Pulse radiolytic formation of solvated electrons in hydrazine

Seddon, W. A.; Fletcher, John; Sopchyshyn, F.C.

doi:10.1139/v76-397

Cited by 17 publications

(13 citation statements)

References 28 publications

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“…These observations are entirely consistent with the mechanism deduced by pulse radiolysis for solutions in ethylamine (6) (Csf, es-)loose, respectively. However, since the absorption spectra of the ( K f , e,-),,,,, and ( N a f , es-),oose are virtually the same at 213 K the distinction between the potassium and cesium ion-pairs is made by analogy with T H F solutions.…”

Section: Mixed Metal Solutions In Dme-spectrasupporting

confidence: 89%

“…The primary photolysis step metal solutions containing sodium/potassium, sois considered to be reaction [ l ] involving the forma-diumlrubidium, and sodium/cesium. The results tion of solvated electrons, e,-, and a species of clearly substantiate the conclusions reached earlier stoichiometry M, best regarded as a n ion-pair by pulse radiolysis (4,6). However, because of Na+ contamination and, what been given elsewhere (7).…”

Section: Introductionsupporting

confidence: 85%

“…As in KIDME solutions, we attribute this absorption to the formation of (K', e,-),,,,, or [7], followed by [6], [lo], and [ l l ] , are essentially complete to form (M', e,-). Some Na-is reformed on a -ps time scale by a combination of reactions [8], [9], :…”

Section: Mixed Metal Solutions In Dme-spectramentioning

confidence: 99%

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Flash photolysis of alkali metal anions in tetrahydrofuran and dimethoxyethane

Seddon¹,

Fletcher²,

Sopchyshyn³

et al. 1979

Can. J. Chem.

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Flash photolysis of K-, Rb-, and Cs-in tetrahydrofuran (THF) produces the corresponding ion-pairs ( K + , e,-), (Rb+, es-), and (Cs', e,-), followed by the regeneration of the parent metal anion, M u . In mixed-metal solutions containing Na and M where M is K, Rb, or Cs, photolysis of Na-also forms the ( M + , e,-) ion-pair and M-, but with the latter then reforming Na-on an extended time scale. Similar results were obtained in dimethoxyethane (DME) at 213 K, but in this case with the initial formation of a loose ion-pair, (M+, e,-),,,,,.

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Section: Mixed Metal Solutions In Dme-spectrasupporting

confidence: 89%

Section: Introductionsupporting

confidence: 85%

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Flash photolysis of alkali metal anions in tetrahydrofuran and dimethoxyethane

Seddon¹,

Fletcher²,

Sopchyshyn³

et al. 1979

Can. J. Chem.

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“…et al (1967), based on the data prepared by Maryott and Buckley (1953). They calculated the hydrazine's electric dipole moment based on their principal methods of dipole moment measurement and obtained a value of 1.75 D, which though in good agreement, underestimated the experimental value of 1.85 D reported by Seddon et al (1976). However, due to the advent of more powerful computational techniques and methods, researchers have shown more interest in calculating the electric dipole moment of hydrazine to the nearest accuracy, all in an attempt to bridge the gap between experiment and theory.…”

Section: Introductionmentioning

confidence: 69%

DMC and VMC Calculations of the Electric Dipole Moment and the Ground-State Total Energy of Hydrazine Molecule Using CASINO-Code

Ekong

Akpan

Ebomwonyi

2015

ILCPA

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In this study quantum Monte Carlo (QMC) calculations of the electric dipole moment and ground-state total energy of hydrazine (N 2 H 4 ) molecule using CASINO-code is presented. By employing the restricted HartreeFock (RHF) scheme, two QMC techniques were used in this work: variational Monte Carlo (VMC) and diffusion Monte Carlo (DMC) techniques. The optimization of the Slater-Jastrow trial wave-function was done using variance-minimization scheme. The simulations require that the configurations must evolve on the time scale of the electronic motion, and after equilibration, the estimated effective time-step be obtained. In this study, the electric dipole moment of N 2 H 4 molecule was calculated using only the DMC technique. The result obtained gives an electric dipole moment value of 2.0 D, which is in good agreement with the experimental value of 1.85 D. Similarly, the ground-state total energy of N 2 H 4 molecule was calculated using both VMC and DMC methods. It was observed that the result obtained from the VMC technique agrees very-well with the best theoretical value while the DMC technique gave a ground-state total energy value lower than all other theoretical values in literature, suggesting that the DMC result -111.842774 ± 0.00394 a.u., should be the exact ground-state total energy of hydrazine molecule. However, the results from this study are found to be precisely approaching the required order of chemical accuracy.

