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GibbsFreeEnergyGinkJ
G=HTS
WhereH=Enthalpy(kJ)
S=Entropy(Joules/Kelvin)
T=Temperature(Kelvin)
*RememberthatG=0duringaphasetransition(e.g.Fusion,Sublimation,etc).
Go=GoproductsGoreactants
G=Go+RTlnQ
Go=RTlnK
G=nFE
Go=nFEo
WhereGo=StandardGibbsFreeEnergy(at25oCand100kPafor1mol)
R=UniversalGasConstant8.314J/K.mol
Q=ReactionQuotient
K=EquilibriumConstant
n=numberofelectronstransferred
F=FaradayConstant(96500C/mol.electron)
E=Cell/ElectrodePotential(inVolts)
Eo=StandardCell/ElectrodePotential(inVolts)
ClausiusClapeyronEquation
lnPvap=
+C
WherePvap=VapourPressure(Pa)
Hvap=Heat/EnthalphyofVaporization(kJ)
C=Constant
NotethattheClausisClapeyronEquationcanbeusedforthesamegasatdifferent
temperaturesorpressuresbytheform:
lnP1=lnP2+
Entropy
S=SproductsSreactants
Stotal=Ssystem+Ssurrounding
S=klnW
WhereK=BoltzmannsConstant(1.38x1023)
W=Numberofwaysastateisachievable
RateLaws
Rate=k[A]m[B]n
WhereAandBarereactantconcentrations
mandnareordersfortheirrespectivereactant.
*mandnarenotsimplythecoefficientsofthereactants
*Rate=concentrationchangeovertime
Orderofareaction=m+n
FirstOrderIntegratedRateLaw
ln[A]t=kt+ln[A]o
Where[A]t=ConcentrationofAattimet
[A]o=InitialConcentrationofA
k=RateConstant
t=Time
FirstOrderHalfLife
t=ln2/k
Eachsuccessivehalflifeinafirstorderreactionoccursatanequaltime.
SecondOrderIntegratedRateLaw
SecondOrderHalfLife
1/[A]t=kt+1/[A]o
t=1/k[A]o
Eachsuccessivehalflifeinafirstorderreactionoccursatanequaltime.
ZerothOrderIntegratedRateLaw
[A]t=kt+ln[A]o
Reactionisindependentofconcentration.
ZerothOrderHalfLife
t=0.693/k
ArheniusEquation
k=AeEa/RT
Wherek=rateconstant
A=Collisionfactor
Ea=ActivationEnergy(kJorJ)
R=GasConstant(makesuretheunitscorrespondtotheactivationenergyinkJorJ)
T=Temperature(K)
Hintsfortheexponentialfunction:
e=Eulersnumber2.718
lnex=x
elnx=x
ThelnfunctionandEulersnumbercancelouteachother.
GasEquilibriumConstant
Kp=Kc(RT)n
WhereR=GasConstant=0.082058Latm/Kmol(notetheunitsforRusedforthisequation)
Kp=RateEquilibriumconstantintermsofgases
Kc=EquilibriumConstant
n=molratioofproductsmolratioofreactants(gaseouselementsonly)
HendersonHasselbalchEquation(Buffers)
pH=pKa+log([A]/[HA])
Where[A]=concentrationofconjugatebase
[HA]=concentrationofacid
pKa=logmeasureoftheaciddissociationconstant(Ka)
Note:
atmaximumbuffercapacity(when[A]=[HA]),
pH=pKa+log(1)
pH=pKa+0
pH=pKa
MiscellaneousEquationsConcerningpH
Kw=[H3O+][OH]=KaKb=1.0x1014
WhereKw=DissociationConstantforwater
Ka=AcidDissociationConstant,MeasureofAcidStrength
Kb=BaseDissociationConstant,MeasureofBaseStrength
pH=log[H3O+]=log[H+]
Note:H+andH3O+areinterchangeable.
pOH=log[OH]Ka=[H3O+][A]/[HA]
pH+pOH=14pKa+pKb=14pKa=logKa
NernstEquation
WhereEocell=Standardcellpotential(inVolts)
K=Equilibriumconstant
n=molsoftransferredelectrons
WhereQ=ReactionQuotientatacertaintemperature.