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Full Manual HSC Chemistry 5 PDF
Full Manual HSC Chemistry 5 PDF
ChemicalReactionandEquilibriumSoftware
withExtensiveThermochemicalDatabase
ABSTRACT
HSC Chemistry is designed for various kinds of chemical reactions and equilibria
calculations. The current version contains fourteen calculation modules displayed as
fourteenoptionsintheHSCmainmenu:
1. ReactionEquations 8. H,S,CandGDiagrams
2. HeatandMaterialBalances 9. PhaseStabilityDiagrams
3. HeatLossCalculations 10. MineralogyIterations
4. EquilibriumCompositions 11. CompositionConversions
5. ElectrochemicalEquilibria 12. Elements
6. FormulaWeights 13. Water(SteamTables)
7. Eh pHDiagrams 14. Units
The name of the program is based on the feature that all fourteen calculation options
automaticallyutilizethesameextensive thermochemicaldatabasewhichcontainsenthalpy
(H), entropy (S) and heat capacity (C) data for more than 17000 chemical compounds.
Thisdatabaseisequivalenttomorethanseventeenthickdatabooks.
TheobjectiveofHSCistomakeconventionalthermodynamiccalculationsfastandeasyto
carry out using personal computers. Therefore HSC has a wide range of application
possibilitiesinscientificeducation,industryandresearch.Thermochemicalcalculationsare
useful,forexample,whendevelopingnewchemicalprocessesandimprovingoldones.
HSCChemistryisalsoausefultoolforuniversitiesandschoolsinchemicalpracticalsand
studies.
HSC Chemistry offers powerful calculation methods for studying the effects of different
variables on the chemical system at equilibrium. For example, if the user gives the raw
materials,amountsandotherconditions ofalmostanychemicalprocess,theprogramwill
give the amounts of the product as a result. HSC also makes heat and material balance
calculationsofdifferentprocessesmuchmoreeasilythananymanualmethod.TheEhpH
diagrams option of HSC also offers a very fast way of studying the dissolution and
corrosionbehaviorofdifferentmaterials.
Ofcourse,HSCdoesnotsolveallchemicalproblems,becauseitdoesnottakeintoaccount
the kinetics (rates) of the chemical reactions and nonideality of solutions. However, in
manycasesitisaveryinexpensiveandusefultoolwhichhelpstofindtheoptimumreaction
conditions and yields for experimental investigations without expensive trialanderror
chemistry.
CONTENTS
ABSTRACT
1. COPYRIGHTNOTICEANDWARRANTY 11
2. TECHNICALSUPPORT 21
3. ERRORSANDBUGS 31
4. LICENSEAGREEMENTFORENDUSEROFHSCCHEMISTRY 41
4.1 TheLicence 41
4.2 UseofHSCChemistryModulesandDatabasesSeparately 41
4.3 Copyright 41
4.4 Copying 42
4.5 TransferoftheLicense 42
4.6 Warranty 42
4.7 Liability 42
4.8 Registration 43
4.9 TechnicalSupport 43
4.10 ApplicableLawandArbitration 43
4.11 Millenium(Y2K)Compliance 43
5. REGISTRATIONCARD 51
6. WHAT'SNEWINHSCCHEMISTRY5.0 61
6.1 Updatedheatandmassbalancemodule 61
6.2 NewHSCAddInfuntionsforExcel2000 62
6.3 NewDrawingToolbar 63
6.4 NewDiagramOptions 64
6.5 LargerDatabasewithnewOptions 66
6.6 ImprovedEquilibriumModule 67
6.7 NewHeatLossModule 610
6.8 NewSteamCalculatorModule 614
6.9 NewHelpRoutine 616
6.10 OtherImprovements 616
6.11 NewWindowsMe,2000andXPCompatibility 617
6.12 WhatsNewinHSCChemistry4.0 618
7. INSTALLATIONTOHARDDISK 71
7.1 SystemRequirements 71
7.2 Installation 71
7.3 ImportantNotes 71
7.4 InstallationandOperationProblems 73
7.5 RemovingHSCfromComputer(Uninstallation) 73
8. INTRODUCTION 81
8.1 InvitationtonewAuthors 82
8.2 PhysicalBackgroundofH,S,CandG 83
9. OPERATINGINSTRUCTIONS 91
9.1 StartingHSC 91
9.2 MainMenuofHSC 91
9.3 PrinterSettings 93
9.4 UsingtheHelpButton 94
10. REACTIONEQUATIONS 101
10.1 OneChemicalSubstance 101
10.2 OneChemicalSubstanceResults 104
10.3 ReactionEquations 105
10.4 ReactionEquationsResults 1012
11. HEATANDMASSBALANCE 111
11.1 BasicCalculationProcedure 112
11.2 FormattingtheWorksheet 115
11.3 SpecificationofSubstanceGroups(Streams) 115
11.4 FormulaeintheCells 118
11.5 ElementalCompositions 1110
11.6 AdditionalSheets 1112
11.7 TargetDialog 1113
11.8 Graphics 1115
11.9 Multiplebalanceareas 1118
11.10 GeneralConsiderations 1124
11.11 HeatBalanceExamples 1126
12. HEATLOSS 121
12.1 BasicCalculationProcedure 122
12.2 HeatLossExamples 125
12.2.1 ExamplesprovidedbyHSC 125
12.2.2 SimpleStepbystepExample(creatingsmeltingl.HTR) 128
12.3 DetailedDescriptionoftheProgram 1211
12.3.1 UsingtheFixValueButtonandthelogicbehingit 1211
12.3.2 MainWindow 1212
12.3.3 ConductionDatabase 1214
12.3.4 ConvectionDatabase,Tablesheet 1216
12.3.5 ConvectionDatabase,Functionsheet 1217
12.3.6 SurfaceRadiationDatabase 1218
12.3.7 GasMixtureRadiationCalculator 1219
12.3.8 PracticleRadiationCalculator 1220
12.3.9 TargetCalculations(TargetDialog) 1221
12.3.10 Userspecifieddiagrams(DiagramDialog) 1222
12.3.11 Limitations 1224
12.4 BasicTheorybehindHeatTransfer 1226
12.4.1 Conduction 1225
12.4.2 Convection 1230
12.4.3 Radiation 1239
13. EQUILIBRIUMMODULE 131
13.1 StartingfromdefiningtheElements 133
13.2 GivingInputDataforEquilibriumCalculations 136
13.3 AqueousEquilibria 1314
13.4 GeneralConsiderations 1316
13.5 Limitations 1319
13.6 CalculationRoutines 1320
13.6.1 GIBBSEquilibriumSolver 1320
13.6.2 SOLGASMIXEquilibriumSolver 1321
13.7 DrawingEquilibriumDiagrams 1323
13.7.1 SelectingDataTypefortheXandYaxis 1326
13.7.2 ResultGraphics(EquilibriumDiagram) 1327
13.7.3 EquilibriumDiagramTable 1331
13.8 Nonidealmixture:GaAsExamplewithActivityformulae 1332
13.9 CaCO3Example(Aqueoussolutionexists) 1334
13.10 VaporPressures 1338
14. HSCEQUILIBRIUMMODULESAMPLES 141
15. CELLEQUILIBRIA 151
15.1 CellModule 153
16. FORMULAWEIGHTS 161
17. EhpHDIAGRAMS(Pourbaixdiagrams) 171
17.1 Introduction 171
17.2 ChemicalSystemSpecifications 174
17.3 EhpH DiagramMenu 176
17.4 NormalEhpHDiagrams 179
17.5 SpecificationsforCombinedDiagrams 1714
17.6 CombinedEhpHDiagrams 1718
17.7 CalculationResultsofCombinedDiagrams 1721
17.8 EhpH DiagramsinPractice 1721
18. EppHSamples 181
19. H,S,CANDGDIAGRAMS 191
20. DIAGRAMGRAPHICS 201
20.1 GraphicalObjects 201
20.2 FormattingtheDiagram 205
20.3 EditingandCombiningDiagrams 2011
21. PHASESTABILITYDIAGRAM 211
21.1 TppDiagramModule 212
21.2 TppDiagrams 214
21.3 LppDiagramModule 215
21.4 LppDiagramMenu 217
21.5 LppModuleDiagram 218
22. MINERALOGYITERATIONS 221
23. COMPOSITIONCONVERSIONS 231
24. ELEMENTSMODULE 241
25. WATER 251
25.1 BasicCalculationProcedure 252
25.2 Calculationexamples 255
25.2.1 Icemeltingathighpressure 255
25.2.2 Evaporationprocessinaheatrecoveryboiler 257
25.2.3 Steamturbineprocess 258
25.3 DetailedDescription 259
25.3.1 Pressurecorrectioninthedatabase 259
25.3.2 Basictheory 2512
25.4 Limitations 2513
26. UNITSMODULE 261
27. EXCELADDINFUNCTIONS 271
27.1 Gettingstarted 271
27.2 OpeningandmovingfilesthatuseHSC5.0functions 271
27.3 Briefdescriptionofthefunctions 273
27.4 MoreaboutregisteringDLLfiles 276
27.5 UnactivationofExcelAddInFunctions 276
28. HSCDATABASES 281
28.1 DatabaseMenu 281
28.2 NotationsandAbbreviationsusedintheDatabase 282
28.2.1 HSCFormulaSyntax 284
28.3 ReferenceStates 287
28.4 AqueousIons 287
28.5 SearchOption 289
28.6 FindingSpecieswiththesameStoichiometry 2811
28.7 ListingSpeciesNames 2813
28.8 ListingSpeciesFormulae 2814
28.9 ListingSpeciesDataintheOwnandMainDatabase 2816
28.10 EditingDatainOwnandMainDatabase 2818
28.11 SavingDatainOwnDatabase 2820
28.12 FittingCpData 2826
28.13 ConvertingCpFunctions 2827
28.14 ConvertingThermochemicalDatatoH,SandCpformat. 2829
28.15 ConvertDatabaseFileFormat 2831
28.16 ConvertingoldHSC2.0DatabasestoHSC4.0Format 2834
28.17 SelectingActiveDatabases 2835
28.18 ColorCodes 2836
29. HSCFORMULASYNTAXFORHYDROCARBONSPECIES 291
29.1 Basichydrocarbons,CxHy 291
29.1.1 Appendagegroups 292
29.1.2 Aromaticcompounds 292
29.2 Halogencompounds 292
29.3 Hydrocarbonscontainingnitrogen 293
29.3.1 Amines,RNH3,R1NHR2,R1,R2NR3 293
29.3.2 Aminoacids 293
29.3.3 Hydrazines,RNHNH3 293
29.3.4 Amines,RC=0NH2 294
29.3.5 Nitriles,R=N 294
29.3.6 Nitrocompounds,nittrates,RNO2 294
29.4 Hydrocarbonscontainingoxygen 294
29.4.1 Ethers,R1OR2 294
29.4.2 Aldehydes,RC=0H 295
29.4.3 Ketones,R1C=OR2 295
29.4.4 Esters 295
29.4.5 Alcoholsandcarbohydrates 295
29.4.6 Phenols 296
29.4.7 Acids 296
29.5 Hydrocarbonscontainigsulfide 297
29.5.1 Thiols,RSH 297
29.5.2 Sulfides,thiacompounds,R1SR2 297
29.5.3 Disulfides,dithiacompounds,R1SSR2 297
29.5.4 Sulfoxides 297
29.5.5 Sulfones 297
29.6 Reference 297
30. ACKNOWLEDGMENTS 301
31. THERMOCHEMICALDATASOURCES 311
32. REFERENCES 321
33. DATAREFERENCES 331
34. SPECIES 341
35. HSCDLLTOOLS 351
35.1 GettingStarted 351
35.2 ExampleFiles 351
35.3 DescriptionofavailableSubroutines 354
HSCChemistry5.0 61
6. WHAT'SNEWINHSCCHEMISTRY5.0
ThenewHSCversion5containsseveralnewcalculationroutines,newpropertiesanda
largerdatabasewithupdateddata.ThefamiliarHSCstyleuserinterfaceandfileformats
have been maintained in order to minimize the training requirements for current HSC
users.Thenewfeaturescanbesummarizedasfollows:
6.1 UpdatedHeatandMassBalanceModule
HSCversion4calculatedonlyonebalanceareaatatime.WiththenewHSC5
upto127balancesmaybecalculatedsimultaneously.
Balanceareasmaybeconnectedwitheachotherusingcellreferencesorbuiltin
elementamountfunctions.
Temperaturesmaybeusedasvariables.
TargetroutineisalsoavailableinDiagramoption.
Newstreamelementalcompositioncalculator.
Graphicalobjectsmaybeaddedtosheets.
LinktothenewSteamenthalpycalculator(0.01 1000bar).
LinktothenewHeatLossroutine.
Manysmallimprovementssuchasiterationroutinefixes.
HSCChemistry5.0 62
6.2 NewHSCAddInFunctionsforExcel2000
HSC Excel AddIn makes native HSC functions and databases available directly
withina normalExcelspreadsheet.Highlyspecializedapplications maybecreated
withthesenewExcelAddInfunctions.
These functions work like normal Excel functions such as the SUM function. For
example, H("FeO"500) function returns the enthalpy of FeO at 500 Kelvin. An
otherexampleisWTP("Na""Na2SO4")functionwhichreturnstheweightpercent
ofsodiuminsodiumsulphate.
Upto45different HSCfunctions areavailable inExcel whichautomaticallyreads
theHSCdatabase.
HSCChemistry5.0 63
6.3 NewDrawingToolbar
The new Drawing Toolbar may be used to draw basic graphical objects (lines,
arrows, rectangles, ellipses) in HSC diagrams. These shapes may be used, for
example,to illustrate experimental conditions. Versatileformatting options maybe
usedtoeditlinesoraddfillcolour,linewidthsandstyles.
Drawing Objects may be created and edited with the mouse or using the Object
Editor, which enables very exact editing with numerical values. Drawing Objects
maybefixedsothattheycanbeusedinalldiagramsortheymaybesavedforlater
useinfiles.
HSCChemistry5.0 64
6.4 NewDiagramOptions
HSC4wasabletosavediagramsusingonlyoneWMFformat.Nowmorethan
30fileformatsareavailable,suchasJPG,BMP,etc.
DiagramsmayalsobeeditedusingthenewHSCImageEditor.
Several diagrams may be combined with the new HSC Image Combiner if the
sameXandYscaleshavebeenused.
There is a new Diagram Grid format option as well as some new formatting
optionsfordiagramcurves.
HSCChemistry5.0 65
6.5 LargerDatabasewithnewOptions
The number of species in the database has been increased from 15000 to more
than17000.The qualityofthe databasehas beenimprovedandthetemperature
ranges of the available data have also been expanded more than 5000 changes
havebeenmade.
Newwaterdataatpressuresfrom0.01 1000bararenowavailable.
Limitationof2000specieshasbeenremovedfromtheSearchroutine.
NewSearchmodehasbeenadded(Allelementsmustexist).
NewfastTableandDiagramroutineshavebeenaddedtoDatabaseEditor.
Severalothersmallimprovementshavealsobeenmade.
HSCChemistry5.0 66
6.6 ImprovedEquilibriumModule
Calculationreliabilityhasbeenimprovedinmanyofthetestcases.
Newdatabasesearchoptionswithoutthelimitof2000species.
NewSpeciesNamedisplayaddedtothedatabasesearchroutine.
NewWarningsroutinefortemperaturerangeextrapolation.
Smallfixese.g.speciesnamelengthincreasedfrom20to24characters.
HSCChemistry5.0 67
6.7 NewHeatLossModule
ThenewHeatLoss modulemaybeused,forexample,toestimateheat lossvalues
needed in the Balance module. The user must first specify the wall layers, layer
materials and thickness of these layers. Two basic types of calculations may be
carriedout:
1 Temperatureprofilewithfixedheatlossandonetemperaturepoint.
2 HeatLosswithtwofixedtemperaturepointswillreturntheheatlossbutalsothe
temperatureprofile.
The calculation routine handles conduction, convection and radiation properties as
functions oftemperature,but fixed values mayalsobeusedbyselectingthe value
and pressing the Fix Value button. These fixed values are shown in red on the
calculationsheet.
Temperature profile as well as some other user specified values may also be
presented in graphical form. The Target Dialog may be used to find, for example,
minimum layer thickness. The calculation specifications may be saved to files for
lateruse.
HSCChemistry5.0 69
TheHeatLossmoduleisintegrated withthreedatabasesandtwocalculators:
Conductiondatabasewith718substances
Convectiondatabasewith111substancesand4functions
Radiationdatabasewith61surfacematerials
GasRadiationCalculatorwithH2O,CO2,CO,NO,SO2andCH4data
ParticleRadiationCalculator.
Theusermayeditoraddnewdatatothesedatabases.
HSCChemistry5.0 610
6.8 NewSteamCalculatorModule
ThenewSteamCalculatormoduleoffersamuchmoreconvenient waytoestimate
enthalpies,entropiesanddensitiesofsteam,waterandicethanthetraditionalSteam
Tables and Mollier Diagrams within 4 2273 K and 0.01 1000 bar. Steam
enthalpies may be needed, for example, when calculating the heat and material
balancesofboilersorturbines.
HSCChemistry5.0 612
6.9 NewHelpRoutine
The new Help routine contains all the information, graphics and formulae of the
HSCprintedmanualwithconvenientsearch,print,editandsaveoptions.
6.10 OtherImprovements
ThenewfolderstructuredividesHSCfilesintologicalgroups.
HSCtablesnowalsohaveExcel97and2000filesupport.
The lengthof formulas has been increasedfrom20to 24characters intheEpH
module.
Formresizepropertieshavebeenimproved.
Manysmallbugfixesandcosmeticadjustmentsetc.
6.11 NewWindowsMe,2000andXPCompatibility
Newinstallationroutine.
Newcompilerandprogrammingtoolversionsused.
HSCChemistry5.0 614
HSC5.0iscompatiblewithWindows95,98,NT,Me,2000andXP.
HSCChemistry5.0 615
6.12 What'sNewinHSC5.1vs.5.0
1. Databasefixes:
HSCnowfindsalltheFandZrcontainingspecies.
Database Editor bug which sometimes created empty records to Own
Databasehasbeenfixed.
Al(NO3)3(a)>Al(NO3)3(ia)
AlF(+2a),AlF2(+a),AlF3(a)added
AmSO4(a)>Am(SO4)2(a)(TypoinHSCdatabase)
BF4NaS34.728replacedwithNaBF4S34.728cal/mol*K
(Co(NH3)5H2O)Cl3>Co(NH3)5*H2O*Cl3(Duplicate)
CrS1.333H37.3 >37.3kcal/mol(TypoinHSCdatabase,Mills74)
Cr2NiO4replacedwithNiO*Cr2O3(duplicate)
FeCr2O4replacedwithCr2FeO4(duplicate)
HFe2O(a)removed(TypoinSlop98:HFe2O(a)>HFeO2(a)
H2OCpconstantwhenT>600K
HO(g):typoinHandSvaluesfixed
HOI(g)>HIO:ReliabilityClass1>5(GasinPankratz95?).Compareto
HIO(g)(Cor90,Landolt01)
I(3a)>I3(a)(Typo inHSCdatabase,Fabricius94)
K3AlCl9>K3Al2Cl9(TypoinKarapet70)
K3Al2F6>K3AlF6(TypoinKarapet70)
MoF2toostable:ReliabilityClass2>5(Ruzinov75)
MoO2(+2a),CH3COO(a),CH3COOHadded
Na2Omeltingpoint1405K>1405K
NaAlO2replacedwithNa2O*Al2O3(duplicate)
Np(+4a)dataNAGRA91>Phillips88
Np(OH)3(+a)H313.983> 313.983kcal/mol(TypoinHSCdatabase)
Np(H2PO4)(+a)>Np(H2PO4)2(+a)(TypoinHSCdatabase)
PbSO4*PbOwasremoved(EnthalpyvaluetypoinBard85)
(Pt(NH3)4)Cl2>Pt(NH3)4Cl2
(Pt(NH3)4)I2>Pt(NH3)4I2
Pu(+4a)dataNAGRA91>Phillips88
PuO2(SO4)(2a)>PuO2(SO4)2(2a)(TypoinHSCdatabase)
SCN(a)replacedwithCNS(a)(duplicate)
SrZr(Si2O7)wasrenamedSrZrSi2O7(Huntelaar95)
UO2(G)>UO3(G):(TypoinHSCdatabase,Phillips88)
UO2.25replacedwithU4O9(duplicate)
U3O5deleted:(TypoinSamsonov78,dataseemstobeforU3O8)
ZrF2toostable:ReliabilityClass1 >3(Barin77,Glushko94,Landolt00)
Someaqueous(a)specieswaschangedto(ia).
Somenewspecies
Smallfixin"Allmustexist"optioninFindElementsdialog.
2. Tpp Modulefixes:
ScaleandPrintDialogbugfixed.
DiagramAreaColorDialogbugfixed.
PrintandLabeldialogswithH,SandCpdiagrams.
3. Watermodule:
Fixed:SmallchangesinPoint1didnotalwayseffectthePhaseoption.
Moredensityvaluesathigherpressuresandtemperatures.
HSCChemistry5.0 616
4. EquilibriumModule:
Speciesselectiondialog:Sortmodebug fixed.
AutomaticadditionofN2(g).
WarningofSGMlimitations.
Gibbsroutine fix: Diagram button may be pressed before the calculations
arereadywithoutcrashingapplication.
Picroutine improvement: Enter key moves forvard after X and Yaxis
speciesselection.
GibbsandSGMroutines:Problemwithphasetransitiondatabelow298.15
Kfixed.
5. New "Key Word Find" Option in Database Menu finds, for example, all the
specieswhichcontaintheKeyWord"benzene".
6. "KeyWordFind"mayalsobe usedfromDatabasePeeproutine.
7. CleareroptioncaptionsinDatabaseMenu
8. Morewarningdialogs.
PeepDatabasedialog:Warningofhighnumberofprintpages
ElementFindDialog:MoreToolTipText
Lppmodule:Improved"TriplePointOutside Range"warning.
9. SeveralsmallfixesinHelpandManualfiles.
10. Maximum number of records in HSC databases was increased from 32767 to
2147483647records.
11. "HSCDLLTools"opens nativeHSCfunctionsanddatabaseforuseinVisual
Basicapplicationsandotherprogrammingenvironments.
12. "WNDTLS32.DLLcouldnotbefound"errormessagebuginHSCHelproutine
wasfixed.
13. HeatandMaterialBalanceModule:
Streamtemperaturelinkrefreshbugwasfixed.
"CalculateRecalc"optionclearsalso columns0S.
ArrowGraphicalObjectadded.
New"IdealGasDensity"option.
14. Some other small fixes. For example, HSC main menu flicker n some
computerswasfixed.
ManythanksforthefeedbackreportstoallactiveHSCusers.
HSCChemistry5.0 617
The new HSC version 4.0 contains several new calculation modules, new properties
andalargerdatabasewithalot ofupdateddata.ThefamiliarHSCstyleuserinterface
hasbeenmaintainedinordertominimizethetrainingrequirementsofcurrentHSCusers.
Thenewfeaturescanbesummarizedasfollows:
Installation
The HSC 4.0 installation routine has been updated and is now compatible with
Windows 95,98andNT.However,systemrequirementsarestillquitereasonable.
HeatandMaterialBalances
Severalnewfeatureshavebeen addedtotheHeatandMaterialBalancemodule:
1. The new Target calculation feature can be used to iterate sequential variable
valuesinordertoreachcertaintargetvalues.Forexample,theusercansetthezero
heat balance as a target and find out the feed amount which satisfies the given
targetcondition.
2. The graphics feature enables the user to draw diagrams of heat balance
calculationsheets.Theusermayeasilyselectonevariableandrangeforthexaxis
and several others whose values are drawn on the diagram as a function of x
variablechange.
3. The user can easily import additional MS Excel sheets to the module. These
sheetscanbeusedtocalculateinputdatafortheINPUTsheetorprocessresultsof
the OUTPUTsheet. Files can be saved in Excel format for further treatment of
results.
4. Several small improvements and new properties. For example, the user can now
resizetheformswithoutstepvalues.Theprintingcapabilitieshavebeenimproved,
forexample,thefinaltemperaturecalculationresultscanalsobeprintednow.
HSCChemistry5.0 618
EquilibriumCalculations
FormulaWeights
Thenewfeatureoftheformulaweightcalculatorallowstheusertospecifytheamountof
thespeciesin kilograms or moles.This enables the moduletocalculatetheamountsof
elementsinadditiontothecompositionsandformulaweights.
TppPhaseStabilityDiagrams
Thisnewmoduleallowsyoutodrawphasestabilitydiagramswithtemperatureasthex
axisandaselectedpartialpressureastheyaxis.Diagramswithpartialpressuresonboth
axes can also be drawn. Partial pressures of sulfur, oxygen, sulfur dioxide, carbon
monoxide,etc.canbeuseddependingontheselectedsystem.
Thesediagramscanbeused,forexample,toestimatewhatkindsofphasesprevailinthe
roastingfurnace in different conditions orto evaluatewhich condensedsubstances may
becomestablewhentheprocessgastemperaturedecreases.
Eh pHDiagrams
EhpHdiagrams are used to estimate the prevailing species in aqueous solutions as a
functionofpHandchemicalpotential.Acompletelynewoptionhasbeenaddedtothis
module.Thenewfeaturescanbesummarizedinthefollowinglist:
1. The new routine can be used to combine several diagrams with different
concentrations, temperatures or main elements into a single diagram. The
traditional concentration diagrams are widely used, but more special temperature
andmainelementdiagramsmayalsogivevaluableinformation.
2. The possibility to change the size of printed diagrams is also very useful when
there areseveralsmallstabilityareasinthesamediagram.
3. The selection of different electrode potential scales is also a useful new feature,
whereHydrogen,CalomelandAg/AgClscalescanbeused.
4. Improvedcalculationreliability.
HSCChemistry5.0 619
5. The calculation system specification can easily be modified with the user's own
Gibbsenergydata.Thesemodificationscanbesavedforlateruse.
H,S,CandGDiagrams
Thenewdiagrammodulecanbeusedtodrawseveraldifferenttypesofthermochemical
diagrams. The same new versatile graphics and printing features are included as in the
othermodules.Themainfeaturescanbesummarizedasfollows:
1. Eightdifferentdiagramtypescanbedrawnasafunctionoftemperature:
HEnthalpy(total)
HEnthalpy(latent)
SEntropy
CpHeatCapacity
GGibbsEnergy
DH
DS
DG(Ellinghamdiagrams)
MineralogyModule
Composition conversions between substance (mineralogy) and elemental analyses are
often needed in chemical R&D work. The new Mineralogy module easily converts
mineralogicalcompositionsintoelementalcompositions.
Theconversionoftheelementalcompositionofasubstanceintoamineralogicaloneisa
moredifficulttask,forexample,duetosmallanalyticalerrors.This moduleoffersthree
toolsforconvertingelementalanalyzesintomineralogicalones:
1. TheSolvemethod,whichusesmatrixalgebratosolvethemineralogy.Itisuseful
ifthegivenamountsofelementsfitthegivensubstancesexactly.
2. The Automatic iterative method, which fits the given elements to the given
substances by changing the species contents to achieve the given elemental
compositions.
3. The Manual iterative method, which may be needed especially if the same
elementexistsinseveralspecies.
ElementsModule
The thermochemical behavior of species is based on the properties of elements. The
locationoftheelementintheperiodicsystemtellsusalotaboutitschemicalnature.The
newElementsModule offers afast wayto comparethebasicproperties of elements in
tabularandgraphicalformat.
HSCChemistry5.0 620
UnitsModule
Traditionally, several types of energy, temperature, mass and volume units have been
used in thermochemical calculations. Therefore, some inconvenient conversions are
neededtocomparetheresultsfromdifferentsources.ThenewUnitsConversionmodule
is an easytoolforfastunit conversions inthermochemicalas wellas otherengineering
fields.Thespecificationsofthismodulecanbesummarizedasfollows:
1. Some90 different quantitiesand444unitsareavailable.Theusercan easilyadd
his/herownunitsandcoefficientsintotheconversioncalculatordatabase.
2. The Units Module also offers data sheets for chemical constants, particle mesh
sizes, air humidity and water pressure tables. The user can modify these tables
accordingtopersonalrequirements.
Database
Generalimprovements
The graphics,printingandformat properties as wellas resizingcapabilities ofthetable
forms havebeenimprovedinmostcalculationmodules.This makes iteasiertoproduce
highqualityhardcopiesoftheresults.
HSCChemistry5.0 621
8. INTRODUCTION
HSC Chemistry is designed for many different kinds of chemical reactions and
equilibriumcalculations.Thecurrentversioncontains14calculationoptions:
1. ReactionEquations
2. HeatandMaterialBalances
3. HeatLossCalculations
4. EquilibriumCompositions
5. ElectrochemicalCellEquilibria
6. FormulaWeights
7. PhaseStabilityDiagrams(TppandLppversions)
8. Eh pHDiagramswithconcentrationandtemperaturevariables
9. Enthalpy,entropy,heatcapacity,GibbsenergyandEllinghamdiagrams.
10. MineralogyIterations
11. Compositionconversions
12. WaterSteamTablesandMollierDiagrams
13. UnitsConversions
14. PropertiesofElementsintabularandgraphicalformat.
The name of the program is based on the fact that all fourteen calculation options
automatically utilize the same extensive thermochemical database which contains
enthalpy (H), entropy (S) and heat capacity (Cp) data for more than 17000 chemical
compounds.Thisdatabaseisequivalenttomorethanseventeenthickdatabooks.
The HSC Chemistry software enables the user to simulate chemical reactions and
processes on the thermochemical basis. This method does not take into account all the
necessaryfactors,suchasratesofreactions,heatandmasstransferissues,etc.However,
in many cases a pure thermochemical approach may easily give useful and versatile
informationfordevelopingnewchemicalprocessesandimprovingtheoldones.
Perfect simulation for all processes means that any chemical process can be designed
completelyinthecomputerwithoutanyexperimentalwork.Thisgoalis,however,farin
the future, because there is no complete general theory or basic data available which
would successfully combine thermodynamics, nonideality of solutions as well as
dynamics (kinetics) for all processes. Nearly perfect simulation may be achieved for a
single individual process step by measuring experimentally all the necessary parameters
for solution models, kinetic models, as well as for flow and heat transfer models.
However, this needs several months or years work to be able to simulate one single
processstep.Quiteoftenafastmainframecomputerisneeded.
Inthethermodynamicequilibriumtheratesofreactionsandreversereactionsmaybothbe
interpreted to have the same rate, ie. this state is only one special case of kinetic
phenomena.Ofcourse,someprogramsareavailablewhichalsotakesomekineticaspects
intoaccount.However,theseare not generallikethermodynamic equilibriumcodes are,
ie.theyareusuallyvalidonlyforcertaingeometriesandenvironments.
8.1 InvitationtonewAuthors
Ifyouhaveathermochemicalcomputerprogramorbasicthermodynamicdatawhichmay
beofmoregeneralinterest,pleasesendittotheauthor:
AnttiRoine
OutokumpuResearchOy
P.O.Box60
FIN28101PORI,FINLAND
Fax:+358 2 626 5310
WemayalsoaddyourcodetofutureversionsofHSCChemistry.ConnectiontotheHSC
database and fitting the code and user interface to HSC format can be carried out in
OutokumpuResearch.IntegrationiseasiestiftheoriginalcodeiswritteninVisualBasic,
QuickBASICorBASIC.
The new thermodynamic data which is saved in OwnDB5.HSC database can easily be
transferredtoMainDB5.HSCatOutokumpuResearch.
