-19thPartlymiscible(twoliquids) ：miscibleliquid,whichareliquidsthatdonotmixinallproportionsatalltemperatures.：SupposeasmallamountofliquidBisaddedtoasampleofanotherliquidAatatemperatureT,itdissolvescompley,andthebinarysystemremainsasinglephase.AsmoreBisadded,astagecomesatwhichnomoredissolves.Thesamplenowconsistsoftwoliquidphasesinequilibriumwitheachother.Now,wedon’tconsidergasphase,itisdividedintofourPartI.Phasediagramcontainingtheuppercriticaltemperature,att1(℃),addphenolintowater,systempointchangesfromatod,abcl1............l2hewater

water

phenolatt2(℃),addphenolinto systempointchangesfroma’tod’,a'b'c'l'1......l'2h'e'water

water

phenolTheamountofphenolinwatershowsl1’>l1,andthatofwaterinphenolshowsl2’>l2,whichindicatesthemutualsolubilityincreaseswithtemperature. Themutualsolubilityincreaseswiththetemperature,tillthecompositionoftwosaturatedsolutionissameatTuc.Hereitremainsasinglephase.WhentemperatureismorethanTuc,itisalwaysasinglephase.TheamountofeachphasecanbecalculatedbytheleverH2O-C6H5NH2system,twocomponentsis partlymiscible,itremainstwolayeratnormaltemperature. f*K1211f*K1221在373K時，兩液層的組成分別為A’和A”，稱為共軛層，A’和A”稱為共軛配對點。兩層的相對含量用杠桿規(guī)則規(guī)定。An是共軛層組成的平均值。所有平均值的連線與平衡Part2.Phasediagramcontainingthelowercriticaltemperature thanTB proportions.Mutual ItissingleliquidareabelowtheTB. Part3.PhasediagramcontainingTucandTwoliquidsismiscible,atwhichthetemperatureislowerthanTlc(334K),and

liquidsispartlybetweenTlcandAclosecurvedividesthephasediagramintotwoparts:twophaseareaofliquid-liquidatequilibriumiswithinthecurve.Andsinglephaseareaisoutsidethecurve.Part4.PhasediagramhavingnoTucorConsiderapairofliquidsofpartiallymiscibleandformalow-boilingazeotrope.PartI:oneinwhichthe efullymisciblebeforetheyboilPartII:otherinwhichboilingoccursbeforemixingiscomplete.isnouppercriticaltemperaturePartgl

Part ggh Phasediagramofliquid-liquidatequilibriuminmisciblesystemforliquidoftwo

p=常

Threepoints:C,D,andt*t At*A

lll

[l(A+B)+

l l

f C1231Six

n-

AFCH,BGDI,andatequilibriumofH2O(A)-n-C4H9OH(B)

FCEDG,HCE,andLine

p=常

AFCH:unsaturatedsolution(l)

I

ofn-C

OHin

O,

f At*A

llC

B492ofHOinn-CHOH,andf* 2B492 HEI:singlegasphaseareaofHlll

l

andn-CHOH, f

equilibriumland

n-

HCE: phasesatbetweengasphaseandl,f atequilibriumH2O(A)-n-

IDE：two betweengasphaseandl, yimmiscible(twoliquids)supposemutualsolubilityofAandBisverylittle,andthevaluesmaybeignored.Thepartialvaporpressureofeachcomponentisthesameasthevaporpressureofpurecomponent,andtotalvaporpressureisequaltothesumofvaporpressureofpurecomponentforbinarysystem.pp* p* Thetotalvaporpressureisalwaysmorethanthepartialvaporpressureofeachcomponentwhentwoimmiscibleliquidcoexist,similartheboilingpointisalwaysislowerthanthatofeachPhasediagramofliquid-liquidatequilibriumin systemforliquidoftwocomponentstt

p=t*tB

Phasediagramofthepartlymiscibleliquid-liquidatequilibrium2.1.

p=p*

O)+P*

p*p* TPlotofdependenceofvaporpressuretemperatureofwaterandAtanyexternalpressurep,Tb(A+B)<T*b(A)，Tb(A+B)<物蒸氣壓曲沸溴水水+溴pTheratioofmassoftwocomponent:Frompartialpressurelaw,wehave:p* B

wB/M

wBMA / w p

p p

p Bp

MB p p pp

*organic"

"w有機"

求M有機物

p*MB A BMp* §5-3.3.Phasediagramofsolid-liquidequilibriumponent(1). yimmisciblesystemofPartI.SysteminwhichnewcompoundhasnotDrawphasediagrambymeansofthecoolingBasic ponentsystem,andpressureisf*CΦ12Φ13

f*f*

twovariablessystemonevariables f*

unvariables步冷曲線的斜率改變。f*1，出現(xiàn)轉(zhuǎn)折點f*0出現(xiàn)水Example:drawthephasediagramofBi-CdDrawthecoolingcurveofpureBiandpureCdMakepuresolidBimelts, curve.Bistartto at546K,andreleasethe doesn'tchangebefore Onthecoolingcurveline

f*C1121lineOAorA’B: f*C1111ForpureCd,similarprocessoccursoncoolingcurveDrawthecoolingcurveofMakethemixturemelt,andnotethecoolingcurveb.BistartzeatCpoint,andreleasethe zingenergy,whichmakethespeedofTdescentslowandresultinthecurveturningpointatCpoint:2,f*AtDpointCdstartto zetilltoD’point,themeltingliquid ze.Thetemperatureofsystemdoesn'tchangefromDto

