# CHEM105: Physical Chemistry I

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.

Completing this unit should take you approximately 33 hours.

☐  Subunit 1.1: 3 hours

☐  Subunit 1.2: 9.5 hours

☐  Subunit 1.3: 20.5 hours

Unit1 Learning Outcomes
Upon successful completion of this unit, you should be able to: - define the units of force, work, energy, heat, and temperature in the SI system; - perform conversions between different types of thermodynamic - review the history of thermodynamics and its domain; - define systems, surroundings, and equilibrium states, as they are understood within a thermodynamic context; - distinguish between state functions and path functions; - perform simple calculations with ideal and real gases by using their equations of state; - define heat and heat capacity and describe the relationship between these concepts and the concept of work; and - define the zeroth (0th) law of thermodynamics and its relation to temperature.

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 Non-SI 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

Reading these webpages should take approximately 1 hour.

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 On-Line 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 On-Line 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 On-Line 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 non-SI units, please refer to Subunit 1.2 of Saylor’s CHEM101.

Reading this material should take approximately 30 minutes.

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.

displayed on the webpage above.
``````

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,”
Carefully examine and interpret the “Concept Map” provided at the
end of each section in order to review this material and solidify

Reading this material should take approximately 1 hour.

attributed to Dr. Stephen Lower.
``````

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](http://ocw.mit.edu/courses/chemistry/5-60-thermodynamics-kinetics-spring-2008/video-lectures/lecture-1-state-of-a-system-0th-law-equation-of-state/)

[MP4](http://ocw.mit.edu/courses/chemistry/5-60-thermodynamics-kinetics-spring-2008/video-lectures/lecture-1-state-of-a-system-0th-law-equation-of-state/)

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.

``````
• 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 (2nd 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.

• 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.

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.

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.

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
PDF” at the top of the webpage.

Reading this material should take approximately 1 hour.

``````

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.

displayed on the webpage above.
``````

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
webpage.

Reading this material should take approximately 1 hour.

``````

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](http://ocw.mit.edu/courses/chemistry/5-60-thermodynamics-kinetics-spring-2008/video-lectures/lecture-2-work-heat-first-law/)

[MP4](http://ocw.mit.edu/courses/chemistry/5-60-thermodynamics-kinetics-spring-2008/video-lectures/lecture-2-work-heat-first-law/)

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.

``````

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
equations-of-state for ideal and real gases represent their P-V-T
properties. Also, be sure to work through the kinetic-molecular
theory of gases, as it is formulated in lecture 3, and be able to
derive the ideal-gas equation-of-state based on this theory.

Reading this material should take approximately 3 hours.

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.

• 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 P-V-T 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.

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.

displayed on the webpages above.
``````

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.

``````
• 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. Re-read 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.

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 (2nd 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.