HSCChemistry5.0 83
8.2 PhysicalBackgroundofH,S,CandG
Cp = (dH/dT)P,n [1]
Equation(1)allowsthecalculationofenthalpyas
T
H(T) = Hf(298.15)+ CpdT+ SHtr [2]
298.15
where Hf(298.15) is the enthalpy of formation at 298.15 K and Htr is the enthalpy of
transformation of the substance. Calorimetric measurements at different temperatures
yieldtheenthalpycurveofzincshowninFig.2.
The enthalpy scale in Eq. 2 is fixed by definingH = 0 for the elements in their most
stable state at 25 C and 1 bar, mainly because this is convenient for calculations at
elevated temperatures. This is called the reference state. (Another fix point could have
beenH=0at0K,becausethethermalmotionofatomsandelectronsstopscompletelyat
thistemperature.)
Theabilityofachemicalsubstancetoabsorboremitheatdependsonthetemperature,and
thereforethecurveinFig.2isnotlinear.Inaddition,atphasetransformationtemperatures
the curve is discontinuous, because heat is needed for the phase transformations (ie. for
crystalstructurechanges,aswellasformeltingandboiling).
The enthalpy of compounds also contains their enthalpy of formation DHf from
elements. This is usually measured calorimetrically by letting pure constituent elements
react and form the compound at 298.15 K and 1 bar. The enthalpy of the compound is
therefore calculated by adding the enthalpy of formation to the experimental enthalpy
differenceH(T)H(298),seethesolidlineinFig.3.
Theenthalpyvaluesofgaseouszinccanbeextrapolatedtolowertemperaturesasshown
inFig.2bythedottedline.Thereferencestateforzincat25 Cand1barishexagonal
crystal.Theenthalpyofgaseouszincis130.415kJ/mollargercomparedtosolidpurezinc
at298.15K.Thisamountofheatisneededtoevaporateonemoleofzincat25 Cand1
bar,andiscalledtheenthalpyofformationofzincgasfromsolidzinc.
HSCChemistry5.0 84
120
100
115.311
80
130.415
60
40
liquid
20
solid 7.322
0
0
20
0 200 400 600 800 1000 Temperature,K 1400
Fig.2. Enthalpyofpurezincfrom0Kto1400Kwithreferencetosolid,hexagonalZnat298.15K.
H,kJ/molEnthalpyofZincSulfide
100
13.389
50 298.15K
50
EnthalpyofFormation=
100
201.669kJ/mol solid,beta
150 solid,alfa
200
250
0 200 400 600 800 1000 1200
Temperature,K 1400
Fig.3.Enthalpyofzincsulfide().EnthalpydifferenceH(T)H(298)()andenthalpyofformation
havebeenmeasuredbycalorimeter.Notecrystalstructuretransformationat1293K.
HSCChemistry5.0 85
where S(298.15) is the standard entropy of the substance which can be calculated by
integratingCp/Tfunctionfrom0to298.15Kelvins,TistemperatureandHtr isenthalpy
ofphasetransformationatatemperatureTtr,seeFig.4.
Entropiesofcrystallinesubstancesapproachzeroat0K.Thisfundamentalexperimental
observationiscompatiblewiththethirdlawofthermodynamics.Ifentropyisunderstood
asameasureofdisorder,thedisorderreachesitsminimum atabsolutezeroandinperfect
crystalstructures.
Thetemperaturedependenceofheatcapacityatelevatedtemperaturescannotbepredicted
theoretically by thermodynamics. A fully mathematical correlation is therefore adopted
for fitting experimental heat capacities. The Kelley equation is used throughout this
programinthefollowingform:
whereA,B,CandDarecoefficientsestimatedfromexperimentaldata.
Gibbs Energy G: The mutual stability of substances (elements, compounds, ions, etc.)
cannotbecomparedusingenthalpy,entropyorheatcapacityfunctionssolely.Itmustbe
doneusingtheGibbsenergydefinedbyEquation(5).TheGibbsenergyofpurezinchas
beencalculatedusingthisequationanddatainFigs.2and4.Theresultscanbeseenin
Fig.6.
G = H T.S [5]
Experimental Methods: Many experimental and theoretical methods are available for
evaluating the basic thermochemical enthalpy, entropy and heat capacity data than it is
practicaltodescribeinthiscontext.Usuallyacriticalanalysisofthevaluesisbasedona
thorough simultaneous crosscorrelation of thermochemical data from different sources,
measurement methods (calorimetric, spectroscopic, electromotive force, solubility, etc.)
andtheoretical calculations.More information ofthe assessment methods canbefound,
forexample,inthereferencesmentionedinChapters32and33.
HSCChemistry5.0 86
S,J/(mol*K)Entropyof
200 Zinc
160
140 97.721
120
100 160.415
liquid
80
solid 10.571
60
40
20 41.631
0
0 200 400 600 800 1000 Temperature,K 1400
Fig.4. Entropyofzinccalculatedfromtheexperimentalheatcapacity,byEq.(3).
Cp,J/(mol*K)HeatCapacityof
35 Zinc
liquid
30 298.15K
solid
mp=692.7K bp=1180K
25
gas
20
15
25.403
10
0
0 200 400 600 800 1000 Temperature,K 1400
Fig.5. Heatcapacityofzincfrom0Kto1400Kcalculatedfromcalorimetricdata,byEq.(1).
HSCChemistry5.0 87
G,kJ/molGibbsEnergyof
0 Zinc
12.412
solid
20 33.841
40 74.825
liquid
60
298.15K
692.7K
80
gas
100 1180K
120
0 200 400 600 800 1000 Temperature,K 1400
Fig.6.Gibbsenergyofzincat01400KcalculatedfromtheenthalpyandentropyvaluesusingEquation
(5).
Data Format in the HSC Databases: Traditionally, experimental heat capacity values
seeFig.5havebeenfittedusingtheempiricalEquation(4).ThecoefficientsA,B,Cand
DprovidedinHSCarevalidinlimitedtemperaturerangesonly.Usuallythetemperature
ranges are the same as the stability ranges of solid, liquid and gaseous states of the
substances.
The heat capacity coefficients can be saved in the HSC database as data sets for each
temperature range, together with the enthalpy and entropy values for formation and
transformations. The first data set contains the enthalpy of the formation Hf(298.15),
standard entropy S and the coefficients A, B, Cand D for the most stable form of the
substance at room temperature. The second set contains the enthalpy and entropy of
transformation as well as the coefficients for the second temperature range, etc. For
furtherdetails,seeChapter28.11.
Note that the data for gaseous substances as Zn(g) has been saved separately. Such a
selection allows, for example, equilibrium calculations with the gaseous substances also
belowtheirboilingpoints.
HSCChemistry5.0 88
Table1. ThermochemicaldataofzincasprintedfromtheHSCdatabase.
All thermochemical data required in HSC and its modules, including heat capacity,
enthalpy, entropy and Gibbs energy of the substances, can be calculated from the basic
data in its databases using Equations (1)(11). HSC Chemistry utilizes the equations
automaticallywheneverneeded.
wherethefollowingabbreviationshavebeenused:
[A] = activityorpartialpressureofspeciesA,B,C,etc.
a = stoichiometriccoefficientofspeciesAinreaction
n = stoichiometriccoefficientofaspeciesinreaction(a,b,c,...)
R = gasconstant=1.987cal/(Kmol)=8.314J/(Kmol)
T = TemperatureinK
HSCChemistry5.0 101
10. REACTIONEQUATIONS
ClickingtheReactionEquationsbuttoninthemainmenushowstheReactionEquations
Window, see Fig. 1. With this calculation option you can calculate the heat capacity,
enthalpy, entropy and Gibbs energy values of a single species as well as of specified
reactionsbetweenpuresubstances.
Seethereferencestatedefinitions,validnotationsandabbreviationsforthedescriptionof
thechemicalformulaeinChapter28.Databases,chapter2.
10.1 OneChemicalSubstance
Fig.1. ReactionEquationsWindowofHSCChemistry.
HSCChemistry5.0 102
Fig. 2. Thermodynamic data of A12O3 (alumina) displayed by the Reaction Equation option of HSC
Chemistry.
ByenteringasinglechemicalformulaintotheFormula boxyouwillgetsimilartablesof
thermochemical data as presented in many thermochemical data books. HSC will,
however, provide the results faster and exactly at those temperatures which you really
want.Pleasefollowthesesteps:
1. Writeachemicalformulaintothebox,Fig.1.
Forexample:Fe,Na2SO4,Al2O3,SO4(a),H(+a)orSO2(g).
SeethevalidnotationandsyntaxofchemicalformulaeinChapter21.2.
2. Selectthelowerlimit,upperlimitandtemperaturestep.
3. SelecttheTemperatureandEnergyUnits,byclickingthecorrespondingbuttons.
4. SelecttheFormatoftheresults.
Normal(Absolutescale):
H(species),S(species)andC(species)
This format is used for example in the famous I. Barin, O. Knacke, and O.
Kubaschewskidatacompilation1.
Delta(Formationfunctions):
HSCChemistry5.0 103
DH =H(species) SH(elements)
DS =S(species) SS(elements)
DG =G(species) SG(elements)
DG =G(ions) SG(elements)+z/2*G(H2(g))z*G(H(+a))
z =charge.
ThisformatisusedforexampleintheNBSTablesNBS82.
5. The CollecttoSheetoptionwillcollectseveraltablesonthesamespreadsheet.
6. Select theShow Transitions option if you also want to see the data at the phase
transformationtemperatures,suchascrystalstructurechangesandmelting.
7. Select the CrissCobble option if you want a CrissCobble extrapolation for the
heatcapacityofaqueousspecies,seeChapter21.4.
8. PressCalculate(orEnter)togettheresultsonthescreen.
9. PressPrinttoprinttheresults,seeFig.2.Notethatyoucancollectseveralsetsof
resultsinthesamesheetifyouhaveselectedtheCollecttoSheetoptioninFig.1.
Youcanclearthewholesheetbypressing Clear.
10. PressCopyAll togetalltheresultsintotheClipboard,thenyoucaneasilypastethe
resultstootherWindowsapplications,forexample,toMSExcel,seeFig.2.Using
Copy it is possible to copy and paste contents of individual cells to other
applications.
11. IfyouwanttosavetheformulaandresultsinanASCIIfilepressSave,seeFig.2.
YoucanreadthesefilesbacktotheReactionmoduleusingFileOpen,seeFig.1.
NotethatSavesavesalltheselectionsinFig.1,soyoucanreturntheseusingFile
Open.TheFileOpenHSC2FilebuttonreadsonlyoldHSC2.0fileswhichreturn
onlyformula,butnottheselectionsnortemperaturerange.
Note: 1. Youcaneasilycheckthebasicdatafromthedatabase,whichhasbeenusedinthe
reactionmodulecalculations.InFig.1selecttheformulaintheReactionEquation
box and press Peep Database. The same procedure can be found in Fig. 2 by
pressingtherightmousebuttonorselecting Editfromthemenu.
2. The table in Fig. 2 has some formatting and Copy Paste functions as do other
tables inHSCChemistry.Thesefeatureshelptocreateagoodprintedcopyofthe
resultsforvariouspurposes.
3. HSCsearchesforthespeciesdatafirstfromtheOwndatabase(OwnDB5.HSC).If
it does not find a species there, it will search from the Main database
(MainDB5.HSC).ThereforeHSCalwaysusesdataintheOwndatabaseifthesame
speciesexistsinbothOwnandMaindatabases.
4. IfyouhaveselectedDeltaformatfortheresults,HSCwillalsosearchfordatafor
the necessary elements and calculate the formation functions of enthalpy, entropy
andGibbsenergy.Usuallytheoriginalexperimentaldataisinthisformat:however,
sometimesthecomparisonofdatainthisformatmaybemoredifficultbecausethe
datasourcesoftenusedifferentdataforelements.
5. HSC will make a CrissCobble extrapolation for the heat capacity of aqueous
species at elevated temperatures (> 25 C) if the CrissCobble option is selected.
Theextrapolationis not doneifAandBoftheheatcapacitycoefficientsA,B,C
HSCChemistry5.0 104
10.2 OneChemicalSubstanceResults
10.3 ReactionEquations
Fig.3. InputdataforReactionEquationcalculations.
HSCChemistry5.0 106
Fig.4. ResultsofReactionEquationcalculations.
You can write almost any kind of reaction equation into the Reaction Equation box of
HSC,Fig.3.Herearesomeexamplesofvalidequationsyntax:
2Cu+S=Cu2S
H2O=H(+a)+OH(a)
H2(g)=2H(+a)+2e
H2O=1/2O2(g)+2H(+a)+2e
Ag=Ag(+a)+e
3NO2(a)+2H(+a)=2NO(g)+H2O+NO3(a)
2Al(+3a)+3S(2a)+6H2O=2Al(OH)3+3H2S(g)
HSCChemistry5.0 107
Ontherightsideofthebuttonyoumaygiveamultiplier,whichwillbeusedtomultiply
allthecoefficientsinthereactionequation.Thedefaultvalueis1,whichmeansthatthe
smalleststoichiometriccoefficientinthereactionequationis1.
YoucancontinueinthesamewayasintheOneChemicalFormulaoptionChapter10.1.
NotethattheDeltaFormatandShowTransitionsoptionshavenoeffectontheresults,
becausetheenthalpyandGibbsenergyofareactionareintheDeltaformatbydefinition.
HSCcalculatesthestoichiometryofthereactiongivenbytheuser,andpointsouterrorsif
theelementbalanceisincorrect.
The example in Fig. 3 refers to the Mondprocess for refining impure nickel. In the
processrawimpurenickelisfirsttreatedwith COgasat60Ctoevaporatethenickelasa
carbonyl gas. In the second stage, the temperature of the gas is increased to 200 C to
decomposethenickelcarbonylgasintopuremetallicnickelandCO.Thisprocessworks
becausetheequilibriumofthisreactionisontherightside(EquilibriumconstantK>1)at
lower temperatures and on the left side (K < 1) at higher temperatures. The reaction is
exothermic(DHisnegative)atalltemperatures.
Vaporpressurespcanbecalculatedbywritingthereactionequationforthevaporization
reactionconcerned.Forexample,forpuremagnesiumtheequilibriumisMg=Mg(g),Fig.
5.Theactivityaofpuremagnesiumis1andthusthevaporpressureinbarisequaltothe
equilibrium constant according to Eq. (10) in Chapter 8. Introductionand Eq. (1). See
alsoFig.6.
Ifasubstancevaporizesintoseveralpolymers,allofthemmustbetakenintoaccount.The
totalvaporpressureisthenthesumofalltheindividualpartialpressures,ifthegasphase
behavesideally.
You can also calculate more complicated reactions. First write the reaction as shown in
Fig.7,thenpressBalanceforthecoefficients,seeFig.8andfinallypressCalculatefor
the results, see Fig. 9. Note that for aqueous ionic reactions HSC also calculates the
electrode potential versus Standard Hydrogen Electrode if electron (e) is used in the
formula.
Youcancalculatemassbalancesinmoles,gramsandlitersforanyreaction.Thespecies
doesnotneedtoexistintheHSCdatabases.
HSCChemistry5.0 108
Fig.5. InputdataforReactionEquationcalculations.
HSCChemistry5.0 109
Fig.7. WritethereactionequationwithoutstoichiometriccoefficientsandpressBalanceEquation.
Fig.8. PressCalculatetodisplaytheresults.
HSCChemistry5.0 1011
Fig.9. Resultsforanaqueousionicreaction.
Thedatausedtocalculatetheresultscanbedisplayedbyselectingonesubstanceinthe
ReactionEquation box,seeFig.3andpressingPeepDatabase.Thesameprocedurecan
be found in the Results window, see Fig. 4, by pressing the right mouse button. The
databasecontentisshowninFig.10.Insertisavailableforinsertingaselectedformula
intotheReactionEquationbox.Removewillremoveaselectedformulafromthissame
box. Note that the selections and editing in Fig. 10 do not haveany effect on the HSC
databases.
HSCChemistry5.0 1012
Fig.10. Thedatabasewindow.
10.4 ReactionEquationsResults
TheoperationofthebuttonsinFig.3aredescribedinthepreviouschapter.Themeaning
oftheresultscanbesummarizedasthefollowing:
1. IftheequilibriumconstantKis<1(orlog(K)<0)thereactiongoestotheleft.
2. IftheequilibriumconstantKis>1(orlog(K)>0)thereactiongoestotheright.
3. NegativeEnthalpyHofthereactionmeansthatthereactionisexothermic,i.e.heat
isreleased,Equation7in 8.Introduction.
4. PositiveEnthalpyHofthereactionmeansthatthereactionisendothermic,i.e.heat
isneeded,Equation7in 8.Introduction.
5. DeltaFormathasnoeffectontheresultsofreactionequations.
6. In ionic reactions POTENTIAL E yields the electrochemical potential (in Volts)
versustheStandardHydrogenElectrode.
7. EquilibriumconstantKiscalculatedusingEquation11in 8.Introduction.
HSCChemistry5.0 111
11. HEATANDMATERIALBALANCE
Fig.1. HeatandMaterialBalanceworkbookwithIN1,OUT1andBALsheets.
Heat balance calculations are usually carried out when developing new chemical
processes and improving old ones, because no process can work if too much heat is
releasedorifthereisalackofthermalenergytomaintainthereactiontemperature.This
modulecalculatestherealorconstrainedheatbalances,withgivenmassbalancesasthe
boundaryconditions,butnotthetheoreticalbalancesatequilibriumconditions.
TheheatbalanceapplicationalwayscontainsIN1,OUT1andBALsheets.ApairofIN
and OUT sheets is called a Balance area, which may be considered equivalent to a
controlvolume.Atotalnumberof127balanceareasmaybeinserted,tocreateamultiple
balanceareaworkbook.Multiplebalanceareaworkbooksareexplainedinmoredetailin
chapter 10. Multiple balance areas. For simplicity only the first balance area (IN1,
OUT1)willbedescribedinthefollowingchapters.
Thebasic idea oftheheat balance module is that theuserspecifiestheIN1andOUT1
species,temperaturesandamountsandtheHeatBalancemoduleautomaticallycalculates
theheatandmaterialbalancesusingtheBALsheet.TheHeatbalancemoduleupdatesthe
calculated results on the BALANCE row at the bottom of the form each time the user
changestheinputdata.PleasedonotmodifytheBALsheet.
HSCChemistry5.0 112
Since the program uses and creates new balance areas according to the name of the
sheets,itisextremelyimportantthattheautomaticallycreatedsheetnames,i.e.theBAL,
INxandOUTxsheets,shouldnotbemodified.
You can also add new sheets for other spreadsheet calculations using theInsert Sheet
and InsertExcelSheetselectionsinthemenu.TheothersheetsworkverymuchlikeMS
Excelworksheets,forexample,youcan:
renamethesheetnamebydoubleclickingthesheettab
typeformulaeintothecells
usesimilarcellreferencesasinExcel
usemostoftheExcelfunctions
link the sheet to IN1 sheet using normal Excel cell references, for example, for
convertingelementalanalysisoftherawmaterialtoamountsofthecomponents.
usetheheatbalancecalculationresultsinOUT1sheetastheinitialvaluesforother
spreadsheetcalculations.
InadditiontheHeatBalancemenuprovidesawiderangeofExceltypefeatures,suchas:
number, font, alignment and border formatting, defined names settings and cell
protection. Because they are not necessarily needed in heat balance calculations, these
featuresarenotdescribedhereindetail.
Thenewheatbalancemoduleoffersseveralwaystocalculateheatandmaterialbalances:
1. Theusertypestheinputandoutputspecies,temperaturesandamountsintotheIN1
andOUT1sheetsrespectively.Thisisasimplewaytocalculateheatandmaterial
balancesandwasavailablealreadyinHSC2.0.However,theproblemwiththeold
versionwasthattheuserhadtomanuallymaintainthematerialbalancewhenthe
inputfeedchanged.
2. Materials (species) are given as groups of substances, called streams. These
streamscanbethesameasthephases,buttheycanalsobeamixtureofphases.
3. The output amounts can be linked with the input amounts with Excel type cell
references,orviceversa.
11.1 BasicCalculationProcedure
ThefollowingprocedurewilldescribethemostsimplewaytocalculateHeatBalance:
1. Introduce the input substances (raw materials), temperatures and amounts on the
IN1sheet.Itispossibletoeithertypeamountsinkmol,kgorNm3.Itisadvisedto
use kmol and kg because missing density data may cause inaccuracy with Nm3
units.
2. Introducetheoutputsubstances(products),temperaturesandamountsontheOUT1
sheet.Typeamountsineitherkmol,kgorNm3 aspreferred.
3. Whenfeedingadditionalenergy(electricity)totheprocess,enterthisamountinto
theTotalcolumn in the last empty row of the IN1 sheet. You can also type for
example Extra Heat in the first column of this row, see Fig. 20. The Database
modulewillconvertthecolorofallinerttextinthefirstcolumntogreen,ifthis
textisnotidentifiedinthedatabaseasasubstance.Noticethat:
1kWh=3.6MJ=0.8604Mcal(th).
However, the Balance module will automatically recalculate green text when
changing units from the menu. If the green text cell contains a formula, it will
HSCChemistry5.0 113
automaticallybechangedaccordingto thenewunit.Forexampleachangefrom
CtoKwilladd +273.15 totheendoftheformula.
4. IfheatlossvaluesareknownthentypethemintothelastemptyrowoftheOUT1
sheet in the last column (Total). A first estimate of heat losses for an aircooled
reactor(naturalconvection)caneasilybecalculatedusingthefollowingformulain
kcal/h:
Hloss= (6.8+0.046*T2)*(T2 T1)*A [1]
Where: A = Outersurfaceareaofthereactor(m2)
T2 = Surfacetemperatureofthereactor(C)
T1 = Roomtemperature(C)
Please use the Heat Loss module if more accurate heat loss approximations are
needed.
5. HSCautomaticallyandimmediatelyupdatestheheatbalanceonthebottomlineas
soonaschangestoanyinputdataaremade.
6. HSCalsoautomaticallyupdatesthematerialamountbalancesinmol,kgandNm3
units.Noticethat onlythe mass balance inkgunitsonthebottomrowshouldbe
zerothemoleorvolumebalancescaneasilychangeinanychemicalprocess.
7. The element balance can be checked by selecting Element Balance from the
Calculatemenu,seeFigs.1and2.
8. ByselectingTemperatureBalancefromtheCalculatemenuitispossibletosee
the estimatedtemperature oftheproducts whenthe heat balance=0,seeFigs.1
and3.
Fig.2. ElementBalance.
HSCChemistry5.0 114
Fig.3. Temperatureoftheproducts(adiabaticprocess).
9. To insert an empty row in the table, select Row from the Insert menu or by
pressingtherightmousebuttonandselecting InsertRowfromthepopupmenu.
10. RowscanbedeletedbyselectingRowfromtheDeletemenuorpressingtheright
mousebuttonandselecting DelRowfromthepopupmenu.
11. Youcanchangethe order ofthesubstances byinsertingan emptyrowandusing
the Copy Pastemethodtoinsertthesubstanceinthenewrow.TheDragandDrop
methodcanalsobeused.However,itisextremelyimportant to CopyandPaste
the whole row not only the formula, because of auxiliary data in the hidden
columnsontherightsideoftheIN1andOUT1sheets.
Please keeptheCopyModeselectiononintheEdit menu whenrearrangingthe
species,asthiswillforcetheprogramtoselectthewholerow.Whenformattingthe
columnsandcells,turnthe CopyModeselection off inthe Editmenu.
12. Temperatureunitscanbechangedbyselectingthe CorKfromthe Unitsmenu.
13. Energyunitscanbechangedbyselecting Mcal,MJorkWh fromthe Unitsmenu.
14. Ifapapercopyisneeded,selectPrintfromtheFilemenu.This optionwillcopy
allthedataonthesamePrintsheetandwillalsoprintthissheetonpaperiftheuser
presses OK. Notice that you can delete this Print sheet by activating it and then
selectingSheetfromtheDeletemenu.ThePrintSheetselectionintheFilemenu
willprintonly theactivesheet.
15. Tosavethesheets,selectSavefromtheFilemenu.Pleasesavesheetsoftenusing
differentnames,becauseyoumaywishtomakesmallchangeslaterortoreturnto
the original sheet. Saving sheets is important, because the Undo feature is not
availableinHSCChemistry.
16. It is possible to take into account the water/steam pressure compensation by
moving the cursor to an H2O or H2O(g) species and selecting Insert/Pressure
correction H2O from the menu. This will open the Pressure and Temperature
calculator,whereitispossibletospecifythepressureforthespecies.Thisisuseful
whencalculatingforexamplesteamprocesses.
11.2 FormattingtheWorksheet
TheheatbalancemoduleoffersseveralExceltypeformattingpossibilities.Thesemaybe
selectedintheFormatmenu:
Number, Font, Font Default, Alignment, Border, Pattern, Object (for graphical
objects),Sheet,Options
ColumnWidth,RowHeight
DefineNames,RefreshNames
ProtectionOn,Off,LockallCells,UnlockallCells
HSCChemistry5.0 115
ThewindowsizemayalsobechangedfromtheViewmenu.TheNormalselectiongives
aVGAsizewindow,FullHeightselectionusesthewholeheightofthescreenandFull
Width fillsthewholescreen.
11.3 SpecificationofSubstanceGroups(Streams)
The new HSC Chemistry 5.0 offers the possibility to specify the input and output
substances instreams.Thesestreams canbe made ofone orseveralphysical phases or
specieswhichhavethesamefixedtemperatureandelementalcomposition.Althoughheat
and material balance calculations can be made without using the streams, division into
streams helps considerably when changing temperatures and material amounts. Notice
thatwhenusing formulae/linksintemperaturecellsthetemperaturecellsarenotupdated
ifthespeciesarenotdividedintostreams.
Examplesofonephasestreamsare,forexample:
1. Airfeed.
2. Processgasoutput.
3. Homogenousliquidandsolidinputsandoutputs.
Examplesofmultiphasestreamsare,forexample:
1. Liquidmaterialwithsolidparticles(suspension)asinputoroutput.
2. Solid feed mixture of the process, made of different substances, such as mineral
concentrate,coalandsand.
3. Gasfeedwithliquiddropletsorsolidpowder.
ThespeciesrowsintheIN1andOUT1sheetsaredividedintoseparategroupsbyspecial
streamrows.Theserows canbe inserted inthesheet usingtheStreamselection inthe
Insertmenuorusingthesameselectioninthepopupmenufromtherightmousebutton.
The heat balance moduleautomatically makes the following modifications to the sheet
whenyouinsertanewstream(group)rowinthesheet:
1. Asksforanameforthenewgroup,whichyoucanchangelaterifnecessary.
2. Insertsanewemptyrowabovetheselectedcellwithalightbluepattern.
3. HSCassumesthatallrowsunderthenewgrouprowwillbelongtothenewgroup
downtothenextgrouprow.
4. Inserts Excel type SUM formulae in the new group row for calculating the total
amountinthegroupusingkmol,kgandNm3 units.
Oncetheinsertprocedureisready,youcaneditthegrouprowinthefollowingway:
1. Thestreamname(label)canbeediteddirectlyinthecell.
2. Thestreamtemperaturecanalsobechangeddirectlyinthecellandwillaffectthe
temperatureofallthespeciesinthisgroup.
3. The total material amount of the group can be changed simply by typing a new
amount in the group row in kmol, kg or Nm3 units. This amount can be typed
directly over the SUM formula and the program will automatically change the
amountsofthespecieskeepingtheoverallcompositionconstant.Theprogramwill
thenregeneratetheoriginalSUMformulaaftercalculatingthenewamounts.
4. It is important to note that you are unable to type formulae in the amount and
enthalpy columns of the stream row, because the SUM formulae must be in the
streamrow.
HSCChemistry5.0 116
Tochangetheamountsofspeciesinastreamusingkmol,kgorNm3 units,simplytype
the new amount in the corresponding cell. The program will automatically update the
amountsintheothercolumns,totalamountofthestreamandthetotalmaterialandheat
balanceaswell.
An example ofthespecies streams canbeseen inFig.4.The outputspecies havebeen
divided into four streams. In this example the species in each stream exist in the same
phase. Process Gas is a gaseous mixture phase, Slag is a molten mixture phase and
WhiteMetal isapuremoltensubstance.
11.4 FormulaeintheCells
Exceltype formulae and cell references can be used, for example, in order to link the
input and output amounts with each other and to maintain the material balance
automatically when the input amounts change. The input and output amounts can be
linkedusingtwomainmethods:
1. An Exceltype formula can be typed in the kmol column, which expresses the
dependenceoftheoutputmoleamountontheinputmoleamount.Forexample,if
Cu2S in the cell OUT1!C10 contains 93.8 % of copper input then you may type
formula =0.938*IN1!C7incellOUT1!C10,seeFig5.
2. TheHeatbalancemoduleautomaticallycalculatesinputandoutputmoleamounts
for elements.Thecell names forinput amountsare:InAc,InAg,InAl,InAmand
the equivalentfor output elementsarecalledOutAc, OutAg,OutAl,OutAm, etc.
Forbalanceareaswithahighernumber(forexampletheIN2andOUT2sheets)the
corresponding cell names are simply InAc2, InAc3 and OutAc2, OutAc3, etc.
Thesenamescanbeusedintheformulae.Theformulainthepreviousexamplecan
alsobewritten:=0.938*(InCuC12)/2usingthesedefinednames,seeFig.5.The
cellswithelementamountsarenotvisibletotheuser.
Pleasebeverycarefulwhenusingdefaultinputandoutputnamessimultaneously,
because it is very easy to end up with circular references. An indication of a
circularreference is that the heat and materialbalance, whichcanbeseen onthe
BALANCE row, changes even after a recalculation (Calculate/ReCalc from the
menu). By selecting Format/Options from the menu and highlighting the
Iteration checkboxunderthe Calculation tab,itispossibletoautomaticallyiterate
the circular references. This is, however, not recommended for very large
worksheets.
Within the IN1 and OUT1 sheets it is recommended to use formulae only in the kmol
column and not in the other Amount columns. You can use the formulae also in other
columns,butpleasebeverycareful.Intheothersheetstherearenospeciallimitationsfor
theformulae.
HSCChemistry5.0 118
11.5 ElementalCompositions
The elemental compositions of the species groups may be calculated using the Stream
CompositionsselectionintheCalculatemenu,seeFig.6.Thisprocedurecalculatesthe
elementalcompositionsofeachgroup,createsnewIn1%andOut1%sheetsandprints
resultsonthesenewsheetsinmol%andwt%units.
11.6 AdditionalSheets
TheHeatBalanceworkbookconsistsatleastoftheIN1,OUT1andBALsheets.Theuser
may, however, add up to 256 sheets to one workbook. These additional sheets may be
used,forexample,toconverttheelementalcompositionsofrawmaterialstoamountsof
species whichare neededinthe IN1sheet.Thesesheetscanalsobeusedtocollect the
mainresultsfromtheOUT1sheetinonesummarytable.Donotusethereservednames
IN1,OUT1,BALandTargetassheetnames.
ToaddsheetsselectInsertSheetfromthemenu.Thiswilladdonesheetontheselected
location.Torenamethisnewsheet,doubleclicktheTabonthebottomoftheform.You
can also import Excel sheets by selecting Insert Excel Sheet from the menu. This
selectionallowsyoufirsttoselectthefileandthenthesheetwhichyouwanttoinsertinto
theactiveHeatBalanceworkbook.
