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GeneralChapterGeneralChapter4:ReactionsinAqueousInstructorDrO6S4C4Ar)LungWaCHUNG(鐘龍華)(Email:oscarchung@)DepartmentofChemistryAssignments&Assignments&Chapter1(Ch01):Duedate(27thSep.(Sun),10am)Chapter2(Ch02):Duedate(30thSep.(Wed),10am)Chapter3(Ch03):willbeready~thisweekendAdditionalexerciseforthosewhoareinterestedtodomore.(OPTIONALandNOTcountedtoyourgrade):Practice1&PracticeOurQQforumI(Announcement&LectureMaterials):OurQQforumII(Discussion):TAQ&ASessionTAQ&ASession&TAQ&ASession(optional,1Youaskcometoaskyourquestionsto~40-50studentperQ&Asession;Time:oneweekdaynight(1hour)Dateofthe1stSimpleQuiz(~20-30Option1(week4beforenationaldayOption2(week5afternationaldayholiday):Chapters1-4ReviewonChapterStoichiometry:ReviewonChapterStoichiometry:QuantityofSubstances;BalancedChemicalFormulasandEquationsChemicalEquations:LawofConservationofMass;Reactant∏States;Coefficients;SubscriptsReactionTypes:Combination,Decomposition&CombustionFormulaWeight;MolecularWeight;PercentMoles:Avogadro’sNumber;MolarMass;StoichiometricCalculations:LimitingReactants;Reagent;Theoretical/ActualOutlineofChapterOutlineofChapter(aqueous)Solution,Solvent,Dissociation:(Strong&Weak)Electrolyte;Precipitation:Solubility;Metathesis(Exchange)Reactions;Molecularand(Net)IonicEquationsAcid-Base:Arrhenius/Br?nstedAcids&Bases;Neutralization;Salt;Gas-formingReactionsOxidation-Reduction(Redox)Reaction:Oxidationnumbers;DisplacementReactions;ActivitySeriesConcentration:Molarity;Dilution;(learn(learnmorefromChapter13)Solutions(溶液?mixturesoftwoormorepuresubstances(one:Solutions(溶液?mixturesoftwoormorepuresubstances(one:liquidnormally).?Thesolvent(溶劑isingreatestquantity&actsasadissolvingmedium.Ifwateristhesolvent,→aqueoussolution.?Theother(smallestamountaresolutes(溶質(zhì))&dissolved(溶解)inthee.g.AsolutionofNaCl+Methanol+H2O(excess)H2O(l)H2O(l)+CO2(aq)+water+carbondioxide+calcium→calciumbicarbonate(orcalciumhydrogenEffectofSolventonSomeChemicalEffectofSolventonSomeChemical(ExtraEnergysurface(chapterSN2reaction(nucleophilic(BraumanScience2002,295,Anomalous異常orAnomalous異常orUnusualPropertiesofWater(ExtraInfo.)http://www1.lsbu.ac.uk/water/anmlies.html(somewerelistedaboAqu)eous/Physical_Chemistry/Physical_PropetiatinsIsthedensityofIsthedensityoficealwayslowerthanthatofH2Oicein1protonfor（氫D2Oicein1proton+1fordeuteriumD重氫MolecularDynamics分子動(dòng)力學(xué)MolecularDynamics分子動(dòng)力學(xué)(ExtraFreezingandMeltingofWater(IwaoOhmine,aformerstudentProf.MartinKarplus2013NobelWinner(卡普拉斯)Natureuos416,6879;Nature2013,498,?(解離Whenan?