氫、堿金屬和堿土金屬課件

氫、堿金屬和堿土金屬

Hydrogen,AlkaliandAlkali-earthmetals氫、堿金屬和堿土金屬

Hydrogen,Alkali§1氫及其化合物（Hydrogenantitscompounds）

氫在周期表中排ⅠA，又能排ⅦA，這是由于第一周期的稀有氣體電了構(gòu)型為1s2

。一、單質(zhì)氫（Simplesubstanceofhydrogen）

1、氫的同位素（isotope）

(1)PP+nP+2nProtiumDeuteriumTritium

氕氘氚

§1氫及其化合物（Hydrogenantitscomp(2)存在：H:D=6800:1(原子個(gè)數(shù))H:T=1e10:1HeatCool(2)存在：H:D=6800:1(原子個(gè)數(shù))H:T=(4)氫同位素形成的單質(zhì)H2、D2、T2,在化學(xué)性質(zhì)上完全相同，但物理性質(zhì)（熔沸點(diǎn)）上有差別。2.Properties:(1)Physicalproperties:H2：極難溶于水和有機(jī)溶劑，可以貯存在金屬(Pt、Pd)和合金(LaNi5)中固態(tài)氫（黑色）又稱為金屬氫：在晶格質(zhì)點(diǎn)上為質(zhì)子，而電子為整個(gè)晶體享，所以這樣的晶體具有導(dǎo)電性，固態(tài)氫可能為立方或六方分子晶格。(4)氫同位素形成的單質(zhì)H2、D2、T2,在化學(xué)性質(zhì)上(2)Chemicalproperties:a.成鍵特點(diǎn)：電子構(gòu)型為1s，可以放在ⅠA類，但第一電離勢(shì)高于堿金屬的第一電離勢(shì)；也可放在

ⅦA類。

b.化合反應(yīng)：與金屬:2Na+H2=2NaHCa+H2=CaH2

與非金屬:H2+F2=2HFc.還原反應(yīng)：CuO+H2=Cu+H2OWO3+3H2=W+3H2O(2)Chemicalproperties:

3.Preparation(1)實(shí)驗(yàn)室：

(2)工業(yè)上：二、氫化物（Hydride）放在以后各章元素中講解http://www.chemsys.t.u-tokyo.ac.jp/laboratory_domen-kubota_e.htmlSi(s)+Ca(OH)2(s)+2NaOH(s)=Na2SiO3(s)+CaO(?)+2H2(g)3.Preparation二、氫化物（Hydride）放在§2堿金屬元素及其化合物

AlkalimetalsandtheircompoundsLithiumSodiumPotassiumLiNaKRubidiumCesiumFranciumRbCsFr§2堿金屬元素及其化合物forstructuralandmechanisticstudiesofionchannelsRoderickMacKinnon

