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ThermodynamicsNotes

Introduction
Someusefulconstantsinthermodynamics:
1eV=9.6522E4J/mol
kBoltzmann'sconstant=1.38E23J/K
volume:1cm3=0.1kJ/kbar=0.1J/bar
mole:1moleofasubstancecontainsAvogadro'snumber(N=6.02E23)ofmolecules.
Abbreviatedas'mol'.
atomicweightsarebasedaroundthedefinitionthat12Cisexactly12g/mol
Rgasconstant=Nk=8.314Jmol1K1

UnitsofTemperature:DegreesCelsiusandKelvin
TheCelsiusscaleisbasedondefining0Casthefreezingpointofwaterand100Castheboiling
point.
TheKelvinscaleisbasedondefining0K,"absolutezero,"asthetemperatureatzeropressurewhere
thevolumesofallgasesiszerothisturnsouttobe273.15C.Thisdefinitionmeansthatthe
freezingtemperatureofwateris273.15K.AllthermodynamiccalculationsaredoneinKelvin!
kiloandkelvin:writekfor1000'sandKforkelvin.NeverwriteK.

UnitsofEnergy:JoulesandCalories
Joulesandcaloriesandkilocalories:Acalorieisdefinedastheamountofenergyrequiredtoraisethe
temperatureof1gofwaterfrom14.5to15.5Cat1atm.
4.184J=1calallfood'calories'arereallykcal.
Manytimesitiseasiesttosolveequationsorproblemsbyconducting"dimensionalanalysis,"which
justmeansusingthesameunitsthroughoutanequation,seeingthatbothsidesofanequationcontain
balancedunits,andthattheansweriscastintermsofunitsthatyouwant.Asanexample,considerthe
differencebetweentemperature(unitsofK)andheat(unitsofJ).Twobodiesmayhavethesame
temperature,butcontaindifferentamountsofheatlikewise,twobodiesmaycontainthesameheat,
butbeatdifferenttemperatures.ThequantitythatlinksthesetwovariablesmusthaveunitsofJ/Kor
K/J.Infact,theheatcapacityCdescribestheamountofheatdQinvolvedinchangingonemoleofa
substancebyagiventemperatureincrementdT:
dQ=CdT
TheheatcapacityCisthen
C=dQ/dT
andmusthaveunitsofJK1mol1.(Thespecificheatisessentiallythesamenumber,butisexpressed
pergramratherthanpermole.)
Don'tforgetsignificantdigits.1*2=21.1*2=21.1*2.0=2.21.0*2.0=2.0

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ThermodynamicsNotes

WhyThermodynamics?
Thinkaboutsomeeverydayexperiencesyouhavewithchemicalreactions.
YourabilitytomeltandrefreezeiceshowsyouthatH2Ohastwophasesandthatthereaction
transformingonetotheotherisreversibleapparentlythecrystallizationoficerequiresremoving
someheat.
Fryinganeggisanexampleofanirreversiblereaction.
IfyoudissolvehaliteinwateryoucantellthattheNaClisstillpresentinsomeformbytastingthe
water.WhydoestheNaCldissolve?Doesitgiveoffheat?Doesitrequireenergy?
Howisitthatdiamond,ahighpressureformofC,cancoexistwiththelowpressureform,graphite,at
Earth'ssurface?Dodiamondandgraphitebothhavethesameenergy?Ifyouburngraphiteand
diamond,whichgivesyoumoreenergy?
Whendynamiteexplodes,whydoesitchangeintoarapidlyexpandinggas,whichprovidestheenergy
release,plusafewsolids?
Chemicalthermodynamicsprovidesuswithameansofansweringthesequestionsandmore.

AFewDefinitions
Asystemisanypartoftheuniversewechoosetoconsider.
Matterandenergycanflowinoroutofanopensystembutonlyenergycanbeaddedtoorsubtracted
fromaclosedsystem.Anisolatedsystemisoneinwhichmatterandenergyareconserved.
Aphaseisahomogeneousbodyofmatter.Thecomponentsofasystemaredefinedbyasetof
chemicalformulausedtodescribethesystem.
Thephaserule:
F+P=C+2.
Extensiveparametersareproportionaltomass(e.g.,V,mass,energy).
Intensiveparametersareindependentofmass(e.g.,P,T)thesearethe"degreesoffreedom"F
containedinthephaserule.

Thermodynamics:PowerandLimitations
Thermodynamicsallowsyoutopredicthowchemicalsystemsshouldbehavefromasupraatomic
"blackbox"levelitsaysnothingabouthowchemicalsystemswillbehave.Thermodynamicsalso
pertainstothestateofasystem,andsaysnothingaboutthepathtakenbythesysteminchanging
fromonestatetoanother.

ChemicalReactionsandEquations
Howtowritechemicalreactionsstoichiometry.
Massandchargebalance:e.g.,
2Fe3+ +3H2O=Fe2O3+6H+

ReactionProducedChangeinMass,Density,Volume
Thechangeinvolume rVofareactionisthevolumeVoftheproductsminusthevolumeofthe
reactants:
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ThermodynamicsNotes

rV=VproductsVreactants

Thus,iftheproductsaresmallerthanthereactants, rV<0.
Inageneralizedreactionsuchas
aA+bB...=cC+dD...
rV=cVC+dVDaVAbVB

Thissortofadditiverelationshipistrueforotherstatevariablesandisusuallystatedas
r

where iarethestoichiometriccoefficients,positiveforproductsandnegativeforreactants.

WhatActuallyDrivesReactions?IsitEnergy?CanWeJust
CalculateorMeasuretheEnergyDifferenceofReactantsand
ProductsandKnowWhichWaytheReactionWillGo?
Formanyyearspeoplefeltthatchemicalreactionsoccurredbecausethereactantshadsomekindof
energytogiveup(i.e.,usetodowork)andthatthereforetheenergyoftheproductswouldbeless
thantheenergyofthereactants.However,weallknowthatwhenicemeltsitconsumesratherthan
releasesheat,sotheremustbemoretothestorybehindwhychemicalreactionsoccur.

LeChatelier'sPrinciple
"Ifachangeismadetoasystem,thesystemwillrespondsoastoabsorbtheforcecausingthe
change."

Equilibrium
Amechanicalanalogyforchemicalchangeisthatofaballrollingdownaslopewithmultiplevalleys
weexplaintheball'sbehaviorbysayingthatmechanicalsystemshaveatendencytoreducetheir
potentialenergy.
Atequilibriumnoneofthepropertiesofasystemchangewithtime.Asystematequilibriumreturns
toequilibriumifdisturbed.
"Stable"describesasystemorphaseinitslowestenergystate.
"Metastable"describesasystemorphaseinanyotherenergystate.

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ThermodynamicsNotes

ThefigureaboveshowsthemechanicalanalogyforH2Oat5Cand+5Cand1atm.Left:at5C,
solidH2Ohasthelowestpossibleenergystate.Right:at+5C,liquidH2Ohasthelowestpossible
energystate.WhensolidH2Oisactuallypresentat+5C,thedifferencebetweenthefreeenergyof
solidH2OandliquidH2OisavailabletodrivethereactiontoformthestablesolidH2Ophase,and
thereactionwillgotocompletionifkineticallypossible.

