Manual Aspen

Physical Property
Methods and Models

S T E A D Y S T A T E S I M U L A T I O N
10
AspenTech
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Physi cal Property Methods and Model s i i i
Rel ease 10
Contents
About Physi cal Property Methods and Model s
For More I nformati on.............................................................................................................vi
Techni cal Support .................................................................................................................vi i
1 Overview of ASPEN PLUS Property Methods
Thermodynami c Property Methods.....................................................................................1-2
Equati on-of-State Method.................................................................................................1-3
Vapor-Li qui d Equi l i bri a ...........................................................................................1-4
Pressure-Temperature Di agram......................................................................1-5
Retrograde Condensati on .................................................................................1-6
Li qui d-Li qui d and Li qui d-Li qui d-Vapor Equi l i bri a................................................1-6
Li qui d Phase Noni deal i ty.................................................................................1-6
Cri ti cal Sol uti on Temperature ..................................................................................1-7
Cal cul ati on of Properti es Usi ng an Equati on-of-State Property Method .................1-7
Advantages and Di sadvantages of the Equati on-of-State Method...........................1-8
References ...................................................................................................................1-9
Acti vi ty Coeffi ci ent Method ............................................................................................1-10
Vapor-Li qui d Equi l i bri a ..........................................................................................1-11
Li qui d Phase Reference Fugaci ty ..................................................................1-11
El ectrol yte and Mul ti component VLE...........................................................1-12
Li qui d-Li qui d and Li qui d-Li qui d-Vapor Equi l i bri a................................................1-13
Phase Equi l i bri a I nvol vi ng Sol i ds ...........................................................................1-16
Sal t Preci pi tati on ............................................................................................1-17
Phase Equi l i bri a I nvol vi ng Sol i ds for Metal l urgi cal Appl i cati ons...............1-17
Cal cul ati on of Other Properti es Usi ng Acti vi ty Coeffi ci ents................................1-19
Advantages and Di sadvantages of the Acti vi ty Coeffi ci ent Method.......................1-21
References ................................................................................................................1-21
Equati on-of-State Model s................................................................................................1-22
Cubi c Equati ons of State .........................................................................................1-22
Pure Components............................................................................................1-23
Mi xtures ..........................................................................................................1-24
Vi ri al Equati ons of State........................................................................................1-25
Vapor Phase Associ ati on ........................................................................................1-26
References ...............................................................................................................1-30
Acti vi ty Coeffi ci ent Model s .............................................................................................1-32
Mol ecul ar Model s.....................................................................................................1-32
Group Contri buti on Model s.....................................................................................1-33
El ectrol yte Model s ...................................................................................................1-33
References ................................................................................................................1-34
Transport Property Methods .............................................................................................1-34
Vi scosi ty and Thermal Conducti vi ty Methods ...............................................................1-35
Di ffusi on Coeffi ci ent Methods.........................................................................................1-36
Surface Tensi on Methods ................................................................................................1-37
Physi cal Property Methods and Model s
Versi on 10
i v
References....................................................................................................................... 1-37
Nonconventi onal Component Enthal py Cal cul ati on ....................................................... 1-37
Footnotes ............................................................................................................................ 1-39
2 Property Method Descriptions
Cl assi fi cati on of Property Methods and Recommended Use............................................. 2-2
I DEAL Property Method ..................................................................................................... 2-7
Mi xture Types .......................................................................................................... 2-8
Range ........................................................................................................................ 2-8
Use of Henrys Law .................................................................................................. 2-8
Property Methods for Petrol eum Mi xtures ...................................................................... 2-10
Li qui d Fugaci ty and K-Val ue Model Property Methods................................................ 2-11
BK10............................................................................................................................... 2-11
Mi xture Types ........................................................................................................ 2-12
Range ...................................................................................................................... 2-12
CHAO-SEA..................................................................................................................... 2-12
Mi xture Types ........................................................................................................ 2-13
Range ...................................................................................................................... 2-13
GRAYSON...................................................................................................................... 2-14
Mi xture Types ........................................................................................................ 2-14
Range ...................................................................................................................... 2-14
Petrol eum-Tuned Equati on-of-State Property Methods ............................................. 2-15
PENG-ROB .................................................................................................................... 2-15
Mi xture Types ........................................................................................................ 2-16
Range ...................................................................................................................... 2-16
RK-SOAVE ..................................................................................................................... 2-17
Mi xture Types ........................................................................................................ 2-17
Range ...................................................................................................................... 2-17
Common Model s ............................................................................................................. 2-18
Equati on-of-State Property Methods for Hi gh-Pressure Hydrocarbon Appl i cati ons .... 2-20
BWR-LS.......................................................................................................................... 2-21
Mi xture Types ........................................................................................................ 2-21
Range ...................................................................................................................... 2-22
LK-PLOCK ..................................................................................................................... 2-22
Mi xture Types ........................................................................................................ 2-23
Range ...................................................................................................................... 2-23
PR-BM............................................................................................................................ 2-23
Mi xture Types ........................................................................................................ 2-24
Range ...................................................................................................................... 2-24
RKS-BM.......................................................................................................................... 2-24
Mi xture Types ........................................................................................................ 2-24
Range ...................................................................................................................... 2-25
Common Model s ............................................................................................................. 2-25
Fl exi bl e and Predi cti ve Equati on-of-State Property Methods ........................................ 2-26
PRMHV2 ........................................................................................................................ 2-28
Mi xture Types ........................................................................................................ 2-29
Range ...................................................................................................................... 2-29
PRWS.............................................................................................................................. 2-29
Mi xture Types ........................................................................................................ 2-30
Range ...................................................................................................................... 2-30
Physi cal Property Methods and Model s v
Rel ease 10
PSRK ...............................................................................................................................2-30
Mi xture Types .........................................................................................................2-31
Range .......................................................................................................................2-31
RK-ASPEN......................................................................................................................2-31
Mi xture Types .........................................................................................................2-32
Range .......................................................................................................................2-32
RKSMHV2.......................................................................................................................2-32
Mi xture Types .........................................................................................................2-33
Range .......................................................................................................................2-33
RKSWS............................................................................................................................2-33
Mi xture Types .........................................................................................................2-34
Range .......................................................................................................................2-34
SR-POLAR ......................................................................................................................2-34
Mi xture Types .........................................................................................................2-35
Range .......................................................................................................................2-35
Common Model s ..............................................................................................................2-36
Li qui d Acti vi ty Coeffi ci ent Property Methods ..................................................................2-37
Equati ons of State...........................................................................................................2-37
I deal Gas Law .........................................................................................................2-39
Mi xture Types .................................................................................................2-39
Range...............................................................................................................2-39
Redl i ch-Kwong ........................................................................................................2-40
Mi xture Types .................................................................................................2-40
Range...............................................................................................................2-40
Nothnagel ................................................................................................................2-40
Mi xture Types .................................................................................................2-41
Range...............................................................................................................2-41
Hayden-OConnel l ...................................................................................................2-41
Mi xture Types .................................................................................................2-42
Range...............................................................................................................2-42
HF Equati on of State..............................................................................................2-42
Mi xture Types .................................................................................................2-42
Range...............................................................................................................2-42
NRTL .......................................................................................................................2-43
Mi xture Types .................................................................................................2-44
Range...............................................................................................................2-44
UNI FAC ..................................................................................................................2-45
Mi xture Types .................................................................................................2-47
Range...............................................................................................................2-47
UNI QUAC ...............................................................................................................2-48
Mi xture Types .................................................................................................2-49
Range...............................................................................................................2-49
Van Laar ..................................................................................................................2-49
Mi xture Types .................................................................................................2-50
Range...............................................................................................................2-50
Wi l son ......................................................................................................................2-51
Mi xture Types .................................................................................................2-52
Range...............................................................................................................2-52
Common Model s ..............................................................................................................2-53
El ectrol yte Property Methods............................................................................................2-54
Versi on 10
vi
AMI NES ......................................................................................................................... 2-55
Range ...................................................................................................................... 2-56
API SOUR ....................................................................................................................... 2-57
ELECNRTL .................................................................................................................... 2-58
Mi xture Types ........................................................................................................ 2-59
Range ...................................................................................................................... 2-59
ENRTL-HF ..................................................................................................................... 2-60
Mi xture Types ........................................................................................................ 2-60
Range ...................................................................................................................... 2-60
ENRTL-HG..................................................................................................................... 2-61
Mi xture Types ........................................................................................................ 2-61
Range ...................................................................................................................... 2-61
PI TZER........................................................................................................................... 2-62
Mi xture Types ........................................................................................................ 2-62
Range ...................................................................................................................... 2-62
B-PI TZER....................................................................................................................... 2-64
Mi xture Types ........................................................................................................ 2-64
Range ...................................................................................................................... 2-64
PI TZ-HG......................................................................................................................... 2-66
Mi xture Types ........................................................................................................ 2-66
Range ...................................................................................................................... 2-66
General and Transport Property Model Parameter Requi rements .............................. 2-66
Sol i ds Handl i ng Property Method .................................................................................... 2-67
Steam Tabl es...................................................................................................................... 2-71
STEAM-TA..................................................................................................................... 2-71
Range ...................................................................................................................... 2-72
STEAMNBS ................................................................................................................... 2-72
Range ...................................................................................................................... 2-72
3 Property Model Descriptions
Thermodynami c Property Model s ...................................................................................... 3-3
Equati on-of-State Model s.................................................................................................... 3-7
ASME Steam Tabl es ................................................................................................ 3-8
References......................................................................................................... 3-8
BWR-Lee-Starl i ng..................................................................................................... 3-8
References......................................................................................................... 3-9
Hayden-OConnel l ..................................................................................................... 3-9
Cross-I nteracti ons........................................................................................... 3-10
Chemi cal Theory ............................................................................................ 3-11
References....................................................................................................... 3-13
HF Equati on-of-State.............................................................................................. 3-13
Mol ar Vol ume Cal cul ati on.............................................................................. 3-13
True Mol e Fracti on (Parti al Pressure) Cal cul ati on ....................................... 3-14
Gi bbs Energy and Fugaci ty ............................................................................ 3-15
Enthal py and Entropy .................................................................................... 3-16
Usage .............................................................................................................. 3-16
References....................................................................................................... 3-17
I deal Gas ................................................................................................................. 3-17
Lee-Kesl er ............................................................................................................... 3-18
References....................................................................................................... 3-19
Physi cal Property Methods and Model s vi i
Rel ease 10
Lee-Kesl er-Pl cker ...................................................................................................3-19
References .......................................................................................................3-21
NBS/NRC Steam Tabl es..........................................................................................3-21
References .......................................................................................................3-21
Nothnagel ................................................................................................................3-22
References .......................................................................................................3-24
Peng-Robi nson-Boston-Mathi as ..............................................................................3-25
References........................................................................................................3-26
Peng-Robi nson-MHV2 .............................................................................................3-26
Predi cti ve SRK (PSRK) ..........................................................................................3-26
Peng-Robi nson-Wong-Sandl er .................................................................................3-26
Redl i ch-Kwong.........................................................................................................3-27
References........................................................................................................3-27
Redl i ch-Kwong-Aspen .............................................................................................3-28
References........................................................................................................3-29
Redl i ch-Kwong-Soave-Boston-Mathi as ...................................................................3-29
References........................................................................................................3-30
Redl i ch-Kwong-Soave-Wong-Sandl er .....................................................................3-30
Redl i ch-Kwong-Soave-MHV2..................................................................................3-31
Schwartzentruber-Renon ........................................................................................3-31
References........................................................................................................3-33
Standard Peng-Robi nson .........................................................................................3-34
References........................................................................................................3-35
Standard Redl i ch-Kwong-Soave..............................................................................3-35
References........................................................................................................3-36
Peng-Robi nson Al pha Functi ons .............................................................................3-36
Boston-Mathi as Extrapol ati on ........................................................................3-37
Mathi as-Copeman Al pha Functi on .................................................................3-37
Schwartzentruber-Renon-Watanasi ri Al pha Functi on ..................................3-38
Use of Al pha Functi ons ...................................................................................3-39
References........................................................................................................3-39
Soave Al pha Functi ons ............................................................................................3-40
Soave Modi fi cati on ..........................................................................................3-40
Boston-Mathi as Extrapol ati on ........................................................................3-41
Mathi as Al pha Functi on..................................................................................3-41
Extended Mathi as Al pha Functi on .................................................................3-42
Mathi as-Copeman Al pha Functi on .................................................................3-43
Schwartzentruber-Renon-Watanasi ri Al pha Functi on ..................................3-43
Use of Al pha Functi ons ...................................................................................3-44
References........................................................................................................3-45
Huron-Vi dal Mi xi ng Rul es .....................................................................................3-46
References........................................................................................................3-47
MHV2 Mi xi ng Rul es ................................................................................................3-48
References .........................................................................................................3-49
Predi cti ve Soave-Redl i ch-Kwong-Gmehl i ng Mi xi ng Rul es.....................................3-49
References........................................................................................................3-51
Wong-Sandl er Mi xi ng Rul es....................................................................................3-51
References........................................................................................................3-53
Broml ey-Pi tzer Acti vi ty Coeffi ci ent Model ..............................................................3-54
Chi en-Nul l ...............................................................................................................3-55
Constant Acti vi ty Coeffi ci ent .................................................................................3-58
Versi on 10
vi i i
El ectrol yte NRTL Acti vi ty Coeffi ci ent Model ....................................................... 3-58
I deal Li qui d ............................................................................................................ 3-62
NRTL (Non-Random Two-Li qui d)......................................................................... 3-62
References....................................................................................................... 3-63
Pi tzer Acti vi ty Coeffi ci ent Model ............................................................................ 3-63
Pol ynomi al Acti vi ty Coeffi ci ent .............................................................................. 3-65
Redl i ch-Ki ster ......................................................................................................... 3-66
Scatchard-Hi l debrand............................................................................................. 3-67
Three-Suffi x Margul es ........................................................................................... 3-68
References....................................................................................................... 3-69
UNI FAC.................................................................................................................. 3-69
References....................................................................................................... 3-71
UNI FAC (Dortmund Modi fi ed) .............................................................................. 3-71
References....................................................................................................... 3-72
UNI FAC (Lyngby Modi fi ed)................................................................................... 3-72
References....................................................................................................... 3-74
UNI QUAC............................................................................................................... 3-74
References ....................................................................................................... 3-75
Van Laar ................................................................................................................. 3-75
References....................................................................................................... 3-76
Wagner I nteracti on Parameter .............................................................................. 3-77
References....................................................................................................... 3-78
Wi l son...................................................................................................................... 3-78
References....................................................................................................... 3-79
Wi l son Model wi th Li qui d Mol ar Vol ume............................................................. 3-79
References....................................................................................................... 3-79
Vapor Pressure and Li qui d Fugaci ty Model s ................................................................ 3-80
Extended Antoi ne/Wagner...................................................................................... 3-80
Extended Antoi ne Equati on ........................................................................... 3-80
Wagner Vapor Pressure Equati on.................................................................. 3-81
References ....................................................................................................... 3-81
Chao-Seader ............................................................................................................ 3-81
References ....................................................................................................... 3-82
Grayson-Streed ....................................................................................................... 3-82
References ....................................................................................................... 3-82
Kent-Ei senberg ....................................................................................................... 3-82
References ....................................................................................................... 3-84
Heat of Vapori zati on Model ............................................................................................ 3-85
DI PPR Equati on ..................................................................................................... 3-85
Watson Equati on .................................................................................................... 3-85
Cl ausi us-Cl apeyron Equati on ............................................................................... 3-86
Mol ar Vol ume and Densi ty Model s ................................................................................ 3-86
API Li qui d Vol ume ................................................................................................. 3-87
Brel vi -OConnel l ...................................................................................................... 3-88
References ....................................................................................................... 3-89
Cl arke Aqueous El ectrol yte Vol ume....................................................................... 3-89
Apparent Component Approach ..................................................................... 3-89
True Component Approach ............................................................................ 3-90
Temperature Dependence .............................................................................. 3-90
COSTALD Li qui d Vol ume ...................................................................................... 3-91
References ....................................................................................................... 3-92
Debi je-Hckel Vol ume ............................................................................................ 3-92
Physi cal Property Methods and Model s i x
Rel ease 10
References........................................................................................................3-93
Rackett/DI PPR Pure Component Li qui d Vol ume...................................................3-93
DI PPR..............................................................................................................3-94
Rackett.............................................................................................................3-94
References........................................................................................................3-95
Rackett Mi xture Li qui d Vol ume ............................................................................3-95
References .......................................................................................................3-96
Modi fi ed Rackett.............................................................................................3-96
References .......................................................................................................3-97
Sol i ds Vol ume Pol ynomi al .......................................................................................3-97
Heat Capaci ty Model s .....................................................................................................3-98
Aqueous I nfi ni te Di l uti on Heat Capaci ty................................................................3-98
Cri ss-Cobbl e Aqueous I nfi ni te Di l uti on I oni c Heat Capaci ty .................................3-98
DI PPR Li qui d Heat Capaci ty ..................................................................................3-99
I deal Gas Heat Capaci ty/DI PPR ...........................................................................3-100
DI PPR............................................................................................................3-100
I deal Gas Heat Capaci ty Pol ynomi al ............................................................3-101
References......................................................................................................3-102
Sol i ds Heat Capaci ty Pol ynomi al ..........................................................................3-102
Sol ubi l i ty Correl ati ons ..................................................................................................3-102
Henrys Constant ...................................................................................................3-103
Water Sol ubi l i ty ....................................................................................................3-104
Other Thermodynami c Property Model s ......................................................................3-105
Cavett.....................................................................................................................3-105
BARI N Equati ons for Gi bbs Energy, Enthal py, Entropy, and Heat Capaci ty ....3-106
Sol i d Phase ....................................................................................................3-106
Li qui d Phase .................................................................................................3-107
I deal Gas Phase ............................................................................................3-108
El ectrol yte NRTL Enthal py .................................................................................3-109
El ectrol yte NRTL Gi bbs Energy ...........................................................................3-110
Li qui d Enthal py from Li qui d Heat Capaci ty Correl ati on ..................................3-111
Enthal pi es Based on Di fferent Reference States ................................................3-112
Saturated Li qui d as Reference State...........................................................3-113
I deal Gas as Reference State........................................................................3-115
Hel geson Equati ons of State ................................................................................3-117
References .....................................................................................................3-119
Transport Property Model s..............................................................................................3-120
Vi scosi ty Model s ...........................................................................................................3-121
Andrade/DI PPR ....................................................................................................3-122
Andrade .........................................................................................................3-123
DI PPR Li qui d Vi scosi ty................................................................................3-123
References .....................................................................................................3-123
API Li qui d Vi scosi ty ..............................................................................................3-124
Chapman-Enskog-Brokaw/DI PPR.......................................................................3-124
Chapman-Enskog-Brokaw ............................................................................3-124
DI PPR Vapor Vi scosi ty..................................................................................3-125
References......................................................................................................3-126
Chapman-Enskog-Brokaw-Wi l ke Mi xi ng Rul e.....................................................3-126
References......................................................................................................3-127
Chung-Lee-Starl i ng Low-Pressure Vapor Vi scosi ty .............................................3-127
References......................................................................................................3-129
Chung-Lee-Starl i ng Vi scosi ty ...............................................................................3-129
Versi on 10
x
References ..................................................................................................... 3-131
Dean-Sti el Pressure Correcti on ............................................................................ 3-131
I APS Vi scosi ty for Water ...................................................................................... 3-132
Jones-Dol e El ectrol yte Correcti on ........................................................................ 3-133
Jones-Dol e..................................................................................................... 3-133
Bresl au-Mi l l er ............................................................................................... 3-134
Carbonel l ....................................................................................................... 3-134
References ..................................................................................................... 3-134
Letsou-Sti el ........................................................................................................... 3-135
References ..................................................................................................... 3-135
Lucas Vapor Vi scosi ty........................................................................................... 3-135
References ..................................................................................................... 3-137
TRAPP Vi scosi ty Model ........................................................................................ 3-137
References ..................................................................................................... 3-137
Thermal Conducti vi ty Model s..................................................................................... 3-138
Chung-Lee-Starl i ng Thermal Conducti vi ty........................................................ 3-138
References..................................................................................................... 3-140
I APS Thermal Conducti vi ty for Water ................................................................. 3-140
Li Mi xi ng Rul e...................................................................................................... 3-140
Ri edel El ectrol yte Correcti on................................................................................ 3-141
Sato-Ri edel /DI PPR................................................................................................ 3-142
Sato-Ri edel .................................................................................................... 3-142
DI PPR........................................................................................................... 3-142
Vredevel d Mi xi ng Rul e ................................................................................ 3-143
References ..................................................................................................... 3-143
Sti el -Thodos/DI PPR.............................................................................................. 3-143
Sti el -Thodos .................................................................................................. 3-144
DI PPR Vapor Thermal Conducti vi ty ........................................................... 3-144
References ..................................................................................................... 3-145
Sti el -Thodos Pressure Correcti on Model .............................................................. 3-145
References..................................................................................................... 3-145
TRAPP Thermal Conducti vi ty Model ................................................................. 3-145
References..................................................................................................... 3-146
Wassi l jewa-Mason-Saxena Mi xi ng Rul e............................................................. 3-146
References..................................................................................................... 3-147
Di ffusi vi ty Model s........................................................................................................ 3-148
Chapman-Enskog-Wi l ke-Lee (Bi nary)................................................................ 3-148
References ..................................................................................................... 3-149
Chapman-Enskog-Wi l ke-Lee (Mi xture)............................................................... 3-149
References ..................................................................................................... 3-150
Dawson-Khoury-Kobayashi (Bi nary)................................................................... 3-150
References ..................................................................................................... 3-150
Dawson-Khoury-Kobayashi (Mi xture) ................................................................. 3-151
References ..................................................................................................... 3-151
Nernst-Hartl ey...................................................................................................... 3-151
References ..................................................................................................... 3-152
Wi l ke-Chang (Bi nary)........................................................................................... 3-152
References ..................................................................................................... 3-153
Wi l ke-Chang (Mi xture)......................................................................................... 3-153
References ..................................................................................................... 3-154
Surface Tensi on Model s ............................................................................................... 3-154
API Surface Tensi on ............................................................................................. 3-154
Physi cal Property Methods and Model s xi
Rel ease 10
I APS Surface Tensi on for Water ...........................................................................3-155
Haki m-Stei nberg-Sti el /DI PPR.............................................................................3-155
Haki m-Stei nberg-Sti el ...................................................................................3-155
DI PPR Li qui d Surface Tensi on .....................................................................3-156
References......................................................................................................3-156
Onsager-Samaras ..................................................................................................3-156
References......................................................................................................3-157
Nonconventi onal Sol i d Property Model s .........................................................................3-158
General Enthal py and Densi ty Model s ........................................................................3-158
General Densi ty Pol ynomi al ..................................................................................3-158
General Heat Capaci ty Pol ynomi al .......................................................................3-159
Enthal py and Densi ty Model s for Coal and Char ........................................................3-160
Notati on .................................................................................................................3-161
General Coal Enthal py Model ...............................................................................3-163
Heat of Combusti on Correl ati ons ..................................................................3-163
Standard Heat of Formati on Correl ati ons ....................................................3-167
Heat Capaci ty Ki rov Correl ati ons.................................................................3-168
Cubi c Temperature Equati on........................................................................3-170
I GT Coal Densi ty Model .......................................................................................3-171
I GT Char Densi ty Model .......................................................................................3-173
References .......................................................................................................3-174
4 Property Calculation Methods and Routes
I ntroducti on ..........................................................................................................................4-2
Physi cal Properti es i n ASPEN PLUS .................................................................................4-3
Methods .................................................................................................................................4-9
Routes And Model s .............................................................................................................4-36
Concept of Routes ............................................................................................................4-36
Model s .............................................................................................................................4-39
Property Model Opti on Codes ........................................................................................4-45
Traci ng a Route...............................................................................................................4-50
Modi fyi ng and Creati ng Property Method .........................................................................4-51
Modi fyi ng Exi sti ng Property Methods............................................................................4-51
Repl aci ng Routes .....................................................................................................4-51
Repl aci ng Model s and Usi ng Mul ti pl e Data Sets ...................................................4-53
Confl i cti ng Route and Model Speci fi cati ons............................................................4-54
Creati ng New Property Methods ....................................................................................4-55
Usi ng Mul ti pl e Data Sets i n Mul ti pl e Property Methods.......................................4-56
Modi fyi ng and Creati ng Routes ..........................................................................................4-57
5 Electrolyte Simulation
Sol uti on Chemi stry ...........................................................................................................5-2
Apparent Component and True Component Approaches ..............................................5-3
Choosi ng the True or Apparent Approach ................................................................5-4
Reconsti tuti on of Apparent Component Mol e Fracti ons...........................................5-6
El ectrol yte Thermodynami c Model s .................................................................................5-7
Pi tzer Equati on..........................................................................................................5-7
El ectrol yte NRTL Equati on......................................................................................5-8
Zemai ti s Equati on (Broml ey-Pi tzer Model ) ..............................................................5-8
Future Model s............................................................................................................5-8
Versi on 10
xi i
El ectrol yte Data Regressi on ............................................................................................. 5-9
References......................................................................................................................... 5-9
6 Free-Water and Rigorous Three-Phase Calculations
Free-Water I mmi sci bi l i ty Si mpl i fi cati on ......................................................................... 6-2
Speci fyi ng Free-Water Cal cul ati ons ....................................................................... 6-3
Free-Water Phase Properti es.................................................................................... 6-3
Organi c Phase Properti es ......................................................................................... 6-4
Ri gorous Three-Phase Cal cul ati ons ................................................................................. 6-5
7 Petroleum Components Characterization Methods
Property Methods for Characteri zati on of Petrol eum Components ............................. 7-3
References ........................................................................................................................ 7-6
8 Property Parameter Estimation
Descri pti on of Esti mati on Methods .................................................................................... 8-3
Mol ecul ar Wei ght (MW)............................................................................................ 8-3
Normal Boi l i ng Poi nt (TB)........................................................................................ 8-4
Joback Method ................................................................................................. 8-4
Ogata-Tsuchi da Method .................................................................................. 8-4
Gani Method..................................................................................................... 8-4
Mani Method .................................................................................................... 8-5
Cri ti cal Temperature (TC)....................................................................................... 8-5
Joback Method ................................................................................................. 8-5
Lydersen Method ............................................................................................. 8-5
Ambrose Method .............................................................................................. 8-6
Fedors Method.................................................................................................. 8-6
Si mpl e Method ................................................................................................. 8-6
Gani Method..................................................................................................... 8-6
Mani Method .................................................................................................... 8-6
Cri ti cal Pressure (PC).............................................................................................. 8-7
Joback Method ................................................................................................. 8-7
Lydersen Method ............................................................................................. 8-7
Ambrose Method .............................................................................................. 8-7
Gani Method..................................................................................................... 8-7
Cri ti cal Vol ume (VC)................................................................................................ 8-8
Joback Method ................................................................................................. 8-8
Lydersen Method ............................................................................................. 8-8
Ambrose Method .............................................................................................. 8-8
Ri edel Method .................................................................................................. 8-8
Fedors Method.................................................................................................. 8-9
Gani Method..................................................................................................... 8-9
Cri ti cal Compressi bi l i ty Factor (ZC)....................................................................... 8-9
Acentri c Factor (OMEGA) ....................................................................................... 8-9
Defi ni ti on Method .......................................................................................... 8-10
Lee-Kesl er Method......................................................................................... 8-10
Standard Enthal py of Formati on (DHFORM) ..................................................... 8-10
Benson Method............................................................................................... 8-10
Joback Method ............................................................................................... 8-11
BensonR8 Method .......................................................................................... 8-11
Physi cal Property Methods and Model s xi i i
Rel ease 10
Gani Method....................................................................................................8-11
Standard Gi bbs Free Energy of Formati on (DGFORM).......................................8-11
Benson Method ...............................................................................................8-11
Joback Method ................................................................................................8-12
Gani Method....................................................................................................8-12
Heat of Vapori zati on at TB (DHVLB)....................................................................8-12
Li qui d Mol ar Vol ume at TB (VB)...........................................................................8-12
Standard Li qui d Vol ume (VLSTD)........................................................................8-12
Radi us of Gyrati on (RGYR)....................................................................................8-12
Sol ubi l i ty Parameter (DELTA)..............................................................................8-12
UNI QUAC R and Q Parameters (GMUQR, GMUQQ).........................................8-13
Parachor (PARC).....................................................................................................8-13
I deal Gas Heat Capaci ty (CPI G)............................................................................8-13
Benson Method ...............................................................................................8-13
Joback Method ................................................................................................8-13
Data Method ...................................................................................................8-14
Vapor Pressure (PLXANT).....................................................................................8-14
Data Method ...................................................................................................8-14
Ri edel Method .................................................................................................8-14
Li -Ma Method..................................................................................................8-14
Mani Method ...................................................................................................8-15
Heat of Vapori zati on (DHVLWT)...........................................................................8-15
Data Method ...................................................................................................8-15
Defi ni ti on Method...........................................................................................8-15
Vetere Method.................................................................................................8-15
Gani Method....................................................................................................8-16
Ducros Method ................................................................................................8-16
Li -Ma Method..................................................................................................8-16
Li qui d Mol ar Vol ume (RKTZRA)...........................................................................8-16
Gunn-Yamada Method ...................................................................................8-17
Le Bas Method ................................................................................................8-17
Data Method ...................................................................................................8-17
Li qui d Vi scosi ty (MULAND)..................................................................................8-17
Orri ck-Erbar Method......................................................................................8-17
Letsou-Sti el Method........................................................................................8-18
Data Method ...................................................................................................8-18
Vapor Vi scosi ty (MUVDI P) ....................................................................................8-18
Rei chenberg Method .......................................................................................8-18
Data Method ...................................................................................................8-18
Li qui d Thermal Conducti vi ty (KLDI P) .................................................................8-18
Sato-Ri edel Method.........................................................................................8-19
Data Method ...................................................................................................8-19
Vapor Thermal Conducti vi ty (KVDI P)..................................................................8-19
Surface Tensi on (SI GDI P)......................................................................................8-19
Data Method ...................................................................................................8-19
Brock-Bi rd Method .........................................................................................8-19
Macl eod-Sugden Method ................................................................................8-19
Li -Ma Method..................................................................................................8-20
Li qui d Heat Capaci ty (CPLDI P)............................................................................8-20
Data Method ...................................................................................................8-20
Ruzi cka Method ..............................................................................................8-20
Sol i d Heat Capaci ty (CPSPO1)..............................................................................8-21
Versi on 10
xi v
Data Method................................................................................................... 8-21
Mostafa Method ............................................................................................. 8-21
Sol i d Standard Enthal py of Formati on (DHSFRM)............................................. 8-21
Mostafa Method ............................................................................................. 8-21
Sol i d Standard Gi bbs Free Energy of Formati on (DGSFRM)............................. 8-22
Mostafa Method ............................................................................................. 8-22
Standard Enthal py of Formati on of Aqueous Speci es (DHAQHG)..................... 8-22
AQU-DATA Method ....................................................................................... 8-22
THERMO Method .......................................................................................... 8-22
AQU-EST1 Method ........................................................................................ 8-23
AQU-EST2 Method ........................................................................................ 8-23
Standard Gi bbs Free Energy of Formati on of Aqueous Speci es (DGAQHG)..... 8-23
AQU-DATA Method ....................................................................................... 8-23
THERMO Method .......................................................................................... 8-23
AQU-EST1 Method ........................................................................................ 8-24
AQU-EST2 Method ........................................................................................ 8-24
Absol ute Entropy of Aqueous Speci es (S25HG) ................................................... 8-24
AQU-DATA Method ....................................................................................... 8-24
THERMO Method .......................................................................................... 8-24
AQU-EST1 Method ........................................................................................ 8-25
AQU-EST2 Method ........................................................................................ 8-25
Born Coeffi ci ent (OMEGHG)................................................................................. 8-25
Hel geson Capaci ty Parameters (CHGPAR).......................................................... 8-25
HG-AQU Method ........................................................................................... 8-25
HG-CRI S Method ........................................................................................... 8-25
HG-EST Method............................................................................................. 8-25
Bi nary Parameters (WI LSON, NRTL, UNI Q) ..................................................... 8-26
UNI FAC R and Q Parameters (GMUFR, GMUFQ, GMUFDR, GMUFDQ,
GMUFLR, GMUFLQ)............................................................................................. 8-26
A Bromley-Pitzer Activity Coefficient Model
Worki ng Equati ons..............................................................................................................A-1
Parameter Conversi on.........................................................................................................A-2
References ............................................................................................................................A-3
B Electrolyte NRTL Activity Coefficient Model
Theoreti cal Basi s and Worki ng Equati ons.........................................................................B-1
Devel opment of the Model ...............................................................................................B-2
Long-Range I nteracti on Contri buti on ............................................................................B-3
Local I nteracti on Contri buti on .......................................................................................B-4
Apparent Bi nary Systems ...............................................................................................B-5
Mul ti component Systems ................................................................................................B-9
Parameters.....................................................................................................................B-11
Obtai ni ng Parameters .......................................................................................................B-11
References ..........................................................................................................................B-12
C Pitzer Activity Coefficient Model
Model Devel opment .............................................................................................................C-1
Appl i cati on of the Pi tzer Model to Aqueous Strong El ectrol yte Systems.........................C-3
Physi cal Property Methods and Model s xv
Rel ease 10
Cal cul ati on of Acti vi ty Coeffi ci ents .................................................................................... C-5
Appl i cati on of the Pi tzer Model to Aqueous El ectrol yte Systems wi th Mol ecul ar
Sol utes.............................................................................................................................. C-8
Parameters....................................................................................................................... C-9
Parameter Conversi on ............................................................................................. C-9
Parameter Sources................................................................................................. C-10
References .......................................................................................................................... C-11
Index Index-1
Versi on 10
xvi
Versi on 10
xvi i
About Physical Property
Methods and Models
Physical Property Methods and Models provi des an overvi ew of ASPEN PLUS
physi cal property methods and detai l ed techni cal reference i nformati on on
property opti on sets, property cal cul ati on methods and routes, property model s,
and parameter esti mati on. Thi s vol ume al so i ncl udes techni cal reference
i nformati on for handl i ng physi cal properti es i n el ectrol ytes si mul ati ons, ri gorous
and three-phase cal cul ati ons, and petrol eum components characteri zati on
methods. Much of thi s i nformati on i s al so avai l abl e i n onl i ne prompts and hel p.
At Rel ease 9.3, correcti ons were made to property model s i n Chapter 3. Many
property model s have been added to ASPEN PLUS Rel ease 9.3 and are now
documented, for exampl e the Wi l son model wi th l i qui d mol ar vol ume, the Li
mi xi ng rul es for l i qui d thermal conducti vi ty and the new enthal py methods.
For i nformati on and l i sti ngs for al l ASPEN PLUS databanks, el ectrol ytes data,
group contri buti on method functi onal groups, and property sets, see
ASPEN PLUS Physical Property Data.
An overvi ew of the ASPEN PLUS physi cal property system, and i nformati on
about how to use i ts ful l range and power, i s i n the ASPEN PLUS User Guide, as
wel l as i n onl i ne hel p and prompts i n ASPEN PLUS.
Versi on 10.0
xvi i i
For More Information
Onl i ne Hel p ASPEN PLUS has a compl ete system of onl i ne hel p and
context-sensi ti ve prompts. The hel p system contai ns both context-sensi ti ve hel p
and reference i nformati on. For more i nformati on about usi ng ASPEN PLUS hel p,
see the ASPEN PLUS User Guide, Chapter 3.
ASPEN PLUS Getti ng Started Bui l di ng and Runni ng a Process Model
Thi s tutori al i ncl udes several hands-on sessi ons to fami l i ari ze you wi th
ASPEN PLUS. The gui de takes you step-by-step to l earn the ful l power and scope
of ASPEN PLUS.
ASPEN PLUS User Gui de The three-vol ume ASPEN PLUS User Guide
provi des step-by-step procedures for devel opi ng and usi ng an ASPEN PLUS
process si mul ati on model . The gui de i s task -ori ented to hel p you accompl i sh the
engi neeri ng work you need to do, usi ng the powerful capabi l i ti es of
ASPEN PLUS.
ASPEN PLUS reference manual seri es ASPEN PLUS reference manual s
provi de detai l ed techni cal reference i nformati on. These manual s i ncl ude
background i nformati on about the uni t operati on model s and the physi cal
properti es methods and model s avai l abl e i n ASPEN PLUS, tabl es of
ASPEN PLUS databank parameters, group contri buti on method functi onal
groups, and a wi de range of other reference i nformati on. The set compri ses:
Unit Operation Models
Physical Property Methods and Models
Physical Property Data
User Models
System Management
Summary File Toolkit
ASPEN PLUS appl i cati on exampl es A sui te of sampl e onl i ne ASPEN PLUS
si mul ati ons i l l ustrati ng speci fi c processes i s del i vered wi th ASPEN PLUS.
ASPEN PLUS I nstal l ati on Gui des These gui des provi de i nstructi ons on
pl atform and network i nstal l ati on of ASPEN PLUS. The set compri ses:
ASPEN PLUS I nstallation Guide for Wi ndows
ASPEN PLUS I nstallation Guide for OpenVMS
ASPEN PLUS I nstallation Guide for UNI X
The ASPEN PLUS manual s are del i vered i n Adobe portabl e document format
(PDF) on the ASPEN PLUS Documentati on CD. You can al so order pri nted
manual s from AspenTech.
Versi on 10
xi x
Technical Support
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O O O O
Versi on 10.0
xx
Physi cal Property Methods and Model s 1-1
Versi on 10
Chapter 1
1 Overview of ASPEN PLUS
Property Methods
Al l uni t operati on model s need property cal cul ati ons to generate resul ts. The
most often requested properti es are fugaci ti es for thermodynami c equi l i bri um
(fl ash cal cul ati on). Enthal py cal cul ati ons are al so often requested. Fugaci ti es and
enthal pi es are often suffi ci ent i nformati on to cal cul ate a mass and heat bal ance.
However, other thermodynami c properti es (and, i f requested, transport
properti es) are cal cul ated for al l process streams.
The i mpact of property cal cul ati on on the si mul ati on resul t i s great. Thi s i s due to
the qual i ty and the choi ce of the equi l i bri um and property cal cul ati ons.
Equi l i bri um cal cul ati on and the bases of property cal cul ati on are expl ai ned i n thi s
chapter. The understandi ng of these bases i s i mportant to choose the appropri ate
property cal cul ati on. Chapter 2 gi ves more hel p on thi s subject. The qual i ty of the
property cal cul ati on i s determi ned by the model equati ons themsel ves and by the
usage. For opti mal usage, you may need detai l s on property cal cul ati on. These are
gi ven i n the Chapters 3 and 4.
Thi s chapter contai ns three secti ons:
Thermodynami c property methods
Transport property methods
Nonconventi onal component enthal py cal cul ati on
The thermodynami c property methods secti on di scusses the two methods of
cal cul ati ng vapor-l i qui d equi l i bri um (VLE): the equati on-of-state method and the
acti vi ty coeffi ci ent method. Each method contai ns the fol l owi ng:
Fundamental concepts of phase equi l i bri a and the equati ons used
Appl i cati on to vapor-l i qui d equi l i bri a and other types of equi l i bri a, such as
l i qui d-l i qui d
Cal cul ati ons of other thermodynami c properti es
The l ast part of thi s secti on gi ves an overvi ew of the current equati on of state and
acti vi ty coeffi ci ent technol ogy.
1-2 Physi cal Property Methods and Model s
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
The tabl e l abel ed Symbol Defi ni ti ons on page 1-38 defi nes the symbol s used i n
equati ons.
Thermodynamic Property Methods
The key thermodynami c property cal cul ati on performed i n a si mul ati on i s phase
equi l i bri um. The basi c rel ati onshi p for every component i i n the vapor and l i qui d
phases of a system at equi l i bri um i s:
f f
i
v
i
l
(1)
Where:
f
i
v
= Fugaci ty of component i i n the vapor phase
f
i
l
= Fugaci ty of component i i n the l i qui d phase
Appl i ed thermodynami cs provi des two methods for representi ng the fugaci ti es from
the phase equi l i bri um rel ati onshi p i n terms of measurabl e state vari abl es, the
equati on-of-state method and the acti vi ty coeffi ci ent method.
I n the equati on of state method:
f y p
i
v
i
v
i
(2)
f x p
i
l
i
l
i
(3)
Wi th
ln ln
, ,
i
i
T V n
V
m
RT
p
n
RT
V
d V Z
iej

_
,

1
]
1
1

1
(4)
Where:
= v or l
V = Total vol ume
n
i
= Mol e number of component i
Versi on 10
Chapter 1
Equati ons 2 and 3 are i denti cal wi th the onl y di fference bei ng the phase to whi ch
the vari abl es appl y. The fugaci ty coeffi ci ent
i
i s obtai ned from the equati on of
state, represented by p i n equati on 4. See equati on 45 for an exampl e of an
equati on of state.
I n the acti vi ty coeffi ci ent method:
f
i
v
=
i
v
i
y p (5)
f
i
l
= x f
i i i
l
*,
(6)
Where
i
v
i s cal cul ated accordi ng to equati on 4,
i
= Li qui d acti vi ty coeffi ci ent of component i
f
i
l *,
= Li qui d fugaci ty of pure component i at mi xture temperature
Equati on 5 i s i denti cal to equati on 2. Agai n, the fugaci ty coeffi ci ent i s cal cul ated
from an equati on of state. Equati on 6 i s total l y di fferent.
Each property method i n ASPEN PLUS i s based on ei ther the equati on-of-state
method or the acti vi ty coeffi ci ent method for phase equi l i bri um cal cul ati ons. The
phase equi l i bri um method determi nes how other thermodynami c properti es, such
as enthal pi es and mol ar vol umes, are cal cul ated.
Wi th an equati on-of-state method, al l properti es can be deri ved from the
equati on of state, for both phases. Usi ng an acti vi ty coeffi ci ent method, the vapor
phase properti es are deri ved from an equati on of state, exactl y as i n the
equati on-of- state method. However the l i qui d properti es are determi ned from
summati on of the pure component properti es to whi ch a mi xi ng term or an excess
term i s added.
Equation-of-State Method
The parti al pressure of a component i i n a gas mi xture i s:
p y p
i i
(7)
The fugaci ty of a component i n an i deal gas mi xture i s equal to i ts parti al
pressure. The fugaci ty i n a real mi xture i s the effecti ve parti al pressure:
f y p
i
v
i
v
i
(8)
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
The correcti on factor
i
v
i s the fugaci ty coeffi ci ent. For a vapor at moderate
pressures,
i
v
i s cl ose to uni ty. The same equati on can be appl i ed to a l i qui d:
f x p
i
l
i
l
i
(9)
A l i qui d di ffers from an i deal gas much more than a real gas di ffers from an i deal
gas. Thus fugaci ty coeffi ci ents for a l i qui d are very di fferent from uni ty. For
exampl e, the fugaci ty coeffi ci ent of l i qui d water at atmospheri c pressure and
room temperature i s about 0.03 (Haar et al ., 1984).
An equati on of state descri bes the pressure, vol ume and temperature (p,V,T)
behavi or of pure components and mi xtures. Usual l y i t i s expl i ci t i n pressure.
Most equati ons of state have di fferent terms to represent attracti ve and repul si ve
forces between mol ecul es. Any thermodynami c property, such as fugaci ty
coeffi ci ents and enthal pi es, can be cal cul ated from the equati on of state.
Equati on-of-state properti es are cal cul ated rel ati ve to the i deal gas properti es of
the same mi xture at the same condi ti ons. See Cal cul ati on of Properti es Usi ng an
Equati on-of-State Property Method on page 1-7.
Vapor-Liquid Equilibria
The rel ati onshi p for vapor-l i qui d equi l i bri um i s obtai ned by substi tuti ng equati ons
8 and 9 i n equati on 1 and di vi di ng by p:

i
v
i i
l
i
y x (10)
Fugaci ty coeffi ci ents are obtai ned from the equati on of state (see equati on 4 and
Cal cul ati on of Properti es Usi ng an Equati on-of-State Property Method on page 1-
7). The cal cul ati on i s the same for supercri ti cal and subcri ti cal components (see
Acti vi ty Coeffi ci ent Method on page 1-10).
Versi on 10
Chapter 1
Pressure-Temperature Diagram
Fl ui d phase equi l i bri a depend not onl y on temperature but al so on pressure. At
constant temperature (and bel ow the mi xture cri ti cal temperature), a mul ti -
component mi xture wi l l be i n the vapor state at very l ow pressure and i n the l i qui d
state at very hi gh pressure. There i s an i ntermedi ate pressure range for whi ch
vapor and l i qui d phases co-exi st. Comi ng from l ow pressures, fi rst a dew poi nt i s
found. Then more and more l i qui d wi l l form unti l the vapor di sappears at the
bubbl e poi nt pressure. Thi s i s i l l ustrated i n the fi gure l abel ed Phase Envel ope of a
Methane-Ri ch Hydrocarbon Mi xture. Curves of constant vapor fracti on (0.0, 0.2,
0.4, 0.6, 0.8 and 1.0) are pl otted as a functi on of temperature. A vapor fracti on of
uni ty corresponds to a dew-poi nt; a vapor fracti on of zero corresponds to a bubbl e
poi nt. The area confi ned between dew-poi nt and bubbl e-poi nt curves i s the two-
phase regi on. The dew-poi nt and bubbl e-poi nt curves meet at hi gh temperatures
and pressures at the cri ti cal poi nt. The other l i nes of constant vapor fracti ons meet
at the same poi nt. I n Phase Envel ope of a Methane-Ri ch Hydrocarbon Mi xture,
the cri ti cal poi nt i s found at the pressure maxi mum of the phase envel ope
(cri condenbar). Thi s i s not a general rul e.
At the cri ti cal poi nt the di fferences between vapor and l i qui d vani sh; the mol e
fracti ons and properti es of the two phases become i denti cal . Equati on 10 can
handl e thi s phenomenon because the same equati on of state i s used to eval uate
i
v
and
i
l
. Engi neeri ng type equati ons of state can model the pressure
dependence of vapor-l i qui d equi l i bri a very wel l . However, they cannot yet model
cri ti cal phenomena accuratel y (see Equati on-of-State Model s on page 1-22).
Phase Envelope of a Methane-Rich Hydrocarbon Mixture
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
Retrograde Condensation
Compressi ng the methane-ri ch mi xture shown i n the fi gure l abel ed Phase
Envel ope of a Methane-Ri ch Hydrocarbon Mi xture at 270 K (above the mi xture
cri ti cal temperature) wi l l show a dew-poi nt. Then l i qui d wi l l be formed up to a
vapor fracti on of about 0.75 (110 bar). Upon further compressi on the vapor fracti on
wi l l decrease agai n unti l a second dew-poi nt i s reached. I f the process i s carri ed out
wi th decreasi ng pressure, l i qui d i s formed when expandi ng. Thi s i s the opposi te of
the more usual condensati on upon compressi on. I t i s cal l ed retrograde
condensati on and i t happens often i n natural gas mi xtures.
Liquid-Liquid and Liquid-Liquid-Vapor Equilibria
Li qui d-l i qui d equi l i bri a are l ess pressure dependent than vapor-l i qui d equi l i bri a,
but certai nl y not pressure i ndependent. The acti vi ty coeffi ci ent method can model
l i qui d-l i qui d and l i qui d-l i qui d-vapor equi l i bri a at l ow pressure as a functi on of
temperature. However, wi th varyi ng pressure the equati on of state method i s
needed (compare Acti vi ty Coeffi ci ent Method on page 1-10, Li qui d-Li qui d and
Li qui d-Li qui d-Vapor Equi l i bri a). The equati on-of-state method (equati on 10) can be
appl i ed to l i qui d-l i qui d equi l i bri a:

i
l
i
l
i
l
i
l
x x
1 1 2 2
(11)
and al so to l i qui d-l i qui d-vapor equi l i bri a:

i
v
i i
l
i
l
i
l
i
l
y x x
1 1 2 2
(12)
Fugaci ty coeffi ci ents i n al l the phases are cal cul ated usi ng the same equati on of
state. Fugaci ty coeffi ci ents from equati ons of state are a functi on of composi ti on,
temperature, and pressure. Therefore, the pressure dependency of l i qui d-l i qui d
equi l i bri a can be descri bed.
Liquid Phase Nonideality
Li qui d-l i qui d separati on occurs i n systems wi th very di ssi mi l ar mol ecul es. Ei ther
the si ze or the i ntermol ecul ar i nteracti ons between components may be di ssi mi l ar.
Systems that demi x at l ow pressures, have usual l y strongl y di ssi mi l ar
i ntermol ecul ar i nteracti ons, as for exampl e i n mi xtures of pol ar and non-pol ar
mol ecul es. I n thi s case, the mi sci bi l i ty gap i s l i kel y to exi st at hi gh pressures as
wel l . An exampl es i s the system di methyl -ether and water (Pozo and Street, 1984).
Thi s behavi or al so occurs i n systems of a ful l y- or near ful l y-fl uori nated al i phati c or
al i cycl i c fl uorocarbon wi th the correspondi ng hydrocarbon (Rowl i nson and Swi nton,
1982), for exampl e cycl ohexane and perfl uorocycl ohexane (Dyke et al ., 1959; Hi cks
and Young, 1971).
Systems whi ch have si mi l ar i nteracti ons, but whi ch are very di fferent i n si ze, do
demi x at hi gher pressures. For bi nary systems, thi s happens often i n the vi ci ni ty
of the cri ti cal poi nt of the l i ght component (Rowl i nson and Swi nton , 1982).
Versi on 10
Chapter 1
Exampl es are:
Methane wi th hexane or heptane (van der Kooi , 1981; Davenport and
Rowl i nson, 1963; Kohn, 1961)
Ethane wi th n-al kanes wi th carbon numbers from 18 to 26 (Peters et al ., 1986)
Carbon di oxi de wi th n-al kanes wi th carbon numbers from 7 to 20 (Fal l et al .,
1985)
The more the demi xi ng compounds di ffer i n mol ecul ar si ze, the more l i kel y i t i s
that the l i qui d-l i qui d and l i qui d-l i qui d-vapor equi l i bri a wi l l i nterfere wi th
sol i di fi cati on of the heavy component. For exampl e, ethane and pentacosane or
hexacosane show thi s. I ncreasi ng the di fference i n carbon number further causes
the l i qui d-l i qui d separati on to di sappear. For exampl e i n mi xtures of ethane wi th
n-al kanes wi th carbon numbers hi gher than 26, the l i qui d-l i qui d separati on
becomes metastabl e wi th respect to the sol i d-fl ui d (gas or l i qui d) equi l i bri a (Peters
et al ., 1986). The sol i d cannot be handl ed by an equati on-of-state method.
Critical Solution Temperature
I n l i qui d-l i qui d equi l i bri a, mutual sol ubi l i ti es depend on temperature and pressure.
Sol ubi l i ti es can i ncrease or decrease wi th i ncreasi ng or decreasi ng temperature or
pressure. The trend depends on thermodynami c mi xture properti es but cannot be
predi cted a priori. I mmi sci bl e phases can become mi sci bl e wi th i ncreasi ng or
decreasi ng temperature or pressure. I n that case a l i qui d-l i qui d cri ti cal poi nt
occurs. Equati ons 11 and 12 can handl e thi s behavi or, but engi neeri ng type
equati ons of state cannot model these phenomena accuratel y.
Calculation of Properties Using an Equation-of-State
Property Method
The equati on of state can be rel ated to other properti es through fundamental
thermodynami c equati ons :
Fugaci ty coeffi ci ent:
f y p
i
v
i
v
i
(13)
Enthal py departure:
( ) ( ) ( ) H H p
RT
V
dV RT
V
V
T S S RT Z
m m
ig
ig m m
ig
m
V

_
,
_
,
+ +
ln 1 (14)
Entropy departure:
( )
S S
p
T
R
V
dV R
V
V
m m
ig
v
ig
V

_
,
1
]
1
+

_
,
ln (15)
Gi bbs energy departure:
( ) ( ) G G p
RT
V
dV RT
V
V
RT Z
m m
ig
ig
V
m

_
,
_
,
ln 1 (16)
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
Mol ar vol ume:
Sol ve ( ) p T V
m
, for V
m
.
From a gi ven equati on of state, fugaci ti es are cal cul ated accordi ng to equati on 13.
The other thermodynami c properti es of a mi xture can be computed from the
departure functi ons:
Vapor enthal py:
( )
H H H H
m
v
m
ig
m
v
m
ig
+ (17)
Li qui d enthal py:
( )
H H H H
m
l
m
ig
m
l
m
ig
+ (18)
The mol ar i deal gas enthal py, H
m
ig
i s computed by the expressi on
( ) H y H C T dT
m
ig
i f i
ig
p i
ig
T
T
i
ref
+
1
]
1

,
(19)
Where:
C
p i
ig
,
= I deal gas heat capaci ty
f i
ig
H
= Standard enthal py of formati on for i deal gas at 298.15 K and 1
atm
T
ref
= Reference temperature = 298.15 K
Entropy and Gi bbs energy can be computed i n a si mi l ar manner:
( )
G G G G
m
v
m
ig
m
v
m
ig
+ (20)
( )
G G G G
m
l
m
ig
m
l
m
ig
+ (21)
( )
S S S S
m
v
m
ig
m
v
m
ig
+ (22)
( )
S S S S
m
l
m
ig
m
l
m
ig
+ (23)
Vapor and l i qui d vol ume i s computed by sol vi ng p(T,V
m
) for V
m
or computed by
an empi ri cal correl ati on.
Advantages and Disadvantages of the Equation-of-State
Method
You can use equati ons of state over wi de ranges of temperature and pressure,
i ncl udi ng subcri ti cal and supercri ti cal regi ons. For i deal or sl i ghtl y non-i deal
systems, thermodynami c properti es for both the vapor and l i qui d phases can be
computed wi th a mi ni mum amount of component data. Equati ons of state are
sui tabl e for model i ng hydrocarbon systems wi th l i ght gases such as CO
2
, N
2
, and
H S
2
.
Versi on 10
Chapter 1
For the best representati on of non-i deal systems, you must obtai n bi nary
i nteracti on parameters from regressi on of experi mental vapor-l i qui d equi l i bri um
(VLE) data. Equati on of state bi nary parameters for many component pai rs are
avai l abl e i n ASPEN PLUS.
The assumpti ons i n the si mpl er equati ons of state (Redl i ch-Kwong-Soave, Peng-
Robi nson, Lee-Kesl er-Pl cker) are not capabl e of representi ng hi ghl y non-i deal
chemi cal systems, such as al cohol -water systems. Use the acti vi ty-coeffi ci ent
opti ons sets for these systems at l ow pressures. At hi gh pressures, use the
fl exi bl e and predi cti ve equati ons of state.
References
A.J. Davenport and J.S. Rowl i nson, Trans. Faraday Soc., Vol . 59 (1963), p. 78,
(ci ted after van der Kooi , 1981).
D.E.L. Dyke, J.S. Rowl i nson and R. Thacker, Trans. Faraday Soc., Vol . 55,
(1959), p. 903, (ci ted after Rowl i nson and Swi nton, 1982).
D.J. Fal l , J.L. Fal l , and K.D. Luks, "Li qui d-l i qui d-vapor i mmi sci bi l i ty Li mi ts i n
Carbon Di oxi de + n-Paraffi n Mi xtures," J . Chem. Eng. Data , Vol . 30, No. 1,
(1985), pp. 82-88.
L. Haar, J.S. Gal l agher, and J.H. Kel l , NBSI NRC Steam Tables (Washi ngton:
Hemi sphere Publ i shi ng Corporati on, 1984).
C.P. Hi cks and C.L. Young, Trans. Faraday Soc., Vol . 67, (1971), p.1605, (ci ted
after Rowl i nson and Swi nton, 1982).
J.P. Kohn, AI ChE J . , Vol 7, (1961), p. 514, (ci ted after van der Kooi , 1981).
H.J. van der Kooi , Metingen en berekeningen aan het systeem methaan-n-
eiscosaan, Ph.D. thesi s, Del ft Uni versi ty of Technol ogy (Del ft: Del ftse
Uni versi tai re Pers, 1981) (I n Dutch).
C.J. Peters, R.N. Li chtenthal er, and J. de Swaan Arons, "Three Phase Equi l i bri a
I n Bi nary Mi xtures Of Ethane And Hi gher N-Al kanes," Fluid Phase Eq., Vol . 29,
(1986), pp. 495-504.
M.E. Pozo and W.B. Street, "Fl ui d Phase Equi l i bri a for the System Di methyl
Ether/Water from 50 to 200 C and Pressures to 50.9 MPa," J . Chem. Eng. Data,
Vol . 29, No. 3, (1984), pp. 324-329.
J.S. Rowl i nson and F.L. Swi nton, Liquids and Liquid Mixtures, 3rd ed. (London,
etc.:Butterworths, 1982), ch. 6.
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
Activity Coefficient Method
I n an i deal l i qui d sol uti on, the l i qui d fugaci ty of each component i n the mi xture i s
di rectl y proporti onal to the mol e fracti on of the component.
f x f
i
l
i i
l
*,
(24)
The i deal sol uti on assumes that al l mol ecul es i n the l i qui d sol uti on are i denti cal
i n si ze and are randoml y di stri buted. Thi s assumpti on i s val i d for mi xtures
contai ni ng mol ecul es of si mi l ar si ze and character. An exampl e i s a mi xture of
pentane (n-pentane) and 2,2-di methyl propane (neopentane) (Gmehl i ng et al .,
1980, pp. 95-99). For thi s mi xture, the mol ecul es are of si mi l ar si ze and the
i ntermol ecul ar i nteracti ons between di fferent component mol ecul es are smal l (as
for al l nonpol ar systems). I deal i ty can al so exi st between pol ar mol ecul es, i f the
i nteracti ons cancel out. An exampl e i s the system water and 1,2-ethanedi ol
(ethyl enegl ycol ) at 363 K (Gmehl i ng et al ., 1988, p. 124).
I n general , you can expect non-i deal i ty i n mi xtures of unl i ke mol ecul es. Ei ther
the si ze and shape or the i ntermol ecul ar i nteracti ons between components may
be di ssi mi l ar. For short these are cal l ed si ze and energy asymmetry. Energy
asymmetry occurs between pol ar and non-pol ar mol ecul es and al so between
di fferent pol ar mol ecul es. An exampl e i s a mi xture of al cohol and water.
The acti vi ty coeffi ci ent
i
represents the devi ati on of the mi xture from i deal i ty
(as defi ned by the i deal sol uti on):
f x f
i
l
i i i
l

*,
(25)
The greater
i
devi ates from uni ty, the more non-i deal the mi xture. For a pure
component x
i
1 and
i
1, so by thi s defi ni ti on a pure component i s i deal . A
mi xture that behaves as the sum of i ts pure components i s al so defi ned as i deal
(compare equati on 24). Thi s defi ni ti on of i deal i ty, rel ati ve to the pure l i qui d, i s
total l y di fferent from the defi ni ti on of the i deal i ty of an i deal gas, whi ch has an
absol ute meani ng (see Equati on-of-State Method on page 1-3). These forms of
i deal i ty can be used next to each other.
I n the majori ty of mi xtures,
i
i s greater than uni ty. The resul t i s a hi gher
fugaci ty than i deal (compare equati on 25 to equati on 24). The fugaci ty can be
i nterpreted as the tendency to vapori ze. I f compounds vapori ze more than i n an
i deal sol uti on, then they i ncrease thei r average di stance. So acti vi ty coeffi ci ents
greater than uni ty i ndi cate repul si on between unl i ke mol ecul es. I f the repul si on
i s strong, l i qui d-l i qui d separati on occurs. Thi s i s another mechani sm that
decreases cl ose contact between unl i ke mol ecul es.
I t i s l ess common that
i
i s smal l er than uni ty. Usi ng the same reasoni ng, thi s
can be i nterpreted as strong attracti on between unl i ke mol ecul es. I n thi s case,
l i qui d-l i qui d separati on does not occur. I nstead formati on of compl exes i s
possi bl e.
Versi on 10
Chapter 1
Vapor-Liquid Equilibria
I n the acti vi ty coeffi ci ent approach, the basi c vapor-l i qui d equi l i bri um
rel ati onshi p i s represented by:

i
v
i i i i
l
y p x f
*,
(26)
The vapor phase fugaci ty coeffi ci ent
i
v
i s computed from an equati on of state
(see Equati on-of-State Method on page 1-3). The l i qui d acti vi ty coeffi ci ent
i
i s
computed from an acti vi ty coeffi ci ent model .
For an i deal gas,
i
v
1. For an i deal l i qui d,
i
1. Combi ni ng thi s wi th equati on
26 gi ves Raoul ts l aw:
y p x p
i i i
l
*,
(27)
At l ow to moderate pressures, the mai n di fference between equati ons 26 and 27
i s due to the acti vi ty coeffi ci ent. I f the acti vi ty coeffi ci ent i s l arger than uni ty, the
system i s sai d to show posi ti ve devi ati ons from Raoul ts l aw. Negati ve devi ati ons
from Raoul ts l aw occur when the acti vi ty coeffi ci ent i s smal l er than uni ty.
Liquid Phase Reference Fugacity
The l i qui d phase reference fugaci ty f
i
l *,
from equati on 26 can be computed i n three
ways:
For sol vents: The reference state for a sol vent i s defi ned as pure component i n
the l i qui d state, at the temperature and pressure of the system. By thi s defi ni ti on
i
approaches uni ty as x
i
approaches uni ty.
The l i qui d phase reference fugaci ty f
i
l *,
i s computed as
( )
f T p p
i
l
i
v
i
l
i
l
i
l *, *, *, *, *,
, (28)
Where:
i
v *,
= Fugaci ty coeffi ci ent of pure component i at the system
temperature and vapor pressures, as cal cul ated from the vapor
phase equati on of state
p
i
l *,
= Li qui d vapor pressures of component i at the system temperature
i
l *,
= Poynti ng correcti on for pressure
=
exp
*,
*,
1
RT
V dp
i
l
p
p
i
l
_
,

Versi on 10
Overview of
ASPEN PLUS
Property
Methods
At l ow pressures, the Poynti ng correcti on i s near uni ty, and can be i gnored.
For di ssol ved gases: Li ght gases (such as O
2
and N
2
) are usual l y supercri ti cal
at the temperature and pressure of the sol uti on. I n that case pure component
vapor pressure i s meani ngl ess and therefore i t cannot serve as the reference
fugaci ty. The reference state for a di ssol ved gas i s redefi ned to be at i nfi ni te
di l uti on and at the temperature and pressure of the mi xtures. The l i qui d phase
reference fugaci ty f
i
l *,
becomes H
i
(the Henrys constant for component i i n the
mi xture).
The acti vi ty coeffi ci ent
i
i s converted to the i nfi ni te di l uti on reference state
through the rel ati onshi p
( )

i i
i
*

(29)
Where:
= The i nfi ni te di l uti on acti vi ty coeffi ci ent of component i i n the

mi xture
By thi s defi ni ti on
i
*
approaches uni ty as x
i
approaches zero. The phase
equi l i bri um rel ati onshi p for di ssol ved gases becomes

i
v
i i i i
y p x H
*
(30)
To compute H
i
, you must suppl y the Henrys constant for the di ssol ved-gas
component i i n each subcri ti cal sol vent component.
Usi ng an Empi ri cal Correl ati on: The reference state fugaci ty i s cal cul ated
usi ng an empi ri cal correl ati on. Exampl es are the Chao-Seader or the Grayson-
Streed model .
Electrolyte and Multicomponent VLE
The vapor-l i qui d equi l i bri um equati ons 26 and 30, onl y appl y for components
whi ch occur i n both phases. I ons are components whi ch do not parti ci pate di rectl y
i n vapor-l i qui d equi l i bri um. Thi s i s true as wel l for sol i ds whi ch do not di ssol ve or
vapori ze. However, i ons i nfl uence acti vi ty coeffi ci ents of the other speci es by
i nteracti ons. As a resul t they parti ci pate i ndi rectl y i n the vapor-l i qui d equi l i bri a.
An exampl e i s the l oweri ng of the vapor pressure of a sol uti on upon addi ti on of an
el ectrol yte. For more on el ectrol yte acti vi ty coeffi ci ent model s, see Acti vi ty
Coeffi ci ent Model s on page 1-32.
Versi on 10
Chapter 1
Mul ti component vapor-l i qui d equi l i bri a are cal cul ated from bi nary parameters.
These parameters are usual l y fi tted to bi nary phase equi l i bri um data (and not
mul ti component data) and represent therefore bi nary i nformati on. The predi cti on
of mul ti component phase behavi or from bi nary i nformati on i s general l y good.
Liquid-Liquid and Liquid-Liquid-Vapor Equilibria
The basi c l i qui d-l i qui d-vapor equi l i bri um rel ati onshi p i s:
x f x f y p
i
l
i
l l
i
l
i
l
i
l
i
v
i
i
1 1 2 2

*, *,
(31)
Equati on 31 can be deri ved from the l i qui d-vapor equi l i bri um rel ati onshi p by
anal ogy. For l i qui d-l i qui d equi l i bri a, the vapor phase term can be omi tted, and
the pure component l i qui d fugaci ty cancel s out:
x x
i
l
i
l
i
l
i
l 1 1 2 2
(32)
The acti vi ty coeffi ci ents depend on temperature, and so do l i qui d-l i qui d
equi l i bri a. However, equati on 32 i s i ndependent of pressure. The acti vi ty
coeffi ci ent method i s very wel l sui ted for l i qui d-l i qui d equi l i bri a at l ow to
moderate pressures. Mutual sol ubi l i ti es do not change wi th pressure i n thi s case.
For hi gh-pressure l i qui d-l i qui d equi l i bri a, mutual sol ubi l i ti es become a functi on
of pressure. I n that case, use an equati on-of-state method.
For the computati on of the di fferent terms i n equati ons 31 and 32, see Vapor-
Li qui d Equi l i bri a on page 1-4.
Mul ti -component l i qui d-l i qui d equi l i bri a cannot be rel i abl y predi cted from bi nary
i nteracti on parameters fi tted to bi nary data onl y. I n general , regressi on of bi nary
parameters from mul ti -component data wi l l be necessary. See the ASPEN PLUS
User Guide, Chapter 31 for detai l s.
The abi l i ty of acti vi ty coeffi ci ent model s i n descri bi ng experi mental l i qui d-l i qui d
equi l i bri a di ffers. The Wi l son model cannot descri be l i qui d-l i qui d separati on at
al l ; UNI QUAC, UNI FAC and NRTL are sui tabl e. For detai l s, see Acti vi ty
Coeffi ci ent Model s on page 1-32. Acti vi ty coeffi ci ent model s someti mes show
anomal ous behavi or i n the metastabl e and unstabl e composi ti on regi on. Phase
equi l i bri um cal cul ati on usi ng the equal i ty of fugaci ti es of al l components i n al l
phases (as i n equati ons 31 and 32), can l ead to unstabl e sol uti ons. I nstead, phase
equi l i bri um cal cul ati on usi ng the mi ni mi zati on of Gi bbs energy al ways yi el ds
stabl e sol uti ons.
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
The fi gure l abel ed (T,x,x,y)Di agram of Water and Butanol -1 at 1.01325 bar, a
graphi cal Gi bbs energy mi ni mi zati on of the system n-butanol + water, shows
thi s:
(T,x,x,y)Diagram of Water and Butanol-1 at 1.01325 bar
The phase di agram of n-butanol + water at 1 bar i s shown i n thi s fi gure. There i s
l i qui d-l i qui d separati on bel ow 367 K and there are vapor-l i qui d equi l i bri a above
thi s temperature. The di agram i s cal cul ated usi ng the UNI FAC acti vi ty
coeffi ci ent model wi th the l i qui d-l i qui d data set.
Versi on 10
Chapter 1
The Gi bbs energi es of vapor and l i qui d phases at 1 bar and 365 K are gi ven i n the
fi gure l abel ed Mol ar Gi bbs Energy of Butanol -1 and Water at 365 K and 1 atm
1
.
Thi s corresponds to a secti on of the phase di agram at 365 K. The Gi bbs energy of
the vapor phase i s hi gher than that of the l i qui d phase at any mol e fracti on. Thi s
means that the vapor i s unstabl e wi th respect to the l i qui d at these condi ti ons.
The mi ni mum Gi bbs energy of the system as a functi on of the mol e fracti on can
be found graphi cal l y by stretchi ng an i magi nary stri ng from bel ow around the
Gi bbs curves. For the case of the fi gure l abel ed Mol ar Gi bbs Energy of Butanol -1
and Water at 365 K and 1 atm, the stri ng never touches the vapor Gi bbs energy
curve. For the l i qui d the si tuati on i s more subtl e: the stri ng touches the curve at
the extremi ti es but not at mol e fracti ons between 0.56 and 0.97. I n that range the
stri ng forms a doubl e tangent to the curve. A hypotheti cal l i qui d mi xture wi th
mol e fracti on of 0.8 has a hi gher Gi bbs energy and i s unstabl e wi th respect to two
l i qui d phases wi th mol e fracti ons correspondi ng to the poi nts where the tangent
and the curve touch. The overal l Gi bbs energy of these two phases i s a l i near
combi nati on of thei r i ndi vi dual Gi bbs energi es and i s found on the tangent (on
the stri ng). The mol e fracti ons of the two l i qui d phases found by graphi cal Gi bbs
energy mi ni mi zati on are al so i ndi cated i n the fi gure l abel ed (T,x,x,y)Di agram
of Water and Butanol -1 at 1.01325 bar.
Molar Gibbs Energy of Butanol-1 and Water at 365 K and 1 atm
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
At a temperature of 370 K, the vapor has become stabl e i n the mol e fracti on
range of 0.67 to 0.90 (see the fi gure l abel ed Mol ar Gi bbs Energy of Butanol -1 and
Water at 370 K and 1 atm). Graphi cal Gi bbs energy mi ni mi zati on resul ts i n two
vapor-l i qui d equi l i bri a, i ndi cated i n the fi gure l abel ed Mol ar Gi bbs Energy of
Butanol -1 and Water at 370 K and 1 atm. I gnori ng the Gi bbs energy of the vapor
and usi ng a doubl e tangent to the l i qui d Gi bbs energy curve a l i qui d-l i qui d
equi l i bri um i s found. Thi s i s unstabl e wi th respect to the vapor-l i qui d equi l i bri a.
Thi s unstabl e equi l i bri um wi l l not be found wi th Gi bbs mi ni mi zati on (unl ess the
vapor i s i gnored) but can easi l y be found wi th the method of equal i ty of
fugaci ti es.
Molar Gibbs Energy of Butanol-1 and Water at 370 K and 1 atm
The techni que of Gi bbs energy mi ni mi zati on can be used for any number of
phases and components, and gi ves accurate resul ts when handl ed by a computer
al gori thm. Thi s techni que i s al ways used i n the equi l i bri um reactor uni t
operati on model RGi bbs, and can be used opti onal l y for l i qui d phase separati on
i n the di sti l l ati on model RadFrac.
Phase Equilibria Involving Solids
I n most i nstances, sol i ds are treated as i nert wi th respect to phase equi l i bri um
(CI SOLI D). Thi s i s useful i f the components do not di ssol ve or vapori ze. An
exampl e i s sand i n a water stream. CI SOLI D components are stored i n separate
substreams.
Versi on 10
Chapter 1
There are two areas of appl i cati on where phase equi l i bri um i nvol vi ng sol i ds may
occur:
Sal t preci pi tati on i n el ectrol yte sol uti ons
Pyrometal l urgi cal appl i cati ons
Salt Precipitation
El ectrol ytes i n sol uti on often have a sol i d sol ubi l i ty l i mi t. Sol i d sol ubi l i ti es can be
cal cul ated i f the acti vi ty coeffi ci ents of the speci es and the sol ubi l i ty product are
known (for detai l s see Chapter 5). The acti vi ty of the i oni c speci es can be computed
from an el ectrol yte acti vi ty coeffi ci ent model (see Acti vi ty Coeffi ci ent Model s on
page 1-32). The sol ubi l i ty product can be computed from the Gi bbs energi es of
formati on of the speci es parti ci pati ng i n the preci pi tati on reacti on or can be
entered as the temperature functi on (K-SALT) on the Reacti ons Chemi stry
Equi l i bri um Constants sheet.
Sal t preci pi tati on i s onl y cal cul ated when the component i s decl ared as a Sal t on
the Reacti ons Chemi stry Stoi chi ometry sheet. The sal t components are part of
the MI XED substream, because they parti ci pate i n phase equi l i bri um. The types
of equi l i bri a are l i qui d-sol i d or vapor-l i qui d-sol i d. Each preci pi tati ng sal t i s
treated as a separate, pure component, sol i d phase.
Sol i d compounds, whi ch are composed of stoi chi ometri c amounts of other
components, are treated as pure components. Exampl es are sal ts wi th crystal
water, l i ke CaSO
4
, H O
2
.
Phase Equilibria Involving Solids for Metallurgical Applications
Mi neral and metal l i c sol i ds can undergo phase equi l i bri a i n a si mi l ar way as
organi c l i qui ds. Typi cal pyrometal l urgi cal appl i cati ons have speci fi c characteri sti cs:
Si mul taneous occurrence of mul ti pl e sol i d and l i qui d phases
Occurrence of si mul taneous phase and chemi cal equi l i bri a
Occurrence of mi xed crystal s or sol i d sol uti ons
These speci fi c characteri sti cs are i ncompati bl e wi th the chemi cal and phase
equi l i bri um cal cul ati ons by fl ash al gori thms as used for chemi cal and
petrochemi cal appl i cati ons. I nstead, these equi l i bri a can be cal cul ated by usi ng
Gi bbs energy mi ni mi zati on techni ques. I n ASPEN PLUS, the uni t operati on model
RGi bbs i s speci al l y desi gned for thi s purpose.
Gi bbs energy mi ni mi zati on techni ques are equi val ent to phase equi l i bri um
computati ons based on equal i ty of fugaci ti es. I f the di stri buti on of the
components of a system i s found, such that the Gi bbs energy i s mi ni mal ,
equi l i bri um i s obtai ned. (Compare the di scussi on of phase equi l i bri um
cal cul ati on usi ng Gi bbs energy mi ni mi zati on i n Equi l i bri a on page 1-6) As a
resul t, the anal og of equati on 31 hol ds:
x f x f x f x f y p
i
l
i
l
i
l
i
l
i
l
i
l
i
s
i
s
i
s
i
s
i
s
i
s
i
v
i
1 1 2 2 1 1 2 2

*, *, *, *,
... ... (33)
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
Thi s equati on can be si mpl i fi ed for pure component sol i ds and l i qui ds, or be
extended for any number of phases.
For exampl e, the pure component vapor pressure (or subl i mati on) curve can be
cal cul ated from the pure component Gi bbs energi es of vapor and l i qui d (or sol i d).
The fi gure l abel ed Thermodynami c Potenti al of Mercury at 7, 5, 10, and 20 bar
shows the pure component mol ar Gi bbs energy or thermodynami c potenti al of
l i qui d and vapor mercury as a functi on of temperature and at four di fferent
pressures: 1,5,10 and 20 bar
2
. The thermodynami c potenti al of the l i qui d i s not
dependent on temperature and i ndependent of pressure: the four curves coi nci de.
The vapor thermodynami c potenti al i s cl earl y di fferent at each pressure. The
i ntersecti on poi nt of the l i qui d and vapor thermodynami c potenti al s at 1 bar i s at
about 630 K. At thi s poi nt the thermodynami c potenti al s of the two phases are
equal , so there i s equi l i bri um. A poi nt of the vapor pressure curve i s found. Bel ow
thi s temperature the l i qui d has the l ower thermodynami c potenti al and i s the
stabl e phase; above thi s temperature the vapor has the l ower thermodynami c
potenti al . Repeati ng the procedure for al l four pressures gi ves the four poi nts
i ndi cated on the vapor pressure curve (see the fi gure l abel ed Vapor Pressure
Curve of Li qui d Mercury). Thi s i s a si mi l ar resul t as a di rect cal cul ati on wi th the
Antoi ne equati on. The procedure can be repeated for a l arge number of pressures
to construct the curve wi th suffi ci ent accuracy. The subl i mati on curve can al so be
cal cul ated usi ng an Antoi ne type model , si mi l ar to the vapor pressure curve of a
l i qui d.
Thermodynamic Potential of Mercury at 7, 5, 10, and 20 bar
Versi on 10
Chapter 1
Vapor Pressure Curve of Liquid Mercury
The majori ty of sol i d databank components occur i n the I NORGANI C databank.
I n that case, pure component Gi bbs energy, enthal py and entropy of sol i d, l i qui d
or vapor are cal cul ated by pol ynomi al s (see Chapter 3).
The pure component sol i d properti es (Gi bbs energy and enthal py) together wi th
the l i qui d and vapor mi xture properti es are suffi ci ent i nput to cal cul ate chemi cal
and phase equi l i bri a i nvol vi ng pure sol i d phases. I n some cases mi xed crystal s or
sol i d sol uti ons can occur. These are separate phases. The concept of i deal i ty and
noni deal i ty of sol i d sol uti ons are si mi l ar to those of l i qui d phases (see Vapor-
Li qui d Equi l i bri a on page 1-4). The acti vi ty coeffi ci ent model s used to descri be
noni deal i ty of the sol i d phase are di fferent than those general l y used for l i qui d
phases. However some of the model s (Margul es, Redl i ch-Ki ster) can be used for
l i qui ds as wel l . I f mul ti pl e l i qui d and sol i d mi xture phases occur si mul taneousl y,
the acti vi ty coeffi ci ent model s used can di ffer from phase to phase.
To be abl e to di sti ngui sh pure component sol i ds from sol i d sol uti ons i n the
stream summary, the pure component sol i ds are pl aced i n the CI SOLI D
substream and the sol i d sol uti ons i n the MI XED substream.
Calculation of Other Properties Using Activity
Coefficients
Properti es can be cal cul ated for vapor, l i qui d or sol i d phases:
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
Vapor phase: Vapor enthal py, entropy, Gi bbs energy and densi ty are computed
from an equati on of state (see Cal cul ati on of Properti es Usi ng an Equati on-of-
State Property Method on page 1-7).
Li qui d phase: Li qui d mi xture enthal py i s computed as
( )
H x H H H
m
l
i i
v
vap i m
E l
i
+
*, * ,
(34)
Where:
H
i
v *,
= Pure component vapor enthal py at T and vapor pressure
vap i
H
*
= Component vapori zati on enthal py
H
m
E l ,
= Excess l i qui d enthal py
Excess l i qui d enthal py H
m
E l ,
i s rel ated to the acti vi ty coeffi ci ent through the
expressi on
H RT x
T
m
E l
i
i
i
,
ln

2

(35)
Li qui d mi xture Gi bbs free energy and entropy are computed as:
( )
S
T
H G
m
l
m
l
m
l

1
(36)
G G RT G
m
l
m
v
i
l
m
E l
i
+ ln
*, ,
(37)
Where:
G RT x
m
E l
i i
i
,
ln (38)
Li qui d densi ty i s computed usi ng an empi ri cal correl ati on.
Sol i d phase: Sol i d mi xture enthal py i s computed as:
H x H H
m
s s
i
s
m
E s
i
i
+
*, ,
(39)
Where:
H
i
s *,
= Pure component sol i d enthal py at T
Versi on 10
Chapter 1
H
m
E s ,
= The excess sol i d enthal py
Excess sol i d enthal py H
m
E s ,
i s rel ated to the acti vi ty coeffi ci ent through the
expressi on H RT x
T
m
E s
i
i
i
,
ln

2

(40)
Sol i d mi xture Gi bbs energy i s computed as:
G x G RT x x
m
s
i i
s
m
E s
i
i
s
i
s
i
+ +

*, ,
ln (41)
Where:
G RT x
m
E s
i
s
i
s
i
,
ln

(42)
The sol i d mi xture entropy fol l ows from the Gi bbs energy and enthal py:
( )
S
T
H G
m
s
m
s
m
s

1
(43)
Advantages and Disadvantages of the Activity Coefficient
Method
The acti vi ty coeffi ci ent method i s the best way to represent hi ghl y non-i deal l i qui d
mi xtures at l ow pressures. You must esti mate or obtai n bi nary parameters from
experi mental data, such as phase equi l i bri um data. Bi nary parameters for the
Wi l son, NRTL, and UNI QUAC model s are avai l abl e i n ASPEN PLUS for a l arge
number of component pai rs. These bi nary parameters are used automati cal l y. See
ASPEN PLUS Physical Property Data, Chapter 1, for detai l s.
Bi nary parameters are val i d onl y over the temperature and pressure ranges of
the data. Bi nary parameters outsi de the val i d range shoul d be used wi th cauti on,
especi al l y i n l i qui d-l i qui d equi l i bri um appl i cati ons. I f no parameters are
avai l abl e, the predi cti ve UNI FAC model s can be used.
The acti vi ty coeffi ci ent approach shoul d be used onl y at l ow pressures (bel ow 10
atm). For systems contai ni ng di ssol ved gases at l ow pressures and at smal l
concentrati ons, use Henrys l aw. For hi ghl y non-i deal chemi cal systems at hi gh
pressures, use the fl exi bl e and predi cti ve equati ons of state.
References
Col l ecti on, Al i phati c Hydrocarbons, C4 - C6, Chemistry Data Series Vol 1, Part 6a,
D. Bi erens and R.Eckerman, eds., (Frankfurt/Mai n: Dechema, 1980).
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
J. Gmehl i ng, U. Onken and W. Arl t, "Vapor-Li qui d Equi l i bri um Data Col l ecti on,
Aqueous-Organi c Systems, Suppl ement 2," Chemistry Data Series Vol 1, Part 1b ,
D. Bi erens and R.Eckerman, eds., (Frankfurt/Mai n: Dechema, 1988).
H.A.J. Oonk, Phase Theory, The Thermodynamics of Heterogeneous Equilibria,
(Amsterdam, etc.: El sevi er Sci enti fi c Publ i shi ng Company, 1981), Ch. 4.
Equation-of-State Models
The si mpl est equati on of state i s the i deal gas l aw:
p
RT
V
m
(44)
The i deal gas l aw assumes that mol ecul es have no si ze and that there are no
i ntermol ecul ar i nteracti ons. Thi s can be cal l ed absol ute i deal i ty, i n contrast to
i deal i ty defi ned rel ati ve to pure component behavi or, as used i n the acti vi ty
coeffi ci ent approach (see Acti vi ty Coeffi ci ent Method on page 1-10).
There are two mai n types of engi neeri ng equati ons of state: cubi c equati ons of
state and the vi ri al equati ons of state. Steam tabl es are an exampl e of another
type of equati on of state.
Cubic Equations of State
I n an i deal gas, mol ecul es have no si ze and therefore no repul si on. To correct the
i deal gas l aw for repul si on, the total vol ume must be corrected for the vol ume of the
mol ecul e(s), or covol ume b. (Compare the fi rst term of equati on 45 to equati on 44.
The covol ume can be i nterpreted as the mol ar vol ume at cl osest packi ng.
The attracti on must decrease the total pressure compared to an i deal gas, so a
negati ve term i s added, proporti onal to an attracti on parameter a. Thi s term i s
di vi ded by an expressi on wi th di mensi on m
3
, because attracti ve forces are
proporti onal to
1
6
r
, wi th r bei ng the di stance between mol ecul es. An exampl e of
thi s cl ass of equati ons i s the Soave-Redl i ch-Kwong equati on of state (Soave,
1972):
( )
( )
( )
p
RT
V b
a T
V V b
m m m

+
(45)
Versi on 10
Chapter 1
Equati on 45 can be wri tten as a cubi c pol ynomi al i n V
m
. Wi th the two terms of
equati on 45 and usi ng si mpl e mi xi ng rul es (see Mi xtures, thi s chapter ). the
Soave-Redl i ch-Kwong equati on of state can represent non-i deal i ty due to
compressi bi l i ty effects. The Peng-Robi nson equati on of state (Peng and Robi nson,
1976) i s si mi l ar to the Soave-Redl i ch-Kwong equati on of state. Si nce the
publ i cati on of these equati ons, many i mprovements and modi fi cati ons have been
suggested. A sel ecti on of i mportant modi fi cati ons i s avai l abl e i n ASPEN PLUS.
The ori gi nal Redl i ch-Kwong-Soave and Peng-Robi nson equati ons wi l l be cal l ed
standard cubi c equati ons of state. Cubi c equati ons of state i n ASPEN PLUS are
based on the Redl i ch-Kwong-Soave and Peng-Robi nson equati ons of state.
Equati ons are l i sted i n the fol l owi ng tabl e.
Cubic Equations of State in ASPEN PLUS
Redlich-Kwong(-Soave) based Peng-Robinson based
Redlich-Kwong Standard Peng-Robinson
Standard Redlich-Kwong-Soave Peng-Robinson
Redlich-Kwong-Soave Peng-Robinson-MHV2
Redlich-Kwong-ASPEN Peng-Robinson-WS
Schwartzentruber-Renon
Redlich-Kwong-Soave-MHV2
Predictive SRK
Redlich-Kwong-Soave-WS
Pure Components
I n a standard cubi c equati on of state, the pure component parameters are
cal cul ated from correl ati ons based on cri ti cal temperature, cri ti cal pressure, and
acentri c factor. These correl ati ons are not accurate for pol ar compounds or l ong
chai n hydrocarbons. I ntroduci ng a more fl exi bl e temperature dependency of the
attracti on parameter (the al pha-functi on), the qual i ty of vapor pressure
representati on i mproves. Up to three di fferent al pha functi ons are bui l t-i n to the
fol l owi ng cubi c equati on-of-state model s i n ASPEN PLUS: Redl i ch-Kwong-Aspen,
Schwartzenruber-Renon, Peng-Robi nson-MHV2, Peng-Robi nson-WS, Predi cti ve
RKS, Redl i ch-Kwong-Soave-MHV2, and Redl i ch-Kwong-Soave-WS.
Cubi c equati ons of state do not represent l i qui d mol ar vol ume accuratel y. To
correct thi s you can use vol ume transl ati on, whi ch i s i ndependent of VLE
computati on. The Schwartzenruber-Renon equati on of state model has vol ume
transl ati on.
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
Mixtures
The cubi c equati on of state cal cul ates the properti es of a fl ui d as i f i t consi sted of
one (i magi nary) component. I f the fl ui d i s a mi xture, the parameters a and b of the
i magi nary component must be cal cul ated from the pure component parameters of
the real components usi ng mi xi ng rul es. The cl assi cal mi xi ng rul es, wi th one bi nary
i nteracti on parameter for the attracti on parameter, are not suffi ci entl y fl exi bl e to
descri be mi xtures wi th strong shape and si ze asymmetry:
( ) ( )
a x x a a k
i j i j a ij
j i

1
2
1
,
(46)
b x b x x
b b
i i
i
i j
i j
j i

_
,

2
(47)
A second i nteracti on coeffi ci ent i s added for the b parameter i n the Redl i ch-
Kwong-Aspen (Mathi as, 1983) and Schwartzentruber-Renon (Schwartzentruber
and Renon, 1989) equati ons of state:
( )
b x x
b b
k
i j
i j
j i
b ij
_
,

2
1
,
(48)
Thi s i s effecti ve to fi t vapor-l i qui d equi l i bri um data for systems wi th strong si ze
and shape asymmetry but i t has the di sadvantage that k
b ij ,
i s strongl y correl ated
wi th k
a ij ,
and that k
b ij ,
affects the excess mol ar vol ume (Lermi te and Vi dal ,
1988).
For strong energy asymmetry, i n mi xtures of pol ar and non-pol ar compounds, the
i nteracti on parameters shoul d depend on composi ti on to achi eve the desi red
accuracy of representi ng VLE data. Huron-Vi dal mi xi ng rul es use acti vi ty
coeffi ci ent model s as mol e fracti on functi ons (Huron and Vi dal , 1979). These
mi xi ng rul es are extremel y successful i n fi tti ng because they combi ne the
advantages of fl exi bi l i ty wi th a mi ni mum of drawbacks (Lermi te and Vi dal ,
1988). However, wi th the ori gi nal Huron-Vi dal approach i t i s not possi bl e to use
acti vi ty coeffi ci ent parameters, determi ned at l ow pressures, to predi ct the hi gh
pressure equati on-of-state i nteracti ons.
Several modi fi cati ons of Huron-Vi dal mi xi ng rul es exi st whi ch use acti vi ty
coeffi ci ent parameters obtai ned at l ow pressure di rectl y i n the mi xi ng rul es (see
the tabl e l abel ed Cubi c Equati ons of State i n ASPEN PLUS). They accuratel y
predi ct bi nary i nteracti ons at hi gh pressure. I n practi ce thi s means that the l arge
database of acti vi ty coeffi ci ent data at l ow pressures (DECHEMA Chemi stry
Data Seri es, Dortmund DataBank) i s now extended to hi gh pressures.
The MHV2 mi xi ng rul es (Dahl and Mi chel sen, 1990), use the Lyngby modi fi ed
UNI FAC acti vi ty coeffi ci ent model (See Acti vi ty Coeffi ci ent Model s on page 1-32).
The qual i ty of the VLE predi cti ons i s good.
Versi on 10
Chapter 1
The predi cti ve SRK method (Hol derbaum and Gmehl i ng, 1991; Fi scher , 1993)
uses the ori gi nal UNI FAC model . The predi cti on of VLE i s good. The mi xi ng
rul es can be used wi th any equati on of state, but i t has been i ntegrated wi th the
Redl i ch-Kwong-Soave equati on of state i n the fol l owi ng way: new UNI FAC
groups have been defi ned for gaseous components, such as hydrogen. I nteracti on
parameters for the new groups have been regressed and added to the exi sti ng
parameter matri x. Thi s extends the exi sti ng l ow pressure acti vi ty coeffi ci ent data
to hi gh pressures, and adds predi cti on of gas sol ubi l i ti es at hi gh pressures.
The Wong-Sandl er mi xi ng rul es (Wong and Sandl er, 1992; Orbey et al ., 1993)
predi ct VLE at hi gh pressure equal l y wel l as the MHV2 mi xi ng rul es. Speci al
attenti on has been pai d to the theoreti cal correctness of the mi xi ng rul es at
pressures approachi ng zero.
Virial Equations of State
Vi ri al equati ons of state i n ASPEN PLUS are:
Hayden-OConnel l
BWR-Lee-Starl i ng
Lee-Kesl er-Pl cker
Thi s type of equati on of state i s based on a sel ecti on of powers of the expansi on:
p RT
V
B
V
C
V
m m m
+ + +
_
,
1
3 3
... (49)
Truncati on of equati on 49 after the second term and the use of the second vi ri al
coeffi ci ent B can descri be the behavi or of gases up to several bar. The Hayden-
O'Connel l equati on of state uses a compl ex computati on of B to account for the
associ ati on and chemi cal bondi ng i n the vapor phase (see Vapor Phase
Associ ati on on page 1-26).
Li ke cubi c equati ons of state, some of these terms must be rel ated to ei ther
repul si on or attracti on. To descri be l i qui d and vapor properti es, hi gher order
terms are needed. The order of the equati ons i n V i s usual l y hi gher than cubi c.
The Benedi ct-Webb-Rubi n equati on of state i s a good exampl e of thi s approach. I t
had many parameters general i zed i n terms of cri ti cal properti es and acentri c
factor by Lee and Starl i ng (Brul et al ., 1982). The Lee-Kesl er-Pl cker equati on
of state i s another exampl e of thi s approach.
Vi ri al equati ons of state for l i qui d and vapor are more fl exi bl e i n descri bi ng a
(p,V) i sotherm because of the hi gher degree of the equati on i n the vol ume. They
are more accurate than cubi c equati ons of state. General i zati ons have been
focused mai nl y on hydrocarbons, therefore these compounds obtai n excel l ent
resul ts. They are not recommended for pol ar compounds.
The standard mi xi ng rul es gi ve good resul ts for mi xtures of hydrocarbons and
l i ght gases.
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
Vapor Phase Association
Nonpol ar substances i n the vapor phase at l ow pressures behave al most i deal l y.
Pol ar substances can exhi bi t noni deal behavi or or even associ ati on i n the vapor
phase. Associ ati on can be expected i n systems wi th hydrogen bondi ng such as
al cohol s, al dehydes and carboxyl i c aci ds. Most hydrogen bondi ng l eads to di mers.
HF i s an excepti on; i t forms mai nl y hexamers. Thi s secti on uses di meri zati on as an
exampl e to di scuss the chemi cal theory used to descri be strong associ ati on.
Chemi cal theory can be used for any type of reacti on.
I f associ ati on occurs, chemi cal reacti ons take pl ace. Therefore, a model based on
physi cal forces i s not suffi ci ent. Some reasons are:
Two monomer mol ecul es form one di mer mol ecul e, so the total number of
speci es decreases. As a resul t the mol e fracti ons change. Thi s has i nfl uence on
VLE and mol ar vol ume (densi ty).
The heat of reacti on affects thermal properti es l i ke enthal py C
p
.
The equi l i bri um constant of a di meri zati on reacti on
2
2
A A (50)
i n the vapor phase i s defi ned i n terms of fugaci ti es:
K
f
f
A
A
2
2
(51)
Wi th:
f y p
i
v
i
v
i
(52)
and real i zi ng that
i
v
i s approxi matel y uni ty at l ow pressures:
K
y
y p
A
A
2
2
(53)
Equati ons 51-53 are expressed i n terms of true speci es properti es. Thi s may seem
natural , but unl ess measurements are done, the true composi ti ons are not
known. On the contrary, the composi ti on i s usual l y gi ven i n terms of unreacted or
apparent speci es (Abbott and van Ness, 1992), whi ch represents the i magi nary
state of the system i f no reacti on takes pl ace. Superscri pts t and a are used to
di sti ngui sh cl earl y between true and apparent speci es. (For more on the use of
apparent and true speci es approach, see Chapter 5).
Versi on 10
Chapter 1
K i n equati on 53 i s onl y a functi on of temperature. I f the pressure approaches
zero at constant temperature,
y
y
A
A
2
2
,whi ch i s a measure of the degree of
associ ati on, must decrease. I t must go to zero for zero pressure where the i deal
gas behavi or i s recovered. The degree of associ ati on can be consi derabl e at
atmospheri c pressure: for exampl e aceti c aci d at 293 K and 1 bar i s di meri zed at
about 95% (Prausni tz et al ., 1986).
The equi l i bri um constant i s rel ated to the thermodynami c properti es of reacti on:
ln K
G
RT
H
RT
S
R
r r r
+

