Diels-Alder Reaction Experimental Design

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Model Formulation

Differential equation system:

$\begin{array}{rcl}\dot{n_1}(t)& =& -k\cdot \frac{n_1(t)\cdot n_2(t)}{m_{tot}},\\ & & \\ \dot{n_2}(t)& =& -k\cdot \frac{n_1(t)\cdot n_2(t)}{m_{tot}},\\ & & \\ \dot{n_2}(t)& =& k\cdot \frac{n_1(t)\cdot n_2(t)}{m_{tot}}\end{array}$

Solvent:

$\begin{array}{rcl}{n}_4& =& n_{a4}\end{array}$

Reaction velocity constant:

$k=k_1\cdot exp(-\frac{E_1}{R}\cdot (\frac{1}{T(t)}-\frac{1}{T_{ref}}))+k_{cat}\cdot c_{cat}\cdot exp(-\lambda \cdot t)\cdot exp(-\frac{E_{cat}}{R}\cdot (\frac{1}{T(t)}-\frac{1}{T_{ref}}))$

Total mass:

$m_{tot}=n_1\cdot M_1+n_2\cdot M_2+n_3\cdot M_3+n_4\cdot M_4$

Temperature in Kelvin:

$T(t)=\vartheta (t)+273$

The ODE system is summarized to:

$\begin{array}{rcl}\dot{x}(t)& =& f(x(t),u(t),p)\end{array}$

Optimum Experimental Design Problem

$\begin{array}{cll}\underset{x,G,F,u}{\min }& & trace(F^{-1}(t_{t_f}))\\ \text{s.t.}\\ \dot{x}(t)& =& f(x(t),u(t),p),\\ \\ \dot{h}(t)& =& \frac{n_3(t)\cdot M_3}{m_{tot}}\cdot 100\\ \\ \dot{G}(t)& =& f_x(x(t),u(t),p)G(t)+f_p(x(t),u(t),p)\\ \\ \dot{F}(t)& =& w(t)(h_x(x(t),u(t),p)G(t){)}^T(h_x(x(t),u(t),p)G(t))\\ \\ 0& =& g(x(t_o),x(t_f),p)\\ 0& \ge & c(x,u,p),\mathrm{\forall }t\in I\\ 0& =& h(x,u,p),\mathrm{\forall }t\in I\\ x& \in & {𝒳},u\in {𝒰},p\in P.\end{array}$

State variables

Name	Symbol	Initial value ($t_0$)
Molar number 1	$n_1(t)$	$n_1(t_0)=n_{a1}$
Molar number 2	$n_2(t)$	$n_2(t_0)=n_{a2}$
Molar number 3	$n_3(t)$	$n_3(t_0)=0$

Constants

Name	Symbol	Value
Molar Mass	$M_1$	0.1362
Molar Mass	$M_2$	0.09806
Molar Mass	$M_3$	0.23426
Molar Mass	$M_4$	0.236
Universal gas constant	$R$	8.314
Reference temperature	$T_{ref}$	293

Parameters

Name	Symbol	Value
Steric factor	$k_1$	$p_1\cdot 0.01$
Steric factor	$k_{kat}$	$p_2\cdot 0.10$
Activation energie	$E_1$	$p_3\cdot 60000$
Activation energie	$E_{kat}$	$p_4\cdot 40000$
Catalyst deactivation coefficient	$\lambda$	$p_5\cdot 0.25$

with $p_j=1,j=1,\dots ,5$

Control variables

Name	Symbol	Interval
Initial molar number 1	$n_{a1}$	[0.4,9.0]
Initial molar number 2	$n_{a2}$	[0.4,9.0]
Initial molar number 3	$n_{a3}$	[0.4,9.0]
Concentration of the catalyst	$c_{kat}$	[0.0,6.0]
Initial molar number 1	$\vartheta (t)$	[20.0,100.0]