General Chemistry PDF

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GeneralChemistry/Printversion
GeneralChemistry
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Athreedimensionalrepresentationofanatomic4forbital.
AboutGeneralChemistry
en.wikibooks.org/wiki/General_Chemistry/Print_version
GeneralChemistryisanintroductiontothebasicconceptsofchemistry,includingatomicstructureandbonding,chemicalreactions,andsolutions.Othertopicscoveredinclude
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GeneralChemistryisanintroductiontothebasicconceptsofchemistry,includingatomicstructureandbonding,chemicalreactions,andsolutions.Othertopicscoveredinclude gases,thermodynamics,kineticsandequilibrium,thermodynamics,redox,andchemistryoftheelements. Itisassumedthatthereaderhasbasicscientificunderstanding.Otherwise,minimalknowledgeofchemistryisneededpriortoreadingthisbook.
BeyondGeneralChemistry
OrganicChemistryChemistrystudiesfocusingonthecarbonatomandcompounds. InorganicChemistryChemistrystudiesfocusingonsalts,metals,andothercompoundsnotbasedoncarbon. BiochemistryChemistrystudiesoforrelatingtolivingorganisms.
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AuthorsandSignificantContributors
NipplesMeCool Orngjce223
Introduction
ChemistryisEverywhere
Themodernhumanexperienceplacesalargeemphasisuponthematerialworld.Fromthedayofourbirthtothedaywedie,wearefrequently preoccupiedwiththeworldaroundus.Whetherstrugglingtofeedourselves,occupyingourselveswithmoderninventions,interactingwithotherpeople oranimals,orsimplymeditatingontheairwebreathe,ourattentionisfocusedondifferentaspectsofthematerialworld.Infactonlyahandfulof disciplinescertainsubsetsofreligion,philosophy,andabstractmathcanbeconsideredcompletelyunrelatedtothematerialworld.Everythingelse issomehowrelatedto chemistry,thescientificdisciplinewhichstudiestheproperties,composition,andtransformationofmatter.
BranchesofChemistry
Chemistryitselfhasanumberofbranches:
Chemistry:thestudyofthe properties,composition,and transformationofmatter.
Analyticalchemistryseekstodeterminethecompositionofsubstances. Biochemistryisthestudyofchemicalsfoundinlivingthings(suchasDNAandproteins). InorganicChemistrystudiessubstancesthatdonotcontaincarbon. Organicchemistrystudiescarbonbasedsubstances.Carbon,asdescribedinmoredetailinthisbook,hasuniquepropertiesthatallowittomakecomplexchemicals,including thoseoflivingorganisms.Anentirefieldofchemistryisdevotedtosubstanceswiththiselement. Physicalchemistryisthestudyofthe physicalpropertiesofchemicals,whicharecharacteristicsthatcanbemeasuredwithoutchangingthecompositionofthesubstance.

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Chemistryasadisciplineisbasedonanumberofotherfields.Becauseitisameasurementbasedscience,mathplaysanimportantrolein itsstudyandusage.Aproficiencyinhighschoollevelalgebrashouldbeallthatisneededinthistext,andcanbeobtainedfromanumberof sources.Chemistryitselfisdeterminedbytherulesandprinciplesofphysics.Basicprinciplesfromphysicsmaybeintroducedinthistext whennecessary.
WhyStudyChemistry?
Therearemanyreasonstostudychemistry.Itisonepillarofthenaturalsciencesnecessaryfordetailedstudiesinthephysicalsciencesor engineering.Theprinciplesofbiologyandpsychologyarerootedinthebiochemistryoftheanimalworld,inwaysthatareonlynowbeginning tobeunderstood.Modernmedicineisfirmlyrootedinthechemicalnatureofthehumanbody.Evenstudentswithoutlongtermaspirationsin sciencefindbeautyintheinfinitepossibilitiesthatoriginatefromthesmallsetofrulesfoundinchemistry.
Thisisthestructureoftablesalt,or sodiumchloride.
Chemistryhasthepowertoexplaineverythinginthisworld,fromtheordinarytothebizarre.Whydoesironrust?Whatmakespropanesuch anefficient,cleanburningfuel?Howcansootanddiamondbesodifferentinappearance,yetsosimilarchemically?Chemistryhasthe answertothesequestions,andsomanymore.Understandingchemistryisthekeytounderstandingtheworldasweknowit.
ThisBook:GeneralChemistry
Anintroductiontothechemicalworldissetforthinthistext.Theunitsofstudyareorganizedasfollows. 1. PropertiesofMatter:Anexplanationofthemostfundamentalconceptinchemistry: matter. 2. AtomicStructure:Whiletechnicallyinthedomainofphysics, atomsdeterminethebehaviorofmatter,makingthemanecessarystartingpoint foranydiscussionofchemistry. 3. CompoundsandBonding:Chemical bondingisintroduced,whichexplainshowlessthanonehundrednaturallyoccurringelementscan combinetoformallthedifferentcompoundsthatfillourworld. 4. ChemicalReactions:Thingsgetinterestingoncechemical reactionsstartmakingandbreakingbonds. 5. AqueousSolutions:Substances dissolvedinwaterhavespecialproperties.Thisiswhen acidsandbasesareintroduced. 6. PhasesofMatter:Adetailedlookatthe organizationofsubstances,withparticularfocuson gases. 7. ChemicalEquilibria:Chemicalreactionsdon'tgoonforever. Equilibriumisthebalancethatreactionsseektoachieve. 8. ChemicalKinetics: Kineticsexplainwhyittakesyearsforanironnailtorust,butonlyasplitsecondforahydrogenfilledhotairballoontoexplode. 9. Thermodynamics:Twothingsdecidewhichreactionscanoccurandwhichreactionscannot:heatandchaos.Or enthalpyandentropy,astheyarecalledinthermodynamics 10. ChemistriesofVariousElements:Anexplorationofthe elementsthatmakeupallsubstance.Includesanintroductionto nuclearchemistryandcarbon,theessenceof organicchemistry.
<<BeginYourStudyofGeneralChemistry!>>
BasicPropertiesofMatter
Matter
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WhatisMatter?
Matterisdefinedasanythingthathas massand volume. Massisameasureofanobject'sinertia.Itisproportionaltoweight:themoremassanobjecthas,themoreweightithas.However, massisnotthesameasweight.Weightisaforcecreatedbytheactionofgravityonasubstancewhilemassisameasureofanobject's resistancetochangeinmotion.MassismeasuredbycomparingthesubstanceofinteresttoastandardkilogramcalledtheInternational PrototypeKilogram(IPK).TheIPKisametalcylinderwheretheheightanddiameterbothequal39.17millimetersandismadeofan alloyof90%platinumand10%iridium.Thus,thestandardkilogramisdefinedandallothermassesareacomparisontothiskilogram. Whenatommassesaremeasuredinamassspectrometer,adifferentinternalstandardisused.Yourtakehomelessonwithregardto massisthatmassisarelativetermjudgedbyacomparison. Volumeisameasureoftheamountofspaceoccupiedbyanobject.Volumecanbemeasureddirectlywithequipmentdesignedusing graduationsmarksorindirectlyusinglengthmeasurementsdependingonthestate(gas,liquid,orsolid)ofthematerial.A graduated cylinder,forexample,isatubethatcanholdaliquidwhichismarkedandlabeledatregularintervals,usuallyevery1or10mL.Oncea liquidisplacedinthecylinder,onecanreadthegraduationmarksandrecordthevolumemeasurement.Sincevolumechangeswith temperature,graduatedequipmenthaslimitstotheprecisionwithwhichonecanreadthemeasurement.Solidobjectsthathaveregular shapecanhavetheirvolumecalculatedbymeasuringtheirdimensions.Inthecaseofabox,it'svolumeequalslengthtimeswidthtimesheight.
Matterhasmassandvolume,as exemplifiedbythisconcreteblock.
Itisparticularlyinterestingtonotethatmeasuringisdifferentfromcalculatingaspecificvalue.Whilemassandvolumecanbothbedetermineddirectlyrelativetoeitheradefined standardorlinemarksonglass,calculatingothervaluesfrommeasurementsisnotconsideredmeasuring.Forexample,onceyouhavemeasuredthemassandvolumeofaliquid directly,onecanthencalculatethedensityofasubstancebydividingthemassbythevolume.Thisisconsideredindirectlydeterminingdensity.Interestinglyenough,onecanalso measuredensitydirectlyifanexperimentwhichallowsthecomparisonofdensitytoastandardissetup. Anotherquantityofmatterdirectlyorindirectlydeterminedisthe amountofsubstance.Thiscaneitherrepresentacountedquantityofobjects(e.g.threemiceoradozenbagels) ortheindirectlydeterminednumberofparticlesofasubstancebeingdealtwithsuchashowmanyatomsarecontainedinasampleofapuresubstance.Thelatterquantityis describedintermsofmoles.Onemoleisaspecificallydefinedasthenumberofparticlesin12gramsoftheisotopeCarbon12.Thisnumberis6.02214078(18)x1023particles. UnitsofMeasure Mass:thekilogram(kg).Also,thegram(g)andmilligram(mg). 1kg=1000g 1000mg=1g. Volume:theliter(L),milliliter(mL).Also,cubiccentimeters(cc)andcubicmeters(m3). 1cc=1mL 1000mL=1L 1000L=1m3 Amount:themole(mol). 1mol=6.02214078(18)x1023particles
Atoms,Elements,andCompounds
Thefundamentalbuildingblockofmatteristheatom.
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Anyatomiscomposedofalittlenucleussurroundedbya"cloud"ofelectrons.Inthenucleusthereareprotonsandneutrons. However,theterm"atom"justreferstoabuildingblockofmatteritdoesn'tspecifytheidentityoftheatom.Itcouldbeanatomof carbon,oranatomofhydrogen,oranyotherkindofatom. Thisiswheretheterm"element"comesintoplay.Whenanatomisdefinedbythenumberofprotonscontainedinitsnucleus,chemists refertoitasan element.Allelementshaveaveryspecificidentitythatmakesthemuniquefromotherelements.Forexample,anatom with6protonsinitsnucleusisknownastheelement carbon.Whenspeakingoftheelement fluorine,chemistsmeananatomthat contains9protonsinitsnucleus.
Thereddotsareprotons,theblackdotsare neutrons,andthebluedotsareelectrons.
Atom:Afundamentalbuildingblockofmattercomposedofprotons,neutrons,andelectrons. Element:Auniquelyidentifiableatomrecognizedbythenumberofprotonsinthenucleus.
Despitethefactthatwedefineanelementasauniqueidentifiableatom,whenwespeak,forexample,5elements,wedon'tusuallymeanthose5atomsareofthesametype (havingthesamenumberofprotonsintheirnucleus).Wemean5'types'ofatoms.Itisnotnecessarythereareonly5atoms.Theremaybe10,or100,etc.atoms,butthoseatoms belongtooneof5typesofatoms.I'dratherdefine'element'as'typeofatom'.Ithinkitismoreprecise.Ifwe'dliketoreferto5atomshavingthesame6protonsintheirnucleus,I'd say'5carbonatoms'or'5atomsofcarbon'. Itisimportanttonotethatifthenumberofprotonsinthenucleusofanatomchanges,sodoestheidentityofthatelement.Ifwecouldremoveaprotonfromnitrogen(7protons),it isnolongernitrogen.Wewould,infact,havetoidentifytheatomascarbon(6protons).Remember,elementsareuniqueandarealwaysdefinedbythenumberofprotonsinthe nucleus.The PeriodicTableoftheElementsshowsallknownelementsorganizedbythenumberofprotonstheyhave. Anelementiscomposedofthesametypeofatom elementalcarboncontainsanynumberofatoms,allhaving6protonsintheirnuclei.Incontrast, compoundsarecomposedof differenttypeofatoms.Moreprecisely,acompoundisachemicalsubstancethatconsistsoftwoormoreelements.A carboncompoundcontainssomecarbonatoms(with6protons each)andsomeotheratomswithdifferentnumbersofprotons. Compoundshavepropertiesdifferentfromtheelementsthatcreatedthem.Water,forexample,iscomposedofhydrogenandoxygen.Hydrogenisanexplosivegasandoxygenisa gasthatfuelsfire.Waterhascompletelydifferentproperties,beingaliquidthatisusedtoextinguishfires. Thesmallestrepresentativeforacompound(whichmeansitretainscharacteristicsofthecompound)iscalleda molecule.Moleculesarecomposedofatomsthathave"bonded" together.Asanexample,the formulaofawatermoleculeis"H2O":twohydrogenatomsandoneoxygenatom.
PropertiesofMatter
Propertiesofmattercanbedividedintwoways:extensive/intensive,orphysical/chemical.
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Extensivepropertiesdependontheamountofmatterthatisbeingmeasured. Theseincludemassandvolume. Intensivepropertiesdonotdependontheamountofmatter.Theseinclude densityandcolor.
Physicalpropertiescanbemeasuredwithoutchangingthechemical'sidentity. Thefreezingpointofasubstanceisphysical.Whenwaterfreezes,it'sstillH2O. Chemicalpropertiesdealwithhowonechemicalreactswithanother.Weknow thatwoodisflammablebecauseitbecomesheat,ash,andcarbondioxidewhen heatedinthepresenceofoxygen.
StatesofMatter
Oneimportantphysicalpropertyisthe stateofmatter.Threearecommonineverydaylife:solid,liquid,andgas.Thefourth, plasma,isobservedinspecialconditionssuchasthe onesfoundinthesunandfluorescentlamps.Substancescanexistinanyofthestates.Waterisacompoundthatcanbeliquid,solid(ice),orgas(steam).
Solids
Solidshaveadefiniteshapeandadefinitevolume.Mosteverydayobjectsaresolids:rocks, chairs,ice,andanythingwithaspecificshapeandsize.Themoleculesinasolidareclose togetherandconnectedby intermolecularbonds.Solidscanbe amorphous,meaningthatthey havenoparticularstructure,ortheycanbearrangedintocrystallinestructuresornetworks.For instance,soot,graphite,anddiamondareallmadeofelementalcarbon,andtheyareall solids.Whatmakesthemsodifferent?Sootisamorphous,sotheatomsarerandomlystuck together.Graphiteformsparallellayersthatcanslippasteachother.Diamond,however, formsacrystalstructurethatmakesitverystrong.
Liquids
Thestatesofmatterdependonthebonding betweenmolecules.
Liquidshaveadefinitevolume,buttheydonothaveadefiniteshape.Instead,theytakethe shapeoftheircontainertotheextenttheyareindeed"contained"bysomethingsuchas beakeroracuppedhandorevenapuddle.Ifnot"contained"byaformalorinformalvessel, theshapeisdeterminedbyotherinternal(e.g.intermolecular)andexternal(e.g.gravity,wind,inertial)forces.Themoleculesareclose, butnotascloseasasolid.Theintermolecularbondsareweak,sothemoleculesarefreetoslippasteachother,flowingsmoothly.A propertyofliquidsis viscosity,themeasureof"thickness"whenflowing.Waterisnotnearlyasviscousasmolasses,forexample.
Theiceinthispictureisasolid.Thewater inthepictureisaliquid.Intheairthereis watervapor,whichisagas.
Gases
Gaseshavenodefinitevolumeandnodefiniteshape.Theyexpandtofillthesizeandshapeoftheircontainer.Theoxygenthatwebreatheandsteamfromapotarebothexamples ofgases.Themoleculesareveryfarapartinagas,andthereareminimalintermolecularforces.Eachatomisfreetomoveinanydirection.Gasesundergoeffusionanddiffusion. Effusionoccurswhenagasseepsthroughasmallhole,anddiffusionoccurswhenagasspreadsoutacrossaroom.Ifsomeoneleavesabottleofammoniaonadesk,andthereisa holeinit,eventuallytheentireroomwillreekofammoniagas.Thatisduetothediffusionandeffusion.Thesepropertiesofgasoccurbecausethemoleculesarenotbondedtoeach other. Ingases,intermolecularforcesareveryweak,hencemoleculesmoverandomlycollidingwiththemselves,andwiththewalloftheircontainer,thusexertingpressureontheir container.Whenheatisgivenoutbygases,theinternalmolecularenergydecreaseseventually,thepointisreachedwhenthegasliquifies.
ChangesinMatter
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Therearetwotypesofchangeinmatter: physicalchangeand chemicalchange.Asthenamessuggest,physicalchangesaffectphysicalproperties,andchemicalchangesaffect chemicalproperties. Chemicalchangesarealsoknownaschemicalreactions.The"ingredients"ofareactionarethereactants,andtheendresultsarecalledthe"products".Thechangefromreactants toproductscanbesignifiedbyanarrow.
AChemicalReaction ReactantsProducts
Notethatthenumberofreactantsandproductsdon'tnecessarilyhavetobethesame.However,thenumberofeachtypeofatommustremainconstant.Thisiscalledthe Lawof ConservationofMatter.Itstatesthatmattercanneverbecreatedordestroyed,onlychangedandrearranged.Ifachemicalreactionbeginswith17molesofcarbonatoms,itmust endwith17molesofcarbonatoms.Theymaybebondedintodifferentmolecules,orinadifferentstateofmatter,buttheycannotdisappear. Whenchangesoccur,energyisoftentransformed.However,likeatoms,energycannotdisappear.Thisiscalledthe LawofConservationofEnergy.Asimpleexamplewouldbe puttingicecubesintoasoftdrink.Theicecubesgetwarmerasthedrinkgetscolder,becauseenergycannotbecreatedordestroyed,onlytransferred.Notethatenergycanbe "released"or"stored"bymakingandbreakingbonds.Whenaplantconvertstheenergyfromsunlightintofood,thatenergyisstoredinthechemicalbondswithinthesugar molecules.
ChemicalorPhysical?
Physicalchangesdonotcauseasubstancetobecomeafundamentallydifferentsubstance.Chemicalchanges,ontheotherhand,cause asubstancetochangeintosomethingentirelynew.Chemicalchangesaretypicallyirreversible,butthatisnotalwaysthecase.Itiseasier tounderstandthedifferencebetweenphysicalandchemicalchangeswithexamples.
Statechangesarephysical.
Phasechangesarewhenyoumelt,freeze,boil,condense,sublimate,ordeposita substance.Theydonotchangethenatureofthesubstanceunlessachemicalchange occursalongwiththephysicalchange.
Cutting,tearing,shattering,and grindingarephysical.
Thesemaybeirreversible,buttheresultisstillcomposedofthesamemolecules.When youcutyourhair,thatisaphysicalchange,eventhoughyoucan'tputthehairbackon yourheadagain.
Mixingtogethersubstancesis physical.
Forexample,youcouldmixsaltandpepper,dissolvesaltinwater,ormixmoltenmetals togethertoproduceanalloy.
Isblendingtogetherasmoothieaphysical orchemicalchange?
Gasbubblesformingischemical.
Nottobeconfusedwithbubblesfromboiling,whichwouldbephysical(aphasechange). Gasbubblesindicatethatachemicalreactionhasoccurred.
Precipitatesformingischemical.
Whendissolvedsubstancesaremixed,andacloudyprecipitateappears,therehasbeena chemicalchange.
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Rotting,burning,cooking,and rusting(forexample)arechemical.
Theresultingsubstancesareentirelynewchemicalcompounds.Forinstance,wood becomesashandheatironbecomesrustsugarfermentsintoalcohol.
Changesofcolororreleaseof odors(i.e.releaseofagas)might bechemical.
Asanexample,theelementchromiumshowsdifferentcolorswhenitisindifferent compounds,butasinglechromiumcompoundwillnotchangecoloronitsownwithout somesortofreaction.
Release/absorptionofenergy (heat,light,sound)isgenerallynot easilycategorized.
Hot/coldpacksinvolvedissolvingasaltinwatertochangeitstemperature(moreonthatin laterchapters)poppingpopcornismostly(butnotcompletely).
ClassificationofMatter
Mattercanbeclassifiedbyitsstate. Solidshaveasetvolumeandshape.Theintermolecularforceofattractionforsolidmatterisverystrong. Liquidshaveasetvolume,butchangeshape.Theintermolecularforceofattractionforliquidmatterisweakerthansolidmatter. Gaseshaveneitherdefinitevolumenorshape.Theintermolecularforceofattractionforgaseousmatterisnegligible. Plasmawhichareusuallygaseousstateofmatterinwhichapartoralloftheatomsormoleculesaredissociatedtoformions. Mattercanalsobeclassifiedbyitschemicalcomposition. Anelementisapuresubstancemadeupofatomswiththesamenumberofprotons.Asof2011,118elementshavebeenobserved,92ofwhichoccurnaturally.Carbon(C), Oxygen(O),Hydrogen(H)areexamplesofelements.Theperiodictableisatabularrepresentationoftheknownelements. Acompoundconsistsoftwoormorechemicalelementsthatarechemicallybondedtogether.Water(H2O)andtablesugar(C12H22O11)areexamplesofchemical compounds.Theratiooftheelementsinacompoundisalwaysthesame.Forexampleinwater,thenumberofHatomsisalwaystwicethenumberofOatoms. Amixtureconsistsoftwoormoresubstances(elementorcompound)mixedtogetherwithoutanychemicalbond.Saladisagoodexample.Amixturecanbeseparatedinto itsindividualcomponentsbymechanicalmeans.
TypesofMixtures
Therearemanykindsofmixtures.Theyareclassifiedbythebehaviorofthe phases,orsubstancesthathavebeenmixed.
HomogeneousMixtures
Ahomogeneousmixtureisuniform,whichmeansthatanygivensampleofthemixturewillhavethesamecomposition.Air,seawater,andcarbonationdissolvedinsodaareall examplesofhomogeneousmixtures,orsolutions.Nomatterwhatsampleyoutakefromthemixture,itwillalwaysbecomposedofthesamecombinationofphases.Chocolatechip icecreamisnothomogeneousonespoonfultakenmighthavetwochips,andthenanotherspoonfulmighthaveseveralchips.
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Anexampleforahomogeneousmixtureisasolution.Thesubstancethatgetsdissolvedisthe solute.Thesubstancethatdoesthedissolvingisthe solvent.Togethertheymakea solution.Ifyoustiraspoonfulofsaltintoaglassofwater,saltisthesolutethatgetsdissolved.Wateristhesolvent.Thesaltywaterisnowasolution,orhomogeneousmixture,of saltandwater. Whendifferentgasesaremixed,theyalwaysformasolution.Thegasmoleculesquicklyspreadoutintoauniformcomposition.
HeterogeneousMixtures
A heterogeneousmixtureisnotuniform.Differentsamplesmayhavedifferentcompositions,liketheexampleofchocolatechipice cream.Concrete,soil,blood,andsaladareallexamplesofheterogeneousmixtures. Suspensions Whensandgetskickedupinapond,itcloudsthewater.Soonthesandsettlesdown,andis nolongermixedintothewater.Thisisanexampleofa suspension.Suspensionsare heterogeneousmixturesthatwilleventuallysettle.Theyareusually,butnotnecessarily, composedofphasesindifferentstatesofmatter.Italiansaladdressinghasthreephases:the water,theoil,andthesmallpiecesofseasoning.Theseasoningsaresolidsthatwillsinkto thebottom,andtheoilandwaterareliquidsthatwillseparate. Colloids
Thisdustisasuspensionbecauseit settlesaftertheworkisdone. Sodawaterisahomogeneousmixture. (Thestrawlooksbrokenbecauseof refraction.)
Whatexactlyistoothpaste?Wecan'texactlyclassifyitbyitsstateofmatter.Ithasadefinite shapeandvolume,likeasolid.Butthenyousqueezethetube,anditflowsalmostlikea liquid.Andthenthere'sjelly,shavingcream,smoke,dough,andSillyPutty...
Theseareexamplesof colloids.Acolloidisaheterogeneousmixtureoftwosubstancesofdifferentphases.Shavingcreamandother foamsaregasdispersedinliquid.Jello,toothpaste,andothergelsareliquiddispersedinsolid.Doughisasoliddispersedinaliquid. Smokeisasoliddispersedinagas. Colloidsconsistoftwophases:a dispersedphaseinsideofa continuousmedium. TheTyndallEffect

Toothpasteisacolloid,becauseit'spart TheTyndalleffectdistinguishescolloidsfromsolutions.Inasolution,theparticlesaresofinethattheywillnotscatterlight.Thisisnot solidandpartliquid. trueforacolloid.Ifyoushinelightthroughasolution,thebeamoflightwillnotbevisible.Itwillbevisibleinacolloid.Forinstance,ifyou haveeverplayedwithalaserpointer,youhaveseentheTyndalleffect.Youcannotseethelaserbeaminair(asolution),butifyoushine itintoamist(acolloid,orsuspension,actually),thebeamisvisible.Cloudslookwhite(orgray),asopposedtoblue,becauseoftheTyndalleffectthelightisscatteredbythesmall dropletsofsuspendedwater.
MethodsforSeparatingMixtures
Becausethereisnochemicalbondinginamixture,thephasescanbeseparatedbymechanicalmeans.Inaheterogeneousmixturelikeasalad,thepiecescaneasilybepickedout andseparated.Itisassimpleassiftingthroughthesaladandpickingoutallthetomatoesandradishes,forexample.However,manymixturescontainparticlesthataretoosmall, liquids,ortoomanyparticlestobeseparatedmanually.Wemustusemoresophisticatedmethodstoseparatethemixture.
Filtration
Imagineyouhaveasandbox,buttherearebitsofbrokenglassinit.Allyouwouldneedissomesortoffilter.Thesandparticlesaremuchsmallerthantheglasschips,soamesh
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Imagineyouhaveasandbox,buttherearebitsofbrokenglassinit.Allyouwouldneedissomesortoffilter.Thesandparticlesaremuchsmallerthantheglasschips,soamesh filterwouldletsandpassbutstoptheglass.Filtrationisusedinallsortsofpurificationmethods.Somefilters,likedialysistubing,aresuchfinefiltersthatwatercanpass,but dissolvedglucosecannot.
Distillation
Ifyouweregivenaglassofsaltwater,couldyoudrinkit?Sure,ifyoudistillitfirst.Distillationistheboilingofamixturetoseparateitsphases.Saltisasolidatroomtemperature, andwaterisaliquid.Waterwillboilfarbeforesaltevenbeginstomelt.Soseparatingthetwo isassimpleasboilingthewateruntilallthatremainsisthesolidsalt.Ifdesired,thewater vaporcanbecollected,condensed,andusedasasourceofpurewater. Distillationcanalsobeusediftwoliquidsaremixedbuthavedifferentboilingpoints. Separationofseveralliquidswithsimilarboilingpointscanbeachievedusingfractionation.
CentrifugationandSedimentation
Theseprocessesrelyondifferencesindensity.Inamedicallab,bloodoftengoesintoa centrifuge.Acentrifugeisamachinethatspinsasampleatfairlyhighratesofspeed.Red bloodcellsaremuchdenserthanthewaterysubstance(calledplasma,butit'snottheplasma stateofmatter)thatmakesupblood.Asaresultofthespinning,thedenserphasesmove outwardandthelessdensephasesmoveinward,towardstheaxisofrotation.Then,thered bloodcellscanbeseparatedfromtheplasma. Sedimentationissimilar,butithappenswhenparticlesofdifferentdensitieshavesettled withinaliquid.Ifajarofmuddywaterislefttosettle,theheaviestparticlessinktothebottom first.Thelightestparticlessinklastandformalayerontoptheheavierparticles.Youmay haveseenthiseffectinabottleofsaladdressing.Theseasoningssinktothebottom,the waterformsalowerlayer,andtheoilformsanupperlayer.Theseparatephasescanbe skimmedout.Toreturnittoamixture,simplyshakeituptodisturbthelayers.
Filtrationisonewaytoseparateamixture.
UniqueProperties
Sedimentationisusedtopurifywaste water,bylettingitsettleandremovingthe settledmaterial(sludge,inthiscase).
Adistillationapparatushasaboilingflask, aplacetocoolthevapordown,anda collectingflask.
Thedifferencesinsubstances'propertiescanbeexploitedtoallowseparation.Considertheseexamples:
Amixtureofsandandironfilingscanbeseparatedbymagnet. Saltandsandcanbeseparatedbysolution(sandwillnotdissolveinwater,saltwill) Heliumcanbeseparatedfromamixturewithhydrogenbycombustion(thisisaverydangerousoperation,sincehydrogeninthepresenceofoxygenishighlyexplosive). Hydrogenisflammable,butheliumisnot.
Othermethods
Therearecountlessotherwaystoseparatemixtures.Forinstance,gelelectrophoresisisusedtoseparatedifferentsizedpiecesofDNA.Theyareplacedintogel,andanelectric currentisapplied.Thesmallerpiecesmovefasterandseparatefromthelargerpieces. Chromatographyseparatesphasesdissolvedinliquid.Ifyouwanttoseeanexample,takeastripofpaperanddrawadotonitwithacoloredmarker.Dipthestripintowater,and waitawhile.Youshouldseetheinkseparateintodifferentcolorsastheyspreadoutfromthedot.
NumbersUsedtoDescribeAtoms
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Numbers
The Atomicnumberisthenumberofprotonsinthenucleusofanatom.Thisnumberdeterminestheelementtypeoftheatom.Forinstance,allneonatomshave exactlytenprotons.Ifanatomhastenprotons,thenitmustbeneon.Ifanatomisneon,thenitmusthavetenprotons. Theatomicnumberissometimesdenoted Z.Continuingwiththeexampleofneon, .
The Neutronnumberisthenumberofneutronsinthenucleusofanatom.Rememberthatneutronshavenoelectriccharge,sotheydonotaffectthechemistryof anelement.However,theydoaffectthenuclearpropertiesoftheelement.Forinstance,Carbon12hassixneutrons,anditisstable.Carbon14haseightneutrons, andithappenstoberadioactive.Despitethesedifferences,bothformsofcarbonbehavethesamewaywhenformingchemicalcompounds. Theneutronnumberissometimesdenoted N.
Chromatography separates things dissolved inliquid.
Iftheredpartsareprotonsandthegreen partsareneutrons,what'stheatomic, neutron,andmassnumberofthisatom? (lithium)
The Massnumberisthesumofprotonsandneutronsinanatom.Itisdenoted A.Tofindthemassnumberofanatom,rememberthat A=Z+N.Themassnumberofanatomis
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The Massnumberisthesumofprotonsandneutronsinanatom.Itisdenoted A.Tofindthemassnumberofanatom,rememberthat A=Z+N.Themassnumberofanatomis alwaysaninteger.Becausethenumberofneutronscanvaryamongdifferentatomsofthesameelement,therecanbedifferentmassnumbersofagivenelement.Lookbacktothe exampleofcarbon.Carbon14hasamassnumberof14,andCarbon12hasamassnumberof12.Everycarbonatom must havesixprotons,soCarbon14haseightneutronsand Carbon12hassixneutrons. Isotopesofthesameelementhavenearlyidenticalchemicalproperties(becausetheyhavethesamenumberofprotonsandelectrons).Theironlydifferenceisthenumberof neutrons,whichchangestheirnuclearpropertieslikeradioactivity.
Notation
Thereisaconvenientwayofwritingthenumbersthatdescribeatoms.Itiseasiesttolearnbyexamples.
HelpfulHint!
Thisishowwewritefluorine19.Theatomicnumberisbelowandthemassnumberisabove,followedbyits symbolontheperiodictableoftheelements.
Keepinmindthatanyofthethree numberswrittenaroundtheelement symbolareoptional,buttheyshould bewrittenifitisimportanttothegiven situation.Thechargenumberisleftoff iftheatomhaszerocharge(equal numberofprotonsandelectrons). Themassnumberandatomicnumber areusuallyleftoff.
Thisexampleshowscarbon12.Noticehowtheatomicnumberismissing.Youknowwhichelementitis becauseoftheC,sothereisnoneedtowritethenumberofprotons.Theatomicnumberisrarelywritten becausetheelementsymbolimplieshowmanyprotonsthereare.
Thelastexampleshowsboththeatomicnumberandmassnumber,alongwithacharge.Thechargeisthe differenceinthenumberofprotonscomparedtothenumberofelectrons.Youcanreadmoreaboutcharge, protons,andelectronslateron.Fromtheexample,youcanseethatthismagnesiumatomwouldhave12 protons,13neutrons,and10electrons.Itsmassis25(12p+13n)anditschargeis+2(12p10e).
Exerciseforthereader! Trywritingthesymbolforanatomwithsevenprotons,sevenneutrons,andeightelectrons.Youwillneedtolookupitssymbolontheperiodic table.
AtomicMass
Themassofanatomismeasuredin atomicmassunits(amu).Anatom'smasscanbefoundbysummingthenumberofprotonsandneutrons.Bydefinition,12amuequalsthe atomicmassofcarbon12.Protonsandneutronshaveanapproximatemassof1amu,andelectronshaveanegligiblemass. Usually,apureelementismadeupofanumberofisotopesinspecificratios.Becauseofthis,themeasuredatomicmassofcarbonisnotexactly12.Itisanaverageofallthe massesofalltheisotopes,withthemorecommononescontributingmoretothemeasuredatomicmass.Byconventionatomicmassesaregivennounits.
Example
PretendthattheelementWikibookiumhastwoisotopes.Thefirsthasamassnumberof104,andthesecondhasamassnumberof107.
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PretendthattheelementWikibookiumhastwoisotopes.Thefirsthasamassnumberof104,andthesecondhasamassnumberof107. Consideringthat75%ofthenaturallyoccurringatomsareofthefirstisotope,andtherestareofthesecond.Theaverageatomicmassis calculatedas 0.75104+0.25107=104.75 Inthiscase,abunchofWikibookiumatomswouldhaveanaveragemassof104.75amu,buteachindividualatommighthaveamassnumberof 104or107.Keepinmindthatalloftheatomswouldhavethesamenumberofprotons.Theirmassesaredifferentbecauseofthenumberof neutrons.
Moles
Amoleisdefinedastheamountofanelementwhosenumberofparticlesareequaltothatin12gofC12carbon,alsoknownasAvogrado'snumber.Avogadro'snumberequals 6.0221023.Molesarenotveryconfusing:ifyouhaveadozenatoms,youwouldhave12.Ifyouhaveamoleofatoms,youwouldhave6.0221023.Whyisthisridiculouslylarge numberimportant?Itcanbeusedtoconvertbetweenatomicmassunitsandgrams.Onemoleofcarbon12isexactly12grams,bydefinition.Similarly,onemoleofanyelementis theatomicmassofthatelementexpressedasaweightingrams.Theatomicmassisequaltothenumberofgramspermoleofthatelement.
Example Thereare128.2gofrubidium(atomicmass=85.47amu).Howmanyatomsarethere? (128.2g)/(85.47g/mol)=1.5mol (1.5mol)(6.0221023)= 9.031023atomsofrubidium
Molesarealsoimportantbecauseevery22.4litersofgascontain1moleofgasmoleculesatstandardtemperatureandpressure(STP,0 Cand1atmosphereofpressure).Avogradodiscoveredthis.(That'swhyit'shisnumber.)Acontainerfilledwithfluorinegaswouldhave tobe22.4LlargetoholdonemoleofF2molecules.Knowingthisfactallowsyoutodeterminethemassofagasmoleculeifyouknow thevolumeofthecontainer.Thisholdstrueforeverygas. Whyeverysinglegas?Atomsandmoleculesare tiny.Thevolumeofagasismostlyemptyspace,sothemoleculeshavean insignificantlysmallvolume.Asyouwilleventuallylearn,thisensuresthatthereisalwaysonemoleofgasatomsforevery22.4litersat STP.
Historyof Atomic Structure