TheNobelPrizeinChemistry2003PeterAgre,RoderickMacKinnonK+channelforstructuralandmechanistic氫、堿金屬和堿土金屬課件氫、堿金屬和堿土金屬課件氫、堿金屬和堿土金屬課件IwasbornonFebruary19,1956inthemiddleofasnowstorm.Itremainsoneofthosehumorousfamilystoriesthatmymotherlikestotell.Myfathertheplannerhadrehearsedthewaytothehospitalbutapparentlythingslookedalotdifferentatnightinablizzard.EventuallytheymadeitandsodidI,thefourthofsevenchildren.MyfatherwasapostalworkerwhenIwasveryyoungbutstudiedcomputersandbecameaprogrammeronthebigIBMmainframes.Mymotherworkedasaparttimeschoolteacher,butmostlytookcareofthechildrenathome.ThinkingbackonitnowIknowwedidnothavemuchmoneybutIneverknewthatgrowingup.Myparentsprovidedahappyenvironmentandmadetheirexpectationscleartous.Televisionisbadforyou,readingisgoodforyou,andyoubettergetanAforeffortinschool.Whatyouendupdoinginlifeisuptoyou.Justmakesureyouenjoywhatyoudobecausethenyouwilldoitwell.Weallpursuedcompletelydifferentwalksoflife.Ibecamethescientist.Isupposethereweresomeearlyindicationsofmytendencytoalifeofcuriosity.ApparentlyfromaveryyoungageIhadahabitofaskinglotsofquestions:'whatwouldhappenif.?'wasafavorite.AndIlikedhavingfactsstraightandknowinghowthingsworkanddidnothesitatetogiveexplanationstothosearoundme,apparentlytoanannoyingdegreesometimes.Irememberonedaymyfather,attheendofhispatience,commentingthatIwasa'compendiumofuselessinformation'.Icertainlycanunderstandhisplightwithoneofthesevenhavingwaytoomanyquestionsandanswersallthetime.Onthepositiveside,IlearnedanewwordthatdaywhenIlookedupcompendiuminthedictionary.Therewereprobablyevenindicationsthatmycuriositymightbescientific.BurlingtonMassachusettswasruralwhenIwasyoungandIlovedtoroamandexplore.Ihadrockcollectionsandreadchildren'sbooksongeologyandthehistoryoftheearth.Imadelittlevolcanoesoutofplasterofparisandaddedbakingsodaandvinegartothecraterstosimulatevolcaniceruptions.Ihadanaccidentonedaythatmademymotherlaughtomyutterfrustration:atthatyoungageIfailedtoappreciatethehumorinalittleboytellinghismotherhehaddroppedavolcanoonhistoe!InthesummerIcollectedbutterflies,turtles,snakesandotherlivingthings.OnesummermymotherenrolledmeinascienceenrichmentclassforelementaryschoolstudentsandIwasallowedtotakehomeamicroscope.IusedittolookateverythingIcouldfind:microorganismsfromthenearbypond,leavesandbladesofgrass.Ispenthourafterhouralone,mesmerizedbythetinylittlethingsthatIcouldsee.IwasbornonFebruary19,195Myscientificcuriositytookabackseattoathleticsthroughjuniorhighandhighschool.Gymnasticswasagoodmatchtomysmallbuildandtomysolitarynature.Iwasamemberofateambutgymnasticsisanindividualsport.Youlearnatechnique,thena'move',andthena'routine'.Andthenyouperfectitthroughpractice,workingmostlyalone.Ihadaverygoodnononsenseteacher,coachHayes,whoreallyinstilledinmetheideaofperfectionthroughpractice.Iwasactuallynotallthatbad,particularlyatfloorexerciseandhighbar.Ievenconsideredpursuinggymnasticsincollege,butduringmyfinalyearofhighschoolIbegantowonderwhatIshouldpursueforacareer.IattendedtheUniversityofMassachusettsinBostonforoneyearandthentransferredtoBrandeisUniversity.Brandeiswasaneyeopeningexperienceforme.ForthefirsttimeinmylifeIwasinaseriouslyintellectualenvironment.Theclassestendedtobesmall,intense,andstimulating.IdiscoveredthatIhadapassionforscience,andthatIwasverygoodatit.IchoseBiochemistryasamajorandanewlyarrivedassistantprofessornamedChrisMillerformyhonorsthesisadvisor.Hehadalittlelaboratorywithbigwindowsandlotsoflightshiningin.Istudiedcalciumtransportandlearnedaboutthecellmembraneasanelectrode.IcouldseethatChrisMillerwasamanhavinglotsoffuninhisdailylifeanditwasinspiringtome,andthememoryofthisstayedwithme.ButthebiggestinfluenceBrandeishadonmylifehappenedinPhysicsclass.ThereImetmyfuturewifeAliceLee,whosesparklingeyesandsharpmindcaughtmyattention.AgainstChrisMiller'sadviceIwenttomedicalschoolafterBrandeis.IstudiedatTuftsUniversitySchoolofMedicineandthenatBethIsraelHospitalBostonforhouseofficertraininginInternalMedicine.IlearnedalotbutintheendIshouldhavetakenChris'advicetopursuescience.Medicinerequiredalotofmemorizationandlittleanalyticalproblemsolving.TokeepacertainpartofmybrainactiveIbegantostudymathematics,andcontinuethiseventoday,learningnewmethodsandsolvingproblemswiththesamedisciplinedapproachIhadlearnedingymnastics.IstartedbacktoscienceneartheendofhouseofficertrainingworkingwithJimMorganstudyingcalciumincardiacmusclecontractility,whichwasveryenjoyableandkeptmeconnectedtomedicine.ButIhadayearningtoworkonaverybasicscienceproblem,whichmeantIwouldhavetobreakmymedicalties.ThiswasadifficultdecisionbecauseIhadinvestedsomanyyearsinmedicaleducation;toabandonitwastoadmittomyselfthatIhadmisspentabigpieceofmylife.Andtherewerepracticalconsiderationsaswell.Itwastimefinallytogetapermanentjob;afterall,mywifeAlicehadsupportedmethroughyearsoftraining.NottomentionIwasnearly30yearsoldwithnorealbasicsciencetrainingbeyondmyBrandeisundergraduateeducation:wouldIevenbeabletomakeitasascientist?MyscientificcuriositytookaTwofactorshadthegreatestinfluenceonmydecision.BackinmyfirstyearofmedicalschoolIlostmysisterElley,anartistonlytwoyearsmysenior.DiagnosedwithleukemiaduringmyhematologyclerkshipasIlearnedaboutthedreadeddisease,shelastedonlytwomonths.Thishorrifyingeventimpresseduponmehowfragileandpreciouslifeis,andhowimportantitistoseizethemomentandenjoywhatyoudowhileyoucan.IrememberthinkingwhenIlookbackuponmylifeattheageofseventy,thirtywillseemyoung:justgoforit.AndthesecondfactorwasAlice.Shehadcompletefaithinmyabilitytosucceed.Nevermindthatpostdoctoralstudiesmeantareductionofmyalreadypiddlinghouseofficersalary.Shesimplysaidyouhavenochoice;wewillmanagesomehow.MemoriesofChrisMiller'slaboratorybeckonedsoIreturnedforpostdoctoralstudies.OfcourseIwillneveroutlivehisremindingmethatIshouldhavelistenedtohiminthefirstplace.FeelingfarbehindinmyknowledgeIapproachedmypostdoctoralstudieswithintensity,learningtechniquesandtheory.IfeltIshouldbeanexpertinelectrochemistry,stochasticprocesses,linearsystemstheory,andmanymoresubjects.Ireadbooks,solvedtheproblemsets,masteredthesubjects,andcarriedoutexperiments.IhadtheverygoodfortuneofacoworkerJacquesNeyton,apostdoctoralscientistfromFrance.Jacquesisaverycriticalthinkerwhowouldbroodonaproblem.Weexchangedideasoften.WhenIwouldtellhimoneofmyideashehadatendencyjusttolistenquietly.Then,afterawhile,ifhisresponsestartedwith'HeyRoddy,there'ssomethingIdon'tunderstand'IknewIwasintrouble-myideawasprobablynogood!AfterIcompletedaseriesofbiophysicalstudiesonK+channelsitcametimetoapplyforanacademicposition.Duringthelate1980sphysiologydepartmentsweremoreinterestedinhiringchannelgeneclonersthanbio-physicists.ButPeterHessconvincedhiscolleaguesatHarvardthatmyworkshowedpromiseandIwasofferedanassistantprofessorshipthere.MylaboratorymadegoodprogressonK+channels.ItwasexcitingforawhilebutinjustafewyearsIbegantofeelthatthereturnonwhatwecouldlearnfromstudyingthefunctionaleffectsofmutationswasdiminishing.WehadidentifiedtheK+channelsignaturesequence,butwithoutknowingitsstructureweneverwouldunderstandthechemicalprinciplesofionselectivityinK+channels.IdecidedatthatpointtolearnX-raycrystallographytosomedayseeaK+channel.TwofactorshadthegreatestiIbegantolearnmethodsofproteinpurificationandX-raycrystallographywhilestillatHarvard,initiallyworkingwithchanneltoxinsandasmallsolubleproteincalledaPDZdomain.However,IthoughtitbesttomoveawayfrommyfamiliarenvironmentatHarvardtopursuechannelstructure.Therewerereallytworeasonsmotivatingmetomove.FirstwasthepracticalissueofobtainingfundingtoworkinanareainwhichIhadnobackground:start-upfundsassociatedwithmovingtoanewuniversitywouldbeusefulforthispurpose.Thesecondandfarmoreimportantreasonwasthatmovingwouldenablemetoimmersemyselfcompletelyinthenewendeavor.Achangeofenvironmentwouldremovethedistractionsofeverydaylife,isolatemefromthetemptationtofallbackonchannelphysiologystudiesthatIwasalreadygoodat,andallowmetofocuswithsingularpurposeonthestructuralstudies.IneededthistobecomeanexpertinmembraneproteinbiochemistryandX-raycrystallography,andtodevelopa'feel'forproteinstructure.WhenthepresidentofRockefellerUniversityTorstenWieselheardaboutmyscientificplanshesuggestedthatImovetoRockefellerUniversityandIdid.Rockefellerprovidedawonderfulenvironmentforconcentratingonadifficultproblem.IthasbeensaidthatgivingupmyalreadysuccessfullabatHarvardinordertopursuethestructureofaK+channelwasariskythingtodo.AtthetimeIwastoldthatmyaspirationswerealtogetherunrealistic.FrommyperspectiveIhadlittlechoicebecauseIwantedtounderstandK+selectivityandIknewthattheatomicstructureprovidedtheonlypathtounderstanding.Iwouldratherfailtryingthannevertryatall.IthelpedthatIwasaccustomedtomakingtransitionsandhadbecomegoodatteachingmyselfnewsubjects.Ihavetoadmitthatfewpeopleworkingwithmeatthetimewantedmuchtodowiththenewendeavor-onlyonenewpostdoctoralscientistDeclanDoylewasenthusiastic.MywifeAlice,anorganicchemist,sawthatIwasgoingtobeprettylonelyanddecidedtojoinmeinthelab.Andtomygoodfortuneshehasworkedwithmesince.IhavelearnedthatmostpeopledonotlikechangebutIdo.Formechangeischallenging,goodforcreativity,anditdefinitelykeepslifeinteresting.IbegantolearnmethodsofprIthinkofthepasteightyearsofmylifeinNewYorkatRockefellerUniversityasapersonalodyssey.Thenewlaboratorystartedoutverysmall,withonlyDeclan,Aliceandme.Butitgrewinthefirstyearwiththeadditionofotherenthusiasticpostdoctoralscientists,includingJo?oMoraisCabralandJohnImredy.Workingwithmembraneproteinswasverydifficultasexpected.Wehadourperiodsofdespair,buteverytimewefeltleftwithoutoptionssomethinggoodhappenedanddespairgavewaytoexcitement.Persistenceanddedicationeventuallypaidoff.TheatomicstructureoftheK+selectivityfilterwasmoreinformativeandmorebeautifulthanIevercouldhaveimagined.Mylaboratorynowisanincredibleplace,overflowingwithexcitementandideassustainedbythecontinualinfusionofbrightyoungscientistswhocomefromaroundtheworldtoworkwithme.Itgivesmegreatsatisfactiontoknowthattheseyoungscientistswhoaresophisticatedintheirknowledgeofproteinchemistryandstructurewillleadthefieldofionchannelresearchintothefuture.Thishasbeenawonderfuladventure.IowethanksforthelifeIhave:toAlice,toallmylovingfamilyofMacKinnonsandLees,tomyscientificfamilyofstudents,postdocsandcolleagues,toseniorcolleagueswhohavehelpedmealongmywaytopursuemypassion,andtotheRockefellerUniversity,theHowardHughesMedicalInstitute,andtheNationalInstitutesofHealthfortheirsupport.Iamverythankfulformylifeasascientist,fortheopportunitytounderstandinsomesmallwaytheworldaroundme.Ihopemybestexperimentandscientificideasareyettocome.Thishopekeepsmegoing./nobel_prizes/chemistry/laureates/2003/mackinnon.htmlIthinkofthepasteightyear

