Physical Chemistry I
Purpose of Course showclose
This course will teach you the fundamentals of thermodynamics. Thermodynamics is the study of energy and its transformations. Energy is a physical property that can be converted from one form to another in order to perform work. For example, a stone rolling down a hill is converting gravitational potential energy into the kinetic energy of motion. Thermodynamics can be applied to systems we use every day—such as, for example, heat pumps and refrigerators, internal combustion engines, batteries, and both electrical and mechanical power generators. An awareness of thermodynamics will help you examine other concepts involving chemical processes more quickly and will enable you to understand why many physical phenomena (such as automobile engines or chemical explosives) work the way they do. The knowledge you will gain in this course also will help you determine how much work an object can put out and predict how to optimize an object’s operation.
In this course, you will learn about the laws of thermodynamics; thermodynamic principles; ideal and real gases; the phases of matter; and equations of state and state changes. You also will explore kinetic molecular theory and statistical mechanics, fields that relate the atomiclevel motion of the high number of small particles that make up a system to the average thermodynamic behavior of the system as a whole.
In this course, you will concentrate on the largescale, bulk properties of systems that can be described using the principles of classical mechanics. In addition to these largescale properties, there also are many systems in which smallscale, quantummechanical effects influence or dominate the behavior of the system as a whole. These quantummechanical systems will be explored in Saylor’s CHEM106: Physical Chemistry II.
Course Information showclose
Course Designers: Edward Perry, Brian Dodson, and Karen Duca
Primary Resources: This course makes use of a range of different free, online educational materials. The structure of this course is built around a series of lectures delivered by Dr. Moungi Bawendi and Dr. Keith Nelson at the Massachusetts Institute of Technology titled “Thermodynamics and Kinetics,” made available by the Massachusetts Institute of Technology’s OpenCourseWare project. All the lecture notes for this series, as well as some PowerPoint slideshows on kinetics, are available for bulk download at Massachusetts Institute of Technology’s OpenCourseWare website.
This course also makes primary use of the following online textbooks:
 Dr. Howard DeVoe’s Thermodynamics and Chemistry (2^{nd} ed.) (PDF)
 The University of Arizona: Dr. W.R. Salzman’s “Dynamic Textbook” of Physical Chemistry (HTML)
 Dr. Stephen Lower’s Chem1 Virtual Textbook (HTML)
 Institute of Chemical Technology, Prague: Ing. Anatol Malijevský, CSc. et al.’s Physical Chemistry in Brief (PDF)
Time Commitment: This course should take you a total of approximately 153 hours to complete. Each unit includes a time advisory that lists the amount of time you are expected to spend on each subunit and assignment. These time advisories should help you plan your time accordingly. It may be useful to take a look at the time advisories before beginning this course in order to determine how much time you have over the next few weeks to complete each unit. Then, you can set goals for yourself. For example, Unit 1 should take you approximately 33 hours to complete. Perhaps you can sit down with your calendar and decide to complete Subunit 1.1 (a total of 3 hours) on Monday night, Subunit 1.2 (a total of 12.5 hours) on Tuesday, Wednesday, and Thursday nights, etc.
Tips/Suggestions: For most students, learning thermodynamics is a cumulative process that involves reviewing previously learned material so that foundational concepts are solidified and new ideas and perspectives are discovered with each rereading. Overall, because many of the readings in this course are theoretical and therefore very dense, you may have to reread them—or at least certain sections of them—several times to gain mastery of the subject matter. In particular, some of the resources in this course are assigned more than once so that you can take time to review key concepts and/or focus on a particular aspect of an important text. In addition, some readings in this course have been deemed “optional” and are primarily intended to enrich and reinforce material you already have learned. These optional readings do not include time advisories because they are not essential to your completion of this course.
It is recommended that you take comprehensive notes as you complete each reading and assignment in this course. These notes will serve as a useful tool to you as you review course material and study for the Final Exam.
Throughout this course, every effort has been made to supply informational links to images and discussions of works that you may be unfamiliar with. However, you also are encouraged to briefly research works or concepts discussed in the readings that you have not seen or do not know much about.
Learning Outcomes showclose
 state and apply the laws of thermodynamics;
 perform calculations with ideal and real gases;
 design practical engines by using thermodynamic cycles;
 predict chemical equilibrium and spontaneity of reactions by using thermodynamic principles;
 describe the thermodynamic properties of ideal and real solutions;
 define the phases of matter; describe phase changes; and interpret and/or construct phase diagrams;
 relate macroscopic thermodynamic properties to microscopic states by using the principles of statistical thermodynamics;
 describe reaction rates and perform calculations to determine them;
 relate reaction kinetics to potential reaction mechanisms;
 calculate the temperature dependence of rate constants and relate this calculation to activation energy;
 describe a variety of complex reactions;
 describe catalysis; and
 describe enzymatic catalysis.
Course Requirements showclose
√ have access to a computer;
√ have continuous broadband Internet access;
√ have the ability and permission to install plugins and/or software (e.g., Adobe Reader or Flash)h
√ have the ability to download and save files and documents to a computer;
√ have the ability to open Microsoft Office files and documents (.doc, .docx, .ppt., .xls, etc.);
√ have competency in the English language;
√ have read the Saylor Student Handbook; and
√ have completed at least two semesters of collegelevel introductory chemistry, two semesters of introductory collegelevel physics, and two semesters of calculus, including calculating and working with partial derivatives. For a review of the concepts you will need to have mastered for this course, see Saylor’s CHEM101, CHEM102, PHYS101, PHYS102, MA101, MA102, and MA103.
Unit Outline show close
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Unit 1: An Introduction to Thermodynamics
In this first unit, you will learn about the important foundational thermodynamic concepts and terminology that you will need to know in order to work through the more advanced material presented later in this course. Any thermodynamic system can be defined by the observer or experimenter as having particular properties. For example, a system is called isolated if nothing—neither mass nor energy—can pass through its boundaries. Another type of system is a closed system, in which mass cannot pass through the system boundaries, but energy can. Finally, an open system has completely permeable boundaries; anything can pass in and out of such a system. You also will examine thermodynamic properties and states and review common units, relationships, and conversions that will prove valuable throughout this course. For example, how do you define pressure? How can you make conversions between SI (metric) and imperial (English) units? You may be familiar with some or all of these concepts and tools; if this is the case, you can approach this unit of the course as a refresher and review of information.
Unit 1 Time Advisory show close
Unit 1 Learning Outcomes show close

1.1 A Review of Units, Conversions, and Mathematics
Note: Most students taking physical chemistry already will have learned the information provided in Subunits 1.1.1 and 1.1.2 of this course. You can skim these sections quickly to decide whether you need a further review of this material. If so, you should return to any of the relevant sections of Saylor’s CHEM001, CHEM002, MA101, MA102, CHEM101, and CHEM102 in order to revisit the important foundational topics presented in these courses.

1.1.1 SI Units and NonSI Units
 Reading: The National Institute of Standards and Technology: NIST Reference on Constants, Units, and Uncertainty: International System of Units (SI): “Introduction; Some Useful Definitions,” “SI Base Units; SI Derived Units,” “SI Prefixes,” “Units Outside the SI,” and “Rules and Style Conventions”
Link: The National Institute of Standards and Technology: NIST Reference on Constants, Units, and Uncertainty: International System of Units (SI): “Introduction; Some Useful Definitions”, “SI Base Units; SI Derived Units”, “SI Prefixes”, “Units Outside the SI”, and “Rules and Style Conventions” (HTML)
Instructions: Read these webpages. The information provided on these webpages will help you solidify your knowledge of SI units.
Reading these webpages should take approximately 1 hour.
Terms of Use: Please respect the copyright and terms of use displayed on the webpages above.  Reading: The National Institute of Standards and Technology: NIST Reference on Constants, Units, and Uncertainty: International System of Units (SI): “Definitions of the SI Base Units,” “Background: Historical Context of the SI Base Units,” “International Aspects of the SI,” and “Links to OnLine Unit Conversions”
Link: The National Institute of Standards and Technology: NIST Reference on Constants, Units, and Uncertainty: International System of Units (SI): “Definitions of the SI Base Units”, “Background: Historical Context of the SI Base Units”, “International Aspects of the SI”, and “Links to OnLine Unit Conversions” (HTML)
Instructions: Read these webpages. For the link titled “Background: Historical Context of the SI Base Units,” click on the individual links in the middle of the webpage to read the history of each unit of measurement. For the link titled “Links to OnLine Unit Conversions,” click on the individual links on the webpage to access different online conversion tools.
Note: If you need a deeper review of SI and nonSI units, please refer to Subunit 1.2 of Saylor’s CHEM101.
Reading this material should take approximately 30 minutes.
Terms of Use: Please respect the copyright and terms of use displayed on the webpages above.
 Reading: The National Institute of Standards and Technology: NIST Reference on Constants, Units, and Uncertainty: International System of Units (SI): “Introduction; Some Useful Definitions,” “SI Base Units; SI Derived Units,” “SI Prefixes,” “Units Outside the SI,” and “Rules and Style Conventions”

