Envr 725Introduction to Environmental Physical Organic ChemistryClass objectives:Slide 4ThermodynamicsVapor pressureVapor pressure and Henry’s lawAdditional PrinciplesHomework, quizzes, examsPowerPoint PresentationSlide 11Slide 12Important Environmental IssuesSlide 14Slide 15Slide 16Combustion Formation of PAHSome PAH structuresSlide 19Slide 20Slide 21Slide 22Slide 23Slide 24Slide 25Professor Grimmer fractionated the exhaust extractsWhat did Grimmer see when exposed rats and mice to the different fractions?Slide 28Analysis of reaction productsSlide 30PFBHA O-(2,3,4,5,6-pentafluorobenzyl) -hydroxylamine for carbonyl groupsPentafluorobenzyl bromide (PFBBr) derivatization for carboxylic and hydroxyl groupsBSTFA for carbonyl, hydroxyl, and/or carboxylicSlide 34Thermal desorption particle beam mass spectrometry (Paul Ziemann)Slide 36Combustion Formation of Dioxins from Polychlorinated phenolSlide 38Slide 39Slide 40Slide 41Slide 42Environmental Fate of Chlorinated Dioxins and Furans (Czuczwa and Hites, 1984)US coal consumption vs chlorinated aromatic productionChlorinated aromatic production vs dioxin and furan conc. in lake core samplesPCBs in the U.S. Great LakesPolychlorinated biphenyls (PCBs)Slide 48Slide 49Slide 50Slide 51Slide 52Slide 53Slide 54What do we do now, when new compounds are introduced into the environment...??An example is a new compound called D5. It is a silicon-oxygen compoundNew compounds are introduced into the environment ... Toxicity? Where will it go?Slide 58Seveso, Italy Dioxin releaseA similar observation has been made in the bird population1. There is a general concern that if we observe abnormalities in wildlife, similar kinds of mechanisms may exist in humans.Mercury poisoning off the coast of Minamata, Japan is an example2. Toxic loadsSlide 64Slide 65Slide 663. Pesticide exposures4. The end points may not only be cancer, but compromised immune systems and generally poorer health.4. Immune systems & Mother’s milk4. Mother’s milkSlide 71Slide 72Slide 735. PCBs and lower intelligenceSlide 75Slide 76Slide 776. DDT and immune system damageSlide 79Slide 807. Sexual impairmentSlide 827a. Sexual impairment7b. Sexual impairment8. Endocrine disruptersSlide 869. Other chemicalsSlide 88Slide 899. PhthalatesSlide 91Recommendations1Envr 725Tues. and Thurs- 3 credit hours, room 2303 MHRC 2 pm to 3:15 pmSnow days call 942 4880 or cell 919 619 3701http://www.unc.edu/courses/2010spring/envr/725/001/Envr725.html (use internet explorer)Rich Kamens: 966 5452; [email protected];Rose Cory: 966-3529; [email protected] 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, 19943Class 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.4Class objectives:Partitioning is a thread that runs through the courseLinear free energy relationships will be used to help quantify equilibrium and kinetic processes5Thermodynamicsui = uo1 +RT ln pi/p*iLfi = i Xipi*pure liquidRT ln fi hx /fiopure liq = RT lnfi H2O /fiopure liqfi hx = fi H2Oln Kp = a 1/T+b6ambambmfusiLTTTRSppis)()(lnln**Vapor pressure)]()(ln.*lnTTTTpbbiL58119 How to calculate boiling points7Vapor pressure and Henry’s lawKPCP ViawiiwiwsatsatsatsatiL*iw  Solubility and activity coefficientsOctanol-water partitioning coefficients8Additional PrinciplesOrganic Acid-bases and LFERsdiffusion chemical spills and mass transferOrganic reactions in the environmentSolid- liquid interactions photochemistry9Homework, 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.10Another option is a set of short questions to be answered and handed in before most lectures (5% of grade)—your choice!11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.12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 three exams (70% of your grade ), 25% homeworks, 5%???13Important Environmental IssuesGlobal warming and stratospheric ozone depletionConcentration of environmental pollutants at the poles; pesticides in foods, etc.Buildup of environmental chemicals in the oceans; contamination of soil and ground waterParticle exposure, photochemical oxidant exposure, acid deposition Energy shortagesThere are more than 70,000 100, 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–pharmaceuticals Why the interest? Polynuclear Aromatic HC (PAHs) Dioxins Ketones PCBs CFCs DDT O3, NO2, aerosols, SO2Some examples of environmental chemicals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??PAHs17Combustion Formation of PAHBadger and Spotswood 1960(I)(II)(III)(IV)CCCCCCCCCCCC(VII) (VI)(V)Benzo a Pyrene18Some PAH structuresanthracenephenanthrenefluoranthenenaphthalenebenz(a)anthracenebenzo(a)pyrene [BaP]Naphthalene, phenanthrene and anthracene are found in the gas phase pyrene and fluoranthene are in both the gas and particle phaseBaA and BaP are mostly on the particles, Why???PAHsMetabolized to epoxides which are carcinogenic; O PAH are indirect acting