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PhaseTransitions:Howdoeswaterevaporatebelowitsboilingpoint?
howboilingpointofacomponentreduceswhenpartialpressurereduces?
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JesseBerezovsky,ProfessorofPhysics,CaseWesternReserveUniversity

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13.2kViewsUpvotedbyChristopherVanLang,PhDinChemicalEngineeringatStanfordUniversityEdwinKhoo,
PhDstudentinChemicalEngineeringatMITLeoC.Stein,Ph.D.fromMIT,B.S.fromCaltech.Specializingin
gravity.
Jessehas9endorsementsinPhysics.

Ifwaterreallyboilsandevaporatesat100C,thenwhyisitthat
watervaporexistsintheair(humidity)eveninsubze...

Iwilltrytocombinethecorrectaspectsoftheanswersandcommentspostedsofar,and
elaborateabit.
1.Evaporation.Aphasetransition,inthiscasefromliquidtogas,occurswhenconditions
(temperatureandpressure)aresuchthereisanetreductionoffreeenergytotakea
moleculeoutoftheliquidandputitinthegas.Ataninterfacebetweenaliquidandagas,
awatermoleculecanrandomlyflyoutoftheliquidandjointhegas,ordropoutofthegas
andjointheliquid.Thisgas/liquidsystemisatequilibriumifthechangeinfreeenergyis
thesameforamoleculetogoineitherdirection.Inthiscase,themoleculesare
transferredinbothdirectionsatthesamerate,andthereisnonetchange.Ifyouhavea
situationthatisnotinequilibrium,thenmoleculeswillbetransferredfromtheliquidtothe
gasorthegastotheliquidpreferentially,andthiswillcontinueuntilthepressureor
temperaturehavechangedtoachieveequilibrium,oruntilonephaseiscompletelygone.
Inmanycommonexamples,equilibriumisneverreached.Forexample,atroom
temperature,theequilibriumpointforwaterwillbeatapressureofabout20Torr.Ifthe
relativehumidityislessthan100%,thenthepartialpressureofwaterintheairislessthan
20Torr.So,ifyouputaglassofwaterinsuchanatmosphere,thewatermoleculeswill
tendtoleavetheliquidandjointhegas.Sincetheatmosphereismuchlargerthanthe
glassofwater,thisevaporationwillnotnoticeablychangethepartialpressureofwaterin
theatmosphere,sothewaterwillcontinuetoevaporateuntilitisentirelyconvertedinto
gas.Ontheotherhand,ifyouputacapontheglass,theevaporationwouldonlycontinue
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untilthepartialpressureofwaterwentupto20Torr.

Doeswaterevaporateunder0degreecelsius?
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OK,sowhendoesboilingoccur?Thedifferencebetweenboilingandevaporationisthatin
boiling,bubblesofgasform,withinoratthesurfaceoftheliquid.Theformationofthese
bubblestakesextraenergy.Soboilingtakesplacewhenthereisanetreductioninfree
energytotakeamoleculeoutoftheliquidandputinthegaswhileexpandingabubble.
Forbubbleformation,firstamicroscopicbubblehastorandomlyform(nucleate),and
thenithastogrow.Theenergyofabubblecomesfromsurfacetension(thegas/liquid
interfacehashigherenergythanaliquid/liquid"interface")andfromtheneedtoexpand
againstpressure(thebubblehastoliftthewateraboveit).Asdiscussedabove,atroom
temperaturetheequilibriumpointbetweenliquidandgaseouswaterisat20Torr.Ifa
bubbleweretonucleateatroomtemperature,gaswouldonlybeaddedtoituptoa
pressureof20Torr,whichisnotenoughtogrowthebubbleagainstatmosphericpressure
of760Torr.Sothisdoesnothappen,andwaterdoesnotboilatroomtemperatureand
atmosphericpressure.Itonlyevaporates.Weseethatforboilingtooccur,theequilibrium
vaporpressureofthegaseouswatermustbeatleast760Torr(thatis,thewatervapor
pressuremustbeatleastatmosphericpressure).Forwaterat1atm,thispointisreached
at100C.Atthispoint(orjustabove),bubblescangrownearthesurfaceofliquidwater
becausethepressurewithinthebubbleisgreaterthanthepressuretryingtocollapsethe
bubble.Boilingmaystillnotoccurhowever,becausethebubblesmustnucleatebeforethey
cangrow.Nucleationiscomplicated,anddependsontheparticularsituation(e.g.water
inasmoothglasscontainermaynotboilabove100C).
2.Passagearoundthecriticalpoint.Theansweralongtheselinesisalsocorrect.At
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sufficientlyhighpressureandtemperaturethedistinctionbetweenliquidandgasbreaks
down,andthereisnophasetransitionbetweenthetwo,hencenoevaporationorboiling.
Bystartingasaliquid,goingintothesupercriticalregime,thencomingbackintothe
subcriticalregimeinthegasphase,youavoidboiling.
3.Sublimation.Althoughmaybetheaskerwasjustthinkingofliquidtogastransitions,
solidtogastransitionscanalsooccur,inthiscase,whenthereisanetreductioninthefree
energyfromtakingamoleculeoutthesolidandputtingitintoagas.Forwater,thistakes
placeatpressurebelowabout5Torr.
Updated12JulViewUpvotesAskedtoanswerbyYishanWong

