# PChemFall2018

### From Predictive Chemistry

**Physical Chemistry I**

Course Info

- Course Numbers CHM 4410-001
- Credit Hours: 4
- Meeting Dates: Aug. 21 - Nov. 27, 2018
- No Class Aug. 24 or Nov. 22-23

- Meeting Times: Tues. and Thurs., 3:30-4:45 pm in CIS 3064
- Regular quizzes on Tuesdays
- Problem Sessions: Fri., 2-2:50 pm in CIS 3064
- Office Hours: Tues. and Thurs., 2:30-3:20 pm in IDR 200

- Grading:
- Quiz (40%)
- To succeed in the quiz, complete the homework and study the topics covered in the previous week!

- Midterm (30%) Thurs., Oct. 11 3:30-4:45 pm (CIS 3064)
- Final (30%) Thurs., Dec. 6 12:30-2:30 pm (CIS 3064)

- Quiz (40%)

## Contents |

## Overview

This is the first part of a 2-semester course in thermodynamics. This course will cover the mathematical theory of chemical equilibrium, heat, and work. These are the driving forces behind the operation of Le Châtelier's principle, and are routinely used to understand and control chemical reactions, states of matter, and amount and efficiency of energy production.

## Textbooks

- McQuarrie and Simon, Physical Chemistry: A Molecular Approach, University Science Books, 1997. ISBN: 0935702997.

## Resources

- Kinetic Theory at HyperPhysics
- Heat Concepts at HyperPhysics
- Note: McQuarrie says dU = dQ + dW, while Nave says dU = dQ - dW. There is no contradiction, since McQuarrie's dW = -P dV (work done on the system), while Nave's dW = P dV (work done by the system). I prefer the first definition.

- News from the frontlines of exploring entropy: Information: From Maxwell’s demon to Landauer’s eraser
- Notes on transformations of variables.
- Course Page from 2017
- Course Page from 2016
- Course Page from 2015 -- contains previous quizzes and keys.
- Pretest key
- Quiz 1 Key -- for more information and practice problems, see The Vallance Chemistry Group, U. Oxford (http://vallance.chem.ox.ac.uk under Teaching -> Units and Dimensions).
- Gas Thermodynamics Videos:
- P-V work demonstrated by a Steel Drum Implosion
- Adiabatic Compression in a Fire Piston
- Complete thermodynamic cycle Stirling Engine
- Pressure (concentration gradient) driven chemical work ATP Synthetase

## Topics

- Moving Freely in P-V-T space (Chapter H, with examples from Ch. 16-[2,3,5,6,7], 17-[4,5], and 19-1)
- Isobaric, isothermal, and isochoric processes
- State functions
- Implicit, partial, and total derivatives
- Integration along a path
- Relations between partial derivatives
- Transformations using substitution
- Transformations using the chain rule

- Visualizing isosurfaces
- Using P(V,T) / V(P,T) / T(P,V)

- First Law of Thermodynamics – conserved quantities (Ch. 19-[2 to 9])
- Mechanisms of energy flow: work, heat, mass/chemical
- Integrating work and heat for common processes
- Energy of a molecule vs. a collection – translation, rotation, intermolecular, etc.
- Extensive and intensive quantities
- Using energy balance for fun and profit.

- Standard States and Energies (Ch. 19-[10,11,12], Ch 26-[3,6,7,8,9])
- Connecting to analytical chemistry.
- Spontaneous, irreversible, processes vs. quasistatic processes.
- Experimentally measuring reaction constants and heats. (Ch. 21-5)

- The Second Law of Thermodynamics: Energy, Enthalpy, Entropy, and Free Energy (Ch. 20)
- The absolute temperature scale. (Ch. 16-1)
- Inequalities followed by each path type. (Ch. 22-[1,2])
- Heat, measurement, information, Maxwell’s demon and Landauer’s principle.

- Basic Probability
- Simple counting (Ch. J)
- Velocity distribution function (Ch 27-[1,2,3,4])
- Boltzmann distributions (Ch. 17-[1,2,3,6 to 8])

- Applications:
- Quantitative Prediction of Reaction Equilibria (Ch. 26)
- Liquid solutions: osmotic pressure, vapor pressure, Henry’s and Raoult’s Laws (Ch. 24)
- Phase Equilibria and Basic Phase Diagrams (Ch. 23)
- Thermodynamic Cycles, Examples with Refrigeration and Galvanic Cell (Ch. 20-7)

## Assigned Homework Problems

- Moving Freely in P-V-T space
- H: 1-5,7,10-14
- 16:1-21,25,26(1st part),29,35-42,44-45,52-56,58-59,33(optional)
- sketch a plot for 16.4 and 16.5

- 17: 9-17

- First Law (sec. 19-1 through 19-9)
- 19:1-31
- You can skip 19-27 and 28 (we'll do in class)

- Standard States and Energies (sec. 19-10 through 19-12, 21-5 and 26-3 through 26-9)
- 19:34-49
- 21: 1-7, 10-26, 29, 48, 42-43, 45-47
- 26: 2,6,8-11,13,16-17,21
- 26: 61 -- only integrate dG = V dP at constant V=1/rho.

- Midterm!
- Entropy, Free Energy and the Second Law (all of Ch. 20, sections 16:1, 22:1-2)
- 20: 2-4, 6-16, 18-19, 24-25, 27-30, 32-33
- 22: 1-5 (for 4 and 5 use 1st law and Gibbs relation from A)
- 16: 4,6-11

- Basic Probability (Ch. J, 17 and 27)
- J: 1-7
- 17: 1, 3, 4, 7-8 [for 7, use a 3-state system with E(0) = 0, E(-1) = -1, E(1) = 1]
- 27:1-9

- Applications:
- Reaction Equilibria (Ch. 26)
- 26: 3-7, 12, 14-15, 33, 59, 61, 62-65

- Phase Equilibria and Basic Phase Diagrams (Ch. 23)
- Liquid Solutions: Osmotic Pressure, Henry's and Raoult's Law (Ch. 24)

- Reaction Equilibria (Ch. 26)

## Online Tutorials

There are some excellent introductory videos on Khan Academy that are useful if you need a refresher or extra practice with some of the topics in the course.

- Moving Freely in P-V-T space
- Isobars & Work [1]
- Isotherms, Isochors, Adiabats [2]
- Implicit Derivatives (explained with practice problems) [3]
- Partial Derivatives (explained with practice problems) [4]
- State Functions (Macrostates vs Microstates) [5]
- Quasistatic and Reversible Processes [6]
- Integration along a path (using PV-diagrams and expansion/compression Work) [7]

- First Law of Thermodynamics – conserved quantities (Ch. 19-[2 to 9])
- PV work [8]