Handbook on Applications of Ultrasound - Dong Chen

Handbook on Applications of

UltrAsoUnd

EditEd by

dong CHen | sAnjAy K. sHArmA | ACKmez mUdHoo

Sonochemistry for Sustainability


UltrAsoUndSonochemistry for Sustainability

CRC Press is an imprint of theTaylor & Francis Group, an informa business

Boca Raton London New York


UltrAsoUnd

EditEd by

dong CHen | sAnjAy K. sHArmA | ACKmez mUdHoo

Sonochemistry for Sustainability

MATLAB is a trademark of The MathWorks, Inc. and is used with permission. The MathWorks does not warrant the accuracy of the text or exercises in this book. This books use or discussion of MATLAB software or related products does not constitute endorsement or sponsorship by The MathWorks of a particular pedagogical approach or particular use of the MATLAB software.

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To my lovely parents, wife Wei, and daughters Elena and Elisa

Dong Chen

In memory of my grandfather, Pt. Vishwambhar Dayal Sharma

Sanjay K. Sharma

For Yana, Teena, Assad, mum and dad

Ackmez Mudhoo

vii

ContentsForewordxiPreface xiiiAcknowledgmentsxvEditorsxviiContributorsxix

Chapter 1 EmergingUbiquityofGreenChemistryinEngineeringandTechnology1

Pavel Pazdera

Chapter 2 IntroductiontoSonochemistry:AHistoricalandConceptualOverview23

Giancarlo Cravotto and Pedro Cintas

Chapter 3 AspectsofUltrasoundandMaterialsScience 41

Andrew Cobley, Timothy J. Mason, Larisa Paniwnyk, and Veronica Saez

Chapter 4 Ultrasound-AssistedParticleEngineering 75

Anant Paradkar and Ravindra Dhumal

Chapter 5 ApplicationsofSonochemistryinPharmaceuticalSciences97

Robina Farooq

Chapter 6 Ultrasound-AssistedSynthesisofNanomaterials 105

Siamak Dadras, Mohammad Javad Torkamany, and Jamshid Sabbaghzadeh

Chapter 7 UltrasoundforFruitandVegetableQualityEvaluation 129

Amos Mizrach

Chapter 8 UltrasoundinFoodTechnology 163

Taner Baysal and Aslihan Demirdoven

Chapter 9 UseofUltrasoundinCoordinationandOrganometallicChemistry 183

Boris Ildusovich Kharisov, Oxana Vasilievna Kharissova, and Ubaldo Ortiz-Mndez

Chapter 10 UltrasoundinSyntheticApplicationsandOrganicChemistry 213

Murlidhar S. Shingare and Bapurao B. Shingate

viii Contents

Chapter 11 UltrasoundinSyntheticApplicationsandOrganicChemistry 263

Rodrigo Cella

Chapter 12 UltrasoundApplicationsinSyntheticOrganicChemistry 281

Mohammad Majid Mojtahedi and Mohammad Saeed Abaee

Chapter 13 Ultrasound-AssistedAnaerobicDigestionofSludge 323

Ackmez Mudhoo and Sanjay K. Sharma

Chapter 14 UltrasoundApplicationinAnalysesofOrganicPollutantsinEnvironment 345

Senar Ozcan, Ali Tor, and Mehmet Emin Aydin

Chapter 15 ApplicationsofUltrasoundinWaterandWastewaterTreatment 373

Dong Chen

Chapter 16 UltrasoundandSonochemistryintheTreatmentofContaminatedSoilsbyPersistentOrganicPollutants407

Reena Amatya Shrestha, Ackmez Mudhoo, Thuy-Duong Pham, and Mika Sillanp

Chapter 17 RoleofHeterogeneousCatalysisintheSonocatalyticDegradationofOrganicPollutantsinWastewater 419

Juan A. Melero, Fernando Martnez, RaulMolina, and Yolanda Segura

Chapter 18 DegradationofOrganicPollutantsUsingUltrasound447

Kandasamy Thangavadivel, Mallavarapu Megharaj, Ackmez Mudhoo, andRavi Naidu

Chapter 19 ApplicationsofUltrasoundtoPolymerSynthesis 475

Boon Mian Teo, Franz Grieser, andMuthupandian Ashokkumar

Chapter 20 MechanisticAspectsofUltrasound-EnhancedPhysicalandChemicalProcesses501

Vijayanand S. Moholkar, Thirugnanasambandam Sivasankar, and Venkata Swamy Nalajala

Chapter 21 Ultrasound-AssistedIndustrialSynthesisandProcesses 535

Cezar Augusto Bizzi, Edson Irineu Mller, ricoMarlondeMoraes Flores, Fbio Andrei Duarte, Mauro Korn, Matheus Augusto Gonalves Nunes, Paolade Azevedo Mello, and Valderi Luiz Dressler

Contents ix

Chapter 22 DevelopmentofSonochemicalReactor 581

Keiji Yasuda and Shinobu Koda

Chapter 23 UltrasoundforBetterReactorDesign:HowChemicalEngineeringToolsCanHelpSonoreactorCharacterizationandScale-Up 599

Jean-Yves Hihn, Marie-Laure Doche, AudreyMandroyan, Loic Hallez, andBruno G. Pollet

Chapter 24 Sonoelectrochemistry:FromTheorytoApplications 623

Bruno G. Pollet and Jean-Yves Hihn

Chapter 25 CombinedUltrasoundMicrowaveTechnologies 659

Pedro Cintas, Giancarlo Cravotto, and Antonio Canals

Chapter 26 IntegratingUltrasoundwithOtherGreenTechnologies:TowardSustainableChemistry 675

Julien Estager

xi

ForewordIn theeyesofnature,wecannotachieveasustainable futureby the linearextensionofexistingtechnologiesThisobservationdrivesthequestfornewwaystopracticechemistryOverthepast20years,anapproachtochemistryandengineeringdefinedbythe12principlesofgreenchemistryandgreenengineeringoffersusaprovenandsystematicwaytoaddresssustainabilityfromafirstdesignbasisWeknowtherearemorethan85,000chemicalsusedincommercearoundtheworldandthevastmajorityhasneverbeentestedforhumanhealthandenvironmentalimpactsWeknowtherearetrillionsofdollarsofcapitalinvestedinexistingchemicalmanufacturingplantsthatmustbeconsideredinanytransitionplanTherearenosilverbulletstoaddressingthesystemsalreadyinplaceHowever,asteadyandever-expandingapplicationoftheprinciplesofgreenchemistryandengineeringovertimewillallowustomakeprogressinreplacingourdependenceonpetroleum-derivedfuelsandfeedstocks

Chemists todaycangototheliteratureandfindtools tosynthesizejustaboutanycompoundonecanconceivebasedonestablishedtransformations,manyofwhichhavebeenaroundformorethanahundredyearsYetweknowmandoesnotpracticechemistrythewaynaturedoeschemistryandthereinliesourhopeforthefutureWemustcontinuetoinventanddevelopthetoolsofgreenchemistrytoallowatransitiontobio-inspiredchemistry

ThisbookisonesuchcommitmenttobuildingthenewgreenchemistrytoolboxItisfocusedprimarily on transformations aided by the use of sonochemistry (acoustic cavitation) The abil-ity todeliver rapid,high-densityenergy toasystemfacilitatesnewpossibilitiesWhile thecon-ceptsofsonochemistryhavebeenknownformorethan80years,in-depthunderstandingofthisphenomenoncontinues toevolveRecently, the techniquehasbegun to seeapplications rangingfromnanoparticleformationtocarbohydratesynthesistowastedestructionThus,sonochemistryappearstobeapplicabletoawidevarietyofchemicaltransformationsandhasthepotentialtoinflu-enceyields,dramaticallyreducereaction times,andincrease throughputAll theseelementsareconsistentwiththeprinciplesofgreenchemistryandengineering

Aswithanynewtechnology,agradualdevelopmentandadoptionprocesssetsinInitialeffortsfocusonunderstandingandscopingthenewtoolsandwenowseesyntheticsonochemistrytechnol-ogyfindinganever-increasingvarietyofapplications

Thisbookrepresentsawonderfulefforttobringtogetherthelatestdevelopmentsinthefieldandshouldproveusefultoallpracticingscientistswhohaveaninterestinexploringnewmethodstoinputenergyintoareactionprocess

P. Robert Peoples, PhDAmerican Chemical SocietyGreen Chemistry Institute

Washington, District of Columbia

xiii

PrefaceFollowingtheestablishmentofthe12 Principles of Green Chemistry(AnastasandWarner,1998),therehasbeenasteadygrowthinourunderstandingofwhatgreenchemistrymeansGreenchem-istryisarelativelyyoungscienceinitsownrespectInterestinthisdisciplineisgrowingrapidlyandistransgressingseveralcascadingresearchareasinscience,engineering,andtechnology(SharmaandMudhoo,2010)Theunderstandingoftheprinciplesthatbackbonegreenchemistryhasspurredmanyoutstanding efforts to implement chemical processes and innovative technologies that areincrementallytakingmodernsocietytowardsaferandmoresustainablepracticesandproductsthatembodyandfosterenvironmentalstewardship

Sonochemistryisabranchofchemicalresearchdealingwiththechemicaleffectsandapplica-tions of ultrasonic waves, ie, longitudinal sound waves with frequencies above 20kHz that liebeyond theupper limit of humanhearingalthough the rangeof ultrasonic frequencies canbeextendedupto100MHz(CravottoandCintas,2006)Sonochemistryshareswithsustainablechem-istrysuchaimsastheuseoflesshazardouschemicalsandsolvents,areducedenergyconsumption,andanincreasedproductselectivity(CravottoandCintas,2006)In thisregard,ultrasonicheat-ingand irradiationare inmany instancescomplementary techniques fordrivingchemical reac-tionswithahigherefficiencyandeffectivenessUltrasound,anefficientandvirtuallyinnocuousmeansofactivationinsyntheticchemistry,hasbeenemployedfordecadeswithvariedsuccesses(CravottoandCintas,2006)Notonlycan thishigh-energy inputenhancemechanicaleffects inheterogeneousprocesses,butitisalsoknowntoinducenewreactivitiesleadingtotheformationofunexpectedchemicalspeciesSonochemistryisuniqueinitsremarkablephenomenonofcavitation,currentlythesubjectofintenseresearch,andhasalreadyproducedinterestingresults

Imagingtechniquesusingecholocation,suchasSONARsystemsfortargetdetectionorechog-raphyinhealthcare,representperhaps thebest-knownuseofultrasoundChemicalapplicationsextendtosuchvariedareasasorganicandorganometallicchemistry,materialsscience,aerogels,water and wastewater treatment, food chemistry, and medicinal research (Cravotto and Cintas,2006)Thewritingofthishandbookhasbeenundertakenbecauseitwasearnestlyfelttobringfor-wardanupdatedpoolofthelatestresearchanddevelopmentfindingsthatreasonablyencompassafairnumberofmostrelevantaspectslinkedtoandlinkinggreenchemistrypracticestoenvironmen-talsustainabilitythroughtheusesandapplicationsofultrasound-mediatedandultrasound-assistedbiological,biochemical,chemical,andphysicalprocessesInthishandbook,arichpanoplyofnovelresearchfindingsandapplicationsofultrasonicradiationandsonochemistryhavebeenpresentedSeveralchaptershavebeenpresentedinthefollowingareas:medicalapplications,drugandgenedelivery,nanotechnology,foodtechnology,syntheticapplicationsandorganicchemistry,anaero-bicdigestion,pollutantdegradation,polymerchemistry,industrialsynthesesandprocesses,reactordesign,electrochemicalsystems,andcombinedultrasoundmicrowavetechnologies

Wesincerelyhope thishandbookprovidesa robustpoolofknowledgeon thegreenapplica-tionsofsonochemistryWealsofeelitprovidesup-to-dateinformationonsomeselectedfieldsofappliedresearchofultrasoundwheretheprinciplesofgreenchemistryarebeingembracedbythescientific,engineering,andtechnologicalcommunitiesforsafeguardingandimprovingthequalityoftheenvironmentandhumanlife,atlargeWealsowanttosharethatProfessorSanjayKSharmaandAMudhoohaverecentlyeditedabook,Green Chemistry for Environmental Sustainability(CRCPress,Taylor&FrancisGroup,2010),whichisanup-to-dateandhumblecontributiontotheliteratureongreenchemistry

xiv Preface

ForMATLABandSimulinkproductinformation,pleasecontact:

TheMathWorks,Inc3AppleHillDriveNatick,MA,01760-2098USATel:508-647-7000Fax:508-647-7001E-mail:info@mathworkscomWeb:wwwmathworkscom

REFERENCES

Anastas,PTandWarner,JC1998Green Chemistry: Theory and PracticeNewYork:OxfordUniversityPress

Cravotto,GandCintas,P2006Powerultrasoundinorganicsynthesis:Movingcavitationalchemistryfromacademiatoinnovativeandlarge-scaleapplicationsChemical Society Reviews,35:18096

Sharma,SKandMudhoo,A2010Green Chemistry for Environmental SustainabilityBocaRaton,FL:CRCPress,Taylor&FrancisGroup

Dong ChenSanjay K. Sharma

Ackmez Mudhoo

xv

AcknowledgmentsThisboldundertakinghasprovideduswithauniqueopportunitytorenewsomeoldfriendshipsandhopefullyweavesomenewonesinpursuitofgatheringanddistillingtheexpertiserequiredforedit-ingandcompilingthishandbookontheapplicationsofsonochemistryforsustainabalityWithoutany reservation, we heartily thank our esteemed contributors for the way they have graciouslyrespondedwithcharacteristicgoodhumorandpatiencetoourdeadlinesWealsoappreciatetheirconstructivecriticismsandsuggestions,whichhaveenhancedthecontentofthisworkWehopetheyeffortlesslyfeelthatthefinalresultdoesamplejusticetotheirpainstakingeffortsdeployedinpreparingtheirrespectivechapter(s)Weareequallyappreciativetowardothercolleaguesandfel-lowresearcherswhovolunteeredtheirhelpinreviewingthescientificcontentsofthemanuscripts

ProfessorSanjayKSharmaespeciallyexpresseshisheartfeltgratitudetohisrespectedparents,DrMPSharmaandSmtParmeshwariDeviHealsoextendshisregardstoProfessorRKBansal,whohasbeenasourceofinspirationtohim,andtoDrVKAgrawal,chairmanoftheInstituteofEngineeringandTechnology,Alwar(India),forhisencouragingwords

Ackmez Mudhoo expresses his appreciation for the faith his parents, Azad A Mudhoo andRuxanaBMudhoo,hisbrotherAssad, sister-in-lawTeena,and lovelynieceYannahaveplacedinhimthroughoutthewritingandcompilationofthishandbookHeisalsothankfultoProfessorKonradMorgan(vice-chancellorandchairmanofSenateof theUniversityofMauritius,Rduit,Mauritius), Professor Romeela Mohee (dean, Faculty of Engineering, University of Mauritius,Rduit,Mauritius),ProfessorPavelPazdera(MasarykUniversity,Brno,CzechRepublic),ProfessorMuthupandian Ashokkumar (Particulate Fluids Processing Centre, University of Melbourne,Australia),ProfessorGiancarloCravotto(UniversitdiTorino,Torino,Italy)andDrVinodKGarg(GuruJambheshwarUniversityofScienceandTechnology,Hisar,Haryana,India)fortheirpres-ence,encouragement,andsupport

Note:Thisworkwas supportedbyNewFacultyStartingFund fromIndianaUniversityPurdueUniversityFortWayne

xvii

EditorsDr. Dong Chen is an assistant professor at Indiana University-Purdue University Fort Wayne, Indiana He has been doingimportantfundamentalresearchinsonochemistry,environmentalchemistry,andwaterandwastewater treatment technologiesHehas served as the principal and coprincipal investigator of sev-eralfundedscientificresearchprojectsworthover$1millionDrChensworkenjoysahighreputationintheinternationalscientificcommunityandhasbeenwidelycitedbyhispeersHisresearchintheareaofultrasoniccontrolofmembranefoulingwasreportedbymanyscientificnewsmedia,includingNatureHehasmorethan30journal,book,andconferencepublicationsand2USpatentsHehasbeenservingasagrantreviewerfortheUSDepartmentof

AgricultureandNationalInstituteforWaterResourcesresearchprogramsInaddition,DrChenisaroutinereviewerfor12scientificjournalsandbooksHereceivedhisPhDincivil(environmental)engineeringwithaminoringeologicalsciencefromTheOhioStateUniversity,Columbus,Ohio,in2005Besideshisresearchexperience,DrChenhadbeenworkingasafull-timeengineeringconsultantformorethantwoyearsHeisalicensedprofessionalengineerinthestateofOhio

Professor (Dr.) Sanjay K. Sharmaisawell-knownauthorandeditor of many books, research journals, and hundreds of arti-cles over the last 20yearsOneof his books,Green Chemistry for Environmental Sustainability,hasbeenrecentlypublishedbyCRCTaylor&FrancisGroup,LLC,BocaRaton,FloridaHehasalsobeenappointedasserieseditorbySpringersLondonfortheirprestigiousbookseriesGreen Chemistry for Sustainability

DrSharmacompletedhispostgraduationin1995andreceivedhis PhD from the University of Rajasthan, Jaipur, in 1999 HisPhDthesiscoveredthefieldofsyntheticorganophosphoruschem-istry and computational chemistry In 1999, he started workingadditionally in the field of environmental chemistry and green

chemistryandproducedverygoodresearchpapersandbooksduringhis12yearlongstayattheInstituteofEngineeringandTechnology,Alwar,Rajasthan,India

Hisworkinthefieldofgreencorrosioninhibitorsiswellrecognizedandhasbeenwellreceivedby the international research community He is also actively involved in raising environmentalawareness,especiallywithregardtorainwaterharvesting

Presently, Dr Sharma works as a professor of chemistry at Jaipur Engineering College andResearchCentre,JECRCFoundation,Jaipur,Rajasthan,Indiaoneof thebestengineeringcol-leges in North Indiawhere he teaches engineering chemistry and environmental engineeringcoursestoBTechstudentsandpursueshisresearchinterestsHehasdeliveredmanyguestlecturesondifferenttopicsofappliedchemistryinvariousreputedinstitutionsHisstudentsappreciatehisteachingskillsandholdhiminhighesteem

DrSharmaisamemberoftheAmericanChemicalSociety(UnitedStates),theInternationalSocietyforEnvironmentalInformationSciences(Canada),andGreenChemistryNetwork(RoyalSocietyofChemists,UnitedKingdom)Heisalsoalifememberofvariousinternationalprofes-sionalsocieties,includingtheInternationalSocietyofAnalyticalScientists,theIndianCouncilof

xviii Editors

Chemists, the International Congress of Chemistry and Environment, and the Indian ChemicalSociety

DrSharmahas9booksonchemistryandover40researchpapersofnationalandinternationalreputetohiscredit,whichissufficientevidenceofhisfair trackrecordasaresearcherHealsoworksaseditorinchiefforthreeinternationalresearchjournals,RASAYAN Journal of Chemistry; the International Journal of Chemical, Environmental and Pharmaceutical Research; and the International Journal of Water Treatment and Green Chemistry,andservesasareviewerformanyotherinternationaljournals,includingtheprestigiousGreen Chemistry Letters and Reviews

Ackmez Mudhoo obtained his BEng (Hons) in chemical andenvironmental engineering from the University of Mauritius in2004 His research interests encompass the bioremediation ofsolid wastes and wastewaters by composting, anaerobic diges-tion, phytoremediation, and biosorption Ackmez has 48 inter-national journal publications (original research papers, criticalreviews,andbookchapters)and5conferencepaperstohiscredit,and an additional 7 research and review papers in the pipelinein his early career Ackmez also serves as peer reviewer forWaste Management; the International Journal of Environment and Waste Management; the Journal of Hazardous Materials;the Journal of Environmental Informatics; Environmental

Engineering Science;RASAYAN Journal of Chemistry;Ecological Engineering;Green Chemistry Letters and Reviews;Chemical Engineering Journal;andWater ResearchHeisalsotheeditorinchieffortheInternational Journal of Process Wastes TreatmentandtheInternational Journal of Wastewater Treatment and Green Chemistry,andservesashandlingeditorfortheInternational Journal of Environment and Waste ManagementandtheInternational Journal of Environmental EngineeringAckmezalsoreckonsprofessionalexperienceasconsultantchemicalprocessengineerforChinaInternationalWater&ElectricCorp(CWE,Mauritius)fromFebruary2006toMarch2008 He is also the coeditor of Green Chemistry for Environmental Sustainability (Publisher:CRCPress,Taylor&FrancisGroup,LLC,BocaRaton,Florida,454pp,ISBN:978-1-4398-2473-3)HeispresentlyalecturerintheDepartmentofChemicalandEnvironmentalEngineeringat theUniversityofMauritius

xix

Contributors

Mohammad Saeed AbaeeFacultyofOrganicChemistryandNatural

ProductsChemistryandChemicalEngineering

ResearchCenterofIranTehran,Iran

Muthupandian AshokkumarSchoolofChemistryUniversityofMelbourneParkville,Victoria,Australia

Mehmet Emin AydinEnvironmentalEngineeringDepartmentSelcukUniversityKonya,Turkey

Taner BaysalFacultyofEngineeringDepartmentofFoodEngineeringEgeUniversityIzmir,Turkey

Cezar Augusto BizziDepartmentofChemistryFederalUniversityofSantaMariaSantaMaria,Brazil

Antonio CanalsDepartmentofAnalyticalChemistryNutritionandFoodScienceandInstitute

ofMaterialsUniversityofAlicanteAlicante,Spain

Rodrigo CellaOxitenoS/AIndustryandTradeSantoAndre,Brazil

Dong ChenDepartmentofEngineeringIndianaUniversityPurdueUniversityFortWayne,Indiana

Pedro CintasFacultyofScienceDepartmentofOrganicandInorganic

ChemistryUniversityofExtremaduraBadajoz,Spain

Andrew CobleyFacultyofHealthandLifeSciencesTheSonochemistryCentreCoventryUniversityCoventry,UnitedKingdom

Giancarlo CravottoDepartmentofScienceandTechnology

ofDrugUniversityofTurinTorino,Italy

Siamak DadrasLaserMaterialsProcessingLaboratoryIranianNationalCentreforLaserScience

andTechnologyTehran,Iran

Aslihan DemirdovenFacultyofEngineeringandNaturalSciencesDepartmentofFoodEngineeringGaziosmanpaaUniversityTokat,Turkey

Ravindra DhumalCentreforPharmaceutical

EngineeringScienceUniversityofBradfordWestYorkshire,UnitedKingdom

Marie-Laure DocheNationalCentreforScientificResearchUniversityofFranche-ComteBesanon,France

Valderi Luiz DresslerDepartmentofChemistryFederalUniversityofSantaMariaSantaMaria,Brazil

xx Contributors

Fbio Andrei DuarteSchoolofChemicalandFoodFederalUniversityofRioGrandeRioGrandedoSul,Brazil

Julien EstagerTheQUILLResearchCentreTheQueensUniversityofBelfastBelfast,UnitedKingdom

Robina FarooqDepartmentofChemicalEngineeringCOMSATSInstituteofInformation

TechnologyLahore,Pakistan

rico Marlon de Moraes FloresDepartmentofChemistryFederalUniversityofSantaMariaSantaMaria,Brazil

Franz GrieserSchoolofChemistryUniversityofMelbourneParkville,Victoria,Australia

Loic HallezNationalCentreforScientificResearchUniversityofFranche-ComteBesanon,France

Jean-Yves HihnNationalCentreforScientificResearchUniversityofFranche-ComteBesanon,France

Boris Ildusovich KharisovSchoolofChemicalSciencesAutonomousUniversityofNuevoLeonMonterrey,Mexico

Oxana Vasilievna KharissovaSchoolofPhysico-MathematicalSciencesAutonomousUniversityofNuevoLeonMonterrey,Mexico

Shinobu KodaDepartmentofMolecularDesign

andEngineeringGraduationSchoolofEngineeringNagoyaUniversityAichi,Japan

Mauro KornDepartmentofMathematicalSciencesandEarthUniversityofBahiaSalvador,Brazil

Audrey MandroyanCentreNationaldelaRechercheScientifiqueUniversitdeFranche-ComtBesanon,France

Fernando MartnezDepartmentofChemicalandEnvironmental

TechnologyUniversidadReyJuanCarlosMadrid,Spain

Timothy J. MasonFacultyofHealthandLifeSciencesTheSonochemistryCentreCoventryUniversityCoventry,UnitedKingdom

