THERMOCHEMISTRY

(Naturetendstowardthelowestenergystate!)

Energy(
E
)
theabilitytodoworkorproduceheatthesumofallpotentialandkineticenergyina
systemisknownasthe
internalenergy
ofthesystem

Potentialenergy
Energyduetopositionor
composition

Inchemistrythisisusuallytheenergystoredin
bonds.

Whenbondedatomsareseparated,thePEis

decreasedbecauseenergymustbe
usedtoovercomethecoulombic
attractionbetweeneachnucleusandtheshared
electrons.

Whenatomsbond,theabovementioned
coulombic
attractionresultsinenergybeingabsorbedand
asubsequentincreasedinPE.

Kineticenergy
Energyofmotion,dependson
massandvelocityofobject

Particularlythemotionofparticles

ItisproportionaltoKelvintemperaturekineticenergydependsonthemassandthevelocityofthe
object:
KE
=
mv2

CheckoutthissimulationregardingtheBoltzmanndistribution:
http://phet.colorado.edu/en/simulation/atomicinteractions
Andthisoneregardingtheeffectoftemperatureonmolecular
motion:
http://phet.colorado.edu/en/simulation/statesofmatterbasics

LawofConservationofEnergy
Energyisnevercreatedordestroyed

AKA
energyoftheuniverseisconstant&the
FirstLawofThermodynamics
Heat(
q
)
Transferofenergy
(flowsfromawarmerobjecttoacoolerone,duetotemperaturedifferencebut,remember,
temperature
is
notameasureofenergyitjustreflectsthemotionofparticles)
Temperature(T)
Averagekineticenergy

Heatemupandspeedemupasyousawinthestatesofmatteranimation.

Enthalpy(
H
)
Heatcontentatconstantpressurewhentwosystemsareincontact.
Enthalpyofreaction(

H
amountofheatreleased(negativevalues)orabsorbed(positive
rxn)

values)
byachemicalreactionatconstantpressureinkJ/mol
rxn

Enthalpyofcombustion(

H
)
heatabsorbedorreleasedbyburning(usuallywithO
)
comb
2
inkJ/mol
rxn

Enthalpyofformation(

H
f)
heatabsorbedorreleasedwhenonemoleofacompoundisformed
fromelementsintheirstandardstatesinkJ/mol
rxn

Enthalpyoffusion
(

Hfus)
heatneededtomeltonemoleofasubstancefromsolidtoliquidin
kj/mol
lrxn
Enthalpyofvaporization(

H
vap)
heatneededtochangeonemoleofasubstancefromliquidtogas
in kJ/mol
rxn

Pathway
thespecificconditionssomethingistravellingover

Statefunction
referstoapropertyofthesystemthatdependsonlyonitspresentstate

System
The part of the universe where attention is being focused

Surroundings
Everythingelseintheuniverse

**Energygainedbythesystem=energylostbythesurroundings**

Endothermic
whenheatisgained
+
H

Exothermic
whenheatislost

Work
Forceactingoveradistance

(work=PVwheregasesareinvolvedexpressedinJoulesorkJ)

StandardConditions
youalreadyknowaboutSTP,butrecallthatthe
T
isSTPis0

Candhumans
arenothappylabworkerswhenitisthatcold!
So,thinkofstandard
conditions
asstandard
lab
conditionswhichare1atmofpressure,25

C(muchmorecomfy!)andifsolutionsareinvolved,their
concentrationis1.0
M
.
Allofthisinformationiscommunicatedbyaddingthesymbol

to
G,HorS
.
So,ifyousee
H

,thenyouautomaticallyknowthepressure,temperatureandconditionsthatapply
tothatvalue!

 There has recently been a change in how enthalpy,entropyandfreeenergyunitsareexpressed.

For example, you may see
H

valuesexpressedaskJinolderprintedmaterial.Currently,they
should be expressed in kJ/mol
the mol
rxn where

rxn
is moles of reaction. See Jim Spencers
articleonAPCentralforadditionalinformation.