(54)
The Gi bbs energy, the enthal py, and the entropy of reacti on can be approxi mated
as i ndependent of temperature. Then from equati on 54 i t fol l ows that l n K
pl otted agai nst
1
T
i s approxi matel y a strai ght l i ne wi th a posi ti ve sl ope (si nce the
reacti on i s exothermi c) wi th i ncreasi ng
1
T
. Thi s represents a decrease of l n K
wi th i ncreasi ng temperature. From thi s i t fol l ows (usi ng equati on 53) that the
degree of associ ati on decreases wi th i ncreasi ng temperature.
I t i s conveni ent to cal cul ate equi l i bri a and to report mol e fracti ons i n terms of
apparent components. The concentrati ons of the true speci es have to be
cal cul ated, but are not reported. Vapor-l i qui d equi l i bri a i n terms of apparent
components requi re apparent fugaci ty coeffi ci ents. The fugaci ty coeffi ci ents of the
true speci es are expected to be cl ose to uni ty (i deal ) at atmospheri c pressure.
However the apparent fugaci ty coeffi ci ent needs to refl ect the decrease i n
apparent parti al pressure caused by the decrease i n number of speci es. The
apparent parti al pressure i s represented by the term y p
i
a
i n the vapor fugaci ty
equati on appl i ed to apparent components:
f y p
i
a v
i
a v
i
a , ,
(55)
I n fact the apparent and true fugaci ty coeffi ci ents are di rectl y rel ated to each
other by the change i n number of components (Nothnagel et al ., 1973; Abbott and
van Ness, 1992):

i
a v
i
t v i
t
i
a
y
y
, ,
(56)
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
Thi s i s why apparent fugaci ty coeffi ci ents of associ ati ng speci es are wel l bel ow
uni ty. Thi s i s i l l ustrated i n the fi gure l abel ed Apparent Fugaci ty of Vapor
Benzene and Propi oni c Aci d for the system benzene + propi oni c aci d at 415 K and
101.325 kPa (1 atm) (Nothnagel et al ., 1973). The effect of di meri zati on cl earl y
decreases bel ow apparent propi oni c aci d mol e fracti ons of about 0.2 (parti al
pressures of 20 kPa). The effect vani shes at parti al pressures of zero, as expected
from the pressure dependence of equati on 53. The apparent fugaci ty coeffi ci ent of
benzene i ncreases wi th i ncreasi ng propi oni c aci d mol e fracti on. Thi s i s because
the true mol e fracti on of propi oni c aci d i s hi gher than i ts apparent mol e fracti on
(see equati on 56).
Apparent Fugacity of Vapor Benzene and Propionic Acid
The vapor enthal py departure needs to be corrected for the heat of associ ati on.
The true heat of associ ati on can be obtai ned from the equi l i bri um constant:
( ) ( )

r m
t
r m
t
H T
d G
dT
RT
d K
dT

2 2
ln
(57)
The val ue obtai ned from equati on 57 must be corrected for the rati o of true to
apparent number of speci es to be consi stent wi th the apparent vapor enthal py
departure. Wi th the enthal py and Gi bbs energy of associ ati on (equati ons 57 and
54), the entropy of associ ati on can be cal cul ated.
Versi on 10
Chapter 1
The apparent heat of vapori zati on of associ ati ng components as a functi on of
temperature can show a maxi mum. The i ncrease of the heat of vapori zati on wi th
temperature i s probabl y rel ated to the decrease of the degree of associ ati on wi th
i ncreasi ng temperature. However, the heat of vapori zati on must decrease to zero
when the temperature approaches the cri ti cal temperature. The fi gure l abel ed
Li qui d and Vapor Enthal py of Aceti c Aci d i l l ustrates the enthal pi c behavi or of
aceti c aci d. Note that the enthal py effect due to associ ati on i s very l arge.
Liquid and Vapor Enthalpy of Acetic Acid
The true mol ar vol ume of an associ ati ng component i s cl ose to the true mol ar
vol ume of a non-associ ati ng component. At l ow pressures, where the i deal gas
l aw i s val i d, the true mol ar vol ume i s constant and equal to p/RT, i ndependent of
associ ati on. Thi s means that associ ated mol ecul es have a hi gher mol ecul ar mass
than thei r monomers, but they behave as an i deal gas, just as thei r monomers.
Thi s al so i mpl i es that the mass densi ty of an associ ated gas i s hi gher than that of
a gas consi sti ng of the monomers. The apparent mol ar vol ume i s defi ned as the
true total vol ume per apparent number of speci es. Si nce the number of apparent
speci es i s hi gher than the true number of speci es the apparent mol ar vol ume i s
cl earl y smal l er than the true mol ar vol ume.
The chemi cal theory can be used wi th any equati on of state to compute true
fugaci ty coeffi ci ents. At l ow pressures, the i deal gas l aw can be used.
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
For di meri zati on, two approaches are commonl y used: the Nothagel and the
Hayden-OConnel equati ons of state. For HF hexameri zati on a dedi cated
equati on of state i s avai l abl e i n ASPEN PLUS.
Nothnagel et al . (1973) used a truncated van der Waal s equati on of state. They
correl ated the equi l i bri um constants wi th the covol ume b, a pol ari ty parameter p
and the parameter d. b can be determi ned from group contri buti on methods
(Bondi , 1968) (or a correl ati on of the cri ti cal temperature and pressure (as i n
ASPEN PLUS). D and p are adjustabl e parameters. Many val ues for d and p are
avai l abl e i n the Nothnagel equati on of state i n ASPEN PLUS. Al so correcti on
terms for the heats of associ ati on of unl i ke mol ecul es are bui l t-i n. The
equi l i bri um constant, K, has been correl ated to T
b
, T
c
, b, d, and p.
Hayden and OConnel l (1975) used the vi ri al equati on of state (equati on 49),
truncated after the second term. They devel oped a correl ati on for the second
vi ri al coeffi ci ent of pol ar, nonpol ar and associ ati ng speci es based on the cri ti cal
temperature and pressure, the di pol e moment and the mean radi us of gyrati on.
Associ ati on of l i ke and unl i ke mol ecul es i s descri bed wi th the adjustabl e
parameter . Pure component and bi nary val ues for are avai l abl e i n
ASPEN PLUS.
The HF equati on of state (de Leeuw and Watanasi ri , 1993) assumes the
formati on of hexamers onl y. The fugaci ti es of the true speci es are assumed to be
i deal , and i s therefore sui ted for l ow pressures. Speci al attenti on has been pai d to
the robustness of the al gori thm, and the consi stency of the resul ts wi th theory.
The equati on of state has been i ntegrated wi th the el ectrol yte NRTL acti vi ty
coeffi ci ent model to al l ow the ri gorous representati on of absorpti on and stri ppi ng
of HF wi th water. I t can be used wi th other acti vi ty coeffi ci ent model s for
hydrocarbon + HF mi xtures.
References
M. Abbott and M. C. Van Ness, "Thermodynami cs of Sol uti ons Contai ni ng
Reacti ve Speci es: A Gui de to Fundamental s and Appl i cati ons," Fluid Phase
Equilibria, Vol 77, (1992), pp. 53-119.
Bondi , "Physi cal Properti es of Moel cul ar Li qui ds, Crystal s, and Gl asses," Wi l ey,
New York, 1968.
M.R. Brul , C.T. Li n, L.L. Lee, and K.E. Starl i ng, "Mul ti parameter Correspondi ng
States Correl ati on of Coal -Fl ui d Thermodynami c Properti es," AI ChE J ., Vol . 28,
No. 4, (1982), pp. 616 637.
Dahl and M.L. Mi chel sen, "Hi gh-Pressure Vapor-Li qui d Equi l i bri um wi th a
UNI FAC-based Equati on of State", AI ChE J ., Vol . 36, No. 12 (1990), pp. 1829-
1836.
Versi on 10
Chapter 1
Fi scher, Di e PSRK-Methode: Eine Zustandsgleichung unter Verwendung des
UNI FAC-Gruppenbeitragsmodells, VDI Fortschri ttberi chte, Rei he 3:
Verfahrenstechni k, Nr. 324 (Dssel dorf: VDI Verl ag GmbH, 1993).
J.G. Hayden and J.P. O'Connel l , " A General i zed Method for Predi cti ng Second
Vi ri al Coeffi ci ents, " I nd. Eng. Chem. Process Des. Dev., Vol . 14, No. 3, (1975),
pp. 209-216.
Hol derbaum and J. Gmehl i ng, "PSRK: A Group Contri buti on Equati on of State
based on UNI FAC", Fluid Phase Eq., Vol . 70, (1991), pp. 251-265.
M.-J. Huron and J. Vi dal , "New Mi xi ng Rul es i n Si mpl e Equati ons of state for
representi ng Vapour-Li qui d Equi l i bri a of Strongl y Non-i deal Mi xtures," Fluid
Phase Eq., Vol . 3, (1979), pp. 255-271.
V.V. de Leeuw and S. Watanasi ri , " Model l i ng Phase Equi l i bri a And Enthal pi es
Of The System Water And Hydrofl uori c Aci d Usi ng A 'HF Equati on Of State' I n
Conjuncti on Wi th The El ectrol yte NRTL Acti vi ty Coeffi ci ent Model ," Presented
at the 13
th
European Semi nar on Appl i ed Thermodynami cs, 9
th
-12
th
June 1993,
Carry-l e-Rouet, France.
Ch. Lermi te and J. Vi dal , "Les rgl es de ml ange appl i ques aux quati ons
d'tat." Revue de l 'I nsti tut Franai s du Ptrol e, Vol . 43, No. 1, (1988), pp. 73-94.
P.M. Mathi as, "A Versati l e Phase Equi l i bri um Equati on of State," I nd. Eng.
Chem. Process Des. Dev. Vol . 22, (1983), pp. 385-391.
K.-H. Nothnagel , D.S. Abrams, and J.M. Prausni tz, "General i zed Correl ati on for
Fugaci ty Coeffi ci ents i n Mi xtures at Moderate Pressures. Appl i cati ons of
Chemi cal Theory of Vapor I mperfecti ons," I nd. Eng. Chem. Process Des. Dev.,
Vol . 12, No. 1, (1973), pp. 25-35.
Orbey, S.I . Sandl er, and D.S. Wong, "Accurate equati on of state predi cti ons at
hi gh temperatures and pressures usi ng the exi sti ng UNI FAC model ," Fluid
Phase Eq., Vol . 85, (1993), pp. 41-54.
D.-Y. Peng and D.B. Robi nson, "A New Two-Constant Equati on of state," I nd.
Eng. Chem. Fundam., Vol . 15, (1976), pp. 59-64.
J.M. Prausni tz, R.N. Li chtenthal er, and E. Gomes de Azevedo, Molecular
Thermodynamics of Fluid-Phase Equilibria, 2
nd
ed., (Engl ewood Cl i ffs: Prenti ce-
Hal l I nc., 1986), pp. 137-151.
Schwartzentruber and H. Renon, "Extensi on of UNI FAC to Hi gh Pressures and
Temperatures by the Use of a Cubi c Equati on of State," I nd. Eng. Chem. Res.,
Vol . 28, (1989), pp. 1049-1955.
Soave, "Equi l i bri um Constants for a Modi fi ed Redl i ch-Kwong Equati on of State,"
Chem. Eng. Sci., Vol . 27, (1972), pp. 1196-1203.
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
D.S. Wong and S.I . Sandl er, "A Theoreti cal l y Correct New Mi xi ng Rul e for Cubi c
Equati ons of State for Both Hi ghl y and Sl i ghtl y Non-i deal Mi xtures," AI ChE J .,
Vol . 38, (1992), pp. 671-680.
Activity Coefficient Models
Thi s secti on di scusses the characteri sti cs of acti vi ty coeffi ci ent model s. The
descri pti on i s di vi ded i nto the fol l owi ng categori es:
Mol ecul ar model s (correl ati ve model s for non-el ectrol yte sol uti ons )
Group contri buti on model s (predi cti ve model s for non-el ectrol yte sol uti ons)
El ectrol yte acti vi ty coeffi ci ent model s
Molecular Models
The earl y acti vi ty coeffi ci ent model s such as van Laar and Scatchard-Hi l debrand,
are based on the same assumpti ons and pri nci pl es of regul ar sol uti ons. Excess
entropy and excess mol ar vol ume are assumed to be zero, and for unl i ke
i nteracti ons, Londons geometri c mean rul e i s used. Bi nary parameters were
esti mated from pure component properti es. The van Laar model i s onl y useful as
correl ati ve model . The Scatchard-Hi l debrand can predi ct i nteracti ons from
sol ubi l i ty parameters for non-pol ar mi xtures. Both model s predi ct onl y posi ti ve
devi ati ons from Raoul ts l aw (see Acti vi ty Coeffi ci ent Method on page 1-10).
The three-suffi x Margul es and the Redl i ch-Ki ster acti vi ty coeffi ci ent model s are
fl exi bl e ari thmeti c expressi ons.
Local composi ti on model s are very fl exi bl e, and the parameters have much more
physi cal si gni fi cance. These model s assume orderi ng of the l i qui d sol uti on,
accordi ng to the i nteracti on energi es between di fferent mol ecul es. The Wi l son
model i s sui ted for many types of non-i deal i ty but cannot model l i qui d-l i qui d
separati on. The NRTL and UNI QUAC model s can be used to descri be VLE, LLE
and enthal pi c behavi or of hi ghl y non-i deal systems. The WI LSON, NRTL and
UNI QUAC model s are wel l accepted and are used on a regul ar basi s to model
hi ghl y non-i deal systems at l ow pressures.
A detai l ed di scussi on of mol ecul ar acti vi ty coeffi ci ent model s and underl yi ng
theori es can be found i n Prausni tz et al . (1986).
Versi on 10
Chapter 1
Group Contribution Models
The UNI FAC acti vi ty coeffi ci ent model i s an extensi on of the UNI QUAC model . I t
appl i es the same theory to functi onal groups that UNI QUAC uses for mol ecul es. A
l i mi ted number of functi onal groups i s suffi ci ent to form an i nfi ni te number of
di fferent mol ecul es. The number of possi bl e i nteracti ons between groups i s very
smal l compared to the number of possi bl e i nteracti ons between components from a
pure component database (500 to 2000 components). Group-group i nteracti ons
determi ned from a l i mi ted, wel l chosen set of experi mental data are suffi ci ent to
predi ct acti vi ty coeffi ci ents between al most any pai r of components.
UNI FAC (Fredensl und et al ., 1975; 1977) can be used to predi ct acti vi ty
coeffi ci ents for VLE. For LLE a di fferent dataset must be used. Mi xture
enthal pi es, deri ved from the acti vi ty coeffi ci ents (see Acti vi ty Coeffi ci ent Method
on page 1-10) are not accurate.
UNI FAC has been modi fi ed at the Techni cal Uni versi ty of Lyngby (Denmark).
The modi fi cati on i ncl udes an i mproved combi natori al term for entropy and the
group-group i nteracti on has been made temperature dependent. The three
UNI FAC model s are avai l abl e i n ASPEN PLUS. For detai l ed i nformati on on each
model , see Chapter 3.
Thi s model can be appl i ed to VLE, LLE and enthal pi es (Larsen et al ., 1987).
Another UNI FAC modi fi cati on comes from the Uni versi ty of Dortmund
(Germany). Thi s modi fi cati on i s si mi l ar to Lyngby modi fi ed UNI FAC, but i t can
al so predi ct acti vi ty coeffi ci ents at i nfi ni te di l uti on (Wei dl i ch and Gmehl i ng,
1987).
Electrolyte Models
I n el ectrol yte sol uti ons a l arger vari ety of i nteracti ons and phenomena exi st than
i n non-el ectrol yte sol uti ons. Besi des physi cal and chemi cal mol ecul e-mol ecul e
i nteracti ons, i oni c reacti ons and i nteracti ons occur (mol ecul e-i on and i on-i on).
El ectrol yte acti vi ty coeffi ci ent model s (El ectrol yte NRTL, Pi tzer) are therefore more
compl i cated than non-el ectrol yte acti vi ty coeffi ci ent model s. El ectrol ytes di ssoci ate
so a few components can form many speci es i n a sol uti on. Thi s causes a mul ti tude
of i nteracti ons, some of whi ch are strong. Thi s secti on gi ves a summary of the
capabi l i ti es of the el ectrol yte acti vi ty coeffi ci ent model s i n ASPEN PLUS. For
detai l s, see Chapter 3 and Appendi ces A, B, and C.
The Pi tzer el ectrol yte acti vi ty coeffi ci ent model can be used for the
representati on of aqueous el ectrol yte sol uti ons up to 6 mol al strength (for
l i terature references, see Appendi x C). The model handl es gas sol ubi l i ti es.
Excel l ent resul ts can be obtai ned, but many parameters are needed.
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
The El ectrol yte NRTL model i s an extensi on of the mol ecul ar NRTL model (for
l i terature references, see Appendi x B). I t can handl e el ectrol yte sol uti ons of any
strength, and i s sui ted for sol uti ons wi th mul ti pl e sol vents, and di ssol ved gases.
The fl exi bi l i ty of thi s model makes i t very sui tabl e for any l ow-to-moderate
pressure appl i cati on.
El ectrol yte parameter databanks and data packages for i ndustri al l y i mportant
appl i cati ons have been devel oped for both model s (see ASPEN PLUS Physical
Property Data, Chapter 1). I f parameters are not avai l abl e, use data regressi on,
or the Broml ey-Pi tzer acti vi ty coeffi ci ent model .
The Broml ey-Pi tzer acti vi ty coeffi ci ent model i s a si mpl i fi cati on of the Pi tzer
model (for l i terature references, see Appendi x A). A correl ati on i s used to
cal cul ate the i nteracti on parameters. The model i s l i mi ted i n accuracy, but
predi cti ve.
References
Fredensl und, R.L. Jones, and J.M. Prausni tz, "Group-Contri buti on Esti mati on of
Acti vi ty Coeffi ci ents i n Noni deal Li qui d Mi xtures," AI ChE J ., Vol . 21, (1975), pp.
1086-1099.
Fredensl und, J. Gmehl i ng, and P. Rasmussen , Vapor-Liquid Equilibria Using
UNI FAC, (Amsterdam: El sevi er, 1977).
B.L. Larsen, P. Rasmussen, and Aa. Fredensl und, "A Modi fi ed UNI FAC Group-
Contri buti on Model for the Predi cti on of Phase Equi l i bri a and Heats of Mi xi ng,"
I nd. Eng. Chem. Res., Vol . 26, (1987), pp. 2274-2286.
J.M. Prausni tz, R.N. Li chtenthal er, and E. Gomes de Azevedo, Molecular
Thermodynamics of Fluid-Phase Equilibria, 2
nd
ed., (Engl ewood Cl i ffs: Prenti ce-
Hal l I nc., 1986), pp. 137-151.
Wei dl i ch and J. Gmehl i ng, "A Modi fi ed UNI FAC Model . 1. Predi cti on of VLE, h
E
,
," I nd. Eng. Chem. Res., Vol . 26, (1987), pp. 1372-1381.
Transport Property Methods
ASPEN PLUS property methods can compute the fol l owi ng transport properti es:
Vi scosi ty
Thermal conducti vi ty
Di ffusi on coeffi ci ent
Surface tensi on
Versi on 10
Chapter 1
Each pure component property i s cal cul ated ei ther from an empi ri cal equati on or
from a semi -empi ri cal (theoreti cal ) correl ati on. The coeffi ci ents for the empi ri cal
equati on are determi ned from experi mental data and are stored i n the
ASPEN PLUS databank. The mi xture properti es are cal cul ated usi ng appropri ate
mi xi ng rul es. Thi s secti on di scusses the methods for transport property cal cul ati on.
The properti es that have the most i n common i n thei r behavi or are vi scosi ty and
thermal conducti vi ty. Thi s i s refl ected i n si mi l ar methods that exi st for these
properti es and therefore they are di scussed together.
Viscosity and Thermal Conductivity Methods
When the pressure approaches zero, vi scosi ty and thermal conducti vi ty are l i near
functi ons of temperature wi th a posi ti ve sl ope. At a gi ven temperature, vi scosi ty
and thermal conducti vi ty i ncrease wi th i ncreasi ng densi ty (densi ty i ncreases for
any fl ui d wi th i ncreasi ng pressure).
Detai l ed mol ecul ar theori es exi st for gas phase vi scosi ty and thermal
conducti vi ty at l ow pressures. Some of these can account for pol ari ty. These l ow
pressure properti es are not exactl y i deal gas properti es because non-i deal i ty i s
taken i nto account. Exampl es are the Chapman-Enskog-Brokaw and the Chung-
Lee-Starl i ng l ow pressure vapor vi scosi ty model s and the Sti el -Thodos l ow
pressure vapor thermal conducti vi ty model . Resi dual property model s are
avai l abl e to account for pressure or densi ty effects. These model s cal cul ate the
di fference of a certai n property wi th respect to the l ow pressure val ue. The
method used i s:
( ) ( ) ( ) ( ) ( )
x p x p x p x p + 0 0 (58)
Where:
x = Vi scosi ty or thermal conducti vi ty
Most of the l ow pressure model s requi re mi xi ng rul es for cal cul ati ng mi xture
properti es.
Another cl ass of model s cal cul ate the hi gh pressure property di rectl y from
mol ecul ar parameters and state vari abl es. For exampl e the TRAPP model s for
hydrocarbons use cri ti cal parameters and acentri c factor as mol ecul ar
parameters. The model s use temperature and pressure as state vari abl es.
The Chung-Lee-Starl i ng model s use cri ti cal parameters, acentri c factor, and
di pol e moment as mol ecul ar parameters. The model s use temperature and
densi ty as state vari abl es. These model s general l y use mi xi ng rul es for mol ecul ar
parameters, rather than mi xi ng rul es for pure component properti es.
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
Vapor vi scosi ty, thermal conducti vi ty, and vapor di ffusi vi ty are i nterrel ated by
mol ecul ar theori es. Many thermal conducti vi ty methods therefore requi re l ow
pressure vapor vi scosi ty ei ther i n cal cul ati ng thermal conducti vi ty or i n the
mi xi ng rul es.
Li qui d properti es are often descri bed by empi ri cal , correl ati ve model s:
Andrade/DI PPR for l i qui d vi scosi ty and Sato-Ri edel for thermal conducti vi ty.
These are accurate i n the temperature and pressure ranges of the experi mental
data used i n the fi t. Mi xi ng rul es for these properti es do not provi de a good
descri pti on for the excess properti es.
Correspondi ng-states model s such as Chung-Lee-Starl i ng and TRAPP can
descri be both l i qui d and vapor properti es. These model s are more predi cti ve and
l ess accurate than a correl ati ve model , but extrapol ate wel l wi th temperature
and pressure. Chung-Lee-Starl i ng al l ows the use of bi nary i nteracti on
parameters and an associ ati on parameter, whi ch can be adjusted to experi mental
data.
Diffusion Coefficient Methods
I t i s evi dent that di ffusi on i s rel ated to vi scosi ty, so several di ffusi on coeffi ci ent
methods, requi re vi scosi ty, for both l i qui d and for vapor di ffusi on coeffi ci ents.
(Chapman-Enskog-Wi l ke-Lee and Wi l ke-Chang model s).
Vapor di ffusi on coeffi ci ents can be cal cul ated from mol ecul ar theori es si mi l ar to
those di scussed for l ow pressure vapor vi scosi ty and thermal conducti vi ty.
Si mi l arl y, pressure correcti on methods exi st. The Dawson-Khoury-Kobayashi
model cal cul ates a pressure correcti on factor whi ch requi res the densi ty as i nput.
Li qui d di ffusi on coeffi ci ents depend on acti vi ty and l i qui d vi scosi ty.
Bi nary di ffusi on coeffi ci ents are requi red i n processes where mass transfer i s
l i mi ted. Bi nary di ffusi on coeffi ci ents descri be the di ffusi on of one component at
i nfi ni te di l uti on i n another component. I n mul ti component systems thi s
corresponds to a matri x of val ues.
The average di ffusi on coeffi ci ent of a component i n a mi xture does not have any
quanti tati ve appl i cati ons; i t i s an i nformati ve property. I t i s computed usi ng a
mi xi ng rul e for vapor di ffusi on coeffi ci ents and usi ng mi xture i nput parameters
for the Wi l ke-Chang model .
Versi on 10
Chapter 1
Surface Tension Methods
Surface tensi on i s cal cul ated by empi ri cal , correl ati ve model s such as Haki m-
Stei nberg-Sti el /DI PPR. An empi ri cal l i near mi xi ng rul e i s used to compute mi xture
surface tensi on.
References
R.C. Rei d, J.M. Prausni tz, and B.E. Pol i ng, The Properties Of Gases And Liquids,
4
th
ed., (New York, etc: McGraw-Hi l l Book Company, 1987).
Nonconventional Component Enthalpy
Calculation
Nonconventi onal components general l y do not parti ci pate i n phase equi l i bri um
cal cul ati ons, but are i ncl uded i n enthal py bal ances. For a process uni t i n whi ch
no chemi cal change occurs, onl y sensi bl e heat effects of nonconventi onal
components are si gni fi cant. I n thi s case, the enthal py reference state may be
taken as the component at any arbi trary reference temperatures (for exampl e,
298.15 K). I f a nonconventi onal component i s i nvol ved i n a chemi cal reacti on, an
enthal py bal ance i s meani ngful onl y i f the enthal py reference state i s consi stent
wi th that adopted for conventi onal components: the consti tuents el ements must
be i n thei r standard states at 1 atm and 298.15 K. The enthal py i s cal cul ated as:
H h C dT
s
f
s
p
s
T
T
ref
+
(59)
Frequentl y the heat of formati on
f
s
h i s unknown and cannot be obtai ned
di rectl y because the mol ecul ar structure of the component i s unknown. I n many
cases, i t i s possi bl e to cal cul ate the heat of formati on from the heat of combusti on
c
s
h , because the combusti on products and el emental composi ti on of the
components are known:

f
s
c
s
f cp
s
h h h + (60)
f cp
s
h i s the sum of the heats of formati on of the combusti on products mul ti pl i ed
by the mass fracti ons of the respecti ve el ements i n the nonconventi onal
component. Thi s i s the approach used i n the coal enthal py model HCOALGEN
(see Chapter 3). Thi s approach i s recommended for computi ng DHFGEN for the
ENTHGEN model .
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
Symbol Definitions
Roman Letters Definitions
a Equation of state energy parameter
b Equation of state co-volume
B Second virial coefficient
C
p
Heat capacity at constant pressure
C Third virial coefficient
f Fugacity
G Gibbs energy
H Henrys constant
H Enthalpy
k Equation of state binary parameter
K Chemical equilibrium constant
n Mole number
p Pressure
R Universal gas constant
S Entropy
T Temperature
V Volume
x,y Molefraction
Z Compressibility factor
Greek Letters Definitions
Activity coefficient
Poynting correction
Fugacity coefficient
Thermodynamic potential
Superscripts Definitions
c Combustion property
I Component index
f Formation property
continued
Versi on 10
Chapter 1
Symbol Definitions (Continued)
Roman Letters Definitions
m Molar property
vap Vaporization property
r Reaction property
ref Reference state property
* Pure component property, asymmetric convention
At infinite dilution
a Apparent property
E Excess property
ig Ideal gas property
l Liquid property
l2 Second liquid property
l1 First liquid property
s Solid property
t True property
v Vapor property
Footnotes
1
The Gi bbs energy has been transformed by a contri buti on l i near i n the mol e
fracti on, such that the Gi bbs energy of pure l i qui d water (thermodynami c
potenti al of water) has been shi fted to the val ue of pure l i qui d n-butanol . Thi s i s
done to make the Gi bbs energy mi ni mi zati on vi si bl e on the scal e of the graph.
Thi s transformati on has no i nfl uence on the resul t of Gi bbs energy mi ni mi zati on
(Oonk, 1981).
2
The pure component mol ar Gi bbs energy i s equal to the pure component
thermodynami c potenti al . The I SO and I UPAC recommendati on to use the
thermodynami c potenti al i s fol l owed.
O O O O
Versi on 10
Overview of
ASPEN PLUS
Property
Methods
Versi on 10
Chapter 2
2 Property Method
Descriptions
Thi s chapter descri bes the ASPEN PLUS property methods. Topi cs i ncl ude:
Cl assi fi cati on of property methods
Recommended use
Property method descri pti ons, organi zed by appl i cati on
Si nce ASPEN PLUS property methods are tai l ored to cl asses of compounds and
operati ng condi ti ons, they fi t most engi neeri ng needs. Customi zati on of property
methods i s expl ai ned i n Chapter 4.
Versi on 10
Property
Method
Descriptions
Classification of Property Methods and
Recommended Use
A property method i s a col l ecti on of property cal cul ati on routes. (For more on
routes, see Chapter 4). The properti es i nvol ved are needed by uni t operati on
model s.
Thermodynami c properti es:
Fugaci ty coeffi ci ent (or equi val ent: chemi cal potenti al , K-val ue)
Enthal py
Entropy
Gi bbs energy
Vol ume
Transport properti es:
Vi scosi ty
Surface tensi on
Property methods al l ow you to speci fy a col l ecti on of property cal cul ati on
procedures as one enti ty, for exampl e, you mi ght use them i n a uni t operati on, or i n
a fl owsheet (see ASPEN PLUS User Guide, Chapter 7).
I t i s i mportant to choose the ri ght property method for an appl i cati on to ensure
the success of your si mul ati on. To hel p you choose a property method, frequentl y
encountered appl i cati ons are l i sted wi th recommended property methods.
(Mul ti pl e property methods often appl y. A cl ass of property methods i s
recommended, as opposed to an i ndi vi dual property method.)
The cl asses of property methods avai l abl e are:
I DEAL
Li qui d fugaci ty and K-val ue correl ati ons
Petrol eum tuned equati ons of state
Equati ons of state for hi gh pressure hydrocarbon appl i cati ons
Fl exi bl e and predi cti ve equati ons of state
Li qui d acti vi ty coeffi ci ents
El ectrol yte acti vi ty coeffi ci ents and correl ati ons
Sol i ds processi ng
Steam tabl es
After you have deci ded whi ch property method cl ass your appl i cati on needs, refer
to the correspondi ng secti on i n thi s chapter for more detai l ed recommendati ons.
See Chapter 3 for detai l ed i nformati on on model s and thei r parameter
requi rements. General usage i ssues, such as usi ng Henrys l aw and the free-water
approxi mati on, are di scussed i n ASPEN PLUS User Guide, Chapter 7.
Versi on 10
Chapter 2
Recommended Classes of Property Methods for Different Applications
Oil and Gas Production
Application Recommended Property Method
Reservoir systems Equations of state for high pressure hydrocarbon applications
Platform separation Equations of state for high pressure hydrocarbon applications
Transportation of oil and gas by pipeline Equations of state for high pressure hydrocarbon applications
Refinery
Low pressure applications(up to several atm)
Vacuum tower Atmospheric crude tower
Petroleum fugacity and K-value correlations (and assay data analysis)
Medium pressure applications (up to several
tens of atm) Coker main fractionator, FCC
main fractionator
Petroleum fugacity and K-value correlations Petroleum-tuned equations of state
(and assay data analysis)
Hydrogen-rich applications Reformer
Hydrofiner
Selected petroleum fugacity correlations Petroleum-tuned equations of state (and
assay data analysis)
Lube oil unit De-asphalting unit Petroleum-tuned equations of state (and assay data analysis)
Gas Processing
Hydrocarbon separations Demethanizer C3-
splitter
Equations of state for high pressure hydrocarbon applications (with k
ij
)
Cryogenic gas processing Air separation Equations of state for high pressure hydrocarbon applications Flexible and
predictive equations of state
Gas dehydration with glycols Flexible and predictive equations of state
Acid gas absorption with
Methanol (rectisol)
NMP (purisol)
Flexible and predictive equations of state
Continued
Versi on 10
Property
Method
Descriptions
Gas Processing (continued)
Acid gas absorption with
Water
Ammonia
Amines
Amines + methanol (amisol)
Caustic
Lime
Hot carbonate
Electrolyte activity coefficients
Claus process Flexible and predictive equations of state
Petrochemicals
Ethylene plant
Primary fractionator
Light hydrocarbons separation train
Quench tower
Petroleum fugacity correlations
(and assay data analysis)
Equations of state for high pressure hydrocarbon applications
Aromatics
BTX extraction
Liquid activity coefficients (very sensitive to parameters)
Substituted hydrocarbons
VCM plant
Acrylonitrile plant
Ether production
MTBE, ETBE, TAME
Liquid activity coefficients
Ethylbenzene and styrene plants Equations of state for high pressure hydrocarbon applications and Ideal (with
Watsol) or liquid activity coefficient
Terephthalic acid Liquid activity coefficients (with dimerization in acetic acid section)
Chemicals
Azeotropic separations
Alcohol separation
Carboxylic acids
Acetic acid plant
Phenol plant Liquid activity coefficients
Liquid phase reactions
Estrification
continued
Versi on 10
Chapter 2
Chemicals (continued)
Ammonia plant Equations of state for high pressure hydrocarbon applications (with k
ij
)
Fluorochemicals Liquid activity coefficients (and HF equation of state)
Inorganic Chemicals
Caustic
Acids
Phosphoric acid
Sulphuric acid
Nitric acid
Hydrochloric acid
Hydrofluoric acid
Electrolyte activity coefficient (and HF equation of state)
Coal Processing
Size reduction
crushing, grinding
Solids processing (with coal analysis and particle size distribution)
Separation and cleaning
sieving, cyclones,
preciptition, washing
Solids processing (with coal analysis and and particle size distribution)
Combustion Equations of state for high pressure hydrocarbon applications (with combustion
databank)
Acid gas absorption See Gas Processing earlier in this discussion.
Coal gasification and liquefaction See Synthetic Fuel later in this discussion.
Power Generation
Combustion
Coal
Oil
Equations of state for high pressure hydrocarbon applications (with combustion
databank)
(and assay analyis with coal correlations)
(and assay analyis)
Steam cycles
Compressors
Turbines
Steam tables
Acid gas absorption See Gas Processing earlier in this discussion.
continued
Versi on 10
Property
Method
Descriptions
Synthetic Fuel
Synthesis gas Equations of state for high pressure hydrocarbon applications
Coal gasification Equations of state for high pressure hydrocarbon applications
Coal liquefaction Equations of state for high pressure hydrocarbon applications with k
ij
and assay
analysis with coal correlations)
Environmental
Solvent recovery Liquid activity coefficients
(Substituted) hydrocarbon stripping Liquid activity coefficients
Acid gas stripping from
Methanol (rectisol)
NMP (purisol)
Flexible and predictive equations of state
Acid gas stripping from
Water
Ammonia
Amines
Amines + methanol (amisol)
Caustic
Lime
Hot carbonate
Claus process Flexible and predictive equations of state
Acids
Stripping
Neutralization
Water and Steam
Steam systems Steam tables
Coolant Steam tables
continued
Versi on 10
Chapter 2
Mineral and Metallurgical Processes
Mechanical processing
crushing, grinding,
sieving, washing
Solids Processing (with inorganic databank)
Hydrometallurgy
Mineral leaching
Pyrometallurgy
Smelter
Converter
Solids Processing (with inorganic databank)
IDEAL Property Method
The I DEAL property method accommodates both Raoul ts l aw and Henrys l aw.
Thi s method uses the:
I deal acti vi ty coeffi ci ent model for the l i qui d phase ( 1)
I deal gas equati on of state Pv RT for the vapor phase
Rackett model for l i qui d mol ar vol ume
The I DEAL property method i s recommended for systems i n whi ch i deal behavi or
can be assumed, such as:
Systems at vacuum pressures
I someri c systems at l ow pressures
I n the vapor phase, smal l devi ati ons from the i deal gas l aw are al l owed. These
devi ati ons occur at:
Low pressures (ei ther bel ow atmospheri c pressure, or at pressures not
exceedi ng 2 bar)
Very hi gh temperatures
I deal behavi or i n the l i qui d phase i s exhi bi ted by mol ecul es wi th ei ther:
Very smal l i nteracti ons (for exampl e, paraffi n of si mi l ar carbon number)
I nteracti ons that cancel each other out (for exampl e, water and acetone)
The I DEAL property method:
Can be used for systems wi th and wi thout noncondensabl e components.
Permanent gases can be di ssol ved i n the l i qui d. You can use Henrys l aw,
whi ch i s val i d at l ow concentrati ons, to model thi s behavi or.
Does not i ncl ude the Poynti ng correcti on
Returns heat of mi xi ng of zero
I s used to i ni ti al i ze FLASH al gori thm
The transport property model s for the vapor phase are al l wel l sui ted for i deal
gases. The transport property model s for the l i qui d phase are empi ri cal equati ons
for fi tti ng experi mental data.
Versi on 10
Property
Method
Descriptions
The I DEAL property method i s someti mes used for sol i ds processi ng where VLE
i s uni mportant (for exampl e, i n coal processi ng). For these, however, the SOLI DS
property method i s recommended. See Sol i ds Handl i ng Property Method on page
2-67 for documentati on on sol i d phase properti es.
Mixture Types
I deal mi xtures wi th and wi thout noncondensabl e components. You shoul d not
use I DEAL for noni deal mi xtures.
Range
I DEAL i s appropri ate onl y at l ow pressure and l ow l i qui d mol e fracti ons of the
noncondensabl e components (i f present).
Use of Henrys Law
To use Henrys l aw for noncondensabl e components, you must desi gnate these
components as Henrys components on the Components Henry-Comps form.
Henry's constant model parameters (HENRY) must be avai l abl e for the sol ute
wi th at l east one sol vent. Use the Properti es Parameters Bi nary I nteracti on form
(HENRY-1) to enter Henry's constants or to revi ew bui l t-i n parameters. ASPEN
PLUS contai ns an extensi ve col l ecti on of Henrys constants for many sol utes i n
sol vents. Sol vents are water and other organi c components. ASPEN PLUS uses
these parameters automati cal l y when you speci fy the I DEAL property method.
The fol l owi ng tabl e l i sts thermodynami c and transport property model s used i n
I DEAL, and thei r mi ni mum parameter requi rements.
Parameters Required for the IDEAL Property Method
General
Property/Purpose Parameter Requirements
Mass balance,
Conversion Mass-basisMole-basis
MW
Conversion Stdvol-basisMole-basis VLSTD
Using Free-water option: solubility of water in
organic phase
WATSOL
Enthalpy of reaction DHFORM
Gibbs energy of reaction DGFORM
continued
Versi on 10
Chapter 2
Thermodynamic Properties
Properties Models Parameter Requirements
Vapor mixture
Enthalpy, entropy,
Gibbs energy
Density
Ideal gas law
Ideal gas heat capacity
Ideal gas law
CPIG or CPIGDP
Liquid mixture
Ideal liquid activity coefficient
Extended Antoine vapor pressure
Henrys constant
Brelvi-OConnell
PLXANT
Solvent: VC, Solute-solvent: HENRY
Solvent: TC, PC, (ZC or RKTZRA), Solute:
(VC or VLBROC)
Enthalpy, entropy Watson/DIPPR TC, (DHVLWT or DHVLDP)
Density Rackett TC, PC, (VC or VCRKT), (ZC or RKTZRA)
Transport Properties
Vapor mixture
Viscosity
Thermal conductivity
Diffusivity
Chapman-Enskog-Brokaw/
DIPPR
Stiel-Thodos low pres./
DIPPR
Chapman-Enskog-Wilke-Lee
MW; (MUP and (STKPAR or LJPAR)) or
MUVDIP
MW or
KVDIP
MW; MUP and (STKPAR or LJPAR)
Surface tension Hakim-Steinberg-Stiel/
DIPPR
(TC, PC, OMEGA) or
SIGDIP
Liquid mixture
Viscosity
Thermal Conductivity
Diffusivity
Andrade/DIPPR
Sato-Riedel/DIPPR
Wilke-Chan
MULAND or MULDIP
(MW, TC, TB) or KLDIP
MW, VB
Versi on 10
Property
Method
Descriptions
Property Methods for Petroleum Mixtures
The property methods i n the fol l owi ng tabl e are desi gned for mi xtures of
hydrocarbons and l i ght gases. K-val ue model s and l i qui d fugaci ty correl ati ons are
used at l ow and medi um pressures. Petrol eum-tuned equati ons of state are used at
hi gh pressures. The hydrocarbons can be from natural gas or crude oi l : that i s,
compl ex mi xtures that are treated usi ng pseudocomponents. These property
methods are often used for refi nery appl i cati ons. Densi ty and transport properti es
are cal cul ated by API procedures when possi bl e.
The fol l owi ng tabl e l i sts the common and the di sti ncti ve model s of the property
methods. The parameter requi rements of the di sti ncti ve model s are gi ven i n the
tabl es l abel ed Parameters Requi red for the CHAO-SEA Property Method on page
2-13, Parameters Requi red for the GRAYSON Property Method on page 2-15,
Parameters Requi red for the PENG-ROB Property Method on page 2-16, and
Parameters Requi red for the RK-SOAVE Property Method on page 2-18.
Parameter requi rements for the common model s are i n the tabl e l abel ed
Parameters Requi red for Common Model s on page 2-18. For detai l s on these
model s, see Chapter 3
Property Methods for Petroleum Mixtures
Liquid Fugacity and K-Value Models
Property Method Name Models
BK10 Braun K10 K-value model
CHAO-SEA Chao-Seader liquid fugacity, Scatchard-Hildebrand activity coefficient
GRAYSON Grayson-Streed liquid fugacity, Scatchard-Hildebrand activity coefficient
Petroleum-Tuned Equations of State
PENG-ROB Peng-Robinson
RK-SOAVE Redlich-Kwong-Soave
Common Models for Property Methods for Petroleum Mixtures
Property Model
Liquid enthalpy Lee-Kesler
Liquid molar volume API
continued
Versi on 10
Chapter 2
Common Models for Property Methods for Petroleum Mixtures (Continued)
Property Model
Vapor viscosity Chapman-Enskog-Brokaw
Vapor thermal conductivity Stiel-Thodos/DIPPR
Vapor diffusivity Dawson-Khoury-Kobayashi
Surface tension API surface tension
Liquid viscosity API
Liquid thermal conductivity Sato-Riedel/DIPPR
Liquid diffusivity Wilke-Chang
Liquid Fugacity and K-Value Model Property Methods
The BK10 property method i s general l y used for vacuum and l ow pressure
appl i cati ons (up to several atm). The CHAO-SEA property method and the
GRAYSON property method can be used at hi gher pressures. GRAYSON has the
wi dest ranges of appl i cabi l i ty (up to several tens of atm). For hydrogen-ri ch
systems, GRAYSON i s recommended.
These property methods are l ess sui ted for hi gh-pressure appl i cati ons i n refi nery
(above about 50 atm). Petrol eum-tuned equati on of state property methods are
preferred for hi gh pressures.
These property methods are not sui ted for condi ti ons cl ose to cri ti cal i ty, as occur
i n l i ght oi l reservoi rs, transportati on of gas by pi pel i nes, and i n some gas
processi ng appl i cati ons. Standard equati ons of state for non-pol ar components
are preferred. I f pol ar compounds are present, such as i n gas treatment, use
fl exi bl e and predi cti ve equati ons of state for pol ar compounds.
BK10
The BK10 property method uses the Braun K-10 K-val ue correl ati ons. The
correl ati ons were devel oped from the K10 charts for both real components and oi l
fracti ons. The real components i ncl ude 70 hydrocarbons and l i ght gases. The oi l
fracti ons cover boi l i ng ranges 450 700 K (350 800F). Propri etary methods were
devel oped to cover heavi er oi l fracti ons.
Versi on 10
Property
Method
Descriptions
Mixture Types
Best resul ts are obtai ned wi th purel y al i phati c or purel y aromati c mi xtures wi th
normal boi l i ng poi nts rangi ng from 450 to 700 K. For mi xtures of al i phati c and
aromati c components, or naphteni c mi xtures, the accuracy decreases. For mi xtures
wi th l i ght gases, and medi um pressures, CHAO-SEA or GRAYSON are
recommended.
Range
The BK10 property method i s sui ted for vacuum and l ow pressure appl i cati ons (up
to several atm). For hi gh pressures, petrol eum-tuned equati ons of state are best
sui ted.
The appl i cabl e temperature range of the K10 chart i s 133 800 K (-220 980F).
I t can be used up to 1100 K (1520F).
The parameters for the Braun K-10 are al l bui l t-i n. You do not need to suppl y
them. See the tabl e Parameters Requi red for Common Model s on page 2-18 for
parameter requi rements of model s common to petrol eum property methods.
CHAO-SEA
The CHAO-SEA property method uses the:
Chao-Seader correl ati on for reference state fugaci ty coeffi ci ent
Scatchard-Hi l debrand model for acti vi ty coeffi ci ent
Redl i ch-Kwong equati on of state for vapor phase properti es
Lee-Kesl er equati on of state for l i qui d and vapor enthal py
API method for l i qui d mol ar vol ume, vi scosi ty and surface tensi on
Model s l i sted i n the tabl es l abel ed Parameters Requi red for the CHAO-SEA
Property Method on page 2-13 and Parameters Required for Common Models on
page 2-18
The tabl es l abel ed Parameters Requi red for the CHAO-SEA Property Method on
page 2-13 and Parameters Required for Common Models on page 2-18 provi de
thermodynami c and transport property model s, and thei r parameter requi rements.
The CHAO-SEA property method i s predi cti ve. I t can be used for crude towers,
vacuum towers, and some parts of the ethyl ene process. I t i s not recommended
for systems contai ni ng hydrogen.
Versi on 10
Chapter 2
Mixture Types
The CHAO-SEA property method was devel oped for systems contai ni ng
hydrocarbons and l i ght gases, such as carbon di oxi de and hydrogen sul fi de, but
wi th the excepti on of hydrogen. I f the system contai ns hydrogen, use the
GRAYSON property method.
Range
Use the CHAO-SEA property method for systems wi th temperature and pressure
l i mi ts of
200 < T < 533 K
0.5 < T
ri
< 1.3
T
rm
< 0.93
P < 140 atm
Where:
T
ri
= Reduced temperature of a component
T
rm
= Reduced temperature of the mi xture
Do not use thi s property method at very hi gh pressures, especi al l y near the
mi xture cri ti cal poi nt, because of anomal ous behavi or i n these regi ons.
Parameters Required for the CHAO-SEA Property Method
Thermodynamic Properties Models Parameter Requirements
Vapor mixture
Fugacity coefficient,
Density
Enthalpy, entropy,
Gibbs free energy
Redlich-Kwong
Ideal gas heat capacity,
Redlich-Kwong
TC, PC
CPIG or CPIGDP
TC, PC
Liquid mixture
Gibbs free energy
Scatchard-Hildebrand activity coefficient
Chao-Seader pure component fugacity
coefficient
TC, DELTA, VLCVT1; GMSHVL
TC, PC, OMEGA
Versi on 10
Property
Method
Descriptions
GRAYSON
The GRAYSON property method uses the:
Grayson-Streed correl ati on for reference state fugaci ty coeffi ci ents
Scratchard-Hi l dl ebrand model for acti vi ty coeffi ci ents
Redl i ch-Kwong equati on of state for vapor phase properti es
Lee-Kesl er equati on of state for l i qui d and vapor enthal py
API method for l i qui d mol ar vol ume, vi scosi ty and surface tensi on
Refer to the tabl es l abel ed Parameters Required for the GRAYSON Property Method
on page 2-15 and Parameters Requi red for Common Model s on page 2-18 for
thermodynami c and transport property model s, and thei r parameter requi rements.
The GRAYSON property method i s predi cti ve. I t can be used for crude towers,
vacuum towers, and some parts of the ethyl ene process. I t i s recommended for
systems contai ni ng hydrogen.
Mixture Types
The GRAYSON property method was devel oped for systems contai ni ng
hydrocarbons and l i ght gases, such as carbon di oxi de and hydrogen sul fi de. I t i s
recommended over the CHAO-SEA property method when the system contai ns
hydrogen.
Range
Use the GRAYSON property method for systems wi th temperature and pressure
l i mi ts of:
200K < T < 700K
05 . < T
ri
P < 210 atm
Where:
T
ri
= Reduced temperature coeffi ci ent
Do not use thi s property method at very hi gh pressures, especi al l y near the
mi xture cri ti cal poi nt, because of anomal ous behavi or i n these regi ons.
Versi on 10
Chapter 2
Parameters Required for the GRAYSON Property Method
Vapor mixture
Density
Enthalpy, entropy,
Gibbs free energy
Redlich-Kwong
Ideal gas heat capacity, Redlich-Kwong
TC, PC
CPIG or CPIGDP
TC, PC
Liquid mixture
Gibbs free energy
Scatchard-Hildebrand activity coefficient
Grayson-Streed pure component fugacity
coefficient
TC, DELTA, VLCVT1;GMSHVL
TC, PC, OMEGA
Petroleum-Tuned Equation-of-State Property Methods
Petrol eum-tuned equati on-of-state property methods are based on equati ons of
state for nonpol ar compounds wi th bui l t-i n bi nary parameters. These property
methods use the API /Rackett model for l i qui d densi ty to overcome the drawback of
poor l i qui d densi ty cal cul ated by cubi c equati ons of state. Li qui d vi scosi ty and
surface tensi ons are cal cul ated by API model s.
Equati ons of state are comparabl e i n performance when compari ng VLE. BWR-
LS i s recommended for hydrogen-ri ch systems.
Property methods based on l i qui d fugaci ty correl ati ons or K-val ue model s are
general l y preferred for l ow pressure refi nery appl i cati ons. Petrol eum-tuned
equati on-of-state model s can handl e cri ti cal poi nts, but some other model s of the
property methods (such as l i qui d densi ty and l i qui d vi scosi ty) are not sui ted for
condi ti ons cl ose to cri ti cal i ty, as occur i n l i ght oi l reservoi rs, transportati on of gas
by pi pe l i nes, and i n some gas processi ng appl i cati ons. For these cases, equati on-
of-state property methods for hi gh pressure hydrocarbon appl i cati ons are
preferred. I f pol ar compounds are present, such as i n gas treatment, use fl exi bl e
and predi cti ve equati ons of state for pol ar compounds.
PENG-ROB
The PENG-ROB property method uses the:
Peng-Robi nson cubi c equati on of state for al l thermodynami c properti es except
l i qui d mol ar vol ume
API method for l i qui d mol ar vol ume of pseudocomponents and the Rackett
model for real components
Versi on 10
Property
Method
Descriptions
Refer to the tabl es l abel ed Parameters Required for the PENG-ROB Property Method
on page 16 and Parameters Requi red for Common Model s on page 2-18 for
thermodynami c and transport property model s, and thei r requi red parameters.
Thi s property method i s comparabl e to the RK-SOAVE property method. I t i s
recommended for gas-processi ng, refi nery, and petrochemi cal appl i cati ons.
Sampl e appl i cati ons i ncl ude gas pl ants, crude towers, and ethyl ene pl ants.
For accurate resul ts i n your VLE or LLE cal cul ati ons, you must use bi nary
parameters, such as the ASPEN PLUS bui l t-i n bi nary parameters. Use the
Properti es Parameters Bi nary I nteracti on PRKI J-1 form to revi ew avai l abl e
bui l t-i n bi nary parameters. You can al so use the Data Regressi on System (DRS)
to determi ne the bi nary parameters from experi mental phase equi l i bri um data
(usual l y bi nary VLE data).
Mixture Types
Use the PENG-ROB property method for nonpol ar or mi l dl y pol ar mi xtures.
Exampl es are hydrocarbons and l i ght gases, such as carbon di oxi de, hydrogen
sul fi de, and hydrogen. For systems wi th pol ar components, use the SR-POLAR,
PRWS, RKSWS, PRMHV2, RKSMHV2, PSRK, WI LSON, NRTL, VANLAAR, or
UNI QUAC property methods.
Thi s property method i s parti cul arl y sui tabl e i n the hi gh temperature and hi gh
pressure regi ons, such as i n hydrocarbon processi ng appl i cati ons or supercri ti cal
extracti ons.
Range
You can expect reasonabl e resul ts at al l temperatures and pressures. The PENG-
ROB property method i s consi stent i n the cri ti cal regi on. Therefore, i t does not
exhi bi t anomal ous behavi or, unl i ke the acti vi ty coeffi ci ent property methods.
Resul ts are l east accurate i n the regi on near the mi xture cri ti cal poi nt.
Parameters Required for the PENG-ROB Property Method
Vapor mixture
Density
Enthalpy, entropy,
Gibbs free energy
Peng-Robinson
Peng-Robinson
TCPR or TC; PCPR or PC; OMGPR or
OMEGA CPIG or CPIGDP
Liquid mixture
Enthalpy, entropy,
Gibbs energy
Peng-Robinson
Peng-Robinson
TCPR or TC; PCPR or PC; OMGPR or
OMEGA CPIG or CPIGDP
Versi on 10
Chapter 2
RK-SOAVE
The RK-SOAVE property method uses the:
Redl i ch-Kwong-Soave (RKS) cubi c equati on of state for al l thermodynami c
properti es except l i qui d mol ar vol ume
Refer to the tabl es l abel ed Parameters Requi red for the RK-SOAVE Property
Method on page 2-18 and Parameters Requi red for Common Model s on page 2-18
for thermodynami c and transport property model s, and requi red parameters for
thi s property method.
Thi s property method i s comparabl e to the PENG-ROB property method. I t i s
Exampl e appl i cati ons i ncl ude gas pl ants, crude towers, and ethyl ene pl ants. The
RK-SOAVE property method has bui l t-i n bi nary parameters, RKSKI J, that are
used automati cal l y i n ASPEN PLUS.
For accurate resul ts i n your VLE and LLE cal cul ati ons, you must use bi nary
parameters. You can use the ASPEN PLUS bui l t-i n parameters. Use the
Properti es Parameters Bi nary I nteracti on RKSKI J-1 form to revi ew avai l abl e
bui l t-i n bi nary parameters. You can al so use the Data Regressi on System (DRS)
to determi ne the bi nary parameters from experi mental phase equi l i bri um data
(usual l y bi nary VLE data).
Mixture Types
Use the RK-SOAVE property method for nonpol ar or mi l dl y pol ar mi xtures.
sul fi de, and hydrogen. For systems wi th pol ar components, such as al cohol s, use
the SR-POLAR, WI LSON, NRTL, VANLAAR, or UNI QUAC property methods.
Thi s property method i s parti cul arl y sui tabl e i n the hi gh temperature and hi gh
pressure regi ons, such as i n hydrocarbon processi ng appl i cati ons or supercri ti cal
extracti ons.
Range
You can expect reasonabl e resul ts at al l temperatures and pressures. The RK-
SOAVE property method i s consi stent i n the cri ti cal regi on. Therefore, unl i ke the
acti vi ty coeffi ci ent property methods, i t does not exhi bi t anomal ous behavi or.
Resul ts are l east accurate i n the regi on near the mi xture cri ti cal poi nt.
Versi on 10
Property
Method
Descriptions
Parameters Required for the RK-SOAVE Property Method
Vapor mixture
Density
Enthalpy, entropy
Gibbs free energy
Redlich-Kwong-Soave
Redlich-Kwong-Soave
TC, PC, OMEGA
CPIG or CPIGDP,
TC, PC, OMEGA
Liquid mixture
Enthalpy, entropy,
Gibbs free energy
Redlich-Kwong-Soave
Redlich-Kwong-Soave
TC, PC, OMEGA
CPIG or CPIGDP
TC, PC, OMEGA
Common Models
The following tabl e l i sts the model s used i n al l petrol eum property methods and
thei r parameter requi rements.
Parameters Required for Common Models
General
Mass balance, Conversion Mass-basisMole-basis MW
Initialization of Flash calculations PLXANT
Using Free-water option: solubility of water in organic phase WATSOL
Versi on 10
Chapter 2
Property Models Parameter Requirements
Liquid mixture
Enthalpy,
Entropy
Density
Ideal heat capacity,
Lee-Kesler
Real components:
Rackett/DIPPR
Pseudo components:
(CPIG or CPIGDP)
TC, PC, OMEGA
TC, PC, VCRKT
TB, API
Property Models Paremeter Requirements
Vapor mixture
Viscosity
Diffusivity
Chapman-Enskog-Brokaw/
DIPPR
Stiel-Thodos/
DIPPR
Dawson Khoury-Kobayashi -
MW, (MUP and (STKPAR or LJPAR)) or MUVDIP
MW or KVDIP (and vapor viscosity parameters)
MW, MUP, (STKPAR or LJPAR), VC
Liquid mixture
Viscosity
Diffusivity
API
Sato-Riedel/
DIPPR
Wilke-Chang
TB, API
(MW, TB, TC) or
KLDIP
MW, VB
Surface tension API TB, TC, SG
Versi on 10
Property
Method
Descriptions
Equation-of-State Property Methods for
High-Pressure Hydrocarbon Applications
The following tabl e, Equati on of State Property Methods for Hydrocarbons at
Hi gh Pressure, l i sts property methods for mi xtures of hydrocarbons and l i ght
gases. The property methods can deal wi th hi gh pressures and temperatures, and
mi xtures cl ose to thei r cri ti cal poi nt (for exampl e, pi pel i ne transportati on of gas
or supercri ti cal extracti on). Al l thermodynami c properti es of vapor and l i qui d
phases are cal cul ated from the equati ons of state. (See Chapter 1). The TRAPP
model s for vi scosi ty and thermal conducti vi ty can descri be the conti nui ty of gas
and l i qui d beyond the cri ti cal poi nt, comparabl e to an equati on of state.
The hydrocarbons can be from compl ex crude or gas mi xtures treated usi ng
pseudocomponents. But the property methods for petrol eum mi xtures are better
tuned for these appl i cati ons at l ow to medi um pressures. Unl ess you use fi tted
bi nary i nteracti on parameters, no great accuracy shoul d be expected cl ose to the
cri ti cal poi nt. Li qui d densi ti es are not accuratel y predi cted for the cubi c
equati ons of state.
I n the presence of pol ar components (for exampl e, i n gas treatment), fl exi bl e and
predi cti ve equati ons of state shoul d be used. For mi xtures of pol ar and nonpol ar
compounds at l ow pressures, use an acti vi ty-coeffi ci ent-based property method.
The fol l owi ng tabl e l i sts the common and di sti ncti ve model s of the property
methods BWR-LS, LK-PLOCK, PR-BM, and RKS-BM. The parameter
requi rements of the common model s are gi ven i n the tabl e l abel ed Parameters
Requi red for Common Model s on page 2-25. The parameter requi rements for the
di sti ncti ve model s are i n the tabl es l abel ed Parameters Requi red for the BWR-LS
Property Method on page 2-22, Parameters Requi red for the LK-PLOCK Property
Method on page 2-23, Parameters Requi red for the PR-BM Property Method on
page 2-24, and Parameters Requi red for the RKS-BM Property Method on page
2-25.
Equation-of-State Property Methods for Hydrocarbons at High Pressure
BWR-LS BWR-Lee-Starling
LK-PLOCK Lee-Kesler-Plcker
PR-BM Peng-Robinson-Boston-Mathias
RKS-BM Redlich-Kwong-Soave-Boston-Mathias
continued
Versi on 10
Chapter 2
Equation-of-State Property Methods for Hydrocarbons at High Pressure
Property Common Models
Vapor viscosity TRAPP
Vapor thermal conductivity TRAPP
Surface tension API surface tension
Liquid viscosity TRAPP
Liquid thermal conductivity TRAPP
BWR-LS
The BWR-LS property method i s based on the BWR-Lee-Starl i ng equati on of state.
I t i s the general i zati on (i n terms of pure component cri ti cal properti es) of the
Benedi ct-Webb-Rubi n vi ri al equati on of state. The property method uses the
equati on of state for al l thermodynami c properti es. Refer to the tabl e l abel ed
Parameters Requi red for the BWR-LS Property Method on page 2-22 and
Parameters Requi red for Common Model s on page 2-25 for thermodynami c and
transport property model s and thei r parameter requi rements.
The BWR-LS property method i s comparabl e to PENG-ROB, RK-SOAVE, and LK-
PLOCK for phase equi l i bri um cal cul ati ons, but i s more accurate than PENG-
ROB and RK-SOAVE for l i qui d mol ar vol ume and enthal py. You can use i t for
gas processi ng and refi nery appl i cati ons. I t i s sui ted for hydrogen-contai ni ng
systems, and has shown good resul ts i n coal l i quefacti on appl i cati ons.
For accurate resul ts, use the bi nary i nteracti on parameters. Bui l t-i n bi nary
parameters BWRKV and BWRKT are avai l abl e for a l arge number of component
pai rs. ASPEN PLUS uses these bi nary parameters automati cal l y. Use the
Properti es Parameters Bi nary I nteracti on BWRKV-1 and BWRKT-1 forms to
revi ew avai l abl e bui l t-i n bi nary parameters. You can al so use the Data
Regressi on System (DRS) to determi ne the bi nary parameters from experi mental
phase equi l i bri um data (usual l y bi nary VLE data).
Mixture Types
Use the BWR-LS property method for nonpol ar or sl i ghtl y pol ar mi xtures, and l i ght
gases. Asymmetri c i nteracti ons between l ong and short mol ecul es are wel l
predi cted.
Versi on 10
Property
Method
Descriptions
Range
You can expect reasonabl e resul ts up to medi um pressures. At very hi gh pressures,
unreal i sti c l i qui d-l i qui d demi xi ng may be predi cted. Hi gh pressure l i qui d-l i qui d
demi xi ng occurs between short and l ong chai n hydrocarbons and al so, for exampl e,
between carbon di oxi de and l onger hydrocarbon chai ns at hi gh pressures.
Parameters Required for the BWR-LS Property Method
Vapor mixture
Density
Enthalpy,
Entropy,
Gibbs energy
BWR-Lee-Starling
BWR-Lee-Starling
TC, VC, OMEGA
(CPIG or CPIGDP) and
TC, VC, OMEGA
Liquid mixture
Density
Enthalpy,
Entropy,
Gibbs energy
BWR-Lee-Starling
BWR-Lee-Starling
TC, VC, OMEGA
(CPIG or CPIGDP) and
TC, VC, OMEGA
LK-PLOCK
The LK-PLOCK property method i s based on the Lee-Kesl er-Pl cker equati on of
state, whi ch i s a vi ri al -type equati on. LK-PLOCK uses the:
EOS to cal cul ate al l thermodynami c properti es except l i qui d mol ar vol ume
You can use LK-PLOCK for gas-processi ng and refi nery appl i cati ons, but the RK-
SOAVE or the PENG-ROB property methods are preferred.
Refer to the tabl es l abel ed Parameters Requi red for the LK-PLOCK Property
for thermodynami c and transport property model s, and thei r parameter
requi rements.
For accurate resul ts i n VLE cal cul ati ons, use bi nary parameters. Bui l t-i n bi nary
parameters LKPKI J are avai l abl e for a l arge number of component pai rs. ASPEN
PLUS uses these bi nary parameters automati cal l y. Use the Properti es
Parameters Bi nary I nteracti on LKPKI J-1 form to revi ew avai l abl e bui l t-i n bi nary
parameters. You can al so use the Data Regressi on System (DRS) to determi ne
the bi nary parameters from experi mental phase equi l i bri um data (usual l y bi nary
VLE data).
Versi on 10
Chapter 2
Thi s property method al so has bui l t-i n correl ati ons for esti mati ng bi nary
parameters among the components CO, CO
2
, N
2
, H
2
, CH
4
, al cohol s, and
hydrocarbons. Components not bel ongi ng to the cl asses l i sted above are assumed
to be hydrocarbons.
Mixture Types
Use the LK-PLOCK property method for nonpol ar or mi l dl y pol ar mi xtures.
sul fi de, and hydrogen.
Range
You can expect reasonabl e resul ts at al l temperatures and pressures. The
LK-PLOCK property method i s consi stent i n the cri ti cal regi on. I t does not exhi bi t
anomal ous behavi or, unl i ke the acti vi ty coeffi ci ent property methods. Resul ts are
l east accurate i n the regi on near the mi xture cri ti cal poi nt.
Parameters Required for the LK-PLOCK Property Method
Vapor mixture
Density
Enthalpy, entropy
Gibbs free energy
Lee-Kesler-Plcker
Lee-Kesler-Plcker
TC, PC, VC, OMEGA
(CPIG or CPIGDP)
and TC, PC, VC, OMEGA
Liquid mixture
Density
Enthalpy, entropy
Gibbs free energy
Lee-Kesler-Plcker
Lee-Kesler-Plcker
TC, PC, VC, OMEGA
(CPIG or CPIGDP)
and TC, PC, VC, OMEGA
PR-BM
The PR-BM property method uses the Peng Robi nson cubi c equati on of state wi th
the Boston-Mathi as al pha functi on for al l thermodynami c properti es.
Refer to the tabl es l abel ed Parameters Requi red for the PR-BM Property Method
on page 2-24 and Parameters Requi red for Common Model s on page 2-25 for
thermodynami c and transport property model s, and thei r requi red parameters.
Thi s property method i s comparabl e to the RKS-BM property method. I t i s
Sampl e appl i cati ons i ncl ude gas pl ants, crude towers, and ethyl ene pl ants.
Versi on 10
Property
Method
Descriptions
For accurate resul ts i n your VLE cal cul ati ons, you must use bi nary parameters.
ASPEN PLUS does not have bui l t-i n bi nary parameters for thi s property method.
Mixture Types
Use the PR-BM property method for nonpol ar or mi l dl y pol ar mi xtures. Exampl es
are hydrocarbons and l i ght gases, such as carbon di oxi de, hydrogen sul fi de, and
hydrogen.
Range
You can expect reasonabl e resul ts at al l temperatures and pressures. The PR-BM
property method i s consi stent i n the cri ti cal regi on. Resul ts are l east accurate i n
the regi on near the mi xture cri ti cal poi nt.
Parameters Required for the PR-BM Property Method
Vapor or liquid mixture
Density
Enthalpy, entropy,
Gibbs free energy
Peng-Robinson
Peng-Robinson
PC, TC, OMEGA
CPIG or CPIGDP,
TC,PC, OMEGA
RKS-BM
The RKS-BM property method uses the Redl i ch-Kwong-Soave (RKS) cubi c
equati on of state wi th Boston-Mathi as al pha functi on for al l thermodynami c
properti es.
Thi s property method i s comparabl e to the PR-BM property method. I t i s
Exampl e appl i cati ons i ncl ude gas pl ants, crude towers, and ethyl ene pl ants.
For accurate resul ts i n your VLE cal cul ati ons, you must use bi nary parameters.
ASPEN PLUS does not have bui l t-i n bi nary parameters for thi s property method.
Mixture Types
Use the RKS-BM property method for nonpol ar or mi l dl y pol ar mi xtures. Exampl es
are hydrocarbons and l i ght gases, such as carbon di oxi de, hydrogen sul fi de, and
hydrogen.
Versi on 10
Chapter 2
Range
You can expect reasonabl e resul ts at al l temperatures and pressures. The RKS-BM
property method i s consi stent i n the cri ti cal regi on. Resul ts are l east accurate i n
the regi on near the mi xture cri ti cal poi nt.
Refer to the tabl es l abel ed Parameters Requi red for the RKS-BM Property
for thermodynami c and transport property model s, and thei r requi red
parameters.
Parameters Required for the RKS-BM Property Method
Vapor or liquid mixture
Density
Enthalpy, entropy,
Gibbs free energy
Redlich-Kwong-Soave
Redlich-Kwong-Soave
TC, PC, OMEGA
CPIG or CPIGDP,
TC,PC, OMEGA
Common Models
The following tabl e l abel ed Parameters Requi red for Common Model s l i sts the
model s common to equati on-of-state property methods for hi ghpressure
hydrocarbon appl i cati ons and thei r parameter requi rements.
Parameters Required for Common Models
General
Mass balance, Conversion Mass-
basisMole-basis
MW
organic phase
WATSOL
continued
Versi on 10
Property
Method
Descriptions
Transport
Vapor Mixture
Viscosity
Diffusivity
TRAPP
TRAPP
Dawson-Khoury-Kobayashi
TC, PC, OMEGA
TC, PC, OMEGA
Surface tension API TB, TC, SG
Liquid mixture
Viscosity
Diffusivity
TRAPP
TRAPP
Wilke-Chang
TC, PC, OMEGA
TC, PC, OMEGA
MW, VB
Flexible and Predictive Equation-of-State
Property Methods
The tabl e l abel ed Flexible and Predictive Equation-of-State Property Methods on page
2-28 l i sts property methods for mi xtures of pol ar and non-pol ar components and
l i ght gases. The property methods can deal wi th hi gh pressures and temperatures,
mi xtures cl ose to thei r cri ti cal poi nt, and l i qui d-l i qui d separati on at hi gh pressure.
Exampl es of appl i cati ons are gas dryi ng wi th gl ycol s, gas sweeteni ng wi th
methanol , and supercri ti cal extracti on.
Pure component thermodynami c behavi or i s model ed usi ng the Peng-Robi nson or
Redl i ch-Kwong-Soave equati ons of state. They are extended wi th fl exi bl e al pha-
functi ons wi th up to three parameters, for very accurate fi tti ng of vapor
pressures. Thi s i s i mportant i n separati ons of very cl osel y boi l i ng systems and for
pol ar compounds. I n some cases they are extended wi th a vol ume transl ati on
term for accurate fi tti ng of l i qui d densi ti es (see the tabl e l abel ed Fl exi bl e and
Predi cti ve Equati on-of-State Property Methods on page 2-28).
Parameters for the Schwartzentruber-Renon and Mathi as-Copeman al pha
functi ons are avai l abl e for many components i n the PURECOMP databank.
Versi on 10
Chapter 2
Mi xi ng rul es for these model s vary. Extended cl assi cal mi xi ng rul es are used for
fi tti ng hydrogen-ri ch systems or systems wi th strong si ze and shape asymmetry
(Redl i ch-Kwong-Aspen). Composi ti on and temperature-dependent mi xi ng rul es
fi t strongl y non-i deal hi gh pressure systems (SR-POLAR). Modi fi ed Huron-Vi dal
mi xi ng rul es can predi ct non-i deal i ty at hi gh pressure from l ow-pressure (group-
contri buti on) acti vi ty coeffi ent model s (Wong-Sandl er, MHV2, PSRK). The
predi cti ve capabi l i ti es of modi fi ed Huron-Vi dal mi xi ng rul es are superi or to the
predi cti ve capabi l i ti es of SR-POLAR. The di fferences among capabi l i ti es of the
modi fi ed Huron-Vi dal mi xi ng rul es are smal l (see Chapter 3).
The Wong-Sandl er, MHV2, and Hol derbaum-Gmehl i ng mi xi ng rul es use acti vi ty
coeffi ci ent model s to cal cul ate excess Gi bbs or Hel mhol tz energy for the mi xi ng
rul es. The property methods wi th these mi xi ng rul es use the UNI FAC or Lyngby
modi fi ed UNI FAC group contri buti on model s. Therefore, they are predi cti ve. You
can use any ASPEN PLUS acti vi ty coeffi ci ent model s wi th these mi xi ng rul es,
i ncl udi ng user model s. Use the Properti es Methods Model s sheet to modi fy the
property method. See Chapter 4 for detai l s on how to modi fy a property method.
The Chung-Lee-Starl i ng model s for vi scosi ty and thermal conducti vi ty can
descri be the conti nui ty of gas and l i qui d beyond the cri ti cal poi nt. Thi s i s
comparabl e to an equati on of state. These model s can fi t the behavi or of pol ar
and associ ati ng components. Detai l s about the pure component model s and
mi xi ng rul es are found i n Chapter 3.
For mi xtures of pol ar and non-pol ar compounds at l ow pressures, acti vi ty
coeffi ci ent model s are preferred. For non-pol ar mi xtures of petrol eum fl ui ds and
l i ght gases at l ow to medi um pressures, the property methods for petrol eum
mi xtures are recommended. The fl exi bl e and predi cti ve equati ons of state are not
sui ted for el ectrol yte sol uti ons.
The fol l owi ng tabl e, Fl exi bl e and Predi cti ve Equati on-of-State Property Methods,
l i sts fl exi bl e and predi cti ve equati on-of-state property methods, the di sti ncti ve
equati on-of-state model s on whi ch they are based, and some of thei r
characteri sti cs. The tabl e al so gi ves the model s that the property methods have
i n common. Parameter requi rements of the common model s are gi ven i n the tabl e
l abel ed Parameters Requi red for Common Fl exi bl e and Predi cti ve Model s on
page 2-36. Parameter requi rements for the di sti ncti ve model s are i n the tabl es
l abel ed Parameters Requi red for the PRMHV2 Property Method on page 2-29,
Parameters Requi red for the PRWS Property Method on page 2-30, Parameters
Requi red for the PSRK Property Method on page 2-31, Parameters Requi red for
the RK-ASPEN Property Method on page 2-32, Parameters Requi red for the
RKSMHV2 Property Method on page 2-33, Parameters Requi red for the RKSWS
Property Method on page 2-34, and Parameters Requi red for the SR-POLAR
Property Method on page 2-35.
Versi on 10
Property
Method
Descriptions
Flexible and Predictive Equation-of-State Property Methods
Property Method Name Equation of State Volume Shift
Mixing Rule Predictive
PRMHV2 Peng-Robinson MHV2 X

PRWS Peng-Robinson Wong-Sandler X
PSRK Redlich-Kwong-Soave Holderbaum-Gmehling X
RK-ASPEN Redlich-Kwong-Soave Mathias
RKSMHV2 Redlich-Kwong-Soave MHV2 X
RKSWS Redlich-Kwong-Soave Wong-Sandler X
SR-POLAR Redlich-Kwong-Soave X Schwartzentruber-Renon
Vapor viscosity Chung-Lee-Starling
Vapor thermal conductivity Chung-Lee-Starling
Surface tension Hakim-Steinberg-Stiel/DIPPR
Liquid viscosity Chung-Lee-Starling
Thermal conductivity Chung-Lee-Starling
Liquid diffusivity Wilke-Chang liquid
An X indicates volume shift is included in the property method.
An X indicates that the property method is predictive.

PRMHV2
The PRMHV2 property method i s based on the Peng-Robi nson-MHV2 equati on-of-
state model , whi ch i s an extensi on of the Peng-Robi nson equati on of state. The
UNI FAC model i s used by defaul t to cal cul ate excess Gi bbs energy i n the MHV2
mi xi ng rul es. Other modi fi ed UNI FAC model s and acti vi ty coeffi ci ent model s can
be used for excess Gi bbs energy.
Besi des the acentri c factor, up to three pol ar parameters can be used to fi t more
accuratel y the vapor pressure of pol ar compounds.
The MHV2 mi xi ng rul es predi ct the bi nary i nteracti ons at any pressure. Usi ng
the UNI FAC model the MHV2 mi xi ng rul es are predi cti ve for any i nteracti on
that can be predi cted by the UNI FAC model at l ow pressure.
Versi on 10
Chapter 2
The mi ni mum parameter requi rements of the PRMHV2 property method are
gi ven i n the tabl es l abel ed Parameters Requi red for the PRMHV2 Property
Method on page 2-29 and Parameters Requi red for Common Fl exi bl e and
Predi cti ve Model s on page 2-36. For detai l s about opti onal parameters, and
cal cul ati on of pure component and mi xture properti es, see Chapter 3.
Mixture Types
You can use the PRMHV2 property method for mi xtures of non-pol ar and pol ar
compounds. For l i ght gases UNI FAC does not provi de any i nteracti on.
Range
You can use the PRMHV2 property method up to hi gh temperatures and
pressures. You can expect accurate predi cti ons (4% i n pressure and 2% i n mol e
fracti on at gi ven temperature) up to about 150 bar. You can expect reasonabl e
resul ts at any condi ti on, provi ded the UNI FAC i nteracti on parameters are
avai l abl e. Resul ts are l east accurate cl ose to the cri ti cal poi nt.
Parameters Required for the PRMHV2 Property Method
Vapor and liquid mixture
Density
Enthalpy,
Entropy,
Gibbs energy
Peng-Robinson-MHV2,
UNIFAC
Peng-Robinson-MHV2,
UNIFAC
TC, PC, OMEGA,
UFGRP, GMUFQ, GMUFR
(CPIG or CPIGDP),
TC, PC, OMEGA,
UFGRP, GMUFQ, GMUFR
PRWS
The PRWS property method i s based on the Peng-Robi nson-Wong-Sandl er
equati on-of-state model , whi ch i s based on an extensi on of the Peng-Robi nson
equati on of state. The UNI FAC model i s used to cal cul ate excess Hel mhol tz energy
for the mi xi ng rul es.
Besi des the acentri c factor, you can use up to three pol ar parameters to fi t more
accuratel y the vapor pressure of pol ar compounds. The Wong-Sandl er mi xi ng
rul es predi ct the bi nary i nteracti ons at any pressure. Usi ng the UNI FAC model
the PRWS property method i s predi cti ve for any i nteracti on that can be predi cted
by UNI FAC at l ow pressure.
Versi on 10
Property
Method
Descriptions
The mi ni mum parameter requi rements of the property method are gi ven i n the
tabl es l abel ed Parameters Requi red for the PRWS Property Method on page 2-30
and Parameters Requi red for Common Fl exi bl e and Predi cti ve Model s on page 2-
36. For detai l s about the opti onal parameters, and about cal cul ati on of pure
component and mi xture properti es, see Chapter 3.
Mixture Types
You can use the PRWS property method for mi xtures of non-pol ar and pol ar
compounds, i n combi nati on wi th l i ght gases.
Range
You can use the PRWS property method up to hi gh temperatures and pressures.
You can expect accurate predi cti ons (3% i n pressure and 2% i n mol e fracti on at a
gi ven temperature) up to about 150 bar. You can expect reasonabl e resul ts at any
condi ti on, provi ded UNI FAC i nteracti on parameters are avai l abl e. Resul ts are
l east accurate cl ose to the cri ti cal poi nt.
Parameters Required for the PRWS Property Method
Density
Enthalpy,
Entropy,
Gibbs energy
Peng-Robinson-WS,
UNIFAC
Ideal heat capacity, PengRobinson-WS,
UNIFAC
TC, PC, OMEGA, UFGRP, GMUFR, GMUFQ
(CPIG or CPIGDP),TC, PC, OMEGA, UFGRP,
GMUFR, GMUFQ
PSRK
The PSRK property method i s based on the Predi cti ve Soave-Redl i ch-Kwong
equati on-of-state model , whi ch i s an extensi on of the Redl i ch-Kwong-Soave
equati on of state.
accuratel y the vapor pressure of pol ar compounds. The Hol derbaum-Gmehl i ng
mi xi ng rul es or PSRK method predi ct the bi nary i nteracti ons at any pressure.
Usi ng UNI FAC the PSRK method i s predi cti ve for any i nteracti on that can be
predi cted by UNI FAC at l ow pressure. The UNI FAC i nteracti on parameter tabl e
has been extended for gases, for the PSRK method.
Versi on 10
Chapter 2
The mi ni mum parameter requi rements of the PSRK property method are gi ven
i n the tabl es l abel ed Parameters Requi red for the PSRK Property Method on
page 2-31 and Parameters Requi red for Common Fl exi bl e and Predi cti ve Model s
on page 2-36. For detai l s about the opti onal parameters, and about cal cul ati on of
pure component and mi xture properti es, see Chapter 3.
Mixture Types
You can use the PSRK property method for mi xtures of non-pol ar and pol ar
Range
You can use the PSRK property method up to hi gh temperatures and pressures.
You can expect accurate predi cti ons at any condi ti ons provi ded UNI FAC
i nteracti on parameters are avai l abl e. Resul ts are l east accurate cl ose to the cri ti cal
poi nt.
Parameters Required for the PSRK Property Method
Density
Enthalpy,
Entropy,
Gibbs energy
PSRK,
UNIFAC
Ideal heat capacity, PSKR, UNIFAC
GMUFR, GMUFQ
RK-ASPEN
The RK-ASPEN property method i s based on the Redl i ch-Kwong-Aspen equati on-
of-state model , whi ch i s an extensi on of Redl i ch-Kwong-Soave.
Thi s property method i s si mi l ar to RKS-BM, but i t al so appl i es to pol ar
components such as al cohol s and water. RKS-BM requi res pol ar parameters that
must be determi ned from regressi on of experi mental vapor pressure data usi ng
DRS. Use the bi nary parameters to obtai n best possi bl e resul ts for phase
equi l i bri a. RK-ASPEN al l ows temperature-dependent bi nary parameters. I f the
pol ar parameters are zero for al l components and the bi nary parameters are
constant, RK-ASPEN i s i denti cal to RKS-BM.
Versi on 10
Property
Method
Descriptions
The mi ni mum parameter requi rements of the RK-ASPEN property method are
gi ven i n the tabl es l abel ed Parameters Requi red for the RK-ASPEN Property
Predi cti ve Model s on page 2-36. For detai l s about the opti onal parameters for
thi s model , see Chapter 3.
Mixture Types
You can use the RK-ASPEN property method for mi xtures of non-pol ar and sl i ghtl y
pol ar compounds, i n combi nati on wi th l i ght gases. I t i s especi al l y sui ted for
combi nati ons of smal l and l arge mol ecul es, such as ni trogen wi th n-Decane, or
hydrogen-ri ch systems.
Range
You can use the RK-ASPEN property method up to hi gh temperatures and
pressures. You can expect reasonabl e resul ts at any condi ti on, but resul ts are l east
accurate cl ose to the cri ti cal poi nt.
Parameters Required for the RK-ASPEN Property Method
Density
Enthalpy,
Entropy,
Gibbs energy
Redlich-Kwong-Aspen
Redlich-Kwong-Aspen
(CPIG or CPIGDP) and TC, PC, OMEGA
RKSMHV2
The RKSMHV2 property method i s based on the Redl i ch-Kwong-Soave MHV2
equati on of state. The Lyngby modi fi ed UNI FAC model i s used to cal cul ate excess
Gi bbs energy for the MHV2 mi xi ng rul es.
accuratel y the vapor pressure of pol ar compounds. The MHV2 mi xi ng rul es
predi ct the bi nary i nteracti ons at any pressure. Usi ng the Lyngby modi fi ed
UNI FAC model , the Redl i ch-Kwong-Soave MHV2 model i s predi cti ve for any
i nteracti on that can be predi cted by Lyngby modi fi ed UNI FAC at l ow pressure.
The Lyngby modi fi ed UNI FAC i nteracti on parameter tabl e has been extended for
gases for the MHV2 method.
Versi on 10
Chapter 2
The mi ni mum parameter requi rements of the RKSMHV2 property method are
gi ven i n the tabl es l abel ed Parameters Requi red for the RKSMHV2 Property
Predi cti ve Model s on page 2-36. For detai l s about opti onal parameters and
cal cul ati on of pure component and mi xture properti es, see Chapter 3.
Mixture Types
You can use the RKSMHV2 property method for mi xtures of non-pol ar and pol ar
Range
You can use the RKSMHV2 property method up to hi gh temperatures and
pressures. You can expect accurate predi cti ons (4% i n pressure and 2% i n mol e
fracti on at gi ven temperature) up to about 150 bar. You can expect reasonabl e
resul ts at any condi ti on, provi ded Lyngby modi fi ed UNI FAC i nteracti ons are
avai l abl e. Resul ts are l east accurate cl ose to the cri ti cal poi nt.
Parameters Required for the RKSMHV2 Property Method
Density
Enthalpy,
Entropy,
Gibbs energy
Redlich-Kwong-Soave-MHV2, Lyngby
modified UNIFAC
Redlich-Kwong-Soave-MHV2,
Lyngby modified UNIFAC
TC, PC, OMEGA, UFGRPL, GMUFLR,
GMUFLQ
(CPIG or CPIGDP),TC, PC, OMEGA,
UFGRPL, GMUFLR, GMUFLQ
RKSWS
The RKSWS property method i s based on the Redl i ch-Kwong-Soave-Wong-Sandl er
equati on of state. The UNI FAC model i s used to cal cul ate excess Hel mhol tz energy
for the mi xi ng rul es.
Besi des the acentri c factor,you can use up to three pol ar parameters to fi t more
accuratel y the vapor pressure of pol ar compounds. The Wong-Sandl er mi xi ng
rul es predi ct the bi nary i nteracti ons at any pressure. Usi ng the UNI FAC model i t
i s predi cti ve for any i nteracti on that can be predi cted by UNI FAC at l ow
pressure.
Versi on 10
Property
Method
Descriptions
The mi ni mum parameter requi rements of the RKSWS property method are gi ven
i n the tabl es l abel ed Parameters Requi red for the RKSWS Property Method on
page 2-34 and Parameters Requi red for Common Fl exi bl e and Predi cti ve Model s
on page 2-36. For detai l s about opti onal parameters and cal cul ati on of pure
component and mi xture properti es, see Chapter 3.
Mixture Types
You can use the RKSWS property method for mi xtures of non-pol ar and pol ar
Range
You can use the RKSWS property method up to hi gh temperatures and pressures.
You can expect accurate predi cti ons (3% i n pressure and 2% i n mol e fracti on at a
gi ven temperature) up to about 150 bar. You can expect reasonabl e resul ts at any
condi ti on, provi ded UNI FAC i nteracti on parameters are avai l abl e. But resul ts are
l east accurate cl ose to the cri ti cal poi nt.
Parameters Required for the RKSWS Property Method
Density
Enthalpy,
Entropy,
Gibbs energy
Redlich-Kwong-Soave-WS, UNIFAC
Redlich-Kwong-Soave-WS,
UNIFAC
GMUFR, GMUFQ
SR-POLAR
The SR-POLAR property method i s based on an equati on-of-state model by
Schwarzentruber and Renon, whi ch i s an extensi on of the Redl i ch-Kwong-Soave
equati on of state. You can appl y the SR-POLAR method to both non-pol ar and
hi ghl y pol ar components, and to hi ghl y noni deal mi xtures. Thi s method i s
recommended for hi gh temperature and pressure appl i cati ons
SR-POLAR requi res:
Pol ar parameters for pol ar components. These parameters are determi ned
automati cal l y usi ng vapor pressure data generated from the extended
Antoi ne model .
Bi nary parameters to accuratel y represent phase equi l i bri a. The bi nary
parameters are temperature-dependent.
Versi on 10
Chapter 2
I f you do not enter bi nary parameters, ASPEN PLUS esti mates them
automati cal l y usi ng VLE data generated from the UNI FAC group contri buti on
method. Therefore, the SR-POLAR property method i s predi cti ve for any
i nteracti on that UNI FAC can predi ct at l ow pressures. The accuracy of the
predi cti on decreases wi th i ncreasi ng pressure. You cannot use UNI FAC to
predi ct i nteracti ons wi th l i ght gases.
SR-POLAR i s an al ternati ve property method that you can use for noni deal
systems, i nstead of usi ng an acti vi ty coeffi ci ent property method, such as
WI LSON.
Parameter requi rements for the SR-POLAR property method are i n the tabl es
l abel ed Parameters Requi red for the SR-POLAR Property Method on page 2-35
and Parameters Requi red for Common Fl exi bl e and Predi cti ve Model s on page 2-
36. For detai l s about opti onal parameters, and cal cul ati on of pure component and
mi xture properti es, see Chapter 3.
Mixture Types
You can use the SR-POLAR property method for mi xtures of non-pol ar and pol ar
Range
You can use the SR-POLAR property method up to hi gh temperatures and
pressures. You can expect fai r predi cti ons up to about 50 bar. You can expect
reasonabl e resul ts at any condi ti on, provi ded UNI FAC i nteracti on parameters are
avai l abl e. But resul ts are l east accurate cl ose to the cri ti cal poi nt.
Parameters Required for the SR-POLAR Property Method
Density
Enthalpy,
Entropy,
Gibbs energy
Ideal gas heat capacity/DIPPR
TC, PC, OMEGA, Optional:
RKUPPn, RKUCn,
RKUKAn, RKULAn, RKUKBn
n = 0, 1, 2
(CPIG or CPIGDP)
Optional:
RKUPPn, RKUCn,
RKUKAn, RKULAn, RKUKBn
n = 0, 1, 2
Versi on 10
Property
Method
Descriptions
Common Models
The following table descri bes the model s common to fl exi bl e and predi cti ve property
methods and thei r parameter requi rements.
Parameters Required for Common Flexible and Predictive Models
General
basisMole-basis
MW
organic phase
WATSOL
Vapor mixture
Viscosity
Diffusivity
Chung-Lee-Starling
Chung-Lee-Starling
TC, PC, OMEGA
TC, PC, OMEGA
Surface tension Hakim-Steinberg-Stiel/ DIPPR (TC, PC, OMEGA) or SIGDIP
Liquid mixture
Viscosity
Diffusivity
Chung-Lee-Starling
Chung-Lee-Starling
Wilke-Chang
TC, PC, OMEGA
TC, PC, OMEGA
MW, VB
Versi on 10
Chapter 2
Liquid Activity Coefficient Property
Methods
The tabl e l abel ed Liquid Activity Coefficient Property Methods on page 2-38 l i sts
property methods for noni deal and strongl y noni deal mi xtures at l ow pressures
(maxi mum 10 atm). You can model permanent gases i n l i qui d sol uti on usi ng
Henrys l aw. Bi nary parameters for many component pai rs are avai l abl e i n the
ASPEN PLUS databanks. The UNI FAC based property methods are predi cti ve.
These property methods are not sui ted for el ectrol ytes. I n that case use an
el ectrol yte acti vi ty coeffi ci ent property method. Model pol ar mi xtures at hi gh
pressures wi th fl exi bl e and predi cti ve equati ons of state. Non-pol ar mi xtures are
more conveni entl y model ed wi th equati ons-of-state. Petrol eum mi xtures are more
accuratel y model ed wi th l i qui d fugaci ty correl ati ons and equati ons of state.
I n the tabl e l abel ed Li qui d Acti vi ty Coeffi ci ent Property Methods on page 2-
38,there are fi ve di fferent acti vi ty coeffi ci ent model s and si x di fferent equati on-
of-state model s. Each acti vi ty coeffi ci ent model i s pai red wi th a number of
equati on-of-state model s to form 26 property methods. The descri pti on of the
property methods are therefore di vi ded i nto two parts:
Equati on of state
Acti vi ty coeffi ci ent model
Each part di scusses the characteri sti cs of the speci fi c model and i ts parameter
requi rements. Parameters of the model s occurri ng i n al l property methods are
gi ven i n the tabl e l abel ed Parameters Requi red For Common Model s on page 2-
53.
Equations of State
Thi s secti on di scusses the characteri sti cs and parameter requi rements of the
fol l owi ng equati ons of state:
I deal gas l aw
Redl i ch-Kwong
Nothnagel
Hayden-OConnel l
HF equati on of state
Versi on 10
Property
Method
Descriptions
Liquid Activity Coefficient Property Methods
Property Method Gamma Model Name Vapor Phase EOS Name
NRTL NRTL Ideal gas law
NRTL-2 NRTL Ideal gas law
NRTL-RK NRTL Redlich-Kwong
NRTL-HOC NRTL Hayden-OConnell
NRTL-NTH NRTL Nothnagel
UNIFAC UNIFAC Redlich-Kwong
UNIF-LL UNIFAC Redlich-Kwong
UNIF-HOC UNIFAC Hayden-OConnell
UNIF-DMD Dortmund modified UNIFAC Redlich-Kwong-Soave
UNIF-LBY Lyngby modified UNIFAC Ideal Gas law
UNIQUAC UNIQUAC Ideal gas law
UNIQ-2 UNIQUAC Ideal gas law
UNIQ-RK UNIQUAC Redlich-Kwong
UNIQ-HOC UNIQUAC Hayden-OConnell
UNIQ-NTH UNIQUAC Nothnagel
VANLAAR Van Laar Ideal gas law
VANL-2 Van Laar Ideal gas law
VANL-RK Van Laar Redlich-Kwong
VANL-HOC Van Laar Hayden-OConnell
VANL-NTH Van Laar Nothnagel
WILSON Wilson Ideal gas law
WILS-2 Wilson Ideal gas law
WILS-GLR Wilson Ideal gas law
WILS-LR Wilson Ideal gas law
WILS-RK Wilson Redlich-Kwong
WILS-HOC Wilson Hayden-OConnell
WILS-NTH Wilson Nothnagel
WILS-HF Wilson HF equation of state
Versi on 10
Chapter 2
Vapor pressure Extended Antoine
Liquid molar volume Rackett
Heat of vaporization Watson
Surface tension Hakim-Steinberg-Stiel/DIPPR
Liquid viscosity Andrade/DIPPR
Liquid thermal conductivity Sato-Riedel/DIPPR
Ideal Gas Law
The property methods that use the i deal gas l aw as the vapor phase model are:
NRTL
NRTL-2
UNI F-LBY
UNI QUAC
UNI Q-2
VANLAAR
VANL-2
WI LSON
WI LS-2
WI LS-GLR
WI LS-LR
The i deal gas l aw i s the si mpl est equati on of state. I t i s al so known as the
combi ned l aws of Boyl e and Gay-Lussac.
Mixture Types
The i deal gas l aw cannot model associ ati on behavi or i n the vapor phase, as occurs
wi th carboxyl i c aci ds. Choose Hayden-OConnel l or Nothnagel to model thi s
behavi or.
Range
The i deal gas l aw i s val i d for l ow pressures. I t i s not sui ted for model i ng pressures
exceedi ng several atm. For medi um pressures, choose a Redl i ch-Kwong-based
property method.
There are no component-speci fi c parameters associ ated wi th the i deal gas l aw.
Versi on 10
Property
Method
Descriptions
Redlich-Kwong
The property methods that use the Redl i ch-Kwong equati on of state as the vapor
phase model are:
NRTL-RK
UNI FAC
UNI F-LL
UNI Q-RK
VANL-RK
WI LS-RK
The Redl i ch-Kwong equati on of state i s a si mpl e cubi c equati on of state.
Mixture Types
The Redl i ch-Kwong equati on of state cannot model associ ati on behavi or i n the
vapor phase, as occurs wi th carboxyl i c aci ds.
Range
The Redl i ch-Kwong equati on of state descri bes vapor phase properti es accuratel y
up to medi um pressures.
The parameter requi rements for the Redl i ch-Kwong equati on of state are gi ven
i n the fol l owi ng tabl e. For detai l s about the model , see Chapter 3.
Parameters Required for Redlich-Kwong Property Methods
Vapor mixture
Density
Enthalpy,
Entropy,
Gibbs energy
Redlich-Kwong
Redlich-Kwong
TC, PC
(CPIG or CPIGDP), TC, PC
Nothnagel
The property methods that use the Nothnagel equati on of state as vapor phase
model are:
NRTL-NTH
UNI Q-NTH
VANL-NTH
WI LS-NTH
Versi on 10
Chapter 2
The Nothnagel equati on of state accounts for di meri zati on i n the vapor phase at
l ow pressure. Di meri zati on affects VLE; vapor phase properti es, such as enthal py
and densi ty; and l i qui d phase properti es, such as enthal py.
Mixture Types
The Nothnagel equati on of state can model di meri zati on i n the vapor phase, as
occurs wi th mi xtures contai ni ng carboxyl i c aci ds.
Range
Do not use the Nothnagel based property methods at pressures exceedi ng several
atm. For vapor phase associ ati on up to medi um pressure choose the Hayden-
OConnel l equati on.
Parameter requi rements for the Nothnagel equati on of state are gi ven i n the
fol l owi ng tabl e. Enter equi l i bri um constants of associ ati on di rectl y (NTHK). Or
cal cul ate them from the pure component parameters NTHA, el ements 1 to 3 (b
i
,
p
i
and d
i
). I f parameters are not avai l abl e, ASPEN PLUS uses defaul t val ues. For
predi cti on, the Hayden-OConnel l correl ati on i s more accurate. For detai l s about
the model s, see Chapter 3.
Parameters Required for Nothnagel Property Methods
Vapor mixture
Density
Enthalpy,
Entropy,
Gibbs energy
Nothnagel
Nothnagel
TB, TC, PC and (NTHA or NTHK)
(CPIG or CPIGDP), TB, TC, PC and (NTHA or
NTHK)
Hayden-OConnell
The property methods that use the Hayden-OConnel l equati on of state as vapor
phase model are:
NRTL-HOC
UNI F-HOC
UNI Q-HOC
VANL-HOC
WI LS-HOC
The Hayden-OConnel l equati on of state predi cts sol vati on and di meri zati on i n the
vapor phase, up to medi um pressure. Di meri zati on affects VLE; vapor phase
properti es, such as enthal py and densi ty; and l i qui d phase properti es, such as
enthal py.
Versi on 10
Property
Method
Descriptions
Mixture Types
The Hayden-OConnel l equati on rel i abl y predi cts sol vati on of pol ar compounds and
di meri zati on i n the vapor phase, as occurs wi th mi xtures contai ni ng carboxyl i c
aci ds.
Range
Do not use the Hayden-OConnel l -based property methods at pressures exceedi ng
10 to 15 atm.
Parameter requi rements for the Hayden-OConnel l equati on of state are gi ven i n
the fol l owi ng tabl e. For detai l s about the model , see Chapter 3.
Parameters Required for Hayden-OConnell Property Methods
Vapor mixture
Density
Enthalpy,
Entropy,
Gibbs energy
Hayden-OConnell
Hayden-OConnell
TC, PC, RGYR, MUP, HOCETA
(CPIG or CPIGDP), TC, PC, RGYR, MUP,
HOCETA
HF Equation of State
The onl y property method that has the HF equati on of state as the vapor phase
model i s WI LS-HF.
For HF-hydrocarbon mi xtures, the Wi l son acti vi ty coeffi ci ent model i s usual l y
best sui ted for preventi ng nonreal i sti c l i qui d phase spl i tti ng.
The HF equati on of state predi cts the strong associ ati on of HF the vapor phase at
l ow pressures. Associ ati on (mai nl y hexameri zati on) affects VLE, vapor phase
properti es, such as enthal py and densi ty, and l i qui d phase properti es, such as
enthal py.
Mixture Types
The HF equati on of state rel i abl y predi cts the strong associ ati on effects of HF i n a
mi xture.
Range
Do not use the WI LS-HF property method at pressures exceedi ng 3 atm.
Versi on 10
Chapter 2
Parameters for the HF equati on of state are bui l t-i n for temperatures up to 373
K. You can enter parameters and regress them usi ng the ASPEN PLUS Data
Regressi on System (DRS), i f necessary. For detai l s about the model , see Chapter
3.
Thi s secti on di scusses the characteri sti cs and parameter requi rements of the
fol l owi ng acti vi ty coeffi ci ent model s:
NRTL
UNI FAC
UNI QUAC
Van Laar
Wi l son
NRTL
The property methods that use the NRTL acti vi ty coeffi ci ent model are l i sted i n
the following table.
NRTL Property Methods
Binary Parameters
Property Method
Name
Dataset Number VLE
Lit
Reg
LLE
Lit
Reg
Henry
Lit
Reg
Vapor Phase
EOS Name
Poynting
Correction
NRTL 1 X X X X X Ideal Gas law
NRTL-2 2 X X X X X Ideal Gas law
NRTL-RK 1 X X X Redlich-Kwong X
NRTL-HOC 1 X X X Hayden-O'Connell X
NRTL-NTH 1 X X Nothnagel X
An X indicates the parameters were obtained from the literature.
An X indicates the parameters were regressed by AspenTech from experimental data in the Dortmund
Databank (DDB).
The NRTL model can descri be VLE and LLE of strongl y noni deal sol uti ons. The
model requi res bi nary parameters. Many bi nary parameters for VLE and LLE,
from l i terature and from regressi on of experi mental data, are i ncl uded i n the
ASPEN PLUS databanks. For detai l s, see ASPEN PLUS Physical Property Data,
Chapter 1.
Versi on 10
Property
Method
Descriptions
You can model the sol ubi l i ty of supercri ti cal gases usi ng Henrys l aw. Henry
coeffi ci ents are avai l abl e i n the ASPEN PLUS databanks for many sol utes wi th
water and other sol vents (see ASPEN PLUS Physical Property Data, Chapter 1).
The property methods wi th a vapor phase model that can be used up to moderate
pressures, have the Poynti ng correcti on i ncl uded i n the l i qui d fugaci ty coeffi ci ent
cal cul ati on (see the tabl e l abel ed NRTL Property Methods on page 2-44.
Heat of mi xi ng i s cal cul ated usi ng the NRTL model .
You can use separate data sets for the NRTL bi nary parameters to model
properti es or equi l i bri a at di fferent condi ti ons. I t i s al so possi bl e to use one data
set for VLE and a second data set for LLE (use NRTL and NRTL-2) property
methods are i denti cal except for the data set number they use. For exampl e, you
can use these property methods i n di fferent fl owsheet secti ons or col umn
secti ons.
Mixture Types
The NRTL model can handl e any combi nati on of pol ar and non-pol ar compounds,
up to very strong noni deal i ty.
Range
Parameters shoul d be fi tted i n the temperature, pressure, and composi ti on range of
operati on. No component shoul d be cl ose to i ts cri ti cal temperature.
Parameter requi rements for the NRTL acti vi ty coeffi ci ent model are gi ven i n the
tabl e l abel ed Parameters Requi red for NRTL Property Methods on page 2-45. For
detai l s about the model , see Chapter 3.
Versi on 10
Chapter 2
Parameters Required for NRTL Property Methods
Liquid mixture
Gibbs energy
Enthalpy,
Entropy
Density
NRTL liquid activity coefficient
Extended Antoine vapor pressure
Henrys constant
Brelvi-OConnell
Ideal gas heat capacity
Watson/DIPPR heat of vaporization
NRTL liquid activity coefficient
Rackett
NRTL
PLXANT
Solvent: VC,
Solute-solvent: HENRY
Solvent: TC, PC, (ZC or RKTZRA), Solute:
(VC or VLBROC)
CPIG or CPIGDP
TC, (DHVLWT or DHVLDP)
NRTL
TC, PC, (VC or VCRKT),
(ZC or ZCRKT)
UNIFAC
UNI FAC i s an acti vi ty coeffi ci ent model , l i ke NRTL or UNI QUAC. But i t i s based
on group contri buti ons, rather than mol ecul ar contri buti ons. Wi th a l i mi ted
number of group parameters and group-group i nteracti on parameters, UNI FAC
can predi ct acti vi ty coeffi ci ents. The following table l i sts the property methods based
on UNI FAC.
Versi on 10
Property
Method
Descriptions
UNIFAC Property Methods
Property
Method Name
Model
Name
Parameters
Rev. Yr
Tmin
/K
Tmax
/K
Henry
Lit
Reg
Vapor Phase
EOS Name
Poynting
Correction
UNIFAC UNIFAC 5, 1991 290 420 X X Redlich-
Kwong
X
UNIF-LL UNIFAC , 1991 280 310 X X Redlich-
Kwong
X
UNIF-HOC UNIFAC 5, 1991 290 420 X X Hayden-
O'Connell
X
UNIF-DMD DMD-UNIF 1, 1993 290 420 X X Redlich-
Kwong-
Soave
X
UNIF-LBY LBY-UNIF , 1987 290 420 X X Ideal Gas
law
Databank (DDB).
The ori gi nal versi on of UNI FAC can predi ct VLE and LLE, usi ng two sets of
parameters. So there are two property methods based on the ori gi nal UNI FAC
model , one usi ng the VLE datas et (UNI FAC), the other usi ng the LLE data set
(UNI F-LL).
There are two modi fi cati ons to the UNI FAC model . They are named after the
l ocati on of the uni versi ti es where they were devel oped: Lyngby i n Denmark, and
Dortmund i n Germany. The correspondi ng property methods are UNI F-LBY and
UNI F-DMD. Both modi fi cati ons:
I ncl ude more temperature-dependent terms of the group-group i nteracti on
parameters
Predi ct VLE and LLE wi th a si ngl e set of parameters
Predi ct heats of mi xi ng better
I n the Dortmund modi fi cati on, the predi cti on for acti vi ty coeffi ci ents at i nfi ni te
di l uti on i s i mproved. For detai l s on the model s, see Chapter 3.
coeffi ci ents are avai l abl e i n the ASPEN PLUS databanks for many sol utes wi th
water and other sol vents (see ASPEN PLUS Physical Property Data, Chapter 1).
The opti ons sets wi th a vapor phase model that can be used up to moderate
cal cul ati on (see the tabl e l abel ed UNI FAC Property Methods on page 2-47).
Heats of mi xi ng are cal cul ated usi ng the UNI FAC or modi fi ed UNI FAC model s.
Versi on 10
Chapter 2
Mixture Types
The UNI FAC and modi fi ed UNI FAC model s can handl e any combi nati on of pol ar
and nonpol ar compounds. Di ssol ved gas i n sol uti ons can be handl ed wi th Henrys
Law. However, gas-sol vent i nteracti ons are not predi cted by UNI FAC.
Range
No component shoul d be cl ose to i ts cri ti cal temperature. Approxi mate temperature
ranges are i ndi cated i n the tabl e l abel ed UNI FAC Property Methods on page 2-47.
The parameter sets for al l UNI FAC model s are regul arl y revi sed and extended.
The tabl e l abel ed UNI FAC Property Methods on page 2-47 gi ves the revi si on
number currentl y used i n ASPEN PLUS. For detai l s on the parameters used, see
Physical Property Data, Chapter 3.
The mi ni mum parameter requi rements for the UNI FAC and modi fi ed UNI FAC
model s are gi ven i n the fol l owi ng tabl e. For detai l s about the model s, see Chapter
3.
Parameters Required for the UNIFAC Property Methods
Liquid mixture
Fugacity coefficient, UNIFAC UFGRPD
Gibbs energy or:
Dortmund modified UNIFAC UFGRPL
or:
Lyngby modified UNIFAC PLXANT
Extended Antoine vapor pressure Solvent: VC,
Henrys constant Solute-solvent: HENRY
Brelvi-OConnell Solvent: TC, PC, (ZC or RKTZRA), Solute:
(VC or VLBROC)
Enthalpy, Entropy Ideal gas heat capacity CPIG or CPIGDP
Watson/DIPPR heat of vaporization TC, (DHVLWT or DHVLDP)
UNIFAC UFGRP
or:
Dortmund modified UNIFAC UFGRPD
or:
Lyngby modified UNIFAC UFGRPL
Density Rackett TC, PC, (VC or VCRKT), (ZC or ZCRKT)
Versi on 10
Property
Method
Descriptions
UNIQUAC
The property methods that use the UNI QUAC acti vi ty coeffi ci ent model are
l i sted i n the following table.
UNIQUAC Property Methods
Binary Parameters
Property Method
Name
Dataset Number VLE
Lit
Reg
LLE
Lit
Reg
Henry
Lit
Reg
Vapor Phase
EOS Name
Poynting
Correction
UNIQUAC 1 X X X X X X Ideal Gas law
UNIQ-2 2 X X X X X X Ideal Gas law
UNIQ-RK 1 X X X Redlich-Kwong X
UNIQ-HOC 1 X X X Hayden-O'Connell X
UNIQ-NTH 1 X X Nothnagel X
Databank (DDB).
The UNI QUAC model can descri be strongl y noni deal l i qui d sol uti ons and l i qui d-
l i qui d equi l i bri a. The model requi res bi nary parameters. Many bi nary parameters
for VLE and LLE, from l i terature and from regressi on of experi mental data, are
i ncl uded i n the ASPEN PLUS databanks (for detai l s, see ASPEN PLUS Physical
Property Data, Chapter 1).
coeffi ci ents are avai l abl e from the databank (see ASPEN PLUS Physical Property
Data, Chapter 1).
cal cul ati on (see the tabl e l abel ed UNI QUAC Property Methods on page 2-49).
Heats of mi xi ng are cal cul ated usi ng the UNI QUAC model .
You can use separate data sets for the UNI QUAC bi nary parameters to model
properti es or equi l i bri a at di fferent condi ti ons. I t i s al so possi bl e to use one data
set for VLE and a second data set for LLE (use UNI QUAC and UNI Q-2). The
property methods are i denti cal except for the data set number they use. For
exampl e, you can use these opti ons sets i n di fferent fl owsheet secti ons or col umn
secti ons.
Versi on 10
Chapter 2
Mixture Types
The UNI QUAC model can handl e any combi nati on of pol ar and non-pol ar
compounds, up to very strong noni deal i ty.
Range
Parameter requi rements for the UNI QUAC acti vi ty coeffi ci ent model are gi ven i n
the fol l owi ng tabl e. For detai l s about the model , see Chapter 3.
Parameters Required for UNIQUAC Property Methods
Liquid mixture
Gibbs energy UNIQUAC liquid activity coefficient GMUQR, GMUQQ, UNIQ
Extended Antoine vapor pressure PLXANT
Henrys constant Solvent: VC,
Brelvi-OConnell Solvent: TC, PC, (ZC or RKTZRA),
Solute: (VC or VLBROC)
Enthalpy,
Entropy Ideal gas heat capacity CPIG or CPIGDP
UNIQUAC liquid activity coefficient GMUQR, GMUQQ, UNIQ
Van Laar
The property methods that use the Van Laar acti vi ty coeffi ci ent model are l i sted
i n the following table.
Versi on 10
Property
Method
Descriptions
Van Laar Property Methods
Binary Parameters
Property Method
Name
Dataset number VLE
Lit
Reg
LLE
Lit
Reg
Henry
Lit
Reg
Vapor Phase EOS Name Poynting

