression factor, virial coefficients 045 050 Van der Waals equation of state 045 050 4 Mon, 10/6 VDW s loops and Maxwell construction Corresponding states, reduced variables, 049-053 - 1 -
Other equations of state 049 053 Interlude: Read and familiarize yourself with differentiation and integration relevant to this 069-062 Course on pp 59-62. 5 Wed, 10/8 First Law of thermodynamics; concepts. Acquisitive form of the first law 063-067 Thermodynamic systems, heat and work, Internal energy 063-067 6 Fri, 10/10 Formulation of the first law, expansion work, constant pressure expansion 067 071 Isothermal expansion work 070 071 7 Mon, 10/13 Calculation of Cp work done. Calorimetry, heat capacity 071 074 Enthalpy and enthalpy change 074-076 8 Wed, 10/15 Variation of enthalpy with T at Cp, Relationship of Cv and Cp 076-079 Adiabatic changes, standard enthalpy changes 079-081 9 Fri, 10/17 Thermochemistry, Born-Haber cycle, Hess Law, calculations 081-084 Hess Law, Kirchoff s Law; standard enthalpy of formation 084-086 10 Mon, 10/20 Differential scanning calorimetry, isorthermal titration calorimetry 087 089 Exact and inexact differentials, changes in internal energy 090-092 075 081 Joule-Thompson coefficient, measurement of isothermal JTC 079 085-2 - Interlude: Students may want to read on the section on multivariate calculus profiled on 109-111
pages 109-111 before tackling the subject matter profiled on pages 90 95 11 Wed, 10/22 The Joule experiment, change of internal energy at Cp, 092 094 Joule-Thompson coefficient, isothermal Joule-Thompson coefficient 094 099 12 Fri, 10/24 Adiabatic changes, change in temperature 100 101 Change in pressure 101-103 13 Mon, 10/27 Second Law of thermodynamics, spontaneity, energy dispersal and entropy 112-115 Entropy as a state function 115 118 Mon, 10/27 First exam given, covers lectures 1 13 (this is a take-home exam) 14 Wed, 10/29 Entropy and the Carnot cycle, thermodynamic temperature, Clausius Inequality 118-125 Entropy and phase transitions. 118 125 15 Fri, 10/31 Third law of thermodynamics, Nernst theorem 126-128 Absolute entropies, Helmholtz energy and work 128 130 16 Mon, 11/03 Gibbs and non-expansion work, molar Gibbs energies 131 134 Maximum work, spontaneity, Born equation 134-139 - 3 -
17 Wed, 11/05 Maxwell relations, internal pressure, fundamental equation of thermodynamics 140 145 Properties of Gibbs Energy; variation with pressure 145 146 18 Fri, 11/07 Properties of Gibbs energy, cont d; fugacity 146-148 Problem solving, taken from pp 147-153 147 153 19 Mon, 11/10 Physical transformations of substances, phase diagrams 154-157 Phase rule 157 160 20 Wed, 11/12 Some specific phase diagrams, water, helium and carbon dioxide 160-162 Phase stabilities 164-166 21 Fri, 11/14 Slopes and loci of phase boundaries, the liquid-vapor equilibrium 167-170 Ehrenfest transitions, lambda transitions 171 173 22 Mon, 11/17 Simple mixtures, description of mixtures, partial molar volumes 180 185 The Gibbs-Duhem equation Mon, 11/17 Second take-home exam, covers lectures 1-21 - 4-23 Wed, 11/19 Thermodynamics of mixing, excess functions, ideal solutions 185-188
Raoult and Henry s laws 188-191 24 Fri, 11/21 Liquid mixtures, ideal solutions, more excess functions 192 194 Colligative properties, elevation of boiling points, etc 194 197 25 Mon, 11/24 Solubility, Osmosis 198-201 26 Wed, 11/26 Make up Class Fri, 11/28 The day after Thanksgiving, no university exercises 27 Mon, 12/01 Temperature-composition phase diagrams, lever rule 202-204 Phase separation, critical solution temperatures 205 210 28 Wed, 12/03 Activities, activity coefficients, Biological standard state 220 225 Mean activity coefficients 226 228 29 Fri, 12/06 The Debye-Huckel limiting law, ionic strength 228-232 30 Mon, 12/08 Final Exam, 12:30 PM 2:20 PM (Venue will be the same as the one for our normal lectures) - 5 -
Professor Simoyi, however, will not be continuing with the class for Chem 441/541. A new professor will take over for the winter term. - 6 -