Binary Systems. Part 4: Binary Systems from Mn-Mo to Y-Zr: Phase Diagrams, Phase Transition Data, Integral and Partial Quantities of Alloys

329 Pages·2006·7.782 MB·English

by  P. Franke, D. Neuschütz (auth.), P. Franke, D. Neuschütz (eds.)

Introduction 1
Introduction
Thefirst4volumesofthisseries,underthegeneralheadingThermodynamicPropertiesofInorganicMa-
terials, presentsSGTE-compiledthermodynamicdataforpuresubstances, includingtheelementsintheir
stablestates. Theseriesnowcontinueswithafurther4volumesofSGTEselectedandcompileddata–this
timeforbinaryalloysystems. Forthermodynamiccalculationsinvolvingalloysolutionphases,Gibbsen-
ergies of the pure elements in different stable and metastable states are required. Such data have been
compiled on behalf of SGTE by Dinsdale [91Din] and have recently been updated [02Din]. The values
havefoundwideuseinternationallyasthebasisforthermodynamicassessmentsofhigherordersystems.
Aswiththepureelementvalues,thebinaryalloydescriptionscontainedinthepresent4-volumeseriesare
notonlycompleteinthemselves,butalsoextendthebasisforthermodynamicassessmentsandcalculations
relatingtomulticomponentalloys.
MembersofSGTEhaveplayedaprincipleroleinpromotingtheconceptof“computationalthermochem-
istry”asatimeandcost-savingbasisforguidingmaterialsdevelopmentandprocessinginmanydifferent
areas of technology. At the same time, through organisation of workshops and participation in CODATA
Task Groups, SGTE members have contributed significantly to the broader international effort to unify
thermodynamicdataandassessmentmethods.
TheSGTEdatacanbeobtainedviamembersandtheiragentsworld-wideforusewithcommerciallyavail-
able software developed by some of the members, to enable users to undertake calculations of complex
chemicalequilibriaefficientlyandreliably.
TheSGTEMemberorganisationsare:
Canada: –THERMFACTLTD.LTEE
France: –InstitutNationalPolytechnique(LTPCM),Grenoble
–AssociationTHERMODATA,Grenoble
–IRSID,Maizie`res-le`s-Metz
–Universite´ deParis-Sud(EA401)
Germany: –Rheinisch-Westfa¨lischeTechnischeHochschule(MCh),Aachen
–GTT-Technologies,Herzogenrath
–MPIfu¨rMetallforschung(PML),Stuttgart
Sweden: –RoyalInstituteofTechnology(MSE),Stockholm
–Thermo-CalcSoftwareAB,Stockholm
UnitedKingdom: –NationalPhysicalLaboratory(MATC),Teddington
–AEATechnologyplc,Harwell
USA: –TheSpencerGroup
Assessmentandselectionprocedures
Theassessmentsofthebinaryalloysystemspresentedinthis4-volumeserieshaveallbeenmadeusingthe
so-called“CALPHADmethod”[98Sau]. Thismethodresultsinanoptimisedparametricdescriptionofthe
Gibbs energies of the phases of the system when taking into account the crystallographic structure of the
phases and all the experimental thermodynamic and phase boundary data available. The thermodynamic
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2 Introduction
parametersprovideaconsistentanalyticaldescriptionofthephasediagram,chemicalpotentials,enthalpies
ofmixing,heatcapacities,etc.
Asanexample,therelationsbetweentheGibbsenergycurvesandthephasediagramfortheBi-Snsystem
are demonstrated in Figs. 1 and 2, respectively. In Fig. 1 the Gibbs energy curves for the phases in the
Bi-Sn system are given as a function of the mole fraction of Sn, x , at T = 450 K. At fixed pressure,
Sn
temperatureandcomposition,theequilibriumofthesystemisdeterminedbythestatewiththelowestGibbs
energy. All equilibrium states are located on the convex hull of the set of G-curves which is constructed
by applying double-tangents to the curves. The tangent points denote the boundaries between one- and
two-phase regions. In Fig. 2, these points are marked on the selected isotherm of T = 450 K. If this
constructionisrepeatedforothertemperaturesthecompletephasediagramofthesystemisobtained.
Fig. 1. GibbsenergyfunctionsforthephasesintheBi-Sn Fig.2.PhasediagramforthesystemBi-Sn.
systemat450K.