The example inFig.7shows aFEEDsheet,which isusedtospecifytheraw materials
amountstotheIN1sheet.TheusermaygivethecompositionsandamountsincolumnC,
thisdatawillthenbeusedtocalculatetheamountsofspeciesincolumnF.Thematerial
amountsinIN1sheet aregivenusingrelevant cellreferences tocolumnFintheFEED
sheet. This example can be found from your HSC5\Balance directory under the name
CUCONV2.BAL.Theusercanconstructthelayoutoftheadditionalsheetsfreely.
TheRedFontShieldpropertyisausefulwaytopreventaccidentalmodificationofthe
datainthecells.Ifthis propertyis set using menuselectionFormat,Red FontShield
thenonlycellswithredfontcanbeedited.However,itisrecommendedtosavethework
regularlyusingdifferentnames,forexample,test1.bal,test2.bal,test3.bal,etc.inorderto
recovertheoriginalsituationafterharmfulmodifications.
HSCChemistry5.0 1112
Fig.7. AdditionalsheetscanbeaddedtotheHeatBalanceworkbook.
11.7 TargetDialog
Theusercaniteratemanually,forexample,thefuelamount whichis neededtoachieve
zeroheatbalancebychangingthefuelamountuntiltheheatbalanceiszero.TheTarget
sheet offers a faster automatic way to carry out these kind of iterations. The following
instructionswillexplainthisprocedureinmoredetail:
1. SelectTargetDialogfromthemenu.This willalsoautomaticallycreateaTarget
sheet,whichissimilartopreviousHSCversions.
2. Selectonecellonrow4intheTargetdialogifnotselected.
3. Select onecellwhichwillbeusedasafirstvariableandselectSetvariablecell.
This willaddthecellreferenceofthisvariabletotheTargetdialogincolumnB.
Youcanalsotypethecellreferences manuallyintheTarget dialog.Note:Please
useonlyStreamtemperaturecellsasvariablesforthetemperatureiterations,ie.do
notusespeciestemperaturecells.
4. SelectonecellwhichwillbeusedasfirstvariableandselectSettargetcell.This
willaddthecellreferenceofthisvariabletotheTargetdialogincolumnB.
5. Repeatsteps3and4ifyouwanttoaddmorevariablesandtargets.
6. SetvalidMinandMaxlimitsincolumnsDandEaswellastheTargetValuein
columnH.YoumayalsotypenamesincolumnsAandF.
HSCChemistry5.0 1113
Fig.8. Targetdialogspecifiesthevariablesandtargetcellreferences.
HSCChemistry5.0 1114
11.8 Graphics
Fig.9. Simpleheatbalancediagram.
In the following diagram (Fig. 10) the heat balance is automatically calculated before
eachstep,whichisindicatedbythenumber4intheTargetrow1 column.Thisisdone
bypressingtheTargetiteration button,selectingrow4ontheTargetsheetandclicking
the SetTargetrowsbutton.ThexaxisnowgivestheFewt%andtheyaxisthecooling
scrap required. The diagram may then be interpreted as the quantity of cooling scrap
requiredtomaketheheatbalancezero,whentheFewt%variesfrom20%to25%.
HSCChemistry5.0 1116
Fig.10. Diagramwheretheheatbalanceisautomaticallyiteratedtozerobeforeeverycalculationstep.
11.9 Multiplebalanceareas
HSCChemistry5.0 1117
The previous Balance modules up to HSC 4.0 were restricted to one balance area (or
control volume) only. Since most processes consist of multiple balance areas, the new
Balance module enables the user to create up to 127 multiple balance areas. A balance
areaconsists ofanINxandanOUTxsheet,wherexdenotesthenumberofthebalance
area. These can then be connected to each other creating a realistic simulation of a
process.The example file FSF_process.BAL contains a highly simplified multibalance
modelofanOutokumpuFlashSmeltingFurnaceprocess.
Linking the balance areas with each other is recommended to carry out after each
individual balance areas operate properly. Linking may be achieved either manually
withformulaeorautomaticallywiththeCopyPasteStream combination.Simplyplace
thecursoronastreamrowinanOUTxsheet,oronarowthatbelongstoastream,and
selectEdit/Copy.ThenplacethecursoronarowinanINxsheetandselectEdit/Paste
HSCChemistry5.0 1118
Stream. The stream will now be copied here so that the first row of the stream is the
cursorposition.Thekmolcolumnofthepastedstreamwillconsistoflinks(formulae)to
the copied stream, so that the material amounts of the streams will remain equal. The
other cells are directly copied as values. If the stream temperature cell in the copied
streamisaformulaethenit willnotbecopied.Inthiscaseitisuptotheusertodecide
howthestreamtemperatureforthepastedstreamshouldbecalculated.
Itisalsopossibletocreate returnstreams,i.e.streamsthatreturntoapreviouspartofthe
process,thuscreatingloopsintheprocess.Whenpastingastreamintoanalreadylinked
part,acircularreferencemightoccur.Thisisthecasewhenlinkseventuallyreferbackto
eachother,i.e.iterationsareneededtocalculatetheworksheet.Automaticiterationsmay
be done by selecting Format/Options from the menu and highlighting the Iteration
checkbox under the Calculation tab. Please be careful when changing the inputs of a
worksheet consisting of circular references. For example if a cell, which is part of a
circularreference,shows the message#VALUE!,it will not recoverunless thelinks in
thecellsarechangedthusbreakingthecircularreference.Savingtheworksheetregularly
usingdifferentnames(Test1,Test2,etc.)isthusalwaysrecommended.
HSCChemistry5.0 1119
Fig. 12. The IN1 sheet (Flash Furnace) of the FSF_process.BAL example. The stream Flue dust is a
returnstreamfromtheboiler(Copy/Pastestream),thuscreating circularreferencesintheworksheet.
Automaticallyupdateddefinednames(inputandoutputkmolamounts)varyaccordingtothe
balance area. For example InAl, InC, OutFe for the first balance area will become InAl2,
InC2,OutFe2forthesecondetc.Notethatthedefinednamesofthefirstbalanceareadonot
haveindexnumbers.
Fig.13.TheOUT2sheet(ConverterI),givestheoutputfromthefirstpartoftheconverter.Theformula
=InCa2*Analysis!L29/100incellC5meansthatthetotalCaisdistributedasthepercentagegivenincell
L29ontheAnalysissheet.
HSCChemistry5.0 1120
DrawingFlowsheets(Flowcharts)
Additionalsheetsmaybeusedtocollect,forexample,allthenecessaryinputfortheprocess
into onesheet.They mayalsobeusedtocollect calculatedprocess parameters,forexample
the amount of Cu in a stream. Figure 14 shows the process layout for the Flash Smelting
Furnaceprocess.
"Insert,GraphicalObject,..."selectiongivespossibilitytodrawlines,rectangles,etc. onthe
additionalsheets.However,itisrecommendedtodrawflowsheetsusing"Format,Border,..."
and "Format,Pattern,..."selectionbecausetheseproperties are morecompatible withExcel
95,97and2000.Arrowsmaybedrawnusing"Insert,GraphicalObject,Arrow"selection.
HSCgraphicalobjectsarecompatibleonlywithExcel95.Thismeansthatifyouwanttoget
the graphical objects to Excelfiles then you should save using "File, Save XLS 5 file, ..."
dialog.
Fig.14. ProcesslayoutandinputsheetfortheFlashSmeltingFurnaceprocess.
HSCChemistry5.0 1121
Figure15providesamoredetailedanalysis oftheprocess.Themodelisconstructedsothat
the inputs are given as species analysis and the outputs are calculated. The elemental
distributions are also inputs, in other words the user defines the wt% for the elemental
distributions into the given species and streams. This is achieved using the automatically
definednames,forexampleInCaandInO2,andthusalwayskeepingtheelementalbalanceat
zero.Themodelmaythenbeusedtobalancetheheatbalancesoftheprocess,whichenables
the user to calculate one unknown parameter per balance area. The unknown parameters
calculatedintheFSF_process.BALexampleareindicatedbyalightbluecellbackground.The
calculatedparameters maybechangedusingtheTargetDialogoption,whichis describedin
furtherdetailinchapter8.TargetDialog.
Fig.15. Detailedanalysisoftheinputandoutputstreamsandtheelementaldistributionsintodifferent
species.Thedistributionsaregiveninwt%(weightpercentage).
HSCChemistry5.0 1122
11.10 GeneralConsiderations
In the Heat Balance module it is possible to use the new addin functions provided by
HSC5.0.Thefunctionsshouldbeenabledautomatically,thismaybeseenfromtheFile
selectioninthemenu.AcheckedHSC5.dllOnindicatesthatthefunctionsareavailable
andachecked HSC5.dllOffindicatesthattheyaredisabled.Sometimesitisnecessaryto
browsethe locationoftheaddinfile manually.This is donebyselectingFile/AddIns
from the menu and then browsing to your Windows system directory (for example
c:\Windows\System in Windows 98) by pressing the Browse... button. Select the file
HSC5.dll. A more detailed description of the functions available may be found in
Chapter27.ExcelAddIns.Itis,however,notrecommendedtouseaddinfunctions for
verylargeworksheets,sinceacompleterecalculationoftheworksheetisnecessaryeach
time a change is made in the worksheet. This is the case only when using addin
functions.
Pleasedonotusetemperatureformulaethatarelinkedtoothertemperaturevalueswithin
a stream, instead link them to the stream temperature cell or any cell in a user sheet.
Otherwisethetemperatureswillbeupdatedonlyafterthenextchange.Noticealsothata
change in the temperature value is required for the whole stream to be updated
accordingly.
SimplegraphicalobjectsmaybeinsertedbyselectingInsert/GraphicalObjectfromthe
menu. The shapes are: Line, Rectangle, Oval, Arc and Polygon. After inserting, the
objectsmaybemodifiedbyfirstselectingtheobject andthenselectingFormat/Object
fromthemenu.
The Latent H column (= specific heat) is used to describe the energy which may be
releasedwhenthecompoundiscooleddownfromthegiventemperatureto298.15K.In
otherwords,itcontains latent heats(=enthalpiesofthepossiblephasetransformations)
butalsospecificheats.TheenthalpiesgivenintheTotalHcolumncontainthevaluesof
theLatentHcolumnaswellastheheatsofformationreactions.Thesevaluesareusedto
calculateheatbalances.
In molten mixtures such as oxide slags, substances can exist in liquid state at lower
temperaturesthantheirmeltingpoints.Inthesecasesitispossibletousean(l)suffixat
theendoftheformulae,seeFig.1.ThiswillforceHSCtousedataoftheliquidstatefor
specieswithan(l)suffix.
Ifyouhavecarriedoutalaboratoryorindustrialscaleexperimentorprocesscalculations
youusuallyknow:
1. Theraw(input)materialsandtheiramountsandtemperatures.
2. Theproduct(output)materialsandtheiramounts,temperaturesandanalysis.
3. Theinputheatandheatlossescanfirstbeestimatedaszero,ifnotavailable.
In order to calculate a heat balance you must first convert the (elemental) chemical
analysisoftherawmaterialsandtheproductsintoinputandoutputsubstances(species).
Sometimesthisstepisthemostdifficult,soyoumaychoosetocarryoutthisprocedure
HSCChemistry5.0 1123
using the HSC Mineralogy Iterations module, see Chapter 22. Mineralogy iterations.
Whenthisiscompleted,simplytypetheinputsubstances(species)intotheIN1Sheetand
the outputsubstances intotheOUT1sheet.Immediatelyafterthat you willseethe heat
and material balance on the bottom line. You can also test the procedure described in
chapter5.
ItisimportanttochecktheelementbalancebyselectingCalculate/ElementBalance,in
order to avoid incorrect material and heat balances. This can also be used to check the
validityofthechemicalanalysesandtheotheramountmeasurementsoftheexperimentif
theuserinputisbasedonthisdata.
Whencreatingamultiplebalanceareamodel,selectingCalculate/TotalBalanceshows
anoverviewofallbalanceareasinonewindow.Thisisusefulforaquickcheckwhere
thematerialand/orheatbalancearenotzero.Italsoshowsthetotal(ornet)materialand
heatbalanceforallbalanceareas.Itistheneasytoseewhichbalanceareasproduceheat,
which require heat, and indications of how the heat could be tranferred within the
process.
Itisimportanttonotethatthisisarealheatbalanceforengineeringpurposes,whichalso
takesintoaccountthekineticaspectsiftheuserinputisbasedonrealexperimentaldata.
Theheatbalance,whichcanbeobtainedfromtheequilibriumcalculations,istheoretical
inthisrespect.Itisvalidonlyiftheequilibrium isreachedintherealprocess.
HSCChemistry5.0 1124
11.11 HeatBalanceExamples
SeetheexamplesprovidedbytheHSCpackagebyselectingFile/Openfromthemenu,
seeFig.1,andselectsomeofthereadymadefiles inthedirectoryforediting.HSC5.0
can read the old HSC 2.0 Heat Balance textfiles, but it cannot save them in the old
format.ThenewHSC5.0HeatBalancefilessaveallthesheetsandformats,notonlythe
textdata.
1. Preliminarycheckforaheatbalance(CUSMELT.BALfile)
For some processes based on reaction equations or equilibrium calculations, the
heat balance can easily be checked by entering the assumed input and output
substancesaswellastheirtemperaturesandamounts,seeexampleCUCONV.OHE
andCUSMELT.OHE,Fig.1.
2. Adiabatictemperatureoftheflame(BUTANE.BALfile)
Inanadiabaticprocessheatlossesfromandheatinputtothesystemarezero,i.e.
there is no heat exchange with the surroundings through the system boundaries.
Therefore,theadiabatictemperatureequalsthehighestattainabletemperaturefrom
aflameorachemicalreaction.BytypingtherawmaterialsintotheIN1sheetand
theproductsintotheOUT1sheetitispossibletoseetheadiabatictemperatureby
selecting Calculate/Temperature Balance from the menu, Fig. 3, see example
BUTANE.OHE.
3. Dimensioningofanevaporator(H2O.BALfile)
The evaporator dimensions can be optimized manually by typing the input
substances into the IN1 sheet and the desired output substances, amounts and
temperaturesintotheOUT1sheet.Oncethesehavebeenentered,youcanstartto
change the amount or temperature of the input vapor (input heat if heated by
electricity)manually,inordertofindtheoptimumvalues.SeeexampleH2O.OHE.
4. Netandgrossheatvalueofcoal,fueloilandnaturalgas.
(Coal1,Coal2,FuelOil1,FuelOil2,NatGas1.balfiles)
TheHeatbalancemodulemakesitpossibletocalculatetheHeatValues(Calorific
Values)fordifferentfuels.Examplesforcoal,fueloilandnaturalgasarefoundin
the example files. Notice that the chemical structures of the fuel oil and coal are
very complicated, however, heat values based on the elemental analysis will
usuallygivesufficientlyaccurateresultsforpracticalapplications.
5. OutokumpuFlashSmeltingFurnaceprocess(FSF_process.BALfile).
Thishighlysimplifiedprocesscaseconsistoffivebalanceareaslinkedtogether.
Thebalanceareasare:
1)FlashSmeltingFurnace
2)ConverterI
3)ConverterII
. 4)Boiler
5)ESP
The process input values are provided in the Process flow sheet and in the
Analysissheet.Bypressing F8orbyselecting IterateAll fromthe TargetDialog,
HSCChemistry5.0 1125
the heat balances are calculated. The values calculated are in the Process flow
sheetandindicatedbyalightbluecellbackground.
6. Ironproductionprocess(Iron_process.BALfile).
The example inthis file is averysimplified model ofanironproductionprocess
consistingofthreebalanceareas:
1)Pelletizing
2)Coking
3)Reduction
The process and its most important parameters are shown in the Process flow
sheet, with a more detailed analysis available in the Analysis sheet. Notice that
only the material balances are zero and iterated according to what is set in the
Targetsheet(orTargetdialog).Theheatbalancesarenotiteratedandthereforenot
zero.
HSCChemistry5.0 121
12. HEATLOSS
Themainuseofthismoduleistoestimatetotalheatlossordrawthetemperatureprofile
of a wall or reactor. However, it can also be used to compare different materials and
differentsetups,forexampletheuseofinsulationwhenamaterialhasacriticalmaximum
temperatureorwhentheoutsideaircannotexceedacertaintemperature.Theconduction,
convectionandradiationdatabasesalsoprovidearesourceassimplereferencetablesfor
material properties. Figure 1 shows an example of a heat loss wall calculation for a
smeltingreactorwiththetemperatureprofileshowninrows9and10.
Figure1:HeatLosscalculationexampleofasmeltingreactorwall.
12.1 BasicCalculationProcedure
1.Selectgeometry.
Toselect thechoice of geometry,clickonthe desiredoptionbuttonintheframe
ShapeandDimensions.Theavailableoptionsarewall,cube,cylinderandsphere.
Itishighlyrecommendedtostartthecalculationswithasimplewallcaseandthen
tocontinuewithmorecomplicatedshapeslater.
2.Selectdimension.
Whenselectingthe geometry,appropriatedimensiontextboxes automaticallypop
up.Thedimensionsarealwaysinnerdimensions.
3.Insertnewcolumn.
Theusermayspecifythelayoutoftheheattransferobjectbyselecting Insertfrom
themenubarandthenthedesiredcolumntype.Therearefourtypesofcolumns:
Surface,Enclosure,LayerandLayercontact.Surfacecolumnsmustbeinserted
to the left and/or to the right of the other columns. Enclosure columns must be
inserted between two Layer columns. Finally Layer contact, Enclosure and
Layercolumnsmustallbeinsertedbetween Surfacecolumns.
4.Specifyheattransfertype.
Youcanselect thetype of heat transfertostudy intwo ways: either manuallyor
usingthedatabase.
Manually:
1. Writethenameofthematerial/gas/liquidonthesecondrowofthetableinthe
currentcolumn.
2. Selectthedesiredheattransferfactor:
- Layercolumn:Enterthemeanconductivityforthematerial(k)onrow6.
- Surfacecolumn:Entertheconvectionand/ortheradiationcoefficient
HSCChemistry5.0 123
Usingthedatabase:
1. Pressthecorrespondingbuttonintheframe GetDataforColumn:
- Layercolumn: Conductionbutton.
- Surfacecolumn: ConvectionorRadiation button.
- Enclosure column: Convection or Radiation button (radiation for adjacent
layercolumns).
- Tospecifythedesired material/gas/liquid,placethecursorontop of it and
pressSelect.Nowthedataforthematerialwillbetransferredautomatically
to the column on the main sheet where the cursor is located. Note that
sometimesseveraldatabasesheetsareavailable,forexampletheconvection
table or function sheet. You will know that the data has been transferred
from the database sheet to the calculation sheet, once the selected material
nameappearsonthematerialnamerows2or3.
5.Specifythicknesses.
TypetheThickness x onrow4for everyLayer andEnclosure column.Surface
and Layercontactcolumnshavezerothickness.
6.Repeatsteps3,4and5untilthedesiredlayoutisachieved.
7.Calculateresults.
To calculate results for a cylinder or cube, first select whether to calculate all
sheets or just the active sheet, by pressing the appropriate option button in the
Calculate frame. By, for example, calculating only the wall sheet of a cylinder,
pipecalculationscanbeobtained.Thetwobasiccalculationtypesare:
TemperatureProfile(pressthe Temperatureprofilebutton):
- Specifythetotalheatlossbyselectingtheappropriateunit(W,kWorMW)and
bytypingtheheatlossinthetextbox.
- Specify onefixedtemperaturepointbythecursor.
- For cube or cylinder geometry, specify calculation range by selecting either
Calculateallsheets(calculatesallwalls)orCalculateactivesheet(calculates
activewall)fromtheoptionbuttons.
- Notethatwhencalculatingallsheets,thetemperatureprofileswillbeiteratedso
that thetemperatures inthe firstcolumns (insidetemperatures), as wellas the
outsidetemperatures,arethesameforallsheets.
HSCChemistry5.0 124
8.PresstheDrawDiagram buttonforagraphicalplotofthetemperatureprofile.
HSCChemistry5.0 125
12.2 HeatLossExamples
12.2.1 ExamplesprovidedbyHSC
1. SimpleCasewithfixedconductionandconvectionvalues(SimpleCase.HTR)
In this example the furnace wall is made of two layers, the inside temperature is
700 C and the outer surface is cooled with air (20 C). The conduction and
convection values are fixed. In this case the heat flow through each layer and
throughthesurfacemayeasilyalsobecalculatedmanually:
Firebrick: 1.5m2 *(700418C)*0.4W/(mK)/(0.23m)=735W
Silicabrick: 1.5m2 *(41850.63C)*0.2W/(mK)/(0.15m)=735W
Air: 1.5m2 *(50.6320C)*16W/(m2K)=735W
2. Radiatorheat(Radiator.HTRfile)
This examplecalculatestheheatoutputofaradiatoratroomtemperature(20C)
and at three different water temperatures, when the water flow to the radiator is
zero.Selecttheappropriatesheetaccordingtotheinsidewatertemperature(40C,
50Cor60C)andpresstheHeatflowbuttontoviewchangesintheoutputheat.
Adjustmentscanalsobemadetothewidthorlength(heightforaverticalwall)of
theradiatortoexaminewhatinfluencethishasontheresult.
HSCChemistry5.0 126
Figure2:Radiatorcalculationexample.
HSCChemistry5.0 127
4. HeatlossfrominsulatedpipeatconstantT(incropera94_504.HTRfile)
Example3aboveis extendedbyinsulatingthepipewitha25mmthickurethane
layer.Noticehowtheheatlossdecreasessignificantly.
5. Heatlossfromahotwatertank(Hotwatertank.HTRfile)
Thisexampleisacalculationofheatlossfromahotwatertank.Byspecifyingthe
materials,dimensions,geometry,waterandairtemperaturesthetotalheatlossfor
the tank can be calculated. The insulation thickness can easily be increased
separatelyforthetop,wallandbottomsides,inordertolowertheheat lossfrom
thetank.
Figure3:Temperatureprofilesforthehotwatertank.
6. Oilfurnace(OilFurnace.HTRfile)
In this example the heat flow due to hot flue gases and internal convection in a
furnaceiscalculated.ThefluegascompositioncanbeseenfromtheGasMixture
Radiation dialog by pressing the Radiation (gas) button. The gas contains the
followingradiatingspecies:H2O(g)11.08vol%,CO2(g)11.69vol%andSO2(g)
0.05vol%.Thisisatypicalfluegascompositionforfueloils.Thegastemperature
HSCChemistry5.0 128
7. Reactorheatlosscalculation(Reactor1.HTRandReactor2.HTR)
Inthisexamplethetotalheatlossofareactorisestimated.Thegiveninputdataare
the dimensions of the reactor, the surface temperature and the surrounding
temperature (room temperature). The surface material in the Reactor1 example is
Steel (sheet with rough oxide layer) and in Reactor2 Paint, white (acrylic).
The convective gas is Air (p = 1 bar) in both examples. Since the surface
emissivityislowerinReactor2,theheatlossissmaller.
12.2.2 SimpleStepbystepExample(creatingSmelting1.HTR)
The following steps describe how to create the Smelting1.HTR example from the very
beginning.Thefinalexamplecanbeusedtoapproximateheatlossesthroughasmelting
reactor wall. The temperature profiles for different inside temperatures can be plotted
usingtheDrawDiagrambutton.
1. SelectFile/Newfromthemenu.
2. SelectInsert/Surfacecolumn andpressthe Convection button.
3. FromtheConvectionwindow(totheleft),selectthe Function sheet.
4. SelectWater,Copperelementscoolingbymovingthecursortorow10.
5. Pressthe Selectbutton.
6. SelectInsert/Layercolumn inthemainsheetandpressthe Conduction button.
7. Type REXAL2SEXTRAintheyellowtextboxintheConductionwindowandpress
the Find button.Thecursorwillnowautomaticallymovetothecorrectpositioninthe
database.
8. Pressthe Selectbutton.
9. Type 1asthelayerthicknessonrow4inthemainwindow.
10. SelectInsert/Surfacecolumn andpressthe Convection button.
11. SelecttheFunction sheetfromtheConvectionwindow.
HSCChemistry5.0 129
Figure4:TemperatureprofilesforSmelting1.HTRcalculationexample.
HSCChemistry5.0 1211
12.3. DetailedDescriptionoftheProgram
12.3.1 UsingtheFixValueButtonandthelogicbehindit
Figure5:Mainwindowlayout.
1.Headingsarea
Thisistheheadingsareaanditcannotbealtered,exceptforthesecondandthird
rowifthematerialisuserspecified.
2.Calculationarea
Themaininputsareenteredinthisarea,withthethicknessofalayerorenclosure
columnbeingmandatory.Thesurfacearearowisautomaticallycalculatedfromthe
geometryand layerthicknesses.
HSCChemistry5.0 1213
12.3.3 ConductionDatabase
Figure6:ThermalConductiondatabasewindow.
TheconductiondatabasecanbeeditedbyselectingEdit/ConductionDatabasefromthe
menubar.SincethefilesareofXLStypeyoucanalsoeditthemdirectlyfromExcel.Itis
important to notice that when editing or adding new materials it is very important to
follow the same pattern and syntax as the rest of the table. Temperature units can be
enteredineitherKorCandtheprogramwillautomaticallycalculateaccordingly.The
maximumandminimumtemperaturesareavailableincolumnAandarealwaysgivenin
Kelvin. This window is used when selecting the layer material by pressing the
Conduction button.
HSCChemistry5.0 1215
Figure7:ThermalConvectiondatabasewindow,Tablesheet.
TheconvectiondatabasecanbeeditedbyselectingEdit/ConvectionDatabasefromthe
menu bar. Since the files are of XLS type you can also edit them directly from Excel.
TemperatureunitsavailableareKand C.Thedensityisnotakeyrequirement,although
it can be used in order to calculate the other properties. If the thermal expansion
coefficient is not given, the program will assume that the material is an ideal gas and
calculatethecoefficient as b =1/T.The maximum and minimumtemperatures arein
the hidden column A and are always given in Kelvins. This window is used when
selectingthesurfaceorenclosurematerialand pressingthe Convection button.
HSCChemistry5.0 1216
12.3.5 ConvectionDatabase,Functionsheet
Figure8:ThermalConvectiondatabasewindow,Functionsheet.
Thefunctionsheetcanbeusedforspecialcases offorcedconvection.Forexample,the
Moltenmetalselectionisanapproximationofhc basedonapolynomialfunctionofthe
speedofthemoltenmetalinsideasmeltingreactor.Thedatabaseusesafunctionofthe
typehc (v)=Av^a+Bv^b++Gv^gwherevis[m/s].Thecoefficients(AG)arelocated
betweencolumnEandKandtheexponents(ag)inthecells directlyunderneaththese.
This sheet canalsobeusedifthe convectioncoefficient is considered constant:simply
typetheconstant valuein columnEandazerounderneath.This is shown inrows 6,8
and10.
Forawallorcylinderitispossibletospecifyanangleof0or90,whichmeanseithera
horizontaloraverticalobject.WhenselectingtheForcedConvectionoptionbutton,a
textboxforthefluid/gasspeedappearsundertheoptionbuttons.
HSCChemistry5.0 1217
12.3.6 SurfaceRadiationDatabase
Figure9:ThermalRadiationdatabasewindow.
The radiation database can be edited by selecting Edit/Radiation Database from the
menu bar. Since the files are of XLS type you can also edit them directly from Excel.
Temperature units available are K and C. An (n) after the material indicates that the
emissivities are normal emissivities and an (h) indicates that they are hemispherical
emissivities. Note that the emissivity for a material can vary a lot depending on the
surface, for example, a polished surface emits much less radiation than an unpolished
one.ThiswindowisusedwhenselectingthesurfacematerialandpressingtheRadiation
button.
HSCChemistry5.0 1218
12.3.7 GasMixtureRadiationCalculator
Figure10:Thermalradiationfromagasmixture.
Using this window it is possible to calculate the gas emissivity and absorptivity by
specifying the volume fractions (indicated by a red font), pressure, gas temperature
andsurface (wall) temperature. If the object is a cube, cylinder or sphere theoptical
depth is automatically calculated accordingly, although it can still be changed in the
textbox.SeeTable1forexamplesofopticaldepthsforsimplegeometries.
The Calculate button calculates using the specified inputs. The Gas sheet shows the
detailedresultsforthegasemissivityatthegastemperatureandtheWall sheetshowsthe
detailedresultsforthegasabsorptivityatthewalltemperature.
Therearetwowaysofusingtheresultsfromthecalculationinthemainsheet:
SelectatfixedT:Byselectingthisthegastemperature,surfacetemperatureandsurface
emissivitywillbeuseddirectlyinthemainsheet.Thisisafastwayofcalculatingifthe
gasandsurfacetemperaturesareknown.
Selectiterative:Byselectingthistheprogramiteratesemissivityandabsorptivityvalues
intherange0C3000Cforevery50Cstep.Theresultsaretransferredtothemain
sheetforuseiniterativecalculations.Outsidethisrangethevalues willbeextrapolated.
Thisisusefulwhenthe gastemperatureand/orsurfacetemperatureareunknown.
HSCChemistry5.0 1219
12.3.8 ParticleRadiationCalculator
Figure11:Particleradiationwindow.
Using this window it is possible to calculate a particle cloud emissivity when some
detaileddataabouttheparticlesandthegeometryofthecontainerareknown.Theresults
canalsobeusedatafixedToriterativelyasintheGasMixtureRadiationdialog.The
Diagrambuttonshows asimple drawing ofaparticledistributioninthecontainer.The
Gas emissivity at gas temperature and the gas absorptivity at surface temperature are
automaticallytakenfromthe GasMixtureRadiation dialogwhenavailable.
HSCChemistry5.0 1220
12.3.9 TargetCalculations(TargetDialog)
Figure12:TargetDialogwindow.
12.3.10 UserspecifiedDiagrams(DiagramDialog)
Instead of only iterating a certain goal value, the Diagram Dialog may be used for
graphicallyplottingthewholerange.Intheexamplebelow(Figure13),theinfluenceof
the inside water temperature on the heat flow (in this case the radiator heat output), is
shown.Stepbystepthediagrammaybeachievedinthefollowingmanner:
1. Open Radiator.HTRfromthe Hsc5\HeatLossdirectory.
2. SelectDiagram/DiagramDialogfromthemenu.
3. SelectWorksheetcell fromthedropdownboxintheXvalueframe.
4. MovetocellC9inthemainwindow(innertemperature)andpressSetXvalueinthe
dialogbox.
5. Select Heat loss from the dropdown box in the Yvalue frame and press Set Y1
value.
6. SelectCalculateHeatlossfromthedropdownboxinthe Diagram frame.
7. Type90intheMAXtextboxand5intheSTEPtextbox.This means that theinner
temperature willrange from30 Cto 90C calculated every5C.Thedialog box
shouldnowlooksimilartoFigure13.
Figure13:Diagramdialogwindow.Specifyingthediagram.
8. PressDiagram.
9. Inthe DiagramTablewindow,itispossibletospecifypropertiesindetail.However,
ifthisisnotnecessaryjustpressDiagramheretoo.Theresultingdiagramisshown
inFigure14.
HSCChemistry5.0 1222
Figure14:Diagramshowingtheinfluenceoftheinsidetemperatureontheradiatorheatoutput.
Anotherusefuldiagramwouldbetostudytheoptimuminsulationthicknessofacylinder
geometry(forexampleapipe oracylindricaltank).An optimumthickness is available
due to an increasing outside surface area, thus increasing convective and radiative heat
loss.Thefollowingstepbystepinstructionsshowhowthisdiagrammaybecreated:
1.Open Hotwatertank.HTRfromthe Hsc5\HeatLossdirectory.
