PressureCookerandThermodynamics

ReferenceReading: M.Galleano,A.Boveris,andS.Puntarulo,J.Chem.Educ.,85,(2),276278,2008 Objective: 1.TounderstandtheClausiusClapeyronEquationbystudyingthePressure Cooker. 2.Toconnecteverydaylifeexperiencewithconceptsinthermodynamics. HowDoesaPressureCookerWork? Aliquidboilswhenthevaporpressureofthe gasescapingfromtheliquidisequaltothepressure exertedontheliquidbyitssurroundings(Pvap=Pext). Asaconsequence,theboilingpointcanbe manipulatedbyincreasingtheexternalpressure.In aregularcooker,waterisexposedtonormal externalpressure(normalbarometricpressure= 101kPa)andboilsat100C(373K).Whenthelidis notinitspositionorthevalveisuncovered(Fig.2A), thepressurecookerworksasaregularcooker. However,ifthevalveiscoveredtherewillbea changeintheinnerpressureofthechamberandthe liquidvaporequilibriumpointwillbedisplaced(Fig 2b).Whenthevalveiscovered,theconditionofthe systemchangesbecausethevaporphaseisnow restrictedtothechamber.Asaconsequenceofthe addedmass(thevalvelid),thepressureraisesand theequilibriumbetweenphasesisdisplacedtoa highertemperature,resultinginanewboilingpoint (Fig.2C).Themassofthevalveliddeterminesthe pressureinsidethechamberbecausetheholeofthe

valveletsgasescapewhenthepressureexceedssomefixedvalue.Excess pressureiseliminatedthroughsmallquantitiesofvaporescapingthroughthe valve(Fig.2D)establishingasituationofintermittentconstantvolume(Fig2C and2D). HowToVerifytheClausiusClapeyron Equation? Waterisheatedinthepressure cookerunderdifferentpressuresbyadding varyingwasherstothevalvelid.Firstwater heatingstartswiththevalveuncovered. Priortocoveringthevalvethechamber mustbepurgedorcleansedtoensurethe absenceofair.Whenwaterboils,vaporwill displacetheairandafterafewminutesthe vaporescapingthroughtheholeofthevalve becomescontinuous,indicatingthatonly waterisinthechamber.Atthispoint,the valvelidisplacedonthevalveandthenew pressureandtemperatureofthetransitionprocessaremeasured.Afterreaching thisnewequilibrium,theheatsourceisremovedforfiveminutes,awasheris placedonthevalvelid,andtheheatingisrestarteduntilthenextequilibrium pointisreached.Attheendof4or5additionsorexchangesofdifferentwahers studentshaveacorrelationbetweenthemassofthemodifiedvalvelidandthe measuredpressureandtemperature,asshowinTable1. AccordingtotheClausiusClapeyronequation,

herePisthemeasuredpressure(gaugevalueandatmosphere),Tisthe measuredtemperature,Risthegasconstant,andcisavariable,aplotoflnP versus(1/T)resultsinastraightlinewithaslopeof isthe enthalpyofvaporizationthatmaybetakenasconstantoverasmalltemperature range).UndertheconditionsshowninFig.3,therelationshipwasverifiedand wasestimatedas .Theuncertaintyintheslopeis calculatedaccordingtoref2.Theexperimentalvaluecomparesfavorablywith thevaluefromtables(40.4kJ/mol).