1

Bin Liu
E5-02-17
Cheliub@nus.edu.sg
Chapter 6
Multiphase Systems
2
LearningObjectives
Understandseparation,distillation,absorption,extractionand
crystallization
Sketchaphasediagram
Estimatethevaporpressureofapuresubstance
Distinguishbetweenintensiveandextensivevariables
Understandsaturatedvapor,superheatedvapor,dewpoint,bubble
pointandboilingpoint
Raoults lawandHerrys law
Degreeoffreedomanalysis
UseTxy andPxy diagram
Explainsaturatedsolutionandhydratedsalt
Explaindistributioncoefficientandadsorptionisotherm
3
Phasechangeoperationsemployedonmixturesto
separatecomponentsorpurifyaproduct
Phasechangephenomenaandoperations
freezing
melting
evaporation
condensation
leaching
distillation
adsorption/scrubbing
crystallization
PhaseChangeOperations
4
Example:CO
2
Adsorption
5
Phaseequilibrium:theconcentrationsofallspeciesineach
phaseceasetochange
PhaseEquilibrium
6
Atmosttemperatures/pressures,
apuresubstanceexistsinasingle
phase:solid,liquid,orgas.
Atsomeconditions,twoorthree
phasesmaycoexist.
A phase diagram of a pure
substance is a plot system
variables that shows the
conditions at which the substance
exists in various phases.
PhaseDiagrams
7
SingleComponentPhaseDiagram
H
2
O
8
Severalterms:
1. IfTandPcorrespondtoapointonthevaporliquidequilibriumcurve
forasubstance,Pisthevaporpressure ofthesubstanceattemperature
T,andTistheboilingpoint ofthesubstanceatpressureP.
2. If(T,P)fallsonthesolidliquidequilibriumcurve,thenTismeltingpoint
orfreezingpoint atpressureP.
3. If(T,P)fallsonthesolidvaporequilibriumcurve,thenPisthevapor
pressureofthesolidattemperatureTandTisthesublimationpoint at
pressureP.
4. Thepoint(T,P)atwhichsolid,liquidandvaporphasescoexistiscalled
thetriplepoint ofthesubstance.
5. Thevaporliquidequilibriumcurveterminatesatcriticaltemperature
andcriticalpressure (T
c
,andP
c
).Aboveandtotherightofthecritical
point,twoseparatephasesnevercoexist.
9
EstimationofVaporPressure
10
Example: VaporpressureestimationusingtheClausiusClapeyron equation
T
1
=7.6C,p
1
*=40mmHg
T
2
=15.4C,p
2
*=60mmHg
CalculatethelatentheatofvaporizationandtheparameterBintheClausius
Clapeyron equationandthenestimatep*at42.2Cusingthisequation.
T
1
=7.6C=7.6+273.2=280.8K
T
2
=15.4C=15.4+273.2=288.6K
Theslopeofthelinethroughthetwodatapointsonaplotoflnp*versus
1/Tis
H
v
ln(p
2
*/p
1
*)
R [(1/T
2
) (1/T
1
)]
T
1
T
2
ln(p
2
*/p
1
*)
(T
1
T
2
)
= =

=
(280.8K)(288.6K)ln(60mmHg/40mmHg)
(280.8 288.6)K
= 4213K
Thevaporpressureofbenzeneismeasuredattwotemperatures:
27
B=lnp
1
*+=ln40+(4213/280.8)=18.69
H
v
RT
1
TheClausiusClapeyron equationistherefore
lnp*= +18.69 p*inmmHg
4213K
T(K)
Check:T=15.4C,288.6K
lnp*= +18.69=4.093
p*=exp(4.093)=60mmHg
Finally,atT=42.2C=315.4K
4213K
288.6
lnp*= +18.69=5.334p*=exp(5.334)=207mmHg
4213K
315.4
H
v
=4213Kx8.314J/molK=35030J/mol
12
CoxChart
Antoineequation
log
10
p*=A
B
T+C
WhereA,B,andCareempiricalconstantsuniquetoeachcompound
13
Intensivevariables(e.g.temperature,pressure,density,specific
volume,massfractionandmolefraction)donotdependuponthe
sizeofthesystem.
