Handbook on applications of ultrasound sonochemistry for sustainability

Preface Followingtheestablishmentofthe12 Principles of Green ChemistryAnastasandWarner,1998, istryisarelativelyyoungscienceinitsownrespect�Interestinthisdisciplineisgrowingrapidlyandistr

Handbook on Applications of UltrAsoUnd

EditEd by

Sonochemistry for Sustainability

Handbook on Applications of

UltrAsoUnd Sonochemistry for Sustainability

CRC Press is an imprint of the

Taylor & Francis Group, an informa business

Boca Raton London New York

Handbook on Applications of UltrAsoUnd

EditEd by

Sonochemistry for Sustainability

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Contents

Foreword�������������������������������������������������������������������������������������������������������������������������������������������xiPreface�������������������������������������������������������������������������������������������������������������������������������������������� xiiiAcknowledgments����������������������������������������������������������������������������������������������������������������������������xvEditors��������������������������������������������������������������������������������������������������������������������������������������������xviiContributors������������������������������������������������������������������������������������������������������������������������������������xix

Boris Ildusovich Kharisov, Oxana Vasilievna Kharissova,

and Ubaldo Ortiz-Méndez

Chapter 10 UltrasoundinSyntheticApplicationsandOrganicChemistry�������������������������������� 213

Murlidhar S Shingare and Bapurao B Shingate

Reena Amatya Shrestha, Ackmez Mudhoo, Thuy-Duong Pham,

and Mika Sillanpää

Vijayanand S Moholkar, Thirugnanasambandam Sivasankar,

and Venkata Swamy Nalajala

Chapter 21 Ultrasound-AssistedIndustrialSynthesisandProcesses����������������������������������������� 535

Cezar Augusto Bizzi, Edson Irineu Müller, Érico Marlon de Moraes Flores,

Fábio Andrei Duarte, Mauro Korn, Matheus Augusto Gonçalves Nunes,

Paola de Azevedo Mello, and Valderi Luiz Dressler

Contents ix Chapter 22 DevelopmentofSonochemicalReactor������������������������������������������������������������������� 581

Keiji Yasuda and Shinobu Koda

Foreword

Intheeyesofnature,wecannotachieveasustainablefuturebythelinearextensionofexistingtechnologies�Thisobservationdrivesthequestfornewwaystopracticechemistry�Overthepast20years,anapproachtochemistryandengineeringdefinedbythe12principlesofgreenchemistryandgreenengineeringoffersusaprovenandsystematicwaytoaddresssustainabilityfromafirstdesignbasis�Weknowtherearemorethan85,000chemicalsusedincommercearoundtheworldandthevastmajorityhasneverbeentestedforhumanhealthandenvironmentalimpacts�Weknowtherearetrillionsofdollarsofcapitalinvestedinexistingchemicalmanufacturingplantsthatmustbeconsideredinanytransitionplan�Therearenosilverbulletstoaddressingthesystemsalreadyinplace�However,asteadyandever-expandingapplicationoftheprinciplesofgreenchemistryandengineeringovertimewillallowustomakeprogressinreplacingourdependenceonpetroleum-derivedfuelsandfeedstocks�

Chemiststodaycangototheliteratureandfindtoolstosynthesizejustaboutanycompoundonecanconceivebasedonestablishedtransformations,manyofwhichhavebeenaroundformorethanahundredyears�Yetweknowmandoesnotpracticechemistrythewaynaturedoeschemistryandthereinliesourhopeforthefuture�Wemustcontinuetoinventanddevelopthetoolsofgreenchemistrytoallowatransitiontobio-inspiredchemistry�

Thisbookisonesuchcommitmenttobuildingthenewgreenchemistrytoolbox�Itisfocusedprimarily on transformations aided by the use of sonochemistry (acoustic cavitation)� The abil-itytodeliverrapid,high-densityenergytoasystemfacilitatesnewpossibilities�Whilethecon-ceptsofsonochemistryhavebeenknownformorethan80years,in-depthunderstandingofthisphenomenon continues to evolve� Recently, the technique has begun to see applications rangingfromnanoparticleformationtocarbohydratesynthesistowastedestruction�Thus,sonochemistryappearstobeapplicabletoawidevarietyofchemicaltransformationsandhasthepotentialtoinflu-enceyields,dramaticallyreducereactiontimes,andincreasethroughput�Alltheseelementsareconsistentwiththeprinciplesofgreenchemistryandengineering�

Aswithanynewtechnology,agradualdevelopmentandadoptionprocesssetsin�Initialeffortsfocusonunderstandingandscopingthenewtoolsandwenowseesyntheticsonochemistrytechnol-ogyfindinganever-increasingvarietyofapplications�

Thisbookrepresentsawonderfulefforttobringtogetherthelatestdevelopmentsinthefieldandshouldproveusefultoallpracticingscientistswhohaveaninterestinexploringnewmethodstoinputenergyintoareactionprocess�

Preface

Followingtheestablishmentofthe12 Principles of Green Chemistry(AnastasandWarner,1998),

istryisarelativelyyoungscienceinitsownrespect�Interestinthisdisciplineisgrowingrapidlyandistransgressingseveralcascadingresearchareasinscience,engineering,andtechnology(SharmaandMudhoo,2010)�Theunderstandingoftheprinciplesthatbackbonegreenchemistryhasspurredmany outstanding efforts to implement chemical processes and innovative technologies that areincrementallytakingmodernsocietytowardsaferandmoresustainablepracticesandproductsthatembodyandfosterenvironmentalstewardship�

therehasbeenasteadygrowthinourunderstandingofwhatgreenchemistrymeans�Greenchem-tions of ultrasonic waves, i�e�, longitudinal sound waves with frequencies above 20kHz that liebeyond the upper limit of human hearing—although the range of ultrasonic frequencies can beextendedupto100MHz(CravottoandCintas,2006)�Sonochemistryshareswithsustainablechem-istrysuchaimsastheuseoflesshazardouschemicalsandsolvents,areducedenergyconsumption,andanincreasedproductselectivity(CravottoandCintas,2006)�Inthisregard,ultrasonicheat-ing and irradiation are in many instances complementary techniques for driving chemical reac-tionswithahigherefficiencyandeffectiveness�Ultrasound,anefficientandvirtuallyinnocuousmeansofactivationinsyntheticchemistry,hasbeenemployedfordecadeswithvariedsuccesses(CravottoandCintas,2006)�Notonlycanthishigh-energyinputenhancemechanicaleffectsinheterogeneousprocesses,butitisalsoknowntoinducenewreactivitiesleadingtotheformationofunexpectedchemicalspecies�Sonochemistryisuniqueinitsremarkablephenomenonofcavitation,currentlythesubjectofintenseresearch,andhasalreadyproducedinterestingresults�

Sonochemistryisabranchofchemicalresearchdealingwiththechemicaleffectsandapplica-raphyinhealthcare,representperhapsthebest-knownuseofultrasound�Chemicalapplicationsextendtosuchvariedareasasorganicandorganometallicchemistry,materialsscience,aerogels,water and wastewater treatment, food chemistry, and medicinal research (Cravotto and Cintas,2006)�Thewritingofthishandbookhasbeenundertakenbecauseitwasearnestlyfelttobringfor-wardanupdatedpoolofthelatestresearchanddevelopmentfindingsthatreasonablyencompassafairnumberofmostrelevantaspectslinkedtoandlinkinggreenchemistrypracticestoenvironmen-talsustainabilitythroughtheusesandapplicationsofultrasound-mediatedandultrasound-assistedbiological,biochemical,chemical,andphysicalprocesses�Inthishandbook,arichpanoplyofnovelresearchfindingsandapplicationsofultrasonicradiationandsonochemistryhavebeenpresented�Severalchaptershavebeenpresentedinthefollowingareas:medicalapplications,drugandgenedelivery,nanotechnology,foodtechnology,syntheticapplicationsandorganicchemistry,anaero-bicdigestion,pollutantdegradation,polymerchemistry,industrialsynthesesandprocesses,reactordesign,electrochemicalsystems,andcombinedultrasound−microwavetechnologies�

Imagingtechniquesusingecholocation,suchasSONARsystemsfortargetdetectionorechog-We sincerely hope this handbook provides a robust pool of knowledge on the green tionsofsonochemistry�Wealsofeelitprovidesup-to-dateinformationonsomeselectedfieldsofappliedresearchofultrasoundwheretheprinciplesofgreenchemistryarebeingembracedbythescientific,engineering,andtechnologicalcommunitiesforsafeguardingandimprovingthequalityoftheenvironmentandhumanlife,atlarge�WealsowanttosharethatProfessorSanjayK�Sharma

applica-andA�Mudhoohaverecentlyeditedabook,Green Chemistry for Environmental Sustainability

(CRCPress,Taylor&FrancisGroup,2010),whichisanup-to-dateandhumblecontributiontotheliteratureongreenchemistry�

xiv PrefaceForMATLAB®andSimulink®productinformation,pleasecontact:

academiatoinnovativeandlarge-scaleapplications�Chemical Society Reviews,35:180–96�

Sharma,S�K�andMudhoo,A�2010�Green Chemistry for Environmental Sustainability�BocaRaton,FL:CRC

Press,Taylor&FrancisGroup�

Dong Chen Sanjay K Sharma Ackmez Mudhoo

Acknowledgments

Thisboldundertakinghasprovideduswithauniqueopportunitytorenewsomeoldfriendshipsandhopefullyweavesomenewonesinpursuitofgatheringanddistillingtheexpertiserequiredforedit-ingandcompilingthishandbookontheapplicationsofsonochemistryforsustainabality�Withoutany reservation, we heartily thank our esteemed contributors for the way they have graciouslyrespondedwithcharacteristicgoodhumorandpatiencetoourdeadlines�Wealsoappreciatetheirconstructivecriticismsandsuggestions,whichhaveenhancedthecontentofthiswork�Wehopetheyeffortlesslyfeelthatthefinalresultdoesamplejusticetotheirpainstakingeffortsdeployedinpreparingtheirrespectivechapter(s)�Weareequallyappreciativetowardothercolleaguesandfel-lowresearcherswhovolunteeredtheirhelpinreviewingthescientificcontentsofthemanuscripts�ProfessorSanjayK�Sharmaespeciallyexpresseshisheartfeltgratitudetohisrespectedparents,Dr�M�P�SharmaandSmt�ParmeshwariDevi�HealsoextendshisregardstoProfessorR�K�Bansal,whohasbeenasourceofinspirationtohim,andtoDr�V�K�Agrawal,chairmanoftheInstituteofEngineeringandTechnology,Alwar(India),forhisencouragingwords�

