Reactions of Atomic Hydrogen with Formic Acid and Carbon Monoxide in Solid Parahydrogen I: Anomalous Effect of Temperature

Paulson, Leif O.; Mutunga, Fredrick M.; Follett, Shelby E.; Anderson, David T.

doi:10.1021/jp502470j

Cited by 29 publications

(27 citation statements)

References 58 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…50,78,79 In particular, the formation of carboxyl radical by local reaction of hot OH radicals with CO molecules was observed in argon matrices by Mielke et al 79 Very recently, Paulson et al reported spectroscopic characterization of this radical resulting from reaction of hydrogen atoms with formic acid in a solid para-hydrogen matrix. 80 On the other hand, such a reaction was not found in a solid krypton matrix. 81 Meanwhile, here we present the first observation of formation of the HOCO radical as a result of radiation-induced evolution of the CO 2 −H 2 O system in condensed media.…”

Section: Resultsmentioning

confidence: 99%

Matrix-Isolation Studies on the Radiation-Induced Chemistry in H₂O/CO₂ Systems: Reactions of Oxygen Atoms and Formation of HOCO Radical

Ryazantsev

Feldman

2014

J. Phys. Chem. A

View full text Add to dashboard Cite

The radiation-induced transformations occurring upon X-ray irradiation of solid CO2/H2O/Ng systems (Ng = Ar, Kr, Xe) at 8-10 K and subsequent annealing up to 45 K were studied by Fourier transform infrared spectroscopy. The infrared (IR) spectra of deposited matrices revealed the presence of isolated monomers, dimers, and intermolecular H2O···CO2 complexes. Irradiation resulted in effective decomposition of matrix-isolated carbon dioxide and water yielding CO molecules and OH radicals, respectively. Annealing of the irradiated samples led to formation of O3, HO2, and a number of xenon hydrides of HXeY type (in the case of xenon matrices). The formation of these species was used for monitoring of the postirradiation thermally induced chemical reactions involving O and H atoms generated by radiolysis. It was shown that the radiolysis of CO2 in noble-gas matrices produced high yields of stabilized oxygen atoms. In all cases, the temperatures at which O atoms become mobile and react are lower than those of H atoms. Dynamics and reactivity of oxygen atoms was found to be independent of the precursor nature. In addition, the formation of HOCO radicals was observed in all the noble-gas matrices at remarkably low temperatures. The IR spectra of HOCO and DOCO were first characterized in krypton and xenon matrices. It was concluded that the formation of HOCO was mainly due to the radiation-induced evolution of the weakly bound H2O···CO2 complexes. This result indicates the significance of weak intermolecular interactions in the radiation-induced chemical processes in inert low-temperature media.

show abstract

Section: Resultsmentioning

confidence: 99%

Matrix-Isolation Studies on the Radiation-Induced Chemistry in H₂O/CO₂ Systems: Reactions of Oxygen Atoms and Formation of HOCO Radical

Ryazantsev

Feldman

2014

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…Similar H atom tunneling reactions have been observed for the reactions of H atoms with HONO (∼21 kJ mol –1 ), CH 3 OH (∼35 kJ mol –1 ), , H 2 NC(O)H (∼26 kJ mol –1 ), C 5 H 5 N (∼8 kJ mol –1 ), HC(O)OCH 3 (∼41 and 46 kJ mol –1 for the formation of HC(O)CH 2 and C(O)OCH 3 radicals, respectively), and CH 3 CONH 2 (∼41 kJ mol –1 ); predicted barriers are provided in parentheses. Paulson et al photolyzed HC(O)OH in solid p -H 2 at 1.7 K with laser light at 193 nm and observed tunneling reaction H + HC(O)OH because some H atoms were produced from photolysis; the reaction proceeded even after photolysis was terminated, resulting in the formation of HOCO from abstraction of the hydrogen on the carbon atom rather than the hydroxyl hydrogen. Similarly, in this work the H + CH 3 C(O)OH reaction proceeds through H-abstraction of the alkyl (CH 3 ) group that leads to the formation of the •CH 2 C(O)OH radical.…”

Section: Discussionmentioning

confidence: 99%

Hydrogen Abstraction of Acetic Acid by Hydrogen Atom to Form Carboxymethyl Radical •CH₂C(O)OH in Solid para-Hydrogen and Its Implication in Astrochemistry

Joshi¹,

How

Lee

2021

ACS Earth Space Chem.

