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Refining-Petrochemicals-Chemicals-Engineering

APPLIED CHEMICAL ENGINEERING

APPLIED THERMODYNAMICS

I - LIQUID/VAPOR EQUILIBRIUM OF PURE SUBSTANCES ...................................................... 1


1
2
3
4

Phase diagram of a pure substance.............................................................................................1


Pressure/volume diagram, critical point........................................................................................ 2
Vaporization and vapor pressure curves...................................................................................... 4
Enthalpic diagrams of pure substances........................................................................................ 6

II - BEHAVIOR OF GASES........................................................................................................... 12
1
2
3
4
5
6

Perfect gas .................................................................................................................................12


Behavior of real fluids .................................................................................................................19
Law of corresponding states ...................................................................................................... 21
Law of corresponding states with three parameters ..................................................................25
Concept of equation of state ...................................................................................................... 27
Use of equations of state ...........................................................................................................29

III - LIQUID-VAPOR EQUILIBRIA OF HYDROCARBON MIXTURES........................................... 30


1
2
3
4
5

Equilibrium range for a hydrocarbon mixture..............................................................................30


Flash or liquid/vapor separation of a hydrocarbon mixture ........................................................ 32
Deviations from ideality - Modern methods for determining equilibrium coefficients.................. 37
General principles of calculating liquid/vapor equilibria.............................................................. 46
Isobaric equilibrium diagram of binary mixtures or equilibrium lens........................................... 50

IV - LIQUID/VAPOR EQUILIBRIA OF MIXTURES OF UNIDENTIFIED COMPONENTS ............. 56


1 - Characterization of the volatility of petroleum cuts and crude oils ............................................. 56
2 - Vaporization curve .....................................................................................................................60
3 - Methods for calculating liquid/vapor equilibria of mixtures of unidentified components ............. 61

V - LIQUID/VAPOR EQUILIBRIA OF NON-IDEAL MIXTURES.................................................... 68


1 - Relationship between liquid phase properties and vaporization behavior, definition of the
azeotrope ...................................................................................................................................68
2 - Examples of non-ideal mixtures and homoazeotropes separation ............................................ 72
3 - Shift of the azeotropic composition with pressure ......................................................................78
4 - Heteroazeotropy .........................................................................................................................81

BA ELV - 00052_A_A - Rev. 6

03/09/2004

2004 ENSPM Formation Industrie - IFP Training

I-

LIQUID/VAPOR EQUILIBRIUM OF PURE SUBSTANCES


1-

PHASE DIAGRAM OF A PURE SUBSTANCE


In a pressure/temperature diagram, the domains of existence of a pure substance in its three physical
states: solid, liquid, and gas or vapor, are bounded by three curves which join at the triple point T.
The pressure and temperature at this point allow all three phases to co-exist.
From the triple point, the diagram below shows the characteristic shape of the curves on which two
phases co-exist in equilibrium.

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

- the fusion curve determines the solid/liquid equilibrium conditions


- the sublimation curve corresponds to the solid/vapor equilibrium
- the vaporization curve, often called the vapor pressure curve, characterizes the
liquid/vapor equilibrium: this is limited at a point C called the critical point of the pure
substance.
Apart from a few special cases, the triple point of pure substances corresponds to a very low pressure,
lower than atmospheric. At the same time, the y-axis coordinated of the critical point C is located in the
interval from 20 to 80 atmospheres for most organic and inorganic compounds.

00052_A_A

2004 ENSPM Formation Industrie - IFP Training

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/VOLUME DIAGRAM, CRITICAL POINT


The figure below, for n-pentane, shows the correspondence between the vapor pressure curve of the
pressure/temperature diagram and the volume characteristics of the fluids at constant temperature
plotted in the pressure/volume diagram.

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

2004 ENSPM Formation Industrie - IFP Training

vap

or

5 0 100

10

190

20

150

D TH 082 B

20

Critical
point

Saturated liquid

LIQUID

Critical temperature 196.7C

30

205C

Critical
pressure
33.3 atm

33.3

40
150C

Critical
point C

190C

40

5 0 0 1000

Specific volume in cm3/g

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 n-pentane 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
two-phase 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, McGraw-Hill Book Company.

00052_A_A

2004 ENSPM Formation Industrie - IFP Training

3-

VAPORIZATION OR VAPOR PRESSURE CURVES


The vapor pressure curves help to determine the essential properties of pure substances for their
behavior with respect to liquid/vapor equilibria: the boiling point and the vapor pressure.
The boiling point of a pure substance, at constant pressure P, is the fixed temperature of the
vaporization of a pure substance. Under the same pressure P, the pure substance is found in the liquid
state if the temperature is lower than its boiling point, and in the gas state if it is higher.
The boiling point rises with pressure to reach its highest value at the critical temperature.
Note that, if the vaporization pressure is the normal atmospheric pressure of 1.013 bar, the boiling
point is said to be the normal boiling point, and is the figure given in the physical constants of the
pure substance.
C

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

2004 ENSPM Formation Industrie - IFP Training

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

vapor pressure of the pure substance (mmHg),


boiling point (K),
characteristic constants of each pure substance,

- 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 Tmin-Tmax 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

2004 ENSPM Formation Industrie - IFP Training

4-

ENTHALPIC DIAGRAMS OF PURE SUBSTANCES


a - Quantities of heat involved in heating and cooling a fluid: enthalpies, heat capacities
Starting with the liquid state, for example, suppose one adds heat to a pure substance at constant
pressure. The quantity of heat supplied to a unit mass of fluid as a function of temperature measures
its variation in enthalpy. This enthalpy is denoted H and its variation H. They are often expressed in
kJ/kg; sometimes in kcal/kg or BTU/lb. Based on a reference state, it gives the heat energy content
per unit mass of the pure substance.
The figure below shows, on pressure/temperature and enthalpy/temperature diagrams, the path
followed by a pure substance between a point L in the liquid zone and a point V in the vapor zone.
They help to clarify the terminology used and the correspondence between the pressure and
temperature conditions and the enthalpy.

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 sub-cooled.
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

liquid water at low temperature


liquid hydrocarbons
glycerine
mercury

4.185 kJ/kg.C
2.0 to 3.0 kJ/kg.C
2.43 kJ/kg.C
0.138 kJ/kg.C

2004 ENSPM Formation Industrie - IFP Training

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 sub-cooling 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

2004 ENSPM Formation Industrie - IFP Training

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

Average specified heat of fluid: c

D TH 2024 B

Same physical state in step

Temperature T2
Pressure P2

The sensible heat rate involved is given by:

Q = M . c . T

Q
M
c
T =

sensible heat input in kW


fluid flowrate in kg/s
specific heat in kJ/kg
T 2 T 1 or T 1 T 2
change in temperature of fluid

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 (H-t 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

2004 ENSPM Formation Industrie - IFP Training

By matching the results obtained, we obtain an enthalpy/temperature diagram which is characteristic


of the pure substance. The characteristic shape of this diagram is shown in the figure below for
n-pentane.

