基礎普化已課件chapter1含氧酸鹽的結構及酸性

互互鹵化d=1.0(5)d=1.3(0)d=1.45(5)d=1.4(0)NanoLett.,2007,7(6),1532-Cl2(g)d=1.0(5)d=1.3(0)d=1.45(5)d=1.4(0)NanoLett.,2007,7(6),1532-(Xheavier,H2(g)+X2(g)→CaF2(s)+2H2SO4(aq,→Ca(HSO4)2(aq)+價層電子對互斥理 氫

KI(s)+H3PO4(aq)→KH2PO4(aq)+HI(g) (HF+ froststheglassSiO2(s4HF(aqSiF4(g)2H2O(l)Go12.0kJ/mol

升華熱+3高

..Cl2Cl2(g)+H2O(aq)→HClO(aq)+Cl2(g)+2OH-(aq)→ClO-(aq)+Cl-(aq)+Cl2(g)CaO(s)(生石灰)→Ca(ClO)2次HX(V)O3，ClOClO3-(aq)+H2O(l)→ClO4-(aq)+2H+(aq)+ 3Cl2(g)+6OH-(aq)△→ClO3-(aq)+5Cl-(aq)+4KClO3(s)△→3KClO4(s)+2KClO3(s)△(MnO2)→2KCl(s)+氧化劑(焰火，火柴2NaClO3(aq)+SO2(g)+→2NaHSO4(aq)+(paramagneticyellowgas漂白紙漿含氧含氧X氧化命次鹵亞鹵(正)鹵高鹵化軌亞氯

..4n酸性n酸性例0弱(10-5-10-3.210-5.810-1(10-2-10-1.110-1.110-2強(10-1-3等電子原 32/5(電子數(shù)/原子數(shù)）等電子 PO3-，SO2-，SiO4- ，，5鍵型4(sp3-px),2(d-pπ85

32/5:酸與酸根：()鍵型及構型相氧化性與穩(wěn)定性 HNO2[(HO)NO]>HNO3[(HO)NO2]NOH2SO3[(HO)2SO]>H2SO4[(HO)2SO2]S穩(wěn)定性

7 Cl7 Cl鍵1234氧化 弱

穩(wěn)定性KNO3<HNO3<氧化性5I2(s,紫紅

ClBrCl

二、氧，硫不同氧化數(shù)的氧化某些O-2的共價分3(檢出I)AgBr(s,淺黃 [Ag(NH)3H2OZn(攪

H2O2(O-超氧化物、臭氧化Cl2(檢出Br)

AgCl(s,白(檢出

硫的含氧酸（鹽多硫化物和硫化 原子半徑和離子半 電負 23%ofthemassoftheLiquidoxygenispaleblue(<-183oC)Thegasiscolorless.2×1010kgLO2/yMetalliccharacterincreasesMetalliccharacterincreasesdownGroup16aselectronegativitydecreases.Oxygenandsulfuroccurnaturallyintheelementalstate.Sulfurformslongchainsandringswithitself,butoxygendoesnot.SteelSteel光解水光解水 2H2O(l)→2H2(g)+光合作用：6CO2(g)6H2O(l)C6H12O6(s)+6CompoundswithNewInsightsintotheStructureofWaterwithCompoundswithYanZubavicusandMichael2H2O(l)+2e-→2OH-(aq)+H2(g)E=-0.42Vat2Na(s)+2H2O(l)BUT,除非有強還原劑，H2O只有在高溫下才起氧化劑作用，如CH4(g)+H2O(g)△→CO(g)+3H2(g)(合成氣H2O是還原劑2H2O(l)→4H+(aq)+O2(g)+4e-E=-0.81VatLewisbase→StructuralLiquidwater,probedonthesub-femtosecondtimescalebyx-rayabsorptionspectroscopy,consistsofstructureswithtwostronghydrogenbondsofeachmoleculetoitsneighbors,resultinginwaterchainsandrings共價小分子氧化物(O-2，氧化數(shù)2⑴單鍵

⑶三鍵

:N

C⑵雙鍵3 3

⑷離域π4π3

C= C

OC π3

π4π2過氧化物(O2，氧化數(shù)2下態(tài)氣下態(tài)氣

O：sp3

Eθ(V):O20.695H2O21.776AEθ(V):Fe3+0.771Fe2+-0.44OOO94.8

工業(yè)應用: Hairbleach漂白VerypaleVerypaleblueliquid;d:144g/mlat25°C;mp,bp:-04,152°CVeryweakacid,pKa1=11Goodoxidizingagentinbothacidicandbasicsolution;(Fe,Mn)Alsoactasareducingagent(MnO4-,Cl2)7Eθ(V):O20.695H2O21.776A

