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John Chisholm
Texas A&M University Kingsville
Chemical & Natural Gas Engineering
Kingsville, TX 78363
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 molecules
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. Boyles 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
momentum of a molecule is its mass times its velocity, The Kinetic Theory shows that each impact contributes
so the change of momentum at the wall is given by: to the pressure. If the temperature increases, the velocity
increases, the round trip time goes down, and the number
momentum = mv - m(-v) = 2mv impacts goes up, hence, more pressure. If the number of
molecules in the container increases, the number of
where m is the mass of each molecule and the stands impacts increase and the pressure increases. Finally, if
for change. Consider a ball thrown at a wall. The wall the volume of the container is reduced, it takes less time
must first stop the bals momentum (mv) and then send for the molecules to travel back and forth, so each
it away again with momentum mv. So from the point of molecule makes more impacts in a unit of time. More
view of the wall it had to impart to the ball 2mv, half just impacts produced more pressure. The reverse of each of
to stop it and half to send it away. these events produces less pressure.
The change in momentum of a molecule per unit time is Both Charles and Boyles Laws have been derived from
given by: the Kinetic Theory. Some other very useful laws can be
2mv * 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.) Avogadros 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 mv 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,
Daltons Law of Partial Pressures can be found. Daltons
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.
As the pressure continues to increase, the molecules, and molecular weights of the individual gases are
which have a real volume and velocity, begin to interfere available from any gas handbook.
with the other molecules in the gas. Personifying the gas,
one can think of each molecule fighting for its own space. EXAMPLE 1 A turbine meter indicates that 4,000 macf
This results in repulsive forces. So the z-factor begins to of gas passed through it in one day. The line pressure
increase and returns to and then exceeds 1.0, so that at and temperature were 500 psia and 122F. The gas
high pressures the gas will occupy more volume than stream was 85% methane, 9% ethane, 4% propane, and
that predicted by the ideal gas law. 2% butane+. What volume of gas in mscf was delivered
that day?
As many pure gases and mixtures of gases were tested
it was observed that their behavior matched that The calculation of the critical properties of this gas is given
described above. Although the z-factors for methane in Table 1.
followed the same trends as that of ethane, the z-factors
were by no means identical. To unify these relations all 122F + 460 = 582R
the tests were related to the reduced temperature and
pressure. p Tr = 582R / 384.5R = 1.51
Pr = 500 psia / 664.2 psia = 0.75
Tr = T and Pr = P
p
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 520R 1.0
Vsc = 4,000 macf
compressibility factor chart to be developed. 14.7psia 582R 0.925
where MWg is the molecular weight of the gas and g 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
500psia 520R 1.0
Vsc = 70,000 acf
14.7psia 582R 0.925
Vsc = 2,127,311 cubic ft = 2,127mscf
REFERENCES
John Chisholm