Table Of ContentEnvironmental Chemistry
Environmental Chemistry
Fundamentals
Jorge G. Ibanez
MargaritaHemandez-Esparza
Carmen Doria-Serrano
Arturo Fregoso-Infante
MexicanMicroscale Chemistry Center
Dept.ofChemicalandEngineering Sciences
UniversidadIberoamericana-Mexico City
Mono Mohan Singh
National Microscale Chemistry Center
MerrimackCollege-NorthAndover, MA
~
Springer
Library ofCongressControlNumber:2007920054
ISBN-13:978-0-387-26061-7
eISBN-13:978-0-387-31435-8
Printedonacid-freepaper.
©2007SpringerScience-BusinessMedia,LLC
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springer.com
Foreword
When I was about eight years old, the beautiful wetland that stretched out beside my
home wasdestroyedand wasreplaced by alarge office park. My father,upon seeing how
upset I was,said to me, "Ifyou care aboutsomething, you care enough to learn about it."
This event perhaps more than anything else caused me to dedicate my life to sustaining
our environment, our world, through the power of chemistry. And perhaps, more than
anything else, this is also the lesson of this excellent textbook, Environmental Chem
istry: Fundamentals and Microscale Experiments. It is the knowledge and perspective
contained in this textbook that allows all of us as scientists to understand the way our
environmentfunctionsonamolecularlevelandhowto identifypotentialthreatsto human
health and the environment that need to be addressed. But it does more than that. It also
gives us the fundamental basis for ensuring that those problems never arise by using the
Principles ofGreen 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. Ifwe were able to identify
the problems, we then sought ways to clean them up sometimes elegantly, sometimes
expensively, sometimes both. Because ofthe knowledge and fundamentals presented in
this textbook we are able to build on those historical approaches and incorporate the
principles of sustainable design into the chemical products and processes of tomorrow.
The authors deserve tremendous credit for their extraordinary efforts that have resulted
in this comprehensive and much needed volume. This book will provide an excellent
resource for those aspiring scientists to understand that the way to protect the Earth is
through intimately and rigorously understanding the Earth.
Paul T. Anastas
Yale University
December, 2006
v
Preface
Modernscienceisnotstraightforward. Intricaterelationshipsexistamongthe differentdisciplinesinvolved
intheunderstandingofvirtuallyevery scientificissueandphenomenon.ThedaysoftheRenaissance,when
a single person could master a large portion of the knowledge then available, are long gone. This is not
due to alack ofindividual capacity, but rathertothe explosion ofknowledge,characteristicofourtimes.
Environmental Science-andmore specifically,EnvironmentalChemistry-finds itselfcompletely im
mersed insuch a scenario.In thisregard,a book written byseveral authors having complementary back
grounds and interests appeared to be an appropriate project to pursue. On the other hand, multiauthored
undergraduatetextbooksrun the risk oflackingsmoothnessand continuityinthe presentationofideasand
concepts. The present project involved many meetings and cross-checking among the five authors. This
iswhywe perceivethis finished task asvaluable, and we hope that the reader finds aflowing progression
and fair treatmentofthe varioussubjects.
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 presented in such a way that General Chem
istry students- and even graduate studenrs-i-can find subjects of interest applicable to their level. The
book consists ofa theoretical section (12 chapters) and a companion book with an experimental section
(24 experiments).A briefdescriptionnow follows (initialsofthe main authors ofeachchapterandexper
iment appear inparentheses).
The beginning ofthe theoretical sectioncomprises ageneral introduction to Environmental Chemistry
(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). We assume that the students have the
minimumbackgroundinOrganicChemistryand inBiochemistrynecessaryfor EnvironmentalChemistry.
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(Chapter8,11,CD and MS; Chapter9,CD), their treatment(Chapter10,JI and CD;Chapter II,
CD),and the minimization and preventionofpollution, emphasizingGreenChemistry (Chapter 12, CD).
