PROBLEM 1

FLUID SELECTED
CARBON DIOXIDE
Ttri = 217 K
Ptrip = 0.517 MPa
Tc = 304.1282 K
Pc = 7.3773 MPa
W = 0.22394 MPa

TASK 1
1) Algorithm to calculate a molar volume at a set temperature and pressure
syms Z;
format long g;
R=8.314; %[L.KPa/(k*mol)]
T=217;
p=0.517*10^3;
Tc=304.1282;
Pc=7.3773*10^3;
omega=0.22394;
Tr=T/Tc;
alpha=exp((2.0+0.836*Tr)*(1-Tr^(0.134+0.508*omega-0.0467*omega^2)));
a=0.457535*alpha*R^2*Tc^2/Pc;
b=0.077796*R*Tc/Pc;
A=a*p/(R*T)^2;
B=b*p/R/T;
f=Z^3-(1-B)*Z^2+(A-2*B-3*B^2)*Z-(A*B-B^2-B^3);
df=diff(f,Z);
lambda=((1-B)^2)/9-(A-3*B^2-2*B)/3;
if lambda<=0
Z1=1;
Z2=(4/3)*B;
else
Z1=(1-B)/3-sqrt(lambda);
Z2=(1-B)/3+sqrt(lambda);
end

% Solve for vapor root of Z

if double(subs(f,{Z},{Z2}))>0
Zvap=(Z1+B)/2;
else
Zvap=(Z2+1)/2;
end

for j=1:200
fZ=double(subs(f,Z,Zvap));
dfZ=double(subs(df,Z,Zvap));
if dfZ<0
Zvapnew=Zvap+1;
 else
Zvapnew=Zvap-fZ/dfZ;
end
if abs(Zvapnew-Zvap)<1e-6
fprintf('The vapor root of Z is %6.4d\n', Zvapnew);
fprintf('Iteration number is %4.d\n', j);
vvap=Zvap*R*T/p;
fprintf('The molar volume of vapor root is %6.4d\n', vvap);
break;
end
Zvap=Zvapnew;
end

if double(subs(f,{Z},{Z1}))>0
Zliq=(Z1+B)/2;
else
Zliq=(Z2+1)/2;
end
for i=1:200
fZ=double(subs(f,Z,Zliq));
dfZ=double(subs(df,Z,Zliq));
if dfZ<0
Zliqnew=Zliq+1;
else
Zliqnew=Zliq-fZ/dfZ;
end
if abs(Zliqnew-Zliq)<1e-6
fprintf('The liquid root of Z is %6.4d\n', Zliqnew);
fprintf('Iteration number is %4.d\n', i);
vliq=Zliq*R*T/p;
fprintf('The molar volume of vapor root is %6.4d\n', vliq);
break;
end
Zliq=Zliqnew;
end

Results:
The vapor root of Z is 9.2607e-01
Iteration number is 5
The molar volume of vapor root is 3.2316e+00
The liquid root of Z is 1.0269e-02
Iteration number is 5
The molar volume of vapor root is 3.5834e-02

This results are very close with those found in the webpage given as a reference
TASK 2
2) Code for the Temperature range

syms Z;
format long g;
R=8.314; %[L.KPa/(k*mol)]
p=0.517*10^3;
Tc=304.1282;
Pc=7.3773*10^3;
omega=0.22394;
Tt=217;
Pt=0.517*10^3;
Trt=Tt/Tc;
Prt=Pt/Pc;
vdata=zeros(length([Trt:(10-Trt)/100:10]),3);
vdata(:,1)=[Trt:(10-Trt)/100:10]*Tc;
count=1;

for Tr=Trt:(10-Trt)/100:10
T=Tr*Tc;
alpha=exp((2.0+0.836*Tr)*(1-Tr^(0.134+0.508*omega-0.0467*omega^2)));
a=0.457535*alpha*R^2*Tc^2/Pc;
b=0.077796*R*Tc/Pc;
A=a*p/(R*T)^2;
B=b*p/R/T;
f=Z^3-(1-B)*Z^2+(A-2*B-3*B^2)*Z-(A*B-B^2-B^3);
df=diff(f,Z);
lambda=((1-B)/3)^2-(A-2*B-3*B^2)/3;
Z1=(1-B)/3-sqrt(lambda);
Z2=(1-B)/3+sqrt(lambda);
if lambda<=0
Z1=B;
Z2=1.01*B;
else
Z1=(1-B)/3-sqrt(lambda);
Z2=(1-B)/3+sqrt(lambda);
end
 % Solve for vapor root of Z

if double(subs(f,{Z},{Z2}))>0
Zvap=(Z1+B)/2;
else Zvap=(Z2+1)/2;
end
for j=1:100
fZ=double(subs(f,{Z},{Zvap}));
dfZ=double(subs(df,{Z},{Zvap}));
if dfZ<0
Zvapnew=Zvap+1;
else
Zvapnew=Zvap-fZ/dfZ;
end
if abs(Zvapnew-Zvap)<1e-6
break;
end
Zvap=Zvapnew;
end
vdata(count,3)=Zvap*R*T/p;

