Section 3

IMPORTANT PROPERTIES OF
HYDROCARBONS
TABLE OF CONTENTS
PAGE #
SOME BASIC PRINCIPLES ........................................................................................................................ 3.1
The Three States of Matter ................ ..... ............................... ................. ... .. .......................................... 3.1
The Behavior of Fluids .... ............................. .. ....................................................................................... 3.2
PHYSICAL PROPERTIES ............................................................................................................................ 3.5
Boiling Point. .......................................................................................................................................... 3.5
Vapor Pressure: Practical Applications .......... .. ..... ................................................. ... ... .................. .. .... 3.8
Vapor Pressure of NGL Mixtures .......................................................................................................... 3.12
Consequences and Applications of Vapor Pressure Effects ...................................... ........... " .............. 3.14
Reid Vapor Pressure ............................................................................................................................... 3.16
Summary ................................................................................................................................................. 3.18
Heat of Combustion .......... .. .. ......... .............. " ................................................................... ... .. ... ............. 3.18
Flammability Limits ....... ....... .. .......... ... ...... ....... .. ...... ......... ......................... ......... ..... ... ......... .. .. ............. 3.18
Density - Gases ................................................................ .................... ................... ........................ ..... 3.19
Change of Volume ................................................................................. ....................... .. ........ .. ............. 3.19
General Ideal Gas Law ........ ................................................ ................. ..... ........... ... ...................... .. ....... 3.21
Ideal Gas Density ............................ .. ... ........... .. ............ ...... .. ... .... ........ .. ........... ............ ............... .......... 3.22
Density of a Real Gas ................................................................................................................... ......... 3.23
Densities of Liquids ............... ... ... .. ............ ..... ............ .................... ............................ .. ....................... .. 3.23
Crude Oil Distillation ............................................................................................................................. 3.25
Crude Oil Density ................................................................................................................................... 3.26
Density ofNGL's ................................................................................................................................... 3.26

VER: P3GEN_Ol-Ol-2001

GAS PROCESSING OPERATIONS 3.1

 IMPORTANT PROPERTIES OF HYDROCARBONS

LIST OF FIGURES
FIGURE # PAGE #
3.1 The Three Phases of Matter ............................................................................................................ 3.1
3.2 Molecules in Motion ........................................................................................................................ 3.3
3.3 Molecules Trapped in a Closed Container .......................... .................... .......................... ............. 3.3
3.4 Vapor Pressure vs. Boiling Temperature for an Example Liquid in a Closed Vessel .................. 3.5
3.5 Pressure Gauge Reads Vapor Pressure of Liquid in Separator. ..................................................... 3.8
3.6(a) Vapor Pressure of Pure Hydrocarbons - SI Units ........................................................... ............. 3.9
3.6(b) Vapor Pressure of Pure Hydrocarbons - English Units ............................................................... 3.10
3.7 Operating Pressure of Fractionation Tower is Determined by Vapor Pressure of Top Product .. 3.15
3.8 LP Gas Vapor Pressure Apparatus .................................................................................................. 3.16
3.9 Reid Vapor Pressure Apparatus ... .............. ........... .... ............................... .. ... .. .. .. .. .. ...... ................... 3.16
3.10 Reid Vapor Pressure vs. True Vapor Pressure for Crude Oils ....................................................... 3.17
3.11 Some Representative TBP Distillation Curves ............................................................................... 3.25
3.12 Density Correlation for Crude Oils ................................................................................................. 3.27

LIST OF TABLES
TABLE # PAGE #
3.1(a) Properties of Paraffin Hydrocarbons - SI Units .................... ... ...... ..... ... .......... .. ................... .... ..3.6
3.1(b) Properties of Paraffin Hydrocarbons - English Units ................. ........ ............. ................ ...... ..... 3.7

3.11 SANTOS LTD.

 Section 3
IMPORTANT PROPERTIES OF
HYDROCARBONS
SOME BASIC PRINCIPLES
A full understanding of various plant processes depends upon a familiarity with certain basic,
physical principles. These principles are offered here as a review and reference for the operator.

The Three States of Motter

All matter can exist in three possible states: solid, liquid or gas. Another name for state is
phase. Water is an example commonly used to demonstrate these three phases:
• Solid water is called ice.
• Liquid water is called water.
• Gaseous water is called steam.
The three phases of matter are shown graphically in Figure 3.1, in which the individual mole-
cules of the substance are represented by little balls.

In each of these three phases, the individual water molecules do not change; the water mole-
cule, H20, is the same for all phases. What does change is the distance between the individual water
molecules. The molecules of a solid are packed tightly together in a rigid structure while those in a
liquid are much less confined and are free to move about or flow. The molecules of a gas are even
more loosely spaced and can also flow freely. A gas can also be called a vapor. Since liquids and
gases both exhibit the ability to flow, they are both referred to as being fluids.

0 0
0
0

s
0
0
0 0
0
Solid Liquid Gas

Figure 3.1 The Three Phases of Matter

GAS PROCESSING OPERATIONS 3.1

 IMPORTANT PROPERTIES OF HYDROCARBONS

The Behavior of Fluids

Fluids Defined
The hydrocarbons and other substances that we deal with in gas processing plants are fluids.
That is, they are always (we hope) in either the liquid or vapor phase. Whenever you see a pipe, a
steam or air line, a tank, a pump, a compressor, a tower or even a filled sample container in a gas plant,
it almost certainly contains a fluid. What is a fluid? Anything that can flow is a fluid. Fluids have no
definite shape; they assume the shape of the container into which they are placed.

Every fluid has properties which distinguish it from other fluids under specific conditions.
Some properties by which fluids may differ from each other are:

temperature pressure boiling point

gravity miscibility solubility
freezing point phase composition
vapor pressure hydrate point heat capacity
flammability density molecular weight
heat of vaporization and more ...

Phase Changes
Experience tells us that the phase in which we find water at any given time depends somehow
on its temperature. After all, ice is cold and steam is hot. Furthermore, we know that if we were to
place a chunk of ice in a warm place, it would melt (change phase) and become liquid water. We also
know that if we were to put liquid water into a pan, place it on a stove and begin to heat it, the water
will eventually vaporize or boil away as steam, which is just another way of changing phase.

Experience also tells us that these phase changes can be reversed: we can condense steam back
to a liquid by bringing it into contact with a cool surface, and we can freeze water to solid ice by
placing it in the kitchen freezer for awhile. All the phase changes just described had something to do
with the addition or subtraction of heat.

The Role Of Heat In Phase Changes

If we could look very closely at the molecules of solids, liquids and gases, we would observe a
curious thing; the molecules of all substances are constantly in motion. Molecules that are in the fluid
phase, either liquid or gas, can move about freely. The molecules in a liquid are held somewhat closely
together by a natural attraction which tends to keep them together on the inside of a distinct surface
boundary. Gas molecules are far enough apart, however, to escape this attraction and can move about
randomly in space. Since solids cannot flow and individual molecules are rigidly held in the structure
so that they cannot break free, the motion they exhibit is vibration.

The strength of these vibrations in a solid, and the velocity of the molecules in a fluid are
caused by and are indications of the amount of heat energy the molecules contain. The greater the heat
energy, the faster the molecules move about or vibrate. These molecular movements occur on such a
small scale that we are not generally aware of them as being motions, but we are able to provide a
somewhat indirect measure of them. This indirect measure of molecular motion is what we call tem-
perature.

