THERMOPHYSICALPROPERTIESOFPETROLEUM

FRACTIONSANDCRUDEOILS

3.1Introduction

A petroleum refinery is a collection of unit operations, such as fractionation

towers, pumps, and heat exchangers. Analysis and design of these units
require knowledge of the thermodynamic and physical properties of the
petroleumfluids.Designingacrudedistillationtowerrequireknowledgeon
howthehydrocarbonsinthecrudeoildistributethemselvesoneachtrayon
thetower,i.e.vaporliquiddistribution,andthedensitiesofthemixture.Heat
exchanger design depends on enthalpies, thermal conductivity and viscosity
oftheflowingstreams.Table3.1liststhethermophysicalpropertiesrequired
forthedesignandoperationofalmosteverypieceofprocessingequipmentin
therefinery.

Table3.1
ThermopysicalPropertyPrediction
___________________________________________________

ThermodynamicProperties:
Enthalpy
HeatCapacity
CompressibilityFactors
EquilibriumKvalues
FlashCurves

TransportProperties:
Viscosity
ThermalConductivity
Diffusivity

PhysicalProperties:
Densities
Volumes

Due to the complexity of the composition of petroleum fractions and crude

oilsitisnotpossibletomeasureorcalculateaccuratelyalloftheseproperties.
Furthermore, calculation methods developed for pure hydrocarbons are not
alwaysapplicable.Thereforechemicalandpetroleumrefiningengineersover
the years have developed special methods or correlations to estimate the
1

properties of petroleum fraction from easily measured properties like the

normal boiling point and specific gravity. Such methods and schemes
characterize these petroleum fractions. Traditionally these correlations are
developed to be simple to use, requiring minimum input data, and are
usuallypresentedingraphicalform.Atthisstageitisinstructivetopointout
that there is a difference between the characterization of crude oils and
narrow boiling petroleum fractions. For crude oils, mixture bulk properties
cannot directly be used to estimate the properties of the mixture. While for
narrowboilingfractions,mixturepropertiessuchastheaverageboilingpoint,
specificgravity,molecularweightmaydirectlybeusedtopredictmanyother
propertiesasoutlinedintheAPITechnicalDataBookPetroleumRefining(1).

3.2BasicInputData

The characterization of petroleum fractions require several laboratory

measurableproperties:
aSpecificgravity(S)
bBoilingpointcurve(ASTMorTrueBoilingPointdistillation)
cKinematicviscosityat100and210F( 100 , 210 )
dRefractiveindex(n)
eMolecularweight(M)
With the exception of True Boiling Point distillation and molecular weight,
these properties can be readily measured in any petroleum characterization
laboratory.Themeaningofthesepropertieswillbeexplainedlater.

3.2.1Gravity:

Specificgravityforliquidoilsisdefinedas:

S liq =

liq

water

3.1

Both densities of oil and water are at some standard temperature and
pressure.Thesestandardconditionsforspecificgravityofpetroleumliquids
are1atmand60F.Sinceunderthesameconditions,mostpetroleumfractions
arelighterthanwater, liq 1 .
AnotherparameterforoildensityisAPIgravitydefinedas:
141.5
API =
131.5

S
HeavyoilshavelowAPIandlightoilshighAPIgravities.

3.2

Density measurement of petroleum fractions and crude oils are carried out
usingeitherapycnometeroraMettler/Parrdensitometer.Thelattermethod
is based on densitydependent frequency changes of an oscillating glass U
tube.

3.2.2BoilingPointCurves

ASTM or true boiling point distillations (TBP) characterize the volatility of

petroleum fractions and crude oils. Both are batch distillations, which differ
mainlyinthedegreeoffractionationobtainedduringthedistillation.

3.3.3ASTMDistillation:

This is carried out in a relatively simple apparatus consisting of a flask

holdingthesampleconnectedtoaninclinedcondenser,whichcondensedthe
risingvapors.Thefractionsdistilledarecollectedinagraduatedcylinder.The
temperature of the rising vapors is recorded at specific interval of the
collected distillates. This is essentially a batch distillation with one
equilibriumstageandnorefluxandminimumseparationofthecomponents
ofthefractions.Forgasolines,kerosines,gasoilandsimilarlightandmiddle
distillatestheASTMmethodD86whichcarriedoutatatmosphericpressureis
used.HeavypetroleumproductswhichtendtodecomposeintheASTMD86
method but can be partially or completely vaporized at a maximum
temperature of 750 F (400 C) at pressures down to 1mm Hg are distilled
using the ASTM D1160 method. It is carried out at pressures between 1
mmHgand760mmHg.

Thetemperatureatwhichthefirstdropofcondensateiscollectediscalledthe
initial boiling point (IBP). The end point (EP) is the maximum vapor
temperaturewhenalmosttheentiresampleisdistilled(above95%).
Boilingtemperaturesatsubatmosphericpressures(lessthan760mmHg)can
beconvertedtonormalboilingpoints(at760mmHg)usingprocedure5A1.13
ofAPITDB.
SinceminimumfractionationoccursinASTMdistillation,componentsinthe
mixture do not distill one by one in the order of their boiling points, but as
mixtures of successively higher boiling points. Thus, components boiling
below the IBP and above the EP are present in the sample. Nevertheless,
becauseASTMdistillationsarequicklyconductedandhavebeensuccessfully
automated,requireonlyasmallsample,andarequitereproducible,theyare
widelyusedforcomparisonandspecificationofpetroleumfractions.

3.2.3TrueBoilingPointDistillation:

Data from TBP distillation provides a more detailed characterization of the

volatility of the crude oil or petroleum fraction. It is performed in columns
with15to100theoreticalplatesorequilibriumstagesatrelativelyhighreflux.
The rising vapors are condensed and collected either at a constant rate of
boiling points or constant rate of sample vaporized. Operation is at 760
mmHgforboilingpointsbelow750F.Forhigherboilingpointfractions;the
distillationisconductedatreducedpressuresaslowas0.5mmHgbypulling
vacuum at the top of the column. Results from vacuum operation are
extrapolated to atmospheric pressure by the vapor pressure correlation of
Maxwell and Bonner. The high degree of fractionation in this test gives
accuratecomponentdistribution.BecausethedegreeofseparationforaTBP
distillation test is much higher than for an ASTM distillation test, the IBP is
lowerandtheEPishigherfortheTBPmethodascomparedwiththeASTM
method.TheTBPcurvewhichisaplotofthenormalboilingpointversusthe
percentsampledistilledisusuallyusedasbasisforthecharacterizationofthe
crudeoilorpetroleumproductforthepurposedofdesignandanalysis.

