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Thermochemistry

Chapter 6

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Energy isthecapacitytodowork.
Radiant energy comesfromthesunandis
earthsprimaryenergysource
Thermal energyistheenergyassociatedwith
therandommotionofatomsandmolecules
Chemical energyistheenergystoredwithinthe
bondsofchemicalsubstances
Nuclear energyistheenergystoredwithinthe
collectionofneutronsandprotonsintheatom
Potential energy istheenergyavailablebyvirtue
ofanobjectsposition

2
EnergyChangesinChemicalReactions

Heatisthetransferofthermal energybetween
twobodiesthatareatdifferenttemperatures.

Temperatureisameasureofthe
thermal energy.

Temperature=ThermalEnergy

3
Thermochemistryisthestudyofheatchangeinchemical
reactions.
Thesystemisthespecificpartoftheuniversethatisof
interestinthestudy.

open closed isolated


Exchange: mass&energy energy nothing 4
Exothermic processisanyprocessthatgivesoffheat
transfersthermalenergyfromthesystemtothesurroundings.

2H2(g)+O2(g)2H2O(l)+energy

H2O(g)H2O(l)+energy

Endothermic processisanyprocessinwhichheathastobe
suppliedtothesystemfromthesurroundings.

energy+2HgO(s)2Hg(l)+O2(g)

energy+H2O(s)H2O(l)

5
SchematicofExothermicandEndothermicProcesses

6
Thermodynamicsisthescientificstudyofthe
interconversionofheatandotherkindsofenergy.

State functionsarepropertiesthataredeterminedbythestate
ofthesystem,regardlessofhowthatconditionwasachieved.
energy,pressure,volume,temperature

DE=Efinal-Einitial
DP=Pfinal-Pinitial

DV=Vfinal-Vinitial
DT=Tfinal-Tinitial

Potentialenergyofhiker1andhiker2
isthesameeventhoughtheytook
7
differentpaths.
First law of thermodynamicsenergycanbe
convertedfromoneformtoanother,butcannotbe
createdordestroyed.
DEsystem+DEsurroundings=0
or
DEsystem=-DEsurroundings

C3H8+5O23CO2+4H2O
Exothermicchemicalreaction!

Chemicalenergylostbycombustion=Energygainedbythesurroundings
8
system surroundings
Anotherformofthefirst lawforDEsystem
DE=q+w
DE isthechangeininternalenergyofasystem
qistheheatexchangebetweenthesystemandthesurroundings
wistheworkdoneon(orby)thesystem
w=-PDVwhenagasexpandsagainstaconstantexternalpressure

9
WorkDoneOntheSystem
w=F x d

w=-P DV
DV>0
F
PxV= x d 3
=Fxd=w -PDV < 0
d 2

wsys<0

Workis
nota
state
function.
Dw=wfinal-winitial

10
initial final
Asampleofnitrogengasexpandsinvolumefrom1.6Lto5.4L
atconstanttemperature.Whatistheworkdoneinjoulesifthe
gasexpands(a)againstavacuumand(b)againstaconstant
pressureof3.7atm?

w=-P DV

(a) DV=5.4L1.6L=3.8L P=0atm


W=-0atmx3.8L=0Latm=0joules

(b) DV=5.4L1.6L=3.8L P=3.7atm

w=-3.7atmx3.8L=-14.1Latm
101.3J =-1430J
w=-14.1Latmx
1Latm
11
Chemistry in Action: Making Snow

DE=q+w

q=0

w<0,DE<0

DE=CDT

DT<0,SNOW!

12
EnthalpyandtheFirstLawofThermodynamics
DE=q+w
Atconstantpressure:
q=DHandw=-PDV
DE=DH -PDV
DH=DE +PDV

13
Enthalpy (H)isusedtoquantifytheheatflowintooroutofa
systeminaprocessthatoccursatconstantpressure.
DH=H(products)H(reactants)
DH=heatgivenofforabsorbedduringareactionat constant pressure

Hproducts<Hreactants Hproducts>Hreactants
14
DH<0 DH>0
ThermochemicalEquations

IsDHnegativeorpositive?

