OutokumpuHSCChemistry forWindows

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.
2.
3.
4.
5.
6.
7.

ReactionEquations
HeatandMaterialBalances
HeatLossCalculations
EquilibriumCompositions
ElectrochemicalEquilibria
FormulaWeights
Eh pHDiagrams

8.
9.
10.
11.
12.
13.
14.

H,S,CandGDiagrams
PhaseStabilityDiagrams
MineralogyIterations
CompositionConversions
Elements
Water(SteamTables)
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.
Traditionally, thermodynamic calculations based on experimental or assessed data have
utilized stability functions in various thermodynamic data books and papers in scientific
journals. The difficult searching stage and complicated calculations, as well as
inconsistenciesarisingfromdifferentselectionsofstandardandreferencestates,havemade
thiscalculationprocedurequitetimeconsuming.
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
2.
TECHNICALSUPPORT
3.
ERRORSANDBUGS
4.
LICENSEAGREEMENTFORENDUSEROFHSCCHEMISTRY
4.1
TheLicence
4.2
UseofHSCChemistryModulesandDatabasesSeparately
4.3
Copyright
4.4
Copying
4.5
TransferoftheLicense
4.6
Warranty
4.7
Liability
4.8
Registration
4.9
TechnicalSupport
4.10
ApplicableLawandArbitration
4.11
Millenium(Y2K)Compliance
5.
REGISTRATIONCARD
6.
WHAT'SNEWINHSCCHEMISTRY5.0
6.1
Updatedheatandmassbalancemodule
6.2
NewHSCAddInfuntionsforExcel2000
6.3
NewDrawingToolbar
6.4
NewDiagramOptions
6.5
LargerDatabasewithnewOptions
6.6
ImprovedEquilibriumModule
6.7
NewHeatLossModule
6.8
NewSteamCalculatorModule
6.9
NewHelpRoutine
6.10
OtherImprovements
6.11
NewWindowsMe,2000andXPCompatibility
6.12
WhatsNewinHSCChemistry4.0
7.
INSTALLATIONTOHARDDISK
7.1
SystemRequirements
7.2
Installation
7.3
ImportantNotes
7.4
InstallationandOperationProblems
7.5
RemovingHSCfromComputer(Uninstallation)
8.
INTRODUCTION
8.1
InvitationtonewAuthors
8.2
PhysicalBackgroundofH,S,CandG
9.
OPERATINGINSTRUCTIONS
9.1
StartingHSC
9.2
MainMenuofHSC
9.3
PrinterSettings
9.4
UsingtheHelpButton
10. REACTIONEQUATIONS
10.1
OneChemicalSubstance
10.2
OneChemicalSubstanceResults
10.3
ReactionEquations
10.4
ReactionEquationsResults
11. HEATANDMASSBALANCE
11.1
BasicCalculationProcedure
11.2
FormattingtheWorksheet
11.3
SpecificationofSubstanceGroups(Streams)
11.4
FormulaeintheCells

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11.5
ElementalCompositions
11.6
AdditionalSheets
11.7
TargetDialog
11.8
Graphics
11.9
Multiplebalanceareas
11.10
GeneralConsiderations
11.11
HeatBalanceExamples
12. HEATLOSS
12.1
BasicCalculationProcedure
12.2
HeatLossExamples
12.2.1 ExamplesprovidedbyHSC
12.2.2 SimpleStepbystepExample(creatingsmeltingl.HTR)
12.3
DetailedDescriptionoftheProgram
12.3.1 UsingtheFixValueButtonandthelogicbehingit
12.3.2 MainWindow
12.3.3 ConductionDatabase
12.3.4 ConvectionDatabase,Tablesheet
12.3.5 ConvectionDatabase,Functionsheet
12.3.6 SurfaceRadiationDatabase
12.3.7 GasMixtureRadiationCalculator
12.3.8 PracticleRadiationCalculator
12.3.9 TargetCalculations(TargetDialog)
12.3.10 Userspecifieddiagrams(DiagramDialog)
12.3.11 Limitations
12.4
BasicTheorybehindHeatTransfer
12.4.1 Conduction
12.4.2 Convection
12.4.3 Radiation
13. EQUILIBRIUMMODULE
13.1
StartingfromdefiningtheElements
13.2
GivingInputDataforEquilibriumCalculations
13.3
AqueousEquilibria
13.4
GeneralConsiderations
13.5
Limitations
13.6
CalculationRoutines
13.6.1 GIBBSEquilibriumSolver
13.6.2 SOLGASMIXEquilibriumSolver
13.7
DrawingEquilibriumDiagrams
13.7.1 SelectingDataTypefortheXandYaxis
13.7.2 ResultGraphics(EquilibriumDiagram)
13.7.3 EquilibriumDiagramTable
13.8
Nonidealmixture:GaAsExamplewithActivityformulae
13.9
CaCO3Example(Aqueoussolutionexists)
13.10
VaporPressures
14. HSCEQUILIBRIUMMODULESAMPLES
15. CELLEQUILIBRIA
15.1
CellModule
16. FORMULAWEIGHTS
17. EhpHDIAGRAMS(Pourbaixdiagrams)
17.1
Introduction
17.2
ChemicalSystemSpecifications
17.3
EhpH DiagramMenu
17.4
NormalEhpHDiagrams
17.5
SpecificationsforCombinedDiagrams
17.6
CombinedEhpHDiagrams

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17.7
CalculationResultsofCombinedDiagrams
17.8
EhpH DiagramsinPractice
18. EppHSamples
19. H,S,CANDGDIAGRAMS
20. DIAGRAMGRAPHICS
20.1
GraphicalObjects
20.2
FormattingtheDiagram
20.3
EditingandCombiningDiagrams
21. PHASESTABILITYDIAGRAM
21.1
TppDiagramModule
21.2
TppDiagrams
21.3
LppDiagramModule
21.4
LppDiagramMenu
21.5
LppModuleDiagram
22. MINERALOGYITERATIONS
23. COMPOSITIONCONVERSIONS
24. ELEMENTSMODULE
25. WATER
25.1
BasicCalculationProcedure
25.2
Calculationexamples
25.2.1 Icemeltingathighpressure
25.2.2 Evaporationprocessinaheatrecoveryboiler
25.2.3 Steamturbineprocess
25.3
DetailedDescription
25.3.1 Pressurecorrectioninthedatabase
25.3.2 Basictheory
25.4
Limitations
26. UNITSMODULE
27. EXCELADDINFUNCTIONS
27.1
Gettingstarted
27.2
OpeningandmovingfilesthatuseHSC5.0functions
27.3
Briefdescriptionofthefunctions
27.4
MoreaboutregisteringDLLfiles
27.5
UnactivationofExcelAddInFunctions
28. HSCDATABASES
28.1
DatabaseMenu
28.2
NotationsandAbbreviationsusedintheDatabase
28.2.1 HSCFormulaSyntax
28.3
ReferenceStates
28.4
AqueousIons
28.5
SearchOption
28.6
FindingSpecieswiththesameStoichiometry
28.7
ListingSpeciesNames
28.8
ListingSpeciesFormulae
28.9
ListingSpeciesDataintheOwnandMainDatabase
28.10
EditingDatainOwnandMainDatabase
28.11
SavingDatainOwnDatabase
28.12
FittingCpData
28.13
ConvertingCpFunctions
28.14
ConvertingThermochemicalDatatoH,SandCpformat.
28.15
ConvertDatabaseFileFormat
28.16
ConvertingoldHSC2.0DatabasestoHSC4.0Format
28.17
SelectingActiveDatabases
28.18
ColorCodes
29. HSCFORMULASYNTAXFORHYDROCARBONSPECIES

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29.1
Basichydrocarbons,CxHy
29.1.1 Appendagegroups
29.1.2 Aromaticcompounds
29.2
Halogencompounds
29.3
Hydrocarbonscontainingnitrogen
29.3.1 Amines,RNH3,R1NHR2,R1,R2NR3
29.3.2 Aminoacids
29.3.3 Hydrazines,RNHNH3
29.3.4 Amines,RC=0NH2
29.3.5 Nitriles,R=N
29.3.6 Nitrocompounds,nittrates,RNO2
29.4
Hydrocarbonscontainingoxygen
29.4.1 Ethers,R1OR2
29.4.2 Aldehydes,RC=0H
29.4.3 Ketones,R1C=OR2
29.4.4 Esters
29.4.5 Alcoholsandcarbohydrates
29.4.6 Phenols
29.4.7 Acids
29.5
Hydrocarbonscontainigsulfide
29.5.1 Thiols,RSH
29.5.2 Sulfides,thiacompounds,R1SR2
29.5.3 Disulfides,dithiacompounds,R1SSR2
29.5.4 Sulfoxides
29.5.5 Sulfones
29.6
Reference
30. ACKNOWLEDGMENTS
31. THERMOCHEMICALDATASOURCES
32. REFERENCES
33. DATAREFERENCES
34. SPECIES
35. HSCDLLTOOLS
35.1
GettingStarted
35.2
ExampleFiles
35.3
DescriptionofavailableSubroutines

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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.

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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.

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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.

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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.

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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.

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ImprovedEquilibriumModule

Calculationreliabilityhasbeenimprovedinmanyofthetestcases.
Newdatabasesearchoptionswithoutthelimitof2000species.
NewSpeciesNamedisplayaddedtothedatabasesearchroutine.
NewWarningsroutinefortemperaturerangeextrapolation.
Smallfixese.g.speciesnamelengthincreasedfrom20to24characters.

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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.

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TheHeatLossmoduleisintegrated withthreedatabasesandtwocalculators:
Conductiondatabasewith718substances
Convectiondatabasewith111substancesand4functions
Radiationdatabasewith61surfacematerials
GasRadiationCalculatorwithH2O,CO2,CO,NO,SO2andCH4data
ParticleRadiationCalculator.
Theusermayeditoraddnewdatatothesedatabases.

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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.

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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.

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HSC5.0iscompatiblewithWindows95,98,NT,Me,2000andXP.

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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.

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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.

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WhatsNewin HSCChemistry4.0
The new HSC version 4.0 contains several new calculation modules, new properties
andalargerdatabasewithalot ofupdateddata.ThefamiliarHSCstyleuserinterface
hasbeenmaintainedinordertominimizethetrainingrequirementsofcurrentHSCusers.
Thenewfeaturescanbesummarizedasfollows:
1. The numberofsubstances inthe databasehas been increased from11000to more
than15000.Alotofolddatahasalsobeenupdatedandextended.
2. Improvedgraphics,printingandformatpropertiesinallmodules.
3. TargetcalculationsintheHeatBalancemoduleforautomaticiterations.
4. ImprovedcalculationreliabilityandspeedintheEquilibriummodule.
5. EhpHdiagramswithconcentrationandtemperaturelines.
6. A new Tppmodule for stability diagrams with partial pressure and temperature
axes.
7. AnewDiagrammoduleforH,S,Cp,G,DH,DG Tgraphics.
8. AnewMineralogymoduleforfastconversionbetweenmineralogicalandelemental
compositions.
9. AnewElementmodulewithbasicdataofelementsandgraphics.
10. AnewUnitsmodulewithausefulunitsconversioncalculator.
11. Alotofsmallfixesandtuningofpropertiesbasedonuserfeedback.
12. New32bitHSCversionforWindows95,98andNT.
Thefollowingsectionswillgiveaideaofthesenewfeaturesinmoredetail.

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.

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EquilibriumCalculations
EquilibriumCalculations is one ofthe mostused modules inHSCsoftware,thereforea
lotofefforthasbeenspentonimprovingit.Forexample:
1.

ThecalculationreliabilityandspeedofGibbssolverisbetterthanintheprevious
version.

2.
3.

TheprocessingofExceltypeactivityformulaehasbeenimproved.
Thespeciestableformcaneasilyberesized.

4.

The diagrams can be printed in any size. A greater number of lines can be
visualizedsimultaneouslybyincreasingtheheightoftheprinteddiagram.

5.

Theenthalpyofthereactioncanbedrawnonthediagram.

6.

Themaximumnumberofpuresubstancesinthediagramshasbeenincreasedfrom
99to999.

7.

ThismodulenowmakesinputfilesforChemSage2,3and4versions.
(ChemSageisaregisteredtrademarkofGTTTechnologies)

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.

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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)

2.

Several species can be selected to the enthalpy diagrams simultaneously to

comparetotalorlatententhalpies.

3.

DGdiagrams (Ellinghamdiagrams), offeraveryfastwaytocomparetherelative

stabilities of substances. For example, you can find out which oxide or chloride
compound is the moststable one.This information isuseful when comparingthe
reductionandoxidationtendenciesofdifferentelements.

4.

This module can also be used to compare the basic thermochemical data from
different sources, in order to see the differences and select the best data for
subsequentcalculations.

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.

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The database contains data on 56 different properties of elements. As in other HSC

modules,theuserispermittedtomodifyandaddnewdatatothis databaseaccordingto
personalrequirements.

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
The thermochemical database is an essential part of HSC Chemistry, because the
accuracyofthecalculationresultsofallHSCmodulesdependsonthequalityofthebasic
data in the integrated database. Considerable development work has been carried out,
whichcanbesummarizedasfollows:
1.

Thenumberofspeciesinthedatabasehasbeenincreasedfrom11000tomorethan
15000. This data is not critically evaluated, but gives fast access to data and
references,whichcanbefoundfromliterature.

2.

The quality of the database has been improved and the number of unnecessary
duplicatespecieshasbeendecreased.

3.

Further supporting data, such as structural formulae, chemical names, common

names,CAS numbers, meltingpoints,boilingpoints,etc. havebeenaddedtothe
database.

4.

HSC4usesthesamedatabaseformatasHSC3,therefore,theuser'sowndatabases
canalsobeusedwiththenewHSC4.0.

5.

The search procedure for species in "Database Editor" and "Show Database"
windowshasbeenimproved.Thespecieslistsnowshowthelocationoftheclosest
matchifthegivenformulaisnotfoundinthedatabase.

6.

Adirectlinktothegraphics modulehasbeenaddedtotheCpdatafittingoption.
Thisallowstheeasycomparisonofexperimentalandfitteddata.

7.

Important Note: The main reason for the small differences with HSC 3 and 4
calculationresultsisthenewdataintheHSC4database.

Generalimprovements
The graphics,printingandformat properties as wellas resizingcapabilities ofthetable
forms havebeenimprovedinmostcalculationmodules.This makes iteasiertoproduce
highqualityhardcopiesoftheresults.

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Numerous minor improvementsandadjustments havebeen made whichare not always

visible. However, they will make the life of the HSC user easier. This work has been
basedmainlyonfeedbackfromHSCusers.

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INTRODUCTION
HSC Chemistry is designed for many different kinds of chemical reactions and
equilibriumcalculations.Thecurrentversioncontains14calculationoptions:
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.

ReactionEquations
HeatandMaterialBalances
HeatLossCalculations
EquilibriumCompositions
ElectrochemicalCellEquilibria
FormulaWeights
PhaseStabilityDiagrams(TppandLppversions)
Eh pHDiagramswithconcentrationandtemperaturevariables
Enthalpy,entropy,heatcapacity,GibbsenergyandEllinghamdiagrams.
MineralogyIterations
Compositionconversions
WaterSteamTablesandMollierDiagrams
UnitsConversions
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.
With HSC Chemistry it is possible to calculate chemical equilibria between pure
substances and the ideal and also, to some extent, nonideal solutions. For these
calculations onlyenthalpy(H),entropy(S)andheatcapacity(Cp)dataforallprevailing
compounds or pure substances is needed. In many cases these calculation results may
simulatetherealchemicalreactionsandprocessesatsufficientaccuracyforthepractical
applications. Important advantage is also that specification of the chemical system, data
retrieval and final calculations may be carried out in normal Intel Pentium personal
computerswithinfewminutes.

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Ofcourse,experimentalworkisneededtoverifytheresults,becauseHSCdoes nottake
kineticphenomenaintoaccount.However,HSChelpstoavoid expensivetrialanderror
chemistry, because it quickly and easily gives some kind of clue as to the effects of
process parameters on the reaction products and process conditions. Usually,
thermochemical calculations at least show what is physically possible and what is
impossible, which is highly valuable information when making plans for experimental
investigations.
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.
A number of solution models are available in literature to describe the nonideality of
mixture phases. The practical problem is quite often a lack of valid data for solution
parameters.AlthoughsolutionmodelshavenotbeeninstalledintheHSCChemistry,the
nonideality of solutions can be taken into account in the equilibrium calculations to a
certain extent by including constant activity coefficients or simple activity coefficient
formulaeintheGibbsequilibriumsolver.