一、Generalproperties1.Valenceelectronofalkalimetals:(1)其氧化數(shù)為+1，不會(huì)有其它正氧化態(tài)。在無(wú)水無(wú)氧條件下，可以制得低氧化態(tài)的非尋常化合物。例如鈉在乙二胺和甲胺中所形成的溶液也具有導(dǎo)電性，觀察到Na-的光譜帶，說(shuō)明主要的導(dǎo)電體應(yīng)是鈉電離出的Na+

和Na-。cryptand-222

一、Generalpropertiescryptand-Inversesodiumhydride+?H2Inversesodiumhydride+?H2(2)由于價(jià)電子數(shù)少，所以堿金屬原子之間的作用力比絕大多數(shù)其他金屬原子之間的作用力要小，因此堿金屬很軟，低熔沸點(diǎn)，且半徑大、密度小。

Li的密度是所有金屬中最小的，它的密度比煤油小。(2)由于價(jià)電子數(shù)少，所以堿金屬原2.在形成化合物時(shí)，堿金屬元素以離子鍵結(jié)合為特征，但也呈現(xiàn)一定程度的共價(jià)性。

(1)氣態(tài)雙原子分子Na2

、Cs2以共價(jià)鍵結(jié)合

(2)Li的一些化合物共價(jià)成份最大，從LiCs的化合物，共價(jià)傾向減小。

2.在形成化合物時(shí)，堿金屬元素以離子鍵(3)某些堿金屬的有機(jī)物，有共價(jià)特征。例如Li4(CH3)4甲基鋰(3)某些堿金屬的有機(jī)物，有共價(jià)特征。氫、堿金屬和堿土金屬課件二、Lithiumanditscompounds1.Generalproperties:Li的性質(zhì)與堿金屬有很大區(qū)別，但與堿土金屬，特別是Mg的化學(xué)性質(zhì)相似，這種關(guān)系稱為對(duì)角線關(guān)系（diagonalrelationship）。