2. SelectDiagram/DiagramDialogfromthemenu.
3. SelectWorksheetcell fromthedropdownboxinthe Xvalueframe.
4.MovetocellE4inthe mainwindow(urethane insulationthickness)andpressSetX
valueinthedialogbox.
5. Select Heat loss from the dropdown box in the Yvalue frame and press Set Y1
value.
6. SelectCalculateHeatlossfromthedropdownboxinthe Diagram frame.
7.Type0.2intheMINtextbox,0.5intheMAXtextboxand0.02intheSTEPtextbox.
This means that the insulation thickness varies from 0.2 m to 0.5 m and is calculated
every 0.02m.
8. PressDiagram.Noticethatthecalculationtimemaybesignificantonslowcomputers.
9. Press Diagramagain in theDiagram table window. The final diagram should look
similartoFigure15.Thetheoreticaloptimuminsulationthicknessisnowroughly33cm.
HSCChemistry5.0 1223
Figure15:Diagramshowingthetheoreticaloptimumsidewallinsulationthicknessforacylindricalhot
watertank.
12.3.11 Limitations
ThecurrentversionofHeatLosshassomelimitations,someofwhicharelistedbelow.
Themaximumnumberofcalculationsheetsforthewallandthesphereisten,for
thecubefourandthecylinderthree.Itispossibletoinsertupto255 ownsheets.
Inaccuracyincreaseswiththickwallsforthecubeandcylinder,sincetheroofand
bottomlayersarestretchedtooverlapthewalls.Pleaseusesurfacecolumnsonly
if the outer surface temperature is known, see examples Reactor1.HTR and
Reactor2.HTR.
If minimum and/or maximum temperatures are not entered into the database, or
directly on the sheet on rows 17 and/or 18, then the extrapolated heat transfer
coefficients(k,hc andhr)maybeinaccurate.
The convection correlations are not valid for all ranges and the results cannot be
trustedoutsidetheseranges.Detailedspecificationsofthevalidrangesaregivenin
Chapter12.4.
Inaccuracyincreaseswithconvectionforsmallgeometries.
Forced convection cannot be used for internal calculations (gas/liquid to surface)
with a cube, cylinder and sphere, since the correlations are only validfor forced
HSCChemistry5.0 1224
12.4. BasicTheorybehindHeatTransfer
Thischapterexplainsthebasictheoryofheattransferusedbythemodule.Theequations
andtheorygivenareutilizedwithintheprogram.
qx = q'x' A, [1]
T1 - T2
R = , [2]
qx
where T1 and T2 are the temperature points and qx is the heat flow. The thermal
conductanceisthen
1
G = , [3]
R
whereRisthethermalresistance.
Timedependentheatflows,whereqx =q(x,t),andsteadystatenontimedependentheat
flowsqx=q(x)aretwobasicwaysofidentifyingheattransferproblems.Thisprogramis
concerned only with steadystate nontimedependent conditions, which means that the
conditionisvalidforinfinitet.
The thermaldiffusivityisdefinedas
k
a = , [4]
cpr
The kinematicviscosityisdefinedas
m
n = , [5]
r
where m isthedynamicviscosity.
HSCChemistry5.0 1226
ThePrandtlnumberdescribestheratioofthemomentumandthermaldiffusivities.This
isdefinedas
n
Pr = , [6]
a
1 r 1 Dr
b =- - , [7]
r T p r DT
wherepdenotesthederivativeatconstantpressure.
In order to calculate the heat flux, it must be separated into the three main forms:
conduction,convectionandradiation.Amoredetaileddescriptionoftheseformswillbe
giveninthefollowingchapters.
HSCChemistry5.0 1227
12.4.1 Conduction
Heat transfer due to conduction occurs between points inside a material or materials
connected to each other. Thermal conductivity is very dependent on the phase the
material is in and on the temperature of the material/materials. Therefore accurate
calculations withasimplenoniterativeformulaaresometimes impossible.Theuseofa
numericaltechniquesuchasanelementmethodcanbeappliedinordertoachievemore
accurateresults.
Theconductionheatfluxforonedimension(Fourierslaw)iscalculatedas
dT
qx'' = - k , [8]
dx
m
- kn (Tn+1/2 - Tn-1/2)
'' n=1
q =
x m
, [9]
m Dxn
n=1
Inordertobeabletocalculateothergeometries,theshapefactorSinthetotalheatrate
''
equation q =qx A= SkDT isdefinedfordifferentgeometriesaccordingtoequations[10]
to[12].
Foronedimensionalplanewallsandforcubewalls,Sisdefinedas
S = A/ x, [10]
whereAistheunitareaforthelayerandxisthethicknessofthelayer.
Forcylindricalwalls(cylindricalcoordinates),Sisdefinedas
2ph
S = , [11]
ln( xo /xi )
HSCChemistry5.0 1228
Forsphericalwalls(sphericalcoordinates),Sisdefinedas
4pxixo
S= . [12]
xo - xi
HSCChemistry5.0 1229
12.4.2 Convection
Heattransferduetoconvectionoccursbetweentwopoints,whereoneisonasurfaceand
theotherinafluid/gas.Convectioncannotnormallybesolvedmathematicallyexceptfor
some laminar cases. Therefore convection calculations are mostly based on empirical
equationsorcorrelationsandtheuncertainty,orthemarginoferrorinthesecalculations
canbeashighas 20%.Intheliteraturethesecorrelationscanalsovaryandthevalidity
oftheresultismostlylimitedtosomerangeofoneormorethermophysicalpropertiesof
thefluid/gas.Thecorrelationequationsusedintheprogramaretakenfromreferences/1/
and/2/.
Theheatfluxduetoconvectioniscalculatedas
hcL
NuL = , [14]
k
The Nusselt number can be related through empirical data to other properties of the
convectivegas/fluid.Thesepropertiesarenormallytemperatureandpressuredependent,
hence the film temperature, Tf = (Ts+T)/2, should be used when determining these
properties.Thetaskisthensimplytodescribetheproblemasaccuratelyaspossibleand
toselecttheappropriatecorrelation.Usingequation[14]andtheappropriatecorrelation
equationthevalueofhc canbecalculated.Thecorrelationsdependonwhetherforcedor
free(natural)convectionisstudied.Inforcedconvectionthemotionofthefluidisdueto
an external pressure gradient caused by a fan or a pump. In free convection the fluid
motion is due to buoyancy forces only, such as gravitational or centrifugal forces. In
some forced convection cases when the speed of the fluid is low there is a mixture of
forced and free convection called mixed convection, however this is not taken into
accountinthiswork.See3.11Limitationsforamoredetaileddescriptionofwhenmixed
convectionconditionsarenoticeable.
Convectioncanalsobesubdividedintointernalandexternalflow,whichmeansthatthe
fluidiseithercontainedinsideanenclosureorflowingfreelyoutsideageometry.Flowin
pipes is an example of a forced internal flow that has been studied thoroughly. Forced
internalflowismoredifficulttoexaminedueto,forinstance,theinfluenceofcentrifugal
forcesinsidereactors.Theconvectioncoefficientarealsodependentonthewaythefluid
isputintomotion,forexample,differenttypesofpropellersgivedifferentcoefficients.In
some cases simple experimental correlations for the convection coefficient in the form
hc =hc(u)maybeused.Externalflowhasalsobeenstudiedextensivelyandlistedbelow
arethedifferentcorrelations,whichmaybeusedfordifferentcases.Notethatforaplane
walltheinternalconvectionisequivalenttotheexternalconvection.
HSCChemistry5.0 1230
The correlation describing the nature of the flow for free convection is called the
Rayleighnumber andisdefinedaccordingto
gb(Ts - T )L3
RaL = , [15]
na
wheregistheaccelerationduetogravityand bthethermalexpansioncoefficient.
SometimestheGrashofnumber,whichdescribestheratioofbuoyancyforcestoviscous
forces,isusedincorrelationsandisdefinedas
AdescriptionofhowtocalculatethefreeconvectionNusseltnumber,definedinequation
14,fordifferentgeometriesisexplainedbelow.
Wall,verticalposition qv=0/1/:
Surface:
Characteristiclength:L=z
Laminarflow(RaL <109):
0.670Ra1L/ 4
Nu L =0.68+ [17]
[1+ (0.492/Pr) ] 9/16 4/9
Turbulentflow(RaL109):
2
0.387Ra1L/6
Nu L = 0 .825 + 8/27 [18]
[
1+ (0.492 /Pr)9/16 ]
Enclosure:
Characteristiclength:L=thicknessofwallenclosure
H=z(heightofenclosure)
H/L2:
0.29
Pr
Nu L =0.18 RaL [19]
0.2+ Pr
Validwhen:
1<H/L<2
103 <Pr<105
103 <(RaLPr)/(0.2+Pr)
2<H/L<10:
0.28 -1/ 4
Pr H
Nu L =0.22 RaL [20]
0.2+ Pr L
Validwhen:
2<H/L<10
HSCChemistry5.0 1231
H/L10:
-0.3
H
Nu L =0.42Ra1L/ 4 Pr0.012 [21]
L
Validwhen:
10<H/L<40
1<Pr<2104
104 <RaL <107
Wall,horizontalposition qv=90/1/,/2/:
Surface:
Characteristiclength:L=A/P,i.e.thesurfaceareadividedbytheperimeter
Hotuppersurfaceorcoldlowersurface:
Nu L =0.27Ra1L/4 [22]
Colduppersurfaceorhotuppersurface:
RaL <107:
Nu L =0.54Ra1L/ 4 [23]
RaL 107:
Nu L =0.15Ra1L/3 [24]
Enclosure:
Characteristiclength:L=thicknessofwallenclosure
Hotlowersurface:
RaL 1708:
NuL =1 (pureconduction)
RaL >1708:
Nu L =0.069Ra1L/3 Pr0.074 [25]
Validwhen:
3105 <RaL <7109
Coldlowersurface:
NuL =1 (pureconduction)
Cube/1/:
Surface:
Internalflow:
Characteristiclength:L=zi
Nusseltnumberaccordingtoequation[17]or[18]forallwalls
Theflowisassumedtocooldownatthewalls(downflow),thuscreating
acirculatingflowwithanupflowthroughthecenterofthecube.
Notvalidforsmallcubes
Externalflow:
Cubewalls:
Characteristiclength:L=zo
HSCChemistry5.0 1232
Cylinder,vertical qv=0/1/:
Surface:
Internalflow:
Characteristiclength:L=zi
Nusselt number according to equation [17] or [18] for wall, roof and
bottom
Theflowisassumedtocooldownatthewalls(downflow),thuscreating
acirculatingflowwithanupflowthroughthecenterofthecylinder
Notvalidforsmallcylinders
Externalflow:
Cylinderwall:
Characteristiclength:L=zo
Nusseltnumberaccordingtoequation[17]or[18]
Validwhen:
D /L 35/(RaL /Pr)1/4
Roofandbottom:
Characteristiclength:L=A/P=D/4,i.e.thesurfaceareadividedby
theperimeter
Nuwallaccordingtoequation[17]or[18]
NuroofandNubottomaccordingtoequation[22],[23]or[24]
Enclosure:
Approximated asverticalwallenclosure
Cylinder,horizontal qv =90/1/:
Surface:
Internalflow:
Characteristiclength:L=Di
Nusseltnumbercalculatedaccordingtoequation[17]or[18]
Theflowisassumedtocooldownatthewalls(downflow),thuscreating
acirculatingflowwithanupflowthroughthecenterofthecylinder
Notvalidforsmallcylinders
Externalflow:
Cylinderwall:
Characteristiclength:L=Do
HSCChemistry5.0 1233
Rac* <100:
k
hc = [28]
ln(Do / Di ) Di /2
Rac* 100:
1/ 4
Pr
keff =0.386 (Ra ) * 1/ 4
c k [29]
0.861+ Pr
keff
hc = [30]
ln(Do / Di ) Di /2
validwhen:
102 Rac* 107
Sphere/1/:
Surface:
Internalflow:
Characteristiclength:L=zi
Nusseltnumberaccordingtoequation[17]or[18]
Theflowisassumedtocooldownatthewalls(downflow),thuscreating
acirculatingflowwithanupflowthroughthecenterofthesphere
Notvalidforsmallspheres
Externalflow:
Characteristiclength:L=Do
0.589Ra1D/4
NuD = 2 + [31]
[1+ (0.469/Pr) ] 9/16 4/9
Validwhen:
RaD 1011
Pr 0.7
Enclosure:
Characteristiclength:L=thicknessofthesphereenclosure
hccalculateddirectly,notthroughtheNusseltnumber(NuL)
HSCChemistry5.0 1234
Ras* <100:
DiDo
hc = kp [33]
L
Ras* 100:
1/ 4
Pr
keff =0.74 (Ra )
* 1/ 4
s k [34]
0.861+ Pr
D D
hc = keff p i o [35]
L
Validwhen:
102 Ras* 104
HSCChemistry5.0 1235
u L
ReL = [36]
n
whereuisthespeedofthefluid/gas.Notethatthedirectionoftheflowisassumedtobe
horizontalinthisprogramandthatforcedconvectioninsideenclosuresis nottakeninto
consideration.
Wall/1/:
Laminarflow,ReL 5105:
Nu L =0.664Re1L/2 Pr1/3 [37]
Validwhen:
Pr 0.6
Turbulentflow(flowseparation),ReL 5105:
NuL =(0.037Re4L/5- 871)Pr1/3 [38]
Validwhen:
0.6 Pr 60
5105 ReL 108
Cube/1/:
Tangentialhorizontalflowon allsidesassumed
Cube walls:
Characteristiclengthfrontandbackwall:L=xo
Characteristiclengthleftandrightwall:L=yo
Nusseltnumbercalculatedas[37]or[38]
Roofandbottom:
Characteristiclength:L=yo
Nusseltnumbercalculatedas[37]or[38]
Cylinder/1/:
Cylinderwall:
Characteristiclength:L=Do
5/8 4/5
0.62Re1D/ 2 Pr1/3 ReD
Nu D =0.3+ 1+ [39]
[
1+ (0.4/ Pr) ]
2/3 1/4
282000
Validwhen:
ReDPr 0.2
Roofandbottom:
HSCChemistry5.0 1236
Characteristiclength: L = ro p ,i.e.squarewithsamearea
Nusseltnumbercalculatedas[37]or[38]
Sphere/1/,/2/:
Characteristiclength:L=Do
1/4
1/2 2/3 m
0.4
Nu D = 2 + (0.4Re + 0.06Re )Pr
D D , [40]
m s
where m is the dynamic viscosity at the fluid/gas temperature and ms is the
dynamicviscosityatthesurfacetemperature.
validwhen:
0.71 Pr 380
3.5 ReD 7.6104
1.0 (m/ms) 3.2
HSCChemistry5.0 1237
12.4.3 Radiation
Radiation heat transfer can be subdivided into three types: Surface radiation, gas
radiation and combined gas and particle radiation. These are described more closely
below.
Surfaceradiation
Surface radiation means that the heat flux is due to a surface (at temperature Ts) that
radiatestotheoutsideenvironment(attemperatureT),whichisassumedtobeverylarge
comparedtotheradiatingsurface.Atypicalcasecouldbethewalls ofabigroom.The
netheatfluxiscalculatedaccordingto
( )
q' '=es s Ts4 - T4 , [41]
For easier comparison with the convection heat rate, we can define the heat radiation
coefficientas
(
hr =ess (Ts + T ) Ts2 + T2 ) [42]
andbyusingequations[41]and[42]theheatratecanbeexpressedas
which is of the same form as equation [13]. The surface emissivity can be found from
tablesintheliterature.Thenormalemissivity(en)orthehemisphericalortotalemissivity
(eh) may be listed depending on the material. The normal emissivity is the normal
directional emissivity while the hemispherical emissivity is the averaged value for all
solidanglespassingthroughahemispherecenteredoverthesurfaceelement/3/.
HSCChemistry5.0 1238
Theheatfluxduetoradiationfromagastoasurfaceiscalculatedas/4/
e s + 1
q''= s (e gTg4 - a gTs4 ), [44]
2
Theheatradiationcoefficientisnow
wherepisthepressure,Listheopticaldepthandxisthemolarfractionoftheindividual
gasspecies.Notethatthesumoftheradiatinggases canbesmallerthanone, xsp 1,
sincetherestofthemixturecanconsistofnonradiatinggases.
Table1:Examplesofopticaldepthsforsimplegeometries
Thegasabsorptivityatthesurfacetemperaturecanbecalculatedusingthesamemodelif
twotemperaturecorrectionfactorsareintroduced.Thefunctionthenbecomes
1.5 0.5
T Tg
ag =e g (T g ,p,L s ,xH2O ,xCO2,xCO,xNO ,xSO2,xCH4) [47]
T
g Ts
andasseenfromthecorrectionfactors,thesurfacetemperatureTs isnowalsoneededas
aninput.Forfurtherinformationanddetailonthismodelreferences/5/and/6/shouldbe
consulted. The gas radiation calculation code used by HSC is based on code made by
TapioAhokainen.
Combinedgasandparticleradiation
Aparticlecloudemissivitycanbecalculatedwhenthemeansizeoftheparticlesandthe
particlecloudgeometryareknown,accordingto/4/
- e pnpLAp
e c = 1- e , [48]
where ep is the emissivity of a single particle, np is the number of particles per unit
volumeofcloud,ListhethicknessofthecloudandAp istheaveragecrosssectionalarea
oftheparticle.Iftheparticlesinthecloudarenotuniforminsize,thenthesurfacemean
diametercanbeusedaccordingto
n
2
pd 2
s p nd
i=1
i i
A= = n
, [49]
4 4
n
i=1
i
where ds is the surface mean diameter and ni is the number of particles of the same
diameterdi.Thetotalgasandparticlecloudemissivitycanthenbeapproximatedas/7/
e g +c = e g + e c - e ge c , [50]
a g +c = a g + e c - a ge c , [51]
HSCChemistry5.0 1240
where ag isthegasabsorptivitycalculatedaccordingtothemodelbehindequation[47].
es
q''= s (e g+ cTg4 - a g+ cTs4 ) [52]
a g+ c + e s - a g+ ce s
andtheheatradiationcoefficientas
References
1. Incropera,F.P.&DeWitt,D.P.:FundamentalsofHeatandMassTransfer,FourthEdition.John
Wiley&Sons,NewYork,1996.ISBN0471304603.
2. TaineJ.&PetitJP.:HeatTransfer.PrenticeHall,Hempstead,1993.ISBN0133879941.
3. SiegelR.&HowellJ.R.:ThermalRadiationHeatTransfer,SecondEdition.HemispherePublishing
Corporation,1972.ISBN0070573166.
4. ThemelisN.J.:TransportandChemicalRatePhenomena.GordonandBreachScience PublishersSA,
1995.ISBN2884491279.
5. Edwards,D.K.,BalakrishnanA.ThermalRadiationbyCombustionGases.Int.J.HeatMassTransfer,
vol.16,pp.2540,1973.
6. LallemantN.&WeberR.:Acomputationallyefficientprocedureforcalculatinggasradiative
propertiesusingtheexponentialwidebandmodel.Int.J.HeatMassTransfer,vol.39,No.15,pp.
32733286,1996.
7. VDIHeatAtlas.DsseldorfVDIVerlag,1993.
8. HaarL.&GallagherJ.S.&KellG.S.:NBS/NRCSteamTables:ThermodynamicandTransport
PropertiesandComputerProgramsforVaporandLiquidStatesofWaterinSIUnits.Hemisphere
PublishingCorporation,1984. ISBN0891163530.
9. JokilaaksoA.:Virtaustekniikan,lmmnsiirronjaaineensiirronperusteet.TechnicalUniversityof
Helsinki,Otakustantamo,1987.ISBN9516720153.
10. Edwards,D.K.Gasradiationproperties.HeatExhangerDesignHandbook,No.5Physical
Properties.VDIVerlagGmbH,HemispherePublishingCorp.1983(about250p.)
HSCChemistry5.0 131
13. EQUILIBRIUMMODULE
Fig.1. EquilibriumModuleMenu.
TheEquilibriummodulereadsandwritesthefollowingfileformats:
1. *.GEMFileFormat
This file format contains all the data and formatting settings of each definition
sheet as well as the phase names, etc. The equilibrium module always saves this
HSCChemistry5.0 132
The equilibrium solvers GIBBS, Solgasmix and ChemSAGE deliver their results in
ASCIItextfiles.ThePICmodulereads thesefiles and generates graphicsandtables as
describedinChapter13.7.
Therearethreewaysofcreatinganinputfile(*.IGI,*.ISG):
1. Pressthetopbuttoninthemenu,seeFig.1.Thenspecifytheelementswhichare
present in your system, see Fig. 2. The HSCprogram will search for all the
availablespeciesinthe databaseand dividethem,as default,into gas,condensed
andaqueousphases.Theusercantheneditthispreliminaryinputtable.
2. Press the second button of the menu if you already know for sure the possible
substancesandthephasesofthesystem,seeFig.1.
3. PressEditOldInputFileifyoualreadyhaveaninputfilewhichcanbeusedasa
startingfile.Edittheinputtableandsaveitusingadifferentname,seeFig.1.
If you only want to calculatethe equilibriumcompositions withthe existing *.IGIfiles
press Calculate, see Fig. 1. If you want to draw pictures from the existing *.OGI files
madebytheGIBBSsolverpressDraw,seeFig.1.UsingPrintyoucangetapapercopy
ofthe*.IGIand*.OGIfiles.
HSCChemistry5.0 133
13.1 StartingfromdefiningtheElements
Fig.2. Specifyingtheelementsofthesystem.
If you do not know the substances of the system you may also start by specifying its
elements, i.e. a selection of the system components. The elements selected will be
displayed in the Elements Window, see Fig. 2. After pressing Elements in the
EquilibriumMenu,seeFig.1,youcancontinuewiththefollowingsteps:
1. Select one or moreelements:Press buttons ortypethe elements directly intothe
box.TryforexampleNi,C,O,asgiveninFig.2.Donotselecttoomanyelements,
toavoidalargenumberofspecies.Inpractice15elementsisOK
2. Select the form of species from Search Mode in which you are interested. You
mayspecifyupto9carbonlimitsfortheorganicspecies,forexample4,6,7.
3. PressOKand you willseethespecies found,seeFig.3.TheHSCprogram will
searchforallspecies whichcontainoneormoreoftheelementsgiven,firstfrom
theOwndatabaseand,ifnotfoundthere,fromtheMaindatabase.
By decreasingthenumber ofspecies you mayincreasethecalculationspeedand make
thesolutioneasier.Thereforeselectonlythosespecies,whichyouaresuretobeunstable
in your system and press Delete Selected. Be careful, because if you delete the stable
ones the calculated equilibrium results will be incorrect. If you are not sure of some
substancethendonotdeleteit.
HSCChemistry5.0 134
Fig.3. Deletingundesiredspecies.
Iftherearesomeoddspeciesinthelistthenyoucandoubleclickthatformulainthelist
or press the Peep Database button and see the whole data set of the species in the
database. If you want to remove it press Remove in the Database Window. This will
removethespeciesfromthelistbutnotfromthedatabase.
When making firsttimecalculations it maybea good ideatotakeapapercopy ofthe
speciesselectedbypressingPrint.Thenyoucanalsoeasilyaddordeletespeciesinthe
followingwindow,seeFig.4.
The species have been divided into rough reliability classes in the database you may
selectthespeciesavailableinthemostreliableclass1bypressing SelectClass1.
You may also set the sorting order for the species using the option buttons above the
Continuebutton.ThesortingorderwilldeterminetheorderofspeciesintheEquilibrium
Editor,seeFig.4.
HSCChemistry5.0 135
13.2 GivingInputDataforEquilibriumCalculations
Fig.4. Specificationofthespeciesandphasesforthereactionsystem.
HSCChemistry5.0 137
Fig.5. Specificationofthecalculationmode.
HSCChemistry5.0 138
1.Species(substances,elements,ions...)
You may write the names of the species directly into the Species column, without a
preliminarysearchintheElementswindow.Ifyouhavemadethesearchonthebasisof
theelementsyoualreadyhavethespeciesinthe Speciescolumn.
Youcancheckthenamesandthedataofthespeciesbypressingtherightmousebutton
andselecting PeepDatabasefromthepopupmenu.IfyoupresstheInsertbuttonyoucan
collect species for the equilibrium calculations sheet. PressingRemove will remove an
activespeciesfromtheequilibriumcalculations.
You can insert an empty row in the table by selecting Row from the Insert menu or
pressingtherightmousebuttonandselecting InsRow fromthepopupmenu.
Rows can be deleted by selecting Row from the Insert menu or by pressing the right
mousebuttonandthenelecting DelRowfromthepopupmenu.
Youcanchangetheorderofthesubstancesbyinsertinganemptyrowandusingthecopy
pastemethodtoinsertsubstanceinthenewrow.Thedraganddropmethodcanalsobe
used.However,itisextremelyimportanttomovethewholerow,becausethereisalot
ofauxiliarydatainthehiddencolumnsontherightsideofthesheet.
Please keep the Copy Mode selection on in the Edit menu when rearranging species.
This willforcetheprogramtoselect the wholerow. When formattingthecolumns and
cells,turn off the CopyModeselectioninthe Editmenu.
Usethe(l)suffixforaspeciesonlyifyouwanttousethedataofliquidphasesattempe
raturesbelowitsmeltingpoint.Forexample,typeSiO2(l)ifSiO2 ispresent inaliquid
oxidephaseattemperaturesbelowthemeltingpointofpureSiO2.SeeChapter28.2.
2.Phases
The species selected in the previous step must be divided into physically meaningful
phasesasdeterminedbythephaserows.Thisfinallydefinesthechemicalreactionsystem
fortheequilibriumcalculationroutines.Definitionofthephasesisnecessarybecausethe
behavior of a substance in a mixture phase is different from that in pure form. For
example,ifwehaveonemoleofpuremagnesiumat1000C,itsvaporpressureis0.45
bar. However, the magnesium vapor pressure is much smaller if the same amount has
beendissolvedintoanothermetal.
HSCChemistry5.0 139
3.InputTemperaturesoftheSpecies
Inputtemperaturesfortherawmaterialspeciesareessentialonlyintheequilibriumheat
balancecalculations,i.e.ifyouprovidesomeinputamountforaspeciesyoushouldalso
giveitstemperature.Theinputtemperaturedoes notaffecttheequilibriumcomposition.
Youmayselectthetemperatureunitbyselecting CfromtheUnitsmenu,seeFig.4.
HSCChemistry5.0 1310
4.AmountoftheSpecies
In this column you give the input amounts of the raw material species. The most
important thing for the equilibrium composition is to give the correct amounts of
elements tothesystem.Youmaydividetheseamountsbetweenthespeciesasyoulike.If
thecorrect heatbalance is required,you must dividetheamountsof elements exactly
intothesamephasesandinasimilarmannerasintherealphysicalworld.
Youmaychoosebetweenkmolorkg/Nm3 unitsbyselectingmolor kgfromtheUnits
menu. Note that kilograms refer to condensed substances and standard cubic meters
(Nm3)togaseoussubstances,seeFig.4.
5.AmountStepforRawMaterials
Ifyouwishtocalculateseveralsuccessiveequilibriayougiveanincrementalstepforone
or more raw material species. Then the programs automatically calculate several
equilibriabyincreasingtheamountofthisspeciesbythegivenstep.Pleaserememberto
select theIncreaseAmount option,seeFig.5,and givealsothe number ofsteps.The
maximumnumberofsteps whichcanbedrawnis251fortheGIBBSsolverand50for
Solgasmix solver. Some 21 51 steps are usually enough to give smooth curves to the
equilibriumdiagram.
Youmaygivestepvaluesforseveralspeciessimultaneously.Forexample,ifyouwantto
addairtothesystemgiveastepvalueforbothO2(g)andN2(g).Pleasedonotforgetto
specifythenumberofsteps,ifadiagramistobedrawnfromtheresults.
6.ActivityCoefficients(inGibbssolver)
The simple definition of Raoultian activity is the ratio between vapor pressure of the
substance over the solution and vapor pressure of the pure substance at the same
temperature.
a= p(oversolution)/p(pure) [1]
Activity coefficient describes the deviation of a real solution from an ideal mixture.
Activitycoefficientfisdefinedastheratiobetweenactivityaandmolefractionxofthe
speciesinthemixture.
f= a/x [2]
In an ideal solution they are therefore defined as a = x and f = 1. As a default in
GIBBSandSOLGASMIX,theactivitycoefficientofaspeciesinthemixturephases
is always 1. However, if nonideal activity coefficients are available they may be
introducedintherightcolumn.Onlysimplebinaryorternaryexpressionscanbeutilized
directlybytheGIBBSsolverwithinHSC,suchas:
Ln(f) = 8495/T2.653
Ln(f) = 0.69+56.8*X24+5.45*X25
Ln(f) = 3926/T
Ln(f) = 1.21*X7^22.44*X8^2
where:
T = TemperatureinK
X24 = Molefractionofthespecieswitharownumber24inthesheet.
f = Activitycoefficient.
FormulaearewrittenusingthesamesyntaxasinExcel,thedefinednamesTandPare
available for temperature and pressure. Mole fractions are given as cell references to
HSCChemistry5.0 1311
7.Heading
Youmayaddanykindofheadingfortheinputfile,seeFig.5.Themaximumnumberof
charactersallowedintheheadingis80.ThePICpostprocessingprogramautomatically
addstheheadingtothediagrams,seeFigs.11and17.
8.EquilibriumTemperature
Equilibriumwillbecalculatedatthistemperature,andeachequilibriumisisothermaland
thushasaconstanttemperaturethroughoutthesystem,seeFig.5.Youmayalsogivethe
temperaturerangeifyouwishtocalculateseveralsequentialequilibria.Pleaseremember
toalsoselecttheIncreaseTemperatureoptionandgivetheNumberofSteps,seeFig.
5.Severalequilibriaareneededinordertocreategraphicsfromtheresults.
Temperatures in the Species Sheet, Fig. 4, have no effect on the equilibrium
compositions. They are only needed if the reaction enthalpy is necessary to calculate
correctly,seeChapter13.7.1,Fig.10andYAxisselections.
9.Equilibrium Pressure
10.NumberofSteps
Ifyouhavedefinedincrements(steps)forrawmaterialspeciesorspecifiedatemperature
orapressurerangethenyoushouldalsogivetheNumberofStepsrequired,seeFig.5
ThemaximumnumberofstepsinGibbssolveris251andforSolgasmixthemaximum
available is 51. Usually 21 51 steps give quite smooth curves in the equilibrium
diagram. A large number will only give more points to the picture and a longer
calculationtime.
Ifyouhave givenanamount stepforaraw material species,thecalculations shouldbe
made using an increasing species amount. If you have given a temperature or pressure
range,thenthecalculationsshouldbemadebyincreasingthetemperatureorpressure.No
simultaneousincrementsincomposition,temperatureandpressureareallowed.Pleasedo
notforgettoselectthecorrectincreaseoption,seeFig.5
11.CrissCobbleandMixingEntropyofAqueousSpecies
HSCChemistry5.0 1312
12.GIBBS,SOLGASMIXandChemSAGEFileFormat
With this option you can select the input file formats accepted by the GIBBS,
SOLGASMIX3 orChemSAGE4 Gibbsenergyminimizationroutines,Fig.5
IfyousavethefileinGIBBSformatyoucancarryoutthecalculationsinHSCChemistry
with the GIBBSsolver by pressing Gibbs. If you have selected SOLGASMIX format
you can carry out the calculations with a modified SOLGASMIXsolver by pressing
SGM,seeFig.5ChemSAGEisaseparatesoftwareproduct,whichisnotincludedinthe
HSCChemistrypackage.
