Chapter 1

Course Manual Crude Distillation (Theoretical Principles)
Chapter 1
Theoretical Principles of Fractional

Distillation
MIDOM (Rev.0) Jan. 2006 Chapter # 1 Page # 1 of 35

Chapter 1 Contents
1.1 Introduction
1.2 Vapor Pressure
1.3 Partial Pressure
1.4 Fundamentals
1.4.1 Henry’s Law
1.4.2 Dalton’s Law
1.5 Analysis of Mixtures
1.6 Boiling Point Calculation
1.7 Dew Point Calculation
1.8 Flash Calculation

Chapter 1
Theoretical Principles of Fractional Distillation

1.1 INTRODUCTION
A detailed discussion of the entire theory of fractional distillation and all the
problems connected herewith is not possible within the scope of this Course and has
not been attempted. The most important features of this vast subject have been dealt
with and a number of references are given which should enable the reader to tackle
any specific problem requiring a deeper knowledge of the various methods used in
fractionation calculations. Since the majority of the Group's technologists are
engaged in other fields than design work, complete discussion of tray-to-tray
calculations has been omitted. However, it is felt that the technologist should be
familiar with simple column evaluations, boiling point, dew point and flash
calculations and be able to interpret intelligently design work should the necessity
arise.
1.2 VAPOR PRESSURE
A gas or vapor consists of molecules in random and chaotic motion. Millions of

small particles moving in all directions in the air in the room, they collide with each
other repeatedly.
There are many collisions between molecules in a gas. The molecules of a vapor in a
container repeatedly have collisions with the walls of the container. When many gas
molecules collide repeatedly with the walls of a container, these collisions add up to
a pressure exerted on the walls. If the temperature of a gas is increased, the
molecules in the gas move faster. At a lower temperature, the vapor molecules move
slower. The more rapid motion at higher temperatures results in more violent
collisions of the molecules. As the molecules move faster and the collisions become
more violent, molecules in a closed container strike the walls with more force. The
pressure, therefore, increases.
The pressure of a gas in an open container cannot be increased, since some of the gas
would escape to equalize the pressure with the surroundings. The pressure of a gas
in an open container cannot be increased by increasing the temperature.

Like the molecules of gases, the molecules of a liquid are constantly in motion.
Unlike the molecules of gases, the molecules of a liquid are held close together by
natural attraction between the molecules. In a liquid, the attraction between
molecules tends to keep each molecule confined to a small space. Within this space a
molecule is usually in violent motion. The violent motion of the molecules at the
surface of a liquid causes many of these molecules to escape from the liquid. If the
temperature of a liquid is increased, the motion of the molecules becomes more
violent.
If an empty container is partially filled with liquid, molecules escape from the
surface of the liquid, forming a vapor in the space above the surface. Gas molecules
which strike the surface of a liquid tend to stick to the liquid. Thus, molecules may
be escaping the liquid and returning to the liquid from the gas at the same time.
When a vessel contains both a liquid and a vapor, molecules are continually going
from the liquid to the vapor or gas and from the vapor to the liquid. When the
number of molecules leaving the liquid equals the number entering the liquid, the gas
and the liquid are said to be in equilibrium with each other. So at equilibrium, equal
numbers of molecules pass between the liquid and the vapor, or gas.
When more molecules are escaping the liquid than returning, the liquid is said to be
evaporating. The process in which a greater number of molecules leave the liquid
than enters it is called evaporation. When more molecules are entering the liquid
from the vapor than are escaping the liquid, the vapor is condensing. The process in
which a greater number of molecules enter the liquid than leave it is called
condensation.
When the temperature of a liquid is increased, the pressure of the vapor in

equilibrium with it increases and maintains equilibrium. On the other hand, when the
temperature of a liquid is decreased, the pressure of the vapor decreases and
maintains equilibrium. When a liquid and a vapor are at equilibrium, the pressure of
the vapor is called the vapor pressure of the liquid.
The pressure of a gas or vapor above the surface of a liquid in a closed container is
not necessarily the same as the vapor pressure of the liquid. In order for the pressure
of the gas to be equal to the vapor pressure of the liquid, the gas and the liquid must
be in equilibrium with each other. When the temperature of a liquid in a closed
container is increased, the pressure of the vapor increases until the vapor and the
liquid are at equilibrium with each other.