Energy:HowDoWeCalculateandMeasureEnergyandHow
CanWeUsethisKnowledgetoPredictReactionBehavior?
Thermodynamicsworksequallywelltodescribeanykindofworkorenergy:magnetic,potential,
kinetic,etc.Forgeologicalsystemswetypicallytalkaboutpressurevolumework,which,because
mechanicalworkisF x,youcanimaginemightbe
P V
or
V P
Becausewenotedthat rV<0iftheproductsaresmallerthanthereactants,wechoosetowritethe
PVworktermas
P V
sothatadecreaseinvolume Visseenaspositiveworkorthatanincreaseinvolume+ Vresults
inadecreaseincrystalenergy.
TheabsoluteenergyofabodycanbecalculatedfromEinstein'sequationU=mc2,butthepresenceof
thec2termmeansthattheenergyofanysystemisquitelargeandthatmeasuringthisenergyis
impractical.Itismorepracticaltomeasuredifferencesinenergy U,andwealwaysdiscussor
measuredifferencesrelativetosomearbitrarystandardstate.Analogoustothismightbeifsomeone
inNamibiaaskedyoutomeasuretheelevationofthecrestsofwavesatCampusPointwithout
agreementonsomekindofstandard,youwouldn'tbeabletodomuchmorethanmeasuretheheights
ofindividualwaves.Ifhowever,youcouldbothagreeonanequivalent"sealevel"atbothlocalities,
youcouldthencomparetheabsoluteelevationsofthewavecrests.
Atypicalthermodynamicstandardstateisnormallaboratoryconditions:25C(298.15K)and1atm
(oftencalledSTPforstandardtemperatureandpressure).
TheinternalenergyUofamineralisthesumofthepotentialenergystoredintheinteratomicbonds
andthekineticenergyoftheatomicvibrations.Thus,youmightexpectthatweaklybondedminerals
haverelativelylowpotentialenergyandthuslowinternalenergy,andwhenamineraliscoldsuch
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ThermodynamicsNotes

thatitsatomicvibrationsareslowitwillhavelowkineticenergyandthuslowinternalenergy.
Internalenergiesarealwaysdefinedrelativetosomenonzerostandardstate,sowetypicallytalk
aboutchangesininternalenergydU.
AnAsideonDifferencesandDifferentials
What'sthedifferenceamong
,d ,and
?
isusedtoindicateanykindofdifference.
disusedtoindicateadifferential.
isusedtoindicateapartialdifferential.Forexample,thepartialdifferential,withrespecttoy,of
f(x,y)=x3y4
is
=4x3y3

FirstLawofThermodynamics
AddingheatQtoacrystalincreasesitsinternalenergyU:
dU dQ
( indicates'proportional')butifthecrystalisallowedtoexpand,someoftheaddedenergywillbe
consumedbyexpansiondV,sothetotalenergyofthecrystalisreduced:
dU=dQPdV
ThisiseffectivelytheFirstLawofThermo:thattotalenergy(heat+PVwork)isconserved.

HeatCapacity
HeatcapacityCdescribestheamountofheatrequiredtochangethetemperatureofasubstance:
C=
Bydefinition,theheatcapacityofwaterat15Cis1calK1g1or18calK1mol1(i.e.,theheat
requiredtoheat1gramofwaterfrom14.5to15.5Cis1calorie).
Heatcapacitiesofsolidsapproachzeroasabsolutezeroisapproached:
C=0
TheheatcapacityiswrittenwithasubscriptPorVdependingonwhetheritobtainsforconstant
pressureCPorconstantvolumeCV.
Asanaside,
CP=CV+TV 2/
where and aretheexpansivityandcompressibilityforsolidsthedifferencebetweenCPandCV
isminimalandcanbeignoredasafirstapproximation.Forgases,CP=CV+R,andisquite
significant.
Heatcapacitiesaremeasuredbycalorimetryandoftenfitbyafunctionoftheform:
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ThermodynamicsNotes

CP=a+bT+cT2+dT0.5
butthereareotherexpansionsfortheheatcapacityinvolvingmoreorfewerterms.
Belowaresomeexamplesofheatcapacitiesofminerals.Notehowsilicateshaveanearlyconstant
heatcapacityof~1JK1g1above400K.

Enthalpy
Wehavealreadytalkedaboutthefamiliarconceptofheatasenergy.
Let'sdefineanothermeasureofenergycalledenthalpyHakindofmeasureofthethermalenergyof
acrystal.Aswewillseebelow,
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ThermodynamicsNotes

dH=dQ+VdP
Recallthatweinterpreted
dU=dQPdV
tomeanthattheinternalenergychangeistheheatchangeminustheenergylosttorelaxationofthe
crystal.Thus,
dH=dQ+VdP
meansthattheenthalpychangeistheheatchangeplustheenergythecrystalgainsbyvirtueofnot
beingallowedtoexpand.
EnthalpyincludesthevibrationalandbondingenergyatabsolutezeroH0,plustheenergyrequiredto
increasetemperature:
H=H0+

CPdT

i.e.,wecanfindtheenthalpychange Hproducedbychangingtemperaturebyintegratingtheheat
capacityCP:
H=

CPdT
IntegrationReminder

Howtointegratetheheatcapacity(todeterminechangeinenthalpy H):
CPdT=

(a+bT+cT2+dT0.5)

=aT+bT2/2c/T+2dT0.5
andisevaluatedas
=a(T2T1)+b(T22T12)/2c/(T21T11)+2d(T20.5T10.5)
HowtointegratetheheatcapacitydividedbyT(todetermineentropyS):

dT=

(a/T+b+cT3+dT1.5)

=alnT+bTcT2/22dT0.5
andisevaluatedas
a(lnT2lnT1)+b(T2T1)c(T22T12)/22d(T20.5T10.5)

Asanexample,let'scalculatethechangeinenthalpy H2981000thatresultsfromheatingquartz
from298Kto1000K,giventhefollowingheatcapacityexpansioncoefficients:
a=104.35,b=6.07E3,c=3.4E+4,d=1070
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ThermodynamicsNotes

(a+bT+cT2+dT0.5)

(CPdT=

=aT+bT2/2c/T+2dT0.5
evaluatedfrom298to1000K
=a*(1000298)+b*(100022982)/2c*(100012981)+2d*(10000.52980.5)
=45.37kJ/mol

RelationAmongEnthalpy,Heat,andHeatCapacity( HP= QP)


Animportantrelationshipbetweenenthalpychange Handheatchange Qisrevealedby
differentiatingH=U+PVtoobtainthetotaldifferential
dH=dU+PdV+VdP
substitutingdU=dQPdVweget
dH=dQ+VdP
dividingbydTgives
=

atconstantpressure,

=0,leaving

=
whichisequaltoCP:
=

=CP

DeterminingEnthalpies
Thus,ifwewanttomeasurehowtheinternalenergyUofacrystalchanges Uwithincreasing
temperatureatconstantpressure,wewanttoknow H,andwecangetthatbyintegratingtheheat
capacityCPoverthetemperaturerangeofinterest.
There'sanotherwaytomeasure H,though:calorimetry.Bydissolvingamineralinacidand
measuringtheheatproducedbythedissolution,wegetaheatofdissolution(usuallypositive).The
enthalpyof"formation" fHofthemineralisthenjusttheoppositeoftheheatofdissolution
(usuallynegative).Exceptionstothe"usuallypositive/negative"ruleincludeCN,HCN,Cu2+ ,Hg2+ ,
NO,Ag+ ,andS2.Enthalpiesofformationappearintablesofthermodynamicdataandareusually
referencedto298Kand1atm.