Correction
VANLAAR 1 X X Ideal Gas law
VANL-2 2 X X Ideal Gas law
VANL-RK 1 X X Redlich-Kwong X
VANL-HOC 1 X X Hayden-O'Connell X
VANL-NTH 1 X X Nothnagel X
Databank (DDB).
The Van Laar model can descri be noni deal l i qui d sol uti ons wi th posi ti ve devi ati ons
from Raoul ts l aw (see Chapter 1). The model requi res bi nary parameters.
coeffi ci ents are avai l abl e from the ASPEN PLUS databank (see ASPEN PLUS
Physical Property Data, Chapter 1).
cal cul ati on (see the tabl e l abel ed Van Laar Property Methods on page 2-51).
Heats of mi xi ng are cal cul ated usi ng the Van Laar model .
You can use separate data sets to model properti es or equi l i bri a at di fferent
condi ti ons (use VANLAAR and VANL-2). The property methods are i denti cal
except for the data set number they use. For exampl e, you can use these property
methods i n di fferent fl owsheet or col umn secti ons.
Mixture Types
The Van Laar model can handl e any combi nati on of pol ar and non-pol ar
compounds wi th posi ti ve devi ati ons from Raoul ts l aw.
Range
Parameters shoul d be fi tted i n the temperature range of operati on. No component
shoul d be cl ose to i ts cri ti cal temperature.
Parameter requi rements for the Van Laar acti vi ty coeffi ci ent model are gi ven i n
the tabl e l abel ed Parameters Requi red for Van Laar Property Methods on page 2-
51. For detai l s about the model , see Chapter 3.
Versi on 10
Chapter 2
Parameters Required for Van Laar Property Methods
Liquid mixture
Gibbs energy Van Laar liquid activity coefficient VANL
Henrys constant Solvent: VC,
Brelvi-OConnell Solvent: TC, PC, ( ZC or RKTZRA),
Enthalpy,
Entropy Ideal gas heat capacity CPIG or CPIGDP
Van Laar liquid activity coefficient VANL
Wilson
The property methods that use the Wi l son acti vi ty coeffi ci ent model are l i sted i n
the following table.
Wilson Property Methods
Binary Parameters
Property Method
Name
Dataset number VLE
Lit
Reg
LLE
Lit
Reg
Henry
Lit
Reg
Vapor Phase
EOS Name
Poynting
Correction
WILSON 1 X X X X Ideal Gas law
WILS-2 2 X X X X Ideal Gas law
WILS-GLR 1 X X Ideal Gas law ----
WILS-LR 1 X X Ideal Gas law ----
WILS-RK 1 X X X Redlich-Kwong X
WILS-HOC 1 X X X Hayden-O'Connell X
WILS-NTH 1 X X Nothnagel X
Databank (DDB).
Versi on 10
Property
Method
Descriptions
The Wi l son model can descri be strongl y noni deal l i qui d sol uti ons. The model
cannot handl e two l i qui d phases. I n that case use NRTL or UNI QUAC. The model
requi res bi nary parameters. Many bi nary parameters for VLE, from l i terature and
from regressi on of experi mental data, are i ncl uded i n the ASPEN PLUS databanks
(for detai l s, see ASPEN PLUS Physical Property Data, Chapter 1).
The sol ubi l i ty of supercri ti cal gases can be model ed usi ng Henrys l aw. Henry
coeffi ci ents are avai l abl e from the databank for many sol utes wi th water and
other sol vents (see ASPEN PLUS Physical Property Data, Chapter 1).
cal cul ati on (see the tabl e l abel ed Wi l son Property Methods on page 2-52).
Heats of mi xi ng are cal cul ated usi ng the Wi l son model .
You can use separate data sets for the Wi l son bi nary parameters to model
properti es or equi l i bri a at di fferent condi ti ons (use WI LSON and WI LS-2). The
property methods are i denti cal except for the data set number they use. For
exampl e, you can use these property methods i n di fferent fl owsheet or col umn
secti ons.
Mixture Types
The Wi l son model can handl e any combi nati on of pol ar and non-pol ar compounds,
up to very strong noni deal i ty.
Range
Parameter requi rements for the Wi l son acti vi ty coeffi ci ent model are gi ven i n the
tabl e bel ow. For detai l s about the model , see Chapter 3.
Parameters Required for the Wilson Property Methods
Liquid mixture
Gibbs energy Wilson liquid activity coefficient WILSON
Henrys constant Solvent: VC, Solute-solvent: HENRY
Brelvi-OConnell Solvent: TC, PC, (ZC or RKTZRA), Solute: (VC or
VLBROC)
Versi on 10
Chapter 2
Parameters Required for the Wilson Property Methods (continued)
Enthalpy,
Entropy
Ideal gas heat capacity CPIG or CPIGDP
Watson/DIPPR heat of
vaporization
TC, (DHVLWT or DHVLDP)
Wilson liquid activity coefficient WILSON
Common Models
The following table descri bes the model s common to acti vi ty coeffi ci ent property
methods and thei r parameter requi rements.
Parameters Required For Common Models
General
Vapor mixture
Viscosity Chapman-Enskog-Brokaw/ DIPPR MW; (MUP and (STKPAR or LJPAR)) or
MUVDIP
Thermal conductivity Stiel-Thodos low pres./ DIPPR MW or KVDIP
Diffusivity Chapman-Enskog-Wilke-Lee MW; MUP and (STKPAR or LJPAR)
Liquid mixture
Viscosity Andrade/DIPPR MULAND or MULDIP
Thermal Conductivity Sato-Riedel/DIPPR (MW, TC, TB) or KLDIP
Diffusivity Wilke-Chang MW, VB
Versi on 10
Property
Method
Descriptions
Electrolyte Property Methods
The fol l owi ng tabl e lists property methods for el ectrol yte sol uti ons. El ectrol yte
sol uti ons are extremel y noni deal because of the presence of charged speci es.
Property methods based on correl ati ons can handl e speci fi c components under
wel l -descri bed condi ti ons; ri gorous model s are general l y appl i cabl e. The
ELECNRTL property method can handl e mi xed sol vent systems at any
concentrati on. The PI TZER property method i s accurate for aqueous sol uti ons up
to 6M. Bi nary parameters for many component pai rs are avai l abl e i n the
databanks. B-PI TZER i s predi cti ve but l ess accurate. You can use these property
methods at l ow pressures (maxi mum 10 atm). ENRTL-HF i s si mi l ar to
ELECNRTL, but wi th a vapor phase model for the strong HF associ ati on. Thi s
property method shoul d be used at l ow pressures (maxi mum 3 atm). Permanent
gases i n l i qui d sol uti on can be model ed by usi ng Henrys l aw. Transport properti es
are cal cul ated by standard correl ati ons wi th correcti ons for the presence of
el ectrol ytes.
Electrolyte Property Methods
Correlation-Based Property Methods
Property Method Correlation System
AMINES Kent-Eisenberg MEA, DEA, DIPA, DGA
APISOUR API Sour water correlation H2O, NH3, CO2, H2S
Activity Coefficient Model-Based Property Methods
Property Method Gamma Model Name Vapor Phase EOS Name
ELECNRTL Electrolyte NRTL Redlich-Kwong
ENRTL-HF Electrolyte NRTL HF equation of state
ENRTL-HG Electrolyte NRTL Redlich-Kwong
PITZER Pitzer Redlich-Kwong-Soave
PITZ-HG Pitzer Redlich-Kwong-Soave
B-PITZER Bromley-Pitzer Redlich-Kwong-Soave
Common Models For Rigorous Property Methods
Property Model
Vapor pressure Extended Antoine
Liquid molar volume Rackett/Clarke
continued
Versi on 10
Chapter 2
Common Models For Rigorous Property Methods (continued)
Property Model
Heat of vaporization Watson/DIPPR
Infinite dilution heat capacity Criss-Cobble
Surface tension Hakim-Steinberg-Stiel/DIPPR - Onsager-Samara
Liquid viscosity Andrade/DIPPR - Jones-Dole
Liquid thermal conductivity Sato-Riedel/DIPPR - Riedel
Liquid diffusivity Wilke-Chang - Nernst-Hartley
Do not use the el ectrol yte property methods for nonel ectrol yte systems. See
Cl assi fi cati on of Property Methods and Recommended Use on page 2-2 for more
hel p.
For general thermodynami c pri nci pl es, see Chapter 1. Chapter 5 contai ns
speci fi cs on el ectrol yte si mul ati on. For detai l s on methods, see Chapter 4. The
property method descri pti ons gi ve the mi ni mum parameter requi rements for the
thermodynami c property model s used, al so of the common thermodynami c
property model s. The general and transport property parameter requi rements for
coeffi ci ent-based property methods are i n the tabl e l abel ed Parameters Requi red
for General and Transport Property Model s on page 2-66. For detai l s on model s,
see Chapter 3.
AMINES
The AMI NES property methoduses the Kent-Ei senberg method for K-val ues and
enthal py. I t i s desi gned for systems contai ni ng water, one of four ethanol ami nes,
hydrogen sul fi de, carbon di oxi de, and other components typi cal l y present i n gas-
sweeteni ng processes. I t can be used for the fol l owi ng four ami nes:
Monoethanol ami ne (MEA)
Di ethanol ami ne (DEA)
Di i sopropanol ami ne (DI PA)
Di gl ycol ami ne (DGA)
Versi on 10
Property
Method
Descriptions
Range
Use the AMI NES property method for ami ne systems wi th ranges of:
MEA DEA DIPA DGA
Temperature (F) 90 280 90 275 90 260 90 280
Maximum H2s or CO2 Loading (moles
gas/mole amine)
0.5 0.8 0.75 0.5
Amine Concentration in Solution (mass
percent)
15 30 20 40 20 40 40 65
I f the ami ne concentrati on i s outsi de the recommended range, the Chao-Seader
method i s used for K-val ues (onl y for that parti cul ar property eval uati on).
Refer to the fol l owi ng tabl e for parameter requi rements for thi s property method.
Parameters Required for the AMINES Property Method
General
Using free-water option: solubility of water in organic phase WATSOL
Vapor mixture
Density
Redlich-Kwong, TC; PC
Enthalpy, entropy Ideal gas heat capacity/DIPPR CPIG or CPIGDP
Liquid mixture
Gibbs energy
Scatchard-Hildebrand activity coefficient TC; DELTA; VLCVT1; GMSHVL
Chao-Seader pure component fugacity
coefficient
TC; PC; OMEGA
continued
Versi on 10
Chapter 2
Thermodynamic Properties (continued)
Extended Antoine vapor pressure (amines and
water only)
PLXANT
Kent-Eisenberg (H2S and CO2 only)
Enthalpy, entropy Watson heat of vaporization and DIPPR model TC; PC;DHVLWT or DHVLDP
Density Rackett molar volume TC; PC: VC or VCRKT; ZC or ZCRKT
Vapor mixture Dean-Stiel
Viscosity MW; (MUP and (STKPAR or LJPAR)) or
MUVDIP; TC, PC, VC
Thermal conductivity Stiel-Thodos MW, TC, PC, VC, ZC
Diffusivity Dawson-Khoury-Kobayaski MW; MUP and (STKPAR or LJPAR); VC
Liquid mixture
APISOUR
The API SOUR property method:
Uses the API procedure for K-val ues and enthal py of sour water systems.
I s desi gned for sour water systems contai ni ng onl y water, ammoni a, hydrogen
sul fi de and carbon di oxi de.
I s appl i cabl e i n the temperature range of 20 140C.
Has an overal l average error between measured and predi cted parti al
pressures of about 30% for ammoni a, carbon di oxi de, and hydrogen sul fi de.
Does not requi re any user-suppl i ed parameters.
I s recommended for fast si mul ati on of sour water systems at l i mi ted
concentrati on. For more accurate resul ts, use the ELECNRTL property method.
Parameter requi rements for the API SOUR property method are l i sted i n the
following table.
Versi on 10
Property
Method
Descriptions
Parameters Required for the APISOUR Property Method
General
Vapor mixture
MUVDIP
Liquid mixture
ELECNRTL
The ELECNRTL property methodi s the most versati l e el ectrol yte property method.
I t can handl e very l ow and very hi gh concentrati ons. I t can handl e aqueous and
mi xed sol vent systems.
The ELECNRTL i s ful l y consi stent wi th the NRTL-RK property method: the
mol ecul ar i nteracti ons are cal cul ated exactl y the same way, therefore
ELECNRTL can use the databank for bi nary mol ecul ar i nteracti on parameters
for the NRTL-RK property method.
Many bi nary and pai r parameters and chemi cal equi l i bri um constants from
regressi on of experi mental data are i ncl uded i n ASPEN PLUS databanks. See
ASPEN PLUS Physical Property Data, Chapter 2, for detai l s on the systems
i ncl uded, the sources of the data, and the ranges of appl i cati on.
Versi on 10
Chapter 2
The sol ubi l i ty of supercri ti cal gases can be model ed usi ng Henrys l aw. Henry
coeffi ci ents are avai l abl e from the databank (see Chapter 1).
Heats of mi xi ng are cal cul ated usi ng the el ectrol yte NRTL model .
The Redl i ch-Kwong equati on of state i s used for al l vapor phase properti es,
whi ch cannot model associ ati on behavi or i n the vapor phase as occurs wi th
carboxyl i c aci ds or HF. For carboxyl i c aci ds, choose Hayden-OConnel l or
Nothnagel ; for HF choose ENRTL-HF.
Mixture Types
Any l i qui d el ectrol yte sol uti on unl ess there i s associ ati on i n the vapor phase.
Range
Vapor phase properti es are descri bed accuratel y up to medi um pressures.
I nteracti on parameters shoul d be fi tted i n the range of operati on.
The parameter requi rements for the ELECNRTL property method are gi ven i n
the fol l owi ng tabl e, Parameters Requi red for the ELECNRTL Property Method,
and Parameters Requi red for General and Transport Property Model s on page 2-
66. For detai l s about the model see Chapter 3.
Parameters Required for the ELECNRTL Property Method
Vapor mixture
Density Redlich-Kwong TC, PC
Enthalpy,
Entropy,
Gibbs energy
[Ideal gas heat capacity/
DIPPR/
Barin correlation
and
Redlich-Kwong
CPIG or
CPIGDP or
CPIXP1, CPIXP2, CPIXP3]
TC, PC
Liquid mixture
Gibbs energy
Electrolyte NRTL Mol.: CPDIEC
Ion: RADIUS
Mol.-Mol.: NRTL
Mol.-Ion, Ion-Ion: GMELCC, GMELCD
GMELCE, GMELCN
Henrys constant Solvent: VC, Mol. solute-solvent: HENRY
continued
Versi on 10
Property
Method
Descriptions
Parameters Required for the ELECNRTL Property Method (continued)
Brelvi-OConnell Solvent: TC, PC, (ZC or RKTZRA), Mol.
solute: (VC or VLBROC)
Enthalpy,
Entropy
DIPPR
and
or
[Infinite dilution heat capacity / Criss-Cobble
Electrolyte NRTL
CPIG or
CPIGDP
Solvent: TC, (DHVLWT or DHVLDP)]
Ions: CPAQ0 or
Ions: IONTYP, S025C ]
Mol.: CPDIEC
Ion: RADIUS
Mol.-Mol.: NRTL
Mol.-Ion, Ion-Ion: GMELCC, GMELCD
GMELCE, GMELCN
Density Rackett/Clarke Mol.: TC, PC, (VC or VCRKT), (ZC or ZCRKT)
Ion-ion: VLCLK
Solid pure (and mixture)
Enthalpy,
Entropy
Solids heat capacity polynomial/ Barin
correlation
CPSP01 or CPSXP1 to CPSXP7
Density Solids molar volume polynomial VSPOLY
ENRTL-HF
The ENRTL-HF property method i s si mi l ar to the ELECNRTL property method
except that i t uses the HF equati on of state as vapor phase model .
The HF equati on of state predi cts the strong associ ati on of HF i n the vapor phase
at l ow pressures. Associ ati on (mai nl y hexameri zati on) affects both vapor phase
properti es (for exampl e, enthal py and densi ty) and l i qui d phase properti es (for
exampl e, enthal py).
A data package i s avai l abl e to accuratel y model vapor and l i qui d phases of HF
and water mi xtures i n any proporti on.
Mixture Types
The HF equati on of state rel i abl y predi cts the strong associ ati on effects of HF i n
the vapor phase. The l i qui d can be any l i qui d el ectrol yte sol uti on.
Range
Usage shoul d not exceed pressures of 3 atm.
Versi on 10
Chapter 2
Parameters for the HF equati on of state are bui l t-i n for temperatures up to 373
K. Parameters can be entered and regressed usi ng the ASPEN PLUS Data
Regressi on System (DRS) i f needed. For detai l s about the model , see Chapter 3.
For the parameter requi rements for the el ectrol yte NRTL model , refer to the
ELECNRTL property method, i n the tabl e l abel ed Parameters Requi red for the
ELECNRTL Property Method on page 2-59. For general and transport property
parameter requi rements, see the tabl e l abel ed Parameters Requi red for General
and Transport Property Model s on page 2-66.
ENRTL-HG
The ENRTL-HG property method i s si mi l ar to the ELECNRTL property method,
except i t uses the Hel geson model for standard properti es cal cul ati ons. The
Hel geson model i s a very accurate and fl exi bl e equati on of state that cal cul ates
standard enthal py, entropy, Gi bbs free energy and vol ume for components i n
aqueous sol uti ons. The Hel geson model shoul d provi de more accurate enthal py and
Gi bbs free energy of process streams up to hi gh temperatures and pressures. The
model i s al so used to cal cul ate Gi bbs free energy for use i n esti mati ng chemi cal
equi l i bri um constants (for both equi l i bri um and sal t preci pi tati on reacti ons) when
they are mi ssi ng. Equi l i bri um constants cal cul ated usi ng the Hel geson model have
been found to be reasonabl y accurate and extrapol ate wel l wi th respect to
temperature.
Mixture Types
Any l i qui d el ectrol yte sol uti on i s acceptabl e, unl ess there i s associ ati on i n the vapor
phase.
Range
Vapor phase properti es are descri bed accuratel y up to medi um pressures.
For parameter requi rements for the el ectrol yte NRTL model , see the ELECNRTL
property method, i n the tabl e l abel ed Parameters Requi red for the ELECNRTL
Property Method on page 2-59. For general and transport property parameter
requi rements, see the tabl e l abel ed Parameters Requi red for General and
Transport Property Model s on page 2-66.
Versi on 10
Property
Method
Descriptions
PITZER
The PI TZER property method i s based on an aqueous el ectrol yte acti vi ty coeffi ci ent
model . I t has no overl ap wi th other acti vi ty coeffi ci ent model s. I t can accuratel y
cal cul ate the behavi or of aqueous el ectrol yte sol uti ons wi th or wi thout mol ecul ar
sol utes up to 6 mol al i oni c strength.
Many i nteracti on parameters from regressi on of experi mental data are i ncl uded
i n databanks and data packages (for detai l s, see Chapter 1).
coeffi ci ents are avai l abl e from the ASPEN PLUS databanks (see Chapter 1).
Heats of mi xi ng are cal cul ated usi ng the Pi tzer model .
The Redl i ch-Kwong-Soave equati on of state i s used for the vapor phase fugaci ty
coeffi ci ent, al l other vapor phase properti es are assumed i deal . Redl i ch-Kwong-
Soave cannot model associ ati on behavi or i n the vapor phase (for exampl e,
carboxyl i c aci ds or HF). For carboxyl i c aci ds, choose a non-el ectrol yte acti vi ty
coeffi ci ent model wi th Hayden-OConnel l or Nothnagel ; for HF choose ENRTL-
HF or WI LS-HF.
Mixture Types
You can use the Pi tzer model for any aqueous el ectrol yte sol uti on up to 6M i oni c
strength, not showi ng associ ati on i n the vapor phase.
Range
Vapor phase fugaci ti es are descri bed accuratel y up to medi um pressures.
The parameter requi rements for the PI TZER property method are gi ven i n the
tabl e l abel ed Parameters Requi red for the PI TZER Property Method on page 2-63
and the tabl e l abel ed Parameters Requi red for General and Transport Property
Model s on page 2-66. For detai l s about the model , see Chapter 3.
Versi on 10
Chapter 2
Parameters Required for the PITZER Property Method
Vapor mixture
Density
Redlich-Kwong-Soave TC, PC, OMEGA
Enthalpy,
Entropy,
Gibbs energy
DIPPR/
Barin correlation
and
Redlich-Kwong
CPIG or
CPIGDP or
CPIXP1, CPIXP2, CPIXP3]
TC, PC, OMEGA
Liquid mixture
Gibbs energy
Pitzer Cation-anion: GMPTB0, GMPTB1, GMPTB2,
GMPTB3, GMPTC
Cation-cation: GMPTTH
Anion-anion: GMPTTH
Cation1-cation2-common anion: GMPTPS
Anion1-anion2-common cation: GMPTPS
Molecule-ion, Mol. Mol.: GMPTB0,
GMPTB1, GMPTC
Henry's constant Solvent: VC, Mol. Solute-solvent: HENRY
Brelvi-O'Connell Solvent: TC, PC, (ZC or RKTZRA), Mol.
Enthalpy,
Entropy [Ideal gas heat capacity/ DIPPR
and
or
[Infinite dilution heat capacity /
CPIG or
CPIGDP
Ions: CPAQ0 or
Criss-Cobble Ions: IONTYP, S025C ]
Pitzer Cation-anion:
GMPTB0,GMPTB1,GMPTB2,GMPTB3,GMPT
C
Anion-anion: GMPTTH
Cation1-cation2-common anion: GMPTPS
Anion1-anion2-common cation: GMPTPS
Molecule-ion, Mol. Mol.:
GMPTB0,GMPTB1,GMPTC
Ion-ion: VLCLK
continued
Versi on 10
Property
Method
Descriptions
Parameters Required for the PITZER Property Method (continued)
Enthalpy,
Entropy
Solids heat capacity polynomial/
Barin correlation
CPSP01 or
CPSXP1 to CPSXP7
B-PITZER
The B-PI TZER property method i s based on the si mpl i fi ed Pi tzer aqueous
el ectrol yte acti vi ty coeffi ci ent model , whi ch negl ects thi rd order i nteracti ons. I t can
predi ct the behavi or of aqueous el ectrol yte sol uti ons up to 6 mol al i oni c strength. I t
i s not as accurate as ELECNRTL or PI TZER wi th fi tted parameters. But, i t i s
better than usi ng these property methods wi thout i nteracti on parameters.
coeffi ci ents are avai l abl e from the ASPEN PLUS databanks (see Chapter 1).
Heats of mi xi ng are cal cul ated usi ng the Broml ey-Pi tzer model .
The Redl i ch-Kwong-Soave equati on of state i s used for the vapor phase fugaci ty
coeffi ci ent. Al l other vapor phase properti es are assumed i deal . Redl i ch-Kwong-
Soave cannot model associ ati on behavi or i n the vapor phase (for exampl e wi th
carboxyl i c aci ds or HF). For carboxyl i c aci ds, choose a non-el ectrol yte acti vi ty
coeffi ci ent model wi th Hayden-OConnel l or Nothnagel ; for HF, choose ENRTL-
HF or WI LS-HF.
Mixture Types
You can use the B-PI TZER model for any aqueous el ectrol yte sol uti on up to 6M
i oni c strength, not showi ng associ ati on i n the vapor phase.
Range
The parameter requi rements for the B-PI TZER property method are gi ven i n the
tabl e l abel ed Parameters Requi red for the B-PI TZER Property Method on page 2-
65 and the tabl e l abel ed Parameters Requi red for General and Transport
Property Model s on page 2-66. For detai l s about the model , see Chapter 3.
Versi on 10
Chapter 2
Parameters Required for the B-PITZER Property Method
Vapor mixture
Density Redlich-Kwong-Soave TC, PC, OMEGA
Enthalpy,
Entropy,
Gibbs energy
[Ideal gas heat capacity/ DIPPR/ Barin
correlation and Redlich-Kwong
CPIG or CPIGDP or CPIXP1, CPIXP2,
CPIXP3] TC, PC, OMEGA
Liquid mixture
Gibbs energy
Bromley-Pitzer Ionic: GMBPB, GMBPD Optional:
Cation-anion: GMPTB0, GMPTB1, GMPTB2,
GMPTB3
Anion-anion: GMPTTH
Molecule-ion, Mol.-Mol.: GMPTB0, GMPTB1
Henrys constant Solvent: VC, Mol. Solute-solvent: HENRY
Brelvi-OConnell Solvent: TC, PC, (ZC or RKTZRA), Mol.
Enthalpy,
Entropy
[Ideal gas heat capacity/ DIPPR and
Watson/DIPPR heat of vaporization or[Infinite
dilution heat capacity / Criss-Cobble
CPIG or
CPIGDP
Ions: CPAQ0 or
Ions: IONTYP, S025C ]
Bromley-Pitzer Ionic: GMBPB, GMBPD
Optional:
Cation-anion: GMPTB0, GMPTB1, GMPTB2,
GMPTB3
Cation-cation:GMPTTH
Anion-anion: GMPTTH
Molecule-ion, Mol.-Mol.: GMPTB0, GMPTB1
Ion-ion: VLCLK
Enthalpy,
Entropy
Solids heat capacity polynomial/ Barin
correlation
CPSP01 or CPSXP1 to CPSXP7
Versi on 10
Property
Method
Descriptions
PITZ-HG
The PI TZ-HG property method i s si mi l ar to the PI TZER property method, except i t
uses the Hel geson model for standard properti es cal cul ati ons. The Hel geson model
i s a very accurate and fl exi bl e equati on of state that cal cul ates standard enthal py,
entropy, Gi bbs free energy and vol ume for components i n aqueous sol uti ons. The
Hel geson model shoul d provi de more accurate enthal py and Gi bbs free energy of
process streams up to hi gh temperatures and pressures. The Hel geson model i s
al so used to cal cul ate Gi bbs free energy for use i n esti mati ng chemi cal equi l i bri um
constants (for both equi l i bri um and sal t preci pi tati on reacti ons) when they are
mi ssi ng. Equi l i bri um constants cal cul ated usi ng the Hel geson model have been
found to be reasonabl y accurate and extrapol ate wel l wi th respect to temperature.
Mixture Types
You can use thi s property method for any aqueous el ectrol yte sol uti on up to 6M
i oni c strength, not showi ng associ ati on i n the vapor phase.
Range
The parameter requi rements for the PI TZ-HG property method are gi ven i n the
tabl e l abel ed Parameters Requi red for the PI TZER Property Method on page 2-63
and the fol l owi ng tabl e, Parameters Requi red for General and Transport
Property Model s. For detai l s about the model , see Chapter 3.
General and Transport Property Model Parameter
Requirements
The following table descri bes the general and transport property model s used and
thei r parameter requi rements for acti vi ty coeffi ci ent-based el ectrol yte property
methods.
Parameters Required for General and Transport Property Models
General
Mass balance,
Continued
Versi on 10
Chapter 2
General (continued)
Conversion Mass-
basisMole-basis
MW
Enthalpy of reaction Solvents, Mol. Solutes: DHFORM
Solids, Salts: (DHSFRM or CPSXP1 to CPSXP7)
Ions: DHAQFM
Gibbs energy of reaction Solvents, Mol. Solutes: DGFORM
Solids,Salts: (DGSFRM or CPSXP1 to CPSXP7)
Ions: DGAQFM
Vapor mixture
MUVDIP
Surface tension Hakim-Steinberg-Stiel/ DIPPR Onsager-
Samaras
Solv., Mol.sol.: (TC, PC, OMEGA) or SIGDIP

Ion: CHARGE
Liquid mixture
Viscosity Andrade/DIPPR Jones-Dole
Solv., Mol.sol.: MULAND or MULDIP Ion:

IONMUB, IONMOB
Thermal Conductivity Sato-Riedel/ DIPPR Riedel
Solv., Mol.sol.: (MW, TC, TB) or KLDIP Ion:

IONRDL
Diffusivity Wilke-Chang/ Nernst-Hartley
Solv., Mol.sol.: MW, VB Ion: CHARGE,

IONMOB
Onl y for ri gorous el ectrol yte property methods

Solids Handling Property Method
The SOLI DS property method i s desi gned for many ki nds of sol i ds processi ng:
Coal processi ng
Pyrometal l urgi cal processes
Mi scel l aneous other sol i ds processi ng (such as starch and pol ymers)
Versi on 10
Property
Method
Descriptions
The properti es of sol i ds and fl ui d phases cannot be cal cul ated wi th the same type of
model s. Therefore the components are di stri buted over the substreams of types
MI XED, CI SOLI D and NC and thei r properti es are cal cul ated wi th appropri ate
model s (for detai l s on the use of substreams, see ASPEN PLUS User Guide,
Chapter 9).
Duri ng the mechani cal processi ng of raw materi al s (ore, coal , wood), physi cal
properti es can often be handl ed as nonconventi onal components wi th an overal l
densi ty and an overal l heat capaci ty. The characteri zati on of nonconventi onal
components and the speci fi cati on of property model s i s di scussed i n the
ASPEN PLUS User Guide, Chapter 7. Detai l s on nonconventi onal property
methods and model s are gi ven i n chapters 1 and 3 of thi s manual , respecti vel y.
When the sol i ds are decomposed i nto i ndi vi dual components (for exampl e, to
sel ecti vel y undergo chemi cal reacti ons), they occur i n the CI SOLI D substream.
The property model s for these components are pure component property model s
of the pol ynomi al type. The components are not i n phase equi l i bri um wi th the
fl ui d components. Some exampl es are coal dust i n ai r, burni ng carbon, and sand
i n water.
I n pyrometal l urgi cal appl i cati ons, a CI SOLI D component can be i n si mul taneous
phase and chemi cal equi l i bri um. Thi s can happen onl y i n the RGI BBS model , an
equi l i bri um reactor based on Gi bbs energy mi ni mi zati on. Under other condi ti ons,
the CI SOLI D component can undergo reacti ons but not phase equi l i bri um. As
another excepti on, homogeneous sol i d mi xture phases can occur i n the same
reactor. The noni deal i ty of sol i d mi xtures can be handl ed usi ng acti vi ty
coeffi ci ent model s. To di sti ngui sh a sol i d mi xture from si ngl e CI SOLI D
components, they are pl aced i n the MI XED substream.
I n pyrometal l urgi cal appl i cati ons, many phases can occur si mul taneousl y. These
phases may need to be treated wi th di fferent acti vi ty coeffi ci ent model s (use the
SOLI DS property method). For detai l s, see ASPEN PLUS Getting Started
Modeling Processes with Solids.
Fl ui d components al ways occur i n the MI XED substream. They are treated wi th
the same fl ui d phase model s as di scussed i n I DEAL. I f non-i deal i ty i n the l i qui d
phase occurs, the i deal acti vi ty coeffi ci ent model can be repl aced.
Permanent gases may be di ssol ved i n the l i qui d. You can model them usi ng
Henrys l aw, whi ch i s val i d at l ow concentrati ons.
Hydrometal l urgi cal appl i cati ons cannot be handl ed by the SOLI DS property
method. Use an el ectrol yte property method.
The transport property model s for the vapor phase are al l wel l sui ted for i deal
gases. The transport property model s for the l i qui d phase are empi ri cal equati ons
for fi tti ng of experi mental data.
The fol l owi ng tabl e l i sts the model s used i n the SOLI DS property method and
thei r parameter requi rements. For detai l s on these model s, see Chapter 3.
Versi on 10
Chapter 2
Parameters Required for the SOLIDS Property Method
General
basisMole-basis
MW
Free-water option: solubility of water in organic
phase
WATSOL
Enthalpy of reaction DHFORM, (DHSFRM or CPSXP1 to CPSXP7)
Gibbs energy of reaction DGFORM, (DGSFRM or CPSXP1 to CPSXP7)
Vapor pure and mixture
Fugacity
Coefficient
Ideal gas law
Enthalpy,
Entropy,
Gibbs energy
Ideal gas heat capacity/ DIPPR/ Barin
correlation
CPIG or CPIGDP or CPIXP1, CPIXP2,
CPIXP3
Density Ideal gas law
Liquid pure and mixture
Fugacity
Coefficient,
Gibbs energy
Extended Antoine vapor pressure/
Barin correlation
PLXANT or
CPIXP1, CPIXP2
Henry's constant Solvent: VC, Solute-solvent: HENRY
Brelvi-O'Connell Solvent: TC, PC, (ZC or RKTZRA), Solute:
(VC or VLBROC)
Enthalpy,
Entropy
DIPPR
and
CPIG or
CPIGDP
TC, (DHVLWT or DHVLDP)]
continued
Versi on 10
Property
Method
Descriptions
Thermodynamic Properties (continued)
DIPPR heat capacity correlation/
Barin correlation
(CPLDIP or
CPLXP1, CPLXP2
Density Constant Volume,
Ideal mixing
VLCONS
Fugacity
Coefficient,
Gibbs energy
Extended Antoine vapor pressure/
Barin correlation
PLXANT
CPSXP1 to CPSXP7
Enthalpy,
Entropy
Solids heat capacity polynomial/
Barin correlation
CPSP01 or
CPSXP1 to CPSXP7
Vapor pure and mixture
Viscosity Chapman-Enskog-Brokaw/
DIPPR
MW; (MUP and (STKPAR or LJPAR))
or MUVDIP
Thermal conductivity
DIPPR
Stiel-Thodos low pres./
KVDIP
MW or
Surface tension Hakim-Steinberg-Stiel/
DIPPR
(TC, PC, OMEGA) or
SIGDIP
Solids pure
Thermal Conductivity Solids, polynomial KSPOLY
Versi on 10
Chapter 2
Steam Tables
The following table l i sts the names of the two steam tabl e property methods
avai l abl e i n ASPEN PLUS.
Steam Tables Property Methods
Steam Tables:
STEAM-TA
STEAMNBS
ASME 1967
NBS/NRC 1984
Common models:
IAPS vapor viscosity
IAPS vapor thermal conductivity
IAPS surface tension
IAPS liquid viscosity
IAPS liquid thermal conductivity
Steam tabl es can cal cul ate al l thermodynami c properti es for systems contai ni ng
pure water or steam. For mi xtures of water and other components, refer to the
begi nni ng of thi s chapter for more hel p. The NBS/NRC steam tabl es are more
recent and accurate.
The transport property model s for both property methods are from the
I nternati onal Associ ati on for Properti es of Steam (I APS).
Al l model s have bui l t-i n parameters. For detai l s, see Chapter 3.
STEAM-TA
The STEAM-TA property method uses the:
1967 ASME steam tabl e correl ati ons for thermodynami c properti es
I nternati onal Associ ati on for Properti es of Steam (I APS) correl ati ons for
transport properti es
Use thi s property method for pure water and steam. ASPEN PLUS uses
STEAM-TA as the defaul t property method for the free-water phase, when free-
water cal cul ati ons are performed.
Versi on 10
Property
Method
Descriptions
Range
Use the STEAM-TA property method for pure water and steam wi th temperature
ranges of 273.15 K to 1073 K. The maxi mum pressure i s 1000 bar.
STEAMNBS
The STEAMNBS property method uses:
1984 NBS/NRC steam tabl e correl ati ons for thermodynami c properti es
I nternati onal Associ ati on for Properti es of Steam (I APS) correl ati ons for
transport properti es
Use thi s property method for pure water and steam.
Range
Use the STEAMNBS property method for pure water and steam wi th temperature
ranges of 273.15 K to 2000 K. The maxi mum pressure i s over 10000 bar.
O O O O
Versi on 10
Chapter 3
3 Property Model
Descriptions
Thi s chapter descri bes the property model s avai l abl e i n ASPEN PLUS and
defi nes the parameters used i n each model . The descri pti on for each model l i sts
the parameter names used to enter val ues i n ASPEN PLUS on the Properti es
Parameters forms.
Many parameters have defaul t val ues i ndi cated i n the Defaul t col umn. A dash ()
i ndi cates that the parameter has no defaul t val ue and you must provi de a val ue.
I f a parameter i s mi ssi ng, si mul ati on cal cul ati ons stop. The l ower l i mi t and
upper l i mi t for each parameter, when avai l abl e, i ndi cate the reasonabl e bounds
for the parameter. The l i mi ts are used to detect grossl y erroneous parameter
val ues.
The property model s are di vi ded i nto the fol l owi ng categori es:
Thermodynami c property model s
Transport property model s
Nonconventi onal sol i d property model s
The property types for each category are di scussed i n separate secti ons of thi s
chapter. The fol l owi ng tabl e provi des an organi zati onal overvi ew of thi s chapter.
The tabl es l abel ed Thermodynami c Property Model s, Transport Property Model s,
and Nonconventi onal Sol i d Property Model s i n thi s chapter present detai l ed l i sts
of model s. These tabl es al so l i st the ASPEN PLUS model names, and thei r
possi bl e use i n di fferent phase types, for pure components and mi xtures.
El ectrol yte and conventi onal sol i d property model s are presented i n
Thermodynami c Property Model s, thi s chapter. For more detai l s on el ectrol yte
coeffi ci ent model s, see Appendi ces A, B, and C.
Versi on10
Property
Model
Descriptions
Categories of Models
Category Sections Details
Thermodynamic Property
Models
Vapor Pressure and Liquid Fugacity Models
Heat of Vaporization Models
Molar Volume and Density Models
Heat Capacity Models
Solubility Correlations
Other
Thermodynamic
Property Models
Transport Property Models Viscosity Models
Thermal Conductivity Models
Diffusivity Models
Surface Tension Models
Transport
Property Models
Nonconventional Solid Property
Models
General Enthalpy and Density Models
Enthalpy and Density Models for Coal and Char
Nonconventional
Solid Property
Models
Versi on 10
Chapter 3
Thermodynamic Property Models
Thi s secti on descri bes the avai l abl e thermodynami c property model s i n
ASPEN PLUS. The fol l owi ng tabl e provi des a l i st of avai l abl e model s, wi th
correspondi ng ASPEN PLUS model names. The tabl e provi des phase types for
whi ch the model can be used and i nformati on on use of the model for pure
components and mi xtures.
ASPEN PLUS thermodynami c property model s i ncl ude cl assi cal thermodynami c
property model s, such as acti vi ty coeffi ci ent model s and equati ons of state, as
wel l as sol i ds and el ectrol yte model s. The model s are grouped accordi ng to the
type of property they descri be.
Thermodynamic Property Models
Property Model Model Name(s) Phase(s)
Pure
Mixture
ASME Steam Tables ESH2O0, ESH2O V L X

BWR-Lee-Starling ESBWR0, ESCSTBWR V L X X
Hayden-O'Connell ESHOC0, ESHOC V X X
HF equation-of-state ESHF0, ESHF V X X
Ideal Gas ESIG V X X
Lee-Kesler ESLK V L X
Lee-Kesler-Plcker ESLKP0, ESLKP V L X X
NBS/NRC Steam Tables ESSTEAM0, ESSTEAM V L X
Nothnagel ESNTH0, ESNTH V X X
Peng-Robinson-Boston-Mathias ESPR0, ESPR V L X X
Peng-Robinson-Wong-Sandler ESPRWS0, ESPRWS V L X X
Peng-Robinson-MHV2 ESPRV20, ESPRV2 V L X X
Predictive SRK ESRKSV10, ESRKSV1 V L X X
Redlich-Kwong ESRK0, ESRK V X X
Redlich-Kwong-Aspen ESRKA0, ESRKA V L X X
Redlich-Kwong-Soave-Boston-Mathias ESRKS0, ESRKS V L X X
Redlich-Kwong-Soave-Wong-Sandler ESRKSWS0, ESRKSWS V L X X

V =Vapor; L =Liquid; S =Solid
An X indicates applicable to Pure or Mixture

continued
Versi on10
Property
Model
Descriptions
Equation-of-State Models (continued)
Property Model Model Name(s) Phase(s)
Pure
Mixture
Redlich-Kwong-Soave-MHV2 ESRKSV20, ESRKSV2 V L X X

Standard Peng-Robinson ESPRSTD0, ESPRSTD V L X X
Standard Redlich-Kwong-Soave ESRKSTD0, ESRKSTD V L X X
Peng-Robinson Alpha functions V L X
RK-Soave Alpha functions V L X
Huron-Vidal mixing rules V L X
MHV2 mixing rules V L X
PSRK mixing rules V L X
Wong-Sandler mixing rules V L X
Property Model Model Name Phase(s)
Pure
Mixture
Bromley-Pitzer (Chien-Null) GMPT2 L X

Chien-Null GMCHNULL L X
Constant Activity Coefficient GMCONS S X
Electrolyte NRTL GMELC L L1 L2 X
Ideal Liquid GMIDL L X
NRTL (Non-Random-Two-Liquid) GMRENON L L1 L2 X
Pitzer GMPT1 L X
Polynomial Activity Coefficient GMPOLY S X
Redlich-Kister GMREDKIS L S X
Scatchard-Hildebrand GMXSH L X
Three-Suffix Margules GMMARGUL L S X
UNIFAC GMUFAC L L1 L2 X
UNIFAC (Lyngby modified) GMUFLBY L L1 L2 X
UNIFAC (Dortmund modified) GMUFDMD L L1 L2 X
UNIQUAC GMUQUAC L L1 L2 X
van Laar GMVLAAR L X


continued
Versi on 10
Chapter 3
Vapor Pressure and Liquid Fugacity Models (continued)
Pure
Mixture
Wagner interaction parameter GMWIP S X

Wilson GMWILSON L X
Wilson model with liquid molar volume GMWSNVOL L X
Extended Antoine/Wagner PL0XANT L L1 L2 X
Chao-Seader PHL0CS L X
Grayson-Streed PHL0GS L X
Kent-Eisenberg ESAMIN L X
Heat of Vaporization Models
Pure
Mixture
Watson / DIPPR DHVLWTSN L X

Clausius-Clapeyron Equation DHVLWTSN L X
Pure
Mixture
API Liquid Volume VL2API L X

Brelvi-O'Connell VL1BROC L X
Clarke Aqueous Electrolyte Volume VAQCLK L X
Costald Liquid Volume VL0CTD, VL2CTD L X X
Debije-Hckel Volume VAQDH L X
Rackett / DIPPR Liquid Volume VL0RKT, VL2RKT L X
Rackett Mixture Liquid Volume VL2RKT L X X
Modified Rackett VL2MRK L X X
Solids Volume Polynomial VS0POLY S X

continued
Versi on10
Property
Model
Descriptions
Pure
Mixture
Aqueous Infinite Dilution

Heat Capacity Polynomial
L X
Criss-Cobble Aqueous Infinite
Dilution Ionic Heat Capacity
L X
DIPPR Liquid Heat Capacity HL0DIP L X
Ideal Gas Heat Capacity / DIPPR V X X
Solids Heat Capacity Polynomial HS0POLY S X
Solubility Correlation Models
Pure
Mixture
Henrys constant HENRY1 L X

Water solubility L X
Other Models
Pure
Mixture
Cavett Liquid Enthalpy Departure DHL0CVT, DHL2CVT L X X

BARIN Equations for Gibbs Energy,
Enthalpy, Entropy and Heat Capacity
S L V X
Electrolyte NRTL Enthalpy HAQELC, HMXELC L X
Electrolyte NRTL Gibbs Energy GAQELC, GMXELC L X
Liquid Enthalpy from Liquid Heat Capacity
Correlation
DHL0DIP L X X
Enthalpies Based on Different Reference
Status
DHL0HREF L V X X


Versi on 10
Chapter 3
ASPEN PLUS has 20 bui l t-i n equati on-of-state property model s. Thi s secti on
descri bes the equati on-of-state property model s avai l abl e.
Model Type
ASME Steam Tables Fundamental
BWR-Lee-Starling Virial
Hayden-OConnell Virial and association
HF Ideal and association
Huron-Vidal mixing rules Mixing rules
Ideal Gas Ideal
Lee-Kesler Virial
Lee-Kesler-Plcker Virial
MHV2 mixing rules Mixing rules
NBS/NCR Steam Tables Fundamental
Nothnagel Ideal
Peng-Robinson alpha functions Alpha functions
Peng-Robinson-Boston-Mathias Cubic
Peng-Robinson-MHV2 Cubic
Peng-Robinson-Wong-Sandler Cubic
Predictive SRK Cubic
PSRK mixing rules Mixing rules
Redlich-Kwong Cubic
Redlich-Kwong-Aspen Cubic
Redlich-Kwong-Soave-Boston-Mathias Cubic
Redlich-Kwong-Soave-MHV2 Cubic
Redlich-Kwong-Soave-Wong-Sandler Cubic
RK-Soave alpha functions Alpha functions
Schwartzentruber-Renon Cubic
Standard Peng-Robinson Cubic
Standard Redlich-Kwong-Soave Cubic
Wong-Sandler mixing rules Mixing rules
Versi on10
Property
Model
Descriptions
ASME Steam Tables
The ASME steam tabl es (1967) are i mpl emented l i ke any other equati on-of-state
i n ASPEN PLUS. The steam tabl es can cal cul ate any thermodynami c property of
water or steam and form the basi s of the STEAM-TA property method. There are
no parameter requi rements. The ASME steam tabl es are l ess accurate than the
NBS/NRC steam tabl es.
References
ASME Steam Tables, Thermodynami c and Transport Properti es of Steam, (1967).
K. V. Moore, Aerojet Nucl ear Company, prepared for the U.S. Atomi c Energy
Commi si on, ASTEM - A Col l ecti on of FORTRAN Subrouti nes to Eval uate the
1967 ASME equati ons of state for water/steam and deri vati ves of these
equati ons.
BWR-Lee-Starling
The Benedi ct-Webb-Rubi n-Lee-Starl i ng equati on-of-state i s the basi s of the
BWR-LS property method. I t i s a general i zati on by Lee and Starl i ng of the vi ri al
equati on-of-state for pure fl ui ds by Benedi ct, Webb and Rubi n. The equati on i s
used for non-pol ar components, and can manage hydrogen-contai ni ng systems.
General Form:
Z Z Z
m m m
+
( ) (1) 0
Where:
Z Z fcn T T V V
m m c m cm
( ) (1)
, ( , , , )
0
Mi xi ng Rul es:
V x x V
cm
a
i j cij
a
j i

*,
V T x x T V
cm
b
c i j cij cij
b
j i

V T x x V
cm
b
c i j ij cij
c
j i

Where:
a b c 4 5 3 35 5 . / ; . /
V V V
cij ij ci cj
( ) ( )
* * /
1
3 1 2

Versi on 10
Chapter 3
T n T T
cij ij ci cj
( )( )
/
1
1 2

( )
/
i j
1 2
Parameter Name/Element Symbol Default MDS Lower Limit Upper Limit Units
TCBWR
T
ci
TC X 5.0 2000.0 TEMPERATURE
VCBWR
V
ci
*
VC X 0.001 3.5 MOLE-VOLUME
BWRGMA

i
OMEGA X -0.5 3.0
BWRKV
ij
0 X -5.0 1.0
BWRKT
ij
0 X -5.0 1.0
Binary interaction parameters BWRKV and BWRKT are available in ASPEN PLUS for a large number
of components. (See ASPEN PLUS Physi cal Property Data, Chapter 1).
References
M.R. Brul , C.T. Li n, L.L. Lee, and K.E. Starl i ng, AI ChE J ., Vol . 28, (1982) p.
616.
Brul et al ., Chem. Eng., (Nov., 1979) p. 155.
Watanasi ri et al ., AI ChE J ., Vol . 28, (1982) p. 626.
Hayden-OConnell
The Hayden-O'Connel l equati on-of-state cal cul ates thermodynami c properti es for
the vapor phase. I t i s used i n property methods NRTL-HOC, UNI F-HOC,
UNI Q-HOC, VANL-HOC, and WI LS-HOC, and i s recommended for nonpol ar,
pol ar, and associ ati ng compounds. Hayden-O'Connel l i ncorporates the chemi cal
theory of di meri zati on. Thi s model accounts for strong associ ati on and sol vati on
effects, i ncl udi ng those found i n systems contai ni ng organi c aci ds, such as aceti c
aci d. The equati on-of-state i s:
Z
B
RT
m
p
+ 1
Where:
B x x B T
i
i j
j
ij

( )
B B B B B B
ij free nonpolar ij free polar ij metastable ij bound ij chem ij
+ + + +

( ) ( ) ( ) ( ) ( )
Versi on10
Property
Model
Descriptions
For nonpol ar, non-associ ati ng speci es:
B f T
free nonpolar I np np np
( , , , ) , wi th

np np c c
g T p
1
( , , )

np np c
g T
2
( , )
, where
np
gyr
f r
2
( )
For pol ar, associ ati ng speci es:
B f T
free nonpolar fp fp np

3
( , , , ) , wi th

fp np np
g
3
( , , )

fp np np
g
4
( , , ) , where

5
( , , , )
np np np
T p,
For chemi cal l y bondi ng speci es:
B B f T
metastable bound c c
+
4
( , , , ) p , and
B f T
chem c c
5
( , , , )

c np np
g
3
( , , )

c np np
g
6
( , , , )
Cross-Interactions
The previ ous equati ons are val i d for di meri zati on and cross-di meri zati on i f these
mi xi ng rul es are appl i ed:

+ +
_
,
0 7 0 6
1 1
1 2
. ( ) .
/
i j
i j
( )
/
i j
1 2

+ +
_
,
0 7 0 6
1 1
1 2
. ( ) .
/
i j
i j
( )
/
i j
1 2

np
n pi n pj
+ ( )
, ,
2
Versi on 10
Chapter 3
p p p ( )
/
i j
1 2
0 unl ess a speci al sol vati on contri buti on can be justi fi ed (for exampl e, i and j
are i n the same cl ass of compounds). Many val ues are present i n ASPEN
PLUS.
Chemical Theory
When a compound wi th strong associ ati on ( . ) 45 i s present i n a mi xture, the
enti re mi xture i s treated accordi ng to the chemi cal theory of di meri zati on.
The chemi cal reacti on for the general case of a mi xture of di meri zi ng components
i and j i s:
K
ij
i j ij +
Where i and j refer to the same component.
The equati on-of-state becomes:
pV
RT
n
Bp
RT
t
+
_
,
1 wi th B y B
i
nc
ij free ij
j
nc

1 1
( )
I n thi s case, mol ar vol ume i s equal to:
V
n
t
Thi s represents true total vol ume over the true number of speci es n
t
. However,
the reported mol ar vol ume i s:
V
n
a
Thi s represents the true total vol ume over the apparent number of speci es n
a
. I f
di meri zati on does not occur, n
a
i s defi ned as the number of speci es.
V
n
a
refl ects
the apparentl y l ower mol ar vol ume of an associ ati ng gas mi xture.
The chemi cal equi l i bri um constant for the di meri zati on reacti on on pressure
basi s K
p
, i s rel ated to the true mol e fracti ons and fugaci ty coeffi ci ents:
y
y y
K p
ij
i j
ij
i j
ij

Versi on10
Property
Model
Descriptions
Where:
y
i
and y
j
= True mol e fracti ons of monomers
y
ij
= True mol e fracti on of di mer
i
= True fugaci ty coeffi ci ent of component i
K
ij
= Equi l i bri um constant for the di meri zati on of i and j, on a
pressure basi s
=
+ + ( ) ( ) / B B B RT
bound metastable chem ij ij
2
ij
= 1 for i=j
= 0 for i j
Apparent mol e fracti ons y
i
a
are reported, but i n the cal cul ati on real mol e
fracti ons y
i
, y
j
, and y
ij
are used.
The heat of reacti on due to each di meri zati on i s cal cul ated accordi ng to:

r m
r m
ij
H T
G
T
RT
K
T

2 2
d
d
d
( )
(ln )
d
The sum of the contri buti ons of al l di meri zati on reacti ons, corrected for the rati o
of apparent and true number of mol es i s added to the mol ar enthal py departure
H H
m m
ig
.
Parameter Name/ Element Symbol Default MDS Lower Limit Upper Limit Units
TC
T
ci
5.0 2000.0 TEMPERATURE
PC
p
ci

10
5
10
8
PRESSURE
RGYR
r
i
gyr

10
11
5 10
5 9
x

LENGTH
MUP
p
i
0.0
5 10
5 24
x

DIPOLEMOMENT
HOCETA
0.0 x
The binary parameters HOCETA for many component pairs are available in ASPEN PLUS. These
parameters are retrieved automatically when you specify any of the following property methods: NRTL-
HOC, UNI F-HOC, UNI Q-HOC, VANL-HOC, and WI LS-HOC.
Versi on 10
Chapter 3
References
J.G. Hayden and J.P. OConnel l , "A General i zed Method for Predi cti ng Second
Vi ri al Coeffi ci ents," I nd. Eng. Chem., Process Des. Dev., Vol . 14,No. 3, (1974), pp.
209 216.
HF Equation-of-State
HF forms ol i gomers i n the vapor phase. The non-i deal i ty i n the vapor phase i s
found i n i mportant devi ati ons from i deal i ty i n al l thermodynami c properti es. The
HF equati on accounts for the vapor phase noni deal i ti es. The model i s based on
chemi cal theory and assumes the formati on of hexamers.
Speci es l i ke HF that associ ate l i nearl y behave as si ngl e speci es. For exampl e,
they have a vapor pressure curve, l i ke pure components. The component on
whi ch a hypotheti cal unreacted system i s based i s often cal l ed the apparent (or
parent) component. Apparent components react to the true speci es. El ectrol yte
Si mul ati on, Chapter 5, di scusses apparent and true speci es. Abbott and van Ness
(1992) provi de detai l s and basi c thermodynami cs of reacti ve systems.
The temperature-dependent hexameri zati on equi l i bri um constant, can fi t the
experi mental l y determi ned associ ati on factors. The bui l t-i n functi onal i ty i s:
10
0
1
2 3
log ln K C
C
T
C T C T + + + (1)
The constants C
0
and C
1
are from Long et al . (1943), and C
2
and C
3
are set to 0.
The correl ati on i s val i d between 270 and 330 K, and can be extrapol ated to about
370 K (cf. sec. 4). Di fferent sets of constants can be determi ned by experi mental
data regressi on.
Molar Volume Calculation
The non-i deal i ty of HF i s often expressed usi ng the associ ati on factor, f,
i ndi cati ng the rati o of apparent number of speci es to the real number or speci es.
Assumi ng the i deal gas l aw for al l true speci es i n terms of (p, V, T) behavi or
i mpl i es:
pV
f
RT
m

_
,
1
(2)
Where the true number of speci es i s gi ven by
1
f
. The associ ati on factor i s easi l y
determi ned from (p, V, T) experi ments. For a cri ti cal eval uati on of data refer to
Vanderzee and Rodenburg (1970).
I f onl y one reacti on i s assumed for a mi xture of HF and i ts associ ated speci es,
(refer to Long et al ., 1943), then:
Versi on10
Property
Model
Descriptions
6
6
HF HF ( ) (3)
I f p
1
represents the true parti al pressure of the HF monomer, and p
6
represents
the true parti al pressure of the hexamer, then the equi l i bri um constant i s
defi ned as:
K
p
p
6
1
6
( )
(4)
The true total pressure i s:
p p p +
1 6
(5)
I f al l hexamer were di ssoci ated, the apparent total pressure woul d be the
hypotheti cal pressure where:
p p p p p
a
+ +
1 6 6
6 5 (6)
When physi cal i deal i ty i s assumed, parti al pressures and mol e fracti ons are
proporti onal . The total pressure i n equati on 5 represents the true number of
speci es. The apparent total pressure from equati on 6 represents the apparent
number of speci es:
f
p
p
p p
p p
p p
p
y
a

+
+

+
+
1 6
1 6
6
6
6 5
1 5 (7)
Note that the outcome of equati on 7 i s i ndependent of the assumpti on of i deal i ty.
Equati on 7 can be used to compute the number of true speci es
1
f
for a mi xture
contai ni ng HF, but the associ ati on factor i s defi ned di fferentl y.
I f p
1
and p
6
are known, the mol ar vol ume or densi ty of a vapor contai ni ng HF
can be cal cul ated usi ng equati ons 2 and 7. The mol ar vol ume cal cul ated i s the
true mol ar vol ume for 1 apparent mol e of HF. Thi s i s because the vol ume of 1
mol e of i deal gas (the true mol ar vol ume per true number of mol es) i s al ways
equal to about 0.0224 m3/mol at 298.15 K.
True Mole Fraction (Partial Pressure) Calculation
I f you assume the i deal gas l aw for a mi xture contai ni ng HF, the apparent HF
mol e fracti on i s:
y
p
p
p p
p p
a
a
a

+
+
1 1 6
6
6
5
(8)
Versi on 10
Chapter 3
The denomi nator of equati on 8 i s gi ven by equati on 6. The numerator (the
apparent parti al pressure of HF) i s the hypotheti cal parti al pressure onl y i f al l of
the hexamer was di ssoci ated. I f you substi tute equati on 4, then equati on 8
becomes:
y
p K p
p K p
a
+
+
1 1
6
1
6
6
5
( )
( )
(9)
K i s known from Long et al ., or can be regressed from (p,V,T) data. The apparent
mol e fracti on of HF, y
a
, i s known to the user and the si mul ator, but
p
1
, or y
p
p
1
must al so be known i n order to cal cul ate the thermodynami c
properti es of the mi xture. Equati on 9 must be sol ved for p
1
Equati on 9 can be wri tten as a pol ynomi al i n p
1
of degree 6:
K y p p py
a a
( )( ) 6 5 0
1
6
1
+ (9a)
A second order Newton-Raphson techni que i s used to determi ne p
1
. Then p
6
can
be cal cul ated by equati on 5, and f i s known (equati on 7).
Gibbs Energy and Fugacity
The apparent fugaci ty coeffi ci ent i s rel ated to the true fugaci ty coeffi ci ent and
mol e fracti ons:
ln ln ln
i
a
i a
y
y

_
,
1
(10)
Equati on 10 represents a correcti on to the i deal mi xi ng term of the fugaci ty. The
rati o of the true number of speci es to the apparent number of speci es i s si mi l ar to
the correcti on appl i ed i n equati on 2. Si nce the i deal gas l aw i s assumed, the
apparent fugaci ty coeffi ci ent i s gi ven by the equati on. Al l vari abl es on the ri ght
si de are known.
i
a
a a
y
y
p
py

1 1
(11)
For pure HF, y
a
1:
ln ln
*,
i
a
y
1
Versi on10
Property
Model
Descriptions
From the fugaci ty coeffi ci ent, the Gi bbs energy departure of the mi xture or pure
apparent components can be cal cul ated:
G G RT RT
p
p
ig
i
a
ref
i
+
ln ln (12)
+
*, *,
ln ln
ig
i
a
ref
RT RT
p
p
(12a)
Enthalpy and Entropy
For the enthal py departure, the heat of reacti on i s consi dered. For an arbi trary
gas phase reacti on:
v A v B v C v D
A B C D
+ + (13)
RT K RT
p p
p p
C
v
D
v
A
v
B
v
c D
A B
ln ln (14)
Where
i
*
i s the pure component thermodynami c potenti al or mol ar Gi bbs energy
of a component. Equati on 4 represents the fi rst two terms of the general equati on
14. The second or thi rd equal i ty rel ates the equi l i bri um constant to the Gi bbs
energy of reacti on, whi ch i s thus rel ated to the enthal py of reacti on:

r m
r m
H T
G
T
RT
K
T

2 2
d
d
(ln )
(15)
Al l components are assumed to be i deal . The enthal py departure i s equal to the
heat of reacti on, per apparent number of mol es:
H H
f
H
m m
ig
r m

1
(16)
H H
f
H
HF HF
ig
r m
* *,

1
(17)
From the Gi bbs energy departure and enthal py departure, the entropy departure
can be cal cul ated:
G H TS
m m m
(18)
Temperature deri vati ves for the thermodynami c properti es can be obtai ned by
strai ghtforward di fferenti ati on.
Usage
The HF equati on-of-state shoul d onl y be used for vapor phase cal cul ati ons. I t i s
not sui ted for l i qui d phase cal cul ati ons.
Versi on 10
Chapter 3
The HF equati on-of-state can be used wi th any acti vi ty coeffi ci ent model for
nonel ectrol yte VLE. Usi ng the El ectrol yte NRTL model and the data package
MHF2 i s strongl y recommended for aqueous mi xtures (de Leeuw and Watanasi ri ,
1993).
ESHFK/1
C
0
43.65
ESHFK/2
C
1
-8910
ESHFK/3
C
2
0
ESHFK/4
C
3
0
References
M. M. Abbott and H. C. van Ness, "Thermodynami cs of Sol uti ons Contai ni ng
Reacti ve Speci es, a Gui de to Fundamental s and Appl i cati ons," Fl ui d Phase Eq.,
Vol . 77, (1992) pp. 53 119.
V. V. De Leeuw and S. Watanasi ri , "Model l i ng Phase Equi l i bri a and Enthal pi es
of the System Water and Hydrofl ouri c Aci d Usi ng an HF Equati on-of-state i n
Conjuncti on wi th the El ectrol yte NRTL Acti vi ty Coeffi ci ent Model ," Paper
presented at the 13th European Semi nar on Appl i ed Thermodynami cs, June 9
12, Carry-l e-Rouet, France, 1993.
R. W. Long, J. H. Hi l debrand, and W. E. Morrel l , "The Pol ymeri zati on of Gaseous
Hydrogen and Deuteri um Fl ouri des," J. Am. Chem. Soc., Vol . 65, (1943), pp.
182 187.
C. E. Vanderzee and W. WM. Rodenburg, "Gas I mperfecti ons and
Thermodynami c Excess Properti es of Gaseous Hydrogen Fl ouri de," J. Chem.
Thermodynami cs, Vol . 2, (1970), pp. 461 478.
Ideal Gas
The i deal gas l aw (i deal gas equati on-of-state) combi nes the l aws of Boyl e and
Gay-Lussac. I t model s a vapor as i f i t consi sted of poi nt masses wi thout any
i nteracti ons. The i deal gas l aw i s used as a reference state for equati on-of-state
cal cul ati ons, and can be used to model gas mi xtures at l ow pressures (wi thout
speci fi c gas phase i nteracti ons).
The equati on i s:
p
RT
V
m

Versi on10
Property
Model
Descriptions
Lee-Kesler
Thi s equati on-of-state model i s based on the work of Lee and Kesl er (1975). I n
thi s equati on, the vol umetri c and thermodynami c properti es of fl ui ds based on
the Curl and Pi tzer approach (1958) have been anal yti cal l y represented by a
modi fi ed Benedi ct-Webb-Rubi n equati on-of-state (1940). The model cal cul ates the
mol ar vol ume, enthal py departure, Gi bbs free energy departure, and entropy
departure of a mi xture at a gi ven temperature, pressure, and composi ti on for
ei ther a vapor or a l i qui d phase. Parti al deri vati ves of these quanti ti es wi th
respect to temperature can al so be cal cul ated.
Unl i ke the other equati on-of-state model s, thi s model does not cal cul ate fugaci ty
coeffi ci ents.
The compressi bi l i ty factor and other deri ved thermodynami c functi ons of
nonpol ar and sl i ghtl y pol ar fl ui ds can be adequatel y represented, at constant
reduced temperature and pressure, by a l i near functi on of the acentri c factor. I n
parti cul ar, the compressi bi l i ty factor of a fl ui d whose acentri c factor i s , i s
gi ven by the fol l owi ng equati on:
Z Z Z +
( ) ( ) 0 1
Where:
Z
( ) 0
= Compressi bi l i ty factor of a si mpl e fl ui d ( ) 0
Z
( ) 1
=
Devi ati on of the compressi bi l i ty factor of the real fl ui d from Z
( ) 0
Z
( ) 0
and Z
( ) 1
are assumed uni versal functi ons of the reduced temperature and
pressure.
Curl and Pi tzer (1958) were qui te successful i n correl ati ng thermodynami c and
vol umetri c properti es usi ng the above approach. Thei r appl i cati on empl oyed
tabl es of properti es i n terms of reduced temperature and pressure. A si gni fi cant
weakness of thi s method i s that the vari ous properti es (for exampl e, entropy
departure and enthal py departure) wi l l not be exactl y thermodynami cal l y
consi stent wi th each other. Lee and Kesl er (1975) overcame thi s drawback by an
anal yti c representati on of the tabl es wi th an equati on-of-state. I n addi ti on, the
range was extended by i ncl udi ng new data.
I n the Lee-Kesl er i mpl ementati on, the compressi bi l i ty factor of any fl ui d has
been wri tten i n terms of a si mpl e fl ui d and a reference as fol l ows:
Z Z Z Z
r
r +
( ) ( ) ( )
( ) ( )
0 0
I n the above equati on both Z

( ) 0
and Z
( ) 1
are represented as general i zed
equati ons of the BWR form i n terms of reduced temperature and pressure. Thus,
Z f
T
T
P
P
c c
( ) ( )
( )
,
0 0

Versi on 10
Chapter 3
Z f
r r
T
T
P
P
c c
( ) ( )
( )
,
Equati ons for the enthal py departure, Gi bbs free energy departure, and entropy
departure are obtai ned from the compressi bi l i ty factor usi ng standard
thermodynami c rel ati onshi ps, thus ensuri ng thermodynami c consi stency.
I n the case of mi xtures, mi xi ng rul es (wi thout any bi nary parameters) are used to
obtai n the mi xture val ues of the cri ti cal temperature and pressure, and the
acentri c factor.
Thi s equati on has been found to provi de a good descri pti on of the vol umetri c and
thermodynami c properti es of mi xtures contai ni ng nonpol ar and sl i ghtl y pol ar
components.
Symbol Parameter Name Default Definition
T
c
TCLK TC Critical temperature
P
c
PCLK PC Critical pressure
OMGLK OMEGA Acentric factor
References
B. I . Lee and M.G. Kesl er, AI ChEJ , Vol . 21, (1975), p. 510.
R. F. Curl and K.S. Pi tzer, I nd. Eng. Chem., Vol . 50, (1958), p. 265.
M. Benedi ct, G. B. Webb, and L. C. Rubi n, J . Chem. Phys., Vol . 8, (1940), p. 334.
Lee-Kesler-Plcker
The Lee-Kesl er-Pl cker equati on-of-state i s the basi s for the LK-PLOCK property
method. Thi s equati on-of-state appl i es to hydrocarbon systems that i ncl ude the
common l i ght gases, such as H S
2
and CO
2
. I t can be used i n gas-processi ng,
refi nery, and petrochemi cal appl i cati ons.
The general form of the equati on i s:
Z Z Z Z
m m
o
R m
o
m
R
+
( )
Where:
Z f T T V V
m
o
o c m cm
( , , , )
Z f T T V V
m
R
R c m cm
( , , , )
Versi on10
Property
Model
Descriptions
The f
o
and f
R
parameters are functi ons of the BWR form. The f
o
parameter i s
for a si mpl e fl ui d, and f
R
i s for reference fl ui d n-octane.
p Z RT V
c cm c cm
/
The mi xi ng rul es are:
V
cm
=
i
i
j
j cij
x x V

V T
cm c
1
4
=
i
i
j
j cij cij
x x V T

1
4
=
x
i i
i
Z
m
=
x Z
i ci
i
Where:
V
cij
=
[ ]
V V
ci cj
1
3
1
3
3
8
+
T
cij
=
( )( ) 1
1
2
+ k T T
ij ci cj
Z
ci
= 0 2905 0 085
1
2
. .
( )
( )

'
i
ci ci
ci
p V
RT
Method
Method
k
ij
= k
ji
The bi nary parameter k
ij
i s determi ned from phase-equi l i bri um data regressi on,
such as VLE data. ASPEN PLUS stores the bi nary parameters for a l arge
number of component pai rs. These bi nary parameters are used automati cal l y
wi th the LK-PLOCK property method. I f bi nary parameters for certai n
component pai rs are not avai l abl e, they can be esti mated usi ng bui l t-i n
correl ati ons. The correl ati ons are desi gned for bi nary i nteracti ons among the
components CO CO N H CH , , , ,
2 2 2 4
al cohol s and hydrocarbons. I f a component i s
not CO CO N H CH , , , ,
2 2 2 4
or an al cohol , i t i s assumed to be a hydrocarbon.
Versi on 10
Chapter 3
Parameter Name/Element Symbol Default MDS Upper Limit Lower Limit Units
TCLKP
T
ci
TC x 5.0 2000.0 TEMPERATURE
PCLKP
p
ci
PC x
10
5
10
8
PRESSURE
VCLKP
V
ci
VC x 0.001 3.5 MOLE-VOLUME
OMGLKP

I
OMEGA x -0.5 2.0
LKPZC
Z
ci
fcn( )
(Method 1)
fcn p V T
ci ci ci
( , , )
(Method 2)
x 0.1 0.5
LKPKIJ
k
ij
fcn
T
T V
ci
V
ci
cj cj
( )
x 5.0 5.0
Method 1 is the default; Method 2 can be invoked by setting the value of LKPZC equal to zero.
Binary interaction parameters LKPKI J are availablefor a large number of components in ASPEN PLUS.
References
B.I . Lee and M.G. Kesl er, AI ChE J., Vol . 21, (1975) p. 510; errata: AI ChE J .,
Vol . 21, (1975) p. 1040.
V. Pl cker, H. Knapp, and J.M. Prausni tz, I nd. Eng. Chem., Process Des. Dev.,
Vol . 17, (1978), p. 324.
NBS/NRC Steam Tables
The NBS/NRC Steam Tabl es are i mpl emented l i ke any other equati on-of-state i n
ASPEN PLUS. These steam tabl es can cal cul ate any thermodynami c property of
water. The tabl es form the basi s of the STEAMNBS property method. There are
no parameter requi rements. They are the most accurate steam tabl es i n
ASPEN PLUS.
References
L. Haar, J.S. Gal l agher, and J.H. Kel l , "NBS/NRC Steam Tabl es," (Washi ngton:
Hemi sphere Publ i shi ng Corporati on, 1984).
Versi on10
Property
Model
Descriptions
Nothnagel
The Nothnagel equati on-of-state cal cul ates thermodynami c properti es for the
vapor phase. I t i s used i n property methods NRTL-NTH, UNI Q-NTH, VANL-
NTH, and WI LS-NTH. I t i s recommended for systems that exhi bi t strong vapor
phase associ ati on. The model i ncorporates the chemi cal theory of di meri zati on to
account for strong associ ati on and sol vati on effects, such as those found i n
organi c aci ds, l i ke aceti c aci d. The equati on-of-state i s:
p
RT
V b
m
Where:
b =
y b y b
i i ij ij
j
i
i
nc
i
nc
+

1 1 1
b
ij
=
( ) b b
i j
1 1
3 3
3
8
+
nc = Number of components i n the mi xture
The chemi cal reacti on for the general case of a mi xture of di meri zi ng components
i and j i s:
K
i j ij +
The chemi cal equi l i bri um constant for the di meri zati on reacti on on pressure
basi s K
p
i s rel ated to the true mol e fracti ons and fugaci ty coeffi ci ents:
y
y y
K p
ij
i j
ij
i j
ij

Where:
y
i
and y
j
= True mol e fracti ons of monomers
y
ij
= True mol e fracti on of di mer
i
= True fugaci ty coeffi ci ent of component i
K
ij
= Equi l i bri um constant for the di meri zati on of i and j, on a
pressure basi s
Versi on 10
Chapter 3
When accounti ng for chemi cal reacti ons, the number of true speci es n
t
i n the
mi xture changes. The true mol ar vol ume
V
n
t
_
,
i s cal cul ated from the equati on-of-

state. Si nce both V and n
t
change i n about the same proporti on, thi s number
does not change much. However, the reported mol ar vol ume i s the total vol ume
over the apparent number of speci es:
V
n
a
. Si nce the apparent number of speci es i s
constant and the total vol ume decreases wi th associ ati on, the quanti ty
V
n
a
refl ects the apparent contracti on i n an associ ati ng mi xture.
The heat of reacti on due to each di meri zati on can be cal cul ated:

r m
r m
ij
H T
d G
dT
RT
d K
dT

2 2
( )
(ln )
The sum of the contri buti ons of al l di meri zati on reacti ons, corrected for the rati o
of apparent and true number of mol es, i s added to the mol ar enthal py departure:
( ) H H
m
v
m
ig
The equi l i bri um constants can be computed usi ng ei ther bui l t-i n cal cul ati ons or
parameters you entered.
Bui l t-i n correl ati ons:
ln( ) ( , , , , , , ) RTK fcn T b b d d p p
IJ i j i j i j
The pure component parameters b, d, and p are stored i n ASPEN PLUS for
many components.
Parameters you entered:
ln ln K A
B
T
C T DT
ii i
i
i i
+ + +
I n thi s method, you enter A
i
B
i
, C
i
, and D
i
on the Properti es Parameters
Unary.T-Dependent form. The uni ts for
K
ii
i s pressure
1
; use absol ute uni ts for
temperature. I f you enter
K
ii
and
K
jj
, then
K
jj
i s computed from
K K K
ij ii jj
2
I f you enter A
i
B
i
, C
i
, and D
i
, the equi l i bri um constants are computed usi ng
the parameters you entered. Otherwi se the equi l i bri um constants are computed
usi ng bui l t-i n correl ati ons.
Versi on10
Property
Model
Descriptions
Parameter Name/Element Symbol Default Upper Limit Lower Limit Units
TC
T
ci
TB
T
bi
PC
p
ci
10
5
10
8
PRESSURE
NTHA/1
b
i
0199 . RT
p
ci
ci
0.01 1.0 MOLE-VOLUME
NTHA/2
d
i
0.33 0.01 3.0
NTHA/3
p
i
0 0.0 1.0
NTHK/1
A
i
PRESSURE
NTHK/2
B
i
0 TEMPERATURE
NTHK/3
C
i
0 TEMPERATURE
NTHK/4
D
i
0 TEMPERATURE
References
K.-H. Nothnagel , D. S. Abrams, and J.M. Prausni tz, "General i zed Correl ati on for
Fugaci ty Coeffi ci ents i n Mi xtures at Moderate Pressures," I nd. Eng. Chem.,
Process Des. Dev., Vol . 12, No. 1 (1973), pp. 25 35.
Versi on 10
Chapter 3
Peng-Robinson-Boston-Mathias
The Peng-Robi nson-Boston-Mathi as equati on-of-state i s the basi s for the PR-BM
property method. I t i s the Peng-Robi nson equati on-of-state wi th the Boston-
Mathi as al pha functi on (see Peng-Robi nson Al pha Functi ons). I t i s recommended
for hydrocarbon processi ng appl i cati ons such as gas processi ng, refi nery, and
petrochemi cal processes. I ts resul ts are comparabl e to those of the Redl i ch-
Kwong-Soave equati on-of-state.
The equati on for the BM model i s:
p =
RT
V b
a
V V b b V b
m m m m

+ + ( ) ( )
Where:
b =
x b
i i
i
a =
x x a a k
i j i j ij
j i
( ) ( )
. 0 5
1

b
i
= fcn T p
ci ci
( , )
a
i
= fcn T T p
ci ci i
( , , , )
k
ij
= k
ji
The parameter
i
i s cal cul ated by the standard Peng-Robi nson formul ati on at
supercri ti cal temperatures. I f the component i s supercri ti cal , the Boston-Mathi as
extrapol ati on i s used (see Peng-Robi nson Al pha Functi ons on page 3-36).
For best resul ts, the bi nary parameter k
ij
must be determi ned from phase
equi l i bri um data regressi on, (for exampl e, VLE data).
TCPR
T
ci
PCPR
p
ci
PC x
10
5
10
8
PRESSURE
OMGPR

i
OMEGA x -0.5 2.0
PRKIJ
k
ij
0 x -5.0 5.0
Binary interaction parameters PRKI J are available for a large number of components in ASPEN PLUS.
Versi on 10
Property
Model
Descriptions
References
D.-Y. Peng and D. B. Robi nson, "A New Two-Constant Equati on-of-state,"
I nd Eng. Chem. Fundam., Vol . 15, (1976), pp. 5964.
Peng-Robinson-MHV2
Thi s model uses the Peng-Robi nson equati on-of-state for pure compounds. The
mi xi ng rul es are the predi cti ve MHV2 rul es. Several al pha functi ons can be used
i n the Peng-Robi nson-MHV2 equati on-of-state model . For a more accurate
descri pti on of the pure component behavi or. The pure component behavi or and
parameter requi rements are descri bed i n Standard Peng-Robi nson on page 3-34,
or i n Peng-Robi nson Al pha Functi ons on page 3-36.
The MHV2 mi xi ng rul es are an exampl e of modi fi ed Huron-Vi dal mi xi ng rul es. A
bri ef i ntroducti on i s provi ded i n Huron-Vi dal Mi xi ng Rul es on page 3-46. For
more detai l s, see MHV2 Mi xi ng Rul es, thi s chapter.
Predictive SRK (PSRK)
Thi s model uses the Redl i ch-Kwong-Soave equati on-of-state for pure compounds.
The mi xi ng rul es are the predi cti ve Hol derbaum rul es, or PSRK method. Several
al pha functi ons can be used i n the PSRK equati on-of-state model . For a more
accurate descri pti on of the pure component behavi or. The pure component
behavi or and parameter requi rements are descri bed i n Standard Redl i ch-Kwong-
Soave on page 3-35 and i n Soave Al pha Functi ons on page 3-40.
The PSRK method i s an exampl e of modi fi ed Huron-Vi dal mi xi ng rul es. A bri ef
i ntroducti on i s provi ded i n Huron-Vi dal Mi xi ng Rul es on page 3-46. For more
detai l s, see Predi cti ve Soave-Redl i ch-Kwong-Gmehl i ng Mi xi ng Rul es, thi s
chapter.
Peng-Robinson-Wong-Sandler
Thi s model uses the Peng-Robi nson equati on-of-state for pure compounds. The
mi xi ng rul es are the predi cti ve Wong-Sandl er rul es. Several al pha functi ons can
be used i n the Peng-Robi nson-Wong-Sandl er equati on-of-state model . For a more
accurate descri pti on of the pure component behavi or. The pure component
behavi or and parameter requi rements are descri bed i n Peng-Robi nson, and i n
Peng-Robi nson Al pha Functi ons on page 3-36.
The Wong-Sandl er mi xi ng rul es are an exampl e of modi fi ed Huron-Vi dal mi xi ng
rul es. A bri ef i ntroducti on i s provi ded i n Huron-Vi dal Mi xi ng Rul es on page 3-46.
For more detai l s see Wong-Sandl er Mi xi ng Rul es, thi s chapter.
Versi on 10
Chapter 3
Redlich-Kwong
The Redl i ch-Kwong equati on-of-state can cal cul ate vapor phase thermodynami c
properti es for the fol l owi ng property methods: NRTL-RK, UNI FAC, UNI F-LL,
UNI Q-RK, VANL-RK, and WI LS-RK. I t i s appl i cabl e for systems at l ow to
moderate pressures (maxi mum pressure 10 atm) for whi ch the vapor-phase
noni deal i ty i s smal l . The Hayden-OConnel l model i s recommended for a more
noni deal vapor phase, such as i n systems contai ni ng organi c aci ds. I t i s not
recommended for cal cul ati ng l i qui d phase properti es.
The equati on for the model i s:
p =
RT
V b
a
T
V V b
m m m

+
0 5 .
( )
Where:
a
=
x a
i i
i
b =
x b
i i
i
a
i
=
0 42748023
2 1 5
.
.
R T
p
ci
ci
b
i
=
0 08664035 . RT
p
ci
ci
TC T
ci
PC p
ci
10
5
10
8
PRESSURE
References
O. Redl i ch and J.N.S. Kwong, "On the Thermodynami cs of Sol uti ons V. An
Equati on-of-state. Fugaci ti es of Gaseous Sol uti ons," Chem. Rev., Vol . 44, (1979),
pp. 223 244.
Versi on 10
Property
Model
Descriptions
Redlich-Kwong-Aspen
The Redl i ch-Kwong-Aspen equati on-of-state i s the basi s for the RK-ASPEN
property method. I t can be used for hydrocarbon processi ng appl i cati ons. I t i s
al so used for more pol ar components and mi xtures of hydrocarbons, and for l i ght
gases at medi um to hi gh pressures.
The equati on i s the same as Redl i ch-Kwong-Soave:
p =
RT
V b
a
V V b
m m m

+ ( )
A quadrati c mi xi ng rul e i s mai ntai ned for:
a =
x x a a k
i j i j a ij
j i
( ) ( )
.
,
0 5
1

An i nteracti on parameter i s i ntroduced i n the mi xi ng rul e for:
b =
x x
b b
k
i j
i j
b ij
j i
( )
( )
,
2
1

For a
i
an extra pol ar parameter i s used:
a
i
= fcn T T p
ci ci i i
( , , , , )
b
i
= fcn T p
ci ci
( , )
The i nteracti on parameters are temperature-dependent:
k
a ij ,
=
k k
T
a ij a ij , ,
0 1
1000
+
k
b ij ,
=
k k
T
b ij b ij , ,
0 1
1000
+
For best resul ts, bi nary parameters k
ij
must be determi ned from phase-
equi l i bri um data regressi on, such as VLE data.
TCRKS
T
ci
PCRKA
p
ci
PC x 10
5
10
8
PRESSURE
continued
Versi on 10
Chapter 3
OMGRKA

i
OMEGA x -0.5 2.0
RKAPOL

i
0 x -2.0 2.0
RKAKA0
k
a ij ,
0
0 x -5.0 5.0
RKAKA1
k
a ij ,
1
0 x -15.0 15.0 TEMPERATURE
RKAKB0
k
b ij ,
0
0 x -5.0 5.0
RKAKB1
k
b ij ,
1
Absolute temperature units are assumed. See the ASPEN PLUS User Gui de.
References
Mathi as, P.M., "A Versati l e Phase Equi l i bri um Equati on-of-state", I nd. Eng.
Chem. Process Des. Dev., Vol . 22, (1983), pp. 385 391.
Redlich-Kwong-Soave-Boston-Mathias
The Redl i ch-Kwong-Soave-Boston-Mathi as equati on-of-state i s the basi s for the
RKS-BM property method. I t i s the Redl i ch-Kwong-Soave equati on-of-state wi th
the Boston-Mathi as al pha functi on (see Soave Al pha Functi ons on page 3-40). I t i s
recommended for hydrocarbon processi ng appl i cati ons, such as gas-processi ng,
refi nery, and petrochemi cal processes. I ts resul ts are comparabl e to those of the
Peng-Robi nson-Boston-Mathi as equati on-of-state.
The equati on i s:
p =
RT
V b
a
V V b
m m m

+ ( )
Where:
a =
x x a a k
i j i j ij
j i
( ) ( )
. 0 5
1

b =
x b
i i
i
a
i
= fcn T T p
ci ci i
( , , , )
b
i
= fcn T p
ci ci
( , )
Versi on 10
Property
Model
Descriptions
k
ij
= k
ji
The parameter a
i
i s cal cul ated by the standard Soave formul ati on at
supercri ti cal temperatures. I f the component i s supercri ti cal , the Boston-Mathi as
extrapol ati on i s used (see Soave Al pha Functi ons on page 3-40).
ij
equi l i bri um data regressi on (for exampl e, VLE data).
TCRKS
T
ci
PCRKS
p
ci
PC x 10
5
10
8
PRESSURE
OMGRKS

i
OMEGA x -0.5 2.0
RKSKIJ
k
ij
0 x -5.0 5.0
Binary interaction parameters RKSKI J are available for a large number of components in ASPEN PLUS.
References
G. Soave, "Equi l i bri um Constants for Modi fi ed Redl i ch-Kwong Equati on-of-
state," Chem. Eng. Sci ., Vol . 27, (1972), pp. 1196 1203.
Redlich-Kwong-Soave-Wong-Sandler
Thi s equati on-of-state model uses the Redl i ch-Kwong-Soave equati on-of-state for
pure compounds. The predi cti ve Wong-Sandl er mi xi ng rul es are used. Several
al pha functi ons can be used i n the Redl i ch-Kwong-Soave-Wong-Sandl er equati on-
of-state model for a more accurate descri pti on of the pure component behavi or.
The pure component behavi or and parameter requi rements are descri bed i n
Standard Redl i ch-Kwong-Soave on page 3-35, and i n Soave Al pha Functi ons on
page 3-40.
The Wong-Sandl er mi xi ng rul es are an exampl e of modi fi ed Huron-Vi dal mi xi ng
rul es. A bri ef i ntroducti on i s provi ded i n Huron-Vi dal Mi xi ng Rul es on page 3-46.
For more detai l s, see Wong-Sandl er Mi xi ng Rul es, thi s chapter.
Versi on 10
Chapter 3
Redlich-Kwong-Soave-MHV2
Thi s equati on-of-state model uses the Redl i ch-Kwong-Soave equati on-of-state for
pure compounds. The predi cti ve MHV2 mi xi ng rul es are used. Several al pha
functi ons can be used i n the RK-Soave-MHV2 equati on-of-state model . For a
more accurate descri pti on of the pure component behavi or. The pure component
behavi or and i ts parameter requi rements are descri bed i n Standard Redl i ch-
Kwong-Soave on page 3-35, and i n Soave Al pha Functi ons on page 3-40.
The MHV2 mi xi ng rul es are an exampl e of modi fi ed Huron-Vi dal mi xi ng rul es. A
bri ef i ntroducti on i s provi ded i n Huron-Vi dal Mi xi ng Rul es on page 3-46. For
more detai l s, see MHV2 Mi xi ng Rul es, thi s chapter.
The Schwartzentruber-Renon equati on-of-state i s the basi s for the SR-POLAR
property method. I t can be used to model chemi cal l y noni deal systems wi th the
same accuracy as acti vi ty coeffi ci ent property methods, such as the WI LSON
property method. Thi s equati on-of-state i s recommended for hi ghl y non-i deal
systems at hi gh temperatures and pressures, such as i n methanol synthesi s and
supercri ti cal extracti on appl i cati ons.
The equati on for the model i s:
p =
RT
V c b
a
V c V c b
M m m
+

+ + + ( )( )
Where:
a =
x x a a k l x x
i j
j i
i j a ij ij i j
( ) [ ( )]
,
0.5
1
b =
x x
b b
k
i j
j i
i j
b ij
+
2
1 ( )
,
c =
x c
i i
i
a
i
= fcn T T p q q q
ci ci i i i i
( , , , , , , )
0 1 2
b
i
= fcn T p
ci ci
( , )
c
i
=
fcn
T
T
c c c
ci
i i i
, , ,
0 1 2
_
,

Versi on 10
Property
Model
Descriptions
k
a ij ,
=
k k T k T
a ij a ij a ij , , ,
0 1 2
+ +
l
ij
=
l l T l T
ij ij ij
0 1 2
+ +
k
b ij ,
=
k k T k T
b ij b ij b ij , , ,
0 1 2
+ +
k
a ij ,
= k
a ji ,
l
ij
= l
ji
k
b ij ,
= k
b ji ,
The bi nary parameters k
a ij ,
, k
b ij ,
, and l
ij
are temperature-dependent. I n most
cases, k
a ij ,
0
and l
ij
0
are suffi ci ent to represent the system of i nterest.
VLE cal cul ati ons are i ndependent of c. However, c does i nfl uence the fugaci ty
val ues and can be adjusted to (l i qui d) mol ar vol umes. For a wi de temperature
range, adjust c
io
to the mol ar vol ume at 298.15K or at boi l i ng temperature.
TCRKU
T
ci
PCRKU
p
ci
PC x 105 108 PRESSURE
OMGRKU

i
OMEGA x -0.5 2.0
RKUPP0
q
i 0
x
RKUPP1
q
i 1
0 x
RKUPP2
q
i 2
0 x
RKUC0
c
i 0
0 x
RKUC1
c
i 1
0 x
RKUC2
c
i 2
0 x
For polar components (dipole moment >>0), if you do not enter q

i 0
, the system estimates q
i 0
, q
i 1
, q
i 2
from vapor pressures using the Antoine vapor pressure model.
continued
Versi on 10
Chapter 3
RKUKA0
k
a ij ,
0
0 x
RKUKA1
k
a ij ,
1
0 x TEMPERATURE
RKUKA2
k
a ij ,
2
0 x TEMPERATURE
RKULA0
l
ij
0
0 x
RKULA1
l
ij
1
0 x TEMPERATURE
RKULA2
l
ij
2
0 x TEMPERATURE
RKUKB0
k
b ij ,
0
0 x
RKUKB1
k
b ij ,
1
0 x TEMPERATURE
RKUKB2
k
b ij ,
2
0 x TEMPERATURE
For polar components (dipole moment >>0), if you do not enter q

i 0
, the system estimates q
i 0
, q
i 1
, q
i 2
from vapor pressures using the Antoine vapor pressure model.
I f you do not enter at least one of the binary parameters k

a ij ,
0
, k
a ij ,
2
, l
ij
0
, l
ij
2
, k
b ij ,
0
, or k
b ij ,
2
the system
estimates k
a ij ,
0
, k
a ij ,
2
, l
ij
0
, and l
ij
2
, from the UNI FAC model.
Absolute temperature units are assumed.

