Thermodynamics

Studiesofheatenergyanditstransformationintoor
fromotherformsofenergy.
Normallythetransformationisaccompaniedbya
changeoftemperatureorevenphaseofasystem.
Animportantaimofthermodynamicstudiesisto
findoutwaystoimprovetheefficiencyofthe
processofanenergytransformation.
Examples:
Howasteamenginemovemechanically,
Howarefrigeratorisabletocoolitscontents,
Whathappenstothekineticenergyofanobjectasit
comestoarest.

 Theprinciplesandlawsofthermodynamicsare
empirical,
basedonobservationandexperience
(experiment)
Theyareconcernedwiththemacroscopic
propertiessuchpressureandtemperature.
Themacroscopicpropertiesaretheaverageeffect
causedbythechangeoftheenergystateofthe
system.
Atthemicroscopicscale,theenergyofthe
particlesinthesystemfollowsacertain
distribution:
Statisticalconsideration
Theorykinetic

Thermodynamicssystems
Athermodynamicsystemisapartoftheuniverse
enclosedbyaboundary.
Boundary realorimaginary

Threetypesofsystem:
(a)Isolatedsystem nointeractionwithothersystem
(b)Closedsystem nomaterialcanflowintooroutof
thesystem
(c)Opensystem materialcanflowintooroutofthe
system

Thestateofthesystem
Definedbythepropertiesofsystemssuchas
temperature,pressure,volumeandothers
2typesofproperties:
(a)Extensiveproperty willchangeifthemassofthe
systemischanged.
e.g.totalvolume;totalenergy
(a)Intensiveproperty willnotchangeevenifthemass
ofthesystemischanged.
e.g.temperature;pressure;density

Thermodynamicequilibrium
Twoobjectsareinthermalcontactwitheachother
ifenergycanbeexchangedbetweenthem.

Theexchangeofenergywillbeintheformof
heat(vibrationsofatoms/molecules),flowoffluid
orelectromagneticradiation.
Theenergyisexchangedduetoatemperature
difference.
Thermalequilibriumisasituationinwhichtwo
objectswouldnothavenetexchangeoftheenergy
iftheywereplacedinthermalcontact.

BesidesThermalEquilibrium,asystemcanalsobeat:
MechanicalEquilibrium allelementsinthesystem
haveweightsthatbalancetheforceactingonthem
duetopressure.
ChemicalEquilibrium ifthesystemconsistsof
reactivecomponents,eitherthereactionshave
stoppedorforreversiblereactions,reactionsinboth
directionsoccuratequalrates.
Systemthathasachievedallthreeequilibriumissaid
tobeatThermodynamicEquilibrium.

ThermodynamicProcesses
Ifthepropertiesofasystemischanging,thesystemis
saidtobeundergoingacertainprocess.
Ifthepistonispushedrapidly,theprocessisnon
quasistatic equilibriumisdisturbed.
Ifthepistonispushedveryslowlysothatthesystem
ismaintainedatequilibrium,theprocessissaidtobe
quasistatic.
Ifthequasistaticprocessisreversible,itisa
reversibleprocess (ifnoenergyislossduringthe
process).

Zerothlawofthermodynamic
IfobjectsAandBareseparatelyinthermal
equilibriumwithathirdobjectC,thenAandBare
inthermalequilibriumwitheachother.
LetobjectCbethethermometer,
Sincetheyareinthermalequilibriumwitheach
other,thereisnoenergyexchangedamongthem.

Example1:

ObjectC(thermometer)isplacedincontactwithAuntilthey
achievethermalequilibrium.ThereadingonCisrecorded.
ObjectCisthenplacedincontactwithobjectBuntiltheyachieve
thermalequilibrium.ThereadingonCisrecordedagain.
Ifthetworeadingsarethesame,wecanconcludethatAandBare
inthermalequilibriumwitheachother.

Temperature
Temperatureisafundamental
physicalparameter.Itisan
experimentalfactthatmany
propertiesofanobjectdependon
temperature.
Forexample,theresistanceofa
conductor.Intheupperfigurewe
plottheresistivity, ofcopperasa
functionofT.WecanuseRorany
otherparameterthatdependsonT
topindowntheconceptof
temperature.

 Temperaturecanbethoughtofasthepropertythat
determineswhetheranobjectisinthermalequilibrium
withotherobjects.
Twoobjectsinthermalequilibriumwitheachotherareat
thesametemperature.
Iftwoobjectshavedifferenttemperatures,theyarenotin
thermalequilibriumwitheachother.
Temperatureissomethingthatdetermineswhetherornot
energywilltransferbetweentwoobjectsinthermal
contact.

Example2:Absolutetemperatures

Thermometers
Athermometerisadevicethatisusedtomeasurethe
temperatureofasystem.
Thermometersarebasedontheprinciplethatsome
physicalpropertyofasystemchangesasthesystems
temperaturechanges.
Thesepropertiesincludes:

Thevolumeofaliquid
Thedimensionsofasolid
Thepressureofagasataconstantvolume
Thevolumeofagasataconstantpressure
Theelectricresistanceofaconductor
Atemperaturescalecanbeestablishedonthebasisof
anyofthesephysicsproperties.

Typeofthermometers
(a)Commonthermometer
Expansionofmercuryorsomeliquid
Lengthofcolumn(volume)indicateslevel
oftemperature

(b)Gasthermometer
PV
m , isconstant
Gaslaw:m
T

V T
IfPisconstant,then
P T
IfVisconstant,then
P,Varecalledthermometricproperties

 ConstantP,levelAindicatestemperature.
ConstantV:LevelBadjustedtozerolevel,thenlevelA
indicatestemperature.

Absolutezero

Forthepressureextrapolatestozeroatatemperature
pointat273.15C,calledabsolutezero(0K).
Thesizeofthedegreeontheabsolutescaleisthesame
asthesizeofthedegreeontheCelsiusscale.
RelationbetweenKelvinscaleandCelsiusscale:

T K TC 2 7 3 . 1 5 K

 CelsiusscaleandFahrenheitscalehavedifferentsized
degreesanddifferentstartingpoints.
RelationbetweenFahrenheitscaleandCelsiusscale:

TF

9
o
TC 3 2 F
5

Icepointtemperatures
0oC=273.15K=32oF
Steampointtemperatures
100oC=373.15K=212oF

Example3:

Givethetemperaturepointof50CinKscale
andoFscale.

(c)Resistivethermometer
Resistance

R Ro 1 T T

and aretemperaturecoefficients,
Ro isresistanceatT =0oC

(d)Thermocouple
emfproducedbetweenthetwojunctionsofCuFe,one
whichisaticepoint(C)

Referencetemperatures

PressurePs isthatatthenormalboilingpointofwater(thesteampoint).
Thegraphshowsallthecurvesextrapolatedatacommonpointcalled
empiricalgastemperatureTs as:
Tg T 3

lim
P3 0

,
P3 V

V indicatingthatthepressuresaremeasuredatconstantvolume.

Example4:
Calibrationonthethermometerscale
Referencepoints(purewater)atatmosphericpressure
Thesteampoint,Ts
Theicepoint,Ti
Usingtheconstantvolumegasthermometer,

Pi
Ti

Ts
P
s V
1 0 0 Pi
ChooseTs Ti =100 T 1 0 0 Pi
i
Ps Pi
Ps 1

P
i

Fromexperiment,Ps/Pi=1.3661
ObtainPs andPi

Ti =273.15KandTs =373.15K