APPLIED THERMODYNAMICS
II  BEHAVIOR OF GASES........................................................................................................... 12
1
2
3
4
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03/09/2004
I
Pressure
Critical
point
Fusion
LIQUID
io
SOLID
PT
S ub
lim
n
at i o
Triple point
TT
za
GAS
or
VAPOR
D TH 081 B
o ri
Vap
Temperature
00052_A_A
The table below gives the triple point pressures and temperatures of a number of pure substances.
TRIPLE POINT
Hydrogen
Oxygen
Nitrogen
Chlorine
Hydrogen
sulfide
Ammonia
Carbon
dioxide
Methane
H2
O2
N2
Cl2
H 2S
NH3
CO2
CH4
Temperature
(C)
259.2
218.8
210.0
101
85.7
77.8
56.6
182.5
Pressure (bar)
0.072
0.00152
0.1253
0.014
0.227
6.08 10 4
5.2
0.117
The domain of existence of a pure substance in the fluid state includes all the areas at the right of the
fusion and sublimation curves, naturally including those that lie above the critical point. The
significance of this particular point can be illustrated by the pressure/volume diagram.
2
Pressure
in atm
Pressure
in atm
30
Ls
Vs
190C
20
150C
Ls
Temperature in C
00052_A_A
200
150
ate
100
tur
50
Sa
10
VAPOR
0
Vs
205
10
196.7C
33.3 atm
4.3 cm3/g
vap
or
5 0 100
10
190
20
150
D TH 082 B
20
Critical
point
Saturated liquid
LIQUID
30
205C
Critical
pressure
33.3 atm
33.3
40
150C
Critical
point C
190C
40
5 0 0 1000
At a given temperature lower than the critical point temperature, the pressure/volume diagram shows
the break in volume existing between the saturated liquid and vapor phases LS and VS.
At 150 C, for example, under 16 atm pressure, the above diagram shows that the volume per unit
mass of npentane in the saturated liquid state is about 2 cm3 /g (point LS). For the same pure
substance in the saturated vapor state in the same conditions it is 20 cm3/g (point VS).
Segment LS/V S is called the state change plateau, and its length, which materializes the difference in
volume between the two phases, is found to become shorter as the temperature and pressure
increase. When the pressure and temperature increase, in fact, the volume per unit mass of the liquid
phase increases by expansion, while that of the vapor phase decreases under the effect of the
pressure. The break in volume is ultimately nullified at the critical point, where the properties of both
phases are identical, thus marking the terminal point of the vapor pressure curve. The critical
conditions common to both phases are defined by the critical volume VC, critical pressure PC and
the critical temperature TC.
Outside the liquid/vapor equilibrium conditions, this diagram also shows the variation in the volume of
the fluids with pressure. If we observe the isotherms which show the change in volume with pressure,
we find that:
 the liquid phase is practically incompressible except when approaching the critical point
(vertical isotherm in the P.V diagram),
 the vapor phase increases in volume as the pressure decreases: at low pressure, P.V (P
multiplied by V) is approximately constant,
 the isotherm corresponding to the critical temperature displays a break point with a
horizontal tangent to the critical point: at this temperature, the two saturated phases VS and
LS have the same volume VC,
 the pure substance at a temperature above its critical temperature can no longer exhibit
twophase equilibrium: it behaves as a compressible fluid up to high pressures, and it is
accordingly said to be a hypercritical or supercritical fluid.
P
Supercritical
fluid
Supercritical
fluid
D TH 110 B
Liquid
Vapor
T
The critical coordinates, and especially the critical pressure PC and the critical temperature TC,
are important data for pure substances, in so far as they are necessary for determining other
thermodynamic properties. Plates A2 give these figures for a large number of pure substances.
Additional data can be obtained in the reference book The Properties of Gases and Liquids,
R.C. Reid, J.M. Prausnitz, and T.K. Sherwood, 3rd Edition, McGrawHill Book Company.
00052_A_A
3
cur
ve
Pressure
LIQUID
ure
ss
P
1.013 bar
VAPOR
Boiling point
Normal
boiling point
Temperature
D TH 083 B
pre
or
p
a
V
The vapor pressure of the liquid pure substance is the equilibrium pressure of the liquid/vapor
mixture at a given temperature t. Hence it is the pressure in a storage vessel where the pure substance
is present in the liquid state and the gas state simultaneously. It reflects the capacity of the liquid to
allow molecules to escape in the gas phase. This property is directly related to the intermolecular
bonding forces existing in the liquid phase.
Vapor pressure
of pure liquid substance
at temperature t
Ps
LIQUID
VAPOR
D TH 084 B
Equilibrium
pressure or
vapor
pressure
t
Since the two phases in equilibrium are saturated phases, the vapor pressure is often called the
saturation pressure. It is denoted PS.
The vapor pressure of a pure substance increases with temperature and reaches its maximum value,
the critical pressure, at the critical temperature.
Note that, at any temperature lower than the critical temperature, the pure substance is in the vapor
state at any pressure below its vapor pressure, and in the liquid state in the opposite case.
00052_A_A
The data on boiling points, critical conditions and vapor pressures are essential for all calculations
pertaining to the behavior of fluids and liquid/vapor equilibria. Some of them are accessible from Plates
A, B and C, which show:
 the physical properties of many pure substances (Plates A1 and A2): overall chemical
formula, melting point, normal boiling point, critical coordinates, density etc.,
 the Cox Chart, which shows the vapor pressure curves of hydrocarbons in the form of
lines (Plate B1),
 the coefficients of Antoines equation which help to represent the vapor pressure curves
by the equation:
ln P S = A
B
C+T
where:
PS
T
A, B, C
 plate B2 gives the values of the constants A, B and C for a large number of pure
substances: it also indicates the temperature interval TminTmax in which Antoines
equation gives the vapor pressure curve with a good degree of accuracy. Plates B5, B6
and B7 give a graphic representation of a number of vapor pressure curves obtained by
Antoines equation,
 data on the vapor pressure curve of water (Plates C),
 coefficients A, B, C and D of Harlachers equation.
Harlachers equation is a more elaborate form of Antoines equation for representing the
vapor pressure curve of a pure substance. It has four coefficients and is written as follows:
ln P S = A +
B
D PS
+ C ln T + 2
T
T
T is temperature in Kelvin
PS is pressure in mmHg
ln is the Napierian logarithm (or natural)
Constants A, B, C and D are given on Plate B8 for a number of pure substances.
Note that the use of Harlachers equation requires an iterative calculation. At a given temperature T,
successive approximations are used to determine the value of PS, which confirms the equality of the
two members of Harlachers equation.
The following recommendations help to deal with a problem of determining the vapor pressure of a
pure substance.
 If the vapor pressure is less than 10 mmHg, the above methods are inaccurate.
 If the vapor pressure is lower than 1500 mmHg, Antoines equation gives good results.
 If the constants A, B, C and D are available, Harlachers equation gives good results in
the interval 10 mmHg < PS < PC.
00052_A_A
4
Enthalpy
Pressure
H
H S
V
V
LS
VS
h S
L
h
L
t
V
Temperature
LS
D TH 085 B
L
P
VS
L
t
t
V
Temperature
The initial liquid (point L) is at a pressure P considered at a temperature lower than its boiling point. It is
said to be subcooled.
Progressive heating of the liquid to its boiling point is achieved by adding sensible heat because it
produces a variation in temperature. The difference hLs  hL gives this variation in sensible heat.
Related to the corresponding temperature difference, it helps to determine the heat capacity c of the
pure liquid substance. Thus we have:
hLs hL
c =
tb tL
hLs hL
tb
tL
c
: in kJ/kg
: in C
: in C
: heat capacity in kJ/kg.C
Over a not too much long temperature interval, the heat capacity c can be considered constant. The
usual values are the following:

00052_A_A
4.185 kJ/kg.C
2.0 to 3.0 kJ/kg.C
2.43 kJ/kg.C
0.138 kJ/kg.C
The saturated liquid (L S ) begins to vaporize at the boiling point and its vaporization continues at
constant temperature. The quantity of heat required to obtain the change in state is called the enthalpy
of vaporization or latent heat of vaporization ():
enthalpy of vaporization
or
heat of vaporization
= HVs hLs
The enthalpies of vaporization at temperatures sufficiently distant from the critical temperature range
from 250 to 420 kJ/kg for hydrocarbons, and about 2000 kJ/kg for water.
At the end of vaporization, the vapor obtained is said to be saturated (V S ). Throughout the
vaporization, the two phases present are in liquid/vapor equilibrium and are saturated.
The input of sensible heat to the vapor again raises its temperature, removing it from the saturation
conditions. This indicates a dry or superheated vapor. HV  HVs measures the corresponding
sensible heat.
As for the liquid phase, we can define a mean heat capacity c for heating the vapor over a given
temperature interval. The routine values for some pure substances are:
 2 kJ/kg.C for steam
 1 kJ/kg.C for air
 14.5 kJ/kg.C for hydrogen
The reverse path is obtained by removing heat. Starting with a dry vapor, it leads successively to the
desuperheat of this vapor down to saturation, and then to its condensation with the restoration of
latent heat, in this case called the heat of condensation, and finally to the subcooling of the liquid
obtained.
b  Calculation of a heat flow rate
When a fluid undergoes additions or removals of heat accompanied or unaccompanied by changes in
physical state, it is easy to determine the heat flow rates involved if we have its enthalpy before and
after the transformations achieved.
Conditions
Input M
HEAT EXCHANGERS
enthalpy H1
Physical state L or V
Temperature T1
Pressure P1
00052_A_A
Enthalpy H2
Physical state L or V
Temperature T2
Pressure P2
D TH 2024 A
Conditions
If the enthalpies are mass enthalpies, the heat flow rate Q involved is given by the expression:
Q heat input in kW
Q = M . (H2 H 1 ) M mass flowrate in kg/s
H 2 and H 1 specific enthalpies in kJ/kg
If the transformation concerns a fluid without a change in physical state, i.e. for sensible heat only, it is
often advantageous to calculate the heat flow rate involved by using the heat capacity figure.
Input M
Temperature T1
Pressure P1
and step
D TH 2024 B
Temperature T2
Pressure P2
Q = M . c . T
Q
M
c
T =
This formula, which is very convenient and commonly used, is limited to heat exchanges without
change in phase. In the general case, it is necessary to use the enthalpy and to have diagrams used
to determine the enthalpy of a fluid as a function of the conditions in which it is found.
c  Enthalpy/temperature diagram (Ht diagram)
The previous experiment in the vaporization of a pure substance can be repeated for various
pressures. Starting with a low pressure and by increasing it progressively, we observe:
 an elevation in the vaporization temperature as shown by the vapor pressure curve, up to
the critical temperature
 an increase in the enthalpies of the saturated phases and, in contrast, a decrease in the
latent heat of change of state, which is ultimately nullified when the critical temperature is
reached
The heat of vaporization decreases as the pressure increases and becomes zero at the
critical point.
 a steady unbroken change in the enthalpy of the fluid as the pressure becomes higher than
the critical pressure.
