Oxidation of Hydrazine in Aqueous Solution

Stanbury, David M.

doi:10.1002/9780470166482.ch5

Cited by 15 publications

(5 citation statements)

References 151 publications

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“…While the mechanism in Scheme shows stepwise additions of electrons and protons, it seems likely (at least to us) that at least some of these steps in catalysis would involve concerted transfers of both particles . Additionally, although the emphasis of this review is the transfer of equimolar amounts of H + / e – , significant effort has been dedicated to understanding reactions that have an excess of protons, e.g., N 2 to N 2 H 5 + , and we direct the readers to the following references for further details. , These basic principles should be general to most mechanisms for small-molecule transformations going through multiple PCET processes.…”

Section: Insights and Emerging Areas Of Pcet Thermochemistrymentioning

confidence: 97%

“…In many cases, the citation associated with a BDFE is for the related BDE, and the tabulated value was calculated using eq . Values in [square brackets] have been calculated from the other values in the row using Hess’ law. b E °(V vs H 2 ) of HN • NH-H in H 2 O was derived from those of N 2 /N 2 H 4 , N 2 /N 2 H 2 , and H 2 NNH-H. c Related values in MeCN or H 2 O have been reported, but they include computational components or different numbers of protons and electrons and therefore are not included here. , d –Δ G °/ n values are average free energies for the overall reaction shown except to form H • [rather than add H 2(g) ]. See Section . e Other values of Δ H ° f of N 2 H 4 exist, but a similar value was obtained from another thermochemical cycle in ref . f E °(V vs H 2 ) of N 2 /N 2 H 2 in the gas phase was derived from those of H 2 NNH-H, HN • NH-H, and N 2 /N 2 H 4 . …”

Section: Guide To the Thermochemical Tablesmentioning

confidence: 99%

“… c Related values in MeCN or H 2 O have been reported, but they include computational components or different numbers of protons and electrons and therefore are not included here. , …”

Section: Guide To the Thermochemical Tablesmentioning

confidence: 99%

“…135 Additionally, although the emphasis of this review is the transfer of equimolar amounts of H + /e − , significant effort has been dedicated to understanding reactions that have an excess of protons, e.g., N 2 to N 2 H 5 + , and we direct the readers to the following references for further details. 179,180 These basic principles should be general to most mechanisms for small-molecule transformations going through multiple PCET processes. The overall reaction 2NH 3 → N 2 + 6H • has a free energy per H atom (ΔG°/n) of 53.5 kcal mol −1 in MeCN (Table 13).…”

Section: N 2 Fixation and Ammonia Oxidationmentioning

confidence: 99%

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Free Energies of Proton-Coupled Electron Transfer Reagents and Their Applications

et al. 2021

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We present an update and revision to our 2010 review on the topic of protoncoupled electron transfer (PCET) reagent thermochemistry. Over the past decade, the data and thermochemical formalisms presented in that review have been of value to multiple fields. Concurrently, there have been advances in the thermochemical cycles and experimental methods used to measure these values. This Review (i) summarizes those advancements, (ii) corrects systematic errors in our prior review that shifted many of the absolute values in the tabulated data, (iii) provides updated tables of thermochemical values, and (iv) discusses new conclusions and opportunities from the assembled data and associated techniques. We advocate for updated thermochemical cycles that provide greater clarity and reduce experimental barriers to the calculation and measurement of Gibbs free energies for the conversion of X to XH n in PCET reactions. In particular, we demonstrate the utility and generality of reporting potentials of hydrogenation, E°(V vs H 2 ), in almost any solvent and how these values are connected to more widely reported bond dissociation free energies (BDFEs). The tabulated data demonstrate that E°(V vs H 2 ) and BDFEs are generally insensitive to the nature of the solvent and, in some cases, even to the phase (gas versus solution). This Review also presents introductions to several emerging fields in PCET thermochemistry to give readers windows into the diversity of research being performed. Some of the next frontiers in this rapidly growing field are coordination-induced bond weakening, PCET in novel solvent environments, and reactions at material interfaces.