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.

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PhysicalBackgroundofH,S,CandG
Thermochemical calculations are based on enthalpy H, entropy S, heat capacity Cp or
GibbsenergyGvaluesforchemicalspecies.Theycanallbemathematicallyderivedfrom
experimental observations. The following presentation gives a brief and simplified but
illustrativeideaofthethermochemicalquantitiesandmethods.
Enthalpy H: Absolute values of enthalpy H of substances cannot be measured, but
enthalpy differences between two temperatures can be determined with a calorimeter.
HeatcapacityCpatconstantpressure(specificheat)canbecalculatedfromthisdatausing
Eq.(1).
Cp

(dH/dT)P,n

[1]

Equation(1)allowsthecalculationofenthalpyas

H(T) =

T
Hf(298.15)+ CpdT+
298.15

SHtr

[2]

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.

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H,kJ/molEnthalpyofZincSulfide
160
298.15K

140

gas

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

298.15K

50
0
50

EnthalpyofFormation=
201.669kJ/mol

100

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.

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EntropyS:Absolute entropy values canbecalculatedfromthe experimental heat capacityvalues using

Equation(3)andnumericalintegration.
T
S

S(298.15)+

(Cp/T)dT+
298.15

SHtr/Ttr

[3]

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.
HeatCapacityCp:Theabsolute heat capacity ofsubstances at constant pressure canbe
calculatedasafirstderivativeoftheenthalpycurveinFig.2,usingEquation(1).Theheat
capacitycurveisdiscontinuousatphasetransformationtemperatures,seeFig.5.Theheat
capacityvaluesofcrystallinesubstancesinequilibriumapproacheszerovalueat0K.
Thetemperaturedependenceofheatcapacityatelevatedtemperaturescannotbepredicted
theoretically by thermodynamics. A fully mathematical correlation is therefore adopted
for fitting experimental heat capacities. The Kelley equation is used throughout this
programinthefollowingform:
Cp

A+B.103 .T+C.105 .T2+D.106 .T2

[4]

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.

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S,J/(mol*K)Entropyof
200 Zinc
gas

298.15K

180
160

97.721

140
120
160.415

100

liquid

80
solid

60

10.571

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
298.15K

30

solid
mp=692.7K

bp=1180K

25

gas
20
15
25.403
10
5
0
0

200

400

600

800

1000

Temperature,K

Fig.5. Heatcapacityofzincfrom0Kto1400Kcalculatedfromcalorimetricdata,byEq.(1).

1400

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G,kJ/molGibbsEnergyof
0 Zinc

12.412
solid

33.841

20

74.825

40

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.
Table1shows thethermochemical dataofzincas printedfromtheHSCmain database.
ThesameenthalpyvaluescanbefoundinFig.2,aswellastheentropyvaluesinFig.4.
The coefficients A, B, C and D have been derived from the experimental heat capacity
values,Fig.5,usingcurvefittingandEquation(4),seeChapter28.12.
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.

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Species State Enthalpy
H
kJ/mol
Zn
Zn
Zn(g)

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Entropy
S
J/(mol*K)

0.000
7.322
130.415

HeatCapacityCp
A
B
J/(mol*K)

41.631 20.736 12.510

10.571 31.380 0.000
160.984 20.786 0.000

TemperatureRange
C

0.833
0.000
0.000

0.000
0.000
0.000

T1
K
298.150
692.655
298.150

T2
K
692.655
1180.000
2000.000

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.
ChemicalReactions:Thethermodynamic enthalpy, entropyand Gibbs energy functions
forachemicalreactionarecalculatedasthedifferencebetweentheproductsandreactants,
usingEquations(6)(9).ThecommonlyneededequilibriumconstantKcanbecalculated
usingEquation(11).Thephysicalmeaningofthesefunctionsandvalueswillbedescribed
inmoredetailinChapters10.1 10.4.
Chemicalreaction:

aA+bB+...=cC+dD+...

[6]

Enthalpyofreaction:

DHrSniHi(Products) SniHi(Reactants)

[7]

=(c*HC + d*HD+...) (a*HA + b*HB+...)

Entropyofreaction:

DSr SniSi(Products) SniSi(Reactants)

[8]

=(c*SC + d*SD+...) (a*SA + b*SB+...)

Gibbsenergyofreaction:

DGrSniGi(Products) SniGi(Reactants)

[9]

=(c*GC + d*GD+...) (a*GA + b*GB+...)

Equilibriumconstant:

[C]c *[D]d *...

K=
[A]a *[B]b *...

[10]

lnK = DGr/(RT)

[11]

wherethefollowingabbreviationshavebeenused:
[A] =
activityorpartialpressureofspeciesA,B,C,etc.
a
=
stoichiometriccoefficientofspeciesAinreaction
n
=
stoichiometriccoefficientofaspeciesinreaction(a,b,c,...)
R
=
gasconstant=1.987cal/(Kmol)=8.314J/(Kmol)
T
=
TemperatureinK

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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.

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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):

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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

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and D exist in the HSC Chemistry databases. The extrapolation error increases
rapidly at higher temperatures. More information on extrapolation is given in
Chapter28.4.
6.

10.2

Foraqueousspeciesitisrecommendedtoset:
Lowertemperature
=25C
Uppertemperature
=300C
Step
=25C

OneChemicalSubstanceResults
AfterpressingtheCalculatebuttonin theprevious screen,Fig.1,you willarrivein the
resultswindow,Fig.2.Fromthisresultsscreenyoucansaveandprinttheresults:
1.

Press Save if you wish to recalculate the results later. The Save button will also
savethesettingsusedinFig.1.YoucanreadthesefilesbacktoHSCusingtheFile
Open button,seeFig.1.

2.

Press Print if you want a paper copy. If you have selected the Collect to Sheet
option in Fig. 1, then all results will be collected on the same sheet and can be
printedtogether.Clearwillcleartheresultssheet.

3.

Press Copy to get the results of selected cells into the Clipboard, then you can
easilypastetheresults,forexample,toMSExcel,seeFig.2.

4.

PressCopyAllto get alltheresults ofthesheet into theClipboard,then youcan

easilypastetheresults,forexample,toMSExcel,seeFig.2.

5.

PressOK toreturntothepreviousWindow.

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ReactionEquations

Fig.3. InputdataforReactionEquationcalculations.

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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)

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Write the reaction equation into the box, see Fig. 3. If you have not given the
stoichiometric coefficients for the species, you can press Balance Equationfor solving
unknowncoefficients.Thebalancebuttonsolvesthecoefficientsonthebasis ofelement
balanceequations.Thereforeitcannotsolveunknowncoefficientsiftheirnumberislarger
thanthenumberofelementsinthecorrespondingreaction.
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.
K=pMg/aMg =pMg

[1]

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.

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Fig.5. InputdataforReactionEquationcalculations.

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Fig.6.TheequilibriumconstantKis equaltothevaporpressureinatmaccordingtoEquation(1)ifthe
activity of magnesium is 1. The boiling point of magnesium is about 1100 C beyond which its vapor
pressureexceeds1atm.

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Fig.7. WritethereactionequationwithoutstoichiometriccoefficientsandpressBalanceEquation.

Fig.8. PressCalculatetodisplaytheresults.

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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.

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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.

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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.

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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.

2.
3.

11.1

Theusertypestheinputandoutputspecies,temperaturesandamountsintotheIN1
andOUT1sheetsrespectively.Thisisasimplewaytocalculateheatandmaterial
balancesandwasavailablealreadyinHSC2.0.However,theproblemwiththeold
versionwasthattheuserhadtomanuallymaintainthematerialbalancewhenthe
inputfeedchanged.
Materials (species) are given as groups of substances, called streams. These
streamscanbethesameasthephases,buttheycanalsobeamixtureofphases.
The output amounts can be linked with the input amounts with Excel type cell
references,orviceversa.

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

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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
Where:

A
T2
T1

=
=
=

[1]

Outersurfaceareaofthereactor(m2)
Surfacetemperatureofthereactor(C)
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.

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Fig.3. Temperatureoftheproducts(adiabaticprocess).
9.
10.
11.

12.
13.
14.

15.

16.

11.2

To insert an empty row in the table, select Row from the Insert menu or by
pressingtherightmousebuttonandselecting InsertRowfromthepopupmenu.
RowscanbedeletedbyselectingRowfromtheDeletemenuorpressingtheright
mousebuttonandselecting DelRowfromthepopupmenu.
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.
Temperatureunitscanbechangedbyselectingthe CorKfromthe Unitsmenu.
Energyunitscanbechangedbyselecting Mcal,MJorkWh fromthe Unitsmenu.
Ifapapercopyisneeded,selectPrintfromtheFilemenu.This optionwillcopy
allthedataonthesamePrintsheetandwillalsoprintthissheetonpaperiftheuser
presses OK. Notice that you can delete this Print sheet by activating it and then
selectingSheetfromtheDeletemenu.ThePrintSheetselectionintheFilemenu
willprintonly theactivesheet.
Tosavethesheets,selectSavefromtheFilemenu.Pleasesavesheetsoftenusing
differentnames,becauseyoumaywishtomakesmallchangeslaterortoreturnto
the original sheet. Saving sheets is important, because the Undo feature is not
availableinHSCChemistry.
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.

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

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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.
2.
3.

Airfeed.
Processgasoutput.
Homogenousliquidandsolidinputsandoutputs.

Examplesofmultiphasestreamsare,forexample:
1.
2.
3.

Liquidmaterialwithsolidparticles(suspension)asinputoroutput.
Solid feed mixture of the process, made of different substances, such as mineral
concentrate,coalandsand.
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.
2.
3.
4.

Asksforanameforthenewgroup,whichyoucanchangelaterifnecessary.
Insertsanewemptyrowabovetheselectedcellwithalightbluepattern.
HSCassumesthatallrowsunderthenewgrouprowwillbelongtothenewgroup
downtothenextgrouprow.
Inserts Excel type SUM formulae in the new group row for calculating the total
amountinthegroupusingkmol,kgandNm3 units.

Oncetheinsertprocedureisready,youcaneditthegrouprowinthefollowingway:
1.
2.
3.

4.

Thestreamname(label)canbeediteddirectlyinthecell.
Thestreamtemperaturecanalsobechangeddirectlyinthecellandwillaffectthe
temperatureofallthespeciesinthisgroup.
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.
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.

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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.

Fig.4.TheOUT1sheet oftheHeatBalancemodule.Thespecies havebeendividedintothreestreams,

whicharethesameastheexistingphases.

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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.

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Fig.5.TheOUT1sheet oftheHeat Balance module.Copperoutputhas beenlinked withcopperinput

withaformulaanddefinedname:InCu.

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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.
Noticethataproceduretoconvert elementalanalysis backtospeciesanalysis is notyet
availableintheheatbalancemodule.Ageneralsolutiontothiskindofproblemis quite
difficult and in many cases impossible. However, a custommade solution for an
individualcaseispossiblewithalittleeffortandnormalExceltypeformulae:
1.

Createanewsheetusingthe Sheetselectioninthe Insertmenu,seeFig.6.

2.

Renamethenewsheetbydoubleclickingthetab,forexampletoCompositions.
NoticethatyoucanusealsotheInput%sheetasthestartingpointasyourename
it.

3.

Typetheelementalandspeciescompositionsonthenewsheet.

4.

Notice that you can insert Formula Weights in this new sheet by selecting the
chemicalformulacellsandthenselecting MolWeightfromthe Insertmenu.

5.

Create Exceltype formulae, which convert the elemental analysis of a group to

moleamountsofspeciesusingformulaweightsoftheelementsandspecies.

6.

Type formulae in the kmol columns of the IN1 sheet, which refer to species
amountsintheCompositionssheet.

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Fig.6.TheOut1%sheet oftheHeat Balancemodule.Thissheetshowstheelementalcompositions of

thephases,aftertheStreamCompositionsoptionhasbeenselectedfromtheCalculatemenu.

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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.

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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.

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7.

8.

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Usuallyit is also necessaryto give estimatedinitial Test Values incolumnCfor

the automatic iterations. Iteration ends when the target value (col H) or iteration
number(colI)isreached.Accuracycanbeimprovedbyincreasingthenumberof
decimalsusedincolumnsGandHwiththeFormatNumberselection.
Select the rows (> 3) on the Target sheet which you want to iterate and press
Iterate selected rows or F8. If all rows should be iterated, simply press Iterate
All.

Inthefollowing example,showninFig.8,youcanselect for examplerow4andpress

F8. This will evaluate the copper scrap amount which is needed to maintain the heat
balanceinthegivenconditions.Row5canbeusedtoiteratetheironcontentofthematte
inthesameconditionsandrow6to achieveagivenFeSamount.
Importantnote:PleaseuseonlyStreamtemperaturecellsasvariablesforthetemperature
iterations,ie.donotusespeciestemperaturecells.

Fig.8. Targetdialogspecifiesthevariablesandtargetcellreferences.

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Graphics
Occasionally it is usefultoseetheresults,offorexampleaheat balancecalculation,in
graphicalformat.Thiscanbecarriedoutmanuallybymakingstepbystepchangestoone
variable cell and collecting data from interesting cells, for example, to an Excel sheet.
Sometimesfurthercalculations mayberequiredaftereverystep,whichcanbespecified
usingtheDiagramDialog.Stepbysteptheprocedureisasfollows:
1.
SelectDiagram/DiagramDialogfromthemenu.
2.
Select the variablecellandpressSetXcellfromthe dialog.Select,forexample,
cellC11,seeFig.7.
3.
Select a cell for the yaxis and press Set Ycell from the dialog. Select, for
example,theHeatBalancecellatthebottomrightoftheform.Youmayrepeatthis
stepandcollectseveralcellswhosevalueswillbedrawntothediagram.
4.
If other calculations are required between every step, press Target iterationand
theTargetsheetwillautomaticallyopen.Selectthecalculationrowsthatshouldbe
iteratedbeforetheYrowandpressSetTargetrowsfromthemenu.Therowdata
willnowbetranferredtotheDiagramdialogintocolumns4,5,etc.
5.
FilltheDiagramSettingsasshowninFig.9.YoumustspecifytheMIN,MAXand
STEPvalues fortheXAxis. Youcanalsospecifythecellreferences, labelsand
unitsmanuallyinthisform.
6.
PressDiagramtocreatethetabulardataforthediagramandDiagramonceagain
toseethefinaldiagram,Fig9.
7.
The diagram can be modified, copied and printed in the same manner as other
diagramsinHSCChemistry.
8.
Show/Toolbar shows the drawing menu and Show/Object Editor shows the
objecteditor,whichletsyouspecifytheobjectsmanually.
9.
ToreturntotheHeat Balance module,pressExitat thebottom left cornerofthe
diagramform.
FromthediagramshowninFig.9youcanseethatroughly68kg/hofscrapisneededto
adjusttheheatbalancetozero.Noticethattheunitsinthediagramarekg/handkW.

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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%.

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Fig.10. Diagramwheretheheatbalanceisautomaticallyiteratedtozerobeforeeverycalculationstep.

11.9

Multiplebalanceareas

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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.
A new balance area is created by selecting either Insert/Balance Area to Right or
Insert/Balance Areato Left from the menu. This will insert a pair of INx and OUTx
sheetstothecorrespondingposition.Abalancearea may easilybe deletedbyselecting
Delete/Balance Area. Deleting a single sheet of a balance area, for example an INx
sheet,isnotpossible.ThebalancesareallautomaticallycollectedintotheBALsheetso
pleasedonotmodifythissheet.

Fig.11. The BALsheetwhentheworksheetconsistsof5balanceareas.

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

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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.

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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.

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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.

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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).

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11.10

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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.
TheRed FontShieldproperty is sometimes useful if you want toprevent accidental
changes to cells. You can activate this property by selecting Format Red Font Shield
fromthemenu.Afterthisselectionyoucaneditonlythosecellswhichcontainredfont.
Ifyouhavecarriedoutalaboratoryorindustrialscaleexperimentorprocesscalculations
youusuallyknow:
1.
2.
3.

Theraw(input)materialsandtheiramountsandtemperatures.
Theproduct(output)materialsandtheiramounts,temperaturesandanalysis.
Theinputheatandheatlossescanfirstbeestimatedaszero,ifnotavailable.