Whyisthehistoryoftheatomsoimportant?
AtomicStructure
Theseonelitercontainerseachhold0.045 molesofnitrogenbasedgas.(1L)/(22.4 L/mol)=0.045mol
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Itisfundamentaltotheunderstandingofsciencethatscienceisunderstoodtobeaprocessoftrialandimprovementandrepresentsthebestknownatthetime,notanunerring oracleoftruth.Developmentofanideaandrefinementthroughtestingisshownmoreintheunderstandingofatomicstructure.
TheGreekTheorists
TheearliestknownproponentofanythingresemblingmodernatomictheorywastheancientGreekthinkerDemocritus.Heproposedthe existenceofindivisibleatomsasaresponsetotheargumentsofParmenides,andtheparadoxesofZeno. Parmenidesarguedagainstthepossibilityofmovement,change,andpluralityonthepremisethatsomethingcannotcomefromnothing. ZenoattemptedtoproveParmenides'pointbyaseriesofparadoxesbasedondifficultieswithinfinitedivisibility. Inresponsetotheseideas,Democrituspositedtheexistenceofindestructibleatomsthatexistinavoid.Theirindestructibilityprovideda retorttoZeno,andthevoidallowedhimtoaccountforplurality,change,andmovement.Itremainedforhimtoaccountfortheproperties ofatoms,andhowtheyrelatedtoourexperiencesofobjectsintheworld. Democritusproposedthatatomspossessedfewactualproperties,withsize,shape,andmassbeingthemostimportant.Allother properties,heargued,couldbeexplainedintermsofthethreeprimaryproperties.Asmoothsubstance,forinstance,mightbecomposed ofprimarilysmoothatoms,whileasoursubstanceiscomposedofroughorsharpones.Solidsubstancesmightbecomposedofatoms withnumeroushooks,bywhichtheyconnecttoeachother,whiletheatomsofliquidsubstancespossessfarfewerpointsofconnection. Democritusproposed8pointstohistheoryofatoms. [1]Theseare: 1. Allmatteriscomposedofatoms,whicharebitsofmattertoosmalltobeseen.TheseatomsCANNOTbefurthersplitintosmaller portions. 2. Thereisavoid,whichisemptyspacebetweenatoms. 3. Atomsarecompletelysolid 4. Atomsarehomogeneous,withnointernalstructure. 5. Atomsaredifferentin:theirsizes,theirshapes,andtheirweights. 6. Atomsarethebuildingblocksoflife
AbustofDemocritus(orDemocrites),who cameupwiththeideaofindivisibleatoms.
Alchemy
Empedoclesproposedthattherewerefourelements,air,earth,water,andfireandthateverythingelsewasa mixtureofthese.Thisbeliefwasverypopularinthemedievalagesandintroducedthescienceofalchemy. Alchemywasbasedonthebeliefthatsinceeverythingwasmadeofonlyfourelements,youcouldtransmutea mixtureintoanothermixtureofthesametype.Forexample,itwasbelievedthatleadcouldbemadeintogold. Alchemy'sproblemwasexposedbyAntoineLavoisierwhenheheatedmetallictininasealedflask.Agrayishash appearedonthesurfaceofthemeltingtin,whichLavoisierheateduntilnomoreashformed.Aftertheflaskcooled, heinverteditandopeneditunderwater.Hediscoveredthewaterroseonefifthofthewayintotheglass,leading Lavoisiertoconcludethatairitselfisamixture,withonefifthofithavingcombinedwiththetin,yettheotherfour fifthsdidnot,showingthatairwasnotanelement.
Althoughalchemywasfutile,the alchemistsdidcomeupwithseveraluseful methods,includingdistillation(shown here).
Lavoisierrepeatedtheexperimentagain,substitutingmercuryfortin,andfoundthatthesamehappened.Yetafter heatinggently,hefoundthattheashreleasedtheair,showingthattheexperimentcouldbereversed.He concludedthattheashwasacompoundofthemetalandoxygen,whichheprovedbyweighingthemetalandthe ash,andshowingthattheircombinedweightwasgreaterthanthatoftheoriginalmetal. Lavoisierthenstatedthatcombustionwasnotanelement,butinsteadwasachemicalreactionofafueland
Afire,shownby Lavoisiertobea chemicalreaction andnotanelement.
oxygen.
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JohnDalton
ModernatomictheorywasbornwithDaltonwhenhepublishedhistheoriesin1803.Histheoryconsistsoffiveimportantpoints,whichare consideredtobemostlytruetoday:(fromWikipedia) Elementsarecomposedoftinyparticlescalledatoms. Allatomsofagivenelementareidentical. Theatomsofagivenelementaredifferentfromthoseofanyotherelementtheatomsofdifferentelementscanbedistinguishedfromone Differentelements,different anotherbytheirrespectiverelativeweights. atoms. Atomsofoneelementcancombinewithatomsofotherelementstoformchemicalcompoundsagivencompoundalwayshasthesame relativenumbersoftypesofatoms. Atomscannotbecreated,dividedintosmallerparticles,nordestroyedinthechemicalprocessachemicalreactionsimplychangesthewayatomsaregroupedtogether. Wenowknowthatelementshavedifferentisotopes,whichhaveslightlydifferentweights.Also,nuclearreactionscandivideatomsintosmallerparts(butnuclearreactionsaren't reallyconsidered chemicalreactions).Otherwise,histheorystillstandstoday.
DmitriMendeleev
Whilewritingaseriesoftextbooks,Mendeleevrealizedhewasrunningoutofspacetotreateachelementindividually.Hesortedtheelementsbyweight,regularly"linewrapped"the elementsontothenextline,andmadewhatisnowcalledtheperiodictableoftheelements.Usinghistable,hepredictedtheexistenceof"ekaaluminum"and"ekasilicon"(gallium andselenium)successfully,confirmingtheusefulnessofhistable.Latertheories,thoseoftheelectronsaroundtheatom,explainwhyelementsinthesameperiod,orgroup,have similarchemicalproperties.
J.J.Thompson
DiscoveryoftheElectron
Intheyear1889theBritishphysicistJ.J.Thomsondiscoveredtheelectron.Thomsonconductedanumberofexperimentsusing cathode raytube.Cathoderaysareconstructedbysealingtwoelectrodesinaglasstubeandremovingtheairfromit.Whentheelectrodesare attachedtohighvoltage,abeamofradiationisemittedfromthenegativeelectrode.Thesebeamsarecalledcathoderays. Thompsondiscoveredthatcathoderaystravelinstraightlinesexceptwhentheyarebentbyelectricormagneticfields.Becausethe cathoderaysbentawayfromanegativelychargedplate,Thomsonconcludedthattheseraysaremadeofnegativelychargedparticles todaywecallthemelectrons.Thompsonfoundthathecouldproducecathoderaysusingelectrodesofvariousmaterials.Hethen concludedthatelectronswerefoundinallatomsandareoverathousandtimessmallerthanprotons.
The"PlumPudding"AtomicModel
Soonafterthediscoveryoftheelectron,Thompsonbeganspeculatingonthenatureoftheatom.Hesuggesteda"plumpudding"model. Inthismodelthebitsof"plum"weretheelectronswhichwerefloatingaroundina"pudding"ofpositivechargetomatchthatofthe electronsandmakeanelectricallyneutralatom.Amodernillustrationofthisideawouldbeachocolatechipcookie,withthechipsrepresentingnegativelychargedelectronsandthe doughrepresentingpositivecharge.
Cathoderaysareactuallymadeof electrons.
Rutherford
ErnestRutherfordisknownforhisfamous goldfoilexperimentin1911.Alphaparticles,whichareheavyandpositivelycharged(actually,heliumnuclei,butthat'sbesidethepoint),
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ErnestRutherfordisknownforhisfamous goldfoilexperimentin1911.Alphaparticles,whichareheavyandpositivelycharged(actually,heliumnuclei,butthat'sbesidethepoint), werefiredataverythinlayerofgold.Mostofthealphaparticlespassedstraightthrough,asexpected.Accordingtotheplumpuddingmodel alloftheparticlesshouldhaveslowed astheypassedthroughthe"pudding",butnoneshouldhavebeendeflected.Surprisingly,afewalphaparticlesweredeflectedbackthe waytheycame.Hestatedthatitwas"asifyoufireda15inchshellatapieceoftissuepaperanditcamebackandhityou." TheresultoftheexperimentallowedRutherfordtoconcludethattheplumpuddingmodeliswrong. Atomshavea nucleus,verysmallanddense,containingthepositivechargeandmostoftheatom'smass. Theatomconsistsofmostlyemptyspace. Theelectronsareattractedtothenucleus,butremainfaroutsideit.
NielsBohr
Bohrcreatedhisownmodeloftheatom,improvingonRutherford's.Bohrcreatedanequation thatcouldpredictthespectrallinesofthehydrogenatom.Hethenrealizedthatelectrons mustorbitthenucleusin"shells",eachwithacertainenergylevel.Anatomwillabsorband releasephotonsthathaveaspecificamountofenergy.Theenergyistheresultofanelectron jumpingtoadifferentshell.TheBohrmodeldepictstheatomasanucleuswithelectrons orbitingarounditatspecificdistances.
Millikan
Theresultsofthegoldfoilexperiment disprovedthe"plumpudding"model:the alphaparticlesshouldhavepassedthrough (top),butafewofthemdeflectedatlarge angles(bottom).
RobertMillikanisaccreditedforthe"OilDropExperiment",inwhichthevalueoftheelectron chargewasdetermined.Hecreatedamechanismwherehecouldsprayoildropsthatwould settleintoabeamofXrays.ThebeamofXrayscausedtheoildropstobecomechargedwith electrons.Theoildropletswereinbetweenapositivelychargedplateandanegatively chargedplatewhich,whenproperelectricvoltagewasapplied,causedtheoildropletto remainstill.RobertMillikanmeasuredthediameterofeachindividualoildropusinga microscope. Millikanwasabletocalculatethemassofeachoildropletbecauseheknewthedensityofthe ).Usingthemassofeachoildropletandtheequationfortheforceofgravitationalattraction to ,where isthemassofeachindividualoildroplet, is istheelectricalforcewhichequalsforceinthefirstequation),Millikanwasabletofindthevalue
oil( (whichherearrangedfrom theaccelerationduetogravity,and ofthechargeoftheelectron, .
TheBohrmodeloftheatomhasshellswith numberedsphericalenergylevelsthe largernumbersmeanlargerspheresand higherenergylevels.Thewaveexitingthe pictureonthelefthascomefroman electronjump,resultinginaphoton.(Level sizesnottoscale.)
TheXrays,however,didnotalwaysproduceanoildropwithonlyonenegativecharge.Thus,thevaluesMillikanobtainedmayhavelookedlikethis: coulomb coulomb coulomb coulomb Millikanfoundthatthesevaluesallhadacommondivisor: 3,and2,asinthisexample.Thus,hestatedthatthecommondivisor, coulomb.Heconcludedthatdifferentvaluesoccurredbecausethedropletsacquiredchargesof5,4, coulomb,wasthechargeoftheelectron.
References
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1. http://dbhs.wvusd.k12.ca.us/webdocs/AtomicStructure/Greeks.html
SubatomicParticles
ParticleProperties
Beforelearningaboutsubatomicparticles,somebasicpropertiesshouldbeunderstood.
Charge
Particlesmaybeelectricallycharged. Chargeisapropertywhichdefinestheforcethataparticlewillexertonotherchargedparticles.Thereisawellknownsayingthatapplies perfectly:"Oppositesattract."(Likewise,likechargesrepel.)Positivechargesandnegativechargeswillattracteachotherandcometogether.Twopositiveortwonegativecharges willpusheachotheraway. Theamountofchargeaparticlehasismeasuredincoulombs,butitismoreconvenientlyexpressedintermsofaninteger.For instance,aheliumionthathas2lesselectronsthanusualhasachargeof+2,andabromideionwithonemoreelectronthanusual hasachargeof1.(Thismayseembackwards,butrememberthatanelectronhasanegativecharge.)Noticethatchargenotonly appliestosubatomicparticles,butalsoionsandotherthingsaswell.Alwaysremembertospecifyifachargeispositiveornegative. Unlikeordinarynumbers,we alwayswritetheplussignforpositivechargestoavoidconfusionwithanegativecharge.
HelpfulHint!
Notallparticleshavecharge.
Mass
Massisthemeasureofinertia.Fromasubatomicpointofview,masscanalsobeunderstoodintermsofenergy,butthatdoesnotconcernuswhendealingwithchemistry.Massfor particles,atoms,andmoleculesisnotmeasuredingrams,aswithordinarysubstances.Instead,itismeasuredin atomicmassunits,or amu.Formoreinformationaboutmassand amu,readthepreviouschaptersonpropertiesofmatter.
TheNucleus
Atthecenterofeachatomliesthenucleus.Itisincrediblysmall:ifyouweretotaketheaverageatom(itselfminisculeinsize)andexpanditto thesizeofafootballstadium,thenthenucleuswouldbeaboutthesizeofamarble.Itis,however,astoundinglydense:despitethetiny percentageoftheatom'svolumeitcontainsnearlyalloftheatom'smass.Thenucleusalmostneverchangesundernormalconditions, remainingconstantthroughoutchemicalreactions.Nucleiarethemselvesmadeupofapairofsmallerandmoredenseparticles,the proton andthe neutron.Theseparticlesarecollectivelydubbed nucleons.
Protons
Protonshaveachargeof+1andamassof1amu.Theyareoftenrepresentedbya . Protonswillbeimportantwhenlearningaboutacidsandbasestheyaretheessenceofacid.Rememberthatthenumberofprotonsinan atomisits atomicnumber,anddefineswhatelementitwillbe.Thenumberofprotonsinanucleusrangesfrom onetooverahundred. Considertheelementhydrogen.Itsatomicnumberis1,soithasoneprotonandoneelectron.Ifitismadeintoanion(anatomwithmissing orextraelectrons),itwillsimplybealoneproton.Thus,aproton isthenucleusofahydrogenatom,andaproton isahydrogenion.Therefore, aprotoncanbewrittenas or ,bothsymbolsforahydrogenion.
Anatom(nottoscale!)
Neutrons
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Neutronshavenochargeandamassof1amu.Aneutronisslightlyheavierthanaproton,butthedifferenceisinsignificant.Neutronsareoftenwritten . Unliketheprotons,neutronscannotexistoutsidethenucleusindefinitelyastheybecomeunstableandbreakdown.Withinone nucleustherecanbemanyprotonsandneutronsallincloseproximitytooneanother.Thenumberofneutronsinanucleusranges from zerotooverahundred. Youmaywonderwhyneutronsexist.Theyhavenocharge,socantheydoanything?Theanswerisyesneutronsarevery important.Rememberthatoppositesattractandlikesrepel.Ifso,thenhowcanseveralprotonsstayclumpedtogetherinthedense nucleusofanatom?Itwouldseemasiftheprotonswouldrepelandscatterthenucleus.However,thereisa strongnuclearforce thatholdsthenucleustogether.Thisincredibleforcecausesnucleonstoattracteachotherwithmuchgreaterstrengththanthe electricforcecanrepelthem,butonlyoverextremelyshortdistances.
Adelicatebalanceexistsbetweenthenumberofprotonsandneutrons.Protons,whichareattractedtooneanotherviathestrong forcebutsimultaneouslyrepelledbytheirelectromagneticcharges,cannotexistingreatnumberswithinthenucleuswithoutthe stabilizingactionofneutrons,whichareattractedviathestrongforcebutarenotcharged.Conversely,neutronslendtheirinherentinstabilitytothenucleusandtoomanywill destabilizeit.
Ourfriendsthephysicistssaythatneutrons andprotonsaremadeofevensmaller particlescalled quarks.Fortunately,we don'tneedtoknowaboutthatbecause quarksdonotaffectchemistry.Instead, quarksfallinthefieldofQuantum Mechanics.
Lastly,neutronsareveryimportantinnuclearreactions,suchasthoseusedinpowerplants.Neutronsactlikeabulletthatcansplitanatom'snucleus.Becausetheyhavenocharge, neutronsareneitherattractednorrepelledbyatomsandions.
TheElectronCloud
Surroundingthedensenucleusisacloudofelectrons.Electronshaveachargeof1andamassof0amu.Thatdoesnotmeantheyaremassless.Electronsdohavemass,butitis sosmallthatithasnoeffectontheoverallmassofanatom.Anelectronhasapproximately1/1800themassofaprotonorneutron.Electronsarewritten . Electronsorbittheoutsideofanucleus,unaffectedbythestrongnuclearforce.Theydefinethechemicalpropertiesofanatombecausevirtuallyeverychemicalreactiondealswith theinteractionorexchangeoftheouterelectronsofatomsandmolecules. Electronsareattractedtothenucleusofanatombecausetheyarenegativeandthenucleus(beingmadeofprotonsandneutrons)ispositive.Oppositesattract.However,electrons don'tfallintothenucleus.Theyorbitarounditatspecificdistancesbecausetheelectronshaveacertainamountofenergy.Thatenergypreventsthemfromgettingtooclose,asthey mustmaintainaspecificspeedanddistance.Changesintheenergylevelsofelectronscausedifferentphenomenasuchasspectrallines,thecolorofsubstances,andthecreationof ions(atomswithmissingorextraelectrons).
ElectronInteractions
Atomswillalwayshaveequalnumbersofprotonsandelectrons,sotheiroverallchargeiszero.Atomsareneutral.Ions,ontheotherhand,areatomsthathavegainedorlost electronsandnowhaveanunequalnumberofprotonsandelectrons.Ifthereareextraelectrons,theionwillbenegativelycharged.Iftherearemissingelectrons,theionwillbe positivelycharged,duetothemajorityofpositiveprotons. Valenceelectrons(theoutermostelectrons)areresponsibleforanatom'sbehaviorinchemicalbonds.The coreelectronsarealloftheelectronsnotintheoutermostshell,andthey rarelygetinvolved.Anatomwillattempttofillitsvalenceshell.Thisoccurswhenanatomhaseightvalenceelectrons(asexplainedinthenextchapter),soatomswillundergo chemicalbondstoeithershare,give,ortaketheelectronsitneeds.Sodium,forexample,isverylikelytogiveupitsonevalenceelectron,sothatitsoutershellisempty(theshell underneathitisfull).Chlorineisverylikelytotakeanelectronbecauseithassevenandwantseight.Whensodiumandchlorinearemixed,theyexchangeelectronsandcreate sodiumchloride(tablesalt).Asaresult,bothelementshavefullvalenceshells,andaverystablecompoundisformed.
IntroductiontoQuantumTheory
IntroductiontoQuantumMechanics
Inthelate18thcentury,manyphysicistsbelievedthattheyhadmadegreatprogressinphysics,andtherewasn'tmuchmorethatneededtobediscovered.Theclassicalphysicsat
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Inthelate18thcentury,manyphysicistsbelievedthattheyhadmadegreatprogressinphysics,andtherewasn'tmuchmorethatneededtobediscovered.Theclassicalphysicsat thetimewaswidelyacceptedinthescientificcommunity.However,bytheearly20thcentury,physicistsdiscoveredthatthelawsofclassicalmechanicsbreakdownintheatomic world,andexperimentssuchasthephotoelectriceffectcompletelycontradictthelawsofclassicalphysics.Asaresultofthesecrises,physicistsbegantoconstructnewlawsof physicswhichwouldapplytotheatomicworldthesetheorieswouldbecollectivelyknownas quantummechanics.Quantummechanics,insomeways,completelychangedtheway physicistsviewtheuniverse,anditalsomarkedtheendoftheideaofaclockworkuniverse(theideathatuniversewaspredictable).
ElectromagneticRadiation
Electromagneticradiation(ER)is aformofenergythatsometimesactslikeawave,andothertimesactslikeaparticle.Visiblelightisawellknownexample.AllformsofERhave twoinverselyproportionalproperties:wavelengthandfrequency.Wavelengthisthedistancefromonewavepeaktothenext,whichcanbemeasuredinmeters.Frequencyisthe numberofwavepeaksobservedinagivenpointduringasecond.Theunitforfrequencyishertz.
Sincewavelengthandfrequencyareinverselyrelated,theirproduct(multiplication)alwaysequalsaconstantspecifically,3.0x108m/sec,whichisbetterknownasthespeedof light. ThewavelengthandfrequencyofanyspecificoccurrenceofERdetermineitspositiononthe electromagneticspectrum.
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Asyoucansee,visiblelightisonlyatinyfractionofthespectrum. Theenergyofanelectromagneticwaveisgivenby frequencywilldoubletheenergy. ,where isPlank'sconstantand isthefrequency.Energyisdirectlyproportionaltofrequencydoublingthe
TheDiscoveryoftheQuantum
Sofarwehaveonlydiscussedthewavecharacteristicsofenergy.However,thewavemodelcannotaccountforsomethingknownasthe photoelectriceffect.Thiseffectisobservedwhenlightfocusedoncertainmetalsapparentlycauseselectronstobeemitted. (Photoelectricorsolarpanelsworkonthisprinciple.) Foreachmetalitwasfoundthatthereisaminimumthresholdfrequencyofelectromagneticradiationthatisneededtobeshoneonitin orderforittoemitelectrons.Onecouldnotreplaceacertainamountoflightatonefrequencywithtwiceasmuchlightofhalfthe frequency.Iflightonlyactsasawave,theeffectoflightshouldbecumulativethelightshouldaddup,littlebylittle,untilitcauses electronstobeemitted.Instead,thereisaclearcutminimumofthefrequencyoflightthattriggerstheelectronemissions. Theimplicationofthisisthatfrequencyisdirectlylinkedtoenergy,thehigherlightfrequencieshavingmoreenergy.Thisobservationled tothediscoveryoftheminimumamountofenergythatcouldbegainedorlostbyanatom.MaxPlancknamedthisminimumamountthe quantum,plural"quanta",meaning"howmuch".One photonoflightcarriesexactlyonequantumofenergy.
MoreEvidenceforaParticleTheoryofEnergy
Whenanelectriccurrentispassedthroughagas,someofthegasmolecules'electronsmovefromtheir groundstatetoan excitedstate thatisfurtherawayfromtheirnuclei.Whentheelectronsreturntothegroundstate,theyemitenergyofvariouswavelengths.Aprismcan beusedtoseparatethewavelengths,makingthemeasytoidentify.
Asphotonsstrikeametal,electronsare freed.Thephotoelectriceffectdependsonly onthelight'sfrequency,notintensity,which defieswavebehavior.
Iflightactedonlyasawave,thenthereshouldhavebeenacontinuousrainbowcreatedbytheprism.Instead,therewerediscretelinescreatedbydifferentwavelengths.Thisis becauseelectronsreleasespecificwavelengthsoflightwhenmovingfromanexcitedstatetoagroundstate.
Theemissionspectrumofnitrogengas.Thespectrallinesoccuratspecificwavelengths,showingtheparticlebehavioroflight.
TheQuantumModel
Uncertainty
Itturnsoutthatphotonsarenottheonlythingthatactlikewavesandparticles.Electrons,too,havethisdualcharacteristic.Electronscanbethoughtofaswavesofacertainlength, thustheywouldonlybeabletoformacirclearoundthenucleusatcertaindistances.Ofcourse,thisbringsupaproblem:areelectronsparticlesinaspecificlocation,orwavesina generalarea?WernerHeisenbergtriedusingphotonstolocateelectrons.Ofcourse,whenphotonsreachelectrons,theelectronschangevelocity,andmovetoanexcitedstate.Asa result,itisimpossibletoknowthevelocityandlocationofanelectronatthesametime.Thisisknownasthe Heisenberguncertaintyprinciple.TheHeisenberguncertainty principleisakindofscientificdilemma:themoreyouknowaboutsomething'svelocity,thelessyouknowaboutitspositionandthemoreyouknowaboutitsposition,thelessyou knowaboutitsvelocity.Thesignificanceofthisuncertaintyisthatyoucanneverknowexactlywhereanatom'selectronsare. Onthetinyscaleofanatom,theparticlemodelofanelectrondoesnotaccuratelydescribeitsproperties.Anelectrontendstoactmorelikeawaterwavethanabilliardball.Atany onemomentintimetheballisinsomedefiniteplaceitisalsomovinginsomedefinitedirectionatadefinitespeed.Thisiscertainlynottrueforwavesorelectronsingeneral.The Heisenberguncertaintyprinciplestatesthattheexactpositionandmomentumofanelectroncannotbesimultaneouslydetermined.Thisisbecauseelectronssimplydon'thavea
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definiteposition,anddirectionofmotion,atthesametime! Onewaytotrytounderstandthisistothinkofanelectronnotasaparticlebutasawave.Thinkofdroppingastoneintoapond.Theripplesstarttospreadoutfromthatpoint.We cananswerthequestion"Whereisthewave?"with"It'swhereyouplonkedthestonein".Butwecan'tanswerthequestion"Whatdirectionisthewavemoving?"becauseit'smoving inalldirections.It'sspreadingout.Nowthinkofawaveattheseaside.Weknowthedirectionofmotion.It'sstraightintowardsthebeach.Butwhereisthewave?Wecan'tpinpoint anexactlocation.It'sallalongthewater.
TheWaveFunction
Ifwecanneverknowexactlywhereanelectronis,thenhowdowekeeptrackofthemasthey orbitatoms?ErwinSchrdingermadetheconceptofthe SchrdingerWaveFunction.It tellstheprobabilityofanelectronbeingfoundatagivenposition.Youdon'tknowwherethe electronis,butyouknowwhereitismostlikelyandleastlikelytobefound.Theelectroncould beanywhere,butitisprobablygoingtobeacertaindistancefromtheatom,stayingwithina certainshape.
Orbitals
Inthefollowingsections,wewilllearnabouttheshells,subshells,andorbitalsthatthe electronsarein.Trynottogetconfuseditcanbedifficult.Understandingthisinformationwill helpyoutolearnaboutbonding,whichisveryimportant. Inessence,eachelectronorbitinganatomhasasetoffournumbersthatdescribeit.Those fournumbers,called quantumnumbers, tellushowfarawaytheelectronis,whatshapeof pathitislikelytofollow,andwhichdirectionitsorbitgoes.Eachelectroninanatomhasa Awaveformingacircle uniquesetofnumbers,andthenumberscanchangeifbondingoccursoranelectronis energizedintoahigherenergyorbit.Inthenextchapter,wewilllearntheexactmeaningof thosefourvaluesandhowtheyaffectthepaththeelectronfollows.
WernerHeisenberg(1927)
TheQuantumAtom
TheQuantumNumbers
Thesefournumbersareusedtodescribethelocationofanelectroninanatom. Number PrincipalQuantumNumber AngularMomentumQuantumNumber MagneticQuantumNumber SpinQuantumNumber Symbol PossibleValues
Thinkofthewaveequationlikeasprinkler youcannotpredicttheexactpathofa particularwaterdroplet,butyoudoknow (basedontherangeandshapeofthe sprinkler)whereitismostlikelytogo.
PrincipalQuantumNumber(n)
Determinesthe shell theelectronisin.Theshellisthemaincomponentthatdeterminestheenergyoftheelectron(higher ncorrespondstohigherenergy),aswellasnuclear
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Determinesthe shell theelectronisin.Theshellisthemaincomponentthatdeterminestheenergyoftheelectron(higher ncorrespondstohigherenergy),aswellasnuclear distance(higher nmeansfurtherfromthenucleus).Therowthatanelementisplacedontheperiodictabletellshowmanyshellstherewillbe.Helium(n=1),neon(n=2),argon(n =3),etc.
AngularMomentumQuantumNumber(l)
Alsoknownasazimuthalquantumnumber.Determinesthe subshell theelectronisin.Eachsubshellhasauniqueshapeandalettername.The sorbitalisshapedlikeasphere andoccurswhen l=0.The porbitals(therearethree)areshapedliketeardropsandoccurwhen l=1.The dorbitals(therearefive)occurwhen l=2.The forbitals(thereareseven) occurwhen l=3.(Bytheway,when l=4,theorbitalsare"gorbitals",butthey(andthe l=5"horbitals")cansafelybeignoredingeneralchemistry.) Thisnumberalsogivesinformationastowhatthe angularnodeofanorbitalis.Anodeisdefinedasapointonastandingwavewherethewavehasminimalamplitude.When appliedtochemistrythisisthepointofzerodisplacementandthuswherenoelectronsarefound.Inturnangularnodemeanstheplanarorconicalsurfaceinwhichnoelectronsare foundorwherethereisnoelectrondensity. Herearepicturesoftheorbitals.Keepinmindthattheydonotshowtheactualpathoftheelectrons,duetotheHeisenbergUncertaintyPrinciple.Instead,theyshowtheareawhere theelectronismostlikelytooccur(say,90%oftheprobability).Thetwocolorsrepresentthetwodifferentspinnumbers(thechoiceisarbitrary). m1 Sorbital 3 2 1 0 1 2 3
Porbitals
Dorbitals
Forbitals
MagneticQuantumNumber(ml)
Determinesthe orbital inwhichtheelectronlies.Forexample,therearethreeporbitalsinshell n=2:themagneticquantumnumberdetermineswhichoneoftheseorbitalsthe electronsresidein.Thedifferentorbitalsareorientedatdifferentanglesaroundthenucleus.Seehoweachporbitalhasthesamegeneralshape,buttheypointindifferentdirections aroundthenucleus.
SpinQuantumNumber(ms)
Determinesthe spinontheelectron.
SomeExamples
Let'sexaminethequantumnumbersofelectronsfromamagnesiumatom.Rememberthateachlistofnumberscorrespondsto(n, l, ml , ms). Twoselectrons: (1,0,0,+) (1,0,0,)
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Twoselectrons: (2,0,0,+) (2,0,0,) Sixpelectrons: (2,1,1,+) (2,1,1,) (2,1,0,+) (2,1,0,) (2,1,1,+) (2,1,1,) Twoselectrons: (3,0,0,+) (3,0,0,)
ThePeriodicTable
Noticeapatternontheperiodictable.Differentareas,orblocks,havedifferenttypesofelectrons.Thetwocolumnsontheleftmakethesblock.Thesixcolumnsontherightmake thepblock.Thelargeareainthemiddle(transitionmetals)makesthedblock.Thebottomportionmakesthefblock.Eachrowintroducesanewshell(akaenergylevel).Basically, therowtellsyouhowmanyshellsofelectronstherewillbe,andthecolumntellsyouwhichsubshellswilloccur(andwhichshellstheyoccurin).Thevalueofml canbedetermined bysomeoftheruleswewilllearninthenextchapter.Thevalueofmsdoesn'treallymatteraslongastherearenorepeatingvaluesinthesameorbital.
ShellsandOrbitals
Electronshells
Each shell issubdividedinto subshells,whicharemadeupof orbitals,eachofwhichhaselectronswithdifferentangularmomentum.Eachorbitalinashellhasacharacteristic shape,andisnamedbyaletter.Theyare: s, p, d,and f.Inaoneelectronatom(e.g.H,He+ ,Li+ ,etc.)theenergyofeachorbitalwithinaparticularshellisidentical.Howeverwhen thereismorethanoneelectron,theyinteractwithoneanotherandsplittheorbitalsintoslightlydifferentenergies.Withinanyparticularshell,theenergyoftheorbitalsdependson theangularmomentum,withthesorbitalhavingthelowestenergy,thenp,thend,thenf.
Thisimageshowstheorbitals(alongwithhybridorbitalsforbondingandasampleelectronconfiguration,explainedlater).
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Thisimageshowstheorbitals(alongwithhybridorbitalsforbondingandasampleelectronconfiguration,explainedlater).
Thesorbital
Thesimplestorbitalintheatomisthe1sorbital.Ithasnoradialorangular nodes:the1sorbitalissimplyasphereofelectrondensity.Anodeisapointwheretheelectron probabilityiszero.Aswithallorbitalsthenumberofradialnodesincreaseswiththeprinciplequantumnumber(i.e.the2sorbitalhasoneradialnode,the3shastwoetc.).Because theangularmomentumquantumnumberis0,thereisonlyonechoiceforthemagneticquantumnumberthereisonlyonesorbitalpershell.Thesorbitalcanholdtwoelectrons, aslongastheyhavedifferentspinquantumnumbers.
Theporbitals
Startingfromthe2ndshell,thereisasetofporbitals.Theangularmomentumquantumnumberoftheelectronsconfinedtoporbitalsis1,soeachorbitalhasone angularnode. Thereare3choicesforthemagneticquantumnumber,whichindicates3differentlyorientedporbitals.Finally,eachorbitalcanaccommodatetwoelectrons(withoppositespins), givingtheporbitalsatotalcapacityof6electrons.
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Theporbitalsallhavetwolobesofelectrondensitypointingalongeachoftheaxes.Eachoneissymmetricalalongitsaxis.Thenotationfortheporbitalsindicatewhichaxisit pointsdown,i.e.pxpointsalongthexaxis,pyontheyaxisandpzupanddownthezaxis.Theporbitalsare degeneratetheyallhavethesameenergy.Porbitalsareveryoften involvedin bonding. 2px 2py 2pz
Thedorbitals
Thefirstsetofdorbitalsisthe3dset.Theangularmomentumquantumnumberis2,soeachorbitalhastwo angularnodes.Thereare5choicesforthemagneticquantum number,whichgivesriseto5differentdorbitals.Eachorbitalcanholdtwoelectrons(withoppositespins),givingthedorbitalsatotalcapacityof10electrons.
Notethatallthedorbitalshavefourlobesofelectrondensity,exceptforthedz2orbital,whichhastwoopposinglobesandadoughnutofelectrondensityaroundthemiddle.Thed orbitalscanbefurthersubdividedintotwosmallersets.Thedx2y2anddz2allpointdirectlyalongthex,y,andzaxes.Theyforman egset.Ontheotherhand,thelobesofthedxy, dxzanddyzalllineupinthequadrants,withnoelectrondensityontheaxes.Thesethreeorbitalsformthe t2gset.Inmostcases,thedorbitalsare degenerate,butsometimesthey cansplit,withtheegandt 2gsubsetshavingdifferentenergy. CrystalFieldTheorypredictsandaccountsforthis.Dorbitalsaresometimesinvolvedinbonding,especiallyin inorganicchemistry.
Theforbitals
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Thefirstsetofforbitalsisthe4fsubshell.Thereare7possiblemagneticquantumnumbers,sothereare7forbitals.Theirshapesarefairlycomplicated,andtheyrarelycomeup whenstudyingchemistry.Thereare14felectronsbecauseeachorbitalcanholdtwoelectrons(withoppositespins).
FillingElectronShells
FillingElectronShells
Whenanatomorionreceiveselectronsintoitsorbitals,theorbitalsandshellsfillupinaparticularmanner.
Aufbauprinciple
Youmayconsideranatomasbeing"builtup"fromanakednucleusbygraduallyaddingtoitoneelectronafteranother,untilalltheelectronsitwillholdhavebeenadded.Muchas onefillsupacontainerwithliquidfromthebottomup,theorbitalsofanatomarefilledfromthelowestenergyorbitalstothehighestenergyorbitals. Orbitalswiththelowestprincipalquantumnumber( )havethelowestenergyandwillfillupfirst.Withinashell,theremaybeseveralorbitalswiththesameprincipalquantum number.Inthatcase,morespecificrulesmustbeapplied.Forexample,thethreeporbitalsofagivenshellalloccuratthesameenergylevel.So,howaretheyfilledup?ans:all thethreeporbitalshavesameenergysowhilefillingtheporbitalswecanfillanyoneofthePx,PyorPzfirst.itisaconventionthatwechosetofillPxfirst,thenPyandthenPzfor oursimplicity.Henceyoucanoptforfillingthesethreeorbitalsfromrighttoleftalso.
Hund'sRule
AccordingtoHund'srule,orbitalsofthesameenergyareeachfilledwithoneelectronbeforefillinganywithasecond.Also,thesefirstelectronshavethesamespin. Thisruleissometimescalledthe"busseatingrule".Aspeopleloadontoabus,eachpersontakeshisownseat,sittingalone.Onlyafteralltheseatshavebeenfilledwillpeople startdoublingup.
PauliExclusionprinciple
Notwoelectronscanhaveallfourquantumnumbersthesame.Whatthistranslatestointermsofourpictureoforbitalsisthateachorbitalcanonlyholdtwoelectrons,one"spinup" (+)andone"spindown"().
OrbitalOrder
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1s,2s,2p,3s,3p,4s,3d,4p,5s,4d,5p,6s,4f,5d,6p,7s,5f,6d,7p,8s. Althoughthislooksconfusing,thereisaneasywaytoremember.
ThisanimationdemonstratestheAufbau principle,Hund'sRule,andthePauliExclusion principle.
Understandingtheaboverulesanddiagramswillallowyoutodeterminetheelectronconfigurationofalmostanyatomorion.
HowtoWritetheElectronConfigurationofanAtom
Electronconfigurationnotationisrelativelystraightforward.Calcium,forexample,wouldbe1s22s22p63s23p64s2.Thiscouldbeabbreviatedbyusingthepreceding noblegas(the elementsfoundallthewayontherightoftheperiodictable)as[Ar]4s2,whereArisargon.Noblegasseshaveverystableconfigurations,andareextremelyreluctanttolose electrons.
RuleofStability
Asubshellisparticularlystableifitishalffullorfull.Giventwoconfigurations,theatomwould"choose"themorestableone. Example:Inthefollowingconfiguration,Cu:[Ar]4s23d9,copper'sdshellisjustoneawayfromstability,andtherefore,oneelectronfromthesshelljumpsintothedshell: [Ar]4s13d10.Thisway,thedshellisfull,andisthereforestable,andthesshellishalffull,andisalsostable.
Anotherexample:Chromiumhasaconfigurationof[Ar]4s13d5,althoughyouwouldexpecttoseefourdelectronsinsteadoffive.Thisisbecauseanselectronhasjumpedintothed orbital,givingtheatomtwohalffullshellsmuchmorestablethanadorbitalwithonlyfourelectrons. Thestabilityruleappliestoatomsinthesamegroupaschromiumandcopper.
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Ifoneoftheseatomshasbeenionized,thatis,itlosesanelectron,itwillcomefromthesorbitalratherthanthedorbital.Forinstance,theconfigurationofCu+ is[Ar]4s03d10.If moreelectronsareremoved,theywillcomefromthedorbital.
Magnetism
Magnetismisawellknowneffect.Chancesare,youhavemagnetsonyourrefrigerator.Asyoualreadyknow,onlycertainelementsaremagnetic. Electronconfigurationshelptoexplainwhy. Diamagnetismisactuallyaveryweakrepulsiontomagneticfields.Allelementshavediamagnestismtosomedegree.Itoccurswhentherearepair electrons. Paramagnetismisanattractiontoexternalmagneticfields.Itisalsoveryweak.Itoccurswheneverthereisanunpairedelectroninanorbital. Ferromagnetismisthepermanentmagnetismthatweencounterinourdailylives.Itonlyoccurswiththreeelements:iron(Fe),nickel(Ni),andcobalt (Co).
PeriodicityandElectronConfigurations
BlocksofthePeriodicTable
ThePeriodicTabledoesmorethanjustlisttheelements.Theword periodicmeansthatineachrow,orperiod,thereisapatternofcharacteristicsin theelements.Thisisbecausetheelementsarelistedinpartbytheirelectronconfiguration.TheAlkalimetalsandAlkalineearthmetalshaveoneand two valenceelectrons(electronsintheoutershell)respectively.Theseelementsloseelectronstoformbondseasily,andarethusveryreactive. Theseelementsarethe sblockoftheperiodictable.The pblock,ontheright,containscommonnonmetalssuchaschlorineandhelium.Thenoble gases,inthecolumnontheright,almostneverreact,sincetheyhaveeightvalenceelectrons,whichmakesitverystable.Thehalogens,directlyto theleftofthenoblegases,readilygainelectronsandreactwithmetals.Thesandpblocksmakeupthe maingroupelements,alsoknownas representativeelements.The dblock,whichisthelargest,consistsof transitionmetalssuchascopper,iron,andgold.The fblock,onthebottom,containsrarermetalsincluding uranium.Elementsinthesame Groupor Familyhavethesameconfigurationofvalenceelectrons,makingthembehaveinchemicallysimilarways.
Thespinofanelectron createsamagneticfield (albeitridiculouslyweak),so unpairedelectronscreatea smallmagneticfield.Paired electronshaveoppositespin, sothemagneticfieldscancel eachotherout,leadingto diamagnetism.
CausesforTrends
Therearecertainphenomenathatcausetheperiodictrendstooccur.Youmustunderstandthembeforelearningthetrends.
EffectiveNuclearCharge
The effectivenuclearchargeistheamountofpositivechargeactingonanelectron.Itisthenumberofprotonsinthenucleusminusthe numberofelectronsinbetweenthenucleusandtheelectroninquestion.Basically,thenucleusattractsanelectron,butotherelectronsin lowershellsrepelit(oppositesattract,likesrepel).
ShieldingEffect
OrganizationofSubshells
The shielding(or screening) effect issimilartoeffectivenuclearcharge.The coreelectronsrepelthevalenceelectronstosomedegree. Themoreelectronshellsthereare(anewshellforeachrowintheperiodictable),thegreatertheshieldingeffectis.Essentially,thecoreelectrons shieldthevalenceelectronsfrom thepositivechargeofthenucleus.
ElectronElectronRepulsions
Whentwoelectronsareinthesameshell,theywillrepeleachotherslightly.Thiseffectismostlycanceledoutduetothestrongattractiontothenucleus,butitdoescauseelectrons inthesameshelltospreadoutalittlebit.Lowershellsexperiencethiseffectmorebecausetheyaresmallerandallowtheelectronstointeractmore.
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Coulomb'sLaw
Coulomb'slawisanequationthatdeterminestheamountofforcewithwhichtwochargedparticlesattractorrepeleachother.Itis ,where istheamountofcharge(+1eforprotons,1eforelectrons), isthedistancebetweenthem,and isa
constant.Youcanseethatdoublingthedistancewouldquartertheforce.Also,alargenumberofprotonswouldattractanelectronwith muchmoreforcethanjustafewprotonswould.
TrendsinthePeriodictable
MostoftheelementsoccurnaturallyonEarth.However,allelementsbeyonduranium(number92)arecalled transuraniumelementsand neveroccuroutsideofalaboratory.MostoftheelementsoccurassolidsorgasesatSTP. STP is standardtemperatureandpressure, whichis0Cand1atmosphereofpressure.ThereareonlytwoelementsthatoccurasliquidsatSTP:mercury(Hg)andbromine(Br). Bismuth(Bi)isthelaststableelementonthechart.Allelementsafterbismuthareradioactiveanddecayintomorestableelements. Someelements beforebismuthareradioactive,however.
Potassiumhasmanycoreelectronsthe loneouterelectroncaneasilybepeeledoff duetothe"shielding"effect.
AtomicRadius
Leavingoutthenoblegases,atomicradiiarelargerontheleftsideoftheperiodicchartandareprogressivelysmallerasyoumovetothe rightacrosstheperiod.Conversely,asyoumovedownthegroup,radiiincrease. Atomicradiidecreasealongaperiodduetogreatereffectivenuclearcharge.Atomicradiiincreasedownagroupduetotheshieldingeffectoftheadditionalcoreelectrons,andthe presenceofanotherelectronshell.
IonicRadius
Fornonmetals,ionsarebiggerthanatoms,astheionshaveextraelectrons.Formetals,itistheopposite. Extraelectrons(negativeions,calledanions)causeadditionalelectronelectronrepulsions,makingthemspreadoutfarther.Fewerelectrons(positiveions,calledcations)causefewer repulsions,allowingthemtobecloser.
IonizationEnergy(http://en.wikipedia.org/wiki/Ionization_energy)
Ionizationenergyisalsoaperiodictrendwithintheperiodictableorganization.Movinglefttorightwithinaperiodorupwardwithinagroup,thefirstionizationenergygenerally increases.Astheatomicradiusdecreases,itbecomeshardertoremoveanelectronthatisclosertoamorepositivelychargednucleus. Ionizationenergydecreasesgoingleftacrossaperiodbecausethereisalowereffectivenuclearchargekeepingtheelectronsattractedtothenucleus,solessenergyisneededto pulloneout.Itdecreasesgoingdownagroupduetotheshieldingeffect.RememberCoulomb'sLaw:asthedistancebetweenthenucleusandelectronsincreases,theforce decreasesataquadraticrate. Itisconsideredameasureofthetendencyofanatomoriontosurrenderanelectron,orthestrengthoftheelectronbindingthegreatertheionizationenergy,themoredifficultitis toremoveanelectron.Theionizationenergymaybeanindicatorofthereactivityofanelement.Elementswithalowionizationenergytendtobereducingagentsandformcations, whichinturncombinewithanionstoformsalts.
ElectronAffinity
Electronaffinityishighestintheupperleft,lowestonthebottomright.However,electronaffinityisactuallynegativeforthenoblegasses.Theyalreadyhaveacompletevalence shell,sothereisnoroomintheirorbitalsforanotherelectron.Addinganelectronwouldrequirecreatingawholenewshell,which takesenergyinsteadofreleasingit.Severalother elementshaveextremelylowelectronaffinitiesbecausetheyarealreadyinastableconfiguration,andaddinganelectronwoulddecreasestability.
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Electronaffinityoccursduetothesamereasonsasionizationenergy.
Electronegativity
Electronegativityishowmuchanatomattractselectronswithinabond.Itismeasuredonascalewithfluorineat4.0andfranciumat0.7.Electronegativitydecreasesfromupper righttolowerleft. Electronegativitydecreasesbecauseofatomicradius,shieldingeffect,andeffectivenuclearchargeinthesamemannerthationizationenergydecreases.
MetallicCharacter
Metallicelementsareshiny,usuallygrayorsilvercolored,andgoodconductorsofheatandelectricity.Theyaremalleable (canbehammeredintothinsheets),andductile(canbestretchedintowires).Somemetals,likesodium,aresoftandcan becutwithaknife.Others,likeiron,areveryhard.Nonmetallicatomsaredull,usuallycolorfulorcolorless,andpoor conductors.Theyarebrittlewhensolid,andmanyaregasesatSTP.Metalsgiveawaytheirvalenceelectronswhen bonding,whereasnonmetalstakeelectrons. Themetalsaretowardstheleftandcenteroftheperiodictableinthesblock,dblock,andfblock.Poormetalsand metalloids(somewhatmetal,somewhatnonmetal)areinthelowerleftofthepblock.Nonmetalsareontherightofthe table. Metalliccharacterincreasesfromrighttoleftandtoptobottom.Nonmetalliccharacterisjusttheopposite.Thisisbecause oftheothertrends:ionizationenergy,electronaffinity,andelectronegativity. Metallic/Nonmetallic
Periodictrendforionizationenergy.Eachperiodbeginsat aminimumforthealkalimetals,andendsatamaximumfor thenoblegases.
Electronaffinityistheenergyreleased whenanelectronisaddedtoanatom, producinganegativeion.
Sodium,verymetallic
Sulfur,verynonmetallic
OctetRuleandExceptions
The octetrulereferstothetendencyofatomstoprefertohaveeightelectronsinthe valenceshell.Whenatomshavefewerthaneightelectrons,theytendtoreactandformmore stablecompounds.Whendiscussingtheoctetrule,wedonotconsiderdorfelectrons.Onlythesandpelectronsareinvolvedintheoctetrule,makingitusefulforthe representativeelements(elementsnotinthetransitionmetalorinnertransitionmetalblocks).Anoctetcorrespondstoanelectronconfigurationendingwiths2p6.
Stability
Atomswillreacttogetinthemoststablestatepossible.Acompleteoctetisverystablebecauseallorbitalswillbefull.Atomswithgreaterstabilityhavelessenergy,soareaction
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Atomswillreacttogetinthemoststablestatepossible.Acompleteoctetisverystablebecauseallorbitalswillbefull.Atomswithgreaterstabilityhavelessenergy,soareaction thatincreasesthestabilityoftheatomswillreleaseenergyintheformofheatorlight.Reactionsthatdecreasestabilitymustabsorbenergy,gettingcolder. Theothertendencyofatomsistomaintainaneutralcharge.Onlythenoblegases(theelementsontherightmostcolumnoftheperiodictable)havezerochargewithfilledvalence octets.Alloftheotherelementshaveachargewhentheyhaveeightelectronsalltothemselves.Theresultofthesetwoguidingprinciplesistheexplanationformuchofthe reactivityandbondingthatisobservedwithinatoms: atomsseektoshareelectronsinawaythatminimizeschargewhilefulfillinganoctetinthevalenceshell .
Example
TheformulafortablesaltisNaCl.ItistheresultofNa+ ionsandClionsbondingtogether.Ifsodiummetalandchlorinegasmixundertherightconditions,theywillformsalt.The sodiumlosesanelectron,andthechlorinegainsthatelectron.Intheprocess,agreatamountoflightandheatisreleased.Theresultingsaltismostlyunreactiveitisstable.It won'tundergoanyexplosivereactions,unlikethesodiumandchlorinethatitismadeof. Why?Referringtotheoctetrule,atomsattempttogetanoblegaselectronconfiguration,whichiseightvalenceelectrons.Sodiumhasonevalenceelectron,sogivingitupwould resultinthesameelectronconfigurationasneon.Chlorinehassevenvalenceelectrons,soifittakesoneitwillhaveeight(anoctet).Chlorinehastheelectronconfigurationofargon whenitgainsanelectron. Theoctetrulecouldhavebeensatisfiedifchlorinegaveupallsevenofitsvalenceelectronsandsodiumtookthem.Inthatcase,bothwouldhavetheelectronconfigurationsof noblegasses,withafullvalenceshell.However,theirchargeswouldbemuchhigher.ItwouldbeNa7andCl7+ ,whichismuchlessstablethanNa+ andCl.Atomsaremorestable whentheyhavenocharge,orasmallcharge.
Exceptions
Theoctetruleisausefulaidwhenpredictingthebehaviorofelements,butitdoeshavelimitations.
TwoElectrons
Themainexceptiontotheruleishydrogen,whichisatitslowestenergywhenithastwoelectronsinitsvalenceshell.Helium(He)issimilarinthatit,too,onlyhasroomfortwo electronsinitsonlyvalenceshell. Hydrogenandheliumhaveonlyoneelectronshell.Thefirstshellhasonlyonesorbitalandnoporbital,soitholdsonlytwoelectrons.Therefore,theseelementsaremoststable whentheyhavetwoelectrons.Youwilloccasionallyseehydrogenwithnoelectrons,butH+ ismuchlessstablethanhydrogenwithoneortwoelectrons. Lithium,withthreeprotonsandelectrons,ismoststablewhenitgivesupanelectron.
LessThananOctet
Othernotableexceptionsarealuminumandboron,whichcanfunctionwellwithsixvalenceelectrons.ConsiderBF3.Theboronsharesitsthreeelectronswiththreefluorineatoms. Thefluorinesfollowtheoctetrule,butboronhasonlysixelectrons.Althoughatomswithlessthananoctetmaybestable,theywillusuallyattempttoformafourthbondtogeteight electrons.BF3isstable,butitwillformBF4whenpossible.
MoreThananOctet
InPeriod3,theelementsontherightsideoftheperiodictablehaveemptydorbitals.Thedorbitalsmayacceptelectrons,allowingelementslikesulfurandphosphorustohave morethananoctet.CompoundssuchasPCl5andSF6canform.Thesecompoundshave10and12electronsaroundtheircentralatoms,respectively.
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Xenonhexafluorideusesdelectronstoformmorethananoctet.Thiscompoundshowsanotherexception:anoblegascompound.
OddNumbers
Someelements,notablynitrogen,haveanoddnumberofelectronsandwillformsomewhatstablecompounds.NitricoxidehastheformulaNO.Nomatterhowelectronsareshared betweenthenitrogenandoxygenatoms,thereisnowayfornitrogentohaveanoctet.Itwillhavesevenelectronsinstead.Anatomwithanunpairedelectroniscalleda freeradical andishighlyreactive.
Nitrogendioxidehasanunpairedelectron.(NotethepositivechargeabovetheN).
OverviewofBonding
IntroductiontoBonding
CompoundsandBonding
Putsimply, chemicalbondsjoinatomstogethertoformmore complexstructures(likemoleculesorcrystals).Bondscanformbetweenatomsofthesameelement,orbetweenatomsofdifferentelements.Thereareseveraltypesofchemical bondswhichhavedifferentpropertiesandgiverisetodifferentstructures. Ingeneral,atomstrytoreacttoformvalenceshellscontainingeightelectrons.The octetruledescribesthis.
Ionicbondsformbetweenpositiveions(cations)andnegativeions(anions).Inanionicsolid,theionsarrangethemselvesintoarigid crystallattice.NaCl(commonsalt)isanexampleofanionicsubstance.Whenionicbondsform,thereisanattractiveforceestablished betweenthepositivecationandthenegativeanion.Thisattractionbetweenoppositelychargedionsistheionicbond. Covalentbondsareformedwhentheorbitalsoftwononmetalatomsphysicallyoverlapandshareelectronswitheachother.Thereare twotypesofstructurestowhichthiscangiverise:moleculesandcovalentnetworksolids.Methane(CH4)andwater(H2O)areexamplesof covalentlybondedmolecules,andglassisacovalentnetworksolid. Metallicbondsoccurbetweenmetalatoms.Inametallicallybondedsubstance,theatoms'outerelectronsareabletofreelymovearound theyaredelocalisedtoforman'electronpool'.Ironisametallicallybondedsubstance.
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Chemicalbondingisoneofthemostcrucialconceptsinthestudyofchemistry.Infact,thepropertiesofmaterialsarebasicallydefinedbythetypeandnumberofatomstheycontain andhowtheyarebondedtogether. Sofar,youhaveseenexamplesof intramolecularbonds.Thesebondsconnectatomsintomolecules.Therearealso intermolecularbondsthatconnectmoleculesintolarge substances.Sometimes,thereisnodifferencebetweenintramolecularandintermolecularbonds.Inthecaseofioniccrystals(likesalt)orcovalentnetworks(likediamond),thesame bondingforcesconnectalloftheatomstogether.Inthecaseofmetallicbonding,theatomsareallinterconnectedintoonelargepieceofmetal. Ontheotherhand,theremaybeintermolecularbondsdifferentfromthosethatjoinatomsintomolecules.Intermolecularbondsholdindividualmoleculesofwaterintoapuddle,and theyarebrokenwhenthewaterboilsintoagas.
Electronegativity
Whatdeterminesthetypeofbondformedbetweentwoelements?Therearetwowaysofclassifyingelementstodeterminethebondformed:byelectronegativity,orbymetallic/non metalliccharacter.
Electronegativity
Electronegativityisapropertyofatomswhichisreflectedinthelayoutoftheperiodictableoftheelements.Electronegativityisgreatestintheelementsintheupperrightofthe table(e.g.,fluorine),andlowestinthelowerleft(e.g.,francium). Electronegativityisarelativemeasureofhowstronglyanatomwillattracttheelectronsinabond.Althoughbondsaretheresultofatomssharingtheirelectrons,theelectronscan besharedunequally.Themoreelectronegativeatominabondwillhaveaslightnegativecharge,andthelesselectronegativeatomwillhaveaslightpositivecharge.Overall,the moleculemayhavenocharge,buttheindividualatomswill.Thisisaresultoftheelectronegativitybyattractingtheelectronsinabond,anatomgainsaslightnegativecharge.Of course,iftwoelementshaveequalelectronegativity,theywillsharetheelectronsequally. Metallicelementshavelowelectronegativity,andnonmetallicelementshavehighelectronegativity.Iftwoelementsareclosetoeachotherontheperiodictable,theywillhave similarelectronegativities. Electronegativityismeasuredonavarietyofscales,themostcommonbeingthe Paulingscale.CreatedbychemistLinusPauling,itassigns4.0tofluorine(thehighest)and0.7to francium(thelowest).
Bonds
Nonpolarcovalentbondsoccurwhenthereisequalornearequalsharingofelectronsbetweenthetwobondedatoms.Thisshouldmakesensebecausecovalentbondsarethe sharingofelectronsbetweentwoatoms.MoleculessuchasCl2,H2andF2aregoodexamples.Typically,adifferenceinelectronegativitybetween0.0and0.4indicatesanonpolar covalentbond. Polarcovalentbondsoccurwhenthereisunequalsharingoftheelectronsbetweentheatoms.MoleculessuchasNH3andH2Oareexamplesofthis.Thetypicalruleisthatbonds withanelectronegativitydifferencebetween0.5and1.7areconsideredpolar.Theelectronsarestillbeingsharedbetweentwoatoms,butoneatomattractstheelectronsmorethan theother. Ionicbondsoccurwhenthereiscompletetransferoftheelectronsinthebond.Thisbonddoesnotcontainatomsatall,butratherconsistsoftwoions.SubstancessuchasNaCl andMgCl2areexamples.Generally,electronegativitydifferencesof1.8orgreatercreateionicbonds.Theelectronegativitydifferenceissogreatthatoneatomcanattractthe electronsenoughto"take"themfromtheotheratom.
Notation
Whendrawingdiagramsofbonds,weindicatecovalentbondswithaline.Wemaywritetheelectronegativityusingthesymbols and .Lookatthisexample.
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Hydrogenfluoride(HF): Theplusgoesoverthelesselectronegativeatom.Fromtheabovediagram,wecanseethatthefluorineattractstheelectronsinthe covalentbondmorethanthehydrogendoes.Fluorinewillhaveaslightnegativechargebecauseofthis,andhydrogenwillhaveaslight positivecharge.Overall,hydrogenfluorideisneutral.
IonicBonds
Whatareions?
Ionsareatomsormoleculeswhichareelectricallycharged. Cationsarepositivelychargedand anionscarryanegativecharge.Ionsform whenatomsgainorloseelectrons.Sinceelectronsarenegativelycharged,anatomthatlosesoneormoreelectronswillbecome positivelychargedanatomthatgainsoneormoreelectronsbecomesnegativelycharged.
DescriptionofIonicBonds
Ionicbondingistheattractionbetweenpositivelyandnegativelycharged ions.Theseoppositelychargedionsattracteachothertoform ionicnetworks(orlattices).Electrostaticsexplainswhythishappens:oppositechargesattractandlikechargesrepel.Whenmanyions attracteachother,theyformlarge,ordered,crystallatticesinwhicheachionissurroundedbyionsoftheoppositecharge.Generally, whenmetalsreactwithnonmetals,electronsaretransferredfromthemetalstothenonmetals.Themetalsformpositivelychargedions andthenonmetalsformnegativelychargedions.Thesmallestunitofanioniccompoundisthe formulaunit.
LinusPaulingcreatedacommonlyused measureofelectronegativity.
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Theionsarrangethemselvesintoalatticewhereeachionissurroundedbyions oftheoppositetype.
Characteristics
Exampleioniccompounds:Sodiumchloride( ),potassiumnitrate( ). Ionicallybondedsubstancestypicallyhavethefollowingcharacteristics. Highmeltingpoint(solidatroomtemperature) Hardbutbrittle(canshatter) Manydissolveinwater Conductorsofelectricitywhendissolvedormelted
Formation
Ionicbondsformwhenmetalsandnonmetalschemicallyreact.Bydefinition,ametalisrelativelystableifitloseselectronstoforma completevalenceshellandbecomespositivelycharged.Likewise,anonmetalbecomesstablebygainingelectronstocompleteits valenceshellandbecomenegativelycharged.Whenmetalsandnonmetalsreact,themetalsloseelectronsbytransferringthemtothe nonmetals,whichgainthem.Consequently,ionsareformed,whichinstantlyattracteachotherionicbonding. Forinstance,inthereactionofNa(sodium)andCl(chlorine),eachClatomtakesoneelectronfromaNaatom.ThereforeeachNa becomesaNa+ cationandeachClatombecomesaClanion.Duetotheiroppositecharges,theyattracteachothertoformanionic lattice.Theformula(ratioofpositivetonegativeions)inthelatticeis NaCl .
Lewisstructureoftheionicbondbetween sodiumandchlorine.
Thechargesmustbalancebecausetheoverallcompoundisneutral.Inthecaseofmagnesiumchloride,themagnesiumatomgivesuptwoelectronstobecomestable.Notethatitis inthesecondgroup,soithastwovalenceelectrons.Thechlorineatomcanonlyacceptoneelectron,sotheremustbetwochlorineionsforeachmagnesiumion.Therefore,the formulaformagnesiumchlorideis MgCl 2.Ifmagnesiumoxidewereforming,theformulawouldbe MgObecauseoxygencanacceptbothofmagnesium'selectrons.
Exerciseforthereader Tryfiguringoutwhattheformulaformagnesiumnitridewouldbe.Usetheperiodictabletohelp.
Itshouldalsobenotedthatsomeatomscanformmorethanoneion.Thisusuallyhappenswiththetransitionmetals.ForinstanceFe(iron)canbecomeFe2+ (callediron(I I )or ferrous).Fecan alsobecomeFe3+ (callediron(I I I )orferric).
CommonIons
Ionicbondingoccursalmostexclusivelybetweenametalandnonmetal.Therearealsocertainmoleculescalled polyatomicionsthatundergoionicbonding.Withinthepolyatomic ions,thereiscovalentbonding,butasaunititundergoesionicbonding.Therearecountlesspolyatomicions,butyoushouldbefamiliarwiththemostcommonones.Youwouldbe welladvisedtomemorizetheseions.
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Name Ammonium Peroxide Nitrite Sulfite
Formula NH4+ O22 NO2 SO32
Name Hydronium Hydroxide Nitrate Sulfate Phosphate Chlorite
Formula H3O+ OH NO3 SO42 PO43 ClO2 ClO4
Hydrogensulfite HSO3 Hypochlorite ClO ClO3 CO32
Chlorate Carbonate
Perchlorate
Hydrogencarbonate HCO3
CovalentBonds
Covalentbondscreate molecules,whichcanberepresentedbya molecularformula.Forchemicalssuchasabasicsugar(C6H12O6),theratiosofatomshaveacommonmultiple, andthusthe empiricalformulaisCH2O.Notethatamoleculewithacertainempiricalformulaisnotnecessarilythesameasonewiththesamemolecularformula.
FormationofCovalentBonds
Covalentbondsformbetweentwoatomswhichhaveincompleteoctetsthatis,theiroutermostshellshavefewerthaneightelectrons.Theycansharetheirelectronsina covalent bond.Thesimplestexampleiswater(H2O).Oxygenhassixvalenceelectrons(andneedseight)andthehydrogenshaveoneelectroneach(andneedtwo).Theoxygensharestwoof itselectronswiththehydrogens,andthehydrogenssharetheirelectronswiththeoxygen.Theresultisacovalentbondbetweentheoxygenandeachhydrogen.Theoxygenhasa completeoctetandthehydrogenshavethetwoelectronstheyeachneed. Whenatomsmovecloser,theirorbitalschangeshape,lettingoffenergy.However,thereisalimittohowclosetheatomsgettoeachothertooclose,andthenucleirepeleach other.
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Onewaytothinkofthisisaballrollingdownintoavalley.Itwillsettleatthelowestpoint.Asaresultofthispotentialenergy"valley",thereisaspecific bondlengthforeachtype ofbond.Also,thereisaspecificamountofenergy,measuredinkilojoulespermole(kJ/mol)thatisrequiredtobreakthebondsinonemoleofthesubstance.Strongerbondshavea shorterbondlengthandagreaterbondenergy.
TheValenceBondModel
Oneusefulmodelofcovalentbondingiscalledthe ValenceBondmodel.Itstatesthatcovalentbondsformwhenatomsshareelectronswitheachotherinordertocompletetheir valence(outer)electronshells.Theyaremainlyformedbetweennonmetals. Anexampleofacovalentlybondedsubstanceishydrogengas(H2).Ahydrogenatomonitsownhasoneelectronitneedstwotocompleteitsvalenceshell.Whentwohydrogen atomsbond,eachonesharesitselectronwiththeothersothattheelectronsmoveaboutbothatomsinsteadofjustone.Bothatomsnowhaveaccesstotwoelectrons:theybecome astableH2moleculejoinedbya singlecovalentbond.
DoubleandTripleBonds
Covalentbondscanalsoformbetweenothernonmetals,forexamplechlorine.Achlorineatomhas7electronsinitsvalenceshellitneeds8tocompleteit.Twochlorineatoms canshare1electroneachtoformasinglecovalentbond.TheybecomeaCl2molecule. Oxygencanalsoformcovalentbonds,however,itneedsafurther2electronstocompleteitsvalenceshell(ithas6).Twooxygenatomsmustshare2electronseachtocomplete eachother'sshells,makingatotalof4sharedelectrons.Becausetwiceasmanyelectronsareshared,thisiscalleda doublecovalentbond.Doublebondsaremuchstrongerthan singlebonds,sothebondlengthisshorterandthebondenergyishigher.
Furthermore,nitrogenhas5valenceelectrons(itneedsafurther3).Twonitrogenatomscanshare3electronseachtomakeaN2moleculejoinedbya triplecovalentbond.Triple
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Furthermore,nitrogenhas5valenceelectrons(itneedsafurther3).Twonitrogenatomscanshare3electronseachtomakeaN2moleculejoinedbya triplecovalentbond.Triple bondsarestrongerthandoublebonds.Theyhavetheshortestbondlengthsandhighestbondenergies.
ElectronSharingandOrbitals
Carbon,contrarytothetrend,doesnotsharefourelectronstomakeaquadruplebond.Thereasonforthisisthatthefourthpairofelectronsincarboncannotphysicallymoveclose enoughtobeshared.Thevalencebondmodelexplainsthisbyconsideringthe orbitalsinvolved. Recallthatelectronsorbitthenucleuswithinacloudofelectrondensity(orbitals).Thevalencebondmodelworksontheprinciplethatorbitalsondifferentatomsmust overlapto formabond.Thereareseveraldifferentwaysthattheorbitalscanoverlap,formingseveraldistinctkindsofcovalentbonds.
TheSigmaBond
Thefirstandsimplestkindofoverlapiswhentwosorbitalscometogether.Itiscalleda sigmabond(sigma,or,istheGreekequivalentof's').Sigmabondscanalsoformbetween twoporbitalsthatliepointingtowardseachother.Wheneveryouseeasinglecovalentbond,itexistsasasigmabond.Whentwoatomsarejoinedbyasigmabond,theyareheld closetoeachother,buttheyarefreetorotatelikebeadsonastring.
Theelectrondensityisinbetweenthetwo atomsinanbond.
ThePiBond
Thesecond,andequallyimportantkindofoverlapisbetweentwoparallelporbitals.Insteadofoverlappingheadtohead(asinthesigmabond),theyjoinsidetoside,formingtwo areasofelectrondensityaboveandbelowthemolecule.Thistypeofoverlapisreferredtoasa pi (,fromtheGreekequivalentofp)bond.Wheneveryouseeadoubleortriple covalentbond,itexistsasonesigmabondandoneortwopibonds.Duetothesidebysideoverlapofapibond,thereisnowaytheatomscantwistaroundeachotherasina sigmabond.Pibondsgivethemoleculearigidshape. Pibondsareweakerthansigmabondssincethereislessoverlap.Thus,twosinglebondsarestrongerthanadoublebond,andmoreenergyisneededtobreaktwosinglebonds thanasingledoublebond.
Theelectrondensityliesaboveandbelow theatomsinabond.
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Hybridization
Consideramoleculeofmethane:acarbonatomattachedtofourhydrogenatoms.Eachatomissatisfyingtheoctetrule,andeachbondisasinglecovalentbond. Nowlookattheelectronconfigurationofcarbon:1s22s22p2.Initsvalenceshell,ithastwoselectronsandtwopelectrons.Itwouldnotbepossibleforthefourelectronstomake equalbondswiththefourhydrogenatoms(eachofwhichhasoneselectron).Weknow,bymeasuringbondlengthandbondenergy,thatthefourbondsinmethaneareequal,yet carbonhaselectronsintwodifferentorbitals,whichshouldoverlapwiththehydrogen1sorbitalindifferentways. Tosolvetheproblem, hybridizationoccurs.Insteadofasorbitalandthreeporbital,theorbitalsmix,toformfourorbitals,eachwith25%scharacterand75%pcharacter.These hybridorbitalsarecalled sp3orbitals,andtheyareidentical.Observe:
Nowtheseorbitalscanoverlapwithhydrogen1sorbitalstoformfourequalbonds.Hybridizationmayinvolvedorbitalsintheatomsthathavethem,allowinguptoa sp3d2 hybridization.
Exerciseforthereader Predictthehybridizedelectronconfigurationofcarbonin ethene.Howmanysigmabondsarethere?Howmanypibonds?
Hint:Hybridizedelectronsformonlysigmabonds.Pibondsformonlybetweenpelectrons.
MetallicBonds
Metallicbondsoccuramongmetalatoms.Whereasionicbondsjoinmetalstononmetals, metallicbondingjoinsabulkofmetalatoms.Asheetofaluminumfoilandacopperwire arebothplaceswhereyoucanseemetallicbondinginaction. Whenmetallicbondsform,thesandpelectrons delocalize.Insteadoforbitingtheiratoms,theyforma"seaofelectrons"surroundingthepositivemetalions.Theelectronsarefree tomovethroughouttheresultingnetwork.Thedelocalizednatureoftheelectronsexplainsanumberofuniquecharacteristicsofmetals:
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The"seaofelectrons"isfreetoflowabout thecrystalofpositivemetalions.
Metalsaregoodconductorsofelectricity
Theseaofelectronsisfreetoflow,allowingelectricalcurrents.
Metalsareductile(abletodrawintowires) andmalleable(abletobehammeredintothin sheets)
Asthemetalisdeformed,localbondsarebrokenbutquicklyreformedinanewposition.
Metalsaregrayandshiny
Photons(particlesoflight)cannotpenetratethemetal,sotheybounceofftheseaofelectrons.
Goldisyellowandcopperisreddishbrown
Thereisactuallyanupperlimittothefrequencythatisreflected.Itistoohightobevisibleinmostmetals,butnotgold andcopper.
Metalshaveveryhighmeltingandboilingpoints
Metallicbondingisverystrong,sotheatomsarereluctanttobreakapartintoaliquidorgas.
Metallicbondscanoccurbetweendifferentelements.Amixtureoftwoormoremetalsiscalledan alloy.Dependingonthesizeoftheatomsbeingmixed,therearetwodifferent kindsofalloysthatcanform:
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Substitutionalalloy
Interstitialalloy
Theresultingmixturewillhaveacombinationofthepropertiesofbothmetalsinvolved.
MolecularShape
Covalentmoleculesarebondedtootheratomsbyelectronpairs.Beingmutuallynegativelycharged,theelectronpairsrepeltheotherelectronpairsandattempttomoveasfarapart aspossibleinordertostabilizethemolecule.Thisrepulsioncausescovalentmoleculestohavedistinctiveshapes,knownasthemolecule's moleculargeometry.Thereareseveral differentmethodsofdeterminingmoleculargeometry.Ascientificmodel,calledtheVSEPR(valenceshellelectronpairrepulsion)modelcanbeusedtoqualitativelypredictthe shapesofmolecules.Withinthismodel,the AXEmethodisusedindeterminingmoleculargeometrybycountingthenumbersofelectronsandbondsrelatedtothecenteratom(s)of themolecule. TheVSEPRmodelisbynomeansaperfectmodelofmolecularshape!Itissimplyasystemwhichexplainstheknownshapesofmoleculargeometryasdiscoveredbyexperiment. Thiscanallowustopredictthegeometryofsimilarmolecules,makingitafairlyusefulmodel.Modernmethodsofquantitativelycalculatingthemoststable(lowestenergy)shapesof moleculescantakeseveralhoursofsupercomputertime,andisthedomainofcomputationalchemistry.
TableofGeometries
OrbitalHybridization sp 2Groups Linear Bent 3Groups 4Groups 5Groups 6Groups sp2 Bent sp3 Linear sp3d sp3d2
TrigonalPlanar TrigonalPyramidal TShaped Tetrahedral Seesaw SquarePlanar
TrigonalBipyramidal SquarePyramidal Octahedral
Thehybridizationisdeterminedbyhowmany"things"areattachedtothecentralatom.Those"things"canbeotheratomsornonbondingpairsofelectrons.Thenumberofgroups ishowmanyatomsorelectronpairsarebondedtothecentralatom.Forexample,methane(CH4)istetrahedralshapedbecausethecarbonisattachedtofourhydrogens.Ammonia (NH3)isnottrigonalplanar,however.Itistrigonalpyramidalbecauseitisattachedtofour"things":thethreehydrogensandanonbondingpairofelectrons(tofulfillnitrogen'soctet).
TetrahedralShape
Considerasimplecovalentmolecule,methane(CH4).Fourhydrogenatomssurroundacarbonatominthreedimensionalspace.EachCHbondconsistsofonepairofelectrons,and en.wikibooks.org/wiki/General_Chemistry/Print_version 41/184
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Considerasimplecovalentmolecule,methane(CH4).Fourhydrogenatomssurroundacarbonatominthreedimensionalspace.EachCHbondconsistsofonepairofelectrons,and thesepairstrytomoveasfarawayfromeachotheraspossible(duetoelectrostaticrepulsion).Youmightthinkthiswouldleadtoaflat shape,witheachhydrogenatom90apart.However,inthreedimensions,thereisamoreefficientarrangementofthehydrogenatoms.If eachhydrogenatomisatacornerofatetrahedroncenteredaroundthecarbonatom,theyareseparatedbyaboutcos1(1/3) 109.5 themaximumpossible.
Hybridization
Toalignfourorbitalsinthistetrahedralshaperequiresthereformationofonesandthreeporbitalsintoansp3orbital.
LoneElectronPairs
TheVSEPRmodeltreatsloneelectronpairsinasimilarwaytobondingelectrons.Inammonia(NH3)forexample,therearethree hydrogenatomsandonelonepairofelectronssurroundingthecentralnitrogenatom.Becausetherearefourgroups,ammoniahasa tetrahedralshapebutunlikemethane,theanglebetweenthehydrogenatomsisslightlysmaller, 107.3.Thiscanbeexplainedby theorizingthatloneelectronpairstakeupmorespacephysicallythanbondingpairs.Thisisareasonabletheory:inabond,theelectron pairisdistributedovertwoatomswhereasalonepairisonlylocatedonone.Becauseitisbigger,thelonepairforcestheotherelectron pairstogether. Testingthisassumptionwithwaterprovidesfurtherevidence.Inwater(H2O)therearetwohydrogenatomsandtwo lonepairs,againmakingfourgroupsintotal.Theelectronpairsrepeleachotherintoatetrahedralshape.The anglebetweenthehydrogenatomsis 104.5,whichiswhatweexpectfromourmodel.Thetwolonepairsboth pushthebondsclosertogether,givingasmalleranglethaninammonia.
Thelonepair occupiesmore spacethana bondingpair, decreasingthe angles.
LinearandPlanarShapes
ElectronPoorAtoms
Insomemolecules,therearelessthanfourpairsofvalenceelectrons.Thisoccursinelectrondeficientatomssuch asboronandberyllium,whichdon'tconformtotheoctetrule(theycanhave6and4valenceelectrons respectively).Inborontrifluoride(BF3),thereareonlythreeelectronpairswhichrepeleachothertoformaflat
CH4isatetrahedralmolecule.
plane.Eachfluorineatomisseparatedbycos1(1/2)=120.Adifferentsetofhybridorbitalsisformedinthismolecule:the2sandtwo 2porbitalscombinetoformthree sp2hybridorbitals.Theremainingporbitalisemptyandsitsaboveandbelowtheplaneofthe molecule.
Beryllium,ontheotherhand,formsonlytwopairsofvalenceelectrons.Theserepeleachotheratcos1(1)=180,forminga linearmolecule.Anexampleisberylliumchloride, whichhastwochlorineatomssituatedonoppositesidesofaberylliumatom.Thistime,one2sandone2porbitalcombinetoformtwo sphybridorbitals.Thetworemainingp orbitalssitaboveandtothesideoftheberylliumatom(theyareempty).
Bentvs.Linear
Someelementswillhaveabentshape,othershavealinearshape.Bothareattachedtotwogroups,soitdependsonhowmanynonbondingpairsthecentralatomhas. Takealookatsulfurdioxide(SO2)andcarbondioxide(CO2).Bothhavetwooxygenatomsattachedwithdoublecovalentbonds.Carbondioxideislinear,andsulfurdioxideisbent. Thedifferenceisintheirvalenceshells.Carbonhasfourvalenceelectrons,sulfurhassix.Whentheybond,carbonhasnononbondingpairs,butsulfurhasone.
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FiveandSixGroups
Thenonbonding paircausessp2 hybridization, leadingtoabent shape.
Recallthatsomeelements,especiallysulfurandphosphorus,canbondwithfiveorsixgroups.Thehybridizationissp3dorsp3d2,witha trigonalbipyramidaloroctahedralshaperespectively.Whentherearenonbondingpairs,othershapecanarise(seetheabovechart).
HowTheShapesLook
Theyellowgroupsarenonbondingelectronpairs.Thewhitegroupsarebondedatoms,andthepinkisthecentralatom.Thisisreferred toasthe AXEmethodAisthecentralatom,X'sarebondedatoms,andE'sarenonbondingelectronpairs.
Nononbonding pairscausessp hybridization, leadingtoalinear shape.
Moleculesarenotstatictheirbondsare continuallytwisting,stretchingandbending. Accordingtoquantumtheory,theenergies ofthesebondmovementsarequantized, andthisfactformsthebasisof infrared spectroscopy,animportantchemicaltool inanalyzingorganicmolecules.
linear
trigonalplanar
bent
tetrahedral
trigonalpyramidal
bent
trigonalbipyramidal
seesaw
tshape
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octahedral
squarepyramid
squareplanar
IntermolecularBonds
Dipoles
Covalentbondscanbepolarornonpolar,andsocantheoverallcompounddependingonitsshape.Whenabondispolar,itcreatesa dipole,apair ofcharges(onepositiveandonenegative).Iftheyarearrangedinasymmetricalshape,sothattheypointinoppositedirections,theywillcanceleach other.Forexample,sincethefourhydrogensinmethane(CH4)arefacingawayfromeachother,thereisnooveralldipoleandthemoleculeisnon polar.Inammonia(NH3),however,thereisanegativedipoleatthenitrogen,duetotheasymmetrycausedbythenonbondingelectronpair.The polarityofacompounddeterminesitsintermolecularbondingabilities.
PolarandNonPolarShapes
Whenamoleculehasalinear,trigonalplanar,tetrahedral,trigonalbipyramidal,oroctahedralshape,itwillbenonpolar.Thesearetheshapesthatdo nothavenonbondinglonepairs.(e.g.Methane,CH4)Butifsomebondsarepolarwhileothersarenot,therewillbeanoveralldipole,andthe moleculewillbepolar(e.g.Chloroform,CHCl3). Theothershapes(withnonbondingpairs)willbepolar.(e.g.Water,H2O)Unless,ofcourse,allthecovalentbondsarenonpolar,inwhichcasethere wouldbenodipolestobeginwith.
DipoleDipoleBonds
Whentwopolarmoleculesareneareachother,theywillarrangethemselvessothatthenegativeandpositivesideslineup.Therewillbeanattractive forceholdingthetwomoleculestogether,butitisnotnearlyasstrongaforceastheintramolecularbonds.Thisishowmanytypesofmoleculesbond togethertoformlargesolidsorliquids.
Thepolarbondsare symmetric,buttheydon't pointinoppositedirections. Theresultisadipole (positivepointingdown).
DipoledipoleforcesholdthesetwoHCl moleculestogether.
HydrogenBonding
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Certainchemicalswithhydrogenintheirchemicalformulahaveaspecialtypeofintermolecularbond,called hydrogenbonds.Hydrogenbondswilloccurwhenahydrogenatomis attachedtoanoxygen,nitrogen,orfluorineatom.Thisisbecausethereisalargeelectronegativitydifferencebetweenhydrogenandfluorine,oxygen,andnitrogen.Thus,molecules suchas , , areextremelypolarmoleculeswithverystrongdipoledipoleforces.Asaresultofthehighelectronegativitiesoffluorine,oxygen,andnitrogen,these elementswillpulltheelectronsalmostcompletelyawayfromthehydrogen.Thehydrogenbecomesabareprotonstickingoutfromthemolecule,anditwillbestronglyattractedto thenegativesideofanyotherpolarmolecules.Hydrogenbondingisanextremetypeofdipoledipolebonding.Theseforcesareweakerthanintramolecularbonds,butaremuch strongerthanotherintermolecularforces,causingthesecompoundstohavehighboilingpoints.
Thedottedlinerepresentsahydrogen bond.
CovalentNetworks
Silicondioxideformsacovalentnetwork.Unlikecarbondioxide(withdoublebonds),silicondioxideformsonlysinglecovalentbonds.Asaresult,the individualmoleculescovalentlybondintoalargenetwork.Thesebondsareverystrong(beingcovalent)andthereisnodistinctionbetweenindividual moleculesandtheoverallnetwork.Covalentnetworksholddiamondstogether.Diamondsaremadeofnothingbutcarbon,andsoissoot.Unlikesoot, diamondshavecovalentnetworks,makingthemveryhardandcrystalline.
VanderWaalsforces
VanderWaals,or Londondispersionforcesarecausedbytemporarydipolescreatedwhenelectronlocationsarelopsided.Theelectronsare constantlyorbitingthenucleus,andbychancetheycouldendupclosetogether.Theunevenconcentrationofelectronscouldmakeonesideofthe atommorenegativelychargedthantheother,creatingatemporarydipole.Astherearemoreelectronsinanatom,andtheshellsarefurtheraway fromthenucleus,theseforcesbecomestronger. VanderWaalsforcesexplainhownitrogencanbeliquified.NitrogengasisdiatomicitsequationisN2.Sincebothatomshavethesame electronegativity,thereisnodipoleandthemoleculeisnonpolar.Iftherearenodipoles,whatwouldmakethenitrogenatomssticktogethertoform aliquid?VanderWaalsforcesaretheanswer.Theyallowotherwisenonpolarmoleculestohaveattractiveforces.Thesearebyfartheweakest forcesthatholdmoleculestogether.
Acovalentnetwork
MeltingandBoilingPoints
Whencomparingtwosubstances,theirmeltingandboilingpointsmaybequestioned.Todeterminewhichsubstancehasthehighermeltingorboilingpoint,youmustdecidewhich onehasthestrongestintermolecularforce.Metallicbonds,ionicbonds,andcovalentnetworksareverystrong,astheyareactuallyintramolecularforces.Thesesubstanceshavethe highestmeltingandboilingpointsbecausetheyonlyseparateintoindividualmoleculeswhenthepowerfulbondshavebeenbroken.Breakingtheseintramolecularforcesrequires greatamountsofheatenergy. Substanceswithhydrogenbondingwillhavemuchhighermeltingandboilingpointsthanthosethathaveordinarydipoledipoleforces.Nonpolarmoleculeshavethelowestmelting andboilingpoints,becausetheyareheldtogetherbytheweakvanderWaalsforces. Ifyouneedtocomparetheboilingpointsoftwometals,themetalwiththelargeratomicradiuswillhaveweakerbonding,duetothelowerconcentrationofcharge.Whencomparing boilingpointsofthenonpolargases,likethenoblegases,thegaswiththelargestradiuswillhavethehighestpointsbecauseithasthemostpotentialforvanderWaalsforces.
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IoniccompoundscanbecomparedusingCoulomb'sLaw.Lookforsubstanceswithhighionicchargesandlowionicradii.
NamingSubstances
ChemicalReactions
Substanceswithcarbonandhydrogenare organiccompounds.Theyhavespecial namesthatarebeyondthescopeofthis book.Formoreinformation,seethe OrganicChemistryWikibook.
Somecompoundshavecommonnames,like waterforH2O. However,therearethousandsofothercompoundsthatare uncommonorhavemultiplenames.Also,thecommonnameis usuallynotrecognizedinternationally.Whatlookslike watertoyoumightlooklike aguaor vattentosomeoneelse.Toallow chemiststocommunicatewithoutconfusion,therearenamingconventionstodeterminethe systematicnameofachemical.
NamingIonsandIonicCompounds
Ionsareatomsthathavelostorgainedelectrons.Notethatina polyatomicion,theionitselfisheldtogetherbycovalentbonds. Monoatomiccations(positive)arenamedthesamewayastheirelement,andtheycomefirstwhennamingacompound. Monoatomicanions(negative)havethesuffixideandcomeattheendofthecompound'sname.
Examplesofioniccompounds NaCl Sodiumchloride MgCl2 Magnesiumchloride Ca3N2 Calciumnitride
Noticethatthereisnoneedtowritehowmanyionsthereare.Betweentheperiodictableandourknowledgeofionicbonding,wecandeterminethenumberofionsbasedonwhich elementsareused.
PolyatomicIons
Polyatomicionshavespecialnames.Manyofthemcontainoxygenandarecalled oxyanions.Whendifferentoxyanionsaremadeofthesameelementbuthaveadifferentnumber ofoxygenatoms,prefixesandsuffixesareusedtotellthemapart.Thechlorinefamilyofionsisanexcellentexample.
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Name Chloride
Formula Cl
Hypochlorite ClO Chlorite Chlorate ClO2 ClO3
Perchlorate ClO4 Theatesuffixisusedonthemostcommonoxyanion(likesulfateSO42ornitrateNO3).Theitesuffixisusedontheoxyanionwithonelessoxygen(likesulfiteSO32ornitrite NO2).Sometimestherecanbea hypoprefix,meaningonelessoxygenthantheite.Thereisalsoa perprefix,meaningonemoreoxygenthantheate. Onelastprefixyoumayfindis thio.Itmeansanoxygenhasbeenreplacedwithasulfurwithintheoxyanion.CyanateisOCN,andthiocyanateisSCN.
Examplesofpolyatomicions NH4Cl Ammoniumchloride K(HCO3) Potassiumhydrogencarbonate AgNO3 Silvernitrate CuSO3 Copper(I I )sulfite
Inthelastexample,copperhadaromannumeral2afteritsnamebecausethetransitionmetalscanhavemorethanonecharge.Thechargeontheionmustbeknown,soitis writtenoutforionsthathavemorethanonecommoncharge.Silveralwayshasachargeof1+,soitisn'tnecessary(butnotwrong)tonameitscharge.Zincalwayshasachargeof 2+,soyoudon'thavetonameitschargeeither.Aluminumwillalwayshaveachargeof+3.Allothermetals(excepttheGroup1and2elements)musthaveromannumeralstoshow theircharge. Commonpolyatomicionsthatyoushouldknowarelistedinthefollowingtable
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Name Acetate Ammonium Cyanide Cyanate Thiocyanate Hypochlorite Chlorite Chlorate Perchlorate Hypobromite Bromite Bromate Perbromate Hypoiodite Iodite Iodate Periodate Nitrite Nitrate Peroxide
Formula C2H3O2 NH4+ CN CNO CNS ClO ClO2 ClO3 ClO4 BrO BrO2 BrO3 BrO4 IO IO2 IO3 IO4 NO2 NO3 O22
Permanganate MnO4 Sulfite Sulfate SO32 SO42
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StockSystem
Furtherexplanationoftheromannumeralsisinorder.Manyatoms(especiallythetransitionmetals)arecapableofionizinginmore thanoneway.Thenameofanioniccompoundmustmakeitveryclearwhattheexactchemicalformulais.Ifyouwrote"copper chloride",itcouldbeCuClorCuCl2becausecoppercanloseoneortwoelectronswhenitformsanion.Thechargemustbe balanced,sotherewouldbeoneortwochlorideionstoaccepttheelectrons.Tobecorrect,youmustwrite"copper(I I )chloride"if youwantCuCl2and"copper(I )chloride"ifyouwantCuCl.Keepinmindthattheromannumeralsrefertothechargeofthecation, nothowmanyanionsareattached. Commonmetalionsarelistedbelowandshouldbelearned: Name Iron(II)/Ferrous Iron(III)/Ferric Copper(I)/Cuprous Copper(II)/Cupric Tin(II)/Stannous Tin(IV)/Stannic Lead(II)/Plumbous(mostcommon) Lead(IV)/Plumbic Formula Fe2+ Fe3+ Cu+ Cu2+ Sn2+ Sn4+ Pb2+ Pb4+ Inoldertexts,ionswereassignednames basedontheirLatinrootandasuffix. Commonionswiththisnamingsystem include"plumbous/plumbic"for lead(II)/lead(IV)and"ferrous/ferric"for iron(II)/iron(III).TheseLatinbasednames areoutdated,soit'snotimportanttolearn them.Wenowusethe Stocksystem instead.
Mercury(I)(Note:Mercury(I)isapolyatomicion) Hg22+ Mercury(II) Hg2+
NamingMolecules
Therearetwosystemsofnamingmolecularcompounds.Thefirstusesprefixestoindicatethenumberofatomsofanelementthatareinthecompound.Ifthesubstanceisbinary (containingonlytwoelements),thesuffixideisaddedtothesecondelement.Thuswateris dihydrogenmonoxide.Aprefixisnotnecessaryforthefirstelementifthereisonlyone, soSF6is sulfurhexafluoride.Theprefixsystemisusedwhenbothelementsarenonmetallic.
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Number Prefix 1 2 3 4 5 6 7 8 9 10 11 12 Mono Di Tri Tetra Penta Hexa Hepta Octa Nona Deca Undeca Dodeca
Thesecondsystem,the stocksystem,uses oxidationnumberstorepresenthowtheelectronsaredistributedthroughthecompound.Thisisessentiallytheromannumeralsystem thathasalreadybeenexplained,butitappliestononioniccompoundsaswell.Themostelectronegativecomponentofthemoleculehasanegativeoxidationnumberthatdepends onthenumberofpairsofelectronsitshares.Thelesselectronegativepartisassignedapositivenumber.Inthestocksystem,onlythecation'snumberiswritten,andinRoman numerals.Thestocksystemisusedwhenthereisametallicelementinthecompound.InthecaseofV 2O5,itcouldalsobecalledvanadium(V )oxide.Knowingthatoxygen'scharge isalways2,wecandeterminethattherearefiveoxygensandtwovanadiumsifweweregiventhenamewithouttheformula.
Namingacids
Ifanacidisabinarycompound,itisnamedashydro[element]icacid.Ifitcontainsapolyatomicion,thenitisnamed[ionname]icacidiftheionendsinate.Iftheionendsinite thentheacidwillendinous.Theseexamplesshouldhelp.
Examplesofacidnames HCl Hydrochloricacid HClO Hypochlorousacid HClO2 Chlorousacid HClO3 Chloricacid HClO4 Perchloricacid
FormulasandNumbers
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CalculatingFormulaMasses
Thecalculationofacompound'sformulamass(themassofitsmoleculeorformulaunit)isstraightforward.Simplyaddthe individualmassofeachatominthecompound(foundontheperiodictable).Forexample,theformulamassofglucose(C6H12O6) is180amu. Molarmassesarejustaseasytocalculate.Themolarmassisequaltotheformulamass,exceptthattheunitisgramspermole insteadofamu. Inmoleculesbutnotioniccompounds,the formulamassisalsoknownasthe molecularmass.
CalculatingPercentageComposition
Percentagecompositionistherelativemassofonesubstanceinacompoundcomparedtothewhole.Forexample,inmethane(CH4),thepercentagemassofhydrogenis25% becausehydrogenmakesupatotalof4amuoutof16amuoverall.
UsingPercentageComposition
Percentagecompositioncanbeusedtofindthe empiricalformulaofacompound,whichshowstheratiosofelementsinthecompound.However,thisisnotthesameasthe molecularformula.Forexample,manysugarshavetheempiricalformulaCH2O,whichcouldcorrespondtoamolecularformulaofCH2O,C2H4O2,C6H12O6,etc.
Tofindtheempiricalformulafrompercentagecomposition,followtheseproceduresforeachelement. 1. Convertfrompercentagetograms(forsimplicity,assumea100gsample). 2. Dividebytheelement'smolarmasstofindmoles. 3. Simplifytolowestwholenumberratio.
Forexample,acompoundiscomposedof75%carbonand25%hydrogenbymass.Findtheempiricalformula. 75gC/(12g/molC)=6.25molC 25gH/(1g/molH)=25molH 6.25molC/6.25=1molC 25molH/6.25=4molH ThustheempiricalformulaisCH4.
CalculatingMolecularFormula
Ifyoufindtheempiricalformulaofacompoundanditsmolar/molecularmass,thenyoucanfinditsexactmolecularformula.Rememberthatthemolecularformulaisalwaysa wholenumbermultipleoftheempiricalformula.Forexample,acompoundwiththeempiricalformulaHOhasamolecularmassof34.0amu.SinceHOwouldonlybe17.0amu, whichishalfof34.0,themolecularformulamustbeH2O2.
Exerciseforthereader Anunknownsubstancemustbeidentified.Labanalysishasfoundthatthesubstanceiscomposedof80%Fluorineand20%Nitrogenwitha molecularmassof71amu.Whatistheempiricalformula?Whatisthemolecularformula?