1.1.2 Units of Energy
 Reading: The American Physical Society’s “Energy Units”
Link: The American Physical Society’s “Energy Units” (HTML)
Instructions: Read the sections of the webpage titled “Introduction” and “Basic Units” in order to review the basic units of energy. As you study thermodynamics, you will make many energy calculations using these units.
Reading this material should take approximately 30 minutes.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.
 Reading: The American Physical Society’s “Energy Units”

1.1.3 Unit Conversions
 Reading: Dr. Stephen Lower’s Chem1 Virtual Textbook: “The Measure of Matter: Understanding the Units of Scientific Measurement”
Link: Dr.Stephen Lower’s Chem1 Virtual Textbook: “The Measure of Matter: Understanding the Units of Scientific Measurement” (HTML)
Instructions: Read all the material in the sections titled “Units & Dimensions,” “Measurement Error,” and “Significant Figures,” available via the hyperlinked menu at the top of the webpage. Carefully examine and interpret the “Concept Map” provided at the end of each section in order to review this material and solidify your knowledge of measurements.
Reading this material should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercial 2.5 License. It is attributed to Dr. Stephen Lower.
 Reading: Dr. Stephen Lower’s Chem1 Virtual Textbook: “The Measure of Matter: Understanding the Units of Scientific Measurement”

1.2 Basic Thermodynamic Concepts and Definitions
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 1: State of a System, 0th Law, Equation of State”
Link: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 1: State of a System, 0th Law, Equation of State”
Also available in:
iTunes U
MP4
Instructions: Watch the video (approximately 47 minutes in length) on the field of thermodynamics and its basic concepts and goals. You will learn about what the term thermodynamics actually means as well as get a sense of the scope of the field and the very important concepts of systems and their surroundings. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States.  Reading: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2nd ed.): “Chapter 1: Introduction and Chapter 2: Systems and Their Properties”
Dr. Howard DeVoe’s Thermodynamics and Chemistry (2^{nd} ed.): “Chapter 1: Introduction and Chapter 2: Systems and Their Properties” (PDF)
Instructions: Navigate to chapter 1, which begins on page 19, and read chapters 1 and 2, ending on page 55, for a general introduction to thermodynamic systems and processes as they are encountered in chemistry. Make sure you set aside time to study in detail the mathematical formulations and sample problems provided on these pages.
Reading this material should take approximately 3 hours.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialNoDervis 3.0 Unported License.
 Optional: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 1: Introduction,” “Chapter 2: Some Concepts and Definitions,” and “Chapter 3: Properties of a Pure Substance”
Link: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 1: Introduction”, “Chapter 2: Some Concepts and Definitions”, and “Chapter 3: Properties of a Pure Substance” (PDF)
Instructions: Read the first three chapters of Dr. Powers’s lecture notes. This optional reading may be used to enrich and reinforce the concepts you explored in the DeVoe reading assignment above, helping you to further develop your understanding of the fundamental properties and characteristics of thermodynamic systems and processes. If you choose to complete this reading, you may also find it helpful to work through the sample exercises provided within these lecture notes.
Terms of Use: This resource is licensed under a Creative Commons Attribution 2.5 Generic license.
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 1: State of a System, 0th Law, Equation of State”

1.2.1 History of the Field: An Empirical Discipline
 Reading: The University of Waterloo: Dr. Richard Culham’s “History of Thermodynamics”
Link: The University of Waterloo: Dr. Richard Culham’s “History of Thermodynamics” (HTML)
Instructions: Click on the individual webpage links and read all seven biographies, which provide a short history of the field by profiling some of its major contributors. Note that the field of thermodynamics was formalized during the nineteenth century, developing as an empirical discipline that was originally concerned with heat energy and how heat could be harnessed to do work. Today, we apply thermodynamics to a range of disciplines, from surface and materials science to bioenergetics.
Reading this material should take approximately 1 hour.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.  Reading: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 1: Introduction”
Link: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 1: Introduction” (PDF)
Instructions: Read chapter 1 of Dr. Powers’s lecture notes. Note that you previously have encountered this chapter in an earlier subunit of this course. As you read this time, focus on the historical development of thermodynamics as a science, the principal participants in this development, and the relationship of thermodynamics to early technological advances during the Industrial Revolution.
Reading this material should take approximately 2 hours.
Terms of Use: This resource is licensed under a Creative Commons Attribution 2.5 Generic license.
 Reading: The University of Waterloo: Dr. Richard Culham’s “History of Thermodynamics”

1.2.2 Thermodynamic Systems: Open, Closed, or Isolated
 Reading: The University of California at Davis: ChemWiki: “A System and Its Surroundings”
Link: The University of California at Davis: ChemWiki: “A System and Its Surroundings” (HTML or PDF)
Instructions: Read the sections titled “Open System,” “Closed System,” and “Isolated System” on the webpage to learn about the types of systems that are defined within thermodynamics. Pay special attention to the photos illustrating these systems, and be sure to work through the practice problems provided in the reading. To access a PDF version of this page, click on the link titled “Make PDF” at the top of the webpage.
Reading this material should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.
 Reading: The University of California at Davis: ChemWiki: “A System and Its Surroundings”

1.2.3 Thermodynamic Equilibrium and the 0th Law
 Reading: The National Aeronautics and Space Administration: “Thermodynamic Equilibrium (Zeroth Law)”
Link: The National Aeronautics and Space Administration: “Thermodynamic Equilibrium (Zeroth Law)” (HTML)
Instructions: View the illustration and explanation of thermodynamic equilibrium provided on the webpage. This illustration demonstrates how thermodynamic equilibrium allows us to establish a macroscopic view of temperature.
Reading this material should take approximately 30 minutes.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.
 Reading: The National Aeronautics and Space Administration: “Thermodynamic Equilibrium (Zeroth Law)”

1.2.4 Thermodynamic Processes: Changes of State and Path Dependence
 Reading: The University of California at Davis: ChemWiki: “State Functions”
Link: The University of California at Davis: ChemWiki: “State Functions” (HMTL or PDF)
Instructions: Read the sections titled “Introduction,” “Mathematics of State Functions,” and “State Functions vs. Path Functions” on the webpage. Thermodynamics deals primarily with state functions, which are independent of the path taken to reach them. Consider all the examples provided in the text and to work through the sample problems provided at the end of the reading (you can check your answers at the bottom of the webpage). To access a PDF version of this article, click on the link titled “Make PDF” at the top of the webpage.
Reading this material should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.
 Reading: The University of California at Davis: ChemWiki: “State Functions”

1.3 Properties of Gases, Work, and Heat
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 2: Work, Heat, First Law”
Link: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 2: Work, Heat, First Law”
Also available in:
iTunesU
MP4
Instructions: Watch the video (approximately 51 minutes in length) about equations of state for ideal and real gases, work, heat, and heat capacity. The last part of this video introduces the first law of thermodynamics, which you will explore in more detail in Unit 2 of this course. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1.5 hours.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 2: Work, Heat, First Law”

1.3.1 Ideal Gases vs. Real Gases
 Reading: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 1: Properties of Gases,” “Lecture 2: The Gas Laws,” “Lecture 3: Kinetic Model of Gases,” and “Lecture 4: Real Gases”
Link: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes:“Lecture 1: Properties of Gases”, “Lecture 2: The Gas Laws”, “Lecture 3: Kinetic Model of Gases”, and “Lecture 4: Real Gases”(PDF)
Instructions: Read the selections from Dr. Schurko’s course notes. Consider the data shown in the figures and sketches in this reading, and focus on developing an understanding of how the equationsofstate for ideal and real gases represent their PVT properties. Also, be sure to work through the kineticmolecular theory of gases, as it is formulated in lecture 3, and be able to derive the idealgas equationofstate based on this theory.
Reading this material should take approximately 3 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpages above.
 Reading: The University of Arizona: Dr. W. Ron Salzman’s “Chemical Thermodynamics”
Link: The University of Arizona: Dr. W. Ron Salzman’s “Chemical Thermodynamics” (HTML)
Instructions: Click on the individual webpage links and read the first eight sections of the notes (from “Introduction” to “Work, Energy, the First Law”). Read each section, working through all the equations presented in the reading.
Reading this material should take approximately 3 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.  Optional: The University of Oxford: Dr. Claire Vallance’s “Properties of Gases” Lecture Notes
Link: The University of Oxford: Dr. Claire Vallance’s “Properties of Gases”Lecture Notes (PDF)
Instructions: Read through the set of lecture notes, which address both macroscopic and microscopic properties of gases under a variety of PVT conditions. The presentations found in this optional reading may be used to enrich and reinforce concepts you have explored in the previously assigned Unit 1.3.1 readings, above. If you choose to complete this reading, please pay special attention to the state variables and the equations of state that govern gas properties, and be sure to acquire a familiarity with how the equations of state are derived from either empirical data or theoretical models of molecular behavior.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.
 Reading: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 1: Properties of Gases,” “Lecture 2: The Gas Laws,” “Lecture 3: Kinetic Model of Gases,” and “Lecture 4: Real Gases”