Mallavarapu MegharajCentreforEnvironmentalRiskAssessment

andRemediationUniversityofSouthAustraliaAdelaide,SouthAustralia,Australia

and

CooperativeResearchCentreforContaminationAssessmentandRemediationoftheEnvironment

Salisbury,SouthAustralia,Australia

Juan A. MeleroDepartmentofChemicalandEnvironmental


Paola de Azevedo MelloDepartmentofChemistryFederalUniversityofSantaMariaSantaMaria,Brazil

Amos MizrachAgriculturalResearchOrganizationTheVolcaniCenterTheInstituteofAgriculturalEngineeringBetDagan,Israel

Contributors xxi

Vijayanand S. MoholkarDepartmentofChemicalEngineeringIndianInstituteofTechnologyGuwahatiGuwahati,India

Mohammad Majid MojtahediFacultyofOrganicChemistryandNatural

ProductsChemistryandChemicalEngineering

ResearchCenterofIranTehran,Iran

Raul MolinaDepartmentofChemicalandEnvironmental

TechnologyKingJuanCarlosUniversityMadrid,Spain

Ackmez MudhooFacultyofEngineeringDepartmentofChemicalandEnvironmental

EngineeringUniversityofMauritiusReduit,Mauritius

Edson Irineu MllerDepartmentofChemistryFederalUniversityofSantaMariaSantaMaria,Brazil

Ravi NaiduCentreforEnvironmentalRiskAssessment


and



Venkata Swamy NalajalaDepartmentofChemicalEngineeringIndianInstituteofTechnologyGuwahatiGuwahati,India

Matheus Augusto Gonalves NunesDepartmentofChemistryFederalUniversityofSantaMariaSantaMaria,Brazil

Ubaldo Ortiz-MndezSchoolofMechanicalandElectrical

EngineeringAutonomousUniversityofNuevoLeonMonterrey,Mxico

Senar OzcanEnvironmentalEngineeringDepartmentSelcukUniversityKonya,Turkey

Larisa PaniwnykFacultyofHealthandLifeSciencesTheSonochemistryCentreCoventryUniversityCoventry,UnitedKingdom

Anant ParadkarCentreforPharmaceutical

EngineeringScienceUniversityofBradfordWestYorkshire,UnitedKingdom

Pavel PazderaFacultyofSciencesDepartmentofChemistryCentreforSynthesesatSustainableConditions

andTheirManagementMasarykUniversityBrno,CzechRepublic

Thuy-Duong PhamLaboratoryofAppliedEnvironmental

ChemistryDepartmentofEnvironmentalSciencesUniversityofEasternFinlandMikkeli,Finland

Bruno G. PolletPEMFuelCellResearchGroupCentreforHydrogenandFuelCellResearchSchoolofChemicalEngineeringTheUniversityofBirminghamEdgbaston,UnitedKingdom

xxii Contributors

Jamshid SabbaghzadehIranianNationalCentreforLaserScience


Veronica SaezFacultyofHealthandLifeSciencesTheSonochemistryCenterCoventryUniversityCoventry,UnitedKingdom

Yolanda SeguraDepartmentofChemicalandEnvironmental


Sanjay K. SharmaJaipurEngineeringCollege&

ResearchCentreJaipur,Rajasthan,India

Murlidhar S. ShingareDepartmentofChemistryDrBabasahebAmbedkarMarathwada

UniversityAurangabad,India

Bapurao B. ShingateDepartmentofChemistryDrBabasahebAmbedkarMarathwada

UniversityAurangabad,India

Reena Amatya ShresthaDepartmentofCivilandEnvironmental

EngineeringLehighUniversityBethlehem,Pennsylvania

Mika SillanpLaboratoryofAppliedEnvironmental

ChemistryDepartmentofEnvironmentalSciencesUniversityofEasternFinland

and

FacultyofTechnologyLappeenrantaUniversityofTechnologyMikkeli,Finland

Thirugnanasambandam SivasankarDepartmentofChemicalEngineeringNationalInstituteofTechnologyTiruchirappalli,India

Boon Mian TeoSchoolofChemistryUniversityofMelbourneParkville,Victoria,Australia

Kandasamy ThangavadivelCentreforEnvironmentalRiskAssessment


and



Ali TorEnvironmentalEngineeringDepartmentSelcukUniversityKonya,Turkey

Mohammad Javad TorkamanyLaserMaterialsProcessingLaboratoryIranianNationalCentreforLaserScience


Keiji YasudaDepartmentofChemicalEngineeringGraduateSchoolofEngineeringNagoyaUniversityAichi,Japan

11 EmergingUbiquityofGreenChemistryinEngineeringandTechnology

Pavel Pazdera

CAUSES OF A CHEMISTRY CURSE

Thetermschemistry,chemicalindustry,andchemicalsevokeinthemindsofpeopleverynegativeassociationsandoftentimesexcitefearsThereasonsforthesenegativeassociationsareobservedfromthedaysofantiquityuptothepresentduetonegativeorratherbadhumanexperiencesinanumberofphenomenaconnectedwithchemistryanditsconquest

Atthepresenttime,thesenegativeassociationsarealsoevokedandprovokedbythemediaorbysomeecologicalactivistsItmayalsobesaidthatsuchnegativeassociationswithregardtochemis-tryanditssymptomsarebasedonrationalorirrationalfictionsandfeelings

InancienttimesandintheMiddleAgeswhenalchemyreignedasthepredecessorofpresentchemistry,peopleconnectedalchemyandalchemistactivitieswithevils,ghosts,demons,ghouls,devils,andSataninspiteofallpositivethingsthatitbroughttohumancivilizationsuchasnewpracticalandapplicableknowledge,findingsandobservations,chemicalelements,compounds,andnewmedicalproductsOntheotherhand,newpoisonsandtoxicdrugs,causticagents,blackgun-powder,andothernegativitieswereinventedandused(Armitage,2010;Brown,2006)

ThenineteenthandthetwentiethcenturiesbroughttomankindagreatdealofnewdiscoveriesaswellaspracticalandapplicableknowledgeAlso,duringthistimechemistrygavehumankindnewmaterials,medicalproducts,phytoeffectors,newtechnologies,andsyntheticprocedures(phytoef-fectorsmaybedefinedassubstancesortheirmixturesthatenablevegetablestodevelopprosper-ouslyfromgerminationtoharvesttimeandtheycontainnotonlypesticidesbutalsostimulantsforgrowthandimmunity)

Chemistry helped to boost the quality of human life and its development though it had itsowndisadvantagesMoreover,chemistryanditsproductsmaybemisappropriatedknowinglyor

CONTENTS

CausesofaChemistryCurse1WastesasRealEffectoftheAnthropogenicActivities4AnthropogenicWastesandTheirImpactsonNatureandDevelopmentofHumankind4ChemicalWastes7ChemicalWastesandSyntheticChemistryMetrics9SustainableDevelopment:StartingPointandPreventionofanUlteriorBeingofHumanCivilization 12SustainableDevelopment,Chemistry,andItsEngineeringandTechnologicalApplication 14PrinciplesandGoalsofGreenChemistry 16MethodologyandMethodsofGreenChemistry 17ReferencesandLiteratureResources 19

2 HandbookonApplicationsofUltrasound:SonochemistryforSustainability

unpredictably Several examples of badly applied chemistry can be demonstrated Phosgene(carbonyl dichloride, dichloromethane) (Merck Index, 11th edition, 7310), yperite (mustard gas,1,5-dichloro-3-thiapentaneorbis(2-chloroethyl)sulfide)(Cook,1999),newbrilliantexplosives(eg,2,4,6-trinitrophenolTNP, 2,4,6-trinitrotolueneTNT) (Urbanski, 1964; Ferro and Morrow Jr,2005),andotherchemicalproductsweredevelopedandusedforkillingsoldiersduringWorldWarIPhosgeneaswellasdiphosgene(trichloromethylchloroformate)ortriphosgene(bis(trichloromethyl)carbonate),safertohandlethanphosgene(KuritaandIwakura,1979),wasusedforthesynthesisoffunctionalderivativesofcarbonicacidForexample,carbamateshavebeenappliedaspesticidesorplastics(polyurethane)

AtthetimeofWorldWarII,manymen,mainlyJews,werepoisonedwithCyclonB(ie,hydro-gencyanide)(Zabecki,1999)ingaschambersofNaziconcentrationcampsWidespreadbiologi-calapplicationofhydrogencyanidewasinitiallylimitedtothefumigationofvaluabletreecrops,namely,citrusfruit,spreadingin1887fromCaliforniatoSpainandothercountries(Baur,1984)HydrogencyanideisstillinproductionintheCzechRepublicintheSyntheticFactoryDraslovkaKolnCo in thecityofKolnunder the trademarknameUraganD2and issoldforeradicatinginsectsandsmallanimalsOtherfumigantssuchasmethylbromide,cyanogens(dicyan),andcar-bonylsulfidearealsoused(MessengerandBraun,2000)Since2000BC,thehumanpopulationhasutilizedsubstancesor theirmixtureswithphytoeffectoraction toprotectand intensify theircropsSomeofthephytoeffectors,whichwerelatercalledpesticides,wereatfirstappliedasnaturalcompounds,eg,sulfurorextractsfromtobaccoOvertime,thepreparationofsyntheticmoleculesandsubstancesbegan

Two types of pesticides played a key role in the middle of the twentieth century: the veryunfortunate case of DDT (1,1,1-trichloro-2,2-di(4-chlorophenyl)ethane) and the 1:1 mixtureof isooctyl 2,4-dichlorophenoxyacetate and 2,4,5-trichlorophenoxyacetate contaminated by2,3,7,8-tetrachlordibenzo-p-dioxine (TCDD), well known as Agent Orange DDT is one of theworldsmostfamoussyntheticpesticideswithalong,unique,andcontroversialhistoryTheSwisschemistPaulHermannMllerwasawarded theNobelPrize inPhysiologyorMedicine in1948forhisdiscoveryofthehighefficiencyofDDTasacontactpoisonagainstseveralarthropods(http://nobelprizeorg/nobel_prizes/medicine/laureates/1948/)AfterWorldWarII,DDTwasusedasanagriculturalmiraculousinsecticide,andsoonitsproductionandwidespreaduseeruptedItsdeclineoccurredafter thediscovery thatDDTisapersistentorganicpollutantand isextremelyhydrophobicandstronglyabsorbedbysoilFurther,DDTanditsmetabolitesaretoxictoawiderange of animals in addition to insects, includingmarine animals suchas crayfish,daphnids, seashrimp,andmanyspeciesoffishTheyarelesstoxictomammalsbutmaybemoderatelytoxictosomeamphibianspecies,especiallyinthelarvalstageMostsignificantly,theyareareproductivetoxicantforcertainmarineandcontinentalbirdspeciesThesearchforfurthernegativeeffectsofDDThasbeenpursuedrelentlesslybytheWorldHealthOrganizationandbyotherinternationalandnationalspecializedagenciesItisaterriblefactthatsomepoorAfricancountriesusedDDTtilllately(USEnvironmentalProtectionAgency,1975)

AgentOrange is thecodenameforoneof theherbicidesanddefoliantsusedby theUSArmyinitsherbicidalwarfareprogramduringtheSecondVietnamWar(from1961to1971)(Stellman,2003)

Dioxin,namely,2,3,7,8-tetrachlordibenzo-p-dioxin, is thesyntheticby-productof thereactionof two phenoxyl herbicides mentioned earlier: iso-octyl ester of 2,4-dichlorophenoxyacetic acidand2,4,5-trichlorophenoxyaceticacidAgentOrangeisnotachemicalagentagainstmilitantsItwasappliedtoaidthesapperagentindestroyingthelandscapeblanketedbyfull-grownplantsandforestswhichservedasanaturalcoverforthenativewarriorsofVietConginVietnam,Laos,andCambodiaHowever, allnegative impactsofAgentOrangewereobservedbothon thewarriorsofVietCongandtheUSmilitaryVietnamesescientistshavebeenconductingepidemiologicalresearchontheimpactofdioxinonhumanhealthsincethelate1960sAccordingtotheVietnam