References
state," Chem. Eng. Sci., Vol . 27, (1972), pp. 1196 - 1203.
J. Schwartzentruber and H. Renon, "Extensi on of UNI FAC to Hi gh Pressures
and Temperatures by the Use of a Cubi c Equati on-of-State," I nd. Eng. Chem.
Res., Vol . 28, (1989), pp. 1049 1955.
A. Penel oux, E. Rauzy, and R. Freze, "A Consi stent Correcti on For Redl i ch-
Kwong-Soave Vol umes", Fluid Phase Eq., Vol . 8, (1982), pp. 723.
Versi on 10
Property
Model
Descriptions
Standard Peng-Robinson
The Standard Peng-Robi nson equati on-of-state i s the basi s for the PENG-ROB
property method. I t i s the Peng-Robi nson equati on-of-state wi th the Boston-
Mathi as al pha functi on (see Peng-Robi nson Al pha Functi ons on page 3-36). I t i s
recommended for hydrocarbon processi ng appl i cati ons such as gas processi ng,
refi nery, and petrochemi cal processes. I ts resul ts are comparabl e to those of the
Standard Redl i ch-Kwong-Soave equati on-of-state.
The equati on for the BM model i s:
p
RT
V b
a
V V b b V b
m m m m

+ + ( ) ( )
Where:
b =
x b
i i
i
a =
x x a a k
i j i j ij
j i
( ) ( )
. 0 5
1

b
i
= fcn T p
ci ci
( , )
a
i
= fcn T T p
ci ci i
( , , , )
k
ij
= k
ji
The parameter a
i
i s cal cul ated accordi ng to the standard Peng-Robi nson
formul ati on (see Peng-Robi nson Al pha Functi ons on page 36, equati ons 1 through
5).
For best resul ts, the bi nary parameter k
ij
must be determi ned from phase
equi l i bri um data regressi on, (for exampl e, VLE data). ASPEN PLUS al so has
bui l t-i n k
ij
for al arge number of component pai rs. These parameters are used
automati cal l y wi th the PENG-ROB property method.
TCPR
T
ci
PCPR
p
ci
PC x
10
5
10
8
PRESSURE
OMGPR

i
OMEGA x -0.5 2.0
PRKIJ
k
ij
0 x -5.0 5.0
Versi on 10
Chapter 3
References
D.-Y. Peng and D. B. Robi nson, "A New Two-Constant Equati on-of-state," I nd.
Eng. Chem. Fundam., Vol . 15, (1976), pp. 5964.
Standard Redlich-Kwong-Soave
The Standard Redl i ch-Kwong-Soave-Boston-Mathi as equati on-of-state i s the
basi s for the RK-SOAVE property method. I t i s I t i s recommended for
hydrocarbon processi ng appl i cati ons, such as gas-processi ng, refi nery, and
petrochemi cal processes. I ts resul ts are comparabl e to those of the Peng-
Robi nson equati on-of-state.
The equati on i s:
p
RT
V b
a
V V b
m m m

+ ( )
Where:
p
RT
V b
a
V V b b V b
m m m m

+ + ( ) ( )
Where:
a =
x x a a k
i j i j ij
j i
( ) ( )
. 0 5
1

b =
x b
i i
i
a
i
= fcn T T p
ci ci i
( , , , )
b
i
= fcn T p
ci ci
( , )
k
ij
= k
ji
The parameter a
i
i s cal cul ated accordi ng to the standard Soave formul ati on (see
Soave Al pha Functi ons on page 3-40, equati ons 1, 2, 3, 5, and 6).
ij
equi l i bri um data regressi on (for exampl e, VLE data). ASPEN PLUS al so has
bui l t-i n k
ij
for a l arge number of component pai rs. These bi nary parameters are
used automati cal l y wi th the RK-SOAVE property method.
Versi on 10
Property
Model
Descriptions
TCRKS
T
ci
PCRKS
p
ci
PC x
10
5
10
8
PRESSURE
OMGRKS

i
OMEGA x -0.5 2.0
RKSKIJ
k
ij
0 x -5.0 5.0
Binary interaction parameters RKSKI J are available for a large number of components in ASPEN PLUS.
References
state," Chem. Eng. Sci., Vol . 27, (1972), pp. 1196 1203.
and Temperatures by the Use of a Cubi c Equati on-of-state," I nd. Eng. Chem.
Res., Vol . 28, (1989), pp. 1049 1955.
A. Penel oux, E. Rauzy, and R. Freze, "A Consi stent Correcti on For Redl i ch-
Kwong-Soave Vol umes", Fluid Phase Eq., Vol . 8, (1982), pp. 723.
Peng-Robinson Alpha Functions
The pure component parameters for the Peng-Robi nson equati on-of-state are
cal cul ated as fol l ows:
a
R T
p
i i
ci
ci
0 45724
2 2
. (1)
b
RT
p
i
ci
ci
0 07780 . (2)
These expressi ons are deri ved by appl yi ng the cri ti cal constrai nts to the
equati on-of-state under these condi ti ons:
i ci
T ( ) . 10 (3)
The parameter i s a temperature functi on. I t was ori gi nal l y i ntroduced by
Soave i n the Redl i ch-Kwong equati on-of-state. Thi s parameter i mproves the
correl ati on of the pure component vapor pressure. Thi s approach was al so
adopted by Peng and Robi nson:
i i ri
T m T ( ) [ ( )] + 1 1
1
2
2
(4)
Versi on 10
Chapter 3
Equati on 3 i s sti l l represented. The parameter m
i
can be correl ated wi th the
acentri c factor:
m
i i i
+ 037464 154226 0 26992
2
. . . (5)
Equati ons 1 through 5 are the standard Peng-Robi nson formul ati on.
TCPR
T
ci
PCPR
p
ci
PC X
10
5
10
8
PRESSURE
OMGPR

i
OMEGA X -0.5 2.0
Boston-Mathias Extrapolation
For l i ght gases at hi gh reduced temperatures (> 5), equati on 4 gi ves unreal i sti c
resul ts. The boundary condi ti ons are that attracti on between mol ecul es shoul d
vani sh for extremel y hi gh temperatures, and reduces asymptoti cal l y to zero.
Boston and Mathi as deri ved an al ternati ve functi on for temperatures hi gher
than cri ti cal :
i i ri
d
T c T
i
( ) [exp[ ( )]] 1
2
(6)
Wi th
d
i
=
1
2
+
m
i
c
i
=
1
1
d
i
Where m
i
i s computed by equati on 5. and equati on 4 i s used for subcri ti cal
temperatures. Addi ti onal parameters are not needed.
Mathias-Copeman Alpha Function
m
i
i s a constant for each component i n equati on 4. For very hi gh accuracy or
strongl y curved vapor pressure behavi or as a functi on of temperature, the
Mathi as-Copeman functi on i s hi ghl y fl exi bl e
i T i ri i ri i ri
c T c T c T
( ) , , ,
[ ( ) ( ) ( ) ] + + + 1 1 1 1
1 2
2
3
3 2
1
2
1
2
1
2
(7)
Versi on 10
Property
Model
Descriptions
For c
i 2,
= 0 and thi s expressi on reduces to the standard Peng-Robi nson
formul ati on i f c m
i i 1,
= . You can use vapor pressure data i f the temperature i s
subcri ti cal to regress the constants. I f the temperature i s supercri ti cal , c
i 2,
and
c
i 3,
are set to 0.
TCPR
T
ci
PCPR
p
ci
PC X
10
5
10
8
PRESSURE
PRMCP/1
c
i 1,
X
PRMCP/2
c
i 2,
0 X
PRMCP/3
c
i 3,
0 X
Schwartzentruber-Renon-Watanasiri Alpha Function
Thi s method combi nes the fl exi bi l i ty of the Mathi as-Copeman approach and the
correcti on for hi ghl y reduced temperatures by Boston and Mathi as:
i i ri ri i i ri ri
T m T T p p T p T ( ) [ ( ) ( )( )]
, , ,
+ + + 1 1 1
1
2
1
2
1 2 3 1
2 2
(8)
Where m
i
i s computed by equati on 5. The pol ar parameters p
i 1,
, p
i 2,
and p
i 3,
are
comparabl e wi th the c parameters of the Mathi as-Copeman expressi on. Equati on
8 reduces to the standard Peng-Robi nson formul ati on i f the pol ar parameters are
zero. You can use vapor pressure data to regress the constants i f the temperature
i s subcri ti cal . Equati on 8 i s used onl y for bel ow-cri ti cal temperatures. For above-
cri ti cal temperatures, the Boston-Mathi as extrapol ati on i s used. Use equati on 6
wi th:
d m p p p
i i i i i
+ + + 1
1
2 1 2 3
( )
, , ,
(9)
c
d
i
i
1
1
(10)
Versi on 10
Chapter 3
TCPR
T
ci
PCPR
p
ci
C X
10
5
10
8
PRESSURE
OMGPR

i
OMEGA X -0.5 2.0
PRSRP/1
p
i 1,
X
PRSRP/2
p
i 2,
0 X
PRSRP/3
p
i 3,
0 X
Use of Alpha Functions
The al pha functi ons i n Peng-Robi nson-based equati on-of-state model s i s provi ded
i n the fol l owi ng tabl e. You can veri fy and change the val ue of possi bl e opti on
codes on the Properti es Property Method Model form.
Alpha function Model name First Option code
Standard Peng Robinson ESPRSTD0, ESPRSTD
Standard PR/Boston-Mathias ESPR0, ESPR
ESPRWS0, ESPRWS
ESPRV20, ESPRV2
1
1
Mathias-Copeman ESPRWS0, ESPRWS
ESPRV20, ESPRV2
2
2
Schwartzentruber-Renon-Watanasiri ESPRWS0, ESPRWS
ESPRV20, ESPRV2
3 (default)
3 (default)
References
J. F. Boston and P.M. Mathi as, "Phase Equi l i bri a i n a Thi rd-Generati on Process
Si mul ator" i n Proceedi ngs of the 2nd I nternati onal Conference on Phase
Equi l i bri a and Fl ui d Properti es i n the Chemi cal Process I ndustri es, West Berl i n,
(17-21 March 1980) pp. 823-849.
D.-Y. Peng and D.B. Robi nson, "A New Two-Constant Equati on-of-state," I nd.
Eng. Chem. Fundam., Vol . 15, (1976), pp. 59-64.
P.M. Mathi as and T.W. Copeman, "Extensi on of the Peng-Robi nson Equati on-of-
state To Compl ex Mi xtures: Eval uati on of the Vari ous Forms of the Local
Composi ti on Concept",Fluid Phase Eq., Vol . 13, (1983), p. 91.
Versi on 10
Property
Model
Descriptions
J. Schwartzentruber, H. Renon, and S. Watanasi ri , "K-val ues for Non-I deal
Systems:An Easi er Way," Chem. Eng., March 1990, pp. 118-124.
G. Soave, "Equi l i bri um Constants for a Modi fi ed Redl i ch-Kwong Equati on-of-
state," Chem Eng. Sci ., Vol . 27, (1972), pp. 1196-1203.
Soave Alpha Functions
The pure component parameters for the Redl i ch-Kwong equati on-of-state are
cal cul ated as:
a
R T
p
i i
ci
ci
0 42747
2 2
. (1)
b
RT
p
i
ci
ci
0 08664 . (2)
These expressi ons are deri ved by appl yi ng the cri ti cal constrai nt to the equati on-
of-state under these condi ti ons:
i ci
T ( ) . 10 (3)
I n the Redl i ch-Kwong equati on-of-state, al pha i s:
i
ri
T
1
1
2
(4)
I t was not referred to as al pha but equati on 4 was i ncorporated i nto equati on 1.
TC
T
ci
PC
p
ci

10
5
10
8
PRESSURE
Soave Modification
The parameter i s a temperature functi on i ntroduced by Soave i n the Redl i ch-
Kwong equati on-of-state to i mprove the correl ati on of the pure component vapor
pressure:
i i ri
T m T ( ) [ ( )] + 1 1
1
2
2
(5)
Equati on 3 sti l l hol ds. The parameter m
i
can be correl ated wi th the acentri c
factor:
Versi on 10
Chapter 3
m
i i i
+ 0 48 157 0176
2
. . . (6)
Equati ons 1, 2, 3, 5 and 6 are the standard Redl i ch-Kwong-Soave formul ati on.
TCRKS
T
ci
PCRKS
p
ci
PC X
10
5
10
8
PRESSURE
OMGRKS

i
OMEGA X -0.5 2.0
Boston-Mathias Extrapolation
For l i ght gases at hi gh reduced temperatures (> 5), equati on 4 gi ves unreal i sti c
resul ts. The boundary condi ti ons are that attracti on between mol ecul es shoul d
vani sh for extremel y hi gh temperatures, and reduces asymptoti cal l y to zero.
Boston and Mathi as deri ved an al ternati ve functi on for temperatures hi gher
than cri ti cal :
i i ri
d
T c T
i
( ) [exp[ ( )]] 1
2
(7)
Wi th
d
i
=
1
2
+
m
i
c
i
=
1
1
d
i
Where:
m
i
= Computed by equati on 6
Equati on 5 = Used for subcri ti cal temperatures
Addi ti onal parameters are not needed.
Mathias Alpha Function
I n equati on 4, m
i
i s a constant for each component. For hi gh accuracy or for
hi ghl y curved vapor pressure behavi or as a functi on of temperature, such as wi th
pol ar compounds, the Mathi as functi on i s more fl exi bl e:
Versi on 10
Property
Model
Descriptions

i i ro i ri ri
T m T T T ( ) [ ( ) ( )( . )] + 1 1 1 0 7
1
2
1
2
2
(8)
For
i
0 , equati on 8 reduces to the standard Redl i ch-Kwong-Soave
formul ati on, i ncl udi ng equati on 6 for m
i
. For temperatures above cri ti cal , the
Boston-Mathi as extrapol ati on i s used, that i s, equati on 6 wi th:
d
m
i
i
i
+ + 1
2
03 . (9)
c
d
i
i
1
1
(10)
Parameter Name/
Element
Symbol Default MDS Upper Limit Lower Limit Units
TCRKA
T
ci
PCRKA
p
ci
PC X
10
5
10
8
PRESSURE
OMGRKA

i
OMEGA X -0.5 2.0
RKAPOL

i
X -2.0 2.0
Extended Mathias Alpha Function
An extensi on of the Mathi as approach i s:
( )
i i ri
i
ri i i ri
T m T p T p T p T + + + [ ( ) ( )( )]
,
, ,
1 1 1 1
1
2
1
2
1
2 3
2 2
(11)
Where m
i
i s computed by equati on 6. I f the pol ar parameters p
i 1,
, p
i 2,
and p
i 3,
are zero, equati on 11 reduces to the standard Redl i ch-Kwong-Soave formul ati on.
You can use vapor pressure data to regress the constants i f the temperature i s
subcri ti cal . Equati on 11 i s used onl y for temperatures bel ow cri ti cal . The Boston-
Mathi as extrapol ati on i s used for temperatures above cri ti cal , that i s, wi th:
( )
d m p p p
i i i i i
+ +
1
2 1 2 3
1
, , ,
(12)
c
d
i
i
1
1
(13)
Versi on 10
Chapter 3
TCRKU
T
ci
PCRKU
p
ci
PC X
10
5
10
8
PRESSURE
OMGRKU

i
OMEGA X -0.5 2.0
RKUPP0
p
i 1,
X
RKUPP1
p
i 2,
0 X
RKUPP2
p
i 3,
0 X
Mathias-Copeman Alpha Function
The Mathi as-Copeman Al pha Functi on approach i s another extensi on of the
Mathi as approach. For hi gh accuracy or strongl y curved vapor pressure behavi or
as a functi on of temperature, the Mathi as-Copeman functi on i s hi ghl y fl exi bl e:
i i ri i ri i ri
T m T c T c T ( ) [ ( ) ( ) ( ) ]
, ,
+ + + 1 1 1 1
1
2
1
2
1
2
2
2
3
3 2
(14)
For c
i 2
0
,
and c
i 3
0
,
thi s expressi on reduces to the standard Redl i ch-Kwong-
Soave formul ati on i f c m
i i 1,
. I f the temperature i s subcri ti cal , use vapor
pressure data to regress the constants. I f the temperature i s supercri ti cal , set c
i 2,
and c
i 3,
to 0.
TCRKS
T
ci
PCRKS
p
ci
PC X
10
5
10
8
PRESSURE
RKSMCP/1
c
i 1,
X
RKSMCP/2
c
i 2,
0 X
RKSMCP/3
c
i 3,
0 X
Schwartzentruber-Renon-Watanasiri Alpha Function
Thi s method combi nes the fl exi bi l i ty of the Mathi as-Copeman approach and the
correcti on for hi gh reduced temperatures by Boston and Mathi as:
i i ri ri i i ri i ri
T m T T p p T p T ( ) [ ( ) ( )( )]
, , ,
+ + + 1 1 1
1
2
1 2 3
2 2
(15)
Versi on 10
Property
Model
Descriptions
Where m
i
i s computed by equati on 6 and the pol ar parameters p
i 1,
, p
i 2,
and
p
i 3,
are comparabl e wi th the c parameters of the Mathi as-Copeman expressi on.
Equati on 15 reduces to the standard Redl i ch-Kwong-Soave formul ati on i f the
pol ar parameters are zero. Use vapor pressure data to regress the constants i f
the temperature i s subcri ti cal . Equati on 15 i s very si mi l ar to the extended
Mathi as equati on, but i t i s easi er to use i n data regressi on. I t i s used onl y for
temperatures bel ow cri ti cal . The Boston-Mathi as extrapol ati on i s used for
temperatures above cri ti cal , that i s, use equati on 6 wi th:
d
m
p p p
i
i
i i i
+ + + 1
2
1 2 3
( )
, , ,
(16)
c
d
i
i
1
1
(17)
TCPR
T
ci
PCPR
p
ci
PC X
10
5
10
8
PRESSURE
OMGPR

i
OMEGA X -0.5 2.0
RKSSRP/1
p
i 1,
X
RKSSRP/2
p
i 2,
0 X
RKSSRP/3
p
i 3,
0 X
Use of Alpha Functions
The use of al pha functi ons i n Soave-Redl i ch-Kwong based equati on-of-state
model s i s gi ven i n the fol l owi ng tabl e. You can veri fy and change the val ue of
possi bl e opti on codes on the Properti es Property Method Model form.
Alpha Function Model Name First Option Code
original RK ESRK0, ESRK
standard RKS ESRKSTD0, ESRKSTD
standard RKS/Boston-Mathias ESRKS0, ESRKS0
ESRKSWS0, ESRKSWS
ESRKSV10, ESRKV1
ESRKSV20, ESRKSV2
1
1
1
continued
Versi on 10
Chapter 3
Alpha Function Model Name First Option Code
Mathias/Boston-Mathias ESRKA0, ESRKA
Extended Mathias/Boston-Mathias ESRKU0, ESRKU
Mathias-Copeman ESRKSW0, ESRKSW
ESRKSV10, ESRKSV1
ESRKSV20, ESRKSV2
2
2
2
Schwartzentruber-Renon-Watanasiri ESPRWS0, ESPRWS
ESRKSV10, ESRKSV1
ESRKSV20, ESRKSV2
3 (default)
3 (default)
3 (default)
References
J. F. Boston and P.M. Mathi as, "Phase Equi l i bri a i n a Thi rd-Generati on Process
Si mul ator" i n Proceedi ngs of the 2nd I nternati onal Conference on Phase
Equi l i bri a and Fl ui d Properti es i n the Chemi cal Process I ndustri es, West Berl i n,
(17-21 March 1980), pp. 823-849.
P. M. Mathi as, "A Versati l e Phase Equi l i bri um Equati on-of-state", I nd. Eng.
Chem. Process Des. Dev., Vol . 22, (1983), pp. 385391.
P.M. Mathi as and T.W. Copeman, "Extensi on of the Peng-Robi nson Equati on-of-
state To Compl ex Mi xtures: Eval uati on of the Vari ous Forms of the Local
Composi ti on Concept", Fluid Phase Eq., Vol . 13, (1983), p. 91.
O. Redl i ch and J. N. S. Kwong, "On the Thermodynami cs of Sol uti ons V. An
Equati on-of-state. Fugaci ti es of Gaseous Sol uti ons," Chem. Rev., Vol . 44, (1949),
pp. 223244.
and Temperatures by the Use of a Cubi c Equati on-of-state," I nd. Eng. Chem.
Res., Vol . 28, (1989), pp. 10491055.
J. Schwartzentruber, H. Renon, and S. Watanasi ri , "K-val ues for Non-I deal
Systems:An Easi er Way," Chem. Eng., March 1990, pp. 118-124.
G. Soave, "Equi l i bri um Constants for a Modi fi ed Redl i ch-Kwong Equati on-of-
state," Chem Eng. Sci., Vol . 27, (1972), pp. 1196-1203.
Versi on 10
Property
Model
Descriptions
Huron-Vidal Mixing Rules
Huron and Vi dal (1979) used a si mpl e thermodynami c rel ati onshi p to equate the
excess Gi bbs energy to expressi ons for the fugaci ty coeffi ci ent as computed by
equati ons of state:
G RT x RT
m
E
i i
i

ln ln
*
(1)
Equati on 1 i s val i d at any pressure, but cannot be eval uated unl ess some
assumpti ons are made. I f Equati on 1 i s eval uated at i nfi ni te pressure, the
mi xture must be l i qui d-l i ke and extremel y dense. I t can be assumed that:
V p b ( ) (2)
V p
E
( ) 0 (3)
Usi ng equati ons 2 and 3 i n equati on 1 resul ts i n an expressi on for a/b that
contai ns the excess Gi bbs energy at an i nfi ni te pressure:
a
b
x
a
b
G p
i
i
i
m
E
i

( ) (4)
Where:

+
+
_
,
1 1
1
1 2
1
2

ln (5)
The parameters
1
and
2
depend on the equati on-of-state used. I n general a
cubi c equati on-of-state can be wri tten as:
p
RT
V b
a
V b V b
m m

+ + ( ) ( )( )
1 2
(6)
Val ues for
1
and
2
for the Peng-Robi nson and the Soave-Redl i ch-Kwong
equati ons of state are:
Equation-of-state

1

2
Peng-Robinson
1 2 1 2 +
Redlich-Kwong-Soave 1 0
Versi on 10
Chapter 3
Thi s expressi on can be used at any pressure as a mi xi ng rul e for the parameter.
The mi xi ng rul e for b i s fi xed by equati on 3. Even when used at other pressures,
thi s expressi on contai ns the excess Gi bbs energy at i nfi ni te pressure. You can use
any acti vi ty coeffeci ent model to eval uate the excess Gi bbs energy at i nfi ni te
pressure. Bi nary i nteracti on coeffi ci ents must be regressed. The mi xi ng rul e used
contai ns as many bi nary parameters as the acti vi ty coeffi ci ent model chosen.
Thi s mi xi ng rul e has been used successful l y for pol ar mi xtures at hi gh pressures,
such as systems contai ni ng l i ght gases. I n theory, any acti vi ty coeffi ci ent model
can be used. But the NRTL equati on (as modi fi ed by Huron and Vi dal ) has
demonstrated better performance.
The Huron-Vi dal mi xi ng rul es combi ne extreme fl exi bi l i ty wi th thermodynami c
consi stency, unl i ke many other mol e-fracti on-dependent equati on-of-state mi xi ng
rul es. The Huron-Vi dal mi xi ng rul es do not al l ow fl exi bi l i ty i n the descri pti on of
the excess mol ar vol ume, but al ways predi ct reasonabl e excess vol umes.
The Huron-Vi dal mi xi ng rul es are theoreti cal l y i ncorrect for l ow pressure,
because quadrati c mol e fracti on dependence of the second vi ri al coeffi ci ent (i f
deri ved from the equati on-of-state) i s not preserved. Si nce equati ons of state are
pri mari l y used at hi gh pressure, the practi cal consequences of thi s drawback are
mi ni mal .
The Gi bbs energy at i nfi ni te pressure and the Gi bbs energy at an arbi trary hi gh
pressure are si mi l ar. But the correspondence i s not cl ose enough to make the
mi xi ng rul e predi cti ve. There are several methods for modi fyi ng the Huron-Vi dal
mi xi ng rul e to make i t more predi cti ve. The fol l owi ng three methods are used i n
ASPEN PLUS equati on-of-state model s:
The modi fi ed Huron-Vi dal mi xi ng rul e, second order approxi mati on (MHV2)
The Predi cti ve SRK Method (PSRK)
The Wong-Sandl er modi fi ed Huron-Vi dal mi xi ng rul e (WS)
These mi xi ng rul es are di scussed separatel y i n the fol l owi ng secti ons. They have
major advantages over other composi ti on-dependent equati on-of-state mi xi ng
rul es.
References
M.- J. Huron and J. Vi dal ,"New Mi xi ng Rul es i n Si mpl e Equati ons of State for
representi ng Vapour-l i qui d equi l i bri a of strongl y non-i deal mi xtures," Fl ui d
Phase Eq., Vol . 3, (1979), pp. 255-271.
Versi on 10
Property
Model
Descriptions
MHV2 Mixing Rules
Dahl and Mi chel sen (1990) use a thermodynami c rel ati onshi p between excess
Gi bbs energy and the fugaci ty computed by equati ons of state. Thi s rel ati onshi p
i s equi val ent to the one used by Huron and Vi dal :
G
RT
f
RT
x
f
RT
m
E
i
i
i
_
,
_
,
ln ln (1)
The advantage i s that the expressi ons for mi xture and pure component fugaci ti es
do not contai n the pressure. They are functi ons of compaci ty V/b and :
ln ln ,
* *
f
RT
b Q
V
b
i
i
i
i
i
_
,
_
,
(2)
Where:
i
i
i
a
b RT
(3)
and
ln ln ,
f
RT
b Q
V
b
i
m
_
,
+

_
,
(4)
wi th

a
bRT
(5)
The constants
1
and
2
,whi ch depend onl y on the equati on-of-state (see Huron-
Vi dal Mi xi ng Rul es, thi s chapter ) occur i n equati ons 2 and 4.
I nstead of usi ng i nfi ni te pressure for si mpl i fi cati on of equati on 1, the condi ti on of
zero pressure i s used. At p= 0 an exact rel ati onshi p between the compaci ty and
can be deri ved. By substi tuti on the si mpl i fi ed equati on q( ) i s obtai ned, and
equati on 1 becomes:
G p
RT
x
b
b
q x q
m
E
i
i
i i
i i
( )
ln ( ) ( )
_
,

0
(6)
However, q( ) can onl y be wri tten expl i ci tl y for 58 . . Onl y an approxi mati on
i s possi bl e bel ow that threshol d. Dahl and Mi chel sen use a second order
pol ynomi al fi tted to the anal yti cal sol uti on for 10 13 < < that can be
extrapol ated to l ow al pha:
q q q
i
( ) +
2
2
(7)
Versi on 10
Chapter 3
Si nce q( ) i s a uni versal functi on (for each equati on-of-state), the combi nati on of
equati ons 6 and 7 form the MHV2 mi xi ng rul e. Excess Gi bbs energi es, from any
acti vi ty coeffi ci ent model wi th parameters opti mi zed at l ow pressures, can be
used to determi ne , i f
i
, b
i
, and b are known. To compute b, a l i near mi xi ng
rul e i s assumed as i n the ori gi nal Huron-Vi dal mi xi ng rul es:
b x b
i i
i
(8)
Thi s equati on i s equi val ent to the assumpti on of zero excess mol ar vol ume.
The MHV2 mi xi ng rul e was the fi rst successful predi cti ve mi xi ng rul e for
equati ons of state. Thi s mi xi ng rul e uses previ ousl y determi ned acti vi ty
coeffi ci ent parameters for predi cti ons at hi gh pressures. UNI FAC was chosen as
a defaul t for i ts predi cti ve character. The Lyngby modi fi ed UNI FAC formul ati on
was chosen for opti mum performance (see UNI FAC (Lyngby Modi fi ed) on page 3-
72). However, any acti vi ty coeffi ci ent model can be used when i ts bi nary
i nteracti on parameters are known.
Li ke the Huron-Vi dal mi xi ng rul es, the MHV2 mi xi ng rul es are not fl exi bl e i n the
descri pti on of the excess mol ar vol ume. The MHV2 mi xi ng rul es are theoreti cal l y
i ncorrect at the l ow pressure l i mi t. But the practi cal consequences of thi s
drawback are mi ni mal (see Huron-Vi dal Mi xi ng Rul es, thi s chapter ).
References
S. Dahl and M.L. Mi chel sen, "Hi gh-Pressure Vapor-Li qui d Equi l i bri um wi th a
UNI FAC-based Equati on-of-state," AI ChE J., Vol . 36, (1990), pp. 1829-1836.
Predictive Soave-Redlich-Kwong-Gmehling Mixing Rules
These mi xi ng rul es by Hol derbaum and Gmehl i ng (1991) use a rel ati onshi p
between the excess Hel mhol tz energy and equati on-of-state. They do not use a
rel ati onshi p between equati on-of-state properti es and excess Gi bbs energy, as i n
the Huron-Vi dal mi xi ng rul es. The pressure-expl i ci t expressi on for the equati on-
of-state i s substi tuted i n the thermodynami c equati on:
p
A
V
T

_
,
(1)
The Hel mhol tz energy i s cal cul ated by i ntegrati on. A
E
i s obtai ned by:
A A x A RT x x
m
E
m i i i i
I i

*
ln (2)
Where both A
i
*
and A
m
are cal cul ated by usi ng equati on 1. A
i
*
and A
m
are
wri tten i n terms of equati on-of-state parameters.
Versi on 10
Property
Model
Descriptions
The si mpl i fi cati on of constant packi ng fracti on ( / ) V b
m
i s used:
V
b
V
b
i
l
i
m
l *,
(3)
Wi th:
b x b
i i
i
(4)
Therefore:
V p
m
E
( ) 0 (5)
The mi xi ng rul e i s:
a
b
x
a
b
A p
i
i
i
m
E
i

( ) (6)
Where i s sl i ghtl y di fferent from for the Huron-Vi dal mi xi ng rul e:
ln
+
+
_
,
1
1 2
1
2

V
b
L
V
b
m
m
(7)
Where
1
and
2
, depend on the equati on-of-state (see Huron-Vi dal Mi xi ng
Rul es, thi s chapter ). I f equati on 6 i s appl i ed at i nfi ni te pressure, the packi ng
fracti on goes to 1. The excess Hel mhol tz energy i s equal to the excess Gi bbs
energy. The Huron-Vi dal mi xi ng rul es are recovered.
The goal of these mi xi ng rul es i s to be abl e to use bi nary i nteracti on parameters
for acti vi ty coeffi ci ent model s at any pressure. These parameters have been
opti mi zed at l ow pressures. UNI FAC i s chosen for i ts predi cti ve character. Two
i ssues exi st: the packi ng fracti on i s not equal to one, and the excess Gi bbs and
Hel mhol tz energy are not equal at the l ow pressure where the UNI FAC
parameters have been deri ved.
Fi scher (1993) determi ned that boi l i ng poi nt, the average packi ng fracti on for
about 80 di fferent l i qui ds wi th di fferent chemi cal natures was 1.1. Adopti ng thi s
val ue, the di fference between l i qui d excess Gi bbs energy and l i qui d excess
Hel mhol tz energy can be computed as:
A p G p atm pdV x pdV
m
E l
m
E l
m
l
i i
l
V b
V b
i
V b
V b
i
l
i
l
m
l
m
l
, , *,
. .
( ) ( )
*,
*,
+
1
11 11
(8)
Versi on 10
Chapter 3
The resul t i s a predi cti ve mi xi ng rul e for cubi c equati ons of state. But the
ori gi nal UNI FAC formul ati on gi ves the best performance for any bi nary pai r
wi th i nteracti ons avai l abl e from UNI FAC. Gas-sol vent i nteracti ons are
unavai l abl e.
At the Uni versi ty of Ol denburg i n Germany, the UNI FAC groups were extended
wi th often-occurri ng gases. New group i nteracti ons were determi ned from gas-
sol vent data, speci fi c to the Redl i ch-Kwong-Soave equati on-of-state. The new
bui l t-i n parameters to ASPEN PLUS are acti vated when usi ng the PSRK
equati on-of-state model .
The PSRK method has a l ot i n common wi th the Huron-Vi dal mi xi ng rul es. The
mol e fracti on i s dependent on the second vi ri al coeffi ci ent and excess vol ume i s
predi cted. These are mi nor di sadvantages.
References
T. Hol derbaum and J. Gmehl i ng, "PSRK: A Group Contri buti on Equati on-of-state
based on UNI FAC," Fluid Phase Eq., Vol . 70, (1991), pp. 251-265.
K. Fi scher, "Di e PSRK-Methode: Ei ne Zustandsgl ei chung unter Verwendung des
UNI FAC-Gruppenbei tragsmodel l s," (Dssel dorf: VDI Fortschri ttberi chte, Rei he
3: Verfahrenstechni k, Nr. 324, VDI Verl ag GmbH, 1993).
Wong-Sandler Mixing Rules
These mi xi ng rul es use a rel ati onshi p between the excess Hel mhol tz energy and
equati on-of-state. They do not use a rel ati onshi p between equati on-of-state
properti es and excess Gi bbs energy, as i n the Huron-Vi dal mi xi ng rul es. The
pressure-expl i ci t expressi on for the equati on-of-state i s substi tuted i n the
thermodynami c equati on:
p
A
V
T

_
,
(1)
The Hel mhol tz energy i s obtai ned by i ntegrati on, A
E
i s obtai ned by:
A A x A RT x x
m
E
m i i i i
i i

*
ln (2)
Where both A
i
*
and A
m
are cal cul ated by usi ng equati on 1. A
i
*
and A
m
are
wri tten i n terms of equati on-of-state parameters.
Li ke Huron and Vi dal , the l i mi ti ng case of i nfi ni te pressure i s used. Thi s
si mpl i fi es the expressi ons for A
i
*
and A
m
. Equati on 2 becomes:
a
b
x
a
b
A p
i
i
i
m
E
i

( ) (3)
Versi on 10
Property
Model
Descriptions
Where depends on the equati on-of-state (see Huron-Vi dal Mi xi ng Rul es, thi s
chapter).
Equati on 3 i s compl etel y anal ogous to the Huron-Vi dal mi xi ng rul e for the excess
Gi bbs energy at i nfi ni te pressure. (See equati on 4, Huron-Vi dal Mi xi ng Rul es,
thi s chapter.) The excess Hel mhol tz energy can be approxi mated by the excess
Gi bbs energy at l ow pressure from any l i qui d acti vi ty coeffi ci ent model . Usi ng the
Hel mhol tz energy permi ts another mi xi ng rul e for b than the l i near mi xi ng rul e.
The mi xi ng rul e for b i s deri ved as fol l ows. The second vi ri al coeffi ci ent must
depend quadrati cal l y on the mol e fracti on:
B T x x B
i j ij
j i
( )

(4)
Wi th:
B
B B
k
ij
ii jj
ij
( )
( )
2
1 (5)
The rel ati onshi p between the equati on-of-state at l ow pressure and the vi ri al
coeffi ci ent i s:
B b
a
RT
(6)
B b
a
RT
ii i
i
(7)
Wong and Sandl er di scovered the fol l owi ng mi xi ng rul e to sati sfy equati on 4
(usi ng equati ons 6 and 7):
b
x x B
A p
RT
x B
i j ij
j i
m
E
i ij
i
1
( )
The excess Hel mhol tz energy i s al most i ndependent of pressure. I t can be

approxi mated by the Gi bbs energy at l ow pressure. The di fference between the
two functi ons i s corrected by fi tti ng k
ij
unti l the excess Gi bbs energy from the
equati on-of-state (usi ng the mi xi ng rul es 3 and 8) i s equal to the excess Gi bbs
energy computed by an acti vi ty coeffeci ent model . Thi s i s done at a speci fi c mol e
fracti on and temperature.
Thi s mi xi ng rul e accuratel y predi cts the VLE of pol ar mi xtures at hi gh pressures.
UNI FAC or other acti vi ty coeffeci ent model s and parameters from the l i terature
are used. Gas sol ubi l i ti es are not predi cted. They must be regressed from
experi mental data.
Versi on 10
Chapter 3
Unl i ke other (modi fi ed) Huron-Vi dal mi xi ng rul es, the Wong and Sandl er mi xi ng
rul e meets the theoreti cal l i mi t at l ow pressure. The use of k
ij
does i nfl uence
excess mol ar vol ume behavi or. For cal cul ati ons where densi ti es are i mportant,
check whether they are real i sti c.
References
D. S. Wong and S. I . Sandl er, "A Theoreti cal l y Correct New Mi xi ng Rul e for
Cubi c Equati ons of State for Both Hi ghl y and Sl i ghtl y Non-i deal Mi xtures,"
AI ChE J., Vol . 38, (1992), pp. 671 680.
D. S. Wong, H. Orbey, and S. I . Sandl er, "Equati on-of-state Mi xi ng Rul e for Non-
i deal Mi xtures Usi ng Avai l abl e Acti vi ty Coeffi ci ent Model Parameters and That
Al l ows Extrapol ati on over Large Ranges of Temperature and Pressure", I nd Eng
Chem. Res., Vol . 31, (1992), pp. 2033 2039.
H. Orbey, S. I . Sandl er and D. S. Wong, "Accurate Equati on-of-state Predi cti ons
at Hi gh Temperatures and Pressures Usi ng the Exi sti ng UNI FAC Model ," Fluid
Phase Eq., Vol . 85, (1993), pp. 41 54.
ASPEN PLUS has 18 bui l t-i n acti vi ty coeffi ci ent model s. Thi s secti on descri bes
the acti vi ty coeffi ci ent model s avai l abl e.
Model Type
Bromley-Pitzer Electrolyte
Chien-Null Regular solution, local composition
Constant Activity Coefficient Arithmetic
Electrolyte NRTL Electrolyte
Ideal Liquid Ideal
NRTL (Non-Random-Two-Liquid) Local composition
Pitzer Electrolyte
Polynomial Activity Coefficient Arithmetic
Redlich-Kister Arithmetic
continued
Versi on 10
Property
Model
Descriptions
Model Type
Scatchard-Hildebrand Regular solution
Three-Suffix Margules Arithmetic
UNIFAC Group contribution
UNIFAC (Lyngby modified) Group contribution
UNIFAC (Dortmund modified) Group contribution
UNIQUAC Local composition
Van Laar Regular solution
Wagner interaction parameter Arithmetic
Wilson Local composition
Wilson with Liquid Molar Volume Local composition
Bromley-Pitzer Activity Coefficient Model
The Broml ey-Pi tzer acti vi ty coeffi ci ent model i s a si mpl i fi ed Pi tzer acti vi ty
coeffi ci ent model wi th Broml ey correl ati ons for the i nteracti on parameters. See
Appendi x A for a detai l ed descri pti on. Thi s model has predi cti ve capabi l i ti es. I t
can be used up to 6M i oni c strength, but i s l ess accurate than the Pi tzer model i f
the parameter correl ati ons are used.
The Broml ey-Pi tzer model i n ASPEN PLUS i nvol ves user-suppl i ed parameters,
used i n the cal cul ati on of bi nary parameters for the el ectrol yte system.
Parameters
( ) 0
,
( ) 1
,
( ) 2
,
( ) 3
and have fi ve el ements to account for
temperature dependenci es. El ements P1 through P5 fol l ow the temperature
dependency rel ati on:
f T P P T T P
T T
P
T
T
P T T
ref
ref ref
ref
( ) ( ) ln ( ( ) ) + +
_
,
+

_
,
+
1 2 3 4 5
2 2
1 1
Where:
T
ref
= 298.15K.
The user must:
Suppl y these el ements usi ng a Properti es Parameters Bi nary.T-Dependent
form.
Speci fy Comp I D i and Comp I D j on thi s form, usi ng the same order that
appears on the Components.Mai n form.
Versi on 10
Chapter 3
Parameter Name Symbol No. of Elements Default Units
Ionic Unary Parameters
GMBPB

ion
1 0
GMBPD

ion
1
1 0
Cation-Anion Parameters
GMBPB0
( ) 0
5 0
GMBPB1
( ) 1
5 0
GMBPB2
( ) 2
5 0
GMBPB3
( ) 3
5 0
Cation-Cation Parameters
GMBPTH

cc
5 0
Anion-Anion Parameters
GMBPTH

aa
5 0
Molecule-IonParameters
Molecule-Molecule
Parameters
GMBPB0
( ) 0
5 0
GMBPB1
( ) 1
5 0
Chien-Null
The Chi en-Nul l model cal cul ates l i qui d acti vi ty coeffi ci ents and i t can be used for
hi ghl y non-i deal systems. The general i zed expressi on used i n i ts deri vati on can
be adapted to represent other wel l known formal i sms for the acti vi ty coeffi ci ent
by properl y defi ni ng i ts bi nary terms. Thi s characteri sti c al l ows the model the
use of al ready avai l abl e bi nary parameters regressed for those other l i qui d
acti vi ty model s wi th thermodynami c consi stency.
The equati on for the Chi en-Nul l l i qui d acti vi ty coefi ci ent i s:
ln
i
ji i ji j
j j
ji j ji j
j j
k
jk i jk j
j j
jk j jk j
j j
ik
jk j
j
ik
jk j
j
ik
jk j
j
ik
jk j
j
k
A x R x
S x V x
x
A x R x
S x V x
A
A x
R
R x
S
S x
V
V x
+ +
_
,
1
]
1
1
1
1

1
2
Versi on 10
Property
Model
Descriptions
Where:
R
A
A
ji
ji
ij
A
ii
0
A
A
ji
ij
1
A a
b
T
ij ij
ij
+
Subscri pts i and j are component i ndi ces.
The choi ce of model and parameters can be set for each bi nary pai r consti tuti ng
the process mi xture by assi gni ng the appropri ate val ue to the I CHNUL
parameter.
The Regul ar Sol uti on and Scatchard-Hamer model s are regai ned by substi tuti ng
i n the general expressi on (I CHNUL = 1 or 2).
V S
V
V
ji ji
j
l
i
l

*,
*,
Where:
V
j
l *,
= Li qui d mol ar vol ume of component i
The Chi en-Nul l acti vi ty coeffi ci ent model col l apses to the Margul es l i qui d acti vi ty
coeffi ci ent expressi on by setti ng (I CHNUL = 3):
V S
ji ji
1
The Van Laar Li qui d acti vi ty coeffi ci ent model i s the obtai ned when the V and S
parameters i n the Chi en-Nul l model s are set to the rati o of the cross terms of A
(I CHNUL = 4:)
V S
A
A
ji ji
ji
ij

Fi nal l y, the Renon or NRTL model i s obtai ned when we make the fol l owi ng
susbsti tuti ons i n the Chi en-Nul l expressi on for the l i qui d acti vi ty (I CHNUL = 5).
S R
A
A
ji ji
ji
ij

Versi on 10
Chapter 3
A G
ji ji ji
2
V G
ji ji
The fol l owi ng are defi ned for the Non-Random Two-Li qui d acti vi ty coeffi ci ent
model .
Where:
G e
ji
C
ji ji
( )
ij ij
ij
a
b
T
+
C c d T K
ij ij ij
+ ( . ) 27315
c c
ji ij
d d
ji ij
The bi nary parameters CHNULL/1, CHNULL/2, and CHNULL/3 can be

determi ned from regressi on of VLE and/or LLE data. Al so, i f you have
parameters for many of the mi xture pai rs for the Margul es, Van Laar, Scatchard-
Hi l debrand, and NRTL (Non-Random-Two-Li qui d) acti vi ty model s, you can use
them di rectl y wi th the Chi en-Nul l acti vi ty model after sel ecti ng the proper code
(I CHNUL) to i denti fy the source model and enteri ng the appropri ate acti vi ty
model parameters.
Parameter
Name/Element
Symbol Default Upper Limit Lower Limit Units
ICHNUL
3 1 6
CHNULL/1
a
ij
0
CHNULL/2
b
ij
0
CHNULL/3 Vij 0
The parameter I CHNUL is used to identify the activity model parameters available for each binary pair
of interest. The following values are allowed for I CHNUL:
I CHNUL =1 or 2, sets the model to the Scatchard-Hamer or regular solution model for the associated
binary;
I CHNUL =3, sets the model to the Three-Suffix Margules activity model for the associated binary;
I CHNUL =4, sets the model to the Van Laar formalism for the activity model for the associated binary;
I CHNUL =5, sets the model to the NRTL (Renon) formalism for the activity model for the associated
binary.
Versi on 10
Property
Model
Descriptions
I CHNUL =6, sets the model to the full Chien-Null formalism for the activity model for the associated
binary.
When you specify a value for the I CHNUL parameter that is different than the default, you must enter
the appropriate binary model parameters for the chosen activity model directly. The routine will
automatically convert the expressions and parameters to conform to the Chien-Null formulation.
Constant Activity Coefficient
Thi s approach i s used excl usi vel y i n metal l urgi cal appl i cati ons where mul ti pl e
l i qui d and sol i d phases can coexi st. You can assi gn any val ue to the acti vi ty
coeffi ci ent of component i . Use the Properti es Parameters Unary.Scal ar form.
The equati on i s:
i i
a
GMCONS
a
i
1.0 x
Electrolyte NRTL Activity Coefficient Model
ASPEN PLUS uses the el ectrol yte NRTL model to cal cul ate acti vi ty coeffi ci ents,
enthal pi es, and Gi bbs energi es for el ectrol yte systems. Model devel opment and
worki ng equati ons are provi ded i n Appendi x B.
The adjustabl e parameters for the el ectrol yte NRTL model i ncl ude the:
Pure component di el ectri c constant coeffi ci ent of nonaqueous sol vents
Born radi us of i oni c speci es
NRTL parameters for mol ecul e-mol ecul e, mol ecul e-el ectrol yte, and
el ectrol yte-el ectrol yte pai rs
The pure component di el ectri c constant coeffi ci ents of nonaqueous sol vents and
Born radi us of i oni c speci es are requi red onl y for mi xed-sol vent el ectrol yte
systems. The temperature dependency of the di el ectri c constant of sol vent B i s:
B B B
B
T A B
T C
( ) +
_
,
1 1
Each type of el ectrol yte NRTL parameter consi sts of both the nonrandomness
factor, , and energy parameters, . The temperature dependency rel ati ons of
the el ectrol yte NRTL parameters are:
Mol ecul e-Mol ecul e Bi nary Parameters:
BB BB
BB
BB BB
A
B
T
F T G T

ln( ) + + +
Versi on 10
Chapter 3
El ectrol yte-Mol ecul e Pai r Parameters:
ca B ca B
ca B
ca B
ref
ref
C
D
T
E
T T
T
T
T
, ,
,
,
( )
ln + +

+

_
,
1
]
1
B ca B ca
B ca
B ca
ref
ref
C
D
T
E
T T
T
T
T
, ,
,
,
( )
ln + +

+

_
,
1
]
1
El ectrol yte-El ectrol yte Pai r Parameters:
For the el ectrol yte-el ectrol yte pai r parameters, the two el ectrol ytes must share
ei ther one common cati on or one common ani on:
c a c a c a c a
c a c a
c a c a
ref
ref
C
D
T
E
T T
T
T
T
, ,
,
,
( )
ln + +

+

_
,
1
]
1
ca ca ca ca
ca ca
ca ca
ref
ref
C
D
T
E
T T
T
T
T
, ,
,
,
( )
ln + +

+

_
,
1
]
1
Where:
T
ref
= 298.15K
Many parameter pai rs are i ncl uded i n the el ectrol yte NRTL model parameter
databank (see ASPEN PLUS Physical Property Data, Chapter 1).
Parameter Name Symbol No. of
Elements
Default MDS Units
Dielectric Constant Unary Parameters
CPDIEC
A
B
1
B
B
1 0
C
B
1 298.15 TEMPERATURE
Ionic Born Radius Unary Parameters

RADIUS
r
i
1 3x10-10 LENGTH
Molecule-Molecule Binary Parameters
I f dielectric constant parameters are missing for a solvent, the dielectric constant of water is
automatically assigned.
Absolute temperature units are assumed (ASPEN PLUS User Gui de).
continued
Versi on 10
Property
Model
Descriptions
Elements
Default MDS Units
NRTL/1
A
BB
0 x
A
B B
0 x
NRTL/2
B
BB
0 x TEMPERATURE
B
B B
0 x TEMPERATURE
NRTL/3

BB B B
.3 x
NRTL/4 0 x TEMPERATURE
NRTL/5
F
BB
0 x TEMPERATURE
F
B B
0 x TEMPERATURE
NRTL/6
G
BB
0 x TEMPERATURE
G
B B
0 x TEMPERATURE
Electrolyte-Molecule Pair Parameters
GMELCC
C
ca B ,
1 0 x
C
B ca ,
1 0 x
GMELCD
D
ca B ,
1 0 x TEMPERATURE
D
B ca ,
1 0 x TEMPERATURE
GMELCE
E
ca B ,
1 0 x
E
B ca ,
1 0 x
GMELCN

ca B B ca , ,
1 .2 x
I f an electrolyte-molecule parameter is missing, the following defaults are used:

Electrolyte-water -4
Water-electrolyte 8
Electolyte-solvent -2
Solvent-electrolyte 10
Electrolyte-solute -2
Solute-electrolyte 10
continued
Versi on 10
Chapter 3
Elements
Default MDS Units
Electrolyte-Electrolyte Pair
Parameters
GMELCC
C
ca ca ,
1 0 x
C
ca ca ,
1 0 x
C
c a c a ,
1 0 x
C
c a c a ,
1 0 x
GMELCD
D
ca ca ,
1 0 x TEMPERATURE
D
ca ca ,
1 0 x TEMPERATURE
D
c a c a ,
1 0 x TEMPERATURE
D
c a c a ,
1 0 x TEMPERATURE
GMELCE
E
ca ca ,
1 0 x
E
ca ca ,
1 0 x
E
c a c a ,
1 0 x
E
c a c a ,
1 0 x
GMELCN

ca ca ca ca , ,
1 .2 x

c a c a c a c a , ,
1 .2 x
I f dielectric constant parameters are missing for a solvent, the dielectric constant of water is
automatically assigned.
I f an electrolyte-molecule parameter is missing, the following defaults are used:

Electrolyte-water -4
Water-electrolyte 8
Electolyte-solvent -2
Solvent-electrolyte 10
Electrolyte-solute -2
Solute-electrolyte 10
Versi on 10
Property
Model
Descriptions
Ideal Liquid
Thi s model i s used i n Raoul ts l aw. I t represents i deal i ty of the l i qui d phase. Thi s
model can be used for mi xtures of hydrocarbons of si mi l ar carbon number. I t can
be used as a reference to compare the resul ts of other acti vi ty coeffi ci ent model s.
The equati on i s:
ln
i
0
NRTL (Non-Random Two-Liquid)
The NRTL model cal cul ates l i qui d acti vi ty coeffi ci ents for the fol l owi ng property
methods: NRTL, NRTL-2, NRTL-HOC, NRTL-NTH, and NRTL-RK. I t i s
recommended for hi ghl y non-i deal chemi cal systems, and can be used for VLE
and LLE appl i cati ons. The model can al so be used i n the advanced equati on-of-
state mi xi ng rul es, such as Wong-Sandl er and MHV2.
The equati on for the NRTL model i s:
ln
i
j ji ji
j
k ki
k
j ij
k kj
k
ij
m mj mj
m
k kj
k
j
x G
x G
x G
x G
x G
x G
+
_
,
Where:
G
ij
= exp( )
ij ij
ij
= a
b
T
e T f T
ij
ij
ij ij
+ + + ln
ij
= c d T K
ij ij
+ ( . ) 27315
ii
= 0
G
ii
= 1
a
ij
a
ji
b
ij
b
ji
c
ij
c
ji
d
ij
d
ji
Versi on 10
Chapter 3
Recommended
c
ij
Values for Different Types of Mixtures
c
ij
Mixtures
0.30 Nonpolar substances; nonpolar with polar non-associated liquids; small deviations from
ideality
0.20 Saturated hydrocarbons with polar non-associated liquids and systems that exhibit
liquid-liquid immiscibility
0.47 Strongly self-associated substances with nonpolar substances
The bi nary parameters a
ij
, b
ij
, c
ij
, d
ij
, e
ij
, and f
ij
can be determi ned from VLE
and/or LLE data regressi on. ASPEN PLUS has a l arge number of bui l t-i n bi nary
parameters for the NRTL model . The bi nary parameters have been regressed
usi ng VLE and LLE data from the Dortmund Databank. The bi nary parameters
for the VLE appl i cati ons were regressed usi ng the i deal gas, Redl i ch-Kwong, and
Hayden OConnel l equati ons of state. See ASPEN PLUS Physical Property Data,
Chapter 1 for detai l s.
NRTL/1
a
ij
0 x -100.0 100.0
NRTL/2
b
ij
0 x -30000 30000.0 TEMPERATURE
NRTL/3
c
ij
0.30 x 0.0 1.0
NRTL/4
d
ij
NRTL/5
e
ij
0 x TEMPERATURE
NRTL/6
f
ij
0 x TEMPERATURE

References
H. Renon and J.M. Prausni tz, "Local Composi ti ons i n Thermodynami c Excess
Functi ons for Li qui d Mi xtures," AI ChE J ., Vol . 14, No. 1, (1968), pp. 135 144.
Pitzer Activity Coefficient Model
The Pi tzer model i s commonl y used i n the cal cul ati on of acti vi ty coeffi ci ents for
aqueous el ectrol ytes up to 6 mol al i oni c strength. Do not use thi s model i f a non-
aqueous sol vent exi sts. The model devel opment and worki ng equati ons are
provi ded i n Appendi x C. Parameter conversi on between the Pi tzer notati on and
our notati on i s al so provi ded.
Versi on 10
Property
Model
Descriptions
The Pi tzer model i n ASPEN PLUS i nvol ves user-suppl i ed parameters that are
used i n the cal cul ati on of bi nary and ternary parameters for the el ectrol yte
system.
Fi ve el ements (P1 through P5) account for the temperature dependenci es of
parameters
( )
0
,
( )
1
,
( )
2
,
( )
3
, c
, and . These parameters fol l ow the

temperature dependency rel ati on:
( )
( )
f T P P T T P
T T
P
T
T
P T T
i i
ref
i ref i ref i
ref
( ) ( ) ln + +
_
,
+

_
,
+
1 2 3 4 5
2
2 1 1
Where:
Tref = 298.15 K
The user must:
Suppl y these el ements usi ng a Properti es Parameters Bi nary.T-Dependent
form.
Speci fy Comp I D i and Comp I D j on thi s form, usi ng the same order that
appears on the Components.Mai n form.
The parameters are summari zed i n the fol l owi ng tabl e. There i s a Pi tzer
parameter databank i n ASPEN PLUS (see ASPEN PLUS Physical Property
Data, Chapter 1).
Parameter Name Symbol No. of Elements Default MDS Units
Cation-Anion Parameters
GMPTB0
( ) 0
5 0 x
GMPTB1
( ) 1
5 0 x
GMPTB2
( ) 2
5 0 x
GMPTB3
( ) 3
5 0 x
GMPTC
C
5 0 x
Cation-Cation Parameters
GMPTTH

cc
5 0 x
Anion-Anion Parameters
GMPTTH

aa
5 0 x
Cation1-Cation 2-Common Anion Parameters
GMPTPS

cc a
1 0 x
continued
Versi on 10
Chapter 3
Parameter Name Symbol No. of Elements Default MDS Units
Anion1-Anion2-Common Cation Parameters
GMPTPS

ca a
1 0 x
Molecule-Ion and Molecule-Molecule Parameters
GMPTB0
( ) 0
5 0 x
GMPTB1
( ) 1
5 0 x
GMPTC
C
5 0 x
Polynomial Activity Coefficient
Thi s model represents acti vi ty coefi ci ent as an empi ri cal functi on of composi ti on
and temperature. I t i s used frequentl y i n metal l urgi cal appl i cati ons where
mul ti pl e l i qui d and sol i d sol uti on phases can exi st.
The equati on i s:
ln
i i i i i i i i i i
A B x C x D x E x + + + +
2 3 4
Where:
A
i
= a T a a T
i i i 1 2 3
+ + ln( )
B
i
= b T b b T
i i i 1 2 3
+ + ln( )
C
i
= c T c c T
i i i 1 2 3
+ + ln( )
D
i
= d T d d T
i i i 1 2 3
+ + ln( )
E
i
= e T e e T
i i i 1 2 3
+ + ln( )
For any component i , the val ue of the acti vi ty coeffi ci ent can be fi xed:
i i
f
GMPLYP/1
a
i1
0 x
GMPLYP/2
a
i2
0 x
GMPLYP/3
a
i3
0 x
GMPLYP/4
b
i1
0 x
continued
Versi on 10
Property
Model
Descriptions
GMPLYP/5
b
i 2
0 x
GMPLYP/6
b
i3
0 x
GMPLYP/7
c
i1
0 x
GMPLYP/8
c
i 2
0 x
GMPLYP/9
c
i3
0 x
GMPLYP/10
d
i1
0 x
GMPLYP/11
d
i2
0 x
GMPLYP/12
d
i3
0 x
GMPLYP/13
e
i1
0 x
GMPLYP/14
e
i2
0 x
GMPLYP/15
e
i3
0 x
GMPLYO
f
i
x
Redlich-Kister
Thi s model cal cul ates acti vi ty coeffi ci ents. I t i s a pol ynomi al i n the di fference
between mol e fracti ons i n the mi xture. I t can be used for l i qui d and sol i d
mi xtures (mi xed crystal s).
The equati on i s:
( )
( )
( ) ( )
( )
( )
[ ]
ln
, ,
i j n ij i j
n
i j j k n jk j k
n
j k
n k
nc
n j
nc
x A x x nx x x x A x x n x x
1
]
1

2
1
2
2
1
5
1 1
5
1
2 1
Where:
nc = Number of components
A
ij 1,
= a T b
ij ij
+
A
ij 2,
= c T d
ij ij
+
A
ij 3,
= e T f
ij ij
+
A
ij 4,
= g T h
ij ij
+
Versi on 10
Chapter 3
A
ij 5,
= m T n
ij ij
+
For any component i, the val ue of the acti vi ty coeffi ci ent can be fi xed:
i i
v
Parameter Name/ Element Symbol Default MDS Upper Limit Lower Limit Units
GMRKTB/1
a
ij
0 x
GMRKTB/2
b
ij
0 x
GMRKTB/3
c
ij
0 x
GMRKTB/4
d
ij
0 x
GMRKTB/5
e
ij
0 x
GMRKTB/6
f
ij
0 x
GMRKTB/7
g
ij
0 x
GMRKTB/8
h
ij
0 x
GMRKTB/9
m
ij
0 x
GMRKTB/10
n
ij
0 x
GMRKTO
v
i
x
Scatchard-Hildebrand
The Scatchard-Hi l debrand model cal cul ates l i qui d acti vi ty coeffi ci ents. I t i s used
i n the CHAO-SEA property method and the GRAYSON property method.
The equati on for the Scatchard-Hi l debrand model i s:
ln ( )
*,

i
i
l
j k ji jk
k j
V
RT
A A

1 2
Where:
A
ij
=
( )
2
2

i j
i
=
x V
V
i i
l
m
l
*,
Versi on 10
Property
Model
Descriptions
V
m
L *,
= x V
i i
l
i
*,
The Scatchard-Hi l debrand model does not requi re bi nary parameters.

Parameter
Name/Element
Symbol Default MDS Upper Limit Lower Limit Units
TC
T
ci
x 5.0 2000.0 TEMPERATURE
DELTA

i
x
10
3
10
5
SOLUPARAM
VLCVT1
V
i
CVT *,
x 0.0005 1.0 MOLE-VOLUME
GMSHVL
V
i
I *,
V V
T
i
I
i
CVT
ci
*, *,
. .
.
_
,
57 30
29815
Three-Suffix Margules
Thi s model can be used to descri be the excess properti es of l i qui d and sol i d
sol uti ons. I t does not fi nd much use i n chemi cal engi neeri ng appl i cati ons, but i s
sti l l wi del y used i n metal l urgi cal appl i cati ons. Note that the bi nary parameters
for thi s model do not have physi cal si gni fi cance.
The equati on i s:
( ) ( ) ( ) ( )
ln
i ij ji j jl j l ij jl j j i jl ljj l j
l
nc
j
nc
j
nc
l
nc
j
nc
j
nc
k k x k x x k k x x x k k x x + +

1
2
2
2
Where k
ij
i s a bi nary parameter:
( ) k a T b c T
ij ij ij ij
+ + ln
For any component i, the val ue of the acti vi ty coeffi ci ent can be fi xed:
i i
d
Parameter Name/ Element Symbol Default MDS Upper Limit Lower Limit Units
GMMRGB/1
a
ij
0 x TEMPERATURE
GMMRGB/2
b
ij
0 x
GMMRGB/3
c
ij
0 x
GMMRGO
d
i
x
Versi on 10
Chapter 3
References
M. Margul es, "ber di e Zusammensetzung der gestti gten Dmpfe von
Mi schungen," Si tzungsber. Akad. Wi ss. Vi enna, Vol . 104, (1895), p. 1293.
D.A. Gaskel l , I ntroducti on to Metal l urgi cal Thermodyani cs, 2nd ed., (New York:
Hemi sphere Publ i shi ng Corp., 1981), p. 360.
R.C. Rei d, J.M. Prausni tz, and B.E. Pol i ng, The Properti es of Gases and Li qui ds,
4th ed., (New York: McGraw-Hi l l , 1987).
UNIFAC
The UNI FAC model cal cul ates l i qui d acti vi ty coeffi ci ents for the fol l owi ng
property methods: UNI FAC, UNI F-HOC, and UNI F-LL. Because the UNI FAC
model i s a group-contri buti on model , i t i s predi cti ve. Al l publ i shed group
parameters and group bi nary parameters are stored i n ASPEN PLUS.
The equati on for the ori gi nal UNI FAC l i qui d acti vi ty coeffi ci ent model i s made up
of a combi natori al and resi dual term:
ln = ln ln
i
c
i
r
+
ln
i
c
= ln ln

i
i
i
i
i
i
i
i
x x
Z
_
,
+ +
1
]
1
1
2
1

Where the mol ecul ar vol ume and surface fracti ons are:
i
i i
j j
j
nc
x r
x r
and
i
i i
j j
j
nc
x
z
q
x
z
q
2
2
Where nc i s the number of components i n the mi xture. The coordi nati on number
z i s set to 10. The parameters ri and qi are cal cul ated from the group vol ume and
area parameters:
r v R
i ki k
k
ng
and q v Q
i ki k
k
ng
Where
ki
i s the number of groups of type k i n mol ecul e i, and ng i s the number
of groups i n the mi xture. The resi dual term i s:
[ ]
ln ln ln
i
r
ki k k
i
k
ng

Versi on 10
Property
Model
Descriptions
k
i s the acti vi ty coeffi ci ent of a group at mi xture composi ti on, and
k
i
i s the
acti vi ty coeffi ci ent of group k i n a mi xture of groups correspondi ng to pure i. The
parameters
k
and
k
i
are defi ned by:
ln ln
k k m mk
m km
n nm
n
ng
m
ng
m
ng
Q
_
,
_
,

1

Wi th:
k
k k
m m
m
ng
X
z
Q
X
z
Q
2
2
And:
mn
b T
mn

e
/
The parameter X
k
i s the group mol e fracti on of group k i n the l i qui d:
X
x
x
k
kj j
j
nc
mj j
m
ng
j
nc
Parameter Name/Element SymbolT Default MDS Lower Limit Upper Limit Units
UFGRP
( )
ki mi
...

GMUFQ
Q
k

GMUFR
R
k

GMUFB
b
kn
TEMPERATURE
The parameter UFGRP stores the UNI FAC functi onal group number and number
of occurrences of each group. UFGRP i s stored i n the ASPEN PLUS pure
component databank for most components. For nondatabank components, enter
UFGRP on the Properti es Mol ecul ar Structure Functi onal Group sheet. See
ASPEN PLUS Physical Property Data, Chapter 3, for a l i st of the UNI FAC
functi onal groups.
Versi on 10
Chapter 3
References
Aa. Fredensl und, R.L. Jones and J.M. Prausni tz, AI ChE J ., Vol . 21, (1975),
p. 1086.
Aa. Fredensl und, J. Gmehl i ng and P. Rasmussen, "Vapor-Li qui d Equi l i bri a usi ng
UNI FAC," (Amsterdam: El sevi er, 1977).
H.K. Hansen, P. Rasmussen, Aa. Fredensl und, M. Schi l l er, and J. Gmehl i ng,
"Vapor-Li qui d Equi l i bri a by UNI FAC Group Contri buti on. 5 Revi si on and
Extensi on", I nd. Eng. Chem. Res., Vol . 30, (1991), pp. 2352-2355.
UNIFAC (Dortmund Modified)
The UNI FAC modi fi cati on by Gmehl i ng and coworkers (Wei dl i ch and Gmehl i ng,
1987; Gmehl i ng et al ., 1993), i s sl i ghtl y di fferent i n the combi natori al part. I t i s
otherwi se unchanged compared to the ori gi nal UNI FAC:
ln ln ln

i
c i
i
i
i
i
i
i
i
i
x x
z
q

_
,
+ +
_
,

1
2
1
Wi th:
i
i
i
j j
j
x
r
x r
3
4
3
4
The temperature dependency of the i nteracti on parameters i s:
a a a T a T
mn mn mn mn
+ +
, , , 1 2 3
2
Parameter Name/Element SymbolT Default MDS Lower Limit Upper Limit Units
UFGRPD
( ) k m
ki mi
...

GMUFDQ
Q
k

GMUFDR
R
k

UNIFDM/1
a
mn,1
0 TEMPERATURE
UINFDM/2
a
mn, 2
0 TEMPERATURE
UNIFDM/3
a
mn,3
0 TEMPERATURE
Versi on 10
Property
Model
Descriptions
The parameter UFGRPD stores the group number and the number of occurrences
of each group. UFGRPD i s stored i n the ASPEN PLUS pure component
databank. For nondatabank components, enter UFGRPD on the Properti es
Mol ecul ar Structure Functi onal Group sheet. See ASPEN PLUS Physical
Property Data, Chapter 3, for a l i st of the Dortmund modi fi ed UNI FAC functi onal
groups.
References
U. Wei dl i ch and J. Gmehl i ng, "A Modi fi ed UNI FAC Model 1. Predi cti on of VLE,
h
E
and

," I nd. Eng. Chem. Res., Vol . 26, (1987), pp. 13721381.
J. Gmehl i ng, J. Li , and M. Schi l l er, "A Modi fi ed UNI FAC Model . 2. Present
Parameter Matri x and Resul ts for Di fferent Thermodynami c Properti es," I nd.
Eng. Chem. Res., Vol . 32, (1993), pp. 178193.
UNIFAC (Lyngby Modified)
The equati ons for the "temperature-dependent UNI FAC" (Larsen et al ., 1987) are
si mi l ar to the ori gi nal UNI FAC:
ln ln ln
i i
c
i
r
+ ,
ln ln

i
c i
i
i
i
x x
_
,
+ 1
Vol ume fracti ons are modi fi ed:
i
i i
j j
j
nc
x r
x r
2
3
2
3
Wi th:
r R
i ki k
k
ng
( )
ln ln ln
i
r
ki k k
i
k
ng

Versi on 10
Chapter 3
Where
k
and
k
i
have the same meani ng as i n the ori gi nal UNI FAC, but
defi ned as:
ln ln
k k m mk
m
ng
m km
n nm
n
ng
m
ng
z
Q

_
,
_
,
1
]
1
1
1
1
2
1

Wi th:
k
k k
m m
m
ng
X
z
Q
X
z
Q
2
2
mn
a T
e
mn

The temperature dependency of a i s descri bed by a functi on i nstead of a constant:
( ) a a a T a T
T
T
mn mn mn mn
+ + +
_
,
, , ,
. ln
.
.
1 2 3
29815
29815
29815
Parameter Name/Element Symbol T Default MDS Lower Limit Upper Limit Units
UFGRPL
( )
ki mi
...