1.3.2 Work: Processes for Changing the Energy of a System
 Reading: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 5: Introduction to Thermodynamics” and “Lecture 6: Work, Heat and Energy”
Link: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 5: Introduction to Thermodynamics”and “Lecture 6: Work and Heat” (PDF)
Instructions: Read both sets of notes, paying special attention to how thermodynamic work is defined and manifested in various types of thermodynamic processes.
Reading this material should take approximately 3 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpages above.
 Reading: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 5: Introduction to Thermodynamics” and “Lecture 6: Work, Heat and Energy”

1.3.3 Heat: Energy Transfers Driven by Temperature Differences
 Reading: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 4: Work and Heat”
Link: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 4: Work and Heat” (PDF)
Instructions: Read chapter 4 of Dr. Powers’s lecture notes. Work through all the equations presented, paying particular attention to the formulation of thermodynamic work and heat as path functions (as opposed to state functions).
Reading this material should take approximately 3 hours.
Terms of Use: This resource is licensed under a Creative Commons Attribution 2.5 Generic license.  Reading: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 6: Work and Heat,” “Lecture 7: Enthalpy and Adiabatic Changes,” “Lecture 8: Thermochemistry”
Link: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 6: Work and Heat”,“Lecture 7: Enthalpy and Adiabatic Changes”, “Lecture 8: Thermochemistry” (PDF)
Instructions: Note that you previously have encountered the lecture 6 notes in an earlier subunit of this course. Reread the lecture 6 notes (“Work and Heat”) followed by the notes for lectures 7 and 8. Focus on how thermodynamic heat is defined and manifested in various types of thermodynamic processes, and how heat transactions are measured. The heat given off or taken up in chemical reactions is addressed in lecture 8 (“Thermochemistry”).
Reading this material should take approximately 3 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpages above.
 Reading: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 4: Work and Heat”

1.3.4 Heat Capacity: Linking Heat to Temperature Changes
 Reading: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2nd ed.): “Chapter 3: The First Law”
Link: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2^{nd} ed.): “Chapter 3: The First Law” (PDF)
Instructions: Navigate to chapter 3, which begins on page 56. In this reading you willacquire an understanding of how heat capacity quantities are defined and measured. You also will learn about their practical significance in the design and uses of material systems.
Reading this material should take approximately 4 hours.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialNoDervis 3.0 Unported License.
 Optional: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 6: Work Heat”
Link: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 6: Work and Heat” (PDF)
Instructions: Note that you already have encountered these lecture notes in earlier subunits; at this point in the course, your review of this material is optional and may be used to enrich and reinforce the concepts you have explored so far. If you choose to complete this optional reading, pay special attention to the excellent sections that deal with heat capacity properties (discussed close to the end of the lecture notes).
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialNoDervis 3.0 Unported License.
 Reading: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2nd ed.): “Chapter 3: The First Law”

Unit 2: The First Law of Thermodynamics
The first law of thermodynamics states, simply, that energy is conserved. While energy can be changed from one form to another—say, by converting chemical energy into heat by burning a candle and then converting that heat into mechanical work by heating a gas within a balloon—energy cannot be gained or lost once all transfers and conversions of energy are accounted for.
Unit 2 Time Advisory show close
Unit 2 Learning Outcomes show close

2.1 Internal Energy and Expansion Work
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Robert Field, Dr. Moungi Bawendi, and Dr. Keith Nelson’s “Lecture 3: Internal Energy, Expansion Work”
Link: The Massachusetts Institute of Technology OpenCourseWare: Dr. Robert Field, Dr. Moungi Bawendi, and Dr. Keith Nelson’s “Lecture 3: Internal Energy, Expansion Work”
Also available in:
iTunesU
MP4
Instructions: Watch the video (approximately 52 minutes long), in which you will further explore the concept of heat capacity, which was introduced in Unit 1 of this course. You also will learn more about the first law of thermodynamics, discover how gases can do work under different conditions, and see how to maximize the work that gases can do. You will also learn about an important state function: U, the internal energy. You can find the lecture notes for this video here(PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.  Reading: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2nd ed.): “Chapter 3: The First Law”
Link: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2^{nd} ed.): “Chapter 3: The First Law”(PDF)
Instructions: Read chapter 3, beginning on page 56. Note that you already have encountered this chapter earlier in this course; this time, reread itfor an overview of the first law of thermodynamics. Be sure to work through the details of each section in the chapter, paying special attention to the mathematical formulation of first law properties. You should also work through the problems at the end of chapter 3 to gauge your understanding of the material in this chapter.
Reading this material and completing the problems should take approximately 3 hours.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialNoDervis 3.0 Unported License.
 Reading: McGill University: Dr. David Ronis’s “Notes on the First Law of Thermodynamics Chemistry 223”
Link: McGill University: Dr. David Ronis’s “Notes on the First Law of Thermodynamics Chemistry 223” (PDF)
Instructions: Read these notes. This reading offers particularly clear illustrations of mechanical work and the differences between reversible and irreversible (or spontaneous) thermodynamic processes. At this point in the course, you should be able to work through the derivations of all the equations presented in the reading and feel comfortable with the underlying differential, multivariate calculus. If you are still struggling with the mathematical aspects of thermodynamics, you may find it useful to read these notes again. The mathematical formulations and manipulations found in Dr. Ronis’s notes are presented with special care and clarity.
Reading this material should take approximately 2 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.  Reading: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 9: The First Law: Machinery”
Link: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 9: The First Law: Machinery” (PDF)
Instructions: Read the course material. Be sure to carefully review all the sketches.
Reading this material should takeapproximately 3 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.  Optional: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 5: The First Law of Thermodynamics”
Link: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 5: The First Law of Thermodynamics” (PDF)
Instructions: Note that this reading is optional and primarily intended for enrichment and review purposes. If you choose to complete this reading, compare the material presented in these lecture notes with the concepts you have explored in the previous assignments in this subunit.
Terms of Use: This resource is licensed under a Creative Commons Attribution 2.5 Generic license.
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Robert Field, Dr. Moungi Bawendi, and Dr. Keith Nelson’s “Lecture 3: Internal Energy, Expansion Work”

2.2 Enthalpy
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 4: Enthalpy”
Link: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 4: Enthalpy”
Also available in:
iTunesU
MP4
Instructions: Watch the video (approximately 55 minutes in length) to learn about the important state function enthalpy, H, which allows you to know the heat flow into or out of a system. ΔH = Δ(U + PV) = q_{p}. You also will explore the dependence of the enthalpy on P and V as well as look at the JouleThompson experiment. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 4: Enthalpy”

2.3 Thermodynamics of Adiabatic Processes
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 5: Adiabatic Changes” and “Lecture 6: Thermochemistry”
Link: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 5: Adiabatic Changes” and “Lecture 6: Thermochemistry”
Also available in:
iTunesU (Lecture 5)
MP4 (Lecture 5)
iTunesU (Lecture 6)
MP4 (Lecture 6)
Instructions: Watch the two videos (approximately 50 minutes and 52 minutes in length, respectively) to learn about changes of state that occur for ideal gases undergoing various thermodynamic processes along, for example, isothermal, isobaric, and adiabatic paths. This discussion leads us to the topic of thermodynamic cycles, which we can exploit to do work. In these videos you also will explore the topic of entropy and see the first application of thermodynamic principles and analysis to nongaseous systems. You can find the lecture notes for “Lecture 5: Adiabatic Changes” here (PDF) and those for “Lecture 6: Thermochemistry” here (PDF).
Watching this lecture should take approximately 2 hours.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 5: Adiabatic Changes” and “Lecture 6: Thermochemistry”