Note:theactivitycoefficientsandformulaespecifications,seeFig.4arevalidonlyinthe
GIBBSsolver. Nonideal mixtures for SOLGASMIX and ChemSAGE must be defined
separately.
13.PureSubstances(Invariantphases)
The SOLGASMIX and ChemSAGE solvers require information on the number of pure
substancesdefinedinthesystem.Theinternalnameforpuresubstancesintheprograms
istheinvariantphase,referringtothefixedorinvariantcompositionofapuresubstance.
All species in the last substance group can be set to be pure substances with the Pure
SubstancesintheLastPhaseoption,seeFig.5
14.FileSaveandFileOpen
You must first save the input data for the calculations, see Figs. 4 and 5. When this is
done you may activate the equilibrium program and carry out the calculations. With
File/Openyoucanreadanoldinputfileforediting.NotethatfromFilemenuyoucan
easilyselectfiletypesforOpen and Save.Notealsothatthe*.IGI,*.ISGand*.DATfile
types do not save editedphase names andformatting settings.TheEquilibrium module
alwayssavesautomaticallya*.GEMfilewhichcanbeusedtoreturnthesesettings.
15.Exit
IfyouwanttoreturntothepreviousmenupressExit.Remember,however,tosaveyour
inputdatafirst!
HSCChemistry5.0 1313
13.3 AqueousEquilibria
Equilibrium calculations of aqueous solutions can be made in a similar manner as
presented previously for nonelectrolyte solutions. However, some points need special
attention(seealsoChapter28.4forinformationofaqueousspecies):
1. Alwaysremembertoaddwatertotheaqueousphase.Forexample,55.509mol(=
1kg)isagoodselectioniftheamountofionsissome0.01 5moles.
2. Add some charged species (electrons) to the system, for example, by 0.001 mol
OH(a)andthesameamountofH(+a).Besuretomaintaintheelectronicneutrality
ofthesystemifyouwillcarryoutthecalculationswiththeGibbssolver.
3. Ifyouarecalculating,forexample,thedissolutionof1moleofCaCO3 intowater
andyouhavestoichiometricrawmaterialamounts,pleasealsoaddasmallamount
of O2(g) to the gas phase, for example, 1E5 moles. If you have stoichiometric
NaCl in the system please add a minor amount of Cl2(g) to the gas phase (1E5
mol). These tricks help the GIBBS and SOLGASMIX solvers to find the
equilibriumcompositionincasesoffullystoichiometricoverallcompositions.
4. HSCconvertstheentropyvaluesofaqueouscomponentsfromthe molalityscaleto
molefractionscale iftheMixingEntropy option is selected,Fig.33.Therefore,
the entropy values in the input files are not the same as in the HSC database.
Identical results will be achieved if the Raoultian activity coefficients of the
aqueous species are changed to 55.509/X(H2O) which converts the Raoultian
activityscaletotheaqueousactivityscale.
5. ForsomeaqueousspeciesonlyGvaluesareavailableat25C.Thesecanbesaved
inthedatabaseasHvaluesifS=0.Note,however,thatthesecanonlybeusedin
thecalculationsat25C.
6. Youmaychecktheequilibriumresultsbydoingsimpleelementbalancechecksor
comparing the equilibrium constants. For example, you can calculate the
equilibriumconstantforreaction18usingtheReactionEquations optionat25C,
seeFig.12:
Youmayalsocalculatethesameequilibriumconstantfromtheequilibriumresults
oftheGIBBSprogramusingequation10inChapter8.Introduction.Youcanread
the necessary molal concentrations, for example, from the equilibrium results
\HSC3\CaCO3.OGIfile,seeTable1.Thiscalculationshouldgivenearlythesame
resultsastheReactionEquationoption.
[H(+a)]*[OH(a)] 4.735E13*2.159E2
K = = =1.023E14 [6]
[H2O] 55.468/55.509
INPUTAMOUNTEQUILAMOUNTMOLEFRACTACTIVITYACTIVITY
PHASE1: molmolCOEFFICI
N2(g) 1.0000E+001.0000E+0009.683E011.00E+009.683E01
H2O(g) 0.0000E+00 3.2678E0023.164E021.00E+003.164E02
O2(g) 1.0000E051.0000E0059.683E061.00E+009.683E06
CO2(g) 1.0000E031.5986E0131.548E131.00E+001.548E13
HSCChemistry5.0 1314
PHASE2: MOLEFRACT
H2O 5.5500E+01 5.5468E+001 9.994E011.00E+009.994E01
CO3(2a) 0.0000E+004.7507E0078.560E091.00E+008.560E09
C2O4(2a) 0.0000E+008.0560E0610.000E+001.00E+000.000E+00
Ca(+2a) 1.0000E+001.0797E0021.945E041.00E+001.945E04
CaOH(+a) 0.0000E+001.4656E0102.641E121.00E+002.641E12
H(+a) 0.0000E+00 4.7348E013 8.531E151.00E+008.531E15
HCO2(a) 0.0000E+008.1514E0480.000E+001.00E+000.000E+00
HCO3(a) 0.0000E+004.9071E0098.842E111.00E+008.842E11
HO2(a) 0.0000E+001.1549E0202.081E221.00E+002.081E22
OH(a) 2.0000E+00 2.1593E002 3.890E041.00E+003.890E04
Total: 5.8500E+015.5501E+0011.000E+00
Table1.Apartoftheequilibriumresultfile \HSC5\GIBBS\CaCO3.OGI.
HSCChemistry5.0 1315
13.4 GeneralConsiderations
Although equilibrium calculations are easy to carry out with HSC Chemistry, previous
experience and knowledge of the fundamental principles of thermodynamics is also
needed.Otherwise,theprobabilityofmakingseriouserrorsinbasicassumptionsishigh.
Thereareseveralaspects,whichshouldbetakenintoaccount,becausethese may have
considerableeffectsontheresultsandcanalsosaveagreatdealofwork.Forexample:
1. Before any calculations are made, the system components (elements in HSC
Chemistry) and substances must be carefully defined in order to build up all the
species and substances as well as mixture phases which may be stable in the
system. Phase diagrams and solubility data as well as other experimental
observations are often useful when evaluating possible stable substances and
phases.
2. Definingallthephasesforthecalculation,whichmaystabilizeinthesystem,isas
important as the selection of system components. You may also select a large
number ofpotentialphases justtobesure ofthe equilibriumconfiguration,but it
increases the calculation time and may also cause problems in finding the
equilibrium.
3. The definition of mixtures is necessary because the behavior of a substance
(species) in a mixture phase is different from that in the pure form. The
microstructure or activity dataavailable often determines the selection of species
for each mixture. Many alternatives are available even for a single system,
dependingonthesolutionmodelusedforcorrelating thethermochemicaldata.
Note:thesamespeciesmayexistinseveralphasessimultaneouslytheirchemical
characters insuchacaseare essentially controlledbythe mixtureand not bythe
individualspecies.
4. Ifyouexpectasubstancetoexistinthepureformorprecipitatefromamixtureas
a pure substance, define such a species in the system also as a pure (invariant)
phase.This is oftenavalidapproximationalthoughpuresubstances oftencontain
someimpuritiesinrealprocesses.Allspeciesinthelastphasecanbesettobepure
substancesusingthePureSubstancesintheLastPhaseoption,seeFig.5
5. Therawmaterialsmustbegivenintheiractualstate(s,l,g,a)andtemperatureif
the correct enthalpy and entropy values for equilibrium heat balance calculations
arerequired.Thesedonotaffecttheequilibriumcompositions.
6. Gibbs energy minimization routines do not always find the equilibrium
configuration. You may check the results by a known equilibrium coefficient or
mass balance tests. SOLGASMIX provides a note on error in such cases. It is
evident that results are in error if you get random scatter in the curves of the
diagram, see Figs. 11, 17 and 19. You can then try to change species and their
amountsasdescribedinChapter13.2(2.Phases,4.AmountofSpecies).
7. Sometimeswhencalculatingequilibriaincompletelycondensedsystemsitisalso
necessarytoaddsmallamountsofaninertgasasthegasphase,forexample,Ar(g)
orN2(g).Thismakescalculationseasierfortheequilibriumprograms.
8. It may also be necessary to avoid stoichiometric raw material atom ratios by
inserting an additional substance, which does not interfere with the existing
equilibrium. For example, if you have given 1 mol Na and 1 mol Cl as the raw
HSCChemistry5.0 1316
The definition of phases and their species is the crucial step in the equilibrium
calculationsanditmustbedonecarefullybytheuser.Theprogramisabletoremove
unstablephasesandsubstances,butitcannotinventthosestablephasesorspecieswhich
have not been specified by the user. The definition of phases is often a problem,
especiallyifworkingwithanunknownsystem.
Usuallyitiswise,asafirstapproximation,toinsertallgas,liquidandaqueousspeciesin
theirownmixturephases,aswellassuchsubstanceswhichdonotdissolveintothem,for
example,carbon,metals,sulfides,oxides,etc.intheirowninvariantphases(onespecies
perphase),accordingtobasicchemistry.Ifworkingwithaknownsystemitis,ofcourse,
cleartoselectthesamephasecombinationsandstructuralunitsforthesystemasfound
experimentally. These kinds of simplifications make the calculations much easier and
faster.
Theusershouldgivesomeamountforallthecomponents(elements)whichexistinthe
systemforGibbssolver.However,Solgasmixsolverisalsoabletoreducethenumberof
components(elements)automaticallyifacomponentisabsentintherawmaterials.
Itisalsoimportanttounderstandthatduetosimplifications(idealsolutions,purephases,
etc.)thecalculations donotalways givethesameamountsofspeciesandsubstancesas
foundexperimentally.However,thetrendsandtendenciesofthecalculationsareusually
correct.Inmanycases,whendevelopingchemicalprocesses,averyprecisedescriptionof
thesystemis notnecessaryandtheproblemsareoftenmuchsimplerthan,forexample,
calculationofphasediagrams.
For example, the user might only want to know at which temperature Na2SO4 can be
reducedbycoaltoNa2S,orhowmuchoxygenisneededtosulfatizezincsulfide,etc.:
TheNa2SO4.IGIexampleinthe\HSC5\GIBBSdirectoryshowstheeffectoftemperature
on Na2SO4 reduction with coal the same example can be seen also in the HSC color
brochure, page 3. The calculated compositions are not exactly the same as found
experimentally,butfromtheseresultswecaneasilyseethatatleast900Cwillbeneeded
toreducetheNa2SO4toNa2S,whichhasalsobeenverifiedexperimentally.
HSCChemistry5.0 1317
13.5 Limitations
ThepresentversionoftheGIBBSprogramhasnolimitationsastonumbersofsubstances
andphasesbecauseitusesdynamicarrays.Howeverinpractice,3250speciesand15
phasesaresuitablenumberstocarryoutthecalculationswithinareasonabletime.
AlthoughthemaximumnumberofrowsinthespreadsheeteditorusedinFig.4is16384,
the practical maximum number of species is much smaller. The maximum number of
equilibriumpoints,whichcanbedrawnontheEquilibriumdiagram,is251.However,a
muchsmallernumberofequilibriumpointsusuallygivesmoothcurvestothediagram.
ThemodifiedSOLGASMIXprovidedintheHSCpackagehasthefollowinglimitations:
maximumnumberofcomponents 20
maximumnumberofmixtures 31
maximumnumberofpuresubstances(invariantphases) 30
maximumnumberofspeciesinthemixturephases 150
maximumnumberofCprangesininputfiles 7
SGMneglectphasetransitions<298.15K
The most important limitation of the old GIBBS 2.0was that, in some cases, only one
pure substance was allowed. Otherwise the program provided unpredictable results. If
puresubstances(invariantphases)donot,however,containthesameelements,severalof
them are usually accepted. You can avoid this limitation by putting a minor amount of
dissolvingspecies intosuchapuresubstanceanddefiningitasasolutionphase.Inany
case,thenewGIBBS5.0ismuchmorereliableinthesesituations.
Atleastatinyamountforallelementsdefinedinthesystemmustbegivenasinputifyou
usetheGIBBSroutine.Forexample,ifyouhaveanyFecontainingspeciesinthesystem,
youmustalsogivesomeFe totherawmaterials.
SOLGASMIX can handle systems with several pure substances usually without
difficulty. It also can calculate equilibria in systems smaller than originally defined in
HSC.TheSOLGASMIXroutinecanthereforetreat systems with less componentsthan
defined in its inputfileandthusacertainsystem component maybeabsentin theraw
materials.
TheSOLGASMIXprovidedwiththeHSCpackageisamodifiedversionoftheoriginal
codefromtheUniversityofUme,Sweden.Themodificationallowstheuseofgramsas
inputandinthiscasetheresultis givenbothinmolarfractionsandmolesas wellasin
weight percentages and grams. The input file has therefore additional rows for each
systemcomponents(elements).Thelocationsandcontentsoftheserowscanbefoundin
theinputfilelistinginChapter14.Equilibriumsamples.
If you have an aqueous phase with ionic species you should also be sure to maintain
electric neutrality in thesystem,becausetheGIBBS solvertreats electrons inthesame
wayas elements.SOLGASMIXcanusually handleasmall deviationfromthe electron
neutrality.
HSCChemistry5.0 1319
13.6 CalculationRoutines
13.6.1 GIBBSEquilibriumSolver
Fig.6. GIBBSequilibriumsolver.
Equilibrium calculations in the GIBBS routine are made using the Gibbs energy
minimizationmethod.TheGIBBSprogramfindsthemoststablephasecombinationand
seeksthephasecompositionswheretheGibbsenergyofthesystemreachesitsminimum
at a fixed mass balance (a constraint minimization problem), constant pressure and
temperature.Thismethodhasbeendescribedindetailelsewhere5.
OperationInstructions:
1. Select *.IGI file for calculations by pressing File Open, if the file is not already
selected.
2. Usepreviousresultsastheinitialguessoptionwill slightlyspeedupcalculations,
butitisrecommendedtodisablethis option,becausesometimesGIBBSdoes not
givevalidresultswiththisoption.Thedefaultsettingisoff.
3. Fastcalculationsoptionwillspeedupthecalculationsthedefaultvalueison.
4. PressCalculateandwaitfortheAllCalculatedmessage.
5. PressDrawDiagram ifyouwanttheresultsingraphicalform.
6. PressExittoreturntoHSC.
Advancedoptionsbelongtoproperties notsupportedyet,thesemaybeavailableinthe
nextHSCversionastestedandsupportedform.
HSCChemistry5.0 1320
13.6.2 SOLGASMIXEquilibriumSolver
Fig.7. MessageboxoftheSOLGASMIXprogram.
The SOLGASMIX equilibrium routine has been integrated in the HSC Chemistry
package in a different way to the GIBBS routine, because it is not a Windowsbased
program. No own icon is provided, but the program has been connected with the HSC
interfacethroughadirectdatalinkusingfiles.
TheSOLGASMIXroutineusesasimilarGibbsenergyminimizationcalculationmethod
astheGIBBSprogram.Allitsmixturephasescanbedefinedasnonidealmixturesinthe
FACTOR subroutine, but this option is not supported by HSC interface. For further
reference, the original input guide and the thesis of Gunnar Eriksson should be
consulted6.
TheoriginalSOLGASMIXcodehasbeenmodifiedtoaccept gramsinsteadofmolesas
input amounts. The equilibrium composition in the gram mode is given both as a
conventional table with moles and mole fractions and also as grams and weight
percentages. The alterations in the input files due to this modification can be found in
Chapter14.Equilibriumsamples.
SOLGASMIXcanalsobeactivatedintheHSCdirectoryasanindependent,standalone
equilibrium solver. In this case, its input file name created in HSC must be defined as
INPUT.TheequilibriumcalculationsresultswillbestoredwiththefilenameRESULT.
Equilibriacalculatedasafunctionoftemperature,pressureorotherprocessvariablescan
belaterpostprocessedtographicsusingthePICmodulebyHSCChemistry.
13.7 DrawingEquilibriumDiagrams
Fig.8. SelectingthexaxisforanEquilibriumDiagram.
HSCChemistry5.0 1322
Fig.9. SelectingthexaxisforanEquilibriumDiagram.
HSCChemistry5.0 1323
The PIC postprocessor draws diagrams on the basis of the output files of the GIBBS
program (*.OGIfiles), as well as from the SOLGASMIX (*.OSG) and ChemSAGE
(*.RES) result files. These diagrams can be drawn, for example, as a function of a
specifiedreactantamountorequilibriumtemperature.StartthePICprogrambypressing
DrawinFig.6or7andfollowtheseinstructions:
1. Selectthe*.OGIfilefordiagrambypressingFileOpen ifnotyetselected,seeFig.
8.Thisfilecontainstheresultsoftheequilibriumprogram.
2. Selectthespeciesortemperatureforthexaxisbyclickingthedesirediteminthe
listboxusingthemouse.Theprogramshowstherecommendedselectionwithan
arrow,whichisthevariableusedinthecalculations,seeFig.8.
3. PressOK.
4. SelectthespeciesfortheyaxisbykeepingCtrlKeydownandclickingwiththe
mouse.Sometimesit isconvenienttoselect onlythosespecies,whichcontainthe
sameelement,forexampleNi,foronediagram.Thiscaneasilybedoneusingthe
elementlist,seeFig.9.Instandardcasesyoucangetmoreillustrativediagramsby
drawingallgaseousspeciesononediagramandallotherspeciesonanother.
The number of selected species is not limited. All species included in the
calculationcanbeselectedtothediagram.
5. PressOK.
6. Note:YoucanreturntoHSCbypressing Cancel orExit.
HSCChemistry5.0 1324
13.7.1 SelectingDataTypefortheXandYaxis
Fig.10. Selectingdatatypeforthexandyaxis.
In this menu you can select the data type for the diagram. Usually you may accept the
default selections by pressingDiagram, but the output may be modified. For example,
you can draw the composition of a gas phase by clicking Equilibrium Compositions
optionfortheyaxisinsteadofEquilibriumAmount.Allthespeciesinonephasemust
beselectedifcompositionofthisphasewillbedrawntothediagram.
If you are working with an aqueous system you will get a pH option for the X Axis.
ThisoptionwilldrawtheresultsasafunctionofpH.
Bypressing Speciesyouwillreturnto thepreviouswindow,seeFig.9.
Ifyouonlywanttheresultsintabularformat,pressTable.
You can also sort the species in descending order, or leave them in the original order
using SortingOrderofSpeciesoption.Thisselectionwilldeterminetheorderofspecies
intheresultstable.
Temperature and amount units may be selected using the Temperature and Amount
options.
The number of species is not limited, and all the species included in the equilibrium
calculationscanbeselectedtothediagram.
HSCChemistry5.0 1325
13.7.2 ResultGraphics(EquilibriumDiagram)
Fig.11. EquilibriumDiagram.
WhenyoupressDiagramintheAxismenu,Fig.10,thenthePICpostprocessormodule
readstheequilibriumresultsfromthefileanddrawsthediagramusingdefaultscale,font,
line width, etc. selections, see Fig. 11. Note that the program inserts the species labels
automaticallyabovethemaximumpointofthecurveusingthesamecolorforthecurve
andlabel.Ifthelineis notwithintheselectedxandyrangeoritis ontheborderthen
theprogramwillnotdrawthelineorthelabel.
Youcaneditthediagram,Fig.11,byusingseveralformattingoptions:
1. Double click the x or yscale numbers or select XAxis or YAxis from the
Format menuto change,forexample,the minimum and maximum values ofthe
XandYaxis,seeFig.12.Insomecasesitisalsoadvantageoustochangethey
axis to logarithmic scale in order to display the large variations in amounts or
concentrations.
From the same window you can change the number format of x and yaxis
numbersaswellastheirfontsize,color,etc.
2. When the scales are OK, you can relocate any label (species, x and yaxis
heading,etc.)bymouseusingthedraganddropmethod.Firstselectthelabel,keep
HSCChemistry5.0 1326
Fig.12. Changingscales,scalenumberformatandfontsettings.
Fig.13. Changinglabelandlinespecifications.
HSCChemistry5.0 1327
Fig.14. HSCprintdialogforgraphics.
8. Ifyouwanttoseethediagraminatabularformatorusethedataofthediagramin
otherprograms,suchasMSExcel,pressTable.
9. You can copy the diagram to the Clipboard by pressing Copy, and paste the
diagram to other Windows programs. The Copy command uses the Windows
Metafile format, which enables you to resize the diagram in other Windows
applicationsinfullresolution.
10. With Saveyoucansavethediagraminto afileusingtheWindowsMetafileformat.
11. PressAxistoreturntothepreviousAxismenu,Fig10.
12. PressExittoreturntheSpecieswindow,Fig.8,ortoexitthePICprogram.
HSCChemistry5.0 1328
13.7.3 EquilibriumDiagramTable
Fig.15. EquilibriumDiagramTable.
13.8 Nonidealmixture:GaAsExamplewithActivityformulae
Fig.16. Inputdataofanactivityformulaexample.
LOGf(1)=((1X1)^2)*(25503.64.3109*T+5174.7*(14*X1))/(8.31431*T)
LOGf(2)=((X1)^2)*(25503.64.3109*T+5174.7*(34*X1))/(8.31431*T)
HSCChemistry5.0 1330
Fig.17.Resultsasafunctionofarsenicamount.Differentcolorshavebeenusedforspecies,butthesedo
notshowupwellinthisB&Wcopy.
HSCChemistry5.0 1331
13.9 CaCO3Example(Aqueoussolutionexists)
Fig.18. InputdataofexampleCaCO3.IGI.
HSCChemistry5.0 1332
Fig.19.ResultsasafunctionofaddedCO2(g).Differentcolorshavebeenusedforthespecies,butthese
donotshowupwellinthisB&Wcopy.
HSCChemistry5.0 1333
Fig.20. Resultsonlogarithmicscale,thedefaultexampleisshowninFig.19.
HSCChemistry5.0 1334
Fig.21. ResultsasafunctionofpH,thedefaultexampleisshowninFig.19.
HSCChemistry5.0 1335
13.10VaporPressures
HSC Equilibrium module may be used to calculate vapor pressures for substances.
"VaporPressurePbS.igi" sample case is available in your \HSC5\Gibbs folder, see Fig.
22.Itis made for PbSvaporpressurecalculation.This casehas beencreated withthe
sameprocedureasdescribedinChapter13.1.Notethat:
1. NearlyallPbandScontainingspecieshavebeenselectedtothechemicalsystem.
2. Somenitrogenhasbeenaddedtostabilizethegasphase.
3. Some extra sulfur has been added to make the case easier to solve for Gibbs.exe.
Usuallythistrickisnotneededbutitmaybeusedjusttobesafe.
4. Calculationsaremadefrom0to2000C.
5. Selectionof100bartotalpressuremakespossiblecalculationofvaporpressureupto
100bar.Totalpressure1barwouldgivevaporpressuresupto1bar.
6. Theequilibriummodulecalculatestheequilibriumcompositionofthephases.Inthis
case,theequilibriumcompositionofthegasphase.
7. Allgas species havebeenselectedtothe diagraminthespecies dialog,seeFig.9.
DonotselectPbS!
8. "EquilibriumComposition"hasbeenselectedtoYaxisintheAxisdialog,seeFig.
10.
9. ThecalculationresultsareshowninFig.23.ThedefaultYscaleofthediagramis0
100mol%,butishasbeenchangedto02mol%.
10. PbS(g)compositionat1330Cis1mol%.PbS(g)partialpressureisthen0.01,this
meansthatPbS(g)vaporpressureis0.01*100bar=1bar,seeFig.23.
11. The total pressure of PbS is the sum of all the partial pressures of the gas species
formedofPbS,ie.sumof:PbS(g),Pb(g),S2(g),Pb2S2(g),Pb2(g),etc.
HSC5.0cannotcalculatethetotalvaporpressuresautomatically.However,thismaybe
carriedout,forexample,inMSExcel.PresstheTablebuttoninthediagrammenu(see
Fig.23)toseethediagram dataintabularformand usetheCopyPasteprocedureto
transferthisdatatoMSExcel.YoumayalsosavethistableinExcelformat.InExcelyou
may calculate the sum of all the partial pressures, see the VaporPressurePbS.XLS
exampleinyour \HSC5\Gibbsfolder.
HSC database reference Knacke 91 gives 1314 C for PbS boiling point and Janaf 98
gives13201344Cdependingonthemeasurementorcalculationmethod.Thesevalues
are in reasonable agreement with the calculated PbS boiling point of 1327 C in
VaporPressurePbS.XLS.
ThegasphaseabovePbScontainsmainlyPbS(g).However,inmanycasesthegasabove
puresubstancesmaybecomposedofmanydifferentspecies.Inthesecasesitisimportant
tonotethatthetotalvaporpressureisthesumofthepartialpressuresofallthedifferent
gasspeciesformedoftheevaporatingsusbstance(notN2(g)).
HSCChemistry5.0 1336
Fig.22. ChemicalsystemspecificationforPbSvaporpressurecalculations.
HSCChemistry5.0 1337
Fig.23. ResultsofPbSvaporpressurecalculations.
HSCChemistry5.0 141
14. HSCEQUILIBRIUMMODULESAMPLES
ContentsofanInputFileforGIBBSProgram
CopperSmeltingat1300C 'Heading
1 '0=resultstoscreen,1=resultstofile
6403321 'Elements,phases,inv.phases,and
'^numberofcomponents/phase1.,etc.
'N2(g)'2.000.000.000.000.000.00 'stoichiomet.
'O2(g)'0.002.000.000.000.000.00 'matrix
'SO2(g)'0.002.001.000.000.000.00
'*2FeO*SiO2(l) '0.004.000.002.001.000.00
'SiO2(l)'0.002.000.000.001.000.00
'Cu2O(l)'0.001.000.000.000.002.00
'Cu2S'0.000.001.000.000.002.00
'FeS'0.000.001.001.000.000.00
'Cu'0.000.000.000.000.001.00
4
1573.150 'Equilibriumtemperature(K)
0.000000E+001.916105E+023 'H,S,numberoftemperatureintervals
2.919177E+011.121312E030.000000E+004.091976E060.000000E+000.000000E+00
400.0000.000000E+00 '^A,B,C,D,E,F(J/(mol*K))
2.255176E+011.320889E023.129632E+053.389040E060.000000E+000.000000E+00
1600.0000.000000E+00 'Temperature(K),H(J/mol)
3.684012E+012.594080E045.478948E+060.000000E+000.000000E+000.000000E+00
0.000000E+002.051470E+021 'H(J/mol),S(J/(mol*K)),()
3.132312E+013.893657E033.105337E+053.349854E070.000000E+000.000000E+00
2.968130E+052.482210E+023
1.734500E+017.922700E022.646000E+054.563100E050.000000E+000.000000E+00
700.0000.000000E+00
5.164756E+016.297887E032.158751E+061.367747E060.000000E+000.000000E+00
2000.0000.000000E+00
6.665800E+014.478000E031.128930E+078.430000E070.000000E+000.000000E+00
1.458188E+069.729792E+011
2.405800E+020.000000E+000.000000E+000.000000E+000.000000E+000.000000E+00
9.275245E+059.310607E+001
8.577200E+010.000000E+000.000000E+000.000000E+000.000000E+000.000000E+00
1.302203E+059.640145E+011
9.991399E+010.000000E+000.000000E+000.000000E+000.000000E+000.000000E+00
8.117000E+041.161520E+024
4.793800E+019.717300E020.000000E+000.000000E+000.000000E+000.000000E+00
376.0003.619000E+03
1.184100E+025.818200E027.920001E+042.231700E050.000000E+000.000000E+00
720.0001.172000E+03
8.372372E+011.253259E032.450114E+056.180060E070.000000E+000.000000E+00
1400.0001.284500E+04
8.966300E+010.000000E+000.000000E+000.000000E+000.000000E+000.000000E+00
1.016710E+056.032100E+014
2.732690E+027.791840E018.124200E+060.000000E+000.000000E+000.000000E+00
411.0001.665000E+03
7.235800E+010.000000E+000.000000E+000.000000E+000.000000E+000.000000E+00
598.0003.970000E+02
9.458400E+018.366901E021.411000E+054.794300E050.000000E+000.000000E+00
1465.0003.246400E+04
6.255100E+010.000000E+000.000000E+000.000000E+000.000000E+000.000000E+00
0.000000E+003.316400E+012
4.057800E+011.132500E023.284000E+059.800000E060.000000E+000.000000E+00
1358.0001.313800E+04
3.284400E+010.000000E+000.000000E+000.000000E+000.000000E+000.000000E+00
512578 'Rawmaterials,andtheirserialnumbers
298.150298.150298.150298.150298.150
2 '^Temperaturesoftherawmaterials(K)
13 'Numberofequilibriatobecalculated
33322 '2=constantinputamount,3=increases
1.0000000E031.8850000E+00 'Amountofrawmaterial1.,step(mol)
1.0000000E035.0000000E01 'Amountofrawmaterial2.,step(mol)
1.0000000E031.2500000E01 'Amountofrawmaterial5.,step(mol)
1.0000000E+00 'Amountofrawmaterial7.(mol)
2.0000000E+00 'Amountofrawmaterial8.(mol)
10 'Exit
'9=ActivityCoefficientsifvaluesotherthan1
HSCChemistry5.0 142
Case1:HydrationofMagnesiaChromeBricks
Magnesia chrome bricks are widely used as a lining material in pyrometallurgical
applications because of their stability in process conditions. However, at room
temperaturestheyeasilyreactwithmoistureandcrumbleduetohydrationreactions.HSC
software can be used to estimate the lowest temperature, which must be exceeded to
preventsuchreactionsandtospecifythesereactions.
Magnesia chrome bricks contain magnesium, chromium, iron and oxygen. All species,
which contain these elements and hydrogen, can easily be collected to the Equilibrium
modulefromthedatabase.Thefollowingideaswereusedtospecifythesystem(seeFig
2):
Metallicsubstanceswereremoved,astheyarenotneededintheseconditions.
Gasspecies(16)wereinsertedinthegasphase.
Other species (25) were assumed to exist as pure substances (invariant phases),
becauseofthelowtemperatureswheremoltenmixturesdonotexist.
MgO, Cr2O3and Fe2O3 raw materials were added according to their amount in
thebrick:MgO60,Cr2O318andFe2O314kg.
Water gas was added to the gas phase. The amount was set slightly higher than
neededtohydrateallspeciesinthebrick.
Asmallamountofnitrogenwasaddedtothegasphase.
TheresultsofthecalculationsareshowninFig.1.Thisdiagramshowsthathydrationof
the bricks is possible if the temperature of the lining is lower than 270 C. Hydration
damageiscausedonlyduetotheformationofmagnesiumhydroxidethechromiumand
iron do not take part in hydration reactions. Magnesium oxide (periclase) forms the
matrix of the brick, therefore hydration of magnesium oxide crumbles the whole
construction.
HSCChemistry5.0 145
Figure1.Calculationresultsforhydrationofmagnesiachromebrick.
HSCChemistry5.0 146
HydrationofMagnesiaChromiteBrick
FileFormat: GIBBS C:\Hsc5\Gibbs\Ankrom01.igi
PureSubstancesintheLastPhase YES
IncreaseTemperature 101 Steps CrissCobbleOn
TemperatureRange: 1000.000 0.000 C
PressureRange: 1.000 1.000 bar
Case2:AmmoniaSynthesis(byPanuTalonen)
Ammoniawasexpensivetoproducebeforethecurrentprocess,whichuseshighpressure
and iron catalyst, was invented. The synthesis is usually made at temperature of 370
540 C.The effect of pressure on the ammonia formation can easily be evaluated with
HSCEquilibriummodule.Theformationreactioncanbewrittenasfollows:
N2(g)+3H2(g)>2NH3(g)
The number of gas moles decreases inthis reactionandtherefore highpressure maybe
assumed to favor the synthesis. The equilibrium calculation may be carried out as
described in Chapter 13. The chemical system specification and other calculation
parameters are shown in Fig. 2. The calculations are carried out by increasing the
pressurefrom 0.001to1000barataconstanttemperatureof480C.