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Section: Insights and Emerging Areas Of Pcet Thermochemistrymentioning

confidence: 97%

Section: Guide To the Thermochemical Tablesmentioning

confidence: 99%

“… c Related values in MeCN or H 2 O have been reported, but they include computational components or different numbers of protons and electrons and therefore are not included here. , …”

Section: Guide To the Thermochemical Tablesmentioning

confidence: 99%

Section: N 2 Fixation and Ammonia Oxidationmentioning

confidence: 99%

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Free Energies of Proton-Coupled Electron Transfer Reagents and Their Applications

et al. 2021

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“…The nucleophilic reaction of hydrazine with NO + to undergo nitrosation has been well thought out in the in vitro studies of dissimilatory nitrite reductases . The reactivity of hydrazine toward simple compounds as well as metal complexes is of much interest even at the mechanistic level, because it acts as a one-, two-, or four-equivalent reducing agent depending on the reaction conditions . The reaction between nitrous acid and hydrazine in aqueous solution is known to be a normal N-nitrosation .…”

Section: Introductionmentioning

confidence: 99%

Hydrazine Nitrosation of a Metal-Bound Nitric Oxide: Structural Evidence for the Formation of an Ammine Complex

et al. 2006

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Hydrazine nitrosation of [Ru(NO)(py(si)S4)]Br.THF (1) (py(si)S4(2-) = 2,6-bis(3-triphenylsilyl-2-sulfanylphenylthiomethyl)pyridine2-) in methanol/DMF led to the formation of mononuclear ammine complex [Ru(NH3)(py(si)S4)] (2) and N2O, whereas the reaction performed in THF/CH2Cl2/toluene afforded thioether-bridged dinuclear ammine complex [(NH3)Ru(mu-py(si)S4)Ru(py(si)S4)] (3). Compound 2 dimerizes in solution at room temperature to form 3 and is regenerated upon treatment of 3 with NH3. A plausible mechanism for the hydrazine nitrosation of 1 has been proposed. The reaction of 1 with NH3 or N3- does not lead to a nucleophilic attack at the NO+ ligand but to a deprotonation that yields neutral nitrosyl complex [Ru(NO){py(si)S4(H+)}] (4), which is supported by density functional theory calculations.

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Nitrogen: Inorganic ChemistryBased in part on the article Nitrogen: Inorganic Chemistry by Harry H. Sisler which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Hammerl¹,

Klap��tke²

2005

Encyclopedia of Inorganic Chemistry

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The chemistry of nitrogen and its compounds with hydrogen, oxygen, and halogens is discussed in this article. The high stability of the nitrogen–nitrogen triple bond in dinitrogen in comparison with nitrogen–nitrogen single or double bonds makes polynitrogen compounds promising, highly energetic materials. Recently, several new polynitrogen species have been detected experimentally and salts of the polynitrogen cation N 5 + have been isolated in bulk. Salts of the azide anion N 3 − are already used as highly energetic materials. Binary compounds of nitrogen and hydrogen include ammonia, hydrazine, and several metastable species with nitrogen–nitrogen bonds. Ammonia, which is the starting material for all industrially produced nitrogen compounds, is probably the most important industrial chemical. Most of the ammonia produced is used as fertilizer, whereas hydrazine is used as an energetic material. The monomeric nitrogen oxides are among the most simple odd‐electron molecules and play an important role in the chemistry of the atmosphere. In combustion engines, huge amounts of nitric oxide are formed, which influence the ozone cycle both in the troposphere and in the stratosphere. Nitric oxide is a chemical messenger in biological systems and it helps to regulate a diverse array of physiological processes, such as neurotransmission, blood pressure and blood clot prevention. Oxoacids of nitrogen include hydroxylamine, nitrous acid, and nitric acid. Nitric acid is a major industrial chemical, which is primarily used for nitrate fertilizer production. Hydroxylamine is a starting material for the production of polyamide synthetics. Chlorine, bromine, and iodine halogen nitrogen compounds include halogensubstituted derivatives of ammonia, hydrazine, and diimine. They are unstable species that decompose to molecules in excited states. Nitrogen fluorides are thermodynamically more stable than the other nitrogen halides. Ternary compounds of nitrogen, oxygen, and halogens include nitrosyl‐ and nitrylhalides as well as the halogen nitrates. The stability of these compounds decreases from fluorine to iodine.

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Oxidation of Hydrazine in Aqueous Solution

Cited by 15 publications

References 151 publications

Free Energies of Proton-Coupled Electron Transfer Reagents and Their Applications

Free Energies of Proton-Coupled Electron Transfer Reagents and Their Applications

Hydrazine Nitrosation of a Metal-Bound Nitric Oxide: Structural Evidence for the Formation of an Ammine Complex

Nitrogen: Inorganic ChemistryBased in part on the article Nitrogen: Inorganic Chemistry by Harry H. Sisler which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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