Unit 3: Application of the First Law of Thermodynamics
In the third unit of this course, you will learn about measuring thermodynamic properties for reactions and exploring the fundamentals of how heat engines operate. Steam engines, internal combustion engines, diesel engines, jet engines, and rocket engines are all heat engines, as are refrigerators and heat pumps. In ideal cycle analysis, the operations of these engines will be treated as thermodynamic cycles, and you will use the first law of thermodynamics to calculate their cycle efficiency and work output. While such methods overlook effects that happen in nonideal systems, this basic approach can be adapted to treat more realistic engines. Moreover, you can use thermodynamic cycles (Hess’s law) to arrive at values for thermodynamic state changes that cannot easily be measured by using the actual path the reaction takes. Such state changes can be computed by using cycles involving quantities that you can measure along different paths.
Unit 3 Time Advisory show close
Unit 3 Learning Outcomes show close

3.1 Calorimetry: Measuring the Enthalpy
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 7: Calorimetry”
Link: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 7: Calorimetry”
Also available in:
iTunesU
MP4
Instructions: Watch the video (approximately 55 minutes long) to see how one uses calorimetry to obtain the enthalpy of the formation of compounds and the enthalpy of reactions. In fact, many thermochemical parameters can be measured in a calorimeter. In situations in which you cannot measure enthalpy directly, Hess’s law allows you to use a thermodynamic cycle (taking a different path) to find it. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.  Reading: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 8: Thermochemistry”
Link: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 8: Thermochemistry” (PDF)
Instructions: Read the notes. Note that these notes have been assigned previously in this course; as you read this time, focus on the detailed description of how the enthalpy changes that accompany chemical processes are defined and measured, and how the acquired enthalpy data may be analyzed within the context of the first law of thermodynamics. Also be sure to work through all the examples provided in the reading.
Reading this material should take approximately 2 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.  Reading: Dr. David Ronis’s “Thermochemistry”
Link: McGill University: Dr. David Ronis’s “Thermochemistry” (PDF)
Instructions: Read Dr. Ronis’s lecture notes on thermochemistry. This reading focuses on enthalpy changes that accompany chemical reactions. Read through the notes and work through all the illustrations and examples presented in the reading.
Reading this material should take approximately 3 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 7: Calorimetry”

3.2 Heat Engines
 Web Media: Georgia State University: Dr. Rod Nave’s “Heat Engine Concepts”
Link: Georgia State University: Dr. Rod Nave’s “Heat Engine Concepts” (HTML)
Instructions: Review the chart on the webpage to explore the concept of heat engines. Explore the links on this webpage to see some practical engines based on thermodynamic cycles. Focus on getting a sense of these engines and how they work. You will revisit them in more detail in Unit 4 of this course, at which point you will perform calculations with them.
Completing this web media assignment should take approximately 1 hour.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.
 Web Media: Georgia State University: Dr. Rod Nave’s “Heat Engine Concepts”

3.3 The Carnot Cycle
 Web Media: Georgia State University: Dr. Rod Nave’s “Carnot Cycle”
Link: Georgia State University: Dr. Rod Nave’s “Carnot Cycle” (HTML)
Instructions: Read the webpage, which discusses the most efficient thermodynamic engine possible. It is based on a cycle with two isothermal and two adiabatic paths. Using the embedded formula on the webpage, you can input two temperatures to obtain the Carnot efficiency for that engine. Are you surprised by what you see?
Completing this web media assignment should take approximately 1 hour.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.
 Web Media: Georgia State University: Dr. Rod Nave’s “Carnot Cycle”

3.4 The Otto Cycle (Internal Combustion)
 Web Media: Georgia State University: Dr. Rod Nave’s “The Otto Cycle”
Link: Georgia State University: Dr. Rod Nave’s “The Otto Cycle” (HTML)
Instructions: Click on the link and read the section titled “Step through engine cycle” to view a short web schematic that shows you how a car’s engine works. Continue clicking on the “Step through engine cycle” link in order to view each part of the schematic, paying special attention to the path taken around the cycle.
Completing this web media assignment should take approximately 1 hour.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.
 Web Media: Georgia State University: Dr. Rod Nave’s “The Otto Cycle”

3.5 Refrigerators and Heat Pumps
 Reading: Georgia State University: Dr. Rod Nave’s “Refrigerator” and “Heat Pump”
Link: Georgia State University: Dr. Rod Nave’s “Refrigerator”and “Heat Pump” (HTML)
Instructions: Read the two sections titled “Refrigerator” and “Heat Pump” to learn about heat flow from a hotter to a colder region and how refrigerators and heat pumps work. Also take time to read the “Coefficient of Performance” section on the “Heat Pumps” webpage. Work through each of the calculations illustrated in these sections and make sure you understand how the calculations are set up and executed.
Reading this material should take approximately 2 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpages above.
 Reading: Georgia State University: Dr. Rod Nave’s “Refrigerator” and “Heat Pump”

Unit 4: The Second Law of Thermodynamics
The second law of thermodynamics reflects the universal observation that moving things eventually stop and broken eggs never can become whole again. The law expresses this observation in terms of a thermodynamic parameter known as entropy, which is a measure of the disorder in a system. Renowned British physicist Sir Arthur Eddington believed that the second law of thermodynamics is the most fundamental law of science and that, at its foundation, it is a far broader concept than is required by the narrow physical laws of our particular universe.
Unit 4 Time Advisory show close
Unit 4 Learning Outcomes show close

4.1 The Second Law of Thermodynamics
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 8: Second Law”
Link: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 8: Second Law”
Also available in:
iTunesU
MP4
Instructions: Watch the video (approximately 50 minutes in length) on the second law of thermodynamics. This lecture begins with a discussion of the relationship between enthalpies of formation and bond energies, following up on the lectures on thermochemistry. You also will learn about how the second law complements the first. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.  Reading: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2nd ed.): “Chapter 4: The Second Law”
Link: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2^{nd} ed.): “Chapter 4: The Second Law” (PDF)
Instructions: Navigate to chapter 4, which begins on page 102, and read and work through the chapter, including completing the problems at the end of the chapter. The material in this chapter provides an exceptional foundation for studying the remaining concepts in this subunit of the course. Be sure to work through all of chapter 4 before moving on to the subsequent assignments in this unit.
Reading this material should take approximately 4 hours.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialNoDervis 3.0 Unported License.
 Reading: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 10: The Second Law: The Concepts” and “Lecture 11: Entropy Changes & Processes”
Link: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 10: The Second Law: The Concepts”and “Lecture 11: Entropy Changes & Processes” (PDF)
Instructions: Read these notes, but pay particular attention to the illustrations shown and consider how they are related to the accompanying mathematical formulation of the second law of thermodynamics.
Reading this material should take approximately 3 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpages above.  Optional: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 7: The Second Law of Thermodynamics” and “Chapter 8: Entropy” (PDF)
Link: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 7: The Second Law of Thermodynamics”and “Chapter 8: Entropy” (PDF)
Instructions: Read Dr. Powers’s lecture notes. You may find this optional reading especially useful for helping you to understand the various statements of the second law that are found in the thermodynamics literature.
Terms of Use: This resource is licensed under a Creative Commons Attribution 2.5 Generic license.  Optional: McGill University: Dr. David Ronis’s “The Second Law of Thermodynamics” (PDF)
Link: McGill University: Dr. David Ronis’s “The Second Law of Thermodynamics” (PDF)
Instructions: Read Dr. Ronis’s brief handout. This optional reading provides you with a concise summary of principles related to the second law of thermodynamics.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 8: Second Law”

4.2 Entropy and the Clausius Inequality
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 9: Entropy and the Clausius Inequality”
Link: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 9: Entropy and the Clausius Inequality”
Also available in:
iTunesU
MP4
Instructions: Watch this video (approximately 50 minutes in length). In this lecture, you will revisit some of the thermodynamic cycles and their corresponding engines—concepts you saw in Unit 3 of this course. You also will learn about entropy around thermodynamic cycles in which there are reversible and irreversible paths involved. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.  Reading: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 8: Entropy”
Link: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 8: Entropy” (PDF)
Instructions: Read through chapter 8 of Dr. Powers’s lecture notes. Note that this chapter has been assigned previously in this course; as you review the material this time, be sure to work through all the example problems provided in the text.
Reading this material should take approximately 3 hours.
Terms of Use: This resource is licensed under a Creative Commons Attribution 2.5 Generic license.  Reading: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 11: Entropy Changes & Processes” (PDF)
Link: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 11: Entropy Changes & Processes” (PDF)
Instructions: Read Dr. Schurko’s course material. Note that you have been assigned this reading previously in this course; as you read this time, focus on understanding how entropy changes are determined for various kinds of physical and chemical processes. Read the material and be sure to work through all the exercises and example problems provided in the text.
Reading this material should take approximately 2 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.  Optional: McGill University: Dr. David Ronis’s “Why the Efﬁciency of a Carnot Engine Is Independent of the Kind of Working Material” and “The Clausius Inequality and the Mathematical Statement of the Second Law of Thermodynmamics”
Link: McGill University: Dr. David Ronis’s “Why the Efﬁciency of a Carnot Engine Is Independent of the Kind of Working Material”and “The Clausius Inequality and the Mathematical Statement of the Second Law of Thermodynmamics” (PDF)
Instructions: Read Dr. Ronis’s course notes. Please note that this reading is optional. The first handout offers a concise description of the Carnot heat engine and a thermodynamic analysis of its operation. The second handout provides you with an overview of the profound significance of the Clausius inequality.
Terms of Use: Please respect the copyright and terms of use displayed on the webpages above.
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 9: Entropy and the Clausius Inequality”