When a liquid is placed in an open container and heated, both its vapor pressure and
its rate of evaporation increase. When liquid in an open container is heated until the
vapor pressure equals the pressure of the atmosphere, evaporation becomes very
rapid, and the liquid boils.
If the pressure over a boiling liquid is increased, the boiling temperature is increased
and if the pressure over a boiling liquid is decreased, the boiling temperature is
decreased. Since the pressure of the atmosphere on the top of a mountain is lower
than at sea level, liquids boil at lower temperatures on top of a mountain.
The vapor pressures for different liquids at the same temperature are not the same.
Therefore, water and pentane have different vapor pressures at 100 °F. (Figure 1.1).
The vapor pressure of pentane is 18 approximately pounds per square inch at 100°F.
Water has a vapor pressure of 5 pounds per square inch at a temperature of 162 ºF.
Recall that the vapor pressure of the liquid must be equal to the pressure of the
surroundings for a liquid to boil. If the pressure of the atmosphere is 14.7 psi, water
boils at 212°F. A pressure cooker cooks food faster than an open container, because
the temperature inside is increased by the increase in pressure.

Figure 1.1 Vapor Pressure of Water and Pentane

1.3 PARTIAL PRESSURE
The pressure that a gas exerts on the walls of a container depends on the number of
collisions between the molecules and the container wall. If more molecules are
present, there are more collisions and a greater pressure. If two containers of the
same volume are filled with gas to the same pressure and temperature, each contains
the same number of gas molecules. For the same volume and temperature, the
greater the number of molecules in a gas, the greater the pressure of the gas must be.
When two or more gases are mixed, each gas exerts a pressure on the walls of the
container. Although these separate pressures cannot be measured, the total pressure
can be measured. The total pressure of a gas mixture is equal to the sum of the
pressures of the different gases in the mixture; the separate pressures of the gases are
called partial pressures.
For a mixture of two gases, if the partial pressure of each gas is the same, there must
be equal numbers of each kind of molecule. If a tank contains 5 times as many
ethane molecules as propane molecules, the partial pressure of ethane is 5 times as
great as propane, the gas is said to be richer in ethane. When two or more pure
liquids (or gases) are mixed, the components of the mixture are the original pure
liquids, or substances. Enrichment is a process by which a mixture (for example, a
mixture of several gases) becomes more pure, enriched, or rich in one of its
components.
If a closed container is partially filled with a mixture of two liquids, molecules of

both liquids escape to the gas from the liquid and return to the liquid from the gas.
When the number of molecules escaping equals the number returning- for both
components, the gas and the liquid are said to be at equilibrium with each other. At
equilibrium, the number of molecules escaping from the liquid is equal to the number
returning to the liquid for each component. The drawing shows a tank containing a
mixture of two components, one heavy and one light. An example of such a system
would be butane-hexane, where butane would be the light molecules and hexane the
heavy molecules.

At equilibrium the number of light molecules escaping from the liquid is equal to the
number returning to the liquid. Also, at equilibrium the number of heavy molecules
escaping from the liquid is equal to the number of heavy molecules returning to the
liquid. However, at equilibrium the number of light molecules escaping and
returning to the liquid is not equal to the number of heavy molecules escaping and
returning to the liquid. Light molecules are able to escape the liquid more rapidly
than the heavy ones. Therefore, at equilibrium, there are more light molecules
escaping and returning to the liquid. Because the light molecules are able to escape
the liquid faster than the heavy ones, the light molecules tend to concentrate or to be
enriched in the vapor. For example, if the liquid contains half light and half heavy
molecules at equilibrium, the gas contains more light molecules than heavy
molecules.
When the gas and the liquid are at equilibrium, the gas is richer in the light
component and the liquid is richer in the heavy component. Therefore, if a liquid
mixture is partially vaporized, the light component in the vapor becomes more con-
centrated than the light component in the liquid. In other words, the vapors are
enriched in the lighter component.

