Fugacity

Computer Methods in Chemical Engineering

Problem Statement: The following polynomial describes the gas behavior.
0 = P*V4 - R*T*V3 + (R*c/T2-R*T*B0+A0)*V2 + ... + (R*c*B0/T2+R*T*B0*b-A0*a)*V - R*c*B0*b/T2 where P = pressure T = temperature V = specific volume A0, a, B0, b, c, and R are constants.

Write a FORTRAN function V(P,T) that returns the specific volume V as a function of P and T. You can assume that all the constants in the equation (i.e., A0, a, B0, b, c, and R) are passed into the function through a common block. Solution:
c----------------------------------------------------------------------function V(P,T) c----------------------------------------------------------------------c Return the specific volume of an nonideal gas c calculated from Beattie-Bridgemen Equation of State c V ... specific volume in m^3/kmole=liter/mole (output) c P ... pressure in kPa (1atm = 101.325kPa) (input) c T ... temperature in Kelvin (input) c All the necessary constants are available in a common block c----------------------------------------------------------------------c Beattie-Bridgeman Equation of State (EOS) c R*T*(1-e) A c P = ---------*(V+B) - ---c V**2 V**2 c where c A = A0*(1-a/V) c B = B0*(1-b/V) c e = c/(V*T**3) c Multiply both sides of the EOS by V**4 gives a 4th degree polynomial c P*V**4 = R*T*(V-c/T**3)*(V**2+B0*(V-b)) - V*A0*(V-a) c Collect terms ... c 0 = P*V**4 - R*T*V**3 + (R*c/T**2-R*T*B0+A0)*V**2 + ... c + (R*c*B0/T**2+R*T*B0*b-A0*a)*V - R*c*B0*b/T**2 c----------------------------------------------------------------------c Programmin Note: c Call of ZPORC of IMSL to find the polynomial roots. c----------------------------------------------------------------------c Declare variables ---------------------------------------------------parameter (n=4) real coeff(n+1) complex roots(n) c All species-dependent constants comes through the common block. common /cblock/A0, a, B0, b, c, R, Temp c Make up the coefficient vector --------------------------------------coeff(5) = P ! V**4 term coeff(4) = -R*T ! V**3 term coeff(3) = R*c/T**2 - R*T*B0+A0 ! V**2 term coeff(2) = R*c*B0/T**2 + R*T*B0*b - A0*a ! V term coeff(1) = -R*c*B0*b/T**2 ! constant term c Call a routine to find the roots ------------------------------------c CALL ZRHQR(coeff, n, rootr, rooti) ! from Numerical Recipes CALL ZPORC (n, coeff, roots) c Return a valid root; pick the root near the ideal gas law. ----------c The 4th root seems to be the right one v = roots(4) end

Assume you are given a function V(P,T) that returns the specific volume V as a function of P and T. Write a FORTRAN function fugacity(P,T) to evaluate the fugacity at a given pressure P and temperature T based on the following defining equation:
fugacity P ln(--------) = P 0 p*V/(R*T) - 1 ------------- dp p (if you don't see the integral symbol above)

