Hydrogen-bond breaking and proton exchange in collisions of gaseous formic acid with liquid sulfuric acid

Science

Volumn 273, Issue 5273, 1996, Pages 333-335

  Klassen, Jane K ^a,b   Nathanson, Gilbert M ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

^b SRI INTERNATIONAL   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

FORMIC ACID; SULFURIC ACID;

ARTICLE; DIMERIZATION; HYDROGEN BOND; ION TRANSPORT; MOLECULAR INTERACTION; PRIORITY JOURNAL; PROTON TRANSPORT; SOLVATION;

EID: 0029972894     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.273.5273.333     Document Type: Article

References (24)

1. S. K. Chaudhuri and M. M. Sharma, Ind. Eng. Chem. Res. 30,339 (1991); D. R. Hanson and E. R. Lovejoy, Science 267, 1326 (1995).
2. S. K. Chaudhuri and M. M. Sharma, Ind. Eng. Chem. Res. 30,339 (1991); D. R. Hanson and E. R. Lovejoy, Science 267, 1326 (1995).
3. J. E. Hurst et al., Phys. Rev. Lett. 43, 1175 (1979); C. T. Rettner, E. K. Schweizer, C. B. Mullins, J. Chem. Phys. 90, 3800 (1989); M. E. Saecker and G. M. Nathanson, ibid. 99, 7056 (1993).
4. J. E. Hurst et al., Phys. Rev. Lett. 43, 1175 (1979); C. T. Rettner, E. K. Schweizer, C. B. Mullins, J. Chem. Phys. 90, 3800 (1989); M. E. Saecker and G. M. Nathanson, ibid. 99, 7056 (1993).
5. J. E. Hurst et al., Phys. Rev. Lett. 43, 1175 (1979); C. T. Rettner, E. K. Schweizer, C. B. Mullins, J. Chem. Phys. 90, 3800 (1989); M. E. Saecker and G. M. Nathanson, ibid. 99, 7056 (1993).
6. S. T. Govoni and G. M. Nathanson, J. Am. Chem. Soc. 116, 779 (1994).
7. See also J. H. Hu et al, J. Phys. Chem. 99, 8768 (1995); E. D. Guldan, L. R. Schindler, J. T. Roberts, ibid.,p. 16059; K. B. Eisenthal, Acc. Chem. Res. 26, 636 (1993).
8. See also J. H. Hu et al, J. Phys. Chem. 99, 8768 (1995); E. D. Guldan, L. R. Schindler, J. T. Roberts, ibid.,p. 16059; K. B. Eisenthal, Acc. Chem. Res. 26, 636 (1993).
9. See also J. H. Hu et al, J. Phys. Chem. 99, 8768 (1995); E. D. Guldan, L. R. Schindler, J. T. Roberts, ibid.,p. 16059; K. B. Eisenthal, Acc. Chem. Res. 26, 636 (1993).
10. M. Eigen, Angew. Chem. Int. Ed. Engl. 3, 1 (1964); K. Ando and J. T. Hynes, J. Mol. Liq. 64, 25 (1995); and references therein.
11. M. Eigen, Angew. Chem. Int. Ed. Engl. 3, 1 (1964); K. Ando and J. T. Hynes, J. Mol. Liq. 64, 25 (1995); and references therein.
12. 0. See M. Liler, Reaction Mechanisms in Sulfuric Acid (Academic Press, New York, 1971), p. 256.
13. Uptake measurements indicate that roughly 60% of the impinging formic acid molecules dissolve in and remain within the acid during the 0.05-s observation time of the surface (K. M. Fiehrer and G. M. Nathanson, in preparation).
14. R. A. Cox, J. Am. Chem. Soc. 96, 1059 (1974).
15. S. A. Lednovich and J. B. Fenn, AIChE J. 23, 454 (1977).
16. 2. See K. W. Smith, R. M. Noyes, P. G. Bowers, J. Phys. Chem. 87, 1514 (1983).
17. +.
18. The lower limit of 3:1 is imposed by the noise in the DCOOD spectrum. The ratio of the TD intensities at a 45° exit angle should reflect the angle-integrated TD ratio because the TD channels typically follow nearly identical, cosine-like angular distributions.
19. J. Chao and B. J. Zwolinski, J. Phys. Chem. Ref. Data 7, 363 (1978).
20. Enhanced nonpairwise, cooperative effects are expected to increase the basicity of the dimer over the monomer. R. Zhang and C. Lifshitz, J. Phys. Chem. 100, 960 (1996); A. E. Reed, L A. Curtiss, F. Weinhold, Chem. Rev. 88, 899 (1988).
21. Enhanced nonpairwise, cooperative effects are expected to increase the basicity of the dimer over the monomer. R. Zhang and C. Lifshitz, J. Phys. Chem. 100, 960 (1996); A. E. Reed, L A. Curtiss, F. Weinhold, Chem. Rev. 88, 899 (1988).
22. At lower impact energies, the monomer ion/dimer ion ratio increases as more dimers become trapped and dissociate into monomers.
23. I. Benjamin, M. A. Wilson, A. Pohorille, G. M. Nathanson, Chem. Phys. Lett. 243, 222 (1995).
24. We thank F. Weinhold for discussions concerning hydrogen bonding and K. Fiehrer for the formic acid uptake measurement. This work was supported by NSF (CHE-9417909) and Presidential Young Investigator and Dreyfus Teacher-Scholar Awards to G.M.N.