ENERGYANDWORK

Energyisoftendefinedastheabilitytodowork.
InternalEnergy
(systemsKE+PE)

E
=
q
(heat)+
w
(work)

Signsof
q
o +
q
ifheatabsorbed
o
q
ifheatreleased

Signof
w
asitrelatesto
workdoneby
or
workdoneon
gases

o +
w
ifworkdoneonthesystem(i.e.,compression)
o
w
ifworkdonebythesystem(i.e.,expansion)
Whenrelatedtogases,workisafunctionofpressure
Pressureisdefinedasforceperunitofarea,sowhenthevolumeischangedworkwaseitherdoneon
thegasorbythegas.

work=P

Exercise1InternalEnergy
Calculate
E
forasystemundergoinganendothermicprocessinwhich15.6kJofheatflowsandwhere1.4kJ
ofworkisdoneonthesystem.

Exercise2
PVWork
Calculatetheworkassociatedwiththeexpansionofagasfrom46Lto64Lataconstantexternalpressureof
15atm.

Exercise3InternalEnergy,Heat,andWork
A balloon is being inflated to its full extent by heatingtheairinsideit.Inthefinalstagesofthisprocess,the
6
6
8
volume of the balloon changes from 4.00 10
L to 4.50 10
L by theadditionof 1.3 10
Jofenergyas
heat. Assuming that the balloon expands againstaconstantpressureof1.0atm,calculate
E
forthe process.
(ToconvertbetweenL

atmandJ,use1L

atm=101.3J.)

ENTHALPY
Measureonlythechangeinenthalpy,

H
(thedifferencebetweenthepotentialenergiesofthe
productsandthereactants)


H
isastatefunction
(HPVEallstatefunctions)

H
=
q
atconstantpressure(i.e.
atmosphericpressure)

Enthalpycanbecalculatedfrom
severalsourcesincluding:
Stoichiometry
Calorimetry
Fromtablesofstandardvalues
HesssLaw
Bondenergies

Stoichiometrically:

Exercise4
Uponaddingsolidpotassiumhydroxidepelletstowaterthefollowingreactiontakesplace:
KOH(
s
)

KOH(
aq
)+43kJ/mol

Answerthefollowingquestionsregardingtheadditionof14.0gofKOHtowater:
Doesthebeakergetwarmerorcolder?
Isthereactionendothermicorexothermic?
Whatistheenthalpychangeforthedissolutionofthe14.0gramsofKOH?

Calorimetry:
(experimentalydeterminetheheatofachemicalreactionthroughobservedT.)

CoffeeCupcalorimetry:
Inthelabthisishowweexperimenttofindenergyofaparticularsystem.Weuse
aStyrofoamcup,reactantsthatbeginatthesametemperatureandlookfor
changeintemperature.Afteralldataiscollected(massorvolumeinitialand
finaltemperatures)wecanusethespecificformulatofindtheenergyreleasedor
absorbed.Werefertothisprocessasconstantpressurecalorimetry.**
q
=

H
@
theseconditions**

Termstoknow:
Heatcapacity
___________________________________________________________________
Specificheatcapacity(
Cp
)
sameasabovebutspecificto1gramofsubstanceandtheexperimentis
carriedoutatconstantpressure.Constantpressureisachievedusingopencontainers,soyouwillbedoing
experimentsofthatkindinlab.
specificheat
=

Molarheatcapacity
sameasabovebutspecifictoonemoleofsubstance(
J/molKorJ/mol

C)

Energy(
q
)
releasedorgainedatconstantpressure:
q=mCp

TCp=s(usedinterchangeably)
q
=quantityofheat(Joulesorcalories)
m
=mass
ingrams

T=Tf
Ti

(finalinitial)

Cp
=specificheatcapacity(J/g

C)
Specificheatofwater(liquidstate)=4.184J/g

C(or1.00cal/g

C)
Waterhasoneofthehighestspecificheatsknown!Thispropertymakeslifeonearthpossibleandregulates
earthstemperatureyearround!
Heatlostbysubstance=heatgainedbywater


UnitsofEnergy:
calorie
amountofheatneededtoraisethetemp.of1.00gramofwater1.00

C
kilocalorie
1,000caloriesANDthefoodlabelcaloriewithacapitalC.
1
KE
=mv2

joule
SIunitofenergy1cal=4.184J

kgm
2
s

Exercise5
Inacoffeecupcalorimeter,100.0mLof1.0
M
NaOHand100.0mLof1.0
M
HClaremixed.Bothsolutions
wereoriginallyat24.6

C.Afterthereaction,thefinaltemperatureis31.3

C.Assumingthatallsolutions
3
haveadensityof1.0g/cm
andaspecificheatcapacityof4.184J/g

C,calculatetheenthalpychangeforthe
neutralizationofHClbyNaOH.Assumethatnoheatislosttothesurroundingsorthecalorimeter.Isthe
amountofenergyreleasedanintensiveorextensiveproperty?Howmuchheatisreleasedpermoleof
reaction?

