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EAS3603/6140ThermodynamicsofAtmospheresandOceans

Worksheet6Entropy
Reversibleandirreversibleprocesses
1.Circlethefollowingiftheyareirreversibleprocesses
a)Heattransferthroughafinitetemperaturedifference
b)Absorptionofsolarradiation
c)Expansionintoavacuum
d)Infinitesimallyslowexpansionagainstanopposingpressure
2.Listtwoexamplesofirreversibleprocessesintheatmosphere
Precipitation,lightening
Entropy
1.Writethefirstlawofthermodynamics,intensive,enthalpyform,expansionwork.
c p dT dq vdp dq c p dT vdp
2.Forthereversibleexpansionofanidealgas,wemaysubstituteforthespecificvolume
fromtheequationofstate.Makethissubstitutionin#1.Youshouldnowhavean
equationthatisafunctiononlyofq,T,andp,withdqonthelefthandside.
RT
pv RT v
p
RTdp
dq c p dT
p

3.Dividebothsidesoftheequationin#2byT(youshouldgetequation(2.23))
dq
dT Rdp
cp

c p d (ln T ) Rd (ln p )
T
T
p

4.Withtheterminvolvingdqonthelefthandsideoftheequation,thetwotermsonthe
righthandsideoftheequationare(exact,inexact)differentials
exact
5.Thesumoftwoexactdifferentialsis(always,never,sometimes)anexactdifferential
always
6.Thesomeoftwoinexactdifferentialsis(always,never,sometimes)anexactdifferential

sometimes
From #4-5 above, it is clear that dq/T is an exact differential for reversible processes
dq
T

rev

=0

where the subscript rev emphasizes that this relationship holds only for a reversible process.
Dividing heat by temperature thus converts the inexact differential dq into an exact differential.
dq

We can now define a new thermodynamic state function, the entropy, to be d = T

rev

It is important to remember that entropy is defined so that the change in entropy from one state to
another is associated with a reversible process connecting the two states.
When a change in entropy between two given states occurs via an irreversible process, the change
in entropy is exactly the same as for a reversible process: this is a consequence of entropy being
a state variable and d an exact differential, which means that integration of d does not depend
on the path (reversible or irreversible). Although the change in entropy is exactly the same for
reversible and irreversible processes that have the same initial and final states, dq/T is not the
same for reversible and irreversible processes. To accomplish a given change in entropy (or state)
by an irreversible process, more heat is required than when a reversible process is involved. This
implies that reversible processes are more efficient than irreversible processes.

7.Duringacyclic,reversibleprocess,entropy(increases,decreases,remainsthesame)
remainsthesame
8.Irreversibilitiesinasystemcauseentropyto(increase,decrease,remainthesame)
increase
9.Asystemundergoesaprocessbetweentwofixedstatesfirstinareversiblemanner
andtheninanirreversiblemanner.Forwhichcaseistheentropychangeofthesystem
greater?Why?
Itisgreaterfortheirreversiblemannerbecauseentropymustalwaysincreasein
thiscase
10.Isthevalueoftheintegral12dq/Tthesameforallprocessesbetweenstates1and2?
Explain
No,becauseirreversibleprocessesarepathdependent
11.Isthevalueoftheintegral12dq/Tthesameforallreversibleprocessesbetween
states1and2?
Yes,becauseinthiscasethepathdoesnotmatter
12.Todeterminetheentropychangeforanirreversibleprocessesbetweenstates1and2,
shouldtheintegral12dq/Tbeperformedalongtheactualprocesspathoranimaginary
reversiblepath?Explain
Itshouldbeperformedalonganimaginaryreversiblepathorsegmentsbecause
thisallowsthepropercalculationasanexactdifferential

13.Howdoesthevalueoftheintegral12dq/Tcompareforareversibleandirreversible
processbetweenthesameendstates?
reversible>irreversible
14.Isitpossibletocreateentropy?Isitpossibletodestroyit?
YesandNo,entropycanonlybecreated,neverdestroyed
15.Isitpossiblefortheentropychangeofaclosedsystemtobezeroduringan
irreversibleprocess?Explain
Thefactthatitisanirreversibleprocessthetotalentropymustbe>0
15a.Entropyisanexactdifferential(true,false)
true
15b.If>0,theprocessis(never,sometimes,always)irreversible
sometimes
15c.
4.