GMUFLQ
Q
k

GMUFLR
R
k

UNIFLB/1
a
mn,1
0 TEMPERATURE
UNIFLB/2
a
mn, 2
0 TEMPERATURE
UNIFLB/3
a
mn,3
0 TEMPERATURE
The parameter UFGRPL stores the modi fi ed UNI FAC functi onal group number
and the number of occurrences of each group. UFGRPL i s stored i n the
ASPEN PLUS pure component databank. For nondatabank components, enter
UFGRP on the Properti es Mol ec-Struct.Func Group form. See ASPEN PLUS
Physical Property Data, Chapter 3, for a l i st of the Larsen modi fi ed UNI FAC
functi onal groups.
Versi on 10
Property
Model
Descriptions
References
B. Larsen, P. Rasmussen, and Aa. Fredensl und, "A Modi fi ed UNI FAC Group-
Contri buti on Model for Predi cti on of Phase Equi l i bri a and Heats of Mi xi ng," I nd.
Eng. Chem. Res., Vol . 26, (1987), pp. 2274 2286.
UNIQUAC
The UNI QUAC model cal cul ates l i qui d acti vi ty coeffi ci ents for these property
methods: UNI QUAC, UNI Q-2, UNI Q-HOC, UNI Q-NTH, and UNI Q-RK. I t i s
recommended for hi ghl y non-i deal chemi cal systems, and can be used for VLE
and LLE appl i cati ons. Thi s model can al so be used i n the advanced equati ons of
state mi xi ng rul es, such as Wong-Sandl er and MHV2.
The equati on for the UNI QUAC model i s:
ln ln ln ln

i
i
i
i
i
i
i i i j ij j i i
i
i
j j
j j
x
z
q q t q t l q
x
x l + + +

2
Where:
i
= q x q q q x
i i T T k k
k
;

i
=
q x q q q x
i i T T k k
k
;
i
=
i i i T T k k
k
r x r r r x
;
l
i
= ( )
z
r q r
i i i
2
1 +
t
i
=

k ki
k
ij
= exp( ln a b T C T d T
ij ij ij ij
+ + +
z = 10
a
ij
a
ji
b
ij
b
ji
c
ij
c
ji
Versi on 10
Chapter 3
d
ij
d
ji
ij
, b
ij
, c
ij
, and d
ij
can be determi ned from VLE and/or
LLE data regressi on. ASPEN PLUS has a l arge number of bui l t-i n parameters
for the UNI QUAC model . The bi nary parameters have been regressed usi ng VLE
and LLE data from the Dortmund Databank. The bi nary parameters for VLE
appl i cati ons were regressed usi ng the i deal gas, Redl i ch-Kwong, and Hayden-
OConnel l equati ons of state. See Chapter 1, ASPEN PLUS Physical Property
Data, for detai l s.
GMUQR
r
i
x
GMUQQ
q
i
x
GMUQQ1
q
i
q x
UNIQ/1
a
ij
0 x -50.0 50.0
UNIQ/2
b
ij
0 x -15000.0 15000.0 TEMPERATURE
UNIQ/3
c
ij
0 x TEMPERATURE
UNIQ/4
d
ij
0 x TEMPERATURE

References
D.S. Abrams and J.M. Prausni tz, "Stati sti cal Thermodynami cs of l i qui d
mi xtures: A new expressi on for the Excess Gi bbs Energy of Partl y or Compl etel y
Mi sci bl e Systems," AI ChE J ., Vol . 21, (1975), p. 116.
A. Bondi , "Physi cal Properti es of Mol ecul ar Crystal s, Li qui ds and Gases,"
(New York: Wi l ey, 1960).
Si monetty, Yee and Tassi os, "Predi cti on and Correl ati on of LLE," I nd. Eng.
Chem., Process Des. Dev., Vol . 21, (1982), p. 174.
Van Laar
The Van Laar model (Van Laar 1910) cal cul ates l i qui d acti vi ty coeffi ci ents for the
property methods: VANLAAR, VANL-2, VANL-HOC, VANL-NTH, and VANL-
RK. I t can be used for hi ghl y noni deal systems.
( ) ( )
[ ]
ln ( )
i i i i i i i i i i i
A z C z z z A B A B + + 1 1 2 1
2
2
3
Versi on 10
Property
Model
Descriptions
Where:
z
i
=
( )
A x
A x B x
i i
i i i i
+ 1
A
i
= ( ) x A x
j ij i
j
1
B
i
= ( ) x A x
j ji i
j
1
C
i
= x C x
j ij i
j
( ) 1
A
ij
= a b T
ij ij
+
C
ij
= c d T
ij ij
+
C
ij
= C
ji
A
ii
= B C
ii ii
0
a
ij
a
ji
b
ij
b
ji
Parameters
Name/Element
Symbol Default MDS Lower Limit Upper Limit Units
VANL/1
a
ij
0 x -50.0 50.0
VANL/2
b
ij
0 x -15000.0 15000.0 TEMPERATURE
VANL/3
c
ij
0 x -50.0 50.0
VANL/4
d
ij
0 x -15000.0 15000.0 TEMPERATURE

References
J.J. Van Laar, "The Vapor Pressure of Bi nary Mi xtures," Z. Phys. Chem., Vol . 72,
(1910), p. 723.
R.C. Rei d, J.M. Prausni tz, and B.E. Pol i ng, The Properties of Gases and Liquids,
4th ed. (New York: McGraw-Hi l l , 1987).
Versi on 10
Chapter 3
Wagner Interaction Parameter
The Wagner I nteracti on Parameter model cal cul ates acti vi ty coeffi ci ents. Thi s
model i s used for di l ute sol uti ons i n metal l urgi cal appl i cati ons.
The rel ati ve acti vi ty coeffi ci ent wi th respect tothe reference acti vi ty coeffi ci ent of
a sol ute i (i n a mi xture of sol utes i, j, and l and sol vent A) i s:
( )
ln ln
i i
ref
A ij i
j
nc
k x j A +
1
Where:
ln
A jl j l
l
nc
j
nc
k x x j l A

1
2
and
The parameter
i
ref
i s the reference acti vi ty coeffi ci ent of sol ute i:
( ) ln ln
i
ref
i i i
a T b c T + +
k
ij
i s a bi nary parameter:
( ) k d T e f T
ij ij ij ij
+ + ln
For any component i , the val ue of the acti vi ty coeffi ci ent can be fi xed:
i i
g
Thi s model i s recommended for di l ute sol uti ons.
Parameter Name/ Element Symbol Default MDS Lower Limit Upper Limit Units
GMWIPR/1
a
i
0 x TEMPERATURE
GMWIPR/2
b
i
0 x
GMWIPR/3
c
i
0 x
GMWIPB/1
d
ij
0 x TEMPERATURE
GMWIPB/2
e
ij
0 x
GMWIPB/3
f
ij
0 x
GMWIPO
g
i
x
GMWIPS
0 x
GMWI PS is used to identify the solvent component. You must set GMWI PS to 1.0 for the solvent
component. This model allows only one solvent.
Versi on 10
Property
Model
Descriptions
References
A.D. Pel ton and C. W. Bal l , "A Modi fi ed I nteracti on Parameter Formal i sm for
Non-Di l ute Sol uti ons," Metallurgical Transactions A, Vol . 17A, (Jul y 1986),
p. 1211.
Wilson
The Wi l son model cal cul ates l i qui d acti vi ty coeffi ci ents for the property methods:
WI LSON, WI LS2, WI LS-HOC, WI LS-NTH, WI LS-RK, and WI LS-HF. I t i s
recommended for hi ghl y noni deal systems, especi al l y al cohol -water systems. I t
can al so be used i n the advanced equati on-of-state mi xi ng rul es, such as Wong-
Sandl er and MHV2. Thi s model cannot be used for l i qui d-l i qui d equi l i bri um
cal cul ati ons.
The equati on for the Wi l son model i s:
ln ln
i ij j
j
ji j
jk k
k
j
A x
A x
A x

_
,

1
Where:
ln A
ij
= a b T c T d T
ij ij ij ij
+ + + ln
a
ij
a
ji
b
ij
b
ji
c
ij
c
ji
d
ij
d
ji
ij
, b
ij
, c
ij
, and d
ij
must be determi ned from VLE data
regressi on. ASPEN PLUS has a l arge number of bui l t-i n bi nary parameters for
the Wi l son model . The bi nary parameters have been regressed usi ng VLE data
from the Dortmund Databank. The bi nary parameters were regressed usi ng the
i deal gas, Redl i ch-Kwong, and Hayden-OConnel l equati ons of state. See Chapter
1, ASPEN PLUS Physical Property Data, for detai l s.
WILSON/1 a
ij
0 x -50.0 50.0
WILSON/2 b
ij
0 x -15000.0 15000.0 TEMPERATURE
WILSON/3 c
ij
0 x - TEMPERATURE
WILSON/4 d
ij
0 x TEMPERATURE

Versi on 10
Chapter 3
References
G.M. Wi l son, J . Am. Chem. Soc., Vol . 86, (1964), p. 127.
Wilson Model with Liquid Molar Volume
Thi s Wi l son model cal cul ates l i qui d acti vi ty coeffi ci ents usi ng the ori gi nal
formul ati on of Wi l son (Wi l son 1964) except that l i qui d mol ar vol ume i s cal cul ated
at system temperature, i nstead of at 25C. I t i s recommended for hi ghl y noni deal
systems, especi al l y al cohol -water systems. I t can be used i n any acti vi ty
coeffi ci ent property method or i n the advanced equati on-of-state mi xi ng rul es,
such as Wong-Sandl er and MHV2. Thi s model cannot be used for l i qui d-l i qui d
equi l i bri um cal cul ati ons.
The equati on for the Wi l son model i s:
ln ln
i ij j
j
ji j
jk k
k
j
A x
A x
A x

_
,

1
Where:
ln A
ij
=
ln
V
V
b
T
j
i
ij
+
b
ij
b
ji
V
i
and V
j
are l i qui d mol ar vol ume at the system temperature cal cul ated usi ng
the Rackett model .
The bi nary parameters b
ij
and b
ji
must be determi ned from VLE data regressi on.
There are no bui l t-i n bi nary parameters for thi s model .
WSNVOL/1
b
ij
0 x -15000.0 15000.0 TEMPERATURE

Pure component parameters for the Rackett model are al so requi red.
References
G.M. Wi l son, J . Am. Chem. Soc., Vol . 86, (1964), p. 127.
Versi on 10
Property
Model
Descriptions
Vapor Pressure and Liquid Fugacity Models
ASPEN PLUS has 4 bui l t-i n vapor pressure and l i qui d fugaci ty model s. Thi s
secti on descri bes the vapor pressure and l i qui d fugaci ty model s avai l abl e.
Model Type
Extended Antoine/Wagner Vapor pressure
Chao-Seader Fugacity
Grayson-Streed Fugacity
Kent-Eisenberg Fugacity
Extended Antoine/Wagner
The vapor pressure of a l i qui d can be cal cul ated usi ng the extended Antoi ne
equati on or the Wagner equati on.
Extended Antoine Equation
Many parameters are avai l abl e for the extended Antoi ne equati on from the
ASPEN PLUS pure component databank. Thi s equati on i s used whenever the
parameter PLXANT i s avai l abl e.
The equati on for the extended Antoi ne vapor pressure model i s:
ln ln
*,
p C
C
T C
C T C T C t for C C
i
l
i
i
i
i i i
C
i i
i
+
+
+ + +
1
2
3
4 5 6 8 9
7
Extrapol ati on of ln
*,
p
i
l
versus 1/T occurs outsi de of temperature bounds.
Parameter
Name/Element
PLXANT/1
C
i 1
x PRESSURE,
TEMPERATURE
PLXANT/2
C
i 2
x TEMPERATURE
PLXANT/3, . . . , 7
C C
i i 3 7
, ...,
0 x TEMPERATURE
PLXANT/8
C
i 8
0 x TEMPERATURE
PLXANT/9
C
i 9
1000 x TEMPERATURE
I f elements 5, 6, or 7 are non-zero, absolute temperature units are assumed for elements 1 through 7.
Versi on 10
Chapter 3
Wagner Vapor Pressure Equation
The Wagner vapor pressure equati on i s the best equati on for correl ati on.
However, i ts resul ts are sensi ti ve to the val ues of Tc and pc. The equati on i s used
i f the parameter WAGNER i s avai l abl e:
( ) ( ) ( ) ( )
[ ]
ln
*,
.
p C T C T C T C T T
ri
l
i ri i ri i ri i ri ri
+ + +
1 2
1 5
3
3
4
4
1 1 1 1
Where:
T T T
ri ci
p p p
ri
l
i
l
ci
*, *,
Parameter Name/ElementSymbol Default MDS Lower Limit Upper Limit Units

WAGNER/1
C
i 1
x
WAGNER/2
C
i 2
0 x
WAGNER/3
C
i 3
0 x
WAGNER/4
C
i 4
0 x
TC
T
ci
TEMPERATURE
PC
p
ci
PRESSURE
References
Rei d, Prausni tz, and Pol i ng, The Properties of Gases and Liquids, 4th ed., (New
York: McGraw-Hi l l , 1987).
Harl acher and Braun, "A Four-Parameter Extensi on of the Theorem of
Correspondi ng States," I nd. Eng. Chem. Process Des. Dev., Vol . 9, (1970), p. 479.
W. Wagner, Cryogenics, Vol . 13, (1973), pp. 470-482.
Chao-Seader
The Chao-Seader model cal cul ates pure component fugaci ty coeffi ci ent, for
l i qui ds. I t i s used i n the CHAO-SEA property method. Thi s i s an empi ri cal model
wi th the Curl -Pi tzer form. The general form of the model i s:
( ) ( )
ln ln ln
*,

i
l
i i i
+
0 1
Where:
( ) ( )

i i
0 1
, = ( ) fcn T T p p
ci ci
, , ,
Versi on 10
Property
Model
Descriptions
TC
T
ci
PC
p
ci

10
5
10
8
PRESSURE
OMEGA

i
-0.5 2.0
References
K.C. Chao and J.D. Seader, "A General Correl ati on of Vapor-Li qui d Equi l i bri a i n
Hydrocarbon Mi xtures," AI ChE J ., Vol . 7, (1961), p. 598.
Grayson-Streed
The Grayson-Streed model cal cul ates pure component fugaci ty coeffi ci ents for
l i qui ds, and i s used i n the GRAYSON property method. I t i s an empi ri cal model
wi th the Curl -Pi tzer form. The general form of the model i s:
( ) ( )
ln ln ln
*,

i
l
i i i
+
0 1
Where:
( ) ( )
( )
i i ci ci
fcn T T p p
0 1
, , , ,
TC
T
ci
PC
p
ci
10
5
10
8
PRESSURE
OMEGA

i
-0.5 2.0
References
H.G. Grayson and C.W. Streed, Paper 20-PO7, Si xth Worl d Petrol eum
Conference, Frankfurt, June 1963.
Kent-Eisenberg
The Kent-Ei senberg model cal cul ates l i qui d mi xture component fugaci ty
coeffi ci ents and l i qui d enthal py for the AMI NES property method.
Versi on 10
Chapter 3
The chemi cal equi l i bri a i n H S CO
2 2
+ + amine systems are descri bed usi ng these
chemi cal reacti ons:
RR NH
K
H RR NH
+
+ +
2
1
RR NCOO H O
K
RR NH HCO +
+

2
2
3
H O CO
K
H HCO
2 2
3
3
+
+
+
H O
K
H OH
2
4
+
+
HCO
K
H CO
3
5
3
2 +
+
H S
K
H HS
2
6 2
+
+
HS
K
H S
+
+
7 2
Where:
R and R = Al cohol substi tuted al kyl groups
The equi l i bri um constants are gi ven by:
ln K A A T A T A T A T
i i i i i i
+ + + +
1 2 3
2
4
3
5
4
The chemi cal equi l i bri um equati ons are sol ved si mul taneousl y wi th the bal ance
equati ons. Thi s obtai ns the mol e fracti ons of free H S
2
and CO
2
i n sol uti on. The
equi l i bri um parti al pressures of H S
2
and CO
2
are rel ated to the respecti ve free
concentrati ons by Henrys constants:
ln H B B T
i i i
+
1 2
The apparent fugaci ti es and parti al mol ar enthal pi es, Gi bbs energi es and
entropi es of H S
2
and CO
2
are cal cul ated by standard thermodynami c
rel ati onshi ps. The chemi cal reacti ons are al ways consi dered.
Versi on 10
Property
Model
Descriptions
The val ues of the coeffi ci ents for the seven equi l i bri um constants ( ) A A
i i 1 5
, ..., and
for the two Henrys constants B
i 1
and B
i 2
are bui l t i nto ASPEN PLUS. The
coeffi ci ents for the equi l i bri um constants were determi ned by regressi on. Al l
avai l abl e data for the four ami nes were used: monoethanol ami ne,
di ethanol ami ne, di sopropanol ami ne and di gl ycol ami ne.
You are not requi red to enter any parameters for thi s model .
References
R.L. Kent and B. Ei senberg, Hydrocarbon Processing, (February 1976), pp. 87-92.
Versi on 10
Chapter 3
Heat of Vaporization Model
ASPEN PLUS uses two model s to cal cul ate pure component heat of vapori zati on:
the Watson/DI PPR model and the Cl ausi us-Cl apeyron model . For the
Watson/DI PPR model , the DI PPR equati on i s the pri mary equati on used for al l
components. The Watson equati on i s used i n PCES.
DIPPR Equation
The equati on for the DI PPR heat of vapori zati on model i s:
( )
( )
vap i i ri
C C T C T C T
i i
H C T C T C
i i ri i ri i ri *

+ + +
1 6 7
1
2 3 4
2
5
3
for
Where:
T T T
ri ci
Extrapol ati on of
vap i
H
*
versus T occurs outsi de of temperature bounds.
Parameter
Name/Element Symbol Default MDS Lower Limit Upper Limit Units
DHVLDP/1
C
i 1
x MOLE-ENTHALPY
DHVLDP/2, . , 5
C C
i i 2 5
, ...,
0 x
DHVLDP/6
C
i 6
0 x TEMPERATURE
DHVLDP/7
C
i 7
1000 x TEMPERATURE
TC
T
ci
Watson Equation
The equati on for the Watson model i s:
( ) ( )
( )

vap i vap i
ci
ci
a b T T
H T H T
T T
T T
for T T
i i ci
* *
min
_
,
>
+
1
1
1 1
1
1
Where:
( )
vap i
H T
*
1
= Heat of vapori zati on at temperature T
1
Versi on 10
Property
Model
Descriptions
Parameter Name/Element Symbol Default Lower Limit Upper Limit Units
TC
T
ci
DHVLWT/1
( )
vap i
H T
*
1
5 10
4
X 5 10
8
X
MOLE-ENTHALPY
DHVLWT/2
T
1
DHVLWT/3
a
i
0.38 -2.0 2.0
DHVLWT/4
b
i
0 -2.0 2.0
DHVLWT/5
T
min
0 0.0 1500.0 TEMPERATURE
Clausius-Clapeyron Equation
ASPEN PLUS can cal cul ate heat of vapori zati on usi ng the Cl ausi us-Cl apeyron
equati on:
( )
vap i
i
l
i
v
i
l
H
d p
dT
T V V
*
*,
*, *,

Where:
d p
dT
i
l *,
= Sl ope of the vapor pressure curve cal cul ated from the Extended
Antoi ne equati on
V
i
v *,
= Vapor mol ar vol ume cal cul ated from the Redl i ch-Kwong
equati on-of-state
V
i
l *,
= Li qui d mol ar vol ume cal cul ated from the Rackett equati on
For parameter requi rements, see Extended Antoi ne/Wagner , the Rackett model ,
and Redl i ch-Kwong, al l i n thi s chapter.
ASPEN PLUS has 10 bui l t-i n mol ar vol ume and densi ty model s avai l abl e. Thi s
secti on descri bes the mol ar vol ume and densi ty model s.
Model Type
API Liquid Volume Liquid volume
Brelvi-O'Connell Partial molar liquid volume of gases
continued
Versi on 10
Chapter 3
Model Type
Clarke Aqueous Electrolyte Volume Liquid volume
Costald Liquid Volume Liquid volume
Debije-Hckel Volume Electrolyte liquid volume
Rackett/DIPPR Pure Component Liquid Volume Liquid volume/liquid density
Rackett Mixture Liquid Volume Liquid volume
Modified Rackett Liquid volume
Solids Volume Polynomial Solid volume
API Liquid Volume
Thi s model cal cul ates l i qui d mol ar vol ume for a mi xture, usi ng the API procedure
and the Rackett model . I deal mi xi ng i s assumed:
V x V x V
m
l
p p
l
r r
l
+
Where:
x
p
= Mol e fracti on of pseudocomponents
x
r
= Mol e fracti on of real components
For pseudocomponents, the API procedure i s used:
( ) V fcn T T API
p
l
b
, ,
Where:
fcn = A correl ati on based on API Fi gure 6A3.5 (API Technical Data Book,
Petrol eum Refi ni ng, 4th edi ti on)
For real components, the mi xture Rackett model i s used:
( )
[ ]
V
RT Z
p
r
l
c
RA T
c
r
+ 1 1
2 7
See the Rackett model for descri pti ons.
TB
T
b
API API -60.0 500.0
Versi on 10
Property
Model
Descriptions
TB
T
b
API API -60.0 500.0
TC
T
c
PC
p
c

10
5
10
8
PRESSURE
RKTZRA
Z
RA
r
ZC 0.1 0.5
Brelvi-OConnell
The Brel vi -OConnel l model cal cul ates parti al mol ar vol ume of a supercri ti cal
component i at i nfi ni te di l uti on i n pure sol vent A. Parti al mol ar vol ume at
i nfi ni te di l uti on i s requi red to compute the effect of pressure on Henrys constant.
(See Henrys Constant on page 3-103.) The general form of the Brel vi -OConnel l
model i s:
( )
V fcn V V V
iA i
BO
A
BO
A
l
, ,
*
Where:
i = Sol ute or di ssol ved-gas component
A = Sol vent component
The l i qui d mol ar vol ume of sol vent i s obtai ned from the Rackett model :
( )
[ ]
V
RT Z
p
i
l cA A
RA T
cA
rA
*,
+ 1 1
2 7
TC
T
cA
PC
p
cA
105 108 PRESSURE
continued
Versi on 10
Chapter 3
RKTZRA
Z
A
RA
ZC x 0.1 1.0
VLBROC/1
V
i
BO
VC x -1.0 1.0 MOLE-VOLUME
VLBROC/2 0 x -0.1 0.1 TEMPERATURE
References
S.W. Brel vi and J.P. OConnel l , AI ChE J., Vol . 18, (1972), p. 1239.
S.W. Brel vi and J.P. OConnel l , AI ChE J., Vol . 21, (1975), p. 157.
Clarke Aqueous Electrolyte Volume
The Cl arke model cal cul ates l i qui d mol ar vol ume for el ectrol ytes sol uti ons. The
model i s appl i cabl e to mi xed sol vents and i s based on:
Amagats l aw (equati on 1)
The rel ati onshi p between the parti al mol ar vol ume of an el ectrol yte and i ts
mol e fracti on i n the sol vent (equati on 2)
Al l quanti ti es are expressed i n terms of apparent components.
Apparent Component Approach
Amagats l aw i s:
V x V
m
l
i i
i
(1)
For water and mol ecul ar sol utes, V V
i i
*
and i s computed from the Rackett
equati on. I f water i s the onl y mol ecul ar component, the ASME steam tabl e i s
used to compute V
i
*
for water.
For el ectrol ytes:
V V A
x
x
ca ca ca
ca
ca
+
+
1
(2)
Where:
x
ca
= Apparent el ectrol yte mol e fracti on
The mol e fracti ons x
ca
are reconsti tuted arbi trari l y from the true i oni c
concentrati ons, even i f you use the apparent component approach. Thi s techni que
i s expl ai ned i n El ectrol yte Si mul ati on, Chapter 5.
Versi on 10
Property
Model
Descriptions
The resul t i s that el ectrol ytes are generated from al l possi bl e combi nati ons of
i ons i n sol uti on. For exampl e: gi ven an aqueous sol uti on of CA
2+
, Na
+
, SO
4
2
,
Cl
four el ectrol ytes are found: CaCl

2
, Na SO
2 4
, CaSO
4
and NaCl . The Cl arke
parameters of al l four el ectrol ytes are used. You can rel y on the defaul t, whi ch
cal cul ates the Cl arke parameters from i oni c parameters. Otherwi se, you must
enter parameters for any el ectrol ytes that may not exi st i n the components l i st. I f
you do not want to use the defaul t, the fi rst step i n usi ng the Cl arke model i s to
enter any needed component I Ds for el ectrol ytes not i n the components l i st.
The mol e fracti ons of apparent el ectrol ytes used i n the cal cul ati on are al l
nonzero, but are arbi trary val ues. For a gi ven i oni c sol uti on, the Cl arke model
al ways yi el ds the same vol ume, i ndependent of the mol e fracti ons of the
el ectrol ytes. Constrai nts between the Cl arke parameters resul t:
V V V V
CaCl Na SO CaSO
NaCl 2 2 4 4
2

+ +
A si mi l ar equati on exi sts for A
ca
You can consi der these constrai nts i n si mpl e
parameter i nput and i n data regressi on.
True Component Approach
The true mol ar vol ume i s obtai ned from the apparent mol ar vol ume:
V V
n
n
m
l t
m
l a
a
t
, ,
Where:
V
m
l t ,
= Li qui d vol ume per number of true speci es
V
m
l a ,
=
Li qui d vol ume per number of apparent speci es, V
m
l
of equati on 1
n
a
= Number of apparent speci es
n
t
= Number of true speci es
The apparent mol ar vol ume i s cal cul ated as expl ai ned i n the precedi ng
subsecti on.
Temperature Dependence
The temperature dependence of the mol ar vol ume of the sol uti on i s
approxi matel y equal to the temperature dependence of the mol ar vol ume of the
sol vent mi xture:
( ) ( )
( )
( )
V T V K
x V T
x V K
m
l
m
l
B B
l
B
B B
l
B
298
298
*,
*,
Versi on 10
Chapter 3
Where:
B = Any sol vent
Parameter Name/Element Applicable Components Symbol Default Units
VLCLK/1 Cation-Anion
V
ca

MOLE-VOLUME
VLCLK/2 Cation-Anion
A
ca
0.020 MOLE-VOLUME
I f VLCLK/ 1 is missing, it is calculated based on VLBROC and CHARGE. I f VLBROC is missing, the
default value of

012 10
2
. x is used.
COSTALD Liquid Volume
The equati on for the COSTALD l i qui d vol ume model i s:
( )
V V V V
m
sat
m
CTD
m
R
m
R

, , 0
1

Where:
V
m
R, 0
and V
m
R, 5
are functi ons or T
r
for 0 25 095 . . < T
r
For 095 10 . . < T
r
, there i s a l i near i nterpol ati on between the l i qui d densi ty at
T
r
= 0.95 and the vapor densi ty at T
r
= 1.05. Thi s model can be used to cal cul ate
saturated and compressed l i qui d mol ar vol ume. The compresed l i qui d mol ar
vol ume i s cal cul ated usi ng the Tai t equati on.
Mi xi ng Rul es:
V xV xV xV
m
CTD
i i
CTD
i
i i
CTD
i i
CTD
I
+
_
,
_
,
1
]
1
1

1
4
2 3 1 3
3
*. *. *,
V T x x V T
m
CTD
c i j ij
CTD
cij
j i
x
i i
i
Where:
( )
V T V T V T
ij
CTD
cij i
CTD
ci j
CTD
cj
*, *,
1
2
Versi on 10
Property
Model
Descriptions
TC
T
ci
VSTCTD
V
i
CTD *,
VC X 0.001 3.5 MOLE-VOLUME
OMGCTD

i
OMEGA X -0.5 2.0
References
R.W. Hanki nson and G.H. Thomson, AI ChE J., Vol . 25, (1979), p. 653.
G.H. Thomson, K.R. Brobst, and R.W. Hanki nson, AI ChE J., Vol . 28, (1982), p. 4,
p. 671.
Debije-Hckel Volume
The Debi je-Hckel model cal cul ates l i qui d mol ar vol ume for aqueous el ectrol yte
sol uti ons.
The equati on for the Debi je-Hckel vol ume model i s:
V x V x V
m w w k k
k
+
*
Where:
V
k
i s the mol ar vol ume for water and i s cal cul ated from the ASME steam tabl e.
V
k
i s cal cul ated from the Debi je-Hckel l i mi ti ng l aw for i oni c speci es. I t i s
assumed to be the i nfi ni te di l uti on parti al vol ume for mol ecul ar sol utes.
( )
V V z
A
b
bI
k k k
V
+

_
,
+

10
3
1
3
1
2
ln
Where:
V
k
= Parti al mol ar i oni c vol ume at i nfi ni te di l uti on

z
k
= Charge number of i on k
A
V
= Debi je-Hckel constant for vol ume
b = 1.2
Versi on 10
Chapter 3
I = 1
2
2
m z
k k
k
, the i oni c strength, wi th

m
k
= Mol ari ty of i on k
A
V
i s computed as fol l ows:
A A R
l
p p
V
w
w
+
_
,
2 10 3
1
6
x
ln
p
w
Where:
A
= Debi je-Hckel constant for the osmoti c coeffi ci ents (Pi tzer, 1979)

( ) ( )
1
3
3
2
2 10
1
2
3
2

_
,
w A
e
w B
N
Q
k T
w
= Densi ty of water (kg / m
-3
)
w
= Di el ectri c constant of water ( Fm
1
), a functi on of pressure and
temperature (Bradl ey and Pi tzer, 1979)
Parameter Name Applicable Components Symbol Default Units
VLBROC Ions, molecular Solutes
V
k
0 MOLE-VOLUME
References
H.C. Hel geson and D.H. Ki rkham, "Theoreti cal predi cti on of the thermodynami c
behavi or of aqueous el ectrol ytes at hi gh pressure and temperature. I .
Thermodynami c/el ectrostati c properti es of the sol vent", Am. J . Sci., 274, 1089
(1974).
Rackett/DIPPR Pure Component Liquid Volume
Two equati ons are avai l abl e for pure component l i qui d mol ar vol ume: the Rackett
equati on and the DI PPR equati on. The DI PPR equati on i s used i f the parameter
DNLDI P i s avai l abl e for a gi ven component. The Rackett equati on i s used i f the
parameter RKTZRA i s avai l abl e.
For l i qui d mol ar vol ume of mi xtures, the Rackett mi xture equati on i s al ways
used. Thi s i s not necessari l y consi stent wi th the pure component mol ar vol ume or
densi ty.
Versi on 10
Property
Model
Descriptions
DIPPR
The DI PPR equati on i s:
( )
*, ( / )
/
l
i i
T C
i i
C C C T C
i
C
i

+
1 2
1 1
6 7
3
4
for
Thi s equati on i s si mi l ar to the Rackett equati on. I t returns l i qui d mol ar vol ume
for pure components.
/1
C
i 1
x MOLE-DENSITY
DNLDIP/2
C
i 2
0 x
DNLDIP/3
C
i 3
T
ci
x TEMPERATURE
DNLDIP/4
C
i 4
0 x
DNLDIP/5
C
i 5
0 x
DNLDIP/6
C
i 6
0 x TEMPERATURE
DNLDIP/7
C
i 7
1000 x TEMPERATURE
I f element 3 is non-zero, absolute temperature units are assumed for element 3. (See Chapter 5.)
Rackett
The equati on for the Rackett model i s:
( )
[ ]
V
RT Z
p
i
l
ci i
RA
T
ci
r
_
,
+
*,
1 1
2 7
Where:
T
r
=
T
T
ci
Parameter Name/
Element
TC
T
ci
PC
p
ci

10
5
10
8
PRESSURE
RKTZRA
Z
i
RA *,
ZC x 0.1 1.0
Versi on 10
Chapter 3
References
H.G. Rackett, J.Chem, Eng. Data., Vol . 15, (1970), p. 514.
C.F. Spencer and R.P. Danner, J. Chem. Eng. Data, Vol . 17, (1972), p. 236.
Rackett Mixture Liquid Volume
The Rackett equati on cal cul ates l i qui d mol ar vol ume for al l acti vi ty
coeffi ci ent-based and petrol eum-tuned equati on-of-state based property methods.
I n the l ast category of property methods, the equati on i s used i n conjuncti on wi th
the API model . The API model i s used for pseudocomponents, whi l e the Rackett
model i s used for real components. (See API Li qui d Vol ume on page 3-87.)
The equati on for the Rackett model i s:
( )
( )
V
RT Z
P
m
l
c m
RA
c
T
r
1
]
1
1 1
2
7
Where:
T
c
=
( ) ( )
x x V V T T k V
i j ci cj ci cj ij
j i
cm
1
2
1
2

T
P
c
c
=
x
T
P
i
ci
ci
i
Z
m
RA
=
x Z
i i
RA
i
*,
V
cm
=
xV
i ci
i
T
r
= T
T
c
Versi on 10
Property
Model
Descriptions
Parameter
Name/Element
TC
T
ci
PC
p
ci

10
5
10
8
PRESSURE
VCRKT
V
ci
RKTZRA
Z
i
RA *,
ZC x 0.1 1.0
RKTKIJ
k
ij
( )
( )
1
8
1
2
1
3
1
3
3
+
V V
V V
ci cj
ci cj
x -5.0 5.0
References
H.G. Rackett, J .Chem, Eng. Data., Vol . 15, (1970), p. 514.
C.F. Spencer and R.P. Danner, J . Chem. Eng. Data, Vol . 17, (1972), p. 236.
Modified Rackett
The Modi fi ed Rackett equati on i mproves the accuracy of l i qui d mi xture mol ar
vol ume cal cul ati on by i ntroduci ng addi ti onal parameters to compute the pure
component parameter RKTZRA and the bi nary parameter k
ij
.
The equati on for the Modi fi ed Rackett model i s:
( )
( )
V
RT Z
P
m
l c m
RA
c
T
r
1
]
1
1 1
2
7
Where:
T
c
=
( ) ( )
x x V V T T k V
i j ci cj ci cj ij
j i
cm
1
2
1
2

k
ij
=
A B T C T
ij ij ij
+ +
2
T
P
c
c
=
x
T
P
i
ci
ci
i
Z
m
RA
=
x Z
i i
RA
i
*,

Versi on 10
Chapter 3
V
cm
=
xV
i ci
i
T
r
= T
T
c
MRKZRA/1
a
i
RKTZRA x 0.1 0.5
MRKZRA/2
b
i
0 x
MRKZRA/3
c
i
0 x
MRKKIJ/1
A
ij
0 x
MRKKIJ/2
B
ij
0 x
MRKKIJ/3
C
ij
0 x
References
H.G. Rackett, J .Chem, Eng. Data., Vol . 15, (1970), p. 514.
C.F. Spencer and R.P. Danner, J . Chem. Eng. Data, Vol . 17, (1972), p. 236.
Solids Volume Polynomial
The equati on for the sol i ds vol ume pol ynomi al i s:
( ) V T C C T C T C T C T C T C
i
s
i i i i i i
*,
+ + + +
1 2 3
2
4
3
5
4
6 7
for
Parameter Name Applicable Components Symbol MDS Default Units
VSPOLY/1 Salts, CI solids
C
i 1
x

VSPOLY/2, . . . , 5 Salts, CI solids
C C
i i 2 5
, ...,
x 0

C
i 6
x 0

C
i 7
x 1000

The units are TEMPERATURE and MOLE-VOLUME.

Versi on 10
Property
Model
Descriptions
ASPEN PLUS has fi ve bui l t-i n heat capaci ty model s. Thi s secti on descri bes the
heat capaci ty model s avai l abl e.
Model Type
Aqueous Infinite Dilution Heat Capacity Polynomial Electrolyte liquid
Criss-Cobble Aqueous Infinite Dilution Ionic Heat Capacity Electrolyte liquid
DIPPR Liquid Heat Capacity Liquid
Ideal Gas Heat Capacity/DIPPR Ideal gas
Solids Heat Capacity Polynomial Solid
Aqueous Infinite Dilution Heat Capacity
The aqueous phase i nfi ni te di l uti on enthal pi es, entropi es, and Gi bbs energi es are
cal cul ated from the heat capaci ty pol ynomi al . The val ues are used i n the
cal cul ati on of aqueous and mi xed sol vent properti es of el ectrol yte sol uti ons:
C C C T C T
C
T
C
T
C
T
C T C
p i
aq
i
i i i
i i ,
,
+ + + + +
1 2 3
2 4 5
2
6
7 8
for
C
p i
aq
,
,
i s l i nearl y extrapol ated usi ng the sl ope at C T C
i i 7 7
for <
C
p i
aq
,
,
i s l i nearl y extrapol ated usi ng the sl ope at C T C
i i 8 8
for >
Parameter Name/Element Applicable Components Symbol Default Units
CPAQ0 Ions, molecular solutes
C
i 1

C C
i i 2 5
, ...,
0

C
i 6
0

C
i 7
1000

The units are TEMPERATURE and HEAT CAPACI TY.

Criss-Cobble Aqueous Infinite Dilution Ionic Heat
Capacity
The Cri ss-Cobbl e correl ati on for aqueous i nfi ni te di l uti on i oni c heat capaci ty i s
used i f no parameters are avai l abl e for the aqueous i nfi ni te di l uti on heat capaci ty
pol ynomi al . From the cal cul ated heat capaci ty, the thermodynami c properti es
entropy, enthal py and Gi bbs energy at i nfi nte di l uti on i n water are deri ved:
Versi on 10
Chapter 3
( ) ( ) ( ) ( )
C f S T S T ion type T
p i
aq
a
aq
c
aq
,
, , ,
, ,

298 298 or
Parameter NameApplicable
Components
Symbol Default Units
IONTYP
Ions Ion Type 0

SO25C Anions
S
a
aq ,
( ) ( )
f a
aq
f a
aq
H T G T

, ,
.
298 298
29815
MOLE-ENTROPY
Cations
S
a
aq ,
( ) ( )
f a
aq
f a
aq
H T G T

, ,
.
298 298
29815
MOLE-ENTROPY
I ONTYP = 1 for cations

= 2 for simple anions and hydroxide ions
= 3 for oxy anions
= 4 for acid oxy anions
= 5 for hydrogen ion
DIPPR Liquid Heat Capacity
The DI PPR l i qui d heat capaci ty model i s used for the cal cul ati on of pure
component l i qui d heat capaci ty and pure component l i qui d enthal py. To use thi s
model , two condi ti ons must exi st:
The parameter CPLDI P i s avai l abl e.
The component i s not supercri ti cal (HENRY-COMP).
The model uses a speci fi c method (see Chapter 4):
( ) ( )
H T H T C dT
i
l
i
l ref
p i
l
T
T
ref
*, *,
,
*,

( )
H T
i
l ref *,
i s cal cul ated as:
( ) ( )
H T H H H H
i
l ref
i
ig
i
v
i
ig
vap i
l *, *, *, *, *,
+
T
ref
i s the reference temperature; i t defaul ts to 298.15 K. You can enter a
di fferent val ue for the reference temperature. Thi s i s useful when you want to
use thi s model for very l i ght components or for components that are sol i ds at
298.15K.
Acti vate thi s method by speci fyi ng the route DHL09 for the property DHL on the
Properti es Property Methods Routes sheet. For equati on-of-state property method,
you must al so modi fy the route for the property DHLMX to use a route wi th
method 2 or 3, i nstead of method 1. For exampl e, you can use the route DHLMX00
or DHLMX30. You must ascertai n that the route for DHLMX that you sel ect
contai ns the appropri ate vapor phase model and heat of mi xi ng cal cul ati ons. Cl i ck
the Vi ew button on the form to see detai l s of the route.
Versi on 10
Property
Model
Descriptions
Opti onal l y, you can speci fy that thi s model i s used for onl y certai n components.
The properti es for the remai ni ng components are then cal cul ated by the standard
model . Use the parameter COMPHL to speci fy the components for whi ch thi s
model i s used. By defaul t, al l components wi th the CPLDI P parameters use thi s
model .
The equati on i s:
C C C T C T C T C T for C T C
p i
l
i i i i i i i ,
*,
+ + + +
1 2 3
2
4
3
5
4
6 7
Li near extrapol ati on occurs for C
p
l *,
versus T outsi de of bounds.
Parameter
CPLDIP/1
C
i 1
T
x MOLE-HEAT-CAPACITY,
TEMPERATURE
CPLDIP/2,...,5
C C
i i 2 5
, ...,
0 x MOLE-HEAT-CAPACITY,
TEMPERATURE
CPLDIP/6
C
i 6
0 x TEMPERATURE
CPLDIP/7
C
i 7
1000 x TEMPERATURE
TREFHL
T
ref
298.15 TEMPERATURE
COMPHL
TEMPERATURE
To specify that the model is used for a component, enter a value of 1.0 for this component parameter.
Ideal Gas Heat Capacity/DIPPR
The DI PPR i deal gas heat capaci ty equati on i s used for most components i n the
ASPEN PLUS pure components databank. I t i s used when the parameter
CPI GDP i s avai l abl e for a gi ven component.
DIPPR
The equati on for the DI PPR i deal gas heat capaci ty model by Al i and Lee 1981 i s:
( ) ( )
C C C
C T
C T
C
C T
C T
C T C
p
ig
i i
i
i
i
i
i
i i
*,
sinh cosh
+

_
,
+

_
,

1 2
3
3
2
4
5
5
2
6 7
for
Thi s model i s al so used to cal cul ate i deal gas enthal pi es, entropi es, and Gi bbs
energi es.
Versi on 10
Chapter 3
Parameter
CPIGDP/1
C
i 1
x MOLE-HEAT-CAPACITY
CPIGDP/2
C
i 2
0 x MOLE-HEAT-CAPACITY
CPIGDP/3
C
i 3
0 x TEMPERATURE
CPIGDP/4
C
i 4
0 x MOLE-HEAT-CAPACITY
CPIGDP/5
C
i 5
0 x TEMPERATURE
CPIGDP/6
C
i 6
0 x TEMPERATURE
CPIGDP/7
C
i 7
1000 x TEMPERATURE
I f elements 3 or 5 are non-zero, absolute temperature units are assumed.

Ideal Gas Heat Capacity Polynomial
The i deal gas heat capaci ty pol ynomi al i s used for components stored i n
ASPENPCD, AQUEOUS, and SOLI DS databanks. Thi s model i s al so used i n
PCES.
C C C T C T C T C T C T C T C
p
ig
i i i i i i i i
*,
+ + + + +
1 2 3
2
4
3
5
4
6
5
6 7
for
C C C T T C
p
ig
i i
C
i
i
*,
+ <
9 10 7
11
for
C
p
ig *,
i s l i nearl y extrapol ated usi ng sl ope at C T C
i i 8 8
for >
Thi s model i s al so used to cal cul ate i deal gas enthal pi es, entropi es, and Gi bbs
energi es.
Parameter
Name/Element
Symbol Default MDS Lower
Limit
Upper
Limit
Units
CPIG/1
C
i 1
MOLE-HEAT-CAPACITY,
TEMPERATURE
CPIG/2, . . . , 6
C C
i i 2 6
, ...,
0 MOLE-HEAT-CAPACITY,
TEMPERATURE
CPIG/7
C
i 7
0 TEMPERATURE
CPIG/8
C
i 8
1000 TEMPERATURE
CPIG/9, 10, 11 C C C
i i i 9 1 0 1 1
, , MOLE-HEAT-CAPACITY,
TEMPERATURE
I f elements 10 or 11 are non-zero, absolute temperature units are assumed for elements 9 through 11.
Versi on 10
Property
Model
Descriptions
References
Data for the I deal Gas Heat Capaci ty Pol ynomi al : Rei d, Prausni tz and Pol i ng,
The Properties of Gases and Liquids, 4th ed., (New York: McGraw-Hi l l , 1987).
ASPEN PLUS combusti on data bank, JANAF Thermochemi cal Data, Compi l ed
and cal cul ated by the Thermal Research Laboratory of Dow Chemi cal Company.
F. A. Al y and L. L. Lee, "Sel f-Consi stent Equati ons for Cal cul ati ng the I deal Gas
Heat Capaci ty, Enthal py, and Entropy, Fluid Phase Eq., Vol . 6, (1981), p. 169.
Solids Heat Capacity Polynomial
The enthal py, entropy, and Gi bbs energy of sol i ds are cal cul ated from the heat
capaci ty pol ynomi al :
C C C T C T
C
T
C
T
C
T
C T C
p i
s
i i i
i i i
i i ,
*,
+ + + + +
1 2 3
2 4 5
2
6
7 8
for
C
p i ,
*,8
l i nearl y extrapol ated usi ng the sl ope at C
i 7
for T C
i
<
7
and
C
p i ,
*,8
l i nearl y extrapol ated usi ng the sl ope at C
i 8
for T C
i
>
8
Parameter Name
Applicable
Components
Symbol MDS Default Units
CPSPO1/1 Solids, Salts
C
i 1
x

CPSPO1/2, . . . , 6 Solids, Salts
C C
i i 2 6
, ...,
x 0

C
i 7
x 0

C
i 8
x 1000

The units are TEMPERATURE and HEAT CAPACI TY.

Solubility Correlations
ASPEN PLUS has two bui l t-i n sol ubi l i ty correl ati on model s. Thi s secti on
descri bes the sol ubi l i ty correl ati on model s avai l abl e.
Model Type
Henrys constant Gas solubility in liquid
Water solubility Water solubility in organic liquid
Versi on 10
Chapter 3
Henrys Constant
The Henrys constant model i s used when Henrys Law i s appl i ed to cal cul ate K-
val ues for di ssol ved gas components i n a mi xture. Henrys Law i s avai l abl e i n al l
acti vi ty coeffi ci ent property methods, such as the WI LSON property method. The
model cal cul ates Henrys constant for a di ssol ved gas component (i ) i n one or
more sol vents (A or B):
( ) ( )
ln ln H w H
i i A iA iA
A

Where:
w
A
=
( )
( )
x V
x V
A cA
B cB
B
2
3
2
3
( )
ln ,
*,
H T p
iA A
l
= a b T c T d T T T T
iA iA iA iA L H
+ + + ln for
( ) H T P
iA
, =
( )
H T p
RT
V dp
iA A
l
iA
p
p
a
l
, exp
*,
*,
1

_
,
The parameter V
iA
i s obtai ned from the Brel vi -OConnel l model . p

A
l *,
i s obtai ned
from the Antoi ne model .
i s obtai ned from the appropri ate acti vi ty coeffi ci ent

model .
The Henrys constants a
iA
, b
iA
, c
iA
, and d
iA
are speci fi c to a sol ute-sol vent pai r.
They can be obtai ned from regressi on of gas sol ubi l i ty data. ASPEN PLUS has a
l arge number of bui l t-i n Henrys constants for many sol utes i n sol vents. These
parameters were obtai ned usi ng data from the Dortmund Databank. See ASPEN
PLUS Physical Property Data, Chapter 1, for detai l s.
Versi on 10
Property
Model
Descriptions
VC
V
cA
HENRY/1
a
iA
x PRESSURE,
TEMPERATURE
HENRY/2
b
iA
0 x TEMPERATURE
HENRY/3
c
iA
0 x TEMPERATURE
HENRY/4
d
iA
0 x TEMPERATURE
HENRY/5
T
L
0 x TEMPERATURE
HENRY/6
T
H
2000 x TEMPERATURE
I f a
iA
is missing, ln
H
iA
iA
is set to zero and the weighting factor w

A
is renormalized.
I f elements 2 or 3 are non-zero, absolute temperature units are assumed for elements 1 through 4.
Water Solubility
Thi s model cal cul ates sol ubi l i ty of water i n a hydrocarbon-ri ch l i qui d phase. The
model i s used automati cal l y when you model a hydrocarbon-water system wi th
the free-water opti on. See Chapter 6 for detai l s.
The expressi on for the l i qui d mol e fracti on of water i n the i th hydrocarbon
speci es i s:
ln x C
C
T
C T C T C
wi i
i
i i i
+ +
1
2
3 4 5
for
The parameters for 60 hydrocarbon components are stored i n the ASPEN PLUS
pure component databank.
Parameter
WATSOL/1
C
i 1
( ) fcn T ASG M
bi i i
, ,
-10.0 33.0 TEMPERATURE
WATSOL/2
C
i 2
( ) fcn T ASG M
bi i i
, ,
-10000.0 3000.0 TEMPERATURE
WATSOL/3
C
i 3
0 -0.05 0.05 TEMPERATURE
Absolute temperature units are assumed

continued
Versi on 10
Chapter 3
Parameter
WATSOL/4
C
i 4
0 0.0 500 TEMPERATURE
WATSOL/5
C
i 5
1000 4.0 1000 TEMPERATURE
Absolute temperature units are assumed

Other Thermodynamic Property Models
ASPEN PLUS has four bui l t-i n addi ti onal thermodynami c property model s that
do not fi t i n any other category. Thi s secti on descri bes these model s:
Cavett Li qui d Enthal py Departure
BARI N Equati ons for Gi bbs Energy, Enthal py, Entropy and Heat Capaci ty
El ectrol yte NRTL Enthal py
El ectrol yte NRTL Gi bbs Energy
Li qui d Enthal py from Li qui d Heat Capaci ty Correl ati on
Enthal pi es Based on Di fferent Reference States
Cavett
The general form for the Cavett model i s:
( ) ( )
H H fcn T T p p Z
i
l
i
ig
ci ci i
*, *, *
, , , ,

( ) ( )
H H x H H
m
l
m
ig
i i
l
i
ig
i

*, *,
TC
T
ci
PC
p
ci

10
5
10
8
PRESSURE
DHLCVT
Z
i ,
ZC X 0.1 0.5
Versi on 10
Property
Model
Descriptions
BARIN Equations for Gibbs Energy, Enthalpy, Entropy,
and Heat Capacity
The fol l owi ng equati ons are used when parmeters from the ASPEN PLUS
i norgani c databank are retri eved.
Gi bbs energy:
( ) G a b T c T T d T e T f T g T h T
i n i n i n i n i n i n i n i n i
*,
, , , , , , , ,
ln

+ + + + + + +
2 3 4 1 2
(1)
Enthal py:
H a c T d T e T ef T g T eh T
i n i n i n i n i n i n i n i
*,
, , , , , , ,

+ + + +
2 3 4 1 2
2 2 (2)
Entropy:
( ) S b c T d T e T f T g T h T
i n i n i n i n i n i n i n i
*,
, , , , , , ,
ln

+ + +

1 2 3 4 2
2 3 2 3
(3)
Heat capaci ty:
C c d T e T f T g T h T
p i n i n i n i n i n i n i ,
*,
, , , , , ,

2 6 12 2 6
2 3 2 3
(4)
refers to an arbi trary phase whi ch can be sol i d, l i qui d, or i deal gas. For each
phase, mul ti pl e sets of parameters from 1 to n are present to cover mul ti pl e
temperature ranges. The val ue of the parameter n depends on the phase. (See
tabl es that fol l ow.)
The four properti es C
p
, H, S, and G are i nterrel ated as a resul t of the
thermodynami c rel ati onshi ps:
( ) ( )
H T H T C dT
i i
ref
p i
T
T
ref
*, *,
,
*,

( ) ( )
S T S T
C
T
dT
i i
ref p i
T
T
ref
*, *, ,
*,

G H TS
i i i
*, *, *,

There are anal yti cal rel ati onshi ps between the expressi ons descri bi ng the
properti es C
p
, H, S, and G (equati ons 1 to 4). The parameters a
n i ,
to h
n i ,
can occur
i n more than one equati on.
Solid Phase
The parameters i n range n
are val i d for temperature:

T T T
n l
s
n h
s
, ,
< <
Versi on 10
Chapter 3
Parameter Name
/Element Symbol Default MDS Lower Limit Upper Limit Units

CPSXPn/1
T
n l
s
,
x TEMPERATURE
CPSXPn/2
T
n h
s
,
x TEMPERATURE
CPSXPn/3
a
n i
s
,
x

CPSXPn/4
b
n i
s
,
0 x

CPSXPn/5
c
n i
s
,
0 x

CPSXPn/6
d
n i
s
,
0 x

CPSXPn/7
e
n i
s
,
0 x

CPSXPn/8
f
n i
s
,
0 x

CPSXPn/9
g
n i
s
,
0 x

CPSXPn/10
h
n i
s
,
0 x

n is 1 through 7.CPSXP1 vector stores solid parameters for the first temperature range. CPSXP2 vector
stores solid parameters for the second temperature range, and so on.
TEMPERATURE, ENTHALPY, ENTROPY

Liquid Phase
are val i d for temperature: T T T

n l
l
n h
l
, ,
< <
Parameter Name

CPLXPn/1
T
n l
l
,
x TEMPERATURE
CPLXPn/2
T
n h
l
,
x TEMPERATURE
CPLXPn/3
a
n i
l
,
x

CPLXPn/4
b
n i
l
,
0 x

CPLXPn/5
c
n i
l
,
0 x

n is 1 through 2. CPLXP1 stores liquid parameters for the first temperature range. CPLXP2 stores
liquid parameters for the second temperature range.

continued
Versi on 10
Property
Model
Descriptions
Parameter Name

CPLXPn/6
d
n i
l
,
0 x

CPLXPn/7
e
n i
l
,
0 x

CPLXPn/8
f
n i
l
,
0 x

CPLXPn/9
g
n i
l
,
0 x

CPLXPn/10
h
n i
l
,
0 x

n is 1 through 2. CPLXP1 stores liquid parameters for the first temperature range. CPLXP2 stores
liquid parameters for the second temperature range.

Ideal Gas Phase
are val i d for temperature: T T T

n l
ig
n h
ig
, ,
< <
Parameter Name

CPIXPn/1
T
n l
ig
,
x TEMPERATURE
CPIXPn/2
T
n l
ig
,
x TEMPERATURE
CPIXPn/3
a
n i
ig
,
x

CPIXPn/4
b
n i
ig
,
0 x

CPIXPn/5
c
n i
ig
,
0 x

CPIXPn/6
d
n i
ig
,
0 x

CPIXPn/7
e
n i
ig
,
0 x

CPIXPn/8
f
n i
ig
,
0 x

CPIXPn/9
g
n i
ig
,
0 x

CPIXPn/10
h
n i
ig
,
0 x

n is 1 through 3. CPI XP1 vector stores ideal gas parameters for the first temperature range. CPI XP2
vector stores ideal gas parameters for the second temperature range, and so on.

Versi on 10
Chapter 3
Electrolyte NRTL Enthalpy
The equati on for the el ectrol yte NRTL enthal py model i s:
H x H x H H
m w w k k m
E
k
* * *
+ +
The mol ar enthal py H

m
*
and the mol ar excess enthal py H
m
E *
are defi ned wi th the
asymmetri cal reference state: the pure sol vent water and i nfi ni te di l uti on of
mol ecul ar sol utes and i ons. (here * refers to the asymmetri cal reference state.)
H
w
*
i s the pure water mol ar enthal py, cal cul ated from the I deal Gas model and
the ASME Steam Tabl e equati on-of-state. (here * refers to pure component.)
( ) ( ) ( ) ( )
H H T C dT H T p H T p
w f
ig
p k
ig
w w
ig
T
* *,
,
.
. , ) , + +
29815
298 15
The property H
k
i s cal cul ated from the i nfi ni te di l uti on aqueous phase heat
capaci ty pol ynomi al model , by defaul t. I f pol ynomi al model parameters are not
avai l abl e, i t i s cal cul ated from the Cri ss-Cobbl e model for i ons and from Henrys
l aw for mol ecul ar sol utes.
The subscri pt k can refer to a mol ecul ar sol ute (i), to a cati on (c), or an ani on (a):
H H C
k f k
aq
p k
aq
T

+
,
,
,
. 298 15
H
m
E *
i s excess enthal py and i s cal cul ated from the el ectrol yte NRTL acti vi ty
coeffi ci ent model .
See Cri ss-Cobbl e model and Henrys l aw model , thi s chapter, for more
i nformati on
IONTYP Ions
Ion 0
SO25C Cations
( ) S T
c
aq
,
298
MOLE-ENTROPY
Anions
( ) S T
a
aq
,
298
MOLE-ENTROPY
DHAQFM Ions, Molecular Solutes
f k
aq
H
,
MOLE-ENTHALPY
CPAQ0 Ions, Molecular Solutes
C
p k
aq
,
,
HEAT-CAPACITY
Not needed if CPAQ0 is given for ions

continued
Versi on 10
Property
Model
Descriptions
DHFORM Molecular Solutes
f i
ig
H
*,
MOLE-EHTHALPY
Water
f w
ig
H
*,
MOLE-ENTHALPY
CPIG Molecular Solutes
C
p i
ig
,
*,

Water
C
p w
ig
,
*,
Not needed if DHAQFM and CPAQ0 are given for molecular solutes
The unit keywords for CPI G are TEMPERATURE and HEAT-CAPACI TY. I f elements 10 or 11 of CPI G
are non-zero, absolute temperature units are assumed for all elements. (See ASPEN PLUS User Gui de.)
Electrolyte NRTL Gibbs Energy
The equati on for the NRTL Gi bbs energy model i s:
G x x x x G
m w w k k j j m
E
j k
* * *
ln + + +

The mol ar Gi bbs energy and the mol ar excess Gi bbs energy G
m
*
and G
m
E *
are
defi ned wi th the asymmetri cal reference state: as pure water and i nfi ni te
di l uti on of mol ecul ar sol utes and i ons. (* refers to the asymmetri cal reference
state.) The i deal mi xi ng term i s cal cul ated normal l y, where j refers to any
component. The mol ar Gi bbs energy of pure water (or thermodynami c potenti al )
w
*
i s cal cul ated from the i deal gas contri buti on. Thi s i s a functi on of the i deal
gas heat capaci ty and the departure functi on. (here * refers to the pure
component.)
( )

w w
ig
w w
ig * *, * *,
+
The departure functi on i s obtai ned from the ASME steam tabl es.
The aqueous i nfi ni te di l uti on thermodynami c potenti al
k
i s cal cul ated from the

i nfi ni te di l uti on aqueous phase heat capaci ty pol ynomi al model , by defaul t.
k refers to any i on or mol ecul ar sol ute. I f pol ynomi al model parameters are not
avai l abl e, i t i s cal cul ated from the Cri ss-Cobbl e model for i ons and from Henrys
l aw for mol ecul ar sol utes:
( )
k f k
aq
pk
aq
fcn G C

, ,
,
G
E *
i s cal cul ated from the el ectrol yte NRTL acti vi ty coeffi ci ent model .
Versi on 10
Chapter 3
See the Cri ss-Cobbl e model and Henrys l aw model , thi s chapter, for more
i nformati on.
Parameter Name
Applicable
Components Symbol Default Units
IONTYP Ions
Ion 0
SO25C Cations
( ) S T
c
aq
,
298
MOLE-ENTROPY
Anions
( ) S T
a
aq
,
298
MOLE-ENTROPY
DGAQFM Ions, molecular solutes
f k
aq
G
,
MOLE-ENTHALPY
C
p k
aq
,
,
HEAT-CAPACITY
DGFORM Molecular solutes
f i
G
MOLE-ENTHALPY
Water

f w
G
MOLE-ENTHALPY
CPIG Molecular solutes
C
p i
ig
,
*,

Water
C
p w
ig
,
*,
Not needed if DHAQFM and CPAQ0 are given for molecular solutes
The unit keywords for CPI G are TEMPERATURE and HEAT-CAPACI TY. I f elements 10 or 11 of CPI G
are non-zero, absolute temperature units are assumed for all elements. (See ASPEN PLUS User Gui de.)
Liquid Enthalpy from Liquid Heat Capacity Correlation
Li qui d enthal py i s di rectl y cal cul ated by i ntegrati on of l i qui d heat capaci ty:
( ) ( ) H T H T C dT
i
l
i
l ref
p i
l
T
T
ref
*, *,
,
*,
+
The reference enthal py i s cal cul ated at T

ref
as:
( ) ( ) H T H H H H
i
l ref
i
ig
i
v
i
ig
vap i
l *, *, *, *, *,
+
Versi on 10
Property
Model
Descriptions
Where:
H
i
ig *,
= I deal gas enthal py
H H
i
v
i
ig *, *,
= Vapor enthal py departure from equati on-of-state
vap i
l
H
*,
= Heat of vapori zati on from Watson/DI PPR model
T
ref
= Reference temperature, speci fi ed by user. Defaul ts to 298.15
K
See DI PPR Li qui d Heat Capaci ty on page 3-99 for parameter requi rement and
addi ti onal detai l s.
Enthalpies Based on Different Reference States
Two property methods, WI LS-LR and WI LS-GLR, are avai l abl e to cal cul ate
enthal pi es based on di fferent reference states. The WI LS-LR property method i s
based on saturated l i qui d reference state for al l components. The WI LS-GLR
property method al l ows both i deal gas and saturated l i qui d reference states.
These property methods use an enthal py method that opti mi zes the accuracy
tradeoff between l i qui d heat capaci ty, heat of vapori zati on, and vapor heat
capaci ty at actual process condi ti ons. Thi s hi ghl y recommended method
el i mi nates many of the probl ems associ ated wi th accurate thermal properti es for
both phases, especi al l y the l i qui d phase.
The l i qui d enthal py of mi xture i s cal cul ated by the fol l owi ng equati on (see the
tabl e l abel ed Li qui d Enthal py Methods i n Chapter 4):
( ) H H H H
m
l
m
ig
m
l
m
ig
+
Where:
H
m
ig
= Enthal py of i deal gas mi xture
=
x H
i i
ig
i
*,
H
i
ig *,
= I deal gas enthal py of pure component i
( ) H H
m
l
m
ig
= Enthal py departure of mi xture

Versi on 10
Chapter 3
For supercri ti cal components, decl ared as Henrys components, the enthal py
departure i s cal cul ated as fol l ows:
H H RT x
T
m
l
m
ig
i
i
l
i

_
,
ln
For subcri ti cal components:
H H
m
l
m
ig
=
( )
x H H H
A A
l
A
ig
A
m
E l *, *, ,
+
H
m
E l ,
=
_
,
RT x
T
B
B
B
2

ln
H H
A
l
A
ig *, *,
= Enthal py departure of pure component A

H
ig *,
and H
l *,
can be cal cul ated based on ei ther saturated l i qui d or i deal gas as
reference state.
Saturated Liquid as Reference State
The saturated l i qui d enthal py at temperature T i s cal cul ated as fol l ows:
H H C dT
i
l
i
ref l
p i
l
T
T
i
ref l
*, ,
,
*,
,
+
Where:
H
i
ref l ,
=
Reference enthal py for l i qui d state at T
i
ref l ,
=
0 at T
i
ref l ,
of 273.15 K by defaul t
C
p i
l
,
*,
= Li qui d heat capaci ty of component i
The i deal gas enthal py at temperature T i s cal cul ated from l i qui d enthal py as
fol l ows:
( ) ( ) H H C dT H T H T p C dT
i
ig
i
ref l
p i
l
vap i i
con l
T
T
v i i
con l
i
l
p i
ig
T
T
i
ref l
i
con l
i
con l
*, ,
,
*, * ,
,
* , *,
,
*,
,
,
,
, + + +

Where:
T
i
con l ,
= Temperature of conversi on from l i qui d to vapor enthal py
for component i
( )
vap i i
con l
H T
* ,
= Heat of vapori zati on of component i at temperature of
T
con l ,
Versi on 10
Property
Model
Descriptions
( ) H T p
v i
con l
i
l
,
* , *,
,
= Vapor enthal py departure of component i at the
conversi on temperature and vapor pressure p
i
l *,
p
i
l *,
= Li qui d vapor pressure of component i
C
p i
ig
,
*,
= I deal gas heat capaci ty of component i
T
i
con l ,
i s the temperature at whi ch one crosses from l i qui d state to the vapor
state. Thi s i s a user -defi ned temperature that defaul ts to the system temperature
T. T
i
con l ,
may be sel ected such that heat of vapori zati on for component i at the
temperature i s most accurate.
The vapor enthal py i s cal cul ated from i deal gas enthal py as fol l ows:
( ) H H H T P
i
v
i
ig
v i
*, *,
,
*
, +
Where:
( ) H T P
v i ,
*
,
= Vapor enthal py departure of pure component i at the system
temperature and pressure
The l i qui d heat capaci ty and the i deal gas heat capaci ty can be cal cul ated from
the ASPEN, DI PPR, or BARI N model s. The heat of vapori zati on can be
cal cul ated from the Watson/DI PPR model . The enthal py departure i s obtai ned
from an equati on-of-state.
Parameter
Name/Element Symbol Default MDS
Lower
Limit Upper Limit Units
RSTATE
2
TREFHL
T
i
ref l ,

TEMPERATURE
DHLFRM
H
i
ref l ,
O MOLE-ENTHALPY
TCONHL
T
i
con l ,
T TEMPERATURE
Enthalpy reference state, RSTATE=2 denotes saturated liquid as reference state.
For WI LS-LR property method TREFHL defaults to 273.15K. For WI LS-GLR property method,
TREFHL defaults to 298.15 K.
Li qui d heat capaci ty i s requi red for al l components.
Versi on 10
Chapter 3
Ideal Gas as Reference State
The saturated l i qui d enthal py i s cal cul ated as fol l ows:
( ) ( ) H H C dT H T p H T p C dT
i
l
i
ref ig
p i
ig
v i i
con ig
i
l
T
T
vap i i
con ig
i
l
p i
l
T
T
i
ref ig
con ig
i
con ig
*, ,
,
*,
,
* , *, * , *,
,
*,
, ,
,
,
,
+ + +

Where:
H
i
ref ig ,
=
Reference state enthal py for i deal gas at T
i
ref ig ,
= Heat of formati on of i deal gas at 298.15 K by defaul t
T
i
ref ig ,
=
Reference temperature correspondi ng to H
i
ref ig ,
. Defaul ts to
298.15 K
T
i
con ig ,
= The temperature at whi ch one crosses from vapor state to l i qui d
state. Thi s i s a user -defi ned temperature that defaul ts to the
system temperature T. T
i
con ig ,
may be sel ected such that heat of
vapori zati on of component i at the temperature i s most accurate.
The i deal gas enthal py i s cal cul ated as fol l ows:
H H C dT
i
ig
i
ref ig
p i
ig
T
T
i
ref ig
*, ,
,
*,
,
+
The vapor enthal py i s cal cul ated as fol l ows:

( ) H H H T P
i
v
i
ig
v i
*, *,
,
, +
The l i qui d heat capaci ty and the i deal gas heat capaci ty can be cal cul ated from
the ASPEN, DI PPR or BARI N model s. The heat of vapori zati on can be cal cul ated
from the Watson/DI PPR model . The enthal py departure i s obtai ned from an
equati on-of-state.
Versi on 10
Property
Model
Descriptions
Parameter
Name/Element
RSTATE 1 or 2

TREFHI
T
i
ref ig ,

TEMPERATURE
DHFORM
H
i
ref ig ,
MOLE-ENTHALPY
TCONHI
T
i
con l ,
T TEMPERATURE
Enthalpy reference state. RSTATE can be 1 (for ideal gas) or 2 (for liquid)
For components with TB <<298.15 K, RSTATE defaults to 1 (ideal gas). TREFHI defaults to 298.15 K.
For components with TB >>298.15 K, RSTATE defaults to 2 (liquid). TREFHL defaults to 298.15 K.
Versi on 10
Chapter 3
Helgeson Equations of State
The Hel geson equati ons of state for standard vol ume V
o
, heat capaci ty C
p
o
,
entropy S
o
, enthal py of formati on H
o
, and Gi bbs energy of formati on G
o
at
i nfi ni te di l uti on i n aqueous phase are:
( ) ( )
( )
V
p p T
Q
p
C
T
T
T
p p
p
p
TX TY
T
T
o
T
p
o
r
r
p
a a a a
c
c
a a
+
+
_
,
+ +
+
_
,
1
]
1
_
,
+
_
,
_
,
+
+
+
_
,
1
]
1
+ +

_
,
_
1 2 3 4
1
2
2 3 3 4
1 1 1 1
1
2
2
1
1

ln

( )
( )
( )
,
_
,
_
,
_
,
1
]
1
1
+
_
,
+
+
+
_
,
1
]
1
+
_
,
_
,

2
2
1
2
2
3 4
1 1 1
1 1
1
T
S S
T
T T T
T T
T T
T
p p
p
p
Y
T
Y
p
o
Tr
o
r r
r
r
r
r
p
Tr Tr
c
c
a a
Pr
Pr Pr
ln ln
ln
( ) ( )
( )
( )
H H T T
T T
p p
p
p
T
T
p p
p
p
TY
T
T
o
f
o
r
r
r
r
r
r
p
Tr
Tr
c c a a
a a
+
_
,
+ +
+
+
_
,
_
,
+
+
+
_
,
1
]
1
+
_
,
+

_
,
_
,
1 2 1 2
2 3 4
1 1
2 1
1
1
1
1

ln
ln

Pr
Pr
( ) ( )
( )
( )
1
1 1
1
1 1 2
2 2
3
_
,
_
,
+
1
]
1
+ +
+
+
_
,
_
,
_
,
_
,
1
]
1
1
+
Tr r Tr
o
f
o
Tr
o
r
r
r r
r
r
r
r
T Y
G G S T T T
T
T
T T p p
p
p
T T
T T T T
T T
T
p p
c a a
c
a
Pr Pr
Pr
ln ln
ln
( )
( )
r
r
Tr
Tr
Tr Tr r
a
p
p
Y T T
+
+
+
_
,
1
]
1
+
_
,
_
,
+
4
1
1
1
1
ln

Pr
Pr
Pr Pr
Versi on 10
Property
Model
Descriptions
Where:
Q
P
X
T T
Y
T
T
P P
P
_
,
_
,
_
,
1
]
1
1
_
,
1
1
1
2
2
2
ln
ln ln
ln
Where:
= Pressure constant for a sol vent (2600 bar for water)

= Temperature constant for a sol vent (228 K for water)
= Born coeffi ci ent
= Di el ectri c constant of a sol vent
T
r
= Reference temperature (298.15 K)
P
r
= Reference pressure (1 bar)
Parameter
AHGPAR/1, . , 4
1 4 a a
, ...,
0
CHGPAR/1, . , 2
1 2 c c
,
x
DHAQHG
H
f
o 0 -0.5*10
10
0.5*10
10
MOLE-ENTHALPY
DGAQHG
G
f
o 0 -0.5*10
10
0.5*10
10
MOLE-ENTHALPY
S25HG
S
Tr
o
Pr
0 -0.5*10
10
0.5*10
10
MOLE-ENTROPY
OMEGHG

Tr Pr
0 -0.5*10
10
0.5*10
10
MOLE-ENTHALPY
I f pressure is under 200 bar, AHGPAR may not be required.

Versi on 10
Chapter 3
References
Tanger J.C. I V and H.C. Hel geson, Cal cul ati on of the thermodynami c and
transport properti es of aqueous speci es at hi gh pressures and temperatures:
Revi sed equati on of state for the standard parti al properti es of i ons and
el ectrol ytes, American J ournal of Science, Vol . 288, (1988), p. 19-98.
Shock E.L. and H.C. Hel geson, Cal cul ati on of the thermodynami c and transport
properti es of aqueous speci es at hi gh pressures and temperatures: Correl ati on
al gori thms for i oni c speci es and equati on of state predi cti ons to 5 kb and 1000C,
Geochi mi ca et Cosmochi mi ca Acta, Vol . 52, p. 2009-2036.
Shock E.L. H.C. Hel geson and D.A. Sverjensky, Cal cul ati on of the
thermodynami c and transport properti es of aqueous speci es at hi gh pressures
and temperatures: Standard parti al mol al properti es of i norgani c neutral speci es,
Geochi mi ca et Cosmochi mi ca Acta, Vol . 53, p. 2157-2183.
Versi on 10
Property
Model
Descriptions
Transport Property Models
Thi s secti on descri bes the transport property model s avai l abl e i n ASPEN PLUS.
The fol l owi ng tabl e provi des an overvi ew of the avai l abl e model s. Thi s tabl e l i sts
the ASPEN PLUS model names, and thei r possi bl e use i n di fferent phase types,
for pure components and mi xtures.
Viscosity models Model name Phase(s) Pure Mixture
Andrade / DIPPR MUL0ANDR, MUL2ANDR L X X
API Liquid Viscosity MUL2API L X
Chapman-Enskog-Brokaw
/DIPPR
MUV0CEB V X
Chapman-Enskog-Brokaw-Wilke
Mixing Rule
MUV2BROK, MUV2WILK V X
Chung-Lee-Starling Low Pressure MUL0CLSL, MUL2CLSL V X X
Chung-Lee-Starling MUV0CLS2, MUV0CLS2,
MUL0CLS2, MUL2CLS2
V L X X
Dean-Stiel Pressure Correction MUV0DSPC, MUV2DSPC V X X
IAPS Viscosity MUV0H2O
MUL0H2O
V
L
X
X
Jones-Dole Electrolyte Correction MUL2JONS L X

Letsou-Stiel MUL0LEST, MUL2LEST L X X
Lucas MUV0LUC, MUV2LUC V X X
Thermal conductivity models
Chung-Lee-StarlingThermal
Conductivtity
KV0CLS2, KV2CLS2,
KL0CLS2, KL2CLS2
V L X X
IAPS Thermal Conductivity KV0H2O
KL0H2O
V
L
X
X
Li Mixing Rule KL2LI L X X

Riedel Electrolyte Correction KL2RDL L X
Sato-Riedel / DIPPR KL0SR, KL2SRVR L X X
Stiel-Thodos / DIPPR KV0STLP V X
continued
Versi on 10
Chapter 3
Thermal conductivity models (continued)
Stiel-Thodos Pressure Correction KV0STPC, KV2STPC V X X
TRAPP Thermal Conductivity KV0TRAP, KV2TRAP,
KL0TRAP, KL2TRAP
V L X X
Vredeveld Mixing Rule KL2SRVR L X X
Diffusivity models Model name Phase(s) Pure Mixture
Binary
DV0CEWL V X
Mixture
DV1CEWL V X
Binary
DV1DKK V X
Mixture
DV1DKK V X
Nernst-Hartley Electrolytes DL0NST, DL1NST L X
Wilke-Chang Binary DL0WC2 L X
Surface tension models
API Surface Tension SIG2API L X
Hakim-Steinberg-Stiel / DIPPR SIG0HSS, SIG2HSS L X
IAPS thermal conductivity SIG0H2O L X
Onsager-Samaras Electrolyte
Correction
SIG2ONSG L X
Viscosity Models
ASPEN PLUS has 12 bui l t-i n vi scosi ty model s.
Model Type
Andrade/DIPPR Liquid
API liquid viscosity Liquid
Chapman-Enskog-Brokaw/DIPPR Low pressure vapor, pure components
Chapman-Enskog-Brokaw-Wilke Mixing Rule Low pressure vapor, mixture
continued
Versi on 10
Property
Model
Descriptions
Model Type
Chung-Lee-Starling Low Pressure Low pressure vapor
Chung-Lee-Starling Liquid or vapor
Dean-Stiel Pressure correction Vapor
IAPS viscosity Water or steam
Jones-Dole Electrolyte Correction Electrolyte
Letsou-Stiel High temperature liquid
Lucas Vapor
TRAPP viscosity Vapor or liquid
Andrade/DIPPR
The l i qui d mi xture vi scosi ty i s cal cul ated by the equati on:
( )
ln
l
i j
ij i j ij i j
k x x m x x +
2 2
Where:
k
ij
=
a
b
T
ij
ij
+
m
ij
=
c
d
T
ij
ij
+
The pure component l i qui d vi scosi ty
i
l *,
can be cal cul ated by two equati ons:
Andrade
DI PPR l i qui d vi scosi ty
The bi nary parameters k
ij
and m
ij
al l ow accurate representati on of compl ex l i qui d
mi xture vi scosi ty. Both bi nary parameters defaul t to zero.
ANDKIJ/1
a
ij
0
ANDKIJ/2
b
ij
0
ANDMIJ/1
c
ij
0
ANDMIJ/2
d
ij
0
Versi on 10
Chapter 3
Andrade
The Andrade equati on i s:
ln ln
*,
i
l
i
i
i l h
A
B
T
C T T T T + + for
MULAND/1
A
i
X VISCOSITY,
TEMPERATURE
MULAND/2
B
i
X TEMPERATURE
MULAND/3
C
i
X TEMPERATURE
MULAND/4
T
l
0.0 X TEMPERATURE
MULAND/5
T
h
500.0 X TEMPERATURE
I f elements 2 or 3 are non-zero, absolute temperature units are assumed for elements 1 to 3.
DIPPR Liquid Viscosity
The equati on for the DI PPR l i qui d vi scosi ty model i s:
ln ln
*,
i
l
i i i i
C
i i
C C T C T C T C T C
i
+ + +
1 2 3 4 6 7
5
for
I f the MULDI P parameters for a gi ven component are avai l abl e, the DI PPR
equati on i s used i nstead of the Andrade model . The Andrade model i s al so used
by PCES.
MULDIP/1
C
i 1
X VISCOSITY,
TEMPERATURE
MULDIP/2,..., 5
C C
i i 2 5
, ...,
0 X TEMPERATURE
MULDIP/6
C
i 6
0 X TEMPERATURE
MULDIP/7
C
i 7
1000 X TEMPERATURE
I f el ements 3, 4, or 5 are non-zero, absol ute temperature uni ts are assumed for el ements 1 to 5.
References
4th ed., (New York: McGraw-Hi l l , 1987), p. 439.
Versi on 10
Property
Model
Descriptions
API Liquid Viscosity
The l i qui d mi xture vi scosi ty i s cal cul ated usi ng a combi nati on of the API and
Andrade/DI PPR equati ons. Thi s model i s recommended for petrol eum and
petrochemi cal appl i cati ons. I t i s used i n the CHAO-SEA, GRAYSON, LK-PLOCK,
PENG-ROB, and RK-SOAVE opti on sets.
For pseudocomponents, the API model i s used:
( )
l
bi i m
l
fcn T x T API V , , , ,
Where:
fcn = A correl ati on based on API Procedures and Fi gures 11A4.1, 11A4.2,
and 11A4.3 (API Technical Data Book, Petrol eum Refi ni ng, 4th edi ti on)
V
m
l
i s obtai ned from the API l i qui d vol ume model .
For real components, the Andrade/DI PPR model i s used.
TB
T
bi
API
API
i
-60.0 500.0
Chapman-Enskog-Brokaw/DIPPR
The pure component l ow pressure vapor vi scosi ty

i
*,
(p = 0) can be cal cul ated
usi ng two equati ons:
Chapman-Enskog
DI PPR vapor vi scosi ty
Chapman-Enskog-Brokaw
The equati on for the Chapman-Enskog model i s:
( )
i
i
i
p
M T
*,
. x

0 2 669 10
26
2
Where:
=
( ) fcn T k
i
,
Versi on 10
Chapter 3
Pol ar parameter i s used to determi ne whether to use the Stockmayer or
Lennard-Jones potenti al parameters: k (energy parameter) and (col l i si on
di ameter). To cal cul ate , the di pol e moment p and ei ther the Stockmayer
parameters or the di pol e moment T
b
and V
bm
are needed. The pol ari ty correcti on
i s from Brokaw.
Parameter
MW
M
i
1.0 5000.0
MUP
p
i
0.0 5x10-24 DIPOLEMOMENT
STKPAR/1
( )
i
ST
k
( ) fcn T V
bi bi i
, , p
X TEMPERATURE
STKPAR/2
i
ST
( ) fcn T V
bi bi i
, , p
X LENGTH
LJPAR/1
( )
i
LJ
k
( ) fcn T
ci i
,
X TEMPERATURE
LJPAR/2
i
LJ
( ) fcn T p
ci ci i
, ,
X LENGTH
DIPPR Vapor Viscosity
The equati on for the DI PPR vapor vi scosi ty model i s:
( ) ( )

i i
C
i i i i
p C T C T C T C T C
i
*,
/ + + 0 1
1 3 4
2
6 7
2
for
I f the MUVDI P parameters for a gi ven component are avai l abl e, the DI PPR
equati on i s used i nstead of the Chapman-Enskog-Brokaw model . PCES uses the
DI PPR vapor vi scosi ty model .
Parameter Name/Element Symbol Default MDS LoweLimit Upper Limit Units
MUVDIP/1
C
i 1
X VISCOSITY
MUVDIP/2
C
i 2
0 X
MUVDIP/3, 4
C C
i i 3 4
,
0 X TEMPERATURE
MUVDIP/5
C
i 5
0 X
MUVDIP/6
C
i 6
0 X TEMPERATURE
MUVDIP/7
C
i 7
1000 X TEMPERATURE
Versi on 10
Property
Model
Descriptions
References
R.C. Rei d, J.M. Prausni tz, and B.E. Pol i ng. The Properties of Gases and Liquids,
Chapman-Enskog-Brokaw-Wilke Mixing Rule
The l ow pressure vapor mi xture vi scosi ty i s cal cul ated by the Wi l ke approxi mati on
of the Chapman-Enskog equati on:
( )
( )
p
y p
y
i
i i
j ij
j

0
0
*,
For
ij
,the formul ati on by Brokaw i s used:
( )
ij
i
j
p
1
]
1
1
*,
*,
0
Where:
A
ij
=
( )
fcn M M
i j
, , and the correcti on factor for pol ar gases
Sij =
( )
( )
fcn k T
ST
, ,
Lennard-Jones potenti al parameters: k (energy parameter ) and (col l i si on
di ameter). To cal cul ate , the di pol e moment p, and ei ther the Stockmayer
parameters or T
b
and V
bm
are needed.
The pure component vapor vi scosi ty

i
*,
(p = 0) can be cal cul ated usi ng the
Chapman- Enskog-Brokaw/DI PPR (or another) l ow pressure vapor vi scosi ty
model .
Ensure that you suppl y parameters for

i
*,
(p = 0).
Versi on 10
Chapter 3
Parameter
MW
M
i
1.0 5000.0
MUP
p
i
0.0 5x10-24 DIPOLEMOMENT
STKPAR/1
( )
i
ST
k
( ) fcn T V
bi bi i
, , p
X TEMPERATURE
STKPAR/2
i
ST
( ) fcn T V
bi bi i
, , p
X LENGTH
References
R.C. Rei d, J.M. Prausni tz, and T.K. Sherwood, The Properties of Gases and
Liquids, 3rd ed., (New York: McGraw-Hi l l , 1977), pp. 410416.
Chung-Lee-Starling Low-Pressure Vapor Viscosity
The l ow-pressure vapor vi scosi ty by Chung, Lee, and Starl i ng i s:
( )
( )
p
MT F
V
C
cm
0
0 40785
1
2
2
3
.
Where the vi scosi ty col l i si on i ntegral i s:

( )
fcn T
r
The shape and pol ari ty correcti on i s:
( ) F fcn
c r
, , p
The parameter p
r
i s the reduced di pol emoment:
( )
p
p
r
cm c
V T
4152
1
2
.
The pol ar parameter i s tabul ated for certai n al cohol s and carboxyl i c aci ds.
The previ ous equati ons can be used for mi xtures when appl yi ng these mi xi ng
rul es:
V y y V
cm i j cij
j i

T
y y T V
V
c
i j cij cij
j i
cm

Versi on 10
Property
Model
Descriptions
M
x x T V M
T V
i j cij cij ij
j i
c cm
1
]
1
1

2
3
2
3
2

x x V
V
i j ij cij
j i
cm
p
p
r
cm c
V T
1313
1
2
.
p
p p
4
i
2
j
2

x x V
V
i j c
j i
cij

x x
i j ij
j i
Where:
V
cij
=
( )( )
1
1
2

ij ci cj
V V
ij
= 0 (i n al most al l cases)
T
cij
=
( )( )
1
1
2

ij ci cj
T T
ij
ij
=
( )

i j
+
2
M
ij
=
( )
2
1
2
M M
M M
i j
i j
+
1
]
1
1
ij
=
( )

i j
1
2
Versi on 10
Chapter 3
TCCLS
T
ci
VCCLS
V
ci
MW
M
i
1.0 5000.0
MUP
p
i
0.0
5 10
24
x

DIPOLEMOMENT
OMGCLS
i
OMEGA x -0.5 2.0
CLSK
i
0.0 x 0.0 0.5
CLSKV
ij
0.0 x -0.5 -0.5
CLSKT
ij
0.0 x -0.5 0.5
The model specific parameters also affect the Chung-Lee-Starling Viscosity and the Chung-Lee-Starling
Thermal Conductivity models.
References
4th ed., (New York: McGraw-Hi l l , 1987), p. 396, p. 413.
Chung-Lee-Starling Viscosity
The Chung-Lee-Starl i ng vi scosi ty equati on for vapor and l i qui d, hi gh and l ow
pressure i s:
( ) ( )
+
40 785 36344
1
2
2
3
1
2
2
3
1 2
. . MT F
V
f
MT
V
f
C
cm
c
cm
Wi th:
f
1
=
( ) fcn V
m cm r
, , , , p
f
2
=
( ) fcn
r
, , p
F
2
=
( ) fcn
r
, , p
The mol ar densi ty can be cal cul ated usi ng an equati on-of-state model (for exampl e,
the Benedi ct-Webb-Rubi n). The parameter p
r
i s the reduced di pol emoment:
( )
p
p
r
cm c
V T
4152
1
2
.
Versi on 10
Property
Model
Descriptions
For l ow pressures, f
1
i s reduced to 1.0 and f
2
becomes negl i gi bl e. The equati on
reduces to the l ow pressure vapor vi scosi ty model by Chung-Lee and Starl i ng.
The previ ous equati ons can be used for mi xtures when appl yi ng these mi xi ng
rul es:
V y y V
cm i j cij
j i

T
y y T V
V
c
i j cij cij
j i
cm

M
x x T V M
T V
i j cij cij ij
j i
c cm
1
]
1
1

2
3
2
3
2

x x V
V
i j ij cij
j i
cm
p
p
r
cm c
V T
1313
1
2
.
p
p p
4
i
2
j
2

x x V
V
i j c
j i
cij

x x
i j ij
j i
Where:
V
cij
=
( )( )
1
1
2

ij ci cj
V V
ij
T
cij
=
( )( )
1
1
2

ij ci cj
T T
ij
ij
=
( )

i j
+
2
Versi on 10
Chapter 3
M
ij
=
( )
2
1
2
M M
M M
i j
i j
+
1
]
1
1
ij
=
( )

i j
1
2
TCCLS
T
ci
VCCLS
V
ci
MW
M
i
1.0 5000.0
MUP
p
i
0.0
5 10
24
x

DIPOLEMOMENT
OMGCLS
i
OMEGA x -0.5 2.0
CLSK
i
0.0 x 0.0 0.5
CLSKV
ij
0.0 x -0.5 -0.5
CLSKT
ij
0.0 x -0.5 0.5
The model specific parameters affect the results of the Chung-Lee-Starling Thermal Conductivity and Low
Pressure Viscosity models as well.
References
Dean-Stiel Pressure Correction
The pressure correcti on to l ow pressure vapor vi scosi ty or the resi dual vapor
vi scosi ty by Dean and Sti el i s:
( ) ( )
( )

p p
m
rm

1
]
1
0
108
10 10
1 439
1111
1 858
.
.
.
.
Where
(p = 0) i s obtai ned from a l ow pressure vi scosi ty model (for exampl e,

Chapman-Enskog-Brokaw). The di mensi onl ess-maki ng factor i s:
= N
T
M p
A
c
c
2
1
6
1
2
2
3
Versi on 10
Property
Model
Descriptions
T
c
= y T
i ci
i
M =
y M
i i
i
p
c
=
Z RT
V
cm c
cm
V
cm
= y V
i ci
i
Z
cm
= y Z
i ci
i
rm
=
V
V
cm
m
The parameter <$EV sub m sup {^v}> i s obtai ned from Redl i ch-Kwong equati on-
of-state.
MW
M
i
1.0 5000.0
VC
V
ci
IAPS Viscosity for Water
The I APS vi scosi ty model s, devel oped by the I nternati onal Associ ati on for
Properti es of Steam, cal cul ate vapor and l i qui d vi scosi ty for water and steam.
These model s are used i n opti on sets STEAMNBS and STEAM-TA.
The general form of the equati on for the I APS vi scosi ty model s i s:
( )
w
fcn T p ,
Where:
fcn = Correl ati on devel oped by I APS
The model s are onl y appl i cabl e to water. There are no parameters requi red for the
model s.
Versi on 10
Chapter 3
J ones-Dole Electrolyte Correction
The Jones-Dol e model cal cul ates the correcti on to the l i qui d mi xture vi scosi ty of a
sol vent mi xture, due to the presence of el ectrol ytes:

l
solv ca
l
ca
+
_
,
1 (1)
Where:
solv
= Vi scosi ty of the l i qui d sol vent mi xture, cal cul ated by the
Andrade/DI PPR model
ca
l
= Contri buti on to the vi scosi ty correcti on due to apparent el ectrol yte
ca
The parameter
ca
l
can be cal cul ated by three di fferent equati ons.
If these parameters are available Use this equation
IONMOB and IONMUB Dole-Jones
IONMUB Breslau-Miller
Carbonell
J ones-Dole
The Jones-Dol e equati on i s:
ca
l
ca ca
a
ca ca
a
A c B c + 2)
Where:
c
x
V
ca
a ca
a
m
l
= Concentrati on of apparent el ectrol yte ca (3)

x
ca
a
= Mol e fracti on of apparent el ectrol yte ca
A
ca
=
( ) ( )
( )
145
2
4
3 2
1
2
.

solv
l
c a
c a
c a
c a c a
T
L L
L L
L L
L L L L
+

+ +
1
]
1
1
(4)
L
a
= l l T
a a , , 1 2
+ (5)
L
c
= l l T
c c , , 1 2
+ (6)
Versi on 10
Property
Model
Descriptions
B
ca
=
( ) ( )
b b T b b T
c c a a , , , , 1 2 1 2
+ + + (7)
Breslau-Miller
The Bresl au-Mi l l er equati on i s:
( )
ca
l
e ca
a
ca
a
V c c + 25 10 05
2
. . V
e
(8)
Where the effecti ve vol ume V
c
i s gi ven by:
( )
V
B
e
ca
0 002
2 60
.
.
for sal ts i nvol vi ng uni val ent i ons (9)
( )
V
B
e
ca
0 011
506
.
.
for other sal ts (9a)
Carbonell
The Carbonel l equati on i s:
ca
l
k k
a
k
ca
a
M x
c
T
_
,
1
]
1
exp . . 0 48193 10 (10)

Where:
M
k
= Mol ecul ar wei ght of an apparent el ectrol yte component k
You must provi de parameters for the Andrade model , used for the cal cul ati on of
the l i qui d mi xture vi scosi ty of the sol vent mi xture.
CHARGE z 0.0
MW M 1.0 5000.0
IONMOB/1
I
1
AREA, MOLES
IONMOB/2
I
2
0.0 AREA, MOLES,
TEMPERATURE
IONMUB/1
b
1
MOLE-VOLUME
IONMUB/2
b
2
0,0 MOLE-VOLUME,
TEMPERATURE
References
A. L. Horvath, Handbook of Aqueous Elecrolyte Solutions, (Chi chester: El l i s
Horwood, 1985).
Versi on 10
Chapter 3
Letsou-Stiel
The Letsou-Sti el model cal cul ates l i qui d vi scosi ty at hi gh temperatures for
0 76 098 . . T
r
. Thi s model i s used i n PCES.
The general form for the model i s:
( ) ( )

l l l
+
0 1
Where:
( )

l
0
= ( ) fcn T x T
i ci
, ,
( )

l
1
= ( ) fcn T x T
i ci
, ,
= ( ) fcn x M T p
i i ci ci i
, , , ,
= x
i i
i

MW
M
i
1.0 5000.0
TC
T
ci
PC
p
ci

10
5
10
5
PRESSURE
OMEGA

i
-0.5 2.0
References
R.C. Rei d, J.M. Pransni tz, and B.E. Pol i ng, The Properties of Gases and Liquids,
Lucas Vapor Viscosity
The equati on for the Lucas vapor vi scosi ty model i s:
( ) ( )

p
YF F
p Q
0
Where the di mensi onl ess l ow pressure vi scosi ty i s gi ven by:
( ) ( ) ( ) ( ) ( )
p fcn T F p F p
r P Q
0 0 0
Versi on 10
Property
Model
Descriptions
The di mensi onl ess-maki ng group i s:
N
T
M p
A
c
c
2
1
6
1
2
2
3
The pressure correcti on factor Y i s:
( ) Y fcn p T
r r
,
The pol ar and quantum correcti on factors at hi gh and l ow pressure are:
F
P
=
( ) ( )
fcn Y F p
P
, 0
F
Q
=
( ) ( )
fcn Y F p
Q
, 0
( ) F p
Pi
0 =
( ) fcn T p Z
ri ci ci i
, , , p
( ) F p
Qi
0 =
( ) fcn T
ri
, but i s onl y nonuni ty for the quantum gates i H E
2 2
,
and He.
The Lucas mi xi ng rul es are:
T
c
= y T
i ci
i
p
c
=
RT
y Z
y V
V
RZ T
p
c
i ci
i
i ci
i
ci
ci ci
ci
,
M =
y M
i i
i
( ) F p
P
0 = ( ) y F p
i Pi

0
( ) F p
Q
0 = ( ) A y F p
i Qi

0 ,
Where A di ffers from uni ty onl y for certai n mi xtures.
Versi on 10
Chapter 3
TCLUC
T
ci
PCLUC
p
ci
PC x
10
5
10
8
PRESSURE
ZCLUC
Z
ci
ZC x 0.1 0.5
MW
M
i
1.0 5000.0
MUP
p
i
0.0
5 10
24
x

DIPOLEMOMENT
References
4th ed., (New York: McGraw-Hi l l , 1987), p. 421, 431.
TRAPP Viscosity Model
The general form for the TRAPP vi scosi ty model i s:
( ) fcn t p x M T p V Z
i ci ci ci ci i
, , , , , , , ,
Where:
The parameter x i s the mol e fracti on vector; fcn i s a correspondi ng states
correl ati on based on the model for vapor and l i qui d vi scosi ty TRAPP, by the
Nati onal Bureau of Standards (NBS, currentl y NI ST). The model can be used for
both pure components and mi xtures. The model shoul d be used for nonpol ar
components onl y.
MW
M
i
1.0 5000.0
TCTRAP
T
ci
PCTRAP
p
ci
PC x
10
5
10
8
PRESSURE
VCTRAP
V
ci
ZCTRAP
Z
ci
ZC x 0.1 1.0
OMGRAP

i
OMEGA x -0.5 3.0
References
J.F. El y and H.J.M. Hanl ey, "Predi cti on of Transport Properti es. 1. Vi scosi ti es of
Fl ui ds and Mi xtures," I nd. Eng. Chem. Fundam., Vol . 20, (1981), pp. 323332.
Versi on 10
Property
Model
Descriptions
Thermal Conductivity Models
ASPEN PLUS has ei ght bui l t-i n thermal conducti vi ty model s. Thi s secti on
descri bes the thermal conducti vi ty model s avai l abl e.
Model Type
Chung-Lee-Starling Vapor or liquid
IAPS Water or stream
Li Mixing Rule Liquid mixture
Riedel Electrolyte Correction Electrolyte
Sato-Riedel/DIPPR Liquid
Stiel-Thodos/DIPPR Low pressure vapor
Stiel-Thodos Pressure Correction Vapor
TRAPP Thermal Conductivity Vapor or liquid
Vredeveld Mixing Rule Liquid mixture
Wassiljewa-Mason-Saxena Mixing Rule Low pressure vapor
Chung-Lee-Starling Thermal Conductivity
The mai n equati on for the Chung-Lee-Starl i ng thermal conducti vi ty model i s:
( )

+
312 0
1 2
. p
M
f f
Where:
f
1
= ( ) fcn
m r
, , , p
f
2
= ( ) fcn T M V
c cm rm r
, , , , , , p
= ( ) fcn C T
r
, ,
( ) p 0 can be cal cuated by the l ow pressure Chung-Lee-Starl i ng model . The
mol ar densi ty can be cal cul ated usi ng an equati on-of-state model (for exampl e,
the Benedi ct-Webb-Rubi n equati on-of-state). The parameter p
r
i s the reduced
di pol emoment:
( )
p
p
r
cm c
V T
4152
1
2
.
Versi on 10
Chapter 3
For l ow pressures, f
1
i s reduced to 1.0 and f
2
i s reduced to zero. Thi s gi ves the
Chung-Lee-Starl i ng expressi on for thermal conducti vi ty of l ow pressure gases.
The same expressi ons are used for mi xtures. The mi xture expressi on for ( ) p 0
must be used. (See Chung-Lee-Starl i ng Low-Pressure Vapor Vi scosi ty on page 3-
127.)
C x C
i i
i

,
M
x x T V M
T V
i j cij cij ij
j i
c cm
1
]
1
1

2
3
2
3
2

x x V
V
i j ij cij
j i
cm
p
p
r
cm c
V T
1313
1
2
.
p
p p
4
i
2
j
2

x x V
V
i j c
j i
cij

x x
i j ij
j i
Where:
V
cij
=
( )( )
1
1
2

ij ci cj
V V
ij
T
cij
=
( )( )
1
1
2

ij ci cj
T T
ij
ij
=
( )

i j
+
2
M
ij
=
( )
2
1
2
M M
M M
i j
i j
+
1
]
1
1
ij
=
( )

i j
1
2
Versi on 10
Property
Model
Descriptions
TCCLS
T
ci
VCCLS
V
ci
MW
M
i
1.0 5000.0
MUP
p
i
0.0 5 10
24
x

DIPOLEMOMENT
OMGCLS
i
OMEGA x -0.5 2.0
CLSK
i
0.0 x 0.0 0.5
CLSKV
ij
0.0 x -0.5 -0.5
CLSKT
ij
0.0 x -0.5 0.5
The model-specific parameters also affect the results of the Chung-Lee-Starling viscosity models.
References
4th ed., (New York: McGraw-Hi l l , 1987), p. 505, 523.
IAPS Thermal Conductivity for Water
The I APS thermal conducti vi ty model s were devel oped by the I nternati onal
Associ ati on for Properti es of Steam. These model s can cal cul ate vapor and l i qui d
thermal conducti vi ty for water and steam. They are used i n opti on sets
STEAMNBS and STEAM-TA.
The general form of the equati on for the I APS thermal conducti vi ty model s i s:
( )
w
fcn T p ,
Where:
The model s are onl y appl i cabl e to water. No parameters are requi red.
Li Mixing Rule
Li qui d mi xture thermal conducti vi ty i s cal cul ated usi ng Li equati on (Rei d et.al .,
1987):

l
i j i j ij

Versi on 10
Chapter 3
Where:
( ) ( )

ij i
l
j
l
+
1
]
1

2
1
1
1
*, *,
i
i i
l
j i j
l
xV
xV
*,
*,
The pure component l i qui d mol ar vol ume V
i
l *,
i s cal cul ated from the Rackett
model .
The pure component thermal conducti vi ty
i
l *,
can be cal cul ated by two equati ons:
Sato-Ri edel
DI PPR
See the Sato-Ri edel /DI PPR model for descri pti ons.
Riedel Electrolyte Correction
The Ri edel model can cal cul ate the correcti on to the l i qui d mi xture thermal
conducti vi ty of a sol vent mi xture, due to the presence of el ectrol ytes:
( ) ( ) ( )
( )
( )

l
solv
l
c a
a
m
l
ca
solv
l
solv
l
T T a a
x
V
T
T
ca
+ +
1
]
1
1

293
293
Where:
solv
l
= Thermal conducti vi ty of the l i qui d sol vent mi xture, cal cul ated by
the Sato-Ri edel model
x
ca
a
= Mol e fracti on of the apparent el ectrol yte ca
a a
c a
, = Rei del i oni c coeffi ci ent
V
m
l
= Apparent mol ar vol ume computed by the Cl arke densi ty model
Apparent el ectrol yte mol e fracti ons are computed from the true i on mol e-fracti ons
and i oni c charge number. They can al so be computed i f you use the apparent
component approach. A more detai l ed di scussi on of thi s method i s found i n
Chapter 5.
You must provi de parameters for the Sato-Ri edel model . Thi s model i s used for
the cal cul ati on of the thermal conducti vi ty of sol vent mi xtures.
Versi on 10
Property
Model
Descriptions
CHARGE z 0.0
IONRDL a 0.0
THERMAL CONDUCTI VI TY, MOLE-VOLUME

Sato-Riedel/DIPPR
The pure component thermal conducti vi ty can be cal cul ated by two equati ons:
Sato-Ri edel
DI PPR
Sato-Riedel
The Sato-Ri edel equati on i s (Rei d et al ., 1987):
( )
( )
i
l
i
ri
bri
M
T
T
*,
.
+
+
_
,
11053152 3 20 1
3 20 1
1
2
2
3
2
3
Where:
T
bri
= T T
bi ci
T
ri
= T T
ci
MW
M
i
1.0 5000.0
TC
T
ci
TB
T
bi
DIPPR
The DI PPR equati on i s:
i
l
i i i i i i i
C C T C T C T C T C T C
*,
+ + + +
1 2 3
2
4
3
5
4
6 7
for
Li near extrapol ati on of
*,l
versus T occurs outsi de of bounds.
I f the KLDI P parameters for a gi ven component are avai l abl e, the DI PPR model
i s used i nstead of the Sato-Ri edel model . The DI PPR model i s al so used by PCES.
Versi on 10
Chapter 3
KLDIP/1
C
i 1
x THERMAL-
CONDUCTIVITY,
TEMPERATURE
KLDIP/2, , 5
C C
i i 2 5
, ...,
0 x THERMAL-
CONDUCTIVITY,
TEMPERATURE
KLDIP/6
C
i 6
0 x TEMPERATURE
KLDIP/7
C
i 7
100
0
x TEMPERATURE
Vredeveld Mixing Rule
Li qui d mi xture thermal conducti vi ty i s cal cul ated usi ng the Vredevel d equati on
(Rei d et al ., 1977):
( )

l
i
l
i i
j j
j i
x M
x M
_
,
1
]
1
1

*,
2
1
2
Pure component thermal conducti vi ty
i
l *,
can be cal cual ted by two equati ons:
Sato-Ri edel
DI PPR
See the Sato-Ri edel /DI PPR model for descri pti ons.
References
R.C. Rei d, J.M. Prausni tz, and T.K. Sherwood, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hi l l , 1977), p. 533.
Stiel-Thodos/DIPPR
The pure component thermal conducti vi ty for l ow pressure gasses can be cal cul ated
by two equati ons:
Sti el -Thodos
DI PPR vapor thermal conducti vi ty
Versi on 10
Property
Model
Descriptions
Stiel-Thodos
The Sti el -Thodos equati on i s:
( ) ( )

i i pi
ig
i
C R M
*, *, *,
. . x + 115 169 10
4
Where:
( )

i
p
*,
0 can be obtai ned from the Chapman-Enskog-Brokaw model .
C
pi
ig *,
i s obtai ned from the I deal Gas Heat Capaci ty model .
R i s the uni versal gas constant.
MW
M
i
1.0 5000.0
DIPPR Vapor Thermal Conductivity
The DI PPR equati on for vapor thermal conducti vi ty i s:
( )
i
l
i
C
i i i i
C T C T C T C T C
i
*,
+ +
1 3 4
2
6 7
2
1 for
Li near extrapol ati on of

i
*
versus T occurs outsi de of bounds.
I f the KVDI P parameters for a gi ven component are avai l abl e, the DI PPR
equati on i s used i nstead of the Sti el -Thodos equati on. The DI PPR equati on i s
al so used i n PCES.
KVDIP/1
C
i 1
x THERMAL
CONDUCTIVITY
KVDIP/2
C
i 2
0 x
KVDIP/3, 4
C C
i i 3 4
,
0 x TEMPERATURE
KVDIP/5 0 x
KVDIP/6
C
i 6
0 x TEMPERATURE
KVDIP/7
C
i 7
1000 x TEMPERATURE
Versi on 10
Chapter 3
References
R.C. Rei d, J.M. Prauni tz, and B.E. Pol i ng, The Properties of Gases and Liquid,
Stiel-Thodos Pressure Correction Model
The pressure correcti on to a pure component or mi xture thermal conducti vi ty at
l ow pressure i s gi ven by:
( ) ( )

fcn p y M T V Z
n
rm i i ci ci ci
0 , , , , , ,
Where:
rm
= y
V
V
i
ci
m
i

The parameter V
m
can be obtai ned from Redl i ch-Kwong.