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 sub-cooled 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

2004 ENSPM Formation Industrie - IFP Training

10

d - Reference conditions of the enthalpy diagram


Enthalpic diagrams are plotted from a reference state chosen arbitrarily, for which the enthalpy is
zero. For the diagram given above, the enthalpy reference 0 kcal/kg corresponds to the saturated
liquid state at 100C. It was plotted from diagrams of J.B. Maxwell, for which the reference is the
saturated liquid state at 200F. Other sources use different references, such as the saturated liquid
state at 0C. Caution is therefore necessary when simultaneously using diagrams from various
sources.
Plates E1 to E4 show the enthalpy diagrams of a number of hydrocarbons prepared after
J.B. Maxwell. Others can be obtained from plates E10 to E15.
These diagrams help to determine the enthalpy for a pure substance from the knowledge of its
physical state, the pressure and the temperature. They offer the possibility of determining the
enthalpy of mixtures of known composition by weighting the enthalpies of the pure substances. Other
graphic tools are also available for determining the thermal properties of pure substances. Among
these, the most commonly used are the Mollier chart and the pressure/enthalpy diagram.

rs

tur

n lin
5
0.9
0
0.9

entropy

D TH 112 B

enthalpy

sa

isotherms

isoba

atio

Mollier charts offer a good representation


of the changes in temperature and
pressure undergone by a pure gaseous
substance in compression and expansion
processes. It is an enthalpy/entropy
diagram (H/S) which shows the saturation
curve giving the properties of the pure
substance in the saturated vapor state.
Networks of isotherms and isobars help to
locate the superheated vapor and to
determine its enthalpy in given conditions
of temperature and pressure.

e - Enthalpy/entropy diagram or Mollier chart (H/S diagram)

Entropy is an important thermodynamic function which is involved in particular in energy


conversion processes. It is denoted S and expressed, for example, in kJ/kg.C.
An isentropic change undergone by a gas during compression or expansion is represented in this
diagram by a vertical. It is defined as an adiabatic transformation, hence without exchanges of heat
with the exterior, and reversible, i.e. without any degradation in energy. Applied to the expansion of
water vapor in a steam turbine, it would correspond to a perfectly insulated machine in which the
thermal energy of the steam is fully converted into mechanical energy. A real transformation involving
friction and a degradation of energy in the form of heat would cause an increase in entropy.
Note that Mollier charts, beyond the saturation limit in the two-phase liquid/vapor domain, often have a
network of curves corresponding to a partial condensation of the pure gaseous substance. These are
identified by a content or mass fraction of vapor in the liquid/vapor mixture.
Plate E5 shows the Mollier chart for propane and plate C7 the Mollier chart for steam and water.

00052_A_A

2004 ENSPM Formation Industrie - IFP Training

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

2004 ENSPM Formation Industrie - IFP Training

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

absolute pressure exerted by the gas,


volume occupied by the gas or volume flow rate of gas,
quantity of gas expressed as the number of moles or molar flow rate,
absolute temperature of the gas,
universal gas constant, of which the value depends on the units selected.

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

2004 ENSPM Formation Industrie - IFP Training

13

MOLAR VOLUME OF IDEAL GASES Vm

In normal conditions:

t = 0C

the well-known value is obtained:

molar volume in m3 /kmol


temperature in K
pressure in bar
universal gas constant = 0.08314

Vm
T
P
R

R.T
Vm =
P

or

T = 273.15 K
P = 1 atm = 1.013 bar

Vm = 22.42 m3 /kmol

DENSITY OF AN IDEAL GAS


The density of any gas of molecular weight M (in kg/kmol) is given by the equation as follows:
molecular weight

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

CONVERSION FROM MASS FLOW RATE TO VOLUME FLOW RATE


In a process operating in steady-state conditions, the mass and volume flow rates of a fluid are related
by the following equation:

Qm = . Qv

00052_A_A

Qm
Qv

mass flowrate kg/h


volume flowrate m3/h
density kg/m 3

2004 ENSPM Formation Industrie - IFP Training

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.

CORRECTION OF VOLUME FLOW RATES


At constant mass flow rate and for a given perfect gas, the above equation shows that if the
Qv . P
remains constant.
temperature and pressure change, the expression
T
For reference conditions 1 and 2 , therefore:
Qv1 . P 1 Qv2. P2
=
T1
T2

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)

P = 1 atm = 1.013 bar

which correspond to flow rates expressed in normal m 3 per hour (Nm3/h).


Using Q VCN to denote the volume flow rate of ideal gas in normal conditions:
QVCN = QV .
QV
T
P
QVCN

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

2004 ENSPM Formation Industrie - IFP Training

15

b - Perfect gas: mixtures and partial pressures


If we consider a gas mixture in given conditions exerting a total pressure P, it is often advantageous to
know the participation of each component of the gas mixture to this total pressure.
The share of pressure exerted by a particular component i is its partial pressure (PPi). It is defined
as the pressure that this component would exert if it alone made up the entire volume flow rate
of the mixture.
The figure below shows a flow of a mixture of several pure gaseous substances at temperature T and
pressure P. The total volume flow rate is Qv.

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

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2004 ENSPM Formation Industrie - IFP Training

(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

partial pressure of component i


total pressure (same units as PPi)
molar fraction of i in vapor phase

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

is the molecular weight of component i,


is the average molecular weight of the gas mixture.

2004 ENSPM Formation Industrie - IFP Training

17

c - Other properties of ideal gases


While ideal gases all display identical behavior in terms of the properties of pressure, volume, quantity
and temperature, this rule does not apply for many of their physical properties, especially their
thermal properties. Tables are given in the literature which list the following for the different pure
substances in the ideal gas state.
MOLAR OR MASS SPECIFIC HEATS AT CONSTANT PRESSURE Cp
The molar specific heat at constant pressure Cp is usually given in joule per mole by Kelvin
(J/mol.K) and expresses the quantity of heat to be supplied to a mole of ideal gas to raise its
temperature by 1 K at constant pressure. Sometimes other units as calories or BTU per mol by Kelvin
are used.
Its value varies with the temperature, so that Cp is usually given in the form of polynomial functions of
temperature:
Cp = a + bT + cT2 + dT3
T
a, b, c

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

isentropic coefficient of the ideal gas


molar specific heat at constant pressure
molar specific heat at constant volume

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

2004 ENSPM Formation Industrie - IFP Training

18

The isentropic coefficient k is then obtained by the following equations:


k =

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

STANDARD ENTHALPIES OF FORMATION

( )

The standard enthalpy of formation H T F is defined as the variation in enthalpy which


accompanies the chemical reaction of the formation of a compound from its elements, all taken in
standard conditions: same temperature, pressure 1 atmosphere, ideal gas state with some exceptions
(e.g. graphite for the element carbon).

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.

STANDARD FREE ENTHALPIES OF FORMATION (GT )F


The standard free enthalpy of formation helps to calculate chemical equilibria. The values of

(GT)

are given on plates E19. As for enthalpy H, the free enthalpy G is expressed in cal/mol. It is

often called the Gibbs Energy in English literature.