3.2 SANTOS LTD.

 SOME BASIC PRINCIPLES

Temperature is a relative measure of the extent to which a substance is either "hot" or "cold".
Temperature gives us some idea of the heat energy possessed by a substance but temperature is not the
same thing as heat. For instance, two identical substances may be at exactly the same temperature but
may contain quite different amounts of heat energy as can be illustrated by making a comparison
between a burning match stick and a burning bam.
The greater the heat content of a substance, the greater will be its molecules' motion. The
molecules of a "cold" solid may have only small vibrational energies; but if heat is applied from some
outside source, the vibrational energies or heat content of the solid will begin to increase. If sufficient
heat is added, the vibrations may become so great that the mutual attractions among the individual
molecules is overcome and the molecules will begin to break out of the rigid structure, that is, begin to
flow. When this happens to a solid, we say that it is melting.
In a similar fashion, as shown in Figure -
3.2, if a liquid is sufficiently heated, the motion of o o
individual molecules can become so great that they
can escape the surface of the liquid to become a
vapor. The greater the amount of applied heat, the
greater the number of molecules that will escape .? 0
000 0
the liquid. When this occurs, we say that the liquid 0 0
600
0
is vaporizing. '\ 0 0
0 0 ..-0
The above processes are reversible: Liquids ~ ~ ~
can freeze or solidify, and vapors can condense to Heat
liquids. In each of these cases, heat is removed
from the substance to the point where the attrac- Figure 3.2 Molecules in Motion
tions among the molecules become greater than the
heat energy remaining in the molecules.
The phase in which we find a given substance depends primarily, therefore, upon the amount of
heat energy that is contained within the molecules of the substance. The most important lesson to be
remembered, however, is that by controlling the amount of heat energy that a substance is subjected
to, we can control the phase of that substance.

Pressure
As mentioned earlier, in gas processing we are concerned with the behavior of fluids. There-
fore we are interested in the behavior of liquids and gases and the phase changes that occur between
them. In order to get the big picture, we need to
understand what gas pressure is all about.

Consider the molecules in a gas (or vapor)

which are moving rapidly in all directions. These
~!
molecules collide with each other and with any-
thing else that gets in their way, such as the walls
\1
of a container designed to hold them. If the con-
tainer depicted in Figure 3.2 were closed at the top,
as in Figure 3.3, the molecules with enough energy
to break free of the surface are trapped by the walls
and roof of the vessel. As they hit the sides and
roof of the container, some of their energy is trans- Figure 3.3 Molecules Trapped in a Closed
ferred the vessel walls. Container

GAS PROCESSING OPERATIONS 3.3

 IMPORTANT PROPERTIES OF HYDROCARBONS

Gas pressure inside a closed container is the sum total of the individual impacting forces
exerted by the molecules which collide with the walls of the vessel. Gas pressure is exerted equally in
all directions, even upon the surface of the liquid, if present. The magnitude of this pressure depends
on two things: the number of such collisions and the surface area over which they occur. However,
when talking about the gases inside closed vessels, we are dealing with three-dimensional objects, so it
becomes more useful to think in terms of the volume enclosed by those surface areas, a direct and
useful relationship. Therefore, in terms of vessel volume and number of collisions, the following rela-
tionships can be observed:

• If the number of collisions per unit volume increases, the pressure will also increase, and,
conversely,
• If the number of collisions per unit volume decreases, pressure decreases as well.

This means that the pressure exerted by a gas in a closed container can be controlled by vary-
ing either the volume or the rate at which collisions occur. If we consider the volume to be fixed, we
are left with controlling the number of collisions, which is easy to do.

If we add heat to the closed vessel in our example, two things can happen: one, more liquid
molecules may vaporize and, two, the molecules already in the vapor will move faster. Either of these
events will cause the number of collisions to increase and so, therefore, will the pressure. The reverse
will happen if the vessel is cooled.

This relationship is true even if there is no liquid but only gas present in the vessel. The gas
pressure inside a closed vessel is therefore directly related to the heat content of the gas. In fact, if
there is no liquid present, all gases, of any kind, will exert exactly the same pressure if their volume
and temperature are equal.

Vapor - liquid Equilibrium

Refer again to Figure 3.3. Some of the molecules in the vapor are shown to be colliding with
the surface of the liquid. When this happens, those molecules tend to stick there; that is, they return to
the liquid phase or "condense". When these molecules go into the liquid, their motion energy is trans-
ferred to other molecules which may then have sufficient energy to escape from the surface. In fact, at
a given temperature and pressure for a liquid and its vapor in a closed container, individual molecules
are constantly escaping from and returning to the liquid phase.

If we hold the temperature constant on such a liquid/vapor system, the number of molecules
becoming vapor will eventually be exactly equal to the number that are condensing. This state of
affairs is defined as being one of vapor-liquid equilibrium. This does not mean that the gas and
liquid are equal in volume or mass, but that the rate of evaporation equals the rate of condensation.
When more molecules are escaping from the liquid than are returning, the liquid is vaporizing. When
more molecules are returning to the liquid than are escaping, the vapor is condensing.

There is a special name given to the pressure that exists inside a closed liquid/vapor system
that has achieved equilibrium; that name is vapor pressure.

When the liquid and vapor phases of a substance are in equilibrium at constant temperature, we
say that the pressure exerted by the liquid/vapor system is the vapor pressure of the liquid at that
temperature.

3.4 SANTOS LTD.

 PHYSICAL PROPERTIES

Pressure-Temperature Relationships
When the temperature of a liquid and its vapor in a closed vessel is increased to a new con-
stant, the pressure of the vapor above the liquid increases until the vapor and liquid are once again in
equilibrium with each other. Therefore, when the temperature of a liquid in a closed vessel is in-
creased, its vapor pressure is also higher.

,A liquid is said to boil when its vapor pressure becomes equal to the pressure exerted upon its
surface/ When boiling starts, equilibrium is upset, and the number of molecules going into the vapor
phase greatly exceeds the number, if any, returning to the liquid. If the pressure on a liquid is fixed,
either by the force of the vapor on a liquid in a closed vessel or by the force of the atmosphere on a
liquid in an open vessel, then for a liquid to boil, heat must be added. If a liquid is already boiling,
and it is desirable to halt the boiling action, then the heat input must be reduced.
The pressure on the liquid need not be
fixed, however. For every liquid, over a range of 300

pressures, there is a range of corresponding tem- <is

'(jj

peratures at which the liquid will boil. The tem- So

~ 200
perature at which boiling starts is known as the liq- ::l
CIl
CIl
uid's boiling point at the given pressure. Should ~
a..
the pressure be increased, the temperature must be 00.
100
increased for boiling to continue. Another way of co
>
saying the same thing is that for each temperature,
o~--~--~----~-------
there is a pressure at which the liquid will boil. o 100 200
This pressure is equal to the vapor pressure of the BOiling Temperature (OF)

liquid at that temperature. If we were to plot the

Figure 3.4 Vapor Pressure vs. Boiling Tempera-
vapor pressure versus the boiling temperature of a
ture for an Example Liquid in a
liquid, the graph shown in Figure 3.4 would be the Closed Vessel
result.

PHYSICAL PROPERTIES
The physical properties of substances include such things as boiling point, density, viscosity,
etc. Each hydrocarbon has different properties from the others. Tables 3.1(a) and 3.1(b) show some of
the more common properties of hydrocarbons. The most important of the properties are discussed
below.

Boiling Point
The normal boiling point is the temperature at which a liquid boils at atmospheric pressure.
Water boils at lOOoe [212°F] at atmospheric pressure. The boiling points of hydrocarbons are related to
the number of carbon atoms. The more carbon atoms, the higher the boiling point. Propane, which has
three carbon atoms, boils at -42°e [-43.7°F]; normal butane has four carbon atoms and its boiling
point is -O.5°e [31.1°F] which is just below the freezing point of water. Heptane, with seven carbon
atoms, boils at 98.4°e [209.2°F] which is about the boiling point of water.

The difference in boiling points makes possible the separation of different hydrocarbons. Sev-
eral different hydrocarbons in a mixture can be separated by boiling out the lightest or lowest boiling
component first, and then successively boiling out each higher boiling component.

