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ENVIRONMENTAL INORGANIC CHEMISTRY FOR ENGINEERS ENVIRONMENTAL INORGANIC CHEMISTRY FOR ENGINEERS DR. JAMES G. SPEIGHT CD& W inc., Laramie,Wyoming, United States Butterworth-HeinemannisanimprintofElsevier TheBoulevard,LangfordLane,Kidlington,OxfordOX51GB,UnitedKingdom 50HampshireStreet,5thFloor,Cambridge,MA02139,UnitedStates Copyright©2017ElsevierInc.Allrightsreserved. Nopartofthispublicationmaybereproducedortransmittedinanyformorbyany means,electronicormechanical,includingphotocopying,recording,oranyinformation storageandretrievalsystem,withoutpermissioninwritingfromthepublisher.Detailson howtoseekpermission,furtherinformationaboutthePublisher’spermissionspoliciesand ourarrangementswithorganizationssuchastheCopyrightClearanceCenterandthe CopyrightLicensingAgency,canbefoundatourwebsite:www.elsevier.com/permissions. Thisbookandtheindividualcontributionscontainedinitareprotectedundercopyrightby thePublisher(otherthanasmaybenotedherein). Notices Knowledgeandbestpracticeinthisfieldareconstantlychanging.Asnewresearchand experiencebroadenourunderstanding,changesinresearchmethods,professionalpractices, ormedicaltreatmentmaybecomenecessary. Practitionersandresearchersmustalwaysrelyontheirownexperienceandknowledgein evaluatingandusinganyinformation,methods,compounds,orexperimentsdescribed herein.Inusingsuchinformationormethodstheyshouldbemindfuloftheirownsafetyand thesafetyofothers,includingpartiesforwhomtheyhaveaprofessionalresponsibility. Tothefullestextentofthelaw,neitherthePublishernortheauthors,contributors,oreditors, assumeanyliabilityforanyinjuryand/ordamagetopersonsorpropertyasamatterof productsliability,negligenceorotherwise,orfromanyuseoroperationofanymethods, products,instructions,orideascontainedinthematerialherein. LibraryofCongressCataloging-in-PublicationData AcatalogrecordforthisbookisavailablefromtheLibraryofCongress BritishLibraryCataloguing-in-PublicationData AcataloguerecordforthisbookisavailablefromtheBritishLibrary ISBN:978-0-12-849891-0 ForinformationonallButterworth-Heinemannpublications visitourwebsiteathttps://www.elsevier.com/books-and-journals Publisher:MatthewDeans AcquisitionEditor:KenMcCombs EditorialProjectManager:PeterJardim ProductionProjectManager:KiruthikaGovindaraju CoverDesigner:VitoriaPearson TypesetbySPiGlobal,India AUTHOR BIOGRAPHY Dr.JamesG.SpeightCChem.,FRSC,FCIC,andFACSearnedhisBSc andPhDdegreesfromtheUniversityofManchester,England;healsoholds aDScingeologicsciencesandaPhDinpetroleumengineering.Dr.Speight is the author of more than 70 books in fossil fuel and engineering and environmentalsciences.Now,beinganindependentconsultant,hewasfor- merlytheCEOoftheWesternResearchandhasservedasadjunctprofessor intheDepartmentofChemicalandFuelsEngineeringattheUniversityof Utah and in the Departments of Chemistry and Chemical and Petroleum Engineering at the University of Wyoming. In addition, he has also been a visiting professor in chemical engineering at the following universities: the University of Missouri-Columbia, the Technical University of Denmark, and the University of Trinidad and Tobago. Dr.SpeightwaselectedtotheRussianAcademyofSciencesin1996and awarded the gold Medal of Honor that same year for the outstanding contributions to the field of petroleum sciences. He has also received the Scientists without Borders Medal of Honor of the Russian Academy of Sciences.In2001,theacademyalsoawardedDr.SpeighttheEinsteinmedal for the outstanding contributions and service in the field of geologic sciences. ix PREFACE Thelatterpartofthe20thcenturysawtherealizationarisethatallchemicals canactasenvironmentalpollutants,andinaddition,therecametherealiza- tion that emissions of inorganic chemicals such as carbon dioxide (CO ), 2 methane (CH ), and nitrous oxide (N O) to the atmosphere and a host 4 2 