3,f*DrawthecoolingcurveofMakethemixturemelts,andnotethecoolingcurveatFpoint:2,f*atG 3,f*DrawthecoolingcurveofMakethemixturemelt,andnotethecoolingcurvec.atEpoint:3,f*0FinishtheT-xofBi-

FourphaseUpperofAEH:meltingliquidWithintheBi(s)+meltingliquid(l)WithinofHEM:Cd(s)+meltingliquidBelowofBEM:LineACE (f*1):twophasecoexists,Bi(s)+l.Line (f*1):twophasecoexists,Cd(s)+lLineBDEGM(f*0):threephasecoexists,Bi(s)+Cd(s)+Threespecialpoints(f*0)A:meltingpointofpureBi(s)H:meltingpointofpureCd(s)E:triplepointofBi(s)+Cd(s)+lThecomponentsofthreephasesarerepresentedrespectivelybythemolefractionsatB,E,andMpoints.因為EA點和H低共。在該點析出的混合物稱為低共熔混合物。它不是化合物，由三相組E，在這xDrawphasediagramofwater-saltsystemfromDeterminethesolubilityofmixtureatdifferentT,andthendrawtheT-xphasediagramofH2O-(NH4)2SO4.UpperofLAN,f*K1211WithintheLAB,ice+f*K1221upperof(NH4)2SO4(s)+f*K1221BelowofthelineBAC,ice+(NH4)2SO4(sf*K1LineLA(f*1):ice+l,orcurveofdescentoficeLineAN(f*1):(NH)SO(s)+l,orcurveofsaturatedsolubilityof4 LineBAC(f*0):ice+(NH)SO(s)+4 Apoint:triplepointofice+(NH4)2SO4(s)+Lpoint:meltingpointofCoolthesolution,icefirstseparateswhenthecomponentofsolutionisbeingintheleftofApoint,whereas(NH4)2SO4(s)firstseparateswhenthecomponentofsolutionisbeingintherightofApoint. H2O-NaCl(s)H2O-CaCl2(s)H2O-KCl(s)H2O-NH4Cl(s)

252218262.5257.8應(yīng)用2：粗(NH4)2SO4首先將粗鹽溶解，加溫至353K，濾去不溶性雜質(zhì)，設(shè)這時物接近三相線，但要防止冰同時析出)后，過濾得到純(NH4)2SO4再升溫至O點，加入粗鹽，使其完全溶解后濾去固體雜質(zhì)，使物系點移到SPartII.Systeminwhichnewcompoundhas(I)Stablecompound:thereisitselfmeltingpointinthephasediagram,andthecomponentsinliquidandgasphaseissameatthemeltingpoint,forexample:(II)Unstablecompound:thereisnotitselfmeltingpointinthephasediagram.The posesintoliquidandsolidphasebelowthetemperatureofmeltingpoint,forexample:

CuCl(s)-FeCl3Au(s)-2Fe(s)CuCl2KClFeCl3H2OH2SO4H2CaF2-CaCl2Au-Sb22KCl-CuCl2K-Na(I)PhasediagramformingstableThediagrammayberegardedasthetwosimplephasediagramofcompleyimmisciblesystemofsolid.AddCuCl(A)orFeCl3(B)intoCompoundCthatresultsinthedescentofmeltingpointofcompoundC.Threekindsofhydratesareformed,H2SO44H2O(C1),H2SO42H2O(C2andH2SO4H2O(C3),theyhavethemselvesmelting01 01--70

·1E

I|乓I ，-K+-90 (H20)心EH2AB—H2

2SOi)0B(II)PhasediagramformingunstableCistheunstablecompoundconsistsofAandB.IfcompoundCisheatedtilltothetemperatureofOpoint,whichwillposeinto meltingliquidwhosecomponentisO(s)

F(s)+N(l)所以將O點的溫度稱為轉(zhuǎn)熔溫O(s)

F(s)+N(l) crystaliscoated(包晶現(xiàn)象)Lineb:Linea:Line

LA(s)LA(s)C(s)L(N)LA(s)LA(s)C(s)L(N)A(s)LA(s)LA(s)C(s)L(N)C(s)C(s)B(s)L(D)C(s)ToobtainpureC,maketheconcentrationofmeltingliquidisbetweenNDpoint,andtemperaturebetweentwothreephaseequilibrium

·

加熱3Al23加23

SiO2—Al2O3相圖可當成由一個低零的相區(qū)有GEH，DSF及CI三個三相水平結(jié)線，有Al2O3之B及白硅石的A，還有C點是鱗SiO2二種變體：鱗石英(C點以下)； Al2O3為剛玉(s)+l不穩(wěn)定化合物在固液平衡時，二相組成不同。加熱時 之前它分解為另一固相和組成與它不相同的液相，在相圖上不具有最 為101.325kPa。組分A的正常沸點比組分B的正常沸點高10℃。在101.325kPa將8molA和2molB混合加熱到60℃產(chǎn)生第一個氣泡，其組成為yB=0.4，繼續(xù)在101.325kPa下恒將7molB和3molA氣體混合，在101.325kP