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Proceedings 2003: American School of Gas Measurement Technology
Proceedings 2003: American School of Gas Measurement Technology
2003
THE IDEAL AND REAL GAS LAWS Pressure is the force per unit area. The force on the wall
of a container containing gas is the number of impacts of
The ideal gas law is given as gas molecules on the wall. So, anything that increases
PV = nRT the number of impacts or the velocity of the impacts will
increase the force, and, hence, the pressure.
and the real gas law as
PV = znRT The Kinetic Theory of Gases states that the kinetic energy
where P = pressure, psia (KE) of a molecule is directly proportional to its
V = volume, cubic feet temperature.
z = compressibility factor, dimensionless KE(T) = 1 mv 2 = cT
n = number of moles of gas, lb mol 2
T = temperature °R
R = 10.732 psia ft3/(lb mol °R) for this system of Where m is the mass of the molecule, v is the molecule’s
units. (The value of R will change depending
velocity, and c is a constant.
on the system of units.)
The Ideal Gas Law can be derived using the Kinetic
The difference between the ideal and the real gas law is
Theory. And the derivation explains a great deal about
the compressibility factor, z. The ideal gas law assumes
what pressure is and how gases react.
that the molecules of gas have no volume and there are
no attractive or repulsive forces acting between the
~ 1.0 and gases Consider a cubic container with sides of length L,
molecules. At very low pressures z =
behave as if they are ideal gases. At higher pressures
the attractive and repulsive forces (often called the
dynamic pressure) are significant and the behavior of
gases deviates from the ideal. The compressibility factor
is often called the gas deviation factor or, simply, the
z-factor.
L
Early experiments were conducted at low pressures and
the gases tested acted as ideal gases. Boyle’s Law states
that at a constant temperature the product of the pressure L
and the volume is a constant, so any two conditions, 1 L
and 2, of a gas were related by
P1V1 - P2V2 In a container of fixed volume, the velocity controls how
long it will take a molecule to travel from one side of the
Charles’ Law states the ratio of volume to temperature container to the other and back again.
is constant at constant pressure,
V1 V Length of a round trip = 2L
= 2
T1 T2 The number of impacts on a given wall is then:
These can be combined into one of the most common v
Number of impacts per unit time =
expressions of the ideal gas law. 2L
P1V1 P2V2 where v is the average velocity of the molecule. Each
=
T1 T2 molecule of gas hits the wall at v and rebounds at –v. The
The change in momentum of a molecule per unit time is Both Charles’ and Boyle’s Laws have been derived from
given by: the Kinetic Theory. Some other very useful laws can be
2m’v * v = m v
’ 2 derived from the Kinetic Theory. (For the record, the Laws
2L L were determined experimentally before the Kinetic Theory
n’ was developed.) Avogadro’s Law states that, at the same
Only a third of the molecules, 3 in the box are hitting
temperature and pressure, equal volumes of an ideal gas
each wall.
contains the same number of molecules. Also the volume
containing one molecular weight of a given gas will be
The force acting on a wall is the number of molecules
equivalent to the volume containing one molecular weight
times the change in momentum per unit time.
of another gas at the same temperature and pressure.
n’ m’v 2 There are 2.73 x 1026 molecules per pound mole of an
F = ideal gas.
3 L
And pressure is the force per unit area.
When the Kinetic Theory is extended to mixtures of gases,
Dalton’s Law of Partial Pressures can be found. Dalton’s
P = n’ m’ v 12 = n’ m3’ v
2 2
P = n’ m’ v or PV = n’ m’ v
2 2
Ptotal = PA + PB + PC + ...
3V 3
The beginning assumption was that the kinetic energy and that the partial pressures are proportional to the mole
was a function of temperature alone. fractions of each component. The partial pressures
become especially important if liquid water is in contact
Then, with the gas. The partial pressures can be used to
m’ v 2 = 2cT and PV = n’ 2cT determine what fraction of each gas is in solution in the
3
liquid. If significant quantities of CO2 or H2S are present,
where c is a constant. they will produce corrosive acids in solution with water.
Now
A 3 ( )
PV = n’ 2 cA T
z =
VACTUAL
VIDEAL
n’ = n and we set 2 cA = R
As the pressure increases from near atmospheric, the
A 3 molecules are pushed closer together. Both gravitational
Then, and electrical attractions cause the molecules to pull
PV = nRT towards one another with the result that the volume
occupied by the gas is less than that predicated by the
which is the ideal gas law. gas law. The z-factor becomes less than one.
Tc Pc
z = 0.925
For mixtures, the pseudo-critical properties can be used Vsc = Vline Pline Tsc zsc
in these calculations. When plotted for each and every Psc Tline zline
hydrocarbon gas the z-factor lines now tracked together.
This discovery is commonly called the Law of
Corresponding States. This allowed a generalized 500psia 520°R 1.0
Vsc = 4,000 macf
compressibility factor chart to be developed. 14.7psia 582°R 0.925
where MWg is the molecular weight of the gas and ρg is Initial gas in the pipeline:
the density of the gas. Values of the critical properties
Ppipe Tsc zsc
Vsc = Vpipe
Psc Tpipe zpipe
Table 1. Pseudo-Property Calculation for Example 1.
Component Mole Fraction Tc yjTcj Pc yjPcj
yj °Rankine °Rankine psia psia
C1 0.85 343.3 291.8 666.4 566.4
C2 0.09 549.9 49.5 706.5 63.6
C3 0.04 666.1 26.6 616 24.6
C4+ 0.02 830.0 16.6 482 9.6
384.5 664.2
REFERENCES
John Chisholm
ORIFICE DEVICES
FIGURE 3. FIGURE 4.
Orifice Flange Union Single Chamber Fitting
Flow computers have increased in use in recent years The new AGA #3/API 14.3 measurement standard has
due to the requirements for measurements information greatly tightened the tolerances for the manufacture of
on a more “real time” basis. Flow computers, like the orifice devices and meter tubes. It is very much in the
pneumatic chart, take the flow information from the best interest of the users of these devices to have sound
differential pressure, static pressure and the temperature maintenance programs in place to insure that the like-
transmitter and calculates flow volumes. Unlike the chart, new quality of the tubes be maintained for as long as
flow computers do not have to go through an integration possible. The primary device, whether a fitting or flange,
step to come up with these figures. There are several cannot be expected to provide accurate, reliable flow
levels of sophistication available in flow computers. The information if the orifice plate is bowed or otherwise
battery-powered, solar charged devices have the best degraded in some way. The vast body of data supporting
utility as field devices, which can store the flow orifice measurement over the years becomes
information on site, do the volume calculations and then meaningless if the guidelines for the design, manufacture,
send that information on to a higher device such as a installation and maintenance of these devices are not
mainframe computer. The higher-level flow computers followed.
Bill Buckley