1.4 FUNDAMENTALS
Fractional distillation is an operation which is based on the differences in volatility or

different “escaping tendencies” of the products which have to be separated. It is
obvious that for solving the numerous problems in technical fractionation a thorough
knowledge of the fundamental laws and rules governing the volatility characteristics
of systems consisting of two or more components is a prerequisite.
1.4.1 Henry's Law
This law states that at a given temperature the partial vapour pressure of a relatively
volatile substance above its solution (in a relatively non-volatile solvent) is
proportional to its concentration in the solution.
This can be expressed by:
Pi = Ci xi …………………………………………….. (1)
Where xi = mole fraction of a certain component in the liquid,

Pi = partial vapour pressure of this component,
Ci = proportionality factor.
In general, this law holds only for low concentrations of component “i”. In certain
cases, however, it is applicable throughout the entire range of concentrations. Such
solutions are said to behave ideally and on extrapolating Henry's law in such cases to
the pure compound (i.e. increasing the concentration of the dissolved substance) we
see that, since when xi becomes 1, Ci equals Pi, this factor is then equal to the vapour
pressure (Pi) of the pure substance and to the system pressure.
Thus the mathematical expression becomes:
Pi = Pi xi …………………………………………….. (2)
In this form and restricted to ideal solutions Henry's law is known as Raoult's law.
Many hydrocarbon systems closely approach the hypothetical ideal solution and
Raoult's law can therefore be applied in these cases without introducing too serious
an error. Mixtures of paraffin and naphthene are, in general, very nearly ideal, while
mixtures of aromatics with naphthenes or paraffins are further away from ideal
solutions.

It must be realized, however, that ideal behaviour only occurs with substances as
closely related as hydrocarbons, and is most uncommon for other instances.
A particularly simple case where Raoult's law is not valid is the case of two or more
components completely immiscible in the liquid phase. In this case the total pressure
is independent of the relative amounts in which these components are present and is
simply equal to the sum p =  Pi of the vapour pressures of the pure components at
the given temperature. The total pressure is therefore higher than the vapour pressure
of any component. Such a system is called a pseudo-azeotrope.
1.4.2 Dalton's Law
The second important law underlying the theory of fractional distillation is Dalton's
law regarding partial pressures and their additively. Mathematically, Dalton's law is
expressed as follows:
Pi = P Yi and  Pi =P …………………………. (3)
Where Pi= partial pressure of component “i”,

P = total pressure of system,
Yi = mole fraction of component “i” in the vapour phase.
It follows from (2) and (3) that
Pi xi = P Yi
Yi Pi
 ………………………………. (4)
xi P
From equation (4) (known as Raoult-Dalton's law) it follows that the concentration of
any component in a vapour which is in equilibrium with a liquid mixture can be
calculated by multiplying the concentration of that component in the liquid phase by
the ratio of the vapour pressure of the pure component to the total pressure of the
system. All concentrations are to be expressed as mole fractions.
1.5 K VALUES
The fact that components in a non-ideal mixture do influence the volatility of the
other components results in deviations from Raoult – Dalton’s law which are of the
same order of magnitude as the ones which can be corrected for by the introduction
of fugacities. As the theoretical treatment of this subject is very complicated, a
solution of the problem is found by introducing the concept of “k values”.

