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# Cutlip and Shacham: Problem Solving in Chemical and Biochemical Engineering

Chapter 5
Problem Solving with MATLAB
Cheng-Liang Chen
PSE
LABORATORY
Department of Chemical Engineering
National TAIWAN University
Chen CL 1
Molar Volume and Compressibility
from Redlich-Kwong Equation
Concepts Utilized: Analytical solution of the cubic Redlich-Kwong equation for
compressibility factor and calculation of the molar volume at various reduced
temperature and pressure values.
Numerical Methods: Solution of a set of explicit equations.
Problem Statement:
The Redlich-Kwong equation of state is given by
P =
RT
(V b)

a
V (V +b)

T
(1)
a = 0.42747
_
R
2
T
5/2
c
P
c
_
b = 0.08664
_
RT
c
P
c
_
Chen CL 2
where P = pressure in atm
V = molar volume in liters/g-mol
T = temperature in K
R = gas constant (R = 0.08206 (atm-liter/g-mol-K))
Te = critical temperature in K
Pe = critical pressure in atm
The compressibility factor is given by
z =
PV
RT
Equation (1) can be written, after considerable algebra, in terms of the
compressibility factor as a cubic equation (see Seader and Henley)
f(z) = z
3
z
2
qz r = 0 (5)
where r = A
2
B, q = B
2
+B A
2
A
2
= 0.42747
_
P
r
T
5/2
r
_
B = 0.0866
_
P
r
T
r
_
in which P
r
is the reduced pressure (P/P
c
) and T
r
is the reduced temperature
(T/T
c
). Equation (5) can be solved analytically for three roots. Some of these
Chen CL 3
roots are complex. Considering only the real roots, the sequence of calculations
involves the steps
C =
_
f
3
_
3
+
_
g
2
_
2
f =
3q 1
3
g =
27r 9q 2
27
If C > 0, there is one real solution for z given by
z = D +E + 1/3
D = (g/2 +

C)
1/3
E = (g/2

C)
1/3
If C < 0, there are three real solutions
z
k
= 2
_
f
3
cos
_

3
+
2(k 1)
3
_
+
1
3
, k = 1, 2, 3
= a cos

g
2
/4
f
3
/27
In the supercritical region when T
r
10, two of these solutions are negative, so
Chen CL 4
the maximal z
k
is selected as the true compressibility factor. (Note: let z = 0 for
C < 0 in the following)
Calculate the cpmpressibility factor and molar volume of steam for the reduced
temperatures T
r
= 1 3 and pressures P
r
= 0.1 10. Prepare a table and a plot
of the compressibility factor versus T
r
and P
r
as well as a table and a plot of the
molar volume versus pressure and T
r
. The pressure and the volume should be in a
logarithmic scale in the second plot.
Chen CL 5
%filename P5_01A_CCL
R = 0.08206;%Gas constant (L-atm/g-mol-K)
Tc = 647.4; %Critical temperature (K)
Pc = 218.3; %Critical pressure (atm)
a = 0.42747 * R ^ 2 * Tc ^ (5 / 2) / Pc;%Eq. (4-2), RK equation constant
b = 0.08664 * R * Tc / Pc; %Eq. (4-3),RK equation constant
Pr = 10 %1.2;%0.1; %Reduced pressure (dimensionless)
Tr = 3 %1; %Reduced temperature (dimensionless)
Asqr = 0.42747 * Pr / (Tr ^ 2.5);%Eq. (4-8)
B = 0.08664 * Pr / Tr; %Eq. (4-9)
r = Asqr * B; %Eq. (4-6)
q = B ^ 2 + B - Asqr; %Eq. (4-7)
g = (-27 * r - (9 * q) - 2) / 27;%Eq. (4-12)
f = (-3 * q - 1) / 3; %Eq. (4-11)
C = (f / 3) ^ 3 + (g / 2) ^ 2; %Eq. (4-10)
if (C > 0)
E1 = 0 - (g / 2) - sqrt(C); %Eq. (4-15)
D = (0 - (g / 2) + sqrt(C)) ^ (1 / 3);%Eq. (4-14)
E = sign(E1) * abs(E1) ^ (1 / 3);%Eq. (4-15)
z = D + E + 1 / 3;%Eq. (4-13), Compressibility factor (dimensionless)
else
z = 0;
Chen CL 6
end
P = Pr * Pc; %Pressure (atm)
T = Tr * Tc; %Temperature (K)
V = z * R * T / P %Molar volume (L/g-mol)
Pr =
10
Tr =
3
V =
0.0837
Chen CL 7
%filename P5_01B_CCL
clear, clc, format compact, format short g
Tc = 647.4; %Critical temperature (K)
Pc = 218.3; %Critical pressure (atm)
Tr_set=[1 1.2 1.5 2 3];
Pr_set(1) = 0.1;
Pr_set(2) = 0.2;
i = 2;
while Pr_set(i)<=10
i=i+1;
Pr_set(i)=Pr_set(i-1)+0.2;
end
n_Tr = size(Tr_set,2);
n_Pr = size(Pr_set,2);
for i=1:n_Tr
Tr=Tr_set(i);
for j=1:n_Pr
Pr=Pr_set(j);
[z(j,i), V(j,i)] = RKfun(Tr,Pr,Tc,Pc) ;
if z(j,i)==0
disp([ No solution obtained for Tr = num2str(Tr) ...
and Pr = num2str(Pr)]);
Chen CL 8
end
end
end
disp( Compressibility Factor Versus Tr and Pr);
disp( Tabular Results);
disp( );
disp(Pr\Tr 1.0 1.2 1.5 2 3 );
Res=[Pr_set z];
disp(Res);
subplot(1,2,1)
plot(Pr_set,z(:,1),-,Pr_set,z(:,2),+,Pr_set,z(:,3),*,...
Pr_set,z(:,4),x,Pr_set,z(:,5),o,LineWidth,2);
set(gca,FontSize,14,Linewidth,2)
legend(Tr=1,Tr=1.2,Tr=1.5,Tr=2,Tr=3);
title(\bf Compressibility Factor Versus Tr and Pr,FontSize,12)
xlabel(\bf Reduced Pressure (Pr),FontSize,14);
ylabel(\bf Compressibility Factor (z),FontSize,14);
disp( Pause; Please press any key to continue ... )
pause
P_set=Pr_set.*Pc;
disp( Molar Volume Versus Tr and P);
disp( Tabular Results);
Chen CL 9
disp( );
disp(Pr\Tr 1.0 1.2 1.5 2 3 );
Res=[P_set V];
disp(Res);
subplot(1,2,2)
loglog(P_set,V(:,1),-,P_set,V(:,2),+,P_set,V(:,3),*,...
P_set,V(:,4),x,P_set,V(:,5),o,LineWidth,2);
legend(Tr=1,Tr=1.2,Tr=1.5,Tr=2,Tr=3);
set(gca,FontSize,14,Linewidth,2)
title(\bf Molar Volume Versus Tr and P,FontSize,12)
xlabel(\bf Pressure (atm),FontSize,14);
ylabel(\bf Molar Volume (L/g-mol),FontSize,14);
Chen CL 10
function [z, V] = RKfun(Tr,Pr,Tc,Pc)
R = 0.08206; %Gas constant (L-atm/g-mol-K)
a = 0.42747 * R ^ 2 * Tc ^ (5 / 2) / Pc;%Eq. (4-2), RK equation constant
b = 0.08664 * R * Tc / Pc; %Eq. (4-3),RK equation constant
Asqr = 0.42747 * Pr / (Tr ^ 2.5); %Eq. (4-8)
B = 0.08664 * Pr / Tr; %Eq. (4-9)
r = Asqr * B; %Eq. (4-6)
q = B ^ 2 + B - Asqr; %Eq. (4-7)
g = (-27 * r - (9 * q) - 2) / 27; %Eq. (4-12)
f = (-3 * q - 1) / 3; %Eq. (4-11)
C = (f / 3) ^ 3 + (g / 2) ^ 2; %Eq. (4-10)
if (C > 0)
E1 = 0 - (g / 2) - sqrt(C); %Eq. (4-15)
D = (0 - (g / 2) + sqrt(C)) ^ (1 / 3); %Eq. (4-14)
E = sign(E1) * abs(E1) ^ (1 / 3); %Eq. (4-15)
z = D + E + 1 / 3; %Eq. (4-13), Compressibility factor (dimensionless)
else
z = 0;
end
P = Pr * Pc; %Pressure (atm)
T = Tr * Tc; %Temperature (K)
V = z * R * T / P; %Molar volume (L/g-mol)
Chen CL 11
Calculation of Flow Rate In A Pipeline
Concepts Utilized: Application of the general mechanical energy balance for
incompressible uids, and calculation of ow rate in a pipeline for various pipe
diameters and lengths.
Numerical Methods: Solution of a single nonlinear algebraic equation and
alternative solution using the successive substitution method.
Problem Statement:
The following gure shows a pipeline that delivers water at a constant
temperature T = 60
o
F from point 1 where the pressure is P
1
= 150 psig and the
elevation is z
1
= 0 ft to point 2 where the pressure is atmospheric and the
elevation is z
2
= 300 ft.
The density and viscosity of the water can be calculated from the following
Chen CL 12
equations.
= 62.122 + 0.0122T 1.54 10
4
T
2
+ 2.65 10
7
T
3
2.24 10
10
T
4
ln = 11.0318 +
1057.51
T + 214.624
where T is in
o
F, is in lb
m
/ft
3
, and is in lb
m
/fts.
(a) Calculate the ow rate q (in gal/min) for a pipeline with eective length of
L = 1000 ft and made of nominal 8-inch diameter schedule 40 commercial steel
pipe. (Solution: v = 11.61 ft/s, gpm =1811 gal/min)
(b) Calculate the ow velocities in ft/s and ow rates in gal/min for pipelines at
60
o
F with eective lengths of L = 500, 1000, . . . 10, 000 ft and made of nominal
4-, 5-, 6- and 8-inch schedule 40 commercial steel pipe. Use the successive
substitution method for solving the equations for the various cases and present
the results in tabular form. Prepare plots of ow velocity v versus D and L, and
ow rate q versus D and L.
(c) Repeat part (a) at temperatures T = 40, 60, and 100
o
F and display the results
in a table showing temperature, density, viscosity, and ow rate.
Chen CL 13
Solution:
The general mechanical energy balance on an incompressible liquid applied to this
case yields