EnthalpyofReaction
Togetanenthalpyofreaction rHwecanmeasuretheenthalpiesofformationofthereactantsand
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ThermodynamicsNotes

products fHandthentakethedifferencebetweenthemas
rH= fHproducts fHreactants

Forexample,wecancomputetheenthalpyofthereaction
anhydrite+water=gypsum:
CaSO4+2H2O=CaSO4 2H2O
from
Ca+S+2O2=CaSO4

fH=1434.11kJ/mol

H2+0.5O2=H2O

fH=285.830kJ/mol

Ca+S+3O2+2H2=CaSO4 2H2O

fH=2022.63kJ/mol

Thus,
rH= fHgypsum fHanhydrite fHwater=16.86kJ/mol.

Exothermicvs.Endothermic
If rH<0thereactionproducesareductioninenthalpyandisexothermic(heatisgivenupbythe
rockandgainedbythesurroundings).If rH>0thereactionproducesanincreaseinenthalpyandis
endothermic(heatfromthesurroundingsisconsumedbytherock).Aneasywaytorememberthisis
thatspontaneousreactionsproduceadecreaseininternalenergy,andbecauseweknowthat
UP HP
adecreaseinHPisalsoadecreaseinUP.

Calculating fHatTemperaturesOtherThan298K
Sofarweknowhowtocalculatethechangeinenthalpycausedbyheatingandweknowthatwecan
getenthalpiesofformationfromtables.Whatifwewanttoknowtheenthalpyofformationofa
mineralatatemperatureotherthan298K?
Wedothisbycalculating rCPforthereactionthatformsthemineralofinterest:
rCP= rCPproducts rCPreactants

andthenintegrating.Thus,forexampleifwewanttoknow fHforquartzat1000K,weget
coefficientsfortheheatcapacitiesofSi,O2andSiO2:
compound

Si

31.778 5.3878E4 1.4654E5 1.7864E2

O2

48.318 6.9132E4 4.9923E5

4.2066E2

SiO2

104.35 6.07E3

1070

3.4E4

forthereaction
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ThermodynamicsNotes

Si+O2=SiO2
andwecalculate
a=24.254
b=6.2225E3
c=3.5E5
d=470.7
andthus,
CPdT= a*(1000298)+
fH1000 fH298=
2981)+2 d*(10000.52980.5)=5.511kJ/mol

b/2*(100022982) c*(10001

Thisisthechangeintheenthalpyofformationthatresultsfromheating.Weaddthistotheenthalpy
offormationat298Ktogettheenthalpyofformationat1000K:
fH1000=( fH1000 fH298)+ fH298=5.511910.700=905.2kJ/mol

Inotherwords,formingquartzfromtheelementsat1000Kyieldsslightlylessheatthanat298K.
Comparethiswiththechangeinenthalpy H2981000thatresultsfromheatingquartzfrom298Kto
1000K,whichwecalculatedis45.37kJ/mol.

Entropy
Wehavediscussedtheintuitivestatementthatreactionsprobablyproceedbecausethereactantscan
decreasetheirinternalenergybyreacting.Wealsonotedthatinternalenergyscaleswithenthalpy,
suggestingthatreactionsmight'go'becauseofadecreaseinenthalpy.However,wethennotedthat
notallreactionsgiveoffheatsome,suchasthemeltingofice,proceedinspiteofconsumingheat.
Moreover,thereareotherprocessesthatproceedintheapparentabsenceofanyheatchange:e.g.,
mixingofgasesorthespreadingofdyeinwater.Whatisitthatcausesthesereactionstoproceed
spontaneouslyeveniftheheatchangeiszeroorendothermic?
TheanswerisentropyS,whichisameasureoftheorderordisorder.Entropyhasthreesources:
configurational,electronic,andvibrational.

Configurationalentropyreferstotheentropyresultingfromimperfectmixingofdifferentatomsin
thesamesiteinacrystal,andisdescribedbytheBoltzmanndistribution:
Sconfigurational=kln (ThisisengravedonBoltzmann'stombinVienna!)
where istheprobabilitythatagivennumberofatomsinagivennumberofsiteswillhavea
particularconfiguration.
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ThermodynamicsNotes

ForNatomicsitesthatcancontainfractionXAAatomsandXBBatoms,
=
Nisalwayslargewheremolesofmaterialareconcerned,sowecansimplifythis(usingStirling's
approximation)to
S=nR(XAlnXA+XBlnXB)
wherenisthenumberofsitespermole.Forexampleincordieritethereare4Alatomsand5Siatoms
distributedover9tetrahedralsites.Forarandomdistributiontheentropyis
S=9R(4/9ln4/9+5/9ln5/9)=51.39Jmol1K1
Notethattheformoftheconfigurationalentropyequation(andelectronicentropyaswell)indicates
thatifXAorXBare0or1,Sconfigiszero:

Electronicentropyariseswhenanelectroninanunfilledorbitalcanoccupymorethanoneorbital
e.g.,forTi3+ ,thesingle3delectroncanoccupyoneofthreepossiblet2gorbitalsandSelectronic=9J
mol1K1.Vibrational(orcalorimetric)entropyarisesbecausetheenergyoflatticevibrationscan
onlyincreaseordecreaseindiscretestepsandtheenergyquanta(phonons)canbedistributedwithin
thepossibleenergystepsindifferentways.Vibrationalentropyisverydifficulttocalculatefrom
statisticalmechanicsbutcanbecalculatedeasilyfromheatcapacity.Here'swhy:
Theentropyofasystemalwaysincreasesduringirreversibleprocessesi.e.,forareversibleprocess,
dS=0,whereasforirreversibleprocessesdS>0.ThisistheSecondLawofThermobetterknown
as"Youcan'tfeeds**tintotherearofahorseandgethayoutthefront."
Ifamineralbecomesmoreorderedduringareaction,reducingitsentropy,theheatliberatedmust
increasetheentropyofthesurroundingsbyanevengreateramount.Thus,wewrite
dS>
then
>
andrecallingthat
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ThermodynamicsNotes

CP=
then
>
and
S=

dT

Inotherwords,thevibrationalentropycanbefoundbyintegratingtheheatcapacitydividedby
temperature.
Inaperfectlyordered,purecrystallinematerialtheentropyiszero.Thisisasimplestatementofthe
ThirdLawofThermo,whichfollowsfromthefactthatheatcapacitiesapproachzeroatzeroK:
C=0
However,becausetherateofatomicdiffusionalsogoestozeroat0K,allcompoundshavesome
zeropointentropyS0.
Entropyisthustheonlythermodynamicpotentialforwhichwecancalculateanabsolutevalue.What
wetypicallydoisdeterminetheheatcapacityfromnearabsolutezerotoambientconditionsandthen
integrateittogetthe(absolute)entropy(infactthisgivesusonlythevibrationalentropyandignores
configurationalandelectroniccontributionstoentropy).

