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    Chapter 5 2014

    Uploaded by

    Minh Tieu
    asdf

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    © All Rights Reserved
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    Chapter 5 2014

    Uploaded by

    Minh Tieu
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    22 views32 pages

    Chapter 5 2014

    Uploaded by

    Minh Tieu
    asdf

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 32

    Chapter 5

    Single Phase Systems


    Bin Liu
    E5-02-17
    [email protected]
    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

    23

    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.

    24

    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
    25

    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
    28

    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
    31

    LawofCorrespondingStates
    TheLawofCorrespondingStatesholdsthatthevaluesof
    certainphysicalpropertiesofagas,suchasthe
    compressibilityfactor,dependtogreatextentonthe
    proximityofthegastoitscriticalstate.
    Tr andPrprovidetherelativeproximity.
    EstimatezforaspeciesatagivenTandPas:
    Lookupthecriticaltemperatureandpressure
    calculatethereducedtemperatureandpressure
    lookupzinageneralizedcompressibilitychart

    32

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