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ANINTRODUCTIONTOSATURATED
VAPOURPRESSURE

Thispagelooksathowtheequilibriumbetweenaliquid(ora
solid)anditsvapourleadstotheideaofasaturatedvapour
pressure.Italsolooksathowsaturatedvapourpressurevaries
withtemperature,andtherelationshipbetweensaturatedvapour
pressureandboilingpoint.

Theoriginofsaturatedvapourpressure

Theevaporationofaliquid

Theaverageenergyoftheparticlesinaliquidisgovernedby
thetemperature.Thehigherthetemperature,thehigherthe
averageenergy.Butwithinthataverage,someparticleshave
energieshigherthantheaverage,andothershaveenergies
lowerthantheaverage.

Someofthemoreenergeticparticlesonthesurfaceoftheliquid
canbemovingfastenoughtoescapefromtheattractiveforces
holdingtheliquidtogether.Theyevaporate.

Thediagramshowsasmallregionofaliquidnearitssurface.

Noticethatevaporationonlytakesplaceonthesurfaceofthe
liquid.That'squitedifferentfromboilingwhichhappenswhen
thereisenoughenergytodisrupttheattractiveforces
throughouttheliquid.That'swhy,ifyoulookatboilingwater,you
seebubblesofgasbeingformedallthewaythroughtheliquid.

Ifyoulookatwaterwhichisjustevaporatinginthesun,you
don'tseeanybubbles.Watermoleculesaresimplybreaking
awayfromthesurfacelayer.

Eventually,thewaterwillallevaporateinthisway.Theenergy
whichislostastheparticlesevaporateisreplacedfromthe
surroundings.Asthemoleculesinthewaterjostlewitheach

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other,newmoleculeswillgainenoughenergytoescapefrom
thesurface.

Theevaporationofaliquidinaclosedcontainer

Nowimaginewhathappensiftheliquidisinaclosedcontainer.
Commonsensetellsyouthatwaterinasealedbottledoesn't
seemtoevaporateoratleast,itdoesn'tdisappearovertime.

Butthereisconstantevaporationfromthesurface.Particles
continuetobreakawayfromthesurfaceoftheliquidbutthis
timetheyaretrappedinthespaceabovetheliquid.

Asthegaseousparticlesbouncearound,someofthemwillhit
thesurfaceoftheliquidagain,andbetrappedthere.Therewill
rapidlybeanequilibriumsetupinwhichthenumberofparticles
leavingthesurfaceisexactlybalancedbythenumberrejoining
it.

Inthisequilibrium,therewillbeafixednumberofthegaseous
particlesinthespaceabovetheliquid.

Whentheseparticleshitthewallsofthecontainer,theyexerta
pressure.Thispressureiscalledthesaturatedvapour

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pressure(alsoknownassaturationvapourpressure)ofthe
liquid.

Measuringthesaturatedvapourpressure

Itisn'tdifficulttoshowtheexistenceofthissaturatedvapour
pressure(andtomeasureit)usingasimplepieceofapparatus.

Note:Thisexperimentismucheasiertotalkaboutthando,
giventhesafetyproblemsinhandlingmercurybecauseofits
poisonousvapour.Thisisparticularlygoingtobeaproblemif
youwanttofindthesaturatedvapourpressureofaliquidata
highertemperature.Youwouldhavetouseamorecomplex
bitofapparatus.Thatisn'taproblemyouneedtoworryabout
forUKAlevelpurposes.

Ifyouhaveamercurybarometertubeinatroughofmercury,at
1atmospherepressurethecolumnwillbe760mmtall.1
atmosphereissometimesquotedas760mmHg("millimetresof
mercury").

Ifyousquirtafewdropsofliquidintothetube,itwillrisetoform
athinlayerfloatingontopofthemercury.Someoftheliquidwill
evaporateandyouwillgettheequilibriumwe'vejustbeen
talkingaboutprovidedthereisstillsomeliquidontopofthe
mercury.Itisonlyanequilibriumifbothliquidandvapourare
present.

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Thesaturatedvapourpressureoftheliquidwillforcethe
mercuryleveldownabit.Youcanmeasurethedropandthis
givesavalueforthesaturatedvapourpressureoftheliquidat
thistemperature.Inthiscase,themercuryhasbeenforced
downbyadistanceof760630mm.Thesaturatedvapour
pressureofthisliquidatthetemperatureoftheexperimentis
130mmHg.

YoucouldconvertthisintoproperSIunits(pascals)ifyou
wantedto.760mmHgisequivalentto101325Pa.

Avalueof130mmHgisquiteahighvapourpressureifweare
talkingaboutroomtemperature.Water'ssaturatedvapour
pressureisabout20mmHgatthistemperature.Ahighvapour
pressuremeansthattheliquidmustbevolatilemolecules
escapefromitssurfacerelativelyeasily,andaren'tverygoodat
stickingbackonagaineither.