4.3 Entropy and Irreversibility
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 10: Entropy and Irreversibility”
Link: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 10: Entropy and Irreversibility”
Also available in:
iTunesU
MP4
Instructions: Watch the video (approximately 53 minutes in length), which continues entropy calculations around cycles that involve reversible and irreversible processes, with particular emphasis on the direction of spontaneous change. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.  Reading: Connexions: “Entropy and the Second Law of Thermodynamics: Disorder and the Unavailability of Energy”
Link: Connexions: “Entropy and the Second Law of Thermodynamics: Disorder and the Unavailability of Energy” (HTML)
Instructions: Read the webpage. This source has a particularly good set of questions and problems to be addressed. Work through all the questions and problems in this reading—both the conceptual problems and those requiring numerical calculations.
Reading this material should take approximately 2 hours.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialNoDervis 3.0 Unported License.
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 10: Entropy and Irreversibility”

4.4 Maxwell’s Demon
 Reading: The Institute of Mathematical Sciences: Dr. Sitabhra Sinha, Brajendra Kumar Singh, and Albert Smith’s “Maxwell’s Demon”
Link: The Institute of Mathematical Sciences: Dr. Sitabhra Sinha, Brajendra Kumar Singh, and Albert Smith’s “Maxwell’s Demon” (Java)
Instructions: Explore this Java applet, which is based on a thought experiment that Scottish physicist James Clerk Maxwell devised nearly 150 years ago in an attempt to disprove the second law of thermodynamics. Although Maxwell did not succeed, his idea raised interesting questions about the relationship between information and entropy. As you explore the applet, try to separate the fast from the slow molecules. Are you violating the second law of thermodynamics when you attempt this? No, because the amount of information needed to do this separation requires quite a large energy input!
Completing this web media assignment should take approximately 1 hour.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.
 Reading: The Institute of Mathematical Sciences: Dr. Sitabhra Sinha, Brajendra Kumar Singh, and Albert Smith’s “Maxwell’s Demon”

4.5 Statistical Entropy: Microscopic vs. Macroscopic Viewpoints
 Reading: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 8: Entropy (Sections 8.9 and 8.10)”
Link: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 8: Entropy (Sections 8.9 and 8.10)” (PDF)
Instructions: Review chapter 8 of Dr. Powers’s lecture notes, which have been assigned previously in this course. As you read this time, focus specifically on sections 8.9 (“Probablistic approach to entropy”) and 8.10 (“Summary statement of thermodynamics”) of the chapter. Most of the material in this reading will be familiar to you from previous assignments in this course. However, whereas previously the emphasis was on the definition and interpretation of entropy as a macroscopic property of state, here the entropy state function is defined in terms of microscopic material properties.
Reading this material should take approximately 1.5 hours.
Terms of Use: This resource is licensed under a Creative Commons Attribution 2.5 Generic license.  Reading: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2nd ed.): “Chapter 4: The Second Law (Section 4.8)”
Link: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2^{nd} ed.): “Chapter 4: The Second Law (Section 4.8)” (PDF)
Instructions: Navigate to section 4.8, titled “The Statistical Interpretation of Entropy,” on page 130, and read through page 132. Please note that chapter 4 of this textbook has been previously assigned in this course; as you review section 4.8 this time, note that only the conceptual basis of the term statistical entropy is addressed here. You will encounter a more rigorous treatment of statistical entropy in Unit 9 of this course.
Reading this material should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialNoDervis 3.0 Unported License.
 Reading: Tim Thompson’s “Adventures in Entropy”
Link: Tim Thompson’s “Adventures in Entropy” (HTML)
Instructions: Access and peruse the hyperlinked material on this website. The material presented here will help you gain some exposure to “thinking outside the box” about thermodynamic entropy. The information on this site is intellectually sound, enormously thoughtprovoking, and one heck of a lot of fun to ponder.
Reading this material should take approximately 1 hour.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.
 Reading: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 8: Entropy (Sections 8.9 and 8.10)”

Unit 5: The Third Law of Thermodynamics
The third law of thermodynamics is the odd man out, so to speak. The 0th (zeroth) law states that two bodies having the same temperature as a third have the same temperature as each other; the first law states that energy is conserved; and the second law states that heat cannot flow from a cold object to a hot object. These principles seem reasonably clear, although not beyond dispute. However, the third law is not as straightforward. It states that as a system approaches absolute zero, the entropy of the system, in turn, approaches a minimum value. However, despite the fact that the interpretation of the third law becomes rather confusing when quantum effects are included, there is no experimental example or reasonable theoretical result that violates the third law.
Unit 5 Time Advisory show close
Unit 5 Learning Outcomes show close

5.1 Fundamental Equation, Absolute Entropy, and the Third Law
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 11: Fundamental Equation, Absolute S, Third Law”
Link: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 11: Fundamental Equation, Absolute S, Third Law”
Also available in:
iTunesU
MP4
Instructions: Watch the video (approximately 52 minutes long), which describes the third law of thermodynamics and the definition of absolute entropy. Although we can never reach absolute zero of temperature, it is an important reference point for defining an absolute entropy scale. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.  Reading: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 12: Entropy Changes and Processes”
Link: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 12: Entropy Changes and Processes” (PDF)
Instructions: Read Dr. Schurko’s course notes. Read the set of notes, but pay special attention to the first part, which deals with the third law of thermodynamics.
Reading this material should take approximately 1.5 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.  Reading: McGill University: Dr. David Ronis’s “Entropy Calculations and the Third Law of Thermodynamics”
Link: McGill University: Dr. David Ronis’s “Entropy Calculations and the Third Law of Thermodynamics” (PDF)
Instructions: Read the online PDF of Dr. Ronis’s handout. This reading gives you a short, concise description of the third law of thermodynamics. It also presents several examples of how absolute thirdlaw entropies are determined.
Reading this material should take approximately 1.5 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.  Reading: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2nd ed.): “Chapter 6: The Third Law and Cryogenics”
Link: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2^{nd} ed.): “Chapter 6: The Third Law and Cryogenics” (PDF)
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 11: Fundamental Equation, Absolute S, Third Law”

5.2 Entropy of Mixing
 Reading: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 8: Entropy”
Link: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 8: Entropy (Section 8.8)” (PDF)
Instructions: Read and review chapter 8, which has been assigned earlier in this course. As you read this time, focus specifically on section 8.8, titled “Entropy of thermomechanical mixing,” beginning on page 261. This section of the text focuses on the entropyofmixing phenomenon. The entropyofmixing phenomenon accounts for the spontaneous mixing of two or more substances under conditions in which the mixing process is isoenergetic.
Reading this material should take approximately 2 hours.
Terms of Use: This resource is licensed under a Creative Commons Attribution 2.5 Generic license.
 Reading: The University of Notre Dame OpenCourseWare: Dr. Joseph M. Powers’s Lecture Notes on Thermodynamics: “Chapter 8: Entropy”

Unit 6: Spontaneous Changes, Chemical Potential, and Equilibrium
A chemical system is in equilibrium when the activities and concentrations of the reactants and products do not change with time. This usually comes about when the forward reaction rate and the reverse reaction rate are the same. In this situation, known as dynamic equilibrium, chemical reactions are still in progress, and specific atoms move between molecules, but the total amount of the various chemical species remains the same. As we will see, a chemical system in dynamic equilibrium tends to remain in equilibrium even when it is disturbed by a change in the conditions associated with the original equilibrium. Equilibrium is associated with a global minimum in the relevant free energy function. Metastability is associated with local minima in the free energy that are separated from the global minimum by activation energy barriers. Many chemical processes lead to metastable states rather than an equilibrium state, thus allowing for the possibility of further, spontaneous change (in the direction of a true, thermodynamic equilibrium state). Controlling and changing chemical equilibria is perhaps the most important skill that a chemist must develop.
Unit 6 Time Advisory show close
Unit 6 Learning Outcomes show close