Li與堿金屬元素（Na、K、Rb、Cs）的區(qū)別：

(1)鋰的硬度比其它堿金屬都大，但與堿土金屬相似。

(2)鋰形成正常氧化物，而不形成過(guò)氧、超氧化合物。

(3)鋰與氮?dú)庑纬傻?，其他堿金屬不能與N2直接化合，而堿土金屬與N2能直接化合。

(4)只有鋰與碳反應(yīng)生成Li2C2（乙炔鋰），堿土金屬都能形成MC2。

(5)三種鋰鹽（Li2CO3、Li3PO4和LiF）溶解度小，堿土金屬這三種鹽的溶解度也小。二、Lithiumanditscompounds二、Lithiumanditscompounds1.Generalproperties:6.鋰的有機(jī)金屬化合物與鎂的有機(jī)金屬化合物相似7.許多鋰的鹽有高度的共價(jià)性，與鎂相似。8.鋰的氫氧化物、碳酸鹽加熱（與Mg相似）分解成氧化物和水或二氧化碳；其他堿金屬的氫氧化物、碳酸鹽加熱難分解；而氫化鋰加熱不分解，氫化鈉加熱分解成氫氣和氣態(tài)Na2

C2H5MgBr二、LithiumanditscompoundsC2H2.Thesimplesubstance(1)Lithiumisasoft,silverywhitemetal,thelightestofallmetals(2)preparation:電解LiCl(55%)—KCl(45%)(3)與非金屬反應(yīng).加熱時(shí)，它直接與S,C,H2反應(yīng)

(4)在空氣中被氧化，生成Li2O和Li3N；在CO2中加強(qiáng)熱，可以燃燒

(5)與金屬反應(yīng)，生成金屬互化物2.Thesimplesubstance氫、堿金屬和堿土金屬課件(6)與H2O,H+劇烈反應(yīng)，但在水中反應(yīng)會(huì)減慢，由于LiOH溶解度小

(7)它是Tritium的來(lái)源3.化合物

(1)Li的二元化合物的化學(xué)性質(zhì)、溶解度和水解性與相應(yīng)的Ca、Mg化合物相似

(2)LiF,Li2CO3,Li3PO4溶解度小

(3)LiOH=Li2O+H2O這與其它堿不同，LiOH作為蓄電池的電解質(zhì)Heat(6)與H2O,H+劇烈反應(yīng)，但在水中反應(yīng)會(huì)減慢，由He(4)鋰鹽與相類似的其他堿金屬鹽形成

a.低共熔混合物

LiNO3—KNO3LiNO3—NaNO3—KNO3b.復(fù)鹽

M+LiSO4Na3Li(SO4)26H2O(5)過(guò)氧化物（peroxide）不是Li的特征

(6)Li的某些礦物和人造化合物可用來(lái)制備琺瑯，特殊玻璃（透過(guò)紫外光）(4)鋰鹽與相類似的其他堿金屬鹽形成GraphiteIntercalationCompounds(GICs)

GraphiteIntercalationCompounGraphiteIntercalationCompounds(GICs)

GraphiteIntercalationCompounGraphiteIntercalationCompounds(GICs)

FromthefollowingarticleSuperconductivityintheintercalatedgraphitecompoundsC6YbandC6CaThomasE.Weller,MarkEllerby,SiddharthS.Saxena,RobertP.SmithandNealT.SkipperNaturePhysics1,39-41(2005)doi:10.1038/nphys0010GraphiteIntercalationCompounGraphiteIntercalationCompounds(GICs)