ofotherinorganicchemicalstowatersystemsandtolandsystemshadeither a direct or indirect impacts on the various floral and faunal systems. As a result,unprecedentedeffortshavebeenmadetoreduceallglobalemissions andchemicalsdisposalinordertomaintainagreenperspective.Furthermore, operations have been designed to reduce the direct emissions of inorganic chemical products (such as carbon dioxide, sulfur oxides, and nitrogen oxides) into the air (the atmosphere), inorganic chemicals into water systems (theaquasphere),andinorganicchemicalsontothesoil(theterrestrialbiosphere). This has been accompanied by efforts to recycle and to reuse as much of these chemicals and chemical waste as possible. Theprimarypurposeofthisbookistofocusonthevariousissuesrelated totheproductionanduseofinorganicchemicalissuesthatarethefocusof anyenvironmentalchemistryprogram.Inthecontextofinorganicchemis- try,thebookalsopresentsanunderstandingofinformationonenvironmen- tallyimportantphysiochemicalpropertiesofinorganicchemicalsforuseby engineersandmanagersaswellasanynonchemists.Thisbookisacompan- iontexttoabook(EnvironmentalOrganicChemistryforEngineers,James G.Speight,Elsevier,2017)previouslypreparedforenvironmentallyimpor- tant effects and properties of organic chemicals. Like the “organics” book, this“inorganics”bookdescribesavailableinformationthatrelatestothepro- perties of inorganic chemicals and the effects of these chemicals on the environment.Thisinformationsupportstheprimaryobjectiveofthebook, which is to assist environmental engineers and managers (many of whom may not have a detailed knowledge or understanding of inorganic envi- ronmentalchemistry)inovercomingthecommonproblemofpropertydata gaps and developing timely responses to environmental problems. This “inorganics” book presents not only generic discussion of these properties butalsoasummaryofenvironmentallyimportantdataforthemostcommon elements and pollutants. The topics covered in this book are the basis topics that serve to intro- duce the reader to not only inorganic chemistry but also the effect of xi xii Preface inorganicchemicalsonvariousecosystems.Basicrulesofnomenclatureare presented. Understanding the mechanism of how a reaction takes place is particularlycrucialinthisandofnecessity;thebookbringsalogicandsim- plicitytothereactionsofthedifferentfunctionalgroups.Thisinturntrans- forms a list of apparently unrelated facts into a sensible theme. Thus, this chapter will serve as an introduction to the physicochemical properties of inorganic chemicals and their effect on the floral and faunal environments. Thebookwillserveasaninformationsourcetheengineersinpresenting details of the various aspects of inorganic chemicals as they pertain to pol- lution of the environment. To accomplish this goal, the initial section (Chapters1–4)presentsanintroductiontoandadescriptionofthenomen- clature of inorganic compounds and the properties of these materials. The remaining part of the book (Chapters 5–9) presents information relevant to the sources of inorganic contaminants, the behavior of inorganic chemicals, the fate and consequences of chemicals in the environment, and cleanup of the environment. Fromthebook,thereaderwillgainanunderstandingofthefundamental inorganic chemistry and chemical processes that are central to a range of importantenvironmentalproblemsandtoutilizethisknowledgeinmaking criticalevaluationsoftheseproblems.Specificknowledgewillbeinthearea of(i)anunderstandingofthechemistryofthestratosphericozonelayerand of the important ozone depletion processes; (ii) an understanding of the chemistry of important tropospheric processes, including photochemical smog and acid precipitation; (iii) understanding of the basic physics of the greenhouse effect and of the sources and sinks of the family of greenhouse gases; (iv) an understanding of the