Yi
For a number of pure hydrocarbons and a few other compounds the x ratios for
i
mixtures have been determined experimentally over a wide range of temperatures

and pressures, and the values thus obtained, the so-called k values, have been plotted
versus P and T in "k value charts" (Figures 1.3 through 1.15).
It should be mentioned that some of the k charts are based on experimental data and
some of the graphs are calculated from fugacities.
Using k values, equation (4) becomes:
Yi
xi
= ki or Yi = ki xi ………………………….. (4a)
Applications
Using the simple relationship:
Yi
xi
= ki or Yi = ki xi ………………………… (4a)
It is possible to calculate boiling points, dew points, vapour pressures and dew
pressures of mixtures.
1.6 BOILING POINT CALCULATION
The boiling point of a mixture (at a given pressure) is defined as the temperature at
which, when the temperature of the liquid mixture is raised, the first infinitesimal
amount of vapour escapes as a bubble. This temperature is also known as the
"bubble point". The vapour will contain a certain amount of each component,
depending on the volatility of that component, and it is clear that if the concentration
in the vapour phase (Yi) is expressed in mole fraction,  Yi must equal 1.
Starting with a liquid of known composition the problem has to be solved by trial and
error, since at a given pressure the temperature has to be found, at which the
corresponding ki values, when multiplied by xi, result in Yi values adding up to 1.
The following example illustrates the procedure:

System pressure: 150 psia
By graphical interpolation we find a boiling point of 169°F under 150 psia. With this
temperature a check calculation should be made and, if necessary, the procedure
should be repeated within narrower limits until the correct value is found. In those
cases, where no k values of the components are available, the vapour pressure will
have to be used.
Vapour pressures should not, however, be used in combination with k values.
Vapour Pressure Calculation for Hydrocarbon Mixtures

The calculation of the vapour pressure of mixtures at a given temperature is very
simply made if Raoult-Dalton's law is valid. The mole fraction of each component is
multiplied by the vapour pressure of the component at the desired temperature and
the values obtained are added together. The sum represents the vapour pressure of
the mixture.
A more exact method would be to use k values and to determine the boiling pressure
for the given temperature in essentially the same fashion as has been shown in the
preceding section for the determination of the bubble point at a given pressure.
1.7 DEW POINT CALCULATION
The dew point of a mixture is the temperature at which, when the temperature of the
vapour is lowered, the first infinitesimal droplet of condensate is formed. This
temperature is of practical importance for establishing the top temperature of a
fractionating column. In the case of a dew point calculation the vapour composition
is known and by dividing the Yi values by the corresponding ki values one arrives at
xi values which should add up to 1. At trial and error calculation similar to that
carried out for the bubble point leads to the dew point. The same remarks regarding
the use of k values and vapour pressures as made under "Boiling Point Calculation"
also apply to the dew point calculation.
Calculation of Dew Pressure
The dew pressure at a given temperature is the pressure at which condensation

starts to take place and is, therefore, an important value in connection with partial
condensation for making reflux. According to Raoult-Dalton's law:
Yi P
Xi = P
i
Yi
And since  xi = p  =1
Pi
1
P =  Yi
Pi
For the calculation of p (the dew pressure) the molal concentration of each
component is divided by its vapour pressure and the values obtained are added
together. The reciprocal of the sum is the dew pressure.
Also in this case a more exact solution can be obtained by using k values and
determining dew pressures at the given temperature by trial and error.
1.8 FLASH CALCULATION
So far we have only considered vaporization and condensation of infinitesimal

amounts of material at the boiling and dew points. In many cases it is desired to
know the amount and composition of the vapour in equilibrium with liquid at
temperature and pressure conditions in between the bubble point and the dew point.
For instance, the degree of vaporization of a crude oil or some other feedstock after
leaving the furnace is an important item in design calculations. Often it is desired to
know the amount vaporized at a series of temperatures and pressures for a given
material. When such a series of values is plotted against temperature with pressure
as a parameter, the resulting graph is called a "flash curve". A flash calculation is
based on a combination of a material balance and vapour liquid equilibrium relations.

