Professional Documents
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G:gas
MultiphaseSystems
L:Liquid
SL,GL,GS,LL, ..etc.
..etc.
Bytheendofthischapteryoushouldknowandunderstandthefollowingterms
1
Separationprocess( Distillation,absorption,scrubbing,liquidextraction,
crystallization,adsorptionandleaching)
Sketchthephasediagram(Pvs.T)forasinglespeciesandfullylabelallthe
regionsandpoints..etc
TheAntoineequation,theCoxchartandtheClausiusClapeyron equation :
theirapplicationandhowtousethemtoestimatethevaporpressureat
3
aspecifiedT,ortheboilingpointatspecifiedP.etc
4 Intensiveandextensivevariablesgivingexamplesofeach
5 Gibbsphaserule:todetermineNo D.Fformulticomponentandmultiphasesystem
Explainthemeaningofthefollowingterms:saturatedvapor,superheated
vapor, dewpoint, degreeofsuperheat, relativesaturationandrelativehumidity
RaoultslawandHenrys:writeandclearlyexplaintheirformula,definition,and
theirapplications.Explainthemeaningofthetermidealsolutionbehavior
Bubblepoint,boilingpointanddewpointofamixtureandtheircalculationsat
specificconditionsofcomposition,pressure/temperature
10
Explaininyourownwordsthefollowingterms
Solubility.Saturatedsolution.hydratesalt..
distributioncoefficient adsorptionisothermand
theircalculations .etc
Introduction
1. Almostallchemicalprocessinvolveoperationsinwhichmaterial
istransferredfromonephaseintoanother
2. Separationprocessaredesignedtoseparatethecomponentsofmixturefromone
another.Mostseparationoperationsinvolvethetransferofspeciesbetweentwo
phases.Ingeneral,theseparationtechniquesareachievedbyenhancingtherate
ofmasstransferofcertainspeciesrelativetomasstransferof allspecies.
Herearesome
Herearesome
examplesof
examplesof
multiphase
multiphase
separation
separation
process
process
Leaching
Extraction
Absorption
Distillation
Crystallization
Adsorption
Leaching
Itistheoperationconcernedwiththeextractionofasoluble
component(constituent)fromasolidphasebymeansofaliquidsolvent.
Thesolidsaregroundandbroughtintocontactwithaliquidsolvent,thesoluble
componentofthesolidistransferredfromthesolidphaseinto theliquidphase
Then,theresidualsolidsarefilteredfromthesolution.
Anexampleofleachingistheextractionofvegetableoilsfromseeds.
Extraction
Itistheoperation,inwhichtheconstituentsofaliquidmixtureare
separatedfromeachotherbyblendingitwithanotherliquidsolvent.
Thissolventhastheabilitytodissolveoneormorecomponentofthemixture.
Anexampleistheseparationof paraffinic andaromatichydrocarbons.
Seeexample4.42&problem4.7,
Absorptionor
Scrubbing
Theremovalofoneormoreselectedcomponentsfromamixtureofgases
byabsorptionintoasuitableliquid.
Anexampleistheremovalofsulfurdioxidefromacombustionproductgas
Distillation
Distillationsprocess,areusedtoseparatethecomponentsofamixture
fromeachotherdependingonthedifferenceintheirboilingpoints.On
otherwordsitistheseparationofthelowvolatilecomponents(LVC)
fromhighvolatilecomponents(HVC)whichhasagreatertendency to
vaporize.Therefore,distillationexploitsthisdifferencebypartially
vaporizingaliquidmixture.
Anexampleistherecoveryofmethanolfromanaqueoussolution, and
thedistillationofcrudeoil.
Crystallization
Crystallizationutilizethedifferenceinfreezingpointsand
bycoolingthemixturetoatemperatureatwhichcrystals
ofonecomponentcomeoutofthesolution.Seeexample
4.52andproblem434
Adsorption:
Isusedtoseparate(remove)componentspresentinliquidor
gasmixturebyselectiveadsorptiononsolids.
No t
etha
1. Whenaspeciestransfersfromonephaseto
another,thetransferrategenerallydecreaseswith
timeuntilthesecondphaseissaturatedwiththe
species,holdingasmuchasitcanholdatthe
processconditions.