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ThermodynamicsNotes

EntropyChangeofReaction
Justlike rHand rV,wecancalculateentropiesofreactionsbyusingabsoluteentropiesSand
calculatingadifferenceinentropy rS.Forexample,ifweknowthat
SCaSO4=106.7Jmol1K1
SCa=41.42Jmol1K1
SS=31.80Jmol1K1
SO2=205.138Jmol1K1
thentheentropyofthereaction
Ca+S+2O2=CaSO4
is rS=106.741.4231.802*205.138=376.8Jmol1K1

EnergyAssociatedWithEntropy
TheunitsofentropysuggestthattheenergyassociatedwithSscaleswithtemperature:
dU TS
(TheminussignisthereforreasonssimilartothePVweencounteredearlier.)
TheenergyassociatedwithconfigurationalentropyintheAl4Si5cordieritewetalkedaboutearlier
lookslikethis:

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ThermodynamicsNotes

Theenergyassociatedwithvibrationalentropyintremolite,quartz,andchalcopyritelookslikethis:

(JosiahWillard)GibbsFreeEnergyofaPhase
TheGibbsfreeenergyGisthethermodynamicpotentialthattellsuswhichwayareactiongoesata
givensetofphysicalconditionsneithertheenthalpychangenortheentropychangeforareaction
alonecanprovideuswiththisinformation.Thetwomeasuresofenergy(enthalpyHandentropic
energyTS)arebroughttogetherintheGibbsfreeenergyequation:(thechemicalpotentialisthe
equivalentforacomponent)
G=U+PVTS
whichsaysthattheGibbsfreeenergyGistheinternalenergyofthecrystalUplustheenergythe
crystalgainsbyvirtueofnotbeingallowedtoexpandminustheentropicenergyTS.Recallingthat
H=U+PV
wecanwritethisinamoreunderstandableway
G=HTS
whichsaysthatGisthedifferencebetweentheheatenergyandtheentropicenergy.

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ThermodynamicsNotes

RelationshipAmongG,S,andV
Ifwedifferentiate
G=U+PVTS
toobtain
dG=dU+PdV+VdPTdSSdT
andsubstitute
TdS=dU+PdV
(thiscomesfromdS=dQ/TanddU=dQPdV)weareleftwith
dG=VdPSdT
meaningthatchangesinGibbsfreeenergyareproducedbychangesinpressureandtemperature
actingonthevolumeandentropyofaphase.
Realizethatwhenwewrite
dG=VdPSdT
weareimplicitlywriting
dG=

dP

dT

whichmeansthat
=V
and
=S
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ThermodynamicsNotes

TheserelationsindicatethatthechangeinGibbsfreeenergywithrespecttopressureisthemolar
volumeVandthechangeinGibbsfreeenergywithrespecttotemperatureisminustheentropyS.

GibbsFreeEnergyofFormation
ThedefiningequationforGibbsfreeenergy
G=HTS
canbewrittenas
G= HT S
suchthattheGibbsfreeenergyofformation fGis
fG= fHT fS

Forexample,tocalculatetheGibbsfreeenergyofformationofanhydrite,wecanuse
fHCaSO4 =1434.11kJ/mole
SCaSO4=106.7Jmol1K1
SCa=41.42Jmol1K1
SS=31.80Jmol1K1
SO2=205.138Jmol1K1

andwecalculatetheentropyofformationofanhydrite
1 1
fS=SCaSO4 SCaSS2*SO2 =376.796Jmol K
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ThermodynamicsNotes

andthenuse
fG= fHT fS=1434,110298.15*376.796=1321.77kJ/mol

GibbsFreeEnergyofReaction
WecanwritetheGibbsfreeenergyofreactionastheenthalpychangeofreactionminustheentropic
energychangeofreaction
rG= rHT rS

Iftheheatenergyequalstheentropicenergy
rH=T rS

then
rG=0

andthereisnoreaction.Finallywehavecometoasatisfyingpointwecannowdeterminewhethera
givenreactionwilloccurifweknow Hand S,andbothofthesearemeasurableorcanbe
calculated.

If rG<0,theGibbsfreeenergyoftheproductsislowerthantheGibbsfreeenergyofthereactants
andthereactionmovestoproducemoreproducts.If rG>0,theGibbsfreeenergyoftheproductsis
greaterthantheGibbsfreeenergyofthereactantsandthereactionmovestoproducemorereactants.
Forexample,tocalculate rGatSTPforthereaction
aragonite=calcite
weuse
rH=370J
1 1
rS=3.7Jmol K

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ThermodynamicsNotes

tocalculate
rG=370298.15*3.7=733J/mol

Thenegativevalueof GtellsusthatcalcitehaslowerGibbsfreeenergyandthatthereactionruns
forward(aragonite calcite).

ClapeyronRelation
ThereisausefulrelationbetweentheslopeofareactioninPTspace(i.e.,dP/dT)andtheentropyand
volumechangesofthereactionthatfollowsfrom
rG=

VrdP SrdT

Atequilibrium G=0,suchthat
rVdP= rSdT

or
=
So,thePTslopeofareactionisequaltotheratiooftheentropychangetothevolumechange.
Alternatively,alongtheequilibriumcurve,thechangesinpressuretimesthevolumechangeareequal
tochangesintemperaturetimestheentropychange.ThisistheClapeyronEquation.

So,aphasediagramisakindoffreeenergymap. = alonganequilibrium,
< athighP
andlowT,and
> athighTandlowP.AlongtheequilibriumboundarytheGibbsFree
energiesofthereactantsandproductsareequalandtheGibbsFreeenergyofreaction rG,iszero.

Shortcutting Hand SandFinding GDirectly


Likeotherthermodynamicpotentials,wecanwritethechangeinGibbsfreeenergyofreactionas
rG= fGproducts fGreactants
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ThermodynamicsNotes

Insteadofusing fHand fS,itisoftenpossibletoobtain fGvaluesformostcompoundsfrom


electronicdatabases.Forexample,ifthefollowingGibbsfreeenergiesofformationareknown:
fGCaSO4 2H2 O=1707.280kJ/mol
fGCaSO4 =1321.790kJ/mol
fGH2 O=237.129kJ/mol

thenfor
CaSO4+2H2O=CaSO4 2H2O
rG=1.232kJ/mol

GibbsFreeEnergyatAnyPressureandTemperature
Weknowmanywaystodetermine rGatSTPbuthowdowecalculate rGforotherpressuresand
temperatures?RecallthatthechangesinGibbsfreeenergywithpressureandtemperaturearegiven
bytwoofMaxwell'srelations
= rVand

= rS

Ifwerecasttheseas
= rV P
and
= rS T
andintegrate,weget
rGdP= rGP rGPref=

rVdP

or
rGP= rGPref+

rVdP

and
rGdT= rGT rGTref=

rSdT

or
rGT= rGTref

rSdT

thus
rGPT= rGPrefTref+

rVdP

rSdT

SolvingthePressureIntegralatConstantTemperature
Toafirstapproximation,wecanignoretheexpansivityandcompressibilityofsolidsanduse
rVsdP= rVs(P1)
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ThermodynamicsNotes

asasimplification.Don'tforgetthatthisapproximationisvalidforsolidsonly!Anevenmore
commonassumptionforP>>1is
rVsdP= rVsP

Forexample,calculatethechangeinGibbsfreeenergyforthereaction
2jadeite=albite+nepheline
ifpressureincreasesfrom1barto10kbar,given
3
nepheline=54.16cm
3
albite=100.43cm
3
jadeite=60.40cm

Firstwecalculate rVandfind
r

= nepheline+ albite2 jadeite=33.79cm3=3.379J/bar

andthus
rGPT rG1,T= rVsP=33.79kJ/mol

SolvingtheTemperatureIntegralatConstantPressure
Recallthattheeffectoftemperatureontheentropychangeofreaction rSdependsontheheat
capacitychangeofreaction rCP:
rS=

dT

Thus
rGT= rGTref

rSdT

expandsto
rGT= rGTref

STref+

dT dT

Iftheformoftheheatcapacityexpansionis
CP=a+bT+cT2+dT0.5
thentheabovedoubleintegralis
a(TTlnT) bT2/2 cT1/2+4 dT0.5 aTref bTref2/2+ cTref12 dTref0.5+
aTlnTref+ bTTref cTTref2/22 dTTref0.5T rSTref+Tref rSTref
Notethatthisconsidersonlyvibrationalentropyandignoresconfigurationalentropy.Thismeansof
solvingfor rGrequiresthatyouknow rGatthereferencetemperature.
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ThermodynamicsNotes

Analternativepaththatrequiresthatyouknowtheenthalpychange rHatthereferencetemperature
is
rGT= rHTref+

CPdTT

rSTref+

dT

SolvingtheTemperatureandPressureIntegralsfor rGP,T
TocalculatetheGibbsfreeenergychangeofareactionatanypressureandtemperature,wecanuse
eitherofthefollowingequations,dependingonwhetherweknow rHor rG
rGP,T= rG1,Tref

rSTref+

rGP,T= rH1,Tref+

CPdTT

dT dT+ rVsP
rSTref+

dT + rVsP

Ifyoudon'thaveheatcapacitydataforthereactionofinterest,theseequationscanberoughly
approximatedas
rGP,T= rG1,Tref rS1,Tref(TTref)+ rVsP
rGP,T= rH1,TrefT rS1,Tref+ rVsP

Forexample,calculate rGforjadeite+quartz=albiteat800Kand20kbar.Thedataat298Kand
1barare
rH=15.86kJ/mol
rS=51.47JK

1mol1

3
rVs=1.7342J/bar=17.342cm /mol

Using
rGP,T= rH1,TrefT rS1,Tref+ rVsP

=15,860800*51.47+1.7342*20,000=9.37kJ/mol
Ifwehadusedthecompleteequationforsolids,integratingtheheatcapacities,wewouldhave
obtainedananswerof9.86kJ/molnothorrificallydifferent.

CalculatingthePTPositionofaReaction
Ifwesaythat rG=0atequilibrium,thenwecanwriteoursolidsonlyandconstantheatcapacity
approximationsas
0= rG1,T rS1,Tref(TTref)+ rVsP
0= rH1,TrefT rS1,Tref+ rVsP
andthuswecancalculatethepressureofareactionatdifferenttemperaturesby
P=

rG1,Tref rS1,Tref(TTref)

P=

rH1,TrefT rS1,Tref

/ rVs

/ rVs

andwecancalculatethetemperatureofareactionatdifferentpressuresby
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ThermodynamicsNotes

T=Tref+

rG1,Tref+ rVsP

/ rS1,Tref

T=Tref+

rH1,Tref+ rVsP

/ rS1,Tref

Let'sdothisforthealbite=jadeite+quartzreactionatT=400KandT=1000K:
P=(15,8605147*400)/1.7342=2.7kbar
P=(15,8605147*1000)/1.7342=20.6kbar
AssumingthatdP/dTisconstant(abadassumption,weknow),thereactionlookslikethis

IntroductiontotheEquilibriumConstant
AbitfartherdowntheroadwewillencounteramonstercalledtheequilibriumconstantK:
K=exp( rG/RT)
or
lnK= rG/RT
Atequilibrium,where rG=0,lnK=0andK=1.Let'sseewhatKlookslikeforjadeite+quartz=
albiteat800Kand20kbar:
lnK=( rH1,TrefT rSTref+ rVsP)/RT
=(15,860800*51.47+1.7342*20,000)/(8.314*800)=1.4
IfwedothisforallofPTspace,wecancontourPTspaceintermsoflnK:

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ThermodynamicsNotes

Solutions
Almostnophasesarepure,buttypicallyaremixturesofcomponents.Forexample,olivinevaries
frompureforsteriteMg2SiO4topurefayaliteFe2SiO4,andcanhaveanycompositioninbetweenit
isasolidsolution.Weneedawaytocalculatethethermodynamicpropertiesofsuchsolutions.
Asameasureofconvenience,weusemolefractiontodescribethecompositionsofphasesthatare
solidsolutions.Forexample,amixof1partforsteriteand3partsfayaliteyieldsanolivinewith25
mol%forsteriteand75mol%fayalite,whichcanbewrittenas(Mg0.25Fe0.75)2SiO4orfo25fa75,etc.
MolefractionsaredenotedasXi.
WeneedawayofsplittinguptheGibbsfreeenergyofaphaseamongthevariouscomponentsofthe
phasehowforexampledowedecidehowmuchoftheGibbsfreeenergyofanolivineisrelatedto
theforsteritecomponentandhowmuchderivesfromthefayalitecomponent?Likewise,howdoesthe
Gibbsfreeenergyofaphasevarywithcompositionistherelationshiplinearbetweenendmembers??
WeaddresstheseissuesbydefiningapartialGibbsfreeenergyforeachcomponentatconstant
pressureandtemperatureandconstantcompositionofothercomponents,calledthepartialmolar
Gibbsfreeenergyorchemicalpotential
i=

wherenistheamountofsubstance.Forolivinesolidsolutioncomposedoffayaliteandforsterite
componentsorendmembers,wewrite
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ThermodynamicsNotes

dG=

dnfayalite+

dnforsterite

VolumeofMixing
ImaginethatmolefractionsofphaseAandphaseBwithmolarvolumesVAandVB,aremixed
together.Wecandescribethevolumeofthemixtureas
V=XAVA+XBVB
anditisalinearmixingofthetwoendmembervolumes.Wecallthisidealmixingormechanical
mixing.Realsolutions,however,donotbehavethisway,andthemixingisalwaysnonideal,
althoughsometimesonlyweaklyso.Thefigureshowsmixingthatproducesasmallervolumethan
expected,butitisnotpossibletopredicttheshapesandpositionsofsuchmixingcurves.

PartialMolarVolume
Thepartialmolarvolumeisdefinedas
i

IfyoumixtwocompoundsAandBtogetherandfindavolumeofmixingthatisnonideal,howcan
youdeterminethecontributionthatAandBeachmaketothevolume?Thatis,whatarethepartial
molarvolumesofAandB, Aand B??Graphically,thepartialmolarvolumesaretheAandB
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ThermodynamicsNotes

axisinterceptsofthetangenttothemixingcurve,andcanbedescribedbythesimplerelationship:
Vmix=XA A+XB B
or
Vmix= Xi i
ThebehaviorofthisfunctionissuchthatwhenXAis1,Vmix=VAandwhenXAis0,Vmix=VB.
Alternatively,
A=(VmixXB

B)/XA

EntropyofMixing
Theentropyofmixingisneverzerobecausemixingincreasesentropy.Aswediscusseddaysago,the
entropyofmixing(i.e.,theconfigurationalentropy)is
Smix=R (XilnXi)
wherei=1..nisthenumberofsitesoverwhichmixingisoccurring.

EnthalpyofMixing
Enthalpiesalsodonotcombinedideally(linearly)inmixturesbecausethemixturemayhavestronger
bondsthanwerepresentineitheroftheunmixedphases.Theexcessenthalpyis
Hmix=0.5*NzXAXB[2 AB AA BB]
where ABistheinteractionenergyamongABatoms, AAistheinteractionenergyamongAA
atoms,and BBistheinteractionenergyamongBBatoms.

GibbsFreeEnergyofMixing
Recallthatallspontaneousprocesses/reactionsoccurbecauseofadecreaseinGibbsfreeenergy.It
shouldthereforenotsurpriseyouthattheGibbsfreeenergyofmixingisalwaysnegativeotherwise
mixingwouldnotoccur.Thefactthat A<GAand B<GBillustrateswhycompoundscombine
spontaneouslyeachcompoundisabletoloweritsfreeenergy.

