Hydrogen forming reactions of thermal electrons in hydrogen halides: kinetics and thermodynamics

Nagra, Surjit S.

doi:10.1139/v76-515

Cited by 25 publications

(13 citation statements)

References 25 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The slow electrons from the gas discharge attach to the growing clusters, which are "hot" due to the heat of condensation liberated in the clustering process. The existence of the (HC1)~ has been inferred earlier from reactions in v-irradiated high pressure HC1 [11]. As will be discussed elsewhere in more detail, Nmi .…”

Section: Discussionmentioning

confidence: 67%

Electron attachment to clusters composed of closed shell, hydrogen containing molecules

Haberland

Ludewigt

Richter

1989

Z Phys D - Atoms, Molecules and Clusters

View full text Add to dashboard Cite

Electron attachment to clusters of HC1, H20, D20, C2H4(OH)2, NH 3, and ND 3 is compared. The clusters are produced in a seeded supersonic beam traversing a sustained gas discharge. For the first four molecules Nm~ n = 2 is the lowest number of molecules necessary to support a bound negative ion state. A much larger Nmin and an isotope effect is observed for ammonia, Nmin(NH3) = 35, and Nmin(ND3) = 41.

show abstract

Section: Discussionmentioning

confidence: 67%

Electron attachment to clusters composed of closed shell, hydrogen containing molecules

Haberland

Ludewigt

Richter

1989

Z Phys D - Atoms, Molecules and Clusters

View full text Add to dashboard Cite

show abstract

“…The magnitude of k,,, which determines the rate wheneveryN0-undergoes [21] (12) we find that 13% nitric oxide in HCl will captureelectrons at one tenth, one twentieth, and one fortieth the rate by HCI at concentrations of9.7 x 1018, 19.4 x 1018, and 38.9 x 1018 molecules cn1C3 respectively.…”

Section: Discussionmentioning

confidence: 76%

Effect of nitric oxide on hydrogen formation in irradiated HCl

Ballash¹,

Nagra²

1977

Can. J. Chem.

Self Cite

View full text Add to dashboard Cite

Nitric oxide reduces the production of hydrogen in irradiated HCl and leads to ClNO formation. The results can be interpreted on the basis of a competition between HCl and NO for H atoms and (HCl)x− negative ion intermediates. The yield of (HCl)x− = 2.4 ± 0.3 per 100 eV is similar to that found from experiments with chlorine, as was the total yield of scavengable H atoms plus electrons, ge + gH. From analyses of the competition kinetics for experiments both with and without added SF6, the ratio of the termolecular rate constant for reaction of H with NO in the presence of HCl as third body to that for reaction of H with HCl was estimated to be 6.3 ± 0.8 × 10−19 cm3 molecule−1 at 298 K.

show abstract

“…However, neither study gave a clear picture of the role of dimers or of the threshold energy for reaction (1). Evidence from radiation chemical studies conducted with gaseous HCl at 0.1 to 2 atmosphere pressure showed that thermal electrons could be captured, but the process was not an elementary DA as in reaction (1) 6, 22, 23. In that respect HCl differs from HBr, for which the threshold energy for reaction (1) is 0.0 eV and capture with thermal electrons is rapid 23–25.…”

Section: Introductionmentioning

confidence: 99%

Potential energy barriers for dissociative attachment to HF.HF and HCl.HCl: Ab initio study

Rauk

2003

Int J of Quantum Chemistry

View full text Add to dashboard Cite

has been investigated by theoretical calculations at MP2 and CCSD(T) levels with large basis sets. Transition structures (TSs) for the loss of an H atom and formation of the FHF Ϫ and ClHCl Ϫ anions were located by analytic methods. Initial electron attachment to HF.HF dimer occurs without activation and yields a dipole-bound anion state (DBS) as shown previously. Reaction (1) is endothermic by 65.8 kJ/mol at the CCSD(T)/augcc-pVDZ level. An intermediate ion-induced dipole complex between H ⅐ and FHF Ϫ is reached from the DBS over a potential barrier of 66.6 kJ/mol. Analysis of the charge distribution as a function of the distance to the departing H ⅐ reveals that the diffuse DBS collapses to a much more compact valence configuration prior to the TS being reached. In the valence configuration, the electron occupies the * orbital of the terminal HOF bond. DA to HCl.HCl differs from the fluorine case in several important respects. HCl.HCl does not form a DBS. Rather, electron attachment occurs by direct insertion into the * orbital of the terminal HOCl bond with an activation energy of 20.3 kJ/mol. As in the fluorine case, electron capture occurs before the TS. The electron density collapses to a valence configuration when the HOCl bond is stretched to about 1.45 Å, intermediate between that in the neutral dimer, 1.28 Å, and in the TS to DA, 1.57 Å. A "T-shaped" ion-induced dipole complex, bound by about 2 kJ/mol, lies between the TS and the separated H atom and ClHCl Ϫ anion products. With respect to DA, the chlorine system is intermediate between the fluorine system and the previously reported bromine system. The latter was found to undergo DA with a 0.0-kJ/mol barrier.

show abstract

Hydrogen forming reactions of thermal electrons in hydrogen halides: kinetics and thermodynamics

Cited by 25 publications

References 25 publications

Electron attachment to clusters composed of closed shell, hydrogen containing molecules

Electron attachment to clusters composed of closed shell, hydrogen containing molecules

Effect of nitric oxide on hydrogen formation in irradiated HCl

Potential energy barriers for dissociative attachment to HF.HF and HCl.HCl: Ab initio study

Contact Info

Product

Resources

About