6/20/2017 solidliquidphasediagrams:tinandlead

SOLIDLIQUIDPHASEDIAGRAMS:TIN
ANDLEAD

Thispageexplainstherelationshipbetweenthecoolingcurves
forliquidmixturesoftinandlead,andtheresultingphase
diagram.Italsooffersasimpleintroductiontotheideaofa
eutecticmixture.

Important:Thispageisonlyreallydesignedtobean
introductiontothetopicsuitableforcoursesfor1618year
oldssuchasUKAlevelchemistry.Beawarethatthephase
diagramusedisasimplifiedversionoftherealthing.In
particular,itignorestheformationofsolidsolutionsoftinand
lead.Iwillgivealinktothecorrectphasediagramlater.

Coolingcurves

Coolingcurvesforpuresubstances

Supposeyouhavesomepuremoltenleadandallowittocool
downuntilithasallsolidified,plottingthetemperatureofthe
leadagainsttimeasyougo.Youwouldendupwithatypical
coolingcurveforapuresubstance.

Note:Justbeforetheliquidfreezes,thereissometimesa
slightdipinthecurvebelowthefreezingpoint.Thisiscalled
supercooling.Assoonassomesolidforms,thetemperature
recoverstothenormalfreezingpoint.Supercoolingisn't
importantforthepresentdiscussion,soI'mignoringitonthe
diagrams.

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6/20/2017 solidliquidphasediagrams:tinandlead

Throughoutthewholeexperiment,heatisbeinglosttothe
surroundingsandyetthetemperaturedoesn'tfallatallwhile
theleadisfreezing.Thisisbecausethefreezingprocess
liberatesheatatexactlythesameratethatitisbeinglosttothe
surroundings.

Energyisreleasedwhennewbondsforminthiscase,the
strongmetallicbondsinthesolidlead.

Ifyourepeatedthisprocessforpureliquidtin,theshapeofthe
graphwouldbeexactlythesame,exceptthatthefreezingpoint
wouldnowbeat232C.(Thegraphforthisisfurtherdownthe
page.)

Coolingcurvesfortinleadmixtures

Asamplecurve

Ifyouaddsometintothelead,theshapeofthecoolingcurve
changes.Thenextgraphshowswhathappensifyoucoola
liquidmixturecontainingabout67%leadand33%tinbymass.

Therearelotsofthingstolookat:

Noticethatnothinghappensatallatthenormalfreezing
pointofthelead.Addingthetintoitlowersitsfreezing
point.

Freezingstartsforthismixtureatabout250C.Youwould
starttogetsomesolidleadformedbutnotin.Atthat
pointtherateofcoolingslowsdownthecurvegetsless
steep.

However,thegraphdoesn'tgohorizontalyet.Although
energyisbeinggivenoffastheleadturnstoasolid,there
isn'tanythingsimilarhappeningtothetin.Thatmeansthat

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6/20/2017 solidliquidphasediagrams:tinandlead

thereisn'tenoughenergyreleasedtokeepthe
temperatureconstant.

Thetemperaturedoesstopfallingat183C.Nowbothtin
andleadarefreezing.Onceeverythinghassolidified,the
temperaturecontinuestofall.

Changingtheproportionsoftinandlead

Ifyouhadlesstininthemixture,theoverallshapeofthecurve
staysmuchthesame,butthepointatwhichtheleadfirststarts
tofreezechanges.

Thelesstinthereis,thesmallerthedropinthefreezingpointof
thelead.

Foramixturecontainingonly20%oftin,thefreezingpointofthe
leadisabout275C.That'swherethegraphwouldsuddenly
becomelesssteep.

BUT...youwillstillgetthegraphgoinghorizontal(showingthe
freezingofboththetinandlead)atexactlythesame
temperature:183C.

Asyouincreasetheproportionoftin,thefirstsignsofsolidlead
appearatlowerandlowertemperatures,butthefinalfreezingof
thewholemixturestillhappensat183C.

Thatcontinuesuntilyouhaveaddedenoughtinthatthemixture
contains62%tinand38%lead.Atthatpoint,thegraph
changes.

Thisparticularmixtureofleadandtinhasacoolingcurvewhich
looksexactlylikethatofapuresubstanceratherthanamixture.
Thereisjustthesinglehorizontalpartofthegraphwhere
everythingisfreezing.

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6/20/2017 solidliquidphasediagrams:tinandlead

However,itisstillamixture.Ifyouuseamicroscopetolookat
thesolidformedafterfreezing,youcanseetheindividual
crystalsoftinandlead.

