ThermodynamicsofFlowProcesses

References

J.M.Smith,H.C.VanNess,M.M.Abbot,”IntroductiontoChemical
EngineeringThermodynamics”,McGrawHill,1996,Chapter7.

J.Winnick,“ChemicalEngineeringThermodynamics”,JohnWiley
&Sons,Inc.,1997,Chapters6&7
 Oil&GasProcessingfromtheWelltotheConsumer

heat
exchangers compressor

gas-liquid
Pipeline
separator
Q W
pump Oil
valve Refinery separationdevice
(e.g.distillation,
Q W gasabsorption)

Gas
reservoir
WewanttotodescribehowtheEnthalpy
andEntropychangethroughthesedevices
 FlowThroughProcessEquipment

•ForthefollowingitemsofProcessEquipment
-HeatExchangers
-Pumps
-Compressors/Expanders(Turbines)
-Valves

wecanestablishtheprinciplesthatdescribehowEnthalpyandEntropychange
asliquid/gasflowthroughthem.

•Theseprincipalsarevalidforbothpuresubstancesandmulti-component
mixtures.

•Thebasisofourcalculationsisacombinationoftheenergyandentropy
balanceswiththeequationsthattellushowHandSchangewithTandP
 EnergyBalance

Fluidin Fluidout
P1,T1,u1,z1,H1 P2,T2,u2,z2,H2
P=pressure
T=temperature
u=velocity
z=height Q W
H=enthalpy

Balancethekineticenergy,potentialenergyandenthalpychangeswith
theheattransferredandtheworkdone.
˙ ( H 2 + z2 g + 12 u22 ) = m˙ ( H1 + z1g + 12 u12 ) + Q + W
m ˙ =massflowrate
m

Forprocessequipmentthechangesinkineticandpotentialaresmalland
†
generallyignored.Theenergybalancebecomes:
†

˙ H 2 = m˙ H1 + Q + W
m OR m˙ DH = Q + W

† †
HeatExchangers

ShellandTube

Plate
 HeatExchangers

In Out

Q
•Heatexchangersareusedtoaddorremoveheatfromaprocessstream.

•Qiscalledtheheatloadanditsunitsarewatts(W).

•HeatTransferoccursat(almost)constantpressure.

•Theenthalpybalanceforaflowprocessis

˙ DH = m˙ ( H out - H in ) = Q + W
m

• AsnoworkisdoneinaheatexchangerW=0andtheenthalpybalanceis
†
˙ DH = Q
m

†
 HeatExchangers

•AlltheflowprocessescanberepresentedonTemperature-Entropy(TS)
co-ordinates.
Saturation
T line Criticalpoint

liquid vapour

S
vapour-liquid
mixture

S
Takeconstantpressure“slices”andprojectontoTSCoordinates
 HeatExchangers
Temperature
Temperature(K)HKL
500
TSdiagramfor
Refrigerant123
450

oling
g
heatin

liquidco
400
vapourcooling
liquid

andcondensation
350

liquidevaporation
300

250 Entropy
Entropy (kJ kgK- 1-1)K- 1L
kg-1
HkJ
0.2 0.4 0.6 0.8
 HeatExchangers PHdiagramfor
Refrigerant123
4000
Criticalpoint
3500

3000
Pressure (kPa)

2500
Liquid Vapour
2000 evaporation
1500
liquidcooling
1000
vapour
500
heating
0
0 100 200 300
-1
Enthalpy (kJ kg )

Heatexchangeisgenerallyaconstantpressureprocess
 HeatExchangers

•Forconstantpressureheating/coolingtheenthalpyandentropychanges
aregivenbythefollowingequations

