Study of nButyl Acrylate SelfInitiation Reaction Experimentally and via Macroscopic Mechanistic Modeling
Abstract
:1. Introduction
 (i)
 Two monomers react and form a singlet diradical$$M+M\stackrel{\text{\hspace{1em}\hspace{1em}\hspace{1em}\hspace{1em}\hspace{1em}\hspace{1em}\hspace{1em}}}{\to}{}^{*}M{M}_{s}^{*}$$
 (ii)
 The singlet diradical then undergoes intersystem crossing to form a triplet diradical:$${}^{*}M{M}_{s}^{*}\stackrel{\text{\hspace{1em}\hspace{1em}\hspace{1em}\hspace{1em}\hspace{1em}\hspace{1em}\hspace{1em}}}{\to}{}^{*}M{M}_{t}^{*}$$
 (iii)
 The triplet diradical finally reacts with a third monomer, leading to the formation of two monoradicals:$${}^{*}M{M}_{t}^{*}+M\stackrel{\text{\hspace{1em}\hspace{1em}\hspace{1em}\hspace{1em}\hspace{1em}\hspace{1em}\hspace{1em}}}{\to}M{M}^{*}+{M}^{*}$$
2. Mathematical Modeling
2.1. Reaction Mechanisms
2.2. Rate Equations
2.3. Batch Reactor Model
3. Experimental and Analytical Procedures
4. Results and Discussion
Parameter Estimation
5. Concluding Remarks
Acknowledgments
Author Contributions
Conflicts of Interest
Appendix: Reaction Rate Equations
References
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Parameter  Frequency Factor  Activation Energy (kJ.mol^{−1})  Ref.  

${k}_{p}$  2.21 × 10^{7}  L·mol^{−1}·s^{−1}  17.9  [30] 
${k}_{p}^{t}$  1.20 × 10^{6}  L·mol^{−1}·s^{−1}  28.6  [49] 
${k}_{bb}$  7.41 × 10^{7}  s^{−1}  32.7  [33] 
${k}_{trM}$  2.90 × 10^{5}  L·mol^{−1}·s^{−1}  32.6  [47] 
${k}_{t}$  3.89 × 10^{9}  L·mol^{−1}·s^{−1}  8.4  [31] 
${k}_{t}^{tt}$  5.30 × 10^{9}  L·mol^{−1}·s^{−1}  19.6  [34] 
${k}_{\beta}$  1.49 × 10^{9}  s^{−1}  63.9  [34] 
${k}_{trP}$  4.01 × 10^{3}  L·mol^{−1}·s^{−1}  29.0  [15] 
${C}_{trS}$  1.07 × 10^{2}  35.4  [34] 
${k}_{t}={k}_{tc}+{k}_{td}$ 
${k}_{t}^{t}={k}_{tc}^{t}+{k}_{td}^{t}$ 
${k}_{t}^{tt}={k}_{tc}^{tt}+{k}_{td}^{tt}$ 
${k}_{td}={\delta}_{s}{k}_{t}$ 
${k}_{td}^{tt}={\delta}_{t}{k}_{t}^{tt}$ 
${k}_{td}^{t}={\delta}_{st}\sqrt{{k}_{t}{k}_{t}^{tt}}$ 
${k}_{tc}=\left(1{\delta}_{s}\right){k}_{t}$ 
${k}_{tc}^{tt}=\left(1{\delta}_{t}\right){k}_{t}^{tt}$ 
${k}_{tc}^{t}=(1{\delta}_{st})\sqrt{{k}_{t}{k}_{t}^{tt}}$ 
${k}_{trS}={C}_{trS}{k}_{p}$ 
${k}_{trM}^{t}=\frac{{k}_{p}^{t}}{{k}_{p}}{k}_{trM}$ 
${k}_{mac}=\gamma {k}_{p}$ 
Parameter  Dimensionless Value 

${\delta}_{s}$  0.1 
${\delta}_{st}$  0.7 
${\delta}_{t}$  0.9 
$\gamma $  0.5 
Temperature  This Work  Theoretical [11]  Theoretical [12] 
$T$  ${k}_{i}$  ${k}_{i}$  ${k}_{i}$ 
413  3.30 × 10^{−15}  2.81 × 10^{−18}  1.04 × 10^{−14} 
433  2.20 × 10^{−14}  2.86 × 10^{−17}  4.72 × 10^{−14} 
453  4.00 × 10^{−13}  2.37 × 10^{−16}  1.95 × 10^{−13} 
473  1.50 × 10^{−12}  1.64 × 10^{−15}  7.11 × 10^{−13} 
493  6.80 × 10^{−12}  9.74 × 10^{−15}  2.34 × 10^{−12} 
Parameter  This Work  Theoretical [11]  Theoretical [12] 
${E}_{i}$  165.51 ± 4.52  172.50  115.00 
$\mathrm{ln}{A}_{i}$  14.86 ± 1.20  9.68  1.38 
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Arabi Shamsabadi, A.; Moghadam, N.; Srinivasan, S.; Corcoran, P.; Grady, M.C.; Rappe, A.M.; Soroush, M. Study of nButyl Acrylate SelfInitiation Reaction Experimentally and via Macroscopic Mechanistic Modeling. Processes 2016, 4, 15. https://doi.org/10.3390/pr4020015
Arabi Shamsabadi A, Moghadam N, Srinivasan S, Corcoran P, Grady MC, Rappe AM, Soroush M. Study of nButyl Acrylate SelfInitiation Reaction Experimentally and via Macroscopic Mechanistic Modeling. Processes. 2016; 4(2):15. https://doi.org/10.3390/pr4020015
Chicago/Turabian StyleArabi Shamsabadi, Ahmad, Nazanin Moghadam, Sriraj Srinivasan, Patrick Corcoran, Michael C. Grady, Andrew M. Rappe, and Masoud Soroush. 2016. "Study of nButyl Acrylate SelfInitiation Reaction Experimentally and via Macroscopic Mechanistic Modeling" Processes 4, no. 2: 15. https://doi.org/10.3390/pr4020015