3.2.4ConversionbetweenASTMandTBPdistillation:

SinceTBPdistillationisbothtediousandtimeconsumingvisvistheASTM
method,therehasbeenanincentivetodevelopcorrelationtoconvertASTM
toTBPdistillationandachievingthebenefitofthedetailedseparationofTBP
withthelittleeffortinASTMdistillation.Thefollowingequationssuggested
by Riazi and Duabert and published by the API(1) are used for the
interconversion:

TBP = a( ASTM D86) b

3.3

a,b=constantsvaryingwithpercentofliquidsampledistilledasgivenin
Table3.2.
TBP=trueboilingpointtemperaturesat0,10,30,50,70,90,and95volume
percentdistilled,indegreesRankine.
ASTMD86=observedASTMD86temperaturesatcorrespondingvolume
percentdistilled,indegreesRankine.
AverageerrorbetweenthecalculatedandmeasuredTBPisintherangeof5
C.

Table3.2
Constantsforequation3.3

Volume%
distilled
0
10
30
50
70
90
95

0.9167
0.5277
0.7429
0.8920
0.8705
0.9490
0.8008

1.0019
1.0900
1.0425
1.0176
1.0226
1.0110
1.0355

Morerecently,Daubert(2)publishedanewmethodfordistillationcurves
interconversionusingthefollowingequations:
T50' = A4 (T50 ) B 4
T30' = T50' T3'
T10' = T30' T2'

T0' = T10' T1'

T95' = T90' + T7'
where

T70' = T50' + T5'

T90' = T70' + T6'

Ti = Ai (Ti )
T2 = T30 T10
T6 = T90 T70
'

Bi

T1 = T10 T0
T3 = T50 T30
T7 = T f T90

3.4

T2 = T30 T10
T5 = T70 T50

The symbol T and T stands for ASTM D86 and TBP temperatures
respectively, both in F. The subscript 0 and f stands for the initial andfinal
temperaturesrespectively.AiandBiareconstantsgiveninTable3.3

Table3.3
ConstantsforDaubertsDistillationCurvesInterconversion
Method

Index
Ai
Bi
numberi
1
7.4012
0.6024
2
4.9004
0.7164
3
3.0305
0.8008
4
0.8718
1.0258
5
2.5282
0.8200
6
3.0419
0.7750
7
0.1180
1.6606

Thereportedaverageerrorforthismethodisabout3C
Example3.1:


ApetroleumcuthasthefollowingASTMD86Distillationdata:

Volume%
0
10
30
50
70
90
95
distilled
Temperature,
36.5
54
77
101.5
131
171
186.5
C

ConvertthesedatatoTBPdatausingtheAPImethodofRiaziandDaubert
andDaubertsmethod.Plottheresultsandcompare.

Solution:

ApplicationofAPImethodisstraightforwardusingtheconstantsinTable3.2.
FortheDaubersmethod,theconstantsinTable3.3areusedtocalculateTBP
at50vol%.the TarecalculatedfromtheASTMdata,theTfortheTBPare
calculated.ThenTforTBParecalculatedusingtheformulasinequation3.2.
TheresultsareshowninTable3.4

Table3.4:Example3.1

Volume% D86T, TBP,C TBP,C

distilled
C
API
Daubert
0
36.5
14.1
5.3
10
54
33.4
27.5
30
77
69.0
66.7
50
101.5
101.6
101.7
70
131
135.2
138.1
90
171
180.5
180.8
95
186.5
194.1
197.3

250.0

200.0

Temperature,C

APITBPCurve
ASTMD86

150.0

DuabertTBP
100.0

50.0

0.0
0

10

20

30

40

50

60

70

80

90

100

50.0

Volume%Distilled

Figure3.1ConversionofASTMD86intoTBP(Example3.1)

AscanbeseenfromFigure3.1,TheTBPdistillationcurveisbelowtheASTM
curveatvolumedistilledbelow50%andaboveitforvolumedistilledabove
50%.TheAPIandDuabertsmethodsgivecomparableresultsexceptforthe
lowrange,lessthan10%distilled.

Based on the distillation curve, five different average boiling points can be
estimated. Among these, the volume average boiling point (VABP) and the
mean average boiling points (MeABP) are the most widely used in property
estimation and design. The mean average boiling point is utilized in the
definition of an important parameter, the Watson characterization factor K
givenby:

( MeABP) 3

3.5
K =
S
WhereMeABPisindegreesRankine.

Thefollowingistheprocedureforestimatingtheaverageboilingpointwhen
theASTMD86distillationdataisavailable.TheVABPiscalculatedfromthe
boilingtemperaturesateachofthe10,30,50,70,and90percentdistilled:

T + T30 + T50 + T70 + T90

VABP = 10

3.6
5

WherealltemperaturesareindegreesF.

TheMeABPiscalculatedusingthefollowingequation:

MeABP = VABP

3.7

Where isgivenby:

ln = 0.94402 0.00865(VABP 32) 0.6667 + 2.99791SL0.333

T T10

SL = 90
90 10

AsmentionedbeforeASTMandTBPdistillationcanbeperformedoncrude
oils and petroleum products. The petroleum fractions are cuts from the
crude oil with specific boiling point range and with special specification of
propertiessuchasAPIgravityandviscosity.Eachofthesecutscanbefurther
defined by dividing them into narrow boiling fractions, called pseudo (not
real) components. For these pseudocomponents, the average boiling point
canbeestimatedaseithermidboilingpointormidpercentageboilingpoint.
TheTBPcurveisdividedintoanarbitrarynumberofpseudocomponentsor
narrowboilingcuts.Theaverageboilingpointiseithertheaveragebetween
the IBP and the EP of that pseudocomponent. The midvolume percentage
point is the temperature at the arithmetic average of the volume distilled at
theIBPandEPofthatpseudocomponent.Sinceboilingrangeissmall,both
averages are close to each other and can be considered the VABP or the
MeABPforthatpseudocomponent.

Example3.2:

Calculatethemeanaverageboilingpointofthepetroleumfractionofexample
3.1. If the API gravity of this fraction is 66, calculate the Watsons
characterizationfactor.