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2004 ENSPM Formation Industrie - IFP Training

19

2-

BEHAVIOR OF REAL FLUIDS


a - Definition of the compressibility factor
The differences in behavior between a real fluid and a perfect gas can be identified by observing the
change in the ratio of the volume of real fluid V to that of the perfect gas Vpg as a function of the
pressure and temperature of the fluid.
This ratio denoted Z is called the compressibility factor:
Z =

V
Vpg

V
Vpg

volume of real fluid


volume of ideal gas

The volume of an ideal gas is given by the equation: V pg =

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.

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20

In these conditions, the value of Z is observed to undergo the following changes.


- At zero or very low pressure, the real gas is similar to the ideal gas and the compressibility factor
is approximately equal to 1.
- At higher pressure, the gas
approaches saturation, Z decreases
as the temperature selected
approaches TC. The compressibility
factor of the saturated vapor, ZV s ,
may then be much lower than 1.

LIQUID
LS

PS

VS

VAPOR
0

D TH 088 B

- The change of state then leads to a


sudden decrease in the
compressibility factor, which takes the
value ZLs corresponding to the
saturated liquid.

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

2004 ENSPM Formation Industrie - IFP Training

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-

LAW OF CORRESPONDING STATES


a - Definitions and general diagrams
The law of corresponding states declares that some properties of pure substances are identical
when they are in identically reduced conditions. These conditions are defined as follows:

Reduced pressure

PR =

Reduced temperature

TR =

P
PC

T
TC

same pressure units for P and PC


P pressure of the fluid
PC critical pressure of the pure substance

T and TC in Kelvin
T temperature of the fluid
PC critical temperature of the pure substance

P and T are the pressure and temperature of the fluid.


PC and T C are the critical pressure and the critical temperature of the pure substance.

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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
pseudo-reduced 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 pseudo-critical pressure of the
mixture PPC and its pseudo-critical temperature TPC:

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2004 ENSPM Formation Industrie - IFP Training

23

PPC = yi P Ci

Pseudo-critical pressure for a mixture

Pseudo-reduced pressure

PPR =

P
PPC

Pseudo-critical temperature for a mixture T PC = yi TCi


i

Pseudo-reduced temperature

T PR =

T
T PC

yi

molar fraction of i

PCi
P

critical pressure of i
operating pressure

PPC
PPR

pseudo-critical pressure
pseudo-reduced pressure

yi

molar fraction of i

T Ci
T

critical temperature of i
operating temperature

T PC
T PR

pseudo-critical temperature
pseudo-reduced temperature

b - Use of the compressibility factor


The introduction of the compressibility factor in the ideal gas law leads to the real gas law in which the
units used and the value of the constant are identical to those already presented:
P.V=Z.n.R.T
Introducing the volume flow rate Qv gives:
P . Qv = Z . n . R . T
The introduction of Z in the other equations written for the ideal gas leads to the following expressions:
R.T
P

- molar volume of a real gas:

Vm = Z

- density of a real gas:

=
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

- correction of volume flow rates of real gases:


P . Qv
= constant
Z.T

hence

Q v2 = Q v1 .

Z2
.
Z1

T 2 P1
.
T1
P2

where Z 1 and Z 2 are the compressibility factors in conditions 1 and 2 .


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2004 ENSPM Formation Industrie - IFP Training

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c - Validity of the law of corresponding states with two parameters


Limited to the generalized diagrams on Plate I2, it appears that the law of corresponding states
remains fairly approximate, and it assigns the same critical compressibility factor ZC = 0.27 to all
substances, whereas this actually varies from 0.23 for water to 0.3 for hydrogen, while remaining close
to 0.27 for most hydrocarbons.
For other properties to which the law of corresponding states applies, some differences are similarly
observed in the behavior of the different pure substances. This applies to the vapor pressure curves
which, plotted in reduced coordinates, should lead to a single generalized curve reflecting the
behavior of any compound at liquid/vapor equilibrium. In fact, the figure below shows that a group of
vapor pressure curves is obtained, showing differences in behavior related to the type and size of the
molecules making up the pure substances.

Reduced 1
saturation
pressure
Ps
P

Vapor pressure curves


in reduced coordinates

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.

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2004 ENSPM Formation Industrie - IFP Training

25

4-

LAW OF CORRESPONDING STATES WITH THREE PARAMETERS


a - Main parameters used
The third parameter is a physicochemical characteristic defined for each pure substance, which can be
determined for mixtures by weighting. Depending on the choice of this third parameter, many
correlations have been proposed. The most widely recognized are due to the following:
- J.B. Maxwell, who introduced the molecular weight M of the fluid. The compressibility
factor Z is thus obtained in a series of charts as a function of TR, PR and M
- Pitzer, who used the acentric factor . Related to the volatility characteristics, this factor
frequently appears in data on pure substances. The properties of fluids are then obtained as
a function of PR, T R and
- Hougen-Watson-Ragatz, who used the value of the critical compressibility factor ZC. A
series of diagrams gives the properties of the fluids as a function of PR, T R and Z C.
Among these methods, the one that involves the acentric factor has undoubtedly found the largest
number of applications.
b - Definition of the acentric factor
The definition of the acentric factor is based on the differences displayed by hydrocarbons in their
reduced vapor pressure curves.
For simple fluids, like methane, which obey the law of corresponding states with two parameters T R
and P R, it is observed that the reduced vapor pressure is very close to 0.1 when the reduced
temperature is 0.7:
for simple fluids

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

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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

atmospheric boiling point in K


in atmosphere
in K

c - Application of the law of corresponding states with three parameters


The calculation of the compressibility factor, for example, using the law of corresponding states with
three parameters, TR, PR and , employs the following formula:
Z = Z 0 + . Z1
Z0
Z1

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 pseudo-coordinates PPR and TPR can be calculated, and the acentric
factor is calculated for the mixture m:

m = yi i
i

i
yi

is the acentric factor of component i


is the molar fraction of i in the mixture

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.

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5-

CONCEPT OF EQUATION OF STATE


Equations of state are intended to represent the behavior of real fluids using a mathematical
expression f(P,V,T,n) = 0.
The earliest is the Van der Waals equation of state (1872) which modifies the ideal gas law by
introducing two corrective terms:
- the ideal gas pressure is reduced to account for intermolecular bonding forces existing in
real gases. These slow down the molecules, which consequently generate a lower pressure.
The corresponding correction factor, called the bonding pressure, is taken as a/V2 , where
a is a constant that depends on the type of gas, and V is the volume of gas:
a
Preal gas = Pperfect gas 2
V
a
P = Ppg 2
V

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 co-volume:
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

which is Van der Waals equation of state (1872).

