TheFirstLawofThermodynamics:ClosedSystems

The first law of thermodynamics can be simply stated as follows: during an interaction
betweenasystemanditssurroundings,theamountofenergygainedbythesystemmust
beexactlyequaltotheamountofenergylostbythesurroundings.
A closed system can exchange energy with its surroundings through heat and work
transfer. In other words, work and heat are the forms that energy can be transferred
acrossthesystemboundary.
Based on kinetic theory, heat is defined as the energy associated with the random
motionsofatomsandmolecules.

HeatTransfer
Heatisdefinedastheformofenergythatistransferredbetweentwosystemsbyvirtueof
atemperaturedifference.
Note:therecannotbeanyheattransferbetweentwosystemsthatareatthesame
temperature.
Note:Itisthethermal(internal)energythatcanbestoredinasystem.Heatisaformof
energyintransitionandasaresultcanonlybeidentifiedatthesystemboundary.
HeathasenergyunitskJ(orBTU).Rateofheattransferistheamountofheattransferred
perunittime.
Heat is a directional (or vector) quantity; thus, it has magnitude, direction and point of
action.
Notation:
Q(kJ)amountofheattransfer
Q(kW)rateofheattransfer(power)
q(kJ/kg)heattransferperunitmass
q(kW/kg)powerperunitmass
Signconvention:HeatTransfertoasystemispositive,andheattransferfromasystemis
negative.Itmeansanyheattransferthatincreasestheenergyofasystemispositive,and
heattransferthatdecreasestheenergyofasystemisnegative.

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System

Heatout

Heatin

Q=5kJ

Q=5kJ

Fig.1:Signconvention:positiveiftothesystem,negativeiffromthesystem.

ModesofHeatTransfer
Heatcanbetransferredinthreedifferentmodesconduction,convection,andradiation.
Allmodesofheattransferrequiretheexistenceofatemperaturedifference.
Conduction: is the transfer of energy from the more energetic particles to the adjacent
lessenergeticparticlesasaresultofinteractionsbetweenparticles.
Insolids,conductionisduetothecombinationofvibrationsofthemoleculesinalattice
andtheenergytransportbyfreeelectrons.
Convection: is the mode of energy transfer between a solid surface and the adjacent
liquidorgaswhichisinmotion,anditinvolvesthecombinedeffectsofconductionand
fluidmotion(advection).
Convectioniscalledforcedifthefluidisforcedtoflowbyexternalmeanssuchasafanor
apump.Itiscalledfreeornaturalifthefluidmotioniscausedbybuoyancyforcesthatare
inducedbydensitydifferencesduetothetemperaturevariationinafluid.
Radiation: is the energy emitted by matter in the form of electromagnetic waves (or
photons) as a result of the changes in the electronic configurations of the atoms or
molecules.

Work
Workistheenergyinteractionbetweenasystemanditssurroundings.Morespecifically,
workistheenergytransferassociatedwithforceactingthroughadistance.
Notation:
W(kJ)amountofworktransfer
W(kW)power
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w(kJ/kg)workperunitmass
w(kW/kg)powerperunitmass
Sign convention: work done by a system is positive, and the work done on a system is
negative.
()
Q
(+)
System

(+)
()

Fig.2:Signconventionforheatandwork.
Similaritiesbetweenworkandheattransfer:
Botharerecognizedattheboundariesofthesystemastheycrossthem(boundary
phenomena).
Systemspossesenergy,butnotheatorwork(transferphenomena).
Bothareassociatedwithaprocess,notastate.Heatorworkhasnomeaningata
state.
Botharepathfunctions,theirmagnitudesdependonthepathfollowedduringa
processaswellastheendstates.
Path functions: have inexact differentials designated by symbol . Properties, on the
other hand, are point functions which depend on the state only (not on how a system
reachesthatstate),andtheyhaveexactdifferentials.
2

dV V

V1 V

(Point function)

W W

12

(Path function, not W nor W2 - W1 )

ElectricalWork
The work that is done on a system by electrons. When N coulombs of electrons move
throughapotentialdifferenceV,theelectricalworkdoneis:

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We VN

(kJ )

Which can be explained in the rate form as

We VI

(kW )