00052_A_A
500
n PENTANE
Enthalpy  Temperature diagram
400
Enthalpy kcal/kg
0
40 8
0
15
200
ted
tura
20
or
vap
10
al
ritic
Sa
30
40
50
60
300
poin
100
id
liqu
Sat
0
100
D TH 111 B
d
rate
Temperature in C
100
200
300
400
500
This diagram mainly consists of the two enthalpic curves relative to the saturated vapor HVs (t) and the
saturated liquid hLs (t). At a given temperature, the difference between vapor and liquid enthalpy:
H Vs  hLs =
represents the heat of vaporization of the pure substance. This decreases progressively as the
temperature rises, and ultimately becomes zero at the critical point, where the enthalpic curves of both
saturated phases meet.
At a temperature distant from the critical point, the enthalpy of the unsaturated phases is unaffected by
the pressure. This means that, at a given temperature, the enthalpies of the subcooled liquid or of the
dry vapor are respectively equal to the enthalpies of the saturated liquid and vapor.
As the temperature approaches the critical point, isobars help to account for the influence of the
pressure, particularly for the vapor phase.
Above the critical point, the enthalpy of the pure substance in the state of a hypercritical fluid can be
obtained as a function of temperature and pressure by prolonging the network of isobaric curves.
00052_A_A
10
rs
tur
n lin
5
0.9
0
0.9
entropy
D TH 112 B
enthalpy
sa
isotherms
isoba
atio
00052_A_A
11
f  Pressure/enthalpy diagram
Another representation of thermal properties of pure substances is the pressure/enthalpy (P/H)
diagram. Plates E6, E16 and E17 are illustrations for propane and for freons 12 and 22. The operating
conditions of refrigerating cycles, which generally operate between two and three different pressures,
are extremely well represented by this type of diagram.
isotherms
t
iqu
dl
ate
tur
Sa
d va
por
rate
Satu
id
Critical
pressure
t
t
D TH 086 B
Pressure P
Enthalpy
Changes in state appear in the form of horizontal plateaux of which the length corresponds to the heat
of vaporization.
The isotherms help to locate the representative point of the pure substance as a function of the
pressure and temperature. These isotherms show a break corresponding to the state change when
t < TC (t1 in the diagram). They appear in the form of a continuous curve when t > TC (t0 in the
diagram). P/H diagrams often show other properties, such as entropy S and volume per unit mass v (in
m 3/kg).
00052_A_A
12
II 
BEHAVIOR OF GASES
1
PERFECT GAS
a  Ideal gas law
The perfect gas represents the limit state of any fluid when the pressure tends towards zero. It is a
valid approximation of the behavior of real gases when the pressure is low.
The properties of the perfect gas correspond to those of a fluid in which no intermolecular bonding
force appears. The resulting laws are therefore relatively simple and the behavior of real fluids can be
inferred by introducing correction factors due to molecular interactions.
The behavior of the perfect gas, irrespective of the type of gas, is characterized by a law called the
ideal gas law or Avogadros law, which is written:
P.V=n.R.T
P
V
n
T
R
The most common units and the corresponding values of R are given in the table below.
P
bar
atm
kg/cm2
PSI a
m3 or m3/h
m3 or m3/h
m3 or m3/h
Ft3 or Ft3/h
kmoles or
kmoles/h
kmoles or
kmoles/h
kmoles or
kmoles/h
lbmoles or
lbmoles/h
0.08314
0.08205
0.084478
10.73
This law, although approximate for real gases, allows a number of simple calculations. The accuracy,
although limited, is often sufficient for an approximate representation of the behavior of real gases. A
number of applications is given below.
00052_A_A
13
In normal conditions:
t = 0C
Vm
T
P
R
R.T
Vm =
P
or
T = 273.15 K
P = 1 atm = 1.013 bar
Vm = 22.42 m3 /kmol
Vm in m 3 /kmol
= molar volume = V
m
For an ideal gas:
density in kg/m3
molecular weight in kg/kmol
pressure in bar
temperature in K
universal gas constant = 0.08314
M.P
R.T
M
P
T
R
The specific gravity of an ideal gas with respect to air (sp.gr. gas) can be obtained from the
following equation:
sp.gr. gas =
gas
air
Mgas
M air
Air consists essentially of nitrogen (M = 28) and oxygen (M = 32) and has a molecular weight
M air = 29 kg/kmol.
Thus we obtain:
sp.gr. gas =
M
29
M in kg/kmol
Qm = . Qv
00052_A_A
Qm
Qv
14
M.P
; where M is the molecular weight of the gas, and P and T are
R.T
the flow conditions, the volume flow rate Qv is then obtained from the mass flow rate Qm by the
equation:
If the fluid is an ideal gas: =
Qv
Qm
T
P
M
R
R.T
Qv = Qm .
M.P
in m3 /h
in kg/h
in K
in bar
in kg/kmol
= 0.08314
Sometimes, the ratio R/M is used, denoted R and called gas constant.
or
QV2 = QV1 .
T 2 P1
.
T 1 P2
This expression is often used for the gas volume flow rates in normal or standard conditions.
Normal conditions are defined as follows:
t = 0C (273 K)
273
P
.
T
1.013
or
T
1.013
QV = QVCN .
.
273
P
in m3 /h
in K
in bar
in Nm 3 /h
In practice, gas volume flow rates are often expressed in conditions slightly different from normal
conditions. This has led to the use of standard conditions: P = 1 atm and t = 60F being the
conditions most commonly recognized internationally. For reasons of convenience, it is customary in
France to use P = 1 atm and t = 15C, values which are very close to the above, since 60F = 15.6C.
These different definitions could cause confusion, and it is always preferable to specify the exact
conditions in which a gas volume flow rate is given.
00052_A_A
15
P
T
x
x
x
x
x
x x
x
x x
x
x
x
x
x x
x
D TH 087 A
Qv
If ni is the molar flow rate of component i, the above definition of partial pressure leads to the
following law:
PPi . QV = ni . R . T
This equation can also be written for each one of the components of the mixture.
The summation of these equations for all the components gives:
PPi . Q V = n i . R . T
i
(1)
At the same time, the ideal gas law can be applied to the entire gas mixture by denoting, as N, the total
molar flowrate N = n i. This gives:
i
P . QV = N . R . T
By identifying equations (1) and (2), we obtain:
P = PP i
i
00052_A_A
(2)
16
The total pressure P exerted by the gas mixture is equal to the sum of the partial pressures of each of
the components of the mixture.
The ideal gas law applied to component i and to the gas mixture leads to the two following equations:
PPi . Q V = ni . R . T
P . QV = N . R . T
Combining these two equations gives:
PPi ni
=
P
N
ni
is the molar fraction yi of component i in the gas mixture or:
N
PPi
= yi
P
PPi
P
yi
or
PPi = P . y
The partial pressure of a component of a gas mixture is obtained by multiplying the total pressure by its
molar fraction in the mixture (Daltons law).
These equations, known by the name of Daltons law, give the partial pressure of a component of a
mixture of ideal gases from:
 the total pressure exerted by the mixture which is usually readily accessible by
measurement
 the molar fraction of the component concerned in the mixture: for ideal gases, the molar
fraction y i mol of component i is equal to the volume concentration yi volume:
y i mol = yi volume
If the mass concentration yi mass is known, a conversion is necessary using the following
formula:
M
y i mol = yi mass .
Mi
Mi
M
00052_A_A
17
in Kelvin
are given for a large number of pure substances on plate D1
If the temperature of an ideal gas varies from T 1 to T 2, its corresponding variation in molar enthalpy
can be calculated by the equation:
H = Cp . (T1 T 2 )
where Cp is an average value determined for the temperature interval (T1 T 2 ).
The molar specific heat at constant volume of the ideal gas Cv is also defined, of which the value is
different from Cp. Cv expresses the quantity of heat to be supplied to one mole of ideal gas to raise its
temperature by 1 K at constant volume. The value of Cv is used in the definition of the isentropic
coefficient k of the ideal gas, which determines the behavior of the gas in compression and expansion
processes.
k =
k
Cp
CV
Cp
CV
The value k can be obtained simply for ideal gases using the Mayer equation, which relates Cp and
Cv to the universal gas constant R. It is written:
Cp CV = R
C p , C V in kcal/kmol . K
R
= 1.987 kcal/kmol . K = 8.317 kJ/kmol.K
or:
Cp CV =
00052_A_A
R
M
C p , C V in kcal/kg.C
R
= 1.987 kcal/kmol.K = 8.317 kJ/kmol.K
M
molecular weight of gas in kg/kmol
18
Cp
Cp R
Cp
R
in kcal/kmol.K
= 1.987 kcal/kmol.K = 8.317 kJ/kmol.K
Cp
Cp
R
M
in kcal/kmol.K
= 1.987 kcal/kmol.K = 8.317 kJ/kmol.K
in kg/kmol
or:
k =
Cp
R
M
Note also that the molar specific heat Cpm of a mixture of ideal gases is obtained from the Cpi of
the components of the mixture by molar weighting:
C pm = yi Cpi
i
yi
molar fraction of i
( )
The (HT)F help to determine the enthalpy variations during chemical conversions.
They are given on Plates E18 in cal/mol at different temperatures: 0 K, 298 K, 400 K, 600 K, 800 K
and 1000 K for a large number of pure organic and inorganic substances.
(GT)
are given on plates E19. As for enthalpy H, the free enthalpy G is expressed in cal/mol. It is
00052_A_A
19
2
V
Vpg
V
Vpg
n.R.T
P
Consequently:
Z =
P.V
n.R.T
Hence:
P.V=Z.n.R.T
This law can be qualified as the real gas law, and the compressibility factor appears as a corrective
factor to the ideal gas law. If the compressibility factor of the real fluid takes the value 1, its behavior is
identical to that of the ideal gas, and this happens when the fluid is a gas at very low pressure.
If we glance at all the conditions in which a fluid may be found (vapor, saturated or unsaturated liquid,
supercritical fluid), we find that, in practice, the compressibility factor deviates quite significantly from
the value 1, which is characteristic of the ideal gas.
This is obvious for the liquid state in which the real fluid volume is much lower than that of the ideal gas
(Z << 1). In the gas state, especially for condensable vapors, wide differences from ideal gas behavior
are also observed. The representation of the volume behavior of a pure substance in the fluid state is
clearly illustrated by Amagats diagram, which gives isotherms for the variation in Z as a function of
pressure.
b  Amagats diagram
The shape of the isotherms plotted on the Amagat diagram shown below can be analyzed on the
pressure/temperature diagram, for example by assuming a temperature lower than the critical
temperature and by increasing the pressure from zero.
00052_A_A
20
LIQUID
LS
PS
VS
VAPOR
0
D TH 088 B
Pressure
Temperature
 As the pressure then rises in the liquid zone, the compressibility factor increases in so far as the
volume of liquid varies slightly while that of the ideal gas to which it is compared decreases in
inverse proportion to the pressure.