Ackmez Mudhoo expresses his appreciation for the faith his parents, Azad A� Mudhoo andRuxanaB�Mudhoo,hisbrotherAssad,sister-in-lawTeena,andlovelynieceYannahaveplacedinhimthroughoutthewritingandcompilationofthishandbook�HeisalsothankfultoProfessorKonradMorgan(vice-chancellorandchairmanofSenateoftheUniversityofMauritius,Réduit,Mauritius), Professor Romeela Mohee (dean, Faculty of Engineering, University of Mauritius,Réduit,Mauritius),ProfessorPavelPazdera(MasarykUniversity,Brno,CzechRepublic),ProfessorMuthupandian Ashokkumar (Particulate Fluids Processing Centre, University of Melbourne,Australia),ProfessorGiancarloCravotto(UniversitàdiTorino,Torino,Italy)andDr�VinodK�Garg(GuruJambheshwarUniversityofScienceandTechnology,Hisar,Haryana,India)fortheirpres-ence,encouragement,andsupport�

Note: This work was supported by New Faculty Starting Fund from Indiana University−Purdue

UniversityFortWayne�

Editors

Dr Dong Chen is an assistant professor at Indiana

University-Purdue University Fort Wayne, Indiana� He has been doingimportantfundamentalresearchinsonochemistry,environmentalchemistry,andwaterandwastewatertreatmenttechnologies�Hehas served as the principal and coprincipal investigator of sev-eralfundedscientificresearchprojectsworthover$1million�Dr�Chen’sworkenjoysahighreputationintheinternationalscientificcommunityandhasbeenwidelycitedbyhispeers�Hisresearchintheareaofultrasoniccontrolofmembranefoulingwasreportedby

manyscientificnewsmedia,includingNature�Hehasmorethan

30journal,book,andconferencepublicationsand2U�S�patents�HehasbeenservingasagrantreviewerfortheU�S�DepartmentofAgricultureandNationalInstituteforWaterResourcesresearchprograms�Inaddition,Dr�Chenisaroutinereviewerfor12scientificjournalsandbooks�HereceivedhisPhDincivil(environmental)engineeringwithaminoringeologicalsciencefromTheOhioStateUniversity,Columbus,Ohio,in2005�Besideshisresearchexperience,Dr�Chenhadbeenworkingasafull-timeengineeringconsultantformorethantwoyears�HeisalicensedprofessionalengineerinthestateofOhio�

Professor (Dr.) Sanjay K Sharmaisawell-knownauthorand

editor of many books, research journals, and hundreds of

arti-cles over the last 20 years� One of his books, Green Chemistry for Environmental Sustainability,hasbeenrecentlypublishedby

CRCTaylor&FrancisGroup,LLC,BocaRaton,Florida�HehasalsobeenappointedasserieseditorbySpringer’sLondonfortheir

prestigiousbookseriesGreen Chemistry for Sustainability�

Dr�Sharmacompletedhispostgraduationin1995andreceivedhis 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 greenchemistryandproducedverygoodresearchpapersandbooksduringhis12yearlongstayattheInstituteofEngineeringandTechnology,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,India—oneofthebestengineeringcol-leges in North India—where he teaches engineering chemistry and environmental engineeringcoursestoBTechstudentsandpursueshisresearchinterests�Hehasdeliveredmanyguestlecturesondifferenttopicsofappliedchemistryinvariousreputedinstitutions�Hisstudentsappreciatehisteachingskillsandholdhiminhighesteem�

Dr�SharmaisamemberoftheAmericanChemicalSociety(UnitedStates),theInternationalSocietyforEnvironmentalInformationSciences(Canada),andGreenChemistryNetwork(RoyalSocietyofChemists,UnitedKingdom)�Heisalsoalifememberofvariousinternationalprofes-sionalsocieties,includingtheInternationalSocietyofAnalyticalScientists,theIndianCouncilof

xviii Editors

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

Dr�Sharmahas9booksonchemistryandover40researchpapersofnationalandinternationalreputetohiscredit,whichissufficientevidenceofhisfairtrackrecordasaresearcher�Healso

worksaseditorinchiefforthreeinternationalresearchjournals,RASAYAN Journal of Chemistry; the International Journal of Chemical, Environmental and Pharmaceutical Research; and the International Journal of Water Treatment and Green Chemistry,andservesasareviewerformany otherinternationaljournals,includingtheprestigiousGreen Chemistry Letters and Reviews�

Ackmez Mudhoo obtained his BEng (Hons) in chemical and

environmental 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 for

Waste 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 Research�Heisalsotheeditorin chieffortheInternational Journal of Process Wastes TreatmentandtheInternational Journal of Wastewater Treatment and Green Chemistry,andservesashandlingeditorfortheInternational Journal of Environment and Waste ManagementandtheInternational Journal of Environmental Engineering�Ackmezalsoreckonsprofessionalexperienceasconsultantchemicalprocessengineer

forChinaInternationalWater&ElectricCorp�(CWE,Mauritius)fromFebruary2006toMarch

2008� 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)�HeispresentlyalecturerintheDepartmentofChemicalandEnvironmentalEngineeringattheUniversityofMauritius�

Andrew Cobley

FacultyofHealthandLifeSciencesTheSonochemistryCentre

CoventryUniversityCoventry,UnitedKingdom

Giancarlo Cravotto

DepartmentofScienceandTechnology

of DrugUniversityofTurinTorino,Italy

Siamak Dadras

LaserMaterialsProcessingLaboratoryIranianNationalCentreforLaserScienceand Technology

Tehran,Iran

Aslihan Demirdoven

FacultyofEngineeringandNaturalSciencesDepartmentofFoodEngineering

GaziosmanpaşaUniversityTokat,Turkey

Ravindra Dhumal

CentreforPharmaceutical

Engineering ScienceUniversityofBradfordWestYorkshire,UnitedKingdom

Marie-Laure Doche

NationalCentreforScientificResearchUniversityofFranche-Comte

Besançon,France

Valderi Luiz Dressler

DepartmentofChemistryFederalUniversityofSantaMariaSantaMaria,Brazil

Audrey Mandroyan

CentreNationaldelaRechercheScientifiqueUniversitédeFranche-Comté

Besançon,France

Fernando Martínez

DepartmentofChemicalandEnvironmentalTechnology

UniversidadReyJuanCarlosMadrid,Spain

Timothy J Mason

FacultyofHealthandLifeSciencesTheSonochemistryCentre

CoventryUniversityCoventry,UnitedKingdom

Mallavarapu Megharaj

CentreforEnvironmentalRiskAssessmentand Remediation

UniversityofSouthAustraliaAdelaide,SouthAustralia,Australiaand

CooperativeResearchCentrefor

ContaminationAssessmentandRemediationoftheEnvironment

Salisbury,SouthAustralia,Australia

Juan A Melero

DepartmentofChemicalandEnvironmentalTechnology

UniversidadReyJuanCarlosMadrid,Spain

Paola de Azevedo Mello

DepartmentofChemistryFederalUniversityofSantaMariaSantaMaria,Brazil

Amos Mizrach

AgriculturalResearchOrganizationTheVolcaniCenter

TheInstituteofAgriculturalEngineeringBetDagan,Israel

Ubaldo Ortiz-Méndez

SchoolofMechanicalandElectrical

EngineeringAutonomousUniversityofNuevoLeonMonterrey,México

Senar Ozcan

EnvironmentalEngineeringDepartmentSelcukUniversity

Konya,Turkey

Larisa Paniwnyk

FacultyofHealthandLifeSciencesTheSonochemistryCentre

CoventryUniversityCoventry,UnitedKingdom

Anant Paradkar

CentreforPharmaceutical

Engineering ScienceUniversityofBradfordWestYorkshire,UnitedKingdom

Pavel Pazdera

FacultyofSciencesDepartmentofChemistryCentreforSynthesesatSustainableConditionsandTheirManagement

MasarykUniversityBrno,CzechRepublic

Thuy-Duong Pham

LaboratoryofAppliedEnvironmental

ChemistryDepartmentofEnvironmentalSciencesUniversityofEasternFinland

Mikkeli,Finland

Bruno G Pollet

PEMFuelCellResearchGroupCentreforHydrogenandFuelCellResearchSchoolofChemicalEngineering

TheUniversityofBirminghamEdgbaston,UnitedKingdom

Boon Mian Teo

SchoolofChemistryUniversityofMelbourneParkville,Victoria,Australia

Kandasamy Thangavadivel

CentreforEnvironmentalRiskAssessmentand Remediation

UniversityofSouthAustraliaAdelaide,SouthAustralia,Australiaand

CooperativeResearchCentrefor

ContaminationAssessmentandRemediationoftheEnvironment

Salisbury,SouthAustralia,Australia

Ali Tor

EnvironmentalEngineeringDepartmentSelcukUniversity

Konya,Turkey

Mohammad Javad Torkamany

LaserMaterialsProcessingLaboratoryIranianNationalCentreforLaserScienceand Technology

Tehran,Iran

Keiji Yasuda

DepartmentofChemicalEngineeringGraduateSchoolofEngineeringNagoyaUniversity

Aichi,Japan

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

Thenineteenthandthetwentiethcenturiesbroughttomankindagreatdealofnewdiscoveriesaswellaspracticalandapplicableknowledge�Also,duringthistimechemistrygavehumankindnewmaterials,medicalproducts,phytoeffectors,newtechnologies,andsyntheticprocedures(phytoef-fectorsmaybedefinedassubstancesortheirmixturesthatenablevegetablestodevelopprosper-ouslyfromgerminationtoharvesttimeandtheycontainnotonlypesticidesbutalsostimulantsforgrowthandimmunity)�

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

CONTENTS

Causesofa“ChemistryCurse”����������������������������������������������������������������������������������������������������������1WastesasRealEffectoftheAnthropogenicActivities����������������������������������������������������������������������4AnthropogenicWastesandTheirImpactsonNatureandDevelopmentofHumankind�������������������4ChemicalWastes��������������������������������������������������������������������������������������������������������������������������������7ChemicalWastesandSyntheticChemistryMetrics��������������������������������������������������������������������������9SustainableDevelopment:StartingPointandPreventionofanUlteriorBeingofHuman

Civilization��������������������������������������������������������������������������������������������������������������������������������������� 12SustainableDevelopment,Chemistry,andItsEngineeringandTechnologicalApplication����������� 14PrinciplesandGoalsofGreenChemistry���������������������������������������������������������������������������������������� 16MethodologyandMethodsofGreenChemistry����������������������������������������������������������������������������� 17ReferencesandLiteratureResources����������������������������������������������������������������������������������������������� 19

2 Handbook on Applications of Ultrasound: Sonochemistry for Sustainability

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(e�g�,2,4,6-trinitrophenol—TNP, 2,4,6-trinitrotoluene—TNT) (Urbanski, 1964; Ferro and Morrow Jr�,2005),andotherchemicalproductsweredevelopedandusedforkillingsoldiersduringWorldWarI�Phosgeneaswellasdiphosgene(trichloromethylchloroformate)ortriphosgene(bis(trichloromethyl)carbonate),safertohandlethanphosgene(KuritaandIwakura,1979),wasusedforthesynthesisoffunctionalderivativesofcarbonicacid�Forexample,carbamateshavebeenappliedaspesticidesorplastics(polyurethane)�

gencyanide)(Zabecki,1999)ingaschambersofNaziconcentrationcamps�Widespread“biologi-cal”applicationofhydrogencyanidewasinitiallylimitedtothefumigationofvaluabletreecrops,namely,citrusfruit,spreadingin1887fromCaliforniatoSpainandothercountries(Baur,1984)�HydrogencyanideisstillinproductionintheCzechRepublicintheSyntheticFactoryDraslovkaKolínCo�inthecityofKolínunderthetrademarknameUraganD2andissoldforeradicatinginsectsandsmallanimals�Otherfumigantssuchasmethylbromide,cyanogens(dicyan),andcar-bonylsulfidearealsoused(MessengerandBraun,2000)�Since2000BC,thehumanpopulationhasutilizedsubstancesortheirmixtureswithphytoeffectoractiontoprotectandintensifytheircrops�Someofthephytoeffectors,whichwerelatercalledpesticides,wereatfirstappliedasnaturalcompounds,e�g�,sulfurorextractsfromtobacco�Overtime,thepreparationofsyntheticmoleculesandsubstancesbegan�

AtthetimeofWorldWarII,manymen,mainlyJews,werepoisonedwithCyclonB(i�e�,hydro-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 by

2,3,7,8-tetrachlordibenzo-p-dioxine (TCDD), well known as Agent Orange� DDT is one of the

world’smostfamoussyntheticpesticideswithalong,unique,andcontroversialhistory�TheSwisschemistPaulHermannMüllerwasawardedtheNobelPrizeinPhysiologyorMedicinein1948

“forhisdiscoveryofthehighefficiencyofDDTasacontactpoisonagainstseveralarthropods”(http: //nobelprize�org/nobel_prizes/medicine/laureates/1948/)�AfterWorldWarII,DDTwasusedasanagriculturalmiraculousinsecticide,andsoonitsproductionandwidespreaduseerupted�ItsdeclineoccurredafterthediscoverythatDDTisapersistentorganicpollutantandisextremelyhydrophobicandstronglyabsorbedbysoil�Further,DDTanditsmetabolitesaretoxictoawiderange of animals in addition to insects, including marine animals such as crayfish, daphnids, seashrimp,andmanyspeciesoffish�Theyarelesstoxictomammalsbutmaybemoderatelytoxictosomeamphibianspecies,especiallyinthelarvalstage�Mostsignificantly,theyareareproductivetoxicantforcertainmarineandcontinentalbirdspecies�ThesearchforfurthernegativeeffectsofDDThasbeenpursuedrelentlesslybytheWorldHealthOrganizationandbyotherinternationalandnationalspecializedagencies�ItisaterriblefactthatsomepoorAfricancountriesusedDDTtilllately(U�S�EnvironmentalProtectionAgency,1975)�

AgentOrangeisthecodenameforoneoftheherbicidesanddefoliantsusedbytheU�S�ArmyinitsherbicidalwarfareprogramduringtheSecondVietnamWar(from1961to1971)(Stellman,2003)�

Dioxin,namely,2,3,7,8-tetrachlordibenzo-p-dioxin,isthesyntheticby-productofthereaction

of two phenoxyl herbicides mentioned earlier: iso-octyl ester of 2,4-dichlorophenoxyacetic acidand2,4,5-trichlorophenoxyaceticacid�AgentOrangeisnotachemicalagentagainstmilitants�Itwasappliedtoaidthesapperagentindestroyingthelandscapeblanketedbyfull-grownplantsandforestswhichservedasanaturalcoverforthenativewarriorsofVietConginVietnam,Laos,andCambodia� However, all negative impacts of Agent Orange were observed both on the warriorsofVietCongandtheU�S�military�Vietnamesescientistshavebeenconductingepidemiologicalresearchontheimpactofdioxinonhumanhealthsincethelate1960s�AccordingtotheVietnam

Emerging Ubiquity of Green Chemistry in Engineering and Technology 3

RedCross,asmanyas3millionVietnamesepeoplewereaffectedbyAgentOrangeincludingatleast150,000childrenbornwithcongenitaldefects�ThequestionastowhetherornottheexposuretodioxinaffectedthehealthoftheVietnamesewasdebatedsincethetimeofthewarwhenthe

firstanimalstudieswerereleasedshowingthat2,3,7,8-tetrachlorodibenzo-p-dioxinecausedcan-cerandcongenitaldefectsinrodents�StudiesofU�S�veteranswhoservedinthesouthduringthewarcomparedtothosewhodidnotgosouthfoundincreasedratesofcancerandnerve,digestive,skin,andrespiratorydisordersamongtheformer�Amongthecancers,veteransfromthesouthhadhigher rates of throat cancer, acute/chronic leukemia, Hodgkin’s lymphoma and non-Hodgkin’slymphoma,prostatecancer,lungcancer,softtissuesarcoma,andlivercancer(U�S�EnvironmentalProtectionAgency—DioxinWebsite)�

The second very unfortunate case connected with 2,3,7,8-tetrachlordibenzo-p-dioxine took

place on July 10, 1976, in a small chemical manufacturing plant approximately 15km northofMilanintheLombardyregioninItalyandisknownasSevesoDisaster(DeMarchietal�,1972)� The factory of the company Industrie Chimiche Meda Società 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 sodiumhydroxideshouldhaveproceededundercontrolledtemperature�However,excessivepressureputtheoperationoutofcontroland6tonsofreactionmaterialwasdispersedoveranareaof18km2�This material also included about 1kg of 2,3,7,8-tetrachlorodibenzodioxin, which is normallyseenonlyintraceamountsoflessthan1ppm�However,inthehigher-temperatureconditionsassociatedwiththerunawayreaction,theproductionofthementioneddioxinapparentlyreached100ppmormore�IndustrialsafetyregulationscalledtheSevesoDirectivepassedtheEuropeanCommunityin1982imposingmorestringentandharsherindustrialregulations�TheSevesoDirective was updated in 1999, amended again in 2005, and is currently referred to as theSevesoIIDirective(orCOMAHRegulationsintheUnitedKingdom)�Similardirectiveswerealsoestablishedbygovernmentagenciesofothercountries(e�g�,U�S�EnvironmentalProtectionAgency—EPA)�

AnothersimilardisastercausedbyerroneoushandlingoftechnologicalequipmentoccurredduringthenightofDecember2–3,1984,inBhopal,MadhyaPradesh,India�Thisindustrialcatas-tropheisgenerallywellknownastheBhopalDisasterortheBhopalGasTragedy(Broughton,2005)�InapesticideplantofUnionCarbideIndiaLimited(UCIL),atankcontainingabout

40 tonsofmethylisocyanate(MIC)asanintermediateinthemanufacturingthepesticideCarbaryl

(1-naphthylN-methylcarbamate,trademarkSevin)enteredintocontactwithlargeamountsofwater�

Thiscausedveryrapiddecompositioncombinedwithanacuteriseintemperatureandpressure(exothermicreactionundercarbondioxideformation),andleadingtotheworstindustrialdisastertodate�Anexplosionresultedinalargevolumeofmixedtoxicgases,includingMIC,whichcon-taminatedtheregionofBhopal�Theofficialdeathtollwasinitiallyrecordedataround5000�Manysourcesindicatedthat18,000haddiedwithin2weeks,anditisestimatedthataround8000havediedsincethenasvictimsofgas-poisoning-relateddiseasesthatcroppedup(Browning,1993)�Thedecisivefactorsthatcontributedtothedisasterincludethechemicalplant’spoorlychosenlocation,theuseofhazardousingredientchemicalssuchasMICinsteadoflessdangerousones,storageofthesechemicalsinlargetanksinsteadofseveralsmallerstoragetanks,poormaintenanceandcontrolofequipmentatthechemicalplant,failureofseveralsafetysystems,whichwerenotinoperationatthetime(Carbarylisnotatpresentregisteredforpesticideusebecauseitisclassifiedasalikelyhumancarcinogen)�

ogyapplicationsectors�ThetragedyofThalidomide(Mogheetal�,2008)isalsoaverywell-known