GAS PROCESSING OPERATIONS 3.5

 K? e--r-2)~)
d
'c
pi3svt m( .zr£!~U ---;2']] L~
Co)
---
en TABLE 3.1 (a)
Physical Constants of Paraffin Hydrocarbons and Other Components of Natural Gas
(GPA Publication 2145 SI-80 International System (SI) Units [Abridged - Approval Pending])

Component
Methane Ethane Prooane i-Butane n-Butane i·Pentane n-Pentane n·Hexane n-Heptane n-Octane n-Nonane n-Decane
Molecular Weieht 16.043 30.070 44.097 58.124 58.124 72.151 72.151 86.178 100.205 114.232 128.259 142.286
Boiling Point @ 101.3250 kPa (abs), K 111.63 184.57 231.08 261.34 272.66 300.99 309.21 341.89 371.57 398.82 423.97 447.31
Freezing Point @ 101.3250 kPa (abs), K 90.68 90.35 85.47 113.55 134.79 113.25 143.42 177.83 182.57 216.39 219.66 243.51
Vapor Pressure @ 313.15 K, kPa (abs) L./£Pc... (35000.) (6000.) 1341. 528. 377. 151.3 115.66 37.28 12.34 4.143 1.40 0.4732
Density of Liquid @ 288.15 K &
101.3250 kPa (abs)
Relative density (water = 1) (0.3) 0.3581 0.5083 0.5637 0.5847 0.6250 0.6316 0.6644 0.6886 0.7073 0.7224 0.7346 ::
""C
Absolute density, kglm3 (in vacuum) (300.) 357.8 507.8 563.2 584.2 624.4 631.0 663.8 688.0 706.7 721.7 733.9
Apparent density, kg/m3 (in air)
o
(300.) 356.6 506.7 562.1 583.1 623.3 629.9 662.7 686.9 705.6 720.6 732.8 :u
Density of Gas @ 288.15 K & ~
101.3250 kPa (abs) z
-t
Relative density (air = I), ideal gas 0.5539 1.0382 l.5225 2.0068 2.0068 2.4911 2.4911 2.9753 3.4596 3.9439 4.4282 4.9125 ""C
Kilogram per cubic metre, kglm3, ideal gas
Volume @ 288.15 K & 101.3250 kPa (abs)
0.6784 1.2718 1.~650 2.4582 2.4582 3.0516 3.0516 3.6443 4.2373 4.8309 5.4259 6.0168
~
""C
Liquid, cm3/mol (50.) 84.04 86.84 103.2 99.49 115.6 114.3 129.8 145.6 161.6 177.7 193.9 m
Ratio, gas/(liquid in vacuum) (442.) 281.3 272.3 229.1 237.6 204.6 206.8 182.1 162.4 146.3 133.0 122.0 ~
iii
Critical Conditions en
Temperature, K 190.55 305.43 369.82 408.13 425.16 460.39 469.6 507.4 540.2 568.76 594.56 617.4 o"T1
Pressure, kPa (abs) 4604. 4880. 4:<49. 3648. 3797. 3381. 3369. 3012 2736. 2486. 2288. 2099.
Gross Calorific Value, Combustion @
::z:::
288.15 K & Constant Pressure c-<
-
:u
Megajoule per kilogram, MJlkg, liquid 51.586 50008 49.044 49.158 48.579 48.667 48.344 48.104 47.919 47.783 47.670 o
Megajoule per kilogram, MJlkg, ideal gas
Megajoule per cubic metre, MJ/m3 , ideal gas
55.563 51.920 50387 49.396 49.540 48.931 49.041 48.722 48.482 48.290 48.137 48.043
~
37.694 66.032 93972 121.426 121.779 149.319 149.654 177.556 205.431 233.286 261.189 289.066 :u
Megajoule per cubic metre, MJ/m3 , liquid - 18458. 25394. 27621. 28718. 30333. 30709. 32091. 33095 33865. 34485. 34985. I:D
o
Volume air to burn one volume gas, ideal gas 9.54 16.70 23.86 31.02 31.02 38.18 38.18 45.34 52.50 59.65 66.81 73.97 Z
Flammability Limits @ 310.93 K & en
101.3250 kPa (abs)
Lower, volume % in air 5.0 2.9 2.0 1.8 1.5 1.3 1.4 1.1 1.0 0.8 0.7 0.7
Upper, volume % in air 15.0 13.0 9.5 8.5 9.0 8.0 8.3 7.7 7.0 6.5 5.6 5.4
Heat of Vaporization @ 101.3250 kPa (abs)
kJlkg @ boiling point 509.86 489.36 425.73 366.40 385.26 342.20 357.22 334.81 316.33 301.26 288.82 276.06
Specific Heat @ 288.15 K & 101.3250 kPa (abs)
Cp gas, kJ/(kg·K), ideal gas 2.204 1.706 1.625 1.616 1.652 1.600 1.622 1.613 1.606 1.601 1.598 1.595
~ 1.523 1.528 1.533 1.537
z Cv gas, kJ/(kg·K), ideal gas 1.686 1.429 1.436 1.473 1.509 1.485 1.507 1.517
a
en
k = CplCv , ideal gas
Cp liquid, kJ/(kg·K)
1.307
-
1.194
3.807
1.132
2.476
1.097
2.366
1.095
2.366
1.077
2.239
1.076
2.292
1.063
2.231
1.054
2.209
1.048
2.191
1.042
2.184
1.038
2.179
!:4
p
C)
TABLE 3.1(b)
J>
en Physical Constants of Paraffin Hydrocarbons and Other Components of Natural Gas
"'tJ
:lJ (GPA Publication 2145 English (fps) Units [Abridged - Approval Pending])
o
o
m
en Component
en Methane Ethane Propane i-Butane n-Butane i-Pentane n-Pentane n-Hexane n-Heptane n-Octane n-Nonane n-Decane
Z
C) Molecular Weight 16.043 30.070 44.097 58.124 58.124 72.151 72.151 86.178 100.205 114.232 128.259 142.286
o Boiling Point @ 14.696 psia, of -258.73 -127.49 -43.75 10.78 31.08 82.12 96.92 155.72 209.16 258.21 303.47 345.48
"'tJ
m Freezing Point @ 14.696 psia, OF -296.44 -297.04 -305.73 -255.28 -217.05 -255.82 -201.51 -139.58 -131.05 -70.18 -64.28 -21.36
:lJ
Vapor Pressure 100°F, psia (5000.) (800.) 188.4 72.58 51.71 20.445 15.574 4.960 1.620 0.5369 0.1795 0.0609
~
@
Density of Liquid @ 60°F & 14.696 psia
o:z Relative density @ 60°F/60°F (0.3) 0.3562 0.5070 0.5629 0.5840 0.6247 0.6311 0.6638 0.6882 0.7070 0.7219 0.7342
en °API (340.) 265.6 147.3 119.8 110.7 95.1 92.7 81.60 74.08 68.64 64.51 61.23
Absolute density, Ibm/gal (in vacuum) (2.5) 2.970 4.227 4.693 4.870 5.208 5.262 5.534 5.738 5.894 6.018 6.121
Apparent density, Ibm/gal (in air) (2.5) 2.960 4.217 4.683 4.861 5.198 5.252 5.524 5.729 5.885 6.008 6.112
Density of Gas @ 60°F & 14.696 psia "'tJ
::J:
Relative density (air = 1), ideal gas 0.5539 1.0382 1.5225 2.0068 2.0068 2.4911 2.4911 2.9755 3.4598 3.9441 4.4284 4.9127 -<
en
IblM fe, ideal gas
Volume @ 60°F & 14.696 psia
42.28 79.24 116.20 153.16 153.16 190.13 190.13 227.09 264.06 301.02 337.98 374.95
oJ>
Liquid, galllb-mol (6.4) 10.13 10.43 12.39 11.94 13.85 13.72 15.57 17.46 19.38 21.31 23.45 r-
"'tJ
ft3 gas!gal liquid, ideal gas (59.1) 37.48 36.375 30.64 31.79 27.39 27.67 24.37 21.73 19.58 17.81 16.33 :lJ
Ratio, gas!(liquid in vacuum) (442.) 280.4 272.1 229.2 237.8 204.9 207.0 182.3 162.6 146.5 133.2 122.2
o"'tJ
Critical Conditions
m
:lJ
Temperature, OF -116.67 89.92 206.06 274.46 305.62 369.10 385.8 453.6 512.7 564.22 610.68 652.0 ::::!
m
Pressure, psia 666.4 706.5 616.0 527.9 550.6 490.4 488.6 436.9 396.8 360.7 331.8 305.2 en
en
Gross Calorific Value, Combustion @ 60°F
Btu/lb, liquid - 22181. 21489. 21079. 21136. 20891. 20923. 20783. 20679. 20601. 20543. 20494.
Btu/lb, gas 23891. 22332. 21653. 21231. 21299. 21043. 21085. 20942. 20838. 20759. 20700. 20651.
Btu/ft3, ideal gas 1016.0 1769.6 2516.1 3251.9 3262.3 4000.9 4008.9 4755.9 5502.5 6248.9 6996.5 7742.9
Btu/gal, liquid - 65869. 90830. 98917. 102911. 108805. 110091. 115021. 118648. 121422. 123634. 125448 .
Volume air to burn one volume, ideal gas 9.54 16.71 23.87 31.03 31.03 38.19 38.19 45.35 52.52 59.68 66.84 74.00
Flammability Limits @ 100°F & 14.6% psia
Lower, volume % in air 5.0 2.9 2.0 1.8 1.5 1.3 1.4 1.1 1.0 0 .8 0.7 0.7
Upper, volume % in air 15.0 13.0 9.5 8.5 9.0 8.0 8.3 7.7 7.0 6 .5 5.6 5.4
Heat of Vaporization @ 14.696 psia
Btu/lb @ boiling point 219.45 211.14 183.01 157.23 165.93 147.12 153.57 143.94 136.00 129.52 124.36 119.65
Specific Heat @ 60°F & 14.696 psia
Cp gas, Btu/(lb-°F), ideal gas 0.5267 0.4078 0.3885 0.3867 0.3950 0.3844 0.3882 0.3863 0.3845 0.3833 0.3825 0.3818
Cv gas, Btu/(lb- oF), ideal gas 0.4029 0.3418 0.3435 0.3525 0.3608 0.3569 0.3607 0.3633 0.3647 0.3659 0.3670 0.3678
k =CplCv, ideal gas 1.307 1.193 1.131 1.097 1.095 1.077 1.076 1.064 1.054 1.048 1.042 1.038
Co) Cp liquid, Btu/(lb- oF) - 0.9723 0.6200 0.5707 0.5727 0.5333 0.5436 0.5333 0.5280 0.5241 0.5224 0.5210
:.....
 IMPORTANT PROPERTIES OF HYDROCARBONS