Graphiteintercalationcompoundsareintercalationcompoundswithagraphitehost.Inthistypeofcompoundthegraphitelayersremainlargelyintactandtheguestmoleculesoratomsarelocatedinbetween.Whenthehostandtheguestinteractbychargetransferthein-planeelectricalconductivitygenerallyincreases.Whentheguestformscovalentbondswiththegraphitelayersasinfluoridesoroxidestheconductivitydecreasesastheconjugatedsp2systemcollapses.Inagraphiteintercalationcompoundnoteverylayerisnecessarilyoccupiedbyguests.Inso-calledstage1compoundsgraphitelayersandintercalatedlayersalternateandinstage2compoundstwographitelayerswithnoguestmaterialinbetweenalternatewithanintercalatedlayer.Theactualcompositionmayvaryandthereforethesecompoundsareanexampleofnon-stoichiometriccompounds.Itiscustomarytospecifythecompositiontogetherwiththestage.PotassiumgraphiteisdenotedasKC8andisoneofthestrongestreducingagentsknown.Itispreparedunderinertatmospherebymeltingpotassiumovergraphitepowder.Thepotassiumisabsorbedintothegraphiteandacolorchangefromblacktobronzeisobserved.Theresultingsolidisalsoquitepyrophoric.Structurally,compositioncanbeexplainedbyassumingthatthepotassiumtopotassiumdistanceistwicethedistancebetweenhexagonsinthecarbonframework.Thebondbetweengraphiteandpotassiumatomsisionicandthecompoundiselectricallyconductive.GraphiteIntercalationCompoun氫、堿金屬和堿土金屬課件氫、堿金屬和堿土金屬課件Bythistime,ateamofresearchersledbyJohnGoodenough,nowattheUniversityofTexas,haddiscoveredanewfamilyofintercalationcompoundsbasedonoxidesofmanganese,cobaltandnickel.Thefirstcommerciallithium-ionbattery,launchedbySonyin1991,wasarocking-chairdesignthatusedlithium-cobalt-oxideforthepositiveelectrode,andgraphite(carbon)forthenegativeone.Thistypeofbatteryisnowinwidespreaduse,andDrGoodenoughwasawardedthe$450,000JapanPrizein2001inrecognitionofhiswork.Bythistime,ateamofresearThedevelopmentofthelithium-ionbatteryisanobjectlessoninhowpureandappliedresearch,drivenbycommercialinterests,cangeneratetheincrementalimprovementsinatechnologythatarenecessaryfortransformingitintoausefulproduct.Inthiscase,intercalationcompoundswereanoffshootofpureresearchintosuperconductivity.TheywerethenpickedupbyDrGoodenoughandotherresearchersworkingonbatterytechnology;andthefinalpiecesofthepuzzleweresuppliedbySony.(DrGoodenough,whodidhisoriginalresearchatOxford,saysbatteryfirmsintheWestrejectedhisapproaches.)Thedevelopmentofthelithium

三、Sodiumanditscompounds1.Existence:2.Thesimplesubstance(1)與O2反應(yīng)（過(guò)氧化物）:

一般2Na+O2=Na2O2

要得到Na2O需要Na2O2+2Na=2Na2O(2)熔融的鈉與S反應(yīng)

2Na+XS=Na2Sx(3)鈉與NaOH(l)反應(yīng)

2Na+NaOH=Na2O+NaH(4)氨合電子三、Sodiumanditscompounds3.化合物

(1)NaHCO3的溶解度小于Na2CO3的溶解度，可以用氨—氯法制備

NaCl+NH4HCO3=NaHCO3+NH4Cl(2)Na2CO3的制備：

Na2SO4(s)+2C(石墨)+CaCO3(s)=CaS(s)+Na2CO3(s)+2CO2(g)(3)Na2S可溶解單質(zhì)S形成Na2Sx呈現(xiàn)黃色

Na2S+(X-1)S=Na2Sx

(4)OrganometallicCompounds3.化合物聯(lián)合制堿法又稱侯氏制堿法，用于在工業(yè)上制取純堿（Na2CO3）由侯德榜于1943年發(fā)明，是世界上廣泛采用的制純堿法。聯(lián)合制堿法建立在氨堿法的基礎(chǔ)上，反應(yīng)不同點(diǎn)在于：在氨堿法的廢液中加入氯化鈉，并在30～40°C下向廢液中通入二氧化碳和氨氣，使溶液達(dá)到飽和態(tài)，然后降溫到10°C以下，由于氯化銨在30°C時(shí)的溶解度比氯化鈉大，而在10°C下比氯化鈉溶解度小，以及同離子效應(yīng)，使氯化銨從母液析出，其母液又可作為下一次制堿的原料，氯化銨也可以作為一種化肥。蒸乾得到碳酸鈉。主要反應(yīng)方程式為：NH3+CO2+H2O+NaCl=NH4Cl+NaHCO3↓2NaHCO3-加熱→Na2CO3+CO2↑+H2O所謂“聯(lián)合制堿法”中的“聯(lián)合”，指該法將合成氨工業(yè)與制堿工業(yè)組合在一起，利用了生產(chǎn)氨時(shí)的副產(chǎn)品CO2，革除了用石灰石分解來(lái)生產(chǎn)，簡(jiǎn)化了生產(chǎn)設(shè)備。此外，聯(lián)合制堿法也避免了生產(chǎn)氨堿法中用處不大的副產(chǎn)物氯化鈣，而用可作化肥的氯化銨來(lái)回收。聯(lián)合制堿法也存在不足。較氨堿法而言，它的用氨量較大，在有些情況下不適用。維基百科聯(lián)合制堿法又稱侯氏制堿法，用于在工業(yè)上制取純堿（Na2CO3四、PotassiumSubgroup(鉀族元素)1.K，Rb,Cs是最典型的金屬，形成化合物時(shí)離子鍵特征最顯著，而配合物、晶體水合物不是鉀族元素的特征