ThecalculatedresultsareshowninFig.3.Itiseasytoseethatatnormal1barpressureit
is quite impossible to produce high amounts of ammonia. It also seems that synthesis
should be done at the highest possible pressure. However, modern ammonia plants
operateatabout150barpressureforeconomicreasons.Theammoniaiscondensedfrom
thegasmixtureandtheunreactedhydrogenandnitrogenarerecycledbacktothereactor.
Figure3.Calculationresultsforammoniasynthesisexample.
HSCChemistry5.0 148
AmmoniaSynthesisat480C
FileFormat: GIBBS C:\Hsc5\Gibbs\Ammonia.igi
PureSubstancesintheLastPhase YES
IncreasePressure 51 Steps CrissCobbleOn
TemperatureRange: 480.000 480.000 C
PressureRange: 0.001 1000.001 bar
Case3:DecompositionofMgCl2*6H2O
Allcompoundswilldecomposeifthetemperatureishighenough.Especiallysubstances
with combined water will decompose at quite low temperatures. The decomposition
temperatures may be found from many different handbooks, but they may also be
calculated with the HSC Equilibrium module if the basic data is available in the HSC
database. Magnesium chloride forms a MgCl2 *6H2O compound which decomposes
accordingtothereaction:
MgCl2 *6H2O>MgCl2 *4H2O+2H2O(g)
MgCl2 *4H2O>MgCl2 *2H2O+2H2O(g),etc.
The decomposition temperature as well as the decomposition vapor pressure may be
calculated usingthechemicalsystemspecificationshowninFig.5.Theusermustspecify
all possible condensed phases as well as a gas phase. Please note: A) Small nitrogen
amount stabilize the gas phase, B) small Cl2(g) and O2(g) amounts shift the material
balance out from stoichiometric one and C) Mg(g) allows magnesium to enter the gas
phasealso.
Theresultsofthecalculations areshowninFigs.6and7.The decompositionseems to
start at 100 C, see Fig. 6. The vapor composition is drawn in Fig. 7 by selecting the
EquilibriumCompositionoption.Thisdiagramshowsthatthevaporpressureofwateris
0.67 bar at 175 C and 1 bar total pressure. To calculate vapor pressure at higher
temperatures,thetotalpressuremustbeincreased,forexample,to10bar.
DecompositionofMgCl2*6H2Oat1bar
FileFormat: GIBBS C:\Hsc5\Gibbs\Mgcl2.igi
PureSubstancesintheLastPhase YES
IncreaseTemperature 81 Steps CrissCobbleOn
TemperatureRange: 0.000 400.000 C
PressureRange: 1.000 1.000 bar
Figure6.CalculationresultsforMgCl2*6H2Odecompositionexample.
HSCChemistry5.0 1411
Figure7.Vaporcompositionatatotalpressureof1bar.
HSCChemistry5.0 1412
Case4:DecompositionofFeSO4*7H2O(byBenKarlemo)
Thermal decomposition of a chemical compound will sometimes give valuable
information of itsbehaviourinareal chemicalprocess.This evaluation maybe carried
out with the HSC Equilibrium module and with a thermogravimetric analyzer. These
evaluations have been made in this example for FeSO4*7H2O. The chemical system
specifications for the HSC equilibrium module are shown in Fig. 8. Please note (see
Chapter 13.4): A) The small amount of nitrogen stabilizes the gas phase, B) the small
amount1E5kmolofO2(g)shiftsthematerialbalanceawayfromthestoichiometricone,
C)Fe(g)allowsirontoenterthegasphasealso,andD)Solgasmixroutinehasbeenused.
TheresultsareshowninFig.9.
The hydrates gradually decompose at 50 to 200 C and sulfates at 400 to 650 C.
Hematitewillreducetomagnetiteat1250C.Theseresultsmaybeusedtoexplainthe
experimentalthermogravimetricresultsshowninFig.10.TheTGcurveshowstheactual
weightchangeandtheDSCcurveshowstheenthalpychangecomparedtothereference
test.
DecompositionofFeSO4*7H2Oat1bar
FileFormat: GIBBS C:\Hsc5\Gibbs\Feso4.igi
PureSubstancesintheLastPhase YES
IncreaseTemperature 100 Steps CrissCobbleOn
TemperatureRange: 0.000 1600.038 C
PressureRange: 1.000 1.000 bar
Figure9. TheresultofthecalculateddecompositionofFeSO4*7H2O.
ThetheoreticalandexperimentalweightchangecurvesarecomparedinFig.11,whichis
calculated inMSExcel.Bothcurves are in quite goodcorrelation with each other.The
decomposition occurs at slightlyhighertemperatures inthe experimentalresultsthan in
thecalculatedones,butthismaybeexplainedbysomekineticeffects.Thefinalweightof
the sample was nearly the same in the experimental and theoretical results at high
temperatures. The decomposition reactions may also be verified by comparing the
analyzedandthecalculatedgascompositionwitheachother.
HSCChemistry5.0 1414
Figure10.ResultsofFeSO4 *7H2OrunonNETSCHTGDSCanalyzerundernitrogenatmosphere
showingTGandDSCcurves.Heatingratewas5C/min.
HSCChemistry5.0 1415
Case5:AlkalicirculationinBlastFurnace(byRikuSarkkinen)
Alkalimetalstendtoenrichintheironblastfurnace.Thealkalicontentinrawmaterials
(pellets, sinter and coke) is not so high, but they evaporate at the bottom part of the
furnace(~1500C)anddonotexitwiththeproducts(slag,iron)easily.Neitherdothey
exitwiththeprocessgas,whichgoesupward,becausethetemperatureisquitelowatthe
topofthefurnace(~100C).ThisproblemmaybeevaluatedwiththeHSCEquilibrium
module.
The chemical system specification is shown in Fig. 13. The raw material amounts are
basedonthefollowingassumptions:Cokeashanalysis(maincomponents):SiO2 53,CaO
3,MgO2,andAl2O3 27wt%.Processgasisformedbyairreactionwithcoke,themain
componentsinthegasphaseareCO(g),CO2(g)andN2(g).ThealkalielementsareKand
Na. The calculations are carried out as described in Chapter 13 by increasing the
temperaturefrom500to2000C.Ironhasnotbeentakenintoaccountbecausethealkali
circulation occurs above the liquid iron zone. Equilibrium calculations were made as
describedinChapter13.
ThecalculationresultsareshowninFig.12.Athightemperaturesalmostallthesodium
and most of the potassium seems to be in elemental form in the gas phase. These gas
speciesflow with the mainprocessgases upward where cold charge materials decrease
the temperature and alkalis react with the slag components. The reaction products are
mainly sodium and potassium carbonates, sodium silicates and potassium alumina
silicates.Thesesolidcompoundsflowdownwardswiththeblastfurnacechargematerials
tothe hightemperaturezoneat thebottom ofthefurnace,wherethealkalicomponents
vaporizeagain,whichleadstothealkalicirculation.
HSCChemistry5.0 1417
Figure12.Equilibriumresultsofalkalisandslagcomponentsasafunctionoftemperature.
HSCChemistry5.0 1418
Figure13. SpecificationofphasesandspeciesintheBlastFurnaceexample.
HSCChemistry5.0 151
15. CELLEQUILIBRIA
Fig.1. InputdatafortheCellprogram.
BriefInstructions:
IntheCellEquilibriumwindowyoucangivetheinputdatarequiredforthecalculations
and save the input data for the CELL program. You can see examples of the data by
selecting Open fromtheFilemenu.Pleasedothisbeforemakingyourowninputfilesfor
CELL.
1. Youcanmoveinthespreadsheetusingthemouseorarrowkeys.
HSCChemistry5.0 152
Youmustfirstdefinethespeciesnumbers,whichreactattheanodeorcathode,as
wellastheiroxidationnumbers.IntheexampleoxygengasO2(g)isdecomposed
on a cathode, its oxidation number is 2 * (2) = 4. The oxidation number of an
electronisalways1.
Thedischargeamountdefinestheamount ofelectricity,whichistransferredfrom
anode to cathode in the equilibrium. By changing the discharge amount you can
calculatepotentialsandcompositionsatdifferentdischargestatesofthecell.Note:
Q =AmountofelectricityinAs(charge)
F =Faraday'sconstant,96487As/mol
13. Whenyouaresatisfiedwiththedata,saveitbypressing Save.
14. AftersavingyoucangototheCELLprogrambypressing Cell.
HSCChemistry5.0 153
AdditionalInformation:
YoucanobtainmoreinformationontheCELLprogramandthethermodynamicsinthe
backgroundusing Help aswellasfromtheoriginalpublicationsoftheauthors7,8.
15.1 CellModule
Fig.2. Cellprogram.
Runningtheprogram:
1. Openinputdatafilewiththeoption"File|Open..."
2. Select the option "Run|Calculate". The program will then calculate the
equilibrium state. If you want to change the number of iterations, choose the
"Run|Maximum rounds" option which gives the new number of iterations. The
defaultvalueis200.Youmayinterruptthecalculationbypressinganykeyorthe
mousebutton.
HSCChemistry5.0 154
16. FORMULAWEIGHTS
Fig.1. FormulaWeights.
This simplest calculation option of HSC Chemistry is a versatile routine for calculating
formula weights. As input, it accepts almost any form of chemical formula using
conventionalorganicorinorganicexpressions.Typicalentriesmaybe:
NaBO3*4H2O,H2Sn(OH)6,(C2H5)2O,Fe0.998O,etc.
You can collect several results on the sheet. Clear will clear the whole sheet. You can
print the results using Print. The Formula Weight option uses the same routine for
calculatingtheformulaweightsandelementalcompositionasallothercalculationoptions
intheHSC.Thereforeyoucantestthecorrectformulaformatsinthisoption.Copywill
copytheresultsintotheclipboard.Notethatyoucancopyandpastecellrangesalso.
Youcanselect molorkgunitsforcolumnEaswellasthetotalamountfromtheboxat
toprightcorneroftheform.Bypressingmouserightbuttonyoucan,forexample,modify
numberformat.
Limitations:
1. Superscriptsandsubscriptsarenotallowed.
2. Innerparenthesesarenotallowed,forexample:
H2(Sn(OH)6)isnotavalidformula.UseH2Sn(OH)6instead.
3. Lastparenthesesarealwaysreservedforspeciestypedeclarations,forexample:
As(g) Arsenicgas C Carbon
O2(g) Oxygengas C(D) Diamond
Fe(l) Liquidiron FeS2 Pyrite
OH(a) AqueousOHion FeS2(M) Marcasite
HSCChemistry5.0 162
17. Eh pHDIAGRAMS(Pourbaixdiagrams)
EhpHdiagramsshowthethermodynamicstabilityareasofdifferentspeciesin an aqueous
solution. Stability areas are presented as a function of pH and electrochemical potential
scales.Usuallytheupperandlowerstabilitylimitsofwaterarealsoshowninthediagrams
with dotted lines. Traditionally these diagrams have been taken from different
handbooks12.However,inmosthandbooksthesediagramsareavailableonlyforalimited
numberoftemperatures,concentrationsandelementcombinations.
The EhpH module of HSC Chemistry allows the construction of diagrams in a highly
flexible and fast way, because the user can draw the diagrams exactly at the selected
temperatureandconcentration.
TheEhpHmoduleisbasedonSTABCALStabilityCalculationsforAqueousSystems
developedbyH.H.Haung,atMontanaTech.,USA9,10.
17.1 Introduction
EhpHdiagramsarealsoknownasPourbaixDiagramsaccordingtoauthorofthefamous
Pourbaix diagram handbook12. The most simple type of these diagrams is based on a
chemicalsystemconsistingofoneelementandwatersolution,forexample,theMnH2O
system.Thesystemcancontainseveraltypesofspecies,suchasdissolvedions,condensed
oxides, hydroxides, oxides, etc. The EhpHdiagram shows the stability areas of these
speciesintheredoxpotentialpHcoordinates.
UsuallytheredoxpotentialaxisisbasedontheStandartHydrogenElectrode(SHE)scale
designated Eh, but other scales can also be used. The redox potential of the system
represents its ability to change electrons. The system tends to remove electrons from the
species whenthepotentialishigh(Eh>0).Theseconditions mayexistneartheanodein
theelectrochemicalcell,butcanalsobegeneratedwithsomeoxidizingagents(Cu+H2O2
=CuO+H2O).Inreducingconditions,whenpotentialislow(Eh<0),thesystemisable
to supply electrons to the species, for example, with a cathode electrode or with some
reducingagents.
ThepHofthesystemdescribesitsabilitytosupplyprotons(H(+a))tothespecies.Inacid
conditions(pH<7)theconcentrationoftheprotonsishighandincausticconditions(pH>
7)theconcentrationofprotonsislow.
Usuallyalargeamountofdifferentspeciesexistsimultaneouslyintheaqueousmixturesin
fixed EhpHconditions. The Pourbaix diagrams simplify this situation a lot by showing
onlythepredominantspecies whichcontentishighestineachstabilityareas.Thelinesin
the diagrams represent theEhpHconditions wherethecontent oftheadjacent speciesis
thesameintheequilibriumstate.However,thesespeciesalwaysexistinsmallamountson
bothsidesoftheselinesandmayhaveaneffectonpracticalapplications.
Thelinesinthediagramscanalsoberepresentedwithchemicalreactionequations.These
reactionsmaybedividedintothreegroupsaccordingtoreactiontypes:
1. Horizontal lines. These lines represent reactions that are involved with electrons,
but areindependent ofpH. NeitherH(+a)ions norOH(a)ions participatetothese
reactions.
2. Diagonallineswitheitherpositiveornegativeslope.Theselinesrepresentreactions
thatareinvolvedwithbothelectronsandH(+a)andOH(a)ions.
HSCChemistry5.0 172
17.2 ChemicalSystemSpecifications
TheEpHDiagramselectionintheHSCmainmenuwillshowtheEpHform,Fig.1.The
usermustspecifythechemicalsystem,whichwillbeusedtocalculatethediagraminthis
form. Assume that system contains Cu, S and H2O. The following steps should be
specifiedinordertocreatethediagram:
1. SelectMainElement:Selectoneelementfromthelist.Thiselementwillbeusedas
the main element in the first diagram, i.e. all species, which are shown in the
diagram, will contain this element. The user can easily change the main element
selectionlateroninthediagramform,seeFig.3.TheCuhasbeenselectedinthis
example,butS maybeselectedtomainelementbypressingSbuttoninFig.3.
2. SelectOtherElements:Select otherelementstothesystem.Upto7elementscan
beselectedbutitisrecommendedtouseless,becauselargeamountofelementsand
speciesincreasecalculationtimeandcouldcausesomeotherproblems.Shasbeen
selectedinthis example.Note:It isnotnecessarytoselectHandO,becausethese
arealwaysautomaticallyincluded.
3. SearchMode:This selectionspecifies thetype ofspecies,which willbecollected
fromthedatabase.Itisrecommendedtousedefaultselections.Note:Condensed=
HSCChemistry5.0 174
17.3 Eh pHDiagramMenu
TheEpHdiagrammenushowsasummaryofthechemicalsystemspecificationsaswellas
selecteddefault valuesforthediagram.Thefastestwaytogoforwardistoacceptallthe
default values and press Diagram for simple EpH diagrams or Combine for combined
diagrams.Usuallyatthebegining,thereisnoneedformodificationstothedefaultvalues.
However, it is important to understand the meaning of these settings because they may
havestrongeffectonthediagram.Thedetailsofthediagrammenuoptionsareexplainedin
thefollowingparagraphs.
1.FileOpen
TheEpHmodulecanalsobeusedasanindependentapplication,inthesecasesthedatafor
the diagram may be read from *.IEP files by pressing File Open. Normally the system
specifications are automatically transferred from the system specification sheet to the
diagrammenu,Fig.2.
HSCChemistry5.0 176
2.Speciesand DGdataworkbook
The selected species and calculated DGdata based on the enthalpy, entropy and heat
capacity values of the HSC database is shown on the Species sheet of the diagram
workbook, Fig. 2. The species are arranged according to elements and species type. The
usercan modifythe DGdataaswellas add orremovespeciesinthis sheet.TheSpecies
sheetmakesitpossibletousedataandspecieswhichcannotbefoundintheHSCdatabase,
forexample:
A. ThepublishedPourbaixdiagramsareoftenbasedonDGdatawhichisgiveninthe
originalpapers.This DGdatacanbeusedintheSpeciessheettoreplacethedefault
valuesbasedontheHSCdatabaseifnecessary.Notethatthese DGvalues canalso
becalculatedfromthestandardpotentialvaluesusingequation1
DG= - n F E , [1]
where n is the charge transferred in the cell reaction, F is the Faraday constant
(23045 cal/(V*mol)) and E is the standard electrode potential in volts. Note: Give
DGdatafortheselectedtemperatures,usuallythesevaluesareonlyavailableat25
C.
B. Sometimes all necessary species are not available in the HSC database. These
missingspeciescanbeaddedtothechemicalsystemspecificationiftheuserhasthe
DGvalues or chemical potential data for these species. The new species may be
added by inserting empty row with Insert Row selection and typing formula and
DGvaluestothisrow.
Thenewspeciescanbeinsertedintoanylocation,butitisrecommendedtoaddthe
sametypeofspeciessequentially,becauseitmakesthelisteasiertoreadandupdate.
Note:A)Donotinsertanynewelements,newelementsmustbeaddedintheEpH
elementselectionwindow,Fig.1.B)Donotcreateemptyrows.
C. Insomecasesitisnecessarytoremovecertainspeciesfromthesystem,e.g.ifsome
kinetic barriers are found to slow down the reaction rate in the experiments. Such
speciescanberemovedby DeleteRowselection.
The Labels and Lines sheets are in the programs internal use and it is not necessary to
make any modifications to these sheets. The Labels sheet contains format data for the
labels such as text, area number, coordinates, font name and properties, and labels
visibilityandorientation.TheLinessheetcontainsformatdataoftheequilibriumlinesof
the diagram: Species names, line area numbers, line endpoint coordinates, and line
properties.
3.Temperature
The Pourbaixdiagrams are drawn at a constant temperature. The user must select one
temperatureforthe diagram fromthe list oftemperatures,Fig.2.Theactualtemperature
values can only be changed from the system specification form, Fig. 1. No temperature
selectionisneededherefortheCombineddiagrams.
HSCChemistry5.0 177
The default DGvalues in the Species sheet in columns 2 5 are calculated at the given
temperatures.The DGvaluesatcolumn2arecalculatedusingthefirsttemperature,column
2usingthesecondtemperature,etc.
4.Otherparameters
The default values for DielectricConstant andDG ofH2Oareautomatically calculated
on the basis of the selected temperature and pressure. The calculation of Dielectric
Constant is based on experimental values15 and water vapor pressure16, which are valid
from0to373C,andfrom1to5000bar.OutsidethisrangetheDielectricConstantwillbe
extrapolated.
The Ion Strength and Correction Factor constants are automatically calculated by the
programandusuallytheydonotneedtobemodifiedbytheuser.
5.PotentialandpHscaleranges
Theuser maychangethe default range (MaxEhandMinEh)forthepotentialscaleas
well as the range of pH scale (Max pH and Min pH). The scale settings can also be
changed by clicking the x or yaxis on the diagram form. The minimum difference
betweenMinandMaxvaluesis0.2andthereisnoupperlimitforthedifference.
6.MolalityandPressure
Thediagramsarecalculatedusingconstantmolalities(concentrations)foralltheelements.
Thedefault values maybechangedinthetableinthebottomrightcornerofthediagram
menu,seeFig.2.Molalityvaluesaregiveninmol/kgH2Ounits.
ThetotalpressureofthesystemisalsogivenintheMolalitytable.TheEpHmoduleuses
maximumvaluegiveninthePressurecolumnasthechemicalsystemtotalpressure.Itis
not possible to select a smaller pressure value than water vapor pressure at the selected
temperature.Inotherwords,thetotalpressuremustalwaysbebiggerthanthewatervapor
pressureattheselectedtemperature.Thedefaultvalueforthepressureis1bar.
7.ShowPredominanceAreasofIons
TheShowPredominanceAreasofIonsselectioncausestheEpHmoduletocalculate
two diagrams for the same system. The first one is a normal EhpHdiagram with all
species,andthesecondoneisthepredominancediagramwithonlyaqueousspecies.Both
diagramsaredrawnintothesamefigurethefirstdiagraminblackandthesecondonein
blue.ThisoptionisrecommendedforuseonlywithnormalEhpHdiagrams(seeChapter
17.4).
8.DiagramandCombineButtons
Diagram starts the calculations and automatically shows the normal Pourbaixdiagram.
Combinewillshowstillonemoremenuforcombineddiagramspecifications,seeChapter
17.5formoredetails.
9.Otheroptions
TheactiveworksheetmaybeprintedusingFilePrintselection.Youcanmakechangesto
thesettingusingnormalPageSetup,PrintSetup,andPreviewdialogsintheFilemenu.
TheFilePrintAll selectionprintsallthreesheets.
TheEdit Copy selection provides normal copy and paste operations, theEdit Copy All
selectioncopiesallthreesheetstotheclipboard.Theworksheetlayoutmaybechangedby
HSCChemistry5.0 178
10.ExampleofNormalPourbaixDiagrams(CuSH2Osystem)
AcceptallthedefaultvaluesandpressDiagram.ContinuefromChapter17.4.
17.4 NormalEhpHDiagrams
ThecalculatedEhpHdiagramsareshowninFig.3.IntheDiagramwindowitispossible,
for example,to modifythe layout andformat ofthe diagram.Thesolidblacklines show
the stability areas of the most stable species on the pH and Ehscales. The dotted cyan
lines show the upper and lower stability areas of water, see Chapter 17.1. The stability
areas of ions are shown with blue dotted lines if the Show Predominance Areas of
Ionsoptionhasbeenselected,seeFig.2.
1.MainElements
TheEhpHdiagramsshowonlythosespecies,whichcontaintheselectedmainelement.
The default main element (Cu) mustbeselected inthesystemspecificationform,Fig.1.
However,theactivemainelementcaneasilybechangedinthediagramformbypressing
Elementbuttonsontheupperrightsideofthediagramform,seeFig.3fortheCuSH2O
diagram and Fig. 4 for the SCuH2Odiagram. Usually it is useful to check all the
diagramswithdifferentmainelementstogetabetterideaoftheequilibria.
2.LabelsandLines
TheEpHmodule locates thearealabels automaticallyonthewidestpoint ofthestability
areas.Youcaneasilyrelocatethelabelsbydraggingwiththemousecursorifnecessary.
Thetextofthelabelsandheadingscanbemodifiedbyinsertingthecursorintothecorrect
locationwithinthetextrowandthenbystartingtotype.YoucanstarttheLabelFormat
dialogbydoubleclickingthelabelorbytheFormatLabelselection.Thisdialogmakesit
possibletochangetextandlinesproperties,suchasfont,type,size,linewidth,color,etc.
You can insert new labels using the Insert Label selection. You can delete these labels
using theDelete Labelselection. Note that you cannot delete the default labels, but you
canhidetheselabelsbyremovingalltextfromthelabel.
HSCChemistry5.0 179
Fig.3.EhpHdiagramofCuSH2Osystemat25CusingCuasthemainelement.ThemolalitiesofCu
andSare1mol/kgH2O.
HSCChemistry5.0 1710
The Format H2O Stability Lines selection opens the format dialog, which makes it
possibletomodifythewaterstabilitylinesformatsandproperties.This dialogcannotbe
openedbydoubleclickingthewaterstabilitylines.
HSCChemistry5.0 1711
3.Scales
Fig.5. Menuforformattingyaxis,notethedifferentpotentialscaleoptions.
Thescaleformatdialogcanbeopenedbydoubleclickingtheaxisnumbers,seeFig.3,or
by the Format Scale selection, see Fig. 5. A special feature of the EhpHdiagram scale
dialog is thescaleunitoption.Youcanselect betweentheHydrogen,SaturatedCalomel
andAg/AgClscales.ThedefaultscaleisHydrogen,whichisusedinthecalculations.The
differencebetweentheMinandMaxvaluesmustbeatleast0.2units.
HSCChemistry5.0 1712
4.Printing
Fig.6. EpHDiagramPrintDialog.
You may open the Print dialog by pressing Print BW or Print Col or by selecting File
Print Special, see Fig. 3. This dialog allows the user to select margins and size of the
diagramaswellastheorientation,seeFig.6.Ifyouhaveacolorprinteryoucanselectthe
Coloroption.Printwillprintahardcopyofthediagram.
5.OtherOptions
The default diagram font dialog can be opened by pressing Font or with the Format
DefaultFontselectionfromthemenu.Thisdialogallowstheusertosetthedefaultfont,
whichissavedintoHSC.INIfile.
CopyaswellasEditCopyselectionwillcopythediagramintotheWindowsClipboard,
whichmakesitpossibletopastethediagramintootherWindowsapplicationsinWindows
Metafileformat.EditCopyAllselection willalso copythe molalityandpressurevalues
intothediagram.EditCopySpecial willcopyscaleddiagrams.
TheSaveorFileSaveselectionwillsavetheEhpHdiagraminWindowsMetafileformat
(*.WMF).ThesediagramscannotbereadbacktoHSC.
TheMenuorthe FileExit selection will reactivatetheDiagramMenuform,seeFig.3.
The Help selectionwillopentheHSCHelpdialog.
6.Example:CuSH2OSystem
TheCuSandSCuH2OdiagramsareshowninFigs.3and4.Thesediagramsmaygivea
lotofvaluableinformation.Forexample,thedissolutionbehaviorofcoppercaneasilybe
estimatedfromFig.3.Itiseasytoseethatinneutralandcausticsolutionsmetalliccopper
is stable nearzeropotential values.It will form oxides inanode conditions (Eh>0)and
sulfides in cathode conditions (Eh < 0). However, it will dissolve as Cu(+2a) in acid
conditionsatanode(Eh>0)andprecipitateonacathode(Eh<0)inmetallicform.
HSCChemistry5.0 1713
17.5 SpecificationsforCombinedDiagrams
The normalEhpHdiagrams showthe effect ofpHandpotentialonthestabilityareas of
different species.TheCombine option,seeFig.2, enables youto seethe effect of other
variables on the same diagram. Basically, these combined diagrams are made by
superimposing up to four normal diagrams together. These separate diagrams can be
calculatedusingthemainelement,temperature,molality(concentration)orpressureas
avariable.ThetraditionalPourbaixdiagrams12 usuallyshowtheeffectofmolalityonthe
same diagram.Thesecombined diagrams make it easytocomparethe effect ofthe main
processvariablesonthechemicalsystembehavior.
TheCombineoptiononlydrawscombineddiagramsforthesamechemicalsystem.Other
limitationsarethesameasforthenormalEhpHdiagrams.Notethattheusermayselect
differentvariablestobeusedsimultaneouslyinthesamecombineddiagram.However,itis
stronglyrecommendedtouseonlyonevariable,suchasmolalityortemperature,because
multivariable combined diagrams will be difficult to read. The combined diagram may
become extremely complicated if more than two different main elements are selected in
onediagram.
1.ChemicalSystemSpecifications
The chemical system specifications for the combined diagrams are made exactly in the
samemannerasfornormaldiagrams,seeChapter17.2.TheFeSH2Osystemisusedhere
as an example when the combined diagrams approach and properties are described. The
selectionsareshowninFig.7.Theavailabletemperaturesmustbespecifiedinthesystem
specificationsform,Fig1.
2.EhpHDiagramMenu
The modification of the chemical system as well as other settings are made inDiagram
Menu in the same way as for the normal diagrams described in Chapter 17.3. In this
example no changes were made into the default selections. The only action was to press
Combine,seeFig.2.
3.CombineMenu
The variable, which is used to draw the combined diagrams, is selected in the Combine
Menu,seeFig.8.Theuser mayselect uptofourdatasetstobeused inthe calculations
withtheSelectoption.Eachdatasetspecifiessettingsforonenormaldiagram,whichwill
be includedinthecombineddiagram.
Thebasicideaisthatallvaluesmustoriginallybethesameineachdataset.ResetValues
willrestoretheoriginalvalues.Theusermaythengivedifferentvaluesforonevariablein
eachdataset.ThemolalityofironhasbeenselectedforthevariableinFig.8bygivingthe
value1.00E+00forDataSet1,1.00E03forDataSet2and1.00E06forDataSet3.The
Select option and Line Text are usually automatically selected whenever a data set is
modified.
AcombineddiagramcanbedrawnbypressingDiagramwhenthevariablevaluesforthe
datasetshavebeengiven.
Different variables can be used simultaneously in each data set. However, it is
recommendedtouseonlyonevariablebecausemultivariablediagramsaredifficulttoread.
Note also that only the Hydrogen electrode potential is available if more than one
temperatureisusedforthecombinedEhpHdiagram.
HSCChemistry5.0 1714
Fig.7. SpecificationofanFeSH2OsystemforanEhpHdiagram.
HSCChemistry5.0 1715
Fig.8. SpecificationofacombineddiagramlayoutforanFeSH2Osystem.
HSCChemistry5.0 1716
Thefollowing LineTextoptionsmaybeused:
MainElement
Temperature:(allnumbersroundedtointegers)
MolalityandPressure:Onlythelastthreecharactersofthenumbersareused.For
example,1.00E03isshortened to03.
DataSetNumber
None:Linelabelsarenotused.
TheSourceoptionreferstotheelementwhichisusedfortheMolalityandPressureline
labels.It is automaticallyselectedaccordingtothelastedited variable.Howevertheuser
canchangethis beforepressingDiagram.Thelinelabelformat dialogcanbeopenedby
pressing LineTextFont,seeFig.8.
TheEditCopyandPasteselectionsmaybeusedtoedittheMolalityandPressurevalues.
Table shows all the calculation results, which are used to draw the final diagram, see
Chapter17.7.
Diagram calculatesalltheselecteddatasetsandshowsthecombineddiagram,seeChapter
17.6. ExitreturnsthecontroltotheDiagramMenuform,Fig.1.
4.BriefInstructionstocreateaCombinedEhpHdiagram
1. SpecifychemicalsystemandpressEpH,seeFig.7.
2. AcceptdefaultsettingsandpressCombine,seeFig.2.
3. Givevaluesforonevariable,forexample,molality1.00E+00forDataSet1,1.00E
03 for Data Set 2 and 1.00E06 for Data Set 3. Press Diagram to calculate the
combineddiagram,seeFig.8andFig.9.
17.6 CombinedEhpHDiagrams
The calculation basis and appearance of the combined diagrams is the same as for the
normal EhpHdiagrams discussed in previous chapters. The combined diagrams are
reducedtonormaldiagramsifonlyonedatasetisselected,seeFig.8.However,thereare
somedifferenceswhichwillbediscussedinthischapter.ThecombineddiagramoftheFe
SH2OexampleisshowninFig.9.
The main element selection of the combined diagrams is made in the four Data Sets
options,Fig.8.Theselected main element canbeseenfromthe heading ofthe diagram.
ThefirstelementintheheadingFeSH2Osystemat25Cisalwaysthemainelement.
Table shows all the calculation results, which are used to draw the final diagram, see
Chapter17.7fordetails.
