# PChemFall2015

From Predictive Chemistry

**Physical Chemistry I**

Course Info

- Course Numbers CHM 4410
- Credit Hours: 4
- Meeting Dates: Aug. 25 - Dec. 4, 2015
- No Class Nov. 26 & 27

- Meeting Times: Tues. and Thurs., 3:30-4:45 pm in Muma College of Business, 1403
- Problem Session: Fri., 10:10-11:00 am in CHE303
- Office Hours: Tues. and Thurs., 2:30-3:30 pm in SCA 433

- Grading:
- Quiz (40%)
- To succeed in the quiz, do assigned homework.

- Midterm (30%) Thurs., Oct. 8, 3:30-4:45 pm
- Final (30%) Thurs., Dec. 10, 12:30-2:30 pm

- Quiz (40%)

## 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

## Topics

- Partial Differentiation
- First Law of Thermodynamics
- Algebraic Methods
- Energy, Enthalpy, Entropy, and Free Energy
- Counting Statistics
- The Second Law of Thermodynamics
- Standard States and Energies - Third Law of Thermodynamics
- Phase Equilibria and Basic Phase Diagrams
- Thermodynamic Cycles, Examples with Refrigeration and Galvanic Cells

### Notes & Homework

Here are the running notes for the course. You can check the file date to see when there have been updates. By request, here are the quiz keys and quiz keys (or you can quiz your friends with the early blank quizzes and later blank quizzes).

- Introduction to P-Chem
- Excel plot and V-solve for van der Waals Equation of State
- Works fine with LibreOffice

- Homework 1: 16-1 through 16-7, 16-9, H-1, H-4 through H-6, H-10, H-11, 27-1 through 27-7
- Does the vdW equation of state make a prediction for the density of liquid H2?
- What is a critical temperature?
- Who is Fritz London?

- Homework 2: G-1, G-5, H-12, H-13, 16-31 through 16-32, 16-37, 16-38 through 16-40, 16-44, 16-55, 16-56
- Homework 3:
- Use the Lennard Jones spreadsheet for the following:
- Plot Vc vs sigma^3 to find the correlation between the two.
- Compute the exact derivative of the Lennard-Jones function for each r in column M, and compare the results to the numerical approximation in column L.
- Decrease the x-spacing, dx, in the numerical integration of B2v to 0.05. How does the result change?

- Use the 2 state model spreadsheet for the following (DG is an abbreviation for Delta G of folding):
- Fit a line to DG(T) = DH - T DS
- Compute the average of d(beta DG)/dbeta
- Compute and plot d(beta DG) / d(beta P) - this should give you an effective folding volume
- Compute and plot d(DG) / d[Urea] - this should give you the energetic influence of urea

- Use the Lennard Jones spreadsheet for the following:
- Homework 4 (to appear on Quiz 4):
- Chapter 19: 1-7, 9, 19, 29-31
- For 19-3, remember to solve for P = P(V)

- Homework 5:
- Chapter 19: 35-44, 46-50
- Chapter 20: 1-5

- Final Exam Material (updated Oct. 15, 2015)
- The rest of the homework assignments will be based on the above final exam material. It will be updated with more details on related reading and homework questions from McQuarrie as we cover each topic.

- For Quiz on Tues., Oct. 20
- Read Chapter 20 and compute the entropy change on expansion of a gas and for a mixture of 2 ideal gases.
- Write the entropy of isothermal expansion for a mixture of 2 ideal gases from V0 to V1 (p. 832).
- Write the expression for the entropy of mixing for ideal 2 gases (p. 835).
- Why do the entropies of expansion add together (bottom of p. 835, just after Ex. 20-4), while the entropy of mixing the two gases is not zero - phrase your answer in terms of independence and counting the total number of states (see Ex. 20-3)?
- Bonus: How does this relate to reversible vs. irreversible? (we'll discuss)

- For Quiz 8-9, Tues. Nov 3 and Nov 10:
- 21-3, 21-4,5,7 (plotting skills), 22-23,25, 24-1 through 24-6 (note use of Ybar = dY / dn in 24-3), 24-7 (note similarity to 16-9)
- Advanced level problems:
- 22-20 (Note Delta S[ideal -> nonideal] follows Fig. 22.6 on p. 900)
- 24-8 (we'll work this in class)

- For Quiz 11-12 (problems worked in class)
- prob. 26-33; ex. 24-3; prob. 24-13,50-52; prob. 22-33; prob. 24-37,56,57; ex. 25-1,3
- Equilibrium calculations: ex. 26-4 (see also Tbl 26.1); ex. 26-12,13 (mostly uses Eq. 26.66, also prob 58), 21,22,29,31,32,62,63