TOPLINA I TERMODINAMIKA 5 Klasična aproksimacija statističke fizike

5.1 Kvantna stanja i valni paket

1 Priroda topline
5.2 Kanonska raspodjela u klasičnoj aproksimaciji statističke fizike
1.1 Toplinske pojave u prirodi
5.3 Ekviparticijski teorem
1.2 Toplina i energija
5.4 Toplinski kapacitet plinova s višeatomskim molekulama
1.3 Makroskopsko i mikroskopsko stanje tvari
5.5 Primjer makroskopskog njihala u zraku
1.4 Temeljni postulat statističke fizike
5.6 Barometarska formula
1.5 Lokalne fluktuacije
5.7 Princip djelovanja ultracentrifuge
2 Toplinsko medudjelovanje
6 Toplinsko zračenje
2.1 Toplinska ravnoteža
6.1 Elektromagnetski modovi u šupljini
2.2 Temperatura
6.2 Planckov zakon zračenja
2.3 Entropija
6.3 Ukupno zračenje crnog tijela
2.4 Kanonska raspodjela
6.4 Toplinsko zračenje necrnih tijela
2.5 Osvrt na intenzivne i ekstenzivne veličine
6.5 Zračenje Sunca
2.6 Opća definicija entropije
7 Termodinamika
3 Neke toplinske pojave
7.1 Rad kod promjene volumena sustava
3.1 Paramagnetizam
7.2 Prvi zakon termodinamike
3.2 Toplinski kapacitet čvrstih tvari
7.3 Mikroskopska slika promjene energije
3.3 Toplinska svojstva idealnog klasičnog plina
7.4 Gotovo ravnotežni procesi
4 Temperaturna ljestvica 7.5 Neravnotežni procesi
4.1 Definicija jedinice za temperaturu 7.6 Neki primjeri ireverzibilnih procesa
4.2 Baždareni termometri 7.7 Termodinamička ravnoteža
4.3 Boltzmannova konstanta 7.8 Drugi zakon termodinamike
4.4 Smještaj nekih toplinskih pojava na temperaturnoj ljestvici 7.9 Fenomenološka formulacija drugog zakona termodinamike
7.10 Treći zakon termodinamike
7.11 Toplinski kapaciteti
7.12 Termodinamički potencijali
1 2
8 Primjena termodinamike na idealan plin
8.1 Izotermna ekspanzija idealnog plina
8.2 Adijabatska ekspanzija idealnog plina
8.3 Izohorni proces
8.4 Izobarni proces
8.5 Maksimalan tehnički koristan rad
8.6 Entropija idealnog plina
8.7 Smjesa različitih idealnih plinova

9 Temodinamika agregatnih stanja čiste tvari

9.1 Realni plinovi
9.2 PVT dijagram stanja čiste tvari
9.3 Entalpija taljenja i isparivanja

10 Toplinski strojevi
10.1 Carnotov kružni proces
10.2 Benzinski motor
10.3 Dizelski motor
10.4 Parni stroj

3
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 cHAprER6: The Second Law ofThermodynamics 141

CHAPTER 6
n - Iil- or heathasbeenconvertedcompletelyinto work. This process,
'lrruotu.r
how-
Y,-l a changeof stateof the gas. The'volumeincreases and the
::"G decreases until atmosphericpressureis reached,at which point the
The SecondLaw of Thermodvnami llllrr1,"pr. Therefore,
the piocessof isothermalexpansioncannotbe used
indefinitelY' in which a systemis broughtback
what rs neeoeors a serresof processes
,^ ;r.'initiul state, that is,a cycle. Each of the processes that constitutea cycle
,'iuJu.t either the performance of work or a flow of heat betweenthe system
','nJit, a highertemperature
rut.oundings,whichconsistof a heat reservoir at
reservoir") and a heat reservoirat a
ifru'o,t system1i "trigtr+emperature
" the system (a "low-temperature reservoir")' For one
ioirt t.*i..ature than
cornPlete cYcle, let
'
the symbollQpl representthe heat exchangedbetweenthe high-tempera-
ture reservoirand the sYstem;
the symbol lQll representthe heat exchangedbetweenthe low-tempera-
ture reservoirand the sYstem;and
6.1 the symbollIZl representthe work exchangedbetweenthe systemand the
CONVERSION OF WORK INTO HEAT AND VICE VERSA surroundings.

