CHM 3400: Physical Chemistry (for the Biosciences)

Spring 2011
Lectures: Monday 3rd period (9:35-10:25) 207 LEI Wednesday 3rd period (9:35-10:25) 207 LEI Friday 3rd period (9:35-10:25) 207 LEI Mon/Wed (10:30-11:30) (311 CLB)

Office hours (Dr. Polfer)

Office hours (Teaching Assistant Yi Fu): R (12:30-1:30 pm), F(1:30-2:30 pm) (Chemistry Lab Building Room 313) fu@chem.ufl.edu Textbook: Physical Chemistry for the Biosciences, by Raymond Chang; University Science Books, Sausalito, CA. ISBN #1-891389-33-5. Access course material www.chem.ufl.edu/~polfer/CHM3400

Dr. Nick C. Polfer Office: 311 Chemistry Lab Building Phone: 392-0492 polfer@chem.ufl.edu

CHM3400 - Lecture 1 Jan 5

Problem Sets/homework: Problem sets (9) will be assigned periodically throughout the semester as an aid in comprehending the course material. Each of these will be graded out of 10 pts (or 15 pts) max if turned in on time; turning in late will cost 2 points per working day. Model answers will be posted online. Exams: The course consists of two in-class exams during the semester as well as a comprehensive final. The exams will cover homework problems and will emphasize understanding of the lecture material and problem solving. There will be no make-up exams. The in-class exams will be closed book. Exam I: Exam II: Final: Feb 7 (Mon), in class Mar 21 (Mon), in class Apr 27 (Wed), 12:30-2:30 pm, 207 LEI

Only for the final exam: you can bring one letter-size sheet with your own handwritten notes with formulae etc. that aid understanding of the course.

Grading: The in-class exams are worth 100 points, whereas the final counts for 200 points. The total points for homework are 100 point. Total = (2 x 100) + 200 + 100= 500 points Proposed Grade Levels: A: 461 500 A-: 441 - 460 B+: 421 - 440 B: 401 420 B-: 381 - 400 C+: 361 - 380 C: 341 - 360 C-: 321 - 340 D+: 301 - 320 D: 281 - 300 D-: 261 - 280 E: 260 and below
3

HOW TO GET MOST OUT OF THIS COURSE? 1. Pre-read chapter (syllabus) and bring questions to class 2. Homework preparation for exam (numerical examples and problem solving)

WHAT IS EXPECTED (OF YOU)?

Understanding of the course material is essential. Moreover, this course encourages problem-solving and critical thinking

Physical Chemistry : Biosciences

Gases Thermodynamics Electrochemistry Kinetics Quantum mechanics Spectroscopy Luminescence Breathing Protein/ligand binding energies Nerve impulse Enzyme catalysis Predict molecular structure and function Determine molecular structure and function Photosynthesis

Syllabus
Tentative Lecture Schedule CHM 3400
Date W 01/05 F 01/07 M 01/10 W 01/12 F 01/14 M 01/17 W 01/19 F 01/21 M 01/24 W 01/26 F 01/28 M 01/31 Topic Ideal and real gases Kinetic gas theory Maxwell distribution laws and molecular collisions First Law of Thermodynamics Heat capacity and gas expansions No class (MLK Day) Calorimetry Second Law of Thermodynamics: Entropy Second Law of Thermodynamics: Carnot engine, entropy change Third Law of Thermodynamics, Gibbs free energy Phase equilibria Ideal solutions, chem. potential

Chapter (pages)

Textbook 2 (7-21) 2 (21-25) 2 (25-31) 3 (39-49) 3 (49-59) 3 (59-74) 4 (81-86) 4 (87-95) 4 (95-110) 4 (110-117) 5 (127-131)

HW

Homework due date

H1

H2

H3

Ideal and real gases (Chapter 2 p. 721)

Ideal/perfect gas equation Extensions from ideal to real gases Ideal gas law:

PV = nRT
Option 1:

BE CAREFUL WITH UNITS!!!

