function [] = WGS_COOH_ricky()

clear all
clc

global k2 k3 k4 k5 k6
global km2 km3 km4 km5 km6
global Keq1 Keq2 Keq3 Keq4 Keq5 Keq6 Keq7 KWGS
global FN2in FCOin FH2Oin FH2in FCO2in Ptot
global PCO PH2O PCO2 PH2

%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%
% 1.

CO + * <--> CO*

% 2.

H2O + 2* <--> OH* + H*

% 3.

CO* + OH* <--> COOH* + *

% 4.
% 5.
% 6.

COOH* + OH* <--> CO2 + H2O + 2*

2H* <--> H2 + 2*
COOH* + * <--> CO2 + H* + *

% 7. CO2 + 1/2H2 + 2* <--> HCOO**

%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%

%Reaction Feed and Conditions

sites=0.5996*0.000319;
GasN2in=91.3;

% mol
% cm3(STP)/min

GasH2in=201.3;
GasCOin=43.5;
GasCO2in=29.6;
GasH2Oin=180.0;
FN2in=GasN2in/22400/sites/60.0;

% sec-1

FH2in=GasH2in/22400/sites/60.0;
FCOin=GasCOin/22400/sites/60.0;
FCO2in=GasCO2in/22400/sites/60.0;
FH2Oin=GasH2Oin/22400/sites/60.0;
Ptot=2.7;

% atm

Trxn=200.0+273;

%K

%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%

%Initial Guesses for Catalyst Coverages

xOHin=1.0e-05;
xHin=0.2;
xCOOHin=1.0e-05;
xHCOOin=1.0e-05;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%

% Gas-phase Thermodynamics
HCO=-26.42+6.97*(Trxn-298.0)/1000;
HH2O=-57.80+8.03*(Trxn-298.0)/1000;
HH2=6.89*(Trxn-298.0)/1000;

% kcal/mol

HCO2=-94.05+8.87*(Trxn-298.0)/1000;
HOH=9.49+7.17*(Trxn-298.0)/1000;
HH=52.10+4.97*(Trxn-298.0)/1000;
HCOOH=-52.59+10.81*(Trxn-298.0)/1000;
HHCOO=-46.56+10.81*(Trxn-298.0)/1000;
SCO=47.30+6.97*log(Trxn/298.0);

% cal/mol/K

SH2O=45.10+8.03*log(Trxn/298.0);
SH2=31.21+6.89*log(Trxn/298.0);
SCO2=51.07+8.87*log(Trxn/298.0);
SOH=43.88+7.17*log(Trxn/298.0);
SH=27.39+4.97*log(Trxn/298.0);
SCOOH=59.45+10.81*log(Trxn/298.0);
%SHCOO=59.45+10.81*log(Trxn/298.0);
DHWGS=HH2+HCO2-HCO-HH2O;
DSWGS=SH2+SCO2-SCO-SH2O;
KWGS=exp(DSWGS/1.987-DHWGS*1000/1.987/Trxn);
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%

% Surface Thermodynamics
kB=1.38E-16;

% erg/K

hP=6.63e-27;

% erg sec

AMU=1.66e-24;

%g

Floc=1.0;
SOHM=Floc*(SOH-1.987*(log((2.0*3.14*17.0*AMU*kB*Trxn)^1.5/hP^3*kB*Trxn/2.74e

+06)+5.0/2.0));
SHM=Floc*(SH-1.987*(log((2.0*3.14*1.0*AMU*kB*Trxn)^1.5/hP^3*kB*Trxn/2.74e

+06)+5.0/2.0));
SCOOHM=Floc*(SCOOH-1.987*(log((2.0*3.14*45.0*AMU*kB*Trxn)

^1.5/hP^3*kB*Trxn/2.74e+06)+5.0/2.0));
SHCOOM=Floc*(SCOOH-1.987*(log((2.0*3.14*45.0*AMU*kB*Trxn)

^1.5/hP^3*kB*Trxn/2.74e+06)+5.0/2.0));
SCOM=Floc*(SCO-1.987*(log((2.0*3.14*28.0*AMU*kB*Trxn)^1.5/hP^3*kB*Trxn/2.74e

+06)+5.0/2.0));
BEOH=-68.4;

% kcal/mol

BEH=-60.4;
BECOOH=-52.0;
BEHCOO=-71.5;
BECO=-15.1;
HOHM=HOH+BEOH;
HHM=HH+BEH;
HCOOHM=HCOOH+BECOOH;
HHCOOM=HHCOO+BEHCOO;
HCOM=HCO+BECO;
DH1=HCOM-HCO;
DH2=HOHM+HHM-HH2O;
DH3=HCOOHM-HCOM-HOHM;
DH4=HCO2+HH2O-HCOOHM-HOHM;