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ThermodynamicsNotes

TheabovefigureishypotheticalbecausewecannotmeasureorcalculatetheabsoluteGibbsfree
energyofphases.Forthisreason, isalwaysexpressedasadifferencefromsomestandardstate
measurement,as
, ,or G.
ThedifferencebetweentheabsoluteGibbsfreeenergyGpermole ofapurecompoundandthe
chemicalpotentialpermole ofdissolvedcompoundis
AGA= A

A=RTlnXA

Thisfunctionhasthefollowingshape:

implyingthatwhenthemineralispure(X=1)then
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=0,andwhenthemineralisinfinitelydilute
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ThermodynamicsNotes

(X=0)thenthechemicalpotentialisundefined.Forexample,inatwocomponentmineralifXA=
0.4,atT=298K,
A

A=8.314*298ln0.4=2271J
B B=8.314*298ln0.6=1266J
Theequationofthe Gmixlineisthesumofthechemicalpotentialsoftheendmembers:
Gmix=RT(XAlnXA+XBlnXB)or
Gmix=RT (XilnXi)
whichlookslikethisfortwocomponents:

Actually,allthisdiscussionhasbeenpredicatedontheassumptionthat Hmix=0.Ifthisisnottrue,
Gmixisnotasimplefunctionofcomposition,buthasthegeneralform:

Dependingontherelativevaluesof HmixandT Smix,thefreeenergyofmixingmaybenegative


throughoutthewholecompositionrangeiftheentropicenergycontributionoutweighstheenthalpy
increasethisismorelikelyathighertemperature.
Thetwofreeenergyminimaintheabovefigureindicatethatmineralsofintermediatecompositions
canreducetheirfreeenergybyunmixingintotwophases.Thisexplainstheappearanceanddriving
forceforexsolution.Notethatthiscanonlybetrueif Hmix>0,i.e.,if2 AB> AA+ BB,which
makessensebecauseitmeansthattheABbondshaveahigherfreeenergythanthesumofthefree
energiesofseparateAAandBBbonds.
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ThermodynamicsNotes

Activities
Inreality,nophasesbehaveideallythatis,theirchemicalpotentialsareneversimplelogarithmic
functionsofcompositionas
A

A=RTlnXA

implies.Instead,wesaythatthechemicalpotentialisasimplelogarithmicfunctionofactivityand
defineactivityas
a=( X)
whereaistheactivityofacompound, isthe"siteoccupancycoefficient"(e.g., =2forMgin
Mg2SiO4),and istheactivitycoefficientthatdescribesthenonidealbehavior.Thuswewrite
A

A=RTlnaA

Forpurecompoundsa=1becauseX=1.Foridealcompounds =1.Asaspecificexample,the
chemicalpotentialofthealmandine(Fe3Al2Si3O12)componentofagarnetsolidsolution((Fe,Mg,
Ca,Mn)3Al2Si3O12)is
alm= alm+RTlnXalm
Tobeclear, isthechemicalpotentialofthecomponentinitspurereferencestateandvariesasa
functionofpressureandtemperaturethiswemeasurewithcalorimetry. isthechemicalpotential
asitactuallyoccursandvariesasafunctionofphasecompositionthiswemeasurewithanelectron
microprobe.Theactivityformsabridgebetweenidealizedbehaviorandrealbehavior.

TheEquilibriumConstant
AtequilibriumthesumoftheGibbsfreeenergiesofthereactantsequalsthesumoftheGibbsfree
energiesoftheproducts.Equally,thesumofthepartialmolarGibbsfreeenergies(chemical
potentials)ofthereactantsequalsthesumofthepartialmolarGibbsfreeenergies(chemical
potentials)oftheproducts.Inotherwords,for
SiO2+2H2O=H4SiO4
atequilibrium,
H4SiO4= SiO2+2 H2O
Moregenerally,for
aA+bB=cC+dD
then
c C+d D=a A+b B
or,atequilibrium
r

=0=c C+d Da Ab B

whichwecanreformatas
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ThermodynamicsNotes

i i

where iisthestochiometriccoefficientofaproductorreactantandispositiveifforaproductand
negativeifforareactant.Ifwethenrememberthat
=RTlna
andrewriteitas
= +RTlna
wecanreformattheearlierequationas
r

=0=c( C+RTlnaC)+d( D+RTlnaD)a( A+RTlnaA)b( B+RTlnaB)

whichlooksniceras
r

= r +RTln(aCcaDd/aAaaBb)

Tobecompletelygeneralwewrite
r

= r +RTln ai ( meanstomultiplyalliterms)

Thisequationisinvariablysimplifiedto
r

= r +RTlnQ

andQistheactivityproductratio.TheactivitiesintheQtermchangeasthereactionprogresses
towardequilibrium.
Tobeclearagain, r isthedifferenceintheGibbsfreeenergiesoftheproductsandreactants
wheneachisinitspurereferencestateandvariesasafunctionofpressureandtemperature. r is
thedifferenceintheGibbsfreeenergiesoftheproductsandreactantsastheyactuallyoccurand
variesasafunctionofphasecomposition.
Atequilibrium,theproductandreactantactivitieshaveadjustedthemselvessuchthat r =0.We
writethis(withKinsteadofQ,tosignifyequilibrium)as
0= rG=RTlnK
Kiscalledtheequilibriumconstant.IfKisverylarge(lnKpositive),thecombinedactivitiesofthe
reactionproductsareenormousrelativetothecombinedactivitiesofthereactantsandthereaction
willlikelyprogress.Ontheotherhand,ifKissmall(lnKnegative),thereisunlikelytobeany
reaction.
TheutilityofKisthatittellsusforanyreactionandanypressureandtemperature,whattheactivity
ratiosofthephaseswillbeatequilibrium.Forexample,forthereaction
albite=jadeite+quartz
let'ssaythatataparticularPandT,
rG=20.12kJ/mol

Using
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ThermodynamicsNotes

rG=RTlnK

wecalculate
logK=3.52
Thismeansthatatequilibrium,
(ajadeiteaquartz/aNaAlSi3O8)=e3.52
WhereajadeiteistheactivityofNaAlSi2O6inclinopyroxeneandaalbiteistheactivityofNaAlSi3O8
inplagioclase.

AlternativeRoutetotheEquilibriumConstant
Whenwethinkofmassbalanceinareaction,wecanexplicitlywrite
0=

i Mi

where iarethestoichiometriccoefficientsandMiarethemassesorthephasecomponents.
Analogously,wecanexplicitlywriteasimilarbalanceamongthechemicalpotentials:
0=

i i

Foreachchemicalpotentialwecanwrite
i= i+RTlnai
Combiningthesetwoequationswefind
0=

i+

0=

i+ RTln(ai)

0=

0=

iRTlnai

i+RTln ai
i i+RTlnK

andeventually
0= rG+RTlnK
or
rG=RTlnK

Theequation
K= ai
isthelawofmassaction(whichactuallydiscussestheactionofchemicalpotentialratherthanmass).
Wecanalsowritefor298Kand1atm
rHT rS=RTlnK
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ThermodynamicsNotes

andforanyPandTofinterest:
rH1,Tref+

CPdTT

rSTref+

dT +

rVP=RTlnK

Thishasbeencalled"themostimportantequationinthermodynamics,"soyou'dbetterlikeit(!)The
equilibriumconstantKisafunctionof1/T
lnK=( rG/RT)=[( rH/RT)( rS/R)]

Whichlookslike

ActivityModels(ActivityCompositionRelations)for
CrystallineSolutions
Garnetsaresolidsolutionsof
component abbrev.
formula
Mg3Al2Si3O12
pyrope
prp
almandine alm

Fe3Al2Si3O12

grossular

grs

Ca3Al2Si3O12

spessartine sps

Mn3Al2Si3O12

andradite

Ca3Fe23+ Si3O12

and

Mixingmodelsderivefromentropyconsiderations.Inparticulartherelation
Smix=R XilnXi
althoughwewillnotgothroughthederivation.