( )
p 0 can be obtai ned from the l ow pressure Sti el -Thodos Thermal

Conducti vi ty model (Sti el -Thodos/DI PPR).
Thi s model shoul d not be used for pol ar substances, hydrogen, or hel i um.
MW
M
i
1.0 5000.0
TC
T
ci
PC 105 108 PRESSURE
VC
V
ci
ZC
Z
ci
0.1 0.5
References
R.C. Rei d, J.M. Prauni tz, and B.E. Pol i ng, The Properties of Gases and Liquids,
TRAPP Thermal Conductivity Model
The general form for the TRAPP thermal conducti vi ty model i s:
( )
fcn T P x M T p V Z C
i ci ci ci ci i p
ig
i
, , , , , , , , ,
*,
Versi on 10
Property
Model
Descriptions
Where:
x = Mol e fracti on vector
C
p
ig
i
*,
= I deal gas heat capaci ty cal cul ated usi ng the ASPEN PLUS or
DI PPR i deal gas heat capaci ty equati ons
fcn = Correspondi ng states correl ati on based on the model for vapor and
l i qui d thermal conducti vi ty made by the Nati onal Bureau of
standards (NBS, currentl y NI ST)
The model can be used for both pure components and mi xtures. The model shoul d
be used for nonpol ar components onl y.
MW
M
i
1.0 5000.0
TCTRAP
T
ci
PCTRAP
p
ci
PC x 105 108 PRESSURE
VCTRAP
V
ci
ZCTRAP
Z
ci
ZC x 0.1 1.0
OMGRAP

i
OMEGA x -0.5 3.0
References
J.F. El y and H.J. M. Hanl ey, "Predi cti on of Transport Properti es. 2. Thermal
Conducti vi ty of Pure Fl ui ds and Mi xtures," I nd. Eng. Chem. Fundam., Vol . 22,
(1983), pp. 9097.
Wassiljewa-Mason-Saxena Mixing Rule
The vapor mi xture thermal conducti vi ty at l ow pressures i s cal cul ated from the
pure component val ues, usi ng the Wassi l jewa-Mason-Saxena equati on:
( )
( )
p
y p
y A
i i
j ij
j
i

0
0
*,
( )
( )
( ) ( )
[ ]
A
n p
n p
M M M M
ij
i
j
j i i j
+

1
]
1
1
1
]
1
1
+ 1
0
0
8 1
1
2
1
4
1
2
1
2
*,
*,

Versi on 10
Chapter 3
Where:

i
*,
= Cal cul ated by the Sti el -Thodos model or the DI PPR thermal
conducti vi ty model (Sti el -Thodos/DI PPR)
( )

i
p
*,
0
= Obtai ned from the Chapman-Enskog-Brokaw model
C
pi
ig *,
= Obtai ned from the I deal Gas Heat Capaci ty model
R = Uni versal gas constant
You must suppl y parameters for ( )

i
p
*,
0 and

i
*.,
.
MW
M
i
1.0 5000.0
References
4th ed., (New York: McGraw-Hi l l , 1987), pp. 530531.
Versi on 10
Property
Model
Descriptions
Diffusivity Models
ASPEN PLUS has seven bui l t-i n di ffusi vi ty model s. Thi s secti on descri bes the
di ffusi vi ty model s avai l abl e.
Model Type
Chapman-Enskog-Wilke-Lee (Binary) Low pressure vapor
Chapman-Enskog-Wilke-Lee (Mixture) Low pressure vapor
Dawson-Khoury-Kobayashi (Binary) Vapor
Dawson-Khoury-Kobayashi (Mixture) Vapor
Nernst-Hartley Electrolyte
Wilke-Chang (Binary) Liquid
Wilke-Chang (Mixture) Liquid
Chapman-Enskog-Wilke-Lee (Binary)
The bi nary di ffusi on coeffi ci ent at l ow pressures ( ) D p
ij
0 i s cal cul ated usi ng

the Chapman-Enskog-Wi l ke-Lee model :
( ) ( )
[ ]
( )
[ ]
D p f M
T f M
p
ij
ok D

0 21989 10 50665 10
22 3
2
2
3
. x . x
Where:
( ) ( ) ( )
[ ]
f M M M M M
i j i j
+
1
2
The col l i si on i ntegral for di ffusi on i s:
D
=
( )
fcn T k
ij
,
The bi nary si ze and energy parameters are defi ned as:
ij
=
( )

i j
+
2
ij
=
( )

i j
1
2
Lennard-Jones potenti al parameters: k (energy parameter ) and (col l i si on
di ameter). To cal cul ate , the di pol e moment p, and ei ther the Stockmayer
parameters or T
b
and V
bm
are needed.
Versi on 10
Chapter 3
Parameter
Name/Element
MW
M
i
1.0 5000.0
MUP
p
i
0.0
5 10
24
X

DIPOLEMOMENT
STKPAR/1
( ) k
ST
( ) fcn T V
i bi bi
p , ,
x TEMPERATURE
STKPAR/2

ST ( ) fcn T V
i bi bi
p , ,
x LENGTH
LJPAR/1
( ) k
LJ
( ) fcn T
ci i
,
x TEMPERATURE
LJPAR/2

LJ ( ) fcn T
ci i i
, p ,
x LENGTH
References
R.C. Rei d, J.M. Prauni tz, and B.E. Pol i ng, The Properties of Gases and Liquids, 4th
ed., (New York: McGraw-Hi l l , 1987), p. 587.
Chapman-Enskog-Wilke-Lee (Mixture)
The di ffusi on coeffi ci ent of a gas i nto a gas mi xture at l ow pressures i s cal cul ated
usi ng Bl ancs l aw:
( )
( )
D p y
D p
y
i j
ij
j j i j i
1
]
1
1

0
0
The bi nary di ffusi on coeffi ci ent ( ) D p
ij
0 at l ow pressures i s cal cul ated usi ng

the Chapman-Enskog-Wi l ke-Lee model . (See Chapman-Enskog-Wi l ke-Lee
(Bi nary) on page 3-148.)
You must provi de parameters for thi s model .
Versi on 10
Property
Model
Descriptions
DVBLNC
1 x
DVBLNC is set to 1 for a diffusing component and 0 for a non-diffusing component.

References
Dawson-Khoury-Kobayashi (Binary)
The bi nary di ffusi on coeffi ci ent D
ij
at hi gh pressures i s cal cul ated from the

Dawson-Khoury-Kobayashi model :
( ) ( )
[ ]
( ) ( ) D a a p a p D p p atm
ij m rm rm rm ig m

+ + + 1 0 1
1 2
2
3
3

rm cm m
V V

m m
V 1
V
y V y V
y y
cm
i ci j cj
i j
+
+
* *
( ) D p
ij
0 i s the l ow-pressure bi nary di ffusi on coeffi ci ent obtai ned from the
Chapman-Enskog-Wi l ke-Lee model .
The parameters
m
and V
m
are obtai ned from the Redl i ch-Kwong equati on-of-

state model .
You must suppl y parameters for these two model s.
Subscri pt i denotes a di ffusi ng component. j denotes a sol vent.
VC
V
ci
References
R.C. Rei d, J.M. Prausni tz, and T.K. Sherwood. The Properties of Gases and
Liquids, 3rd ed., (New York: McGraw-Hi l l , 1977), pp. 560-565.
Versi on 10
Chapter 3
Dawson-Khoury-Kobayashi (Mixture)
The di ffusi on coeffi ci ent of a gas i nto a gas mi xture at hi gh pressure i s cal cul ated
usi ng Bl ancs l aw:
D y
D
y
i j
ij
j j i j i
1
]
1
1

The bi nary di ffusi on coeffi ci ent D
ij
at hi gh pressures i s cal cul ated from the

Dawson-Khoury-Kobayashi model . (See Dawson-Khoury-Kobayashi (Bi nary) on
page 3-150.)
You must provi de parameters for thi s model .
DVBLNC 1
DVBLNC i s set to 1 for a di ffusi ng component and 0 for a nondi ffusi ng component.
References
Nernst-Hartley
The effecti ve di ffusi vi ty of an i on i i n a l i qui d mi xture wi th el ectrol ytes can be
cal cul ated usi ng the Nernst-Hartl ey model :
( )
D
RT
z F
l l T x
i
i
i e i k
k
_
,
+

2 1, ,
(1)
Where:
F =
9 65 10
7
. x C/kmol e (Faradays number)
x
k
= Mol e fracti on of any mol ecul ar speci es k
z
i
= Charge number of speci es i
The bi nary di ffusi on coeffi ci ent of the i on wi th respect to a mol ecul ar speci es i s set
equal to the effecti ve di ffusi vi ty of the i on i n the l i qui d mi xture:
D D
ik i
(2)
Versi on 10
Property
Model
Descriptions
The bi nary di ffusi on coeffi ci ent of an i on i wi th respect to an i on j i s set to the
mean of the effecti ve di ffusi vi ti es of the two i ons:
( )
D
D D
ij
j
2
Parameter Name/Element Symbol Default
Lower
Limit Upper Limit Units
CHARGE z 0.0
IONMOB/1
I
1
AREA, MOLES
IONMOB/2
I
2
0.0 AREA, MOLES, TEMPERATURE
References
A. L. Horvath, Handbook of Aqueous Electrolyte Solutions, (Chi chester: El l i s
Horwood, Ltd, 1985).
Wilke-Chang (Binary)
The Wi l ke-Chang model cal cul ates the l i qui d di ffusi on coeffi ci ent of component i i n
a mi xture at fi ni te concentrati ons:
( ) ( )
D D D
ij
l
ij
l
x
ji
l
x
j i
, ,
The equati on for the Wi l ke-Chang model at i nfi ni te di l uti on i s:
( )
( )
D
M T
n V
ij
l
j j
j
l
bi
l

,
*,
.
. x 117282 10
16
0 6
1
2
Where i i s the di ffusi ng sol ute and j the sol vent:
j
= Associ ati on factor of sol vent
n
j
l
= Li qui d vi scosi ty of the sol vent si mul ati on. Thi s can be obtai ned from
the Andrade/DI PPR model . You must provi de parameters for one of
these model s.
Versi on 10
Chapter 3
MW
M
j
1.0 5000.0
VB
V
bi
l *,
References
Wilke-Chang (Mixture)
The Wi l ke-Chang model cal cul ates the l i qui d di ffusi on coeffi ci ent of component i i n
a mi xture.
The equati on for the Wi l ke-Chang model i s:
( )
( )
D
M T
n V
i
l
l
bi
l

117282 10
16
0 6
1
2
. x
*,
.
Wi th:
M
x M
x
j j j
j i
j
j i
Where:
j
= Associ ati on factor of sol vent
n
l
= Mi xture l i qui d vi scosi ty of al l nondi ffusi ng components. Thi s can be
obtai ned from the Andrade/DI PPR or another l i qui d mi xture vi scosi ty
model . You must provi de parameters for one of these model s.
MW
M
j
1.0 5000.0
VB
V
bi
l *,
DLWC 1
Versi on 10
Property
Model
Descriptions
References
R.C. Rei d, J.M. Praunsni tz, and B.E. Pol i ng, The Properties of Gases and Liquids,
Surface Tension Models
ASPEN PLUS has four bui l t-i n surface tensi on model s.Thi s secti on descri bes the
surface tensi on model s avai l abl e.
Model Type
API Liquid-vapor
IAPS Water-stream
Hakim-Steinberg-Stiel/DIPPR Liquid-vapor
Onsager-Samaras Electrolyte Correction Electrolyte liquid-vapor
API Surface Tension
The l i qui d mi xture surface tensi on for hydrocarbons i s cal cul ated usi ng the API
model . Thi s model i s recommended for petrol eum and petrochemi cal appl i cati ons.
I t i s used i n the CHAO-SEA, GRAYSON, LK-PLOCK, PENG-ROB, and RK-
SOAVE opti on sets. The general form of the model i s:
( )
l
bi ci
fcn T x T SG T , , , ,
Where:
fcn = A correl ati on based on API Procedure 10A32 (API Technical Data Book,
Petroleum Refining, 4th edition)
TB
T
bi
SG SG 0.1 2.0
TC
T
ci
5.0 2000 TEMPERATURE
Versi on 10
Chapter 3
IAPS Surface Tension for Water
The I APS surface tensi on model was devel oped by the I nternati onal Associ ati on for
Properti es of Steam. I t cal cul ates l i qui d surface tensi on for water and steam. Thi s
model i s used i n opti on sets STEAMNBS and STEAM-TA.
The general form of the equati on for the I APS surface tensi on model i s:
( )
w
fcn T p ,
Where:
The model i s onl y appl i cabl e to water. No parameters are requi red.
Hakim-Steinberg-Stiel/DIPPR
The l i qui d mi xture surface tensi on i s cal cul ated usi ng the equati on:

l
i i
l
i
x
*,
The pure component l i qui d surface tensi on can be cal cul ated by two equati ons:
Haki m-Stei nberg-Sti el
DI PPR l i qui d surface tensi on
Hakim-Steinberg-Stiel
The Haki m-Stei nberg-Sti el equati on i s:
i
l
ci ci pi
ri
m
p T Q
T
i
*,
. x
.
_
,
4 60104 10
1
0 4
7
2
3
1
3
Where:
Q
pi
= 01574 0359 1769 1369 0510 1298
2 2
. . . . . . + +
i i i i i i
m
i
= 1210 05385 14 61 32 07 1656 22 03
2 2
. . . . . . + +
i i i i i i
The parameter
i
i s the Sti el pol ar factor.
Versi on 10
Property
Model
Descriptions
TC
T
ci
PC
p
ci
10
5
10
8
PRESSURE
OMEGA

i
-0.5 2.0
CHI

i
0
DIPPR Liquid Surface Tension
The DI PPR equati on for l i qui d surface tensi on i s:
( )
( )
i
l
i ri
C C T C T C T
i i
C T C T C
i i ri i ri i ri *,

+ + +
1 6 7
1
2 3 4
2
5
3
for
Where:
T
ri
= T T
ci
I f the SI GDI P parameters for a gi ven component are avai l abl e, use the DI PPR
equati on. The DI PPR model i s used by PCES.
SIGDIP/1
C
i 1
SURFACE-TENSION
SIGDIP/2, . . . , 5
C C
i i 2 5
,...,
0
SIGDIP/6
C
i 6
0 TEMPERATURE
SIGDIP/7
C
i 7
1000 TEMPERATURE
References
4th. ed., (New York: McGraw-Hi l l , 1987), p. 638.
Onsager-Samaras
The Onsager-Samaras model cal cul ates the correcti on to the l i qui d mi xture surface
tensi on ofa sol vent mi xture, due to the presence of el ectrol ytes:
+
solv ca
a
ca
ca
x (1)
Versi on 10
Chapter 3
Where:
solv
= Surface tensi on of the sol vent mi xture cal cul ated by the Haki m-
Stei nberg-Sti el model
x
ca
a
= Mol e fracti on of the apparent el ectrol yte ca
ca
= Contri buti on to the surface tensi on correcti on due to apparent
el ectrol yte ca
For each apparent el ectrol yte ca, the contri buti on to the surface tensi on correcti on
i s cal cul ated as:
( )
ca
solv
ca
a solv
ca
a
c
T
c

'
80 0
113 10
13
3
.
log
.
x
(2)
Where:
solv
= Di el ectri c constant of the sol vent mi xture
c
ca
a
=
x
V
ca
a
m
l
V
m
l
= Li qui d mol ar vol ume cal cul ated by the Cl arke model
Apparent el ectrol yte mol e fracti ons are computed from the true i on mol e-fracti ons
and i oni c charge number. They are al so computed i f you use the apparent
component approach. See Chapter 5 for a more detai l ed di scussi on of thi s method.
You must provi de parameters for the Haki m-Stei nberg-Sti el model , used for the
cal cul ati on of the surface tensi on of the sol vent mi xture.
CHARGE z 0.0
References
A. L. Horvath, Handbook of Aqueous Electrolyte Solutions, (Chi chester: El l i s, Ltd.
1985).
Versi on 10
Property
Model
Descriptions
Nonconventional Solid Property Models
Thi s secti on descri bes the nonconventi onal sol i d densi ty and enthal py model s
avai l abl e i n ASPEN PLUS. The following tabl e l i sts the avai l abl e model s and thei r
model names. Nonconventi onal components are sol i d components that cannot be
characteri zed by a mol ecul ar formul a. These components are treated as pure
components for process si mul ati on, though they are compl ex mi xtures.
General Enthalpy and Density Models Model name Phase(s)
General density polynomial DNSTYGEN S
General heat capacity polynomial ENTHGEN S
General coal enthalpy model HCOALGEN S
IGT coal density model DCOALIGT S
IGT char density model DCHARIGT S
General Enthalpy and Density Models
ASPEN PLUS has two bui l t-i n general enthal py and densi ty model s. Thi s secti on
descri bes the general enthal py and densi ty model s avai l abl e.
Model
General Density Polynomial
Heat Capacity Polynomial
General Density Polynomial
DNSTYGEN i s a general model that gi ves the densi ty of any nonconventi onal sol i d
component. I t uses a si mpl e mass fracti on wei ghted average for the reci procal
temperature-dependent speci fi c densi ti es of i ts i ndi vi dual consti tuents. There may
be up to twenty consti tuents wi th mass percentages. You must defi ne these
consti tuents, usi ng the general component attri bute GENANAL. The equati ons
are:
i
s
ij
ij
i
w
1
Versi on 10
Chapter 3
i j
s
i j i j i j i j
a a T a T a T
, , , , ,
+ + +
1 2 3
2
4
3
Where:
w
ij
= Mass fracti on of the jth consti tuent i n component i
i j
s
,
= Densi ty of the jth consi tuent i n component i
DENGEN/1+4 (J-1)
a
i j , 1
x

DENGEN/2+4 (J-1)
a
i j , 2
x 0

DENGEN/3+4 (J-1)
a
i j , 3
x 0

DENGEN/4+4 (J-1)
a
i j , 4
x 0

The units are MASS-DENSI TY and TEMPERATURE.

Use the el ements of GENANAL to i nput the mass percentages of the consti tuents.
The structure of DENGEN i s: four coeffi ci ents for the fi rst consti tuent, four
coeffi ci ents for the second consti tuent, and so on.
General Heat Capacity Polynomial
ENTHGEN i s a general model that gi ves the speci fi c enthal py of any
nonconventi onal component as a si mpl e mass-fracti on-wei ghted-average for the
enthal pi es of i ts i ndi vi dual consti tuents. You may defi ne up to twenty consti tuents
wi th mass percentages, usi ng the general component attri bute GENANAL. The
speci fi c enthal py of each consti tuent at any temperature i s cal cul ated by combi ni ng
speci fi c enthal py of formati on of the sol i d wi th a sensi bl e heat change. (See
Chapter 1.) The equati ons are:
h w h
i
s
i j i j
s
i
, ,
h h C dT
i j
s
f j
s
p j
s
T
, ,
.
+
298 15
C a a T a T a T
p j
s
i j i j i j i j , , , , ,
+ + +
1 2 3
2
4
3
Where:
w
ij
= Mass fracti on of the jth consti tuent i n component i
Versi on 10
Property
Model
Descriptions
h
i
s
= Speci fi c enthal py of sol i d component i
f j
s
h
= Speci fi c enthal py of formati on of consti tuent j
C
P
s
i j ,
= Heat capaci ty of the jth consti tuent i n component i
DHFGEN/J
f j
s
h
x 0 MASS-ENTHALPY
HCGEN/1+4 (J-1)
a
i j , 1
x

HCGEN/2+4
a
i j , 2
x 0

HCGEN/3+4 (J-1)
a
i j , 3
x 0

HCGEN/4+4 (J-1)
a
i j , 4
x 0

The units are MASS-ENTHALPY and TEMPERATURE.

The el ements of GENANAL are used to i nput the mass percentages of the
consti tuents. The structure for HCGEN i s: four coeffi ci ents for the fi rst consti tuent,
four coeffi ci ents for the second consti tuent, and so on.
Coal i s model ed i n ASPEN PLUS as a nonconventi onal sol i d. Coal model s are
empi ri cal correl ati ons, whi ch requi re sol i d materi al characteri zati on i nformati on.
Component attri butes are deri ved from consti tuent anal yses. Defi ni ti ons of coal
component attri butes are gi ven i n the ASPEN PLUS User Guide, Chapter 6.
Enthal py and densi ty are the onl y properti es cal cul ated for nonconventi onal
sol i ds. Thi s secti on descri bes the speci al model s avai l abl e i n ASPEN PLUS for
the enthal py and densi ty of coal and char. The component attri butes requi red by
each model are i ncl uded. The coal model s are:
General coal enthal py
I GT coal densi ty
I GT char densi ty
Versi on 10
Chapter 3
Notation
Most correl ati ons for the cal cul ati on of coal properti es requi re proxi mate, ul ti mate,
and other anal yses. These are converted to a dry, mi neral -matter-free basi s. Onl y
the organi c porti on of the coal i s consi dered.
Moi sture correcti ons are made for al l anal yses except hydrogen, accordi ng to the
formul a:
w
w
w
d
H O
_
,
1
2
Where:
w = The val ue determi ned for wei ght fracti on
w
d
= The val ue on a dry basi s
w
H O
2
= The moi sture wei ght fracti on
For hydrogen, the formul a i ncl udes a correcti on for free-moi sture hydrogen:
w
w w
w
H
d
H H O
H O
0119
1
2
2
.
The mi neral matter content i s cal cul ated usi ng the modi fi ed Parr formul a:
w w w w
MM A Sp Cl
+ + 113 0 47 . .
The ash term corrects for water l ost by decomposi ti on of cl ays i n the ash
determi nati on. The average water consti tuti on of cl ays i s assumed to be 11.2
percent. The sul fur term al l ows for l oss i n wei ght of pyri ti c sul fur when pyri te i s
burned to ferri c oxi de. The ori gi nal Parr formul a assumed that al l sul fur i s
pyri ti c sul fur. Thi s formul a i ncl uded sul fati c and organi c sul fur i n the mi neral -
matter cal cul ati on. When i nformati on regardi ng the forms of sul fur i s avai l abl e,
use the modi fi ed Parr formul a to gi ve a better approxi mati on of the percent of
i norgani c materi al present. Because chl ori ne i s usual l y smal l for Uni ted States
coal s, you can omi t chl ori ne from the cal cul ati on.
Correct anal yses from a dry basi s to a dry, mi neral -matter-free basi s, usi ng the
formul a:
w
w w
w
dm
d d
MM
1
Versi on 10
Property
Model
Descriptions
Where:
w
d
= Correcti on factor for other l osses, such as the l oss of carbon i n
carbonates and the l oss of hydrogen present i n the water
consti tuti on of cl ays
w W W
C
d
A
d
sp
d
+ 0 014 0 005 . .
w w w
H
d
A
d
Sp
d
0 013 0 02 . .
The oxygen and organi c sul fur contents are usual l y cal cul ated by di fference as:
W W W W W
O
dm
C
dm
H
dm
So
dm
N
dm
1
w w w w
S
dm
St
dm
Sp
dm
Ss
dm

Where:
C
p
= Heat capaci ty /(J/kgK)
c
p
= Heat capaci ty /(cal /gC)
h = Speci fi c enthal py
c
h = Speci fi c heat of combusti on
f
h = Speci fi c heat of formati on
R
O
= Mean-maxi mum rel ectance i n oi l
T = Temperature/K
t = Temperature/C
w = Wei ght fracti on
= Speci fi c densi ty
Subscri pts:
A = Ash
C = Carbon
Cl = Chl ori ne
FC = Fi xed carbon
H = Hydrogen
Versi on 10
Chapter 3
H O
2
= Moi sture
MM = Mi neral matter
N = Ni trogen
O = Oxygen
So = Organi c sul fur
Sp = Pyri ti c sul fur
St = Total sul fur
S = Other sul fur
VM = Vol ati l e matter
Superscri pts:
d = Dry basi s
m = Mi neral -matter-free basi s
General Coal Enthalpy Model
The general coal model for computi ng enthal py i n ASPEN PLUS i s HCOALGEN.
Thi s model i ncl udes a number of di fferent correl ati ons for the fol l owi ng:
Heat of combusti on
Heat of formati on
Heat capaci ty
You can sel ect one of these correl ati ons usi ng an opti on code i n the Properti es
Advanced NC-Props form. (See the ASPEN PLUS User Guide, Chapter 6). Use
opti on codes to speci fy a cal cul ati on method for properti es. Each el ement i n the
opti on code vector i s used i n the cal cul ati on of a di fferent property.
The tabl e l abel ed HCOALGEN Opti on Codes l i sts model opti on codes for
HCLOALGEN. The tabl e i s fol l owed by a detai l ed descri pti on of the cal cul ati ons
used for each correl ati on.
The correl ati ons are descri bed i nthe fol l owi ng secti on. The component attri butes
are defi ned i n ASPEN PLUS User Guide, Chapter 6.
Heat of Combustion Correlations
The heat of combusti on of coal i n the HCOALGEN model i s a gross cal ori fi c val ue.
I t i s expressed i n Btu/l b of coal on a dry mi neral -matter-free basi s. ASTM Standard
D-2015 defi nes standard condi ti ons for measuri ng gross cal ori fi c val ue. I ni ti al
oxygen pressure i s 20 to 40 atmospheres. Products are i n the form of ash; l i qui d
water; and gaseous CO
2
, SO
2
, and NO
2
.
Versi on 10
Property
Model
Descriptions
You can cal cul ate net cal ori fi c val ue from gross cal ori fi c val ue by maki ng a
deducti on for the l atent heat of vapori zati on of water.
Heat of combusti on val ues are converted back to a dry, mi neral -matter-
contai ni ng basi s wi th a correcti on for the heat of combusti on of pyri te. The
formul a i s:
( )
c i
d
MMi c i
dm
sp i
h w h w + 1 5400
,
The heat of combusti on correl ati ons were eval uated by the I nsti tute of Gas
Technol ogy (I GT). They used data for 121 sampl es of coal from the Penn State
Data Base (I GT, 1976) and 457 sampl es from a USGS report (Swanson, et al .,
1976). These sampl es i ncl uded a wi de range of Uni ted States coal fi el ds. The
constant terms i n the HCOALGEN correl ati ons are bi as correcti ons obtai ned
from the I GT study.
Boi e Correl ati on:
[ ]
c i
dm
i C i
dm
i H i
dm
i St i
dm
i O i
dm
i N i
dm
i
h a w a w a w a w a w a + + + + +
1 2 3 4 5
2
6
10
, , , , ,
BOIEC/1
a
1i
151.2
BOIEC/2
a
2i
499.77
BOIEC/3
a
3i
45.0
continued
Versi on 10
Chapter 3
BOIEC/4
a
4i
-47.7
BOIEC/5
a
5i
27.0
BOIEC/6
a
6i
-189.0
Dul ong Correl ati on:
[ ]
c i
dm
i C i
dm
i H i
dm
i S i
dm
i O i
dm
i N i
dm
i
h a w a w a w a w a w a + + + + +
1 2 3 4 5
2
5
10
, , , , ,
DLNGC/1
a
1i
145.44
DLNGC/2
a
2i
620.28
DLNGC/3
a
3i
40.5
DLNGC/4
a
4i
-77.54
DLNGC/5
a
5i
-16.0
Grummel and Davi s Correl ati on:
( )
( )
( )
c i
dm
i i H i
dm
A i
d
i C i
dm
i H i
dm
i S i
dm
i O i
dm
i
h
a a w
w
a w a w a w a w a
+
+ + + +
5 2
1 2 3 4
2
6
1
10
,
,
, , , ,
GMLDC/1
a
1i
0.3333
GMLDC/2
a
2i
654.3
GMLDC/3
a
3i
0.125
GMLDC/4
a
4i
0.125
GMLDC/5
a
5i
424.62
GMLDC/6
a
6i
-2.0
Versi on 10
Property
Model
Descriptions
Mott and Spooner Correl ati on:
[ ]
c i
dm
i C i
dm
i H i
dm
i S i
dm
i O i
dm
i O i
dm
h a w a w a w a w a w + + +
1 2 3 4
2
7
10 015
, , , , ,
. for
c i
dm
i C i
dm
i H i
dm
i S i
dm
i
i O i
dm
A i
d O i
dm
i O i
dm
h a w a w a w a
a w
w
w a w + +
_
,
1
]
1
1
+
1 2 3 6
5 2
7
1
10 015
, , ,
,
,
, ,
. for
MTSPC/1
a
1i
144.54
MTSPC/2
a
2i
610.2
MTSPC/3
a
3i
40.3
MTSPC/4
a
4i
62.45
MTSPC/5
a
5i
30.96
MTSPC/6
a
6i
65.88
MTSPC/7
a
7i
-47.0
I GT Correl ati on:
[ ]
c i
dm
i C i
d
i H i
d
i S i
d
i A i
d
i
h a w a w a w a w a + + + +
1 2 3 4
2
5
10
, , , ,
CIGTC/1
a
1i
178.11
CIGTC/2
a
2i
620.31
CIGTC/3
a
3i
80.93
CIGTC/4
a
4i
44.95
CIGTC/5
a
5i
-5153.0
User Input Value of Heat Combustion
HCOMB
c i
d
h
0
Versi on 10
Chapter 3
Standard Heat of Formation Correlations
There are two standard heat of formati on correl ati ons for the HCOALGEN model :
Heat of combusti on-based
Di rect
Heat of Combusti on-Based Correl ati on Thi s i s based on the assumpti on that
combusti on resul ts i n compl ete oxi dati on of al l el ements except sul fati c sul fur and
ash, whi ch are consi dered i nert. The numeri cal coeffi ci ents are combi nati ons of
stoi chi ometri c coeffi ci ents and heat of formati on for CO
2
, H O
2
, HCl , and NO
2
.at
298.15K:

f i
d
c i
d
H i
d
C i
d
S i
d
N i
d
Cl i
d
h h w w w
w w
+ +

( . x . x . x
. x . x )
, , ,
, ,
1418 10 3278 10 9 264 10
2 418 10 1426 10 10
6 5 4
6 4 2
Di rect Correl ati on Normal l y smal l , rel ati ve to i ts heat of combusti on. An
error of 1% i n the heat of a combusti on-based correl ati on produces about a 50%
error when i t i s used to cal cul ate the heat of formati on. For thi s reason, the
fol l owi ng di rect correl ati on was devel oped, usi ng data from the Penn State Data
Base. I t has a standard devi ati on of 112.5 Btu/l b, whi ch i s cl ose to the l i mi t, due
to measurement i n the heat of combusti on:
[ ]
( )
[ ]
( ) ( ) ( ) ( )
[ ]
( ) ( )( )
f i
d
i c i
dm
i H i
dm
i H i
d
i Sp
d
i Ss
d
i o i i C i
d
FC i
d
i VM
d
i C i
dm
i St i
dm
i c i
d
FC i
d
i VM i
d
i o i i VM i
d
C i
d
FC i
d
i
h a w a w a w a w a w
a R a w w a w
a w a w a w w a w
a R a w w w a
+ + + +
+ + + +
+ + + +
+ + +
1 2 3 4 5
2
6 7 8
2
9
2
10
2
11
2
12
2
4
13
2
14
4
15
10
10
10
10
, , ,
, , ,
, , , , ,
, , , ,
Where:
HFC/1
a
1i
1810.123
HFC/2
a
2i
-502.222
HFC/3
a
3i
329.1087
HFC/4
a
4i
121.766
HFC/5
a
5i
-542.393
HFC/6
a
6i
1601.573
HFC/7
a
7i
424.25
continued
Versi on 10
Property
Model
Descriptions
HFC/8
a
8i
-525.199
HFC/9
a
9i
-11.4805
HFC/10
a
10i
31.585
HFC/11
a
11i
13.5256
HFC/12
a
12i
11.5
HFC/13
a
13i
-685.846
HFC/14
a
14i
-22.494
HFC/15
a
15i
-64836.19
Heat Capacity Kirov Correlations
The Ki rov correl ati on (1965) consi dered coal to be a mi xure of moi sture, ash, fi xed
carbon, and pri mary and secondary vol ati l e matter. Pri mary vol ati l e matter i s any
vol ati l e matter equal to the total vol ati l e matter content, up to 10%. The
correl ati on devel oped by Ki rov treats the heat capaci ty as a wei ghted sum of the
heat capaci ti es of the consti tuents:
C w C
p i
d
j p ij
j
ncn
, ,
1
C a a T a T a T
p ij i j i j i j i j , , , , ,
+ + +
1 2 3
2
4
3
Where:
i = Component i ndex
j = Consti tuent i ndex j = 1, 2 , ... , ncn
1 = Moi sture
2 = Fi xed carbon
3 = Pri mary vol ati l e matter
4 = Secondary vol ati l e matter
5 = Ash
w
j
= Mass fracti on of jth consti tuent on dry basi s
Versi on 10
Chapter 3
CP1C/1
a
i,11
1.0
CP1C/2
a
i,12
0
CP1C/3
a
i,13
0
CP1C/4
a
i,14
0
CP1C/5
a
i,21
0.165
CP1C/6
a
i,22
68 10
4
. x

CP1C/7
a
i,23

4 2 10
7
. x
CP1C/8
a
i,24
0
CP1C/9
a
i,31
0.395
CP1C/10
a
i,32
81 10
4
. x

CP1C/11
a
i,33
0
CP1C/12
a
i,34
0
CP1C/13
a
i, 41
0.71
CP1C/14
a
i,42
61 10
4
. x

CP1C/15
a
i,43
0
CP1C/16
a
i,44
0
CP1C/17
a
i,51
0.18
CP1C/18
a
i,52
14 10
4
. x

CP1C/19
a
i,53
0
CP1C/20
a
i,54
0
Versi on 10
Property
Model
Descriptions
Cubic Temperature Equation
The cubi c temperature equati on i s:
c a a t a t a t
p
d
i i i i
+ + +
1 2 3
2
4
3
CP2C/1
a
1i
0.438
CP2C/2
a
2i

7576 10
3
. x
CP2C/3
a
3i 8 793 10
5
. x

CP2C/4
a
4i

2587 10
7
. x
The defaul t val ues of the parameters were devel oped by Gomez, Gayl e, and Tayl or
(1965). They used sel ected data from three l i gni tes and a subbi tumi nous B coal ,
over a temperature range from 32.7 to 176.8C.
HCOALGEN Option Codes
Option Code Number
Option Code
Value Calculation Method Parameter Names Component Attributes
1 Heat of Combustion
1 Boie correlation BOIEC ULTANAL
SULFANAL
PROXANAL
2 Dulong correlation DLNGC ULTANAL
SULFANAL
PROXANAL
3 Grummel and Davis
correlation
GMLDC ULTANAL
SULFANAL
PROXANAL
4 Mott and Spooner
correlation
MTSPC ULTANAL
ULFANAL
ROXANAL
5 IGT correlation CIGTC ULTANAL
ROXANAL
6 User input value HCOMB ULTANAL
ROXANAL
continue
Versi on 10
Chapter 3
HCOALGEN Option Codes (continued)
Option Code Number
Option Code
Value Calculation Method Parameter Names Component Attributes
2 Standard Heat of Formation
1 Heat-of-combusion-
based correlation
ULTANAL
ULFANAL
2 Direct correlation HFC ULTANAL
SULFANAL
PROXANAL
3 Heat Capacity
1 Kirov correlation CP1C PROXANAL
2 Cubic temperature
equation
CP2C
4 Enthalpy Basis
1 Elements in their
standard states at
298.15K and 1 atm
2 Component at 298.15
K

IGT Coal Density Model
The DCOALI GT model gi ves the true (skel etal or sol i d-phase) densi ty of coal on a
dry basi s. I t uses ul ti mate and sul fur anal yses. The model i s based on equati ons
from I GT (1976):
( )
[ ]
i
i
dm
i
dm
A i
d
Sp i
d
A i
d
Sp i
d
w w w w
+ 0 42 015 1 113 05475 . . . .

, , , ,
( ) ( )
i
dm
i i H i
dm
i H i
d m
i H i
dm
a a w a wW a w
+ + +
1
1 2 3 4
3
, ,
,
,
( )
( )
W
W w w
w w
H i
dm
H i
d
A i
d
Sp i
d
A i
d
Sp i
d
,
, , ,
, ,
. .
. .
+

10 0 013 0 02
1 113 0 475
2
The equati on for
i
dm
i s good for a wi de range of hydrogen contents, i ncl udi ng
anthraci ti es and hi gh temperature cokes. The standard devi ati on of thi s correl ati on
for a set of 190 poi nts col l ected by I GT from the l i terature was
Versi on 10
Property
Model
Descriptions
12 10
6
x

m kg
3
. The poi nts are essenti al l y uni form over the whol e range. Thi s i s
equi val ent to a standard devi ati on of about 1.6% for a coal havi ng a hydrogen
content of 5%. I t i ncreases to about 2.2% for a coke or anthraci te havi ng a
hydrogen content of 1%.
Versi on 10
Chapter 3
DENIGT/1
a
1i
0.4397
DENIGT/2
a
2i
0.1223
DENIGT/3
a
3i
-0.01715
DENIGT/4
a
4i
0.001077
IGT Char Density Model
The DGHARI GT model gi ves the true (skel etal or sol i d-phase) densi ty of char or
coke on a dry basi s. I t uses ul ti mate and sul fur anal yses. Thi s model i s based on
equati ons from I GT (1976):
( )
i
d i
dm
A i
d
i
dm
A i
d
w w
+
3
3 1
, ,
( ) ( )
i
d
i i H i
dm
i H i
d m
i H i
dm
a a w a w a w
+ + +
1
1 2 2
2
3
3
, ,
,
,
( )
w
w
w
H i
dm H i
d
A i
d
,
,
,
1
DENIGT/1
a
1i
0.4397
DENIGT/2
a
2i
0.1223
DENIGT/3
a
3i
-0.01715
DENIGT/4
a
4i
0.001077
The densi ti es of graphi ti c hi gh-temperature carbons (i ncl udi ng cokes) range from
2 2 10
3
. x to 2 26 10
3
. x kg m
3
. Densi ti es of nongraphi ti c hi gh-temperature carbons
(deri ved from chars) range from 2 0 10
3
. x to 2 2 10
3
. x kg m
3
. Most of the data used
i n devel opi ng thi s correl ati on were for carboni zed coki ng coal s. Al though data on a
few chars (carboni zed non-coki ng coal s) were i ncl uded, none has a hydrogen
content l ess than 2%. The correl ati on i s probabl y not accurate for hi gh temperature
chars.
Versi on 10
Property
Model
Descriptions
References
I .M. Chang, B.S. Thesi s, Massachusetts I nsti tute of Technol ogy, 1979.
M. Gomez, J.B. Gayl e, and A.R. Tayl or, Jr., Heat Content and Specific Heat of
Coals and Related Products, U.S. Bureau of Mi nes, R.I . 6607, 1965.
I GT (I nsti tute of Gas Technol ogy), Coal Conversion Systems Technical Data
Book, Secti on PMa. 44.1, 1976.
N.Y. Ki rov, "Speci fi c Heats and Total Heat Contents of Coal s and Rel ated
Materi al s are El evated Temperatures," BCURA Monthly Bulletin, (1965), pp. 29,
33.
V.E. Swanson et al ., Collection, Chemical Analysis and Evaluation of Coal
Samples in 1975, U.S. Geol ogi cal Survey, Open-Fi l e Report (1976), pp. 76468.
O O O O
Versi on 10
Chapter 4
4 Property Calculation
Methods and Routes
I n ASPEN PLUS the methods and model s used to cal cul ate thermodynami c and
transport properti es are packaged i n property methods. Each property method
contai ns al l the methods and model s needed for a si mul ati on. A uni que
combi nati on of methods and model s for cal cul ati ng a property i s cal l ed a route.
The ASPEN PLUS User Guide, Chapter 7, descri bes the property methods
avai l abl e i n ASPEN PLUS, provi des gui del i nes for choosi ng an appropri ate
property method for your si mul ati on, and descri bes how to modi fy property
methods to sui t your si mul ati on needs by repl aci ng property model s.
Thi s chapter di scusses:
Major, subordi nate, and i ntermedi ate properti es i n ASPEN PLUS
Cal cul ati on methods avai l abl e
Routi ng concepts
Property model s avai l abl e
Traci ng routes
Modi fyi ng and creati ng property methods
Modi fyi ng and creati ng routes
Versi on 10
Property
Calculation
Methods and
Routes
Introduction
Most properti es are cal cul ated i n several steps. An exampl e i s the cal cul ati on of the
fugaci ty coeffi ci ent of a component i n a l i qui d mi xture:

i
l
i i
l
*,
(1)
Where:
i
l *,
=

i
i
l
p
p
*,
*,
(2)
Equati ons 1 and 2 are both deri ved from thermodynami cs. The equati ons rel ate the
properti es of i nterest
( )

i
l
i
l
,
*,
to other properti es
( )

i i
l
i
l
p , ,
*, *,
and state vari abl es
( ) x p
i
, . I n general , thi s type of equati on i s deri ved from uni versal sci enti fi c
pri nci pl es. These equati ons are cal l ed methods.
I n the computati on of the l i qui d mi xture fugaci ty, you need to cal cul ate:
Acti vi ty coeffi ci ent ( )
i
Vapor pressure
( )
p
i
l *,
Pure component vapor fugaci ty coeffi ci ent
Thi s type of property i s usual l y cal cul ated usi ng equati ons that depend on
uni versal parameters l i ke T
c
and p
c
; state vari abl es, such as T and p; and
correl ati on parameters. The use of correl ati on parameters makes these equati ons
much l ess uni versal and more subjecti ve than methods. For di sti ncti on, we cal l
them models. Often several model s exi st to cal cul ate one property. For exampl e, to
cal cul ate
i
you can use the NRTL, UNI QUAC, or UNI FAC model .
The reason for treati ng model s and methods separatel y i s to al l ow for maxi mum
fl exi bi l i ty i n property cal cul ati ons. Therefore the descri pti ons provi ded shoul d
hel p show the fl exi bi l i ty of the ASPEN PLUS property system, rather than
consti tute defi ni ti ons. For detai l ed descri pti ons and l i sts of avai l abl e methods
and model s, see Methods and Routes and Model s, thi s chapter .
A compl ete cal cul ati on route consi sts of a combi nati on of methods and model s. A
number of frequentl y used routes have been defi ned i n ASPEN PLUS. Routes
that bel ong l ogi cal l y together have been grouped to form property methods. For
more about property methods, see Chapter 2. Routes are di scussed i n detai l i n
Routes and Model s, thi s chapter.
To choose a di fferent cal cul ati on route for a gi ven property route than what i s
defi ned i n a property method, you can exchange routes or model s i n property
methods (see Modi fyi ng and Creati ng Property Methods, thi s chapter ).
Versi on 10
Chapter 4
For a speci fi c property, there are many choi ces of model s and methods used to
bui l d a route. Therefore ASPEN PLUS does not contai n al l possi bl e routes as
predefi ned routes. However you can freel y construct cal cul ati on routes accordi ng
to your needs. Thi s i s a uni que feature of ASPEN PLUS. Modi fyi ng and creati ng
new routes from exi sti ng methods, routes and model s, and usi ng them i n
modi fi ed or new property methods i s expl ai ned i n Modi fyi ng and Creati ng
Routes, thi s chapter.
Physical Properties in ASPEN PLUS
The fol l owi ng properti es may be requi red by uni t operati ons i n ASPEN PLUS
si mul ati ons:
Thermodynami c Properti es
Fugaci ty coeffi ci ents (for K-val ues)
Enthal py
Entropy
Gi bbs energy
Mol ar vol ume
Transport Properti es
Vi scosi ty
Surface tensi on
The properti es requi red by uni t operati on model s i n ASPEN PLUS are cal l ed major
properties and are l i sted i n the tabl e l abel ed Major Properti es i n ASPEN PLUS on
page 4-4. A major property may depend on other major properti es. I n addi ti on, a
major property may depend on other properti es that are not major properti es.
These other properti es can be di vi ded i nto two categori es: subordi nate properti es
and i ntermedi ate properti es.
Subordinate properties may depend on other major, subordi nate or i ntermedi ate
properti es, but are not di rectl y requi red for uni t operati on model cal cul ati ons.
Exampl es of subordi nate properti es are enthal py departure and excess enthal py.
The tabl e l abel ed Subordi nate Properti es i n ASPEN PLUS on page 4-6 l i sts the
subordi nate properti es.
I ntermediate properties are cal cul ated di rectl y by property model s, rather than as
fundamental combi nati ons of other properti es. Common exampl es of
i ntermedi ate properti es are vapor pressure and acti vi ty coeffi ci ents. The tabl e
l abel ed I ntermedi ate Properti es i n ASPEN PLUS on page 4-8 l i sts the
i ntermedi ate properti es.
Major and subordi nate properti es are obtai ned by a method eval uati on.
I ntermedi ate properti es are obtai ned by a model eval uati on.
Versi on 10
Property
Calculation
Methods and
Routes
Major Properties in ASPEN PLUS
Property Name Symbol Description
PHlV
i
v *,
Vapor pure component fugacity coefficient
PHIL
i
l *,
Liquid pure component fugacity coefficient
PHlS
i
s *,
Solid pure component fugacity coefficient
PHlV
i
v
Vapor fugacity coefficient of a component in a mixture
PHlLMX
i
l
Liquid fugacity coefficient of a component in a mixture
PHlSMX
i
s
Solid fugacity coefficient of a component in a mixture
HV
H
i
v *,
Vapor pure component molar enthalpy
HL
H
i
l *,
Liquid pure component molar enthalpy
HS
H
i
s *,
Solid pure component molar enthalpy
HVMX
H
i
v
Vapor mixture molar enthalpy
HLMX
H
i
l
Liquid mixture molar enthalpy
HSMX
H
i
s
Solid mixture molar enthalpy
GV
i
v *,
Vapor pure component molar Gibbs free energy
GL
i
l *,
Liquid pure component molar Gibbs free energy
GS
i
s *,
Solid pure component molar Gibbs free energy
GVMX
G
i
v
Vapor mixture molar Gibbs free energy
GLMX
G
i
l
Liquid mixture molar Gibbs free energy
GSMX
G
i
s
Solid mixture molar Gibbs free energy
SV
S
i
v *,
Vapor pure component molar entropy
SL
S
i
l *,
Liquid pure component molar entropy
SS
S
i
s *,
Solid pure component molar entropy
SVMX
S
i
v
Vapor mixture molar entropy
continued
Versi on 10
Chapter 4
Major Properties in ASPEN PLUS
SLMX
S
i
l
Liquid mixture molar entropy
SSMX
S
i
s
Solid mixture molar entropy
VV
V
i
v *,
Vapor pure component molar volume
VL
V
i
l *,
Liquid pure component molar volume
VS
V
i
s *,
Solid pure component molar volume
VVMX
V
i
v
Vapor mixture molar volume
VLMX
V
i
l
Liquid mixture molar volume
VSMX
V
i
s
Solid mixture molar volume<F20MI>
MUV
i
v *,
Vapor pure component viscosity
MUL
i
l *,
Liquid pure component viscosity
MUVMX
i
v
Vapor mixture viscosity
MULMX
i
l
Liquid mixture viscosity
KV
i
v *,
Vapor pure component thermal conductivity
KL
i
l *,
Liquid pure component thermal conductivity
KS
i
s *,
Solid pure component thermal conductivity
KVMX
i
v
Vapor mixture thermal conductivity
KLMX
i
l
Liquid mixture thermal conductivity
KSMX
i
s
Solid mixture thermal conductivity
DV
D
ij
v
Vapor binary diffusion coefficient
DL
D
ij
l
Liquid binary diffusion coefficient
DVMX
D
i
v
Vapor diffusion coefficient of a component in a mixture
DLMX
D
i
l
Liquid diffusion coefficient of a component in a mixture
SIGL
i
l *,
Pure component surface tension
SIGLMX
l
Mixture surface tension
Versi on 10
Property
Calculation
Methods and
Routes
Subordinate Properties in ASPEN PLUS
DHV
H H
i
v
i
ig *, *,
Vapor pure component molar enthalpy departure

DHL
H H
i
l
i
ig *, *,
Liquid pure component molar enthalpy departure

DHS
H H
i
s
i
ig *, *,
Solid pure component molar enthalpy departure

DHVMX
H H
m
v
m
ig
Vapor mixture molar enthalpy departure

DHLMX
H H
m
l
m
ig
Liquid mixture molar enthalpy departure

DHSMX
H H
m
s
m
ig
Solid mixture molar enthalpy departure

DHVPC
H p H p
i
v
i
v
i
*, *, *
( ) ( )
Vapor pure component molar enthalpy departure pressure
correction
DHLPC
H p H p
i
l
i
l
i
*, *, *
( ) ( )
Liquid pure component molar enthalpy departure pressure
correction
DHSPC
H p H p
i
s
i
s
i
*, *, *
( ) ( )
Solid pure component molar enthalpy departure pressure
correction
DGV

i
v
i
ig *, *,
Vapor pure component molar Gibbs energy departure

DGL

i
l
i
ig *, *,
Liquid pure component molar Gibbs energy departure

DGS

i
s
i
ig *, *,
Solid pure component molar Gibbs energy departure

DGVMX
G G
m
v
m
ig
Vapor mixture molar Gibbs energy departure

DGLMX
G G
m
l
m
ig
Liquid mixture molar Gibbs energy departure

DGSMX
G G
m
s
m
ig
Solid mixture molar Gibbs energy departure

DGVPC

i
v
i
v
i
p p
*, *, *
( ) ( )
Vapor pure component molar Gibbs energy departure
pressure correction
DGLPC

i
l
i
l
i
p p
*, *, *
( ) ( )
Liquid pure component molar Gibbs energy departure
pressure correction
DGSPC

i
s
i
s
i
p p
*, *, *
( ) ( )
Solid pure component molar Gibbs energy departure
pressure correction
DSV
S S
i
v
i
ig *, *,
Vapor pure component molar entropy departure

DSL
S S
i
l
i
ig *, *,
Liquid pure component molar entropy departure

continued
Versi on 10
Chapter 4
DSS
S S
i
s
i
ig *, *,
Solid pure component molar entropy departure

DSVMX
S S
m
v
m
ig
Vapor mixture molar entropy departure

DSLMX
S S
m
l
m
ig
Liquid mixture molar entropy departure

DSSMX
S S
m
s
m
ig
Solid mixture molar entropy departure

HNRY
H
iA
Henrys constant of supercritical component i in subcritical
component A
HLXS
H
m
E l ,
Liquid mixture molar excess enthalpy
HSXS
H
m
E s ,
Solid mixture molar excess enthalpy
GLXS
G
m
E l ,
Liquid mixture molar excess Gibbs energy
GSXS
G
m
E s ,
Solid mixture molar excess Gibbs energy
PHILPC
*,l
Pure component liquid fugacity coefficient pressure
correction
PHISPC
*,s
Pure component solid fugacity coefficient pressure
correction
GAMPC
E
Liquid activity coefficient pressure correction, symmetric
convention
GAMPC1
*E
Liquid activity coefficient pressure correction, asymmetric
convention
HNRYPC
iA
Henrys constant pressure correction for supercritical

component i in subcritical component A
XTRUE
x
true
True composition
MUVLP
i
v
p
*,
( ) 0
Pure component low pressure vapor viscosity
MUVPC

i
v
i
v
p p
*, *,
( ) ( ) 0
Pure component vapor viscosity pressure correction
MUVMXLP
v
p ( ) 0
Low pressure vapor mixture viscosity
MUVMXPC

v v
p p ( ) ( ) 0
Vapor mixture viscosity pressure correction
KVLP
i
v
p
*,
( ) 0
Pure component low pressure vapor thermal conductivity
continued
Versi on 10
Property
Calculation
Methods and
Routes
KVLP

i
v
i
v
p p
*, *,
( ) ( ) 0 0
Pure component vapor thermal conductivity pressure
correction
KVMXLP
v
p ( ) 0
Low pressure, vapor mixture thermal conductivity
KVMXPC

v v
p p ( ) ( ) 0
Vapor mixture thermal conductivity pressure correction
Intermediate Properties in ASPEN PLUS
GAMMA

Liquid phase activity coefficient
GAMUS
*
Liquid phase activity coefficient, unsymmetric convention
GAMMAS
s
Solid phase activity coefficient
WHNRY w Henrys constant mixing rule weighting factor
PL
p
i
l *,
Liquid pure component vapor pressure
PS
p
i
s *,
Solid pure component vapor pressure
DHVL
vap i
H
*
Pure component enthalpy of vaporization
DHLS
fus i
H
*
Pure component enthalpy of fusion
DHVS
sub i
H
*
Pure component enthalpy of sublimation
VLPM
V
i
l
Partial molar liquid volume
Versi on 10
Chapter 4
Methods
Thi s secti on descri bes the methods avai l abl e for cal cul ati ng the major and
subordi nate properti es i n ASPEN PLUS.
A method i s an equati on used to cal cul ate physi cal properti es based on uni versal
sci enti fi c pri nci pl es onl y, such as thermodynami cs. Thi s equati on may contai n
assumpti ons, such as the vapor can be treated as i deal gas or the pressure i s l ow
enough to negl ect the pressure correcti on. The equati on may need properti es and
state vari abl es but not correl ati on parameters to cal cul ate a speci fi c property.
Appl i ed thermodynami cs i ndi cate that there usual l y i s more than one method for
cal cul ati ng a parti cul ar property. For exampl e, the enthal py departure of a
component i n the l i qui d phase, H H
i
l
i
ig *, *,
can be cal cul ated from i ts fugaci ty
coeffi ci ent i n the l i qui d phase:
H H RT
T
i
l
i
ig i
l
*, *,
*,
ln

2

Thi s method i s often used for supercri ti cal sol utes i n l i qui d sol uti on.
Al ternati vel y, the l i qui d departure functi on can be cal cul ated from the vapor
enthal py departure and the heat of vapori zati on:
H H H H H
i
l
i
ig
i i
ig
vap i
*, *, *, *,

Both methods are equal l y val i d. There i s another possi bi l i ty, whi ch i s to cal cul ate
the departure functi on di rectl y by an equati on of state. Equati ons of state use
correl ati on parameters and are therefore cl assi fi ed as model s, so:
( ) H H f p T
i
l
i
ig *, *,
, , correlation parameters
Thi s i s not a method but rather a val i d al ternati ve to cal cul ate the enthal py
departure. To make the model avai l abl e to the l i st of methods, a si mpl e method i s
used that refers to a model :
( ) H H f p T
i
l
i
ig *, *,
, , specified model
I n general , a l i st of methods avai l abl e for a property wi l l be si mi l ar to the l i st
presented here for the enthal py departure. Compare the tabl es on pages 4-11
through 4-36.
Versi on 10
Property
Calculation
Methods and
Routes
I n a method you can have any number of major properti es, subordi nate
properti es, or model s. Usual l y there i s a method that can be used wi th an
equati on-of-state approach and an al ternati ve that i s used wi th the acti vi ty
coeffi ci ent approach (see Chapter 1). There i s al ways a method that refers to a
model . Al though there are a l i mi ted number of thermodynami c methods, i n
general , al l the exi sti ng thermodynami c methods for each property are present.
Transport property methods are not as uni versal as thermodynami c methods.
Therefore the transport property methods offered i n ASPEN PLUS mi ght not be
exhausti ve, but mul ti pl e methods for one property al so exi st.
Al l physi cal property methods avai l abl e for cal cul ati ng major and subordi nate
properti es i n ASPEN PLUS are provi ded i n the tabl es on pages 4-11 through 4-
36. For each major or subordi nate property, these tabl es l i st:
Property symbol and name
Property type: major or subordi nate
Methods avai l abl e for cal cul ati ng the property
For each method the fundamental equati on i s gi ven. The tabl e al so l i sts whi ch
i nformati on i s needed to speci fy each step i n the method (see Routes and Model s,
this chapter).
Example 1 Methods for calculating liquid mixture enthalpy
From the tabl e l abel ed Li qui d Enthal py Methods on page 4-18, there are four
methods for cal cul ati ng HLMX:
Method 1 HLMX i s cal cul ated di rectl y by an empi ri cal model . The model may
depend on temperature T, pressure p, l i qui d composi ti on, and certai n
model -speci fi c parameters.
( ) H f T p x parameters
l l
i
, , ,
Method 2 HLMX i s cal cul ated from the i deal l i qui d mi xture enthal py and
excess enthal py.
H x H H
m
l
i i
l
m
E l
+
*, ,
( ) HLMX x HL HLXS
i i
+
The major property HLMX depends on the l i qui d pure component enthal py, HL,
and the l i qui d mi xture excess enthal py, HLXS. HL i s al so a major property, whi l e
HLXS i s a subordi nate property.
Versi on 10
Chapter 4
Method 3 HLMX i s cal cul ated from the i deal gas mi xture enthal py, HI GMX, and
the l i qui d mi xture enthal py departure, DHLMX.
( )
H H H H
m
l
m
ig
m
l
m
ig
+
( ) HLMX HIGMX DHLMX +
The subordi nate property DHLMX can be cal cul ated by one of two methods as
l i sted i n the tabl e l abel ed Li qui d Enthal py Methods on page 4-18. I n al l the
equati on-of-state property methods, DHLMX i s cal cul ated di rectl y by an equati on
of state (that i s, method 1 i s used for DHLMX).
Method 4 HLMX i s cal cul ated di rectl y by the El ectrol yte model .
( )
H f x
m
l t
Where:
x
t
= The component true mol e fracti ons
( x
t
i s al so the symbol for the subordi nate property XTRUE:
HLMX = f (XTRUE)).
Vapor Fugacity Coefficient Methods
Property Symbol
and Name
Property Type Method
Code
Method Route Structure Information Required
i
v *,
PHIV
Major 1 Specified model
i
v *,
Model name
i
v
PHIVMX
i
v
Model name (Default:
i
v
1)
2
( )

i
v
i i
v
f y ,
*,
i
v *,
Route ID
i
v
Model name
3
( )
i
v
i
f

i
Model name
i
v
Model name
Versi on 10
Property
Calculation
Methods and
Routes
Liquid Fugacity Coefficient Methods
Property
Symbol and
Name
Property
Type
Method
Code
Method Route Structure Information
Required
i
l *,
PHIL
i
l *,
Model name
2
( )

i
v
i
l
i
l
i
l
T p p
p
*, *, *, *,
, p
l *,
Model name
i
v *,
Model name
(Default:
*,v
1)
*,l
Route ID
(Default:
i
l *,
1)
3 Specified model for supercritical components For
subcritical components:
( )
i
v
i
l i
l
l
p
p
T p
p
p RT
V dp
i
l
*, *,
*,
*,
, exp
*,
1
_
,
i
l *,
Model name
p
l *,
Model name
i
l *,
Model name
V
i
l *,
Model Name
i
l *,
PHILPC
Subord. 1
exp
*,
*,
1
RT
V dp
l
p
p
i
l
_
,
p
l *,
Model name
V
i
l *,
Model Name
Integration option code
(Default:1 point)
2 Specified model
i
l *,
Model name
i
l
PHILMX
i
l
Model name
2

i i
l
i
E *,
i
Model name
(Default:
i
1)
i
l *,
Route ID
i
E
Route ID
(Default:
i
E
1)
3 Unsymmetric Convention
For subcritical components (A or B):
A
l *,
Route ID
continued
Versi on 10
Chapter 4
Liquid Fugacity Coefficient Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
Required

A
l
A A A
l
*,
A
Model name
(Default:
A
1)
For supercritical components (I or j)

i
l
i
i
i
H
p
_
,
Where:
ln ln ln

A
A
A
j
jA
j
j j
w
x
x
H H
iA
_
,
_
,
1
]
1
1

H
jA
Route ID
ln ln
H
w
H
i
i
B
B iB
iB

_
,

_
,

w
B
Model name
( ) ln lim ln
i
x
i
j j
0
w
B
Model option code (see
Chapter 3)
w
B
B
1
Method Option code
0: Do not calculate H
i
1: Calculate H
i
(Default = 0 )
4

i i
l
i
E *,
i
Model name
(Default:
i
1)
i
l *,
Route ID
i
E
Route ID
(Default:
i
E
1)
Where:
( )
i
t
f x (Default:
i
E
1)
x
t
Route ID
5 Unsymmetric Convention
For subcritical components (A or B):
i
l *,
Route ID
continued
Versi on 10
Property
Calculation
Methods and
Routes
Property
Symbol and
Name
Property
Type
Method
Code
Required

A
l
A A A
l
*,
A
Model name
(Default:
A
1)
Where:
( )
A
t
f x x
t
Route ID
For supercritical components (i or j)

i
l
i
i
i
H
p
_
,
Where:
ln ln ln

A
A
A
j
jA
j
j j
W
X
x
H H
iA
_
,
_
,
1
]
1
1

H
jA
Route ID
ln ln
H
w
H
i
i
B
B
iB
iB

_
,

_
,

w
B
Model name
( ) ln lim ln
i
x
i
j j
0
w
B
Model option code (see
Chapter 3)
w
B
B
1
Method Option code
0: Do not calculate H
i
1: Calculate H
i
(Default = 0 )
6

i
l
i
f ( )

i
Model name
i
l
Model name
x
t
XTRUE
Subord. 1
( ) x f T x
t
i i
, , , Chemistry

i
Model name
i
E
GAMPC
Subord. 1
( )
exp
*,
1
RT
V V dp
i
l
i
l
p
p
ref
_
,
V
i
l
Model name
V
i
l *,
Model name
continued
Versi on 10
Chapter 4
Property
Symbol and
Name
Property
Type
Method
Code
Required
(Default: 1 point)
2 Specified model
i
E
Model name
i
E *,
GAMPC1
Subord. 1
exp
1
RT
V dp
i
l
p
p
ref
_
,
V
i
l
Model name
(Default: 1 point)
2 Specified model
i
E *,
Model name
H
iA
HNRY
Subord. 1 Specified model
H
iA
Model name
2
( )
H p T
iA
ref
iA
,
H
iA
Model name
iA
Route ID
(Default:
iA
= 1)
p
ref
defined by the p
ref
option code of HNRYPC
iA
HNRYPC
Subord. 1
exp
1
RT
V dp
i
l
p
p
ref
_
,
p
A
l *,
Model name (if
needed for p
ref
)
p
ref
Option code
1: p
ref
= 0
2: p
ref
= 1 atm
3: p
ref
= p
A
l *,
(T)
(Default = 2)
V
i
Model name
Integration code
(Default: 1 point)
2 Specified model
iA
Model name
Versi on 10
Property
Calculation
Methods and
Routes
Solid Fugacity Coefficient Methods
Property
Symbol and
Name
Property
Type
Method
Code
Required
i
s *,
PHIS
Major 1 Specified Model
i
s *,
Model name
2
( )

i
v
i
s
i
s i
s
T p p
p
*, *, *,
*,
,
p
i
s *,
Model name
i
v *,
Model name
(Default:
i
v *,
= 1)
i
s *,
Route ID
(Default:
i
s *,
= 1)
3

i
s
i
l *, *,
i
s *,
Model name
i
l *,
Route ID
i
s *,
PHISPC
Subord. 1
exp
*,
*,
1
RT
V dp
i
s
p
p
s
_
,
p
i
s *,
Model name
V
i
s *,
Model name
(Default: 1 point)
2 Specified model
i
s *,
Model name
i
s
PHISMX
i
s
Model name
2
( )

i
s
i
s
i
s
f x ,
*,
i
s *,
Route ID
i
s
Model name
3

i
s
i
s *,
i
s
Model name
i
s *,
Route ID
Versi on 10
Chapter 4
Vapor Enthalpy Methods
Property
Symbol and
Name
Property
Type
Method
Code
H
i
*,
HV
H
i
*,
Model name
2
( )
H H H
i
ig
i i
ig *, *, *,
+
( )
H H
i i
ig *, *,
Route ID
(Default: H H
i i
ig *, *,
= 0)
3
H H
i
l
vap i
*, *
+ H
i
l *,
Route ID
vap i
H
*
Model name
H H
i i
ig *, *,
DHV
( )
H H
i i
ig *, *,
Model name
2
_
,
RT
T
i
v
2

ln
*,
i
v *,
Model name
H
m
HVMX
H
m
Model name
2
y H
i i
i
*,
H
i
*,
Route ID
3
( )
H H H
m
ig
m m
ig
+
( )
H H
m m
ig
Route ID
(Default: H H
m m
ig
=0 )
H H
m m
ig
DHVMX
( )
H H
m m
ig
Model name
2
_
,
RT y
T
i
i
i
v
2

ln

i
v
Model name
Versi on 10
Property
Calculation
Methods and
Routes
Liquid Enthalpy Methods
Property
Symbol and
Name
Property
Type
Method
Code
Required
H
i
l *,
HL
H
i
l *,
Model name
2
( )
H H H
i
ig
i
l
i
ig *, *, *,
+
( )
H H
i
l
i
ig *, *,
Route
ID
H H
i
l
i
ig *, *,
DHL
Subor
d.
1 Specified model
( )
H H
i
l
i
ig *, *,
Model
name
2
_
,
RT
T
i
l
2

ln
*,
i
l *,
Model name
3
( )
( )
( )
( )
( ) ( ) ( )
H T p H T H T
H T p H T p
i
v
i
l
i
ig
vap i
i
l
i
l
i
l
*, *, *, *
*, *, *,
,
, ,

+
p
i
l
Model name
( )
H H
i
v
i
ig *, *,
Route ID
(Default: H H
i
v
i
ig *, *,
= 0 )
vap i
l
H Model name
( ) ( ) ( )
H T p H T p
i
l
i
l
i
l *, *, *,
, ,
Route ID
(Default:
( ) ( )
H T p H T p
i
l
i
l
i
l *, *, *,
, ,
= 0)
( )
( )
H T p
H T p
i
l
i
l
i
l
*,
*, *,
,
,
DHLPC
Subor
d.
1
( ) ( ) ( )
( ) ( )
( )
H T p H T
H T p H T
i
l
i
ig
i
l
pi
l
i
ig
*, *,
*, *, *,
,
,

p
i
l *,
Model name
( )
H H
i
l
i
ig *, *,
Route
ID
2
V T
V
T
dp
i
l i
l
p p
p
i
*,
*,
_
,
1
]
1
1
p
i
l *,
Model name
V
i
l *,
Model name
(Default: 1 point )
3 Specified model
( ) ( ) ( )
H T p H T p
i
l
i
l
i
l *, *, *,
, ,
Model name
continued
Versi on 10
Chapter 4
Liquid Enthalpy Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
Required
H
m
l
HLMX
H
m
l
Model name
2
x H H
i
i i
l
m
E l *, ,
+
H
i
l *,
Route ID
H
i
E l ,
Route ID
(Default: H
i
E l ,
=0)
3
( )
H H H
m
ig
m
l
m
ig
+
( )
H H
m
l
m
ig
Route ID
4
Electrolyte model
( )
x
t
H
m
l
Model name
x
t
Route ID
H H
m
l
m
ig
DHLMX
Subor
d.
1 Specified model
( )
H H
m
l
m
ig
Model
name
2
( )
x H H H
i i
l
i
ig
i
m
E I *, *, ,
+

( )
H H
i
l
i
ig *, *,
Route ID
H
m
E l ,
Route ID
(Default: H
m
E l ,
= 0 )
continued
Versi on 10
Property
Calculation
Methods and
Routes
Liquid Enthalpy Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
Required
3 Unsymmetric convention For subcritical components A or
B:
( )
x H H H
A A
I
A
ig
i
m
E I *, *, ,
+
H RT x
T
m
E I
B
B
B
,
ln

_
,
For supercritical component i or j:
_
,
RT x
T
j
j
j
I
2

ln
where:

_
,
i
i
i
H
p
ln ln
H H
i
B
iB

_
,

_
,
( ) ln lim ln
x
i
i
0
w
B
B
1
( )
H H
A
I
A
ig *, *,
Route
ID
where:
B
Model name
H
iB
Route ID
w
B
Model name
w
B
Model option code
(see Chapter 3)
H
m
E l ,
HLXS
Subor
d.
1 Specified model
H
m
E l ,
Model name
2
H RT x
T
m
E l
i
i
i
,
ln

_
,

2

i
Model name
Versi on 10
Chapter 4
Solid Enthalpy Methods
Property
Symbol and
Name
Property
Type
Method
Code
H
i
s *,
HL
H
i
s *,
Model name
2
( )
H H H
i
ig
i
s
i
ig *, *, *,
+
( )
H H
i
s
i
ig *, *,
Route ID
H H
i
s
i
ig *, *,
DHS
( )
H H
i
s
i
ig *, *,
Model name
2
( ) ( )
( )
( )
( ) ( ) ( )
H T p H T H T
H T p H T p
i
v
i
s
i
g
sub i
i
s
i
s
i
s
*, *, *, *
*, *, *,
,
, ,

+
p
i
s *,
Model name
( )
H H
i
v
i
ig *, *,
Route ID
(Default: H H
i
v
i
ig *, *,
= 0 )
( )
sub i
H T
*
Model name
( ) ( ) ( )
H T p H T p
i
s
i
s
i
s *, *, *,
, ,
Route ID
(Default:
( ) ( )
H T p H T p
i
s
i
s
i
s *, *, *,
, ,
= 0 )
( ) ( )
H T p H T p
i
s
i
s
i
s *, *, *,
, ,
DHSPC
Subord. 1
V T
V
T
dp
i
s i
s
p
p
*,
*,
_
,
1
]
1
p
i
s *,
Model name
V
i
s *,
Model name
(Default: 1 point)
H
m
s
HSMX
Major 1 Specified model Model name
2
x H H
i
s
i
s
m
E s
i
*, ,
+
H
m
s
Route ID
H
i
s *,
Route ID
H
m
E s ,
(Default: H
m
E s ,
= 0 )
3
( )
H H H
m
ig
m
s
m
ig
+
( )
H H
m
s
m
ig
Route ID
continued
Versi on 10
Property
Calculation
Methods and
Routes
Solid Enthalpy Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
H H
m
s
m
ig
DHSMX
( )
H H
m
s
m
ig
Model name
2
( )
x H H H
i
s
i
s
i
ig
m
E s
i
*, *, ,
+
( )
H H
i
s
i
ig *, *,
Route ID
H
m
E s ,
Route ID
(Default: H
m
E s ,
= 0 )
H
m
E s ,
HSXS
H
m
E s ,
Model name
2
H RT x
T
m
E s
i
s i
s
i
,
ln

_
,
i
Model name
Vapor Gibbs Energy Methods
Property
Symbol and
Name
Property
Type
Method
Code
i
v *,
GV
i
v *,
Model name
2
( )

i
ig
i
v
i
ig *, *, *,
+
( )

i
v
i
ig *, *,
Route ID
(Default:
i
v
i
ig *, *,
= 0 )

i
v
i
ig *, *,
DGV
( )

i
v
i
ig *, *,
Model name
2
RT RT
p
p
i
v
ref
ln ln
*,
+

_
,

i
v *,
Route ID
G
m
v
GVMX
G
m
v
Model name
continued
Versi on 10
Chapter 4
Vapor Gibbs Energy Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
2
y RT y y
i i
v
i i
i i
*,
ln +

i
v *,
Route ID
3
( )
G G G
m
ig
m
v
m
ig
+
( )
G G
m
v
m
ig
Route ID
(Default: G G
m
v
m
ig
= 0 )
G G
m
v
m
ig
DGVMX
( )
G G
m
v
m
ig
Model name
2
RT y RT
p
p
i i
v
ref
i
ln ln +

_
,

i
v *,
Route ID
(Default:
i
v *,
= 1 )
Liquid Gibbs Energy Methods
Property Symbol
and Name
Property
Type
Method
Code
i
l *,
GL
i
l *,
Model name
2
( )

i
ig
i
l
i
ig *, *, *,
+
( )

i
l
i
ig *, *,
Route ID

i
l
i
ig *, *,
DGL
( )

i
l
i
ig *, *,
Model name
2
RT RT
p
p
l
ref
ln ln
*,
+

_
,

i
l *,
Route ID
3
( ) ( )
( )
( ) ( ) ( )

i
l
i
l
i
ig
i
l
i
l
i
l
T p T
T p T p
*, *, *,
*, *, *,
,
, ,
+
p
i
l *,
Model name
( )

i
l
i
ig *, *,
Route ID
(Default:
i
l
i
ig *, *,
= 0)
( ) ( ) ( )

i
l
i
l
i
l
T p T p
*, *, *,
, , R
oute ID
(Default:
( ) ( )

i
l
i
l
i
l
T p T p
*, *, *,
, , =
0 )
continued
Versi on 10
Property
Calculation
Methods and
Routes
Liquid Gibbs Energy Methods (continued)
Property Symbol
and Name
Property
Type
Method
Code
( )
( )
i
l
i
l
i
l
T p
T p
*,
*, *,
,
,
DGLPC
Subord. 1
( ) ( ) ( )
( ) ( )
( )

*, *,
*, *, *,
,
,
l
i
ig
i
l
i
l
i
ig
T p T
T p T

p
i
l *,
Model name
( )

i
l
i
ig *, *,
Route ID
2
V dp
i
l
p
p
i
l
*,
*,
p
i
l *,
Model name
V
i
l *,
Model Name
(Default: 1 point)
G
m
l
GLMX
G
m
l
Model name
2
x RT x x G
i i
l
i i m
E l
i i
*, ,
ln + +

i
l *,
Route ID
G
m
E l ,
Route ID
(Default: G
m
E l ,
= 0 )
3
( )
G G G
m
ig
m
l
m
ig
+
4
Electrolyte model
( )
x
t Model name
x
t
Route ID
G G
m
l
m
ig
DGLMX
( )
G G
m
l
m
ig
Model name
2
( )
x G
i i
l
i
ig
m
E l
i

*, *, ,
+
( )

i
l
i
ig *, *,
Route ID
G
m
E l ,
Route ID
(Default: G
m
E l ,
= 0 )
G
m
E l ,
GLXS
G
m
E l ,
Model name
2
RT x
i
i
i
ln

i
Model name
Versi on 10
Chapter 4
Solid Gibbs Energy Methods
Property
Symbol and
Name
Property
Type
Method
Code
i
s *,
GL
i
s *,
Model name
2
( )

i
ig
i
s
i
ig *, *, *,
+
( )

i
s
i
ig *, *,
Route ID

i
s
i
ig *, *,
DGL
( )

i
s
i
ig *, *,
Model name
2
RT RT
p
p
s
ref
ln ln
*,
+

_
,

i
s *,
Route ID
3
( ) ( )
( )
( ) ( ) ( )

i
s
i
s
i
ig
i
s
i
s
i
s
T p T
T p T p
*, *, *,
*, *, *,
,
, ,
+
p
i
s *,
Model name
( ) ( )
( )

i
s
i
s
i
ig
T p T
*, *, *,
,
Route ID
(Default:
( ) ( )
i
l
i
s
i
ig
T p T
*, *, *,
, =
0)
( ) ( ) ( )

i
s
i
s
i
s
T p T p
*, *, *,
, , R
oute ID
(Default:
( ) ( )

i
s
i
s
i
s
T p T p
*, *, *,
, , =
0 )
( )
( )
i
s
i
s
i
s
T p
T p
*,
*, *,
,
,
DGLPC
Subord. 1
V dp
i
l
p
p
i
l
*,
*,
p
i
l *,
Model name
V
i
l *,
Model Name
(Default: 1 point)
G
m
s
GLMX
G
m
s
Model name
2
x G RT x x
i
s
i
s
m
E s
i
s
i
s
i i
*, ,
ln + +

i
s *,
Route ID
G
m
E s ,
Route ID
(Default: G
m
E s ,
= 0 )
3
( )
G G G
m
ig
m
s
m
ig
+
continued
Versi on 10
Property
Calculation
Methods and
Routes
Solid Gibbs Energy Methods
Property
Symbol and
Name
Property
Type
Method
Code
G G
m
s
m
ig
DGLMX
( )
G G
m
s
m
ig
Model name
2
( )
x G
i
s
i
s
i
ig
m
E s
i

*, *, ,
+
( )

i
s
i
ig *, *,
Route ID
G
m
E s ,
Route ID
(Default: G
m
E s ,
= 0 )
G
m
E s ,
GLXS
G
m
E s ,
Model name
2
RT x
i
s
i
i
s
ln

i
Model name
Vapor Entropy Methods
Property
Symbol and
Name
Property
Type
Method
Code
S
i
v *,
SV
Major 1
( )
1
T
H
i
v
i
v *, *,

H
i
v *,
Route ID
2
( )
S S S
i
ig
i
v
i
ig *, *, *,
+
( )
S S
i
v
i
ig *, *,
Route ID
(Default: S S
i
v
i
ig *, *,
= 0 )
3 Specified model
S
i
v *,
Model name
S S
i
v
i
ig *, *,
DSV
Subord. 1
H H
T T
i
v
i
ig
i
v
i
ig *, *, *, *,

_
,
_
,

( )
H H
i
v
i
ig *, *,
Route ID
(Default: H H
i
v
i
ig *, *,
= 0 )
( )

i
v
i
ig *, *,
Route ID
(Default:
i
v
i
ig *, *,
= 0)
2
( )

T
i
v
i
ig *, *,
( )

i
v
i
ig *, *,
Model name
S
m
v
Major 1
( )
1
T
H G
m
v
m
v
H
m
v
Route ID
G
m
v
Route ID
continued
Versi on 10
Chapter 4
Vapor Entropy Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
2
( )
S S S
m
ig
m
v
m
ig
+
( )
S S
m
v
m
ig
Route ID
(Default: S S
m
v
m
ig
= 0 )
3 Specified model
S
m
v
Model name
S S
m
v
m
ig
DSVMX
( )
S S
m
v
m
ig
Model name
2
H H
T
G G
T
m
v
m
ig
m
v
m
ig

_
,

_
,
( )
H H
m
v
m
ig
Route ID
(Default: H H
m
v
m
ig
= 0 )
( )
G G
m
v
m
ig
Route ID
(Default G G
m
v
m
ig
= 0)
3
( )

T
G G
m
v
m
ig
( )
G G
m
v
m
ig
Model name
Liquid Entropy Methods
Property
Symbol and
Name
Property
Type
Method
Code
Required
S
i
l *,
SL
Major 1
( )
1
T
H
i
l
i
l *, *,

H
i
l *,
Route ID
i
l *,
Route ID
2
( )
S S S
i
ig
i
v
i
ig *, *, *,
+
( )
S S
i
l
i
ig *, *,
Route ID
3 Specified model
S
i
l *,
Model name
S S
i
l
i
ig *, *,
DSL
Subord. 1
H H
T T
i
l
i
ig
i
l
i
ig *, *, *, *,

_
,
_
,

( )
H H
i
l
i
ig *, *,
Route ID
2
( )

T
i
l
i
ig *, *,
( )

i
l
i
ig *, *,
Route ID
( )

i
l
i
ig *, *,
Model name
continued
Versi on 10
Property
Calculation
Methods and
Routes
Liquid Entropy Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
Required
3 Specified Model
( )
S S
i
l
i
ig *, *,
Model name
S
m
l
SLMX
Major 1
( )
1
T
H G
m
l
m
l
H
m
l
Route ID
G
m
l
Route ID
2
( )
S S S
m
ig
m
l
m
ig
+
( )
S S
m
l
m
ig
Route ID
3 Specified model
S
m
l
Model name
4
( )
S f H G x
m
l
m
l
m
l t
, , H
m
l
model
G
m
l
model
x
t
Route ID
S S
m
l
m
ig
DSLMX
( )
S S
m
l
m
ig
Model name
2
H H
T
G G
T
m
l
m
ig
m
l
m
ig

_
,

_
,
( )
H H
m
l
m
ig
Route ID
( )
G G
m
l
m
ig
Route ID
3
( )

T
G G
m
l
m
ig
( )
G G
m
l
m
ig
Model name
Solid Entropy Methods
Property
Symbol and
Name
Property
Type
Method
Code
S
i
s *,
SS
S
i
s *,
Model name
2
( )
1
T
H
i
s
i
s *, *,

H
i
s *,
Route ID
i
s *,
Route ID
continued
Versi on 10
Chapter 4
Solid Entropy Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
S S
i
s
i
ig *, *,
DSS
Subord. 1
H H
T T
i
s
i
ig
i
s
i
ig *, *, *, *,

_
,
_
,

( )
H H
i
s
i
ig *, *,
Route ID
( )

i
s
i
ig *, *,
Route ID
2 Specified model
( )
S S
i
s
i
ig *, *,
Model name
S
m
s
SSMX
Major 1
( )
1
T
H G
m
s
m
s
H
m
s
Route ID
G
m
s
Route ID
2
( )
S S S
m
ig
m
s
m
ig
+
( )
S S
m
s
m
ig
Route ID
S S
m
s
m
ig
DSSMX
( )
S S
m
s
m
ig
Model name
2
H H
T
G G
T
m
s
m
ig
m
s
m
ig

_
,

_
,
( )
H H
m
s
m
ig
Route ID
( )
G G
m
s
m
ig
Route ID
3
( )

T
G G
m
s
m
ig
( )
G G
m
s
m
ig
Model name
Molar Volume Methods
Property
Symbol and
Name
Property
Type
Method
Code
V
i
v *,
VV
V
i
v *,
Model name
V
m
v
VVMX
V
m
v
Model name
2
( )
V f y V
m
v
i i
v
,
*,
V
i
v *,
Route ID
V
m
v
Model name
continued
Versi on 10
Property
Calculation
Methods and
Routes
Molar Volume Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
3
( ) V f
m
v
i

i
Model name
V
m
v
Model name (eos only)
V
i
l *,
VL
V
i
l *,
Model name
V
m
l
VLMX
V
m
l
Model name
2
( )
V f x V
m
l
i i
l
,
*,
V
i
l *,
Route ID
V
m
l
Model name
3
Electrolyte model
( )
x
t
V
i
l *,
Model name
x
t
Route ID
4
( ) V f
m
l
i

i
Model name
V
m
l
Model name (eos only)
V
i
s *,
VS
V
i
s *,
Model name
V
m
s
VSMX
V
m
s
Model name
2
( )
V f x V
m
s
i
s
i
s
,
*,
V
i
s *,
Route ID
V
m
s
Model name
Versi on 10
Chapter 4
Viscosity Methods
Property
Symbol and
Name
Property
Type
Method
Code
n
i
v *,
MUV
i
v *,
Model name
2
( )
i
v
i
v
p
*, *,
0
( ) ( )
i
v
p
*,
0 Route ID
3
( )
i
v
i
v
f V
*, *,
V
i
v *,
Route ID
i
v *,
Model name
4
( )
( ) ( ) ( )

i
v
i
v
i
v
i
v
p
p p
*, *,
*, *,

+
0
0
( ) ( )
i
v
p
*,
0 Route ID
( ) ( ) ( )

i
v
i
v
p p
*, *,
0
Route
ID
( )
i
v
p
*,
0
MUVLP
( ) ( )
i
v
p
*,
0 Model name
( )
( )
i
v
i
v
p
p
*,
*,
_
,
0
MUVPC
( ) ( ) ( )

i
v
o
v
p p
*, *,
0 M
odel name
2
( ) ( ) ( ) ( )

i
v
o
v
i
v
p p f V
*, *, *,
0 V
i
v *,
Route ID
Model name
n
v
MUVMX
v
Model name
2

( )

v
i i
v
f y ,
*,
i
v *,
Route ID
v
Model name
3
( )
v v
p 0
( ) ( )
v
p 0 Route ID
4
( )
v
m
v
f V V
m
v
Route ID
5
( )
( ) ( ) ( )

i
v
i
v
i
v
i
v
p
p p
+

0
0
v
Model name
( ) ( )
v
p 0 Route ID
( ) ( ) ( )

i
v
i
v
p p 0
Route ID
continued
Versi on 10
Property
Calculation
Methods and
Routes
Viscosity Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
( ) ( )
v
p 0
MUVMXLP
( ) ( )
v
p 0 Model name
2
( ) ( ) ( ) ( )

v
i i
v
p f y p 0 0 ,
*,
( ) ( )
i
v
p
*,
0
Route ID
( ) ( )
v
p 0
Model name
( )
( )
v
v
p
p
_
,
0
MUVMXP
C
( ) ( ) ( )

v v
p p 0
Model
name
2
( ) ( ) ( ) ( )

v v
m
v
p p f V 0
V
m
v
Route ID
( ) ( ) ( )

v v
p p 0
Model
name
i
l *,
MUL
i
l *,
Model name
2
( )
i
l
i
l
f V
*, *,
V
i
l *,
Route ID
i
l *,
Model Name
l
MULMX
l
Model name
2
( )

l
i i
l
f x ,
*,
i
l *,
Route ID
l
Model name
3
( )
l
m
l
f V V
m
l
Route ID
l
Model name
Versi on 10
Chapter 4
Thermal Conductivity Methods
Property
Symbol and
Name
Property
Type
Method
Code
i
v *,
MUV
i
v *,
Model name
2
( ) ( )

i
v
i
v
p
*, *,
0 ( ) ( )
i
v
p
*,
0 Route ID
3
( )
( ) ( ) ( )

i
v
i
v
i
v
i
v
p
p p
*, *,
*, *,

+
0
0
( ) ( )
i
v
p
*,
0 Route ID
( ) ( ) ( )

i
v
i
v
p p
*, *,
0
Route ID
4
( ) ( )

i
v
i
v
i
v
f V p
*, *, *,
, 0 V
i
v *,
Route ID
( )
i
v
p
*,
0 Model name
i
v *,
Model Name
( )
i
v
p
*,
0
KVLP
( )
i
v
p
*,
0 Model name
2
( ) ( ) ( )

i
v
i
v
p f p
*, *,
0 0 ( )
i
v
p
*,
0 Route ID
i
v *,
Model name
( )
( )
i
v
i
v
p
p
*,
*,
0
KVPC
( ) ( ) ( )

i
v
i
v
p p
*, *,
0
Model name
2
( ) ( ) ( ) ( )

i
v
i
v
i
v
p p f V
*, *, *,
0 V
i
v *,
Route ID
( ) ( ) ( )

i
v
i
v
p p
*, *,
0
Model name
v
KVMX
v
Model name
2
( )

v
i i
v
f y ,
*,
i
v *,
Route ID
v
Model name
3
( )
v v
p 0
( ) ( )
v
p 0 Route ID
continued
Versi on 10
Property
Calculation
Methods and
Routes
Thermal Conductivity Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
4
( )
( ) ( ) ( )

v v
v v
p
p p
+

0
0
( ) ( )
v
p 0 Route ID
( ) ( ) ( )

v v
p p 0 Route
ID
5
( ) ( )

v
m
v v
f V p , 0 V
m
v
Route ID
( ) ( )
v
p 0 Route ID
v
Model name
( )
v
p 0
KVMXLP
( ) ( )
v
p 0 Model name
2
( )
( ) ( ) ( )

v
i i
v
i
v
p
f y p p

0
0 0 , ,
*, *,
i
v *,
Route ID
( )
i
v
p
*,
0 Route ID
( ) ( )
v
p 0 Model name
( ) ( )
v v
p p 0
KVMXPC
( ) ( ) ( )

v v
p p 0
Model name
2
( ) ( ) ( ) ( )

v v
m
v
p p f V 0
Route ID
( ) ( ) ( ) ( ) ( ) ( )

v v v v
p p p p 0 0
Model name
i
l *,
KL
i
l *,
Model name
2
( ) ( )

i
l
i
l
i
v
f V p
*, *, *,
, 0 V
i
l *,
Route ID
( ) ( )
i
v
p
*,
0 Route ID
i
l *,
Model name
l
KLMX
l
Model name
2
( )

l
i i
l
f x ,
*,
i
l *,
Route ID
l
Model name
continued
Versi on 10
Chapter 4
Thermal Conductivity Methods (continued)
Property
Symbol and
Name
Property
Type
Method
Code
3
( ) ( )

l
m
l v
f V p , 0 V
m
l
Route ID
( ) ( )
v
p 0 Route ID
l
Model name
i
s *,
KS
i
s *,
Model name
s
KSMX
s
Model name
2
( )

s
i
s
i
s
f x ,
*,
i
s *,
Route ID
s
Model name
Diffusion Coefficient Methods
Property
Symbol and
Name
Property
Type
Method
Code
D
ij
v
DV
D
ij
v
Model name
D
i
v
DVMX
D
i
v
Model name
2
( )
D f y D
i
v
i ij
v
, D
ij
v
Route ID
y
i
Model name
D
ij
l
DL
D
i
l
DLMX
2
( )
D f x D
i
l
i ij
l
, D
ij
l
Route ID
D
i
l
Model name
Versi on 10
Property
Calculation
Methods and
Routes
Surface Tension Methods
Property
Symbol and
Name
Property
Type
Method
Code
i
l *,
SIGL
l
SIGLMX
2
( )

l
i i
l
f x ,
*,
i
l *,
Route ID
l
Model name
Routes And Models
Thi s secti on expl ai ns the structure of physi cal property cal cul ati ons by showi ng the
rel ati onshi p between model s and routes, and between routes on di fferent l evel s. I t
al so expl ai ns how to trace a cal cul ati on route.
Concept of Routes
Each property val ue needed for a method eval uati on i s obtai ned from ei ther
another method eval uati on or a model eval uati on. Properti es obtai ned by method
eval uati on are major or subordi nate properti es. Properti es obtai ned by a model
eval uati on are i ntermedi ate properti es. The cal cul ati on of the top-l evel property i s
di ctated by:
Property name
Method
Sub-l evel route for each major or subordi nate property
Model name for each i ntermedi ate property (someti mes wi th a model opti on
code)
Thi s i nformati on i s cal l ed a route. There i s not necessari l y a major or subordi nate
property i n each method, but i f one occurs i n the method of the property of i nterest,
then the route depends on sub-l evel routes. There can be any number of l evel s i n a
route. Each l evel needs the i nformati on l i sted previ ousl y to be compl etel y speci fi ed.
Thi s way a tree of i nformati on i s formed. Si nce a model does not depend on
l ower-l evel i nformati on, you can thi nk of i t as an end-poi nt of a tree branch. Model
opti on codes are di scussed i n Model s, this chapter. (Exampl e 1 di scusses a route
that does not depend on other routes.)
Versi on 10
Chapter 4
Each bui l t-i n route i n ASPEN PLUS has a uni que route I D, whi ch i s composed of
the property name (see the tabl es l abel ed Major Properti es i n ASPEN PLUS,
Subordi nate Properti es i n ASPEN PLUS, and I ntermedi ate Properti es i n ASPEN
PLUS, al l earl i er i n thi s chapter ) and a number, for exampl e HLMX10. Therefore
the route I D can be used to represent the route i nformati on. (See exampl e 2 for a
route whi ch depends on a secondary route.)
Route I Ds associ ated wi th the route i nformati on represent a uni que combi nati on
of sub-l evel routes and model s. Therefore, a top-l evel route I D speci fi es the ful l
cal cul ati on tree. Because of the uni queness of route I Ds, you can use them for
documenti ng your si mul ati on.
A property method can cal cul ate a fi xed l i st of properti es (see Physi cal Properti es
i n ASPEN PLUS, thi s chapter ). The cal cul ati on procedure of each property
consti tutes a route and has a route I D. Therefore, a property method consi sts of a
col l ecti on of the route I Ds of the properti es i t can cal cul ate. The Property
Methods Routes sheet shows the routes used i n a property method. I f you want to
see al l of the bui l t-i n routes used for cal cul ati ng the property speci fi ed i n the
Property fi el d, use the l i st box i n a Route I D fi el d (see the fi gure l abel ed
Properti es Property Methods Routes Sheet.
Properties Property Methods Routes Sheet
Versi on 10
Property
Calculation
Methods and
Routes
Example 1 Route information for PHILMX, method 1
The fi rst method from the tabl e l abel ed Li qui d Fugaci ty Coeffi ci ent Methods on
page 4-12 for the cal cul ati on of the fugaci ty coeffi ci ent of component i n a l i qui d
mi xture i s speci fi ed model . The model can be an equati on-of-state model , that
cal cul ates the fugaci ty coeffi ci ent as a functi on of state vari abl es and correl ati on
parameters:
( )
l
i i
f p T x , , , correlation parameters
There are many model s that can be used to cal cul ate
l
i
, such as the
Redl i ch-Kwong-Soave model , the Peng-Robi nson model , or the Hayden-OConnel l
model . I t i s suffi ci ent to sel ect a model name i n order to compl etel y speci fy a
route accordi ng to thi s method.
Example 2 Route information for HLMX, method 3
The thi rd method for cal cul ati ng the l i qui d mi xture enthal py H
l
m
(see the tabl e
l abel ed Li qui d Enthal py Methods on page 4-18):
( )
H H H H
l
m
ig
m
l
m
ig
m
+
I n thi s method, H
l
m
depends on the i deal gas enthal py and the enthal py
departure H H
l
m
ig
m
, a subordi nate property. The tabl e l abel ed Li qui d Enthal py
Methods on page 4-18 i ndi cates i n the ri ghtmost col umn that the requi red
i nformati on i s the route I D for the subordi nate property. The top-l evel route now
refers to a sub-l evel route I D. For al l methods that use both an i deal gas
contri buti on and a departure functi on, ASPEN PLUS automati cal l y fi l l s i n the
i deal gas cal cul ati on. You need to speci fy onl y the departure functi on. To speci fy
the sub-l evel route for the enthal py departure, you must choose a method. For
exampl e, method 1: speci fi ed model (see the tabl e l abel ed Li qui d Enthal py
Methods on page 4-18). For thi s method, the requi red i nformati on i s the model
name, such as the Redl i ch-Kwong-Soave equati on-of-state model .
Versi on 10
Chapter 4
Models
A model consi sts of one or more equati ons to eval uate a property, and has state
vari abl es, uni versal parameters, and correl ati on parameters as i nput vari abl es.
Properti es obtai ned by model eval uati on are cal l ed i ntermedi ate properti es. They
never depend on major or subordi nate properti es, whi ch need a method eval uati on.
I n contrast to methods whi ch are based on uni versal sci enti fi c pri nci pl es onl y,
model s are much more arbi trary i n nature, and have constants whi ch need to be
determi ned by data fi tti ng. An exampl e of a model i s the Extended Antoi ne vapor
pressure equati on (see Chapter 3). Equati ons of state have bui l t-i n correl ati on
parameters and are al so model s.
Model s are someti mes used i n mul ti pl e routes of a property method. For
exampl e, an equati on-of-state model can be used to cal cul ate al l vapor and l i qui d
departure functi ons of an equati on-of-state-based property method. The Rackett
model can be used to cal cul ate the pure component and mi xture l i qui d mol ar
vol umes, (V
l
i
*,
and V
l
m
), and i t can al so be used i n the cal cul ati on of the Poynti ng
correcti on factor, as part of the cal cul ati on of the pure component l i qui d fugaci ty
coeffi ci ent.
The Properti es Property Methods Model s sheet di spl ays the model s that are
gl obal l y used i n the routes of the current property method (see the fi gure l abel ed
Properti es Property Methods Model s Sheet). I n speci fi c routes, excepti ons to the
gl obal usage may occur. Modi fyi ng and Creati ng Routes, thi s chapter, di scusses
how to i denti fy these excepti ons. For a gi ven model , cl i ck on the Affected
Properti es button to di spl ay a l i st of properti es whi ch are affected by the model
cal cul ati ons. Use the l i st box on the Model Name fi el d to di spl ay a l i st of al l
avai l abl e model s for a speci fi c property. You can al so use the tabl es l abel ed
Thermodynami c Physi cal Property Model s on page 4-41, Transport Property
Model s on page 4-43, and Nonconventi onal Sol i d Property Model s on page 4-44. I f
you need to use a propri etary model or a new model from the l i terature, you can
i nterface these to ASPEN PLUS (See ASPEN PLUS User Models.)
Versi on 10
Property
Calculation
Methods and
Routes
Properties Property Methods Models Sheet
Some model s have model opti on codes to speci fy di fferent possi bl e cal cul ati on
opti ons. For exampl e, the model WHNRY has three opti ons to cal cul ate the
wei ghti ng factor from the cri ti cal mol ar vol ume. The cal cul ati on opti on i s
i denti fi ed by the model opti on code. On the Property Methods Model s sheet, fi rst
sel ect the model , then cl i ck the Opti on Codes button to di spl ay a l i st of opti on
code val ues for the model . Use Hel p for descri pti ons of the opti on codes.
Versi on 10
Chapter 4
Thermodynamic Physical Property Models
Thermodynamic Properties Model Model Name Phase Properties
Antoine/Wagner PL0XANT L L1 L2 PL
API liquid volume VL2API L VLMX
Aqueous Electrolyte NRTL Enthalpy HAQELC L HLMX
Aqueous Electrolyte NRTL Gibbs Energy GAQELC L GLMX
ASME Steam Tables ESH2O0,ESH2O V L
Brelvi-OConnell VL1BROC L VLPM