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Stoichiometry
Theword stoichiometryderivesfromtwoGreekwords: stoicheion(meaning"element")and metron(meaning"measure").Stoichiometrydealswithcalculationsaboutthemasses (sometimesvolumes)ofreactantsandproductsinvolvedinachemicalreaction.Itisaverymathematicalpartofchemistry,sobepreparedforlotsofcalculatoruse. JeremiasBenjaimRichter(17621807)wasthefirsttolaydowntheprinciplesofstoichiometry.In1792hewrote:" Diestchyometrie(Stchyometria)istdieWissenschaftdie quantitativenoderMassenverhltnissezumessen,inwelchendiechymischenElementegegeneinanderstehen. "[Stoichiometryisthescienceofmeasuringthequantitative proportionsormassratiosinwhichchemicalelementsstandtooneanother.]
MolarCalculations
YourTool:DimensionalAnalysis
Luckily,almostallofstoichiometrycanbesolvedrelativelyeasilyusingdimensionalanalysis.Dimensionalanalysisisjustusingunits,insteadofnumbersorvariables,todomath, usuallytoseehowtheycancelout.Forinstance,itiseasytoseethat:
Itisthisprinciplethatwillguideyouthroughsolvingmostofthestoichiometryproblems(chemicalreactionproblems)youwillseeinGeneralChemistry.Beforeyouattempttosolve aproblem,askyourself:whatdoIhavenow?whereamIgoing?Aslongasyouknowhowmany(units)per(otherunits),thiswillmakestoichiometrysignificantlyeasier.
MolestoMass
Howheavyis1.5moloflead?Howmanymolesin22.34gofwater?Calculatingthemassofasamplefromthenumberofmolesit containsisquitesimple.Weusethe molarmass(massofonemole)ofthesubstancetoconvertbetweenmassandmoles.When writingcalculations,wedenotethemolarmassofasubstancebyanuppercase"M"(e.g.M(Ne)means"themolarmassofneon"). Asalways,"n"standsforthenumberofmolesand"m"indicatesthemassofasubstance.Tofindthesolutionstothetwo questionswejustasked,let'sapplysomedimensionalanalysis: Wherecanyoufindthemolarmassof theseelements?Theperiodictable.You shouldalwayshaveoneonhanddon't expecttogetveryfarwithoutone!
Canyouseehowtheunitscanceltogiveyoutheansweryouwant?Allyouneededtoknowwasthatyouhad1.5molPb(lead),andthat1molPbweighs207.2grams.Thus, multiplying1.5molPbby207.2gPbanddividingby1molPbgivesyou310.8gPb,youranswer.
MasstoMoles
Butwehadonemorequestion:"Howmanymolesin22.34gofwater?"Thisisjustaseasy:
Wheredidthe18gH2Ocomefrom?Welookedattheperiodictableandsimplyaddeduptheatomicmassesoftwohydrogensandanoxygentogetthemolecularweightofwater. en.wikibooks.org/wiki/General_Chemistry/Print_version 52/184
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Wheredidthe18gH2Ocomefrom?Welookedattheperiodictableandsimplyaddeduptheatomicmassesoftwohydrogensandanoxygentogetthemolecularweightofwater. Thisturnedouttobe18,andsinceallthemassesontheperiodictablearegivenwithrespectto1mole,weknewthat1molofwaterweighed18grams.Thisgaveusthe relationshipabove,whichisreallyjust(again)watchingunitscancelout!
CalculatingMolarMasses
Beforewecandothesetypesofcalculations,wefirsthavetoknowthemolarmass.Fortunately,thisisnotdifficult,asthemolarmassisexactlythesameasthe atomicweightof anelement.Atableofatomicweightscanbeusedtofindthemolarmassofelements(thisinformationisoftenincludedintheperiodictable).Forexample,theatomicweightof oxygenis 16.00amu,soitsmolarmassis16.00g/mol. Forspecieswithmorethanoneelement,wesimplyadduptheatomicweightsofeachelementtoobtainthemolarmassofthecompound.Forexample,sulfurtrioxidegasismade upofsulfurandoxygen,whoseatomicweightsare32.06and16.00respectively.
Theprocedureformorecomplexcompoundsisessentiallythesame.Aluminiumcarbonate,forexample,containsaluminium,carbon,andoxygen.Tofindthemolarmass,wehave tobecarefultofindthe totalnumberofatomsofeachelement.Threecarbonateionseachcontainingthreeoxygenatomsgivesatotalofnineoxygens.Theatomicweightsof aluminiumandcarbonare26.98and12.01respectively.
EmpiricalFormulae
Theempiricalformulaofasubstanceis thesimplestratioofthenumberofmolesofeachelementinacompound.Theempiricalformulaisambiguous,e.g.theformulaCHcould representCH,C2H2,C3H3etc.Theselatterformulaearecalled molecularformulae.Itfollowsthatthemolecularformulaisalwaysa wholenumbermultipleoftheempirical formulaforacompound. Calculatingtheempiricalformulaiseasyiftherelativeamountsofeachelementinthecompoundareknown.Forexample,ifasamplecontains1.37moloxygenand2.74mol hydrogen,wecancalculatetheempiricalformula.Agoodstrategytouseistodivideallamountsgivenbythesmallest nonintegeramount,thenmultiplybywholenumbersuntil thesimplestratioisfound.Wecanmakeatableshowingthesuccessiveratios. Hydrogen Oxygen 2.74 2 1.37 1 divideby1.37 ANSWER
TheempiricalformulaofthecompoundisH2O. Here'sanotherexample.Asampleofpiperonalcontains1.384molcarbon,1.033molhydrogenand0.519moloxygen. Carbon Hydrogen Oxygen 1.384 2.666 8 1.033 2 6 0.519 1 3 divideby0.519 multiplyby3 ANSWER
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TheempiricalformulaofpiperonalisC8H6O3.
ConvertingfromMasses
Often,wearegiventherelativecompositionbymassofasubstanceandaskedtofindtheempiricalformula.Thesemassesmustfirstbeconvertedtomolesusingthetechniques outlinedabove.Forexample,asampleofethanolcontains52.1%carbon,13.2%hydrogen,and34.7%oxygenbymass.Hypothetically,100gofthissubstancewillcontain52.1g carbon,13.2ghydrogenand34.7goxygen.Dividingthesebytheirrespectivemolarmassesgivestheamountinmolesofeachelement(aswelearnedabove).Theseare4.34mol, 13.1mol,and2.17molrespectively. Carbon Hydrogen Oxygen 4.34 2 13.1 6 2.17 1 divideby2.17 ANSWER
TheempiricalformulaofethanolisC2H6O.
MolecularFormula
Asmentionedabove,themolecularformulaforasubstanceequalsthecountofatomsofeachtypeinamolecule.Thisisalwaysa wholenumbermultipleoftheempiricalformula.Tocalculatethemolecularformulafromtheempiricalformula,weneedtoknow the molarmassofthesubstance.Forexample,theempiricalformulafor benzeneisCH,anditsmolarmassis78.12g/mol. Dividetheactualmolarmassbythemassoftheempiricalformula,13.02g/mol,todeterminethemultipleoftheempiricalformula, "n".Themolecularformulaequalstheempiricalformulamultipliedby"n". Beware:InthecaseofH2O,thewhole numbermultipleis1,soitsempirical formulaisthesameasitsmolecular formula.Thisisnotalwaysthecase!
Thisshowsthatthemolecularformulaforbenzeneis6timestheempiricalformulaofCH.ThemolecularformulaforbenzeneisC6H6.
SolvingMassMassEquations
Atypicalmassmassequationwillgiveyouanamountingramsandaskforanotheransweringrams.
Tosolveamassmassequation,followtheserules 1. 2. 3. 4. Balancetheequationifitisnotalready. Convertthegivenquantitytomoles. Multiplybythemolarratioofthedemandedsubstanceoverthegivensubstance. Convertthedemandedsubstanceintograms.
Forexample,giventheequation reacting.
,findouthowmanygramsofsilver(Ag)willresultfrom43.0gramsofcopper(Cu)
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Convertthegivenquantitytomoles.
Multiplybythemolarratioofthedemandedsubstanceandthegivensubstance.
Convertthedemandedsubstancetograms.
Summary
Tosolveastoichiometricproblem,youneedtoknowwhatyoualreadyhaveandwhatyouwanttofind.Everythinginbetweenisbasicalgebra.
KeyTerms Molarmass: mass(ingrams)ofonemoleofasubstance. Empiricalformula: thesimplestratioofthenumberofmolesofeachelementinacompound Molecularformula: theactualratioofthenumberofmolesofeachelementinacompound
Ingeneral,allyouhavetodoiskeeptrackoftheunitsandhowtheycancel,andyouwillbeonyourway!
ChemicalEquations
Chemicalequationsareaconvenient,standardizedsystemfordescribingchemicalreactions.Theycontainthefollowinginformation. Thetypeof reactantsconsumedand productsformed Therelativeamountsofreactantsandproducts Theelectricalchargesonions Thephysicalstateofeachspecies(e.g.solid,liquid) Thereactionconditions(e.g.temperature,catalysts) Thefinaltwopointsareoptionalandsometimesomitted.
AnatomyofanEquation
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Hydrogengasandchlorinegaswillreactvigorouslytoproducehydrogenchloridegas.Theequationaboveillustratesthisreaction.Thereactants,hydrogenandchlorine,arewritten ontheleftandtheproducts(hydrogenchloride)ontheright.Thelargenumber2infrontofHClindicatesthattwomoleculesofHClareproducedforeach1moleculeofhydrogen andchlorinegasconsumed.The2insubscriptbelowHindicatesthattherearetwohydrogenatomsineachmoleculeofhydrogengas.Finally,the(g)symbolssubscripttoeach speciesindicatesthattheyaregases.
ReactingSpecies
Speciesinachemicalreactionisageneraltermusedtomeanatoms,moleculesorions.Aspeciescancontainmorethanonechemicalelement(HCl,forexample,contains hydrogenandchlorine).Eachspeciesinachemicalequationiswritten:
E isthechemicalsymbolfortheelement, xisthenumberofatomsofthatelementinthespecies, yisthecharge(ifitisanion)and (s)isthephysicalstate. Thesymbolsinparentheses(insubscriptbeloweachspecies)indicatethephysicalstateofeachreactantorproduct. (s)meanssolid (l)meansliquid (g)meansgas (aq)meansaqueoussolution(i.e.dissolvedinwater)
Forexample,ethylalcoholwouldbewritten chargeof1+.
becauseeachmoleculecontains2carbon,6hydrogenand1oxygenatom.Amagnesiumionwouldbewritten becauseeachmoleculecontains1nitrogenand4hydrogenatomsandhasa
becauseithasadoublepositive("twoplus")charge.Finally,anammoniumionwouldbewritten
Coefficients
Thenumbersinfrontofeachspecieshaveaveryimportantmeaningtheyindicatetherelativeamountsoftheatomsthatreact.Thenumberinfrontofeachspeciesiscalleda coefficient.Intheaboveequation,forexample,oneH2moleculereactswithoneCl2moleculetoproducetwomoleculesofHCl.Thiscanalsobeinterpretedas moles(i.e.1molH2 and1molCl2produces2molHCl). Itisimportantthatthe LawofConservationofMassisnotviolated.Theremustbethesamenumberofeachtypeofatomsoneithersideoftheequation.Coefficientsareusefulfor keepingthesamenumberofatomsonbothsides:
Ifyoucounttheatoms,therearefourhydrogensandtwooxygensoneachside.Thecoefficientsallowusto balancetheequationwithoutthemtheequationwouldhavethewrong numberofatoms.Balancingequationsisthetopicofthenextchapter.
OtherInformation
Occasionally,otherinformationaboutachemicalreactionwillbesuppliedinanequation(suchastemperatureorotherreactionconditions).Thisinformationisoftenwrittentothe rightoftheequationorabovethereactionarrow.Asimpleexamplewouldbethemeltingofice. ,whichcouldbewrittenas
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Reactionscommonlyinvolve catalysts,whicharesubstancesthatspeedupareactionwithoutbeingconsumed.Catalystsareoftenwrittenoverthearrow.Aperfectexampleofa catalyzedreactionisphotosynthesis.Insideplantcells,asubstancecalled chlorophyllconvertssunlightintofood.Thereactioniswritten:
Examples
Thisistheequationforburningmethanegas(CH4)inthepresenceofoxygen(O2)toformcarbon dioxideandwater:CO2andH2Orespectively.NoticetheuseofcoefficientstoobeytheLawof ConservationofMatter.
Thisisa precipitationreactioninwhichdissolvedleadcationsandiodideanionscombinetoforma solidyellowprecipitateofleadiodide(anionicsolid).
Thesetwoequationsinvolveacatalyst.Theyoccuroneafteranother,usingdivanadiumpentoxideto convertsulfurdioxideintosulfurtrioxide.Ifyoulookclosely,youcanseethatthevanadiumcatalystis involvedinthereaction,butitdoesnotgetconsumed.Itisbothareactantandaproduct,butitis necessaryforthereactiontooccur,makingitacatalyst.
Ifweaddbothequationstogether,wecancancelouttermsthatappearonbothsides.Theresulting equationismuchsimplerandselfexplanatory(althoughtheoriginalpairofequationsismoreaccurate indescribinghowthereactionproceeds).
BalancingEquations
BalancingEquations
Chemicalequationsareusefulbecausetheygivetherelativeamountsofthesubstancesthatreactinachemicalequation.Forexample,fromthechemicalequationfortheformation ofammonia,wecanseethatonemoleofnitrogengaswillcombinewiththreemolesofhydrogengastoformtwomolesofammoniagas.
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Insomecases,however,wemaynotknowtherelativeamountsofeachsubstancethatreacts.Fortunately,wecanalwaysfindthecorrect coefficientsofanequation(therelative amountsofeachreactantandproduct).Theprocessoffindingthecoefficientsisknownas balancingtheequation. Duringachemicalreaction,atomsareneithercreatedordestroyed.Thesameatomsarepresentbeforeandafterareactiontakesplacetheyarejustrearranged.Thisiscalledthe LawofConservationofMatter,andwecanusethislawtohelpusfindtherightcoefficientstobalanceanequation. Forexample,assumeintheaboveequationthatwedonotknowhowmanymolesofammoniagaswillbeproduced:
Fromtheleftsideofthisequation,weseethatthereare2atomsofnitrogengasinthemoleculeN2(2atomspermoleculex1molecule),and6atomsofhydrogengasinthe3H2 molecules(2atomspermoleculex3molecules).BecauseoftheLawofConservationofMatter,theremustalsobe2atomsnitrogengasand6atomsofhydrogengasontheright side.Sinceeachmoleculeoftheresultantammoniagas(NH3)contains1atomofnitrogenand3atomsofhydrogen,2moleculesareneededtoobtain2atomsofnitrogenand6 atomsofhydrogen.
AnExample
Thischemicalequationshowsthecompoundsbeingconsumedandproducedhowever,itdoesnotappropriatelydealwiththequantitiesof thecompounds.Thereappeartobetwooxygenatomsontheleftandonlyoneontheright.Butweknowthatthereshouldbethesame numberofatomsonbothsides.Thisequationissaidtobe unbalanced,becausethenumberofatomsaredifferent.
Tomaketheequationbalanced,addcoefficientsinfrontofeachmoleculeasneeded.The2infrontofhydrogenontheleftindicatesthat twiceasmanyatomsofhydrogenareneededtoreactwithacertainnumberofoxygenatoms.Thecoefficient1isnotwritten,sinceit assumedintheabsenceofanycoefficient.
Now,let'sconsiderasimilarreactionbetweenhydrogenandnitrogen.
Typically,itiseasiesttobalanceallpureelementslast,especiallyhydrogen.First,byplacingatwoinfrontofammonia,thenitrogensare balanced.
Thisleaves6molesofatomichydrogenintheproductsandonlytwomolesinthereactants.Acoefficientof3isthenplacedinfrontofthe hydrogentogiveafullybalancedreaction.
Tricksinbalancingcertainreactions
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Combustion
Acombustionreactionisareactionbetweenacarbonchain(basically,amoleculeconsistingofcarbons,hydrogen,andperhapsoxygen)withoxygentoformcarbondioxideand water,plusheat.Combustionreactionscouldgetverycomplex:
Fortunately,thereisaneasywaytobalancethesereactions. First,notethatthecarboninC6H6canonlyappearontheproductsideinCO2.Thus,wecanwriteacoefficientof6infrontofCO2. Next,notethatthehydrogeninC6H6canonlygotoH2O.Thus,weputa3infrontofH2O. Wehave15oxygenatomsontheproductside,sothereare O2moleculesonthereactantside.Tomakethisaninteger,wemultiplyallcoefficientsby2.
AnotherExample
HelpfulHint!
Asreactionsbecomemorecomplex,theybecomemoredifficultto balance.Forexample,thecombustionofbutane(lighterfluid).
Note:Fractionsaretechnically
allowedascoefficients,buttheyare generallyavoided.Multiplyall coefficientsbythedenominatorto removeafraction.
Onceagain,itisbettertoleavepureelementsuntiltheend,sofirst we'llbalancecarbonandhydrogen.Oxygencanthenbebalancedafter. Itiseasytoseethatonemoleofbutanewillproducefourmolesof carbondioxideandfivemolesofwater.
Nowthereare13oxygenatomsontherightandtwoontheleft.The oddnumberofoxygenspreventsbalancingwithelementaloxygen. Becauseelementaloxygenisdiatomic,thisproblemcomesupinnearly everycombustionreaction.Simplydoubleeveryspeciesexceptfor oxygentogetanevennumberofoxygenatomsintheproduct.
Thecarbonandhydrogensarestillbalanced,andnowthereareaneven numberofoxygensintheproduct.Finally,thereactioncanbebalanced.
LimitingReactantsandPercentYield
LimitingReactants
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Whenchemicalreactionsoccur,thereactantsundergochangetocreatetheproducts.The coefficientsofthechemicalequationshowtherelativeamountsofsubstanceneededfor thereactiontooccur.Considerthecombustionofpropane:
Foreveryonemoleofpropane,theremustbefivemolesofoxygen.Foreveryonemoleofpropanecombusted,therewillbethreemolesofcarbondioxideandfourmolesofwater produced(alongwithmuchheat).Ifapropanegrillisburning,therewillbeaverylargeamountofoxygenavailabletoreactwiththepropanegas.Inthiscase,oxygenisthe excess reactant.Thereissomuchoxygenthattheexactamountdoesn'tmatteritwillnotrunout. Ontheotherhand,thereisnotanunlimitedamountofpropane.Itwillrunoutfarbeforetheoxygenrunsout,makingita limitingreactant.Theamountofpropaneavailablewill decidehowfarthereactionwillgo.
Example 2H2+O22H2O Iftherearethreemolesofhydrogen,andonemoleofoxygen,whichisthelimitingreactant?Howmuchproductiscreated? Twiceasmuchhydrogenthanoxygenisrequired.However,thereismorethantwiceasmuchhydrogen.Thushydrogenistheexcessreactantand oxygenisthelimitingreactant.Ifthereactionproceedstocompletion,alloftheoxygenwillbeusedup,andonemoleofhydrogenwillremain.You canimaginethissituationlikethis: 3H2+O22H2O+H2 Thereactantthatisleftoverafterthereactioniscompleteiscalledthe"excessreactant".Often,youwillwanttofigureouthowmuchoftheexcessreactantisleftafterthereaction iscomplete.todothis,firstusemoleratiostodeterminehowmuchexcessreactantisusedupinthereaction. Herearetheratiosthatneedtobeused:
PercentYield
Usually,lessproductismadethantheoreticallypossible.The actualyieldislowerthanthe theoreticalyield.Tocomparethetwo,onecancalculate percentyield,whichis . Thepercentyieldtellsushowfarthereactionactuallywent.
TypesofChemicalReactions
Chemicalreactionscanbedividedintoseveralclasseseachhavingsimilarcharacteristics.Thesedifferenttypesofreactionswillbediscussedingreaterdetailthroughoutthebook. Youwillfindthatalmosteveryreactionyouseecanfallintooneofthesecategories,somakesurethatyouunderstandthem.
SynthesisReactions
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ThegeneralformofasynthesisreactionisA+BAB.Synthesisreactions"putthingstogether".
HelpfulHint!
Synthesisreactionsalwaysyieldone
Thisisthemostwellknownexampleofasynthesisreactiontheformationof waterviathefusionofhydrogengasandoxygengas.
product.Reversingasynthesis reactionwillgiveyouadecomposition
reaction.
Anotherexampleofasynthesisreactionistheformationofsodiumchloride(table salt).
Becauseoftheveryhighreactivitiesofsodiummetalandchlorinegas,thisreactionreleasesatremendousamountofheatandlightenergy.Recallthatatomsreleaseenergyas theybecomestable,andconsidertheoctetrulewhendeterminingwhythisreactionissofavorable.
DecompositionReactions
Thesearetheoppositeofsynthesisreactions,withtheformatABA+B.Decompositionreactions"takethingsapart".Justassynthesisreactionscanonlyformoneproduct, decompositionreactionscanonlystartwithonereactant.Compoundsthatareunstablewilldecomposequicklywithoutoutsideassistance.
Oneexampleistheelectrolysisofwater(passingwaterthroughelectricalcurrent)toformhydrogengasandoxygengas.
Hydrogenperoxideslowlydecomposesintowaterandoxygenbecauseitissomewhatunstable.Theprocessisspedupby theenergyfromlight,sohydrogenperoxideisstoredindarkcontainerstoslowdownthedecomposition.
Carbonicacidisthecarbonationthatisdissolvedinsoda.Itdecomposesintocarbondioxideandwater,whichiswhyan openeddrinkwillnotloseitsfizz.
SingleReplacementReactions
Singlereplacementreactions,alsocalledsingledisplacement,swaponecomponentwithanother,intheformatAB+CAC+B. Addinghydrochloricacidtozincwillcauseagastobubbleout:
DoubleReplacementReactions
Inthesereactions,alsoknownas"doubledisplacementreactions",twocompoundsswapcomponents,intheformatAB+CDAD+CB
Doubledecomposition
thisisalsocalledan"exchange".herearetheexamplesbelow:
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1.)HCl+NaOH>NaCl+H2O
Precipitation
Aprecipitationreactionoccurswhenan ionicsubstancecomesoutofsolutionandformsaninsoluble(orslightlysoluble)solid.Thesolidwhichcomesoutofsolutioniscalleda precipitate.Thiscanoccurwhentwosolublesalts(ioniccompounds)aremixedandformaninsolubleonetheprecipitate.
Anexampleisleadnitratemixedwithpotassiumiodide,whichformsa brightyellowprecipitateofleadiodide.
Notethattheleadiodideisformedasasolid.Thepreviousequationis writteninmolecularform,whichisnotthebestwayofdescribingthe reaction.Eachoftheelementsreallyexistinsolutionasindividualions, notbondedtoeachother(asinpotassiumiodidecrystals).Ifwewrite theaboveasan ionicequation,wegetamuchbetterideaofwhatis actuallyhappening.
Noticetheliketermsonbothsidesoftheequation.Thesearecalled spectatorionsbecausetheydonotparticipateinthereaction.Theycan beignored,andthe netionicequationiswritten.
Inthesolution,thereexistsbothleadandiodideions.Becauseleadiodideisinsoluble,theyspontaneouslycrystalliseandformtheprecipitate.
AcidBaseNeutralization
Insimpleterms,anacidisasubstancewhichcanloseaH+ ion(i.e.aproton)andabaseisasubstancewhichcanacceptaproton.Whenequalamountsofanacidandbasereact, they neutralizeeachother,formingspecieswhicharen'tasacidicorbasic.
Forexample,whenhydrochloricacidandsodiumhydroxidereact,theyformwaterandsodiumchloride(table salt).
Again,wegetaclearerpictureofwhat'shappeningifwewriteanetionicequation.
Acidbasereactionsoftenhappeninaqueoussolution,buttheycanalsooccurinthegaseousstate.Acidsandbaseswillbediscussedinmuchgreaterdetailintheacidsandbases section.
Combustion
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Combustion,betterknownasburning,isthecombinationofasubstancewithoxygen.Theproductsarecarbondioxide,water,and possibleotherwasteproducts.Combustionreactionsreleaselargeamountsofheat.C3H8,betterknownaspropane,undergoes combustion.Thebalancedequationis:
Combustionissimilartoadecompositionreaction,exceptthatoxygenandheatarerequiredforittooccur.Ifthereisnotenoughoxygen, Thecombustionofmethane(releasingheat thereactionmaynotoccur.Sometimes,withlimitedoxygen,thereactionwilloccur,butitproducescarbonmonoxide(CO)orevensoot. andlight) Inthatcase,itiscalled incompletecombustion.Ifthesubstancesbeingburnedcontainatomsotherthanhydrogenandoxygen,then wasteproductswillalsoform.Coalisburnedforheatingandenergypurposes,anditcontainssulfur.Asaresult,sulfurdioxideis released,whichisapollutant.Coalwithlowersulfurcontentismoredesirable,butmoreexpensive,becauseitwillreleaselessofthesulfurbasedpollutants.
OrganicReactions
Organicreactionsoccurbetweenorganicmolecules(moleculescontainingcarbonandhydrogen).Sincethereisavirtuallyunlimitednumberof organicmolecules,thescopeoforganicreactionsisverylarge.However,manyofthecharacteristicsoforganicmoleculesaredeterminedby functionalgroupssmallgroupsofatomsthatreactinpredictableways. AnotherkeyconceptinorganicreactionsisLewisbasicity.Partsoforganicmoleculescanbeelectrophillic(electronloving)ornucleophillic (nucleus,orpositiveloving).Nucleophillicregionshavean excessofelectronstheyactasLewisbaseswhereaselectrophillicareasareelectron deficientandactasLewisacids.Thenucleophillicandelectrophillicregionsattractandreactwitheachother(needlesstosay,thishasinspired manyterribleorganicchemistryjokes). Organicreactionsarebeyondthescopeofthisbook,andarecoveredinmoredetailinOrganicChemistry.However,mostorganicsubstancescan undergoreplacementreactionsandcombustionreactions,asyouhavealreadylearned.
Thisiscarboxylicacid.All functionalgroupsendwithan "R"aplaceholderfortherestof themolecule.
Redox
Redoxisanabbreviationof reduction/oxidationreactions.Thisisexactlywhathappensinaredox reaction,onespeciesis reducedandanotheris oxidized.Reductioninvolvesagainofelectronsand oxidationinvolvesaloss,soaredoxreactionisoneinwhichelectronsare transferredbetweenspecies.Reactionswheresomethingis "burnt"(burningmeansbeingoxidised)areexamplesofredoxreactions,however,oxidationreactionsalsooccurinsolution,whichisvery usefulandformsthebasisofelectrochemistry. Redoxreactionsareoftenwrittenastwo halfreactionsshowingthereductionandoxidationprocessesseparately.Thesehalfreactions arebalanced(bymultiplyingeachbyacoefficient)andaddedtogethertoformthefullequation.Whenmagnesiumisburntinoxygen,it loseselectrons(itisoxidised).Conversely,theoxygengainselectronsfromthemagnesium(itisreduced).
Theformationofhydrogenfluoridecauses fluoridetooxidizeandhydrogentoreduce.
Redoxreactionswillbediscussedingreaterdetailintheredoxsection.
EnergyChangesinChemicalReactions
ExothermicandEndothermicReactions
Thereleaseofenergyinchemicalreactionsoccurswhenthereactantshavehigherchemicalenergythantheproducts.Thechemicalenergyinasubstanceisatypeofpotential
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Thereleaseofenergyinchemicalreactionsoccurswhenthereactantshavehigherchemicalenergythantheproducts.Thechemicalenergyinasubstanceisatypeofpotential energystoredwithinthesubstance.Thisstoredchemicalpotentialenergyisthe heatcontent or enthalpyofthesubstance. Thecollectionofsubstancesthatisinvolvedinachemicalreactionisreferredtoasa systemandanythingelsearounditiscalledthe surroundings. Iftheenthalpydecreasesduringachemicalreaction,acorrespondingamountofenergymustbereleasedtothesurroundings.Conversely,iftheenthalpyincreasesduringareaction, acorrespondingamountofenergymustbeabsorbedfromthesurroundings.Thisissimplythe LawofConservationofEnergy. Endothermicreactionsincreasetheirenthalpybyabsorbingheat.Theyfeelcoldtothetouchaftertheyhaveoccurred. Exothermicreactionsdecreasetheirenthalpybyreleasingheat.Theywillgetwarm,andmayevenburnorexplodeiftheyreleaseenoughheat. Youarealreadyfamiliarwithenthalpy:meltingiceisendothermicandfreezingwaterisexothermic. Examples Whenmethaneburnsinairtheheatgivenoffequalsthedecreaseinenthalpythat occursasthereactantsareconvertedtoproducts. Whenammoniumnitrateisdissolvedinwater,energyisabsorbedandthewatercools. Thisconceptisusedin"coldpacks".
Theenthalpydifferencebetweenthereactantsandtheproductsisequaltotheamount ofenergyreleasedtothesurroundings.Areactioninwhichenergyisreleasedtothe surroundingsiscalledan exothermicreaction.Inthistypeofreactiontheenthalpy,or storedchemicalenergy,islowerfortheproductsthanthereactants.
Theenthalpydifferencebetweenthereactantsandtheproductsisequaltotheamount ofenergyabsorbedfromthesurroundings.Areactioninwhichenergyisabsorbedfrom thesurroundingsiscalledan endothermicreaction.Inendothermicreactionsthe enthalpyoftheproductsisgreaterthantheenthalpyofthereactants.
Becausereactionsreleaseorabsorbenergy,theyaffectthetemperatureoftheirsurroundings.Exothermicreactionsheatuptheirsurroundingswhileendothermicreactionscoolthem down.Thestudyofenthalpy,alongwithmanyotherenergyrelatedtopics,iscoveredintheThermodynamicsUnit.
ActivationEnergy
Thinkaboutthecombustionofmethane.Itreleasesenoughheatenergytocauseafire.However,thereactiondoesnotoccurautomatically.Whenmethaneandoxygenaremixed, anexplosiondoesnotinstantlyoccur.First,themethanemustbeignited,usuallywithalighterormatchstick.Thisrevealssomethingaboutreactions:theywillnotoccurunlessa certainamountof activationenergyisaddedfirst.Inthissense,allreactionsabsorbenergybeforetheybegin,buttheexothermicreactionsreleaseevenmoreenergy.Thiscanbe explainedwithagraphofpotentialenergy:
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Thisgraphshowsanexothermicreactionbecausetheproductsareatalowerenergythanthereactants(soheathasbeenreleased).Beforethatcanhappen,theenergymust actually increase.Theamountofenergyaddedbeforethereactioncancompleteistheactivationenergy,symbolized E a.
PredictingChemicalReactions
TypesofReactions
Thereareseveralguidelinesthatcanhelpyoupredictwhatkindofchemicalreactionwilloccurbetweenamixtureofchemicals:
Severalpureelementsmixedtogethermayundergoasynthesisreaction. Asinglecompoundmayundergoadecompositionreaction.Itoftenformswaterorhydrogengas. Apureelementmixedwithanioniccompoundmayundergoasinglereplacementreaction. Twodifferentioniccompoundsareverylikelytoundergoadoublereplacementreaction. Anorganiccompound(containingcarbonandhydrogen)canusuallyreactwithoxygeninacombustionreaction.
However,notallelementswillreactwitheachother.Tobetterpredictachemicalreaction,knowledgeofthe reactivityseriesisneeded.
Reactivity
Whencombiningtwochemicals,asingleordoublereplacementreactiondoesn'talwayshappen.Thiscanbeexplainedbyalistknownasthe reactivityseries,whichlistselements inorderofreactivity.Thehigheronthelistanelementis,themoreelementsitcanreplaceinasingleordoublereplacementreaction.Whendecidingifareplacementreactionwill occur,lookupthetwoelementsinquestion.Thehigheronewillreplacethelowerone. Elementsattheverytopoftheseriesaresoreactivethattheycanreplacehydrogenfromwater.Thisexplainstheexplosivereactionbetweensodiumandwater:
Elementsinthemiddleofthelistwillreactwithacids(butnotwater)toproduceasaltandhydrogengas.Elementsatthebottomofthelistaremostlynonreactive. Elementsnearthetopofthelistwillcorrode(rust,tarnish,etc.)inoxygenmuchfasterthanthoseatthebottomofthelist.
TheReactivitySeries
MostReactive Red:elementsthatreactwithwaterandacidstoformhydrogengas,andwith oxygen. Orange:elementsthatreactveryslowlywithwaterbutstronglywithacids. Yellow:elementsthatreactwithacidtoformhydrogengas,andwithoxygen. Grey:elementsthatreactwithoxygen(tarnish). White:elementsthatareoftenfoundpurerelativelynonreactive.
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Cs K Na Li Sr Ca Rb Ba Mg Al (C) Mn Zn Cr Fe Cd Co Ni Sn Pb (H2) Sb Bi Cu Hg Ag Pt Au LeastReactive
OxidationStates
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Oxidationstatesareusedtodeterminethedegreeof oxidationor reductionthatanelementhasundergonewhenbonding.Theoxidationstateofacompoundisthesumofthe oxidationstatesofallatomswithinthecompound,whichequalszerounlessthecompoundisionic. Theoxidationstateofanatomwithinamoleculeisthechargeit wouldhave if thebondingwerecompletelyionic,eventhoughcovalentbondsdonotactuallyresultinchargedions.
Methodofnotation
Oxidationstatesarewrittenabovetheelementorgroupofelementsthattheybelongto(whendrawingthemolecule),orwrittenwithromannumeralsinparenthesiswhennaming theelements. Examples aluminum aluminum(III),anion
Determiningoxidationstate
Forsingleatomsorions
Becauseoxidationnumbersarejustthesumoftheelectronsgainedorlost,calculatingthemforsingleelementsiseasy. Examples
Noticethattheoxidationstatesofioniccompoundsaresimpletodetermine.
Forlargermolecules
Althoughcovalentbondsdonotresultincharges,oxidationstatesarestilluseful.Theylabelthehypotheticaltransferofelectrons if the substancewereionic.Determiningtheoxidationstatesofatomsinacovalentmoleculeisveryimportantwhenanalyzing"redox" reactions.Whensubstancesreact,theymaytransferelectronswhentheyformtheproducts,socomparingtheoxidationstatesofthe productsandreactantsallowsustokeeptrackoftheelectrons.
HelpfulHint!
Rememberthatalltheindividual oxidationstatesmustadduptothe chargeonthewholesubstance.
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Examples forhydrogenchloride forwater forthechloriteion (noticetheoverallcharge)
DETERMININGOXIDATIONSTATES Thedeterminationofoxidationstatesisbasedonknowingwhichelementscanhaveonlyoneoxidationstateotherthantheelementalstateandwhichelementsareabletoform morethanoneoxidationstateotherthantheelementalstate.Let'slookatsomeofthe"rules"fordeterminingtheoxidationstates. 1.Theoxidationstateofanelementisalwayszero. 2.Formetals,thechargeoftheionisthesameastheoxidationstate.Thefollowingmetalsformonlyoneion:GroupIA,GroupIIA,GroupIIIA(exceptTl),Zn2+,Cd2+. 3.Formonatomicanionsandcations,thechargeisthesameastheoxidationstate. 4.Oxygeninacompoundis2,unlessaperoxideispresent.Theoxidationstateofoxygeninperoxideion,O22is1. 5.Forcompoundscontainingpolyatomicions,usetheoverallchargeofthepolyatomiciontodeterminethechargeofthecation.Hereisaconvenientmethodfordetermining oxidationstates.Basically,youtreatthechargesinthecompoundasasimplealgebraicexpression.Forexample,let'sdeterminetheoxidationstatesoftheelementsinthe compound,KMnO4.Applyingrule2,weknowthattheoxidationstateofpotassiumis+1.Wewillassign"x"toMnfornow,sincemanganesemaybeofseveraloxidationstates. Thereare4oxygensat2.Theoverallchargeofthecompoundiszero:KMnO4+1x4(2) Thealgebraicexpressiongeneratedis:1+x8=0 Solvingforxgivestheoxidationstateofmanganese:x7=0x=+7KMnO4+1+74(2) Supposethespeciesunderconsiderationisapolyatomicion.Forexample,whatistheoxidationstateofchromiumindichromateion,(Cr2O72)? Asbefore,assigntheoxidationstateforoxygen,whichisknowntobe2.Sincetheoxidationstateforchromiumisnotknown,andtwochromiumatomsarepresent,assignthe algebraicvalueof2xforchromium:Cr2O722x7(2) Setupthealgebraicequationtosolveforx.Sincetheoverallchargeoftheionis2,theexpressionissetequalto2ratherthan0:2x+7(2)=2 Solveforx:2x14=22x=12x=+6 Eachchromiumintheionhasanoxidationstateof+6.Let'sdoonelastexample,whereapolyatomicionisinvolved.Supposeyouneedtofindtheoxidationstateofallatomsin Fe2(CO3)3.Heretwoatoms,ironandcarbon,havemorethanonepossibleoxidationstate.Whathappensifyoudon'tknowtheoxidationstateofcarbonincarbonateion?Infact, knowledgeoftheoxidationstateofcarbonisunnecessary.Whatyouneedtoknowisthechargeofcarbonateion(2).Setupanalgebraicexpressionwhileconsideringjusttheiron ionandthecarbonateion:Fe2(CO3)32x3(2)2x6=02x=6x=3 Eachironioninthecompoundhasanoxidationstateof+3.Nextconsiderthecarbonateionindependentoftheiron(III)ion:CO32x3(2)x6=2x=+4 Theoxidationstateofcarbonis+4andeachoxygenis2.
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Guidelines
Determiningoxidationstatesisnotalwayseasy,buttherearemanyguidelinesthatcanhelp.Thisguidelinesinthistablearelistedinorderofimportance.Thehighestoxidation statethatanyelementcanreachis+8inXeO4. Element Fluorine Hydrogen UsualOxidationState Fluorine,beingthemostelectronegativeelement,willalwayshaveanoxidationof1(exceptwhenitisbondedtoitselfinF2,whenitsoxidationstateis0). Hydrogenalwayshasanoxidationof+1,1,or0.Itis+1whenitisbondedtoanonmetal(e.g.HCl,hydrochloricacid).Itis1whenitisbondedtometal(e.g.NaH, sodiumhydride).Itis0whenitisbondedtoitselfinH2. Oxygenisusuallygivenanoxidationnumberof2initscompounds,suchasH2O.Theexceptionisinperoxides(O22)whereitisgivenanoxidationof1.Also,inF2O oxygenisgivenanoxidationof+2(becausefluorinemusthave1),andinO2,whereitisbondedonlytoitself,theoxidationis0. TheGroup1Ametalsalwayshaveanoxidationof+1,asinNaCl.TheGroup2Ametalsalwayshaveanoxidationof+2,asinCaF2.Therearesomerareexceptions thatdon'tneedconsideration. Theotherhalogens(Cl,Br,I,As)usuallyhaveanoxidationof1.Whenbondedtoanotherhalogen,itsoxidationwillbe0.However,theycanalsohave+1,+3,+5,or +7.Lookingatthefamilyofchlorides,youcanseeeachoxidationstate(Cl2(0),Cl(1),ClO(+1),ClO2(+3),ClO3(+5),ClO4(+7)).
Oxygen Alkali Metals Halogens
Nitrogen Nitrogen(andtheotherGroup5Aelements,suchasphosphorus,P)oftenhave3(asinammonia,NH3),butmayhave+3(asinNI 3)or+5(asinphosphate,PO43). Carbon Carboncanliterallyhaveanyoxidationstate(from4,asinCH4,to+4,asinCF4).Itisbesttofindtheoxidationofotherelementsfirst.
Ingeneral, themoreelectronegativeelementhasthenegativenumber.Usingachartofelectronegativities,youcandeterminetheoxidationstateofanyatomwithinacompound.
Periodicity
Oxidationstatesareanotherperiodictrend.Theyseemtorepeatapatternacrosseachperiod.
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RedoxReactions
Redox
Redoxreactionsarechemicalreactionsinwhichelementsareoxidizedandreduced. Specifically,atthemostbasicleveloneelementgets oxidizedbylosing,ordonating,electronstothe oxidizingagent .Indoingso,theoxidizingagentgets reducedbyacceptingthe electronslost,ordonated,bythe reducingagent (i.e.theelementgettingoxidized). Ifitseemsasthoughtherearetwoseparatethingsgoingonhere,youarecorrect:redoxreactionscanbesplitintotwo halfreactions,onedealingwithoxidation,theother, reduction.
Mnemonic
OilRig Oxidation I s Loss. Reduction I s Gain Alternatively: LEOGER Loose E lectrons Oxidation. Gain E lectrons Reduction
Example
Thisisthecompletereaction.Ironisoxidized,thusitisthereducingagent.Copperisreduced,makingittheoxidizingagent.
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Thisistheoxidationhalfreaction.
Thisisthereductionhalfreaction.
Whenthetwohalfreactionsaresummed,theresultis:
HelpfulHint!
Ifyoucancelouttheelectronsonboth sides,yougettheoriginalequation.
BalancingRedoxEquations
Inaredoxreaction, allelectronsmustcancelout .Ifyouareaddingtwohalfreactionswithunequalnumbersofelectrons,thentheequationsmustbemultipliedbyacommon denominator.Thisprocessissimilartobalancingregularequations,butnowyouaretryingtobalancetheelectronsbetweentwohalfreactions.
Example
Theelectronsdon'tcompletelycancelout.Thereisoneelectronmoreontheleft.However,ifyoudouble alltermsinthefirsthalfreaction,thenaddittothesecondhalfreaction, theelectronswillcanceloutcompletely.Thatmeansthehalfreactionsforthisredoxreactionareactually:
BalancingRedoxEquationsinanAcidicorBasicSolution
Ifareactionoccursinanacidicorbasicenvironment,theredoxequationisbalancedasfollows:
1. 2. 3. 4.
Writetheoxidationandreductionhalfreactions,butwiththewholecompound,notjusttheelementthatisreduced/oxidized. Balancebothreactionsforallelements except oxygenandhydrogen. Iftheoxygenatomsarenotbalancedineitherreaction,addwatermoleculestothesidemissingtheoxygen. Ifthehydrogenatomsarenotbalanced,addhydrogenionsuntilthehydrogenatomsarebalanced.

