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Inthistipofthemonth(TOTM)wewilldescribethedensephaseofapurecompound,whatitis,andhowit
impactsprocesses.Wewillillustratehowthermophysicalpropertieschangeinthedensephaseaswellas
intheneighboringphases.Theapplicationofdensephaseintheoilandgasindustrywillbediscussed
briefly.InnextmonthTOTM,wewilldiscussthedensephasebehaviorofmulticomponentsystems.
Whenapurecompound,ingaseousorliquidstate,isheatedandcompressedabovethecritical
temperatureandpressure,itbecomesadense,highlycompressiblefluidthatdemonstratespropertiesof
bothliquidandgas.Forapurecompound,abovecriticalpressureandcriticaltemperature,thesystemis
oftentimesreferredtoasadensefluidorsupercriticalfluidtodistinguishitfromnormalvaporandliquid
(seeFigure1forcarbondioxide).Densephaseisafourth(Solid,Liquid,Gas,Dense)phasethatcannotbe
describedbythesenses.Thewordfluidreferstoanythingthatwillflowandappliesequallywelltogas
andliquid.Purecompoundsinthedensephaseorsupercriticalfluidstatenormallyhavebetterdissolving
abilitythandothesamesubstancesintheliquidstate.Thedensephasehasaviscositysimilartothatofa
gas,butadensityclosertothatofaliquid.Becauseofitsuniqueproperties,densephasehasbecome
attractivefortransportationofnaturalgas,enhancedoilrecovery,foodprocessingandpharmaceutical
processingproducts.

Thelowviscosityofdensephase,supercriticalcarbondioxide(comparedwithfamiliarliquidsolvents),makesit
attractiveforenhancedoilrecovery(EOR)sinceitcanpenetratethroughporousmedia(reservoirformation).Ascarbon
dioxidedissolvesinoil,itreducesviscosityandoilwaterinterfacialtension,swellstheoilandcanprovidehighly
efficientdisplacementifmiscibilityisachieved.Additionally,substancesdispersethroughoutthedensephaserapidly,
duetohighdiffusioncoefficients.Carbondioxideisofparticularinterestindensefluidtechnologybecauseitis
inexpensive,nonflammable,nontoxic,andodorless.Pipelineshavebeenbuilttotransportnaturalgasinthedense
phaseregionduetoitshigherdensity,andthisalsoprovidestheaddedbenefitofnoliquidsformationinthepipeline.
Inthefollowingsectionwewillillustratethevariationofthermophysicalpropertiesinthedensephaseandits
neighboringphases.MethanepropertieshavebeencalculatedwithHYSYSsoftwareforaseriesoftemperaturesand
pressures.Table1presents,thepressuresandtemperaturesandtheirpathsusedinthisstudy.

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ThecalculatedthermophysicalpropertiesareplottedasafunctionofpressureandtemperatureinFigures2to9.The
thermophysicalpropertyisshownonthelefthandsideyaxis,temperatureonthexaxisandpressureontherighthand
sideyaxis.
Table1.PressureTemperaturecombinationandthepathschosenformethane

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Density:

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Figure2presentsthevariationofdensityindifferentphasesasafunctionofpressureandtemperature.Intheisobaric
subcoolingpathofAB,liquiddensityincreasesgradually.However,intheisothermalcompressionofBCpath,asmall
increaseofdensityisobserved.IntheisobaricCDpath,compressedliquiddensitydecreasesgraduallyastemperature
isincreasedwellintothedensephaseregion.However,asthetemperatureincreasesfurtherinthedensephase,
densityreductionisaccelerated.ReductionofdensityisfurtheracceleratedduringisothermalexpansionofDE.Isobaric
coolingofvaporalongEFpathcorrespondswithagradualincreaseindensity.Itcanbenotedthevaluesofdense
phasedensityareclosetotheliquidphasedensityinsomeareasofthedensephaseregion,andisoverallsignificantly
higherthanthevaporphasedensities.