RyanCarlyle,BSChE,SubseaHydraulicsEngineer
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OriginallyAnswered:Howdoeswaterevaporatebelowitsboilingpoint?

There'saverysimplepieceofthepuzzlemissingfromtheotheranswers.Liquidwater
alwayshassomepressureofwatervaporaboveitthehigherthetemperature,themore
pressureofvaporyougetabovethewater.The"boilingpoint"isnotsomemagical
temperaturewherethepropertiesofwaterchange,itismerelythetemperatureatwhich
thevaporpressureproducedbythewaterishigherthanlocalatmosphericpressure.Ifthe
watervaporpushesoutharderthantheairpushesitin,thevaporisabletoforceitsway
awayfromthesurfaceoftheliquidandescape.Insteadofneedingtodiffuseawayorbe
blownbyexternalwind,thevaporcanflowawayatarapidrateunderitsownpower.Ina
roilingboil,thevaporpressureatthehotsurfaceishigherthanthehydrostaticpressurein
thepotofwaterplusatmosphericpressure,sothemostenergeticwatermoleculeshave
enoughforcetoformgasbubblesbelowthesurface.
Boilingisjustnormalevaporationthatisabletooccurmuchmorerapidlybecausethe
evaporationrateisnolongerlimitedbylocalairpressure.Lowerairpressuremeansa
lowerboilingpoint.InDenver,ittakeslongertoboilaneggthaninHouston.Inapressure
cooker,waterboilsatahighertemperaturebecausethecontainerpreventsthevaporfrom
escaping.Andinavacuum,waterwillboilawayintoacloudoficecrystalsalmost
instantaneously,becausetheboilingpointisactuallybelowthefreezingpoint.
Written31Dec2012ViewUpvotes
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S.MarshallPriddy,Biochemicalengineer
2.9kViewsUpvotedbyAbrahamBuditama,PhDstudentinchemistryatUCLA;BSfromCaltech(2010)
OriginallyAnswered:Howdoeswaterevaporatebelowitsboilingpoint?

Allsubstancesarecomposedofmolecules.Foragivenbodysay,aglassofwaterthe
temperatureofthewholeisreallyjusttheaveragemolecularenergyofthemoleculesit
comprises.Buttheaverageisonlyanaverage,andatagivenmoment,thespeedsof
individualmoleculesvary,withagenerallybellshapeddistribution.Thatmeanssomeare
travellingmuchslower,andothersmuchfaster.Sincethethermalenergyisintheformof
randommolecularmovements,witheverythingsmashingandcrashingaround,forany
givenmolecule,thespeedwithwhichittravelschangeswitheachnewcollision.
Nowwaterisheldtogethernotonlybythesimpleweightofgravityholdingitdown,butby
acollectionofweakbondscalledhydrogenbonds.Thisisbecauseoftheuniquely"bent"
shapeofthewatermolecule.