Extensivevariables(e.g.mass,volume)aresizedependent.
GibbsPhaseRule
Thenumberofintensivevariablesthatcanbespecifiedindependentlyfor
asystematequilibriumiscalledthedegreeoffreedom(DF)ofthe
system.Itisrelatedtothenumberofchemicalspecies(c),thenumberof
phases()inthesystematequilibriumandthenumberofreactions(r).
Ifnoreactionsoccur DF=2+c
Ifrindependentreactionsoccur, DF=2+c r
14
ApplicationofGibbsPhaseRule
Considerpureliquidwater
DF=2+c r
=2+1 1 0
=2
2intensivevariablesmaybe
specified,afterwhichother
intensivevariablesmaybe
determined.
15
ApplicationofGibbsPhaseRule
Considerthetriplepointofwater
DF=2+c r
=2+1 3 0
=0
Allintensivevariablesarefixedbythegiveninformation.
Considera2phaseliquid/vaporsystemofwater
DF=2+c r
=2+1 2 0
=1
1intensivevariablemaybespecified.
16
ApplicationofGibbsPhaseRule
Consideravapor/liquidmixtureofacetoneandmethylethyl
ketone
DF=2+c r
=2+2 2 0
=2
2intensivevariablesmaybespecified.
17
Systemsofmultiplecomponentsofwhichonly1maycondense
atprocessconditionsarecommon.
evaporation,drying,humidification allofwhichinvolvethe
transferofliquidtothegasphase.
condensationanddehumidificationinvolvethetransferofthe
condensablespeciesfromthegastotheliquidphase.
GasLiquidSystems:1condensable
18
Consideracontainerofdryairintowhichwaterisintroduced.
Waterevaporatesintotheair,resultinginanincreaseinyH
2
O
andpH
2
Ointhegasphase.
Evaporationcontinuesuntiltheairisasaturatedvapor(i.e.,
canholdnoadditionalwater)atTandPofthesystem.
FromGibbsPhaseRule,itfollowsthatonlytwoofT,P,and
yH
2
Ocanbeindependentlyspecified.
GasLiquidSystems:1condensable
DF=2+c r
=2+2 2 0
=2
19
Nonsoluble gas and liquid: Drying and evaporation
Variables: p, T and y
vapor
A gas at T and P contains a saturated vapor whose mole fraction is
y
i
(mol vapor/mol total gas), and if the vapor is the only species that
would condense if the temperature were slightly lowered, then the
partial pressure of the vapor in the gas equals the purecomponent
vapor pressure P
i
*(T) at the system temperature.
Raoults Law
Raoults lawforasingle
condensableliquid(e.g.
water)
p
i
=y
i
P=p
i
*(T)
20
ThingstoConsider
A gas in equilibrium with a liquid must be saturated with
the volatile components of the liquid.
The partial pressure of a vapor at equilibrium in a gas
mixture containing a single condensable component
cannot exceed the vapor pressure of the pure component
at the system temperature.
If p
i
= p
i
*(T), the vapor is saturated. Any attempt to
increase p
i
will result in condensation occurring.
21
SuperheatedVapor
A vapor present in a gas in less than its saturation amount is
referred to as a superheated vapor. For such a vapor,
p
i
= y
i
P < p
i
* (T)
If a gas containing a single superheated vapor is cooled at
constant P, the temperature at which the vapor becomes
saturated is referred to as the dew point.
From Raoults law, p
i
= y
i
P = p
i
*(T
dp
)
Difference (T T
dp
) is called degrees of superheat.
