APchemistry review packetAP化学复习详细大纲

RhondaAlexanderRobertE.LeeHighSchool,Tyler,TXAPQUICKREVIEWSTP=00Cand1atmatSTP1mole=22.4LK=°C+273SolutionStoichiometry:DeterminingMolarity:MolarityandVolume:M1V1=M2V2USEFORDILUTIONPROBLEMSKEYSOLUBILITYRULES1.Saltsofammonium(NH4+)andGroupIarealwayssoluble.2.AllCl-,Br-,I-aresolubleexceptwithAg+,Hg22+,andPb2+whichareinsoluble.3.ClO3-,NO3-,andCH3COO-aresoluble.4.SO4-2aresolubleexceptwithCa2+,Sr2+,Ba2+,Hg22+,Pb2+,whichareinsoluble.Doubledisplacement.Precipitation,neutralization,gasforming.H2CO3inwater=H2O&CO2Singledisplacementorredoxreplacement:(metalsdisplacemetalsandnonmetalsdisplacenonmetals)Combinationorsynthesis=tworeactantsresultinasingleproduct•Metaloxide+waterÆmetallichydroxide(base)•Nonmetaloxide+waterÆnonbinaryacid•Metaloxide+nonmetaloxideÆnonbinarysaltDecomposition=onereactantbecomesseveralproducts•MetallichydroxideÆmetaloxide+water•NonbinaryacidÆnonmetaloxide+water•NonbinarysaltÆmetaloxide+nonmetaloxide•MetallicchloratesÆmetallicchlorides+oxygen•Electrolysisdecomposecompoundintoelements(waterindiluteacidsorsolutionsofdiluteacids)•HydrogenperoxideÆwater+oxygen•MetalliccarbonatesÆmetaloxides+carbondioxide•AmmoniumcarbonateÆammonia,waterandcarbondioxide.Hydrolysis=compoundreactingwithwater.•Watchforsolublesaltsthatcontainanionsofweakacidtheanionisaconjugatebaseandcationsofweakbasesthatareconjugateacids.Reactionsofcoordinatecompoundsandcomplex•ComplexformationbyaddingexcesssourceofligandtotransitionalmetalofhighlychargedmetalionsuchasAl3+Al=4ligandsothers2Xox#•BreakupofcomplexbyaddinganacidÆmetalionandthespeciesformedwhenhydrogenfromtheacidreactswiththeligandLewisacidbasereactions=formationofcoordinatecovalentbondRedox=changeinoxidationstate=areactionbetweenanoxidizerandareducer.Recognized:1.Familiarizationwithimportantoxidizersandreducers2.“addedacid”or“acidified”3.anoxidizerreactswithareducerofthesameelementtoproducetheelementatintermediateoxidationstateAPQuickReview2RhondaAlexanderRobertE.LeeHighSchool,Tyler,TXOXIDIZERSREDUCERSMnO4-inacidMn2+HalideionsHalogensMnO2inacidMn2+MetalelementMetalionMnO4-inneutralorbasicsolutionMnO2SulfiteSulfateCr2O72-inacidCr3+NitiriteNitiriteHNO3concentratedNO2HalogenelementindilutebasicsolutionHypohaliteionanhalideionHNO3diluteNOHalogenelementinconcentratedbasicsolutionHaliteionH2SO4,hot,concentratedSO2MetalousionMetallicionMetalicionsMetalousionsH2O2O2HalogensdiatomicHalideionsC2O42-CO2Na2O2NaOHHClO4Cl-H2O2H2OCombustion-completecombustionofhydrocarbonsresultsinCO2andH2O.