Each chapteralso containsalist ofeducationalexperimentsin the literaturerelatedto its subjectand alist
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,and environmentaldamage,we presentourexperimentsatthe microscalelevel (sometimes
also called small-scale).Such experiments typically use microliters ormicromoles ofat least one ofthe
reagents. The main authors ofeachexperimentare as follows: Experiments 1-4,MH; 5, 6, 11;7, AFand
JI; 8, JI; 9, MH; 10, AF;ll,12, JI; 13,14,JI and MS; 15,JI; 16, JI and AF; 17, JI and MH; 18-20, JI;
vii
viii Preface
21, 11(from an experimentby Viktor Obendrauf); 22-24, CD. Theanswers to selectedproblems from the
variousexperiments are given in the book'swebsite atwww.springer.com.Manyopen-ended projectsare
suggested in the additional relatedprojects section ofeach experiment.
The possibilities for accidents orpersonal injury while performing these experiments are fairly small.
However,owingto the incalculablenumberof variables involved whenmany individuals perform experi
mentsinseparateplaceswith differentmaterialsandreagents,wecannotacceptanyresponsibilityinsuch
unlikely events. In the same vein, we cannot accept responsibility for any possible consequences when
performing the additional relatedprojectsdescribed above.
The book contains 240 questions, problems, and examples; of these, over 100 are solved in the text.
It also contains more than 150 figures, 70 tables, and 1300 references to the literature (almost 50% of
thesereferencesare relatedtoeducationalenvironmentalactivitiesand experiments).Lastly,80additional
relatedprojects are suggested in theexperimental section.
Furthertechnical notes are inorder:
(a) Even though the IUPAC (International Union for Pure and AppliedChemistry)has advised using the
symbol e (forthe electron) without itsnegative charge as superscript, we have circumventedthis rule
for didactic purposes since, inour experience, students are less confused when balancing charges in
redox equationswhen they actuallysee the minus sign of the electroncharge.
(b) Physical states are written here assubscriptsjustbelow the participants inchemical reactions,except
for aqueous species. Afew yearsago, such physicalstates startedto be writtenasnormal letters rather
than subscripts; however, we use the traditional convention here for the sake of clarity. In addition,
followingthe usagesetforth byperhaps themostreferencedbookworldwideinAquaticEnvironmental
Chemistry (Stumm and Morgan),we adhere in this text to the practice that aqueousspecies are to be
understood assuch,even when theyappearwithout thecorrespondingphysicalstateassubscript. This
undoubtedlyimprovesthe readabilityofalargenumberofreactions.Asimilarideaappliestothegases
inChapter4,where it would becumbersometo write theirphysical states.
(c) Some chapters and subjects lend themselves more naturally than others to exercises (shown as
examples).
(d) Old and new styles of writing references have been combined in this book. Most of the references
appear only with initials ofthe authors, as in the traditional manner. However,other references are
written according toan emergingtrend that includes entire names.
(e) Equations and figures in the worked examples are not numbered, unless they need to for a practical
reason.
(f) AplethoraofEnvironmentalChemistryexperimentsareperformedthroughouttheworld. Asthisbook
presents merely a few of these subjects, each chapter also has references to other experimentation
found inthe literature.The readerisencouragedtoinform the authors of any omissions,sothatfuture
editionsmay be as complete aspossible.
(g) Environmental Analytical Chemistry isof the utmost importance in understanding alarge numberof
environmentalissues,and therearemanyexcellenttextbooksand laboratorymanualsdealingwiththis
area ofinterest. Unfortunately,this rather extensive subject requires a stronger background than that
assumedfor readersofthe present book. Furthermore,the methods and techniquesinvolvedoften call
for somewhatsophisticatedequipmentnot available inall schools.It isfor these reasons that wehave
chosen toemphasizeotheraspectsinthe present text, and thus urge the readerstoseek keyreferences
inthis fieldelsewhere. With such athoughtinmind, acomprehensive listofEnvironmentalChemistry
experiments that give prominence to analysis-and that require instrumentation beyond that used in
the present book-isgiven in the Appendix.