1
2
v
2
+gz +
g
c
P

+ 2
f
F
Lv
2
D
= 0 (4 20)
where v is the ow velocity in ft/s, g is the acceleration of gravity given by
g = 32.174 ft/s
2
, z = z
2
z
1
is the dierence in elevation (ft), g
c
is a
conversion factor (in English units g
c
= 32.174 ft-lb
m
/lb
f
s
2
), P = P
2
P
1
is the
dierence in pressure lb
m
/ft
2
), f
F
is the Fanning friction factor, L is the length of
the pipe (ft) and D is the inside diameter of the pipe (ft). The use of the
successive substitution method requires Equation (4-20) to be solved for v as
v =

_
gz +
g
c
P

_
_
_
1
2
2
f
F
Lv
2
D
_
The equation for calculation of the Fanning friction factor depends on the
Reynolds number, Re = vD/, where is the viscosity in lb
m
/ft-s. For laminar
ow (Re < 2100), the Fanning friction factor can be calculated from the equation
f
F
=
16
Re
Chen CL 14
For turbulent ow (Re > 2100) the Shacham equation can be used
f
F
=
1
16
_
log
_
/D
3.7

5.02
Re
log
_
/D
3.7
+
14.5
Re
___
2
where /D is the surface roughness of the pipe ( = 0.00015 ft for commercial
steel pipes). The ow velocity in the pipeline can be converted to ow rate by
multiplying it by the cross section area of the pipe, the density of water (7.481
gal/ft
3
), and factor (60 s/min). Thus q has units of (gal/min). The inside
diameters (D) of nominal 4-, 5-, 6-, and 8-inch schedule 40 commercial steel pipes
are provided in Appendix Table D-5.
The problem is set up rst for solving for one length and one diameter value. The
iteration function of the successive substitution method for calculation of the ow
velocity is given by
v
i+l
= F(v
i
), i = 0, l, . . .
An error estimate at iteration i is provided by