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5. Multiplythehalfreactionsbytheappropriatenumber(sothattheyhaveequalnumbersofelectrons). 6. Addthetwoequationstocancelouttheelectrons,asinthepreviousmethod,andtheequationisbalanced!
Ifthereactionoccursinabasicenvironment,proceedasifitisinanacidenvironment,but,afterstep4,foreachhydrogenionadded,addahydroxideiontobothsidesofthe equation.Then,combinethehydroxideionsandhydrogenionstoformwater.Then,cancelallthewatermoleculesthatappearonbothsides.
Electrochemistry
RedoxReactions(review)
Redox(shorthandforreduction/oxidationreaction)describesallchemicalreactionsinwhichatomshavetheiroxidationnumber(oxidationstate)changed. Thiscanbeeitherasimpleredoxprocesssuchastheoxidationofcarbontoyieldcarbondioxide,orthereductionofcarbonbyhydrogentoyieldmethane(CH4),oritcanbea complexprocesssuchastheoxidationofsugarinthehumanbodythroughaseriesofverycomplexelectrontransferprocesses. Thetermredoxcomesfromthetwoconceptsofreductionandoxidation.Itcanbeexplainedinsimpleterms: Oxidationdescribesthelossofelectronsbyamolecule,atom,orion Reductiondescribesthegainofelectronsbyamolecule,atom,orion
However,thesedescriptions(thoughsufficientformanypurposes)arenottrulycorrect.Oxidationandreductionproperlyrefertoa changeinoxidationnumbertheactualtransferofelectronsmayneveroccur.Thus,oxidationisbetterdefinedasanincreasein oxidationnumber,andreductionasadecreaseinoxidationnumber.Inpractice,thetransferofelectronswillalwayscauseachange inoxidationnumber,buttherearemanyreactionswhichareclassedas"redox"eventhoughnoelectrontransferoccurs(suchasthoseinvolvingcovalentbonds).
Nonredoxreactions,whichdonotinvolve changesinformalcharge,areknownas metathesisreactions.
Electrochemistry
Electrochemistryisabranchofchemistrythatdealswiththeflowofelectricitybychemicalreactions.Theelectronsinabalancedhalfreactionshowthedirectrelationshipbetween electricityandthespecificredoxreaction.Electrochemicalreactionsareeitherspontaneous,ornonspontaneous.Aspontaneousredoxreactiongeneratesavoltageitself.A nonspontaneousredoxreactionoccurswhenanexternalvoltageisapplied.Thereactionsthatoccurinanelectricbatteryareelectrochemicalreactions.
Threecomponentsofanelectrochemicalreaction Asolutionwhereredoxreactionsmayoccur(solutionsaresubstancesdissolvedinliquid,usuallywater) Aconductorforelectronstobetransferred(suchasametalwire) Aconductorforionstobetransferred(usuallya saltbridge)
e.g.filterpaperdippedinasaltsolution.
Electrolysis
An electrolysisexperimentforcesanonspontaneouschemicalreactiontooccur.Thisisachievedwhentwoelectrodesaresubmersedinanelectricallyconductivesolution,andthe electricalvoltageappliedtothetwoelectrodesisincreaseduntilelectronsflow.Theelectrodereceivingtheelectrons,orwherethereductionreactionsoccur,iscalledthecathode. Theelectrodewhichsuppliestheelectrons,orwheretheoxidationreactionsoccur,iscalledtheanode. Amoltensaltisanexampleofsomethingthatmaybeelectrolyzedbecausesaltsarecomposedofions.Whenthesaltisinitssolidstate,theionsarenotabletofreelymove.
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Amoltensaltisanexampleofsomethingthatmaybeelectrolyzedbecausesaltsarecomposedofions.Whenthesaltisinitssolidstate,theionsarenotabletofreelymove. However,whenthesaltisheatedenoughuntilitmelts(makingitamoltensalt),theionsarefreetomove.Thismobilityoftheionsinthemoltensaltmakesthesaltelectrically conductive.Intheelectrolysisofamoltensalt,forexamplemelted ,thecationofthesalt(inthiscase )willbereducedatthecathode,andtheanionofthesalt(in thiscase )willbeoxidizedattheanode: Cathodereaction:Na+ +e Na Anodereaction:2ClCl2+2e Aqueoussolutionsofsaltscanbeelectrolyzedaswellbecausetheyarealsoelectricallyconductive.Inaqueoussolutions,thereisanadditionalreactionpossibleateachthecathode andtheanode: Cathode:2H2O+2e H2+2OH (reductionofwater) Anode:2H2O4H+ +O2+4e (oxidationofwater) Withtheadditionofthesetworeactions,therearenowtwopossiblereactionsateachelectrode.Atthecathode,eitherthereductionofthecationorthereductionofwaterwilloccur. Attheanode,eithertheoxidationoftheanionortheoxidationofwaterwilloccur.Thefollowingrulesdeterminewhichreactiontakesplaceateachelectrode: Cathode:Ifthecationisaveryactivemetal,waterwillbereduced.VeryactivemetalsincludeLi,Na,K,Rb,Cs,Ca,Sr,andBa.Ifthecationisanactiveorinactivemetal, thecationwillbereduced. Anode:Iftheanionisapolyatomicion,waterwillgenerallybeoxidized.Specifically,sulfate,perchlorate,andnitrateionsarenotoxidizedwaterwilloxidizeinstead.Chloride, bromide,andiodideionswillbeoxidized.Iftheanioninonesaltisoxidizedinanaqueouselectrolysis,thatsameanionwillalsobeoxidizedinanyothersalt.
GalvanicCells
Theenergyofaspontaneousredoxreactioniscapturedusinga galvaniccell .Thefollowingpartsarenecessarytomakeagalvaniccell: 1. 2. 3. 4. 5. Twohalfcells Twoelectrodes Oneelectricallyconductivewire Onesaltbridge Onedevice,usuallyanammeteroravoltmeter
Agalvaniccellisconstructedasshownintheimagetotheright.Thetwohalfreactionsareseparatedintotwohalfcells.Allofthe reactantsintheoxidationhalfreactionareplacedinonehalfcell(theanode),andallthereactantsofthereductionhalfreactionare placedintheotherhalfcell(thecathode).Ifthehalfreactioncontainsametal,themetalservesastheelectrodeforthathalfcell. Otherwise,aninertelectrodemadeofplatinum,silver,orgoldisused.Theelectrodesareconnectedwithawirewhichallowstheflowof electrons.Theelectronsalwaysflowfromtheanodetothecathode.Thehalfcellsareconnectedbyasaltbridgewhichallowstheionsin thesolutiontomovefromonehalfcelltotheother,sothatthereactioncancontinue.Sincetheoverallreactionisspontaneous,theflow ofelectronswillmovespontaneouslythroughtheoutercircuitryfromwhichtheenergycanbeextirpated.Theenergyharnessedisuseful becauseitcanbeusedtodowork.Forexample,ifanelectricalcomponentsuchasalightbulbisattachedtothewire,itwillreceive powerfromtheflowingelectrons. Consistentresultsfromagalvaniccellaredependentonthreevariables:pressure,temperature,andconcentration.Thus,chemists definedastandardstateforgalvaniccells.Thestandardstateforthegalvaniccellisapressureof1.00atmosphericpressure(atm)forall gases,atemperatureof298kelvin(K )andconcentrationsof1.00molarity(M)forallsolublecompounds,liquids,andsolids.
The"ammeter"atthetopmeasuresthe electricalcurrentflowingthroughthewire. Electronsareflowingfromcoppertozinc, makingzinctheoxidizingagent.
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Voltage
Voltageisameasureofspontaneityofredoxreactions,anditcanbemeasuredbyavoltmeter.Ifthevoltageofareactionispositive,thereactionoccursspontaneously,butwhen negative,itdoesnotoccurspontaneously. Tocomputethevoltageofaredoxequation,splittheequationintoitsoxidationcomponentandreductioncomponent.Then,lookupthevoltagesofeachcomponentonastandard electrodepotentialtable.Thistablewilllistthevoltageforthereductionequation.Theoxidationreaction'svoltageisnegativeofthecorrespondingreductionequation'svoltage.To findtheequation'svoltage,addthestandardvoltagesforeachhalfreaction.voltageiswhatabelincolnusedtomaryhiswife.
Solubility
TypesofSolutions
AqueousSolutions
A solutionisahomogenousmixture,composedofsolvent(s)and solute(s).A solventisanysubstancewhichallowsothersubstancestodissolveinit.Therefore,itisusuallypresentinthegreateramount. Solutesaresubstancespresentina solution.Notethatwhenasolutedissolvesinasolvent,nochemicalbondsformbetweenthesolventandsolute. Solutionshavevariablecomposition,unlikepurecompoundswhosecompositionisfixed.Forexample,a500mLsolutionoflemonadecanconsistof70%water,20%lemonjuice, and10%sugar.Therecanalsobea500mLsolutionoflemonadeconsistingof60%water,25%lemonjuice,and15%sugar. Whentwoliquidscanbereadilycombinedinanyproportions,theyaresaidtobe miscible.Anexamplewouldbealcoholandwater.Eitherofthetwocantotallydissolveeachother inanyproportion.Twoliquidsaredefinedas immiscibleiftheywillnotformasolution,suchasoilandwater.Solidsolutesinametallicsolventareknownas alloys.Goldisan exampleofanalloy.Itistoosoftinitspureform,soothermetalsaredissolvedinit.Jewelersmayuse14karatgold,whichcontainstwothirdsgoldandonethirdothermetals.
VariablesAffectingSolubility
Factor Concept Example Powderedsugarwilldissolveinwaterfasterthanrockcandy. Sugardissolvesmorereadilyinhotwater,butCO2dissolves betterincoldsodathanwarmsoda. Surfacearea Moresurfaceareagivesmoreopportunityforsolutesolventcontact Temperature Solidsaremoresolubleinhotsolvents,gasesaremoresolubleincoldsolvents Polarity Pressure Agitation
Nonpolarcompoundsdissolveinnonpolarsolvents,andpolarcompoundsdissolveinpolarsolvents. Alcoholandwaterarebothpolar,andtheyaremiscible.Oilis Ifoneliquidispolar,andtheotherisn't,theyareimmiscible. nonpolarandisimmiscibleinwater. Gasesdissolvebetterunderhigherpressure,duetogreaterforcespushingthegasmoleculesintothe Leavingthecapoffasodabottlewillletthecarbonationout. solvent. Ifasolutionisagitatedbystirringorshaking,thereisanincreaseinkineticmotionandcontactof particles.Therefore,therateofsolubilityincreases. Everyoneknowstostirtheircoffeeafteraddingsugar.
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DissolvingattheMolecularLevel
1. Theforcesbetweentheparticlesinthesolidmustbebroken.Thisisanendothermicprocesscalled dissociation. 2. Someoftheintermolecularforcesbetweentheparticlesintheliquidmustalsobebroken.Thisisendothermic. 3. Theparticlesofthesolidandtheparticlesinaliquidbecomeattracted.Thisisanexothermicprocesscalled solvation.
Example:DissolvingNaCl
Whensodiumchlorideisaddedtowater,itwilldissolve.Watermoleculesarepolar,andsodiumchlorideisionic(whichisverypolar).The positiveendsofthewatermolecules(thehydrogens)willbeattractedtothenegativechlorideions,andthenegativeendsofthewater molecules(theoxygens)willbeattractedtothepositivesodiumions.Theattractionsarestrongenoughtoseparatesodiumfromchloride, sothesolute dissociates,orbreaksapart.Thesoluteisthenspreadthroughoutthesolvent.Thepolarwatermoleculespreventtheions fromreattachingtoeachother,sothesaltstaysinsolution.
ImportantConcepts
Saturation
Asodiumioninsolvationwithwater.
Whenasolutioncanholdnomoresolute,itissaidtobe saturated.Thisoccurswhenthereisan equilibriumbetweenthe dissolvedandundissolvedsolute. Ifmoresolutecanbeadded,thesolutionis unsaturated. Ifasolutionhasmoresolutethanisnormallypossible,duetotheloweringorheighteningoftemperature,itissaidtobe supersaturated.Ifdisturbed,thesolutionwillrapidly formsolidcrystals. Solubilityisthemeasureofhowmanygramsofsolutecandissolvein100gramsofsolvent(orinthecaseofwater,soluteper100milliliters.)
Hydration
Sometimes,compoundsformcrystalswithaspecificamountofwaterinthem.Forexample,copper(II)sulfateiswrittenasCuSO45H2O.Foreverymoleofcopper(II)sulfate,there arefivemolesofwaterattached.Theatomsarearrangedinacrystallattice.Evenifdried,thecompoundwillstillbehydrated.Itwillnotfeelmoist,buttherearewatermolecules withinthecrystalstructureofthesolid. Intenseheatwillreleasethewaterfromthecompound.Itscolormaychange,indicatingachemicalchange.Whenthe anhydrouscompoundisdissolvedinwater,itwillbecome hydratedagain.
HeatsofSolution
Somechemicalschangetemperaturewhendissolved.Thisisduetoareleaseorabsorptionofheat.Thespecificchangeisknownasthe heatofsolution,measuredinkJ/mol.
Electrolytes
Somesubstancesbreakupintoionsandconductelectricitywhendissolved.Thesearecalled electrolytes.Allioniccompoundsareelectrolytes.Nonelectrolytes,ontheotherhand, donotconductelectricitywhendissolved.Electrolytesarethereasonthattapwaterconductselectricity.Tapwatercontainssaltsandotherions.Ifyouhavepurifiedwater,youwill findthatitdoesnotconductelectricityatall.Upondissolvingsomesalt,itconductselectricityverywell.Thepresenceofionsallowselectronstomovethroughthesolution,and electricitywillbeconducted.
SolubilityPracticeQuestions
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1.Inamixtureof50mLofbenzeneand48mLofoctane, a)whichsubstanceisthesolute? b)wouldthesetwosubstancesformasolution? 2.Solutionsareformedasphysicalreactions.Usingthisprinciple,nametwowaysinwhichsolutescanbeseparatedfromsolvents. 3.Threedifferentclear,colourlessliquidsweregentlyheatedinanevaporatingdish.LiquidAleftawhiteresidue,liquidBleftnoresidue,andliquidCleftwater.Identifyeachliquid solutionasapuresubstanceorasolution. 4.Comparethreebottlesofsoda.BottleAwasstoredatroomtemperature(25C),bottleBwasstoredat10C,andbottleCwasstoredat30C. a)Ifyouwantedafizzydrink,whichbottlewouldyouchoose? b)IfyouwantedtochangethegaspressureofbottleCtothatofbottleB,whatcouldyoudo? AnswerstoSolubilityPracticeQuestions
PropertiesofSolutions
Concentration
The concentrationofasolutionisthemeasureofhowmuchsoluteandsolventthereis.Asolutionis concentratedifitcontainsalargeamountofsolute,or diluteifcontainsa smallamount.
Molarity
Molarityisthenumberofmolesofsoluteperliterofsolution.ItisabbreviatedwiththesymbolM,andissometimesusedasaunitofmeasurement,e.g.a0.3molarsolutionofHCl. Inthatexample,therewouldbe3molesofHClforevery10litersofwater(orwhateverthesolventwas).
Molality
Molalityisthenumberofmolesofsoluteperkilogramofsolvent.Itisabbreviatedwiththesymbolm(lowercase),andissometimesusedasaunitofmeasurement,e.g.a0.3molal solutionofHBr.Inthatexample,therewouldbe3molesofHBrforevery10kilogramsofwater(orwhateverthesolventwas).
MoleFraction
Themolefractionissimplythemolesofsolutepermolesofsolution.Asanexample,youdissolveonemoleofNaClintothreemolesofwater.RememberthattheNaClwill dissociateintoitsions,sotherearenowfivemolesofparticles:onemoleNa+ ,onemoleCl,andthreemoleswater.Themolefractionofsodiumis0.2,themolefractionofchloride is0.2,andthemolefractionofwateris0.6. ThemolefractionissymbolizedwiththeGreekletter (chi),whichisoftenwrittensimplyasanX.
Dilution
Dilutionisaddingsolventtoasolutiontoobtainalessconcentratedsolution.Perhapsyouhaveuseddilutionwhenrunningalemonadestand.Tocutcosts,youcouldtakeahalffull jugofrich,concentratedlemonadeandfillitupwithwater.Theresultingsolutionwouldhavethesametotalamountofsugarandlemonjuice,butdoublethetotalvolume.Itsflavor wouldbeweakerduetotheaddedwater.
Thekeyconceptisthattheamountofsoluteisconstantbeforeandafterthedilutionprocess.Theconcentrationisdecreased(and
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Thekeyconceptisthattheamountofsoluteisconstantbeforeandafterthedilutionprocess.Theconcentrationisdecreased(and volumeincreased)onlybyaddingsolvent.
Thus,thenumberofmolesofsolutebeforeandafterdilutionareequal.
Chemistsoftenkeephighlyconcentrated solutionsofusefulchemicals.Theycan quicklyobtainmoredilutesolutionsof knownconcentrationbythismethod.
Bydefinitionofmolarity,youcanfindthemolesofsolvent.
Substitutingthesecondequationintothefirstgivesthe dilutionequation.
Todeterminetheamountofsolvent(usuallywater)thatmustbeadded,youmustknowtheinitialvolumeandconcentration,andthedesiredconcentration.Solvingfor inthe aboveequationwillgiveyouthe totalvolumeofthedilutedsolution.Subtractingtheinitialvolumefromthetotalvolumewilldeterminetheamountofpuresolventthatmustbe added.
IonicSolutes
Whenioniccompoundsdissolveinwater,theyseparateintoions.Thisprocessiscalled dissociation.Notethatbecauseofdissociation,therearemoremolesofparticlesinthe solutioncontainingionsthantherewouldbewiththesoluteandsolventseparated. Ifyouhavetwoglassesofwater,andyoudissolvesaltintooneandsugarintotheother,therewillbeabigdifferenceinconcentration.Thesaltwilldissociateintoitsions,butsugar (amolecule)willnotdissociate.IfthesaltwereNaCl,theconcentrationwouldbedoublethatofthesugar.IfthesaltwereMgCl2,theconcentrationwouldbetriple(therearethree ions).
SolubilityRules
Notallioniccompoundsaresoluble.Someioniccompoundshavesomuchattractiveforcebetweentheiranionsandcationsthattheywillnotdissociate.Thesesubstancesare insolubleandwillnotdissolve.Instead,theyclumptogetherasasolidinthebottomofsolution.Manyioniccompounds,however,willdissociateinwateranddissolve.Inthese cases,theattractiveforcebetweenionandwaterisgreaterthanthatbetweencationandanion.Thereareseveralrulestohelpyoudeterminewhichcompoundswilldissolveand whichwillnot.
SolubilityRules 1. AllcompoundswithGroup1ionsorammoniumionsaresoluble. 2. Nitrates,acetates,andchloratesaresoluble. 3. Compoundscontainingahalogenaresoluble,exceptthosewithfluorine,silver,ormercury.Iftheyhavelead,theyaresolubleonlyinhot water. 4. Sulfatesaresoluble,exceptwhencombinedwithsilver,lead,calcium,barium,orstrontium. 5. Carbonates,sulfides,oxides,silicates,andphosphatesareinsoluble,exceptforrule#1. 6. Hydroxidesareinsolubleexceptwhencombinedwithcalcium,barium,strontium,orrule#1.
Sometimes,whentwodifferentioniccompoundsaredissolved,theyreact,forminga precipitatethatisinsoluble.Predictingthesereactionsrequiresknowledgeoftheactivityseries
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Sometimes,whentwodifferentioniccompoundsaredissolved,theyreact,forminga precipitatethatisinsoluble.Predictingthesereactionsrequiresknowledgeoftheactivityseries andsolubilityrules.Thesereactionscanbewrittenwithallions,orwithoutthe spectatorions(theionthatdon'treact,presentonbothsidesofthereaction),aformatknownasthe netionicequation. Forexample,silvernitrateissoluble,butsilverchlorideisnotsoluble(seetheaboverules).Mixingsilvernitrateintosodiumchloridewouldcauseacloudywhiteprecipitatetoform. Thishappensbecauseofadoublereplacementreaction.
Electrolytes
Whensolutesdissociate(orifamolecule ionizes),thesolutioncanconductelectricity.Compoundsthatreadilyformions,thusbeinggoodconductors,areknownas strong electrolytes.Ifonlyasmallamountofionsareformed,electricityispoorlyconducted,meaningthecompoundisa weakelectrolyte.
ColligativeProperties
Somepropertiesarethesameforallsoluteparticlesregardlessofwhatkind.Theseareknownasthe colligativeproperties.Thesepropertiesapplyto idealsolutions,soin reality,thepropertiesmaynotbeexactlyascalculated.Inanidealsolution,therearenoforcesactingbetweenthesoluteparticles,whichisgenerallynotthecase.
VaporPressure
Allliquidshaveatendencyfortheirsurfacemoleculestoescapeandevaporate,eveniftheliquidisnotatitsboilingpoint.Thisisbecausetheaverageenergyofthemoleculesis toosmallforevaporation,butsomemoleculescouldgainaboveaverageenergyandescape. Vaporpressureisthemeasureofthepressureoftheevaporatedvapor,andit dependsonthetemperatureofthesolutionandthequantitiesofsolute.Moresolutewilldecreasevaporpressure.
Thevaporpressureisgivenby Rauolt'sLaw,where isthemolefractionofthesolvent.Noticethatthevaporpressure equalsthatofthepuresolventwhenthereisnosolute( ).If ,therewouldbenovaporpressureatall.This couldonlyhappeniftherewerenosolvent,onlysolute.Asolidsolutehasnovaporpressure. Iftwo volatilesubstances(bothhavevaporpressures)areinsolution,Rauolt'sLawisstillused.Inthiscase,Rauolt'sLaw isessentiallyalinearcombinationofthevaporpressuresofthesubstances.Twoliquidsinsolutionbothhavevapor pressures,sothisequationmustbeused.
Thesecondequationshowstherelationshipbetweenthesolvents.Iftwoliquidsweremixedexactlyhalfandhalf,thevaporpressureoftheresultingsolutionwouldbeexactly halfwaybetweenthevaporpressuresofthetwosolvents. Anotherrelationin Henry'sLaw,whichshowstherelationshipbetweengasandpressure.ItisgivenbyCg=kP g,whereCisconcentrationandPispressure.Asthepressuregoes up,theconcentrationofgasinsolutionmustalsoincrease.ThisiswhysodacansreleasegaswhentheyareopenedThedecreaseinpressureresultsinadecreaseinconcentration ofCO2inthesoda.
Exerciseforthereader At50Cthevaporpressureofwateris11kPaandthevaporpressureofethanolis30kPa.Determinetheresultingvaporpressureifasolution contains75%waterand25%ethanol(bymoles,notmass).
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BoilingPointElevation
Aliquidreachesitsboilingpointwhenitsvaporpressureisequaltotheatmospherearoundit.Becausethepresenceofsolutelowersthevaporpressure,theboilingpointisraised. Theboilingpointincreaseisgivenby:
Thereducedvaporpressureincreasestheboilingpointoftheliquidonlyifthesoluteitselfis nonvolatile,meaningitdoesn'thaveatendencytoevaporate.Foreverymoleofnon volatilesoluteperkilogramofsolvent,theboilingpointincreasesbyaconstantamount,knownasthe molalboilingpointconstant( ).Becausethisisacolligativeproperty, isnotaffectedbythekindofsolute.
FreezingPointDepression
Aliquidreachesitsfreezingtemperaturewhenitsvaporpressureisequaltothatofitssolidform.Becausethepresenceofthe solutelowersthevaporpressure,thefreezingpointislowered.Thefreezingpointdepressionisgivenby: Thisexplainswhyroadsaresaltedinthe winter.
Again,thisequationworksonlyfornonvolatilesolutes.Thetemperatureofthefreezingpointdecreasesbyaconstantamountforeveryonemoleofsoluteaddedperkilogram solvent.Thisconstant( )isknownasthe molarfreezingpointconstant.
Osmosis
Ifyoustudiedbiology,youwouldknowthat osmosisisthemovementofwaterthroughamembrane.Iftwosolutionsofdifferentmolarity areplacedonoppositesidesofa semipermiablemembrane,thenwaterwilltravelthroughthemembranetothesidewithhighermolarity. Thishappensbecausethewatermoleculesare"attached"tothesolventmolecules,sotheycannottravelthroughthemembrane.Asa result,thewateronthesidewithlowermolaritycanmoreeasilytravelthroughthemembranethanthewaterontheotherside. Thepressureofthisosmosisisgivenintheequation
Wherepiisthepressure,Mismolarity,Risthegasconstant,andTistemperatureinKelvin.
ElectrolytesandColligativeProperties
Osmosisresultsfromthetendencyfor concentrationtodistributeitselfevenly.
Whenonemoleoftablesaltisaddedtowater,thecolligativeeffectsare doublethosethatwouldhaveoccurredifsugarwereadded instead.Thisisbecausethesaltdissociates,formingtwiceasmanyparticlesassugarwould.Thisdissociation,calledthe Van'tHoffFactordescribeshowmanyparticlesthatare dissociatedintothesolutionandmustbemultipliedintotheBoilingPointElevationorVaporPressureLoweringequations.
Sugarisacovalentmolecule.Nodissociationoccurswhendissolved. Tablesaltisanioniccompoundandastrongelectrolyte.Total dissociationoccurswhendissolved,doublingtheeffectsofcolligative properties.
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Magnesiumbromideisalsoionic.Thecolligativeeffectswillbetripled.
ThoughextremelyusefulforcalculatingthegeneralVan'tHoffFactor,thissystemofcalculationisslightlyinaccuratewhenconsideringions.Thisisbecausewhenionsarein solution,theymayinteractandclumptogether,lessingtheeffectoftheVan'tHofffactor.Inaddition,morestronglychargedionsmayhaveasmallereffect.Forexample,CaOwould belesseffectiveasanelectrolytethanNaCl.
AcidsandBases
AcidBaseReactionTheories
Acidsandbasesareeverywhere.Somefoodscontainacid,likethecitricacidinlemonsandthelacticacidindairy.Cleaningproductslikebleachandammoniaarebases.Chemicals thatareacidicorbasicareanimportantpartofchemistry. Severaldifferenttheoriesexplainwhatcomposesan acidanda base.Thefirstscientificdefinitionofanacidwasproposedbythe FrenchchemistAntoineLavoisierintheeighteenthcentury.Heproposedthatacidscontainedoxygen,althoughhedidnotknowthe dualcompositionofacidssuchashydrochloricacid(HCl).Overtheyears,muchmoreaccuratedefinitionsofacidsandbaseshave beencreated.
HelpfulHint!
Youmayneedtorefreshyour memoryonnamingacids.
ArrheniusTheory
TheSwedishchemistSvanteArrheniuspublishedhistheoryofacidsandbasesin1887.Itcanbesimplyexplainedbythesetwopoints:
ArrheniusAcidsandBases 1. Anacidisasubstancewhichdissociatesinwatertoproduceoneormorehydrogenions(H+ ). 2. Abaseisasubstancewhichdissociatesinwatertoproduceoneormorehydroxideions(OH).
Basedonthisdefinition,youcanseethatArrheniusacidsmustbesolubleinwater.Arrheniusacidbasereactionscanbesummarizedwiththreegenericequations:
Anacidwilldissociateinwaterproducinghydrogenions.
Abase(usuallycontainingametal)willdissociateinwatertoproducthydroxideions.
Acidsandbaseswillneutralizeeachotherwhenmixed.Theyproducewaterandanionicsalt,neitherofwhichare acidicorbasic.
TheArrheniustheoryissimpleanduseful.Itexplainsmanypropertiesandreactionsofacidsandbases.Forinstance,mixinghydrochloricacid(HCl)withsodiumhydroxide(NaOH) resultsinaneutralsolutioncontainingtablesalt(NaCl).
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However,theArrheniustheoryisnotwithoutflaws.Therearemanywellknownbases,suchasammonia(NH3)thatdonotcontainthehydroxideion.Furthermore,acidbase reactionsareobservedinsolutionsthatdonotcontainwater.Toresolvetheseproblems,thereisamoreadvancedacidbasetheory.
BrnstedLowryTheory
TheBrnstedLowrytheorywasproposedin1923.ItismoregeneralthantheArrheniustheoryallArrheniusacids/basesarealsoBrnstedLowryacids/bases(butnotnecessarily viceversa).
SvanteArrhenius
BrnstedLowryAcidsandBases 1. Anacidisasubstancefromwhichaproton(H+ ion)canberemoved.Essentially,anacid donatesprotonstobases. 2. Abaseisasubstancetowhichaproton(H+ )canbeadded.Essentially,abase acceptsprotonsfromacids.
Acidsthatcandonateonlyoneprotonare monoprotic,andacidsthatcandonatemorethanoneprotonare polyprotic. ThesereactionsdemonstratethebehaviorofBrnstedLowryacidsandbases:
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Anacid(inthiscase,hydrochloricacid)willdonateaprotontoabase(inthiscase,wateristhebase).Theacid losesitsprotonandthebasegainsit.
Waterisnotnecessary.Inthiscase,hydrochloricacidisstilltheacid,butammoniaactsasthebase.
Thesamereactionishappening,butnowinreverse.Whatwasonceanacidisnowabase(HClCl)andwhat wasonceabaseisnowanacid(NH3NH4+ ).Thisconceptiscalled conjugates,anditwillbeexplainedinmore detaillater.
Twoexamplesofacids(HClandH3O+ )mixingwithbases(NaOHandOH)toformneutralsubstances(NaCland H2O).
Abase(sodiumhydroxide)willacceptaprotonfromanacid(ammonia).Aneutralsubstanceisproduced(water), whichisnotnecessarilyapartofeveryreaction.Comparethisreactiontothesecondone.Ammoniawasabase, andnowitisanacid.Thisconcept,called amphoterism,isexplainedlater.
TheBrnstedLowrytheoryisbyfarthemostusefulandcommonlyuseddefinition.FortheremainderofGeneralChemistry,youcanassumethatanyacids/basesusetheBrnsted Lowrydefinition,unlessstatedotherwise.
ThisBrnstedLowryaciddonatesaproton (ingreen)towater(thebase).
LewisTheory
TheLewisdefinitionisthemostgeneraltheory,havingnorequirementsforsolubilityorprotons.
LewisAcidsandBases 1. Anacidisasubstancethatacceptsalonepairofelectrons. 2. Abaseisasubstancethatdonatesalonepairelectrons.
Lewisacidsandbasesreacttocreatean adduct,acompoundinwhichtheacidandbasehavebondedbysharingtheelectronpair.Lewisacid/basereactionsaredifferentfrom redoxreactionsbecausethereisnochangeinoxidationstate.

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ThisreactionshowsaLewisbase(NH3) donatinganelectronpairtoaLewisacid (H+ )toformanadduct(NH4+ ).
AmphoterismandWater
Substancescapableofactingaseitheranacidorabaseare amphoteric.Wateristhemostimportantamphotericsubstance.Itcanionizeintohydroxide(OH,abase)orhydronium (H3O+ ,anacid).Bydoingso,wateris 1. IncreasingtheH+ orOHconcentration(Arrhenius), 2. Donatingoracceptingaproton(BrnstedLowry),and 3. Acceptingordonatinganelectronpair(Lewis). Waterwilldissociateveryslightly(whichfurtherexplainsitsamphotericproperties).
Thepresenceofhydrogenionsindicatesanacid,whereasthepresenceofhydroxideions indicatesabase.Beingneutral,waterdissociatesintobothequally.
Thisequationismoreaccuratehydrogenionsdonotexistinwaterbecausetheybond toformhydronium.
Ammonia
Anothercommonexampleofanamphotericsubstanceisammonia.Ammoniaisnormallyabase,butinsomereactionsitcanactlikean acid.
H+ ionsactuallyexistashydronium,H3O+ .
Ammoniaactsasabase.Itacceptsaprotontoform ammonium.
Ammoniaalsoactsasanacid.Here,itdonatesaprotontoform amide.
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Ammonia'samphotericpropertiesarenotoftenseenbecauseammoniatypicallyactslikeabase.Water,ontheotherhand,iscompletelyneutral,soitsacidandbasebehaviorsare bothobservedcommonly.
ConjugateAcidsandBases
Inallthetheories,theproductsofanacidbasereactionarerelatedtotheinitialreactantsofthereaction.Forexample,intheBrnstedLowrytheory,thisrelationshipisthe differenceofaprotonbetweenareactantandproduct.Twosubstanceswhichexhibitthisrelationshipforma conjugateacidbasepair.
BrnstedLowryConjugatePairs Anacidthathasdonateditsprotonbecomesa conjugatebase. Abasethathasacceptedaprotonbecomesa conjugateacid.
Hydroiodicacidreactswithwater(whichservesasabase).Theconjugatebaseistheiodideionandthe conjugateacidisthehydroniumion.Theacidsarewritteninred,andthebasesarewritteninblue.One conjugatepairiswrittenboldandtheotherconjugatepairisincursive.
Ammonia(basic)reactswithwater(theacid).Theconjugateacidisammoniumandtheconjugatebaseis hydroxide.Again,acidsarewritteninred,andthebasesarewritteninblue.Theconjugatepairsare distinguishedwithmatchingfonts.
StrongandWeakAcids/Bases
A strongacidisanacidwhichdissociatescompletelyinwater.Thatis, alltheacidmoleculesbreakupintoionsandsolvate(attach)towatermolecules.Therefore,the concentrationofhydroniumionsinastrongacidsolutionisequaltotheconcentrationoftheacid. Themajorityofacidsexistas weakacids,anacidwhichdissociatesonlypartially.Onaverage,onlyabout1%ofaweakacidsolutiondissociatesinwaterina0.1mol/Lsolution. Therefore,theconcentrationofhydroniumionsinaweakacidsolutionisalwayslessthantheconcentrationofthedissolvedacid. Strongbasesand weakbasesdonotrequireadditionalexplanationtheconceptisthesame. Thisexplainswhy,inalloftheaboveexamplereactions,thereversechemicalreactiondoesnotoccur.Thestrongeracid/basewillprevail,andtheweakeronewillnotcontributeto theoverallacidity/basicity.Forexample,hydrochloricacidisstrong,andupondissociationchlorideionsareformed.Chlorideionsareaweakbase,butthesolutionisnotbasic becausetheacidityofHClisoverwhelminglystrongerthanbasicityofCl. Mostacidsandbasesareweak.Youshouldbefamiliarwiththemostcommonstrongacidsandassumethatanyotheracidsareweak.
HelpfulHint!
Althoughtheotherhalogensmake strongacids,hydrofluoricacid(HF)is
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Formula HClO4 HNO3 H2SO4
StrongAcid Perchloricacid Nitricacid Sulfuricacid
aweakacid.Despitebeingweak,itis incrediblycorrosivehydrofluoric aciddissolvesglassandmetal!
HCl,HBr,HI Hydrohalicacids Withinaseriesof oxyacids,theionswiththegreatestnumberofoxygenmoleculesarethestrongest.Forexample,nitricacid(HNO3)isstrong,butnitrousacid(HNO2)isweak. Perchloricacid(HClO4)isstrongerthanchloricacid(HClO3),whichisstrongerthantheweakchlorousacid(HClO2).Hypochlorousacid(HClO)istheweakestofthefour. CommonstrongbasesarethehydroxidesofGroup1andmostGroup2metals.Forexample,potassiumhydroxideandcalciumhydroxidearesomeofthestrongestbases.Youcan assumethatanyotherbases(includingammoniaandammoniumhydroxide)areweak. Formula LiOH NaOH KOH RbOH CsOH StrongBase Lithiumhydroxide Sodiumhydroxide Potassiumhydroxide Rubidiumhydroxide Cesiumhydroxide
Ca(OH)2 Calciumhydroxide Sr(OH)2 Strontiumhydroxide Ba(OH)2 Bariumhydroxide

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PropertiesofAcidsandBases
Nowthatyouareawareoftheacidbasetheories,youcanlearnaboutthephysicalandchemicalpropertiesofacidsandbases.Acidsandbaseshaveverydifferentproperties, allowingthemtobedistinguishedbyobservation.
Indicators
Madewithspecialchemicalcompoundsthatreactslightlywithanacidorbase, indicatorswillchangecolorinthepresenceofanacidorbase.Acommonindicatoris litmuspaper. Litmuspaperturnsredinacidicconditionsandblueinbasicconditions. Phenolphthaleinpurpleiscolorlessinacidicandneutralsolutions,butitturnspurpleoncethesolution becomesbasic.Itisusefulwhenattemptingtoneutralizeanacidicsolutiononcetheindicatorturnspurple,enoughbasehasbeenadded.
Conductivity
Alessinformativemethodistotestforconductivity.Acidsandbasesinaqueoussolutionswillconductelectricitybecausetheycontaindissolvedions.Therefore,acidsandbasesare electrolytes.Strongacidsandbaseswillbestrongelectrolytes.Weakacidsandbaseswillbeweakelectrolytes.Thisaffectstheamountofconductivity.
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However,acidswillreactwithmetal,sotestingconductivitymaynotbeplausible.
Physicalproperties
Thephysicalpropertiesofacidsandbasesareopposites. Acids Taste sour Bases bitter
Feel stinging slippery Odor sharp odorless
Thesepropertiesareverygeneraltheymaynotbetrueforeverysingleacidorbase. Anotherwarning:ifanacidorbaseisspilled,itmustbecleanedupimmediatelyandproperly(accordingtotheproceduresofthelabyou areworkingin).If,forexample,sodiumhydroxideisspilled,thewaterwillbegintoevaporate.Sodiumhydroxidedoesnotevaporate,so theconcentrationofthebasesteadilyincreasesuntilitbecomesdamagingtoitssurroundingsurfaces.
ChemicalReactions
Neutralization Acidswillreactwithbasestoformasaltandwater.Thisisa neutralizationreaction.Theproductsofaneutralizationreactionaremuch lessacidicorbasicthanthereactantswere.Forexample,sodiumhydroxide(abase)isaddedtohydrochloricacid.
Bromothymolblueisanindicatorthat turnsblueinabase,oryellowinacid.
Thisisadoublereplacementreaction. Acids
Acidsreactwithmetaltoproduceametalsaltandhydrogengasbubbles.
Acidsreactwithmetalcarbonatestoproducewater,CO2gasbubbles,andasalt.
Acidsreactwithmetaloxidestoproducewaterandasalt.
Bases
Basesaretypicallylessreactiveandviolentthanacids.Theydostillundergomanychemicalreactions,especiallywithorganiccompounds.Acommonreactionsis saponificiation:the
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Basesaretypicallylessreactiveandviolentthanacids.Theydostillundergomanychemicalreactions,especiallywithorganiccompounds.Acommonreactionsis saponificiation:the reactionofabasewithfatoroiltocreatesoap.
Saponificationconvertsan"ester"intoan "alcohol"andsalt.Thisisanorganicreaction outsidethescopeofGeneralChemistry.
PracticeQuestions
1.Namethefollowingcompoundsthatwillform,andidentifyasanacidorbase: a)Br+H b)2H+SO3 c)K+H d)2H+SO6 e)3He+P 2 f)H+BrO100 g)N+C duckseverywhere 2.justifyyouranswerwithequationthatsodiumacetategivesbasicsolutionwhileammoniumchlorideanacidicsolutionwithwater. 3.Inaconductivitytest,5differentsolutionsweresetupwithlightbulbs.Thefollowingobservationswererecorded: SolutionAglowedbrightly. SolutionBgloweddimly. SolutionCgloweddimly. SolutionDdidnotglow. SolutionEglowedbrightly. a)Whichsolution(s)couldcontainstrongbases? b)Whichsolution(s)couldcontainweakacids? c)Whichsolution(s)couldcontainions? d)Whichsolution(s)couldcontainpurewater? e)Basedsolelyontheseobservations,woulditbepossibletodistinguishbetweenacidicandbasicsolutions? 4.Identitytheconjugatebaseandconjugateacidinthesefollowingequations:
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a)HCl+H2OH3O+ +Cl b)HClO+H2OClO+H3O+ c)CH3CH2NH2+H2OCH3CH2NH3+ +OH
5.IdentifythesebasesasArrhenius,BrnstedLowry,orboth. a)strontiumhydroxide b)butyllithium(C4H9Li) c)ammonia d)potassiumhydroxide e)potassiumiodide 6.BasedontheBrnstedLowryTheoryofAcidsandBases,wouldyouexpectpurewatertohavenodissolvedionswhatsoever?Explain,usingabalancedchemicalequation.
Notes
1. ^Brown,TheodoreE.Lemay,H.EugeneBursten,BruceE.Murphy,CatherineWoodward,Patrick(2009),Chemistry:TheCentralScience(11thed.),NewYork:Prentice Hall,ISBN0136006175. AnswerstoPropertiesofAcidsandBasesPracticeQuestions
TitrationandpH
IonizationofWater
Waterisaveryweakelectrolyte.Itwilldissociateintohydroxideandhydroniumions,althoughonlyinaverysmallamount.Becausepurewateriscompletelyneutral,italways dissociatesinequalamountsofbothhydroxideandhydronium.Onceacidicorbasicsubstanceshavebeenaddedtopurewater,theconcentrationoftheionswillchange.Regardless ofwhichacidbasetheoryisused,acidsandbasesallhaveoneimportantthingincommon:
AllacidsincreasetheH+ concentrationofwater. AllbasesincreasetheOHconcentrationofwater.
Furthermore,theconcentrationofhydrogenionsmultipliedbytheconcentrationofhydroxideionsisaconstant.Thisconstantisknownasthe ionizationconstantofwater,or Kw.At roomtemperatureitequals1014mol2/L2.Thus:
Inaneutralsolution,theconcentrationsofH+ andOHarebothequalto107.Usingtheaboveequation,theconcentrationofoneioncanbedeterminediftheconcentrationofthe otherionisknown.Thisequationfurtherdemonstratestherelationshipbetweenacidsandbases:astheacidity(H+ )increases,thebasicity(OH)mustdecrease.

