Chemistry 223: Introductory Physical Chemistry I

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Chemistry 223: Introductory Physical

Chemistry I David Ronis McGill University

Chemistry 223 Introductory Physical

Chemistry I David Ronis

? 2015 McGill University

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All truths are easy to understand once they are discovered; the point is to discover them.

Philosophy is written in this grand book-I mean the universe-which stands continually open to our gaze, but it cannot be understood unless one first learns to comprehend the language and interpret the characters in which it is written. It is written in the language of mathematics, and its characters are triangles, circles, and other geometrical figures, without which it is humanly impossible to understand a single word of it.

Opere Il Saggiatore Galileo Galilei (1564 - 1642)

A theory is the more impressive the greater the simplicity of its premises is, the more different kinds of things it relates, and the more extended is its area of applicability. Therefore the deep impression which classical thermodynamics made upon me. It is the only physical theory of universal content concerning which I am convinced that within the framework of the applicability of its basic concepts, it will never be overthrown.

Albert Einstein (1879 - 1955)

The Founders of Thermodynamics and the Kinetic Theory of Gases

Joule

Carnot

Clausius

Maxwell

Kelvin

Gibbs

Boltzmann

Fall Term, 2015

Table of Contents

1. General Information . . . . . . . . . . . . . . . . . . 4

1.1. Contact Information . . . . . . . . . . . . . . . . . 4

1.2. Texts . . . . . . . . . . . . . . . . . . . . . . 5

1.3. Supplementary Texts . . . . . . . . . . . . . . . . . 5

1.4. Grades . . . . . . . . . . . . . . . . . . . . . 5

1.5. Random, McGill Specific, Notes . . . . . . . . . . . . . 6

1.6. Tentative Course Outline . . . . . . . . . . . . . . . . 7

2. Divertissements . . . . . . . . . . . . . . . . . . . 8

2.1. Divertissement 1: Founders of the first law of thermodynamics . . . . 8

2.2. Divertissement 2: Why do we have winter heating? . . . . . . . 8

2.3. Divertissement 3: Nicolas Leonard Sadi Carnot . . . . . . . . 10

2.4. Divertissement 4: Absolute Temperature . . . . . . . . . . . 10

2.5. Divertissement 8: On the names of thermodynamic functions . . . . 11

3. Some Properties of Ideal and Non-Ideal Materials . . . . . . . . 13

3.1. Ideal Gases . . . . . . . . . . . . . . . . . . . . 13

3.2. Dalton's Law . . . . . . . . . . . . . . . . . . . . 13

3.3. Beyond Ideal Gases . . . . . . . . . . . . . . . . . . 14

3.4. Liquids and Solids . . . . . . . . . . . . . . . . . . 20

4. Probability and Statistics . . . . . . . . . . . . . . . . 22

5. Maxwell-Boltzmann Distribution . . . . . . . . . . . . . . 25

5.1. Appendix: Proof of Equation (5.4) . . . . . . . . . . . . . 30

6. Collisions, Reactions, and Transport . . . . . . . . . . . . . 32

6.1. Effusion, Surface Collisions and Reactions . . . . . . . . . . 32

6.2. Gas Phase Collisions and Chemical Reactions . . . . . . . . . 32

6.3. Mean Free Path and Transport Phenomena . . . . . . . . . . 35

6.4. Appendix: The Center of Mass Frame . . . . . . . . . . . 40

7. Work, Heat, and Energy . . . . . . . . . . . . . . . . . 42

7.1. Zeroth Law of Thermodynamics . . . . . . . . . . . . . 42

7.2. Some Definitions . . . . . . . . . . . . . . . . . . 42

7.3. Euler's Theorem, Partial Molar Quantities, . . . . . . . . . . 44

7.4. Work and Heat in Thermodynamics . . . . . . . . . . . . 45

7.5. The First Law of Thermodynamics: . . . . . . . . . . . . 48

7.7. Appendix: Energy in Classical Mechanics . . . . . . . . . . 50

8. Thermochemistry . . . . . . . . . . . . . . . . . . . 53

8.1. Enthalpy Calculations: Chemical Reactions and Hess' Law . . . . . 53

8.2.

Measuring

H

0 f

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54

8.3. Reactions at Different Temperatures: Kirchoff's Law . . . . . . . 55

8.4. Bond Energies . . . . . . . . . . . . . . . . . . . 56

8.5. Some Manipulations Involving Thermodynamic Functions . . . . . 58

8.5.1. The relationship between CP and CV . . . . . . . . . . . 58 8.5.2. The Joule-Thompson Experiment . . . . . . . . . . . . . 59

9. Ideal Gas Carnot Engines and Efficiency . . . . . . . . . . . 62

9.1. Energy in an Ideal Gas: Joule's Experiment . . . . . . . . . . 62

Fall Term, 2015

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