Example1:Electricalwork
A wellinsulated electrical oven is being heated through its heating element. Determine
whetheritisworkorheatinteraction.Considertwosystems:a)theentireoven(including
theheater),andb)onlytheairintheoven(withouttheheater)seeFig33.
Solution:
Theenergycontentoftheovenisincreasedduringthisprocess.
a) The energy transfer to the oven is not caused by a temperature difference
between the oven and air. Instead, it is caused by electrical energy crossing the
systemboundaryandthus:thisisaworktransferprocess.
b) Thistime,thesystemboundaryincludestheoutersurfaceoftheheaterandwill
notcutthroughit.Therefore,noelectronswillbecrossingthesystemboundary.
Instead,theenergytransferisaresult ofatemperaturedifferencebetweenthe
electricalheaterandair,thus:thisisaheattransferprocess.

Electric
oven

Electric
oven

air

air

Heater

Heater

Systemboundary

Systemboundary

Fig.3:Schematicforexample1.

Mechanicalwork
Thereareseveralwaysofdoingwork,eachinsomewayrelatedtoaforceactingthrough
adistance.

W F .s

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(kJ )

LawofThermodynamics:ClosedSystems4

Iftheforceisnotconstant,weneedtointegrate:
2

W F .ds

(kJ )

Therearetworequirementsforaworkinteraction:
theremustbeaforceactingontheboundary
theboundarymustmove
Therefore, the displacement of the boundary without any force to oppose or drive this
motion(suchasexpansionofagasintoevacuatedspace)isnotaworkinteraction,W=0.
Also,iftherearenodisplacementsoftheboundary,evenifanactingforceexists,there
willbenoworktransferW=0(suchasincreasinggaspressureinarigidtank).

MovingBoundaryWork
The expansion and compression work is often called moving boundary work, or simply
boundarywork.
Weanalyzethemovingboundaryworkforaquasiequilibriumprocess.Considerthegas
enclosedinapistoncylinderatinitialPandV.Ifthepistonisallowedtomoveadistance
dsinaquasiequilibriummanner,thedifferentialworkis:

Wb F .ds PAds PdV

The quasiequilibrium expansion process is shown in Fig. 4. On this diagram, the
differentialareadAundertheprocesscurveinPVdiagramisequaltoPdV,whichisthe
differentialwork.
Note:agascanfollowseveraldifferentpathsfromstate1to2,andeachpathwillhavea
differentareaunderneathit(workispathdependent).
ThenetworkorcycleworkisshowninFig.5.Inacycle,thenetchangeforanyproperties
(point functions orexactdifferentials)is zero.However, the networkandheattransfer
dependonthecyclepath.
U=P=T=(anyproperty)=0foracycle

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Fig.4:theareaunderPVdiagramrepresentstheboundarywork.
P

2
Wnet
1
V2

V1

Fig.5:networkdoneduringacycle.

PolytropicProcess
During expansion and compression processes of real gases, pressure and volume are
oftenrelatedbyPVn=C,wherenandCareconstants.Themovingworkforapolytropic
processcanbefound:
2

W polytopic PdV CV n dV

P2V2 P1V1

1 n

Since P1V1n P2V2n C .Foranidealgas(PV=mRT)itbecomes:

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W polytropic

mR T2 T1
, n 1 (kJ )
1 n

The special case n =1 is the isothermal expansion P1V1 = P2V2 = mRT0= C, which can be
foundfrom:
2
2
V
C
Wb ,isothermal PdV dV P1V1 ln 2
V
V1
1
1

, n 1

(kJ )

Sinceforanidealgas,PV=mRT0atconstanttemperatureT0,orP=C/V.

Example2:Polytropicwork
Agasinpistoncylinderassemblyundergoesapolytropicexpansion.Theinitialpressureis
3bar,theinitialvolumeis0.1m3,andthefinalvolumeis0.2m3.Determinetheworkfor
theprocess,inkJ,ifa)n=1.5,b)n=1.0,andc)n=0.
Solution:
Assumethati)thegasisaclosedsystem,ii)themovingboundaryisonlyworkmode,and
iii)theexpansionispolytropic.
a)n=1.5
V2

PdV

V1

P2V2 P1V1

1 n

WeneedP2thatcanbefoundfrom P1V1n P2V2n :

