HowEnthalpyandEntropyChangewithPressureandTemperature

References
J.M.Smith,H.C.van-Ness,M.M.Abbott,`IntroductiontoChemicalEngineeringThermodynamics`,
McGraw-Hill,5thEdition1996,Chapters3,6
 HowEnthalpyChangeswithTemperatureandPressure

Temperature Enthalpy
changeon
vapourisation
vapour

liquid
Enthalpy

saturationline

Pressure
 EnthalpyChangeswhenHeatisAddedtoaSystem

A-B-sensibleheatingofthe
T liquid.
D
C B-C-evaporationofthe
B
liquidtoavapour
(latentheating)
Enthalpy
A
C-D-sensibleheatingofthe
vapour/gas
P
 EnthalpyChangeswhenWorkisdoneonaSystem

Whenasubstancehasworkdone
T onit,bothpressureand
E temperaturechange.
D F
C

A-BPumpingofaliquid,small
Enthalpy A changeinT,nochangein
B volume.

C-DCompressionofagas,P,T
P andvolumechange.

E-FExpansionofagasina
turbine
 HowEnthalpyChangeswithTemperatureandPressure

FromThermodynamictheoryitispossibletoshowthatEnthalpy(H)
changeswithtemperatureandpressureaccordingtotheequation.

È Ê ∂v ˆ ˘
dH = CP dT + Ív - T Á ˜ ˙dP
Î Ë ∂T ¯P ˚

Havetoknowheatcapacityofthefluid(Cp)andhowthevolume,
pressureandtemperatureofthefluidarerelated.
†

Liquidsaregenerallyassumedtobeincompressible,sotheirenthalpy
doesnotchangewithpressure.

Foragasthereanumberofwaysofrepresentingtherelationship
betweenpressure,volumeandtemperature.
 RelationshipsbetweenPressure,VolumeandTemperatureforaGas

AllrelationshipsbetweenP,VandTforasubstancearecalledan
equationofstate.

Forgasesupto500kPa(5timesatmosphericpressure)weusethe
idealgaslaw.

RT
Pn =
M

whereRiscalledthegasconstant(8.314Jmol-1K-1)andMiscalled
themolarmass,itsunitsarekgmol-1(waterhasamolarmassof
†
0.018kgmol-1).

ThepressureisinPa,thevolumeisinm3kg-1andthetemperatureis
inKelvin
 RelationshipsbetweenPressure,VolumeandTemperatureforaGas

Forpressuresupto2000kPa,weusedamodifiedversionoftheIdealgas
law,calledtheVirialequationofstate.

RT B
v= +
PM M

Biscalledthesecondvirialcoefficient,andisacorrectionfactortoaccount
forattractiveforcesbetweengasmolecules.Itsunitsarem3mol-1
†

Forhigherpressuresweusecubicequationsofstatewhichhavethegeneral
form
È RT aM ˘
P = MÍ - ˙
Î n - b T n (n - b )˚

aandbareconstants,equationalsopredictsliquidvolumes
†
 ExampleofCalculatingtheEnthalpyChange

5kgofwateraretobeheatedandcompressedfrom298Kand101300
Pa,toformavapourat450Kand600000Pa.
Data
At298Kand101300Pa,theEnthalpyofthevapouris1587944Jkg-1.

Theheatcapacityoftheliquidisgivenby Cp = 4024 + 0.577T (Jkg-1K-1)

Theheatofevaporationat373Kand101300Pais2256900Jkg-1
†
Theheatcapacityofthevapourisgivenby Cp = 1602.7 + 0.670T (Jkg-1K-1)
Heatcapacityofvapourisvalidat101300Pa

Thevirialcoefficientanditsderivativewithrespecttotemperatureare
†
∂B
B = -2.187¥10-4 m3mol-1 = -1.276 ¥10-6 m3mol-1K-1
∂T