⑴2IO3+5H2O2+2H+=I2+5O2+6HEθ(V):O

HO0.878

⑵I2+5H2O2=2IO+4H2O+ E(左) 鍵OOCOClCN≡

E(右)（岐化發(fā)應） 鍵

IO+6H++5e1I2+3H2O 酸性中2 HO+2H++2e2H 2 O+2H++2eH

Eθ 2 堿性中2HO+HO+2e22

))

臭氧(O3)與臭氧化物

,O氧化數(shù)B33O+HO+2eHO+ B33

O+O

2超氧化物(O，氧化數(shù)1224KO(NaO)+2CO=2KCO(NaCO

2(sp2-OOO π4π3 OO3O+2H++2eO+HOEθ 2

BB③極性單質Abluegas,darkblueliquid;Pungentsmell;CovertheAbluegas,darkblueliquid;Pungentsmell;CovertheEarth 8KO3氧化性和不穩(wěn)定性O+2(氧化數(shù) 6O(氧化數(shù)1 6

S8(s)→113°C△→Chain(red-△→S3,S2(likeSulfuricacid,vulcanizeO2+PtF6

[O

PtF](深紅色

Needlelikemonoclinic

113-113-J.Mater.Chem.,2011,21,171-4-J.J.Am.Chem.Soc.,2010,132,13840-SulfurSulfuroxidesandSO3的結構

SO2，SO3,H2S(IV)O3,→H2S(g)+3O2(g)→2SO2(g)+酸性氧化SO2(g)+H2O(l)→H2SO3(aq)(anequilibrium還原性和氧化SO2(g)+Br2(aq)→Br(aq)+SO2SO2(g)O2(g)→2SO3(g),slowreactioncatalyzedV2O5SO3(g)+H2O(l)→H2SO4(aq)酸雨（SOx,NOx,H2O）H2SO4,無色腐蝕油狀液體；強酸，脫水劑，氧化+化肥 產(chǎn)品 ，清潔劑p 4BCl3、COCl2結構與SO3的相 K2S2O7焦硫酸鉀K2S2O7K2SO4SO3(強氧化性Sulfurdioxide(SOSulfurdioxide(SO2)istheacidanhydride(酸酐)ofsulfurousacid亞硫酸andsulfurtrioxideSO3istheanhydrideofsulfuricacid(硫酸).SO2(g)SO2(g)+→Br-(aq)+SO4-H2SO4(濃→

C12C12H22O11(s)→12C(s)+Sulfuricacid(硫酸isastrongacidadehydratingagent,andanoxidizingagent.還原性

配位性 S- -ONa S- -ONa SOS 2遇酸分解

23SO2+2H+=S(s,黃SO(g)+H2 2I-2Ag+orSO 2I-2①2Ag+(過量)+SO2(適量)=AgSO(s,白2 22Ag2S2O3(s,白)+H2O=Ag2S(s,黑②SO2+2H+=S(s,黃SO(g)+H2Na2S2O3+I2=Na2S4O6+

2 多硫化物Na2Sx1)S=Na2Sx(S2+O2(空氣遇酸分解Na2Sx+2H+=2Na+弱氧化性SnS+S2=SnS2(硫代錫酸鹽

HgS的溶解24HgS+Na2S=Na2HgS2(HgS2)HgS+4I-+2H+=HgI2+H2S24 3HgS+2NO+12Cl- 22

E=–0.48V

+3S+2NO+4H NN2(76%ofairbyN2強的N≡N鍵(944kJ/molalmostasinertasthenoblegases.FixedN:lightning,bacteria;Habersynthesisof電負性高(3.0),半徑小。鍵連原子數(shù)≤43氧化數(shù)：-3to+5,1/3inN3

Angew.Chem.Int.Ed.1995,34,NP NP 2Ca3(PO4)2(s)+6SiO2(s)+△→P4(g)+6CaSiO3(l)+白磷△→紅磷（intheabsenceofFeitilizers,explosives, Thebacteriathatinhabittherenodulesontherootsofapea ntareabletoThebacteriathatinhabittherenodulesontherootsofapea ntareabletofixatmosphericnitrogenandmakeitavailableto nt.根瘤菌GaN,(N,- (N,-Nitrogenishighlyunreactiveasanelement,largelybecauseofitsstrongtriplebond;whitephosphorousishighlyreactive.3Mg(s)+N2(g)△→Mg3N2(s)+6H2O→3Mg(OH)2(s)+NaN3,heatedinasealed,NaN3,heatedinasealed,evacuatedtube, posesintoNaand(N,-Theimpotantcompoundsofnitrogenwithhydrogenareammonia(氨),hydrazine(肼),andhydrazoicacid(疊氮酸)theparentoftheshock-sensitive（疊氮化物Phosphine(PH3)formsneutralsolutionsinwater;PCl3(l)+3H2O(l)→H3PO3(aq)+3HCl(g)PCl5(s)+4H2O(l)→H3PO4(aq)+hydrolysisofnonmetalhalidesproducesoxoacidswithnochangeinoxidationnumber.疊氮N2O(g)+NaNH2(l)175oC NH3+ClO-→N2H4+Cl-氨