Att thr.. quantitieslQnl,lQrl, andlwl, areexpressed asabsolutevalues,that

when two stonesare rubbedtogetherunder water,the work doneagainsttJ positivi numbers only. in ait ctrapters of this book, except this chapterand
i.
'iln
force of friction is transformedinto internal energytending to producea ri n r, one, the symbols Q and VI/ arc algebraic quantities that may take on
of temperatureof the stones.As soon as the temperatureof the stones positiveor negativevalues.In thesetwo chapters,we shall deal with engines
andrefrigerators,so we shallknow at all times the directionof flow of Q and
above that of the surrounding water, however, there is heating of the water.
the mass of water is large enough, then there will be no appreciable rise the absolutevaluesof Q and W'
temperature, and thewatercan be regardedasa heatreservoir,asdiscussed ' .W and*. ut interestedonly in
i It lQul is larger than lQTl and if lvl is done by the system,then the
sec.4.l0.Sincethe stateofthe stonesis the sameat the end ofthe process as' nactrineitrat cauies the system to undergo the cycleis called a heat engine'
at the beginning,the net result of the processis merely the conversionof Th, purpor. of a heat .ngitt" is to deliver work continuouslyto the surround-
mechanicalwork into heat.Similarly,when an electriccurrent is maintained ingsty performingthe sime cycleover and over again'The net work in the
in a resistorimmersedeitherin runningwater or in a very largemassof wate{ .uil. is the output,andtheheaiabsorbedfrom the high-temperature reservoir
thereis alsoa conversionof electricalwork into heat, without any changein by rii
systemis
ttresystem input. The
the lnpul. thermalefficiency
LAe tttr of the engine, symbolized
,i1uy by the ls tne
the thermodynamiccoordinatesof the wire. In general,work of any kind II( i

may be doneon a systemin contactwith a reservoir,causingheate to leavri , I (Greekletter eta), is de{inedas il

the systemwithout alteringthe stateof the system.The systemactsmerelyas work outPut

an intermediary.It is apparentfrom the first law that the work is equalto the Thermalefliciency:
l.ut irrpua,
heat, W : Q; in otherwords,the transformationof work into heafis accom-
plished with 100 percentefliciency.Moreover, this transformationcan be lwl
continuedindefinitely. ': re;l' (6.1)

