Rates of Neutralization of C<sub>1</sub> to C<sub>4</sub> Nitroparaffins

Elving, Philip J.; Lakritz, Julian

doi:10.1021/ja01617a019

Cited by 8 publications

(4 citation statements)

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“…Our observed isotope effect of 9*3 is close to the value of 10 reported by Wynne-Jones (1934), though his deuterium experiments involved the reaction of nitroethane -1 -d2 with deuteroxide ions in deuterium oxide. For 2-nitropropane our value of &qH agrees well with 0*34 + 0*0 1m-1 s-1 found conductometrically in this laboratory (Kuhn i960), but is rather higher than 0*27 m-1 s-1 found by Elving & Lakritz (1955)-…”

Section: Kinetic Hydrogen Isotope Effects 287supporting

confidence: 90%

“…This was done by Maron & La Mer (1938) under conditions where nitromethane was only about half neutral ized, and their velocity constants for this substance are therefore probably in error. A similar, though smaller, error is involved in the measurements of Elving & Lakritz (1955) on the same reaction. The reactions of nitromethane and nitroethane with hydroxide ions have also been studied by the thermal maximum method (Bell & Clunie 1952;Bell & Panckhurst 1956;Jones, Longridge & Wynne-Jones 1965) which can be used for half-times down to a few seconds.…”

Section: Measurement Of Reaction Velocitiesmentioning

confidence: 92%

“…All our kinetic measurements have been carried out with ordinary water as solvent in order to avoid complications due to a solvent isotope effect in deuterium oxide. Most previous kinetic measurements on the reaction of nitroparaffins with hydroxide ions have been made by following the change in conductivity (Hantzsch & Veit 1889;Wynne-Jones 1934;Maron & La Mer 1938;Bell & Norris 1941;Elving & Lakritz 1955). In most instances the concentration of hydroxide was sufficiently high to make the neutralization of the nitroparaffin effectively complete, so th a t the kinetic equations for irreversible second order reactions can be used.…”

Section: Measurement Of Reaction Velocitiesmentioning

confidence: 99%

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Kinetic hydrogen isotope effects in the ionization of some nitroparaffins

Bell

Goodall

1966

Proc. R. Soc. Lond. A

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Values are reported for the kinetic hydrogen isotope effects for proton-transfer reactions between hydroxide ions and nitromethane, nitroethane, nitrocyclohexane and 2-nitropropane, and between 2-nitropropane and pyridine, 2, 6-lutidine and acetate ions. In conjunction with earlier work the results suggest that the isotope effect has a maximum value for proton transfers between two acid-base systems of approximately equal p K , in agreement with theoretical predictions. We have confirmed that the abstraction of a proton from 2-nitropropane by 2, 6-lutidine exhibits an abnormally high isotope effect ( k H / k D = 20), probably attributable to a considerable tunnelling correction.

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Section: Kinetic Hydrogen Isotope Effects 287supporting

confidence: 90%

Section: Measurement Of Reaction Velocitiesmentioning

confidence: 92%

Section: Measurement Of Reaction Velocitiesmentioning

confidence: 99%

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Kinetic hydrogen isotope effects in the ionization of some nitroparaffins

Bell

Goodall

1966

Proc. R. Soc. Lond. A

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“…The application of high frequency oscillators to the measurement of rate constants has been described previously (1)(2)(3), and their suitability for such determinations has been fully established. These workers made use of rather elaborate temperature-regulating equipment which pumped the sample solution (1) or the thermoregulating liquid (2) through a cell placed within the coil of a tuned oscillator circuit.…”

mentioning

confidence: 99%