NH3(:NH3)的性質加合反應(與H+,Mn+,H2O,BF3等加合)BF3+:NH3=F3BNH3 4 NH3+H2O→NH4

Lewis

LewisBF3為缺電子化合物(價電子數(shù)<價軌道數(shù)還原反應(與O2,X2,CuO等的反應2NH3+3X2(X=Cl,Br)=N2+取代反3Mg+2NH?MgN

1.溶解與水解=MgNHPO(s,白)+2NH+H 3 3Ag2O+2NH3=3H2O+2Ag3N(雷銀

4(檢出Mg2orNH4HgCl

=HgNHCl(s,白)+NH

2.穩(wěn)定(NH4)2CO3=H2CO3+2NH

Hg(NO3)2+2NH3=HgNH2NO3(s,白)+ O- 質子轉 H2CO3

+3darkblueliquidHNO2KNO3(s)+Pb(s)NH4NO3(s)△+3darkblueliquidHNO2KNO3(s)+Pb(s)4NH(g)+5O(g)(250°C,Pt)→4NO(g)+6H )( )(3NO2(g)+H2O(l)3NO2(g)+H2O(l)+4， AnoxidizingagentandanUsedextensivelyintheproductionoffertilizersandActasaneurotransmitter(神經(jīng)傳遞素)andparticipatesinthephysiologicalchanges panying ualarousal. TheThe1998NobelprizeforchemistrywasawardedtoRobertFurchgott,LouisLgnarro,andFeridMurad,whoidentifiedthephysiologicalroleofnitricoxide.andoxoacidsandoxoacidscanbeexinedbyconsideringtheoxidationstateofnitrogen.Nitrogenformsoxidesineachofitsintegraloxidationstatesfrom+1to+5;Thepropertiesofthe66 3(sp2-p)+ 鍵長136(單鍵)>124>118(雙鍵HNO3的氧化性介NO+Al+OH-NH+[Al(OH)]

HNO3(濃)+Sn(As,Sb,Mo,W,S)SnO(SbO,MoO,WO)xHO(水合氧化物 NO+Zn+OH-NH 還原劑及其生成氧化HNO(冷,濃)+Fe(Cr,Al)MO

2 orH3AsO4(H2SO4)(含氧酸生成硝酸HNO3(濃)+其它金屬3HNO3(濃)+C生成水合氧化物或含氧

x M+HNO3

(12mol/dm3)NO2為主(6-8mol/dm3)NO為主2mol/dm3)N2O為

磷紅 白

黑(

orN為 )+33NO2+H2O=NO 磷(3s23p3)的成鍵特

磷的配位磷的配位3456成鍵軌分子構三角四面三角雙八面實PF6

磷酸命名及結 分子 P氧化數(shù)命 次磷據(jù)含H2O

亞磷 (正)磷1H

H

HPO(偏磷酸

4H2H3PO

PHPO(焦磷酸

42 xHP4O10+2H2O=4HPO3(偏磷酸)P4O104H2O=2H4P2O7(焦磷酸)P4O10+6H2O=4H3PO4(正磷酸)干燥 干燥效果

10-10-

強的吸水 磷酸的酸P4(s,white)+3O2(g)→P4(s,white)+3O2(g)→(不足 Ca3(POCa3(PO4)2(s)+2H2SO4(l)→2CaSO4(s)+Ca3(PO4)2(s4H3PO4(l)3Ca(H2PO4)2(s)(重過磷酸鈣→三磷酸腺苷二磷酸腺苷△G=-30kJatpH=7.Releaseslargeamountofenergythatareusedtopowerenergy-demandingprocessesincell. (HO)3PO H(HO)2PO(P+3)H2(HO)PO P 5O544