View full text Add to dashboard Cite

Acetic acid CH 3 C(O)OH attracts significant attention in interstellar chemistry because it is considered to be a potential precursor for the formation of amino acids, such as glycine and alanine. The reaction NH 2 + •CH 2 C(O)OH within the ice mantles and on an ice surface is considered to be responsible for the formation of glycine from CH 3 C(O)OH. However, detailed experimental investigations are scarce. We took advantage of the unique properties of para-hydrogen (p-H 2 ), which serves as a quantum-solid matrix host and a medium for hydrogen-atom tunneling reactions, to investigate the reaction between CH 3 C(O)OH and H atoms. On photolysis at 365 nm of a CH 3 C(O)OH/Cl 2 /p-H 2 matrix to produce Cl atoms and subsequent infrared irradiation to produce H atoms by promoting Cl + H 2 (v = 1)

show abstract

“…Therefore, we decided to reinvestigate this system at two different temperatures, 1.8 and 4.3 K, respectively, to measure the effect of temperature on the reaction rate. Another reason to revisit this system is the anomalous results we have recently measured − for other H atom reactions in solid pH 2 . For example, in the case of the H + N 2 O → cis -HNNO reaction we observed a very strange temperature dependence .…”

Section: Introductionmentioning

confidence: 99%

Quantum Diffusion-Controlled Chemistry: Reactions of Atomic Hydrogen with Nitric Oxide in Solid Parahydrogen

Ruzi

Anderson

2015

J. Phys. Chem. A

Self Cite

View full text Add to dashboard Cite

Our group has been working to develop parahydrogen (pH2) matrix isolation spectroscopy as a method to study low-temperature condensed-phase reactions of atomic hydrogen with various reaction partners. Guided by the well-defined studies of cold atom chemistry in rare-gas solids, the special properties of quantum hosts such as solid pH2 afford new opportunities to study the analogous chemical reactions under quantum diffusion conditions in hopes of discovering new types of chemical reaction mechanisms. In this study, we present Fourier transform infrared spectroscopic studies of the 193 nm photoinduced chemistry of nitric oxide (NO) isolated in solid pH2 over the 1.8 to 4.3 K temperature range. Upon short-term in situ irradiation the NO readily undergoes photolysis to yield HNO, NOH, NH, NH3, H2O, and H atoms. We map the postphotolysis reactions of mobile H atoms with NO and document first-order growth in HNO and NOH reaction products for up to 5 h after photolysis. We perform three experiments at 4.3 K and one at 1.8 K to permit the temperature dependence of the reaction kinetics to be quantified. We observe Arrhenius-type behavior with a pre-exponential factor of A = 0.036(2) min(-1) and Ea = 2.39(1) cm(-1). This is in sharp contrast to previous H atom reactions we have studied in solid pH2 that display definitively non-Arrhenius behavior. The contrasting temperature dependence measured for the H + NO reaction is likely related to the details of H atom quantum diffusion in solid pH2 and deserves further study.

show abstract

Reactions of Atomic Hydrogen with Formic Acid and Carbon Monoxide in Solid Parahydrogen I: Anomalous Effect of Temperature

Cited by 29 publications

References 58 publications

Matrix-Isolation Studies on the Radiation-Induced Chemistry in H₂O/CO₂ Systems: Reactions of Oxygen Atoms and Formation of HOCO Radical

Matrix-Isolation Studies on the Radiation-Induced Chemistry in H₂O/CO₂ Systems: Reactions of Oxygen Atoms and Formation of HOCO Radical

Hydrogen Abstraction of Acetic Acid by Hydrogen Atom to Form Carboxymethyl Radical •CH₂C(O)OH in Solid para-Hydrogen and Its Implication in Astrochemistry

Quantum Diffusion-Controlled Chemistry: Reactions of Atomic Hydrogen with Nitric Oxide in Solid Parahydrogen

Contact Info

Product

Resources

About

Reactions of Atomic Hydrogen with Formic Acid and Carbon Monoxide in Solid Parahydrogen I: Anomalous Effect of Temperature

Cited by 29 publications

References 58 publications

Matrix-Isolation Studies on the Radiation-Induced Chemistry in H2O/CO2 Systems: Reactions of Oxygen Atoms and Formation of HOCO Radical

Matrix-Isolation Studies on the Radiation-Induced Chemistry in H2O/CO2 Systems: Reactions of Oxygen Atoms and Formation of HOCO Radical

Hydrogen Abstraction of Acetic Acid by Hydrogen Atom to Form Carboxymethyl Radical •CH2C(O)OH in Solid para-Hydrogen and Its Implication in Astrochemistry

Quantum Diffusion-Controlled Chemistry: Reactions of Atomic Hydrogen with Nitric Oxide in Solid Parahydrogen

Contact Info

Product

Resources

About

Matrix-Isolation Studies on the Radiation-Induced Chemistry in H₂O/CO₂ Systems: Reactions of Oxygen Atoms and Formation of HOCO Radical

Matrix-Isolation Studies on the Radiation-Induced Chemistry in H₂O/CO₂ Systems: Reactions of Oxygen Atoms and Formation of HOCO Radical

Hydrogen Abstraction of Acetic Acid by Hydrogen Atom to Form Carboxymethyl Radical •CH₂C(O)OH in Solid para-Hydrogen and Its Implication in Astrochemistry