2. Whentheconcentrationsofallspeciesineach
phasenolongerchangewithtime,thephasesare
saidtobeinphaseequilibrium.
Single
Component
Phase
Equilibrium
1. Singlepuresubstanceexistsassolid,liquid,orgas(i.,e.,singlephase)
2. Twoandevenallthreephasesmaycoexistatcertainconditions of
temperatureandpressure.
a.)Waterisagasat130oCand100mmHg.
for
b.)Whileat 40oCand10atmisasolid
exam
ple
c.)Butat100oCand1atmitmaybeagas,
aliquidoramixtureofboth.
d.)at 0.0098oCand4.58mmHgmaybeasolid,
aliquid,agasoranycombinationofthethreephases.
Theaboveinformationisfoundoutfromwaterphasediagram
Phase
D i ag r
a m
1. Itisaplotofonesystemvariableagainstanotherthatshowsthe
conditionsatwhichthesubstanceexistsasasolid,aliquid,andagas.
2. Themostimportantofthesediagramsistheplotofpressureonthe
verticalaxisversusTonthehorizontalaxis.
3. Theboundariesbetweenthesinglephaseregionsrepresentthe
pressuresandtemperaturesatwhichtwophasesmaycoexist.
F=forceonpiston
PhaseDiagramofwater
1. Purewaterisplacedinanevacuatedcylinderfitted
withamovablepiston,asshowninfigure.
2. Heatcanbeaddedorwithdrawnfromthecylinder,
sothatthetemperaturecanbeadjustedtoanydesired
value.
3. Theabsolutepressureofthecylindercontentsequals
(F+W)/A,cansimilarlybeadjustedbyvaryingthe
forceFonthepiston
A=areaof
thepiston
W=weightof
thepiston
H2Ovapor
H2OLiquid
3. However,atdifferentconditionsofpressuresandtemperatures,the
statesofwaterarenoticedandtheconditionsarerecorded,sothatthe
phasediagramofwatercanbeconstructed.
Forexample:
Supposethesystemisinitiallyat20oCandtheissetatavaluesuch
thatthepressureis3.0mmHg.
Anyliquidwaterthatmayinitiallyhavebeeninthecylinder
evaporates,untilfinallythecylindercontainsonlywatervapor.
Sothat,watercanonlyexistasavaporattheseconditions(seewater
phasediagram,pointA,nextslide).
Nextslide,showsthephasediagramofwater,inwhichpointsA,B,C,D,E ,
representdifferentconditionsatvariousstagesoftheprocess.
Point T,oC
P,mmHg
state
20
20
17.54
20
760
100
760
L+V
130
760
L+V
PhaseDiagrams
Supercriticalpoint
Criticalpoint
218.3atm
Point
Liquid
Solid
760mmHg
17.535mmHg
4.58mmHg
T,oC
P,mmHg
state
20
20
17.54
20
760
100
760
L+V
130
760
V
L+V
Gas
Vapor
3mmHg
A
Liquid
5 0.0098
20
T,oC
vapor
Liquid
vapor
H2O
vapor
PointB
20 C,17.54mmHg
o
PointE
130oC,760mmHg
PointA
20oC,3mmHg
Triple
point
vapor
vapor
vapor
Liquid
PointD
o
100 C,760mmHg
Liquid
Liquid
PointC
20 C,760mmHg
o
Supercriticalpoint
Notethat:
Criticalpoint
218.3atm
Liquid
1. Phasetransitionlikecondensationatpoint Band
evaporationatpointD,takeplaceatboundarieson
thephasediagramsuchthatthesystemcannot
moveofftheseboundariesuntilthetransitionsare
complete.
Solid
760mmHg
17.535mmHg
4.58mmHg
Triple
point
Gas
Vapor
3mmHg
A
5 0.0098
20
T,oC
2. Foranypointfallsonthevaporliquidcurve
equilibrium,Pisthevaporpressureofthe
substanceattemperatureT,whileTistheboiling
pointtemperatureatpressureP.
3. Theboilingpointofasubstance
atP=1atmisthenormal
boilingpoint
4. Forapoint(T,P)fallsonthesolidliquidequilibriumcurve,thenT isthemeltingpoint
orfreezingpointatpressure P.
