M.

BahramiENSC388(F09)PropertiesofPureSubstances

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PropertiesofPureSubstances
PureSubstance
Asubstancethathasafixedchemicalcompositionthroughoutiscalledapuresubstance
suchaswater,air,andnitrogen.
Apuresubstancedoesnothavetobeofasingleelementorcompound.Amixtureoftwo
or more phases of a pure substance is still a pure substance as long as the chemical
compositionofallphasesisthesame.
PhasesofaPureSubstance
A pure substance may exist in different phases. There are three principal phases solid,
liquid,andgas.
A phase: is defined as having a distinct molecular arrangement that is homogenous
throughoutandseparatedfromothers(ifany)byeasilyidentifiableboundarysurfaces.
A substance may have several phases within a principal phase, each with a different
molecular structure. For example, carbon may exist as graphite or diamond in the solid
phase,andicemayexistinsevendifferentphasesathighpressure.
Molecularbondsarethestrongestinsolidsandtheweakestingases.
Solid:themoleculesarearrangedinathreedimensionalpattern(lattice)throughoutthe
solid. The molecules cannot move relative to each other; however, they continually
oscillateabouttheirequilibriumposition.
Liquid: the molecular spacing in liquid phase is not much different from that of the solid
phase (generally slightly higher), except the molecules are no longer at fixed positions
relativetoeachother.
Gas: the molecules are far apart from each other, and a molecular order does not exist.
Gas molecules move randomly, and continually collide with each other and the walls of
thecontainertheyarein.
Molecules in the gas phase are at a considerably higher energy level than they are in
liquidsorsolidphases.
PhaseChangeProcessesofPureSubstances
Consideraprocesswhereapuresubstancestartsasasolidandisheatedupatconstant
pressure until it all becomes gas. Depending on the prevailing pressure, the matter will
passthroughvariousphasetransformations.AtP
0
:
1.Solid
2.Mixedphaseofliquidandsolid
M.BahramiENSC388(F09)PropertiesofPureSubstances

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3.Subcooledorcompressedliquid(meansitisnotabouttovaporize)
4.Wetvapororsaturatedliquidvapormixture,thetemperaturewillstoprisinguntilthe
liquidiscompletelyvaporized.
5.Superheatedvapor(avaporthatisnotabouttocondense).

Fig.1:Tvdiagramfortheheatingprocessofapuresubstance.
+ Atagivenpressure,thetemperatureatwhichapuresubstancestartsboilingiscalled
thesaturationtemperature,T
sat
.
+ Likewise,atagiventemperature,thepressureatwhichapuresubstancestartsboiling
iscalledthesaturationpressure,P
sat
.
M.BahramiENSC388(F09)PropertiesofPureSubstances

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+ Duringaphasechangeprocess,pressureandtemperaturearedependentproperties,
T
sat
=f(P
sat
).
+ The critical point is the point at which the liquid and vapor phases are not
distinguishable
+ The triple point is the point at which the liquid, solid, and vapor phases can exist
together.OnPvorTvdiagrams,thesetriplephasestatesformalinecalledthetriple
line.
Table1:Criticalandtriplepointforwaterandoxygen.
CriticalPoint TriplePoint
P(atm) T(K/C) P(atm) T(K/C)
H
2
O 218 647.30/(374.14) 0.006 273.17(0.01)
O
2
50.136 154.80/(118.36) 0.0015 54.16/(219)
VaporDome
The general shape of a Pv diagram for a pure substance is very similar to that of a Tv
diagram.

Fig.2:Pvdiagramofapuresubstance.
sat.vaporline
sat. liquid
line
SUPERHEATED
VAPORREGION
COMPRESSED
LIQUID
REGION
SATURATED LIQUID
VAPORREGION
v
T
2
=const.>T
1

T
1
=const
criticalpoint
P
M.BahramiENSC388(F09)PropertiesofPureSubstances

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ThePTorPhaseChangeDiagram
Thisiscalledphasediagramsinceallthreephasesareseparatedfromeachotherbythree
lines.Mostpuresubstancesexhibitthesamebehavior.
+ Oneexceptioniswater.Waterexpandsuponfreezing.

