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Introduction to Real Gases

Dr. Crystal Cooper • Updated May 27, 2011

The ideal gas law fails for gases that are near condensation. A physics graduate student
came up with a modified equation by amending the kinetic theory of gases. How did he
do this, and who was he?

Limitations of the Ideal Gas Law

Real gases approximate ideal gas behavior at relatively low densities and atmospheric
pressure. But for deviations outside of these ranges, near condensation, the ideal gas
law is no longer accurate enough. A more precise representation had to be found. The
problem was eventually solved by a physics grad student who later on became a Nobel
prize winner.

J. D. van der Waals

The grad student in question was J. D. (Johannes Diderik) van der Waals (1837 - 1923),

a Dutch physicis t. Van der Waals became inspired to study thermodynamics by

reading a treatise by Clausius. Despite van der Waals' being a self-taught school
teacher armed with only an elementary education, he was allowed to enter the
University of Leyden. A lack of knowledge of classical languages prevented him from
enrolling as a regular student to obtain degrees, but he took courses. He was also able
to earn teaching certificates in math and physics by studying in his spare time.
Afterwards, he became a secondary school director. New regulations finally let science
students be exempted from the classical language requirements, and he was allowed to
take doctoral qualifying exams, which he passed with flying colors. At the age of 35 and
with a wife and kids, van der Waals earned his doctorate in physics. For his dissertation,
he derived his eponymous equation of state.

Van der Waals arrived at the equation by considering the kinetic theory of gases, but
with some important differences.

Differences From the Basic Postulates

Van der Waals modified the basic postulates of kinetic energy in two significant ways.

Volume: In our previous examination of the basic postulates, we ignored the volume of
the molecules themselves, focusing on the total volume of the container. This allowed us
to assume that all of the molecules were point masses, and that they were evenly
distributed throughout the container. Van der Waals decided that the space or volume
occupied by individual gas molecules should be taken into account. Thus the
assumption of the uniform distribution of the molecules throughout the entire container
no longer holds true.
Intermolecular Forces: These were neglected, as we considered them to be too small
compared with the kinetic energy generated by molecular collisions. Only direct contact
between the molecules was allowed into our calculations. Van der Waals assumed that
these forces are actually quite large, being greater than the size of the molecules
themselves, and hence must be taken into consideration. Therefore, there is indeed an

action at a distance, albeit quite small and weak.

These two changes transformed the basic postulates into something more fitting for real
gases, and allowed the derivation of van der Waals' formula. As before, assume the
molecules are spherical with a radius of r, and that they collide with each other but
bounce back. These collisions will occur when the distance between their centers
become small, as shown in figure 2.

In the next article, we will use the ideal gas law and van der Waals' postulates to derive
the equation of state for a real gas.

Derivation of the van der Waals Equation of State for Real Gases Part One

Dr. Crystal Cooper • Updated Jun 7, 2011

In this article, we begin deriving an equation of state for real gases by using van der
Waals' modification of kinetic theory.

The Reduced Volume

The number and size of molecules limit their motion inside the container, and the
space they cannot reach is referred to as the unavailable volume. For the kinetic theory
of gases, where we consider ideal gases, we assume that our molecules are point sized
and can take up the entire volume of the container. An example is shown in figure 1. The
size, placement, and motion of the molecules are exaggerated, and a large enough
number is not shown, but it is easy to picture that extremely small molecules would fill up

the space. For the van der Waals model, where we consider real gases, the
molecules have an actual size and thus are unable to fill up a container space, even
after they collide. An exaggeration of their size and motion is shown in figure 2. The
container is the same size as that of figure 1, but the molecules are prevented from
inhabiting all of the volume.

In other real gas models, the molecules are further limited in the amount of space they
can occupy by a repulsive force that exists between them if they are too close to each
other, but we do not consider that here.