Z=
PV
RT
t = 1.227C
Ideal
Z=1
gas
d
ate
tur
Sa apor
v
t = 177C
7C
0.75
t=
V
Vs
77
AMAGAT'S
DIAGRAM
FOR
ETHANE
t = 7C
Z
0.25
2.5C
t=tc=3
t = 37C
D TH 113 B
Critical
compressibility
factor
t = 25C
0.5
Change of
state plateau
Ls ted
ra
Satu iquid
l
0
00052_A_A
L
25
A
50
75
P (atm) 1 0 0
21
Amagats diagram given above for ethane C 2 H 6 shows the variation in the compressibility factor at
different temperatures.
 the isotherms 7 and 25C illustrate the above path.
 the critical isotherm plotted for t = tc = 32.5C shows an inflexion point at the critical
pressure PC. In these conditions, the compressibility factors of the liquid and vapor phases
are equal, and correspond to the critical compressibility factor Zc. It may be observed that
the value of Z C is 0.285.
 the isotherms plotted at temperatures higher than tC correspond to increasing
compressibility factors which approach the value of 1 at very high temperature. In the
hypothetical conditions t = 1227C, ethane is virtually an ideal gas irrespective of the
pressure
A specific Amagat diagram can be plotted for every pure substance. However, all the diagrams, which
are different in terms of temperature and pressure, reveal identical behavior and an approximately
universal value of the critical compressibility factor ZC. Plates A2 give the values of ZC for many
pure substances. They are close to 0.27 for hydrocarbons. For other compounds, ZC differs from this
value while note deviating from it excessively:
Hydrogen
Oxygen
Nitrogen
Water
Z C = 0.305
Z C = 0.288
Z C = 0.290
Z C = 0.229
This similarity in the behavior of different pure substances at the critical point is also found when they
are in relatively identical conditions with respect to critical conditions. This leads to a very
important law called the law of corresponding states, which applies not only to compressibility
factors, but also to many other properties of pure substances.
3
Reduced pressure
PR =
Reduced temperature
TR =
P
PC
T
TC
T and TC in Kelvin
T temperature of the fluid
PC critical temperature of the pure substance
00052_A_A
22
This law applies primarily to the compressibility factor Z. Plate I2 shows the universal diagram used
to determine Z as a function of PR and T R.
The diagram below, taken from The Properties of Gases and Liquids (Reid and Sherwood) gives,
as an example, the value of the compressibility factor for reduced pressures lower than 1 and reduced
temperatures between 0.6 and 3.
3.00
2.00
1.60
1.40
1.30
1.00
0.90
0.8
0.80
1.20
1.15
0.9
0.70
1.00
0.50
0.95
2.00
1.40
1.10
1.00
0.90
0.85
0.70
0.30
0.0
0.80
0.75
0.90
0.00
0.05
0.10
0.1
0.2
0.3
Satu
ratio
n lin
1.05
e
TR
TR
PR
0.4
0.5
0.6
1.00
0.7
0.8
0.9
1.0
Reduced pressure P R
D TH 114 B
0.60
0.40
1.10
0.9
5
0.6
0.60
Compressability factor Z =
PV
RT
0.8
0
All the isotherms can be seen to converge towards Z = 1 as the reduced pressure tends towards zero.
Complementary diagrams help to obtain Z in all conditions up to reduced pressures of 40.
These generalized diagrams actually correspond to an average behavior of the different hydrocarbons
and other compounds. They therefore give a good approximation of the value of the compressibility
factor.
In using the foregoing correlations for a mixture, it is assumed that PR and TR are replaced by
pseudoreduced coordinates P PR and TPR. These are obtained by molar weighting of the critical
coordinates of the components, which leads to the calculation of the pseudocritical pressure of the
mixture PPC and its pseudocritical temperature TPC:
00052_A_A
23
PPC = yi P Ci
Pseudoreduced pressure
PPR =
P
PPC
Pseudoreduced temperature
T PR =
T
T PC
yi
molar fraction of i
PCi
P
critical pressure of i
operating pressure
PPC
PPR
pseudocritical pressure
pseudoreduced pressure
yi
molar fraction of i
T Ci
T
critical temperature of i
operating temperature
T PC
T PR
pseudocritical temperature
pseudoreduced temperature
Vm = Z
=
Z.R.T
M.P
 relationship between mass flow rate and volume flow rate for a real gas:
Qv =
Qm
or
Qv = Qm .
Z.R.T
M.P
hence
Q v2 = Q v1 .
Z2
.
Z1
T 2 P1
.
T1
P2
24
Reduced 1
saturation
pressure
Ps
P
0.5
c
LIQUID
0.1
VAPOR
D TH 115 B
wate
ne
buta
met
han
0.05
ammonia
0.01
0.4
0.5
0.6
0.7
0.8
0.9
1
Reduced temperature
T
T
In consequence, many improvements to the law of corresponding states have been suggested to
obtain greater accuracy in determining the properties of fluids. These commonly consist of introducing
a third parameter in addition to TR and PR, to characterize the type of fluid and thus to refine the
method. This is referred to as the law of corresponding states with three parameters.
00052_A_A
25
4
PS
= 0.1
PC
if
TR =
T
= 0.7
TC
The differences in behavior of simple fluids are characterized by the value of the acentric factor defined
as follows:
PS
= log 10 1
P
C
PS
acentric factor
vapor pressure at TR = 0.7.
PS
= 0.1, the acentric factor is zero, and consequently the law with two parameters suffices
PC
to obtain the properties of the pure substances. In practice, as indicated by Plates A2, rather
diversified values of the acentric factor are observed.
Clearly if
00052_A_A
26
It may be advantageous to determine the value of the acentric factor from readily accessible
parameters like TC, PC and Tnb, the normal boiling point of the pure substance. It can be shown that a
good approximation of can be obtained by the formula:
3 log P
7 T 10 C 1
C 1
T nb
T nb
PC
TC
main term obtained as a function of P R and TR, on the chart of Plate I3, or from the table on
Plate I3B,
correction factor given as a function of PR and T R by Plates I3 or I3 bis
acentric factor of pure substance, Plates A2.
For mixtures, the reduced pseudocoordinates PPR and TPR can be calculated, and the acentric
factor is calculated for the mixture m:
m = yi i
i
i
yi
The law of corresponding states with three parameters also helps to determine the other properties of
real fluids. The corresponding correlations are usually presented in the form of generalized charts
giving, as a function of TR, P R and , for example, either the correction factors to be applied to the
properties of the fluid considered as an ideal gas (enthalpy, entropy, etc.) or direct values of certain
properties: vapor pressure, fugacity coefficient, etc.
Another method for solving the same type of problem, which is more appropriate for numerical
calculations on a computer, has developed rapidly in the last twenty years: the use of equations of
state.
00052_A_A
27
5
or:
 the ideal gas volume is increased by a factor b which accounts for the actual volume of the
molecules of the real gas. b depends on the type of gas and is called the covolume:
Vreal gas = Videal gas + b
The equation of state of ideal gases is written for one mole of gas:
Ppg . Vpg = R . T
It consequently becomes:
a
P + V2 (V b) = RT
From the end of the nineteenth century until recently, many equations of state have appeared for a
closer representation of the behavior of real fluids: Clausius (1880), Berthelot (1900), BenedictWebbRubins (1940), RedlichKwong, etc. The latter, the RedlichKwong equation of state, appeared
in 1949 and has a form quite similar to the Van der Waals equation:
a
P +
(V b) = RT
T V (V + b)
Since its origin, this empirical equation has undergone several hundred changes intended to make it
more efficient. The latest forms (SoaveRedlichKwong and PengRobinson) are widely used in all
computer programs for calculating the thermodynamic properties of fluids.
For a pure substance, parameters a and b can be determined from its critical conditions T C and PC:
2.5
a = 0.4278
00052_A_A
R 2 TC
PC
b = 0.0867
RTC
PC
28
Since a and b are determined, the equation of state also helps to calculate the critical compressibility
PC V C
.
factor ZC =
RTC
The value obtained, ZC = 1/3 is too high compared with those obtained by experiment, that usually
range between 0.27 and 0.29. This difference shows that the behavior of real fluids is inaccurately
represented by this equation of state in the neighborhood of the critical point.
It is more convenient to use the equation of state by changing the variables.
P.V
the RedlichKwong equation of state is transformed
R.T
into a thirddegree equation in Z which is often presented as follows:
Z=
Z
A2 BP
.
Z BP B Z + BP
In this equation, A and B are constants that depend on the type of substance and the operating
conditions:
a 0.5
=
A = 2 2.5
R T
B =
0.6542
1.25 0.5
PC
TR
b
0.0867
=
RT T R P C
A2
and BP are given by:
B
BP =
0.0867 PR
TR
The resolution of this equation implies an iterative calculation which is initiated by assigning an initial
value to Z in order to calculate the righthand expression, i.e. to obtain a new value of Z which, if
different from the previous one, is reintroduced into the equation until convergence is obtained.
The equation of state applies to gas mixtures using parameters Am and Bm defined as follows:
Am = y i Ai
i
Bm = yi Bi
i
where Ai and Bi are parameters A and B of component i, and yi is the molar fraction of i.
00052_A_A
29
The RedlichKwong equation of state has undergone more than 700 changes since 1949. Among the
new forms most widely used are the following:
 the SoaveRedlichKwong equation of state (SRK, 1972)
a (T, )
P +
V (V + b) (V b) = RT
a
is replaced by a function a (T,) depending on the
T
a (T, )
P +
V (V + b) + b (V b) (V b) = RT
6
3 A 2
H = H0 RT
ln
2 B
H
H0
A,B
1 + BP + 1 Z
There does not exist today a single equation of state capable of giving excellent results for all these
properties and for all fluids. Good accuracy can nevertheless be anticipated in the specific validity
range of a proposed equation.
00052_A_A
30
ur v
e
ur v
e
C2
C3
iC4
nC4
iC5
nC5
bu
bbl
ec
%
molar
8
22
14
24
10
22
De
wc
15
Pressure (atm.)
20
L+V
LS
50
70
10
30
LIQUID
90
10
VS
10
VAPOR
Temperature (C)
0
50
50
100
Starting with the liquid state on the lefthand side of the diagram and by following the change in the
mixture at constant pressure and rising temperature by continuous input of heat, the following steps
are observed:
 initial subcooled liquid state (point L)
 heating of liquid by input of sensible heat
 initiation of vaporization at the bubble point (or boiling point) of the mixture: the mixture is
in the saturated liquid state (point LS)
 progressive vaporization by input of latent heat at rising temperature: the liquid and vapor
phases are saturated and in equilibrium, and their composition changes throughout
vaporization
 end of vaporization at the dewpoint of the mixture, which is in the saturated vapor state
(point VS)
 this is followed by the superheated or dry vapor state at any temperature above the dewpoint (point V)
The locus of the bubble points, (corresponding to the bubble point temperature and bubble point
pressure), defines the bubble point curve of the mixture. Similarly, the locus of the dewpoints (dewpoint temperature and dewpoint pressure), characterizes the dewpoint curve of the mixture.
00052_A_A
D TH 025 B
31
These two curves appear to be approximately parallel to the vapor pressure curves in the low pressure
zone. At higher pressure, they close the liquid/vapor domain by joining the critical point C of the
mixture.
The figure below, which applies to mixtures of ethane and heptane, shows complete ranges of
liquid/vapor equilibria. These are inscribed between the two vapor pressure curves of the pure
substances. They approach one or the other as a function of composition.
100
Mixture
Mixture
Mixture
Mixture
90
70
Atm  pressure
80
60
containing
containing
containing
containing
96.8
77.1
58.7
26.5
mol
mol
mol
mol
%
%
%
%
of
of
of
of
ethane
ethane
ethane
ethane
1
C
50
1
2
3
4
eth
20
e
nh
pta
ne
10
Temperature C
0
40
80
120
160
200
240
D TH 116 B
30
ane
40
280
It may be observed in a given range that the critical point C of the mixture located at the junction of
the bubble point and dewpoint curves of the mixture does not occupy a particular position.
It is generally not found at the maximum pressure point of the liquid/vapor equilibrium range
(cricondenbar) nor at the maximum temperature (cricondentherm).