% Solve for liquid root of Z

if double(subs(f,{Z},{Z1}))>=0
Zliq=(Z1+B)/2;
else Zliq=(Z2+1)/2;
end
for i=1:100
fZ=double(subs(f,{Z},{Zliq}));
dfZ=double(subs(df,{Z},{Zliq}));
if dfZ<0
Zliqnew=Zliq-1;
else
Zliqnew=Zliq-fZ/dfZ;
end
if abs(Zliqnew-Zliq)<1e-12
if Zliqnew<0
Zliqnew=Zvapnew;
vliq=Zliqnew*R*T/p;
end
break;
end
Zliq=Zliqnew;
end
vdata(count,2)=Zliqnew*R*T/p;
count=count+1;
end
plot(vdata(:,1),vdata(:,2),'or');
hold on
plot(vdata(:,1),vdata(:,3),'ob');
grid on
axis([200 1100 2.5 20]);
xlabel('Temperature K');
ylabel('Molar volume L/mol');
RESULTS

REFERENCE WEBPAGE RESULT

Both result were obtained at the same pressure (0.517 MPa).

3) Code for the Pressure range and for “Z vs Pr”

clear all;
syms Z;
format long g;
R=8.314;
T=217;
Tc=304.1282;
Pc=7.3773*10^3;
omega=0.22394;
Tt=217;
Pt=0.517*10^3;
Trt=Tt/Tc;
Prt=Pt/Pc;
Tr=T/Tc;
vdata=zeros(length([Prt:(10-Prt)/100:10]),3);
vdata(:,1)=[Prt:(10-Prt)/100:10]*Pc;
Zdata=zeros(length([Prt:(10-Prt)/100:10]),3);
Zdata(:,1)=[Prt:(10-Prt)/100:10]*Pc;
count=1;
for Pr=Prt:(10-Prt)/100:10
p=Pc*Pr;
alpha=exp((2.0+0.836*Tr)*(1-Tr^(0.134+0.508*omega-0.0467*omega^2)));
a=0.457535*alpha*R^2*Tc^2/Pc;
b=0.077796*R*Tc/Pc;
A=a*p/(R*T)^2;
B=b*p/R/T;
f=Z^3-(1-B)*Z^2+(A-2*B-3*B^2)*Z-(A*B-B^2-B^3);
df=diff(f,Z);
lambda=((1-B)/3)^2-(A-2*B-3*B^2)/3;
Z1=(1-B)/3-sqrt(lambda);
Z2=(1-B)/3+sqrt(lambda);
if lambda<=0
Z1=B;
Z2=1.01*B;
else
Z1=(1-B)/3-sqrt(lambda);
Z2=(1-B)/3+sqrt(lambda);
end

% Solve for vapor root of Z

if double(subs(f,{Z},{Z2}))>0
Zvap=(Z1+B)/2;
else Zvap=(Z2+1)/2;
end
for j=1:100
fZ=double(subs(f,{Z},{Zvap}));
dfZ=double(subs(df,{Z},{Zvap}));
if dfZ<0
Zvapnew=Zvap+1;
else
Zvapnew=Zvap-fZ/dfZ;
end
if abs(Zvapnew-Zvap)<1e-6
break;
end
Zvap=Zvapnew;
end
Zdata(count,3)=Zvap;
vdata(count,3)=Zvap*R*T/p*1000;

% Solve for liquid root of Z

if double(subs(f,{Z},{Z1}))>=0
Zliq=(Z1+B)/2;
else Zliq=(Z2+1)/2;
end
for i=1:100
fZ=double(subs(f,{Z},{Zliq}));
dfZ=double(subs(df,{Z},{Zliq}));
if dfZ<0
Zliqnew=Zliq-1;
else
Zliqnew=Zliq-fZ/dfZ;
end
if abs(Zliqnew-Zliq)<1e-12
if Zliqnew<0
Zliqnew=Zvapnew;
 vliq=Zliqnew*R*T/p;
end
break;
end
Zliq=Zliqnew;
end
Zdata(count,2)=Zliqnew;
vdata(count,2)=Zliqnew*R*T/p*1000;

count=count+1;
end
plot(vdata(:,1)/1e3,vdata(:,2),'or',vdata(:,1)/1e3,vdata(:,3),'or');
title('Molar volume Vs Pr')
xlabel('P');
ylabel('Molar volume L/mol');

figure

semilogy(Zdata(:,1)/1e3,Zdata(:,2),'or',Zdata(:,1)/1e3,Zdata(:,3),'ob');
title('Z vs Pr');
xlabel('Pr');
ylabel('Z');

RESULTS

Molar volume Vs Pressure

RESOURCE
As we can see, or results are very close to those on the resource webpage.

4) Z Vs Pr

Main Resource
http://webbook.nist.gov/chemistry/fluid/
Fluid selected “CO2”