Environmental Chemistry Environmental Chemistry Microscale Laboratory Experiments Jorge G.Ibanez Margarita Hemandez-Esparza Carmen Doria-Serrano Arturo Fregoso-Infante Mexican Microscale Chemistry Center Dept. ofChemicaland EngineeringSciences UniversidadIberoamericana-Mexico City Mono Mohan Singh NationalMicroscale Chemistry Center MerrimackCollege-NorthAndover,MA ~ Springer LibraryofCongress ControlNumber: 2007920429 ISBN-13:978-0-387-49492-0 eISBN-13: 978-0-387-49492-8 Printedonacid-freepaper. ©2008SpringerScience+BusinessMedia,LLC Allrights reserved. This workmaynotbetranslatedorcopied inwholeorinpartwithout thewritten permissionofthepublisher (Springer Science+BusinessMedia,LLC, 233SpringStreet,NewYork,NY 10013,USA),exceptforbriefexcerpts inconnection with reviews or scholarly analysis. Use in connectionwith anyform of informationstorage andretrieval, electronic adaptation, computersoftware,orbysimilarordissimilarmethodologynowknownorhereafterdevelopedisforbidden. Theuseinthispublicationoftradenames, trademarks, servicemarks, andsimilar terms,eveniftheyarenotidentifiedassuch,is nottobetakenasanexpressionofopinionastowhetherornottheyaresubjecttoproprietaryrights. 9 8 7 6 5 4 3 2 1 springer.com Foreword Environmental Chemistry: Fundamentals and Microscale Experiments When I was about eight years old, the beautiful wetland that stretched out beside my home wasdestroyedand wasreplacedbyalarge officepark. My father,upon seeing how upset Iwas, saidtome, "Ifyou care about something, you care enoughtolearn about it." This event perhaps more than anything else caused me to dedicate my life to sustaining ourenvironment,ourworld,through thepowerofchemistry.Andperhaps,morethanany thing else, this is also the lesson ofthese excellenttextbooks, EnvironmentalChemistry: FundamentalsandMicroscaleExperiments.Itistheknowledge andperspectivecontained in these textbooks that allows all of us as scientists to understand the way our environ ment functions onamolecularlevelandhowtoidentify potentialthreats tohumanhealth and the environment that need to be addressed. But they do more than that. They also give us the fundamental basis for ensuring that those problems never arise by using the Principles of Green Chemistry that emphasize avoiding hazards through innovations in chemistry. For much of the history of the environmental movement, the scientific community has sought to identify and quantify environmental problems. If we were able to identify the problems, we then sought ways to clean them up sometimes elegantly, sometimes expensively, sometimes both. Because of the knowledge and fundamentals presented in these textbooks we are able to build on those historical approaches and incorporate the principles of sustainable design into the chemical products and processes oftomorrow. The authors deserve tremendous credit for their extraordinary efforts that have resulted in these comprehensive and much needed volumes. These books will provide excellent resources for those aspiring scientists to understand that the way to protect the Earth is through intimately and rigorously understanding the Earth. Paul T.Anastas YaleUniversity December, 2006 v Preface Modemscienceisnotstraightforward.Intricaterelationshipsexistamongthedifferentdisciplinesinvolved intheunderstandingofvirtuallyeveryscientificissueandphenomenon.ThedaysoftheRenaissance,when a single person could master a large portion of the knowledge then available, are long gone. This is not due toalack ofindividual capacity, butrather totheexplosionofknowledge,characteristicofourtimes. EnvironmentalScience-andmore specifically,EnvironmentalChemistry-findsitselfcompletelyim mersed in such ascenario. Inthis regard, abook written by severalauthors having complementaryback grounds and interests appeared to be an appropriate projectto pursue. On the other hand, multiauthored undergraduatetextbooks runtheriskoflacking smoothnessandcontinuityinthepresentationofideasand concepts. The present project involved many meetings and cross-checking among the fiveauthors. This iswhy weperceive this finished task asvaluable, and wehope thatthereaderfindsaflowingprogression andfair treatmentofthevarious subjects. The book is written with sophomore or junior college students in mind (i.e., undergraduate students in their second or third year). However, issues are often presentedin such a way that General Chemistry students-and even graduate students----canfind subjects of interest applicable to their level. The book consists of a theoretical section (12 chapters) and a companion book with an experimental section (24experiments)intwoseparate volumes. Abriefdescriptionnowfollows (initials ofthemain authors of each chapterandexperimentappear inparentheses). The beginning ofthe theoretical section comprises ageneral introductiontoEnvironmentalChemistry (Chapter 1, MH), and a summary of the main background concepts that a student of Environmental Chemistry ought to know (Chapter 2, JI; Chapter 3, JI, AF,MS). Weassume that the students have the