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Volumn 112, Issue 39, 2008, Pages 15449-15457

Evidence for interfacial [FDC1]- in collisions between DCl and F- in KF-glycerol solutions

Author keywords

[No Author keywords available]

Indexed keywords

FLUORIDE IONS; GAS PHASES; HALIDE IONS; HF EXCHANGES; HF MOLECULES; IN VACUUMS; INTERFACIAL REGIONS; RESIDENCE TIMES; SUBMICROSECOND; SURFACE REGIONS;

EID: 54249112875     PISSN: 19327447     EISSN: 19327455     Source Type: Journal    
DOI: 10.1021/jp805224p     Document Type: Article
Times cited : (8)

References (58)
  • 31
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    • K+F~ ion pairs may also be more surface-active than F- alone because of their lower effective charge, although computer simulations show fewer Na+Cl- pairs at the surface than in bulk water. See Jungwirth, P, Tobias, D. J. J. Phys. Chem B 2000, 104, 7702 In addition, ion pairing between F- and K+ may also reduce the reactivity of F, but our studies indicate that CaI 2 is more effective than NaI in catalyzing interfacial D → H exchange and DCl desorption at high concentrations, even though Ca2+ and I- are more likely to be paired than Na+ and I, See ref 22
    • -. See ref 22.
  • 35
    • 85178702377 scopus 로고    scopus 로고
    • Gly, is estimated from trends in Rondonini, S.; Longhi, P.; Mussini, P. R.; Mussini, T. Pure Appl. Chem. 1987, 59, 1693.
    • Gly, is estimated from trends in Rondonini, S.; Longhi, P.; Mussini, P. R.; Mussini, T. Pure Appl. Chem. 1987, 59, 1693.
  • 40
    • 0004047722 scopus 로고
    • 3rd ed, McGraw-Hill: New York
    • Pitzer, K. S. Thermodynamics, 3rd ed.; McGraw-Hill: New York, 1995.
    • (1995) S. Thermodynamics
    • Pitzer, K.1
  • 43
    • 0000391511 scopus 로고    scopus 로고
    • The residence time τhalf can be extracted from the postchopper spectra by measuring the ratio ITD(texp, ITD(texp, where J is the integrated signal intensity at two exposure times texp and texp, For a solution in which F- is in excess, ITD(texp, τ/texp, erfc((texp/τ)1/2) exp(texp/τ, 2(texp/τ)1/2-1, r is the time in which the outgoing HF flux reaches 57% of the incoming DCl flux, and τhalf, 0.6τ is the analogous 50% time. See also Appendix I of Shi, Q, Davidovits, P, Jayne, J. T, Worsnop, D. W, Kolb, C. E. J. Phys. Chem. A 1999, 103, 8812
    • half = 0.6τ is the analogous 50% time. See also Appendix I of Shi, Q.; Davidovits, P.; Jayne, J. T.; Worsnop, D. W.; Kolb, C. E. J. Phys. Chem. A 1999, 103, 8812.
  • 44
    • 54249109285 scopus 로고    scopus 로고
    • -1.
    • -1.
  • 45
    • 54249129228 scopus 로고    scopus 로고
    • -1 are obtained from calculations in ref 23 assuming that the viscosities of pure glycerol and the 0.5 M KF solutions are equal. The coefficients should drop by half in 2.5 M KP-glycerol, which is approximately twice as viscous as pure glycerol.
    • -1 are obtained from calculations in ref 23 assuming that the viscosities of pure glycerol and the 0.5 M KF solutions are equal. The coefficients should drop by half in 2.5 M KP-glycerol, which is approximately twice as viscous as pure glycerol.
  • 46
    • 36448996163 scopus 로고    scopus 로고
    • For recent studies of ion-water interactions, see also Park, S.; Feyer, M. D. Proc. Nat. Aca. Sci 2007, 104, 16731
    • (a) For recent studies of ion-water interactions, see also Park, S.; Feyer, M. D. Proc. Nat. Aca. Sci 2007, 104, 16731
  • 47
    • 36148935198 scopus 로고    scopus 로고
    • and. (b) Smith, J. D.; Saykally, R. J.; Geissler, P. L. J. Am. Chem. Soc. 2007, 129, 13847.
    • and. (b) Smith, J. D.; Saykally, R. J.; Geissler, P. L. J. Am. Chem. Soc. 2007, 129, 13847.
  • 52
    • 54249142066 scopus 로고    scopus 로고
    • The 103 s-1 estimate for the HF dissociation rate constant kf and a diffusion-limited recombination rate of kr, 4πRD, 3 × 108 M-1 s -1 for R, 10 Å and D, 5 × 10-7 cm2 s-1 yields a dissociation constant for HF in glycerol of Kacid, kf/kr ≈ 3 × 10-6, or approximately 100 times smaller than in water. The constant KGly ≈10-15.5 further yields a base dissociation constant of ∼1 × 10-10, which predicts a GlyO- concentration of ∼2 × 10-5 M in the 2 M KF solution. This value is close to the lower limit of the estimate of 10-4±1 using pH paper, as stated in the Experimental Procedure section
    • -4±1 using pH paper, as stated in the Experimental Procedure section.
  • 58
    • 54249098177 scopus 로고    scopus 로고
    • Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M. Advanced Inorganic Chemistry, 6th ed.; Wiley: New York, 1999; Appendix 4.
    • Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M. Advanced Inorganic Chemistry, 6th ed.; Wiley: New York, 1999; Appendix 4.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.