Note that the liquid/vapor equilibrium range of mixtures extends much further in pressure than that of
the pure substances. It is limited by the bell curve which joins the critical points of the different
mixtures.
00052_A_A
32
2
composition zi
composition yi
Feed
Saturated
vapor
composition xi
Saturated
liquid
D TH 089 B
The temperature and pressure maintained in the drum determine the vaporized percentage of the
mixture, and hence, considering the feed flow rate A, the vapor and liquid flow rates V and L
respectively.
The liquid and vapor phases in contact at the same temperature and the same pressure are said to be
in liquid/vapor equilibrium.
 the vapor phase is a saturated vapor at its dewpoint
 the liquid phase is a saturated liquid at its bubble point.
Both phases have different compositions:
 the molar fractions in the vapor phase are denoted yi
 the molar fractions in the liquid phase are denoted xi
The relationship between the compositions of the two phases can be identified in terms of the vapor
pressure of the liquid phase.
00052_A_A
33
b  Vapor pressure or bubble point pressure of the liquid phase, Raoults law
The operating pressure P of the above vessel is the vapor pressure which is also called the bubble
point pressure of the liquid mixture:
S
P = Pm
P
S
Pm
S
P i . xi
RAOULTS LAW
xi
Liquid mixtures which obey this law are said to be ideal solutions and this can be considered to apply
to mixtures of hydrocarbons belonging to the same chemical family and at low pressure.
Varying deviations from the behavior of ideal solutions appear when:
 the mixture contains aromatics or hydrocarbons of very different sizes
 polar compounds are present: CO2 , H 2 S, water etc.
Using Raoults law, it is possible to determine the vapor phase composition and, using a liquid/vapor
equilibrium coefficient, identify the differences in composition between the two phases.
c  Vapor composition and equilibrium coefficient
Raoults law helps to identify the contribution of each component present in the liquid phase to the
vapor pressure of the liquid, i.e. to the operating pressure P.
For substance i, for example, this contribution is called the partial vapor pressure of i, and
corresponds to the partial pressure PPi of this component in the gas phase:
S
00052_A_A
34
Daltons law, which is applicable assuming that the vapor phase is an ideal gas, serves to use yi, the
molar fraction of i in the gas phase:
yi =
PPi
P
hence
yi =
PSi . x i
P
This equation helps to determine the composition of the vapor phase from the calculation of the partial
vapor pressures of each component of the liquid phase.
It is also advantageous to use the ratio y i/xi of the molar fractions of component i in the two phases,
which characterizes the behavior of this component in the liquid/vapor separation.
This ratio is called Ki, the equilibrium coefficient (or K value) of component i.
The above equation helps to write:
yi Pi
Ki = =
xi
P
Ki
yi
xi
equilibrium coefficient of i
molar fraction of i in the vapor phase
molar fraction of i in the liquid phase
Pi
P
Ki characterizes the volatility of i in the liquid/vapor separation conditions. For ideal liquid phases and
ideal gas vapor phases, the above expression shows that Ki only depends on:
 the type of component i
This factor is extremely important in all calculations of liquid/vapor separation (flash, distillation,
absorption, stripping etc.) because the practical approach to these problems always first requires the
determination of the values of the equilibrium coefficients of the components concerned.
Many methods have therefore been developed for determining the values of these equilibrium
coefficients as accurately as possible. The simplest and also the most limited are graphic methods.
d  Simple graphic methods for determining equilibrium coefficients
Determining the equilibrium coefficients is only a simple problem for ideal solutions or mixtures which
display behavior relatively similar to that of ideal solutions.
This applies to hydrocarbon mixtures of similar size and chemical family and at low pressure.
The methods applicable in this case include:
Pi
00052_A_A
35
Faced with a problem of liquid/vapor separation, access to the equilibrium coefficient helps to calculate
the flash conditions, and especially the compositions of the liquid and vapor phases. Yet this access is
relatively complex when deviations in behavior from ideal solutions appear.
The equilibrium coefficients also help to measure and compare volatilities of different components
involved in liquid/vapor separations.
e  Volatility and relative volatility
Irrespective of the complexity of the method used to determine an equilibrium coefficient, its value
appears as an indicator of its volatility in the flash conditions:
K i > 1 indicates a light or volatile component
K i < 1 corresponds to a nonvolatile or heavy substance
In the main industrial separation processes based on differences in volatility, it is often advantageous
to characterize the volatility difference existing between two components to be separated and thus to
gauge the difficulty of the process.
For ideal mixtures, the volatility difference between two substances i and j can be characterized from
the ratio of their equilibrium coefficients.
This leads to the definition of a relative volatility of component i with respect to component j ij.
K
ij = Ki
j
ij
Pi
Pi
K
P
ij = K i = S = S
j
Pj
Pj
P
By using Raoults expression, ij appears to be given by the ratio of the vapor pressures of i and j. It is
S S
possible to conceive that, in a column, despite the variations in temperature, the ratio Pi /P j remains
relatively constant. An average value can be selected corresponding, for example, to an intermediate
temperature in the column. This offers a qualitative indication of the volatility difference existing
between the substances to be separated.
00052_A_A
36
Applied to a number of common refinery and petrochemical separations, this method for determining
the relative volatility gives the following results.
Component 1
Component 2
Operating
pressure
12
Industrial column
Propane
nbutane
Isopentane
Metaxylene
Isobutane
Isopentane
npentane
Orthoxylene
17 bar
11 bar
2.5 bar
1 bar
2.44
2.07
1.23
1.15
Depropanizer
Debutanizer
Deisopentanizer
Aromatics
Note that the volatility difference between two substances is very sensitive to the pressure, and that it
increases when the pressure decreases for hydrocarbon mixtures. A separation of such mixtures by
distillation is hence always easier at lower pressure.
The table below shows the change in relative volatility of isopentane with respect to npentane at
different pressures. In each case, the temperature selected corresponds to the average of the boiling
points of the two components.
00052_A_A
Pressure in atm
Average
temperature
K ic5
K nc5
ic5/nc5
0.2
1
2.5
5
10
10
32
62
91
120
1.17
1.13
1.07
1.07
1.04
0.76
0.85
0.87
0.92
0.93
1.54
1.33
1.23
1.16
1.09
37
Vapor
pressure
Constant temperature
PS
a
PS
m
PS
b
t's la
x
0
D TH 090 B
l
Raou
a
1
a
xa = 1
xa = 0
PSm = PSa
PSm = PSb
The line thus obtained helps to determine the vapor pressure of liquid mixtures a/b graphically as a
function of their composition xa.
Starting with this diagram, the demonstration of nonideal behavior of a real solution is reflected by
the appearance of a deviation in the evolution of the vapor pressure.
As indicated in the figures below, positive or negative deviations are observed with respect to the vapor
pressure values indicated by the Raoults law.
00052_A_A
38
P
T
PS
b
(heavy)
ssu
ixtur
of m
re
ult
Rao
's la
PSa
(light)
es
u
Rao
aw
PS
b
(heavy)
Positive
deviation
0
lt's l
PaS
(light)
Negative
deviation
1
D TH 091 B
Va
or
pre
1
a
These deviations indicate the extent of the molecular interactions in the liquid phase.
Raoults law reflects the forces of attraction existing in the liquid phase between the hydrocarbon
molecules of the same size and the same chemical family. The appearance of stronger forces of
attraction leads to greater cohesion of the liquid phase and a lower vapor pressure than the one
indicated by Raoult (negative deviation).
On the contrary, a higher vapor pressure than the Raoult figure indicates weaker forces of attraction
between the molecules of the liquid phase (positive deviation).
The consideration of a nonideal behavior corresponding to the deviations from Raoults law uses a
correction factor for the partial vapor pressures of each component. This factor, denoted i, is called
the activity coefficient of component i. It depends on the temperature, the type and the
concentrations of the other components.
The vapor pressure of the liquid mixture is written then:
PSm = PSi . xi . i
i
00052_A_A
PSi
xi
PSm
39
For a nonideal solution in equilibrium with a perfect gas/gas phase, we can write:
S
PPi P i . xi . i
=
yi =
P
P
or
Ki =
yi
=
xi
PSi . i
P
Ki
PSi
equilibrium coefficient
vapor pressure of i
activity coefficient of i
total pressure
The determination of the equilibrium coefficient Ki therefore requires the knowledge of the activity
coefficient i, whose value depends on the composition of the liquid phase. Ki then depends on i, T, P
and all the x i.
Depending on the type of mixture, different methods are proposed:
 for mixtures of nonpolar compounds (e.g. hydrocarbons), the deviations are smaller and
the activity coefficients can be determined by the theory of regular solutions due to
Scatchard and Hildebrand. The calculation is then predictive. The recent equations of
state also help to characterize the behavior of the liquid phase in this case
 for mixtures containing polar compounds, the deviations are much wider and the activity
coefficients can only be calculated from a minimum of experimental data.
The application of the different existing models is relatively complex. The most commonly
used are the following ones:
Models for determining the activity coefficients of nonideal mixtures:
Wilson (1963)
UNIQUAC (1975)
NRTL (1968)
UNIFAC (1975)
Note that the development of these methods designed to calculate the behavior of liquid mixtures of
polar compounds is relatively recent.
Moreover, in addition to the deviations encountered in the liquid phase are those relative to the vapor
phase. Consideration of these differences from ideal solutions and from ideal gases involves a specific
thermodynamic quantity, the fugacity.
00052_A_A
40
b  Concept of fugacity
A situation of liquid/vapor equilibrium
illustrated by the figure opposite is
characterized by the coexistence of two
phases, separated by an interface, at the
same temperature and pressure.
P
V
T
D TH 092 A
This concept of what occurs is perfectly justified for ideal solutions and ideal gases, but not for real
fluids. For these, the equilibrium conditions require a definition of a corrected pressure which is really
the effective pressure governing the liquid/vapor equilibria. Apart from ideal gases, this effective
pressure is different from the real pressure, and is called the fugacity (f). It is naturally expressed in
pressure units and the condition of liquid/vapor equilibrium of the two saturated phases VS and LS is
written:
fVS
Liquid/vapor equilibrium
fLS
For a mixture at liquid/vapor equilibrium, the equilibrium condition is that the fugacities in the liquid and
vapor phases must be equal for each component i:
V
fi
fi
Fugacity of i component in the vapor phase = fugacity of i component in the liquid phase
Based on this equality, it is possible to determine the equilibrium coefficient Ki of each component by
expressing the fugacities.
If the vapor phase can be considered as an ideal gas, and if the liquid phase is an ideal solution, we
have:
00052_A_A
f i = P . y i = PP i
f i = Pi . x i
at liquid/vapor equilibrium
fi = fi
thus:
P . y i = Pi . x i
41
This returns us to the expression already obtained from the laws of Raoult and Dalton, which gives the
ideal equilibrium coefficient:
S
yi Pi
Ki = =
xi P
Ki
For the more general case of a real gas vapor phase and a nonideal solution liquid phase, the
fugacities of the components in each of the phases are expressed in a more complex manner.
c  Fugacity of component i in vapor phase
The fugacity of i in the vapor phase is obtained by correcting the foregoing expression and by
V
introducing a correction factor called i , the fugacity coefficient of component i in the vapor
phase. This gives:
V
f i = P . yi . i
V
i 1 when
P0
A number of methods are used to determine the fugacity coefficient of i in the vapor phase. They
include the following ones:
V
 equations of state: by way of example, the expression below gives the value of i
obtained from the RedlichKwong equation of state:
V
ln i = (Z 1)
A,B
Ai,B i
Z
00052_A_A
Bi
A2 Ai Bi BP
ln (Z BP)
2
ln 1 +
Z
B
B A B
42
Two main forms are available for expressing fi , the fugacity of component i in the liquid phase.
 the first and the most classic consists in expressing the activity coefficient i of
component i in the liquid phase.