To study the oppositeprocess,namely,the conversionof heat into work,

we mustalsohaveat handa process,or seriesof processes, by meansof which wherelwl and lQsl aremeaasuredin joules. Applying the first law to one
sucha conversionmay continueindefinitelywithout involving any resulting completecycle,rememberingthat thereis no changeof internalenergy'we get
changesin the stateof the system.At first thought, it might appearthat thi
isothermalexpansionof an idealgasmight be a suitablep.ocesJtoconsiderin l Q n-l l Q d : l w l ,
discussingthe conversionof heat into work. In this case,there is no change
of internal energy,sincethe temperatureremainsconstant,and, therefore, and.therefore.
l Q u l - l Q t,l
,t -- --
leul
 142 PARTI:Fundamental ConcePts
,:t- (6.2\
wQ{l
It is seenfrom this equationthat 17will be unity (efficiency100percent)if
Q7 is zero-In other words,if an enginecould be buiit to opeiatein a cyclein
which there is no outflow of heat from the working substanceto the low-
temperaturereservoir,then there would be 100 percentconversionof heat
from
_theligh-temperature reservoir into work. But, as we shall see in
Sec.6.6, there must alwaysbe an outflow of heat from an engine,so the
effrciencyof a heat engineis alwayslessthan 100percent.
The transformationof heatinto work is usuallyaccomplished, in practice,
uv ty.o generaltypesof heatengine:theinternal-combustioi engrre,suchas the
gasolineengineand the dieselengine;and the external-combuslion engine,such
asthe s.team engineand the Stirlingengine.In both typesof heat u gu,
or a mixture of gasesis containedin the spacebetweena cylinderlclosed
"ng'i.r", at
one end, and a piston. The gas in the confined spaceis the system,which
undergoesa cycle,therebycausinga reciprocatingpistott to imiart a motion
of rotation to a shaft,whichactsagainstin oppoJingforce.It is necessary,
in
all engines,that the gasin the confinedspace,at sometime in the cycli,
be
raisedlo a high temperatureand a high pressure,the pressureproviding the
forcethat performsexternalwork. In the gasolineand diesel
the rapid
"confined
burning of the fuel and oxygenfrom the air tukesplacein the "ngin"r, spice
calledthe combustion chamber,-thereby raising the temperatureand pd;;;
of the system.In the steamand stirling engiries,the increasein temperature
and pressureof the gas is accomplisGdbt high-temperaturesuiroundings
that transferheat to the systeminiide the clamb"r.
6.2
TIIE GASOLINE ENGINE
In the gasolineengine,the cycleinvolvesthe performanceof six processes,
four of which requireverticalmotion of the piiton and are calleditrokes:
l. Intake stroke. The systemis a mixture of gasolinevapor and air, which
moves.intothe cylinderdue to suctionas thi recediogpirton enlargesthe
accessible volume.The outsidepressureis greaterttrai ihe pressurein the
cylinder,so the mixture is pushedinto theiombustion chamber.
2. compression stroke.. The mixture of gasolinevapor and air is compressed
until its pressureand temperaturerise considera-bly.This is uccomplished
b-vth9 advancingpiston, which decreases the volume of the combustion
chamber.
3. combustion. Burning of the hot mixture occursvery rapidly after ignition
by an electricspark.The resultingcombustionproductsattain a veiy high
pressureand temperature,but the volume remainsunchangedduring
this
cHAprER6: The Second Law ofThermodvnamics 143
very short time interval.The pistonremainsessentiallymotionless during
this very rapid process.
4. Powerstroke. The hot combustionproductsexpandand pushthe piston
away,thusincreasingthe volumeand decreasing the pressureand tempera-
ture. The system,acting through the piston, performs work on the sur-
roundings(crankshaft,transmission, etc.).
5. Exhaust. The combustion products at theendof the powerstrokearestill
at a higher pressureand temperaturethan the surroundings.An exhaust
valveallows somegasto escapeuntil the pressuredrops almostto atmo-
sphericpressure. Thepistonremainsessentiallymotionlessduringthispro-
cess.
6. Exhauststroke. The piston pushesalmostall the remainingcombustion
productsout ofthe cylinderby exertinga pressuresignificantlylargerthan
atmosphericpressure.
In the aboveprocesses, thereare severalphenomenathat renderan exact
mathematicalanalysisquite difficult. Among theseare friction, turbulence,
lossof heatby conduction,and the chemicalreactionbetweengasolinevapor
andoxygen.A drasticbut usefulsimplificationis providedby neglectingthese
troublesomeeffects.When this is done,we havean idealizedgasolineengine
that performsa cycleknown as an Otto cycle.The cycle is namedafter the
GermanengineerNikolausOtto for his inventionin 1876,but the ideafor a
four-strokeenginecamefrom the FrenchmanAlphonse Beaude Rochasin
t862.
The behaviorof a gasolineenginecan be approximatedby assuminga set
of idealconditionsas follows:(l) the working substance is at all timesair,
whichbehaveslike an idealgaswith constantheatcapacities;(2) all processes
are quasi-static;(3) thereis no friction or turbulence;(4) there is no loss of
heatthrough the walls of the combustionchamber;and (5) the processes are
reversible.Theseassumptionsthen lead to the idealizedair-standardOtto
cycle,which is composedof six simpleprocesses of an ideal gas;thesepro-
cessesare plotted on a PV diagram in Fig. 6-l and describedbelow.
Process5 -- I representsa quasi-staticintake stroke, isobaricat atmo-
sphericpressure.The volumeof the combustionchambervariesfrom zero to
h as the numberof molesvariesfrom zeroto n, accordingto the equation
PsV : nRT1,
wherePs is atmosphericpressureand ?'1is the temperatureof the outsideair.
ProcessI ---+2 representsa quasi-static,adiabatic compressionstroke.
Thereis no friction, and no loss of heat through the cylinderwall. The tem-
peraturerisesfrom the ambient T1 to 72, accordingto the equation
rt4-t : Tz4-1,
144 PARrI: Fundamental Concepts 6: The SecondLaw of Thermodynamics 145
cHAprER