Ifseveralpublishedassessmentsareavailableforaparticularsystem,selectionhasbeenmadefollowingan
analysis of how well the available experimental data are reproduced by the description. Compatibility of
themodellingusedwithrespecttoassemblyofadatasetforhigherordersystemshasalsobeentakeninto
account.
There are many different phases present in binary systems and, in order to combine their thermodynamic
descriptionsinhigherordersystems,itisimportanttoknowtheircrystalstructuresaswellasthesolubilities
ofalloyedelementsinthem. Inthesevolumes,thenamingofphaseshasbeencarriedoutasconsistentlyas
possiblesoastofacilitateidentificationofthesamephaseappearingindifferentbinarysystems.
Themaincharacteristicsofeachsystemarepresentedinindividualreportswhichgenerallyinclude
– thecalculatedphasediagram
– anabstractsummarisingthemainfeaturesofthesystem
– a summary of the various stable and metastable phases defined in the system together with crys-
tallographic information, the phase name used in the database and the thermodynamic model used,
includingtheoccupationofthesublattices
– atableoftheinvariantreactions
– tablesanddiagramswithintegralquantities
– tablesanddiagramswithpartialquantities
– plotsofcalculatedthermodynamicfunctions
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Introduction 3
Criteriaforselectionofbinaryalloyassessments
Inordertoqualifyforselection,thefollowinginformationwasreviewed:
– phasediagram
– thermodynamicinformation
– documentation
– modelsusedforsolutionphases
– modelsusedforstoichiometricphases
– feasibilityofextrapolation
– compatibilitywithSGTEunarydata
ThermodynamicModelling
Elements
TheGibbsenergyofthepureelementi,◦Gφ(T),referredtotheenthalpyforitsstablestateφat298.15K,
i
◦Hiφ(298.15K), is denoted by GHSERi. This quantity is described as a function of temperature by the
followingequation:
GHSERi = ◦Gφi(T) − ◦Hiφ(298.15K)
= a+bT +cT ·lnT +dT2+eT3+f T−1+gT7+hT−9 (1)
Anumberoftemperaturerangesmaybeused. Thefirstandsecondderivativesofthisquantitywithrespect
totemperaturearerelatedtotheabsoluteentropyandheatcapacityofthecompoundatthesametemper-
ature. Experimental values for heat capacities can thus be directly used in the optimisation and will be
relatedtothecoefficientsc,d,e,f,gandh.
Forelementswhichhaveamagneticordering,e.g. Co,Cr,Fe,NiandMn,thetermGHSERisreferredto
apara-magneticstate. AnadditionaltermisthusaddedtothemolarGibbsenergyofthemagneticphase.
Forelementsaswellasforsolutions,thistermisequalto:
Gmag =RTln(β+1)f(τ) (2)
where τ is T/T∗ , T∗ being the critical temperature for magnetic ordering (Curie temperature T for
C
ferromagnetic materials or the Ne´el temperature T for antiferromagnetic materials), and β the average
N
magneticmomentperatomofthealloyexpressedinBohrmagnetons.
Thefunctionf(τ)isgivenas:
τ <=1 : f(τ)=1−[79τ−1/140p+(474/497)(1/p−1)(τ3/6+τ9/135+τ15/600)]/A
τ >1 : f(τ)=−[τ−5/10+τ−15/315+τ−25/1500]/A
withA=518/1125+(11692/15975)(1/p−1).
These equations were derived by Hillert et al. [78Hil] from an expression of the magnetic heat capacity
Cmag describedbyInden[81Ind].
P
Thevalueofpdependsonthecrystalstructure. Forexample,pisequalto0.28forfccandhcpmetalsand
0.40forbccmetals[81Ind]. Foranti-ferromagneticalloystheT∗ andβ aremodelledasnegativeandthey
aredividedbyananti-ferromagneticfactorof-1forbccand-3forfccandhcpbeforethevaluesareused
inequation(2).
For each element, equation (1) is taken from the SGTE unary database. These data have been published
previouslyastheSGTEdataforthepureelementsbyDinsdale[91Din,02Din].
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4 Introduction
ThefunctionGHSERi isalsooftenusedtoexpressthethermodynamicfunctionsofmetastablestructures
ϕ,differentfromthestablestructureofthepureelement. Theexpression◦Gϕ(T) − ◦Hφ(298.15K)is
i i
equivalent to ◦Gϕi(T) − ◦Gφi(T)+GHSERi. The term ◦Gϕi(T) − ◦Gφi(T) is often called the lattice
stabilityofelementiinphaseϕ.
