Envr 725

1. Envr 725 • Tues. and Thurs- 3 credit hours, room 0015 MHRC • 11:00 am to 12:15 pm • Snow days call 942 4880 or cell 919 614 4730 • http://www.unc.edu/courses/2007spring/envr/725/001/Envr725.html • Rich Kamens; 966 5452 • kamens@unc.edu • http://airsite.unc.edu/~kamens/

2. Textbook • Environmental Organic Chemistry by René P. Schwarzenbach, Philip M. Gschwend, and Dieter M. Imboden, John Wiley & Sons, Inc., New York, 2003, ISBN 0-471-35053-2, pages:1313.

3. UNC outdoor chamber

4. Gas/Particle partitioning of toxics organics on different aerosols

5. New UNC Aerosol Smog Chamber

6. Dual 270m3 chamber fine particle t 1/2 >17 h

7. From a Modeling perspective Equilibrium Organic Gas-particle partitioning provides a context for addressing SOA Formation • Numerical fitting • Semi-explicit

8. cis-pinonaldhyde Gas phase reactions C=O C=O O O particle Link gas and particle phases

9. kon koff particle C=O O kon koff • [ igas] + [part] [ipart] Kp = kon/koff

10. + CO, HO OH 2, CHO O norpinonaldehyde COOH O O O O norpinonic O acid Criegee1 3 COOH O O O pinonic acid O a -pinene CH CHO O 3 + other O COOH products Criegee2 COOH pinic acid Mechanism

11. pinonaldehyde

12. Overall kinetic Mechanism • linked gas and particle phase rate expressions

14. Particle Phase reactions cis-pinonaldhyde Gas phase reactions C=O C=O O O polymers particle

15. Particle Phase reactions cis-pinonaldhyde C=O C=O O O Gas phase reactions particle polymers

16. Particle Phase reactions cis-pinonaldhyde C=O C=O O O Gas phase reactions polymers

17. Particle phase pinonaldehyde dimers from acida-pinene +O3 M Na+(ESI-QTOF Tolocka et al, 2003)

18. Chemical System + NOx+ sunlight + ozone----> aerosols a-pinene

19. data NO model O3 NO2 ppmV NO2 Time in hours EST 0.95 ppm a-pinene + 0. 44ppm NOx

20. O O 3 mg/m Gas phase pinonaldehdye Time in hours EST

21. 3 mg/m Measured particle mass vs. model Particle phase Particle phase data 3 mg/m model TSP model TSP Time in hours EST

22. UNC outdoor chamber group

23. Air Pollution in NorthernThailand

30. Introduction to Environmental Physical Organic Chemistry • Environmental chemistry may be defined as "the study of sources, reactions, transport, effects, and fates of chemical species in water, soil, and air environments, and the effects of technology thereon.” Manahan, 1994

31. Class objectives: • Highlight some important areas in environmental chemistry • present some of the common techniques that environmental chemists use to quantify process that occur in the environment • It is assumed that everyone has courses in organic and physical chemistry.

32. Class objectives: • Partitioning is a thread that runs through the course • Linear free energy relationships will be used to help quantify equilibrium and kinetic processes

33. Thermodynamics • ui = uo1 +RT ln pi/p*iL • fi = i Xipi*pure liquid • RT lnfi hx /fiopure liq = RT lnfi H2O/fiopure liqfihx = fi H2O • ln Kp = a 1/T+b

34. Vapor pressure How to calculate boiling points

35. Vapor pressure and Henry’s law sat P sat sat *    i K P V iL iw sat iaw iw C iw Solubility and activity coefficients Octanol-water partitioning coefficients

36. Additional Principles • Organic Acid-bases and LFERs • diffusion • chemical spills and mass transfer • Organic reactions in the environment • Solid- liquid interactions • photochemistry

37. Homework, quizzes, exams • To insure that most of us stay reasonably current with the lectures and readings, an option is to have 6-8 unannounced quizzes throughout the semester. • They will take ~10 minutes. The first quiz will be on Chapter 2 since we will not cover Chapter 2. Quizzes will count 10% of your grade.

38. Another option is a set of short questions to be answered and handed in before most lectures (10% of grade)—your choice!

39. There will be a homework problem set associated with each assigned chapter of the book. It is due a week after the completion of the book chapter. • These problem sets should take between 3 and 10 hrs. Answers will graded and returned to you as soon as possible. These will count for 25% of your grade.

40. In addition, you are expected to work through the illustrative examples and problemswhich have answers in the test on your own. • Some of these could appear on exams • There will be two exams (70% of your grade) 25% homeworks, 5%???

41. Learning • Read Chapter • Simple or short Homeworks • Lecture ??? • Long Homeworks • Exams

42. Why the interest? There are more than 70,000 synthetic chemicals that are in daily use: solvents components of detergents dyes and varnishes additives in plastics and textiles chemicals used for construction antifouling agents herbicides, insecticides,fungicides

43. Some examples of environmental chemicals Polynuclear Aromatic HC (PAHs) Dioxins Ketones PCBs CFCs DDT O3, NO2, aerosols, SO2

44. PAHs Formed from small ethylene radicals “building blocks” produced when carbon based fuels are burned Sources are all types of burning in ChiangMai, Thailand:a) 2-stroke motorcycle engines b) cars- light diesels c) open burning d) barbecued meat??

45. Combustion Formation of PAH Badger and Spotswood 1960

46. PAHs Metabolized to epoxides which are carcinogenic; O PAH are indirect acting mutagens in bacterial mutagenicity tests (Ames-TA98+s9) methyl PAHs are often more biologically active than PAHs

47. Carcinogenic tests with PAHs Professor Gernot Grimmer extracted different types of smoke particles He then took the extract and applied it to mouse skin and implanted it into rat lungs How did he obtain extracts? How did he fractionate his extracts??

48. Extraction by soxhlet extraction starts with solvent (MeCl2) in a flask

49. Extraction by soxhlet extraction starts with solvent (MeCl2) in a flask MeCl2

50. The solvent is heated and starts to evaporate Heat