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Source

Theeffectisthatahydrogenatomfromonemoleculehasatendencyto"stick"tothe
oxygenatomofanadjacentmolecule.Thisiswhatmakeswaterremaininaliquidstateat
amuchhighertemperaturethanyouwouldexpectbyitsmolecularweightalone.
Nowwhathappensisthatatthesurfaceoftheliquid,agivenmoleculemightgetenough
energytosimplybreakfreeofthehydrogenbondsthatkeepitintheliquid.Whenitdoes
this,itbecomesavapor,anditstartsbehavingasagasthemoleculeswithwhichitnow
interactsaretravelingwithamuchhighervelocity,andtheydonotcollideatspeedslow
enough(ingeneral)forhydrogenbondingtoresume.Theexceptiontothatlastpointisin
theformationoffog,clouds,andultimatelyrain.
Allthewhile,however,thereareotherwatermoleculesinthegasphase(byphasehere,I
meanthedesignationofeitherliquid,solid,gas,etc.)directlyabovethesurfaceofthe
liquidphase.Fortheconversereason,thedistributionofspeedsinthegasphasewill
includeafewmoleculeswithsucha*low*speed,thatwhenitcollideswiththesurfaceof
theliquid,itlosestheenergyitwouldneedtoremainasavapor,andsuccumbstothe
hydrogenbondsthatmakeitnowapartoftheliquid.
Theneteffecthereisthattheliquidwillgainsome,anditwilllosesome.Thenetdirection
dependsonwhethertheairissaturatedwithH2Oornot.
Usually,itisnotsaturated,soyouexpectapuddletodryupovertime,evenifthe
temperatreofthewaternevergetsnearboiling.Butthedriertheairisthatistosay,
morearid,lesshumidthelessthelossofwatermoleculesfromliquidtogaswillbeoffset
bytransfersfromgastoliquid.Soafterarainstorm,theairisclosetosaturatedwith
water,andpuddlesdryveryslowly.Thisisalsowhyspilledwaterwilldrymuchquickerin
PhonixorLasVegas,evenifit'snotahotday.Andit'sthereasonwhyblowingonthings
driesitoutyou'reforcingthesaturatedvaporatthesurfaceaway,andpushinginair
that'smuchdrierandcanremovemoremoisture.

Theconversecanalsohappen,butwedon'tnormallynoticeitintheliquiditself.Ifyou
haveacupoficedbeveragewithanopentop,waterfromtheairarounditwillcrashinto
thesurface,losetheenergyneededtoescape,andincreasetheoveralamountofliquidin
thecup.Butit'sasamllamountgenerallynotnoticed.Whatwe*do*tendtonoticeis
whenthishappenstothecold,dryexteriorofthecupitself.Thiscondensesontothecup
anmakestheoutsideofitwetthatwaterontheoutsideofthecupisfromtheairaround
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itcondensing,ratherthanfromthebeverageinthecupitself.

Youcanalsohaveasituationwheretherateofchangefromliquidtogasisexactlythe
sameastherateofchangefromgastoliquid.Thisiscalledequilibrium,andthere'snonet
changeintheliquidvolume.Thebestexampleofthiswouldbeonaclosedbottleorjar.
Theairinthecontainersoonbecomessaturated,andsolongasthejarremainsclosedand
there'snogreatchangeintemperatureforthejar,theliquidvolumeremainsfixed.
Written31Dec2012ViewUpvotes
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KumarPranay,Youmademe.
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OriginallyAnswered:Whydoeswaterbecomesteambefore100C?

Othersanswershavealreadyaddressedtheissueofdifferencebetweenboilingand
evaporationwhichexplainsthevapors(whichisnotsteam)ofwaterattemperaturesbelow
100C.
AlsonotethatBoilingpointTemperatureofanyliquidisafunctionofpressuretoo.The
boilingpointtemperaturedecreasesifsurroundingpressureislow.Soathighaltitudes(or
anylocationwherepressureislessthan1atm)waterboilsatlowertemperature.Reverse
happensifsurroundingpressureishigh.
Alsoboilingpointtemperatureofaliquidcanbeincreasedbyaddinganonvolatilesolute
intheliquid.Soifyouhaveseawater,youcandecreaseitsboilingpointbypurifyingit.
HopeyouknowthatBoilingpoint(BP)isthetemperatureatwhichvaporpressureofthe
liquidisequaltothesurroundingpressure(whichif1atmthenitscallednormalBP100C
incaseofpurewater).
Thereareotherdimensionstoitifwanttogoinbitdepth:
>Amixtureoftwovolatileidealliquids(whichfollowRaoult'slaw)hasarangeof
boilingpointswhichrangefromBPoflessvolatiletoBPofmorevolatileliquid.
DependingonthecompositionofthemixtureyoucanhaveacorrespondingBPofthe
mixture.