Fig.3:phasediagramofpuresubstances.
Therearetwowaysthatasubstancecanpassfromsolidphasetovaporphasei)itmelts
first into a liquid and subsequently evaporates, ii) it evaporates directly without melting
(sublimation).
+ thesublimationlineseparatesthesolidandthevapor.
+ thevaporizationlineseparatestheliquidandvaporregions
+ themeltingorfusionlineseparatesthesolidandliquid.
+ thesethreelinesmeetatthetriplepoint.
ifP<P
TP
,thesolidphasecanchangedirectlytoavaporphase
atP<P
TP
thepuresubstancecannotexistintheliquidphase.Normally(P>P
TP

)thesubstancemeltsintoaliquidandthenevaporates.
matter (like CO
2
) which has a triple point above 1 atm sublimate under
atmosphericconditions(dryice)
M.BahramiENSC388(F09)PropertiesofPureSubstances

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forwater(asthemostcommonworkingfluid)wearemainlyinterestedinthe
liquid and vapor regions. Hence, we are mostly interested in boiling and
condensation.
PropertyTables
Formostsubstances,therelationshipsamongthermodynamicpropertiesaretoocomplex
to be expressed by simple equations. Thus, properties are frequently presented in the
formoftables,seeTableA4.
Thesubscriptfisusedtodenotepropertiesofasaturatedliquidandgforsaturated
vapor. Another subscript, fg, denotes the difference between the saturated vapor and
saturatedliquidvaluesofthesameproperty.
Forexample:
v
f
=specificvolumeofsaturatedliquid
v
g
=specificvolumeofsaturatedvapor
v
fg
=differencebetweenv
g
andv
f
(v
fg
=v
g
v
f
)
Enthalpy:isapropertydefinedasH=U+PV(kJ)orh=u+Pv(kJ/kg)(permassunit).
Enthalpy of vaporization (or latent heat): represents the amount of energy needed to
vaporizeaunitmass of saturatedliquidat agiventemperatureorpressure.Itdecreases
asthetemperatureorpressureincrease,andbecomeszeroatthecriticalpoint.
1SaturatedLiquidVaporMixture
Duringvaporization,amixtureofpartliquidpartvaporexists.Toanalyzethismixture,we
needtoknowtheproportionsoftheliquidandvaporinthemixture.Theratioofthemass
ofvaportothemassofthetotalmixtureiscalledquality,x:
g f
m m m m m x + = + = =
vapor liquid total
total
vapor
m
m

Saturated liquidvapor mixture is treated as a combination of two subsystems (two

phases). The properties of the mixture are the average properties of the saturated
liquidvapormixture.
M.BahramiENSC388(F09)PropertiesofPureSubstances

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( )
( )
( )
fg
f ave
fg f ave
t g g f ave
g g f g t ave t g t f
g g f f ave t
g f
v
v v
x
kg m xv v v
m m x xv v x v
v m v m m v m m m m
v m v m v m
V V V

=
+ =
= + =
+ = =
+ =
+ =
or,
/
/ and 1
m by dividing
3
t

Fig.4:Therelativeamountsofliquidandvaporphases(qualityx)areusedtocalculatethe
mixtureproperties.
Similarly,
fg f ave
fg f ave
xh h h
xu u u
+ =
+ =

Oringeneral,itcanbesummarizedasy
ave
=y
f
+x.y
fg
.Notethat:
g ave f
y y y
x
s s
s s 1 0

Note:pressureandtemperaturearedependentinthesaturatedmixtureregion.
criticalpoint
sat.
liquid
states
sat.
vapor
states
sat.vapor

sat.liquid
P or
T
v
M.BahramiENSC388(F09)PropertiesofPureSubstances

Fig.5:Qualitydefinedonlyforsaturatedliquidvapormixture.