Exercise6
Enthalpy
When1moleofmethane(CH
)isburnedatconstantpressure,890kJ/molofenergyisreleasedasheat.
4
Calculate
H
foraprocessinwhicha5.8gramsampleofmethaneisburnedatconstantpressure.

Exercise7

ConstantPressureCalorimetry

When1.00Lof1.00
M
Ba(NO
)
solutionat25.0

Cismixedwith1.00Lof1.00
M
Na
SO
solutionat25

Cin
3
2
2
4
acalorimeter,thewhitesolidBaSO
formsandthetemperatureofthemixtureincreasesto28.1

C.Assuming
4
thatthecalorimeterabsorbsonlyanegligiblequantityofheat,andthatthespecificheatcapacityofthesolution
is4.18J/

g,andthatthedensityofthefinalsolutionis1.0g/mL,calculatetheenthalpychangepermoleof
BaSO
formed.
4

 HesssLawbecause

Hisastatefunction,goingfromaparticularsetofreactantstoaparticularsetof
products,thedeltaHisthesamewhetherwedothisinonesteporaseriesofsteps.
Twocharacteristicsof:
1. Ifareactionisreversed,thesignof

Hisreversed.
2. Themagnitudeof

Hisdirectlyproportionaltothequantitiesofreactantsandproductsinareaction.
IFthecoefficientsinabalancedreactionaremultipliedbyaninteger,thevalueof

Hismultipliedby
thesameinteger.

Standardenthalpyofformation(
Hf
)

Productionof
ONE
mole
ofcompoundFROMitsE
LEMENTS
in

their
standardstate.

StandardStates:forcompoundsat25

C(298K)
Gasesareat1atm
Pureliquidorsolidisasis
Solutionis1M
Elementsinstandardstate=0

H
n

H
p
r
rxn=

f
(products)
f
(reactants)

Exercise11

C
H
O
(
s
)+6O
(
g
)

6CO
(g)+6H
O(
l
)+2800kJ
6
12
6
2
2
2

Occasionally,notallvaluesarefoundinthetableofthermodynamicdata.Formostsubstancesitisimpossible
togointoalabanddirectlysynthesizeacompoundfromitsfreeelements.Theheatofformationforthe
substancemustbecalculatedbyworkingbackwardsfromitsheatofcombustion.Calculatethe

H
fof

C
H
O
(
s
)

giventhecombustionreactionabovealongwiththefollowinginformation.
6 12 6
Substance

(kJ/mol)
CO
(
g
)
2
H
O(
l
)
2

393.5
285.8

Exercise12
Thethermitereactionoccurswhenamixtureofpowderedaluminumandiron(III)oxideisignitedwitha
magnesiumfuse.Usingenthalpiesofformation,calculatethestandardchangeinenthalpyforthethermite
reaction:
2Al(
s
)+Fe
O
(
s
)

A1
O
(
s
)+2Fe(
s
)A1
O
(
s
)=1676kJ/mol
2
3
2
3
2
3
Fe
O
(
s
)=826kJ/mol
2
3

BondEnergies
Energymustbeadded/absorbedtoBREAKbonds
(endothermic)inordertoovercomethecoulombic
attractionbetweeneachnucleiandthesharedelectrons.
EnergyisreleasedwhenbondsareFORMED
(exothermic)becausetheresultantcoulombicattractionbetweenthebondedatomslowerspotential
energycausingarelease.Thisisagiantmisconceptionamongstudents!Onceagain,ittakesenergyto
breakbondsandreleaseenergytomakebonds.

H
=sum(

)oftheenergiesrequiredtobreakoldbonds(positivesignssinceenergyisadded
tothesystem)plusthesumoftheenergiesreleasedintheformationofnewbonds(negative
signssinceenergyislostfromthesystem).