5. If,point(T,P)fallsonthesolidvaporequilibriumcurve,then Pisthevaporpressureof
thesolidattemperatureT,andT isthesublimationpointatpressureP.
6. Thepoint(T,P)atwhichthethreephasesarecoexistiscalledthetriplepointofthe
substance
7. TheVaporliquidcurveterminatesatthecriticaltemperatureandcriticalpressure
(Tc and Pc).Aboveandtotherightofthecriticalpoint,twophasesnevercoexist.
Estimationofvaporpressure
1. Volatility ofaspeciesisthedegreetowhichittends
totransferfromliquid(orsolid)tovaporstate.
2. MoreVolatileComponent(MVC) ismuchmore
likelytobefoundasavapor.
Introduction
3. LessVolatileComponent(LVC) ismorelikelyto
befoundincondensedphase(liquidorsolid)
4. Vaporpressureofaspecies isameasureofits
volatility.Thehigherthevolatilitythehigherthevapor
pressure.
5. Sometimesthetabulatedvaporpressuresdata
arenotavailable attemperaturesofinterest,or
theymaynotavailableatallforagivenspecies.
So,thealternativewayistoestimatethevapor
pressuresusingempiricalcorrelation.
Methodsofestimatingvaporpressure
1.ClausiusClapeyronEquation
2.CoxCharts(figure6.14,p247)
3.Antoineequation
1
ClassiusClapeyronEquation
Equation
ClassiusClapeyron
DH
v
ln p =+ B
RT
*
Where:
P* isVaporpressure
isLatentheatofvaporization.
T
istemperature(absolute)
R isuniversalgasconstant
B isconstantforthecomponent
AccordingtoClausiusClapeyron Equation
DH
lnp =- v + B
RT
*
Theslopeofthelinethroughthetwodatapointsonaplotof ln P*versus1/Tis
DH
ln(P2* /P1* )
ln(60/40)
v
-
=
=
= - 4211.14K
1 1
1
1
R
+
T2 T1
15.4+ 273.15 7.6+ 273.17
DH
v
B = lnP +
= ln(40)+ (4211.14/280.0) = 18.69
RT1
*
1
lnP* =-
4211.14
+ 18.69
T
DH
- v = - 4211.14
R
Since,
ThetruevaluelistedinTableB.1is 31000J/mol
Q
4211.14
42.2+ 273.15= 315.35K
+ 8.69
\ at
T=
T
4211.14
lnP* = + 8.69 = 5.336
P = 207.7mmHg
315.35
lnP* = -
2
AntoineEquation
AntoineEquation
B
log10 p = AT + C
*
Where:
P*isVaporpressure
Tistemperature
A,BandCareconstantsforthecomponent.
ValuesaregiveninTableB4onpage640
3
CoxChart
CoxChart
Coxchartofvaporpressuresforvarioussubstance
areshowninfigure6.14.Inwhich,LogP* on
theordinateandthetemperatureontheabscissa.
1. Whentwophasesarebroughtintocontactwitheachother,aredistributionofthecomponentsof
eachphasetakesplaceuntilastateofequilibriumisreached.
2. Atequilibrium,temperaturesandpressuresofbothphasesarethesameandthecompositionof
eachphasenolongerchangeswithtime.
3. Thevariablesthatdescribetheconditionofaprocesssystemfallintotwocategories:
Intensivevariables: Variablesthatdonotdependonthequantity(size)ofthesysteme.g.
temperature,pressure,density,molecularweight,massandmole fractions...etc.
Extensivevariables: Variablesthatdependonthequantityofthesysteme.g.mass,volumeetc.
4. Degreeoffreedom:Thenumberofindependentintensivevariablesneededtospecify thesystem
inequilibriumiscalleddegreesoffreedom.ItisdefinedbytheGibbsphase
ruleasfollows:
DF =2 + c-
Where:
DF:Degreeoffreedomofthesystem.
:numberofphasesinasystematequilibrium.
c:numberofchemicalspecies.
Notethat:Forthesystemsincludingchemicalreactions
If(r)istheindependentreactionsoccuramongthesystemcomponentsand
thereactionsproceedtoequilibrium,thentherighthandsideofphaserule
mustbereducedby(r).So,
DF =2+ c- r-
ThemeaningofthetermdegreeoffreedomintheGibbsphaseruleissimilartoitsmeaningin
thedegreeoffreedomanalysisdiscussedin Ch4.