MixingonaSingleSite
Thesimplesttypeofusefulactivitymodelistheionicmodel,whereinweassumethatmixingoccurs
oncrystallographicsites.ForaMgFeCaMngarnetwithmixingononesite,whichwecanidealize
as(A,B,C,D) Al2Si3O12,theactivitiesare
aprp= Mg3XMg3
aalm= Fe3XFe3
agrs= Ca3XCa3
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ThermodynamicsNotes

asps= Mn3XMn3

Thepyropeactivityisshownintheabovefigure.
Ingeneral,foridealmixinginamineralwithasinglecrystallographicsitethatcancontain ions,
ai=Xj
wherea,theactivityofcomponenti,isthemolefractionofelementjraisedtothe power.Fornon
idealmixing,weincludeanactivitycoefficient
ai= j Xj

MixingonaSeveralSites
Formineralswithtwodistinctsitesandthegeneralformula
(A,B) (Y,Z)
therearefourpossibleendmembercomponentsA Y ,A Z ,B Y ,andB Z .
Theidealactivitiesofthesecomponentsare
aA Y =XA XY
aA Z =XA XZ
aB Y =XB XY
aB Z =XB XZ
Fornonidealgarnetactivitieswewrite
aprp=XMg3XAl2or Mg3XMg3 Al2XAl2
aalm=XFe3XAl2or Fe3XFe3 Al2XAl2
agrs=XCa3XAl2or Ca3XCa3 Al2XAl2
asps=XMn3XAl2or Mn3XMn3 Al2XAl2
aand=XCa3XFe3+ 2or Ca3XMn3 Fe3+ 2XFe3+ 2
wheretheX3termdescribesmixingonthe8foldtrivalentsiteandtheX2termdescribesmixingon
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ThermodynamicsNotes

theoctahedraldivalentsite.

ThepyropeactivityisshownintheabovefigureforMgfrom0 3andAlfrom0 2.
Itiscommontomodifysuchmodelsthatarebasedoncompletelyrandommixingofelementswith
modelsthatconsiderlocalchargebalanceoncertainsitesortheAlavoidanceprinciple.

GeothermometryandGeobarometry
ExchangeReactions
Manythermometersarebasedonexchangereactions,whicharereactionsthatexchangeelementsbut
preservereactantandproductphases.Forexample:
Fe3Al2Si3O12 +KMg AlSi O (OH) =Mg Al Si O +KFe AlSi O (OH)
3

almandine

3 10

+phlogopite

=pyrope

3 12

3 10

+annite

Wecanreducethisreactiontoasimpleexchangevector:
(FeMg)gar+1=(FeMg)bio1
Popularthermometersincludegarnetbiotite(GARB),garnetclinopyroxene,garnethornblende,and
clinopyroxeneorthopyroxeneallofthesearebasedontheexchangeofFeandMg,andareexcellent
thermometersbecause rVissmall,suchthat
=
islarge(i.e.,thereactionshavesteepslopesandarelittleinfluencedbypressure).Let'swritethe
equilibriumconstantfortheGARBexchangereaction
K=(aprpaann)/(aalmaphl)
thus
rG=RTln(aprpaann)/(aalmaphl)

ThisequationimpliesthattheactivitiesoftheFeandMgcomponentsofbiotiteandgarnetarea
functionofGibbsfreeenergychangeandthusarefunctionsofpressureandtemperature.
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ThermodynamicsNotes

Ifweassumeidealbehavior( =1)ingarnetandbiotiteandassumethatthereismixingononly1
site
aalm=Xalm3=[Fe/(Fe+Mg+Ca+Mn)]3
aprp=Xprp3=[Mg/(Fe+Mg)]3
aann=Xann3=[Fe/(Fe+Mg)]3
aphl=Xphl3=[Mg/(Fe+Mg)]3
Thustheequilibriumconstantis
K=(XMggarXFebio)/(XFegarXMgbio)
WhendiscussingelementpartitioningitiscommontodefineadistributioncoefficientKD,whichis
justtheequilibriumconstantwithouttheexponent(thisjustdescribesthepartitioningofelementsand
notthepartitioningofchemicalpotential):
KD=(XMggarXFebio)/(XFegarXMgbio)=(Mg/Fe)gar/(Mg/Fe)bio=K1/3
Longbeforemostofyouwereplaygroundbullies(1978)acoupleofdeitiesnamedJohnFerryand
FrankSpearmeasuredexperimentallythedistributionofFeandMgbetweenbiotiteandgarnetat2
kbarandfoundthefollowingrelationship:

Ifyoucomparetheirempiricalequation
lnKD=2109/T+0.782
thisimmediatelyremindsyouof
lnK=( rG/RT)=( rH/RT)(P rV/RT)+( rS/R)
andyourealizethatforthisreaction
rS=3*0.782*R=19.51J/molK

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ThermodynamicsNotes

(thethreecomesfromthesiteoccupancycoefficienti.e.,K=KD3)and
( rH/R)(P rV/R)=2109
or
rH=3*2109*R2070* rV

Molarvolumemeasurementsshowthatforthisexchangereaction rV=0.238J/bar,thus
rH=52.11kJ/mol

Thefullequationisthen
52,11019.51*T(K)+0.238*P(bar)+3RTlnKD=0
ToplottheKDlinesinPTspace

NetTransferReactions
Nettransferreactionsarethosethatcausephasestoappearordisappear.Geobarometersareoften
basedonnettransferreactionsbecause rVislargeandrelativelyinsensitivetotemperature.A
popularoneisGASP:
3CaAl2Si2O8
=Ca3Al2Si3O12 +2Al2SiO5 +SiO2
anorthite

=grossular

+kyanite

+quartz

whichdescribesthehighpressurebreakdownofanorthite.