Option 2:

P = pressure (atm) V = volume (L) n = no. of moles (mol) R = ideal gas constant = 0.08206 (L atm K-1 mol-1) T = temperature (K)
Conversion factors: 1 atm = 1.01325*105 Pa (=Nm-2) 1 L = 1 dm3 = 10-3 m3

P = pressure (Nm-2) V = volume (m3) n = no. of moles (mol) R = ideal gas constant = 8.31451 (J K-1 mol-1) T = temperature (K)

Degrees of freedom
Depends on the type of experiment/system

Open system

Closed system

Isolated system

Mass transfer

Heat transfer

Historical perspective
Boyles Law (1662)
P

What type of system?

P vs. V at constant T ?

P 1/V PV = constant
http://www.grc.nasa.gov/WWW/K-12/airplane/aboyle.html
9

Historical perspective
Charles and Gay-Lussac (~1800)
P vs. T at constant V ? P
William Thomson (Lord Kelvin) (1848)

PT VT

10

Historical perspective
Avogadros Law (1811)

Vn

Summary: PV = constant P/T = constant V/T = constant V/n = constant

PV = nRT

11

Numerical example
Example 2.1 Air entering the lungs ends up in tiny sacs called alveoli, from which oxygen diffuses into the blood. The average radius of the alveoli is 0.005 cm, and the air inside contains 14 percent oxygen. Assuming that the pressure in the alveoli is 1.0 atm and the temperature is 37 oC, calculate the number of oxygen molecules in the alveoli.

PV = nRT
Where P = pressure (atm) V = volume (L) n = no. of moles (mol) R = ideal gas constant = 0.08206 (L atm K-1 mol-1) T = temperature (K)
Notice: 14% O2. What happens if we have a mixture of gases?

12

Daltons Law of Partial Pressures

Ptotal = P1 + P 2 + ... + Pi = Pi
1 i

Add partial pressures to obtain total pressure Cannot distinguish between different gases

13

Ideal Gas - Assumptions

1. Gases are composed of many individual particles 2. Gas particles have no volume 3. Gas particles do not interact (inter-particle forces)
Which gas is closest to an ideal gas?

smallest volume least inter-particle forces Atomic radius: Boiling point: 31 pm 4.22 K

14

Deviations from ideal gas behavior

At high P: At low T: At low V: particles interact more frequently less kinetic energy to overcome attraction forces self-volume becomes more important

Compressibility factor

PV PV Z= = nRT nRT
What is V ?

What would Z be for an ideal gas?

15

Compressibility factor vs. P

T = 273 K

Attractive forces long range Repulsive forces short range

Z > 1: high P,T many collisions non-zero self volume causes larger V than expected (repulsive forces dominate) Z < 1: low P,T particles cannot overcome attraction forces lower V than expected (attractive forces dominate)
16

Models for non-ideal (real) gases

Van der Waals model (Physical model) Virial equation of state (Numeric fitting)

B C D Z = 1+ + + + ... V V2 V3

Z = 1 + B ' P + C ' P 2 + D' P 3 + ...

17

Van der Waals equation

Measured pressure Self-volume

2 an ( ) + P V nb = nRT 2 V

Intermolecular forces reduce pressure on wall a

Expected pressure in absence of intermolecular forces proportionality factor for intermolecular attraction. Depends on density (n/V) squared. b

Expected volume in absence of selfvolume proportionality factor for self-volume. Depends on no. of moles (n).
18

Examples for a and b factors

weighted with intermolecular force (use boiling point as a reference point) weighted with self-volume and molecular repulsion
19

Limitations of the Van der Waals equation

Isotherm The Van der Waals equation fails, where gas and liquid co-exist.

Condensation of the gas to liquid

Can a gas be liquified at a temperature above the critical point?

20

Condensation of gases

Why is the P/V slope horizontal here?

21

Supercritical fluids
Gas T > Tc: Carbon dioxide - flow properties of a gas - solvent properties of a liquid

Decaf coffee: extract caffeine from raw beans Oil-free chips: extract cooking oil Environmental clean-ups: dissolves chlorinated hydrocarbons

22

Homework:
Homework (1) Chapter 2: 2.2, 2.10, 2.19, 2.25, 2.32, 2.43, 2.52, 2.63, 2.73, 2.85. Due date: W 01/14

Next lecture:

Bring your CALCULATOR

23