Binarycompounds
TheGibbsenergyofthecompoundA B maybeexpressedas:
a b
G (T)−a◦Hφ(298.15K)−b◦Hφ(298.15K) = f(T) (3)
AaBb A B
whereaandbarestoichiometricnumbers.Theexpressionforf(T)isidenticaltothatgivenbyequation(1).
Equation(3)canbetransformedbyapplyingequation(1)foreachcomponent
f(T) = G (T)−a◦Gφ(T)−b◦Gφ(T)+aGHSER +bGHSER
AaBb A B A B
= ∆ G (T)+aGHSER +bGHSER (4)
f AaBb A B
Theterm∆ G (T)istheGibbsenergyofformationofthecompoundreferredtothestableelementsat
f AaBb
temperatureT. ItcanoftenbetakenasalinearfunctionofT.
Gaseousspecies
An expression identical to equation (1) may be used to describe the Gibbs energy of the gaseous species
withtheadditionalRT ln(P/P )term,whereP isthetotalpressureandP thereferencepressure,usually
0 0
0.1MPa. Thespeciesinthegasphaseareassumedtoformanidealsolution. Thereferencestateforeach
vapourspeciesistakentobethepurecomponentsat0.1MPapressure. Thethermodynamicpropertiesof
the gas species are normally obtained fromvapour pressuremeasurements coupled to spectroscopic data.
Dataforgaseoussubstancesarecoveredinmoredetailinsubvolume(A)forpuresubstances.
Many species, i.e. molecules, may existin the gas phase and each has a Gibbs energy of formation. The
equilibriumwithinagasforagivencompositionatagiventemperatureandpressureiscalculatedbymin-
imisingtheGibbsenergyvaryingthefractionofthespecies. AstheGibbsenergyisusedasthemodelling
functioninmostsolutiondatabasesitisnotpossibletocalculatethecriticalpointforgas/liquid.Themodels
usedforthedifferentliquidsarealsonotcompatiblewiththeidealmodelforthegas.
Condensedphases
Thecondensedphasescanbedividedintothreegroups.
1: Substitutionalsolutions
Forthesubstitutionalsolutionφ,themolarGibbsenergyisexpressedasfollows:
Gφ =Gφ,srf +Gφ,id+Gφ,E (5)
m m m m
with
(cid:1)
Gφm,srf = xioGφ (6)
i (cid:1)
Gφm,id = RT xilnxi (7)
i
(cid:2)
xi isthemolarfractionofcomponentiwith ixi = 1. ThetermGφm,srf istheGibbsenergyofthephase
relativetothereferencestateforthecomponentsandGφ,idisthecontributionofidealmixingentropy.
m
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Introduction 5
TheRedlich-Kisterequation[48Red],apowerseriesexpansion,isusedtoexpresstheexcessGibbsenergy,
Gφ,E,fortheinteractionbetweenthetwoelementsiandj asfollows:
m
(cid:1)
Gφm,E = xixj νLφij (xi−xj)ν (8)
ν=0
Themodelparameter νLφ canbetemperaturedependent.
ij
Ifexperimentalinformationforternarysolutionsisavailablethenanextratermcanbeaddedtoequation(8).
ForaternarysystemA–B–C,thistermisequalto:
x x x L (9)
A B C ABC
Theliquidisinmostcasestreatedasasubstitutionalsolution.Forliquidswithverystrongshortrangeorder
theassociatemodel[78Som]ortheionicliquidmodel[85Hil]hassometimesbeenused.
Formagneticalloys,thecompositiondependenceofT∗andβ areexpressedby:
(cid:1)
T∗(x) = xi◦Ti∗+T∗,E (10)
(cid:1)i
β(x) = xi◦βi+βE (11)
i
whereT∗,EandβEarebothrepresentedbyanexpressionsimilartoequation(8).
2: OrderedPhases
Theuseofthesublatticemodel,developedbyHillertandStaffansson[70Hil]basedonTemkin’smodelfor
ionicsolutions[45Tem]andextendedbySundmanandA˚gren[81Sun],allowsavarietyofsolutionphases
tobetreated,forexampleinterstitialsolutions,intermediatephases,carbidesetc. Alloftheserepresentan
orderingoftheconstituentsondifferentsublattices.