Forthisreaction
rG=RTln[(aqtzaky

2a )/a 3]=RTlna /a 3
grs
an
grs an

(theactivitiesofquartzandkyaniteareonebecausetheyarepurephases).Abestfitthroughthe
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ThermodynamicsNotes

experimentaldataforthisreactionbyAndreaKoziolandBobNewtonyields
P(bar)=22.80T(K)7317
for rV=6.608J/bar.Again,ifweuse
lnK=( rH/RT)(P rV/RT)+( rS/R)
andsetlnK=0tocalculatevaluesatequilibrium,wecanrewritetheaboveas
(P rV/R)=( rH/R)+(T rS/R)
or
P=T rS/ rV rH/ rV
ifT rS/ rV=22.8then rS=150.66J/molK
if rH/ rV=7317then rH=48.357kJ/mol
So,wecanwritethewholeshmearas
0=48,357+150.66T(K)6.608P(bar)+RTlnK
ContoursoflnKonaPTdiagramforGASPlooklikethis:

Kinetics
Thermodynamicsplacesnoconstraintsontherateormechanismofreactionthatistherealmof
kinetics.Apopularmethodfordescribingtherateatwhichreactionsproceedistotalkofanactivated
statethroughwhichthereactionmustpass:

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ThermodynamicsNotes

Whenasystempassesfromaninitialtoafinalstateitmustovercomeanactivationenergybarrier
G*.
Theadvantagesofthisactivationenergybarrierparadigmarethatitqualitativelyexplainsthei)
persistenceofmetastablestatesii)effectofcatalystsinlowering G*iii)temperaturedependence
oftransformation.Wecandrawasimilardiagramforachangeinenthalpyinducedbythereaction
rHandanactivationenthalpybarrier H*(usuallycalledanactivationenergyQ*).Ofcourse,
unlike rG, rHcanbepositiveornegative:

Itisnoteasytogeneralizeabouttheactivationentropy S*,however,ingeneral,reactionswith
positiveentropychange rSarefaster.Forexample,evaporationisfasterthancondensation,melting
isfasterthancrystallization,anddisorderingisfasterthanordering.
Becausethermalenergydictateswhetheranatomhassufficientenergytoovercomeanactivation
energybarrier,wewillwritethatthefractionofatomswiththermalenergygreaterthan H*is
f=exp( H*/RT)
i.e.,iff<<1,fewatomshaveenoughthermalenergytoovercometheactivationenergybarrier,
whereasiff=1allatomscanovercometheactivationenergybarrier.

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ThermodynamicsNotes

Forreactionsthatinvolveasinglestepcharacterizedbyasingleactivationenergy,therateofthe
reactiondependsonthei)frequencywithwhichatomsattempttojumpfromonesitetothenext ii)
fractionofatomswiththermalenergygreaterthanQ*andiii)probabilitypthattheatomjumping
satisfiessomegeometricalconsideration(thisisafancynameforafudgefactor):
rate p exp(Q*/RT)
Oftenthisisrewrittenasrate (kT/h) exp(Q*/RT)

wherekisBoltzmann'sconstant,andhisPlanck'sconstant.Thus,therate atwhichatomsjumpis
relatedtotemperatureandtoatomscaleprocessesdescribedbykandh.

Nucleation
Mosttransformationstakeplacebynucleationandgrowth.Thedrivingforcefornucleationresults
fromthefactthattheformationofthenewphaselowersthetotalfreeenergyby VG,theGibbsfree
energychangeofreactionperunitvolume.Nucleationisopposedbyaninterfacialenergy anda
strainenergy .Theoverallchangeinnucleationenergyforasphericalnucleusofradiusristhen
3
2 +(4/3) r3
nG= VG+ Ginterfacial+ Gstrain=(4/3) r
VG+4 r
Thesedifferentenergycontributionsyieldanincreaseintotalfreeenergyuptoacertainradiustermed
thecriticalradius,beyondwhichthetotalfreeenergydecreases.

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ThermodynamicsNotes

Thischangefromincreasingtodecreasingnucleationfreeenergyhappensbecausethesurface:volume
ratiodecreaseswithincreasingradius,sothenegativevolumefreeenergytermthatfavorsnucleation
eventuallyoverwhelmsthepositivesurfaceandstrainfreeenergytermsthatopposenucleation.We
canreorderthetermsintheaboveequationtocalculatethecriticalsizeofthenucleusrc
rc=2 /( VG+ )
If,atthecriticalradius, nG= G*,theactivationenergyfornucleationis
G*=16

3/3(

VG+

)2

Growth
Followingnucleation,grainsoftheproductphase(s)growtoreplacetheparentphase(s).Eitherthe
reactionispolymorphic,oratomsoftheparentphasemustdissolve,betransported,andthenattach
themselvestotheproductphase.Therateofgrowthisthuscontrolledbytherateoftheslowestof
thesethreesteps,andisdescribedaseitherinterfacecontrolledordiffusioncontrolled.
Turnbull's(1956)formulationtoquantifyinterfacecontrolledgrowthrate is:
= (kT/h)exp(Q*/RT)[( rG/RT)]
where isan"interfacejumpdistance"andtherestyouwillrecognizefrompreviousequations.The
[( rG/RT)]termindicatesthattherateofgrowthdependsontheGibbsfreeenergychangeof
reaction.As rG 0,thistermalsoapproacheszero.As rG ,thistermapproaches1.

Transformation:Nucleation+Growth
Acompletetransformationinvolvesnucleationandgrowththeproductphasesmustformandgrow
andtheparentphasesmustbeconsumed.Theletter_isoftenusedtoindicate'reactionprogress'or
'degreeoftransformation,'andvariesfrom0(noreaction)to1(completereaction).The
transformationisthetimeintegratedresultofongoingnucleationandgrowth,whichcanvaryintime
andspace:
=1exp[(4/3)

dt]

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ThermodynamicsNotes

Justasanexample,thegeneralrateequationforinterfacecontrolled(i.e.,notdiffusioncontrolled)
growthofnucleiformedongrainboundariesis
=1exp{(6.7/d) [1exp(

[ 2(t )2y2]d )]dy}

Intheirsimplestform,theseequationshavetheform
=1exp(ktn)
Flipthisaroundto
exp(ktn)=1
linearizebymeansoflogarithms
ktn=ln(1 )
changesignsandcleverlyinsertln1
ktn=ln1ln(1 )
rewritethetwologarithmsasone,recallingthatln(a/b)=lnalnb
ktn=ln[1/(1 )]
andlinearizeoncemorewithlogarithmstogetthefinalgloriousequation
nlnt+lnk=ln[ln(1 )]

TheLastSupper:AStillLifeofThermodynamics&Kinetics
Zeolites,likelaumontiteandwairakite,forminoilfieldsasalterationproductsofplagioclaseand
otherCabearingphases.Thethermodynamicproperties( H,S,V,CP)ofzeoliteshavebeen
measured,andwecanusethosepropertiestocalculateaphasediagramfortheCASHsystem:
LaumontiteisthephasethatisstableatthelowestPandT.Wairakiteisthenextphasetoform,andit
doessoviathereactionlaumontite_wairakite+H2O.Athighertemperaturewairakite+H2O
decomposetoanorthite+quartz+H2O.

Kineticexperimentsconductedonthereactionlaumontite_wairakite+H2O,usingcrystalsof
laumontitesuspendedinH2O,revealthetransformationvs.timedatainthefigureabove.
Onecouldusetheequation
tointerpretthetwosubfigurestorevealdifferentnandkvaluesforeachtemperature.Thisistheway
ratedatawereinterpretedinthebadolddays,butthisapproachlacksanyphysicalormechanistic
basis.Instead,wecanmeasuretherateofgrowthateachtemperatureandrelatetherateofgrowthto
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ThermodynamicsNotes

theTurnbullequation.Aboveisanexampleofgraingrowthdatacollectedfor450C.Therateof
growthisinterpretedtobeaconstant2.00.3E10m/s.Ifgrowthratedatalikethiscanbecollected
foreverytemperatureofinterest,anactivationenergyforgrowthcanbecalculated:
Theactivationenergyforgrowthapparentlyvariesfrom~196kJ/molto~72kJ/moldependingonthe
reactionmechanism.Thegrowthratedatacanbecombinedwithsimilarnucleationratedatatoyielda
completetransformationrateequationthatcanbeextrapolatedtogeologicconditionsofinterest.The
figurebelowshowsextrapolatedgrowthrates(m/s)forthelaumontite_wairakite+H2Oreaction.

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