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), BenedictWebb-Rubins (1940), Redlich-Kwong, etc. The latter, the Redlich-Kwong 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)

Redlich-Kwong equation of state (1949)

Since its origin, this empirical equation has undergone several hundred changes intended to make it
more efficient. The latest forms (Soave-Redlich-Kwong and Peng-Robinson) 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

2004 ENSPM Formation Industrie - IFP Training

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 Redlich-Kwong equation of state is transformed
R.T
into a third-degree equation in Z which is often presented as follows:

By introducing the compressibility factor Z =

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

Starting with the expression of A and B, the factors


A2 4.933
= 1.5
B
TR

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 right-hand 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.

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The Redlich-Kwong equation of state has undergone more than 700 changes since 1949. Among the
new forms most widely used are the following:
- the Soave-Redlich-Kwong 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

temperature and the acentric factor.

in which the Redlich-Kwong term

- the Peng-Robinson equation of state (PR 1976)

a (T, )
P +

V (V + b) + b (V b) (V b) = RT

6-

USE OF EQUATIONS OF STATE


Equations of state not only offer an advantage in their ability to give the volume properties of fluids, but
are in fact an excellent basic tool for determining:
- volumes or densities of the vapor and liquid phases: the correct representation of the
volume of the liquid phase is one of the advances achieved by the new equations of the
SRK and PR type
- vapor pressures
- liquid/vapor equilibria by means of fugacity coefficients
- enthalpy of real fluids from the enthalpy of the same fluid considered as an ideal gas
- entropy by the same approach
As for the calculation of the thermodynamic properties, such as enthalpy and entropy, the expression
below shows the corrective term determined from Redlich-Kwong to be applied to the enthalpy of the
ideal gas:

3 A 2
H = H0 RT
ln
2 B
H
H0
A,B

1 + BP + 1 Z

enthalpy of real fluid,


enthalpy of ideal gas,
constants of RK equation.

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.

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III - LIQUID-VAPOR EQUILIBRIA OF HYDROCARBON MIXTURES


1-

EQUILIBRIUM RANGE FOR A HYDROCARBON MIXTURE


An example of a liquid/vapor equilibrium range for a mixture of some hydrocarbons is shown in the
pressure/temperature diagram below.

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 left-hand 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 sub-cooled 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 dew-point 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 dew-points (dewpoint temperature and dew-point pressure), characterizes the dew-point curve of the mixture.

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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.

LIQUID-VAPOR EQUILIBRIUM DOMAINS


OF MIXTURES OF ETHANE AND n-HEPTANE

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
n-h

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 dew-point 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.

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2-

FLASH OR LIQUID/VAPOR SEPARATION OF A HYDROCARBON MIXTURE


a - Liquid/vapor separation
A liquid/vapor separation or flash of a hydrocarbon mixture is achieved by carrying out a partial
vaporization and then separating the liquid and vapor phases in a separator drum.
The vapor phase leaves at the top of the drum, and the liquid phase at the bottom.

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 dew-point
- 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.

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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

operating pressure of drum


vapor pressure or bubble point pressure of liquid mixture
S

This vapor pressure Pm is related to:


- the type and molar fraction of the components in the liquid phase
- the operating temperature of the drum
For hydrocarbon mixtures of the same chemical family and at low pressure, it can be estimated by a
simple calculation resulting from the application of the approximate Raoults law.
This postulates that the vapor pressure of the liquid is obtained from the specific vapor pressures of
the components weighted by the molar fractions:
PSi
PSm =
i

S
P i . xi

RAOULTS LAW

is the vapor pressure of component i at


temperature of drum
is the molar fraction of i in the liquid
phase

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

partial vapor pressure of i = Pi . xi = PPi

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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

vapor pressure of i at operating temperature


total operating pressure

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

- the temperature through P i


- the pressure P

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

- Raoults law already presented Ki =


valid at low pressure and for similar hydrocarbons
P
with similar volatilities,
- the Scheibel and Jenny nomograph (Plate J1), very practical to use and self-correcting in
so far as it inherently limits the number and type of components: 18 components from C1 to
C 14
- the Maxwell fugacity function of which the diagrams (Plates J2) give the product P . Ki
as a function of temperature and pressure for the first eight paraffinic hydrocarbons.

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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 non-volatile 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

is the relative volatility of i with respect to j

If i is more volatile than j: Ki > Kj and ij > 1. If not, ij < 1.


This parameter is highly advantageous in distillation studies of hydrocarbon mixtures, because it
remains approximately constant for all the operating conditions of a column:
S

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.

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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

1-2

Industrial column

Propane
n-butane
Isopentane
Metaxylene

Isobutane
Isopentane
n-pentane
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 n-pentane 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

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3 - DEVIATIONS FROM IDEALITY - MODERN METHODS FOR DETERMINING


EQUILIBRIUM COEFFICIENTS
a - Behavior of non-ideal solutions - Activity coefficient
Applied to a binary mixture a/b (a light component, b heavy component), Raoults law can be shown
graphically by an isothermal diagram giving the vapor pressure of liquid mixtures a/b at constant
temperature as a function of their composition expressed in molar fractions xa and x b .

Vapor
pressure
Constant temperature
PS
a
PS
m
PS
b

t's la

x
0

D TH 090 B

l
Raou

a
1
a

PSm = PSa . xa + PSb . xb


PSm = PSa . xa + PSb . (1 xa )

PSm = (PSa PSb) . xa + PSb


At a given temperature, this equation is that of a line which is based on the vapor pressures of the pure
substances:
if
if

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 non-ideal 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.

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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 non-ideal 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

vapor pressure of i component


molar fraction of i in the liquid phase
activity coefficient of i

PSm

vapor pressure of the mixture

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For a non-ideal 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 non-polar 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 non-ideal 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.

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b - Concept of fugacity
A situation of liquid/vapor equilibrium
illustrated by the figure opposite is
characterized by the co-existence of two
phases, separated by an interface, at the
same temperature and pressure.

P
V
T

Considering the movements of the


molecules, equilibrium means that
molecular transfers from one phase to
another occur in equal numbers.
Intuitively, moreover, these transfers
appear to be the result of two driving
properties specific to the fluids: the vapor
pressure of the liquid causes transfer in
the liquid/vapor direction, and the vapor
phase pressure is the driving force of
transfer from vapor to liquid.

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

fugacity of saturated vapor = fugacity of saturated liquid

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

for each component i of the mixture

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

fugacity of i in vapor phase

f i = P . y i = PP i

fugacity of i in liquid phase

f i = Pi . x i

at liquid/vapor equilibrium

fi = fi

thus:

P . y i = Pi . x i

partial pressure of i in vapor phase


partial vapor pressure of i
for each component

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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

ideal equilibrium coefficient

For the more general case of a real gas vapor phase and a non-ideal 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

is the fugacity coefficient of component i. It depends on the temperature, pressure and


composition of the mixture. Its value naturally tends towards 1 as the pressure tends towards
zero:
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

- the law of corresponding states which usually gives i as a function of TR and PR in


generalized graphic form, and possibly a third parameter.
V

- equations of state: by way of example, the expression below gives the value of i
obtained from the Redlich-Kwong 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

parameters of the mixture,


parameters of component i,
compressibility factor of the vapor mixture.

