Chapter 5

Single Phase Systems

Bin Liu
E5-02-17
Cheliub@nus.edu.sg
1

FindingPhysicalProperties
Lookitup

PerrysChemicalEngineersHandbook
CRCHandbookofChemistryandPhysics
TRCDatabasesinChemistryandEngineering
PhysicalandThermodynamicPropertiesofPure
ChemicalsDataCompilation(DesignInstituteofPhysical
PropertiesResearch)
Estimateit
Virial equation,Cubicequations,Compressibilityfactor
Measureit
2

MixtureDensityofaSolidorLiquid
Onemayassumevolumeormassadditivity tocalculatemixture
densitiesfromthoseofpurecomponents.

(1)

(2)

MixtureDensityofaSolidorLiquid
(50%H2SO4,20C)=1.3951g/cm3
(H2SO4,18C)=1.834g/cm3
(H2O,20C)=0.998g/cm3

= 0.5 0.998+0.5 1.834=1.42g/cm3

1.8%error

1/
1

0.5

0.5 +=1.29g/cm
3
=

/
0.998
1.834

7.5%error

IdealGases
Anequationofstate(EOS)relatesmolarquantityand
volumeofagastotemperatureandpressure.
IdealGasLawissimplestandmostwidelyusedEOS
PV=nRT

PV=nRT

P V=RT =PM/RT

M/
V=

whereisthespecificmolarvolumeofthegas
V
ingeneral,itissafetousetheidealgasEOSwhen

V>5L/mol(80ft3/lbmol)fordiatomicgases
Or>20L/mol(320ft3/lbmol)forothergases
5

Ideal Gases

10

11

12

GasConstants

R=8.314Jmol1K1
R=0.082Latm mol1K1
R=8.314x102 Lbarmol1K1
R=1.986Btulbmol1 R1

13

IdealGases
Example:OnehundredgramsofN2 isstoredinacontainerat
23.0Cand3.00psi. Assumingidealgasbehavior,calculate
thecontainervolumeinliters.
100.0g
n==3.57molT=23.0+273=296K
28.0g/mol
nRT
V==
P

3.57mol 296K0.08206liter atm 14.7psi

17.7psimol Katm

= 72.0L

VerifythattheidealgasEOSisvalidforthegivenconditions:
72.0L

RT
V
V===
n
P
3.57mol

=20.2L/mol >5L/mol

14

StandardTemperatureandPressure
Standardconditions:Ts =273K,Ps =1atm.

PV
PsVs

T
Ts

15

EffectofT&PonVolumetricFlowRate
Example: Ten cubic feet of air at 70F and 1.00 atm is heated to
610F and compressed to 2.50 atm. What volume does the gas
occupy in its final state?
Let1denotetheinitialstateofthegasand2thefinalstate.
Notethatn1 =n2. Assumeidealgasbehavior:

10

SCMH m3 (STP)/h;SCFH ft3(STP)/h

Example:Whatisthetruevolumeflowrateforagasstream
with23.8SCMHat150Cand2.5atm?

23.8m3
T2
P1
Vtrue =VSCMH(
)(
)=
T1
P2
h

423K

273K

)(

1atm
) =14.8m3/h
2.5atm

17

IdealGasMixtures
ThepartialpressureofagascomponentAisthatpressure
exertedbythenA molesofAaloneinthesametotalvolumeV
andatthesametemperatureT.
PA V = nA RT

PA = yA P

Thepurecomponentvolumeisthevolumethatwouldbe
occupiedbynA molesofAatthetotalpressurePand
temperatureTofthemixture.
P VA = nA RT

VA = yA V

18

Non-Ideal Gas

---non-ideal
---non-ideal
19

CriticalPressureandTemperature
Aquantityofwaterinaclosedpistonfittedcylinder.

Systemisinitiallyallvapor.
Watervaporiscompressedatconstanttemperatureby
loweringthepistonuntiladropofcondensateforms.
Atthispoint,thepressure(Pcond),
vapordensity(v),andliquiddensity(L)
arenoted,andtheexperimentis
repeatedataseriesofdifferent
Temperatures.

20

CriticalPressureandTemperature

Thehighesttemperatureatwhichtwophases(liq./vap.)
cancoexististhecriticaltemperatureofthatspecies.
Thecorrespondingpressureisthecriticalpressure.
21

CriticalPressureandTemperature
AsubstanceatTc andPc isinitscriticalstate.
SubstancesaboveTc andPc areconsideredtobeina
supercriticalstate.
Avapor isaspeciesbelowitscriticaltemperature.
Agas isaspeciesaboveitscriticaltemperature.

