D Textbook: P. Atkins and J. De Paula, Physical Chemistry, 9th edition, Oxford ...
Understand the concepts of internal energy, enthalpy, entropy and free ... Apply
the principles of Thermodynamics to the study of the spontaneity of chemical.
Chemistry 217 Thermodynamics and Chemical Dynamics
Fall 2013-2014 R. Sultan COURSE SYLLABUS
• Email:
[email protected]
Homepage: www.aub.edu.lb/∼rsultan • Lectures:
9:30-10:45 T Th
101 Chemistry (CRN 10880)
• Office hours: M 12-1; W 2-3; Th 11:30-12:30
Room 518 Chemisrty
• Resources available to the students: Textbook: P. Atkins and J. De Paula, Physical Chemistry, 9th edition, Oxford
University Press (2010) + Solutions manual (Atkins,Trapp, Cady and Giunta). The Thermodynamics section covers Chapters from Part 1: EQUIILIBRIUM (13,5,6) while the DYNAMICS section covers Chapters from Part 3: CHANGE (20,21,22). Full media support: http://global.oup.com/uk/orc/chemistry/pchem9e/ MOODLE course access: Check for announcements, class notes, problem sets and quizzes grades at the Chem. 217 course page, On the AUB Moodle facility. Hand-outs: will be posted on MOODLE. Problems: You must solve all the assigned problems listed in this syllabus in a gradual manner, i.e. parallel to the advancement in the course material. Additional problems from Atkins are helpful and encouraged. Separate problem sets will also be posted throughout the semester, notably in the Dynamics part. They will be posted on MOODLE. Solutions: Solutions to the problem sets will be placed on the reserve shelf in the Science Library. Also check the Electronic Reserve facility under Jafet Library, on the AUB homepage. Go to: libraries/Jafet library/e-resources/electronic reserve
• Grading:
3 Quizzes: Final Exam
(best grade: 25%; middle: 20%; lowest: 15%) 40%
• Quiz dates:
Quiz I Quiz II Quiz III Final
Monday October 7, 2013 5:30 pm - 001 Chem Monday November 11, 2013 5:30 pm - 001 Chem Monday December 9, 2013 5:30 pm - 001 Chem will be announced later.
1
• Learning outcomes: 1. Understand the laws of Thermodynamics, and know how to apply them numerically 2. 3. 4. 5. 6. 7. 8. 9. 10. 11.
to simple processes, notably the expansion and compression of gases. Acquire skills of manipulating the mathematical machinery of Thermodynamics, and develop the ability of handling the theory and derivations. Understand the concepts of internal energy, enthalpy, entropy and free energy (state functions), and the quantities heat and work (path functions). Apply the principles of Thermodynamics to the study of the spontaneity of chemical reactions. Understand chemical equilibrum and its thermodynamic significance. Apply the principles of Thermodynamics to the properties of solutions. Assimilate the Ideal Solution Theory. Apply to the derivation of colligative properties. Understand the principles of molecular motion, and learn how to manipulate the dynamics that governs it. Study the phenomenolgy of transport: diffusion - thermal conductivity - viscosity - ion transport. Develop an understanding of the measurement of the rates of chemical reactions (Chemical Kinetics), and the determination of the rate law of a chemical reaction. Understand the method of reaction rate analysis, and the derivation of integrated rate laws. Learn how to establish a close relation between the rate law and the mechanism of a chemical reaction. Learn the molecular basis for the occurrence of chemical reactions, and the molecular dynamics yielding the observed (measured) rate laws.
CONTENTS Subject
Section in Atkins
Assigned Problems
Thermodynamics Chapter 1 Introduction The Zeroth law
Reading Chapter 2
The First law (heat,work and conservation of energy) Work - Work of expansion and compression Heat - Heat capacity - Calorimetry Enthalpy Adiabatic changes
2.1,2.2 Exercises: 2.1-7,10-16 19,20
2.3 2.4 2.5 2.6 - FI 2.1 2
Thermochemistry (Enthalpy of physical and chemical change The standard state - Hess’s law) Standard enthalpies of formation Kirchhoff’s law
State functions and path functions Exact and inexact differentials Changes in internal energy Isothermal ideal gas expansion Joule’s experiment Changes in enthalpy The relation between Cp & Cv
2.7
Exercises: 2.25-28
2.8 2.9
Problems: 2.1-4,15,17
2.10 2.10 2.11 2.11
Exercises: 2.31,32
2.11 2.11 - FI 2.2
Problems: 2.20-27 2.33,35,36,38
Chapter 3 The direction of spontaneous change - Chaos & dispersal The entropy (statistical and thermodynamic views) The Second law - Clausius inequality - Carnot cycle Transformation of heat into mechanical work - Efficiency Entropy of some specific processes The absolute zero and the Third law - Third law entropies Gibbs & Helmholtz functions
The four fundamental equations Maxwell relations Properties of the Gibbs free energy Gibbs-Helmholtz equation The pressure dependence of the Gibbs function Fugacity and real gases
3.1 3.2 Exercises: 3.1-3,5-9, 12-16 3.3 3.4
Problems: 3.1,5,6,8,9
3.5
3.7 3.8 3.9 3.9 3.9
Exercises: 3.18-22 Problems: 3.24-28
FI 3.2
3
Thermodynamics of chemical reactions Chapter 6 Free energy and chemical reactions Direction of a chemical reaction Description of equilibrium Relation between standard free energy and the equilibrium constant Response of equilibria to pressure Temperature dependence of the equilibrium constant Applications
6.1 6.1 6.2 6.2
Exercises: 6.1-10 Problems: 6.2,5,6
6.3 6.4 6.5-6.8
Thermodynamics of solutions Chapter 5 Partial molal quantities Gibbs-Duhem equation Thermodynamics of mixing Chemical potential of liquids Ideal solutions - Raoult’s and Henry’s laws Liquid mixtures Colligative properties Activity
5.1 5.1 5.2 5.3
Exercises: 5.5-8,10-13 16,17
5.4 5.5 5.10-13
Problems: 5.30,31
Molecular Motion Chapter 20 Intermolecular collisions 20.1b Mean free path 20.1c Collisions with walls and surfaces 20.2 Rate of effusion 20.3 Flux: Transport down gradients 20.4 Application: Transport Properties in Gases Diffusion - Thermal conductivity 20.4 Viscosity Ion Transport Conductivity of electrolyte solutions - 20.5,6 4
Exercises: 20.2-9 13-17,20,25-27
Motion of ions - Mobility Transport numbers Molecular Diffusion Thermodynamic view - Fick’s 1st law Diffusion equation: Fick’s 2nd law
20.7 20.8 20.9
Problems: 20.5-7,10,12,15
Chemical Kinetics: The Rates of Chemical Reactions Chapter 21 Rate of a chemical reaction 21.2 Rate law - Rate constant - Reaction order Experimental determination of the rate law Integrated rate laws: 21.3 Zero, first and second order reactions Half-lives Opposing reactions 21.4 Molecularity in elementary reactions 21.6 Temperature dependence of reaction 21.5 rates Consecutive reactions 21.7 Rate-determining step - pre-equilibria Steady-state approximation Kinetic isotope effect Reaction Mechanisms Unimolecular recations (LindemannHinshelwood mechanism Chain reactions
21.8 21.9
Molecular Reaction Dynamics Chapter 22 Collision theory Diffusion-controled reactions Material balance equation Activated complex/Transition state theory Eyring equation - Case of reactants as structureless atoms
22.1 22.2 22.3 22.4 22.4
5
Thermodynamic Analogy Reactions between ions Kinetic salt effect
22.5 22.5
6
