Virial equation, minimum pressure point

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SUMMARY

The discussion centers on determining the minimum pressure point of nitrogen (N2) using the virial equation at -50° C. The virial coefficients provided are A = 18.31, B = -2.88x10-2, C = 14.98x10-5, D = -14.47x10-8, and E = 4.66x10-11. Two differentiation approaches were attempted: the first involves differentiating the function PVm = A + BP + CP2 + DP3 + EP4, leading to a cubic equation, while the second expresses Vm as a function of P before differentiation. The real solution found using computational tools is approximately 113 atm, which is assumed to be the minimum pressure.

PREREQUISITES
  • Understanding of the virial equation and its coefficients
  • Knowledge of calculus, specifically differentiation and critical points
  • Familiarity with cubic equations and their solutions
  • Experience with computational tools like WolframAlpha or Excel for solving equations
NEXT STEPS
  • Research the analytical methods for solving cubic equations
  • Learn about graphical methods for estimating minima in functions
  • Explore the implications of virial coefficients on gas behavior
  • Study the product rule in calculus for differentiating products of functions
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Students and professionals in chemistry and physics, particularly those studying thermodynamics and gas behavior, will benefit from this discussion.

MexChemE
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Good evening PF! I'm having trouble figuring out how to attack this problem. I have tried two different ways but I don't know if either of them is correct.

Homework Statement


Using the provided virial coefficients, determine analytically the pressure at which the graph of PV versus P for N2 at -50° C, reaches a minimum point.
Virial coefficients for N2 at -50° C:
A = 18.31
B = -2.88x10-2
C = 14.98x10-5
D = -14.47x10-8
E = 4.66x10-11

Homework Equations


PV_m=A+BP+CP^2+DP^3+EP^4

The Attempt at a Solution


So, in order to find the minimum point I need two differentiate the function, and I'm trying two ways of doing this. I hope at least one of them is correct.

Option A:
\frac {d(PV_m)}{dP} = B+2CP+3DP^2+4EP^3
In order to find the critical points I equate the above derivative to zero.
B+2CP+3DP^2+4EP^3 = 0
Now I have to solve this cubic equation analytically, I could solve it with the help of a CAS, but the problem is asking for an analytic solution. This is as far as I can go. I did solve the equation with a software, and got two complex solutions and a real one. I assume the only solution that is relevant to me is the real one, right?

Option B:
I cleared Vm and expressed it as a function of P first, then differentiated.
V_m(P) = \frac{A}{P} +B+CP+DP^2+EP^3
\frac{dV_m}{dP} = -\frac{A}{P^2} +C+2DP+3EP^2
Equating to zero.
-\frac{A}{P^2}+C+2DP+3EP^2=0
I have to solve this equation analytically too, but I have no idea with this one.

Well, I hope at least one of my procedures is right. Any help or insight will be greatly appreciated!
 
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If PV is the quantity to be minimised then PV is what you must differentiate. dV/dP = 0 will find where V is minimised, which will be a different point.
There is an equation for solving cubics (Google it), but I'd be surprised if you were expected to know it or use it.
 
Yeah, option A seemed the most sound. I solved the equation with both WolframAlpha and Excel, the former gave me ~113 atm as a result, and the latter ~114 atm. Since this was the only real solution for the equation I'm assuming it is the minimum point I'm looking for and skipping the second derivative step. I also googled the equation you mentioned, I might try to solve it tomorrow. It's a LONG formula but it's just plug and chug. Thank you!

Now, I have a minor concern with notation, how should I denote the derivative of PV? d(PV) (applying product rule), VdP or PdV?
 
MexChemE said:
Yeah, option A seemed the most sound. I solved the equation with both WolframAlpha and Excel, the former gave me ~113 atm as a result, and the latter ~114 atm. Since this was the only real solution for the equation I'm assuming it is the minimum point I'm looking for and skipping the second derivative step. I also googled the equation you mentioned, I might try to solve it tomorrow. It's a LONG formula but it's just plug and chug. Thank you!

Now, I have a minor concern with notation, how should I denote the derivative of PV? d(PV) (applying product rule), VdP or PdV?

I would just leave it as d(PV). PV is the entity to be minimised.
 
MexChemE said:
I also googled the equation you mentioned, I might try to solve it tomorrow. It's a LONG formula but it's just plug and chug. Thank you!
"LONG" is way too mildly put. You will be surprised by how many pages you have to fill before you get to the solution (if ever).
It may be that by "analytically" they mean exactly what you did. They did not say find an analytic solution. What would be the point in giving you the values of the parameters, if this were what they mean?
But you could have just plotted the (PV) function and graphically estimate the minimum. This would be a graphical method.
 

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