In order to calculate a heat balance you must first convert the (elemental) chemical
analysisoftherawmaterialsandtheproductsintoinputandoutputsubstances(species).
Sometimesthisstepisthemostdifficult,soyoumaychoosetocarryoutthisprocedure

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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.
Onthebasis ofthefinalresults,conclusions canbemadeas towhetherextraenergyis
neededorincreasedinsulationisrequiredorifthereactorneedscoolingonalargescale.
TheheatlossesmayalsobedeterminedusingtheHeatLossmodule.Combiningthetwo
modulesprovidesapowerfulwayofcalculatingprocesses.
Itisimportanttonotethatthisisarealheatbalanceforengineeringpurposes,whichalso
takesintoaccountthekineticaspectsiftheuserinputisbasedonrealexperimentaldata.
Theheatbalance,whichcanbeobtainedfromtheequilibriumcalculations,istheoretical
inthisrespect.Itisvalidonlyiftheequilibrium isreachedintherealprocess.

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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,

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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.

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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.
Thebasicconcept ofthe module is that theuserspecifies thesystemsetup byselecting
the geometry of the object, inserting columns, specifying a material for each column,
specifyingthicknesses(ifany)andenteringeitheronetemperaturepointandatotalheat
loss or two arbitary temperature points within the same sheet. From these inputs the
program can calculate either the temperature profile or the total heat loss. The
temperatureprofile(profiles)canthenbeplottedgraphically.

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The main workbook is verysimilartoExceltype worksheets interms oftheproperties

that can be found in the menu and also most of the Excel worksheet functions are
available.
ThenewHeatLossmodulemaybeused,forexample,toestimateheatlossvaluesneeded
intheBalancemodule.Theusermustfirstspecifythecolumntypes,whichcanbe Layer,
Layercontact,SurfaceandEnclosure.Thethickness mustbespecifiedforLayerand
Enclosurecolumns,while Layercontactand Surfacecolumnshavezerothickness.Two
basictypesofcalculationsmaybecarriedout:
1. Temperatureprofilewithfixedheatlossandonetemperaturepoint.
2. HeatLosswithtwofixedtemperaturepoints.Thiswillreturntheheatlossbutalso
thetemperatureprofile.
The calculation routine handles conduction, convection and radiation properties as
functions of temperature but fixed values may also be used by selecting the value and
pressing the Fix Value button. These fixed values are shown in red on the calculation
sheet.
Temperatureprofileaswellassomeotheruserspecifiedvaluesmayalsobepresentedin
graphicalform. Targetdialogmaybeusedtofind,forexample,minimumlayerthickness.
Thecalculationspecificationsmaybesavedtofilesforlateruse.

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

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(hc and/or hr) on row 7 and/or row 8. It is also possible to specify the
emissivities and/or absorptivities on rows 2023, in this case please make
surethattheradiationcoefficientisunfixed.
- Layercontactcolumn:Enterthethermalresistanceonrow11.
- Enclosure column: Enter the convection coefficient on row 7 and/or the
radiationcoefficient onrow8.It isalsopossibletospecifytheemissivities
on the adjacent layer columns, in this case please make sure that the
radiationcoefficientisunfixed.
3. Foreach value enteredpress theFixValuebutton,unless the valueis already
fixed.Bydoingthistheprogramwillusethesegivenvalues,indicatedbyared
font,whencalculatinginsteadofthedatabasevalues.
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.

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HeatFlow (pressthe Heatflowbutton):

- Specifytemperaturepointsusingthecursor.
- 0or1pointselected (bycursorposition):Thewholerangewillbecalculated.
- Cube or cylinder geometry: Specify calculation range by selecting either
Calculate all sheets (calculates all walls) or Calculate active sheet
(calculatesactivewall).
- All sheets will have the same inside and outside temperatures as on the
currentsheet,oncethecalculationiscompleted.
- 2 points selected (by selection): The range between these points will be
calculated.
- Cubeorcylindergeometry:Theothersheetswill notbecalculated.
- The endtemperaturepoints intheselectionwillremainconstant.
8.PresstheDrawDiagram buttonforagraphicalplotofthetemperatureprofile.

PeterBjorklund

12.2

HeatLossExamples

12.2.1

ExamplesprovidedbyHSC

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Seethe examples providedbytheHSCpackagebyselectingFile/Openfromthe menu

andselectingtheappropriatefile(examplesexistin\HSC5\Heatlossfolder).
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.

PeterBjorklund

Figure2:Radiatorcalculationexample.

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PeterBjorklund
3.

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HeatlossfromuninsulatedpipeatconstantT(incropera94_503.HTRfile)
This isanexampletakenfromFundamentals ofHeat andMassTransferbyF.P.
Incropera and D. P. DeWitt (page 503 in the 4th edition) /1/. In this example the
heat loss fromanuninsulated horizontalpipeis calculated with knowledge ofthe
surfacetemperature(165C)andtheairtemperature(23C).

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

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is1200Candthewalltemperatureis500C.ThewallsurfacematerialisSteel
(sheet with skin due to rolling)and the convective gas is approximated as Air
(p=1bar).Thesecanbothbefoundfromthedatabase.Thereisa10mmthick
Plain carbon steel layer surrounding the furnace. It is important to insert a
LayeroraLayercontactcolumntotherightoftheSurfacecolumn,inorderto
calculateinternalradiation (or convection), since the program otherwise assumes
outside radiation (or convection). By entering a very low thickness value for the
Layer column (row 4), or by entering zero thermal resistance for the Layer
contact column (row 11), the inside surface temperature may still be used in the
LayerorLayercontactcolumn.
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.

8.

Smelting reactor calculation

Smelting3.HTRfiles)

(Smelting1.HTR,

Smelting2.HTR

and

Inthisexamplethetemperatureprofilesandheatlossesofthreedifferenttypesof
smelting reactors are calculated. The default input values given in this example
havenotbeentakenfromanyspecificreactortype,howevertheinputvaluesmay
easilybechangedinordertoachieveamorerealisticsituation.
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.

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12. SelectMoltenmetal bymovingthecursortorow4.

13. ClicktheForcedConvection optionbuttonandtype 0.02(=2cm/s)inthespeed
textbox.
14. Pressthe Selectbutton.
15. Type 1200astheinsidetemperatureincellC9and 20astheoutsidetemperaturein
cellE10.
16. Pressthe Heatlossbutton.
HeatLosswillnowcalculatethetotalheatlossfroma1x1msquareofthereactorwall.
The inside and outside convection coefficients, calculated from the Function sheet, are
based on generalized empirical data. They can, however, be used up to a reasonable
accuracy for smelting reactor walls with corresponding cooling methods. The
temperature profile may be plotted graphically by pressing the Draw Diagrambutton.
The following procedure describes how it is possible to compare several temperature
profileswithinthesamediagram.
1. SelectInsert/Wallsheetfromthemenutwice.Twocopiesofthereactorwallare
created.
2. SelectWall2sheetandtype 1400astheinsidetemperature(cellC9).
3. Pressthe Heatlossbutton.
4. SelectWall3sheetandtype 1600astheinsidetemperature(cellC9).
5. Pressthe Heatlossbutton.
6. Pressthe DrawDiagram button.
Now the temperature profiles for three different inner temperatures (1200 C, 1400 C
and1600C)areplotted.After modifying the diagram labels andtheirpositioning,the
final diagram might look similar to the enclosed diagram (Figure 4). The setup should
nowalsobesimilartothatoftheSmelting1.HTRexample.

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Figure4:TemperatureprofilesforSmelting1.HTRcalculationexample.

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12.3. DetailedDescriptionoftheProgram
12.3.1

UsingtheFixValueButtonandthelogicbehindit
OncetheFixValuebuttonisactivatedtheuseris ableto fix values manuallyto make
these a direct input for the calculation. A fixed value is indicated by red font and the
captiononthebuttonchangingto UnfixValue.If,forexample,theuserwishestospecify
the convection coefficient hc directly, the specified value must be fixed (and the fluid
nametypedmanually),otherwisetheprogramwilliteratethevalueusingthedatabasefor
theselectedfluid.Theprogramwillalwaysfirstlookforfixedvaluesandifthevalueis
unfixedthenitwilluseiterativemethodsandthedatabases.Intheendtheiterationresult
will be returned to the cell, for example the hcvalue. Using fixed values significantly
improvesthecalculationspeed,howeverthesevaluesarenotalwaysavailable.Asarule
ofthumb,theaccuracyoftheresultwillimproveifitispossibletoaccuratelyspecifyand
fixvalues,forexampletheconvectionandtheradiation coefficients.Thecellsonrows6
8and2023canbefixed,aswellasrow11ifthecolumnisofLayercontacttype.

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MainWindow

Figure5:Mainwindowlayout.
1.Headingsarea
Thisistheheadingsareaanditcannotbealtered,exceptforthesecondandthird
rowifthematerialisuserspecified.
2.Calculationarea
Themaininputsareenteredinthisarea,withthethicknessofalayerorenclosure
columnbeingmandatory.Thesurfacearearowisautomaticallycalculatedfromthe
geometryand layerthicknesses.

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3.Temperatureinputs/results
Inthisareathetemperaturepointsareentered.Inordertocalculatethetemperature
profileonetemperaturepointmustbespecified.Inordertocalculatetheheatloss
twopointsmustbespecified.Forthreedimensionalobjects(cubeandcylinder),
theusercanselectCalculateallsheets(calculatethewholeobjectsimultaneously)
or Calculate active sheet (calculate only the active wall), by selecting the
appropriateoptionbuttonfromthe Calculation frame.Itisalsopossibletoselecta
calculationareabyselectingatemperaturerangewiththemouse.Inthiscaseonly
therangewithinthisselectionwillbecalculated.Anexampleofthis wouldbeto
selecttherangebetweenC9andF10infigure5.
4.Detailedinformation
Hereyoucanfindmoredetailedinformationaboutthesetup.Ifmorepreciselayer
calculationsarerequired,theCalculationgrid (row13)valuemaybechanged.By
default this is set to 10, i.e. the layer is divided into 10 elements. Note that the
calculation time increases with an increasing grid size. Speed(row 16) indicates
the speed of the fluid for forced convection. If this is zero, free convection is
assumed.Theminimum andmaximumtemperatures(rows1718)givethevalid
rangeforacertain material N/A indicates that the limit is not available fromthe
database. If a temperature point in the calculation result exceeds one of these
points,itwillbeindicatedbyawarningmessagebox.
5.Availabledata(frame)
These buttons are enabled/disabled depending on the column type the cursor is
placedon.
Conduction:Layercolumn
Convection:SurfacecolumnorEnclosurecolumn
Radiation (surface): Surface column or Layer column (adjacent to an Enclosure
columnonly)
Radiation(gas):Surfacecolumn,leftofaLayerorLayercontactcolumn(internal
radiation)
Radiation (particles): Surface column, left of a Layer or Layer contact column
(internalradiation)
6.Geometryinput
Theoptionboxselectsthegeometryandtheappropriatedimensiontextboxes.Note
that when changing from a wall or sphere (one sheet calculations) to a cube or
cylinder(oneormultiplesheetscalculations)thewallsheetwillbecopiedtothe
joiningsheetsofthecubeorcylinder.Thisisusefulifallwallsconsistofthesame
materials,sincetheuserthus only has tospecifythe layout of one wallandthen
changetothe correct geometry.TheDrawbutton draws asimpledrawing ofthe
currentgeometry.
7.Heatlossinput/result
Thiscanbeusedbothasinputoroutputdata.Ifcalculatingthetemperatureprofile
the total heat loss must be entered here, but when calculating heat loss, this can
alsobeusedasastartingapproximationtoachievefastercalculations.Thestarting
approximationhasamaximumvalueof10MW.Ifahighervalueisspecified,the
maximumvalueissimplyinsertedinthetextboxbydefault.

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8.Radiationinputs/results
Rows 30349 consist of Convection and Conduction data and rows 350 of
Radiation data. These are automatically collected from the database sheet when
pressingthe Selectbuttonandtheseshouldnotbechanged.

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.

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ConvectionDatabase,Tablesheet

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.

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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.

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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.

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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.

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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.

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TargetCalculations(TargetDialog)

Figure12:TargetDialogwindow.
TheTargetDialog extends the calculationpossibilities ofHeat Loss.Forexample it is
possibletocalculatetherequiredinsulationthicknesstoachieveacertainheatlossor,as
theexampleinFigure12,therequiredwidthofaradiatortoachieveaheatloss(inthis
case heat output) of 0.5 kW. The following stepbystep procedure describes how the
Targetdialogcanbeusedforthisiteration.
1. Openthefile Radiator.HTRfromthe Hsc5\HeatLossdirectory.
2. SelectTarget/TargetDialogfromthemenu.
3. Choose Width fromthedropdownboxinthe Variablevalueframe.
4. PressSetvariable,whichsetsthewidthoftheradiatorasthevariablevalue.
5. Choose Heatflowfromthedropdownboxinthe Targetvalueframe.
6. PressSettarget, whichsetstheHeat loss oftheradiator(heat output)asthetarget
value.
7. Choose Calculate Heat flow (calculation method) from the dropdown box in the
Iteration frame.
8. Write1intheMincolumn,10intheMaxcolumnand0.5intheValuecolumn.This
specifies the minimum and maximum widths and the goal value for the heat loss
(heatoutput).
9. PressIterateSelectedRows,whichcalculatestherequiredwidthforaheatoutputof
0.5kW.Therequiredwidthoftheradiatoris5.747m,ascanbeseenfromthemain
window.
IftheWorksheetcelloptioninadropdownboxisselected,anyworksheet cells inthe
mainwindowmaybeusedaseitheravariableortargetvalue.Anexampleofthiscould

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beto iteratetherequiredthickness ofalayer(row4)in ordertoachieveacertain heat

loss.
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.

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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.

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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

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external convection. Instead the heat convection coefficient hc must be specified

manuallyorusingtheFunction sheetinthe ConductionDatabase.

If only surface columns are given for a cube, cylinder or sphere, then external
convectionisassumed.

If the speed of a fluid is very low and the Table sheet is selected as input, the
combinedfreeandforcedconvectionplaysanimportantrole,howeverthis is not
takenintoaccountinthismodule.

Radiation from a surface to the surroundings (or vice versa): the surface is
considered gray and diffuse, that is a(T) = e(T) only, this is however a valid
approximationformostcases.

Radiationemissivitiesforsurfacesinthedatabasearegivenaseithernormal(n)or
hemispherical(h).

Theminimumtemperatureis200Candthemaximumis8000C,howeverdata
forextremetemperaturessuchastheseareseldomavailable.

Sometimestheprogramis notabletoiteratetheanswercorrectly.Ifthishappens
try using a different starting heat loss (better starting approximation) and
recalculate.Makesurethattheminimumormaximumtemperatureisnotexceeded.

When calculating temperature profiles it is advised to fix the outer (cooler)

temperature and let the program calculate the inner temperature. The reverse
selectionmayeasilyleadtotemperatureslowerthan0Kiftheheatlossspecified
istoohigh.

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BasicTheorybehindHeatTransfer
Thischapterexplainsthebasictheoryofheattransferusedbythemodule.Theequations
andtheorygivenareutilizedwithintheprogram.
The totalheatflow in onedimension(x)is

qx = q'x' A,

[1]

where q'x' is the heat fluxand A is theunit area.It is oftenpracticaltouseananalogy

betweenheattransferandOhmslawinelectricity.Thethermalresistanceisdefined as

R =

T1 - T2
,
qx

[2]

where T1 and T2 are the temperature points and qx is the heat flow. The thermal
conductanceisthen

G =

1
,
R

[3]

whereRisthethermalresistance.
Timedependentheatflows,whereqx =q(x,t),andsteadystatenontimedependentheat
flowsqx=q(x)aretwobasicwaysofidentifyingheattransferproblems.Thisprogramis
concerned only with steadystate nontimedependent conditions, which means that the
conditionisvalidforinfinitet.
A number of dimensionlessparameters areused inthischapter.Some ofthemareonly
materialspecific and can be listed in a table, while others are geometryspecific or
directlyrelated.Equations[4]to[7]showthemostimportantones.
The thermaldiffusivityisdefinedas

a =

k
,
cpr

[4]

wherekisthethermalconductivity,cp istheheatcapacityatconstantpressureand ris

thedensity.
The kinematicviscosityisdefinedas

m
n = ,
r
where m isthedynamicviscosity.