minimumbackgroundinOrganic ChemistryandinBiochemistrynecessaryforEnvironmentalChemistry. Subsequent chapters discuss the composition and characteristics of the natural chemical processes that occur in the atmosphere (Chapter4, AF), the lithosphere (Chapter 5, JI), and the hydrosphere (Chapter 6, MH and JI). This discussion concludes by examining natural biochemical processes and introducing the organisms in the biosphere (Chapter 7, CD). Chapters that follow then analyze the effects of many pollutants(Chapter8,JI,CDandMS;Chapter9,CD),theirtreatment(Chapter10,JIandCD;Chapter11, CD), and theminimizationandpreventionofpollution, emphasizingGreen Chemistry(Chapter 12,CD). Each chapteralsocontains alistofeducationalexperimentsintheliterature related toitssubject andalist ofother useful references. The experiments are rather varied, ranging from the characterization of aqueous media to pollutant treatment schemes. For increased safety, savings, and environmental awareness, as well as for reduced costs, wastes, andenvironmentaldamage, wepresentourexperimentsatthe microscalelevel (sometimes also called small-scale). Such experiments typically use microliters or micromoles of at least one of the reagents. The main authors ofeach experimentare asfollows: Experiments 1-4,MH; 5,6,JI; 7, AF and JI; 8, JI; 9, MH; 10, AF;11,12, JI; 13,14, JI and MS; 15, JI; 16,JI and AF; 17,JI and MH; 18-20, JI; vii viii Preface 21,JI(from anexperimentbyViktorObendraut); 22-24,CD.The answers toselected problemsfrom the various experimentsaregiveninthebook'swebsite atwww.springer.com. Many open-endedprojects are suggestedintheadditionalrelatedprojectssection ofeach experiment. The possibilities for accidents or personal injury while performing these experiments are fairly small. However,owingtotheincalculablenumberofvariables involvedwhen many individuals performexperi ments inseparate places withdifferent materialsandreagents,wecannotaccept anyresponsibilityinsuch unlikely events. In the same vein, we cannot accept responsibility for any possible consequences when performingtheadditionalrelatedprojectsdescribedabove. The books contain a total of 240 questions, problems, and examples; of these, over 100are solved in the text.They also containmore than 150figures, 70tables, and 1300references tothe literature(almost 50% of these references are related to educational environmental activities and experiments). Lastly, 80 additionalrelatedprojectsare suggestedintheexperimentalsection. Furthertechnicalnotes areinorder: (a) Even though the IUPAC(InternationalUnion for Pure and Applied Chemistry)has advised using the symbol e(for the electron)without itsnegative charge as superscript, wehave circumventedthis rule for didactic purposes since, in our experience, students are less confusedwhen balancing charges in redox equationswhen theyactuallyseetheminus signoftheelectroncharge. (b) Physicalstates are written here assubscriptsjustbelow theparticipantsinchemicalreactions,except foraqueous species. Afewyearsago, suchphysicalstates startedtobewritten asnormal letters rather than subscripts; however, we use the traditional convention here for the sake of clarity. In addition, following theusagesetforthbyperhapsthemostreferencedbookworldwideinAquaticEnvironmental Chemistry(Stummand Morgan), we adhere inthis text tothe practice that aqueous species aretobe understoodassuch,evenwhentheyappear withoutthecorrespondingphysicalstateassubscript. This undoubtedlyimproves thereadabilityofalargenumberofreactions. Asimilarideaappliestothegases inChapter4, where itwould becumbersometowrite their physicalstates. (c) Some chapters and subjects lend themselves more naturally than others to exercises (shown as examples). (d) All the experiments refer to specific chapters from the theoretical section, as written below each experiment'stitle. (e) Equations and figures in the worked examples are not numbered, unless they need to for apractical reason. (t) AplethoraofEnvironmentalChemistryexperimentsareperformedthroughouttheworld.Asthisbook presents merely a few of these subjects, each chapter also has references to other experimentation found intheliterature. The readerisencouragedtoinform theauthors ofanyomissions,sothatfuture editionsmaybeascompleteaspossible. (g) EnvironmentalAnalyticalChemistry isofthe utmost importanceinunderstandingalarge numberof environmentalissues, andthere aremanyexcellenttextbooks andlaboratorymanuals dealing withthis area of interest. Unfortunately, this rather extensive subjectrequires a strongerbackgroundthan that assumedforreaders ofthepresentbooks.Furthermore,themethodsandtechniquesinvolvedoftencall for somewhatsophisticatedequipmentnot available inallschools. Itisforthese reasons that wehave chosen toemphasizeotheraspects inthepresenttexts, andthusurgethereaders toseekkeyreferences inthisfieldelsewhere. Withsuchathoughtinmind, acomprehensivelistofEnvironmentalChemistry experiments that give prominence to analysis-and that require instrumentationbeyond that used in