(resultsinformingtheoxideoftheelementsofthecompound)GasLaws:KineticmolecularTheory:particlesinconstantrandommotionparticlesdonothavevolumeparticlesdonotattractT↑with↑KE=½m×v2Ideal:particles0volumenoattraction,deviatefromidealatlowtemperatureandhighpressureVanderWaal’sEquationacorrectsforattraction&bcorrectsforvolumemoleculesthatdeviatefromidealgasbehavior:largevolumeandlargeattractionbetweenmoleculesidealgases:molecules:havezerovolumeanddonotattractorrepeleachotherTheIdealGasLaw:(P=pressureinatm,V=volumeinliters,n=moles,R=0.08201L*atm/mol*K,T=temperatureinKelvins)PV=nRTCombineGasLawPVTPVT111222=Boyle’sLaw:PV=KCharlesLaw:V/T=KRootMeanSquare:(R=8.3145J/K*mol,M=massofamoleofthegasinkg)RateofEffusion:APQuickReview3RhondaAlexanderRobertE.LeeHighSchool,Tyler,TXMolefraction;χ=molesAtotalmolesPA=PtotalχAPtotal=PA+PB+Pc+….AtomicTheory:(n=integer,h=Planck’sconstant=6.626x10-34J*s)Energyperphoton:(c=2.99979x108m/s)ν=deBroglie’sequation:Beer’sLaw:whereA=absorbance,a=wavelength-dependentabsorptivitycoefficient,b=pathlength,andc=analyteconcentration.∆E=−×−FHGIKJ−2178101822.J1n1nfinalinitialPrincipleQuantumNumber(n)hasintegralvalues1,2,3,......Theprinciplequantumnumberisrelatedtosizeoftheelectroncloud,n=1,2,3,...determinestheenergyofthee–.AngularMomentumQuantumNumber(l)hasintegralvalues{0ton-1}.Thisquantumnumbergivesustheshapeoftheprobabilitypatternandeachshapeisreferredtoasasublevell={0to(n–1)}thetypeoforbital(subshell)0═s,1═p,2═d,3═fMagneticQuantumNumber(ml)hasintegralvalues{-lto+l}.TheMagneticquantumnumberreferstotheorientationofeachsublevel.morml={–lto+l}whichorientationoftheorbital(x,y,z…forporbitals)MagneticSpinQuantumNumber(ms)differentiatesthetwoelectronsthatcanexistinanorbitalandhasthevalueof+1/2and-1/2.sorms=+½or-½the“spin”oftheelectronDiamagnetic=paired–eParamagnetic=unpaired–eDalton-AtomicTheory,Thomson-cathoderayexperiment/electronandproton,Rutherford’s-goldleaf/nucleus,Bohr-energylevels,Schrodinger-quantumtheory(Heisenberg’s-uncertaintyprincipleanddeBroglie-dualnature)Millikan-chargeofelectron,Chadwick-neutron,Mosley-atomicnumber,Pauli’s-exclusionprinciple,Mendeleev-periodictableAPQuickReview4RhondaAlexanderRobertE.LeeHighSchool,Tyler,TXElectronAffinityExceptionsWHY?-Xs2<0:diamagneticatomwithallpairedelectrons.Electron-electronrepulsion.Xp3<0:atomwith3unpairedp-orbitalelectronseachoccupyingitsownsubshell.Thefourthelectronwillbethesecondelectroninanorbitalandwillexperienceelectron-electronrepulsion.Xp6<0:nextelectroninenergylevelfurtherfromnucleus-Statingthetrendisnotanexplanation:easeofremoving–e:f>d>p>sbecauseofpenetration-se-spendsagreaterpercentoftimeclosertonucleusthanpandpmorethand↑norradiusofatom↓Zeff,↑Zsamen↑Zeff,↑shielding↓Zeff(shieldingisonlyafactorwhencomparing–efromdifferentn’s)IonizationenergyExceptions1)Xs2>Xp1e.g.4Be>5BWHY?-.