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“…This extremely short lifetimes. Extensive kinetic stud-paper deals with potential-sweep voltammetry and ies on the formation of chemical species composed potential-step chr~noamperometr~ of the anodic of alkali metal cation, M+, and free solvated oxidation of solvated electrons in methylamine and electron, e,-, in amines and ethers have been methylamine-ammonia mixtures in order to obtain carried out by means of this technique (2)(3)(4)(5)(6)(7)(8).…”

Section: Introductionmentioning

confidence: 99%

Dissociation kinetics of the solvated electron species in methylamine and methylamine–ammonia mixtures

Harima¹,

Kurihara²,

Nishiki³

et al. 1982

Can. J. Chem.

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Y. HARIMA, H. KURIHARA, Y. NISHIKI, S. AOYAGUI, K. TOKUDA, and H. MATSUDA. Can. J. Chem. 60, 445 (1982). Potential-sweep voltammetric and potential-step chronoamperometric experiments were made at -50°C with solvated electrons in methylamine containing LiC1, KI, or CsI. The dissociation rate constants of the ion pairs, (M+.e,-), M being alkali metal and e,-free solvated electron. were greater than lo3 s ' . The pseudo-first-order rate constant of the dissociation of K into the one-electron species, e , and (K',e,-) in rapid equilibrium, was determined as 40s-I by chronoamperometry with 0.5 M KI solutions. The formation constants of K-from the one-electron species determined by chronoamperometry and voltammetry were 4.5 x lo4 M-I and 5.6 x lo4 M-', respectively. An addition of a small amount of ammonia to methylamine caused a decrease in the formation constant of K and an increase in its dissociation rate constant. The appendix deals with a theoretical treatment of chronoamperograms for an electrode process preceded by the dissociation of a dimer. The boundary value problem was solved by the explicit finite difference method and the analytical method which was based on the concept of reaction layer. Chem. 60,445 (1982). Operant 8 -5O0C, on a procede a des experiences voltammetriques a variation lineaire de potentiel et chronoamperometriques a saut de potentiel avec des electrons solvates dans de la methylamine contenant du LiCL, du KI ou du CsI. Les constantes de vitesse de dissociation des paires d'ions, (M+.e,-), M etant le metal alcalin et e , I'electron solvate libre, sont plus grandes que lo3 s l . On a etabli que la constante de vitesse de dissociation de pseudo premier ordre de K en especes mono-electroniques, e,-et (M+.e,-) en Cquilibre rapide, est Cgale a 40 s-I, en faisant appel a la chronoamperometrie sur des solutions a 0.5 M de KI. Les constantes de formation de K-, telles que determinees par chronoamperometrie et voltammetrie, sont respectivement egales 84.5 x 104 M-' et 5.6 x 104 M 1 . L'addition de petites quantites d'ammoniac a la methylamine a provoque un accroissement de la vitesse de dissociation de l'espece bi-electronique et une decroissance de sa constante de formation. L'appendice presente un traitement theorique des chronoamperogrammes pour un processus d'electrode qui est procede par la dissociation d'un dimere. On a resolu le probleme de la valeur aux limites par la methode de la difference finie explicite et la methode analytique qui est basee sur le concept de la couche de reaction.[Traduit par le journal] Introduction (M+.e,-), and alkali metal anion, (M+.2eSp) or M-. Since Hart and Boag (I) in 1963 revealed the In Our electrochemical experiments e , and presence of solvated electrons in water by generat-(M+.es-) were recognized as species having one ing them with pulse radiolysis and detecting them excess electron, and M-, two excess electrons. with spectroscopy, this technique has developed were termed the One-and the two-electron quickly as a powerful tool to investigate solvated ...

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Pulse radiolytic formation of solvated electrons in hydrazine

Cited by 17 publications

References 28 publications

Flash photolysis of alkali metal anions in tetrahydrofuran and dimethoxyethane

Flash photolysis of alkali metal anions in tetrahydrofuran and dimethoxyethane

DMC and VMC Calculations of the Electric Dipole Moment and the Ground-State Total Energy of Hydrazine Molecule Using CASINO-Code

Dissociation kinetics of the solvated electron species in methylamine and methylamine–ammonia mixtures

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