WhatisThermodynamics?

Thermodynamics:Asetofofmathematical
modelsandconceptsthatallowustodescribethe
waychangesinthesystemstate(temperature,
pressure,andcomposition)affectequilibrium.
Canbeusedtopredicthowrockformingsystemswill
respondtochangesinstate
Invertobservedchemicalcompositionsofmineralsand
meltstoinferthepressureandtemperatureconditions
ororigin

ThermodynamicSystemsDefinitions
IsolatedSystem:Nomatter
orenergycrosssystem
boundaries.Noworkcanbe
doneonthesystem.
OpenSystem:Freeexchange
acrosssystemboundaries.
ClosedSystem:Energycanbe
exchangedbutmattercannot.
AdiabaticSystem:Specialcase
wherenoheatcanbeexchanged
butworkcanbedoneonthe
system(e.g.PVwork).

ThermodynamicStateProperties
Extensive:Thesevariablesorproperties
dependontheamountofmaterialpresent
(e.g.massorvolume).
Intensive:ThesevariablesorpropertiesDO
NOTdependontheamountofmaterial
(e.g.density,pressure,andtemperature).

IdealizedThermodynamicProcesses
Irreversible:Initialsystemstateisunstableor
metastableandspontaneouschangeinthesystem
yieldsasystemwithalowerenergyfinalstate.
Reversible:Bothinitialandfinalstatesarestable
equilibriumstatesandthepathbetweenthemisa
continuoussequenceofequilibriumstates.NOT
ACTUALLYREALIZEDINNATURE.

SpontaneousReactionDirection

FirstLawofThermodynamics
Theincreaseininternalenergyasaresultof
heatabsorbedisdiminishedbytheamountof
workdoneonthesurroundings:

dEi=dqdw=dqPdV
Byconvention,heataddedtothesystem,dq,
ispositiveandworkdonebythesystem,dw,
onitssurroundingsisnegative.
ThisisalsocalledtheLawofConservationofEnergy

DefinitionofEnthalpy
Wecandefineanewstatevariable(onewherethepathto
itscurrentstatedoesnotaffectitsvalue)calledenthalpy:

H=Ei+PV
Enthalpy=InternalEnergy+PV
Upondifferentiationandcombingwithourearlierdefinition
forinternalenergy:
dH=dEi+PdV+VdP
dEi=dqPdV

dH=dq+VdP

Enthalpy,Melting,andHeat
Forisobaric(constantpressure)systems,dP=0andthenthe
changeinenthalpyisequaltothechangeinheat:

dHp=dqp
Threepossiblechangesinasystemmayoccur:
1)Chemicalreactions(heterogeneous)
2)Changeinstate(e.g.melting)
3)ChangeinTwithnostatechange
Heatcapacityisdefinedbytheamountofheatthatmaybeabsorbed
asaresultoftemperturechangeatconstantpressure:

Cp=(dH/dT)p

EnthalpyofMelting

SecondLawofThermodynamics
Onestatementdefiningthesecondlawisthata
spontaneousnaturalprocessestendtoevenout
theenergygradientsinaisolatedsystem.
Canbequantifiedbasedontheentropyofthe
system,S,suchthatSisatamaximumwhen
energyismostuniform.Canalsobeviewedasa
measureofdisorder.

S=SfinalSinitial>0

ChangeinEntropy
RelativeEntropyExample:
Ssteam>Sliquidwater>Sice

ISOLATEDSYSTEM

ThirdLawEntropies:
Allcrystalsbecome
increasinglyordered
asabsolutezerois
approached(0K=
273.15C)andat
0Kallatomsarefixed
inspacesothatentropy
iszero.