From the ideal gas law, we know that

1) PV = nRT
where P is pressure, V is volume, T is temperature, R is the universal gas constant, and
n is the number of moles. If we let b equal the amount of the unavailable or excluded
volume per mole of the gas, then the actual volume will be the total minus this excluded
amount:

2) V (actual) = V - nb

Substituting 2 into equation 1 gives us:

3) P(V - nb) = nRT

Dividing both sides by n we finally have:

4) P(V/n - b) = RT

What does this equation tell us? Suppose we have a set volume V and temperature T.
Then the pressure P is greater for our real gas than that of our ideal gas in equation 1.
This is because the number of molecules colliding with the walls will increase since the
available volume is smaller.

In part two, we will finish our derivation of van der Waals' equation by considering
intermolecular forces.

Derivation of the van der Waals Equation of State for Real Gases Part Two

Dr. Crystal Cooper • Published May 14, 2009

In this article, we conclude our derivation of the van der Waals equation of state for real
gases.

Intermolecular Forces

We can use equation 4 in the preceding article to help us derive the final form of the van
der Waals equation of state for real gases. To recall, we found that

4) P(V/n - b) = RT.

We begin by considering intermolecular forces. Intermolecular forces have a behavior

that is nonexistent at long distances, attractive at intermediate distances, and repulsive
at short distances. Here, we take into account only their attractive forces, which are
electrical in nature.

Molecules that are close can attract each other over certain ranges, and if the attraction
is great enough gases condense into liquids. We saw in our discussion on the kinetic
theory of gases that the kinetic energy of collisions affects the pressure that the
molecules exert on the container walls. Under certain conditions, short-range
intermolecular forces also contribute to wall pressure. How so?
 Because of weak electrical attraction, molecules that are near the container wall
at the edge of the gas have a net force that tends to pull them back, thus lessening the
number of molecules impacting the wall and hence the gas pressure. This pressure is
reduced in proportion to the density of the molecules, namely those that reside in the
surface layer as well as in the layer directly underneath. The layer that is directly
underneath the surface contributes by exerting an inward force on the edge molecules,
as seen in figure 1. The weak attraction that exists between the molecules is akin to that
of Newton's law of gravitation, and the effect is that the net pressure is reduced by a
factor proportional to 1/V2.

Taking all this into account, we can replace P by an effective pressure

5) P (effective) = P + a/(V/n)2,

where a is a constant dependent on the amount of attraction between the molecules; it

takes into account the overlap of their electron clouds. Substituting this into equation 4
above gives us

6) (P + a/(V/n)2)(V/n - b) = RT.

If we let V/n = the specific volume V, then we have:

7) (P + a/V2)(V - b) = RT.

Equations 6 and 7 are known as the van der Waals equation of state. The constants a
and b are chosen to fit the experimental data for the gas under consideration. When a
and b are zero, the equation reduces to that of the ideal gas law.

In the next part, we will see how to use this equation of state to plot isotherms.

Resources

 Professor Brucat's Equation of State Calculator

 Some van der Waals Coefficients from Wikipedia

Van der Waals' Equation and Isotherms for Real Gases

Dr. Crystal Cooper • Published May 18, 2009

An isothermal plot for an ideal gas shows one or more hyperbolas where PV is a
constant. How is an isothermal plot for a van der Waals gas different?

Obtaining the Cubic Equation

We can use the van der Waals equation to plot isotherms for real gases. To recall, the
equation is
1) (P + a/V2)(V - b) = RT

where P is pressure, V is volume, T is temperature, R is the universal gas constant, and

a and b are constants that are determined experimentally and are dependent on the gas.
Because we are considering isotherms, the pressure and volume vary along a curve
while the temperature does not.

If we multiply equation 1 by V2, we obtain

2) PV3 - (Pb + RT)V2 + aV - ab = 0.

This is a cubic equation with three roots of which two must be real, and in this form it is
easier to use it to make our graphs.

Isotherms for Ideal Gases

Figure 1 shows a typical PV plot of isothermal processes for an ideal gas. T 1, T2,
and T3 represent isotherms of increasing temperature. The curves show hyperbolas of
PV = constant. As the pressure decreases, the volume increases and vice versa.