22
OtherMeansofExpressingSaturation
Relativesaturation
(relativehumidity)S
r
(h
r
)=x100%
Molarsaturation
(relativehumidity)S
m
(h
m
)==
Absolutesaturation
(absolutehumidity)
Percentsaturation
(percenthumidity)S
p
(h
p
)=x100%= x 100%
p
i
p
i
*(T)
p
i
P p
i
molesofvapor
molesofvaporfreegas
p
i
M
i
(P p
i
)M
dry
massofvapor
massofdrygas
= =
S
m
S
m
*
p
i
/(Pp
i
)
p
i
*/(Pp
i
*)
S
a
(h
a
)
http://www.youtube.com/watch?v=6oZ7HxrnSWo
23
Example:calculatethecompositionofasaturatedGasLiquid
system
1. Airandliquidwaterareinaclosedchamberat75Cand760
mmHg.Calculatethemolarcompositionofthegasphase.
Sincethegasandliquidareinequilibrium,theairmustbesaturatedwith
watervapor(ifnot,morewaterwouldevaporate),sothatRaoults lawmay
beapplied:
y
H2O
=p
H2O
*(75C)/P
FromTableB.3inAppendixB,p
H2O
(75C) =289mmHg.Consequently,
y
H2O
==0.380
289mmHgmol H
2
O
760mmHgmol
y
dry air
=1 y
H2O
=0.620
mol dryair
mol
24
2. Airat100Cand5260mmHgcontaining10.0%waterbyvolumeenters
acondenser.
a) Calculatedewpointanddegreesofsuperheatoftheair
b) Calculatethefractionofthevaporthatcondensesandthefinalcompositionof
thegasphaseiftheairiscooledto80Catconstantpressure.
p*
H2O
(90C)=526mmHgp*
H2O
(80C)=355mmHg
p
H2O
=y
H2O
P=(0.100)(5260mmHg)=526mmHg
p
H2O
(100C)=760mmHg>p
H2O
Thevaporissuperheated.
FromEquation6.33
p
H2O
= p
H2O
*(T
dp
)=526mm Hg
FromTableB.3(Vaporpressureofwater),
T
dp
=90C
Theairhas100C 90C=10Cofsuperheat
1atm =1.01325bar=101.3kPa =14.696psi(lb
f
/in
2
)=760mmHg=10.33
mH
2
O=760torr =29.92inHg =1013mbar
33
b) Since the air becomes saturated at 90 C, further cooling must lead
to condensation. As the products are liquid water in equilibrium with a
gas phase, the water vapor in the gas must remain saturated.
CONDENSER
100mol n
2
(mol)
0.100mol H
2
O(v)/mol y[mol H
2
O(v)/mol]
0.900mol BDA/mol (1y)(mol BDA/mol)
T =100C,P=5260mmHgT =80C,P=5260mmHg,
saturatedwithH
2
O
n
1
[mol H
2
O(l)]
Raoults LawatOutletyP = P*
H2O
(T)
y= ==0.0675
p
H2O
* (80C)355mmHg
P5260mmHg
mol H
2
O
mol
34
100mol 0.900mol BDA
mol
=n
2
(1y)
y=0.0675
n
2
=96.5mol
BalanceonDryAir
Totalmolebalance100mol =n
1
+n
2
n
2
=96.5mol
n
1
=3.5mol H
2
Ocondensed
Percentagecondensation
3.5mol H
2
Ocondensed
(0.100x100)mol H
2
Ofed
x 100%=35%
27
Manyprocessesbywhichthevariouscomponentsofasystem
areseparatedtypicallyinvolvesequilibriumofgasandliquid
phases.
Evaluationofmultiplecomponentgasliquidsystemsrequires
theuseofvaporliquidequilibriumdata(i.e.,equilibrium
compositionsofthevariouscomponentsineachphase).
Phaseequilibriumthermodynamicsdealswiththerelationships
thatgovernthedistributionofasubstancebetweengasand
liquidphases.
