Kinetic mass spectrometric investigation of the reactions of t-C4H9+ ions with some simple polar molecules at thermal energies

Hellner, L.; Sieck, L. Wayne

doi:10.6028/jres.075a.039

Cited by 11 publications

(7 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The above observations concerning ion-dipole effects are in contrast to the conclusions reached by Hellner and Sieck (24). They observed that proton-transfer reactions from t-C,H,+ (produced by photoionization of neopentane) to acetone, ammonia, and various methyl amines all had rate coefficients which could be ex~lained by ion-induced dipole interactions only and they concluded that ion-dipole effects were unimportant.…”

Section: Discussioncontrasting

confidence: 55%

“…The thermochemically permitted reactions are1 ' "Thermochemical calculation employs AH,((CH,),-COH+) = 125 kcal mol-' (22,23). A value of 111 kcal mol-I has also been reported (24 Figure 9a shows the variation of ion intensities with time between 0.5 and 2.0 ms in a 157: 1.0 CH4-(CH,),CO mixture where CH5+ is the only reactant ion produced from methane. Figure 9b shows the plot of product ion intensities us.…”

Section: Methane-acetonementioning

confidence: 99%

See 1 more Smart Citation

Bimolecular Reactions of Trapped Ions. VI. Ion–Molecule Reactions Involving CH₅⁺ and C₂H₅⁺

Blair¹,

Harrison²

1973

Can. J. Chem.

View full text Add to dashboard Cite

The ion-molecule reactions in mixtures of methane with the polar molecules dimethyl-& ether, ethylene-d4 oxide, acetaldehyde-d,, acetone, and acetonitrile have been studied sing the trapped-ion technique. The C H s + and C2Hs+ ions produced by ion-molecule reactions in methane react rapidly (predominantly by proton transfer) with the polar molecules; the rate coefficients range from 1.98 x cm3 molecule-I s-' (C2HS+ + C2D40) to 5.26 x cm3 molecule-' s-I (CHSi f (CH3),CO). The rate coefficients are much larger than those predicted from ion -induced dipole interactions only indicating that ion-dipole interactions play a large role in the collision process.Rate coefficients for reaction of CH3+ and CH,+ with the polar molecules also have been measured. Most of these also are larger than predicted from ion -induced dipole interactions indicating in this case as well substantial effects due to ion-dipole interactions.Les reactions ion-molecule dans des melanges de methane avec des molCcules polaires du type dimethylether-d6, oxyde d'ethylene-rl,, acetone et acetonitrile, ont ete t t~~d i e e s par la technique de captage ionique. Les ions CH, + et C2H,+ issus des reactions ion-moltcule dans le methane rkagissent rapidement (surtout par transfert de proton) avec les molecules polaires; I'intervalle des coefficients de vitesse va de

show abstract

Section: Discussioncontrasting

confidence: 55%

Section: Methane-acetonementioning

confidence: 99%

Bimolecular Reactions of Trapped Ions. VI. Ion–Molecule Reactions Involving CH₅⁺ and C₂H₅⁺

Blair¹,

Harrison²

1973

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…At low CH4 pressures, reaction 14 competes with reaction 13. As the C2H2CI2 pressure is increased, the CH4 •+ intensity decreases via reaction 14 with a resultant decrease in the amount of CHS+ formed via reaction 13. Thus it appears that CHS+ is reacting with C2H2CI2 at a larger rate than the true rate of reaction 15.…”

Section: Methodsmentioning

confidence: 99%

“…The ion cyclotron resonance spectrometer used for the experimental studies is of conventional design and has been discussed in detail elsewhere.1*17 All experiments were carried out at about 300°K. Reactant ions H3+ (or D3+) and CHS+ (or CD5+) were produced by the reactions H,• + + H2-> H3+ + • H ( 12) and CH4-+ + CH4 -CHs+ + • CH3 (13) 30-eV electrons were used to form the methane and hydrogen ions. Thermal energy rate constants were measured by observing the decrease of reactant ion intensity at constant methane or hydrogen pressure while increasing the target gas pressure.…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Ion-polar molecule collisions. Proton transfer reactions of H3+ and CH5+ to the geometric isomers of difluoroethylene, dichloroethylene, and difluorobenzene