At low pressure, we have the following expression already presented:
L
f i = Pi . xi . i
S
*L
If the pressure is higher, the vapor pressure Pi must be replaced by fi , the fugacity of pure
*L
*L
f i = fi . x i . i
The fugacity of pure component i in the saturated liquid state is obtained by:
*L
*S
f i = Pi . i . e
S
V*iL P Pi
RT
Pi
is the fugacity coefficient of pure component i in the vapor state and at the
P
V*iL
*S
 the second uses the same formalism as for the vapor phase. A fugacity coefficient of
L
L
L
f i = P . xi . i
00052_A_A
fi
P
43
Since i , i depends on the temperature, pressure and composition of the liquid phase, it
can be calculated from an equation of state capable of representing the liquid phase. The
V
expression giving the fugacity coefficient is of the same type as that which gives i , but the
compressibility factor used is that of the liquid phase. For hydrocarbon mixtures, the
L
Using the explanation thus obtained for fugacities fi and f i , it is possible to clarify overall
the contents of the different thermodynamic methods available for calculating the
liquid/vapor equilibria.
e  Methods for determining equilibrium coefficients
Apart from a number of graphic methods already presented, the determination of the equilibrium
coefficients Ki requires thermodynamic calculations that are relatively complex, and are also capable of
predicting the properties of the phases in liquid/vapor equilibrium. The methods used are often
qualified as thermodynamic models. For the user of chemical engineering software, the problem
often faced is to select, from a range of thermodynamic models, the one which is appropriate to the
mixtures treated and the operating conditions. It is therefore important to know the general properties
and fields of application of the main models used. Plate J4, Choice of a thermodynamic model,
indicates the main possibilities available today in this area. Among these, the following can be
distinguished.

MODELS OF CHAO AND SEADER (1961) AND OF GRAYSON AND STREED (1963)
V
fi = P . yi . i
and
fi = fi . xi . i
*L
i
yi f i
Ki = = P .
xi
v
The equilibrium coefficient in this correlation is calculated from three distinct parameters:
v
*L
fi
RT . ln . i = Vi . ( i m)2
00052_A_A
44
*L
Vi
V
H25
RT 1
2
i =
V*L
25
V25
m = i xvi . i
x vi
volume fraction of i
*L
fi
P
*L 0
f i
= log
log
P
P
fi
*L
f 1
+ i log i
*L
fi 0
A1
2
2
2
log = A0 +
+ A2 TR + A3 TR + (As + A6 TR + A7 TR) P R + (A8 + A9 TR) PR log P R
P
TR
f *L 1
i
1.22060
3
log = 4.23893 + 8.65808 TR
3.15224 TR 0.025 (PR 0.6)
P
TR
A0 to A 9 are universal constants except for methane and hydrogen, for which special constants are
defined.
To summarize, the data on each component needed to make these correlations are limited to:

*L
This models few data requirements have helped to use it to deal with liquid/vapor equilibria of
mixtures of unidentified components: petroleum cuts, crude oils.
00052_A_A
45
This is because these can be divided into pseudocomponents characterized by their specific gravity at
15C, their tmav and their molecular weight. Using these data alone, correlations usually based on the
properties of pure substances of similar volatility help to assign values for the five parameters Tc, Pc,
V
*L
, H25, v25.
This makes it possible to calculate the equilibrium coefficients of these pseudocomponents, and thus
offers predictive models capable of calculating the liquid/vapor equilibria of mixtures of identified
hydrocarbons and petroleum cuts.
The range of validity of the Chao and Seader model was limited to 500F (260C) and 2000 psia
(140 bar). It was extended by Grayson and Streed in 1963 to 900F (482C) and 8000 psi (560 bar).
The accuracy of this method, has been evaluated by different authors at a relative mean error of 8% in
the equilibrium coefficients. But it deteriorates considerably if the reduced temperature of certain
components exceeds the value of 1.3 or if the mixture contains H2S and CO2.

In this recent model, the fugacities of component i in the two phases are expressed as follows:
V
f i = P . yi . i
f i = P . xi . i
L
At equilibrium: f i = f i
hence:
y i i
Ki = = V
xi
In this case, both fugacity coefficients are calculated from the same equation of state, which is
the RedlichKwong equation improved by Soave. This equation introduces interaction parameters kij
between the components of the mixture, which are adjusted to experimental data. The parameters kij
offer a better representation of nonideality.
For hydrocarbon mixtures belonging to the same chemical family, the kij can be taken as zero, but this
does not apply in the presence of hydrocarbons of different families, H2S, CO 2 etc.
Even in the absence of these coefficients kij , this new method is considered superior to the method of
Chao and Seader. It helps to deal with pseudocomponents, but it remains limited to nonpolar
compounds.
It also offers the advantage of dealing better with liquid/vapor equilibria at high pressure.
00052_A_A
46
Similar to the SRK model, the PengRobinson model is derived from the RedlichKwong equation of
state. It offers greater accuracy in predicting the densities of the liquid phase.
OTHER MODELS
Plate J4 shows other models capable of determining the equilibrium coefficients of hydrocarbons from
an equation of state. The BenedictWebbRubin model, which has eight parameters, is ideal for
calculating liquid/vapor equilibria at low temperature (t < 30C).
The sour water model applies to mixtures of H 2S, NH3, CO2 and H2O. It applies to process water
strippers, and is essentially based on experimental data.
Models that represent the liquid phase (activity coefficients i) are indispensable if the problem is
concerned with mixtures of polar compounds. The models already presented (Wilson, NRTL,
UNIQUAC etc.) are difficult to use, and demand the availability of binary experimental data or a data
bank. The Wilson model is restricted to the representation of liquid/vapor equilibria. The NRTL and
UNIQUAC models can also deal with liquid/liquid equilibria.
Note also that, in the absence of experimental data, use can be made of the semipredictive UNIFAC
model, which is based on set contributions.
4
t
A
zi
D TH 093 A
V, yi
L, xi
00052_A_A
47
A
A . zi
=
=
L+V
L . x i + V . yi
Normation equation
xi
of
or
compositions
yi
yi
Ki . xi
and
and
yi
L
1 equation
n equations
1 equation
n equations
2 n + 2 equations
UNKNOWN VARIABLES
Concentrations
Flow rates
Pressure P and temperature T
xi
V
2 unknown variables
2 unknown variables
2 unknown variables
2 n + 4 unknown variables
The system is hence defined if two parameters are fixed. The most common cases are described
below.
Different kinds of problem to be solved:
 bubble point temperature at a given pressure
 dew point temperature at a given pressure
 flash at a given pressure and temperature
a  Calculation of the bubble point of a mixture at a given pressure
Data:
P imposed
bubble point V = 0)
In this case:
x i = zi
hence:
y i = Ki . zi
yi = 1
i
00052_A_A
48
Hypothesis on t
=1
Calculation of Ki zi
Calculation of Ki
t = t bubble
D TH 2061 A
The following resolution flow chart applies when Ki only depends on the pressure and temperature
(ideal mixtures).
To account for the influence of vapor and liquid phase compositions on Ki, it is necessary to add an
internal redefinition loop of the Ki after calculating the compositions.
yi = Ct
Calculation of Ki zi
Calculation of Ki
yi = 1
t = t bubble
D TH 2061 B
Hypothesis on t
yi varies
yi 1
b  Calculation of the dewpoint of a mixture at a given pressure
Data:
P imposed
dewpoint L = 0
In this case:
hence:
z i = Ki . xi
zi
= xi
Ki
or
xi = 1
with
The trial and error calculation is represented on the following flow chart:
Calculation of Ki
Calculation of
zi
Ki
=1
00052_A_A
t = t dew
D TH 2061 C
Hypothesis on t
49
As above, a complementary loop redefining the Ki after calculating the compositions is necessary if Ki
is a function of xi and y i.
c  Calculation of a flash
Data:
flash pressure
flash temperature
Az i
L + V . Ki
A . zi
L
+
V . Ki
i
xi = 1 =
i
If Ki only depend on P and t, their value can be determined and the following trial and error method
implemented:
V=AL
Calculation of xi
Calculation of xi
=1
L solution
D TH 2061 D
Hypothesis on L
V=AL
Calculation of Ki
Calculation of xi
and yi
xi = Ct
=1
L solution
xi varies
1
00052_A_A
D TH 2061 E
Hypothesis on L
50
Pressure (atm)
Mixture number
ce a
3
4
of s
ubs
tan
ce
of su
1
ve
30% b
50% a
4
4
50% b
30% a
5
5
70% b
10% a
90% b
D TH 026 B
10% b
70% a
cur
90% a
urve
VP c
Mixtures
bstan
VP
bp a
Bubble Dew
point of point of
mixture mixture
3
bp b
Temperature (C)
An horizontal plotted for the pressure selected P gives the equilibrium temperatures of the different
mixtures, and particularly the extreme equilibrium temperatures which correspond to the boiling points
of the two pure substances. Plotted on a composition/temperature graph, these temperatures reveal
two sets of points defining two curves which make up the equilibrium diagram of mixture a/b under
pressure P.
00052_A_A
51
The upper curve connects the dewpoints and the lower curve connects the bubble points.
Temperature
Temperature
P
VAPOR
Boiling point
of b
Boiling point
of a
0 10
Mixtures
30
50
70
9 0 100
D TH 094 B
LIQUID
This diagram is very useful, particularly in distillation, because, at constant pressure, it helps to
determine the relationships between the compositions of the saturated phases (liquid or vapor)
and their temperature.
If the equilibrium coefficients Ka and Kb of the two components are available at pressure P and in
the temperature interval between the boiling points tbp.a and t bp.b, the lens can be generated as
follows:
t bp.a < t < t bp.b
choice of a temperature t
determination of
Ka =
ya
xa
and
Ka xa + Kb xb = 1
x a + xb = 1
Ka xa + Kb (1 xa ) = 1
xa =
Kb =
yb
at t and P
xb
(bubble point)
1 Kb
Ka Kb
This calculation can be repeated for different temperatures until a sufficient number of points has been
obtained to plot the two curves.
The use of this diagram can be illustrated by the study of a flash.
00052_A_A
52
t (C)
t (C)
P
Boiling
point of b
VAPOR
L+V
A
L
Boiling
point of a
L
x
0
z, x, y
x
1
A = L+V
Balance on a
Az = Lx + Vy
Or
Az = (A V) x + y
Hence
V=A.
zx
yx
and
L = AV
The application of this formula is known by the name of the lever rule or rule of inverse segments.
Geometrically, in fact, (z  x) represents segment AL and (y  x) represents segment LV:
V=A.
00052_A_A
AL
LV
L=A.
AV
LV
D TH 095 B
LIQUID
53
To facilitate the analysis of the operation of distillation columns, it is also advantageous to represent
the molar enthalpy diagram of binary mixtures. The standard representation corresponding to an
ideal mixture is shown below.