(解離Whenansubstance(e.g.NaCl,sodiumchloride)dissolves(溶解)insolvent(e.g.water),thesolventpullstheindividualionsfromthecrystal();thesolventsolvatesions(Na+(aq)andCl-?ThisprocessisElectrolytesand?AnelectrolyteisElectrolytesand?Anelectrolyteissubstancesdissociatesinto(Na+Cl-whenitisdissolvesinElectrolytesandElectrolytesandAnonelectrolyte(非電解maydissolveinwater,butitdoesNOTintoions?Soluble(可溶的)Soluble(可溶的)ioniccompounds(metalcations+nonmetalanions)tendtobeelectrolytes.Molecularcompounds(mostlynonmetals,e.g.CH3OH)tendtobenonelectrolytes,exceptforacids(e.g.HCl)andbases.K+(aq)K+(aq)andH2O(l)K+(aq)andCN-Na+(aq)andClO-4Na+(aq)andClO4-鈉離子Nasodium鉀離子Kpotassium高氯酸根離子ClO4-perchlorate氰離子CNcyanideElectrolytesConductivity(導(dǎo)電性ElectrolytesConductivity(導(dǎo)電性Astrongelectrolytedissociates(nearly)completelyintoionswhendissolvedinwater→agoodAweakelectrolyteonlydissociatespartially?dissolvedinwater→apoorCannotdetermineCannotdeterminefromFigureNa+(aq)+OH-strongelectrolytecompletelydissociatesintoCH3COO-(aq)+weakelectrolytepartiallydissociates:Strong???SolubleionicsaltsStrong???SolubleionicsaltsStrongacidsStrongbasesIonicsaltsarestrongelectrolytesifthedissolvedpartcompletelydissociatedinwatersilverAg+(aq)+Cl-StrongAcidsStrongAcids&TheaccompanyingdiagramrepresentsanaqueoussolutionofTheaccompanyingdiagramrepresentsanaqueoussolutionofeitherMgCl2,KCl,orK2SO4.Whichsolutiondoesthedrawingbestrepresent?ClassifytheseClassifythesedissolvedsubstancesasstrong,weak,ornonelectrolyte:CaCl2,HNO3,C2H5OH(ethanol),HCOOH(formicacid),KOH.Checkioniccompoundormolecular1.Ioniccompounds:CaCl2andKOH→strong2.Molecularcompounds:HNO3,HCOOHandC2H5OH2a.HNO3andHCOOHareacids.HNO3isastrongacid→strongelectrolyteHCOOHisweakacids→weakelectrolyte2b.C2H5OH,isneitheranacidnorabase→HCOOHformicacid(甲酸,蟻酸Precipitation(沉淀Precipitation(沉淀反Whenonemixesionsthatformcompoundsthatareinsoluble(不可溶的(couldbepredictedbythesolubilityguidelines),aprecipitate(沉淀物)inasolidformisformed.Interactionsbetweenthecationsandanionsaretoostrongtobeseparated(dissolved).Nitrate,acetate,chloride,bromide,iodide,Nitrate,acetate,chloride,bromide,iodide,sulfate,sulfide,carbonate,phosphate,hydroxideiodideionIBr-溴離子bromideionBrbromineCl-chlorideionCl氟離子fluorideion;FClassifytheseioniccompoundsassolubleorinsolubleinwater:(a)sodiumClassifytheseioniccompoundsassolubleorinsolubleinwater:(a)sodiumcarbonate,Na2CO3,(b)leadsulfate,(a)Mostcarbonatesareinsoluble,carbonatesofthealkalimetalcations(suchasNa+)areanexception:(b)Althoughmostsulfatesarewatersoluble,PbSRactionsWhenFe(NO3)2dissolvesinwater,theparticlesWhenFe(NO3)2dissolvesinwater,theparticlesinsolutionareFe+and(NO3)2-and2NO3-Feand2FeandN2and3WhichcompoundbelowisNOTsolubleinMetathesis(Exchange)復(fù)Metathesis(Exchange)復(fù)分解（交換）反應(yīng)Metathesis:fromaGreekwordthatmeans?AX+BY→AY+AgNO3(aq)+KCl(aq)Metathesis(Exchange)復(fù)Metathesis(Exchange)復(fù)分解（交換）反應(yīng)Metathesis:fromaGreekwordthat“totranspose(調(diào)換?Appearsasthoughtheionsinthecompoundsexchange,ortranspose,AgNO3