The Properties of Gases and Liquids, Fifth Edition

803 Pages·2000·4.281 MB·English

by  Bruce E. Poling, John M. Prausnitz, John P. O'Connell

THEPROPERTIESOF
GASESANDLIQUIDS
Bruce E. Poling
Professor of Chemical Engineering
University of Toledo
John M. Prausnitz
Professor of Chemical Engineering
University of California at Berkeley
John P. O’Connell
Professor of Chemical Engineering
University of Virginia
Fifth Edition
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DOI: 10.1036/0070116822
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CONTENTS
Preface vii
Chapter 1 The Estimationof Physical Properties 1.1
1-1 Introduction / 1.1
1-2 EstimationofProperties / 1.3
1-3 TypesofEstimation / 1.3
1-4 OrganizationoftheBook / 1.6
Chapter 2 Pure ComponentConstants 2.1
2-1 Scope / 2.1
2-2 Vapor-LiquidCriticalProperties / 2.2
2-3 AcentricFactor / 2.23
2-4 BoilingandFreezingPoints / 2.26
2-5 DiscussionofEstimationMethodsforPureComponentConstants / 2.33
2-6 DipoleMoments / 2.34
2-7 AvailabilityofDataandComputerSoftware / 2.35
Chapter 3 ThermodynamicPropertiesof Ideal Gases 3.1
3-1 ScopeandDefinitions / 3.1
3-2 EstimationMethods / 3.5
3-3 MethodofJoback / 3.6
3-4 MethodofConstantinouandGani(CG) / 3.8
3-5 MethodofBenson[1968;1969] / 3.14
3-6 DiscussionandRecommendations / 3.46
3-7 HeatofCombustion / 3.47
Chapter 4 Pressure-Volume-TemperatureRelationshipsof Pure
Gases and Liquids 4.1
4-1 Scope / 4.1
4-2 IntroductiontoVolumetricProperties / 4.1
4-3 CorrespondingStatesPrinciple / 4.5
4-4 EquationsofState / 4.8
4-5 VirialEquationofState / 4.11
4-6 AnalyticalEquationsofState / 4.17
4-7 NonanalyticEquationsofState / 4.25
4-8 DiscussionofEquationsofState / 4.31
4-9 PVTPropertiesofLiquids—GeneralConsiderations / 4.32
iii
iv CONTENTS
4-10 EstimationoftheLiquidMolarVolumeattheNormalBoilingPoint / 4.33
4-11 SaturatedLiquidDensitiesasaFunctionofTemperature / 4.35
4-12 CompressedLiquidDensities / 4.43
Chapter 5 Pressure-Volume-TemperatureRelationshipsof Mixtures 5.1
5-1 Scope / 5.1
5-2 MixtureProperties—GeneralDiscussion / 5.2
5-3 CorrespondingStatesPrinciple(CSP):ThePseudocriticalMethod / 5.5
5-4 VirialEquationsofStateforMixtures / 5.8
5-5 AnalyticalEquationsofStateforMixtures / 5.12
5-6 NonanalyticEquationsofStateforMixtures / 5.18
5-7 DiscussionofMixtureEquationsofState / 5.22
5-8 DensitiesofLiquidMixturesatTheirBubblePoint / 5.23
5-9 DensitiesofCompressedLiquidMixtures / 5.26
Chapter 6 ThermodynamicPropertiesof Pure Components
and Mixtures 6.1
6-1 Scope / 6.1
6-2 FundamentalThermodynamicRelationshipsforPureComponents / 6.1
6-3 DepartureFunctionsforThermodynamicProperties / 6.4
6-4 EvaluationofDepartureFunctionsforEquationsofState / 6.6
6-5 HeatCapacitiesofRealGases / 6.16
6-6 HeatCapacitiesofLiquids / 6.17
6-7 PartialPropertiesandFugacitiesofComponentsinMixtures / 6.26
6-8 TrueCriticalPointsofMixtures / 6.30
Chapter 7 VaporPressures and Enthalpiesof Vaporizationof
Pure Fluids 7.1
7-1 Scope / 7.1
7-2 Theory / 7.1
7-3 CorrelationandExtrapolationofVapor-PressureData / 7.3
7-4 Ambrose-WaltonCorresponding-StatesMethod / 7.7
