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9/24/2016

thermochemistry

Thermodynamics:Temperature,Heat,andWork
ThermodynamicsThestudyoftherelationshipbetweenheat,work,andotherformsofenergy.
ThermochemistryAbranchofthermodynamicswhichfocusesonthestudyofheatgivenoffor
absorbedinachemicalreaction.

TemperatureAnintensivepropertyofmatteraquantitativemeasurementofthedegreetowhich
anobjectiseither"hot"or"cold".
1.Thereare3scalesformeasuringtemperature
Fahrenheitrelative
32 Fisthenormalfreezingpointtemperatureofwater212 Fisthenormalboiling
pointtemperatureofwater.
Celsius(centigrade)relative
0 Cisthenormalfreezingpointtemperatureofwater100 Cisthenormalboiling
pointtemperatureofwater.
Kelvinabsolute
0Kisthetemperatureatwhichthevolumeandpressureofanidealgasextrapolate
tozero.

ConversionFactorsforTemperature

Heat(q)
Aformofenergyassociatedwiththerandommotionoftheelementaryparticlesinmatter.
HeatcapacityTheamountofheatneededtoraisethetemperatureofadefinedamountofapure
substancebyonedegree.
SpecificheatTheamountofheatneededtoraisethetemperatureofonegramofasubstanceby1
C(or1K)
SIunitforspecificheatisjoulespergram1Kelvin1(J/gK)
CalorieThespecificheatofwater=4.184J/gK
MolarheatcapacityTheamountofheatrequiredtoraisethetemperatureofonemoleofa
substanceby1 C(or1K)
SIunitformolarheatcapacityisjoulespermole1Kelvin1(J/molK)
Btu(Britishthermalunit)Theamountofheatneededtoraisethetemperatureof1lbwaterby1
F.
NOTE:Thespecificheatofwater(4.184J/gK)isverylargerelativetoothersubstances.Theoceans
(whichcoverover70%oftheearth)actasagiant"heatsink,"moderatingdrasticchangesintemperature.
Ourbodytemperaturesarealsocontrolledbywateranditshighspecificheat.Perspirationisaformof
evaporativecoolingwhichkeepsourbodytemperaturesfromgettingtoohigh.
https://www.chem.tamu.edu/class/majors/tutorialnotefiles/thermo.htm

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thermochemistry

LatentHeatversusSensibleHeat
SensibleheatHeatthatcanbedetectedbyachangeinthetemperatureofasystem.
LatentheatHeatthatcannotbedetectedbecausethereisnochangeintemperatureofthesystem.
e.g.Theheatthatisusedtomelticeortoevaporatewaterislatentheat.
Therearetwoformsoflatentheat:
HeatoffusionTheheatthatmustbeabsorbedtomeltamoleofasolid.
e.g.meltingicetoliquidwater
HeatofvaporizationTheheatthatmustbeabsorbedtoboilamoleofaliquid.
e.g.boilingliquidwatertosteam

CaloricTheoryofHeat
Servedasthebasisofthermodynamics.
Isnowknowntobeobsolete
Basedonthefollowingassumptions
Heatisafluidthatflowsfromhottocoldsubstances.
Heathasastrongattractiontomatterwhichcanholdalotofheat.
Heatisconserved.
Sensibleheatcausesanincreaseinthetemperatureofanobjectwhenitflowsintotheobject.
Latentheatcombineswithparticlesinmatter(causingsubstancestomeltorboil)
Heatisweightless.
Theonlyvalidpartofthecalorictheoryisthatheatisweightless.
HeatisNOTafluid,atitisNOTconserved.

1798SirBenjaminThompson(CountRumford)

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thermochemistry

Canonboringexperimentshowedthatfrictionwasaninexhaustiblesourceof
heat.Heconcludedthatheat,therefore,wasnotconserved.
Thisexperimentservedasastartingpointforthedevelopmentofanewtheory,
thekinetictheoryofheat.

KineticTheoryofHeat
1.Dividestheuniverseintotwoparts:
1.SystemThesmallportionoftheuniverseinwhichweareinterested.
2.SurroundingsEverythingnotincludedinthesystem,i.e.therestoftheuniverse.
ABOUNDARYseparatesthesystemandthesurroundingsfromeachotherandcanbetangibleor
imaginary.
Heatissomethingthatistransferredbackandforthacrossboundarybetweenasystemandits
surroundings
HeatisNOTconserved.
Thekinetictheoryofheatisbaseduponthelastpostulateinthekineticmoleculartheorywhichstates
thattheaveragekineticenergyofacollectionofgasparticlesisdependentonlyuponthe
temperatureofthegas.(SeeKineticMolecularTheorynotes)

whereRistheidealgasconstant(0.0821Latm/molK)andTistemperature(Kelvin)
Thekinetictheoryofheatcanbesummarizedasfollows:

Whenheatentersasystem,itcausesanincreaseinthespeed
atwhichtheparticlesinthesystemmove.

Work(w)
Definedasmechanicalenergyequaltotheproductoftheforce(F)appliedtoanobjectandthe
distance(d)thattheobjectismoved:

Work,likeheat,resultsfrominteractionbetweenasystemanditssurroundings.
Chemicalreactionscandotwotypesofwork:
ElectricalworkWhenareactionisusedtodriveanelectriccurrentthroughawire.
e.g.alightbulb
WorkofexpansionWhenareactioncausesachangeinthevolumeofthesystem.
https://www.chem.tamu.edu/class/majors/tutorialnotefiles/thermo.htm

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e.g.agaspushingupapiston
Themagnitudeofworkdonewhenagasexpandsisequaltotheproductofthepressureof
thegasandthechangeinvolumeofthegas:

HeatandWork
Thompson'scanonboringexperimentshowedhowwork(boringthecanon)couldproduceheat.

1838JamesPrescottJoule

Didseveralexperimentsmeasuringhowmuchheatcouldbeproducedfroma
givenamountofheat.
Inhismostwellknownexperiment,Jouleusedfallingweightsconnectedtoa
ropewrappedaroundrotatingpaddles.Thepaddleswereplacedineitherwater,
mercury,oroilandhemeasuredthechangeintemperatureoftheseliquidswhen
theweightsweredropped.
Onejouleisbydefinitiontheworkdonewhenaforceofonenewton(N)isused
tomoveanobjectonemeter(m):

Next:"FirstLawofThermodynamics"

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