(aq)+KCl(aq)AgCl(s)+SolutionItishelpfultopayattentiontoSolutionItishelpfultopayattentiontoexactlywhatspeciesarepresentinareactionmixture(i.e.,solid,liquid,gas,aqueoussolution).BaCl2(aq)+BaSO4(s)+2?Ifwearetounderstandreactivity,wemustbeofjustwhatischangingduringthecourseofaMolecularTheMolecularThemolecularequationliststhereactantsandproductsintheirmolecularform:AgNO3(aq)+KCl(aq)AgCl(s)+IonicIntheionicequation,IonicIntheionicequation,allstrongelectrolytes(strongacids,strongbases,andsolubleionicsalts)aredissociatedintotheirions(e.g.Na+(aq)andThismoreaccuratelyreflectsthespeciesthatarefoundinthereactionmixture:Ag+(aq)+NO3?(aq)+K+(aq)+Cl?(aq)AgCl(s)+K+(aq)+NO3?Ionswhichdonotinvolvethereactionarespectatorions(theyweredeletedfromtheneAqueous?ionicequation)e.g.NO3?(aq)&NetIonicEquation(凈NetIonicEquation(凈離子方程式Toformthenetionicequation,deleteanything(spectatorions)thatdoesnotchangefromboththeleftandrightsidesoftheequation:Ag+(aq)+NO3?(aq)+K+(aq)+Cl?(aq)AgCl(s)+K+(aq)+NO3?Theonlythingsleftintheequationareionsthatchange(i.e.,react)duringthecourseofthereaction:Ag+(aq)+Cl?(aq)AgCl(s)H+(aq)+OH?(aq)?Whichions,ifany,areWhichions,ifany,arespectatorionsintheBa(NO3)2(aq)+Na2SO4(aq)BaSO4(s)3-NO3-(aq)andSO42-(aq)Na+(aq)andNO3-(aq)NospectatorionsareWritingNetIonicWriteaWritingNetIonicWriteabalancedmolecularAgNO3(aq)+KCl(aq)AgCl(s)+Expressdissociationofallelectrolytesintoions(e.g.K+(aq),Cl-Ag+(aq)+NO3?(aq)+K+(aq)+Cl?(aq)AgCl(s)+K+(aq)+DeletespectatorionsfromboththeoftheAg+(aq)+Cl?(aq)AcidsAcids&(learnmorefromChapters16-17)?ArrheniusdefinedacidssubstancesthatincreasetheconcentrationofH+(aq?ArrheniusdefinedacidssubstancesthatincreasetheconcentrationofH+(aq)whendissolvedinwater(Arrheniusacid-?BothBr?nstedandLowrythemasprotondonors(質(zhì)子供體）(Br?nsted-Lowryacid-basetheory布朗斯特-勞里酸堿理論).H+:protonion;H:hydrogenH-:hydrideExtraInfo.:moregeneraldefinitionbyLewisacid-theory(intermsof“electron”,ChapterSevenstrongacids(completeionizationSevenstrongacids(completeionizationtogiveH+(aq),strongelectrolyte):HydrochloricAcid(HCl)HydrobromicAcid(HBr)HydroiodicAcid(HI)NitricAcid(HNO3)SulfuricAcid(H2SO4)ChloricAcidHClO3)（氯酸PerchloricAcidHClO4)（高氯酸H+(aq)+A-Weakacids(partialionizationtogiveH+(aq)):e.g.Aceticacid(CH3CO2H)H+(aq)+A-Monoproticacid(HA)&Diproticacid0120123?Arrheniusdefinedassubstancesthatincreasetheconcentrationof?ArrheniusdefinedassubstancesthatincreasetheconcentrationofOH?(aq)whendissolvedinwater.?Br?nstedanddefinedthemas（質(zhì)子受體Litmuspaper石蕊試紙ThestrongbasesareThestrongbasesarethesolublemetalhydroxide(MOH)withcompleteionization(dissociation):Metals(M):Alkalimetals（堿金屬）Calcium（鈣）Strontium（鍶）Barium（鋇H+(aq)+B-Weake.g.H+(aq)+B-isisnotbasicinwater.isinsolubleinisastrongacidinwater,notisaweakacidinwater,notAcid-BaseInanAcid-BaseInanacid–basereactiontheaciddonates(給aproton(H+)tothebase.