i
= |v
i
v
i+1
|
The solution is acceptable when the error is small enough, typically
i
< 1 10
5
.
Chen CL 15
function P5_2C_CCL
clear, clc, format short g, format compact
D_list=[4.026/12 5.047/12 6.065/12 7.981/12]; % Inside diameter of pipe (ft)
T = 60; %Temperature (deg. F)
for i = 1:4
D = D_list(i);
j=0;
for L=500:500:10000
j = j+1;
L_list(j)=L; % Effective length of pipe (ft)
[v(j,i),fval]=fzero(@NLEfun,[1 20],[],D,L,T);
if abs(fval)>1e-10
disp([No Conv. for L = num2str(L) and D = num2str(D)]);
end
q(j,i) = v(j,i) * pi * D ^ 2 / 4* 7.481 * 60; %Flow rate (gpm)
end
end
disp( Flow Velocity (ft/s) versus Pipe Length and Diameter);
disp( Tabular Results);
disp();
disp( L\D D=4" D=5" D=6" D=8");
Res=[L_list v];
Chen CL 16
disp(Res);
subplot(1,2,1)
plot(L_list,v(:,1),-,L_list,v(:,2),+,L_list,v(:,3),*,...
L_list,v(:,4),x,LineWidth,2);
set(gca,FontSize,14,Linewidth,2)
legend( D=4", D=5", D=6", D=8");
title(\bf Flow Velocity,FontSize,12)
xlabel(\bf Pipe Length (ft),FontSize,14);
ylabel(\bf Velocity (ft/s),FontSize,14);
disp( Pause; Please press any key to continue ... )
pause
disp( Flow Rate (gpm) versus Pipe Length and Diameter);
disp( Tabular Results); disp();
disp( L\D D=4" D=5" D=6" D=8");
Res=[L_list q(:,1) q(:,2) q(:,3) q(:,4)];
disp(Res);
subplot(1,2,2)
plot(L_list,q(:,1),-,L_list,q(:,2),+,L_list,q(:,3),*,...
L_list,q(:,4),x,Linewidth,2);
set(gca,FontSize,14,Linewidth,2)
legend( D=4", D=5", D=6", D=8");
title(\bf Flow rate,FontSize,14)
Chen CL 17
xlabel(\bf Pipe Length (ft),FontSize,14);
ylabel(\bf Flow rate (gpm),FontSize,14);
function fv = NLEfun(v,D,L,T)
epsilon = 0.00015;%Surface rougness of the pipe (ft)
rho = 62.122+T*(0.0122+T*(-0.000154+T*(0.000000265-...
(T*0.000000000224)))); %Fluid density (lb/cu. ft.)
deltaz = 300; %Elevation difference (ft)
deltaP = -150; %Pressure difference (psi)
vis = exp(-11.0318 + 1057.51 / (T + 214.624)); %Fluid viscosity (lbm/ft-s)
pi = 3.1416; %The constant pi
eoD = epsilon / D; %Pipe roughness to diameter ratio (dimensionless)
Re = D * v * rho / vis; %Reynolds number (dimesionless)
if (Re < 2100) %Fanning friction factor (dimensionless)
fF = 16 / Re;
else
fF=1/(16*log10(eoD/3.7-(5.02*log10(eoD/3.7+14.5/Re)/Re))^2);
end
fv=v-sqrt((32.174*deltaz+deltaP*144*32.174/rho)...
/(0.5-(2*fF*L/D))); %velocity (ft/s)
Chen CL 18
Flow Velocity (ft/s) versus Pipe Length and Diameter
Tabular Results
L\D D=4" D=5" D=6" D=8"
500 10.773 12.516 14.15 17.035
1000 7.4207 8.6048 9.7032 11.613
1500 5.9721 6.9243 7.8051 9.3295
2000 5.1188 5.9361 6.6912 7.9953
2500 4.5409 5.2674 5.9382 7.0953
3000 4.1168 4.7769 5.3861 6.4362
3500 3.7888 4.3975 4.9592 5.927
4000 3.5255 4.093 4.6166 5.5185
4500 3.3082 3.8416 4.3338 5.1815
5000 3.1249 3.6297 4.0953 4.8973
5500 2.9677 3.4478 3.8907 4.6535
6000 2.8309 3.2896 3.7128 4.4415
6500 2.7106 3.1504 3.5561 4.2548
7000 2.6036 3.0266 3.4169 4.0889
7500 2.5077 2.9156 3.292 3.9402
8000 2.4211 2.8154 3.1793 3.8059
8500 2.3424 2.7244 3.0769 3.6838
9000 2.2706 2.6412 2.9832 3.5723
9500 2.2046 2.5648 2.8972 3.4698
Chen CL 19
10000 2.1437 2.4943 2.8179 3.3752
Pause; Please press any key to continue ...
Flow Rate (gpm) versus Pipe Length and Diameter
Tabular Results
L\D D=4" D=5" D=6" D=8"
500 427.5 780.53 1274.2 2656.4
1000 294.46 536.59 873.81 1811
1500 236.98 431.8 702.87 1454.8
2000 203.12 370.17 602.56 1246.8
2500 180.19 328.48 534.75 1106.4
3000 163.36 297.89 485.03 1003.7
3500 150.35 274.23 446.59 924.25
4000 139.9 255.24 415.74 860.55
4500 131.27 239.56 390.27 807.99
5000 124 226.35 368.8 763.68
5500 117.76 215.01 350.37 725.66
6000 112.33 205.14 334.35 692.6
6500 107.56 196.46 320.24 663.49
7000 103.31 188.74 307.7 637.62
7500 99.508 181.82 296.46 614.43
8000 96.073 175.57 286.31 593.48
8500 92.951 169.89 277.08 574.45
Chen CL 20
9000 90.099 164.71 268.65 557.05
9500 87.48 159.94 260.91 541.07
10000 85.064 155.54 253.76 526.33
Chen CL 21
Adiabatic Operation of A Tabular Reactor for
Cracking of Acetone
Concepts Utilized: Calculation of the conversion and temperature prole in an
adiabatic tubular reactor. Demonstration of the eect of pressure and heat
capacity change on the conversion in the reactor.
Numerical Methods:
Solution of simultaneous ordinary dierential equations.
Problem Statement:
The irreversible, vapor-phase cracking of acetone (A) to ketene (B) and methane
(C) that is given by the reaction
CH
3
COCH
3
CH
2
CO +CH
4
is carried out adiabatically in a tubular reactor. The reaction is rst order with
respect to acetone and the specic reaction rate can be expressed by
ln(k) = 34.34
34222
T
(4-26)
Chen CL 22
where k is in s
1
and T is in K. The acetone feed ow rate to the reactor is 8000
kg/hr, the inlet temperature is T = 1150 K and the reactor operates at the
constant pressure of P = 162 kPa (1.6 atm). The volume of the reactor is 4 m
3
.
The material balance equations for the plug-ow reactor are given by
dF
A
dV
= r
A
(4-27)
dF
B
dV
= r
A
(4-28)
dF
C
dV
= r
A
(4-29)
where F
A
, F
B
, and F
C
are ow rates of acetone, ketene, and methane in g-mol/s,
respectively and r
A
is the reaction rate of A in g-mol/m
3
s. The reaction is rst
order with respect to acetone, thus
r
A
= kC
A
where C
A
is the concentration of acetone in g-mol/m
3
. For a gas phase reactor,
using the appropriate units of the gas constant, the concentration of the acetone
in g-mol/m
3
is obtained by
C
A
=
1000y
A
P
8.31T
Chen CL 23
The mole fractions of the various components are given by
y
A
=
F
A
F
A
+F
B
+F
C
, y
B
=
F
B
F
A
+F
B
+F
C
, y
C
=
F
C
F
A
+F
B
+F
C
The conversion of acetone can be calculated from
x
A
=
F
A0
F
A
F
A0
An enthalpy (energy) balance on a dierential volume of the reactor yields
dT
dV
=
r
A
(H)
F
A
C
pA
+F
B
C
pB
+F
C
C
pC
where H is the heat of the reaction at temperature T (in J/g-mol) and C
pA
,
CpB, and C
pC
are the molar heat capacities of acetone, ketene and methane (in
J/gmolK). Fogler provides the following equations for calculating the heat of
Chen CL 24
reaction and the molar heat capacities.
H = 80770 + 6.8(T 298) 0.00575(T
2
298
2