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ThepHScale
Tomeasuretheacidityorbasicityofasubstance,thepHscaleisemployed.
ThepHScale AcompletelyneutralsubstancehasapHof7. AcidshaveapHbelow7 BaseshaveapHabove7.
pHusuallyrangesbetween0and14,butitcanbeanyvalue.Batteryacid,forexample,hasanegativepHbecauseitissoacidic.
DefinitionofpH
ThepHscaleismathematicallydefinedas:
Substancesthatreleaseprotonsorincreasetheconcentrationofhydrogenions(orhydroniumions)willlowerthepHvalue.
pOH
Thereisalsoalesscommonscale,thepOHscale.Itisdefinedas:
SubstancesthatabsorbprotonsorincreasetheconcentrationofhydroxideionswilllowerthepOHvalue. ThesumofpHandpOHisalways14atroomtemperature:
VariouspHvalues.
CalculatingpH
Astrongacidorstrongbasewillcompletelydissociateinwater,sotheconcentrationoftheacid/baseisequaltotheconcentrationofH+ orOH.Ifyouknowtheconcentrationofthe acidorbase,thenyoucansimplyplugthatnumberintothepHorpOHformula.ThesumofpHandpOHwillalwaysequal14atroomtemperature,soyoucaninterconvertthese twovalues. IfyouknowtheH+ concentrationandneedtoknowtheOHconcentration(orviceversa),usethedefinitionofK wabove.Theproductofthetwoionconcentrationswillalwaysequal 1014atroomtemperature.
Titration
Titrationisthecontrolledmixingofasolutionwithknownconcentration(the standardsolution)toanothersolutiontodetermineitsconcentration.Onesolutionisacidicandthe
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Titrationisthecontrolledmixingofasolutionwithknownconcentration(the standardsolution)toanothersolutiontodetermineitsconcentration.Onesolutionisacidicandthe otherisbasic.An indicatorisaddedtothemixture.Anindicatormustbeselectedsothatitchangescolorwhenequalamountsofacidandbasehavebeenadded.Thisisknownas the equivalencepoint.ThisdoesnotnecessarilymeanthatthepHis7.0. Oncetheequivalencepointhasbeenreached,theunknownconcentrationcanbedeterminedmathematically.
PracticeQuestions
1)5.00gofNaOHaredissolvedtomake1.00Lofsolution. aWhatistheconcentrationofH+ ? bWhatisthepH? AnswersforTitrationandpH
Polyproticacidshavemultipleequivalence points.
BufferSystems
Introduction
Buffersystemsaresystemsinwhichthereisasignificant(andnearlyequivalent)amountofaweakacidanditsconjugatebaseoraweakbaseanditsconjugateacidpresentin solution.Thiscouplingprovidesaresistancetochangeinthesolution'spH.Whenstrongacidisadded,itisneutralizedbytheconjugatebase.Whenstrongbaseisadded,itis neutralizedbytheweakacid.However,toomuchacidorbasewillexceedthebuffer's capacity,resultinginsignificantpHchanges.
Consideranarbitraryweakacid,HA,anditsconjugatebase,A ,inequilibrium.
TheadditionofastrongacidwillcauseonlyaslightchangeinpHduetoneutralization.
Likewise,theadditionofastrongbasewillcauseonlyaslightchangeinpH.
BuffersareusefulwhenasolutionmustmaintainaspecificpH.Forexample,bloodisabuffersystembecausethelifeprocessesinahumanonlyfunctionwithinaspecificpHrange of7.35to7.45.When,forexample,lacticacidisreleasedbythemusclesduringexercise,bufferswithinthebloodneutralizeittomaintainahealthypH.
MakingaBuffer
Onceagain,let'sconsideranarbitraryweakacid,HA,whichispresentinasolution.Ifweintroduceasaltoftheacid'sconjugatebase,sayNaA(whichwillprovidetheA ion),we nowhaveabuffersolution.Ideally,thebufferwouldcontainequalamountsoftheweakacidandconjugatebase. InsteadofaddingNaA,whatifastrongbasewereadded,suchasNaOH?Inthatcase,thehydroxideionswouldneutralizetheweakacidandcreatewaterandA ions.Ifthe solutioncontainedonlyA ions,thenastrongacidlikeHClwereadded,theywouldneutralizeandcreateHA. Asyoucansee,therearethreewaystocreateabuffer:
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Buffers 1HA+1A 1HA+OH 1A +H+ 1B+1HB + 1B+H+ 1HB + +OH
Allsixofthecombinationswillcreateequalamountsofaweakacidanditsconjugatebase,oraweakbaseanditsconjugateacid.
BuffersandpH
TodeterminethepHofabuffersystem,youmustknowtheacid's dissociationconstant.Thisvalue, (or forabase)determinesthestrengthofanacid(orbase).Itis exploredmorethoroughlyintheEquilibriumunit,butfornowitsufficestosaythatthisvalueissimplyameasureofstrengthforacidsandbases.Thedissociationconstantsforacids andbasesaredeterminedexperimentally. The HendersonHasselbalchequationallowsthecalculationofabuffer'spH.Itis:
Forabuffercreatedfromabase,theequationis:
Usingtheseequationsrequiresdeterminingtheratioofbasetoacidinthesolution.
ReactionsofAcidsandBases
Overview
Tosummarizethepropertiesandbehaviorsofacidsandbases,thischapterlistsandexplainsthevariouschemicalreactionsthattheyundergo.Youmaywishtoreviewchemical equationsandtypesofreactionsbeforeattemptingthischapter. Thefollowingreactionsare netionicequations.Inotherwords, spectatorionsarenotwritten.Ifaniondoesnotpartakeinthereaction,itissimplyexcluded.Thespectatorions canbefoundbecausetheyoccuronboththereactantandtheproductsideoftheequation.Crossthemoutandrewritetheequationwithoutthem.Ofcourse,thecoefficientsmust beequal. Cancelingoutthespectatorionsexplainsthe net ofnetionicequations.The ionicpartmeansthatdissolvedcompoundsarewrittenasionsinsteadofcompounds.Acids,bases,and saltsareallionic,sotheyarewrittenasseparateionsiftheyhavedissociated.
NetIonicEquations Solublesaltsarewrittenasions.
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e.g.:Na+ +Cl Solids,liquids,andgasesarewrittenascompounds. e.g.:NaCl(s),H2O(l),HCl(g) Strongacidsandstrongbasesarewrittenasions(becausetheydissociatealmostcompletely). e.g.:H+ +NO3 Weakacidsandweakbasesarewrittenascompounds(becausetheybarelydissociate). e.g.:HNO2
Asanexample,sodiumbicarbonate(NaHCO3)wouldbewrittenasNa+ andHCO3becausethesaltwilldissociate,butthebicarbonatewillnotdissociate(it'sa weakacid).
Neutralization
Whenanacidandabasereact,theyformaneutralsubstance,oftenwaterandasalt. First,let'sexaminetheneutralizationofastrongacidwithastrongbase.
Solidpotassiumhydroxideisaddedtoanaqueoussolutionofhydrochloricacid.Noticehowthesolidis writtenasacompound,buttheacidiswrittenasionsbecauseitdissociates.
Thehydrogenionswillreactwithhydroxideionstoformwater.
Ignoringspectatorions,thisisthe netionicequation.
Now,let'sseesomeexamplesinvolvingweakacidsandweakbases. Excesshydrochloricacidisaddedtoasolutionofsodiumphosphate.Phosphoricacidisweak,sothephosphateionswill reactwithhydrogenions.Theresultisasolutionwithsome,butmuchless,hydrogenions,soitismuchclosertoneutral thaneitheroftheoriginalreactants.
Equimolaramountsofsodiumphosphateandhydrochloricacidaremixed.Noticethedifferencebetweenthisreactionand thepreviousone.
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Astrongbaseisaddedtoasolutionofcalciumbicarbonate.(Bicarbonateisaweakacid.)
Astrongacidisaddedtoasolutionofcalciumbicarbonate.Gasbubblesappear.
Manyreactionsresultintheformationofgasbubblesorasolidprecipitatethatwillmakethesolutioncloudy.Thelastequationbringsupaninterestingapplication.Manyrocksand mineralscontaincalciumcarbonateorcalciumbicarbonate.Toidentifytheserocks,geologistscanperformthe"acidtest".Adropofacidisapplied,andthepresenceofgasbubbles indicatescarbonate. Herearemoreexamplesofneutralizationreactions.
Solidammoniumchloridecrystalsaredissolvedintoasolutionofsodiumhydroxide.Thesmellofammoniais detected.
Ammoniagasisbubbledthroughasolutionofhydrochloricacid.Thisreactionisessentiallytheoppositeof theprevious.Inthatreaction,ammoniumionsreactwithbasetoformammoniagas.Inthisreaction, ammoniagasreactswithacidtoformammoniumions.
Ammonia(aweakbase)reactswithaceticacid(alsoweak).Theresultingsolutionisnearlyneutral,butitwill beslightlybasicbecauseammoniaisstrongerthanaceticacid.
Hydrogensulfidegasisbubbledintoastrongbase.
Astrongacidisaddedtotheaboveresult,andhydrogensulfidegasisreleased.
Anhydrides
An anhydrideisasubstancethatdoesnotcontainwater.Morespecifically,itisasubstancethatreactswithwatertoformanacidorbase.Anhydridesareusuallyintheformofa gasthatdissolvesintowaterandreactstoformanacidorbase.Theycanalsobesolidsthatwillreactwithwater.
Gaseousdinitrogenpentoxideisbubbledthroughwatertoformnitricacid.
Dinitrogentrioxideismixedwithwatertoformnitrousacid.
Themaindifferencebetweenthosetwoequationsisthefactthatnitrousacidisweakandthusdoesnotdissociate,whereasnitricacidisstronganddissociatesintoions.
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Hereareafewmoreexamplesofanhydridereactions.
Solidpotassiumoxideisaddedtowatertoformastrongbase.
Phosphorus(V)oxidepowderismixedintowatertoformaweakacid.
Itisimportanttorememberwhichacidsarestrongandwhichareweak.Reviewthisifnecessary. Forexample,sulfurdioxidegas(acidicanhydride)isbubbledthroughasolutionofcalciumhydroxide(basic).
First,determinethereactionoftheanhydridewithwater.
Then,determinethereactionoftheacidandbase.Thisisadouble replacementreaction.
Addthetworeactionstogether.
Canceloutspectators.Also,calciumhydroxideshouldbeionized(butcalcium sulfiteisasolidprecipitate).Thisisthefinal netionicequation.
Herearemoreexamples.
Calciumoxidecrystals(basicanhydrides)areaddedtoastrongacid.Noticethatitdoesnotmatterwhattheacidis(nitric, sulfuric,etc.)becauseitisstrongandthisreactiononlyrequiresthehydrogenions.Inotherwords,theanionsofthestrongacid arespectatorsandarenotwritten.
Excesssulfurdioxidegasisbubbledintoadilutesolutionofstrongbase.Thebaseisthelimitingreactant.
Sulfurdioxidegasisbubbledintoanexcessofbasicsolution.
Rememberthatwaterisinvolvedinthesereactions,butitnotwrittenifitoccursonbothsidesoftheequation. Solidcalciumoxide(basicanhydride)isexposedtodryicegas(acidicanhydride).Theresultingsolidisasalt.
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Solidcalciumoxideisexposedtoastreamofsulfurtrioxdegas.Theresultingsolidisaneutralsalt.
Hydrolysis
AsaltofaweakacidandstrongbasedissociatesandreactsinwatertoformOH.AsaltofastrongacidandweakbasedissociatesandreactsinwatertoformH+ .Thisprocessis called hydrolysis. Inthisfirstexample,aluminumnitrateisdissolvedinwater.
First,thesaltdissociatesinthewater.Itisn'tnecessarytowriteH2Ointhisreaction.
Now,atleastoneoftheionswillreactwithwater.Youknowthatnitricacidisstrong,sothenitrateion willnottakeanH+ ionfromwater.Instead,thealuminumionwillreactwithwater,releasinga hydrogenion.
Thisisthe netionicequation.Theresultingsolutionisacidic.
Thesolutionisacidicnotbecausenitricacidisstrong,butbecausealuminumisaweakbase. Hereisaneasierexample.
First,thesaltdissociates.Again,theH2Oneednotbewritten.
Sodiumionswillnotreactwithwater.Eveniftheydid,theywouldformNaOH,whichisastrongbase,soit wouldimmediatelydissociate.Instead,theNO2reactswithwater.Beingtheconjugateofaweakacid,the nitriteionswillacceptaprotonfromwatertoformnitrousacid(weak)andhydroxideions(basic).
Thisisthenetionicequationforthehydrolysisofsodiumnitrite.Theresultingsolutionisbasic.
LewisAcids/Bases
Lewisacidsacceptanelectronpair.Lewisbasesdonateanelectronpair.Togethertheyreactandbondtoforman adduct . Lewisacids/basesdonotrequirethepresenceofwater.However,H+ canbethoughofasaLewisacidbecauseitacceptselectronpairs.OHcandonateanelectronpair,makingit aLewisbase.
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Borontrifluoride(Lewisacid)isexposedtoammonia(aLewisbase,asshownbytheelectronpairovertheN).Theelectronpairis sharedbetweenthenitrogenandboron,creatingabond.(TheborontrifluorideiswrittenbackwardsasF3Bonlytodemonstrate theBNbond.Itsstructurehasnotchanged.)
DiboraneacceptsthetwoelectronsfromHandformsaLewisadduct.
PracticeProblems
Writethenetionicequationsforthefollowing.Makenoteofanysolidprecipitatesorgasbubblesthatwouldform. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Equimolarsolutionsofsodiumbiphosphateandpotassiumhydroxidearemixed. Equimolarsolutionsofsodiumbiphosphateandhydrochloricacidaremixed. Excesssulfurdioxidegasisbubbledintoadilutesolutionofsodiumhydroxide.Acidisthenadded. Aluminumchlorideisdissolvedintowater. Sodiumfluorideisdissolvedintowater.Strongacidisthenadded. Solidcalciumoxideisexposedtoastreamofsulfurtrioxidegas.Iftheresultingcompoundisdissolved,willthesolutionbeacidic,basic,orneutral? Gaseoushydrogenchlorideisbubbledintoasolutionofsilvernitrate. Ammoniumchloridecrystalsaredissolvedinwater.Sodiumhydroxideisthenadded. Calciumhydroxidecrystalsaredissolvedintoasolutionofsodiumbicarbonate. Phosphinegasissprayedontopebblesofaluminumtrichloride.(Hint:theseareLewisacids/bases.)
AnswerstoPracticeProblems
Solids
CharacteristicsofSolids
PhasesofMatter
Shapeandvolumearebothdefiniteinsolids.Althoughsolidshave arigidshape,alargeamountofforcecancausedeformationtothestructureofasolid.Therearethreetypesofdeformation:
Brittledeformationcausesbondstobreakinanirregularway.Shreddingpaperandshatteringglassaregoodexamples. Elasticdeformationistemporary.Themoleculeswillreturntotheiroriginalpositionsassoonastheforceisremoved.Rubberbandsand tiresareelastic,aswellassteelrodsandwoodenboards.

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Plasticdeformationispermanent.Plasticdeformationcanbeobservedbybendingametalspoon.
Mostmaterialsarecapableofallthreetypesofdeformation.Smallamountsofstresscauseelasticdeformation,butlargeamountswill causeplasticdeformation.Intheeventofrepeateddeformationortremendousstress,brittledeformationoccurs. Solidsare incompressible.Solidsmaybreakordeformunderstress,buttheytoleratelittlecompression.Forinstance,awoodenplank willbreakifforceisapplied,butitwillnotcompresslikeasponge.Theonlyreasonspongescompressisbecausetheycontainairpockets andundergoelasticdeformation.Otherwise,solidswillnotcompress.Atthemolecularlevel,thishappensbecausetheintermolecular bondsdonotchangesizewithoutbreaking. Somesolids,usuallymetals,havepropertieslike ductilityand malleability.Aductilematerialcanbestretchedintolong,thinwires.A malleablesubstancecanbehammeredintoverythinsheets.Goldandcopperaresomeofthemostmalleableandductilesubstances known.Thesepropertiesoccurasaresultofthemetallicbonding.
SolidsattheMolecularLevel
Solidsoccurwhenthereisenoughintermolecularbondingtoholdthemoleculesofasubstanceintoarelativelyrigidstructure.The (a)Brittle(b)and(c)showsductility moleculesareclosetogether,andtheirmovementisrestrictedtovibration.Solidsoccuratthelowesttemperaturesandhighest pressures.Asthetemperatureofasolidincreases,sodoesthekineticenergyofitsmolecules.Atthe meltingpoint ,themoleculeshave enoughenergytoovercometheirbondsand meltintoaliquid.Likewise,aliquidwill freezeonceitsmoleculesarenotmovingfastenoughtoavoidstrongintermolecularbonds. Compoundsthathaveionicbondingormetallicbondingaremostlikelytobefoundinthesolidphaseduetotheirhighmeltingpoints.Also,covalentnetworksubstances(like diamondorquartz)aresolidsbecausetheatomsaresecuredwithcovalentbonds,requiringextremeamountsofenergytoseparatethem.
TypesofSolids
Crystallinesolidshaveamolecularstructurewithaspecificgeometricshape.Thesolidhasaspecificmeltingpointatwhichallmoleculesbegintobreakfreeoftheirbonds. Substanceslikesalt,diamond,andquartzarecrystallinesolids.Thesesolidsusuallyformbycoolingaliquidslowly,sothatthemoleculeshavetimetoarrangethemselvesin acrystallinestructureastheirbondsform. Amorphoussolidshaveamolecularstructurewithnospecificshape.Thesolidmeltsoverarangeoftemperaturesbecausetheamountofenergyneededtobreakthebonds variesfrommoleculetomolecule.Substanceslikecoalandglassareamorphous.Amorphoussolidsusuallyformwhenaliquidiscooledquickly,sothereisnotimeforthe moleculestoarrangethemselvesintoacrystal. Crystallinesolidsaretypicallyharderandmorerigid.Coalanddiamondarebothmadefromelementalcarbon,butcoalisamorphousanddiamondiscrystalline.Becauseofits crystalstructure,diamondisoneofthehardestsubstancesknown,whereascoalcanbescratchedawaywithafingernail.Thecrystalstructurealsoexplainsdiamond'sbrilliant, transparentappearance.Coalisblackanddullbecausethedisorderoftheatomsdoesnotallowlighttopass.
PackingandUnitCells
Incrystallinesolids,theatomsarearrangedinaspecificpattern.Thesmallestrepeatingpartofthispatterniscalledthe unitcell .Theunitcellmayhavemoreatomsthanthe empiricalformulaofasubstancebecausethegeometricshapemayrequireseveralatoms.Inthecaseofsodiumchloride,theempiricalformulacontainsonlytwoatoms,buttheunit cellhas27atoms. Themoleculesofasolidare closepacked.Theyarrangethemselvesinthedensestshapepossible.Usually,twodifferentpatternsoccur. Facecenteredcubicor FCC Hexagonalclosepackedor HCP
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FCCcrystalshavethreealternatinglayers,describedasABCABCABC(everythirdlayeristhesame).Thelayersarearrangedsothateachunitcellishalfwaybetweenthetwounit cellsaboveorbelowit.HCPcrystalshavetwoalternatinglayers,describedasABABABAB(everyotherlayeristhesame).
FCClattice
HCPlattice
Liquids
Halite,orrocksalt,exhibitsFCCpacking.
LiquidsataMolecularLevel
Theunitcellofsodiumchloride
Liquidshavesomeintermolecularbonding,butitisnotnearlyasstrongasthatofasolid.Asaresult,themoleculesaresomewhatclose together,buttheyarenottightlypacked.Instead,theyarefreetoslidepasteachother.Liquidsoccurattemperaturesabovethe melting point ofasubstance,butbelowits boilingpoint .Atthemeltingpoint,themoleculesaremovingslowenoughtoformrigidbondsand becomeasolid.Attheboilingpoint,themoleculesaremovingsofastthattheycannotformanybondsandbecomeagas.
CharacteristicsofLiquids
Liquidshave definitevolume,but indefiniteshape.Theyarefreetoformdropletsandpuddleswhentheyarenotinsideacontainer. Whenaliquidisinsideacontainer,itwilltakeitsshape.Unlikegases,aliquidwillnotchangeitsvolumetospreadoutandcompletelyfill acontainer.Thereisenoughintermolecularbondingtogiveliquidsadefinitevolume. Liquidsare fluid,abletoflowandtakeanyshape.Thisoccursduetotheweakintermolecularbondingthatallowsthemoleculestoslide pasteachotherfreely.Asaresultofbeingfluid,liquidsexhibitmanyinterestingpropertiesthatsolidsdonot,includingcapillaryaction anddiffusion. Liquids,likegases,undergo diffusionwhenmixed.Thiscanbeseenbyaddingfoodcoloringtowater.Differentliquids,whenadded,will chaoticallyspreadoutandmixtogether.Diffusionwilloccurfasterwhentheliquidiswarmerbecausetheincreasedkineticenergyallows themoleculestomovefasterandcollidemorefrequently. Liquidsareusuallyconsidered incompressible.Themoleculesarealreadyclosetogether,soitisdifficulttocompressthemanymore. Underveryhighpressures,liquidswillactuallycompress,butnotverymuch. Liquids,unlikegases,haveadistinct surfacetheyneednottaketheircontainer'sshape.Thisallowstheformationofdropletsand puddles.
Diffusionisthechaoticmixingoffluids.The jaronthelefthaswarmerwater.
SpecialProperties
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CohesionandAdhesion
Themoleculesofaliquidareattractedtoeachother.Thisiscalled cohesion.Moleculeslikemethanearenonpolar,sotheyareheld togetheronlybyvanderWaalsforces(theweakest).Thesemoleculeswillhaveminimalcohesion.Incontrast,watermoleculesuse hydrogenbonding(verystrong),sotheydisplaystrongcohesion.Acohesiveliquidwillformmoresphericaldropletsandhavemuchhigher surfacetension(explainedbelow). Adhesionistheattractionofaliquidmoleculetoitssurroundings.Adhesiveliquidswilldemonstrate capillaryaction(explainedbelow). Theyarealsomore"wet".Mercuryisverycohesive,butnotadhesive.Asaresult,itdoesn'tleavebehindresidueasitrollsacrossa surface.Water,ontheotherhand,ismuchmoreadhesive.Whenwaterrollsacrossasurface,itwetsthatsurfacebecausesomeofthe moleculesadheretoit.
SurfaceTensionandCapillaryAction
Whenwaterdropsareonan impermeable(waterproof)surface,theytendtoformbeads.Thisisduetoits surfacetension.Liquid moleculespullateachother,andasaresulttheydecreasetheirsurfacearea.Themoleculesattheboundaryoftheliquidarepulledin, causingadropletshape.Whenwaterisona permeablesurface,itspreadsout,ascanbeseenwithwateronapapertowel.This capillaryactionexplainshowwaterinthegroundreachesthetopoftreesthatarehundredsoffeettall.
Waterdropletsadheretoaspiderweb. Theirroundshapeiscausedbycohesion.
Adhesiveliquids(like waterbutnotmercury)will riseupanarrowtube.
Cohesiveliquidshave surfacetensiontohold themselvesintodroplets.
Pressure
Liquidswilldistributepressureevenly.Thisconcept,knownas Pascal'sLaw,iscrucialforequipmentlikehydraulicbrakes.Itisaresultoftheirincompressibility. Liquidswill evaporate.Althoughtheaveragekineticenergyofthemoleculesistoolowtoovercomebondingandbecomeagas, individualmoleculeswilloccasionallyhaveaboveaverageenergyandbreakfreefromthesurfaceoftheliquid.Themoleculethen escapesescapestothegasphase.Atthesametime,however,agasmoleculemayhitthesurfaceoftheliquidandslowdown enoughtojointheliquid.Aglassofwaterleftoutsideinthesunwilleventuallybecomeempty.Thesunlightaddsenergytothe molecules,allowingsometoescapeasagas.Eventually,allmoleculeswillescape.Thetendencyofaliquidtoevaporatedependson itsintermolecularforces. Volatileliquidstendtoevaporatequicklyhaverelativelyweakintermolecularforceskeepingthemolecules together,makingiteasierforthemtoescapetheliquidphase.Conversely,nonvolatileliquidsdonotevaporatetoanyvisibleextent duetothepresenceverystrongintermolecularforces.
HelpfulHint!
Ifthereisnoatmosphericpressure(a vacuum,likeouterspace),liquids cannotform.
Theevaporationincreaseswithtemperature.Itcanbemeasuredby vaporpressure,theamountofpressureexertedbytheevaporatedgasabovetheliquid'ssurface.Vapor pressureincreaseswithtemperature,andonceitreachesthepressureofthesurroundingatmosphere,theliquidwillboil.Vaporpressurealsodependsontheintensityof intermolecularforcesintheliquid.

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Viscosity
Viscosityreferstotheliquid'sresistancetoflow.Forexample,maplesyruphasarelativelyhighviscositywhencomparedtowaterbecausemaplesyrupflowsmuchslowerthan water,whichflowsrelativelyquicklyandeasily.Thedifferenceinviscositybetweenthesetwoliquidsisduetotheattractiveforceswithinthespecificliquid.Inordertoflow, moleculesmustrollandmoveovereachother.Asolutionwithlowattractiveforceswouldallowthemoleculestomoveinamorefreeandeasymanner,decreasingtheviscosity. Inmostcases,theviscosityofaliquiddecreasesasthetemperatureofaliquidisincreased.Increasingthetemperatureofaliquidcausesthemoleculestohaveahigherkinetic energy.Thisincreaseinkineticenergybreaksdowntheintermolecularforcespresentintheliquid.Sinceviscosityisdependentontheseattractiveforces,theviscositywilldecrease whenthekineticenergyisincreased.
Gases
CharacteristicsofGases
Gaseshaveanumberofspecialcharacteristicsthatdifferentiatethemfromotherstatesofmatter.Hereisalistofcharacteristicsofgases:
CharacteristicsofGases Gaseshaveneither definiteshapenor definitevolume.Theyexpandtothesizeoftheircontainer. Gasesare fluid,andfloweasily. Gaseshave lowdensity,unlesscompressed.Beingmadeoftinyparticlesinalarge,openspace,gasesareverycompressible. Gases diffuse(mixandspreadout)and effuse(travelthroughsmallholes).
StandardTemperatureandPressure
StandardTemperatureandPressure,or STP ,is0Cand1atmosphereofpressure.Expressedinotherunits,STPis273 Kand760 torr.TheKelvinandtorrareusefulunitsof temperatureandpressurerespectivelythatwewilldiscusslaterinthefollowingsections.
Avogadro'sLaw
Avogadro'sLawstatesthatequalvolumesofgasesatthesametemperatureandpressurecontainthesamenumberofmolecules.SobothonemoleofXenonatSTP(131.3 grams)andonemoleofheliumatSTP(4.00grams)takeup22.4liters.Even1moleofair,whichisamixtureofseveralgases,takesup22.4litersofvolume.22.4Listhestandard molarvolumeofagas.
. where: V isthevolumeofthegas. nisthenumberofmolesofthegas. kisaproportionalityconstant. ThemostimportantconsequenceofAvogadro'slawisthatthe'idealgasconstanthasthesamevalueforallgases.Thismeansthattheconstant

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where: pisthepressureofthegas Tisthetemperatureofthegas hasthesamevalueforallgases,independentofthesizeormassofthegasmolecules.
[Avogadro'sLaw]
AmedeoAvogadro,theItalianchemist. Avogadro'sLawisnamedafterhimand hisdiscoveriesaboutthebehaviorof gases
Pressure
Gasesexertpressureontheircontainersandallotherobjects.Pressureismeasuredasforceperunitarea.Abarometerisadevicethatmeasurespressure.Thereareanumberof differentunitstomeasurepressure: torr,equaltomillimetersofmercury(mmHg):ifaglasscylinderwithnogasinitisplacedinadishofliquidmercury,themercurywillriseinthecylindertoacertainnumber ofmillimeters. atmosphere(atm),thepressureofairatsealevel.
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pascal(Pa),equaltoonenewton(N)persquaremeter.Anewtonistheforcenecessarytoaccelerateonekilogrambyonemeterpersecondsquared. Youshouldknowthat 1atm=760torr=101.3kPa.
IdealGases
Gasesarecomplicatedthingscomposedalargenumbersoftinyparticleszippingaroundathighspeeds.Thereareanumberofcomplexforcesgoverningtheinteractionsbetween moleculesinthegas,whichinturnaffectthequalitiesofthegasasawhole.Togetaroundthesevariouscomplexitiesandtosimplifyourstudy,wewilltalkabout idealgases. Anidealgasisasimplifiedmodelofagasthatfollowsseveralstrictrulesandsatisfiesseverallimitingassumptions.Idealgasescanbeperfectlymodeledandpredictedwitha handfulofequations. Idealgasesfollow,amongothers,theseimportantrules:
RulesofIdealGasses 1. Themoleculesthatmakeupagasareapointmasses,meaning theyhavenovolume. 2. Gasparticlesarespreadoutwithverygreatdistancebetweeneachmolecule.Thus, intermolecularforcesareessentiallyzero,meaning thattheyneitherattractnorrepeleachother. 3. Ifcollisionsdooccurbetweengasparticles,these collisionsareelastic,meaningthereisnolossofkinetic(motion)energy. 4. Gasmoleculesarein continuousrandommotion. 5. Temperatureisdirectlyproportionatetokineticenergy.
IdealGasLaw
Idealgasescanbecompletelydescribedusingthe idealgaslaw:
[IdealGasLaw]
where istheabsolutepressureofthegas, isthevolumeofthegas, isthenumberofmolesofgas, istheidealgasconstant, istheabsolutetemperature,inKelvin.
IdealGasConstant
Theidealgasconstant, R,isaconstantfromtheidealgasequation,above,thathelpstorelatethevariousquantitiestogether.Thegasconstantrepresentsthesamevalue,butthe exactnumericalrepresentationofitmaybedifferentdependingontheunitsusedforeachterm.Thetableatrightshowssomevaluesof Rfordifferentunits.Hereisthevalueof R usingJoulesforenergy,Kelvinfortemperature,andmolesforquantity:
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[IdealGasConstant]
Valuesof R 8.314 472(15) 8.314 472(15) 8.314 472(15)
Units J K 1 mol1 m3 Pa K 1 mol1 cm3 MPa K 1 mol1
0.082 057 46(14) L atm K 1 mol1 62.363 67(11) L Torr K 1 mol1
RealGases
All realgases(or nonidealgases)deviatefromtheidealgaslawsthatwediscussedabove.Thesedeviationscanoccurforseveralreasons: Realmoleculeshavemassandvolume.Theyaretoobigandnolongerbehavelikeidealpointmasses Lowvolumesandhighpressurescausemoleculestobecloseenoughforintermolecularforces.Polarmoleculesexaggeratetheproblem. Lowtemperaturemeanslowkineticenergy.Atlowertemperatures,intermolecularforcesbecomesignificantandcannotbeignoredliketheyareinidealgasses Othercomplicatedfactorsmaypreventidealbehavior. Whentheseissuesarepresent,gasmoleculesattracteachother,andmayevencondenseintoaliquid.Gasesactmostlikeidealgaseswhenthemoleculeshavelowmass(small volume),arenotpolar,andareathightemperatureandlowpressure.NoblegaseslikeXenonorArgonactthemostlikeidealgasesbecausetheyaremostlyelectricalneutraland noninteractive.
KineticMolecularTheory
Thistheorydescribeswhygasesexhibittheirproperties.Itonlyappliesaccuratelytoidealgases.Becausethereisnosuchthingasanidealgas,the KineticMolecularTheorycan onlyapproximategasbehavior.Itisstillveryusefultochemists. TheKineticMolecularTheoryexplainsthepressure,temperature,kineticenergy,andspeedofgasesandtheirmolecules.SeeWikipediafortheexactequationsoftheKinetic MolecularTheory,aswellasdetailedexplanations.Whatismostimportantisunderstandingthegeneralconcepts,notthespecificequations.
KineticEnergyandTemperature
Kineticenergyisthemechanical,ormovement,energy.Itisgivenbytheequation:
where ismassand istheaveragevelocity Explainedwithwords,kineticenergyisdependentontheproductofaparticle'smassanditsvelocitysquared.Themorekineticenergy,thefasteraparticlemoves.Conversely,the fasteraparticlemoves,themorekineticenergyithas.

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TheKineticMolecularTheorystatesthatkineticenergyandtemperaturearedirectlyproportionate.Thus,adoubleintemperaturewillresultinadoubleinkineticenergyandan increaseinvelocitybyafactorof1.4(thesquarerootof2,seetheKEequation).Thismeansthatthehigherthetemperatureofagas,thefastertheindividualparticlesinthatgas aremoving. Ahottergashasmorekineticenergythanacoldergas.Iftwogasesareatthesametemperature,theywillhavethesamekineticenergy.Thelightermassedgaswillhaveahigher averagespeedforitsparticlesatthesameenergylevel.Itisimportanttoknowthatgastemperature mustbemeasuredinkelvin.ZerodegreesCelsiusis273kelvin.OneCelsius degreeisequaltoonekelvin,butthekelvinscalehaswater'sfreezingpointat273andboilingpointat373.Itisnecessarytousekelvinbecausetemperaturesmustalwaysbe positivewhenusingtheKineticMolecularTheory.
Questionforthereader Agas'stemperatureisincreasedfrom20Cto40C.Whatfactordoesitskineticenergyincrease?Velocity?
PressureandCollisions
Pressureexistsbecausethegasmoleculesareincontinuousrandommotion,andtheywillconstantlystrikethewallsoftheircontainer.Pressurewillincreaseasthespeedofthe moleculesincreases,duetogreaterforcesofcollision.Pressurewillalsoincreaseasthemassofthemoleculesincrease.Asmall,slowmoleculehaslessmomentumthanalarge, fastmolecule,whichexplainstheirdifferenceinpressure.
Questionforthereader Therearetwojarsofidealgas,forexample.InJarAthereisnitrogengas(N2).InJarBthereismethanegas(CH4).Bothjarsareatthesame temperature.Whichwillhavegreaterpressure?
Questionforthereader Now,JarsAandBbothhavepropanegas(C3H8).JarAisat300KandJarBisat500K.Whichwillhavegreaterpressure?
PhaseChanges
PhaseDiagrams
Phasediagramspredictthephaseofasubstanceatacertainpressureandtemperature.
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The triplepointiswhereallthreephasesofmattercanexistinequilibrium.Pointsthatareonalinearewheretwophasesofmattercancoexist. The criticalpointisthehighestpressureandtemperaturethatthethreenormalphasescanexist.Anyfurther,andthecharacteristicsbecomeablendofliquidandgas.
ChangesinState
Ifthetemperatureandpressurechangeandmoveacrossalineinthediagram,thephasewillalsotochange.Therearesixwaysthiscanhappen: Solidtoliquid: melting Liquidtosolid: freezing Liquidtogas: evaporation Gastoliquid: condensation Gastosolid: deposition Solidtogas: sublimation Thediagramontherightalsoshowsthe plasmastateofmatter.Aplasmaissimplyagasthathasbeencompletelyionized,sothatthereisamixtureofpositiveionsandelectrons. Ithasinterestingelectricalproperties,butitisnotimportantinthescopeofGeneralChemistry.
EnergyChanges
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Ifyouboilwater,itnevergoesabove100degreesCelsius.Onlyafterithascompletelyevaporatedwillitgetanyhotter.Thisisbecauseoncewaterreachestheboilingpoint,extra energyisusedtochangethestateofmatterandincreasethepotentialenergyinsteadofthekineticenergy.Theoppositehappenswhenwaterfreezes.Toboilormeltonemoleofa substance,acertainamountofenergyisrequired.Theseamountsofenergyarethe molarheatofvaporizationand molarheatoffusion.Ifthatamountofenergyisaddedtoa moleofthatsubstanceatboilingorfreezingpoint,allofitwillmeltorboil,butthetemperaturewon'tchange.
HelpfulHint!
Thekineticenergyofamoleculeis directlyproportionaltoits temperature.Potentialenergyisused tobreakbonds.
Thegraphshowsthetemperatureoficeasheatisadded.Temperatureincreaseslinearlywithheat,untilthemeltingpoint.Then,theheataddeddoesnotchangethetemperature. Thatheatenergyisinsteadusedtobreakintermolecularbondsandconverticeintowater.Atthispoint,thereisamixtureofbothiceandwater.Onceallicehasbeenmelted,the temperatureagainriseslinearlywithheatadded.Attheboilingpoint,temperaturenolongerriseswithheataddedbecausetheenergyisonceagainbeingusedtobreak intermolecularbonds.Onceallwaterhasbeenboiledtosteam,thetemperaturewillcontinuetoriselinearlyasheatisadded.
BehaviorofGases
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EvaporationofLiquids
Anopenbottleofvinegarstandingatroomtemperaturewillspreadodoracrosstheroomdespitethefactthatitisnotboiling.Thisisbecausekineticenergyisunevenlydistributed throughoutaliquid.Somemoleculesaremovingfasterthanothers.Thisallowstheliquidto evaporateintoagas.Inorderforevaporationtooccur,theentireliquiddoesnotneedto beattheboilingtemperatureonlysomeindividualmolecules.Atagiventemperaturealiquidevaporatesataspecificrate,causinggaspressureabovetheliquidinthesystemthat containsit.Canyouguessthevaporpressureofwaterat100degreesCelsius?Ifyouguessed760torror1atm,you'reright.Liquidsboilwhentheirvaporpressuresequalthe atmosphericpressurearoundthem.Someliquidsaremore volatilethanothers,meaningtheyevaporatemorereadily.
ABoltzmanndistributionatvarious temperatures.
Evaporationoccursbecauseoftheunevendistributionofkineticenergy.Thisiscalleda Boltzmanndistribution.Althoughtheaveragekineticenergyoftheliquidisbelowtheboiling point,somemoleculeshaveaboveaverageenergy.Thatgivesthemenoughenergytoovercometheirbondsandbreakfreeoftheliquid.Atthesametime,agasmoleculecould striketheliquidandslowdownenoughtobecomepartofit.Thereisan equilibriumbetweentheamountofevaporatingliquidandtheamountofliquifyinggas.Highertemperatures willhaveanequilibriumthatfavorsmoregas.
MotionofGasParticles
Gasparticlesmoveinrandom,straightlinemotion.Gasparticlespossessagreaterkineticenergythantheparticlesofaliquidorsolid. Thegreaterkineticenergyisduetogasesexistingathighertemperaturesthanliquidsorsolids.Astemperatureincreases,particlesmove fasterand,thus,havegreaterkineticenergy.Theparticlesofagashaveminimalinteractions,exceptcollisionswitheachother.
DiffusionandEffusion
Duetotheirrandommotion,gaseswilleventuallyescapefromacontainerifthereisaholeinit.Thisiscalled effusion.Gasesalso spreadoutacrossaroom,ormixtogetherinacontainer.Thisiscalled diffusion. Moreinformationaboutdiffusionandeffusionispresentedinthenextchapter.
Dalton'sLawofPartialPressures
Thetotalamountofpressureexertedbyagasisequaltothesumofitscomponents:
Thisanimationdemonstratesthemotionof gasparticles.
Forinstance,ifyouadd300torrofnitrogengastoacontainer,thenyouadd250torrofoxygentothatcontainer,thetotalpressurewillbe550torr(assumingvolumeand temperaturestayedconstant).
Anotherwayofstatingthislawisthatthepressureexertedbyaparticulargasinamixture(gasesalwaysformhomogeneousmixtureswitheachother)isequaltoitsmolefraction
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Anotherwayofstatingthislawisthatthepressureexertedbyaparticulargasinamixture(gasesalwaysformhomogeneousmixtureswitheachother)isequaltoitsmolefraction multipliedbythetotalpressure.
Diffusion
Diffusionistheprocessofasubstancespreadingouttoevenlyfillitscontainerorenvironment.Inasolution,aconcentratedsolutediffusestospreadevenlyinitssolvent.Inair,gas moleculesdiffusetomixthoroughly.Substancesdiffusefromareasofhighconcentrationtolowconcentration.Diffusionexplainswhyanopenbottleofammoniawillfillanentire roomwithodor.Thegasmoleculesescapingfromthebottlespreadouttofilltheirnewcontainer:theroom.Asaresult,thewholeroomsmells.Uponopeningthewindows,thegas willdiffuseintotheenvironment. Diffusionisalsotheprocessoftwogasesmixingtogether,ifbothstoredinthesamecontainer.Theywillspreadoutevenly,resultinginasolution(homogeneousmixture).
Effusion
Effusionistheprocessofgasmoleculesescapingfromasmallholeinthecontainer.Effusionexplainswhyfumesarenoticeablenearaleakyfuelpipe. Effusionobviouslydependsonthesizeofthehole.Ifsmallenough,effusionmaynotoccurbecause,likeabeachballhittingabasketballhoop,themoleculescan'tfit.Largerholes obviouslyallowmoleculestoescapefaster.Iftheholeislargeenough,theprocessmaybeconsidereddiffusioninsteadofeffusion. Effusioncanbeseenwithballoons.Effusionprovesthattheballoonhasholesinit,eventhoughitlookstotallyimpassable.Whenleftaloneforseveraldays,aballoonfilledwith heliumwilleventuallydeflate.Ifthatballoonwerefilledwithhydrogen,itwoulddeflateinlesstimebecausethemoleculesaresmallerandescapewithease.andyoucantrythat
Graham'sLawofEffusion
Themoremassiveagasis,thesloweriteffuses.Therelationshipisgivenby Graham'sLaw. ,whereMisthemolarmassofagasmolecule. Graham'sLawcanbeusedtoapproximate diffusion.However,diffusioninvolvestwoor moregasesinteractingwitheachother,so theequationisnotaccurate.
Asanexample,assumetherearetwoidenticalcontainerswithholes.ContainerAhashydrogengas(M=2g/mol)andContainerB hasheliumgas(M=4g/mol).Ifthehydrogengaseffusesatarateof4mol/hr,theheliumgaswouldeffuseataslowerrate(being heavier).UsingGraham'sLaw,wecanseethatitwouldeffuseatarateofabout2.8mol/hr.
GasLaws
GasLaws
Astheresultofmanydifferentscientistsandexperiments,several gaslawshavebeendiscovered.Theselawsrelatethevarious statevariablesofagas.
StateVariablesofaGas Pressure(P)
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Volume(V) Temperature(T) Molarmass(n)
Thesegaslawscanbeusedtocomparetwodifferentgases,ordeterminethepropertiesofagasafteroneofitsstatevariableshavechanged.
Avogadro'sLawstatesthatequalvolumesofallidealgases(atthesametemperatureandpressure) containthesamenumberofmolecules.
Boyle'sLawstatesthatequalpressureisinverselyproportionaltovolume(whentemperatureis constant).
Charles'sLawstatesthatvolumeisproportionaltotemperature(whenpressureisconstant). RememberthattemperaturemustbemeasuredinKelvin.
GayLussac'sLawstatesthatpressureisproportionaltotemperature(whenvolumeisconstant).
CombinedGasLaw
CombiningCharles'sLaw,Boyle'sLaw,andGayLussac'sLawgivesusthe combinedgaslaw.
Foragaswithconstantmolarmass,thethreeotherstatevariablesareinterrelated.
TheCombinedGasLawcanbeusedforcomparisonsbetweengases.
IdealGasLaw
WhenAvogadro'sLawisconsidered,allfourstatevariablescanbecombinedintooneequation.Furthermore,the"constant"thatisusedintheabovegaslawsbecomesthe
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WhenAvogadro'sLawisconsidered,allfourstatevariablescanbecombinedintooneequation.Furthermore,the"constant"thatisusedintheabovegaslawsbecomesthe UniversalGasConstant(R). TobetterunderstandtheIdealGasLaw,youshouldfirstseehowitisderivedfromtheabovegaslaws.
and
ThisissimplyarestatementofAvogadro'sLawandtheCombinedGasLaw.
Wecannowcombinethelawstogether.
LetRbeaconstant,andwritetheproportionintheformofanequation.
Rearrangingthefractiongivesoneformofthe idealgaslaw.
Theidealgaslawisthemostusefullaw,anditshouldbememorized.Ifyouknowtheidealgaslaw,youdonotneedtoknowanyothergaslaws,foritisacombinationofallthe otherlaws.Ifyouknowanythreeofthefourstatevariablesofagas,theunknowncanbefoundwiththislaw.Ifyouhavetwogaseswithdifferentstatevariables,theycanbe compared. Therearethreewaysofwritingtheidealgaslaw,butallofthemaresimplyalgebraicrearrangementsofeachother.
Thisisthemostcommonform.
Thisformisusefulforpredictingtheeffectsofchangingastatevariable.TomaintainaconstantvalueofR,anchangeinthenumeratormust resultinaproportionalchangeinthedenominator,andviceversa.If,forexample,thepressureisdecreasedinaconstantvolumecontainer,you canusethisformtoeasilypredictthatthetemperaturemustdecrease.
BecauseRisthesameconstantforallgases,thisequationcanbeusedtorelatetwogasestoeachother.
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KineticMolecularTheory
TheKineticMolecularTheoryattemptstoexplainthegaslaws.Itdescribesthebehaviorofmicroscopicgasmoleculestoexplainthemacroscopicbehaviorofgases.Accordingto thistheory,anidealgasiscomposedofcontinuallymovingmoleculesofnegligiblevolume.Themoleculesmoveinstraightlinesunlesstheycollideintoeachotherorthewallsof theircontainer.
The pressureofthegasonthecontainerisexplainedastheforcethemoleculesexertonthewallsduringacollision.Pressureisequaltothe averageforceofcollisionsdividedbythetotalsurfaceareaofthecontainer.
The temperatureofthegasisproportionaltotheaveragekineticenergyofthemolecules. and isthe Boltzmanconstant (1.388x1023).
denotestheaveragekineticenergyofthemolecules,
Thegaslawsarenowexplainedbythemicroscopicbehaviorofgasmolecules: Boyle'sLaw:Thepressureofagasisinverselyproportionaltoitsvolume.Acontainer'svolumeandsurfaceareaareobviouslyproportional.Basedonthepressureequation, anincreaseinvolume(andthussurfacearea)willdecreasepressure. Charles'Law:thevolumeofagasisproportionaltoitstemperature.Asthevolume(andsurfacearea)increases,thepressurewilldecreaseunlesstheforcealsoincrease. Whenpressureisconstant,thevolumeandtemperaturemustbeproportional.Thetemperatureequationaboveexplainswhy:theenergyofthemolecules(andtheircollision force)isproportionaltotemperature. GayLussac'sLaw:Thetemperatureofagasisdirectlyproportionaltoitspressure.Anincreaseintemperaturewillincreasethekineticenergyofthemolecules(shownbythe temperatureequation).Greaterkineticenergycausesthemoleculestomovefaster.Theircollisionswiththecontainerwillhavemoreforce,whichincreasespressure. Avogadro'sLaw:Equalvolumesofallidealgases(atthesametemperatureandpressure)containthesamenumberofmolecules.AccordingtotheKineticMolecularTheory, thesizeofindividualmoleculesisnegligiblecomparedtodistancesbetweenmolecules.Eventhoughdifferentgaseshavedifferentsizedmolecules,thesizedifferenceis negligible,andthevolumesarethesame.
DerivationofIdealGasLaw
Supposethereare molecules,eachwithmass ,inacubiccontainerwithsidelength .Eventhoughthemoleculesaremovinginalldirections,wemayassume,on average,thatonethirdofthemoleculesaremovingalongthexaxis,onethirdalongtheyaxis,andonethirdalongthezaxis.Wemayassumethisbecausethemotionofthe moleculesisrandom,sonodirectionispreferred.
Supposetheaveragespeedofthemoleculesis .LetaspecificwallofthecontainerbelabeledA.BecausethecollisionsinKineticMolecularTheoryareperfectlyelastic,the speedafteracollisionis .Therefore,theaveragechangein momentum(theproductofmassandvelocity)percollisionis . Eachmolecule,onaverage,travelsadistanceof betweentwoconsecutivecollisionswithwallA.Therefore,itwillcollide timespersecondwithwallA.
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Theaveragechangeinmomentumpermoleculepersecond.
Therefore,thisisthetotalchangeinmomentumpersecondforthe
moleculesthatcollideintowallA.Thisisthemomentum
persecondthatwasexertedontowallA.Becauseforceequalsthechangeinmomentumovertime,thisvalueistheforceexertedonwall A.
Pressureisdefinedasforceperunitarea,sothisisthepressure
ofthegas.
Becausethevolumeofthecontaineris
,wecanrearrangetheequation.
Thekineticenergyofasingleparticleisgivenbythisequation.
Substitutekineticenergyintothe
equation.
Substitutethetemperatureequation(fromtheprevioussection).
Avogadro'snumber
isequaltothenumberofmoleculespermole.
Bydefinition,theidealgasconstantisequaltotheBoltzmannconstanttimesAvogadro'snumber.
TheidealgaslawisderivedfromtheKineticMolecularTheory.
DeviationsfromtheIdealGasLaw
Inanidealgas,therearenointermolecularattractions,andthevolumeofthegasparticlesisnegligible.However,thereisnorealgasthatcanperfectlyfitsthisbehavior,sothe IdealGasLawonlyapproximatesthebehaviorofgases.Thisapproximationisverygoodathightemperaturesandlowpressures.
Athightemperaturethemoleculeshavehighkineticenergy,sointermolecularattractionsareminimized.Atlowpressurethegasoccupiesmorevolume,makingthesizeofthe
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Athightemperaturethemoleculeshavehighkineticenergy,sointermolecularattractionsareminimized.Atlowpressurethegasoccupiesmorevolume,makingthesizeofthe individualmoleculesnegligible.Thesetwofactorsmakethegasbehaveideally. Atlowtemperatureorhighpressure,thesizeoftheindividualmoleculesandintermolecularattractionsbecomessignificant,andtheidealgasapproximationbecomesinaccurate.
EudiometersandWaterVapor
A eudiometerisadevicethatmeasuresthe downwarddisplacement ofagas.Theapparatusforthisprocedureinvolvesaninverted containerorjarfilledwithwaterandsubmergedinawaterbasin.Thelidofthejarhasanopeningforatubethroughwhichthegasto becollectedcanpass.Asthegasenterstheinvertedcontainer,itforceswatertoleavethejar(displacingitdownward).Tofillthe entirecontainerwithgas,theremustenoughgaspumpedintothecontainertoexpelallofthewater.
HelpfulHint!
Incalculationsforagasabovea liquid,thevaporpressureoftheliquid mustbeconsidered.
Gasiscreatedbyburningasubstancethatreleasesmethane.The eudiometerontherightwasfullofwaterbeforethegaswascreated. Bymeasuringthechangeinvolume,theamountofgascanbe calculated.
Asseeninthisdiagram,thedownwarddisplacementinvolveswater.Therefore,inthecontainerwherethegasiscollected,thereisunwantedwatervapor.Toaccountforthewater vapor,subtractthepressureofwatervaporfromthepressureofthegasesinthecontainertofindthepressureofthecollectedgas.ThisissimplyarestatementofDalton'sLawof PartialPressure:
Thepressureofwatervapourcanbefoundonthiswebpage(http://eweb.chemeng.ed.ac.uk/chemeng/water.html).
GasLawsPracticeQuestions
1. 2. 3. 4. BetweentheCombinedGasLawandtheIdealGasLaw,whichoneaccountsforchemicalchange?Explain. Calculatethedensityofhydrogenatatemperatureof298Kandpressureof100.0kPa. Whatvolumedoes5.3molesofoxygentakeupat313Kand96.0kPa? Hydrogenandsulfurchemicallycombinetoformthegashydrogensulfide,accordingtothereaction:H2(g)+S (s)H2S (g).Howmanylitersofhydrogenarerequiredtoform 7.4Lofhydrogensulfide(atSTP:273K,101.3kPa)? AnswerstoGasLawsPracticeQuestions
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ChemicalEquilibrium
Equilibria
Chemicalequilibriumoccurswhena reversiblereactionis occurringbackwardsandforwardsatthesametimebythesame amount.Itisthebalancingpointofachemicalreaction,whenit seemstostophappening.Althoughsomereactions(likethecombustionofpropane)occurtocompletion(nobackwardsreaction),mostreactionsoccurinboththeforwardand backwarddirection.Onereactionwilloccuratafasterratethantheother,causinganetresult.Asthereactionprogresses,theforwardreactionslowsdownandthebackward reactionspeedsup.Whentheratesareequal, equilibriumhasoccurred.Thereactionappearstohavestopped,andthetotalamountofproductsandreactantsremainsstable.
TheEquilibriumConstant
Theratioofproductstoreactants,or isknownasthe equilibriumconstant.ForthegenericreactionmA+nBxC+yD,theequilibriumconstantis
where[X]detonatesthe activityofX.TheactivityofXis: itsconcentrationifXisagasorinasolution 1ifXisapuresolidorpureliquid Inotherwords,puresolidsandliquidsdon'taffecttheequilibriumconstant,aslongasthereisenoughforthereactiontoproceed.Theiractivityis1,sotheydon'tneedtobewritten intheequilibriumconstant.
KpandKc
Therearetwotypesof .Oneis ,andtheactivitiesare concentrations.Youarealreadyfamiliarwiththisexpressionitisthenormallyused .Forgaseousreactions,
youmayusetheconcentrationequilibrium.Youmayalsouse partialpressuresinsteadofconcentrations.Thisexpressionisdenoted ofconcentrations.Thiscanonlybeusedwhenallproductsandreactantsareinthegaseousphase. Toconvertbetween and ,thereisanequation:
.Theactivitiesarepartialpressuresinstead
RistheUniversalGasConstantandTisthetemperatureatwhichthereactionisoccurring. bezero(inwhichcaseK p=K c).
isthechange(inmoles)ofgasmoleculesbetweenproductsandreactants.Itmay
Examples
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Example1 15.0molesofXand20.0molesofYareputintoanempty2.0litercontainer.Theyreact,andeventuallyreachequilibriumwith7.0molesofZ accordingtothehypotheticalequation:
Calculatetheequilibriumconstant.
Solution:Becausethecontainerwasoriginallyemptyandatequilibrium,all7.0molesofZareproducedbythereaction.Therefore,7.0molesofXand14.0molesofYare consumedinthereaction,soatequilibriumthereremain8.0molesofX,6.0molesofY,and7.0molesofZ.Dividethesevaluesby2.0literstodeterminetheconcentration,then substituteintotheequilibriumexpression:
Example2 5.00molesofhydrogenareputintoanempty1.00Lcontainerwith5.00molesofiodine,wheretheyreactaccordingtothisequation:
Theequilibriumconstantis51.5atthetemperatureofthereaction.CalculatethenumberofmolesofHIthatwillform. Solution:Suppose2ymolesofHIforms.Then, ymolesofH2andI 2areconsumed.Therefore,atequilibrium,thereare2ymolesofHI,and(5.00 y)molesofbothH2andI 2. Dividingby1.00liters(tofindconcentration)andwritinganequilibriumexpressiongives:
Solvingthisequationgivesy=3.91(rejecttheothersolution,asitisgreaterthan5.00).Atequilibrium,thereare7.82molofHI.
CalculationsWithK
TheexactvalueofKdoesn'treallymatter.Whatisimportantisits magnitude. K>1 Reactionsfavorsproducts K<1 Reactionfavorsreactants Ifthereactionfavorsproducts,itwilloccurintheforward(lefttoright)direction.IfKisverylarge,thereactionwilloccurmostlytocompletion,usingupalmostallthereactants. Ifthereactionfavorsreactants,itwilloccurinthereverse(righttoleft)direction.IfKisverysmall,thereactionwilluseupalmostalltheproductsandmakethemintoreactants.The reversereactionisfavored.
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ReactionArithmetic
Ifyoureversethereaction(changingthedirectionofthearrow,orflippingtheleftandrightsides),thenewvalueofK eqwillbeitsreciprocal. AB (K=x) BA (K=1/x) Ifyouaddtworeactions,theirequilibriumconstantsaremultiplied. AB GH (K=x) (K=y)
A+GB+H (K=xy) Thesebasicprinciplescanhelpyoudetermineanunknownequilibriumconstantbycombiningknownconstants.
Q
K eqisonlyusedwhenareactionisinequilibrium.Tofindit,writeitsconcentration(orpartialpressure)expression,thenpluginallthemeasuredvalues.TheresultingKcanbeused topredictotherequilibriumpositions. Ifareactionisnotatequilibrium,youcanstillpluginthemeasuredconcentrations.InsteadofcallingthisvalueK eq,itiscalledQ. Q>K Theproductsmustdecreaseandthereactantswillincrease. Q=K Thereisequilibrium. Q<K Thereactantsmustdecreaseandtheproductswillincrease. So,ifyouknowtheequilibriumconstantforareaction,andyouknowalltheconcentrations,youcanpredictwhatdirectionthereactionwillproceed.
ICECharts
Let'ssayyouknowKforareaction,andyouknowsomeconcentrations.Youcancalculatethefinal(equilibrium)concentrationsusingan"InitialChangeEquilibrium"chart.Hereis anexample.
At25C,K c=23.2forthisreaction. First,writetheequilibriumexpression:
Inasealedcontainerof2.00L:3molH2O,4molCO,1molH2havebeenadded.(WritetheICEchart): CO
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H2O CO2 Initial Change 2 x 1.5 x 0 +x
H2 0.5 +x 0.5+x
Equilibrium 2x 1.5x x
Now,pluginthe"equilibrium"valuesintotheKexpression.Substituteallknownvaluesandsolveforx.Then,substitutexforthefinalvaluestodeterminetheequilibrium concentrations. BysubstitutingeverythingintotheKexpression,wehave:
Solvingthiswillrequiretheuseofthequadraticequation.Itmaybeeasiertouseapproximationsoragraphingcalculator.Whensolved, (disregardvaluesofxthat wouldgivenegativeconcentrations).Bysubstitutingxintothe"equilibrium"valuesintheICEchart,wecandeterminetheconcentrationsofallsubstanceswhenthereactionreaches equilibrium. CO H2O CO2 H2
0.66M 0.16M 1.34M 1.84M Tocheckyouranswer,youcouldsubstitutethesevaluesintotheequilibriumexpressionandseeifitequals23.3(thegivenK eqvalue). Thepurposeofdoingthisistoseethefinalconcentrationsofthesubstancesinvolvedinachemicalreaction.UnlessK eqisincrediblylarge,notallthereactantswillbeconsumed.
EquilibriuminDetail
Thenextfewchaptersinthisbookwillprovidemoredetailsonequilibrium.
ShiftsinEquilibrium
LeChatelier'sprinciplestatesthatasystemwilladapttominimizeachange.Ifreactantsareadded,theywillbeconsumedandproductswillform.Likewise,ifproductsareadded, theywillbeconsumed(bythereversereaction)andreactantswillform. TheonlychangeinasystemthatwillaffectthevalueofK eqistemperature.ThevalueofK eqisneverchangedbytheconcentrationsorpressuresofthesubstances.
SpecialConstants
Acidsandbaseshavespecial ionizationconstants,whichshowhowtheyreactwithwater.Theacidionizationconstant,orK a,tellshowstrong anacidis.
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Thebaseionizationconstant,K b,similarlytellshowstrongabaseis.
The solubilityproductK spshowshowmuchanionicsubstancewilldissociatewhendissolved.
RelationtoE
Thereisaspecialrelationbetweenthestandardpotentialofaredoxreactionandtheequilibriumconstant transferred.Thisisasignificantequation,becausethisallowsustocalculatethehardtomeasureKfromtheeasytomeasureE. ,wherenisthenumberofmolesofelectrons
LeChatelier'sPrinciple
LeChatelier'sPrinciple
LeChatelier'sPrinciplestatesthatwhenasystemthatisindynamicequilibriumisdisruptedinsomeway,thesystemwillrespondwithchemicalorphysicalchangestorestoreanew equilibriumstate. Thereareseveralchangesthatcaneffecttheequilibriumpositionofasystem: Concentration Pressure/Volume Temperature
Concentration
Iftheconcentrationsinasystemarechanged,LeChatelier'sPrinciplepredictsthattheequilibriumpositionwillshifttominimizethechange.
Forexample,letussaythatthereactionaboveisatequilibrium.Addingmorereactants( concentration.Thesystemwillthenproducemoreproducts( and nowatanewequilibriumposition,andthechangecreatedhasbeenminimized.
and
)willdisturbtheequilibriumsystembecauseitraisesthereactant
)andwilldecreasethereactantconcentrationinordertoobtainequilibriumagain.Thesystemis
Theaboveexampleshowsthatincreasingthereactantsinanequilibriumsystemfavorstheproductsbecausethesystemproducesmoreproductsandreducestheamountof reactants.Thetablebelowshowstheresponseofanequilibriumsystemtochangesinconcentration: ChangeinConcentration Systemresponse Increasereactant Decreasereactant Favorsproducts Favorsreactants