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Viscosity:
Figure3presentsthevariationofviscosityindifferentphasesasafunctionofpressureandtemperature.Intheisobaric
subcoolingpathofAB,liquidviscosityincreasesrapidly.However,intheisothermalcompressionofBCpath,avery
smallchangeofviscosityisobserved.IntheisobaricCDpath,compressedliquidviscositydecreaseslinearlyand
sharplyastemperatureisincreasedwellintothedensephaseregion.Asthetemperatureincreasesfurtherinthedense
phase,viscosityreductionbecomesgradualandapproachesthegasphasevalues.Reductionofviscosityisquitesmall
duringisothermalexpansionofDE.IsobariccoolingofvaporalongEFpathcorrespondswithnoappreciablechangein
viscosity.

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CompressibilityFactor:
Ingeneral,thecompressibilityfactorZ,calculatedbyanequationofstateisnotaccuratefortheliquidphase.Therefore,
Figure4whichpresentscompressibilityfactorasafunctionofpressureandtemperatureshouldbeconsideredfor
qualitativestudyonly.IntheisobaricsubcoolingpathofAB,Zremainsalmostconstant.However,intheisothermal
compressionofBCpath,Zincreasesdrastically.IntheisobaricCDpath,Zincreasesgraduallyastemperatureis
increasedwellintothedensephaseregion.Asthetemperatureincreasesfurtherinthedensephase,theincreaseinZ
isaccelerated.TheincreaseinZisfurtheracceleratedduringisothermalexpansionofDE.Isobariccoolingofvapor
alongFFpathcorrespondswithagradualdecreaseinZ.

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SurfaceTension:
Figure5showsthatintheliquidphase,surfacetensionisastrongfunctionoftemperaturebutindependentofpressure.
Abovethecriticaltemperature,surfacetensionisnotapplicableanditsvalueiszero.
HeatCapacity:
Generally,heatcapacityisapplicableinasinglephaseregionandshouldnotbeusedwhenthereisaphasechange.
Figure6presentsthevariationofdensityindifferentphasesasafunctionofpressureandtemperature.Intheisobaric
subcoolingpathofAB,liquidheatcapacitydecreases.IntheisothermalcompressionofBCpath,asmalldecreaseof
heatcapacityisobserved.IntheisobaricCDpath,compressedliquidheatcapacityincreasesgraduallyastemperature
isincreasedwellintothedensephaseregion.Asthetemperatureincreasesfurtherinthedensephase,heatcapacity
reachesamaximumvalueandthenstartstodecrease.Thisisstrangebehaviorandsurprisinglyhighvaluesare
calculated.SimilarresultswereobtainedusingProMaxsoftware.Reductionofheatcapacityisfurthernoticedduring
isothermalexpansionofDE.IsobariccoolingofvaporalongEFpathcorrespondswithagradualincreaseinheat
capacity.
ThermalConductivity:
Figure7presentsthevariationofthermalconductivityindifferentphasesasafunctionofpressureandtemperature.In
theisobaricsubcoolingpathofAB,liquidthermalconductivityincreases.IntheisothermalcompressionofBCpath,no
changeisobserved.IntheisobaricCDpath,compressedliquidthermalconductivitydecreasesgraduallyas
temperatureisincreasedwellintothedensephaseregion.However,asthetemperatureincreasesfurtherinthedense
phase,thermalconductivityreductionisaccelerated.Reductionofthermalconductivityisfurthernoticedduring
isothermalexpansionofDE.IsobariccoolingofvaporalongEFpathcorrespondswithasmalldecreaseinthermal
conductivity.

