Expansion of Van der waals for small pressure

AI Thread Summary
The discussion focuses on expanding the Van der Waals (VDW) equation of state for small pressures to derive the first terms of a Virial expansion. The equation is expressed as Pv = RT + (b - a/RT)P + O(P^2), with the initial term at P=0 yielding RT. Participants suggest using Taylor series expansion around small pressures and differentiating the equation with respect to P to find the necessary derivatives. There is a focus on substituting variables for simplification and evaluating derivatives at P=0. The conversation emphasizes the mathematical approach to derive the desired expansion terms accurately.
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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Try rewriting the equation as:

Pv+\frac{a}{v}-Pb-\frac{ab}{v^2}=RT

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

Now, for convenience, substitute Pv = x:

x+\frac{aP}{x}-Pb-\frac{abP^2}{x^2}=RT

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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