) 1.27 10
6
(T
3
298
3
)
C
pA
= 26.60 + 0.183T 45.86 10
6
T
2
C
pB
= 20.04 +.0945T 30.95 10
6
T
2
C
pC
= 13.39 + 0.077T 18.71 10
6
T
2
Galculate the nal conversion and the nal temperature of P = 1.6, 1.8, . . . , 5.0
atm, for acetone feed rates of F
A0
= 10, 20, 30, 35, and 38.3 mol/s where nitrogen
is fed to maintain the total feed rate 38.3 mol/s in all cases. Present the results in
tabular form and prepare plots of nal conversion versus P and F
A0
and nal
temperature versus P and F
A0
.
function P5_03C_CCL
clear, clc, format short g, format compact
FA0set = [10 20 30 35 38.3]; %Feed rate of acetone in kg-mol/s
P_set(1)=1.6;
i=1;
while P_set(i)<=5;
i=i+1;
P_set(i)=P_set(i-1)+0.2; % Pressure in atm
Chen CL 25
end
n_P = size(P_set);
for i=1:5
FA0=FA0set(i);
for j=1:n_P
P=P_set(j)*101.325; % Pressure in kPa
y0=[FA0; 0; 0; 1035; 0];
[V,y] = ode45(@ODEfun,[0 4],y0,[],FA0,P);
Xfin(j,i)=y(end,5);
Tfin(j,i)=y(end,4);
end
end
% -------------------------------------------------------------------------
disp( Final Conversion versus FA0 and Pressure);
disp( Tabular Results);
disp();
disp( Pressure FA0=10 FA0=20 FA0=30 FA0=35 FA0=38.3 );
Res=[P_set Xfin(:,1) Xfin(:,2) Xfin(:,3) Xfin(:,4) Xfin(:,5)];
disp(Res);
subplot(1,2,1)
plot(P_set,Xfin(:,1),-,P_set,Xfin(:,2),+,P_set,Xfin(:,3),*,...
P_set,Xfin(:,4),x,P_set,Xfin(:,5),o,LineWidth,2);
Chen CL 26
set(gca,FontSize,14,Linewidth,2)
legend(FA0=10,FA0=20,FA0=30,FA0=35,FA0=38.3);
title(\bf Final Conversion versus FA0 and Pressure,FontSize,12)
xlabel(\bf Pressure (atm),FontSize,14);
ylabel(\bf Final Conversion,FontSize,14);
disp( Pause; Please press any key to continue ... )
pause
disp( Final Temperature versus FA0 and Pressure);
disp( Tabular Results);
disp();
disp( Pressure FA0=10 FA0=20 FA0=30 FA0=35 FA0=38.3 );
Res=[P_set Tfin(:,1) Tfin(:,2) Tfin(:,3) Tfin(:,4) Tfin(:,5)];
disp(Res);
subplot(1,2,2)
plot(P_set,Tfin(:,1),-,P_set,Tfin(:,2),+,P_set,Tfin(:,3),*,...
P_set,Tfin(:,4),x,P_set,Tfin(:,5),o,Linewidth,2);
set(gca,FontSize,14,Linewidth,2)
legend(FA0=10,FA0=20,FA0=30,FA0=35,FA0=38.3);
title(\bf Final Temperature versus FA0 and Pressure,FontSize,12)
xlabel(\bf Pressure (atm),FontSize,14);
ylabel(\bf Temperature (K),FontSize,14);
% %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
Chen CL 27
function dYfuncvecdV = ODEfun(V,Yfuncvec,FA0,P);
FA = Yfuncvec(1);
FB = Yfuncvec(2);
FC = Yfuncvec(3);
T = Yfuncvec(4);
XA = Yfuncvec(5);
k = 8.2E14 * exp(-34222 / T); %Reaction rate constant in s-1
FN = 38.3 - FA0; %Feed rate of nitrogene in kg-mol/s
yA = FA / (FA + FB + FC + FN); %Mole fraction of acetone
CA = yA * P * 1000 / (8.31 * T); %Concentration of acetone in k-mol/m3
yB = FB / (FA + FB + FC + FN); %Mole fraction of ketene
yC = FC / (FA + FB + FC + FN); %Mole fraction of methane
rA = -k * CA; %Reaction rate in kg-mole/m3-s
deltaH = 80770 + 6.8 * (T - 298) - .00575 * (T ^ 2 - 298 ^ 2)...
- 1.27e-6 * (T ^ 3 - 298 ^ 3);
CpA = 26.6 + .183 * T - 45.86e-6 * T ^ 2; %Heat capacity of acetone in J/mol-K
CpB = 20.04 + 0.0945 * T - 30.95e-6 * T ^ 2; %Heat capacity of ketene in J/mol-K
CpC = 13.39 + 0.077 * T - 18.71e-6 * T ^ 2; %Heat capacity of methane in J/mol-K
CpN = 6.25 + 8.78e-3 * T - 2.1e-8 * T ^ 2; %Heat capacity of nitrogen in J/mol-K
dFAdV = rA; %Differential mass balance on acetone
dFBdV = -rA; %Differential mass balance on ketene
dFCdV = -rA; %Differential mass balance on methane
Chen CL 28
dTdV = (-deltaH)*(-rA)/(FA*CpA+FB*CpB+FC*CpC+FN*CpN);
%Differential enthalpy balance
dXAdV = -rA / FA0; %Conversion of acetone
Final Conversion versus FA0 and Pressure
Tabular Results
Pressure FA0=10 FA0=20 FA0=30 FA0=35 FA0=38.3
1.6 0.31358 0.27759 0.26394 0.25964
1.8 0.32043 0.28346 0.26946 0.26505
2 0.32651 0.28867 0.27436 0.26986
2.2 0.33197 0.29335 0.27877 0.27419
2.4 0.33693 0.2976 0.28277 0.27811
2.6 0.34147 0.30149 0.28643 0.2817
2.8 0.34565 0.30508 0.2898 0.28501
3 0.34952 0.3084 0.29293 0.28808
3.2 0.35313 0.31149 0.29584 0.29094
3.4 0.3565 0.31438 0.29856 0.29361
3.6 0.35967 0.3171 0.30112 0.29612
3.8 0.36266 0.31966 0.30353 0.29849
4 0.36548 0.32208 0.30581 0.30073
4.2 0.36815 0.32438 0.30797 0.30285
Chen CL 29
4.4 0.37069 0.32656 0.31002 0.30486
4.6 0.37311 0.32863 0.31198 0.30678
4.8 0.37543 0.33062 0.31385 0.30862
5 0.37764 0.33251 0.31563 0.31037
Column 6
0.25729
0.26265
0.26741
0.27169
0.27558
0.27913
0.28241
0.28545
0.28828
0.29092
0.29341
0.29575
0.29796
0.30006
0.30206
0.30396
0.30578
Chen CL 30
0.30752
Pause; Please press any key to continue ...
Final Temperature versus FA0 and Pressure
Tabular Results
Pressure FA0=10 FA0=20 FA0=30 FA0=35 FA0=38.3
Columns 1 through 5
1.6 911.84 908.14 907.47 907.47
1.8 909.02 905.32 904.66 904.67
2 906.5 902.81 902.16 902.18
2.2 904.24 900.55 899.91 899.93
2.4 902.18 898.49 897.87 897.89
2.6 900.3 896.61 895.99 896.02
2.8 898.56 894.87 894.26 894.29
3 896.94 893.26 892.66 892.69
3.2 895.44 891.76 891.16 891.2
3.4 894.03 890.35 889.76 889.8
3.6 892.7 889.03 888.44 888.48
3.8 891.45 887.78 887.19 887.24
4 890.27 886.59 886.02 886.07
4.2 889.15 885.47 884.9 884.95
4.4 888.08 884.4 883.84 883.89
4.6 887.07 883.39 882.82 882.88
Chen CL 31
4.8 886.09 882.42 881.86 881.92
5 885.16 881.49 880.93 880.99
Chen CL 32
Column 6
907.53
904.74
902.25
900.01
897.97
896.1
894.38
892.78
891.29
889.89
888.58
887.34
886.17
885.05
883.99
882.98
882.02
881.1
Chen CL 33
Correlation of The Physical Properties of Ethane
Concepts Utilized:
Correlations for heat capacity, vapor pressure, and liquid viscosity for an ideal gas.
Numerical Methods:
Polynomial, multiple linear, and nonlinear regression of data with linearization and
transformation functions.
Problem Statement:
Tables F-l through F-4 of Appendix F present values for dierent properties
of ethane (ideal gas heat capacity, vapor pressure, and liquid viscosity) as function
of temperature. Various regression models will be tted to the properties of
Appendix using MATLAB.
(a) Construct a MATLAB function which solves the linear regression problem
Xb = y, where X is the matrix of the independent variable values, y is the