InCh4,thedegreeoffreedomrepresents thenumberofprocessvariablesthatmustbe
specifiedforaprocesssystembeforetheremainingvariablescanbecalculated.
IntheGibbsphaserule, thedegreeoffreedomequalsthenumberofintensivevariables
thatmustbespecifiedforasystematequilibriumbeforeremainingintensivevariablescan
becalculated.
Herearesomeexamplesfordeterminingthedegreeoffreedomforthesystemsat
equilibriumandforspecifyingafeasiblesetofindependentvariablesforeachsystem.
DF =2+ c-
DF =2+ c- r-
NoChem.reactions
WithChem.reactions
System
c DF
feasiblesetofindependentvariables
Pureliquidwater
1 1
Twointensivevariablesmustbespecified,forexampleTand
P.Oncethesevariableshavebeenspecified,otherintensive
variablesuchas,canbedetermined.
Amixtureofliquid,solidand
vaporwater
3 1
Nofurtherinformationneededandallintensivevariablesare
fixed.(notefromwaterphasediagramthatthethreephases
coexistatequilibriumatonlyonetemperatureandpressure)
Avaporliquidmixtureof
acetoneandmethylethylketone
2 2
Twovariablemustbespecifiedtofixthestateofthesystem.
Forexample,settingTandPfixestheacetoneandMEKmole
fractioninbothvaporandliquidphases.
Or,settingTandacetonemolefractioninvaporphasefixesP
theacetonemolefractionintheliquidphase.
AgaseousmixtureofH2,Br2,
andHBr,giventhethisreaction
H2 +Br2 2HBr
1 3
TherighthandsideofGibbsphaseruleisreducedby(r=1),
whichisthenumberofindependentreaction
Avaporliquidmixtureoffour
hydrocarbons
2 4
Onecondensablecomponent
concernedwiththesystemscontainingseveralcomponents
andonlyoneofthemiscapableofexistingasaliquid
attheprocessconditions.
1. Separationprocesslikeevaporation, drying,and
humidificationinvolvegasandliquidphaseincontact,in
whichtransferofliquidintogasphaseoccurs.
2. Whileseparationprocesslikecondensationand
dehumidificationinvolvetransferofcondensablecomponents
fromthegastotheliquidphase.
3. Saturatedgas:itisthegascontainsalltheliquiditcanholdat
thesystemtemperatureandpressure,andtheliquidinthegas
phaseisreferredtoasasaturatedvapor.
Raoults
law
Thelawthatdescribesthebehaviorofgasliquidsystemsovera
widerangeofconditions.
Forsinglecondensablespecies
Pi = yi.P= Pi*(T)
Thismeansthatifagascontainsasaturatedvaporwhosemolefractionisyi andifthis
vaporistheonlyspeciesthatwouldcondenseifthetemperaturewasslightlylowered,the
partialpressureofthevaporinthegasequalsthepurecomponentvaporpressureatthe
systemtemperature.
MulticomponentGasLiquidSystem
Systemscontainstwoor
morecondensable
components
*
i i
P
P= x.P(T)
i =y
i.
Example:Airandliquidwaterarecontainedatequilibriuminaclosedchamberat75oCand760mm
Hg.Determinethedegreeoffreedomandthemolarcompositionofthegasphase.?
Soln
Sincetherearetwophasesandtwocomponents
Then
DF=2+c =2
Raoultslawmaybeapplied
yH2O.P=PH*2O
yH2O =
PH*2O
P
1. Ifagasliquidsystemisatequilibrium,thegasmustbesaturatedwiththevolatilecomponentsof
thatliquid.
2. Atequilibrium,thepartialpressureofacomponent iinthegasphasecannotexceedsitsvapor
pressureatthesystemtemperature.
3. Avaporpresentinagasphaseinlessthanitssaturationamountisreferredtoasasuperheated
vapor.Forsuchavapor.
*
Eq.(1)
4. Toachievethesaturationconditionforthesystemscontaininga superheatedvapor,oneor
morevariablesoftheequation(1)mustbechanged,sothatthe inequalitybecomesequalityof
Raoultslaw.Thiscanbedonebyincreasingthepressureatconstanttemperature,orby
decreasingthetemperatureatconstantpressure.