Multicomponent GasLiquidSystems
28
Suppose A is a substance contained in a gasliquid system in equilibrium
at temperature T and pressure P. Two simple expressions: Raoults law
and Henrys law provide relationships between p
A
, the partial pressure
of A in the gas phase, and X
A
, the mole fraction of A in the liquid phase.
Raoults Law: p
A
= y
A
P = x
A
p*
A
(T)
p*
A
: vapor pressure of pure liquid a at T; y
A
: mole fraction of A in the gas
phase
Raoults Law is an approximation that is generally valid when x
A
~ 1.
HenrysLaw:p
A
=y
A
P =x
A
H
A
(T)
Provided that A does not dissociate, ionize or react in the liquid phase.
The law is often applied to solutions of noncondensable gases.
Raoults andHenrysLaw:
x
A
~ 0
29
Examples:UseRaoults orHenrysLawtosolvetheproblems
1.Agascontaining1.00mole%ethaneisincontactwithwaterat20.0
Cand20.0atm.Estimatethemolefractionofdissolvedethane.
Hydrocarbonsnormallyarerelativelyinsolubleinwater,sothatthe
solutionofethaneisprobablyextremelydilute.Henryslawissuitable
inthiscase.
x
C2H6
=
y
C2H6
P
H
C2H6
=
0.01x20.0atm
2.63x10
4
atm/molefraction
=
mol C
2
H
6
mol
ThevalueforH
C2H6
isfoundfromPerrysChemicalEngineersHandbook.
7.60x10
6
30
2.Anequimolar liquidmixtureofbenzeneandTolueneisinequilibrium
withitsvaporat30C.Whatisthesystempressureandthetotal
compositionofthevapor?
Sincebenzeneandtoluenearestructurallysimilarcompounds,wemay
applyRaoults law.
FromTableB.4(AntoineEquationConstants)
log
10
p*=A p*inmmHg,TinC
B
T+C
log
10
p
B
*=6.906 p
B
*=119mmHg
1211
T+220.8
1343.9
T+219.38
T=30C
log
10
p
T
*=6.953 p
T
*=36.7mmHg
T=30C
31
p
B
=x
B
p
B
*=0.500x119mmHg=59.5mmHg
p
T
=x
T
p
T
*=0.500x36.7mmHg=18.35mmHg
P=p
B
+ p
T
=77.9mmHg
y
B
=p
B
/P=0.764molebenzene/mole
y
T
=p
T
/P=0.236moletoluene/mole
32
Ifheatisaddedtoamixtureofcomponents,liquid
temperaturerisesuntilabubbleofvaporisformed.
Inmostcases,thecompositionofthisvaporbubblediffers
fromthatoftheliquidfromwhichitformed.
Asvaporizationproceeds,thecompositionoftheremaining
liquidcontinuouslychanges,andhencesodoesits
vaporizationtemperature.
Ananalogousprocessoccurswhencondensingavapor
comprisedofanumberofcomponents.
VaporLiquidEquilibriumofIdealSolutions
33
VaporLiquidEquilibriumofIdealSolutions
When a liquid is heated slowly at constant pressure, the
temperature at which the first vapor bubble forms is called
the bubblepoint temperature.
When a vapor is cooled slowly at constant pressure, the
temperature at which the first liquid droplet forms is the dew
point temperature.
Formixturesthatbehaveasidealsolutions(Raoults and
Henryslawsapply),andthegasphasecanbeconsidered
ideal,calculationofthesetemperaturesisrelativelysimple.
34
35
36
Calculatethetemperatureandcompositionofavaporinequilibrium
withaliquidthatis40.0mol%benzeneand60.0mol%tolueneat1
atm.
BubblePointCalculation
37
LetA=benzeneandB=toluene
0.400p
A
*(T
bp
)+0.600p
B
*(T
bp
)=760mmHg
Thesolutionprocedureistochooseatemperature,evaluatep
A
*and
p
B
*forthattemperaturefromtheAntoineequationusingconstants
fromTableB.4.