Jorge Ibanez first conceived the ideafor this book. Zvi Szafran (New England College,USA)induced
us into making this a full textbook and not simply a laboratory manual. Margarita Hernandez was the
architect and Jorge Ibanez the main driving force behind the project-they weaved the threads from the
differentchapters into anorderly whole.Inaddition,Carmen Doriaendowed this book withherexpertise
Preface ix
intheLifeSciencesand GreenChemistry,ArturoFregoso inthe AtmosphericSciences,and MohanSingh
in MicroscaleChemistry. Inaddition,all theauthors participated inand reviewedotherchaptersas well.
Workon the book greatly benefited from commentsandsuggestions made by HugoSolis(Universidad
NacionalAutonomadeMexico-UniversidadAutonomaMetropolitana- Azcapotzalco,Mexico)and Mario
Avila (Ecole Nationale Superiure de Chimie de Paris,France - Universidad de Guanajuato, Mexico). In
addition,Dara Salcedo(Massachusetts InstituteofTechnology, USA - UniversidadAutonomadel Estado
deMorelos,Mexico),PedroF.Zarate-DelValle(UniversitePierreet MarieCurie,France- Universidadde
Guadalajara, Mexico), Sergio Gomez-Salazar(Syracuse University, USA - Universidad de Guadalajara,
Mexico),MartinAdolfoGarcia-Sanchez(ITESO- Guadalajara),and LorenaPedraza-Segura(Universidad
Iberoamericana)also helped reading some portions.
AndreaSilva-Beardgavethebookthefinaladministrative"push"foritscompletion.RosaMariaNoriega
provided the magic touch to the use of language through editing English grammar and style in most of
the manuscript. AidaSerrano,PatriciaHernandez-Esparza,Marcelaand DanielaDelgado-Velasco revised
some parts of the book.JuanPerez-Hernandez(PROVITEC) helped in getting all the authors togetherfor
meetings,and Elizabeth Garcia-Pintor tested most of the experiments. Alberto Sosa-Benavides,Adriana
Canales-Goerne,GabrielaCastaneda-Delgado,andAlejandro Correa-Ibarguengoitiatransformedmanyof
our rough sketches into understandable figures.The cover wasdeveloped after an idea first conceived by
Carmen MarfaTort-Oviedo (Universidad Iberoamericana).
Weareespeciallythankful toKen Howell (Springer)forbelievinginus,and for hispatienceand encour
agement. Wealso thank the many otherco-authorsand experimenters from otherinstitutions that partici
patedatdifferentstages:ZviSzafran(MerrimackCollege- GeorgiaTechnicalUniversity,USA),RonaldM.
Pike(MerrimackCollege- University ofUtah,USA),Patricia Balderas-Hernandez(UniversidadNacional
AutonomadeMexico- UniversidadAutonomadelEstadodeMexico),Bruceand SusanMattson,Michael
P.Anderson,Jiro Fujita,and Trisha Hoette (CreightonJesuitUniversity, 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), Maria Teresa Ramirez-Silva (Universidad Autonoma Metropoli
tana - Iztapalapa, Mexico),ChristerGruvberg (Universityof Halmstad, Sweden), Alanah Fitch (Loyola
University-Chicago,USA),and Adolfode Pablos-Miranda(InstitutQuimic de Sarria,Spain).
Also, many thanks are in order for extensive experimental assistance in some cases and excep
tional clerical help in others, to colleagues and students at Universidad Iberoamericana: Samuel
Macias-Bravo, Veronica Garces-Castellanos, Sebastian Terrazas-Moreno, Rodrigo Mena-Brito, Carlos
Navarro-Monsivais, Ignacio Gallo-Perez, J. Clemente Miranda-Trevifio, Jose Topete-Pastor, Luis C.