5. Ifagascontainingasinglesuperheatedvaporiscooledatconstantpressure,thetemperatureat
whichthevaporbecomessaturatedisreferredtoasthe dewpointofthegas.So,fromRaoults
law
*
Pi =P.yi = Pi (Tdp)
Eq.(2)
Thedifferencebetweenthetemperatureandthedewpointiscalledthedegreeofsuperheat.Ifanytwo
ofthequantitiesyi,PandTdp (or,equivalentlyTofthegasandthedegreeofsuperheat)are known,the
thirdquantitymaybedeterminedfromEq.(2)andtable,graphorequationrelating Pi* andT
Example:Astreamofairat100oC and5260mmHgcontains10.0%waterbyvolume.
1. Calculatethedewpointanddegreeofsuperheatoftheair.
2. Calculatethepercentageofthevaporthatcondensesandthefinalcompositionofthegas
phaseiftheairiscooledto80oC atconstantpressure.
3. Calculatethepercentagecondensationandthefinalcomposition ofthegasphaseif,insteadof
beingcooled,theairiscompressedisothermallyto8500mmHg.
4. Supposetheprocessofpart2isrun,theproductgasisanalyzed,andthemolefractionof
waterdiffersconsiderablyfromthecalculatedvalue.Whatcould beresponsibleforthe
disparitybetweencalculatedandmeasurevalues?(listseveralpossibilities)
Solution
1 Partial pressureof H O is
2
From Eq.
PH*2O(100oC)= 760mmHg
Thenthevaporissuperheated
Pi = yi .P= Pi*(Tdp)
*
So,thevaporwillbesaturated withPH2O
= 526 atT = 90 oC (seetableB.3)
Thenthedegreeofsuperheat=100 90=10oC
Sincetheairbecomessaturatedat90oC,furthercoolingmustleadtocondensation.
Basis: 100molfeedgas
100molfeedgas
n2 molairsaturatedwithwater
Condenser
0.1molH2O(v)/mol
ymolH2O(V)/mol
0.9molDA/mol
1ymolDA/mol
T=100 C,P=5260mmHg
Condensedwater
T=80oC,P=5260mmHg
n1 molH2O(L)
Degreeoffreedomanalysis:
3unknowns(n1,n2,y)
2massbalance
===========
Sincetheoutletgasissaturated,then
Raoultslawcanbeapplied
Then
DF=0
1DF
y.P= PH*2O(T)
y=
PH*2O(80oC)
P
355
= 0.0675 mol H2O/mol
5260
OverallDryAirBalance:
n2 =96.5mol.
(100)(0.9)=n2(1y)=n2 (10.0675)
Overallallmassbalance:
3.5 condensed
Percentage condensation=
100 = 35%
(100)(0.1) mol H2O fed
3
Initially
i.e.,
PH*2O(100oC) 760mm
Psaturation =
=
= 7600 mm Hg
yH2O
0.1
AnyincreaseinPabove7600mmHgmustcausecondensation
Basis: 100molfeedgas
100molfeedgas
0.1molH2O(v)/mol
n2 molairsaturatedwithwater
Condenser
ymolH2O(V)/mol
0.9molDA/mol
y1molDA/mol
T=100 C,P=5260mmHg
Condensedwater
T=100oC,P=8500mmHg
n1 molH2O(L)
y.P=PH*2O(T)
y=
PH*2O(100oC)
P
760
= 0.0894 molH2O/mol
8500
OverallDryAirBalance:
(100)(0.9)=n2(1y)=n2 (10.0894)
n2 =98.8mol.
Overallallmassbalance:
100=n1 +n2 100=n1 +98.8 n1 =1.2molH2Ocondensed
1.2 condensed
Percentage condensation=
100 = 12%
(100)(0.1) mol H2O fed
Seethebookp.252253.