Solution:

The D86 distillation temperatures are converted to degrees F. The volume

averageboilingpointisobtainedfromequation3.6
129.2 + 170.6 + 214.7 + 267.8 + 339.8
= 224.4 F
VABP =
5
SL=2.6325
=18.279

MeBP=224.418.3=206.1For96.8C
Fromequation3.2
141.4
S=
= 0.7313
62 + 131.5

(206.1 + 459.6)
K =
0.7313

= 11.94

3.3PseudoComponents

Calculations involving crude oil and petroleum fractions require the

compositionofeachprocessstream.Sincemostoftheactualcomponentsare
not known, the petroleum fractions is characterized as a mixture of discrete
pseudo components with defined boiling point ranges or cut points on the
TBP distillation curve. Each pseudocomponent corresponds to several
unknownactualcompounds(e.g.paraffins,naphthenesandaromatics)which
boilinagiventemperaturerange.
Usuallyeachpseudocomponentischaracterizedbyanaveragenormalpoint,
specific gravity and molecular weight. The first properties are obtained
experimentallyfromtheTBPcurveandgravityversusvolumedistilledcurve.
Insomecasesonlytheoverallspecificgravityofthefractionismeasured.The
molecular weight is usually calculated through a correlation. Once these
parameters are determined the pseudo components can be treated as any
definedcomponentforthecalculationofthermophysicalandthermodynamic
property like enthalpy, entropy, and transport properties like viscosity,
thermalconductivityanddiffusivity.Somepropertieslikepourpointdepend
on the chemical nature of the compounds represented in the pseudo
components and the information on the chemical compositions in terms of
percentageofparaffins,naphthenesandaromaticsbecomenecessary.

3.3.1BreakupofTBPcurveintoPseudocomponents

TheTBPforthecrudeoilorthepetroleumfractionhastobeavailable,either
by direct laboratory measurements through ASTM D1160 distillation or
throughtheconversionofASTMD86distillationintoTBPdistillationcurve.
TBP cut point ranges are used to define pseudocomponents , with the
averagetemperatureofthecutorthemidpointnormalboilingpoint(NBP).If
the petroleum fraction contains components lighter than pentanes, the
composition of the lighter ends has to be available experimentally through
chromatographic analysis of the vapors. Otherwise the lighter ends are
lumped with lightest pseudo component. The number of such pseudo
components depends on the boiling point range of the whole petroleum

fraction. This number is a trade off between producing a smooth calculated

property curve and having too many components which leads to excessive
computationtime.
Thefollowingcutpointrangesarereasonableformostrefiningcalculations:
TBPrange,C
Numberofcuts
<37.8
Use actual components (pentanes and
lighter)
37.8427
28
427649
8
649871
4

Ageneralguidelinefordeterminingthenumberofpseudocomponentsisas
follows:
10Cforlightfractionswithboilingpointslessthan200C
15Cforfractionswithboilingpointsbetween200to400C
20Cforfractionswithboilingpointsbetween400to600C
30Cforfractionswithboilingpointsbeyond600C
Thenumberofpseudocomponentdependsontheapplication.Indistillation
calculations, more NBP cuts might be needed to represent narrow boiling
products.Figure3.2showshowtheTBPcurveiscutintoseveralpseudo
components.

Figure3.2RepresentationofTBPcurvebyPseudoComponents
_____________________________________________________________________
Example3.3
Using the TBP curve of the petroleum cut of example 1, divide it into 20
pseudocomponents. Calculate the volume percentage of each pseudo
component.

10


Solution:

TheTBPcurveobtainedextendsto95volumepercentdistilledonly.Inorder
to obtain the average boiling point of the last fractions, the curve is
extrapolated to the final point of the distillation (100%) by using fitting the
curve a suitable polynomial function and extrapolating the results. In this
chapter Excel spreadsheet program was used with a fifth order polynomial
functionwasused.Theresultsareshownbelow.
TBP Curve
300
y = 0.0000001x5 - 0.0000287x4 + 0.0027144x3 -

250

0.1208156x 2 + 4.2608778x - 5.3573689

R 2 = 0.9999966

TBP, C

200
150
100

TBP Curve
ASTM D86

50

Poly. (TBP Curve)

0
-50

10

20

30

40

50

60

70

80

90

100

Vol%

Figure3.3ExtrapolationofTBPcurve

The end point of the cut is 218.2 C and the IBP is 5.4 C. Therefore each
pseudocomponent has a temperature interval of (218.2+5.4)/2 or 11.2 C
.Thenthecurvecanbecutasfollows.TheEBPofthefirstcutisIBP+11.2 C
or 5.8 C. The average boiling point for the first pseudocomponent is (
5.4+5.8)/2or0.2C.Thevol%is2.84asreadfromtheTBPcurve.Thesecond
cut has an end boiling point of 17 C and end volume percent of 6.19.
Therefore the volume % of this cut is 6.19 2.84 or 3.36 vol%. The average
boiling point for the second cut is (17+5.8)/2 or 11.2 C . For the subsequent
cuttheresultsareshowninTable3.4

11

EBPofcut,C
5.8
17.0
28.2
39.4
50.5
61.7
72.9
84.1
95.3
106.4
117.6
128.8
140.0
151.1
162.3
173.5
184.7
195.9
207.0
218.2

Table3.5Pseudocomponentstable

Vol%atendof
NBPofcut,C
cut
0.2
2.84
11.4
6.19
22.6
10.22
33.8
15.09
44.9
20.82
56.1
27.15
67.3
33.68
78.5
40.10
89.7
46.36
100.8
52.53
112.0
58.69
123.2
64.89
134.4
71.09
145.6
77.07
156.7
82.53
167.9
87.25
179.1
91.25
190.3
94.63
201.5
97.51
212.6
100.00

Cutvol%
2.84
3.36
4.03
4.87
5.73
6.34
6.52
6.42
6.26
6.17
6.16
6.21
6.20
5.98
5.45
4.73
4.00
3.37
2.88
2.49

3.3.2CalculationofpseudocomponentsSpecificGravities

As pointed out earlier, the distillation test might include measurement of

gravity versus volume distilled. Sometimes this not available and only the
averagethegravityofthewholepetroleumfractionismeasured.Inthiscase
the following procedure is used to obtain the gravity for each pseudo
component.Thisstepisnecessaryinordertocalculatethemolecularweight
of the pseudocomponent and hence to convert volume fractions into mass
fractionsormolefractions.
Any petroleum fraction or NBP cut can be characterized by the Watson
Characterization K factor defined in equation 3.5. For the petroleum cut
comprising the pseudocomponents the K factor for the pseudocomponents
isassumedconstantandequaltoitsvalueforthewholepetroleumcut.Hence

12

the above definition of the K factor is used to calculate the gravity of each
pseudocomponentgivenitsaveragenormalboilingpoint.