Assume a feed of n components and take F moles of total feed as a basis.
Let V = total moles of feed-vapour

L = total moles of feed-liquid
So V + L = F
xi = mole fraction of component i in the liquid phase
Yi = mole fraction of component i in the vapour phase
Zi = mole fraction of component i in the total feed
ki = k value for component i at flash conditions.
The following material balance for a component holds true:
Lxi + VYi = Fzi

or
Lxi + Vki xi = Fzi

Vk i x i
 Lxi (1 + Lx i
) = Fzi
Fz i
Hence Lxi = 1  k V
i
L
This is the most convenient form of the so-called flash equation. When temperature
V
and pressure are set, a value of L
is assumed and Lxi for all components is
calculated.
V
Now as  Lx i = L  x i = L, and as V = F-L, the assumed value of L
can be
checked against the calculated one. The flash calculation has to be repeated until the
V
calculated L
value is equal (within the limits of k value accuracy) to the assumed
V
value of L
.
When the above-mentioned procedure has been finished the vapour-liquid

composition of the feed at the given temperature and pressure can be calculated
from:

Lx i Lx i
xi = =  Lx and Yi = ki xi
L i
Fzi  Lx i
Or Yi =
V
By keeping the pressure constant and changing the temperature, a series of values of
V (all in mole fractions) at different temperatures can be obtained and a flash curve
for the pressure under consideration can be plotted.
As an illustration of the use of the flash equation one point of a flash curve (at 50
psia) of a crude oil will be calculated. In order to be able to carry out this calculation
the composition of the crude should be known. Above C5, narrow boiling cuts (10-
20°F boiling range) are considered to be "components". For obtaining the necessary
data a precision distillation of the crude has to be carried out in the laboratory and the
volume percentage distilled is plotted against the top temperature. This type of
distillation is carried out in an apparatus allowing a high degree of fractionation and
should, therefore, not be confused with the conventional ASTM distillation. The
yield vs. temperature curve obtained by the precision distillation is known as a "true
boiling point curve" (TBP curve) and is the basis of our flash calculations. As the
precision distillation proceeds, the gravities of the distillates are determined and
plotted in a similar manner.
Figure 1.2 shows the TBP curve of a crude oil. This curve is already plotted on a
weight basis, but usually the volumetric mid points of the fractions (the sum of the
volumes of all lighter fractions plus half the volume of the fraction in question) are
plotted versus the cutting temperature of each fraction and the weight percentages are
calculated from the corresponding volume yields as read from the TBP curve and the
gravities of the fractions. The mid-boiling temperature of each cut is its reference
boiling point when reading the vapour pressure from the Shell Data Book Chart. The
amount of vapour flashed off from given crude at 400°F at a pressure of 50 psia is
now calculated. The various data are tabulated in Table 1.3. For the sake of
convenience somewhat wider fractions (30-50°F) were used in this example.

Figure 1.2 Typical Crude Oil Yield – True Boiling Point

Relationship

Table1.1 Bubble Point Calculation Worksheet
Equipment Number:____________________
Bubble Point Conditions: Pressure ________________________ Pisa;
Convergence Pressure ____________________ Psia
Liquid Trial Temperatures Final Temp
Mol. T= ºF T= ºF T= ºF T= ºF
Comp MW
Frac. y y
k k y k y k
x =kx =kx
C1 16 0. 0. 0. 0. 0.
C2 30 0. 0. 0. 0. 0.
C3 44 0. 0. 0. 0. 0.
iC4 58 0. 0. 0. 0. 0.
nC4 58 0. 0. 0. 0. 0.
iC5 72 0. 0. 0. 0. 0.
nC5 72 0. 0. 0. 0. 0.
nC6 86 0. 0. 0. 0. 0.
nC7 100 0. 0. 0. 0. 0.
nC8 114 0. 0. 0. 0. 0.
H2 2 0. 0. 0. 0. 0.
N2 28 0. 0. 0. 0. 0.
CO 28 0. 0. 0. 0. 0.
CO2 44 0. 0. 0. 0. 0.
H2S 34 0. 0. 0. 0. 0.
Total 1.0000 1.0000