7-5 RiedelCorresponding-StatesMethod / 7.9
7-6 DiscussionandRecommendationsforVapor-PressureEstimationand
Correlation / 7.11
7-7 EnthalpyofVaporizationofPureCompounds / 7.13
7-8 Estimationof(cid:2)H fromVapor-PressureEquations / 7.14
v
7-9 Estimationof(cid:2)H fromtheLawofCorrespondingStates / 7.16
v
7-10 (cid:2)H attheNormalBoilingPoint / 7.19
v
7-11 Variationof(cid:2)H withTemperature / 7.23
v
7-12 DiscussionandRecommendationsforEnthalpyofVaporization / 7.24
7-13 EnthalpyofFusion / 7.25
7-14 EnthalpyofSublimation;VaporPressuresofSolids / 7.28
Chapter 8 Fluid Phase Equilibriain MulticomponentSystems 8.1
8-1 Scope / 8.1
8-2 ThermodynamicsofVapor-LiquidEquilibria / 8.9
CONTENTS v
8-3 FugacityofaPureLiquid / 8.11
8-4 SimplificationsintheVapor-LiquidEquilibriumRelation / 8.12
8-5 ActivityCoefficients;Gibbs-DuhamEquationandExcessGibbsEnergy / 8.12
8-6 CalculationofLow-PressureBinaryVapor-LiquidEquilibriawithActivity
Coefficients / 8.19
8-7 EffectofTemperatureonLow-PressureVapor-LiquidEquilibria / 8.22
8-8 BinaryVapor-LiquidEquilibria:Low-PressureExamples / 8.23
8-9 MulticomponentVapor-LiquidEquilibriaatLowPressure / 8.32
8-10 DeterminationofActivityCoefficients / 8.42
8-11 PhaseEquilibriumwithHenry’sLaw / 8.111
8-12 Vapor-LiquidEquilibriawithEquationsofState / 8.120
8-13 SolubilitiesofSolidsinHigh-PressureGases / 8.158
8-14 Liquid-LiquidEquilibria / 8.159
8-15 PhaseEquilibriainPolymerSolutions / 8.177
8-16 SolubilitiesofSolidsinLiquids / 8.180
8-17 AqueousSolutionsofElectrolytes / 8.191
8-18 ConcludingRemarks / 8.193
Chapter 9 Viscosity 9.1
9-1 Scope / 9.1
9-2 DefinitionsofUnitsofViscosity / 9.1
9-3 TheoryofGasTransportProperties / 9.2
9-4 EstimationofLow-PressureGasViscosity / 9.4
9-5 ViscositiesofGasMixturesatLowPressures / 9.15
9-6 EffectofPressureontheViscosityofPureGases / 9.29
9-7 ViscosityofGasMixturesatHighPressures / 9.47
9-8 LiquidViscosity / 9.51
9-9 EffectofHighPressureonLiquidViscosity / 9.55
9-10 EffectofTemperatureonLiquidViscosity / 9.56
9-11 EstimationofLow-TemperatureLiquidViscosity / 9.59
9-12 EstimationofLiquidViscosityatHighTemperatures / 9.75
9-13 LiquidMixtureViscosity / 9.77
Chapter 10 ThermalConductivity 10.1
10-1 Scope / 10.1
10-2 TheoryofThermalConductivity / 10.1
10-3 ThermalConductivitiesofPolyatomicGases / 10.2
10-4 EffectofTemperatureontheLow-PressureThermalConductivitiesofGases / 10.18
10-5 EffectofPressureontheThermalConductivitiesofGases / 10.18
10-6 ThermalConductivitiesofLow-PressureGasMixtures / 10.29
10-7 ThermalConductivitiesofGasMixturesatHighPressures / 10.35
10-8 ThermalConductivitiesofLiquids / 10.42
10-9 EstimationoftheThermalConductivitiesofPureLiquids / 10.44
10-10 EffectofTemperatureontheThermalConductivitiesofLiquids / 10.51
10-11 EffectofPressureontheThermalConductivitiesofLiquids / 10.52
10-12 ThermalConductivitiesofLiquidMixtures / 10.56
Chapter 11 DiffusionCoefficients 11.1
11-1 Scope / 11.1
vi CONTENTS
11-2 BasicConceptsandDefinitions / 11.1
11-3 DiffusionCoefficientsforBinaryGasSystemsatLowPressures:Predictionfrom
Theory / 11.5
11-4 DiffusionCoefficientsforBinaryGasSystemsatLowPressures:Empirical