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EnthalpyandEntropy:
Figures8and9presentthevariationofenthalpyandentropyindifferentphasesasafunctionofpressureand
temperature.Asshowninthesefigures,theirqualitativevariationsaresimilar.IntheisobaricsubcoolingpathofAB,
liquidenthalpyandentropydecrease.IntheisothermalcompressionofBCpath,nochangeisobserved.Duringthe
isobaricCDpath,compressedliquidenthalpyandentropyvaluesincreasegraduallyastemperatureisincreasedwell
intothedensephaseregion.However,asthetemperatureincreasesfurtherinthedensephase,theenthalpyand
entropyincreasebecomeslarger.Theincreaseinenthalpyandentropyisfurthernoticedduringisothermalexpansion
ofDE.IsobariccoolingofvaporalongEFpathcorrespondswithadecreaseinenthalpyandentropy.

Conclusions:
Densephasebehaviorisuniqueandhasspecialfeatures.Thethermophysicalpropertiesinthisphasemayvary
abnormally.Careshouldbetakenwhenequationsofstateareusedtopredictthermophysicalpropertiesindense
phase.Evaluationofequationsofstateshouldbeperformedinadvancetoassuretheiraccuracyinthisregion.Many
simulatorsoffertheoptiontouseliquidbasedalgorithms(e.g.COSTALD)forthisregion.
AsshowninFigure1,thereisagradualchangeofphasetransitionfromgastodenseanddensetoliquidphasesor
viceversa.Densephaseisahighlycompressiblefluidthatdemonstratespropertiesofbothliquidandgas.Thedense
phasehasaviscositysimilartothatofagas,butadensityclosertothatofaliquid.Thisisafavorableconditionfor
transportingnaturalgasindensephaseaswellascarbondioxideinjectionintocrudeoilreservoirforenhancedoil
recovery.
Tolearnmoreaboutsimilarcasesandhowtominimizeoperationalproblems,wesuggestattendingourG40
(Process/FacilityFundamentals),G4(GasConditioningandProcessing),PF81(CO2 SurfaceFacilities),andPF4
(OilProductionandProcessingFacilities)courses.
JohnM.CampbellConsulting(JMCC)offersconsultingexpertiseonthissubjectandmanyothers.Formoreinformation
abouttheservicesJMCCprovides,visitourwebsiteatwww.jmcampbellconsulting.com,oremailyourconsulting
needstoconsulting@jmcampbell.com.
By:MarkBothamleyandMahmoodMoshfeghian
Reference:
1. ASPENone,EngineeringSuite,HYSYSVersion2006,AspenTechnology,Inc.,Cambridge,Massachusetts
U.S.A.,2006.

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PostedonDecember1,2009at3:50pm
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WrittenbyDr.MahmoodMoshfeghian
Dr.MahmoodMoshfeghianisaninstructorandconsultantwithJohnMCampbellandCompany(JMC).Heistheauthor
ofmostofCampbellTipsoftheMonthanddevelopstechnicalsoftwareforJMC.Hehas35yearsteachingexperiencein
universities(OklahomaStateUniversity,UniversityofShiraz,UniversityofSydneyandUniversityofQatar)aswellasfor
oilandgasindustries.Dr.MoshfeghianjoinedJMCin1990asaparttimeconsultantandthenasfulltime
instructor/consultantin2005.PrevioustojoiningJMC,Dr.MoshfeghianwasaSeniorResearchScientistatKuwait
InstituteforScientificResearchandProfessorofChemicalEngineeringatShirazUniversity.Dr.Moshfeghianisasenior
memberofAIChEandhaspublishednumeroustechnicalpapersonthermodynamicproperties,andProcess
Engineering.Dr.Moshfeghianhaspresentedinvitedpapersininternationalconferences.HeholdsaB.S.,anM.S.anda
Ph.D.inChemicalEngineering,allfromOklahomaStateUniversity.
Viewallpostsby:Dr.MahmoodMoshfeghian
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4ResponsestoVariationofpropertiesinthedensephaseregionPart1Pure
Compounds
1. TransportationofCO2inDensePhase|CampbellTipoftheMonthsays:
January3,2012at8:35am
[]fluidtodistinguishitfromnormalvaporandliquid(seeFigure1forcarbondioxideinDecember2009TOTM
[1]).Densephaseisafourth(Solid,Liquid,Gas,Dense)phasethatcannotbedescribedbythe[]
Reply
2. TransportedelCO2enlaFaseDensa|CampbellTipoftheMonthSpanishsays:
January11,2012at2:57pm
[]M.,VariationofpropertiesinthedensephaseregionPart1Purecompounds,
http://www.jmcampbell.com/tipofthemonth/2009/12/variationofpropertiesinthedensephaseregion,
December[]