6.1 Spontaneous Changes in Chemical Systems
 Reading: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2nd ed.): “Chapter 5: Thermodynamic Potentials”
Link: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2^{nd} ed.): “Chapter 5: Thermodynamic Potentials” (PDF)
Instructions: Navigate to chapter 5, starting on page 135, and read the chapter through page 149. Pay special attention to section 5.8, titled “Criteria for Spontaneity,” beginning on page 145. Also, be sure to work through the problems presented at the end of the chapter. Note that the criteria for spontaneous change in the thermodynamic state of a system depend on both the compositional and PVT (physical) variables of the system, as well as whether the system is isolated, closed, or open with respect to its boundary with surroundings. Pay very close attention to how the criteria for spontaneous change are expressed in terms of changes in various thermodynamic state functions.
Reading this material should take approximately 4 hours.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialNoDervis 3.0 Unported License.
 Optional: Dr. Stephen Lower’s Chem1 Virtual Textbook: “Thermodynamics of Chemical Equilibrium: All about Entropy and Free Energy (Sections 13)”
Link: Dr. Stephen Lower’s Chem1 Virtual Textbook: “Thermodynamics of Chemical Equilibrium: All about Entropy and Free Energy (Sections 13)” (HTML)
Instructions: Read the material presented in sections 13 (from “Energy spreading drives spontaneous change” to “The Second Law and the availability of energy”) of the webpage, including all the hyperlinked material within each section. Note that this reading is optional, but it will provide you with an excellent review of the thermodynamic concepts and principles you have learned thus far (and will most likely deepen your understanding of thermodynamics as an applied science). If you choose to complete this reading, you may also wish to peruse the supplementary material provided via the related links found at the bottom of the webpage.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialNoDervis 3.0 Unported License.
 Lecture: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 12: Criteria for Spontaneous Change”
Link: The Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 12: Criteria for Spontaneous Change”
Also available in:
iTunesU
MP4
Instructions: Watch the video (approximately 48 minutes in length) to learn about how we judge whether a system is moving spontaneously toward an equilibrium state or is already there. You also will learn about the Gibbs and Helmholtz free energies, which are ways of predicting spontaneity under different conditions. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.  Reading: McGill University: Dr. David Ronis’s “Thermodynamic Stability: Free Energy and Chemical Equilibrium” (PDF)
Link: McGill University: Dr. David Ronis’s “Thermodynamic Stability: Free Energy and Chemical Equilibrium” (PDF)
Instructions: Read the online PDF of Dr. Ronis’s handout. Read the handout to acquire an understanding of the thermodynamic criteria for a spontaneous change of state in a material system.
Reading this material should take approximately 3 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.
 Reading: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2nd ed.): “Chapter 5: Thermodynamic Potentials”

6.2 Gibbs Free Energy
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 13: Gibbs Free Energy”
Link: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 13: Gibbs Free Energy”
Also available in:
iTunesU
MP4
Instructions: Watch the video (approximately 50 minutes in length) to learn about what is arguably the most important thermodynamic function in chemistry: the Gibbs free energy. This function helps us determine the direction of spontaneity in any chemical reaction. You can find the lecture notes for this video here (PDF).
Watching this lecture should take you approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.  Reading: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2nd ed.): “Chapter 5: Thermodynamic Potentials”
Link: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2^{nd} ed.): “Chapter 5: Thermodynamic Potentials” (PDF)
Instructions: Navigate to chapter 5, titled “Thermodynamic Potentials,” starting on page 135, and read the chapter through page 149. Note that this chapter has been assigned earlier in this course; as you read this time, carefully review how the thermodynamic freeenergy state functions (i.e., the Helmholtz and Gibbs functions) are defined and used in thermodynamic analyses and calculations.
Reading this material should take approximately 2 hours.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialNoDervis 3.0 Unported License.
 Reading: Dr. Stephen Lower’s Chem1 Virtual Textbook: “Thermodynamics of Chemical Equilibrium: All about Entropy and Free Energy (Sections 46)”
Link: Dr. Stephen Lower’s Chem1 Virtual Textbook: “Thermodynamics of Chemical Equilibrium: All about Entropy and Free Energy (Sections 46)” (HTML)
Instructions: Read sections 46 of the webpage (from “Free energy and the Gibbs function” to “Some applications of entropy and free energy”), including all the hyperlinked material within each section. The subject matter presented in sections 46 assumes familiarity with the material in sections 13, which you read in an earlier assignment in this course. You may wish to refer back to this resource as you progress through the remaining units of this course, as it provides an excellent review of important thermodynamic concepts and principles.
Reading this material should take approximately 2 hours.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialNoDervis 3.0 Unported License.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 13: Gibbs Free Energy”

6.3 Multicomponent Systems and Chemical Potential
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 14: Multicomponent Systems, Chemical Potential”
Link: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 14: Multicomponent Systems, Chemical Potential”
Also available in:
iTunesU
MP4
Instructions: Watch the video (approximately 47 minutes in length) to learn about how to calculate the Gibbs free energy per mole of systems with multiple components. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.  Reading: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2nd ed.): “Chapter 12: Equilibrium Conditions in Multicomponent Systems”
Link: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2^{nd} ed.): “Chapter 12: Equilibrium Conditions in Multicomponent Systems” (PDF)
Instructions: Navigate to chapter 12, starting on page 367, and read the chapter through page 418. Be sure to work through all the practice problems at the end of the chapter.
Reading this material should take approximately 4 hours.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialNoDervis 3.0 Unported License.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 14: Multicomponent Systems, Chemical Potential”

6.4 Le Chatelier’s Principle
 Lecture: Academic Earth: The University of California at Berkeley: Dr. Angelica Stacy’s “How Pushy: Le Chatelier’s Principle”
Link: Academic Earth: The University of California at Berkeley: Dr. Angelica Stacy’s “How Pushy: Le Chatelier’s Principle” (Adobe Flash)
Instructions: Watch the video (approximately 50 minutes in length) to learn about how Le Chatelier’s principle can qualitatively predict the shift in equilibrium under different kinds of perturbations.
Watching this lecture should take approximately 1 hour.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.
 Lecture: Academic Earth: The University of California at Berkeley: Dr. Angelica Stacy’s “How Pushy: Le Chatelier’s Principle”

6.5 Chemical Equilibrium
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 15: Chemical Equilibrium”
Link: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 15: Chemical Equilibrium”
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Instructions: Watch the video (approximately 51 minutes in length) to derive the relationship among Gibbs free energy, chemical potential, and equilibrium. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.  Reading: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2nd ed.): “Chapter 11: Reactions and Other Chemical Processes” and “Chapter 12: Equilibrium Conditions in Multicomponent Systems”
Link: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2^{nd} ed.): “Chapter 11: Reactions and Other Chemical Processes” and “Chapter 12: Equilibrium Conditions in Multicomponent Systems” (PDF)
Instructions: Navigate to chapter 11, starting on page 303. Read all of chapters 11 and 12, through page 418. Be sure to work through all the practice problems at the end of these chapters. Note that chapter 12 has been assigned earlier in this course; as you read this time, focus on changes in the thermodynamic properties that occur as a consequence of changes in compositional variables attendant to a chemical reaction (as opposed to changes in physical variables).
Reading this material should take approximately 4 hours.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialNoDervis 3.0 Unported License.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 15: Chemical Equilibrium”

6.6 The Effect of Temperature and Pressure on Chemical Equilibrium
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 16: Temperature, Pressure and Kp”
Link: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 16: Temperature, Pressure and K_{p}”
Also available in:
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Instructions: Watch the video (approximately 52 minutes in length) to learn how to express the equilibrium constant in two ways: K_{p}, which is independent of total pressure; and K_{x}, which depends on pressure. You also will see a more quantitative presentation of Le Chatelier’s principle, as well as assess how varying temperature, pressure, and volume affect the chemical potential and, thus, the equilibrium position of a system. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 16: Temperature, Pressure and Kp”

6.7 Biological Applications of Equilibrium
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 17: Equilibrium: Application to Drug Design”
Link: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 17: Equilibrium: Application to Drug Design”
Also available in:
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Instructions: Watch the video (approximately 32 minutes in length) to see an interesting modern application of equilibrium thermodynamics in the field of drug discovery You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 30 minutes.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 17: Equilibrium: Application to Drug Design”

Unit 7: Phase Changes and Phase Equilibria
Phase changes deal with physical transformations of pure substances. An important kind of equilibrium is one in which the pure substance exists in two or more states of matter. We exploit this property in many ways in all branches of science. For example, in chemistry experiments we often freeze cells in liquid nitrogen vapor, which is in equilibrium with its liquid in the storage tank. In this unit, you will learn how to generate phase diagrams and perform calculations related to energy requirements for phase changes.
Unit 7 Time Advisory show close
Unit 7 Learning Outcomes show close