dq
T

rev

istruefor(irreversible,reversible,both)processes
both
16.Fromtheequationyouderivedin#3,writetheexpressionforentropychangeforan
idealgasinenthalpyform(youshouldget(2.26b))
dq
d c p d (ln T ) Rd (ln p )
T
Wenowwouldliketoderivetheentropychangeequationforanidealgasininternal
energyform.#17#19
17.Writethefirstlawofthermodynamics,intensive,internalenergyform,expansion
work.
cv dT dq pdv dq cv dT pdv
18.Forthereversibleexpansionofanidealgas,wemaysubstituteforthepressurefrom
theequationofstate.Makethissubstitutionin#17.Youshouldnowhaveanequation
thatisafunctiononlyofq,T,andv,withdqonthelefthandside.

pv RT

RT
v

RTdv
v
19.From#18,writeanexpressionfortheentropychangeofanidealgas.
dq
dT
dv
d c p
R
T
T
v
dq c p dT

Usetheexpressionsin#16and#19forentropychangetoanswerthefollowingquestions
23. Entropywill(increase,decrease,remainthesame)inacyclicreversibleadiabatic
process
remainthesame
24.Entropywill(increase,decrease,remainthesame)forisobariccooling
decrease
25.Entropywill(increase,decrease,remainthesame)forisothermalexpansion
increase
27.ConsidertheisobaricheatingofairfromT=300KtoT=400K.Whatistheentropy
changeforthisprocess?
T2
400
4
T1 c p d (ln T ) c p ln( 300 ) c p ln( 3 )
28.Ahotpotatocoolsbyheattransfertothecoolerair.
a)Doesentropyofthepotatoincreaseordecreaseinthisprocess?decrease
b)Doestheentropyoftheuniverseincreaseordecreaseinthisprocess?increase

29.Considerthesystempicturedbelow:

GasisconfinedtoasubvolumeV1inaninsulatedrigidcontainer.Thecontainerhasanadjoining
subvolumeV2,initiallyevacuated,whichcanbeconnectedtoV1byopeningavalve(V1=V2).
SupposethevalveisopenedandthegasflowsoutofV1,fillingtheentirevolume,V1+V2.
a)Theworkdonebythegasinthisexpansionis(positive,negative,zero).zero

b) Theinternalenergyofthegasaftertheexpansion(increases,decreases,remainsthesame).
remainsthesame
c)Theentropyofthegasaftertheexpansion(increases,decreases,remainsthesame).increase
d)Isthisprocessadiabatic?YESNO
Yes
e)Isthisprocessreversible?YESNO
No

2ndLawofThermodynamics
1.Ifeachbodyhasthesamemassandcomposition(i.e.sameheatcapacity),and
body1hasinitialtemperature40oCandbodytwohasinitialtemperature20oC,what
wouldyouexpectthefinaltemperatureofeachbodytobe?
30C

2.WouldfinaltemperaturesT1f=50oCandT2f=10oCviolatethefirstlawof
thermodynamics?
No
3.Whatwasassumedin#1thatwasnotassumedin#2?
Heatcannotflowspontaneouslyfromcoldtohot
4.Heatcanflowfromacoldsubstancetoawarmersubstance
a)never
b)always
c)onlyifworkisdoneonthesystem
5.Heatflowingfromacoldsubstancetoawarmersubstancewouldviolate
a)1stlawofthermodynamics
b)2ndlawofthermodynamics
c)neitherthe1stor2ndlaw
6.Inarefrigerator,heatistransferredfromalowertemperaturemedium(the
refrigeratedspace)toahighertemperatureone(thekitchenair).Isthisaviolationofthe
secondlawofthermodynamics?Explain

No,becauseworkisdonetoextracttheheatfromtheinternalcasingusingenergy
fromtheenvironment.Thesecombinedmakeupthewholesystem.

7.Considerapersonwhoorganizeshisroom,andthusdecreasestheentropyofthe
room.Doesthisprocessviolatethesecondlawofthermodynamics?
No,roomisnotanisolatedsystem

8. In a Carnot cycle, heat is transferred from a hot reservoir at T2, partly converted to
work, and partly discarded into a cold reservoir at T1. The engine is returned to the initial
state after one cycle. Sketch the Carnot cycle in the T- plane on the diagram below,
labelling T1 and T2, and the steps 1 through 4.
Step 1: isothermal expansion at T2
Step 2: adiabatic expansion to T1
Step 3: isothermal compression at T1
Step 4: adiabatic compression back to T2.
1
T

4
3

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