Boththesedisastersledtotighterspecificationsofsafetyinthechemicalindustryandtechnol- dioxopiperidin-3-yl)-1H-isoindole-1,3(2H)-dione) was introduced as a sedative drug in the late

chemicaldisasterbecauseofliteraryandcinematographicelaborations�Thalidomide((RS)-2-(2,6-1950sinWestGermanyandconsequentlyintherestoftheworldexcepttheUnitedStates�Inthe

4 Handbook on Applications of Ultrasound: Sonochemistry for Sustainability

late1950sandearly1960s,morethan10,000childrenin46countrieswerebornwithdeformitiessuchasphocomeliaasaconsequenceofthalidomideuse�

In1962,theU�S�CongressenactedlawsrequiringtestsforsafetyduringpregnancybeforeadrugcouldreceiveapprovalforsaleintheUnitedStates�Othercountriesenactedsimilarlegislation,andthalidomidewasnotprescribedorsoldfordecades�Thelaterexamplesofa“sad”and“bad”appliedchemistry,riskofsomechemicals,chemicaltechnologies,industry,andpollutionoftheenvironmentbydifferentwastescontributetotheexplanationoftheexecrationofchemistry�Ontheotherhand,chemistryanditsproductsareemployedbypeopledaily,and,withoutthem,thenatureandcontemporarycharacteristicsofhumanlifeandqualitywouldbecomegenerallyverydifficult�

WASTES AS REAL EFFECT OF THE ANTHROPOGENIC ACTIVITIES

Often,wehearviewsthatregardchemicalsassomethingbad,intheformofafoodand/oradrink�If we define the term “chemicals” as elements, their compounds, and compound mixtures (Hilletal�,2005),itrevealstheabsurdityoftheseviews,because,bystrictdefinition,drinkingwater,air,bread,hamandeggs,steak,housefly,dog,manyothers,and,evenmancouldbe“chemicals�”Finally,wecandefinelifeasahighlysophisticatedself-organizedsetoftransformationsandpro-cessesofsomechemicalsintootherchemicalswhichtakeplaceinsidealivingorganismfromthetimeoftheirconceptiontothemomentoftheirfatality(Koshland,2002)�Inthecourseoftheirlifecycle, wastes are formed (containing water, inorganic, and organic substances), and products ofaerobicand/oranaerobicrespiration(carbondioxideandoxygen),deadmatteroftabernacles,andotherresiduesareproduced�

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

Processesofwasteformationandtheircirculationareinevitableforlife�Becauseotherorgan-Allhighlysophisticatedself-organizedtransformationprocessesofwastes,andtheiruseandreuseintheenvironment,includingthebiosphere,proceedthereforeinclosedandwell-balancedcycles(Beckett,1981)�Anyorganismneedschemicalsubstancessuchasfoodandproductsotherthanchemicalsubstancessuchaswastesandalloccurthroughoutthecomplexfoodchainsandfoodwebs�Asimpleexamplewouldbegreenplantsthatarefoodforfauna,astheyyieldoxygenfortheanimalkingdomandplants�Viceversa,animalsproduceexcrementsandexpiredcarbondioxideasafoodforflora(PolisandWinemiller,1996)�

ANTHROPOGENIC WASTES AND THEIR IMPACTS ON NATURE

AND DEVELOPMENT OF HUMANKIND

ferentqualitiesandquantitiesofthewastesthatareproducedattheendofthesecomplexprocesses�Thequantityofwastesincreasesduetoariseinpopulation,andthequalityofwasteismorediversebecause of the ever-increasing industrial activities and their complexity� Both are affected by achangeinlifestyleofhumansandbythegrowthintheirconsumptionpatterns�Overtime,thedevel-opmentofhumankindleadstothereleaseoftoxicchemicalsintotheenvironment�Thesetoxicchemicalsascompoundsofheavymetalsorradioactivechemicalsgetconcentratedintheenvironment�Theconcentrationoftoxicorhazardoussubstanceshasaverynegativeeffectontheenvironmentincludingthebiosphere�Thisisbecausethenaturalenvironmentalcyclescannotassimilateanddegradethesepollutantsanyfurtherinasustainableandeffectivemanner�Processesofwasteaccu-mulationarethereforenon-sustainable�Atthetimeoftheindustrialandpostindustrialsociety,theterm“waste”tookonanewdimension(PongráczandPohjola,2004)�

Wastesproducedbythehumansocietyprofoundlyunderliedifferentprocessesbecauseofthedif-Emerging Ubiquity of Green Chemistry in Engineering and Technology 5

Wastemaybedefinedasmass(orenergy)thatisformedduringthemanufacturingprocessofaproductwithautilityvalueandwhichremainswhenthisproductlosesitsutilityvalue�Thiswastecontinuestobeawasteuntilitiseitherreintegratedintoanenvironmentoritischangedintoanewproduct(s)withanewutilityvalue�

AcopyofthenewspaperThe Timescanhelpasanexamplefortheabove-mentioneddefinition� ItisevidentthatduringthepreparationprocessofacopyofThe Timesadifferentbutbroadspec-

trumofwastesisproduced�However,thisisnotaproblemformostnewspaperreaderssincetheylookforwardtolearnaboutcurrentnews�Thenewspaperhasforthemanactualutilityvalueequaltothepriceof£1,whichforamajorityofreadersacquireszero-valueafteraread-throughandturnsintowasteendingupinacontainer�Itisinprinciple“bad”whenthiswasteisterminatedasmunicipalwastebecauseitscurrentutilityvalueisnegative�Ontheotherhand,thiswastepapermaybereusedasfiringmaterial(smallbutstillwithapositiveutilityvalue)orpreferablyrecycledasfreshrawmaterial(anetmorepositiveutilityvalue)�Archivingnewspapersinlibraries,archives,orinrecordofficesisanunusualwayofusingread-throughnewspapers�Theutilityvalueofthis

read-throughcopyofThe Timesispositiveand,overaperiodoftime,itincreases�

In this context, it points toward a product of life-cycle assessment (LCA)� LCA (Cooper andFava,2006)maybedefinedasamethodtoassesstheenvironmentalaspectsandpotentialimpactsassociatedwithaproductbasedoncompilinganinventoryofrelevantenergy,materialinputs,andenvironmentalreleases,onevaluatingthepotentialenvironmentalimpactsassociatedwithidenti-fiedinputsandreleasesincludingpotentialhazards,andoninterpretingtheresultshelptocomeupwithamoreinformeddecision�

tant factor in the development of humankind� These sources can be classified in terms of theiravailabilityaspermanent(e�g�,basematerialssuchaswater,saltyseaandoceanwater,nitrogen,oxygen,andotherairgasesandenergysuchassolarandgeothermalenergyandkineticorpotentialenergyofflowingwaterandagitateair)orasrenewable(e�g�,greenalgaeandplants,charcoal,andnuclearenergy)biomass�Thepermanentandrenewablesourcesarethereforeclassifiedassustain-ablewhereasthenonrenewablesourcesarecategorizedasnon-sustainable(Lancaster,2002)�Inthesequel,anumberofhumanactivitiesconnectedwiththeirdevelopment,namelyinthetimeofindustrialandpostindustrialsociety,havealwaysresultedinhazardousconsequences�Asexamples,clearingofforestandtropicalrainforest(Moran,1993)forobtainingagriculturalfarms,landforcivilconstructions,orforobtainingroundwoodasrawmaterial(Hartman,1992);theuseofcyanideforgoldmining(Ali,2006);ortheuseofsulfuricacidforuraniumminingresultinthepollutionofwaters,productionofgreenhouseandotherhazardousatmosphericgases�Furthermore,theproduc-tionandexploitationofgenerallytoxicandhazardousproductsandtheapplicationofmethodsfortheirproductionleadtoenvironmentalpollution�

Thepossibilityofaccessingthesourcesofbasematerialsandenergyisthesecondmostimpor-Thepossibilityofhazardisthethirdimportantfactorinthedevelopmentofhumankind(EricsonIII,2005)�Bynature,hazardinvolvessomethingthatcouldpotentiallybeharmfultoaperson’slife,health,property,ortheenvironment(MacCollum,2006)�Onekeyconceptinidentifyinganyhaz-ardisthepresenceofstoredenergythat,whenreleased,cancausedamage�Storedenergycanoccurinmanyforms:chemical,mechanical,thermal,radioactive,orelectrical�Anotherclassofhazarddoesnotinvolvethereleaseofstoredenergy�Rather,itinvolvesthepresenceofhazardoussitua-tions�Examplesincludeconfinedorlimitedegress,oxygen-depletedatmospheres,awkwardposi-tions,repetitivemotions,andlow-hangingorprotrudingobjects�Hazardandvulnerabilityinteracttogethertocreaterisk�

Thecauseofthe2008–2009worldwidefinancialandeconomiccrisis,whichhadarisenasa result of derivatives of dangerous financial products or phosgene substitution by dimethylcarbonate—whichisproducedduringahazardoushigh-pressuresynthesisfrommethanolandcarbondioxide—constitutesthepossibilityofhazard�Hazardcannotbecompletelyeliminatedbutcanbeavoidedbyexperthandlingofsafetydevices,andcanthusbeminimized�Itisneces-sarytoeliminatehazardoussituationsorstateswhicharenon-sustainable�Itstandstoreason