As non-stoichiometric phases are formed by several sublattices, they can be schematically described as
follows:
(A,B,...)p(A,B,...)q...
wheretheconstituentsA,B,... canbeatoms,vacancies,moleculesorionsonthedifferentsublattices....p,
q,... arethenumberofsites. Ifp+q+...=1,thenthethermodynamicquantitiesarereferredtoonemole
ofsites. Mostoftenpandqareselectedtobethesmallestsetofintegers.
Foreachsublattices,thesitefractionofthespeciesi,ys,isequalto
i
ns ns (cid:1) (cid:1)
ys = (cid:2) i = i with ys =1 and ns =n (12)
i ns ns i
j j i s
where ns is the number of speciesiin sublattice s, ns the number of sitesin sublattice s, and n the total
i
numberofsites. ns isrelatedtonbyns = n·p/(p+q+...). Thenumberofsublatticesandthespecies
occupyingthem,isgenerallyobtainedfromcrystallographicalinformation.Themolefractionofanelement
isobtainedby (cid:2)
nsys
xi = (cid:2) nss(1−iys ) (13)
s Va
whereys isthefractionofvacantsitesonsublattices.
Va
Thismodelalsodescribesstoichiometricphases,inwhichcasethesublatticesareoccupiedonlybyasingle
species,andsubstitutionalphaseswhichhaveasinglelattice.
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6 Introduction
ThemolarGibbsenergyforaphaseφexpressedbythesublatticemodelisequalto
Gφ =Gφ,srf +Gφ,id+Gφ,E (14)
m m m m
Asanexample,atwosublatticephasewithtwoelementsAandBineachofthesublatticesisconsidered.
Denotingthesublatticeswithprimesatthesymbols,thesurfaceofreferencefortheGibbsenergyis
Gsrf =y(cid:1) y(cid:1)(cid:1) oG +y(cid:1) y(cid:1)(cid:1) oG +y(cid:1) y(cid:1)(cid:1) oG +y(cid:1) y(cid:1)(cid:1) oG (15)
A A A:A A B A:B B A B:A B B B:B
Theterms oG and oG representtheGibbsenergiesofthephaseφfortheconstituentelementsA
A:A B:B
and B. The colon separates the different sublattices. The terms oG and oG represent the Gibbs
A:B B:A
energies of the stoichiometric compounds ApBq and BpAq, which may be stable or metastable. oGA:A,
oG , oG and oG arenumericallygivenbyequations(3)and(1).
B:B A:B B:A
ThetermGidisrelatedtothemolarconfigurationalentropyandisequalto:
m
Gid =RT[p(y(cid:1) lny(cid:1) +y(cid:1) lny(cid:1) )+q(y(cid:1)(cid:1) lny(cid:1)(cid:1) +y(cid:1)(cid:1)lny(cid:1)(cid:1))] (16)
m A A B B A A B B
Finally,theexcessGibbsenergyGE isequalto
m
GEm =yA(cid:1) yB(cid:1) [yA(cid:1)(cid:1)LA,B:A+yB(cid:1)(cid:1)LA,B:B]
+yA(cid:1)(cid:1)yB(cid:1)(cid:1)[yA(cid:1) LA:A,B+yB(cid:1) LB:A,B]
+yA(cid:1) yB(cid:1) yA(cid:1)(cid:1)yB(cid:1)(cid:1)LA,B:A,B (17)
The termsLi,j:i and Li:i,j represent the interaction parameters between the atoms on one sublattice fora
givenoccupancyoftheother,andcanbedescribedbyaRedlich-Kisterpolynomial,asfollows:
(cid:1)
Li,j:i = (yi(cid:1) −yj(cid:1))ν νLi,j:i (18)
ν=0
Theparameters νLi,j:icanbetemperaturedependent. ThetermLi,j:i,j isknownasthereciprocalparame-
terwhichmayberelatedtotheexchangereactionofAandBbetweenthesublattices. Itisusuallyassumed
tobecompositionindependentbutmaydependontemperature.
Theaboveequationscaneasilybeextendedtoternaryandhigherordersystems.