vector of dependent variable values, and b is the vector of the linear regression
model parameters. The input parameters of the function are X, y, and a
logical variable which indicates whether there is a free parameter. The returned
parameters are: and the respective condence intervals, the calculated values
of the dependent variable y
calc
, the linear correlation coecient R
2
, and the
Chen CL 34
variance. Test the function by tting the Wagner equation to vapor pressure
data of ethane from TableF-3 of Appendix F.
(b) Fit 3rd- and 5th-degree polynomials to the heat capacity of ethane for for the
data given in Tables F-l and F-2 of Appendix F by using the multiple linear
regression function developed in (a). Compare the quality of the representation
of the various data sets with the polynomials of dierent degrees.
(c) Fit the Antoine equation to liquid viscosity of ethane given in Table F-4 of
Appendix F.
Chen CL 35
% filename P5_04A_CCL
clear, clc, format short g, format compact
prob_title = ([Vapor Pressure Correlation for Ethane]);
ind_var_name=[\bf Functions of Reduced Temp.];
dep_var_name=[\bf Logarithm of Reduced Pressure];
fname=input(Please enter the data file name > ); % VPfile.txt
X=xyData(:,2:end);
y=xyData(:,1);
[m,n]=size(X);
freeparm=input(Input 1 if there is a free par., otherwise input 0>);
[Beta,ConfInt, ycal,Var, R2]=MlinReg(X,y,freeparm);
disp([ Results, prob_title]);
Res=[];
if freeparm==0, nparm = n-1; else nparm = n; end
for i=0:nparm
if freeparm==0; ii=i+1; else ii=i; end
Res=[Res; ii Beta(i+1) ConfInt(i+1)];
end
disp( Parameter No. Beta Conf_int);
disp(Res);
disp([ Variance , num2str(Var)]);
Chen CL 36
disp([ Correlation Coefficient , num2str(R2)]);
disp( Pause; Please press any key to continue ... )
pause
subplot(1,2,1)
plot(y,y-ycal,*,Linewidth,2) % residual plot
set(gca,FontSize,14,Linewidth,2)
title([\bf Residual, prob_title],FontSize,12)
xlabel([dep_var_name \bf (Measured)],FontSize,14)
ylabel(\bf Residual,FontSize,14)
disp( Pause; Please press any key to continue ... )
pause
subplot(1,2,2)
plot(X,ycal, r-,X,y,bo,Linewidth,2)
title([\bf Cal/Exp Data prob_title],FontSize,12)
set(gca,FontSize,14,Linewidth,2)
xlabel([ind_var_name],FontSize,14)
ylabel([dep_var_name],FontSize,14)
% VPfile.txt : data file provided elsewhere
Please enter the data file name > VPfile.txt
Chen CL 37
Input 1 if there is a free parameter, otherwise input 0> 0
Results,Vapor Pressure Correlation for Ethane
Parameter No. Beta Conf_int
1 -6.4585 0.09508
2 1.2895 0.21514
3 -1.6712 0.26773
4 -1.2599 0.29417
Variance 9.3486e-005
Correlation Coefficient 1
Pause; Please press any key to continue ...
Pause; Please press any key to continue ...
Chen CL 38
% filename P5_04B_CCL
clear, clc, format short g, format compact
prob_title = ([Heat Capacity of Ethane]);
ind_var_name=[\bf Normalized Temp];
dep_var_name=[\bf Heat Capacity J/kmol*K ];
fname=input(Please enter the data file name > ); % CPfile.txt
X=xyData(:,2:end);
y=xyData(:,1);
[m,n]=size(X);
freeparm=input(Input 1 if there is a free par., otherwise input 0>);
[Beta, ConfInt,ycal, Var, R2]=MlinReg(X,y,freeparm);
disp([ Results, prob_title]);
Res=[];
if freeparm==0, nparm = n-1; else nparm = n; end
for i=0:nparm
if freeparm, ii=i+1; else ii=i; end
Res=[Res; ii Beta(i+1) ConfInt(i+1)];
end
disp( Parameter No. Beta Conf_int);
disp(Res);
disp([ Variance , num2str(Var)]);
Chen CL 39
disp([ Correlation Coefficient , num2str(R2)]);
plot(y,y-ycal,*,Linewidth,2)
set(gca,FontSize,14,Linewidth,2)
title([\bf Residual, prob_title],FontSize,12) % residual plot
xlabel([dep_var_name \bf (Measured)],FontSize,14)
ylabel(\bf Residual,FontSize,14)
disp( Pause; Please press any key to continue ... )
pause
plot(X(:,2),ycal, r-,X(:,2),y,bo,Linewidth,2)
set(gca,FontSize,14,Linewidth,2)
title([\bf Cal/Exp Data prob_title],FontSize,12)
xlabel([ind_var_name],FontSize,14)
ylabel([dep_var_name],FontSize,14)
Please enter the data file name > Cpfile.txt
Input 1 if there is a free parameter, 0 otherwise > 1
Results, Heat Capacity of Ethane
Parameter No. Beta Conf_int
1 34267 1176.6
2 -48870 22701
3 1.0826e+006 1.3785e+005
4 -2.1962e+006 3.4361e+005
Chen CL 40
5 1.8628e+006 3.7147e+005
6 -5.8886e+005 1.4465e+005
Variance 121322.8071
Correlation Coefficient 0.99995
Pause; Please press any key to continue ...
Chen CL 41
Complex Chemical Equilibrium
by Gibbs Energy Minimization
Concepts Utilized:
Formulation of the chemical equilibrium problem as a Gibbs energy minimization
problem with atomic balance constraints. The use of Lagrange multipliers to
introduce the constraints into the objective function. Conversion of the
minimization problem into a system of nonlinear algebraic equations.
Numerical Methods:
Solution of a system of nonlinear algebraic equations.
Problem Statement:
Ethane reacts with steam to form hydrogen over a cracking catalyst at a
temperature of T = 1000 K and pressure of P = 1 atm. The feed contains 4
moles of H
2
O per mole of CH
4
. Balzisher et al. suggest that only the compounds
shown in Table 4-10 are present in the equilibrium mixture (assuming that no
carbon is deposited). The Gibbs energies of formation of the various compounds
at the temperature of the reaction (1000K) are also given in Table 4-10. The
equilibrium composition of the euent mixture is to be calculated using these
data.
Chen CL 42
Table 4-10: Compounds Present in Euent
of Steam Cracking Reactor
Gibbs Energy Feed Euent
No. Comp. kcal/gm-mol gm-mol Ini. Est.
1 CH
4
4.61 0.001
2 C
2
H
4
28.249 0.001
3 C
2
H
2
40.604 0.001
4 CO
2
94.61 0.993
5 CO 47.942 1.
6 O
2
0. 0.0001
7 H
2
0. 5.992
8 H
2
O 46.03 4 1.
9 C
2
H
6
26.13 1 0.001
Formulate the problem as a constrained minimization problem. Introduce the
constraints into the objective function using Lagrange multipliers and dierentiate
this function to obtain a system of nonlinear algebraic equations.
Chen CL 43
Solution:
The objective function to be minimized is the total Gibbs energy given by
min
n
i
G
RT
=