6 Handbook on Applications of Ultrasound: Sonochemistry for Sustainability

thattheLCAforapapercopyoftheThe Timesandfortheabove-mentionedherbicideAgent Orangewillbetotallydifferent�ThepaperversionoftheThe Timesthereforecontinuestobe

issuedwhereasAgentOrangeisforbiddenforuse�

Thequantityofwasteduringamanufacturingprocessofatargetproductcanbedefinedasthemassdifferencebetweentheamountofrawmaterialsandthetargetproduct�Thevalueiscommen-surabletotheefficiencyofrawmaterialexploitation,productioncosts,andthefinalpriceofproducts�Waste is directly linked to human development, both technologically and socially� The com-position of different wastes has varied over time and location, with industrial development andinnovation�Examplesofthisincludeplasticsandnucleartechnology�Anthropogenicwastetypesdefinedbymodernsystemsofwastemanagement(Rhyner,1995)aremunicipalsolidwaste(MSW),constructionanddemolitionwaste(C&DW),institutionalwaste,commercialwaste,andindustrialwaste(IC&I),medicalwaste(alsoknownasclinicalwaste),hazardouswaste,radioactivewaste,andelectronicwaste�

ment,i�e�,onthesurfaceoftheEarthinsoils,inthewaterofrivers,seas,oceansandsubterraneanwaters,andintheatmosphere�Chemicalsubstanceswhicharecontainedinanthropogenicwastesmaybetransformedintheenvironmentbynaturalenvironmentalprocesses,e�g�,duringbiodegra-dationinsoil,water,andairbytheenzymaticactionoflivingorganismssuchasbacteria,yeasts,andgreenplantsunderaerobicand/oranaerobicconditions(Diaz,2008)�

Wastesthatareformedduringanthropogenicactivitiesmaybelocalizedinanintegralenviron-ablederivatives,theyfunctionaspollutantswithallnegativeresults,e�g�,asgeneraltoxicresiduesandagentsdepletingtheozonelayer�Itisgenerallyknownthatchemicalcompoundswithstrongchemicalbondssuchaspolyaromatichydrocarbons(PAHs),chlorinatedand/orfluorinatedhydro-carbons such as chlorofluorocarbons (CFCs, freons), chloromethanes, and the above-mentioneddioxinsaredangerousfortheenvironment(Williamsetal�,2000)�

Solongaswastesarenottransformedintheenvironmentintoenvironment-friendlyandaccept-Wastes can also be classified according to their state of matter such as solid, liquid, and/orgaseousortheirmaterialuniformitysuchashomogeneousorheterogeneous;industrialwastecanbecategorizedbythelocationoftheirgenesis,e�g�,“atsource”or“endofpipe”wastes�Thebestsituationistohavewastesthatarenotgenerated�Preventionofwasteproductionandpreventionofpollutionareprincipalapproachesofwastemanagement(ClarkandMacquarrie,2002)�Disposalof

“endofpipe”wastesincludesallanthropogenicwastetypesandmaybedescribedbythefollowingsequenceofprocedures:

Moreover,somecompaniesmovepollutingmanufacturingprocessesfromdevelopedcountriestothepoorerdevelopingcountries(least-developedcountries),forreasonsthatneednocomment,inanefforttosavecoststhereafter�Thissolutiondoesnotpreventtheconsequences�Ontheotherhand,itcreatesforthesecompaniesproblemswithflexibilityofproductionandtransport�Forthepreventionofhazardousorriskysituations,disasters,andaccidents,themonitoringandanalysisofallhazardousfactors(Mannan,2005)areimportant�Themonitoringandanalysisofthemovement

Emerging Ubiquity of Green Chemistry in Engineering and Technology 7

ofchemicalsubstancesincludeallwastetypesintheenvironment,atoxicityanalysisofcurrentandnewchemicals,acapacityassessmentofmaterialandenergysources,otherhazardousfactors,andenvironmentalcosts�Consequently,ariseinthequalityandquantityofwastes,theirlocalandtemporalconcentrations,andtheself-regulatedprocessesintheenvironmentmaybeinhibitedandtheentiresystemmaybedeflectedfrombalance�

Anumberofpersons(environmentalistsandpoliticians)haverealizedthis“fatal”problemofenvironmentalpollution�Andfortheperpetuityofhumancivilization,thesepeoplehaverecentlystartedseekingsolutions�Theapproachestoaddresstheseimpendingenvironmentalhealththreatsarediscussedinthefollowingsection�

CHEMICAL WASTES

cals,andthepharmaceuticalindustry,andwithoutchemicalprocessesasapplicableintheprocess-ingindustryandenergyindustryishardlyconceivable�However,humanactivitiesconnectedwithchemistry,chemicalengineeringprocesses,andthechemicalindustryyieldverynegativeimpactsontheenvironmentandcreateallsortsofhazards�

Asmentionedearlier,theexistenceofcontemporaryhumancivilizationwithoutchemistry,chemi-trile(vinylcyanide)isaresinous,fibrous,orrubberyorganicpolymer(Morgan,2005)�Thesyn-theticretro-projectionofPANmanufacturingisillustratedinScheme1�1�Itisgenerallyknownasamaterialforuseinthetextileindustry,oftenincombinationwithnaturalfiberssuchascottonandwool�PANfibersarealsothechemicalprecursorsofhigh-qualitycarbonfibers�Theyarechemicallymodifiedtomakecarbonfibersfoundinplentyofbothhigh-techandcommondailyapplications such as primary and secondary structures of civil and military aircraft, missiles,solidpropellantrocketmotors,pressurevessels,fishingrods,tennisrackets,badmintonrackets,andhigh-techbicycles�AlmostallPANresinsarecopolymersmadefrommixturesofmonomerswithacrylonitrileasthemaincomponent�Itisacomponentrepeatunitinseveralimportantcopo-lymers,suchasstyrene–acrylonitrile(SAN)andacrylonitrilebutadienestyrene(ABS)plastic�Evidently,PANanditscopolymersareveryimportantfortheexistenceofcontemporaryhumanlife�Ontheotherhand,PANisaverystablematerialwhichishoweverproblematicallyintegratedintotheenvironmentbecauseofitsincompletecombustionthatproduceshydrogencyanideandnitrogenoxides�

Polyacrylonitrile(PAN)preparedbyfree-radicalvinylpolymerizationofmonomeracryloni-Monomeracrylonitrile(Dalinetal�,1971)ismanufacturedbythecatalyticammoxidationofpropyleneorbythecatalyticadditivereactionofhydrogencyanidewithacetylene(Goodrichpro-cess)�HydrogencyanideisproducedmainlybytheAndrussovoxidationprocessinwhichmethaneandammoniareactinthepresenceofoxygenatabout1200°Coveraplatinumcatalyst�Methane,propylene,andacetylenearepetrochemicalproducts,andthereforenonrenewablerawmaterials�However,ammoniacanbecharacterizedasarenewablerawmaterialandoxygenasapermanentone�Allthechemicalsusedforacrylonitrilemanufacturingincludingacrylonitrileitselfarehighly

CN CN

8 Handbook on Applications of Ultrasound: Sonochemistry for Sustainability

hazardousandexplosiveinamixturewithair,flammable,andgenerallytoxic�Thesetechnologicalprocessesarealsohazardousbecausetheyinvolvehighpressuresandhightemperatures�

Ibuprofen is manufactured currently (procedure of Hoechst company, Presidential [USA]GreenChemistryChallenge:GreenerSyntheticPathwaysAwardin1997)byathree-stepsynthe-sisstartingwiththeFriedel–Craftspara-acetylationofiso-butylbenzenebyacetanhydrideinthepresenceofhydrogenfluorideastheLewisacidcatalyst�Thissyntheticstepproducesaceticacidandhydrogenfluorideaswaste,butaceticacidcanbeusedasarawmaterialforotherchemicalsynthesesandhydrogenfluoridecanbereused�JustusinghydrogenfluorideisveryinnovativebecauseFriedel–CraftsacetylationofaromaticsusingaluminiumchlorideasaLewisacidarecommonlyapplied�

Ontheotherhand,thereisnodoubtthatbothaceticacidandincreasinglyhydrogenfluoridearehazardoussubstances�Inthenextstep,4-acetylatediso-butylbenzeneishydrogenatedonRaneynickelasaheterogeneouscatalystunderpressuretogivethecorrespondingalcohol,whichinathirdstepundergoespalladium-catalyzedcarbonylationbycarbonmonoxide�

Onceagain,alltheabovereagents,intermediateproducts,andcatalystsaresomehowhazardous�Intermsofthesourceinputs,nickelandpalladiumarenon-renewable,andhydrogenandcarbon

O

O O ClCH2COOC2H5

(CH3CO)2O AlCl3

O OH

O

H2, Raney Ni

CO, [Pd]

(CH3CO)2O HF

SCHEME 1.3 Syntheticretro-projectionofibuprofenmanufacturingbyHoechstmethod�

Emerging Ubiquity of Green Chemistry in Engineering and Technology 9

monoxidecanbemarkedaspartlyrenewablerawmaterials�Classificationinbothcasesdependsontheusedenergyandcarbonmonoxideoncarbonsource�Asustainablemethodforcarbonmonoxidemanufacturingishencebasedeitheronthereactionofcarbon(i�e�,charcoal)withcarbondioxide,controlledoxidationofcharcoal,orcellulosepyrolysis�

Evaluations of synthetic processes are necessary for an assessment of their environmentalimpacts,theutilizationofmaterialandenergyinputs,wasteproduction,andcostsinvolved�Wethereforeneedtodefinethecontentof“asyntheticprocess”orofachemicalsynthesis�Chemicalsynthesismaybedefinedasaprocessthatstartsfromthetimeoflocationofreagent(s),possiblesolvent(s),catalyst(s),andauxiliariesinareactoruptothepointofendingtheirreaction,separation,andpurificationprocessofreactionproduct(s),finallyculminatingintheadjustmentofproduct(s)�Thefirstandlastpartsofthedefinitionareimportantbecausetheyhelptoexploretherequirementofenergyandworkandtheircostsforallprocesses�Ontheotherhand,theyhelptoobtainarealoutlookonsomesensationalso-calledsolvent-freesyntheses�Thesecasesarereportedveryoften,but, in a further view, they are not solvent-free syntheses� Respective reactions proceed indeedwithoutasolvent,butamixtureofreagentshavebeenmixedinsolvents(fordepositiononsolidsupport)and/orthefinal(solid)producthasbeenpurifiedbyusingasolvent�Theadvantagesofone-pot,multicomponent,anddominoreactionsexcelinthecontextofthesyntheticprocessdefinedearlierbecauseseveralsyntheticorreactionstepsarelocatedinthesamereactorwithoutseparation,purification,transport,andadjustmentoftheintermediaryproduct�

CHEMICAL WASTES AND SYNTHETIC CHEMISTRYMETRICS

Achemicalone-stepsynthesismaybedescribedasinScheme1�4�

AnidealgoalofsyntheticprocessesisthefullconversionofstartingreactantsintoapurefinaltargetproductCwithouttheapplicationofothersubstances(catalyst,solvent,auxiliaries)andwith-outenergyclaims�Inaddition,thisprocessshouldbeconductedwithouttheformationofregio-and/orstereoisomersofthetargetproductC′,C″,by-product(s)D,nonconvertededucts%A,%B,catalyst,solvents,andauxiliaries,whichareabreedinggroundforwasteformationbecausetheyarenotembeddedintheproduct,andadditionalenergyandlaborareneededfortheirseparation�However,idealsyntheticproceduresoccurverysporadically�Hence,trade-offsmustbesoughtandconsidered�Designingsyntheticprocesseshelpsoptimizethesecompromises�

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

 1�ConversionXofreactantAorB(oneoftwoismarkedaskeyorlimitingreactant)isthedegreeofitsutilizationforanyproductformationinagivenmoment�Thisindex(avalueof

0–1or0%–100%,theoreticalmaximumX=1orX=100%)showshowmanykeyreactants

areutilizedforproductformationandsignifieshowmuchofitisleftaswasteforwastemanagement� 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:acid–base,metalcomplex,homogeneousorhetero- geneoussolventforreactionand/orforpurification;auxiliaries:sorbentforpurification,surfactant,inert gas;energyforheating,cooling,stirring,highpressure,vacuum,transportandworkofstaff�)

10 Handbook on Applications of Ultrasound: Sonochemistry for Sustainability

conditions,e�g�,byachangeofsolvent,andapossiblepressure-ortemperature-induceddisplacementofchemical/dynamicequilibrium�

 2�YieldofthetargetproductCistheamountofproductobtainedasaresultofachemical reaction�TherelationshipbetweenyieldYandconversionXisgivenbythemultiplication operationY=X×S,whereSisaselectivityofreactionforthetargetproduct,allcalculated

onmolarbasis�Otherwise,arelationshipisfoundbetweenthemassofthetargetproductanditstheoreticalcalculatedvalue,rangingfrom0to1or0%to100%,withatheoretical

maximumforY=1orY(%)=100%�Yieldaswellasconversionandreactionselectivity

maybeincreasedbyachangeofsyntheticprocedureconditions�

 3�Effectivemassyieldisdefinedastheratiobetweentheweightofthetargetproductandthemassofallnon-benignmaterialsincidentinthecourseofitssynthesis(i�e�,regio-and/orstereoisomersofthetargetproduct,by-product(s),catalyst,solvents,andauxilia-ries)�Theweaknessofthismetricistherequirementforafurtherdefinitionofabenignsubstance�Itisassumedthatthesehavenoenvironmentalriskassociatedwiththem,e�g�,water,low-concentrationbrine,inertgases,diluteethanol,autoclavedcellmassmaybereferredtoasbenign�Thisdefinitionisverysubjectivebecauseenvironmentaldatamaybeincomplete�

 4�Environmentalfactor(E-factor):RogerSheldon’sE-factor(Sheldon,1992,1994,1997a,b,

2000,2007,2008)canbeviewedascomplexandthoroughandontheotherhandassimplewhenrequired�Assumptionsonsolventandotherfactorscanbemadeoratotalanalysis

canbeperformed�TheE-factorcalculationisdefinedbytheratioofthemassofwasteper unitofproduct�Thisvalueisverysimpletounderstandandtouse�E-factorignoresrecy-

clablefactorssuchasrecycledsolventsandreusedcatalysts,whichobviouslyincreasethe

accuracybutignoretheenergyinvolvedintherecovery�ThemaindifficultywithE-factors

istheneedtodefinesystemboundariesbeforereliableandmeaningfulcalculationscanbeperformedandthesedifferfromassessortoassessor�Thislimitationisthemaindraw-backofallmetricswiththeexceptionoftheextremelycomplexLCAofaproduct�By

incorporatingyield,stoichiometry,andsolventusage,theE-factorisanexcellentmetric� Crucially,E-factorscanbecombinedtoassessmultistepreactionsstepbysteporinone

calculation�Sheldondemonstratedinhisdocumentsthatthechemicalindustrysectorwith

abulkytonnageofannualproductionachievingrelativelysmallvaluesofE-factor,e�g�, petrochemicalindustryandindustry,producedbulkchemicalshavinganE-factorof0�1–5

atanannualproductionof104–108ingfinechemicalsandpharmaceuticalshadfortheirannualproductionof104–10tonsan

tons�Ontheotherhand,chemicalcompaniesproduc-E-factorincomparablyhigherat5–100�Thesedatahencedemonstratethatoilcompanies

producealotlesswastethanpharmaceuticalsasapercentageofmaterialprocessed�Thisreflectsthefactthattheprofitmarginsintheoilindustryrequirethemtominimizewasteandfindalternativeusesforproductswhichwould“normally”bediscardedaswaste,oritmaybetransformedbycatalyticprocessestoreusablefundamentalproducts(methane,ethane,ethylene,andhydro-craftingof“heavy”naturalresinparaffines)�Bycontrast,thepharmaceuticalsectorismorefocusedonmoleculemanufacturingandquality�Theactuallyhighprofitmarginswithinthepharmaceuticalsectormeanthatthereislessconcernaboutthecomparativelylargeamountsofwastethatareproduced(especiallyconsideringthe

volumesused)althoughithastobenotedthat,despitethepercentageofwasteandE-factor

beinghigh,thepharmaceuticalsectorproducesmuchlowertonnageofwasteperproductunit than any other sector� As mentioned earlier, by obtaining the relevant data for the

calculationofaconversion,yield,effectivemassyield,andE-factor,asyntheticorprocess

experiment may be performed� Synthetic or process experiments are not necessary forthecalculationofafurther4–6chemistrymetricsbecauseofthechemicalsynthesisandsyntheticprocessmodelingdiscussedbelow�

Emerging Ubiquity of Green Chemistry in Engineering and Technology 11

 5�Atomeconomy(atomefficiency—AE)isdesignedinadifferentwayfromalltheabovemetrics�Itcanbedesignedasamethodbywhichorganicchemistswouldplanon“cleaner”syntheticprocessesverysimply�Theessentialdefinitionofatomeconomyisbasedonhowmuchofthereactantremainsinthefinalproduct�Forasingle-stepprocedureoftheabovesynthesis,atomeconomymaybecalculatedas

foratheoreticalmaximumY=1orY(%)=100%achievableforisomerizationreactions,

rearrangement, additive reactions including Diels–Alder and similar cyclo-additions iftheseproceedwithoutmoreisomerformation�Inthesereactiontypes,onlyoneproductisformed�Ontheotherhand,intheWittigreactionorMitsunobureaction,averypoorAEisobtainedbecauseheavytriphenylphosphineoxideisformed�OtherexamplesofpoorAEmaybethenucleophilicsubstitutionreactionsofhalogensonsaturatedcarbonatomunder

SN2reactionconditions�Alkyliodidesareveryreactiveatthesealkylatingreactions�

 ciencyofcarbonatomsinvolvedinthesyntheticprocess�ThemathematicalrepresentationisaccordingtoAE,butinlieuofmassofallatomsthemassofcarbonatomsisconsidered�Thismetricisagoodsimplificationforuseinthepharmaceuticalindustry(andinsus-tainablepetrochemistrytoo)asittakesintoaccountthestoichiometryofreactantsandproducts� Furthermore, this metric is of interest to the pharmaceutical industry wherethedevelopmentofcarbonskeletonsisimportantforthework�Thegoalistoconserveallcarbonatomsinthematrixofthecompound�AvalueofCElessthan1isconnectedwithcrackinganddecarboxylationreactions�Bulkydecarboxylationreactionsobservedinpetrochemistrymightbethesourceofmassivevolumesofgreenhousecarbondioxide�Hence,thisindexshowsthatthepotentialtransformationofplantoilsintohighalkanesor alkenes as renewable products will not be based on hydrolysis and decarboxylationreactions,butonreductionthroughthecatalytichydrogenationoffunctionalizedcarboxylgroupsinplantoils�

6�Carbonefficiency(CE)isanothermetricderivedfromAE,butisusedonlyfortheeffi- 7�ReactionmassefficiencyisalsoanothermetricderivedfromAE,butinthecalculation,themassofproductandeductsisusedinlieuofmolecularweight�ThedifferencebetweenAEandreactionmassefficiencyvaluesmayariseifeductsreactnotinarealreactionbutonastoichiometricbasis(excessofnon-keyreactant)�Inthiscase,avalueforreactionmassefficiencylessthantheatomeconomyisobtained�

 8�TheEcoScale(VanAkenetal�,2006)isarecentlydevelopedmetrictoolfortheevaluationoftheeffectivenessofasyntheticreaction�Itischaracterizedbysimplicityandgeneral

12 Handbook on Applications of Ultrasound: Sonochemistry for Sustainability

applicability�Liketheyield-basedscale,theEcoScalegivesascorefrom0to100,butalsotakesintoaccountcost,safety,technicalsetup,energy,source,andpurificationaspects�Itisobtainedbyassigningavalueof100toanidealreaction�Theproposedapproachisbasedonassigningarangeofpenaltypointstotheseparameters:

  This semiquantitative analysis can easily be modified by other synthetic chemists whomayfeelthatdifferentrelativepenaltypointsshouldbeassignedtosomeparameters�It isapowerfultooltocompareseveralpreparationsofthesameproductbasedonsafety,economical,source,andenvironmentalfeatures�

SUSTAINABLE DEVELOPMENT: STARTING POINT AND PREVENTION

OF AN ULTERIOR BEING OF HUMAN CIVILIZATION

Since the late 1960s and early 1970s some people from academia, civil society, diplomacy, andindustryhavebeguntobeawarethatthecurrentlifestyleanddevelopmentofhumankindisnotfur-thersustainable�Amassivepollutionoftheenvironmentinconsequenceofindustrialactivitiesandmanufacturing,andoverexploitationofnaturalrawmaterialandenergysourceshavetakenplace�Hence,inApril1968,TheClubofRome(KingandSchneider,1993)wasfoundedasaglobalthinktankthatwoulddealwithavarietyofinternationalpoliticalissues�Ithasraisedconsiderable

publicattentionin1972withitsreportbookThe Limits to Growth(Donellaetal�,1972),whichused

theWorld3modeltosimulatetheconsequencesofinteractionsbetweentheEarth’ssystemsandhumansystems�Theclubstatedthatitsmissionis“toactasaglobalcatalystforchangethroughtheidentificationandanalysisofthecrucialproblemsfacinghumanityandthecommunicationofsuchproblemstothemostimportantpublicandprivatedecisionmakersaswellastothegeneralpublic�”OnJuly9,1970,citingrisingconcernsoverenvironmentalprotectionandconservation,U�S�presi-dentRichardNixontransmittedReorganizationPlanNo�3totheUnitedStatesCongressbyexecutiveorder,creatingtheEPAasasingle,independentagencyfromanumberofsmallerarmsofdifferentfederalagencies�PriortotheestablishmentoftheEPA,thefederalU�S�governmentwasnotstructuredtocomprehensivelyregulateenvironmentalpollutants�TheUnitedNations(UN)ConferenceontheHumanEnvironment(alsoknownastheStockholmConference)wasaninternationalconferencecon-venedundertheUNauspicesheldinStockholm,Sweden,fromJune5to16,1972�

ItwastheUN’sfirstmajorconferenceoninternationalenvironmentalissues,andmarkedaturningpointinthedevelopmentofinternationalenvironmentalpolitics�Themeetingagreeduponadeclara-tioncontaining26principlesconcerningtheenvironmentanddevelopment,anActionPlanwith109recommendations,andaResolution�In1973theEuropeanUnion(EU)createdtheEnvironmentalandConsumerProtectionDirectorate,andcomposedthefirstEnvironmentalActionProgram�In1987,“OurCommonFuture”(OurCommonFuture(1987),Oxford:OxfordUniversityPress),also known as the Brundtland Report, from the UN World Commission on Environment andDevelopment(WCED)waspublished�Thepublicationof“OurCommonFuture”andtheworkoftheWCEDlaidthegroundworkfortheconveningofthe1992EarthSummitandtheadoptionofAgenda21,theRioDeclaration,andtheestablishmentoftheCommissiononSustainableDevelopment�Anoft-quoteddefinitionofsustainabledevelopment(SD)isdefinedinthereport:“Developmentthatmeetstheneedsofthepresentwithoutcompromisingtheabilityoffuturegenerationstomeettheirownneeds�”

ognitionthatthemanycrisesfacingtheplanetareinterlockingcrisesthatareelementsofasinglecrisisofthewholeandofthevitalneedfortheactiveparticipationofallsectorsofsocietyincon-sultationanddecisionsrelatingtoSD�

Inaddition,keycontributionsof“OurCommonFuture”totheconceptofSDincludetherec-Emerging Ubiquity of Green Chemistry in Engineering and Technology 13

Agenda21(http://www�un�org/esa/dsd/agenda21/)isaprogramrunbytheUNrelatedtoSDandwastheplanet’sfirstsummittodiscussglobalwarming–relatedissues�Agenda21clearlyidenti-fiedinformation,integration,andparticipationaskeybuildingblockstohelpcountriestoachievedevelopmentthatrecognizestheseinterdependentpillars�ItemphasizesthatinSDeveryoneisauserandproviderofinformation�Itstressestheneedtochangefromoldsector-centeredwaysofdoingbusinesstonewapproachesthatinvolvecross-sectoralcoordinationandtheintegrationofenviron-mentalandsocialconcernsintoalldevelopmentprocesses�Furthermore,Agenda21emphasizesthatbroadpublicparticipationindecisionmakingisafundamentalprerequisiteforachievingSD�Itisacomprehensiveblueprintofactiontobetakenglobally,nationally,andlocallybyorganizationsoftheUN,governments,andmajorgroupsineveryareainwhichhumansdirectlyaffecttheenvironment�Suchincreasedinterestandresearchcollaborationarguablypavedthewayforfurtherunder-standingofglobalwarming,whichhasledtosuchagreementsastheKyotoProtocol�ThisisaprotocoltotheUnitedNationsFrameworkConventiononClimateChange(UNFCCCorFCCC),aimedatfightingglobalwarming�TheUNFCCCisaninternationalenvironmentaltreatywiththegoalofachieving“stabilizationofgreenhousegasconcentrationsintheatmosphereatalevelthatwouldpreventdangerousanthropogenicinterferencewiththeclimatesystem�”TheProtocolwasinitiallyadoptedonDecember11,1997inKyoto,Japan,andenteredintoforceonFebruary16,2005�AsofNovember2009,187stateshavesignedandratifiedtheprotocol,butwithouttheUnitedStatesandothercountries�

tersoftheUnitedNations,theGeneralAssemblyadoptedtheMillenniumDeclaration�Afollow-upoutcomeoftheresolutionpassedtheGeneralAssemblyonDecember14,2000toguideitsimple-mentation�ProgressonimplementationoftheDeclarationwasreviewedatthe2005WorldSummitofleaders�

OnSeptember8,2000,followinga3-dayMillenniumSummitofworldleadersattheheadquar-TheWorldSummitonSustainableDevelopment(WSSD)orEarthSummit2002tookplaceinJohannesburg,SouthAfrica,fromAugust26toSeptember4,2002�ItwasconvenedtodiscussSDbytheUN�WSSDgatheredanumberofleadersfrombusinessandnongovernmentalorgani-zations,10yearsafterthefirstEarthSummitinRiodeJaneiro�(Itwasthereforealsoinformallynicknamed“Rio+10”�)

The2009UNClimateChangeConference,commonlyknownastheCopenhagenSummit,washeldinCopenhagen,Denmark,betweenDecember7and18�

Theconferenceincludedthe15thConferenceoftheParties(COP15)intheUNFCCCandthe5thMeetingoftheParties(COP/MOP5)intheKyotoProtocol�AccordingtotheBaliRoadMap,aframeworkforclimatechangemitigationbeyond2012wastobeagreedthere�Theconferencewaspreceded by the Climate Change: Global Risks, Challenges, and Decisions scientific conference,whichtookplaceinMarch2009andwasalsoheldattheBellaCentre�ThenegotiationsbegantotakeanewformatwheninMay2009UNSecretaryGeneralBanKi-moonattendedtheWorldBusinessSummitonClimateChangeinCopenhagen,organizedbytheCopenhagenClimateCouncil(COC),whereherequestedCOCcouncilorstoattendNewYork’sClimateWeekattheSummitonClimateChangeonSeptember22andengagewithheadsofgovernmentonthetopicoftheclimateproblem�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�

SDisanoptimalintersectionofsetsofallentitiesintheenvironment,economy(includingproduction), and human society� SD could be viable (for production, economy, and the environ-ment),sociallyandeconomicallyequitable,andsociallyandenvironmentallybearableinallandfor all� Most countries have no problem in accepting these environmental pillars� However, theacceptanceoftheseeconomicalandsocialpillarsmaygeneratescrupleorevenasilentoppositioninpoorerdevelopingcountriesorleast-developedcountriesontheonehand,butalsoindevelopedcountriesontheother,namely,thosewithaneoliberalgovernmentonprincipleasa“ThirdWay�”

14 Handbook on Applications of Ultrasound: Sonochemistry for Sustainability

SDalsohassomeshortfallsatitsstart�Theproportionbetweenthesizeofthepopulationandnonrenewableresourcesisincommensurableandthistrendwillgrowevenfurther(Cohen,1995)�Theproportionbetweenthestandardoflifeofthepeopleindevelopedcountriesandthatinleast-developedcountriesisincommensurableandthisdifferencewillnotceaseduringthelifetimeofonehumangeneration�Everyoneofthreerichestmenintheworldisinpossessionofmorepropertythanthewealthof48mostneedycountriesintheworld,whiletherichestwomaninFrancehasanannualincomethatequalsthatof15,700ofherfellowcitizenswhodrawminimalwages(Keller,2010)�

Theseproportionsshowthattheinequalitybetweensomepeopleandsomecountriesproducesadifferencethatwillprobablyrisefurther�Moreover,iftheeconomyindevelopedcountriesdoesnotshowcharacteristicsofgrowthinhumanconsumption,theglobaleconomywillsufferproblems�

AlbertBartlett,inhiscontribution“TheLawsofSustainability”intheanthologyThe Future of Sustainability(Keiner,2006),isveryskepticalabouttheword“sustainability”inconnectionwith

the term “development” and in the context of an exponentially growing human population� Heassertsinhisfirstof21“LawsofSustainability”thattheterm“SustainableGrowth”isanoxymo-ron�Inthenextlaws,hedeclaresthat“Onecannotsustainaworldinwhichsomeregionshavehighstandardsoflivingwhileothershavelowstandardsofliving”(5thLaw),“Thebenefitsofpopula-tiongrowthandofgrowthintheratesofconsumptionofresourcesaccruetoafew;thecostsofpopulationgrowthandgrowthintheratesofconsumptionofresourcesarebornebyallofsociety”(9thLaw),“Humanswillalwaysbedependentonagriculture”(16thLaw),“If,forwhateverreason,humansfailtostoppopulationgrowthandgrowthintheratesofconsumptionofresources,Naturewillstopthesegrowths”(18thLaw),“Starvingpeopledon’tcareaboutsustainability”(19thLaw),