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Reply
3. NonIsothermalTransportationofCO2intheDensePhase|CampbellTipoftheMonthsays:
February1,2012at6:01am
[]fluidtodistinguishitfromnormalvaporandliquid(seeFigure1forcarbondioxideinDecember2009TOTM
[]
Reply
4. TransporteNoIsotrmicodelCO2enlaFaseDensa|CampbellTipoftheMonthSpanishsays:
February8,2012at12:05pm
[]Parauncompuestopuro,porencimadelapresinytemperaturacrtica,selerefierealsistemacon
frecuenciacomounodefasedensa,ofluidosupercrticoparadiferenciarlodeunvaporolquidonormal
(vaselaFigura1paraeldixidodecarbonoenelPDMdeDiciembre2009[1]).[]
Reply
5. EffectofNitrogenImpuritiesonCO2DensePhaseTransportation|CampbellTipoftheMonthsays:
March1,2012at8:30am
[]fluidtodistinguishitfromnormalvaporandliquid(seeFigure1forcarbondioxideinDecember2009TOTM
[]
Reply
6. EffectofNitrogenImpuritiesonCO2DensePhaseTransportation|CampbellTipoftheMonthSpanish
says:
March12,2012at2:27pm
[]M.,VariationofpropertiesinthedesephaseregionPart1Purecompounds,TOTM,
http://www.jmcampbell.com/tipofthemonth/2009/12/variationofpropertiesinthedensephaseregion,
Dec[]
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7. searchtoolssays:
June22,2012at6:10am
SubmitComment
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8. TransportationofNaturalGasinDensePhase|CampbellTipoftheMonthsays:
October23,2012at8:14am
[]orsupercriticalfluidtodistinguishitfromnormalvaporandliquid(seeFigure1inDecember2009TipOf
TheMont(TOTM)[1]forcarbondioxideandinJanuary2010TOTM[2]foratypicalnaturalgas).Densephaseis
a[]
Reply
9. TransportationofEthanebyPipelineintheDensePhase|CampbellTipoftheMonthsays:
March1,2014at11:12am
[]fluidtodistinguishitfromnormalvaporandliquid(seeFigure1forcarbondioxideinDecember2009TOTM
[]
Reply
10. TransportedelEtanoporGasoductoenlaFaseDensa|CampbellTipoftheMonthSpanishsays:
March2,2014at1:22pm
[]M.,VariationofpropertiesinthedesephaseregionPart1Purecompounds,TOTM,
http://www.jmcampbell.com/tipofthemonth/2009/12/variationofpropertiesinthedensephaseregion,
Dec[]
Reply
11. retenciondeliquidoscausasyremediossays:
July13,2014at10:35am
Buenosdasmeheledotupostymeapetecaagradecertequehayasgastadotutiempoenrecopilartodaesta
informacintannecesariaparalosquenosencontramosperdiendopeso.graciasportuarticulo!!Yunsaludo!!
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12. RosarioBolmansays:
November17,2014at4:14am
Goodpost.Iamaregularvisitorofyourwebsiteandappreciateyoutakingthetimetomaintainthenicesite.I
willbearegularvisitorforalongtime.
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13. MuhammadShehreyarKhansays:
January15,2015at4:10am
Infirst&2nddiagramsAB&CDarereferredasisobaricprocessesalthoughpressureseemstochangefrom
approx4.4MPa(g)to5.4MPa(g)incaseofAB(asindicatedbyblackline).
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