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Increaseproduct Decreaseproduct
Favorsreactants Favorsproducts
Pressure/Volume
Ifsomethesubstancesinasystemaregas,changingtheirpartialpressureisthesameaschangingtheirconcentrations. Ifthevolumeisincreased,theoverallpressuredecreases(andviceversa).ConsiderthereactionA+B3C.Therearethreemolesofproductsforeverytwomolesofreactants. Theproductsidehashigherpressurethanthereactantside.So,ifpressureisincreased(orvolumedecreased),equilibriumwillshifttowardsthelowerpressureside.Productswillbe consumed(bythereversereaction)andreactantswillform. Ifpressureisdecreased(orvolumeincreased),equilibriumwillshifttowardsthehigherpressureside.
Temperature
Changesinconcentration,pressure,andvolumeaffecttheequilibriumposition,buttheequilibriumconstantK eqisunchanged.Thesechangescanbecalculatedusingthe equilibriumexpressionandknownvaluesofK eqandconcentrations. Temperature,however,doeschangethevalueofK eq.WhengivenavalueofK,youwillalsobegivenatemperaturebecauseKisdependentonthetemperature. Anincreaseintemperaturewillfavortheendothermic(heatabsorbing)sideofareaction.Adecreaseintemperaturewillfavortheexothermic(heatreleasing)sideofareaction. Forexample,thefollowingreactionisveryexothermic:
Becauseitisexothermic,youcanthinkofitlikethis:
Atroomtemperature,K eqforthisreactionis3.2x1081.Ifthisreactionhappensataveryhightemperature,whatwillhappen?Lessproductwillform(ormaybethereversereaction willoccurifthetemperatureishighenough)andK eqwillbesmaller.Whatwillhappenifthisreactionoccursataverylowtemperature?MoreproductwillformandK eqwillbelarger.
AcidBaseEquilibrium
Consideranacid,HA,inwater.AccordingtotheBrnstedLowryacid/basetheory,theacidshouldprotonatethewatertoformhydroniumandthe conjugatebase,A .Therewillbe an equilibriumbetweentheacidandwater,andhydroniumandtheconjugatebase.
Thisequilibriumcanbeusedtocalculatetheconcentrationsofspeciesinthesolution.
AcidDissociationConstant
Likeallequilibria,anacid/basedissociationwillhaveaparticular equilibriumconstantwhichwilldeterminetheextentofthereaction(whetheritliestotheleftorrightofthe equation).Astheequilibriumconstantapproacheszero,thereactiontendstoform100%reactants.Astheequilibriumconstantapproachesinfinity,thereactiontendstoform100% products.TheequilibriumconstantK=1statesthattherewillbe50%productsand50%reactants.
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Becausetheequilibriumisusedforcalculatingtheconcentrationsofweakacids,verylittlewateractuallyreacts.Theconcentrationof waterduringthereactionis,therefore,aconstant,andcanbeexcludedfromtheexpressionforK.Thisgivesrisetoaspecial equilibriumconstant,K a,knownasthe aciddissociationconstant.ItissimplyKmultipliedbytheconcentrationofwater.
HelpfulHint!
Strongacids/basesdissociate completely,sotheirequilibrium constantsareoverwhelminglylarge.
TheK aofaweakaciddetermineshowacidicitis,i.e.,howfaritsequilibriumliestotheright. TheK avaluesofweakacidscanandhavebeendeterminedexperimentally.
BaseDissociationConstant
Asimilarequilibriumexistswhenaweakbaseisdissolvedinwater.Thebasewillacceptaprotonfromwaterandformaconjugateacid,BH+ .
Thisequilibriumhasitsownspecialconstant,K b,knownasthe basedissociationconstant.Liketheaciddissociationconstant,itisdefinedastheequilibriumconstantmultiplied bytheconcentrationofwater.
IonProductConstant
Aspecialequilibriumexistsbetweenordinarywatermolecules.Occasionally,onewatermoleculewillactasanacid,anddonateaprotontoanotherwatermolecule(whichactsasa base).Thisisthe autoionizationofwater.
BytheLeChatelierPrinciple,wecanseethatifthehydroniumionconcentrationisincreased(byaddinganacid),theequilibriumwillmovetotheleftandtherewillbea lower concentrationofhydroxide.Thus,hydroniumandhydroxideconcentrationareinverselyrelatedanincreaseinonewillresultinadecreaseintheother,andviceversa. Theequilibriumexpressionforthisreactionisgivenaspecialname,K w.Becauseitsimplifiestotheproductofhydroniumandhydroxideconcentration,itissometimescalledthe ion productconstant.Thevalueofthisconstantis1.01014at25C.
ThisexpressioncanbeusedtofindthepHofpurewater.RecallthatpHisthenegativelogarithmofhydroniumionconcentration.Ifwesetthehydroniumionconcentrationinthe aboveexpressiontobex,wecanderivethepH.Thehydroxideionconcentrationmustalsobex(sinceeachmoleculeofhydroxideisaresultofamoleculeofhydroniumforming). Wehave:
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ThistechniquecanbeusedtodeterminethepHofanysolutionifeitheroneoftheionconcentrationsareknown.
ConjugateBaseExpressions
Theconjugatebasesofweakacidshavearelationshipwiththeirparentacids.Considertheequilibriumexpressionoftheconjugatebase,A ,oftheweakacidHA.
Ifwemultiplytheexpressionforanacidbytheexpressionforitsconjugatebase,theconcentrationsoftheacidandconjugatebasecancelandweobtaintheionproductconstantfor water!ThisallowsustocalculatetheK bofabaseiftheK aofitsconjugateacidisknown(andviceversa).
Summary
Thedefinitionsoftheacidandbase dissociationconstantsareveryimportant.Theyarepresentedhereforreference.
The aciddissociationconstant measuresthestrengthofanaciddissolvedinwater.
The basedissociationconstant measuresthestrengthofabasedissolvedinwater.
The ionproductconstant relatestheconcentrationsofacids/basesandtheirconjugatesinasolution.
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SolutionsinEquilibrium
Solution
Allioniccompoundsaresolubleinwatertosomeextent,butthedegreeofsolubilityvaries.Whilesomecompoundsdissolvealmost completely,othersdissolvetosuchasmallextentthattheyaresimplycalled insolublecompounds.Suchcompoundsincludecalcium sulfate,silverchloride,andleadhydroxide.Generally,ioniccompoundswhosecomponentionshavelargerchargemagnitudesareless solublebecausetheionsareattractedtoomuchtodissociate.Asolublecompoundwilldissociatebecauseoftheattractionswiththe surroundingwatermoleculesarestrongenoughtoseparatetheions.
HelpfulHint!
Youmayneedtoreviewsolubilityand thepropertiesofsolutions.
Foranioniccompoundtodissociate,theforcesofattractionbetweenitscomponentionsandthesurroundingwatermoleculesmustbegreaterthantheforcesofattractionbetween theionswithinthecompound.Whenintroducedtoanaqueousenvironment,ioniccompoundssuchassodiumchloride,sodiumhydroxide,andammoniumbromidedissolvebecause ofthis.
SolubilityConstant
ThisreactionshowsanioniccompoundABdissolvingintoitsionsA + andB .
Thisistheequilibriumconstantforthereaction.Waterisexcludedbecause,althoughinvolved,itisnotaproductorreactant.
BecausetheundissolvedABisasolid,puresubstance,itcanbeexcludedfromtheexpression.Theresultisthe solubility constantKsp.Itmeasuresthedegreeofsolubilityofanioniccompound.
Iftwoormoreofthesameionarecreatedbythedissociationofoneparticleoftheioniccompound,themolarconcentrationofthisionisraisedtothepowerofhowmanysuchions thereare.Forexample,whencalciumchloridedissociates,twochlorideionsarecreatedinthedissociationofoneparticle,sotheconcentrationofthechlorideionissquaredwhen calculatingK sp.
Anexampleofaslightlysolublesubstanceiscalciumhydroxide.Inveryminutequantities,itwilldissolvecompletely,butinlargequantitiesitremainsmostlyundissolved.
CalculationswithKsp
FindingKsp
Itwouldnotbeanuncommonsituationifyouknowasubstance's solubility(g/mL),butyouneedtoknowitsK spvalue.Followthisexample:
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Thisisthesolubilityconstantforcalciumhydroxide.Wewishtodetermineisnumericalvalue, butweonlyknowthatitssolubilityis0.185gper100mL.
Weneedtoknowits molarsolubility,soweconvertunitsanddividebymolarmass.
Now,pluginthemolarsolubilityintotheK spexpression.Noticethatthehydroxide concentrationisdoubledbecausetherewillbetwiceasmanymolesastheundissolved substance.
WehavenowdeterminedtheK spvalueforcalciumhydroxide.Itwillallowustodetermineotherinformationaboutsolutionscontainingtheseions,suchaspercentionizationandthe formationofprecipitates.
Questionsforthereader Lead(II)iodideisslightlysolubleinwater.Itformsabrightyellowprecipitateiftoomuchisdissolved.Youhavedeterminedthat0.75gwilldissolve inoneliterofcoldwater.Whatisthemolarsolubilityoflead(II)iodide?WhatistheK spvalue? Afterheatingthewater,thesolubilityrisesto4.3gperliter.WhatisthenewK spvalue?
Asimilarprocesscanbeusedtodetermineasubstance'ssolubilitybyworkingbackwardsfromthesolubilityconstant.
PercentIonization
Onceanioniccompound'sK spvalueisknown,itispossibletodeterminethe percentionization,orrelativeamountofdissociatedions.
WeknowtheK spforsilversulfate,whichisslightlysoluble,andwewanttoknowthepercentionization.
Substitute xfortheconcentrationofsulfateand 2xforsilver.Solveforx.
Wenowknowthemaximumconcentrationoftheions.Anyremainingsilvernitratewillbeundissolved becausethesolubilityhasbeenexceededandthesolutionissaturated.Todeterminepercentionization, wemustknowhowmuchsilversulfatewasdissolved.Forthisexample,assume1.00molewasdissolved into0.500Lofwater.
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Asyoucansee,thepercentionizationdecreasesastheamountofsoluteincreases.Thisisbecausethesolutionissaturatedandnomoreionswilldissociate.
Questionforthereader LithiumfluoridehasaK spof1.84x103.If1.5garedissolved,whatwillbethepercentionization?
Precipitates
Obviously,thedissociatereactionoccursinreverseiftherearetoomanyions.Inthiscase,thesolutionissaturated,andanyexcessionswillsolidifyandformaprecipitate. Iftwosolublesolutionsaremixed,butthecanformaninsolublecompound,aprecipitatewillform.
Forexample,asolutionofsilvernitrateismixedwithasolutionofsodiumchloride.Botharesoluble. Silverchloride,however,isinsoluble.
If1.00mgNaCland1.00mgAgNO3aredissolvedinto1.00Lofwater,willaprecipitateform?
No,aprecipitatewillnotform.
Now,anothermilligramofsodiumchlorideisdissolved.
Theextrachlorideionswillbondwithsilverionsandformasolidprecipitate.
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Inthiscase,theprecipitatewouldprobablybetoosmallanddilutetobenoticed.Asmoreionsareadded,however,thesolutionwillbecomevisiblycloudy.
Questionforthereader CalciumcarbonatehasaK spof3.36x109.Ina0.01Msolutionofcalciumchloride(soluble),howmanymolesofsodiumcarbonate(alsosoluble) canbeaddedbeforeprecipitatesform?
Introduction
Kinetics
Chemicalkineticsisthestudyoftheratesofchemicalreactions. Youmayknowifareactioniscapableofhappening,andyoumay knowhowfarthereactionwillproceed,butyoudon'tknowfastit willhappen.Considertworeactions:therustingofanironnailandthecombustionofpropane.Bothreactionswilloccur,andbothwilloccurtocompletion.Therustingwilltakeyears tocomplete,butpropanewillcombustinaninstant.Furthermore,thenailwillrustfasterwhenit'smoist,andslowerinthepresenceoflessoxygen.Obviously,therearefactorsthat affecttheratesofchemicalreactions.Thestudyofthesefactorsandratesis chemicalkinetics.
Thisironwirehastaken yearstobecomerusty.
Thisfiretookonlya momenttostart.
ReactionRate
Considerthisgenericchemicalreaction.(Lowercaselettersrepresentthemolarcoefficients.)
Thereactionrate isdefinedastherateofchangeoftheconcentrationofthesubstances.Remember thatasubstancewritteninsidebracketsisitsconcentration,anditisalwaysraisedtothepowerofits

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coefficientinthereaction(justlikeequilibriumexpressions).ThereactionrateinvolvesCalculus,butinnon mathematicaltermsitissimplytherateofchangeoftheconcentrations.
Actuallymeasuringtherateofchangeofthereactantsandproductsisdifficult.Instead,thereactionrate canbeaccuratelymodeledbya rateequation.Thisisanexampleofarateequationthatmightmodelthe abovereaction,where isaconstant. Insummary,the reactionratecanbedeterminedusinga rateequation,whichdependson(amongotherthings)theconcentrationofthereactants.Thereactionrateessentially measuresthespeedatwhichareactionproceeds.
CollisionTheory
Collisiontheorypredictsthatreactionsoccurwhenmoleculescollide.Inorderforreactantstoformproducts,thereactantmolecules mustphysicallycollidesothattheycanrearrangethemselvesintoproductmolecules.Onlysomecollisionsare effectivebecausethe collisionmustinvolveenoughenergytoallowthereactiontooccur.Thisiscalled activationenergy,theenergyneededtobegina reaction. Activationenergyexplainswhygasolinewillnotspontaneouslyignite.First,asmallsparkorflamemustbepresent.Theheat generatedbythesparkgivesthegasolinemoleculesenoughenergytoactivatethereaction.Beinghighlyexothermic,the combustionofgasolinereleasesalargeamountofheatmorethanenoughtoactivatefurtherreactionsandcreateafire. Collisiontheoryallowsustopredictthe rateconstant forarateequation(seeabove).Atagiventemperature , where istheUniversalGasConstant, istheactivationenergyforthereaction, isapredictedtoactualcorrectionfactor,and canalsobecalculatedmathematically.Itistheaveragenumberofreactantparticlecollisionsperunittime. isthe collisionfactor.Thecollisionfactor ,therateconstantis: Allreactionshaveactivationenergy regardlessofbeingendothermicor exothermic.
FactorsAffectingRate
Therateofareactionisaffectedbymanyfactors.Theseeffectscanbemeasuredempiricallyorexplainedbycollisiontheory.
Concentration
Thisisthemostobviousfactoraffectingrate.Increasingtheconcentrationofthereactantswillincreasetheratetheyreact.Thisisthemainpurposeofwritingarateequationthe concentrationscanbepluggedinlikevariablesandtheratecanbesolvedmathematically.Inarateequationintheform ,theconcentrationsarethevariables (raisedtothepowersoftheircoefficientsinthereaction).Allotherfactorsthatcanaffectratearelumpedinto ,whichisconsideredaconstant. Collisiontheoryexplainsthis.Higherconcentrationsmeansmoremoleculespackedintoagivenspace.Therefore,therewillbemorecollisionsandthusafasterreaction.
Pressure
Inareactionofgaseousreactants,thepartialpressureofthegaseshasthesamefunctionastheconcentration. However,increasingtheoverallpressure(ordecreasingthevolumeifyourememberthegaslaws)willalsoresultinagreater
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However,increasingtheoverallpressure(ordecreasingthevolumeifyourememberthegaslaws)willalsoresultinagreater reactionrate.Theincreasedpressurecausesthemoleculestocollidewithmoreforce.Morecollisionswillbeeffectiveandtherefore productswillformfaster.
Addinganinertgaslikeargonwillnotaffect theratebecausethepartialpressuresof thereactinggasesremainthesame.
Temperature
Asyoushouldalreadyknow,amolecule'skineticenergyisdirectlyproportionaltoitstemperature.Byincreasingthetemperature,moleculescollidemorevigorously,andmore collisionswillbeeffective.
Stirring
Ina heterogeneousreactiontherearetwoormorephasesofmatterinteracting,suchasasoliddissolvingintoaliquid.Stirringorshakingthemixturewillspeedupthereactionrate. Thisiscommonsense.Whenyouaddsugartoadrink,youstiritbecauseyouknowitwilldissolvefaster.Collisiontheorywouldpredictthisbecausethestirringwouldincreasethe numberofcollisionsbetweenreactantmolecules. Inasimilarmanner,increasingthesurfaceareaofasolidreactantwillincreasethereactionrate.
Catalysts/Enzyme
A catalystisasubstancethathelpsareactionproceedwithoutbeingconsumed.Catalystshavealreadybeenexploredinthisbook.One wayoranother,theyreducetheactivationenergyneededforareactiontooccur,makingitoccurfaster. Inbiochemistry,an enzymeisaproteinthatservesasacatalyst.
ReactionRates
Introduction
Reactionratesofachemicalsystemprovidetheunderpinningsofmanytheoriesinthermodynamicsandchemicalequilibria. Elementaryreactionsareonestepprocessesinwhichthereactantsbecometheproductswithoutany intermediatesteps.Thereactions areunimolecular(Aproducts)orbimolecular(A+Bproducts).Veryrarely,theycouldbetrimolecular(A+B+Cproducts),but thisisnotcommonduetotherarityofthreemoleculescollidingatthesametime.
TheactivationenergyE aisdecreasedbya catalyst,buttheoverallreactiondoesnot change.
Acomplexreactionismadeupofseveralelementaryreactions,withtheproductsofonereactionbecomingthereactantsofthenextuntiltheoverallreactioniscomplete.
RateEquation
Consideranarbitrarychemicalreaction.
Therateatwhichtheproductswillformfromthereactantsisgivenbythis rateequation.
Therateofthereversereaction(whichalsooccurstoalesserextent)hasitsownrateequation.
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Note[A]israisedtothepowerofm,itscoefficient,justlikeanequilibriumexpression.Therateofthereactionmayrelyonthemolarcoefficientsofthereactantspecies,butitmight not.However,foranelementaryreaction,theconcentrationsofthespeciesAandBarealwaysraisedtotheirmolarcoefficients.Thisonlyappliesto elementaryreactions,whichis averyimportantdistinctiontomake.
Order
Theorderofanequationiswhattheconcentrationofasubstanceisraisedtointherateequation.Thegreaterthenumber,thegreatereffectitwillhaveonrate.Forexample,zero orderequationsdonoteffecttherate.Tofindtheorder,youmustalteroneconcentrationandkeeptherestthesame,Dividinggivesanequationwhichcanbeusedtosolveforthe order.Tofindoverallorder,simplyaddallorderstogether.
ZeroOrderEquations
Zeroorderequationsdonotdependontheconcentrationsofthereactants.
Thereisonlyaratecoefficientwithnoconcentrations.Therateprobablydependsontemperature,andpossiblyotherfactorslikesurfacearea, sunlightintensity,oranythingelseexceptforconcentration.Thesereactionsusuallyoccurwhenasubstanceisreactingwithsomesortof catalystorsolidsurface.
The integratedratelawtellsushowmuchreactantwillremainafteragivenamountoftime.Integratedratelawscanbefoundusingcalculus, butthatisn'tnecessary.Inthiszeroorderintegratedratelaw, istheratecoefficientfromtherateequation, istime,and isthe startingconcentration.
FirstOrderEquations
Firstorderequationsdependontheconcentrationofaunimolecularreaction.
Thereisaratecoefficientmultipliedbytheconcentrationofthereactant.Aswithazeroorderequation,thecoefficientcanbethoughof asaconstant,butitactuallyvariesbytheotherfactorsliketemperature.Therecanbeotherreactantspresentinthereaction,buttheir concentrationsdonoteffecttherate.Firstorderequationsareoftenseenindecompositionreactions.
Thisistheintegratedratelaw.
The halflifeofareactionistheamountoftimeittakesforonehalfofthereactantstobecomeproducts.Onehalflifeis50% completion,twohalfliveswouldleadto75%completion,threehalflives88%,andsoon.Thereactionneverquitereaches100%,butit doescomecloseenough.Tofindthehalflife,youcanalgebraicallymanipulatetheintegratedratelaw.
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SecondOrderEquations
Secondorderequationsdependonthetwoconcentrationsofabimolecularreaction.
Thisistheratelawforasecondorderequation.
Iftherearetwomoleculesofthesamekindreactingtogether,theratelawcanbesimplified.
Inthatcase,thisistheintegratedratelaw.
Thisisthehalflifeforasecondorderreaction(withonlyonereactant).
Equilibrium
Equilibriumwilloccurwhentheforwardandreverseratesareequal.Asyoumayhavealreadynoticed,theequilibriumexpressionofareactionisequaltotherateequationsdivided.
Considerthisreaction,the dimerizationofnitrogendioxideintodinitrogentetraoxide.
Theforwardreactionrateissecondorder,andthereversereactionrateisfirstorder.
Theratecoefficientsmaybedifferentforthetworeactions.Ifthereactionisinequilibrium,theforwardandreverseratesmustbe equal.
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Rearrangingtheequationgivestheequilibriumexpression.
Understandingkineticsexplainsvariousconceptsofequilibrium.Nowitshouldmakesensewhyincreasingthereactantconcentrationwillmakemoreproducts.Theforwardrate increases,whichusesupreactants,whichdecreasestheforwardrate.Atthesametime,productsaremade,whichincreasesthereversereaction,untilbothreactionratesareequal again.
ArrheniusEquation
TheArrheniusequationdeterminesaratecoefficientbasedontemperatureandactivationenergy.Itissurprisinglyaccurateandveryuseful.TheArrheniusequationis:
istheactivationenergyforthereaction,injoulespermole. determinedexperimentally.
istheUniversalGasConstant,
isthetemperature(inkelvin),and
isthe prefactor.Prefactorsareusually
ReactionMechanisms
Chemistsoftenwritechemicalequationsforreactionsasasinglestep,whichonlyshowsthenetresultofareaction.However,most chemicalreactionsoccurinaseriesofstepscalledelementaryreactions.Alloftheseelementaryreactionsmustadduptoequaltheoverall balancedequation.Thecompletesequenceoftheseelementarystepsiscalleda reactionmechanism.Thereactionmechanismisthe stepbystepprocessbywhichreactantsactuallybecomeproducts.Itisthe"how"ofthereaction,whereastheoverallbalancedequation onlyshowsthe"what"ofthereaction.
RateDeterminingSteps
Sometimes, intermediatesubstancesarecreatedintheprocessthatdisappearintheend.Takethefollowingexampleofahomogeneous reaction(whereproductsandreactantsareallinthesamephase):
Thereareactuallytworeactionsoccurringatdifferentspeeds. (slow) (fast) Sincethefirststepistheslowest,andtheentirereactionmustwaitforit,itisknownasthe ratedeterminingstep.Theoverallreaction ratedependsalmostentirelyontherateofthesloweststep.Theotherstepsarefastenoughthattheirrateisinsignificant,astheyare alwayswaitingfortheslowersteptocomplete.

Astepbystepbreakdownofareaction showsitsmechanism,theactualprocess ofreactionsbecomingproducts.
Whyisthefirststepslower?Collisiontheoryexplainswhetherornotparticlesreactwhentheycollide.Theparticlesmustcollidewithaminimumenergyandaproperorientationifa reactionistooccur. Theminimumenergyneededforareactiontooccurisits activationenergy.Theparticlesmustbemovingfastenoughfortheircollisiontosatisfytheactivationenergy.Withoutthe necessaryenergy,theparticleswillbounceoffeachotherwithnoreaction.Agoodexampleofactivationenergyisabutanelighter,whichneedsasparkbeforethefluidburns.The sparkprovidesenoughenergytotheparticlestomaketheircollisionseffective.
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Reactionswithhighactivationenergywillbeslowerthanthosewithlowactivationenergy.Withahighactivationenergy,lessparticlesarelikelytogeneratetheneededenergywhen theycollide.Reactionsthatbreakbonds,especiallydoubleortriplecovalentbonds,willhavehigheractivationenergy. Theparticlesmustalsocollidewiththeproperorientation.Forexample,thereactionintheanimationaboveshowsanammoniumionreactingwithaNCOion.Forthereactionto occur,theammoniumionmustcollidewiththenitrogenoftheNCO.Iftheionsdon'tcollideintherightplacewhilefacingintherightdirection,thereactioncannotoccur. Reactionsthathaveveryspecificrequirementsfortheorientationofthecollidingparticleswillbemuchslower.Reactionsthatcanoccurwithoutaspecificorientationwillhappen faster.
DeterminingtheValidityofanElementaryStepModel
Inorderforaproposedelementarystepequationtobevaliditmustfulfiltheserequirements. 1.Therateequationoftheslowstepmuchmatchtherateequationoftheoverallreaction. 2.Thereactantsandproductsofalltheelementarystepsaddedtogethermustequaltheoneoftheactualequation. 3.Theratelawfortheelementarystepmustbeabletobewrittenwithouttheconcentrationoftheintermediates,becausetheintermediatesaretoosmalltobeaccurately measured. Forexample,ifgiventhisequationandaskedtoprovetheratemechanism Equation ProposedMechanism (fast) (slow)
Weknowthatwhenthereactionoccursbackwards,thekchangesfromktok^{1}.So,wesubstituteinthebackwardsrateforO_3,andplugitintotheslowstep.Then,taketherate equationoftheslowstep.Wefindthatitisthesameastheratelawfortheoverallequationandmeetsthethreecriteriaabove,sothisproposedmechanismisvalid.
Introduction
Thermodynamicsisthestudyofthechangesinenergythatoccurin reactions.
Thermodynamics
Systems
A systemisthesetofsubstancesandenergythatisbeingstudied.If,forexample,reactionsareoccurringinajar,everythinginsidethejaristhesystem,andeverythingoutsidethe
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A systemisthesetofsubstancesandenergythatisbeingstudied.If,forexample,reactionsareoccurringinajar,everythinginsidethejaristhesystem,andeverythingoutsidethe jaristhe surroundings.Thesurroundingsareeverythingnotinthesystem,whichmeanstherestoftheuniverse.Thesystemandthesurroundingstogetherarecalledthe "universe". Oneimportantissueiswhatkindofinteractionsexistbetweenthesystemanditssurroundings.Somesystemsmayexchangematterandheatwiththesurroundings(likeasystemof boilingliquidlosingmatterandheatwiththevapor).Thisiscalledan opensystem.Ifthereisjustheatexchangeoccurringbetweenthesystemanditssurroundingsitiscalleda closedsystem.Nomattercanenterorleaveaclosedsystem.And,finally,ifthereisnoexchangeofheatandnoexchangeofmatter,thesystemiscompletely isolated.
Temperaturevs.Heat
Ifyouputahotironpotundercoldwater,itcoolsdownveryquickly.Thisisbecauseironhasalow specificheat,whichistheamountofenergyrequiredtoincreasethe temperatureofonegramofasubstancebyonedegreeCelsius(orKelvin).Solidirononlyrequires0.45J/(g*K),whileliquidwaterholdsaboutninetimesasmuchenergy(heat)per degree(temperature).Sowhenwaterreceivesenergyfromthepot,itonlywarmsupbyafewdegrees,whilethepotcoolsdownsubstantially.
ThermochemicalEquations
Equationsdon'tjustshowchemicalstheyalsoshowhowmuchenergyisrequiredorreleased.Thisenergyiscalled enthalpy.Therearetwowaystowriteathermochemical reaction,forexample:
Notethatthenumberisnegativeinthesecondformat.Also,noticehowthefirstequationhasdoubletheenergybecausetherearetwomolesofwater.Thesecondequationshows theamountofheat permole,sothenumberofmolesdoesnotaffectit. Fromathermochemicalreaction,onecantellthe molarheatofformationofacompound.Usually,thisismeasuredat25C,andiswrittenasHf.Itistheamountofheat requiredtomakeonemoleofthesubstance.Thesmallsymbolmeans"standard",asinStandardTemperatureandPressure. Molarheatofcombustionistheoppositeofthemolarheatofformation.Itmeasurestheamountofenergyreleasedwhenamoleofthecompoundisburned.ItiswrittenasHc.
Enthalpy
Theenthalpyofachemicalsystemisthe"heatcontent"ofthesystemtheenergyitcontains.Enthalpyisrepresentedbythe symbol .
EnthalpyofReaction
Allreactionshavesomeamountofenthalpy.Itissimplytheamountofheatabsorbedorreleasedbythereaction.Combustion reactionsobviouslyreleaselargeamountsofheat.Theyhavenegativeenthalpy.Anegativeenthalpyrepresentsanexothermic reaction,releasingheat.Areactionthatabsorbsheatisendothermic.Itsenthalpywillbepositive,anditwillcooldownits surroundings. Considerthesetworeactions:
Theabsoluteenthalpyofasystemcannot bemeasureddirectly.However,itis possibletomeasurechangesinenthalpy (H)bymeasuringtemperaturechanges, whichrepresentheatbeinglostorgained.
Thisreactionisexothermic(negativeenthalpy,releaseofheat).Whenthereactionoccurs,the surroundingswillincreaseintemperatureduetothegainofheatthesystemreleases.Foreverymole
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ofpropane(C3H8)formed,104.67kilojoulesofenergyarereleased.
Thisreactionisendothermic(positiveenthalpy,absorptionofheat).Whenthereactionoccurs,the surroundingswilldecreaseintemperatureduetothelossofheatthesystemabsorbed.Forevery moleofNOformed,378.3kilojoulesofheatareabsorbed.(Notethatthereactionshows twomoles beingformed,sotheenthalpyisdoublethatof onemolebeingformed.)
Althougheveryreactionhasachangeinenthalpy,theamountdependsonthetemperature.Thesamereactioncouldbeendothermicatonetemperatureandexothermicatanother. Enthalpiesmustbegivenataspecifictemperature.Thereactionsaboveshowtheenthalpiesat25C.
TemperatureandHeat
Thereisarelationshipbetweentemperatureandheat.Ifanobjectgainsorlosesheat without anyphasechanges,thisreactionrelatestemperaturetoheat:
istheamountofheat(injoulesorkilojoules)and specificheat.
isthechangeintemperature(Celsiusdegrees).
isthemassoftheobject(ingrams,usually)and istheobject's
Specificheatisaconstantthatdependsontheparticularmaterialoftheobject.Itismeasuredinjoulespergramdegree.Itisdeterminedexperimentally.Youcanlookitupina chart,oryoucancalculateitifyoumeasuretheamountofheataddedandthechangeintemperature.Thetoeinhereheatofwateris4.186J/gdegree.Foronegramofwater,the temperaturerises/fallsbyonedegreeCelsiusforevery4.186joulesofheatadded/removed.
Entropy
Entropyisthemeasureofdisorderinasystem.
AnExample
First,let'sexamineanonchemistryexample.Sayyouhaveonecardfromadeckofplayingcards.Itcanhaveoneof52possiblevalues.Nowyoupickupfourmorecards.Ifthe deckwereshuffledrandomly,theoddsofyouholding,say,a"straightflush"are0.00154%.Theoddsofhavinga"highcard",whichisessentiallya"nothing"hand,is50.12%.Inthe caseofastraightflush,thecardsyouareholdingarehighlyorganized.Theymustbeinaspecific,exactpattern(like109876ofthesamesuit).Tohaveahighcard,notwocards musthavethesamerankandthecardscannotbeinorder. Thereisaverylowprobabilityofhavingastraightflushbecausethecardsareinaveryorderlystate.Thereisalargeprobabilityofhaving"nothing"becausethecardsareina random,disorderlystate.Inourcardplayingsystem,straightflusheshave lowentropybecausetheyaresoorderly."Nothing"handshave highentropybecausetheyaredisorderly andrandom.Furthermore,ittakesminimalefforttotossallthecardsintheairandrandomizetheirorder.Increasingtheentropyofthesystemcomesnaturally.Ontheotherhand, sortingthecardsinordertakestimeandeffort.Itdoesnothappenrandomly.Decreasingtheentropyofthesystemisunnaturalandtakeseffort,orenergy.
InChemistry
Theentropyofachemicalsystemisameasureofitsdisorderorchaos.Moreprecisely,itisameasureofthe dispersionofenergy.Asolidhaslowentropy(lowchaos,orderly) becausethemoleculesarelockedintoarigidstructure.Theirenergyisnotdispersedfreely.Agashashighentropy(highchaos,disorderly)becausethemoleculesarefreetomove aboutrandomly.Theenergyofthesystemisdispersedoveralargeareawithunlimitedpossibilitiesofthelocationofeachmolecule.
Astemperaturedecreases,sodoesentropy.Theoretically,at absolutezero(0K,or273C),theentropyofthesystemwouldbe
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Astemperaturedecreases,sodoesentropy.Theoretically,at absolutezero(0K,or273C),theentropyofthesystemwouldbe zero.Thisisbecausethesolidwouldbeperfectlycrystallizedsothatitsenergyisnotdispersedatall.
Absolutezerocanneverbeachieved.
Asyouwillsoonlearn,theSecondLawofThermodynamicstellsusthattheentropyoftheuniversealwaysincreases.Thinkaboutit.Ifyouhavebuiltahouseofcards,theentropy ofthesystemislow.Ahouseofcardsisveryorderly,witheachcardhavingaveryspecificlocation.Thehouseofcardswillundoubtedlycollapse.Theresultingpileofcardsisvery disorderly.Thecardscanbeinanypositionandstillbearandompileofcards.Theentropyhasincreasedspontaneously.Housesofcardswillspontaneouslycollapse,buttheynever spontaneouslybuildthemselvesup.Thisisbecausehighentropyisnaturalandlowentropyisunnatural.
EntropyChanges
Whenanalyzingtheentropychangeofachemicalreaction,youwouldneedspecificnumbers.Asaguideline,youcanestimatetheentropychangebasedonsomebasicrules:
Meltingandboiling increasesentropy Freezingandcondensing decreasesentropy Dissolvingasolute increasesentropy Formingprecipitates decreasesentropy
Ifyoudohappentoknowtheabsoluteentropyofsubstancesinareaction(bylookingitupinachart),youcancalculatethechangeinentropy.Entropyissymbolizedwith .The changeinentropyis .Aswithenthalpy,thedegreesymbol( )representsSTP.Thechangeinentropyistheabsoluteentropyoftheproductsminustheabsoluteentropyof thereactants.
Seealso
EntropyforbeginnersaWikibookthatprovidesamathematicalexplanation.
TheFirstLaw
The FirstLawofThermodynamicsissimplyarestatementofthe LawofConservationofEnergy.Thereareafewwaysofstatingit,buttheyallmeanthesamething: "Energyisneithercreatednordestroyed.Itcanonlychangeform." "Thechangeinthesystem'sthermalenergyisequaltotheheataddedtothesystemminustheworkdonebythesystem."
Thefirstdefinitionisselfexplanatory.Asanexample,apropanegrilldoesnot"create"energywhenitcooksfood.Theenergystoredwithinpropanemoleculesandoxygenatomsis releasedintheformofheatandlightwhenthepropanemoleculesreassemblethemselvesintocarbondioxideandwater(thecombustionreaction).Energyhasnotbeencreatedor destroyed.Ithassimplychangedfromchemicalpotentialenergyintolightandthermalenergy. Thesecondexplanationcomesfromaphysicspointofview.Itmeansthataddingheattoasystemincreasesitsinternalenergy,andasystemthatdoeswork(likebreakingbondsor assemblinglargemoleculesfromsmallones)decreasesitsinternalenergy.Overall,thetotalamountofheat,work,andenergyremainsconstant.Thisshouldmakesensebecause heatisenergyandworkisenergybeingapplied,sobasedonthefirstdefinition,allformsofenergymustbeaccountedfor.
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TheSecondLaw
Introduction:Apowerfullaw.
Thesecondlawofthermodynamicsisbasedonourcommonhumanexperience.Itdidn'tbeginwithcomplicatedapparatusorcomplextheories,butratherwiththinkingabouthow oldfashionedsteamenginesworkedandthefirstimportantequationappearedtobeverysimple:justq/T. Yetthesecondlawisprobablyourmostpowerfulaidinhelpingusunderstandwhytheworldworksasitdoesbothinsimpleandincomplexways:whyhotpanscooldown,whyping pongballsdon'tbounceforeverwhentheyaredropped,whygasoline(plustheoxygeninair)makesenginesrun,whyour"engines"ourbodiesrunandwecontinuetoliveandour bodiesstaywarmevenwhenit'scold,butalsowhywediewhensomechemicalreactionswithinusfail.Infact,thesecondlawhelpstoexplaineverythingthathappensinour physicalworld.Inchemistry,it'sespeciallyimportantbecauseitcantelluswhetheranychemicalreactionthatwewriteonpaperwillprobablybespontaneousandgoaswehave writtenit.
TheBigProblem
Unfortunately,foralmostacenturyandahalf,thesecondlawhasbeenexpressedbyexpertsinwaysthatabeginnerinchemistrycouldnotpossiblyunderstandwithoutagreatdeal ofadditionalexplanation.Herearejustthreeofsome25explanationsthathavebeenmostprominent: "Theentropyoftheuniverseincreasestowardamaximum"(Clausius) "Itisimpossibleinanywaytodiminishtheentropyofasystemofbodieswithouttherebyleavingbehindchangesinotherbodies"(Planck) "Inanyirreversibleprocessthetotalentropyofallbodiesconcernedisincreased."(Lewis) Entropy,entropy,entropy!Butwhatisentropy?Evensometextbooksstillsaysomethinglike"Don'taskaboutunderstandingit.Justworktheproblemsthathaveentropyinthemand you'llgraduallyunderstanditbecauseyouwillbeabletoworkwithit"!That'stheoldwaywhichfortunatelyhasbeendiscardedbymostUSgeneralchemistrytexts.(Seelistat http://www.entropysite.com/#whatsnew.)Thegoodnewsofthetwentyfirstcenturyisthatnowentropycanbedescribedasasimple idea(nomatterhowcomplextocalculateand dealwithinadvancedcoursesandresearch.)Becauseofournewconceptualapproach,abasicversionofthesecondlawcanbeunderstoodeasily.
AModernVersion
Whatdoesthat"energyofalltypes"and"becomingdispersed"mean?Let'sfirstthinkaboutlight(whichtechnicallyiselectromagneticradiation).Doestheradiationfromalightbulb stayinsidethatglassofthebulb?Ofcoursenot.Itspreadsoutjustasfarasitcan,hinderedfromdispersingtomilesandevenfartheronlybydustorairdensitydifferences.What aboutthesoundfromastereospeakerdoesitstayinsideadormroomoracar?Itdispersesfartherthanotherpeoplewanttohearit,usually!Andwhathappenstothekinetic energyofafastmovingcarifthecarshouldhitabrickwall?Itspreadsoutinacrashingsound,intwistingmetalandheatingitandtearingapartthebricksofthewallsothattheyfly around,slightlywarmerthantheywere.Thosearejustafewexamplesofdifferenttypesofenergyandsomewaysinwhichtheybecomedispersedorspreadout.
TheImportanceoftheSecondLaw
Inchemistry,thetypeofenergyinwhichwearemostofteninterestedisthekineticenergyofmolecules,molecularmotionenergy.WeknowfromKineticMolecularTheorythat moleculesareinconstantmotioniftheirtemperaturesareabove0K.Ingaseslikenitrogenandoxygen,theyaremovingatanaveragespeedofathousandmiles(1600km)anhour at298Kandgoabout200timestheirdiameterbeforebumpingintoanothermolecule[citationneeded].Themoleculesinliquidsmaybemovingapproximatelyasfasteventhough theyareconstantlyhittingoneanotherastheymovealittlehereandthere.Insolidstheparticles,moleculesoratomsorions,canonly"danceinoneplace"(vibratingincoordination withtheotherparticlesinthesolid).Thisisakineticenergyofvibrationthatisequivalenttothemotionenergyofgasesorliquidsatthesametemperature. Themotionenergyofmoleculesconsistsoftheirtranslation,rotation,andvibration(Figure1ofhttp://www.2ndlaw.com/entropy.html.)Notethatthisvibrationisvibration insidea moleculeandbyitself,asthoughthechemicalbondsbetweenatomswerelikesprings.Thevibrationinacrystalthatwewerejusttalkingaboutisavibrationofawholemoleculeor otherparticleinoneplaceandcoordinatedwiththeothermoleculesinthecrystal.
ExamplesfromEverydayLife
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Let'sseehowthesecondlawhelpsustounderstandourcommonexperiencebetter,toseehowsomanytotallydifferenteventsreallyarejustexamplesofenergydispersingor spreadingout,i.e.,ofthesecondlaw.Arockwillfallifyouliftitupandthenletgo.Hotfryingpanscooldownwhentakenoffthestove.Ironrusts(oxidizes)intheair.Airinatireis atahighpressureandshootsoutevenfromasmallpuncturetothelowerpressureatmosphere.Icecubesmeltinawarmroom.
AFallingRock
Arockhaspotentialenergy(PE)localizedinitwhenyouliftitupabovetheground.Therockisthe systemeverythingelseitencountersisthe surroundings.Droptherockandits PEchangestokineticenergy(energyofmovement,KE),pushingairasideasitfalls(thereforespreadingouttherocksKEabit)beforeithitstheground,dispersingatinybitof soundenergy(compressedair)andcausingalittleheating(molecularmotionenergy)ofthegroundithitsandintherockitself.Therockisunchanged(afteraminutewhenit dispersestotheairthesmallamountofheatitgotfromhittingtheground).Butthepotentialenergythatyourmuscleslocalizedinbyliftingitupisnowtotallyspreadoutand dispersedalloverinalittleairmovementandalittleheatingoftheairandground.
AHotFryingPan
Ahotfryingpan?Theironatomsinahotfryingpan(system)inaroom(surroundings)arevibratingveryrapidly,likefast"dancinginplace".Therefore,consideringboththepanand theroom,themotionenergyinthehotpanislocalized.Thatmotionenergywilldisperseifitisnothindered,accordingtothesecondlaw.Wheneverthelessrapidlymoving moleculesinthecoolerairoftheroomhitthehotpan,thefastvibratingironatomstransfersomeoftheirenergytotheairmolecules.Thepanslocalizedenergythusbecomes dispersed,spreadoutmorewidelytomoleculesintheroomair.
SomeRustingIron
Inachemicalreactionsuchasironrusting,i.e.,ironplusoxygentoformironoxide(rust),thereactantsofironandoxygendon'thavetobeatahightemperaturetohaveenergy localizedwithinthem.Ironatoms(asFeFeFe)plusoxygenmoleculesoftheair(OO)havemoreenergylocalizedwithintheirbondsthandoestheproductoftheirreaction,iron rust(ironoxide). Thatswhyironreactswithoxygentoreleaseenergyfromtheircombinedtotalofhigherenergybondsandformthelowerenergybondsinironoxide.Then,allthatdifferencein energybecomesdispersedtothesurroundingsas heat i.e.,thereactionisexothermicandmakesmoleculesinthesurroundingsmovefaster.Butrememberhowchemicalreactions occur!Rememberthatitrequiresenergytobreakbondsandthereforetostartanyreactiontheremustbesomeextraenergy,anactivationenergysuppliedsomehowtobreakabond ormanybondsinthereactingsubstances.(Forinformationaboutactivationenergies,seehttp://www.2ndlaw.com/obstructions.html)Then,ifthebondsthatarebeingformedinthe productaremuchstrongerthanthosebeingbrokeninthereactants,thatdifferenceinenergy(whichusuallycausesgreatermotionenergyofallthemolecules)canfeedbackto breakmorebondsinthereactants. However,inthecaseofironreactingwithoxygenatnormalroomtemperaturearound298K,theprocessisveryslowbecauseonlyafewoxygenatomsaremovingexceptionallyfast andhittheironjustrightsoanFeFebondandanOObondarebrokenandanFeObondcanform.Thereisn'tenoughheat(motionenergy)localizedinnearbyironatoms,and therearenootherunusuallyfastmovingoxygenmolecules.It'saslowprocessdependingoncollisionofthesmallamountoffastmovingoxygenatomsinthesurroundingstomake ithappen. Therefore,eveninmoistair(thatspeedsupanotherprocessyieldingironoxide),irondoesn'treactveryrapidlywithoxygenbutitsteadilydoessoandintime,boththeironatoms andtheoxygenmoleculespreadouttothesurroundingstheportionoftheirbondenergythatironoxidedoesn'tneedforitsexistenceatthattemperature.
ALeakyTire
Airinatireisatahigherpressurethantheatmospherearoundit,soitshootsoutevenfromasmallhole.WhatcouldthathavetodowithabigdealliketheSecondLawof Thermodynamics?(Everyspontaneousphysicalorchemicalprocessinvolvesthesecondlaw!)Thosenitrogenandoxygenmoleculesinthetireeachhavemotionenergybutitisfar morelocalized,compressedinthesmallvolumeofthetire,thanitwouldbeinthehugevolumeoftheatmosphere.Thus,thesecondlawexplainswhypuncturesorblowoutsoccur: themotionenergyofthoselocalizedmoleculeswillbecomedispersedandspreadouttothelowerpressure,largervolumeatmosphereifitisnolongerhinderedbythetirewallsfrom becomingso.
AMeltingIceCube
Anicecubemeltsinabigwarmroom.Howcanthemeltingofalittleicecubeinawarmroommaybe200,000timesbiggerthanitisbeanexampleofthesecondlaw?Howcould
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Anicecubemeltsinabigwarmroom.Howcanthemeltingofalittleicecubeinawarmroommaybe200,000timesbiggerthanitisbeanexampleofthesecondlaw?Howcould thatpossiblybeaspreadingoutofenergy?Butthesecondlawhastodowithenergydispersalandthere'salittlespreadingoutinthat200,001stpartofthattotalofsystemplus surroundings! Lotsofthingsarehappeningwhenmoleculesofthewarmairdispersesomeoftheirenergytothemoleculesthatarevibrating(likedancingrapidlyinoneplace)intheicecube. Rightatthesurfacemanyhydrogenbondsbetweenthewatermoleculesoftheicearebrokenbythemotionenergyoftheairmoleculesbeingtransferredtothethosesurface molecules.(Thisdoesn'tchangetheamountofmotionenergyofthosemoleculesandthereforetheirtemperaturedoesn'tchange.Theyincreasein potentialenergyduetothe hydrogenbondbreaking.)Now,becausethewatermoleculeswhosehydrogenbondstoothermoleculesintherigidicestructurearebroken,theyarefreetoformhydrogenbondsto otherwatermoleculesthatareliquidtheycanexchangepartnersandmovefromonetoanother.Thevibrationalenergythatallowedthemtodanceinplaceinthecrystalis changedtotranslationalenergyintheliquidandthemoleculescanmovejustabit. Thus,althoughthetruepictureisjustabitmorecomplex(i.e.,itisthecloserenergylevelsintranslationthaninsolidvibrationthatmaketheenergyfarmoredispersedinliquidthan solid),wecansensethatthemovementofmoleculesinliquidwaterallowstheenergytobemorespreadoutthanincrystallineice,evenatmeltingtemperature.Itisnotamatterof orderand"disorder"!(That'sasmisleadingasmagicandasobsoleteas1898fashions.http://www.entropysite.com/order_to_disorder.pdf)
OrdertoDisorder
Thesecondlawtellsusaboutenergydispersal,and entropyisthewordforhowthatenergydispersalismeasuredhowspreadouttheenergybecomesinasystem,howmuch moredispersedithasbecomecomparedtohowlocalizeditwas.Suchenergychangesandconsequententropychangesarethefocusforunderstandinghowandwhyspontaneous eventsoccurinnature.Onlysometimesdothestructuresorarrangementsofmoleculesinanobjecthelpustoseegreaterorlesserlocalizationofenergy(thatusedtobecalled "ordertodisorder"). Nowwecanunderstandwhatscientistshavebeentalkingaboutthelastcenturyandahalfwhentheyspokeinapparentlymysterioussentenceslike"Theentropyoftheuniverse increasestowardamaximum."Alltheymeantwassimplythatenergy,everywhere,spreadsoutasmuchasitcan(andthatspreadingoutofenergyismeasuredbyentropy).
RecapandConclusion
Rocksfallingdownmountains,hotpanscoolingincoolrooms,anythingmadeofironrusting,anythingburningorreactingwithoxygen,allthesetypesofspontaneouseventsand chemicalreactionsthatoccurbythemselvesareduetoenergydispersingorspreadingout.Entropyisthequantitativemeasureofhowmuchenergyandhowmuchdispersaloccurs inaprocessorareaction.Therefore,entropyisconstantlyincreasingbecausespontaneouseventscontinuetooccurinourenergyrichuniverse.Thus,wecandecipherthefollowing statementofthesecondlaw: "Inanyirreversibleprocessthetotalentropyofallbodiesconcernedisincreased." Thatjustmeans:"Inanyprocessinwhichenergybecomesspreadout,themeasureofthatspreadingoutordispersing(i.e.,thetotalentropy)increaseswhenyouincludebothwhat happensinthesystemANDitssurroundings. Nowwecantranslate"secondlawlanguage"!Itseemsveryconfusingifyoureaditrapidly,buttakingitafewwordsatatimeandknowingwhatwehavejustreviewed,theideasare notcomplicated.
FreeEnergy
Introduction
What'sthepointofentropyandenthalpy?Sofar,youhavestudiedequilibriumtotellyouhowfarareactionoccursandkineticstotellyouhowfastareactionoccurs. Thermodynamicscantellyou if areactionwilloccur,andatwhattemperatures.Itmayseemtooobvious,butwhydoesanicecubespontaneouslymeltwhenitisat30C?Melting isendothermic,soitwouldseemthatthereversereaction(freezing)isfavored.Afterall,reactionsthatreleaseheatareusuallymorefavorablethanthosethatabsorbheat. Theansweris freeenergy(alsocalled GibbsFreeEnergy).Thechangeinfreeenergyforareactionultimatelydeterminesifitcanoccurspontaneouslyornot.Freeenergyisa combinationofentropyandenthalpy,andwhenareactiondecreasesthefreeenergy,itwilloccurspontaneously.
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TheEquation
Freeenergyisdefinedby .Bymeasuringorcalculatingtheentropychangeandenthalpychangeofareaction,youcandeterminethechangeinfree energy.Noticethatfreeenergydependsontemperatureaswell.Inthisequation(aswithallotherthermoequations) mustbean absolutetemperature,measuredinKelvin.So thefreezingpointofwaterisnotzerobutrather273K.ByusingtheKelvintemperaturescale,alltemperatureswillbegreaterthanzero. Whenyouhavesolvedfor foraparticularreactionatacertaintemperature,youwillfindoneofthreepossibleoutcomes: Reactiontype exergonic Means... thereactionoccursspontaneously. thereactionisatequilibrium. endergonic thereactionwillnotoccur. Equippedwiththisknowledge,youcandeterminethetemperatureatwhichareactionwillbeatequilibrium(bysettingGto0andsolvingforT).Ifareactionisendergonic,itwillnot occur spontaneously.However,atadifferenttemperature,thereactionmightoccur.Also,thereversereactionwillhaveanoppositevalueforG.Forexample,thecombustionof propanewillhavealargenegativevalueforitschangeinfreeenergy.Thereversereactionwouldhavethesamelargevalue,butpositive.Thismakessense,knowingthatpropane doesnotspontaneouslyprecipitatefromthesmokeyexhaustofagrill.
Spontaneity
Let'sreturntotheexampleofameltingicecube.AtT=273K(0C)theprocessesoffreezingandmeltingareatequilibrium.Gmustequalzero.Athighertemperatures,the meltingprocessoccursspontaneously,sowecandeducethatHispositiveandSisalsopositive.Wealreadyknowthatmeltingisendothermicandincreasesentropy,soitseems thefreeenergyequationworks. Betweenentropyandenthalpy,therecanbefourpossibleoutcomes: Result + + + + always+ always neverspontaneous alwaysspontaneous
+forlowT,andforhighT dependsonT forlowT,and+forhighT dependsonT
Wecanseethatthemeltingofanicecubeisspontaneousforhightemperatures.
RelatingFreeEnergy
Freeenergyisrelatedtoequilibrium,aswehavealreadyseen.Thereisanequationthatwillallowyoutoconvertbetweenreactionfreeenergyandtheequilibriumconstantfora particularreactionatagiventemperature:
istheUniversalGasconstant,and
isthe naturallogarithm.Ascientificcalculatorwillhavea [ L N ] tocalculatelogarithmsanda [ e ^ ] buttontocalculateantilogarithms.
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Group1
AlkaliMetals
The alkalimetalsaretheelementsin Group1(1A).Theyarelithium,sodium,potassium,rubidium,cesium,andfrancium.
TheElements
Theseelementsarebestmarkedbytheirreactivity.Physicallytheyaresoft,shiny(whenfreshlyprepared)solidswithlowmeltingpoints theyconductelectricitywell.Theyallhaveonevalenceelectronthattheyloseeasilytoalmostanyelectronegativesubstance.Alkali metalsareneverfoundintheirelementalformoutsidethelabbecausetheyaretooreactive.Eventhesmallestamountofoxygenor waterwouldreactwiththemetal.Forthisreason,alkalimetalshavenostructuraluse.Theymustbekeptunderinertliquidssuchas keroseneorininertgases(nitrogensufficesforanyoftheseelementsotherthanlithium). Alkalimetalshavemanyusesinbothbiologicallifeandindustry.Francium,however,isradioactiveanddecaysrapidlytootherelements, soithasnocommercialuseanditschemicalpropertiesarevaguelyunderstood. Alloxidizeeasilytothe+1oxidationstate.
Safety
Leaveexperimentswithalkalimetalstotheexperiencedchemists.
Sodiummetalissoftenoughtobecutwith aknife.
Reactions
Alkalimetalsreactviolentlywithwater,halogens,andacids.Thereactionsreleasesurprisingamountsofheatandlight.Inachemicalequation,alkalimetalsarerepresentedwithan M.Herearesomeexampleequations:
Alkalimetalsreactwithoxygentoform oxides,whichhaveadullerappearanceandlowerreactivity.The oxidesaremuchlessreactivethanthepuremetals.
However,theoxidesdoreactvigorouslywithwatertoforma hydroxide.Theresultinghydroxidesofthese elementsdissociatecompletelyinwatertoformsomeofthestrongestbasesknown."Lye"isanindustrial strengthbase,whichissodiumhydroxide(NaOH).
Thesehydroxidesreactreadilywithacidstoformwaterandtheircorrespondingalkali saltinaneutralization reaction.
Thepurealkalimetalcanalsoreactdirectlywithwater.Inthiscase,themetalisabasic anhydride.Gaseous hydrogenisreleased,whichisflammable.
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Exposinganalkalimetaltoahalogenwillcauseanextremelyexothermicreactionthatresultsinanionic salt.
Almosteverysaltofanalkalimetalishighlysolubleinwater.Theyformconductingsolutions,provingtheirionicnature.
FlameTests
Whenburnedinaflame,thealkalimetalsgiveoffauniquecolorthatcanbeusedtoidentifythem. FlameTests
Lithium(pinkishred flame)
Sodium(yellowflame)
Potassium(paleviolet flame)
Group2
AlkalineEarthMetals
The alkalineearthmetalsaretheelementsin Group2(2A).Theyareberyllium,magnesium,calcium,strontium,barium,andradium. Theyaresimilartoalkalimetals,butlessreactive. Alkalineearthmetalsallhavetwovalenceelectrons,andtheyeasilyoxidizetothe+2state.Withincreasingmass,theseelements becomesofter,havelowermeltingandboilingpoints,andbecomemorereactive.Noneappearuncombinedinnature,andallare separatedfromtheircompoundswithdifficulty.Alkalineearthmetalsreactwithhalogensand(exceptforberyllium)withwaterand oxygen.Magnesium,beinglessreactive,reactsonlyathighertemperaturesthantheotheralkalineearthmetals.Radiumisradioactive, soitschemicalpropertiesaredifficulttostudy. Thealkalineearthmetalsarechemicallyandphysicallysimilartothealkalimetals,buttheyarelessreactive.
Puremagnesiumcrystals
Safety Reactions
Thealkalineearthmetalsundergoreactionssimilartothealkalimetals,buttheir+2oxidationstatecausestheircompoundstobedifferent.Thefollowingreactionsusemagnesium asanexample,buttheotheralkalineearthmetalsundergothesamereactionsaswell.
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Magnesium oxideformsslowlyunlessignited.Powdersorthinslicesofmagnesiumcanbeignitedwitha match,somagnesiumisusedinfirestartingdevices.
Magnesiumburnsreadilyinoxygen,andsurprisinglynitrogenaswell.Airiscomposedmostlyofnitrogen, butmostelementswillnotreactwithnitrogenbecausenitrogenissostable.
Magnesiumoxideisabasic anhydride.Magnesiumhydroxideisastrongbase,althoughitssolubilityistoo lowforthispropertytobesignificant.
Magnesium nitridewillreactwithwaterorthemoistureinair.Thisreactionisdetectedbythepungentsmell ofammonia.
Magnesiummetalreactswithwatertoforma hydroxide,butonlyathightemperaturesorinthepresence ofacid.Calcium,beingmorereactive,willreactwithwateraslongasitshot.Theotherelementswillreact inwarmwater.Noticetheflammablehydrogengasthatisreleased.
Magnesiumwillreactexothermicallywithacidstoformanionic saltandhydrogengas.
Rememberthatallofthealkalineearthmetalscanundergothesereactionsmagnesiumwasjustanexample.Beryllium,however,ismuch lessreactivethantheothermetals,soit mightnotreact.
Uses
Berylliumisrareanditscompoundsaretoxic,soitisinlittleuse. Magnesiummetalhassomeuseinapplicationsneedingasoft,lightmetal.Magnesiummetalcanbeusedaneasilyburnedsubstancewithabrightlightinphotographicflashbulbs. Magnesiumhydroxideiscommonlyusedasastrongbutgenerallysafeantacid.MagnesiumsulfateiscommonlyknownasEpsomsalts. Evenmoresignificantly,magnesiumappearsinacompoundknownaschlorophyll,thegreenishpigmentinplantsandalgaethatallowsplantstoperformphotosynthesis.Itis essentialtoanimallife. Calciumhasnouseasastructuralmetal,butitscompoundcalciumcarbonateisamajorbuildingmaterialaslimestone.Calciumcarbonateisessentialtobonesandtoplantlife. Calciumandheavierelementsinthisgroupreactwithwarmwatertoformhighlyalkalinehydroxides. Strontium,muchrarerthancalcium,hasfewuses.Barium,alsorarer,hasfewusesotherthanitssulfate,acoatingusedforliningthedigestiveorgansforXrays. Radiumisrareandstronglyradioactiveitisextremelydangerousduetoitsintenseradioactivity.
Group13
Group13(IIIA)consistsofboron,aluminum,gallium,indium,andthallium.Boronisametalloid,buttheotherelementsaremetals.Allelementsinthisgrouphavethreevalence
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Group13(IIIA)consistsofboron,aluminum,gallium,indium,andthallium.Boronisametalloid,buttheotherelementsaremetals.Allelementsinthisgrouphavethreevalence electrons.
Boron
Boronisa metalloid,exhibitingcharacteristicsofbothmetalsandnonmetals.ItisneverfoundinitspureforminEarth,butitisa componentofsomeminerals.However,pureboroncanformasaresultofchemicalreactions.Itcanbeabrownamorphoussolid,ora crystallinesolid.Inthecrystallineform,itisblackandveryhard. Boronisapoorconductorofelectricityatnormaltemperatures,butathightemperaturesitdoesconductelectricity.Itschemical propertiesaremostly,butnotentirely,nonmetallic.Boronistheleastelectronegativenonmetal,soitreadilyloseselectronswhen reacting.Boronisalmostentirelyinthe+3oxidationstate.BoronhasanoxideB 2O3,anditisacidic.
Boric halidesarevolatilesubstancesthatattackwaterwiththeformationof boricacidB(OH)3andhydrogenhalides.