Tboil T2
DH = Ú C (liq.)dT
P + DHV + Ú C (vap.)dT
P
T1 Tboil

Tboil T2
CP (liq.) DHV CP ( vap.)
DS = Ú T
dT +
Tboil
+ Ú T
dT
T1 Tboil

sensibleheating evaporation sensibleheating

†
ofliquid ofvapour
 HeatExchangers-Examples
Aflowof1.5kgs-1ofwaterpassesthroughaheatexchangerwhere165kW
ofheatareadded.Calculatethetemperatureofthewaterattheexitofthe
heatexchanger.
Data
TI N=308K(30C) CP =4.21kJkg-1K-1 HIN=158kJkg-1 m=1.5kgs-1
Startwiththeenthalpybalancefortheheatexchanger(inconsistentunits)

mHOUT-mHIN=Q
1.5HOUT-1.5x158=165 fromwhichHOUT=268kJkg-1

UsingtheequationthattellsushowenthalpychangeswithPressureand
Temperature
TOUT TOUT
HOUT = H IN + Ú CP dT = 158 + Ú 4.21dT
TIN 308
268 = 158 + 4.21(TOUT - 308) fi TOUT = 334.1 K
 HeatExchangers-Examples
0.4kgs-1ofEthanolat200kPaareheatedfrom350Ktoproducea
saturatedvapourat370K.Asaturatedvapourisavapourattheboiling
pointofthesubstance.

Calculatetheamountofenergythatmustbetransferredinaheat
exchangertoproducetheethanolvapour.

Data
Heatcapacityofethanol=3270Jkg-1K-1
Heatofvapourisationat370K=931700Jkg-1
 Compressors,ExpandersandPumps

axialflowcompressor

axialflowcompressor

reciprocatingcompressor centrifugalpump
 Compressors,ExpandersandPumps
Compressor Expander Pump
High
Low High High Low Low Pressure
Pressure Pressure Pressure Pressure Pressure

Work Work Work

GasesandVapours Liquids
Inacompressor,expanderorpumpnoheatistransferredtothefluid,only
work.Theenthalpybalancebecomes

˙ DH = m˙ ( H out - H in ) = W
m

Inacompressor,expanderorpumpthepressureandtemperatureofthe
fluidchange.Theseprocessesareirreversibleandwehavetotakethatinto
†
accountindoingcalculations
 Compressors,ExpandersandPumps

Temperature
Temperature(K)HKL
500
TSdiagramfor
Refrigerant123
450

400

expansio
ssion
compre
350

n
pump

300

250 Entropy
Entropy (kJ kgK- 1-1)K- 1L
kg-1
HkJ
0.2 0.4 0.6 0.8
 Compressors,ExpandersandPumps PHdiagramfor
Refrigerant123
4000
Criticalpoint
3500

3000
Pressure (kPa)

2500

2000

pump
1500

r
resso
1000

comp
500

0
0 100 200 300
-1
Enthalpy (kJ kg )
 compressor
Significantgas/vapourheating
occursinacompressor!
outlet
Particularlyiftheefficiencyislow
recycle

inlet
 Compressors,ExpandersandPumps

Totakeaccountoftheirreversibiltiesintheseprocessesweusemeasured
valuesoftheefficiency.

Wisentropic
ForCompressorsandpumps hisentropic =
Typicalvaluesfor hisentropic 
W
forpumps,expandersand
W compressorsareintherange
ForExpanders hisentropic = 0.6-0.9
† Wisentropic †

Theisentropicprocessisareversibleprocesswhichachievesthesamepressure
increase/decreaseastherealone.
†

Itiscalledisentropicbecausetheentropyofthegasenteringtheprocessis
equaltotheentropyofthegasleavingtheprocess.
 CompressorExample

0.5kgs-1ofpropaneat298Kand101.3kPaarecompressedto500kPa
inacompressorwithanisentropicefficiencyof80%.Thegasobeysthe
Virialequationofstate.Calculate
(1)TheWorkdoneduringcompression.
(2)Thetemperatureofthegasaftercompression.