Correlations / 11.9
11-5 TheEffectofPressureontheBinaryDiffusionCoefficientsofGases / 11.12
11-6 TheEffectofTemperatureonDiffusioninGases / 11.19
11-7 DiffusioninMulticomponentGasMixtures / 11.19
11-8 DiffusioninLiquids:Theory / 11.20
11-9 EstimationofBinaryLiquidDiffusionCoefficientsatInfiniteDilution / 11.21
11-10 ConcentrationDependenceofBinaryLiquidDiffusionCoefficients / 11.33
11-11 TheEffectsofTemperatureandPressureonDiffusioninLiquids / 11.38
11-12 DiffusioninMulticomponentLiquidMixtures / 11.41
11-13 DiffusioninElectrolyteSolutions / 11.43
Chapter 12 Surface Tension 12.1
12-1 Scope / 12.1
12-2 Introduction / 12.1
12-3 EstimationofPure-LiquidSurfaceTension / 12.2
12-4 VariationofPure-LiquidSurfaceTensionwithTemperature / 12.11
12-5 SurfaceTensionsofMixtures / 12.12
AppendixA PropertyDataBank A.1
AppendixB Lennard-JonesPotentialsasDeterminedfromViscosityData B.1
AppendixC GroupContributionsforMultipropertyMethods C.1
IndexfollowsAppendixC
PREFACE
Reliable values of the properties of materials are necessary for the design of in-
dustrial processes. An enormous amount of data has been collected and correlated
over the years, but the rapid advance of technology into new fields seems always
tomaintainasignificantgapbetweendemandandavailability.Theengineerisstill
required to rely primarily on common sense, experience, and a variety of methods
for estimating physical properties.
This book presents a critical review of various estimation procedures for alim-
ited number of properties of gases and liquids: critical and other pure component
properties; PVT and thermodynamic properties of pure components and mixtures;
vapor pressures and phase-change enthalpies; standard enthalpies of formation;
standard Gibbs energies of formation; heat capacities; surfacetensions;viscosities;
thermal conductivities; diffusion coefficients; and phase equilibria. Formostcases,
estimated properties arecompared toexperimenttoindicatereliability.Mostmeth-
ods are illustrated by examples.
The procedures described are necessarily limited to those that appear to the
authors to have the greatest validity and practical use. Whereverpossible,wehave
included recommendations delineating the best methods for estimating each prop-
erty and the most reliable techniques for extrapolating or interpolating available
data.
Although the book is intended to serve primarily the practicing engineer, espe-
cially the process or chemical engineer, other engineers and scientists concerned
with gases and liquids may find it useful.
The first edition of this book was published in 1958, the second in 1966, the
thirdin1977andthefourthin1987.Inasense,eacheditionisanewbookbecause
numerous estimation methods are proposed each year; over a (roughly) 10-year
span, many earlier methods are modified or displaced by more accurate or more
generaltechniques.Whilemostestimationmethodsrelyheavilyonempiricism,the
better ones—those that are most reliable—often have a theoretical basis. In some
cases,thetheoryisoutlinedtoprovidetheuserwiththefoundationoftheproposed
estimation method.