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d - Fugacity of component i in the liquid phase


L

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

component i in the liquid state in the conditions of liquid/vapor equilibrium. fi appears as


the corrected vapor pressure. In consequence:
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 vapor pressure of i at equilibrium temperature,

is the fugacity coefficient of pure component i in the vapor state and at the

P
V*iL

equilibrium temperature under pressure Pi


is the equilibrium pressure
molar volume of pure substance i in the saturated liquid state at the
equilibrium temperature

*S

- the second uses the same formalism as for the vapor phase. A fugacity coefficient of
L

component i in the liquid phase i is accordingly defined.


Since the total pressure is P, and the molar fractions in the liquid phase are xi, we have:
L

L
L
f i = P . xi . i

00052_A_A

fi
P

fugacity of i in the liquid phase


total pressure
fugacity coefficient of pure i in the liquid phase

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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

calculation of i is obtained for example:


by the SRK equation of state
by the Peng-Robinson equation of state
V

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

The definition of the fugacities

fi = P . yi . i

and

fi = fi . xi . i

*L

helps to write at equilibrium f i = f i , or:


*L

i
yi f i
Ki = = P .
xi
v

The equilibrium coefficient in this correlation is calculated from three distinct parameters:
v

fugacity coefficient of component i in gas phase, determined using the Redlich-Kwong


equation of state and the expression previously presented

activity coefficient, calculated from the Scatchard-Hildebrand theory of regular solutions

*L

fi

fugacity of pure component i in the liquid state


*L

RT . ln . i = Vi . ( i m)2

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*L

Vi

molar volume of pure liquid component i at 25C


solubility parameter of component i defined by the expression below: it is calculated at 25C
because its value varies little with temperature:
V

V
H25
RT 1

2
i =
V*L

25

H25 enthalpy of vaporization at 25C


*L

V25

liquid molar volume at 25C

average solubility parameter calculated by volumetric weighting of i

m = i xvi . i

x vi

volume fraction of i

*L

fi
P

is obtained by the law of corresponding states with three parameters:


*L

*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:
-

critical temperature Tci


critical pressure Pci
acentric factor i

enthalpy of vaporization at 25C Hi25

liquid molar volume at 25C Vi25

*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.

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This is because these can be divided into pseudo-components 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 pseudo-components, 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.
-

THE SOAVE-REDLICH-KWONG MODEL (SRK) (1972)

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 Redlich-Kwong 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 non-ideality.
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 pseudo-components, but it remains limited to non-polar
compounds.
It also offers the advantage of dealing better with liquid/vapor equilibria at high pressure.

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THE PENG-ROBINSON MODEL (1976)

Similar to the SRK model, the Peng-Robinson model is derived from the Redlich-Kwong 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 Benedict-Webb-Rubin 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 semi-predictive UNIFAC
model, which is based on set contributions.

4-

GENERAL PRINCIPLES OF CALCULATING LIQUID/VAPOR EQUILIBRIA

In the general case of the calculation of a


flash: bubble point, dew-point, partially
vaporized mixture, the following data are
available:
feed flow rate A,

feed composition Zi (n components),

model for determining equilibrium


coefficients K i as a function of
temperature t, pressure P and, if
applicable, vapor and liquid phase
compositions y i and x i respectively.

t
A
zi

D TH 093 A

V, yi

L, xi

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EQUATIONS GOVERNING THE SYSTEM


Material balance equations
Overall balance
Balance on one component i

A
A . zi

=
=

L+V
L . x i + V . yi

Normation equation

xi

of

or

compositions

yi

Liquid/vapor equilibrium equations

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

i (the feed is liquid)


with

yi = 1
i

The system to be resolved is thus reduced to:


K i . zi = 1
i

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The trial and error method is implemented.

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 dew-point of a mixture at a given pressure

Data:

P imposed
dew-point L = 0

In this case:

y i = zi (the feed is vapor)

hence:

z i = Ki . xi

zi
= xi
Ki

or

xi = 1

with

The system is reduced to:


zi
=1
K
i i

The trial and error calculation is represented on the following flow chart:
Calculation of Ki

Calculation of

zi
Ki

=1

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2004 ENSPM Formation Industrie - IFP Training

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

The flow rates and compositions of two phases are calculated:


A . zi = V . y i + L . x i
y i = Ki . xi
xi =
and

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=A-L

Calculation of xi

Calculation of xi

=1
L solution
D TH 2061 D

Hypothesis on L

If the K i depend on P, t, xi and y i, an additional loop is necessary:

V=A-L

Calculation of Ki

Calculation of xi
and yi

xi = Ct

=1
L solution

xi varies
1

00052_A_A

2004 ENSPM Formation Industrie - IFP Training

D TH 2061 E

Hypothesis on L

50

5 - ISOBARIC EQUILIBRIUM DIAGRAM OF BINARY MIXTURES OR EQUILIBRIUM


LENS
a - Construction of the equilibrium lens
The equilibrium lens of a binary mixture is an isobaric diagram which gives the equilibrium
temperatures (bubble point and dew-point) of a binary mixture as a function of its composition.
This diagram is easily obtained by graphic construction from the liquid/vapor equilibrium domains
presented below for different mixtures of two components a and b, where a is the volatile component
and b is the heavy component.

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

Bubble point curve


Dew point curve

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.

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51

The upper curve connects the dew-points 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

determination of liquid composition at its bubble point at temperature t:


with
hence

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

determination of vapor composition in equilibrium with the liquid:


y a = Ka xa

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.

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b - Flash of a binary mixture


The representation of a flash is shown below.

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

Compositions z, y and x are fractions or molar percentages of volatile component a.


Point A representing the feed of composition z is located in the liquid/vapor domain at temperature t.
The two phases in liquid/vapor equilibrium at temperature t are at their bubble and dew-points
respectively. This helps to position points L and V and to determine the compositions x and y of
these two phases. The difference between the values of y and x illustrates the separation made by an
equilibrium stage and materializes the selectivity of the operation.
The vapor flow rate V and liquid flow rate L can be obtained from the compositions. The material
balance of the flash drum is written:
Overall balance

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

2004 ENSPM Formation Industrie - IFP Training

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

By using h a and h b to denote the


molar enthalpies of a and b in the
state of pure liquid substances at
temperature t, and H a and H b the
molar enthalpies of the same
components in the vapor state, the
molar enthalpies HV and hL of the
liquid and vapor phases in
equilibrium can be obtained by the
equations:

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.

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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

2004 ENSPM Formation Industrie - IFP Training

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

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2004 ENSPM Formation Industrie - IFP Training

D TH 099 B

y1

56

IV - LIQUID/VAPOR EQUILIBRIA OF MIXTURES OF UNIDENTIFIED COMPONENTS


Mixtures of unidentified components are petroleum cuts, petroleum products, crude oils or pyrolysis cuts.
Their components are so numerous and similar in terms of volatility that it is impossible to identify them by
standard analytical methods like chromatography. These products are also sometimes qualified as complex
continuums.