Thatwillresultinlargernumbersoftheminthegasstateonce
equilibriumisreached.

Theliquidintheexamplemusthavesignificantlyweaker
intermolecularforcesthanwater.

Thevariationofsaturatedvapourpressurewith
temperature

Theeffectoftemperatureontheequilibriumbetweenliquid
andvapour

Youcanlookatthisintwoways.

Thereisacommonsenseway.Ifyouincreasethetemperature,
youareincreasingtheaverageenergyoftheparticlespresent.
Thatmeansthatmoreofthemarelikelytohaveenoughenergy

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toescapefromthesurfaceoftheliquid.Thatwilltendto
increasethesaturatedvapourpressure.

OryoucanlookatitintermsofLeChatelier'sPrinciplewhich
worksjustaswellinthiskindofphysicalsituationasitdoesin
themorefamiliarchemicalexamples.

Note:Youcouldfollowthislinkifyouaren'tsureaboutLe
Chatelier'sPrinciple.

UsetheBACKbuttononyourbrowsertoreturntothispage
later.

Whenthespaceabovetheliquidissaturatedwithvapour
particles,youhavethisequilibriumoccurringonthesurfaceof
theliquid:

Theforwardchange(liquidtovapour)isendothermic.Itneeds
heattoconverttheliquidintothevapour.

AccordingtoLeChatelier,increasingthetemperatureofa
systeminadynamicequilibriumfavourstheendothermic
change.Thatmeansthatincreasingthetemperatureincreases
theamountofvapourpresent,andsoincreasesthesaturated
vapourpressure.

Theeffectoftemperatureonthesaturatedvapourpressure
ofwater

Thegraphshowshowthesaturatedvapourpressure(svp)of
watervariesfrom0Cto100C.Thepressurescale(thevertical
one)ismeasuredinkilopascals(kPa).1atmospherepressureis
101.325kPa.

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Saturatedvapourpressureandboilingpoint

Aliquidboilswhenitssaturatedvapourpressurebecomesequal
totheexternalpressureontheliquid.Whenthathappens,it
enablesbubblesofvapourtoformthroughouttheliquidthose
arethebubblesyouseewhenaliquidboils.

Iftheexternalpressureishigherthanthesaturatedvapour
pressure,thesebubblesarepreventedfromforming,andyou
justgetevaporationatthesurfaceoftheliquid.

Iftheliquidisinanopencontainerandexposedtonormal
atmosphericpressure,theliquidboilswhenitssaturatedvapour
pressurebecomesequalto1atmosphere(or101325Paor
101.325kPaor760mmHg).Thishappenswithwaterwhenthe
temperaturereaches100C.

Butatdifferentpressures,waterwillboilatdifferent
temperatures.Forexample,atthetopofMountEverestthe
pressureissolowthatwaterwillboilatabout70C.
DepressionsfromtheAtlanticcaneasilylowertheatmospheric
pressureintheUKenoughsothatwaterwillboilat99Ceven
lowerwithverydeepdepressions.

Wheneverwejusttalkabout"theboilingpoint"ofaliquid,we
alwaysassumethatitisbeingmeasuredatexactly1
atmospherepressure.Inpractice,ofcourse,thatisrarely
exactlytrue.

Saturatedvapourpressureandsolids

Sublimation

Solidscanalsoloseparticlesfromtheirsurfacetoforma
vapour,exceptthatinthiscasewecalltheeffectsublimation
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ratherthanevaporation.Sublimationisthedirectchangefrom
solidtovapour(orviceversa)withoutgoingthroughtheliquid
stage.

Inmostcases,atordinarytemperatures,thesaturatedvapour
pressuresofsolidsrangefromlowtovery,very,verylow.The
forcesofattractioninmanysolidsaretoohightoallowmuch
lossofparticlesfromthesurface.

However,therearesomewhichdoeasilyformvapours.For
example,naphthalene(usedinoldfashioned"mothballs"to
deterclothesmoths)hasquiteastrongsmell.Moleculesmust
bebreakingawayfromthesurfaceasavapour,because
otherwiseyouwouldn'tbeabletosmellit.

Anotherfairlycommonexample(discussedindetailonanother
page)issolidcarbondioxide"dryice".Thisneverformsa
liquidatatmosphericpressureandalwaysconvertsdirectlyfrom
solidtovapour.That'swhyitisknownasdryice.

Note:Thislinkwilltakeyoustraighttothepageaboutphase
diagramswherethisisdiscussedindetail.Followthislinkas
wellifyouareinterestedinthelogicalnextstepinthistopic
whichisadiscussionofthephasediagramsofpure
substances,includingwaterandcarbondioxide.

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JimClark2004(modifiedJanuary2014)

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