i=1
cn
i
_
G
o
i
RT
+ ln
n
i

n
i
_
(4 49)
where n
i
is the number of moles of component i, c is the total number of
compounds, R is the gas constant, and G
o
is the Gibbs energy of pure component
i at temperature T. The minimization of Equation (4-49) must be carried out
subject to atomic balance constraints
Oxygen Balance 0 = g
1
= 2n
4
+n
5
+ 2n
6
+n
7
4 (4 50)
Hydrogen Balance 0 = g
2
= 4n
1
+ 4n
2
+ 2n
3
+ 2n
7
+ 2n
8
+ 6n
9
14 (4 51)
Carbon Balance 0 = g
3
= n
1
+ 2n
2
+ 2n
3
+n
4
+n
5
+ 2n
9
2 (4 52)
The identication of the various components is given in Table 4-10. These three
constraints can be introduced into the objective functions using Lagrange
multipliers:
1
,
2
,
3
. The extended objective function is
min
n
i
,
j
F =

i=1
cn
i
_
G
o
i
RT
+ ln
n
i

n
i
_
+
3

j=1

j
g
j
(4 53)
Chen CL 44
The condition for minimum of this function at a particular point is that all the
partial derivatives of F with respect to n
i
and
j
vanish at this point. The partial
derivative of F with respect to n
1
for example, is
F
n
1
=
G
o
1
RT
+ ln
n
1

n
i
+ 4
2
+
3
(4 54)
The other partial derivatives with respect to n
i
can be obtained similarly. If it is
expected that the amount of a particular compound at equilibrium is very close to
zero, it is preferable to rewrite the equation in a form that does not require
calculation of the logarithm of a very small number. Rearranging Equation (4-54),
for example, yields
n
1