Table1.2 Dew Point Calculation Worksheet
Equipment Number: __________________________________

Dew Point Conditions: Pressure ________________________ Pisa;
Convergence Pressure ____________________ Psia
Vapor Trial Temperatures Final Temp
Mol. T= ºF T= ºF T= ºF T= ºF
Comp MW
Frac. x x
k k x k x k
y =y/k =y/k
C1 16 0. 0. 0. 0. 0.
C2 30 0. 0. 0. 0. 0.
C3 44 0. 0. 0. 0. 0.
iC4 58 0. 0. 0. 0. 0.
nC4 58 0. 0. 0. 0. 0.
iC5 72 0. 0. 0. 0. 0.
nC5 72 0. 0. 0. 0. 0.
nC6 86 0. 0. 0. 0. 0.
nC7 100 0. 0. 0. 0. 0.
nC8 114 0. 0. 0. 0. 0.
H2 2 0. 0. 0. 0. 0.
N2 28 0. 0. 0. 0. 0.
CO 28 0. 0. 0. 0. 0.
CO2 44 0. 0. 0. 0. 0.
H2S 34 0. 0. 0. 0. 0.
Total 1.0000 1.0000

Table 1-3
Sample Flash Calculation at 400ºF and 50 psia (Kuwait Crude)
Lower than 75 slightly

Higher than
70
Graphical interpolation (3) gives
V = 29.2 mole %
L = 70.8 mole %
(1) Determined experimentally.
(2) From Shell Data Char.
(3) Graphical interpolation is only permitted if a well defined
point of intersection is obtained. Extrapolation is never
permitted. Figures thus obtained must be verified by a subsequent
check calculation.
Table 1-4 Flash Calculation Worksheet
Flash Vessel Number: _____________

Flash Condition: Temperature __________________________ ºF
Pressure ______________________________ Pisa
Convergence Pressure ___________________ psia
Liquid Trial Values of L Final L
Feed L= L= L= L= V=
Comp MW Mol. k x
Frac. x
x x y = kx
“N” =N/(L +Vk)
=N/(L +Vk)
C1 16 0. 0. 0. 0. 0. 0.
C2 30 0. 0. 0. 0. 0. 0.
C3 44 0. 0. 0. 0. 0. 0.
iC4 58 0. 0. 0. 0. 0. 0.
nC4 58 0. 0. 0. 0. 0. 0.
iC5 72 0. 0. 0. 0. 0. 0.
nC5 72 0. 0. 0. 0. 0. 0.
nC6 86 0. 0. 0. 0. 0. 0.
nC7 100 0. 0. 0. 0. 0. 0.
nC8 114 0. 0. 0. 0. 0. 0.
H2 2 0. 0. 0. 0. 0. 0.
N2 28 0. 0. 0. 0. 0. 0.
CO 28 0. 0. 0. 0. 0. 0.
CO2 44 0. 0. 0. 0. 0. 0.
H2S 34 0. 0. 0. 0. 0. 0.
Total 1.0000 1.0000 1.0000

Table 1-5 Flash Material Balance Worksheet
Flash Vessel Number:

Lb Mol/Hr Lbs/Hr
Comp MW
Feed Liquid Vapor Feed Liquid Vapor
C1 16
C2 30
C3 44
iC4 58
nC4 58
iC5 72
nC5 72
nC6 86
nC7 100
nC8 114
H2 2
N2 28
CO 28
CO2 44
H2S 34
Total

Figure 1.3a Vapor Liquid Equilibria (Hydrocarbon Systems)