PressureP The two isobaric pro@ssesJ + I and I ---+5 obviously cancel each other
and need not be consideredfurther. Of the four remaining processes,only two
involve a flow of heat. There is an absorptionof lQnl units of heat at high
tenperatures from 2 * 3, and a rejection of lQrl units of heat at lower tem-
Deratures
' from 4 ---+l, as indicated in Fig. 6-l'
Assuming Cy to be constant along the line 2 * 3, we find for heat enter-
ing the system,

lQnl :r; Cv dT : Cv(Tz - Tz).

Similarly,for process4-. I, we find for heatleavingthe system,

lTr
- Tr)'
lQtl: -
FIGUREGI dr : Cv(T+
Y2 l/r IdealizedOtto cyclefor gasoline )r,"
Volume Z enginesshownon a PV diagram.
is, therefore,
Thethermalefficiency
Tq-Tr
'', , : ''| - l Q d ' (6.3)
where tr! is the larger volume when the piston is at the bottom of the com- lQnl rt - Tz
pressionstrokeand Z2 the smallervolumewhen the piston is at the top. The
ratio of heat capacitiesis assumedto be constant. during the compressionstrokeand powerstroke
Thetwo adiabaticprocesses
Process2 -' 3 representsa quasi-staticisochoricincreaseof temperature are given bY
and pressureof n molesof air, imaginedto be broughtabout by an absorption rr4-' : Tzvl-',
of heat lQyl from a seriesof external high-temperaturereservoirswhose
temperaturesrange from T2 to 7]3.If there were only one reservoirat the and ro4-' : Ttv]-t,
temperature13, then the flow of heat would not be quasi-static,because
which yield, after division,
there would be a substantialdifferencein temperaturebetweenthe system
apd the singlereservoirat 7:3.This processis meantto approximatethe effect T1 T2
-: -. (6.4)
of the combustionin a gasolineenginewhen the piston is essentiallymotion- Ta, Tz
lessat the top of the stroke.
Changesignsand add unity to obtain
ProcessI ---+4 representsa quasi-staticadiabaticpowerstroke,involving a i:

drop in temperaturefrom T3 to Ta, accordingto the equation Tc-Tr Tt-Tz

iI4:m'
rt4-t : Tq4-t,
T+- Tr Ta
where Z1 is larger than V2.This processrepresentsthe power stroke.
Process4 -' I represents a quasi-staticisochoricdrop in temperatureand Combinethis resultwith Eq. (6.4)and Eq. (6.3)to obtain the thermaleffi-
pressureof n molesof air, broughtabout by a rejectionof heat lQr,l to a series ciency4 of an idealizedgasolineengine,
of low-temperature externalreservoirsrangingin temperaturefrom Ta to 71,
where T1 is the temperatureof the outside air. This processis meant to q : r -, 8
7 1, (6.s)
approximatethe drop to atmosphericpressureupon opening the exhaust
valve,but, in reality, the temperaturedoesnot actuallydrop to the tempera- where I1 and T2 are the temperatures at the beginning and end of the com-
ture of the outsideair as it leavesthe exhaustport. pression stroke. This is the most important expression in connection with the
Process1 -* 5 representsa quasi-staticexhauststroke,isobaricat atmo- gasoline engine. It shows that the thermal efficiency of a gasoline engine
sphericpressure.The volumevariesfrom Vt to zeroasthe numberof molesof working in the Otto cycle depends on the temperature before and after com-
exhaustgasvariesfrom n to zero,the temperatureremainingconstantat the pression.[n a gasolineenginewith temperaturesZ1 : 300K and T2: 580K,
valueZ. the efficiency is 48 percent.
 cHAprER6: The Second Law of Thermodynamics l4'1
146 PARTI:FundamentalConcePts

PressureP
This is the optimum efficiency for a gasoline engine operating in an idea-
lized quasi-static Otto cycle for the temperatures cited. All the troublesome
effects present in an actual gasoline engine, such as friction, turbulence, and
heat conduction through the engine walls, are such that they make the effi-
ciency much lower than that of the idealized Otto cycle. The actual operating
thermal efficiency of a gasoline engine is in the range of 20-30 percent.

6.3
THE DIESEL ENGINE
FIGURE 62
In the dieselengine,only air is admittedon the intake stroke.The air is Idealized Diesel cycle for oil-
compressed adiabaticallyuntil the temperatureis high enoughto ignite oil Y, frred enginesshown on a PIl
that is sprayedinto the cylinder after the compression.The rate of supply of VolumeZ diagram.
oil is adjustedso that combustiontakesplaceapproximatelyisobarically,the
piston moving out during combustion.The rest of the cycle,namely,power
stroke,exhaust,and exhauststroke, is exactly the sameas in the gasoline l(r]-l) T1
engine.The usual troublesomeeffectstake place in the dieselengineas in T t : t. - l 1 r r : q ' Z 2 , (6.6)
thegasolineengine.Eliminatingtheseeffectsby makingthe sameassumptions
as before,we are left with an idealizeddieselenginethat performs a cycle is
wherethe expansionratio rs (also called the "cutoffratio" in engineering)
known as the air-standardDieselcycle,namedafter Rudolf Dieselwho con- givenby
structedthe first successful dieselengineusingliquid fuel in 1897.If the line Yt
2 - 3 in Fig. 6-l is imaginedhorizontalinsteadof vertical,the resultingcycle rz:
is shownin Fig. 6-2. Vs
The line 2 -- 3 in Fig. 6-2 representsthe quasi-staticisobaricabsorption and Tr and T2are the temperaturesat the beginningand end of the compres-
of heatfrom a seriesof externalreservoirsrangingin temperaturefrom Z2 to sion stroke, respectively.Interestingly, the efliciency of the Diesel cycle
?n3. This proc€ssis meantto approximatethe isobaricburning of the oil. All expressedin Eq. (6.6)doesnot dependon the compression ratio rs givenby
the othercurveshavethe samemeaningasin the caseof the air-standardOtto
Vt
cycle. ,c :
AssumingCp to be constantalong the line 2 -- 3, we get vz
tTt
tE:5, ''l:1.4, ?"r: 300K,andT2:990K' we
Taking,for example,
lQnl: I crar : Cr(Tt_ Tz), obtain
Jrz
, (5t'4- l) 3ooK
and, as in the caseof the Otto cycle,
Tt:r-na(s:T ee0K
: 54 percent.
lQrl: Cv(74- Tt).
Therefore,the thermalefhciencyof an idealizeddieselengineis given by The thermal efficienciesof actual dieselenginesare, of course,lower, for the
reasonsmentionedin connectionwith the gasolineengine,typically being in
t(74-Tt) the rangeof 3G-35percent.
,. -r t : ir _
In ihe dieseletrginejust considered,four strokesof the piston are needed
17.:Tj
for the completionof a Cycle,and only one of the four is a powerstroke'Since
Notice that, unlike the thermal efficiency of the Otto cycle expressedin only air is iompressedin the diesel engine,it is possibleto eliminatethe
Eq. (6-3), the efficiencyof the Diesel cycle dependsupon 7, the ratio of exhiust and intike strokesand thus completethe cycle in two strokes.In
heatcapacities.This expressionmay be transformedinto the two-stroke-cycle dieselengine,every other stroke is a power stroke,and
 148 peitrt: Fundamental
ConcePts cHAprER6: The Second Law of Thermodynamics 149