V
P2 P1 1
V2

0.1
3bar

0.2

1.5

1.06bar 0.2m 3 30.1 10 5 N / m 2

W
1 1 .5
1 bar

1.06 bar
1 kJ
3
17.6 kJ
10 N .m

b)n=1,thepressurevolumerelationshipisPV=constant.Theworkis:
2
V
W PdV P1V1 ln 2
V1
1

5
2
0.2
3 10 N / m 1 kJ
W 3bar 0.1 m
ln
20.79 kJ
3
1 bar 10 N .m 0.1

c)Forn=0,thepressurevolumerelationreducestoP=constant(isobaricprocess)andthe
integralbecomeW=P(V2V1).
Substitutingvaluesandconvertingunitsasabove,W=30kJ.
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Springwork
Forlinearelasticsprings,thedisplacementxisproportionaltotheforceapplied:

F ks x
whereksisthespringconstantandhastheunitkN/m.Thedisplacementxismeasured
fromtheundisturbedpositionofthespring.Thespringworkis:

Wspring

1
k s x 22 x12
2

(kJ )

Note:theworkdoneonaspringequalstheenergystoredinthespring.

Nonmechanicalformsofwork
Nonmechanical forms of work can be treated in a similar manner to mechanical work.
SpecifyageneralizedforceFactinginthedirectionofageneralizeddisplacementx,the
worktransferassociatedwiththedisplacementdxis:

W F .dx
Example3:Mechanicalwork
Calculatetheworktransferinthefollowingprocess:
P
2

P2

P1

V1

V2

Fig.6:SchematicPVdiagramforExample3.
Solution:
Process12isanexpansion(V2>V1)andthesystemisdoingwork(W12>0),thus:
W12=P1(V2V1)+[0.5(P1+P2)P1](V2V1)
=(V2V1)(P1+P2)/2
Process23isanisometricprocess(constantvolumeV3=V2),soW23=0
Process31isacompression(V3>V1),workisdoneonthesystem,(W31<0)
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W31=P1(V2V1)
Wcycle=Wnet=W12+W23+W31=(V2V1)(P2P1)/2
NotethatinacycleU=P=T=(anyproperty)=0

FirstLawofThermodynamics
Firstlaw,ortheconservationofenergyprinciple,statesthatenergycanbeneithercreated
nordestroyed;itcanonlychangeforms.
Thefirstlawcannotbeprovedmathematically,itisbasedonexperimentalobservations,
i.e.,therearenoprocessinthenaturethatviolatesthefirstlaw.
Thefirstlawforaclosedsystemorafixedmassmaybeexpressedas:
net energy transfer to (or from) = net increase (or decrease) in the total
thesystemasheatandwork
energyofthesystem
QW=E

(kJ)

where
Q=netheattransfer(=QinQout)
W=networkdoneinallforms(=WinWout)
E=netchangeintotalenergy(=E2E1)
Thechangeintotalenergyofasystemduringaprocesscanbeexpressedasthesumof
thechangesinitsinternal,kinetic,andpotentialenergies:
E=U+KE+PE (kJ)

U m u 2 u1

1
m V22 V12
2
PE mg z 2 z1
KE

Note:forstationarysystemsPE=KE=0,thefirstlawreducesto
QW=U
Thefirstlawcanbewrittenonaunitmassbasis:
qw=e

(kJ/kg)

orindifferentialform:
QW=dU (kJ)
qW=du

(kJ/kg)

orintherateform:
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QW=dE/dt

(kW)

For a cyclic process, the initial and final states are identical, thus E=0. The first law
becomes:
QW=0

(kJ)

Note:fromthefirstlawpointofview,thereisnodifferencebetweenheattransferand
work,theyarebothenergyinteractions.Butfromthesecondlawpointofview,heatand
workareverydifferent.
Example4:Fistlaw
Airiscontainedinaverticalpistoncylinderassemblyfittedwithanelectricalresistor.The
atmosphericpressureis100kPaandpistonhasamassof50kgandafaceareaof0.1m2.
Electric current passes through the resistor, and the volume of air slowly increases by
0.045 m3. The mass of the air is 0.3 kg and its specific energy increases by 42.2 kJ/kg.
Assumetheassembly(includingthepiston)isinsulatedandneglectthefrictionbetween
thecylinderandpiston,g=9.8m/s2.Determinetheheattransferfromtheresistortoair
forasystemconsistinga)theairalone,b)theairandthepiston.