7.1 A Review of Phase Changes
 Lecture: Academic Earth: The University of California at Berkeley: Dr. Angelica Stacy’s “It’s Just a Phase: Phase Changes”
Link: Academic Earth: The University of California at Berkeley: Dr. Angelica Stacy’s “It’s Just a Phase: Phase Changes” (Adobe Flash)
Instructions: Watch the video (approximately 52 minutes in length) to learn about the different phases of matter and the conditions under which they may coexist or transform into one another.
Watching this lecture should take approximately 1 hour.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.  Reading: Institute of Chemical Technology, Prague: Ing. Anatol Malijevský, CSc. et al.’s Physical Chemistry in Brief: “Chapter 7: Phase Equilibria”
Link: Institute of Chemical Technology, Prague: Ing. Anatol Malijevský, CSc. et al.’s Physical Chemistry in Brief: “Chapter 7: Phase Equilibria” (PDF)
Instructions: Read chapter 7, titled “Phase equilibria,” beginning on page 171 and ending on page 225. In this reading, you will encounter a systematic development of the thermodynamic principles that govern phase equilibria in physical systems, as well as a description of the thermodynamic properties associated with changes in phase. Be sure to carefully review all the diagrams and example problems presented in this reading.
Reading this material should take approximately 3 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.  Reading: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2nd ed.): “Chapter 8: Phase Transitions and Equilibria of Pure Substances”
Link: Dr. Howard DeVoe’s Thermodynamics and Chemistry (2^{nd} ed.): “Chapter 8: Phase Transitions and Equilibria of Pure Substances” (PDF)
Instructions: Navigate to chapter 8, beginning on page 193, and read the chapter, ending on page 222. Be sure to work through all the exercises and problems provided throughout the chapter. Focus on understanding the physical basis and mathematical formulation of all the expressions given in the chapter. There is no need to develop a facility for deriving all the equations, but you should be able to identify when and where the various equations are applicable as well as be able to use them in performing calculations.
Reading this material should take approximately 4 hours.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialNoDervis 3.0 Unported License.
 Lecture: Academic Earth: The University of California at Berkeley: Dr. Angelica Stacy’s “It’s Just a Phase: Phase Changes”

7.2 Phase Equilibria: OneComponent Systems
 Lecture: Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 18: Phase Equilibria – One Component”
Link: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 18: Phase Equilibria – One Component”
Also available in:
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Instructions: Watch the video (approximately 51 minutes in length) to learn about phase changes—first in onecomponent systems and then in multiplecomponent systems. Phase changes are little bit different from chemical reactions; there are some different results and different equations that we use to describe them. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.  Reading: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 14: Physical Transformations of Pure Substances” and “Lecture 15: Phase Transitions & Interfaces”
Link: The University of Windsor: Introductory Physical Chemistry: Dr. Rob Schurko’s Course Notes: “Lecture 14: Physical Transformations of Pure Substances”and “Lecture 15: Phase Transitions & Interfaces” (PDF)
Instructions: Read Dr. Schurko’s course material. As you read, pay special attention to the diagrams and figures presented in both sets of notes. Also, be sure to carefully review the equations that give the mathematical representations relevant to the thermodynamic data displayed in the figures.
Reading this material should take approximately 4 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpages above.
 Lecture: Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 18: Phase Equilibria – One Component”

7.3 ClausiusClapeyron Equation
Note: Some of the material you need to know for this subunit is covered by the Malijevský and DeVoe readings assigned beneath Subunit 7.1 of this course.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 19: ClausiusClapeyron Equation”
Link: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 19: ClausiusClapeyron Equation”
Also available in:
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Instructions: Watch the video (approximately 50 minutes in length) on the ClausiusClapeyron equation. This equation helps us to construct the phase diagram of a singlecomponent system with two phases. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.  Reading: The University of Arizona: Professor W.R. Salzman’s “Dynamic Textbook” of Physical Chemistry: “Clapeyron and ClausiusClapeyron Equations”
Link: The University of Arizona: Professor W.R. Salzman’s “Dynamic Textbook” of Physical Chemistry: “Clapeyron and ClausiusClapeyron Equations” (HTML)
Instructions: Read the webpage and work through the equations presented on the webpage. This resource will help you understand how the Clapeyron and ClausiusClapeyron equations are derived from the combined first and second laws of thermodynamics, and how these equations are used to ascertain the conditions for phase equilibria and the details of phase diagrams.
Reading this material should take approximately 2 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 19: ClausiusClapeyron Equation”

7.4 Phase Equilibria: TwoComponent Systems
Note: Some of the material you need to know for this subunit is covered by the Malijevskýand DeVoe readings assigned beneath Subunit 7.1 of this course.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 20: Phase Equilibria – Two Components”
Link: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 20: Phase Equilibria – Two Components”
Also available in:
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Instructions: Watch the video (approximately 50 minutes in length) to learn about equilibrium in multicomponent systems. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 20: Phase Equilibria – Two Components”

Unit 8: Thermodynamic Properties of Solutions
A solution is a homogeneous mixture comprising two or more substances that are mutually miscible. Common examples of solutions include Earth’s atmosphere, salt water, alcoholic beverages, and many metallic alloys. Compound materials that are not solutions include milk, precipitatehardened alloys, and carbonfiber composites. The special thermodynamic properties of solutions reflect large entropic contributions from the atomic or molecularlevel disorder that characterizes most homogeneous solutions. The thermodynamic behavior of solutions is, in large part, dominated by entropic effects. In this unit we will identify the thermodynamic driving forces that govern the formation and stability of solution media. We also will show how the thermodynamic properties of a solution reflect the physical properties and interaction dynamics of the molecular constituents of the solution.
Unit 8 Time Advisory show close
Unit 8 Learning Outcomes show close

8.1 Ideal Solutions
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 21: Ideal Solutions”
Link: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 21: Ideal Solutions”
Also available in:
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Instructions: Watch the video (approximately 50 minutes in length) to learn about ideal solutions and their associated vapor pressures. Raoult’s law and Henry’s law also are presented in this lecture. Raoult’s law applies to the partial vapor pressure of the solvent component of a solution in the limit of infinite dilution, whereas Henry’s law applies to the partial vapor pressure of the solute component of a solution in the limit of infinite dilution. Observed deviations from Raoult’s law and Henry’s law behavior provide diagnostics of solutesolvent interactions in solution media. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.  Reading: The University of Arizona: Professor W.R. Salzman’s “Dynamic Textbook” of Physical Chemistry: “Open Systems” and “Mixtures; Partial Molar Quantities; Ideal Solutions”
Link: The University of Arizona: Professor W.R. Salzman’s “Dynamic Textbook” of Physical Chemistry: “Open Systems”and “Mixtures; Partial Molar Quantities; Ideal Solutions” (HTML)
Instructions: Study the material on the “Open Systems” and “Mixtures; Partial Molar Quantities; Ideal Solutions” webpages. Focus on acquiring an understanding of how the thermodynamic properties of an open, multicomponent system are dependent on the number and relative amounts of the constituent components.
Reading this material should take approximately 3 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpages above.  Optional: Institute of Chemical Technology, Prague: Ing. Anatol Malijevský, CSc. et al.’s Physical Chemistry in Brief: “Chapter 6: Thermodynamics of Homogeneous Mixtures (Sections 6.16.4)”
Link: Institute of Chemical Technology, Prague: Ing. Anatol Malijevský, CSc. et al.’s Physical Chemistry in Brief: “Chapter 6: Thermodynamics of Homogeneous Mixtures (Sections 6.16.4)” (PDF)
Instructions: Read sections 6.16.4 (from “Ideal mixtures” through “Chemical potential,” on pages 139157) from chapter 6 of the textbook. Please note that this reading is optional; if you choose to complete it, you are encouraged to work through all the example problems provided in the text, as these examples will help you assess your ability to apply the relevant thermodynamic principles.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 21: Ideal Solutions”

8.2 NonIdeal Solutions
Note: Some of the material you need to know for this subunit is covered by lecture and readings assigned beneath Subunit 8.1, found above.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 22: NonIdeal Solutions”
Link: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 22: NonIdeal Solutions”
Also available in:
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Instructions: Watch the video (approximately 51 minutes in length) to learn more about how real solutions behave. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.  Reading: The University of Arizona: Professor W.R. Salzman’s “Dynamic Textbook” of Physical Chemistry: “Activity and Activity Coefficients” and “Vapor Pressure Diagrams and Boiling Diagrams”
Link: The University of Arizona: Professor W.R. Salzman’s “Dynamic Textbook” of Physical Chemistry: “Activity and Activity Coefficients” and “Vapor Pressure Diagrams and Boiling Diagrams” (HTML)
Instructions: Study the material displayed on both webpages. In this reading, you will encounter the definitions of the terms activity and activity coefficient as they are used in thermodynamic descriptions of physical systems (under equilibrium conditions).
Reading this material should take approximately 2 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpages above.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 22: NonIdeal Solutions”

