Letter Cite This: J. Phys. Chem. Lett. 2018, 9, 7040−7044
pubs.acs.org/JPCL
Criegee Intermediate Reaction with Alcohol Is Enhanced by a Single Water Molecule Yen-Hsiu Lin,†,‡ Cangtao Yin,† Wei-Hong Lin,† Yu-Lin Li,†,‡ Kaito Takahashi,*,† and Jim Jr-Min Lin*,†,‡ †
Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan
‡
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S Supporting Information *
ABSTRACT: The role of water in gas-phase reactions has gained considerable interest. Here we report a direct kinetic measurement of the reaction of synCH3CHOO (a Criegee intermediate or carbonyl oxide) with methanol at various relative humidity (RH = 0−80%) under near-ambient conditions (298 K, 250−755 Torr). The data indicate that a single water molecule expedites the reaction by up to a factor of three. The rate coefficient of the corresponding reaction, syn-CH3CHOO + CH3OH + H2O → products, has been determined to be (1.95 ± 0.11) × 10−32 cm6 s−1 at 298 K, with no observable pressure dependence for 250−755 Torr. Quantum chemistry calculation shows that the dominating pathway involves a hydrogen-bonded ring structure, in which methanol is donating a hydrogen atom to water, water is donating a hydrogen atom to the terminal oxygen atom of the Criegee intermediate, and, on the product side, H2O is reformed and acts as a catalyst.
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of the water-assisted reaction prevails over its energy gain (−ΔH) at the reaction barrier. More recently, Jara-Toro et al. reported water catalysis of the reaction of CH3OH with OH at near room temperature (294 K).8 However, because the rate coefficients of that work were determined by a relative measurement (CH3OH+OH versus C5H12+OH) in a simulation chamber (80 L collapsible Teflon bag), in which the reaction time (>102 s) was much longer than the lifetime of the involved radical species (3 kcal mol−1, resulting in a much larger rate coefficient (by ∼100 times). As a result, the corresponding product channel of CH3O(CH3)C(H)OOH formation (Figure 3K) would have a predominant yield. The origin of the methanol incorporation channel (Figure 3C,G) being much more favorable than the analogous water incorporation (Figure 3D,H) is an interesting question, and we are investigating the underlying mechanism for understanding the reactivity trend. Other minor channels (not shown in 7042
DOI: 10.1021/acs.jpclett.8b03349 J. Phys. Chem. Lett. 2018, 9, 7040−7044
Letter
The Journal of Physical Chemistry Letters
Computational. Geometry optimization and vibrational frequency calculations were performed by using the B3LYP functional with the 6-311+G(2d,2p) basis sets. The energies of prereactive complexes and transition states were refined using QCISD(T) complete basis set (CBS) extrapolation with Dunning’s basis sets, aug-cc-pVDZ, aug-cc-pVTZ, and augcc-pVQZ, at the B3LYP geometries. We performed conventional canonical transition state theory with the rigid-rotor harmonic-oscillator approximation using the Multiwell program to obtain the rate coefficients, which are given as k = Keqkrκ, where Keq is the equilibrium constant between the reactants and the prereactive complex, kr is the canonical reaction rate coefficient of the prereactive complex, and κ is the tunneling correction, which is estimated by the asymmetric Eckart barrier approximation. See the SI for details. The uncertainty in the quantum-chemistry energies is estimated to be about ±1 kcal mol−1, and the errors in the partition function calculations and tunneling corrections may lead to variations of a factor of ≤3 in the rate coefficients.
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Figure 4. Water enhancement factor plotted against relative humidity (RH) at 298 K with [H2O] shown on the top axis. The lines are linear fit. The color code (red, green, cyan, blue) follows the sequence of [CH3OH] (1.70, 2.66, ∼4, ∼7) × 1016 cm−3.
ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpclett.8b03349.
investigated the kinetics of the reactions of the simplest Criegee intermediate CH2OO with methanol, ethanol, and 2propanol. However, these groups did not study the effect of water on the reactions. Alcohol has been used as a scavenger for Criegee intermediates for decades.33−38 Whereas this scavenging is very efficient for anti conformers,23 our results indicate that the CH3OH monomer has only limited reactivity toward synCH3CHOO. Nonetheless, the alcohol scavenging may become more efficient under humid conditions. After N2 and O2, water is the third abundant gas in our atmosphere. This is the main reason why there are long-lasting discussions on water-assisted reactions. The title reaction adds a clear example to the quite scarce atmospheric reactions showing water enhancement. This work monitored synCH3CHOO with direct UV absorption in real time and thus avoided the complications arising from the uncertainty in the reaction mechanisms encountered in many relative rate measurements. Our experiment clearly demonstrates that a single H2O molecule is capable of significantly enhancing the reaction rate. Notably, this enhancement can be observed under near-ambient conditions (0.3 to 1 atm, 298 K, relative humidity = 20−80%).
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Experimental and theoretical methods and details (PDF)
AUTHOR INFORMATION
Corresponding Authors
*K.T.: E-mail:
[email protected]. *J.J.-M.L.: E-mail:
[email protected]. ORCID
Kaito Takahashi: 0000-0003-2339-4295 Jim Jr-Min Lin: 0000-0002-8308-2552 Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This work is supported by Academia Sinica and Ministry of Science and Technology, Taiwan (MOST 106-2113-M-001026-MY3 and MOST 106-2113-M-001-007-MY3).
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REFERENCES
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METHODS Experimental. A mixture of vapor or gases of CH3CHI2, CH3OH, ultrapure water, O2, and N2 was photolyzed by an excimer laser pulse (248 nm) in the reactor tube (ID 19 mm, L 750 mm) to initiate the reactions: CH3CHI2 + hν → CH3CHI + I and CH3CHI + O2 → CH3CHOO + I. The produced CH3CHOO was monitored by their strong UV absorption. The probe light (Energetiq, EQ-99) passed the reactor six times to enhance the absorption signal. The absorption change after the photolysis pulse (with respect to that before the photolysis pulse) at 340 nm (or 313 nm, used only in exp #1) was monitored in real time by using a balanced photodiode detector and recorded by a digital oscilloscope. The time traces were averaged for 120 laser pulses. See the SI for more details. 7043
DOI: 10.1021/acs.jpclett.8b03349 J. Phys. Chem. Lett. 2018, 9, 7040−7044
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DOI: 10.1021/acs.jpclett.8b03349 J. Phys. Chem. Lett. 2018, 9, 7040−7044
