Mathematical tools and Thermodynamic properties to analyze non ideal gases

Abstract:
At this point in time we know how to solve problems that involve ideal gases.
Common questions are to find the amount of work a piston does when expanding
adiabatically or isothermally or perhaps to find the change in temperature a system
undergoes when doing a given amount of work. We also keep track of entropy while
doing these sorts of problems. Now, however, as we transition to real systems,
systems that involve non ideal gases, it becomes important to understand where
these ideal gas law properties originate from. In doing this, we will understand how
to manipulate certain thermodynamic equations that will allow us to solve a greater
variety of questions: questions involving non ideal gases.
One key but profound concept to understand is that previously we believed
that the internal energy of a material, in this case an ideal gas, to only depend on
temperature. While this is true, we learn that this is not the case for non ideal gases.
Instead, the internal energy of a non ideal gas is dependent on both the temperature
and pressure (or the specific volume) of the gas. Conceptually this makes sense
because for non ideal gases we accept that molecules have both a relatively
significant physical size and have a significant amount of attractive forces between
each other. Both of these factors result in a decrease in internal energy and can be
imagined as if the bulkier molecules have a harder time moving around and the
attractive forces causing the molecules to want to stick to each other. It then follows
that higher the pressure of the system that the molecules would have to interact
more with each other, therefore increasing the effects of the attractive forces. From
there we can conclude that the internal energy is also affected by a change in
pressure.

Koshu Takatsuji

To learn the difference between ideal and non ideal gases, let us refer to the
Joule Thompson experiment. In the Joule Thompson experiment, a gas stream A has
a temperature of 300K and pressure of 10bar and is allowed to expand in a
compartment that allows the pressure to reach 1bar.

By first identifying our system to be the gas that is undergoing adiabatic

expansion in the chamber, using the first fundamental thermodynamic equation for
open systems we can say that:

We can safely assume that the system is at steady state because otherwise we
know that system would be changing. With that, we can say that is equal to 0.
Also assuming that the gas is allowed to adiabatically expand, we can say that the
heat flow out or is also equal to 0. Also, because no shaft works is done we can
safely say that
is also 0. Canceling out those terms, our fundamental equation
becomes:

Because our system is at steady state we know that the flow in is equal to the
flow out. With that we can simplify the above to be:

Further simplifying the equation by diving by n we get:

Then by assuming that the gas is an ideal gas, we can say that the enthalpy is
equal to CpT. This causes our equation to become:
Dividing both sides by Cp, we can then say that the temperature that is
coming in is equal to the temperature coming out.
I think this is a rather profound concept to understand because it shows how
ideal gases that undergo adiabatic expansion do not undergo a change in
temperature. And this only occurs because ideal gases have internal energies that do
Koshu Takatsuji

not depend on the change in pressure, meaning that no matter how much of a
change in pressure there is, temperature will remain constant.
As great as this is, we must understand that in real life scenarios we do not
use ideal gases, but instead use non-ideal gases. This leads to a certain property that
differs from the ideal case. In the ideal case we could confidently say that the
temperature is a function independent of pressure, but in a non-ideal case, we
cannot say that. In other words, a change in pressure can actually lead to a change in
temperature.
With that in mind, it then becomes our duty as engineers to understand how
this works.
Using what we derived before, that for the Joule-thompson experiment, that

, we can state that we are trying to find:

]
The equation above can be literally translated into: finding what the change
in temperature is with respect to a change in pressure holding H (enthalpy)
constant
Although it is theoretically possible to perform experiments and measure out
the change in temperature as a change in pressure with a constant enthalpy, it is
hard to do. It is hard to do because we humans do not have an intuitive sense of
what enthalpy is, neither do we have tools to measure enthalpy directly. It then
becomes our duty as engineers to alter the equation into something more
measurable, something that only includes pressure, temperature, and volume terms.
And to do that we must use a set of mathematical tools and thermodynamic
properties.
The mathematical tools include:
The inverse rule:

The chain rule:

And the triplet point rule:

Koshu Takatsuji

]
]

One way of describing a system is by the amount of potential/internal

energy it has. And depending on the way you want to describe the amount of
energy a system has, you use different potential functions. The potential
functions are then defined as:
dU = TdS PdV
dH = TdS + VdP
dA = -SdT PdV
dG = -SdT + VdP
By manipulating the above potential functions you can discover different
thermodynamic relationships. One of the main manipulation techniques is to use the
following second derivative:

Using the above, we can say that:

By plugging in dU = TdS PdV, we can then find that:

]

And this is called a Maxwell relationship. Likewise, you can do this for any of
the other thermodynamic equations and get a similar property. The other three
Maxwells relationships are:
]

Koshu Takatsuji

Aside from the Maxwell relationships, we should know the basic definitions
of what Cv and Cp are equal to.
]

and:

Now, armed with the basic mathematical tools and the basic thermodynamic
properties, we can proceed to solve our original problem of what:
]
is.
As I said previously, we are trying to get rid of the enthalpy term in this
equation. And when the enthalpy term, or even U,A,G, or S appears in the constants
area, the first thing we should try is the triple point rule. This allows us to put the
enthalpy term or the unwanted term into the denominator or numerator part of our
differential. We want the enthalpy term in the denominator or numerator term
because it becomes easier to manipulate with the thermodynamic properties.
So following suite, using the triplet rule, the above becomes:
]
]
]
Now that we have the enthalpy term in the numerator section, it has become
time to refer back to our thermodynamic properties. If we look carefully at the
thermodynamic properties list, we see that:
]
To evaluate

] however, we will start with and manipulate one of our

thermodynamic potential functions:

Koshu Takatsuji

dH = TdS + VdP

Because

] is a function that tells us the change in enthalpy as a change in

pressure holding temperature constant, we will divide our potential function for
enthalpy by the change in pressure at constant temperature:
]

And with simple division we can say that,

]

, therefore say making

. Rewriting our equation, we then get:

]

As we can see, we were able to find what

] is. But at the same time, we introduced

this new weird variable called entropy, and that isnt something we want. However,
if we take a quick glance at our Maxwell Rules, we find that we do know what ] is.
]

So by substituting it into
]

we get:
]
With that, we now have what

]
] and

] are equal to. So we can simplify

out what:
]
]
is equal to.
]

]
And with that we have our equation in terms we can physically feasibly
measure.

Koshu Takatsuji

Another question that I thought that was particularly useful and

encompassing of this non ideal concept has to do with finding out the increase or
decrease in the temperature of a gas that undergoes an adiabatic expansion or
compression. In other words, how much does the temperature of a non ideal gas
increase or decrease when it undergoes expansion or compression under adiabatic
conditions, knowing what the initial temperature is and what the initial and final
volume is.
I mean, to start this we would obviously go to our closed system
thermodynamic equations, the one for work being:
U = Q + W.
And because this system undergoes adiabatic change we can say that dQ is
equal to 0, giving us:
U=W
And by saying that W =
and by saying that the pressure is the
external pressure or some other pressure they give us, we can find out what work is
equal to. It then becomes our duty to see how the temperature of the gas changed
accounting for the work it did. In an ideal case scenario, we can say that
U = nCv(Tfinal Tinitial)
And by knowing what the initial temperature is, we can find out what the
final temperature is by equating U with W (which we have found previously).
The catch, however, is that now we are saying that the gas we are using is non ideal.
Therefore, we cannot say that U = nCv(Tfinal Tinitial). Instead we have to derive and
create our own equation for what U is equal to.
To do this, we have to set U as a function of two independent variables that it
is dependent on. Pressure and temperature would work just as well as volume and
temperature. And for the sake of this problem, we will say that our U is going to be a
function of temperature and volume.
U = f(T,V)
And now it is our duty to rewrite this equation into a more useful form. The
form being:
]

This is valid because the change in temperature exists in both the numerator
and denominator and will cancel out to become dU, and the same occurs for the
change in volume for the right part of the right hand side of the equation. It is
important to note that this idea can be done with any of the other variables so long
as the derivatives you are dividing by are independent of each other.

Koshu Takatsuji

As good as this equation this looks, it gives us no important information

because the dU term, a term we cant measure, still exists on the right hand side.
Now if we look at our Cp and Cv definitions, we find that:
]
So we can rewrite the above equation to become:
]

Now the only term we cannot easily solve for is the

] term. But luckily, we

have our potential function of what dU is equal to. dU = TdS PdV, so we can use
brute force to find out what

] is equal to. Because

] is simply dividing the

change in U by the change in volume at constant temperature, that is what we are

going to do to the dU = TdS PdV equation. This gives us:

And again, because dividing the change in volume by the change in volume is
equal to 1, we can rewrite the above as:

As good as this is, we are still left with a term that we do not want: the
change in entropy term. And we do not like this because entropy is not something
we can easily measure. However, luckily, one of Maxwells rule is:
]

so by substituting it in, we get:

]

Koshu Takatsuji

Now that we are here, we can use the non ideal gas law that relates pressure
to temperature and volume. And it is:

where both a and b are given constants for different gases, R is the ideal gas
constant and n is the number of moles.
Using the above non ideal gas law, we can then find out what

] is by

simply taking the derivative of the non ideal gas law with respect to the change in
temperature. This tells us that
]
and that by multiplying T onto both sides that:
]

We can then substitute the above equation into our

equation. This gives us:

]
By substituting our non ideal gas law (vander waals equation)
into the above, we get:
]
or that:
]
That would then make our original dU equation of
become:

Koshu Takatsuji

And by integrating both sides, we get:

(

And because previously we said that U = W, and because we know what W is, and
what the initial temperature and initial and final volume is, we can find out what the
final temperature is.
I hope that through these two examples that you, the reader, understand the
basic mathematical principles of working with non ideal gases. And that
conceptually you understand that this is necessary because it allows us to work with
non ideal gases easily. In other words, this section allows us to rewrite certain
equations that account for non ideal gas properties (i.e the non ideal gas law).

Koshu Takatsuji