Bromley-Pitzer GMPT2 L GAMMA
Bromley-Pitzer Enthalpy HAQPT2 L HLMX
Bromley-Pitzer Gibbs Energy GAQPT2 L GLMX
BWR-Lee-Starling ESBWR0, ESCSTBWR V L
Cavett Liquid Enthalpy Departure DHL0CVT, DHL2CVT L DHL,DHLMX

Chao-Seader PHL0CS L PHIL
Clarke Aqueous Electrolyte Density VAQCLK L VLMX
Constant Activity Coefficient GMCONS S GAMMA
Costald Liquid Volume VL0CTD,VL2CTD L VL,VLMX
Debije-Hckel Volume VAQDH L VLMX
DIPPR Liquid Heat Capacity HL0DIP, DHL0DIP L HL, DHL
Electrolyte NRTL GMENRTL L L1 L2 GAMMA
Electrolyte NRTL Enthalpy HMXENRTL L HLMX
Electrolyte NRTL Gibbs Energy GMXENRTL L GLMX
Grayson-Streed PHL0GS L PHIL
Hayden-O'Connell ESHOC0, ESHOC V
Henrys constant HENRY1 L HNRY,WHNRY

HF equation of state ESHF0, ESHF V
Ideal Gas ESIG0, ESIG V
Kent-Eisenberg ESAMIN L PHILMX, GLMX,

HLMX, SLMX
A pure component equation-of-state model calculates:

PHI L,PHI V,DHL,DHV,DGL,DGV,DSL,DSV,VL,VV
A mixture equation-of-state model calculates:

PHI LMX,PHI VMX,DHLMX,DHVMX,DGLMX,DGVMX,DSLMX,DSVMX,VLMX,VVMX
DHLMX,DHVMX,DGLMX,DGVMX,DSLMX,DSVMX,VLMX,VVMX
continued
Versi on 10
Property
Calculation
Methods and
Routes
Thermodynamic Physical Property Models (continued)
Lee-Kesler ESLK V L
Lee-Kesler-Plcker ESLKP0, ESLKP V L
Modified UNIFAC Dortmund GMUFDMD L L1 L2 GAMMA

NBS/NCR Steam Tables ESSTEAM0, ESSTEAM V L
Nothnagel ESNTH0, ESNTH V
NRTL (Non-Random Two Liquid) GMRENON L GAMMA

Peng-Robinson-Boston-Mathias ESPR0, ESPR V L
Pitzer GMPT1 L GAMMA

Pitzer Enthalpy HAQPT1 L HLMX
Pitzer Gibbs Energy GAQPT1 L GLMX
Polynomial Activity Coefficient GMPOLY S GAMMA
Predictive SRK ESRKSV10, ESRKSV1 V L
Peng-Robinson-Wong-Sandler ESPRWS0, ESPRWS V L
Peng-Robinson-MHV2 ESPRV20, ESPRV2 V L
Rackett / DIPPR Liquid Density VL0RKT, VL2RKT L VL,VLMX

Redlich-Kister GMREDKIS L S GAMMA
Redlich-Kwong ESRK0, ESRK V
Redlich-Kwong-Soave-Boston-
Mathias
ESRKS0, ESRKS V L
Redlich-Kwong-Aspen ESRKA0, ESRKA V L
RKS-MHV2 ESRKSV20, ESRKSV2 V L
RKS-Wong-Sandler ESRKWSWS0, ESRKSWS V L
Schwartzentruber-Renon ESRKU0, ESRKU V L
Scatchard-Hildebrand GMXSH L GAMMA

Solids Heat Capacity Polynomial HS0POLY S HS
Solids Volume Polynomial VS0POLY S VS
Standard Peng-Robinson ESPRSTD0, ESPRSTD V L
Standard Redlich-Kwong-Soave ESRKSTD0, ESRKSTD V L


continued
Versi on 10
Chapter 4
Thermodynamic Physical Property Models (continued)
Three-Suffix Margules GMMARGUL L S GAMMA
UNIFAC GMUFAC L L1 L2 GAMMA
UNIQUAC GMUQUAC L L1 L2 GAMMA
Van Laar GMVLAAR L GAMMA
Wagner interaction parameter GMWIP S GAMMA
Watson / DIPPR DHVLWTSN L DHVL
Wilson GMWILSON L GAMMA


Andrade / DIPPR MUL0ANDR, MUL2ANDR L MUL, MULMX
API liquid viscosity MUL2API L MULMX
API surface tension SIG2API L SIGLMX
Chapman-Enskog-Brokaw / DIPPR MUV0CEB V MUVLP
Chapman-Enskog-Brokaw mixing rule MUV2CEB V MUVMXLP
Chapman-Enskog-Wilke-Lee Binary DV0CEWL V DV
Chapman-Enskog-Wilke-Lee Mixture DV1CEWL V DVMX
Chung-Lee-Starling low pressure Viscosity MUL0CLSL, MUL2CLSL V MUVLP,
MUVMXLP
Chung-Lee-Starling Viscosity MUV0CLS2, MUV0CLS2 V L MUV, MUVMX
Chung-Lee-Starling KV0CLS2, KV2CLS2 V KV, KVMX
thermal conductivity KL0CLS2, KL2CLS2 L KL, KLMX
Dawson-Khoury-Kobayashi Binary DV1DKK V DV
Dawson-Khoury-Kobayashi Mixture DV1DKK V DVMX
Dean-Stiel pressure correction MUV0DSPC, MUV2DSPC V MUVPC,
MUVMXPC
Hakim-Steinberg-Stiel / DIPPR SIG0HSS, SIG2HSS L SIGL, SIGLMX
IAPS viscosity MUV0H2O
MUL0H2O
V
L
MUV
MUL
continued
Versi on 10
Property
Calculation
Methods and
Routes
Transport Property Models (continued)
IAPS thermal conductivity KV0H2O
KL0H2O
V
L
KV
KL
IAPS thermal surface tension SIG0H2O L SIGL
Jones-Dole electrolyte correction MUL2JONS L MULMX
Letsou-Stiel MUL0LEST, MUL2LEST L MUL, MULMX
Lucas MUV0LUC, MUV2LUC V MUV, MUVMX
Nernst-Hartley DL0NST, DL1nst L DL, DLMX
Onsager-Samaras electrolyte correction SIG2ONSG L SIGLMX
Riedel electrolyte correction KL2RDL L KLMX
Sato-Riedel / DIPPR KL0SR, KL2SRVR L KL, KLMX
Stiel-Thodos / DIPPR KV0STLP V KVLP
Stiel-Thodos pressure correction KV0STPC, KV2STPC V KVPC
TRAPP viscosity MUV0TRAP, MUV2TRAP
MUL0TRAP, MUL2TRAP
V
L
MUV, MUVMX,
MUL, MULMX
TRAPP thermal conductivity KV0TRAP, KV2TRAP V KV, KVMX
KL0TRAP, KL2TRAP L KL, KLMX
Wassiljewa-Saxena-Maxon mixing rule KV2WMSM V KVMXLP
Wilke-Chang binary DL0WC2 L DL
Wilke-Chang mixture DL1WC L DLMX
Thermodynamic Properties Model Model Name Phase
General Coal Enthalpy Model HCOALGEN S
General Density Polynomial DNSTYGEN S
General Heat Capacity Polynomial ENTHGEN S
IGT Coal Density Model DCOALIGT S
IGT Char Density Model DCHARIGT S
Versi on 10
Chapter 4
Property Model Option Codes
The fol l owi ng tabl es l i st the model opti on codes avai l abl e:
Transport Property Model s
Acti vi ty Coeffi ci ent Model s
Equati on of State Model s
K-val ue Model s
Enthal py Model s
Option Codes for Transport Property Models
Model Name Option
Code
Value Descriptions
SIG2HSS 1 1 Exponent in mixing rule (default)
-1,-2,-3 Exponent in mixing rule
SIG2ONSG 1 1 Exponent in mixing rule (default)
-1,-2,-3 Exponent in mixing rule
MUL2API,
MULAPI92
1 0 Release 9 method. First, the API, SG of the mixture is calculated, then
the API correlation is used (default)
1 Pre-release 9 method. Liquid viscosity is calculated for each
pseudocomponent using the API method. Then mixture viscosity is
calculated by mixing rules.
Option Codes for Activity Coefficient Models
Model Name Option
Code
Value Descriptions
GMXSH 1 0 No volume term (default)
1 Includes volume term
WHENRY 1 1 Equal weighting
2 Size - VC****(1/3)
3 Area - VC****(2/3) (default)
4 Volume - VC
GMELC, HAQELC, 1 Defaults for pair parameters
HMXELC,GAQELC, 1 Pair parameters default to zero
continued
Versi on 10
Property
Calculation
Methods and
Routes
Option Codes for Activity Coefficient Models (continued)
Model Name Option
Code
Value Descriptions
GMXELC 2 Solvent/solute pair parameters default to water parameters.
Water/solute pair parameters default to zero (default)
3 Default water parameters to 8, -4. Default solvent/solute parameters to
10, -2
2 Vapor phase EOS for liquid enthalpy and Gibbs energy
0 Ideal gas EOS (default)
1 HF EOS for hydrogen fluoride
3 Solvent/solvent binary parameter names
0 Use scalar GMELCA, GMELCB and GMELCM (default)
1 Use vector NRTL(8)
GMENRTL, 1 Defaults for pair parameters
HMXENRTL, 1 Pair parameters default to zero
GMXENRTL 2 Solvent/solute pair parameters default to water parameters.
Water/solute pair parameters default to zero
10, -2 (default)
GMXENRHG, 1 Defaults for pair parameters
GMENRHG, 1 Pair parameters default to zero
HMXENRHG 2 Solvent/solute pair parameters default to water parameters.
Water/solute pair parameters default to zero
10, -2 (default)
continued
Versi on 10
Chapter 4
Option Codes for Activity Coefficient Models (continued)
Model Name Option
Code
Value Descriptions
4 Standard enthalpy calculation
0 Standard electrolytes method (Pre release 10)
1 Helgeson method (default)
5 Reaction temperature dependency estimation
0 Do not calculate
1 Calculate (default)
GMPT1 1 Defaults for pair mixing rule
-1 No unsymmetric mixing
0 Unsymmetric mixing polynomial (default)
1 Unsymmetric mixing integral
GAQPT3, GMPT3, 1 Defaults for pair mixing rule
HAQPT3 -1 No unsymmetric mixing
0 Unsymmetric mixing polynomial (default)
1 Unsymmetric mixing integral
2 Standard enthalpy calculation
0 Standard electrolytes method (Pre-release 10)
1 Helgeson method (Default)
3 Estimation of K-stoic temperature dependency
0 Use value at 298.15 K
1 Helgeson Method (default)
HS0POL1, 1 Reference temperature usage
GS0POL1, 0 Use standard reference temperature (default)
SS0POL1 1 Use liquid reference temperature
Versi on 10
Property
Calculation
Methods and
Routes
Option Codes for Equation of State Models
Model Name Option
Code
Value Descriptions
ESHOC, ESHOC0,
PHV0HOC
1 0 Hayden-OConnell model. Use chemical theory only if one component
has HOCETA=4.5 (default)
1
2
Always use the chemical theory regardless of HOCETA values
Never use the chemical theory regardless of HOCETA values
ESPR, ESPR0 1 0 ASPEN Boston/Mathias alpha function (default)
1 Original literature alpha function
ESPRSTD,
ESPRSTD0
1 0 ASPEN Boston/Mathias alpha function
1 Original literature alpha function (default)
ESRKS, ESRKS0 1 0 ASPEN Boston/Mathias alpha function (default)
2 Grabowski and Daubert alpha function for H2 above TC (alpha =
1.202 exp(-0.30228 ** Tri)
ESRKSTD,
ESRKSTD0
1 0 ASPEN Boston/Mathias alpha function
1 Original literature alpha function (default)
1.202 exp(-0.30228 ** Tri)
ESRKSW,
ESRKSW0
1 0 ASPEN Boston/Mathias alpha function (default)
1.202 exp(-0.30228 ** Tri)
ESRKU, ESRKU0 1 Initial temperature for binary parameter estimation
0 At TREF=25 C (default)
1 The lower of TB(i) or TB(j)
2 (TB(i) + TB(j))/2
> 2 Value entered used as temperature
2 VLE or LLE UNIFAC
0 VLE (default)
1 LLE
3 Property diagnostic level flag (-1 to 8)
4 Vapor phase EOS used in generation of TPxy data with UNIFAC
0 Hayden-OConnell (default)
continued
Versi on 10
Chapter 4
Option Codes for Equation of State Models (continued)
Model Name Option
Code
Value Descriptions
1 Redlich-Kwong
5 Do/do not estimate binary parameters
0 Estimate (default)
1 Set to zero
ESHF, ESHF0 1 0 Equation form for Log(k) expression: LOG(K) = A + B/T + C**LN(T) +
D**T (default)
1 LOG(K) = A + B/T + C**T + D/T^2 + E**LOG(P)
ESPRWS,
ESPRWS0,
1 Equation form for alpha function
ESPRV1, ESPRV10, 1 Original literature alpha function
ESPRV2, ESPRV20, 2 Mathias-Copeman alpha function
3 Schwartzentruber-Renon alpha function (default)
ESRKSWS,
ESRKSWS0 ,
1 Equation form for alpha function
ESRKSV1,
ESRKSV10,
ESRKSV2,
ESRKSV20,
2 Mathias-Copeman alpha function
3 Schwartzentruber-Renon alpha function (default)
ESSTEAM, 1 0 ASME 1967 correlations
ESSTEAM0 1 NBS 1984 equation of state (default)
ESH2O, ESH2O0 1 0 ASME 1967 correlations (default)
1 NBS 1984 equation of state
Option Codes for K-value Models
Model Name Option Code Value Descriptions
BK10 1 0 Treat pseudocomponents as paraffins (default)
1 Treat pseudocomponents as aromatics
Versi on 10
Property
Calculation
Methods and
Routes
Option Codes for Enthalpy Models
Model Name Option
Code
Value Descriptions
DHL0HREF 1 1 Use Liquid reference state for all components (Default)
2 Use liquid and gaseous reference states based on the state of each
component
Tracing a Route
The structure of a ful l cal cul ati on route i s general l y shaped as a tree control . Each
poi nt i n the tree where a branch spl i ts off (a node) represents a method. The
branches themsel ves are the routes. The ends of the branches are model s. The
starti ng poi nt for traci ng a route i s usual l y fi ndi ng a route I D on the Property
Methods Routes sheet, for whi ch you want to know the cal cul ati on procedure. The
following example descri bes how you can trace a known route I D.
Example 1 Tracing the route HLMX08
The route I D i s on the Properti es Property Methods Routes sheet for the Wi l son
property method. I t appears i n the second col umn, next to the property HLMX:
HLMX08 (a si mi l ar sheet i s shown i n the fi gure l abel ed Properti es Property
Methods Routes Sheet).
Cl i ck on the property HLMX or the route I D HLMX08, then cl i ck the Vi ew
button. The Vi ew Route di al og box appears.
I f you cl i ck on a route or model on the tree, a short descri pti ons of the route or
model appears i n the Prompt area. At the fi rst node, the route HLMX08 appears,
whi ch uses method 3. I n thi s method, the l i qui d mi xture enthal py i s cal cul ated
from the i deal gas enthal py and the enthal py departure. ASPEN PLUS
automati cal l y fi l l s i n the i deal gas cal cul ati ons. Onl y the departure functi on
route I D must be speci fi ed. Therefore, there i s onl y one branch attached to the
node for route HLMX08.
There are two ways to l ook up the equati on correspondi ng to the method number
of a route.
The fi rst method, i f you are i n ASPEN PLUS i s to:
1. Cl ose the Vi ew Route di al og box.
2. Go to the Property fi el d correspondi ng to the route.
3. Use Hel p to get onl i ne hel p on methods correspondi ng to thi s property.
4. Locate the formul a correspondi ng to the method number.
Versi on 10
Chapter 4
The second method i s to l ook up the method i n the tabl e l abel ed Vapor Fugaci ty
Coeffi ci ent Methods on page 4-11 i n the secti on correspondi ng to the property for
whi ch you trace the route (HLMX). The formul a i s l i sted next to the method
number.
The next step i n the route HLMX08 i s the cal cul ati on of the l i qui d mi xture
enthal py departure wi th route I D: DHLMX08. Thi s cal cul ati on i s based on
method 2, whi ch cal cul ates DHLMX as the mol e fracti on average of pure
component enthal py departure (DHL) and the excess enthal py (HLXS).
Therefore, two branches spl i t from thi s route and the compl ete route can be
traced thi s way.
These two steps i n traci ng the route HLMX08 show that a route I D i s
characteri sti c for the methods, routes and model s speci fi ed on i ts own l evel .
However, by speci fyi ng DHLMX08 on the top l evel , the top l evel route i s al so
characteri sti c for the l evel bel ow because DHLMX08 stands for a ful l
speci fi cati on on i ts secondary l evel . I f we conti nue thi s reasoni ng down the tree to
the model s, then i t becomes cl ear that HLMX08 represents the ful l speci fi cati on
of the ful l tree. And DHLMX08 represents the ful l speci fi cati on of the ful l tree,
mi nus the top l evel . Therefore every bui l t-i n route has a uni que I D. Thi s feature
wi l l be used i n Modi fyi ng and Creati ng Routes on page 4-57.
Modifying and Creating Property Method
The bui l t-i n property methods i n ASPEN PLUS contai n choi ces of major property
routes that fi t most engi neeri ng needs. The combi nati ons of the routes for di fferent
properti es are chosen i n a l ogi cal way, as expl ai ned i n Chapter 2. You may
someti mes need to customi ze property methods. For exampl e, to change model s or
routes on a mai n or a sub-l evel . Thi s secti on expl ai ns how to do thi s and gi ves
exampl es of how to i mpl ement the most frequentl y used modi fi cati ons.
Modifying Existing Property Methods
The fol l owi ng subsecti ons expl ai n the di fferent types of modi fi cati ons that can be
made to property methods.
Replacing Routes
The Property Methods Routes sheet al l ows you to see whi ch routes are used i n a
certai n property method and to trace a route (see Routes and Model s, this chapter).
Thi s form al so al l ows you to repl ace routes. A route repl acement i nfl uences the
cal cul ati ons of one property at a ti me.
Versi on 10
Property
Calculation
Methods and
Routes
To repl ace routes:
1. From the Data menu, sel ect Properti es, then Property Method.
The Property Methods Object Manager appears.
2. Sel ect the property method and cl i ck on Edi t.
The Property Methods form appears.
3. Go to the Routes sheet.
4. I n the Route I D fi el d of the property of i nterest, use Li st to l i st al l avai l abl e
routes for thi s property.
As you scrol l through the l i st, the prompt di spl ays a short descri pti on of the
route. When you gai n experi ence, the descri pti on from the prompt shoul d be
suffi ci ent. I f you requi re more i nformati on,
a) Sel ect the route, the cl i ck on the Vi ew button to get the tree di agram for
thi s route (see Routes And Model s on page 4-36). You can now trace the
route i n detai l .
b) Cl ose the Vi ew Route di al og box to return to the Routes sheet.
5. Sel ect a route that fi ts your needs.
The newl y sel ected route changes col or, so that you are abl e to l ocate your property
method modi fi cati ons i mmedi atel y on thi s sheet.
The techni que i s i denti cal for subordi nate properti es.
Example 1 Using COSTALD liquid molar volume in PENG-ROB
I n the PENG-ROB property method, the Rackett equati on i s used for the l i qui d
mol ar vol ume (route VLMX01, property VLMX). For hi gh pressure cal cul ati ons,
use the COSTALD model whi ch i s sui ted for compressed l i qui ds. The route sel ected
i s VLMX22. For consi stency wi th pure component resul ts, repl ace the VL
cal cul ati on wi th VL06.
Example 2 Using Lee-Kesler liquid volume in RK-SOAVE
For a hi gh pressure hydrocarbon appl i cati on, use the Lee-Kesl er l i qui d mol ar
vol ume cal cul ati on rather than the atmospheri c API densi ty cal cul ati on. Sel ect
VLMX13 for VLMX. No correspondi ng pure component routes are avai l abl e, si nce
these cal cul ati ons are for compl ex petrol eum mi xtures, of whi ch the pure
components are onl y parti al l y known.
Versi on 10
Chapter 4
Example 3 Using ideal mixing for the liquid molar volume in WILSON
You want to compare the Rackett mi xture equati on wi th i deal mi xi ng. The pure
component l i qui d mol ar vol ume shoul d remai n as i t i s (Model : VL0RKT, Route I D:
VL01). Sel ect the route VLMX23 to use the i deal mi xi ng rul e (mol e fracti on average
of pure component l i qui d mol ar vol umes).
Example 4 Removing Poynting correction of an activity coefficient
based property method
The Poynti ng correcti on i s the pressure correcti on to the pure component l i qui d
fugaci ty coeffi ci ent. For val i dati on purposes, you need to compare your si mul ati on
wi th previ ous resul ts that have been obtai ned wi thout the Poynti ng correcti on.
I n al l acti vi ty coeffi ci ent based property methods wi th the Redl i ch-Kwong
equati on of state as the vapor phase model , the route PHI L04 i s used for the pure
component l i qui d fugaci ty coeffi ci ent. Traci ng PHI L04 (usi ng the Vi ew button)
shows that the pressure correcti on i s cal cul ated by the subordi nate property
PHI LPC wi th route I D PHI LPC01.
On the Property Methods Routes sheet, sel ect Subordi nate property i n the
Property route fi el d. Locate the property PHI LPC i n the Property fi el d, then
repl ace PHI LPC01 wi th PHI LPC00 (no correcti on) i n the Route I D fi el d. I f you
trace PHI L04 agai n (usi ng the Vi ew button), you wi l l noti ce that the tree i s
dynami c; i t refl ects the changes you made i n a sub-l evel route, i n thi s case for
PHI LPC.
I n the acti vi ty coeffi ci ent based property methods wi th the i deal gas l aw as the
vapor phase model , the route PHI L00 i s used. Traci ng PHI L00 shows that
PHI LPC00 i s used by defaul t. No changes are needed.
Replacing Models and Using Multiple Data Sets
The Property Methods Model s sheet al l ows you to see whi ch model s are used i n a
certai n property method (see Routes And Model s on page 36). Thi s sheet al so al l ows
you to repl ace model s. Route repl acements i nfl uence onl y one property at a ti me. I n
contrast, a model repl acement i nfl uences al l the properti es that use the same
model . You can trace the routes of these properti es to determi ne where exactl y the
model i s used i n the cal cul ati on. I f you want to l i mi t the effect of a model
repl acement to a si ngl e route, you can modi fy an exi sti ng route or create a new
route (see Modi fyi ng and Creati ng Routes on page 4-57). Cl i ck the Affected
properti es button to see a l i st of properti es affected by the model .
I f you need to change both routes and model s, you must change the routes fi rst
usi ng the Routes sheet, then change the model s. I f you use the Model s sheet before
usi ng the Routes sheet, the changes you made on the Model s sheet wi l l be l ost.
Versi on 10
Property
Calculation
Methods and
Routes
To repl ace model s:
1. From the Data menu, sel ect Properti es, then Property Methods.
3. Go to the Model s sheet.
4. On the Model name fi el d of the property of i nterest, use Li st for al l avai l abl e
model s for thi s property. (You can al so use the tabl e l abel ed Li qui d Fugaci ty
Coeffi ci ent Methods, thi s chapter .)
As you scrol l through the l i st, the prompt di spl ays a short descri pti on of
the model .
5. Sel ect a model .
The newl y sel ected model changes col or, so that you are abl e to l ocate your
property method modi fi cati ons i mmedi atel y on thi s form. Al l properti es usi ng the
same model wi l l al so be changed.
I f you draw a tree di agram of a property i n whi ch the new model i s used, the
modi fi cati on i s al so shown(see Traci ng a Route on page 4-50).
Conflicting Route and Model Specifications
I f you speci fy a route for a certai n property and you al so speci fy a model that
cal cul ates a property that i s part of the route you speci fi ed, the i nformati on can be
confl i cti ng. I n ASPEN PLUS both repl acements wi l l be executed. The resul t, i n
most cases, i s that the model takes precedence, but you can al ways predi ct the
resul t by anal yzi ng the route and checki ng i f there i s an occurrence of thi s type of
model i n the tree.
Example 1 Using COSTALD liquid molar volume in PENG-ROB
The reasoni ng i s the same as i n Exampl e 1, Repl aci ng Routes, thi s chapter. The
approach here i s to repl ace the Rackett model s (VL0RKT, VL2RKT) by the
COSTALD model s (VL0CTD, VL2CTD). The resul t i s exactl y the same as for the
route repl acement.
Versi on 10
Chapter 4
Example 2 Using Peng-Robinson for vapor phase properties in NRTL-RK
You want to use the Peng-Robi nson equati on of state as the vapor phase model of
an acti vi ty coeffi ci ent based property method. I nstead of repl aci ng every vapor
phase property route, i t i s more effi ci ent to repl ace the equati on-of-state model
used for al l vapor phase properti es. I n the model fi el d, i f you sel ect ESPR for a
si ngl e vapor phase property, ASPEN PLUS repl aces al l other vapor phase
properti es by the ESPR model as wel l . For consi stency, use ESPR0 for pure
component vapor phase properti es.
Creating New Property Methods
The purpose of creati ng new property methods i s not so much to bui l d the col l ecti on
of routes from scratch, al though thi s i s possi bl e. I t i s more a matter of methodol ogy
and documentati on of your work. Suppose you make changes to exi sti ng property
methods, and you have successful l y compl eted your si mul ati ons. One year l ater you
may have a si mi l ar project where you begi n wi th your ol d si mul ati on model s. You
may not remember that the WI LSON property method you used i s not the
standard versi on. Therefore, i t i s recommended that you:
1. Create a new property method wi th an I D si mi l ar to the property method on
whi ch i t i s based.
2. Copy the base property method to the new property method
3. Make your changes.
There are two ways to begi n the creati on of a property method.
The first way to begin is:
1. On the Properti es Speci fi cati ons Gl obal sheet, sel ect the base property
method on the Base method fi el d.
2. Check the Modi fy property model s checkbox. The Modi fy Property Method
di al og box appears.
3. Enter the new property method name, then cl i ck OK.
4. Go to the Properti es Property Methods Object Manager.
5. Sel ect the new property method, then cl i ck Edi t.
The second way to begin is:
2. Cl i ck on New and enter the new property method name.
Versi on 10
Property
Calculation
Methods and
Routes
Then for both methods do the following steps:
1. Sel ect the Property Methods .Routes or the Property Methods .Model s sheet.
2. On the Base property method fi el d, use Li st and sel ect an exi sti ng property
method name.
ASPEN PLUS fi l l s i n al l the routes and model s i n both sheets.
3. Make your changes.
4. Use the newl y created property method i n a fl owsheet, a bl ock, a property
anal ysi s, or a col umn secti on.
Using Multiple Data Sets in Multiple Property Methods
To use a second data set wi th a model :
3. Go to the Model s sheet.
The DataSet col umn i s to the ri ght of the Model name col umn. The defaul t for
a data set number i s 1.
4. Change the data set number to 2 to i ntroduce a second set of parameters for a
model .
A second data set i s frequentl y used for acti vi ty coeffi ci ent model s. For exampl e,
the VLE are cal cul ated wi th one set of parameters, the LLE wi th another set. I f
you i ntroduce a second data set for an acti vi ty coeffi ci ent model , i t i s effecti ve
throughout the property method. To use two data sets i n di fferent parts of the
fl owsheet or a di sti l l ati on col umn, you must use two property methods: one
property method that uses the defaul t data set 1, and another property method
that uses the data set 2. I f you create a second data set for a model , ASPEN PLUS
automati cal l y defi nes the second set of parameters on the Properti es Parameters
forms. So you must enter the parameters val ues for the second data set after
creati ng the property method i n whi ch they are to be used.
Versi on 10
Chapter 4
Modifying and Creating Routes
The bui l t-i n routes i n ASPEN PLUS cover most engi neeri ng needs (see Routes And
Model s on page 4-36). However, whi l e modi fyi ng or creati ng property methods you
may need a route that i s not bui l t-i n (see Modi fyi ng and Creati ng Property Method
on page 4-51). You can create such a route based on the avai l abl e methods. Thi s
secti on expl ai ns and gi ves exampl es of modi fyi ng and creati ng routes.
To deci de i f you want to create a new route or modi fy an exi sti ng route, appl y the
same reasoni ng as for deci di ng whether to modi fy or create a new property
method (see Creati ng New Property Methods on page 4-55).We recommend you
choose a new route I D.
To modi fy an exi sti ng route or create a new route:
1. Fol l ow the procedure to trace routes, and consi der the avai l abl e methods for
the property of i nterest. Deci de on the route you want to modi fy, or the
method you want to use to create a route.
2. From the Data menu, sel ect Properti es, then Advanced, then
Routes.
The Routes Object Manager appears. There are no objects l i sted because
there are hundreds of avai l abl e routes. So you need to know from the anal ysi s
you di d on the Property Methods Routes sheet whi ch route you want to
modi fy.
3. Cl i ck on New. Enter a new route I D to create a new route, or enter an
exi sti ng route I D to modi fy an exi sti ng route.
The Routes Speci fi cati ons sheet. appears. At the top are the:
Property name
Method code
Route I D of the route to modi fy
4. When you base your new route on an exi sti ng route, enter the property name
i n the Property name fi el d and the base route I D i n the Copy route from fi el d,
and make your changes.
Or
When you create a compl etel y new route, enter the property name and
method code. Fi l l the Route I D and Model name fi el ds.
Versi on 10
Property
Calculation
Methods and
Routes
5. Use the Property Methods Routes sheet and enter the new route i n a property
method.
Or
Use the Routes Speci fi cati ons sheet of another route to use the newl y created
route i n another route.
Example 1 Use a second data set of NRTL parameters for HLXS
The representati on of two properti es wi th one data set i s someti mes not
sati sfactory, for exampl e wi th VLE and excess enthal py data. I f two data sets can
descri be the properti es separatel y, you wi l l need to use both sets i n the si mul ati on.
I n thi s exampl e, one set of bi nary parameters for the NRTL model i s used for
VLE cal cul ati ons. A second set of bi nary parameters i s used for excess enthal py
(HLXS).
Create a new route to cal cul ate HLXS. The si mpl est way i s to modi fy the exi sti ng
route used i n the NRTL property method. The Route I D i s HLXS10. On the
Properti es Advanced Routes Speci fi cati on sheet, change Data Set from 1 to 2.
Example 2 Using your own model for the liquid enthalpy
Your company has devel oped a correl ati on for the enthal py i n a speci fi c process
stream that you want to use. The necessary user model subrouti nes have been
wri tten accordi ng to ASPEN PLUS User Models. Al l bui l t-i n routes i n
ASPEN PLUS for the l i qui d mol ar enthal py are based on methods 2, 3 or 4.
However, to use the user model , method 1 (Speci fi ed model ) i s needed. Because no
exi sti ng route uses method 1 or needs thi s type of model , there i s no model for
l i qui d enthal py on the Property Methods Model s sheet.
Create a new route, for exampl e HLMXAP, usi ng method 1. On the Routes
Speci fi cati ons sheet,. the property name HLMX appears i n the Model area. Use
Li st from the Model name fi el d to sel ect HL2USR, the l i qui d mi xture enthal py
user model .
Reference the route HLMXAP i n the property method on the Property Methods
Routes sheet. You can check that the user enthal py model HL2USR appears on
the Property Methods Model s sheet.
O O O O
Versi on 10
Chapter 5
5 Electrolyte Simulation
El ectrol yte process si mul ati on has many appl i cati ons. I n ASPEN PLUS, you can
anal yze and opti mi ze processes i nvol vi ng i oni c speci es, compl ex i ons, sal t
preci pi tati on, wi th strong aci ds, weak aci ds and bases.
Exampl es of appl i cati ons for el ectrol yte process si mul ati on wi th ASPEN PLUS
i ncl ude:
Sour water stri ppi ng (petrochemi cal i ndustry)
Causti c bri ne evaporati on and crystal l i zati on (chl or-al kal i i ndustry)
Aci d gas removal (chemi cal and gas i ndustri es)
Ni tri c aci d separati on (nucl ear chemi cal i ndustry)
Trona processi ng (mi ni ng i ndustry)
Organi c sal t separati on (bi ochemi cal i ndustry)
Bl ack l i quor evaporati on (pul p and paper i ndustry)
El ectrol yte systems have three i mportant characteri sti cs:
Sol uti on chemi stry i n the l i qui d phase
Apparent and true component composi ti ons are di fferent
Non-i deal l i qui d phase thermodynami c behavi or
Thi s chapter descri bes appl i cati ons of el ectrol yte process si mul ati on and revi ews
the fol l owi ng fundamental characteri sti cs of el ectrol yte systems:
Sol uti on chemi stry
Apparent component and true component approaches
El ectrol yte thermodynami cs model s
El ectrol yte data regressi on
Versi on 10
Electrolyte
Simulation
Solution Chemistry
The sol uti on chemi stry i nvol ves a vari ety of chemi cal reacti ons i n the l i qui d phase.
Exampl es of such chemi cal reacti ons are:
Compl ete di ssoci ati on of strong el ectrol ytes
Parti al di ssoci ati on of weak el ectrol ytes
I oni c reacti ons among i oni c speci es
Compl ex i on formati on
Sal t preci pi tati on and di ssol uti on
These chemi cal reacti ons occur rapi dl y i n sol uti on, so chemi cal equi l i bri um
condi ti ons are assumed.
Sol uti on chemi stry affects el ectrol yte process si mul ati on by i nfl uenci ng physi cal
properti es, phase equi l i bri um, and other fundamental characteri sti cs of
el ectrol yte systems. For most nonel ectrol yte systems, chemi cal reacti ons occur
onl y i n reactors. For el ectrol yte systems, chemi cal equi l i bri um cal cul ati ons are
essenti al to al l types of uni t operati ons model i ng.
Sol uti on chemi stry di ctates the true components i n sol uti on and i mposes equal i ty
constrai nts on thei r composi ti on. The chemi cal equi l i bri um rel ati onshi p for
reacti on j i s expressed as:
ln ln
,
K v a
j i j i
i
(1)
Where:
K
j
= Chemi cal equi l i bri um constant
v
i j ,
= Reacti on stoi chi ometri c coeffi ci ent of component i
a
i
= Acti vi ty of component i
Computati on of the sol uti on chemi stry i s often combi ned wi th phase equi l i bri um
cal cul ati ons. Typi cal el ectrol yte si mul ati ons i nvol vi ng sol uti on chemi stry are:
Li qui d (aqueous) phase equi l i bri um (for exampl e, cal cul ati ng the pH for the
ti trati on of organi c aci d wi th causti c sol uti on)
Vapor-l i qui d (aqueous) phase equi l i bri um (for exampl e, extracti ve di sti l l ati on
wi th sal ts as extracti ve agents, and sour water stri ppi ng)
Li qui d (aqueous)-l i qui d (organi c) phase equi l i bri um (for exampl e, hydrocarbon-
sour water system and l i qui d-l i qui d extracti on of metal s)
Li qui d (aqueous)-sol i d equi l i bri um of sal t preci pi tati on (for exampl e,
crystal l i zati on of organi c or i norgani c sal ts)
Versi on 10
Chapter 5
To si mul ate an el ectrol yte system, you must properl y i denti fy al l rel evant chemi cal
reacti ons. Physi cal i nteracti ons i n sol uti ons are someti mes descri bed by
postul ati ng chemi cal reacti ons at equi l i bri um. The chemi cal theory of sol uti ons i s
used onl y for real chemi cal reacti ons. I ncorrect assumpti ons about the sol uti on
chemi stry i s the major cause of i naccuraci es i n si mul ati ons of reacti ve chemi cal
systems.
Use the El ectrol yte Expert System to i denti fy al l rel evant chemi cal reacti ons.
Starti ng from thi s set of reacti ons, you can remove and/or add reacti ons as
requi red to properl y represent your process.
You can use the Reacti ons Chemi stry form to descri be the sol uti on chemi stry and
to enter the chemi cal equi l i bri um constants. However, we strongl y recommend
that you use the El ec button on the Components.Mai n form and al l ow the
El ectrol ytes Expert System to set up the property speci fi cati ons for you.
For a system wi th a sol vent di el ectri c constant l ess than 10, i oni c reacti ons do
not take pl ace. Therefore, ASPEN PLUS bypasses al l sol uti on chemi stry
cal cul ati ons for such systems.
I f you defi ne the reacti ons on the Reacti ons Chemi stry form, ASPEN PLUS
checks for i nfeasi bl e or redundant reacti ons. I f such reacti ons exi st,
ASPEN PLUS i gnores them duri ng the cal cul ati ons.
Apparent Component and True Component Approaches
As a resul t of the sol uti on chemi stry, a set of true speci es i s present i n the l i qui d
phase that di ffers from apparent mol ecul ar components. Apparent or parent
components are present i n the system i f no reacti ons occurred. For exampl e, the
sour water stri pper system has three apparent mol ecul ar components: water,
ammoni a, and hydrogen sul fi de. The three mol ecul ar components di ssoci ate i n the
l i qui d phase. There are four i oni c reacti ons:
2
2 3
H O H O OH +
+
(2)
NH H O NH OH
3 2 4
+ +
+
(3)
H S H O H O HS
2 2 3
+ +
+
(4)
HS H O H O S
+
+ +
2 3
2
(5)
Fi ve i oni c speci es are thereby produced from these aqueous phase i oni c reacti ons.
Al l components i n these reacti ons exi st at chemi cal equi l i bri um condi ti ons and are
the true components of the el ectrol yte system. The apparent components are H O
2
NH
3
,and H S
2
.
Versi on 10
Electrolyte
Simulation
These two sets of components have major effects on the treatment of el ectrol yte
process si mul ati on. Apparent components are of major concern to some
el ectrol yte processes si nce process measurements are usual l y expressed i n terms
of apparent components. To other el ectrol yte processes, expressi on i n terms of
true speci es i s the onl y way to characteri ze an el ectrol yte system. The sel ecti on of
apparent components or true components therefore depends on the type of
el ectrol yte system you si mul ate.
Three types of mol ecul ar components may be present i n an el ectrol yte system:
sol vents, mol ecul ar sol utes, and el ectrol ytes. As a resul t of el ectrol yte sol uti on
chemi stry, i ons, sal ts, and nonvol ati l e mol ecul ar sol utes may be present as
addi ti onal true speci es. These components are defi ned as:
Sol vent: water i s the sol vent for aqueous el ectol yte systems. For mi xed-sol vent
el ectrol yte systems, there are other sol vent components i n addi ti on to water.
Mol ecul ar sol utes are mol ecul ar speci es, other than sol vent compounds, that
exi st i n the l i qui d phase i n mol ecul ar form. Al l mol ecul ar sol utes are treated
wi th Henrys l aw. They are often supercri ti cal components.
El ectrol ytes are al so mol ecul ar speci es. However, strong el ectrol ytes di ssoci ate
compl etel y to i oni c speci es i n the l i qui d phase. Undi ssoci ated weak el ectrol ytes
can be sol vent components or mol ecul ar sol utes.
I ons are nonvol ati l e i oni c speci es that exi st onl y i n the l i qui d phase.
Sal ts are nonvol ati l e mol ecul ar speci es that exi st as sol i ds.
Choosing the True or Apparent Approach
The apparent component approach and the true component approach are
i nterchangeabl e because sol uti on chemi stry based on apparent component
composi ti on defi nes the true component composi ti on of a system. ASPEN PLUS
cal cul ates thermodynami c properti es of components and mi xtures expressed i n
terms of apparent component composi ti on from properti es expressed i n terms of
true component composi ti on. For exampl e, the l i qui d fugaci ty coeffi ci ent of
ammoni a wi th the apparent component approach i s cal cul ated from the l i qui d
fugaci ty coeffi ci ent of ammoni a wi th the true component approach:

i
a l
i
t l i
t
i
a
x
x
, ,
(6)
Where:
i
a l ,
= Fugaci ty coeffi ci ent of apparent component i
i
t l ,
= Fugaci ty coeffi ci ent of true component i
x
i
= Li qui d component mol e fracti on of component i (superscri pt a
i ndi cates apparent composi ti on, t i ndi cates true composi ti on)
Versi on 10
Chapter 5
Si mi l ar rel ati onshi ps are establ i shed for other properti es (Chen et al ., 1983).
However, the apparent component mol e fracti ons are not al ways cal cul ated from
the true component mol e fracti ons because ambi gui ty can exi st i n the
stoi chi ometri c rel ati ons.
Usi ng the apparent component approach i n vapor-l i qui d equi l i bri um i mpl i es:
The vapor-l i qui d equi l i bri um i s sol ved i n terms of apparent components onl y.
The l i qui d sol uti on chemi stry i n the l i qui d i s sol ved i n terms of true and
apparent components.
Thi s approach restri cts the speci fi cati on of the chemi stry, because the reacti on
products (whi ch are true components onl y by defi ni ti on) cannot contai n vol ati l e
components. Onl y apparent components can take part i n vapor-l i qui d equi l i bri um.
The true component approach does not have thi s restri cti on.
I n process si mul ati on, the true component approach requi res that you speci fy the
process i n terms of true components. ASPEN PLUS carri es true components and
thei r composi ti ons i n each process stream and each uni t operati on. Uni t
operati on computati onal al gori thms have been devel oped to sol ve the chemi cal
equi l i bri um rel ati onshi p i n addi ti on to the uni t-operati on descri bi ng equati ons.
The apparent component approach requi res that you speci fy the process onl y i n
terms of apparent components. The sol uti on chemi stry and the true components
are handl ed by the physi cal property system and are transparent to process
fl owsheets and uni t operati ons. The apparent component approach makes i t
possi bl e to use exi sti ng uni t operati on computati onal al gori thms, such as:
Fl ash al gori thms for vapor-l i qui d equi l i bri um
Li qui d phase spl i tti ng al gori thms for l i qui d-l i qui d equi l i bri um
Di sti l l ati on al gori thms
Ri gorous representati on of the (effecti ve) parti al mol ar properti es of apparent
components requi res the sol uti on of the chemi cal equi l i bri um and the knowl edge of
the parti al mol ar properti es of the true components.
Deci di ng whether to use the apparent component or true component approach
can depend on:
Your personal preference
The way you speci fy the process (i n terms of apparent components or true
components)
Convergence consi derati ons
General l y, the apparent component approach i s preferred for si mpl e el ectrol yte
systems. I t offers the advantage that onl y apparent components need to be
comsi dered. When the system grows more compl ex and i t becomes di ffi cul t to sel ect
the apparent components, the true component approach i s preferred. For compl ex
di sti l l ati on col umns or fl owsheet speci fi cati ons, the true component approach can
i mprove convergence. When the apparent components yi el d vol ati l e reacti on
products, al ways use the true component approach.
I f you use the apparent component approach, sol uti on chemi stry i s requi red.
Versi on 10
Electrolyte
Simulation
Reconstitution of Apparent Component Mole Fractions
Several el ectrol yte property model s i n ASPEN PLUS use the techni que of
constructi ng a set of arbi trary mol e fracti ons of al l possi bl e apparent components
from a mi xture descri bed i n terms of composi ti ons of true components. These
model s are l i sted i n the fol l owi ng tabl e, and are di scussed i n detai l i n Chapter 3.
Model Name Property
Clarke aqueous electrolyte volume Molar volume
Jones-Dole Viscosity
Riedel Thermal conductivity
Nernst-Hartley Diffusivity
Onsager-Samaras Surface tension
The mol e fracti ons of the apparent components are reconsti tuted from mol e
fracti ons of true components, even i f you use the apparent component approach. Al l
possi bl e apparent components ca from cati ons c and ani ons a are consi dered. For
exampl e, i f you di ssol ve cal ci um sul phate and sodi um chl ori de i n water, then the
sol uti on contai ns: Na
+
, Ca
2+
, SO
4
2
, and C1
. Thi s sol uti on coul d have been made

from water and an i nfi ni te number of di fferent combi nati ons of amounts of the
apparent components CaSO
4
, CaCl
2
, NaCl , and Na SO
2 4
.
From al l possi bl e sol uti ons, ASPEN PLUS uses one arbi trary sol uti on of the
amounts of apparent el ectrol ytes:
n
n n
z n
ca
a c
t
a
t
c c
t
c
(7)
Thi s sol uti on generates al l possi bl e combi nati ons of ani ons and cati ons. However,
for the case of 2-2 el ectrol ytes, the amount i s mul ti pl i ed by 2, to avoi d the
creati on of, for exampl e, ( ) Ca SO
2 4
2
i nstead of CaSO
4
. I n general , the correcti on
factor shoul d be the hi ghest common factor of the charges ( ) z
c
and ( ) z
a
, but the
3-3 or 2-4 el ectrol ytes are not known.
From thi s the total amount of apparent mol es and apparent mol e fracti ons can be
cal cul ated:
x
n
n
k
a k
a
tot
a
(8)
Where k can refer to any sol vent B, mol ecul ar sol ute i, or apparent el ectrol yte ca.
Versi on 10
Chapter 5
Electrolyte Thermodynamic Models
I n el ectrol yte process si mul ati on, the fol l owi ng thermophysi cal properti es must be
computed at a gi ven temperature, pressure and composi ti on:
Acti vi ty coeffi ci ent
Enthal py
Reference state Gi bbs energy
These properti es are necessary to perform phase equi l i bri um, chemi cal
equi l i bri um, and mass and energy bal ance cal cul ati ons. Acti vi ty coeffi ci ents are the
most cri ti cal properti es for process si mul ati on. They determi ne the fl ow rates,
composi ti ons, and stabi l i ty of phases.
Advances i n el ectrol yte thermodynami cs have produced several semi -empi ri cal
excess Gi bbs energy model s that correl ate and predi ct: acti vi ty coeffi ci ents of
i ndi vi dual i ons, mean i oni c acti vi ty coeffi ci ents, and acti vi ty coeffi ci ents of
mol ecul ar sol vents and sol utes. The Pi tzer equati on, the el ectrol yte NRTL Model ,
and the Zemai ti s equati ons are the most wi del y adopted equati ons among these
model s.
Pitzer Equation
The Pi tzer equati on i s a vi ri al expansi on equati on. The model requi res second-
order parameters at l ow concentrati ons, and both second- and thi rd-order
parameters at hi gh concentrati ons. The equati on has been appl i ed successful l y to
represent data wi thi n experi mental error from di l ute sol uti ons up to an i oni c
strength of si x mol al for both aqueous si ngl e strong el ectrol yte systems and
mul ti component strong el ectrol yte systems (Pi tzer, 1973). The Pi tzer equati on i s
al so extended to model aqueous weak el ectrol yte systems (Chen et al ., 1982). I t
provi des a thermodynami cal l y consi stent model that accuratel y represents
el ectrol yte noni deal i ty for many i ndustri al aqueous el ectrol yte systems.
Thi s model i s the basi s for the PI TZER property method. For detai l s on the
model , see Pi tzer Acti vi ty Coeffi ci ent Model , Chapter 3.
Versi on 10
Electrolyte
Simulation
Electrolyte NRTL Equation
The el ectrol yte NRTL equati on provi des another thermodynami cal l y consi stent
model for aqueous el ectrol yte systems. Thi s equati on was devel oped wi th the l ocal
composi ti on concept. Thi s concept i s si mi l ar to the NRTL (Non-Random Two
Li qui d) model for nonel ectrol yte systems (Renon and Prausni tz, 1968). Wi th onl y
bi nary parameters, the equati on sati sfactori l y represents physi cal i nteracti ons of
true speci es i n aqueous si ngl e el ectrol yte systems and mul ti component el ectrol yte
systems over wi de ranges of concentrati ons and temperatures. Thi s model can
represent i nfi ni tel y di l ute el ectrol yte systems (where i t reduces to the Debi je-
Hckel model ), nonel ectrol yte systems (where i t reduces to the NRTL model ), and
pure fused sal ts. I t connects these l i mi ti ng systems. The equati on has been
extended to model mi xed sol vent el ectrol yte-systems (Mock et al ., 1984).
Thi s model i s the basi s for the ELECNRTL property method. For detai l s on the
model , see El ectrol yte NRTL Acti vi ty Coeffi ci ent Model , Chapter 3.
Zemaitis Equation (Bromley-Pitzer Model)
The Zemai ti s equati on i s based on the Bronsted-Guggenhei m mean i oni c acti vi ty
coeffi ci ent equati on wi th the Guggenhei m term expressed i n Broml ey's form as
an expansi on of i oni c strength. The acti vi ty of sol vent water i n si ngl e el ectrol yte
systems i s then computed by appl i cati on of the Gi bbs-Duhem i ntegrati on on the
mean i oni c acti vi ty coeffi ci ent equati on. I n mul ti component el ectrol yte systems, the
acti vi ty coeffi ci ent of sol vent water i s computed wi th the Mei ssner approxi mati on
to avoi d excessi ve Gi bbs-Duhem i ntegrati on (Broml ey, 1973). Acti vi ty coeffi ci ents of
mol ecul ar sol utes are esti mated wi th the Setschenow equati on. The Zemai ti s
equati on i s not a thermodynami cal l y consi stent model , and bi nary parameters are
empi ri cal functi ons of i oni c strength. The model offers the advantage of predi cti ng
mean i oni c acti vi ty coeffi ci ents for unmeasured el ectrol yte systems from Broml ey's
correl ati on of bi nary parameters (Mei ssner and Kusi k, 1973). For detai l s on the
model , see Broml ey-Pi tzer Acti vi ty Coeffi ci ent Model , Chapter 3.
Future Models
Acti ve research i s bei ng conducted i n the fi el d of el ectrol yte thermodynami cs
(Maurer, 1983). For exampl e, model s based on Mean Spheri cal Approxi mati on
(Pl anche and Renon, 1981, Watanasi ri et al ., 1982) and equati on of state el ectrol yte
model s (Frst and Renon, 1993) are bei ng devel oped. General l y, the trend i s
toward devel opi ng thermodynami cal l y consi stent model s wi th fewer adjustabl e
parameters, broader appl i cabi l i ty, and greater predi cti ve capabi l i ty. A broad range
of el ectrol yte acti vi ty coeffi ci ent model s wi l l soon be avai l abl e.
Versi on 10
Chapter 5
Electrolyte Data Regression
Data regressi on i s a cri ti cal part of el ectrol yte process si mul ati on. For exampl e,
el ectrol yte acti vi ty coeffi ci ent model s requi re regressi on of experi mental data to
determi ne model parameters. I t may al so be necessary to determi ne chemi cal
equi l i bri um constants by data regressi on.
The ASPEN PLUS Data Regressi on System (DRS) can be used for el ectrol ytes.
There are two uni que consi derati ons for el ectrol yte systems:
I ons are nonvol ati l e, so vapor-l i qui d phase equi l i bri um constrai nts for i ons are
not appl i cabl e.
The chemi cal equi l i bri um constrai nt of the sol uti on chemi stry must be
sati sfi ed.
Experi mental data for el ectrol yte systems can be di vi ded i nto four mai n categori es
for both si ngl e el ectrol yte systems and mul ti component el ectrol yte systems:
El ectrol yte properti es, such as mean i oni c coeffi ci ents
Mol ecul ar properti es, such as osmoti c coeffi ci ent, sol vent vapor pressure, vapor-
l i qui d phase equi l i bri um data, and l i qui d-l i qui d phase equi l i bri um data
Sol uti on properti es, such as l i qui d mi xture enthal py and densi ty
Sal t sol ubi l i ty
El ectrol yte data regressi on i s most often performed on el ectrol yte properti es and
mol ecul ar properti es to determi ne acti vi ty coeffi ci ent model parameters. Sol uti on
enthal py data provi de val uabl e i nformati on on temperature deri vati ves of acti vi ty
coeffi ci ents and can be used wi th other data to determi ne the temperature
dependency of acti vi ty coeffi ci ent model parameters. These data can al so be used to
regress chemi cal equi l i bri um constants and acti vi ty coeffi ci ent model parameters.
Sal t saturati on l i mi ts can be used to obtai n equi l i bri um constants for sal t
preci pi tati on (sal t sol ubi l i ty product).
See ASPEN PLUS User Guide, Chapter 31, for detai l s on data regressi on.
References
L.A. Broml ey, "Thermodynami c Properti es of Strong El ectrol ytes i n Aqueous
Sol uti ons," AI ChE J ., Vol . 18, (1973), p. 313.
C.C. Chen, H.I . Bri tt, J.F Boston, and L.B. Evans, "Local Composi ti on Model for
Excess Gi bbs Energy of El ectrol yte Systems," AI ChE J ., Vol . 28, (1982), p. 588.
C.C. Chen, H.I . Bri tt, J.F. Boston, and W.M. Cl arke, "Thermodynami c Property
Eval uati on i n Computer-Based Fl owsheet Si mul ati on for Aqueous El ectrol yte
Systems," Paper presented at the Denver AI ChE Meeti ng, August, 1983.
Versi on 10
Electrolyte
Simulation
W. Frst and H. Renon. "Representati on of Excess Properti es of El ectrol yte
Sol uti ons Usi ng a New Equati on of State." AI ChE J ., Vol . 39, No. 2, (1993), pp.
335-343.
G., Mauer, "El ectrol yte Sol uti ons," Fluid Phase Equilibria, Vol . 13, (1983), p. 269.
H.P. Mei ssner and C.L. Kusi k, "Aqueous Sol uti ons of Two or More Strong
El ectrol ytes-Vapor Pressures and Sol ubi l i ti es," I nd. Eng. Chem. Process Res.
Develop., Vol . 12, (1973), p. 205.
B. Mock, L.B. Evans, and C.-C. Chen, "Phase Equi l i bri a i n Mul ti pl e-Sol vent
El ectrol yte Systems: A New Thermodynami c Model ," Paper presented at the
Boston Summer Computer Si mul ati on Conference, Jul y 1984.
Pi tzer, K.S., "Thermodynami cs of El ectrol ytes.I . Theoreti cal Basi s and General
Equati ons," J . Phys. Chem., Vol . 77, (1973), p. 268.
H. Pl anche and H. Renon, "Mean Spheri cal Approxi mati on Appl i ed to a Si mpl e
but Nonpri mi ti ve Model of I nteracti on for El ectrol yte Sol uti ons and Pol ar
Substance," J . Phys. Chem, Vol . 85, (1981), p. 3924.
H. Renon and J.M. Prausni tz, "Local Composi ti ons i n Thermodynami c Excess
Functi on for Li qui d Mi xtures," AI ChE J ., Vol . 14, (1968), p. 135.
S. Watanasi ri , M.R. Brul e, and L.L. Lee, "Predi cti on of Thermodynami c
Properti es of El ectrol yti c Sol uti ons Usi ng the Me an Spheri cal
Approxi mati on," J . Phys. Chem., Vol . 86, (1982), p. 282.
O O O O
Versi on 10
Chapter 6
6 Free-Water and Rigorous
Three-Phase Calculations
Thi s chapter descri bes free-water and ri gorous three-phase cal cul ati ons i n
ASPEN PLUS. Gui del i nes to hel p you choose the most appropri ate method are
i ncl uded.
The fol l owi ng tabl e l i sts the uni t operati on model s that al l ow three-phase
cal cul ati ons. The tabl e shows, for each model , whether or not free-water and/or
ri gorous three-phase cal cul ati ons can be performed.
Unit Operation Models That Allow Three-Phase Calculations
Name Description
Free-Water
Calculations
Water Decant
Stream
Rigorous Three-Phase
Calculations
Mixer
FSplit
Sep
Sep2
Stream mixer
Stream splitter
Component separator
Two outlet separator
YES
YES
YES
YES
YES
NO
NO
NO
YES
YES
YES
YES
DSTWU
Distl
SCFrac
RadFrac
MultiFrac
PetroFrac
BATCHFRAC
RATEFRAC
Extract
Shortcut distillation design
Shortcut distillation rating
Shortcut petroleum distillation
Rigorous distillation
Rigorous multicolumn distillation
Rigorous petroleum distillation
Rigorous batch distillation
Rate-based distillation
Rigorous liquid-liquid extractor
YES
YES
YES
YES
YES
YES
YES
YES
NO
YES
YES
YES
YES
YES
YES
NO
YES
NO
NO
NO
NO
YES
NO
NO
YES
NO
Condenser only
Rigorous liquid-liquid equilibrium calculations

continued
Versi on 10
Free-Water
and
Rigorous
Three-
Phase
Calculations
Unit Operation Models That Allow Three-Phase Calculations
Name Description
Free-Water
Calculations
Water Decant
Stream
Rigorous Three-Phase
Calculations
Heater
Flash2
Flash3
Decanter
Heatx
MHeatx
Heater/cooler
Two outlet flash
Three outlet flash
Liquid-liquid decanter
Two stream heat exchanger
Multistream heat exchanger
YES
YES
NO
YES
YES
YES
YES
YES
NO
NO
YES
YES
YES
YES
YES
YES
YES
RStoic
RYield
RGibbs
Stoichiometric reactor
Yield reactor
Equilibrium reactor
Gibbs energy minimization
YES
YES
NO
YES
YES
NO
YES
YES
YES
Pump
Compr
MCompr
Pump/hydraulic turbine
Compressor/turbine
Multistage compressor/turbine
YES
YES
YES
YES
YES
YES
YES
YES
YES
Crystallizer Crystallizer NO NO NO
Pipeline
Dupl
Mult
Pipeline
Stream duplicator
Stream multiplier
YES
NO
YES
Condenser only
Rigorous liquid-liquid equilibrium calculations
Rgibbs handles any number of phases rigorously.

Free-Water Immiscibility Simplification
The uni t operati on model s i n the tabl e l abel ed Uni t Operati on Model s That Al l ow
Three-Phase Cal cul ati ons on page 6-1 can handl e the presence and the decanti ng
of free water, when performi ng fl ash cal cul ati ons or l i qui d-l i qui d equi l i bri um
cal cul ati ons on water-organi c systems i n whi ch the water phase i s essenti al l y pure.
Free-water cal cul ati ons i nvol ve speci al methods for cal cul ati ng the sol ubi l i ty of
water i n the organi c phase and a test for the presence of a pure water phase.
Free-water cal cul ati ons are al ways faster than ri gorous three-phase cal cul ati ons
and requi re mi ni mal physi cal property data preparati on.
For water-hydrocarbon systems, free-water cal cul ati ons are normal l y adequate.
The hydrocarbon sol ubi l i ty i n the water phase i s general l y negl i gi bl e. I n
appl i cati ons where the hydrocarbon sol ubi l i ty i n the water phase i s of great
concern (such as i n an envi ronmental study), use ri gorous three-phase
cal cul ati ons.
Versi on 10
Chapter 6
For chemi cal systems such as water-hi gher al cohol s, free-water cal cul ati ons do
not appl y. Sol ubi l i ty of the organi cs i n the water phase i s si gni fi cant. Ri gorous
three-phase cal cul ati ons are requi red.
Specifying Free-Water Calculations
The free-water cal cul ati ons are compl etel y ri gorous, except for the assumpti on
that the water phase i s pure. I f free water i s present and you speci fy a decant
stream for the bl ock, ASPEN PLUS pl aces the water phase i n the decant stream.
I f you do not speci fy a decant stream, ASPEN PLUS mi xes the water phase wi th
the organi c phase.
To request free-water calculations for Use the Free-Water field on the
The entire flowsheet Setup.Main form
An individual unit operation block Blockops form for the block
An individual outlet stream in some blocks Flash-Specs form for the block
For al l uni t operati on bl ocks except the di sti l l ati on model s, you can sel ect two types
of free-water cal cul ati ons usi ng the fol l owi ng fl ash speci fi cati on:
NPHASE=2, to consi der vapor and l i qui d phases
NPHASE=1, to consi der onl y l i qui d phases
NPHASE=3 i s reserved for ri gorous three-phase cal cul ati ons. I f you speci fy
NPHASE=3, any free-water speci fi cati on i s i gnored.
For al l di sti l l ati on model s except RadFrac, Mul ti Frac, and PetroFrac, free water
cal cul ati ons are performed i n the condenser onl y. For RadFrac, Mul ti Frac, and
PetroFrac, you can request free-water cal cul ati ons for addi ti onal stages i n the
col umn. For detai l s, pl ease see the ASPEN PLUS User Guide, Chapter 10.
Free-Water Phase Properties
The free-water phase K-val ue, K
w
*
, i s cal cul ated as fol l ows:
K
w w
l
w
v * *,

Where:
w
l *,
= The fugaci ty coeffi ci ent of pure l i qui d water, cal cul ated usi ng a free-
water property method (for exampl e, the STEAM-TA property
method)
w
v
= The fugaci ty coeffi ci ent of water i n the vapor phase mi xture,
cal cul ated usi ng the pri mary property method
Versi on 10
Free-Water
and
Rigorous
Three-
Phase
Calculations
When a free-water phase i s present, i ts other thermodynami c properti es (such as
enthal py) and transport properti es (such as vi scosi ty) are cal cul ated usi ng the free-
water property method.
Organic Phase Properties
The K-val ue of water i n the organi c phase i s:
K
w w w
l
w
v * *,

Where:
w
= The acti vi ty coeffi ci ent of water i n the organi c phase
w
l *,
= The fugaci ty coeffi ci ent of pure l i qui d water, cal cul ated usi ng the
free-water property method
w
v
= The fugaci ty coeffi ci ent of water i n the vapor phase mi xture,
cal cul ated usi ng the pri mary property method
You can sel ect the cal cul ati on methods for
w
and
w
v
usi ng the Sol u-water fi el d
on the Properti es.Mai n form or the Bl ockops form.
Solu-water option
Calculate
w
from
Calculate
w
v
from
0
w
w
sol
x
1
Free-water property method
1
w
w
sol
x
1
Primary property method
2
( )
w w
f T x , where
w
w
sol
x
1
when x x
w w
sol
Primary property method

3 Primary property method Primary property method
Sol u-water opti on 3 i s not recommended unl ess bi nary i nteracti on parameters
regressed from l i qui d-l i qui d equi l i bri um data are avai l abl e.
Versi on 10
Chapter 6
The l i mi ti ng sol ubi l i ty of water i n the organi c phase
( )
x
w
sol
i s cal cul ated as a mol e
fracti on wei ghted average of the sol ubi l i ti es of water i n the i ndi vi dual organi c
speci es:
x
a
a
w
sol
+ 1
a x
x
x
i
wi
sol
wi
sol
i
1
Where:
x
i
= Water-free mol e fracti on of the ith organi c speci es
x
wi
sol
= Mol e fracti on sol ubi l i ty of water i n the ith speci es
The val ue of x
wi
sol
i s cal cul ated as a functi on of temperature, usi ng the Water
Sol ubi l i ty model (WATSOL) descri bed i n Chapter 3.
Rigorous Three-Phase Calculations
The uni t operati on model s that can perform ri gorous three-phase or two-l i qui d-
phase cal cul ati ons are i ndi cated i n the tabl e l abel ed Uni t Operati on Model s That
Al l ow Three-Phase Cal cul ati ons on page 6-1.These cal cul ati ons make no
assumpti ons about the nature of the two l i qui d phases. ASPEN PLUS uses the
pri mary property method to cal cul ate the K-val ues of al l components i n both l i qui d
phases. The second l i qui d phase does not have to be aqueous. I f the second l i qui d
phase i s aqueous, the sol ubi l i ty of organi cs i n water i s treated ri gorousl y. To obtai n
correct three-phase resul ts, you must use the appropri ate bi nary parameters for
the property model used i n the property method.
Speci fy ri gorous three-phase cal cul ati ons at the i ndi vi dual bl ock l evel , usi ng the
fl ash opti on NPHASE=3, except for Fl ash3. Fl ash3 has no fl ash opti ons, si nce i t
performs onl y ri gorous three-phase fl ashes.
Extract al ways performs ri gorous two-l i qui d-phase cal cul ati ons.
O O O O
Versi on 10
Free-Water
and
Rigorous
Three-
Phase
Calculations
Versi on 10
Chapter 7
7 Petroleum Components
Characterization Methods
ASPEN PLUS provi des a wi de range of methods for characteri zati on of petrol eum
components, or pseudocomponents. These methods are used to esti mate property
parameters, such as cri ti cal properti es, i deal gas heat capaci ty, vapor pressure, and
l i qui d vi scosi ty. The fol l owi ng tabl e l i sts:
Parameters that ASPEN PLUS esti mates for petrol eum components
Methods avai l abl e (the literature references for each method are listed at the end of
this chapter)
Petroleum Components Characterization Methods
Parameter Description Model Available
MW Molecular weight Brule et al. (1982)
Hariu-Sage (1969)
Hariu-Sage-Aspen (1994)
Kesler-Lee (1976)
Riazi API (1987)
Riazi-Daubert (1980)
Tsang-Aspen (1978)
TC Critical temperature Brule et al. (1982)
Cavett (1962)
Kesler-Lee (1976)
Riazi API (1987)
Tsang-Aspen (1978)
Twu (1984)
PC Critical pressure Cavett (1962)
Kesler-Lee (1976)
Riazi API (1987)
Tsang-Aspen (1978)
Twu (1984)
continued
Versi on 10
Petroleum
Components
Characterization
Methods
Petroleum Components Characterization Methods (continued)
Parameter Description Model Available
VC Critical volume Brule et al. (1982)
Reidel (1954)
Twu (1984)
PL Vapor pressure BK-10
Kesler-Lee (1980)
Maxwell-Bonnell (1955)
Tsang-SWAP (1978)
CPIG Ideal gas heat capacity Brule et al. (1982)
Cavett (1962)
Kesler-Lee (1976)
Mathias-Monks (1982)
Tsang-Aspen (1978)
VL Liquid molar volume Cavett
Rackett (Spencer, 1972)
DHVL Enthalpy of vaporization Vetere (1973)
OMEGA Acentric factor Defining relation
Kesler-Lee (1976)
Kesler-Lee-Aspen (1994)
MUL Liquid viscosity Watson (1935)
BWRGMA BWR orientation parameter Brule et al. (1982)
TCBWR BWR critical temperature Brule et al. (1982)
VCBWR BWR critical volume Brule et al. (1982)
DHFORM Standard enthalpy of formation Default to zero
Montgomery (1988)
DGFORM Standard Gibbs energy of formation Default to zero
Montgomery (1988)
WATSOL Water solubility in hydrocarbon ASPEN PLUS
API Kerosene
Hibbard-Schalla
RKSKIJ RKS binary parameters API 1978
API 1987
Versi on 10
Chapter 7
Property Methods for Characterization of Petroleum
Components
Si nce there are several methods avai l abl e for esti mati on of a gi ven parameter,
ASPEN PLUS sel ects the most appropri ate method for a gi ven appl i cati on. These
sel ected methods are used to create an property method. There are fi ve property
methods avai l abl e:
The API -METH property method consi sts of methods based mai nl y on the API
procedure. Thi s property method i s appropri ate for refi nery appl i cati ons.
COAL-LI Q property method consi sts of methods devel oped for coal l i qui d
appl i cati ons. The database used to devel op the correl ati ons contai ns a l arge
percentage of aromati c compounds.
ASPEN property method consi sts of methods devel oped by AspenTech for
petrol eum components and methods based on the API procedure. Thi s method
i s recommended.
LK property method i s based mai nl y on the methods of Kesl er and Lee.
API -TWU property method i s based on the ASPEN property method, but uses
the Twu correl ati ons for cri ti cal properti es.
The property methods avai l abl e for characteri zati on of pseudocomponents are
l i sted i n the following tabl e.
Property Methods for Pseudocomponents Characterization
Property Method ASPEN: Aspen Tech and API procedures
Property Method
Molecular weight Hariu-Sage-ASPEN
T
c
Riazi-Daubert
P
c
Riazi-Daubert
V
c
Reidel
Vapor pressure BK-10
Ideal gas capacity Kesler-Lee
Enthalpy of vaporization Vetere
Acentric factor Kesler-Lee-ASPEN
Viscosity Watson
Water solubility ASPEN PLUS
Standard enthalpy of formation Montgomery
Standard Gibbs energy of formation Montgomery
RKS binary parameters API 1978
continued
Versi on 10
Petroleum
Components
Characterization
Methods
Property Method API-METH: API Procedures
Property Method
Molecular weight Hariu-Sage
T
c
Riazi-Daubert
P
c
Riazi-Daubert
V
c
Reidel
Vapor pressure Maxwell-Bonnell
Ideal gas heat capacity Kesler-Lee
Acentric factor Kesler-Lee
Viscosity Watson
Water Solubility ASPEN PLUS
Standard enthalpy of formation Default to zero
Standard Gibbs energy of formation Default to zero
Water solubility in hydrocarbon ASPEN PLUS
Property Method API-METH: For COAL-LIQ; For coal Liquids
Property Method
Molecular weight Hariu-Sage
Tc Tsang-ASPEN
Pc Tsang-ASPEN
Vc Reidel
Vapor pressure Tsang-SWAP
Ideal gas heat capacity Mathias-Monks
Viscosity Watson
BWR orientation parameter Brule et al.
BWR Tc Brule et al.
BWR Vc Brule et al.
Continued
Versi on 10
Chapter 7
Property Method API-METH: For COAL-LIQ; For coal Liquids (Continued)
Property Method
Standard enthalpy of formation Default to zero
Standard Gibbs energy of formation Default to zero
Property Method LK: Lee-Kesler
Property Method
Molecular weight Kesler-Lee
T
c
Kesler-Lee
P
c
Kesler-Lee
V
c
Reidel
Vapor pressure Kesler-Lee
Viscosity Watson
Standard enthalpy of formation ASPEN PLUS
Water solubility in hydrocarbon Montgomery
Property Method API-TWU: AspenTech, API, and Twu
Property Method
Molecular weight Hariu-Sage-ASPEN
T
c
Twu
P
c
Twu
V
c
Twu
Vapor pressure BK-10
Continued
Versi on 10
Petroleum
Components
Characterization
Methods
Property Method API-TWU: AspenTech, API, and Twu (Continued)
Property Method
Acentric factor Kesler-ASPEN
Viscosity Watson
Water solubility API kerosene-line
Standard enthalpy of formation Montgomery
References
M.R. Brul , C.T. Li m, L.L. Lee, and K.E. Starl i ng, AI CHE J., 28, p. 616 (1982).
R.H. Cavett, "Physi cal Data for Di sti l l ati on Cal cul ati ons Vapor-Li qui d
Equi l i bri a," Presented at 27th Mi dyear Meeti ng of API Di vi si on of Refi ni ng, May
15, 1982.
R.H. Cavett, FLOWTRAN Physi cal Properti es Reference Manual , Monsanto
Company.
C.W. Edmi ster, e. Appl i ed Hydrocarbon Thermodynami cs, 2nd edi ti on, Gul f
Publ i shi ng Co., (1988).
O.H. Hari u and R.C. Sage, Hydro. Proc., (1969).
M.G. Kesl er and B.I . Lee, Hydro. Proc., 55 (3), p. 153, (1976).
M.G. Kesl er and B.I . Lee, Hydro. Proc., 59 (7), p. 163, (1980).
P.M. Mathi as, and K.G. Monks, SRC-I Quarterl y Progress Report, Ai r Products
and Chemi cal s, I nc., Apri l June 1982.
Maxwel l and Bonnel l , API Procedure 5A1.15.
L. Rei del , API Prodedure 4A3.1.
M.R. Ri azi and T.E. Daubert, Hydro. Proc., 59 (3), p. 115, (1980).
D. B. Robi nson and D. Y. Peng "The Characteri zati on of the Heptanes and
Heavi er Fracti ons for the GPA Peng-Robi nson Programs," GPA Research Report
RR-28, March (1978).
C.F. Spencer and R.P. Danner, J . Chem Eng. Data., 17, (1972).
Versi on 10
Chapter 7
M. Tsang, Computer-Ai ded I ndustri al Process Desi gn, The ASPEN Project,
Second Annual Report, June 1, 1977 to May 30, 1978; Submi tted to U.S. D.O.E.
by M.I .T. Department of Chemi cal Engi neeri ng and Energy Laboratory under
Contract No. E(4918) 2295, Task No. 9, June 15, 1978.
A. Vetere, "Modi fi cati on of the Ki sti akowsky Equati on for the Cal cul ati on of the
Enthal pi es of Vapori zati on of Pure Compounds," Laboratory Ri cherche Chi mi ca
I ndustri al e SNAM PROGETTI , San Donato, Mi l anese, 1973.
K. Watson et al ., API Fi gure 11A4.1.
C. H. Twu, Fl ui d Phase Equi l i bri a, 16, p. 137 (1984).
O O O O
Versi on 10
Petroleum
Components
Characterization
Methods
Versi on 10
Chapter 8
8 Property Parameter
Estimation
Thi s chapter descri bes:
Esti mati on methods used by the Property Constant Esti mati on System (PCES)
How to generate a report for the esti mated parameters
I f you request esti mati on, ASPEN PLUS, by defaul t, esti mates al l mi ssi ng property
parameters requi red by physi cal property model s. These parameters i ncl ude any
not avai l abl e i n the databank and not speci fi ed on Properti es Parameters forms.
The following tabl e l i sts al l the parameters that ASPEN PLUS can esti mate.
Parameters Estimated by ASPEN PLUS
Pure Component Constants
Parameter Description Model
MW Molecular weight
TB Normal boiling point
TC Critical temperature
PC Critical pressure
VC Critical volume
ZC Critical compressibility factor
DHFORM Standard heat of formation at 25C
DGFORM Standard Gibbs free energy of formation at 25C
OMEGA Pitzer acentric factor
See Chapter 3.
continued
Versi on 10
Property
Parameter
Estimation
Pure Component Constants (continued)
DHVLB Heat of vaporization at TB

VB Liquid molar volume at TB
VLSTD Standard liquid volume
RGYR Radius of gyration
DELTA Solubility parameter at 25C
GMUQR UNIQUAC R parameter UNIQUAC
GMUQQ UNIQUAC Q parameter UNIQUAC
PARC Parachor
DHSFRM Solid enthalpy of formation at 25

o
C
DGSFRM Solid Gibbs energy of formation at 25
o
C
DHAQHG Aqueous infinite dilution enthalpy of formation Helgeson
DGAQHG Aqueous infinite dilution Gibbs energy of formation Helgeson
S25HG Entropy at 25
o
C Helgeson
Temperature-Dependent Property Correlation Parameters
CPIG Ideal gas heat capacity Ideal Gas Heat Capacity/DIPPR

CPLDIP Liquid heat capacity Liquid Heat Capacity, DIPPR
CPSPO1 Solid heat capacity Solid Heat Capacity
PLXANT Vapor pressure Antoine/Wagner
DHVLWT Heat of vaporization Watson/DIPPR
RKTZRA Liquid molar volume Rackett/DIPPR
OMEGHG Helgeson OMEGA heat capacity coefficient Helgeson
CHGPAR Helgeson C Heat capacity coefficient Helgeson
MUVDIP Vapor viscosity Chapman-Enskog-Brokaw/DIPPR
MULAND Liquid viscosity Andrade/DIPPR
KVDIP Vapor thermal conductivity Stiel-Thodos/DIPPR
KLDIP Liquid thermal conductivity Sato-Riedel/DIPPR
SIGDIP Surface tension Hakim-Steinberg-Stiel/DIPPR
See Chapter 3.
Needed in estimating surface tension and radius of gyration

Continued
Versi on 10
Chapter 8
Binary Parameters
WILSON/1, WILSON/2 Wilson parameters Wilson

NRTL/1, NRTL/2 NRTL parameters NRTL
UNIQ/1, UNIQ/2 UNIQUAC parameters UNIQUAC
UNIFAC Group Parameters
GMUFR UNIFAC R Parameter UNIFAC

GMUFQ UNIFAC Q Parameter UNIFAC
GMUFDR R parameter for Dortmund UNIFAC Dortmund UNIFAC
GMUFDQ Q parameter for Dortmund UNIFAC Dortmund UNIFAC
GMUFLR R parameter for Lyngby UNIFAC Lyngby UNIFAC
GMUFLQ Q parameter for Lyngby UNIFAC Lyngby UNIFAC
See Chapter 3.
Needed in estimating surface tension and radius of gyration

Description of Estimation Methods
Thi s secti on descri bes the:
Methods avai l abl e for esti mati ng property parameters
Appl i cati on range for each method (when appropri ate)
Expected error for each method (when appropri ate)
The expected error i nformati on can hel p you to eval uate a method.
Molecular Weight (MW)
I f you use the general method to enter mol ecul ar structure on the Properti es
Mol ecul ar Structure General sheet, ASPEN PLUS esti mates mol ecul ar wei ght
from the mol ecul ar formul a. I f you do not use the general method, then ei ther:
You must enter mol ecul ar wei ght usi ng the Properti es Parameters Pure
Component Scal ar form
The mol ecul ar wei ght must be avai l abl e from the ASPEN PLUS databank.
Versi on 10
Property
Parameter
Estimation
Normal Boiling Point (TB)
ASPEN PLUS uses the normal boi l i ng poi nt to esti mate many other parameters,
such as cri ti cal temperature and cri ti cal pressure, i f they are mi ssi ng. Normal
boi l i ng poi nt i s one of the most i mportant pi eces of i nformati on requi red for
property/parameter esti mati on. Therefore, i f you have an experi mental normal
boi l i ng poi nt, you shoul d enter i t usi ng the Properti es Parameters Pure
Component Scal ar form.
PCES provi des the fol l owi ng methods for esti mati ng normal boi l i ng poi nt:
Method Information Required
Joback Structure
Ogata-Tsuchida Structure
Gani Structure
Mani TC, PC, Vapor pressure data
J oback Method
The Joback method gi ves onl y an approxi mate esti mate of normal boi l i ng poi nt.
Absol ute average error i s 12.9 K for 408 di verse organi c compounds. The Joback
method i s l ess accurate than the Ogata-Tsuchi da method, but i t i s easi er to use
and appl i es to a wi der range of compounds.
Tabl e 3.5 i n ASPEN PLUS Physical Property Data l i sts the functi onal groups for
the Joback method.
Ogata-Tsuchida Method
The Ogata-Tsuchi da method i s for compounds wi th a si ngl e functi onal group (such
as -OH) and a radi cal type (such as methyl ). Thi s method performed rel i abl y for
600 compounds tested; 80% were wi thi n 2 K, 89% were wi thi n 3 K, and 98% were
wi thi n 5 K. Devi ati ons l arger than 5 K were general l y for compounds contai ni ng
the methyl radi cal .
the Ogata-Tsuchi da method.
Gani Method
The Gani method uses contri buti ons from both fi rst-order and second-order groups.
The second order groups account for the effect of nei ghbori ng atoms. Use of second
order groups resul ts i n hi gher accuracy. The esti mati on error of thi s method i s
about 2/5 of that of the Joback method. (AIChE J . 40,1697,1994).
Versi on 10
Chapter 8
Tabl e 3.4A i n ASPEN PLUS Physical Property Data l i sts the functi onal groups for
thi s method.
Mani Method
The Mani method was devel oped by Juan-Carl os Mani of Aspen Technol ogy. Thi s
method esti mates TB from the Ri edel equati on when one or two experi mental
vapor pressure data are avai l abl e. Thi s method can al so be used to esti mate TC
and vapor pressure.
Thi s method provi des very accurate and rel i abl e esti mate of TB, TC and vapor
pressure curve when some experi mental vapor pressure data i s avai l abl e. I t i s very
useful for compl ex compounds that decompose at temperatures bel ow the normal
boi l i ng poi nts.
Critical Temperature (TC)
PCES provi des the fol l owi ng methods for esti mati ng cri ti cal temperature:
Joback Structure, TB
Lydersen Structure, TB
Ambrose Structure, TB
Fedors Structure
Simple MW, TB
Gani Structure
Mani PC, Vapor pressure
J oback Method
The Joback method i s based on the Lydersen method, except i t uses a l arger
database and has fewer functi onal groups. Joback tested approxi matel y 400
organi c compounds. The average rel ati ve error i s 0.8%. The average error i s 4.8K.
the Joback method.
Lydersen Method
The Lydersen method i s one of the fi rst successful methods for esti mati ng cri ti cal
parameters. The functi onal groups l i sted i n Tabl e 3.7, ASPEN PLUS Physical
Property Data, are al most i denti cal to those for the Joback method. The esti mated
error for TC i s usual l y l ess than 2%. For hi gh mol ecul ar wei ght nonpol ar
compounds (MW >> 100), the errors are 5% or hi gher.
Versi on 10
Property
Parameter
Estimation
Ambrose Method
The Ambrose method yi el ds smal l er errors than the Joback and Lydersen
methods, but i s more di ffi cul t to use. Tabl e 3.1 i n ASPEN PLUS Physical
Property Data l i sts the functi onal groups for thi s method. The errors for
approxi matel y 400 organi c compounds are: average rel ati ve error = 0.7%; average
error=4.3K.
Fedors Method
The Fedors method i s not as accurate as the Joback, Lydersen, and Ambrose
methods. For some compounds, the errors can be very l arge. Kl i ncewi cz and Rei d
(AIChE J . 30, 137, 1984) reported an average error of 4% for 199 compounds. Use
thi s method onl y when TB i s unknown. Tabl e 3.4 i n ASPEN PLUS Physical
Property Data l i sts the functi onal groups for thi s method.
Simple Method
The Si mpl e method does not depend on mol ecul ar structure, but requi res MW and
TB as i nput. Thi s method was devel oped by Kl i ncewi cz and Rei d. The average error
for about 200 di verse organi c compounds tested i s 2.3%.
Gani Method
order groups resul ts i n hi gher accuracy (AIChE J . 40,1697,1994). Esti mati on
accuracy i s general l y superi or to other methods For 400 compounds tested, the
average rel ati ve error i s 0.85%. The average error i s 4.85K. Tabl e 3.4A i n ASPEN
PLUS Physical Property Data l i sts the functi onal groups for thi s method.
Mani Method
method esti mates TC from the Ri edel equati on when one or two experi mental
vapor pressure val ues are avai l abl e. Thi s method can al so be used to esti mate TB
and vapor pressure.
Thi s method provi des very accurate and rel i abl e esti mate of TB, TC and vapor
pressure curve when some experi mental vapor pressure data i s avai l abl e. I t i s very
useful for compl ex compounds that decompose at temperatures bel ow the normal
boi l i ng poi nts.
Versi on 10
Chapter 8
Critical Pressure (PC)
PCES provi des the fol l owi ng methods for esti mati ng cri ti cal pressure:
Joback Structure
Lydersen Structure, MW
Ambrose Structure, MW
Gani Structure
J oback Method
database and has fewer functi onal groups. For 390 organi c compounds tested, the
average rel ati ve error i s 5.2%; the average error i s 2.1bar.
the Joback method.
Lydersen Method
parameters. The functi onal groups l i sted i n Tabl e 3.7, ASPEN PLUS Physical
Property Data, are al most i denti cal to those for the Joback method. The esti mated
error i s approxi matel y 4%.
Ambrose Method
Property Data l i sts the functi onal groups for thi s method. For 390 organi c
compounds tested, the average rel ati ve error i s 4.6 %; the average error i s 1.8
bar.
Gani Method
order groups resul ts i n hi gher accuracy (AIChE J . 40, 1697, 1994). Esti mati on
accuracy i s general l y superi or to other methods. For 390 organi c compounds
tested, the average rel ati ve error i s 2.89 %; the average error i s 1.13 bar. Tabl e
3.4A i n ASPEN PLUS Physical Property Data l i sts the functi onal groups for thi s
method.
Versi on 10
Property
Parameter
Estimation
Critical Volume (VC)
PCES provi des the fol l owi ng methods for esti mati ng cri ti cal vol ume:
Joback Structure
Lydersen Structure
Ambrose Structure
Riedel TB, TC, PC
Fedors Structure
Gani Structure
J oback Method
database and has fewer functi onal groups. For 310 organi c compounds tested, the
average rel ati ve error i s 2.3%; the average error i s 7.5 cc/mol e.
the Joback method.
Lydersen Method
parameters. The functi onal groups l i sted i n Tabl e 3.7 ASPEN PLUS Physical
Property Data are al most i denti cal to those for the Joback method. The esti mated
error i s approxi matel y 4%.
Ambrose Method
Property Data l i sts the functi onal groups for thi s method. For 310 organi c
compounds tested, the average rel ati ve error i s 2.8%; the average error i s 8.5
cc/mol e.
Riedel Method
Thi s method i s recommended for hydrocarbons onl y.
Versi on 10
Chapter 8
Fedors Method
The Fedors method i s not as accurate as the Joback, Lydersen, and Ambrose
methods. For some compounds, the errors can be very l arge. Kl i ncewi cz and Rei d
(AIChE J . 30, 137, 1984) reported an average error of 4% for 199 compounds. Use
thi s method onl y when TB i s unknown. Tabl e 3.4 i n ASPEN PLUS Physical
Property Data l i sts the functi onal groups for thi s method.
Gani Method
order groups resul ts i n hi gher accuracy (AIChE J . 40, 1697, 1994). Esti mati on
accuracy i s general l y superi or to other methods. For 310 organi c compounds
tested, the average rel ati ve error i s 1.79%; the average error i s 6.0 cc/mol e. Tabl e
3.4A i n ASPEN PLUS Physical Property Data l i sts the functi onal groups for thi s
method.
Critical Compressibility Factor (ZC)
ASPEN PLUS cal cul ates the cri ti cal compressi bi l i ty factor (ZC) by:
Z
PV
RT
c
c c
c
Where:
R = Uni versal gas constant
P
c
= Cri ti cal pressure
V
c
= Cri ti cal vol ume
T
c
= Cri ti cal temperature
Acentric Factor (OMEGA)
PCES provi des two methods for esti mati ng acentri c factor:
Defi ni ti on method
Lee-Kesl er method
Versi on 10
Property
Parameter
Estimation
Definition Method
When you use the defi ni ti on method, the acentri c factor i s cal cul ated from i ts
defi ni ti on:
i
i
ci
P
P

