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- W2000205185 abstract "The effect of pressure on the kinetic isotope ratio kH/kD and tunnelling factor Q has been examined for proton and deutron transfer from 2,4,6-trinitrotoluene (TNT) to 1-ethylpiperidine in acetonitrile. The reaction rate has been measured in the pressure range 1–1000 bar and in the temperature range 15–35 °C by means of a high-pressure stopped-flow method. Even at 1000 bar, the kinetic isotope ratio kH/kD(16.4), the activation energy difference Ea(D)–Ea(H)(10.0 kJ mol–1) and the ratio of Arrhenius pre-exponential factor A(D)/A(H)(4.0) are large, suggesting a considerable tunnelling contribution. However, the tunnelling factor Q(H), calculated according to Bell's equation, hardly changes with pressure (being 2.39 at 1 bar and 2.26 at 1000 bar). Tunnelling phenomena and related pressure effects are discussed in relation to the curvature of potential-energy barriers. The present results lead us to conclude that large changes of kH/kD with pressure do not always confirm the occurrence of tunnelling." @default.
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- W2000205185 date "1985-01-01" @default.
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- W2000205185 title "Kinetic hydrogen isotope effects in the reaction between 2,4,6-trinitrotoluene and 1-ethylpiperidine in acetonitrile. The effect of pressure" @default.
- W2000205185 doi "https://doi.org/10.1039/f19858102959" @default.
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