(sshieldsp∴p<Zeffthans)(s–espendsmoretimeclosertonucleusthan–einp)Therefore,itrequireslessenergytoremovethefirstelectroninaporbitalthanitistoremoveonefromafilledsorbital.Or:TheenergyofanelectroninanXporbitalisgreaterthantheenergyofanelectroninitsrespectiveXsorbital.Therefore,itrequireslessenergytoremovethefirstelectroninaporbitalthanitistoremoveonefromafilledsorbital.2)Xp3>Xp4e.g.7N>8OWHY?-Aftertheseparatedegenerateorbitalshavebeenfilledwithsingleelectrons,thefourthelectronmustbepaired.Theelectron-electronrepulsionmakesiteasiertoremovetheoutermost,pairedelectron.Subsequentionizationenergiesincreasegreatlyonceanionhasreachedthestatelikethatofanoblegas(whatnotwhy!!).Whyis--.Fewercoreelectrons,closertonucleus,greaterZeffÆTakesmoreenergytoremove.APQuickReview5RhondaAlexanderRobertE.LeeHighSchool,Tyler,TXBonding:knowthedifferencebetweenstructuralpairgeometryandmoleculargeometryAPQuickReview6RhondaAlexanderRobertE.LeeHighSchool,Tyler,TXHybribsexplainswhybondsinmoleculeswithdifferentatomicorbitalsbehaveasidenticalbondsie.CH4Resonancesexplainswhybondsinmoleculeswithacombinationofsingle,doubleortriplebondsbehaveidenticalie.C6H60Æ0.4NONpolarcovalent0.41Æ1.67POLARcovalentabove1.67—IONICCalculatinglatticeenergy(kisproportionalityconstant,Qischargeofions,r=shortestdistancebetweencentersofthecationsandanions)strengthofionicbond∆Hrxn=∑bondenergyofreactants-∑bondenergyofproductsbondbrokenbondsformedBondOrder:#ofsharedpairslinkingX&Y÷#ofX-YlinksFormalCharge:notonAPtest#valence–e−lonepairs+½shared–eIntermolecularForces:TYPEOFINTERACTIONCHARACTERISTICSOFINTERACTIONTYPEOFSUBSTANCEMAGNITUDERANGEKJ/MOLEDIPOLE-DIPOLEPositiveendofapermanentdipolealignsitselfwithnegativeendofapermanentdipoleonanothermolecule.{dipolemoment}TWOPOLARMOLECULAE5-25HYDROGENBONDSpecialtypeofdipole-dipole.Isstrongduetothelackofshieldingaroundahydrogennucleus(whenhydrogenisbondedtoahighlyelectronegativeatom.){dipolemoment}TWOPOLARMOLECULESWITHHYDROGENBONDEDTOAN,F,OROATOM5-25INDUCEDDIPOLE-INDUCEDDIPOLE(LONDONDISPERSION)Attractiveforcesbetweenmoleculesresultingfrommomentarymutualdistortion(induceddipole)ofelectronclouds.(temporarydipoles)Increaseinstrengthwithincreasemolecularweight(electroncloudsize)calledpolarizability.{induceddipole,-induceddipole}TWONONPOLARMOLECULES0.05-40Metallicbond:delocalized–eIonic:transferof–eNonpolarCovalent:equalsharingof–ePolarCovalent:unequalsharingof–eσoverlaps/s,s/p,p/p-πoverlapp/psingleσ,doubleσ-π,tripleσ-π-πsingle<double<triple:strengthsingle>double>triple>:lengthResonanceoccurswhenyouhaveacombinationofamultipleandsingleAPQuickReview7RhondaAlexanderRobertE.LeeHighSchool,Tyler,TXMETALNONMETALTYPESOFSOLIDSBOTHMETALLICIONICMOLECULARNETWORKTYPEOFSOLIDTYPEOFATOMSINFORMULAATOMS+&-IONSPOLARMOLECULESNONPOLARMOLECULESATOMSTYPEOFPARTICLEFORMINGCRYSTALSTRUCTUREHNOTBONDEDTON,O,ORFHBONDEDTON,OORFMETALLICBONDIONICBONDDIPOLEDIPOLEHBONDLONDONCOVALENTTYPEOFFORCEBETWEENPARTICLESFORMINGCRYSTALSTRUCTURECONDUCTORHIGHM.P.MALLEABLEDUCTILELUSTERSOLIDNON-CONDUCTORAQUEOUSCONDUCTORBRITTLEHIGHM.P.NON-CONDUCTORVARIABLEM.P.