Gonzalez-Rosas, Iraida Valdovinos-Rodriguez, Maria Lozano-Cusi, Ana Lozano-Cusi, Enrique Lopez
Mejia, Jose A. Echevarria-Eugui, Karla Garcia, Juan Jose Godinez-Ramirez, Fernando Almada-Calvo,
LeticiaEspinoza-Marvan,RosaMargaritaRuiz-Martin,JuanJoseArrieta,AlejandroMoreno-Arguello,and
Denise Salas.
Fundingwas-withoutadoubt--ofparamountimportancefor the developmentofexperimentsthrough
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 of State (USA), the Linnaeus - Palme Program ofthe Swedish Agency for
International Development(Sweden),the Alfa Programof the European Commission (Belgium),Loyola
University of Chicago (USA), CreightonJesuit University (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 highly demanding hours that this book required.
Weare convincedthat among the most importantissues inEnvironmental Science are the appreciation
andknowledgeofthedifferentphenomenainvolvedinourenvironment,andtheon-goingneedtoparticipate
in itscare.Weare hopeful that through this book weare contributing with agrain ofsand to suchan end.
x Preface
Ourenvironmentisundoubtedlypartofagreater,transcendentalreality-itisinthissensethatwededicate
the presentbookadmajorem Deigloriam.
(Note:Namesoftheauthorsappearbelowfollowedbytheinstitutionswheretheydidgraduatework,then
by theirpresentaffiliations).
MargaritaHernandez-Esparza(Stanford University).UniversidadIberoamericana,Mexico City.
Ma.delCarmenDoria-Serrano(UniversidadNacionalAutonomadeMexico).UniversidadIberoamericana,
MexicoCity.
Arturo Fregoso-Infante (UniversityofMissouri-KansasCity).Universidad Iberoamericana, Mexico City.
Mono MohanSingh (St. Petersburg Institute ofTechnology).MerrimackCollege,MA, USA.
JorgeG.Ibanez (University ofHouston).Universidad Iberoamericana,Mexico City.
Mexico City andNorth Andover,MA,USA
Springof 2007
Contents
Foreword.............................................................................................................. v
Preface................................................................................................................. vii
Part 1 Introductory Concepts
1 Introduction toEnvironmental Chemistry............................................................... 3
1.1 Chemistry ofthe Natural ProcessesintheBiosphere.............................................. 3
1.2 Chemistry Associated withPollutionProcesses........................ 4
1.3 Chemistry Applied to the AnalysisofPollutantsand Natural Compounds. 6
1.4 Chemistry Applied totheTreatment andRemediation ofPollution...... ..... ....... 8
1.5 GreenChemistry.. .. . ............. ..... ............... 8
1.6 Importance ofEnvironmentalChemistry................ ..... . ...... .................. 9
Referencesand FurtherReading... ..... . .. . ... . ....... 10
2 Chemistry Fundamentals, Part A . .. ..... ............ 11
2.1 Chemical Equilibria.... ........ ....... ..... . . 11
2.1.1 Equilibrium ValuesandCalculations 12
2.1.2 Exchange Reaction Equilibria:Systemsofthe Type MLn/MLn- Ii ML/M...... 12
2.2 Acid-BaseReactions..................................................................................... 15
2.2.1 Acid-BaseCharacteristicsofCommon Chemical Species.............................. 15
2.2.2 Buffers............................................................................................. 16
2.2.3 Acid/Base CharacterofOxides..... .. . ..... .. . 21
2.3 RedoxProcesses.......... ..... .. ... . ... . 23
2.3.1 LatimerDiagrams....................... . . . ...... ... .. 25
2.3.2 Frost Diagrams................................................................................... 27
2.3.3 NemstEquation.................................................................................. 27
2.3.4 PourbaixDiagrams.............................................................................. 28
2.3.5 The pE Scale 33
References and Further Reading............... ........ .......... . ..... 41
3 Chemistry Fundamentals,Part B 43
3.1 Complexes and ComplexFormation............. 43
3.1.1 Definitionand Generalities.................................................................... 43
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