[5]

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ThePrandtlnumberdescribestheratioofthemomentumandthermaldiffusivities.This
isdefinedas

Pr =

n
,
a

[6]

where nisthekinematicviscosityand a isthethermaldiffusivity.

The thermalexpansioncoefficient isdefinedas

b =-

1 r
1 Dr
,

r T p
r DT

[7]

wherepdenotesthederivativeatconstantpressure.
In order to calculate the heat flux, it must be separated into the three main forms:
conduction,convectionandradiation.Amoredetaileddescriptionoftheseformswillbe
giveninthefollowingchapters.

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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

qx'' = - k

dT
,
dx

[8]

where dT/dx is the temperature derivative in xdirection. The function k = k(T) is

generallynotexpressedthesamewayastheheatcapacityfunctioncp =cp(T),whichisa
fittedequationinotherpartsofHSC,i.e.theKelleyequation.Insteadthevaluesofkare
known at certain temperature points and linear interpolation and extrapolation may be
usedfortemperatures outsidethesepoints.Whencalculatingthe heat flux(orflow)the
distance between the two temperature points is divided into a grid. Hence we can
calculate the heat flux by using the following approximate equation that calculates the
averageheatfluxthroughalayer
m

''
x

- kn (Tn+1/2 - Tn-1/2)

q =

n=1

[9]

m Dxn
n=1

wherekn =kn (Tn)istheheatconductioncoefficientatTn (middleofthegrid),misagrid

step(theamountofstepsthedistancexisdividedinto),nisthepointinthemiddleofone
grid step, Tn+1/2 is the temperature point between grid n and grid n+1, Tn1/2 is the
temperaturepointbetweengridnandgridn1and Dxnisthethicknessofthegrid.
Inordertobeabletocalculateothergeometries,theshapefactorSinthetotalheatrate
''
equation q =qx A= SkDT isdefinedfordifferentgeometriesaccordingtoequations[10]
to[12].
Foronedimensionalplanewallsandforcubewalls,Sisdefinedas

S = A/ x,

[10]

whereAistheunitareaforthelayerandxisthethicknessofthelayer.
Forcylindricalwalls(cylindricalcoordinates),Sisdefinedas

S =

2ph
,
ln( xo /xi )

[11]

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where h is the height of the cylinder, xo the outer radius of the layer and xi the inner
radiusofthelayer.
Forsphericalwalls(sphericalcoordinates),Sisdefinedas

S=

4pxixo
.
xo - xi

[12]

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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

q''= hc(Ts - T ) ,

[13]

where hc is the convection coefficient, Ts is the surface temperature and T is the

fluid/gas temperature.The mathematical models for hc,based on experimental data, are
givenindimensionlessformusingtheNusseltnumber,whichisdefinedas

NuL =

hcL
,
k

[14]

whereListhe characteristiclength fortheprescribedgeometry.

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.

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Freeconvection
The correlation describing the nature of the flow for free convection is called the
Rayleighnumber andisdefinedaccordingto

RaL =

gb(Ts - T )L3

na

[15]

wheregistheaccelerationduetogravityand bthethermalexpansioncoefficient.
SometimestheGrashofnumber,whichdescribestheratioofbuoyancyforcestoviscous
forces,isusedincorrelationsandisdefinedas

GrL =

gb(Ts - T )L3

RaL
Pr

[16]

AdescriptionofhowtocalculatethefreeconvectionNusseltnumber,definedinequation
14,fordifferentgeometriesisexplainedbelow.
Wall,verticalposition qv=0/1/:
Surface:
Characteristiclength:L=z
Laminarflow(RaL <109):

Nu L =0.68+

0.670Ra1L/ 4

[17]

[1+ (0.492/Pr) ]

9/16 4/9

Turbulentflow(RaL109):

0.387Ra1L/6
Nu L = 0 .825 +

1+ (0.492 /Pr)9/16

8/27

[18]

Enclosure:
Characteristiclength:L=thicknessofwallenclosure
H=z(heightofenclosure)
H/L2:

Pr

Nu L =0.18
RaL
0.2+ Pr

0.29

[19]

Validwhen:
1<H/L<2
103 <Pr<105
103 <(RaLPr)/(0.2+Pr)
2<H/L<10:

Pr

Nu L =0.22
RaL
0.2+ Pr

Validwhen:
2<H/L<10

0.28

H

L

-1/ 4

[20]

PeterBjorklund

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Pr<10
103 <RaL <1010
H/L10:

H
Nu L =0.42Ra1L/ 4 Pr0.012
L

-0.3

[21]

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

PeterBjorklund

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Nusseltnumberaccordingtoequation[17]or[18]
Roofandbottom:
Characteristic length: L = A/P, i.e. the roof/bottom surface area
dividedbytheperimeter
NuroofandNubottomaccordingtoequation[22],[23]or[24]
Enclosure:
Sameasforwalldependingonhorizontalorverticalcubeenclosure

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

PeterBjorklund

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0.387Ra1D/6
NuD = 0.60+
8/27

1+ (0.559/Pr)9/16

[26]

Validwhen:
RaD 1012
Roofandbottom:
Characteristiclength: L = ro p ,i.e.squarewithsamearea
NuroofandNubottomaccordingtoequation[17]or[18]
Enclosure:
CharacteristiclengthL=thicknessofcylinderenclosure
hc calculateddirectly,notthroughtheNusseltnumber(NuL)
*
c

Ra =

[ln(Do / Di)]4
L3(Di-3/5 + Do-3/5)

RaL

[27]

Rac* <100:

hc =

k
ln(Do / Di ) Di /2

[28]

Rac* 100:

Pr

keff =0.386

0.861+ Pr
keff
hc =
ln(Do / Di ) Di /2

1/ 4

(Ra )

* 1/ 4
c

[29]
[30]

validwhen:
102 Rac* 107
Sphere/1/:
Surface:
Internalflow:
Characteristiclength:L=zi
Nusseltnumberaccordingtoequation[17]or[18]
Theflowisassumedtocooldownatthewalls(downflow),thuscreating
acirculatingflowwithanupflowthroughthecenterofthesphere
Notvalidforsmallspheres
Externalflow:
Characteristiclength:L=Do

NuD = 2 +

0.589Ra1D/4

[1+ (0.469/Pr) ]

9/16 4/9

Validwhen:
RaD 1011
Pr 0.7
Enclosure:
Characteristiclength:L=thicknessofthesphereenclosure
hccalculateddirectly,notthroughtheNusseltnumber(NuL)

[31]

PeterBjorklund

Ra *s =

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RaL

(DoDi)

(D

- 7/5
i

+ Do-7/5

[32]

Ras* <100:

hc = kp

DiDo
L

[33]

Ras* 100:

Pr

keff =0.74

0.861+ Pr
D D
hc = keff p i o
L
Validwhen:
102 Ras* 104

1/ 4

(Ra )

* 1/ 4
s

[34]
[35]

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Forcedconvection
Forced convection is here assumed to be external only. The correlation number
describing the nature of the flow for forced convection is called the Reynolds number,
whichdescribestheratioofinertiaforcestoviscousforcesofaflowandisdefinedas

ReL =

u L
n

[36]

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
0.62Re1D/ 2 Pr1/3 ReD
Nu D =0.3+

1+
2/3 1/4
1+ (0.4/ Pr)
282000

Validwhen:
ReDPr 0.2
Roofandbottom:

4/5

[39]

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Characteristiclength: L = ro p ,i.e.squarewithsamearea
Nusseltnumbercalculatedas[37]or[38]
Sphere/1/,/2/:
Characteristiclength:L=Do

m
Nu D = 2 + (0.4Re + 0.06Re )Pr
m s
1/2
D

2/3
D

0.4

1/4

[40]

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

PeterBjorklund
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Radiation
Heattransferduetoradiationoccursintherangeofapproximately0.4 mmto1000 mmof
theelectromagneticwavelengthspectrum/3/.Thisspectrumincludesbothvisiblelightas
wellasinfraredradiation.Radiationheattransferbetweentwopointsoccurswhenwaves
are emitted at one point and absorbed at another. Sometimes the wave is reflected or
transmitted and thus there is no radiation heat transfer between these two points.
However,the wavecanbeabsorbedat anotherpoint thus creatinga heat flowbetween
thesenewpointsinstead.Sinceradiationconsistsofelectromagneticwavesitistherefore
notdependent onthemedium,infactradiationheattransferthroughavacuumishigher
thanthroughothermediumssincealmostnoradiationisabsorbedthere.Radiationplaysa
significant roleat hightemperatures andradiation heat transferis inthis instance much
higherthanconvectionheattransfer.Thiscanbeseenfromequations[41],[44]and[52],
withtemperaturesraisedtoapoweroffour.
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]

where es is the surface emissivity, which is a function of the surface temperature,

es = es (Ts)and sis theStefanBoltzmannconstant.Thesurface is assumedtobe gray,
which means that the surface absorptivity is equal to the surface emissivity
(as(T)= es (T)).
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

q''=hr (Ts - T )

[43]

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/.

PeterBjorklund

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Gasradiation
Theheatfluxduetoradiationfromagastoasurfaceiscalculatedas/4/

q''=

e s + 1
s (e gTg4 - a gTs4 ),

[44]

where es isthesurfaceemissivity, eg = eg (Tg)isthegasemissivityatthegastemperature

and ag = ag (T g ,Ts) is the gas absorptivity as a function of both the gas and surface
temperatures. It is natural that ag also depends on Ts as this defines the spectrum of
incomingradiationandthisisclearbecauseTg definesthestateofthegasandtherefore
its thermal properties. The surface is also here assumed to be gray. The coefficient
(es+1)/2isanapproximationfortheeffectiveemissivityofthesolid.
Theheatradiationcoefficientisnow

hr =

(es + 1)s (e gTg4 - a gTs4)

2(Tg - Ts )

[45]

In ordertocalculate eg and ag theexponential widebandmodelproposed in/5/canbe

used.Thismodelhasbeenoptimizedandmademoreefficientcomputationallyin/6/.The
modelcantreatmixturescontainingH2O,CO2,CO,NO,SO2 andCH4 in,forexample,a
nonradiatingnitrogengas.Themodelalsotakesintoaccountthepressureandtheoptical
depthofthegeometry.Thegasemissivityfunctionis

e g =e g (T g ,p,L,xH2O ,xCO2,xCO,xNO ,xSO2,xCH4),

[46]

wherepisthepressure,Listheopticaldepthandxisthemolarfractionoftheindividual
gasspecies.Notethatthesumoftheradiatinggases canbesmallerthanone, xsp 1,
sincetherestofthemixturecanconsistofnonradiatinggases.
This model is applicableforthetemperaturerangeT=300Kto25003000Kandthe
pressure range p = 0.5 to 20 bar.The optical depth L depends on the geometry and is
listed in the following table for the most common geometries /7/. All surfaces are
assumedtobeabletoabsorbradiation.
Geometry
1.Sphere
2.1Cylinder(h=0.5D)
2.2Cylinder (h=D)
2.3Cylinder(h=2D)
3.1Cube(1x1x1)
3.2Cube(1x1x4)
3.3Cube(1x2x6)

Characteristicdimension
Diameter(D)
Diameter(D)
Diameter(D)
Diameter(D)
Anyside(x)
Shortestside(x)
Shortestside(x)

Opticaldepth(L)
0.63D
0.45D
0.6D
0.73D
0.6x
0.81x
1.06x

Table1:Examplesofopticaldepthsforsimplegeometries
Fordimensions not listedinTable1the optical depthcoefficient canbe interpolatedor
extrapolated.Asimpleexampleis:

PeterBjorklund

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Calculatetheopticaldepthforacubewiththedimensions1x4x7.
1. Extrapolatedasa1x1x7cubeusinggeometries3.1and3.2gives
L1x1x7=0.6+(0.810.6)[(71)/(41)]=1.02
2. Extrapolatedasa1x2.5x7cubeusinggeometries3.2and3.3gives
L1x2.5x7=0.81+(1.060.81) [(2.51)/(21)]=1.185.
3. These two results can then be used again to extrapolate into the 1x4x7 cube which
givesL1x4x7=1.02+(1.1851.02)[(41)/(2.51)]=1.35.Thisistheanswersincethe
shortestsideisx=1.
Thegasabsorptivityatthesurfacetemperaturecanbecalculatedusingthesamemodelif
twotemperaturecorrectionfactorsareintroduced.Thefunctionthenbecomes
1.5

T
Tg
ag =e g (T g ,p,L s ,xH2O ,xCO2,xCO,xNO ,xSO2,xCH4)
T
Ts
g

0.5

[47]

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 c = 1- e

- e pnpLAp

[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

A=

2
s

pd
4

p
4

2
i i

nd
i=1
n

[49]

i=1

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]

where ec istheparticlecloudemissivityand eg isthegasemissivitycalculatedaccording

to the model behind equation [46]. The total gas and particle cloud absorptivity can be
approximatedas

a g +c = a g + e c - a ge c ,

[51]

PeterBjorklund

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where ag isthegasabsorptivitycalculatedaccordingtothemodelbehindequation[47].
Finally,the heat fluxduetoradiationfromagas and particlecloudtoasurfaceis then
calculatedaccordingto/7/

q''=

es
s (e g+ cTg4 - a g+ cTs4 )
a g+ c + e s - a g+ ce s

[52]

andtheheatradiationcoefficientas

ess (e g+ cTg4 - a g+ cTs4 )

hr =
(a g+c + e s - a g+ce s )(Tg - Ts ).

[53]

PeterBjorklund

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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.)

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13. EQUILIBRIUMMODULE

Fig.1. EquilibriumModuleMenu.
This module enables you to calculate multicomponent equilibrium compositions in
heterogeneoussystemseasily.Theusersimplyneedstospecifythereactionsystem,with
its phases and species, and gives the amounts of the raw materials. The program
calculatestheamountsofproductsatequilibriuminisothermalandisobaricconditions.
The user must specify the substances and potentially stable phases to be taken into
account in the calculations as well as the amounts and temperatures of raw materials.
Notethatifastablesubstanceorphaseismissinginthesystemdefinition,theresultswill
beincorrect.ThespecificationcaneasilybemadeintheHSCprograminterface,andthe
inputdatafilemustbesavedbeforethefinalcalculationsaremade.
The equilibrium composition is calculated using the GIBBS or SOLGASMIX solvers,
which use the Gibbs energy minimization method. The results are saved in *.OGI or
*.OSGtextfilesrespectively.ThepostprocessingPICprogramreadstheresultfilesand
draws pictures of the equilibrium configurations if several equilibria have been
calculated. The user can toggle between the equilibrium and graphics programs by
pressingthebuttonsshowninFigs.1,4,6and7.
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

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fileregardless of whichfileformat isselectedforsavingtheactual input file for

equilibrium calculations. If you want to use formatting settings, please use the
OpenNormal selectionfrom Filemenu,seeFig.4.
2.

*.IGIfileFormat
ThisfileformatcontainsthedataforcalculationsfortheGIBBSsolveronlyandit
canreadthesefiles.

3.

*.ISGfileFormat
This fileformat contains the dataforcalculations withtheSolgasmixsolveronly
anditcanreadthesefiles.

4.

*.DA2fileFormat
ThisfileformatcontainsthedataforcalculationsfortheChemSAGE2.0only.The
equilibrium module also reads *.DA2files, but not if solution model parameters
have been added to the file manually. Note that this equilibrium solver is not
includedinHSC5.0.

5.

*.DATfileFormat
ThisfileformatcontainsthedataforcalculationsforChemSAGE3.0and4.0only.
The equilibrium module also reads *.DATfiles, but not if solution model
parameters have been added to the file manually. Note that this equilibrium
programisnotincludedinHSC5.0.

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.

A.Roine

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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.

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Ifyouwanttouseonlysomeofthespeciesinthecalculationsthenselectonlytheseand
pressDeleteUnselected,whichwillremovetheunnecessaryspecies.
EspeciallyifyouhaveselectedCand/orHamongtheotherelementsyouwillgetavery
largenumberofspeciesforthecalculationandyouareadvisedtodecreasethenumberof
species.SeeChapter13.4forselectioncriteriaforphasesandspecies.

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.

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Whenyouhavefinisheddeletingthespecies,pressContinueandyouwillreturntothe
EquilibriumEditorwindow,seeFig.4.

A.Roine

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GivingInputDataforEquilibriumCalculations

Fig.4. Specificationofthespeciesandphasesforthereactionsystem.

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Fig.5. Specificationofthecalculationmode.

