ORIGINAL VERSION

The Peng-Robinson EOS - Example 2.9

Source: „Chemical Thermodynamics for Process Simulation, WILEY-VCH Verlag GmbH & Co.
KgaA, 1st Reprint 2012, pages 50-52“

Task:

Calculate the density of propylene at T=300K and P=10bar using the Peng-Robinson equation
of state. (The vapor pressure of propylene is Ps (300K)=12,12bar)

Given specifications:

• Molar mass \(M\) = 42.08 \(\frac{g}{mol}\)

• Critical temperature \(T_c\) = 364.21 K
• Critical pressure \(P_c\) = 45.55 * 105 \(Pa\)
• Acentric factor \(\omega\) = 0.1408
• Diagram: propylene vapor pressure - Temperature [\(P_s(T)\)]:

Source:
http://encyclopedia.airliquide.com/images_encyclopedie/VaporPressureGraph/Propylene_Vap
or_Pressure.GIF

Gas Properties:
http://encyclopedia.airliquide.com/Encyclopedia.asp?GasID=54#GeneralData
Notes:

• Pay attentions to the requestet units!

• Always round to 4 decimal places, if not told otherwise.
• When putting in a formula: mark indices with "_" und exponents with "^"! Dont forget
to use brackets! (e.g: \(\frac{T_c^2}{P_c}\)=(T_c^2)/(P_c))

Solution

The Peng-Robinson equation of state is given by

• z = v/v-b – [(a(T)*v)/ (R*T*(v*(v+b)+b*(v-b)))] Formula

The Equation can be rewritten as

z^3+(((bP)/(R*T))-1)*z^2+((aP)/(R^2*T^2)-3*((bP)/(RT))^2 – 2
*((bP)/(RT)))*z+[((bp)/(RT))^3+((bp)/(RT))^2- ((aP*bP)/(R^2*T^2*RT))]

The advantage of this formulation is that all coefficients and z itself remain dimensionless.

In order to calculate z you need to determine b and a(T)

´
Give the correct formula und value for b!
• b=[0.0778*(R*T_c)/P_c] (Formula)
• b=[MAXIMA: b=(0.0778*R*T_c)/P_c] *10-5 m3/mol (Value)
The term a(T) ist given as a(T)=a*alpha (T)
Determine a, T_r, alpha (T) in order to get a value for a(T)
• a=[0.45724*((R^2*T_c^2)/P_c) (Formula)
• a=[MAXIMA: a=0.45724*((R^2*T_c^2)/P_c)] Nm4/mol2

• T_r=[MAXIMA: T_r=((thetha+273.15)/T_c) (Value)

• alpha(T)=[MAXIMA: alpha=[1+(0.37464+1.54226*ω-0.26992* ω2)*(1-Tr0,5)]2 ]
(Value) 1P
• a(T)=[MAXIMA: a(T)=alpha(T)*a] J*m3/mol2 0,5P

Caution! In Order to minimize consequential errors, you are required to use the now given
values for the upcoming Caluclations!

• \(a(T)\)={NewAT}\(\frac{Jm^3}{mol^2}\)
• \(b\)={NewB}*\(10^{-5}\frac{m^3}{mol}\)

To solve the given cubic equation for z you can apply Cardano’s formula in this form:

• z^3+L*z^2+M*z+N=0

Calculate the coefficients U, S and T

• L= [MAXIMA: (bP)/(RT) – 1](value)
• M= (value)
• N= (value)
The terms in Cardano’s formula are

• P= (3*M-L^2)/3
• Q= (2*L^3)/27 – (LM/3)+N

Giving the discriminant

D=(P/3)^3+(Q/2)^2=…(Value)

For D< 0, there are 3 real solutions obtained. With the abbreviations:

Thetha=(-(p^3)/27)=(Value) and phi=arcos(-Q/2thetha)Value

Calculate all 3 real solutions and give the values from high (z_1) to low (z_3)!

z_1=2*Thetha^(1/3)*cos(phi/3)-(L/3)= (value)
z_2=2*Thetha^(1/3)*cos(phi/3+(2*pi)/3)-(L/3) (value)
z_3=2*Thetha^(1/3)*cos(phi/3+(4*pi)/3)-(L/3) (value)

Which solution is relevant relevant for the given problem?

The Pressure P={varP} is [lower] [lower,higher] than P_s({varT}K), so the fluid is in [liquid,
vapor] phase. This makes [ z_1](z_1,z_2,z_3) the relevant solution for the present case.