Systemabsorbsheat

Endothermic

DH>0

6.01kJareabsorbedforevery1moleoficethat
meltsat00Cand1atm.

H2O(s)H2O(l) DH =6.01kJ/mol
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ThermochemicalEquations

IsDHnegativeorpositive?

Systemgivesoffheat

Exothermic

DH<0

890.4kJarereleasedforevery1moleofmethane
thatiscombustedat250Cand1atm.

CH4(g)+2O2(g)CO2(g) + 2H2O(l) DH =-890.4kJ/mol


16
ThermochemicalEquations

Thestoichiometriccoefficientsalwaysrefertothenumber
ofmolesofasubstance
H2O(s)H2O(l) DH =6.01kJ/mol

Ifyoureverseareaction,thesignofDHchanges
H2O(l)H2O(s) DH =-6.01kJ/mol

Ifyoumultiplybothsidesoftheequationbyafactorn,
thenDHmustchangebythesamefactorn.

2H2O(s)2H2O(l) DH =2x6.01=12.0kJ

17
ThermochemicalEquations

Thephysicalstatesofallreactantsandproductsmustbe
specifiedinthermochemicalequations.
H2O(s)H2O(l) DH =6.01kJ/mol
H2O(l)H2O(g) DH =44.0kJ/mol

Howmuchheatisevolvedwhen266gofwhitephosphorus(P4)
burninair?
P4(s)+5O2(g)P4O10(s)DH=-3013kJ/mol

1molP4 3013kJ
266gP4 x x =6470kJ
123.9gP4 1molP4

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AComparisonofDHandDE

2Na(s)+2H2O(l)2NaOH(aq)+H2(g)DH=-367.5kJ/mol
DE=DH -PDV At25oC,1moleH2=24.5Lat1atm
PDV=1atmx24.5L=2.5kJ

DE=-367.5kJ/mol2.5kJ/mol=-370.0kJ/mol

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Thespecific heat(s)ofasubstanceistheamountofheat(q)
requiredtoraisethetemperatureofone gramofthe
substancebyone degreeCelsius.
Theheat capacity(C)ofasubstanceistheamountofheat
(q)requiredtoraisethetemperatureofa given quantity(m)
ofthesubstancebyone degreeCelsius.
C=m x s

Heat(q)absorbedorreleased:

q=m x s x Dt
q=C x Dt
Dt=tfinal-tinitial

20
Howmuchheatisgivenoffwhenan869gironbarcools
from94oCto5oC?

sofFe=0.444J/goC

Dt=tfinaltinitial=5oC94oC=-89oC

q=msDt =869gx0.444J/goCx89oC =-34,000J

21
Constant-VolumeCalorimetry

qsys=qwater+qbomb+qrxn
qsys=0
qrxn=-(qwater+qbomb)
qwater=m x sxDt
qbomb=Cbomb x Dt

ReactionatConstantV
DH=qrxn
DH~qrxn
Noheatentersorleaves! 22
Constant-PressureCalorimetry

qsys=qwater+qcal+qrxn
qsys=0
qrxn=-(qwater+qcal)
qwater=m x sxDt
qcal=Ccal x Dt

ReactionatConstantP
DH=qrxn

Noheatentersorleaves! 23
24
Chemistry in Action:
FuelValuesofFoodsandOtherSubstances
C6H12O6(s)+6O2(g)6CO2(g)+6H2O(l)DH=-2801kJ/mol

1cal=4.184J
1Cal=1000cal=4184J

Substance DHcombustion(kJ/g)

Apple -2

Beef -8

Beer -1.5

Gasoline -34
25
Becausethereisnowaytomeasuretheabsolutevalueof
theenthalpyofasubstance,mustImeasuretheenthalpy
changeforeveryreactionofinterest?
Establishanarbitraryscalewiththestandard enthalpy of
formation(DH0f )asareferencepointforallenthalpy
expressions.