1-

CHARACTERIZATION OF THE VOLATILITY OF PETROLEUM CUTS AND CRUDE


OILS
Chromatographic analysis helps to identify the lightest components up to the C7 to C 10 hydrocarbons.
As a rule, analyses of crude oils stop at C5 . Two standard methods are available beyond this level to
characterize the volatility of a cut: TBP distillation, a rigorous, lengthy and costly analysis, and ASTM
distillation, a rapid routine quality control analysis.
In recent years, simulated distillation, which helps to determine the distribution of the boiling
ranges of petroleum fractions by gas chromatography appears capable of providing a more
rigorous approach in determining the composition of petroleum cuts.
a - TBP (True Boiling Point) distillation
This is a batch distillation which exploits a high separating power obtained by using a large number
of contact stages and a high reflux rate.
Standard ASTM D 2892 describes a TBP distillation method called 15/5 because the distillation
column has 15 theoretical contact stages and the operating reflux ratio is maintained at 5.
The analysis consists in distilling about 10 liters of product or crude oil in this column and recording the
correspondences between the quantities collected (mass and volume) and the temperatures observed
at the top of the column, which is illustrated below.
The operation is performed first at atmospheric pressure and then under vacuum to prevent thermal
degradation of the hydrocarbons.
The temperatures observed under vacuum are corrected and adjusted to atmospheric pressure.

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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.

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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 non-distillable 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.

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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 n-paraffins with known
boiling points, which help to make a temperature graduation of the chromatogram obtained.
Measuring the areas between the peaks of the n-paraffins makes it possible to determine the
relationship between the mass percentages and the boiling points.

Elution time
corresponding to
boiling temperatures

Example of result
370-535C cut
C42
C40
C38
C36
C34
C32
C30
C29
C28
C27
C26
C25
C24
C23
D TH 2029 B

C22

1 l cut 370-535C
Signal intensity

Two ASTM methods using this principle exist:


- D 2887 available for petroleum cuts with boiling points lower than 538C
- D 3710 available for lighter cuts (< 250C)

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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 draw-off 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 dew-point 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

The atmospheric flash curve corresponds to the normal pressure of 1 atm.


Compared with the ASTM and TBP curves, this curve is flatter as shown by the figures below for a
complex cut and for a binary mixture.

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

2004 ENSPM Formation Industrie - IFP Training

D TH 2022 A

TBP
ASTM
FC

61

3 - METHODS FOR CALCULATING LIQUID/VAPOR EQUILIBRIA OF MIXTURES OF


UNIDENTIFIED COMPONENTS
a - Breakdown into pseudo-components
The modern approach of these calculations makes use of the breakdown of the mixture analyzed into
pseudo-components whose physical properties can be defined sufficiently as inputs in computerized
methods for calculating liquid/vapor equilibria.
This method requires the availability of a TBP distillation curve of the mixture. The fine breakdown
gives the characteristics of small range cuts (2 or 3C width or 2%). Then the breakdown policy often
consists in defining the pseudo-components corresponding to a constant temperature interval t
(e.g. 10, 20 and 30C). Their characteristics are obtained by weighting the properties of the small
range cuts.
The figure below locates the pseudo-component i of which the following can be defined:
- mass concentration in the mixture
- the weighted average boiling point which can be treated as tmav for narrow cuts

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

possible to determine the d4 of pseudo-component i.


Pseudo component i

t mavi

boiling temperature

zi

mass concentration

15

d4i

00052_A_A

specific gravity at 15C

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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 pseudo-component 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

(or solubility parameter i)

The basic data required to characterize each pseudo-component are:


- weighted average boiling point treated as tmav
- specific gravity
15

15

60

d15 or Spgr 60 = 1.00096 d4


or API = A =

141.5
60

Spgr60

131.5

- and possibly the molecular weight M, which can be determined as follows:


2.3776

M = 5.805 x 105

tmav

tmav in K

spgr0.9371

Critical coordinates can be obtained by:


- correlations using the Winn chart:
TC =

exp (4.2009 tmav0.08615 Spgr 0.04614)


1.8

t mav
TC

PC =

6.1483 . 1012 Spgr2.4853


t mav2.3177

PC in Pa

in K

- Cavetts correlation, which uses a set of universal constants a0 to a 6 and b0 to b 7 :


2

T C = a0 + a1 tmav + a2 t mav + a3 t mav + a4 A t mav + a5 A t mav + a6 A 2 t mav


PC = b0 + b1 tmav + b2 t mav + b3 t mav + b4 A t mav + b5 A t mav + b6 A 2 t mav
- Lee-Kesler method (1975)
T C = 189.8 + 450.6 spgr + t mav (0.4244 + 0.1174 spgr) +
ln P C = 5.68925

(14410 100688 spgr)


t mav

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

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63

The acentric factor of which the definition is:


PS
= log10 P

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

can also be determined by the Lee-Kesler equation (1975) with:


PSbR
T bR

reduced saturation pressure (at normal boiling point P S = 1 atm)


reduced normal boiling point = t mav/TC

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

The liquid molar volume at 25C is given by:


liquid molar volume V25 =

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 pseudo-component 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

= 7.58 + 4.571 ln (tmav)


t mav in R

Watsons formula then gives the variation in HV with temperature:


V

H25
V

Ht
00052_A_A

mav

0.38

T C 537
=
T C T mav

T C in R

2004 ENSPM Formation Industrie - IFP Training

64

The solubility parameter i can then be calculated by the equation:


V
1
H25
RT
2

i =
V25

The work done for each pseudo-component transforms a product with an infinite number of unidentified
components into a perfectly defined mixture of pseudo-components 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 pseudo-components, 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 ring-binder 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 right-hand 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

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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

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PASSAGE FROM TBP OR ASTM TO THE ATMOSPHERIC VAPORIZATION CURVE


Two main methods are available for this transformation:
- the J.B. Maxwell method is presented on Plate J10
- the Edmister method is presented on Plate J11
Maxwells correlation is based on the different slopes of the distillation curves and the flash curve. It
consists successively of the following:
- defining a DRL line (distillation curve reference line) from the 10 and 70% points of the TBP
TBP real DRL
- plotting an FRL line (flash curve reference line) from the correlations giving the following as
a function of the 10 to 70 slope of the DRL:
the slope of the FRL
the t 50 (DRL - FRL), i.e. t 50FRL
DRL FRL
- from the differences read for each percent distilled between DRL and TBP (tD),
determining the differences tF between FRL and atmospheric flash curve: the graphic
correlation shows that, except for the low percentages distilled, tF is one-third of tD,
tD tF
- finally plotting the atmospheric flash curve.
FRL FCATM
Edmisters correlation uses a similar approach to the one for passage from TBP to ASTM.

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67

SHIFT OF THE FLASH CURVE WITH PRESSURE


The figure below shows the characteristic shape of the liquid/vapor domain of a petroleum cut shown
on a Cox Chart. The iso percentage vaporized curves are lines approximately parallel to the vapor
pressure lines of the hydrocarbons, but they converge at high pressure at a point F. This point only has
geometric significance, and is called the focal point. It is obviously different from the critical point C of
the mixture.