Thisparticularmixtureisknownasaeutecticmixture.The
word"eutectic"comesfromGreekandmeans"easilymelted".

Theeutecticmixturehasthelowestmeltingpoint(whichis,of
course,thesameasthefreezingpoint)ofanymixtureoflead
andtin.Thetemperatureatwhichtheeutecticmixturefreezesor
meltsisknownastheeutectictemperature.

Whathappensifthereismorethan62%oftininthe
mixture?

Youcantraceitthroughinexactlythesameway,byimagining
startingwithpuretinandthenaddingleadtoit.

Thecoolingcurveforpureliquidtinlookslikethis:

It'sjustlikethepureleadcoolingcurveexceptthattin'sfreezing
pointislower.

Ifyouaddsmallamountsofleadtothetin,sothatyouhave
perhaps80%tinand20%lead,youwillgetacurvelikethis:

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6/20/2017 solidliquidphasediagrams:tinandlead

Noticetheloweredfreezingpointofthetin.Noticealsothefinal
freezingofthewholemixtureagaintakesplaceat183C.

Asyouincreasetheamountoflead(ordecreasetheamountof
tinsamething!)untilthereis62%oftinand38%oflead,you
willagaingettheeutecticmixturewiththecurvewe'vealready
lookedat.

Thephasediagram

Constructingthephasediagram

Youstartfromdataobtainedfromthecoolingcurves.Youdraw
agraphofthetemperatureatwhichfreezingfirststartsagainst
theproportionoftinandleadinthemixture.Theonlyunusual
thingisthatyoudrawthetemperaturescaleateachendofthe
diagraminsteadofonlyatthelefthandside.

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6/20/2017 solidliquidphasediagrams:tinandlead

Noticethatatthelefthandsideandrighthandsidesofthe
curvesyouhavethefreezingpoints(meltingpoints)ofthepure
leadandtin.

Note:Thetwolinesmeetingattheeutecticpointhavebeen
simplifiedslightlysothattheyaredrawnasstraightlines
ratherthanslightcurves.Itdoesn'taffecttheargumentin
anyway.Ihaven'tbeenabletofindtheactualdatatoplot
themaccurately,sothesimplificationistoavoidgivingthe
impressionthatIactuallyknowexactlywhatthecurveslook
like!

Tofinishoffthephasediagram,allyouhavetodoisdrawa
singlehorizontallineacrossattheeutectictemperature.Then
youlabeleachareaofthediagramwithwhatyouwouldfind
underthevariousdifferentconditions.

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6/20/2017 solidliquidphasediagrams:tinandlead

Important:Thisisasimplifiedversionoftherealtinlead
phasediagram.Inparticular,itignorestheformationofsolid
solutionsoftinandlead.Youwillfindthecorrectdiagramon
thisNISTwebpage.Bewarethatonthatpage,thetinlead
axisisreversedfromtheoneIhavedrawnaboveinother
words100%leadisontherightratherthantheleft.

Ifyouarejustusingthispageasanintroductiontothissort
ofphasediagram,youdon'tneedtoworryaboutthis.

Usingthephasediagram

Important:Oneoftheproblemswiththevarioussortsof
phasediagramsisthattheyareallinterpretedslightly
differently.Youcan'tassumethatbecauseyouknowhowto
useonesortofphasediagramthatyoucantreatothers
exactlythesame.Ifyoualreadyknowaboutotherphase
diagrams,lookatthisonecompletelyafresh.

Supposeyouhaveamixtureof67%leadand33%tin.That's
themixturefromthefirstcoolingcurveplottedabove.Supposeit
isatatemperatureof300C.

Thatcorrespondstoasetofconditionsintheareaofthephase
diagramlabelledasmoltentinandlead.

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6/20/2017 solidliquidphasediagrams:tinandlead

Nowconsiderwhathappensifyoucoolthatmixture.Eventually
thetemperaturewilldroptoapointwhereitcrossesthelineinto
thenextregionofthediagram.

Atthatpoint,themixturewillstarttoproducesomesolidleadin
otherwords,thelead(butnotthetin)startstofreeze.That
happensatatemperatureofabout250C.

Nowthereisabitofaproblem,becauseyoumightcomeacross
twodifferentwaysofexplainingwhathappensnext.We'lllookat
both.

Thinkingaboutchangesinthecompositionoftheliquid

Whenthefirstoftheleadfreezes,thecompositionofthe
remainingliquidchanges.Itobviouslybecomesproportionally
richerintin.Thatlowersthefreezingpointoftheleadabitmore,
andsothenextbitofleadfreezesataslightlylower
temperatureleavingaliquidstillricherintin.