Isotherms for Real Gases

Figure 2 shows an isothermal plot for a real gas. For large T, the isotherms look
like those of an ideal gas. But as T falls, especially below a critical temperature T C, we
see that the behavior is no longer ideal. The curves below Tc pass through a phase
change of liquid to vapor.

The critical temperature TC has a inflection or critical point CP, where the pressure is
transitioning from decreasing to increasing. As we go along an isotherm along or below
TC, the pressure decreases, and begins increasing til we reach a maximum. Then the
pressure begins falling again and becomes more or less constant. Because the pressure
no longer increases as the volume becomes less, these regions are unstable.

Figure 3 shows an isotherm below TC that is labelled for clarification purposes.

Starting at the right side of the diagram, the area after point c is where the pressure
eventually becomes basically constant and the volume is small. Point c is where
condensation occurs as the gas begins liquefying as we continue along the left of the
plot. Between c and b is a phase where the liquid and vapor are in equilibrium. Point e is
a maximum, and point d is a minimum. Ed is unstable and has not been observed in a
lab. Pure supersaturated vapors have been measured along ec, and supercooled liquids
have been measured along ad. Remember, supersaturated liquids have dissolved solute
beyond the solubility limit, and supercooled liquids are those that are cooled to
temperatures below that of their ordinary freezing points.
At point a, the substance is now wholly a liquid. The pressure begins rising rapidly
because it takes a great deal of it to compress a liquid.

Is is important to note that above TC, no matter how large the pressure, it is not possible
to liquefy a gas.

In the next part of the series, we will examine the van der Waals equation in light of
carbon dioxide.

Image Credits

Figure 1 from Pezhe.com

Figure 2 from from Wikimedia Commons

Figure 3 from Answers.com

Resources

Pressure-Volume Isotherm applet For Real Gases (Java is required)

Read more:
http://www.brighthub.com/engineering/mechanical/articles/35392.aspx#ixzz1L7tGl4W9
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Van der Waals' Equation and Carbon Dioxide

Dr. Crystal Cooper • Published May 20, 2009

What do airports, soda, and Nazi Germany have to with the van der Waals equation of
state as applied to carbon dioxide?

Introduction

We will now examine how the van der Waals equation applies to isotherms for carbon
dioxide (CO2).

Carbon dioxide is a common gas that is odorless, colorless, and water soluble, and is
found mainly in air. It is vital to life, but deadly if we breathe too much of it in. We expire
it when we exhale, and plants use it during photosynthesis. CO2 is emitted during the
combustion of fossil fuels and also by man-made activities. In solid form, CO2 is dry ice,
which is quite handy in refrigeration.

Carbon Dioxide Isothermal Plot

Figure 4, courtesy of Citizendium.org, shows a van der Waals plot for carbon
dioxide. Here, the constant a is 0.366 m6 Pa (pascals) while constant b is 42.9 10-6 m3.
The critical pressure is 73.7 kPa or 73.7 atm. At 10 oC, we are below the critical
temperature of 31oC. Point B is where the gas begins condensing or liquefying, and
point A is in the area of total liquefaction. Between A and B is where CO 2 is in liquid-
vapor equilibrium.

Supersaturated and Supercooled Carbon Dioxide

The supersaturated and supercooled forms of CO2 are not specifically pointed
out on this plot, but they are between points A and B.

One supersaturated solution of CO2 is carbonated water, a favorite enjoyed by many the
world over, especially when it is flavored or added to another drink.

Supercooled CO2 was once used for nefarious purposes. The Nazis injected it into the
fallopian tubes of women suffering from traits they deemed genetically undesirable, such
as epilepsy, blindness, deafness, or alcoholism. The subsequent scarring rendered the
women sterile. Boastful and merciless gynecologist Dr. Carl Clauberg told SS head
Himmler that with only a staff of ten people, he could use the substance to sterilize 1,000
women per day.

A more appropriate use of supercooled carbon dioxide is to freeze fog water at airports,
so that they turn into ice crystals that drop to the ground.