ln(fugacity/P) = integral (from 0 to P) (p*V/(R*T)-1)/p dp

Suggestion: If you have difficulty comprehending the question, first numerically integrate for a uninteresting problem, say V(P)=exp(-P). When you finally get what you are doing, switch to the more practical case of V(P)=vbb(P,T) For those who have not had thermodynamics: the integrand in the above equation is 0 for the ideal gas law, leading to fugacity=P. Thus, fugacity is a measure of the "real concentration" -- the chemical engineering term is "chemical potential". Note that you do not have to know anything about the meaning of fugacity to do this assignment; just evaluate the given integral. And if you already know the term fugacity, now you know how it is calculated. Solution:
c----------------------------------------------------------------------function fugacity(P,T) c----------------------------------------------------------------------c Return the fugacity based on the Beattie-Bridgemen Equation of State c fugacity ... fugacity of a gas in kPa (output) c P ... pressure in kPa (1atm = 101.325kPa) (input) c T ... temperature in Kelvin (input) c----------------------------------------------------------------------c Fugacity is calculated from the following equation. c P c ln(fugacity/P) = (p*V/(R*T)-1)/p dp c 0 c ln(fugacity/P) = integral (from 0 to P) (p*V/(R*T)-1)/p dp c----------------------------------------------------------------------c Programmin Note: c Call QDAGS of IMSL to integrate c----------------------------------------------------------------------external fugafcn common /cblock/A0, a, B0, b, c, R, Temp c Cannot include the function argument in COMMON; so store it in another variable Temp = T c Numerically evaluate the integral first, then find the fugacity -----c call QDAGS(func, a, b, errabs, errrel, s, errest) c where func ... name of the function to integrate, c must be in the form func(x) c a ... lower integration limit (input) c b ... upper integration limit (input) c errabs.. absolute error tolerance (input) c errrel.. relative error tolerance (input) c s ... estimate of the integral (output) c errest ... estimated error (output) call QDAGS(fugafcn, 0., P, 1.E-4, 0., xintegral, errest) fugacity = exp(xintegral)*P end

c----------------------------------------------------------------------function fugafcn(P) c----------------------------------------------------------------------c Specify the integrand function in fugacity calculation c c Fugacity is calculated from the following equation. c ln(fugacity/P) = integral (from 0 to P) (p*V/(R*T)-1)/p dp c----------------------------------------------------------------------common /cblock/A0, a, B0, b, c, R, T c Create an output vector whose size matches the input fugafcn = ( P*V(P,T) / (R*T) - 1.) / P end

Combined into a stand-alone program. FORTRAN Source Code (fugacity.for) Executable Program (fugacity.exe) Solve the same problem in MATLAB. Test case: At 500atm and 50C, fugacity(500*101.325, 273.15+50)=51292kPa=506.21atm (The given value is what my MATLAB program, more specifically the MATLAB's "quad8" function, gives. Since I do not have an analytical solution to compare my answer, I do not know the exact answer. Nevertheless, I highly suspect the value because 1) it does not agree with the experimental results and 2) from the class demo, e.g., xqdags.m in 3/18's Handout section, I know MATLAB's quad or quad8 cannot handle more demanding integration problems.) Solution: M-Script File (fugacity.m) Integrand Function (fugafcn.m)

Extra Credit Only: Modify the fugacity function to include physical units, i.e., write a MATLAB function fugacitu(P,uP,T,uT) to return the fugaricy in a unit consistent with the input. Return fugacity in atm when the input is given in atm, and so on. Since all sorts of pressure units are commonly in use (e.g., mmHg, psi, atm, bar, Pa, ...), "uP" in the argument informs the function the physical unit of the input pressure. Likewise, "uT" tells the function the unit of the input temperature (Celsius, Kelvin, Rankine, Fahrenheit, etc.). Solution: M-Script File (fugacitu.m) Re-work with Mathcad. In finding V(P,T), the specific volume as a function of pressure P and temperature T, either we can provide the polynomial coefficients and find the roots, or we can simply solve the equation of state for V. I prefer tackling the problem with the latter approach because it requires less work. Solution: Fugacity with V(P,T) via the Polynomial Root "polyroots". Snapshot of Mathcad Screen (fugacity.gif) Mathcad File (fugacity.mcd) Fugacity with V(P,T) via the Given-Find Block. Snapshot of Mathcad Screen (fugacit1.gif) Mathcad File (fugacit1.mcd) Ditto with Physical Units. Snapshot of Mathcad Screen (fugacit2.gif) Mathcad File (fugacit2.mcd) Return to Prof. Nam Sun Wang's Home Page Return to Computer Methods in Chemical Engineering (ENCH250) Computer Methods in Chemical Engineering -- Fugacity Forward comments to:

Nam Sun Wang Department of Chemical & Biomolecular Engineering University of Maryland College Park, MD 20742-2111 301-405-1910 (voice) 301-314-9126 (FAX) e-mail: nsw@umd.edu 1996-2006 by Nam Sun Wang