System
boundary

Piston

Piston

parta

System
boundary
partb

Air

Air

Fig.7:Schematicforproblem4.
Assumptions:
Twoclosedsystemsareunderconsideration,asshowninschematic.
Theonlyheattransferisfromtheresistortotheair.KE=PE=0(forair)
Theinternalenergyofthepistonisnotaffectedbytheheattransfer.
a)Takingtheairasthesystem,
(KE+PE+U)air=QW
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Q=W+Uair
Forthissystemworkisdoneatthebottomofthepiston.Theworkdonebythesystemis
(atconstantpressure):
V2

PdV PV

V1

V1

Thepressureactingontheaircanbefoundfrom:
PApiston=mpistong+PatmApiston
P

mpiston g
Apiston

Patm

50kg 9.81m / s 2
P

0.1m
2

1Pa 1kPa

100kPa 104.91 kPa

2
1N / m 1000 Pa

Thus,theworkis
W=(104.91kPa)(0.045m3)=4.721kJ
WithUair=mairuair,theheattransferis
Q=W+mairuair=4.721kJ+(0.3kg)(42.2kJ/kg)=17.38kJ
b)systemconsistingtheairandthepiston.Thefirstlawbecomes:
(KE+PE+U)air+(KE+PE+U)piston=QW
where(KE=PE)air=0and(KE=U)piston=0.Thus,itsimplifiesto:
(U)air+(PE)piston=QW
For this system, work is done at the top of the piston and pressure is the atmospheric
pressure.Theworkbecomes
W=PatmV=(100kPa)(0.045m3)=4.5kJ
Theelevationchangerequiredtoevaluatethepotentialenergychangeofthepistoncan
befoundfromthevolumechange:
z=V/Apiston=0.045m3/0.1m2=0.45m
(PE)piston=mpistongz=(50kg)(9.81m/s2)(0.45m)=220.73J=0.221kJ
Q=W+(PE)piston+mairuair
Q=4.5kJ+0.221kJ+(0.3kg)(42.2kJ/kg)=17.38kJ
Notethattheheattransferisidenticalinbothsystems.

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SpecificHeats
Thespecificheatisdefinedastheenergyrequiredtoraisethetemperatureofaunitmass
ofasubstancebyonedegree.Therearetwokindsofspecificheats:
specific heat at constant volume, Cv (the energy required when the volume is
maintainedconstant)
specific heat at constant pressure, Cp (the energy required when the pressure is
maintainedconstant)
The specific heat at constant pressure Cp is always higher than Cv because at constant
pressure the system is allowed to expand and energy for this expansion must also be
suppliedtothesystem.
Letsconsiderastationaryclosedsystemundergoingaconstantvolumeprocess(wb=0).
Applyingthefirstlawinthedifferentialform:
qw=du
atconstantvolume(nowork)andbyusingthedefinitionofCv,onecanwrite:
C v dT du

or
u
Cv

T v

Similarly,anexpressionforthespecificheatatconstantpressureCpcanbefound.From
thefirstlaw,foraconstantpressureprocess(wb+u=h).Ityields:

h
Cp

T p
specific heats (both Cv and Cp) are properties and therefore independent of the
typeofprocesses.
Cvisrelatedtothechangesininternalenergyu,andCptothechangesinenthalpy,
h.
It would be more appropriate to define: Cv is the change in specific internal energy per
unitchangeintemperatureatconstantvolume.Cpisthechangeinspecificenthalpyper
unitchangeintemperatureatconstantpressure.

Specificheatsforidealgases
It has been shown mathematically and experimentally that the internal energy is a
functionoftemperatureonly.
u=u(T)

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Usingthedefinitionofenthalpy(h=u+Pv)andtheidealgasequationofstate(Pv=RT),
wehave:
h=u+RT
SinceRisaconstantanduisafunctionofTonly:
h=h(T)
Therefore, at a given temperature, u, h, Cv and Cp of an ideal gas will have fixed values
regardlessofthespecificvolumeorpressure.Foranidealgas,wehave:

du C v T dT

dh C p T dT

The changes in internal energy or enthalpy for an ideal gas during a process are
determinedbyintegrating:
2

u u 2 u1 C v T dT

(kJ / kg )

h h2 h1 C p T dT

(kJ / kg )