Conclusion and Caveats

Ideal gas approximations are still mainly used as the basis for statistical physics,
because real gases are close to this behavior under many conditions. But for gases of
high density and very low temperatures that are close to liquid condensation, the van der
Waals equation of state is a very good approximation, though it is not accurate for all
gases under all conditions.

Equations for real gases under other conditions are based on the van der Waals model,
but modify the potential energy term. For example, the intermolecular forces we
considered neglected repulsive forces between molecules. Newtonian physics was used
to treat these molecules as hard spheres that bounced back upon collision with non-
elastic walls. Other real gas models take repulsion, elasticity, and quantum mechanics
into consideration. Perturbation theory and Monte Carlo theory are some of the
techniques used to achieve more accuracy for the potential energy term.

Image Credits

van der Waals for CO2 from en.Citizendium.org

Sodas by Austin C. Kiser

Resources
Shockwave video by Chemistry Department at Okalahoma State Comparing an Ideal
Gas with Real Gases (includes carbon dioxide; click several times on the graph)

Read more:
http://www.brighthub.com/engineering/mechanical/articles/35632.aspx#ixzz1L7tRxdAy

Equations of State

David Young
Cytoclonal Pharmaceutics Inc.

An equation of state is a formula describing the interconnection between various

macroscopically measurable properties of a system. This document only adresses the
behavior of physical states of matter, not the conversion from one state to another.

For physical states of matter, this equation usually relates the thermodynamic variables
of pressure, temperature, volume and number of atoms to one another.

In materials science the important properties are often what are termed "mechanical
properties" rather than physical properties. Examples of mechanical properties would be
hardness and ductility. Mechanical properties will not be addressed here.

Gas - There are several types of gases with slightly different behaviors. These are ideal
gasses, real gasses, super critical fluids, plasmas and critical opalescent conditions. The
ideal gas law is often used as the first order description of any gas although this practice
is questionable in the case of critical opalescent conditions.

Ideal Gas - Although no gas is truly ideal, many gasses follow the ideal gas law very
closely at sufficiently low pressures. The ideal gas law was originally determined
empirically and is simply

pV=nRT

p = absolute pressure (not gage pressure)

V = volume
n = amount of substance (usually in moles)
R = ideal gas constant
T = absolute temperature (not F or C)

where some values for R are

8.3145 J mol-1 K-1

0.0831451 L bar K-1 mol-1

82.058 cm3 atm mol-1 K-1

 0.0820578 L atom mol-1 K-1

1.98722 cal mol-1 K-1

62.364 L Torr K-1 mol-1

Real Gas - Real gas laws try to predict the true behavior of a gas better than the ideal
gas law by putting in terms to describe attractions and repulsions between molecules.
These laws have been determined empirically or based on a conceptual model of
molecular interactions or from statistical mechanics.

A well known real gas law is the van der Waals equation

( P + a / Vm2 )( Vm - b ) = R T

P = pressure
Vm = molar volume
R = ideal gas constant
T = temperature
where a and b are either determined empirically for each individual compound or
estimated from the relations.
a = 27 R2 Tc2
--------
64 Pc

b = R Tc
----
8 Pc

Tc = critical temperature
Pc = critical pressure
The first parameter, a, is dependent upon the attractive forces between molecules while
the second parameter, b, is dependent upon repulsive forces.

Another two parameter real gas equation is the Redlich-Kwong equation. It is almost
always more accurate than the van der Waals equation and often more accurate than
some equations with more than two parameters. The Redlich-Kwong equation is

(p+ a ) ( Vm - b ) = R T
------------------
Vm ( Vm + b ) T1/2

p = pressure
a = empirical constant
Vm = molar volume
R = ideal gas constant
b = empirical constant
T = temperature
where a and b are not identical to the a and b in the van der Waals equation.
Equations of state in terms of reduced variables give reasonable results without any
empirically determined constants for a specific substance. However, these are not
generally as accurate as equations using empirical constants. One such equation is

( Pr + 3 / Vr2 ) ( Vr - 1/3 ) = 8/3 * Tr

Pr = reduced pressure
Tr = reduced temperature
Vr = reduced volume
where reduced pressure and temperature are the unitless quantities obtained by dividing
the value by the critical value. In the case of reduced volume, molar volume is divided by
critical molar volume.