Example3.4

Calculate the specific gravity of each pseudocomponents of the previous

example.
Solution:
The K factor for this cut is 11.94. Using this value for each of the pseudo
componentsandtheNBPofeachcomponentintable3.5,thespecificgravity
ofthepseudocompontnsisgeneratedasshownintable3.6

Table3.6SpecificgravityofPseudocomponents
NBPofcut,C
S
0.2
0.6615
11.4
0.6704
22.6
0.6790
33.8
0.6875
44.9
0.6957
56.1
0.7038
67.3
0.7117
78.5
0.7194
89.7
0.7269
100.8
0.7343
112.0
0.7416
123.2
0.7487
134.4
0.7556
145.6
0.7625
156.7
0.7692
167.9
0.7758
0.7823
179.1
190.3
0.7887
201.5
0.7950
212.6
0.8012

13

3.4ThermophysicalPropertiesCalculation

3.4.1MolecularWeight

Any material or energy balance calculations would certainly require the

estimation of molecular weight of petroleum fraction. Experimentally, the
average molecular weight can be determined by several methods such as
freezing point depression osmometry, and gel permeation chromatography.
Mostoilfractionshavemolecularweightsintherangeof100700.Themethod
most suitable for determining molecular weights within this range is that
basedonfreezingpointdepression.
Predictionofthemolecularweightofpetroleumfractionsisachievedthrough
thefollowingequation(1):

1.26007 4.98308
M = 42.965 exp(2.097 10 4 Tb 7.78712 S + 2.08476 10 3 Tb S ) Tb
S
3.8

Where:
M=molecularweightofpetroleumfraction.
Tb =MeanaverageboilingpointofpetroleumfractionindegreesK.
S=specificgravity,60F/60F.

Example3.6
CalculatethemolecularweightforthecutwithNBPof216.4C.

Solution:
This cut has a NBP of 216.4 C or 489.55 K and a specific gravity of 0.6718
from table 3.6. Using equation 3.8, the molecular weight is calculated to be
170.8.

3.4.2Viscosity:

The following equations can be used to calculate the liquid viscosities of

petroleum fractions at atmospheric pressure and at temperatures of 100 F
and210F.

14

log 100 = 4.39371 1.94733K + 0.127690 K 2 + 3.2629 10 4 ( API ) 1.18246 10 2 K ( API )

0.17161K 2 + 10.9943( API ) + 9.50663 10 2 ( API ) 0.860218K ( API )
+
API + 50.3642 4.78231K
2

3.9

log 210 = 0.463634 0.166532( API ) + 5.13447 10 4 ( API ) 8.48995 10 3 K ( API )

2

8.0325 10 2 K + 1.24899( API ) + 0.197680( API )

+
API + 26.786 2.6296 K

3.10

Where 100 and 210 are the kinematic viscosities at 100 F and 210 F, in
centistockes.

3.4.3RefractiveIndex:

The refractive index is a readily measured property that can be used as an

input parameter for other correlations. It is defined as the speed of light in
vacuum with respect to the speed of light in the medium. Since refractive
indicesofpetroleumfractionsarenotalwaysknown,itisimportanttopredict
therefractiveindex.Thefollowingequationmaybeused:

1/ 2

1 + 2I
n=

1 I

ValuesofImaybecalculatedfrom:

e
I = a exp(bTb + cS + dTb S )Tb S f

3.11

3.12

Where:
a,b,c...f=constantsvaryingwithmolecularweightrangeasgivenbelow.

ConstantsLightFractionsHeavyFractions
Molecularweightrange70300
300600
Boilingpointrange,F 90650
6501000
2

a
2.266x10 2.341x102

b
3.905x104 6.464x104

c
2.468
5.144
4

d
5.704x10 3.289x104

e
0.0572
0.407

f
0.720
3.333

15


n=refractiveindexat68F.
I=Huangcharacterizationparameterat68F.
Tb=meanaverageboilingpoint,indegreesRankine.
M=molecularweightofpetroleumfractions.
S = specific gravity of petroleum fraction, 60 F/60 F.
____________________________________________________________________

Example3.7
Calculate the kinematic viscosities and the refractive index for an oil which
hasameanaverageboilingpointof320Cand34APIgravity.

Solution:
The boiling point is 593.15 K or 1067.7 R. Using equations 3.2 and 3.5, The
specificgravityis0.855andtheWatsonKfactoris11.95.Fromequations3.9
and3.10:
100=5.823CSt,and210=1.196CSt.
From equation 3.11 and 3.12, the refractive index n is calculated to be 1.481
(Mis257.1ascalculatedfromequation3.8).

3.4.4MolecularTypeCompositionofPetroleumfractions

The following equations are used to predict the fractional composition of

paraffins, naphthenes, and aromatics contained in both light and heavy
petroleum fractions. Viscosity, specific gravity, and refractive index of the
desiredfractionareusedasinputparameters.

xp=a+bRI+c(VG)

xn=d+e(RI)+f(VG)

3.13

xa=g+h(RI)+i(VG)
Where:

a,b,c,...,i=constantsvaryingwithmolecularweightrangeas
givenbelow.

16

Constants
Molecularweight
range
a
b
c
d
e
f
g
h
i

LightFraction
70200

HeavyFractions
200600

13.359
+14.4591
1.41344
+23.9825
23.333
+0.81517
9.6235
+8.8739
+0.59827

2.5737
+1.0133
3.573
+2.464
3.6701
+1.96312
4.0377
+2.6568
+1.60988

xp , xn , xa = mole fraction of paraffins, naphthenes, and aromatics,

respectively.
RI=refractivityinterceptasgivenbyequationbelow.
VG=viscositygravityconstant(VGC)asgivenbyequationsbelowforheavy
fractionsorviscositygravityfunction(VGF)asgivenbyequationsforlight
fractions.

d
RI = n
2

Where:
n=refractiveindexat68Fand1atmosphere.
d = liquid density at 68 F and1 atomosphere in
gramspercubiccentimeter.

VGC =

10S 1.0752 log(V100 38)

10 log(V100 38)

or
VGC =

S 0.24 0.022 log(v 210 35.5)

0.755

Where:
S=specificgravityat60F160F
V=Sayboltuniversalviscosityat100or210F,inSayboltuniversal
seconds.