A.Roine

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The Equilibrium Editor consists of two sheets for determining the conditions of the
equilibriumcalculations.InSpeciesandOptionssheets,Figs.4and5,you giveallthe
data required to create an input file for the equilibrium solvers and for calculating the
equilibriumcompositions.Equilibriumcalculationsaremadeinthreesteps:
1.

TheusergivesthenecessaryinputdatausingtheSpeciesandOptionssheetsinthe
EquilibriumEditorWindow,Fig.4,andsavesthisdataasatextfile.

2.

The equilibrium compositions will be calculated using the equilibrium solvers,

whichreadtheinputfilesandsave theresultsincorrespondingoutputfiles.

3.

Theresultsintheoutputfilecanbefurtherprocessedtographicalformbypressing
DrawinFig.1or6ifseveralsuccessiveequilibriahavebeencalculated.

Themostdemandingstepistheselectionofthespeciesandphases,ie.thedefinitionof
thechemicalsystem.ThisisdoneintheSpeciessheetoftheEquilibriumEditor,Fig.4.
You can move around the table using the mouse, or Tab and Arrow keys. The other
thingswhichyoushouldconsiderare:

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.

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The phase rows must be inserted in the sheet using Phase selection inInsert menu or
usingthesameselectioninthepopupmenuoftheright mousebutton.TheEquilibrium
modulemakesthefollowingmodificationstothesheetautomaticallywhenyouinserta
newphaserowinthesheetand:
1.
2.
3.
4.

Asksanameforthenewphase,whichyoucanchangelater,ifnecessary.
Inserts a new empty row above the selected cell of the sheet with a light blue
pattern.
Assumesthatallrowsunderthenewrowwillbelongtothenewphasedowntothe
nextphaserow.
Inserts new Excel type SUM formulae in the new phase row. These formulae
calculatethetotalspeciesamountinthephaseusingkmol,kgorNm3 units.

Whentheinsertprocedureisready,youmayeditthephaserowinthefollowingway:
1.
Thephasenamecanbeediteddirectlyinthecell.
2.
Thephasetemperaturecanalsobechanged directlyinthecellandit willchange
thetemperaturesofallthespecieswithinthephase.
3.
Note that you can not type formulae to the amount column of the phase row,
because theSUMformulaearelocatedthere.
You can change the amount of species in a phase using kmol, kg or Nm3 units,
simply by typing the new amount to the corresponding cell. The program will
automaticallyupdatethetotalamountandthecompositionofthephase.
Thefirstphasetobedefinedisalwaysthegasphase,andallgaseousspecies mustexist
underthegasphaserow.Speciesofthesamephasemustbegivenconsecutivelyoneafter
anotherin thetable. As default,HSCChemistryautomaticallyrelocates allthe gaseous
species,condensedoxides,metals,aqueousspecies,etc.intotheirownphasesifyoustart
fromthegiveElementsoption,seeFig.1.Thefinalallocation,however,mustbedone
bytheuser.
Ifthereisnoaqueousphase,allaqueousspeciesmustbedeleted.Notethatifyouhavean
aqueousphasewithaqueousions,youmustalsohavewaterinthephase!
Ifyouexpectpuresubstances(invariantphases)toexistintheequilibriumconfiguration,
insertthemastheirownphasesbygivingthemtheirownphaserows orinsertallthese
species under the last phase row and select the Pure Substances in the Last Phase
option,seeFig.5.Formationofpuresubstancesispossibleespeciallyinthesolidstateat
lowtemperatures.Forexample,carbonC,ironsulfideFeS2,calciumcarbonateCaCO3,
etc.mightformtheirownpurephases.
Oneofthemostcommonmistakesistoinsertalargeamountofrelativelyinertsubs
tancetothemixturephase.Forexample,largeamountsofsolidcarbonat1500Cdonot
dissolveintomolteniron.However,ifthesebothspeciesareinsertedintothesamephase
thentheequilibriumprogramassumesthatironandcarbonformanidealmixtureat1500
C. This will, for example, cause much too low vapor pressure for the iron. Therefore
carbonshouldnearlyalwaysbeinsertedintoitsownphaseatlowtemperatures.

3.InputTemperaturesoftheSpecies
Inputtemperaturesfortherawmaterialspeciesareessentialonlyintheequilibriumheat
balancecalculations,i.e.ifyouprovidesomeinputamountforaspeciesyoushouldalso
giveitstemperature.Theinputtemperaturedoes notaffecttheequilibriumcomposition.
Youmayselectthetemperatureunitbyselecting CfromtheUnitsmenu,seeFig.4.

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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)
Ln(f)
Ln(f)
Ln(f)
where:
T
X24
f

=
=
=
=

8495/T2.653
0.69+56.8*X24+5.45*X25
3926/T
1.21*X7^22.44*X8^2

=
=
=

TemperatureinK
Molefractionofthespecieswitharownumber24inthesheet.
Activitycoefficient.

FormulaearewrittenusingthesamesyntaxasinExcel,thedefinednamesTandPare
available for temperature and pressure. Mole fractions are given as cell references to

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columnX.Pleasenotethatthereturningvaluesoftheformulaeareinsignificant,because
themolefractionvaluesincolumnXarezero,seeFigs.16 17.

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
Equilibriumcalculationsarealways madeinconstant pressureorinisobaricconditions.
Normally a total pressure of 1 bar is used, and it is also given as default in HSC. In
autoclaveorvacuumfurnaceapplicationsyoumayneedtochangethepressure.Youcan
also increase pressure incrementally by giving a Pressure Range, please remember to
alsodefinethe IncreasePressureoptionforthisselection,seeFig.5
ThetotalpressurePhaseffectongasphaseactivityvaluesaiinformula3.Thefugacity
Fiofgasspeciesimaybecalculatedfromthisvaluewithformula4.
ai=

P*xi

[3]

Fi=

ai *1bar

[4]

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

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HSCwillutilizeCrissCobbleextrapolationfortheheatcapacityofaqueousspeciesat
elevatedtemperatures(>25C)iftheCrissCobbleoptionisselected,Fig.5Refertothe
detailsinChapter28.4.Notethat:
A)

It is necessary to select the Mixing Entropy option for the GIBBS and
SOLGASMIXroutines.Inthis case,theactivities oftheresultswillbepresented
ontheRaoultianscalewhichisbasedonmolefractions,seeChapter13.3.

B)

ItisnotrecommendedtoselecttheMixingEntropyoptionfortheChemSAGEor
for the SOLGASMIX if the conventional activity coefficients of aqueous species
aretobegivenintheFACTORsubprogram.

If the CrissCobble and Mixing Entropy options are not selected for the GIBBS or
SOLGASMIXprograms,thentheactivitycoefficientsofaqueous species maybeset to
55.509/X(H2O), which will convert the Raoultian activity scale to the aqueous activity
scale.Thistrickwillalsogivetheactivitiesoftheresultsonanaqueousscale,wherethe
concentrationsunitsareexpressedasmolesperliterofH2O(mol/l).

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!

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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:
H2O=H(+a)+OH(a)

K=1.020E14

[5]

Youmayalsocalculatethesameequilibriumconstantfromtheequilibriumresults
oftheGIBBSprogramusingequation10inChapter8.Introduction.Youcanread
the necessary molal concentrations, for example, from the equilibrium results
\HSC3\CaCO3.OGIfile,seeTable1.Thiscalculationshouldgivenearlythesame
resultsastheReactionEquationoption.
[H(+a)]*[OH(a)]
K = =
[H2O]

PHASE1:
N2(g)
H2O(g)
O2(g)
CO2(g)

4.735E13*2.159E2

55.468/55.509

=1.023E14

INPUTAMOUNTEQUILAMOUNTMOLEFRACTACTIVITYACTIVITY
molmolCOEFFICI
1.0000E+001.0000E+0009.683E011.00E+009.683E01
0.0000E+00 3.2678E0023.164E021.00E+003.164E02
1.0000E051.0000E0059.683E061.00E+009.683E06
1.0000E031.5986E0131.548E131.00E+001.548E13

[6]

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Total:

1.0010E+001.0327E+0001.000E+00

PHASE2:
H2O
CO3(2a)
C2O4(2a)
Ca(+2a)
CaOH(+a)
H(+a)
HCO2(a)
HCO3(a)
HO2(a)
OH(a)
Total:

MOLEFRACT
5.5500E+01 5.5468E+001 9.994E011.00E+009.994E01
0.0000E+004.7507E0078.560E091.00E+008.560E09
0.0000E+008.0560E0610.000E+001.00E+000.000E+00
1.0000E+001.0797E0021.945E041.00E+001.945E04
0.0000E+001.4656E0102.641E121.00E+002.641E12
0.0000E+00 4.7348E013 8.531E151.00E+008.531E15
0.0000E+008.1514E0480.000E+001.00E+000.000E+00
0.0000E+004.9071E0098.842E111.00E+008.842E11
0.0000E+001.1549E0202.081E221.00E+002.081E22
2.0000E+00 2.1593E002 3.890E041.00E+003.890E04
5.8500E+015.5501E+0011.000E+00

Table1.Apartoftheequilibriumresultfile \HSC5\GIBBS\CaCO3.OGI.

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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

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materialsandyouhaveNaClasthepuresubstance,allrawmaterials mayfitinto
NaCldueitshighstability.Theroutines meet difficulties incalculations,because
theamountsofalltheotherphasesandspecies,exceptthestoichiometricone,goto
zero.Youcanavoidthissituationbygivinganadditional1E5molCl2(g)tothe
gasphase,seeFig.46.
9.

Quite often the most simple examples are the most difficult ones for the Gibbs
energyminimizationroutinesduetomatrixoperations.However,thenewGIBBS
4.0versionusually finds thesolution forthesimplesystems too,suchas thetwo
phaseH2O(g)H2Osystembetween0200C.

10.

Sometimes a substance is very stable thermodynamically, but its amount in

experimentsremainsquite low, obviously dueto kineticreasons.You maytryto
eliminate such a substance in the calculations in order to simulate the kinetic
(rate)phenomena,whichhavebeenprovenexperimentally.

11.

It is also important to note that different basic thermochemical data may cause
differencestothecalculationresults.Forexample,useofHSCMainDB4.HSCor
MainDB5.HSCdatabasefilesmayleadtodifferentresults.

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.

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TherealNaSOCsystemisquitecomplicated.Inordertodescribethissystemprecisely
from0to1000C,solutionmodelsforeachmixturephasewouldbeneededtodescribe
the activities of the species. Kinetic models would also be necessary at least for low
temperatures.Tofindthecorrectparametersfromtheliteratureforallthesemodelsmight
takeseveralmonths.However,withHSCChemistrytheusercangetpreliminaryresults
injustminutes.Thisinformationisoftenenoughtodesignlaboratoryandindustrialscale
experiments.

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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.

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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.

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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.
YoumayrunSOLGASMIXbypressing SGMwhen SGMformathasbeenselected,see
Fig.5,orbyselectingSolgasmixintheCalculate menu.Wait forthecalculations until
DrawDiagramisactivated,seeFig.7.Aftercalculationsyoucandrawadiagramfrom
the results by pressing Draw Diagram or return to Equilibrium Window by pressing
Exit.

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DrawingEquilibriumDiagrams

Fig.8. SelectingthexaxisforanEquilibriumDiagram.

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Fig.9. SelectingthexaxisforanEquilibriumDiagram.

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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.

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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.

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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

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theleftmousebuttondownanddragthelabeltoanewlocation,releasethemouse
buttonandthelabelwilldrop.
3.

The line width of curves, species label font, etc. may be changed by double
clickingthespecieslabelsorselectingthelabelwithmouseandselectingFormat
Label fromthemenu.Youcannotdothisbydoubleclickingtheline.Thelabeland
curveeditingwindowisshowninFig.13.Notethatotherlinestylesthansolidare
availableonlyforlinewidthssmallerthan0.3mm.

Fig.12. Changingscales,scalenumberformatandfontsettings.

Fig.13. Changinglabelandlinespecifications.

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4.

Youcaneditanylabelandheadingonthescreenbysimplyclickingthetextinthe
labelbymouseandstartingtoedit.ForexampleyoucanchangethelabelNitoa
nonabbreviatedformNickel.

5.

You can create new labels by selectingLabelfrom theInsert menu. These new
labels canbedeletedusingtheLabelselectionintheDeletemenu.Default labels
cannotbedeleted,andtheonlypossibilityistoremovealltextfromthem.

6.

The firsttime youuseHSCChemistry it maybe necessaryto changethe default

fontsbyselectingtheDefaultFontfromtheFormatmenu,becausetheavailable
fontsvaryfromonecomputertoanother.UsuallyTimesNewRoman,bold,size11
fontisagoodselection.TheselectionwillbeautomaticallysavedintheHSC.INI
fileinyourWindowsdirectory.

7.

WhenyouaresatisfiedwiththediagramyoucanprintitbypressingPrintB&W.
If you haveacolorprinterpress PrintCol.Theprintdialog gives severaluseful
optionsforahardcopy,seeFig.14.

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.

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13.7.3 EquilibriumDiagramTable

Fig.15. EquilibriumDiagramTable.
You can displaythe equilibriumresults inatabularformat bypressingTablethe Axis
menu,Fig.10,orintheDiagramwindow,Fig.11.TheTablewindowhasseveralExcel
type features in a similar way to the other spreadsheets in HSC. The most important
featuresare:
1.

With CopyAllyoucangetthewholetableintotheClipboard,andpastethistable,
forexample,toMSExcel.Youcanalsocopyandpastesmallercellrangesusing
the CopyandPasteselectionsinthe Editmenu,seeFig.15.

2.

Youcanalsosavethetableusingdifferentformats,suchasASCIItextandExcel
byselecting SavefromtheFilemenu.

3.

The Table window has two sheets. The Species sheet contains the data of the
diagram the figures in this sheet can be edited, if you are not satisfied with the
results.TheFormat sheet contains the format specifications ofthe diagram.It is
notrecommendedtoedittheFormatsheet.

There are several formatting options in the Format menu, which can be used to create
representativetablesforprinting.ThetablecanbeprintedusingthePrintselectioninthe
Filemenu,Fig.15.TherearealsoavailableoptionsSetupandPreviewforprinting.
TheAxisbuttonwillopentheAxismenu,Fig.10,andDiagramwilldrawthediagram,
Fig.11.

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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)

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Fig.17.Resultsasafunctionofarsenicamount.Differentcolorshavebeenusedforspecies,butthesedo
notshowupwellinthisB&Wcopy.

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CaCO3Example(Aqueoussolutionexists)

Fig.18. InputdataofexampleCaCO3.IGI.

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Fig.19.ResultsasafunctionofaddedCO2(g).Differentcolorshavebeenusedforthespecies,butthese
donotshowupwellinthisB&Wcopy.

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Fig.20. Resultsonlogarithmicscale,thedefaultexampleisshowninFig.19.

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Fig.21. ResultsasafunctionofpH,thedefaultexampleisshowninFig.19.

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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)).

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Fig.22. ChemicalsystemspecificationforPbSvaporpressurecalculations.

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Fig.23. ResultsofPbSvaporpressurecalculations.

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HSCEQUILIBRIUMMODULESAMPLES

ContentsofanInputFileforGIBBSProgram
'Heading
'0=resultstoscreen,1=resultstofile
'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
CopperSmeltingat1300C
1
6403321

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InputFileforSOLGASMIXProgram(Amountsinmoles)
'Heading
'0=molemode,1=grammode
'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+00 0.000000E+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
720.000
1.172000E+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,andtheirrownumbersinthestoichiometrymatrix
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
CopperSmeltingat1300C
0
641332

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InputFileforSOLGASMIX(Inputamountsingrams)
CopperSmeltingat1300C
'Heading
1
'0=molemode,1=grammode
641332 ' Elements,phases,inv.phases,andnumberofcomponents/phase1...
'N2(g)'2.00 0.000.000.000.000.00
'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'0.000.00 0.000.000.001.00
14.007
'NMol.Weightg/mol
15.999
'O
32.060
'S
55.847
'Fe
28.086
'Si
63.546
'Cu
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,andtheirrownumbersinthestoichiometrymatrix
298.150298.150298.150298.150298.150
2
'^Temperaturesoftherawmaterials(K)
13
'Numberofequilibriatobecalculated
33322
'2=constantinputamount,3=increases
2.8013401E025.2805256E+01
'Amountofrawmaterial1.,step(g)
3.1998802E021.5999400E+01
'Amountofrawmaterial2.,step(g)
6.0084306E027.5105376E+00
'Amountofrawmaterial5.,step(g)
1.5915201E+02
'Amountofrawmaterial7.(g)
1.7581400E+02
'Amountofrawmaterial8.(g)
10
'Exit

A.Roine

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02103ORCT

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.