8.3 Colligative Properties
Note: Some of the material you need to know for this subunit is covered by the lecture and readings assigned beneath Subunit 8.1, found above.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 23: Colligative Properties”
Link: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 23: Colligative Properties”
Also available in:
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Instructions: Watch the video (approximately 51 minutes in length). Colligative properties of solutions are those that depend only on the number of dissolved solutes and not on their chemical identity. Examples of colligative properties include freezingpoint depression, boilingpoint elevation, and osmotic pressure. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.  Reading: The University of Arizona: Professor W.R. Salzman’s “Dynamic Textbook” of Physical Chemistry: “Colligative Properties”
Link: The University of Arizona: Professor W.R. Salzman’s “Dynamic Textbook” of Physical Chemistry: “Colligative Properties” (HTML)
Instructions: Read webpage. Be sure to work through the derivations of all the equations shown in this section. Focus on developing a facility for using the equations to calculate the colligative properties of a system under a specified set of physical conditions.
Reading this material should take approximately 3 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 23: Colligative Properties”

8.4 Surface Properties of Solutions
 Web Media: Purdue University Department of Chemistry’s “Surface Tension”
Link: Purdue University Department of Chemistry’s “Surface Tension” (HTML)
Instructions: Study the webpage, including the general definition of surface tension and the animation of microscopic behavior at the surface of a liquid. Surface tension is an important property of a solution. It is defined as the amount of force needed to increase the surface of a solution by unit area. Capillary action results from surface tension and the adhesive forces between the substance and the tube.
Completing this web media assignment should take approximately 30 minutes.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.  Web Media: The University of Florida: Dr. Elsa Susana Sepúlveda Bustos’s “Surface Tension”
Link: The University of Florida: Dr. Elsa Susana Sepúlveda Bustos’s “Surface Tension” (HTML)
Instructions: Explore the webpage. This resource has many interesting animations, videos, and pictures to help you get an intuitive grasp of surface tension and capillary action. Be sure to watch the video of capillary action comparing two different substances in glass tubes. To find this video, navigate to the index at the top left of the webpage, then click on the section titled “Capillary Rise.” After clicking on the webpage links to view the illustrations and examples, try the three sample problems and the selftest at the bottom of the webpage.
Completing this web media assignment should take approximately 1 hour.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.  Reading: Institute of Chemical Technology, Prague: Ing. Anatol Malijevský, CSc. et al.’s Physical Chemistry in Brief: “Chapter 13: Physical Chemistry of Surfaces”
Link: Institute of Chemical Technology, Prague: Ing. Anatol Malijevský, CSc. et al.’s Physical Chemistry in Brief: “Chapter 13: Physical Chemistry of Surfaces” (PDF)
Instructions: Navigate to chapter 13 of the textbook, beginning on page 436 and ending on page 455. Read the chapter. This reading provides an excellent treatment of the thermodynamic properties that are characteristic of surfaces and interfacial phenomena.
Reading this material should take approximately 1.5 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpage above.
 Web Media: Purdue University Department of Chemistry’s “Surface Tension”

Unit 9: Statistical Thermodynamics: A Brief Overview
Thermodynamics describes the behavior of huge collections of microscopic particles through the use of such averaged properties as temperature, density, volume, entropy, energy, and so forth. In doing so, thermodynamics avoids the extraordinarily difficult task of directly computing the behavior of such collections of particles by using Newton’s equations of motion. The “dynamics” of thermodynamics has to do with changes in these averaged properties and not with the details of the microscopic configuration of the materials in the system.
Unit 9 Time Advisory show close
However, statistical mechanics is based on one fundamental assumption: that all possible microscopic configurations that are consistent with the observed averaged thermodynamic properties are equally likely to occur. This is an application of a philosophical position that has proven extremely useful in science: that we do not occupy a special place in the universe. (This idea is often called the “mediocrity principle” and may originally have been introduced by 16^{th}century astronomer Nicolaus Copernicus.) If all possible microscopic configurations are equally likely, then the physics we measure are most likely to be those of the most common possible configurations. This simple principle allows us to interpret the thermodynamic properties of materials in terms of their component particles and the interactions between them, which in turn leads to a more fundamental understanding of why matter behaves the way it does.
Unit 9 Learning Outcomes show close

9.1 Introduction to Statistical Mechanics
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 24: Introduction to Statistical Mechanics”
Link: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 24: Introduction to Statistical Mechanics”
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Instructions: Watch the video (approximately 52 minutes long), which begins with a review of some topics covered in Unit 8 of this course and then moves into a consideration of statistical mechanics. Pay particular attention to how you can calculate the probability of finding a molecule in a particular energy state. If we know the distribution of all the molecules of a system in its various states, then we can arrive at the macroscopic thermodynamic functions for that system. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.  Reading: The University of Arizona: Professor W.R. Salzman’s “Dynamic Textbook” of Physical Chemistry: “Notes on Statistical Thermodynamics – Partition Functions” and “Other Useful Information and Some Simple Models”
Link: The University of Arizona: Professor W.R. Salzman’s “Dynamic Textbook” of Physical Chemistry: “Notes on Statistical Thermodynamics – Partition Functions”and “Other Useful Information and Some Simple Models” (HTML)
Instructions: Study the material presented on both webpages. This reading essentially covers everything you need to know in order to meet the learning objectives set out for this unit of the course. You will learn how partition functions are defined, how they may be evaluated, and how they can be used to calculate the various thermodynamic functions of state. Focus on gaining a firm mastery of the material found in these readings, as an understanding of these topics will be crucial as you approach the remaining material in this unit of the course.
Reading this material should take approximately 4 hours.
Terms of Use: Please respect the copyright and terms of use displayed on the webpages above.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 24: Introduction to Statistical Mechanics”

9.2 Partition Function (q): Large N Limit
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 25: Partition Function (q)—Large N Limit”
Link: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 25: Partition Function (q)—Large N Limit”
Also available in:
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Instructions: Watch the video (approximately 51 minutes in length) to learn about partition functions and how we use them to determine what microstates are available to any given system. The lecture’s examples of a perfect crystal, a monoatomic gas, and a polymer in solution will help you visualize these abstract ideas in a more concrete way. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 25: Partition Function (q)—Large N Limit”

9.3 Partition Function (Q): Many Particles
Note: Some of the material you need to know for this subunit is covered by the reading assigned beneath Subunit 9.1, found above.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 26: Partition Function (Q) — Many Particles”
Link: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 26: Partition Function (Q) — Many Particles”
Also available in:
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Instructions: Watch the video (approximately 51 minutes in length) to learn how we can use the partition functions to calculate the thermodynamic functions for a system, thereby relating the microscopic and macroscopic properties of the system. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 26: Partition Function (Q) — Many Particles”

9.4 Statistical Mechanics and Discrete Energy Levels
Note: Some of the material you need to know for this subunit is covered by the reading assigned beneath Subunit 9.1, found above.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s“Lecture 27: Statistical Mechanics and Discrete Energy Levels”
Link: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 27: Statistical Mechanics and Discrete Energy Levels”
Also available in:
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Instructions: Watch the video (approximately 52 minutes in length) to learn about the statistical mechanical treatment of entropically driven processes. You will see how to calculate the entropy of mixing by using statistical mechanics. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s“Lecture 27: Statistical Mechanics and Discrete Energy Levels”

9.5 Model Systems
Note: Some of the material you need to know for this subunit is covered by the reading assigned beneath Subunit 9.1, found above.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s“Lecture 28: Model Systems”
Link: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 28: Model Systems”
Also available in:
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Instructions: Watch the video (approximately 51 minutes in length) to see an example of a statistical mechanical calculation carried out on a system in which the possible number of configurations (states) is nearly infinite. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s“Lecture 28: Model Systems”

9.6 Applications: Chemical and Phase Equilibria
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 29: Applications: Chemical and Phase Equilibria”
Link: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 29: Applications: Chemical and Phase Equilibria”
Also available in:
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Instructions: Watch the video (approximately 52 minutes in length) to learn how to use the partition function to determine K. You can find the lecture notes for this video here (PDF).
Watching this lecture should take approximately 1 hour.
Terms of Use: This resource is licensed under a Creative Commons AttributionNonCommercialShareAlike 3.0 United States license.
 Lecture: Massachusetts Institute of Technology OpenCourseWare: Dr. Moungi Bawendi and Dr. Keith Nelson’s “Lecture 29: Applications: Chemical and Phase Equilibria”