>IfthemixturebehavesNonideallythenthereareotherpossibilities
1.PositivedeviationsfromRaoult'sLaw
Thevaporpressureofthismixtureisalwayshigherthanyouwouldexpectfromanideal
mixture.
Thefactthatthevaporpressureishigherthanidealinthesemixturesmeansthat
moleculesarebreakingawaymoreeasilythantheydointhepureliquids.Thatisbecause
theintermolecularforcesbetweenmoleculesofAandBarelessthantheyareinthepure
liquids.
Youcanseethiswhenyoumixtheliquids.Lessheatisevolvedwhenthenewattractions
aresetupthanwasabsorbedtobreaktheoriginalones.Heatwillthereforebeabsorbed
whentheliquidsmix.Theenthalpychangeofmixingisendothermic.Theclassicexample
ofamixtureofthiskindisethanolandwater.

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Ifthedeviationsarequitelarge,thenamaximumboilingpointAZEOTROPE(A
mixtureoftwoormoreliquidswhoseproportionscannotbealteredbysimpledistillation)
isformed.Mixtureisthenknownasaconstantboilingmixtureoranazeotropicmixtureor
anazeotrope.Thepointwherethetwocurvestouchinthefigurebelowgivesthe
azeotropiccomposition.

2.NegativedeviationsfromRaoult'sLaw
ThevaporpressureswhicharelessthanwouldbeexpectedbyRaoult'sLaw.
Thesearecaseswherethemoleculesbreakawayfromthemixturelesseasilythantheydo
fromthepureliquids.Newstrongerforcesmustexistinthemixturethanintheoriginal
liquids.Youcanrecognizethishappeningbecauseheatisevolvedwhenyoumixthe
liquidsmoreheatisgivenoutwhenthenewstrongerbondsaremadethanwasusedin
breakingtheoriginalweakerones.

Ifthenegativedeviationsarequitelarge,thenaminimumboilingpointAzeotropeis
formedasshownbelow.

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>Atlasttheaboveisonlyforbinarymixtures.Youcanimaginethecomplexityinareal
fluidwithallsortsofsolutes,surroundingpressureandofcoursemulticomponents.
NoteTherearennumberofreasonsforyouranswer.Chooseyoursaccordingtowhatsuits
yourdepthofknowledge.
Written11FebViewUpvotesAskedtoanswerbyMalanBalasubramaniam
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MatthieuRouif,Entrepreneur,Co-Founder@HeyCrowd,Founder@As-App,MSinMaterials
Science...
1.2kViews
OriginallyAnswered:Howdoeswaterevaporatebelowitsboilingpoint?

AfundamentalruleofPhysicsisthatwhentemperatureisabove0K(273,15C,459,67
F)thereissomemovementinthere.Forliquidsitmeansmoleculesareconstantlyejected
fromtheliquid'ssurfacetothesurroundingvapourenvironment.So,nexttoliquidwater,
thereisliquidvapour,actuallythereisa"concentration"ofwatermoleculeintheair,
calledvaporpressure,whichistheequilibrium(thebeststate).(File:Watervaporpressure
graph.jpg ).Thehotter,themoremoleculecanbeintheair.
Ifyou'reinacloseroomlikeyourshower,waterwillevaporatesuntilitreachesthisvapour
pressureconcentrationandthenitwon'tevaporateanymoreandactuallyitwill
condensate(turnliquid)onsurfaceslikemirrorsorwallsaspartofthedynamic
equilibrium.Whenyouopenthedoor,vapourpressurewillimmediatelylowerasthe
volumeexpands.Thenwaterdropwillevaporatetotrytoreachvapourpressure.Mostof
thetimevolumeistoobig(bighouseoreventheearthatmosphereifyouopenthewindow
ofyourhouse)sowaterdropswilltotallyevaporatewithoutbeingabletoreachvapour
pressure.
Boilingpointonlymeansthatthereissomuchagitation(keepinmindtemperature=
agitation)liquidwatercan'texistandturnsintovapoureveninsideavolumeofliquid
vapour(itformsbubblesofwatervapour)
Written30Jul2013ViewUpvotes
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AravindRavikumar
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Vaporizationofaliquidisaphasetransitionfromtheliquidphasetovapor.
Evaporationofaliquidisaphenomenonthatoccursfromthesurfaceofaliquidintoa
gaseousphasethatisnotsaturatedwiththeevaporatingsubstance.
Waterbecomingsteamat100degreecentigradeisvaporization,whilewaterinpondsgets
evaporated.
Asubstancevaporizesonlyataparticulartemperatureataparticularpressure(called
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boilingpoint),whilealiquidcanevaporateatanytemperature.
DifferenceBetweenEvaporationandVaporization

Written22Mar
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