~1partialNeutralizationReactionsNeutralizationReactions(中和反應(yīng)Generally,whensolutionsofanacidandabasearecombined,theproductsareasaltandwater:CH3COOH(aq)+NaOH(aq)CH3COONa(aq)+Whenastrongacidreactswithastrongbase,theWhenastrongacidreactswithastrongbase,thenetionicequationisHCl(aq)+NaOH(aq)NaCl(aq)+H+(aq)+Cl?(aq)+Na+(aq)+OH?(aq)Na+(aq)+Cl?(aq)+ +WhenanacidreactswithaWhenanacidreactswithabase,theresultadductWhichcompoundbelowisNOTastrongGas-Forming1.WhenaGas-Forming1.Whenacarbonate(CO32-)or(hydrogencarbonateHCO3-)reactswithanacid,theproductsareasalt,gaseouscarbondioxide,andwaterNaHCO3(aq)+HBr(aq)NaBr(aq)H2CO3(aq)NaBr(aq)+CO2(g)+CaCO3(s)+HCl(aq)CaCl2(aq)+CO2(g)+CalciumCarbonate2.Whenasulfite2.Whenasulfite(SO32-)reactswithanacid,theproductsareasalt,sulfurdioxide,andwater:SrSO3(s)+2HI(aq)SrI2(aq)+SO2(g)+Strontiumsulfite3.Whenasulfide(S2-)reactswithanacid,theproductsareasaltandbad-smellgas(H2S):Na2S(aq)+H2SO4(aq)Na2SO4(aq)+SulfuricacidHydrogensulfidesodiumsulfite亞硫酸鈉Sodiumsulfide硫化鈉Sodiumsulfate硫酸鈉sulfurdioxide二氧化硫Sulfiteionsodiumsulfite亞硫酸鈉Sodiumsulfide硫化鈉Sodiumsulfate硫酸鈉sulfurdioxide二氧化硫SulfiteionB.亞硫酸氫根SulfateionNa2SO3(aq)+SO32-(aq)+SO2(g)+NaCl(aq)+SO2(g)+Antacids(Antacids(抗酸劑ReactionsReactions(learnmorefromOxidation-(氧化-還原反應(yīng)?AnoxidationoccursOxidation-(氧化-還原反應(yīng)?Anoxidationoccurswhenanatomorion?Areductionoccurswhenanatomorion?OneCANNOToccurwithouttheOxidationNumbers(氧化數(shù)ForOxidationNumbers(氧化數(shù)Foranoxidation–reductionreaction,weassignanoxidationnumber(oxidationstate)toeachelementinaneutralcompoundorchargedentity.?Atoms(i.e.neutral)intheirelementalformhaveoxidationnumberofe.g.He,Li,H2,O2,N2,?Theoxidationnumberofamonatomicionissameasitscharge.+1:Li+,-1:F-,Cl-+2:Mg2+,-2:O2-,+3:?Nonmetals（非金屬）?Nonmetals（非金屬）tendtohavenegativenumbers,althoughsomearepositiveincertaincompoundsorions.e.g.Oxygenusuallyhasanoxidationnumberof?2(e.g.H2O)exceptperoxidecompounds:?1（H2O2）andunusually+2forOF2體助燃劑?1whenbondedtoametal(e.g.NaH,sodium+1whenbondedtoanonmetal(e.g.H2O,Fluorine（氟）alwayshasanoxidationnumberFluorine（氟）alwayshasanoxidationnumberof?1(e.g.HF)inallcompounds:thehighestTheotherhalogens（鹵素）haveanoxidationnumberof?1inmostbinarycompounds,buttheycanhavepositiveoxidationnumbersinoxyanions:e.g.(perchlorate):x+4*(-2)=-1?x=(chlorate):x+3*(-2)=-1?x=+7:-4+5:-3+3: (chlorite):x+2*(-2)=-1?x=-2+1:ClO-(hypochlorite):x+-2=-1?x=-1:HCl:1+x=0?x=-?Thesumoftheoxidationnumbersof?Thesumoftheoxidationnumbersofallatomsinneutralcompoundis0.e.g.H2Se:2*(+1)+x=0?x=-2?ThesumoftheoxidationnumbersofallatomsinpolyatomicionisthechargeontheSulfateion:x+4*(-2)=-2?x=+6Nitrateion:x+3*(-2)=-1?x=+5Carbonateion:x+3*(-2)=-2?x=+4-33(置換反應(yīng)(置換反應(yīng)A+BX→AX+Mg(s)+2HCl(aq)→MgCl2(aq)+The(H+)ioninsolutionisdisplaced