Example1:Saturatedliquidvapormixture
Aclosed,rigidcontainerofvolume0.5m
3
isplacedonahotplate.Initiallythecontainer
holds a twophase mixture of saturated liquid water and saturated water vapor at P
1
= 1
barwithaqualityof0.5.Afterheating,thepressureinthecontainerisP
2
=1.5bar.Indicate
theinitialandfinalstatesonaTvdiagram,anddetermine:
a)thetemperature,inC,ateachstate.
b)themassofvaporpresentateachstate,inkg.
c) if heating continues, determine the pressure, in bar, when the container holds only
saturatedvapor.
Solution:
Assumptions:
1. Waterinthecontainerisaclosedsystem.
2. States1,2,and3areequilibriumstates.
3. Thevolumeofcontainerremainsconstant.
Two independent properties are required to fix state 1 and 2. At the initial state, the
pressureandqualityareknown.Thusstate1isknown,asmentionedintheproblem.The
specificvolumeatstate1isfoundusingthegivenquality:
( )
kg m v
v v x v v
f g f
/ 8475 . 0 ) 001043 . 0 694 . 1 ( 5 . 0 001043 . 0
kPa 100 bar 1 P at 5 - A Table From
3
1
1 1 1 1 1
= + =
= =
+ =

At state 2, the pressure is known. Volume and mass remain constant during the heating
process within the container, so v
2
=v
1
. For P
2
= 0.15 MPa, Table A5 gives v
f2
= 0.001053
andv
g2
=1.1593m
3
/kg.Since
M.BahramiENSC388(F09)PropertiesofPureSubstances

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v
f2
<v
2
<v
g2
State2mustbeinthetwophaseregionaswell.Sincestate1and2areinthetwophase
liquidvaporregion,thetemperaturescorrespondtothesaturationtemperaturesforthe
given.TableA5:
T
1
=99.63CandT
2
=111.4C
Tofindthemassofwatervaporpresent,wefirstfindthetotalmass,m.
( ) kg kg m x m
kg
kg m
m
v
V
m
g
295 . 0 59 . 0 5 . 0
59 . 0
/ 8475 . 0
5 . 0
1 1
3
3
= = =
= = =

Themassofvaporatstate2isfoundsimilarlyusingqualityx
2
.FromTableA5,forP
2
=1.5
bar,wehave:
( ) kg kg m
x
v v
v v
x
g
f g
f
431 . 0 59 . 0 731 . 0
731 . 0
001053 . 0 159 . 1
001053 . 0 8475 . 0
2
2
2 2
2
2
= =
=

Ifheatingcontinued,state3wouldbeonthesaturatedvaporline,asshowninontheTv
diagram above. Thus, the pressure would be the corresponding saturation pressure.
InterpolatinginTableA5atv
g
=0.8475m
3
/kg,wegetP
3
=2.11bar.
v
P
2
=1.5bar
P
1
=1bar
3
1
2
T
M.BahramiENSC388(F09)PropertiesofPureSubstances

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2SuperheatedVapor
Superheated region is a single phase region (vapor only), temperature and pressure are
nolongerdependent.SeeTableA6forsuperheatedvaporproperties.
IfT>>T
critical
orP<<P
critical
,thenthevaporcanbeapproximatedasanidealgas.
3Compressed(orSubcooled)Liquid
Thepropertiesofaliquidarerelativelyindependentofpressure(incompressible).
A general approximation is to treat compressed liquid as saturated liquid at the given
saturationtemperature.
T f
y y
@
~
The property most affected by pressure is enthalpy. For enthalpy use the following
approximation:
( )
sat f T f
P P v h h + ~
@