thusthe poweris doubled.The principleis very simple:At the conclusionof

the power stroke,whenthe cylinderis full of combustionproducts,the valve
opens,exhausttakesplaceuntil the combustionproductsare at atmospheric
pressur€,and,then,insteadof usingthepistonitselfto exhaustthe remiining lQul
-\r,
gases,freshair is blowninto thecylinder,replacingthe combustionproducts.
A blower,operatedby the engineitself, is usedfor this purpose,and thus it
accomplishes in one simpleoperationwhat formerlyrequiredtwo separate
pistonstrokes.

Feed-water
6.4 pumP
THE STEAM ENGINE

The steamengineis historicallyquite important,because it wasthe hrst engine

drivenby heat,ratherthan animals,water,or wind. The initial function of the
steamenginewasto pump water out of minesin England.The first practical
and safesteamengine,a reciprocatingpiston-+ylinderdevice,wasinvinted by
ThomasNewcomenin l7l2 and had the greatestimpactin bringingabout th! FIGURE63(a)
IndustrialRevolution.Jameswatt greatlyimprovedthe steame-ngine in 1j64, diagramof a simplesteam
Schematic
and william Rankinewas the first to describethe thermodynamiccyclefor engine.
adiabaticsteamenginesin 1859.currently, steamenginesarl usedin electric
power plants,and in nuclear-powered aircraft carriersand submarines.
- _A rjlt.-atic diagram of an elementary steamengineis shown in Fig.
6'3(a).The operationof suchan enginecan be undersloodby following the
pressure and volumechangesof a smallconstantmassof wateras it ision-
veyedfrom the condenser,through the boiler, into the expansionchamber,
and back to the condenser.The water in the condenseris at a pressureless
than atmosphericand at a temperaturelessthan the normal boiling point. By PressureP
meansof a pump, it is introducedinto the boiler, which is at a muitr highei
pressureand temperature.In the boiler, the water is first heatedto its boiiing
point_andthen vaporized,both processes taking placeapproximatelyat con-
stanthigh pressure.The steamis thenraisedto a temperituregreateithan the
normal boiling point at the samepressure.It is then allowed to flow into a
cylinder,whereit expandsapproximatelyadiabaticallyagainsta piston or a
set of turbine blades,until its pressureand temperaturedrop to ihat of the TTGURE C3(D)
condenser. In the condenser,finally, the steamcondenses PV diagram of the Rankine cYcle
intoihe waterat the
sametemperatureand pressureasat the beginning,and the cycleis complete. for a steam engine.ProcessI + 2
is not an isochoric comPressionof
- In the actual operationof the steamengine,there are slveral processes steam,but an adiabatic
that renderan exactanalysisdiffrcult: turbulencecausedby the pressuredif-
compressionof water, which Yields
ferencerequiredto causethe flow ofthe steamfrom onepuit of the apparatus
a nearly vertical line. Process3 - 4
to another,friction, conductionof heatthrough thewa[J during expansionof is an adiabatic expansionof steam'
the steam,and heat transfersdue to a finite temperaturedifferenie between For more detail, seeFig- 7-2.
Volume /
the furnaceand the boiler.
, A first approximationto the discussionof the steamenginemay be made
by introducingsomesimplifyingassumptionswhich, althou-ghin no way rea-
lizablein practice,provide at leastan upper limit to the eficiency of sucha