n
i
exp
_
G
o
1
RT
+ 4
2
+
3
_
= 0
The partial derivatives of F with respect to
1
,
2
, and
3
are g
1
, g
2
, and g
3
,
respectively.
Chen CL 45
function P5_05A1_CCL
clear, clc, format short g, format compact
xguess = [10. 10. 10. 5.992 1. 1. 0.993 0.001 ...
0.001 0.001 0.001 0.0001]; % initial guess vector
disp(Variable values at the initial estimate);
fguess = MNLEfun(xguess);
disp( Variable Value Function Value)
for i=1:size(xguess,2);
disp([xint2str(i) num2str(xguess(i)) num2str(fguess(i))]);
end
options = optimset(Diagnostics,[off],TolFun,[1e-9],...
TolX,[1e-9]);
xsolv = fsolve(@MNLEfun,xguess,options);
disp(Variable values at the solution);
fsolv = MNLEfun(xsolv);
disp( Variable Value Function Value)
for i=1:size(xguess,2);
disp([xint2str(i) num2str(xsolv(i)) num2str(fsolv(i))])
end
Chen CL 46
function fx = MNLEfun(x)
lamda1 = x(1);
lamda2 = x(2);
lamda3 = x(3);
H2 = x(4);
H2O = x(5);
CO = x(6);
CO2 = x(7);
CH4 = x(8);
C2H6 = x(9);
C2H4 = x(10);
C2H2 = x(11);
O2 = x(12);
R = 1.9872;
sum = H2 + O2 + H2O + CO + CO2 + CH4 + C2H6 + C2H4 + C2H2;
fx(1,1) = 2 * CO2 + CO + 2 * O2 + H2O - 4; %Oxygen balance
fx(2,1) = 4*CH4+4*C2H4+2*C2H2+2*H2+2*H2O+6*C2H6-14; %Hydrogen balance
fx(3,1) = CH4 + 2 * C2H4 + 2 * C2H2 + CO2 + CO + 2 * C2H6 - 2; %Carbon balance
fx(4,1) = log(H2 / sum) + 2 * lamda2;
fx(5,1) = -46.03 / R + log(H2O / sum) + lamda1 + 2 * lamda2;
fx(6,1) = -47.942 / R + log(CO / sum) + lamda1 + lamda3;
fx(7,1) = -94.61 / R + log(CO2 / sum) + 2 * lamda1 + lamda3;
Chen CL 47
fx(8,1) = 4.61 / R + log(CH4 / sum) + 4 * lamda2 + lamda3;
fx(9,1) = 26.13 / R + log(C2H6 / sum) + 6 * lamda2 + 2 * lamda3;
fx(10,1) = 28.249 / R + log(C2H4 / sum) + 4 * lamda2 + 2 * lamda3;
fx(11,1) = C2H2-exp(-(40.604/R+2*lamda2+2*lamda3))*sum;
fx(12,1) = O2 - exp(-2 * lamda1) * sum;
Variable values at the initial estimate
Variable Value Function Value
x1 10 -0.0138
x2 10 0
x3 10 0
x4 5.992 19.5944
x5 1 4.6407
x6 1 -6.3214
x7 0.993 -19.8127
x8 0.001 43.2161
x9 0.001 84.0454
x10 0.001 65.1117
x11 0.001 0.001
x12 0.0001 9.9981e-005
Optimization terminated: no further progress can be made.
Chen CL 48
Problem may be ill-conditioned or Jacobian may be inaccurate.
Try using exact Jacobian or check Jacobian for errors.
Variable values at the solution
Variable Value Function Value
x1 10+7.44066e-015i -0.013798+4.9091e-009i
x2 10-3.7436e-008i -0.015082-0.00022231i
x3 10-1.4705e-008i -0.0054569-7.4103e-005i
x4 5.992+8.1803e-010i 19.5947+4.04813e-006i
x5 1+8.1803e-010i 4.6411+4.0488e-006i
x6 1+8.182e-010i -6.3211+4.109e-006i
x7 0.993+8.182e-010i -19.8124+4.10898e-006i
x8 0.00029165+6.9845e-010i 41.9842+6.35319e-006i
x9 -0.00037496-3.7053e-005i 83.0696-3.04309i
x10 -5.5221e-009-1.0635e-009i 53.0235-2.95132i
x11 0.0010003+8.1796e-010i 0.0010003+8.1796e-010i
x12 0.00010027+8.1823e-010i 0.00010025+8.183e-010i
Chen CL 49
function P5_05A2_CCL
clear, clc, format short g, format compact
xguess = [10. 10. 10. 5.992 1. 1. 0.993 0.001...
0.001 0.001 0.001 0.0001]; % initial guess vector
disp(Variable values at the initial estimate);
fguess = MNLEfun(xguess);
disp( Variable Value Function Value)
for i=1:size(xguess,2);
disp([xint2str(i) num2str(xguess(i)) num2str(fguess(i))]);
end
options = optimset(Diagnostics,off,TolFun,1e-9,...
TolX,1e-16,NonlEqnAlgorithm,gn);
xsolv = fsolve(@MNLEfun,xguess,options);
disp(Variable values at the solution);
fsolv=MNLEfun(real(xsolv));
disp( Variable Value Function Value)
for i=1:size(xguess,2);
disp([x int2str(i) num2str(real(xsolv(i))) num2str(fsolv(i))])
end
Chen CL 50
function fx = MNLEfun(x)
lamda1 = x(1);
lamda2 = x(2);
lamda3 = x(3);
H2 = x(4);
H2O = x(5);
CO = x(6);
CO2 = x(7);
CH4 = x(8);
C2H6 = x(9);
C2H4 = x(10);
C2H2 = x(11);
O2 = x(12);
R = 1.9872;
sum = H2 + O2 + H2O + CO + CO2 + CH4 + C2H6 + C2H4 + C2H2;
fx(1,1) = 2 * CO2 + CO + 2 * O2 + H2O - 4; %Oxygen balance
fx(2,1) =4*CH4+4*C2H4+2*C2H2+2*H2+2*H2O+6*C2H6-14; %Hydrogen balance
fx(3,1) = CH4 + 2 * C2H4 + 2 * C2H2 + CO2 + CO + 2 * C2H6 - 2; %Carbon balance
fx(4,1) = log(H2 / sum) + 2 * lamda2;
fx(5,1) = -46.03 / R + log(H2O / sum) + lamda1 + 2 * lamda2;
fx(6,1) = -47.942 / R + log(CO / sum) + lamda1 + lamda3;
fx(7,1) = -94.61 / R + log(CO2 / sum) + 2 * lamda1 + lamda3;
Chen CL 51
fx(8,1) = 4.61 / R + log(CH4 / sum) + 4 * lamda2 + lamda3;
fx(9,1) = 26.13 / R + log(C2H6 / sum) + 6 * lamda2 + 2 * lamda3;
fx(10,1) = 28.249 / R + log(C2H4 / sum) + 4 * lamda2 + 2 * lamda3;
fx(11,1) = C2H2-exp(-(40.604/R+2*lamda2+2*lamda3))*sum;
fx(12,1) = O2 - exp(-2 * lamda1) * sum;
Variable values at the initial estimate
Variable Value Function Value
x1 10 -0.0138
x2 10 0
x3 10 0
x4 5.992 19.5944
x5 1 4.6407
x6 1 -6.3214
x7 0.993 -19.8127
x8 0.001 43.2161
x9 0.001 84.0454
x10 0.001 65.1117
x11 0.001 0.001
x12 0.0001 9.9981e-005
Maximum number of function evaluations exceeded. Increase OPTIONS.MaxFunEvals.
Variable values at the solution
Chen CL 52
Variable Value Function Value
x1 24.4197 0
x2 0.25306 1.7764e-015
x3 1.5598 0
x4 5.3452 -1.1102e-016
x5 1.5216 2.1094e-015
x6 1.3885 2.2204e-016
x7 0.54492 -3.3307e-015
x8 0.066564 0
x9 1.6707e-007 1.3323e-015
x10 9.5412e-008 1.3323e-015
x11 3.157e-010 1.4387e-020
x12 7.0058e-021 1.5466e-021
Chen CL 53
function P5_05B_CCL
clear, clc, format short g, format compact
xguess = [10. 10. 10. 5.992 1. 1. 0.993 0.001...