Temperature
P
Boiling
point of b
L+V
A
L
Boiling
point of a
H V = Ha y + Hb (1 y)
hL = ha x + hb (1 x)
This calculation, which assumes
ideal behavior of the mixture, can be
repeated for different compositions
of the saturated liquid and vapor
phases. The result is an upper curve
giving HV as a function of y and a
lower curve giving h L as a function of
x.
This diagram shows a and b
which are the molar heats of
vaporization of substances a and b
under pressure P. It may be
observed that, for an ideal mixture,
the molar enthalpy curves of the two
phases approach two parallels and,
in consequence, the molar heats of
vaporization vary only slightly with
the composition.
molar
enthalpy
Hv
H
a
hL
L
h
x
0
b
x, y, z
y
1
a
D TH 096 B
The oblique line joining the two phases in equilibrium is usually represented by an arrow, and is called
the tie line.
The relative constancy of molar heats of vaporization is important in distillation columns. Indeed, on
their trays we observe a partial condensation of the vapor flow and partial vaporization of the liquid
flow. These phenomena concern mixtures of different compositions but with similar molar heat
vaporization.
Consequently, molar flowrates concerned by vaporization and condensation are roughly equal which
leads, finally, to a certain constancy of the molar flowrates of saturated liquid and vapor in the industrial
distillation columns.
00052_A_A
54
In general, the shape of the equilibrium lens shows the selectivity of the phase equilibria, and the
diagrams corresponding to two components of similar volatilities or, on the contrary, very different
volatilities are shown below.
close to 1
high compared to 1
P
z y
For the same ideal hydrocarbon mixture, the influence of pressure in differences in volatility leads to
the lenses below. The equilibrium temperatures are obviously shifted with the pressure, and a
simultaneous drop in selectivity of liquid/vapor equilibria which accompanies an increase in pressure is
simultaneously observed.
t (C)
P
3
P
t
P <P <P
1
2
3
P
00052_A_A
y y
3
2 1
mol % of component a
in mixture
D TH 098 B
D TH 097 B
55
c  y/x diagram
To illustrate the selectivity of liquid/vapor equilibria, it is also advantageous to represent the vapor
phase composition y at a given pressure as a function of the liquid phase composition x. The diagram
obtained is a square diagram. Since the values of y and x are conventionally related to the volatile
component, y is greater than x and the corresponding curve is located above the diagonal of the
square which corresponds to equation y = x.
The construction of this diagram from the lens is shown below. The y/x diagram is the basis of a
number of methods of graphic calculation of distillation columns for binary mixtures. It is used
particularly in the MacCabe and Thiele method.
Temperature
t
t1
Equilibrium
lens
t2
y : Composition
of vapor
100
y1 x2
x1
y2
Pure light
component
P
y2
y=
y  x Diagram
Pure heavy
component
0
x1
x2
100
x : Composition
of liquid
00052_A_A
D TH 099 B
y1
56
1
00052_A_A
57
Solenoid
T.B.P. DISTILLATION
principle
Water on condenser
Condenser
Thermocouple
Vent
Valve
Vent
To vacuum
pump
Heating circuit
compensation
Packed column
 15 18 theoretical
contact stages
 reflux ratio = 5
Flask
Heating
control
D ANA 095 B
Thermocouple
Due to the separating power employed, the components of the product analyzed are relatively well
fractionated in this test and proceed towards the top of the column by order of volatility. The top
temperature therefore reflects the boiling points of the components which reach the top of the column
successively.
One of the test results is the TBP distillation curve, which gives the correspondence between volume
or mass collected and boiling point. It thus indicates the composition of a cut or a crude oil in the sense
of the volatility of its components.
00052_A_A
58
The curves below show the shape of the TBP curves for a complex continuum and for a binary mixture.
Temperature C
Temperature C
Temperature C
tbpb
1 atm.
is
Pd
B
T
till a
ti o
ur
nc
ve
% distilled
% distilled
100
b
TBP curve
for a complex cut
100
D TH 2021 B
tbpa
Equilibrium lens
under P = 1 atm
for mixture a b
TBP curve
of mixture m
b  ASTM distillation
ASTM distillation is a batch distillation without reflux using about one liquid/vapor equilibrium stage.
For light products, Standard ASTM D 86 is used, which corresponds to atmospheric distillation. For
heavy products, vacuum distillation is performed to prevent thermal degradation according to Standard
ASTM D 1160.
In terms of significance, the ASTM method resembles the simple progressive vaporization SPV,
which is a theoretical batch distillation strictly comprising one theoretical stage.
The SPV analysis shows that:
 its initial point is logically the bubble point of the product
 its final point is the boiling point of the heaviest component of the mixture
In actual fact, the following differences are observed with ASTM:
 the ASTM IP is related to the bubble point of the product, but is lower than it because of
the initial rectification that occurs following the generation of a reflux by the cold column
during temperature conditioning
 the ASTM FP is much lower than the boiling point of the heaviest components, because
distillation is generally incomplete, and a nondistillable residue usually remains in the test
conditions
Note that the ASTM IP is affected by the overall composition of a cut, whereas the ASTM FP mainly
depends on the heaviest components of the mixture.
00052_A_A
59
c  Simulated distillation
The simulated distillation of a petroleum cut gives correspondence between the percentage distilled
and the boiling point by a gas chromatography analysis.
The chromatographic column actually separates the hydrocarbons of the sample analyzed according to
their volatility. This column is calibrated by the injection of a mixture of nparaffins with known
boiling points, which help to make a temperature graduation of the chromatogram obtained.
Measuring the areas between the peaks of the nparaffins makes it possible to determine the
relationship between the mass percentages and the boiling points.
Elution time
corresponding to
boiling temperatures
Example of result
370535C cut
C42
C40
C38
C36
C34
C32
C30
C29
C28
C27
C26
C25
C24
C23
D TH 2029 B
C22
1 l cut 370535C
Signal intensity
00052_A_A
60
2
VAPORIZATION CURVE
The vaporization curve, which is also called the Flash Curve, gives the percentage vaporized as a
function of temperature for a given cut and at a given pressure.
Widely used in simplified design methods for drawoff columns, the flash curve is characterized by its
two extreme points:
 the initial point or point 0% vaporized, which is the bubble point of the mixture
 the final point or point 100% vaporized is the dewpoint of the mixture
P
t(C)
0%
100%
F C at
t
tbubble
tdew
FC at
D ANA 2039 B
1 atm
t
tdew
tbubble
% vaporized
100
Temperature C
Temperature C
% distilled
or vaporised
Complex cut
TBP
ASTM
FC
100
b
% distilled
or vaporised
100
Binary mixture
The flash curve naturally shifts with the pressure. It is important because, prior to the existence of the
recent thermodynamic models, it offered a relatively simple means of dealing with problems of
liquid/vapor equilibria in complex continuums.
Indeed, determination of crude oils and atmospheric residues flash curves is necessary in shortcut
calculations of atmospheric distillation and vacuum distillation.
00052_A_A
D TH 2022 A
TBP
ASTM
FC
61
TB
Pd
ist
ill a
ti o
nc
urv
e
Temperature C
t mav
i
Defined
components
pseudo
component i
% weight distilled
D TH 2023 A
% weight
At the same time, if a curve giving the specific gravities of the small range cuts is available, it is
15
t mavi
boiling temperature
zi
mass concentration
15
d4i
00052_A_A
62
Using these basic data, the values of the different parameters needed for the thermodynamic models
must be generated. Taking the case of the Chao and Seader model, the calculation of the equilibrium
coefficient Ki of pseudocomponent i requires:
T Ci
PCi
V25
H25
critical temperature
critical pressure
acentric factor
liquid molar volume at 25 C
enthalpy of vaporization at 25 C
15
60
141.5
60
Spgr60
131.5
M = 5.805 x 105
tmav
tmav in K
spgr0.9371
t mav
TC
PC =
PC in Pa
in K
0.0566
4.12164 0.213426
103 tmav 0.436392 +
+
spgr
spgr
spgr 2
2
11.819 1.53015
9.901
3
+ 107 tmav 4.75794 +
+
1010 t mav 2.45055 +
2
spgr
spgr
spgr 2
00052_A_A
63
C TR = 0.7
may be placed in the following form in order to obtain from TC, PC and t mav:
3 log P
= 7 . T 10 C
C
t mav
PC in atm
T C and t mav in K
6
S
ln PbR 5.92714 + 6.09648/T bR + 1.28862 ln TbR 0.169347 TbR
6
15.2518 15.6875/TbR 13.4721 ln TbR + 0.43577 T bR
Molecular weight
M
=
Density at 25C
25
60
25 = 0.98907 Spgr 60
M obtained by the chart of the characterization factor or by the formula:
M = 42.965 exp (2.097 . 104 tmav) 7.78712 spgr + 2.08476103 . tmav . spgr
] (tmav
1.26007
. spgr4.98308
This formula can be applied to pseudocomponent with a density at 15C less than 0.97 and a boiling
point less than 840K.
Other equations established by Lee Kesler (1975) are given in literature.
V
The enthalpy of vaporization at 25C H25 is calculated using Kistiakowskis formula which gives
HV for the normal boiling point:
Ht
mav
H25
V
Ht
00052_A_A
mav
0.38
T C 537
=
T C T mav
T C in R
64
i =
V25
The work done for each pseudocomponent transforms a product with an infinite number of unidentified
components into a perfectly defined mixture of pseudocomponents which can be treated like pure
substances by chemical engineering software.
Yet the results thus obtained can only approach reality and require very close attention on the part of
the user.
Before the advent of these modern methods, the treatment of the liquid/vapor equilibria of the cuts
essentially made use of the vaporization curves. Many statistical correlations were developed in the
past to obtain them, and several of them are still equally valid today.
b  Statistical correlations
Statistical correlations are generally presented in graphic form. Some of them are digitized. They help
in particular to:
 switch from TBP to ASTM and vice versa
 switch from TBP or ASTM to the atmospheric flash or vacuum flash curve
Simultaneously, other correlations help to correct the flash curves as a function of pressure, and even,
in a liquid/vapor equilibrium, to determine the properties of the saturated phases.
We shall now describe some of these correlations.
PASSAGE FROM TBP TO ASTM
Edmister correlation
This correlation is very widely used, particularly in the following cases:
 conversion of the TBP portions of the crude oil corresponding to the desired distillation cuts
into ASTM, in order to characterize the products.
 determination of the TBP of a cut when the ASTM is available.
 use of computer distillation calculations which give the compositions of the cuts in the form
of compositions of pseudocomponents, each of them corresponding to a boiling point tmav.
Using these data, it is therefore possible to define a TBP, which can then be transformed
into ASTM if necessary. This use entailed the digitization of the correlation.
Plate J9 from ringbinder 0 shows the curves used.
The principle of the method consists of the following:
 first, positioning the 50% point of the required curve from the 50% point of the known curve
(bottom righthand part of the diagram)
 secondly, correlating the temperature differences 0 to 10C, 10 to 30C, 30 to 50C etc. of
the known curve with the corresponding differences in the desired curve
 thirdly, constructing the curve from the 50% point by adding or deducting the calculated
differences
00052_A_A
65
Riazi method
This method published by API, allows to transform a ASTM D86 curve into a TBP curve with the
following relation:
b
T TBP = a TASTM
a and b are parameters linked to % distilled volume.