A.Roine

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Figure1.Calculationresultsforhydrationofmagnesiachromebrick.

A.Roine

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HydrationofMagnesiaChromiteBrick
GIBBS
FileFormat:
YES
PureSubstancesintheLastPhase
101
Steps
IncreaseTemperature
1000.000
0.000
TemperatureRange:
1.000
1.000
PressureRange:
SPECIES
Formula
PHASE1:
N2(g)
H2O(g)
H2(g)
O2(g)
Cr(g)
CrO(g)
CrO2(g)
CrO3(g)
Fe(g)
FeO(g)
Fe(OH)2(g)
Mg(g)
Mg2(g)
MgH(g)
MgO(g)
MgOH(g)
Mg(OH)2(g)
PURESUBSTANCES:
Cr2FeO4
Cr2MgO4
CrO2
CrO3
Cr2O3
Cr5O12
Cr8O21
Cr(OH)2
Cr(OH)3
Fe2MgO4
Fe0.945O
Fe0.947O
FeO
FeO1.056
Fe2O3
Fe3O4
Fe(OH)2
Fe(OH)3
Fe2O3*H2O
H2O
MgCr2O3
MgFe2O4
MgO
MgO2
Mg(OH)2

Temper.
C
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000

C:\Hsc5\Gibbs\Ankrom01.igi
CrissCobbleOn
C
bar

Amount
kmol
5.000
1.000
4.000

Amount
%
100.000
20.000
80.000

1.695

100.000

0.118

6.988

0.088

5.173

1.489

87.839

Step
kmol

Step
%

Figure2.SpecificationofphasesandspeciesintheMagnesiaChromebrickexample.

Activity
Coeff.
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000

A.Roine

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02103ORCT

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.

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AmmoniaSynthesisat480C
FileFormat:
PureSubstancesintheLastPhase
51
IncreasePressure
480.000
TemperatureRange:
0.001
PressureRange:

GIBBS
YES
Steps
480.000 C
1000.001 bar

SPECIES
Formula
PHASE1:
H(g)
H2(g)
HN3(g)
N(g)
N2(g)
N3(g)
NH(g)
NH2(g)
NH3(g)
N2H2(g)
N2H4(g)
N3H(g)
NH(H3)2(g)
PURESUBSTANCES:
NH4N3

Temper.
C
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000

C:\Hsc5\Gibbs\Ammonia.igi
CrissCobbleOn

Amount
kmol
4.001

Amount
%
100.000

3.000

74.981

1.001

25.019

Step
kmol

25.000

Figure4.Specificationofphasesandspeciesinammoniasynthesisexample.

Step
%

Activity
Coeff.
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000

A.Roine

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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:
PureSubstancesintheLastPhase
81
IncreaseTemperature
0.000
TemperatureRange:
1.000
PressureRange:
SPECIES
Formula
PHASE1:
N2(g)
Cl2(g)
HCl(g)
H2O(g)
O2(g)
H2(g)
Mg(g)
PURESUBSTANCES:
MgCl2*6H2O
MgCl2*4H2O
MgCl2*2H2O
MgCl2*H2O
MgCl2
Mg(OH)Cl
MgO
H2O

Temper.
C
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000

GIBBS
YES
Steps
400.000
1.000

C:\Hsc5\Gibbs\Mgcl2.igi
CrissCobbleOn
C
bar

Amount
kmol
0.100
0.100
0.000

Amount
%
100.000
99.980
0.010

0.000

0.010

1.000
1.000

100.000
100.000

Figure5.SpecificationofphasesandspeciesinMgCl2*6H2Oexample.

Step
kmol

Step
%

Activity
Coeff.
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000

A.Roine

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02103ORCT

Figure6.CalculationresultsforMgCl2*6H2Odecompositionexample.

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Figure7.Vaporcompositionatatotalpressureof1bar.

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02103ORCT

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:
PureSubstancesintheLastPhase
100
IncreaseTemperature
0.000
TemperatureRange:
1.000
PressureRange:
SPECIES
Formula
PHASE1:
N2(g)
O2(g)
SO2(g)
S2(g)
H2S(g)
H2O(g)
H2(g)
Fe(g)
PURESUBSTANCES:
FeSO4*7H2O
FeSO4*4H2O
FeSO4*H2O
Fe2(SO4)3
FeSO4
FeO*OH
FeO
Fe2O3
Fe3O4
H2O

Temper.
C
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000

GIBBS
YES
Steps
1600.038 C
1.000
bar

C:\Hsc5\Gibbs\Feso4.igi
CrissCobbleOn

Amount
kmol
0.004
0.004
0.000

Amount
%
100.000
99.990
0.010

0.360
0.360

100.000
100.000

Step
kmol

Figure8. Thespecificationofphasesandspeciesfortheequilibriumcalculations.

Step
%

Activity
Coeff.
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000

A.Roine

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02103ORCT

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.

A.Roine

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02103ORCT

Figure10.ResultsofFeSO4 *7H2OrunonNETSCHTGDSCanalyzerundernitrogenatmosphere
showingTGandDSCcurves.Heatingratewas5C/min.

A.Roine

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02103ORCT

Figure11. ThecomparisonofthemeasuredandcalculatedmasschangeofFeSO4 *7H2O.

A.Roine

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02103ORCT

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.

A.Roine

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02103ORCT

Figure12.Equilibriumresultsofalkalisandslagcomponentsasafunctionoftemperature.

A.Roine
FileFormat:
PureSubstancesintheLastPhase
200
IncreaseTemperature
500.000
TemperatureRange:
1.000
PressureRange:
SPECIES
Formula
PHASE1:
AlO(g)
CO(g)
CO2(g)
Ca(g)
K(g)
K2(g)
K2CO3(g)
KNa(g)
KO(g)
Mg(g)
MgO(g)
N2(g)
Na(g)
Na2(g)
NaO(g)
O(g)
O2(g)
SiO(g)
PHASE2:
AlO
Al2O3
Al2O3*SiO2(D)
Ca2Al2SiO7
Ca3Al2Si3O12
CaO
Ca2SiO4(A)
KAlO2
KAlSiO4
K2CO3
K2O
K2O*Al2O3*2SiO2
K2O*SiO2
K2O*2SiO2
MgO
MgSiO3
Na2CO3
Na2O
Na2O*Al2O3
*2Na2O*SiO2
Na2SiO3
SiO2
PHASE3:
Al
Ca
K
Mg
Na
Si
PURESUBSTANCES:
C
Al4C3
Na2C2
SiC

Temper.
C

HSCChemistry5.0

1418

June28,2002

02103ORCT

GIBBS
YES
Steps
2000.062 C
1.000
bar
Amount
kmol
197000.000

25.000
25.000
25.000
25.000
25.000
4000.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000 150000.000
25.000
3000.000
25.000
25.000
25.000
25.000 40000.000
25.000
1417.000
25.000
25.000
300.000
25.000
25.000
25.000
25.000
60.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
57.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
1000.000

C:\Hsc5\Gibbs\Alkal1.igi
CrissCobbleOn

Amount
%
100.000

Step
kmol

Step
%

2.030

76.142
1.523

20.305

1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000

100.000
21.171

4.234

4.023

70.572

25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000
25.000

Activity
Coeff.

1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000

70000.000
70000.000

100.000
100.000

Figure13. SpecificationofphasesandspeciesintheBlastFurnaceexample.

1.000
1.000
1.000
1.000

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02103ORCT

15. CELLEQUILIBRIA

Fig.1. InputdatafortheCellprogram.
The CELL module calculates the equilibrium composition of an electrochemical cell
usingthesamecalculationmethodastheGIBBSsolver.However,theCELLmoduleis
especiallydesignedforelectrochemicalcellcalculations.
Inadditionto thephase compositions it also gives the electrochemicalpotentials ofthe
electrodes. The user gives input data for the CELL program in the Cell Equilibrium
window,seeFig.1.
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.

A.Roine

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2.

Ifyouwanttoeditthecelldoubleclickwiththemouseorsimplystarttyping.Use
Esckeytoundotyping.

3.

When you are satisfied with the formula or number, press Enter, Down or Up
keys.Youcanalsoclickanothercellwiththemouse.

4.

TypethenameofthefirstspeciesintotheSpeciescolumn.Notethatyoumuststart
fillinginthespreadsheetfromthefirstrow.

5.

Youcanfirsttypeallspeciesandtheneditthetemperatureandamountvalues,or
youcangivethesevaluesaftereveryspeciesnameinput.

6.

YoucantogglebetweendegreesCelsiusandKelvinsbyselectingCorKfromthe
Unitsmenuandfrommolestokilograms(orNm3forgases)bythemol selection.

7.

You must dividethespecies intophasesin thesame wayas describedin normal

equilibriumcalculations,seeexamplesinChapter15.2.

8.

Everyphasemusthaveitsownphaserow.Allspeciesunderthisphaserowuntil
thenextphaserowbelongtothissamephase.

9.

ForeveryphaseyoumustatleastspecifyitsType(Gas,Liquid,...).Youmustalso
specifytheAnodeandCathodephases.Youcanalsogiveanameandcapacitance
forthephases.

10.

Ifyouwanttochangetheorderofspecies,simplyuseInsertRow,CopyandPaste
ortheDragandDroptechniquedescribedinChapter20.DiagramGraphics.

11.

Youcanalsoinsertanddeleterowsbypressing InsRowand DelRow.

12.

YoucangiveExtraBalancesasatableormatrixintheExtraBalancesBox.For
example:
13

'Species13:Oxidationnumberofe(Pt)

17

'Species17:OxidationnumberofO2(g)

'Dischargeamount:Q/F(mol)

Extra Balances makes it possible to calculate potentials of electrodes and

chemicalcompositionsofphasesatdifferentdischargestatesofanelectrochemical
cell.
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.

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AdditionalInformation:
YoucanobtainmoreinformationontheCELLprogramandthethermodynamicsinthe
backgroundusing Help aswellasfromtheoriginalpublicationsoftheauthors7,8.

15.1

CellModule

Fig.2. Cellprogram.
The CELLprogram calculates the equilibrium configuration of chemical and
electrochemicalsystemsandcells,halfcells,fuelcells,aswellassecondaryandprimary
batteries.
Foracompletecellwithtwoormoreelectrodes,thetotalchargeandtheamountofatoms
present in the system are not sufficient conditions of equilibrium. The additional
constraint used in the CELL routine is the socalled DISCHARGE EQUATION. This
describes howmuchchargecanbetransferredfromthecathodetotheanodeduetothe
redoxreactions takingplace inthe cellbeforethe equilibriumstate is reachedfromthe
initial equilibrium state, see the example fucell.ice. These constraints can be defined in
the ExtraBalancesbox,seeFig.1.
Runningtheprogram:
1.
2.

Openinputdatafilewiththeoption"File|Open..."
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.

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AnswerYEStothequestion"Doyouwanttosaveequilibriumdata?"ifyouwant
tosaveresultsininputdatafileformatonthefile"Equil.ice".OtherwiseselectNO.
YoucanreturntotheHSCMainmenubyselecting"File|Exit".

With the options "File|View input file" and "File|View output file" you can view the
input file and output file, respectively. You may also send files to the printer with the
Printoptionintheviewingwindow.

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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.
2.
3.

Superscriptsandsubscriptsarenotallowed.
Innerparenthesesarenotallowed,forexample:
H2(Sn(OH)6)isnotavalidformula.UseH2Sn(OH)6instead.
Lastparenthesesarealwaysreservedforspeciestypedeclarations,forexample:
As(g)
Arsenicgas
C
Carbon
O2(g)
Oxygengas
C(D)
Diamond
Fe(l)
Liquidiron
FeS2
Pyrite
OH(a)
AqueousOHion
FeS2(M) Marcasite

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Ifyouwanttowritethefollowingformula
pleasewriteitinoneofthefollowingways:
(Lastparenthesisarereservedforsuffix)

AlO(OH)
AlO2H
AlO*(OH)
AlO*OH

Notvalid
Valid
Valid
Valid

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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.

2.

Horizontal lines. These lines represent reactions that are involved with electrons,
but areindependent ofpH. NeitherH(+a)ions norOH(a)ions participatetothese
reactions.
Diagonallineswitheitherpositiveornegativeslope.Theselinesrepresentreactions
thatareinvolvedwithbothelectronsandH(+a)andOH(a)ions.

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Verticallines.TheselinesrepresentreactionsthatareinvolvedeitherwithH(+a)or
OH(a)ions,butareindependentofEh.Inotherwords,electronsdonotparticipate
withthesereactions.

The chemical stability area of the water is shown in the EhpHdiagrams with dotted
lines. The upper stability limit of water is based on the potential when the oxygen
generationstartsontheanode.Itisspecifiedbythereaction:
2H2O=O2(g)+4H(+a)+4e
Thelowerstabilitylimitisbasedonhydrogenformationonthecathode.Itisspecifiedby
thereaction:
2H(+a)+2e=H2(g)
TheconstructionofthediagramswithHSCChemistryEpHmoduleisquiteasimpletask.
However,severalaspectsmustbetakenintoaccountwhenspecifyingthechemicalsystem
andanalyzingthecalculationresults,forexample:
1.
A basic knowledge of chemistry, aqueous systems and electrochemistry or
hydrometallurgyisalwaysneededinordertodrawthecorrectconclusions.
2.
TheEpHmodulecarriesoutthecalculationsusingpurestoichiometricsubstances.
Inpracticemineralsmaycontainimpurityelementsandthecompositionmaydeviate
slightlyfromthestoichiometricone.
3.
Therearealwayssomeerrorsinthebasicthermochemicaldataofthespecies.This
mayhavesignificanteffectontheresults,especiallyifthechemicaldrivingforceof
the reaction is small. Usually small differences between Pourbaix diagrams from
differentsourcescanbeexplainedbytheslightlydifferentbasicdataused.
4.

5.

6.

Sometimes dataforall existingspeciesis not availablefromtheHSCdatabaseor

fromtheothersources.Thiswilldistorttheresultsifthemissingspeciesarestablein
givenconditions.Themissingunstablespecieswillhavenoeffectontheresults.
The EpH module does not take into account the nonideal behavior of aqueous
solutions.However,inmanycasestheseidealdiagramsgiveaquitegoodideaofthe
possible reactions in aqueous solutions, especially if the driving force of the
reactionsishigh.
Thermochemical calculations do not take into account the speed of the reactions
(kinetics).Forexample,the formationoftheSO4(2a)ionmaybeaslowreaction.In
thesecases metastablediagramscreatedbyremovingsuchspeciesfromthesystem
maygivemoreconsistentresultswiththeexperimentallaboratoryresults.

TheHSCusermustbeverycarefulwhendrawingconclusionsfromEhpHdiagramsdue
to these limitations and assumptions. However, these diagrams may offer extremely
valuable information when combining the results with the experimental work and with a
good knowledge of aqueous chemistry. There is no universal kinetic or thermochemical
theory available, which could entirely substitute traditional experimental laboratory work
withpuretheoreticalcalculationmodels.
MoreinformationonEhpHdiagrams,calculationmethodsandapplicationscanbefound
fromdifferenthandbooks,forexample,fromthePourbaixAtlas12.

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ChemicalSystemSpecifications

Fig.1. SelectingelementsandspeciesfortheEh pHdiagram.

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=

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solidsubstances,AqueousNeutrals=dissolvedspecieswithoutcharge,AqueousIons
=dissolvedions,Gases=gaseousspecieswithoutcharge,GasIons=gaseousions,
and Liquids =liquidspecies.
4.

OK:PressOKtostartthesearchfromthedatabase.

5.