2.Thesimplesubstances(1)除了Cs是goldenyellow外，其它都是lustrous,silvery—white,軟，密度低，K比水輕，存放在煤油中。四、PotassiumSubgroup(鉀族元素)(2)與非金屬反應(yīng)

a.與S反應(yīng)：用過(guò)量的S與堿金屬硫化物煮沸或熔融的硫化物與S反應(yīng)，形成M2Snb.與氧反應(yīng)（超氧化物）(i)與O2反應(yīng):M+O2=MO2

在液氨中MO2是紅色晶體同樣MO2+M=M2O2

MO2+3M=2M2O(2)與非金屬反應(yīng)(ii)與O3反應(yīng)（臭氧化物）:MO36KOH(s)+4O3(g)=4KO3(s)+O2(g)+2KOH.H2O(s)(iii)它們都不穩(wěn)定

2KO2+2H+=2K++H2O2+O2

2KO3=2KO2+O2

KO3在水中迅速分解

4KO3+2H2O=4K++4OH-+5O2

c.與Br2反應(yīng)發(fā)生爆炸(ii)與O3反應(yīng)（臭氧化物）:MO3(3)與金屬反應(yīng)，主要生成金屬互化物（金屬間化合物）

(IntermetallicCompounds)(4)與H2O反應(yīng)：Rb,Cs與水反應(yīng)發(fā)生爆炸

(5)制備：KCl(l)+Na(g)=NaCl(l)+K(g)(850degC)

由于K的沸點(diǎn)小于Na，使反應(yīng)向右進(jìn)行在液氨中2KCl+Ca=CaCl2+2K

由于CaCl2不溶于液氨，使反應(yīng)向右進(jìn)行(3)與金屬反應(yīng)，主要生成金屬互化物（金屬間化合物）3.化合物

(1)溶解性：與Li+,Na+相似的化合物相反,MClO4,M2PtCl6溶解度小(barelysolable)(2)硝酸鹽熱分解性：3.化合物§3堿土金屬及其化合物

Alkali-earthmetalsandtheircompoundsBerylliumMagnesiumCalciumBeMgCaStrontiumBariumRadiumSrBaRa§3堿土金屬及其化合物

一、通性Generalproperties:1.堿土金屬顯示+2氧化態(tài)

2.性質(zhì)遞變規(guī)律與堿金屬一致二、Berylliumanditscompounds1.性質(zhì)與Al相似，是典型的兩性金屬，在通常情況下，不形成簡(jiǎn)單離子，而形成正負(fù)配離子Be3Al2(SiO3)6一、通性Generalproperties:Be32.Thesimplesubstance(1)密集的六方金屬晶體，表面易形成氧化層，減小金屬本身的活性

(2)與非金屬反應(yīng)2Be+O2=2BeOBe+S=BeS3Be+N2=Be3N2(3)兩性

Be+2H3O++2H2O=[Be(H2O)4]2++H2

Be+2OH-+2H2O=[Be(OH)4]2-+H2

Be對(duì)冷的濃

HNO3和濃H2SO4起鈍化作用2.Thesimplesubstance(4)與金屬反應(yīng):Be與d區(qū)元素反應(yīng)生成金屬間化合物:MBe12,MBe11,也可作為合金添加劑

(alloyingadditive)，使合金耐腐蝕，增加強(qiáng)度和硬度。

(5)Preparation:BeCl2+Mg=MgCl2+Be熱還原法(4)與金屬反應(yīng):Be與d區(qū)元素反應(yīng)生成金屬間化合氫、堿金屬和堿土金屬課件3.化合物[Be(II)](1)BeO、BeS都具有兩性，Be(OH)2,Be(hal)2也有兩性，例如：

BeO+SiO2=BeSiO3BeS+SiS2=BeSiS3BeO+Na2O=Na2BeO2BeS+Na2S=Na2BeS22KF+BeF2=K2[BeF4]BeF2+SiF4=Be[SiF6](2)BeS徹底水解