EmergingUbiquityofGreenChemistryinEngineeringandTechnology 3

RedCross,asmanyas3millionVietnamesepeoplewereaffectedbyAgentOrangeincludingatleast150,000childrenbornwithcongenitaldefectsThequestionastowhetherornottheexposuretodioxinaffectedthehealthof theVietnamesewasdebatedsincethetimeof thewarwhenthefirstanimalstudieswerereleasedshowingthat2,3,7,8-tetrachlorodibenzo-p-dioxinecausedcan-cerandcongenitaldefectsinrodentsStudiesofUSveteranswhoservedinthesouthduringthewarcomparedtothosewhodidnotgosouthfoundincreasedratesofcancerandnerve,digestive,skin,andrespiratorydisordersamongtheformerAmongthecancers,veteransfromthesouthhadhigher rates of throat cancer, acute/chronic leukemia, Hodgkins lymphoma and non-Hodgkinslymphoma,prostatecancer,lungcancer,softtissuesarcoma,andlivercancer(USEnvironmentalProtectionAgencyDioxinWebsite)

The second very unfortunate case connected with 2,3,7,8-tetrachlordibenzo-p-dioxine tookplace on July 10, 1976, in a small chemical manufacturing plant approximately 15km northofMilan in theLombardy region in Italyand isknownasSevesoDisaster (DeMarchietal,1972) The factory of the company Industrie Chimiche Meda Societ Azionaria (ICMESA)produced 2,4,5-trichlorophenol from 1,2,4,5-tetrachlorobenzene as an intermediate productfor 2,4,5-trichlorophenoxyacetic acid The reaction of 1,2,4,5-tetrachlorobenzene with sodiumhydroxideshouldhaveproceededundercontrolledtemperatureHowever,excessivepressureputtheoperationoutofcontroland6tonsofreactionmaterialwasdispersedoveranareaof18km2This material also included about 1kg of 2,3,7,8-tetrachlorodibenzodioxin, which is normallyseenonly in traceamountsof less than1ppmHowever, in thehigher-temperatureconditionsassociatedwiththerunawayreaction,theproductionofthementioneddioxinapparentlyreached100ppmormore Industrialsafety regulationscalled theSevesoDirectivepassed theEuropeanCommunity in1982 imposingmorestringentandharsher industrial regulationsTheSevesoDirective was updated in 1999, amended again in 2005, and is currently referred to as theSevesoIIDirective(orCOMAHRegulations in theUnitedKingdom)Similardirectiveswerealsoestablishedbygovernmentagenciesofothercountries(eg,USEnvironmentalProtectionAgencyEPA)

AnothersimilardisastercausedbyerroneoushandlingoftechnologicalequipmentoccurredduringthenightofDecember23,1984,inBhopal,MadhyaPradesh,IndiaThisindustrialcatas-trophe isgenerallywellknownas theBhopalDisasteror theBhopalGasTragedy(Broughton,2005)InapesticideplantofUnionCarbideIndiaLimited(UCIL),atankcontainingabout40tonsofmethylisocyanate(MIC)asanintermediateinthemanufacturingthepesticideCarbaryl(1-naphthylN-methylcarbamate,trademarkSevin)enteredintocontactwithlargeamountsofwaterThiscausedveryrapiddecompositioncombinedwithanacuteriseintemperatureandpressure(exothermicreactionundercarbondioxideformation),andleadingtotheworstindustrialdisastertodateAnexplosionresultedinalargevolumeofmixedtoxicgases,includingMIC,whichcon-taminatedtheregionofBhopalTheofficialdeathtollwasinitiallyrecordedataround5000Manysourcesindicatedthat18,000haddiedwithin2weeks,anditisestimatedthataround8000havediedsincethenasvictimsofgas-poisoning-relateddiseasesthatcroppedup(Browning,1993)Thedecisivefactorsthatcontributedtothedisasterincludethechemicalplantspoorlychosenlocation,theuseofhazardousingredientchemicalssuchasMICinsteadoflessdangerousones,storageofthesechemicalsinlargetanksinsteadofseveralsmallerstoragetanks,poormaintenanceandcontrolofequipmentatthechemicalplant,failureofseveralsafetysystems,whichwerenotinoperationatthetime(Carbarylisnotatpresentregisteredforpesticideusebecauseitisclassifiedasalikelyhumancarcinogen)

Boththesedisastersledtotighterspecificationsofsafetyinthechemicalindustryandtechnol-ogyapplicationsectorsThetragedyofThalidomide(Mogheetal,2008)isalsoaverywell-knownchemicaldisasterbecauseofliteraryandcinematographicelaborationsThalidomide((RS)-2-(2,6-dioxopiperidin-3-yl)-1H-isoindole-1,3(2H)-dione) was introduced as a sedative drug in the late1950sinWestGermanyandconsequentlyintherestoftheworldexcepttheUnitedStatesInthe


late1950sandearly1960s,morethan10,000childrenin46countrieswerebornwithdeformitiessuchasphocomeliaasaconsequenceofthalidomideuse

In1962,theUSCongressenactedlawsrequiringtestsforsafetyduringpregnancybeforeadrugcould receiveapproval for sale in theUnitedStatesOthercountriesenactedsimilar legislation,andthalidomidewasnotprescribedorsoldfordecadesThelaterexamplesofasadandbadappliedchemistry, riskofsomechemicals,chemical technologies, industry,andpollutionof theenvironmentbydifferentwastescontributetotheexplanationoftheexecrationofchemistryOntheotherhand,chemistryanditsproductsareemployedbypeopledaily,and,withoutthem,thenatureandcontemporarycharacteristicsofhumanlifeandqualitywouldbecomegenerallyverydifficult

WASTES AS REAL EFFECT OF THE ANTHROPOGENIC ACTIVITIES

Often,wehearviewsthatregardchemicalsassomethingbad,intheformofafoodand/oradrinkIfwedefine the termchemicals as elements, their compounds, andcompoundmixtures (Hilletal,2005),itrevealstheabsurdityoftheseviews,because,bystrictdefinition,drinkingwater,air,bread,hamandeggs,steak,housefly,dog,manyothers,and,evenmancouldbechemicalsFinally,wecandefinelifeasahighlysophisticatedself-organizedsetoftransformationsandpro-cessesofsomechemicalsintootherchemicalswhichtakeplaceinsidealivingorganismfromthetimeoftheirconceptiontothemomentoftheirfatality(Koshland,2002)Inthecourseoftheirlifecycle,wastes are formed (containingwater, inorganic, andorganic substances), andproducts ofaerobicand/oranaerobicrespiration(carbondioxideandoxygen),deadmatteroftabernacles,andotherresiduesareproduced

ProcessesofwasteformationandtheircirculationareinevitableforlifeBecauseotherorgan-ismsconsumeandderivebenefitfromsuchwastesorthesewastesstayintheenvironmentassedi-mentaryrocks(limestone,flintstone,guano,coalbed,andotherrock),onemayfindsomeregionswithhighconcentrationsofthesewastes(Blattetal,1980)

Allhighlysophisticatedself-organized transformationprocessesofwastes,and theiruseandreuseintheenvironment,includingthebiosphere,proceedthereforeinclosedandwell-balancedcycles(Beckett,1981)AnyorganismneedschemicalsubstancessuchasfoodandproductsotherthanchemicalsubstancessuchaswastesandalloccurthroughoutthecomplexfoodchainsandfoodwebsAsimpleexamplewouldbegreenplantsthatarefoodforfauna,astheyyieldoxygenfortheanimalkingdomandplantsViceversa,animalsproduceexcrementsandexpiredcarbondioxideasafoodforflora(PolisandWinemiller,1996)

ANTHROPOGENIC WASTES AND THEIR IMPACTSONNATURE AND DEVELOPMENT OF HUMANKIND

Wastesproducedbythehumansocietyprofoundlyunderliedifferentprocessesbecauseofthedif-ferentqualitiesandquantitiesofthewastesthatareproducedattheendofthesecomplexprocessesThequantityofwastesincreasesduetoariseinpopulation,andthequalityofwasteismorediversebecause of the ever-increasing industrial activities and their complexity Both are affected by achangeinlifestyleofhumansandbythegrowthintheirconsumptionpatternsOvertime,thedevel-opmentofhumankindleadstothereleaseoftoxicchemicalsintotheenvironmentThesetoxicchemicalsascompoundsofheavymetalsorradioactivechemicalsgetconcentratedintheenvironmentTheconcentrationof toxicorhazardoussubstanceshasaverynegativeeffectontheenvironmentincluding thebiosphereThis isbecause thenaturalenvironmentalcyclescannotassimilateanddegradethesepollutantsanyfurtherinasustainableandeffectivemannerProcessesofwasteaccu-mulationarethereforenon-sustainableAtthetimeoftheindustrialandpostindustrialsociety,thetermwastetookonanewdimension(PongrczandPohjola,2004)


Wastemaybedefinedasmass(orenergy)thatisformedduringthemanufacturingprocessofaproductwithautilityvalueandwhichremainswhenthisproductlosesitsutilityvalueThiswastecontinuestobeawasteuntilitiseitherreintegratedintoanenvironmentoritischangedintoanewproduct(s)withanewutilityvalue

AcopyofthenewspaperThe Timescanhelpasanexamplefortheabove-mentioneddefinitionItisevidentthatduringthepreparationprocessofacopyofThe Timesadifferentbutbroadspec-trumofwastesisproducedHowever,thisisnotaproblemformostnewspaperreaderssincetheylookforwardtolearnaboutcurrentnewsThenewspaperhasforthemanactualutilityvalueequaltothepriceof1,whichforamajorityofreadersacquireszero-valueafteraread-throughandturnsintowasteendingupinacontainerItisinprinciplebadwhenthiswasteisterminatedasmunicipalwastebecauseitscurrentutilityvalueisnegativeOntheotherhand,thiswastepapermaybereusedasfiringmaterial(smallbutstillwithapositiveutilityvalue)orpreferablyrecycledasfreshrawmaterial(anetmorepositiveutilityvalue)Archivingnewspapersinlibraries,archives,orinrecordofficesisanunusualwayofusingread-throughnewspapersTheutilityvalueofthisread-throughcopyofThe Timesispositiveand,overaperiodoftime,itincreases

In this context, itpoints towardaproductof life-cycleassessment (LCA)LCA(CooperandFava,2006)maybedefinedasamethodtoassesstheenvironmentalaspectsandpotentialimpactsassociatedwithaproductbasedoncompilinganinventoryofrelevantenergy,materialinputs,andenvironmentalreleases,onevaluatingthepotentialenvironmentalimpactsassociatedwithidenti-fiedinputsandreleasesincludingpotentialhazards,andoninterpretingtheresultshelptocomeupwithamoreinformeddecision

Thepossibilityofaccessingthesourcesofbasematerialsandenergyisthesecondmostimpor-tant factor in the development of humankind These sources can be classified in terms of theiravailabilityaspermanent(eg,basematerialssuchaswater,saltyseaandoceanwater,nitrogen,oxygen,andotherairgasesandenergysuchassolarandgeothermalenergyandkineticorpotentialenergyofflowingwaterandagitateair)orasrenewable(eg,greenalgaeandplants,charcoal,andnuclearenergy)biomassThepermanentandrenewablesourcesarethereforeclassifiedassustain-ablewhereas thenonrenewable sourcesarecategorizedasnon-sustainable (Lancaster,2002) Inthesequel,anumberofhumanactivitiesconnectedwiththeirdevelopment,namelyinthetimeofindustrialandpostindustrialsociety,havealwaysresultedinhazardousconsequencesAsexamples,clearingofforestandtropicalrainforest(Moran,1993)forobtainingagriculturalfarms,landforcivilconstructions,orforobtainingroundwoodasrawmaterial(Hartman,1992);theuseofcyanideforgoldmining(Ali,2006);ortheuseofsulfuricacidforuraniumminingresultinthepollutionofwaters,productionofgreenhouseandotherhazardousatmosphericgasesFurthermore,theproduc-tionandexploitationofgenerallytoxicandhazardousproductsandtheapplicationofmethodsfortheirproductionleadtoenvironmentalpollution

