Reversible adiabatic expansion using Van der Waals' equation

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The discussion centers on deriving the relationship between pressure and volume for a Van der Waals gas during reversible adiabatic expansion. The equation to be shown is (p + A/V2)(V-B)γ = const., with γ expressed in terms of Cv and R. Participants clarify that R is a constant integral to the equations governing real gases, similar to its role in ideal gas equations. The confusion arises from the integration steps, particularly the introduction of R in the final expression. The conversation emphasizes the importance of understanding the underlying principles of thermodynamics and the specific characteristics of Van der Waals gases.
Kweh-chan
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Homework Statement


A real gas obeys Van der Waals‟ equation, which for one mole of gas is

(p + A/V2)(V-B) = RT

and its internal energy is given by

U = CvT - A/V

where the molar heat capacity at constant volume, Cv , is independent of the
temperature and pressure. Show that the relation between the pressure p and
the volume V of the Van der Waals‟ gas during a reversible adiabatic
expansion can be written as

(p + A/V2)(V-B)\gamma = const.

and find the expression for the parameter \gamma in terms of Cv and R .

Homework Equations



(p + A/V2)(V-B) = RT
U = CvT - A/V
Q= U + W

The Attempt at a Solution



There is already a given solution and method for this equation. I worked through this much:

0 = U + W
0 = dU + PdV

dU = (dU/dT)dT - (dU/dV)dV = CvdT + (A/V2)dV

0 = CvdT + (P + A/V2)dV = CvdT + RT/(V-B)
∫R/(V-B) dV = -∫Cv(dT/T)
Rln(V-B) + Cvln(T) = const.
ln(V-B)R + ln(T)CV = const
ln[(V-B)R(T)CV] = const.
(V-B)R(T)CV = const.


I got stuck here and checked the method. My process was right, but according to it, the next line of work is:

(V-B)R(RT)CV = const.

I don't understand where this mystery R comes from. I've tried rearranging the ideal gas equation, and the first given equation to no avail. Could someone please explain how I get this R in the process?

Thanks!
 
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R is the universal molargas constant and is part of the definition of a van der walal gas, just as it is for an ideal gas.

I haven't worked this out completely, but I would:

let p1 = p + A/v2
v1 = v - B
then p1v1 = RT.
By your du = -dw and dT = (1/R)(p1dv1 + v1dp1) you can eliminate T, integrate by parts to get p1v1γ = constant.

I think.
 
I was too thinking the same.

All I can think of, for a simple solution, is that you multiply both sides by R^Cv (which in itself is constant since Cv=1.5R when n=1)

This is valid since the right side remains constant = constant times R^Cv

The left side is now what we require.
 
Last edited:
Kweh-chan said:

(V-B)R(T)CV = const.


I got stuck here and checked the method. My process was right, but according to it, the next line of work is:

(V-B)R(RT)CV = const.

I don't understand where this mystery R comes from. I've tried rearranging the ideal gas equation, and the first given equation to no avail. Could someone please explain how I get this R in the process?

Thanks!

If you have

(V-B)R(T)CV = const.

and you multiply both sides of the equation by RCV, you get


(V-B)R(RT)CV = (const.)(RCV) = New constant

Chet
 

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