nature, reactivity, and environmental fates of toxic inorganic chemicals; and (v) an understanding of societal implications of some environmental problems. An appendix contains a selectionoftablesthatcontaindatarelatingtothepropertiesandcharacter- ization of the elements and inorganic compounds, and a comprehensive glossary will help the reader to understand the common terms that are employed in this field of science and engineering. Dr. James G. Speight Laramie, Wyoming Jan. 2017 CHAPTER ONE Inorganic Chemicals in the Environment 1.1 INTRODUCTION Environmental chemistry focuses on environmental concerns about materials,energy,andproductioncyclesanddemonstrateshowfundamental chemicalprinciplesandmethodologiescanprotectthefloral(plant)andfau- nal(animal,includinghuman)specieswithintheenvironment(Anastasand Kirchhoff,2002).Morespecifically,theprinciplesofchemistrycanbeused to develop how global sustainability can be supportedand maintained. For this, future environmental chemists and environmental engineers must acquirethescientificandtechnicalknowledgetodesignproductsandchem- icalprocesses.Theymustalsoacquireanincreasedawarenessoftheenviron- mental impact of chemicals on the environment and develop an enhanced awareness of the importance of sustainable strategies in chemical research andthechemicalindustry,specificallyinthecontextofthisbooktheinor- ganic chemicals industry. Bywayofintroduction,althoughotherclassificationsystemshavebeen published, a general classification of chemical pollutants is based on the chemicalstructureofthepollutantandincludes(i)organicchemicalpollut- ants and (ii) inorganic chemical pollutants. For the purposes of this text, organic chemical pollutants are those chemicals of organic origin or that couldbeproducedbylivingorganismsorarebasedofmatterformedbyliv- ing organisms (Speight, 2017a). Ontheotherhand,inorganicchemicalpollutantsarethosechemicalsof mineraloriginin(notproducedbylivingorganisms).Ingeneral,substances of mineral origin (such as ceramics, metals, synthetic plastics, and water) as opposed to those of biological or botanical origin (such as crude oil, coal, wood, and food). In addition, minerals are the inorganic, crystalline solid EnvironmentalInorganicChemistryforEngineers Copyright©2017ElsevierInc. 1 http://dx.doi.org/10.1016/B978-0-12-849891-0.00001-1 Allrightsreserved. 2 EnvironmentalInorganicChemistryforEngineers that makes up rocks. With certain exceptions, inorganic substances do not contain carbon or its compounds. In scientific terms, no clear line divides organic and inorganic chemistry. Inorganicchemistryfocusesontheclassificationofinorganiccompounds basedonthepropertiesofthecompound(s)(Welleretal.,2014).Partly,the classification focuses on the position in the periodic table (Fig. 1.1) of the heaviestelement(theelementwiththehighestatomicweight)inthecom- pound,partlybygroupingcompoundsonthebasisofstructuralsimilarities. Also, inorganic compounds aregenerally structuredby ionic bonds and do notcontaincarbonchemicallyboundtohydrogen(hydrocarbons)oranyof theirderivativesthatcontainelementssuchasnitrogen,oxygen,sulfur,and metals.Examplesofinorganiccompoundsincludesodiumchloride(NaCl) and calcium carbonate (CaCO ) and pure elements (Cox, 1995). 3 Thus, this text relates to an introduction to the planned and unplanned effects of inorganic chemicals on the various environmental systems. Inor- ganic chemicals are an essential component of life, but some chemicals are extremely toxic and can severely damage the floral (plant life) and faunal (animal life) environment (Table 1.1). Aswithorganicchemicals(Speight,2017a),contaminationoftheenvi- ronment by inorganic chemicals is a global issue, and toxic inorganic chemicals are found practically in all ecosystems because, at the end of the various inorganic chemical life cycles, inorganic