Data
RT B
V= + M = 0.044 kg mol-1
PM M

B 1 ∂B
= -3.07¥10-3 m3 kg-1† = 2.07 ¥10-5 m3 kg-1 K-1
† M M ∂T

Cp = 1.5 kJ kg -1 K-1
† †

†
 CompressorExample

Westartbydoingcalculationsfortheisentropicprocess.Forisentropic
compression:

SOUT = S IN OR SOUT - S IN = DS = 0

o
S IN = S298
† †
SOUTistheentropyatadifferenttemperatureandpressurefromtheinlet.It
canalsobewrittendownusingthepropertyequationsfromlastweek
†

TOUT POUT
CP Ê ∂V ˆ
SOUT = S IN + Ú dT - Ú Á ˜ dP
Ë ∂T ¯P
298 T PIN

†
 CompressorExample
UsingtheVirialequationofstate
Ê∂V ˆ R 1 ∂B
Á ˜ = +
Ë ∂T ¯P MP M ∂T

Usingknownvalues
TOUT POUT TOUT 500
† o CP Ê ∂V ˆ 1.5 Ê 0.008314 ˆ
SOUT = S298 + Ú dT - Ú Á ˜ dP = -6.13+ Ú dT - Ú Á + 2.07 ¥10 -5 ˜dP
PIN Ë ∂T ¯P 101.3 Ë 0.044P
298 T 298 T ¯

o ÊT ˆ Ê 500 ˆ
SOUT = S298 +1.5 lnÁ OUT ˜ - 0.189lnÁ ˜ - 2.07 ¥10 -5 (500 -101.3)
† Ë 298 ¯ Ë101.3¯
o ÊT ˆ
SOUT = S298 +1.5 lnÁ OUT ˜ - 0.31
Ë 298 ¯
o
Weknowthat SOUT = S IN = S298 ,sowecansolvetofindthetemperatureafter
isentropiccompression.
†
† TOUT=366.4K
 CompressorExample
Usingthistemperature,wecancalculatetheenthalpyafterisentropiccompression.
366.4 500
o Ê B 366.4 ∂B ˆ
HOUT = H 298 + Ú CP dT + Ú ÁË M - M ∂T ˜¯dP
298 101.3

366.4 500
o Ê B 366.4 ∂B ˆ
HOUT - H 298 = DH = Ú CP dT + Ú ÁË M - M ∂T ˜¯dP
298 101.3

Usingvaluesfromthedata
366.4 500
DH = Ú 1.5dT + Ú (-3.07 ¥10-3 - 366.4 ¥ 2.07 ¥10 -5 )dP
298 101.3
DH = 1.5( 366.4 - 298) - 0.0107( 500 -101.3) = 98.3 kJ kg-1

Usingtheenergybalanceforthecompressor,theisentropicworkiscalculatedas:
Wisentropic = m˙ DH isentropic = 0.5 ¥ 98.3 = 49.2 kJ s -1

†
 CompressorExample
Theactualworkisfoundusingtheisentropicefficiency

Wisentropic 49.2
W= = = 61.5 kJ s-1
hisentropic 0.8

Theworkdoneincompressing0.5kgs-1ofpropaneis
†
W=61.5 kW
Tofindthetemperatureaftertherealcompressionweusetheenergybalance
forthecompressortocalculatetherealenthalpychange.
W
W = m˙ DH fi DH =
m˙

65.5
DH = = 122.9 kJ kg-1
0.5

†
 CompressorExample

Thetemperatureaftertherealcompressionisfoundusingtheequationforthe
enthalpyasafunctionofTandP.

T 500
DH = 122.9 = Ú
298
1.5dT + Ú
101.3
( )
-3.07 ¥10 -3 - T ¥ 2.07 ¥10-5 dP

122.9 = 1.5(T - 298) -1.224 - 0.0083T

solvingthisequationforT
†
Taftercompression=382.9K
 ExpanderExample
0.05kgs-1ofairareexpandedfrom620.0kPaand295Kto101.3kPa.If
theexpanderhasanisentropicefficiencyof85%,calculatetheworkdoneby
theexpanderandthetemperatureoftheairafterexpansion.

Data
Theaircanbeassumedtobehaveasanidealgas
RT
V=
PM

M=0.0289kgmol-1
†
CP=1020Jkg-1K-1