HSCChemistry5.0 1717
Fig.9.CombinedEhpHdiagramforanFeSH2Osystemat25C.TheFemolalityvalues1,103,and
106havebeenusedasparameter.
HSCChemistry5.0 1718
Fig.10.Calculationresultsusedtodrawthefinaldiagram.ThisformcanbeopenedbypressingTableon
Diagramform,seeFig.9.
HSCChemistry5.0 1719
17.7 CalculationResultsofCombinedDiagrams
TheEpHmoduleautomaticallycarriesoutallthecalculationsneededtodrawthediagram.
The result workbook may be seen by pressing Table in the Diagram form, see Fig. 9.
Normally you do not need to worry about these sheets at all. You may utilize this
information,forexample,toseetheexactnumericalcoordinatesofthelinesortoidentify
some verysmallandcomplexstabilityareas,etc.Themodification ofthis worksheet has
noeffectonthediagram.
Theresult workbookcontainssixsheets.Thefirstfoursheets(DS1,DS2,DS3,DS4)are
forthelinecoordinatesbasedondatasets1to4.Thesesheetscontainthespecies names,
areanumbers,linecoordinatesandlineproperties.
The Label sheet contains the label names and label coordinates as well as the area
numbers,whichconnectthelabeltothefinallinesspecifiedintheLinessheet.Thissheet
gives the calculated coordinates of the lines in the final diagram. These two sheets also
showalltheformatpropertiesusedtodrawthelabelsandlines onthediagram.Thearea
numberiscalculatedusingtheformula
4
DS= 2(n-1) , [2]
n = 1
wherenisthedatasetnumber.
Forexample,6=2(21)+2(31) meansthatlabeliscombinedfromdatainsets2and3.
You can print the active sheet (or all sheets) by pressing Print. Exit closes the result
workbookandreturnsyoutothepreviousform.
17.8 Eh pHDiagramsinPractice
TheHSCEpHmoduleenablesfastandeasycreationofPourbaixdiagramsfortherequired
chemicalsysteminuserspecifiedconditions.Thesediagramscontainthebasicinformation
oftheaqueoussysteminacompactandillustrativeform.Thesediagramshave foundmany
applications in corrosion engineering, geochemistry and hydrometallurgy since the
publicationofthefamousPourbaixAtlashandbook12.
Some application examples of EpH module and Pourbaix diagrams are given in Chapter
18,aswellasanexampleoftheEpHfileformat.
HSCChemistry5.0 181
18.EppHSamples
EpHmodule: InputFileforEpHModule
EhpHDiagram4.0'=Diagramtype 'Heading
2 'NumberofElements
Cu 'NameofaElement
1.0000,1.0000 'MolalityandpressureofthisElement
S
1.0000, 1.0000
2 'Numberoftemperatures
25.000,75.000 'ValuesofTemperaturesinC
N 'Showstabilityareasofions(Y/N)
56.6781,54.7567 ' DGvaluesofH2Oforalltemperatures
1.0000,1.0000 'DielectricConstant
0 'Ionstrenght
2,2,0,14 'Limitsofthediagram
Cu,0.0000,0.0000 'Nameofaspeciesand DGvaluesforalltemperatures
CuH3 ,67.7313,68.0470
CuO, 30.6627, 29.5533
Cu2O, 35.3446, 34.4294
CuO*CuSO4, 189.3533, 183.9282
Cu(OH)2, 85.8077, 82.4437
CuS , 12.7800, 12.7952
Cu2S, 20.6662, 20.8844
CuSO4, 158.2417, 153.8574
Cu2SO4, 156.4294, 152.5214
CuSO4*3H2O, 334.5808, 323.1528
CuSO4*5H2O, 449.2635, 433.1954
H2SO4, 164.8848, 159.9397
H2SO4*3H2O, 345.1000, 334.0907
H2SO4*4H2O, 402.9123, 389.9613
S,0.0000,0.0000
S(M),0.0190, 0.0068
SO3(B), 89.4025, 86.2283
SO3(G), 89.7786, 86.7094
Cu(+2a),15.6300,15.7317
Cu(+a),11.9450,11.0901
Cu(OH)2(a), 59.5596, 53.6263
CuSO4(a), 162.3104, 155.5767
Cu2SO3(a), 92.2243, 87.8581
H2S(a), 6.5160, 6.1670
HS(a),2.9113,4.2276
H2SO3(a), 128.5529, 125.6145
H2SO4(a) , 177.9474, 171.0575
HSO3(a), 126.1208, 122.2317
HSO3(2a), 121.3430, 116.7342
HSO4(a), 180.6580, 175.4083
HSO4(2a), 175.2501, 169.3171
HSO5(a), 152.3532, 147.0925
S(2a),20.5471,22.6438
S2(2a),19.0406,21.0895
S3(2a),17.6446,19.6504
SO2(a), 71.8354, 71.1981
SO3(a), 125.6315, 121.1608
SO3(2a), 116.2971, 110.0146
SO4(2a), 177.9474, 171.1338
S2O3(2a), 123.9775, 118.6055
S2O4(2a), 143.5482, 137.2786
S2O5(2a), 188.0263, 180.6896
S2O6(2a), 231.6077, 223.3179
S2O8(2a), 266.4866, 257.3452
S3O6(2a), 244.8178, 236.2948
HSCChemistry5.0 182
EpHCase1:MetalCorrosioninFeH2Osystem
EhpHdiagrams maybeusedtoestimatecorrosionbehaviorofdifferentmetalsinaqueous
solutions. Themostcommoncorrosionphenomenonis rustformationontheironsurfaces.
The corrosion rates and types depend on the chemical conditions in the aqueous solution.
TheEhpHdiagramofanFeH2OsystemmayeasilybecreatedasdescribedinChapter17.
ThechemicalsystemspecificationisshowninFig.1andthecalculateddiagraminFig.2.
Thestabilityareasmaybedividedintothreegroups13:
1. Corrosion area: Formation of ions means that metal dissolves into an aqueous
solution.Forexample,Fe(+3a),Fe(+2a),FeO2(a)andHFeO2(a)ionsinanFeH2O
system.
2. Passive area: Formation of oxides or some other condensed compounds may create
tight film (impermeable) on the metal surface which passivates the surface, good
examples areAl2O3 onaluminiumorTiO2 ontitaniumsurfaces.Iftheoxidelayeris
nottightenough(porous)topreventoxygendiffusionintothemetalsurface,corrosion
may continue. This is the case with the most of the iron oxides but they may also
causepassivationinfavourableconditions.
3. Immunityarea:Allmetals arestableiftheelectrochemicalpotentialislowenough.
Mostnoblemetalsarestableevenatzeropotential,butatleast0.6voltsareneeded
atthecathodeforirontoprecipitate,seeFig.2.
Fig.1.SpecificationofFeH2OsystemforEpHdiagramat25C.
HSCChemistry5.0 184
Fig.2.EhpHDiagramofFeH2Osystemat25C.MolalityofFeis106 M.
HSCChemistry5.0 185
EpHCase2: CorrosionInhibitorsinFeCrH2Osystem
Some elements or compounds may prevent corrosion even at very low content in the
chemical system. These substances are called corrosion inhibitors and they can be divided
into anodic and cathodic inhibitors. The anodic inhibitors primarily prevent the anodic
reaction and passivate metals in this way, the latter ones suppress the corrosion rate by
preventingthecathodicreactionorbyreducingthecathodicarea13.
Chromateanddichromateionsarewellknownanodiccorrosioninhibitors.Smallamountsof
chromates will create a tight complex oxide film on the steel surface which prevents
corrosion. The oxide film is mainly formed of magnetite (Fe3O4), hematite (Fe2O3) and
chromicoxide(Cr2O3).
The inhibitor behavior of chromates may be illustrated with EhpHdiagrams. The FeCr
H2Osystemspecifications areshowninFig.3.ThecalculationresultsforFeH2OandFe
CrH2Osystems areshowninFigs 4and5.As showninthediagrams,alargeareainthe
corrosionregionofironFe(+2a),Fig.4,iscoveredbytheCr2O3 andCr2FeO4 stabilityareas
andthusprotectedfromcorrosion,Fig.5.
It is easytocreateEhpHdiagramswiththeEpHmodule.However,youshouldremember
thatthistypediagramgreatlysimplifiestherealsituation.Theydonottakeintoaccount,for
example, the kinetic aspects or nonideality of real solutions. Small errors in the basic
thermochemicaldatamayalsohaveavisibleeffectonthelocationofthestabilityareas.In
any case, these diagrams givevaluablequalitativeinformationofthechemicalreactions in
aqueoussystemsinbriefandillustrativeform.
Fig.3.SpecificationofFeH2OsystemforEpHdiagramat100and300C.
HSCChemistry5.0 186
Fig.4.FeH2Osystemat100C.Molality:Fe102 M,pressure1bar.
HSCChemistry5.0 187
Fig.5.FeCrH2Osystemat100C.Molalities:FeandCr102 M,pressure1bar.
HSCChemistry5.0 188
EpHCase3: SelectionofLeachingConditions
The first step in a hydrometallurgical process is usuallyleachingordissolutionoftheraw
materials inaqueous solution.Theaimis toselect themostsuitableleachingconditionsso
that the valuable metals dissolve and the rest remain in the solid residue. The leaching
conditions may easily be estimated with EhpHdiagrams. In favorable leachingconditions
thevaluablemetalsmustprevailinsolutionasaqueousspeciesandtheothersinsolidstate.
Roasted zinc calcine is the most common raw material for the hydrometallurgical zinc
process. It contains mainly zinc oxide. AnexampleofEhpHdiagrams applicationinzinc
oxide leaching is shown in Fig. 7, see Fig. 6 for chemical system specifications.It canbe
seen from the diagram that acid or caustic conditions are needed to dissolve the ZnO into
solution19.
InacidconditionsthepHofthesolutionmustbeloweredbelowavalueof5.5.Inpractical
processes the pH must be even lower because the relative amount of zinc in the solution
increases if the pH is adjusted farther from the equilibrium line between the ZnO and
Zn(+2a) areas. The dissolution of the ZnO consumes hydrogen ions as can be seen from
reaction(1).Thereforeacidmustcontinuouslybeaddedtothesolutioninordertomaintain
favorableleachingconditions.
ZnO+2H(+a)=Zn(+2a)+H2O [1]
Incausticconditionszincmaybeobtainedinsolutionbytheformationoftheanioncomplex
ZnO2(2a).Theleachingreactionmaybedescribedbyequation(2).
ZnO+H2O=ZnO2(2a)+2H(+a) [2]
The leaching conditions change, for example, if sulfur is included inthe chemical system.
TheeffectofsulfurcanbeseeninFig.10.MuchsmallerpHvaluesareneedtodissolveZnS
which has wide stability area. This will lead to the formation of hydrogen sulfide gas and
ionsaccordingtoreaction(3).
ZnS+2H(+a)=Zn(+2a)+H2S(g) [3]
Inoxidizingconditions anumberofdifferentaqueousspeciesmayresultfromtheleaching
reactionssuchas(4),(5)and(6),seeFig.6.Inthesereactionsitisimportanttonotethatthe
consumptionofreagentsaswellasgenerationofreactionproductscontinuouslychangethe
solution conditions. These conditions must be regulated by feeding more acid and/or
removingreactionproductsinordertothemaintainoptimumconditions.
ZnS =Zn(+2a)+S+2e [4]
ZnS+4H2O=Zn(+2a)+HSO4(a)+7H(+a)+8e [5]
ZnS+4H2O=Zn(+2a)+SO4(2a)+8H(+a)+8e [6]
The HSC database contains a lot of species which may have a long formation time.
Normally it is wise to select only such species which are identified in real solutions for
chemical systemspecifications.Asystemspecificationwithonlycommonspeciesincluded
is showninFig.8andanotheronewithallthespeciesinFig.9.Theselectedspeciesmay
haveavisibleeffectonthediagramsascanbeseenbycomparingFigs.10and12aswellas
Figs. 11 and 13. In some cases, diagrams with all the species selectedintothecalculation
systemmaygivealsovaluableinformation,Figs.12and13.
HSCChemistry5.0 189
Fig.6.ZnH2Osystemspecifications.
HSCChemistry5.0 1810
Fig.7.ZnH2Osystemat25C.DiagramisbasedonspecificationsinFig.6.
HSCChemistry5.0 1811
Fig.8.ZnSH2Osystemspecifications,only identifiedspeciesincluded
HSCChemistry5.0 1812
Fig.9.ZnSH2Osystemspecifications,allspeciesincluded.
HSCChemistry5.0 1813
Fig.10.ZnSH2Osystemat25CbasedonspecificationsinFig.8.
HSCChemistry5.0 1814
Fig.11.SZnH2Osystemat25CbasedonspecificationsinFig.8.
HSCChemistry5.0 1815
Fig.12.ZnSH2Osystemat25CbasedonspecificationsinFig.9.
HSCChemistry5.0 1816
Fig.13.SZnH2Osystemat25CbasedonspecificationsinFig.9.
HSCChemistry5.0 191
19. H,S,CANDGDIAGRAMS
The diagram module presents the basic thermochemical data for the given species in
graphicalformat.Eightdifferentdiagramtypescanbedrawnasafunctionoftemperature:
HEnthalpy(total)
HEnthalpy(latent)
SEntropy
CpHeatCapacity
GGibbsEnergy
DH
DS
DG(Ellinghamdiagrams)
The basic steps for drawing a diagram for all types is quite the same, except the small
differencewiththeDGdiagrams.Thesestepsaredescribedinmoredetailinfollowinglines,
seeexampleinFig.1:
1. TypethespeciesformulaetothefirstcolumnoftheXdatasheet.Thereisnoneedto
opentheothersheets,becausetheseareintheprogramsinternaluseonly.
2. SelectthediagramtypefromDiagramTypelist,inthisexampleHEnthalpy(latent)
hasbeenselected,seeFig.1.
3. DGdiagramsonly:Selectanelementfromthelist(forexample:Oforoxides,Sfor
sulfides,Clforchlorides,etc.)andpressBalanceElementAmount.
4. PressReadDatafromDatabase.Thiswillsearchthedatafromthedatabaseforthe
givenranges.YoucanforcetheHSCtouseitsownormaindatabasebysetting1or2
to theDatabase No column. Without this setting, the diagram module looks for the
datafirstfromHSCowndatabaseandthenfromthemaindatabase.
5. PressDiagram todrawthediagram.Youcanalsomodifyallthedefaultsettingssuch
asxandyaxisrangesandunits.However,youmustalwayspressReadDatafrom
Databaseafterthesemodificationsbeforeyoucanpressthe Diagram.
An example of a diagram is shown in Fig. 2. The solid lines show the values, which are
basedondatainthedatabase,andthedottedlinesshowtheextrapolatedvalues.Sometimes
the extrapolated data may behave irregularly because the Cpfunction extrapolates
incorrectly outside the given range. The scales, lines and labels can be edited in the same
mannerasintheothergraphicsroutines.
The DGdiagrams (Ellingham) show the relative stability of various oxides, sulfates,
chlorides etc. These diagrams must contain only the same type of substances, such as
oxides,sulfides,chlorides,etc.Thespeciesamountsmustbebalancedtocontainexactlythe
sameamountofthemainelement,suchasoxygeninoxidesandsulfurinsulfides.
AnexampleofEllinghamdiagramsettingsisgiveninFig.3.TheresultsinFig.4show,for
example,thatironoxidescanbereducedwithcarbonathighertemperaturesthan700C,i.e.
FeO+C>Fe+CO(g).MetalswhoseoxideDGissmallerataselectedtemperature,Fig.4,
canbeusedtoreducethoseoxideswheretheDGishigher.Themoststableoxides(Cr2O3,
MgO)arelocatedatthebottomofthediagram.
HSCChemistry5.0 192
Fig.1. Thediagrammenu.Enthalpydiagramtypeselected.
HSCChemistry5.0 193
Fig.2. TheEnthalpy(latent)diagrambasedonthesettingsinFig.1.
HSCChemistry5.0 194
Fig.3. DiagramsettingsoftheEllinghamdiagramforoxides.
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Fig.4. EllinghamdiagramofoxidesbasedonthesettingsinFig.3.
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20. DIAGRAMGRAPHICS
20.1 GraphicalObjects
The new Drawing Toolbar can be used to draw basic graphical objects (lines, arrows,
rectangles,ellipses)inHSCdiagrams.Theseshapesmaybeused,forexample,toillustrate
experimental conditions. Versatile formatting options enable the user to edit lines, fill
color,linewidthsandstyles.
Drawing Objects can be created and edited with the mouse or the Object Editor, which
enablesverypreciseeditingusingnumericalvaluesasinputs.DrawingObjectscanalsobe
fixedsothattheycanbeusedinalldiagramsorsavedforlateruse.
Userspecifiedgraphicsmaybeaddedtodiagramsintwoways:
1.UsingtheToolbar(Show/ToolbarfromtheDiagrammenu)
2.UsingtheObjectEditor(Show/ObjectEditorfromtheDiagrammenu)
1.UsingtheToolbar
The Toolbar provides a standard drawing interface for drawing simple shapes and for
inserting text. The same functions are also available from a popup menu by clicking the
right mouse button. In Figure 1 the example file incropera_92_494.HTR in the Heat
Lossmodulehasbeenusedtocomparetheconvectionandradiationcoefficients,whenthe
characteristiclength(verticallength)variesfrom0.2mto0.8m.
HSCChemistry5.0 202
Figure1:Thedrawingtoolbar,shownherefromtheHeatLossmodule.
Thefirstfivebuttonsareusedfordrawinglines,arrows,rectangles,ellipsesandtext.The
nexteightbuttonsareusedformodifyingtheobjects,forexamplethelinethickness.These
optionsarealsoavailablefromtheOptionsdropdownbox.Thexandycoordinatesfor
the mouse cursor are shown on the toolbar. In Figure 2 a simple arrow is inserted and
moved around using the mouse. All objects can be moved around the diagram using the
draganddroptechnique.
HSCChemistry5.0 203
Figure2:Drawinganarrowandmovingitaroundusingdraganddroptechnique.
2.UsingtheObjectEditor
Another method of creating and modifying objects is to use the Object Editor
(Show/ObjectEditor fromthe menu).TheObject Editorconsists ofthreesheets:Lines,
Shapesand Labels. TheLinessheetcontainsalllinesandarrows,theShapessheetcontains
allrectanglesandellipsesandtheLabelssheetcontainsallthelabels.
Thecellswithablueforegroundcolor,maybechangedmanuallybytypingdirectlyinthe
cell,forexample,thecoordinates ofarectangle.Thecells withablackforegroundcolor,
maybechangedbydoubleclickingonthe cell.Theappropriateproperty windowforthe
cell will then appear. For example, by doubleclicking on the Color column, the color
property window appears. In Figure 3 the color of a rectangle, which demonstrates the
approximatetransitionregioninthediagram,ischangedusingtheobjecteditor.
HSCChemistry5.0 204
Figure3:UsingtheObjectEditortochangetheobjectproperties.
Acreatedgraphicallayoutmaybeusefulinfuturediagramstoo,thereforeHSC5.0allows
the user to save the layout as an object file (.OBE file), which may be imported to any
diagram within HSC 5.0. By selecting File/Save from the object editor menu, all the
currentobjectsinthediagramwillbesavedinafileforlateruse,seeFigure4.
Notice that the objects in the HSC Object editor use the same coordinate system as the
diagram,i.e.thesamexandyscales.Thereforethelocationoftheobjectswillbechanged
onthescreenifthexoryscaleminimumormaximumvaluesarechanged.Forexample,
inMSExcelchartstheobjectsusescreencoordinates.
HSCChemistry5.0 205
Figure4:Savingthecurrentdiagramobjects.
20.2 FormattingtheDiagram
MostofthediagramformattingoptionsareavailablewithinallHSCdiagramroutines.The
followingparagraphsgiveasummaryoftheseoptions:
Figure5:Changingscales,scalenumberformatandfontsettings.
3. Gridlines can be edited by selecting Format/Gridlines from the diagram menu and
different settings can be specified for the x and the yaxis. The gridline properties
include:color,linewidth,linestyleanddisabled.Dependingonthetypeofprinterin
use,differentgridlinesettingsmayberequiredinordertoproduceadesirableprintout.
An example of a gridline setting is shown in Figure 6, where three different
temperature profiles are drawn using the example file Smelting2.HTR from the
HeatLossmodule.
HSCChemistry5.0 207
Figure6:Editinggridlines.
4. The line width of curves, species label font and other graphical properties may be
changedbyeitherdoubleclickingonthespecies labelsorbyselectingthelabelwith
themouseandchoosingFormatLabelfromthemenu.Thisfunctionis notpossible
by double clicking on the curve. In the label and curve editing window, shown in
Figure7,thethicknessofthecurvenamedSmelting1200Cischanged.Noticethat
alternativelinestylestosolidareavailableonlyforlinewidthssmallerthan0.3mm.
HSCChemistry5.0 208
Figure7:Changinglabelandlinespecifications.
5. ThePlotAreacanbemodifiedbyselectingFormat/PlotArea fromthemenu.The
backgroundandbordercolorscanbechanged,aswellastheborderlinestyleand
thickness.Changingtheborderlinepropertiesmaybenecessaryinordertoviewa
curvethatisonaborderline.
HSCChemistry5.0 209
Figure8:Changingplotareaspecifications.
6. Toeditanylabelandheadingonthescreen,simplyclickthetextinthelabelwiththe
mouseandstarttoedit.
7. Tocreatenewlabels,selectLabelfromtheInsert menu.Newlabels canbedeleted
usingtheLabelselection intheDelete menu.Defaultlabels cannot be deleted, it is
onlypossibletoremovethetextfromthem.
8. When using HSC Chemistry for the first time it may be necessary to change the
defaultfonts,becausetheavailablefontsvaryfromonecomputertoanother.This is
achievedbyselectingtheDefaultFontfromtheFormatmenu.UsuallyTimesNew
Roman, bold, size 11 font is the recommended selection. The selection made will
automaticallybesavedintheHSC.INIfileinyourWindowsdirectory.
9. Once satisfied with the diagram, you can print it by pressing Print BW. If a color
printeris availablepress PrintCol.Theprint dialog provides severaluseful options
forahardcopy,seeFigure9.
HSCChemistry5.0 2010
Figure9:HSCprintdialogforgraphics.
10. To view the diagram in a tabular format or use the data of the diagram in other
programs, such as MS Excel, press Table. Press Diagram to return back to the
diagram.
11. To copy the diagram to the Clipboard press Copy, and paste the diagram to other
Windows programs. TheCopy command uses the Windows Metafile format, which
enablesyoutoresizethediagraminotherWindowsapplicationsinfullresolution.
12. The SaveVec.buttonsavesthediagramusingtheWindowsMetafileformat(.WMF).
13. The Save Ras. button saves the diagram in raster format. There are a number of
formatsavailableaswellasseveraleditingpossibilities.SeeChapter20.3Editingand
CombiningDiagramsforamoredetaileddescription.
14. PressExittoreturnthemainmodule.
HSCChemistry5.0 2011
20.3 EditingandCombiningDiagrams
Whereas the previous HSC Chemistry 4 was only able to save diagrams using a WMF
format,nowmorethan30fileformatsareavailable,suchasJPGandBMP.HSCdiagrams
can now be saved in vector (.WMF Windows Meta File) andraster formats.The image
dialog may be opened by pressing the Save Ras. button or by selecting File/Save as
RasterFilefromthediagrammenu.
Figure10:Rasterimage propertiesdialog.
Itisnowalsopossibletocombinediagrams(pressViewCombineEditor)usingthenew
HSCImageCombiner,ifthesamexandyscaleshavebeenused.Anothernewfeatureis
the possibility to edit diagrams (press View Image Editor) using the new HSC Image
Editor.
1. Editingdiagrams(HSCImageEditor)
There are a number of functions in the edit mode, for example filtering techniques,
rotating,scaling,tilting,copy/pasteetc.Oncethechangeshavebeenmadeitiseasytosave
the picture in a number of different formats by selecting File/Save from the menu. Any
saved pictures can be used in other programs. Figure 11 shows the editing of a phase
stabilitydiagramcreatedwiththeLppmodule.
HSCChemistry5.0 2012
Figure11:EditingthepictureusingtheHSCImageEditor.
2. Combiningdiagrams(HSCCombineEditor)
SeveraldiagramscanbecombinedwiththenewHSCImageCombinerifthesamexand
yscales havebeenused.It is alsopossibleto opentheImageCombiner fromthe Image
Editor by selecting Combine from the Image Editor menu. Figure 12 shows the
combinationoftwophasestabilitydiagramscreatedwiththeLppmodule.
HSCChemistry5.0 2013
Figure12:CombiningdiagramsusingtheHSCCombineEditor.
HSCChemistry5.0 211
21. PHASESTABILITYDIAGRAMS
Thephasestabilitydiagramsshowstability(predominance)areasofcondensedphasesin
a ternary system as a function of temperature or in isothermal conditions, with the
remaining constraints as the other axis. These diagrams are very useful when a fast
estimation of the prevailing phases is needed. It is assumed that all phases are pure
substances.Mixturephasesarenottakenintoaccountinbasicphasestabilitydiagrams.
The newHSCChemistry5.0can drawtwotypes of phasestability diagrams.Thenew
Tpp Diagram module calculates the diagrams on the basis of minimum Gibbs energy
(area graphics) and the old Lpp Diagram module calculates the phase stability
boundariesaslinesbasedonthereactionequations(vectorgraphics).Thesetwomodules
havetheirownoptionbuttonsintheHSCmainmenu,i.e.TppandLppDiagrambuttons.
TheTppdiagrammoduledrawstemperaturepartialpressurediagrams(Tpdiagrams)as
wellasppdiagramswithpartialpressuresonbothaxes.TheoldLppmoduledrawsonly
diagrams withselectedpartialpressuresonbothaxes.Thesebothmodulesofferslightly
different benefits and limitations for example, the old Lpp module gives exact
coordinatesforthephaseboundaries but the newTpp module givesillustrativepainted
areadiagramsandalsoaversatileTpaxisoption.
A common limitation for both the diagram modules is that only three elements can be
selectedsimultaneouslyinthecalculationsystem.Anotherbasicfeatureisthatonlytwo
variablescanbeselectedforthediagram,i.e.:
1. Ifpartialpressuresareselectedforbothaxesthenthetemperaturemustbefixed.
2. Ifthetemperatureisselectedforthexaxisandpartialpressurefortheyaxis,then
one partial pressure must be fixed. The partial pressure species may not contain
moreelementsthanthespeciesselectedfortheyaxis.
Thepartialpressure piofgasi inagasmixtureisdefinedbyequation(1):
pi= xi*P [1]
where xi is the mole fraction of i in the mixture and P is the total pressure. The HSC
phasestabilitydiagramsuselogarithmicscalesforpartialpressures,whichareexpressed
inbarunits(1bar=100kPa=0.987atm).
HSCChemistry5.0 212
21.1 TppDiagramModule
Fig.1. InputdataforTppphasestabilitydiagrams.
Fig.2. ThecolorpalettedialogfortheTppmodule.
21.2 TppDiagrams
HSCChemistry5.0 214
Fig.3. TppphasestabilitydiagramsbasedondatainFig.1.
The Tpp phase stability diagram is shown in Fig. 3, and the corresponding calculation
system specifications are shown on the previous page. In this diagram we can see, for
example,thatcopperoxidefluedustinahotprocessgastendstosulfatize,whentheflue
dust temperature decreases. It is also very easy to see that when the oxygen pressure
decreases,thesulfatesarereducedfirstintooxidesandfinallyintometalform.
ThesediagramscanbemodifiedinthesamewayasotherHSCdiagrams:
1. Xandyaxisscalesandformatscanbeeditedbydoubleclickingtheaxeswiththe
mouse.
2. Thelabelsandheadingscanbeeditedbydoubleclickingthelabels.
3. ThediagramscanbecopiedtotheClipboardbypressing Copy.
4. Diagrams can be printed by pressing Print. The printing dialog gives several
options for hard copies. The new resize option is very useful if there are several
smallstabilityareasinthediagram.
21.3 LppDiagramModule
HSCChemistry5.0 215
Fig.4. Inputdataforphasestabilitydiagrams.
The Lpp Diagram module draws isothermal phase stability diagrams of three element
systems,alsoknownaspredominanceareadiagrams orKelloggdiagrams.Anexample,
showninFigs.46,isadiagramoftheTiClOsystem,whichshowsthestabilityareasof
titanium containing substances as a function of Cl2(g) and O2(g)pressures in the
atmosphere.Followthesestepstodrawthediagram:
1. SelectthreeelementswiththemouseandpressOK,inthiscaseTi,ClandO.
2. Wait a while until HSC displays the substances from the databases. Press All or
select at least three substances (species) for the diagram. Please select only Ti
containingsubstances.
3. Select one gas species for the xaxis, for example Cl2(g). You may select any
speciesforthexaxisexceptthosewhichcontainTi.
4. Select one gas species for the yaxis, for example O2(g). You may select any
speciesfortheyaxisexceptthosewhichcontainTi.
5. Change the temperature if needed, in this example 300 C. You may choose
betweenCandKbypressingthebutton.
6. PressFileSaveandaccept the name(TiClO700.IPS)forthe input file.ThePSD
programdrawsthediagramonthebasisofthisfile.Itmaybeagoodideatosave
all*.IPSfilesinaseparate \HSC\PSDdirectoryifavailable.
HSCChemistry5.0 216
PSDdiagramsofferaneasywaytoevaluatestabilitiesofdifferentcondensedsubstances
as a function of gas pressures, typically O2(g), S2(g), SO2(g), Cl2(g), etc. These
diagramscanbeused,forexample,tofindthebestconditionsforoxidizingorsulfatizing
reactions,etc.
Limitations:
Ifyouhavemorethanonesubstancewiththesameoverallcomposition(stoichiometry)
inthespecieslist,forexampleNaSandNa2S2,FeOandFeO(l),etc.,pleaseselectonly
onesuchsubstanceforthediagram.InanycaseHSCwillautomaticallyomitsubstances
with identicalstoichiometry.Theusercan makethis selectionhimselfin ordertoselect
exactlythosesubstanceswhichhewantstobetakenintoaccount.
HSCChemistry5.0 217
21.4 LppDiagramMenu
Fig.5. ChangingthedefaultsettingsofthePhaseStabilityDiagram.
OntheDatasheetofthePSDMenuyoucanseethecalculateddataofthePSDdiagram
inatabularform.TheFormatsheetcontainsformattingsettingsofthediagram.Itisnot
recommendedto changethese.HSCevaluates the default values automaticallyforMax
Y,MinY,MaxXandMinXfortheaxes.
Youcancalculateanddisplaythediagraminthefollowingway:
1. Selectthe*.IPSfileforthediagrambypressingFileOpenifnotalreadyselected.
Thisfilecontainsthe DGvaluesfortheselectedspeciesatagiventemperature.
2. Youwillautomaticallygetthediagramon thescreen.
Changethedefaultsettingsofthediagraminthefollowingway:
1. Youmaychangetheminimumandmaximumvalues forthexandyaxissimply
byclickingthevalueusingthemouseandbystartingtoedit.
2. PressDiagram todisplaythediagram.
3. PressPrinttogetapapercopyofthetabularresults.HSCwilldrawthediagramat
thebestresolutionofanyMSWindowssupportedprinter.
4. PressCopytopastethedataontootherWindowsprograms.
5. PressExittoreturntoHSCortoexitthePSDprogram.
HSCChemistry5.0 218
21.5 LppModuleDiagram
22. MINERALOGYITERATIONS
Composition conversions, between substance (mineralogy) and elemental analyzes, are
often needed in chemical R&D work. The Mineralogy module easily converts minera
logical compositions into elemental ones, but is not always able to make reverse
conversion.Conversioncanbemadeusingthefollowingprocedure,seeFig.1:
1. TypethespeciesformulaeintocolumnA,userows>4.Thespeciesdonotneedto
existintheHSCdatabase.However,youmustusetheHSCformulasyntax.
