Hydrolysis of (trimethylamine)borane with ion-exchange resins: effect of ionic surfactants

Bromberg, Lev; Muraviev, Dmitri; Warshawsky, Abraham

doi:10.1021/j100153a077

Cited by 8 publications

(9 citation statements)

References 5 publications

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“…As a class of promising hydrogen storage materials, the hydrolysis mechanism of borohydride-rich compounds (e.g., NaBH 4 ) has been extensively studied. − Also, the interaction of water with ionic liquids in other fields has been discussed widely. − These can be treated as references for the hydrolysis of borohydride-rich anions of HILs. To further understand the relationships between hypergolicity and water stability, here we try to study the chemical transformation pathways and interaction effects of eight borohydride-rich anions, i.e., borohydride (BH 4 – ), cyanoborate (BH 3 CN – ), dicyanoborate (BH 2 (CN) 2 – ), cyanoimidazolylborohydride (CIB – ), bis(borano)hypophosphite ([BH 3 PH 2 BH 3 ] − , BPB – ), cyano-bridged dicyanoborohydride ([BH 3 CNBH 2 CN] − , BCNBCN – ), cyanotetrazolylborohydride (CTB – ), and bishydrobis(tetrazol-1-yl)borate (BTB – ) (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study on Hydrolytic Stability of Borohydride-Rich Hypergolic Ionic Liquids

Jin

Shi

et al. 2020

J. Phys. Chem. A

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Hypergolic ionic liquids (HILs) are a new kind of green rocket fuels, which are used as potential replacements for toxic hydrazine derivatives in liquid bipropellants. These functional HILs can react with oxidizers and release a large amount of heat in a very short time, finally leading to ignition of the propellant system. Among them, most borohydride-rich HILs were very sensitive to water, but a few special examples displayed good hydrophobicity and remained very stable in air even after a month or more. However, the reasons behind their hydrolytic stability are unclear. In this study, several calculation methods including electrostatic potentials (ESPs), molecular orbital energy gaps, and interaction energy were used to explore the water stability of eight typical borohydride-rich HILs. The obtained results demonstrated that negatively charged anions with high absolute ESP values usually reacted more easily with positively charged water. The large molecular orbital energy gap with BPB − , BCNBCN − , CTB − , and BTB − indicates the high degree of difficulty of interactions between anions and water, leading to a better hydrolytic stability of borohydride-rich anions. During the analyses of interaction energy, the relatively water-sensitive borohydride-rich anions (BH 4 − , BH 3 CN − , etc.) generally had lower interaction energy with water than stable anions such as BPB − and BCNBCN − . Studies on their stepwise hydrolysis mechanism demonstrate that, in the case of all the reactions, the first step is the rate-determining step and high energy barrier values of anions correspond to good hydrophobicity. This study will help us understand the hydrolysis of borohydride-rich HILs and provide a guide for the development of new HILs with promising properties.

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Section: Introductionmentioning

confidence: 99%

Theoretical Study on Hydrolytic Stability of Borohydride-Rich Hypergolic Ionic Liquids

Jin

Shi

et al. 2020

J. Phys. Chem. A

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“…In particular, the interaction between a polyelectrolyte and an oppositely charged surfactant, which is the analogue of the poly(VP−DTPA) system, is strongly favored, and a decrease of the cac relative to the critical micelle concentration (cmc) of the surfactant by several orders of magnitude is commonly observed . This interaction is frequently so strong that it can lead to the formation of water-insoluble complexes which if redissolved in organic solvents, still remain in a form of polyelectrolyte−surfactant associates …”

Section: Resultsmentioning

confidence: 99%

Swelling of Polymeric Resins in Organic Solvents Induced by Dialkyldithio-Containing Extractants

Bromberg

1996

J. Phys. Chem.

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The phenomenon of swelling resulting in volume transitions of cross-linked poly(4-vinylpyridine) and poly-(N,N-dimethylacrylamide) resins in organic solvents induced by bis(2-ethylhexyl)dithiophosphoric and bis-(2,4,4-trimethylpentyl)dithiophosphinic acids is demonstrated. Observed volume transitions in resins are explained by the dithioacid-polymer complexation analogous to the surfactant-polymer association in aqueous media.

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“…The cation-exchange membranes composed of highly sulfonated polyethylene were supplied by Soreq Nuclear Research Center, Israel. The kinetics of TMAB hydrolysis was studied under batch conditions as described elsewhere (37,38) and was followed by both FTIR analysis and volumetric measurements of the gas evolving the reactor (see Eq. The isotope-exchange reaction was monitored by Fourier transform infrared (FTIR) analysis following the disappearance of the strong B-H absorption band at 2360 cm Ϫ1 and the appearance of the broad B-D band at 1783 cm Ϫ1 , indicating BH 3 and BD 3 antisymmetric stretches, respectively (36).…”

Section: General Backgroundmentioning

confidence: 99%

“…This inhibition is explained by the surface activity of TMA ions, which resemble the cationic surfactants, known to slow down the process of ion exchange (see below) and even poison resins (38,41). Finally, the gradual loading of the cation exchanger with TMA begins inhibiting the ion-exchange process.…”

Section: Muraviev and Warshawskymentioning

confidence: 99%

Aqua-Impregnated Resins as New Dual-Function Deuterating Agent

Muraviev

Warshawsky

2001

Separation Science and Technology

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This study reviews our work on novel approaches for carrying out hydrogen-deuterium (H-D) exchange reactions, culminating in a process to produce extremely pure deuterated organic compounds using solid (polymeric) reagents, e.g., cation exchangers in the deuterium form pre-swollen in deuterium oxide (D 2 O). H-D exchange reaction carried out by cation-exchange deuterating agents in a tri-phase liquid-liquid-solid systems (TMAB solution in CCl 4 -D 2 O-resin in the D-form) is accompanied by significant hydrolysis of both TMAB and TMAB-d 3 (deuterated TMAB). Substitution of the liquid aqueous phase by D 2 O taken up by the swollen resin phase eliminates the hydrolytic side-reaction. Hydrogen-deuterium exchange reaction on TMAB catalyzed by cation-exchange resins or membranes under batch or under dynamic conditions, in columns, results in 100% yield of spectroscopically pure TMAB-d 3 .

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Hydrolysis of (trimethylamine)borane with ion-exchange resins: effect of ionic surfactants

Cited by 8 publications

References 5 publications

Theoretical Study on Hydrolytic Stability of Borohydride-Rich Hypergolic Ionic Liquids

Theoretical Study on Hydrolytic Stability of Borohydride-Rich Hypergolic Ionic Liquids

Swelling of Polymeric Resins in Organic Solvents Induced by Dialkyldithio-Containing Extractants

Aqua-Impregnated Resins as New Dual-Function Deuterating Agent

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