Thepossibilityofhazardisthethirdimportantfactorinthedevelopmentofhumankind(EricsonIII,2005)Bynature,hazardinvolvessomethingthatcouldpotentiallybeharmfultoapersonslife,health,property,ortheenvironment(MacCollum,2006)Onekeyconceptinidentifyinganyhaz-ardisthepresenceofstoredenergythat,whenreleased,cancausedamageStoredenergycanoccurinmanyforms:chemical,mechanical,thermal,radioactive,orelectricalAnotherclassofhazarddoesnotinvolvethereleaseofstoredenergyRather,itinvolvesthepresenceofhazardoussitua-tionsExamplesincludeconfinedorlimitedegress,oxygen-depletedatmospheres,awkwardposi-tions,repetitivemotions,andlow-hangingorprotrudingobjectsHazardandvulnerabilityinteracttogethertocreaterisk

Thecauseofthe20082009worldwidefinancialandeconomiccrisis,whichhadarisenasa result of derivatives of dangerous financial products or phosgene substitution by dimethylcarbonatewhichisproducedduringahazardoushigh-pressuresynthesisfrommethanolandcarbondioxideconstitutesthepossibilityofhazardHazardcannotbecompletelyeliminatedbutcanbeavoidedbyexperthandlingofsafetydevices,andcanthusbeminimizedItisneces-sarytoeliminatehazardoussituationsorstateswhicharenon-sustainableItstandstoreason


thattheLCAforapapercopyoftheThe Timesandfortheabove-mentionedherbicideAgentOrangewillbetotallydifferentThepaperversionoftheThe TimesthereforecontinuestobeissuedwhereasAgentOrangeisforbiddenforuse

ThequantityofwasteduringamanufacturingprocessofatargetproductcanbedefinedasthemassdifferencebetweentheamountofrawmaterialsandthetargetproductThevalueiscommen-surabletotheefficiencyofrawmaterialexploitation,productioncosts,andthefinalpriceofproducts

Waste isdirectly linked tohumandevelopment,both technologically and sociallyThecom-position of different wastes has varied over time and location, with industrial development andinnovationExamplesofthisincludeplasticsandnucleartechnologyAnthropogenicwastetypesdefinedbymodernsystemsofwastemanagement(Rhyner,1995)aremunicipalsolidwaste(MSW),constructionanddemolitionwaste(C&DW),institutionalwaste,commercialwaste,andindustrialwaste(IC&I),medicalwaste(alsoknownasclinicalwaste),hazardouswaste,radioactivewaste,andelectronicwaste

Wastesthatareformedduringanthropogenicactivitiesmaybelocalizedinanintegralenviron-ment,ie,onthesurfaceoftheEarthinsoils,inthewaterofrivers,seas,oceansandsubterraneanwaters,andintheatmosphereChemicalsubstanceswhicharecontainedinanthropogenicwastesmaybetransformedintheenvironmentbynaturalenvironmentalprocesses,eg,duringbiodegra-dationinsoil,water,andairbytheenzymaticactionoflivingorganismssuchasbacteria,yeasts,andgreenplantsunderaerobicand/oranaerobicconditions(Diaz,2008)

Solongaswastesarenottransformedintheenvironmentintoenvironment-friendlyandaccept-ablederivatives,theyfunctionaspollutantswithallnegativeresults,eg,asgeneraltoxicresiduesandagentsdepletingtheozonelayerItisgenerallyknownthatchemicalcompoundswithstrongchemicalbondssuchaspolyaromatichydrocarbons(PAHs),chlorinatedand/orfluorinatedhydro-carbons such as chlorofluorocarbons (CFCs, freons), chloromethanes, and the above-mentioneddioxinsaredangerousfortheenvironment(Williamsetal,2000)

Wastes can also be classified according to their state of matter such as solid, liquid, and/orgaseousortheirmaterialuniformitysuchashomogeneousorheterogeneous;industrialwastecanbecategorizedbythelocationoftheirgenesis,eg,atsourceorendofpipewastesThebestsituationistohavewastesthatarenotgeneratedPreventionofwasteproductionandpreventionofpollutionareprincipalapproachesofwastemanagement(ClarkandMacquarrie,2002)Disposalofendofpipewastesincludesallanthropogenicwastetypesandmaybedescribedbythefollowingsequenceofprocedures:

1Reuseoforiginalproductmaterialasfreshresourcesofmaterialorenergy 2Biodegradationbycompostingorusageinaerobic/anaerobicsewerageplants 3Wasteincinerationwithcleaningofcombustionproducts 4Controlledwastedumping 5Wasteincinerationwithoutcleaningofcombustionproducts 6Noncontrolledwastedumping

WasteseparationgenerallypreventsitsdisposalTheenvironmentaladvantageofthissequenceisdecreasing,andishenceratheranalogoustomaterialmeritandutilityvalueThehazardofthe presented procedures escalates especially for events 46 Cost-efficiency is variable anddependsonwastecharacteristics,costsofprocedure,andenvironmentalassessment(DobleandKruthiventi,2007)

Moreover,somecompaniesmovepollutingmanufacturingprocessesfromdevelopedcountriestothepoorerdevelopingcountries(least-developedcountries),forreasonsthatneednocomment,inanefforttosavecoststhereafterThissolutiondoesnotpreventtheconsequencesOntheotherhand,itcreatesforthesecompaniesproblemswithflexibilityofproductionandtransportForthepreventionofhazardousorriskysituations,disasters,andaccidents,themonitoringandanalysisofallhazardousfactors(Mannan,2005)areimportantThemonitoringandanalysisofthemovement


ofchemicalsubstancesincludeallwastetypesintheenvironment,a toxicityanalysisofcurrentandnewchemicals,acapacityassessmentofmaterialandenergysources,otherhazardousfactors,andenvironmentalcostsConsequently,ariseinthequalityandquantityofwastes,theirlocalandtemporalconcentrations,andtheself-regulatedprocessesintheenvironmentmaybeinhibitedandtheentiresystemmaybedeflectedfrombalance

Anumberofpersons(environmentalistsandpoliticians)haverealizedthisfatalproblemofenvironmentalpollutionAndfortheperpetuityofhumancivilization,thesepeoplehaverecentlystartedseekingsolutionsTheapproachestoaddresstheseimpendingenvironmentalhealththreatsarediscussedinthefollowingsection

CHEMICAL WASTES

Asmentionedearlier,theexistenceofcontemporaryhumancivilizationwithoutchemistry,chemi-cals,andthepharmaceuticalindustry,andwithoutchemicalprocessesasapplicableintheprocess-ingindustryandenergyindustryishardlyconceivableHowever,humanactivitiesconnectedwithchemistry,chemicalengineeringprocesses,andthechemicalindustryyieldverynegativeimpactsontheenvironmentandcreateallsortsofhazards

Polyacrylonitrile(PAN)preparedbyfree-radicalvinylpolymerizationofmonomeracryloni-trile(vinylcyanide)isaresinous,fibrous,orrubberyorganicpolymer(Morgan,2005)Thesyn-theticretro-projectionofPANmanufacturingisillustratedinScheme11Itisgenerallyknownasamaterialforuseinthetextileindustry,oftenincombinationwithnaturalfiberssuchascottonandwoolPANfibersarealsothechemicalprecursorsofhigh-qualitycarbonfibersTheyarechemicallymodifiedtomakecarbonfibersfoundinplentyofbothhigh-techandcommondailyapplications suchasprimaryand secondary structuresof civil andmilitaryaircraft,missiles,solidpropellantrocketmotors,pressurevessels,fishingrods,tennisrackets,badmintonrackets,andhigh-techbicyclesAlmostallPANresinsarecopolymersmadefrommixturesofmonomerswithacrylonitrileasthemaincomponentItisacomponentrepeatunitinseveralimportantcopo-lymers,suchasstyreneacrylonitrile (SAN)andacrylonitrilebutadienestyrene(ABS)plasticEvidently,PANanditscopolymersareveryimportantfortheexistenceofcontemporaryhumanlifeOntheotherhand,PANisaverystablematerialwhichishoweverproblematicallyintegratedintotheenvironmentbecauseofitsincompletecombustionthatproduceshydrogencyanideandnitrogenoxides

Monomeracrylonitrile (Dalinetal,1971) ismanufacturedby thecatalyticammoxidationofpropyleneorbythecatalyticadditivereactionofhydrogencyanidewithacetylene(Goodrichpro-cess)HydrogencyanideisproducedmainlybytheAndrussovoxidationprocessinwhichmethaneandammoniareactinthepresenceofoxygenatabout1200CoveraplatinumcatalystMethane,propylene,andacetylenearepetrochemicalproducts,andthereforenonrenewablerawmaterialsHowever,ammoniacanbecharacterizedasarenewablerawmaterialandoxygenasapermanentoneAllthechemicalsusedforacrylonitrilemanufacturingincludingacrylonitrileitselfarehighly

CNCN

CH HCN HC

HC

H3C

CH

CH4 + NH3 + O2CH2 + NH3 + O2

+CC* *H

H2

nnH2C

SCHEME 1.1 Syntheticretro-projectionofPANmanufacturing


hazardousandexplosiveinamixturewithair,flammable,andgenerallytoxicThesetechnologicalprocessesarealsohazardousbecausetheyinvolvehighpressuresandhightemperatures

Ibuprofen(nowoutdatedinthenomenclatureiso-butyl-propanoic-phenolicacid,Brufen,Nurofen,andAdvil,systematicchemicalIUPACname(RS)-2-(4-(2-methylpropyl)phenyl)propanoicacid)isoneofthreemass-appliedpharmaceuticals(theothertwobeingaspirinacetylsalicylicacidASA,andParacetamolN-acetyl-4-aminophenolAPAP) with analgesic, antiphlogistic (anti-inflammatory),andantipyreticeffects(Rainsford,1999)Scheme12depictsthesyntheticretro-projectionproductionofibuprofenbytheBootsmethodandScheme13showsthesyntheticretro-projectionofibuprofenmanufacturingbytheHoechstmethod

Ibuprofen is manufactured currently (procedure of Hoechst company, Presidential [USA]GreenChemistryChallenge:GreenerSyntheticPathwaysAwardin1997)byathree-stepsynthe-sisstartingwiththeFriedelCraftspara-acetylationofiso-butylbenzenebyacetanhydrideinthepresenceofhydrogenfluorideastheLewisacidcatalystThissyntheticstepproducesaceticacidandhydrogenfluorideaswaste,butaceticacidcanbeusedasarawmaterialforotherchemicalsynthesesandhydrogenfluoridecanbereusedJustusinghydrogenfluorideisveryinnovativebecauseFriedelCraftsacetylationofaromaticsusingaluminiumchlorideasaLewisacidarecommonlyapplied

Ontheotherhand,thereisnodoubtthatbothaceticacidandincreasinglyhydrogenfluoridearehazardoussubstances In thenext step,4-acetylated iso-butylbenzene ishydrogenatedonRaneynickelasaheterogeneouscatalystunderpressuretogivethecorrespondingalcohol,whichinathirdstepundergoespalladium-catalyzedcarbonylationbycarbonmonoxide

Onceagain,alltheabovereagents,intermediateproducts,andcatalystsaresomehowhazardousIntermsofthesourceinputs,nickelandpalladiumarenon-renewable,andhydrogenandcarbon

O

O

O

ClCH2COOC2H5

NaOC2H5O

(CH3CO)2O

AlCl3

NOH

NH2OH OH+/H2O

O

OH

HydrolysisN

Dehydratation

SCHEME 1.2 Syntheticretro-projectionofibuprofenmanufacturingbyBootsmethod

OH

O

OH

O

H2, Raney Ni

CO, [Pd]

(CH3CO)2O

HF

SCHEME 1.3 Syntheticretro-projectionofibuprofenmanufacturingbyHoechstmethod


monoxidecanbemarkedaspartlyrenewablerawmaterialsClassificationinbothcasesdependsontheusedenergyandcarbonmonoxideoncarbonsourceAsustainablemethodforcarbonmonoxidemanufacturingishencebasedeitheronthereactionofcarbon(ie,charcoal)withcarbondioxide,controlledoxidationofcharcoal,orcellulosepyrolysis