22

SupercriticalCO2

http://www.youtube.com/watch?v=yBRdBrnIlTQ

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Virial EOS
Avirial EOSexpressesthequantitythePVTrelationshipasa
powerseriesintermsofinverseofspecificvolume:

B,C,andDaref(T)andareknownasthe2nd,3rd,
and4thvirial coefficients,respectively.
Theoreticallydeterminedfromstatisticalmechanics.
IdealgasEOSisobtainedbysettingB=C=D=0
Truncatedvirial equationbysettingC=D=0
Useofvirial EOSrestrictedtononpolar species.

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Virial EOS
EstimateV,P,orTfornonpolar species:
LookupTc,Pc and(Pitzer acentricfactor,a
quantificationofmoleculegeometryandpolarity).
Calculatereducedtemperature,Tr =T/Tc
EstimateBusing

B=

RTc
Pc

(B0 +B1)

0.422
Tr1.6
B1 =0.139 0.172
Tr4.2
B0 =0.083

Substitute B in truncated virial

EOS:

PV =1+ B

RTV
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CubicEOS
Whenexpanded,thisgroupofEOSresultinathirdorder
relationshipinspecificvolume.
vander WaalsEOS istheearliestsuchexpression
RT
a
P=

V bV2

a=

27R2Tc2
64Pc

b=

RTc
8Pc

AnumberofotherveryimportantcubicEOSexist
RedlichKwong EOS
SoaveRedlichKwong (SRK)EOS
PengRobinsonEOS

26

CubicEOSSRK
SoaveRedlichKwong (SRK)EOS:
RT
a
P=

V bV(V+b)
(RTc)2
a=0.42747
Pc
RTc
b=0.08664 P
c
m=0.48508+1.55171 0.15612
=[1+m(1 Tr )2]

27

Example:Agascylinderwithavolumeof2.50cm3
contains1.00kmol ofcarbondioxideatT=300K.Usethe
SRKequationofstatetoestimatethegaspressureinatm.
3

2.5m
10 L1kmol
V
V ===2.50L/mol
n
1.00kmol
1m3 103 mol

FromTableB.1(Page629),forCO2,Tc =304.2K,Pc =72.9atm

FromTable5.31(page201), =0.225
{[0.08206Latm/(mol K)](304.2K)}2
a=0.42747=3.654L2 atm/mol2
72.9atm
{[0.08206Latm/(mol K)](304.2K)}2
b=0.08664=0.02967L/mol
72.9atm
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m=0.48508+1.55171 0.15612=0.8263
Tr =T/Tc =300/304.2=0.986
=[1+m(1 Tr )2]=1.0115
RT
a
P=

V bV(V+b)
=

0.08206L atm/(molK)](300K)
[(2.50 0.02967)L/mol]

1.0115(3.654L2atm/mol2)
(2.50L/mol)[(2.50+0.02967)L/mol]

=9.38atm

29

CompressibilityFactorEOS
Thecompressibilityfactorofagas,zisdefinedastheratioof

z =

PV
RT

Idealgaseshaveacompressibilityfactorof1
Rearrangingthedefinitionofzyieldsthecompressibility
factorEOS:

PV=zRT

PV=znRT

PV=znRT

TousethecompressibilityfactorEOSrequiresdeterminationofz.
30

CompressibilityFactors
Compressibilityfactorsaretabulatedinsection2ofPerrys
Handbookasz(T,P)forair,Ar,CO2,CO,H2,CH4,N2, O2 steam,
andalimitednumberofothercompounds.
Example: Fiftycubicmetersperhourofmethaneflowthrough
apipelineat40.0barabsoluteand300.0K.Estimatethemass
flowrate.

(40.0bar)(50.0m3/h)kmol K101.325kPa
PV
n==
zRT
(0.934)(300.0K)8.314m3kPa1.01325bar

=85.9kmol/h

m=85.9kmol/hx16.04kg/kmol =1370kg/h
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LawofCorrespondingStates
TheLawofCorrespondingStatesholdsthatthevaluesof
certainphysicalpropertiesofagas,suchasthe
compressibilityfactor,dependtogreatextentonthe
proximityofthegastoitscriticalstate.
Tr andPrprovidetherelativeproximity.
EstimatezforaspeciesatagivenTandPas:
Lookupthecriticaltemperatureandpressure
calculatethereducedtemperatureandpressure
lookupzinageneralizedcompressibilitychart

32