A two parameter equation which is no longer used much is the Berthelot equation

p= RT - a
----- ----
V - b T V2

p = pressure
a = empirical constant
V = volume
R = ideal gas constant
b = empirical constant
T = temperature
A somewhat more accurate modified Berthelot equation is
p = R T [ 1 + 9 p Tc ( 1 - 6 Tc 2 ) ]
--- -------- -----
V 128 Pc T T2

p = pressure
Pc = critial pressure
V = volume
R = ideal gas constant
T = temperature
Tc = critical temperature
The Dieterici equation is another two parameter equation which has been seldom used
in recent years.
p = R T e-a / ( Vm R T )
------------------
Vm - b

p = pressure
a = empirical constant
Vm = molar volume
R = ideal gas constant
b = empirical constant
T = temperature
The Clausius equation is a simple three parameter equation of state.
[P+ a ] ( Vm - b ) = R T
-------------
 T ( Vm + c )2

a = Vc - R Tc
----
4 Pc

b = 3 R Tc - Vc
------
8 Pc

c = 27 R2 Tc3
--------
64 Pc

P = pressure
T = temperature
R = real gas constant
Vm = molar volume
Tc = critical temperature
Vc = critical volume
Tc = critical temperature
The virial equation is popular because the constants are readily obtained using a
perturbative treatment such as from statistical mechanics. The virial coeficients are also
readily fitted to experimental data because it is a linear curve fit.
p Vm = R T ( 1 + B(T) / Vm + C(T) / Vm2 + D(T) / Vm3 + ... )

or
p Vm = R T ( 1 + B'(T) / p + C'(T) / p2 + D'(T) / p3 + ... )

p = pressure
Vm = molar volume
R = ideal gas constant
T = temperature
B, C, D, .. = constants for a given temperature
B', C', D', .. = constants for a given temperature
where B is not identical to B' and etc.

The equation of state created by Peng and Robinson has been found to be useful for
both liquids and real gasses.

p= RT - a(T)
------ ----------------------------
Vm - b Vm ( Vm + b ) + b ( Vm - b )

p = pressure
a = empirical constant
Vm = molar volume
R = ideal gas constant
b = empirical constant
T = temperature
The Wohl equation is formulated in terms of critial values making it a bit more
convenient for situations where no real gas constants are available
[p+ a - c ] ( Vm - b ) = R T
--------------- ------
T Vm ( Vm - b ) T2 Vm3

a = 6 Pc Tc Vc2

b = Vc / 4

c = 4 Pc Tc2 Vc3

p = pressure
Vm = molar volume
R = ideal gas constant
T = temperature
Pc = critical pressure
Tc = critical temperature
Vc = critical volume
A some what more complex equation is the Beattie-Bridgeman equation
P = R T d + ( B R T - A - R c / T 2 ) d2 + ( - B b R T + A a - R B c / T 2 ) d3

+ R B b c d4 / T2

P = pressure
R = ideal gas constant
T = temperature
d = molal density
a, b, c, A, B = empirical parameters
Benedict, Webb and Rubin suggest the real gas equation of state
P = R T d + d2 { R T [ B + b d ] - [ A + a d - a alpha d4 ]

- 1 [ C - c d ( 1 + gama d2 ) exp ( - gama d2 ) ] }

--
T2

P = pressure
R = ideal gas constant
T = temperature
d = molal density
a, b, c, A, B, C, alpha, gama = empirical parameters

Supercritical Fluids - Supercritical fluids are well described by real and ideal gas laws.