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

Two main methods are used to shift the vaporization curve.


- the first consists in converting the atmospheric curve by the 50% point on the Cox
Chart. By plotting a line from the 50% part of the flash curve, interpolated in the network of
vapor pressure lines, one can determine the variation in temperature undergone by this
point as a function of pressure. The same variation is then applied to all the points of the
curve. This method is valid for a slight variation in pressure
- the second is based on the positioning of the focal point which, once in place, helps to
plot the network of lines corresponding to the different percentages vaporized, and thus to
obtain the vaporization curve at any pressure.
To position the focal point, J.B. Maxwell proposed interpolating a line in the network of vapor
pressure lines of the Cox Chart. This lines passes through the 40% point of the
atmospheric vaporization curve (temperature 40 C, pressure 1 atm) and is prolonged
over a temperature interval of 83 C beyond the intersection with the locus of the critical
points of the paraffins. The terminal point obtained is the desired focal point.

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V-

LIQUID/VAPOR EQUILIBRIA OF NON-IDEAL MIXTURES


1 - RELATIONSHIP BETWEEN LIQUID PHASE PROPERTIES AND VAPORIZATION
BEHAVIOR, DEFINITION OF THE AZEOTROPY
a - Pure substances
The behavior of a pure substance in liquid/vapor equilibria is determined primarily by the properties of
its liquid phase, of which the cohesion is ensured by intermolecular forces. These intermolecular
forces are mainly due to the electron movements within the molecules which give rise to
electromagnetic fields.
The molecules consequently undergo forces of mutual attraction of which the intensity varies
according to the type of the molecule and the conditions in which the molecules are found.
These forces act at short distance and decrease very rapidly as the molecules separate from each
other. They have little effect on the behavior of gases, but are decisive for liquids, whose
vaporization behavior they influence.
Strong forces of attraction reflect good cohesion of the liquid phase. In terms of liquid/vapor
equilibrium, this gives rise to:
- a low vapor pressure: the molecules are retained in the liquid phase
- a high boiling point necessary to overcome these forces during vaporization
By way of example, this makes it possible to explain the following:
- the progression of boiling points and hence of vapor pressures of normal paraffinic
hydrocarbons with the number of carbon atoms, because the forces of attraction are greater
as the chain length increases:
tboiling (C)
C1
C4
C8

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 n-paraffins and iso-paraffins:
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.

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- the abnormally high boiling point of water:

O
H

The water molecule is in fact a polar molecule. The shift of the


electrons in the molecule from the hydrogen atoms to the oxygen
atoms gives rise to a genuine electric dipole.

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

2004 ENSPM Formation Industrie - IFP Training

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 non-ideality: 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 dew-point 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 one-phase 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 non-ideal a-b 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

If the curve Ps = f(x) at constant temperature present an extremum, then:

d P s = 0 thus
d x T

P a a = Pb b

In this conditions, if the equilibrium coefficients are expressed by:


s

ya Pa a
=
Ka =
xa
P

and

yb Pa b
Kb =
=
xb
P

thus

Ka Pa a
a-b =
= s
= 1
Kb
Pb b

There is no more selectivity of liquid-vapor equilibrium for the special composition of this mixture.
The vapor phase occurs during the vaporizations step is the same as the liquid phase.

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The figures below show the two typical cases of homoazeotropy.

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

m 1 : homoazeotrope at minimum boiling point


m 2 : homoazeotrope at maximum boiling point

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

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2-

EXAMPLES OF NON-IDEAL MIXTURES AND HOMOAZEOTROPES SEPARATION


a - Separation of ideal mixtures
A number of examples helps to position the different problems connected with non-ideality and to
demonstrate the resulting difficulties in the feasibility of separations by distillation.
For an ideal binary mixture, the shape of the equilibrium lens guarantees constant selectivity of
liquid/vapor equilibrium. In fact, it can be considered that the ideal equilibrium lens reflects a constant
value for the relative volatility of the light component with respect to the heavy component. In so far as
the volatility difference between the two components to be separated is sufficiently large, a distillation
column helps to obtain each of the two components in the desired purity.

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.

We obtain under pressure supposed constant:


- at the top of the column, the volatile component a and the temperature of the head of the
column is established at teba
- at the bottom of the column the heavy component b is established with its boiling point t ebb
For non-ideal mixtures, the shape of the lens indicates wide variations in volatility, which often restrict
the possibilities of separation by distillation, as shown by the examples below.

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b - Non-ideal mixtures: n-heptane-benzene and n-hexane-benzene


This mixture is characteristic of non-ideality which appears in aromatic/non-aromatic mixtures.

n-heptane-benzene mixture
The figures hereunder show the isothermal (at 80C) and isobaric (at 1 atm) diagram of n-heptanebenzene 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
benzene-n-heptane 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 liquid-vapor 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 n-heptane close to 1 in this
area.
According to this particular behaviour, benzene-n-heptane 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

2004 ENSPM Formation Industrie - IFP Training

D TH 047 D

Vapor tension of
heptane-benzene
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 n-hexane content.

Temperature
(C)

This example also shows the risks of error induced by the assumptions of constant relative volatility for
hydrocarbons.

Equilibrium diagram
Benzene - n-Hexane
Benzene
80.1 C

80

P = 1 atm

75
n-hexane
+
benzene
n-hexane
benzene

70

z,x,y Benzene (molar fraction)

65
0

00052_A_A

0.2

0.4

0.6

0.8

2004 ENSPM Formation Industrie - IFP Training

D TH 118 B

benzene

68.74C
n-Hexane

75

c - Benzene/cyclohexane azeotropic mixture


This is a rare case of azeotropy in a hydrocarbon mixture. It is due to the fact that benzene
(t nb = 80.1C) and cyclohexane (tnb = 80.7C) have very similar volatilities. Their vapor pressure
curves are extremely close to each other and, at a given temperature, indicate nearly identical vapor
pressure for both pure substances.
P
T

Ps
max
Ps

Ps

CH

Bz

The opposite diagram shows the shape of


the vapor pressure curve for cyclohexanebenzene mixtures around 80C.

CH

Azeotrope

D TH 2045 B

A weak non-ideality (positive here)


suffices in this case to confer a higher
vapor pressure on benzene/cyclohexane
mixtures than the vapor pressure of the
pure substances, thus causing azeotropy.

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

Benzene (molar fraction)


0.6

2004 ENSPM Formation Industrie - IFP Training

0.8

76

azeotrope

Depending on the feed composition, a


distillation column helps to obtain one of
the two pure substances at the bottom
and the azeotrope at the top. The figure
opposite corresponds to a feed containing
less than 50% benzene.

cyclohexane
benzene

cyclohexane

D TH 103 B

(Z BZ < 0.5)

d - Ethanol/hexane azeotropic mixture


Ethanol and hexane display very high positive non-ideality in mixtures in the liquid state shown by
a very high maximum vapor pressure on the below drawn at a temperature diagram of 30C. This
gives rise to a vapor pressure extreme which leads to a minimum homoazeotrope at atmospheric
pressure.