Figure 1.3b Vapor – Liquid Equilibria for Heavy Hydrocarbons

Figure 1.4 “K” Values for Methane

Figure 1.5 “K” Values for Ethane

Figure 1.6 “K” Values for Propane

Figure 1.7 “K” Values for i-Butane

Figure 1.8 “K” Values for n-Butane

Figure 1.9 “K” Values for i-Pentane

Figure 1.10 “K” Values for n-Pentane

Figure 1.11 “K” Values for Hexane

Figure 1.12 “K” Values for Heptanes

Figure 1.13 “K” Values for Octane

Figure 1.14 “K” Values for Nonane

Figure 1.15 “K” Values for Decane

Chapter 1

Uploaded by

Copyright:

Available Formats

Chapter 1

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chapter 1

Uploaded by

Copyright:

Available Formats

Course Manual Crude Distillation (Theoretical Principles)

Theoretical Principles of Fractional

MIDOM (Rev.0) Jan. 2006 Chapter # 1 Page # 1 of 35

1.2 Vapor Pressure

1.3 Partial Pressure

1.5 Analysis of Mixtures

1.6 Boiling Point Calculation

1.7 Dew Point Calculation

1.8 Flash Calculation

MIDOM (Rev.0) Jan. 2006 Chapter # 1 Page # 2 of 35

Theoretical Principles of Fractional Distillation

1.2 VAPOR PRESSURE

A gas or vapor consists of molecules in random and chaotic motion. Millions of

MIDOM (Rev.0) Jan. 2006 Chapter # 1 Page # 3 of 35

When the temperature of a liquid is increased, the pressure of the vapor in

MIDOM (Rev.0) Jan. 2006 Chapter # 1 Page # 4 of 35

MIDOM (Rev.0) Jan. 2006 Chapter # 1 Page # 5 of 35

Figure 1.1 Vapor Pressure of Water and Pentane

MIDOM (Rev.0) Jan. 2006 Chapter # 1 Page # 6 of 35

1.3 PARTIAL PRESSURE

If a closed container is partially filled with a mixture of two liquids, molecules of

MIDOM (Rev.0) Jan. 2006 Chapter # 1 Page # 7 of 35

MIDOM (Rev.0) Jan. 2006 Chapter # 1 Page # 8 of 35

Fractional distillation is an operation which is based on the differences in volatility or

1.4.1 Henry's Law

This can be expressed by:

Where xi = mole fraction of a certain component in the liquid,

Thus the mathematical expression becomes:

MIDOM (Rev.0) Jan. 2006 Chapter # 1 Page # 9 of 35

1.4.2 Dalton's Law

Pi = P Yi and  Pi =P …………………………. (3)

Where Pi= partial pressure of component “i”,

It follows from (2) and (3) that

MIDOM (Rev.0) Jan. 2006 Chapter # 1 Page # 10 of 35

mixtures have been determined experimentally over a wide range of temperatures

Using k values, equation (4) becomes:

Using the simple relationship:

1.6 BOILING POINT CALCULATION

The following example illustrates the procedure:

MIDOM (Rev.0) Jan. 2006 Chapter # 1 Page # 11 of 35

System pressure: 150 psia

Vapour pressures should not, however, be used in combination with k values.

Vapour Pressure Calculation for Hydrocarbon Mixtures

Calculation of Dew Pressure

The dew pressure at a given temperature is the pressure at which condensation

1.8 FLASH CALCULATION

So far we have only considered vaporization and condensation of infinitesimal

MIDOM (Rev.0) Jan. 2006 Chapter # 1 Page # 13 of 35

Assume a feed of n components and take F moles of total feed as a basis.

Let V = total moles of feed-vapour

The following material balance for a component holds true:

Lxi + VYi = Fzi

Lxi + Vki xi = Fzi

When the above-mentioned procedure has been finished the vapour-liquid

MIDOM (Rev.0) Jan. 2006 Chapter # 1 Page # 14 of 35

MIDOM (Rev.0) Jan. 2006 Chapter # 1 Page # 15 of 35

Figure 1.2 Typical Crude Oil Yield – True Boiling Point

MIDOM (Rev.0) Jan. 2006 Chapter # 1 Page # 16 of 35

Table1.1 Bubble Point Calculation Worksheet