“Theadditionoftheword‘sustainable’toourvocabulary,toourreports,programs,andpapers,tothenamesofouracademicinstitutesandresearchprograms,andtoourcommunityinitiatives,isnotsufficienttoensurethatoursocietybecomessustainable”(20thLaw),andhefinisheswith

“Extinctionisforever�”

AlltheserealitiesdonotleaveusfeelingoptimisticaboutthefurtherSDofhumankind�Hence,the activities of current political and economic elites, establishments, scientists, engineers, andtechnologistsarefocusedontheenvironmentalandeconomicalpillarsofSDasitsprofitableparts�Ontheotherhand,amutualrelationshipbetweentheenvironment,economy,andproductionactivi-tiesisevident�

ableendeavorsaimingatthebettermentandsurvivalofhumankindfollowingtherationaldevelop-mentandresponsivegrowththatthisconceptentails�

Consequently,theconceptof“sustainabledevelopment”maybeunderstoodasasetofsustain-SUSTAINABLE DEVELOPMENT, CHEMISTRY, AND ITS ENGINEERING

AND TECHNOLOGICAL APPLICATION

Chemical production and its engineering and technological application are economically andsociallyverybeneficialtohumanitybutareverydisadvantageousfornaturalsourcesandfortherestoftheenvironment�Withthegoalofharmonizingthisdisproportionatebalance,thefollowingremedialsolutionshavecomeintodemand�

In1990,thePollutionPreventionActpassedintheUnitedStates�Thisacthelpedtocreateamodusoperandifordealingwithpollutioninanoriginalandinnovativeway�Itaimedatavoidingproblemsbeforetheyactuallyhappened�ShortlyafterthepassageofthePollutionPreventionActof1990,theEPA’sOfficeofPollutionPreventionandToxics(OPPT)begantoexploretheideaofdevelopingneworimprovingexistingchemicalproductsandprocessestomakethemlesshazard-oustohumanhealthandtheenvironment�

In1991,theOPPTlaunchedthemodelresearchgrantsprogram“AlternativeSyntheticPathwaysforPollutionPrevention�”Thisprogramprovided,forthefirsttime,grantsforresearchprojectsthatincludedpollutionpreventioninthesynthesisofchemicals�SincethattimetheGreenChemistry

Emerging Ubiquity of Green Chemistry in Engineering and Technology 15

Programhasbuiltcollaborationswithmanypartnerstopromotepollutionpreventionthroughgreenchemistry�Partneringorganizationsrepresentacademia,industry,othergovernmentagencies,andnongovernmentalorganizations�

triesexceptContinentalEurope�IntheEUanalogousactivitiesmaybepresentundertheindicesofsustainablechemistry�

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

Registration, Evaluation, Authorization and Restriction of Chemicals (REACH) is an EURegulationofDecember2006�REACHaddressestheproductionanduseofchemicalsubstancesandtheirpotentialimpactsonbothhumanhealthandtheenvironment�

REACHhasbeendescribedasthemostcomplexlegislationintheEU’shistoryandthemostimportantin20years�Itisthestrictestlawtodateregulatingchemicalsubstancesandwillaffectindustriesthroughouttheworld�REACHenteredintoforceinJune2007,withaphasedimplemen-tationoverthenextdecade�WhenREACHisfullyenforced,itwillrequireallcompaniesmanu-facturingorimportingchemicalsubstancesintotheEUinquantitiesof1tonormoreperyeartoregisterthesesubstanceswithanewEuropeanChemicalsAgency(ECHA)inHelsinki,Finland�BecauseREACHappliestosomesubstancesthatarecontainedinobjects(“articles”inREACHterminology),anycompanyimportinggoodsintoEuropecouldbeaffected�

About143,000chemicalsubstancesmarketedintheEUwerepreregisteredbytheDecember1,2008deadline�Althoughpreregisteringisnotmandatory,itallowspotentialregistrantsmuchmoretimebeforetheyhavetofullyregister�

SupplyofsubstancestotheEuropeanmarketwhichhavenotbeenpreregisteredorregisteredisillegal(knowninREACHas“nodata,nomarket”)�REACHlegislationcanthereforehelptopre-ventariskconnectedwiththeuseofhazardouschemicals�

IncontrasttotheEPA,theEEAdoesnotorganizeprogramssuchastheEPAGreenChemistryProgram�TheEuropeanTechnologyPlatformforSustainableChemistry(SusChem)isaEuropeanTechnologyPlatform(ETP)initiativetoimprovethecompetitivepositionoftheEUinthefieldofchemistryinthreedomains:industrialbiotechnology,materialstechnology,andreactionandpro-cessdesign�

resenting the European communities and the industry� The main objective of the program is toproduceandimplementaStrategicResearchAgenda(SRA)�

Theprogramisajointinitiative(public–privatepartnership)oftheEuropeanCommission,rep-Sustainablechemistry,itsengineeringandtechnologicalapplicationsarealsofocusedoncleanerchemicalprocessesandtheirdesigningusingthe“bestavailabletechnologies”(BAT)�Theterm

“bestavailabletechnology”isappliedunderregulationsonlimitingpollutantdischargeswithregardtotheabatementstrategy�Similartermsare“bestavailabletechniques,”“bestpracticablemeans,”and “best practicable environmental option�” The term constitutes moving targets on practices,sincedevelopingsocietalvaluesandadvancingtechniquesmaychangewhatiscurrentlyregardedas“reasonablyachievable,”“bestpracticable,”and“bestavailable�”

Aliteralunderstandingwillconnectitwitha“sparenoexpense”doctrinewhichprescribestheacquisitionofthebeststate-of-the-arttechnologyavailable,withoutregardfortraditionalcost–benefitanalysis�Inpracticalusage,thecostaspectisalsotakenintoaccount�

In principle, sustainable chemistry and technology platforms for sustainable chemistry (allEuropeanandnational)andgreenchemistryincludegreenengineering,technology,andproduc-tion,andallhavethesamegoalsandprinciplesanduseanalogousmethodologiesandmethods�FundamentalconnectionsbetweenSDandsustainableandgreenchemistryareexplainedanddescribedbyEissenetal�(2002),Metzger(2004),andinthecontextofindustriesbyPoliakoffand

16 Handbook on Applications of Ultrasound: Sonochemistry for Sustainability

License(2007)�Twoexclusivejournals,Green Chemistry(RSC)since1999andChemSusChem

(WileyInterscience)since2008,publishthemostup-to-dateresultsandsolutionsofsustainableandgreenchemistry�

PRINCIPLES AND GOALS OF GREEN CHEMISTRY

mizingwasteandpollution,efficientexploitationofmaterialandenergysources,minimizinghazard,andminimizingcostsasaresultofthepreviousthree�Thekeytermforthesetofgreenchemistrygoalsis“minimizing”butinthecontextoftermslike“efficiently,”“rationally,”“really,”and“preferably�”Thisisbecausethedeclaredgoalsmaynotbeachievedpromptlyandabsolutely�Forexample,itisgenerally

Thegoalsofgreenchemistryarefocusedonfourofthecurrentdemandsofhumankindwhicharemini-knownthatfreons(CFCs)usedaspropellantsforspraycanswerereplacedbyn-butane(hazardousbut

lessthanCFCs)�Similarly,environmentallyhazardouschlorinatedhydrocarbonsastetrachloromethane,trichloroethylene,andtheotherchlorohydrocarbonswerealternatedbysupercriticalcarbondioxideaswashingmedia�Principlesfortheachievementofthesetgoalsmaybegroupedinthefollowingway:

 A�Minimizing waste and pollution

 1� Preventionofwasteformationispreferredbeforewastedisposal�Itisbettertohandle

waste“atsource”thanat“endofpipe�”

 B�Efficient exploitation of material and energy sources

 2� Syntheses, synthetic processes, must be designed with highest atom economy, i�e�,

 1� Prevention:Itisbettertopreventwastethantotreatorcleanupwasteafterithasbeencreated�

 2�Atom economy:Syntheticmethodsshouldbedesignedtomaximizetheincorporationof

allmaterialsusedintheprocessintothefinalproduct�

Emerging Ubiquity of Green Chemistry in Engineering and Technology 17

 3�Less hazardous chemical syntheses:Whereverpracticable,syntheticmethodsshouldbe

designedtouseandgeneratesubstancesthatpossesslittleornotoxicitytohumanhealthandtheenvironment�

 4�Designing safer chemicals:Chemicalproductsshouldbedesignedtoaffecttheirdesired

 7�Use of renewable feedstocks:Arawmaterialorfeedstockshouldberenewableratherthan

depletingwhenevertechnicallyandeconomicallypracticable�

 8�Reduce

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

 12�Inherently safer chemistry for accident prevention:Substancesandtheformofasubstance

dents,includingreleases,explosions,andfires�

usedinachemicalprocessshouldbechosentominimizethepotentialforchemicalacci-METHODOLOGY AND METHODS OF GREEN CHEMISTRY

ticated methodology and broad scale of methods to current green chemistry� A sophisticatedapproachtosolveenvironmentalproblems,greenchemistry,maybeessentiallycharacterizedasa“trivialsolution”toanontrivialandcomplicatedproblem�Sophisticatedapproachessuchasthefieldofgreenchemistrymethodologyareoftenveryeffectivewithminimalenergyandtechnologydemandsandcosts�Themanufacturingof2,4-dichlorobenzylcyanide,animportantfinechemi-calandintermediateforphytoeffectorproduction,from2,4-dichlorobenzylchlorideandsodium

Scienceandadvancesinengineering,technology,andtechnicalproductionhavegivenasophis-cyanidewitharelativelylowlevelofE-factorandminimumwasteformation(CzechPatent301063

(2009),LucˇebnízávodyDraslovkaCo�Kolín)canserveasanexampleofacompletesophisticatedsolution�Thisprocesswasindustriallyrealizedwithhighyieldandpurityinmethanolassolventandinthecatalyticpresenceofsodiumiodide(Scheme1�5)�

Cl +

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

2,4-dichlorobenzylchlorideandsodiumcyanide