Saturation&
Humidity
Thefollowingareimportantdefinitionsinwhich:
1. Theterm saturationreferstoanygasvaporcombination,while
2. Theterm humidityreferstoanairwatersystem
3. Soforgasattemperature T andpressure Pcontainsavaporwhosepartial
pressureisPi andvaporpressureis Pi*(T)
4. Thedefinitionsare:
Pi
100%
Pi*(T)
Sr (hr ) =
Sm(hm) =
Pi
moles of vapor
=
P- Pi molesof Dry gas
Sa(ha) =
PiMi
mass of vapor
=
(P- Pi)MDry gas massof Drygas
Sp(hp) =
Pi (P- Pi)
moles of vapor
=
*
*
Pi P- Pi
molesof Dry gas
Example:Humidairat75oC,1.1bar,and30%relativehumidityisfedintoaprocessunit
atarateof1000m3/h.Determine
(1) Themolarflowratesofwater,dryair,andoxygenenteringtheprocessunit.
(2) Themolalhumidity,absolutehumidity,andpercentagehumidityoftheair,and
(3) Dewpoint.
(1)
760mmHg
Since 1atm= 760mmHg= 1.01325 bar P= 1.1bar
= 825 mmHg
1.01325 bar
hr =
PH2O
100% 0.30=
PH*2O(75oC)
(825)(yH2O )
289
yH2O = 0.105molH2O/mol
(1.1)(1000)
PV
=
= 38.0 kmol/h
RT (0.08314)(75+ 273.15)
Then
n=
Humidair
75oC,P=1.1bar
hr =30%
V=1000m3
2
molal Humidity(hm )=
OR
molal Humidity(hm )=
PH2O
P- PH2O
86.6
= 0.117molH2O/molDryair
825- 86.6
PH2OMH2O
Absolute Humidity(ha) =
(86.6)(18.0)
= 0.073 kg H2O/kg Dryair
(825- 86.6)(29.0)
(P- P )M
P (P- P )
P (P- P )
Percentage Humidity(h ) =
100=
100=
P (P- P )
P (P- P )
H2O
Since
Dry air
H2O
H2O
H2O
*
H2O
*
H2O
*
H2O
*
H2O
H2O
86.6(825- 289)
100= 21.8%
289(825- 86.6)
PH O =86.6mmHg.
2
*
Thenmustequal=86.6mmHg
H2O dp
P (T )
FromTableB.3
Tdp =48.7oC
Multicomponent GasLiquidSystem
Example:Agasstreamconsistingof100lbmole/hofanSO2airmixturecontaining45mole
%SO2 iscontactedwithliquidwaterinacontinuousabsorberat30oC.Theliquidleavingthe
absorberisanalyzedandfoundtocontain2.00gofSO2 per100gofH2O.Assumingthatthe
gasandliquidstreamsleavingtheabsorberareinequilibriumat30oC and1atm,calculatethe
fractionofenteringSO2 absorbedinthewaterandtherequiredwaterfeedrate.Takethe
equilibriumpartialpressureofH2OandSO2 attheexitgasstreamas:PH O =31.6mmHg&
2
PSO =176mmHg
2
Solution
Basis:100lbmole/hfedgasstream
n1 lbm liquidwater/h
100lbmole/h
0.45lbmoleSO2/lbmole
Absorber
0.55lbmoleair/lbmole
Gasstream
n3 lbmole/h
yair lbmoleair/lbmole
yH O lbmoleair/lbmole
2
ySO lbmoleSO2/ibmole
2
n2 lbm/h
[water+SO2 ]
Equilibriumat
30oCand1atm
Thecompositionoftheexitstream:
Since Pi = yi.P
\
&
\
PH2O
yi =
Pi
P
31.6
= 0.0416 lbmoleH2O/lbmole
P
760
PSO2
176
ySO2 =
yH2O =
= 0.232 lbmoleSO2/lbmole
P
760
yair = (1- 0.0416- 0.232)= 0.726 lbmoleair/lbmole
yH2O =
yH2O =
2
xSO2 =
= 0.0196 lbm SO2/lbm
100+ 2
\ xH2O = 1- 0.0196= 0.9804lbm H2O/lbm
(100)(0.45)=(n2)(0.0196)+(n3)(0.232)
SO2 B. (100)(0.45)=(n2)(0.0196)+(75.7)(0.232) n2 =1399.9lbmol/h
n2 =(1399.9)(64)=89593.6 lbm/h
H2OB.