DH5=HH2-2.0*HHM;
DH6=HHM+HCO2-HCOOHM;
DH7=HHCOOM-HCO2-HH2/2.0;
DS1=SCOM-SCO;
DS2=SOHM+SHM-SH2O;
DS3=SCOOHM-SCOM-SOHM;
DS4=SCO2+SH2O-SCOOHM-SOHM;
DS5=SH2-2.0*SHM;
DS6=SHM+SCO2-SCOOHM;
DS7=SHCOOM-SCO2-SH2/2.0;
Keq1=exp(DS1/1.987-DH1*1000/1.987/Trxn);
Keq2=exp(DS2/1.987-DH2*1000/1.987/Trxn);
Keq3=exp(DS3/1.987-DH3*1000/1.987/Trxn);
Keq4=exp(DS4/1.987-DH4*1000/1.987/Trxn);
Keq5=exp(DS5/1.987-DH5*1000/1.987/Trxn);
Keq6=exp(DS6/1.987-DH6*1000/1.987/Trxn);
Keq7=exp(DS7/1.987-DH7*1000/1.987/Trxn);
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%
% Rate Constants (all k's in units of sec-1)
%%%%%%%%%%%%%%%%%% Step 2 %%%%%
Eact2=15.2;

% kcal/mol

k2=1.01e+06/sqrt(2.0*3.14*18.0*AMU*kB*Trxn)/1.0e+15*exp(-Eact2*1000/1.987/Trxn);
km2=k2/Keq2;
E2=Eact2;
Em2=Eact2-DH2;

%%%%%%%%%%%%%%%%%% Step 3 %%%%%

Eact3=11.4;

% kcal/mol

if (DH3 < 0.0)

k3=1.00e+13*exp(-Eact3*1000/1.987/Trxn);
km3=k3/Keq3;
E3=Eact3;
Em3=Eact3-DH3;
else
km3=1.00e+13*exp(-Eact3*1000/1.987/Trxn);
k3=km3*Keq3;
Em3=Eact3;
E3=Eact3+DH3;
end
%%%%%%%%%%%%%%%%%% Step 4 %%%%%
Eact4=2.0;

% kcal/mol

A4=1.0e+015;
Am4=A4*exp(-DS4/1.987);
if (DH4 < 0.0)
k4=A4*exp(-Eact4*1000/1.987/Trxn);
km4=k4/Keq4;
E4=Eact4;
Em4=Eact4-DH4;
else
km4=Am4*exp(-Eact4*1000/1.987/Trxn);
k4=km4*Keq4;

Em4=Eact4;
E4=Eact4+DH4;
end
%%%%%%%%%%%%%%%%%% Step 5 %%%%%
Eact5=7.5;

% kcal/mol

km5=1.01e+06/sqrt(2.0*3.14*2.0*AMU*kB*Trxn)/1.0e+15*exp(-Eact5*1000/1.987/Trxn);
k5=km5*Keq5;
Em5=Eact5;
E5=Eact5+DH5;
%%%%%%%%%%%%%%%%%% Step 6 %%%%%
Eact6=20.0;

% kcal/mol

A6=1.0e+013;
Am6=A6*exp(-DS6/1.987);
if (DH6 < 0.0)
k6=A6*exp(-Eact6*1000/1.987/Trxn);
km6=k6/Keq6;
E6=Eact6;
Em6=Eact6-DH6;
else
km6=Am6*exp(-Eact6*1000/1.987/Trxn);
k6=km6*Keq6;
Em6=Eact6;
E6=Eact6+DH6;
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%

%Call ODE function

Uo = [FCOin;FH2Oin;FCO2in;FH2in;xOHin;xHin;xCOOHin;xHCOOin]; % Initial guesses
tspan=[0,1];

% Time Span

M=[1 0 0 0 0 0 0 0;
0 1 0 0 0 0 0 0;
0 0 1 0 0 0 0 0;
0 0 0 1 0 0 0 0;
0 0 0 0 0 0 0 0;
0 0 0 0 0 0 0 0;
0 0 0 0 0 0 0 0;
0 0 0 0 0 0 0 0]; % Mass Matrix
options=odeset('MStateDependence','none','MassSingular','yes','Mass',M,

'AbsTol', 1e-11);
[t,U]=ode23t(@eqnWGSFull,tspan,Uo,options);
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%
% final output
olength= length(U(:,1)');
FCO=U(olength,1);
FH2O=U(olength,2);
FCO2=U(olength,3);
FH2=U(olength,4);
xOH=U(olength,5);
xH=U(olength,6);
xCOOH=U(olength,7);

xHCOO=U(olength,8);
xv=(1.0-xH-xCOOH-2.0*xHCOO-xOH)/(1.0+Keq1*PCO);
xCO=Keq1*PCO*xv;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%
% net rates
rate2=k2*PH2O*xv^2-km2*xOH*xH;
rate3=k3*xCO*xOH-km3*xCOOH*xv;
rate4=k4*xCOOH*xOH-km4*PCO2*PH2O*xv^2;
rate5=k5*xH^2-km5*PH2*xv^2;
rate6=k6*xCOOH*xv-km6*PCO2*xH*xv;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%
% forward rates
rate2for=k2*PH2O*xv^2;
rate3for=k3*xCO*xOH;
rate4for=k4*xCOOH*xOH;
rate5for=k5*xH^2;
rate6for=k6*xCOOH*xv;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%
% reverse rates
rate2rev=km2*xOH*xH;
rate3rev=km3*xCOOH*xv;
rate4rev=km4*PCO2*PH2O*xv^2;
rate5rev=km5*PH2*xv^2;
rate6rev=km6*PCO2*xH*xv;