_
,
log .
*
10
10
Where P
i
*
i s vapor pressure cal cul ated at reduced temperature, (
T
T
ci
) of 0.7.
When you use the defi ni ti on method, the vapor pressure correl ati on parameters
PLXANT, TC, and PC must be avai l abl e from the databank or esti mated.
Lee-Kesler Method
The Lee-Kesl er method depends on TB, TC, and PC. Thi s method i s recommended
for hydrocarbons. Lee and Kesl er reported that thi s method yi el ds val ues of
acentri c factors cl ose to those sel ected by Passut and Danner (Ind. Eng. Chem.
Process Des. Dev. 12, 365, 1973).
Standard Enthalpy of Formation (DHFORM)
PCES provi des the fol l owi ng methods for esti mati ng standard enthal py of
formati on:
Benson Structure
Joback Structure
Bensonr8 Structure
Gani Structure
Al l methods are group contri buti on methods that appl y to a wi de range of
compounds. The Benson Method i s recommended.
Benson Method
The Benson method i s a second-order group contri buti on method. Thi s method:
Accounts for the effect of nei ghbori ng atoms
I s more compl ex to use than the Joback method
Reports more accurate resul ts than Joback (average error i s 3.7 kJ/mol )
the Benson method.
Versi on 10
Chapter 8
J oback Method
The Joback method i s a fi rst-order group contri buti on method. I t i s si mpl er to
use than the other avai l abl e methods, but i s l ess accurate. Reported average error
i s 8.9 kJ/mol .
the Joback method.
BensonR8 Method
Thi s i s the Benson method provi ded wi th Rel ease 8 of ASPEN PLUS. I t i s
retai ned for upward compati bi l i ty. The Benson method i s preferred.
Gani Method
The Gani method uses contri buti ons from both fi rst-order and second-order
groups. The second order groups account for the effect of nei ghbori ng atoms. Use
of second order groups resul ts i n hi gher accuracy than the Joback method
(average error i s 3.71 kJ/mol ) (AI ChE J . 40,1697,1994).
Tabl e 3.4A i n ASPEN PLUS Physical Property Data l i sts the functi onal groups
for thi s method.
Standard Gibbs Free Energy of Formation (DGFORM)
PCES provi des the fol l owi ng methods for esti mati ng standard Gi bbs free energy
of formati on:
Joback Structure
Benson Structure
Gani Structure
Benson Method
The Benson method i s a second-order group contri buti on method. For thi s
property, the Benson method requi res you to enter the symmetry number and the
number of possi bl e opti cal i somers, i f appl i cabl e. ASPEN PLUS does not generate
thi s i nformati on automati cal l y from the general mol ecul ar structure.
the Benson method.
Versi on 10
Property
Parameter
Estimation
J oback Method
use than the other avai l abl e methods, but i s l ess accurate. Reported errors are i n
the range of 5 to 10 kJ/mol . The errors are l arger for compl ex materi al s.
the Joback method.
Gani Method
The Gani method uses contri buti ons from both fi rst-order and second-order
groups. The second order groups account for the effect of nei ghbori ng atoms. Use
of second order groups resul ts i n hi gher accuracy (AIChE J . 40, 1697, 1994).
The Gani method:
I s more compl ex to use than the Joback method
Reports more accurate resul ts than Joback (average error i s 3.24 kJ/mol )
for thi s method
Heat of Vaporization at TB (DHVLB)
PCES esti mates heat of vapori zati on at the normal boi l i ng poi nt by appl yi ng the
heat of vapori zati on correl ati on (DHVLWT) at TB.
Liquid Molar Volume at TB (VB)
PCES esti mates l i qui d mol ar vol ume at the normal boi l i ng poi nt by appl yi ng the
Rackett equati on (RKTZRA) at TB.
Standard Liquid Volume (VLSTD)
PCES esti mates standard l i qui d vol ume by appl yi ng the Rackett l i qui d mol ar
vol ume correl ati on (RKTZRA) at 60F.
Radius of Gyration (RGYR)
PCES esti mates radi us of gyrati on from parachor (PARC).
Solubility Parameter (DELTA)
The sol ubi l i ty parameter i s cal cul ated from the defi ni ti on.
Versi on 10
Chapter 8
UNIQUAC R and Q Parameters (GMUQR, GMUQQ)
PCES provi des the Bondi method for esti mati ng the UNI QUAC R and Q
parameters. Thi s method requi res onl y mol ecul ar structure as i nput. Tabl e 3.3 i n
ASPEN PLUS Physical Property Data l i sts the functi onal groups.
Parachor (PARC)
PCES provi des one method for esti mati ng Parachor. The Parachor method i s a
group-contri buti on method. The functi onal groups for thi s method are l i sted i n
Tabl e 3.10 i n ASPEN PLUS Physical Property Data.
Ideal Gas Heat Capacity (CPIG)
PCES provi des three methods for esti mati ng i deal gas heat capaci ty:
Data Ideal gas heat capacity data
Benson Structure
Joback Structure
PCES uses the I deal -Gas-Heat-Capaci ty-Pol ynomi al model for thi s property.
Both the Benson and Joback methods are group-contri buti on methods that appl y
to a wi de range of compounds.
Do not use the Benson or Joback methods outsi de the temperature range of 280
to 1100 K. Errors are general l y l ess than 1 to 2%.
Benson Method
Benson i s the recommended method. I t accounts for the effect of nei ghbori ng
atoms. I n compari son wi th the Joback method, Benson:
I s more compl ex to use
Reports more accurate resul ts (average error 1.1% for 27 di verse compounds)
the Benson method.
J oback Method
use than the Benson method, but i s l ess accurate. Reported average error i s 1.4%
for 28 di verse components.
Versi on 10
Property
Parameter
Estimation
the Joback method.
Data Method
The Data method determi nes parameters for the i deal gas heat capaci ty
pol ynomi al . Experi mental i deal gas heat capaci ty data are fi tted. You enter thi s
data on the Properti es Data Pure Component form.
Vapor Pressure (PLXANT)
PCES provi des the fol l owi ng methods for esti mati ng vapor pressure:
Data Vapor pressure data
Riedel TB, TC, PC, (vapor pressure data)
Li-Ma Structure, TB, (vapor pressure data)
Mani TC, PC, (vapor pressure data)
The Extended Antoi ne model i s used for thi s property.
Data Method
The Data method determi nes parameters for the Extended Antoi ne equati on by
fi tti ng experi mental vapor pressure data that you enter on the Properti es Data
Pure Component form.
Riedel Method
The Ri edel method esti mates parameters for the Extended Antoi ne vapor pressure
equati on by appl yi ng the Ri edel parameter and the Pl ank-Ri edel constrai nt at the
cri ti cal poi nt. I t al so makes use of the condi ti on that at the normal boi l i ng poi nt,
the vapor pressure i s 1 atm. The parameters are val i d from TB to TC. Thi s method
i s accurate for nonpol ar compounds, but not for pol ar compounds.
Li-Ma Method
The Li -Ma method i s a group contri buti on method for esti mati ng parameters for
the Extended Antoi ne vapor pressure equati on. The parameters are val i d from
TB to TC. Thi s method i s accurate for pol ar and nonpol ar compounds. For 28
di verse compounds, the reported average error was 0.61% (Fluid Phase Equilibria,
101, 101, 1994).
for thi s method.
Versi on 10
Chapter 8
Mani Method
method esti mates parameters for the Extended Antoi ne vapor pressure equati on
usi ng the Ri edel equati on when one or two experi mental vapor pressure data
val ues are avai l abl e. Thi s method can al so be used to esti mate TB and TC.
Thi s method provi des very accurate and rel i abl e esti mates of TB, TC and vapor
pressure curve when some experi mental vapor pressure data val ues are avai l abl e.
I t i s very useful for compl ex compounds that decompose at temperatures bel ow the
normal boi l i ng poi nts. The vapor pressure equati on i s appl i cabl e from the l owest
temperature data poi nt to the cri ti cal temperature.
Heat of Vaporization (DHVLWT)
PCES provi des the fol l owi ng methods for esti mati ng heat of vapori zati on:
Data Heat of vaporization data
Definition TC, PC, PL, (Heat of vaporization data)
Vetere MW, TB, (Heat of vaporization data)
Gani Structure, (Heat of vaporization data)
Ducros Structure, (Heat of vaporization data)
Li-Ma Structure, TB, (Heat of vaporization data)
The Watson model i s used for thi s property.
Data Method
The Data method determi nes the Watson parameters by fi tti ng experi mental heat
of vapori zati on data that you enter on the Properti es Data Pure Component form.
Definition Method
The Defi ni ti on method cal cul ates heat of vapori zati on from the Cl ausi us-Cl apeyron
equati on. I t requi res vapor pressure, TC, and PC as i nput. The cal cul ated heat of
vapori zati on val ues are used to determi ne the parameters for the Watson equati on.
When the Ri edel method was used to esti mate vapor pressure, reported average
error for the heat of vapori zati on was 1.8% for 94 compounds.
Vetere Method
The Vetere method esti mates heat of vapori zati on at TB, then uses the Watson
equati on to extrapol ate heat of vapori zati on to TC. Reported average error i s 1.6%.
Versi on 10
Property
Parameter
Estimation
Gani Method
The Gani method i s a group contri buti on method for esti mati ng heat of
vapori zati on at 298 K. I t uses the Watson equati on to extrapol ate heat of
vapori zati on to TC. Thi s method requi res onl y mol ecul ar structure as i nput.
thi s method.
Ducros Method
The Ducros method i s a group contri buti on method for esti mati ng heat of
vapori zati on at 298K. I t uses the Watson equati on to extrapol ate heat of
vapori zati on to TC (Thermochimica Acta, 36, 39, 1980; 44, 131, 1981; 54, 153, 1982; 75,
329, 1984). Thi s method:
Uses more compl ex structure correcti on
Can be appl i ed to organo-metal l i c compounds
thi s method.
Li-Ma Method
The Li -Ma method i s a group contri buti on method for esti mati ng heat of
vapori zati on at di fferent temperatures. Thi s method requi res mol ecul ar structure
and TB as i nput. Reported average error for 400 di verse compounds was 1.05%
(Fluid Phase Equilibria, 1997).
for thi s method.
Liquid Molar Volume (RKTZRA)
PCES provi des three methods for esti mati ng l i qui d mol ar vol ume:
Data Liquid molar volume data
Gunn-Yamada TC, PC.OMEGA
Le Bas Structure
The Rackett model i s used for thi s property.
Versi on 10
Chapter 8
Gunn-Yamada Method
The Gunn-Yamada method esti mates saturated l i qui d mol ar vol ume, when the
reduced temperature i s l ess than 0.99. The cal cul ated val ues are used to determi ne
the Rackett parameter. Thi s method:
Appl i es to nonpol ar and sl i ghtl y pol ar compounds
I s more accurate than the Le Bas method
Le Bas Method
The Le Bas method esti mates l i qui d mol ar vol ume at TB. The resul t i s used to
determi ne the Rackett parameter. For 29 di verse compounds, an average error of
3.9% i s reported. Thi s method requi res onl y mol ecul ar structure as i nput. Tabl e 3.6
i n ASPEN PLUS Physical Property Data l i sts the functi onal groups.
Data Method
The Data method determi nes the Rackett parameter by fi tti ng the experi mental
l i qui d mol ar vol ume data that you enter on the Properti es Data Pure Component
form.
Liquid Viscosity (MULAND)
PCES provi des the fol l owi ng methods for esti mati ng l i qui d vi scosi ty:
Data Liquid viscosity data
Orrick-Erbar Structure, MW, VL, ZC, TC, PC
Letsou-Stiel MW, TC, PC, OMEGA
The Andrade model i s used for thi s property.
Orrick-Erbar Method
Orri ck-Erbar i s a group-contri buti on method that depends on l i qui d mol ar vol ume.
I t i s l i mi ted to l ow temperatures, rangi ng from above the freezi ng poi nt to the
reduced temperature of 0.75. Thi s method:
I s not rel i abl e for hi ghl y branched structures
Does not appl y to i norgani c l i qui ds or sul fur compounds
Reports an average error of 15% for 188 organi c l i qui ds
thi s method.
Versi on 10
Property
Parameter
Estimation
Letsou-Stiel Method
The Letsou-Sti el method i s appropri ate for hi gh temperatures and for reduced
temperatures of 0.76 to 0.92. The average error i s 3% for 14 l i qui ds.
Data Method
The Data method determi nes the Andrade parameters by fi tti ng experi mental
l i qui d vi scosi ty data that you enter on the Properti es Data Pure Component form.
Vapor Viscosity (MUVDIP)
PCES provi des the fol l owi ng methods for esti mati ng vapor vi scosi ty:
Data Vapor viscosity data
Reichenberg Structure, MW,TC, PC
The DI PPR vapor vi scosi ty correl ati on i s used for thi s property.
Reichenberg Method
Rei chenberg i s a group-contri buti on method. For nonpol ar compounds, the
expected error i s between 1 and 3%. For pol ar compounds, the errors are hi gher,
but usual l y l ess than 4%. Tabl e 3.11 i n ASPEN PLUS Physical Property Data l i sts
the functi onal groups for thi s method.
Data Method
The Data method determi nes the DI PPR vapor vi scosi ty correl ati on parameters by
fi tti ng experi mental vapor vi scosi ty data you enter on the Properti es Data Pure
Component form.
Liquid Thermal Conductivity (KLDIP)
PCES provi des the fol l owi ng methods for esti mati ng l i qui d thermal conducti vi ty:
Data Liquid thermal conductivity data
Sato-Riedel MW, TB, TC
The DI PPR l i qui d thermal conducti vi ty correl ati on i s used for thi s property.
Versi on 10
Chapter 8
Sato-Riedel Method
When you use the Sato-Ri edel method, accuracy vari es wi del y from 1 to 20% for the
compounds tested. The accuracy i s poor for l i ght and branched hydrocarbons.
Data Method
The Data method determi nes the DI PPR l i qui d thermal conducti vi ty correl ati on
parameters. Thi s method fi ts experi mental l i qui d thermal conducti vi ty data. Enter
thi s data on the Properti es Data Pure Component form.
Vapor Thermal Conductivity (KVDIP)
No esti mati on method i s avai l abl e for esti mati ng vapor thermal conducti vi ty. You
can use the Data method to fi t experi mental data di rectl y to the DI PPR vapor
thermal conducti vi ty correl ati on. Use the Properti es Data Pure Component form to
enter experi mental vapor thermal conducti vi ty data.
Surface Tension (SIGDIP)
PCES provi des the fol l owi ng methods for esti mati ng surface tensi on:
Data Surface tension data
Brock-Bird TB, TC, PC
Macleod-Sugden TB, TC, PC, VL, PARC
Li-Ma Structure, TB
The DI PPR surface tensi on correl ati on i s used for thi s property.
Data Method
The Data method determi nes the DI PPR surface tensi on correl ati on parameters by
fi tti ng experi mental surface tensi on data. Enter thi s data on the Properti es Data
Pure Component form.
Brock-Bird Method
The Brock-Bi rd method appl i es to non-hydrogen-bonded l i qui ds. The expected error
i s l ess than 5%.
Macleod-Sugden Method
The Macl eod-Sugden method appl i es to nonpol ar, pol ar, and hydrogen-bonded
l i qui ds. For hydrogen-bonded l i qui ds, errors are normal l y l ess than 5 to 10%.
Versi on 10
Property
Parameter
Estimation
Li-Ma Method
The Li -Ma method i s a group contri buti on method for esti mati ng surface tensi on at
di fferent temperature. Thi s method requi res onl y mol ecul ar structure and TB as
i nput. Reported average error for 427 di verse compounds was 1.09% (Fluid Phase
Equilibria, 118, 13, 1996).
thi s method.
Liquid Heat Capacity (CPLDIP)
PCES provi des the fol l owi ng methods for esti mati ng l i qui d heat capaci ty:
Data Liquid heat capacity data
Ruzicka Structure
The DI PPR l i qui d heat capaci ty correl ati on i s used for thi s property.
Data Method
The Data method determi nes the DI PPR l i qui d heat capaci ty correl ati on
parameters by fi tti ng experi mental l i qui d heat capaci ty data. Enter thi s data on
the Properti es Data Pure Component form.
Ruzicka Method
The Ruzi cka method i s a group contri buti on method for esti mati ng parameters for
the DI PPR l i qui d heat capaci ty correl ati on. The parameters are val i d from the
mel ti ng poi nt to the normal boi l i ng poi nt. Thi s method requi res onl y mol ecul ar
structure as i nput. For 9772 di verse compounds, reported average errors were 1.9%
and 2.9% for nonpol ar and pol ar compounds, respecti vel y (J . Phys. Chem. Ref. Data,
22, 597, 1993; 22, 619, 1993).
thi s method.
Versi on 10
Chapter 8
Solid Heat Capacity (CPSPO1)
PCES provi des the fol l owi ng methods for esti mati ng sol i d heat capaci ty:
Data Solid heat capacity data
Mostafa Structure
The sol i d heat capaci ty correl ati on i s used for thi s property.
Data Method
The Data method determi nes the sol i d heat capaci ty correl ati on parameters by
fi tti ng experi mental l i qui d heat capaci ty data. You enter thi s data on the
Properti es Data Pure Component form.
Mostafa Method
The Mostafa method i s a group contri buti on method for esti mati ng parameters for
the sol i d heat capaci ty correl ati on. Thi s method i s appl i ed to sol i d i norgani c sal ts
whi ch are di vi ded to cati ons, ani ons and l i gands. Reported average errors for 664
di verse sol i d i norgani c sal ts, was 3.18% (Ind. Eng. Chem. RES., 35, 343, 1996).
thi s method.
Solid Standard Enthalpy of Formation (DHSFRM)
Onl y the Mostafa method i s avai l abl e for esti mati ng sol i d standard enthal py of
formati on.
Mostafa Method
The Mostafa method i s a group contri buti on method. Thi s method appl i es to sol i d
i norgani c sal ts whi ch can be di vi ded to cati ons, ani ons and l i gands. Reported
average errors for 938 di verse sol i d i norgani c sal ts was 2.57% (Ind. Eng. Chem.
RES., 34, 4577, 1995).
Tabl es 3.7A i n ASPEN PLUS Physical Property Data l i sts the functi onal groups for
thi s method.
Versi on 10
Property
Parameter
Estimation
Solid Standard Gibbs Free Energy of Formation
(DGSFRM)
Onl y the Mostafa method i s avai l abl e for esti mati ng sol i d standard Gi bbs free
energy of formati on.
Mostafa Method
The Mostafa method i s a group contri buti on method. Thi s method appl i es to sol i d
i norgani c sal ts whi ch can be di vi ded to cati ons, ani ons and l i gands. Reported
average errors for 687 di verse sol i d i norgani c sal ts was 2.06% (Ind. Eng. Chem.
RES., 34, 4577, 1995).
Tabl es 3.7A i n ASPEN PLUS Physical Property Data l i sts the functi onal groups for
thi s method.
Standard Enthalpy of Formation of Aqueous Species
(DHAQHG)
PCES provi des the fol l owi ng methods for esti mati ng standard enthal py of
formati on of aqueous speci es for the Hel geson el ectrol yte model :
AQU-DATA DHAQFM
THERMO DGAQFM, S025C
AQU-EST1 DGAQFM
AQU-EST2 S025C
AQU-DATA Method
The AQU-DATA method uses di rectl y experi mental standard enthal py of formati on
at i nfi ni te di l uti on (DHAQFM) i f i t exi sts i n the databank.
THERMO Method
The THERMO method esti mates standard enthal py of formati on accordi ng to
thermodynami c rel ati onshi p i f DGAQFM and S025C exi st i n the databank, as
fol l ows:
( ) DHAQHG DGAQFM + 298.15* S025C S025E
where S E 025 i s the sum of absol ute entropy of the consti tuent el ements of a
compound at 25
o
C.
Versi on 10
Chapter 8
AQU-EST1 Method
I f DGAQFM i s i n the databank, the AQU-EST1 method esti mates standard
enthal py of formati on usi ng an empi ri cal rel ati on devel oped by Aspen Technol ogy,
as fol l ows:
DHAQHG DGAQFM 1105 128228 . * .
AQU-EST2 Method
I f S025C i s i n the databank, the AQU-EST2 method esti mates standard enthal py
of formati on usi ng an empi ri cal rel ati on devel oped by Aspen Technol ogy, as fol l ows:
( ) DHAQHG S C S E + 1221113214 3137 4034 025 025 . . *
compound at 25
o
C.
Standard Gibbs Free Energy of Formation of Aqueous
Species (DGAQHG)
PCES provi des the fol l owi ng methods for esti mati ng standard Gi bbs free energy
of formati on of aqueous speci es for the Hel geson el ectrol yte model :
AQU-DATA DGAQFM
THERMO DHAQFM, S025C
AQU-EST1 DHAQFM
AQU-EST2 S025C
AQU-DATA Method
The AQU-DATA method uses di rectl y experi mental standard Gi bbs free energy of
formati on at i nfi ni te di l uti on (DGAQFM) i f i t exi sts i n the databank.
THERMO Method
I f DHAQFM and S025C are i n the databank, the THERMO method esti mates
standard Gi bbs free energy of formati on accordi ng to thermodynami c rel ati onshi p,
as fol l ows:
( ) DGAQHG DHAQFM S C S E 29815 025 025 . *
compound at 25
o
C.
Versi on 10
Property
Parameter
Estimation
AQU-EST1 Method
I f DHAQFM i s i n the databank, the AQU-EST1 method esti mates standard Gi bbs
free energy of formati on usi ng an empi ri cal rel ati on devel oped by Aspen
Technol ogy, as fol l ows:
( )
DGAQHG
DHAQFM
+128228
1105
.
.
AQU-EST2 Method
I f S C 025 i s i n the databank, the AQU-EST2 method esti mates standard Gi bbs
free energy of formati on usi ng an empi ri cal rel ati on devel oped by Aspen
Technol ogy, as fol l ows:
( ) DGAQHG S C S E + 122110 2752 2839 2534 025 025 . . *
compound at 25
o
C.
Absolute Entropy of Aqueous Species (S25HG)
PCES provi des the fol l owi ng methods for esti mati ng absol ute entropy of aqueous
speci es for the Hel geson el ectrol yte model :
AQU-DATA S025C
THERMO DGAQFM, DHAQFM
AQU-EST1 DGAQFM
AQU-EST2 DHAQFM
AQU-DATA Method
The AQU-DATA method uses di rectl y the experi mental absol ute entropy (S025C) i f
i t exi sts i n the databank.
THERMO Method
I f DGAQFM and DHAQFM are i n the databank, the THERMO method esti mates
absol ute entropy accordi ng to thermodynami c rel ati onshi p, as fol l ows:
( )
S HG
DHAQFM DGAQFM
S E
25
29815 025

+ .
compound at 25
o
C.
Versi on 10
Chapter 8
AQU-EST1 Method
I f DGAQFM i s i n the databank, the AQU-EST1 method esti mates absol ute entropy
usi ng an empi ri cal rel ati on devel oped by Aspen Technol ogy, as fol l ows:
S HG x DGAQFM S E 25 352205 10 4300788 025
4
+
. * .
compound at 25
o
C.
AQU-EST2 Method
I f DHAQFM i s i n the databank, the AQU-EST2 method esti mates absol ute entropy
usi ng an empi ri cal rel ati on devel oped by Aspen Technol ogy, as fol l ows:
S HG x DHAQFM S E 25 3187349 10 389208 025
4
+
. .
*
Born Coefficient (OMEGHG)
Onl y the Hel geson method i s avai l abl e for esti mati ng the Born coeffi ci ent of
aqueous speci es for the Hel geson el ectrol yte model . Thi s method requi res S25HG
and CHARGE as i nput.
Helgeson Capacity Parameters (CHGPAR)
PCES provi des the fol l owi ng methods for esti mati ng the Hel geson capaci ty
parameters of aqueous speci es for the Hel geson el ectrol yte model :
HG-AUQ OMEGHG, CPAQ0
HG-CRIS OMEGHG, S25HG, CHARGE, IONTYP
HG-EST OMEGHG, S25HG
HG-AQU Method
The HG-AQU method esti mates the Hel geson capaci ty parameters from the
i nfi ni te di l uti on heat capaci ty CPAQ0.
HG-CRIS Method
The HG-CRI S method esti mates the Hel geson capaci ty parameters accordi ng to
the Cri ss-Cobbl e method.
HG-EST Method
The HG-EST method esti mates the Hel geson capaci ty parameters usi ng an
empi ri cal rel ati on devel oped by Aspen Technol ogy.
Versi on 10
Property
Parameter
Estimation
Binary Parameters (WILSON, NRTL, UNIQ)
PCES esti mates bi nary parameters for the WI LSON, NRTL, and UNI QUAC
model s, usi ng i nfi ni te-di l uti on acti vi ty coeffi ci ents. I nfi ni te-di l uti on acti vi ty
coeffi ci ents can be suppl i ed by:
Laboratory data entered on the Properti es Data Mi xture form, wi th data
type=GAMI NF
Esti mati on, usi ng the UNI FAC, UNI F-LL, UNI F-DMD or UNI F-LBY method
For best resul ts, use experi mental i nfi ni te-di l uti on acti vi ty coeffi ci ent data. Of
the four UNI FAC methods, the Dortmund method (UNI F-DMD) gi ves the most
accurate esti mate of i nfi ni te-di l uti on acti vi ty coeffi ci ents. Thi s method i s
recommended. See Chapter 3 for detai l ed descri pti ons of these methods.
I f the data i s at a si ngl e temperature, PCES esti mates onl y the second el ement of
the parameter, such as WI LSON/2. I f the data cover a temperature range, PCES
esti mates both el ements of the parameter, such as WI LSON/1 and WI LSON/2.
UNIFAC R and Q Parameters (GMUFR, GMUFQ,
GMUFDR, GMUFDQ, GMUFLR, GMUFLQ)
PCES provi des the Bondi method for esti mati ng the R and Q parameters for
UNI FAC functi onal groups. ASPEN PLUS uses these parameters i n the UNI FAC,
Dortmund UNI FAC, and Lyngby UNI FAC model s. The Bondi method requi res onl y
mol ecul ar structure as i nput. Tabl e 3.3 i n ASPEN PLUS Physical Property Data
l i sts the functi onal groups for the Bondi method.
O O O O
Physi cal Property Methods and Model s A-1
Versi on 10
Appendix A
A Bromley-Pitzer Activity
Coefficient Model
The Broml ey-Pi tzer acti vi ty coeffi ci ent model i s a si mpl i fi ed Pi tzer model wi th the
i nteracti on parameters esti mated wi th the Broml eys method. I t can be used to
compute acti vi ty coeffi ci ents for aqueous el ectrol ytes up to 6 mol al i oni c strength.
Thi s model i s l ess accurate than the Pi tzer model . The model shoul d not be used for
mi xed-sol vent el ectrol yte systems
Working Equations
The compl ete Pi tzer equati on (Frst and Renon, 1982) for the excess Gi bbs energy
i s (see al so Appendi x C, equati on 4):
( )
G
RT
n f I B m m m m m z C m m m m m
E
W ij i j
j i
ij i j k k
k
ij i j
j i
ijk i j k
k j i j i
+ + +

_
,
1
]
1

1
2
1
6
(1)
Where:
G
E
= Excess Gi bbs energy
R = Gas constant
T = Temperature
n
w
= Ki l ograms of water
z
i
= Charge number of i on i
m
x
x
M n
n
i
i
w
w i
w
_
,

1000
= mol al i ty of i on i
A-2 Physi cal Property Methods and Model s
Versi on 10
Bromley-Pitzer
Activity
Coefficient
Model
Where:
x
i
= Mol e fracti on of i on i
x
w
= Mol e fracti on of water
M
w
= Mol ecul ar wei ght of water (g/mol )
n
i
= Mol es of i on i
B, C, and are i nteracti on parameters, and f(I ) i s an el ectrostati c term as a
functi on of i oni c strength; these terms are di scussed i n Appendi x C. See Appendi x
C for a detai l ed di scussi on of the Pi tzer model .
The C term and the term are dropped from equati on 1 to gi ve the si mpl i fi ed
Pi tzer equati on.
( )
G
RT
n f I B m m m m
E
W ij i j
j i
ij i j
j i
+ +
1
]
1
(2)
Where:
B
ij
=
( ) ( ) ( ) ( )
( )
f
ij ij ij ij

0 1 2 3
, , ,
Therefore, the si mpl i fi ed Pi tzer equati on has two types of bi nary i nteracti on
parameters, s and s. There are no ternary i nteracti on parameters wi th the
si mpl i fi ed Pi tzer equati on.
Note that the Pi tzer model parameter databank descri bed i n Physical Property
Data, Chapter 1, i s not appl i cabl e to the si mpl i fi ed Pi tzer equati on.
A bui l t-i n empi ri cal correl ati on esti mates the
( )
0
and
( )
1
parameters for cati on-
ani on pai rs from the Broml ey i oni c parameters,
ion
and
ion
(Broml ey, 1973). The
esti mated val ues of
( )
0
s and
( )
1
s are overri dden by the user's i nput. For
parameter nami ng and requi rements, see Broml ey-Pi tzer Acti vi ty Coeffi ci ent
Model , Chapter 3.
Parameter Conversion
For 2-2 el ectrol ytes, the parameter
( )
3
corresponds to Pi tzer's
( )
1
;
( )
2
i s the same
i n both ASPEN PLUS and ori gi nal Pi tzer model s. Pi tzer refers to the 2-2
el ectrol yte parameters as
( )
1
,
( )
2
,
( )
0
,
( )
0
and
( )
2
retai n thei r meani ngs i n both
model s, but Pi tzer's
( )
1
i s ASPEN PLUS
( )
3
Be careful to make thi s di sti ncti on
when enteri ng 2-2 el ectrol yte parameters.
Physi cal Property Methods and Model s A-3
Versi on 10
Appendix A
References
L.A. Broml ey, "Thermodynami c Properti es of Strong El ectrol ytes i n Aqueous
Sol uti on, " AI ChE J ., Vol . 19, No. 2, (1973), pp. 313 320.
Frst and H. Renon, "Effect of the Vari ous Parameters i n the Appl i cati on of
Pi tzer's Model to Sol i d-Li qui d Equi l i bri um Prel i mi nary Study for Strong 1-1
El ectrol ytes, I nd. Eng. Chem. Process Des. Dev., Vol . 21, No. 3, (1982),
pp. 396 400.
O O O O
A-4 Physi cal Property Methods and Model s
Versi on 10
Bromley-Pitzer
Activity
Coefficient
Model
Physi cal Property Methods and Model s B-1
Versi on 10
Appendix B
B Electrolyte NRTL Activity
Coefficient Model
The El ectrol yte Non-Random Two Li qui d (NRTL) model i s a versati l e model for the
cal cul ati on of acti vi ty coeffi ci ents. Usi ng bi nary and pai r parameters, the model
can represent aqueous el ectrol yte systems as wel l as mi xed sol vent el ectrol yte
systems over the enti re range of el ectrol yte concentrati ons. Thi s model can
cal cul ate acti vi ty coeffi cents for i oni c speci es and mol ecul ar speci es i n aqueous
el ectrol yte systems as wel l as i n mi xed sol vent el ectrol yte systems. The model
reduces to the wel l -known NRTL model when el ectrol yte concentrati ons become
zero (Renon and Prausni tz, 1969).
The el ectrol yte NTRL model uses the i nfi ni te di l uti on aqueous sol uti on as the
reference state for i ons. I t adopts the Born equati on to account for the
transformati on of the reference state of i ons from the i nfi ni te di l uti on mi xed
sol vent sol uti on to the i nfi ni te di l uti on aqueous sol uti on.
Water must be present i n the el ectrol yte system i n order to compute the
transformati on of the reference state of i ons. Thus, i t i s necessary to i ntroduce a
trace amount of water to use the model for nonaqueous el ectrol yte systems.
Theoretical Basis and Working Equations
I n thi s appendi x, the theoreti cal basi s of the model i s expl ai ned and the worki ng
equati ons are gi ven. The di fferent ways parameters can be obtai ned are di scussed
wi th references to the databank di rectori es and the Data Regressi on System
(DRS). The parameter requi rements of the model are gi ven i n El ectrol yte NRTL
Acti vi ty Coeffi ci ent Model , Chapter 3.
B-2 Physi cal Property Methods and Model s
Versi on 10
Electrolyte
NRTL Activity
Coefficient
Model
Development of the Model
The El ectrol yte NRTL model was ori gi nal l y proposed by Chen et al ., for aqueous
el ectrol yte systems. I t was l ater extended to mi xed sol vent el ectrol yte systems
(Mock et al ., 1984, 1986). The model i s based on two fundamental assumpti ons:
The l i ke-i on repul si on assumpti on: states that the l ocal composi ti on of
cati ons around cati ons i s zero (and l i kewi se for ani ons around ani ons). Thi s i s
based on the assumpti on that the repul si ve forces between i ons of l i ke charge
are extremel y l arge. Thi s assumpti on may be justi fi ed on the basi s that
repul si ve forces between i ons of the same si gn are very strong for nei ghbori ng
speci es. For exampl e, i n sal t crystal l atti ces the i mmedi ate nei ghbors of any
central i on are al ways i ons of opposi te charge.
The l ocal el ectroneutral i ty assumpti on: states that the di stri buti on of
cati ons and ani ons around a central mol ecul ar speci es i s such that the net l ocal
i oni c charge i s zero. Local el ectroneutral i ty has been observed for i ntersti ti al
mol ecul es i n sal t crystal s.
Chen proposed an excess Gi bbs energy expressi on whi ch contai ns two
contri buti ons: one contri buti on for the l ong-range i on-i on i nteracti ons that exi st
beyond the i mmedi ate nei ghborhood of a central i oni c speci es, and the other rel ated
to the l ocal i nteracti ons that exi st at the i mmedi ate nei ghborhood of any central
speci es.
The unsymmetri c Pi tzer-Debi je-Hckel model and the Born equati on are used to
represent the contri buti on of the l ong-range i on-i on i nteracti ons, and the Non-
Random Two Li qui d (NRTL) theory i s used to represent the l ocal i nteracti ons.
The l ocal i nteracti on contri buti on model i s devel oped as a symmetri c model ,
based on reference states of pure sol vent and pure compl etel y di ssoci ated l i qui d
el ectrol yte. The model i s then normal i zed by i nfi ni te di l uti on acti vi ty coeffi ci ents
i n order to obtai n an unsymmetri c model . Thi s NRTL expressi on for the l ocal
i nteracti ons, the Pi tzer-Debi je-Hckel expressi on, and the Born equati on are
added to gi ve equati on 1 for the excess Gi bbs energy (see the fol l owi ng note).
G
RT
G
RT
G
RT
G
RT
m
E
m
E PDH
m
E Born
m
E lc * * , * , * ,
+ + (1)
Thi s l eads to
ln ln ln ln
* * * *

i i
PDH
i
Born
i
lc
+ + (2)
NOTE: The notati on usi ng * to denote an unsymmetri c reference state i s wel l -
accepted i n el ectrol yte thermodynami cs and wi l l be mai ntai ned here. The reader
shoul d be warned not to confuse i t wi th the meani ng of * i n cl assi cal
thermodynami cs accordi ng to I UPAC/I SO, referri ng to a pure component
property. I n fact i n the context of G or , the asteri sk as superscri pt i s never
used to denote pure component property, so the ri sk of confusi on i s mi ni mal . For
detai l s on notati on, see Chapter 1.
Versi on 10
Appendix B
Long-Range Interaction Contribution
The Pi tzer-Debi je-Hckel formul a, normal i zed to mol e fracti ons of uni ty for sol vent
and zero for el ectrol ytes, i s used to represent the l ong-range i nteracti on
contri buti on.
( )
G
RT
x
M
A I
I
m
E PDH
k
k B
x
x
* ,
ln
_
,
_
,
_
,
1000
4
1
1
2
1
2
(3)
Where:
x
k
= Mol e fracti on of component k
M
B
= Mol ecul ar wei ght of the sol vent B
A
= Debi je-Hckel parameter:

A
=
1
3
2
2
1000
1
2
3
2
N d Q
kT
A e
w
_
,
_
,
(4)
N
A
= Avogadro's number
d = Densi ty of sol vent
Q
e
= El ectron charge
w
= Di el ectri c constant of water
T = Temperature
k = Bol tzmann constant
I
x
= I oni c strength (mol e fracti on scal e):
I
x
=
1
2
2
x z
i i
i
(5)
x
i
= Mol e fracti on of component i
z
i
= Charge number of i on i
= "Cl osest approach" parameter
Taki ng the appropri ate deri vati ve of equati on 3, an expressi on for the acti vi ty
coeffi ci ent can then be deri ved.
Versi on 10
Electrolyte
NRTL Activity
Coefficient
Model
( )
ln ln
*
i
PDH
B
i
x
i x x
x
M
A
z
I
z I I
I

_
,
_
,
+ +

+
1
]
1
1000 2
1
2
1
1
2
1
2
1
2
3
2
1
2
2 2
(6)
The Born equati on i s used to account for the Gi bbs energy of transfer of i oni c
speci es from the i nfi ni te di l uti on state i n a mi xed-sol vent to the i nfi ni te di l uti on
state i n aqueous phase.
G
RT
Q
kT
x z
r
m
E Born
e
w
i i
i
i
* ,

_
,
_
,
2
2
2
2
1 1
10

(7)
Where:
r
i
= Born radi us
The expressi on for the acti vi ty coeffi ci ent can be deri ved from (7):
ln
*

i
Born e
w
i
i
Q
kT
z
r

_
,

2 2
2
2
1 1
10 (8)
Local Interaction Contribution
The l ocal i nteracti on contri buti on i s accounted for by the Non-Random Two Li qui d
theory. The basi c assumpti on of the NRTL model i s that the noni deal entropy of
mi xi ng i s negl i gi bl e compared to the heat of mi xi ng: thi s i s i ndeed the case for
el ectrol yte systems. Thi s model was adopted because of i ts al gebrai c si mpl i ci ty and
i ts appl i cabi l i ty to mi xtures that exhi bi t l i qui d phase spl i tti ng. The model does not
requi re speci fi c vol ume or area data.
The effecti ve l ocal mol e fracti ons X
ji
and X
ii
of speci es j and i, respecti vel y, i n
the nei ghborhood of i are rel ated by:
X
X
X
X
G
ji
ii
j
i
ji
_
,
(9)
Where:
X
j
= x C
j j
(C z
j j
for i ons and C
j
= uni ty for mol ecul es)
G
ji
=
( )
e
ji ji

Versi on 10
Appendix B
ji
=
g g
RT
ji ii
ji
= Nonrandomness factor
g
ji
and g
ii
are energi es of i nteracti on between speci es j and i, and i and i,
respecti vel y. Both g
ij
and
ij
are i nherentl y symmetri c ( g g
ji ij
and
ji ij
).
Si mi l arl y,
X
X
X
X
G
ji
ki
j
k
ji ki
_
,
,
(10)
Where:
G
ji ki ,
=
( )
e
ji ki ji ki

, ,
ji ki ,
=
g g
RT
ji ki
ji ki ,
= Nonrandomness factor
Apparent Binary Systems
The deri vati ons that fol l ow are based on a si mpl e system of one compl etel y
di ssoci ated l i qui d el ectrol yte ca and one sol vent B. They wi l l be l ater extended to
mul ti component systems. I n thi s si mpl e system, three di fferent arrangements
exi st:
solvent at
center
cation at
center
anion at
center
c
c
a
B
B B
a c
c
a
B
B
a
B
c
a
B
B
Versi on 10
Electrolyte
NRTL Activity
Coefficient
Model
I n the case of a central sol vent mol ecul e wi th other sol vent mol ecul es, cati ons,
and ani ons i n i ts i mmedi ate nei ghborhood, the pri nci pl e of l ocal el ectroneutral i ty
i s fol l owed: the surroundi ng cati ons and ani ons are such that the nei ghborhood of
the sol vent i s el ectri cal l y neutral . I n the case of a central cati on (ani on) wi th
sol vent mol ecul es and ani ons (cati ons) i n i ts i mmedi ate nei ghborhood, the
pri nci pl e of l i ke-i on repul si on i s fol l owed: no i ons of l i ke charge exi st anywhere
near each other, whereas opposi te charged i ons are very cl ose to each other.
The effecti ve l ocal mol e fracti ons are rel ated by the fol l owi ng expressi ons:
X X X
cB aB BB
+ + 1 (central sol vent cel l s) (11)
X X
Bc ac
+ 1 (central cati on cel l s) (12)
X X
Ba ca
+ 1 (central ani on cel l s) (13)
Usi ng equati on 11 through 13 and the notati on i ntroduced i n equati ons 9 and
10 above, expressi ons for the effecti ve l ocal mol e fracti ons i n terms of the overal l
mol e fracti ons can be deri ved.
X
X G
X G X G X G
iB
i iB
a cB c cB B BB
+ +
i =c, a, or B (14)
X
X
X X G
ac
a
a B Bc ac
+
,
(15)
X
X
X X G
ca
c
c B Ba ca
+
,
(16)
To obtai n an expressi on for the excess Gi bbs energy, l et the resi dual Gi bbs
energi es, per mol e of cel l s of central cati on, ani on, or sol vent, respecti vel y, be
( ) G c cell
m
, ( ) G a cell
m
, and ( ) G B cell
m
. These are then rel ated to the
effecti ve l ocal mol e fracti ons:
( ) ( ) G c cell z X g X g
m c Bc Bc ac ac
+ (17)
( ) ( ) G a cell z X g X g
m a Ba Ba ca ca
+ (18)
( ) G B cell X g X g X g
m aB aB cB cB BB BB
+ + (19)
The reference Gi bbs energy i s determi ned for the reference states of compl etel y
di ssoci ated l i qui d el ectrol yte and of pure sol vent. The reference Gi bbs energi es
per mol e are then:
( ) G c cell z g
m c ac
(20)
( ) G a cell z g
m a ca
(21)
Versi on 10
Appendix B
( ) G B cell g
m BB
(22)
Where:
z
c
= Charge number on cati ons
z
a
= Charge number on ani ons
The mol ar excess Gi bbs energy can be found by summi ng al l changes i n resi dual
Gi bbs energy per mol e that resul t when the el ectrol yte and sol vent i n thei r
reference state are mi xed to form the exi sti ng el ectrol yte system. The expressi on
i s:
( ) ( ) ( ) ( ) ( ) ( )
( ) ( ) ( )
G x G B cell G B cell x G c cell G c cell
x G a cell G a cell
m
E lc
m m m
ref
c m m
ref
a m m
ref
,
+
+
(23)
Usi ng the previ ous rel ati on for the excess Gi bbs energy and the expressi ons for
the resi dual and reference Gi bbs energy (equati ons 17 to 19 and 20 to 22), the
fol l owi ng expressi on for the excess Gi bbs energy i s obtai ned:
G
RT
X X X X X X z X X z
m
E lc
B cB cB B aB aB c Bc c Bc ac a Ba a Ba ca
,
, ,
+ + + (24)
The assumpti on of l ocal el ectroneutral i ty appl i ed to cel l s wi th central sol vent
mol ecul es may be stated as:
X X
aB cB
(25)
Combi ni ng thi s expressi on wi th the expressi on for the effecti ve l ocal mol e
fracti ons gi ven i n equati ons 9 and 10, the fol l owi ng equal i ty i s obtai ned:
G G
aB cB
(26)
The fol l owi ng rel ati onshi ps are further assumed for nonrandomness factors:

aB cB ca B

,
(27)

Bc ac Ba ca B ca , , ,
(28)
and,

ca B B ca , ,
(29)
I t can be i nferred from equati ons 9, 10, and 26 to 29 that:

aB cB ca B

,
(30)

Bc ac Ba ca B ca , , ,
(31)
Versi on 10
Electrolyte
NRTL Activity
Coefficient
Model
The bi nary parameters,
ca B ,
,
ca B ,
and
B ca ,
are now the adjustabl e parameters
for an apparent bi nary system of a si ngl e el ectrol yte and a si ngl e sol vent.
The excess Gi bbs energy expressi on (equati on 24) must now be normal i zed to the
i nfi ni te di l uti on reference state for i ons:
G
RT
G
RT
x x
m
E lc
m
E lc
c c a a
* , ,
ln ln

(32)
Thi s l eads to:
( )
( ) ( )
G
RT
X X X X X X X
X G X G
m
E lc
B cB aB ca B c Bc B ca a Ba B ca
c B ca c ca B a B ca aB ca B
* ,
, , ,
, , , ,
+ + +
+ +

(33)
By taki ng the appropri ate deri vati ves of equati on 33, expressi ons for the acti vi ty
coeffi ci ents of al l three speci es can be determi ned.
( ) ( )
( )
1
2
2 2
z
X G
X G X G X
X X G
X X G
X G
X X G
G
c
c
lc B cB cB
c cB a aB B
a Ba B Ba
c B Ba
B Bc Bc
a B Bc
Bc cB cB
ln
*
+ +
+
+
+
+

(34)
( ) ( )
( )
1
2
2 2
z
X G
X G X G X
X X G
X X G
X G
X X G
G
a
a
lc B aB aB
c cB a aB B
c Bc B Bc
a B Bc
B Ba Ba
c B Ba
Ba aB aB
ln
*
+ +
+
+
+
+

(35)
( ) ( )
( ) ( )
ln

B
lc
cB cB aB aB
c Bc B a
a Bc B
a Ba Ba c
c Ba B
c B cB cB
c cB a aB B
a B aB aB
c cB a aB B
X X
X G X
X G X
X G X
X G X
X X G
X G X G X
X X G
X G X G X
+ +
+
+
+
+ +

+ +
2 2
2 2
(36)
Versi on 10
Appendix B
Multicomponent Systems
The El ectrol yte NRTL model can be extended to handl e mul ti component systems.
The excess Gi bbs energy expressi on i s:
G
RT
X
X G
X G
X
X
X
X G
X G
X
X
X
X G
X G
m
E lc
B
B
j jB jB
j
k kB
k
c
c
a
a
a
a
j jc a c jc a c
j
k kc a c
k
a
a
c
c
c
c
j ja c a ja c a
j
k ka c a
k
,
, ,
,
, ,
,
+
_
,
_
,
(37)
Where:
j and k can be any speci es (a, C, or B)
The acti vi ty coeffi ci ent equati on for mol ecul ar components i s gi ven by:
ln
,
,
,
, ,
,
,
,
B
lc
j jB jB
j
k kB
k
B BB
k kB
k
B
BB
k k kB
k
k k
k
a
a
a
a c
c Bc a c
k kc a c
k
Bc a c
k kc a c kc a c
k
k kc a c
k
c
c
c
a Ba c a
k ka c a
k
X G
X G
X G
X G
X G
X G
X
X
X G
X G
X G
X G
X
X
X G
X G
+
_
,
_
,
B
B
_
,
c a
Bc c a
k ka c a ka c a
k
k ka c a
k
X G
X G
,
, ,
,
(38)
The acti vi ty coeffi ci ent equati on for cati ons i s gi ven by:
1
z
X
X
X G
X G
X G
X G
X G
X G
X
X
X G
X G
X G
X G
c
c
lc a
a
a
a
k kc a c kc a c
k
k kc a c
k
B cB
k kB
k
B
cB
k k kB
k
k k
k
c
c
c
a ca c a
k ka c a
k
c a
ca c a
k ka c a ka c a
k
k ka c a
k
ln
, ,
,
,
,
,
, ,
,
_
,
_
,
_
,
B
B
_
,
(39)
Versi on 10
Electrolyte
NRTL Activity
Coefficient
Model
The acti vi ty coeffi ci ent equati on for ani ons i s gi ven by:
1
z
X
X
X G
X G
X G
X G
X G
X G
X
X
X G
X G
X G
X G
a
a
lc c
c
c
c
k ka c a ka c a
k
k ka c a
k
Bm aB
k kB
k
B
aB
k k kB
k
k k
k
a
a
a
c ac a c
k kc a c
k
a c
ac a c
k kc a c kc a c
k
k kc a c
k
ln
, ,
,
,
,
,
, ,
,
_
,
_
,
_
,
B
B
_
,
(40)
Where:
G
X G
X
cB
a ca B
a
a
a
,
(41)
G
X G
X
aB
c ca B
c
c
c
,
(42)

Bc cB
a B ca
a
a
a
X
X

,
(43)

Ba aB
c B ca
c
c
c
X
X

,
(44)
cB
cB
cB
G

ln
(45)
aB
aB
cB
G

ln
(46)

Ba ca aB ca B B ca , , ,
+ (47)

Bc ac cB ca B B ca , , ,
+ (48)
Versi on 10
Appendix B
Parameters
The model adjustabl e parameters i ncl ude:
Pure component di el ectri c constant coeffi ci ent of nonaqueous sol vents
Born radi us of i oni c speci es
NRTL i nteracti on parameters for mol ecul e-mol ecul e, mol ecul e-el ectrol yte, and
el ectrol yte-el ectrol yte pai rs
Note that for the el ectrol yte-el ectrol yte pai r parameters, the two el ectrol ytes must
share ei ther one common cati on or one common ani on.
Each type of the el ectrol yte NRTL parameter consi sts of both the nonrandomness
factor, , and energy parameters, .
The pure component di el ectri c constant coeffi ci ents of nonaqueous sol vents and
Born radi us of i oni c speci es are requi red onl y for mi xed-sol vent el ectrol yte
systems.
The temperature dependency rel ati ons of these parameters are gi ven i n
El ectrol yte NRTL Acti vi ty Coeffi ci ent Model , Chapter 3.
Heat of mi xi ng i s cal cul ated from temperature deri vati ves of acti vi ty coeffi ci ents.
Heat capaci ty i s cal cul ated from secondary temperature deri vati ve of the acti vi ty
coeffi ci ent. As a resul t, the temperature dependent parameters are cri ti cal for
model i ng enthal py correctl y. I t i s recommended that enthal py data and heat
capaci ty data be used to obtai n these temperature dependency parameters. See
al so El ectrol yte NRTL Enthal py and El ectrol yte NRTL Gi bbs Energy, Chapter 3.
Obtaining Parameters
I n the absence of el ectrol ytes, the el ectrol yte NRTL model reduces to the NRTL
equati on whi ch i s wi del y used for non-el ectrol yte systems. Therefore, mol ecul e-
mol ecul e bi nary parameters can be obtai ned from bi nary nonel ectrol yte systems.
El ectrol yte-mol ecul e pai r parameters can be obtai ned from data regressi on of
apparent si ngl e el ectrol yte systems.
El ectrol yte-el ectrol yte pai r parameters are requi red onl y for mi xed el ectrol ytes
wi th a common i on. El ectrol yte-el ectrol yte pai r parameters can affect trace i oni c
acti vi ty preci pi tati on. El ectrol yte-el ectrol yte pai r parameters can be obtai ned by
regressi ng sol ubi l i ty data of mul ti pl e component el ectrol yte systems.
Versi on 10
Electrolyte
NRTL Activity
Coefficient
Model
When the el ectrol yte-mol ecul e and el ectrol yte-el ectrol yte pai r parameters are
zero, the el ectrol yte NRTL model reduces to the Debi je-Hckel l i mi ti ng l aw.
Si mul ati on resul ts wi th el ectrol yte-mol ecul e and el ectrol yte-el ectrol yte pai r
parameters fi xed to zero shoul d be adequate for very di l ute weak el ectrol yte
systems; however, for concentrated systems, pai r parameters are requi red for
accurate representati on.
See Physical Property Data, Chapter 1, for the pai r parameters avai l abl e from
the el ectrol yte NRTL model databank. The tabl e contai ns pai r parameters for
some el ectrol ytes i n aqueous sol uti on at 100C. These val ues were obtai ned by
usi ng the ASPEN PLUS Data Regressi on System (DRS) to regress vapor
pressure and mol e fracti on data at T=100C wi th SYSOP15S (Handbook of
Chemistry and Physics, 1975). I n runni ng the DRS, standard devi ati ons for the
temperature (C), vapor pressure (mmHg), and mol e fracti ons were set at 0.2,
1.0, and 0.001, respecti vel y. I n addi ti on, compl ete di ssoci ati on of the el ectrol yte
was assumed for al l cases.
References
C.-C. Chen, H.I . Bri tt, J.F. Boston, and L.B. Evans, "Local Composi ti ons Model for
Excess Gi bbs Energy of El ectrol yte Systems: Part I : Si ngl e Sol vent, Si ngl e
Compl etel y Di ssoci ated El ectrol yte Systems:, AI ChE J ., Vol . 28, No. 4, (1982),
p. 588-596.
C.-C. Chen, and L.B. Evans, "A Local Composi ti on Model for the Excess Gi bbs
Energy of Aqueous El ectrol yte Systems," AI ChE J ., Vol . 32, No. 3, (1986),
p. 444-459.
Handbook of Chemistry and Physics, 56th Edi ti on, CRC Press, 1975, p. E-1.
B. Mock, L.B. Evans, and C.-C. Chen, "Phase Equi l i bri a i n Mul ti pl e-Sol vent
El ectrol yte Systems: A New Thermodynami c Model ," Proceedi ngs of the 1984
Summer Computer Si mul ati on Conference, p. 558.
B. Mock, L.B. Evans, and C.-C. Chen, "Thermodynami c Representati on of Phase
Equi l i bri a of Mi xed-Sol vent El ectrol yte Systems," AI ChE J ., Vol . 32, No. 10,
(1986), p. 1655-1664.
Renon, and J.M. Prausni tz, "Local Composi ti ons i n Thermodynami c Excess
Functi ons for Li qui d Mi xtures", AI ChE J ., Vol . 14, No. 1, (1968), pp. 135-144.
O O O O
Physi cal Property Methods and Model s C-1
Versi on 10
Appendix C
C Pitzer Activity
Coefficient Model
The Pi tzer model was devel oped as an i mprovement upon an earl i er model
proposed by Guggenhei m (1935, 1955). The earl i er model worked wel l at l ow
el ectrol yte concentrati ons, but contai ned di screpanci es at hi gher concentrati ons
(>0.1M). The Pi tzer model resol ved these di screpanci es, wi thout resorti ng to
excessi ve arrays of hi gher-order terms.
The model can be used for aqueous el ectrol yte systems, up to 6 mol al i oni c
strength. I t cannot be used for mi xed sol vent el ectrol yte systems.
Thi s appendi x provi des theoreti cal background for the model . Al l model
equati ons are i ncl uded. Parameter requi rements are di scussed i n Pi tzer Acti vi ty
Coeffi ci ent Model , Chapter 3.
Model Development
The Pi tzer model anal yzes "hard-core" effects i n the Debi je-Hckel theory. I t uses
the fol l owi ng expansi on as a radi al di stri buti on functi on:
( ) ( ) ( ) g r q r q r
ij ij ij
+ 1
1
2
2
(1)
Where:
g
ij
= Di stri buti on functi on
r = Radi us
q
ij
=
( )
z Q
r
kT
i e
j
(pai r potenti al of mean force)

C-2 Physi cal Properti es Methods and Model s
Versi on 10
Pitzer
Activity
Coefficient
Model
Wi th:
z
i
= Charge of i on i
Q
e
= El ectron charge
( )
j
r = Average el ectri c potenti al for i on j
k = Bol tzmanns constant
T = Temperature
Thi s radi al di stri buti on functi on i s used i n the so-cal l ed pressure equati on that
rel ates thi s functi on and the i ntermol ecul ar potenti al to thermodynami c
properti es. From thi s rel ati on you can obtai n an expressi on for the osmoti c
coeffi ci ent.
Pi tzer proposes a general equati on for the excess Gi bbs energy. The basi c equati on
i s:
( ) ( )
G
n RT
f I m m m m m
E
w
ij i j
j
ijk i j k
k j i i
+ +

1 (2)
Where:
G
E
= Excess Gi bbs energy
R = Gas constant
T = Temperature
n
w
= Ki l ograms of water
m
i
=
x
x
M n
n
i
w
w i
w
1000
_
,
(mol al i ty of i on i)
Wi th:
x
i
= Mol e fracti on of i on i
x
w
= Mol e fracti on of water
M
w
= Mol ecul ar wei ght of water (g/mol )
n
i
= Mol es of i on i
Versi on 10
Appendix C
The functi on f(I ) i s an el ectrostati c term that expresses the effect of l ong-range
el ectrostati c forces between i ons. Thi s takes i nto account the hard-core effects of
the Debi je-Hckel theory. Thi s term i s di scussed i n detai l i n the fol l owi ng secti on.
The parameters
ij
are second vi ri al coeffi ci ents that account for the short-range
forces between sol utes i and j. The parameters
ijk
account for the i nteracti ons
between sol utes, i, j, k. For i on-i on i nteracti ons,
ij
i s a functi on of i oni c strength.
For mol ecul e-i on or mol ecul e-mol ecul e i nteracti ons thi s i oni c strength dependency
i s negl ected. The dependence of
ijk
on i oni c strength i s al ways negl ected. The
matri ces
ij
and
ijk
are al so taken to be symmetri c (that i s,
ij ji
).
Pi tzer modi fi ed thi s expressi on for the Gi bbs energy by i denti fyi ng combi nati ons
of functi ons. He devel oped i nteracti on parameters that can be eval uated usi ng
experi mental data. He sel ected mathemati cal expressi ons for these parameters
that best fi t experi mental data.
Pi tzer's model can be appl i ed to aqueous systems of strong el ectrol ytes and to
aqueous systems of weak el ectrol ytes wi th mol ecul ar sol utes. These appl i cati ons
are di scussed i n the fol l owi ng secti on.
Application of the Pitzer Model to
Aqueous Strong Electrolyte Systems
Pi tzer modi fi ed hi s basi c equati on to make i t more useful for data correl ati on of
aqueous strong el ectrol ytes. He defi ned a set of more di rectl y observabl e
parameters to represent combi nati ons of the second and thi rd vi ri al coeffi ci ents.
The modi fi ed Pi tzer equati on i s:
( )
G
RT
n
f I m m B m z C
m m
m
m m
m
e
w
c a ca c c
c
ca
a c
c c cc
a cc a
a
a a aa
c caa
c
a a c c
+ +
_
,
_
,
+ +
_
,
+ +
_
,
1
]
1
1
1
1
1
1

2
2 2

(3)
z
i
= Charge of i on i
Versi on 10
Pitzer
Activity
Coefficient
Model
Subscri pts c, c , and a, a denote cati ons and ani ons of the sol uti on. B, C, , and
are i nteracti on parameters. f(I ) i s an el ectrostati c term as a functi on of i oni c
strength. The cati on-ani on parameters B and C are characteri sti c for an aqueous
si ngl e-el ectrol yte system. These parameters can be determi ned by the properti es of
pure (apparent) el ectrol ytes. B i s expressed as a functi on of
( )
0
and
( )
1
or
( )
0
,
( )
2
and
( )
3
(see equati ons 11 through 15).
The parameters and are for the di fference of i nteracti on of unl i ke i ons of
the same si gn from the mean of l i ke i ons. These parameters can be measured
from common-i on mi xtures. Exampl es are NaCl KCl H + +
2
0 or
NaCl NaNO H + +
3 2
0 (si c, Pi tzer, 1989). These terms are di scussed i n detai l l ater
i n subsequent secti ons of thi s chapter.
Frst and Renon (1982) propose the fol l owi ng expressi on as the Pi tzer equati on
for the excess Gi bbs energy:
( )
G
RT
n
f I B m m m m m z C m m
m m m
E
w
ij i j
j i
ij i j k k
k j i j i
ij i j
ijk i j k
k j i
+ + +

_
,
1
]
1
1
1
1

1
2
1
6

(4)
The di fference between equati ons 3 and 4 i s that Pi tzer orders cati on before
ani ons. Frst and Renon do not. Al l summati ons are taken over al l i ons i and j
(both cati ons and ani ons). Thi s i nvol ves maki ng the parameter matri ces B
ij
, C
ij
,
ij
, and
ijk
symmetri c, as fol l ows:
Second-order parameters are wri tten B
ij
i f i and j are i ons of di fferent si gn.
B
ij
0 i f the si gn of z
i
= si gn of z
j
, and B
ii
0 . Si nce cati ons are not ordered
before ani ons, B B
ij ji
. Thi s el i mi nates the 2 i n the second term i n brackets i n
Pi tzer's ori gi nal expressi on (equati on 3). Second-order parameters are wri tten
ij
i f i and j are i ons of the same si gn. Thus
ij
i
i s di fferent from
the si gn of z
j
, and
ii
0 wi th
ij ji
.
Thi rd-order parameters are wri tten C
ij
i f i and j are i ons wi th di fferent si gns.
C
ij
i
= si gn of z
i
, and C
ii
0 wi th C C
ij ji
. The factor of 2 i n
the fi fth bracketed term i n Pi tzer's ori gi nal expressi on (equati on 3) becomes 1/2
i n equati on 4. The matri x C i s symmetri c and m z
k k
i s extended to al l i ons to
make the equati on symmetri c.
Versi on 10
Appendix C
ijk
i s wri tten for three di fferent i ons
ijk kij jki
, and
ikk
0 .
ijk
0 i f
the si gn of z
i
=si gn of z
i
=si gn of z
k
. The factor of 1/6 i s di fferent from 1/2 i n the
l ast term i n brackets i n Pi tzers ori gi nal expressi on. Pi tzer di sti ngui shes between
cati ons and ani ons. I n Pi tzers ori gi nal model thi s parameter appears twi ce, as
cc a
and
c ca
. I n thi s modi fi ed model , i t appears si x ti mes, as
cc a
,
c ca
,
acc
,
ac c
,
cac
and
c ac
. Frst and Renon's expressi on, equati on 4, cal cul ates the
expressi ons for acti vi ty coeffi ci ents and osmoti c coeffi ci ents.
Calculation of Activity Coefficients
The natural l ogari thm of the acti vi ty coeffi ci ent for i ons i s cal cul ated from equati on
4 to gi ve:
ln
,
*
m i
E
i
i j ij i ij j k
k i j
ij j i jk j k
k j j
k k
k
ij j ijk j k
k j j
G
RT
n
z f m B z m m
m z C m m
m z C m m m
_
,
+ +
+ +
+

_
,
+

1
2
2
1
2
2
1
2
1
2
2
2
(5)
Where i s negl ected.
For water the l ogari thm of the acti vi ty coeffi ci ent i s cal cul ated si mi l arl y, as
fol l ows:
Appl yi ng:
ln
,
m w
E
w
G
RT
n
_
,
to equati on 3 and usi ng:

n
N M
w
w w
1000
Where N
w
mol es water, gi ves:
Versi on 10
Pitzer
Activity
Coefficient
Model
1000
1
3
M
f If m m B B I m m
m z m m C m m m
w
m w i j ij
j i
ij
j i
i j ij
j i
k k k i j ij
j i
i j k ijk
k j i
ln
,

(6)
f(I ), the el ectrostati c term, i s expressed as a functi on of i oni c strength I :
( )
( )
[ ]
f I A
I
b
bI

_
,
4
1
1
2
ln (7)
I , the i oni c strength, i s defi ned as:
I m z
i i
i

1
2
2
(8)
Taki ng the deri vati ve of equati on 7 wi th respect to I , gi ves:
( )
( )

+
+ +
1
]
1
f I
df
dI
A
I
bI b
bI 2
1
2
1
1
2
1
2
1
2
ln (9)
So that:
f If
A I
bI

+
2
1
3
2
1
2
(10)
Thi s equati on i s used i n equati on 6. I n equati ons 7 and 9, i s the usual Debi je-
Hckel constant for the osmoti c coeffi ci ent, determi ned from:
A
N d Q
kT
A w e
B
_
,
_
,
1
3
2
2
1000
1
2
3
2
(11)
Where:
N
A
= Avogadro's constant
d
w
= Water densi ty
B
= Di el ectri c constant of sol vent B
b i s an adjustabl e parameter, whi ch has been opti mi zed i n thi s model to equal 1.2.
B and B need expressi ons so that equati ons 5 and 6 can compl etel y be sol ved for
the acti vi ty coeffi ci ents. The parameter B i s determi ned di fferentl y for di fferent
el ectrol yte pai ri ngs. For 1-n el ectrol ytes (1-1, 1-2, 2-1, and so on) the fol l owi ng
expressi on gi ves the parameter B:
Versi on 10
Appendix C
( )
( )
( )
B
I
I e
ij
ij
I
+ +
1
]
1
1
_
,

0
1
1
2 1
2
1 1
1
2
1
1
2
(12)
wi th
1
=2.0.
For 2-2 el ectrol ytes, B i s determi ned by the fol l owi ng expressi on:
( )
( )
( )
( )
( )
B
I
I e
I
I e
ij
ij
I
ij
I
+ +
1
]
1
1
+ +
1
]
1
1
_
,

_
,

0
2
2
2 2
3
3
2 3
2
1 1
2
1 1
1
2
2
1
2
1
2
3
1
2
(13)
wi th
2
12 0 . and
3
14 . .
By taki ng appropri ate deri vati ves, expressi ons for B can be deri ved for 1 n
el ectrol ytes:
( )
( )
+ + +
1
]
1
1
_
,
B
I
I I e
I
2
4
1 1 2 2
1
2
2
1
2
1
2
(14)
and for 2-2 el ectrol ytes:
( )
( )
( )
( )
( )
+ + +
1
]
1
1
+ + + +
_
,
1
]
1
1
_
,
_
,
B
I
I I e
I
I
I
e
I
I
2
144
1 1 12 72
2
14
1 1 14
14
2
2
2
2
12
3
2
2
2
1 4
1
2
1
2
1
2
.
.
.
.
(15)
The parameters
( )
0
,
( )
1
,
( )
2
,
( )
3
and al so C, , and can be found i n Pi tzer's
arti cl es (see References on page C-11).
After the acti vi ty coeffi ci ents are cal cul ated, they can be converted to the mol e
fracti on scal e from the mol al i ty scal e by the fol l owi ng rel ati ons:
For i ons:

x i m i
i
i
w
m
x
M
, ,
_
,
_
,
1000
(16)
For water:
x w
m i
i w
i
w
m M
x
,
,
exp
_
,
1000
(17)
Versi on 10
Pitzer
Activity
Coefficient
Model
Where:
m
= Acti vi ty coeffi ci ent (mol al i ty scal e)
x
= Acti vi ty coeffi ci ent (mol e fracti on scal e)
Application of the Pitzer Model to
Aqueous Electrolyte Systems with
Molecular Solutes
I n aqueous weak el ectrol yte systems wi th mol ecul ar sol utes, the second and thi rd
vi ri al coeffi ci ents i n the basi c Pi tzer equati on for mol ecul e-i on and mol ecul e-
mol ecul e i nteracti ons must be consi dered. The fol l owi ng extensi ons of Pi tzers
i nteracti on parameters are made.
The second-order parameters B
ij
are extended to i ncl ude mol ecul e-mol ecul e and
mol ecul e-i on i nteracti on parameters.
The thi rd-order parameters
ijk
are extended to mol ecul e-mol ecul e-mol ecul e
i nteracti ons. The fol l owi ng expressi ons rel ate
ijk
to Pi tzers ori gi nal
ijk
:
iii iii
6
However, mol ecul e-mol ecul e i nteracti ons were not taken i nto account by Pi tzer
and coworkers. So
iii
i s an arti fi ci al l y i ntroduced quanti ty.
The equati ons for acti vi ty coeffi ci ents and the Gi bbs free energy are the same as
equati ons 3 through 6.
Versi on 10
Appendix C
Parameters
The Pi tzer model i n ASPEN PLUS i nvol ves user-suppl i ed parameters. These
parameters are used i n the cal cul ati on of bi nary and ternary parameters for the
el ectrol yte system. These parameters i ncl ude the cati on-ani on parameters
( )
0
,
( )
1
,
( )
2
,
( )
3
and C
, cati on-cati on parameter

cc
, ani on-ani on parameter
aa
, cati on1-cati on2-common ani on parameter
cc a
, ani on1-ani on2-common
cati on parameter
caa
, and the mol ecul e-i on and mol ecul e-mol ecul e parameters
( )
0
,
( )
1
and, C
. The parameter names i n ASPEN PLUS and thei r

requi rements are di scussed i n Pi tzer Acti vi ty Coeffi ci ent Model , Chapter 3.
Parameter Conversion
For 2-2 el ectrol ytes the parameter
( )
3
corresponds to Pi tzers
( )
1
.
( )
2
i s the
same i n both the ASPEN PLUS and ori gi nal Pi tzer model s. Pi tzer refers to the 2-2
el ectrol yte parameters as
( )
1
,
( )
2
,
( )
0
.
( )
0
and
( )
2
retai n thei r meani ngs i n
both model s, but Pi tzers
( )
1
i s
( )
3
i n ASPEN PLUS. Be careful to make thi s
di sti ncti on when enteri ng 2-2 el ectrol yte parameters.
Pi tzer often gi ves val ues of
( )
0
,
( )
1
,
( )
2
,
( )
3
, and C
that are corrected by

some factors (see Pi tzer and Mayorga (1973) for exampl es). These factors
ori gi nate from one of Pi tzers earl i er expressi ons for the excess Gi bbs energy:
( ) ( )
G
n RT
f m n n B m n n
E
w
G
c a
G
c a
C
E E
ca
G
E
+ +

1
]
1
2 3
3
2
2 2
(18)
Where:
C
ca
G
E
= 1 2C
ca
n
a
= Mol e number of ani ons
n
c
= Mol e number of cati on
Here
( )
0
,
( )
1
,
( )
2
, and
( )
3
are mul ti pl i ed by a factor of 2n n
c a
. C i s mul ti pl i ed
by a factor of ( ) 2
3
2
n n
c a
.
ASPEN PLUS accounts for these correcti ng factors. Enter the parameters
wi thout thei r correcti ng factors.
For exampl e, Pi tzer gi ves the val ues of parameters for M Cl
g 2
as:
Versi on 10
Pitzer
Activity
Coefficient
Model
( )
4 3
0
= 0.4698
( )
4 3
1
= 2.242
2
3
5 2
C
= 0.00979
Perform the necessary conversi ons and enter the parameters as:
( )
Mg Cl
2
0
+
,
= 0.3524
( )
Mg Cl
2
0
+
,
= 1.6815
C
Mg Cl
2+
,
= 0.00520
Parameter Sources
Bi nary and ternary parameters for the Pi tzer model for vari ous el ectrol yte
systems are avai l abl e from Pi tzers seri es on the thermodynami cs of el ectrol ytes.
These papers and the el ectrol yte parameters they gi ve are:
Reference Parameters available
(Pitzer, 1973)
Binary parameters
( ) ( )
( )
0 1
, , C for 13 dilute aqueous electrolytes
(Pitzer and Mayorga, 1973) Binary parameters for 1-1 inorganic electrolytes, salts of carboxylic acids (1-1),
tetraalkylammonium halids, sulfonic acids and salts, additional 1-1 organic
salts, 2-1 inorganic compounds, 2-1 organic electrolytes, 3-1 electrolytes, 4-1
and 5-1 electrolytes
(Pitzer and Mayorga, 1974) Binary parameters for 2-2 electrolytes in water at 25C
(Pitzer and Kim, 1974) Binary and ternary parameters for mixed electrolytes, binary mixtures without a
common ion, mixed electrolytes with three or more solutes
(Pitzer, 1975) Ternary parameters for systems mixing doubly and singly charged ions
(Pitzer and Silvester, 1976) Parameters for phosphoric acid and its buffer solutions
(Pitzer, Roy and Silvester, 1977) Parameters and thermodynamic properties for sulfuric acid
(Pitzer and Silvester, 1977) Data for NaCl and aqueous NaCl solutions
(Pitzer, Silvester, and Peterson, 1978) Rare earth chlorides, nitrates, and perchlorates
(Peiper and Pitzer, 1982) Aqueous carbonate solutions, including mixtures of sodium carbonate,
bicarbonate, and chloride
(Phutela and Pitzer, 1983) Aqueous calcium chloride
(Pitzer, Conceicao, and deLima, 1983) Saturated aqueous solutions, including mixtures of sodium chloride, potassium
chloride, and cesium chloride
Versi on 10
Appendix C
References
C.-C. Chen, H.I . Bri tt, J.I . Boston and L.B. Evans, "Extensi on and Appl i cati on of
the Pi tzer Equati on for Vapor-Li qui d Equi l i bri um of Aqueous El ectrol yte Systems
wi th Mol ecul ar Sol utes," AI ChE.J ., Vol . 25, (1979), pp. 820-831.
M. Concei cao, P. de Li ma, and K.S. Pi tzer, "Thermodynami cs of Saturated
Aqueous Sol uti ons I ncl udi ng Mi xtures of NaCl , KCl , and CsCl , "J . Solution
Chem, Vol . 12, No. 3, (1983), pp. 171-185.
W. Frst and H. Renon, "Effects of the Vari ous Parameters i n the Appl i cati on of
Pi tzer's Model to Sol i d-Li qui d Equi l i bri um. Prel i mi nary Study for Strong 1-1
El ectrol ytes," I nd. Eng. Chem. Process Des. Dev., Vol . 21, No. 3, (1982), pp. 396-
400.
E.A. Guggenhei m, Phil. Mag., Vol . 7, No. 19, (1935), p. 588.
E.A. Guggenhei m and J.C. Turgeon, Trans. Faraday Soc., Vol . 51, (1955), p. 747.
J.C. Pei per and K.S. Pi tzer, "Thermodynami cs of Aqueous Carbonate Sol uti ons
I ncl udi ng Mi xtures of Sodi um Carbonate, Bi carbonate, and Chl ori de," J . Chem.
Thermodynamics, Vol . 14, (1982), pp. 613-638.
R.C. Phutel a and K.S. Pi tzer, "Thermodynami cs of Aqueous Cal ci um Chl ori de,"
J . Solution Chem., Vol . 12, No. 3, (1983), pp. 201-207.
K.S. Pi tzer, "Thermodynami cs of El ectrol ytes. I . Theoreti cal Basi s and General
Equati ons, " J . Phys. Chem., Vol . 77, No. 2, (1973), pp. 268-277.
K.S. Pi tzer, J . Solution Chem., Vol . 4, (1975), p. 249.
K.S. Pi tzer, "Theory: I on I nteracti on Approach," Activity Coefficients in
Electrolyte Solutions, Pytkowi cz, R. ed., Vol . I , (CRC Press I nc., Boca Raton,
Fl ori da, 1979).
K.S. Pi tzer, "Fl ui ds, Both I oni c and Non-I oni c, over Wi de Ranges of Temperature
and Composi ti on," J . Chen. Thermodynamics, Vol . 21, (1989), pp. 1-17. (Seventh
Rossi ni l ecture of the commi ssi on on Thermodynami cs of the I UPAC, Aug. 29,
1988, Prague, ex-Czechosl ovaki a).
K.S. Pi tzer and J.J. Ki m, "Thermodynami cs of El ectrol ytes I V; Acti vi ty and
Osmoti c Coeffi ci ents for Mi xed El ectrol ytes," J .Am. Chem. Soc., Vol . 96 (1974),
p. 5701.
K.S. Pi tzer and G. Mayorga, "Thermodynami cs of El ectrol ytes I I ; Acti vi ty and
Osmoti c Coeffi ci ents for Strong El ectrol ytes wi th One or Both I ons Uni val ent,"
J . Phys. Chem., Vol . 77, No. 19, (1973), pp. 2300-2308.
K.S. Pi tzer and L.F. Si l vester, "Thermodynami cs of El ectrol ytes VI . Weak
El ectrol ytes I ncl udi ng H PO
3 4
," J . Solution Chem., Vol . 5, (1976), p. 269.
Versi on 10
Pitzer
Activity
Coefficient
Model
K.S. Pi tzer and G. Mayorga, J . Phys Chem., Vol . 77, (1973), p. 2300.
K.S. Pi tzer and G. Mayorga, J . Solution Chem., Vol . 3, (1974), p. 539.
K.S. Pi tzer and L.F. Si l vester, J . Solution Chem., Vol . 5, (1976), p. 269.
K.S. Pi tzer and R.N. Roy, and L.F. Si l vester, "Thermodynami cs of El ectrol ytes 7
Sul furi c Aci d," J . Am. Chem. Soc., Vol . 99, No. 15, (1977), pp. 4930-4936.
K.S. Pi tzer, J.R. Peterson, and L.F. Si l vester, "Thermodynami cs of El ectrol ytes.
I X. Rare Earth Chl ori des, Ni trates, and Perchl orates, "J . Solution Chem., Vol . 7,
No. 1, (1978), pp. 45-56.
H. Renon, "Devi ati on from I deal i ty i n El ectrol yte Sol uti ons," Foundation of
Computer-Aided Chemical Process Design, Vol. I I , Engineering Foundations,
(1981), New York.
L.F. Si l vester and K.S. Pi tzer, "Thermodynami cs of El ectrol ytes 8 Hi gh-
Temperature Properti es, I ncl udi ng Enthal py and Heat Capaci ty, Wi th
Appl i cati on to Sodi um Chl ori de, "J . Phys. Chem., Vol . 81, No. 19, (1977),
pp. 1822-1828.
O O O O
Physi cal Property Methods and Model s I ndex-1
Rel ease 10
I ndex
A
Acentri c factor esti mati on methods 8-9
Acti vi ty coeffi ci ent method
for cal cul ati ng phase equi l i bri um 1-3
l i st 1-10
Acti vi ty coeffi ci ent model s
characteri sti cs of 1-32
common model s for 2-53
l i st of property methods 2-43
l i st of property model s 3-53
AMI NES property method 2-55
Andrade/DI PPR vi scosi ty model 3-122
Antoi ne/Wagner vapor pressure model 3-80
API model
l i qui d vi scosi ty 3-124
l i qui d vol ume 3-87
surface tensi on 3-154
API -METH property method 7-3
API SOUR property method 2-57
API -TWU pseudocomponent property method 7-3
Apparent component
approach 5-3
mol e fracti ons 5-6
Appl i cati ons
chemi cal 1-17
l i qui d-l i qui d equi l i bri um 1-21
metal l urgi cal 1-17, 3-58
petrochemi cal 1-17
Aqueous i nfi ni te di l uti on heat capaci ty model 3-98
ASPEN pseudocomponent property method 7-3
B
BARI N equati ons thermodynami c property model 3-
106
Bi nary parameters esti mati on methods 8-26
BK10 property method 2-11
B-PI TZER property method 2-64
Brel vi -OConnel l model 3-88
Broml ey-Pi tzer acti vi ty coeffi ci ent model 3-54, 0-1
BWR-Lee-Starl i ng property model 3-8
BWR-LS property method 2-21
C
Cavett thermodynami c property model 3-105
CHAO-SEA property method 2-11, 2-12
Chao-Seader fugaci ty model 3-81
Chapman-Enskog
Brokaw/DI PPR vi scosi ty model 3-124
Brokaw-Wi l ke mi xi ng rul e vi scosi ty model 3-126
Wi l ke-Lee (bi nary) di ffusi on model 3-148
Wi l ke-Lee (mi xture) di ffusi on model 3-149
Chemi cal reacti ons for el ectrol ytes 5-2
Chemi stry 5-2
Chi en-Nul l acti vi ty coeffi ci ent model 3-55
Chung-Lee-Starl i ng model
l ow pressure vapor vi scosi ty 3-127
thermal conducti vi ty 3-138
vi scosi ty 3-129
Cl arke el ectrol yte l i qui d vol ume model 3-89
Cl asses of property methods 2-2
Cl ausi us-Cl apeyron equati on for heat of vapori zati on
3-86
Coal property model s 3-160
COAL-LI Q property method 7-3
Constant acti vi ty coeffi ci ent model 3-58
COSTALD l i qui d vol ume model 3-91
Cri ss-Cobbl e aqueous i nfi ni te di l uti on i oni c heat
capaci ty model 3-98
Cri ti cal compressi bi l i ty factor esti mati on methods 8-
9
Cri ti cal pressure esti mati on methods 8-7
Cri ti cal temperature esti mati on methods 8-5
Cri ti cal vol ume esti mati on methods 8-8
Cubi c equati ons of state 1-22
D
Data regressi on
and el ectrol ytes 5-9
Dawson-Khoury-Kobayashi di ffusi on model
bi nary 3-150
mi xture 3-151
DCOALI GT coal densi ty model 3-171
Dean-Sti el pressure correcti on vi scosi ty model 3-131
Debi je-Huckel vol ume model 3-92
DGHARI GT char densi ty model 3-173
Di ffusi on coeffi ci ent property methods 1-36, 4-35
Di ffusi vi ty model s l i st 3-148
I ndex-2 Physi cal Property Methods and Model s
Versi on 10
DI PPR model
heat of vapori zati on 3-85
i deal gas heat capaci ty 3-100
l i qui d heat capaci ty 3-99
l i qui d surface tensi on 3-156
l i qui d thermal conducti vi ty 3-142
l i qui d vol ume 3-93
vapor thermal conducti vi ty 3-144
vapor vi scosi ty 3-125
vi scosi ty 3-123
DNSTYGEN nonconventi onal component densi ty
model 3-158
E
ELECNRTL property method 2-58
El ectrol yte acti vi ty coeffi ci ent model s 1-33
El ectrol yte data regressi on overvi ew 5-9
El ectrol yte model s
Cl arke l i qui d vol ume 3-89
el ectrol yte NRTL 3-109
Gi bbs energy 3-110
Jones-Dol e vi scosi ty 3-133
Nernst-Hartl ey di ffusi on 3-151
Onsager-Samaras surface tensi on 3-156
Ri edel thermal conducti vi ty 3-141
El ectrol yte NRTL
acti vi ty coeffi ci ent model 3-58, 0-1
enthal py thermodynami c property model 3-109
equati on 5-8
Gi bbs energy thermodynami c property model 3-
110
El ectrol yte property methods 2-54, 2-66
ELECNRTL 2-58
ENRTL-HF 2-60
El ectrol yte si mul ati on
overvi ew 5-1
El ectrol yte thermodynami c model s overvi ew 5-7
ENRTL-HF property method 2-60, 2-61, 2-66
Enthal pi es model based on di fferent reference states
3-112
Enthal py and densi ty model s for coal and char 3-160
Enthal py bal ances
nonconventi onal components 1-37
Enthal py of formati on esti mati on methods
sol i d 8-21
standard i deal gas 8-10
ENTHGEN nonconventi onal component heat
capaci ty model 3-159
Equati on-of-state
common model s for property methods 2-25
method for phase equi l i bri um 1-2, 1-3
property methods
for high-pressure hydrocarbon applications 2-20
property model s 1-22, 3-7
F
Fl exi bl e and predi cti ve property methods
equati on-of-state 2-26
Free-water cal cul ati ons 6-1
Fugaci ty model s l i st 3-80
G
General model s for nonconventi onal components
coal model for enthal py 3-163
densi ty pol ynomi al model 3-158
enthal py and densi ty model s l i st 3-158
heat capaci ty pol ynomi al model 3-159
Gi bbs energy of formati on esti mati on methods
aqueous speci es 8-22
sol i d 8-22
standard i deal gas 8-11
GRAYSON property method 2-11, 2-14
Grayson-Streed fugaci ty model 3-82
Group contri buti on acti vi ty coeffi ci ent model s 1-33
Dortmund-modi fi ed UNI FAC 2-45, 3-71
Lyngby-modi fi ed UNI FAC 2-45, 3-72
UNI FAC 2-45, 3-69
H
Haki m-Stei nberg-Sti el /DI PPR surface tensi on 3-155
Hayden-OConnel l
property methods 2-41
property model 3-9
HCOALGEN general coal model for enthal py 3-163
Heat capaci ty model s l i st 3-98
Heat of vapori zati on
esti mati on method at TB 8-12
esti mati on methods 8-15
model 3-85
Hel geson thermodynami c property model 3-117
Henrys constant sol ubi l i ty correl ati on model 3-103
Henrys Law
noncondensabl e components 2-8
HF equati on of state
ENRTL-HF property method 2-60, 2-61, 2-66
property methods usi ng 2-42
property model 3-13
Huron-Vi dal mi xi ng rul es 3-46
I
I APS model s for water
Rel ease 10
vi scosi ty 3-132
I deal gas heat capaci ty esti mati on methods 8-13
I deal gas l aw 1-22
property methods usi ng 2-39
property model 3-17
I deal gas/DI PPR heat capaci ty model 3-100
I deal l i qui d acti vi ty coeffi ci ent model 3-62
I DEAL property method 2-7
I GT densi ty model for
char 3-173
coal 3-171
I ntermedi ate properti es 4-3
J
Jones-Dol e el ectrol yte correcti on vi scosi ty model 3-
133
K
Kent-Ei senberg fugaci ty model 3-82
L
Lee-Kesl er Pl cker property model 3-19
Lee-Kesl er property model 3-18
Letsou-Sti el vi scosi ty model 3-135
Li mi xi ng rul e thermal conducti vi ty model 3-140
Li qui d acti vi ty coeffi ci ent property methods
l i st 2-37
Li qui d enthal py
methods 4-18, 4-19, 4-20
thermodynami c property model 3-111
Li qui d entrophy methods 4-27, 4-28
Li qui d fugaci ty coeffi ci ent methods 4-12, 4-13, 4-14,
4-15
Li qui d Gi bbs energy methods 4-23, 4-24
Li qui d heat capaci ty esti mati on methods 8-20
Li qui d mol ar vol ume
esti mati on methods (at TB) 8-12
Li qui d thermal conducti vi ty esti mati on methods 8-
18
Li qui d vi scosi ty esti mati on methods 8-17
Li qui d-l i qui d equi l i bri a
acti vi ty coeffi ci ent method 1-13
equati on-of-state method 1-6
Li qui d-l i qui d-vapor equi l i bri a
LK property method 7-3
LK-PLOCK property method 2-22
Lucas vapor vi scosi ty model 3-135
M
Major properti es 4-3
Mathi as al pha functi on 3-41
Mathi as-Copeman al pha functi on 3-37, 3-38, 3-43
Metal l urgi cal appl i cati ons
phase equi l i bri a 1-17, 2-67
MHV2 mi xi ng rul es 3-48
Model s
(physi cal properti es)
definition 4-39
Model s (physi cal properti es)
repl aci ng 4-53
Modi fi ed Rackett model for mol ar vol ume 3-96
Mol ar vol ume and densi ty model s l i st 3-86
Mol ar vol ume methods 4-29, 4-30
Mol ecul ar wei ght esti mati on method 8-3
N
Nernst-Hartl ey el ectrol yte di ffusi on model 3-151
Nonconventi onal components
enthal py cal cul ati ons 1-37
Nonconventi onal sol i d property model s 4-44
densi ty 3-158
enthal py 3-158
l i st of 3-158
Normal boi l i ng poi nt esti mati on methods 8-4
Nothnagel
property model 3-22
NRTL
property model 3-58
NRTL acti vi ty coeffi ci ent model 2-43
O
Onsager-Samaras el ectrol yte surface tensi on model
3-156
P
Parachor esti mati on method 8-13
PCES
PENG-ROB property method 2-15
Peng-Robi nson
al pha functi ons 3-36
Boston-Mathi as property model 3-25
MHV2 property model 3-26
property method 2-15
property model 3-34
Wong-Sandl er property model 3-26
Petrol eum components characteri zati on methods 7-1
Versi on 10
Petrol eum mi xtures
property methods for 2-10, 2-18
Petrol eum-tuned equati on-of-state property methods
2-15
Phase equi l i bri a and sol i ds
Phase equi l i bri um cal cul ati on 1-2
Physi cal properti es
cal cul ati on methods 4-9
major and subordi nate properti es 4-3
model s 3-3, 3-7, 4-39
overvi ew 4-3
routes 4-36
Pi tzer acti vi ty coeffi ci ent model 3-63, 5-7, 0-1
PI TZER property method 2-62
Pol ynomi al acti vi ty coeffi ci ent model 3-65
PR-BM property method 2-23
Predi cti ve property methods
equati on-of-state 2-26
Predi cti ve Soave-Redl i ch-Kwong-Gmehl i ng mi xi ng
rul es 3-49
Predi cti ve SRK property model (PSRK) 3-26
PRMHV2 property method 2-28
Property Constant Esti mati on System
Property methods
acti vi ty coeffi ci ent common model s 2-53
cl asses of 2-2
common model s for equati on-of-state 2-25
common model s for petrol eum mi xtures 2-18
creati ng 4-51, 4-55
defi ni ti on 2-2, 4-1
di sffusi on coeffi ci ent 1-36
equati on-of-state 2-15, 2-20
fl exi bl e and predi cti ve equati on-of-state 2-26
fl exi bl e and predi cti ve model s 2-36
for characteri zi ng petrol eum components 7-3
for el ectrol yte sol uti ons 2-54, 2-66
for K-val ue model s 2-11
for l i qui d fugaci ty 2-11
for petrol eum mi xtures 2-10
l i qui d acti vi ty coeffi ci ent 2-37
l i st 1-1
modi fyi ng 4-51
petrol eum-tuned equati on-of-state 2-15
thermodynami c 1-2
transport 1-34
vi scosi ty 1-35
Property model s
equati on-of-state l i st 3-7
l i st of 3-1
thermodynami c l i st 3-3
Property parameters
esti mati ng 8-1
PRWS property method 2-29
PSRK
property model 3-26
R
Rackett mi xture l i qui d vol ume model 3-95
Rackett/DI PPR pure component l i qui d vol ume model
3-93
Radi us of gyrati on esti mati on method 8-12
Redl i ch-Ki ster acti vi ty coeffi ci ent model 3-66
Redl i ch-Kwong
al pha functi on 3-40
equati on-of-state 2-17, 2-24, 2-26, 2-40, 2-59, 2-
62
property model 3-27
Redl i ch-Kwong-Aspen property model 3-28
Redl i ch-Kwong-Soave
al pha functi on equati ons 3-40
al pha functi on l i st 3-44
Boston-Mathi as property model 3-29
MHV2 property model 3-31
Wong-Sandl er property model 3-30
Redl i ch-Kwong-Soave property model 3-35
Ri edel el ectrol yte correcti on thermal conducti vi ty
model 3-141
Ri gorous three-phase cal cul ati ons
l i st of uni t operati on model s 6-1
RK-ASPEN property method 2-31
RKS-BM property method 2-24
RKSMHV2 property method 2-32
RK-SOAVE property method 2-17
RKSWS property method 2-33
Routes
confl i cti ng 4-54
creati ng 4-57
defi ni ti on 4-1, 4-36
modi fyi ng 4-57
repl aci ng 4-51
traci ng 4-50
S
Sato-Ri edel /DI PPR thermal conducti vi ty model 3-
142
Scatchard-Hi l debrand acti vi ty coeffi ci ent model 3-67
Rel ease 10
Schwartzentruber-Renon property model 3-31
Sol i d enthal py methods 4-21, 4-22
Sol i d enthal py of formati on of aqueous speci es
Sol i d entrophy methods 4-28, 4-29
Sol i d fugaci ty coeffi ci ent methods 4-16
Sol i d Gi bbs energy methods 4-25, 4-26
Sol i d heat capaci ty esti mati on methods 8-21
Sol i d standard enthal py of formati on esti mati on
methods 8-21
Sol i d standard Gi bbs free energy of formati on
Sol i ds acti vi ty coeffi ci ent method 1-16
Sol i ds pol ynomi al heat capaci ty model 3-102
SOLI DS property method 2-67
Sol i ds vol ume pol ynomi al model 3-97
Sol ubi l i ty correl ati on model s
l i st 3-102
Sol ubi l i ty parameter esti mati on method 8-12
Sol uti on chemi stry 5-2
SR-POLAR property method 2-34
Standard enthal py of formati on
Standard Gi bbs free energy of formati on
Standard l i qui d vol ume esti mati on method 8-12
Standard Peng-Robi nson property model 3-34
Standard Redl i ch-Kwong-Soave property model 3-35
Steam tabl es
ASME 2-71
l i st 2-71
NBS/NRC 3-21
property model s 3-8
STEAMNBS property method 2-72, 3-21
STEAM-TA property method 2-71
Sti el -Thodos pressure correcti on thermal
conducti vi ty model 3-145
Sti el -Thodos/DI PPR thermal conducti vi ty model 3-
143
Subordi nate properti es 4-3
Surface tensi on
model s l i st 3-154
Surface tensi on methods 4-36
T
Thermal conducti vi ty methods 4-33, 4-34, 4-35
Thermodynami c property
l i st of model s 4-41, 4-42, 4-43
Thermodynami c property
l i st of addi ti onal model s 3-105
methods 1-2
model s l i st 3-3
Three-suffi x Margul es acti vi ty coeffi ci ent model 3-68
Traci ng routes 4-50
Transport property
methods 1-34
Transport property model s 4-43, 4-44
TRAPP
thermal conducti vi ty model 3-145
vi scosi ty model 3-137
True component approach 5-3
U
UNI FAC
Dortmund modi fi ed acti vi ty coeffi ci ent model 3-
71
Lyngby modi fi ed acti vi ty coeffi ci ent model 3-72
R and Q parameters esti mati on method 8-26
UNI QUAC
R and Q parameters esti mati on method 8-13
Uni t operati on model s
ri gorous three-phase cal cul ati ons 6-1
V
Van Laar acti vi ty coeffi ci ent model 2-49, 3-75
Vapor enthal py methods 4-17
Vapor entrophy methods 4-26, 4-27
Vapor fugaci ty coeffi ci ent methods 4-11
Vapor Gi bbs energy methods 4-22, 4-23
Vapor phase associ ati on 1-26
Vapor pressure esti mati on methods 8-14
Vapor pressure model l i st 3-80
Vapor thermal conducti vi ty esti mati on methods 8-19
Vapor vi scosi ty esti mati on methods 8-18
Vapor-l i qui d equi l i bri a acti vi ty coeffi ci ent method 1-
11
Vapor-l i qui d equl i bri a equati on-of-state method 1-4
Vi ri al equati ons of state 1-25
Vi scosi ty
methods 4-31, 4-32
model s 3-121
Versi on 10
W
Wagner I nteracti on Parameter acti vi ty coeffi ci ent
model 3-77
Wagner vapor pressure model 3-80
Wassi l jewa-Mason-Saxena mi xi ng rul e for thermal
conducti vi ty 3-146
Water sol ubi l i ty model 3-104
Watson equati on for heat of vapori zati on 3-85
Wi l ke-Chang di ffusi on model
bi nary 3-152
mi xture 3-153
WI LS-GLR property method 3-112
WI LS-LR property method 3-112
Wi l son (l i qui d mol ar vol ume) acti vi ty coeffi ci ent
model 3-79
Wi l son acti vi ty coeffi ci ent model 2-51, 3-78
Wong-Sandl er mi xi ng rul es 3-51
Z
Zemai ti s equati on 5-8

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Physical Property

Methods and Models

, Aspen Custom Model er

, the Pl antel l i gence l ogo

, and the aspen l eaf l ogo

are ei ther regi stered

are trademarks of Koch Engi neeri ng Company, I nc.

i s a trademark of Rai nbow Technol ogi es, I nc.

1-12 Physi cal Property Methods and Model s

= The i nfi ni te di l uti on acti vi ty coeffi ci ent of component i i n the

Mixing Rule Predictive

PRMHV2 Peng-Robinson MHV2 X

An X indicates volume shift is included in the property method.

An X indicates that the property method is predictive.

An X indicates the parameters were obtained from the literature.

An X indicates the parameters were obtained from the literature.

An X indicates the parameters were obtained from the literature.

Vapor Phase EOS Name Poynting

An X indicates the parameters were obtained from the literature.

An X indicates the parameters were obtained from the literature.

Solv., Mol.sol.: (TC, PC, OMEGA) or SIGDIP

Solv., Mol.sol.: MULAND or MULDIP Ion:

Solv., Mol.sol.: (MW, TC, TB) or KLDIP Ion:

Solv., Mol.sol.: MW, VB Ion: CHARGE,

Onl y for ri gorous el ectrol yte property methods

ASME Steam Tables ESH2O0, ESH2O V L X

An X indicates applicable to Pure or Mixture

Redlich-Kwong-Soave-MHV2 ESRKSV20, ESRKSV2 V L X X

Bromley-Pitzer (Chien-Null) GMPT2 L X

An X indicates applicable to Pure or Mixture

Wagner interaction parameter GMWIP S X

Watson / DIPPR DHVLWTSN L X

API Liquid Volume VL2API L X

V =Vapor; L =Liquid; S =Solid

An X indicates applicable to Pure or Mixture

Aqueous Infinite Dilution

Henrys constant HENRY1 L X

Cavett Liquid Enthalpy Departure DHL0CVT, DHL2CVT L X X

An X indicates applicable to Pure or Mixture

Physi cal Property Methods and Model s 3-9

3-18 Physi cal Property Methods and Model s

I n the above equati on both Z

Physi cal Property Methods and Model s 3-19

i s cal cul ated from the equati on-of-

3-32 Physi cal Property Methods and Model s

For polar components (dipole moment >>0), if you do not enter q

For polar components (dipole moment >>0), if you do not enter q

I f you do not enter at least one of the binary parameters k

Absolute temperature units are assumed.

The excess Hel mhol tz energy i s al most i ndependent of pressure. I t can be

Physi cal Property Methods and Model s 3-57

The bi nary parameters CHNULL/1, CHNULL/2, and CHNULL/3 can be

Ionic Born Radius Unary Parameters

I f an electrolyte-molecule parameter is missing, the following defaults are used:

I f an electrolyte-molecule parameter is missing, the following defaults are used:

Absolute temperature units are assumed.

, and . These parameters fol l ow the

The Scatchard-Hi l debrand model does not requi re bi nary parameters.

Absolute temperature units are assumed.

Absolute temperature units are assumed.

Absolute temperature units are assumed.

Absolute temperature units are assumed.

Parameter Name/ElementSymbol Default MDS Lower Limit Upper Limit Units

four el ectrol ytes are found: CaCl