% distilled volume
0.9177
1.0019
10
0.5564
1.0900
30
0.7617
1.0425
50
0.9013
1.0176
70
0.8821
1.00226
90
0.9552
1.0110
95
0.8177
1.0355
On the contrary, ASTM D86 curve can be obtained from TBP curve:
b
T ASTM = a TTBP
With following a and b values.
00052_A_A
% distilled volume
or vaporized volume
1.08947
0.99810
10
1.71243
0.91743
30
1.29838
0.95923
50
1.10755
0.98270
70
1.13047
0.97790
90
1.04643
0.98912
95
1.21455
0.96572
66
00052_A_A
67
100
Pressure 8 0
60
atm
F
Critical points
of paraffins
40
20
poin
%d
ew
D TH 117 B
100
90
70
le
rve
30
0%
bb
cu
50
1
0,8
0,6
0,4
bu
10
t
oin
t cu
rve
10
8
6
4
0,2
0,1
10
50
100
150
200
300
400 500
Temperature C
00052_A_A
68
V
161.5
0.5
+ 126
tboiling (C)
C12
C16
C20
217
287
350
tboiling (C)
C24
C28
C34
403
440
492
 the differences in boiling point and vapor pressure between nparaffins and isoparaffins:
nC 4 0.5C
iC 4 11.8C
nC 5 + 36C
iC 5 + 28C
Branched chain hydrocarbons generally have lower boiling points and higher vapor
pressures, because the cohesion forces of the liquid phase are weaker.
This is due to the branches of the chains, which hinder the approach of the molecules
towards each other and thus limit the effect of the forces of attraction by a distance effect.
00052_A_A
69
O
H
This polarity brings about bonds in the liquid phase between the hydrogen atoms of one
molecule and the oxygen atoms of the neighboring molecules.
These intermolecular bonds, called hydrogen bonds, confer an extraordinary cohesion to
liquid water, which therefore has a very low vapor pressure and very high boiling point with
respect to the size of the molecule.
b  Binary mixtures
The vaporization behavior of binary mixtures is conditioned by the extent of the interaction forces which
appear between the mixed molecules in the liquid phase. Between two neighboring hydrocarbons of
the same chemical family, the forces are observed to evolve regularly as a function of the molecular
proportions between those corresponding to one of the pure substances and those corresponding to
the other. This exhibits the ideal behavior characterized by Raoults law.
If the forces of attraction in the liquid mixture phase are weak, or even in the case of repulsion between
the molecules, a higher vapor pressure is observed than the level anticipated by Raoults law.
Simultaneously, the equilibrium lens is deformed because the mixtures with higher vapor pressures
have lower boiling points.
Figures A, B and C show the relationship between the isothermal diagram giving the vapor pressure
of mixtures of two components a/b (a light/b heavy) and the isobaric equilibrium lens.
t
Rao
w
lt la
Ps light C.
Ps heavy C.
Ps light C.
Ps light C.
Ps heavy C.
Ps heavy C.
mol. % light
t
b heavy C.
t
heavy C.
b heavy C.
b light C.
lig h t C .
heavy C.
b heavy C.
b light C.
lig h t C .
heavy C.
b light C.
lig h t C .
Figure A
Ideal mixture
00052_A_A
Figure B
Positive deviation
Figure C
Azeotropy
D TH 100 B
Azeotrope
70
Figure A relates to an ideal mixture where Raoults law is respected and also displays the
corresponding equilibrium lens.
Figure B corresponds to a mixture displaying positive nonideality: the vapor pressure observed is
higher than that predicted by Raoults law. This means a downward deformation of the equilibrium lens
because the mixtures with high vapor pressure have a lower boiling point. Note that light rich mixtures
have a boiling point approximately equal to that of the light component itself. Simultaneously, the
curve for saturated vapors is also shifted downward, causing a proximity of the two curves, which is
detrimental to the selectivity of liquid/vapor equilibria in the zone of high light concentrations.
Figure C is characteristic of azeotropy, which occurs when the curve giving the vapor pressure of the
mixtures passes through an extreme (minimum or maximum). The mixture which has this maximum or
minimum vapor pressure consequently has a minimum or maximum boiling point in the diagram of
equilibrium temperatures.
For this maximum or minimum boiling point, the liquid/vapor equilibrium imposes the presence of a
vapor in equilibrium at the same temperature. Hence, at this point, this requires the junction of the
boiling point curves of the liquids and the dewpoint curves of the vapors. The isobaric equilibrium
diagram is thus divided into two lenses. Figure C is said to be concerned with a minimum azeotrope.
At the same time, since the example presented implies the presence of a onephase mixture in the
liquid phase (no liquid/liquid separation), the azeotrope is called a homoazeotrope.
We know that with a constant temperature, the vapor pressure of a nonideal ab mixture is given by:
s
Ps = Pa x a a + Pb xb b
a and b are the activity coefficients a and b components.
Thus
Ps = Pa xa a + Pb b (1 xa )
(s
= xa Pa a Pb b
) + Pbs b
d P s = 0 thus
d x T
P a a = Pb b
ya Pa a
=
Ka =
xa
P
and
yb Pa b
Kb =
=
xb
P
thus
Ka Pa a
ab =
= s
= 1
Kb
Pb b
There is no more selectivity of liquidvapor equilibrium for the special composition of this mixture.
The vapor phase occurs during the vaporizations step is the same as the liquid phase.
00052_A_A
71
Pressure
Pressure
T
Ps max
Ps light
Ps light
Ps heavy
Ps heavy
Ps min
% mol. light
light C.
heavy C.
m1
heavy C.
m2
Temperature
light C.
Temperature
P
P
bp heavy
bp light
tb min
light C.
heavy C.
m1
bp max
bp light
heavy C.
m2
light C.
D TH 101 B
bp heavy
The presence of azeotropes generally complicates problems of separation by distillation, because the
azeotropes behave as pure substances:
 fixed boiling point
 vapor generated with composition identical to the liquid, hence no liquid/vapor
selectivity
00052_A_A
72
2
light C.
Temperature
P
t
b
heavy C.
constant
b light C.
t
b
light C.
Heavy C.
heavy C.
composition
D TH 102 B
t b heavy C.
Light C.
00052_A_A
73
nheptanebenzene mixture
The figures hereunder show the isothermal (at 80C) and isobaric (at 1 atm) diagram of nheptanebenzene mixture.
P sbenzene
P s(atm) 1
100
nC7 98,42C
Temperature C
T = 80C
lt
ou
a
R
Bz + nC7
P = 1 atm
nC7
90
P
0,75
P sheptane
0,5
Bz 80,10C
Equilibrium diagram of
benzenenheptane mixture
at P = 1 atm
80
0
1
0.5
xheptane
0.5
xbenzene
0
0,2
0,4
0,6
1
0,8
z,x,y benzene
(molar fraction)
Except for areas with high heptane concentrations, this mixture displays a highly positive deviation
from Raoults law without an apparition of azeotropic phenomenon.
The strongest vapor pressures observed lead to lower boiling point in particular for mixtures with high
benzene content.
The isobaric equilibrium diagram shows a bad selectivity of liquidvapor equilibriums, for high
benzene concentration (> 0.9). The values near liquid concentrations x and vapor concentrations y at
the equilibrium displays a relative volatility of benzene in comparison with nheptane close to 1 in this
area.
According to this particular behaviour, benzenenheptane mixture which is treated in a classical
distillation column can be split into a nC7 residue which can be pure and a distillate rich in benzene but
obviously with a small quantity of nC7.
For low benzene concentrations, it displays a highly positive deviation from Raoults law, which
reflects, in the zone of high hexane contents, a vapor pressure nearly as high as that of pure hexane.
This gives a very flat equilibrium curve corresponding to nearly constant equilibrium temperatures in
the neighbourhood of hexane.
00052_A_A
D TH 047 D
Vapor tension of
heptanebenzene
mixtures at 80C
74
From the distillation standpoint, this diagram shows that the volatility difference between these two
compounds varies widely according to the composition:
 hexane/benzene is much larger than 1 for hexane contents lower than 60 vol %
 hexane/benzene is very close to 1 in the zone above 80% hexane
This indicates that separation could help to obtain pure benzene at the bottom, but that, on the
contrary, at the top, hexane may not be purified and may exit with 10 to 20% benzene.
For mixtures with high content of nC6 , the boiling points are very close to nC6 boiling point. These
mixtures which almost present an azeotropic character are characteristic of a bad selectivity in areas
with a high nhexane content.
Temperature
(C)
This example also shows the risks of error induced by the assumptions of constant relative volatility for
hydrocarbons.
Equilibrium diagram
Benzene  nHexane
Benzene
80.1 C
80
P = 1 atm
75
nhexane
+
benzene
nhexane
benzene
70
65
0
00052_A_A
0.2
0.4
0.6
0.8
D TH 118 B
benzene
68.74C
nHexane
75
Ps
max
Ps
Ps
CH
Bz
CH
Azeotrope
D TH 2045 B
Bz
Temperature
(C)
The equilibrium diagram plotted below at 1 atm pressure shows that the azeotropic mixture contains
55 mol % benzene and has a boiling point of 77.4C.
Equilibrium diagram
Benzene  Cyclohexane
85
P = 1 atm
Cyclohexane
80.7C
Benzene
80.1C
80
77.4
z,x,y
0
00052_A_A
0.2
0.4
0.55
D TH 119 B
75
0.8
76
azeotrope
cyclohexane
benzene
cyclohexane
D TH 103 B
(Z BZ < 0.5)
PS
mmHg
T = 30C
PS
maximum
247
200
PS hexane
P
x
Vapor pressure of
hexaneethanol
mixtures at 30C
D TH 046 B
100
S
Pethanol
0
00052_A_A
0,5
0,77
xhexane
77
EQUILIBRIUM CURVES OF
HEXANE  ETHANOL MIXTURES
75
Temperature C
P = 1 atm
70
68.7C
65
60
67.5
55
ETHANOL
mol. % hexane
HEXANE
D TH 048 B
59.6
AZEOTROPE
Z > 0.675
ETHANOL
00052_A_A
HEXANE
D PCD 034 C
Z < 0.675
AZEOTROPE
78
Temperature C
64.5C
64
P = 1 atm
62
61.2
60
Acetone  chloroform
maximum azeotrope
0.345
56
3
0.2
56.5
0.4
0.6
1.0
0.8
Molar concentration of acetone
00052_A_A
P (mmHg)
Composition of azeotrope
(mol % hexane)
760
247
56.4
59.6C
30C
0C
67.5
77
82
D TH 120 B
58
79
For the ethanol/water mixture, it is interesting to see the azeotrope present at atmospheric pressure
(89.5 mol % ethanol, tnb = 78.15C) disappear when going to an absolute pressure of 100 mmHg.
The two diagrams given below show the possibility of a method of separation by distillation of
water/ethanol mixtures.
Temperature C
100
90
P = 760 mm Hg
80
78.3C
78.15C
0.895
70
51.2C
50
P = 100 mm Hg
40
30
00052_A_A
0.2
0.4
0.6
0.8
1
Molar fraction of ethanol
D TH 121 B
35C
80
Starting with a feed of composition Z < 89.5 mol % ethanol, the distillation scheme uses a first column
operating at 100 mmHg. This produces pure water at the bottom and a distillate of composition
x D > 0.895 at the top. This is then separated in an atmospheric column giving the azeotrope at the top,
recycled to the first column, and pure ethanol at the bottom. The flow chart is shown below.
XD > 0.895
1
atm.