Aslowpressures,allrealgasesapproachidealgasbehavior,andthereforetheirspecific
heatsdependontemperatureonly.Thespecificheatsofrealgasesatlowpressuresare
calledidealgasspecificheats(orzeropressurespecificheats)andareoftendenotedby
Cp0andCv0.Tocarryouttheaboveintegrations,weneedtoknowCv(T)andCp(T).These
areavailablefromavarietyofsources:
TableA2a:forvariousmaterialsatafixedtemperatureofT=300K
TableA2b:variousgasesoverarangeoftemperatures250T1000K
TableA2c:variouscommongasesintheformofathirdorderpolynomial
Foranidealgas,wecanwrite:

RT hT u T
dh du
R

dT dT
R C p Cv
Theratioofspecificheatsiscalledthespecificheatratiok=Cp/Cv:
varieswithtemperature,butthisvariationisverymild.
formonatomicgases,itsvalueisessentiallyconstantat1.67.
Manydiatomicgases,includingair,haveaspecificheatratioofabout1.4atroom
temperature.
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Specificheatsforsolidsandliquids
A substance whose specific volume (or density) is constant is called incompressible
substance. The specific volumes of solids and liquids (which can be assumed as
incompressiblesubstances)essentiallyremainconstantduringaprocess.
The constant volume assumption means that the volume work (boundary work) is
negligible compared with other forms of energy. As a result, it can be shown that the
constantvolume and constantpressure specific heats are identical for incompressible
substances:
Cp=Cv=C
Specificheatsofincompressiblesubstancesareonlyafunctionoftemperature,
C=C(T)
Thechangeofinternalenergybetweenstate1and2canbeobtainedbyintegration:
2

u u 2 u1 C T dT

(kJ / kg )

Forsmalltemperatureintervals,aCataveragedtemperaturecanbeusedandtreatedas
aconstant,yielding:

u C ave T2 T1
Theenthalpychangeofincompressiblesubstancecanbedeterminedfromthedefinition
ofenthalpy(h=u+Pv)
h2h1=(u2u1)+v(P2P1)
h=u+vP(kJ/kg)
ThetermvPisoftensmallandcanbeneglected,soh=u.
Example5:Specificheatandfirstlaw
Twotanksareconnectedbyavalve.Onetankcontains2kgofCO2at77Cand0.7bar.
The other tank has 8 kg of the same gas at 27C and 1.2 bar. The valve is opened and
gasesareallowedtomixwhilereceivingenergybyheattransferfromthesurroundings.
Thefinalequilibriumtemperatureis42C.Usingidealgasmodel,determinea)thefinal
equilibriumpressureb)theheattransferfortheprocess.
Assumptions:
ThetotalamountofCO2remainsconstant(closedsystem).
IdealgaswithconstantCv.
Theinitialandfinalstatesinthetanksareequilibrium.Noworktransfer.

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CO2

CO2

8kg,27C,1.2bar

2kg,77C,0.7bar
Valve

Thefinalpressurecanbefoundfromidealgasequationofstate:

Pf

mt RT f

V1 V2

m1 m2 RT f
V1 V2

Fortank1and2,wecanwrite:V1=m1RT1/P1andV2=m2RT2/P2.Thus,thefinalpressure,
Pfbecomes:

m1 m2 RT f

Pf

m1 m2 T f

m1 RT1 m2 RT2 m1T1 m2T2

P1 P2 P1 P2
10kg 315K
Pf
2kg 350 K 8kg 300 K 1.05bar
0.7bar
1.2bar
b)Theheattransfercanbefoundfromanenergybalance:
U=QW
WithW=0,
Q=UfUi
whereinitialinternalenergyis:Ui=m1u(T1)+m2u(T2)
Thefinalinternalenergyis:Uf=(m1+m2)u(Tf)
Theenergybalancebecomes:
Q=m1[u(Tf)u(T1)]+m2[u(Tf)u(T2)]
SincethespecificheatCvisconstant
Q=m1Cv[TfT1]+m2Cv[TfT2]

kJ
kJ
315K 350 K 8kg 0.745
315K 300 K 37.25kJ
Q 2kg 0.745
kg.K
kg.K

Theplussignindicatesthattheheattransferisintothesystem.

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