Thisprocessgoeson.Theliquidgetsricherandricherintin,
andthetemperatureneededtofreezethenextlotoflead
continuestofall.Thesetofconditionsoftemperatureand
compositionoftheliquidessentiallymovesdownthecurve
untilitreachestheeutecticpoint.

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6/20/2017 solidliquidphasediagrams:tinandlead

Onceithasreachedtheeutecticpoint,ifthetemperature
continuestofall,youobviouslyjustmoveintotheregionofa
mixtureofsolidleadandsolidtininotherwords,allthe
remainingliquidfreezes.

Ifyouhaven'tcomeacrossthiswayoflookingatitbefore,then
pleasedon'tbothertolearnitnow!Thesecondwayismorein
linewithhowwelookatotherphasediagrams,andactually
needslessthinkingabout.

Thinkingaboutthecompositionofthesystemasawhole

We'veseenthatastheliquidgraduallyfreezes,itscomposition
changes.Butifyoulookatthesystemasawhole,obviouslythe
proportionsofleadandtinremainconstantyouaren'ttaking
anythingawayoraddinganything.Allthatishappeningisthat
thingsarechangingfromliquidstosolids.

Sosupposewecontinuethecoolingbeyondthetemperature
thatthefirstsolidleadappearsandthetemperaturedropstothe
pointshowninthenextdiagramapointclearlyinthe"solid
leadandmoltenmixture"area.

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6/20/2017 solidliquidphasediagrams:tinandlead

Whatwouldyouseeinthemixture?Tofindout,youdrawa
horizontaltielinethroughthatpoint,andthenlookattheends
ofit.

Atthelefthandend,youhave100%lead.Thatrepresentsthe
solidleadthathasfrozenfromthemixture.Attherighthand
end,youhavethecompositionoftheliquidmixture.Thisisnow
muchricherintinthanthewholesystemisbecauseobviously
afairbitofsolidleadhasseparatedout.

Asthetemperaturecontinuestofall,thecompositionofthe
liquidmixture(asshownbytherighthandendofthetieline)will
getcloserandclosertotheeutecticmixture.

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Itwillfinallyreachtheeutecticcompositionwhenthe
temperaturedropstotheeutectictemperatureandthewhole
lotthenfreezes.

Atatemperaturelowerthantheeutectictemperature,youare
obviouslyinthesolidleadplussolidtinregion.That'sfairly
obvious!

Ifyoucooledaliquidmixtureontherighthandsideofthephase
diagram(totherightoftheeutecticmixture),everythingwould
workexactlythesameexceptthatsolidtinwouldbeformed
insteadofsolidlead.Ifyouhaveunderstoodwhathasgone
before,itisn'tatalldifficulttoworkoutwhathappens.

Finally...whathappensifyoucoolaliquidmixturewhichhas
exactlytheeutecticcomposition?

Itsimplystaysasaliquidmixtureuntilthetemperaturefalls
enoughthatitallsolidifies.Younevergetintotheawkward
areasofthephasediagram.

Tinleadmixturesassolder

Traditionally,tinleadmixtureshavebeenusedassolder,but
thesearebeingphasedoutbecauseofhealthconcernsoverthe
lead.Thisisespeciallythecasewherethesolderisusedtojoin
waterpipeswherethewaterisusedfordrinking.Newnonlead
soldershavebeendevelopedassaferreplacements.

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6/20/2017 solidliquidphasediagrams:tinandlead

Typicaloldfashionedsoldersinclude:

60%tinand40%lead.Thisisclosetotheeutectic
composition(62%tinand38%lead),givingalowmelting
point.Itwillalsomeltandfreezecleanlyoveraverylimited
temperaturerange.Thisisusefulforelectricalwork.

50%tinand50%lead.Thiswillmeltandfreezeovera
widerrangeoftemperatures.Whenitismoltenitwillstart
tofreezeatabout220Candfinallysolidifyattheeutectic
temperatureof183C.Thatmeansthatitstaysworkable
forausefulamountoftime.That'shelpfulifitisbeingused
forplumbingjoints.

Questionstotestyourunderstanding

Ifthisisthefirstsetofquestionsyouhavedone,pleasereadthe
introductorypagebeforeyoustart.YouwillneedtousetheBACKBUTTON
onyourbrowsertocomebackhereafterwards.

questionsonthetinandleadphasediagram

answers

Wherewouldyouliketogonow?

Tothephaseequilibriummenu...

TothePhysicalChemistrymenu...

ToMainMenu...

JimClark2004(modifiedJanuary2014)

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