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S:Solid

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

Constructof Txy orPxy diagramsandusethemtodeterminebubblepointsanddew


pointsandphaseamountsandcomposition

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

100 130 374.3

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

100 130 374.3

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
*

Plotof ln P* vsersus1/T (orasemilog plotof P* versus1/T)shouldbeastraightline


withslope v/Randintercept B.
Example:Thevaporpressureismeasuredattwotemperatures,withthefollowingresults:
T1 =7.6oC,
P1*=40mmHg,
T2=15.4oC,
P2*=60mmHg.
CalculatethelatentheatofvaporizationandtheparameterBinthe ClausisClapeyronequation.
Solution

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,

= (- 4211.14)(8.314)= 35 103 J/mol


DH
v

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

FromTableB.3, PH*2O = 289 mmHgatT = 75 oC


289
= 0.380mol H2O/mol
760
yDryair = 1- yH2O = 0.620moldryair/mol
yH2O =

1. Ifagasliquidsystemisatequilibrium,thegasmustbesaturatedwiththevolatilecomponentsof
thatliquid.
2. Atequilibrium,thepartialpressureofacomponent iinthegasphasecannotexceedsitsvapor
pressureatthesystemtemperature.
3. Avaporpresentinagasphaseinlessthanitssaturationamountisreferredtoasasuperheated
vapor.Forsuchavapor.
*

Pi = P.yi < Pi (T)

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

PH2O =P.yH2O = (5260)(0.1)= 526 mmHg

fromTableB.3, thevapor pressureof H2Oat100is


Since PH2O < PH*2O(100oC)

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)

Raoult' s law at outlet:

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:

100=n1 +n2 100=n1 +96.5 n1 =3.5molH2Ocondensed

3.5 condensed
Percentage condensation=
100 = 35%
(100)(0.1) mol H2O fed

3
Initially

yH2O .P < PH*2O(100 oC)

So,the vapor will be saturated when P is high enough


for the ineqality become equality,

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)

Raoult's law at outlet:

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)

Relative Saturation(Relative Humidity)

Sr (hr ) =

molal Saturation(molal Humidity)

Sm(hm) =

Pi
moles of vapor
=
P- Pi molesof Dry gas

Absolute Saturation(Absolute Humidity)

Sa(ha) =

PiMi
mass of vapor
=
(P- Pi)MDry gas massof Drygas

Percentage Saturation(Percentage Humidity)

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

From Table B.3 PH* 2O(75oC)= 289 mmHg


Q

hr =

PH2O

100% 0.30=
PH*2O(75oC)

(825)(yH2O )
289

yH2O = 0.105molH2O/mol

Themolar flowrateof wetairis givenbyideal gasEOSas follows

(1.1)(1000)
PV
=
= 38.0 kmol/h
RT (0.08314)(75+ 273.15)
Then

n=

nH2O = (38.0)(0.105)= 3.99kmolH2O/h

nDryair = (38.0)(1- 0.105)= 34kmolDryair/h

nO2 = (34.0)(0.21)= 7.14kmolO2/h

Humidair
75oC,P=1.1bar
hr =30%
V=1000m3

2
molal Humidity(hm )=

moles of water vapor 3.99


=
= 0.117molH2O/molDryair
molesof Dry air
34

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 ]

2.00lbm SO2/100lbm liquidwater

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 =

Threeunknownn1,n2,n3 with3independentbalance.Sothesystemisdeterminate (i.e.,solvable)

AirB. (100)(0.55)=(n3)(0.726) n3 =75.7lbmole/h[outletgasstream]


For100lbm waterthereis2lbm massSO2 sothecompositionofthisstreamis
Compositionof
Liquideffluent

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

n1 =n2 (0.9804)+n3 (0.0416)(18)


n1 =(89593.6)(0.9804)+(75.7)(0.0416)(18) n1 =87894.25lbm H2O/h

ionS
O2 A
bso
r b ed

bsorbed/
a

O
S

2
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=1756.0 m
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6
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89593.6
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6
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d=(n2) (0
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b
a
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S O 2
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b
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fed
880 m

O
=

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)
4

2
6
b
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(

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)
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m
absorbe
100)(0.45

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l

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880)=0.
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6
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S O 2

RaoultsLaw and HenrysLaw


1.Foramulticomponentgasliquidsystematequilibriumthe
compositionsofthetwophasesatagiventemperatureand
pressurearenotindependent.

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

Henrysconstantforethaneinwaterat20oC is2.63x104 atm/mole(Perrys,p2126)


Since yA.P = xA.HA(T)
\

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)

PB = xB . PB*(T)= (0.5)(119.5)= 59.75 mmHg


PT = xT . PT*(T)= (0.5)(36.7)= 18.35 mmHg

Then P= PB + PT = 59.75 + 18.35= 78.1 mmHg


yB = PB/ P = 59.75/78.1= 0.765molebenzene/mol
yT = PT / P = 18.35/78.1= 0.235moletoluene/mol