3: Phaseswithorder-disordertransformation
Phaseswithorder-disordertransformation,likeA2/B2andA1/L1 canalsobedescribedwiththesublattice
2
methodalthoughthisdisregardsanyexplicitshortrangeordercontributions.AsingleGibbsenergyfunction
maybeusedtodescribethethermodynamicpropertiesofboththeorderedanddisorderedphasesasfollows:
Gm =Gdmis(xi)+∆Gomrd(yis) (19)
whereGdmis(xi)isthemolarGibbsenergyofthedisorderedphase,givenbyequation(5)and∆Gomrd(yis)is
theorderingenergygivenby:
∆Gomrd =Gsmubl(yis)−Gsmubl(yis =xi) (20)
where Gsubl(ys) is given by equation (14). This must be calculated twice, once with the original site
m i
fractionsysandoncewiththesesitefractionsreplacedbythemolefractions. Ifthephaseisdisorderedthe
i
sitefractionsandmolefractionsareequalandthus∆Gord equaltozero.
m
Toensurestabilityofthedisorderedphase,thefirstdifferentialofGsublwithrespecttoanyvariationinthe
m
siteoccupancymustbezeroatthedisorderedstate. Thisenforcessomerelationsbetweentheparameters
inGsublasisdiscussedin[88Ans].
m
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Introduction 7
DescriptionoftheTablesandDiagrams
The diagrams and tables which are presented for the binary systems provide an overview of the major
thermodynamic properties and the mixing behaviour of these systems. Depending on the nature of the
respectivesystem,thenumberandthetypeofthepresenteddiagramsandtablesvaries. Forallsystems,a
calculatedphasediagram,ashortabstractandatablelistingthecondensedphasesareprovided. Additional
tablesanddiagramspresentdataforinvariantreactions,integralandpartialquantitiesoftheliquidandsolid
phases,andstandardreactionquantitiesofintermetalliccompoundsinthesystem.
Thefollowinglistgivesonoverviewofthequantitiesinthetablesanddiagramsandtheirdesignations. The
definitionofthesequantitiesisprovidedinthefollowingparagraphs.
Symbol Unit Quantity
a thermodynamicactivityofthecomponentAinaliquidorsolidsolution
A
∆ C◦ J mol−1K−1 change of the molar heat capacity at constant pressure upon formation of a
f P
compound
∆CP J mol−1K−1 change of the molar heat capacity at constant pressure upon formation of a
liquidorsolidsolution
∆G J mol−1 integralGibbsenergyofaliquidorsolidsolution
m
GE J mol−1 integralexcessGibbsenergyofaliquidorsolidsolution
m
∆G J mol−1 partialGibbsenergyofthecomponentAinaliquidorsolidsolution
A
GE J mol−1 partialexcessGibbsenergyofthecomponentAinaliquidorsolidsolution
A
∆ G◦ J mol−1 standardGibbsenergyofformationofacompound
f
∆H J mol−1 integralenthalpyofaliquidorsolidsolution
m
∆H J mol−1 partialenthalpyofthecomponentAinaliquidorsolidsolution
A
∆ H◦ J mol−1 standardenthalpyofformationofacompound
f
∆ H J mol−1 enthalpyofreactionpermoleofatoms
r
p Pa partialpressureofspeciesi
i
∆S J mol−1K−1 integralentropyofaliquidorsolidsolution
m
SE J mol−1K−1 integralexcessentropyofaliquidorsolidsolution
m
∆S J mol−1K−1 partialentropyofthecomponentAinaliquidorsolidsolution
A
SE J mol−1K−1 partialexcessentropyofthecomponentAinaliquidorsolidsolution
A
∆ S◦ J mol−1K−1 standardentropyofformationofacompound
f
T K thermodynamictemperature
T K Curietemperature
C
x molefractionofcomponentAinanalloyorcompound
A
γ activitycoefficientofthecomponentAinaliquidorsolidsolution
A
The first diagram shows the phase diagram of the system. The single-phase fields and the compounds
are marked with labels which are used in the tables to refer to the respective phases. All boundaries be-
tween phases which transform into each other by first-order transformations are drawn with solid lines.
Second-orderphasetransformationsandmagnetictransformationsaredenotedbydashedanddottedlines,
respectively.