2. TypethecompositionsincolumnD.
3. Theelementalcompositioncanbeseenonrow4.
YoucanalsogivethetotalamountforthematerialincellC4aswellasnameincellA1.
NotethattheusermayeditonlythecellswithredfontsifFormatRedFontShieldhas
beenselected.
Theconversionoftheelementalcompositionofasubstanceintoamineralogicaloneisa
more difficult task,forexample duetosmallanalyticalerrors.This module offers three
toolsforconvertingelementalanalyzesintomineralogicalones.
1.SolveMethod
TheSolve methoduses matrixalgebratosolvethe mineralogy.It is useful ifthe given
amounts of elements fit exactly to the given substances. The number of unknown
compositions must also be the same as or less than the number of element balance
columns.
AnexampleoftheSolvemethodisshowninFig.2(fileExample1.mnr).Youcancreate
thisexamplefromthepreviousonewiththefollowingprocedure:
1. PressCopyRow4to3 buttontocopyelementalcompositionsfromrow4to3.
2. Type1to cellsD5D8,inordertowipeouttheoriginalcompositions.
3. PressSolve.TheresultswillbeshownincolumnD.Usuallytheelementsdonotfit
exactly to the given species, in these cases the Solve method may add some
elementrowstothesystem.Theserowscanbedeletedby DeleteRowselection.
2.AutomaticIterativeMethod
The Automatic iterative method fits the given elements to the given substances by
changingthespeciescontentsinordertoreachthegivenelementcompositions.Tocarry
outthisconversionfollowthesesteps,seeFig.4:
1. TypespeciesformulaetocolumnA,userows>4.
2. Typeelementalanalyzetorow3,usecolumns>D.
3. Typethetargetelements,whichwillbeusedtoiteratethespecies,intocolumnB.
Pleasedonotusethesameelementforseveralspecies,otherwisemanualiteration
maybeneeded.
4. PressIterateAlltostartiterations.Sometimesitis necessarytopressthisbutton
severaltimesinordertoreachsufficientaccuracy.
3.ManualIterativeMethod
Sometimesthegivenelementalanalysisdoesnotfitwiththegivenelements.Inthiscase
theusermaysearchtheapproximatecompositionmanuallybychangingthecontentsin
column D, in ordertoreachasatisfactory match withthe elementalanalyzes inrows 3
and4.IterateSel canbeusedtoiterateindividualrows.
HSCChemistry5.0 222
Fig. 1. Calculation of the elemental composition of a material mixture. The user has given the species
namesincolumnAandthecontentsincolumnD.Thecalculatedresultisshownonrow4.
HSCChemistry5.0 223
Fig.2.CalculationofthespeciescompositionincolumnDusingtheelementalcompositioninrow3by
Solve.
HSCChemistry5.0 224
Fig. 3. Calculation of the elemental composition of a sulfide material. The user has given the species
namesincolumnAandthecontentsincolumnD.Theresultisonrow4.
HSCChemistry5.0 225
Fig.4.IterationofspeciescompositionsincolumnDonthebasisoftheelementalcompositionsinrow3
with IterateAll.ThetargetelementsincolumnBmustbespecifiedbytheuser.
HSCChemistry5.0 226
SetLastRow
Pressing Set Last Row will set the last row which is used in the calculations. All
compositionsbelowthisrowarekeptconstant.Thispropertycanbeused,forexample,if
thecontentsofsomespecies,suchasSiO2,Al2O3,etc.,areavailable.
CalculateMixtureComposition
The user can insert new sheets into the mineralogy workbook with the Insert Sheet
selection.This will createan identicalsheet ontheright sideoftheselectedsheet.The
newsheet canbecleared withtheEditClearAllselection.Theseidenticalsheets may
alsobeusedformixturecalculations.
Quite often the feed of a chemical process consists of several raw materials. The
compositions ofthese materialsarefixed,but theratios change fromtimetotime.The
totalcompositionofthemixturemaybecalculatedwiththeMineralogymoduleandby
followingthesesteps,seeFig.5(filenameofthisexampleisExample3.mnr):
1. StartfromExample2,showninFig.4andSelectInsertSheet.
2. Doubleclickthesheet1tabandrenamethesheetasRaw1.Renamesheet2inthe
samewayasRaw2,youcanalsouserealnamesforthematerials.
3. Typeorsolvethecompositionsforeachindividualsheetasdescribedbeforeinthis
chapter. Do not add or remove species from the list, the species list must be
identicalineachsheet.GivetheamountsforeachmaterialintheC4cells.
4. Select Calculate Mixture Composition. This will add a mixture sheet and
calculate the mixture composition for all the raw materials and give the total
amountofthefeedincellC4.
HSCChemistry5.0 227
Fig.5. Calculationofthemixturecompositionofthreerawmaterials.
HSCChemistry5.0 228
CopyRow4to3
Thisbuttonwillcopyalltheelementalcompositionvaluesfromrow4torow3.
NumberofIterations
Thedefaultnumberofiterationsis10,butitcanbechangedinthecellleftoftheIterate
Allbutton.Theprogramcarriesoutamaximumof10iterationseachtimeIterateAllis
pressed.Youcandecreasethenumberofnecessaryiterationsbygivingsomepreliminary
guess valuesintocolumnD.Insomecasespreliminaryguessvaluesareneededtohelp
theiterationroutinetofindthecorrectanswer.
OtherProperties
Thesametype of formattingproperties as in otherHSCmodulesareavailable,suchas
FormatNumber,InsertRow,EditCopy,etc.
TheusercanalsosavetheworkbookforlaterusebyselectingFileSaveandreaditback
with the File Open selection. It is recommended to save the files quite often with
differentnamessuchasFeed1,Feed2,etc.inordertorecovertheoriginalsettingsincase
ofmistakes.ThefilescanalsobesavedandopenedusingExcel5format.
HSCChemistry5.0 231
23. COMPOSITIONCONVERSIONS
TheCompositionConversionmoduleisasimplifiedversionoftheMineralogyiteration
module. It is included in HSC Chemistry because the Composition Conversion module
easilygivesthecompositionsandamountsofthespeciesinwt%andkgunits.
TheCompositionConversionismadeusingthesameprogramroutines,whichareusedin
theMineralogyroutine.Thereforethelimitationsarealsothesame.
An example is shown in Fig. 1.The same results can be obtained with the Mineralogy
module,seeFig.1.inChapter22.MineralogyIterations.
24. ELEMENTSMODULE
Thebasicchemicalandphysicalproperties oftheelementshaveadecisiveeffectonthe
thermochemicalpropertiesofcompounds.Forexample,theelectronegativityvaluesofthe
elementshaveastrongeffectonthechemicalbondsbetweentheelementsinallchemical
compounds.Thereforetheperiodicsystemofelementssetsthebaseforthermochemistry.
The Elements module offers an element database in spreadsheet format with some 56
differentpropertiesoftheelements.Theusermayeasilyaddhisowndatatothistablein
thesame wayas inMSExcel applications.This data maybesavedfor laterusebythe
FileSaveselection.ThedefaultnameoftheworkbookisElement4.ele.
Diagram enables the user to draw illustrative diagrams on the basis of the selected
propertyrow.Densityrow7hasbeenselectedintheexampleofFig.1andthediagram,
showninFig.2,maybedrawnbypressing Diagram.
Thediagramshowsataglancethegreatestandsmallestvaluesintheperiodicsystem.The
exact number values behind the spheres may be shown by double clicking the element
square or label in the diagram. The diameter of the sphere shows the magnitude of the
valuecomparedtothemaximumvalue.Themaximumvaluecreatesasphere,whichfits
exactly totheelementboxinFig.2.
The Fix Left 2 Columns selection, Fig. 1, fixes the two left columns. This makes it
possible to see the property headings and units for all the elements, when scrolling the
elementsheet.
The normal copy and paste properties as well as format and printing functions are
availableasinotherHSCmodules.Theworkbookformmayberesizedbydraggingthe
formboundariesusingthemouseorfromtheiconsatthetoprightcorneroftheform.
HSCChemistry5.0 242
Fig.1.TheElementsmodulecontainsseveralbasicpropertiesoftheelements.Theselectedpropertymay
beillustratedingraphicalformatbypressing Diagram.
HSCChemistry5.0 243
Fig.2.Thepropertiesoftheelementsmaybeillustratedingraphicalformat.Thevaluesoftheproperties
maybeshownbydoubleclickingtheelement.
HSCChemistry5.0 251
25.WATER
Figure1:PressureTemperaturecalculatorforwater.
ThiscalculatorisaveryusefulreplacementforsteamtablebooksandMollierdiagrams.
By directly typing the pressure and temperature of the process points, or by simply
clickingonthediagram,theprocessenthalpyandentropyarecalculatedalongwithseveral
other useful thermodynamic data. The module is also available through the Heat and
Material Balances module (Chapter 11. Heat and Material Balance), where the pressure
correctionmaybeinsertedintotheworksheetasacellformula.
HSCChemistry5.0 252
25.1 BasicCalculationProcedure
Thecalculatorletstheuserspecifytwoprocesspointspoint1beingthestartingpointand
point2theendpoint.Thecalculatorthencalculatestheabsolutevaluesforthetwopoints
and then the difference between them. The absolute values are mostly useful for density
and heat capacitydata,whereas the difference ordeltavalues areusefulforenthalpyand
entropydata.Alinebetweenthetwopointsmaybedrawnbyselecting Show/Linefromthe
menu.However,thislinedoesnotnecessarilyrepresenttheactualprocesspath,insteadit
makesthevisualizationofthetwopointseasier.Therearetwobasicways,whichmayalso
becombined,ofspecifyingtheprocesspoints:
Specifyingpointsusingthemouse:
1.Specifytheappropriateunitsfromthecomboboxesandtheamount(kmolorkg)inthe
textbox.
2.Activateoneofthepointsbyclickingontheappropriateboxinthediagram.Ayellow
boxindicatestheactivepointandawhiteboxtheinactivepoint.
3.Clickonapositioninthediagramandtheselectedpointwillmovetothatpositionand
thedatawillautomaticallyberecalculated.Notethatifasaturatedstateisselected,the
point willjumptotheappropriatesaturatedcurveifpossible.It isalsopossibletouse
thedraganddroptechniquetomovetheselectedpoint.
4. Repeatsteps2and3fortheotherpoint.
5.Ifapointisonasaturatedcurve,theusermayspecifythe Mixture%,i.e.thepercentage
of thefirst of the two phases in the mixture shown in the combobox on row 3 of the
worksheet.Thedefaultvalueis50%.
Specifyingpointsmanually:
1.Specifytheappropriateunitsfromthecomboboxesandtheamount(kmolorkg)inthe
textbox.
2. Specify pressures and temperatures for the two points by simply typing them into the
cells oncolumns1and2.Notethat ifasaturatedstateisselected,thetemperatureor
pressure willautomaticallybe calculated.The values that areautomaticallycalculated
areindicatedinablackfont.
3. If a point is on a saturated curve, the user has to specify the Mixture %, i.e. the
percentageofthe firstofthetwophasesinthemixturegiveninthecomboboxonrow3.
Thedefaultvalueis50%.
4.Ifapointisonasaturatedcurve,theusermayspecifytheMixture%,i.e.thepercentage
of thefirst of the two phases in the mixture shown in the combobox on row 3 of the
worksheet.Thedefaultvalueis50%.
Explanationofthep,Tdiagram:
Thep,Tdiagramtotheright ofthewindowcontains afewlabels.Theseareexplainedin
thefollowingpoints:
1.TriplePoint
The triple point refers to the point where all three phases of water may exist
simultaneously.ThispointisatT=0.01Candp=0.0061bar.Moststeamtablesuse
thisasthereferencepoint,i.e.theabsoluteenthalpyandabsoluteentropyaresettozero.
ByselectingEdit/Point2=TriplePointfromthemenu,thesecondprocesspoint will
automaticallybesettothetriple point,whichisalsothedefaultsetting.Thismeansthat
HSCChemistry5.0 253
The results of the calculation are shown in the same table below the input. The data
calculatedincludes:
1.Enthalpy(H)andEntropy(S)
The enthalpies and entropies for the two process points are calculated using the
referencepoint T=25Candp=1bar.This differs from what is normallyfound in
steamtables,wherethereferencepointisT=0.01Candp=0.0061bar(triplepoint
for water). This means that only the differences in enthalpy and entropy are of
importance, since they are independent of the choice of reference points. Point 2 is
thereforebydefault set to thetriplepoint,which means that the enthalpyand entropy
differences,indicatedbyayellowbackground,givethevaluesnormallyfoundinsteam
tables.
2.SpecificEnthalpy(Hspecific)
Thespecific enthalpies arethe enthalpieswhenthephasetransformations areignored.
In other words the enthalpy released/gained when water is cooled/heated to 25 C at
constantpressure.Thereforethespecificenthalpyiszeroat25C.
3.GibbsEnergy(G)
ThesecellsshowtheGibbsEnergyforthetwopoints.
4.HeatCapacity(Cp)
Thesecellsshowthespecificheatcapacityatconstantpressureforthetwopoints.
5.Density
These cells give the densities for the two points. The densities are interpolated or
extrapolated from the Excel file H2O.XLS located in the .\HSC5\PTCalc directory.
Pleasedonotmodifythisfile.
Otherimportantterms:
1.Isentropicprocess
If the entropy is constant through a process, i.e. the entropy difference is zero, the
processiscalledisentropic.Anisentropicprocessisanidealprocessandrealprocesses
areoftencomparedtothecorrespondingisentropicprocess.
2.Isentropicefficiency
An isentropic process generates no entropy and may therefore be considered an ideal
process. It is useful to compare real processes to that of the isentropic through the
isentropicefficiency.Theisentropicefficiencyforacompressororpump isdefinedas
Dhs
hs ,c = , [1]
Dh
25.2.1 Icemeltingathighpressure
Figure2:Meltingoficeatapressureof500bar.
TheexampleinFigure2showstheenthalpyandentropychangeof1kgsolidicemelting
at a constant pressure of 500 bar, until 90 % of the total mixture is liquid water. The
enthalpy difference is ~290 kJ and the process therefore endothermic. The entropy
differenceis~1.079kJ/Candtheprocessthereforegenerates entropy.Themeltingpoint
oficeat500barisautomaticallycalculated,sincethepointisonthesaturatedliquid/solid
curve,andit is roughly4.5C.This pressureis achieved,forexample, whenpressinga
sharp object against an icy surface, which then melts due to the decreased melting point
temperature.
HSCChemistry5.0 256
Figure3:Evaporationprocess.
TheexampleinFigure3showstheevaporationprocessinaheatrecoveryboiler,whenthe
massflowis500t/h(Amount:500000kg,Unit:MWh).Thetemperatureis285Candthe
pressuresareautomaticallycalculated,sincethesaturatedgas/liquidstateisselected.The
transferred heat is ~21 MW, when 10 % of the total water flow evaporates. This is
equivalent to a water/steam ratio of 90%/10% = 9. The entropy generation of ~0.038
MW/Cindicatesthattheprocessisnotisentropic.
HSCChemistry5.0 257
25.2.3 Steamturbineprocess
Figure4:Steamturbineprocess.
25.3 DetailedDescription
25.3.1 Pressurecorrectioninthedatabase
Table1showsthepressurecorrectedwaterspeciescurrentlyfoundintheHSCdatabase.
Table1:Pressurecorrectedspeciescurrentlyavailableinthedatabase.
For the solid/liquid phases, i.e. H2O(Xbar), this reference point does not cause any
problems,sinceatleastoneofthetwophases(liquidand/orsolid)existbelow25Candat
pressure X. They can therefore easily be extrapolated up to 25 C when necessary.
Extrapolation above the boiling/sublimation points at different pressures are shown as
dottedcurves in diagrams, whichalso meansthat theliquid/solid phase does not existat
thesetemperatures.
Figure 5 also shows that the ideal gas approximation, indicated by the label H2O(g), is
generallymoreaccurateforlowpressuresandhightemperatures.Theidealgascurvecan
beseenbelowtheconstantpressurecurves.Theruleofthumbisthattheaccuracyofthe
idealgasapproximationincreasesthefurtherawayyoumovefromthecriticalpoint.
Figure5:Cpfunctionsforsteamatdifferentpressures.
HSCChemistry5.0 2510
In order to calculate the enthalpy and entropy at different pressures, slight modifications
havetobe madetothe enthalpyofformationandstandardentropyat 25C,i.e.theHf
termofequations1and3inChapter8.Introduction.Moststeamtablesusethe triplepoint
ofwater(T=0.01C,p=0.0061bar),insteadofthestandardreferencepointusedinHSC
(T = 25 C, p = 1 bar), therefore the absolute enthalpies and entropies will be different
from those found in steam tables. However, since point 2 is by default set to the triple
point,theenthalpyandentropydifferences(cellsC5andC6)arethesameastheabsolute
values found in steam tables and diagrams. This is achieved by selectingEdit/Point 2 =
TriplePointfromthemenuandchoosingthe liquidphase.
ThepressurecorrectedenthalpyattemperatureTandpressurepiscalculatedas
Cp(T,p)dT + H
'
H(T,p)= H (298.15K,p)+
f tr , [3]
298.15K
T
' Cp(T,p) H
S(T,p)= S (298.15K,p)+
0 dT + tr , [4]
298.15K
T Ttr
where S0 (298.15K, p) is the modified standard entropy at pressure p and Htr is the
enthalpyofaphasetransformationattemperatureTtr.
The Cp function still utilizes the Kelley equation, but the coefficients are now pressure
dependentaccordingto
where A(p), B(p), C(p) and D(p) are the coefficients fitted at different pressures p. See
Table1foralistofthecurrentpressuresavailable.
The temperature or pressure of a saturated curve is calculated through either one of the
equations68.Thepressureforasaturated gas/liquidmixtureis
whereTisthetemperatureinKandpthepressureinMPa.Thetemperatureforasaturated
liquid/solidmixtureis
whereTisthetemperatureinKandpthepressureinMPa.Theseequationscorrespondto
thesaturatedcurvesinthep,Tdiagramandareutilizedinthemodulewheneverasaturated
stateisselected.
In order to calculate the influence of pressure on the enthalpy and entropy below the
freezingpoint,apressurecorrectiontermisused.Thecorrectiontermis
where Tf is the temperature at the freezing point, pf is the pressure at the freezing point,
av ,ice isthecoefficientofthermalexpansionand nice isthespecificvolume.
25.4 Limitations
Thecurrentpressurerangeis200Cto2000Cand0.001barto1000bar.
Accuracyincpvaluesanddensityvaluesdecreasesclosetothecriticalpoint.
Accuracyinsaturatedliquid/gaspressuredecreasesclosetothecriticalpoint.
Uncertaintiesincpvaluesforiceatdifferentpressures.
Thehightemperatureandpressure region(800C2000Cand100bar1000bar)is
extrapolated.
Thelowpressureregion(0.001bar0.01bar)isextrapolated.
HSCChemistry5.0 261
26. UNITSMODULE
Traditionally,severaltypesofenergy,temperature,massandvolumeunitshavebeenused
inthermochemicalcalculations.Therefore,someinconvenientconversionsareneededto
comparetheresultsfromdifferentsources.ThenewUnitsConversionmoduleisaneasy
tool for fast unit conversions in thermochemistry as well as in other engineering fields.
Thespecificationsofthismodulecanbesummarizedasfollows.
1. Some 90 different quantities and 444 units are available. The user can easily add
ownunitsandcoefficientsintotheconversioncalculatordatabase.
2. The Units Module also offers data sheets for chemical constants, particle mesh
sizes,airhumidityand waterpressuretables.Thesetables canbe modifiedbythe
useraccordingtopersonalrequirements.
UnitsConversions(ConvertSheet)
Fig.1. UnitsConversionmodule.
The user interface of the Units module is shown in Fig. 1. All the data is given in the
workbook, whichconsists ofsixsheets.ThefirstConvert sheet works as asimpleunits
conversioncalculator,whichisusedinthefollowingmanner:
1. Selectthequantityyouareinterestedin,forexample,Energy.
2. Selecttheunitandprefixtobeusedincolumns1and2.
3. Selecttheunitandprefixtobeusedincolumns3and4.
HSCChemistry5.0 262
UnitsDatabase(UnitsSheet)
Fig.2. Databasesheetforunitcoefficients.
TheunitcalculatorontheConvertsheetreadsallthequantitiesandunitcoefficientsfrom
theUnitssheet,seeFig.2.Threerowsarereservedforonequantity,andupto255unitsin
thecolumns canbeused foronequantity.Thename ofthe quantity is given inthefirst
column,thequantityfirstrowgivesthenameoftheunit,thesecondonetheabbreviation
andthethirdonetheconversioncoefficient.
The user may easily add own quantities and units to this sheet. However, remember to
savetheworksheetifyouwanttousethisnewdatalateron.
OtherSheets
TheUnitsworkbookalsocontainsothersheets:
1. Constantssheet:Chemicalandphysicalconstants.
2. Meshsheet:Particlesizesinmeshandmmunits.
3. Airsheet:Aircompositionandhumiditytables.
4. H2Osheet:Watervaporpressuretables.
HSCChemistry5.0 263
27. ExcelAddInFunctions
27.1 Gettingstarted
WithHSC5.0AddInFunctionsitispossibletousetheHSC5.0databasedirectlyunder
MSExcel2000andinthatwaycarryoutseveralthermochemicalcalculations.Inorderto
usethesefunctionsinExceltheymust,however,firstbeactivated.Threestagesmaybe
neededtoactivateHSCfunctionsinExcel.Thenumberofstagesneededdependsonthe
computersettingsandWindowsandExcelversions.
ActivationStage1:
1. OpenExcel2000(NOTE: HSCAddInsdonotworkunderearlierExcelversions!)
2. SelectTools,AddIns... fromthemenu.
3. SelectBrowseandlocateHSC5.xlafromyourHSC5\AddInsfolder.
4. SelectHSC5.0FunctionsandpressOK,seeFigure1.Itmaybenecessaryto
restartExcelinorderfortheaddinfunctionstowork.
Figure1:Adding/removingHSC5.0FunctionsunderExcel.
ActivationStage2:
Iftheinstallationisunsuccessful,thefollowingstepsmayhelp:
1. StarttheVBAEditorbypressingAlt+F11.
(orselectTools,Macro,VisualBasicEditor,...)
2. SelectTools,Referencesfromthemenu.
3. SelectBrowseandlocate HSC5_Excel.dll fromyourWindowsSystem
directory(forexampleC:\Windows\System\HSC5_Excel.dll).Itmaybenecessaryto
restartExcelinorderfortheaddinfunctionstowork.
4. Seealsostage3inChapter27.2ifneeded.
TheHSCinstallationroutineautomaticallytakescareoftheDLLregistration.
HSCChemistry5.0 272
27.2 OpeningandMovingFilesthatuseHSC5.0Functions
Onceinstalled,asabove,youarereadytostartusingtheaddinfunctions.Sometimesit
may be essential to change the links of a worksheet in order for Excel to find the
HSC5.xlafile.ThismaybethecaseifopeningafilethatusesHSC5.0functionsforthe
firsttimeorwhenmovingthesefilesfromonecomputertoanother.Thesestepsshould
thenbecarriedout:
ActivationStage3:
1. During opening, answer No when prompted by Excel to update all linked
information(automaticlinkupdatesdonotworkduetosome buginMSExcel).
2. SelectEdit,Linksfromthemenu.
3. Choosethepathcontaining HSC5.xla fromthelistboxandpressChangeSource.
4. BrowsetoyourHSC5\AddInsfolderandchoose HSC5.xla.
Alternatively, it is also possible to first remove HSC 5.0 Functions under Tools,
AddIns, see Figure 1, and then by adding them again, to force an update of the
worksheetlinks.Ifthecellsconatiningthefunctionsreturna#VALUE!errormessage,
pleasesavethe fileandrestart Excel inorderto makethefunctions work.Tryopening
thetestexampleAddInSample.xls,whereallavailablefunctionsaredemonstrated.To
turntheaddin feature off,simply deselect it usingtheTools,AddIns...dialogfrom
themainmenu.
27.3 BriefDescriptionoftheFunctions
TheaddinfunctionsareusedthesamewayasfunctionsingeneralunderMSExcel.For
example by writing =H(A1A2) the enthalpy for the species in cell A1 and at the
temperatureincellA2,isreturned.ToviewallexistingfunctionssimplyselectInsert,
Functionfromthe main menuandthenchooseUserDefinedfromthe left listbox.
TherightlistboxwillnowgiveshowallavailableHSCfunctionsandtheirarguments.A
completedescriptionofthefunctionsisgiveninthefollowingtable(Table1).
GeneralFunctions
UNITS(TE) Changesthecurrentunits,T=C/KandE=Mcal/MJ/kWh.
SheetNOTrecalculated!
BAL(Equation) Balancesgivenequation.
SPECIES(DBNo,Position) ReturnsspeciesindatabaseDBNoandgivenposition.
SpeciesFunctions
H(SpeciesT) Returnstheenthalpy(permol)ofthespeciesatT(temperature).
S(SpeciesT) Returnstheentropy(permol)ofthespeciesatT.
CP(SpeciesT) Returnstheheatcapacityatconstantpressure(permol)ofthespeciesatT.
G(SpeciesT) ReturnstheGibbsenergy(permol)ofthespeciesatT.
HKG(SpeciesT) Returnstheenthalpy(perkg)ofthespeciesatT.
HNM3orHCM(SpeciesT) Returnstheenthalpy(perNm)ofthespeciesatT.
HLAT(SpeciesT) Returnsthelatententhalpy(permol)ofthespeciesatT.
ReactionEquationFunctions
H(EquationT) Returnstheenthalpy(permol)ofthereactionequationatT.
S(EquationT) Returnstheentropy(permol)ofthereactionequationatT.
CP(EquationT) Returnstheheatcapacitydifference(permol)ofthereactionequationatT.
G(EquationT) ReturnstheGibbsenergy(permol)ofthereactionequationatT.
HSCChemistry5.0 273
Iteration(reverse)Functions
TATH(SpeciesH) Returnsthetemperatureofthespecieswithgivenenthalpy(permol).
TATS(SpeciesS) Returnsthetemperatureofthespecieswithgivenentropy(permol).
TATCP(SpeciesCP) Returnsthetemperatureofthespecieswithgivenheatcapacity(permol).
TATG(SpeciesG) ReturnsthetemperatureofthespecieswithgivenGibbsenergy(permol).
FlowFunctions
FLOWH(SpeciesAmountT) Returnstheenthalpyofaflow(SpeciesandAmountasranges)atT.
FLOWS(SpeciesAmountT) Returnstheentropyofaflow(SpeciesandAmountasranges)atT.
FLOWCP(SpeciesAmountT) Returnstheheatcapacityofaflow(SpeciesandAmountasranges)atT.
FLOWG(SpeciesAmountT) ReturnstheGibbsenergyofaflow(SpeciesandAmountasranges)atT.
TemperatureindependentFunctions
STRUCT(Species) Returnsthestructuralformulaofthespecies.
CHNAME(Species) Returnsthechemicalnameofthespecies.
CONAME(Species) Returnsthecommonnameofthespecies.
CAN(Species) Returnsthechemicalabstractnumberofthespecies.
MW(Species) Returnsthemolecularweightofthespecies.
DE(Species) Returnsthedensityofthespecies.
MP(Species) Returnsthemeltingpointofthespecies.
BP(Species) Returnstheboilingpointofthe species.
PHASE(Species) Returnsthephaseofthespecies.
RGBCOLOR(Species) ReturnstheRGBcolorofthespecies.
REF(Species) Returnsthedatabasereferenceofthespecies.
REL(Species) Returnsthereliabilityclassofthespecies.
PercentageFunctions
MOLP(Species1Species2) Returnsthemol%ofSpecies1inSpecies2.
WTP(Species1Species2) Returnsthewt%ofSpecies1inSpecies2.
CpDataFunctions
CPFUNCTION(Species) Returnsthecompleteheatcapacity(cp)polynomialfunction(asastring)ofthe
givenspecies.
CPA(Species) ReturnstheAcoefficient(asanumber)ofthecpfunction.
CPB(Species) ReturnstheBcoefficient(asanumber)ofthecpfunction.
CPC(Species) ReturnstheCcoefficient(asanumber)ofthecpfunction.
CPD(Species) ReturnstheDcoefficient(asanumber)ofthecpfunction.
TMIN(Species) Returnstheminimumvalidtemperatureofthecpfunction.
TMAX(Species) Returnsthemaximumvalidtemperatureofthecpfunction.
Table1:DescriptionofallcurrentlyavailableHSCaddinfunctions.
A useful Excel example file is located in the catalogue \AddIns in your HSC
installation directory. The example, called AddInSample.xls, can be viewed after the
addins havebeenmadeavailable(describedinChapter27.1).Figure2showswhatthe
examplefileshouldlooklikeusingMSExcel2000.
HSCChemistry5.0 274
Figure2:ExampleincludingallavailableExceladdinfunctions(AddInSample.xls).
The functions are all collected in the column Function and their return values under
Return value. A red font indicates the input values with a short description of every
function shown to the right. This example provides an easy method for testing the
functionsandalsoprovidespracticeinlearninghowtousethem.
HSCChemistry5.0 275
27.4 MoreaboutregisteringDLLFiles
The HSC 5.0 installation routine should take care of all necessary DLL registrations.
When selecting/deselecting the HSC 5.0 addin using Excel, HSC5_Excel.dll is
automatically registered/unregistered. However, it is also possible to register/unregister
theHSC5_Excel.dllandHSC5.dll(usedbytheHeatandMaterialBalancesmodule)files
manually. The program to achieve this is called Regsvr32.exe*) and registration is
completedusingthefollowingmethod:
1. SelectStart,Run...fromtheWindowsmenu.
2. Type regsvr32HSC5_Excel.dllforregisteringExcel2000addinfunctions.
3. Type regsvr32HSC5.dllforregisteringHSC5.0addinfunctions.
Alternativelyitcanbeachievedusingthefollowingmethod:
1. Doubleclickthefile HSC5_Excel.dllinyourWindowsSystemdirectory.
2. If the file is not registered automatically, which is indicated by anOpen With
dialogbox,choose Otherinthedialogwindow.
3. SelectRegsvr32.exefromyourWindowsSystemdirectory.Nowdoubleclickthe
fileagainanditshouldregisterautomatically.
Whenunregisteringfilesfollowthesameprocedure,butaddthe/u switchbeforethefile
name,i.e.regsvr32/uHSC5_Excel.dllforunregisteringHSC5_Excel.dll.
*DescriptionofRegsvr32.exe
Toadd.ocxandcertain.dllfiles,it willbenecessarytorunREGSVR32.EXEfromthe
Run option in the Start menu. The following are the commands and switches needed:
regsvr32[/u][/s][n][i[:cmdline]]dllnameorocxname
/u(unregisteredserver)
/s(silentdisplaynomessageboxes)
/c(consoleoutput)
/iCalldllorocxinstallpassingitanoptional[cmdline]
whenusedwith/ucallsdllorocxuninstall
/nDonotcalldllRegisterServerthisoptionmustbeusedwith/i
27.5 UnactivationofExcelAddInFunctions
To remove HSC 5.1 Functions completely from the AddIns list, simply highlight the
checkboxagainandExcelwillaskwhetheryouwanttoremovetheAddInsfromthelist.