VGF = 1.816 + 3.484 S 0.1156 ln 100

or

VGF = 1.948 + 3.535S 0.1613 ln 210

17

3.4.5PseudoCriticalConstantsandAcentricFactors

Almost all the methods which are used to calculate the thermodynamic
properties and transport properties rely on the principle of corresponding
states and an equation of state. In order to use these methods the critical
temperature and pressure and the acentric factor are required as input
constants.Whiletheseconstantsaretabulatedfordefinedcomponents,these
have to be estimated for narrow boiling petroleum cuts or pseudo
components.Thegeneraladoptedmethodinthisregardistocalculatethese
constantsfromtwocharacteristicproperties;theaverageboilingpointandthe
specific gravity or API gravity. While there several equations are available
suchasthoseofRiaziandDaubert,LeeandKesler,Winn,andCavett(3),we
willusethoseofLeeandKesler(4)becausetheyareusedasdefaultmethods
inprocesssimulators.

3.4.5.1PseudoCriticalTemperature:

(14,410 100,688S )
Tc = 189.8 + 450.6S + (0.422 + 0.1174S ) +

3.14
Tb

wherepseudocriticaltemperatureTcandtheaveragenormalboilingpointTb
areindegreesK.

3.4.5.2PseudoCriticalPressure

0.0566
4.12164 0.213426

ln Pc = 5.689S
10 3 Tb 0.436392 +
+

S
S
S2

3.15
11.819 1.53015
9.901
7 2
10 3
+ 10 Tb 4.75794 +
+
10 Tb 2.45055 + 2
S
S2
S

wherePcisinbars.

3.4.5.3AcentricFactor

The equation for calculating the acentric factor depends on the value of the
reducedaveragenormalpointTbr=Tb/Tcasfollows:

= (ln Pbr 5.92714 + 6.09648 / Tbr + 1.28862 ln Tbr 0.169347Tbr6 ) /(15.2518 15.6875 / Tbr
13.4721 ln Tbr + 0.43577Tbr6 )

forTbr<0.8 3.16
where Pbr = Pb /Pc and Pb is the pressure at which Tb is measured which is
atmosphericpressure.ForTbr>0.8theequationtouseis:

18

 = 7.904 + 0.1352 K 0.007465K 2 + 8.359Tbr + (1.408 0.01063K ) / Tbr 3.17

_____________________________________________________________________

Example3.8
Calculatethecriticaltemperatureandpressureandtheacentricfactorforan
oilwhichhasameanaverageboilingpointof320Cand34APIgravity.

Solution:
Theboilingpointis593.15Kandthespecificgravityis0.855.Usingequations
3.14and3.15:
Tc =765.5KandPc =15.26bar.Theacentricfactoris0.777(Tbr =0.755souse
equation3.16).
_____________________________________________________________________

3.4.6GeneralisedEquationforThermophysicalProperties

Riazi and AlSahhaf (5) presented a method for the calculation of different
propertiessuchasthenormalboilingpoint,density,refractiveindex,critical
temperature, pressure and density, acentric factor, solubility parameter and
surface tension given only the molecular weight and using the following
generalequation
= exp(a bM C )

3.18
where can be any one of the properties mentioned above. M is the
molecular weight and is the limiting value for any property as M .
This generalized equation can be used to calculate the following properties
giventhemolecularweight.Thepropertiesare:
ThemeanaverageboilingpointTb,K
ThespecificgravityS.
Theliquiddensityat20Cor68F.d20
TheHuangcharacterizationparameterI.
The reduced boiling point which is used to calculate the critical
temperatureindegreesK.Tbr=Tb/Tc
ThecriticalpressureinbarsPc
Thecriticaldensitydc
Theacentricfactor.
Thesurfacetensionindynes/cm.
Thesolubilityparameter,in(cal/cm3)2,
Theconstantsa,bandcforeachpropertyaregivenintable3.8.Giventhe

Table3.8ConstantsfortheRiaziAlSahhafequation

19

Tb
S
d20
I
Tbr
Pc
dc

1080
1.07
1.05
0.34
1.2
0
0.22
0.3
30.3
8.6

a
b
c
6.97996 0.01964 0.666667
3.56073 2.93886
0.1
3.80258 3.12287
0.1
2.30884 2.96508
0.1
0.34742 0.02327
0.55
6.34492 0.7239
0.3
3.2201
0.0009
1
6.252 3.64457
0.1
17.45018 9.70188
0.1
2.29195 0.54907
0.3

The application of this correlation is simple. You only need to know the
average normal boiling point of the petroleum fraction. First the molecular
weight is calculated from the correlation using the constants for the boiling
point.Oncethemolecularweightisknownotherpropertiescanbecalculated
usingequation3.18withtheappropriateconstantsfromtable3.8.

Example3.9
UsetheRiaziAlSahhafequationtocalculatethepropertiesforanoilwhich
hasameanaverageboilingpointof320Cand34APIgravity.

Solution:
From the boiling point the molecular weight is calculated as 256. Using this
valueotherpropertiesarecalculatedandthevaluesareshownbelow

S
0.859
0.855
d20
I
0.2824
773
Tc
Pc
12.5
dc
0.252

0.798

28.55

8.055

20

3.5CalculationofenthalpyofPetroleumFractions

The design of process equipment such as heat exchangers, and compressors

requires the calculation of enthalpy and entropy. While there are different
methodsforthecalculationofthermodynamicproperties,wewillconcentrate
inthissectiononmethodofLeeKeslerwhichissuitableforhandcalculation.
Equationsofstatesuchas the SoaveRedlichKwongandthePengRobinson
arewidelyusedinprocesssimulationprograms.
TheLeeKeslergeneralizedcorrelation(4)hasthefollowingexpressionforthe
compressibilityfactor:

Z = Z 0 + Z 1

3.19

RT
Equation 3.19 can be used to calculate the molar volume as: V =
or the
P
M
massdensityas =
.
V
Misthemolecularweight.
ThedeparturefunctionsHHigisgivenby

H H ig H H ig
H H ig

=
+

3.20
RT
RT
RT
c
c
c

The superscript 0 and 1 denotes the value for the simple fluid and the
dcorrection terms respectively. These values are obtained from published
tables which can be founds in standard chemical engineering
thermodynamics textbooks as functions of the reduced temperature and
pressure(6)andaretabulatedintheEXCELspreadsheetLeeKesler.xlswhich
willbediscussedinsection3.7.Thecriticaltemperature,criticalpressureand
the acentric factor for the petroleum fraction can be obtained from the
equations in section 3.4.5. If the fraction is treated as being made up of
pseudocomponents, the critical temperature, critical pressure and the
acentric factor can be calculated using the following simple mixing rule
equations:

Tc = yi Tci
i

Pc = y i Pci

3.21

= yii
i

Theenthalpychangeofafluidfromstate1atT1andP1tostate2atT2andP2
isgivenby:

21

H 2 H 1 = ( H 2 H 2ig ) + ( H 2ig H 1ig ) ( H 1 H 1ig )

Tocalculatetheenthalpywithrespecttoareferencestateset

H 1 = H ref = 0

Ifthereferencestateisatlowpressure(idealgas),then

( H 1 H 1ig ) = 0

Theenthalpyequationbecomes

ig
H = ( H H ig ) + ( H ig H ref
)

3.22

3.23

Theidealgasenthalpy changeiscalculated from theintegrationoftheideal

gasheatcapacitywithtemperature:

T2

H 2ig H 1ig = C igp dT

3.24

T1

Theidealgasheatcapacityforpetroleumfractionsisgivenby

C igp = A + BT + CT 2

3.25

Integrationofequation3.23yields:

B
C
H 2ig H 1ig = A(T2 T1 ) + (T22 T12 ) + (T23 T13 )

3.26
2
3

The constants A, B, and C can be estimated from the following relations

proposedbyLeeandKesler(5)as:

A = 4.1843M (0.33886 + 0.02827 K 0.26105CF + 0.59332CF )

3.27

B = 7.5318M ((0.9291 1.1543K + 0.0368K 2 )10 4 + CF (4.56 9.48 )10 4 ) 3.28

C = 13.5573M (1.6658 10 7 + CF (0.536 0.6828 )10 7 )

3.29

where CF = ((12.8 K )(10 K ) /(10 )) 2

and K is Watson characterization factor and M is the molecular weight. The

22

calculated heat capacity in equation 3.24 with T in degreees K is in

kJ/kgmole.K.ToobtaintheconvertthevaluetokJ/kg.KdividebyM.

Example3.10
Calculatethemolarvolumeandenthalpyofanoilat450Cand3.45bar.The
oil has a mean average boiling point of 320 C and 34 API gravity. The
referencestateisidealgasat298K.

Solution:
Thespecificgravityis0.855andtheKfactoris11.95.Usingequations3.14and
3.15:Tc=765.5KandPc=15.26bar.Theacentricfactoris0.777.Themolecular
weightfromequation3.8is257.12.
Tr = 0.9447 and Pr = 0.2261 .
FromtheLeeKeslertables:
Z 0 = 0.9029 , Z 1 = 0.0325
Z = 0.9029 + (.777)(0.0325) = 0.8776
(0.8776)(8.3143)(450 + 273.15)
V =
= 15294.5 cm3/mol
0.345
Fromequation3.23

ig
H = ( H H ig ) + ( H ig H ref
)
FromtheLeeKeslertrables:
o

H H ig
= 0.1487 ,
= 0.2882

RTc

= 0.1487 + (0.777)(0.2882) = 0.3727

ig
( H H ) = 2371.9 kJ/kgmol

H H ig

RTc
H H ig

RTc

Fortheidealheatcapacityandfromequations3.273.29
A = 8.74721 , B = 1.44929 ,and C = 0.000581
Fromequation3.26andfortemperaturesbetween298and723.15K;
ig
( H ig H ref
) = 312088.8 kJ/kgmol
Therefore
H = 314460.8 kJ/kgmolor1223kJ/kg

23

3.6EstimationofPropertiesRelatedtoPhasechanges

In petroleum refining crude oil and petroleum fractions are separated into
narrower fractions by chemical engineering unit operations that utilizes the
phase equilibria between the hydrocarbons in the liquid and vapor phases
suchasdistillation,adsorption,condensationandevaporation.Whenwateris
present such as the case in the atmospheric column of crude distillation,
liquidliquidvaporequilibriumisencountered.
Equilibrium K values, i.e. (yi/xi ) are the fundamental building blocks of all
unit operations involving phase change. Traditional older methods for
calculations of K values rely on methods or charts which were based on
temperatureandpressureonlywithnocompositiondependence.

3.6.1CubicEquationsofState

With the development of more accurate equations of state and with the
widespreaduseofcomputersimulationinprocessdesignthesemethodsare
replacedwithcomputerpackageswhichrelyonequationsofstateforphase
equilibria calculations. Equations of based on the RedlichKwong equation
have proven to be most successful for petroleum systems. The most widely
used modifications of the RedlichKwong equations are the modifications of
Soave and PengRobinson. In this chapter we will concentrate on the latter
equation.
ThePengRobinson(PR)equation(7)isacubicequationinvolumewiththe
form:

V
a (T )

Z=

V b V (V + b) + b(V b)

where Z is the compressibility factor defined as PV/RT , and V is the molar

volume. The equation is characterized by the energy parameter which is a
function of temperature and the size parameter which is constant for a
specific fluid. The equations for calculating these constant given the critical
temperature and pressure and the acentric factor can be found in many
standardchemicalengineeringthermodynamicsbooks(6).
Thisequationcanbeappliedtomixturesbyapplyingthemixingrules:

a = xi x j aij
and b = xi bi
i

thecombiningruleforaijisgivenby

aij = ( ai a j ) 2 (1 k ij )

24

where kij is the binary interaction parameters. Values of kij between

hydrocarbons are usually equal to zero. For non hydrocarbonhydrocarbon
interactionsthevaluesoftheseparametersaretabulated.

3.6.2VaporLiquidEquilibrium

The equilibrium Ki value for a component in a vapor liquid equilibrium

systemisgivenby

Ki =

il

il

iv
and iv arecalledthefugacitycoefficientofcomponentiintheliquidand

vapor phase respectively. These coefficients are functions of temperature,

pressure and composition and are calculated directly from the equation of
state. The expressions for these coefficients for the PR equation of state can
also be found in standard thermodynamics textbook. These K values are
utilized in distillation or flashing in the well known bubble, dew and flash
calculation.
A computer program PRMIX.EXE (7) is provided to do all of these
calculations. It is a general program which performs bubble, dew, vapor
liquid flash for multicomponent mixtures using the PR equation. The input
parameters are Tc, Pc and for the component in the mixture, be it defined
components or pseudocomponents. In the following we will give some
detailsonhowtousetheprogram
To start the program click on the PRMIX icon. The component numbers are
fromthefileCRITPARM.TXT.Toaddapseudocomponenttotheinputfiles,
you will need to modify CRITPARM.TXT. The file can be edited with
NOTEPAD by double clicking on it. Follow the columns carefully, and uses
spaces,NOTTABStoenterblanks.Thecriticalcompressibilityfactorisstored
in the input file for convenient reference, it is not needed for the routines.
CHANGE THE FIRST NUMBER IN THE IN THE TABLE HEADER. This
numberisthenumberofcompoundsinthefile.Ifthenumberisincorrect,the
programwillstillrun,buttheresultscanbeunpredictable.