Aboraxcrystal.Borax(amineral containingboron)hasmanyusesincluding laundrydetergent.
Boric acidreactswithwatertoreleaseaproton.Itisaweakacid.
Boricoxide,atextremelyhightemperatures,canreactwithcarbontoform boron carbide.Boroncarbideisincrediblystrong,findinguseastankarmor.
Boronhasinterestingpropertieswhenitbondscovalently.Ithasthreeelectrons,soitusuallyformsthreesinglecovalentbonds,anexceptiontotheoctetrule. Substanceslikeborontrichloride(BCl3),boricacid,andtheborateion(BO33)areexamplesofboron'stendencytoformthreecovalentbonds.
Aluminum
Boroxin.Notice boron'sthree bonds.
Aluminum(Britishspellingaluminium)isametal,althoughitistooreactivetoexistinpureform.Instead,itisfoundinawidevarietyofmineralsincluding bauxite,theprimary sourceforextractingaluminum.AluminumisthethirdmostabundantelementinEarth'scrust. Unlikeboron,aluminumisanalmoststereotypicalmetalinitsphysicalproperties:itismalleableandductile,anditconductsheatand electricityverywell.Becauseofitslightness,resistancetocorrosion,attractiveness(approachingthatofsilver),andinexpensivenessto processalongwithadequatestrengthformanycommercialanddomesticuses,itisthethirdmostusedofallmetals.Onlyironandzinc exceeditinproduction. Aluminumcompoundstypicallyexistinthe+3oxidationstate.Becauseofitsdurabilityandlightweight,aluminumisusedinmany alloys,mixturesofmetals.Twometals,eachwithdesirablecharacteristics,canbemixedtogethertoproduceanalloythathasthe propertiesofbothmetals.Aluminumusedtobeusedforhouseholdwiring,butitexpandstoomuchwhenheated.Theexpansioncauses thewirestocomeloose,andhousefirescanstart. Aluminumseemsunreactivebecauseofathin,hardsurfaceofaluminumoxideAl2O3whichdoesnotreactwithwateroroxygenand preservesthealuminummetalunderneathitfromchemicalattack.Purealuminumwillimmediatelyformthislayerwhenexposedtoair. Althoughaluminumisveryconductive,aluminumoxidedoesnotconductelectricity.
Aluminummetal
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Aluminumtrichloride
Aluminum oxideisamphotericitreactsviolentlytoneutralizestrongbasesorstrongacids.
Reactingaluminumwithahalogenresultsinanaluminum halide.Aluminumchloridecan existasanionicsolidoracovalentsolid,buteitherwayitisaweakconductor.
Aluminumchlorideisa Lewisacid,abletoneutralizebases.
Moltenaluminumreactsviolentlywithsomemetaloxidesinthe thermitereaction,inwhicha substancelikeironoxideisreducedtoironandaluminumisoxidizedtoitsoxide.Thisisa highlyexothermicreaction,releasingenoughheattoweldmetal.
Generally,aqueousaluminumisfoundasahydroxideAl(OH)3.
Others
Galliumisabrittlemetalthatmeltsslightlyaboveroomtemperature,soholdingitinyourhandwouldliquefyit.Onemagictrick,the 'meltingspoon'involvesstirringahotliquid(usuallyhotwater)withaspoonspeciallymadeofgallium.Thespoonmeltsinthewaterand 'disappears'.(Thegalliumsimplysinkstothebottomofthecupafterthemagictrickisdonethe'magicianremovesthewaterandthe moltengalliumandpoursthegalliumintoamoldthatmakesanewspoonfordoingthetrickagain).Galliumisusedinmany semiconductordevicesandLEDs(lightemittingdiodes).Gallium(III)arsenideisanimportantsemiconductorusedinmanyelectronics. Indium'smostcommonisotopeisradioactiveanddecaysslowlyintotin.Indiumtypicallyhasthe+3oxidationstate. Thalliumtendstoappearinthe+1(thallous)oxidationstateaswellasthe+3(thallic)oxidationstate.Oddly,thalliumactsmuchlikean alkalimetalinitsphysicalandchemicalproperties.Thallousoxide(Tl2O)andthemetalreactviolentlywithwatertoformahydroxide TlOHthatcompletelydissociatesintoTl+ andOHionsasifitwereanalkalimetalhydroxide.Itshalidesarequitesaltlike,dissociating intoionsintosolutionsthat,likesolutionsofsaltsofthealkalimetals,conductelectricity.
Gallium
NeitherthalliummetalnoranythalliumcompoundisreadilyavailableintheUnitedStatesbecauseitissodangerousandhasfewlegitimateuses.
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NeitherthalliummetalnoranythalliumcompoundisreadilyavailableintheUnitedStatesbecauseitissodangerousandhasfewlegitimateuses.
Group14
TheCarbonFamily
Group14(IVA)consistsofcarbon,silicon,germanium,tin,andlead.Carbonisanonmetal,siliconandgermaniumaremetalloids,andtinandleadaremetals. With4valenceshellelectrons,elementsofthecarbonfamilytendtoformcovalentcompounds.Withincreasingmassandatomicradiustheseelementsbecomeincreasinglymetallic andhavelowermeltingandboilingpoints. Group14elementsformgaseoushydrogencompoundswithdifficulty.Theseareeitherunstableorcombustible.Allbutleadformoxides,sulfides,andhalidesinthe+4oxidation state.The+4oxidationstatepredominatesincarbon,silicon,andgermaniumthe+2and+4oxidationstatesbothappearintin,andthe+2oxidationstateprevailsinlead.Halidesin the+4stateformforalloftheseelements,andtheyarecovalent. Carboncompoundsaremuchmorecovalentthananalogouscompoundsofsilicon,germanium,tin,orlead.Evenmoresignificantly,carbonformsdoubleandeventriplebondswith itselforotherelements,formingcompoundsthattheheavierelementsofthisgroupcannotformlikeacetylene(C2H2).Siliconandtheheavierelementsofthisgroupcanformonly singlebonds. ThuscarbondioxideCO2isagasatnormaltemperaturesbecausethedoublebondsbetweencarbonandoxygencreatesinglemolecules,butsilicondioxideSiO2formsahardrock knownasquartzbecauseitisacovalentnetworksolid.Eachsiliconatombondstofourdifferentoxygenatomswithsinglebonds,andeachoxygenatombondswithtwosilicon atoms.Similarpropertiesapplytotheoxidesofgermanium,tin,andlead.Carbondioxidedissolvesinwatertoformcarbonicacid,aweakacidthatreactswithbasestoform carbonatesoxidesoftheotherelementsofthisgrouparepracticallynonreactiveinwater.
Carbon
Carbonisaveryimportantelement.Itisabundantintheearthandatmosphere,anditisfoundinthesubstancesthatmakealllivingthings.Carbonhasmanypropertiesthatmakeit differentfromotherelements,soitdeservesthoroughstudy.
Allotropes
Allotropesaredifferentformsofapureelement.Carbonhasseveralallotropes,threeofwhicharecommon. Amorphouscarboniscoalandsoot.Thecarbonmoleculesarecovalentlybonded,butthereisnoorderorarrangement. Graphiteoccurswhencarbonformsflatcovalentnetworks.Theseflat"sheets"arenotbondedtoeachother,makingthemfreeto slidepasteachother.Graphitecomposesthe"lead"inpencils. Diamondoccurswhencarbonformsathreedimensionalcovalentnetwork.Diamondsaremuchdifferentfromgraphiteand amorphouscarbon.Theyaretransparent,brilliantlooking,andincrediblyhard.Diamondonlyformsatheatandintensepressures. Therearealsoseveralrareandexoticallotropesofcarbon,including: Buckeyballs,orfullerenes,aresphericalshapedballsofcarbon.Covalentbondsjointhecarbonatomsintoasoccerballpatternthat looksmuchlikethegeodesicdomesofBuckminsterFuller.ThemostcommonbuckeyballhasthemolecularformulaC60.Buckeyballs arelargeenoughforasmallatomtogettrappedinside. LonsdaleiteformsuponmeteoriteimpactwiththeEarth. Carbon nanotubesareincrediblysmallbutrigidtubesmadeofcarbon.Theyarecreatedinlabsandareasubjectofresearch.
a)diamondb)graphitec)lonsdaleite d/e/f)buckyballsg)amorphoush) nanotubes
Keepinmindthatallotropesarecomposedofonlyoneelement.Inthiscase,theseallotropescontainonlycarbonatomsandnootherelements.
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Keepinmindthatallotropesarecomposedofonlyoneelement.Inthiscase,theseallotropescontainonlycarbonatomsandnootherelements.
InorganicCompounds
Althoughcarbonisknownmainlyforitsorganiccompounds,itdoesformmanyimportantinorganiccompounds. Oxides Oxidesofcarboncontainonlycarbonatomsandoxygenatoms.Therearetwooxidesthatoccurcommonly: Carbonmonoxide(CO):apoisonousgasreleasedwhencarbonbasedfuelsburninlimitedoxygen. Carbondioxide(CO2):foundnaturallyintheair,buttoomuchisconsideredpollution.Animalsexhalecarbondioxide,andplantsabsorbit.Itisslightlyacidic.Carbondioxide, whensolid,is"dryice". Thereareotheroxidesthatcouldform,buttheyareunstableorunnatural: Carbonsuboxide(C3O2):Consistsofdoublebonds,withoxygensattheends.O=C=C=C=O.Itbreaksapartintocarbondioxideand dicarbonmonoxide. Dicarbonmonoxide(C2O):Veryreactive.Containsonlydoublebonds,buttheendcarbonhasanonbondingpair. Carbontrioxide(CO3):Existsinthreedifferentshapes,veryunstable CompoundsDerivedfromOxides Carbonicacidformswhencarbondioxideisdissolvedinwater.Itisgivenbythereaction:
Carbontrioxide
Carbonateand bicarbonatearetwoionsthatcarbonforms.
TheirformulasareCO32andHCO3,respectively. IonicCompounds
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Alongwiththeoxyanions(carbonateandbicarbonate),carboncanformseveralotherions. Cyanide(CN) Cyanate(OCN) Thiocyante(SCN) Carbides(C22and C34) Alloys Carbonisusedinsome alloys,mixturesofmetals.Ifasmallamount(between0.2%and2.1%byweight)ofcarbonismixedintoiron, theresultis steel .
OrganicCompounds
Compoundscontainingcarbon(exceptfortheaboveinorganiccompounds)areconsidered organic.Theywereoncethoughttobe producedonlybylivingthings,buttheyhavesincebeencreatedinlaboratories.Mostorganiccompoundscontainhydrogenaswellascarbon.
CalciumcarbideCaC2
Manysubstancesareorganiccompounds. Polymersareorganiccompoundsconsistingoflongchainsofrepeatingpatternscontainingcarbonand otheratoms.Plastics,rubbers,andnylonareallorganicpolymers. Hydrocarbonsarecompoundscontainingonlyhydrogenandcarbon,methane beingasimpleexample.Crudeoilisasludgeofvarioushydrocarbonsmixedtogether.Propane,butane,andoctanearewellknownhydrocarbons usedforfuel.Perhapsthemostinterestingtypeoforganiccompoundisthe biomolecule.Carbohydrates,proteins,lipids(fats),andnucleicacids(like DNA)arethemostbasicbiomolecules.They,too,arepolymers(exceptforlipids),beingmadeoflongchainsofsmall,repeatingchemicalsthathave bondedtogether.Biomoleculesmakeupthechemicalsfoundinthelivingcellsthatcomposealllivingthings. Organicchemistryandbiochemistryareverybroadandthoroughtopics.TheyarefaroutsidethescopeofGeneralChemistry.Fortunately,your knowledgeofGeneralChemistryissufficienttobegintheWikibooksOrganicChemistryandBiochemistryifyouareinterested.
Silicon
Siliconisfoundin semiconductors,thebasisofallelectronicdevices.Itselectronconfigurationallowsittodonateoracceptelectrons. Whenpuresiliconis"doped"withelementsthathavemoreorfewerelectronsthansilicon,theslightlyimpuresiliconbecomesa semiconductor.Thesesubstancesmakeupcomplexelectronicsbyactinglikeaswitchthatcanturnonoroffdependingonelectrical signals. Silicondoesnotexistuncombinedinnatureitmostcommonlyoccursinsilica(includingtheverycommonrockquartzandmostsand grains)andinsilicates.Mostsilicatesareinsoluble.Socalled'magicrocks'reactwithdissolvedsodiumsilicateinwaterreactswiththe ionsofsomedissolvedmetalsaltstoformcolumnsofrocklikesilicates. Silicondioxide,ahardsubstancethatmeltsonlyathightemperatures,isverydifferentinitschemicalpropertiesfromcarbondioxide,a gasuntilitfreezesintodryice.Moltensilicacanbecastasglass,ahardandusefulmaterialresistanttoattackbyalmostallchemicals exceptfluorine,hydrofluoricacid,andstrongalkalis.Glassisextremelyusefulinhouseholdcontainersanddrinkingutensilsbecauseitis resistanttochemicals,heat,andtheattackofmicroorganisms.Glasscanbeveryclearifpureorcontainingcertainchemicals,oritcan takeonattractivecolors,makingitafavoritematerialforartobjects.Somesmalllivingcreaturesturndissolvedsilicaintheseaintotheir shellstocreatestructure.Agreatvarietyofsiliconcompoundsknownassiliconeshavewidespreadandvarieduses.
Methane
Transistorelectronicsexistbecauseof silicon'ssemiconductorproperties.
Others
Germaniumisanotherelementusedinsemiconductors.
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Tinisconsidereda"poormetal".IthastwoallotropesatSTP: greytinand whitetin.Greytinhasnonmetalliccharacteristics,butwhitetinismetallic.Tinisusedfrequentlyasan alloy."Tincans"areactuallysteelcanswithatinplatingtoresistcorrosion. Pewterisanalloyofcopperandtin,containingmostlytin. Bronzeisanalloyofcopperandtincontaining mostlycopper. Solderisanalloyoftinandleadusedforitslowmeltingpointforattachingwires. Leadisaheavy,graymetal.Ithadatremendousnumberofuses,butitisnowknowntobeaneurotoxinifingested.Watercarryingpipes weremadeoutoflead,buttheyarenowmadefromcopperorplasticbecauseleadcouldcontaminatethewater.Leadcompounds especiallyifsolubleinwater(likeleadacetateusedasapreservativeandsweetenerofwinesinRomantimes)orstomachacids(likethe leadoxideonceusedinpaints)oringaseousorliquidform(liketetraethylleadonceusedingasoline),andpowderedleadarevery dangerous.Useofleadinfoodstuffs,paint,andvehiclefuelsisnowillegalalmosteverywhere. Leadcrystalglasshasleadoxideinitbutsotightlyboundwithsilicathatitcan'tescapeeasily.Pencil'leads'arenotleadatall,but insteadharmlessgraphite(reallycarbon)boundwithclay.Leadremainsusefulinautomobilebatteries(thatcontainnecessarysulfuricacid muchmoredangerousthanlead)andinnuclearuseasashieldagainstradiationmuchmoredangerousthanleadmetal. Lead oxidesareeasilyreduced.
Leaddoesnotdissolvein hydrochloricacidorsulfuricacid, butitwilldissolveinnitricacid becausenitricacidisastrong oxidizer.
Lead(II)oxidewillform plumbite ionswhenaddedtobasic solutions.
AlargePerpendicularstyleGothicwindow ofeightlightsinCanterburyCathedral,c. 1400,whichcontainsmedievalglass.
Plumbitesformlead(IV)dioxide when chlorinated.
Addinglead(IV)dioxidetoabasic solutionwillform plumbateions.
Group15
TheNitrogenFamily
Group15(VA)containsnitrogen,phosphorous,arsenic,antimony,andbismuth.ElementsinGroup15havefivevalenceelectrons.Becausetheelementscaneithergainthree electronsorlosefivetogainastableconfiguration,theymoreoftenformcovalentcompoundsunlessbondedtoanactivemetal.Theirelectronaffinitiesarenotverylarge.Metallic propertiesincreasemarkedlyfromgaseousnitrogentobarelymetallicbismuthwithincreasingsizeandmass.Nitrogenandphosphorusarenonmetallic,andarsenicandantimony
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aremetalloids. Elementsofthisgroupareknownas pnicogensandtheircompoundsas pniconides.ThenameisderivedfromfromtheGreekword pnicomigsmeaning suffocation. TheseelementsaremuchlessreactivethantheelementsofGroup16,andtheirchemistriesaremorecomplicated.Mostofthechemistryoftheseelementsisinthe+3or+5 oxidationstates,althoughtheyformgaseouscompoundswithhydrogeninthe3oxidationstate:ammoniaNH3,phosphinePH3,arsineAsH3,stibineAsH3,andbismuthineBiH3 theseallburninoxygentogiveoxidesorthefreeelement(inthecaseofnitrogen).
Allformoxidesnitrogenwithdifficulty,theotherswithease.Mostoftheoxidesareacidic,exceptionsbeingnitrousoxideN2O,nitricoxideNO,andbismuthoxideBi2O3.Exceptfor nitrogen,typicaloxidesareinthe+3or+5(bismuthexcluded)oxidationstates.Allformhalidesnitrogenwithdifficulty,butthoseofphosphorus,arsenic,andantimonyfully hydrolyzeinwater. Nitrogenandphosphorusformimportantacidsinthe+5oxidationstate.NitrogenformsnitricacidHNO3,asubstanceusedtocreatemedicinesandexplosives(butthisacidis corrosiveanddangerous,sodon'ttouchitorevenspillitonanything),andsaltsknownas nitratessuchaspotassiumnitrateKNO3,animportantfertilizer.Phosphorusforms phosphoricacid,H3PO4 phosphatesaresaltsofphosphoricacid.Somephosphatesareessentialtorespirationandthuslifeitself.
Nitrogen
NitrogenoccursnaturallyasthediatomicgasN2.Itcomposesabout70%oftheairwebreathe.Thebondholdingthetwonitrogenatoms togetheristriplecovalent,soitisverystrong.Becauseofthat,nitrogenisveryunreactive.Itisusedinmanyplaceswhenaninertgasis needed.However,nitrogenwillreactwithsomesubstances:
Althoughnitrogengasisusuallyconsideredinert,itdoes reactwithsomeelementsbyburning.
The nitridesreactviolentlywithwatertoformammonia gasandabasicsolution.
Thenitrogencycleshowshownitrogenis passedalongorganismsandthe atmosphere.
Initspureform,nitrogenisnotveryuseful.Itismuchmoreimportantwhenitisacomponentofammonia,nitrate,oxides,orbiomoleculeslikeprotein.Dueitisveryunreactive nature,itisdifficulttogetnitrogentoreactandformtheseusefulsubstances.Anyprocessthatcanconvertelementalnitrogenintoanitrogencompoundiscalled nitrogenfixation. Nitrogenfixationisbiologicallyimportantbecauseaminoacids,proteins,andenzymescontainnitrogen.Itiscommerciallyimportantbecauseitisusedinexplosives,rocketfuels,and fertilizers. Therearemanynitrogenfixationreactions:
Thisoccursinbacterialenzymes.Theammonia(NH3)quicklybecomesammonium(NH4+ ).Thenitrogenin thebacteriaentersthesoilwhereplantscanabsorbit.Humansandanimalsthateatthoseplantscangetthe

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nitrogen.
The Haberprocessisusedforcommerciallyproducingammonia.Thisreactiononlyoccursatveryhigh pressuresandtemperatures(around20MPaand500C)andinthepresenceofanironcatalyst.Also,the reactionoccursinsomewhatcomplexequipmentthatmustinputpurereactantsandextracttheammonia.
KeepinmindthatammoniaisagasatSTP.Thehouseholdproductcalled"ammonia"isactuallyanaqueoussolutionofammoniumhydroxide(NH4OH)thatformswhenammonia gasisdissolvedinwater.Ammonia,quiteunlikehydrogencompoundsofGroups16and17,isabaseinitsreactions,formingsaltswithweakandstrongacidsalike.Sucha substanceasammoniumchloride(NH4Cl)isasoluble,stronglyionicsalt. Nitrogencompoundsareoftenextremelyunstablebecausenitrogenatomsinnitrogencompoundstendtoseekeachothertorecombineasnitrogengas.Manynitrogencompounds areliteralexplosives,includingTNTandnitroglycerin.Theseexplosivesareincommonuseinconstructionprojectsforthedemolitionofbuildingsandotherobstaclestonew construction,ortogetaccesstomineralsinminingoperations.
Phosphorus
Phosphorushastwocommonallotropes:redphosphorusandwhitephosphorus.Whitephosphorus(P 4)hasawaxyappearanceandturnsyellowwhenexposed tolight.Whenexposedtooxygeninthedark,itglowspalegreen.
.
White phosphorus atomicstructure
Whitephosphorusignitesunderallbutthemostdelicateconditions.Thecombustionofwhitephosphorusproducesphosphorus(V)oxide:
Oneofitsmostcommonusesisinmilitaryweaponsthatcausesevereburningoftheobjecthitbytheweapon. Redphosphorusisanamorphoussolid.Itismorestableandexplodesattemperatureshigherthanthoseofwhitephosphorus.Itisstill,however,dangerouslyreactive.Bothformsof phosphorusareinsolubleinwaterandcanbeinterconvertedwithvariousapplicationsofheat,pressure,andlight. Therealsoexistblackphosphorusandvioletphosphorus.Unlikenitrogen,phosphoruswillnotreadilyformadiatomicmoleculewithatriplebond.Diphosphorusdoesexist,butonly betweenatemperaturerangeof1200Cand2000C. PhosphorusisessentialtolifeintheformofphosphatesinbonesandinsubstancesknownasADPandATPthattransformfoodintousefulenergyincells.
Others
Arsenicissimilartophosphorus.Ithasthreeallotropes:greyarsenic,yellowarsenic,andblackarsenic.Greyarsenicisthemostcommonform.Itsstructureissimilartographite. Antimonyhasthephysicalpropertiesofametal,butbehaveschemicallyasanonmetal. Bismuthisabrittle,silverymetal.Bismuth isactuallyradioactive,decayingintothallium205.Becauseits halflifeis19x1018years,aboutamilliontimestheageoftheuniverse, bismuthisusuallyconsideredstable.
Bismuthismuchlessradioactivethanthenearlyharmlessandunavoidableradioactiveisotopesofcarbonandpotassiuminlivingthings.Unlikearsenicandantimony,itscompounds
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Bismuthismuchlessradioactivethanthenearlyharmlessandunavoidableradioactiveisotopesofcarbonandpotassiuminlivingthings.Unlikearsenicandantimony,itscompounds aren'ttoxicunlesssomethingelseinthecompoundisitselftoxicorthesubstanceisveryacidicoralkaline.Infact,abismuthcompoundisverycommoninaheavilyusedstomach medicationthatrequiresnoprescription.thereanothertypeofphosphorousisalsoexistsi.e.,blackP.ItispreparedbyheatingwhitePto470Katinertatmosphere.
Group16
TheOxygenFamily
Group16(VIA)ismadeofoxygen,sulphur,selenium,tellurium,andpolonium.Oxygen,sulfur,andseleniumarenonmetals.Tellurium isametalloidandpoloniumisametal. Group16elementshave6valenceelectrons,meaningthattheyrequiretwomoreelectronstocompleteastableelectronoctet.Theystill haverelativelylargeelectronaffinitiesandareratherreactive,formingionswitha2charge.Allbutpoloniumformvolatilecompounds withhydrogen:waterH2O,hydrogensulfideH2S,hydrogenselenideH2Se,andhydrogentellurideH2Te. Electronegativitydecreasesinthisgroupwithincreasingatomicmass,andoxygenismoreelectronegativethananyelementexcept fluorineitactsmuchlikeahalogenexceptforits2oxidationstate.Fluorineandoxygenoxidizetheseelements(exceptoxygen)tothe +6oxidationstate,resultinginsuchsubstances(forsulfur)assulfurhexafluorideSF6andsulfurtrioxideSO3anditsderivativesulfuric acidH2SO4,oneofthemostheavilyusedindustrialchemicals.(Notethatuseofsulfuricacidrequiresextremecarebecauseitcauses chemicalburnsuponflesh,cloth,andpaper).Typically,theseelementswillattainanoxidationstateof2. Oxidesofsulfur,selenium,andtelluriumareacidic.Strongradioactivitylargelymasksthechemicalpropertiesofpolonium.
Oxygen
Oxygenisadiatomicgasthatmakesupabout20%oftheairwebreath.Itisessentialforthelifeofanimals,andplantsreleaseit.Plants absorbsunlightandproduce glucose(sugar)andoxygen.Cellsofplantsandanimalsalike"burn"glucosewithoxygentogainenergy.
Acrystalofbismuth,showingitscolorful iridescenttarnish.
Photosynthesisisactuallyaseriesofcomplex chemicalreactions,involvingseveralsubstances foundinthechloroplastsofplants.Thisistheoverall reaction.
Cellular respirationisthereverseprocess: convertingglucoseintoenergy.