Calculate rho({varT}, {varP})=[MAXIMA rho=(1/v)*M with v=(z_1*R*T)/P] kg/m^3

GERMAN VERSION

Die Peng-Robinson Zustandsgleichung - Example 2.9

Quelle: „Chemical Thermodynamics for Process Simulation, WILEY-VCH Verlag GmbH & Co.
KgaA, 1st Reprint 2012, Seiten 50-52“

Aufgabe:

Calculate the density of propylene at T=300K and P=10bar using the Peng-Robinson equation
of state. (The vapor pressure of propylene is Ps (300K)=12,12bar)

Given specifications:

• Molar mass \(M\) = 42.08 \(\frac{g}{mol}\)

• Critical temperature \(T_c\) = 364.21 K
• Critical pressure \(P_c\) = 45.55 * 105 \(Pa\)
• Acentric factor \(\omega\) = 0.1408
• Diagram: propylene vapor pressure - Temperature [\(P_s(T)\)]:

Source:
http://encyclopedia.airliquide.com/images_encyclopedie/VaporPressureGraph/Propylene_Vap
or_Pressure.GIF

Gas Properties:
http://encyclopedia.airliquide.com/Encyclopedia.asp?GasID=54#GeneralData
Notes:

• Pay attentions to the requestet units!

• Always round to 4 decimal places, if not told otherwise.
• When putting in a formula: mark indices with "_" und exponents with "^"! Dont forget
to use brackets! (e.g: \(\frac{T_c^2}{P_c}\)=(T_c^2)/(P_c))

Solution

The Peng-Robinson equation of state is given by

• z = v/v-b – [(a(T)*v)/ (R*T*(v*(v+b)+b*(v-b)))] Formula

The Equation can be rewritten as

z^3+(((bP)/(R*T))-1)*z^2+((aP)/(R^2*T^2)-3*((bP)/(RT))^2 – 2
*((bP)/(RT)))*z+[((bp)/(RT))^3+((bp)/(RT))^2- ((aP*bP)/(R^2*T^2*RT))]

The advantage of this formulation is that all coefficients and z itself remain dimensionless.

In order to calculate z you need to determine b and a(T)

´
Give the correct formula und value for b!
• b=[0.0778*(R*T_c)/P_c] (Formula)
• b=[MAXIMA: b=(0.0778*R*T_c)/P_c] *10-5 m3/mol (Value)
The term a(T) ist given as a(T)=a*alpha (T)
Determine a, T_r, alpha (T) in order to get a value for a(T)
• a=[0.45724*((R^2*T_c^2)/P_c) (Formula)
• a=[MAXIMA: a=0.45724*((R^2*T_c^2)/P_c)] Nm4/mol2

• T_r=[MAXIMA: T_r=((thetha+273.15)/T_c) (Value)

• alpha(T)=[MAXIMA: alpha=[1+(0.37464+1.54226*ω-0.26992* ω2)*(1-Tr0,5)]2 ]
(Value) 1P
• a(T)=[MAXIMA: a(T)=alpha(T)*a] J*m3/mol2 0,5P

Caution! In Order to minimize consequential errors, you are required to use the now given
values for the upcoming Caluclations!

• \(a(T)\)={NewAT}\(\frac{Jm^3}{mol^2}\)
• \(b\)={NewB}*\(10^{-5}\frac{m^3}{mol}\)

To solve the given cubic equation for z you can apply Cardano’s formula in this form:

• z^3+L*z^2+M*z+N=0

Calculate the coefficients U, S and T

• L= [MAXIMA: (bP)/(RT) – 1](value)
• M= (value)
• N= (value)
 The terms in Cardano’s formula are

• P= (3*M-L^2)/3
• Q= (2*L^3)/27 – (LM/3)+N

Giving the discriminant

D=(P/3)^3+(Q/2)^2=…(Value)

For D< 0, there are 3 real solutions obtained. With the abbreviations:

Thetha=(-(p^3)/27)=(Value) and phi=arcos(-Q/2thetha)Value

Calculate all 3 real solutions and give the values from high (z_1) to low (z_3)!

z_1=2*Thetha^(1/3)*cos(phi/3)-(L/3)= (value)
z_2=2*Thetha^(1/3)*cos(phi/3+(2*pi)/3)-(L/3) (value)
z_3=2*Thetha^(1/3)*cos(phi/3+(4*pi)/3)-(L/3) (value)

Which solution is relevant relevant for the given problem?

The Pressure P={varP} is [lower] [lower,higher] than P_s({varT}K), so the fluid is in [liquid,
vapor] phase. This makes [ z_1](z_1,z_2,z_3) the relevant solution for the present case.

Calculate rho({varT}, {varP})=[MAXIMA rho=(1/v)*M with v=(z_1*R*T)/P] kg/m^3