100
mmHg
Azeotrope
WATER
00052_A_A
ETHANOL
D TH 2046 B
WATER
ETHANOL FEED
Z < 0.895
ethanol
81
4
HETEROAZEOTROPY
Heteroazeotropy adds the presence of partial or total immiscibility in the liquid phase to the
mechanism of azeotropy.
a  Heteroazeotropy with partial immiscibility
WATER ISOBUTANOL DIAGRAM
Solubility diagram  Waterisobutanol diagram
Partial immiscibility is reflected in the temperature/composition binary diagram by the presence of a
liquid/liquid equilibrium curve which divides the diagram into a twophase zone inside the curve and a
onephase zone outside.
In the twophase zone, the mixture is separated into two liquid phases which are said to be in
liquid/liquid equilibrium.
The solubility diagram helps to indicate the conditions of this equilibrium. The figure below gives the
example of the water/isobutanol mixture.
150
Critical temperature
Solubility diagram
Water  isobutanol
Temperature C
of dissolution
100
Domain with
2 liquid phases
1 liquid phase
50
P2
30
P1
0.02
0.2
00052_A_A
0.4
0.6
0.53
0.8
Molar fraction
of isobutanol
D TH 122 B
82
At a given temperature, a liquid mixture represented by a point located in the twophase domain is
separated into two liquid phases whose compositions are given, for the temperature concerned, by the
intersections with the equilibrium curve.
P 1 : 53% iB
M
(20% iB)
P 2 : 2% iB
D TH 2044 A
30C
The compositions of the liquid phases in equilibrium are modified with the temperature. Note that the
equilibrium curves move closer together, so that the difference in composition between the two liquid
phases in equilibrium is reduced as the temperature rises. The two curves ultimately join at a maximum
temperature above which two liquid phases can no longer exist. This temperature is called the critical
dissolution temperature (CDT).
Depending on the choice of a pressure, the liquid/vapor equilibrium temperatures may be lower than
the CDT, giving rise to the presence of a heteroazeotrope.
Isotherm diagram
The figure below shows waterisobutanol isotherm diagram which present a partial immiscibility in
liquid phase.
The mixture displays a high positive nonideality. The immiscibility area is represented by a constant
vapor pressure because liquid phases compositions at the equilibrium are fixed at a constant
temperature.
P
T
Pswater
Water
00052_A_A
Ps
iB
Isobutanol
D TH 2047 B
Zone
of immiscibility
Psdiphasic
mixture
83
Heteroazeotropic diagram
At atmospheric pressure, the diagram above shows that the water/isobutanol mixture has an azeotrope
(34 mol % isobutanol, 89.5C). This is located in the twophase liquid zone, showing that the
heteroazeotropy corresponds to a threephase equilibrium involving:
 a liquid phase with an overall composition of 34% butanol, but separated into two liquid
phases in equilibrium (2 and 40%)
 a vapor phase containing 34% isobutanol
Note that the threephase equilibrium imposes a constant value on the vapor pressure of the mixture,
because all the liquids of which the average composition lies inside the miscibility curves have the
same boiling point.
105
Temperature en C
107.1C
Liquid  Vapor
Equilibrium diagram
Water  isobutanol
P = 1 atm
100
100C
95
89.5
90
85
0
0.035
00052_A_A
0.2
0.4
0.34
0.6
0.8
1
x or y molar fraction of isobutanol
D TH 124 B
2 Liquid phases
84
WATER +
ISOBUTANOL
Z Bi > 40%
C
C
iB rich phase
Water rich
ISOBUTANOL
WATER
D TH 105 B
phase
00052_A_A
85
WATER/FURFURAL DIAGRAMS
162C
Temperature C
140
WATER  FURFUROL
1 ATM
Vapor phase
130
120
110
100C
100
90
80
1 liquid phase
1 liquid phase
97,9
2 Liquid
phases
70
60
Miscibility curve
40
20
10
Furfurol
weight percentage
35
0
10
20
30
40
50
60
70
WATER
00052_A_A
80
90
100%
D TH 125 B
30
FURFUROL
86
260
Temperature C
240
220
P = 34 atm
200
180
P = 17 atm
160
140
P = 6.8 atm
120
P = 3.4 atm
100
80
P = 1 atm
10
20
30
40
50
60
70
80
90
MEC
WATER
This diagram also shows the shift in the composition of the heteroazeotrope with pressure.
At 34 atm, the equilibrium curves leave the solubility diagram and give rise to a homoazeotrope.
00052_A_A
100
D TH 126 B
60
87
MIXTURE WATER
+
HYDROCARBONS
GAS SATURATED
WITH WATER
D TH 106 B
LIQUID
HYDROCARBONS
WATER
 an equilibrium pressure P or vapor pressure Pm of the liquid mixture equal to the sum of
S
the vapor pressures of water Pwater and of the liquid hydrocarbons PHC.
S
S
S
P = Pm = Pwater + PHC
This behavior is explained by the fact that, due to the total immiscibility, no intermolecular
bonding force exists between the water and the hydrocarbons in the liquid phase. Each of
the two components behaves as if it were alone in liquid/vapor equilibrium, and thus
exerts its own vapor pressure.
The first consequence of this behavior is that the addition of liquid water to hydrocarbons
gives rise to an overall mixture whose vapor pressure and hence volatility are increased.
This means lower vaporization temperatures.
00052_A_A
88
 a vapor phase composition which depends directly on the respective values of the vapor
pressures of water and the hydrocarbons. Daltons law, applicable at low pressure, helps to
determine the water content of the vapor phase ywater by relating the partial pressure of
S
This gives:
y water =
Pwater
P
Pwater depends on the temperature of the drum (see vapor pressure curve of water)
P is the total pressure
The gas resulting from this liquid/vapor equilibrium is said to be saturated with water.
Obviously we similarly have:
S
y HC =
PHC
P
= 1 ywater
The behavior of mixtures of water and hydrocarbons is therefore reflected by very simple laws.
Isobaric equilibrium diagram of a waterbenzene mixture
In terms of liquid/vapor equilibria, it is advantageous to apply these properties to construct the isobaric
equilibrium diagram corresponding to a binary water/hydrocarbon mixture. The example given below
for the water/benzene mixture is representative of binary water/hydrocarbon mixtures, with the
understanding that the diagram obtained is deformed according to the specific volatility of the
hydrocarbon combined with the water.
The liquidvapor equilibrium diagram is drawn at atmospheric pressure.
It shows the following results:
 the benzene boiling point: 80.1C
 the water boiling point: 100C
 the fixed boiling point for all twophases liquid benzenewater: 69.4C
 the presence of an heteroazeotrope at 70.5% mol of benzene
 a supposed total immiscibility zone in liquid phase
00052_A_A
89
Applied to the water/benzene binary mixture, the two above equations give the equilibrium diagram
under atmospheric pressure shown below.
Equilibrium diagram
liquid  vapor
WATER  BENZENE
100
tbp water
Temperature C
P = 1 atm
90
Vapor
(water + Benzene)
80.1C
tbp benzene
Liquid (water) +
+ vapor (water+ Benzene)
80
70
Liquid
(Benzene)
+
Vapor
(Water + Benzene)
69,4C
20
40
6 0 70.5 8 0
mol % benzene
100
80
mol % water
60
40
100
0
29.5 2 0
D TH 127 B
2 liquids
(water and benzene)
In fact, all the water/benzene mixtures have the same boiling point at atmospheric pressure. This
must be such that the following equation is satisfied:
S
00052_A_A
and
hence:
Pm = 1 atm
BZ
Water
1
0.705
0.295
Temperature C
69.4
80.1
100
D TH 2052 B
Pressure
90
Consequently, all water/benzene liquid mixtures can be seen to liberate a vapor of the same molar
composition:
S
ybenzene =
Pbenzene
S
Pm
0.705
=
= 0.705
1
ywater =
Pwater
S
Pm
0.295
= 0.295
1
This particular composition, for which contact occurs between the vapor and liquid equilibrium curves,
thus corresponds to the water/benzene heteroazeotrope.
By applying the same method, this mechanism of heteroazeotropy can be identified for all binary
mixtures of water and hydrocarbons. This results in diagrams having a similar shape to that of the
water/benzene mixture. The heteroazeotropic composition approaches the hydrocarbon for mixtures
of water and light hydrocarbons (e.g. water/propane), or, on the contrary, approaches water in the
reverse case (e.g. water/C25).
If we now examine the problem of the condensation of a gaseous mixture of water and benzene
under atmospheric pressure, two different developments can be observed depending on the
composition of the mixture.
Pressure
atm.
s be
p
0.8
e
nz
= 0.8
= 0.2
ne
ter
1.0
y benzene
y water
ps
wa
Benzenerich mixture
Benzene
pp benzene
0.705
0.6
0.4
0.2
Water
pp water
60
69
73
Condensation
water + benzene
80
93.5
100
D TH 107 B
0.295
110
120
Temperature C
condensation
of benzene
The above figure shows the water/benzene gaseous mixture in the pressure/temperature diagram.
Starting with a temperature of 110C, for example, and by cooling the mixture, the representative
points of benzene and water shift towards lower temperatures while remaining at a partial pressure of
0.8 atm for benzene and 0.2 atm for water.
At a temperature of about 73C, the representative point of benzene reaches its vapor pressure curve,
whereas the point of water remains in the gas domain.
00052_A_A
91
Consequently, benzene alone begins to condense at this point. The mixture has reached the dewpoint appearing in the binary equilibrium diagram shown earlier.
The process then continues with a decrease in the temperature as the benzene is condensed. This
leads to a reduction in the partial pressure of benzene, which is now its vapor pressure, and,
consequently, since the total pressure is constant, to an increase in the partial pressure of water vapor.
At 69C, the representative point of water reaches its equilibrium curve and the condensation of both
components of the mixture terminates in heteroazeotropic conditions: constant composition and
temperature.
Pressure
atm.
s be
p
0.8
0.705
e
nz
ne
ps
wa
1.0
= 0.8
= 0.2
ter
y water
y benzene
Waterrich mixture
Water
pp water
0.6
0.4
Benzene
0.2
pp benzene
0
60
69
condensation
water + benzene
80
93.5
100
110
120
Temperature C
condensation
of water
For this mixture, contrary to the previous case, the representative point of water reaches its vapor
pressure curve first at the dewpoint of the mixture: 93.5C. Water is then condensed alone up to
69C, a temperature at which the partial pressure of benzene, which is the complement at 1 atm of the
vapor pressure of water, reaches its equilibrium pressure. Both components continue to condense in
heteroazeotropic conditions.
By repeating this analysis for different compositions, the dewpoint curves appearing in the
heteroazeotropic diagram can be generated point by point.
00052_A_A
D TH 108 B
0.295
92
tbp azeo
WET
HYDROCARBON
tbp HC
DRY HYDROCARBON
D TH 109 B
Water
The heteroazeotrope separates into two liquid phases after condensation. The hydrocarbon phase is
refluxed to the column and the aqueous phase is removed.
In all cases, regardless the hydrocarbons and water volatility, the water is removed at the top of the
column.
Figures above show azeotropic diagrams with water and light or heavy hydrocarbons.
t
t
P
P
tbpwater
Water  light HC
Water  heavy HC
tbpHC
tebwater
tbpazeo
Water
00052_A_A
t
tbpHC
Light HC
Water
tbpazeo
Heavy HC
D TH 2048 B
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