SelectSpecies:UsuallyyoucanselectallspeciestothediagrambypressingAll.In
some cases, however, it is useful to remove unnecessary species from the system.
This will decrease calculation time and simplify diagrams. Note: A) By pressing
simultaneouslyCtrlkeyandclickingwiththemouseitiseasytomakeanykindof
selection.B)Bydoubleclickingthespeciesitispossibletoseemoreinformationof
thespecies.LoadCUS25.IEPfiletoseetheselectedspeciesofthisexample.
The selection of the species is the most critical step of the EpH calculation
specifications.Duetothekineticreasonstheformationespeciallyoflargemolecules
maybetake quitealongtime inaqueous solutions.Forexample,theformation of
large polysulfide, sulfate, etc. molecules (S4O6(2a), HS2O6(a), HS7O3(a), ...)
maytakequiteawhile.Iftheseareincludedintothechemicalsystemthentheymay
easilyconsumeallthesulfurandthe formation ofsimplesulfides (AgS,Cu2S,...)
decreasesduetolackofsulfur.Thereforeinsomecasesthelargemoleculesshould
berejectedfromthechemicalsystem.
Thedataofsomespeciesmayalsobeunreliable,especiallyifthereliabilityclassof
thespeciesisnot1inthedatabase.Suchspeciesmayberejectedfromthechemical
system. Note also that species with (ia) suffix are not recommended to use, see
Chapter28.4fordetails.

6.

Temperature:The usermustspecifyatleastonetemperatureforthediagram.Upto
four temperatures may be specified in order to draw combined diagrams, which
showtheeffect oftemperature.Thetemperatures25,50,75and100Chavebeen
selectedinthisexample,Figs.1and2.

7.

CrissCobble:ThisoptionenablesHSCtoextrapolatetheheatcapacityfunctionof
theaqueousspeciesifthisdataisnotgiveninthedatabase11,seeChapter28.4.

8.

EpH:Press EpHtostart theFileSave dialogandCalculationofthe diagram.You

canalsopress FileSavein ordertosavethe dataforlateruse without runningthe
calculationprocedure.

9.

Diagram: Pressing the EpH button will show the Diagram specification form, see
Chapter 17.3 and Fig 2. By pressing Diagram in Fig. 2 you will see the default
diagram.

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Eh pHDiagramMenu

Fig.2. DefaultvaluesfortheEh pHdiagram.

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.

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The diagram specifications can be modified in the diagram menu. The selections can be
savedforlaterusewithFileSaveIEPselectionfromthemenu.TheIEPfilesmayalsobe
edited by any text editor like Windows Notepad. Please be careful as any mistake may
causeunpredictableresults.Thecalculationresults maybesavedto *.EPHfile withFile
Save EpH selection and loaded back with File Open EPH selection which causes the
diagramtobeautomaticallyrecalculated.
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.

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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

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theFormat menu, which contains dialogs forcolumnwidth,row height,font,alignment

andnumberformats.
Press Exit or select File Exit when you want to return back to the system specifications
form,Fig.1.The HelpmenuopenstheHSCHelpdialog.
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.

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Fig.3.EhpHdiagramofCuSH2Osystemat25CusingCuasthemainelement.ThemolalitiesofCu
andSare1mol/kgH2O.

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Fig.4.EhpHdiagramofSCuH2Osystemat 25CusingSas the main element.The molalities ofCu

andSare1mol/kgH2O.
The Format H2O Stability Lines selection opens the format dialog, which makes it
possibletomodifythewaterstabilitylinesformatsandproperties.This dialogcannotbe
openedbydoubleclickingthewaterstabilitylines.

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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.

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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.

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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.

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Fig.7. SpecificationofanFeSH2OsystemforanEhpHdiagram.

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Fig.8. SpecificationofacombineddiagramlayoutforanFeSH2Osystem.

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TheLineText options specify whichvariable values areusedas line labels. Usuallythe

combineddiagramsaresocomplicatedthatlabelsonthelinesareneededtodistinguishthe
linesofdifferentdatasetsfromeachother.Thelinelabelsareautomaticallylocatedinthe
middlepointofthelines.TheLineTextoptionisautomaticallyselectedonthebasisofthe
lastchangedvariable.However,theusercanchangethisselectionjustbeforestartingthe
final calculationswith Diagram.
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.
2.
3.

17.6

SpecifychemicalsystemandpressEpH,seeFig.7.
AcceptdefaultsettingsandpressCombine,seeFig.2.
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.

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.

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Fig.9.CombinedEhpHdiagramforanFeSH2Osystemat25C.TheFemolalityvalues1,103,and
106havebeenusedasparameter.

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Fig.10.Calculationresultsusedtodrawthefinaldiagram.ThisformcanbeopenedbypressingTableon
Diagramform,seeFig.9.

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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.
In hydrometallurgy, the EhpHdiagrams may be used, for example, to specify the
conditions for selective leaching or precipitation. In corrosion engineering, they may be
used to analyze the dissolution and passivation behavior of different metals in aqueous
environments. These diagrams may also be used to illustrate the chemical behavior of
differentionsinaqueoussolutions.
Geochemists usethePourbaixdiagrams quitecommonlytostudythe weatheringprocess
andchemicalsedimentation.Theweatheringprocessisusedtopredictwhatwillhappento
amineral,whichisexposedtoacidoxidizingconditionsathightemperatureandpressure.
Pourbaixdiagramscanalsobeusedtoestimatetheconditions,whichwereneededtoform
certainsedimentsandotherminerals17inthegeologicalpast.
Some application examples of EpH module and Pourbaix diagrams are given in Chapter
18,aswellasanexampleoftheEpHfileformat.

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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

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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.

Thestabilityareas ofwaterareshownbydottedbluelines inEhpHdiagrams,seeFig.2,

thecolorscannotbeseeninthisB&Wcopy.Usuallyitisdifficulttoexceedtheselimitsdue
to the formation of oxygen at the upper limit and hydrogen at the lower limit. In some
solutions these limits may be exceeded due the necessary overpotential of hydrogen and
oxygenformation.OnthebasisofFig.2itseemsthathydrogenformationoccursoncathode
beforethemetallicironcomesstable.
TheEhpHdiagramsmaybeusedinseveralways,forexample,

tofindpH,potentialandtemperatureregionswhichpreventcorrosion.
tofindoutwhichcompoundsarethecorrosionreactionproducts.
tofindimmunematerialswhichcanbeusedasprotectivecoating.
to find out a metal which may corrode instead of the constructive material. For
example,thezinclayeronasteelsurface.

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Fig.1.SpecificationofFeH2OsystemforEpHdiagramat25C.

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Fig.2.EhpHDiagramofFeH2Osystemat25C.MolalityofFeis106 M.

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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.

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Fig.4.FeH2Osystemat100C.Molality:Fe102 M,pressure1bar.

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Fig.5.FeCrH2Osystemat100C.Molalities:FeandCr102 M,pressure1bar.

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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.

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Fig.6.ZnH2Osystemspecifications.

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Fig.7.ZnH2Osystemat25C.DiagramisbasedonspecificationsinFig.6.

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Fig.8.ZnSH2Osystemspecifications,only identifiedspeciesincluded

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Fig.9.ZnSH2Osystemspecifications,allspeciesincluded.

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Fig.10.ZnSH2Osystemat25CbasedonspecificationsinFig.8.

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Fig.11.SZnH2Osystemat25CbasedonspecificationsinFig.8.

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Fig.12.ZnSH2Osystemat25CbasedonspecificationsinFig.9.

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Fig.13.SZnH2Osystemat25CbasedonspecificationsinFig.9.

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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.

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Fig.1. Thediagrammenu.Enthalpydiagramtypeselected.

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Fig.2. TheEnthalpy(latent)diagrambasedonthesettingsinFig.1.

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Fig.3. DiagramsettingsoftheEllinghamdiagramforoxides.

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Fig.4. EllinghamdiagramofoxidesbasedonthesettingsinFig.3.

PeterBjorklund

20.

DIAGRAMGRAPHICS

20.1

GraphicalObjects

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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.

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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.

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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.

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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.

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Figure4:Savingthecurrentdiagramobjects.

20.2

FormattingtheDiagram
MostofthediagramformattingoptionsareavailablewithinallHSCdiagramroutines.The
followingparagraphsgiveasummaryoftheseoptions:
1. Calculationpoints will be drawn onthe graph ifthe menu optionShow/Markers is
checked.IfthemenuoptionShow/Linesisunchecked,theconnectinglinesbetween
thecalculationpointswillnotbedrawn.Themarkersarenotdrawnbydefaultandthe
connectinglinesaredrawnbydefault.
2. Xandyscalesmaybeformattedbydoubleclickingthexoryscalenumbersorby
selectingXAxisor YAxisfromtheFormat menu.Forexample,the minimumand
maximumvaluesmaybechanged,seeFigure5.Insomecasesitisalsoadvantageous
to change the yaxis to logarithmic scale in order to display the large variations in
amounts or concentrations. Notice that the logarithmic yaxis is not available in all
modules.Fromthesamewindowyoucanalsochangethenumberformatofxandy
axisnumbersaswellastheirfontsize,color,etc.

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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.

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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.

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Figure7:Changinglabelandlinespecifications.
5. ThePlotAreacanbemodifiedbyselectingFormat/PlotArea fromthemenu.The
backgroundandbordercolorscanbechanged,aswellastheborderlinestyleand
thickness.Changingtheborderlinepropertiesmaybenecessaryinordertoviewa
curvethatisonaborderline.

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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.

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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.

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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.

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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.

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Figure12:CombiningdiagramsusingtheHSCCombineEditor.

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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).

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TppDiagramModule

Fig.1. InputdataforTppphasestabilitydiagrams.
TheTppDiagram module calculates phasestability diagrams usingpartialpressures on
both axis or temperature on the xaxis and partial pressure on the yaxis. This module
calculates the diagram on the basis of minimum Gibbs energy. However, it does not
checkeachxandypointinordertodecreasecalculationtime.Thecalculationis made
recursivelyusingthepresetresolutionandaspecificlogoutalgorithm.
TheuserinterfaceoftheTppmoduleisshowninFig.1withanexampleofaCuSO
system.Thediagrammaybedrawnusingthefollowingsteps:
1.

SelectthreeelementsfromtheelementlistandpressOK.

2.

SelectthespeciestodiagramonebyoneorbypressingSelectAll.KeeptheCtrl
keydownifyouwanttoremovesomespeciesfromtheselection.

3.

Select the xaxis species and the range for the xaxis. This selection will always
resetthedefaultxrangesettings.

4.

Select the yaxis species and the range for the yaxis. This selection will always
resetthedefaultyrangesettings.

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5.

Setonevariable,eithertemperatureinppdiagramsoronepartialpressureinTp
diagrams.Pleasealsoremembertogiveavaluefortemperatureoraselectedpartial
pressure.Thedefaultvalueforpartialpressureis1E20andfortemperature25C.
BothCandKunitscanbeused.

6.

Makeaselectionforthediagramlayoutoptionsifneeded:
Show:Showcalculationprogress.
Grid:Showgridondiagram
Color:Paintareaswithcolors
Resolution: Low > coarse resolution diagram, fast calculations. High >
highresolution diagram, long calculationtime.This settingsetsthesize of
the smallest calculated detail. Each step into a higher resolution will halve
thesizeofthesmallestvisibledetail.

7.

PressDiagram.

Thesystemspecifications canbesavedusingtheFileSaveTPPselectionfor lateruse.

ThesefilescanbereadbacktotheTppmoduleusingFileOpenTPP selection.
The Tpp module uses different colors for each stability area if the Color option is
selected. The user can modify the default color palette with the Format Color Palette
selection.Thiswillopenthecolorpalettedialog,seeFig.2.Thecolorscanbemodified
bydoubleclickingthecolorsintheColorcolumnorbytypingthecorrespondingRGB
valuestothe ColorCodecolumn.
This modified palette can be saved for later use by pressing Save Palette. The Tpp
automaticallyloadsthepalettefile,whichisnamedPPTCOL.PAL,butyoucanalsouse
othernames.Thesepalettescanbereloadedby theFileLoadUserPaletteselection.

Fig.2. ThecolorpalettedialogfortheTppmodule.

21.2 TppDiagrams

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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:

21.3

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.

LppDiagramModule

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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.
2.

3.
4.
5.
6.

SelectthreeelementswiththemouseandpressOK,inthiscaseTi,ClandO.
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.
Select one gas species for the xaxis, for example Cl2(g). You may select any
speciesforthexaxisexceptthosewhichcontainTi.
Select one gas species for the yaxis, for example O2(g). You may select any
speciesfortheyaxisexceptthosewhichcontainTi.
Change the temperature if needed, in this example 300 C. You may choose
betweenCandKbypressingthebutton.
PressFileSaveandaccept the name(TiClO700.IPS)forthe input file.ThePSD
programdrawsthediagramonthebasisofthisfile.Itmaybeagoodideatosave
all*.IPSfilesinaseparate \HSC\PSDdirectoryifavailable.

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Press PSD and wait a minute to see the diagram. You can return to HSC by
pressing Exit.
Youcancheckthenameanddataofthespeciesbydoubleclickingthelist.

PSDdiagramsofferaneasywaytoevaluatestabilitiesofdifferentcondensedsubstances
as a function of gas pressures, typically O2(g), S2(g), SO2(g), Cl2(g), etc. These
diagramscanbeused,forexample,tofindthebestconditionsforoxidizingorsulfatizing
reactions,etc.
Limitations:
Notethat allselectedsubstances mustcontainthe mainelement,forexampleTiin
theTiClOsystem,butthespeciesselectedforthexandyaxisshouldnotcontain
thismainelement(Ti)!!!
Ifyouhavemorethanonesubstancewiththesameoverallcomposition(stoichiometry)
inthespecieslist,forexampleNaSandNa2S2,FeOandFeO(l),etc.,pleaseselectonly
onesuchsubstanceforthediagram.InanycaseHSCwillautomaticallyomitsubstances
with identicalstoichiometry.Theusercan makethis selectionhimselfin ordertoselect
exactlythosesubstanceswhichhewantstobetakenintoaccount.

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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.

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LppModuleDiagram

Fig.6. PhaseStabilityDiagramoftheTi Cl O systemat300C.

Thephasestability diagram windowshows theresultsofthePSDprogramin graphical
form.Inthisdiagramitiseasytoseethestabilityareasofdifferentpuresubstancesunder
theprevailingconditions.
Youcaneditthisdiagraminthefollowingways:
1.
2.

3.

4.
5.

PressMenu tochangethescalesoftheaxes.
When you are satisfied with the scales, you can relocate all the labels by mouse
with the drag and drop method. Firstselect the label, keep the left mouse button
downanddragthelabeltotherightlocation,releasethemousebuttonandthelabel
willdropintothenewlocation.
Youcaneditthetextinthelabelsbysimplyclickingthetextusingthemouseand
typing the new text. You can edit the format of the labels and lines by double
clickingthelabel,seeFig.6.
Thexandyscalescanbechangedbydoubleclickingtheaxisnumbers.
ThefirsttimeyouuseHSCChemistryitmaybenecessarytochangethefontsby
pressing Font, because the fonts available vary from one computer to another.
UsuallyTimesNewRoman,bold,size11pointsisagoodselection.Theselection
willbeautomaticallysavedintheHSC.INIfile.

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WhenyouaresatisfiedwiththediagramyoumayprintitbypressingPrintatthe
bestresolutionofyourprinter.
Using Copy you may paste the diagram into other Windows programs using the
WindowsMetafileformat.
PressMenu toreturntoHSCortoexitthePSDprogram.

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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.

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Fig. 1. Calculation of the elemental composition of a material mixture. The user has given the species
namesincolumnAandthecontentsincolumnD.Thecalculatedresultisshownonrow4.

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Fig.2.CalculationofthespeciescompositionincolumnDusingtheelementalcompositioninrow3by
Solve.

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Fig. 3. Calculation of the elemental composition of a sulfide material. The user has given the species
namesincolumnAandthecontentsincolumnD.Theresultisonrow4.

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Fig.4.IterationofspeciescompositionsincolumnDonthebasisoftheelementalcompositionsinrow3
with IterateAll.ThetargetelementsincolumnBmustbespecifiedbytheuser.

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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.

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Fig.5. Calculationofthemixturecompositionofthreerawmaterials.

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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.

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23. COMPOSITIONCONVERSIONS
TheCompositionConversionmoduleisasimplifiedversionoftheMineralogyiteration
module. It is included in HSC Chemistry because the Composition Conversion module
easilygivesthecompositionsandamountsofthespeciesinwt%andkgunits.
Theuser maytypethenames ofthespecies into the firstcolumnandthe compositions
intothesecondcolumn.YoucanusealsootherspeciesthanthoseintheHSCdatabase,
however, you must use HSC formula syntax. The module automatically calculates the
elemental compositions of the species and the total composition of the mixture by
pressingConverttoElements.Thereverseconversionis madebypressingConvertto
Species.
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.

Fig.1. Composition conversions.

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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.