Usingtrialanderror,T
bp
isdeterminedtobe95.1C(bubblepoint).
p
A
=0.400x1181mmHg=472.5mmHg
p
B
=0.600x479mmHg=287.5mmHg
P=(472.5+287.5)mmHg=760.0mmHg
y
A
=472.5/760.0=0.622molbenzene/mol
y
B
=1 y
A
=0.378moltoluene/mol
38
LiquidVaporEquilibrium
Tieline:connectsvaporandliquidphaseinequilibrium
MixtureB/Twith
x
B
=0.5at80C
Twophases:
Vaporwithy
B
=0.55
Liquidwithx
B
=0.12
39
Thesolubility ofasolidinaliquidisthemaximumamountofthe
substancethatcanbedissolvedinaspecifiedamountoftheliquid
atequilibrium.
Asolutionthatcontainsthismaximumofsoluteissaidtobe
saturated withthatspecies.
Ifasaturatedsolutioniscooled,thesolubilitydecreases.Sincethe
crystallizationprocesscanbeslow,thesolutioncanbeinameta
stablestateforwhichthedissolveamountofsoluteexceedsthe
maximumsolubility,astatecalledsupersaturation.
ThisisNOTanequilibriumstate.
Liquid/SolidSystems
40
GibbsPhaseRuleshowsthatspecifyingtemperatureandpressure
foratwocomponentsystematequilibriumcontainingasolid
soluteinaliquidsolutionfixesthevaluesofallotherintensive
variables.
Becausethepropertiesofliquidsandsolidsareonlyslightly
affectedbypressure,asingleplotofsolubilityvs.temperaturecan
beapplicableoverawiderangeofpressure.
SolidSolubilities
DF=2+c =2+2 2=2
41
Solid crystals formed from aqueous solution can contain water
molecules in the crystalline structure. These solids are called
hydrated salts, and the water molecules are referred to as
waters of hydration.
Awaterfreecrystaliscalledananhydroussalt.
HydratedSalts
42
Colligative solution properties are those properties of a
solution that differ from those of the pure solvent, and
depend solely on the concentration of solute in the solution.
Colligative properties of interest in this course:
vapor pressure
boiling point
freezing point
Colligative SolutionProperties
43
Ifwaterandmethylisobutylketone (MIBK)aremixedat25C,
onephaseresultsifthemixturecontains>98%wateror>
97.7%MIBKbymass.
Otherwise,themixtureseparatesintotwoliquidphases:98%
H
2
O/2%MIBKinone,and97.7%MIBK/2.3%H
2
Ointheother.
WaterandMIBKaresaidtobepartiallymiscible.
Iftheseparatingphasescontainednegligibleamountsofthe
otherspecies,thephasesaresaidtobeimmiscible.
Liquid/LiquidEquilibrium
44
If a 3rd component is added to a 2phase liquid mixture, this
component distributes between the 2 liquid phases. This
phenomenon is exploited to achieve a separation by liquid
extraction processes.
Suppose A and S are two nearly immiscible liquids, and B is a
solute distributed between the phases of an AS mixture.
The distribution coefficient K (partition ratio) of component B
is the ratio of mass fraction of B in the S phase to that in A
phase.
Liquid/LiquidEquilibrium
45
RegionAisasinglephaseregion
RegionBisatwoliquidphase
region
TielinesinRegionB
connecttheconcentrations
ofthetwoequilibrium
phases.
TernaryPhaseDiagrams
46
The attraction of chemical species from the gas or liquid phase
to a solid surface is the basis for a class of separation processes
referred to as adsorption. The solid is called the adsorbent,
while the component attracted to the surface is the adsorbate.
The equilibrium data between amount adsorbed vs.
concentration in the bulk phase is called an adsorption
isotherm.
AdsorptiononSolidSurfaces