chemicals have been either recycled for further use or sent for disposal as chemical waste (Bodeketal.,1988).Currentregulationsdonotpermittheunmanageddis- posalofchemicalwastebut,inthepast(particularlyinthefirstdecadesofthe 20th century), the inappropriate management of chemical waste (e.g., through haphazard disposal and unregulated burning) has led to a series of negative and lingering impacts on the floral and faunal species that are part of the environment. Briefly, inorganic chemistry deals with the synthesis and behavior of inorganic and organometallic compounds. The exception to the sub- disciplineisthe multitude ofchemical compoundsthatfall within thesub- discipline of organic chemistry that covers the multitude of organic compounds (carbon-based compounds, usually containing CdH bonds). Thedistinctionbetweenthetwosubdisciplinesisfarfromabsolute,asthere ismuchoverlapwithinthesubdisciplineoforganometallicchemistry.Nev- ertheless, the principles of inorganic chemistry have application in every aspectofthechemicalindustry,includingmaterialsscience,catalysis,surfac- tants, pigments, coatings, medications, fuels, and agriculture. In o 1 6 2 rg H Atomic number He an HY1D.0R0O8G0EN C Chemical symbol Nonmetals 4H.E0L0IU2M6 icC h 3 Li 4 Be Carbon Chemical name 5 B 6 C 7 N 8 O 9 F 10Ne emic L6IT.H9I6U8M BE9R.Y0L1L2IU2M 12.011 Atomic weight 1B0O.R8O1N4 C1A2R.0B1O1N N1IT4R.O0G0E7N O1X5Y.9G9E9N F1LU8O.9R9IN8E 2N0E.1O8N0 als 11 12 13 14 15 16 17 18 in Na Mg Al Si P S Cl Ar th e 2SO2D.9IU9M0 MA2G4N.3E0SI6UM Metals AL2U6M.9IN8U2M 2SI8L.I0CO8N5 PH3O0SP.H97OR4US 3SU2L.0FU6R8 C3H5L.O4R5IN2E 3A9R.G9O4N8 En v 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 iro K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr n m POTASSIUM CALCIUM SCANDIUM TITANIUM VANADIUM CHROMIUM MANGANESE IRON COBALT NICKEL COPPER ZINC GALLIUM GERMANIUM ARSENIC SELENIUM BROMINE KRYPTON e 39.0983 40.078 44.956 47.867 50.942 51.996 54.938 55.845 58.933 58.693 63.546 65.38 69.723 72.630 74.922 78.971 79.904 83.798 n t 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe RUBIDIUM STRONTIUM YTTRIUM ZIRCONIUM NIOBIUM MOLYBDENUMTECHNETIUMRUTHENIUM RHODIUM PALLADIUM SILVER CADMIUM INDIUM TIN ANTIMONY TELLURIUM IODINE XENON 85.468 87.62 88.906 91.224 92.906 95.95 [98] 101.07 102.91 106.42 107.87 112.41 114.82 118.71 121.76 127.60 126.90 131.29 55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn CESIUM BARIUM HAFNIUM TANTALUM TUNGSTEN RHENIUM OSMIUM IRIDIUM PLATINUM GOLD MERCURY THALLIUM LEAD BISMUTH POLONIUM ASTATINE RADON 132.91 137.33 178.49 180.95 183.84 186.21 190.23 192.22 195.08 196.97 200.59 204.38 207.2 208.98 [209] [210] [222] 87 88 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 Fr Ra Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og FRANCIUM RADIUM RUTHERFORDIUM DUBNIUM SEABORGIUM BOHRIUM HASSIUM MEITNERIUMDARMSTADTIUMROENTGENIUMCOPERNICIUM NIHONIUM FLEROVIUM MOSCOVIUMLIVERMORIUMTENNESSINE OGANESSON [223] [226] [263] [268] [271] [270] [270] [278] [281] [281] [285] [286] [289] [289] [293] [294] [294] 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 Key La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu = Solid at room temperature LANTHANUM CERIUM PRASEODYMIUMNEODYMIUMPROMETHIUMSAMARIUM EUROPIUM GADOLINIUM TERBIUM DYSPROSIUM HOLMIUM ERBIUM THULIUM YTTERBIUM LUTETIUM 138.91 140.12 140.91 144.24 [145] 150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.05 174.97 = Liquid at room temperature = Gas at room temperature 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr = Radioactive = Artificially made AC[T2I2N7IU]M T2H3O2R.I0U4M PRO2T3A1C.T0IN4IUM U2R3A8N.0IU3M NEP[T2U3N7I]UM PLU[2TO4N4I]UM AM[E2R4IC3I]UM C[U2R4I7U]M BER[2K4EL7I]UMCAL[IF2O5R1N]IUMEINS[2TE5I2N]IUM FE[R2M57IU]M MEN[D2E5L8EV]IUM NO[B2E5L9IU]M LAW[R2E6N2C]IUM Fig.1.1 Theperiodictableoftheelements. 3