theexperimentalbook-isgiveninthe Appendix. Jorge Ibanezfirstconceivedthe idea for this book. Zvi Szafran(NewEnglandCollege, USA) induced us into making this projectcombine afull textbook and a laboratory manual. MargaritaHernandez was the architect and Jorge Ibanez the main driving force behindthe project-they weaved the threads from the different chapters into an orderly whole. In addition, Carmen Doria endowed these books with her expertise in the Life Sciences and Green Chemistry, Arturo Fregoso in the Atmospheric Sciences, and Preface ix Mohan Singh in Microscale Chemistry. In addition, all the authors participated in and reviewed other chaptersaswell. Workonthebooksgreatlybenefitedfrom commentsandsuggestionsmade byHugoSolis (Universidad NacionalAutonomadeMexico-UniversidadAutonomaMetropolitana- Azcapotzalco,Mexico)andMario Avila (Ecole Nationale Superiure de Chimiede Paris, France- Universidad de Guanajuato, Mexico). In addition,DaraSalcedo(MassachusettsInstituteofTechnology,USA- UniversidadAutonomadelEstado deMorelos,Mexico),PedroF.Zarate-DelValle(UniversitePierreetMarieCurie, France- Universidadde Guadalajara, Mexico), Sergio Gomez-Salazar (Syracuse University, USA - Universidadde Guadalajara, Mexico),MartinAdolfoGarcia-Sanchez(ITESO- Guadalajara),andLorenaPedraza-Segura(Universidad Iberoamericana)also helpedreadingsome portions. Andrea Silva-Beard gave the books the final administrative "push" for their completion. Rosa Maria Noriega provided the magic touch to the use of language through editing English grammar and style in most of the manuscript. Aida Serrano, Patricia Hernandez-Esparza, Marcela and Daniela Delgado Velasco revised some parts ofthe books. Juan Perez-Hernandez (PROVITEC) helped in getting all the authorstogetherfor meetings, and ElizabethGarcia-Pintortestedmost ofthe experiments. Alberto Sosa Benavides,AdrianaCanales-Goerne,GabrielaCastaneda-Delgado, and AlejandroCorrea-Ibargiiengoitia transformed many ofour rough sketches into understandable figures. The cover was developed after an idea firstconceivedby CarmenMariaTort-Oviedo(UniversidadIberoamericana). We are especially thankful to Ken Howell (Springer) for believing in us, and for his patience and encouragement. We also thank the many other co-authors and experimenters from other institutions that participated at different stages: Zvi Szafran (Merrimack College - Georgia Technical University, USA), Ronald M. Pike (Merrimack College - University of Utah, USA), Patricia Balderas-Hernandez (Universidad Nacional Autonoma de Mexico - Universidad Autonoma del Estado de Mexico), Bruce and Susan Mattson, Michael P. Anderson, Jiro Fujita, and Trisha Hoette (Creighton Jesuit University, USA), Alejandro Alatorre-Ordaz (Universidad de Guanajuato, Mexico), Viktor Obendrauf (Graz Pedagogical Academy, Austria), Michael W.Tausch and Michael Seesing (Universitat Duisburg-Essen, Germany), Rodrigo Mayen-Mondragon (CINVESTAV-Queretaro, Mexico), MariaTeresa Ramirez-Silva (UniversidadAutonomaMetropolitana- Iztapalapa,Mexico),ChristerGruvberg(UniversityofHalmstad, Sweden), Alanah Fitch (Loyola University-Chicago, USA), Adolfo de Pablos-Miranda (Institut Quimic de Sarria, Spain),and NorbertoCasillas(UniversidaddeGuadalajara,Mexico). Also, many thanks are in order for extensive experimental assistance in some cases and exceptional clerical help in others, to colleagues and students at Universidad Iberoamericana: Samuel Macias Bravo, Veronica Garces-Castellanos, SebastianTerrazas-Moreno, Rodrigo Mena-Brito, Carlos Navarro Monsivais, Ignacio Gallo-Perez, J. Clemente Miranda-Trevifio, Jose Topete-Pastor, Luis C. Gonzalez Rosas,IraidaValdovinos-Rodriguez,MariaLozano-Cusi,AnaLozano-Cusi,EnriqueLopez-Mejia,JoseA. Echevarria-Eugui,KarlaGarcia,JuanJose Godinez-Ramirez,FernandoAlmada-Calvo,LeticiaEspinoza Marvan,RosaMargaritaRuiz-Martin,Juan Jose Arrieta, AlejandroMoreno-Arguello, and DeniseSalas. Fundingwas-withoutadoubt--ofparamountimportanceforthedevelopmentofexperimentsthrough projects and research stays at diverse stages. This was kindly provided by Universidad Iberoamericana (Mexico), the International Business Office of CONACYT (Mexico), Merrimack College (USA), the National Microscale Chemistry Center (USA), the National Science Foundation (USA), the Fulbright Program of the Department ofState (USA), the Linnaeus - Palme Program ofthe Swedish Agency for InternationalDevelopment(Sweden), the Alfa Programofthe EuropeanCommission(Belgium), Loyola UniversityofChicago(USA), CreightonJesuitUniversity (USA), the UniversityofHalmstad(Sweden), and the UniversityofGuadalajara(Mexico). Above all, we thank our families for their gift of patience and understanding during the seemingly unendingand highlydemandinghours that this bookrequired. Weare convincedthat amongthe mostimportantissues inEnvironmentalScienceare the appreciation andknowledgeofthedifferentphenomenainvolvedinourenvironment,andtheon-goingneedtoparticipate in its care. We are hopeful that through these books we are contributing with a grain of sand to such an