BeS+H2O=Be(OH)2+H2SBe3N2也徹底水解3.化合物[Be(II)]

(3)BeCl2呈纖維狀結(jié)構(gòu)（fibrousstructure）為什么熔融態(tài)的BeCl2導(dǎo)電能力低于CaCl2?2BeCl2=BeCl3-+BeCl+CaCl2=Ca2++2Cl-

即不形成單個(gè)離子，而形成配離子。

(4)BeCO3,Be3(PO4)2難溶于水，但形成復(fù)鹽后可溶,也可溶解在IA或銨的碳酸鹽飽和溶液中。

(NH4)2CO3+BeCO3=(NH4)2[Be(CO3)2]Berylliumcompoundsarepoisonous!!!與碳酸根配位(3)BeCl2呈纖維狀結(jié)構(gòu)（fibrousstru

三、Magnesiumanditscompounds1.鎂的性質(zhì)明顯不同于鈹，原子、離子半徑差別大，即鎂的金屬性比鈹、鋁強(qiáng)。在自然界中以硅酸鹽和碳酸鹽礦存在。

2.Thesimplesubstance(1)白色金屬，軟，比Be有彈性，在空氣中被氧化呈暗色。單質(zhì)具有強(qiáng)還原性。三、Magnesiumanditscompounds(2)MgOMgX2

O2X2MgN2SMg3N2MgS

Mg不能直接與H2反應(yīng)MgH2只能間接獲得。如通過(guò)MgBr2與NaH反應(yīng)或烷基鎂熱分解等。

(3)鎂主要用于合金(2)MgOMagnesiumalloydevelopmentshavetraditionallybeendrivenbyaerospaceindustryrequirementsforlightweightmaterialstooperateunderincreasinglydemandingconditions.Magnesiumalloyshavealwaysbeenattractivetodesignersduetotheirlowdensity,onlytwothirdsthatofaluminium.Thishasbeenamajorfactorinthewidespreaduseofmagnesiumalloycastingsandwroughtproducts.Afurtherrequirementinrecentyearshasbeenforsuperiorcorrosionperformanceanddramaticimprovementshavebeendemonstratedfornewmagnesiumalloys.Improvementsinmechanicalpropertiesandcorrosionresistancehaveledtogreaterinterestinmagnesiumalloysforaerospaceandspecialityapplications,andalloysarenowbeingspecifiedonprogrammessuchastheMcDonnellDouglasMD500helicopter.KeyProperties·

Lightweight·

Lowdensity(twothirdsthatofaluminium)·

Goodhightemperaturemechanicalproperties·

GoodtoexcellentcorrosionresistanceApplications:aerospace,motorracing,bicycle,etc.Magnesiumalloydevelopmentsh(4)制備:a.白云石CaMg(CO3)2=CaO·MgO+2CO2

2CaO·MgO+Si=Ca2SiO4+2Mgb.c.Compounds:

在HCl的氣氛中加熱MgCl2·6H2O脫水

MgCl2·6H2O=MgCl2+6H2O

也可用干法制備：MgO+Cl2+C=MgCl2+CO(4)制備:

四、CalciumsubgroupCa,Sr,Ba1.鈣分族在化合物中以M2+存在，其配合物不穩(wěn)定。

2.Thesimplesubstance(1)銀白色金屬，在空氣中覆蓋上一層淡黃色膜，鈣非常硬，Sr,Ba軟。

(2)與非金屬反應(yīng)：M與N2,H2,C,Si反應(yīng)

(3)與金屬反應(yīng)：生成金屬互化物四、CalciumsubgroupCa,(4)與H2O反應(yīng)

M+2H2O=M(OH)2+H2

M(OH)2

從CaBa的溶解度增加，活潑性增強(qiáng)

(5)Preparation:CaCl2(L)

電解Ca+Cl2SrCl2(L)Sr+Cl23BaO+2Al=3Ba+Al2O3

Ca,Sr,Ba也可貯存在煤油中，

Ca有時(shí)存放在密封的罐子里。(4)與H2O反應(yīng)3.Compounds(1)氧化物CaCO3=CaO+CO2

2Ba(NO3)2=2BaO+4NO2+O2

過(guò)氧化物，可用間接方法制得:Ba(NO3)2+3H2O2+2NH3·H2O=BaO2·H2O2+2NH4NO3+2H2O(2)碳酸鹽

M(OH)2+CO2=MCO3+H2O

從CaCO3BaCO3熱穩(wěn)定性增加。這是由于離子反極化造成的。3.Compounds(3)M(hal)2

MCl2,M