PS
mmHg

T = 30C
PS
maximum

247

200

PS hexane
P

x
Vapor pressure of
hexane-ethanol
mixtures at 30C
D TH 046 B

100
S
Pethanol
0

00052_A_A

0,5

0,77

2004 ENSPM Formation Industrie - IFP Training

xhexane

77

The figure below shows the diagram obtained:


- boiling point of ethanol 78.3C
- boiling point of hexane 68.7C
- boiling point of azeotrope 59.6C, corresponding to a mixture containing 67.5 mol % hexane
80
78.3C

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

In terms of separation, such a mixture cannot be separated by simple distillation:


- a feed of composition Z < 0.675 hexane gives the azeotrope at the top and high
concentration ethanol at the bottom
- a feed of composition Z > 0.675 hexane gives the azeotrope in the distillate and hexane in
the residue

AZEOTROPE

Z > 0.675

ETHANOL

00052_A_A

2004 ENSPM Formation Industrie - IFP Training

HEXANE

D PCD 034 C

Z < 0.675

AZEOTROPE

78

e - Chloroform/acetone azeotropic mixture


Mixtures with high negative non-ideality giving rise to a maximum azeotrope are relatively few in
number. Dilute acidic solutions and the acetone/chloroform mixture shown below are examples.
In this case, distillation produces one of the two pure substances at the top and the azeotrope at the
bottom.

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

SHIFT OF THE AZEOTROPIC COMPOSITION WITH PRESSURE


Pressure alters the equilibrium temperatures, and these affect the cohesion forces in the liquid phase.
The azeotropic diagrams not only undergo a shift in the temperatures as the pressure is changed, but
a change in the azeotropic composition is also observed.
For an ethanol/n-hexane mixture, the azeotropic composition shifts towards higher hexane
concentrations as the pressure is decreased.

00052_A_A

P (mmHg)

Boiling point azeotrope

Composition of azeotrope
(mol % hexane)

760
247
56.4

59.6C
30C
0C

67.5
77
82

2004 ENSPM Formation Industrie - IFP Training

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

Water - Ethanol equilibrium


at 760 and 100 mm Hg
60

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

2004 ENSPM Formation Industrie - IFP Training

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

2004 ENSPM Formation Industrie - IFP Training

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 - Water-isobutanol 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 two-phase zone inside the curve and a
one-phase zone outside.
In the two-phase 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

2004 ENSPM Formation Industrie - IFP Training

D TH 122 B

82

At a given temperature, a liquid mixture represented by a point located in the two-phase 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

At 30C for example, a mixture M


containing 20 mol % isobutanol separates
into a phase P1 containing 53%
isobutanol and a phase P2 containing 2%.

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 water-isobutanol isotherm diagram which present a partial immiscibility in
liquid phase.
The mixture displays a high positive non-ideality. 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

2004 ENSPM Formation Industrie - IFP Training

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 two-phase liquid zone, showing that the
heteroazeotropy corresponds to a three-phase 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 three-phase 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

2004 ENSPM Formation Industrie - IFP Training

D TH 124 B

2 Liquid phases

84

Separation of a binary heteroazeotropic mixture


The separation of heteroazeotropic mixtures by distillation generally requires the use of two
columns.
Starting with a one-phase liquid feed rich in isobutanol (Z > 40%), a first column C1 helps to separate
the isobutanol with the desired purity at the bottom and the heteroazeotrope at the top.
After condensation, the heteroazeotrope settles into two liquid phases of which the compositions are
given by the miscibility curves.
The isobutanol-rich phase is sent as reflux to the first column, and the water-rich phase is treated in the
second column C2 producing:
- the azeotrope at the head, recycled to the condensation system
- water at the bottom in the desired purity
The flow chart of the process is shown below.

WATER +
ISOBUTANOL
Z Bi > 40%

C
C

iB rich phase

Water rich

ISOBUTANOL

WATER
D TH 105 B

phase

Other examples of binary heteroazeotropic mixtures


Water/furfural and water/MEK diagrams are similar to the water/isobutanol diagram. The partial
immiscibility curve in the liquid phase is however wider.
Separation of the mixtures by distillation is carried out as described above.

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2004 ENSPM Formation Industrie - IFP Training

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

Dew point curve

60

Bubble point curve


50

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

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WATER/METHYL-ETHYL-KETONE (MEK) DIAGRAM

260
Temperature C

WATER-METHYL ETHYL KETONE

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

mol % of methyl ethyl ketone


0

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

2004 ENSPM Formation Industrie - IFP Training

D TH 126 B

60

87

b - Heteroazeotrope with total immiscibility


Water/hydrocarbon mixtures provide the most common examples of heteroazeotropy with total
immiscibility. The corresponding solubilities are in fact very low at moderate temperature, and the
water/hydrocarbon liquid mixtures can always be considered as two-phase mixtures.
This gives rise to special behavior which can be approached from the particularly simple vapor
pressure law applicable to these mixtures.
Vapor pressure of a water/hydrocarbon mixture
The figure below shows a water/hydrocarbon mixture in liquid/vapor equilibrium.

MIXTURE WATER
+
HYDROCARBONS

GAS SATURATED
WITH WATER

D TH 106 B

LIQUID
HYDROCARBONS

WATER

The equilibrium conditions are characterized as follows.


S

- 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.

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2004 ENSPM Formation Industrie - IFP Training

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- 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

water or Pwater to the total pressure P.


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 water-benzene 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 liquid-vapor 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 two-phases liquid benzene-water: 69.4C
- the presence of an heteroazeotrope at 70.5% mol of benzene
- a supposed total immiscibility zone in liquid phase

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2004 ENSPM Formation Industrie - IFP Training

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

Pm = Pbenzene + Pwater = 1 atm


This temperature can be determined
by successive approximations, leading
to an equality satisfied at a
temperature of 69C.

Pbenzene = 0.705 atm

00052_A_A

and

Pwater = 0.295 atm

hence:

Pm = 1 atm

BZ
Water
1
0.705

0.295
Temperature C

69.4

2004 ENSPM Formation Industrie - IFP Training

80.1

100

D TH 2052 B

At this temperature, we have:

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

Benzene-rich 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.

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2004 ENSPM Formation Industrie - IFP Training

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

Water-rich 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 dew-point 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 dew-point curves appearing in the
heteroazeotropic diagram can be generated point by point.

00052_A_A

2004 ENSPM Formation Industrie - IFP Training

D TH 108 B

0.295

92

Applications: hydrocarbon drying column


A rather common application of this type of behavior in liquid/vapor equilibrium corresponds to
hydrocarbon drying process by azeotropic distillation.
The wet hydrocarbon (containing dissolved water) is fed to a distillation column. At the bottom the dry
hydrocarbon normally exits, while a composition close to the heteroazeotrope exits at the top.

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

2004 ENSPM Formation Industrie - IFP Training

tbpazeo

Heavy HC

D TH 2048 B