Thetable“phases, structuresandmodels”, containscrystallographicdataandinformationonthethermo-
dynamic model in the database. The designations of the phases according to Strukturbericht, prototype,
Pearsonsymbolandthespacegrouphavebeencollectedfromvarioussources,includingtheoriginalpub-
lication of the assessment and the reference books of Pearson [85Vil], Massalski [90Mas] and Smithells
[92Bra]. The SGTE name is used by the accompanying software on the CD-ROM. The last column of
thistabledenoteshowthesublatticesofthecrystalshavebeenmappedintoathermodynamicmodel. The
species which dissolve in a common sublattice are enclosed in parentheses. The indices denote the stoi-
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8 Introduction
chiometriccoefficientsoftherespectivesublattices. Ifasublatticeisoccupiedbyasinglespeciesonly,the
parentheseshavebeenomitted. Vacanciesaredenotedbyabox((cid:1)).
The table of “invariant reactions” provides detailed data for the invariant equilibria and special transition
pointsshowninthephasediagram. Foreachofthesereactionsthetemperatureandthephasecompositions
areprovided. Thecompositionsoftheparticipatingphasesarelistedinthesamesequenceasgivenbythe
symbolicequation. Thelastcolumngivesthereactionenthalpyoncoolingforonemoleofatomsaccording
totherespectivetransformation.
Thethermodynamicquantitiesfortheliquidandsolidsolutionsareprovidedbyasetofthreetableswhich
are denoted by a suffix a–c after the Roman number. The first of these tables lists the integral quantities
as well as the change of the molar heat capacity. The other two tables give the partial quantities for the
respectivetwocomponents.
Theintegralandpartialquantitiescanoftenbeobtainedeasilyfromexperiments. Partialmolarquantities
are used to describe the thermodynamic behaviour of the individual components. In a binary system, the
partial molar Gibbs energy G of component A can be calculated from the molar Gibbs energy, G , at
A m
constanttemperatureandpressurebythewell-knownrelation:
GA =Gm+(1−xA)(∂Gm/∂xA)P,T (21)
G is also known as the chemical potential of component A and denoted by the symbol µ . Similar
A A
relationsholdforthepartialmolarenthalpy,H ,andthepartialmolarentropy,S .
A A
Partialquantitiesprovidethedifferencebetweenthevaluesofthermodynamicfunctionsofacomponentin
asolutionandthecorrespondingvaluesforthepurecomponents. Thus,thepartialGibbsenergy∆G of
A
componentAiscalculatedfromG inthesolutionandG◦ inthepuresubstanceby:
A A
∆G =G −G◦ (22)
A A A
Usually, the values of the pure components are given for their most stable modification at the respective
temperature and pressure. But in order to avoid ambiguities the reference states for each component are
givenatthetables. Thequantities∆H and∆S aredefinedaccordingly.
A A
Thethermodynamicactivitya ofacomponentAiscloselyrelatedtothepartialGibbsenergyby:
A
a =exp(∆G /RT) (23)
A A
Therefore,theactivityis1forpurecomponentsinthechosenreferencestate.
The integral Gibbs energy, ∆G is equal to the difference between the Gibbs energy of one mole of a
m
solutionG andthesumofthemolarGibbsenergiesofthepurecomponentsG◦ atthesametemperature
m i
andpressure. ForabinarysystemtheintegralGibbsenergyis:
∆G =G −x G◦ −x G◦ (24)
m m A A B B
If the reference state of the components is the same phase as the mixture, ∆G is also called the Gibbs
m
energyofmixing. Ifthereferencestateofatleastonecomponentisdifferentfromthephaseofthemixture
then∆G containsthedifferenceinGibbsenergiesforthepurecomponentsbetweentwophases. Inthese
m
cases ∆G is called the Gibbs energy of formation of the mixture. The quantities ∆H and ∆S are
m m m
definedaccordingly.
The excess quantities describe the deviation of the mixture from the ideal mixing behaviour. The molar
excessGibbsenergy,GE,isgivenbythedifferenceoftheintegralGibbsenergyandtheGibbsenergyof
m
mixingforanidealmixture:
GE =∆G −Gid (25)
m m m
SGTE Landolt-Bo¨rnstein
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Introduction 9
Incaseofaasimplesubstitutionalsolution,Gidisgivenbyequation(7)andforsolidsolutionswithseveral
m
sublatticesanexpressionsimilartoequation(16)applies.