The boiling point of a compound is affected by the pressure at which the compound is held.
Propane, for example, boils at -42°C [-43.7°F] at atmospheric pressure, but if it is contained in a
system at 1207 kPa [175 psi], the boiling point rises to 38°C [lOO°F]. For all hydrocarbons, the boiling
point increases as the pressure increases.
The boiling point is also the temperature at which the vapor of a pure component will con-
dense. Liquid and vapor can exist at the same temperature; the amount of each depends upon the
amount of heat added to or removed from the mixture.
It is important that you remember that the boiling point is also the condensing point for a pure
component. Water boils at lOO°C [212°F] at 1 atm. Steam will condense at lOO°C [212°F] at 1 atm.
Pure propane will boil at a temperature of 38°C [lOO°F] when it is at a pressure of 1207 kPa [175 psi].
Propane Vapors from a compressor will condense at a temperature of 38°C [100°F] when the compres-
sor discharge pressure is 1207 kPa [175 psi].

Vapor Pressure: Practical Applications

When you read the pressure gauge on a separator partially filled with liquid hydrocarbon, you
are reading the vapor pressure of the liquid in the vessel. This applies to all oilfield and process
separators. The pressure gauge reading is due to the vapor pressure of liquid in the vessel. See Figure
3.5.

Figure 3.5 Pressure Gauge Reads Vapor Pressure of Liquid in Separator

The vapor pressure of liquid hydrocarbons will depend on the temperature and composition of
the liquid. Figures 3.6(a) and 3.6(b) show the approximate vapor pressures of pure hydrocarbons. The
vapor pressure of a mixture will approximately equal the sum of the vapor pressures of each compo-
nent times the percent of the component in the mixture. This is demonstrated in a coming section.

3.8 SANTOS LTD.

 PHYSICAL PROPERTIES

-40 o 50 100 150 200

• Critical Point ~

- - - - - Extrapolated ~

~
...

'lS<.0.f l0,L
~ .. ... 1'"

.. ""~-
~
. ~

I"'~
~ . ...
10000

'0
~v~
;pJ~~
./ ~
~ t.
Gr- 2 ':Z L ~ -"- V' I?~

-S::l
"5 /
V
/
L
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L

L
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V~
lL v
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II 1I
v
VV

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........ 1000 ~~
tU
a..
~ ~0
...
oi ~..:~~0
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./ ./ I/-<'~""" / / / II
~0LL

~m
1/ /
! /' ./ V / IL V
a..
...
0
c..
V
/
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v
L
/
/
~
.~ ~
0<::' /
lL j
Ii
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1/

>
tU
/
/' V V V /~' ~- --:.,2r L lL
/ V~ ~V
100 7 1£" V

./ / / / , ,
/ / V L IL
/ / / / / L
,/ / V V IL
/ v/ / / /
V / V V I /

10 / '/ V /
V
V
-40 o 50 100 150 200
Temperature, °C

Figure 3.6(a) Vapor Pressure of Pure Hydrocarbons - 81 Units

GAS PROCESSING OPERATIONS 3.9

 IMPORTANT PROPERTIES OF HYDROCARBONS

-40 -20 o 20 40 60 80 100 150 200 250 300 400

-•-
I Critical Point
r--
5000 r-- Extrapolated
~,
.,.. -
""e~a.t\
-'"
'" .. - '" '"
....~
~
1000

