The Role of (H2O)1-2 in the CH2O + ClO Gas-Phase Reaction
Abstract
:1. Introduction
2. Computational Methods
3. Results and Discussion
3.1. Mechanism of the CH2O + ClO Reaction in the Absence of Water Vapor
3.2. Mechanism of the CH2O + ClO Reaction in the Presence of Water Vapor
3.2.1. Reaction Between (H2O)1–2 and IM1/IM2/IM3 Complexes−
3.2.2. Mechanism of the CH2O···(H2O)1-2 + ClO and ClO···(H2O)1–2 + CH2O Reactions
3.3. Kinetics
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Sample Availability: Samples of the compounds are not available from the authors. |
System | ΔE | Δ(E + ZPE) | ΔH(298 K) | ΔG(298 K) |
---|---|---|---|---|
CH2O + ClO | 0 | 0 | 0 | 0 |
IM1 | −2.5 | −1.7 | −0.7 | 6.0 |
TS1 | 6.9 | 4.6 | 1.7 | 9.8 |
PC1 | −10.0 | −10.2 | −10.0 | −5.3 |
HCO + HOCl | −6.7 | −8.2 | −9.4 | −10.9 |
IM2 | −0.2 | 0.3 | 1.1 | 6.9 |
TS2 | 16.8 | 17.4 | 17.1 | 26.7 |
IM2a | −5.7 | −3.6 | −2.6 | 7.5 |
TS2a | 14.9 | 12.6 | 9.4 | 19.4 |
IM2b | 7.0 | 4.2 | 1.3 | 8.8 |
TS2b | 18.3 | 15.7 | 12.5 | 21.4 |
PC2 | −52.6 | −54.0 | −55.6 | −48.2 |
HCOO + HCl | −49.0 | −52.7 | −56.0 | −56.4 |
IM3 | −3.7 | −2.9 | −1.9 | 4.6 |
TS3 | 12.8 | 13.4 | 13.0 | 22.6 |
IM3a | −6.8 | −4.5 | −3.2 | 6.9 |
TS3a | 13.4 | 11.3 | 8.1 | 18.2 |
PC3a | 4.4 | 1.7 | −1.0 | −1.0 |
H + HC(O)OCl | 4.7 | 1.6 | −1.6 | 1.5 |
TS3b | 27.1 | 25.6 | 23.2 | 32.9 |
PC3b | −62.2 | −58.9 | −56.0 | −48.3 |
Cl + HC(O)OH | −60.5 | −57.5 | −54.9 | −52.6 |
System | ΔE | Δ(E + ZPE) | ΔH(298 K) | ΔG(298 K) |
---|---|---|---|---|
CH2O + ClO + H2O | 0 | 0 | 0 | 0 |
IM1-W | −10.5 | −7.7 | −5.0 | 9.3 |
TS1-W | 0 | −0.2 | −1.2 | 15.2 |
PC1-W | −14.3 | −12.9 | −11.2 | 2.2 |
IM2-W | −7.0 | −4.7 | −2.2 | 9.8 |
TS2-W | 12.8 | 14.7 | 15.8 | 32.4 |
IM2a-W | −10.5 | −7.1 | −4.6 | 12.4 |
TS2a-W | 9.2 | 8.5 | 6.8 | 23.8 |
IM2b-W | 2.0 | 0.8 | −0.5 | 14.4 |
TS2b-W | 12.6 | 11.6 | 9.9 | 24.8 |
PC2-W PC2-W2 | −62.3 −17.4 | −61.0 −15.5 | −61.1 −13.7 | −43.2 0.4 |
HCl + HCOO + H2O | −49.0 | −52.7 | −56.0 | −56.4 |
System | ΔE | Δ(E + ZPE) | ΔH(298 K) | ΔG(298 K) |
---|---|---|---|---|
CH2O + ClO + H2O | 0 | 0 | 0 | 0 |
CH2O···H2O + ClO | −5.6 | −3.7 | −2.0 | 4.5 |
ClO···H2O + CH2O | −3.5 | −2.4 | −1.4 | 4.0 |
H2O···ClO + CH2O | −3.6 | −2.8 | −1.8 | 3.8 |