Evaluations of synthetic processes are necessary for an assessment of their environmentalimpacts, theutilizationofmaterialandenergy inputs,wasteproduction,andcosts involvedWethereforeneedtodefinethecontentofasyntheticprocessorofachemicalsynthesisChemicalsynthesismaybedefinedasaprocessthatstartsfromthetimeoflocationofreagent(s),possiblesolvent(s),catalyst(s),andauxiliariesinareactoruptothepointofendingtheirreaction,separation,andpurificationprocessofreactionproduct(s),finallyculminatingintheadjustmentofproduct(s)ThefirstandlastpartsofthedefinitionareimportantbecausetheyhelptoexploretherequirementofenergyandworkandtheircostsforallprocessesOntheotherhand,theyhelptoobtainarealoutlookonsomesensationalso-calledsolvent-freesynthesesThesecasesarereportedveryoften,but, in a further view, they are not solvent-free syntheses Respective reactions proceed indeedwithoutasolvent,butamixtureofreagentshavebeenmixedinsolvents(fordepositiononsolidsupport)and/or thefinal (solid)producthasbeenpurifiedbyusingasolventTheadvantagesofone-pot,multicomponent,anddominoreactionsexcelinthecontextofthesyntheticprocessdefinedearlierbecauseseveralsyntheticorreactionstepsarelocatedinthesamereactorwithoutseparation,purification,transport,andadjustmentoftheintermediaryproduct

CHEMICAL WASTES AND SYNTHETIC CHEMISTRYMETRICS

Achemicalone-stepsynthesismaybedescribedasinScheme14Anidealgoalofsyntheticprocessesisthefullconversionofstartingreactantsintoapurefinal

targetproductCwithouttheapplicationofothersubstances(catalyst,solvent,auxiliaries)andwith-outenergyclaimsInaddition,thisprocessshouldbeconductedwithouttheformationofregio-and/orstereoisomersofthetargetproductC,C,by-product(s)D,nonconvertededucts%A,%B,catalyst,solvents,andauxiliaries,whichareabreedinggroundforwasteformationbecausetheyarenotembeddedintheproduct,andadditionalenergyandlaborareneededfortheirseparationHowever,idealsyntheticproceduresoccurverysporadicallyHence,trade-offsmustbesoughtandconsideredDesigningsyntheticprocesseshelpsoptimizethesecompromises

Currentchemistry,engineering,andtechnologyuseanumberofindexes(syntheticchemistrymetrics)toassesstheefficiencyofsyntheticprocesses(LapkinandConstable,2008):

1ConversionXofreactantAorB(oneoftwoismarkedaskeyorlimitingreactant)isthedegreeofitsutilizationforanyproductformationinagivenmomentThisindex(avalueof01or0%100%,theoreticalmaximumX=1orX=100%)showshowmanykeyreactantsareutilizedforproductformationandsignifieshowmuchofitisleftaswasteforwastemanagement Conversion may be increased by the arrangement of synthetic procedure

A + B C+C+C+D+%A+%B

Catalyst, solvent,auxiliaries

Energy and work

SCHEME 1.4 Generalschemeofone-stepchemicalsyntheticprocess(A,B:Startingreactants,educts;C:targetproduct;C,C:isomers,bothregioandstereo,ofthetargetproduct(undesirable);D:by-product(undesirable);%A,%B:nonconvertededucts;catalyst:acidbase,metalcomplex,homogeneousorhetero-geneoussolventforreactionand/orforpurification;auxiliaries:sorbentforpurification,surfactant, inertgas;energyforheating,cooling,stirring,highpressure,vacuum,transportandworkofstaff)


conditions,eg,byachangeofsolvent,andapossiblepressure-ortemperature-induceddisplacementofchemical/dynamicequilibrium

2YieldofthetargetproductCistheamountofproductobtainedasaresultofachemicalreactionTherelationshipbetweenyieldYandconversionXisgivenbythemultiplicationoperationY=XS,whereSisaselectivityofreactionforthetargetproduct,allcalculatedonmolarbasisOtherwise,arelationshipisfoundbetweenthemassofthetargetproductanditstheoreticalcalculatedvalue,rangingfrom0to1or0%to100%,withatheoreticalmaximumforY=1orY(%)=100%Yieldaswellasconversionandreactionselectivitymaybeincreasedbyachangeofsyntheticprocedureconditions

3Effectivemassyieldisdefinedastheratiobetweentheweightofthetargetproductandthemassofallnon-benignmaterials incident in thecourseof itssynthesis(ie, regio-and/orstereoisomersofthetargetproduct,by-product(s),catalyst,solvents,andauxilia-ries)TheweaknessofthismetricistherequirementforafurtherdefinitionofabenignsubstanceItisassumedthatthesehavenoenvironmentalriskassociatedwiththem,eg,water,low-concentrationbrine,inertgases,diluteethanol,autoclavedcellmassmaybereferredtoasbenignThisdefinitionisverysubjectivebecauseenvironmentaldatamaybeincomplete

4Environmentalfactor(E-factor):RogerSheldonsE-factor(Sheldon,1992,1994,1997a,b,2000,2007,2008)canbeviewedascomplexandthoroughandontheotherhandassimplewhenrequiredAssumptionsonsolventandotherfactorscanbemadeoratotalanalysiscanbeperformedTheE-factorcalculationisdefinedbytheratioofthemassofwasteperunitofproductThisvalueisverysimpletounderstandandtouseE-factorignoresrecy-clablefactorssuchasrecycledsolventsandreusedcatalysts,whichobviouslyincreasetheaccuracybutignoretheenergyinvolvedintherecoveryThemaindifficultywithE-factorsistheneedtodefinesystemboundariesbeforereliableandmeaningfulcalculationscanbeperformedandthesedifferfromassessortoassessorThislimitationisthemaindraw-backofallmetricswith theexceptionof theextremelycomplexLCAofaproductByincorporatingyield,stoichiometry,andsolventusage,theE-factorisanexcellentmetricCrucially,E-factorscanbecombinedtoassessmultistepreactionsstepbysteporinonecalculationSheldondemonstratedinhisdocumentsthatthechemicalindustrysectorwithabulkytonnageofannualproductionachievingrelativelysmallvaluesofE-factor,eg,petrochemicalindustryandindustry,producedbulkchemicalshavinganE-factorof015atanannualproductionof104108tonsOntheotherhand,chemicalcompaniesproduc-ingfinechemicalsandpharmaceuticalshadfortheirannualproductionof10410tonsanE-factorincomparablyhigherat5100ThesedatahencedemonstratethatoilcompaniesproducealotlesswastethanpharmaceuticalsasapercentageofmaterialprocessedThisreflectsthefactthattheprofitmarginsintheoilindustryrequirethemtominimizewasteandfindalternativeusesforproductswhichwouldnormallybediscardedaswaste,oritmaybetransformedbycatalyticprocessestoreusablefundamentalproducts(methane,ethane,ethylene,andhydro-craftingofheavynaturalresinparaffines)Bycontrast,thepharmaceuticalsectorismorefocusedonmoleculemanufacturingandqualityTheactuallyhighprofitmarginswithinthepharmaceuticalsectormeanthatthereislessconcernaboutthecomparatively largeamountsofwaste thatareproduced(especiallyconsidering thevolumesused)althoughithastobenotedthat,despitethepercentageofwasteandE-factorbeinghigh,thepharmaceuticalsectorproducesmuchlowertonnageofwasteperproductunit thananyother sectorAsmentionedearlier,byobtaining the relevantdata for thecalculationofaconversion,yield,effectivemassyield,andE-factor,asyntheticorprocessexperiment may be performed Synthetic or process experiments are not necessary forthecalculationofafurther46chemistrymetricsbecauseofthechemicalsynthesisandsyntheticprocessmodelingdiscussedbelow


5Atomeconomy(atomefficiencyAE)isdesignedinadifferentwayfromalltheabovemetricsItcanbedesignedasamethodbywhichorganicchemistswouldplanoncleanersyntheticprocessesverysimplyTheessentialdefinitionofatomeconomyisbasedonhowmuchofthereactantremainsinthefinalproductForasingle-stepprocedureoftheabovesynthesis,atomeconomymaybecalculatedas

AE

molecular weight of Cmolecular weight of A B

=

+( )

Forageneralmultistepreactionscheme

A + B C followed C + D E and next E + F G

themathematicaldefinitionofatomeconomyisdescribedas

AE

molecular weight of Gmolecular weight of

=

+ + +(A B D F)

The weakness of AE is that the used catalyst, solvents, and auxiliaries are ignored astheyarenotincorporatedintothefinalproductAEalsoignoresthepossibilityforreuseofsecondaryreactionproductsbyrecyclingAEcalculationisverysimpleandusefulasalowatomeconomyatthedesignstageofareactionpriortoenteringthelaboratorycandriveacleanersyntheticstrategytobeformulatedTherangeofAEis01or0%100%,foratheoreticalmaximumY=1orY(%)=100%achievableforisomerizationreactions,rearrangement, additive reactions including DielsAlder and similar cyclo-additions iftheseproceedwithoutmoreisomerformationInthesereactiontypes,onlyoneproductisformedOntheotherhand,intheWittigreactionorMitsunobureaction,averypoorAEisobtainedbecauseheavytriphenylphosphineoxideisformedOtherexamplesofpoorAEmaybethenucleophilicsubstitutionreactionsofhalogensonsaturatedcarbonatomunderSN2reactionconditionsAlkyliodidesareveryreactiveatthesealkylatingreactions

6Carbonefficiency(CE)isanothermetricderivedfromAE,butisusedonlyfortheeffi-ciencyofcarbonatomsinvolvedinthesyntheticprocessThemathematicalrepresentationisaccordingtoAE,butinlieuofmassofallatomsthemassofcarbonatomsisconsideredThismetricisagoodsimplificationforuseinthepharmaceuticalindustry(andinsus-tainablepetrochemistrytoo)asittakesintoaccountthestoichiometryofreactantsandproductsFurthermore, thismetric is of interest to thepharmaceutical industrywherethedevelopmentofcarbonskeletonsisimportantfortheworkThegoalistoconserveallcarbonatomsinthematrixofthecompoundAvalueofCElessthan1isconnectedwithcrackinganddecarboxylationreactionsBulkydecarboxylationreactionsobservedinpetrochemistrymightbethesourceofmassivevolumesofgreenhousecarbondioxideHence,thisindexshowsthatthepotentialtransformationofplantoilsintohighalkanesor alkenesas renewableproductswillnotbebasedonhydrolysis anddecarboxylationreactions,butonreductionthroughthecatalytichydrogenationoffunctionalizedcarboxylgroupsinplantoils

7ReactionmassefficiencyisalsoanothermetricderivedfromAE,butinthecalculation,themassofproductandeductsisusedinlieuofmolecularweightThedifferencebetweenAEandreactionmassefficiencyvaluesmayariseifeductsreactnotinarealreactionbutonastoichiometricbasis(excessofnon-keyreactant)Inthiscase,avalueforreactionmassefficiencylessthantheatomeconomyisobtained

8TheEcoScale(VanAkenetal,2006)isarecentlydevelopedmetrictoolfortheevaluationoftheeffectivenessofasyntheticreactionIt ischaracterizedbysimplicityandgeneral


applicabilityLiketheyield-basedscale,theEcoScalegivesascorefrom0to100,butalsotakesintoaccountcost,safety, technicalsetup,energy,source,andpurificationaspectsItisobtainedbyassigningavalueof100toanidealreactionTheproposedapproachisbasedonassigningarangeofpenaltypointstotheseparameters:

EcoScale = 100 sum of individual penalties

This semiquantitative analysis can easily be modified by other synthetic chemists whomayfeelthatdifferentrelativepenaltypointsshouldbeassignedtosomeparametersItisapowerful tool tocompareseveralpreparationsof thesameproductbasedonsafety,economical,source,andenvironmentalfeatures

SUSTAINABLE DEVELOPMENT: STARTING POINT AND PREVENTION OF AN ULTERIOR BEING OF HUMAN CIVILIZATION

Since the late1960sandearly1970s somepeople fromacademia, civil society,diplomacy,andindustryhavebeguntobeawarethatthecurrentlifestyleanddevelopmentofhumankindisnotfur-thersustainableAmassivepollutionoftheenvironmentinconsequenceofindustrialactivitiesandmanufacturing,andoverexploitationofnaturalrawmaterialandenergysourceshavetakenplace

Hence,inApril1968,TheClubofRome(KingandSchneider,1993)wasfoundedasaglobalthinktankthatwoulddealwithavarietyofinternationalpoliticalissuesIthasraisedconsiderablepublicattentionin1972withitsreportbookThe Limits to Growth(Donellaetal,1972),whichusedtheWorld3model tosimulate theconsequencesof interactionsbetweentheEarthssystemsandhumansystemsTheclubstatedthatitsmissionistoactasaglobalcatalystforchangethroughtheidentificationandanalysisofthecrucialproblemsfacinghumanityandthecommunicationofsuchproblemstothemostimportantpublicandprivatedecisionmakersaswellastothegeneralpublic