†
 T

alternativepath

actualpath

Thealternativepathconsistsofconstantpressureheatingandconstant
temperaturecompression
 ExampleofCalculatingtheEnthalpyChange
Wedothiscalculationdoingtheheatingatconstantpressure,andthenthe
compressionatconstanttemperature.
Constantpressureheatingat101300Pa
Threestages.Heatingtheliquid,evaporatingandheatingthevapour

sensibleheatingoftheliquid
373 373
DH l = Ú Cpliq dT = Ú 4024 + 0.577T dT = 316.3 kJ kg-1
298 298

evaporation
† DH v = 2256.9 kJ kg -1

sensibleheatingofthevapour
† 450
DH g = Ú 1602.7 + 0.670T dT =144.6 kJ kg -1
373

†
 ExampleofCalculatingtheEnthalpyChange
ForCompression
È Ê ∂n ˆ ˘
dH = Ín - T Á ˜ ˙dP
Î Ë ∂T ¯P ˚

Usingthevirialequationofstate
† 1 Ê RT ˆ Ê ∂n ˆ 1 Ê R ∂B ˆ
n= Á + B˜ Á ˜ = Á + ˜
MË P ¯ Ë∂T ¯P M Ë P ∂T ¯

and
† Ê ∂v ˆ 1 Ê RT
† RT ∂B ˆ 1 Ê ∂B ˆ
n - TÁ ˜ = Á + B- - T ˜ = ÁB - T ˜
Ë ∂T ¯P M Ë P P ∂T ¯ M Ë ∂T ¯

sothat
† 1Ê ∂B ˆ600000
DH c = Á B - T ˜ Ú dP = 9849 J kg-1
MË ∂T ¯101300

Enthalpy=5x(1587944+316319+2256900+144637+9849)=21578245J
†
HowEntropyChangeswithTemperatureandPressure

Temperature

Entropy

Pressure
 How Entropy Changes with Temperature and Pressure

TheEntropychangeswithtemperatureandpressureaccordingto

CP Ê ∂n ˆ
dS = dT - Á ˜ dP
T Ë ∂T ¯P

Asforenthalpy,thespecificheatcapacityandarelationshipbetween
Pressure,VolumeandTemperaturearerequired.
†

Example
Calculatetheentropyof5kgwaterat450Kand600000Paifthe
entropyofwaterat298Kand101300Pais9079Jkg-1K-1

Usethedatagivenpreviously
 How Entropy Changes with Temperature and Pressure
Thecalculationiscarriedoutinthesamewayasthatfortheenthalpy,thatisto
say:
1.Heatthewatertoit’sboilingpointof373Kat101.3kPa
2.Vapourisethewaterat373Kand101.3kPa
3.Heatthevapourto450Kat101.3kPa
4.Compressthevapourto600kPa.

1.Heatthewaterto373K
Thespecificheatcapacityofthewaterisgivenby Cp = 4024 + 0.577T (Jkg-1K-1)
Theentropychangeonheatingisgivenby DS = Ú CP dT .
T
†
373 373
4024 + 0.577T 4024 373
DS = Ú dT = Ú + 0.577dT = [ 4024 ln T + 0.577T ]298 = 946.6 J kg -1 K -1
298 T 298 T
†

†
 How Entropy Changes with Temperature and Pressure

2.VapouriseTheWaterat373K
Theentropychangeforvapourisationisfoundbydividingtheenthalpychange
bythetemperature.
DH V 2256900
DSV = = = 6050.7 J kg -1 K-1
T 373

3.HeatTheWaterVapourto450K
†
Theheatcapacityofthewatervapourisgivenby Cp = 1602.7 + 0.670T (Jkg-1K-1)
Theentropychangeonheatingisgivenby DS = Ú CP dT .
T
450 450
1602.7 + 0.670T 1602.7 450
DS = Ú dT = Ú = [1602.7 lnT + 0.670T ] 373 = 352.4 J kg -1 K -1
+ 0.670dT †
373 T 373 T
†

†
 How Entropy Changes with Temperature and Pressure

4.CompressTheWaterVapourto600kPa
Forentropychangeswithpressure DS = - Ú ÊÁ ∂n ˆ˜ dP
Ë ∂T ¯P
ForagasthatobeystheVirialequationofstate ÊÁ ∂n ˆ˜
1 Ê R ∂B ˆ
=
Á + ˜
Ë∂T ¯P M Ë P ∂T ¯
Carryingouttheintegration(R-gasconstant=8.314Jmol
† -1K-1)
1 600000 Ê R ∂B ˆ 1 Ê Ê 600000 ˆ -6 ˆ
DS = - Ú Á + ˜dP = - 0.018 ÁË R lnÁË 101300 ˜ -1.276 ¥10 (600000 -101300) ˜
M 101300 Ë P ∂T ¯ †¯ ¯
DS = -786.3 J kg-1 K-1