Afterenteringthecomponentsorpseudocomponentsnumbers,theprogram
asksforthebinaryinteractioncoefficients.Asmentionedearlier,thesevalues
canbesettozeroforhydrocarbonhydrocarboninteractions.
Amenuofdifferenttypesofphaseequilibriumcalculationappears.Perform
the desired calculations. For multicomponent mixtures such as the case of
petroleum fractions made up of several pseudocomponents, the program
might not converge or gives a warning. This might be a problem with the
initial guesses which the program takes as it is caked shortcut Ki which
basically the Raoults law values. In such cases, try to get convergence at

25

lower temperatures or pressures, then change the conditions to the desired

temperature and pressure when the program asks if you want to repeat the
calculation.Whenfinishedexittheprogramasinstructed.Theresultsofthe
calculationsarestoredinthefileOUTPUT.TXT.

Example3.11
Anoilmixturecanberepresentedbythefollowingpseudocomponents

Pseudo

Pc,MPa
Mol%
Tc,K
component
1
50.0
190.6
4.60
0.008
2
11.0
338.2
4.56
0.126
3
7.00
464.5
3.36
0.242
4
20.0
619.4
2.56
0.581
5
8.0
760.2
1.52
1.046
5
4.0
925.6
1.14
1.585

Ifisoilisflashedat500Kand3MPa,whatisthefractionofvapor.Whatare
thecompositionsoftheexitingvaporandliquidphases?

Solution:
Firstenterthecriticaltemperatureandpressureandtheacentricfactorforthe
pseudocomponents in CRITPARM.TXT. Start with the number 2001 at
bottomofthelistto2006.UsingtheprogramPRMIX.EXE,thevaporfraction
and the liquid and vapor compositions are shown in the output file ( figure
3.4)

3.7UsingSpreadsheetsforThermophysicalProperties
Calculations
SpreadsheetsprogramssuchasMicrosoftEXCELhavebeenshowntobevery
usefulinsolvingengineeringproblemsandasasubstitutefortedioushand
calculations.Wehavedevelopedspreadsheetsforcalculatingthethermo
physicalpropertiesdiscussedinsections3.2to3.5.Thesespreadsheetsare
PetProp.xlsandLeeKeslerProp.xls.

26


ID NAME

Tc(K)
Pc(MPa)
2001 NBP_1
190.6000
4.6000
2002 NBP_2
338.2000
4.5600
2003 NBP_3
464.5000
3.3600
2004 NBP_4
619.4000
2.5600
2005 NBP_5
760.2000
1.5200
2006 NBP_6
925.6000
1.1400
THE DEFAULT Kij MATRIX IS
2001 2002 2003 2004 2005 2006
2002 .0000
2003 .0000 .0000
2004 .0000 .0000 .0000
2005 .0000 .0000 .0000 .0000
2006 .0000 .0000 .0000 .0000 .0000

vl
REQUIRED NUMBER OF ITERATIONS WAS:
COMPONENT IS NBP_1
ID NO. IS
COMPONENT IS NBP_2
ID NO. IS
COMPONENT IS NBP_3
ID NO. IS
COMPONENT IS NBP_4
ID NO. IS
COMPONENT IS NBP_5
ID NO. IS
COMPONENT IS NBP_6
ID NO. IS
T(K)= 500.00 P(MPa)= 3.000
ZL= .2080
ID
LIQUID X VAPOR Y Yi/Xi
2001
.0604 .6935
11.49
2002
.0313 .1446
4.617
2003
.0527 .0776
1.471
2004
.4659 .0830
.1781
2005
.2588 .0013
.4970E-02
2006
.1309 .0000
.1225E-04

7
2001
2002
2003
2004
2005
2006
ZV= .9544

VAPOR OVER FEED RATIO = .69438

qt

Figure3.4OUTPUT.TXTfileforPRMIX.EXE

ThespreadsheetPetProp.xlscontainsthefollowingworksheets:
Distil_conv: Distillation conversion from D86 to TBP as shown in
section3.2.4
Prop_calc: Calculation of thermophysical properties given the mean
averageboilingpointandtheAPIgravity.
Pseudo_comp: Given the TBP distillation curve and the API gravity,
this worksheet splits the petroleum fraction into pseudocomponents.
The results for splitting the oil into 20, 10 and 5 pseudocomponents
are tabulated. The specific gravity of each pseudocomponent is
calculated assuming that the whole fraction has the same Watson K
factor (see section 3.3.2). The volume percent of each pseudo
component is converted to weight percent and to mole percent with
thecalculationofthemolecularweight.Thepropertiesofeachpseudo
component is then calculated from the average normal boiling point
andthespecificgravity.
RiaziAlSahhaf: this worksheet utilizes the equation of Riazi and Al
Sahhaf. From the mean average boiling point the molecular weight is
calculated.Fromthemolecularweight,otherpropertiesareobtainted.

27

The worksheet calculate the properties of the pseudo components of

theworksheetPseudo_comp.AgraphicalcomparisonbetweentheAPI
methodsandtheRiaziAlSahhafequationisshownforthemolecular
weightandthecriticaltemperaturesasexamples.
Figures3.5and3.6showsampleworksheets.
The spreadsheet LeeKeslerProp.xls calculates the molar volume, the
enthalpy and entropy of petroleum fractions. It contains the following
worksheets:
State_2:Thecriticalproperties,theacentricfactorandtheconstantsof
theidealgasheatcapacityareentered.Thetemperatureandpressure
at which the calculations are desired are the input. Values from the
LeeKesler tables are entered depending on the reduced temperature
andpressure.
Ref_state: The temperature and pressure of the reference state are
entered,aswellastheappropriatevaluesfromtheLeeKeslertables.
Z_tables, H_dep. tables and S_dep. Table: These are the LeeKesler
tablesusedincalculations.
Crit Prop: A table of the critical constants and the acentric factors for
definedcomponents.
IG Cps: Contains the constants of the ideal gas heat capacity for
defined components and for petroleum fractions. The values for the
petroleum fractions which are at the bottom of the table requires the
specific gravity, the average boiling point, the molecular weight and
theacentricfactor.