OnJuly9,1970,citingrisingconcernsoverenvironmentalprotectionandconservation,USpresi-dentRichardNixontransmittedReorganizationPlanNo3totheUnitedStatesCongressbyexecutiveorder,creatingtheEPAasasingle,independentagencyfromanumberofsmallerarmsofdifferentfederalagenciesPriortotheestablishmentoftheEPA,thefederalUSgovernmentwasnotstructuredtocomprehensivelyregulateenvironmentalpollutantsTheUnitedNations(UN)ConferenceontheHumanEnvironment(alsoknownastheStockholmConference)wasaninternationalconferencecon-venedundertheUNauspicesheldinStockholm,Sweden,fromJune5to16,1972

ItwastheUNsfirstmajorconferenceoninternationalenvironmentalissues,andmarkedaturningpointinthedevelopmentofinternationalenvironmentalpoliticsThemeetingagreeduponadeclara-tioncontaining26principlesconcerningtheenvironmentanddevelopment,anActionPlanwith109recommendations,andaResolutionIn1973theEuropeanUnion(EU)createdtheEnvironmentalandConsumerProtectionDirectorate,andcomposedthefirstEnvironmentalActionProgram

In1987,OurCommonFuture(OurCommonFuture(1987),Oxford:OxfordUniversityPress),also known as the Brundtland Report, from the UN World Commission on Environment andDevelopment(WCED)waspublishedThepublicationofOurCommonFutureandtheworkoftheWCEDlaidthegroundworkfortheconveningofthe1992EarthSummitandtheadoptionofAgenda21,theRioDeclaration,andtheestablishmentoftheCommissiononSustainableDevelopment

Anoft-quoteddefinitionofsustainabledevelopment(SD)isdefinedinthereport:Developmentthatmeetstheneedsofthepresentwithoutcompromisingtheabilityoffuturegenerationstomeettheirownneeds

Inaddition,keycontributionsofOurCommonFuturetotheconceptofSDincludetherec-ognitionthatthemanycrisesfacingtheplanetareinterlockingcrisesthatareelementsofasinglecrisisofthewholeandofthevitalneedfortheactiveparticipationofallsectorsofsocietyincon-sultationanddecisionsrelatingtoSD


Agenda21(http://wwwunorg/esa/dsd/agenda21/)isaprogramrunbytheUNrelatedtoSDandwas theplanetsfirstsummit todiscussglobalwarmingrelated issuesAgenda21clearly identi-fiedinformation,integration,andparticipationaskeybuildingblockstohelpcountriestoachievedevelopmentthatrecognizestheseinterdependentpillarsItemphasizesthatinSDeveryoneisauserandproviderofinformationItstressestheneedtochangefromoldsector-centeredwaysofdoingbusinesstonewapproachesthatinvolvecross-sectoralcoordinationandtheintegrationofenviron-mentalandsocialconcernsintoalldevelopmentprocessesFurthermore,Agenda21emphasizesthatbroadpublicparticipationindecisionmakingisafundamentalprerequisiteforachievingSDItisacomprehensiveblueprintofactiontobetakenglobally,nationally,andlocallybyorganizationsoftheUN,governments,andmajorgroupsineveryareainwhichhumansdirectlyaffecttheenvironment

Such increased interestand researchcollaborationarguablypaved theway for furtherunder-standingofglobalwarming,whichhas led to suchagreementsas theKyotoProtocolThis isaprotocoltotheUnitedNationsFrameworkConventiononClimateChange(UNFCCCorFCCC),aimedatfightingglobalwarmingTheUNFCCCisaninternationalenvironmentaltreatywiththegoalofachievingstabilizationofgreenhousegasconcentrationsintheatmosphereatalevelthatwouldpreventdangerousanthropogenicinterferencewiththeclimatesystemTheProtocolwasinitiallyadoptedonDecember11,1997inKyoto,Japan,andentered intoforceonFebruary16,2005AsofNovember2009,187stateshavesignedandratifiedtheprotocol,butwithouttheUnitedStatesandothercountries

OnSeptember8,2000,followinga3-dayMillenniumSummitofworldleadersattheheadquar-tersoftheUnitedNations,theGeneralAssemblyadoptedtheMillenniumDeclarationAfollow-upoutcomeoftheresolutionpassedtheGeneralAssemblyonDecember14,2000toguideitsimple-mentationProgressonimplementationoftheDeclarationwasreviewedatthe2005WorldSummitofleaders

TheWorldSummitonSustainableDevelopment(WSSD)orEarthSummit2002tookplaceinJohannesburg,SouthAfrica,fromAugust26toSeptember4,2002ItwasconvenedtodiscussSDbytheUNWSSDgatheredanumberofleadersfrombusinessandnongovernmentalorgani-zations,10yearsafterthefirstEarthSummitinRiodeJaneiro(ItwasthereforealsoinformallynicknamedRio+10)

The2009UNClimateChangeConference,commonlyknownastheCopenhagenSummit,washeldinCopenhagen,Denmark,betweenDecember7and18

Theconferenceincludedthe15thConferenceoftheParties(COP15)intheUNFCCCandthe5thMeetingoftheParties(COP/MOP5)intheKyotoProtocolAccordingtotheBaliRoadMap,aframeworkforclimatechangemitigationbeyond2012wastobeagreedthereTheconferencewasprecededby theClimateChange:GlobalRisks,Challenges, andDecisions scientific conference,whichtookplaceinMarch2009andwasalsoheldattheBellaCentreThenegotiationsbegantotakeanewformatwheninMay2009UNSecretaryGeneralBanKi-moonattendedtheWorldBusinessSummitonClimateChangeinCopenhagen,organizedbytheCopenhagenClimateCouncil(COC),whereherequestedCOCcouncilorstoattendNewYorksClimateWeekattheSummitonClimateChangeonSeptember22andengagewithheadsofgovernmentonthetopicoftheclimateproblem

WhatresultsfromSDmightbeastartingpoint,solution,andpreventionofanulteriorbeingof human civilization It might optimize close relations between production, economy, humansociety, the biosphere, and the environment Hence, SD is built on three pillars: environment,economy,andsociety

SDisanoptimal intersectionofsetsofallentities in theenvironment,economy(includingproduction), andhumansocietySDcouldbeviable (forproduction, economy,and theenviron-ment),sociallyandeconomicallyequitable,andsociallyandenvironmentallybearableinallandfor all Most countries have no problem in accepting these environmental pillars However, theacceptanceoftheseeconomicalandsocialpillarsmaygeneratescrupleorevenasilentoppositioninpoorerdevelopingcountriesorleast-developedcountriesontheonehand,butalsoindevelopedcountriesontheother,namely,thosewithaneoliberalgovernmentonprincipleasaThirdWay


SDalsohassomeshortfallsatitsstartTheproportionbetweenthesizeofthepopulationandnonrenewableresourcesisincommensurableandthistrendwillgrowevenfurther(Cohen,1995)Theproportionbetweenthestandardoflifeofthepeopleindevelopedcountriesandthatinleast-developedcountries is incommensurableandthisdifferencewillnotceaseduringthe lifetimeofonehumangenerationEveryoneofthreerichestmenintheworldisinpossessionofmorepropertythanthewealthof48mostneedycountriesintheworld,whiletherichestwomaninFrancehasanannualincomethatequalsthatof15,700ofherfellowcitizenswhodrawminimalwages(Keller,2010)

TheseproportionsshowthattheinequalitybetweensomepeopleandsomecountriesproducesadifferencethatwillprobablyrisefurtherMoreover,iftheeconomyindevelopedcountriesdoesnotshowcharacteristicsofgrowthinhumanconsumption,theglobaleconomywillsufferproblemsAlbertBartlett, inhiscontributionTheLawsofSustainabilityintheanthologyThe Future of Sustainability(Keiner,2006),isveryskepticalaboutthewordsustainabilityinconnectionwiththe term development and in the context of an exponentially growing human population Heassertsinhisfirstof21LawsofSustainabilitythatthetermSustainableGrowthisanoxymo-ronInthenextlaws,hedeclaresthatOnecannotsustainaworldinwhichsomeregionshavehighstandardsoflivingwhileothershavelowstandardsofliving(5thLaw),Thebenefitsofpopula-tiongrowthandofgrowthintheratesofconsumptionofresourcesaccruetoafew;thecostsofpopulationgrowthandgrowthintheratesofconsumptionofresourcesarebornebyallofsociety(9thLaw),Humanswillalwaysbedependentonagriculture(16thLaw),If,forwhateverreason,humansfailtostoppopulationgrowthandgrowthintheratesofconsumptionofresources,Naturewillstopthesegrowths(18thLaw),Starvingpeopledontcareaboutsustainability(19thLaw),Theadditionof thewordsustainable toourvocabulary, toourreports,programs,andpapers,tothenamesofouracademicinstitutesandresearchprograms,andtoourcommunityinitiatives,isnotsufficienttoensurethatoursocietybecomessustainable(20thLaw),andhefinisheswithExtinctionisforever

AlltheserealitiesdonotleaveusfeelingoptimisticaboutthefurtherSDofhumankindHence,the activities of current political and economic elites, establishments, scientists, engineers, andtechnologistsarefocusedontheenvironmentalandeconomicalpillarsofSDasitsprofitablepartsOntheotherhand,amutualrelationshipbetweentheenvironment,economy,andproductionactivi-tiesisevident

Consequently,theconceptofsustainabledevelopmentmaybeunderstoodasasetofsustain-ableendeavorsaimingatthebettermentandsurvivalofhumankindfollowingtherationaldevelop-mentandresponsivegrowththatthisconceptentails

SUSTAINABLE DEVELOPMENT, CHEMISTRY, ANDITSENGINEERING AND TECHNOLOGICAL APPLICATION

Chemical production and its engineering and technological application are economically andsociallyverybeneficialtohumanitybutareverydisadvantageousfornaturalsourcesandfortherestoftheenvironmentWiththegoalofharmonizingthisdisproportionatebalance,thefollowingremedialsolutionshavecomeintodemand

In1990,thePollutionPreventionActpassedintheUnitedStatesThisacthelpedtocreateamodusoperandifordealingwithpollutioninanoriginalandinnovativewayItaimedatavoidingproblemsbeforetheyactuallyhappenedShortlyafterthepassageofthePollutionPreventionActof1990,theEPAsOfficeofPollutionPreventionandToxics(OPPT)begantoexploretheideaofdevelopingneworimprovingexistingchemicalproductsandprocessestomakethemlesshazard-oustohumanhealthandtheenvironment

In1991,theOPPTlaunchedthemodelresearchgrantsprogramAlternativeSyntheticPathwaysforPollutionPreventionThisprogramprovided,forthefirsttime,grantsforresearchprojectsthatincludedpollutionpreventioninthesynthesisofchemicalsSincethattimetheGreenChemistry


ProgramhasbuiltcollaborationswithmanypartnerstopromotepollutionpreventionthroughgreenchemistryPartneringorganizationsrepresentacademia,industry,othergovernmentagencies,andnongovernmentalorganizations

Inthenameofgreenchemistry,correspondingactivitieshavestartedforthefirsttimeinallcoun-triesexceptContinentalEuropeIntheEUanalogousactivitiesmaybepresentundertheindicesofsustainablechemistry

TheEuropeanEnvironmentAgency(EEA),anagencydevotedtoestablishinganetworkforthemonitoringoftheEuropeanenvironment,wasfoundedbytheEURegulation(EuropeanEconomicCommittee(EEC)Regulation)1210/1990,asamendedbyEECRegulation933/1999Workstartedin earnest in 1994 The regulation also established the European environment information andobservationnetwork(Eionet)

Registration, Evaluation, Authorization and Restriction of Chemicals (REACH) is an EURegulationofDecember2006REACHaddressestheproductionanduseofchemicalsubstancesandtheirpotentialimpactsonbothhumanhealthandtheenvironment