&B.P.NON-CONDUCTORHARDHIGHM.P.PROPERTIESAPQuickReview8RhondaAlexanderRobertE.LeeHighSchool,Tyler,TXSolutions:Molality:Psoln:vaporpressureofthesolutionXsolvent:molefractionofsolventPsolvent:vaporpressureofpuresolventRaoult’sLawPsoln=χsolventPsolventMassPercent:Osmoticpressureformulaforelectrolytesπ:osmoticpressureM:molarityR:0.0821L*atm/K*molπ═iMRTHenry’sLawP:partialpressureofgaseoussoluteC:concentrationofdissolvedgask:constantP=kCBoilingpointelevationm:molalityKb:constant∆Tb=iKb⋅mFreezingPointDepressionm:molalityKf:constant∆Tf=iKf⋅mvan’tHofffactorChemicalKinetics:FACTORAFFECTONRATECOLLISIONTHEORYCONCENTRATIONOFREACTANTSincreasingconcentrationincreasesrate(onlyreactantsintheratedeterminingstepaffecttherate)moremoleculesmorecollisionsTEMPERATUREincreasingtemperatureincreasesrate(approximatelyevery10oCincreaseintemperaturedoublesrate)moleculeshavemorekineticenergy~collidemoreoftenandharder~collisionsmorefrequentandagreater%ofthecollisionsareeffectiveCATALYST:increasetherateofareactionbutnotconsumedduringthereactionlowerstheactivationenergythereforeagreater%ofcollisionsareeffectiveSURFACEAREAOFREACTANTSincreasesurfaceareaincreasesratemorecollisionsaAbBdDBCCmnp+→rate=kAInstantaneousrate=slopeoflinetangenttothecurvem+n+p=orderofreactionk=rateconstantCiscatalystAPQuickReview9RhondaAlexanderRobertE.LeeHighSchool,Tyler,TXGeneralRateLawrateand[],Integratedratelawtimeand[]Orderin[A]RateLawIntegratedFormy=mx+bStraightLinePlotHalf-Lifet1/2zerothorder(n=0)rate=k[A]o=k[A]t=-kt+[A]o[A]tvst(slope=-k)t1/2=[A]02kfirstorder(n=1)rate=k[A]1ln[A]t=-kt+ln[A]oln[A]tvst(slope=-k)t1/2=ln2k=0.693ksecondorder(n=2)rate=k[A]21[A]t=kt+1[A]01[A]0vst(slope=k)t1/2=1k[A]0ArrheniusEquationthewholee^(stuff)equationrepresentsthefractionofcollisionswithsufficientenergytoproducearxnDerivedArrheniusEquationlnlnk=−FHGIKJ+ER1TAabgy=mx+b[graphicalmethod]lnkkER1T1T21a12FHGIKJ=−FHGIKJ[pluginequation]APQuickReview10RhondaAlexanderRobertE.LeeHighSchool,Tyler,TXChemicalEquilibrium:CalculatingEquilibriumConstant:(leaveoutsolidsandliquids)∆n=coefficientsofgaseousproducts-coefficientsgaseousreactantsKp=Kc(RT)∆nChangingtheCoefficientsWillChangeK:•Multiplyingcoefficientsbya#,Knew=Kold#•Reversingtheequation,Knew=1/Kold•AddingseveralequationstogetanetequationKnew=(Kold)(Kold)…AcidsandBases:pH=-log[H3O+]pOH=-log[OH-]Kw=1X10-14=[H3O+][OH-]14=pH+pOH[H3O+]=10-(pH)[OH-]=10-(pOH)EquilibriumExpressions:HA+H2OÅÆH3O++A-KHOAHAa3=+−<1B+H2OÅÆHB++OH-KOHHBBb-=+<1CB’s(anionsofweakacids)-reactlikenonhydroxidebasesinwater:NaF:F-+H2OÅÆHF+OH-CA’s(cationsofweakbases)-reactlikeacidsinwater:NH4Cl:NH4++H2OÅÆH3O++NH3Kw=[OH-][H+]=10-14@25°CKw=Ka⋅KbpKw=14%DissociationAPQuickReview11RhondaAlexanderRobertE.LeeHighSchool,Tyler,TXpH=pKaat½equivalencepointSolubilityEquilibrium:Qsp<Ksp-Thismeanstherearenotenoughionsinthesolution.Inordertoreturntoequilibrium,moreofthesolidsaltmustdissociateintoitsions.Qsp=Ksp-Thismeansthatthesystemisatequilibrium.Qsp>Ksp-Thismeansthattherearetoomanyionsinthesolution.Inordertoreturntoequilibrium,theexcessionswillprecipitatetoformmoresolid.Therrmochemistry:standardconditions1atmand25OcC=heatcapacityCp=tq∆orCp=mtq×∆Cpalsocalledspecificheatm=massofsolutionortotalmass∆H=qcoffeecupcalorimetryq=mc∆Tq=(m)×(∆Hfusor∆Hvap)APQuickReview12RhondaAlexanderRobertE.LeeHighSchool,Tyler,TX∆Hfoforelement=0∆Ho═∑n∆Hof(products)−∑n∆Hof(reactants)∆So═∑n∆So(products)−∑n∆So(reactants)∆Go═∑n∆Gof(products)−∑n∆Gof(reactants)∆Go═∆Ho−T∆So-∆Go=rxnspontaneous∆G=0atequilibriumDependenceOfSpontaneityOnTemperature∆S∆HCASERESULTSPOSITIVE,NEGATIVESPONTANEOUSALLTEMPERATURESPOSITIVE,POSITIVESPONTANEOUSHIGHTEMPERATURESNEGATIVE,NEGATIVESPONTANEOUSLOWTEMPERATURESNEGATIVE,POSITIVENOTSPONTANEOUSREACTIONSTATEEQUILIBRIUMCONSTANT“K”GIBBSFREEENERGY“∆G”CELLPOTENTIAL“∆E”SPONTANEOUSgreaterthanonenegativepositiveEQUILIBRIUMzeroZeroZeroNON-SPONTANEOUSLessthanonepositivenegativeElectrochemistry:LEOgoesGERloseelectronsoxidizegainelectronsreductionthereactantreducedistheoxidizingagentandvisaversaEocell=Eoox+EoredLargestEoredisreduced!bestoxidizingagentEcellis:+sponrxn,–nonsponrxn,0rxnateqAPQuickReview13RhondaAlexanderRobertE.LeeHighSchool,Tyler,TXAnodeCathode•Oxidation•AnionstoitfromSB•-involtaiccells•+inelectrolyticcells•Electronsflowawayfromit•CellnotationCl-/Cl2•Reduction•CationsflowtoitfromSB•+involtaiccells•-inelectrolyticcells•Electronsflowtowardsit•CellnotationCu2+ÆCu(s)ElectrochemicalCell:VoltaiccellStandardconditions1atm25oC∆Go=-nFEon=numberofmolesofelectronstransferredNernstEquationF=faraday’sconstantn=numberofelectronsE=ERTnFEcellcell0cell0−=−ln.logQnQ00592at25°Clog.Kn=E000592ElectrolysisElectrolysisinvolvesforcingacurrentthroughacelltoproduceachemicalchangeforwhichthecellpotentialisnegative~electricalworkcausesanotherwisenon-spontaneouschemicalreactiontooccur.Ifmorethanonereactantisavailableforreduction,theonewiththehighestEoredpotentialismostlikelytobereduced.Metalionsorwatercanbereduced.Whenelectrolysisoccursinaqueoussolutions,ifthemetalhasareductionpotentialsmallerthan-0.8,thenonlywaterisreducedbecausewaterhasthelargerEored.Negativeionswillbeoxidized