Expansion of Van der waals for small pressure

In summary, the VDW equation of state can be rearranged to express Pv as a function of {P,T} and by expanding it in powers of P, it can be shown that the first terms of a Virial expansion for a VDW gas are given by the equation Pv = RT + (b - a/(RT))P + O(P^2). One method is to express Pv as x and use a Taylor series expansion about x = RT, with the derivative of x with respect to P evaluated at P = 0, x = RT. Another method is to expand the VDW equation about small pressures.
  • #1
CAF123
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Homework Statement


In the VDW eqn of state, ##(P + a/v^2)(v-b)=RT## write Pv as a function of {P,T} and by expanding the result in powers of P or otherwise show that the first terms of a Virial expansion in powers of P for a VDW gas are given by $$Pv = RT + \left(b - \frac{a}{RT}\right)P + O(P^2)$$

Homework Equations


Taylor expansion

The Attempt at a Solution


I have already solved this (I think) via a method belonging in the 'otherwise' category. However, I wish to also solve it via the method outlined. The hint is that we can express y =Pv, x=P and write ##y = y(0,T) + y'(0,T)x + O(x^2)##
This can be rewritten as $$Pv = Pv(0,T) + \frac{d}{dP} (Pv)|_{P=0}P + O(P^2)$$, so essentially we are expanding the VDW eqn about small pressures. The first term on the RHS I think should be RT, which makes sense, yet I don't see how it comes about from subbing P=0 into VDW. The differentiation of the second term gives $$b - a\frac{d}{dP} \frac{1}{v} + ab\frac{d}{dP} \frac{1}{v^2} = b -a \frac{d}{dv}\frac{1}{v}\frac{dv}{dP} + ab\frac{d}{dv} \frac{1}{v^2} \frac{dv}{dP}$$ but I am not sure how to continue from here.
Many thanks.
 
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  • #2
Try rewriting the equation as:

[tex]Pv+\frac{a}{v}-Pb-\frac{ab}{v^2}=RT[/tex]

Next, reexpress this as:
[tex]Pv+\frac{aP}{Pv}-Pb-\frac{abP^2}{(Pv)^2}=RT[/tex]

Now, for convenience, substitute Pv = x:

[tex]x+\frac{aP}{x}-Pb-\frac{abP^2}{x^2}=RT[/tex]

You know that, at P = 0, x = RT

So do your Taylor series expansion about this point. Take the derivative of the equation with respect to P, and then solve for the derivative of x with respect to P. Evaluate this derivative at P=0, x = RT.

Chet
 
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1. What is the Van der Waals equation of state?

The Van der Waals equation of state is a mathematical model used to describe the behavior of real gases, taking into account the intermolecular forces and the finite size of gas particles.

2. How does the Van der Waals equation account for small pressure effects?

The Van der Waals equation includes two additional terms, known as the attraction term and the repulsion term, which account for the intermolecular forces and the finite size of gas particles respectively. These terms become more significant at lower pressures, making the equation more accurate for small pressure ranges.

3. Why is the Van der Waals equation important for studying gas behavior?

The Van der Waals equation provides a more accurate description of gas behavior compared to the ideal gas law, which does not take into account the intermolecular forces and the finite size of gas particles. This is particularly important at high pressures and low temperatures, where the ideal gas law breaks down.

4. How does the Van der Waals equation change at higher pressures?

At higher pressures, the attractive forces between gas particles become more significant, leading to a decrease in the volume of the gas. This is reflected in the Van der Waals equation by a decrease in the value of the repulsion term, resulting in a smaller volume correction.

5. What are the limitations of the Van der Waals equation for small pressure?

The Van der Waals equation is not accurate for all gases, as it assumes that the intermolecular forces and the finite size of gas particles are constant. It also does not take into account the effects of temperature. Additionally, at very low pressures, other factors such as quantum effects may become more significant, making the equation less accurate.

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