Fract
ionS
O2 A
bso
r b ed
bsorbed/
a
O
S
2
b
l
=1756.0 m
)
6
9
1
0
.
0
(
)
89593.6
(
)
6
9
1
0
.
d=(n2) (0
e
b
r
o
fed/h
s
b
a
O
S O 2
2
b
l
fed
880 m
O
=
S
)
4
2
6
b
l
(
/
)
d
m
absorbe
100)(0.45
O
=
2
e
b
f
l
6
m
S O 2
880)=0.
2
/
6
5
7
1
(
absorbed
n
o
i
t
c
a
r
f
S O 2
2.Thereforeoncethecompositionofonephasesisspecified,the
compositionoftheotherphaseisfixedandcanbedetermined
fromphysicalpropertiesofthesystemcomponents.
3.Thecompositionsmaybespecifiedintermsofmolefractions,
massfractions,concentrations,or,partialpressuresforvapor
phase.
4.ForsubstanceAcontainedinagasliquidsysteminequilibrium
attemperatureTandpressureP,RaoultslawandHenryslaw
providerelationshipsbetweenthepartialpressureof A(PA)in
thegasphase,andmolefractionof A(xA)intheliquidphase.
RaoultsLaw
TwomajorassumptionsaremadeforRaoultslaw:
a.)Thevaporphaseisanidealgas(i.e,appliedforlawtomoderatepressure)
b.)Theliquidphaseisanidealsolution(i.e.,thespeciesarechemicallysimilar)
Idealsolution: AsolutionthatcloselyobeysRaoultsandHenryslawforallitsconstituentspecies
Thespeciesarechemicallysimilarwhentheirmoleculesarenottoodifferentinsizesandofthe
samechemicalnature,i.e.,almostofsimilarmolecularweights.
ThemathematicalexpressionofRaoultslawis:
*
A
PA = yA .P= xA .P (T)
Where:
xA :molefractionofspeciesAinliquidphase
yA :molefractionofspeciesAinvaporphase.
PA* :vaporpressureofpurespeciesAatthetemperatureofthesystem
Theproduct yAPontheleftsideofRaoultsequationisthepartialpressureofspeciesA
LimitationofRaoultslaw: itisappliedonlytospeciesofknownvaporpressure,
i.e., thespeciesrequiredtobeatatemperaturebelowitscriticaltemperature.
Oronotherwords,thecriticaltemperatureofthespeciesisbelowthetemperatureof
thesystem
HenrysLaw
Henryslawisgenerallyvalidfor:
1. Vaporphaseisidealgas(lawtomoderatepressure).
2. Speciespresentasverydilutesoluteintheliquidphase(i.e., xAiscloseto0)
3. Specieswhosecriticaltemperatureislessthanthetempofapplication.
Henryslawstates thatthepartialpressureofaspeciesinthevaporphaseisdirectly
proportionaltoitsliquidphasemolefraction.
PA = yA .P= xA .H A(T)
Where
HA(T)istheHenryslawconstantforaspeciesA
Example:UseeitherRaoultslaworHenryslawtosolvethefollowingproblem:
1. Agascontaining1.00mole%ethaneisincontactwithwaterat20oCand20.0atm.
Estimatethemolefractionofdissolvedethane.
2. Anequimolarliquidmixtureofbenzene(B)andToluene(T)isin equilibriumwith
itsvaporat30.0oC.Whatisthesystempressureandcompositionofthevapor?
1
Solution Sincethehydrocarbonsarerelativelyinsolubleinwater,sothesolutionofethaneis
probablydilute.Therefore,Henryslawisappliedhere
xC2 H6 =
yC2H6 .P
HC2H6
(0.01)(20)
= 7.6 10-6molC2H6 /mol
4
2.63 10 atm/mole
2 BenzeneandToluenearestructurallysimilar,thenRaoultslawwillapplied.
UsingAntoineequationtoestimatethevaporpressures.TheconstantsA,B,Cofthe
AntoineequationarelistedintableB.4
B
T + C
log10 P = A-
log10 PB = 6.906-
&
1211
30+ 220.8
1343.9
log10 PT = 6.953330+ 219.38
PB = 119.5 mmHg
PT = 36.7 mmHg
Raoult's law :
\
Pi = yi . P = xi . Pi* (T)