/replacedoxidationofan(reactive)element?2012PearsonEducation,RedoxreactionsRedoxreactions(1)betweenmetalsandaswellasthose(2)betweenmetalsandSilverionsoxidizecoppermetal:Cu(s)+2Ag+(aq)Cu2+(aq)+2Ag(s)ThereverseThereverse(逆reactiondoesNOToccur:ActivitySeries(活性順序A+ActivitySeries(活性順序A+→+Anymetal(A)onthislistcanbeoxidizedbytheionsofelements(B)belowtheenergyExtraThereactivityExtraThereactivityseries:listofmetals(sometimeswithH&Caddedasbaseline)arrangedbytheabilitytoreduceotherchemicalsinnonspecificway.ReactivityK,*Na,*Ca,Mg,Al,Zn,Fe,Sn,Pb,Cu,Hg,Ag,←increasein*:thepositionofCa&Naaredifferentinelectro-chemicalseries,CaismoreelectropositivethanNa,butnotforthereactivityseries.ThisisincontractwiththeelectrochemicalListofreducingagentsarrangedbythewayofpotentialinanelectrochemicalExtraExtraNabeingaboveCaintheReactivityCabeingaboveNaintheElectrochemicalMetalswithlowervalenciestendtobehigherintheReactivitySeriesbecausetheyonlyneedtoloseoneelectrontoformastablenoblegasstructurewithafullouterelectronshell.ThereasonforthisbeingthatmetalswithhighervalenciestendtobehigherintheElectrochemicalSeries,becausemoreelectronsareneededtoproduceeachatom.Cu(s)+Cu(s)+Ag(s)+Zn(s)+Zn(s)+Ag(s)+Zn(s)+Zn(s)+Pb(s)+Z(O3)(aAueoLead（鉛Zn(s)+Zn(s)+H2(s)+Hydrochloricacid鹽酸xH2xH2(s)+Cu(s)+Whenanatomundergoesoxidation,it Whenanatomundergoesreduction,it Whenanatomundergoesoxidation,it Whenanatomundergoesreduction,it -------DeterminetheoxidationnumberDeterminetheoxidationnumberofsulfurin(a)(b)S8,(c)SCl2,(d)Na2SO3,(e) Whenbondedtoanonmetal(S),Hhasanoxidationnumberof+1?2*(+1)+x=0;x=-2S8isanelementalform?Chlorinetohaveanoxidationnumberof–1?x2*(-1)=0;x=Sodium(metal)hasanoxidationnumberof+1.Oxygenhasacommonoxidationstateof–2?2(+1)+x+3(–2)=0;x=(e)TheoxidationstateofOis–2?x+4(–2)=–2;xhydrogensulfide，sulphur，sulfurchloride，sodiumsulfite，sulfateionTheoxidationnumberofboronforthebelowTheoxidationnumberofboronforthebelow-0Al+→Al3++Whentheoxidation-reductionreactionaboveiscorrectlybalanced,thecoefficientsare1,2→1,1,3→1,2,3→2,2,6→2,(learn(learnmorefromChapter13)(摩爾濃度?Twosolutionscancontainthesame(摩爾濃度?Twosolutionscancontainthesamecompounds,butdifferentamountsorproportionsofthecompounds.Molarityisonewaytomeasuretheconcentrationofasolution(1M=1mol/1L):molesof?Molarity(M)volumeofsolutioninMoleMolecularSO42-(aq)+21MK2SO4(aq)=1MSO42-(aq)+2MK+MixingaMixingaTocreateasolutionofaknownmolarity,1.oneweightsoutaknownmassofthesolute?numberofmoles2.thesoluteisaddedtovolumetricflask(容量瓶3.solventisaddedtothelineontheneckoftheflaskDilution(稀釋diluteDilution(稀釋diluteamoreconcentratedsolution1usingapipettodeliveravolumeofsolutiontoanewvolumetricflask,2.addingsolventtothelineontheneckofthenew?2012PearsonEducation,Themolarityofthenewsolutionbydilutioncanbedeterminedasfollows(theThemolarityof