Critical Opalescence - Critical behavior is generally described using real gas equations
which have constants defined in a way which ensures that the slope of reduced pressure
vs. reduced volume is zero at the critical point. These give reasonable estimates of the
relationships between pressure, volume and temperature but do not describe the
opalescence or unique chemical properties very near the critical point.
Plasma - The physical behavior of plasmas is most often described by the ideal gas law
equation which is quite reasonable except at very high pressures.

Liquid - Liquids are much less compressible than gasses. Even when a liquid is
described with an equation similar to a gas equation, the constants in the equation will
result in much less dramatic changes in volume with a change in temperature. Like wise
at constant volume, a temperature change will give a much larger pressure change than
seen in a gas.

A common equation of state for both liquids and solids is

Vm = C1 + C2 T + C3 T2 - C4 p - C5 p T

Vm = molar volume
T = temperature
p = pressure
C1, C2, C3, C4, C5 = empirical constants
where the empirical constants are all positive and specific to each substance.

For constant pressure processes, this equation is often shortened to

Vm = Vmo ( 1 + A T + B T2 )

Vm = molar volume
Vmo = molar volume at 0 degrees C
T = temperature
A, B = empirical constants
where A and B are positive.

The equation of state created by Peng and Robinson has been found to be useful for
both liquids and real gasses.

p= RT - a(T)
------ ----------------------------
Vm - b Vm ( Vm + b ) + b ( Vm - b )

p = pressure
a = empirical constant
Vm = molar volume
R = ideal gas constant
b = empirical constant
T = temperature

Superfluid - Superfluids are physically liquids although they have interesting properties,
which are quantum mechanical in origin. Since this is still an active area of research and
not completely understood, a reference to an introductory article is given, but no
equations will be presented here.

Suspension - Suspensions behave physically most like liquids.

Colloid - A colloid being a type of suspension is also physically most like a liquid.
Liquid Crystal - Depending upon the temperature, liquid crystals may be crystalline,
glassy, flexible thermoplastics or ordered liquids. At sufficiently high temperatures, a true
liquid phase will exist. Most of the physical properties of these are the same as non
liquid crystal compounds. One exception is that as liquid crystal compounds are added
to a solvent the viscosity increases as expected until the concetration becomes high
enough to form a liquid crystal phase, when the viscosity drops.

Visceoelastic - Since visceoelastics behave like solids on short time scales and like
liquids over a long period of time, equations for liquids and solids could be used. Most of
the usefulness of visceoelastics is based on their mechanical properties rather than their
physical properties.

Solid - The volume of a solid will generally change very little with a change in
temperature. However, most solids are very incompressible so a constant volume
heating will give a very large pressure change for even a small change in temperature.
Crystals, glasses and elastomers are all types of solids.

A common equation of state for both liquids and solids is

Vm = C1 + C2 T + C3 T2 - C4 p - C5 p T

Vm = molar volume
T = temperature
p = pressure
C1, C2, C3, C4, C5 = empirical constants
where the empirical constants are all positive and specific to each substance.

For constant pressure processes, this equation is often shortened to

Vm = Vmo ( 1 + A T + B T2 )

Vm = molar volume
Vmo = molar volume at 0 degrees C
T = temperature
A, B = empirical constants
where A and B are positive.

Crystal - Crystals are solids which are often very hard. The equations above are used
for describing the physical properties of crystals.

Glass - Glasses are generally very brittle. The equations above are useful for describing
the physical behavior until the stress becomes too great and the material shatters.

Elastomer - An elastomer is an amorphous solid which can be deformed with out

breaking. The change in volume is generally negligible with deformation. However, the
cross sectional area may change considerably. For changes in temperature and
pressure, elastomers can be considered to be solids although much softer than other
solids.

Superplastic - The unique ability of superplastics to stretch is a mechanical property.

Physically, superplastics are treated as solids.
Bose-Einstein Condensate - At the time of this writing, the first reports of having made
a Bose-Einstein condensate have just been released. No measurements of physical
properties have yet been made. Considering various aspects of the theory predicting the
existence of this state lead to the conclusions that it might be a solid or a very
supercooled gas or one very large single atom.

Refractory - Refractory materials behave physically as solids.