~iSL
500 ~~\. L. ~ ./

o ~ -~~ '/
V 1/
", ./ '" ~~\oe;
k'" v
V V
as "", e~;/"
..v ""
".
,/ ....
'e0-n ~ ~o~
..v y.~'l #~ ~ ~ .... 1
e /
~ V ~tO~ I'~ I~
:::l
tn
tn 100 V ;/ II
e ~0
a.
'-
~~~0
.~~'l>,
:::l
50 ,<~
8.
as ./ ./' ./ &/
> " ./ ~'lI

/'
V"
~ V
.....
.~;r ~~0 IJ
/
~f
V ~~~H:~
V ~ V
V ; V
/' ~.~
/ / '/ I 'r- 01J ~
/

10 /
V /V L
/ V
V
V I~~
~ ~~

5
/
"' L
/ /
II'
/
~ / ,/ /
/ / /' / II II
.... V' / / / II
/ V V / V
1
/
/ V / 1/
V
j
/

-40 -20 o 20 40 60 80 100 150 200 250 300 400

Temperature, of

Figure 3.6(b) Vapor Pressure of Pure Hydrocarbons - English Units

3.10 SANTOS LTD.

 PHYSICAL PROPERTIES

Vapor pressure is a gauge pressure reading. The vapor pressure charts on Figures 3.6(a) and
3.6(b) read in absolute pressure. You must subtract atmospheric pressure (101 kPa [14.7 psi]) from the
pressure shown on the charts to get the gauge pressure.

You may wonder why some liquid hydrocarbons have a low vapor pressure, whereas others are
extremely high. The pressure is due to the speed of movement of the molecules. You can visualize the
molecules inside a separator as being tiny hammers. When the separator pressure is high, the mole-
cules are moving rapidly and beating against the wall of the separator. This is actually what causes the
high pressure. Molecules in a separator operating at low pressures are moving slowly and, thus, their
beating action does not result in as much pressure inside the vessel.

The molecular movement decreases as the number of carbon atoms increases. The hydrocarbon
with only one carbon atom - methane - has the highest molecular movement and, thus, the highest
vapor pressure. As the number of carbon atoms increases, there is less pounding of the molecules, and
the vapor pressure is lower.

Example 3.1: A storage tank contains propane at 38°C [1()()0F]. What will the pressure gauge on
the tank read?

1209 kPa(g)
[173.3 psig]

38°C
[100°F]

SI Units English Units

Tank Temperature 38°C 100°F
Contents of Tank Propane Propane
Vapor Pressure of C3 at 1310 kPa(a) 188 psia
Tank Temperature (Figures 3.6(a) and 3.6(b»
Less atmospheric pressure -101 kPa -14.7 sia
Pressure Gauge Reading 1209 kPa(g) 173.3 psig

We said that the vapor pressure was the pressure exerted by a liquid. The vapor pressure
changes with temperature. In order for us to compare vapor pressure of different components, we must
measure each component at the same temperature. The vapor pressure of n-pentane at 126°C [258°F]
is 1000 kPa [145 psi], which is also the vapor pressure of propane at 27°C [81°F]. In order to compare
the vapor pressure of propane with that of n-pentane, we must take their vapor pressures at the same
temperature. Vapor pressures of petroleum products normally are measured at 38°C [100°F]. When we
refer to 1400 kPa [205 psi] LPG, we mean that its vapor pressure at 38°C [100°F] is 1400 kPa
[205 psi]. Obviously, it will be different at some other temperature.

We have referred to vapor pressure in two ways:

1. The pressure in a vessel partially filled with liquid. The pressure gauge reading is the
liquid vapor pressure at its temperature in the vessel.
2. The vapor pressure of a liquid product, such as propane or butane, which normally is
measured at 38°C [100°F].

GAS PROCESSING OPERATIONS 3.11

 IMPORTANT PROPERTIES OF HYDROCARBONS

Vapor Pressure of NGL Mixtures

Vapor pressure specifications may be expressed in terms of a TVP (True Vapor Pressure) or
RVP (Reid Vapor Pressure). These concepts will be discussed in a later section.
The vapor pressure or volatility specification is probably the most important factor determining
the ultimate amount of NGL's recovered and the type of NGL process selected.
The vapor pressure of an NGL product can be estimated from the following equation:

Py rrax. = £.J
"'" Xi Py I

Where: PYmix = vapor pressure of the NGL mixture, bar abs [psia]
Xi = mol fraction of each component in the mixture
PYj = vapor pressure of each component in the mixture, bar abs [psia]
This equation simply says that the vapor pressure of an NGL mixture is proportional to the
vapor pressure and amount of each individual component in the mixture. For specification purposes,
vapor pressures are almost always expressed at a temperature of 38°C [lOO°F].
For your convenience, Tables 3.1(a) and 3.1(b) present the physical properties of several NGL
components, including the vapor pressures, in both English and SI units.
Notice in the following example that propane has the largest effect on the vapor pressure of the
NGL product. Propane's contribution to the total vapor pressure of the product is (4.0215.11), or al-
most 80%, even though its composition is only 30%.

Example 3.2: Estimate the true vapor pressure (TVP) of an NGL mixture with the following
composition.
mol %
C3 30
nC4 20
nCs 20
nC 6 30
100

Metric English
Component Xi P y.,
I
bar abs XiPYI P yi , psia XiPYj

C3 0.30 13.41 4.02 188.40 56.5

nC 4 0.20 3.77 0.75 51.71 10.3
nCs 0.20 1.16 0.23 15.574 3.1
nC 6 0.30 0.373 0.11 4.96 1.5
1.00 LXi PYj = 5.11 bar abs LXi P = 71.4 psia
Yj

This is an extremely important concept in the design and operation of NGL facilities. We want
the extraction and stabilization processes to be selective. This means we want to drive out as many of
the highly volatile components as possible from the liquid product while retaining the less volatile
components. The highly volatile components raise the vapor pressure of the product unnecessarily and
reduce the "room" (in terms of vapor pressure) for the less volatile components. The following exam-
ple indicates this concept.

3.12 SANTOS LTD.

 PHYSICAL PROPERTIES

In Example 3.3, notice the effect of the selectivity of the stabilization system upon product
recovery. If the stabilization system allows a mere 2% ethane in the liquid product, the product rate
decreased by almost 10%. The small amount of ethane in the product contributes over 30% of vapor
pressure.

Example 3.3: An NGL product must be stabilized to meet a TVP specification of 3.5 bar abs [50
psia] at 38°C [lOOOP]. The unstabilized product has the following composition:
mol%
C2 10
C3 25
nC4 20
nC s 10
nC 6 35

What percent of the unstabilized feed can be recovered as liquid product if

a) no C2 remains in the liquid product?
b) 2% C2 remains in the liquid product?
No ethane in product

(1) (2) (3) (4) (5) (6)

Mol
Component Fraction Py , psi a Prod, mols Prod Mol% (3)x(5)
ethane 0.10 800
propane 0.25 188 13.70 17.41% 32.73
n-butane 0.20 51.74 20.00 25.41% 13.10
n-pentane 0.10 15.575 10.00 12.71% 1.98
n-hexane 0.35 4.96 35.00 44.47% 2.21
1.00 78.70 100.00% 50.02

Py mix = 50 psi a
2 % ethane in product
(1) (2) (3) (4) (5) (6)
Mol
Component Fraction Py , psia Prod, mols Prod Mol% (3)x(5)
ethane 0.10 800 1.45 2.00% 16.00
propane 0.25 188 5.84 8.08% 15.19
n-butane 0.20 51.54 20.00 27.67% 14.26
n-pentane 0.10 15.574 10.00 13.83% 2.15
n-hexane 0.35 4.96 35.00 48.42% 2.40
1.00 72.29 100.00% 50.00

Py mix = 50 psia

GAS PROCESSING OPERATIONS 3.13

 IMPORTANT PROPERTIES OF HYDROCARBONS

Two basic types of stabilization systems are employed in oil production and NGL recovery
facilities. These are:
1. Flash stabilization - NGL product is flashed to progressively lower pressures. Flash va-
pors are recompressed and may be recycled back into the inlet. Heat exchangers may be
used to control the product temperature. The oil-gas separation system on the North Slope
uses this type of stabilization process to meet the TVP specification of the export crude.
2. Distillation - NGL product is stabilized at constant pressure in a packed or trayed tower.
Temperature is varied from the top to bottom. Stabilizer tower may be refluxed or non-re-
fluxed (top tray feed). A non-refluxed stabilizer is often used in gas processing plants to
control the vapor pressure of the NGL product mixture.
The flash stabilization method (1) is the traditional method used in field processing facilities,
especially offshore. It has the advantages of simplicity, ease of control, and it simplifies topside de-
sign. Method (2), distillation, is more common in gas processing facilities. It has the advantages of
more selective separation, so product rates are higher. It also minimizes recompression costs.

Consequences and Applications of Vapor Pressure Effects

One of the more important applications of vapor pressure is that of fixing the operating pres-
sure of equipment used in process plants. In the example above, the tank pressure was 1209 kPa [175.3
psig]. If this was the maximum pressure that would be expected, the tank would be designed for that
pressure. Normally, a margin of safety is provided by adding at least 10% to the maximum pressure
expected.

The operating pressure of fractionating towers is fixed by the vapor pressure of the top product
at its condensing temperature. Suppose we have a mixture of hydrocarbons that includes propane and