(d-3NO的檢出33NO+8Al+5OH-+18HO

─

NO+Zn+2HAc=NO+Zn2++2Ac─+H

NO2NO-+2I-+4HAc=2NO(g)+I+2H CCl萃取I呈紫紅色NO不反應

N

+Ac-+ 2. 2. 4+5NO2+6H=2Mn+5NO3

(玫瑰紅色或褐色沉淀 3Ag++PO3=AgPO(s,

石、石1985C60(Kroto,

NH+12

+濃HNO4

4+24H

=

3(sp2.28-sp2.28)+離域(分布在球內(nèi)外3CCC鍵角=348o360o,故呈球面形POPO34 Sn(s)Sn(s)+2HCl(aq)→SnCl2(aq)Sn(s)+2OH-(aq)+2H2O(l)→[Sn(OH)4]2-(aq)+H2CarbonistheonlymemberofGroup14thatformsmultiplebonds.Siliconcanexpanditsvalence SalineSalinecarbides(I,IImetals,Alcarbides)Al4C3(s)+12H2O(l)→4Al(OH)3(s)+3CH4(g)CaC2(s)+2H2O(l)→Ca(OH)2(s)+HC≡CH(g)Covalentcarbides共SiO2(s)+3C(s)2000oC→SiC(s)+Interstitialcarbides間CO2acidanhydrideofH2CO3CO2acidanhydrideofH2CO3COacidanhydrideofHCOOHCH4(g)+H2O(g)→CO(g)+3H2(g)(synthesisgas,Industry)HCOOH(l)[△150°C,H2SO4(c)]→CO(g)+H2O(l)(Lab)LewisNi(s)+4CO(g)[50oC,1atm]→Toxicity:thevictimsuffocates（窒息ReducingFe2O3(s)+3CO(g)[>50oC]→碳酸度電子型88Oxidesof物分解溫中存在(熱即分解物分解溫

碳酸度=Z 離子勢降低，極化作用減離子極化性越大，越易分解

OC

O OCO OMn+

NH3 O

第三周期元素Si原子較大，相互間3p軌道較少，不易成穩(wěn)定的πp-p鍵。d軌道可參加成鍵H4SiO4=H++ Ka1=2×10- HSiO=H++HSiO2K=1.0×10- O

(d-

055

(3SiO4H

四個硅

—-

83

——六個硅酸-5H2OHSiO(6SiO7H——

146 易脫水縮

60-

(SiO2)n(硅膠Threeofthecommonformsofsilica, quartzite(石英巖 超純硅

2SiO2C2

CoC

4SiO2(s).xH2O(gel)+硅膠，高比表面(caThebasicstructuralunitthemineralscalledpyroxenes(輝石ConsistingofchainsofSiO4units.SilicatestructuresarebasedonSiO4tetrahedrawithdifferentnegativechargesanddifferentnumbersofsharedOatoms.Atypicalsilicone硅樹脂)mica(云母)ConsistoflongchainsbasedonSiO4tetrahedra Hallprocess制 950°Cmelted!(1886)CathodeCathodereaction(陰極反應Al3+(melt)+3e-→Al(l)Anodereaction(陽極反應)2O2-(melt)C(s,gr)CO2(g)+4Al3+(melt)+6O2-(melt)+1A,80h1molAl(27g)兩個易拉罐)Al:lowAl:lowdensity;strongmetalandanexcellentelectricalconductor;Astableoxidefilm2Al(s)+6H+(aq)→2Al3+(aq)+inair2Al(s)+3Cl2(g)→Al2O3(s)+3C(s)+3Cl2(g)→2AlCl3(s)+Boronisahard,largelynonmetallicelement.Aluminiumisalight,strong,amphoteric(兩性),reactivemetallicBoronisahard,largelynonmetallicelement.Aluminiumisalight,strong,amphoteric(兩性),reactivemetallicelementwithasurfacethat espassivated(鈍化)whenexposedtoair.(a)Ruby,Cr3+ (b)Sapphire,Fe3+,Ti4+(c)Topaz,Fe3+ 4NaH+4NaH+BCl3→NaBH4H2BO3-(aq)+5H2O(l)→BH4(aq)+8OH--Eo=-1Ni2+(aq)+2e-→Eo=-0Chemical(在非金屬表面鍍一層金屬B2O3(s)+3Mg(s)△→2B(s)+Al(OH)3△→-(lessAl(OH)3△→-(lessdense,moreAl2O3(s)+2OH-+3H2O(l)→2Al(OH)4-Al2O3(s)+Al2O3(s)+→M+M’3+(SO42-)212H2OJianhuaLinetal.,Angew.Chem.Int.Ed.2003,42(45),5607-ThestructureThestructureofBoronisbasedonlinked12-atomBoricacidB(OH)3whitesolidmeltsat171°C.Itistoxictobacteriaandmanyinsectsaswellashumans.Mildantiseptic(殺菌),andpesticide(殺蟲)。Lewisacid電子對受體)(OH)3BOH2(OH)3B-OH2(weakmonoproticacid，一元弱酸)B(OH)3OH2(aq)+H2O(l)→H3O+(aq)+B(OH)4-(aq)阻燃。Themajoruseofboricacidisasstartingmaterialsforitsanhydride,B2O3.meltsat450°C,flux.Borosilicateglass(expandsverylittlewhenheated,suchasPyrex,耐熱2B(OH)3(s→B2O3(s)+3H2O(g)（工業(yè)Boron2B(s)2B(s)+2NH3(g)△→2BN(s)(Almostashardas