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Fig.1.TheElementsmodulecontainsseveralbasicpropertiesoftheelements.Theselectedpropertymay
beillustratedingraphicalformatbypressing Diagram.

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Fig.2.Thepropertiesoftheelementsmaybeillustratedingraphicalformat.Thevaluesoftheproperties
maybeshownbydoubleclickingtheelement.

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25.WATER

Figure1:PressureTemperaturecalculatorforwater.
The Pressure and Temperature calculator enables a complete thermodynamic description
foraspecies,byallowingtheusertospecifynotonlythetemperature,butalsothepressure
(partial).Thiscalculatoriscurrentlyonlyavailableforwater,sincethepropertiesofsteam
in particular, deviate significantly from those of the ideal gas, i.e. the heat capacity is
purelyatemperaturedependentfunction.Inlettingtheuserspecifywater/steampressure,
caseswherepressureisofextremeimportancecaneasilybecalculated.
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.

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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

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theenthalpyandentropydifferences willhavethesamevaluesasthosefoundinmost
steamtablesifthephaseissetto liquid atthetriplepoint.
2.CriticalPoint
Whenthetemperaturerises abovethe criticalpoint, it is no longerpossibletoclearly
distinguishbetweentheliquidandthegaseousphase.Suchaconditionisreferredtoas
supercritical.ThecriticalpointforwaterisatT=373.946Candp=220.64bar.Itis
important to know that above this point the program still specifies the phase of the
point,althoughtherearenolongeranyactualphasetransitionsbetweenthephases.
3.SaturatedCurves
There are three saturated curves in the diagram. These are gas/liquid, gas/solid and
liquid/solid.Apointlocatedonanyoneofthesecurvesindicatesthatthetwophasesare
inequilibrium.Thethreecurvesjoinatthetriplepoint,whichiswhereallthreephases
can exist simultaneously. The user may force a point onto the saturated curve by
selectingeitherSat.(g,l),Sat.(g,s)orSat.(l,s)fromoneofthephasecomboboxes on
row3.
4. SolidIce
Astabilityareaconsisting ofseveralsolidicephases,withdifferent crystalstructures,
of which some are shown on the diagram. Data is not, however, available for
thehighpressuresolidphases.
Calculationworksheet:
Thecalculationworksheet istotheleftofthewindow.Thefirstfourrowsareinputrows
andthelastsixrowsshowtheresults.Theinputrowsareexplainedinthe followingpoints:
1.Temperature
Thetemperatureunit maybe either inC orinK, depending onthetemperatureunit
combobox. The temperature is automatically calculatad when the Sat. (l,s) state is
selected.
2.Pressure
The pressure unit may be either in bar or in MPa, depending on the pressure unit
combobox.ThepressureisautomaticallycalculatadwhentheSat.(g,l)ortheSat.(g,s)
stateisselected.
3.Phase
Therearethreedifferentpurephasesavailableforwater:Solid(s),Liquid(l)andGas
(g).Thesethreephasesmaybecombinedonthe saturatedcurvesandtheyarespecified
as: Sat. (g,l), Sat. (g,s) and Sat. (l,s). At the triple point a mixture of all of these is
possible,however,onlyamixtureoftwoispossibleinthismodule.Whenapurephase
is selected, the actual phase is automatically selected according to the user input
(manually or with the mouse). When a saturated state is selected, the temperature or
pressure is automatically calculated, which is then indicated in a black font. For the
gas/liquid and gas/solid mixtures the pressure is automatically calculated and for the
liquid/solidmixturethetemperatureisautomaticallycalculated.Notethatwhenmoving
outsidethe limits ofthesaturationcurve,thephase willautomatically changeintothe
correspondingpurephaseofthespecifiedpoint.
4.Mixture%
Itispossibleheretoenterthemixturepercentageofthesaturatedstate.Thisisthesame
asthedrynesspercentageofsteamwhenthepointisonthesaturatedgas/liquidcurve.
Thepercentagealwaysreferstotheamount ofthefirstphaseinthetotalmixture,e.g.
the gas percentage in a gas/liquid mixture. This is set to 50 % by default and only
visiblewhenasaturatedstateisspecified.

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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

hs ,c =

Dhs
,
Dh

[1]

where Dh is thereal enthalpydifferenceand Dhs is theisentropicenthalpydifference.

Theisentropicefficiencyforaturbineisdefinedas

hs,t =

Dh
.
Dhs

[2]

An isentropic process is always adiabatic, however, an adiabatic process is not

necessarilyisentropic.

25.2

Calculation examples

PeterBjorklund
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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.

PeterBjorklund
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Evaporation processinaheatrecoveryboiler

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.

PeterBjorklund
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Steamturbineprocess

Figure4:Steamturbineprocess.
Asimplesteamturbineprocess is shownin Figure4.Thecalculationshowsthat the net
enthalpyforamassflowof10kg/sis10633kWandthusexothermic,i.e.theenthalpyis
released in the form of work on the shaft. The entropy generation is 7.5 kW/C and the
processisthereforenotisentropic.BydecreasingtheMixture%(inthiscase~81.7%)the
process maybecompared withtheideal isentropicprocess for whichthere is no entropy
generation.Theenthalpyreleasedintheisentropicprocessis12903kWandtheisentropic
efficiencyistherefore,accordingtoequation2, hs,t=10633kW/12903kW l0.82.

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25.3

DetailedDescription

25.3.1

Pressurecorrectioninthedatabase
The pressurecorrected calculations are based on new pressurespecific species in the
database. They are of the form S(XbarP), where S denotes the species, X the pressure
(partial)inbarsandPthephase.Thephaseisonlyspecifiedforgaseousspecies.Theonly
currentlyavailablespeciesisH2O(water),andthepressurecorrectedspeciesarefoundin
thedatabaseasH2O(0.01bar),H2O(0.01barg),H2O(100bar),H2O(100barg),etc.Notethat
ifthephaseisnotspecified,itmaybeeithersolidorliquiddependingonthetemperature.
Forsupercriticalsteam,thatisforT m 373.946C,agaseousphaseisusedforp<220.64
bar and a liquid phase for p m 220.64 bar, although the two phases are impossible to
separateinreality.
Table1showsthepressurecorrectedwaterspeciescurrentlyfoundintheHSCdatabase.
Pressure[bar]

Solid/liquidspecies(ice/water)

Gaseousspecies(steam)

0.01
0.05
0.1
0.5
1
5
10
20
30
40
50
60
70
80
90
100
200
300*
400*
500*
600*
700*
800*
900*
1000*

H2O(0.01bar)
H2O(0.05bar)
H2O(0.1bar)
H2O(0.5bar)
H2O(1bar)
H2O(5bar)
H2O(10bar)
H2O(20bar)
H2O(30bar)
H2O(40bar)
H2O(50bar)
H2O(60bar)
H2O(70bar)
H2O(80bar)
H2O(90bar)
H2O(100bar)
H2O(200bar)
H2O(300bar)*
H2O(400bar)*
H2O(500bar)*
H2O(600bar)*
H2O(700bar)*
H2O(800bar)*
H2O(900bar)*
H2O(1000bar)*

H2O(0.01barg)
H2O(0.05barg)
H2O(0.1barg)
H2O(0.5barg)
H2O(1barg)
H2O(5barg)
H2O(10barg)
H2O(20barg)
H2O(30barg)
H2O(40barg)
H2O(50barg)
H2O(60barg)
H2O(70barg)
H2O(80barg)
H2O(90barg)
H2O(100barg)
H2O(200barg)

*Supercriticalpressures

Table1:Pressurecorrectedspeciescurrentlyavailableinthedatabase.
Sincewateris inaliquidformatthereferencetemperatureof25Cforpressures higher
than 0.032 bar, the Cp functions for steam follow the saturated steam curve below the
boilingpoint.This means thatthepressureisnot keptconstantbelowthis pointandthus
thepressurevalueinthespecies name,i.e.XinH2O(Xbarg),isnolongervalidforthese
temperatures.ThismaybeseenfromFigure5,wheretheCpfunctionsofsteamatdifferent
pressuresareshown.WhenthetemperaturedropsbelowtheboilingpointtheCpfunctions
followthesaturationcurve, wherethepartialpressurealsoreduces withthetemperature.
Thisalsomeansthatthetotalenthalpyandentropycurvesbelowtheboilingpointwillnot
joinasexpectedandthereforethesecurvesarecomparablewitheachotheronlyforvalues
aboveorequaltotheboilingpoint.Thisis,however,notanissuewhenstudyingonlyone

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pressurecorrected species at a time since the enthalpy/entropy differences are then still
valid.NaturallythisisneveraprobleminthePressureandTemperaturecalculator,sinceit
automaticallychoosestheliquidphasewhenthetemperaturedropsbelowtheboilingpoint
foraconstantpressure.
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.

PeterBjorklund
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Basictheory
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
T

Cp(T,p)dT + H

'
f

H(T,p)= H (298.15K,p)+

tr

[3]

298.15K

whereHf (298.15K, p)is the modified enthalpy offormationat pressurepandHtr is the

enthalpy of a phase transformation. The entropy at pressure p may be calculated in a
similarmanneras
T

'
0

S(T,p)= S (298.15K,p)+

H
Cp(T,p)
dT + tr ,
T
Ttr
298.15K

[4]

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

Cp (T,p) = A( p) + B( p) 10-3 + C( p) 105 T-2 + D( p) 10-6 T2,

[5]

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

p(T )=0.1 exp(11.78(T - 372.79) /(T - 43.15)),

[6]

whereTis thetemperatureinKandpthepressure inMPa.Thepressure forasaturated

gas/solidmixture is

p(T )=1010.5380997 2663.91/(T+0.01) /10000,

[7]

whereTisthetemperatureinKandpthepressureinMPa.Thetemperatureforasaturated
liquid/solidmixtureis

T ( p)=-0.009p+ 273.16,

[8]

PeterBjorklund

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02103ORCT

whereTisthetemperatureinKandpthepressureinMPa.Theseequationscorrespondto
thesaturatedcurvesinthep,Tdiagramandareutilizedinthemodulewheneverasaturated
stateisselected.
In order to calculate the influence of pressure on the enthalpy and entropy below the
freezingpoint,apressurecorrectiontermisused.Thecorrectiontermis

DhT =const = (1- Tf a v,ice )n ice( pf - p0),

[9]

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.

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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.
2.

Some 90 different quantities and 444 units are available. The user can easily add
ownunitsandcoefficientsintotheconversioncalculatordatabase.
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.
2.
3.

Selectthequantityyouareinterestedin,forexample,Energy.
Selecttheunitandprefixtobeusedincolumns1and2.
Selecttheunitandprefixtobeusedincolumns3and4.

A.Roine
4.

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Type the values into column 1 or 3. This will automatically show the converted
value using the selected units. You can change the quantities, units and prefixes
wheneveryouwant,asseeninFig.1.

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.
2.
3.
4.

Constantssheet:Chemicalandphysicalconstants.
Meshsheet:Particlesizesinmeshandmmunits.
Airsheet:Aircompositionandhumiditytables.
H2Osheet:Watervaporpressuretables.

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Theusermayalsomodifythesesheetsaswellasaddnewsheets.Theworkbookmustbe
savedwiththeFileSaveselectioninordertousethenewdatalateron.
Nearlyallthesameformat,editandprintingproperties,aswellasresizingoftheform,are
availableintheUnitsmodule.

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27. ExcelAddInFunctions
27.1

Gettingstarted
WithHSC5.0AddInFunctionsitispossibletousetheHSC5.0databasedirectlyunder
MSExcel2000andinthatwaycarryoutseveralthermochemicalcalculations.Inorderto
usethesefunctionsinExceltheymust,however,firstbeactivated.Threestagesmaybe
neededtoactivateHSCfunctionsinExcel.Thenumberofstagesneededdependsonthe
computersettingsandWindowsandExcelversions.
ActivationStage1:
1.
2.
3.
4.

OpenExcel2000(NOTE: HSCAddInsdonotworkunderearlierExcelversions!)
SelectTools,AddIns... fromthemenu.
SelectBrowseandlocateHSC5.xlafromyourHSC5\AddInsfolder.
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.

PeterBjorklund

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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)
BAL(Equation)
SPECIES(DBNo,Position)

Changesthecurrentunits,T=C/KandE=Mcal/MJ/kWh.
SheetNOTrecalculated!
Balancesgivenequation.
ReturnsspeciesindatabaseDBNoandgivenposition.

SpeciesFunctions
H(SpeciesT)
S(SpeciesT)
CP(SpeciesT)
G(SpeciesT)
HKG(SpeciesT)
HNM3orHCM(SpeciesT)
HLAT(SpeciesT)

Returnstheenthalpy(permol)ofthespeciesatT(temperature).
Returnstheentropy(permol)ofthespeciesatT.
Returnstheheatcapacityatconstantpressure(permol)ofthespeciesatT.
ReturnstheGibbsenergy(permol)ofthespeciesatT.
Returnstheenthalpy(perkg)ofthespeciesatT.
Returnstheenthalpy(perNm)ofthespeciesatT.
Returnsthelatententhalpy(permol)ofthespeciesatT.

ReactionEquationFunctions
H(EquationT)
S(EquationT)
CP(EquationT)
G(EquationT)

Returnstheenthalpy(permol)ofthereactionequationatT.
Returnstheentropy(permol)ofthereactionequationatT.
Returnstheheatcapacitydifference(permol)ofthereactionequationatT.
ReturnstheGibbsenergy(permol)ofthereactionequationatT.

PeterBjorklund
HKG(EquationT)
K(EquationT)

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Returnstheenthalpy(perkg)ofthereactionequationatT.
ReturnstheequilibriumconstantofthereactionequationatT.

Iteration(reverse)Functions
TATH(SpeciesH)
TATS(SpeciesS)
TATCP(SpeciesCP)
TATG(SpeciesG)

Returnsthetemperatureofthespecieswithgivenenthalpy(permol).
Returnsthetemperatureofthespecieswithgivenentropy(permol).
Returnsthetemperatureofthespecieswithgivenheatcapacity(permol).
ReturnsthetemperatureofthespecieswithgivenGibbsenergy(permol).

FlowFunctions
FLOWH(SpeciesAmountT)
FLOWS(SpeciesAmountT)
FLOWCP(SpeciesAmountT)
FLOWG(SpeciesAmountT)

Returnstheenthalpyofaflow(SpeciesandAmountasranges)atT.
Returnstheentropyofaflow(SpeciesandAmountasranges)atT.
Returnstheheatcapacityofaflow(SpeciesandAmountasranges)atT.
ReturnstheGibbsenergyofaflow(SpeciesandAmountasranges)atT.

TemperatureindependentFunctions
STRUCT(Species)
CHNAME(Species)
CONAME(Species)
CAN(Species)
MW(Species)
DE(Species)
MP(Species)
BP(Species)
PHASE(Species)
RGBCOLOR(Species)
REF(Species)
REL(Species)

Returnsthestructuralformulaofthespecies.
Returnsthechemicalnameofthespecies.
Returnsthecommonnameofthespecies.
Returnsthechemicalabstractnumberofthespecies.
Returnsthemolecularweightofthespecies.
Returnsthedensityofthespecies.
Returnsthemeltingpointofthespecies.
Returnstheboilingpointofthe species.
Returnsthephaseofthespecies.
ReturnstheRGBcolorofthespecies.
Returnsthedatabasereferenceofthespecies.
Returnsthereliabilityclassofthespecies.

PercentageFunctions
MOLP(Species1Species2)
WTP(Species1Species2)

Returnsthemol%ofSpecies1inSpecies2.
Returnsthewt%ofSpecies1inSpecies2.

CpDataFunctions
CPFUNCTION(Species)
CPA(Species)
CPB(Species)
CPC(Species)
CPD(Species)
TMIN(Species)
TMAX(Species)

Returnsthecompleteheatcapacity(cp)polynomialfunction(asastring)ofthe
givenspecies.
ReturnstheAcoefficient(asanumber)ofthecpfunction.
ReturnstheBcoefficient(asanumber)ofthecpfunction.
ReturnstheCcoefficient(asanumber)ofthecpfunction.
ReturnstheDcoefficient(asanumber)ofthecpfunction.
Returnstheminimumvalidtemperatureofthecpfunction.
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.

PeterBjorklund

HSCChemistry5.0

274

June28,2002

02103ORCT

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.

PeterBjorklund

27.4

HSCChemistry5.0

275

June28,2002

02103ORCT

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.