heavier hydrocarbons, and we want to separate the propane from the other components in a fractionat-
ing tower. An aerial cooler is used to condense the propane that will be the overhead product from the
tower. Assume the air temperature is 35°e [95°F], See Figure 3.7.

At this temperature we can expect to condense the top product (propane) at 50 0 e [l22°F], The
vapor pressure of propane at condensing temperature is 1725 kPa(a) [250 psia]. This is the tower
operating pressure.

The temperature in the reboiler will be that required to make the bottom product have a vapor
pressure equal to the tower operating pressure. In this case, the composition of the bottom product is
such that when it is heated to 1200 e [250°F], its vapor pressure is 1725 kPa(a) [250 psia]. We must
provide steam or hot oil to the reboiler at a temperature above 1200 e [250°F] in order to add heat in
the reboiler.

Another application of vapor pressure is that of determining if a liquid, such as crude oil or
gasoline, will boil or partially vaporize if it is stored in an atmospheric tank that is heated from the sun.

A liquid - any liquid - will boil if it is in an open container and its vapor pressure is the
same as atmospheric pressure. Water at 38°e [100°F] has a vapor pressure of 6.5 kPa(a) [0.95 psia]. It
obviously does not boil at that temperature. However, when water is heated to 1000 e [212°F], its
vapor pressure rises to atmospheric and it starts to boil.

If crude oil or gasoline is stored in a tank that is open to the atmosphere, and the tank is heated
from the sun so that its vapor pressure rises to atmospheric pressure, it will start to boil. As a matter of
fact, a product stored in an atmospheric tank cannot have a vapor pressure above atmospheric pressure.

3.14 SANTOS LTD.

 PHYSICAL PROPERTIES

VAPOR PRESSURE OF PROPANE

AT CONDENSING TEMPERATURE
OVERHEAD IS 1725 kPa(a) [250 pslg].
CONDENSER THIS IS THE TOWER OPERATING
PRESSURE

- I

---@ ~ "'_ _-C::l<)_ _" . PROPANE PRODUCT

HEAT
SOURCE

BonOM PRODUCT MUST BE

HEATED TO 121 'c [250 'F] FOR
ITS VAPOR PRESSURE TO BE THE
SAME AS TOWER PRESSURE

BonOM
PRODUCT

Figure 3.7 Operating Pressure of Fractionation Tower is Determined by Vapor Pressure of Top Product

A product stored in an atmospheric tank will not boil as long as its vapor pressure is below
atmospheric pressure. Some of the liquid may evaporate, but no boiling will occur unless the vapor
pressure is the same as atmospheric pressure.

An apparatus for measuring vapor pressure of LP gases and NGL mixtures is shown in Figure
3.8. It is filled with the liquid to be tested. The 20% section is then isolated from the 80% chamber
and the liquid in the smaller chamber is drained. The two chambers are then equalized and thoroughly
shaken, and the pressure gauge reading is the vapor pressure of the liquid inside the container. The
container is usually put in a water bath at 38°C [lOO°F], which is standard temperature for vapor
pressure measurement. The "Standard Test Method for Gage Vapor Pressure of Liquefied Petroleum
(LP) Gases (LP-method)" is covered by an ASTM standard, D 1267-95 (or later). It appears in the
(American) Gas Processors Association Recommended Procedures known as: "Liquefied Petroleum
Gas Specifications and Test Methods," which is designated as GPA Standard 2140-97 (or later).

The vapor pressure determined from the test apparatus is a gauge pressure. If this pressure is to
be compared with a product vapor pressure shown in Figures 3.6(a) and 3.6(b), it must be converted to
absolute pressure by adding atmospheric pressure.

We said that the pressure gauge reading on a separator was the vapor pressure of liquid inside
the vessel. There is another important point to make about liquid inside a separator operating under

GAS PROCESSING OPERATIONS 3.15

 IMPORTANT PROPERTIES OF HYDROCARBONS

pressure: The liquid is at its boiling point. If any heat enters

o
the liquid from the sun or other source, some of the liquid will
Pressure boil or vaporize.
Gauge

The vapor inside a separator operating under pressure

is at its condensing temperature. Any cooling will result in
some of the vapor turning to liquid.

Reid Vapor Pressure

80% Chamber The Reid Vapor Pressure (RVP) is a laboratory testing
procedure developed for measuring the vapor pressure of crude
oil, gasoline, and other hydrocarbon mixtures that have a va-
por pressure less than atmospheric pressure. The Reid Vapor
Pressure differs from other vapor pressure measurements in
that the pressure gauge reading is approximately the absolute
vapor pressure, whereas the vapor pressure measurement pre-
viously discussed is a gauge pressure measurement, and at-
mospheric pressure must be added to it to get the absolute
pressure.

The Reid Vapor Pressure apparatus is shown in Figure

Figure 3.8 LP Gas Vapor Pressure
Apparatus
3.9. While it looks similar to the apparatus shown in Figure
3.8, there are differences, both in configuration and in the test
procedures followed. The main difference in the test proce-
dure is that the 20% chamber is filled with the sample and the
Certified 80% chamber is filled with air. The two chambers are con-
Test
Gauge
nected and vigorously shaken and then put in a water bath at
38°C [100°F]. The pressure gauge reading is the Reid Vapor
Pressure of the liquid sample inside the apparatus. For exam-
ple, if the pressure gauge reads 70 kPa [10 psi], this is ap-
proximately the absolute vapor pressure of the liquid at 38°C
[100°F]. The "Standard Test Method for Vapor Pressure of Pe-
troleum Products (Reid Method)" is covered by an ASTM
Air
standard, D 323-82 (or later).
Chamber
One of the main uses of the Reid Vapor Pressure is
that of determining if crude oil or gasoline will vaporize in an
atmospheric tank or an ocean-going tanker if it is heated from
the sun to 38°C [100°F]. As long as the Reid Vapor Pressure
is less than atmospheric pressure, no boiling will occur. An
approximate conversion of RVP to TVP for crude oil is shown
in Figure 3.10.
Gasoline
Chamber

Figure 3.9 Reid Vapor Pressure

Apparatus

3.16 SANTOS LTD.

 PHYSICAL PROPERTIES

5 140 60
1
130
10 50
120

2 110
2 40
100
20 3 20 3

4 90
30 'iii u. 30 u
4 (IS a.
30 a.. 5 a> ° °
~
..... ~ 80 ~
~ 40 :::J
en :::J :::J
(IS
5 (IS :::J en Cii
..... T!!Q)
a.. 'iii en Q)
..... Q)
~
a. en
Q) 50 a... a. 70 a.
~ 40 ..... ..... E 20 E
6 ~ a.. 0
~
Q)
:::J
en :::J ..... 60 a. I-
en en 0
a.
(IS
en 60
7 10 ~
Q)
Q) (IS
0:..... 50 .....
a.. > 70 'iii
0 8 ..... '0
80 II
a. 0 'iii 50
(IS a. Il: 10
>Q) 9 >
(IS
90
10 .....~ 100
~ 70 I-
15 40
80 0
30
90
100 20
15
110
-10
120 10
130
140 20
150 0
160
170 25

Figure 3.10 Reid Vapor Pressure vs. True Vapor Pressure for Crude Oils

Example 3.4: Atmospheric pressure at Denver, Colorado is 83 kPa [12 psi]. Maximum summer
temperature is 38°C [lOO°F]. The RVP of crude oil stored in atmospheric tanks
should be less than what value?
From Figure 3.8
@ T = 38°C & TVP = 83 kPa, RVP = 62 kPa [9 psi]

GAS PROCESSING OPERATIONS 3.17

 IMPORTANT PROPERTIES OF HYDROCARBONS

Summary
1. The pressure gauge reading on a separator is the vapor pressure of liquid inside the vessel.
2. Liquid inside a separator will boil if it receives any heat from the outside, or if the pressure
is lowered.
3. Some vapor inside a separator will condense if it is cooled.
4. Liquid stored in a tank open to the atmosphere will boil if its vapor pressure equals atmos-
pheric pressure.
5. Vapor pressure is normally measured at 38°C [100°F].
6. The vapor pressure measurement of liquids stored under pressure is normally a gauge pres-
sure. Atmospheric pressure must be added to obtain the absolute vapor pressure of the
liquid.
7. Reid Vapor Pressure is approximately an absolute pressure. It is usually run on liquids
stored in atmospheric tanks.

Heat of Combustion
When hydrocarbons burn they give off different amounts of heat. For example, when a cubic
meter [cubic foot] of methane burns, it releases about 37 800 kJ [1010 Btu] of heat. A cubic meter
[cubic foot] of propane will give off 94241 kJ [2517 Btu]. The higher the number of carbon atoms in
the hydrocarbon, the more heat it releases when it bums. Tables 3.1(a) and 3.1(b) list the heat of
combustion (heating value) for some hydrocarbons.

The heating value is important in designing burners or engines. The burners in a heater de-
signed to operate with methane will not function properly if propane is used for fuel. An engine
equipped to run on propane must have a separate carburetor if gasoline is also to be used for fuel. If a
burner or carburetor is set to use a low heating value fuel such as methane, and a high heating value
fuel such as propane is used, the fuel-air ratio will be too rich, and all of the fuel may not bum. The
exhaust will usually smoke, and the unit will not deliver its rated output. Most burners will accept a
variation in heating value of 5-10% without loss of efficiency. However, a slug of high heating value