Closeupofchloroplasts,thepartofplant cellswherephotosynthesisoccurs
Oxygenhasafewallotropes,butonlytwoarecommon:dioxygenandozone.Dioxygenistheregularformofoxygen,O2,heldtogether withadoublecovalentbond.Ozone,O3,isfoundnaturallyintheupperatmosphereandcanformwhennormaloxygenisexposedtohigh voltage.
Ozone
Ozoneisnotverystable.Itwilldecompose:2O33O2.Ozoneisaverypowerfuloxidizingagent.Metalsandnonmetalsarebothsusceptibletooxidationwhenexposedtoozone.
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Carbonisoxidizedbyozone.
Nitricoxidebecomesnitrogendioxide.
Althoughconsideredapollutantwhenatgroundlevel(itistoxic),ozoneisaveryimportantchemicalfoundintheupperatmosphere.TheSunemitsdangerousultravioletlightthat woulddamagelivingcells,butozoneabsorbsthelightenergyandconvertsitsafelyintoheatenergy: Highpoweredradiationfromthesunsplitsozonemolecules.
Atomicoxygencanreattachitselftodioxygentorecreateozone.
Youcanseethatthenetresultoftheabovereactionsisasystemofozonethatconvertsdangerousradiationintoheatenergy. AtomicoxygenisextremelyunstableandwillattachitselftoformO2orO3immediately:
Theozonecycle
Theamountofozoneintheatmosphereissmall,butsolarradiationwillsplitO2intotwoOatoms,sothereisasmallbutsteadysupplyofozone.Unfortunately,manymanmade productscalled chlorofluorocarbons(CFCs)haveenteredtheupperatmosphereovertheyears.Thechemicalsreleasechlorineradicalsthatactascatalystsforanozonedestroying reaction.Asaresult,theamountofozoneintheatmospherehasdecreased,whichcouldleadtoanincreaseindangeroussolarradiation. Achlorine radical formsfromaCFC. Radicalshaveasinglenonbondingelectron(insteadoftheusualpair),sothey areextremelyreactive.Achlorineradicalissimplyasingleatomofchlorine(whichhassevenelectrons).
Chlorineradicalswillbecomestableby"stealing"anoxygenatomfromozone.
Thechlorinemonoxidereactstoeliminateanotherozonemolecule.Theoriginalradicalisnowavailabletorepeatthe entireprocess.
Asyoucansee,chlorineradicalsconvertozoneintoregularoxygenwithoutbeingusedup.Overtheyears,productshavebeencreatedthatreplaceCFCsandcauseless environmentaldamage.
Oxides
Anychemicalcompoundconsistingofoxygenandsomeotherelementcovalentlybondedisan oxide.Metalsformoxideseasily,exceptforafewincludinggold,platinum,and mercury.Besidesbeingcalled oxidation,theprocessisalsocalled tarnishingor rusting.Inotherwords,anironnailthatturnstorusthasformedironoxide.Thedull,dirtylookingfilm thatcoatsotherwiseshinycopperiscopperoxide.Oxidesformbecauseoxygenissoelectronegative.Whensubstancesburn(includinghydrocarbonsandmetals),theyoxidizeand
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releaselargeamountsofheatquickly. TheoxideionisO2.ThereisalsoperoxideO22andsuperoxideO2.
Sulfur
Sulfurbehavessimilarlytooxygen,butithasover30allotropes.ThemostcommonisS 8.SulfurisasolidatSTP.Itisyellowandis actuallyodorless.ThedistinctodorofsulfurisactuallyH2S,hydrogensulfide.Sulfurisapartofmanyorganicandinorganiccompounds. Sulfurispartofsomeproteinsnecessaryforlife. Chemicalnamesbeginningwith"thio"meananoxygenatomhasbeenreplacedwithasulfuratom.Forexample,cyanateisOCN, whereasthiocyanateisSCN.
Others
Seleniumconductselectricitybetterinthelightthaninthedark,soitisfoundinphotocells,electricalcomponentsthatdetectlight. Telluriumisextremelyrareandverypoisonous. Poloniumisdangerouslyradioactiveandveryrare.Itisusuallyassociatedwithuraniumoreasaproductofradioactivedecayofuranium.
S8
Group17
Halogens
The halogensarefoundin Group17(VIIA).Thehalogensarefluorine,chlorine,bromine,iodine,andastatine. Likethealkalimetals,thehalogensareextremelyreactive.Theyhavesevenvalenceelectrons,meaningtheyrequireonlyonemoreelectronforanobleconfiguration.Thisgives themverylargeelectronaffinitiesandextremereactivitytoformionswitha1charge.Theyaresoreactivethatintheirhomogeneousstate,UVlightwillcatalyzearadicalreaction. Thehalogensexistin diatomicform.Undernormalconditions,theywillalwaysoccurinpairs,covalentlybonded.Thecovalentbondallowsthemtoshareanelectronandpossessa completeoctet.F2isapaleyellowishbrowngas.Itishighlyreactive,causingorganiccompoundsandhydrogengastoexplode,evenwithoutaspark.Cl2isapaleyellowgreengas. Itreactswithwatertoformdisinfectantsandbleaches.Br2isareddishbrownliquid,but,being volatile,itreadilyevaporatesintoareddishvapor.I 2isagraysolidthatformsa violetgasifheated. Fluorineisthemostelectronegativeofallelements,anditissoreactivethatitattacksalmostanyotherelement(noblegases,oxygen,nitrogen,andgoldaretheexceptions)toform fluorides.Chlorineissomewhatlessreactive,brominesomewhatlessreactivethanchlorine,andiodineevenless,buteveniodineisaformidableionizer.Extremeradioactivity masksthechemicalpropertiesofastatine.Withincreasingatomicweightfortheseelements,theelementshavehigherboilingandmeltingpoints.Atnormaltemperatures,fluorine andchlorinearegases,bromineisaliquid,andiodineisasolid. TheHalogens
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Copper(II)Fluoride
Chlorinegas
Bottlecontainingboth liquidandgaseous bromine
Solidiodinepieces
Safety Reactions
Thehalogensindiatomicformreactwithwatertoproduce acids. Iodinedoesnotreactwithwaterandisonlyslightlysoluble.Chlorinealsohaslowsolubility,butitwill reactinwatertoformhypochloricacidandhydrochloricacid.
Inchemicalreactions,anXisusedtosymbolizeanyhalogenelement.Allhalogensformgaseous compoundswithhydrogen:hydrogenfluorideHF,hydrogenchlorideHCl,hydrogenbromideHBr,and hydrogeniodideHI.Theseareacidic,stronglyreactivesubstancescalled hydrogenhalides.
Whenhydrogenhalidesaredissolvedinwater,theyareknownas hydrohalicacids.Exceptfor hydrogenfluoride,theyareamongthestrongestknownacids.
Thesereactionsshowreactionswithmetalsandammoniagastoform saltsand ammoniumhalides, respectively.
Manynonmetallichalidesreactwithwatertoreleasehydrogenhalides.Forexample,siliconchloride andwaterreact.
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OtherCompounds
Halidesofmetalsareknownas salts.Sodiumchloride,betterknownas"tablesalt",isthecrystallinesubstanceoftenusedtoenhancetheflavoroffood.Note,however,thatnotall saltsarehalides(forexample,sodiumsulfateNa2SO4),andnotallhalidesaresalts(carbontetrachloride,CCl4). Interhalogensaremoleculescomposedoftwoormoredifferenthalogenatoms.Theyaresimilartothediatomichalogens.SomeexamplesarechlorinemonofluorideClFand brominemonochlorideBrCl.Therearemanyothers,andtheyareallveryreactiveandsomewhatunstable.InterhalogenstaketheformXY n,wherenis1,3,5,or7.XandYare bothhalogens,Xbeingthelesselectronegative. Noblegascompoundshavebeenformedusingfluorine.Althoughnoblegasesaresupposedlyinert,thelargeroneslikexenonwillformcovalentbondswithaveryelectronegative elementlikefluorine.XenondifluorideXeF2,xenontetrafluorideXeF4,andxenonhexafluorideXeF6areamongthenoblegascompoundsthathavebeencreated.
Group18
NobleGases
The noblegasesarein Group18(8A).Theyarehelium,neon,argon,krypton,xenon,andradon.Theywereoncecalled inertgasesbecausetheywerethoughttobecompletely inertunabletoformcompounds.Thisisareasonablebeliefbecausethenoblegaseshaveacompleteoctet,makingthemverystableandunlikelytogainorloseanyelectrons. However,somecompoundshavebeenformedwiththelargerelementsofthisgroup,likexenontetrafluoride(XeF4).Nonormalcompoundsofhelium,neon,orargonarestableat anybutthecoldestoftemperatures. Radonisdangerouslyradioactiveitcausescancer.Itissounstablethatitsradioactivitymakesanychemicalexperimentswithitnearlyimpossible.
Ionization
Ifanelectriccurrentispassedthroughagas,itselectronswillbecomeexcited.Theelectronwilljumptoahigherenergylevel,butthenitfallsbackdowntoastablestateand releasestheenergythatithadabsorbed.Theenergyisreleasedintheformofa photon,orparticleoflight.Inotherwords,gasescanbeusedtoconvertelectricityintolightthe conceptof"neonsigns".Neonsignsarenotnecessarilyfilledwithneon.Theyarefilledwithanymixtureofgasestogetthedesiredcolor.Eachgashasauniquecolorthatitemits. Colorsofdifferentnoblegaseswhenusedin"neon"signs
Helium(pink)
Neon(redorange)
Argon(blue)
Krypton(palegreen)
Xenon(paleblue)
Ofcourse,othergasescanbeusedbesidesthenoblegases.
Helium
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Heliumisauniquenoblegas.Itisthesecondmostabundantelementintheuniverse.Lighterthanair,itisusedinblimpsbecauseitwillallowthemto floatwithouttheriskofanexplosion.Neonistheonlyelementlessreactivethanhelium. Heliumwillnotfreezeundernormalpressure.Therecannotbeenoughintermolecularforcetolocktheatomsintoasolid.Itremainsagasuntil4K,then becomesaliquid.Withtherightconditions,heliumbecomesa superfluid.Itisaliquidthatwillcreepalongtheedgesofitscontainerwithzeroviscosity.
Hydrogen
Hydrogen
HydrogenisbyfarthemostcommonelementintheuniverseasagasitistoolightforEarth'sgravitytohold.ItisbyfarthelargestconstituentoftheSun andallotherstarsandofthegasgiantplanetsofoursolarsystem.ItexistsonorjustunderthesurfaceoftheEarthasacomponentofwaterandin innumerablecompoundsofcarbon,manyessentialtolife. Theheatandlightfromthesun(oranyotherstar)ariseslargelyfromthenuclearfusionofhydrogenintohelium.Nuclearreactionsarediscussedlater. Essentially,thenucleusoftwoatomscancombineatveryhightemperatures,whichreleasestremendousamountsofenergyintheformofheatandlight.
Heliumwillnotfreeze. Instead,itbecomesa superfluid.
Reactions
Hydrogen,althoughhavingoneoutermostelectron,doesnotfitintothealkalimetalsoranyothergroup.Itdeservesitsowntreatment.Itformscompoundsanalogoustothoseofthe alkalimetals,butsuchhydrogencompoundsaremuchlessalkaline(ormoreacidic),muchlessionic,andmorevolatile.Sodiumchloride,thestereotypicalsalt,isneutralandclearly ionichydrogenchlorideisanonionicgasundernormalconditionsandisastrongacid.Thehydrogenanalogueofsodiumhydroxideisavolatileliquid(water,itsmostcommon compound)undernormalsituationsunlikethestronglyalkalineandsolidsodiumhydroxide,waterisslightlyionicandeffectivelyneutral. Hydrogenisanonmetal,formingadiatomicgaswhichresultsfromthesharingofthesingleelectronsofhydrogenatoms.Itcanachieveastableionicstructure(noelectrons!)by losinganelectronorbygaininganelectronandachievingthecompletedshellconfigurationofhelium.Thehydrogenmoleculeisbestdescribedassharingthetwoelectronsbetween twohydrogenatoms.Thisstructureishighlystableandhaslittleinclinationtoformbondsbetweenotherhydrogenmoleculeshydrogenisagasdowntosomeofthelowest temperaturesknown.Itisalsothelightestofgases,weighinglesseventhanhelium.
Hydrogenreadilysharesitselectronwithastronglyelectronegativeelement,likeanyhalogen,oxygen,orsulfur. Thecombinationwithfluorineisparticularlyviolentandpossibledowntoverylowtemperatures.Lightisenough toforcecombustionbetweenhydrogenandchlorine,andasparkisenoughtocausecombustionbetween hydrogenandoxygen.
Duetothe Hindenburgdisasterof1936,heliumhaslongreplacedhydrogeninlighterthanairaircraft.The reactionresponsibleforthatdisasterwassimplythecombustionofhydrogenandoxygen.(Notethatatthe temperaturesassociatedwithsuchacombustion,waterisinthegaseousstate)
Hydrogencanactsomewhatlikeahalogen,forming hydrideswithsomemetals.Mostofthesereactviolently withwatertoformhydrogengasandthemetalhydroxide.Hydrogencompoundswithnonmetalsaretypically amongthemostvolatilesubstancesofthoseelements.
Underpressure,inaqueoussolutions,orinnonsolidacids,hydrogenisagoodreducingagent.Strongacids
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attackmostmetals.Thisexampleshowshydrochloricacidaddedtozinc. (generalnetionic equation) Intheatmospheresofgasgiantplanets(Jupiter,Saturn,Uranus,andNeptune)gaseoushydrogenundergreat pressurereducesnitrogentoammonia,carboncompoundstomethaneandotherhydrocarbons,andoxidesto water.
Compounds
Almostallcarboncompoundscontainhydrogen,andviceversa,butmoresubstancescontaininghydrogen(withoutcarbon)existthandocompoundsofcarbon(withouthydrogen). Hydrogenformsbondswithmostnonmetals,includingoxygen,nitrogen,andcarbon.Althoughahydrogenatomcanbondwithonlyoneotherelement,andthenonlyinasingle bond,hydrogenallowsverylongchainsofcarbonatomstoform.Mostofthehydrogencompoundswithcarbonalonearecombustiblegasesorvolatileliquidsorwaxysolidsthatcan bevaporizedandburnedtoproducewater,carbondioxide,andmuchheat.Naturalgas,gasoline(amixtureofliquidhydrocarbons),andwaxesasfoundincandlesmakesuitable fuels.Withsuchotherelementsasoxygen,nitrogen,sulfur,andinsomecasesmetals,hydrogenallowstheformationofsubstancesnecessaryforlife,includingcarboxylicacids, sugars,proteins,nucleicacids,haemoglobin,andchlorophyll. SuchcomplexcompoundsareordinarilydiscussedinOrganicChemistry,astudyassociatedmoreobviouslywithcarbon.
Forms
Hydrogenhasthree isotopes.Allhydrogenatomscontainexactlyoneprotoninthenucleus,buttherecanbezero,one,ortwoneutrons.99.98%ofallhydrogenatomsnaturally foundonEarthhavenoneutrons.Thisiscalled protium,or 1H.Itisstable,alongwith deuterium,or 2H.Deuteriumhasoneneutron.Itbehavesexactlylikeregularhydrogen,butit weighstwiceasmuch.Thus,"heavywater"isD2O,whereDisdeuterium. Tritium,or 3H,hastwoneutrons.Itisunstable(radioactive)anddecaysintohelium. Ifhydrogenlosesanelectron,itbecomesH+ ,simplyabareproton.Inanaqueoussolution,H+ formshydrogenbondswithasurroundingwatermoleculetocreate hydroniumH3O+ . Asthehydroniumconcentrationofasolutionincreases,sodoesitsacidity. Althoughuncommon,hydrogencangainanelectrontobecomeanHion.
TransitionMetals
TransitionMetals
Thetransitionmetalsarefoundinthemiddleoftheperiodictable.Therearetwodefinitionsof transitionmetals: 1. Alldblockelements(Groups312) 2. Elementswithpartiallyoccupieddorbitalsorthatcanformcationswithpartiallyoccupieddorbitals Thefirstdefinitionismorecommonandisusedcasually,buttheseconddefinitionemphasizestheuniquepropertiesoftransitionmetalsandistheoneusedbyIUPAC(The InternationalUnionofPureandAppliedChemistry).TheseconddefinitioniscommonlyconsideredtoexcludeZn,CdandHgbecausetheseelementshavea d10electronic configuration(thedorbitalsbeingfully,notpartially,occupied).However,recentlyreportedfluorideHg(IV)compounds,whichhavea d8configurationputthisexemptionintodoubt andmakeitreasonabletoconsiderHg(andpossiblyZnandCdtoo)astransitionmetals. Transitionmetalsbehavedifferentlythanothermetalsbecauseoftheirpartiallyoccupieddorbitals.Addingelectronstoatransitionmetaldoesnotaffectitsvalenceshellbecause theelectronsgointothedorbital(whichisnotpartofthevalenceshell).Alltransitionmetalshaveoneortwovalenceelectrons.
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ElectronsandOxidation
Transitionmetalsareinterestingbecausetheycanhaveseveraloxidationstates,unlikemostothermetals.Thishappensbecausethetransitionmetalscanlosetheirdelectronsin additiontotheirselectronswhenformingions.
Thesoliddotsshowcommonoxidationstates,andthehollowdotsshowpossiblebutunlikelystates.
Rememberthatanelectronorbitalismoststablewhenitisfullorhalffull(orempty).Studyingtheelectronconfigurationsofthetransitionmetalsshowsaninterestingpattern: Sc: [Ar]4s23d1 Ti: [Ar]4s23d2 V: [Ar]4s23d3 Cr: [Ar]4s13d5 Mn: [Ar]4s23d5 Fe: [Ar]4s23d6 Co: [Ar]4s23d7 Ni: [Ar]4s23d8 Cu: [Ar]4s13d10 Zn: [Ar]4s23d10
Tobemorestable,anselectron"jumpsup"tothedorbitalinchromiumandcopper.Thisalsooccursininheaviertransitionmetalslikemolybdenum,tungsten,andplatinum.With heaviertransitionmetalsinPeriods5,6,and7,theeffectsof relativitycausechangesintheenergylevelsoftheorbitals.Inthoseelements,selectrons"jumpup"todshellsmore oftenthanexpectedwiththefull/halffullrule. Whenionsofthetransitionmetalsform,theylosetheirselectronsfirst,thentheylosetheirdelectronsiffurtherionized.Forexample,coppercanformtwodifferentions,and
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Whenionsofthetransitionmetalsform,theylosetheirselectronsfirst,thentheylosetheirdelectronsiffurtherionized.Forexample,coppercanformtwodifferentions,and titaniumcanformthree: Cu: [Ar]4s13d10
Cu+ : [Ar]4s03d10 Cu2+ : [Ar]4s03d9 Ti: [Ar]4s23d2
Ti2+ : [Ar]4s03d2 Ti3+ : [Ar]4s03d1 Ti4+ : [Ar]4s03d0
Colors
Transitionmetalsandtheiroxides,whendissolved,formcoloredcompounds.Group1and2metalsareclearwhendissolvedandwhitewhenprecipitated.Othermetals,likelead, areclearwhendissolvedandmayhavecolorwhenprecipitated(leadprecipitatesareyellow).Transitionmetals,ontheotherhand,arecoloredwhendissolved.Differentmetalsare knownfortheirspecificcolors,findinguseasinksorpaints.
Lefttoright:cobalt(II)nitrate(red)potassiumdichromate(orange)potassium chromate(yellow)nickel(II)chloride(green)copper(II)sulfate(blue) potassiumpermanganate(purple).
Families
CoinageMetals
The"coinagemetals"arecopper,silver,gold,androentgenium.Theseelementsareusedformuchmorethanjustcoins,andmanyotherelementsbesidesthesearemadeinto coins.Furthermore,roentgeniumisradioactivewithahalflifeof3.6seconds,makingituselessforcommercialapplications.Consequently,the"coinagemetals"aremore appropriatelycalled Group11(IB)elements. Copper,silver,andgold,althoughrelativelyrare(copper),rare(silver),orextremelyrare(gold),areamongthelongestknownandmostfamiliarelements.Theyaresoft,shiny,dense metalsresistanttocorrosionandverygoodconductorsofelectricity.Roentgenium,arecentlydiscoveredsyntheticelement,issoshortlivedthatitsphysicalandchemicalproperties areilldefined.
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Copperisbyfarthemostheavilyusedoftheseelementsduetoitselectricalproperties,itscommonness(contrastedtosilverandgold)andtheattractivenessofitsalloysbrassand bronze.Untilaluminumbecamecommonplace,copperwassecondonlytoironinproductionamongthemetals.
Copperpipes
Silver,theshiniest
Gold
Theyareeasytoidentifywhenfoundbecausecopper(reddish)andgold(yellow)aretheonlytwocoloredmetalsthatpeoplearelikelytoencounter.Silveristheshiniestofmetals, anditisusuallyfoundinthepresenceofcopperorgoldandgivesanobviouscontrast.Theyareoftenfounduncombined. Becauseoftheirsoftnesstheyareeasilystruckascoins,andtheircomparativerarityandattractiveness,alongwiththeirresistancetocorrosionmakethemcompactstoresofwealth. Theyaretoosofttohavestructuralvalue,butcopperalloyswithsuchelementsaszincandtintoformharderbrassesandbronzes.Brassandbronzewereessentialintheearliest metaltoolswithoutthem,civilizationasweknowwouldbeimpossible.Goldandsilver,duetotheirattractivenessandtheirresistancetooxidation,havebeenusedheavilyinjewelry andotherornamentalworks.Gold,althoughextremelyexpensive,issomalleablethatatmodestcostasmallamountcanbepoundedintoafoilofextremethinnessthatallowsitto beusedasacoveringofsomearchitecturalobjectsalittlegoldgoesalongway. Copperoxidizeswithsomedifficultytothe+1stateinhalidesandanoxideandtothe+2stateinsaltssuchascoppersulfateCuSO4.Solublecoppercompoundsareeasilyidentified bytheirdistinctivebluegreencolor.Silveroxidizestothe+1stateinsuchsubstancesassilvernitrateAgNO3andsilversulfideAg2S,thelatterthetypicalblackeningofsilver.Gold oxidizestothe+1and+3statewithgreatdifficulty. Theseelementsarepoor(copper)toextremelypoor(gold)reducingagentsandtheircompoundsareverygoodoxidizingagents.Copperionsoxidizemostmetals:
Thereactionisevenstrongerwitheithersilverorgold.Ineffectasolutionofoneofthesemetals'saltsplatesmostothermetals. Silverismostelectricallyconductivemetal,followedbycopperthengold.Thismakescopperafavoritematerialforelectricalwires.Goldtippedwiresareemployedinsituationsthat needelectricalprecision(likehighqualityaudio)becausegoldwillnottarnish(thetarnishofcopperismuchlessconductive).
ZincFamily
The ZincFamilyis Group12(IIB)andconsistsofzinc,cadmium,mercury,andcopernicum. Zinc,cadmium,andmercuryaremetalswithlowmeltingpointsformetals.Thisisbecausetheyhaveanespeciallystableelectronconfiguration.Mercuryissopooratforming metallicbondsthatitisliquidatroomtemperature.
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Azinccoin
Cadmiumpieces
Apuddleofmercury
Zincandcadmiumaresoftmetalsthateasilyoxidizetothe+2oxidationstate.Neitherofthesetwometalsappearsuncombinedinnature.Zincisheavilyusedinalloyswithcopper tocreateahardermetalknownasbrassasacoatingforiron(theprocessiscalled"galvanizing"),itoxidizestoformaprotectivelayerofzincoxide(ZnO)thatprotectstheironfrom oxidation,alsoknownasrust.Zincoxideismuchsaferthanleadoxideandisoftenusedinwhitepaint.Since1982,zinchasbeenthemainmetalusedinAmericanpennies.Itis nowusedinneworganpipes. Cadmiumformstwosubstances,cadmiumyellow(cadmiumsulfide,CdS)andcadmiumred(cadmiumselenide,CdSe)thatappearedinpaints.Thesepaintshadstrongcolorsthat manyofthegreatartistsoftheImpressionistperiodscherishedintheirpaintings.Butthesesubstancesareverypoisonous,andpainterswhousedthemoftendiedyoungand crippled.Modernpaintersordinarilyusedifferentpaintsthatdonotusethesetwopoisonouschemicals. Mercury,incontrast,isashinyliquidatroomtemperatureandoxidizeswithsomedifficulty.Itconductselectricitywell.Becauseitisliquiditisanunusualmetalbutitisametal.It hasbeenusedinthermometers(butnotsooftenafterithasbeenidentifiedasadangerouspoison)becauseitexpandswithheatandinswitcheswhereitcanflowintoaclosed spacetocloseacircuit.Mercuryoxidizestothe+2stateinmercuricchloride(HgCl2)insomestrangecompounds,twomercuryatomsshareanelectronandoffertheir"spare" electronstoformsubstancesinthe+1state,suchasmercurouschloride(Hg2Cl2). Zincisanessentialtraceelementforlivingthingsithassomegermicidalpropertiesandistoxic(poisonous)inlargequantities.Zincpenniesshouldneverbeswallowed.Cadmium, mercury,andtheircompoundsareverydangerouspoisons.Althoughmercuryisattractiveandhasremarkableproperties,itshouldbeusedwithextremecare,andonlybyworkers whohaveappropriateknowledgeofitshazards. TheartificialElement112namedcopernicumin2010isprobablypartofthisgroupinitsproperties,butitisextremelydifficulttoproduceandtoounstabletohaveawelldefined chemistry.Fewatomsofthiselementhaveeverbeenmade. TheelementsofGroups8,9,and10areintwodistinctgroups:thecommonelementsiron,cobalt,andnickeloftheupperrowoftransitionmetalsandtheplatinummetalsofthe secondandthirdrows,andthefarscarcerplatinummetalsofthetwolowerrowsoftransitionelements.
Iron,cobalt,andnickel
Theseelementsarefairlygoodreducingagentssogoodthattheyrarelyappearuncombinedinnature.Ironisbyfarthemostcommonofthese.Oneofthemostcommon elementsintheuniverse,itistheheaviestmetalthatformsinnormalfusioninstars(butonlythelargeststars).Onceastarbeginstoproduceironinitscore,thatstarisdoomedin shortordertoaviolentexplosionthatdestroysthestarandscattersitsmatter,includingalloftheelementsthatithasformedinfusion. Uncombinediron,cobalt,andnickelbutespeciallyironaretobefoundinmeteors,solidobjectsthatstriketheearth.Ironisbyfarthemostcommonofthetransitionelements, andoneofthemostuseful.It'shardtocountalltheusesofiron,themetalmostused(whetherpureorinalloys)inalmostallmachines.Giant"glassbox"skyscrapersdependupon ironbarswithintheirconcrete"skeletons"togivethemstrengthandstability.Therailsofrailroadsarelongironbars.Concretehighwaysandairstripshaveironreenforcingbarsto givethemthestrengthtoholdheavyvehicles.Thevehiclesthemselvesarelargelyironandahardermaterialknownassteel,analloyofiron,carbon,andoftenmetalsotherthan iron.
Ironisthecheapestofallstructuralmetals.Withsomeskillofanartisanknownasablacksmithitcanbeworkedintomanyusefulobjectssuchashorseshoes,nails,plows,chains,
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Ironisthecheapestofallstructuralmetals.Withsomeskillofanartisanknownasablacksmithitcanbeworkedintomanyusefulobjectssuchashorseshoes,nails,plows,chains, pails,ladders,andmanytools.Infoundries,ironandsteelareshapedinfargreaterquantitiesintosuchobjectsasfurnitureandpartsofaircraft,ships,motorvehicles,and appliances. Ironhasonefaultasastructuralmaterial:itrustseasily.Inthepresenceofwater(especiallysaltwater)itcorrodesintooxides: Fe(s)+1/2O2(g)FeO(s)2Fe(s)+3/2O2(g)Fe2O3(s) andamixedoxideknownashematite 2Fe(s)+3/2O2(g)Fe2O3(s) oneofthemostcommonoresofiron.Ironoxidesaremildlyalkaline,soironresistsattacksbyalkalisacidsattackit.Forexample, Fe (s)+H2SO4(l)Fe2+ (aq)+SO42(aq)+H2(g) Evenacomparativelyweakacid,likephosphoricacid,canattackironoxide.Thisisthe"navaljelly"reactionthatremovesrustfromiron: FeO(s)+H3PO4(l)Fe2+ (aq)+HPO4(aq)2+H2O(l) Agreatadvanceofhumanity,thebeginningoftheIronAge,beganwhenpeoplefoundthattheycouldseparateironfromoxygenbyburningitwithcarbon(usuallycharcoal)which canreduceironoxidestoiron: Fe3O4(s)+4C(s)3Fe(s)+4CO(g) Muchofexistingeconomicactivitydependsupontheextractionofironore,thereductionofironoretoiron,thestrengtheningofirontosteel,thecreationofironandsteelobjects, andthevariouspracticesusedinprotectingironfromcorrosion. Importantasthatactivityis,ourliveswouldbeimpossiblewithoutanimportantcompoundofironknownashemoglobinwhichcarriesoxygenthroughthebloodstreamtocellswhere thecellscanusetheoxygentoreleaseenergyfromfoodalsodeliveredtocellsthroughthebloodstream.
twosuspensionbridges
anoldironplow
redbloodcellscontain hemoglobin
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anelectromagnetattracting scrapiron
Theearthitselfhasahot,densecoreoflargelyironandnickel.AtthetemperaturescharacteristicoftheEarth'scoretheironandnickelformagiantnaturalmagnetthatcreatesa magneticfieldthatgoesbeyondtheEarthitselfintotheatmosphere.ThatmagneticfielddrivesoffmuchdangerousradiationthatwouldkilllifeontheEarth'ssurfaceifitreached theEarth'ssurface. Cobaltandnickelarebothfarscarcerthanironandnotasextensivelyusedincommerceasiron,althoughtheyhavespecializeduses.
PlatinumFamily
ThePlatinumgroupmetalsareruthenium,rhodium,palladium,osmium,iridium,andplatinum.Theseelementsarefoundinthesecondtworowsof Groups8/9/10(IIIB). UnliketheirlightercounterpartsinGroups8,9,and10oftheseelementsareresistanttocorrosionandtarnish.Theyserveas catalystsformanychemicalreactions,speedingupthe reactionwithoutbeingconsumedbyit. Palladium,osmium,andtheotherplatinumgroupmetalsabsorbhydrogenwhenpowdered. Rhodiumisusedin catalyticconvertersmetallicstructuresfoundinsidevehicles.Catalyticconvertersconvertnitricoxides(whicharetoxicpollutants)intoelementalnitrogenand oxygen(bothofwhichmakeupbreathableair):
Thatreactionwouldnotoccurwithoutrhodiumtoserveasacatalyst.
InnerTransitionMetals
InnerTransitionMetals
Theinnertransitionmetalsarefoundinthe fblock,usuallyputatthebottomofthePeriodicTable.Theseelementsweresometimescalled rareearthmetalsduetotheirextremely lownaturaloccurrence.Exceptforextremelyunstablepromethiumwhichquicklydecaystoanotherlanthanoidmetal,theseelementsarenotrare.Indeedceriumisabundantin Earth'scrust.)Manyofthemdonotoccurnaturally,butareinsteadcreatedinlabsartificially.Furthermore,theseelementsallhavenearlyidenticalproperties,bothchemicallyand physically,makingthemverydifficulttoidentifyandseparate.Theyarealmostasreactiveasthealkalimetals,andallactinoidsareradioactive,sotheyhavelittlecommercial significance.However,theradioactiveelementscanbeusedinnuclearpowerplantsorasweapons. Mostoftheinnertransitionmetalsformionswitha+3charge.Someofthelighteractinoidscanusetheirfelectronsforbonding,givingthemawiderrangeofoxidationstates,but therestdonotusefelectronsandhaveonlya+3oxidationstate.Ceriumisanotableexception:ithasasomewhatcommon+4oxidationstate,seenincurium(IV)oxideCeO2.
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Theseelementstarnishquicklyinoxygen.Somewilligniteinoxygen.Theyreactwithwatertoreleasehydrogen:
Lanthanoids
Lanthanoidsburninoxygeneasilyandreactviolentlywithnonmetals.Theyareusedinlasersandsometimessteelsdependingontheelement. Neodymiummagnets(Nd2Fe14B)arethestrongestknownpermanentmagnets.Gadoliniumexhibits ferromagnetismbelowroomtemperature. Theterbium(III)cationisvery fluorescent itglowsinthedark. Lantanoidcontractionisaphenomenonthatcausesthelanthanoids(andallelementsafterthem)tohavemuchsmalleratomicradiithanexpected.Thefelectronsdonotshield thenuclearchargeasmuchasexpected,sotheoutermostelectronsareattractedtothenucleusmore.
Actinoids
OnlythoriumanduraniumoccurnaturallyinEarth'scrust(alongwithneptuniumandplutoniumintraceamounts). Theactinoidsareradioactiveanddecayintomorestableelements.Theactinoidsthatdonotoccurnaturallyhavebeencreatedinlabsforexperimentsandresearch.
NuclearChemistry
ThroughoutyourstudyofGeneralChemistry,youhaveundoubtedlyheardof"radioactiveelements"and"unstableisotopes".These elementsarethestudyof nuclearchemistry.Normalchemicalreactionsoccurbetweenatomsandelectrons.Atomsgain,lose,and shareelectronstoformdifferentsubstances.Chemicalreactionsareessentiallyinteractionsofelectrons. Nuclearreactions,ontheother hand,occurwithinthenucleusofanatom.Theyinvolvethegaining,losing,andtransformationofprotons,neutrons,andsometimes otherparticles(electronsandphotons).Nuclearchemistryissomethingthatyoucanstudyonlywithinyourtextbookradioactive substancesaredeadlytolivingthings,cancauseexplosions,andaredifficulttoprocure. Youshouldalreadyknowwhat isotopesare:elementswiththesamenumberofprotons,butdifferentnumbersofneutrons(anda differenttotalmass).Someisotopesare stableanddonotdecay.Theylastindefinitely.Otherisotopesare unstable,meaningthatthey areradioactive.Theywillundergonuclearreactionstobecomeamorestableisotope.Someelementsarealwaysunstable,regardlessof howmanyneutrons,soalloftheirisotopesareunstable. Forexample,carbon12(6protons,6neutrons)isstable.Carbon14(6protons,8neutrons)isunstableanddecaysintonitrogen14.This isunusualfromachemicalpointofviewthereisnowayforanatomtochangeintoadifferentelement.Thisisnuclearchemistry, though,andelements dochangefrequentlyintheirquesttobecomemorestable.
Stability
Thereisnoformulaorexactruletodeterminewhichisotopesarestableandwhichareunstable.Thatmustbedeterminedexperimentally. Patternshaveemergedthroughoutthestudyoftheelements,andtherearesomegeneralguidelinesyoucanusetoguessifanisotope willbestableorradioactive: Lighterelementsarestablewhentheyhaveroughlyequalnumbersofprotonsandneutrons. Heavierelementsarestablewhentheyhavemoreneutronsthanprotonsinabouta3:2ratio. Elementsthathavea"magicnumber"ofprotonsorneutronsareespeciallystable:2,8,20,28,50,82,126.
Anuclearreaction
Inregardtothemagicnumbers,noticehowhelium4(2p,2n)isthemostabundantisotopeintheuniverse.Lead208istheheavieststableisotopeknown(82p,126n).Theairwe
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Inregardtothemagicnumbers,noticehowhelium4(2p,2n)isthemostabundantisotopeintheuniverse.Lead208istheheavieststableisotopeknown(82p,126n).Theairwe breatheisfilledwithoxygen16(8p,8n).Thestabilityoftheseisotopesisnocoincidence.
FusionandFission
Fusionreactionstaketwosmallnucleiand"fuses"themtogetherintoonelargenucleus. Fissionreactionssplitalargenucleusinto smallernuclei.Fissionreleasestremendousamountsofenergy,whichiswhyfissionreactionsareusedinbothnuclearpowerplants(to provideelectricitytoanentirecity)andnuclearbombs(todestroyanentirecity).Fusionreactionsreleaseevengreateramountsof energy,buttheyonlyoccuratunfathomablyhightemperatures.Fusionreactionsoccurinstarsinouterspace.Oursunisbasicallyone giantfusionreactor.Hydrogennucleifusetogetherintoheliumnuclei,releasingthelightandheatthatwarmsourplanet.Herearesome examplenuclearreactions:
Fusion
Fission
NoticethattheLawofConservationofMatterisbentbutnotbroken.Ifyouaddupthemassnumbers,theywillbeequalonbothsidesof thereaction.Thetotalchargenumberswillalsobeequal.
DecayModes
Anunstableisotopewilldecaytobecomemorestable.Therearemanydecaymodes,butafewarecommon:
ThefusionreactionthatpowerstheSun
CommonDecayModes Alphadecayreleasesanalphaparticle(helium4,2p+2n).Occurswhentheisotopeistoobigtobestable. Beta+ decayconvertsaneutronintoaproton,releasingabetaparticle(electron).Occurswhentherearetoomanyneutronstobestable. Betadecayconvertsaprotonintoaneutron,releasingabetaparticle(positron).Occurswhentherearetoomanyprotonstobestable. Gammadecayreleasesagammaparticle(photon).Occurswhenthenucleushastoomuchenergy. Electroncaptureconvertsaprotonintoaneutronbyabsorbinganelectron.Occurswhentherearetoomanyprotonstobestable.
Asfarashealthconcerns,alphaparticlesarethemostdangerous.Theycanbeinhaled,causingbodilydamage.Theyareheavyandhaveadoublepositivecharge,buttheyare easilystoppedbyapieceofpaperorskin.Betaparticlesaresimplyelectrons(orpositrons,anantielectron).Theyaresomewhatdangerous,andtheyarestoppedbyapieceofwood oraluminumfoil.Gammaraysareonlystoppedbythickslabsoflead.Theyareessentiallyxraysthathaveextremeamountsofenergy.Althoughtheyhavethemostenergy,they onlycausedamagetothingsdirectlyexposedtoaradioactivesubstance.Theotherparticlesareworsebecausetheycantravelthroughtheatmosphere. Aparticularisotopealwaysusesthesamedecaymode.Thesereactionswillsummarizethedecaymodes(noticethelawofconservation):
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Alphadecay
Thesamereaction,writtenwiththemorecommonnotation.
Betadecay
Beta+ decay
SyntheticElements
Shortlivednaturalelementsandsyntheticelements
91elementsoftheknown118elementsoccurnaturallyonEarth.TheotherseventeenallelementsbeyondplutoniumonthePeriodictable,andthreeotherstechnetium(43 electrons),promethium(61),andneptunium(93)aretoounstabletoexistonEarthandarenotamongtherareelementsthatarepartsofthenucleardecayprocessofeither thoriumoruranium.Theelementsthatdonotoccurnaturallyare synthetic.Syntheticelementsareelementsthathavebeencreatedinalaboratorybyartificialmeans.Synthetic elementsareveryunstableandhavefewcommercialpurposes.Theydecayintootherelementsinafractionofasecond.Mostarecreatedpurelyforresearchandexperiment. Syntheticelementsarecreatedin particleaccelerators.Twosmallerelementsareacceleratedtoincrediblespeedsandcollidedintoeachother.Theirnucleimergetogetherintoa largerelement.Theelementisstudiedbylabequipmentbeforeitdecays. Sevenofthe91naturallyoccurringelements(polonium,astatine,radon,francium,radium,actinium,andprotactinium)existonlyinthepresenceofnaturallyoccurringradioactive elementsuraniumandthorium.Thesecompriseallelementswithatomicnumbers84through91exceptforthorium(90).Allisotopesoftheseelementsareveryshortlived,and thoseoftheminuseareusedonlyfortheirradioactiveproperties(mostnotablyinradium,andthenasadesperatetherapyforsomecancers).Becauseoftheirshorthalflivesand thehazardsassociatedwiththeirradioactivitythechemistriesoftheseelementsareoftenextremelydifficulttostudy.
Naming
MostsyntheticelementshavebeennamedbytheIUPAC,theinternationalauthorityfornamingchemicals.Theyarenamedafterfamousscientistsorplaceswheretheelementwas formed.Forexample,einsteinium(Es,99)andamericium(Am,95).Someelementsaretoonewtohaveofficialnames.Beforeitcanbenamed,anelementmustbediscovered andproventoexistbyascientistorteam.Then,theelement'sdiscoverer(s)willbeallowedtochooseaname.Untiltheelementhasaname,itisgivena provisionalname. Provisionalnamesaremadeofachainofwords,eachrepresentingadigitintheelement'satomicnumber.Forexample,ununseptiumiselement117,unnilpentiumwaselement 105(sincerenamedasdubnium),andunbioctiumwouldbeelementelement128(notbelievedtoexist).GeneralChemistry/ChemistriesofVariousElements/SalsalLiquidity
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PeriodicTable
Appendices
Group 1 I
Period
2 II
10
11
12
13 III
14 IV
15 V
16 VI
17 VII
18 VIII
hydrogen
helium
H
1.0079 lithium beryllium boron carbon nitrogen oxygen fluorine
He
4.0026 neon
10
Li
6.9412 sodium
Be
9.0122 magnesium
B
10.811 aluminum
C
12.011 silicon
N
14.007 phosphorus
O
15.999 sulfur
F
18.998 chlorine
Ne
20.180 argon
11
12
13
14
15
16
17
18
Na
22.990 potassium
Mg
24.305 calcium scandium titanium vanadium chromium manganese iron cobalt nickel copper zinc
Al
26.982 gallium
Si
28.086 germanium
P
30.974 arsenic
S
32.066 selenium
Cl
35.453 bromine
Ar
39.948 krypton
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
K
39.098 rubidium
Ca
40.078 strontium
Sc
44.956 yttrium
Ti
47.867 zirconium
V
50.942 niobium
Cr
51.996
Mn
54.938
Fe
55.845
Co
58.933 rhodium
Ni
58.693 palladium
Cu
63.546 silver
Zn
65.382 cadmium
Ga
69.723 indium
Ge
72.612 tin
As
74.922 antimony
Se
78.963 tellurium
Br
79.904 iodine
Kr
83.798 xenon
molybdenum technetium ruthenium
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
Rb
85.468 caesium
Sr
87.621 barium
Y
88.906 Innertransitionmetal
Zr
91.224 hafnium
Nb
92.906 tantalum
Mo
95.962 tungsten
Tc
98.906 rhenium
Ru
101.07 osmium
Rh
102.91 iridium
Pd
106.42 platinum
Ag
107.87 gold
Cd
112.41 mercury
In
114.82 thallium
Sn
118.71 lead
Sb
121.76 bismuth
Te
127.60 polonium
I
126.90 astatine
Xe
131.29 radon
55
56
Cs
132.91 francium
Ba
137.33 radium
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
Itm
Hf
178.49
Ta
180.95
W
183.84
Re
186.21
Os
190.23
Ir
192.22
Pt
195.08
Au
196.97
Hg
200.59
Tl
204.38
Pb
207.21
Bi
208.98
Po
[209]
At
[210]
Rn
[222]
87
88
Fr
[223]
Ra
[226]
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lanthanum cerium praseodymium neodymium promethium samarium europium gadolinium terbium dysprosium holmium erbium thulium ytterbium lutetium
*Lanthanides
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
La
138.91 actinium
Ce
140.12 thorium
Pr
140.91 protactinium
Nd
144.24 uranium
Pm
146.92 neptunium
Sm
150.36
Eu
151.96
Gd
157.25 curium
Tb
158.93
Dy
162.50
Ho
164.93
Er
167.26 fermium
Tm
168.93
Yb
173.05
Lu
174.97
plutonium americium
berkelium californium einsteinium
mendelevium nobelium lawrencium
**Actinide
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
Ac
227.03
Th
232.04
Pa
231.04
U
238.03
Np
[237]
Pu
[244]
Am
[243]
Cm
[247]
Bk
[247]
Cf
[251]
Es
[252]
Fm
[257]
Md
[258]
No
[262]
Lr
[263]
Atomicmassesinbracketsarethemoststableisotope.
ChemicalSeriesofthePeriodicTable Alkalimetals Alkalineearths Lanthaniods Actinoids Transitionmetals Poormetals Metalloids Nonmetals Halogens Noblegases
UnitsofMeasure
SIFundamentalUnits
ThesearethesevenbasicSIunitsfromwhichallotherunitsareconstructed. Quantity Length Time Mass Symbol l t m Unit metre second UnitSymbol m s
kilogram kg kelvin mole K mol
Thermodynamictemperature T Amount Electricalcharge Luminousintensity n Q IV
coulomb C candela cd
SIDerivedUnits
Allotherunitsare derivedunits.Theyarebuiltfromfundamentalunits.ThisisasmallselectionofunitsthatmaybefoundinGeneralChemistry.
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Quantity Force Energy Pressure Power Electricalcurrent
Symbol F U P
Unit
UnitSymbol DerivedFrom kgms2 kgm2s2 kgm1s2 kgm2s3 Cs1 JC1
newton N joule pascal watt J Pa W
ampere A volt V
Electricalpotential V
SIPrefixes
Aprefixappearsbeforeaunit'ssymbolwhenexpressingverylargeorverysmallquantities.Forexample:0.001kg=1g=1000mg.
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1000n
10n Prefix Symbol Y Z E P T G
Decimal 1000000000000000000000000 1000000000000000000000 1000000000000000000 1000000000000000 1000000000000 1000000000 1000000 1000 100 10 1 0.1 0.01 0.001 0.000001 0.000000001 0.000000000001 0.000000000000001 0.000000000000000001 0.000000000000000000001 0.000000000000000000000001
10008 1024 yotta 10007 1021 zetta 10006 1018 exa 10005 1015 peta 10004 1012 tera 10003 109 10002 106 10001 103 102 101 10000 100 giga
mega M kilo k
hecto h deca da
(none) (none) d c m
101 deci 102 centi 10001 103 milli
10002 106 micro 10003 109 nano 10004 1012 pico n p
10005 1015 femto f 10006 1018 atto a
10007 1021 zepto z 10008 1024 yocto y
SolutionConcentrationUnits
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Quantity Molarity Molality MoleFraction
Symbol Units M m
Description
mol/L molesofsoluteperliterofsolution mol/kg molesofsoluteperkilogramof solvent (none) molesofsolutepermolesofsolution (none) milligramsofsoluteperkilogramofsolution (none) microgramsofsoluteperkilogramofsolution
Partspermillion ppm Partsperbillion ppb
OtherUsefulUnits
Volume
VolumeUnit Conversion MassofWater(4C) 1L 1cm3 1m3 =1000cm3 1kg =1m/L =1000L 1kg 1000kg
Pressure
Name Atmosphere Pascal Torr(mmHg) Symbol atm Pa torr Conversion =760torr 7.5x103torr 133.3Pa 51.7torr 6.894kPa =101.325kPa
Poundpersquareinch psi
Temperature
OnedegreeCelsiusisequaltooneKelvin(inmagnitude). Name Symbol Abs.Zero M.P.ofWater B.P.ofWater 456.67F 32F 273.15C 0C 0K 273.15K 212F 100C 373.15K
Fahrenheit F Celsius Kelvin C K
*Noticeitis not "degreesKelvin".
Constants
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UsefulPhysical/ChemicalConstants
Constant Avogadro'sNumber FaradayConstant AtomicMassConstant MolarGasConstant MolarGasConstant Coulomb'sConstant SpeedofLight(Vacuum) BoltzmannConstant Value NA =6.022141023mol1 F=96485.33Cmol1 1amu=1.6605381027kg R=8.3144Jmol1K 1 R=0.082 057 46L atm K 1 mol1 ke=8.987551109Nm2C2 c=299792458ms1 k=1.380651023JK 1
ChargeonaProton/Electron e=1.6021761019C TheseconstantswereobtainedfromTheNISTReferenceonConstants,UnitsandUncertainty(http://physics.nist.gov/cuu/).
UsefulEquations
General
Density
Moles
PercentError
PercentComposition(bymass)
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Molarity
AtomicStructure
EnergyofWave Symbol Meaning energy WaveRelation frequency charge Coulomb'sconstant Coulomb'sLaw Symbol Meaning speedoflight wavelength distance Plank'sconstant
Solutions,Liquids,andGases
Symbol Rauolt'sLaw pressure volume BoilingPointElevation numberofmoles temperature(inKelvin) FreezingPointDepression molalfreezingpointconstant molalboilingpointconstant IdealGasLaw molefraction molality molarity CombinedGasLaw Meaning
Titration
Dilution
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Equilibrium
Symbol Meaning equilibriumconstant(general) pOH pressureequilibriumconstant concentrationequilibriumconstant (forwater) gaslawconstant temperature(inKelvin) molesofproductmolesofreactant Pressure/Concentration
pH
Equilibrium, forareaction
Thermochemistry
HeatTransfer Symbol Meaning heatenergy Enthalpy mass specificheat Entropy temperature(inKelvin)
FreeEnergy
StandardReductionPotentials
HalfReaction F2(g)+2 e 2F E o(V) 2.87
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Co3+ + e Au3+ +3e Cl2(g)+2 e O2(g)+4H+ +4 e Br2(l)+2 e 2Hg2+ +2 e Ag+ + e Hg22+ +2 e Fe3+ + e I 2(s)+2 e Cu+ + e Cu2+ +2 e Cu2+ + e Sn4+ +2 e S(s)+2H+ +2 e 2H+ +2 e Pb2+ +2 e Sn2+ +2 e Ni2+ +2 e Co2+ +2 e Tl+ + e Cd2+ +2 e Cr3+ + e Fe2+ +2 e Cr3+ +3 e
Co2+ Au(s) 2Cl
1.82 1.50 1.36
2H2O(l) 1.23 2Br Hg22+ Ag(s) 1.07 0.92 0.80
2Hg(l) Fe2+ 2I Cu(s) Cu(s) Cu+ Sn2+ H2S(g) H2(g) Pb(s) Sn(s) Ni(s) Co(s) Tl(s) Cd(s) Cr2+ Fe(s) Cr(s)
0.79 0.77 0.53 0.52 0.34 0.15 0.15 0.15 0.00 0.13 0.14 0.25 0.28 0.34 0.40 0.41 0.44 0.74
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Zn2+ +2 e Mn2+ +2 e Al3+ +3 e Be2+ +2 e
Zn(s) Mn(s) Al(s) Be(s)
0.76 1.18 1.66 1.70
Mg2+ +2 e
Mg(s) Na(s) Ca(s) Sr(s) Ba(s) Rb(s) K(s) Cs(s) Li(s)
2.37 2.71 2.87 2.89 2.90 2.92 2.92 2.92 3.05
Na+ + e Ca2+ +2 e Sr2+ +2 e Ba2+ +2 e Rb+ + e K + + e Cs+ + e Li+ + e
ElementsandtheirProperties
Name Actinium Aluminium Americium Antimony Argon Arsenic Astatine Barium Berkelium Beryllium Symbol Ac Al Am Sb Ar As At Ba Bk Be Number 89 13 95 51 18 33 85 56 97 4 Atomicmass 227.0278 26.982 (243) 121.75 39.948 74.92159 209.9871 137.327 (247) 9.012182 Density at20C(g/cm3) 10.07 2.70 13.67 6.69 1.66 5.72 7(approx.) 3.65 13.25 1.85 Meltingpoint(C) 1047 660.5 994 630.7 189.4 613(sublimation) 302 725 986 1278 Boilingpoint(C) 3197 2467 2607 1750 185.9 613 337 1640 710 2970 Phase* S S XS S G S S S XS S Oxidation** +3 +3 +3+4+5+6 3+3+5 0 3+3+5 +1+3(prob.) +2 +3+4 +2
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Bismuth Bohrium Boron Bromine Cadmium Caesium Calcium Californium Carbon Cerium Chlorine Chromium Cobalt Copper Copernicium Curium
Bi Bh B Br Cd Cs Ca Cf C Ce Cl Cr Co Cu Cn Cm
83 107 5 35 48 55 20 98 6 58 17 24 27 29 112 96 110 105 66 99 68 63 100 9 87 64 31 32 79 72 108 2
208.98037
9.80 38(est.)
271.4
1560
S XS
+3+5
10.811 79.904 112.411 132.90543 40.078 (251) 12.011 140.115 35.4527 51.9961 58.9332 63.546
2.46 3.14 8.64 1.90 1.54 15.1 3.51 6.77 2.95 7.14 8.89 8.92 13.5336
2300 7.3 321 28.4 839
2550 58.8 765 690 1487
S DL S S S XS
+3 1+1+5 +2 +1 +2 +3 4+2+4 +3+4 1+1+3+5+7 +2+3+6 +2+3 +1+2
3550 798 101 1857 1495 1083.5
4827 3257 34.6 2482 2870 2595
S S DG S S S XL
(247)
13.51 21.46 39(est.)
1067
3110
XS XS XS
+3
Darmstadtium Ds Dubnium Dysprosium Einsteinium Erbium Europium Fermium Fluorine Francium Gadolinium Gallium Germanium Gold Hafnium Hassium Helium Db Dy Es Er Eu Fm F Fr Gd Ga Ge Au Hf Hs He
162.5 (252) 167.26 151.965 (257) 18.9984032 223.0197 157.25 69.723 72.61 196.96654 178.49
8.56 13.5(est.) 9.05 5.25 2781 1.58 1.87 7.89 5.91 5.32 19.32 13.31 41(est.)
1409 860 1522 822
2335
S XS
+3
2510 1597
S S XS
+3 +2+3
219.6 27 1311 29.8 937.4 1064.4 2150
188.1 677 3233 2403 2830 2940 5400
DG S S S S S S XS
1 +1 +3 +3 4+2+4 +1+3 +4
4.002602
0.17
273(n/a)
268.9
0
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Holmium Hydrogen Indium Iodine Iridium Iron Krypton Lanthanum Lawrencium Lead Lithium Lutetium Magnesium Manganese Meitnerium Mendelevium Mercury Molybdenum Neodymium Neon Neptunium Nickel Niobium Nitrogen Nobelium Osmium Oxygen Palladium Phosphorus Platinum Plutonium Polonium
Ho H In I Ir Fe Kr La Lr Pb Li Lu Mg Mn Mt Md Hg Mo Nd Ne Np Ni Nb N No Os O Pd P Pt Pu Po
67 1 49 53 77 26 36 57 103 82 3 71 12 25 109 101 80 42 60 10 93 28 41 7 102 76 8 46 15 78 94 84
164.93032 1.00794 114.82 126.90447 192.22 55.847 83.8 138.9055 (263) 207.2 6.941 174.967 24.305 54.93805
8.78 0.084 7.31 4.94 22.65 7.87 3.48 6.16 9.84 11.34 0.53 9.84 1.74 7.44 35(est.)
1470 259.1 156.2 113.5 2410 1535 156.6 920 2961 327.5 180.5 1656 648.8 1244
2720 252.9 2080 184.4 4130 2750 152.3 3454
S DG S DS S S G S XS
+3 +11 +3 1+1+5+7 +3+4 +2+3 0+2 +3
1740 1317 3315 1107 2097
S S S S S XS XS
+2+4 +1 +3 +2 +2+3+4+7
(258) 200.59 95.94 144.24 20.1797 (237) 58.69 92.90638 14.00674 (259) 190.2 15.9994 106.42 30.973762 195.08 (244) 208.9824
1521 13.55 10.28 7.00 0.84 20.48 8.91 8.58 1.17 1521 22.61 1.33 12.02 1.82 21.45 19.74 9.20 3045 218.4 1552 44(P4) 1772 641 254 5027 182.9 3140 280(P4) 3827 3327 962 38.9 2617 1010 248.7 640 1453 2468 209.9 356.6 5560 3127 246.1 3902 2732 4927 195.8
L S S G S S S DG XS S DG S S S S S
+1+2 +3+6 +3 0 +3+4+5+6 +2+3 +3+5 3+3+5
+3+4 2 +2+4 3+3+5 +2+4 +3+4+5+6 +2+4

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Potassium
19 59 61 91 88 86 75 45 111 37 44 104 62 21 106 34 47 14 11 38 16 73 43 52 65 81 90 69 50 22 74 116
39.0983 140.90765 146.9151 231.0359 226.0254 222.0176 186.207 102.9055
0.86 6.48 7.22 15.37 5.50 9.23 21.03 12.41 19.282
63.7 931 1080 1554 700 71 3180 1966
774 3212 2730 4030 1140 61.8 5627 3727
S S S S S G S S XS
+1 +3 +3 +4+5 +2 0 +4+6+7 +3
Praseodymium Pr Promethium Protactinium Radium Radon Rhenium Rhodium Roentgenium Rubidium Ruthenium Pm Pa Ra Rn Re Rh Rg Rb Ru
85.4678 101.07
1.53 12.45 18.1
39 2310
688 3900
S S XS
+1 +3
Rutherfordium Rf Samarium Scandium Seaborgium Selenium Silver Silicon Sodium Strontium Sulfur Tantalum Technetium Tellurium Terbium Thallium Thorium Thulium Tin Titanium Tungsten Ununhexium Sm Sc Sg Se Ag Si Na Sr S Ta Tc Te Tb Tl Th Tm Sn Ti W Uuh
150.36 44.95591
7.54 2.99 35(est.)
1072 1539
1778 2832
S S XS
+2+3 +3
78.96 107.8682 28.0855 22.989768 87.62 32.066 180.9479 98.9063 127.6 158.92534 204.3833 232.0381 168.93421 118.71 47.88 183.85
4.82 10.49 2.33 0.97 2.63 2.06 16.68 11.49 6.25 8.25 11.85 11.72 9.32 7.29 4.51 19.26 9.32
217 961.9 1410 97.8 769 113 2996 2172 449.6 1360 303.6 1750 1545 232 1660 3407
685 2212 2355 892 1384 444.7 5425 5030 990 3041 1457 4787 1727 2270 3260 5927
S S S S S S S S S S S S S S S S X
2+4+6 +1 4+2+4 +1 +2 2+4+6 +5 +4+6+7 2+4+6 +3 +1+3 +4 +3 +2+4 +2+3+4 +6
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Ununoctium Ununpentium
Uuo Uup
118 115 114 117 113 92 23 54 70 39 30 40 238.0289 50.9415 131.29 173.04 88.90585 65.39 91.224 11.85 18.97 6.09 4.49 6.97 4.47 7.14 6.51 1132.4 1890 111.9 824 1523 419.6 1852 3818 3380 107 1193 3337 907 4377 9.807 11.342
X X X X X S S G S S S S +3+4+5+6 +2+3+4+5 0+2+4+6 +2+3 +3 +2 +4
Ununquadium Uuq Ununseptium Ununtrium Uranium Vanadium Xenon Ytterbium Yttrium Zinc Zirconium Uus Uut U V Xe Yb Y Zn Zr
(*)PhaseatSTP,whereSissolid,Lisliquid,andGisgas.Xisforsynthetic(laboratory)elements,andDisfordiatomicelements. (**)Mostcommonoxidationstates,notanexhaustivelist. Atomicweightsinparenthesesaretheatomicweightsforthemoststableisotope.
GNUFreeDocumentationLicense
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0.PREAMBLE
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1.APPLICABILITYANDDEFINITIONS
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2.VERBATIMCOPYING
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3.COPYINGINQUANTITY
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4.MODIFICATIONS
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M. DeleteanysectionEntitled"Endorsements".SuchasectionmaynotbeincludedintheModifiedversion. N. DonotretitleanyexistingsectiontobeEntitled"Endorsements"ortoconflictintitlewithanyInvariantSection. O. PreserveanyWarrantyDisclaimers. IftheModifiedVersionincludesnewfrontmattersectionsorappendicesthatqualifyasSecondarySectionsandcontainnomaterialcopiedfromtheDocument,youmayatyour optiondesignatesomeorallofthesesectionsasinvariant.Todothis,addtheirtitlestothelistofInvariantSectionsintheModifiedVersion'slicensenotice.Thesetitlesmustbe distinctfromanyothersectiontitles. YoumayaddasectionEntitled"Endorsements",provideditcontainsnothingbutendorsementsofyourModifiedVersionbyvariouspartiesforexample,statementsofpeerreview orthatthetexthasbeenapprovedbyanorganizationastheauthoritativedefinitionofastandard. YoumayaddapassageofuptofivewordsasaFrontCoverText,andapassageofupto25wordsasaBackCoverText,totheendofthelistofCoverTextsintheModified Version.OnlyonepassageofFrontCoverTextandoneofBackCoverTextmaybeaddedby(orthrougharrangementsmadeby)anyoneentity.IftheDocumentalreadyincludesa covertextforthesamecover,previouslyaddedbyyouorbyarrangementmadebythesameentityyouareactingonbehalfof,youmaynotaddanotherbutyoumayreplacethe oldone,onexplicitpermissionfromthepreviouspublisherthataddedtheoldone. Theauthor(s)andpublisher(s)oftheDocumentdonotbythisLicensegivepermissiontousetheirnamesforpublicityforortoassertorimplyendorsementofanyModifiedVersion.
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General Chemistry/Print version - Wikibooks, open books for an open world

General Chemistry/Print version - Wikibooks, open books for an open world

General Chemistry/Print version - Wikibooks, open books for an open world

General Chemistry/Print version - Wikibooks, open books for an open world

General Chemistry/Print version - Wikibooks, open books for an open world

General Chemistry/Print version - Wikibooks, open books for an open world

Extensivepropertiesdependontheamountofmatterthatisbeingmeasured. Theseincludemassandvolume. Intensivepropertiesdonotdependontheamountofmatter.Theseinclude densityandcolor.

Physicalpropertiescanbemeasuredwithoutchangingthechemical'sidentity. Thefreezingpointofasubstanceisphysical.Whenwaterfreezes,it'sstillH2O. Chemicalpropertiesdealwithhowonechemicalreactswithanother.Weknow thatwoodisflammablebecauseitbecomesheat,ash,andcarbondioxidewhen heatedinthepresenceofoxygen.

Theiceinthispictureisasolid.Thewater inthepictureisaliquid.Intheairthereis watervapor,whichisagas.

General Chemistry/Print version - Wikibooks, open books for an open world

Phasechangesarewhenyoumelt,freeze,boil,condense,sublimate,ordeposita substance.Theydonotchangethenatureofthesubstanceunlessachemicalchange occursalongwiththephysicalchange.

Thesemaybeirreversible,buttheresultisstillcomposedofthesamemolecules.When youcutyourhair,thatisaphysicalchange,eventhoughyoucan'tputthehairbackon yourheadagain.

General Chemistry/Print version - Wikibooks, open books for an open world

Changesofcolororreleaseof odors(i.e.releaseofagas)might bechemical.

Asanexample,theelementchromiumshowsdifferentcolorswhenitisindifferent compounds,butasinglechromiumcompoundwillnotchangecoloronitsownwithout somesortofreaction.

Release/absorptionofenergy (heat,light,sound)isgenerallynot easilycategorized.

General Chemistry/Print version - Wikibooks, open books for an open world

Whatexactlyistoothpaste?Wecan'texactlyclassifyitbyitsstateofmatter.Ithasadefinite shapeandvolume,likeasolid.Butthenyousqueezethetube,anditflowsalmostlikea liquid.Andthenthere'sjelly,shavingcream,smoke,dough,andSillyPutty...

General Chemistry/Print version - Wikibooks, open books for an open world

Adistillationapparatushasaboilingflask, aplacetocoolthevapordown,anda collectingflask.

General Chemistry/Print version - Wikibooks, open books for an open world

Chromatography separates things dissolved inliquid.

Iftheredpartsareprotonsandthegreen partsareneutrons,what'stheatomic, neutron,andmassnumberofthisatom? (lithium)

The Massnumberisthesumofprotonsandneutronsinanatom.Itisdenoted A.Tofindthemassnumberofanatom,rememberthat A=Z+N.Themassnumberofanatomis

General Chemistry/Print version - Wikibooks, open books for an open world

Thisexampleshowscarbon12.Noticehowtheatomicnumberismissing.Youknowwhichelementitis becauseoftheC,sothereisnoneedtowritethenumberofprotons.Theatomicnumberisrarelywritten becausetheelementsymbolimplieshowmanyprotonsthereare.

Exerciseforthereader! Trywritingthesymbolforanatomwithsevenprotons,sevenneutrons,andeightelectrons.Youwillneedtolookupitssymbolontheperiodic table.

General Chemistry/Print version - Wikibooks, open books for an open world

Example Thereare128.2gofrubidium(atomicmass=85.47amu).Howmanyatomsarethere? (128.2g)/(85.47g/mol)=1.5mol (1.5mol)(6.0221023)= 9.031023atomsofrubidium

Historyof Atomic Structure

General Chemistry/Print version - Wikibooks, open books for an open world

Afire,shownby Lavoisiertobea chemicalreaction andnotanelement.

General Chemistry/Print version - Wikibooks, open books for an open world

General Chemistry/Print version - Wikibooks, open books for an open world

oil( (whichherearrangedfrom theaccelerationduetogravity,and ofthechargeoftheelectron, .

TheBohrmodeloftheatomhasshellswith numberedsphericalenergylevelsthe largernumbersmeanlargerspheresand higherenergylevels.Thewaveexitingthe pictureonthelefthascomefroman electronjump,resultinginaphoton.(Level sizesnottoscale.)

General Chemistry/Print version - Wikibooks, open books for an open world

General Chemistry/Print version - Wikibooks, open books for an open world

Ourfriendsthephysicistssaythatneutrons andprotonsaremadeofevensmaller particlescalled quarks.Fortunately,we don'tneedtoknowaboutthatbecause quarksdonotaffectchemistry.Instead, quarksfallinthefieldofQuantum Mechanics.

General Chemistry/Print version - Wikibooks, open books for an open world

Sincewavelengthandfrequencyareinverselyrelated,theirproduct(multiplication)alwaysequalsaconstantspecifically,3.0x108m/sec,whichisbetterknownasthespeedof light. ThewavelengthandfrequencyofanyspecificoccurrenceofERdetermineitspositiononthe electromagneticspectrum.

General Chemistry/Print version - Wikibooks, open books for an open world

Asyoucansee,visiblelightisonlyatinyfractionofthespectrum. Theenergyofanelectromagneticwaveisgivenby frequencywilldoubletheenergy. ,where isPlank'sconstantand isthefrequency.Energyisdirectlyproportionaltofrequencydoublingthe

Asphotonsstrikeametal,electronsare freed.Thephotoelectriceffectdependsonly onthelight'sfrequency,notintensity,which defieswavebehavior.

General Chemistry/Print version - Wikibooks, open books for an open world

Thinkofthewaveequationlikeasprinkler youcannotpredicttheexactpathofa particularwaterdroplet,butyoudoknow (basedontherangeandshapeofthe sprinkler)whereitismostlikelytogo.

Determinesthe shell theelectronisin.Theshellisthemaincomponentthatdeterminestheenergyoftheelectron(higher ncorrespondstohigherenergy),aswellasnuclear

General Chemistry/Print version - Wikibooks, open books for an open world

General Chemistry/Print version - Wikibooks, open books for an open world

General Chemistry/Print version - Wikibooks, open books for an open world

General Chemistry/Print version - Wikibooks, open books for an open world

General Chemistry/Print version - Wikibooks, open books for an open world

General Chemistry/Print version - Wikibooks, open books for an open world

ThisanimationdemonstratestheAufbau principle,Hund'sRule,andthePauliExclusion principle.

General Chemistry/Print version - Wikibooks, open books for an open world

Ifoneoftheseatomshasbeenionized,thatis,itlosesanelectron,itwillcomefromthesorbitalratherthanthedorbital.Forinstance,theconfigurationofCu+ is[Ar]4s03d10.If moreelectronsareremoved,theywillcomefromthedorbital.

Thespinofanelectron createsamagneticfield (albeitridiculouslyweak),so unpairedelectronscreatea smallmagneticfield.Paired electronshaveoppositespin, sothemagneticfieldscancel eachotherout,leadingto diamagnetism.

General Chemistry/Print version - Wikibooks, open books for an open world

Potassiumhasmanycoreelectronsthe loneouterelectroncaneasilybepeeledoff duetothe"shielding"effect.

General Chemistry/Print version - Wikibooks, open books for an open world

Periodictrendforionizationenergy.Eachperiodbeginsat aminimumforthealkalimetals,andendsatamaximumfor thenoblegases.

Electronaffinityistheenergyreleased whenanelectronisaddedtoanatom, producinganegativeion.