There are some significant differences between the current edition and the pre-
ceding one:
1. Chapter 2 includes several extensive new group-contribution methods as well
asdiscussionandcomparisonsofmethodsbasedondescriptorscalculatedwith
quantum-mechanicalmethods.Directcomparisonsaregivenformorethan200
substances with data in Appendix A.
2. Chapter 3 includes several new methods as well as updated Benson-Method
tables for ideal-gas properties of formation and heat capacities. Direct com-
parisons are given for more than 100 substances with data in Appendix A.
3. Chapter 4 includes presentation of current equations of state for pure compo-
nents with complete formulae for many models, especially cubics. Anewsec-
vii
Copyright © 2001, 1987, 1977, 1966, 1958 by The McGraw-Hill Companies, Inc.
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viii PREFACE
tion discusses issues associated with near-critical and very high pressure sys-
tems. The Lee–Kesler corresponding-states tables, readily availableelsewhere,
have been removed.
4. Chapter 5 includes presentation of current equations ofstate formixtureswith
completeformulaeformanymodels,especiallycubics.Anewsectiondiscusses
current mixing and combining rules for equation-of-state parameters with at-
tention to inconsistencies.
5. Chapter 6 includes a revised introduction to thermodynamic properties from
equations of state with complete formulae for cubics. A new sectiondiscusses
real-gas and liquid heat capacities. Because they are readily available else-
where, the Lee–Kesler corresponding-statestables have been removed.
6. Chapter 7 gives attention to one form of the Wagner equation that appears to
be particularly successful for representing vapor pressures, and to the useful
tables of Majer and Svoboda for enthalpiesof vaporization. Alsoincludedisa
new discussion of the entropy of fusion.
7. Chapter8hasbeenextendedtoincludediscussionofsystemscontainingsolids,
a new correlation by Eckert et al. for activity coefficents at infinite dilution,
and some new methods for high-pressure vapor-liquid equilibria, including
those based on Wong–Sandler mixing rules.
8. In Chapters 9–12, most of the new methods for transport properties are based
on thermodynamic data or molecular-thermodynamic models. The successful
TRAPPmethod(fromtheNationalInstituteofScienceandTechnology)isnow
explained in more detail.
9. The property data bank in Appendix A has been completely revised. Most of
the properties are the same as in the last edition, but the format has been
changed to identify the sources of values. The introduction to Appendix A
describes the definitions and font usage of the data bank.
We selected only those substances for which we could readily obtain an
evaluated experimental critical temperature; the total number of compounds is
fewer than in the last edition. All of the entries in Appendix A were taken
fromtabulations oftheThermodynamicsResearchCenter(TRC),CollegeSta-
tion, TX, USA, or from other reliable sources as listed in the Appendix. We
also used experimentally-based results for other properties from the same
sources whenever available. Some estimated values are also included.
We tabulate the substancesinalphabeticalformulaorder.IUPACnamesare
used,withsomecommonnamesadded,andChemicalAbstractsRegistrynum-
bers are given for each compound. We indicate origins of the properties by
using different fonts. We are grateful to TRC for permitting us to publish a
significant portion of their values.
10. Appendix C presents complete tables of parameters for the multi-property
group-contribution methods of Joback and of Constantinou and Gani.
The authors want to acknowledge with thanks significant contributions from
colleagues who provided assistance in preparing the current edition; their help has
been essential and we are grateful to them all: David Bush, Joe Downey, Charles
Eckert, Michael Frenkel, Rafiqui Gani and students of the CAPEC Center at the
Technical University of Denmark, Lucinda Garnes, Steven Garrison, Nathan Erb,
K. R. Hall, Keith Harrison, Marcia Huber, Kevin Joback, Kim Knuth, ClaudeLei-
bovicci, Paul Mathias, Amy Nelson, Van Nguyen, Chorng Twu, Philippe Ungerer
and Randolph Wilhoit.