†
† Summingtheentropychangesforallthesteps,wefindthattheentropyof
watervapourat450Kand600kPa
=5x(9079+946.6+6050.7+352.4-786.3)=78212JK-1
 Mixture Properties

•Inthechemicalindustrywearealwaysdealingwithmixturesthatcontain
morethanonechemicalspecies(e.g.saltandwater,oil)

•Anidealmixtureisdefinedasfollows:

-Inthegasphaseitisonewheretherearenointeractionforces
betweenatoms/moleculesinthemixture(becausetheyarealong
wayapart).

-Intheliquidandsolidphasesitisonewheretheinteractionforces
betweentheatoms/moleculesinthemixtureareassumedtobethe
same(becausetheyareclosetogether).
 Mixture Properties
•Foridealmixturestheenthalpy(H)andentropy(S)aregivenbyequations

1and2.

liquid+solid gas
n n
o o
H mix = Â xi H i,T H mix = Â yi H i,T .......(1)
i=1 i=1

n n È o
o Ê y P ˆ˘
Smix = Â [
xi Si,T + R ln xi ] Smix = Â yi ÍSi,T + R lnÁ i o ˜˙ .......(2)
† i=1
† i=1 Î
Ë P ¯˚

† n -numberofcomponentsinthemixture
† xi yi -molefractionofcomponentnumberiinthemixture
P-Pressureofthemixture P o=standardpressure(101325Pa)
T -Temperatureofthemixture
o
† H i,T -enthalpyofpurecomponentnumberiatstandardpressureandthetemperatureofthemixture.
†
o
† Si,T -enthalpyofpurecomponentnumberiatstandardpressureandthetemperatureofthemixture.
†
†
†
 Mole Fractions
• Amolefractionisdefinedasfollows:
number of mole of component i
mole fraction =
total number of moles

Example
Findthemolefractionsofwater,methanolandethanolin10kgofamixture
†
withthefollowingcomposition:42mass%water,37mass%methanol,21
mass%ethanol.

MolarMasses: water=0.018kgmol-1
methanol=0.032kgmol-1
ethanol=0.045kgmol-1
 Mixture Example
•Findtheenthalpyandentropyofamixtureofcontaining59.0mol%water,
29.2%methanoland11.8mole%ethanolat331K(58˚C)and101.3kPa.

Data
At298K(25˚C)theenthalpiesandentropiesofpurewater,methanoland
ethanolare:
o o
water: H 298 =1649Jmol-1 S298 =5.8Jmol-1K-1
o o
methanol: H 298 =1930Jmol-1 S298 =6.8Jmol-1K-1
o o
ethanol: H 298 =2756Jmol-1 S298 =9.7Jmol-1K-1
† †
Thespecificheatcapacitiesare:
† †
water: -1
75.3Jmol K -1
† †
methanol: -1
77.2Jmol K -1
ethanol: 110.2Jmol-1K-1
 Mixture Properties
•Fornon-idealmixturestheenthalpy(H)andentropy(S)aregivenbyequations

1and2.

liquid+solid gas
n n
o o
H mix = Â xi H i,T H mix = Â yi H i,T .......(1)
i=1 i=1

n n È o
o Ê y P ˆ˘
Smix = Â [
xi Si,T + R ln xi ] Smix = Â yi ÍSi,T + R lnÁ i o ˜˙ .......(2)
† i=1
† i=1 Î
Ë P ¯˚

† n -numberofcomponentsinthemixture
† xi yi -molefractionofcomponentnumberiinthemixture
P-Pressureofthemixture P o=standardpressure(101325Pa)
T -Temperatureofthemixture
o
H i,T -enthalpyofpurecomponentnumberiatstandardpressureandthetemperatureofthemixture.
†
o
Si,T -enthalpyofpurecomponentnumberiatstandardpressureandthetemperatureofthemixture.
†