%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%
% reversibilities
z2=(km2*xOH*xH)/(k2*PH2O*xv^2);
z3=(km3*xCOOH*xv)/(k3*xCO*xOH);
z4=(km4*PCO2*PH2O*xv^2)/(k4*xCOOH*xOH);
z5=(km5*PH2*xv^2)/(k5*xH^2);
z6=(km6*PCO2*xH*xv)/(k6*xCOOH*xv);
ztot=PCO2*PH2/PCO/PH2O/KWGS;
z_overall = z2^1*z3^1*z4^1*z5^1*z6^1/ztot
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%
%Print to Screen
sprintf('Conversion = %f',(FCOin-FCO)/FCOin*100.0)
sprintf('TOF = %f',(FCOin-FCO)*60.0)
sprintf('DH1=%f',DH1)
sprintf('E2=%f Em2=%f DH2=%f',E2,Em2,DH2)
sprintf('E3=%f Em3=%f DH3=%f',E3,Em3,DH3)
sprintf('E4=%f Em4=%f DH4=%f',E4,Em4,DH4)
sprintf('E5=%f Em5=%f DH5=%f',E5,Em5,DH5)
sprintf('E6=%f Em6=%f DH6=%f',E6,Em6,DH6)
sprintf('DH7=%f',DH7)
sprintf('r2=%f r2for=%f r2rev=%f z2=%f',rate2,rate2for,rate2rev,z2)
sprintf('r3=%f r3for=%f r3rev=%f z3=%f',rate3,rate3for,rate3rev,z3)
sprintf('r4=%f r4for=%f r4rev=%f z4=%f',rate4,rate4for,rate4rev,z4)
sprintf('r5=%f r5for=%f r5rev=%f z5=%f',rate5,rate5for,rate5rev,z5)

sprintf('r6=%f r6for=%f r6rev=%f z6=%f',rate6,rate6for,rate6rev,z6)

sprintf('xH=%f xCO=%f xHCOO=%f xv=%f',xH,xCO,xHCOO,xv)
sprintf('xOH=%f xCOOH=%f',xOH,xCOOH)
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%
plot(t,(FCOin-U(:,1))*60.0)
xlabel('Length of Reactor')
ylabel('TOF (1/min)')
legend('FCO')

%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%
function [D] = eqnWGSFull(~,U)
global k2 k3 k4 k5 k6
global km2 km3 km4 km5 km6
global Keq1 Keq7
global FN2in Ptot
global PCO PH2O PCO2 PH2
% 1.

CO + * <--> CO*

% 2.

H2O + 2* <--> OH* + H*

% 3.

CO* + OH* <--> COOH* + *

% 4.

COOH* + OH* <--> CO2 + H2O + 2*

% 5.
% 6.

2H* <--> H2 + 2*
COOH* + * <--> CO2 + H* + *

% 7. CO2 + 1/2H2 + 2* <--> HCOO**

%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%
FCO=U(1);
FH2O=U(2);
FCO2=U(3);
FH2=U(4);
xOH=U(5);
xH=U(6);
xCOOH=U(7);
xHCOO=U(8);
Ftot=FCO+FH2O+FCO2+FH2+FN2in;
PCO=FCO/Ftot*Ptot;
PH2O=FH2O/Ftot*Ptot;
PCO2=FCO2/Ftot*Ptot;
PH2=FH2/Ftot*Ptot;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%
% rate expression information
xv=(1.0-xH-xCOOH-2.0*xHCOO-xOH)/(1.0+Keq1*PCO);
xCO=Keq1*PCO*xv;
rate2=k2*PH2O*xv^2-km2*xOH*xH;
rate3=k3*xCO*xOH-km3*xCOOH*xv;
rate4=k4*xCOOH*xOH-km4*PCO2*PH2O*xv^2;

rate5=k5*xH^2-km5*PH2*xv^2;
rate6=k6*xCOOH*xv-km6*PCO2*xH*xv;

%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%
% equations
D(1)= -rate3;
D(2)= -rate3;
D(3)= rate3;
D(4)= rate3;
D(5)= rate2-rate3-rate4;
D(6)= rate2-2.0*rate5+rate6;
D(7)= rate3-rate4-rate6;
D(8)= Keq7*PCO2*PH2^0.5*xv^2-xHCOO;
D=D';