IM1W1 | −8.1 | −5.6 | −3.0 | 10.2 |
TS1W1 | 2.3 | 1.3 | −0.1 | 14.8 |
PC1W1 | −17.4 | −15.5 | −13.7 | 0.4 |
IM2W1 | −4.8 | −2.4 | −0.1 | 14.9 |
TS2W1 | 1.1 | 1.0 | −0.1 | 16.5 |
IM2W2 | −10.5 | −7.7 | −5.0 | 9.3 |
TS2W2 | 0 | −0.2 | −1.2 | 15.2 |
IM2W3 | −9.2 | −6.8 | −4.3 | 9.8 |
TS2W3 | 41.8 | 39.4 | 35.7 | 53.7 |
PC2W1(PC2W2) | −17.4 | −15.5 | −13.7 | 0.4 |
PC2W3 | −19.7 | −17.3 | −15.3 | −0.1 |
HCO + HOCl + H2O | −6.7 | −8.2 | −9.4 | −10.9 |
System | ΔE | Δ(E + ZPE) | ΔH(298 K) | ΔG(298 K) |
---|---|---|---|---|
CH2O + ClO + (H2O)2 | 0 | 0 | 0 | 0 |
CH2O···(H2O)2 + ClO | −14.5 | −9.9 | −6.4 | 9.5 |
ClO···(H2O)2 + CH2O | −10.3 | −7.1 | −4.4 | 10.1 |
IMWW1 | −16.9 | −11.8 | −7.5 | 15.4 |
TSWW1 | −6.8 | −5.3 | −4.9 | 19.4 |
PCWW1 | −22.6 | −18.8 | −15.3 | 6.1 |
IMWW2 | −15.9 | −11.2 | −6.9 | 10.1 |
TSWW2 PCWW2 | −5.4 −22.6 | −4.2 −18.8 | −4.0 −15.3 | 15.2 21.2 |
HCO + HOCl + 2H2O | −6.7 | −8.2 | −9.4 | −10.9 |
h (km) | T (K) | k1 | kIM1-W1 | kRW1 | kRW2 | kRW3 | |
---|---|---|---|---|---|---|---|
0 | 298.15 | 2.6 × 10−16 | 4.2 × 10−20 | 5.7 × 10−20 | 6.7 × 10−21 | 4.2 × 10−20 | |
0 | 288.19 | 1.8 × 10−16 | 3.5 × 10−20 | 4.4 × 10−20 | 5.4 × 10−21 | 3.5 × 10−20 | |
2 | 275.21 | 1.1 × 10−16 | 2.7 × 10−20 | 3.0 × 10−20 | 3.9 × 10−21 | 2.7 × 10−20 | |
4 | 262.23 | 6.5 × 10−17 | 2.1 × 10−20 | 2.0 × 10−20 | 2.8 × 10−21 | 2.1 × 10−20 | |
6 | 249.25 | 3. 6 × 10−17 | 1.5 × 10−20 | 1.3 × 10−20 | 2.0 × 10−21 | 1.5 × 10−20 | |
8 | 236.27 | 1.8 × 10−17 | 1.1 × 10−20 | 8.0 × 10−21 | 1.3 × 10−21 | 1.1 × 10−20 | |
10 | 223.29 | 8.8 × 10−18 | 7.6 × 10−21 | 4.7 × 10−21 | 8.3 × 10−22 | 7.6 × 10−21 | |
12 | 216.69 | 5.9 × 10−18 | 6.2 × 10−21 | 3.5 × 10−21 | 6.5 × 10−22 | 6.2 × 10−21 |
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Li, J.; Tsona, N.T.; Du, L. The Role of (H2O)1-2 in the CH2O + ClO Gas-Phase Reaction. Molecules 2018, 23, 2240. https://doi.org/10.3390/molecules23092240
Li J, Tsona NT, Du L. The Role of (H2O)1-2 in the CH2O + ClO Gas-Phase Reaction. Molecules. 2018; 23(9):2240. https://doi.org/10.3390/molecules23092240
Chicago/Turabian StyleLi, Junyao, Narcisse T. Tsona, and Lin Du. 2018. "The Role of (H2O)1-2 in the CH2O + ClO Gas-Phase Reaction" Molecules 23, no. 9: 2240. https://doi.org/10.3390/molecules23092240