TheIdealGasEquationofState
Anyequationthatrelatesthepressure,temperature,andspecificvolumeofasubstance
iscalledanequationofstate.
The simplest and best known equation of state for substances in the gas phase is the
idealgasequationofstate.
Gas and vapor are often used as synonymous words. The vapor phase of a substance is
calledagas whenitisabovethecriticaltemperature.Vaporusuallyimpliesagasthatis
notfarfromastateofcondensation.
Itisexperimentallyobservedthatatalowpressurethevolumeofagasisproportionalto
itstemperature:
RT Pv =
WhereRisthegasconstant.Theaboveequationiscalledtheidealgasequationofstate
(idealgasrelation).SinceRisaconstantforagas,onecanwrite:
2
2 2
1
1 1
T
v P
T
v P
R = =
where1and2denotetwostatesofanidealgas.TheconstantRisdifferentforeachgas;
seeTable23inCengelbook.
R
u
=8.314kJ/(kmol.K)istheuniversalgasconstant,R=R
u
/M.
The molar mass, M (kg/kmol): is defined as the mass of one mole of a substance. The
massofasystemisequaltotheproductofitsmolarmassMandthemolenumberN:
MN m = (kg)
M.BahramiENSC388(F09)PropertiesofPureSubstances

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SeeTableA1forRandMforseveralsubstances.Anidealgasisanimaginarysubstance
that obeys the relation Pv = RT. It is experimentally observed that the ideal gas closely
approximatethePvTbehaviorofrealgasesatlowdensities.
Intherangeofpracticalinterest,manyfamiliargasessuchasair,nitrogen,oxygen,
hydrogen, helium, argon, neon, and CO
2
can be treated as ideal gases with
negligibleerror.
Water vapor (in general see Fig. 449 Cengel book), refrigerant vapor in
refrigeratorsshouldnotbetreatedasidealgases.
Watervaporatpressuresbelow10kPacanbetreatedasanidealgas,regardless
oftemperature.
M.BahramiENSC388(F09)PropertiesofPureSubstances

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CompressibilityFactor
Theassumptionofidealgasrelationimpliesthat:
thegasparticlestakeupnegligiblevolume
theintermolecularpotentialenergybetweenparticlesissmall
particlesactindependentofoneanother
However,realgasesdeviatefromidealgasbehavior.Thisdeviationatgiventemperature
andpressurecanbeaccuratelyaccountedforbyintroductionofacorrectionfactorcalled
thecompressibilityfactorZ.
ZRT Pv or
RT
Pv
Z = =
orZ=v
actual
/v
ideal
.Obviously,Z=1foridealgases.
Gases behave very much the same at temperatures and pressures normalized with
respecttotheircriticaltemperaturesandpressures.
cr
R
cr
R
T
T
T and
P
P
P = =
HereP
R
andT
R
arecalledthereducedpressureandtemperature,respectively.
By curvefitting all the data, the general compressibility chart is obtained which can be
usedforallgases.

Fig.6:Zfactor,generalcompressibilitychart.
M.BahramiENSC388(F09)PropertiesofPureSubstances

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FromtheZchart,onecanconclude:
at very low pressure (P
R
<<1), the gases behave as an ideal gas regardless of
temperature
athightemperatures(T
R
>2),idealgasbehaviorcanbeassumed.
thedeviationishighestinthevicinityofthecriticalpoint.
Example2:IdealGas
DeterminethespecificvolumeofR134aat1MPaand50C,using(a)idealgasequation
(b) the generalized compressibility chart. Compare the values obtained with the actual
valueof0.02171m
3
/kg.
Solution:
FromTableA1,forR134a,R=0.0815kPa.m
3
/(kg.K),P
cr
=4.067MPa,andT
cr
=374.3K
(a)Idealgasequationofstate
( ) | |( )
( )
kg m
kPa
K K kg m kPa
P
RT
v / 02632 . 0
1000
323 . / . 0815 . 0
3
3
= = =
Comparing with the tabulated value, using ideal gas equation one would get an error of
(0.026320.02171)/0.02171=0.212or21.2%.
(b)TodeterminethecorrectionfactorZ,
863 . 0
3 . 374
323
246 . 0
067 . 4
1
= = =
= = =
K
K
T
T
T
MPa
MPa
P
P
P
cr
R
cr
R

FromFig.A28,Z=0.84.Thus,
v=Zv
ideal
=0.84(0.02632m
3
/kg)=0.02211m
3
/kg
Theerrorislessthan2%.
Therefore, in the absence of exact tabulated data, the generalized compressibility chart
canbeusedwithconfidence.