gas into a fuel system can result in a flame-out in a burner, or shut-down of an engine.

Flammability Limits
The flammability limits of hydrocarbons are the maximum and minimum concentrations of hy-
drocarbons in air that will bum. They also are listed in Tables 3.1(a) and 3.1(b) for some hydrocar-
bons. The concentration of hydrocarbon in air must be within the flammability limit in order for the
mixture to bum.

The flammability limits for methane are 5-15%. This means that a mixture of methane and air
must contain more than 5% and less than 15% methane for it to be able to bum. If a mixture of
methane and air has less than 5% methane, it is too lean to bum; if it has more than 15%, it is too rich
to bum.

Flammability limits are used with heats of combustion in designing burners and carburetors.
They are also of particular concern when air is purged from a system with gas. The danger of fire
exists only as long as the purged mixture is within its flammability limits. As soon as a rich mixture is
present, ignition cannot take place.

3.18 SANTOS LTD.

 PHYSICAL PROPERTIES

Density - Gases
The pressure-volume-temperature of gases is most important to the petroleum industry. The
prediction of behavior is an important part of the design and operation of equipment. This is one
reason why accurate measurement of temperature and pressure is so important.
We will first consider ideal gas principles for these serve as a basis for predicting behavior of
actual gases.
We first need to define again some basic terms.
1. Mass - weight of gas contained in a given volume
Units - SI: kg, or kmols
English: lb or lb mols
2. Mols - mass in kg, or lb divided by molecular weight of the gas
3. Molecular weight - found from the gas analysis or by the equation
MW = (Sp Gr)(29)
4. Density - weight of gas contained per unit volume of gas
Units - SI: kg/m3
English: Ib/ft3
5. Specific Volume - reciprocal of density (1/density)
Units - SI: m3/kg
English: ft3/lb
The units of pressure to be used in this discussion are:
Units - SI: bar (1 bar = 100 kPa =0.987 atmosphere)
English: psi absolute (psi a)
Absolute pressure always must be used in gas calculations - gauge pressure plus atmospheric
(barometric) pressure.

The units of temperature to be used in this discussion are:

Units- SI: K, Kelvin K = °C + 273
English: OR, Rankine OR = OF + 460

Absolute temperature always must be used in gas calculations.

Change of Volume
The volume of gas depends on pressure, temperature and mass. Let
us consider the effect of each one of these, with the other two held constant.
Change of volume with mass (P and T constant)
Consider the cylinder pictured at the top which has a frictionless,
free-moving and perfectly sealed piston. As shown in its starting condition,
the piston has trapped a mass of gas, n j, whose volume is V 1. (We are
expressing the mass of the gas as "n", corresponding to the number of mols
of gas present.) The temperature of the gas, piston and cylinder will all be

GAS PROCESSING OPERATIONS 3.19

 IMPORTANT PROPERTIES OF HYDROCARBONS

held constant since the cylinder is immersed in a sufficiently large heat sink. The pressure on the gas,
P, is represented by the weight imposed on the top side of the piston.
If we pump in more gas and double the mass of gas in the cylinder, the piston will move to a
new position as shown in the bottom picture. The new, larger mass of gas, n2, will occupy a new,
larger volume, V 2. In fact, when the temperature and pressure are held constant, the volume changes
directly with the number of mols of gas and the new volume is also twice the orginal volume. This is
expressed by the equation:

This equation applies if there is no change in pressure and temperature in going from (1) to (2).
Change of volume with temperature (P and mass constant)

n Is constant

The above drawing illustrates this condition. If there is no leakage, the mass is the same in
both states. The pressure does not change because the weight on the piston stays constant. In order for
the pressure to remain constant the collision forces of the molecules beating on the walls must remain
constant. These collision forces are the sum of two factors, the energy of the molecules and their
concentration (density). As we heat them up their energy increases. To compensate for this the density
must decrease to keep pressure constant. Since the total mass is fixed, the only way to decrease
density is to increase volume. This is exactly what happens.
This principle is expressed by Charles' Law which states that "At constant pressure, the volume
of a constant weight of gas varies directly with absolute temperature."
This law can be written in equation form as:

3.20 SANTOS LTD.

 PHYSICAL PROPERTIES

Example 3.5: Gas is held in a container at constant pressure. At 40°C [104°F] the volume is
3 m 3 [106 ft3]. What is the volume if the temperature is increased to 60°C
[140°F]?
SI: Tl = 40 + 273 = 313K, T2 = 60 + 273 = 333K
or

V2 =3 (;i; )= 3.2 m
3

English: Tl = 104 + 460 = 564°R, T2 = 140 + 460 = 6()()OR

V2 = 106 ( ~~) = 113 ft3

Change of volume with pressure (T and mass constant) - The drawing below illustrates this
condition.

n is constant

-.
I~-------- . . -.-
-- -~
(~ Constant T ~c.~1
~~....r.:~-_.:-~::'~~_

If there is no leakage the mass is the same in both states. If the temperature is held constant
the energy of the molecules remains constant. The only way the pressure can increase inside the
cylinder to equal the increased external pressure in state (2) is for the density of molecules to increase.
Since mass is constant the only way for density to increase is for the volume to decrease.

This principle is known as Boyle's Law. It states that the "Volume of a constant weight of gas
varies inversely with the pressure exerted on it, if the temperature is maintained constant."

This law may be expressed in equation form as:

Generolldeol Gos Low

Boyle's and Charles' Laws may be combined to make an equation that relates pressure, volume
and temperature behavior of an ideal gas. It is:

PV = nRT

GAS PROCESSING OPERATIONS 3.21

 IMPORTANT PROPERTIES OF HYDROCARBONS

Example 3.6: Gas is held in a container at constant temperature. The initial volume is 4 m 3 [142
cu ft] at absolute pressure of 2 bar [29 psia]. The pressure on the gas is increased
to 4 bar [58 psia]. What is the final volume? The equation is PlV l = P 2V2 .

SI:

In this equation "n" is the number of mols of gas present in the container holding the gas and
"R" is a constant that is often called the universal gas constant. The value of constant R depends on
the units used for P, V and T. The table below summarizes common values of R.

Common Values of Constant R

p V T n R
bar m3 K lanols 0.0831
psi a ft 3 OR Ib-mols 10.73

The value of n may be found by the equation:

n = (mass of gas)/(MW gas)
If mass is expressed in n is n
grams mols
kilograms lanols
pounds lb-mols

Example 3.7: 10 kg [22 lb] of a 0.6 sp. gr. gas is contained in a tank at 2 bar [29 psia] and a
temperature of 40°C [104 oF]. What is the volume of the tank?

Gas MW = (0.6)(29) = 17.4

SI Units English Units
n = (10)/(17.4) = 0.574 lanols = (22)1(17.4) = 1.264lb-mols
R = 0.0831 = 10.73
T = 40 + 273 = 313 K = 460 + 104 = 564°R
P = 2 bar = 29 psia

Ideal Gos Density

The density (p) of an ideal gas may be found from the equation PV = nRT. This equation may
be converted to the form:

p = (P)(MW)
RT

Where: density (p) may be in gmlcm3, kglm 3 or Ib/ft3 . The proper units to use in
this equation are shown in the table below.

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 PHYSICAL PROPERTIES

Density (p) p R T
gmlcm3 bar 83.1 K
kglm3 bar 0.0831 K
Ib/ft3 psia 10.73 OR

Example 3.8: A 0.7 sp. gr. ideal gas is contained in a vessel at 3 bar [44 psia] and a temperature
of 40°C [l04°P]. What is the density of the natural gas in kglm3 [lb/ft3]?

SI Units English Units

MW (0.7)(29) = 20.3 = 20.3
T 40 + 273 = 313 K = 104 + 460 = 564°R
(3)(20.3) = 2.3 kglm3 (44)(20 .3) = 0.15 Ib/ft3
(0.0831 )(313) (10.73)(564)

Density of a Real Gos

The ideal gas laws assume that gas molecules do not interact; i.e., that there are no attractive or
repulsive forces between the molecules. In reality, gas molecules generally repel one another unless
the pressure becomes very high, in which case they begin to attract one another. A description of the
behavior of a real gas can therefore become quite complicated and difficult to calculate.

Engineers generally rely on computer programs to accurately determine the density of a real
gas once the composition is known. These calculations are performed using a theoretical "equation of
state". However, for quick calculations by hand, the engineer relies on the use of a dimensionless
factor, called the compressibility factor, to estimate how much the actual gas density will vary from the