.Iftherearemixturesofmetalions,themetalswillbereducedinorderoflargestEoredtosmallestEored.AtequilibriumEcell═0APQuickReview14RhondaAlexanderRobertE.LeeHighSchool,Tyler,TXFaraday'sConstant-Thechargeonamoleofelectrons:F=96,500Ccoulomb=(amp)(sec)ORGANIC—carboncontainingcompounds•–ane—CnH2n+2;hasallsinglebondsandisthereforesaturatedwithhydrogens•–ene--CnH2n;hasdoublebondsandisthereforeunsaturated[dieneshave2doublebonds,trieneshave3,etc.;botharepolyunsaturated]•–yne--CnH2n–2;haveatriplebondandarealsounsaturated•ISOMERS—samestructuralformulayetdifferentarrangementofatoms—canchangephysicalproperties;•Alcoholshave–OH—hydroxyl;notabase!!!!!!!!!ƒlargeIMF’sduetoH-bonding;increasesBP,lowersVP,etc.ƒIncreasessolubility•–COOH—carboxylicacidgroup;weakorganicacidsAlkaneAldehydeAlkeneKetoneAlkyneCarboxylicAcidAlcoholEsterEtherAmineAPQuickReview15RhondaAlexanderRobertE.LeeHighSchool,Tyler,TXFlameTestColors:Cugreen,Li&Sr&red,Nayellow,Bayellowgreen,KvioletpinkColorsofstuff:Cr2O72-orange,CrO42-yellow,MnO4-purple,Cr3+Cu2+,Ni2+,greenorblue,PbI2yellow,HFetchesglass,NH3fertilizer,NaN3airbags,ZnaddedtoFepreventrusting,Gases:O2iscolorlessandsustainscombustion,H2iscolorlessandexplodes!,Cl2isgreen,Br2isorange-brown;NO2isbrown;IodinesublimesintoapurplevaporPROCESSCHANGEINACHANGEINZCHANGEINNEUTRON/PROTONRATIOALPHAEMISSION-4-2INCREASEBETAEMISSION01DECREASEGAMMA00XPOSITRONEMISSION0-1INCREASEELECTRONCAPTURE0-1INCREASEALPHABETAGAMMAPOSITRONELECTRONCAPTUREheliumnucleusfastmovingelectronhighenergyelectromagneticradiationantiparticleofanelectroninnerorbitalelectron2protons&2neutronselectron’smassVerysmallnomasselectron’smasselectron’smass+2charge-1chargenocharge+1charge-1chargeα,4He2β,0e-10γ00e10e-1DonottravelfarNotpenetratingMorepenetratingthanalphaVerydangerousGammaraysareproducedCommonwithheavynuclidesNuclideswithtoomanyneutronsAccompaniesotherformsofradiationNuclideswithtoofewneutronsNuclideswithtoofewneutronsA=-4Z=-2A=0Z=+1NoneA=0Z=-1A=0Z=-1TestTakingTipsMultipleChoice:•Donotspendtoomuchtimeondifficultquestions.•Gothroughentiretestandansweralltheeasyquestionsfirst.•Whenyoucometoaquestionthatyoucananswerbutitwilltakeconsiderabletime,markthequestionandcomebacktoitafteryouhavegonethroughtheentiretest.•Youarepenalizedforwronganswerssodonotrandomlyguess.•Youcanmarkinyourtestbookletsoeliminationworkswell.Ifyoucaneliminateseveralchoicesyoumaywanttoguess.FreeResponse:•Questionsrequireyoutoapplyandexplainchemicalconceptsandsolvemultiplestepproblems.•Youdonothavetoanswerinessayformandmaysavetimeusingoneofthefollowingmethods:bulletformat,chartformatoroutlineformat.•Writeyouranswersinthespaceprovidedandnumberyouranswerclearly.•Thereisaslightpenaltyforincorrectsigfigs.