Standard enthalpy of formation(DH0f)istheheatchange


thatresultswhenone moleofacompoundisformedfrom
itselementsatapressureof1atm.

Thestandardenthalpyofformationofanyelementinits
moststableformiszero.
DH 0
f(C,graphite)=0
DH f(O2)=0
0

DH (O )=142kJ/mol
0 DH f(C,diamond)=1.90kJ/mol
0
f 3 26
27
Thestandard enthalpy of reaction(DHrxn
0
)istheenthalpyof
areactioncarriedoutat1atm.

aA+bBcC+dD

DHrxn
0
= [ cDH0f(C) + dDH0f(D) ] - [ aDH0f(A) + bDH0f(B) ]

DHrxn
0
= S nDH0f(products) - S mDHf0(reactants)

Hesss Law:Whenreactantsareconvertedtoproducts,the
changeinenthalpyisthesamewhetherthereactiontakes
placeinonesteporinaseriesofsteps.

(Enthalpyisastatefunction.Itdoesntmatterhowyouget
there,onlywhereyoustartandend.)
28
C(graphite)+1/2O2(g)CO(g)
CO(g)+1/2O2(g)CO2(g)
C(graphite)+O2(g)CO2(g)

29
CalculatethestandardenthalpyofformationofCS2(l)given
that:
C(graphite)+O2(g)CO2(g)DHrxn
0
=-393.5kJ/mol
S(rhombic)+O2(g)SO2(g)DHrxn
0
=-296.1kJ/mol
CS2(l)+3O2(g)CO2(g)+2SO2(g)DH0rxn
=-1072kJ/mol
1.WritetheenthalpyofformationreactionforCS2

C(graphite)+2S(rhombic)CS2(l)
2.Addthegivenrxnssothattheresultisthedesiredrxn.
C(graphite)+O2(g)CO2(g)DH0rxn
=-393.5kJ/mol
2S(rhombic)+2O2(g)2SO2(g)DHrxn0
=-296.1kJ/molx2
+ CO2(g)+2SO2(g)CS2(l)+3O2(g)DH0rxn
=+1072kJ/mol

C(graphite)+2S(rhombic)CS2(l)
30
DH0rxn
=-393.5+(2x-296.1)+1072=86.3kJ/mol
Benzene(C6H6)burnsinairtoproducecarbondioxideand
liquidwater.Howmuchheatisreleasedpermoleofbenzene
combusted?Thestandardenthalpyofformationofbenzeneis
49.04kJ/mol.
2C6H6(l)+15O2(g)12CO2(g)+6H2O(l)

DHrxn
0
= S nDH0f(products) - S mDHf0(reactants)

DHrxn
0
= [ 12DH0f (CO2) + 6DH0f (H2O)] - [ 2DHf0(C6H6) ]

DHrxn
0
= [12x393.5+6x187.6][2x49.04]=-5946kJ

-5946kJ
=-2973kJ/molC6H6
2mol

31
Chemistry in Action: Bombardier Beetle Defense

C6H4(OH)2(aq)+H2O2(aq)C6H4O2(aq)+2H2O(l)DH0=?

C6H4(OH)2(aq)C6H4O2(aq)+H2(g)DH0=177kJ/mol

H2O2(aq)H2O(l)+O2(g)DH0=-94.6kJ/mol

H2(g)+ O2(g)H2O(l)DH0=-286kJ/mol

DH0=177-94.6286=-204kJ/mol
Exothermic!

32
Theenthalpy of solution(D Hsoln)istheheatgeneratedor
absorbedwhenacertainamountofsolutedissolvesina
certainamountofsolvent.
DHsoln=Hsoln-Hcomponents

Whichsubstance(s)couldbe
usedformeltingice?

Whichsubstance(s)couldbe
usedforacoldpack?

33
TheSolutionProcessforNaCl

DHsoln=Step1+Step2=788784=4kJ/mol 34

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