Catalysis of deuterium transfer between liquid chloroform and water by anion-exchange resins*1

Symons, E. A.; Bonnett, J.D.

doi:10.1016/0021-9517(85)90168-x

Cited by 4 publications

(3 citation statements)

References 20 publications

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“…CDCl 3 was prepared by the following procedure. 26 CHCl 3 (5 mL) was mixed with a 1 M NaOH solution in D 2 O (15 mL) at 35 • C under a N 2 atmosphere and the mixture was stirred vigorously for 1.5 h. In order to increase the yield of the deuteration, the product was again treated with NaOH in D 2 O for 1.5 h at 35 • C to obtain 90% isotope purity. CHCl 3 was prepared by an identical procedure using H 2 O rather than D 2 O.…”

Section: Methodsmentioning

confidence: 99%

“…Two samples of the same batch of CHCl 3 were treated with H 2 O-NaOH and D 2 O-NaOH under the same reaction conditions to obtain the samples of CHCl 3 and CDCl 3 with the same "handling history". 26 The formation of CDCl 3 was monitored by 13 C NMR. However, reaction of Au nanoparticles with these two solvents (in the presence of DMPO) confirmed that CHCl 3 gives only •CHCl 2 radical while CDCl 3 gives a mixture of •CCl 3 and •CDCl 2 .…”

Section: Halogen Abstractionmentioning

confidence: 99%

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Gold nanoparticle-initiated free radical oxidations and halogen abstractions

et al. 2007

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We report on the use of EPR spectroscopy and spin trapping technique to detect free radical intermediates formed in the presence of gold nanoparticles. Phosphine- and amine-protected gold nanoparticles were found to initiate air oxidation of organic substrates containing active hydrogen atoms, such as amines and phosphine oxides. Nanoparticles protected by stronger bound ligands (e.g., thiols) were inactive in these reactions. We also found that gold nanoparticles are able to abstract a halogen atom from the halogenated compounds, presumably due to the high affinity of gold metal for halogens. Reaction of Au nanoparticles with chloroform showed an unusual inverse isotope effect. The trichloromethyl spin adduct was observed when Au nanoparticles were mixed with CDCl(3) but not with CHCl(3). This unexpected behaviour suggests that C-H bond breaking is not the rate-determining step in Au-initiated hydrogen abstraction.

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Section: Methodsmentioning

confidence: 99%

Section: Halogen Abstractionmentioning

confidence: 99%

Gold nanoparticle-initiated free radical oxidations and halogen abstractions

et al. 2007

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“…This suggests that chloroform may undergo MPD at lower fluences than fluoroform (4,19,20). (b) The isotopic exchange rate between chloroform and water is faster than between fluoroform and water (21).…”

Section: Introductionmentioning

confidence: 99%

Multiphoton absorption and decomposition studies of chloroform-d induced by a pulsed ¹³CO₂ laser

McAlpine¹,

Goodale²,

Evans³

1985

Can. J. Chem.

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The multiphoton absorption (MPA) and decomposition (MPD) of chloroform-d induced by various "CO, [00°1 4 10°0] lines were studied for pressures from 0.133 to 13.3 kPa. MPA results show a cross-section increasing with pressure up to a plateau value which is likely due to rotational hole-filling. A MPA "spectrum" of the average number of photons absorbed versus wavenumber for different "CO, laser lines is shifted to lower wavenumbers compared to the small signal absorption spectrum by at least 5 cm-' suggesting that a small amount of anharmonicity bottle-necking is occurring in CDCI,. A comparison of the MPD probability versus fluence for CDCI3 with that measured by other workers for fluoroform indicates that the CDC13 is decomposed at a slightly lower fluence by an appropriate line of a pulsed CO, laser.For the pressure range (0.2 to 4.0 kPa) and laser pulse-width used, the MPD is second order in CDCI,. The primary decomposition channel is elimination of DCI followed by reaction of CCI, to give CzCIZ, C2C4, and CI,. The DCI produced exchanges with a source of H,O in the reaction cell to give significant quantities of HCI. A post-pulse reaction between (HCI + DCI) and C2CI2. produces (CrDC13 + C,HCl3). Significant quantities of CCI, are also produced by undetermined reactions.

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Base‐catalyzed tritium exchange between tritium‐containing heavy water and deuterated chloroform–kinetics and equilibrium

Maienschein

Barry

1986

Int J of Chemical Kinetics

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We develop a kinetic model for the exchange of tritium and deuterium between tritium-containing heavy water and deuterated chloroform in a two-phase liquid system, catalyzed by hydroxide ion (sodium hydroxide). For the exchange reaction yielding tritiated chloroform and heavy water, the measured equilibrium constant is 0.518 a t 25-45"C, independent of temperature. The rate constant (for the controlling step, deuteron abstraction from chloroform) is 0.22 L/mol s a t 25"C, 0.72 a t 3 5 T , and 2.0 a t 4 5 T , corresponding to an activation energy of 87 kJ/mol. Comparison is made with literature data, and effects of mass transfer on the apparent rate constant are discussed.

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Catalysis of deuterium transfer between liquid chloroform and water by anion-exchange resins*1

Cited by 4 publications

References 20 publications

Gold nanoparticle-initiated free radical oxidations and halogen abstractions

Gold nanoparticle-initiated free radical oxidations and halogen abstractions

Multiphoton absorption and decomposition studies of chloroform-d induced by a pulsed ¹³CO₂ laser

Base‐catalyzed tritium exchange between tritium‐containing heavy water and deuterated chloroform–kinetics and equilibrium

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Catalysis of deuterium transfer between liquid chloroform and water by anion-exchange resins*1

Cited by 4 publications

References 20 publications

Gold nanoparticle-initiated free radical oxidations and halogen abstractions

Gold nanoparticle-initiated free radical oxidations and halogen abstractions

Multiphoton absorption and decomposition studies of chloroform-d induced by a pulsed 13CO2 laser

Base‐catalyzed tritium exchange between tritium‐containing heavy water and deuterated chloroform–kinetics and equilibrium

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Multiphoton absorption and decomposition studies of chloroform-d induced by a pulsed ¹³CO₂ laser