REACHhasbeendescribedasthemostcomplexlegislationintheEUshistoryandthemostimportantin20yearsItisthestrictestlawtodateregulatingchemicalsubstancesandwillaffectindustriesthroughouttheworldREACHenteredintoforceinJune2007,withaphasedimplemen-tationoverthenextdecadeWhenREACHisfullyenforced,itwillrequireallcompaniesmanu-facturingorimportingchemicalsubstancesintotheEUinquantitiesof1tonormoreperyeartoregisterthesesubstanceswithanewEuropeanChemicalsAgency(ECHA)inHelsinki,FinlandBecauseREACHappliestosomesubstancesthatarecontainedinobjects(articlesinREACHterminology),anycompanyimportinggoodsintoEuropecouldbeaffected

About143,000chemicalsubstancesmarketedintheEUwerepreregisteredbytheDecember1,2008deadlineAlthoughpreregisteringisnotmandatory,itallowspotentialregistrantsmuchmoretimebeforetheyhavetofullyregister

SupplyofsubstancestotheEuropeanmarketwhichhavenotbeenpreregisteredorregisteredisillegal(knowninREACHasnodata,nomarket)REACHlegislationcanthereforehelptopre-ventariskconnectedwiththeuseofhazardouschemicals

IncontrasttotheEPA,theEEAdoesnotorganizeprogramssuchastheEPAGreenChemistryProgramTheEuropeanTechnologyPlatformforSustainableChemistry(SusChem)isaEuropeanTechnologyPlatform(ETP)initiativetoimprovethecompetitivepositionoftheEUinthefieldofchemistryinthreedomains:industrialbiotechnology,materialstechnology,andreactionandpro-cessdesign

Theprogramisajointinitiative(publicprivatepartnership)oftheEuropeanCommission,rep-resenting theEuropean communities and the industryThemainobjectiveof theprogram is toproduceandimplementaStrategicResearchAgenda(SRA)

Sustainablechemistry,itsengineeringandtechnologicalapplicationsarealsofocusedoncleanerchemicalprocessesandtheirdesigningusingthebestavailable technologies(BAT)ThetermbestavailabletechnologyisappliedunderregulationsonlimitingpollutantdischargeswithregardtotheabatementstrategySimilartermsarebestavailabletechniques,bestpracticablemeans,and best practicable environmental option The term constitutes moving targets on practices,sincedevelopingsocietalvaluesandadvancingtechniquesmaychangewhatiscurrentlyregardedasreasonablyachievable,bestpracticable,andbestavailable

Aliteralunderstandingwillconnectitwithasparenoexpensedoctrinewhichprescribestheacquisitionof thebeststate-of-the-art technologyavailable,without regardfor traditionalcostbenefitanalysisInpracticalusage,thecostaspectisalsotakenintoaccount

In principle, sustainable chemistry and technology platforms for sustainable chemistry (allEuropeanandnational)andgreenchemistryincludegreenengineering,technology,andproduc-tion,andallhavethesamegoalsandprinciplesanduseanalogousmethodologiesandmethods

FundamentalconnectionsbetweenSDandsustainableandgreenchemistryareexplainedanddescribedbyEissenetal(2002),Metzger(2004),andinthecontextofindustriesbyPoliakoffand


License(2007)Twoexclusive journals,Green Chemistry (RSC)since1999andChemSusChem(WileyInterscience)since2008,publish themostup-to-dateresultsandsolutionsofsustainableandgreenchemistry

PRINCIPLES AND GOALS OF GREEN CHEMISTRY

Thegoalsofgreenchemistryarefocusedonfourofthecurrentdemandsofhumankindwhicharemini-mizingwasteandpollution,efficientexploitationofmaterialandenergysources,minimizinghazard,andminimizingcostsasaresultofthepreviousthreeThekeytermforthesetofgreenchemistrygoalsisminimizingbutinthecontextoftermslikeefficiently,rationally,really,andpreferablyThisisbecausethedeclaredgoalsmaynotbeachievedpromptlyandabsolutelyForexample,itisgenerallyknownthatfreons(CFCs)usedaspropellantsforspraycanswerereplacedbyn-butane(hazardousbutlessthanCFCs)Similarly,environmentallyhazardouschlorinatedhydrocarbonsastetrachloromethane,trichloroethylene,andtheotherchlorohydrocarbonswerealternatedbysupercriticalcarbondioxideaswashingmediaPrinciplesfortheachievementofthesetgoalsmaybegroupedinthefollowingway:

AMinimizing waste and pollution 1 PreventionofwasteformationispreferredbeforewastedisposalItisbettertohandle

wasteatsourcethanatendofpipe BEfficient exploitation of material and energy sources 2 Syntheses, syntheticprocesses,mustbedesignedwithhighest atomeconomy, ie,

withmaximalincorporationofinputsintotheproduct 3 Rational reduction for theuseof solvents andother auxiliaries ispreferredbefore

theirrecyclingand/orregeneration 4 Preferenceofcatalyticreagents 5 Preferenceof(solid)supportedcatalysts 6 Multistepsynthesesarepreferredtoone-potprocedures,ideallyasmulticomponent

reactions(MCRs)and/ordominosyntheses 7 Permanent and renewable material and energy sources should be practicable and

applicableratherthannonrenewablewherevertechnicallyandeconomicallypossible 8 Rationalreductionfortheuseofarawmaterialorfeedstockderivativeforthesakeof

itsprotection,activation,andothertemporarymodification CMinimizing general hazard 9 Insyntheticprocesses,incomingandoutgoingchemicalsmustbeminimalandgener-

allynothazardous 10 Lifecycleassessmentofchemicalproducts 11 Developmentanduseofpreciseanalyticaltechniquesandmethodstoallowforreal-

time,in-processmonitoringandcontrolpriortotheformationofhazardoussubstances DMinimizing costs 12 Thiscanresultfromarationalandefficientuseoftheabove-presentedprinciples

On theotherhand, it shouldbe remembered thatProfessorPaulAnastasandProfessor JohnCWarner (AnastasandWarner,1998)were thefirst todevelopandformulate the12principlesofgreenchemistryNevertheless, theabove-mentionedprinciples,whicharenewerandmoreinno-vative, reformulate theessenceofgreenchemistryandchemistryforSDemanatingfromnewerunderstandingsofchemistsandengineersThe12principlesofgreenchemistryasformulatedbyAnastasandWarner(1998)aregivenbelowforcomparison:

1Prevention:Itisbettertopreventwastethantotreatorcleanupwasteafterithasbeencreated 2Atom economy:Syntheticmethodsshouldbedesignedtomaximizetheincorporationof

allmaterialsusedintheprocessintothefinalproduct


3Less hazardous chemical syntheses:Whereverpracticable,syntheticmethodsshouldbedesignedtouseandgeneratesubstancesthatpossesslittleornotoxicitytohumanhealthandtheenvironment

4Designing safer chemicals:Chemicalproductsshouldbedesignedtoaffecttheirdesiredfunctionwhileminimizingtheirtoxicity

5Safer solvents and auxiliaries:Theuseofauxiliarysubstances(eg,solvents,separationagents,etc)shouldbemadeunnecessarywhereverpossibleandinnocuouswhenused

6Design for energy efficiency:Energyrequirementsofchemicalprocessesshouldberecog-nizedfortheirenvironmentalandeconomicimpactsandshouldbeminimizedIfpossible,syntheticmethodsshouldbeconductedatambienttemperatureandpressure

7Use of renewable feedstocks:Arawmaterialorfeedstockshouldberenewableratherthandepletingwhenevertechnicallyandeconomicallypracticable

8Reduce derivatives:Unnecessaryderivatization(useofblockinggroups,protection/depro-tection,temporarymodificationofphysical/chemicalprocesses)shouldbeminimizedoravoidedifpossible,becausesuchstepsrequireadditionalreagentsandcangeneratewaste

9Catalysis:Catalyticreagents(asselectiveaspossible)aresuperiortostoichiometricreagents 10Design for degradation:Chemicalproductsshouldbedesignedsothatattheendoftheirfunc-

tiontheybreakdownintoinnocuousdegradationproductsanddonotpersistintheenvironment 11Real-time analysis for pollution prevention:Analyticalmethodologiesneedtobefurther

developedtoallowforreal-time,in-processmonitoringandcontrolpriortotheformationofhazardoussubstances

12 Inherently safer chemistry for accident prevention:Substancesandtheformofasubstanceusedinachemicalprocessshouldbechosentominimizethepotentialforchemicalacci-dents,includingreleases,explosions,andfires

METHODOLOGY AND METHODS OF GREEN CHEMISTRY

Scienceandadvances inengineering, technology,andtechnicalproductionhavegivenasophis-ticated methodology and broad scale of methods to current green chemistry A sophisticatedapproachtosolveenvironmentalproblems,greenchemistry,maybeessentiallycharacterizedasatrivialsolutiontoanontrivialandcomplicatedproblemSophisticatedapproachessuchasthefieldofgreenchemistrymethodologyareoftenveryeffectivewithminimalenergyandtechnologydemandsandcostsThemanufacturingof2,4-dichlorobenzylcyanide,an importantfinechemi-caland intermediateforphytoeffectorproduction, from2,4-dichlorobenzylchlorideandsodiumcyanidewitharelativelylowlevelofE-factorandminimumwasteformation(CzechPatent301063(2009),LucebnzvodyDraslovkaCoKoln)canserveasanexampleofacompletesophisticatedsolutionThisprocesswasindustriallyrealizedwithhighyieldandpurityinmethanolassolventandinthecatalyticpresenceofsodiumiodide(Scheme15)

Cl Cl

ClCN

Cl Cl

N

Cl ClN

Cl

Cl+

SCHEME 1.5 Preparationof2,4-dichlorobenzylcyanideor2,3-bis(2,4-dichlorophenyl)propanenitrilefrom2,4-dichlorobenzylchlorideandsodiumcyanide


Ontheotherhand,thesamereagentsandcatalystyieldinacetonesolventandinthepresenceofthecatalyticadditionofbenzyl-trimethylammoniumchlorideonly2,3-bis(2,4-dichlorophenyl)propanenitrile in high yield and purity (Pazdera and imbera, 2011) In the latter study, a suit-ableselectionofsolventsassophisticatedresolutionforcleanersynthesiswasdemonstratedforthepreparationofbenzoylcyanideand1,1-dicyanobenzyl-benzoate,whichisformedbydominoreac-tion(Scheme16)

Further,similarexamplesofsophisticatedapproachessuchasthefieldofgreenchemistrymeth-odologymightbefoundabundantlyintheliteratureHence,severalsyntheticmethods,approaches,andtechniquescanbepresentedasfeasibleandapplicableroutesfortherealizationofthegreenchemistrygoalsand thefulfillmentof itsprinciplesExamplesofsuchsyntheticmethodsareasfollows:

1Sophisticatedapproachesincludingregio-andstereoselectivesyntheticprocedures(Vgtleetal,2000)

2One-pot, multicomponent (MCRs), and domino reactions (Zhu and Bienaym, 2005;Tietzeetal,2006;Ishikawaetal,2009)

3Acidbase catalysis, catalysis by transition metal and their complexes, and enzymaticcatalysis(Sheldonetal,2007;Anastas,2009)

4 Interphasecatalysis, ie,phasetransfercatalysis(PTC)bothclassicandinverse,andmicellarcatalysis(Goldberg,1992;Starksetal,1994;Khan,2007)

5Synthetic applicationsof supported catalysts and auxiliariesbecauseof their easy sep-aration, regeneration, and reusability, and solid supported and combinatorial syntheses(SeneciandPierfausto,2000;SherringtonandKybett,2001)

6Synthesesrealizedundernonclassicconditions: a Synthesesinsupercritical(sc)waterandsc-carbondioxide(bothsc-fluidswitharisk

factorbecauseoftemperatureandhighpressure,respectively)andinionicliquidsassolvents(LeitnerandJessop,1999;Brunner2004)

b Microwaves(MW)asalow-energyandefficientalternativetoclassicheating(KappeandStadler,2005)

c Ultrasound(US)asalow-energyandefficientalternativetoclassicstirring,shaking,andheating(MasonandLorimer,2002)

7Combinationsoftheabovemethodsandapproaches,whichoftenbearveryeffectiveandsurprisingresultsasaconsequenceoftheirsynergism

Thevariousapplicationsofultrasoundpowerasasuitableandeffectivegreenmethodinscienceandengineeringresearch,chemicalandbiochemicalprocessing,andappliedscienceandengineer-ingtechnologyarediscussedinthesubsequentchapters

Cl

O

O

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O

N

N

Documents

Handbook on Applications of Ultrasound - Dong Chen