ideal gas density. The compressibility factor, Z, is defined by the following equations:

Z = PV or
Z = density of ideal gas
RT density of real gas

Using the compressibility factor, the density of a real gas can be calculated as follows:

(P)(MW)
P = ZRT
The units for p, P, and T will be the same as those shown on page 3.23.

The compressibility factor depends on several gas properties, including its temperature, pres-
sure, composition, critical pressure and temperature, and so on. While methods exist for hand calcula-
tions and estimates of the compressibility factor, it too is most often determined by computer. The
determination of compressibility factors is beyond the scope of this discussion. When required in
example problems, the value of Z will be provided.

Densities of Liquids
Liquid densities can be shown several ways. These are summarized below:

Specific Gravity - Specific gravity is the density of a liquid divided by the density of water.
In the SI system, specific gravity is called the relative density. In this manual it is shown by the Greek
letter, y.

GAS PROCESSING OPERATIONS 3.23

 IMPORTANT PROPERTIES OF HYDROCARBONS

_ density of hydrocarbon liquid _ PHC

Y- density of water - Pw
At 15°C [60°F] the density of water is 1 gm/cm3, 1000 kg/m3, 62.4 Ibo/ft3, so the actual
density of the hydrocarbon can be calculated as follows.
p(g/cm3) =1.0 Y
p(kg/m3) = 1000 Y

p(lbn/ft3) =62.4 Y
In the oil and gas industry, specific gravities are frequently expressed in terms of the API
gravity. The API gravity is related to the specific gravity by the following equation.
141.5

Liquids are relatively incompressible compared to gases. However, the calculation of the prop-
erties of liquid mixtures is complicated by two factors - the presence of high vapor pressure compo-
nents like methane and ethane, and the shrinkage in volume upon mixing two hydrocarbon liquids.
Both effects can be understood by remembering that liquid is made up of molecules of different
sizes and shapes, possessing different amounts of energy.
The size and shape of the molecules affects all properties. If you magnified these molecules
you would see a series of shapes and sizes with space between them. The size would depend on
molecular weight. The larger paraffin molecules would be shaped somewhat like a sausage. The aro-
matic (ring) molecules would be more circular. The small molecules like methane and ethane would be
rather spherical. Molecules like methane are very active, and this movement clears more space be-
tween molecules as collisions occur. The large molecules are more lethargic.
The properties are dependent on size, shape and energy. If you have a container full of large
rocks, there are spaces in-between that can accommodate smaller-sized objects like gravel and sand.
So ... if you mix liquids containing molecules of different sizes there is shrinkage on mixing as little
molecules occupy voids between the bigger ones; i.e., the volumes are not additive. On the other hand,
molecules which are very active (high energy) tend to push the larger molecules away, leading to slight
expansion upon mixing.
All of this says that the physical properties of a liquid mixture are dependent on things that are
measures of energy, size and shape.
Liquid correlations can be divided into two general categories: natural gas liquids (NGL)
where an analysis showing most of the components is available, and complex liquids (like crude oil)
where a detailed analysis is not feasible.
If the NGL is recovered from the gas after any reservoir liquids have been separated previously,
the amount of any component heavier than decane probably will be trivial and NGL correlations will
suffice. If reservoir liquids are involved, some form of characterization is needed other than direct
analysis. The distillation characteristics of the heavier components is the basic analytical tool em-
ployed.
When the liquid is composed of butane and heavier molecules their energy is low enough that
relatively simple correlations may suffice. Some correction for pressure and temperature is required in

3.24 SANTOS LTD.

 PHYSICAL PROPERTIES

many cases. Molecular energy increases with increasing temperature, thus reducing density and other
physical properties. Increasing pressure has the opposite effect since it "squeezes" the molecules closer
together.

Crude Oil Distillation

In order to estimate the density of crude oils, some information is required about the types of
molecules in the crude. It is impossible to analyze crude oils on a chromatographic as there are liter-
ally thousands of components in the oil, so other techniques are used. The most popular of these is a
distillation analysis. In this test the oil is distilled in a batch distillation (usually at atmospheric pres-
sure) and the boiling point of the oil is plotted against the volume boiled off. This results in a charac-
teristic distillation curve for the oil - much like a fingerprint. Typical distillation curves for several
crude oils are shown in Figure 3.11.

1100.--..---~-----.,-,....-..--_...,

Characl~=D~ Facto< ~ ~ &l c--~ ~-.-.--

10001--+---='+="'i=~"""i- -
~ ~ 550
'I' /'J'. /,,,' '/ 500
9001--+-+---+-l~'~v// 1
/.'1/ 450
~ MO I--+-~~~/i/ -T~~~~~,~ / ~~4oo~
~ 700 '--- I - It' ~ .,~ //J.l:.,/I!!
~ I .. )~V/ )~',/ 350 ~
~CIl~E 600 '//}'..'Y..VA~
300 8.
500 1-~<.j;<-m~i(!i'~-t--i-+--:f250 ~
~ 400 VJ /j~~~ 200 ~

~ 300 £'1'1.0.~ 150 ~

'1 V~P'
200 t-h"!'+--+--t--t--t- 'I --l--t---1 1oo
/'~'
100"-'1;«+-+-1--+-+--+--+--+-+--'1 50
o o
0 -8""'0""""""'90~100
40--l5O'--aJ.,-0-7.1.:-0-8,.L-O--L90-1~00
o 0""""1J,-0-2,.L-O--L30--1 o 0'---1....
0---'20--3L..
0 -4"""0""""""'50,......,.,60.,......7....
% Distilled % Distilled
Average of About 550 Samples Average of Mid·East and North Africa Samples

Figure 3.11 Some Representative TBP Distillation Curves

Engineers use the distillation curves to assign properties to the oil and treat it in calculations as
if it were just a few components. Many times a complex crude oil is reduced to only a few pseudo-
components, usually less than 10-15.

Frequently, due to time or cost considerations, a full distillation analysis is not performed.
Even in these cases some information about the types of molecules which make up the oil is still
required. A simple characterization parameter has been developed to do this. It is called the Watson
Characterization Factor, Kw, and it is calculated from the equation below.

(MABP) 1/3
Kw = ..0..-_---''--
Y
Where: MABP = Mean Average Boiling Point, OR
y = specific gravity

For oils with significant amounts of paraffins, Kw is usually near 12. For oils with significant
amounts of aromatics and naphthenes, Kw is closer to 11, sometimes less.

It is important to know about the Watson Characterization Factor because many crude oil corre-
lations use it.

GAS PROCESSING OPERATIONS 3.25

 IMPORTANT PROPERTIES OF HYDROCARBONS

Crude Oil Density

The density of a crude oil at storage tank conditions can usually be measured, and is normally
given in terms of API gravity.
It is usually given at standard or reference conditions, 15°C [60°F] and 1 atm. In other words,
when someone tells you a crude oil has an API gravity of 38, this is at standard conditions.
Frequently we would like to know the density of a crude oil at other conditions, such as a
higher or lower temperature. Figure 3.12 is a useful correlation for estimating the flowing density of
the oil.
Figure 3.12 corrects only for temperature effects on density. Pressure has very little effect on
the density of crude oils.

Density of NGL's
The density of NGL's can be estimated from correlations such as an equation of state. These
correlations are quite complex and will not be covered in this manual. In general, the densities of
mixtures of propanes and heavier NGL's are fairly easy to predict. Liquids with high concentrations of
methane and ethane require more sophisticated models and correlations. One of the best liquid density
correlations available today is the COSTALD method. It is a computer based method.

Example 3.9: A 35° API gravity crude oil is heated to 80°C [176°F] in a heater. Ifthe crude oil
has a KW of 11.8, what is the density of the oil leaving the heater?
Find the pivot point in the center grid @ Kw = 11.8 and API = 35. Draw a
straight line from 176°F through the pivot point and read the density on the right-
hand scale. In this example the density is 0.81, 810 kglm3, 50.5 Ib/fi3.

3.26 SANTOS LTD.

 PHYSICAL PROPERTIES

1000 1.05

900
lOO

800

0.95

700

., ()
0.90
~
.D
600 'b ..,
u.
~
u. ~o
~
0

Q)
,Q 0.85 «
L...
E
::J
+"'
tU
L...
500 en
Q)
a. ~
E
Q) 0.80 ~
en
~
Mean-Average cQ)
400 0
Boiling Point, OF

0.75
~o DEG API
300

0.70

200
0.65

0.60
100
Watson K ....",':>
0.55

0.50
0 1972 0.45
0.40

Figure 3.12 Density Correlation for Crude Oils

GAS PROCESSING OPERATIONS 3.27

 IMPORTANT PROPERTIES OF HYDROCARBONS

NOTES:

3.28 SANTOS LTD.