H
=

BondEnergies

BondEnergies
formed
broken

Exercise13

Calculatethechangeinenergythataccompaniesthefollowingreactiongiventhedatabelow.
H
(
g
)+F
(
g
)

2HF(
g)

BondType
2
2
HH
FF
HF

BondEnergy
432kJ/mol
154kJ/mol
565kJ/mol

Speakingofbondenergies,allowustoclearupsomecommonmisconceptionsAND
makesomedazzlingconnections.
Letsstartwiththevocabulary usedtodescribephasechanges.First,youmustrealizethatthevocabularyis
directional (hencethearrowsonthisdiagram)aswellasveryspecific.Youllhavetomeanwhatyousay
andsaywhatyoumeanwhenansweringafreeresponsequestion!
Phasetransitionsinvolvingovercoming
intermolecularattractions
orIMFswhichshouldneverbeconfusedwithionicorcovalent
chemicalbonds.
Fusion
(melting),
vaporization
, and
sublimation
requirean
input of energy
to overcome the attractive forces between
the particles of the substance. NOTICE we didnotspeakof
breakingbonds.
Freezing
,
condensation
,and
deposition
(oppositeofsublimation)
releaseenergy
asIMFsformsincetheparticlesachievealowerenergy
statemainlyduetoadecreaseintemperature.

Isthereadifferencebetweena
vapor
anda
gas
?Yes,itsprimarilysemantics.Agasisagasat
roomtemperature,wedontspeakofoxygenvapor.However,wedousethetermvapor
whenthesubstanceisnormallyaliquidorsolidatroomtemperature.Wesaywatervapor,
carbondioxidevapor,iodinevapor,etc.
Bevery,veryclearthatchangesinthephasesofmatterinvolvealteringIMFs,notaltering
chemicalbonds.*

Thestrengthoftheintermolecularattractionsbetweenmolecules,andthereforetheamountof
energyrequiredtoovercometheseattractiveforces(aswellastheamountofenergyreleased
whentheattractionsareformed)dependsonthemolecularpropertiesofthesubstance,ionic,
polar,nonpolar,etc.
Generally,themorepolaramoleculeis,thestrongertheattractiveforcesbetweenmolecules
are.
Hence,
morepolarmolecules
typically
requiremoreenergy
toovercometheintermolecular
attractionsinan
endothermicphasetransition
,and
releasemoreenergy
by
forming
intermolecular

attractionsduringanexothermicphasetransition
.

Phasetransitionsinvolvethebreakingorformingofintermolecularforces(attractive
interactionsbetweenmolecules).Hence,aswithotherchemicalreactions,itisnecessaryto
discusstheenergythatisabsorbedorgivenoffduringthebreakingorformingofintermolecular
interactionsinaphasetransition.

*UNLESSyouhaveanetworksolidorcovalentnetworksolidwhichisachemicalcompoundinwhichtheatomsarebondedby
covalentbondsinacontinuousnetwork.Inanetworksolidtherearenoindividualmoleculesandtheentirecrystalmaybe
consideredamacromolecule.Examplesofnetworksolidsincludediamondwithacontinuousnetworkofcarbonatomsandsilicon
dioxideorquartzwithacontinuousthreedimensionalnetworkofSiO
units.Graphiteandthemicagroupofsilicateminerals
2
structurallyconsistofcontinuoustwodimensionallayerscovalentlybondedwithinthelayerwithotherbondtypesholdingthe
layerstogether.Thatmeanstheyessentiallyslideinsheetsthewayyourpencillead(actuallygraphite)glidesacrossthepage
leavingatrail.

YouhaveprobablyseenagraphlikethisbeforearrivinginAPChemistry.Letsmakesomeadditional
dazzlingconnections!
Supposethisheatingcurveisforwater

Takeamomentandponderthedifferencesinmolecularstructureandmolecularmotionamongthedifferentstatesof
waterrepresentedabove,thekineticenergychanges,
and
thepotentialenergychanges.
1. Doestheprocessaboverepresentacollectionofchemicalchanges,physicalchangesorboth?
2. Whattypeofforceisinvolvedinthechangesyouidentifiedinquestion1?
3. Definetemperature:
4. Whichconversionsinvolvetemperaturechanges?
5. Whichmathematicalformulaisappropriateforcalculatingtheenergyassociatedwiththeprocessesyou
identifiedinquestion4?
6. Whichconversionsinvolvepotentialenergychanges?
7. Whichmathematicalformulaisappropriateforcalculatingtheenergyassociatedwiththeprocessesyou
identifiedinquestion4?
8. Howdoyoucalculate
q
fortheprocessesidentifiedinnumber6ifyouaregivenonlythemassofthewater
sample?

9.
Whichportionsofthisgraphrepresentequilibriumconditions?