硼酸及其特 4BF3+3BH4-→3BF4-+4BF3+3BH4-→3BF4-+B2H6(g)+6H2O(l)→2B(OH)3(aq)+穩(wěn)定，溶解度較小(10℃,3.6g/100g水極弱的 Ka=5.810-H 3c-2eH

H3BO3=H++ +

,100C(4H4H3BO3 2

H3BO3一元(價軌道數(shù)>價電子數(shù)，缺電子化合物,典型的Lewis酸)

,

脂化反

B OH OH B濃H

OO2四硼酸HB

24H2B4O7+2H2O=[B4O5(OH)4]2-

Na[BO(OH)]8HO(硼砂

4

(10H(10HNa2[B4O5(OH)4]8H2O(硼砂 +3OB3

pH=pKa=HO

OB

B+

2NaBO2+B2O3(酸性氧化物CuO熔)五、惰性元素

He-RnHe-Rn單原子氣體；Arthe3rdmostabundantgasintheatmosphere(afterN2,O2);He,the2ndabundantelementintheuniverseafterH,rareonEarth.Acomponentofnaturalgases(notablyHe,Buoyancyinairships;diluteO2;coolant;He-Nelasers.Cryogenics,superfluidity(<2K);Onlysubstanceknowntohavemorethanoneliquidphase.Ne,emitsaredglowwhenanelectriccurrentsthroughAr,provideaninertatmosphere.(lightKr,intensewhitelight,airportrunwayXe,inhalogenlamps.Anesthetic(麻醉劑XeXe+PtF6→KrF2;Ke-N(1988,stablebelow–50oC)XeF2,XeF4,XeF6PowerfulfluorinatingPt(s)+XeF4(s)→Xe(g)+Neadvertising Ar:insomelightbulbs導熱Kr:airportrunwaylighting;Xe:inhalogenlampsfor(intensewhitelight) Xe-OnlyxenonisknownOnlyxenonisknowntoformenextensiveseriesofcompoundswithfluorineandXenonfluoridesarepowerfulfluorinatingagents,andxenonoxidesarepowerfuloxidizingagents.P一.氫化

還原性穩(wěn)定性減

還原性減 酸性增二.氧化物

穩(wěn)定性與還原

弱

中 弱三.常見含氧酸堿性(Pauling規(guī)則)及氧化縮合酸及酸根的鍵型和構鹽的熱穩(wěn)定性及溶解性四

(SiH4)更弱更弱

弱 強 弱 強 弱 強常見陰離子的分離(需)檢

酸性增加,還原性增強,穩(wěn)定性減

CH4( )+2O2=CO2+2H2OB2H6+3O2=B2O3+3H2O

氣體小分子CO,CO2,NO,NO2,N2O,液體：Cl(高 H還原性增

2 固體：N2O5(NONO)(m.p.32.4℃升華)P4O10,P4O6(m.p.23.9 SO(m.p41.5℃),SiO(巨型大分子 穩(wěn)定性減

B2O3無定型體，六方晶體極弱中強強 極弱PO(OH)中強ClO強 極強酸性減酸性增HClO4極強酸極難縮4HClO4(濃H2SO4(強酸)難縮合，酸式鹽縮H3PO4(中強酸),MH2PO4

偏,焦,多聚磷酸(鹽酸性 強

Na2SiO3H硅酸凝膠不具氧化

具氧化

H2B4O7,HBO2,酸酸數(shù)數(shù)32100SiO4B(OH)4鍵型ππππππ離域鍵525252525252含氧酸與其酸根為等電子體(硼酸與硼酸3HNO與NO-(HCO與CO2-)為等電子體3 鍵型及構型與上面系列等電子體有區(qū)別

第二部分P區(qū)金屬元 一.Al(OH)3與Al(OH)3及其它兩性氫氧化鹽的