0.001 0.001 0.001 0.0001]; % initial guess vector
disp(Variable values at the initial estimate);
fguess = MNLEfun(xguess);
disp( Variable Value Function Value)
for i=1:size(xguess,2);
disp([x int2str(i) num2str(xguess(i)) num2str(fguess(i))]);
end
pote=[0 0 0 2 2 2 2 2 2 2 2 2];
tol=1e-9;
maxit=100;
derfun=0;
print=0;
[xsolv,y,dy,info]=conles(@MNLEfun,xguess,pote,[],...
tol,maxit,derfun,print);
disp(Variable values at the solution);
fsolv = MNLEfun(xsolv);
disp( Variable Value Function Value)
for i=1:size(xguess,2);
disp([x int2str(i) num2str(xsolv(i)) num2str(fsolv(i))])
Chen CL 54
end
H2=xsolv(4);
H2O=xsolv(5);
CO=xsolv(6);
CO2=xsolv(7);
CH4=xsolv(8);
C2H6=xsolv(9);
C2H4=xsolv(10);
C2H2=xsolv(11);
O2=xsolv(12);
Chen CL 55
function fx = MNLEfun(x)
lamda1 = x(1);
lamda2 = x(2);
lamda3 = x(3);
H2 = x(4);
H2O = x(5);
CO = x(6);
CO2 = x(7);
CH4 = x(8);
C2H6 = x(9);
C2H4 = x(10);
C2H2 = x(11);
O2 = x(12);
R = 1.9872;
sum = H2 + O2 + H2O + CO + CO2 + CH4 + C2H6 + C2H4 + C2H2;
fx(1,1) = 2 * CO2 + CO + 2 * O2 + H2O - 4; %Oxygen balance
fx(2,1) = 4*CH4+4*C2H4+2*C2H2+2*H2+2*H2O+6*C2H6-14; %Hydrogen balance
fx(3,1) = CH4 + 2 * C2H4 + 2 * C2H2 + CO2 + CO + 2 * C2H6 - 2; %Carbon balance
fx(4,1) = log(H2 / sum) + 2 * lamda2;
fx(5,1) = -46.03 / R + log(H2O / sum) + lamda1 + 2 * lamda2;
fx(6,1) = -47.942 / R + log(CO / sum) + lamda1 + lamda3;
fx(7,1) = -94.61 / R + log(CO2 / sum) + 2 * lamda1 + lamda3;
Chen CL 56
fx(8,1) = 4.61 / R + log(CH4 / sum) + 4 * lamda2 + lamda3;
fx(9,1) = 26.13 / R + log(C2H6 / sum) + 6 * lamda2 + 2 * lamda3;
fx(10,1) = 28.249 / R + log(C2H4 / sum) + 4 * lamda2 + 2 * lamda3;
fx(11,1) = C2H2-exp(-(40.604/R+2*lamda2+2*lamda3))*sum;
fx(12,1) = O2 - exp(-2 * lamda1) * sum;
Variable values at the initial estimate
Variable Value Function Value
x1 10 -0.0138
x2 10 0
x3 10 0
x4 5.992 19.5944
x5 1 4.6407
x6 1 -6.3214
x7 0.993 -19.8127
x8 0.001 43.2161
x9 0.001 84.0454
x10 0.001 65.1117
x11 0.001 0.001
x12 0.0001 9.9981e-005
Variable values at the solution
Variable Value Function Value
Chen CL 57
x1 24.4197 0
x2 0.25306 -1.7764e-015
x3 1.5598 0
x4 5.3452 -1.1102e-016
x5 1.5216 -1.6653e-015
x6 1.3885 -1.5543e-015
x7 0.54492 5.5511e-015
x8 0.066564 -4.4409e-016
x9 1.6707e-007 -1.6964e-013
x10 9.5412e-008 -2.589e-013
x11 3.157e-010 9.3058e-025
x12 5.4592e-021 -3.9873e-035
Chen CL 58
function P5_05C_CCL
clear, clc, format short g, format compact
xguess = [10. 10. 10. 5.992 1. 1. 0.993 0.001...
0.001 0.001 0.001 0.0001]; % initial guess vector
disp(Variable values at the initial estimate);
fguess = MNLEfun(xguess);
disp( Variable Value Function Value)
for i=1:size(xguess,2);
disp([x int2str(i) num2str(xguess(i)) num2str(fguess(i))]);
end
pote=[0 0 0 2 2 2 2 2 2 2 2 2];
tol=1e-9; maxit=100;
derfun=0; print=0;
[xsolv,y,dy,info] = conles(@MNLEfun,xguess,pote,[],...
tol,maxit,derfun,print);
disp(Variable values at the solution);
fsolv = MNLEfun(xsolv);
disp( Variable Value Function Value)
for i=1:size(xguess,2);
disp([x int2str(i) num2str(xsolv(i)) num2str(fsolv(i))]);
end
H2 =xsolv(4);
Chen CL 59
H2O =xsolv(5);
CO =xsolv(6);
CO2 =xsolv(7);
CH4 =xsolv(8);
C2H6=xsolv(9);
C2H4=xsolv(10);
C2H2=xsolv(11);
O2 =xsolv(12);
R = 1.9872;
sum = H2 + O2 + H2O + CO + CO2 + CH4 + C2H6 + C2H4 + C2H2;
G_O2 = O2 * log(abs(O2 / sum));
G_H2 = H2 * log(H2 / sum);
G_H2O = H2O * (-46.03 / R + log(H2O / sum));
G_CO = CO * (-47.942 / R + log(CO / sum));
G_CO2 = CO2 * (-94.61 / R + log(CO2 / sum));
G_CH4 = CH4 * (4.61 / R + log(abs(CH4 / sum)));
G_C2H6 = C2H6 * (26.13 / R + log(abs(C2H6 / sum)));
G_C2H4 = C2H4 * (28.249 / R + log(abs(C2H4 / sum)));
G_C2H2 = C2H2 * (40.604 / R + log(abs(C2H2 / sum)));
ObjFun=G_H2+G_H2O+G_CO+G_O2+G_CO2...
+G_CH4+G_C2H6+G_C2H4+G_C2H2
Chen CL 60
function fx = MNLEfun(x)
lamda1 = x(1);
lamda2 = x(2);
lamda3 = x(3);
H2 = x(4);
H2O = x(5);
CO = x(6);
CO2 = x(7);
CH4 = x(8);
C2H6 = x(9);
C2H4 = x(10);
C2H2 = x(11);
O2 = x(12);
R = 1.9872;
sum = H2 + O2 + H2O + CO + CO2 + CH4 + C2H6 + C2H4 + C2H2;
fx(1,1) = 2 * CO2 + CO + 2 * O2 + H2O - 4; %Oxygen balance
fx(2,1) = 4*CH4+4*C2H4+2*C2H2+2*H2+2*H2O+6*C2H6-14; %Hydrogen balance
fx(3,1) = CH4 + 2 * C2H4 + 2 * C2H2 + CO2 + CO + 2 * C2H6 - 2; %Carbon balance
fx(4,1) = log(H2 / sum) + 2 * lamda2;
fx(5,1) = -46.03 / R + log(H2O / sum) + lamda1 + 2 * lamda2;
fx(6,1) = -47.942 / R + log(CO / sum) + lamda1 + lamda3;
fx(7,1) = -94.61 / R + log(CO2 / sum) + 2 * lamda1 + lamda3;
Chen CL 61
fx(8,1) = 4.61 / R + log(CH4 / sum) + 4 * lamda2 + lamda3;
fx(9,1) = 26.13 / R + log(C2H6 / sum) + 6 * lamda2 + 2 * lamda3;
fx(10,1) = 28.249 / R + log(C2H4 / sum) + 4 * lamda2 + 2 * lamda3;
fx(11,1) = C2H2-exp(-(40.604/R+2*lamda2+2*lamda3))*sum;
fx(12,1) = O2 - exp(-2 * lamda1) * sum;
Variable values at the initial estimate
Variable Value Function Value
x1 10 -0.0138
x2 10 0
x3 10 0
x4 5.992 19.5944
x5 1 4.6407
x6 1 -6.3214
x7 0.993 -19.8127
x8 0.001 43.2161
x9 0.001 84.0454
x10 0.001 65.1117
x11 0.001 0.001
x12 0.0001 9.9981e-005
Variable values at the solution
Variable Value Function Value
Chen CL 62
x1 24.4197 0
x2 0.25306 -1.7764e-015
x3 1.5598 0
x4 5.3452 -1.1102e-016
x5 1.5216 -1.6653e-015
x6 1.3885 -1.5543e-015
x7 0.54492 5.5511e-015
x8 0.066564 -4.4409e-016
x9 1.6707e-007 -1.6964e-013
x10 9.5412e-008 -2.589e-013
x11 3.157e-010 9.3058e-025
x12 5.4592e-021 -3.9873e-035
ObjFun =
-104.34
Chen CL 63