Su¹,

Bowers²

1973

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Proton transfer rate constants from CH5+, CD5+, H3+, and D3+ to difluoroethylene, dichloroethylene, and difluorobenzene isomers have been measured at thermal ion energies and compared with a classical theory of the ion-dipole interaction. Most experimental rate constants of nonpolar isomers are close to those predicted by the charge-induced dipole theory. Experimental and theoretical results for the polar isomers are also in good quantitative agreement. The effects of a permanent dipole on proton-transfer reactions are much less than predicted by the locked-dipole approximation, and the dipole effect increases with increasing µ / /'-ratio.Recent papers from this laboratory1•2 have reported . the charge-transfer reactions of rare gas ions with difluoroethylene, dichloroethylene, and difluorobenzene geometric isomers. It was shown that the effects of a permanent dipole on charge-transfer1•2 reactions are much smaller than expected by the "locked-dipole" approximation. The average dipole orientations are near tt/2 with respect to the line of collision. A classical theoretical model considering the thermal molecular rotational energy has been developed2 to estimate the capture cross-sections for ion-dipole reactions. The charge-transfer rate constants previously measured1•2 were considered to be composed of two components k = kcap + ke j(1) kcap corresponds to collisions occurring with impact parameters less than or equal to the capture limit. kej corresponds to collisions exceeding the capture limit where it is assumed the charge-transfer reaction takes place via a nonadiabatic electron jump.3•4 The theoretical predictions were in excellent agreement with experimental values of kcap. It was assumed that the long-range electron jump reactions show little dependence on the dipole moment.5 Here, we report a study of the proton-transfer reactions from CHS+, CD3+, H3+, and D3+ to the three sets of isomers mentioned above and compare the dipole effects with theoretical predictions. H3+ and CH5+ are easily accessible sources of protons that can readily be transferred to most gaseous molecules. Such transfers are often highly exothermic due to the low proton affinities of H26•7 and CH4.8 These reactions differ from the charge transfer reactions in that a massive particle is transferred rather than an electron and that the transferred particle originates on the impacting ion rather than the neutral molecule.(1) . T. Bowers and J. B. Laudenslager, J. Chem. Phys., 56, 4711 (1972).(2) T. Su and . T. Bowers, ibid., in press.(3) . T. Bowers and D. D. Elleman, Chem. Phys. Lett., 16, 486 (1972).(4) J. Gauglhofer and L. Kevan, ibid., 16, 492 (1972).(5) Theoretical calculations (ref 2) indicate that at collision diameters significantly larger than orbiting, virtually no orientation of the dipole occurs.

show abstract

Isomerization of C₄H₉⁺ Ions in the Radiolysis of Gaseous Ethylene

Gawlowski

Niedzielski

1974

Ber Bunsenges Phys Chem

View full text Add to dashboard Cite

The reactions of butyl ions in ethylene irradiated with 60CO γ‐rays in the gas phase were investigated using isopentane as a competitive reagent and ammonia as a proton scavenger. The presence of ions having a tertiary structure was established. The kinetic analysis of two independent sets of data gave, at 500 Torr, G = 0,185 and G = 0,20, respectively. Tert‐C4H9+ ions were found to be unreactive towards ethylene. The rate constant for this reaction was calculated as 8 · 10−14cm3 molecule−1 sec−1

show abstract

Kinetic mass spectrometric investigation of the reactions of t-C4H9+ ions with some simple polar molecules at thermal energies

Cited by 11 publications

References 5 publications

Bimolecular Reactions of Trapped Ions. VI. Ion–Molecule Reactions Involving CH₅⁺ and C₂H₅⁺

Bimolecular Reactions of Trapped Ions. VI. Ion–Molecule Reactions Involving CH₅⁺ and C₂H₅⁺

Ion-polar molecule collisions. Proton transfer reactions of H3+ and CH5+ to the geometric isomers of difluoroethylene, dichloroethylene, and difluorobenzene

Isomerization of C₄H₉⁺ Ions in the Radiolysis of Gaseous Ethylene

Contact Info

Product

Resources

About

Kinetic mass spectrometric investigation of the reactions of t-C4H9+ ions with some simple polar molecules at thermal energies

Cited by 11 publications

References 5 publications

Bimolecular Reactions of Trapped Ions. VI. Ion–Molecule Reactions Involving CH5+ and C2H5+

Bimolecular Reactions of Trapped Ions. VI. Ion–Molecule Reactions Involving CH5+ and C2H5+

Ion-polar molecule collisions. Proton transfer reactions of H3+ and CH5+ to the geometric isomers of difluoroethylene, dichloroethylene, and difluorobenzene

Isomerization of C4H9+ Ions in the Radiolysis of Gaseous Ethylene

Contact Info

Product

Resources

About

Bimolecular Reactions of Trapped Ions. VI. Ion–Molecule Reactions Involving CH₅⁺ and C₂H₅⁺

Bimolecular Reactions of Trapped Ions. VI. Ion–Molecule Reactions Involving CH₅⁺ and C₂H₅⁺

Isomerization of C₄H₉⁺ Ions in the Radiolysis of Gaseous Ethylene