Thepartialexcessquantitiescanbederivedfromtheintegralexcessfunctionsbyrelationssimilartothose
betweenpartialandintegralquantities. Thus, analogoustoequation(21), thepartialexcessGibbsenergy
ofcomponentAisgivenby:
GEA =GEm+(1−xA)(∂GEm/∂xA)P,T (26)
Sincetheheatofmixingiszeroforanidealmixture,theexcessenthalpyisidenticaltotheheatofmixing
and the partial excess enthalpy of a component is equal to its partial enthalpy. Therefore, the partial ex-
cessentropycanbecalculatedfromthepartialexcessGibbsenergybyatemperaturederivativeorbythe
differencefromthepartialenthalpy:
SAE =−(∂GEA/∂T)P,xA =(∆HA−GEA)/T (27)
The activity coefficient is related to the partial excess Gibbs energy by an expression analogous to equa-
tion(23):
γ =exp(GE/RT) (28)
A A
ForthecaseofsimplesubstitutionalsolutionstheactivityofacomponentAisrelatedtoitsmolefraction
by: aA =γAxA.
The preceding equations describe the thermodynamic behaviour of a single phase. In an unconstrained
equilibriumbetweentwophaseseachcomponenthasthesamechemicalpotentialandthesameactivityin
eachphaseandtheintegralquantitiesarelinearfunctionsofthecompositioninatwo-phaseregion. Inthe
diagrams,thefunctionsaredrawnwithdashedlinesintheseregions.
Special considerations apply to stoichiometric compounds. Here, the partial quantities cannot be defined
bytheexpressiongiveninequation(21)becausethecompositioncannotbevaried. Instead,thechemical
potentialsaredefinedbytheequilibriumwiththenextadjacentstablephase.
The table of “standard reaction quantities” provides the Gibbs energy, the enthalpy, and the entropy of
formation for the given compounds from the pure elements in their most stable state at 298.15 K and
0.1MPa. Phosphorusdeviatesfromthisrulesinceherethewhitemodificationisconventionallychosenas
areferencestateinsteadofthemorestableredform. Allvaluesinthistablearegivenforthereactionofa
totalamountof1moleofatoms.
DescriptionoftheSoftware
The software provided with the volumes can calculate the printed phase diagrams but it also has some
additionalcapabilities.
PhaseNames
Thephasenamesarethesameasusedinthevolumes. Ifthephasehasamiscibilitygaporcouldappearas
bothorderedanddisorderedinthesamesystem,a”COMPOSITIONSET”numberisappendedtothename
afterahashsign. ForexampleLIQUIDandLIQUID#2mayappearasphasenamesifthereisamiscibility
gap in the liquid phase. Normally the composition set 1 is not identified explicitly. As both phases are
thermodynamicallyidenticaltheassignmentofaspecificcompositionsetnumberisarbitrary. Forordering
intheAu-CusystemforexampletherearefourdifferentcompositionsetsfortheFCCphase.
Landolt-Bo¨rnstein SGTE
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10 Introduction
DiagramSelection
ThetwobasicwindowsforSGTEbinareshowninFig. 3. Inthetextareaofthebasewindowreferences
fordataandotherkeytextualinformationmayappear. Fortheselectionofasystempressanytwoofthe
elements highlighted in bold print. The four buttons at the bottom of the window will become available.
Fourbasictypesofdiagramscanbegeneratedbyuseofspecificbuttons. Theseare,
– thephasediagram,
– theGibbsenergycurvesforallphasesasafunctionofcompositionataspecifictemperature
– theactivitycurvesofthetwoelementsasafunctionofcompositionataspecifictemperature
– aplotofthephasefractionsasafunctionofthetemperatureforagivencomposition
Fig.3.Basewindowandperiodicchartwindow.
The basic diagrams are obtained by just selecting two elements and the specific button. From these four
calculations an infinite number of modified diagrams can be generated. Some of these will be discussed
below.
Inadditiontoselectingthetwoelementsonecanalsoselectthesetofphases. Thefoldertagged”PHASE”
gives the default selection of stable phases for the selected system. By changing this selection various
metastablediagramscanbecalculated.
PhaseDiagram
Thisbuttonwillgenerateastandardtemperature-compositionphasediagramwiththeaxesinmolefrac-
tions and degrees Celsius, see the example in Fig. 4a and 4b. Magnifications and phase labels can be
obtainedusingspecificbuttonsinthegraphicalwindow. TheREDEFINEbuttonprovidesamenu, which
will allow a change of the axes as shown in Fig. 5. Fig. 6 is equivalent to Fig. 4 but now plotted with
activityandtemperatureinCelsiusasaxesvariables.
SGTE Landolt-Bo¨rnstein
NewSeriesIV/19B