28


Figure3.5Distil_convWorksheet
Conversion between ASTM and TBP distillation:
Method of Riazi and Duabert 1987

TBP= a(D86)b

Volume %
distilled

D86 T, C

D86 T, F

TBP, F

TBP, C

0
10
30
50
70
90
95

0.9167
0.5277
0.7429
0.892
0.8705
0.949
0.8008

1.0019
1.09
1.0425
1.0176
1.0226
1.011
1.0355

36.5
54
77
101.5
131
171
186.5

97.7
129.2
170.6
214.7
267.8
339.8
367.7

57.4
92.0
156.1
214.9
275.3
356.9
381.4

14.1
33.4
69.0
101.6
135.2
180.5
194.1

Calculation of average boiling points

VABP
MeABP

224.42
206.14

F or
F or

106.90
96.75

C
C

29

Conversion of D86 Distillation to TBP distillation

Method of Daubert (Hydrocarbon processing, 1994)
Recommended
Enter the temperature in degree C
%distilled
volume
0
10
30
50
70
90
95

Constant
a
7.4012
4.9004
3.0305
0.8718
2.5282
3.0419
0.118

Constant
b
0.6024
0.7164
0.8008
1.0258
0.82
0.755
1.6606

D86 T, C

D86 T, F

Ti

Ti', F

TBP, F

TBP,C

36.5
54
77
101.5
131
171
186.5

97.7
129.2
170.6
214.7
267.8
339.8
367.7

31.5
41.4
44.1

59.14
70.57
62.86
0.00
65.67
76.81
29.68

22.4
81.6
152.1
215.0
280.7
357.5
387.2

-5.3
27.5
66.7
101.7
138.1
180.8
197.3

53.1
72
27.9

The TBP curve is extrapolated to 100% volume distilled using a 5th order polynomial fit.
Calculation
of average
boiling
points
VABP
MeABP

30

224.42
206.14

F or
F or

106.9
96.75

C
C

Figure3.6Prop_CalcWorksheet

PROPERTIES OF PETROLEUM CUTS

The following cakculations require the API gravity and the mean average boiling point and other variable.
For Clarity these input variables are indicated in
RED
Calculation of Watson Characterization factor and Molecular weight
API gravity =
specific gravity =
MeABP, C =
Watson K Factor =
Mol. Weight

34.00
0.8550
320.00
11.95
257.12

593.15

494.59

Calculation of Kinematic viscosity

=
=

Kinematic viscosity at 100 F, cSt

Kinematic viscosity at 210 F, cSt

5.823
1.916

Calculation of Critical Properties and Acentric factor

Critical Temperature,
Tc

K
765.49

Critical Pressure,
Pc

R
1377.87

bar
15.26

Density Calculation at T =
Tr =
density at 60 F, g/cm3
Tr at 60
F
Zra
molar volume, cm3/gmole
density,g/cm3

Tbr

0.774867

0.7770

20
0.3830
0.8542

0.3772
0.2458
302.0074
0.8514

Refractive Index
Light Fractions MW=70-300
Huang Characterization parameter,
Refrective index
Density at 68 F, g/cm3
Refractivity
intercept

I=
n=
d=

0.284
1.481
0.8514

RI =

1.055

I=
n=
d=

0.308
1.528
0.8514

Heavy Fractions MW=300600

Density at 68 F, g/cm3

31

Constants for I
0.02266
a

0.02341

b
c
d

0.000391
2.468
-0.00057

0.000646
5.144
-0.00033

e
f

0.0572
-0.72

-0.407
-3.333

Refractivity intercept

RI =

1.102

Molecular type composition

Light fractions MW=70-200

Viscosity gravity constant
Paraffins, mol pct.
Naphthenes, mol pct.
Aromatics, mol pct.
TOTAL

VGR =

0.9591
53.83
15.03
31.14
100.00

Heavy fractions MW =200600

Kinematic viscosity at 100 F in Sybolt seconds
Viscosity gravity constant
VGC =
Paraffins, mol pct.
Naphthenes, mol pct.
Aromatics, mol pct.
TOTAL

45.01
0.8346
70.80
5.86
23.33
100.00

Flash Point
ASTM 10% temperature, F
Flash point, F

454
196.35

913.67

Pour Point
Pour point , F

31.57

32

Constants for composition

-13.359
2.5737
a
14.4591
1.0133
b
-1.41344
-3.573
c
23.9825
2.464
d
-23.333
-3.6701
e
0.81517
1.96312
f
-9.6235
-4.0377
g
8.8739
2.6568
h
0.59827
1.60988
I

3.8 QuestionsandExercises

1) AnaphthafractionhasthefollowingASTMD86distillationdata:
Vol%
Temperature,C
0.0
138.8
10.0
149.6
30.0
158.8
50.0
165.8
70.0
169.9
90.0
178.1
95.0
180.4

ObtaintheTBPcurveusingtheDaubertsmethod.Extrapolatethecurveto
100%volumedistilled.

2) Ifthespecificgravityofthisnaphthacutis0.801,Drawthevolume
percentversusspecificgravitycurve.

3) UsethespreadsheetprogramPetProp.xlstosplittheabovenaphtha
cutintopseudocomponents.Use10pseudocomponents.

4) AgasoilhasthefollowingTBPdistillationdata

Vol%
0
10
30
50
70
90
95
100

TBP,C
216
243
268
284
304
318
327
334

Andhasanaverageboilingpointof280Candanaveragedensityof
0.850g/cm3:
a) Splitthisgasoilfractionintofivepseudocomponents.CalculateTc,
PcandforeachpseudocomponentusingtheRiaziAlSahhaf
equation.
b) CalculateTc,Pcandforthewholefractionusingequations3.21.
c) Calculatetheenthalpyofthisgasoilfractionat400Cusingthe
LeeKeslercorrelationwithareferencestateofidealgasat273.15K.

33

5) Anaturalgasstreamhasthefollowingcomposition:

Component
Mol%
C1
80
5
C2
C3
4
3
nC4
iC4
2
nC5
3
iC5
2
C6
0.5
0.5
C7+

IftheaverageboilingpointandspecificgravityofC7+are174Cand0.79,
calculatethedewpointpressure.

References
1) American Petroleum Institute, Technical data bookPetroleum
Refining,1993
2) Duabert,HydrocarbonProcessing,p.75,1994.
3) PedersenK.S.,Aa.FredenslundandP.Rasmussen,PropertiesofOils
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